Controlled Synthesis of AB2 amphiphilic triarm star-shaped block copolymers by ring-opening polymerization

OpenAIRE

Petrova, Svetla; Riva, Raphaël; Jérôme, Christine; Lecomte, Philippe; Mateva, Rosa

2009-01-01

This paper describes the synthesis of a novel amphiphilic AB2 triarm star-shaped copolymer with A = non-toxic and biocompatible hydrophilic poly(ethylene oxide) (PEO) and B = biodegradable and hydrophobic poly(ε-caprolactone) (PCL). A series of AB2 triarm star-shaped copolymers with different molecular weights for the PCL block were successfully synthesized by a three-step procedure. α-methoxy-ω-epoxy-poly(ethylene oxide) (PEO-epoxide) was first synthesized by the nucleophilic substitution of...

Core–Shell Structure and Aggregation Number of Micelles Composed of Amphiphilic Block Copolymers and Amphiphilic Heterografted Polymer Brushes Determined by Small-Angle X-ray Scattering

Energy Technology Data Exchange (ETDEWEB)

Szymusiak, Magdalena; Kalkowski, Joseph; Luo, Hanying; Donovan, Alexander J.; Zhang, Pin; Liu, Chang; Shang, Weifeng; Irving, Thomas; Herrera-Alonso, Margarita; Liu, Ying (JHU); (IIT); (UIC)

2017-08-31

A large group of functional nanomaterials employed in biomedical applications, including targeted drug delivery, relies on amphiphilic polymers to encapsulate therapeutic payloads via self-assembly processes. Knowledge of the micelle structures will provide critical insights into design of polymeric drug delivery systems. Core–shell micelles composed of linear diblock copolymers poly(ethylene glycol)-b-poly(caprolactone) (PEG-b-PCL), poly(ethylene oxide)-b-poly(lactic acid) (PEG-b-PLA), as well as a heterografted brush consisting of a poly(glycidyl methacrylate) backbone with PEG and PLA branches (PGMA-g-PEG/PLA) were characterized by dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS) measurements to gain structural information regarding the particle morphology, core–shell size, and aggregation number. The structural information at this quasi-equilibrium state can also be used as a reference when studying the kinetics of polymer micellization.

Core–Shell Structure and Aggregation Number of Micelles Composed of Amphiphilic Block Copolymers and Amphiphilic Heterografted Polymer Brushes Determined by Small-Angle X-ray Scattering

Energy Technology Data Exchange (ETDEWEB)

Szymusiak, Magdalena [Department; Kalkowski, Joseph [Department; Luo, Hanying [Department; Donovan, Alexander J. [Department; Zhang, Pin [Department; Liu, Chang [Department; Shang, Weifeng [Department; Irving, Thomas [Department; Herrera-Alonso, Margarita [Department; Liu, Ying [Department; Department

2017-08-16

A large group of functional nanomaterials employed in biomedical applications, including targeted drug delivery, relies on amphiphilic polymers to encapsulate therapeutic payloads via self-assembly processes. Knowledge of the micelle structures will provide critical insights into design of polymeric drug delivery systems. Core–shell micelles composed of linear diblock copolymers poly(ethylene glycol)-b-poly(caprolactone) (PEG-b-PCL), poly(ethylene oxide)-b-poly(lactic acid) (PEG-b-PLA), as well as a heterografted brush consisting of a poly(glycidyl methacrylate) backbone with PEG and PLA branches (PGMA-g-PEG/PLA) were characterized by dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS) measurements to gain structural information regarding the particle morphology, core–shell size, and aggregation number. The structural information at this quasi-equilibrium state can also be used as a reference when studying the kinetics of polymer micellization.

Influence of the content of hard segments on the properties of novel urethane-siloxane copolymers based on a poly(ε-caprolactone-b-poly(dimethylsiloxane-b-poly(ε- caprolactone triblock copolymer

Directory of Open Access Journals (Sweden)

Antić Vesna V.

2011-01-01

Full Text Available A series of novel thermoplastic urethane-siloxane copolymers (TPUSs based on a α,ω-dihydroxy-[poly(ε-caprolactone-bpoly( dimethylsiloxane-b-poly(ε-caprolactone] (α,ω-dihydroxy-PCLPDMS- PCL triblock copolymer, 4,4?-methylenediphenyl diisocyanate (MDI and 1,4-butanediol (BD was synthesized. The effects of the content (9-63 wt. % of hard urethane segments and their degree of polymerization on the properties of the segmented TPUSs were investigated. The structure, composition and hard segment degree of polymerization of the hard segments were examined using 1H- and quantitative 13C-NMR spectroscopy. The degree of crystallinity of the synthesized copolymers was determined using wide-angle X-ray scattering (WAXS. The surface properties were evaluated by measuring the water contact angle and water absorption. In the series of the TPUSs, the average degree of polymerization of the hard segments was varied from 1.2 to 14.4 MDI-BD units. It was found that average values from 3.8 to 14.4 MDI-BD units were effective segment lengths for crystallization of hard segments, which resulted in an increase in the degree of microphase separation of the copolymers. Spherulite-like superstructures were observed in copolymer films by scanning electron microscopy (SEM, which are believed to arise from the crystallization of the hard segments and/or PCL segments, depending on the content of the hard segments. The surface of the copolymers became more hydrophobic with increasing weight fraction of PDMS. The synthesized copolymers based on a PCL-PDMS-PCL segment showed good thermal stability, which increased with increasing content of soft PDMS segments, as was confirmed by the value of the starting temperature of thermal degradation.

Dual patterning of a poly(acrylic acid) layer by electron-beam and block copolymer lithographies.

Science.gov (United States)

Pearson, Anthony C; Linford, Matthew R; Harb, John N; Davis, Robert C

2013-06-18

We show the controllable patterning of palladium nanoparticles in both one and two dimensions using electron-beam lithography and reactive ion etching of a thin film of poly(acrylic acid) (PAA). After the initial patterning of the PAA, a monolayer of polystyrene-b-poly-2-vinylpyridine micelles is spun cast onto the surface. A short reactive ion etch is then used to transfer the micelle pattern into the patterned poly(acrylic acid). Finally, PdCl2 is loaded from solution into the patterned poly(acrylic acid) features, and a reactive-ion etching process is used to remove the remaining polymer and form Pd nanoparticles. This method yields location-controlled patches of nanoparticles, including single- and double-file lines and nanoparticle pairs. A locational accuracy of 9 nm or less in one direction was achieved by optimizing the size of the PAA features.

Acute toxicity evaluation of in situ gel-forming controlled drug delivery system based on biodegradable poly(ε-caprolactone)-poly(ethylene glycol)-poly(ε-caprolactone) copolymer

International Nuclear Information System (INIS)

Fang Fang; Gong Changyang; Dong Pengwei; Fu Shaozhi; Gu Yingchun; Guo Gang; Zhao Xia; Wei Yuquan; Qian Zhiyong

2009-01-01

In this paper, biodegradable poly(ε-caprolactone)-poly(ethylene glycol)-poly(ε-caprolactone) (PCL-PEG-PCL) triblock copolymer was synthesized, and was characterized by FTIR, 1 H-NMR and GPC. The PCL-PEG-PCL/dimethyl sulfoxide (DMSO) solution displayed in situ gelling behavior when subcutaneously injected into the body. Toxicity tests and a histopathological study were performed in BALB/c mice. We focused mainly on acute organ toxicity of BALB/c mice by subcutaneous injection. In the acute toxicity test, the dose of subcutaneous injection was 5 g/kg body weight (b.w.), and the mice were observed continuously for 14 days. For the histopathological study, samples including heart, lung, liver, kidneys, spleen, stomach and intestine were histochemically prepared and stained with hematoxylin-eosin for histopathological examination. No mortality or significant signs of toxicity were observed during the whole observation period, and there is no significant lesion to be shown in histopathological study of major organs in the mice. Therefore, the maximal tolerance dose of dimethyl sulfoxide (DMSO) solution of PCL-PEG-PCL copolymer by subcutaneous injection was calculated to be higher than 5 g/kg b.w. Therefore, the PCL-PEG-PCL/DMSO system was thought to be non-toxic after subcutaneous injection, and it might be a candidate for an in situ gelling controlled drug delivery system.

Hydroxyapatite/poly(epsilon-caprolactone) double coating on magnesium for enhanced corrosion resistance and coating flexibility.

Science.gov (United States)

Jo, Ji-Hoon; Li, Yuanlong; Kim, Sae-Mi; Kim, Hyoun-Ee; Koh, Young-Hag

2013-11-01

Hydroxyapatite was deposited on pure magnesium (Mg) with a flexible poly(ε-caprolactone) interlayer to reduce the corrosion rate of Mg and enhance coating flexibility. The poly(ε-caprolactone) interlayer was uniformly coated on Mg by a spraying method, followed by hydroxyapatite deposition on the poly(ε-caprolactone) using an aerosol deposition method. In scanning electron microscopy observations, inorganic/organic composite-like structure was observed between the hydroxyapatite and poly(ε-caprolactone) layers, resulting from the collisions of hydroxyapatite particles into the poly(ε-caprolactone) matrix at the initial stage of the aerosol deposition. The corrosion resistance of the coated Mg was examined using potentiodynamic polarization tests. The hydroxyapatite/poly(ε-caprolactone) double coating remarkably improved the corrosion resistance of Mg in Hank's solution. In the in vitro cell tests, the coated Mg showed better cell adhesion compared with the bare Mg due to the reduced corrosion rate and enhanced biocompatibility. The stability and flexibility of hydroxyapatite/poly(ε-caprolactone) double coating was investigated by scanning electron microscopy inspections after the coated Mg was deformed. The hydroxyapatite coating on the poly(ε-caprolactone) interlayer revealed enhanced coating stability and flexibility without cracking or delamination during bending and stretching compared with the hydroxyapatite single coating. These results demonstrated that the hydroxyapatite/poly(ε-caprolactone) double coating significantly improved the surface corrosion resistance of Mg and enhanced coating flexibility for use of Mg as a biodegradable implant.

Preparation of a non-woven poly(ε-caprolactone) fabric with partially embedded apatite surface for bone tissue engineering applications by partial surface melting of poly(ε-caprolactone) fibers.

Science.gov (United States)

Kim, In Ae; Rhee, Sang-Hoon

2017-07-01

This article describes a novel method for the preparation of a biodegradable non-woven poly(ε-caprolactone) fabric with a partially embedded apatite surface designed for application as a scaffold material for bone tissue engineering. The non-woven poly(ε-caprolactone) fabric was generated by the electro-spinning technique and then apatite was coated in simulated body fluid after coating the PVA solution containing CaCl 2 ·2H 2 O. The apatite crystals were partially embedded or fully embedded into the thermoplastic poly(ε-caprolactone) fibers by controlling the degree of poly(ε-caprolactone) fiber surface melting in a convection oven. Identical apatite-coated poly(ε-caprolactone) fabric that did not undergo heat-treatment was used as a control. The features of the embedded apatite crystals were evaluated by FE-SEM, AFM, EDS, and XRD. The adhesion strengths of the coated apatite layers and the tensile strengths of the apatite coated fabrics with and without heat-treatment were assessed by the tape-test and a universal testing machine, respectively. The degree of water absorbance was assessed by adding a DMEM droplet onto the fabrics. Moreover, cell penetrability was assessed by seeding preosteoblastic MC3T3-E1 cells onto the fabrics and observing the degrees of cell penetration after 1 and 4 weeks by staining nuclei with DAPI. The non-woven poly(ε-caprolactone) fabric with a partially embedded apatite surface showed good water absorbance, cell penetrability, higher apatite adhesion strength, and higher tensile strength compared with the control fabric. These results show that the non-woven poly(ε-caprolactone) fabric with a partially embedded apatite surface is a potential candidate scaffold for bone tissue engineering due to its strong apatite adhesion strength and excellent cell penetrability. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 1973-1983, 2017. © 2017 Wiley Periodicals, Inc.

Influence of clay organic modifier on morphology and performance of poly(ε-caprolactone/clay nanocomposites

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Nikolić Marija S.

2015-01-01

Full Text Available Two series of poly(e-caprolactone nanocomposites with different organo-modified clays (1 to 8 wt% were prepared by the solution casting method. Organoclays with polar (Cloisite®C30B and nonpolar (Cloisite®C15A organic modifier and with different miscibility with poly(e-caprolactone matrix, were chosen. Exfoliated and/or intercalated nanocomposite’s structures were obtained by using high dilution and an ultrasonic treatment for the composite preparation. The effect of the surface modification and clay content on the morphology, mechanical and thermal properties of the nanocomposites was studied. Scanning electron microscopy excluded the formation of microcomposite. The wide-angle X-ray diffraction analysis revealed that the tendency toward exfoliated structure is higher for the Cloisite®C30B, which had better miscibility with poly(e-caprolactone matrix. Differences in spherulites’ sizes and morphology between two series of the nanocomposites were observed by the optical microscopy performed on as-casted films. Enthalpies of fusion and degrees of crystallinity were higher for nanocomposites than for neat poly(e-caprolactone and increase with the clay loading in both series, as a consequence of the clay nucleating effect. Decreased thermal stability of nanocomposites was ascribed to thermal instability of organic modifiers of the clays. The Halpin-Tsai model was used to compare the theoretically predicted values of the Young’s modulus with experimentally obtained ones in tensile tests.[Projekat Ministarstva nauke Republike Srbije, br. 172062

Unexpected differences between thermal and photoinitiated cationic curing of a diglycidyl ether of bisphenol A modified with a multiarm star poly(styrene-b-poly(ε-caprolactone polymer

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J. M. Morancho

2013-07-01

Full Text Available The effect of adding a multiarm star poly(styrene-b-poly(ε-caprolactone polymer on the cationic thermal and photoinitiated curing of diglycidyl ether of bisphenol A was studied. This star-polymer decelerated the thermal curing of diglycidyl ether of bisphenol A and modified the final structure of the epoxy matrix. The photocuring was influenced significantly by the addition of the multiarm star. When the proportion of this modifier added was 5%, much more time was necessary for complete photocuring (160 min at 40ºC. In the presence of 10% of modifier, the degree of photocuring reached was very low (0.196 at 120°C. A subsequent thermal post-curing was necessary to cure completely the system. During photocuring in presence of poly(styrene-b-poly(ε-caprolactone, the formation of dormant species, which are reactivated when the temperature increases, takes places. The kinetics of the thermal curing and the photocuring was analyzed using an isoconversional method due to the complexity of the reactive process. Applying this method, it has been confirmed the dependence of activation energy on the degree of conversion. The fracture morphology analyzed by scanning electron microscopy exhibited a second phase originated during photocuring by the presence of the modifier.

Toxicity evaluation of methoxy poly(ethylene oxide)-block-poly(ε-caprolactone) polymeric micelles following multiple oral and intraperitoneal administration to rats.

Science.gov (United States)

Binkhathlan, Ziyad; Qamar, Wajhul; Ali, Raisuddin; Kfoury, Hala; Alghonaim, Mohammed

2017-09-01

Methoxy poly(ethylene oxide)- block -poly(ɛ-caprolactone) (PEO- b -PCL) copolymers are amphiphilic and biodegradable copolymers designed to deliver a variety of drugs and diagnostic agents. The aim of this study was to synthesize PEO- b -PCL block copolymers and assess the toxic effects of drug-free PEO- b -PCL micelles after multiple-dose administrations via oral or intraperitoneal (ip) administration in rats. Assembly of block copolymers was achieved by co-solvent evaporation method. To investigate the toxicity profile of PEO- b -PCL micelles, sixty animals were divided into two major groups: The first group received PEO- b -PCL micelles (100 mg/kg) by oral gavage daily for seven days, while the other group received the same dose of micelles by ip injections daily for seven days. Twenty-four hours following the last dose, half of the animals from each group were sacrificed and blood and organs (lung, liver, kidneys, heart and spleen) were collected. Remaining animals were observed for further 14 days and was sacrificed at the end of the third week, and blood and organs were collected. None of the polymeric micelles administered caused any significant effects on relative organ weight, animal body weight, leucocytes count, % lymphocytes, liver and kidney toxicity markers and organs histology. Although the dose of copolymers used in this study is much higher than those used for drug delivery, it did not cause any significant toxic effects in rats. Histological examination of all the organs confirmed the nontoxic nature of the micelles.

Toxicity evaluation of methoxy poly(ethylene oxide-block-poly(ε-caprolactone polymeric micelles following multiple oral and intraperitoneal administration to rats

Directory of Open Access Journals (Sweden)

Ziyad Binkhathlan

2017-09-01

Full Text Available Methoxy poly(ethylene oxide-block-poly(ɛ-caprolactone (PEO-b-PCL copolymers are amphiphilic and biodegradable copolymers designed to deliver a variety of drugs and diagnostic agents. The aim of this study was to synthesize PEO-b-PCL block copolymers and assess the toxic effects of drug-free PEO-b-PCL micelles after multiple-dose administrations via oral or intraperitoneal (ip administration in rats. Assembly of block copolymers was achieved by co-solvent evaporation method. To investigate the toxicity profile of PEO-b-PCL micelles, sixty animals were divided into two major groups: The first group received PEO-b-PCL micelles (100 mg/kg by oral gavage daily for seven days, while the other group received the same dose of micelles by ip injections daily for seven days. Twenty-four hours following the last dose, half of the animals from each group were sacrificed and blood and organs (lung, liver, kidneys, heart and spleen were collected. Remaining animals were observed for further 14 days and was sacrificed at the end of the third week, and blood and organs were collected. None of the polymeric micelles administered caused any significant effects on relative organ weight, animal body weight, leucocytes count, % lymphocytes, liver and kidney toxicity markers and organs histology. Although the dose of copolymers used in this study is much higher than those used for drug delivery, it did not cause any significant toxic effects in rats. Histological examination of all the organs confirmed the nontoxic nature of the micelles.

Novel differential refractometry study of the enzymatic degradation kinetics of poly(ethylene oxide)-b-poly(epsilon-caprolactone) particles dispersed in water.

Science.gov (United States)

Lam, HiuFung; Gong, Xiangjun; Wu, Chi

2007-02-22

A poly(ethylene oxide)-b-poly(epsilon-caprolactone) (PEO-b-PCL) diblock copolymer was micronized into small micelle-like particles (approximately 80 nm) via dialysis-induced microphase inversion. The enzymatic biodegradation of the PCL portion of these particles in water was in situ investigated inside a recently developed novel differential refractometer. Using this refractometry method, we were able to monitor the real-time biodegradation via the refractive index change (Deltan) of the dispersion because Deltan is directly proportional to the particle mass concentration. We found that the degradation rate is proportional to either the polymer or enzyme concentration. Our results directly support previous speculation on the basis of the light-scattering data that the biodegradation follows the first-order kinetics for a given enzyme concentration. This study not only leads to a better understanding of the enzymatic biodegradation of PCL, but also demonstrates a novel, rapid, noninvasive, and convenient way to test the degradability of polymers.

Construction of an Immobilized Thermophilic Esterase on Epoxy Support for Poly(ε-caprolactone) Synthesis.

Science.gov (United States)

Ren, Hui; Xing, Zhen; Yang, Jiebing; Jiang, Wei; Zhang, Gang; Tang, Jun; Li, Quanshun

2016-06-18

Developing an efficient immobilized enzyme is of great significance for improving the operational stability of enzymes in poly(ε-caprolactone) synthesis. In this paper, a thermophilic esterase AFEST from the archaeon Archaeoglobus fulgidus was successfully immobilized on the epoxy support Sepabeads EC-EP via covalent attachment, and the immobilized enzyme was then employed as a biocatalyst for poly(ε-caprolactone) synthesis. The enzyme loading and recovered activity of immobilized enzyme was measured to be 72 mg/g and 10.4 U/mg using p-nitrophenyl caprylate as the substrate at 80 °C, respectively. Through the optimization of reaction conditions (enzyme concentration, temperature, reaction time and medium), poly(ε-caprolactone) was obtained with 100% monomer conversion and low number-average molecular weight (Mn enzyme exhibited excellent reusability, with monomer conversion values exceeding 75% during 15 batch reactions. Finally, poly(ε-caprolactone) was enzymatically synthesized with an isolated yield of 75% and Mn value of 3005 g/mol in a gram-scale reaction.

Mechanical properties of a waterborne pressure-sensitive adhesive with a percolating poly(acrylic acid)-based diblock copolymer network: effect of pH.

Science.gov (United States)

Gurney, Robert S; Morse, Andrew; Siband, Elodie; Dupin, Damien; Armes, Steven P; Keddie, Joseph L

2015-06-15

Copolymerizing an acrylic acid comonomer is often beneficial for the adhesive properties of waterborne pressure-sensitive adhesives (PSAs). Here, we demonstrate a new strategy in which poly(acrylic acid) (PAA) is distributed as a percolating network within a PSA film formed from a polymer colloid. A diblock copolymer composed of PAA and poly(n-butyl acrylate) (PBA) blocks was synthesized using reversible addition-fragmentation chain transfer (RAFT) polymerization and adsorbed onto soft acrylic latex particles prior to their film formation. The thin adsorbed shells on the particles create a percolating network that raises the elastic modulus, creep resistance and tensile strength of the final film. When the film formation occurs at pH 10, ionomeric crosslinking occurs, and high tack adhesion is obtained in combination with high creep resistance. The results show that the addition of an amphiphilic PAA-b-PBA diblock copolymer (2.0 wt.%) to a soft latex provides a simple yet effective means of adjusting the mechanical and adhesive properties of the resulting composite film. Copyright © 2015 Elsevier Inc. All rights reserved.

Construction of an Immobilized Thermophilic Esterase on Epoxy Support for Poly(ε-caprolactone Synthesis

Directory of Open Access Journals (Sweden)

Hui Ren

2016-06-01

Full Text Available Developing an efficient immobilized enzyme is of great significance for improving the operational stability of enzymes in poly(ε-caprolactone synthesis. In this paper, a thermophilic esterase AFEST from the archaeon Archaeoglobus fulgidus was successfully immobilized on the epoxy support Sepabeads EC-EP via covalent attachment, and the immobilized enzyme was then employed as a biocatalyst for poly(ε-caprolactone synthesis. The enzyme loading and recovered activity of immobilized enzyme was measured to be 72 mg/g and 10.4 U/mg using p-nitrophenyl caprylate as the substrate at 80 °C, respectively. Through the optimization of reaction conditions (enzyme concentration, temperature, reaction time and medium, poly(ε-caprolactone was obtained with 100% monomer conversion and low number-average molecular weight (Mn < 1300 g/mol. Further, the immobilized enzyme exhibited excellent reusability, with monomer conversion values exceeding 75% during 15 batch reactions. Finally, poly(ε-caprolactone was enzymatically synthesized with an isolated yield of 75% and Mn value of 3005 g/mol in a gram-scale reaction.

Block copolymers of poly(l-lactide) and poly(e-caprolactone) or poly(ethylene glycol) prepared by reactive extrusion

NARCIS (Netherlands)

Stevels, W.M.; Bernard, A.; van de Witte, P.; van de Witte, P.; Dijkstra, Pieter J.; Feijen, Jan

1996-01-01

Blends of poly(L-lactide) (PLLA) and poly(-caprolactone) (PCL) were prepared in a co-rotating twin screw miniextruder (40 rpm, 200°). It was attempted to prepare multiblock copolymers by allowing a controlled number of transesterification reactions. Various cat-alysts (n-Bu3SnOMe, Sn(Oct)2,

Novel self-associating poly(ethylene oxide)-b-poly(epsilon-caprolactone) based drug conjugates and nano-containers for paclitaxel delivery.

Science.gov (United States)

Shahin, Mostafa; Lavasanifar, Afsaneh

2010-04-15

Poly(ethylene oxide)-block-poly(epsilon-caprolactone) (PEO-b-PCL) copolymers bearing paclitaxel (PTX) side groups on PCL (PEO-b-P(CL-PTX) were synthesized and assembled to particles of 123 nm average diameter. At 20% (w/w) PTX to polymer conjugation, PEO-b-P(CL-PTX) demonstrated only 5.0 and 6.7% PTX release after 72 h incubation at pH 7.4 and 5.0, respectively, but revealed signs of chain cleavage at pH 5.0. The cytotoxicity of PEO-b-P(CL-PTX) against MDA-MB-435 cancer cells increased as incubation time was raised from 72 to 96 h (IC(50) of 680 and 475 ng/mL, respectively), but it was still significantly lower than the cytotoxicity of free PTX (IC(50) of 3.5 ng/mL at 72 h). In further studies, micelles of PEO-b-PCL and those bearing benzyl or PTX on PCL were used for physical encapsulation of PTX, where maximum level of loading was achieved by PEO-b-P(CL-PTX) (2.22%, w/w). The release of PTX from this carrier was rapid; however. The in vitro cytotoxicity of physically loaded PTX was independent of carrier and similar to that of free PTX. This was attributed to the low concentration of polymers which fell below their critical micellar concentration in the cytotoxicity study. The results point to the potential of chemically tailored PEO-b-PCL for optimum PTX solubilization and delivery. Copyright 2010 Elsevier B.V. All rights reserved.

Biodegradation of poly(ε-caprolactone in natural water environments

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Heimowska Aleksandra

2017-03-01

Full Text Available The environmental degradation of poly(ε-caprolactone[PCL] in natural fresh water (pond and in The Baltic Sea is presented in this paper. The characteristic parameters of both environments were measured during experiment and their influence on the biodegradation of the samples was discussed. The loss of weight and changes of surface morphology of polymer samples were tested during the period of incubation. The poly(ε-caprolactone was more biodegradable in natural sea water than in pond. PCL samples were completely assimilated over the period of six weeks incubation in The Baltic Sea water, but after forty two weeks incubation in natural fresh water the polymer weight loss was about 39%. The results have confirmed that the investigated polymers are susceptible to an enzymatic attack of microorganisms, but their activity depends on environments.

Polyelectrolyte Complex Nanoparticles of Poly(ethyleneimine) and Poly(acrylic acid): Preparation and Applications

OpenAIRE

Martin Müller; Bernd Keßler; Sebastian Poeschla; Bernhard Torger; Johanna Fröhlich

2011-01-01

In this contribution we outline polyelectrolyte (PEL) complex (PEC) nanoparticles, prepared by mixing solutions of the low cost PEL components poly(ethyleneimine) (PEI) and poly(acrylic acid) (PAC). It was found, that the size and internal structure of PEI/PAC particles can be regulated by process, media and structural parameters. Especially, mixing order, mixing ratio, PEL concentration, pH and molecular weight, were found to be sensible parameters to regulate the size (diameter) of spherica...

Enhanced protein retention on poly(caprolactone) via surface initiated polymerization of acrylamide

International Nuclear Information System (INIS)

Ma, Yuhao; Cai, Mengtan; He, Liu; Luo, Xianglin

2016-01-01

Graphical abstract: - Highlights: • Dense package of poly(acrylamide) on poly(caprolactone) surface was achieved by surface-initiated atom transfer radical polymerization. • Poly(acrylamide) grafted surface exhibited high protein retention ability. • Loaded protein was resistant to detachment and maintained its structure without denaturation. - Abstract: To enhance the biocompatibility or extend the biomedical application of poly(caprolactone) (PCL), protein retention on PCL surface is often required. In this study, poly(acrylamide) (PAAm) brushes were grown from PCL surface via surface-initiated atom transfer radical polymerization (SI-ATRP) and served as a protein-capturing platform. Grafted PAAm was densely packed on surface and exhibited superior protein retention ability. Captured protein was found to be resistant to washing under detergent environment. Furthermore, protein structure after being captured was investigated by circular dichroism (CD) spectroscopy, and the CD spectra verified that secondary structure of captured proteins was maintained, indicating no denaturation of protein happened for retention process.

Adsorption and Aqueous Lubricating Properties of Charged and Neutral Amphiphilic Diblock Copolymers at a Compliant, Hydrophobic Interface

DEFF Research Database (Denmark)

Røn, Troels; Javakhishvili, Irakli; Jankova Atanasova, Katja

2013-01-01

We have investigated the adsorption and lubricating properties of neutral and charged amphiphilic diblock copolymers at a hydrophobic polydimethylsiloxane (PDMS) interface in an aqueous environment. The diblock copolymers consist of a hydrophilic block of either neutral poly(ethylene glycol) (PEG......) or negatively charged poly(acrylic acid) (PAA) and of a hydrophobic block of polystyrene (PS) or poly(2-methoxyethyl acrylate) (PMEA), thus generating PEG-b-X or PAA-b-X, where X block is either PS or PMEA. The molecular weight ratios were roughly 1:1 with each block ca. 5 kDa. Comparing the neutral PEG...... effective adsorption only when PMEA was employed as the anchoring block. For PAA-b-PS, the poor adsorption properties are chiefly attributed to micellization due to the high interfacial tension between the PS core and water. The poor lubricating properties of PAA-b-PS diblock copolymer for a PDMS...

Pervaporation of alcohol-toluene mixtures through polymer blend membranes of poly(acrylic acid) and poly(vinyl alcohol)

NARCIS (Netherlands)

Park, H.C.; Park, H.; Meertens, R.M.; Meertens, R.M.; Mulder, M.H.V.; Smolders, C.A.; Smolders, C.A.

1994-01-01

Homogeneous membranes were prepared by blending poly(acrylic acid) with poly(vinyl alcohol). These blend membranes were evaluated for the selective separation of alcohols from toluene by pervaporation. The flux and selectivity of the membranes were determined both as a function of the blend

Nanoformulation of D-α-tocopheryl polyethylene glycol 1000 succinate-b-poly(ε-caprolactone-ran-glycolide) diblock copolymer for breast cancer therapy.

Science.gov (United States)

Huang, Laiqiang; Chen, Hongbo; Zheng, Yi; Song, Xiaosong; Liu, Ranyi; Liu, Kexin; Zeng, Xiaowei; Mei, Lin

2011-10-01

The purpose of this research was to develop formulation of docetaxel-loaded biodegradable TPGS-b-(PCL-ran-PGA) nanoparticles for breast cancer chemotherapy. A novel diblock copolymer, d-α-tocopheryl polyethylene glycol 1000 succinate-b-poly(ε-caprolactone-ran-glycolide) [TPGS-b-(PCL-ran-PGA)], was synthesized from ε-caprolactone, glycolide and d-α-tocopheryl polyethylene glycol 1000 succinate by ring-opening polymerization using stannous octoate as catalyst. The obtained copolymers were characterized by (1)H NMR, GPC and TGA. The docetaxel-loaded TPGS-b-(PCL-ran-PGA) nanoparticles were prepared and characterized. The data showed that the fluorescence TPGS-b-(PCL-ran-PGA) nanoparticles could be internalized by MCF-7 cells. The TPGS-b-(PCL-ran-PGA) nanoparticles achieved significantly higher level of cytotoxicity than commercial Taxotere®. MCF-7 xenograft tumor model on SCID mice showed that docetaxel formulated in the TPGS-b-(PCL-ran-PGA) nanoparticles could effectively inhibit the growth of tumor over a longer period of time than Taxotere® at the same dose. In conclusion, the TPGS-b-(PCL-ran-PGA) copolymer could be acted as a novel and potential biologically active polymeric material for nanoformulation in breast cancer chemotherapy. This journal is © The Royal Society of Chemistry 2011

Chitosan/poly(epsilon-caprolactone) blend scaffolds for cartilage repair

NARCIS (Netherlands)

Neves, Sara C.; Moreira Teixeira, Liliana; Moroni, Lorenzo; Reis, Rui L.; van Blitterswijk, Clemens; Alves, Natália M.; Karperien, Hermanus Bernardus Johannes; Mano, João F.

2011-01-01

Chitosan (CHT)/poly(ɛ-caprolactone) (PCL) blend 3D fiber-mesh scaffolds were studied as possible support structures for articular cartilage tissue (ACT) repair. Micro-fibers were obtained by wet-spinning of three different polymeric solutions: 100:0 (100CHT), 75:25 (75CHT) and 50:50 (50CHT) wt.%

Effect of Grafted Hydroquinone on the Acid-Base Properties of Poly(acrylic acid in the Presence of Copper (II

Directory of Open Access Journals (Sweden)

Nabila Bensacia

2015-01-01

Full Text Available Potentiometric titration of poly(acrylic acid and hydroquinone-functionalized poly(acrylic acid was conducted in the presence of copper (II. The effects of hydroquinone functionalizing and copper (II complexing on the potentiometric titration of poly(acrylic acid were studied in an ionic environment and in its absence. Henderson-Hasselbalch equation was applied to assess its validity for this titration. Coordination number and the stability constants of the copper- (II-complexed polymers were determined, and results showed the formation of mostly monodentate and bidentate copper- (II-polymer complexes.

Preparing poly (caprolactone) micro-particles through solvent-induced phase separation

DEFF Research Database (Denmark)

Li, Xiaoqiang; Kanjwal, Muzafar Ahmed; Stephansen, Karen

2012-01-01

Poly (caprolactone) (PCL) particles with the size distribution from 1 to 100 μm were prepared through solvent-induced phase separation, in which polyvinyl-alcohol (PVA) was used as the matrix-forming polymer to stabilize PCL particles. The cloud point data of PCL-acetone-water was determined...

Gelatinized and nongelatinized corn starch/ poly(epsilon-caprolactone) blends: characterization by rheological, mechanical and morphological properties

OpenAIRE

Rosa,Derval S.; Guedes,Cristina G. F.; Pedroso,Andréa G.

2004-01-01

Poly(epsilon-caprolactone)/corn starch blends containing 25, 50 and 75 wt.% starch were prepared by mechanical processing and characterized by the melt flow index (MFI), tensile test and scanning electron microscopy (SEM). For comparison, starch was used in gelatinized and nongelatinized forms and was also characterized by viscography. The addition of starch to poly(epsilon-caprolactone) reduced the MFI values, the tensile strength and the elongation at break, whereas the modulus increased. T...

Galactosylated poly(ε-caprolactone) membrane promoted liver-specific functions of HepG2 cells in vitro

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yan, E-mail: zhang_yan@ecust.edu.cn [The Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 (China); Zhang, Yi [The Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 (China); Chen, Min; Zhou, Yan [The State Key Laboratory of Bioreactor Engineering, School of Bioengineering, East China University of Science and Technology, Shanghai, 200237 (China); Lang, Meidong, E-mail: mdlang@ecust.edu.cn [The Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 (China)

2014-08-01

The lack of pendant functional groups on the PCL backbone has been a great challenge for surface bioactivation of poly(ε-caprolactone) (PCL). In the present study, covalently galactosylated PCL (GPCL) was developed through coupling between the amino-functionalized PCL (NPCL) and the lactobionic acid (LA) and its potential application in maintenance of physiological functions of HepG2 cells was further evaluated. The structure and properties of GPCL were explored by {sup 1}H NMR, FT-IR, GPC and DSC. Moreover, the incorporation of galactose ligands onto GPCL membranes not only promoted higher wettability, but also radically changed surface morphology in comparison with PCL and NPCL according to the contact angle measurement and atomic force microscopy. When HepG2 cells were seeded onto these membranes, the cells on GPCL membranes showed more pronounced cell adhesion and tended to form aggregates during the initial adhesion stage and then progressively grew into multi-layer structures compared to those without galactose ligands by the observation with fluorescence microscope and scanning electron microscopy. Furthermore, live–dead assay and functional tests demonstrated that HepG2 cells on GPCL membranes had superior viability and maintained better liver-specific functions. Collectively, GPCL has great potential for hepatic tissue engineering scaffolds. - Graphical abstract: The specific recognition between the galactose ligands on the galactosylated poly(ε-caprolactone) membrane and the ASGPR on the HepG2 cell surface. The galactosylated poly(ε-caprolactone) membranes improved the cell-matrix interaction. The galactosylated functionalized PCL scaffold is a potential candidate for liver tissue engineering. - Highlights: • The specific recognition between the galactose ligands on the galactosylated poly(ε-caprolactone) membrane and the ASGPR on the HepG2 cell surface. • The galactosylated poly(ε-caprolactone) membranes improved the cell-matrix interaction. �

Nanostructures and surface hydrophobicity of self-assembled thermosets involving epoxy resin and poly(2,2,2-trifluoroethyl acrylate)-block-poly(ethylene oxide) amphiphilic diblock copolymer.

Science.gov (United States)

Yi, Fangping; Zheng, Sixun; Liu, Tianxi

2009-02-19

Poly(2,2,2-trifluoroethyl acrylate)-block-poly(ethylene oxide) (PTFEA-b-PEO) amphiphilic diblock copolymer was synthesized via the reversible addition-fragmentation transfer polymerization of 2,2,2-triffluroethyl acrylate with dithiobenzoyl-terminated poly(ethylene oxide) as a chain-transfer agent. The amphiphilic diblock copolymer was incorporated into epoxy resin to prepare the nanostructured epoxy thermosets. The nanostructures were investigated by means of atomic force microscopy, small-angle X-ray scattering, and dynamic mechanical analysis. In terms of the miscibility of the subchains of the block copolymer with epoxy after and before curing reaction, it is judged that the formation of the nanostructures follows the mechanism of self-assembly. The static contact angle measurements indicate that the nanostructured thermosets containing PTFEA-b-PEO diblock copolymer displayed a significant enhancement in surface hydrophobicity as well as a reduction in surface free energy. The improvement in surface properties was ascribed to the enrichment of the fluorine-containing subchain (i.e., PTFEA block) of the amphiphilic diblock copolymer on the surface of the nanostructured thermosets, which was evidenced by surface atomic force microscopy and energy-dispersive X-ray spectroscopy.

Synthesis of poly({epsilon}-caprolactone) by iodine: an interesting route to synthesize bio reabsorbable polymers via green chemistry

Energy Technology Data Exchange (ETDEWEB)

Silva, Lidiane G. da; Leyva, Maria E.; Barrak, Elcio R.; Sachs, Daniela; Queiroz, Alvaro A.A. de [Centro de Investigaco e Inovacao de Materiais Funcionais Avancados, Universidade Federal de Itajuba - UNIFEI, MG (Brazil); Barca, Luiz F. [Laboratorio de Separacao de Fases, Instituto de Engenharia Mecanica, Universidade Federal de Itajuba - UNIFEI, MG (Brazil)

2011-07-01

The poly({epsilon}-caprolactone) (PCL) and their copolymers, are used as biomaterial for tissue engineering and drug delivery system. In the present study the thermal characterization (differential scanning calorimetry, DSC), structural characterization by NMR {sup 1}H {sup 13}C and FTIR spectroscopy, determination of particle size and morphology of Poly(e-caprolactone) synthesized by change transfer complex method using iodine as initiation, were investigated. The FT-IR spectra shows strong of the carbonyl stretching mode around 1720,4 cm.1. The particle size was 2,8 {mu}m and 1,8 {mu}m . The scanning electronic microscopy (SEM) showed porous larger than 2 {mu}m and DSC measuring conferred Tm 57,8 degree C for PCL and 53,04 degree C for SPCL(Sigma-Aldrich- Poly(e-caprolactone).Thus the polymerisation of e- caprolactone is a very clean, easy and efficient method to obtain small polymers of polycaprolactone with controlled molecular weight may be obtained. (author)

Anomalous impact strength for layered double hydroxide-palmitate/poly(e-caprolactone) nanocomposites

CSIR Research Space (South Africa)

Moyo, Lumbidzani

2014-11-01

Full Text Available Inherent physical properties and commercial availability makes poly(e-caprolactone) (PCL) very attractive as a potential substitute material for nondegradable polymers for commodity applications. However, a balance of toughness and stiffness...

Formation of nanophases in epoxy thermosets containing amphiphilic block copolymers with linear and star-like topologies.

Science.gov (United States)

Wang, Lei; Zhang, Chongyin; Cong, Houluo; Li, Lei; Zheng, Sixun; Li, Xiuhong; Wang, Jie

2013-07-11

In this work, we investigated the effect of topological structures of block copolymers on the formation of the nanophase in epoxy thermosets containing amphiphilic block copolymers. Two block copolymers composed of poly(ε-caprolactone) (PCL) and poly(2,2,2-trifluoroethyl acrylate) (PTFEA) blocks were synthesized to possess linear and star-shaped topologies. The star-shaped block copolymer composed a polyhedral oligomeric silsesquioxane (POSS) core and eight poly(ε-caprolactone)-block-poly(2,2,2-trifluoroethyl acrylate) (PCL-b-PTFEA) diblock copolymer arms. Both block copolymers were synthesized via the combination of ring-opening polymerization and reversible addition-fragmentation chain transfer/macromolecular design via the interchange of xanthate (RAFT/MADIX) process; they were controlled to have identical compositions of copolymerization and lengths of blocks. Upon incorporating both block copolymers into epoxy thermosets, the spherical PTFEA nanophases were formed in all the cases. However, the sizes of PTFEA nanophases from the star-like block copolymer were significantly lower than those from the linear diblock copolymer. The difference in the nanostructures gave rise to the different glass transition behavior of the nanostructured thermosets. The dependence of PTFEA nanophases on the topologies of block copolymers is interpreted in terms of the conformation of the miscible subchain (viz. PCL) at the surface of PTFEA microdomains and the restriction of POSS cages on the demixing of the thermoset-philic block (viz. PCL).

Effect of halloysite nanotubes on the thermal degradation behaviour of poly(.epsilon.-caprolactone)/poly(lactic acid) microfibrillar composites

Czech Academy of Sciences Publication Activity Database

Luyt, A. S.; Kelnar, Ivan

2017-01-01

Roč. 60, July (2017), s. 166-172 ISSN 0142-9418 R&D Projects: GA ČR(CZ) GA13-15255S Institutional support: RVO:61389013 Keywords : poly(lactic acid) * poly(epsilon-caprolactone) * halloysite nanotubes Subject RIV: JI - Composite Materials OBOR OECD: Composites (including laminates, reinforced plastics, cermets, combined natural and synthetic fibre fabrics Impact factor: 2.464, year: 2016

Thermoresponsive behaviour of terpolymers containing poly(ethylene oxide), poly(2-ethyl-2-oxazoline) and poly(.epsilon.-caprolactone) blocks in aqueous solutions: an NMR study

Czech Academy of Sciences Publication Activity Database

Konefal, Rafal; Spěváček, Jiří; Jäger, Eliezer; Petrova, Svetlana

2016-01-01

Roč. 294, č. 11 (2016), s. 1717-1726 ISSN 0303-402X R&D Projects: GA ČR(CZ) GA15-13853S; GA MŠk(CZ) 7F14009 Institutional support: RVO:61389013 Keywords : thermoresponsive polymer * terpolymer containing poly(ethylene oxide), poly(2-ethyl-2-oxazoline) and poly(epsilon-caprolactone) blocks * nanoparticles Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.723, year: 2016

An efficient Trojan delivery of tetrandrine by poly(N-vinylpyrrolidone-block-poly(ε-caprolactone (PVP-b-PCL nanoparticles shows enhanced apoptotic induction of lung cancer cells and inhibition of its migration and invasion

Directory of Open Access Journals (Sweden)

Xu H

2013-12-01

Full Text Available Huae Xu,1,2 Zhibo Hou,3 Hao Zhang,4 Hui Kong,2 Xiaolin Li,4 Hong Wang,2 Weiping Xie21Department of Pharmacy, 2Department of Respiratory Medicine, The First Affiliated Hospital of Nanjing Medical University, Nanjing, People's Republic of China; 3First Department of Respiratory Medicine, Nanjing Chest Hospital, Nanjing, People's Republic of China; 4Department of Geriatric Gastroenterology, The First Affiliated Hospital of Nanjing Medical University, Nanjing, People's Republic of ChinaAbstract: Earlier studies have demonstrated the promising antitumor effect of tetrandrine (Tet against a series of cancers. However, the poor solubility of Tet limits its application, while its hydrophobicity makes Tet a potential model drug for nanodelivery systems. We report on a simple way of preparing drug-loaded nanoparticles formed by amphiphilic poly(N-vinylpyrrolidone-block-poly(ε-caprolactone (PVP-b-PCL copolymers with Tet as a model drug. The mean diameters of Tet-loaded PVP-b-PCL nanoparticles (Tet-NPs were between 110 nm and 125 nm with a negative zeta potential slightly below 0 mV. Tet was incorporated into PVP-b-PCL nanoparticles with high loading efficiency. Different feeding ratios showed different influences on sizes, zeta potentials, and the drug loading efficiencies of Tet-NPs. An in vitro release study shows the sustained release pattern of Tet-NPs. It is shown that the uptake of Tet-NPs is mainly mediated by the endocytosis of nanoparticles, which is more efficient than the filtration of free Tet. Further experiments including fluorescence activated cell sorting and Western blotting indicated that this Trojan strategy of delivering Tet in PVP-b-PCL nanoparticles via endocytosis leads to enhanced induction of apoptosis in the non-small cell lung cancer cell A549 line; enhanced apoptosis is achieved by inhibiting the expression of anti-apoptotic Bcl-2 and Bcl-xL proteins. Moreover, Tet-NPs more efficiently inhibit the ability of cell migration and

Enhancement of interfacial adhesion between starch and grafted poly(ε-caprolactone).

Science.gov (United States)

Ortega-Toro, Rodrigo; Santagata, Gabriella; Gomez d'Ayala, Giovanna; Cerruti, Pierfrancesco; Talens Oliag, Pau; Chiralt Boix, M Amparo; Malinconico, Mario

2016-08-20

The use of a modified poly(ε-caprolactone) (gPCL) to enhance polymer miscibility in films based on thermoplastic starch (S) and poly(ε-caprolactone) is reported. PCL was functionalized by grafting with maleic anyhdride (MA) and/or glycidyl methacrylate (GMA) by reactive blending in a batch mixer. gPCL based materials were analysed in terms of their grafting degree, structural and thermal properties. Blends based on starch and PCL (wt. ratio 80:20) with including gPCL (0, 2.5 and 5wt.%), as a compatibilizer, were obtained by extrusion and compression moulding, and their structural, thermal, mechanical and barrier properties were investigated. Blends containing gPCL evidenced better interfacial adhesion between starch and PCL domains, as deduced from both structural (XRD, FTIR, SEM) and bulk properties (DSC, TGA). Moreover, grafted PCL-based compatibilizers greatly improved functional properties of S-PCL blend films, as pointed out from mechanical performance and higher barrier properties, valuable to meet the food packaging requirements. Copyright © 2016 Elsevier Ltd. All rights reserved.

Chemically imaging the effects of the addition of nanofibrillated cellulose on the distribution of poly(acrylic acid) in poly(vinyl alcohol)

Science.gov (United States)

Craig Clemons; Julia Sedlmair; Barbara Illman; Rebecca Ibach; Carol Hirschmugl

2013-01-01

The distribution of poly(acrylic acid) (PAA) in model laminates of nanocellulose and poly(vinyl alcohol) (PVOH) was investigated by FTIR chemical imaging. The method was effective in spatially discerning the three components of the composite. PAA can potentially improve the performance of nanocellulose reinforced PVOH by not only crosslinking the PVOH matrix but also...

Extraction of metal cations by polyterephthalamide microcapsules containing a poly(acrylic acid) gel.

Science.gov (United States)

Laguecir, A; Ernst, B; Frère, Y; Danicher, L; Burgard, M

2002-01-01

Polyterephthalamide microcapsules containing a poly(acrylic acid) gel as a macromolecular ligand (PAA-CAPS) were prepared using an original two step polymerization process in a water-in-oil inverse emulsion system. A polyamide microcapsule containing acrylic acid, initiator and cross-linking agent, is formed by interfacial polycondensation of terephthaloyl dichloride with hexamethylenediamine. In situ radical polymerization of the microcapsule core acrylic acid is initiated to obtain encapsulated poly(acrylic acid) gel. Reference polyamide microcapsules, i.e. without ligand (CAPS), were also synthesized. The mean diameter of synthesized microcapsules was 210 microm, and the microcapsule wall thickness was evaluated by SEM and TEM observations of microcapsule cross-section cuts. The microcapsule water content was determined by thermogravimetric experiments. The extractabilities of Cu(II), Ni(II), Co(II) and Zn(II) into PAA-CAPS were examined. The stripping of the various cations can be promoted in diluted hydrochloric acid solutions.

Study on the crystallization of multiarm stars with a poly(ethyleneimine) core and poly(ϵ-caprolactone) arms of different length

Energy Technology Data Exchange (ETDEWEB)

Díaz, Angélica; Bacaicoa, Anna; Casas, Maria Teresa; Franco, Lourdes [Departament d’Enginyeria Química, Universitat Politècnica de Catalunya, Av. Diagonal 647, Barcelona E-08028 (Spain); Serra, Angels [Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili. C. Marcel.lí Domingo, s/n. Campus Sescelades, Tarragona 43007 (Spain); Puiggalí, Jordi, E-mail: Jordi.Puiggali@upc.edu [Departament d’Enginyeria Química, Universitat Politècnica de Catalunya, Av. Diagonal 647, Barcelona E-08028 (Spain)

2015-05-10

Highlights: • Isothermal crystallization kinetics of multiarm stars. • Influence of the length of poly(ϵ-caprolactone) arms on crystallization kinetics. • Influence of the length of poly(ϵ-caprolactone) arms on secondary nucleation constant. • Crystallization of mixtures of stars having different arm lengths. - Abstract: Crystallization of multiarm star systems constituted by a core of poly(ethyleneimine) (PEI) and arms of poly(ϵ-caprolactone) (PCL) was studied by transmission electron microscopy, calorimetry and optical microscopy techniques. Three systems differing on the degree of polymerization of PCL were studied as well as binary mixtures constituted by systems differing on the length of PCL arms. Samples were able to crystallize from both diluted solutions and the melt state giving rise to well-formed lamellae and spherulites, respectively. Lamellae of samples with large PCL arms were highly regular and corresponded to elongated hexagonal crystals with an aspect ratio that decreased with the length of PCL arms. A significant decrease on equilibrium melting temperatures, degree of crystallinity and glass transition temperature was detected for samples having short PCL arms. Crystallization kinetics were also highly influenced by the length of PCL arms, being both nucleation density and secondary nucleation constant increased as the length of PCL arms decreased. Crystallization of star mixtures having different PCL lengths was determined by the larger arms since they initiated the process and subsequently shorter arms were progressively incorporated. A thermal nucleation was characteristic of multiarm star mixtures due to the different crystallization temperature ranges of samples with large and short PCL arms, whereas samples with a homogeneous arm length rendered an athermal nucleation.

Radiation Synthesis of Poly(N-Vinyl Pyrrolidone) Nanogels and Nanoscale Grafting of Poly(Acrylic Acid) from Cellulose

Energy Technology Data Exchange (ETDEWEB)

Guven, Olgun; Isik, Semiha Duygu; Barsbay, Murat [Hacettepe University, Department of Chemistry, 06800 Ankara (Turkey)

2010-07-01

Ionizing radiation has long been known to be a very useful tool for the preparation of nanogels. Although preparation is straightforward, the control of the sizes of nanogels has been a challenging issue. This report shows the results of our work on using radiation for the synthesis of PVP nanogels in the range of 40-200nm by making use of the principles of solution thermodynamics of aqueous polymer solutions. Nanoscale grafting of responsive polymers however has been of scientific and industrial importance due to fine control of the molecular weight and molecular weight distribution of grafted polymers. The second part of this report deals with the grafting of poly(acrylic acid) onto the surface of cellulose, thus imparting pH response to the substrate. The use of radiation as a constant source of radical generation and Reversible-Addition-Fragmentation-Chain transfer agents for the control of free radical polymerization provided a full control over the molecular weight and distribution of poly(acrylic acid) grafts on cellulose. (author)

Radiation Synthesis of Poly(N-Vinyl Pyrrolidone) Nanogels and Nanoscale Grafting of Poly(Acrylic Acid) from Cellulose

International Nuclear Information System (INIS)

Guven, Olgun; Isik, Semiha Duygu; Barsbay, Murat

2010-01-01

Ionizing radiation has long been known to be a very useful tool for the preparation of nanogels. Although preparation is straightforward, the control of the sizes of nanogels has been a challenging issue. This report shows the results of our work on using radiation for the synthesis of PVP nanogels in the range of 40-200nm by making use of the principles of solution thermodynamics of aqueous polymer solutions. Nanoscale grafting of responsive polymers however has been of scientific and industrial importance due to fine control of the molecular weight and molecular weight distribution of grafted polymers. The second part of this report deals with the grafting of poly(acrylic acid) onto the surface of cellulose, thus imparting pH response to the substrate. The use of radiation as a constant source of radical generation and Reversible-Addition-Fragmentation-Chain transfer agents for the control of free radical polymerization provided a full control over the molecular weight and distribution of poly(acrylic acid) grafts on cellulose. (author)

Tailored Design of Bicontinuous Gyroid Mesoporous Carbon and Nitrogen-Doped Carbon from Poly(ethylene oxide-b-caprolactone) Diblock Copolymers.

Science.gov (United States)

Chu, Wei-Cheng; Bastakoti, Bishnu Prasad; Kaneti, Yusuf Valentino; Li, Jheng-Guang; Alamri, Hatem R; Alothman, Zeid A; Yamauchi, Yusuke; Kuo, Shiao-Wei

2017-10-04

Highly ordered mesoporous resol-type phenolic resin and the corresponding mesoporous carbon materials were synthesized by using poly(ethylene oxide-b-caprolactone) (PEO-b-PCL) diblock copolymer as a soft template. The self-assembled mesoporous phenolic resin was found to form only in a specific resol concentration range of 40-70 wt % due to an intriguing balance of hydrogen-bonding interactions in the resol/PEO-b-PCL mixtures. Furthermore, morphological transitions of the mesostructures from disordered to gyroid to cylindrical and finally to disordered micelle structure were observed with increasing resol concentration. By calcination under nitrogen atmosphere at 800 °C, the bicontinuous mesostructured gyroid phenolic resin could be converted to mesoporous carbon with large pore size without collapse of the original mesostructure. Furthermore, post-treatment of the mesoporous gyroid phenolic resin with melamine gave rise to N-doped mesoporous carbon with unique electronic properties for realizing high CO 2 adsorption capacity (6.72 mmol g -1 at 0 °C). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gelatinized and nongelatinized corn starch/ poly(epsilon-caprolactone blends: characterization by rheological, mechanical and morphological properties

Directory of Open Access Journals (Sweden)

Derval S. Rosa

2004-09-01

Full Text Available Poly(epsilon-caprolactone/corn starch blends containing 25, 50 and 75 wt.% starch were prepared by mechanical processing and characterized by the melt flow index (MFI, tensile test and scanning electron microscopy (SEM. For comparison, starch was used in gelatinized and nongelatinized forms and was also characterized by viscography. The addition of starch to poly(epsilon-caprolactone reduced the MFI values, the tensile strength and the elongation at break, whereas the modulus increased. The reductions in the MFI and tensile properties were most evident when gelatinized starch was used. Viscography and SEM showed that starch was well gelatinized by the gelatinization process. Blends containing nongelatinized starch showed a good dispersion of starch but poor interfacial interactions.

A poly({epsilon}-caprolactone) device for sustained release of an anti-glaucoma drug

Energy Technology Data Exchange (ETDEWEB)

Natu, Madalina V; De Sousa, HermInio C; Gil, M H [Department of Chemical Engineering, University of Coimbra, Polo II, Pinhal de Marrocos, 3030-290, Coimbra (Portugal); Gaspar, Manuel N; Fontes Ribeiro, Carlos A [Institute of Pharmacology and Experimental Therapeutics, University of Coimbra, Azinhaga de Santa Comba, Celas, 3000-354, Coimbra (Portugal); Correia, IlIdio J; Silva, Daniela, E-mail: hgil@eq.uc.pt [Centro de Investigacao em Ciencias da Saude, Faculdade de Ciencias da Saude, Universidade da Beira Interior, Covilha (Portugal)

2011-04-15

Implantable dorzolamide-loaded discs were prepared by blending poly({epsilon}-caprolactone), PCL, with poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide), Lu. By blending, crystallinity, water uptake and mass loss were modified relative to the pure polymers. Burst was diminished by coating the discs with a PCL shell. All samples presented burst release except PCL-coated samples that showed controlled release during 18 days. For PCL-coated samples, barrier control of diffusion coupled with partition control from the core slowed down the release, while for 50/50 Lu/PCL-coated samples, the enhancement in the porosity of the core diminished partition control of drug release. Nonlinear regression analysis suggested that a degradation model fully describes the release curve considering a triphasic release mechanism: the instantaneous diffusion (burst), diffusion and polymer degradation stages. The MTT test indicated that the materials are not cytotoxic for corneal endothelial cells. A good in vitro-in vivo correlation was obtained, with similar amounts of drug released in vitro and in vivo. The discs decreased intraocular pressure (IOP) in normotensive rabbit eyes by 13.0% during 10 days for PCL-coated and by 13.0% during 4 days for 50/50 Lu/PCL-coated samples. The percentages of IOP decrease are similar to those obtained by dorzolamide eyedrop instillation (11.0%).

Synthesis and characterization of amylose grafted poly(acrylic acid) and its application in ammonia adsorption.

Science.gov (United States)

Chen, Qing; Yu, Haojie; Wang, Li; Abdin, Zain-Ul; Yang, Xinpeng; Wang, Junhua; Zhou, Weidong; Zhang, Hongtao; Chen, Xiao

2016-11-20

Amylose grafted poly(acrylic acid) (Am-g-PAA) was synthesized by graft copolymerization of amylose with acrylic acid. The structure of Am-g-PAA was confirmed by (1)H NMR and FT-IR spectra. The morphology, crystallinity and thermal properties of amylose and Am-g-PAA were investigated by SEM, XRD and TGA, respectively. The highest degree of substitution (DS) of carboxyl group was 1.96 which was obtained after reacted for 1h at 60°C. Acrylic acid to anhydroglucose mole ratio for DS was 19.81. It was found that a large number of carboxyl groups were grafted on the backbone of amylose. It was also found that ammonia adsorption capacity of amylose increased by grafting poly(acrylic acid) on the backbone of amylose. Copyright © 2016 Elsevier Ltd. All rights reserved.

Silver-Loaded Cellulose Acetate-g-Poly(ε-caprolactone) Composites

Science.gov (United States)

Tuburan, CR; Dela Rosa, LE; Reyes, LQ

2017-06-01

Cellulose acetate (CA) was grafted with poly(ε-caprolactone) PCL oligomers via the ring-opening of ε-caprolactone (ε-CL) monomer initiated by the hydroxyl functionality of CA. The incorporation of short PCL oligomers in CA’s structure caused the transformation of it crystalline domains into amorphous phases (internal plasticization) as observed by differential scanning calorimetry (DSC). Another evidence of plasticization induced by grafting was the significant reduction of the degradation temperature and stiffness of the copolymers. Proton Nuclear Magnetic Resonance (1H-NMR), Fourier-Transform Infrared (FTIR) Spectroscopies and Gel Permeation Chromatography (GPC) verified success the grafting as suggested by the attachment of PCL on the glucose ring and increase in polymer molecular weights after the reaction. Due to the good films forming ability of the synthesized CA grafted with PCL (CA-g-PCL) material, it was loaded with silver nitrate (AgNO3) and the composite was observed to be have bactericidal against a gram negative bacteria, Escherichia coli, and a gram positive bacteria, Bacillus subtilis.

Study of morphology and mechanical properties of hydrophilic films based on compositions of poly(acrylic acid) and poly(2-hydroxy ethylvinylether)

International Nuclear Information System (INIS)

Bitekenova, A.; Dzhusupbekova, A.; Khutoryanskij, V.; Nurkeeva, Z.

2003-01-01

The hydrophilic films based on compositions of poly(acrylic acid) and poly(2-hydroxy ethylvinylether) were obtained from blend of the corresponding monomers. Radiation crosslinking of composite materials are realize by γ-irradiation method and the gelation doses were calculated. It was shown that mechanical properties of films depend on composition (content of notion component) and conditions of crosslinking. The morphology of polymeric films was investigated by scanning electron microscopy

Effects of sterilisation by high-energy radiation on biomedical poly-(epsilon-caprolactone)/hydroxyapatite composites.

Science.gov (United States)

Di Foggia, Michele; Corda, Ugo; Plescia, Elena; Taddei, Paola; Torreggiani, Armida

2010-06-01

The effects of a high energy sterilization treatment on poly-epsilon-caprolactone/carbonated hydroxyapatite composites have been investigated. Poly-epsilon-caprolactone is a biodegradable polymer used as long-term bioresorbable scaffold for bone tissue engineering and carbonated hydroxyapatite is a bioactive material able to promote bone growth. The composites were gamma-irradiated in air or under nitrogen atmosphere with doses ranging from 10 to 50 kGy (i.e. to a value higher than that recommended for sterilization). The effects of the irradiation treatment were evaluated by vibrational spectroscopy (IR and Raman spectroscopies) coupled to thermal analysis (Differential Scanning Calorimetry and Thermogravimetry) and Electron Paramagnetic Resonance spectroscopy. Irradiation with the doses required for sterilization induced acceptable structural changes and damaging effects: only a very slight fragmentation of the polymeric chains and some defects in the inorganic component were observed. Moreover, the radiation sensitivity of the composites proved almost the same under the two different atmospheres.

Dynamically formed hydrous zirconium (IV) oxide-polyelectrolyte membranes. III: Poly(acrylic acid) and substituted poly(acrylic acid) homo, co and terpolymer membranes

International Nuclear Information System (INIS)

Van Reenen, A.J.; Sanderson, R.D.

1989-01-01

A series of acrylic acid and substituted acrylic acid homo, co and terpolymers was synthesised. These polymers were used as polyelectrolytes in dynamically formed hydrous zirconium (iv) oxide-polyelectrolyte membranes. Substitution of the acrylic acid α-hydrogen was done to increase the number of carboxylic acid groups per monomer unit and to change the acid strength of acrylic acid carboxylic acid group. None of these changes improved the salt rejection of these membranes over that of commercially used poly(acrylic acid). Improvement in rejection was found when a hydrophobic comonomer, vinyl acetate, was used in conjunction with acrylic acid in a copolymer dynamic membrane. 16 refs., 6 figs., 1 tab

Preparation of mono-dispersed silver nanoparticles assisted by chitosan-g-poly(ε-caprolactone) micelles and their antimicrobial application

Energy Technology Data Exchange (ETDEWEB)

Gu, Chunhua [Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 (China); Zhang, Huan [State Key Laboratory of Bioreactor Engineering, New World Biotechnology Institute, East China University of Science and Technology, Shanghai 200237 (China); Lang, Meidong, E-mail: mdlang@ecust.edu.cn [Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 (China)

2014-05-01

Graphical abstract: - Highlights: • Chemical modification of chitosan were conducted after phthaloyl protection of amino groups. • Silver nanoparticles were prepared in the presence of chitosan-based copolymer micelles. • The optimal time scale and weight ratios of silver to micelles were monitored by UV–vis spectrometer. - Abstract: Amphiphilic chitosan-graft-poly(ε-caprolactone) (CS-g-PCLs) copolymers were synthesized by a homogeneous coupling method and characterized by {sup 1}H NMR, FTIR and ninhydrin assay. The graft copolymers were subsequently self-assembled into micelles, which were measured by DLS and TEM. The particle size of the micelles decreased as the segment grafting fraction was increased. Thereafter, silver nanoparticles were prepared in the presence of chitosan-based micelles under UV irradiation. The molar ratio and radiation time of silver to micelles were optimized with process monitored via UV–vis spectrophotometer. DLS and TEM were used to illustrate the particle structure and size while XRD patterns were applied to characterize the crystal structures of polymer-assisted silver nanoparticles. Films impregnated with silver nanoparticles were conducted with results of strong antimicrobial activities against Escherichia coli and Staphylococcus aureus as model Gram-negative and positive bacteria.

Preparation of mono-dispersed silver nanoparticles assisted by chitosan-g-poly(ε-caprolactone) micelles and their antimicrobial application

International Nuclear Information System (INIS)

Gu, Chunhua; Zhang, Huan; Lang, Meidong

2014-01-01

Graphical abstract: - Highlights: • Chemical modification of chitosan were conducted after phthaloyl protection of amino groups. • Silver nanoparticles were prepared in the presence of chitosan-based copolymer micelles. • The optimal time scale and weight ratios of silver to micelles were monitored by UV–vis spectrometer. - Abstract: Amphiphilic chitosan-graft-poly(ε-caprolactone) (CS-g-PCLs) copolymers were synthesized by a homogeneous coupling method and characterized by 1 H NMR, FTIR and ninhydrin assay. The graft copolymers were subsequently self-assembled into micelles, which were measured by DLS and TEM. The particle size of the micelles decreased as the segment grafting fraction was increased. Thereafter, silver nanoparticles were prepared in the presence of chitosan-based micelles under UV irradiation. The molar ratio and radiation time of silver to micelles were optimized with process monitored via UV–vis spectrophotometer. DLS and TEM were used to illustrate the particle structure and size while XRD patterns were applied to characterize the crystal structures of polymer-assisted silver nanoparticles. Films impregnated with silver nanoparticles were conducted with results of strong antimicrobial activities against Escherichia coli and Staphylococcus aureus as model Gram-negative and positive bacteria

Epoxy/anhydride thermosets modified with end-capped star polymers with poly(ethyleneimine cores of different molecular weight and poly(ε–caprolactone arms

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C. Acebo

2015-09-01

Full Text Available Multiarm star polymers, with a hyperbranched poly(ethyleneimine (PEI core and poly(ε-caprolactone (PCL arms end-capped with acetyl groups were synthesized by ring-opening polymerization of ε-caprolactone from PEI cores of different molecular weight. These star polymers were used as toughening agents for epoxy/anhydride thermosets. The curing process was studied by calorimetry, thermomechanical analysis and infrared spectroscopy. The final properties of the resulting materials were determined by thermal and mechanical tests. The addition of the star polymers led to an improvement up to 130% on impact strength and a reduction in the thermal stresses up to 55%. The structure and molecular weight of the modifier used affected the morphology of the resulting materials. Electron microscopy showed phase-separated morphologies with nano-sized fine particles well adhered to the epoxy/anhydride matrix when the higher molecular weight modifier was used.

Bioinspired bioadhesive polymers: dopa-modified poly(acrylic acid) derivatives.

Science.gov (United States)

Laulicht, Bryan; Mancini, Alexis; Geman, Nathanael; Cho, Daniel; Estrellas, Kenneth; Furtado, Stacia; Hopson, Russell; Tripathi, Anubhav; Mathiowitz, Edith

2012-11-01

The one-step synthesis and characterization of novel bioinspired bioadhesive polymers that contain Dopa, implicated in the extremely adhesive byssal fibers of certain gastropods, is reported. The novel polymers consist of combinations of either of two polyanhydride backbones and one of three amino acids, phenylalanine, tyrosine, or Dopa, grafted as side chains. Dopa-grafted hydrophobic backbone polymers exhibit as much as 2.5 × the fracture strength and 2.8 × the tensile work of bioadhesion of a commercially available poly(acrylic acid) derivative as tested on live, excised, rat intestinal tissue. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Resveratrol-loaded poly(ε-caprolactone) microparticles: preparation and characterization

International Nuclear Information System (INIS)

Mendes, Jessica B.E.; Mainardes, Rubiana M.; Farago, Paulo V.; Michel, Milton D.; Zawadzki, Sonia F.

2011-01-01

Resveratrol-loaded poly(ε-caprolactone) (PCL) microparticles were obtained by simple emulsion/solvent evaporation method. Three drug-loaded formulations were prepared with the aim of investigating the influence of composition on the encapsulation efficiency. Morphological and spectroscopic methods were performed for these materials. The microparticles revealed residual moisture close to 1.5% and encapsulation efficiency above 80%. Spherical shape and smooth surface were observed by SEM. No pores were either verified. Resveratrol-loaded microparticles showed an average particle size of around 50 μm. X-ray diffraction analysis demonstrated that the microencapsulation reduced the drug crystallinity. The FTIR results suggest that no chemical bond was formed between polymer and drug. (author)

Poly(CL/DLLA-b-CL multiblock copolymers as biodegradable thermoplastic elastomers

Directory of Open Access Journals (Sweden)

2008-03-01

Full Text Available Lactic acid and ∑-caprolactone based polymers and their derivates are widely used in biomedical applications. Different properties are introduced by modifying the composition. In this study, poly(ε-caprolactone/D,L-lactide-b-poly(ε-caprolactone multiblock copolymers were synthesized as poly(ester-urethanes (PEUs by polymerizing in two steps involving ring-opening polymerization of precursors and by diisocyanate linking of precursors to produce thermoplastic elastomers (TPEs. The precursors and products were characterized by SEC, 1H-NMR and DSC, and dynamic mechanical study (by dynamic mechanical analysis, DMA as well as morphological characterization (by transmission electron microscopy, TEM of the product TPEs was carried out. Tensile and creep recovery properties of them were also studied. According to the characterizations, all the polymerizations were successful, and the prepared TPEs showed clear elastic behavior. In the DMA scans, rubbery plateau in the storage modulus curves between Tg and terminal flow region was clearly detectable indicating elasticity. The TEM images demonstrated phase separation of amorphous and crystalline blocks when the degree of crystallinity of the hard blocks was high enough. The elongations of TPEs varied between 800–1800%, while the modulus was 7–66 MPa. Two different types of recovery tests indicated the creep properties of TPEs to be highly dependent on the degree of crystallinity.

Hydrophilization of poly(caprolactone copolymers through introduction of oligo(ethylene glycol moieties.

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Jonathan J Wurth

Full Text Available In this study, a new family of poly(ε-caprolactone (PCL copolymers that bear oligo(ethylene glycol (OEG moieties is described. The synthesis of three different oligo(ethylene glycol functionalized epoxide monomers derived from 2-methyl-4-pentenoic acid, and their copolymerization with ε-caprolactone (CL to poly(CL-co-OEG-MPO copolymers is presented. The statistical copolymerization initiated with SnOct2/BnOH yielded the copolymers with varying OEG content and composition. The linear relationship between feed ratio and incorporation of the OEG co-monomer enables control over backbone functional group density. The introduction of OEG moieties influenced both the thermal and the hydrophilic characteristics of the copolymers. Both increasing OEG length and backbone content resulted in a decrease in static water contact angle. The introduction of OEG side chains in the PCL copolymers had no adverse influence on MC-3TE3-E1 cell interaction. However, changes to cell form factor (Φ were observed. While unmodified PCL promoted elongated (anisotropic morphologies (Φ = 0.094, PCL copolymer with tri-ethylene glycol side chains at or above seven percent backbone incorporation induced more isotropic cell morphologies (Φ = 0.184 similar to those observed on glass controls (Φ = 0.151.

Poly(acrylic acid) modifying bentonite with in-situ polymerization for removing lead ions.

Science.gov (United States)

He, Y F; Zhang, L; Yan, D Z; Liu, S L; Wang, H; Li, H R; Wang, R M

2012-01-01

In this paper, a new kind of poly(acrylic acid) modified clay adsorbent, the poly(acrylic acid)/bentonite composite (PAA/HB) was prepared by in-situ polymerization, and utilized to remove lead(II) ions from solutions. The maximum adsorption of adsorbent is at pH 5 for metal ions, whereas the adsorption starts at pH 2. The effects of contact time (5-60 min), initial concentration of metal ions (200-1,000 mg/L) and adsorbent dosage (0.04-0.12 g/100 mL) have been reported in this article. The experimental data were investigated by means of kinetic and equilibrium adsorption isotherms. The kinetic data were analyzed by the pseudo-first-order and pseudo-second-order equation. The experimental data fitted the pseudo-second-order kinetic model very well. Langmuir and Freundlich isotherms were tried for the system to better understand the adsorption isotherm process. The maximal adsorption capacity of the lead(II) ions on the PAA/HB, as calculated from the Langmuir model, was 769.2 mg/g. The results in this study indicated that PAA/HB was an attractive candidate for removing lead(II) (99%).

Facile synthesis of linear-dendritic cholesteryl-poly(epsilon-caprolactone)-b-(L-lysine)(G2) by thiol-ene and azide-alkyne "click" reactions

DEFF Research Database (Denmark)

Javakhishvili, Irakli; Binder, W.H.; Tanner, S.

2010-01-01

The construction of a linear-dendritic block copolymer consisting of terminal cholesteryl moiety, poly(epsilon-caprolactone), and a second generation L-lysine dendron has been accomplished by the combination of copper(I) catalyzed azide-alkyne and UV-triggered thiol-ene "click" reactions. Ring-op...... and thiocholesterol. Near to quantitative functionalization of the intermediate and final products has been attained as confirmed by NMR spectroscopy and MALDI-TOF spectrometry....

Morphology in binary blends of poly(vinyl methyl ether) and epsilon-caprolactone-trimethylene carbonate diblock copolymer

NARCIS (Netherlands)

Luyten, MC; Bogels, EJF; vanEkenstein, GORA; tenBrinke, G; Bras, W; Komanschek, BE; Ryan, AJ

The morphology of symmetric diblock copolymer of epsilon-caprolactone (PCL) and trimethylene carbonate (PTMC), in blends with poly(vinyl methyl ether) (PVME) is investigated with (modulated) differential scanning calorimetry (d.s.c.), time resolved small angle (SAXS) and wide angle (WAXS) X-ray

Morphology in binary blends of poly(vinyl methyl ether) and ε-caprolactone-trimethylene carbonate diblock copolymer

NARCIS (Netherlands)

Luyten, M.C.; Bögels, E.J.F.; Alberda van Ekenstein, G.O.R.; Brinke, G. ten; Bras, W.; Komanschek, B.E.; Ryan, A.J.

1997-01-01

The morphology of symmetric diblock copolymer of ε-caprolactone (PCL) and trimethylene carbonate (PTMC), in blends with poly(vinyl methyl ether) (PVME) is investigated with (modulated) differential scanning calorimetry (d.s.c.), time resolved small angle (SAXS) and wide angle (WAXS) X-ray

Functional Poly(ε-caprolactone)s via Copolymerization of ε-Caprolactone and Pyridyl Disulfide-Containing Cyclic Carbonate: Controlled Synthesis and Facile Access to Reduction-Sensitive Biodegradable Graft Copolymer Micelles

NARCIS (Netherlands)

Chen, Wei; Zou, Yan; Jia, Junna; Meng, Fenghua; Cheng, Ru; Deng, Chao; Feijen, Jan; Zhong, Zhiyuan

2013-01-01

Pyridyl disulfide-functionalized cyclic carbonate (PDSC) monomer was obtained in four straightforward steps from 3-methyl-3-oxetanemethanol and exploited for facile preparation of functional poly(ε-caprolactone) (PCL) containing pendant pyridyl disulfide (PDS) groups via ring-opening

Phase Transition of Poly(acrylic acid-co-N-isopropylacrylamide) Core-shell Nanogels

Science.gov (United States)

Liu, Xiao-bing; Zhou, Jian-feng; Ye, Xiao-dong

2012-08-01

A series of poly(acrylic acid) macromolecular chain transfer agents with different molecular weights were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization and characterized by 1H NMR and gel permeation chromatography. Multiresponsive core-shell nanogels were prepared by dispersion polymerization of N-isopropylacrylamide in water using these poly(potassium acrylate) macro-RAFT agents as the electrosteric stabilizer. The size of the nanogels decreases with the amount of the macro-RAFT agent, indicating that the surface area occupied by per polyelectrolyte group is a critical parameter for stabilizing the nanogels. The volume phase transition and the zeta potentials of the nanogels in aqueous solutions were studied by dynamic light scattering and zetasizer analyzer, respectively.

Osteoinduction and proliferation of bone-marrow stromal cells in three-dimensional poly (ε-caprolactone)/ hydroxyapatite/collagen scaffolds.

Science.gov (United States)

Wang, Ting; Yang, Xiaoyan; Qi, Xin; Jiang, Chaoyin

2015-05-08

Osteoinduction and proliferation of bone-marrow stromal cells (BMSCs) in three-dimensional (3D) poly(ε-caprolactone) (PCL) scaffolds have not been studied throughly and are technically challenging. This study aimed to optimize nanocomposites of 3D PCL scaffolds to provide superior adhesion, proliferation and differentiation environment for BMSCs in this scenario. BMSCs were isolated and cultured in a novel 3D tissue culture poly(ε-caprolactone) (PCL) scaffold coated with poly-lysine, hydroxyapatite (HAp), collagen and HAp/collagen. Cell morphology was observed and BMSC biomarkers for osteogenesis, osteoblast differentiation and activation were analyzed. Scanning Electron Microscope (SEM) micrographs showed that coating materials were uniformly deposited on the surface of PCL scaffolds and BMSCs grew and aggregated to form clusters during 3D culture. Both mRNA and protein levels of the key players of osteogenesis and osteoblast differentiation and activation, including runt-related transcription factor 2 (Runx2), alkaline phosphates (ALP), osterix, osteocalcin, and RANKL, were significantly higher in BMSCs seeded in PCL scaffolds coated with HAp or HAp/collagen than those seeded in uncoated PCL scaffolds, whereas the expression levels were not significantly different in collagen or poly-lysine coated PCL scaffolds. In addition, poly-lysine, collagen, HAp/collagen, and HAp coated PCL scaffolds had significantly more viable cells than uncoated PCL scaffolds, especially scaffolds with HAp/collagen and collagen-alone coatings. That BMSCs in HAp or HAp/collagen PCL scaffolds had remarkably higher ALP activities than those in collagen-coated alone or uncoated PCL scaffolds indicating higher osteogenic differentiation levels of BMSCs in HAp or HAp/collagen PCL scaffolds. Moreover, morphological changes of BMSCs after four-week of 3D culture confirmed that BMSCs successfully differentiated into osteoblast with spread-out phenotype in HAp/collagen coated PCL scaffolds

Polyelectrolyte Complex Nanoparticles of Poly(ethyleneimine and Poly(acrylic acid: Preparation and Applications

Directory of Open Access Journals (Sweden)

Martin Müller

2011-04-01

Full Text Available In this contribution we outline polyelectrolyte (PEL complex (PEC nanoparticles, prepared by mixing solutions of the low cost PEL components poly(ethyleneimine (PEI and poly(acrylic acid (PAC. It was found, that the size and internal structure of PEI/PAC particles can be regulated by process, media and structural parameters. Especially, mixing order, mixing ratio, PEL concentration, pH and molecular weight, were found to be sensible parameters to regulate the size (diameter of spherical PEI/PAC nanoparticles, in the range between 80–1,000 nm, in a defined way. Finally, applications of dispersed PEI/PAC particles as additives for the paper making process, as well as for drug delivery, are outlined. PEI/PAC nanoparticles mixed directly on model cellulose film showed a higher adsorption level applying the mixing order 1. PAC 2. PEI compared to 1. PEI 2. PAC. Surface bound PEI/PAC nanoparticles were found to release a model drug compound and to stay immobilized due to the contact with the aqueous release medium.

Anisotropic poly (glycerol sebacate)-poly (ϵ-caprolactone) electrospun fibers promote endothelial cell guidance

International Nuclear Information System (INIS)

Gaharwar, Akhilesh K; Nikkhah, Mehdi; Sant, Shilpa; Khademhosseini, Ali

2015-01-01

Topographical cell guidance is utilized to engineer highly organized and aligned cellular constructs for numerous tissue engineering applications. Recently, electrospun scaffolds fabricated using poly(glycerol sebacate) (PGS) and poly(ϵ-caprolactone) (PCL) have shown a great promise to support valvular interstitial cell functions for the development of tissue engineered heart valves. However, one of the major drawbacks of PGS-PCL scaffolds is the lack of control over cellular alignment. In this work, we investigate the role of scaffold architecture on the endothelial cell alignment, proliferation and formation of organized cellular structures. In particular, PGS-PCL scaffolds with randomly oriented and highly aligned fibers with tunable mechanical properties were fabricated using electrospinning technique. After one week of culture, endothelial cells on the aligned scaffolds exhibited higher proliferation compared to those cultures on randomly oriented fibrous scaffolds. Furthermore, the endothelial cells reorganized in response to the topographical features of aligned scaffolds forming highly organized cellular constructs. Thus, topographical contact guidance, provided by aligned PGS-PCL scaffolds, is envisioned to be useful in developing cellular structures for vascular tissue engineering. (paper)

Blends of poly(hydroxybutyrate and poly (epsilon-caprolactone obtained from melting mixture

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Maria Cecília M. Antunes

2005-06-01

Full Text Available Poly(3-hydroxybutyrate (PHB is a thermoplastic polyester with a great potential owing to its biodegradability, bioreabsorbation and biological synthesis from a renewable source. Despite these characteristics, the applications of this polymer are very restricted due to its poor mechanical properties and thermal instability at temperatures above its melting point (around 175°C. Among the possibilities of improvement of these materials, the development of blends is a relatively fast and inexpensive option. Poly(epsilon-caprolactone (PCL is a semi-crystalline polymer that may be used as a biomaterial. It presents good mechanical properties, a low melting point (around 55 °C, and could be a good option to develop PHB blends, maintaining the biodegradability and bioreabsorption properties. The objective of the present work was to obtain blends of PHB and PCL by melting mixture in an internal mixer. The compositions varied from 0 to 30 wt% of PCL. DSC, DMA, and SEM were used to characterize the blends. The blends were found to be imiscible with no indication of interaction either the amorphous or crystalline state. The morphology shows PHB as the matrix and PCL as the dispersed phase.

Antimicrobial activity of poly(acrylic acid) block copolymers

Energy Technology Data Exchange (ETDEWEB)

Gratzl, Günther, E-mail: guenther.gratzl@jku.at [Johannes Kepler University Linz, Institute for Chemical Technology of Organic Materials, Altenberger Str. 69, 4040 Linz (Austria); Paulik, Christian [Johannes Kepler University Linz, Institute for Chemical Technology of Organic Materials, Altenberger Str. 69, 4040 Linz (Austria); Hild, Sabine [Johannes Kepler University Linz, Institute of Polymer Science, Altenberger Str. 69, 4040 Linz (Austria); Guggenbichler, Josef P.; Lackner, Maximilian [AMiSTec GmbH and Co. KG, Leitweg 13, 6345 Kössen, Tirol (Austria)

2014-05-01

The increasing number of antibiotic-resistant bacterial strains has developed into a major health problem. In particular, biofilms are the main reason for hospital-acquired infections and diseases. Once formed, biofilms are difficult to remove as they have specific defense mechanisms against antimicrobial agents. Antimicrobial surfaces must therefore kill or repel bacteria before they can settle to form a biofilm. In this study, we describe that poly(acrylic acid) (PAA) containing diblock copolymers can kill bacteria and prevent from biofilm formation. The PAA diblock copolymers with poly(styrene) and poly(methyl methacrylate) were synthesized via anionic polymerization of tert-butyl acrylate with styrene or methyl methacrylate and subsequent acid-catalyzed hydrolysis of the tert-butyl ester. The copolymers were characterized via nuclear magnetic resonance spectroscopy (NMR), size-exclusion chromatography (SEC), Fourier transform infrared spectroscopy (FTIR), elemental analysis, and acid–base titrations. Copolymer films with a variety of acrylic acid contents were produced by solvent casting, characterized by atomic force microscopy (AFM) and tested for their antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa. The antimicrobial activity of the acidic diblock copolymers increased with increasing acrylic acid content, independent of the copolymer-partner, the chain length and the nanostructure. - Highlights: • Acrylic acid diblock copolymers are antimicrobially active. • The antimicrobial activity depends on the acrylic acid content in the copolymer. • No salts, metals or other antimicrobial agents are needed.

Antimicrobial activity of poly(acrylic acid) block copolymers

International Nuclear Information System (INIS)

Gratzl, Günther; Paulik, Christian; Hild, Sabine; Guggenbichler, Josef P.; Lackner, Maximilian

2014-01-01

The increasing number of antibiotic-resistant bacterial strains has developed into a major health problem. In particular, biofilms are the main reason for hospital-acquired infections and diseases. Once formed, biofilms are difficult to remove as they have specific defense mechanisms against antimicrobial agents. Antimicrobial surfaces must therefore kill or repel bacteria before they can settle to form a biofilm. In this study, we describe that poly(acrylic acid) (PAA) containing diblock copolymers can kill bacteria and prevent from biofilm formation. The PAA diblock copolymers with poly(styrene) and poly(methyl methacrylate) were synthesized via anionic polymerization of tert-butyl acrylate with styrene or methyl methacrylate and subsequent acid-catalyzed hydrolysis of the tert-butyl ester. The copolymers were characterized via nuclear magnetic resonance spectroscopy (NMR), size-exclusion chromatography (SEC), Fourier transform infrared spectroscopy (FTIR), elemental analysis, and acid–base titrations. Copolymer films with a variety of acrylic acid contents were produced by solvent casting, characterized by atomic force microscopy (AFM) and tested for their antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa. The antimicrobial activity of the acidic diblock copolymers increased with increasing acrylic acid content, independent of the copolymer-partner, the chain length and the nanostructure. - Highlights: • Acrylic acid diblock copolymers are antimicrobially active. • The antimicrobial activity depends on the acrylic acid content in the copolymer. • No salts, metals or other antimicrobial agents are needed

Amphiphilic poly(ether ester amide) multiblock copolymers as biodegradable matrices for the controlled release of proteins

NARCIS (Netherlands)

Bezemer, J.M.; Oude Weme, P.; Grijpma, Dirk W.; Dijkstra, Pieter J.; van Blitterswijk, Clemens; Feijen, Jan

2000-01-01

Amphiphilic poly(ether ester amide) (PEEA) multiblock copolymers were synthesized by polycondensation in the melt from hydrophilic poly(ethylene glycol) (PEG), 1,4-dihydroxybutane and short bisester-bisamide blocks. These amide blocks were prepared by reaction of 1,4-diaminobutane with dimethyl

Development of thiolated poly(acrylic acid) microparticles for the nasal administration of exenatide.

Science.gov (United States)

Millotti, Gioconda; Vetter, Anja; Leithner, Katharina; Sarti, Federica; Shahnaz Bano, Gul; Augustijns, Patrick; Bernkop-Schnürch, Andreas

2014-12-01

The purpose of this study was to develop a microparticulate formulation for nasal delivery of exenatide utilizing a thiolated polymer. Poly(acrylic acid)-cysteine (PAA-cys) and unmodified PAA microparticles loaded with exenatide were prepared via coprecipitation of the drug and the polymer followed by micronization. Particle size, drug load and release of incorporated exenatide were evaluated. Permeation enhancing properties of the formulations were investigated on excised porcine respiratory mucosa. The viability of the mucosa was investigated by histological studies. Furthermore, ciliary beat frequency (CBF) studies were performed. Microparticles displayed a mean size of 70-80 µm. Drug encapsulation was ∼80% for both thiolated and non-thiolated microparticles. Exenatide was released from both thiolated and non-thiolated particles in comparison to exenatide in buffer only within 40 min. As compared to exenatide dissolved in buffer only, non-thiolated and thiolated microparticles resulted in a 2.6- and 4.7-fold uptake, respectively. Histological studies performed before and after permeation studies showed that the mucosa is not damaged during permeation studies. CBF studies showed that the formulations were cilio-friendly. Based on these results, poly(acrylic acid)-cysteine-based microparticles seem to be a promising approach starting point for the nasal delivery of exenatide.

Using X-PEEM to study biomaterials: Protein and peptide adsorption to a polystyrene-poly(methyl methacrylate)-b-polyacrylic acid blend

Energy Technology Data Exchange (ETDEWEB)

Leung, Bonnie O. [Chemistry and Chemical Biology, BIMR, McMaster University, Hamilton, ON, Canada L8S 4M1 (Canada); Hitchcock, Adam P., E-mail: aph@mcmaster.ca [Chemistry and Chemical Biology, BIMR, McMaster University, Hamilton, ON, Canada L8S 4M1 (Canada); Cornelius, Rena M.; Brash, John L. [School of Biomedical Engineering, McMaster University, Hamilton, ON, Canada L8S 4M1 (Canada); Scholl, Andreas; Doran, Andrew [Advanced Light Source, Berkeley Lab, Berkeley, CA 94720 (United States)

2012-10-15

Highlights: Black-Right-Pointing-Pointer We review applications of synchrotron X-PEEM to biomaterials. Black-Right-Pointing-Pointer We report characterization of a PS/PMMA-b-PAA blend surface by AFM and X-PEEM. Black-Right-Pointing-Pointer We report quantitative mapping of protein (HSA) and peptide adsorption on PS/PMMA-b-PAA. Black-Right-Pointing-Pointer We report how this adsorption changes with pH. -- Abstract: Recent synchrotron-based soft X-ray photoemission electron microscopy (X-PEEM) studies of protein and peptide interaction with phase segregated and patterned polymer surfaces in the context of optimization of candidate biomaterials are reviewed and a study of a new system is reported. X-PEEM and atomic force microscopy (AFM) were used to investigate the morphology of a phase-segregated thin film of a polystyrene/poly(methyl methacrylate)-b-polyacrylic acid (PS/PMMA-PAA) blend, and its interactions with negatively charged human serum albumin (HSA) and positively charged SUB-6 (a cationic antimicrobial peptide, RWWKIWVIRWWR-NH{sub 2}) at several pHs. At neutral pH, where the polymer surface is partially negatively charged, HSA and SUB-6 peptide showed contrasting adsorption behavior which is interpreted in terms of differences in their electrostatic interactions with the polymer surface.

Properties of Electrospun Nanofibers of Multi-Block Copolymers of [Poly-ε-caprolactone-b-poly(tetrahydrofuran-co-ε-caprolactone]m Synthesized by Janus Polymerization

Directory of Open Access Journals (Sweden)

Muhammad Ijaz Shah

2017-10-01

Full Text Available Novel biodegradable multiblock copolymers of [PCL-b-P(THF-co-CL]m with PCL fractions of 53.3 and 88.4 wt % were prepared by Janus polymerization of ε-caprolactone (CL and tetrahydrofuran (THF. Their electrospun mats were obtained with optimized parameters containing bead-free nanofibers whose diameters were between 290 and 520 nm. The mechanical properties of the nanofiber scaffolds were measured showing the tensile strength and strain at break of 8–10 MPa and 123–161%, respectively. Annealing improved their mechanical properties and their tensile strength and strain at break of the samples increased to 10–13 MPa and 267–338%, respectively. Due to the porous structure and crystallization in nanoscale confinement, the mechanical properties of the nanofiber scaffolds appeared as plastics, rather than as the elastomers observed in bulk thermal-molded film.

Preparation and characterization of poly(acrylic acid)-hydroxyethyl cellulose graft copolymer.

Science.gov (United States)

Abdel-Halim, E S

2012-10-01

Poly(acrylic acid) hydroxyethyl cellulose [poly(AA)-HEC] graft copolymer was prepared by polymerizing acrylic acid (AA) with hydroxyethyl cellulose (HEC) using potassium bromate/thiourea dioxide (KBrO(3)/TUD) as redox initiation system. The polymerization reaction was carried out under a variety of conditions including concentrations of AA, KBrO(3) and TUD, material to liquor ratio and polymerization temperature. The polymerization reaction was monitored by withdrawing samples from the reaction medium and measuring the total conversion. The rheological properties of the poly(AA)-HEC graft copolymer were investigated. The total conversion and rheological properties of the graft copolymer depended on the ratio of KBrO(3) to TUD and on acrylic acid concentration as well as temperature and material to liquor ratio. Optimum conditions of the graft copolymer preparation were 30 mmol KBrO(3) and 30 mmol TUD/100g HEC, 100% AA (based on weight of HEC), duration 2h at temperature 50 °C using a material to liquor ratio of 1:10. Copyright © 2012. Published by Elsevier Ltd.

Novel star-type methoxy-poly(ethylene glycol) (PEG)-poly({epsilon}-caprolactone) (PCL) copolymeric nanoparticles for controlled release of curcumin

Energy Technology Data Exchange (ETDEWEB)

Feng Runliang; Zhu Wenxia; Song Zhimei, E-mail: zhimei_song@126.com [University of Jinan, Shandong Academy of Medical Science, Department of Pharmaceutical Engineering, School of Medicine and Life Sciences (China); Zhao Liyan [Hebei North University, Department of Pharmacy (China); Zhai Guangxi [Shandong University, Department of Pharmaceutics, College of Pharmacy (China)

2013-06-15

To improve curcumin's (CURs) water solubility and release property, a novel star methoxy poly(ethylene glycol)-poly({epsilon}-caprolactone) (MPEG-PCL) copolymer was synthesized through O-alkylation, basic hydrolysis and ring-opening polymerization reaction with MPEG, epichlorohydrin, and {epsilon}-caprolactone as raw materials. The structure of the novel copolymer was characterized by {sup 1}H NMR, FT-IR, and GPC. The results of FT-IR and differential scanning calorimeter of CUR-loaded nanoparticles (NPs) prepared by dialysis method showed that CUR was successfully encapsulated into the SMP12 copolymeric NPs with 98.2 % of entrapment efficiency, 10.91 % of drug loading, and 88.4 {+-} 11.2 nm of mean particle diameter in amorphous forms. The dissolubility of nanoparticulate CUR was increased by 1.38 Multiplication-Sign 10{sup 5} times over CUR in water. The obtained blank copolymer showed no hemolysis. A sustained CUR release to a total of approximately 56.13 % was discovered from CUR-NPs in 40 % of ethanol saline solution within 72 h on the use of dialysis method. The release behavior fitted the ambiexponent and biphasic kinetics equation. In conclusion, the copolymeric NPs loading CUR might serve as a potential nanocarrier to improve the solubility and release property of CUR.

Novel star-type methoxy-poly(ethylene glycol) (PEG)-poly(ɛ-caprolactone) (PCL) copolymeric nanoparticles for controlled release of curcumin

Science.gov (United States)

Feng, Runliang; Zhu, Wenxia; Song, Zhimei; Zhao, Liyan; Zhai, Guangxi

2013-06-01

To improve curcumin's (CURs) water solubility and release property, a novel star methoxy poly(ethylene glycol)-poly(ɛ-caprolactone) (MPEG-PCL) copolymer was synthesized through O-alkylation, basic hydrolysis and ring-opening polymerization reaction with MPEG, epichlorohydrin, and ɛ-caprolactone as raw materials. The structure of the novel copolymer was characterized by 1H NMR, FT-IR, and GPC. The results of FT-IR and differential scanning calorimeter of CUR-loaded nanoparticles (NPs) prepared by dialysis method showed that CUR was successfully encapsulated into the SMP12 copolymeric NPs with 98.2 % of entrapment efficiency, 10.91 % of drug loading, and 88.4 ± 11.2 nm of mean particle diameter in amorphous forms. The dissolubility of nanoparticulate CUR was increased by 1.38 × 105 times over CUR in water. The obtained blank copolymer showed no hemolysis. A sustained CUR release to a total of approximately 56.13 % was discovered from CUR-NPs in 40 % of ethanol saline solution within 72 h on the use of dialysis method. The release behavior fitted the ambiexponent and biphasic kinetics equation. In conclusion, the copolymeric NPs loading CUR might serve as a potential nanocarrier to improve the solubility and release property of CUR.

Hierarchically organized architecture of potassium hydrogen phthalate and poly(acrylic acid): toward a general strategy for biomimetic crystal design.

Science.gov (United States)

Oaki, Yuya; Imai, Hiroaki

2005-12-28

A hierarchically organized architecture in multiple scales was generated from potassium hydrogen phthalate crystals and poly(acrylic acid) based on our novel biomimetic approach with an exquisite association of polymers on crystallization.

Fluorescence ON–OFF switching using micelle of stimuli-responsive double hydrophilic block copolymers: Nile Red fluorescence in micelles of poly(acrylic acid-b-N-isopropylacrylamide)

Energy Technology Data Exchange (ETDEWEB)

Yee, Min Min; Tsubone, Miyabi; Morita, Takuya [Department of Chemistry, Graduate School of Science & Engineering, Saga University, 1 Honjo, Saga 840-8502 (Japan); Yusa, Shin-ichi [Department of Materials Science and Chemistry, University of Hyogo, 2167 Shosha, Himeji 671-2280 (Japan); Nakashima, Kenichi, E-mail: nakashik@cc.saga-u.ac.jp [Department of Chemistry, Graduate School of Science & Engineering, Saga University, 1 Honjo, Saga 840-8502 (Japan)

2016-08-15

The dual-mode fluorescence ON–OFF switching of Nile Red (NR) by using stimuli-responsive polymeric micelle of poly(acrylic acid-b-N-isopropylacrylamide) (PAA-b-PNIPAM) has been studied. PAA-b-PNIPAM, one of double hydrophilic block copolymers, is known to form PNIPAM-core/PAA-corona micelles in aqueous solutions when the temperature of the solution is elevated up to the lower critical solution temperature (LCST) of PNIPAM block. It also forms PAA-core/PNIPAM-corona micelles when the anionic PAA block is charge-neutralized with cationic cetyltrimethylammonium ion. Fluorescence properties of NR in the micelles are elucidated by observing various fluorescence parameters such as intensity, polarization, and quantum yield. It is found that the fluorescence intensity is negligibly low (OFF-state) when PAA-b-PNIPAM exists as a form of unimer, whereas it is remarkably enhanced (ON-state) when the PNIPAM-core or PAA-core micelles are formed. These results demonstrate that a novel fluorescence ON–OFF switching system can be constructed by using PAA-b-PNIPAM micelles and NR.

Immobilization of pH-sensitive CdTe Quantum Dots in a Poly(acrylate) Hydrogel for Microfluidic Applications

Science.gov (United States)

Franke, M.; Leubner, S.; Dubavik, A.; George, A.; Savchenko, T.; Pini, C.; Frank, P.; Melnikau, D.; Rakovich, Y.; Gaponik, N.; Eychmüller, A.; Richter, A.

2017-04-01

Microfluidic devices present the basis of modern life sciences and chemical information processing. To control the flow and to allow optical readout, a reliable sensor material that can be easily utilized for microfluidic systems is in demand. Here, we present a new optical readout system for pH sensing based on pH sensitive, photoluminescent glutathione capped cadmium telluride quantum dots that are covalently immobilized in a poly(acrylate) hydrogel. For an applicable pH sensing the generated hybrid material is integrated in a microfluidic sensor chip setup. The hybrid material not only allows in situ readout, but also possesses valve properties due to the swelling behavior of the poly(acrylate) hydrogel. In this work, the swelling property of the hybrid material is utilized in a microfluidic valve seat, where a valve opening process is demonstrated by a fluid flow change and in situ monitored by photoluminescence quenching. This discrete photoluminescence detection (ON/OFF) of the fluid flow change (OFF/ON) enables upcoming chemical information processing.

Hollow fibers made from a poly(3-hydroxybutyrate/poly-ε-caprolactone blend

Directory of Open Access Journals (Sweden)

2011-07-01

Full Text Available Since poly(3-hydroxybutyrate (PHB is inherently brittle and possesses poor elastic properties, hollow fibers produced by melt spinning from pure PHB, as described in our earlier study [Macromolecular Materials and Engineering, 2010, 295/6, 585–594], do not meet the required needs regarding the mechanical performance. Besides hardly available PHB copolymers, also blend systems are known to enhance material properties and have thus been considered to be eligible to fabricate flexible or rather pliable hollow fibers based on PHB. Blends of PHB and poly-!-caprolactone (PCL are promising for the application in tissue engineering due to the inherent biocompatibility and biodegradability. A wide range of PHB/PCL compositions have been prepared by melt extrusion. Thermal and mechanical properties of the obtained specimens were analyzed in order to identify miscibility and degree of dispersion as well as to determine the influence on the overall mechanical performance. Even though these constituents are known to be immiscible, PHB/PCL 70/30 was proven to be an adequate composition. This blend showed a highly increased elongation and was found to be easily processable by melt spinning compared to pure PHB. From this blend well defined dimensionally stable bendable hollow fibers were fabricated.

Influence of boehmite nanoparticle loading on the mechanical, thermal, and rheological properties of biodegradable polylactide/ poly(e-caprolactone) blends

CSIR Research Space (South Africa)

Agwuncha, SC

2015-01-01

Full Text Available Blends of polylactide (PLA) and poly(e-caprolactone) (PCL) were melt-processed with boehmite (BAI) nanoparticles to produce ternary biocomposites with the intent of broadening the potential applications of PLA. The mechanical properties...

Manganese oxide electrochemical capacitor with potassium poly(acrylate) hydrogel electrolyte

Science.gov (United States)

Lee, Kuang-Tsin; Wu, Nae-Lih

An aqueous gel electrolyte has for the first time been successfully applied to the MnO 2· nH 2O-based pseudocapacitive electrochemical capacitors (ECs). The gel electrolyte is made of potassium poly(acrylate) (PAAK) polymer and aqueous solution of KCl. With the selected composition, PAAK:KCl:H 2O = 9.0%:6.7%:84.3% by weight, the gel shows no fluidity, possessing an ionic conductivity in the order of 10 -1 S cm -1. The gel electrolyte has been found to give substantially higher specific capacitances than those in the liquid electrolyte with the same salt (KCl) composition (1 M) and high power capability (>10 kW/kg).

Manganese oxide electrochemical capacitor with potassium poly(acrylate) hydrogel electrolyte

Energy Technology Data Exchange (ETDEWEB)

Lee, Kuang-Tsin; Wu, Nae-Lih [Department of Chemical Engineering, National Taiwan University, Taipei 106 (China)

2008-04-15

An aqueous gel electrolyte has for the first time been successfully applied to the MnO{sub 2}.nH{sub 2}O-based pseudocapacitive electrochemical capacitors (ECs). The gel electrolyte is made of potassium poly(acrylate) (PAAK) polymer and aqueous solution of KCl. With the selected composition, PAAK:KCl:H{sub 2}O = 9.0%:6.7%:84.3% by weight, the gel shows no fluidity, possessing an ionic conductivity in the order of 10{sup -1} S cm{sup -1}. The gel electrolyte has been found to give substantially higher specific capacitances than those in the liquid electrolyte with the same salt (KCl) composition (1 M) and high power capability (>10 kW/kg). (author)

Long-term evaluation of degradation and foreign-body reaction of subcutaneously implanted poly(DL-lactide-epsilon-caprolactone)

NARCIS (Netherlands)

denDunnen, WFA; Robinson, PH; vanWessel, R; Pennings, AJ; vanLeeuwen, MBM; Schakenraad, JM

1997-01-01

The aim of this study was to evaluate the degradation and foreign-body reaction of poly(DL-lactide-epsilon-caprolactone) (PLA(85)CL(50)) bars. This specific biomaterial is used for the construction of nerve guides, which can be used in the reconstruction of short nerve gaps. Subcutaneously implanted

Cryogenic grinding of electrospun poly-epsilon-caprolactone mesh submerged in liquid media

Czech Academy of Sciences Publication Activity Database

Knotek, P.; Pouzar, M.; Buzgo, Matej; Křížková, B.; Vlček, Milan; Míčková, Andrea; Plencner, Martin; Návesník, J.; Amler, Evžen; Bělina, P.

2012-01-01

Roč. 32, č. 6 (2012), s. 1366-1374 ISSN 0928-4931 Grant - others:GA MŠk(CZ) GA UK 330611; GA MŠk(CZ) GA UK 384311; GA MŠk(CZ) GA UK 99610; GA MŠk(CZ) ME 10145; GA MŠk(CZ) MSM0021627501; GA MŠk(CZ) ERA-NET Carsila ME10145; EU FP7(XE) BIOSCENT ID 214539 Institutional research plan: CEZ:AV0Z50390703; CEZ:AV0Z40500505 Keywords : cryogenic grinding * poly-epsilon-caprolactone * nano/micro-mesh Subject RIV: BO - Biophysics Impact factor: 2.404, year: 2012

Novel star-type methoxy-poly(ethylene glycol) (PEG)–poly(ε-caprolactone) (PCL) copolymeric nanoparticles for controlled release of curcumin

International Nuclear Information System (INIS)

Feng Runliang; Zhu Wenxia; Song Zhimei; Zhao Liyan; Zhai Guangxi

2013-01-01

To improve curcumin’s (CURs) water solubility and release property, a novel star methoxy poly(ethylene glycol)–poly(ε-caprolactone) (MPEG–PCL) copolymer was synthesized through O-alkylation, basic hydrolysis and ring-opening polymerization reaction with MPEG, epichlorohydrin, and ε-caprolactone as raw materials. The structure of the novel copolymer was characterized by 1 H NMR, FT-IR, and GPC. The results of FT-IR and differential scanning calorimeter of CUR-loaded nanoparticles (NPs) prepared by dialysis method showed that CUR was successfully encapsulated into the SMP12 copolymeric NPs with 98.2 % of entrapment efficiency, 10.91 % of drug loading, and 88.4 ± 11.2 nm of mean particle diameter in amorphous forms. The dissolubility of nanoparticulate CUR was increased by 1.38 × 10 5 times over CUR in water. The obtained blank copolymer showed no hemolysis. A sustained CUR release to a total of approximately 56.13 % was discovered from CUR-NPs in 40 % of ethanol saline solution within 72 h on the use of dialysis method. The release behavior fitted the ambiexponent and biphasic kinetics equation. In conclusion, the copolymeric NPs loading CUR might serve as a potential nanocarrier to improve the solubility and release property of CUR.

Development of biodegradable metaloxide/polymer nanocomposite films based on poly-ε-caprolactone and terephthalic acid.

Science.gov (United States)

Varaprasad, Kokkarachedu; Pariguana, Manuel; Raghavendra, Gownolla Malegowd; Jayaramudu, Tippabattini; Sadiku, Emmanuel Rotimi

2017-01-01

The present investigation describes the development of metal-oxide polymer nanocomposite films from biodegradable poly-ε-caprolactone, disposed poly(ethylene terephthalate) oil bottles monomer and zinc oxide-copper oxide nanoparticles. The terephthalic acid and zinc oxide-copper oxide nanoparticles were synthesized by using a temperature-dependent precipitation technique and double precipitation method, respectively. The terephthalic acid synthesized was confirmed by FTIR analysis and furthermore, it was characterized by thermal analysis. The as-prepared CuO-ZnO nanoparticles structure was confirmed by XRD analysis and its morphology was analyzed by SEM/EDS and TEM. Furthermore, the metal-oxide polymer nanocomposite films have excellent mechanical properties, with tensile strength and modulus better than pure films. The metal-oxide polymer nanocomposite films that were successfully developed show a relatively brighter colour when compared to CuO film. These new metal-oxide polymer nanocomposite films can replace many non-degradable plastics. The new metal-oxide polymer nanocomposite films developed are envisaged to be suitable for use in industrial and domestic packaging applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Novel amphiphilic poly(dimethylsiloxane) based polyurethane networks tethered with carboxybetaine and their combined antibacterial and anti-adhesive property

Energy Technology Data Exchange (ETDEWEB)

Jiang, Jingxian; Fu, Yuchen; Zhang, Qinghua, E-mail: qhzhang@zju.edu.cn; Zhan, Xiaoli; Chen, Fengqiu

2017-08-01

Highlights: • An amphiphilic poly(dimethylsiloxane) (PDMS) based polyurethane (PU) network tethered with carboxybetaine is prepared. • The surface distribution of PDMS and zwitterionic segments produces an obvious amphiphilic heterogeneous surface. • This designed PDMS-based amphiphilic PU network exhibits combined antibacterial and anti-adhesive properties. - Abstract: The traditional nonfouling materials are powerless against bacterial cells attachment, while the hydrophobic bactericidal surfaces always suffer from nonspecific protein adsorption and dead bacterial cells accumulation. Here, amphiphilic polyurethane (PU) networks modified with poly(dimethylsiloxane) (PDMS) and cationic carboxybetaine diol through simple crosslinking reaction were developed, which had an antibacterial efficiency of 97.7%. Thereafter, the hydrolysis of carboxybetaine ester into zwitterionic groups brought about anti-adhesive properties against bacteria and proteins. The surface chemical composition and wettability performance of the PU network surfaces were investigated by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS) and contact angle analysis. The surface distribution of PDMS and zwitterionic segments produced an obvious amphiphilic heterogeneous surface, which was demonstrated by atomic force microscopy (AFM). Enzyme-linked immunosorbent assays (ELISA) were used to test the nonspecific protein adsorption behaviors. With the advantages of the transition from excellent bactericidal performance to anti-adhesion and the combination of fouling resistance and fouling release property, the designed PDMS-based amphiphilic PU network shows great application potential in biomedical devices and marine facilities.

Synthesis and Properties of IPN Hydrogels Based on Konjac Glucomannan and Poly(acrylic acid)

Institute of Scientific and Technical Information of China (English)

Bing LIU; Zhi Lan LIU; Ren Xi ZHUO

2006-01-01

Novel interpenetrating polymer network (IPN) hydrogels based on konjac glucomannan (KGM) and poly(acrylic acid) (PAA) were prepared by polymerization and cross-linking of acrylic acid (AA) in the pre-fabricated KGM gel. The IPN gel was analyzed by FT-IR. The studies on the equilibrium swelling ratio of IPN hydrogels revealed their sensitive response to environmental pH value. The results of in vitro degradation showed that the IPN hydrogels retain the enzymatic degradation character of KGM.

Acid-Labile Amphiphilic PEO-b-PPO-b-PEO Copolymers: Degradable Poloxamer Analogs.

Science.gov (United States)

Worm, Matthias; Kang, Biao; Dingels, Carsten; Wurm, Frederik R; Frey, Holger

2016-05-01

Poly ((ethylene oxide)-b-(propylene oxide)-b-(ethylene oxide)) triblock copolymers commonly known as poloxamers or Pluronics constitute an important class of nonionic, biocompatible surfactants. Here, a method is reported to incorporate two acid-labile acetal moieties in the backbone of poloxamers to generate acid-cleavable nonionic surfactants. Poly(propylene oxide) is functionalized by means of an acetate-protected vinyl ether to introduce acetal units. Three cleavable PEO-PPO-PEO triblock copolymers (Mn,total = 6600, 8000, 9150 g·mol(-1) ; Mn,PEO = 2200, 3600, 4750 g·mol(-1) ) have been synthesized using anionic ring-opening polymerization. The amphiphilic copolymers exhibit narrow molecular weight distributions (Ð = 1.06-1.08). Surface tension measurements reveal surface-active behavior in aqueous solution comparable to established noncleavable poloxamers. Complete hydrolysis of the labile junctions after acidic treatment is verified by size exclusion chromatography. The block copolymers have been employed as surfactants in a miniemulsion polymerization to generate polystyrene (PS) nanoparticles with mean diameters of ≈200 nm and narrow size distribution, as determined by dynamic light scattering and scanning electron microscopy. Acid-triggered precipitation facilitates removal of surfactant fragments from the nanoparticles, which simplifies purification and enables nanoparticle precipitation "on demand." © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication and characterization of injection molded poly (ε-caprolactone) and poly (ε-caprolactone)/hydroxyapatite scaffolds for tissue engineering

International Nuclear Information System (INIS)

Cui Zhixiang; Nelson, Brenton; Peng, YiYan; Li Ke; Pilla, Srikanth; Li Wanju; Turng, Lih-Sheng; Shen Changyu

2012-01-01

In this study, poly(ε-caprolactone) (PCL)/sodium chloride (NaCl), PCL/poly(ethylene oxide) (PEO)/NaCl and PCL/PEO/NaCl/hydroxyapatite (HA) composites were injection molded and characterized. The water soluble and sacrificial polymer, PEO, and NaCl particulates in the composites were leached by deionized water to produce porous and interconnected microstructures. The effect of leaching time on porosity, and residual contents of NaCl and NaCl/HA, as well as the effect of HA addition on mechanical properties was investigated. In addition, the biocompatibility was observed via seeding human mesenchymal stem cells (hMSCs) on PCL and PCL/HA scaffolds. The results showed that the leaching time depends on the spatial distribution of sacrificial PEO phase and NaCl particulates. The addition of HA has significantly improved the elastic (E′) and loss moduli (E″) of PCL/HA scaffolds. Human MSCs were observed to have attached and proliferated on both PCL and PCL/HA scaffolds. Taken together, the molded PCL and PCL/HA scaffolds could be good candidates as tissue engineering scaffolds. Additionally, injection molding would be a potential and high throughput technology to fabricate tissue scaffolds. - Highlights: ►PCL/NaCl, PCL/PEO/NaCl and PCL/PEO/NaCl/HA composites were injection molded. ►Leaching time depends on the distribution of PEO phase and NaCl particulates. ►The elastic and loss moduli of PCL/HA scaffolds have significantly improved. ►Human hMSCs have attached, survived and proliferated well on PCL and PCL/HA scaffolds. ►Molded PCL and PCL/HA scaffolds could be good candidates for tissue engineering.

Sequential crystallization and morphology of triple crystalline biodegradable PEO-b-PCL-b-PLLA triblock terpolymers

KAUST Repository

Palacios, Jordana; Mugica, Agurtzane; Zubitur, Manuela; Iturrospe, Amaia; Arbe, A.; Liu, Guoming; Wang, Dujin; Zhao, Junpeng; Hadjichristidis, Nikolaos; Muller, Alejandro

2016-01-01

The sequential crystallization of poly(ethylene oxide)-b-poly(e-caprolactone)-b-poly(L-lactide) (PEO-b-PCL-b-PLLA) triblock terpolymers, in which the three blocks are able to crystallize separately and sequentially from the melt, is presented. Two

Thermogel-Coated Poly(ε-Caprolactone Composite Scaffold for Enhanced Cartilage Tissue Engineering

Directory of Open Access Journals (Sweden)

Shao-Jie Wang

2016-05-01

Full Text Available A three-dimensional (3D composite scaffold was prepared for enhanced cartilage tissue engineering, which was composed of a poly(ε-caprolactone (PCL backbone network and a poly(lactide-co-glycolide-block-poly(ethylene glycol-block-poly(lactide-co-glycolide (PLGA–PEG–PLGA thermogel surface. The composite scaffold not only possessed adequate mechanical strength similar to native osteochondral tissue as a benefit of the PCL backbone, but also maintained cell-friendly microenvironment of the hydrogel. The PCL network with homogeneously-controlled pore size and total pore interconnectivity was fabricated by fused deposition modeling (FDM, and was impregnated into the PLGA–PEG–PLGA solution at low temperature (e.g., 4 °C. The PCL/Gel composite scaffold was obtained after gelation induced by incubation at body temperature (i.e., 37 °C. The composite scaffold showed a greater number of cell retention and proliferation in comparison to the PCL platform. In addition, the composite scaffold promoted the encapsulated mesenchymal stromal cells (MSCs to differentiate chondrogenically with a greater amount of cartilage-specific matrix production compared to the PCL scaffold or thermogel. Therefore, the 3D PCL/Gel composite scaffold may exhibit great potential for in vivo cartilage regeneration.

Laboratory injection molder for the fabrication of polymeric porous poly-epsilon-caprolactone scaffolds for preliminary mesenchymal stem cells tissue engineering applications

KAUST Repository

Limongi, Tania; Lizzul, Lucia; Giugni, Andrea; Tirinato, Luca; Pagliari, Francesca; Tan, Hua; Das, Gobind; Moretti, Manola; Marini, Monica; Brusatin, Giovanna; Falqui, Andrea; Torre, Bruno; Di Benedetto, Cristiano; Di Fabrizio, Enzo M.

2016-01-01

with the poly-epsilon-caprolactone (PCL) granules using a screwed thermo regulated extruder, than the biocompatible scaffolds are fabricated through injection molding. The micro/nano structure of the samples and their different grade of porosity were

Development of biodegradable metaloxide/polymer nanocomposite films based on poly-ε-caprolactone and terephthalic acid

Energy Technology Data Exchange (ETDEWEB)

Varaprasad, Kokkarachedu, E-mail: varmaindian@gmail.com [Centro de Investigación de Polímeros Avanzados (CIPA), Avenida Collao 1202, Edificio de Laboratorios, Concepción (Chile); Pariguana, Manuel [Centro de Investigación de Polímeros Avanzados (CIPA), Avenida Collao 1202, Edificio de Laboratorios, Concepción (Chile); Centro de Innovación Tecnológica Agroindustrial CITE Agroindustrial, Panamericana Sur Km, 293.3, Ica (Peru); Raghavendra, Gownolla Malegowd [Department of Packaging, Yonsei University, Wonju, Gangwon-do 220 710 (Korea, Republic of); Jayaramudu, Tippabattini [Center for Nano Cellulose Future Composites, Department of Mechanical Engineering, Inha University, 253 Yonghyun-Dong, Nam-Ku, Incheon 402–751 (Korea, Republic of); Sadiku, Emmanuel Rotimi [Department of Polymer Technology, Tshwane University of Technology, CSIR-Campus, Pretoria 0040 (South Africa)

2017-01-01

The present investigation describes the development of metal-oxide polymer nanocomposite films from biodegradable poly-ε-caprolactone, disposed poly(ethylene terephthalate) oil bottles monomer and zinc oxide-copper oxide nanoparticles. The terephthalic acid and zinc oxide-copper oxide nanoparticles were synthesized by using a temperature-dependent precipitation technique and double precipitation method, respectively. The terephthalic acid synthesized was confirmed by FTIR analysis and furthermore, it was characterized by thermal analysis. The as-prepared CuO-ZnO nanoparticles structure was confirmed by XRD analysis and its morphology was analyzed by SEM/EDS and TEM. Furthermore, the metal-oxide polymer nanocomposite films have excellent mechanical properties, with tensile strength and modulus better than pure films. The metal-oxide polymer nanocomposite films that were successfully developed show a relatively brighter colour when compared to CuO film. These new metal-oxide polymer nanocomposite films can replace many non-degradable plastics. The new metal-oxide polymer nanocomposite films developed are envisaged to be suitable for use in industrial and domestic packaging applications. - Graphical abstract: Biodegradable metal-oxide/polymer nanocomposites films prepared by using poly-ε-caprolactone with disposed PET oil bottles terephthalic acid monomer. The development of biodegradable film provides a new material with desirable mechanical, physical and chemical properties and can be utilized for industrial applications. - Highlights: • Terephthalic acid obtained from disposed PET oil bottles via precipitation technique. • New nano metal-oxides were developed by double precipitation technique. • Nano metal-oxide polymer films were synthesized by solvent evaporation method. • Nano metal-oxide polymer films exhibit superior mechanical characteristics.

Synthesis, Properties, and In Vitro Hydrolytic Degradation of Poly(d,l-lactide-co-glycolide-co-ε-caprolactone

Directory of Open Access Journals (Sweden)

Yixiu Liu

2016-01-01

Full Text Available Random copolymers of poly(d,l-lactide-co-glycolide-co-ε-caprolactone (PLGC were synthesized by the ring-opening polymerization of d,l-lactide (DLLA, glycolide (GA, and ε-caprolactone (CL. The effects of CL on the copolymers were evaluated to prepare suitable copolymers with controlled properties. Our results showed that the CL content significantly influenced the thermal and mechanical properties of the copolymers and that the CL content in compositions could be altered to control properties of random copolymers. The in vitro hydrolytic degradation of the resulting implants showed that the degradation rate of PLGC was lower than that of PLGA, which could markedly reduce acidic degradation products. Finally, we demonstrated that higher CL contents in compositions slowed degradation rates.

Ex vivo evaluation of biodegradable poly(ε-caprolactone) films in digestive fluids

Energy Technology Data Exchange (ETDEWEB)

Chang, Hao-Ming [Division of General Surgery, Tri-Service General Hospital, National Defense Medical Center, Taipei 100, Taiwan, ROC (China); Prasannan, Adhimoorthy [Graduate Institute of Applied Science and Technology, National Taiwan University of Science and Technology, Taipei 106, Taiwan, ROC (China); Tsai, Hsieh-Chih, E-mail: h.c.tsai@mail.ntust.edu.tw [Graduate Institute of Applied Science and Technology, National Taiwan University of Science and Technology, Taipei 106, Taiwan, ROC (China); Jhu, Jheng-Jun [Graduate Institute of Applied Science and Technology, National Taiwan University of Science and Technology, Taipei 106, Taiwan, ROC (China)

2014-09-15

Graphical abstract: The biodegradable poly(ε-caprolactone) (PCL) films in several digestive glands using films formed from a solution of PCL in dichloromethane and ether. The PCL films degraded very differently in different digestive glands while they continued to undergo hydrolysis. - Highlights: • Hydrolytic and protein enzymatic degradation of PCL films were studied in terms of weight loss, and the degraded films were characterized using SEM, TGA, FTIR, and DSC. • Degradation of the PCL films in saliva and gastric juice was followed by superficial erosion, while the degradation of the PCL films immersed in bile and PBS was followed by bulk erosion. • For all degraded PCL films, degradation began in the amorphous regions of the films and the fraction of crystalline PCL increased slightly. - Abstract: Successful application of biodegradable implants in the gastrointestinal tract requires intensive research to understand their degradation behavior. We studied biodegradable poly(ε-caprolactone) (PCL) films in several digestive glands using films formed from a solution of PCL in dichloromethane and ether. Examination of the film morphology showed that solvent evaporation resulted in the formation of a smooth and flat surface. In addition, our results revealed that the PCL films degraded very differently in different digestive glands while they continued to undergo hydrolysis. There was also significant weight loss in the PCL films in saliva and gastric juice, which indicates that the degradation was sensitive to protein enzymes. Deconstruction of the PCL film was first discovered when it was incubated with saliva for 6 weeks. These results indicate that the degradation by saliva was mainly responsible for the enzymatic erosion of the film, which was confirmed by scanning electron microscopy.

Morphology and mechanical properties of poly(β-hydroxybutyrate)/poly(ε-caprolactone) blends controlled with cellulosic particles.

Science.gov (United States)

Chen, Jianxiang; Wang, Yuankun; Yin, Zeren; Tam, Kam C; Wu, Defeng

2017-10-15

The rigid microcrystalline cellulose (MCC) particles and semi-rigid ethyl cellulose (EC) were used to control phase morphology and mechanical properties of immiscible poly(β-hydroxybutyrate) (PHB)/poly(ε-caprolactone) (PCL) blends. The interfacial properties were evaluated by the fiber retraction and contact angle methods MCC is incompatible with PHB and PCL, and dispersed independently in the two polymer phases in their blends. However, EC is more compatible with the two polymers, with a higher affinity for PCL. And EC prefers locating in PCL domains and at the phase interface. Selective localization of MCC and EC affects the mechanical properties and phase structure of PHB/PCL blends strongly. For the co-continuous samples, the presence of MCC and EC improves both the tensile and impact strengths. For the 'sea-island' ones, however, the changes of strengths depends strongly on the phase adhesion. This work will help focus efforts on moderating structure and properties of immiscible polymer blends using cellulose particles. Copyright © 2017 Elsevier Ltd. All rights reserved.

Studies on Poly(propylene fumarate-co-caprolactone diol Thermoset Composites towards the Development of Biodegradable Bone Fixation Devices

Directory of Open Access Journals (Sweden)

M. Jayabalan

2009-01-01

Full Text Available The effect of reinforcement in the cross-linked poly(propylene fumarate-co-caprolactone diol thermoset composites based on Kevlar fibres and hydroxyapatite was studied. Cross-linked poly(propylene fumarate-co-caprolactone diol was also studied without any reinforcement for comparison. The reinforcing fibre acts as a barrier for the curing reaction leading to longer setting time and lesser cross-link density. The fibre and HA reinforced composites have almost the same compressive strength. Nonreinforced material undergoes greater degree of swelling. Among the reinforced materials, the hydroxyapatite reinforced composite has a much higher swelling percentage than the fibre reinforced one. The studies on in vitro degradation of the cured materials reveal hydrolytic degradation in Ringer's solution and PBS medium during aging. All the three materials are found to swell initially in Ringer's solution and PBS medium during aging and then undergo gradual degradation. Compression properties of these cross-linked composites increase with aging; HA reinforced composite has the highest compressive strength and compressive modulus, whereas the aged fibre-reinforced composite has the least compressive strength and modulus.

Studies on Poly(propylene fumarate-co-caprolactone diol) Thermoset Composites towards the Development of Biodegradable Bone Fixation Devices.

Science.gov (United States)

Jayabalan, M

2009-01-01

The effect of reinforcement in the cross-linked poly(propylene fumarate-co-caprolactone diol) thermoset composites based on Kevlar fibres and hydroxyapatite was studied. Cross-linked poly(propylene fumarate-co-caprolactone diol) was also studied without any reinforcement for comparison. The reinforcing fibre acts as a barrier for the curing reaction leading to longer setting time and lesser cross-link density. The fibre and HA reinforced composites have almost the same compressive strength. Nonreinforced material undergoes greater degree of swelling. Among the reinforced materials, the hydroxyapatite reinforced composite has a much higher swelling percentage than the fibre reinforced one. The studies on in vitro degradation of the cured materials reveal hydrolytic degradation in Ringer's solution and PBS medium during aging. All the three materials are found to swell initially in Ringer's solution and PBS medium during aging and then undergo gradual degradation. Compression properties of these cross-linked composites increase with aging; HA reinforced composite has the highest compressive strength and compressive modulus, whereas the aged fibre-reinforced composite has the least compressive strength and modulus.

Synthesis, characterizations and biocompatibility of novel biodegradable star block copolymers based on poly[(R)-3-hydroxybutyrate] and poly(epsilon-caprolactone)

DEFF Research Database (Denmark)

Wu, Linping; Wang, Liang; Wang, Xiaojuan

2010-01-01

Star block copolymers based on poly[(R)-3-hydroxybutyrate] (PHB) and poly(epsilon-caprolactone) (PCL), termed SPHBCL, were successfully synthesized with structural variation on arm numbers and lengths via coupling reactions and ring opening polymerizations. Arm numbers 3, 4 and 6 of SPHBCL were...... weights of the SPHBCL due to the discrepancy of star copolymer structures. The melting temperature of SPHBCL decreased with increasing degree of branching. Thermal decomposition temperature was revealed to be lower than that of linear block copolymer LPHBCL counterparts based on PHB and PCL. Films made...... from various SPHBCL copolymers had different porous or networking surface morphology, and all possessed improved biocompatibility in terms of less blood clotting and more osteoblast cell growth compared with their corresponding homopolymers PHB and PCL. Among them, it was found, however, that the 4-arm...

Fabrication and characterization of injection molded poly ({epsilon}-caprolactone) and poly ({epsilon}-caprolactone)/hydroxyapatite scaffolds for tissue engineering

Energy Technology Data Exchange (ETDEWEB)

Cui Zhixiang [Zhengzhou University, Henan (China); Nelson, Brenton; Peng, YiYan [University of Wisconsin-Madison, Wisconsin (United States); Li Ke [South China University of Technology, Guangzhou (China); Pilla, Srikanth; Li Wanju [University of Wisconsin-Madison, Wisconsin (United States); Turng, Lih-Sheng, E-mail: turng@engr.wisc.edu [University of Wisconsin-Madison, Wisconsin (United States); South China University of Technology, Guangzhou (China); Huazhong University of Science of Technology, Wuhan (China); Shen Changyu, E-mail: shency@zzu.edu.cn [Zhengzhou University, Henan (China)

2012-08-01

In this study, poly({epsilon}-caprolactone) (PCL)/sodium chloride (NaCl), PCL/poly(ethylene oxide) (PEO)/NaCl and PCL/PEO/NaCl/hydroxyapatite (HA) composites were injection molded and characterized. The water soluble and sacrificial polymer, PEO, and NaCl particulates in the composites were leached by deionized water to produce porous and interconnected microstructures. The effect of leaching time on porosity, and residual contents of NaCl and NaCl/HA, as well as the effect of HA addition on mechanical properties was investigated. In addition, the biocompatibility was observed via seeding human mesenchymal stem cells (hMSCs) on PCL and PCL/HA scaffolds. The results showed that the leaching time depends on the spatial distribution of sacrificial PEO phase and NaCl particulates. The addition of HA has significantly improved the elastic (E Prime ) and loss moduli (E Double-Prime ) of PCL/HA scaffolds. Human MSCs were observed to have attached and proliferated on both PCL and PCL/HA scaffolds. Taken together, the molded PCL and PCL/HA scaffolds could be good candidates as tissue engineering scaffolds. Additionally, injection molding would be a potential and high throughput technology to fabricate tissue scaffolds. - Highlights: Black-Right-Pointing-Pointer PCL/NaCl, PCL/PEO/NaCl and PCL/PEO/NaCl/HA composites were injection molded. Black-Right-Pointing-Pointer Leaching time depends on the distribution of PEO phase and NaCl particulates. Black-Right-Pointing-Pointer The elastic and loss moduli of PCL/HA scaffolds have significantly improved. Black-Right-Pointing-Pointer Human hMSCs have attached, survived and proliferated well on PCL and PCL/HA scaffolds. Black-Right-Pointing-Pointer Molded PCL and PCL/HA scaffolds could be good candidates for tissue engineering.

Phosphazene-catalyzed ring-opening polymerization of ε-caprolactone: Influence of solvents and initiators

KAUST Repository

Alamri, Haleema; Zhao, Junpeng; Pahovnik, David; Hadjichristidis, Nikolaos

2014-01-01

Phosphazene base (t-BuP2) catalysed metal-free ring-opening polymerization of ε-caprolactone (ε-CL) at room temperature with various protic initiators in different solvents was investigated. The polymerization proceeded, in most cases, in a controlled manner to afford poly(ε-caprolactone) with low dispersities and expected molecular weights. Kinetic studies showed that when a primary alcohol was used as an initiator the polymerization rate in different solvents followed the order of dichloromethane ≫ toluene > 1,4-dioxane ≈ tetrahydrofuran. Extremely fast polymerization of l-lactide (LLA), which was added as a second monomer, was observed in different solvents giving rise to poly(ε-caprolactone)-b- poly(l-lactide) diblock copolymers with neat PLLA blocks despite incomplete conversion of ε-CL. The dependence of polymerization rate on the concentrations of ε-CL and t-BuP2 was also revealed. In addition to primary alcohol, the feasibility of using other protic initiators, such as secondary alcohol (either on a small molecule or a polymer chain-end), (aliphatic/aromatic) amide, carboxylic acid, phenol and thiophenol, was also investigated. These studies provided important information for designing a metal-free route towards polyester-based (bio)materials. © 2014 the Partner Organisations.

Molecular Dynamics Simulations of Adsorption of Poly(acrylic acid) and Poly(methacrylic acid) on Dodecyltrimethylammonium Chloride Micelle in Water: Effect of Charge Density.

Science.gov (United States)

Sulatha, Muralidharan S; Natarajan, Upendra

2015-09-24

We have investigated the interaction of dodecyltrimethylammonium chloride (DoTA) micelle with weak polyelectrolytes, poly(acrylic acid) and poly(methacrylic acid). Anionic as well as un-ionized forms of the polyelectrolytes were studied. Polyelectrolyte-surfactant complexes were formed within 5-11 ns of the simulation time and were found to be stable. Association is driven purely by electrostatic interactions for anionic chains whereas dispersion interactions also play a dominant role in the case of un-ionized chains. Surfactant headgroup nitrogen atoms are in close contact with the carboxylic oxygens of the polyelectrolyte chain at a distance of 0.35 nm. In the complexes, the polyelectrolyte chains are adsorbed on to the hydrophilic micellar surface and do not penetrate into the hydrophobic core of the micelle. Polyacrylate chain shows higher affinity for complex formation with DoTA as compared to polymethacrylate chain. Anionic polyelectrolyte chains show higher interaction strength as compared to corresponding un-ionized chains. Anionic chains act as polymeric counterion in the complexes, resulting in the displacement of counterions (Na(+) and Cl(-)) into the bulk solution. Anionic chains show distinct shrinkage upon adsorption onto the micelle. Detailed information about the microscopic structure and binding characteristics of these complexes is in agreement with available experimental literature.

Fabrication of thermoplastic ductile films of chitin butyrate/poly(ɛ-caprolactone) blends and their cytocompatibility.

Science.gov (United States)

Hashiwaki, Hiroki; Teramoto, Yoshikuni; Nishio, Yoshiyuki

2014-12-19

We fabricate thermoplastic films of chitin burtyrate (ChB)/poly(ɛ-caprolactone) (PCL) blends with different degree of miscibility (miscible (M), partially miscible (PM), and immiscible (IM)), and examined the feasibility as a cell scaffold system through evaluating mechanical properties and cytocompatibility. We found a remediation of the brittleness and an increase in ductility of ChB by blending PCL for the M and PM blends. The blend films were subjected to alkaline hydrolysis (2-M NaOH/37°C/48 h) with expectation of the improvement of the surface hydrophilicity and cell accessibility. ATR-FTIR spectroscopy of the alkaline-treated PM and IM films revealed that PCL component and ester side-chains of acyl chitin were selectively removed from the surface domain. L929 fibroblast cells well adhered and proliferated on these films. Therefore, the materials possess a great potential for the utilization as a thermoplastic cell scaffold in tissue engineering by adequate selection of the degree of miscibility and post treatment. Copyright © 2014 Elsevier Ltd. All rights reserved.

Poly (ɛ-caprolactone) nanoparticles of carboplatin: Preparation, characterization and in vitro cytotoxicity evaluation in U-87 MG cell lines.

Science.gov (United States)

Karanam, Vamshikrishna; Marslin, Gregory; Krishnamoorthy, Balakumar; Chellan, Vijayaraghavan; Siram, Karthik; Natarajan, Tamilselvan; Bhaskar, Balaji; Franklin, Gregory

2015-06-01

Carboplatin is a platinum based drug used in the treatment of several malignancies. Due to poor cellular uptake, generally, a larger dose of drug is administered to achieve therapeutic levels, causing harmful side-effects such as hematologic toxicity. In order to enhance the cellular uptake of carboplatin, we have developed carboplatin loaded nanoparticles using the biodegradable polymer poly (ɛ-caprolactone) (PCL). Nanoparticles ranging from the size of 23.77±1.37 to 96.73±2.79 nm with positive zeta potential and moderate entrapment efficiency (54.21±0.98%) were obtained. Transmission electron microscopy (TEM) and atomic force microscopy (AFM) confirmed the spherical morphology and smooth surface of all nanoformulations. The concentrations of PCL and the stabilizer (DMAB) are found to play a role in determining the size and the entrapment efficiency of the nanoparticles. Drug release from nanoparticles followed a biphasic pattern with an initial burst release followed by a sustained release for 10h. Results of in vitro cellular uptake and cytotoxicity studies revealed that carboplatin in the form of PCL-nanoparticles were efficiently up taken and displayed profound cytotoxicity to U-87 MG (human glioma) cells than the free drug. Importantly, unlike the free carboplatin, carboplatin in the form of PCL nanoparticles did not present any haemolytic activity in rat erythrocytes, a major side effect of this chemotherapeutic drug. This suggests that poly (ɛ-caprolactone) nanoencapsulation of carboplatin might be an efficient approach to treat cancer, while reducing carboplatin induced haemolysis. Copyright © 2015 Elsevier B.V. All rights reserved.

Self-aggregated nanoparticles based on amphiphilic poly(lactic acid-grafted-chitosan copolymer for ocular delivery of amphotericin B

Directory of Open Access Journals (Sweden)

Zhou WJ

2013-09-01

Full Text Available Wenjun Zhou,1 Yuanyuan Wang,2 Jiuying Jian,2 Shengfang Song1 1Department of Ophthalmology, Yongchuan Hospital, Chongqing Medical University, Chongqing, People’s Republic of China; 2College of Life Science, Chongqing Medical University, Chongqing, People’s Republic of China Background: The purpose of this study was to develop a self-aggregated nanoparticulate vehicle using an amphiphilic poly(lactic acid-grafted-chitosan (PLA-g-CS copolymer and to evaluate its potential for ocular delivery of amphotericin B. Methods: A PLA-g-CS copolymer was synthesized via a “protection-graft-deprotection” procedure and its structure was confirmed by Fourier transform infrared spectroscopy, 1H nuclear magnetic resonance, and X-ray diffraction spectra. Amphotericin B-loaded nanoparticles based on PLA-g-CS (AmB/PLA-g-CS were prepared by the dialysis method and characterized for particle size, zeta potential, and encapsulation efficiency. Studies of these AmB/PLA-g-CS nanoparticles, including their mucoadhesive strength, drug release properties, antifungal activity, ocular irritation, ocular pharmacokinetics, and corneal penetration were performed in vitro and in vivo. Results: Fourier transform infrared spectroscopy, 1H nuclear magnetic resonance, and X-ray diffraction spectra showed that the PLA chains were successfully grafted onto chitosan molecules and that crystallization of chitosan was suppressed. The self-aggregated PLA-g-CS nanoparticles had a core-shell structure with an average particle size of approximately 200 nm and zeta potentials higher than 30 mV. Amphotericin B was incorporated into the hydrophobic core of the nanoparticles with high encapsulation efficiency. Sustained drug release from the nanoparticles was observed in vitro. The ocular irritation study showed no sign of irritation after instillation of the PLA-g-CS nanoparticles into rabbit eyes. The minimal inhibitory concentration of the AmB/PLA-g-CS nanoparticles showed antifungal

CONTROL OF DIMENSIONAL STABILITY AND DEGRADATION RATE IN ELECTROSPUN COMPOSITE SCAFFOLDS COMPOSED OF POLY(D,L-LACTIDE-CO-GLYCOLIDE)AND POLY(Ε-CAPROLACTONE)

Institute of Scientific and Technical Information of China (English)

无

2008-01-01

The purpose of this study is to investigate the effect of composition poly(D,L-lactide-co-glycolide)/poly(ε-caprolactone)(PLGA/PCL)blending on the morphology,shrinkage and degradation behaviors of the electrospun fibers.With the increase of PLGA content in the composite fibers,the average diameter of the electrospun fibers increased from 1.35 μm to 1.95μm.The serious shrinking of the electrospun PLGA meshes could be circumvented by adding 20% PCL in the fibers,resulting from the semi-crystalline nature of PCL.The degradation rate of the electrospun meshes could be modulated by PLGA/PCL composition.In addition,the electrospun meshes containing 20% PCL displayed stable dimensional morphology with degradation.

Enzymatic Continuous Flow Synthesis of Thiol-Terminated Poly(δ-Valerolactone) and Block Copolymers.

Science.gov (United States)

Zhu, Ning; Huang, Weijun; Hu, Xin; Liu, Yihuan; Fang, Zheng; Guo, Kai

2018-04-01

Thiol-terminated poly(δ-valerolactone) is directly synthesized via enzymatic 6-mercapto-1-hexanol initiated ring-opening polymerization in both batch and microreactor. By using Candida antartica Lipase B immobilized tubular reactor, narrowly dispersed poly(δ-valerolactone) with higher thiol fidelity is more efficiently prepared in contrast to the batch reactor. Moreover, the integrated enzyme packed tubular reactor system is established to perform the chain extension experiments. Thiol-terminated poly(δ-valerolactone)-block-poly(ε-caprolactone) and poly(ε-caprolactone)-block-poly(δ-valerolactone) are easily prepared by modulating the monomer introduction sequence. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

3D- Printed Poly(ε-caprolactone) Scaffold Integrated with Cell-laden Chitosan Hydrogels for Bone Tissue Engineering

OpenAIRE

Dong, Liang; Wang, Shao-Jie; Zhao, Xin-Rong; Zhu, Yu-Fang; Yu, Jia-Kuo

2017-01-01

Synthetic polymeric scaffolds are commonly used in bone tissue engineering (BTE) due to their biocompatibility and adequate mechanical properties. However, their hydrophobicity and the lack of specific cell recognition sites confined their practical application. In this study, to improve the cell seeding efficiency and osteoinductivity, an injectable thermo-sensitive chitosan hydrogel (CSG) was incorporated into a 3D-printed poly(ε-caprolactone) (PCL) scaffold to form a hybrid scaffold. To de...

Surface characterization and biodegradation behavior of magnesium implanted poly(L-lactide/caprolactone) films

Science.gov (United States)

Sokullu, Emel; Ersoy, Fulya; Yalçın, Eyyup; Öztarhan, Ahmet

2017-11-01

Biopolymers are great source for medical applications such as drug delivery, wound patch, artificial tissue studies etc., food packaging, cosmetic applications etc. due to their biocompatibility and biodegradability. Particularly, the biodegradation ability of a biomaterial makes it even advantageous for the applications. The more tunable the biodegradation rate the more desired the biopolymers. There are many ways to tune degradation rate including surface modification. In this study ion implantation method applied to biopolymer surface to determine its effect on biodegradation rate. In this study, surface modification of poly(L-lactide/caprolactone) copolymer film is practiced via Mg-ion-implantation using a MEVVA ion source. Mg ions were implanted at a fluence of 1 × 1015 ions/cm2 and ion energy of 30 keV. Surface characterization of Mg-ion-implanted samples is examined using Atomic Force Microscopy, Raman spectroscopy, contact angle measurement and FT-IR Spectroscopy. These analyses showed that the surface become more hydrophilic and rougher after the ion implantation process which is advantageous for cell attachment on medical studies. The in vitro enzymatic degradation of Mg-implanted samples was investigated in Lipase PS containing enzyme solution. Enzymatic degradation rate was examined by mass loss calculation and it is shown that Mg-implanted samples lost more than 30% of their weight while control samples lost around 20% of their weight at the end of the 16 weeks. The evaluation of the results confirmed that Mg-ion-implantation on poly(L-lactide/caprolactone) films make the surface rougher and more hydrophilic and changes the organic structure on the surface. On the other hand, ion implantation has increased the biodegradation rate.

Radiolysis of poly(acrylic acid) in aqueous solution

Science.gov (United States)

Ulanski, Piotr; Bothe, Eberhard; Hildenbrand, Knut; Rosiak, Janusz M.; von Sonntag, Clemens

1995-02-01

Poly(acrylic acid), PAA, reacts with OH-radicals yielding -CHCH(CO 2H)- (β-radicals) and -CH 2C(CO 2H)- (α-radicals) in a ratio of approximately 2:1. This estimate is based on pulse radiolysis data where the absorption spectrum of the PAA-radicals was compared with the spectra of α-radicals from model systems. The β-radicals convert slowly into α-radicals ( k = 0.7 s -1 at pH 10). This process has also been observed by ESR. At PAA-concentrations of 10 -2 mol dm -3 chain scission dominates over other competing reactions except at low pH. The rate of chain scission was followed by pulse conductometry and in the pH range 7-9 k = 4 × 10 -2s -1 was observed. Oxygen reacts with PAA-radicals with k = 3.1 × 10 8 dm 3 mol -1 s -1 at pH 3.5 and k = 1.0 × 10 8 dm 3 mol -1 s -1 at pH 10. The corresponding peroxyl radicals undergo slow intramolecular H-transfer yielding a UV-absorbing product whose properties are that of 1,3-diketones.

Amniotic epithelial stem cell biocompatibility for electrospun poly(lactide-co-glycolide), poly(ε-caprolactone), poly(lactic acid) scaffolds

Energy Technology Data Exchange (ETDEWEB)

Russo, Valentina [Faculty of Veterinary Medicine, University of Teramo, Campus Universitario Coste S. Agostino Via R. Balzarini 1, 64100 Teramo (Italy); StemTeCh Group (Italy); Tammaro, Loredana [Department of Industrial Engineering, University of Salerno, Via Giovanni Paolo II 132, 84084 Fisciano, SA (Italy); Di Marcantonio, Lisa, E-mail: ldimarcantonio@unite.it [Faculty of Veterinary Medicine, University of Teramo, Campus Universitario Coste S. Agostino Via R. Balzarini 1, 64100 Teramo (Italy); Sorrentino, Andrea [Institute for Polymers, Composite and Biomaterials (IPCB), CNR, P.le Enrico Fermi 1, I-80055 Portici, Napoli (Italy); Ancora, Massimo [Istituto Zooprofilattico Sperimentale dell' Abruzzo e del Molise ‘G. Caporale’, Teramo (Italy); Valbonetti, Luca [Faculty of Veterinary Medicine, University of Teramo, Campus Universitario Coste S. Agostino Via R. Balzarini 1, 64100 Teramo (Italy); StemTeCh Group (Italy); Turriani, Maura; Martelli, Alessandra [Faculty of Veterinary Medicine, University of Teramo, Campus Universitario Coste S. Agostino Via R. Balzarini 1, 64100 Teramo (Italy); Cammà, Cesare [Istituto Zooprofilattico Sperimentale dell' Abruzzo e del Molise ‘G. Caporale’, Teramo (Italy); Barboni, Barbara [Faculty of Veterinary Medicine, University of Teramo, Campus Universitario Coste S. Agostino Via R. Balzarini 1, 64100 Teramo (Italy); StemTeCh Group (Italy)

2016-12-01

Three biodegradable thermoplastic polymers, poly(ε-caprolactone) (PCL), poly(L-lactide-co-D,L-lactide) (PLA) and poly(L-lactide-co-glycolide) (PLGA), have been used to produce nonwovens scaffolds with uniform micrometer fibres. Scaffolds' physical and morphological characterization was performed by X-ray diffraction, Scanning Electron Microscopy and Contact-Angle test. Morphological investigations revealed that all produced fibres were randomly orientated with interconnected pores ranging between 5 and 12 μm in diameter. An average fibre diameter of 1.5, 0.75 and 1.2 μm was found for PCL, PLA and PLGA, respectively. Moreover, experiments were designed to verify whether the fabricated electrospun substrates were biocompatible for ovine amniotic epithelial stem cells (oAECs) under in vitro conditions. Cell adhesion, survival, spatial organization on fibres, proliferation index, and DNA quantification after 48 h culture, showed an enhanced adhesion and proliferation, especially for PLGA scaffolds. The favourable interaction between oAECs and the fibrous scaffolds was attributed to the greatly improved porosity and pore size distribution of the electrospun scaffolds. In addition, AECs can be considered ideal for tissue engineering especially when using biocompatible and opportunely produced scaffolds. - Highlights: • Scaffolds have random oriented, beadless fibres and similar wettability. • Porosity and pore size distribution are determinant on boosting cell activity. • oAECs activities are influenced by scaffold chemical and physical structure. • In PLGA oAECs showed higher spatial distribution efficiency. • PLGA seeded cells present a rise in cell proliferation activity and in DNA amount.

Resveratrol-loaded poly({epsilon}-caprolactone) microparticles: preparation and characterization; Microparticulas de poli({epsilon}-caprolactona) contendo resveratrol: preparacao e caracterizacao

Energy Technology Data Exchange (ETDEWEB)

NONE

2011-07-01

Resveratrol-loaded poly({epsilon}-caprolactone) (PCL) microparticles were obtained by simple emulsion/solvent evaporation method. Three drug-loaded formulations were prepared with the aim of investigating the influence of composition on the encapsulation efficiency. Morphological and spectroscopic methods were performed for these materials. The microparticles revealed residual moisture close to 1.5% and encapsulation efficiency above 80%. Spherical shape and smooth surface were observed by SEM. No pores were either verified. Resveratrol-loaded microparticles showed an average particle size of around 50 {mu}m. X-ray diffraction analysis demonstrated that the microencapsulation reduced the drug crystallinity. The FTIR results suggest that no chemical bond was formed between polymer and drug. (author)

Cellulose nanocrystal-filled poly(acrylic acid) nanocomposite fibrous membranes

International Nuclear Information System (INIS)

Lu Ping; Hsieh, You-Lo

2009-01-01

Nanocomposite fibrous membranes have been fabricated by electrospinning cellulose nanocrystal (CNC)-loaded poly(acrylic acid) (PAA) ethanol mixtures. Incorporating CNC in PAA significantly reduced fiber diameters and improved fiber uniformity. The average diameters of the as-spun nanocomposite fibers were significantly reduced from 349 nm to 162 nm, 141 nm, 90 nm and 69 nm at 5%, 10%, 15% and 20% CNC loading (by weight of a constant 4% PAA solution), respectively. CNC was well dispersed in the fibers as isolated rods oriented along the fiber axis and as spheres in the PAA matrix. The Young modulus and stress of the PAA/CNC nanocomposite fibers were significantly improved with increasing CNC loadings by up to 35-fold and 16-fold, respectively. Heat-induced esterification between the CNC surface hydroxyls and PAA carboxyl groups produced covalent crosslinks at the CNC-PAA interfaces, rendering the nanocomposite fibrous membranes insoluble in water, more thermally stable and far more superior in tensile strength. With 20% CNC, the crosslinked nanocomposite fibrous membrane exhibited a very impressive 77-fold increase in modulus and 58-fold increase in stress.

Preparation and characterization of photocured poly (ε-caprolactone) diacrylate/poly (ethylene glycol) diacrylate/chitosan for photopolymerization-type 3D printing tissue engineering scaffold application.

Science.gov (United States)

Cheng, Yih-Lin; Chen, Freeman

2017-12-01

Because of its biocompatible, biodegradable and antimicrobial properties, chitosan is an attractive biomaterial for use in tissue engineering scaffolds. This work builds on previous research by incorporating 95% DD chitosan into a visible-light curable resin which is compatible with a digital light processing (DLP™) projection additive manufacturing (3D printing) system. Different concentrations of chitosan were added to a poly (ε-caprolactone)-diacrylate/poly (ethylene glycol)-diacrylate baseline resin and the samples were extensively characterized. Thermal and mechanical analysis conformed to established scaffold requirements. L929 cells were cultured on the photo-crosslinked films and MTT assays were performed at 1, 3, and 5days to assess cytocompatibility of the resins. Data and SEM images verified a correlation between the concentration of chitosan in the photocurable resin and the adhesion, proliferation, and viability of cell cultures. Finally, the processability of the resins with the dynamic masking DLP system was demonstrated by constructing multi-layer scaffolds with actual measurements that were consistent with the CAD models. These findings encourage the use of chitosan as an additive in visible-light curable resins to improve desired properties in tissue engineering scaffolds. Copyright © 2017 Elsevier B.V. All rights reserved.

Versatile Production of Poly(Epsilon-Caprolactone Fibers by Electrospinning Using Benign Solvents

Directory of Open Access Journals (Sweden)

Liliana Liverani

2016-04-01

Full Text Available The electrospinning technique is widely used for the fabrication of micro- and nanofibrous structures. Recent studies have focused on the use of less toxic and harmful solvents (benign solvents for electrospinning, even if those solvents usually require an accurate and longer process of optimization. The aim of the present work is to demonstrate the versatility of the use of benign solvents, like acetic acid and formic acid, for the fabrication of microfibrous and nanofibrous electrospun poly(epsilon-caprolactone mats. The solvent systems were also shown to be suitable for the fabrication of electrospun structures with macroporosity, as well as for the fabrication of composite electrospun mats, fabricated by the addition of bioactive glass (45S5 composition particles in the polymeric solution.

Direct Synthesis of Hyperbranched Poly(acrylic acid-co-3-hydroxypropionate

Directory of Open Access Journals (Sweden)

Efkan Çatıker

2015-01-01

Full Text Available Hyperbranched poly(acrylic acid-co-3-hydroxypropionate (PAcHP was synthesized by base-catalyzed hydrogen transfer polymerization of acrylic acid through one step. The copolymers obtained through solution and bulk polymerization were insoluble in water and all organic solvents tried. Structural and compositional characterizations of hyperbranched PAcHP were performed by using FTIR, solid 13C-NMR, TGA, and titrimetric analysis. Acrylate fraction of the hyperbranched PAcHP obtained via bulk polymerization was determined as 60–65% by comparing TGA curves of hyperbranched PAcHP and pure poly(3-hydroxy propionate (PHP. However, analytical titration of the same sample revealed that acrylic acid units were about 47.3%. The results obtained from TGA and analytical titration were used to evaluate the chemical structure of the copolymer. Hyperbranched PAcHP exhibited hydrogel properties. Swelling behavior of the copolymer was investigated at a wide pH range and ionic strength. The dynamic swelling profiles of hyperbranched PAcHP exhibited a fast swelling behavior in the first hour and achieved the equilibrium state within 12 h in PBS. Depending on the conditions, the copolymers exhibited swelling ratios up to 2100%. As the copolymer has easily biodegradable propionate and versatile functional acrylic acid units, it can be used as not only biodegradable material in medical applications but also raw material in personal care commodities.

Subretinal Implantation of Electrospun, Short Nanowire, and Smooth Poly(e-caprolactone) Scaffolds to the Subretinal Space of Porcine Eyes

DEFF Research Database (Denmark)

Christiansen, A T; Tao, Shanwen; Smith, M

2012-01-01

Biodegradable scaffolds play an important adjunct role in transplantation of retinal progenitor cells (RPCs) to the subretinal space. Poly(e-Caprolactone) (PCL) scaffolds with different modifications were subretinally implanted in 28 porcine eyes and evaluated by multifocal electroretinography (mf...... for the PCL Smooth. We conclude that of the tested scaffolds, PCL Short Nanowire is the best candidate for subretinal implantation....

Fluorescent, thermo-responsive biotin-P(NIPAAm-co-NDAPM)- b-PCL micelles for cell-tracking and drug delivery

International Nuclear Information System (INIS)

Li Yongyong; Zhang Xianzheng; Cheng Han; Zhu Jingling; Li Unnam; Cheng Sixue; Zhuo Renxi

2007-01-01

An amphiphilic, biotinylated poly(N-isopropylacrylamide-co-N-(3-dimethylamino propyl)methacrylamide)-block- poly(ε-caprolactone) (biotin-P(NIPAAm-co-NDAPM)- b-PCL) block copolymer was synthesized. The cytotoxicity study showed that the copolymer exhibited no apparent cytotoxicity. In aqueous solution, biotin-P(NIPAAm-co-NDAPM)- b-PCL copolymer was able to self-assemble into micelles of around 60 nm in diameter with a critical micellar concentration (CMC) of 36 mg l -1 . Biotin-P(NIPAAm- co-NDAPM)-b-PCL micelles were thermo-responsive and the cloud point temperature was at 36.5 deg. C. The fluorescent group, fluorescein isothiocyanate (FITC) was further introduced to label the biotin-P(NIPAAm-co-NDAPM)- b-PCL copolymer. A cell internalization experiment was conducted and it was found that the fluorescent micelles could be internalized into the cells. The drug release behavior of drug-loading micelles was also examined and the drug-loaded biotin-P(NIPAAm-co-NDAPM)- b-PCL micelles showed slow drug release at 27 deg. C and fast drug release at 37 deg. C

Poly(ethylene oxide monomethyl ether)- block-poly(propylene succinate) Nanoparticles: Synthesis and Characterization, Enzymatic and Cellular Degradation, Micellar Solubilization of Paclitaxel, and in Vitro and in Vivo Evaluation.

Science.gov (United States)

Jäger, Alessandro; Jäger, Eliézer; Syrová, Zdeňka; Mazel, Tomas; Kováčik, Lubomír; Raška, Ivan; Höcherl, Anita; Kučka, Jan; Konefal, Rafal; Humajova, Jana; Poučková, Pavla; Štěpánek, Petr; Hrubý, Martin

2018-04-11

Polyester-based nanostructures are widely studied as drug-delivery systems due to their biocompatibility and biodegradability. They are already used in the clinic. In this work, we describe a new and simple biodegradable and biocompatible system as the Food and Drug Administration approved polyesters (poly-ε-caprolactone, polylactic acid, and poly(lactic- co-glycolic acid)) for the delivery of the anticancer drug paclitaxel (PTX) as a model drug. A hydrophobic polyester, poly(propylene succinate) (PPS), was prepared from a nontoxic alcohol (propylene glycol) and monomer from the Krebs's cycle (succinic acid) in two steps via esterification and melt polycondensation. Furthermore, their amphiphilic block copolyester, poly(ethylene oxide monomethyl ether)- block-poly(propylene succinate) (mPEO- b-PPS), was prepared by three steps via esterification followed by melt polycondensation and the addition of mPEO to the PPS macromolecules. Analysis of the in vitro cellular behavior of the prepared nanoparticle carriers (NPs) (enzymatic degradation, uptake, localization, and fluorescence resonance energy-transfer pair degradation studies) was performed by fluorescence studies. PTX was loaded to the NPs of variable sizes (30, 70, and 150 nm), and their in vitro release was evaluated in different cell models and compared with commercial PTX formulations. The mPEO- b-PPS copolymer analysis displays glass transition temperature hydrolysis during transport in bloodstream, and simultaneous enzymatic degradability after uptake into the cells. The detailed cytotoxicity in vitro and in vivo tumor efficacy studies have shown the superior efficacy of the NPs compared with PTX and PTX commercial formulations.

D-Optimal mixture experimental design for stealth biodegradable crosslinked docetaxel-loaded poly-ε-caprolactone nanoparticles manufactured by dispersion polymerization.

Science.gov (United States)

Ogunwuyi, O; Adesina, S; Akala, E O

2015-03-01

We report here our efforts on the development of stealth biodegradable crosslinked poly-ε-caprolactone nanoparticles by free radical dispersion polymerization suitable for the delivery of bioactive agents. The uniqueness of the dispersion polymerization technique is that it is surfactant free, thereby obviating the problems known to be associated with the use of surfactants in the fabrication of nanoparticles for biomedical applications. Aided by a statistical software for experimental design and analysis, we used D-optimal mixture statistical experimental design to generate thirty batches of nanoparticles prepared by varying the proportion of the components (poly-ε-caprolactone macromonomer, crosslinker, initiators and stabilizer) in acetone/water system. Morphology of the nanoparticles was examined using scanning electron microscopy (SEM). Particle size and zeta potential were measured by dynamic light scattering (DLS). Scheffe polynomial models were generated to predict particle size (nm) and particle surface zeta potential (mV) as functions of the proportion of the components. Solutions were returned from simultaneous optimization of the response variables for component combinations to (a) minimize nanoparticle size (small nanoparticles are internalized into disease organs easily, avoid reticuloendothelial clearance and lung filtration) and (b) maximization of the negative zeta potential values, as it is known that, following injection into the blood stream, nanoparticles with a positive zeta potential pose a threat of causing transient embolism and rapid clearance compared to negatively charged particles. In vitro availability isotherms show that the nanoparticles sustained the release of docetaxel for 72 to 120 hours depending on the formulation. The data show that nanotechnology platforms for controlled delivery of bioactive agents can be developed based on the nanoparticles.

Nanosized amorphous calcium carbonate stabilized by poly(ethylene oxide)-b-poly(acrylic acid) block copolymers.

Science.gov (United States)

Guillemet, Baptiste; Faatz, Michael; Gröhn, Franziska; Wegner, Gerhard; Gnanou, Yves

2006-02-14

Particles of amorphous calcium carbonate (ACC), formed in situ from calcium chloride by the slow release of carbon dioxide by alkaline hydrolysis of dimethyl carbonate in water, are stabilized against coalescence in the presence of very small amounts of double hydrophilic block copolymers (DHBCs) composed of poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA) blocks. Under optimized conditions, spherical particles of ACC with diameters less than 100 nm and narrow size distribution are obtained at a concentration of only 3 ppm of PEO-b-PAA as additive. Equivalent triblock or star DHBCs are compared to diblock copolymers. The results are interpreted assuming an interaction of the PAA blocks with the surface of the liquid droplets of the concentrated CaCO3 phase, formed by phase separation from the initially homogeneous reaction mixture. The adsorption layer of the block copolymer protects the liquid precursor of ACC from coalescence and/or coagulation.

Light-microscopic and electron-microscopic evaluation of short-term nerve regeneration using a biodegradable poly(DL-lactide-epsilon-caprolacton) nerve guide

NARCIS (Netherlands)

denDunnen, WFA; Stokroos, [No Value; Blaauw, EH; Holwerda, A; Pennings, AJ; Robinson, PH; Schakenraad, JM

The aim of this study was to evaluate short-term peripheral nerve regeneration across a IO-mm gap, using a biodegradable poly(DL-lactide-epsilon-caprolacton) nerve guide, with an internal diameter of 1.5 mm and a wall thickness of 0.30 mm. To do so, we evaluated regenerating nerves using light

Radiolysis of poly(acrylic acid) in aqueous solution

Energy Technology Data Exchange (ETDEWEB)

Ulanski, P [Max-Planck-Institut fuer Strahlenchemie, Muelheim an der Ruhr (Germany); [Politechnika Lodzka, Lodz (Poland); Bothe, E; Hildenbrand, K; Sonntag, C von [Max-Planck-Institut fuer Strahlenchemie, Muelheim an der Ruhr (Germany); Rosiak, J M [Politechnika Lodzka, Lodz (Poland)

1995-10-01

Poly(acrylic acid), PAA, reacts with OH-radicals yielding -CH-CH(CO{sub 2}H)- ({beta}-radicals) and -CH{sub 2}-C(CO{sub 2}H)-({alpha}-radicals) in a ratio of approximately 2:1. This estimate is based on pulse radiolysis data where the absorption spectrum of the PAA-radicals was compared with the spectra of {alpha}-radicals from model systems. The {beta}-radicals convert slowly into {alpha}-radicals (k = 0.7s {sup -1} at pH 10). This process has also been observed by ESR. At PAA-concentrations of 10{sup -2} mol dm{sup -3} chain scission dominates over other competing reactions except at low pH. The rate of chain scission was followed by pulse conductometry and in the pH range 7-9 k = 4 x 10{sup -2}s{sup -1} was observed. Oxygen reacts with PAA-radicals with k = 3.1 x 10{sup 8} dm{sup 3} mol{sup -1} s{sup -1} at pH 3.5 and k = 1.0 x 10{sup 8} dm{sup 3} mol{sup -1} s{sup -1} at pH 10. The corresponding peroxyl radicals undergo slow intramolecular H-transfer yielding a UV-absorbing product whose properties are that of 1,3-diketones. (Author).

In situ intercalative polymerization of poly (ε-caprolactone)/ 12-amino lauric acid-modified clay nano composites

International Nuclear Information System (INIS)

Reyes, Larry; Monserate, Juvy J.; Sumera, Florentino

2013-01-01

Polymer/layered silicate nano composites were prepared by in situ intercalative polymerization method from from ε-caprolactone (ε-CL) and 12-amino lauric acid modified montmorillonite (AMMT). The organo-modified clay was investigated for its capacity to facilitate ring-opening polymerization of ε-caprolactone within its silicate layers. The effect of varying the organo-modified clay loading (5%, 10% and 15% by weight) on the molecular weight of the poly (ε-caprolactone) (PCL) product was assessed by gel-permeation chromatography. The molecular weight of the polymer with different clay loadings ranged from ∼30,000 g/mo to ∼70,000 g/mol, where the 10% loading produced the highest molecular weight. Fourier Transform infrared (FTIR), and 1 H and 13 C Nuclear Magnetic Resonance (NMR) Spectroscopy were conducted to probe the composition of the polymer and the catalytic activity of AMMT to polymerize ε-CL. FTIR analyses showed two medium intensity and narrow CO-O stretching vibrations for the PCL products at around 1240 cm-1 and 1160 cm-1, which are attributed to ester skeletal backbone. 1 HNMR spectroscopic analysis revealed signals at 4.07 ppm and 3.66 ppm which can be attributed to εmethylene of caprolactone and methyl of ending ester group, respectively. The formation of the nano composites were assessed by X-ray Diffraction (XRD) and Transmission Electron Microscopy (TEM), XRD analyses showed a broadening and disappearance of diffraction peak of AMMT in the nana composite which may indicate the formation of the intercalated and partially exfoliated PCVL/AMMT nana composites. TEM observations corroborated the presence of intercalated and exfoliated layers of AMMT after polymerization. The present work demonstrates that AMMT can be used as an alternative g reen catalyst's for the production of biodegradable polymers, where the in situ intercalative polymerization was employed as a direct method of preparing polymer/layered silicates (author)

Thiolated poly(ɛ-caprolactone) macroligand with vacant coordination sites on gold substrate: Synthesis and surface characterization

Science.gov (United States)

Farah, Abdiaziz A.; Zheng, Susan H.; Morin, Sylvie; Bensebaa, Farid; Pietro, William J.

2007-04-01

Surface-confined telechelic poly(ɛ-caprolactone) macroligand with two distinct functional groups per polymeric chain has been synthesized and characterized. The molecular microstructure of the macroligand with regard to the properties of the end-capped functionalities and with those on surface substrate has been studied by solution and surface analytical methods (i.e., X-ray photoelectron spectroscopy (XPS), grazing angle reflectance-Fourier transform IR spectroscopy (GA-FTIR), water contact angle measurements, and atomic force microscopy (AFM)) to elucidate the structure and properties of such multifunctional polymer on gold (1 1 1) substrate.

Synthesis and characterization of injectable, thermosensitive, and biocompatible acellular bone matrix/poly(ethylene glycol)-poly (ε-caprolactone)-poly(ethylene glycol) hydrogel composite.

Science.gov (United States)

Ni, Pei-Yan; Fan, Min; Qian, Zhi-Yong; Luo, Jing-Cong; Gong, Chang-Yang; Fu, Shao-Zhi; Shi, Shuai; Luo, Feng; Yang, Zhi-Ming

2012-01-01

In orthopedic tissue engineering, the extensively applied acellular bone matrix (ABM) can seldom be prefabricated just right to mold the cavity of the diverse defects, might induce severe inflammation on account of the migration of small granules and usually bring the patients great pain in the treatment. In this study, a new injectable thermosensitive ABM/PECE composite with good biocompatibility was designed and prepared by adding the ABM granules into the triblock copolymer poly(ethylene eglycol)-poly(ε-caprolactone)-poly(ethylene eglycol) (PEG-PCL-PEG, PECE). The PECE was synthesized by ring-opening copolymerization and characterized by ¹H NMR. The ABM was prepared by acellular treatment of natural bone and ground to fine granules. The obtained ABM/PECE composite showed the most important absorption bands of ABM and PECE copolymer in FT-IR spectroscopy and underwent sol-gel phage transition from solution to nonflowing hydrogel at 37°C. SEM results indicated that the ABM/PECE composite with different ABM contents all presented similar porous 3D structure. ABM/PECE composite presented mild cytotoxicity to rat MSCs in vitro and good biocompatibility in the BALB/c mice subcutis up to 4 weeks. In conclusion, all the results confirmed that the injectable thermosensitive ABM/PECE composite was a promising candidate for orthopedic tissue engineering in a minimally-invasive way. Copyright © 2011 Wiley Periodicals, Inc.

Stabilization of gold nanoparticles by thiol functionalized poly(ε-Caprolactone) for the labeling of PCL biocarrier

International Nuclear Information System (INIS)

Aryal, Santosh; Remant Bahadur, K.C.; Bhattarai, Narayan; Lee, Byoung Min; Kim, Hak Yong

2006-01-01

Polymer terminated by 2-(2,4-dinitrophenylsulfanyl) ethanol was synthesized by ring opening bulk polymerization of ε-Caprolactone initiated by the reaction product of aluminum isopropoxide and 2-(2,4-dinitrophenylsulfenyl) ethanol. The corresponding thiolyated poly(ε-Caprolactone) (PCL) was obtained after removal of protecting group under slightly basic condition. Both of PCL end capped by protected thiol and thiolyated PCL (PCLS-H) were characterized by 1 H NMR and the molecular weights were determined by gel permeation chromatography (GPC). Decrease in polydispersity after deprotection was observed. The PCLS-H can be grafted to the gold nanoparticles either by direct incorporation or ligand exchange with the existing undecanethiol on the gold nanoparticles. The resulting nanoparticles were characterized by Raman spectroscopy and transmission electron microscope (TEM). Mixed ligands stabilized gold nanoparticles were further used for the labeling of PCL biocarrier by nanoprecipitation. The sizes of these nanoparticles-labeled biocarrier were determined by TEM. This is an easy and convenient way to label biocarrier by the gold nanoparticles based contrasting agent in order to study its consequences in vivo

The influence of poly(acrylic) acid number average molecular weight and concentration in solution on the compressive fracture strength and modulus of a glass-ionomer restorative.

LENUS (Irish Health Repository)

Dowling, Adam H

2011-06-01

The aim was to investigate the influence of number average molecular weight and concentration of the poly(acrylic) acid (PAA) liquid constituent of a GI restorative on the compressive fracture strength (σ) and modulus (E).

Branched Crystalline Patterns of Poly(ε-caprolactone) and Poly(4-hydroxystyrene) Blends Thin Films.

Science.gov (United States)

Hou, Chunyue; Yang, Tianbo; Sun, Xiaoli; Ren, Zhongjie; Li, Huihui; Yan, Shouke

2016-01-14

The chain organization of poly(ε-caprolactone) (PCL) in its blend with poly(4-hydroxystyrene) (PVPh) in thin films (130 ± 10 nm) has been revealed by grazing incident infrared (GIIR) spectroscopy. It can be found that PCL chains orient preferentially in the surface-normal direction and crystallization occurs simultaneously. The morphology of the PCL/PVPh blends films can be identified by optical microscopy (OM). When crystallized at 35 °C, the blends film shows a seaweed-like structure and becomes more open with increasing PVPh content. In contrast, when crystallized at higher temperatures, i.e., 40 and 45 °C, dendrites with apparent crystallographically favored branches can be observed. This characteristic morphology indicates that the diffusion-limited aggregation (DLA) process controls the crystal growth in the blends films. The detailed lamellar structure can be revealed by the height images of atomic force microscopy (AFM), i.e., the crystalline branches are composed of overlayered flat-on lamellae. The branch width has been found to be dependent on the supercooling and PVPh content. This result differs greatly from pure PCL, in which case the crystal patterns controlled by DLA process developed in ultrathin film or monolayers of several nanometers. In the PCL/PVPh blends case, the strong intermolecular interactions and the dilution effect of PVPh should contribute to these results. That is to say, the mobility of PCL chains can be retarded and diffusion of them to the crystal growth front slows down greatly, even though the film thickness is far more than the lamellar thickness of PCL.

Self-assembly of block copolymer-based ionic supramolecules based upon multi-tail amphiphiles

DEFF Research Database (Denmark)

Asad Ayoubi, M.; Almdal, Kristoffer; Zhu, K.

2015-01-01

Utilising simple acid-base titration chemistry, a new family of Linear-b-Amphiphilic Comb (L-b-AC) ionic supramolecules [Soft Matter 2013, 9, 1540-1555] featuring multi-tail side-chains have been synthesized and examined by synchrotron SAXS. To three different parent diblock copolymers of poly...

Electrospun composite matrices of poly(ε-caprolactone)-montmorillonite made using tenside free Pickering emulsions.

Science.gov (United States)

Samanta, Archana; Takkar, Sonam; Kulshreshtha, Ritu; Nandan, Bhanu; Srivastava, Rajiv K

2016-12-01

The production of composite electrospun matrices of poly(ε-caprolactone) (PCL) using an emulsifier-free emulsion, made with minimal organic solvent, as precursor is reported. Pickering emulsions of PCL were prepared using modified montmorillonite (MMT) clay as the stabilizer. Hydrophobic tallow group of the modified MMT clay resulted in analogous interaction of clay with oil and aqueous phase and its adsorption at the interface to provide stability to the resultant emulsion. Composite fibrous matrices of PCL and MMT were produced using electrospinning under controlled conditions. The fiber fineness was found to alter with PCL concentration and volume fraction of the aqueous and oil phases. A higher tensile strength and modulus was obtained with inclusion of MMT in PCL electrospun matrix in comparison to a matrix made using neat PCL. The presence of clay in the fibrous matrix did not change the cell proliferation efficiency in comparison to neat PCL matrix. Composite fibrous matrices of PCL/MMT bearing enhanced tensile properties may find applications in areas other than tissue engineering for example food packaging and filtration. Copyright © 2016 Elsevier B.V. All rights reserved.

NITROAROMATIC COMPOUND SENSING APPLICATION OF HEXA-ARMED DANSYL END-CAPPED POLY(epsilon-CAPROLACTONE STAR POLYMER WITH PHOSPHAZENE CORE

Directory of Open Access Journals (Sweden)

Merve DANDAN DOGANCI

2016-09-01

Full Text Available Hexa-armed dansyl end-capped poly(ε-caprolactone star polymer with phosphazene core (N3P3-(PCL-Dansyl6 was prepared in a two-step synthetic procedure including ring opening polymerization (ROP of ε-caprolactone (ε-CL and esterification reactions. The obtained fluorescence-active polymer was employed as a fluorescent probe towards certain nitroaromatic compounds (2,4,6-trinitrotoluene (TNT, 2,4-dinitrotoluene, 2,6-dinitrotoluene, 2-nitrotoluene, 3-nitrotoluene, 2,4,6-trinitrophenol (picric acid, 2,4-dinitrophenol, 4-nitrophenol, and 1,2-dinitrobenzene. Fluorescence intensity of N3P3-(PCL-Dansyl6 was decreased gradually upon the addition of nitroaromatic compounds and the highest quenching efficiency was found to be 100% with TNT. Besides, N3P3-(PCL-Dansyl6 gave exceptionally selective response toward nitroaromatic compounds, even in the presence of toxic metal cations such as Pb2+, Co2+, Hg2+, Mn2+, Cd2+ and Zn2+.

Radiation induced deposition of copper nanoparticles inside the nanochannels of poly(acrylic acid)-grafted poly(ethylene terephthalate) track-etched membranes

Science.gov (United States)

Korolkov, Ilya V.; Güven, Olgun; Mashentseva, Anastassiya A.; Atıcı, Ayse Bakar; Gorin, Yevgeniy G.; Zdorovets, Maxim V.; Taltenov, Abzal A.

2017-01-01

Poly(ethylene terephthalate) PET, track-etched membranes (TeMs) with 400 nm average pore size were UV-grafted with poly(acrylic acid) (PAA) after oxidation of inner surfaces by H2O2/UV system. Carboxylate groups of grafted PAA chains were easily complexed with Cu2+ ions in aqueous solutions. These ions were converted into metallic copper nanoparticles (NPs) by radiation-induced reduction of copper ions in aqueous-alcohol solution by gamma rays in the dose range of 46-250 kGy. Copper ions chelating with -COOH groups of PAA chains grafted on PET TeMs form polymer-metal ion complex that prevent the formation of agglomerates during reduction of copper ions to metallic nanoparticles. The detailed analysis by X-Ray diffraction technique (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) confirmed the deposition of copper nanoparticles with the average size of 70 nm on the inner surface of nanochannels of PET TeMs. Samples were also investigated by FTIR, ESR spectroscopies to follow copper ion reduction.

A study on the swelling behavior of poly(acrylic acid) hydrogels obtained by electron beam crosslinking

Science.gov (United States)

Sheikh, N.; Jalili, L.; Anvari, F.

2010-06-01

Poly(acrylic acid) (PAA) hydrogels were prepared by using electron beam (EB) crosslinking of PAA homopolymer from its aqueous solutions. The swelling behavior of the hydrogels was studied as a function of the concentration of PAA solution, radiation dose, pH of the swelling medium and swelling time. Also the environmental pH effect on the water diffusion mode into hydrogels was investigated. These hydrogels clearly showed pH-sensitive swelling behavior with Fickian type of diffusion in the stomach-like pH medium (pH 1.3) and non-Fickian type in the intestine-like pH medium (pH 6.8).

A study on the swelling behavior of poly(acrylic acid) hydrogels obtained by electron beam crosslinking

International Nuclear Information System (INIS)

Sheikh, N.; Jalili, L.; Anvari, F.

2010-01-01

Poly(acrylic acid) (PAA) hydrogels were prepared by using electron beam (EB) crosslinking of PAA homopolymer from its aqueous solutions. The swelling behavior of the hydrogels was studied as a function of the concentration of PAA solution, radiation dose, pH of the swelling medium and swelling time. Also the environmental pH effect on the water diffusion mode into hydrogels was investigated. These hydrogels clearly showed pH-sensitive swelling behavior with Fickian type of diffusion in the stomach-like pH medium (pH 1.3) and non-Fickian type in the intestine-like pH medium (pH 6.8).

Poly(acrylic acid)-block-poly(vinyl alcohol) anchored maghemite nanoparticles designed for multi-stimuli triggered drug release

Science.gov (United States)

Liu, Ji; Detrembleur, Christophe; Debuigne, Antoine; de Pauw-Gillet, Marie-Claire; Mornet, Stéphane; Vander Elst, Luce; Laurent, Sophie; Labrugère, Christine; Duguet, Etienne; Jérôme, Christine

2013-11-01

Original core/corona nanoparticles composed of a maghemite core and a stimuli-responsive polymer coating made of poly(acrylic acid)-block-poly(vinyl alcohol) macromolecules were fabricated for drug delivery system (DDS) application. This kind of DDS aims to combine the advantage of stimuli-responsive polymer coating, in order to regulate the drug release behaviours under different conditions and furthermore, improve the biocompatibility and in vivo circulation half-time of the maghemite nanoparticles. Drug loading capacity was evaluated with methylene blue (MB), a cationic model drug. The triggered release of MB was studied under various stimuli such as pH, ionic strength and temperature. Local heating generated under alternating magnetic field (AMF) application was studied, and remotely AMF-triggered release was also confirmed, while a mild heating-up of the release medium was observed. Furthermore, their potential application as magnetic resonance imaging (MRI) contrast agents was explored via relaxivity measurements and acquisition of T2-weighted images. Preliminary studies on the cytotoxicity against mouse fibroblast-like L929 cell line and also their cellular uptake within human melanoma MEL-5 cell line were carried out. In conclusion, this kind of stimuli-responsive nanoparticles appears to be promising carriers for delivering drugs to some tumour sites or into cellular compartments with an acidic environment.Original core/corona nanoparticles composed of a maghemite core and a stimuli-responsive polymer coating made of poly(acrylic acid)-block-poly(vinyl alcohol) macromolecules were fabricated for drug delivery system (DDS) application. This kind of DDS aims to combine the advantage of stimuli-responsive polymer coating, in order to regulate the drug release behaviours under different conditions and furthermore, improve the biocompatibility and in vivo circulation half-time of the maghemite nanoparticles. Drug loading capacity was evaluated with methylene

Electrospun curcumin loaded poly(ε-caprolactone)/gum tragacanth nanofibers for biomedical application.

Science.gov (United States)

Ranjbar-Mohammadi, Marziyeh; Bahrami, S Hajir

2016-03-01

In this work curcumin (Cur)-loaded poly(ε-caprolactone) (PCL)/gum tragacanth (GT) scaffold membranes which provided the controlled release of curcumin for over 20 days were fabricated by electrospinning. Field Emission Scanning Electron Microscopy (FESEM) analysis, Fourier Transform Infrared Spectroscopy (FTIR) and differential scanning calorimetry (DSC) were applied to characterize the produced nanofibers. These nanofibers were evaluated for water absorption capacity, in vitro drug release, biodegradation test, cell culture and MTT analysis. The water contact angle measurements indicated that addition of GT and curcumin in composition resulted in increase in the hydrophilicity of the nanofibers. Biodegradation test for the fabricated nanofibers exhibited that PCL/GT, PCL/Cur-3% and PCL/GT/Cur-3% nanofibers preserved their structure after 15 days. The in vitro release profile of curcumin showed 6.86, 14 and 30.09% burst release for PCL/GT/Cur-1%, PCL/GT/Cur-3% and PCL/Cur-3% nanofibers respectively. The effect of curcumin concentration in the nanofibers composition on the cell viability was assessed by the MTS assay. The cytotoxic effect of released curcumin on the fibroblast cells was examined. The PCL/GT/Cur-3% with suitable mechanical properties, excellent biological characteristics, and maintaining their original structure in degradation media may have potential application as a wound dressing patch for healing slow rate wounds. Copyright © 2015 Elsevier B.V. All rights reserved.

Synthesis of an amphiphilic dendrimer-like block copolymer and its application on drug delivery

KAUST Repository

Wang, Shuaipeng

2014-10-27

Dendrimer-like amphiphilic copolymer is a kind of three-dimensional spherical structure polymer. An amphiphilic dendrimer-like diblock copolymer, PEEGE-G2-b-PEO(OH)12, constituted of a hydrophobic poly(ethoxyethyl glycidol ether) inner core and a hydrophilic poly(ethylene oxide) outer layer, has been successfully synthesized by the living anionic ring-opening polymerization method. The intermediates and targeted products were characterized with 1H NMR spectroscopy and gel permeation chromatography. The application on drug delivery of dendrimer-like diblock copolymer PEEGE-G2-b-PEO(OH)12 using DOX as a model drug was also studied. The drug loading content and encapsulation efficiency were found at 13.07% and 45.75%, respectively. In vitro release experiment results indicated that the drug-loaded micelles exhibited a sustained release behavior under acidic media.

Synthesis, Amphiphilic Property and Thermal Stability of Novel Main-chain Poly(o-carborane-benzoxazines)

Science.gov (United States)

Yang, Xiaoxue; Han, Guo; Yang, Zhen; Zhang, Xiaoa; Jiang, Shengling; Lyu, Yafei

2017-10-01

Five poly(o-carborane-benzoxazines) were synthesized via Mannich reaction of o-carborane bisphenol, paraformaldehyde, and diamine, and their structures were well characterized. Light transmission and 1H NMR in D2O confirmed that poly(o-carborane-benzoxazines) with PEG segments showed excellent water solubility and amphiphilic property. TGA analyses were conducted under nitrogen and air, and the results showed that the polymers own high initial decomposition temperatures owing to the shielding effect of carborane moiety on its adjacent aromatic structures. Besides, poly(o-carborane-benzoxazines) own high char yield at elevated temperatures, for the boron atom could combine with oxygen from the polymer structure or/and the air and be oxidized to form boron oxide, and thus the polymer weight is retained to a large extent. PEG segments had an adverse effect on the initial decomposition and char yield, and thus their concentration should be adjusted to control the polymer’s thermal stability.

Effects of poly(L-lactide-ε-caprolactone) and magnesium hydroxide additives on physico-mechanical properties and degradation of poly(L-lactic acid).

Science.gov (United States)

Kang, Eun Young; Lih, Eugene; Kim, Ik Hwan; Joung, Yoon Ki; Han, Dong Keun

2016-01-01

Biodegradable poly(L-lactic acid) (PLLA) is one of the most widely used polymer in biomedical devices, but it still has limitations such as inherent brittleness and acidic degradation products. In this work, PLLA blends with poly(L-lactide-ε-caprolactone) (PLCL) and Mg(OH)2 were prepared by the thermal processing to improve their physico-mechanical and thermal properties. In addition, the neutralizing effect of Mg(OH)2 was evaluated by degradation study. The elongation of PLLA remarkably increased from 3 to 164.4 % and the glass transition temperature (Tg) of PLLA was slightly reduced from 61 to 52 °C by adding PLCL additive. Mg(OH)2 in polymeric matrix not only improved the molecular weight reduction and mechanical strength of PLLA, but also neutralized the acidic byproducts generated during polyester degradation. Therefore, the results demonstrated that the presence of PLCL and Mg(OH)2 additives in PLLA matrix could prevent the thermal decomposition and control degradation behavior of polyester.

Microencapsulation of superoxide dismutase into poly(epsilon-caprolactone) microparticles by reverse micelle solvent evaporation.

Science.gov (United States)

Youan, Bi-Botti Célestin

2003-01-01

The aim of this work was to encapsulate superoxide dismutase (SOD) in poly(epsilon-caprolactone) (PCL) microparticles by reverse micelle solvent evaporation. The concentration of PCL, the hydrophile-lipophile balance (HLB), and concentration of the sucrose ester used as surfactant in the organic phase were investigated as formulation variables. Relatively higher encapsulation efficiency (approximately 48%) and retained enzymatic activity (>90%) were obtained with microparticle formulation made from the 20% (w/v) PCL and 0.05% (w/v) sucrose ester of HLB = 6. This formulation allowed the in vitro release of SOD for at least 72 hr. These results showed that reverse micelle solvent evaporation can be used to efficiently encapsulate SOD in PCL microparticles. Such formulations may improve the bioavailability of SOD.

Effect of poly ethylene glycol on the mechanical and thermal properties of bioactive poly(ε-caprolactone) melt extrudates for pharmaceutical applications.

Science.gov (United States)

Douglas, P; Albadarin, Ahmad B; Sajjia, M; Mangwandi, Chirangano; Kuhs, Manuel; Collins, Maurice N; Walker, Gavin M

2016-03-16

This paper investigates the effects of polyethylene glycol (PEG), on the mechanical and thermal properties of nalidixic acid/poly ε-caprolactone (NA)/PCL blends prepared by hot melt extrusion. The blends were characterized by tensile and flexural analysis, dynamic mechanical analysis, differential scanning calorimetry, thermogravimetric analysis and X-ray diffraction. Results show that loading PEG in the PCL had a detrimental effect on the tensile strength and toughness of the blends, reducing them by 20-40%. The partial miscibility of the PCL-PEG system, causes an increase in Tg. While increases in the crystallinity is attributed to the plasticisation effect of PEG and the nucleation effect of NA. The average crystal size increased by 8% upon PEG addition. Experimental data indicated that the addition of NA caused loss of the tensile strength and toughness of PCL. Thermal analysis of the PCL showed that on addition of the thermally unstable NA, thermal degradation occurred early and was autocatalytic. However, the NA did benefit from the heat shielding provided by the PCL matrix resulting in more thermally stable NA particles. Copyright © 2016 Elsevier B.V. All rights reserved.

In-situ polymerization and characterization of poly ({epsilon} -caprolactone) urethane/ SiO{sub 2} nanocomposites

Energy Technology Data Exchange (ETDEWEB)

Chen Xiaodong; Zhou Nanqiao [National Engineering Research Center of Novel Equipment for Polymer Processing, South China University of Technology, Guangzhou, Guangdong, 510640 (China); Zhang Hai [Guangzhou SCUT Bestry Technology Joint-stock Co. Ltd, Guangzhou, Guangdong, 510640 (China)], E-mail: cxdzlgzhnlg2003@163.com

2009-09-01

Nanocomposites of poly({epsilon} -caprolactone) (PCL) castable polyurethane elastomer (CPUE) with nano-SiO{sub 2} particles of different surface properties were prepared via in-situ polymerization. An electronmechanical universal testing machine, a durometer, a rubber resilience experimental machine, a dynamic-mechanical analyzer, a thermogravimetric analysis and a scanning electron microscope were used to investigate the macro -static/dynamic mechanical properties, micro-dispersed state and thermostability. The results showed that the modulus at 100% and 300%, elongation at break, tensile strength and tear strength of poly({epsilon} -caprolactone) urethane nanocomposites were increased by introducing a certain amount of nano-SiO{sub 2}. Especially the tensile strength and tear strength at 100 deg. C of the PCL CPUE with 5% nano-SiO{sub 2} pretreated by {gamma}-glycidochloropropyl methyl trimethoxy silane (trade name A-187) were 1.50 and 1.94 times than those of the pure PCL CPUE, respectively. The addition of the nano-SiO{sub 2} had little effect on the hardness, but the impact resilience decreased slightly. The loss factor peaks of two nano-SiO{sub 2} polyurethane composites were higher obviously than the pure PCL CPUE and the glass transition temperature (T{sub g}) of the two nano-SiO{sub 2} polyurethane composites increased to higher temperature region. The surface treatment by the optimum silane coupling agent influenced the dispersibility of nano-SiO{sub 2} in the PCL CPUE distinctly. The agglomerating phenomenon, and even some nano-agglomerates with more than 1 {mu}m diameter can be observed in the PCL CPUE with 5% untreated nano-SiO{sub 2}, but the nano-SiO{sub 2} pretreated by A-187 was dispersed in the PCL CPUE at nano-scale.

Development of nanofibrous scaffolds containing gum tragacanth/poly (ε-caprolactone) for application as skin scaffolds

Energy Technology Data Exchange (ETDEWEB)

Ranjbar-Mohammadi, Marziyeh [Textile Engineering Department, Amirkabir University of Technology, Tehran (Iran, Islamic Republic of); Bahrami, S. Hajir, E-mail: hajirb@aut.ac.ir [Textile Engineering Department, Amirkabir University of Technology, Tehran (Iran, Islamic Republic of); Center for excellence Modern Textile Characterization, Tehran (Iran, Islamic Republic of)

2015-03-01

Outstanding wound healing activity of gum tragacanth (GT) and higher mechanical strength of poly (ε-caprolactone) (PCL) may produce an excellent nanofibrous patch for either skin tissue engineering or wound dressing application. PCL/GT scaffold containing different concentrations of PCL with different blend ratios of GT/PCL was produced using 90% acetic acid as solvent. The results demonstrated that the PCL/GT (3:1.5) with PCL concentration of 20% (w/v) produced nanofibers with proper morphology. Scanning electron microscopy (SEM) and differential scanning calorimetry (DSC) were utilized to characterize the nanofibers. Surface wettability, functional groups analysis, porosity and tensile properties of nanofibers were evaluated. Morphological characterization showed that the addition of GT to PCL solution results in decreasing the average diameter of the PCL/GT nanofibers. However, the hydrophilicity increased in the PCL/GT nanofibers. Slight increase in melting peaks was observed due to the blending of PCL with GT nanofibers. PCL/GT nanofibers were used for in vitro cell culture of human fibroblast cell lines AGO and NIH 3T3 fibroblast cells. MTT assay and SEM results showed that the biocomposite PCL/GT mats enhanced the fibroblast adhesion and proliferation compared to PCL scaffolds. The antibacterial activity of PCL/GT and GT nanofibers against Staphylococcus aureus and Pseudomonas aeruginosa was also examined. - Highlights: • A new skin tissue engineering scaffold from poly (ε-caprolactone) (PCL) and gum tragacanth (GT) has been developed. • These scaffolds might be an effectual simulator of the structure and composition of native skin. • Very slight increase in melting peaks was observed due to the blending of PCL with GT nanofibers. • Biodegradation, water uptake and hydrophilicity properties of these scaffolds showed that produced scaffolds were adherent. • The electrospun PCL/GT scaffold can promote the skin regeneration of full

Development of nanofibrous scaffolds containing gum tragacanth/poly (ε-caprolactone) for application as skin scaffolds

International Nuclear Information System (INIS)

Ranjbar-Mohammadi, Marziyeh; Bahrami, S. Hajir

2015-01-01

Outstanding wound healing activity of gum tragacanth (GT) and higher mechanical strength of poly (ε-caprolactone) (PCL) may produce an excellent nanofibrous patch for either skin tissue engineering or wound dressing application. PCL/GT scaffold containing different concentrations of PCL with different blend ratios of GT/PCL was produced using 90% acetic acid as solvent. The results demonstrated that the PCL/GT (3:1.5) with PCL concentration of 20% (w/v) produced nanofibers with proper morphology. Scanning electron microscopy (SEM) and differential scanning calorimetry (DSC) were utilized to characterize the nanofibers. Surface wettability, functional groups analysis, porosity and tensile properties of nanofibers were evaluated. Morphological characterization showed that the addition of GT to PCL solution results in decreasing the average diameter of the PCL/GT nanofibers. However, the hydrophilicity increased in the PCL/GT nanofibers. Slight increase in melting peaks was observed due to the blending of PCL with GT nanofibers. PCL/GT nanofibers were used for in vitro cell culture of human fibroblast cell lines AGO and NIH 3T3 fibroblast cells. MTT assay and SEM results showed that the biocomposite PCL/GT mats enhanced the fibroblast adhesion and proliferation compared to PCL scaffolds. The antibacterial activity of PCL/GT and GT nanofibers against Staphylococcus aureus and Pseudomonas aeruginosa was also examined. - Highlights: • A new skin tissue engineering scaffold from poly (ε-caprolactone) (PCL) and gum tragacanth (GT) has been developed. • These scaffolds might be an effectual simulator of the structure and composition of native skin. • Very slight increase in melting peaks was observed due to the blending of PCL with GT nanofibers. • Biodegradation, water uptake and hydrophilicity properties of these scaffolds showed that produced scaffolds were adherent. • The electrospun PCL/GT scaffold can promote the skin regeneration of full

Environmentally Friendly Compatibilizers from Soybean Oil for Ternary Blends of Poly(lactic acid-PLA, Poly(ε-caprolactone-PCL and Poly(3-hydroxybutyrate-PHB

Directory of Open Access Journals (Sweden)

María Jesús Garcia-Campo

2017-11-01

Full Text Available Ternary blends of poly(lactic acid (PLA, poly(3-hydroxybutyrate (PHB and poly(ε-caprolactone (PCL with a constant weight percentage of 60%, 10% and 30% respectively were compatibilized with soybean oil derivatives epoxidized soybean oil (ESO, maleinized soybean oil (MSO and acrylated epoxidized soybean oil (AESO. The potential compatibilization effects of the soybean oil-derivatives was characterized in terms of mechanical, thermal and thermomechanical properties. The effects on morphology were studied by field emission scanning electron microscopy (FESEM. All three soybean oil-based compatibilizers led to a noticeable increase in toughness with a remarkable improvement in elongation at break. On the other hand, both the tensile modulus and strength decreased, but in a lower extent to a typical plasticization effect. Although phase separation occurred, all three soybean oil derivatives led somewhat to compatibilization through reaction between terminal hydroxyl groups in all three biopolyesters (PLA, PHB and PCL and the readily reactive groups in the soybean oil derivatives, that is, epoxy, maleic anhydride and acrylic/epoxy functionalities. In particular, the addition of 5 parts per hundred parts of the blend (phr of ESO gave the maximum elongation at break while the same amount of MSO and AESO gave the maximum toughness, measured through Charpy’s impact tests. In general, the herein-developed materials widen the potential of ternary PLA formulations by a cost effective blending method with PHB and PCL and compatibilization with vegetable oil-based additives.

Environmentally Friendly Compatibilizers from Soybean Oil for Ternary Blends of Poly(lactic acid)-PLA, Poly(ε-caprolactone)-PCL and Poly(3-hydroxybutyrate)-PHB.

Science.gov (United States)

Garcia-Campo, María Jesús; Quiles-Carrillo, Luis; Masia, Jaime; Reig-Pérez, Miguel Jorge; Montanes, Nestor; Balart, Rafael

2017-11-22

Ternary blends of poly(lactic acid) (PLA), poly(3-hydroxybutyrate) (PHB) and poly(ε-caprolactone) (PCL) with a constant weight percentage of 60%, 10% and 30% respectively were compatibilized with soybean oil derivatives epoxidized soybean oil (ESO), maleinized soybean oil (MSO) and acrylated epoxidized soybean oil (AESO). The potential compatibilization effects of the soybean oil-derivatives was characterized in terms of mechanical, thermal and thermomechanical properties. The effects on morphology were studied by field emission scanning electron microscopy (FESEM). All three soybean oil-based compatibilizers led to a noticeable increase in toughness with a remarkable improvement in elongation at break. On the other hand, both the tensile modulus and strength decreased, but in a lower extent to a typical plasticization effect. Although phase separation occurred, all three soybean oil derivatives led somewhat to compatibilization through reaction between terminal hydroxyl groups in all three biopolyesters (PLA, PHB and PCL) and the readily reactive groups in the soybean oil derivatives, that is, epoxy, maleic anhydride and acrylic/epoxy functionalities. In particular, the addition of 5 parts per hundred parts of the blend (phr) of ESO gave the maximum elongation at break while the same amount of MSO and AESO gave the maximum toughness, measured through Charpy's impact tests. In general, the herein-developed materials widen the potential of ternary PLA formulations by a cost effective blending method with PHB and PCL and compatibilization with vegetable oil-based additives.

Micro- and nanophase separations in hierarchical self-assembly of strongly amphiphilic block copolymer-based ionic supramolecules

DEFF Research Database (Denmark)

Ayoubi, Mehran Asad; Zhu, Kaizheng; Nyström, Bo

2013-01-01

block), a class of ionic supramolecules are successfully synthesized whose molecular architecture consists of a poly(styrene) PS block (Linear block) covalently connected to a strongly amphiphilic comb-like block (AmphComb block), i.e. Linear-b-AmphComb. In the melt state, these ionic supramolecules can.......20 (SLL/C and SBCC/C) and ∼0.28 (C/L). Finally, the specific influences of the strongly amphiphilic nature of the AmphComb blocks on the observed morphological and hierarchical behaviours of our system are discussed. For reference, stoichiometric strongly amphiphilic comb-like (AmphComb) ionic...

Radiation-induced synthesis of poly(acrylic acid) nanogels

Science.gov (United States)

Matusiak, Malgorzata; Kadlubowski, Slawomir; Ulanski, Piotr

2018-01-01

Nanogel is a two-component system of a diameter in the range of tens of nanometers, consisting of an intramolecularly crosslinked polymer chain and solvent, typically water, filling the space between segments of the macromolecule. Microgels are bigger than nanogels and their size range is between 100 nm to 100 μm. One of the methods used for synthesizing nanogels is linking the segments of a single macromolecule with the use of ionizing radiation, by intramolecular recombination of radiation-generated polymer radicals. The main advantage of this technique is absence of monomers, catalysts, surfactants or crosslinking agents. This method is an interesting alternative way of synthesizing polymeric carriers for biomedical applications. The aim of the study was radiation synthesis and characterization of poly(acrylic acid) - PAA - nanogels and microgels. The physico-chemical properties were described by determination of weight-average molecular weight and dimensions (radius of gyration, hydrodynamic radius) of the nanogels and microgels. Influence of polymer concentration and dose on these parameters was analyzed. Adjusting the PAA concentration and absorbed dose, one can control the molecular weight and dimensions of nanogels. The solutions of PAA were irradiated with two sources of ionizing radiation: γ-source and electron accelerator. The former method yields mainly microgels due to prevailing intermolecular crosslinking, while the latter promotes intramolecular recombination of PAA-derived radicals and in consequence formation of nanogels. In the future radiation-synthesized PAA nanogels, after functionalization, will be tested as carriers for delivering radionuclides to the tumor cells.

Chitosan grafted methoxy poly(ethylene glycol)-poly(ε-caprolactone) nanosuspension for ocular delivery of hydrophobic diclofenac.

Science.gov (United States)

Shi, Shuai; Zhang, Zhaoliang; Luo, Zichao; Yu, Jing; Liang, Renlong; Li, Xingyi; Chen, Hao

2015-06-12

This study aimed to develop a cationic nanosuspension of chitosan (CS) and methoxy poly(ethylene glycol)-poly(ε-caprolactone) (MPEG-PCL) for ocular delivery of diclofenac (DIC). MPEG-PCL-CS block polymer was synthesized by covalent coupling of MPEG-PCL with CS. The critical micelle concentration of the MPEG-PCL-CS block polymer was 0.000692 g/L. DIC/MPEG-PCL-CS nanosuspension (mean particle size = 105 nm, zeta potential = 8 mV) was prepared and characterized by Fourier transform infrared spectroscopy, X-ray diffraction, and differential scanning calorimetry. The nanosuspension was very stable without apparent physical property changes after storage at 4 °C or 25 °C for 20 days, but it was unstable in the aqueous humor solution after 24 h incubation. Sustained release of the encapsulated DIC from the nanosuspension occurred over 8 h. Neither a blank MPEG-PCL-CS nanosuspension nor a 0.1% (mass fraction) DIC/MPEG-PCL-CS nanosuspension caused ocular irritation after 24 h of instillation. Enhanced penetration and retention in corneal tissue was achieved with a Nile red/MPEG-PCL-CS nanosuspension compared with a Nile red aqueous solution. In vivo pharmacokinetics studies showed enhanced pre-corneal retention and penetration of the DIC/MPEG-PCL-CS nanosuspension, which resulted in a higher concentration of DIC (Cmax) in the aqueous humor and better bioavailability compared with commercial DIC eye drops (P < 0.01).

Evaluation of scission and crosslinking yields in γ-irradiated poly(acrylic acid) and poly(methacrylic acid) from weight- and Ζ-average molecular weights determined by sedimentation equilibrium

International Nuclear Information System (INIS)

Hill, D.J.T.; O'Donnell, J.H.; Winzor, C.L.; Winzor, D.J.

1990-01-01

Weight- and Ζ-average molecular weights, M-bar W (D) and M-bar Ζ (D), of poly(methacrylic acid) (PMMA) and poly(acrylic acid) (PAA) have been determined by sedimentation equilibrium in the ultracentrifuge after various doses D of γ-radiation in vacuum. Relationships between [M i (0)/M i (D)-1]/D and D (i=w or Ζ), derived recently by O'Donnell and coworkers, have been used to determine radiation chemical yields for scission and crosslinking of G(S)=6.0, G(X)=0 for PMAA and G(S)=0, G(X)=0.44 for PAA. Allowance was necessary for the effects of COOH decomposition on the average values of the molecular weight and partial specific volume for irradiated PAA. (author)

Diphtheria toxoid loaded poly-(epsilon-caprolactone) nanoparticles as mucosal vaccine delivery systems.

Science.gov (United States)

Singh, Jasvinder; Pandit, Sreenivas; Bramwell, Vincent W; Alpar, H Oya

2006-02-01

Poly-(epsilon-caprolactone) (PCL), a poly(lactide-co-glycolide) (PLGA)-PCL blend and co-polymer nanoparticles encapsulating diphtheria toxoid (DT) were investigated for their potential as a mucosal vaccine delivery system. The nanoparticles, prepared using a water-in-oil-in-water (w/o/w) double emulsion solvent evaporation method, demonstrated release profiles which were dependent on the properties of the polymers. An in vitro experiment using Caco-2 cells showed significantly higher uptake of PCL nanoparticles in comparison to polymeric PLGA, the PLGA-PCL blend and co-polymer nanoparticles. The highest uptake mediated by the most hydrophobic nanoparticles using Caco-2 cells was mirrored in the in vivo studies following nasal administration. PCL nanoparticles induced DT serum specific IgG antibody responses significantly higher than PLGA. A significant positive correlation between hydrophobicity of the nanoparticles and the immune response was observed following intramuscular administration. The positive correlation between hydrophobicity of the nanoparticles and serum DT specific IgG antibody response was also observed after intranasal administration of the nanoparticles. The cytokine assays showed that the serum IgG antibody response induced is different according to the route of administration, indicated by the differential levels of IL-6 and IFN-gamma. The nanoparticles eliciting the highest IgG antibody response did not necessarily elicit the highest levels of the cytokines IL-6 and IFN-gamma.

Osteointegration of Porous Poly-ε-Caprolactone-Coated and Previtalised Magnesium Implants in Critically Sized Calvarial Bone Defects in the Mouse Model

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Michael Grau

2017-12-01

Full Text Available Metallic biomaterials are widely used in maxillofacial surgery. While titanium is presumed to be the gold standard, magnesium-based implants are a current topic of interest and investigation due to their biocompatible, osteoconductive and degradable properties. This study investigates the effects of poly-ε-caprolactone-coated and previtalised magnesium implants on osteointegration within murine calvarial bone defects: After setting a 3 mm × 3 mm defect into the calvaria of 40 BALB/c mice the animals were treated with poly-ε-caprolactone-coated porous magnesium implants (without previtalisation or previtalised with either osteoblasts or adipose derived mesenchymal stem cells, porous Ti6Al4V implants or without any implant. To evaluate bone formation and implant degradation, micro-computertomographic scans were performed at day 0, 28, 56 and 84 after surgery. Additionally, histological thin sections were prepared and evaluated histomorphometrically. The outcomes revealed no significant differences within the differently treated groups regarding bone formation and the amount of osteoid. While the implant degradation resulted in implant shifting, both implant geometry and previtalisation appeared to have positive effects on vascularisation. Although adjustments in degradation behaviour and implant fixation are indicated, this study still considers magnesium as a promising alternative to titanium-based implants in maxillofacial surgery in future.

Poly-epsilon-caprolactone nanoparticles enhance ursolic acid in vivo efficacy against Trypanosoma cruzi infection.

Science.gov (United States)

Abriata, Juliana Palma; Eloy, Josimar O; Riul, Thalita Bachelli; Campos, Patricia Mazureki; Baruffi, Marcelo Dias; Marchetti, Juliana Maldonado

2017-08-01

Despite affecting millions of people worldwide, Chagas disease is still neglected by the academia and industry and the therapeutic option available, benznidazole, presents limited efficacy and side effects. Within this context, ursolic acid may serve as an option for treatment, however has low bioavailability, which can be enhanced through the encapsulation in polymeric nanoparticles. Therefore, herein we developed ursolic acid-loaded nanoparticles with poly-ε-caprolactone by the nanoprecipitation method and characterized them for particle size, zeta potential, polydispersity, encapsulation efficiency, morphology by scanning electron microscopy and thermal behavior by differential scanning calorimetry. Results indicated that an appropriate ratio of organic phase/aqueous phase and polymer/drug is necessary to produce smaller particles, with low polydispersity, negative zeta potential and high drug encapsulation efficiency. In vitro studies indicated the safety of the formulation against fibroblast culture and its efficacy in killing T. cruzi. Very importantly, the in vivo study revealed that the ursolic acid-loaded nanoparticle is as potent as the benznidazole group to control parasitemia, which could be attributed to improved bioavailability of the encapsulated drug. Finally, the toxicity evaluation showed that while benznidazole group caused liver toxicity, the nanoparticles were safe, indicating that this formulation is promising for future evaluation. Copyright © 2017 Elsevier B.V. All rights reserved.

Changes of porous poly(ε-caprolactone) bone grafts resulted from e-beam sterilization process

International Nuclear Information System (INIS)

Olah, L.; Filipczak, K.; Czvikovszky, T.; Czigany, T.; Borbas, L.

2007-01-01

The most important mechanical feature of poly(ε-caprolactone) (PCL) foams applied in bone tissue engineering as a scaffold, has been investigated as a function of irradiation dose. Radiation is proposed for the sterilization of the polymer before the implantation. Polycaprolactone scaffold foams were obtained by combination of compression molding and particulate leaching techniques. The porogen was changed in the range 74-96 w% and the irradiation dose was varied from 25 to 150 kGy. Our results show that yield strength is not a function of radiation dose, but is rather influenced by the porosity, while the critical strain is mainly dependent on the dose. All these together mean that the modulus of the elasticity of PCL foams is dependent on both the porosity and the dose

Amphiphilic block co-polymers: preparation and application in nanodrug and gene delivery.

Science.gov (United States)

Xiong, Xiao-Bing; Binkhathlan, Ziyad; Molavi, Ommoleila; Lavasanifar, Afsaneh

2012-07-01

Self-assembly of amphiphilic block co-polymers composed of poly(ethylene oxide) (PEO) as the hydrophilic block and poly(ether)s, poly(amino acid)s, poly(ester)s and polypropyleneoxide (PPO) as the hydrophobic block can lead to the formation of nanoscopic structures of different morphologies. These structures have been the subject of extensive research in the past decade as artificial mimics of lipoproteins and viral vectors for drug and gene delivery. The aim of this review is to provide an overview of the synthesis of commonly used amphiphilic block co-polymers. It will also briefly go over some pharmaceutical applications of amphiphilic block co-polymers as "nanodelivery systems" for small molecules and gene therapeutics. Copyright © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Engineering a multi-biofunctional composite using poly(ethylenimine) decorated graphene oxide for bone tissue regeneration

Science.gov (United States)

Kumar, Sachin; Raj, Shammy; Sarkar, Kishor; Chatterjee, Kaushik

2016-03-01

Toward preparing strong multi-biofunctional materials, poly(ethylenimine) (PEI) conjugated graphene oxide (GO_PEI) was synthesized using poly(acrylic acid) (PAA) as a spacer and incorporated in poly(ε-caprolactone) (PCL) at different fractions. GO_PEI significantly promoted the proliferation and formation of focal adhesions in human mesenchymal stem cells (hMSCs) on PCL. GO_PEI was highly potent in inducing stem cell osteogenesis leading to near doubling of alkaline phosphatase expression and mineralization over neat PCL with 5% filler content and was ~50% better than GO. Remarkably, 5% GO_PEI was as potent as soluble osteoinductive factors. Increased adsorption of osteogenic factors due to the amine and oxygen containing functional groups on GO_PEI augment stem cell differentiation. GO_PEI was also highly efficient in imparting bactericidal activity with 85% reduction in counts of E. coli colonies compared to neat PCL at 5% filler content and was more than twice as efficient as GO. This may be attributed to the synergistic effect of the sharp edges of the particles along with the presence of the different chemical moieties. Thus, GO_PEI based polymer composites can be utilized to prepare bioactive resorbable biomaterials as an alternative to using labile biomolecules for fabricating orthopedic devices for fracture fixation and tissue engineering.Toward preparing strong multi-biofunctional materials, poly(ethylenimine) (PEI) conjugated graphene oxide (GO_PEI) was synthesized using poly(acrylic acid) (PAA) as a spacer and incorporated in poly(ε-caprolactone) (PCL) at different fractions. GO_PEI significantly promoted the proliferation and formation of focal adhesions in human mesenchymal stem cells (hMSCs) on PCL. GO_PEI was highly potent in inducing stem cell osteogenesis leading to near doubling of alkaline phosphatase expression and mineralization over neat PCL with 5% filler content and was ~50% better than GO. Remarkably, 5% GO_PEI was as potent as soluble

Synthesis, Characterization, and Aqueous Lubricating Properties of Amphiphilic Graft Copolymers Comprising 2-Methoxyethyl Acrylate

DEFF Research Database (Denmark)

Javakhishvili, Irakli; Røn, Troels; Jankova Atanasova, Katja

2014-01-01

Amphiphilic anionic and cationic graft copolymers possessing poly(2-hydroxyethyl methacrylate) (PHEMA) backbone and poly(methacrylic acid), poly(2-methoxyethyl acrylate-co-methacrylic acid), and poly(2-methoxyethyl acrylate-co-2-(dimethylamino)ethyl methacrylate) grafts are constructed by merging...... of the corresponding monomers followed by deblocking reaction leads to well-defined amphiphiles with narrow molecular weight distributions (PDI ≤ 1.29) and varying content of methacrylic acid. The graft copolymers showed effective surface adsorption and lubrication for self-mated poly(dimethylsiloxane) (PDMS) contacts...

Effect of organically modified clay on mechanical properties, cytotoxicity and bactericidal properties of poly(ɛ-caprolactone) nanocomposites

Science.gov (United States)

Kumar, Sachin; Mishra, Anupam; Chatterjee, Kaushik

2014-12-01

The objective of this study was to evaluate the use of organically-modified clay nanoparticles in poly(ɛ-caprolactone) (PCL) for developing biodegradable composites. PCL nanocomposites reinforced with two different types of organically-modified clay (Cloisite 30B, C30B and Cloisite 93A, C93A) were prepared by melt-mixing. Morphology of PCL/clay nanocomposites characterized by scanning electron microscopy indicated good dispersion of nanoclay in the PCL matrix. Reinforcement of nanoclay in PCL enhanced mechanical properties without affecting thermal and degradation properties of PCL. Cytocompatibility of PCL/clay nanocomposites was studied using both osteoblasts and endothelial cells in vitro. Both composites (PCL/C30B and PCL/C93A) were cytotoxic with high toxicity observed for C30B even at low content of 1 wt %. The cytotoxicity was found to arise due to leachables from PCL/clay composites. Electrical conductivity measurements of aqueous media confirmed leaching of cationic surfactant from the PCL/clay composites PCL matrix. Both composites were found to be bactericidal but C30B was more effective than C93A. Taken together, it was observed that organically-modified nanoclay as fillers in PCL improves mechanical properties and imparts bactericidal properties but with increased risk of toxicity. These PCL/clay composites may be useful as stronger packaging material with antibacterial properties but are not suited as biomedical implants or for food packaging applications.

A Versatile Approach to Unimolecular Water-Soluble Carriers: ATRP of PEGMA with Hydrophobic Star-Shaped Polymeric Core Molecules as an Alternative for PEGylation

NARCIS (Netherlands)

Schramm, O.G.; Pavlov, G.M.; Erp, van H.H.P; Meier, M.A.R.; Hoogenboom, R.; Schubert, U.S.

2009-01-01

New amphiphilic star-shaped architectures with dense hydrophilic shells were synthesized by a combination of ring-opening polymerization (ROP) of e-caprolactone (CL) and atom transfer radical polymerization (ATRP) of different poly(ethylene glycol) methacrylates (PEGMAs). The PCL hydrophobic cores

Promising Poly(ε-caprolactone Composite Reinforced with Weft-Knitted Polyester for Small-Diameter Vascular Graft Application

Directory of Open Access Journals (Sweden)

Fu-Jun Wang

2014-01-01

Full Text Available The present study was designed to improve the mechanical performance of a small-diameter vascular prosthesis made from a flexible membrane of poly(ε-caprolactone (PCL. PCL reinforcement was achieved by embedding a tubular fabric knitted from polyethylene terephthalate (PET yarns within the freeze-dried composite structure. The knitting density of PET fabric influenced the mechanical properties of the new vascular graft. Results showed that the composite prototype has good mechanical properties, water permeability, elastic recovery, and suture retention strength. Increases in loop density increased compressive strength and suture retention strength and decreased elastic recovery. The new composite prototype vascular graft has promising potential applications in clinics because of its excellent mechanical properties.

Novel amphiphilic poly(dimethylsiloxane) based polyurethane networks tethered with carboxybetaine and their combined antibacterial and anti-adhesive property

Science.gov (United States)

Jiang, Jingxian; Fu, Yuchen; Zhang, Qinghua; Zhan, Xiaoli; Chen, Fengqiu

2017-08-01

The traditional nonfouling materials are powerless against bacterial cells attachment, while the hydrophobic bactericidal surfaces always suffer from nonspecific protein adsorption and dead bacterial cells accumulation. Here, amphiphilic polyurethane (PU) networks modified with poly(dimethylsiloxane) (PDMS) and cationic carboxybetaine diol through simple crosslinking reaction were developed, which had an antibacterial efficiency of 97.7%. Thereafter, the hydrolysis of carboxybetaine ester into zwitterionic groups brought about anti-adhesive properties against bacteria and proteins. The surface chemical composition and wettability performance of the PU network surfaces were investigated by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS) and contact angle analysis. The surface distribution of PDMS and zwitterionic segments produced an obvious amphiphilic heterogeneous surface, which was demonstrated by atomic force microscopy (AFM). Enzyme-linked immunosorbent assays (ELISA) were used to test the nonspecific protein adsorption behaviors. With the advantages of the transition from excellent bactericidal performance to anti-adhesion and the combination of fouling resistance and fouling release property, the designed PDMS-based amphiphilic PU network shows great application potential in biomedical devices and marine facilities.

Methotrexate-Loaded Four-Arm Star Amphiphilic Block Copolymer Elicits CD8+ T Cell Response against a Highly Aggressive and Metastatic Experimental Lymphoma.

Science.gov (United States)

Hira, Sumit Kumar; Ramesh, Kalyan; Gupta, Uttam; Mitra, Kheyanath; Misra, Nira; Ray, Biswajit; Manna, Partha Pratim

2015-09-16

We have synthesized a well-defined four-arm star amphiphilic block copolymer [poly(DLLA)-b-poly(NVP)]4 [star-(PDLLA-b-PNVP)4] that consists of D,L-lactide (DLLA) and N-vinylpyrrolidone (NVP) via the combination of ring-opening polymerization (ROP) and xanthate-mediated reversible addition-fragmentation chain transfer (RAFT) polymerization. Synthesis of the polymer was verified by 1H NMR spectroscopy and gel permeation chromatography (GPC). The amphiphilic four-arm star block copolymer forms spherical micelles in water as demonstrated by transmission electron microscopy (TEM) and 1H NMR spectroscopy. Pyrene acts as a probe to ascertain the critical micellar concentration (cmc) by using fluorescence spectroscopy. Methotrexate (MTX)-loaded polymeric micelles of star-(PDLLA15-b-PNVP10)4 amphiphilic block copolymer were prepared and characterized by fluorescence and TEM studies. Star-(PDLLA15-b-PNVP10)4 copolymer was found to be significantly effective with respect to inhibition of proliferation and lysis of human and murine lymphoma cells. The amphiphilic block copolymer causes cell death in parental and MTX-resistant Dalton lymphoma (DL) and Raji cells. The formulation does not cause hemolysis in red blood cells and is tolerant to lymphocytes compared to free MTX. Therapy with MTX-loaded star-(PDLLA15-b-PNVP10)4 amphiphilic block copolymer micelles prolongs the life span of animals with neoplasia by reducing the tumor load, preventing metastasis and augmenting CD8+ T cell-mediated adaptive immune responses.

Nanostructured Polysulfone-Based Block Copolymer Membranes

KAUST Repository

Xie, Yihui

2016-05-01

The aim of this work is to fabricate nanostructured membranes from polysulfone-based block copolymers through self-assembly and non-solvent induced phase separation. Block copolymers containing polysulfone are novel materials for this purpose providing better mechanical and thermal stability to membranes than polystyrene-based copolymers, which have been exclusively used now. Firstly, we synthesized a triblock copolymer, poly(tert-butyl acrylate)-b-polsulfone-b-poly(tert-butyl acrylate) through polycondensation and reversible addition-fragmentation chain-transfer polymerization. The obtained membrane has a highly porous interconnected skin layer composed of elongated micelles with a flower-like arrangement, on top of the graded finger-like macrovoids. Membrane surface hydrolysis was carried out in a combination with metal complexation to obtain metal-chelated membranes. The copper-containing membrane showed improved antibacterial capability. Secondly, a poly(acrylic acid)-b-polysulfone-b-poly(acrylic acid) triblock copolymer obtained by hydrolyzing poly(tert-butyl acrylate)-b-polsulfone-b-poly(tert-butyl acrylate) formed a thin film with cylindrical poly(acrylic acid) microdomains in polysulfone matrix through thermal annealing. A phase inversion membrane was prepared from the same polymer via self-assembly and chelation-assisted non-solvent induced phase separation. The spherical micelles pre-formed in a selective solvent mixture packed into an ordered lattice in aid of metal-poly(acrylic acid) complexation. The space between micelles was filled with poly(acrylic acid)-metal complexes acting as potential water channels. The silver0 nanoparticle-decorated membrane was obtained by surface reduction, having three distinct layers with different particle sizes. Other amphiphilic copolymers containing polysulfone and water-soluble segments such as poly(ethylene glycol) and poly(N-isopropylacrylamide) were also synthesized through coupling reaction and copper0-mediated

Coating electrospun poly(epsilon-caprolactone) fibers with gelatin and calcium phosphate and their use as biomimetic scaffolds for bone tissue engineering.

Science.gov (United States)

Li, Xiaoran; Xie, Jingwei; Yuan, Xiaoyan; Xia, Younan

2008-12-16

Electrospinning was employed to fabricate fibrous scaffolds of poly(epsilon-caprolactone) in the form of nonwoven mats. The surfaces of the fibers were then coated with gelatin through layer-by-layer self-assembly, followed by functionalization with a uniform coating of bonelike calcium phosphate by mineralization in the 10 times concentrated simulated body fluid for 2 h. Transmission electron microscopy, water contact angle, and scanning electron microscopy measurements confirmed the presence of gelatin and calcium phosphate coating layers, and X-ray diffraction results suggested that the deposited mineral phase was a mixture of dicalcium phosphate dehydrate (a precursor to apatite) and apatite. It was also demonstrated that the incorporation of gelatin promoted nucleation and growth of calcium phosphate. The porous scaffolds could mimic the structure, composition, and biological function of bone extracellular matrix. It was found that the preosteoblastic MC3T3-E1 cells attached, spread, and proliferated well with a flat morphology on the mineralized scaffolds. The proliferation rate of the cells on the mineralized scaffolds was significantly higher (by 1.9-fold) than that on the pristine fibrous scaffolds after culture for 7 days. These results indicated that the hybrid system containing poly(epsilon-caprolactone), gelatin, and calcium phosphate could serve as a new class of biomimetic scaffolds for bone tissue engineering.

Polymeric film of 6-arm-poly(ethylene glycol) amine graphene oxide with poly (ε-caprolactone): Adherence and growth of adipose derived mesenchymal stromal cells culture on rat bladder

Science.gov (United States)

Durán, Marcela; Durán, Nelson; Luzo, Angela C. M.; Duarte, Adriana S. S.; Volpe, Bruno B.; Ceragioli, Helder J.; Andrade, Patricia F.; De Souza, Joel G.; Fávaro, Wagner J.

2017-06-01

Nanotechnology has been more present in different fields related to health. The need to find a durable material, of easy use, and which does not interfere significantly in the growth and differentiation of stem cells for the construction of a scaffold for use in urologic surgery, with the purpose of reducing infections, regeneration times and even graft rejection during reconstitution in patients with urethral stricture was conducted a broad survey of information about this and came to the consensus of this project: using graphene oxide, a widely studied nanomaterials which has been presenting numerous beneficial results when in contact with the adipose-derived stem cells. Advanced techniques for the growth, differentiation and proliferation of adipose-derived stem cells were used, as well as the characterization of graphene oxide sheets. For this study, it was prepared the graphene oxide/6 ARM-Poly (ethylene glycol) amine films with poly (ε-caprolactone). The graphene suspension in organic solvent was prepared by using an ultrasonicator bath and subsequently, the film was formed by solvent evaporation. Total characterization of graphene oxide/6 ARM-PEG-amine/ poly (ε-caprolactone) film was carried out. It was tested growth and adhesion of adipose-derived stem cells on the film, as well as, were verified the histopathological effects of this scaffold when implanted in the urinary bladder to repair the lesion. Our results demonstrated that this scaffold with adipose-derived stem cells enhanced the repair in rat urinary bladder defect model, resulting in a regular bladder. Improved organized muscle bundles and urothelial layer were observed in animals treated with this scaffold with adipose-derived stem cells compared with those treated only suture thread or scaffold. Thus, our biomaterial could be suitable for tissue engineered urinary tract reconstruction.

Polymeric film of 6-arm-poly(ethylene glycol) amine graphene oxide with poly (ε-caprolactone): Adherence and growth of adipose derived mesenchymal stromal cells culture on rat bladder

International Nuclear Information System (INIS)

Durán, Marcela; Durán, Nelson; Fávaro, Wagner J.; Luzo, Angela C.M.; Duarte, Adriana S. S.; Volpe, Bruno B.; Ceragioli, Helder J.; Andrade, Patricia F.; De Souza, Joel G.

2017-01-01

Nanotechnology has been more present in different fields related to health. The need to find a durable material, of easy use, and which does not interfere significantly in the growth and differentiation of stem cells for the construction of a scaffold for use in urologic surgery, with the purpose of reducing infections, regeneration times and even graft rejection during reconstitution in patients with urethral stricture was conducted a broad survey of information about this and came to the consensus of this project: using graphene oxide, a widely studied nanomaterials which has been presenting numerous beneficial results when in contact with the adipose-derived stem cells. Advanced techniques for the growth, differentiation and proliferation of adipose-derived stem cells were used, as well as the characterization of graphene oxide sheets. For this study, it was prepared the graphene oxide/6 ARM-Poly (ethylene glycol) amine films with poly (ε-caprolactone). The graphene suspension in organic solvent was prepared by using an ultrasonicator bath and subsequently, the film was formed by solvent evaporation. Total characterization of graphene oxide/6 ARM-PEG-amine/ poly (ε-caprolactone) film was carried out. It was tested growth and adhesion of adipose-derived stem cells on the film, as well as, were verified the histopathological effects of this scaffold when implanted in the urinary bladder to repair the lesion. Our results demonstrated that this scaffold with adipose-derived stem cells enhanced the repair in rat urinary bladder defect model, resulting in a regular bladder. Improved organized muscle bundles and urothelial layer were observed in animals treated with this scaffold with adipose-derived stem cells compared with those treated only suture thread or scaffold. Thus, our biomaterial could be suitable for tissue engineered urinary tract reconstruction. (paper)

Biodegradability and biodegradation rate of poly(caprolactone)-starch blend and poly(butylene succinate) biodegradable polymer under aerobic and anaerobic environment.

Science.gov (United States)

Cho, H S; Moon, H S; Kim, M; Nam, K; Kim, J Y

2011-03-01

The biodegradability and the biodegradation rate of two kinds biodegradable polymers; poly(caprolactone) (PCL)-starch blend and poly(butylene succinate) (PBS), were investigated under both aerobic and anaerobic conditions. PCL-starch blend was easily degraded, with 88% biodegradability in 44 days under aerobic conditions, and showed a biodegradation rate of 0.07 day(-1), whereas the biodegradability of PBS was only 31% in 80 days under the same conditions, with a biodegradation rate of 0.01 day(-1). Anaerobic bacteria degraded well PCL-starch blend (i.e., 83% biodegradability for 139 days); however, its biodegradation rate was relatively slow (6.1 mL CH(4)/g-VS day) compared to that of cellulose (13.5 mL CH(4)/g-VS day), which was used as a reference material. The PBS was barely degraded under anaerobic conditions, with only 2% biodegradability in 100 days. These results were consistent with the visual changes and FE-SEM images of the two biodegradable polymers after the landfill burial test, showing that only PCL-starch blend had various sized pinholes on the surface due to attack by microorganisms. This result may be use in deciding suitable final disposal approaches of different types of biodegradable polymers in the future. Copyright © 2010 Elsevier Ltd. All rights reserved.

Electrospinning of doxorubicin loaded silica/poly(ɛ-caprolactone) hybrid fiber mats for sustained drug release

Science.gov (United States)

El Gohary, Mohammed I.; El Hady, Bothaina M. Abd; Saeed, Aziza A. Al; Tolba, Emad; El Rashedi, Ahlam M. I.; Saleh, Safaa

2018-06-01

Loading of anticancer drugs into electrospun fiber matrices is a portentous approach for clinical treatment of diseased tissues or organs. In this study, doxorubicin hydrochloride (DOX) is added to silica nanoparticles () during the formation of via the sol-gel approach. The obtained nanoparticles are then added to poly(-caprolactone) (PCL) and poly(ethylene oxide) (PEO) blend before electrospinning process via different methods. The effects of DOX addition as a free form or as nanoparticles on physical and chemical properties of obtained PCL-PEO fibers, as well as release profiles are evaluated to give a continual DOX release for several days. The morphology observed with scanning electron microscope (FESEM) revealed significant changes in the average diameter of obtained fibers ranging from 2164 nm to 659 nm and distribution of drug-loaded nanoparticles in the final mats according to the mode of additions. With the same manner, the releasing performances of obtained mats are quite different. Therefore, fabrication of drug loaded mats would offer a powerful approach to minimize serious side effects for clinical patients and allows us to control the drug concentration in the bloodstream.

Phase behaviour of the ternary system {poly(ε-caprolactone) + carbon dioxide + dichloromethane}

International Nuclear Information System (INIS)

Bender, Joao P.; Feitein, Mirian; Mazutti, Marcio A.; Franceschi, Elton; Corazza, Marcos L.; Oliveira, J. Vladimir

2010-01-01

Recently, production of biocompatible and biodegradable polymer microparticles has been a matter of growing interest in pharmaceutical and food areas such as drug or active compounds delivery. To conduct production of microparticles, polymeric particle coating, impregnation of active compounds in polymeric films, the knowledge of phase behaviour involving the biodegradable polymer in supercritical carbon dioxide in the presence of a modifier may be needed to allow developing new industrial applications. In this sense, the aim of this work was to investigate the phase behaviour of the ternary system formed by the biodegradable polymer poly(ε-caprolactone) in (carbon dioxide + dichloromethane). Experimental phase transition (bubble and cloud point) values were obtained by applying the static-synthetic method using a variable-volume view cell over the temperature range of (303 to 343) K and pressures up to 21 MPa, in the CO 2 overall composition range of (25-46) wt%, while polymer concentrations studied were (1, 3, 5, and 7) wt%. For the system investigated, depending on the polymer concentration, vapour-liquid, liquid-liquid, and vapour-liquid-liquid phase transitions were verified.

Self-Assembly of Charged Amphiphilic Diblock Copolymers with Insoluble Blocks of Decreasing Hydrophobicity: From Kinetically Frozen Colloids to Macrosurfactants

Energy Technology Data Exchange (ETDEWEB)

M Jacquin; P Muller; H Cottet; O Theodoly

2011-12-31

We have investigated the self-assembly properties in aqueous solution of amphiphilic diblock copolymers with insoluble blocks of different hydrophobicity and demonstrated that the condition to obtain dynamic micelles is to design samples with insoluble blocks of low enough hydrophobicity. We focus here on results with new water-soluble amphiphilic diblock copolymers poly(diethyleneglycol ethylether acrylate)-b-poly(acrylic acid), or PDEGA-b-PAA. The physical characteristics of PDEGA-b-PAA micelles at high ionization have been determined by small angle neutron scattering (SANS). We show that PDEGA-b-PAA samples form micelles at thermodynamic equilibrium. The critical micelle concentrations (CMCs) decrease strongly with ionic strength and temperature due to a solvent quality decrease for, respectively, the corona and the core. This behavior of reversible aggregation is remarkable as compared to the behavior of kinetically frozen aggregation that has been widely observed with samples of similar architecture and different hydrophobic blocks, for example, poly(styrene)-b-poly(acrylic acid), PS-b-PAA, and poly(butyl acrylate)-b-poly(acrylic acid), PBA-b-PAA. We have measured the interfacial tension between water and the homopolymers PDEGA and PBA at, respectively, 3 and 20 mN/m at room temperature, which permits one to estimate the energy cost to extract a unimer from a micelle. The results are consistent with a micelle association that is fast for PDEGA-b-PAA and kinetically frozen PBA-b-PAA. Hence, PDEGA-b-PAA samples form a new system of synthetic charged macrosurfactant with unique properties of fast dynamic association, tunable charge, and water solubility even at temperatures and NaCl concentrations as high as 65 C and 1 M.

Synthesis, characterization and degradation behavior of admicelled polyacrylate-natural rubber

International Nuclear Information System (INIS)

Pongpilaipruet, Angkana; Magaraphan, Rathanawan

2015-01-01

In order to improve weatherability of the cured natural rubber, the novel introduction of good ozone resistant polymers such as polyacrylates (poly(methyl acrylate) (PMA) or poly(methyl methacrylate) (PMMA)) into natural rubber (NR) by admicellar polymerization was investigated in this work. The admicellar polymerization to synthesize polyacrylate layer over the surface of NR latex particles was performed with varying monomer type (PMA and PMMA) and content (50 and 100 mM). The admicelled PMMA showed higher molecular weight than PMA. Fourier transform infrared spectra of the admicellar synthesized natural rubbers exhibited characteristic peaks of those polyacrylates. Micrographs from transmission electron and field emission scanning electron microscopes (FE-SEM) revealed the coatings of PMA and PMMA over the rubber particles, suggesting a core-shell structure. Thermogravimetric analysis revealed that the admicelled rubbers not only showed an improvement in heat stability but also a single decomposition temperature. After vulcanization, FE-SEM results showed the cured admicelled rubbers had phase transformation from core-shell to phase separation (aggregate domains of polyacrylate-rich phase) with smooth interface. This agreed well to their one glass transition temperature (∼−48 °C) which indicated good miscibility between NR and each polyacrylate. The cracks generated after exposure to ozone found in the admicelled rubbers were smaller than those in NR, suggesting better ozone resistance was achieved. Increasing monomer concentration led to less cracks or much better ozone resistance. Furthermore, changes in mechanical properties after ozone exposure of the admicelled PMA-NR were less than those of the admicelled PMMA-NR (having the same shell content) and the NR, respectively. - Highlights: • We use admicellar technique to add polyacrylates to NR in form of core-shell rubber. • This core-shell structure was physically formed as seen by the phase

Synthesis, characterization and degradation behavior of admicelled polyacrylate-natural rubber

Energy Technology Data Exchange (ETDEWEB)

Pongpilaipruet, Angkana; Magaraphan, Rathanawan, E-mail: rathanawan.k@chula.ac.th

2015-06-15

In order to improve weatherability of the cured natural rubber, the novel introduction of good ozone resistant polymers such as polyacrylates (poly(methyl acrylate) (PMA) or poly(methyl methacrylate) (PMMA)) into natural rubber (NR) by admicellar polymerization was investigated in this work. The admicellar polymerization to synthesize polyacrylate layer over the surface of NR latex particles was performed with varying monomer type (PMA and PMMA) and content (50 and 100 mM). The admicelled PMMA showed higher molecular weight than PMA. Fourier transform infrared spectra of the admicellar synthesized natural rubbers exhibited characteristic peaks of those polyacrylates. Micrographs from transmission electron and field emission scanning electron microscopes (FE-SEM) revealed the coatings of PMA and PMMA over the rubber particles, suggesting a core-shell structure. Thermogravimetric analysis revealed that the admicelled rubbers not only showed an improvement in heat stability but also a single decomposition temperature. After vulcanization, FE-SEM results showed the cured admicelled rubbers had phase transformation from core-shell to phase separation (aggregate domains of polyacrylate-rich phase) with smooth interface. This agreed well to their one glass transition temperature (∼−48 °C) which indicated good miscibility between NR and each polyacrylate. The cracks generated after exposure to ozone found in the admicelled rubbers were smaller than those in NR, suggesting better ozone resistance was achieved. Increasing monomer concentration led to less cracks or much better ozone resistance. Furthermore, changes in mechanical properties after ozone exposure of the admicelled PMA-NR were less than those of the admicelled PMMA-NR (having the same shell content) and the NR, respectively. - Highlights: • We use admicellar technique to add polyacrylates to NR in form of core-shell rubber. • This core-shell structure was physically formed as seen by the phase

Comparison of physical, chemical and cellular responses to nano- and micro-sized calcium silicate/poly(epsilon-caprolactone) bioactive composites.

Science.gov (United States)

Wei, Jie; Heo, S J; Kim, D H; Kim, S E; Hyun, Y T; Shin, Jung-Woog

2008-06-06

In this study, we fabricated nano-sized calcium silicate/poly(epsilon-caprolactone) composite (n-CPC) and micro-sized calcium silicate/poly(epsilon-caprolactone) composite (m-CPC). The composition, mechanical properties, hydrophilicity and degradability of both n-CPC and m-CPC were determined, and in vitro bioactivity was evaluated by investigating apatite forming on their surfaces in simulated body fluid (SBF). In addition, cell responses to the two kinds of composites were comparably investigated. The results indicated that n-CPC has superior hydrophilicity, compressive strength and elastic modulus properties compared with m-CPC. Both n-CPC and m-CPC exhibited good in vitro bioactivity, with different morphologies of apatite formation on their surfaces. The apatite layer on n-CPC was more homogeneous and compact than on m-CPC, due to the elevated levels of calcium and silicon concentrations in SBF from n-CPC throughout the 14-day soaking period. Significantly higher levels of attachment and proliferation of MG63 cells were observed on n-CPC than on m-CPC, and significantly higher levels of alkaline phosphatase activity were observed in human mesenchymal stem cells (hMSCs) on n-CPC than on m-CPC after 7 days. Scanning electron microscopy observations revealed that hMSCs were in intimate contact with both n-CPC and m-CPC surfaces, and significantly cell adhesion, spread and growth were observed on n-CPC and m-CPC. These results indicated that both n-CPC and m-CPC have the ability to support cell attachment, growth, proliferation and differentiation, and also yield good bioactivity and biocompatibility.

Electrospun Poly(L-Lactide-co-ε-Caprolactone/Polyethylene Oxide/Hydroxyapaite Nanofibrous Membrane for Guided Bone Regeneration

Directory of Open Access Journals (Sweden)

Gang Wang

2010-01-01

Full Text Available A series of poly(L-lactide-co-ε-caprolactone/polyethylene oxide/hydroxyapaite (PLCL/PEO/HA composite fibrous membranes were prepared by elecrospinning technology for guided bone regeneration. The morphology, water permeability and mechanical properties of the membranes were investigated. The HA nanocrystals can be well distributed in the PLCL/PEO matrix. And the diameter of composite nanofiber is larger than that of pure PLCL. The fibers with uniform size and large diameter were obtained when the contents of PEO and HA were 0.4% and 0.03%, respectively. In this condition, the obtained membrane presents the best water permeability. Furthermore, the nanofibrous membrane with largest tensile strength was obtained when the contents of PEO and HA were 0.5% and 0.03%, respectively.

Characteristic of Irradiation Result Film of Poly-Propylene-Co-Ethylene/Poly-ε-Caprolactone and Poly-Propylene Grafted Maleic Anhydrate Blend

International Nuclear Information System (INIS)

Nikham

2004-01-01

The effect of gamma rays irradiation to film of melt-blending polypropylene-co-ethylene (CPP) and poly-ε-caprolactone (PCL) with polypropylene grafted maleic anhydride (PP-g-MAH) blend as compatibilizer has been studied. The objective of the research is to prepare the biodegradable polyblend. The composition blend of CPP/PCL with 0, 10, 15, 20 wt % PP-g-MAH i.e. 100/0, 75/25, 50/50, 25/75 and 0/100 were irradiated by using gamma rays 60 Co with activity 420 kCi at doses; 0, 50, 100, 150, 200 kGy, at dose rate 8.2 kGy/hrs and temperature 90 o C. The elongation at break, tensile strength, gel fraction, enzymatic degradation and heat resistance were evaluated. The results showed that the compatibility of PP-g-MAH to reach good enough polyblend is 20 % weight. Elongation at break film of CPP/PCL 50/50 blend which irradiated at dose 200 kGy decreased, whereas the tensile strength increased. Gel fraction and heat resistance of the film irradiated increased. Enzyme of lipase AK can degraded either without irradiated or irradiated film. Thus quality of the polyblend can be called as biodegradable plastic material. (author)

Importance of crystallinity of anchoring block of semi-solid amphiphilic triblock copolymers in stabilization of silicone nanoemulsions.

Science.gov (United States)

Le Kim, Trang Huyen; Jun, Hwiseok; Nam, Yoon Sung

2017-10-01

Polymer emulsifiers solidified at the interface between oil and water can provide exceptional dispersion stability to emulsions due to the formation of unique semi-solid interphase. Our recent works showed that the structural stability of paraffin-in-water emulsions highly depends on the oil wettability of hydrophobic block of methoxy poly(ethylene glycol)-block-poly(ε-caprolactone) (mPEG-b-PCL). Here we investigate the effects of the crystallinity of hydrophobic block of triblock copolymer-based emulsifiers, PCLL-b-PEG-b-PCLL, on the colloidal properties of silicone oil-in-water nanoemulsions. The increased ratio of l-lactide to ε-caprolactone decreases the crystallinity of the hydrophobic block, which in turn reduces the droplet size of silicone oil nanoemulsions due to the increased chain mobility at the interface. All of the prepared nanoemulsions are very stable for a month at 37°C. However, the exposure to repeated freeze-thaw cycles quickly destabilizes the nanoemulsions prepared using the polymer with the reduced crystallinity. This work demonstrates that the anchoring chain crystallization in the semi-solid interphase is critically important for the structural robustness of nanoemulsions under harsh physical stresses. Copyright © 2017 Elsevier Inc. All rights reserved.

Design and characterization of dexamethasone-loaded poly (glycerol sebacate)-poly caprolactone/gelatin scaffold by coaxial electro spinning for soft tissue engineering.

Science.gov (United States)

Nadim, Afsaneh; Khorasani, Saied Nouri; Kharaziha, Mahshid; Davoodi, Seyyed Mohammadreza

2017-09-01

The aim of this research was to fabricate dexamethasone (Dex)-loaded poly (glycerol sebacate) (PGS)-poly (caprolactone) (PCL)/gelatin (Gt) (PGS-PCL/Gt-Dex) fibrous scaffolds in the form of core/shell structure which have potential application in soft tissues. In this regard, after synthesize and characterizations of PGS, PGS-PCL and gelatin fibrous scaffolds were separately developed in order to optimize the electrospinning parameters. In the next step, coaxial electrospun fibrous scaffold of PGS-PCL/Gt fibrous scaffold with PGS-PCL as core and Gt as shell was developed and its mechanical, physical and chemical properties were characterized. Moreover, degradability, hydrophilicity and biocompatibility of PGS-PCL/Gt fibrous scaffold were evaluated. In addition, Dex was encapsulated in PGS-PCL/Gt fibrous scaffold and drug release was assessed for tissue engineering application. Results demonstrated the formation of coaxial fibrous scaffold with average porosity of 79% and average fiber size of 294nm. Moreover, PGS-PCL/Gt fibrous scaffold revealed lower elastic modulus, ultimate tensile and ultimate elongation than those of PGS-PCL scaffold and more close to mechanical properties of natural tissue. Furthermore, lower contact angle of PGS-PCL/Gt than that of PGS-PCL demonstrated improved surface hydrophilicity of scaffold. DEX release was sustained over a period time of 30days from the scaffolds via three steps consisting of an initial burst release, secondary linear phase release pattern with slower rate over 20days followed by an apparent zero-order release phase. MTT observations demonstrated that there was no evidence of toxicity in the samples with and without Dex. Our findings indicated that core/shell PGS-PCL/Gt-Dex fibrous could be used as a carrier for the sustained release of drugs relevant for tissue engineering which makes it appropriate for soft tissue engineering. Copyright © 2017 Elsevier B.V. All rights reserved.

Preparation and Characterization of Amphiphilic Triblock Terpolymer-Based Nanofibers as Antifouling Biomaterials

KAUST Repository

Cho, Youngjin; Cho, Daehwan; Park, Jay Hoon; Frey, Margaret W.; Ober, Christopher K.; Joo, Yong Lak

2012-01-01

as KB) and fabricated amphiphilic nanofibers by electrospinning of solutions prepared by mixing the KB with poly(lactic acid) (PLA) polymer. The resulting fibers with amphiphilic polymer groups exhibited superior antifouling performance to the fibers

Mechanical and thermal properties of conventional and microcellular injection molded poly (lactic acid)/poly (ε-caprolactone) blends.

Science.gov (United States)

Zhao, Haibin; Zhao, Guoqun

2016-01-01

In view of their complementary properties, blending polylactide (PLA) with poly (ε-caprolactone) (PCL) becomes a good choice to improve PLA's properties without compromising its biodegradability. A series of blends of biodegradable PLA and PCL with different mass fraction were prepared by melt mixing. Standard tensile bars were produced by both conventional and microcellular injection molding to study their mechanical and thermal properties. With the increase in PCL content, the blend showed decreased tensile strength and modulus; however, elongation was dramatically increased. With the addition of PCL, the failure mode changed from brittle fracture of the neat PLA to ductile fracture of the blend as demonstrated by tensile test. Various theoretical models based on dispersion and interface adhesion were used to predict the Young's modulus and the results shows the experimental data are consistent with the predictions of the foam model and Kerner-Uemura-Takayangi model. The thermal behavior of the blends was investigated by DSC and TGA. The melting temperature and the degree of crystallinity of PCL in the PLA/PCL did not significantly change with the PCL content increasing in the whole range of blends composition. Copyright © 2015 Elsevier Ltd. All rights reserved.

Rheology and adhesion of poly(acrylic acid)/laponite nanocomposite hydrogels as biocompatible adhesives.

Science.gov (United States)

Shen, Muxian; Li, Li; Sun, Yimin; Xu, Jun; Guo, Xuhong; Prud'homme, Robert K

2014-02-18

Biocompatible nanocomposite hydrogels (NC gels) consisting of poly(acrylic acid) (PAA) and nanosized clay (Laponite) were successfully synthesized by in situ free-radical polymerization of acrylic acid (AA) in aqueous solutions of Laponite. The obtained NC gels were uniform and transparent. Their viscosity, storage modulus G', and loss modulus G″ increased significantly upon increasing the content of Laponite and the dose of AA, while exhibiting a maximum with increasing the neutralization degree of AA. They showed tunable adhesion by changing the dose of Laponite and monomer as well as the neutralization degree of AA, as determined by 180° peel strength measurement. The maximal adhesion was shown when reaching a balance between cohesion and fluidity. A homemade Johnson-Kendall-Roberts (JKR) instrument was employed to study the surface adhesion behavior of the NC gels. The combination of peel strength, rheology, and JKR measurements offers the opportunity of insight into the mechanism of adhesion of hydrogels. The NC gels with tunable adhesion should be ideal candidates for dental adhesive, wound dressing, and tissue engineering.

Application of polyacrylic acid-poly-N,N-dimethyldiallylammonium chloride polyelectrolyte complexes for structuring of polluted soil of Semipalatinsk nuclear test site

International Nuclear Information System (INIS)

Sabantseva, T.; Bashenova, A.; Orazzhanova, L.K.; Yashkarova, M.G.; Bimendina, L.A.

2002-01-01

The present communication is devoted to investigation of structuring efficiency of polyacrylic acid-poly-N,N-dimethyldiallylammonium chloride (PAA-PDMDAACI) polyelectrolyte complexes. The granulometric analysis of selected soil samples before and after the treatment of aqueous solution of PAA, PDMDAACI and PAA-PDMDAACI complexes at different molar ratio of polymer components and polymer concentrations was carried out. Analysis shows that nonstoichiometric polyelectrolyte complex [PAA]:[PDMDAACI]=3:1 possesses the best structuring effect. But this result is worse than in the case using of [PAA]:[polyethylene glycol]=1:1 inter-polymer complex

pH-Responsive Shape Memory Poly(ethylene glycol)-Poly(ε-caprolactone)-based Polyurethane/Cellulose Nanocrystals Nanocomposite.

Science.gov (United States)

Li, Ying; Chen, Hongmei; Liu, Dian; Wang, Wenxi; Liu, Ye; Zhou, Shaobing

2015-06-17

In this study, we developed a pH-responsive shape-memory polymer nanocomposite by blending poly(ethylene glycol)-poly(ε-caprolactone)-based polyurethane (PECU) with functionalized cellulose nanocrystals (CNCs). CNCs were functionalized with pyridine moieties (CNC-C6H4NO2) through hydroxyl substitution of CNCs with pyridine-4-carbonyl chloride and with carboxyl groups (CNC-CO2H) via 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) mediated surface oxidation, respectively. At a high pH value, the CNC-C6H4NO2 had attractive interactions from the hydrogen bonding between pyridine groups and hydroxyl moieties; at a low pH value, the interactions reduced or disappeared due to the protonation of pyridine groups, which are a Lewis base. The CNC-CO2H responded to pH variation in an opposite manner. The hydrogen bonding interactions of both CNC-C6H4NO2 and CNC-CO2H can be readily disassociated by altering pH values, endowing the pH-responsiveness of CNCs. When these functionalized CNCs were added in PECU polymer matrix to form nanocomposite network which was confirmed with rheological measurements, the mechanical properties of PECU were not only obviously improved but also the pH-responsiveness of CNCs could be transferred to the nanocomposite network. The pH-sensitive CNC percolation network in polymer matrix served as the switch units of shape-memory polymers (SMPs). Furthermore, the modified CNC percolation network and polymer molecular chains also had strong hydrogen bonding interactions among hydroxyl, carboxyl, pyridine moieties, and isocyanate groups, which could be formed or destroyed through changing pH value. The shape memory function of the nanocomposite network was only dependent on the pH variation of the environment. Therefore, this pH-responsive shape-memory nancomposite could be potentially developed into a new smart polymer material.

Electrochemical impedance and spectroscopy study of the EDC/NHS activation of the carboxyl groups on poly(ε-caprolactone/poly(m-anthranilic acid nanofibers

Directory of Open Access Journals (Sweden)

Z. Guler

2016-02-01

Full Text Available Electrochemical impedance spectroscopy (EIS and spectroscopy was applied to investigate the surface activation of carboxyl group (–COOH containing nanofibers by the reaction of 1-ethyl-3-(dimethyl-aminopropyl carbodiimide hydrochloride (EDC/N-hydroxyl succinimide (NHS in different concentrations. Poly(!-caprolactone/poly(m-anthranilic acid (PCL/P3ANA nanofibers were fabricated by electrospinning and were activated with 5/0.5, 0.5/5, 5/5 and 50/50 mM of EDC/NHS. The surface activation was investigated by Attenuated Total Reflectance Fourier transform infrared spectroscopy (FTIR-ATR and activation yield was estimated. Albumin was immobilized after surface activation and the amount of covalently immobilized protein was determined by bicinchoninic acid (BCA assay. Morphology and composition of albumin immobilized nanofibers were characterized by Scanning Electron Microscopy/Energy-Dispersive X-ray Spectroscopy (SEM/EDX and Atomic force microscope (AFM. EIS measurements indicated that nanofibers become resistant after albumin immobilization. The obtained data revealed that the highest amount of albumin bound to nanofibers activated with 50/50 mM of EDC/NHS which was found to be the optimum concentration for the activation of PCL/P3ANA nanofibers.

Development of nanofibrous scaffolds containing gum tragacanth/poly (ε-caprolactone) for application as skin scaffolds.

Science.gov (United States)

Ranjbar-Mohammadi, Marziyeh; Bahrami, S Hajir

2015-03-01

Outstanding wound healing activity of gum tragacanth (GT) and higher mechanical strength of poly (ε-caprolactone) (PCL) may produce an excellent nanofibrous patch for either skin tissue engineering or wound dressing application. PCL/GT scaffold containing different concentrations of PCL with different blend ratios of GT/PCL was produced using 90% acetic acid as solvent. The results demonstrated that the PCL/GT (3:1.5) with PCL concentration of 20% (w/v) produced nanofibers with proper morphology. Scanning electron microscopy (SEM) and differential scanning calorimetry (DSC) were utilized to characterize the nanofibers. Surface wettability, functional groups analysis, porosity and tensile properties of nanofibers were evaluated. Morphological characterization showed that the addition of GT to PCL solution results in decreasing the average diameter of the PCL/GT nanofibers. However, the hydrophilicity increased in the PCL/GT nanofibers. Slight increase in melting peaks was observed due to the blending of PCL with GT nanofibers. PCL/GT nanofibers were used for in vitro cell culture of human fibroblast cell lines AGO and NIH 3T3 fibroblast cells. MTT assay and SEM results showed that the biocomposite PCL/GT mats enhanced the fibroblast adhesion and proliferation compared to PCL scaffolds. The antibacterial activity of PCL/GT and GT nanofibers against Staphylococcus aureus and Pseudomonas aeruginosa was also examined. Copyright © 2014 Elsevier B.V. All rights reserved.

Extraction of silver by gels of sodium poly-acrylic-polyacrylate acid. Application: elimination of chloride anions; Extraction de l'argent par des gels d'acide polyacrylique-polyacrylate de sodium. Application a l'elimination des ions chlorures

Energy Technology Data Exchange (ETDEWEB)

Rifi, E.H. [Universite Ibn-Tofail, Lab. de Synthese Organique et Pocedes d' Extraction, Faculte des Sciences, Kenitra (Morocco); Lakkis, D.; Leroy, J.F.M. [Universite Louis Pasteur, Lab. de Chimie Analytique et Minerale, Ecole Europeenne de Chimie, Polymeres et Materiaux, 67 - Strasbourg (France)

2005-05-01

The extraction of silver from diluted aqueous solutions by gels of sodium poly-acrylic-polyacrylate acid was studied. The study of pH variations shows that the extraction is done by cation-cation exchange process. The highest loading of the gel by silver is obtained at R(moles of Ag{sup +} fixed by the gel/moles of -COO(H, Na))=0.75. The silver gel loaded allows the recovery of ions chlorides from the aqueous solutions. (authors)

Hydroxyapatite-armored poly(ε-caprolactone) microspheres and hydroxyapatite microcapsules fabricated via a Pickering emulsion route.

Science.gov (United States)

Fujii, Syuji; Okada, Masahiro; Nishimura, Taiki; Maeda, Hayata; Sugimoto, Tatsuya; Hamasaki, Hiroyuki; Furuzono, Tsutomu; Nakamura, Yoshinobu

2012-05-15

Hydroxyapatite (HAp) nanoparticle-armored poly(ε-caprolactone) (PCL) microspheres were fabricated via a "Pickering-type" emulsion solvent evaporation method in the absence of any molecular surfactants. It was clarified that the interaction between carbonyl/carboxylic acid groups of PCL and the HAp nanoparticles at an oil-water interface played a crucial role in the preparation of the stable Pickering-type emulsions and the HAp nanoparticle-armored microspheres. The HAp nanoparticle-armored PCL microspheres were characterized in terms of size, size distribution, morphology, and chemical compositions using scanning electron microscopy, laser diffraction, energy dispersive X-ray microanalysis, and thermogravimetric analysis. The presence of HAp nanoparticles at the surface of the microspheres was confirmed by scanning electron microscopy and energy dispersive X-ray microanalysis. Pyrolysis of the PCL cores led to the formation of the corresponding HAp hollow microcapsules. Copyright © 2012 Elsevier Inc. All rights reserved.

Femtosecond laser surface texturing of 3D poly-ε-caprolactone matrices for bone tissue engineering applications

Science.gov (United States)

Daskalova, A.; Bliznakova, I.; Zhelyazkova, A.; Ostrowska, B.; Trifonov, A.; Buchvarov, I.; Avramov, L.; Husinsky, W.

2018-03-01

Fibrous 3D matrices were fabricated from poly-ɛ-caprolactone (PCL) by fused deposition modeling. Femtosecond laser irradiation was then used to demonstrate the possibility to affect the porosity of the 3D PCL fiber meshes. The surface characteristics were analyzed by scanning electron microscopy (SEM) and confocal microscopy. The interrelationship was examined between the laser processing parameters (number of pulses, pulse energy applied) and the response of the biomaterial. The formation was demonstrated of well-defined micropores, while the original fiber structure was retained. The study of cells cultivation on the laser-modified scaffolds showed good adhesion compared to a non-modified scaffold. The results obtained showed that femtosecond laser processing can be used as an alternative non-contact tool in enhancing the porosity of artificial constructs, thus influencing the cell adhesion into fibrous meshes.

Structure-property relationship in cytotoxicity and cell uptake of poly(2-oxazoline) amphiphiles

KAUST Repository

Luxenhofer, Robert

2011-07-01

The family of poly(2-oxazoline)s (POx) is being increasingly investigated in the context of biomedical applications. We tested the relative cytotoxicity of POx and were able to confirm that these polymers are typically not cytotoxic even at high concentrations. Furthermore, we report structure-uptake relationships of a series of amphiphilic POx block copolymers that have different architectures, molar mass and chain termini. The rate of endocytosis can be fine-tuned over a broad range by changing the polymer structure. The cellular uptake increases with the hydrophobic character of the polymers and is observed even at nanomolar concentrations. Considering the structural versatility of this class of polymers, the relative ease of preparation and their stability underlines the potential of POx as a promising platform candidate for the preparation of next-generation polymer therapeutics.

Topologically Micropatterned Collagen and Poly(ε-caprolactone) Struts Fabricated Using the Poly(vinyl alcohol) Fibrillation/Leaching Process To Develop Efficiently Engineered Skeletal Muscle Tissue.

Science.gov (United States)

Kim, Minseong; Kim, WonJin; Kim, GeunHyung

2017-12-20

Optimally designed three-dimensional (3D) biomedical scaffolds for skeletal muscle tissue regeneration pose significant research challenges. Currently, most studies on scaffolds focus on the two-dimensional (2D) surface structures that are patterned in the micro-/nanoscales with various repeating sizes and shapes to induce the alignment of myoblasts and myotube formation. The 2D patterned surface clearly provides effective analytical results of pattern size and shape of the myoblast alignment and differentiation. However, it is inconvenient in terms of the direct application for clinical usage due to the limited thickness and 3D shapeability. Hence, the present study suggests an innovative hydrogel or synthetic structure that consists of uniaxially surface-patterned cylindrical struts for skeleton muscle regeneration. The alignment of the pattern on the hydrogel (collagen) and poly(ε-caprolactone) struts was attained with the fibrillation of poly(vinyl alcohol) and the leaching process. Various cell culture results indicate that the C2C12 cells on the micropatterned collagen structure were fully aligned, and that a significantly high level of myotube formation was achieved when compared to the collagen structures that were not treated with the micropatterning process.

Tunable Nanocarrier Morphologies from Glycopolypeptide-based Amphiphilic Biocompatible Star Copolymers and Their Carbohydrate Specific Intracellular Delivery

KAUST Repository

Pati, Debasis

2015-12-21

Nano-carriers with carbohydrates on the surface represent a very interesting class of drug delivery vehicles since carbohydrates are involved in bio-molecular recognition events in vivo. We have synthesized biocompatible miktoarm star copolymers comprising glycopolypeptide and poly(ε-caprolactone) chains, using ring opening polymerization and ‘click chemistry’. The amphiphilic copolymers were self-assembled in water into morphologies such as nanorods, polymersomes and micelles with carbohydrates displayed on the surface. We demonstrate that, the formation of nanostructure could be tuned by chain length of the blocks and was not affected by the type of sugar residue. These nanostructures were characterized in detail using a variety of techniques such as TEM, AFM, cryogenic electron microscopy, spectrally resolved fluorescence imaging and dye encapsulation techniques. We show that it is possible to sequester both hydrophobic as well as hydrophilic dyes within the nanostructures. Finally, we show that these non-cytotoxic manno-sylated rods and polymersomes were selectively and efficiently taken up by MDA-MB-231 breast cancer cells demonstrating their potential as nanocarriers for drug delivery.

Poly(acrylic acid) conjugated hollow mesoporous carbon as a dual-stimuli triggered drug delivery system for chemo-photothermal synergistic therapy

Energy Technology Data Exchange (ETDEWEB)

Li, Xian; Liu, Chang; Wang, Shengyu; Jiao, Jian; Di, Donghua; Jiang, Tongying; Zhao, Qinfu, E-mail: zqf021110505@163.com; Wang, Siling, E-mail: silingwang@syphu.edu.cn

2017-02-01

In this work, we described the development of the redox and pH dual stimuli-responsive drug delivery system and combination of the chemotherapy and photothermal therapy for cancer treatment. The poly(acrylic acid) (PAA) was conjugated on the outlets of hollow mesoporous carbon (HMC) via disulfide bonds. PAA was used as a capping to block drug within the mesopores of HMC for its lots of favorable advantages, such as good biocompatibility, appropriate molecular weight to block the mesopores of HMC, extension of the blood circulation, and the improvement of the dispersity of the nano-carriers in physiological environment. The DOX loaded DOX/HMC-SS-PAA had a high drug loading amount up to 51.9%. The in vitro drug release results illustrated that DOX/HMC-SS-PAA showed redox and pH dual-responsive drug release, and the release rate could be further improved by the near infrared (NIR) irradiation. Cell viability experiment indicated that DOX/HMC-SS-PAA had a synergistic therapeutic effect by combination of chemotherapy and photothermal therapy. This work suggested that HMC-SS-PAA exhibited dual-responsive drug release property and could be used as a NIR-adsorbing drug delivery system for chemo-photothermal synergistic therapy. - Highlights: • Poly(acrylic acid) was grafted on hollow mesoporous carbon (HMC) via disulfide bonds. • The grafted PAA could increase the biocompatibility and stability of HMC. • The DOX-loaded DOX/HMC-SS-PAA had a high drug loading efficiency up to 51.9%. • DOX/HMC-SS-PAA showed redox/pH dual-responsive and NIR-triggered drug release. • DOX/HMC-SS-PAA showed a chemo/photothermal synergistic therapy effect.

Poly(acrylic acid) conjugated hollow mesoporous carbon as a dual-stimuli triggered drug delivery system for chemo-photothermal synergistic therapy

International Nuclear Information System (INIS)

Li, Xian; Liu, Chang; Wang, Shengyu; Jiao, Jian; Di, Donghua; Jiang, Tongying; Zhao, Qinfu; Wang, Siling

2017-01-01

In this work, we described the development of the redox and pH dual stimuli-responsive drug delivery system and combination of the chemotherapy and photothermal therapy for cancer treatment. The poly(acrylic acid) (PAA) was conjugated on the outlets of hollow mesoporous carbon (HMC) via disulfide bonds. PAA was used as a capping to block drug within the mesopores of HMC for its lots of favorable advantages, such as good biocompatibility, appropriate molecular weight to block the mesopores of HMC, extension of the blood circulation, and the improvement of the dispersity of the nano-carriers in physiological environment. The DOX loaded DOX/HMC-SS-PAA had a high drug loading amount up to 51.9%. The in vitro drug release results illustrated that DOX/HMC-SS-PAA showed redox and pH dual-responsive drug release, and the release rate could be further improved by the near infrared (NIR) irradiation. Cell viability experiment indicated that DOX/HMC-SS-PAA had a synergistic therapeutic effect by combination of chemotherapy and photothermal therapy. This work suggested that HMC-SS-PAA exhibited dual-responsive drug release property and could be used as a NIR-adsorbing drug delivery system for chemo-photothermal synergistic therapy. - Highlights: • Poly(acrylic acid) was grafted on hollow mesoporous carbon (HMC) via disulfide bonds. • The grafted PAA could increase the biocompatibility and stability of HMC. • The DOX-loaded DOX/HMC-SS-PAA had a high drug loading efficiency up to 51.9%. • DOX/HMC-SS-PAA showed redox/pH dual-responsive and NIR-triggered drug release. • DOX/HMC-SS-PAA showed a chemo/photothermal synergistic therapy effect.

Thermo-mechanical properties of poly ε-caprolactone/poly L-lactic acid blends: addition of nalidixic acid and polyethylene glycol additives.

Science.gov (United States)

Douglas, P; Albadarin, Ahmad B; Al-Muhtaseb, Ala'a H; Mangwandi, Chirangano; Walker, G M

2015-05-01

The search for ideal biomaterials is still on-going for tissue regeneration. In this study, blends of poly ε-caprolactone (PCL) with poly l-lactic acid (PLLA), nalidixic acid (NA) and polyethylene glycol (PEG) were prepared. Mechanical and thermal properties of the blends were investigated by tensile and flexural analysis, DSC, TGA, WXRD, MFI, BET, SEM and hot stage optical microscopy. Results showed that the loading of PLLA caused a significant decrease in tensile strength and almost total eradication of the elongation at break of PCL matrix, especially after PEG and NA addition. Increased stiffness was also noted with additional NA, PEG and PLLA, resulting in an increase in the flexural modulus of the blends. Isothermal degradation indicated that bulk PCL, PLLA and the blends were thermally stable at 200°C for the duration of 2h making extrusion of the blends at this temperature viable. Morphological study showed that increasing the PLLA content and addition of the very low viscosity PEG and powder NA decreased the Melt Flow Indexer and increased the viscosity. At the higher temperature, the PLLA begins to soften and eventually melts allowing for increased flow and, coupling this with, the natural increase in MFI caused by temperature is enhanced further. The PEG and NA addition increased dramatically the pore volume which is important for cell growth and flow transport of nutrients and metabolic waste. Copyright © 2015 Elsevier Ltd. All rights reserved.

Poly(Acrylic acid–Based Hybrid Inorganic–Organic Electrolytes Membrane for Electrical Double Layer Capacitors Application

Directory of Open Access Journals (Sweden)

Chiam-Wen Liew

2016-05-01

Full Text Available Nanocomposite polymer electrolyte membranes (NCPEMs based on poly(acrylic acid(PAA and titania (TiO2 are prepared by a solution casting technique. The ionic conductivity of NCPEMs increases with the weight ratio of TiO2.The highest ionic conductivity of (8.36 ± 0.01 × 10−4 S·cm−1 is obtained with addition of 6 wt % of TiO2 at ambient temperature. The complexation between PAA, LiTFSI and TiO2 is discussed in Attenuated total reflectance-Fourier Transform Infrared (ATR-FTIR studies. Electrical double layer capacitors (EDLCs are fabricated using the filler-free polymer electrolyte or the most conducting NCPEM and carbon-based electrodes. The electrochemical performances of fabricated EDLCs are studied through cyclic voltammetry (CV and galvanostatic charge-discharge studies. EDLC comprising NCPEM shows the specific capacitance of 28.56 F·g−1 (or equivalent to 29.54 mF·cm−2 with excellent electrochemical stability.

Poly(ethylene-co-acrylic acid)-g-poly(ethylene glycol) graft copolymer templated synthesis of mesoporous TiO{sub 2} thin films for quasi-solid-state dye sensitized solar cells

Energy Technology Data Exchange (ETDEWEB)

Patel, Rajkumar; Jung, Ye Eun; Kim, Dong Jun; Kim, Sang Jin; Kim, Jong Hak, E-mail: jonghak@yonsei.ac.kr

2014-02-03

An amphiphilic graft copolymer, poly(ethylene-co-acrylic acid)-graft-poly(ethylene glycol) (PEAA-g-PEG), consisting of a PEAA backbone and PEG side chains was synthesized via an esterification reaction. {sup 1}H nuclear magnetic resonance and Fourier-transformed infrared analysis demonstrated esterification between carboxylic acid of PEAA and hydroxyl group of PEG. Small angle X-ray scattering results revealed that the crystalline domain spacing of PEAA increased from 11.3 to 12.8 nm upon using a more polar solvent with a higher affinity for poly(acrylic acid), while the crystalline domain spacing of PEAA disappeared with PEG grafting, indicating structural change to an amorphous state. Mesoporous TiO{sub 2} thin films were synthesized via a sol–gel reaction using PEAA-g-PEG graft copolymer as a structure-directing agent. The hydrophilically-preformed TiO{sub 2} nanoparticles were selectively confined in the hydrophilic PEG domains of the graft copolymer, and mesoporous TiO{sub 2} thin films were formed, as confirmed by scanning electron microscopy. The morphology of TiO{sub 2} films was tunable by varying the concentrations of polymer solutions and the amount of preformed TiO{sub 2}. A quasi-solid-state dye-sensitized solar cell fabricated with PEAA-g-PEG templated TiO{sub 2} film exhibited an energy conversion efficiency of 3.8% at 100 mW/cm{sup 2}, which was greater than that of commercially-available paste (2.6%) at a similar film thickness (3 μm). The improved performance was due to the larger surface area for high dye loading and organized structure with good interconnectivity. - Highlights: • Poly(ethylene-co-acrylic acid)-g-poly(ethylene glycol) (PEAA-g-PEG) graft copolymer is synthesized. • Amphiphilic PEAA-g-PEG acts as a structure directing agent. • Mesoporous TiO{sub 2} thin films are prepared by sol–gel reaction using PEAA-g-PEG template. • Efficiency of DSSC with templated TiO{sub 2} is greater than with commercial TiO{sub 2} paste.

Degradation Behaviour of Gamma Irradiated Poly(Acrylic Acid)-graft-Chitosan Superabsorbent Hydrogel

Science.gov (United States)

Ria Barleany, Dhena; Ilhami, Alpin; Yusuf Yudanto, Dea; Erizal

2018-03-01

A series of superabsorbent hydrogels were prepared from chitosan and partially neutralized acrylic acid at room temperature by gamma irradiation technique. The effect of irradiation and chitosan addition to the degradation behaviour of polymer were investigated. The gel content, swelling capacity, Equillibrium Degree of Swelling (EDS), Fourier Transform Infra Red (FTIR), and Scanning Electron Microscopy (SEM) study were also performed. Natural degradation in soil and thermal degradation by using of TGA analysis were observed. The variation of chitosan compositions were 0.5, 1, 1.5, and 2 g and the total irradiation doses were 5, 10, 15, and 20 kGy. The highest water capacity of 583.3 g water/g dry hydrogel was resulted from 5 kGy total irradiation dose and 0,5 g addition of chitosan. From the thermal degradation evaluation by using of TGA analysis showed that irradiation dose did not give a significant influence to the degradation rate. The rate of thermal degradation was ranged between 2.42 to 2.55 mg/min. In the natural test of degradation behaviour by using of soil medium, the hydrogel product with chitosan addition was found to have better degradability compared with the poly(acrylic acid) polymer without chitosan.

Matrigel immobilization on the shish-kebab structured poly(ɛ-caprolactone) nanofibers for skin tissue engineering

Science.gov (United States)

Jing, Xin; Mi, Hao-Yang; Peng, Xiang-Fang; Turng, Lih-Sheng

2016-03-01

Surface properties of tissue engineering scaffolds such as topography, hydrophilicity, and functional groups play a vital role in cell adhesion, migration, proliferation, and apoptosis. First, poly(ɛ-caprolactone) (PCL) shish-kebab scaffolds (PCL-SK), which feature a three-dimensional structure comprised of electrospun PCL nanofibers covered by periodic, self-induced PCL crystal lamellae on the surface, was created to mimic the nanotopography of native collagen fibrils in the extracellular matrix (ECM). Second, matrigel was covalently immobilized on the surface of alkaline hydrolyzed PCL-SK scaffolds to enhance their hydrophilicity. This combined approach not only mimics the nanotopography of native collagen fibrils, but also simulates the surface features of collagen fibrils for cell growth. To investigate the viability of such scaffolds, HEF1 fibroblast cell assays were conducted and the results revealed that the nanotopography of the PCL-SK scaffolds facilitated cell adhesion and proliferation. The matrigel functionalization on PCL-SK scaffolds further enhanced cellular response, which suggested elevated biocompatibility and greater potential for skin tissue engineering applications.

Matrigel immobilization on the shish-kebab structured poly(ε-caprolactone) nanofibers for skin tissue engineering

Energy Technology Data Exchange (ETDEWEB)

Jing, Xin, E-mail: jingxinscut@gmail.com; Mi, Hao-Yang [National Engineer Research Center of Novel Equipment for Polymer Processing, The Key Laboratory of Polymer Processing Engineering of Ministry of Education, South China University of Technology, Guangzhou, 510640 (China); Wisconsin Institutes for Discovery, University of Wisconsin-Madison, 53715 (United States); Peng, Xiang-Fang, E-mail: pmxfpeng@scut.edu.cn, E-mail: turng@engr.wisc.edu [National Engineer Research Center of Novel Equipment for Polymer Processing, The Key Laboratory of Polymer Processing Engineering of Ministry of Education, South China University of Technology, Guangzhou, 510640 (China); Turng, Lih-Sheng, E-mail: pmxfpeng@scut.edu.cn, E-mail: turng@engr.wisc.edu [Wisconsin Institutes for Discovery, University of Wisconsin-Madison, 53715 (United States)

2016-03-09

Surface properties of tissue engineering scaffolds such as topography, hydrophilicity, and functional groups play a vital role in cell adhesion, migration, proliferation, and apoptosis. First, poly(ε-caprolactone) (PCL) shish-kebab scaffolds (PCL-SK), which feature a three-dimensional structure comprised of electrospun PCL nanofibers covered by periodic, self-induced PCL crystal lamellae on the surface, was created to mimic the nanotopography of native collagen fibrils in the extracellular matrix (ECM). Second, matrigel was covalently immobilized on the surface of alkaline hydrolyzed PCL-SK scaffolds to enhance their hydrophilicity. This combined approach not only mimics the nanotopography of native collagen fibrils, but also simulates the surface features of collagen fibrils for cell growth. To investigate the viability of such scaffolds, HEF1 fibroblast cell assays were conducted and the results revealed that the nanotopography of the PCL-SK scaffolds facilitated cell adhesion and proliferation. The matrigel functionalization on PCL-SK scaffolds further enhanced cellular response, which suggested elevated biocompatibility and greater potential for skin tissue engineering applications.

Strontium doped poly-ε-caprolactone composite scaffolds made by reactive foaming

Energy Technology Data Exchange (ETDEWEB)

Zehbe, Rolf, E-mail: zehbe@bls-germany.com [BLS Laboratories GmbH, Berlin (Germany); University of Potsdam, Institute of Physics and Astronomy, Potsdam (Germany); Zehbe, Kerstin [University of Potsdam, Department of Chemistry, Potsdam (Germany)

2016-10-01

In the reconstruction and regeneration of bone tissue, a primary goal is to initiate bone growth and to stabilize the surrounding bone. In this regard, a potentially useful component in biomaterials for bone tissue engineering is strontium, which acts as cationic active agent, triggering certain intracellular pathways and acting as so called dual action bone agent which inhibits bone resorption while stimulating bone regeneration. In this study we established a novel processing for the foaming of a polymer (poly-ε-caprolactone) and simultaneous chemical reaction of a mixture of calcium and strontium hydroxides to the respective carbonates using supercritical carbon dioxide. The resultant porous composite scaffold was optimized in composition and strontium content and was characterized via different spectroscopic (infrared and Raman spectroscopy, energy dispersive X-ray spectroscopy), imaging (SEM, μCT), mechanical testing and in vitro methods (fluorescence vital staining, MTT-assay). As a result, the composite scaffold showed good in vitro biocompatibility with partly open pore structure and the expected chemistry. First mechanical testing results indicate sufficient mechanical stability to support future in vivo applications. - Highlights: • Reactive foaming has been established for the synthesis of a PCL matrix with integrated strontium and calcium species • This material can potentially be useful in bone tissue engineering applications • Comparative in vitro cell culture experiments, imaging and spectroscopy analysis have been conducted.

A novel poly(acrylic acid-co-acrylamide)/diatomite composite flocculant with outstanding flocculation performance.

Science.gov (United States)

Xu, Kun; Liu, Yao; Wang, Yang; Tan, Ying; Liang, Xuecheng; Lu, Cuige; Wang, Haiwei; Liu, Xiusheng; Wang, Pixin

2015-01-01

Series of anionic flocculants with outstanding flocculation performance, poly(acrylic acid-co-acrylamide)/diatomite composite flocculants (PAAD) were successfully prepared through aqueous solution copolymerization and applied to flocculate from oil-field fracturing waste-water. The structure of PAAD was characterized by Fourier transform infra-red spectroscopy, (13)C nuclear magnetic resonance and X-ray diffraction tests, and its properties were systematically evaluated by viscometer, thermogravimetry analysis and flocculation measurements. Furthermore, the influences of various reaction parameters on the apparent viscosity of flocculant solution were studied, and the optimum synthesis condition was determined. The novel composite flocculants exhibited outstanding flocculation properties. Specifically, the dosage of composite flocculants that could make the transmittance of treated wastewater exceed 90% was only approximately 12-35 ppm, which was far lower than that of conventional flocculants. Meanwhile, the settling time was lower than 5 s, which was similar to that of conventional flocculants. This was because PAAD flocculants had a higher absorption capacity, and larger chain extending space than conventional linear flocculants, which could refrain from the entanglement of linear polymer chains and significantly improve flocculation capacity.

Synthesis and characterization of zinc chloride containing poly(acrylic acid) hydrogel by gamma irradiation

International Nuclear Information System (INIS)

Park, Jong-Seok; Kuang, Jia; Gwon, Hui-Jeong; Lim, Youn-Mook; Jeong, Sung-In; Shin, Young-Min; Seob Khil, Myung; Nho, Young-Chang

2013-01-01

In this study, the characterization of zinc chloride incorporated into a poly(acrylic acid) (PAAc) hydrogel prepared by gamma-ray irradiation was investigated. Zinc chloride powder with different concentrations was dissolved in the PAAc solution, and it was crosslinked with gamma-ray irradiation. The effects of various parameters such as zinc ion concentration and irradiation doses on characteristics of the hydrogel formed were investigated in detail for obtaining an antibacterial wound dressing. In addition, the gel content, pH-sensitive (pH 4 or 7) swelling ratio, and UV–vis absorption spectra of the zinc particles in the hydrogels were characterized. Moreover, antibacterial properties of these new materials against Staphylococcus aureus and Escherichia coli strains were observed on solid growth media. The antibacterial tests indicated that the zinc chloride containing PAAc hydrogels have good antibacterial activity. - Highlights: • The characterization of zinc chloride containing PAA hydrogel was investigated. • The gel content increased with an increase in absorbed dose up to 75 kGy. • Finally, the zinc chloride based hydrogels have an antibacterial activity

Chitosan surface modified electrospun poly(ε-caprolactone)/carbon nanotube composite fibers with enhanced mechanical, cell proliferation and antibacterial properties.

Science.gov (United States)

Wang, Siyu; Li, Yumei; Zhao, Rui; Jin, Toufeng; Zhang, Li; Li, Xiang

2017-11-01

The surface modification is one of the most effective methods to improve the bioactivity and cell affinity effect of electrospun poly(ε-caprolactone) (PCL) fibers. In the present study, chitosan (CS), a cationic polysaccharide, was used to modify the surface of electrospun PCL fibers. To obtain strong interaction between CS and PCL fibers, negatively charged PCL fibers were prepared by the incorporation of acid-treated carbon nanotubes (CNTs) into the fibers. In this way, the positively charged chitosan could be immobilized onto the surface of PCL fibers tightly by the electrostatic attraction. Besides, the incorporation of CNTs could significantly improve the mechanical strength of electrospun PCL fibers even after the CS modification, which guaranteed their usability in practical applications. The CS modification could effectively improve the wettability and bioactivity of electrospun PCL fibers. Cultivation of L929 fibroblast cells on the obtained fibers and the antibacterial activity were both evaluated to discuss the influence of chitosan modification. The results indicated that this modification could enhance the cell proliferation and antibacterial ability in comparison to the non-modified groups. Copyright © 2017 Elsevier B.V. All rights reserved.

Poly(acrylic acid)-templated silver nanoclusters as a platform for dual fluorometric turn-on and colorimetric detection of mercury (II) ions.

Science.gov (United States)

Tao, Yu; Lin, Youhui; Huang, Zhenzhen; Ren, Jinsong; Qu, Xiaogang

2012-01-15

An easy prepared fluorescence turn-on and colorimetric dual channel probe was developed for rapid assay of Hg(2+) ions with high sensitivity and selectivity by using poly(acrylic acid)-templated silver nanoclusters (PAA-AgNCs). The PAA-AgNCs exhibited weak fluorescence, while upon the addition of Hg(2+) ions, AgNCs gives a dramatic increase in fluorescence as a result of the changes of the AgNCs states. The detection limit was estimated to be 2 nM, which is much lower than the Hg(2+) detection requirement for drinking water of U.S. Environmental Protection Agency, and the turn-on sensing mode offers additional advantage to efficiently reduce background noise. Also, a colorimetric assay of Hg(2+) ions can be realized due to the observed absorbance changes of the AgNCs. More importantly, the method was successfully applied to the determination of Hg(2+) ions in real water samples, which suggests our proposed method has a great potential of application in environmental monitoring. Copyright © 2011 Elsevier B.V. All rights reserved.

Insulin-loaded poly(epsilon-caprolactone) nanoparticles: efficient, sustained and safe insulin delivery system.

Science.gov (United States)

de Araújo, Thiago M; Teixeira, Zaine; Barbosa-Sampaio, Helena C; Rezende, Luiz F; Boschero, Antonio C; Durán, Nelson; Höehr, Nelci F

2013-06-01

The aim of this work was to develop an efficient, biodegradable, biocompatible and safe controlled release system using insulin-loaded poly(epsilon-caprolactone) (PCL) nanoparticles. The insulin-loaded PCL nanoparticles were prepared by double emulsion method (water-in-oil-in-water) using Pluronic F68 as emulsifier. Using the double emulsion method a high insulin encapsulation efficiency (90.6 +/-1.6%) with a zeta potential of -29 +/-2.7 mV and average particle size of 796 +/-10.5 nm was obtained. Insulin-loaded PCL nanoparticles showed no toxicity to MIN6 cells. Insulin nanoparticles administered subcutaneously and intraperitoneally in rats reduced glycaemia of basal levels after 15 minutes, and presented a sustainable hypoglycemic effect on insulin-dependent type 1 diabetic rats, showing to be more efficient than unencapsulated insulin. Furthermore, these nanoparticles were not hepatotoxic, as evaluated by the effect over liver cell-death and oxidative stress scavenger system in rats. These results suggest that insulin-loaded PCL nanoparticles prepared by water-in-oil-in-water emulsion method are biocompatible, efficient and safe insulin-delivering system with controlled insulin release, which indicates that it may be a powerful tool for insulin-dependent patients care.

Improved surface property of PVDF membrane with amphiphilic zwitterionic copolymer as membrane additive

Energy Technology Data Exchange (ETDEWEB)

Li Jianhua, E-mail: jhli_2005@163.com [Institute of Biomedical and Pharmaceutical Technology and College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou 350001 (China); Li Mizi; Miao Jing; Wang Jiabin; Shao Xisheng [Institute of Biomedical and Pharmaceutical Technology and College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou 350001 (China); Zhang Qiqing, E-mail: zhangqiq@126.com [Institute of Biomedical and Pharmaceutical Technology and College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou 350001 (China) and Institute of Biomedical Engineering, Chinese Academy of Medical Science, Peking Union Medical College, Tianjin 300192 (China)

2012-06-15

An attempt to improve hydrophilicity and anti-fouling properties of PVDF membranes, a novel amphiphilic zwitterionic copolymer poly(vinylidene fluoride)-graft-poly(sulfobetaine methacrylate) (PVDF-g-PSBMA) was firstly synthesized by atom transfer radical polymerization (ATRP) and used as amphiphilic copolymer additive in the preparation of PVDF membranes. The PVDF-g-PSBMA/PVDF blend membranes were prepared by immersion precipitation process. Fourier transform infrared attenuated reflection spectroscopy (FTIR-ATR) and X-ray photoelectronic spectroscopy (XPS) measurements confirmed that PSBMA brushes from amphiphilic additives were preferentially segregated to membrane-coagulant interface during membrane formation. The morphology of membranes was characterized by scanning electron microscopy (SEM). Water contact angle measurements showed that the surface hydrophilicity of PVDF membranes was improved significantly with the increasing of amphiphilic copolymer PVDF-g-PSBMA in cast solution. Protein static adsorption experiment and dynamic fouling resistance experiment revealed that the surface enrichment of PSBMA brush endowed PVDF blend membrane great improvement of surface anti-fouling ability.

Improved surface property of PVDF membrane with amphiphilic zwitterionic copolymer as membrane additive

International Nuclear Information System (INIS)

Li Jianhua; Li Mizi; Miao Jing; Wang Jiabin; Shao Xisheng; Zhang Qiqing

2012-01-01

An attempt to improve hydrophilicity and anti-fouling properties of PVDF membranes, a novel amphiphilic zwitterionic copolymer poly(vinylidene fluoride)-graft-poly(sulfobetaine methacrylate) (PVDF-g-PSBMA) was firstly synthesized by atom transfer radical polymerization (ATRP) and used as amphiphilic copolymer additive in the preparation of PVDF membranes. The PVDF-g-PSBMA/PVDF blend membranes were prepared by immersion precipitation process. Fourier transform infrared attenuated reflection spectroscopy (FTIR-ATR) and X-ray photoelectronic spectroscopy (XPS) measurements confirmed that PSBMA brushes from amphiphilic additives were preferentially segregated to membrane-coagulant interface during membrane formation. The morphology of membranes was characterized by scanning electron microscopy (SEM). Water contact angle measurements showed that the surface hydrophilicity of PVDF membranes was improved significantly with the increasing of amphiphilic copolymer PVDF-g-PSBMA in cast solution. Protein static adsorption experiment and dynamic fouling resistance experiment revealed that the surface enrichment of PSBMA brush endowed PVDF blend membrane great improvement of surface anti-fouling ability.

Surface grafted chitosan gels. Part I. Molecular insight into the formation of chitosan and poly(acrylic acid) multilayers

DEFF Research Database (Denmark)

Liu, Chao; Thormann, Esben; Claesson, Per M.

2014-01-01

Composite polyelectrolyte multilayers of chitosan and low molecular weight poly(acrylic acid) (PAA) have been assembled by sequential adsorption as a first step toward building a surface anchored chitosan gel. Silane chemistry was used to graft the first chitosan layer to prevent film detachment...... and decomposition. The assembly process is characterized by nonlinear growth behavior, with different adsorption kinetics for chitosan and PAA. In situ analysis of the multilayer by means of surface sensitive total internal reflection Raman (TIRR) spectroscopy, combined with target factor analysis of the spectra...... molecular weight chitosan shows a similar behavior, although to a much lower extent. Our data demonstrate that the charged monomeric units of chitosan are mainly compensated by carboxylate ions from PAA. Furthermore, the morphology and mechanical properties of the multilayers were investigated in situ using...

Radiation preparation of drug carriers based polyacrylic acid (PAAc) using poly(vinyl pyrrolidone) (PVP) as a template polymer

Science.gov (United States)

Abd El-Rehim, H. A.; Hegazy, E. A.; Khalil, F. H.; Hamed, N. A.

2007-01-01

The present study deals with the radiation synthesis of stimuli response hydrophilic polymers from polyacrylic acid (PAAc). To maintain the property of PAAc and control the water swellibility for its application as a drug delivery system, radiation polymerization of AAc in the presence of poly(vinyl pyrrolidone) (PVP) as a template polymer was carried out. Characterization of the prepared PAA/PVP inter-polymer complex was investigated by determining gel content, swelling property, hydrogel microstructure and the release rate of caffeine as a model drug. The release rate of caffeine from the PAA/PVP inter-polymer complexes showed pH-dependency, and seemed to be mainly controlled by the dissolution rate of the complex above a p Ka of PAAc. The prepared inter-polymer complex could be used for application as drug carriers.

Poly(ethylene oxide)–Poly(propylene oxide)-Based Copolymers for ...

African Journals Online (AJOL)

Amphiphilic poly(ethylene oxide)–poly(propylene oxide) (PEO–PPO)-based copolymers are thermoresponsive materials having aggregation properties in aqueous medium. As hydrosolubilizers of poorly water-soluble drugs and improved stability of sensitive agents, these materials have been investigated for improvement ...

Assessment of poly(ε-caprolactone)/poly(3-hydroxybutyrate-co-3-hydroxyvalerate) blends processed by solvent casting and electrospinning

International Nuclear Information System (INIS)

Del Gaudio, Costantino; Ercolani, Enrico; Nanni, Francesca; Bianco, Alessandra

2011-01-01

Research highlights: → PHBV, PCL and blends were processed in form of solvent cast films and e-spun mats. → A clear phase separation was observed for cast films when blended in equal amount. → E-spun blends were comprised of uniform and defect-free randomly arranged fibers. → DSC and XRD analyses demonstrated the immiscibility of PHBV and PCL. → Rearrangement of e-spun fibers and neckings, after axial test, were observed. - Abstract: Poly(ε-caprolactone) (PCL) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) were blended in different ratio, e.g. 30/70, 50/50 and 70/30 (w/w), by means of solvent casting or electrospinning. Microstructure, thermal and mechanical properties of cast films and non-woven mats were investigated by means of scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), differential scanning calorimetry (DSC), and uniaxial tensile test. The microstructure of PHBV/PCL solvent cast films (thickness 65-100 μm) was strictly dependent on the composition of the blend, a clean phase separation was observed for the 50/50 (w/w) sample. All electrospun PHBV/PCL blends (thickness 350-800 μm) were characterised by uniform and homogenous fibers, the average size was about 3 μm. Both techniques led to polymeric blends comprised of separate crystalline domains associated to an amorphous interdisperse phase. It has also been demonstrated that electrospun PHBV/PCL blends showed a lower segregation degree among the crystalline domains. Solvent cast blends were characterised by superior mechanical properties in terms of tensile modulus and tensile strength compared to electrospun ones. Fractured electrospun blends showed an overall fiber rearrangement in the direction of the applied load, eventually highlighting multiple necking regions along the fibers.

Aqueous lubricating properties of charged (ABC) and neutral (ABA) triblock copolymer chains

DEFF Research Database (Denmark)

Røn, Troels; Javakhishvili, Irakli; Patil, Navin J.

2014-01-01

Application of charged polymer chains as additives for lubricating neutral surfaces in aqueous envi- ronment, especially via polymer physisorption, is generally impeded by the electrostatic repulsion be- tween adjacent polymers on the surface. In this study, we have investigated the adsorption an...... improvement compared to fully charged polymer chains, e.g. poly(acrylic acid)- block -poly(2-methoxyethyl acrylate) (PAA- b -PMEA), which is attributed to dilution of charged moieties on the surface and subsequent improvement of the lubricating fi lm stability......Application of charged polymer chains as additives for lubricating neutral surfaces in aqueous envi- ronment, especially via polymer physisorption, is generally impeded by the electrostatic repulsion be- tween adjacent polymers on the surface. In this study, we have investigated the adsorption...... and aqueous lubricating properties of an amphiphilic triblock copolymer, comprised of a neutral poly(ethylene glycol) (PEG) block, a hydrophobic poly(2-methoxyethyl acrylate) (PMEA) block, and a charged poly(methacrylic acid) (PMAA) block, namely PEG- b -PMEA- b -PMAA. After adsorption onto a nonpolar...

Thiolated and S-protected hydrophobically modified cross-linked poly(acrylic acid)--a new generation of multifunctional polymers.

Science.gov (United States)

Bonengel, Sonja; Haupstein, Sabine; Perera, Glen; Bernkop-Schnürch, Andreas

2014-10-01

The aim of this study was to create a novel multifunctional polymer by covalent attachment of l-cysteine to the polymeric backbone of hydrophobically modified cross-linked poly(acrylic acid) (AC1030). Secondly, the free thiol groups of the resulting thiomer were activated using 2-mercaptonicotinic acid (2-MNA) to provide full reactivity and stability. Within this study, 1167.36 μmol cysteine and 865.72 μmol 2-MNA could be coupled per gram polymer. Studies evaluating mucoadhesive properties revealed a 4-fold extended adherence time to native small intestinal mucosa for the thiomer (AC1030-cysteine) as well as an 18-fold prolonged adhesion for the preactivated thiomer (AC1030-Cyst-2-MNA) compared to the unmodified polymer. Modification of the polymer led to a higher tablet stability concerning the thiomer and the S-protected thiomer, but a decelerated water uptake could be observed only for the preactivated thiomer. Neither the novel conjugates nor the unmodified polymer showed severe toxicity on Caco-2 cells. Evaluation of emulsification capacity proofed the ability to incorporate lipophilic compounds like medium chain triglycerides and the preservation of the emulsifying properties after the modifications. According to these results thiolated AC1030 as well as the S-protected thiolated polymer might provide a promising tool for solid and semisolid formulations in pharmaceutical development. Copyright © 2014 Elsevier B.V. All rights reserved.

Comparative Study of Poly (ε-Caprolactone) and Poly(Lactic-co-Glycolic Acid) -Based Nanofiber Scaffolds for pH-Sensing.

Science.gov (United States)

Di, Wenjun; Czarny, Ryan S; Fletcher, Nathan A; Krebs, Melissa D; Clark, Heather A

2016-10-01

This study aims to develop biodegradable and biocompatible polymer-based nanofibers that continuously monitor pH within microenvironments of cultured cells in real-time. In the future, these fibers will provide a scaffold for tissue growth while simultaneously monitoring the extracellular environment. Sensors to monitor pH were created by directly electrospinning the sensor components within a polymeric matrix. Specifically, the entire fiber structure is composed of the optical equivalent of an electrode, a pH-sensitive fluorophore, an ionic additive, a plasticizer, and a polymer to impart mechanical stability. The resulting poly(ε-caprolactone) (PCL) and poly(lactic-co-glycolic acid) (PLGA) based sensors were characterized by morphology, dynamic range, reversibility and stability. Since PCL-based nanofibers delivered the most desirable analytical response, this matrix was used for cellular studies. Electrospun nanofiber scaffolds (NFSs) were created directly out of optode material. The resulting NFS sensors respond to pH changes with a dynamic range centered at 7.8 ± 0.1 and 9.6 ± 0.2, for PCL and PLGA respectively. NFSs exhibited multiple cycles of reversibility with a lifetime of at least 15 days with preservation of response characteristics. By comparing the two NFSs, we found PCL-NFSs are more suitable for pH sensing due to their dynamic range and superior reversibility. The proposed sensing platform successfully exhibits a response to pH and compatibility with cultured cells. NSFs will be a useful tool for creating 3D cellular scaffolds that can monitor the cellular environment with applications in fields such as drug discovery and tissue engineering.

Amphiphilic brushes from metallo-supramolecular block copolymers

NARCIS (Netherlands)

Guillet, P.; Fustin, C.A.; Wouters, D.; Höppener, S.; Schubert, U.S.; Gohy, J.M.W.

2009-01-01

A novel strategy to control the formation of amphiphilic brushes from metallo-supramol. block copolymers is described. The investigated copolymer consists of a polystyrene block linked to a poly(ethylene oxide) one via a charged bis-terpyridine ruthenium(ii) complex (PS-[Ru]-PEO). The initial

Biopolymers/poly(ε-caprolactone)/polyethylenimine functionalized nano-hydroxyapatite hybrid cryogel: Synthesis, characterization and application in gene delivery.

Science.gov (United States)

Simionescu, Bogdan C; Drobota, Mioara; Timpu, Daniel; Vasiliu, Tudor; Constantinescu, Cristina Ana; Rebleanu, Daniela; Calin, Manuela; David, Geta

2017-12-01

Nano-hydroxyapatite (nHAp), surface functionalized with linear polyethylenimine (LPEI), was used for the preparation of biocomposites in combination with biopolymers and poly(ε-caprolactone) (PCL), by cryogelation technique, to yield biomimetic scaffolds with controlled interconnected macroporosity, mechanical stability, and predictable degradation behavior. The structural characteristics, swelling and degradation behavior of hydroxyapatite and hydroxyapatite/β-tricalcium phosphate (β-TCP) filled matrices were investigated as compared to the corresponding naked polymer 3D system. It was found that the homogeneity and cohesivity of the composite are significantly dependent on the size and amount of the included inorganic particles, which are thus determining the structural parameters. Surface modification with LPEI and nanodimensions favored the nHAp integration in the organic matrix, with preferential location along protein fibers, while β-TCP microparticles induced an increased disorder in the hybrid system. The biocomposite including nHAp only was further investigated targeting biomedical uses, and proved to be non-cytotoxic and capable of acting as gene-activated matrix (GAM). It allowed sustained delivery over time (until 22days) of embedded PEI 25 -pDNA polyplexes at high levels of transgene expression, while insuring a decrease in cytotoxicity as compared to polyplexes alone. Experimental data recommend such biocomposite as an attractive material for regenerative medicine. Copyright © 2017 Elsevier B.V. All rights reserved.

Aligned poly(ε-caprolactone)/graphene oxide and reduced graphene oxide nanocomposite nanofibers: Morphological, mechanical and structural properties.

Science.gov (United States)

Ramazani, Soghra; Karimi, Mohammad

2015-11-01

A number of studies have demonstrated that the mechanical properties of electrospun polymeric nanofibrous scaffolds are enhanced with the incorporation of graphene and its derivatives, thus developing their applications in hard tissue engineering. However, our understanding of the relationship between the microstructure and properties of these fibrous scaffolds and how they are influenced by graphene oxide (GO) and reduced graphene oxide (RGO) loading is much more limited. Thus, in this paper, poly(ε-caprolactone) (PCL)/GO and RGO nanocomposite nanofibers containing 0, 0.1, 0.5 and 1wt.% GO and RGO were prepared using an electrospinning technique. With the addition of 0.1wt.% of GO and RGO nanosheets in PCL, the tensile strength of PCL scaffolds increased over ~160 and 304% respectively and elastic modulus increased over 103 and 163% due to the good dispersion of the nanosheets and their interaction with the molecular chains of PCL. These were supported by the parallel increase in relaxation time and molecular orientation of PCL chains at the presence of nanosheets with a loading of 0.1wt.%. The enhancement effect of the nanosheets was weakened with an increase in GO and RGO loading up to 1wt.% in which it is connected to a partial exfoliation of the nanosheets. Copyright © 2015 Elsevier B.V. All rights reserved.

Morphology, thermal and mechanical properties of poly (ε-caprolactone) biocomposites reinforced with nano-hydroxyapatite decorated graphene.

Science.gov (United States)

Zhou, Keqing; Gao, Rui; Jiang, Saihua

2017-06-15

In this work, hydroxyapatite (HAP) nanorods decorated on graphene nanosheets (HAP-Gs) was synthesized by a hydrothermal method. The structure, elemental composition and morphology of the HAP-Gs hybrids were characterized by X-ray diffraction, Fourier transform infrared and Transmission electron microscopy. Subsequently, the hybrids were incorporated into poly (ε-caprolactone) (PCL) via a solution blending method. Optical images and scanning electron microscopy observation revealed not only a well dispersion of HAP-Gs hybrids but also a strong interfacial interaction between hybrids and PCL matrix. The influence of HAP-Gs hybrids on the crystallization behavior, crystal structure, thermal stability, mechanical properties and biocompatibility of the PCL nanocomposites was investigated in detail. The results showed that the crystallization temperature of PCL was enhanced obviously, but the crystal structure was not affected by the incorporation of HAP-Gs hybrids. The mechanical properties of PCL bionanocomposites were improved obviously. Copyright © 2017 Elsevier Inc. All rights reserved.

Amphiphilic building blocks for self-assembly: from amphiphiles to supra-amphiphiles.

Science.gov (United States)

Wang, Chao; Wang, Zhiqiang; Zhang, Xi

2012-04-17

The process of self-assembly spontaneously creates well-defined structures from various chemical building blocks. Self-assembly can include different levels of complexity: it can be as simple as the dimerization of two small building blocks driven by hydrogen bonding or as complicated as a cell membrane, a remarkable supramolecular architecture created by a bilayer of phospholipids embedded with functional proteins. The study of self-assembly in simple systems provides a fundamental understanding of the driving forces and cooperativity behind these processes. Once the rules are understood, these guidelines can facilitate the research of highly complex self-assembly processes. Among the various components for self-assembly, an amphiphilic molecule, which contains both hydrophilic and hydrophobic parts, forms one of the most powerful building blocks. When amphiphiles are dispersed in water, the hydrophilic component of the amphiphile preferentially interacts with the aqueous phase while the hydrophobic portion tends to reside in the air or in the nonpolar solvent. Therefore, the amphiphiles aggregate to form different molecular assemblies based on the repelling and coordinating forces between the hydrophilic and hydrophobic parts of the component molecules and the surrounding medium. In contrast to conventional amphiphiles, supra-amphiphiles are constructed on the basis of noncovalent interactions or dynamic covalent bonds. In supra-amphiphiles, the functional groups can be attached to the amphiphiles by noncovalent synthesis, greatly speeding their construction. The building blocks for supra-amphiphiles can be either small organic molecules or polymers. Advances in the development of supra-amphiphiles will not only enrich the family of conventional amphiphiles that are based on covalent bonds but will also provide a new kind of building block for the preparation of complex self-assemblies. When polymers are used to construct supra-amphiphiles, the resulting

Self-assembly behavior of a linear-star supramolecular amphiphile based on host-guest complexation.

Science.gov (United States)

Wang, Juan; Wang, Xing; Yang, Fei; Shen, Hong; You, Yezi; Wu, Decheng

2014-11-04

A star polymer, β-cyclodextrin-poly(l-lactide) (β-CD-PLLA), and a linear polymer, azobenzene-poly(ethylene glycol) (Azo-PEG), could self-assemble into a supramolecular amphiphilic copolymer (β-CD-PLLA@Azo-PEG) based on the host-guest interaction between β-CD and azobenzene moieties. This linear-star supramolecular amphiphilic copolymer further self-assembled into a variety of morphologies, including sphere-like micelle, carambola-like micelle, naan-like micelle, shuttle-like lamellae, tube-like fiber, and random curled-up lamellae, by tuning the length of hydrophilic or hydrophobic chains. The variation of morphology was closely related to the topological structure and block ratio of the supramolecular amphiphiles. These self-assembly structures could disassemble upon an ultraviolet (UV) light irradiation.

Efficient removal of malachite green dye using biodegradable graft copolymer derived from amylopectin and poly(acrylic acid).

Science.gov (United States)

Sarkar, Amit Kumar; Pal, Aniruddha; Ghorai, Soumitra; Mandre, N R; Pal, Sagar

2014-10-13

This article reports on the application of a high performance biodegradable adsorbent based on amylopectin and poly(acrylic acid) (AP-g-PAA) for removal of toxic malachite green dye (MG) from aqueous solution. The graft copolymer has been synthesized and characterized using various techniques including FTIR, GPC, SEM and XRD analyses. Biodegradation study suggests that the co-polymer is biodegradable in nature. The adsorbent shows excellent potential (Qmax, 352.11 mg g(-1); 99.05% of MG has been removed within 30 min) for removal of MG from aqueous solution. It has been observed that point to zero charge (pzc) of graft copolymer plays significant role in adsorption efficacy. The adsorption kinetics and isotherm follow pseudo-second order and Langmuir isotherm models, respectively. Thermodynamics parameters suggest that the process of dye uptake is spontaneous. Finally desorption study shows excellent regeneration efficiency of adsorbent. Copyright © 2014 Elsevier Ltd. All rights reserved.

Poly-ε-caprolactone Coated and Functionalized Porous Titanium and Magnesium Implants for Enhancing Angiogenesis in Critically Sized Bone Defects.

Science.gov (United States)

Roland, Laura; Grau, Michael; Matena, Julia; Teske, Michael; Gieseke, Matthias; Kampmann, Andreas; Beyerbach, Martin; Murua Escobar, Hugo; Haferkamp, Heinz; Gellrich, Nils-Claudius; Nolte, Ingo

2015-12-22

For healing of critically sized bone defects, biocompatible and angiogenesis supporting implants are favorable. Murine osteoblasts showed equal proliferation behavior on the polymers poly-ε-caprolactone (PCL) and poly-(3-hydroxybutyrate)/poly-(4-hydroxybutyrate) (P(3HB)/P(4HB)). As vitality was significantly better for PCL, it was chosen as a suitable coating material for further experiments. Titanium implants with 600 µm pore size were evaluated and found to be a good implant material for bone, as primary osteoblasts showed a vitality and proliferation onto the implants comparable to well bottom (WB). Pure porous titanium implants and PCL coated porous titanium implants were compared using Live Cell Imaging (LCI) with Green fluorescent protein (GFP)-osteoblasts. Cell count and cell covered area did not differ between the implants after seven days. To improve ingrowth of blood vessels into porous implants, proangiogenic factors like Vascular Endothelial Growth Factor (VEGF) and High Mobility Group Box 1 (HMGB1) were incorporated into PCL coated, porous titanium and magnesium implants. An angiogenesis assay was performed to establish an in vitro method for evaluating the impact of metallic implants on angiogenesis to reduce and refine animal experiments in future. Incorporated concentrations of proangiogenic factors were probably too low, as they did not lead to any effect. Magnesium implants did not yield evaluable results, as they led to pH increase and subsequent cell death.

Adjuvant Activity of Poly-ε-caprolactone/Chitosan Nanoparticles Characterized by Mast Cell Activation and IFN-γ and IL-17 Production.

Science.gov (United States)

Jesus, Sandra; Soares, Edna; Borchard, Gerrit; Borges, Olga

2018-01-02

Polymeric nanoparticles (NPs) are extremely attractive vaccine adjuvants, able to promote antigen delivery and in some instances, exert intrinsic immunostimulatory properties that enhance antigen specific humoral and cellular immune responses. The poly-ε-caprolactone (PCL)/chitosan NPs were designed with the aim of being able to combine the properties of the 2 polymers in the preparation of an adjuvant for the hepatitis B surface antigen (HBsAg). This article reports important results of an in vitro mechanistic study and immunization studies with HBsAg associated with different concentrations of the nanoparticles. The results revealed that PCL/chitosan NPs promoted mast cell (MC) activation (β-hexosaminidase release) and that its adjuvant effect is not mediated by the TNF-α secretion. Moreover, we demonstrated that HBsAg loaded PCL/chitosan NPs, administered through the subcutaneous (SC) route, were able to induce higher specific antibody titers without increasing IgE when compared to a commercial vaccine, and that the IgG titers are nanoparticle-dose dependent. The results also revealed the NPs' capability to promote a cellular immune response against HBsAg, characterized by the production of IFN-γ and IL-17. These results demonstrated that PCL/chitosan NPs are a good hepatitis B antigen adjuvant, with direct influence on the intensity and type of the immune response generated.

Breast Cancer Stem Cell Culture and Enrichment Using Poly(ε-Caprolactone Scaffolds

Directory of Open Access Journals (Sweden)

Sònia Palomeras

2016-04-01

Full Text Available The cancer stem cell (CSC population displays self-renewal capabilities, resistance to conventional therapies, and a tendency to post-treatment recurrence. Increasing knowledge about CSCs’ phenotype and functions is needed to investigate new therapeutic strategies against the CSC population. Here, poly(ε-caprolactone (PCL, a biocompatible polymer free of toxic dye, has been used to fabricate scaffolds, solid structures suitable for 3D cancer cell culture. It has been reported that scaffold cell culture enhances the CSCs population. A RepRap BCN3D+ printer and 3 mm PCL wire were used to fabricate circular scaffolds. PCL design and fabrication parameters were first determined and then optimized considering several measurable variables of the resulting scaffolds. MCF7 breast carcinoma cell line was used to assess scaffolds adequacy for 3D cell culture. To evaluate CSC enrichment, the Mammosphere Forming Index (MFI was performed in 2D and 3D MCF7 cultures. Results showed that the 60° scaffolds were more suitable for 3D culture than the 45° and 90° ones. Moreover, 3D culture experiments, in adherent and non-adherent conditions, showed a significant increase in MFI compared to 2D cultures (control. Thus, 3D cell culture with PCL scaffolds could be useful to improve cancer cell culture and enrich the CSCs population.

In vitro evaluation of poly(ethylene glycol)-block-poly(ε-caprolactone) methyl ether copolymer coating effects on cells adhesion and proliferation

Energy Technology Data Exchange (ETDEWEB)

Rusen, Laurentiu [National Institute for Lasers, Plasma and Radiation Physics, Bucharest (Romania); Neacsu, Patricia; Cimpean, Anisoara [University of Bucharest, Department of Biochemistry and Molecular Biology, Bucharest (Romania); Valentin, Ion; Brajnicov, Simona; Dumitrescu, L.N. [National Institute for Lasers, Plasma and Radiation Physics, Bucharest (Romania); Banita, Janina [University of Bucharest, Faculty of Chemistry, Bucharest (Romania); IBAR, Institute of Biochemistry of the Romanian Academy, 296 Splaiul Independentei, RO-060031 Bucharest (Romania); Dinca, Valentina, E-mail: valentina.dinca@inflpr.ro [National Institute for Lasers, Plasma and Radiation Physics, Bucharest (Romania); Dinescu, Maria [National Institute for Lasers, Plasma and Radiation Physics, Bucharest (Romania)

2016-06-30

Understanding and controlling natural and synthetic biointerfaces is known to be the key to a wide variety of application within cell culture and tissue engineering field. As both material characteristics and methods are important in tailoring biointerfaces characteristics, in this work we explore the feasibility of using Matrix Assisted Pulsed Laser Evaporation technique for obtaining synthetic copolymeric biocoatings (i.e. poly(ethylene glycol)-block-poly(ε-caprolactone) methyl ether) for evaluating in vitro Vero and MC3T3-E1 pre-osteoblasts cell response. Characterization and evaluation of the coated substrates were carried out using different techniques. The Fourier transform infrared spectroscopy data demonstrated that the main functional groups in the MAPLE-deposited films remained intact. Atomic Force Microscopy images showed the coatings to be continuous, with the surface roughness depending on the deposition parameters. Moreover, the behaviour of the coatings in medium mimicking the pH and temperature of the human body was studied and corelated to degradation. Spectro-ellipsometry (SE) and AFM measurements revealed the degradation trend during immersion time by the changes in coating thickness and roughness. In vitro biocompatibility was studied by indirect contact tests on Vero cells in accordance with ISO 10993-5/2009. The results obtained in terms of cell morphology (phase contrast microscopy) and cytotoxicity (LDH and MTT assays) proved biocompatibility. Furthermore, direct contact assays on MC3T3-E1 pre-osteoblasts demonstrated the capacity of all analyzed specimens to support cell adhesion, normal cellular morphology and growth.

Modifications induced by swift heavy ions on poly(hydroxybutyrate-hydroxyvalerate) (PHB/HV) and poly(ε-caprolactone) (PCL). Part 2. Radicals characterization

International Nuclear Information System (INIS)

Rouxhet, L.; Mestdagh, M.; Legras, R.

2000-01-01

Modifications induced by different energetic heavy ions ( 40 Ar 9+ , 80 Kr 15+ , 129 Xe 24+ , 208 Pb 53+ and 208 Pb 56+ ) on poly(ε-caprolactone) (PCL) and poly(hydroxybutyrate-hydroxyvalerate) (PHB/HV) have been investigated by electron spin resonance (ESR). Indeed, film irradiation by heavy ions leads to, among other phenomena, the formation of radicals in the ion tracks. Thanks to ESR, it is possible to detect these radicals and to identify them or at least to characterize them by following the evolution of the radical signal as a function of parameters, like temperature, or the kinetic of disappearance of the radical species at ambient temperature in vacuum or ambient atmosphere. This study confirmed the generation of radicals by the irradiation of PHB/HV samples with energetic heavy ions reported in the literature. The study on PCL was not pursued after a few preliminary studies, revealing the presence of an ESR signal in the non-irradiated sample. Electronic stopping power has a major influence on radical decrease at ambient temperature. The ion used for the irradiation did not modify very much the radical signal and the evolution of the radicalar signal intensity with temperature. Different reasoning and experiments revealed that the glass transition temperature is a key temperature above which irreversible recombinations of the most stable radicals take place. A simulation study indicated that the most stable radical produced was probably a tertiary radical formed by the stabilization of the secondary radical resulting from the abstraction of a highly mobile hydrogen adjacent to the carbonyl

In vitro evaluation of poly(ethylene glycol)-block-poly(ɛ-caprolactone) methyl ether copolymer coating effects on cells adhesion and proliferation

Science.gov (United States)

Rusen, Laurentiu; Neacsu, Patricia; Cimpean, Anisoara; Valentin, Ion; Brajnicov, Simona; Dumitrescu, L. N.; Banita, Janina; Dinca, Valentina; Dinescu, Maria

2016-06-01

Understanding and controlling natural and synthetic biointerfaces is known to be the key to a wide variety of application within cell culture and tissue engineering field. As both material characteristics and methods are important in tailoring biointerfaces characteristics, in this work we explore the feasibility of using Matrix Assisted Pulsed Laser Evaporation technique for obtaining synthetic copolymeric biocoatings (i.e. poly(ethylene glycol)-block-poly(ɛ-caprolactone) methyl ether) for evaluating in vitro Vero and MC3T3-E1 pre-osteoblasts cell response. Characterization and evaluation of the coated substrates were carried out using different techniques. The Fourier transform infrared spectroscopy data demonstrated that the main functional groups in the MAPLE-deposited films remained intact. Atomic Force Microscopy images showed the coatings to be continuous, with the surface roughness depending on the deposition parameters. Moreover, the behaviour of the coatings in medium mimicking the pH and temperature of the human body was studied and corelated to degradation. Spectro-ellipsometry (SE) and AFM measurements revealed the degradation trend during immersion time by the changes in coating thickness and roughness. In vitro biocompatibility was studied by indirect contact tests on Vero cells in accordance with ISO 10993-5/2009. The results obtained in terms of cell morphology (phase contrast microscopy) and cytotoxicity (LDH and MTT assays) proved biocompatibility. Furthermore, direct contact assays on MC3T3-E1 pre-osteoblasts demonstrated the capacity of all analyzed specimens to support cell adhesion, normal cellular morphology and growth.

Amphiphilic poly{[α-maleic anhydride-ω-methoxypoly(ethylene glycol]-co-(ethyl cyanoacrylate} graft copolymer nanoparticles as carriers for transdermal drug delivery

Directory of Open Access Journals (Sweden)

Jinfeng Xing

2009-10-01

Full Text Available Jinfeng Xing, Liandong Deng, Jun Li, Anjie DongDepartment of Polymer Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin, People’s Republic of ChinaAbstract: In this study, the transdermal drug delivery properties of D,L-tetrahydropalmatine (THP-loaded amphiphilic poly{[α-maleic anhydride-ω-methoxy-poly(ethylene glycol]-co-(ethyl cyanoacrylate} (PEGECA graft copolymer nanoparticles (PEGECAT NPs were evaluated by skin penetration experiments in vitro. The transdermal permeation experiments in vitro were carried out in Franz diffusion cells using THP-loaded PEGECAT NPs as the donor system. Transmission electron microscopy and Fourier transform infrared spectroscopy were used to characterize the receptor fluid. The results indicate that the THP-loaded PEGECAT NPs are able to penetrate the rat skin. Fluorescent microscopy measurements demonstrate that THP-loaded PEGECAT NPs can penetrate the skin not only via appendage routes but also via epidermal routes. This nanotechnology has potential application in transdermal drug delivery. Keywords: poly{[α-maleic anhydride-ω-methoxy-poly(ethylene glycol]-co-(ethyl cyanoacrylate}, nanoparticles, transdermal drug delivery, D,L-tetrahydropalmatine

A combinatorial variation in surface chemistry and pore size of three-dimensional porous poly(ε-caprolactone) scaffolds modulates the behaviors of mesenchymal stem cells

Energy Technology Data Exchange (ETDEWEB)

Zhao, Yingdi; Tan, Ke; Zhou, Yan; Ye, Zhaoyang, E-mail: zhaoyangye@ecust.edu.cn; Tan, Wen-Song

2016-02-01

Biomaterial properties play significant roles in controlling cellular behaviors. The objective of the present study was to investigate how pore size and surface chemistry of three-dimensional (3D) porous scaffolds regulate the fate of mesenchymal stem cells (MSCs) in vitro in combination. First, on poly(ε-caprolactone) (PCL) films, the hydrolytic treatment was found to stimulate the adhesion, spreading and proliferation of human MSCs (hMSCs) in comparison with pristine films, while the aminolysis showed mixed effects. Then, 3D porous PCL scaffolds with varying pore sizes (100–200 μm, 200–300 μm and 300–450 μm) were fabricated and subjected to either hydrolysis or aminolysis. It was found that a pore size of 200–300 μm with hydrolysis in 3D scaffolds was the most favorable condition for growth of hMSCs. Importantly, while a pore size of 200–300 μm with hydrolysis for 1 h supported the best osteogenic differentiation of hMSCs, the chondrogenic differentiation was greatest in scaffolds with a pore size of 300–450 μm and treated with aminolysis for 1 h. Taken together, these results suggest that surface chemistry and pore size of 3D porous scaffolds may potentially have a synergistic impact on the behaviors of MSCs. - Highlights: • Surface chemistry of poly(ε-caprolactone) films actively modulates MSC behaviors. • Varying surface chemistry and pore size in combination is enabled in 3D scaffolds. • Surface chemistry and pore size potentially dictate MSC fates in synergy.

A combinatorial variation in surface chemistry and pore size of three-dimensional porous poly(ε-caprolactone) scaffolds modulates the behaviors of mesenchymal stem cells

International Nuclear Information System (INIS)

Zhao, Yingdi; Tan, Ke; Zhou, Yan; Ye, Zhaoyang; Tan, Wen-Song

2016-01-01

Biomaterial properties play significant roles in controlling cellular behaviors. The objective of the present study was to investigate how pore size and surface chemistry of three-dimensional (3D) porous scaffolds regulate the fate of mesenchymal stem cells (MSCs) in vitro in combination. First, on poly(ε-caprolactone) (PCL) films, the hydrolytic treatment was found to stimulate the adhesion, spreading and proliferation of human MSCs (hMSCs) in comparison with pristine films, while the aminolysis showed mixed effects. Then, 3D porous PCL scaffolds with varying pore sizes (100–200 μm, 200–300 μm and 300–450 μm) were fabricated and subjected to either hydrolysis or aminolysis. It was found that a pore size of 200–300 μm with hydrolysis in 3D scaffolds was the most favorable condition for growth of hMSCs. Importantly, while a pore size of 200–300 μm with hydrolysis for 1 h supported the best osteogenic differentiation of hMSCs, the chondrogenic differentiation was greatest in scaffolds with a pore size of 300–450 μm and treated with aminolysis for 1 h. Taken together, these results suggest that surface chemistry and pore size of 3D porous scaffolds may potentially have a synergistic impact on the behaviors of MSCs. - Highlights: • Surface chemistry of poly(ε-caprolactone) films actively modulates MSC behaviors. • Varying surface chemistry and pore size in combination is enabled in 3D scaffolds. • Surface chemistry and pore size potentially dictate MSC fates in synergy.

Synthesis, Characterization, and Acute Oral Toxicity Evaluation of pH-Sensitive Hydrogel Based on MPEG, Poly(ε-caprolactone, and Itaconic Acid

Directory of Open Access Journals (Sweden)

Liwei Tan

2013-01-01

Full Text Available A kind of chemically cross-linked pH-sensitive hydrogels based on methoxyl poly(ethylene glycol-poly(caprolactone-acryloyl chloride (MPEG-PCL-AC, PECA, poly(ethylene glycol methyl ether methacrylate (MPEGMA, MEG, N,N-methylenebisacrylamide (BIS, and itaconic acid (IA were prepared without using any organic solvent by heat-initiated free radical method. The obtained macromonomers and hydrogels were characterized by 1H NMR and FT-IR, respectively. Morphology study of hydrogels was also investigated in this paper, and it showed that the hydrogels had good pH-sensitivity. The acute toxicity test and histopathological study were conducted in BALB/c mice. The results indicated that the maximum tolerance dose of the hydrogel was higher than 10000 mg/kg body weight. No morality or signs of toxicity were observed during the whole 7-day observation period. Compared to the control groups, there were no important adverse effects in the variables of hematology routine test and serum chemistry analysis both in male or female treatment group. Histopathological study also did not show any significant lesions, including heart, liver, lung, spleen, kidney, stomach, intestine, and testis. All the results demonstrated that this hydrogel was nontoxic after gavage. Thus, the hydrogel might be the biocompatible potential candidate for oral drug delivery system.

Antibacterial performance and in vivo diabetic wound healing of curcumin loaded gum tragacanth/poly(ε-caprolactone) electrospun nanofibers.

Science.gov (United States)

Ranjbar-Mohammadi, Marziyeh; Rabbani, Shahram; Bahrami, S Hajir; Joghataei, M T; Moayer, F

2016-12-01

In this study we describe the potential of electrospun curcumin-loaded poly(ε-caprolactone) (PCL)/gum tragacanth (GT) (PCL/GT/Cur) nanofibers for wound healing in diabetic rats. These scaffolds with antibacterial property against methicillin resistant Staphylococcus aureus as gram positive bacteria and extended spectrum β lactamase as gram negative bacteria were applied in two forms of acellular and cell-seeded for assessing their capability in healing full thickness wound on the dorsum of rats. After 15days, pathological study showed that the application of GT/PCL/Cur nanofibers caused markedly fast wound closure with well-formed granulation tissue dominated by fibroblast proliferation, collagen deposition, complete early regenerated epithelial layer and formation of sweat glands and hair follicles. No such appendage formation was observed in the untreated controls during this duration. Masson's trichrome staining confirmed the increased presence of collagen in the dermis of the nanofiber treated wounds on day 5 and 15, while the control wounds were largely devoid of collagen on day 5 and exhibited less collagen amount on day 15. Quantification analysis of scaffolds on day 5 confirmed that, tissue engineered scaffolds with increased amount of angiogenesis number, granulation tissue area (μ(2)), fibroblast number, and decreased epithelial gap (μ) can be more effective compared to GT/PCL/Cur nanofibers. Copyright © 2016 Elsevier B.V. All rights reserved.

Modifications induced by swift heavy ions in poly(hydroxybutyrate-hydroxyvalerate) (PHB/HV) and poly(ε-caprolactone) (PCL) films. Part 1. Thermal behaviour and molecular mass modifications

International Nuclear Information System (INIS)

Rouxhet, L.; Legras, R.

2000-01-01

Modifications induced by different energetic heavy ions in poly(ε-caprolactone) (PCL) and poly(hydroxybutyrate-hydroxyvalerate) (PHB/HV) have been investigated by the differential scanning calorimetry (DSC) and steric exclusion chromatography (SEC). A certain dose of damages, depending mainly on the charge and mass of the ion and on the intensity of irradiation, has to be overcome in order to detect any effect on PHB/HV. Actually, at a given intensity of irradiation, superior to 10 10 ions/cm 2 , the level of damage intensity increased with the increase in charge and mass of the ion. Moreover, according to the SEC results, there seems to be a critical mass and/or charge threshold above which the dominant type of damages changes. As a matter of fact, high-density irradiation with Ar 9+ and Kr 15+ resulted mainly in chain scission whereas cross-linking was dominant when irradiating the polymer with Xe 24+ and Pb 56+ . The irradiation of PCL in the conditions studied did not modify significantly the values of the melting point, the crystallisation temperature and the molecular masses of the system studied. The main effect of the irradiation detected by the DSC is the cross-linking of the polymer chains

Improving osteoblasts cells proliferation via femtosecond laser surface modification of 3D-printed poly-ɛ-caprolactone scaffolds for bone tissue engineering applications

Science.gov (United States)

Daskalova, A.; Ostrowska, B.; Zhelyazkova, A.; Święszkowski, W.; Trifonov, A.; Declercq, H.; Nathala, C.; Szlazak, K.; Lojkowski, M.; Husinsky, W.; Buchvarov, I.

2018-06-01

Synthetic polymer biomaterials incorporating cells are a promising technique for treatment of orthopedic injuries. To enhance the integration of biomaterials into the human body, additional functionalization of the scaffold surface should be carried out that would assist one in mimicking the natural cellular environment. In this study, we examined poly-ɛ-caprolactone (PCL) fiber matrices in view of optimizing the porous properties of the constructs. Altering the porosity of a PCL scaffold is expected to improve the material's biocompatibility, thus influencing its osteoconductivity and osteointegration. We produced 3D poly-ɛ-caprolactone (PCL) matrices by a fused deposition modeling method for bone and cartilage tissue engineering and performed femtosecond (fs) laser modification experiments to improve the surface properties of the PCL construct. Femtosecond laser processing is one of the useful tools for creating a vast diversity of surface patterns with reproducibility and precision. The processed surface of the PCL matrix was examined to follow the effect of the laser parameters, namely the laser pulse energy and repetition rate and the number ( N) of applied pulses. The modified zones were characterized by scanning electron microscopy (SEM), confocal microscopy, X-ray computed tomography and contact angle measurements. The results obtained demonstrated changes in the morphology of the processed surface. A decrease in the water contact angle was also seen after fs laser processing of fiber meshes. Our work demonstrated that a precise control of material surface properties could be achieved by applying a different number of laser pulses at various laser fluence values. We concluded that the structural features of the matrix remain unaffected and can be successfully modified through laser postmodification. The cells tests indicated that the micro-modifications created induced MG63 and MC3T3 osteoblast cellular orientation. The analysis of the MG63 and MC3T3

Poly-ε-caprolactone Coated and Functionalized Porous Titanium and Magnesium Implants for Enhancing Angiogenesis in Critically Sized Bone Defects

Directory of Open Access Journals (Sweden)

Laura Roland

2015-12-01

Full Text Available For healing of critically sized bone defects, biocompatible and angiogenesis supporting implants are favorable. Murine osteoblasts showed equal proliferation behavior on the polymers poly-ε-caprolactone (PCL and poly-(3-hydroxybutyrate/poly-(4-hydroxybutyrate (P(3HB/P(4HB. As vitality was significantly better for PCL, it was chosen as a suitable coating material for further experiments. Titanium implants with 600 µm pore size were evaluated and found to be a good implant material for bone, as primary osteoblasts showed a vitality and proliferation onto the implants comparable to well bottom (WB. Pure porous titanium implants and PCL coated porous titanium implants were compared using Live Cell Imaging (LCI with Green fluorescent protein (GFP-osteoblasts. Cell count and cell covered area did not differ between the implants after seven days. To improve ingrowth of blood vessels into porous implants, proangiogenic factors like Vascular Endothelial Growth Factor (VEGF and High Mobility Group Box 1 (HMGB1 were incorporated into PCL coated, porous titanium and magnesium implants. An angiogenesis assay was performed to establish an in vitro method for evaluating the impact of metallic implants on angiogenesis to reduce and refine animal experiments in future. Incorporated concentrations of proangiogenic factors were probably too low, as they did not lead to any effect. Magnesium implants did not yield evaluable results, as they led to pH increase and subsequent cell death.

Mechanical properties of porous β-tricalcium phosphate composites prepared by ice-templating and poly(ε-caprolactone) impregnation.

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Flauder, Stefan; Sajzew, Roman; Müller, Frank A

2015-01-14

In this study ceramic scaffolds of the bioresorbable and osteoconductive bioceramic β-tricalcium phosphate (β-TCP) were impregnated with the bioresorbable and ductile polymer poly(ε-caprolactone) (PCL) to investigate the influence of the impregnation on the mechanical properties of the porous composites. The initial β-TCP scaffolds were fabricated by the ice-templating method and exhibit the typical morphology of aligned, open, and lamellar pores. This pore morphology seems to be appropriate for applications as bone replacement material. The macroporosity of the scaffolds is mostly preserved during the solution-mediated PCL impregnation as the polymer was added only in small amounts so that only the micropores of β-TCP lamellae were infiltrated and the surface of the lamellae were coated with a thin film. Composite scaffolds show a failure behavior with brittle and plastic contributions, which increase their damage tolerance, in contrast to the absolutely brittle behavior of pure β-TCP scaffolds. The energy consumption during bending and compression load was increased in the impregnated scaffolds by (a) elastic and plastic deformation of the introduced polymer, (b) drawing and formation of PCL fibrils which bridge micro- and macrocracks, and (c) friction of ceramic debris still glued together by PCL. PCL addition also increased the compressive and flexural strength of the scaffolds. An explanatory model for this strength enhancement was proposed that implicates the stiffening of cold-drawn PCL present in surface flaws and micropores.

Preparation and icephobic properties of polymethyltrifluoropropylsiloxane–polyacrylate block copolymers

Energy Technology Data Exchange (ETDEWEB)

Li, Xiaohui; Zhao, Yunhui [School of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300072 (China); Li, Hui [School of Chemistry and Chemical Engineering, Shandong Key Laboratory of Fluorine Chemistry and Chemical Engineering Materials, University of Jinan, Jinan 250022 (China); Yuan, Xiaoyan, E-mail: xyuan28@yahoo.com [School of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300072 (China)

2014-10-15

Highlights: • PMTFPS–b-polyacrylate copolymers in five different compositions were synthesized. • Enrichment of PMTFPS amounts at the surface made high F/Si value. • Icing delay time was related to the surface roughness. • Ice shear strength was decreased by the synergistic effect of silicone and fluorine. - Abstract: Five polymethyltrifluoropropylsiloxane (PMTFPS)–polyacrylate block copolymers (PMTFPS–b-polyacrylate) were synthesized by free radical polymerization of methyl methacrylate, n-butyl acrylate and hydroxyethyl methacrylate using PMTFPS macroazoinitiator (PMTFPS-MAI) in range of 10–50 mass percentages. The morphology, surface chemical composition and wettability of the prepared copolymer films were investigated by transmission electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, and water contact angle measurement. Delayed icing time and ice shear strength of the films were also detected for the icephobic purpose. The surface morphologies of the copolymers were different from those of the bulk because of the migration of the PMTFPS segments to the air interface during the film formation. Maximal delayed icing time (186 s at −15 °C) and reduction of the ice shear strength (301 ± 10 kPa) which was significantly lower than that of polyacrylates (804 ± 37 kPa) were achieved when the content of PMTFPS-MAI was 20 wt%. The icephobicity of the copolymers was attributed primarily to the enrichment of PMTFPS on the film surface and synergistic effect of both silicone and fluorine. Thus, the results show that the PMTFPS–b-polyacrylate copolymer can be used as icephobic coating materials potentially.

Shape Memory Properties and Enzymatic Degradability of Poly(ε-caprolactone)-Based Polyurethane Urea Containing Phenylalanine-Derived Chain Extender.

Science.gov (United States)

Wang, Rong; Zhang, Fanjun; Lin, Weiwei; Liu, Wenkai; Li, Jiehua; Luo, Feng; Wang, Yaning; Tan, Hong

2018-04-24

Biodegradable shape memory polymers are promising biomaterials for minimally invasive surgical procedures. Herein, a series of linear biodegradable shape memory poly(ε-caprolactone) (PCL)-based polyurethane ureas (PUUs) containing a novel phenylalanine-derived chain extender is synthesized. The phenylalanine-derived chain extender, phenylalanine-hexamethylenediamine-phenylalanine (PHP), contains two chymotrypsin cleaving sites to enhance the enzymatic degradation of PUUs. The degradation rate, the crystallinity, and mechanical properties of PUUs are tailored by the content of PHP. Meanwhile, semicrystalline PCL is not only hydrolytically degradable but also vital for shape memory. Good shape memory ability under body temperature is achieved for PUUs due to the strong interactions in hard segments for permanent crosslinking and the crystallization-melt transition of PCL to switch temporary shape. The PUUs would have a great potential in application as implanting stent. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Star-pseudopolyrotaxane organized in nanoplatelets for poly(ε-caprolactone)-based nanofibrous scaffolds with enhanced surface reactivity.

Science.gov (United States)

Oster, Murielle; Hébraud, Anne; Gallet, Sébastien; Lapp, Alain; Pollet, Eric; Avérous, Luc; Schlatter, Guy

2015-02-01

Herein, it is demonstrated that star pseudopolyrotaxanes (star-pPRs) obtained from the inclusion complexation of α-cyclodextrin (CD) and four-branched star poly(ε-caprolactone) (star-PCL) organize into nanoplatelets in dimethyl sulfoxide at 35 °C. This peculiar property, not observed for linear pseudopolyrotaxanes, allows the processing of star-pPRs while preserving their supramolecular assembly. Thus, original PCL:star-pPR core:shell nanofibers are elaborated by coaxial electrospinning. The star-pPR shell ensures the presence of available CD hydroxyl functions on the fiber surface allowing its postfunctionalization. As proof of concept, fluorescein isothiocyanate is grafted. Moreover, the morphology of the fibers is maintained due to the star-pPR shell that acts as a shield, preventing the fiber dissolution during chemical modification. The proposed strategy is simple and avoids the synthesis of polyrotaxanes, i.e., pPR end-capping to prevent the CD dethreading. As PCL is widely used for biomedical applications, this strategy paves the way for simple functionalization with any bioactive molecules. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Poly(acrylic acid)/polyethylene glycol hygrogel prepared by using gamma-ray irradiation for mucosa adhesion

Energy Technology Data Exchange (ETDEWEB)

Nho, Young-Chang; Park, Jong-Seok; Shin, Jung-Woong; Lim, Youn-Mook; Jeong, Sung-In; Shin, Young-Min; Gwon, Hui-Jeong [Korea Atomic Energy Research Institute, Jeongeup (Korea, Republic of); Khil, Myung-Seob [Chonbuk National University, Jeonju (Korea, Republic of); Lee, Deok-Won [Maxillofacial Surgery Dental Hospital, Seoul (Korea, Republic of); Ahn, Sung-Jun [JADAM Co., LTD., Seogwipo (Korea, Republic of)

2015-01-15

A buccal delivery system provides a much milder environment for drug delivery compared to an oral delivery which presents a hostile environment for drugs, especially proteins and polypeptides, owing to acid hydrolysis. Local delivery in an oral cavity has particular applications in the treatment of toothaches, periodontal disease, and bacterial infections. Poly(acrylic acid) (PAA)-based hydrogels prepared using a chemical initiator have been attempted for a mucoadhesive system owing to their flexibility and excellent bioadhesion. In this experiment, PAA and polyethylene glycol (PEG) were selected to prepare using a radiation process a bioadhesive hydrogel for adhesion to mucosal surfaces. PAA and PEG were dissolved in purified water to prepare a homogeneous PAA/PEG solution, and the solution was then irradiated using an electron beam at dose up to 70 kGy to make the hydrogels. Their physical properties, such as gel percent, swelling percent, and adhesive strength to mucosal surfaces, were investigated. In this experiment, various amounts of PEG were incorporated into the PAA to enhance the mucoadhesive property of the hydrogels. The effect of the molecular weight of PEG on the mucoadhesion was also examined.

Controlled biomineralization of electrospun poly(ε-caprolactone) fibers to enhance their mechanical properties.

Science.gov (United States)

Xie, Jingwei; Zhong, Shaoping; Ma, Bing; Shuler, Franklin D; Lim, Chwee Teck

2013-03-01

Electrospun polymeric fibers have been investigated as scaffolding materials for bone tissue engineering. However, their mechanical properties, and in particular stiffness and ultimate tensile strength, cannot match those of natural bones. The objective of the study was to develop novel composite nanofiber scaffolds by attaching minerals to polymeric fibers using an adhesive material - the mussel-inspired protein polydopamine - as a "superglue". Herein, we report for the first time the use of dopamine to regulate mineralization of electrospun poly(ε-caprolactone) (PCL) fibers to enhance their mechanical properties. We examined the mineralization of the PCL fibers by adjusting the concentration of HCO(3)(-) and dopamine in the mineralized solution, the reaction time and the surface composition of the fibers. We also examined mineralization on the surface of polydopamine-coated PCL fibers. We demonstrated the control of morphology, grain size and thickness of minerals deposited on the surface of electrospun fibers. The obtained mineral coatings render electrospun fibers with much higher stiffness, ultimate tensile strength and toughness, which could be closer to the mechanical properties of natural bone. Such great enhancement of mechanical properties for electrospun fibers through mussel protein-mediated mineralization has not been seen previously. This study could also be extended to the fabrication of other composite materials to better bridge the interfaces between organic and inorganic phases. Copyright © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Bioactive glass-poly (ε-caprolactone) composite scaffolds with 3 dimensionally hierarchical pore networks

International Nuclear Information System (INIS)

Yun, Hui-suk; Kim, Seung-eon; Park, Eui Kyun

2011-01-01

Hierarchically mesoporous-macroporous-giant-porous bioactive glass/poly ε-caprolactone (PCL) composite scaffolds were prepared using a combination of the sol-gel method, evaporation-induced self-assembly process in the presence of nonionic triblock copolymer, EO 100 PO 65 EO 100 (F127), as template, salt leaching method, and rapid prototyping techniques. F127 acts as a template, inducing the formation of mesopores, NaCl with sizes between 25 and 33 μm provides macro-pores after leaching, and rapid prototyping produces giant-pores. The structure and morphology of the scaffolds were characterized by the field emission scanning electron microscopy, transmission electron microscopy, and Hg porosimetry. The mechanical properties of the scaffolds were examined by the dynamic mechanical analysis. Their in vitro bioactivities were confirmed by immersing the scaffolds in simulated body fluid. Their biocompatibilities were also evaluated by culturing human bone marrow stromal cells on the scaffolds. The scaffolds show good molding capabilities, mechanical properties, 3 dimensionally well-interconnected pore structures, bioactivities, and biocompatibilities in vitro. Depending on the amount of NaCl, the scaffolds also show unique sponge-like properties, but still retain better mechanical properties than general salt leaching derived PCL scaffolds. All of the data provide good evidence that the obtained scaffolds possess excellent potential for applications in the fields of tissue engineering and drug storage.

Electrospun Polyhydroxybutyrate and Poly(L-lactide-co-ε-caprolactone Composites as Nanofibrous Scaffolds

Directory of Open Access Journals (Sweden)

Donraporn Daranarong

2014-01-01

Full Text Available Electrospinning can produce nanofibrous scaffolds that mimic the architecture of the extracellular matrix and support cell attachment for tissue engineering applications. In this study, fibrous membranes of polyhydroxybutyrate (PHB with various loadings of poly(L-lactide-co-ε-caprolactone (PLCL were successfully prepared by electrospinning. In comparison to PLCL scaffolds, PLCL blends with PHB exhibited more irregular fibre diameter distributions and higher average fibre diameters but there were no significant differences in pore size. PLCL/PHB scaffolds were more hydrophilic (<120° with significantly reduced tensile strength (ca. 1 MPa compared to PLCL scaffolds (150.9±2.8∘ and 5.8±0.5 MPa. Increasing PLCL loading in PHB/PLCL scaffolds significantly increased the extension at break, (4–6-fold. PLCL/PHB scaffolds supported greater adhesion and proliferation of olfactory ensheathing cells (OECs than those exhibiting asynchronous growth on culture plates. Mitochondrial activity of cells cultivated on the electrospun blended membranes was enhanced compared to those grown on PLCL and PHB scaffolds (212, 179, and 153%, resp.. Analysis showed that PLCL/PHB nanofibrous membranes promoted cell cycle progression and reduced the onset of necrosis. Thus, electrospun PLCL/PHB composites promoted adhesion and proliferation of OECs when compared to their individual PLCL and PHB components suggesting potential in the repair and engineering of nerve tissue.

Poly-ε-caprolactone microspheres as a drug delivery system for cannabinoid administration: development, characterization and in vitro evaluation of their antitumoral efficacy.

Science.gov (United States)

Hernán Pérez de la Ossa, D; Ligresti, A; Gil-Alegre, M E; Aberturas, M R; Molpeceres, J; Di Marzo, V; Torres Suárez, A I

2012-08-10

Cannabinoids show promise for the treatment of various medical conditions such as emesis, anorexia, pain, cancer, multiple sclerosis, Parkinson's disease and glaucoma. However, their high lipohilicity and instability complicate their handling and dosing, and restrict their use as pharmaceuticals. The objective of the present work was to assess the feasibility of developing cannabinoid loaded poly-ε-caprolactone (PCL) microparticles prepared by the oil-in-water emulsion-solvent evaporation technique as a suitable dosage form for their administration. Spherical microparticles with a size range of 20-50 μm, and high entrapment efficiency (around 100%) were obtained. Cannabidiol (CBD) dissolved in the polymeric matrix of the microspheres was slowly released in vitro within 10 days. In vitro cell viability studies demonstrated the antitumoral activity of CBD released from microparticles. After 4 and 7 days of incubation, CBD in microspheres significantly inhibited the growth of MDA-MB-231 cells by 60% as compared to the 50% attained with free drug. The results suggest that PCL microparticles could be an alternative delivery system for long-term cannabinoid administration, showing potential therapeutic advantages over free drug. Copyright © 2012 Elsevier B.V. All rights reserved.

Characterization and photoconductivity study of well-defined C60 terminated poly(tert-butyl acrylate-b-styrene)

International Nuclear Information System (INIS)

Yang Dong; Li Lang; Wang Changchun

2004-01-01

Atom transfer radical polymerization (ATRP) catalyzed by N,N',N',N'',N''-pentamethyldiethylenetriamine (PMDETA)/CuBr was performed to synthesize poly (tert-butyl acrylate) (PtBA-Br) with predesigned molecular weight and narrow polydispersity. Using the PtBA-Br as macroinitiator, the PtBA-block-PS copolymer was prepared through ATRP. After terminated bromine atom was converted to end-functional azide group (P(tBA-b-St)-N 3 ), C 60 end-capped PtBA-PS block copolymers (P(tBA-b-St)-C 60 ) were synthesized by reacting C 60 with P(tBA-b-St)-N 3 . GPC characterizations showed that C 60 was chemically bonded to the end of P(tBA-b-St) chain and the products were mono-substituted. FT-IR, UV-Vis measurements confirmed that hydrolysis of P(tBA-b-St)-C 60 resulted in amphiphilic C 60 end-capped PAA-PS block copolymers. In additional, the photoconductivity of P(tBA-b-St)-C 60 was measured

Preparation and characterization of poly(acrylic acid)—corn starch blend for use as chemical sand-fixing materials

Science.gov (United States)

Dang, Xugang; Chen, Hui; Shan, Zhihua

2017-07-01

One chemical sand-fixing materials based on poly(acrylic acid)-corn starch (PACS) blend was studied in this work. The PACS blend was prepared by solution mixing method between PA and CS. In order to prepare sand-fixing materials for environmental applications using the well-established method of spraying evenly PACS blend solution on the surfaces of fine sand. Fourier transform infrared spectroscopy (FT-IR) revealed the existence of the intermolecular interactions between the blend components. Scanning electron microscope (SEM) analysis showed a continuous phase of blend, and it also showed the good sand-fixing capacity. The test results of hygroscopicity and water retention experiments indicated that the blends had excellent water-absorbing and water-retention capacity. The results of contact angle measurements between the PACS solutions and fine sand showed that the PACS blend has a satisfactory effect on fine sand wetting. And the PACS, as a sand-fixation material, has excellent sand-fixation rate up to 99.5%.

Sustained intra-articular release of celecoxib from in situ forming gels made of acetyl-capped PCLA-PEG-PCLA triblock copolymers in horses

NARCIS (Netherlands)

Petit, Audrey|info:eu-repo/dai/nl/371748461; Redout, Everaldo M; van de Lest, Chris H|info:eu-repo/dai/nl/146063570; de Grauw, Janny C|info:eu-repo/dai/nl/304822469; Müller, Benno; Meyboom, Ronald; van Midwoud, Paul; Vermonden, Tina|info:eu-repo/dai/nl/275124517; Hennink, Wim E|info:eu-repo/dai/nl/070880409; van Weeren, René|info:eu-repo/dai/nl/074628550

In this study, the intra-articular tolerability and suitability for local and sustained release of an in situ forming gel composed of an acetyl-capped poly(ε-caprolactone-co-lactide)-b-poly(ethylene glycol)-b-poly(ε-caprolactone-co-lactide) (PCLA-PEG-PCLA) copolymer loaded with celecoxib was

Shape Recovery with Concomitant Mechanical Strengthening of Amphiphilic Shape Memory Polymers in Warm Water

International Nuclear Information System (INIS)

Zhang, Ben; DeBartolo, Janae E.; Song, Jie

2017-01-01

Maintaining adequate or enhancing mechanical properties of shape memory polymers (SMPs) after shape recovery in an aqueous environment are greatly desired for biomedical applications of SMPs as self-fitting tissue scaffolds or minimally invasive surgical implants. Here we report stable temporary shape fixing and facile shape recovery of biodegradable triblock amphiphilic SMPs containing a poly(ethylene glycol) (PEG) center block and flanking poly(lactic acid) or poly(lactic-co-glycolic acid) blocks in warm water, accompanied with concomitant enhanced mechanical strengths. Differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WXRD) and small-angle X-ray scattering (SAXS) analyses revealed that the unique stiffening of the amphiphilic SMPs upon hydration was due to hydration-driven microphase separation and PEG crystallization. We further demonstrated that the chemical composition of degradable blocks in these SMPs could be tailored to affect the persistence of hydration-induced stiffening upon subsequent dehydration. These properties combined open new horizons for these amphiphilic SMPs for smart weight-bearing in vivo applications (e.g. as self-fitting intervertebral discs). In conclusion, this study also provides a new material design strategy to strengthen polymers in aqueous environment in general.

Self-assembled amphiphilic polyhedral oligosilsesquioxane (POSS) grafted poly(vinyl alcohol) (PVA) nanoparticles

International Nuclear Information System (INIS)

Sheikh, Faheem A.; Barakat, Nasser A.M.; Kim, Byoung-Suhk; Aryal, Santosh; Khil, Myung-Seob; Kim, Hak-Yong

2009-01-01

In the present study, spherical nanoparticles (NPs) containing polyhedral oligosilsesquioxane (POSS) as an inner hydrophobic core and poly(vinyl alcohol) PVA as a hydrophilic outer shell were prepared by dialysis approach. Preparation of amphiphilic POSS-grafted-PVA co-polymer was characterized by 1 H NMR and FT-IR. The results indicated urethane linkage between monoisocyanate group of POSS macromer and the hydroxyl groups of PVA. The dynamic light scattering (DLS) and electrophoretic light scattering (ELS) of the NPs revealed that they have an average hydrodynamic diameter and negative zeta (ζ)-potential of 215 nm and - 161 mV, respectively. Atomic force microscopy (AFM) and bio-transmission electron microscope (BIO-TEM) have shown unagglomerated NPs within a diameter range of 60-90 nm. The prepared NPs were investigated to improve the control release of anticancer drug; paclitaxel as a model drug. Due to drug loading, the hydrodynamic diameter and negative zeta (ζ)-potential have changed to 325 nm and - 14 mV, respectively. In addition, in-vitro drug release experiments were conducted; the obtained results explicated continuous release for over 40 days. However, in case of using pure drug only, the drug completely released within 1 h.

Influence of excipients on characteristics and release profiles of poly(ε-caprolactone) microspheres containing immunoglobulin G

Energy Technology Data Exchange (ETDEWEB)

Erdemli, Özge [Department of Engineering Sciences, Middle East Technical University, Ankara (Turkey); Keskin, Dilek [Department of Engineering Sciences, Middle East Technical University, Ankara (Turkey); Biomaterials and Tissue Engineering Center of Excellence, Middle East Technical University, Ankara (Turkey); Tezcaner, Ayşen, E-mail: tezcaner@metu.edu.tr [Department of Engineering Sciences, Middle East Technical University, Ankara (Turkey); Biomaterials and Tissue Engineering Center of Excellence, Middle East Technical University, Ankara (Turkey)

2015-03-01

Protein instability during microencapsulation has been one of the major drawbacks of protein delivery systems. In this study, the effects of various excipients (poly vinyl alcohol, glucose, starch, heparin) on the stability of encapsulated human immunoglobulin G (IgG) in poly(ε-caprolactone) (PCL) microspheres and on microsphere characteristics were investigated before and after γ-sterilization. Microspheres formulated without any excipients and with glucose had a mean particle size around 3–4 μm whereas the mean particle sizes of other microspheres were around 5–6 μm. Use of PVA significantly increased the IgG-loading and encapsulation efficiency of microspheres. After γ-irradiation, IgG stability was mostly maintained in the microspheres with excipients compared to microspheres without any excipients. According to the μBCA results, microspheres without any excipient showed a high initial burst release as well as a fast release profile among all groups. Presence of PVA decreased the loss in the activity of IgG released before (completely retained after 6 h and 15.69% loss after 7 days) and after γ-irradiation (26.04% loss and 52.39% loss after 6 h and 7 days, respectively). The stabilization effect of PVA on the retention of the activity of released IgG was found more efficient compared to other groups formulated with carbohydrates. - Highlights: • Good excipient provides retention of protein stability during microencapsulation. • PVA was more effective on retention of the IgG stability compared to carbohydrates. • Starch was not an appropriate excipient for the retention of IgG stability.

Electrochemical lithiation performance and characterization of silicon-graphite composites with lithium, sodium, potassium, and ammonium polyacrylate binders.

Science.gov (United States)

Han, Zhen-Ji; Yamagiwa, Kiyofumi; Yabuuchi, Naoaki; Son, Jin-Young; Cui, Yi-Tao; Oji, Hiroshi; Kogure, Akinori; Harada, Takahiro; Ishikawa, Sumihisa; Aoki, Yasuhito; Komaba, Shinichi

2015-02-07

Poly(acrylic acid) (PAH), which is a water soluble polycarboxylic acid, is neutralized by adding different amounts of LiOH, NaOH, KOH, and ammonia (NH4OH) aqueous solutions to fix neutralization degrees. The differently neutralized polyacid, alkali and ammonium polyacrylates are examined as polymeric binders for the preparation of Si-graphite composite electrodes as negative electrodes for Li-ion batteries. The electrode performance of the Si-graphite composite depends on the alkali chemicals and neutralization degree. It is found that 80% NaOH-neutralized polyacrylate binder (a pH value of the resultant aqueous solution is ca. 6.7) is the most efficient binder to enhance the electrochemical lithiation and de-lithiation performance of the Si-graphite composite electrode compared to that of conventional PVdF and the other binders used in this study. The optimum polyacrylate binder highly improves the dispersion of active material in the composite electrode. The binder also provides the strong adhesion, suitable porosity, and hardness for the composite electrode with 10% (m/m) binder content, resulting in better electrochemical reversibility. From these results, the factors of alkali-neutralized polyacrylate binders affecting the electrode performance of Si-graphite composite electrodes are discussed.

Aminoglycoside-derived amphiphilic nanoparticles for molecular delivery.

Science.gov (United States)

Miryala, Bhavani; Godeshala, Sudhakar; Grandhi, Taraka Sai Pavan; Christensen, Matthew D; Tian, Yanqing; Rege, Kaushal

2016-10-01

The development of effective drug carriers can lead to improved outcomes in a variety of disease conditions. Aminoglycosides have been used as antibacterial therapeutics, and are attractive as monomers for the development of polymeric materials in various applications. Here, we describe the development of novel aminoglycoside-derived amphiphilic nanoparticles for drug delivery, with an eye towards ablation of cancer cells. The aminoglycoside paromomycin was first cross-linked with resorcinol diglycidyl ether leading to the formation of a poly (amino ether), PAE. PAE molecules were further derivatized with methoxy-terminated poly(ethylene glycol) or mPEG resulting in the formation of mPEG-PAE polymer, which self-assembled to form nanoparticles. Formation of the mPEG-PAE amphiphile was characterized using (1)H NMR, (13)C NMR, gel permeation chromatography (GPC) and FTIR spectroscopy. Self-assembly of the polymer into nanoparticles was characterized using dynamic light scattering, zeta potential analyses, atomic force microscopy (AFM) and the pyrene fluorescence assay. mPEG-PAE nanoparticles were able to carry significant amounts of doxorubicin (DOX), presumably by means of hydrophobic interactions between the drug and the core. Cell-based studies indicated that mPEG-PAE nanoparticles, loaded with doxorubicin, were able to induce significant loss in viabilities of PC3 human prostate cancer, MDA-MB-231 human breast cancer, and MB49 murine bladder cancer cells; empty nanoparticles resulted in negligible losses of cell viability under the conditions investigated. Taken together, our results indicate that the mPEG-PAE nanoparticle platform is attractive for drug delivery in different applications, including cancer. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis and controlled self-assembly of UV-responsive gold nanoparticles in block copolymer templates.

Science.gov (United States)

Song, Dong-Po; Wang, Xinyu; Lin, Ying; Watkins, James J

2014-11-06

We demonstrate the facile synthesis of gold nanoparticles (GNPs) functionalized by UV-responsive block copolymer ligands, poly(styrene)-b-poly(o-nitrobenzene acrylate)-SH (PS-b-PNBA-SH), followed by their targeted distribution within a lamellae-forming poly(styrene)-b-poly(2-vinylpyridine) (PS-b-P2VP) block copolymer. The multilayer, micelle-like structure of the GNPs consists of a gold core, an inner PNBA layer, and an outer PS layer. The UV-sensitive PNBA segment can be deprotected into a layer containing poly(acrylic acid) (PAA) when exposed to UV light at 365 nm, which enables the simple and precise tuning of GNP surface properties from hydrophobic to amphiphilic. The GNPs bearing ligands of different chemical compositions were successfully and selectively incorporated into the PS-b-P2VP block copolymer, and UV light showed a profound influence on the spatial distributions of GNPs. Prior to UV exposure, GNPs partition along the interfaces of PS and P2VP domains, while the UV-treated GNPs are incorporated into P2VP domains as a result of hydrogen bond interactions between PAA on the gold surface and P2VP domains. This provides an easy way of controlling the arrangement of nanoparticles in polymer matrices by tailoring the nanoparticle surface using UV light.

Improvement of the titanium implant biological properties by coating with poly (ε-caprolactone)-based hybrid nanocomposites synthesized via sol-gel

Energy Technology Data Exchange (ETDEWEB)

Catauro, Michelina; Bollino, Flavia; Papale, Ferdinando [Department of Industrial and Information Engineering, Second University of Naples, Via Roma 21, 81031 Aversa (Italy)

2016-05-18

When bioactive coatings are applied to medical implants by means of sol-gel dip coating technique, the biological proprieties of the implant surface can be modified to match the properties of the surrounding tissues. In this study organo-inorganic nanocomposites materials were synthesized via sol-gel. They consisted of an inorganic zirconium-based and silica-based matrix, in which a biodegradable polymer (the poly-ε-caprolactone, PCL) was incorporated in different weight percentages. The synthesized materials, in sol phase, were used to dip-coat a substrate of commercially pure titanium grade 4 (CP Ti gr. 4) in order to improve its biological properties. A microstructural analysis of the obtained films was carried out by scanning electron microscopy (SEM) and attenuated total reflectance (ATR) Fourier transform infrared spectroscopy (FT-IR). Biological proprieties of the coated substrates were investigated by means of in vitro tests.

Synthesis of poly(N-isopropylacrylamide-co-acrylic acid) model compounds for filtration experiments

DEFF Research Database (Denmark)

Hinge, Mogens; Christensen, Morten Lykkegaard; Scales, Peter

2005-01-01

rheometry indicates that the blocks of poly(acrylic acid) are placed on the surface of the microgels. The combination of these three results reveal that the microgels have a core mainly consisting of poly(N-isopropylacrylamide) and a diffuse/cloudy surface consisting mainly of poly(acrylic acid).   The core/shell......  Theoretical development within solid/liquid separation in colloidal systems is largely based on inorganic, low charged and incompressible particles. These do not reflect the properties in biosolid/organic systems. There is therefore a need for a development of colloidal and particles which mimic...

Polyacrylate microspheres composite for all-solid-state reference electrodes.

Science.gov (United States)

Kisiel, Anna; Donten, Mikołaj; Mieczkowski, Józef; Rius-Ruiz, F Xavier; Maksymiuk, Krzysztof; Michalska, Agata

2010-09-01

A novel concept is proposed for the encapsulation of components within polyacrylate microspheres, prior to their incorporation into a membrane phase. Thus finer and better controlled dispersion of heterogeneous membrane components can be achieved. This concept was verified by using a poly(n-butyl acrylate) membrane-based reference electrode as an example. In this example the proper dispersion of solid constituents of the heterogeneous membrane and prevention of their leakage are both of primary importance. Potassium chloride-loaded poly(n-butyl acrylate) microspheres were prepared and then left in contact with silver nitrate to convert some of the KCl into AgCl. The material obtained was introduced into a poly(n-butyl acrylate) membrane. The reference electrode membranes obtained in this way were characterized with much more stable potential (both in different electrolytes and over time) compared with electrodes prepared by the direct introduction of KCl and AgCl to the membrane.

Ionization of amphiphilic acidic block copolymers.

Science.gov (United States)

Colombani, Olivier; Lejeune, Elise; Charbonneau, Céline; Chassenieux, Christophe; Nicolai, Taco

2012-06-28

The ionization behavior of an amphiphilic diblock copolymer poly(n-butyl acrylate(50%)-stat-acrylic acid(50%))(100)-block-poly(acrylic acid)(100) (P(nBA(50%)-stat-AA(50%))(100)-b-PAA(100), DH50) and of its equivalent triblock copolymer P(nBA(50%)-stat-AA(50%))(100)-b-PAA(200)-b-P(nBA(50%)-stat-AA(50%))(100) (TH50) were studied by potentiometric titration either in pure water or in 0.5 M NaCl. These polymers consist of a hydrophilic acidic block (PAA) connected to a hydrophobic block, P(nBA(50%)-stat-AA(50%))(100), whose hydrophobic character has been mitigated by copolymerization with hydrophilic units. We show that all AA units, even those in the hydrophobic block could be ionized. However, the AA units within the hydrophobic block were less acidic than those in the hydrophilic block, resulting in the preferential ionization of the latter block. The preferential ionization of PAA over that of P(nBA(50%)-stat-AA(50%))(100) was stronger at higher ionic strength. Remarkably, the covalent bonds between the PAA and P(nBA(50%)-stat-AA(50%))(100) blocks in the diblock or the triblock did not affect the ionization of each block, although the self-association of the block copolymers into spherical aggregates modified the environment of the PAA blocks compared to when PAA was molecularly dispersed.

Synthesis and Phase Behavior of Poly(N-isopropylacrylamide-b- Poly(L-Lysine Hydrochloride and Poly(N-Isopropylacrylamide- co-Acrylamide-b-Poly(L-Lysine Hydrochloride

Directory of Open Access Journals (Sweden)

Milica Spasojević

2014-07-01

Full Text Available The synthesis of poly(N-isopropylacrylamide-b-poly(L-lysine and poly(N- isopropylacrylamide-co-acrylamide-b-poly(L-lysine copolymers was accomplished by combining atom transfer radical polymerization (ATRP and ring opening polymerization (ROP. For this purpose, a di-functional initiator with protected amino group was successfully synthetized. The ATRP of N-isopropylacrylamide yielded narrowly dispersed polymers with consistent high yields (~80%. Lower yields (~50% were observed when narrowly dispersed random copolymers of N-isopropylacrylamide and acrylamide where synthesized. Amino-terminated poly(N-isopropylacrylamide and poly(N-isopropylacrylamide- co-acrylamide were successfully used as macroinitiators for ROP of N6-carbobenzoxy-L- lysine N-carboxyanhydride. The thermal behavior of the homopolymers and copolymers in aqueous solutions was studied by turbidimetry, dynamic light scattering (DLS and proton nuclear magnetic resonance spectroscopy (1H-NMR.

Reinforced Mechanical Properties and Tunable Biodegradability in Nanoporous Cellulose Gels: Poly(L-lactide-co-caprolactone) Nanocomposites.

Science.gov (United States)

Li, Kai; Huang, Junchao; Gao, Huichang; Zhong, Yi; Cao, Xiaodong; Chen, Yun; Zhang, Lina; Cai, Jie

2016-04-11

Incorporation of nanofillers into aliphatic polyesters is a convenient approach to create new nanomaterials with significantly reinforced mechanical properties compared to the neat polymers or conventional composites. Nanoporous cellulose gels (NCG) prepared from aqueous alkali hydroxide/urea solutions can act as alternative reinforcement nanomaterials for polymers with improved mechanical properties. We report a simple and versatile process for the fabrication of NCG/poly(L-lactide-co-caprolactone) (NCG/P(LLA-co-CL) nanocomposites through in situ ring-opening polymerization of L-lactide (LLA) and ε-caprolactone (ε-CL) monomers in the NCG. The volume fraction of the NCG in the nanocomposites was tunable and ranged from 4.5% to 37%. Fourier transform infrared (FT-IR), X-ray diffraction (XRD), and differential scanning calorimetry (DSC) results indicated that P(LLA-co-CL) were synthesized within the NCG and partially grafted onto the surface of the cellulose nanofibrils. The glass-transition temperature (Tg) of the NCG/P(LLA-co-CL) nanocomposites could be altered by varying the molar ratio of LLA/ε-CL and was affected by the volume fraction of NCG. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) images confirmed that the interconnected nanofibrillar cellulose network structure of the NCG was finely distributed and preserved in the P(LLA-co-CL) matrix after polymerization. The dynamic mechanical analysis (DMA) results showed remarkable reinforcement of the tensile storage modulus (E') of the P(LLA-co-CL) nanocomposites in the presence of NCG, especially above the Tg of the P(LLA-co-CL). The modified percolation model agreed well with the mechanical properties of the NCG/P(LLA-co-CL) nanocomposites. The introduction of NCG into the P(LLA-co-CL) matrix improved the mechanical properties and thermal stability of the NCG/P(LLA-co-CL) nanocomposites. Moreover, the NCG/P(LLA-co-CL) nanocomposites have tunable biodegradability and biocompatibility and

Preparation and Characterization of Amphiphilic Triblock Terpolymer-Based Nanofibers as Antifouling Biomaterials

KAUST Repository

Cho, Youngjin

2012-05-14

Antifouling surfaces are critical for the good performance of functional materials in various applications including water filtration, medical implants, and biosensors. In this study, we synthesized amphiphilic triblock terpolymers (tri-BCPs, coded as KB) and fabricated amphiphilic nanofibers by electrospinning of solutions prepared by mixing the KB with poly(lactic acid) (PLA) polymer. The resulting fibers with amphiphilic polymer groups exhibited superior antifouling performance to the fibers without such groups. The adsorption of bovine serum albumin (BSA) on the amphiphilic fibers was about 10-fold less than that on the control surfaces from PLA and PET fibers. With the increase of the KB content in the amphiphilic fibers, the resistance to adsorption of BSA was increased. BSA was released more easily from the surface of the amphiphilic fibers than from the surface of hydrophobic PLA or PET fibers. We have also investigated the structural conformation of KB in fibers before and after annealing by contact angle measurements, transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), and coarse-grained molecular dynamics (CGMD) simulation to probe the effect of amphiphilic chain conformation on antifouling. The results reveal that the amphiphilic KB was evenly distributed within as-spun hybrid fibers, while migrated toward the core from the fiber surface during thermal treatment, leading to the reduction in antifouling. This suggests that the antifouling effect of the amphiphilic fibers is greatly influenced by the arrangement of amphiphilic groups in the fibers. © 2012 American Chemical Society.

Characterization and Antimicrobial Property of Poly(Acrylic Acid Nanogel Containing Silver Particle Prepared by Electron Beam

Directory of Open Access Journals (Sweden)

Jong-Bae Choi

2013-05-01

Full Text Available In this study, we developed a one step process to synthesize nanogel containing silver nanoparticles involving electron beam irradiation. Water-soluble silver nitrate powder is dissolved in the distilled water and then poly(acrylic acid (PAAc and hexane are put into this silver nitrate solution. These samples are irradiated by an electron beam to make the PAAc nanogels containing silver nanoparticles (Ag/PAAc nanogels. The nanoparticles were characterized by scanning electron microscopy (SEM and energy dispersive spectroscopy (EDS. In addition, the particle size and zeta-potential were confirmed by a particle size analyzer (PSA. The antibacterial properties of the nanogels were evaluated by paper diffusion test. The Ag/PAAc nanogels had an antibacterial effect against Escherichia coli and Staphylococcus aureus. The nanogels also demonstrated a good healing effect against diabetic ulcer. The size of the Ag/PAAc nanogels decreased with increasing irradiation doses, and the absolute value of the zeta potential increased with increasing irradiation doses. Also, the Ag/PAAc nanogels exhibited good antibacterial activity against both Gram-negative and Gram-positive bacteria. In in vivo wound healing, the Ag/PAAc nanogels have a good healing effect.

SYNTHESIS OF AMPHIPHILIC COMB-SHAPED COPOLYMERS USED FOR SURFACE MODIFICATION OF PVDF MEMBRANES

Institute of Scientific and Technical Information of China (English)

徐又一

2009-01-01

The synthesis of a novel amphiphilic comb-shaped copolymer consisting of a main chain of styrene-(N-(4- hydroxyphenyl) maleimide)(SHMI) copolymer and poly(ethylene glycol) methyl ether methacrylate(PEGMA) side groups was achieved by atom transfer radical polymerization(ATRP).The amphiphilic copolymers were characterized by ~1H-NMR, Fourier transform infrared(FTIR) spectroscopy and gel permeation chromatography(GPC).From thermogravimetric analysis (TGA),the decomposition temperature of SHMI-g-PEGMA is low...

Preparation and properties of thermoplastic poly(caprolactone) composites containing high amount of esterified starch without plasticizer.

Science.gov (United States)

Sun, Yujie; Hu, Qiongen; Qian, Jiangtao; Li, Ting; Ma, Piming; Shi, Dongjian; Dong, Weifu; Chen, Mingqing

2016-03-30

Based on stearyl chloride and native starch, esterified starch were prepared and the chemical structure was characterized by (1)H NMR and FTIR. It was found that stearyl chloride was an efficient agent to fabricate esterified starch with high degree of substitution (DS). During the melt blending of esterified starch (80 wt%) and poly(caprolactone) (PCL, 20 wt%), it was shown the torque of PCL/esterified starch was much lower than that of PCL/native starch without any plasticizer, and further decreased with increasing DS. Compared with PCL/native starch, the tensile properties of PCL/esterified starch composites were significantly enhanced. The tensile strength and elongation at break were increased from 2.7 MPa to 56% for PCL/native starch composites to 9.1 MPa and 626% for PCL/esterified starch ones with DS of 1.50, respectively. SEM observation revealed the esterified starch particles in matrix became smaller and more uniform. In addition, the water resistance and hydrophobic character of PCL/esterified starch composites were improved. PCL composites containing 80 wt% esterified starch with favorable mechanical properties would have great potential applications in broad areas. Copyright © 2015 Elsevier Ltd. All rights reserved.

Au-coated 3-D nanoporous titania layer prepared using polystyrene-b-poly(2-vinylpyridine) block copolymer nanoparticles.

Science.gov (United States)

Shin, Won-Jeong; Basarir, Fevzihan; Yoon, Tae-Ho; Lee, Jae-Suk

2009-04-09

New nanoporous structures of Au-coated titania layers were prepared by using amphiphilic block copolymer nanoparticles as a template. A 3-D template composed of self-assembled quaternized polystyrene-b-poly(2-vinylpyridine) (Q-PS-b-P2VP) block copolymer nanoparticles below 100 nm was prepared. The core-shell-type nanoparticles were well ordered three-dimensionally using the vertical immersion method on the substrate. The polar solvents were added to the polymer solution to prevent particle merging at 40 degrees C when considering the interaction between polymer nanoparticles and solvents. Furthermore, Au-coated PS-b-P2VP nanoparticles were prepared using thiol-capped Au nanoparticles (3 nm). The 3-D arrays with Au-coated PS-b-P2VP nanoparticles as a template contributed to the preparation of the nanoporous Au-coated titania layer. Therefore, the nanoporous Au-coated titania layer was fabricated by removing PS-b-P2VP block copolymer nanoparticles by oxygen plasma etching.

Fabrication of nanocomposite mat through incorporating bioactive glass particles into gelatin/poly(ε-caprolactone) nanofibers by using Box-Behnken design.

Science.gov (United States)

Gönen, Seza Özge; Erol Taygun, Melek; Aktürk, Ayşen; Küçükbayrak, Sadriye

2016-10-01

The current research was conducted to propose a nanocomposite material, which could be suitable to be used as a scaffold for bone tissue engineering applications. For this purpose, nanocomposite fibers of gelatin, poly(ε-caprolactone) (PCL), and bioactive glass were successfully fabricated via electrospinning process. In this context, response surface methodology based on a three-level, four-variable Box-Behnken design was adopted as an optimization tool to choose the most appropriate parameter settings to obtain the desired fiber diameter. The investigation, based on a second order polynomial model, focused on the analysis of the effect of both solution and processing parameters on the fiber diameter and its standard deviation. In optimum conditions (bioactive glass content of 7.5% (w/v), applied voltage of 25kV, tip-to-collector distance of 12.5cm, and flow rate of 1mL/h), the fiber diameter was found to be 584±337nm which was in good agreement with the predicted value by the developed models (523±290nm). Analytical tools such as scanning electron microscopy, X-ray diffraction analysis, Fourier transform infrared spectroscopy, and differential thermal analyzer were used for further evaluation of the optimized nanocomposite mat. The overall results showed that nanocomposite scaffolds could be promising candidates for tissue engineering applications. Copyright © 2016. Published by Elsevier B.V.

Separation of water and oil by poly (acrylic acid)-coated stainless steel mesh prepared by radiation crosslinking

Energy Technology Data Exchange (ETDEWEB)

Nho, Young Chang; Shin, Jung Woong; Park, Jong Seok; Lim, Young Mook; Jeun, Joon Pyo; Kang, Phil Hyun [Research Division for Industry and Environment, Korea Atomic Energy Research Institute, Jeongeup (Korea, Republic of)

2015-05-15

The stainless steel mesh coated with poly(acrylic acid) hydrogel was fabricated and applied for the separation of water and oil. The stainless steel mesh was immersed in aqueous poly (acrylic acid) solution, and then irradiated by radiation to introduce poly(acrylic acid) hydrogel on the surface of mesh by crosslinking. It was possible to separate oil and water from mixtures of oil/water effectively using the hydrogel-coated mesh. The effect of irradiation dose, coating thickness, size of mesh on the separation efficiency was examined.

Codelivery for Paclitaxel and Bcl-2 Conversion Gene by PHB-PDMAEMA Amphiphilic Cationic Copolymer for Effective Drug Resistant Cancer Therapy.

Science.gov (United States)

Wang, Xiaoyuan; Liow, Sing Shy; Wu, Qiaoqiong; Li, Chuang; Owh, Cally; Li, Zibiao; Loh, Xian Jun; Wu, Yun-Long

2017-11-01

Antiapoptotic Bcl-2 protein's upregulated expression is a key reason for drug resistance leading to failure of chemotherapy. In this report, a series of biocompatible amphiphilic cationic poly[(R)-3-hydroxybutyrate] (PHB)-b-poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) copolymer, comprising hydrophobic PHB block and cationic PDMAEMA block, is designed to codeliver hydrophobic chemotherapeutic paclitaxel and Bcl-2 converting gene Nur77/ΔDBD with enhanced stability, due to the micelle formation by hydrophobic PHB segment. This copolymer shows less toxicity but similar gene transfection efficiency to polyethyenimine (25k). More importantly, this codelivery approach by PHB-PDMAEMA leads to increased drug resistant HepG2/Bcl-2 cancer cell death, by increased expression of Nur77 proteins in the Bcl-2 present intracellular mitochondria. This work signifies for the first time that cationic amphiphilic PHB-b-PDMAEMA copolymers can be utilized for the drug and gene codelivery to drug resistant cancer cells with high expression of antiapoptosis Bcl-2 protein and the positive results are encouraging for the further design of codelivery platforms for combating drug resistant cancer cells. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bioactive Glass Nanoparticles-Loaded Poly(ɛ-caprolactone Nanofiber as Substrate for ARPE-19 Cells

Directory of Open Access Journals (Sweden)

Tadeu Henrique Lima

2016-01-01

Full Text Available Bioactive glass nanoparticles-loaded poly(ɛ-caprolactone nanofibers (BIOG PCL nanofibers were synthesized and evaluated as substrates for ocular cells (ARPE-19. BIOG PCL nanofibers were characterized using SEM, FTIR, and DSC, and the in vitro degradation profile was also investigated. The in vitro ocular biocompatibility of nanofibers was exploited in Müller glial cells (MIO-M1 cells and in chorioallantoic membrane (CAM; and the proliferative capacity, cytotoxicity, and functionality were evaluated. Finally, ARPE-19 cells were seeded onto BIOG PCL nanofibers and they were investigated as supports for in vitro cell adhesion and proliferation. SEM images revealed the incorporation of BIOG nanoparticles into PCL nanofibers. Nanoparticles did not induce modifications in the chemical structure and semicrystalline nature of PCL in the nanofiber, as shown by FTIR and DSC. MIO-M1 cells exposed to BIOG PCL nanofibers showed viability, and they were able to proliferate and to express GFAP, indicating cellular functionality. Moreover, nanofibers were well tolerated by CAM. These findings suggested the in vitro ocular biocompatibility and absence of toxicity of these nanofibers. Finally, the BIOG nanoparticles modulated the protein adsorption, and, subsequently, ARPE-19 cells adhered and proliferated onto the nanostructured supports, establishing cell-substrate interactions. In conclusion, the biodegradable and biocompatible BIOG PCL nanofibers supported the ARPE-19 cells.

pH Triggered Recovery and Reuse of Thiolated Poly(acrylic acid) Functionalized Gold Nanoparticles with Applications in Colloidal Catalysis.

Science.gov (United States)

Ansar, Siyam M; Fellows, Benjamin; Mispireta, Patrick; Mefford, O Thompson; Kitchens, Christopher L

2017-08-08

Thiolated poly(acrylic acid) (PAA-SH) functionalized gold nanoparticles were explored as a colloidal catalyst with potential application as a recoverable catalyst where the PAA provides pH-responsive dispersibility and phase transfer capability between aqueous and organic media. This system demonstrates complete nanoparticle recovery and redispersion over multiple reaction cycles without changes in nanoparticle morphology or reduction in conversion. The catalytic activity (rate constant) was reduced in subsequent reactions when recovery by aggregation was employed, despite unobservable changes in morphology or dispersibility. When colloidal catalyst recovery employed a pH induced phase transfer between two immiscible solvents, the catalytic activity of the recovered nanoparticles was unchanged over four cycles, maintaining the original rate constant and 100% conversion. The ability to recover and reuse colloidal catalysts by aggregation/redispersion and phase transfer methods that occur at low and high pH, respectively, could be used for different gold nanoparticle catalyzed reactions that occur at different pH conditions.

Preparation and self-assembly behavior of polystyrene-block-poly (dimethylaminoethyl methacrylate amphiphilic block copolymer using atom transfer radical polymerization

Directory of Open Access Journals (Sweden)

2008-03-01

Full Text Available Asymmetric and semi-symmetric amphiphilic diblock copolymers polystyrene-block-poly (dimethylaminoethyl methacrylate (PS-b-PDMAEMA with the same PS block length of 62 repeat units and quite short (3 repeat units or equivalent (47 repeat units length of PDMAEMA have been prepared simply by varying the ratio of the bromine-terminated macroinitiator polystyrene (PS-Br to DMAEMA using atom transfer radical polymerization (ATRP. The chemical structures and compositions of the PS-b-PDMAEMA block copolymers are studied by nuclear magnetic resonance (NMR spectroscopy, gel permeation chromatography (GPC, and elementary analysis (EA. The self-assembly behaviors of copolymers in N,N-dimethyl formamide (DMF with different pH and dioxane/water binary solvent mixture by direct dissolution method (DD, are studied by transmission electron microscopy (TEM, electron diffracting analysis (EDA, and energy-dispersive analysis of X-rays (EDAX techniques. Transmission electron microscopy results suggest that asymmetric block copolymer PS62-b-PDMAEMA3 (the numbers in the form of footnotes represent repeated units of each monomer in the copolymer can form spherical core-shell micelles, large compound reverse micelles (LCRMs, hexagonal/rhombic phases, reverse hexagonal/rhombic phases, vesicles, reverse vesicles and necklace-like reverse micelles, controlled by common or selective solvent and pH, while most of the aggregates of semi-symmetric PS62-b-PDMAEMA47 are simply spherical, such as spherical core-shell micelles and reverse spherical core-shell micelles, besides hexagonal/rhombic phases. All above structures are controlled by three components of the free energy of aggregation: core-chain stretching, interfacial energy and intercoronal chain interaction.

Investigation on the ion pair amphiphiles and their in vitro release of amantadine drug based on PLGA–PEG–PLGA gel

International Nuclear Information System (INIS)

Yang, Xiaoxia; Ji, Xiaoqing; Shi, Chunhuan; Liu, Jing; Wang, Haiyang; Luan, Yuxia

2014-01-01

The amantadine drug and oleic acid surfactant are used to form amantadine-based ion pair amphiphiles based on proton transfer reaction between the drug and the surfactant molecules. The ion pair amphiphiles are characterized by 1 H-nuclear magnetic resonance, Fourier transform infrared spectroscopy, and X-ray diffraction. Self-assembly properties of amantadine-based ion pair amphiphiles are studied by surface tension determination, transmission electron microscopy, zeta potential, and dynamic light scattering. The aggregation behavior studies indicate that the as-prepared ion pair amphiphiles can self-assemble into vesicles with the size of 200–300 nm in aqueous solution. The drug release results show that the amantadine release rate could be well controlled by incorporating the amantadine-based ion pair vesicles in poly (lactic-co-glycolic acid)-poly (ethylene glycol)-poly (lactic-co-glycolic acid) (PLGA–PEG–PLGA) copolymer hydrogel. The drug release from the AT–OA vesicle-loaded PLGA–PEG–PLGA hydrogel is significantly inhibited in comparison with the AT-loaded PLGA–PEG–PLGA hydrogel. The present work thus demonstrates that the vesicle-loaded hydrogel is a good candidate for the drug delivery system with long-term controlled drug release behavior

3D printed alendronate-releasing poly(caprolactone) porous scaffolds enhance osteogenic differentiation and bone formation in rat tibial defects.

Science.gov (United States)

Kim, Sung Eun; Yun, Young-Pil; Shim, Kyu-Sik; Kim, Hak-Jun; Park, Kyeongsoon; Song, Hae-Ryong

2016-09-29

The aim of this study was to evaluate the in vitro osteogenic effects and in vivo new bone formation of three-dimensional (3D) printed alendronate (Aln)-releasing poly(caprolactone) (PCL) (Aln/PCL) scaffolds in rat tibial defect models. 3D printed Aln/PCL scaffolds were fabricated via layer-by-layer deposition. The fabricated Aln/PCL scaffolds had high porosity and an interconnected pore structure and showed sustained Aln release. In vitro studies showed that MG-63 cells seeded on the Aln/PCL scaffolds displayed increased alkaline phosphatase (ALP) activity and calcium content in a dose-dependent manner when compared with cell cultures in PCL scaffolds. In addition, in vivo animal studies and histologic evaluation showed that Aln/PCL scaffolds implanted in a rat tibial defect model markedly increased new bone formation and mineralized bone tissues in a dose-dependent manner compared to PCL-only scaffolds. Our results show that 3D printed Aln/PCL scaffolds are promising templates for bone tissue engineering applications.

Evaluation of the antifouling and photocatalytic properties of poly(vinylidene fluoride) plasma-grafted poly(acrylic acid) membrane with self-assembled TiO2

International Nuclear Information System (INIS)

You, Sheng-Jie; Semblante, Galilee Uy; Lu, Shao-Chung; Damodar, Rahul A.; Wei, Ta-Chin

2012-01-01

Highlights: ► Plasma and grafting parameters that maximized TiO 2 binding sites were found. ► PVDF hydrophilicity was vastly improved compared to other modification techniques. ► At least 1.5% TiO 2 and 30 min UV exposure were needed to attain full flux recovery. ► Photocatalytic membranes could remove up to 42% of 50 mg/l RB5 dye. - Abstract: Immobilization of TiO 2 is a promising approach that produces antifouling and photocatalytic membranes that could help advance wastewater treatment and re-use processes. In this study, poly(acrylic acid) (PAA) was plasma-grafted on commercial poly(vinylidene fluoride) (PVDF) to introduce functional groups on the membrane surface that can support the nanoparticles. It was found that plasma treatment at 100 W for 120 s followed by liquid grafting with 70% aqueous AA at 60 °C for 2 h maximized the number of TiO 2 binding sites. Membrane hydrophilicity was tremendously enhanced by the self-assembly of TiO 2 , following a direct proportionality to TiO 2 loading. The membrane with 0.5% TiO 2 loading maintained the highest pure water flux and the best protein antifouling property. UV irradiation triggered the photodegradation of strongly bound foulants, but at least 1.5% TiO 2 and 30 min cumulative irradiation were necessary to completely recover the membrane's original performance. The TiO 2 -modified membranes removed 30–42% of 50 mg/l aqueous Reactive Black 5 (RB5) dye. The fabricated membranes demonstrate huge potential for use in membrane reactors with high hydrophilicity, fouling mitigation, and photocatalytic capability.

Investigation of Complexation of Linear Poly(N-vinyl-2-pyrrolidone) with Poly(methacrylic acid-co-methyl methacrylate) Gel

OpenAIRE

Liu, Guoqin; Yan, Guojin; Zou, Wenjun; Li, Zhengxin

2011-01-01

The contraction of poly(methacrylic acid-co-methyl methacrylate) (P(MAA-co-MMA)) gel induced by complexation with linear poly(N-vinyl-2-pyrrolidone) (PVP) is quite different from that of poly(acrylic acid) (PAA) or poly(methacrylic acid) (PMAA) gel. It was found that the concentration of PVP has a strong effect on the complexation with P(MAA-co-MMA) gel. When PVP was introduced into the P(MAA-co-MMA) network, its dynamic mechanic properties vary greatly between complexed and uncomplexed netwo...

A directional entrapment modification on the polyethylene surface by the amphiphilic modifier of stearyl-alcohol poly(ethylene oxide) ether

Science.gov (United States)

Lu, Qiang; Chen, Yi; Huang, Juexin; Huang, Jian; Wang, Xiaolin; Yao, Jiaying

2018-05-01

A novel entrapment modification method involving directional implantation of the amphiphilic modifier of stearyl-alcohol poly(ethylene oxide) ether (AEO) into the high-density polyethylene (HDPE) surface is proposed. This modification technique allows the AEO modifier to be able to spontaneously attain and subsequently penetrate into the swollen HDPE surface with its hydrophobic stearyl segment, while its hydrophilic poly(ethylene oxide) (PEO) segment spontaneously points to water. The AEO modifier with a HLB number below 8.7 was proved appropriate for the directional entrapment, Nevertheless, AEOs with larger HLB numbers were also effective modifiers in the presence of salt additives. In addition, a larger and hydrophobic micelle, induced respectively by the AEO concentration above 1.3 × 10-2 mol/L and the entrapping temperature above the cloud point of AEO, could lead to a sharp contact angle decline of the modified surface. Finally, a hydrophilic HDPE surface with the modifier coverage of 38.9% was reached by the directional entrapment method, which is far larger than that of 19.2% by the traditional entrapment method.

Evaluation of poly(lactic-co-glycolic acid) and poly(DL-lactide-co-ε-caprolactone) electrospun fibers for the treatment of HSV-2 infection

Energy Technology Data Exchange (ETDEWEB)

Aniagyei, Stella E.; Sims, Lee B. [Department of Bioengineering, University of Louisville, Louisville, KY 40202 (United States); Malik, Danial A. [Department of Pharmacology and Toxicology, University of Louisville, Louisville, KY 40202 (United States); Tyo, Kevin M. [Department of Pharmacology and Toxicology, University of Louisville, Louisville, KY 40202 (United States); Center for Predictive Medicine, University of Louisville, Louisville, KY 40202 (United States); Curry, Keegan C. [Department of Bioengineering, University of Louisville, Louisville, KY 40202 (United States); Kim, Woihwan [Department of Medicine, University of Louisville, Louisville, KY 40202 (United States); Hodge, Daniel A. [Department of Bioengineering, University of Louisville, Louisville, KY 40202 (United States); Duan, Jinghua [Department of Bioengineering, University of Louisville, Louisville, KY 40202 (United States); Center for Predictive Medicine, University of Louisville, Louisville, KY 40202 (United States); Steinbach-Rankins, Jill M., E-mail: jill.steinbach@louisville.edu [Department of Bioengineering, University of Louisville, Louisville, KY 40202 (United States); Department of Pharmacology and Toxicology, University of Louisville, Louisville, KY 40202 (United States); Department of Microbiology and Immunology, University of Louisville, Louisville, KY 40202 (United States); Center for Predictive Medicine, University of Louisville, Louisville, KY 40202 (United States)

2017-03-01

More diverse multipurpose prevention technologies are urgently needed to provide localized, topical pre-exposure prophylaxis against sexually transmitted infections (STIs). In this work, we established the foundation for a multipurpose platform, in the form of polymeric electrospun fibers (EFs), to physicochemically treat herpes simplex virus 2 (HSV-2) infection. To initiate this study, we fabricated different formulations of poly(lactic-co-glycolic acid) (PLGA) and poly(DL-lactide-co-ε-caprolactone) (PLCL) EFs that encapsulate Acyclovir (ACV), to treat HSV-2 infection in vitro. Our goals were to assess the release and efficacy differences provided by these two different biodegradable polymers, and to determine how differing concentrations of ACV affected fiber efficacy against HSV-2 infection and the safety of each platform in vitro. Each formulation of PLGA and PLCL EFs exhibited high encapsulation efficiency of ACV, sustained-delivery of ACV through one month, and in vitro biocompatibility at the highest doses of EFs tested. Additionally, all EF formulations provided complete and efficacious protection against HSV-2 infection in vitro, regardless of the timeframe of collected fiber eluates tested. This work demonstrates the potential for PLGA and PLCL EFs as delivery platforms against HSV-2, and indicates that these delivery vehicles may be expanded upon to provide protection against other sexually transmitted infections. - Highlights: • PLGA and PLCL EFs exhibit sustained-delivery of ACV through one month. • EFs exhibit high ACV encapsulation efficiency and in vitro biocompatibility. • EFs serve as both physical and chemical barriers to HSV-2 infection. • Potent in vitro efficacy is provided against HSV-2 infection for all formulations. • HSV-2 protection is independent of administration times within one month.

Evaluation of poly(lactic-co-glycolic acid) and poly(DL-lactide-co-ε-caprolactone) electrospun fibers for the treatment of HSV-2 infection

International Nuclear Information System (INIS)

Aniagyei, Stella E.; Sims, Lee B.; Malik, Danial A.; Tyo, Kevin M.; Curry, Keegan C.; Kim, Woihwan; Hodge, Daniel A.; Duan, Jinghua; Steinbach-Rankins, Jill M.

2017-01-01

More diverse multipurpose prevention technologies are urgently needed to provide localized, topical pre-exposure prophylaxis against sexually transmitted infections (STIs). In this work, we established the foundation for a multipurpose platform, in the form of polymeric electrospun fibers (EFs), to physicochemically treat herpes simplex virus 2 (HSV-2) infection. To initiate this study, we fabricated different formulations of poly(lactic-co-glycolic acid) (PLGA) and poly(DL-lactide-co-ε-caprolactone) (PLCL) EFs that encapsulate Acyclovir (ACV), to treat HSV-2 infection in vitro. Our goals were to assess the release and efficacy differences provided by these two different biodegradable polymers, and to determine how differing concentrations of ACV affected fiber efficacy against HSV-2 infection and the safety of each platform in vitro. Each formulation of PLGA and PLCL EFs exhibited high encapsulation efficiency of ACV, sustained-delivery of ACV through one month, and in vitro biocompatibility at the highest doses of EFs tested. Additionally, all EF formulations provided complete and efficacious protection against HSV-2 infection in vitro, regardless of the timeframe of collected fiber eluates tested. This work demonstrates the potential for PLGA and PLCL EFs as delivery platforms against HSV-2, and indicates that these delivery vehicles may be expanded upon to provide protection against other sexually transmitted infections. - Highlights: • PLGA and PLCL EFs exhibit sustained-delivery of ACV through one month. • EFs exhibit high ACV encapsulation efficiency and in vitro biocompatibility. • EFs serve as both physical and chemical barriers to HSV-2 infection. • Potent in vitro efficacy is provided against HSV-2 infection for all formulations. • HSV-2 protection is independent of administration times within one month.

Determining the mechanical properties of electrospun poly-ε-caprolactone (PCL) nanofibers using AFM and a novel fiber anchoring technique.

Science.gov (United States)

Baker, Stephen R; Banerjee, Soham; Bonin, Keith; Guthold, Martin

2016-02-01

Due to its low cost, biocompatibility and slow bioresorption, poly-ε-caprolactone (PCL) continues to be a suitable material for select biomedical engineering applications. We used a combined atomic force microscopy (AFM)/optical microscopy technique to determine key mechanical properties of individual electrospun PCL nanofibers with diameters between 440-1040nm. Compared to protein nanofibers, PCL nanofibers showed much lower adhesion, as they slipped on the substrate when mechanically manipulated. We, therefore, first developed a novel technique to anchor individual PCL nanofibers to micrometer-sized ridges on a substrate, and then mechanically tested anchored nanofibers. When held at constant strain, tensile stress relaxed with fast and slow relaxation times of 1.0±0.3s and 8.8±3.1s, respectively. The total tensile modulus was 62±26MPa, the elastic (non-relaxing) component of the tensile modulus was 53±36MPa. Individual PCL fibers could be stretched elastically (without permanent deformation) to strains of 19-23%. PCL nanofibers are rather extensible; they could be stretched to a strain of at least 98%, and a tensile strength of at least 12MPa, before they slipped off the AFM tip. PCL nanofibers that had aged for over a month at ambient conditions became stiffer and less elastic. Our technique provides accurate nanofiber mechanical data, which are needed to guide construction of scaffolds for cells and other biomedical devices. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

Photo-induced green synthesis and antimicrobial efficacy of poly (ɛ-caprolactone)/curcumin/grape leaf extract-silver hybrid nanoparticles.

Science.gov (United States)

El-Sherbiny, Ibrahim M; El-Shibiny, Ayman; Salih, Ehab

2016-07-01

This study reports the photo-induced green synthesis and antimicrobial assessment of poly(ɛ-caprolactone)/curcumin/grape leaf extract-Ag hybrid nanoparticles (PCL/Cur/GLE-Ag NPs). PCL/Cur/GLE NPs were synthesized via emulsion-solvent evaporation in the presence of PVA as a capping agent, then used as active nano-supports for the green synthesis and stabilization of AgNPs on their surfaces. Both Cur and GLE were selected and incorporated into the PCL nano-supports due to their reported promising antimicrobial activity that would further enhance that of the synthesized AgNPs. The developed PCL/Cur/GLE NPs and PCL/Cur/GLE-Ag hybrid NPs were characterized using UV-visible spectrophotometry, high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD). HRTEM images showed that the PCL/Cur/GLE NPs are monodispersed and spherical with size of about 270nm, and the AgNPs were formed mainly on their surfaces with average size in the range 10-30nm. The synthesized AgNPs were found to be crystalline as shown by XRD patterns with fcc phase oriented along the (111), (200), (220) and (311) planes. The antimicrobial characteristics of the newly developed NPs were investigated against gram-positive and gram-negative bacteria in addition to two fungal strains. The results demonstrated that the PCL/Cur/GLE-Ag hybrid NPs have a potential antimicrobial activity against pathogenic bacterial species and could be considered as an alternative antibacterial agent. Copyright © 2016 Elsevier B.V. All rights reserved.

Poly(glycerol adipate)-fatty acid esters as versatile nanocarriers

DEFF Research Database (Denmark)

Weiss, Verena M; Naolou, Toufik; Hause, Gerd

2012-01-01

Poly(glycerol adipate) (PGA) is a biodegradable polymer with promising features for nanoparticulate drug carrier systems. By acylation of PGA with fatty acids, composite systems with amphiphilic properties can be obtained. Variation of the fatty acid (laurate, stearate and behenate) and their sub...... and the nanoparticles. With their diverse particle shapes and internal structures as well as their different thermal behavior, aggregate states and polarities, the systems offer promising possibilities as delivery systems for lipophilic, amphiphilic and water soluble drugs.......Poly(glycerol adipate) (PGA) is a biodegradable polymer with promising features for nanoparticulate drug carrier systems. By acylation of PGA with fatty acids, composite systems with amphiphilic properties can be obtained. Variation of the fatty acid (laurate, stearate and behenate...

Preparation and evaluation of poly(caprolactone fumarate nanoparticles containing doxorubicin HCl

Directory of Open Access Journals (Sweden)

N Shokri

2011-03-01

Full Text Available Background and the purpose of the study: Biodegradable Poly(caprolactone fumarate (PCLF has been used as bioresorbable sutures. In this study, doxorubicin HCl (Dox loaded PCLF nanoparticles were prepared and characterized.  Materials and methods: PCLFs were synthesized by polycondensation of PCL diols (Mws of 530, 1250 and 2000 with fumaryl chloride. The degradation of PCLF in NaOH, water and phosphate buffer saline (PBS, was determined in terms of Mw. Nanoparticles (NPs were prepared by two methods. In microemulsion polymerization method, dichloromethane containing PCLF and photoinitiator were combined with the water containing surfactants and then placed under light for crosslinking. In nanoprecipitation method, the organic solvent containing PCLF was poured into the stirring water. The effect of several variables concentration of PCLF, poly vinyl alcohol (PVA, Dox and Trypan blue (Trb and the Mw of PCLF and PVA on NP size and loading were evaluated. Results: PCLF 530, 1250 and 2000 in PBS or water were not degrade over 28 days. Nanoprecipitaion method gave spherical (revealed by SEM images stable NPs of about 225 with narrow size distribution and a zeta potential of -43 mV. The size of NP increased significantly with increase in Mw or concentration of PCLF. Although PVA was not necessary for formation of NPs but decreased the NP size. Dox loading and EE were 2.5-6.8% and 15-20%, respectively. Increasing the drug concentration, increased the drug loading (DL and NP size. The entrapment efficiency (EE for Trb ranged from 1% for PCLF530 to 6% for PCLF2000. An increase in PCLF concentration resulted in an increase in EE. Dox and Trb release showed a burst followed by 80% and 78% release during 3 and 4 days respectively.                                                                                                            �

Synthesis and characterization of hydroxyl-functionalized caprolactone copolymers and their effect on adhesion, proliferation, and differentiation of human mesenchymal stem cells.

Science.gov (United States)

Seyednejad, Hajar; Vermonden, Tina; Fedorovich, Natalja E; van Eijk, Roel; van Steenbergen, Mies J; Dhert, Wouter J A; van Nostrum, Cornelus F; Hennink, Wim E

2009-11-09

The aim of this study was to develop new hydrophilic polyesters for tissue engineering applications. In our approach, poly(benzyloxymethyl glycolide-co-epsilon-caprolactone)s (pBHMG-CLs) were synthesized through melt copolymerization of epsilon-caprolactone (CL) and benzyl-protected hydroxymethyl glycolide (BHMG). Deprotection of the polymers yielded copolymers with pendant hydroxyl groups, poly(hydroxymethylglycolide-co-epsilon-caprolactone) (pHMG-CL). The synthesized polymers were characterized by GPC, NMR, and DSC techniques. The resulting copolymers consisting of up to 10% of HMG monomer were semicrystalline with a melting temperature above body temperature. Water contact angle measurements of polymeric films showed that increasing HMG content resulted in higher surface hydrophilicity, as evidenced from a decrease in receding contact angle from 68 degrees for PCL to 40 degrees for 10% HMG-CL. Human mesenchymal stem cells showed good adherence onto pHMG-CL films as compared to the more hydrophobic PCL surfaces. The cells survived and were able to differentiate toward osteogenic lineage on pHMG-CL surfaces. This study shows that the aforementioned hydrophilic polymers are attractive candidates for the design of scaffolds for tissue engineering applications.

Preparation of pH-sensitive amphiphilic block star polymers, their self-assembling characteristics and release behavior on encapsulated molecules

KAUST Repository

Song, Xiaowan

2016-05-28

Poly(ethylene glycol) (PEG), a polymer with excellent biocompatibility, was widely used to form nanoparticles for drug delivery applications. In this paper, based on PEG, a series of pH-sensitive amphiphilic block star polymers of poly(ethylene glycol)-block-poly(ethoxy ethyl glycidyl ether) (PEG-b-PEEGE) with different hydrophobic length were synthesized by living anionic ring-opening polymerization method. The products were characterized using 1H NMR and gel permeation chromatography. These copolymers could self-assemble in aqueous solution to form micellar structure with controlled morphologies. Transmission electron microscopy showed that the nanoparticles are spherical or rodlike with different hydrophilic mass fractions. The pH response of polymeric aggregates from PEG-b-PEEGE was detected by fluorescence probe technique at different pH. A pH-dependent release behavior was observed and pH-responsiveness of PEG-b-PEEGE was affected by the hydrophobic block length. These results demonstrated that star-shaped polymers (PEG-b-PEEGE) are attractive candidates as anticancer drug delivery carriers. © 2016 Springer-Verlag Berlin Heidelberg

Preparation of pH-sensitive amphiphilic block star polymers, their self-assembling characteristics and release behavior on encapsulated molecules

KAUST Repository

Song, Xiaowan; Cao, Ming; Chen, Peng; Xia, Ru; Zheng, Zhengzhi; Miao, Jibin; Yang, Bin; Su, Lifen; Qian, Jiasheng; Feng, Xiaoshuang

2016-01-01

Poly(ethylene glycol) (PEG), a polymer with excellent biocompatibility, was widely used to form nanoparticles for drug delivery applications. In this paper, based on PEG, a series of pH-sensitive amphiphilic block star polymers of poly

Amphiphilic Imbalance and Stabilization of Block Copolymer Micelles on-Demand through Combinational Photo-Cleavage and Photo-Crosslinking.

Science.gov (United States)

Zhang, Xuan; Wang, Youpeng; Li, Guo; Liu, Zhaotie; Liu, Zhongwen; Jiang, Jinqiang

2017-01-01

An amphiphilic block copolymer of poly(ethylene oxide)-b-poly((N-methacryloxy phthalimide)-co-(7-(4-vinyl-benzyloxyl)-4-methylcoumarin)) (PEO 45 -b-P(MAPI 36 -co-VBC 4 )) is designed to improve the micellar stability during the photo-triggered release of hydrophobic cargoes. Analysis of absorption and emission spectra, solution transmittance, dynamic light scattering, and transmission electron microscopy supports that polymer micelles of PEO 45 -b-P(MAPI 36 -co-VBC 4 ) upon the combinational irradiation of 365 and 254 nm light can be solubilized through the photolysis of phthalimide esters and simultaneously crosslinked via the partially reversible photo-dimerization of coumarins. The photo-triggered release experiment shows that the leakage of doxorubicin molecules from crosslinked micelles can be predictably regulated by controlling the irradiation time of 365 and 254 nm light. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterization of bioactive RGD peptide immobilized onto poly(acrylic acid) thin films by plasma polymerization

Energy Technology Data Exchange (ETDEWEB)

Seo, Hyun Suk; Ko, Yeong Mu; Shim, Jae Won [Department of Dental Materials, School of Dentistry, MRC Center, Chosun University, Gwangju (Korea, Republic of); Lim, Yun Kyong; Kook, Joong-Ki [Department of Oral Biochemistry, School of Dentistry, Chosun University, Gwangju (Korea, Republic of); Cho, Dong-Lyun [School of Applied Chemical Engineering and Center for Functional Nano Fine Chemicals, Chonnam National University, Gwangju (Korea, Republic of); Kim, Byung Hoon, E-mail: kim5055@chosun.ac.kr [Department of Dental Materials, School of Dentistry, MRC Center, Chosun University, Gwangju (Korea, Republic of)

2010-11-01

Plasma surface modification can be used to improve the surface properties of commercial pure Ti by creating functional groups to produce bioactive materials with different surface topography. In this study, a titanium surface was modified with acrylic acid (AA) using a plasma treatment and immobilized with bioactive arginine-glycine-aspartic acid (RGD) peptide, which may accelerate the tissue integration of bone implants. Both terminals containing the -NH{sub 2} of RGD peptide sequence and -COOH of poly(acrylic acid) (PAA) thin film were combined with a covalent bond in the presence of 1-ethyl-3-3-dimethylaminopropyl carbodiimide (EDC). The chemical structure and morphology of AA film and RGD immobilized surface were investigated by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR), atomic force microscopy (AFM), and scanning electron microscopy (SEM). All chemical analysis showed full coverage of the Ti substrate with the PAA thin film containing COOH groups and the RGD peptide. The MC3T3-E1 cells were cultured on each specimen, and the cell alkaline phosphatase (ALP) activity were examined. The surface-immobilized RGD peptide has a significantly increased the ALP activity of MC3T3-E1 cells. These results suggest that the RGD peptide immobilization on the titanium surface has an effect on osteoblastic differentiation of MC3T3-E1 cells and potential use in osteo-conductive bone implants.

Complexing blends of polyacrylic acid-polyethylene glycol and poly(ethylene-co-acrylic acid)-polyethylene glycol as shape stabilized phase change materials

International Nuclear Information System (INIS)

Alkan, Cemil; Günther, Eva; Hiebler, Stefan; Himpel, Michael

2012-01-01

Highlights: ► Complexing groups to PEGs in a polymer could stabilize PEG at different molecular weights. ► Shape stabilized PEGs for thermal energy storage are prepared using compounds with interacting groups. ► Phase change temperature of PEGs could be changed using a complexing copolymer with acid groups. - Abstract: Blends of poly(ethylene glycol) (PEG) at 1000, 6000, and 10,000 g/mole average molecular weights and poly(acrylic acid) (PAA) or poly(ethylene-co-acrylic acid) (EcoA) have been prepared by solution blending and accounted for thermal energy storage properties as shape stabilized polymer blends. The blends have been analyzed using Fourier transform infrared (FT-IR) spectroscopy and differential scanning calorimetry (DSC) techniques. Total thermal energy values of the complexes have been determined by the method of Mehling et al. As a result of the investigation it is found that polymers with acid groups form interpolymer complexes (IPCs) and miscible and immiscible IPC–PEG blends when blended with PEGs. PEGs formed IPCs with PAA and EcoA polymers in solutions and reach to saturation and turns to be blends of IPC and PEG polymer. PEGs in this work bleed out of the blends when its compositions reach to a degree of immiscibility. In the first range where blends are IPCs and in the third range where bleeding of PEG occurs, blends are not feasible for thermal energy storage applications. However, in the second range, the blends are potential materials for passive thermal energy storage applications.

Biocompatibility and bond degradation of poly-acrylic acid coated copper iodide-adhesives.

Science.gov (United States)

ALGhanem, Adi; Fernandes, Gabriela; Visser, Michelle; Dziak, Rosemary; Renné, Walter G; Sabatini, Camila

2017-09-01

To investigate the effect of poly-acrylic acid (PAA) copper iodide (CuI) adhesives on bond degradation, tensile strength, and biocompatibility. PAA-CuI particles were incorporated into Optibond XTR, Optibond Solo and XP Bond in 0.1 and 0.5mg/ml. Clearfil SE Protect, an MDPB-containing adhesive, was used as control. The adhesives were applied to human dentin, polymerized and restored with composite in 2mm-increments. Resin-dentin beams (0.9±0.1mm 2 ) were evaluated for micro-tensile bond strength after 24h, 6 months and 1year. Hourglass specimens (10×2×1mm) were evaluated for ultimate tensile strength (UTS). Cell metabolic function of human gingival fibroblast cells exposed to adhesive discs (8×1mm) was assessed with MTT assay. Copper release from adhesive discs (5×1mm) was evaluated with UV-vis spectrophotometer after immersion in 0.9% NaCl for 1, 3, 5, 7, 10, 14, 21 and 30 days. SEM, EDX and XRF were conducted for microstructure characterization. XTR and Solo did not show degradation when modified with PAA-CuI regardless of the concentration. The UTS for adhesives containing PAA-CuI remained unaltered relative to the controls. The percent viable cells were reduced for Solo 0.5mg/ml and XP 0.1 or 0.5mg/ml PAA-CuI. XP demonstrated the highest ion release. For all groups, the highest release was observed at days 1 and 14. PAA-CuI particles prevented the bond degradation of XTR and Solo after 1year without an effect on the UTS for any adhesive. Cell viability was affected for some adhesives. A similar pattern of copper release was demonstrated for all adhesives. Copyright © 2017. Published by Elsevier Ltd.

The Effect of Double Crosslinker on Precipitation Polymerization of Poly(acrylic acid

Directory of Open Access Journals (Sweden)

Hajar Es-haghi

2014-06-01

Full Text Available Cross-linked poly(acrylic acids were prepared by dual cross-linkers via precipitation polymerization method in a binary organic solvent. Polyethylene glycol diacrylate (PEGDA-400 as a long-chain cross-linker and di(trimethylol propane tetraacrylate (DTMPTA as multifunctional cross-linker were used. PEGDA-400 was utilized to increase thickening properties and DTMPTA was used to improve the gel strength. The dual cross-linkers effect on the sample features (i.e., equilibrium swelling, thickening properties and rheological properties was investigated. Maximum amount of swelling was obtained by a high percentage of long-chain cross-linker. The apparent viscosity of the microgels was measured to determine their thickening properties for aqueous media. Maximum viscosity occurred at DT25-PE75 which was dependent on the type of cross-linkers in the polymer structure. The Flory-Rehner equation (from swelling ratio data and rubber elasticity theory (from rheometry data were used to discuss the network structure of the polymer. Increasing density of the network was shown by a sample containing high percentage of a four-functional cross-linker. The rheological properties of the cross-linked polymers were measured to determine storage modulus (strength network. The rheological behaviors demonstrated that the synthesized polymer containing a high amount of four-functional cross-linker had higher storage modulus (G′ than other samples. In addition the consistency coefficient (m and flow behavior index (n parameters of Ostwald equation were investigated as well. As a result, n values in each sample were found to be smaller than 1 and these results were fitted clearly with the pseudoplastic model. Apparent and rotational viscosities were used to determine the optimal cross-linker type (synthesized sample contained a high percentage of long-chain cross-linker.

In vitro test and application for guided bone regeneration of {beta}-tricalcium phosphate / poly-(lactide-glycolic acid-{epsilon}-caprolactone) composites

Energy Technology Data Exchange (ETDEWEB)

Kikuchi, M.; Tanaka, J. [National Inst. for Research in Inorganic Materials, Tsukuba (Japan); Koyama, Y.; Takakuda, K.; Miyairi, H. [Tokyo Medical and Dental Univ. (Japan). Inst. of Biomaterials and Bioengineering

2001-07-01

In order to realize easy handling films, novel composites of {beta}-tricalcium phosphate (TCP) and poly-(lactide-glycolic acid-{epsilon}-caprolactone) (PLGC) having a softening temperature of about 40 C were prepared by a heat-kneading method. The composite prepared could be easily formed into a cylindrical membrane at 40 C, and its tensile strength was greater than that of a pure PLGC. From Fourier-transformed infrared spectroscopy, it was shown that the chemical interaction formed between TCP and PLGC. Physiological saline soaking test indicated that TCP inhibited hydrolysis of PLGC by auto-controlling saline pH, resulting in almost constant tensile strength. Mandibular 2-wall bone defects 2 x 1 x 1 cm{sup 3} in size and tibia fully defects 2 cm in length of beagles were filled with new bone 12 weeks after guided bone regeneration (GBR) operation using the composite membrane, although a pure PLGC membrane could not repair such defects. The composite membrane was useful for the GBR membrane. (orig.)

Electrospun composite matrices of poly(ε-caprolactone)-montmorillonite made using tenside free Pickering emulsions

International Nuclear Information System (INIS)

Samanta, Archana; Takkar, Sonam; Kulshreshtha, Ritu; Nandan, Bhanu; Srivastava, Rajiv K.

2016-01-01

The production of composite electrospun matrices of poly(ε-caprolactone) (PCL) using an emulsifier-free emulsion, made with minimal organic solvent, as precursor is reported. Pickering emulsions of PCL were prepared using modified montmorillonite (MMT) clay as the stabilizer. Hydrophobic tallow group of the modified MMT clay resulted in analogous interaction of clay with oil and aqueous phase and its adsorption at the interface to provide stability to the resultant emulsion. Composite fibrous matrices of PCL and MMT were produced using electrospinning under controlled conditions. The fiber fineness was found to alter with PCL concentration and volume fraction of the aqueous and oil phases. A higher tensile strength and modulus was obtained with inclusion of MMT in PCL electrospun matrix in comparison to a matrix made using neat PCL. The presence of clay in the fibrous matrix did not change the cell proliferation efficiency in comparison to neat PCL matrix. Composite fibrous matrices of PCL/MMT bearing enhanced tensile properties may find applications in areas other than tissue engineering for example food packaging and filtration. - Highlights: • Tenside free, clay stabilized Pickering emulsion of PCL is made with minimal organic solvent. • Organic–inorganic composite fibrous matrices were produced via emulsion electrospinning. • Fiber fineness was efficiently controlled by variation in emulsion formulation. • Fibrous matrices of high tensile strength and modulus were obtained in comparison to neat PCL matrix. • PCL/clay matrices showed effective cell proliferation as a neat PCL matrix.

Electrospun composite matrices of poly(ε-caprolactone)-montmorillonite made using tenside free Pickering emulsions

Energy Technology Data Exchange (ETDEWEB)

Samanta, Archana [Department of Textile Technology, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016 (India); Takkar, Sonam; Kulshreshtha, Ritu [Department of Biochemical Engineering and Biotechnology, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016 (India); Nandan, Bhanu [Department of Textile Technology, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016 (India); Srivastava, Rajiv K., E-mail: rajiv@textile.iitd.ac.in [Department of Textile Technology, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016 (India)

2016-12-01

The production of composite electrospun matrices of poly(ε-caprolactone) (PCL) using an emulsifier-free emulsion, made with minimal organic solvent, as precursor is reported. Pickering emulsions of PCL were prepared using modified montmorillonite (MMT) clay as the stabilizer. Hydrophobic tallow group of the modified MMT clay resulted in analogous interaction of clay with oil and aqueous phase and its adsorption at the interface to provide stability to the resultant emulsion. Composite fibrous matrices of PCL and MMT were produced using electrospinning under controlled conditions. The fiber fineness was found to alter with PCL concentration and volume fraction of the aqueous and oil phases. A higher tensile strength and modulus was obtained with inclusion of MMT in PCL electrospun matrix in comparison to a matrix made using neat PCL. The presence of clay in the fibrous matrix did not change the cell proliferation efficiency in comparison to neat PCL matrix. Composite fibrous matrices of PCL/MMT bearing enhanced tensile properties may find applications in areas other than tissue engineering for example food packaging and filtration. - Highlights: • Tenside free, clay stabilized Pickering emulsion of PCL is made with minimal organic solvent. • Organic–inorganic composite fibrous matrices were produced via emulsion electrospinning. • Fiber fineness was efficiently controlled by variation in emulsion formulation. • Fibrous matrices of high tensile strength and modulus were obtained in comparison to neat PCL matrix. • PCL/clay matrices showed effective cell proliferation as a neat PCL matrix.

Laboratory injection molder for the fabrication of polymeric porous poly-epsilon-caprolactone scaffolds for preliminary mesenchymal stem cells tissue engineering applications

KAUST Repository

Limongi, Tania

2016-12-16

This study presents a simple and rapid fabrication technique involving injection molding and particle leaching (IM/PL) to fabricate the porous scaffold for tissue engineering applications. Sodium chloride (NaCl) and Sucrose are separately mixed with the poly-epsilon-caprolactone (PCL) granules using a screwed thermo regulated extruder, than the biocompatible scaffolds are fabricated through injection molding. The micro/nano structure of the samples and their different grade of porosity were characterized by scanning electron microscopy and mercury intrusion porosimetry. Bone marrow-derived mesenchymal stem cells are chose to cell culture and Hoechst 33342 staining was used to verify the biocompatibility of the polymeric porous surfaces. We concluded that, by using the same fast solvent free injection/leaching process, the use of Sucrose as porogen, instead of NaCl, allowed the obtainment of biocompatible scaffolds with a higher grade of porosity with suitable cell adhesion capacity for tissue engineering purpose.

Three dimensional printed calcium phosphate and poly(caprolactone) composites with improved mechanical properties and preserved microstructure.

Science.gov (United States)

Vella, Joseph B; Trombetta, Ryan P; Hoffman, Michael D; Inzana, Jason; Awad, Hani; Benoit, Danielle S W

2018-03-01

Biphasic calcium phosphate scaffolds formed via three dimensional (3D) printing technology to exhibit porosity and chemical resorbability to promote osseointegration often lack the strength and toughness required to withstand loading in bone tissue engineering applications. Herein, sintering and CaP:poly(caprolactone) (PCL) composite formation were explored to improve 3D printed scaffold strength and toughness. Hydroxyapatite and α-tricalcium phosphate (α-TCP) biphasic calcium powders were printed using phosphoric acid binder, which generated monetite and hydroxyapatite scaffolds. Upon sintering, evolution of β-TCP was observed along with an increase in flexural strength and modulus but no effect on fracture toughness was observed. Furthermore, scaffold porosity increased with sintering. Additionally, two techniques of PCL composite formation were employed: postprint precipitation and 3D print codeposition to further augment scaffold mechanical properties. While both techniques significantly improved flexural strength, flexural modulus, and fracture toughness under most conditions explored, precipitation yielded more substantial increases in these properties, which is attributed to better continuity of the PCL phase. However, precipitation also compromised surface porosity due to PCL passivation of the calcium phosphate surface, which may subsequently hinder scaffold integration and bone regeneration. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 106A: 663-672, 2018. © 2017 Wiley Periodicals, Inc.

Wettability modification of electrospun poly(ε-caprolactone) fibers by femtosecond laser irradiation in different gas atmospheres

International Nuclear Information System (INIS)

He Lingna; Chen Jian; Farson, Dave F.; Lannutti, John J.; Rokhlin, Stan I.

2011-01-01

The effect of femtosecond laser irradiation in air and in O 2 and CF 4 gas flows on the wettability of electrospun poly(ε-caprolactone) fiber tissue scaffolds was studied. Laser power, focus spot size, raster scan spacing and gas atmosphere were varied in experiments. SEM imaging showed the average fiber diameter and surface porosity sizes were both altered by ablation. The micro-scale surface roughness measured by scanning laser profilometry was found to have a non-monotonic relationship to the surface wettability measured by the contact angle of sessile water droplets. In contrast, surface water contact angle continuously decreased with increased oxygen atomic percentage and oxygen-containing group fraction as measured by XPS. Further, the oxygen content was larger for more extensively ablated fiber surfaces, regardless of whether the increased ablation was caused by high laser power, smaller scanning space or smaller defocusing distance. Of the three gas atmospheres, O 2 gas flow was the most favorable environment for increasing surface oxidization, resulting in the largest water contact angle decrease for given laser power. For CF 4 gas flow, the least oxidization occurred, and the magnitude of water contact angle decrease was smallest for treatment at a given laser power.

In Vitro Degradation of Borosilicate Bioactive Glass and Poly(l-lactide-co-ε-caprolactone Composite Scaffolds

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Jenna Tainio

2017-11-01

Full Text Available Composite scaffolds were obtained by mixing various amounts (10, 30 and 50 weight % [wt %] of borosilicate bioactive glass and poly(l-lactide-co-ε-caprolactone (PLCL copolymer. The composites were foamed using supercritical CO2. An increase in the glass content led to a decrease in the pore size and density. In vitro dissolution/reaction test was performed in simulated body fluid. As a function of immersion time, the solution pH increased due to the glass dissolution. This was further supported by the increasing amount of Ca in the immersing solution with increasing immersion time and glass content. Furthermore, the change in scaffold mass was significantly greater with increasing the glass content in the scaffold. However, only the scaffolds containing 30 and 50 wt % of glasses exhibited significant hydroxyapatite (HA formation at 72 h of immersion. The compression strength of the samples was also measured. The Young’s modulus was similar for the 10 and 30 wt % glass-containing scaffolds whereas it increased to 90 MPa for the 50 wt % glass containing scaffold. Upon immersion up to 72 h, the Young’s modulus increased and then remained constant for longer immersion times. The scaffold prepared could have great potential for bone and cartilage regeneration.

Influence of Calcium Carbonate Fillers on the Properties of Recycled Poly(e-caprolactone Based Thermoplastic Polyurethane

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Vitalija BETINGYTĖ

2012-09-01

Full Text Available In this work the effects of different crystallographic modifications of calcium carbonate (CaCO3 filler on the melt flow, mechanical properties, hydrolytic degradation, and shape memory behaviour of recycled low-temperature poly(e-caprolactone-based polyurethane (rTPU were evaluated. Composites were prepared by two-roll milling varying filler content from 2 wt % to 6 wt %. It was found that at temperature range from 20 °C to 50 °C CaCO3 fillers do not change Young’s modulus, they decrease tensile stress and deformation of rTPU, but improve its mechanical properties at elevated temperatures (up to 65 °C. rTPU melt flow index increases due to chain scission during the recycling and filler mixing with mill. Therefore, destruction temperature of rTPU is 20 °C lower than that of TPU. The CaCO3 does not change shape memory properties independently of filler type and transition from secondary shape to the primary shape at 70 °C temperature is completed within 17 s for both filled and unfilled rTPU. The investigation of hydrolytic degradation shows that CaCO3 only slightly increases degradation rate of rTPU.DOI: http://dx.doi.org/10.5755/j01.ms.18.3.2433

Probing structure-antifouling activity relationships of polyacrylamides and polyacrylates.

Science.gov (United States)

Zhao, Chao; Zhao, Jun; Li, Xiaosi; Wu, Jiang; Chen, Shenfu; Chen, Qiang; Wang, Qiuming; Gong, Xiong; Li, Lingyan; Zheng, Jie

2013-07-01

We have synthesized two different polyacrylamide polymers with amide groups (polySBAA and polyHEAA) and two corresponding polyacrylate polymers without amide groups (polySBMA and polyHEA), with particular attention to the evaluation of the effect of amide group on the hydration and antifouling ability of these systems using both computational and experimental approaches. The influence of polymer architectures of brushes, hydrogels, and nanogels, prepared by different polymerization methods, on antifouling performance is also studied. SPR and ELISA data reveal that all polymers exhibit excellent antifouling ability to repel proteins from undiluted human blood serum/plasma, and such antifouling ability can be further enhanced by presenting amide groups in polySBAA and polyHEAA as compared to polySBMA and polyHEA. The antifouling performance is positively correlated with the hydration properties. Simulations confirm that four polymers indeed have different hydration characteristics, while all presenting a strong hydration overall. Integration of amide group with pendant hydroxyl or sulfobetaine group in polymer backbones is found to increase their surface hydration of polymer chains and thus to improve their antifouling ability. Importantly, we present a proof-of-concept experiment to synthesize polySBAA nanogels, which show a switchable property between antifouling and pH-responsive functions driven by acid-base conditions, while still maintaining high stability in undiluted fetal bovine serum and minimal toxicity to cultured cells. This work provides important structural insights into how very subtle structural changes in polymers can yield great improvement in biological activity, specifically the inclusion of amide group in polymer backbone/sidechain enables to obtain antifouling materials with better performance for biomedical applications. Copyright © 2013 Elsevier Ltd. All rights reserved.

Tetrazole amphiphile inducing growth of conducting polymers hierarchical nanostructures and their electromagnetic absorption properties

Science.gov (United States)

Xie, Aming; Sun, Mengxiao; Zhang, Kun; Xia, Yilu; Wu, Fan

2018-05-01

Conducting polymers (CPs) at nano scales endow materials with special optical, electrical, and magnetic properties. The crucial factor to construct and regulate the micro-structures of CPs is the inducing reagent, particular in its chemical structure, such active sites, self-assembling properties. In this paper, we design and synthesize an amphiphile bearing tetrazole moiety on its skeleton, and use this amphiphile as an inducing reagent to prepare and regulate the micro-structures of a series of CPs including polypyrrole, polyaniline, poly(3,4-ethylenedioxythiophene) and poly(p-phenylenediamine). Because of the unique electric properties of CPs and size effect, we next explored the electromagnetic absorption performances of these CPs nanostructures. A synergetic combination of electric loss and magnetic loss is used to explain the absorption mechanism of these CPs nano-structures.

Microspheres for protein delivery prepared from amphiphilic multiblock copolymers. 1. influence of preparation techniques on particle characteristics and protein delivery

NARCIS (Netherlands)

Bezemer, J.M.; Radersma, R.; Grijpma, Dirk W.; Dijkstra, Pieter J.; van Blitterswijk, Clemens; Feijen, Jan

2000-01-01

The entrapment of lysozyme in amphiphilic multiblock copolymer microspheres by emulsification and subsequent solvent removal processes was studied. The copolymers are composed of hydrophilic poly(ethylene glycol) (PEG) blocks and hydrophobic poly(butylene terephthalate) (PBT) blocks. Direct solvent

Investigation of Complexation of Linear Poly(N-vinyl-2-pyrrolidone with Poly(methacrylic acid-co-methyl methacrylate Gel

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Guoqin Liu

2011-01-01

Full Text Available The contraction of poly(methacrylic acid-co-methyl methacrylate (P(MAA-co-MMA gel induced by complexation with linear poly(N-vinyl-2-pyrrolidone (PVP is quite different from that of poly(acrylic acid (PAA or poly(methacrylic acid (PMAA gel. It was found that the concentration of PVP has a strong effect on the complexation with P(MAA-co-MMA gel. When PVP was introduced into the P(MAA-co-MMA network, its dynamic mechanic properties vary greatly between complexed and uncomplexed networks. It had the following results: (1 the higher modulus ratio; (2 a slight contraction of gel.

Copolymerization of ε-caprolactone with Epichlorohydrin by a Green Catalyst, Maghnite

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Abdelghani Bouchama

2012-06-01

Full Text Available Most of the cationic initiators used in the synthesis of copolymers are expensive. They may be poisoned by products of the reaction or impurities present in the monomer feed, and contain heavy metals, such as chromium, mercury, antimony, etc., that presents environmental disposal problems for the user. Maghnite is a montmorillonite sheet silicate clay that is exchanged with protons to produce Maghnite-H+ (Mag-H+. This non-toxic and cheaper cationic catalyst was used for the copolymerization of ε-caprolactone (CL with epichlorohydrin (ECH. The effects of the amounts of Mag-H+ and the temperature on the synthesis of poly (ε-caprolactone-co-epichlorohydrin were studied. Increasing Maghnite-H+ proportion and temperature produced the increase in copolymerization yield. The copolymer obtained was characterized by 1H-NMR and IR spectroscopy. Copyright © 2012 BCREC UNDIP. All rights reserved.Received: 24th September 2011, Revised: 12nd December 2011; Accepted: 9th January 2012[How to Cite: A. Bouchama, M.I. Ferrahi, and M. Belbachir. (2012. Copolymerization of ε-caprolactone with Epichlorohydrin by a Green Catalyst, Maghnite. Bulletin of Chemical Reaction Engineering & Catalysis, 7 (1: 43-48.  doi:10.9767/bcrec.7.1.1211.43-48][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.7.1.1211.43-48 ] | View in 

Versatile antifouling polyethersulfone filtration membranes modified via surface grafting of zwitterionic polymers from a reactive amphiphilic copolymer additive.

Science.gov (United States)

Zhao, Yi-Fan; Zhang, Pei-Bin; Sun, Jian; Liu, Cui-Jing; Yi, Zhuan; Zhu, Li-Ping; Xu, You-Yi

2015-06-15

Here we describe the development of versatile antifouling polyethersulfone (PES) filtration membranes modified via surface grafting of zwitterionic polymers from a reactive amphiphilic copolymer additive. Amphiphilic polyethersulfone-block-poly(2-hydroxyethyl methacrylate) (PES-b-PHEMA) was beforehand designed and used as the blending additive of PES membranes prepared by phase inversion technique. The surface enriched PHEMA blocks on membrane surface acted as an anchor to immobilize the initiating site. Poly(sulfobetaine methacrylate) (PSBMA) were subsequently grafted onto the PES blend membranes by surface-initiated atom transfer radical polymerization (SI-ATRP). The analysis of surface chemistry confirmed the successful grafting of zwitterionic PSBMA brushes on PES membrane surface. The resulted PES-g-PSBMA membranes were capable of separating proteins from protein solution and oil from oil/water emulsion efficiently. Furthermore, the modified membranes showed high hydrophilicity and strongly antifouling properties due to the incorporation of well-defined PSBMA layer. In addition, the PES-g-PSBMA membranes exhibited excellent blood compatibility and durability during the washing process. The developed antifouling PES membranes are versatile and can find their applications in protein filtration, blood purification and oil/water separation, etc. Copyright © 2015 Elsevier Inc. All rights reserved.

Biodegradable blends of urea plasticized thermoplastic starch (UTPS) and poly(ε-caprolactone) (PCL): Morphological, rheological, thermal and mechanical properties.

Science.gov (United States)

Correa, Ana Carolina; Carmona, Vitor Brait; Simão, José Alexandre; Capparelli Mattoso, Luiz Henrique; Marconcini, José Manoel

2017-07-01

Biodegradable blends of urea plasticized thermoplastic starch (UTPS) and poly(ε-caprolactone) (PCL) were prepared in a co-rotating twin screw extruder. The UTPS and PCL content varied in a range of 25wt%. The materials were characterized by capillary rheometry, scanning electron microscopy (SEM), termogravimetry (TGA), differential scanning calorimetry (DSC) and tensile tests. Capillary rheometry showed better interaction between UTPS and PCL at 110°C than at 130°C. SEM showed immiscibility of all blends and good dispersion of UTPS in PCL matrix up to 50wt%. However, a co-continuous morphology was found for UTPS/PCL 75/25. Thermal analysis showed that introducing PCL in UTPS, increased T onset due to higher thermal stability of PCL, and blends presented an intermediate behavior of neat polymers. The presence of PCL in blends improved significantly the mechanical properties of neat UTPS. Because they are totally biodegradable, these blends can be vehicles for controlled or slow release of nutrients to the soil while degraded. Copyright © 2017 Elsevier Ltd. All rights reserved.

Fabrication of supramolecular star-shaped amphiphilic copolymers for ROS-triggered drug release.

Science.gov (United States)

Zuo, Cai; Peng, Jinlei; Cong, Yong; Dai, Xianyin; Zhang, Xiaolong; Zhao, Sijie; Zhang, Xianshuo; Ma, Liwei; Wang, Baoyan; Wei, Hua

2018-03-15

Star-shaped copolymers with branched structures can form unimolecular micelles with better stability than the micelles self-assembled from conventional linear copolymers. However, the synthesis of star-shaped copolymers with precisely controlled degree of branching (DB) suffers from complicated sequential polymerizations and multi-step purification procedures, as well as repeated optimizations of polymer compositions. The use of a supramolecular host-guest pair as the block junction would significantly simplify the preparation. Moreover, the star-shaped copolymer-based unimolecular micelle provides an elegant solution to the tradeoff between extracellular stability and intracellular high therapeutic efficacy if the association/dissociation of the supramolecular host-guest joint can be triggered by the biologically relevant stimuli. For this purpose, in this study, a panel of supramolecular star-shaped amphiphilic block copolymers with 9, 12, and 18 arms were designed and fabricated by host-guest complexations between the ring-opening polymerization (ROP)-synthesized star-shaped poly(ε-caprolactone) (PCL) with 3, 4, and 6 arms end-capped with ferrocene (Fc) (PCL-Fc) and the atom transfer radical polymerization (ATRP)-produced 3-arm poly(oligo ethylene glycol) methacrylates (POEGMA) with different degrees of polymerization (DPs) of 24, 30, 47 initiated by β-cyclodextrin (β-CD) (3Br-β-CD-POEGMA). The effect of DB and polymer composition on the self-assembled properties of the five star-shaped copolymers was investigated by dynamic light scattering (DLS), transmission electron microscopy (TEM), and fluorescence spectrometery. Interestingly, the micelles self-assembled from 12-arm star-shaped copolymers exhibited greater stability than the 9- and 18-arm formulations. The potential of the resulting supramolecular star-shaped amphiphilic copolymers as drug carriers was evaluated by an in vitro drug release study, which confirmed the ROS-triggered accelerated drug

Structurally Stable Attractive Nanoscale Emulsions with Dipole-Dipole Interaction-Driven Interdrop Percolation.

Science.gov (United States)

Shin, Kyounghee; Gong, Gyeonghyeon; Cuadrado, Jonas; Jeon, Serim; Seo, Mintae; Choi, Hong Sung; Hwang, Jae Sung; Lee, Youngbok; Fernandez-Nieves, Alberto; Kim, Jin Woong

2017-03-28

This study introduces an extremely stable attractive nanoscale emulsion fluid, in which the amphiphilic block copolymer, poly(ethylene oxide)-block-poly(ϵ-caprolactone) (PEO-b-PCL), is tightly packed with lecithin, thereby forming a mechanically robust thin-film at the oil-water interface. The molecular association of PEO-b-PCL with lecithin is critical for formation of a tighter and denser molecular assembly at the interface, which is systematically confirmed by T 2 relaxation and DSC analyses. Moreover, suspension rheology studies also reflect the interdroplet attractions over a wide volume fraction range of the dispersed oil phase; this results in a percolated network of stable drops that exhibit no signs of coalescence or phase separation. This unique rheological behavior is attributed to the dipolar interaction between the phosphorylcholine groups of lecithin and the methoxy end groups of PEO-b-PCL. Finally, the nanoemulsion system significantly enhances transdermal delivery efficiency due to its favorable attraction to the skin, as well as high diffusivity of the nanoscale emulsion drops. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrospun gelatin/sodium bicarbonate and poly(lactide-co-ε-caprolactone)/sodium bicarbonate nanofibers as drug delivery systems.

Science.gov (United States)

Sang, Qingqing; Williams, Gareth R; Wu, Huanling; Liu, Kailin; Li, Heyu; Zhu, Li-Min

2017-12-01

In this work, we report electrospun nanofibers made of model hydrophobic (poly(lactide-co-ε-caprolactone); PLCL) and hydrophilic (gelatin) polymers. We explored the effect on drug release of the incorporation of sodium bicarbonate (SB) into these fibers, using the potent antibacterial agent ciprofloxacin as a model drug. The fibers prepared are smooth and have relatively uniform diameters lying between ca. 600 and 850nm. The presence of ciprofloxacin in the fibers was confirmed using IR spectroscopy. X-ray diffraction showed the drug to be incorporated into the fibers in the amorphous form. In vitro drug release studies revealed that, as expected, more rapid drug release was seen with gelatin fibers than those made of PLCL, and a greater final release percentage was obtained. The inclusion of SB in the gelatin fibers imparts them with pH sensitivity: gelatin/SB fibers showed faster release at pH5 than pH7.4, while fibers without SB gave the same release profiles at both pHs. The PLCL fibers have no pH sensitivity, even when SB was included, as a result of their hydrophobic structure precluding the ingress of solvent. In vitro cell culture studies showed that all the fibers are able to promote cell proliferation. The ciprofloxacin loaded fibers are effective in inhibiting Escherichia coli and Staphylococcus aureus growth in antibacterial tests. Thus, the gelatin-based fibers can be used as pH-responsive drug delivery systems, with potential applications for instance in the treatment of tumor resection sites. Should these become infected, the pH would drop, resulting in ciprofloxacin being released and the infection halted. Crown Copyright © 2017. Published by Elsevier B.V. All rights reserved.

Synthesis and Swelling Behavior of pH-Sensitive Semi-IPN Superabsorbent Hydrogels Based on Poly(acrylic acid Reinforced with Cellulose Nanocrystals

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Lim Sze Lim

2017-11-01

Full Text Available pH-sensitive poly(acrylic acid (PAA hydrogel reinforced with cellulose nanocrystals (CNC was prepared. Acrylic acid (AA was subjected to chemical cross-linking using the cross-linking agent MBA (N,N-methylenebisacrylamide with CNC entrapped in the PAA matrix. The quantity of CNC was varied between 0, 5, 10, 15, 20, and 25 wt %. X-ray diffraction (XRD data showed an increase in crystallinity with the addition of CNC, while rheology tests demonstrated a significant increase in the storage modulus of the hydrogel with an increase in CNC content. It was found that the hydrogel reached maximum swelling at pH 7. The potential of the resulting hydrogels to act as drug carriers was then evaluated by means of the drug encapsulation efficiency test using theophylline as a model drug. It was observed that 15% CNC/PAA hydrogel showed the potential to be used as drug carrier system.

ULTRAFILTRATION AS PRETREATMENT OF REVERSE OSMOSIS: LOW FOULING ULTRAFILTRATION MEMBRANE PREPARED FROM POLYETHERSULFONE–AMPHIPHILIC BLOCK COPOLYMER BLEND

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Heru Susanto

2012-02-01

Full Text Available This paper demonstrates the preparation of polyethersulfone (PES ultrafiltration (UF membranes via wet phase inversion method using either poly(ethylene oxide-b-poly(propylene oxide-b- poly(ethylene oxide (Pluronic®, Plu or polyethylene glycol (PEG as hydrophilic modifier. Their effects on membrane structure as well as the resulting membrane performance and their stability in membrane polymer matrix were systematically investigated. The investigated membrane characteristics include surface hydrophilicity (by contact angle, surface chemistry (by FTIR spectroscopy and water flux measurement. Visualization of membrane surface and cross section morphology was also done by scanning electron microscopy. The membrane performance was examined by investigation of adsorptive fouling and ultrafiltration using solution of bovine serum albumin as the model system. The stability of additive was examined by incubating the membrane in water (40oC for up to 10 days. The results show that modification effects on membrane characteristic and low fouling behavior were clearly observed. Further, amphiphilic Pluronic generally showed better performance than PEG.   

Evaluation of the antifouling and photocatalytic properties of poly(vinylidene fluoride) plasma-grafted poly(acrylic acid) membrane with self-assembled TiO{sub 2}

Energy Technology Data Exchange (ETDEWEB)

You, Sheng-Jie, E-mail: sjyou@cycu.edu.tw [Department of Bioenvironmental Engineering, Chung Yuan Christian University, Chungli, Taiwan (China); R and D Center for Membrane Technology, Chung Yuan Christian University, Chungli, Taiwan (China); Semblante, Galilee Uy [Department of Bioenvironmental Engineering, Chung Yuan Christian University, Chungli, Taiwan (China); R and D Center for Membrane Technology, Chung Yuan Christian University, Chungli, Taiwan (China); Lu, Shao-Chung [Department of Civil Engineering, Chung Yuan Christian University, Chungli, Taiwan (China); Damodar, Rahul A. [Department of Bioenvironmental Engineering, Chung Yuan Christian University, Chungli, Taiwan (China); R and D Center for Membrane Technology, Chung Yuan Christian University, Chungli, Taiwan (China); Wei, Ta-Chin [R and D Center for Membrane Technology, Chung Yuan Christian University, Chungli, Taiwan (China); Department of Chemical Engineering, Chung Yuan Christian University, Chungli, Taiwan (China)

2012-10-30

Highlights: Black-Right-Pointing-Pointer Plasma and grafting parameters that maximized TiO{sub 2} binding sites were found. Black-Right-Pointing-Pointer PVDF hydrophilicity was vastly improved compared to other modification techniques. Black-Right-Pointing-Pointer At least 1.5% TiO{sub 2} and 30 min UV exposure were needed to attain full flux recovery. Black-Right-Pointing-Pointer Photocatalytic membranes could remove up to 42% of 50 mg/l RB5 dye. - Abstract: Immobilization of TiO{sub 2} is a promising approach that produces antifouling and photocatalytic membranes that could help advance wastewater treatment and re-use processes. In this study, poly(acrylic acid) (PAA) was plasma-grafted on commercial poly(vinylidene fluoride) (PVDF) to introduce functional groups on the membrane surface that can support the nanoparticles. It was found that plasma treatment at 100 W for 120 s followed by liquid grafting with 70% aqueous AA at 60 Degree-Sign C for 2 h maximized the number of TiO{sub 2} binding sites. Membrane hydrophilicity was tremendously enhanced by the self-assembly of TiO{sub 2}, following a direct proportionality to TiO{sub 2} loading. The membrane with 0.5% TiO{sub 2} loading maintained the highest pure water flux and the best protein antifouling property. UV irradiation triggered the photodegradation of strongly bound foulants, but at least 1.5% TiO{sub 2} and 30 min cumulative irradiation were necessary to completely recover the membrane's original performance. The TiO{sub 2}-modified membranes removed 30-42% of 50 mg/l aqueous Reactive Black 5 (RB5) dye. The fabricated membranes demonstrate huge potential for use in membrane reactors with high hydrophilicity, fouling mitigation, and photocatalytic capability.

C3 toxin and poly-DL-lactide-ε-caprolactone conduits in the critically damaged peripheral nervous system: a combined therapeutic approach.

Science.gov (United States)

Leibig, Nico; Boyle, Veronika; Kraus, Daniel; Stark, Gerhard Bjoern; Penna, Vincenzo

2015-03-01

Peripheral nerve regeneration over longer distances through conduits is limited. In the presented study, critical size nerve gap bridging with a poly-DL-lactide-ε-caprolactone (PLC) conduit was combined with application of C3 toxin to facilitate axonal sprouting. The PLC filled with fibrin (n = 10) and fibrin gel loaded with 1-μg C3-C2I and 2-μg C2II (n = 10) were compared to autologous nerve grafts (n = 10) in a 15-mm sciatic nerve gap lesion model of the rat. Functional and electrophysiological analyses were performed before histological evaluation. Evaluation of motor function and nerve conduction velocity at 16 weeks revealed no differences between the groups. All histological parameters and muscle weight were significantly elevated in nerve graft group. No differences were observed in both PLC groups. The PLCs are permissive for nerve regeneration over a 15-mm defect in rats. Intraluminal application of C3 toxin did not lead to significant enhancement of nerve sprouting.

Irradiation of polyacrylate compositions in air

International Nuclear Information System (INIS)

Wendling, L.A.; Covington, J.B.

1983-01-01

The invention relates to processes for polymerizing polyacrylate functional compositions and in particular to processes for the curing in air of certain polyacrylate functional materials by irradiation

Dually cross-linked single network poly(acrylic acid) hydrogels with superior mechanical properties and water absorbency.

Science.gov (United States)

Zhong, Ming; Liu, Yi-Tao; Liu, Xiao-Ying; Shi, Fu-Kuan; Zhang, Li-Qin; Zhu, Mei-Fang; Xie, Xu-Ming

2016-06-28

Poly(acrylic acid) (PAA) hydrogels with superior mechanical properties, based on a single network structure with dual cross-linking, are prepared by one-pot free radical polymerization. The network structure of the PAA hydrogels is composed of dual cross-linking: a dynamic and reversible ionic cross-linking among the PAA chains enabled by Fe(3+) ions, and a sparse covalent cross-linking enabled by a covalent cross-linker (Bis). Under deformation, the covalently cross-linked PAA chains remain intact to maintain their original configuration, while the Fe(3+)-enabled ionic cross-linking among the PAA chains is broken to dissipate energy and then recombined. It is found that the mechanical properties of the PAA hydrogels are significantly influenced by the contents of covalent cross-linkers, Fe(3+) ions and water, which can be adjusted within a substantial range and thus broaden the applications of the hydrogels. Meanwhile, the PAA hydrogels have excellent recoverability based on the dynamic and reversible ionic cross-linking enabled by Fe(3+) ions. Moreover, the swelling capacity of the PAA hydrogels is as high as 1800 times in deionized water due to the synergistic effects of ionic and covalent cross-linkings. The combination of balanced mechanical properties, efficient recoverability, high swelling capacity and facile preparation provides a new method to obtain high-performance hydrogels.

3D- Printed Poly(ε-caprolactone) Scaffold Integrated with Cell-laden Chitosan Hydrogels for Bone Tissue Engineering.

Science.gov (United States)

Dong, Liang; Wang, Shao-Jie; Zhao, Xin-Rong; Zhu, Yu-Fang; Yu, Jia-Kuo

2017-10-17

Synthetic polymeric scaffolds are commonly used in bone tissue engineering (BTE) due to their biocompatibility and adequate mechanical properties. However, their hydrophobicity and the lack of specific cell recognition sites confined their practical application. In this study, to improve the cell seeding efficiency and osteoinductivity, an injectable thermo-sensitive chitosan hydrogel (CSG) was incorporated into a 3D-printed poly(ε-caprolactone) (PCL) scaffold to form a hybrid scaffold. To demonstrate the feasibility of this hybrid system for BTE application, rabbit bone marrow mesenchymal stem cells (BMMSCs) and bone morphogenetic protein-2 (BMP-2) were encapsulated in CSG. Pure PCL scaffolds were used as controls. Cell proliferation and viability were investigated. Osteogenic gene expressions of BMMSCs in various scaffolds were determined with reverse transcription polymerase chain reaction (RT-PCR). Growth factor releasing profile and mechanical tests were performed. CCK-8 assay confirmed greater cell retention and proliferation in chitosan and hybrid groups. Confocal microscopy showed even distribution of cells in the hybrid system. After 2-week osteogenic culture in vitro, BMMSCs in hybrid and chitosan scaffolds showed stronger osteogenesis and bone-matrix formation. To conclude, chitosan/PCL hybrid scaffolds are a favorable platform for BTE due to its capacity to carry cells and drugs, and excellent mechanical strength.

A Long-Acting BMP-2 Release System Based on Poly(3-hydroxybutyrate) Nanoparticles Modified by Amphiphilic Phospholipid for Osteogenic Differentiation

Science.gov (United States)

Peng, Xiaochun; Chen, Yunsu; Li, Yamin; Wang, Yiming

2016-01-01

We explored a novel poly(3-hydroxybutyrate) (PHB) nanoparticle loaded with hydrophilic recombinant human BMP-2 with amphiphilic phospholipid (BPC-PHB NP) for a rapid-acting and long-acting delivery system of BMP-2 for osteogenic differentiation. The BPC-PHB NPs were prepared by a solvent evaporation method and showed a spherical particle with a mean particle size of 253.4 nm, mean zeta potential of −22.42 mV, and high entrapment efficiency of 77.18%, respectively. For BPC-PHB NPs, a short initial burst release of BMP-2 from NPs in 24 h was found and it has steadily risen to reach about 80% in 20 days for in vitro test. BPC-PHB NPs significantly reduced the burst release of BMP-2, as compared to that of PHB NPs loading BMP-2 without PL (B-PHB NPs). BPC-PHB NPs maintained the content of BMP-2 for a long-term osteogenic differentiation. The OCT-1 cells with BPC-PHB NPs have high ALP activity in comparison with others. The gene markers for osteogenic differentiation were significantly upregulated for sample with BPC-PHB NPs, implying that BPC-PHB NPs can be used as a rapid-acting and long-acting BMP-2 delivery system for osteogenic differentiation. PMID:27379249

Novel poly(ε-caprolactone)/gelatin wound dressings prepared by emulsion electrospinning with controlled release capacity of Ketoprofen anti-inflammatory drug.

Science.gov (United States)

Basar, A O; Castro, S; Torres-Giner, S; Lagaron, J M; Turkoglu Sasmazel, H

2017-12-01

In the present study, a single and binary Ketoprofen-loaded mats of ultrathin fibers were developed by electrospinning and their physical properties and drug release capacity was analyzed. The single mat was prepared by solution electrospinning of poly(ε-caprolactone) (PCL) with Ketoprofen at a weight ratio of 5wt%. This Ketoprofen-containing PCL solution was also used as the oil phase in a 7:3 (wt/wt) emulsion with gelatin dissolved in acidified water. The resultant stable oil-in-water (O/W) emulsion of PCL-in-gelatin, also containing Ketoprofen at 5wt%, was electrospun to produce the binary mat. Cross-linking process was performed by means of glutaraldehyde vapor on the electrospun binary mat to prevent dissolution of the hydrophilic gelatin phase. The performed characterization indicated that Ketoprofen was successfully embedded in the single and binary electrospun mats, i.e. PCL and PCL/gelatin, and both mats showed high hydrophobicity but poor thermal resistance. In vitro release studies interestingly revealed that, in comparison to the single PCL electrospun mat, the binary PCL/gelatin mat significantly hindered Ketoprofen burst release and exhibited a sustained release capacity of the drug for up to 4days. In addition, the electrospun Ketoprofen-loaded mats showed enhanced attachment and proliferation of L929 mouse fibroblast cells, presenting the binary mat the highest cell growth yield due to its improved porosity. The here-developed electrospun materials clearly show a great deal of potential as novel wound dressings with an outstanding controlled capacity to release drugs. Copyright © 2017 Elsevier B.V. All rights reserved.

Temperature-responsive poly(ε-caprolactone) cell culture platform with dynamically tunable nano-roughness and elasticity for control of myoblast morphology.

Science.gov (United States)

Uto, Koichiro; Ebara, Mitsuhiro; Aoyagi, Takao

2014-01-21

We developed a dynamic cell culture platform with dynamically tunable nano-roughness and elasticity. Temperature-responsive poly(ε-caprolactone) (PCL) films were successfully prepared by crosslinking linear and tetra-branched PCL macromonomers. By optimizing the mixing ratios, the crystal-amorphous transition temperature (Tm) of the crosslinked film was adjusted to the biological relevant temperature (~33 °C). While the crosslinked films are relatively stiff (50 MPa) below the Tm, they suddenly become soft (1 MPa) above the Tm. Correspondingly, roughness of the surface was decreased from 63.4-12.4 nm. It is noted that the surface wettability was independent of temperature. To investigate the role of dynamic surface roughness and elasticity on cell adhesion, cells were seeded on PCL films at 32 °C. Interestingly, spread myoblasts on the film became rounded when temperature was suddenly increased to 37 °C, while significant changes in cell morphology were not observed for fibroblasts. These results indicate that cells can sense dynamic changes in the surrounding environment but the sensitivity depends on cell types.

Two Players Make a Formidable Combination: In Situ Generated Poly(acrylic anhydride-2-methyl-acrylic acid-2-oxirane-ethyl ester-methyl methacrylate) Cross-Linking Gel Polymer Electrolyte toward 5 V High-Voltage Batteries.

Science.gov (United States)

Ma, Yue; Ma, Jun; Chai, Jingchao; Liu, Zhihong; Ding, Guoliang; Xu, Gaojie; Liu, Haisheng; Chen, Bingbing; Zhou, Xinhong; Cui, Guanglei; Chen, Liquan

2017-11-29

Electrochemical performance of high-voltage lithium batteries with high energy density is limited because of the electrolyte instability and the electrode/electrolyte interfacial reactivity. Hence, a cross-linking polymer network of poly(acrylic anhydride-2-methyl-acrylic acid-2-oxirane-ethyl ester-methyl methacrylate) (PAMM)-based electrolyte was introduced via in situ polymerization inspired by "shuangjian hebi", which is a statement in a traditional Chinese Kungfu story similar to the synergetic effect of 1 + 1 > 2. A poly(acrylic anhydride) and poly(methyl methacrylate)-based system is very promising as electrolyte materials for lithium-ion batteries, in which the anhydride and acrylate groups can provide high voltage resistance and fast ionic conductivity, respectively. As a result, the cross-linking PAMM-based electrolyte possesses a significant comprehensive enhancement, including electrochemical stability window exceeding 5 V vs Li + /Li, an ionic conductivity of 6.79 × 10 -4 S cm -1 at room temperature, high mechanical strength (27.5 MPa), good flame resistance, and excellent interface compatibility with Li metal. It is also demonstrated that this gel polymer electrolyte suppresses the negative effect resulting from dissolution of Mn 2+ ions at 25 and 55 °C. Thus, the LiNi 0.5 Mn 1.5 O 4 /Li and LiNi 0.5 Mn 1.5 O 4 /Li 4 Ti 5 O 12 cells using the optimized in situ polymerized cross-linking PAMM-based gel polymer electrolyte deliver stable charging/discharging profiles and excellent rate performance at room temperature and even at 55 °C. These findings suggest that the cross-linking PAMM is an intriguing candidate for 5 V class high-voltage gel polymer electrolyte toward high-energy lithium-on batteries.

Self-assembly of Polystyrene- b -poly(2-vinylpyridine)- b -poly(ethylene oxide) Triblock Terpolymers

KAUST Repository

Musteata, Valentina-Elena; Sutisna, Burhannudin; Polymeropoulos, Georgios; Avgeropoulos, Apostolos; Meneau, Florian; Peinemann, Klaus-Viktor; Hadjichristidis, Nikolaos; Nunes, Suzana Pereira

2017-01-01

Polystyrene-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO) terpolymer is a versatile polymer to form isoporous films and membranes, due to the possibility of self-assembly control and the properties of the different blocks, such as the P2VP ability of complexation, and H-bond formation, and the PEO biocompatibility. Copolymers with different block ratios and sizes were synthesized. The correlation between their equilibrium bulk morphology, the self-assembly in dilute and semi-dilute solutions and the non-equilibrium porous structures of membranes, obtained by non-solvent induced phase separation, was investigated and discussed in detail. The characterization was performed by small-angle X-ray scattering (SAXS), scanning (SEM) and transmission electron microscopy (TEM). Hexagonal, cubic and lamellar arrangements were observed. The preparation conditions were optimized and a regular, isoporous morphology, suitable for membrane application, was successfully obtained with PS80.5k-b-P2VP64.4k-b-PEO16.1k.

Self-assembly of Polystyrene- b -poly(2-vinylpyridine)- b -poly(ethylene oxide) Triblock Terpolymers

KAUST Repository

Musteata, Valentina-Elena

2017-11-08

Polystyrene-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO) terpolymer is a versatile polymer to form isoporous films and membranes, due to the possibility of self-assembly control and the properties of the different blocks, such as the P2VP ability of complexation, and H-bond formation, and the PEO biocompatibility. Copolymers with different block ratios and sizes were synthesized. The correlation between their equilibrium bulk morphology, the self-assembly in dilute and semi-dilute solutions and the non-equilibrium porous structures of membranes, obtained by non-solvent induced phase separation, was investigated and discussed in detail. The characterization was performed by small-angle X-ray scattering (SAXS), scanning (SEM) and transmission electron microscopy (TEM). Hexagonal, cubic and lamellar arrangements were observed. The preparation conditions were optimized and a regular, isoporous morphology, suitable for membrane application, was successfully obtained with PS80.5k-b-P2VP64.4k-b-PEO16.1k.

Nanoparticles Embedded in Amphiphilic Membranes for Carbon Dioxide Separation and Dehumidification.

Science.gov (United States)

Yong, Wai Fen; Ho, Yan Xun; Chung, Tai-Shung

2017-10-23

Polymers containing ethylene oxide (EO) groups have gained significant interest as the EO groups have favorable interactions with polar molecules such as H 2 O, quadrupolar molecules such as CO 2 , and metal ions. However, the main challenges of poly(ethylene oxide) (PEO) membranes are their weak mechanical properties and high crystallinity nature. The amphiphilic copolymer made from PEO terephthalate and poly(butylene terephthalate) (PEOT/PBT) comprises both hydrophilic and hydrophobic segments. The hydrophilic PEOT segment is thermosensitive, which facilities gas transports whereas the hydrophobic PBT segment is rigid, which provides mechanical robustness. This work demonstrates a new strategy to design amphiphilic mixed matrix membranes (MMMs) by incorporating zeolitic imidazolate framework, ZIF-71, into the PEOT/PBT copolymer. The resultant membrane shows an enhanced CO 2 permeability with an ideal CO 2 /N 2 selectivity surpassing the original PEOT/PBT and Robeson's Upper bound line. The nanoparticles-embedded amphiphilic membranes exhibit characteristics of high transparency and mechanical robustness. Mechanically strong composite hollow fiber membranes consisting of PEOT/PBT/ZIF-71 as the selective layer were also prepared. The resultant hollow fibers possess an excellent CO 2 permeance of 131 GPU (gas permeation units), CO 2 /N 2 selectivity of 52.6, H 2 O permeance of 9300 GPU and H 2 O/N 2 selectivity of 3700, showing great potential for industrial CO 2 capture and dehumidification. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ibuprofen-loaded poly(trimethylene carbonate-co-ε-caprolactone) electrospun fibres for nerve regeneration.

Science.gov (United States)

Pires, Liliana R; Guarino, Vincenzo; Oliveira, Maria J; Ribeiro, Cristina C; Barbosa, Mário A; Ambrosio, Luigi; Pêgo, Ana Paula

2016-03-01

The development of scaffolds that combine the delivery of drugs with the physical support provided by electrospun fibres holds great potential in the field of nerve regeneration. Here it is proposed the incorporation of ibuprofen, a well-known non-steroidal anti-inflammatory drug, in electrospun fibres of the statistical copolymer poly(trimethylene carbonate-co-ε-caprolactone) [P(TMC-CL)] to serve as a drug delivery system to enhance axonal regeneration in the context of a spinal cord lesion, by limiting the inflammatory response. P(TMC-CL) fibres were electrospun from mixtures of dichloromethane (DCM) and dimethylformamide (DMF). The solvent mixture applied influenced fibre morphology, as well as mean fibre diameter, which decreased as the DMF content in solution increased. Ibuprofen-loaded fibres were prepared from P(TMC-CL) solutions containing 5% ibuprofen (w/w of polymer). Increasing drug content to 10% led to jet instability, resulting in the formation of a less homogeneous fibrous mesh. Under the optimized conditions, drug-loading efficiency was above 80%. Confocal Raman mapping showed no preferential distribution of ibuprofen in P(TMC-CL) fibres. Under physiological conditions ibuprofen was released in 24 h. The release process being diffusion-dependent for fibres prepared from DCM solutions, in contrast to fibres prepared from DCM-DMF mixtures where burst release occurred. The biological activity of the drug released was demonstrated using human-derived macrophages. The release of prostaglandin E2 to the cell culture medium was reduced when cells were incubated with ibuprofen-loaded P(TMC-CL) fibres, confirming the biological significance of the drug delivery strategy presented. Overall, this study constitutes an important contribution to the design of a P(TMC-CL)-based nerve conduit with anti-inflammatory properties. Copyright © 2013 John Wiley & Sons, Ltd.

Preliminary In Vitro Assessment of Stem Cell Compatibility with Cross-Linked Poly(ε-caprolactone urethane Scaffolds Designed through High Internal Phase Emulsions

Directory of Open Access Journals (Sweden)

Sylvie Changotade

2015-01-01

Full Text Available By using a high internal phase emulsion process, elastomeric poly(ε-caprolactone urethane (PCLU scaffolds were designed with pores size ranging from below 150 μm to 1800 μm and a porosity of 86% making them suitable for bone tissue engineering applications. Moreover, the pores appeared to be excellently interconnected, promoting cellularization and future bone ingrowth. This study evaluated the in vitro cytotoxicity of the PCLU scaffolds towards human mesenchymal stem cells (hMSCs through the evaluation of cell viability and metabolic activity during extract test and indirect contact test at the beginning of the scaffold lifetime. Both tests demonstrated that PCLU scaffolds did not induce any cytotoxic response. Finally, direct interaction of hMSCs and PCLU scaffolds showed that PCLU scaffolds were suitable for supporting the hMSCs adhesion and that the cells were well spread over the pore walls. We conclude that PCLU scaffolds may be a good candidate for bone tissue regeneration applications using hMSCs.

Development of controlled release formulations of azadirachtin-A employing poly(ethylene glycol) based amphiphilic copolymers.

Science.gov (United States)

Kumar, Jitendra; Shakil, Najam A; Singh, Manish K; Singh, Mukesh K; Pandey, Alka; Pandey, Ravi P

2010-05-01

Controlled release (CR) formulations of azadirachtin-A, a bioactive constituent derived from the seed of Azadirachta indica A. Juss (Meliaceae), have been prepared using commercially available polyvinyl chloride, polyethylene glycol (PEG) and laboratory synthesized poly ethylene glycol-based amphiphilic copolymers. Copolymers of polyethylene glycol and various dimethyl esters, which self assemble into nano micellar aggregates in aqueous media, have been synthesized. The kinetics of azadirachtin-A, release in water from the different formulations was studied. Release from the commercial polyethylene glycol (PEG) formulation was faster than the other CR formulations. The rate of release of encapsulated azadirachtin-A from nano micellar aggregates is reduced by increasing the molecular weight of PEG. The diffusion exponent (n value) of azadirachtin-A, in water ranged from 0.47 to 1.18 in the tested formulations. The release was diffusion controlled with a half release time (t(1/2)) of 3.05 to 42.80 days in water from different matrices. The results suggest that depending upon the polymer matrix used, the application rate of azadirachtin-A can be optimized to achieve insect control at the desired level and period.

Preparation and characterization of monomethoxy poly(ethylene glycol-poly(ε-caprolactone micelles for the solubilization and in vivo delivery of luteolin

Directory of Open Access Journals (Sweden)

Qiu JF

2013-08-01

Full Text Available Jin-Feng Qiu,1 Xiang Gao,1,2 Bi-Lan Wang,1 Xia-Wei Wei,1 Ma-Ling Gou,1 Ke Men,1 Xing-Yu Liu,1 Gang Guo,1 Zhi-Yong Qian,1 Mei-Juan Huang1 1Department of Thoracic Oncology, State Key Laboratory of Biotherapy and Cancer Center, West China Hospital and Medical School, Sichuan University, Chengdu, People’s Republic of China; 2Medical School and Department of Pathophysiology, College of Preclinical and Forensic Medical Sciences, Sichuan University, Chengdu, People’s Republic of China Abstract: Luteolin (Lu is one of the flavonoids with anticancer activity, but its poor water solubility limits its use clinically. In this work, we used monomethoxy poly(ethylene glycol-poly(ε-caprolactone (MPEG-PCL micelles to encapsulate Lu by a self-assembly method, creating a water-soluble Lu/MPEG-PCL micelle. These micelles had a mean particle size of 38.6 ± 0.6 nm (polydispersity index = 0.16 ± 0.02, encapsulation efficiency of 98.32% ± 1.12%, and drug loading of 3.93% ± 0.25%. Lu/MPEG-PCL micelles could slowly release Lu in vitro. Encapsulation of Lu in MPEG-PCL micelles improved the half-life (t½; 152.25 ± 49.92 versus [vs] 7.16 ± 1.23 minutes, P = 0.007, area under the curve (0–t (2914.05 ± 445.17 vs 502.65 ± 140.12 mg/L/minute, P = 0.001, area under the curve (0–∞ (2989.03 ± 433.22 vs 503.81 ± 141.41 mg/L/minute, P = 0.001, and peak concentration (92.70 ± 11.61 vs 38.98 ± 7.73 mg/L, P = 0.003 of Lu when the drug was intravenously administered at a dose of 30 mg/kg in rats. Also, Lu/MPEG-PCL micelles maintained the cytotoxicity of Lu on 4T1 breast cancer cells (IC50 = 6.4 ± 2.30 µg/mL and C-26 colon carcinoma cells (IC50 = 12.62 ± 2.17 µg/mL in vitro. These data suggested that encapsulation of Lu into MPEG-PCL micelles created an aqueous formulation of Lu with potential anticancer effect. Keywords: luteolin, micelle, MPEG-PCL, cancer therapy

Inorganic-organic hybrids based on poly (ε-Caprolactone and silica oxide and characterization by relaxometry applying low-field NMR

Directory of Open Access Journals (Sweden)

Mariana Sato de Souza de Bustamante Monteiro

2012-12-01

Full Text Available Poly (ε-caprolactone (PCL based hybrids containing different amounts of modified (Aerosil® R972 and unmodified (Aerosil® A200 silica oxide were prepared employing the solution method, using chloroform. The relationships of the amount of nanofillers, organic coating, molecular structure and intermolecular interaction of the hybrid materials were investigated mainly using low-field nuclear magnetic resonance (NMR. The NMR analyses involved the hydrogen spin-lattice relaxation time (T1H and hydrogen spin-lattice relaxation time in the rotating frame (T1ρH. The spin-lattice relaxation time measurements revealed that the PCL/silica oxide hybrids were heterogeneous, meaning their components were well dispersed. X-ray diffraction (XRD, differential scanning calorimetry (DSC and thermogravimetric analysis (TGA were also employed. The DSC data showed that all the materials had lower crystallization temperature (Tc and melting temperature (Tm, so the crystallinity degree of the PCL decreased in the hybrids. The TGA analysis demonstrated that the addition of modified and unmodified silica oxide does not cause considerable changes to PCL's thermal stability, since no significant variations in the maximum temperature (Tmax were observed in relation to the neat polymer.

Drug-loaded poly (ε-caprolactone)/Fe3O4 composite microspheres for magnetic resonance imaging and controlled drug delivery

Science.gov (United States)

Wang, Guangshuo; Zhao, Dexing; Li, Nannan; Wang, Xuehan; Ma, Yingying

2018-06-01

In this study, poly (ε-caprolactone) (PCL) microspheres loading magnetic Fe3O4 nanoparticles and anti-cancer drug of doxorubicin hydrochloride (DOX) were successfully prepared by a modified solvent-evaporation method. The obtained magnetic composite microspheres exhibited dual features of magnetic resonance imaging and controlled drug delivery. The morphology, structure, thermal behavior and magnetic properties of the drug-loaded magnetic microspheres were investigated in detail by SEM, XRD, DSC and SQUID. The obtained composite microspheres showed superparamagnetic behavior and T2-weighted enhancement effect. The drug loading, encapsulation efficiency, releasing behavior and in vitro cytotoxicity of the drug-loaded composite microspheres were systematically investigated. It was found that the values of drug loading and encapsulation efficiency were 36.7% and 25.8%, respectively. The composite microspheres were sensitive to pH and released in a sustained way, and both the release curves under various pH conditions (4.0 and 7.4) were well satisfied with the biphase kinetics function. In addition, the magnetic response of the drug-loaded microspheres was studied and the results showed that the composite microspheres had a good magnetic stability and strong targeting ability.

Chitosan functionalized poly-ε-caprolactone electrospun fibers and 3D printed scaffolds as antibacterial materials for tissue engineering applications.

Science.gov (United States)

Tardajos, Myriam G; Cama, Giuseppe; Dash, Mamoni; Misseeuw, Lara; Gheysens, Tom; Gorzelanny, Christian; Coenye, Tom; Dubruel, Peter

2018-07-01

Tissue engineering (TE) approaches often employ polymer-based scaffolds to provide support with a view to the improved regeneration of damaged tissues. The aim of this research was to develop a surface modification method for introducing chitosan as an antibacterial agent in both electrospun membranes and 3D printed poly-ε-caprolactone (PCL) scaffolds. The scaffolds were functionalized by grafting methacrylic acid N-hydroxysuccinimide ester (NHSMA) onto the surface after Ar-plasma/air activation. Subsequently, the newly-introduced NHS groups were used to couple with chitosan of various molecular weights (Mw). High Mw chitosan exhibited a better coverage of the surface as indicated by the higher N% detected by X-ray photoelectron spectroscopy (XPS) and the observations with either scanning electron microscopy (SEM)(for fibers) or Coomassie blue staining (for 3D-printed scaffolds). A lactate dehydrogenase assay (LDH) using L929 fibroblasts demonstrated the cell-adhesion and cell-viability capacity of the modified samples. The antibacterial properties against S. aureus ATCC 6538 and S. epidermidis ET13 revealed a slower bacterial growth rate on the surface of the chitosan modified scaffolds, regardless the chitosan Mw. Copyright © 2018 Elsevier Ltd. All rights reserved.

Unconventional, amphiphilic polymers based on chiral polyethylene oxide derivatives I. Synthesis and Characterization.

NARCIS (Netherlands)

Janssen, H.M.; Peeters, E.; Zundert, van M.F.; Genderen, van M.H.P.; Meijer, E.W.

1997-01-01

The first representatives of a new class of synthetic, amphiphilic polymers based on poly(ethylene oxide) are introduced. These polymers are constituted in a similar way to that for coiled-coil-forming peptides: the polymers possess a regular repeat of apolar (A) residues in a polar (P) sequence of

Porcine carotid artery replacement with biodegradable electrospun poly-e-caprolactone vascular prosthesis.

Science.gov (United States)

Mrówczyński, Wojciech; Mugnai, Damiano; de Valence, Sarra; Tille, Jean-Christophe; Khabiri, Ebrahim; Cikirikcioglu, Mustafa; Möller, Michael; Walpoth, Beat H

2014-01-01

There is a continuous search for shelf-ready small-caliber vascular prostheses with satisfactory early and late results. Biodegradable scaffolds, repopulated by recipient's cells regenerating a neovessel, can be a suitable option for adult and pediatric, urgent and elective cardiovascular procedures. This was a short-term experimental assessment of a new biodegradable vascular prosthesis for arterial replacement in the pig. Eleven pigs underwent bilateral carotid artery replacement with biodegradable electrospun poly-ε-caprolactone (PCL) nanofiber prostheses (internal diameter, 4 mm; length, 5 cm); or expanded polytetrafluoroethylene (ePTFE) prostheses as control. Perioperative anticoagulation was achieved with intravenous heparin (double baseline activated clotting time). Postoperatively, until conclusion of the study at 1 month, animals received aspirin and clopidogrel daily. Transit time flow was measured intraoperatively and at sacrifice. Doppler ultrasound (1 and 4 weeks) and a selective carotid angiography (4 weeks) were performed to assess patency. All explanted grafts were analyzed by histology, morphometry, and scanning electron microscopy in order to study graft-host interaction. Surgical handling and hemostasis of the new prostheses were excellent. Patency rate was 78% (7/9) for PCL grafts, compared with 67% (4/6) for ePTFE grafts. Transit time flow and Doppler ultrasound showed no significant changes in flow and velocity or diameter over time in both groups. Both prostheses showed no detectable in vivo compliance as compared with native carotid artery. Percent neoendothelialization was 86% for PCL and 58% for ePTFE grafts (P = .008). Neointima formation was equal in both grafts. More adventitial infiltration of macrophages, myofibroblasts, and capillaries was seen in PCL grafts with a milder foreign-body reaction when compared with ePTFE implants. Both grafts showed similar endoluminal thrombus formation. Biodegradable, electrospun PCL grafts showed

Three dimensional poly(ε-caprolactone) and silk fibroin nanocomposite fibrous matrix for artificial dermis

Energy Technology Data Exchange (ETDEWEB)

Lee, Jung Min, E-mail: yiyi1124@gmail.com [Nano-Bio Regenerative Medical Institute, College of Medicine, Hallym University, Chuncheon 200-702 (Korea, Republic of); Chae, Taesik, E-mail: apsiky@gmail.com [Department of Materials Engineering, University of British Columbia, Vancouver, BC V6T 1Z4 (Canada); Sheikh, Faheem A., E-mail: faheem99in@yahoo.com [Nano-Bio Regenerative Medical Institute, College of Medicine, Hallym University, Chuncheon 200-702 (Korea, Republic of); Ju, Hyung Woo, E-mail: anabasjoo@gmail.com [Nano-Bio Regenerative Medical Institute, College of Medicine, Hallym University, Chuncheon 200-702 (Korea, Republic of); Moon, Bo Mi, E-mail: toribom@gmail.com [Nano-Bio Regenerative Medical Institute, College of Medicine, Hallym University, Chuncheon 200-702 (Korea, Republic of); Park, Hyun Jung, E-mail: hyunjungpark869@gmail.com [Nano-Bio Regenerative Medical Institute, College of Medicine, Hallym University, Chuncheon 200-702 (Korea, Republic of); Park, Ye Ri, E-mail: payeri89@gmail.com [Nano-Bio Regenerative Medical Institute, College of Medicine, Hallym University, Chuncheon 200-702 (Korea, Republic of); Park, Chan Hum, E-mail: hlpch@paran.com [Nano-Bio Regenerative Medical Institute, College of Medicine, Hallym University, Chuncheon 200-702 (Korea, Republic of); Department of Otorhinolaryngology-Head and Neck Surgery, School of Medicine, Hallym University, Chuncheon 200-704 (Korea, Republic of)

2016-11-01

Ideal dermal substitutes should have comparable physicochemical and biological properties to the natural skin tissue. In this study, we report a novel strategy to “engineer” controlled 3D nanocomposite fibrous matrix of poly(ε-caprolactone) (PCL) and silk fibroin (SF) for an artificial dermis application. Using a custom-designed cold-plate electrospinning and automatic magnet agitation system, up to 6 mm of the thickness was achieved resulting from the accumulation of ice crystal layers on the PCL nanofibers surface-modified with the SF particles. The sacrificed ice crystals induced interconnected macro-pores ranging from tens to hundreds μm. The agitation system introduced uniform distribution of the SF protein within/on the nanofibers, preventing the particles from precipitation and agglomeration. NIH 3T3 fibroblasts proliferated in vitro on the PCL and PCL/SF scaffolds for 7 days, but there was no statistical difference between the groups. Conversely, In vivo rat model studies revealed that the wound healing rate and collagen deposition increased with the SF content within the nanocomposites. The unique 3D construct with the PCL/SF nanocomposite fibers provided desirable spatial cues, surface topography, and surface chemistry for the native cells to infiltrate into the scaffolds. The wound healing potential of the nanocomposites was comparable to the commercial Matriderm® artificial dermis. - Highlights: • 3D macro-porous tissue engineering scaffold constructed with PCL nanofibers and SF nanoparticles. • Fabrication of the PCL/SF nanocomposite fibrous scaffold via a custom-designed cold plate electrospinning (CPE) and automatic magnet agitation (AMA) system. • Comparable wound healing capacity of the PCL/SF scaffolds to the commercial Matriderm® artificial dermis.

Three dimensional poly(ε-caprolactone) and silk fibroin nanocomposite fibrous matrix for artificial dermis

International Nuclear Information System (INIS)

Lee, Jung Min; Chae, Taesik; Sheikh, Faheem A.; Ju, Hyung Woo; Moon, Bo Mi; Park, Hyun Jung; Park, Ye Ri; Park, Chan Hum

2016-01-01

Ideal dermal substitutes should have comparable physicochemical and biological properties to the natural skin tissue. In this study, we report a novel strategy to “engineer” controlled 3D nanocomposite fibrous matrix of poly(ε-caprolactone) (PCL) and silk fibroin (SF) for an artificial dermis application. Using a custom-designed cold-plate electrospinning and automatic magnet agitation system, up to 6 mm of the thickness was achieved resulting from the accumulation of ice crystal layers on the PCL nanofibers surface-modified with the SF particles. The sacrificed ice crystals induced interconnected macro-pores ranging from tens to hundreds μm. The agitation system introduced uniform distribution of the SF protein within/on the nanofibers, preventing the particles from precipitation and agglomeration. NIH 3T3 fibroblasts proliferated in vitro on the PCL and PCL/SF scaffolds for 7 days, but there was no statistical difference between the groups. Conversely, In vivo rat model studies revealed that the wound healing rate and collagen deposition increased with the SF content within the nanocomposites. The unique 3D construct with the PCL/SF nanocomposite fibers provided desirable spatial cues, surface topography, and surface chemistry for the native cells to infiltrate into the scaffolds. The wound healing potential of the nanocomposites was comparable to the commercial Matriderm® artificial dermis. - Highlights: • 3D macro-porous tissue engineering scaffold constructed with PCL nanofibers and SF nanoparticles. • Fabrication of the PCL/SF nanocomposite fibrous scaffold via a custom-designed cold plate electrospinning (CPE) and automatic magnet agitation (AMA) system. • Comparable wound healing capacity of the PCL/SF scaffolds to the commercial Matriderm® artificial dermis.

Triblock Copolymers with Grafted Fluorine-Free Amphiphilic Non-Ionic Side Chains for Antifouling and Fouling-Release Applications

Energy Technology Data Exchange (ETDEWEB)

Y Cho; H Sundaram; C Weinman; M Paik; M Dimitriou; J Finlay; M Callow; J Callow; E Kramer; C Ober

2011-12-31

Fluorine-free, amphiphilic, nonionic surface active block copolymers (SABCs) were synthesized through chemical modification of a polystyrene-block-poly(ethylene-ran-butylene)-block-polyisoprene triblock copolymer precursor with selected amphiphilic nonionic Brij and other surfactants. Amphiphilicity was imparted by a hydrophobic aliphatic group combined with a hydrophilic poly(ethylene glycol) (PEG) group-containing moiety. The surfaces were characterized by dynamic water contact angle, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and near edge X-ray absorption fine structure (NEXAFS) analysis. In biofouling assays, settlement (attachment) of both spores of the green alga Ulva and cells of the diatom Navicula on SABCs modified with Brij nonionic side chains was significantly reduced relative to a PDMS standard, with a nonionic surfactant combining a PEG group and an aliphatic moiety demonstrating the best performance. Additionally, a fouling-release assay using sporelings (young plants) of Ulva and Navicula suggested that the SABC derived from nonionic Brij side chains also out-performed PDMS as a fouling-release material. Good antifouling and fouling-release properties were not demonstrated for the other two amphiphilic surfaces derived from silicone and aromatic group containing nonionic surfactants included in this study. The results suggest that small differences in chemical surface functionality impart more significant changes with respect to the antifouling settlement and fouling-release performance of materials than overall wettability behavior.

Influence of polyacrylic acid nanoparticles on the elastic properties of RBCs membranes in patients with diabetes mellitus type 2

Czech Academy of Sciences Publication Activity Database

Melnikova, G.B.; Kuzhel, N.S.; Tolstaya, T.N.; Konstantinova, E.E.; Drozd, E.S.; Shisko, O.N.; Mokhort, T.G.; Antonova, N.; Říha, Pavel; Kowalczuk, A.; Koseva, N.

2015-01-01

Roč. 29, č. 4 (2015), s. 12-19 ISSN 1313-2458 Institutional support: RVO:67985874 Keywords : red blood cells * nanoparticles * poly(acrylic acid) * elasticity modulus * atomic force microscopy Subject RIV: BK - Fluid Dynamics http://www.imbm.bas.bg/biomechanics/uploads/Archive2015-4/12-19_Melnikova-Konstantinova_et%20al_abstract-1_18.12.15.pdf

Effects of some polymeric additives on the cocrystallization of caffeine

Science.gov (United States)

Chung, Jihae; Kim, Il Won

2011-11-01

Effects of polymeric additives on the model cocrystallization were examined. The model cocrystal was made from caffeine and oxalic acid, and poly(ethylene glycol) (PEG), poly( L-lactide) (PLLA), poly(ɛ-caprolactone) (PCL), and poly(acrylic acid) (PAA) were the additives. The cocrystals were formed as millimeter-sized crystals without additives, and they became microcrystals with PLLA and PCL, and nanocrystals with PAA. XRD and IR revealed that the cocrystal structure was unchanged despite the strong effects of the additives on the crystal morphology, although some decrease in crystallinity was observed with PAA as confirmed by DSC. The DSC study also showed that the cocrystal melted and recrystallized to form α-caffeine upon heating. The present study verified that the polymeric additives can be utilized to modulate the size and morphology of the cocrystals without interfering the intermolecular interactions essential to the integrity of the cocrystal structures.

Control of in vivo disposition and immunogenicity of polymeric micelles by adjusting poly(sarcosine) chain lengths on surface

Science.gov (United States)

Kurihara, Kensuke; Ueda, Motoki; Hara, Isao; Ozeki, Eiichi; Togashi, Kaori; Kimura, Shunsaku

2017-07-01

Four kinds of A3B-type amphiphilic polydepsipeptides, (poly(sarcosine))3- b-poly( l-lactic acid) (the degree of polymerization of poly(sarcosine) are 10, 33, 55, and 85; S10 3 , S33 3 , S55 3 , and S85 3 ) were synthesized to prepare core-shell type polymeric micelles. Their in vivo dispositions and stimulations to trigger immune system to produce IgM upon multiple administrations to mice were examined. With increasing poly(sarcosine) chain lengths, the hydrophilic shell became thicker and the surface density at the most outer surface decreased on the basis of dynamic and static light scattering measurements. These two physical elements of polymeric micelles elicited opposite effects on the immune response in light of the chain length therefore to show an optimized poly(sarcosine) chain length existing between 33mer and 55mer to suppress the accelerated blood clearance phenomenon associated with polymeric micelles.

Selective laser sintered poly-ε-caprolactone scaffold hybridized with collagen hydrogel for cartilage tissue engineering

International Nuclear Information System (INIS)

Chen, Chih-Hao; Chen, Jyh-Ping; Shyu, Victor Bong-Hang; Lee, Ming-Yih

2014-01-01

Selective laser sintering (SLS), an additive manufacturing (AM) technology, can be used to produce tissue engineering scaffolds with pre-designed macro and micro features based on computer-aided design models. An in-house SLS machine was built and 3D poly-ε-caprolactone (PCL) scaffolds were manufactured using a layer-by-layer design of scaffold struts with varying orientations (0°/45°/0°/45°, 0°/90°/0°/90°, 0°/45°/90°/135°), producing scaffolds with pores of different shapes and distribution. To better enhance the scaffold properties, chondrocytes were seeded in collagen gel and loaded in scaffolds for cartilage tissue engineering. Gel uptake and dynamic mechanical analysis demonstrated the better suitability of the 0°/90°/0°/90° scaffolds for reconstructive cartilage tissue engineering purposes. Chondrocytes were then seeded onto the 0°/90°/0°/90° scaffolds in collagen I hydrogel (PCL/COL1) and compared to medium-suspended cells in terms of their cartilage-like tissue engineering parameters. PCL/COL1 allowed better cell proliferation when compared to PCL or two-dimensional tissue culture polystyrene. Scanning electron microscopy and confocal microscopy observations demonstrated a similar trend for extracellular matrix production and cell survival. Glycosaminoglycan and collagen II quantification also demonstrated the superior matrix secretion properties of PCL/COL1 hybrid scaffolds. Collagen-gel-suspended chondrocytes loaded in SLS-manufactured PCL scaffolds may provide a means of producing tissue-engineered cartilage with customized shapes and designs via AM technology. (paper)

Production of Poly(ε-Caprolactone)/Hydroxyapatite Composite Scaffolds with a Tailored Macro/Micro-Porous Structure, High Mechanical Properties, and Excellent Bioactivity.

Science.gov (United States)

Kim, Jong-Woo; Shin, Kwan-Ha; Koh, Young-Hag; Hah, Min Jin; Moon, Jiyoung; Kim, Hyoun-Ee

2017-09-22

We produced poro-us poly(ε-caprolactone) (PCL)/hydroxyapatite (HA) composite scaffolds for bone regeneration, which can have a tailored macro/micro-porous structure with high mechanical properties and excellent in vitro bioactivity using non-solvent-induced phase separation (NIPS)-based 3D plotting. This innovative 3D plotting technique can create highly microporous PCL/HA composite filaments by inducing unique phase separation in PCL/HA solutions through the non-solvent-solvent exchange phenomenon. The PCL/HA composite scaffolds produced with various HA contents (0 wt %, 10 wt %, 15 wt %, and 20 wt %) showed that PCL/HA composite struts with highly microporous structures were well constructed in a controlled periodic pattern. Similar levels of overall porosity (~78 vol %) and pore size (~248 µm) were observed for all the PCL/HA composite scaffolds, which would be highly beneficial to bone tissue regeneration. Mechanical properties, such as ultimate tensile strength and compressive yield strength, increased with an increase in HA content. In addition, incorporating bioactive HA particles into the PCL polymer led to remarkable enhancements in in vitro apatite-forming ability.

Development and evaluation of triclosan loaded poly-ε-caprolactone nanoparticulate system for the treatment of periodontal infections

International Nuclear Information System (INIS)

Aminu, Nafiu; Baboota, Sanjula; Pramod, K.; Singh, Manisha; Dang, Shweta; Ansari, Shahid H.; Sahni, Jasjeet K.; Ali, Javed

2013-01-01

Periodontal disease affects tooth-supporting structures and nanoparticles (NPs) have been a promising approach for its treatment. The purpose of the study was to develop triclosan-loaded poly-ε-caprolactone (PCL) NPs for the treatment of periodontal infections. Solvent displacement method was used to prepare NPs following Box–Behnken design. The NPs were evaluated with respect to particle size, polydispersity index, surface morphology, zeta potential, thermal properties, in vitro drug release, and cell viability assay. The optimized NPs were in the size range of 180–230 nm with a mean size of 205.61 ± 10.4 nm. Entrapment efficiency (EE) of 91.02 ± 2.4 % was obtained with a drug loading of 21.71 ± 1.3 %. About 97 % of drug was released in vitro after 3 h. NPs demonstrated almost 100 % cell viability in L929 cell lines. Shelf life of the nanoparticles was 17.07 months. PCL affected particle size whereas triclosan affected loading and EE. The optimized NPs were spherical with smooth surface and exhibited biphasic in vitro release pattern. NPs had optimum zeta potential and PDI and were stable on storage. Absence of cytotoxicity of NPs to L929 cells indicated its safety. Triclosan-loaded PCL nanoparticles could thus serve as a novel colloidal drug delivery system against periodontal infections

Development and evaluation of triclosan loaded poly-ε-caprolactone nanoparticulate system for the treatment of periodontal infections

Energy Technology Data Exchange (ETDEWEB)

Aminu, Nafiu; Baboota, Sanjula; Pramod, K. [Jamia Hamdard, Department of Pharmaceutics, Faculty of Pharmacy (India); Singh, Manisha; Dang, Shweta [Jaypee Institute of Information Technology, Department of Biotechnology (India); Ansari, Shahid H. [Jamia Hamdard, Department of Pharmacognosy and Phytochemistry, Faculty of Pharmacy (India); Sahni, Jasjeet K.; Ali, Javed, E-mail: javedaali@yahoo.com [Jamia Hamdard, Department of Pharmaceutics, Faculty of Pharmacy (India)

2013-11-15

Periodontal disease affects tooth-supporting structures and nanoparticles (NPs) have been a promising approach for its treatment. The purpose of the study was to develop triclosan-loaded poly-ε-caprolactone (PCL) NPs for the treatment of periodontal infections. Solvent displacement method was used to prepare NPs following Box–Behnken design. The NPs were evaluated with respect to particle size, polydispersity index, surface morphology, zeta potential, thermal properties, in vitro drug release, and cell viability assay. The optimized NPs were in the size range of 180–230 nm with a mean size of 205.61 ± 10.4 nm. Entrapment efficiency (EE) of 91.02 ± 2.4 % was obtained with a drug loading of 21.71 ± 1.3 %. About 97 % of drug was released in vitro after 3 h. NPs demonstrated almost 100 % cell viability in L929 cell lines. Shelf life of the nanoparticles was 17.07 months. PCL affected particle size whereas triclosan affected loading and EE. The optimized NPs were spherical with smooth surface and exhibited biphasic in vitro release pattern. NPs had optimum zeta potential and PDI and were stable on storage. Absence of cytotoxicity of NPs to L929 cells indicated its safety. Triclosan-loaded PCL nanoparticles could thus serve as a novel colloidal drug delivery system against periodontal infections.

Bilayer porous scaffold based on poly-({epsilon}-caprolactone) nanofibrous membrane and gelatin sponge for favoring cell proliferation

Energy Technology Data Exchange (ETDEWEB)

Zhou Zhihua; Zhou Yang [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Chen Yiwang, E-mail: ywchen@ncu.edu.cn [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Institute of Polymers, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Nie Huarong, E-mail: niehr@iccas.ac.cn [Institute of Polymers, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wang Yang [First Affiliated Hospital, Nanchang University, 17 Yongwaizheng Road, Nanchang 330006 (China); Li Fan; Zheng Yan [Institute of Polymers, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China)

2011-12-15

Electrospun poly-({epsilon}-caprolactone) (PCL) nanofibers has been widely used in the medical prosthesis. However, poor hydrophilicity and the lack of natural recognition sites for covalent cell-recognition signal molecules to promote cell attachment have limited its utility as tissue scaffolds. In this study, Bilayer porous scaffolds based on PCL electrospun membranes and gelatin (GE) sponges were fabricated through soft hydrolysis of PCL electrospun followed by grafting gelatin onto the fiber surface, through crosslinking and freeze drying treatment of additional gelatin coat and grafted gelatin surface. GE sponges were stably anchored on PCL membrane surface with the aid of grafted GE molecules. The morphologies of bilayer porous scaffolds were observed through SEM. The contact angle of the scaffolds was 0 Degree-Sign , the mechanical properties of scaffolds were measured by tensile test, Young's moduli of PCL scaffolds before and after hydrolysis are 66-77.3 MPa and 62.3-75.4 MPa, respectively. Thus, the bilayer porous scaffolds showed excellent hydrophilic surface and desirable mechanical strength due to the soft hydrolysis and GE coat. The cell culture results showed that the adipose derived mesenchymal stem cells did more favor to adhere and grow on the bilayer porous scaffolds than on PCL electrospun membranes. The better cell affinity of the final bilayer scaffolds not only attributed to the surface chemistry but also the introduction of bilayer porous structure.

Bilayer porous scaffold based on poly-(ε-caprolactone) nanofibrous membrane and gelatin sponge for favoring cell proliferation

International Nuclear Information System (INIS)

Zhou Zhihua; Zhou Yang; Chen Yiwang; Nie Huarong; Wang Yang; Li Fan; Zheng Yan

2011-01-01

Electrospun poly-(ε-caprolactone) (PCL) nanofibers has been widely used in the medical prosthesis. However, poor hydrophilicity and the lack of natural recognition sites for covalent cell-recognition signal molecules to promote cell attachment have limited its utility as tissue scaffolds. In this study, Bilayer porous scaffolds based on PCL electrospun membranes and gelatin (GE) sponges were fabricated through soft hydrolysis of PCL electrospun followed by grafting gelatin onto the fiber surface, through crosslinking and freeze drying treatment of additional gelatin coat and grafted gelatin surface. GE sponges were stably anchored on PCL membrane surface with the aid of grafted GE molecules. The morphologies of bilayer porous scaffolds were observed through SEM. The contact angle of the scaffolds was 0°, the mechanical properties of scaffolds were measured by tensile test, Young's moduli of PCL scaffolds before and after hydrolysis are 66-77.3 MPa and 62.3-75.4 MPa, respectively. Thus, the bilayer porous scaffolds showed excellent hydrophilic surface and desirable mechanical strength due to the soft hydrolysis and GE coat. The cell culture results showed that the adipose derived mesenchymal stem cells did more favor to adhere and grow on the bilayer porous scaffolds than on PCL electrospun membranes. The better cell affinity of the final bilayer scaffolds not only attributed to the surface chemistry but also the introduction of bilayer porous structure.

Biocompatibility of Poly-ε-caprolactone-hydroxyapatite composite on mouse bone marrow-derived osteoblasts and endothelial cells

Directory of Open Access Journals (Sweden)

Wooley Paul H

2009-02-01

Full Text Available Abstract Background Tissue-engineered bone may be developed by seeding the cells capable of both osteogenesis and vascularization on biocompatible composite scaffolds. The current study investigated the performance of mice bone marrow-derived osteogenic cells and endothelial cells as seeded on hydroxyapatite (HA and poly-ε-caprolactone (PCL composite scaffolds. Methods Mononuclear cells were induced to osteoblasts and endothelial cells respectively, which were defined by the expression of osteocalcin, alkaline phosphatase (ALP, and deposits of calcium-containing crystal for osteoblasts, or by the expression of vascular endothelial growth factor receptor-2 (VEGFR-2 and von Willebrand factor (vWF, and the formation of a capillary network in Matrigel™ for endothelial cells. Both types of cell were seeded respectively on PCL-HA scaffolds at HA to PCL weight ratio of 1:1, 1:4, or 0:1 and were evaluated using scanning electron microscopy, ALP activity (of osteoblasts and nitric oxide production (of endothelial cells plus the assessment of cell viability. Results The results indicated that HA led to a positive stimulation of osteoblasts viability and ALP activity, while HA showed less influence on endothelial cells viability. An elevated nitric oxide production of endothelial cells was observed in HA-containing group. Conclusion Supplement of HA into PCL improved biocompatible for bone marrow-derived osteoblasts and endothelial cells. The PCL-HA composite integrating with two types of cells may provide a useful system for tissue-engineered bone grafts with vascularization.

Preparation of enhanced hydrophobic poly(L-lactide-co-ε-caprolactone) films surface and its blood compatibility

Energy Technology Data Exchange (ETDEWEB)

Kim, Seung Il; Lim, Jin Ik; Jung, Youngmee; Mun, Cho Hay [Division of Life and Health Science, Biomaterials Research Center, Korea Institute of Science and Technology, Seoul (Korea, Republic of); Kim, Ji Heung, E-mail: kimjh@skku.edu [Department of Chemical Engineering, Polymer Technology Institute, Sungkyunkwan University, Suwon, Kyunggi (Korea, Republic of); Kim, Soo Hyun, E-mail: soohkim@kist.re.kr [Division of Life and Health Science, Biomaterials Research Center, Korea Institute of Science and Technology, Seoul (Korea, Republic of); KU-KIST Graduate School of Converging Science and Technology, Korea University, Seoul (Korea, Republic of)

2013-07-01

Hydrophobicity-enhanced poly(L-lactide-co-ε-caprolactone) (PLCL) (50:50) films were cast by using the solvent–nonsolvent casting method. PLCL (50:50) was synthesized by the well-known random copolymerization process and confirmed by {sup 1}H NMR analysis. The molecular weight of the synthesized PLCL was measured by gel permeation chromatography (GPC). Number-average (Mn), weight-average (Mw) molecular weights and polydispersity (Mw/Mn) were 7 × 10{sup 4}, 1.2 × 10{sup 5}, and 1.7, respectively. PLCL films were cast in vacuum condition with various nonsolvents and nonsolvent ratios. Tetrahydrofuran (THF) was used as the solvent and three different alcohols were used as the nonsolvent: methanol, ethanol, and isopropyl alcohol (IPA). Surface hydrophobicity was confirmed by water contact angle. The water contact angle was increased from 81° ± 2° to 107° ± 2°. Water contact angle was influenced by surface porosity and topography. The prepared film surfaces were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The change of crystalline property was characterized by X-ray diffraction (XRD). Platelet adhesion tests on the modified PLCL film surfaces were evaluated by platelet-rich plasma (PRP). The modified film surface exhibited enhanced hydrophobicity and reduced platelet adhesion ratio depending on the surface topography. One of the candidate products proposed as a potential blood compatible material showed a markedly reduced platelet adhesion property.

Towards the understanding of the molecular weight dependence of essential work of fracture in semi-crystalline polymers: A study on poly(ε-caprolactone

Directory of Open Access Journals (Sweden)

F. Tuba

2014-11-01

Full Text Available The plane-stress ductile fracture of poly(#-caprolactone (PCL has been investigated as a function of molecular weight and related crystalline structure. Because of the interacting effects in semi-crystalline polymers a separate study of a given structural parameter is rather challenging. Nevertheless, this polymer seems to be a good model material to study the effect of molecular weight on the essential work of fracture, as the interactions between the separate parameters, at room temperature, are negligible. The molecular characteristics of PCL were determined by size exclusion chromatography. To confirm the entangled molecular structure of studied polymers rheological measurements were performed. The crystalline morphology has been characterized by differential scanning calorimetry and wide angle X-ray diffraction. Quasi-static tensile tests and essential work of fracture tests were performed to study the mechanical behavior. Based on the experimental observations an empirical model has been proposed to outline the molecular weight and crystallinity dependence of the essential work of fracture in this semi-crystalline polymer.

An Experimental and Molecular Dynamics Investigation into the Amphiphilic Nature of Sulforhodamine B

OpenAIRE

Polat, Baris E.; Lin, Shangchao; Mendenhall, Jonathan D.; VanVeller, Brett; Langer, Robert; Blankschtein, Daniel

2011-01-01

Sulforhodamine B (SRB), a common fluorescent dye, is often considered to be a purely hydrophilic molecule, having no impact on bulk or interfacial properties of aqueous solutions. This assumption is due to the high water solubility of SRB relative to most fluorescent probes. However, in the present study, we demonstrate that SRB is in fact an amphiphile, with the ability to adsorb at an air/water interface and to incorporate into sodium dodecyl sulfate (SDS) micelles. In fact, SRB reduces the...

Influence of clay-nanofiller geometry on the structure and properties of poly(lactic acid)/thermoplastic polyurethane nanocomposites

Czech Academy of Sciences Publication Activity Database

Kelnar, Ivan; Kratochvíl, Jaroslav; Fortelný, Ivan; Kaprálková, Ludmila; Zhigunov, Alexander; Nevoralová, Martina; Kotrisová, M.; Khunová, V.

2016-01-01

Roč. 6, č. 36 (2016), s. 30755-30762 ISSN 2046-2069 R&D Projects: GA ČR(CZ) GA13-15255S Institutional support: RVO:61389013 Keywords : poly (epsilon-caprolactone) * poly (lactic acid) * microfibrillar composites Subject RIV: JI - Composite Materials Impact factor: 3.108, year: 2016

Antigen-decorated shell cross-linked nanoparticles: synthesis, characterization, and antibody interactions.

Science.gov (United States)

Joralemon, Maisie J; Smith, Norah L; Holowka, David; Baird, Barbara; Wooley, Karen L

2005-01-01

Antigen-decorated shell cross-linked knedel-like nanoparticles (SCKs) were synthesized and studied as multivalent nanoscale surfaces from which antibody-binding units were presented in a manner that was designed to approach virus particle surfaces. The SCK nanostructures were fabricated with control over the number of antigenic groups, from mixed micellization of amphiphilic diblock copolymer building blocks that contained either an antigen (2,4-dinitrophenyl) or an ethylpropionate group at the hydrophilic alpha-chain terminus. Amphiphilic diblock copolymers were synthesized by atom transfer radical polymerization of tert-butyl acrylate and methyl acrylate sequentially from either a 2,4-dinitrophenyl-functionalized initiator or ethyl 2-bromopropionate, followed by selective removal of the tert-butyl groups to afford 2,4-dinitrophenyl-poly(acrylic acid)60-b-poly(methyl acrylate)60 (DNP-PAA(60)-b-PMA60) and poly(acrylic acid)70-b-poly(methyl acrylate) (PAA70-b-PMA70). Micelles were assembled via addition of water to THF solutions of the polymers in 0:1, 1:1, and 1:0 molar ratios of DNP-PAA60-b-PMA60 to PAA70-b-PMA70, followed by dialysis against water. The acrylic acid groups of the micelle coronas were partially cross-linked (nominally 50%) with 2,2'-(ethylenedioxy)bis(ethylamine), in the presence of 1-(3'-dimethylaminopropyl)-3-ethylcarbodiimide methiodide. Following extensive dialysis against water, the 0%, 50%, and 100% dinitrophenylated shell cross-linked nanoparticles (DNP-SCKs) were characterized with dynamic light scattering (DLS), transmission electron microscopy (TEM), atomic force microscopy (AFM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), infrared and UV-vis spectroscopies, and analytical ultracentrifugation (AU). The surface accessibility and bioavailability of the DNP units upon the DNP-SCKs were investigated by performing quenching titrations of fluorescein-labeled IgE antibody in solution and degranulation of Ig

Amphiphilic graft copolymer based on poly(styrene-co-maleic anhydride with low molecular weight polyethylenimine for efficient gene delivery

Directory of Open Access Journals (Sweden)

Duan XP

2012-09-01

Full Text Available Xiaopin Duan,1,2 Jisheng Xiao,2 Qi Yin,2 Zhiwen Zhang,2 Shirui Mao,1 Yaping Li21School of Pharmacy, Shenyang Pharmaceutical University, Shenyang, 2Center of Pharmaceutics, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Shanghai, ChinaBackground and methods: A new amphiphilic comb-shaped copolymer (SP was synthesized by conjugating poly(styrene-co-maleic anhydride with low molecular weight polyethyleneimine for gene delivery. Fourier transform infrared spectrum, 1H nuclear magnetic resonance, and gel permeation chromatography were used to characterize the graft copolymer.Results: The buffering capability of SP was similar to that of polyethyleneimine within the endosomal pH range. The copolymer could condense DNA effectively to form complexes with a positive charge (13–30 mV and a small particle size (130–200 nm at N/P ratios between 5 and 20, and protect DNA from degradation by DNase I. In addition, SP showed much lower cytotoxicity than polyethyleneimine 25,000. Importantly, the gene transfection activity and cellular uptake of SP-DNA complexes were all markedly higher than that of complexes of polyethyleneimine 25,000 and DNA in MCF-7 and MCF-7/ADR cell lines.Conclusion: This work highlights the promise of SP as a safe and efficient synthetic vector for DNA delivery.Keywords: poly(styrene-co-maleic anhydride, polyethylenimine, DNA, gene delivery

Preparation and characterization of polyacrylamide-modified kaolinite containing poly [acrylic acid-co-methylene bisacrylamide] nanocomposite hydrogels

DEFF Research Database (Denmark)

Zaharia, Anamaria; Sarbu, Andrei; Radu, Anita-Laura

2015-01-01

Novel nanocomposite hydrogel structures based on cross-linked poly(acrylic acid) (PAA) and kaolinite (Kaol), modified with different loadings of polyacrylamide (PAAm), were prepared by inverse dispersion polymerization. Ceric ammonium nitrate as an initiator in the presence of nitric acid was used...... of Kaol particles in the polyacrylic acid matrix, thereby leading to enhanced interactions and furthermore to improved mechanical properties of the final hydrogels....

Investigation of the role of hydrophilic chain length in amphiphilic perfluoropolyether/poly(ethylene glycol) networks: towards high-performance antifouling coatings

Energy Technology Data Exchange (ETDEWEB)

Wang, Yapei; Pitet, Louis M.; Finlay, John A.; Brewer, Lenora H.; Cone, Gemma; Betts, Douglas E.; Callow, Maureen E.; Callow, James A.; Wendt, Dean E.; Hillmyer, Marc A.; DeSimone, Joseph M. (Birmingham UK); (NCSU); (UNC); (Cal. Polytech.); (UMM)

2013-03-07

The facile preparation of amphiphilic network coatings having a hydrophobic dimethacryloxy-functionalized perfluoropolyether (PFPE-DMA; M{sub w} = 1500 g mol{sup -1}) crosslinked with hydrophilic monomethacryloxy functionalized poly(ethylene glycol) macromonomers (PEG-MA; M{sub w} = 300, 475, 1100 g mol{sup -1}), intended as non-toxic high-performance marine coatings exhibiting antifouling characteristics is demonstrated. The PFPE-DMA was found to be miscible with the PEG-MA. Photo-cured blends of these materials containing 10 wt% of PEG-MA oligomers did not swell significantly in water. PFPE-DMA crosslinked with the highest molecular weight PEG oligomer (ie PEG1100) deterred settlement (attachment) of algal cells and cypris larvae of barnacles compared to a PFPE control coating. Dynamic mechanical analysis of these networks revealed a flexible material. Preferential segregation of the PEG segments at the polymer/air interface resulted in enhanced antifouling performance. The cured amphiphilic PFPE/PEG films showed decreased advancing and receding contact angles with increasing PEG chain length. In particular, the PFPE/PEG1100 network had a much lower advancing contact angle than static contact angle, suggesting that the PEG1100 segments diffuse to the polymer/water interface quickly. The preferential interfacial aggregation of the larger PEG segments enables the coating surface to have a substantially enhanced resistance to settlement of spores of the green seaweed Ulva, cells of the diatom Navicula and cypris larvae of the barnacle Balanus amphitrite as well as low adhesion of sporelings (young plants) of Ulva, adhesion being lower than to a polydimethyl elastomer, Silastic T2.

Investigation of the role of hydrophilic chain length in amphiphilic perfluoropolyether/poly(ethylene glycol) networks: towards high-performance antifouling coatings.

Science.gov (United States)

Wang, Yapei; Pitet, Louis M; Finlay, John A; Brewer, Lenora H; Cone, Gemma; Betts, Douglas E; Callow, Maureen E; Callow, James A; Wendt, Dean E; Hillmyer, Marc A; DeSimonea, Joseph M

2011-01-01

The facile preparation of amphiphilic network coatings having a hydrophobic dimethacryloxy-functionalized perfluoropolyether (PFPE-DMA; M(w) = 1500 g mol(-1)) crosslinked with hydrophilic monomethacryloxy functionalized poly(ethylene glycol) macromonomers (PEG-MA; M(w) = 300, 475, 1100 g mol(-1)), intended as non-toxic high-performance marine coatings exhibiting antifouling characteristics is demonstrated. The PFPE-DMA was found to be miscible with the PEG-MA. Photo-cured blends of these materials containing 10 wt% of PEG-MA oligomers did not swell significantly in water. PFPE-DMA crosslinked with the highest molecular weight PEG oligomer (ie PEG1100) deterred settlement (attachment) of algal cells and cypris larvae of barnacles compared to a PFPE control coating. Dynamic mechanical analysis of these networks revealed a flexible material. Preferential segregation of the PEG segments at the polymer/air interface resulted in enhanced antifouling performance. The cured amphiphilic PFPE/PEG films showed decreased advancing and receding contact angles with increasing PEG chain length. In particular, the PFPE/PEG1100 network had a much lower advancing contact angle than static contact angle, suggesting that the PEG1100 segments diffuse to the polymer/water interface quickly. The preferential interfacial aggregation of the larger PEG segments enables the coating surface to have a substantially enhanced resistance to settlement of spores of the green seaweed Ulva, cells of the diatom Navicula and cypris larvae of the barnacle Balanus amphitrite as well as low adhesion of sporelings (young plants) of Ulva, adhesion being lower than to a polydimethyl elastomer, Silastic T2.

Electrochemical sensing using micro- and nanostructured poly(ferrocenylsilane)s

NARCIS (Netherlands)

Folkertsma-Hendriks, Laura

2017-01-01

In this thesis, we look for ways to use the polymer poly(ferrocenylsilane) in sensor applications. Drying a mix of PFS-Vinylimidazole with polyacrylic acid (PAA) results in a partially phase-separated layer. We have visualised this using electron microscopy (SEM) and X-ray scattering (SAXS). When

Preparation of poly (styrene)-b-poly (acrylic acid)/{gamma}-Fe{sub 2}O{sub 3} composites

Energy Technology Data Exchange (ETDEWEB)

Zhang, L.D. [School of Materials Science and Engineering, Shandong Polytechnic University, Key Laboratory of Processing and Testing Technology of Glass Functional Ceramics of Shandong Province, Daxue Road, Western University Science Park, Jinan 250353 (China); Liu, W.L., E-mail: wlliu@sdu.edu.cn [School of Materials Science and Engineering, Shandong Polytechnic University, Key Laboratory of Processing and Testing Technology of Glass Functional Ceramics of Shandong Province, Daxue Road, Western University Science Park, Jinan 250353 (China); Xiao, C.L.; Yao, J.S.; Fan, Z.P.; Sun, X.L.; Zhang, X.; Wang, L. [School of Materials Science and Engineering, Shandong Polytechnic University, Key Laboratory of Processing and Testing Technology of Glass Functional Ceramics of Shandong Province, Daxue Road, Western University Science Park, Jinan 250353 (China); Wang, X.Q. [State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100 (China)

2011-12-15

The use of a block copolymer, poly (styrene)-b-poly (acrylic acid) (PS-b-PAA) to prepare a magnetic nanocomposite was investigated. Poly (styrene)-poly (t-butyl acrylate) block copolymer, being synthesized by atom transfer radical polymerization, was hydrolyzed with hydrochloric acid for obtaining PS-b-PAA. The obtained PS-b-PAA was then compounded with the modified {gamma}-Fe{sub 2}O{sub 3}, and subsequently the magnetic nanocomposite was achieved. The products were characterized by {sup 1}H NMR, FTIR, gel permeation chromatography, thermogravimetric analysis, transmission electron microscopy and vibrating sample magnetometer. The results showed that the nanocomposites exhibited soft magnetism, with the mean diameter of 100 nm approximately. - Highlights: > Magnetic composites were prepared using {gamma}-Fe{sub 2}O{sub 3} and PS-b-PAA. > PS-b-PAA was synthesized by atom transfer radical polymerization. > The obtained composite exhibited soft magnetism.

Surface phase separation, dewetting feature size, and crystal morphology in thin films of polystyrene/poly(ε-caprolactone) blend.

Science.gov (United States)

Ma, Meng; He, Zhoukun; Li, Yuhan; Chen, Feng; Wang, Ke; Zhang, Qing; Deng, Hua; Fu, Qiang

2012-12-01

Thin films of polystyrene (PS)/poly(ε-caprolactone) (PCL) blends were prepared by spin-coating and characterized by tapping mode force microscopy (AFM). Effects of the relative concentration of PS in polymer solution on the surface phase separation and dewetting feature size of the blend films were systematically studied. Due to the coupling of phase separation, dewetting, and crystallization of the blend films with the evaporation of solvent during spin-coating, different size of PS islands decorated with various PCL crystal structures including spherulite-like, flat-on individual lamellae, and flat-on dendritic crystal were obtained in the blend films by changing the film composition. The average distance of PS islands was shown to increase with the relative concentration of PS in casting solution. For a given ratio of PS/PCL, the feature size of PS appeared to increase linearly with the square of PS concentration while the PCL concentration only determined the crystal morphology of the blend films with no influence on the upper PS domain features. This is explained in terms of vertical phase separation and spinodal dewetting of the PS rich layer from the underlying PCL rich layer, leading to the upper PS dewetting process and the underlying PCL crystalline process to be mutually independent. Copyright © 2012 Elsevier Inc. All rights reserved.

Use of lecithin to control fiber morphology in electrospun poly (ɛ-caprolactone) scaffolds for improved tissue engineering applications.

Science.gov (United States)

Coverdale, Benjamin D M; Gough, Julie E; Sampson, William W; Hoyland, Judith A

2017-10-01

We elucidate the effects of incorporating surfactants into electrospun poly (ɛ-caprolactone) (PCL) scaffolds on network homogeneity, cellular adherence and osteogenic differentiation. Lecithin was added with a range of concentrations to PCL solutions, which were electrospun to yield functionalized scaffolds. Addition of lecithin yielded a dose-dependent reduction in scaffold hydrophobicity, whilst reducing fiber width and hence increasing specific surface area. These changes in scaffold morphology were associated with increased cellular attachment of Saos-2 osteoblasts 3-h postseeding. Furthermore, cells on scaffolds showed comparable proliferation over 14 days of incubation to TCP controls. Through model-based interpretation of image analysis combined with gravimetric estimates of porosity, lecithin is shown to reduce scaffold porosity and mean pore size. Additionally, lecithin incorporation is found to reduce fiber curvature, resulting in increased scaffold specific elastic modulus. Low concentrations of lecithin were found to induce upregulation of several genes associated with osteogenesis in primary mesenchymal stem cells. The results demonstrate that functionalization of electrospun PCL scaffolds with lecithin can increase the biocompatibility and regenerative potential of these networks for bone tissue engineering applications. © 2017 The Authors Journal of Biomedical Materials Research Part A Published by Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 2865-2874, 2017. © 2017 The Authors Journal of Biomedical Materials Research Part A Published by Wiley Periodicals, Inc.

Bioactive Sr(II/Chitosan/Poly(ε-caprolactone Scaffolds for Craniofacial Tissue Regeneration. In Vitro and In Vivo Behavior

Directory of Open Access Journals (Sweden)

Itzia Rodríguez-Méndez

2018-03-01

Full Text Available In craniofacial tissue regeneration, the current gold standard treatment is autologous bone grafting, however, it presents some disadvantages. Although new alternatives have emerged there is still an urgent demand of biodegradable scaffolds to act as extracellular matrix in the regeneration process. A potentially useful element in bone regeneration is strontium. It is known to promote stimulation of osteoblasts while inhibiting osteoclasts resorption, leading to neoformed bone. The present paper reports the preparation and characterization of strontium (Sr containing hybrid scaffolds formed by a matrix of ionically cross-linked chitosan and microparticles of poly(ε-caprolactone (PCL. These scaffolds of relatively facile fabrication were seeded with osteoblast-like cells (MG-63 and human bone marrow mesenchymal stem cells (hBMSCs for application in craniofacial tissue regeneration. Membrane scaffolds were prepared using chitosan:PCL ratios of 1:2 and 1:1 and 5 wt % Sr salts. Characterization was performed addressing physico-chemical properties, swelling behavior, in vitro biological performance and in vivo biocompatibility. Overall, the composition, microstructure and swelling degree (≈245% of scaffolds combine with the adequate dimensional stability, lack of toxicity, osteogenic activity in MG-63 cells and hBMSCs, along with the in vivo biocompatibility in rats allow considering this system as a promising biomaterial for the treatment of craniofacial tissue regeneration.

A Novel Docetaxel-Loaded Poly (ɛ-Caprolactone)/Pluronic F68 Nanoparticle Overcoming Multidrug Resistance for Breast Cancer Treatment

Science.gov (United States)

Mei, Lin; Zhang, Yangqing; Zheng, Yi; Tian, Ge; Song, Cunxian; Yang, Dongye; Chen, Hongli; Sun, Hongfan; Tian, Yan; Liu, Kexin; Li, Zhen; Huang, Laiqiang

2009-12-01

Multidrug resistance (MDR) in tumor cells is a significant obstacle to the success of chemotherapy in many cancers. The purpose of this research is to test the possibility of docetaxel-loaded poly (ɛ-caprolactone)/Pluronic F68 (PCL/Pluronic F68) nanoparticles to overcome MDR in docetaxel-resistance human breast cancer cell line. Docetaxel-loaded nanoparticles were prepared by modified solvent displacement method using commercial PCL and self-synthesized PCL/Pluronic F68, respectively. PCL/Pluronic F68 nanoparticles were found to be of spherical shape with a rough and porous surface. The nanoparticles had an average size of around 200 nm with a narrow size distribution. The in vitro drug release profile of both nanoparticle formulations showed a biphasic release pattern. There was an increased level of uptake of PCL/Pluronic F68 nanoparticles in docetaxel-resistance human breast cancer cell line, MCF-7 TAX30, when compared with PCL nanoparticles. The cytotoxicity of PCL nanoparticles was higher than commercial Taxotere® in the MCF-7 TAX30 cell culture, but the differences were not significant ( p > 0.05). However, the PCL/Pluronic F68 nanoparticles achieved significantly higher level of cytotoxicity than both of PCL nanoparticles and Taxotere® ( p < 0.05), indicating docetaxel-loaded PCL/Pluronic F68 nanoparticles could overcome multidrug resistance in human breast cancer cells and therefore have considerable potential for treatment of breast cancer.

Amphiphilic cyclodextrin nanoparticles.

Science.gov (United States)

Varan, Gamze; Varan, Cem; Erdoğar, Nazlı; Hıncal, A Atilla; Bilensoy, Erem

2017-10-15

Cyclodextrins are cyclic oligosaccharides obtained by enzymatic digestion of starch. The α-, β- and γ- cyclodextrins contain respectively 6, 7 and 8 glucopyranose units, with primary and secondary hydroxyl groups located on the narrow and wider rims of a truncated cone shape structure. Such structure is that of a hydrophobic inner cavity with a hydrophilic outer surface allowing to interact with a wide range of molecules like ions, protein and oligonucleotides to form inclusion complexes. Many cyclodextrin applications in the pharmaceutical area have been widely described in the literature due to their low toxicity and low immunogenicity. The most important is to increase the solubility of hydrophobic drugs in water. Chemically modified cyclodextrin derivatives have been synthesized to enhance their properties and more specifically their pharmacological activity. Among these, amphiphilic derivatives were designed to build organized molecular structures, through selfassembling systems or by incorporation in lipid membranes, expected to improve the vectorization in the organism of the drug-containing cyclodextrin cavities. These derivatives can form a variety of supramolecular structures such as micelles, vesicles and nanoparticles. The purpose of this review is to summarize applications of amphiphilic cyclodextrins in different areas of drug delivery, particularly in protein and peptide drug delivery and gene delivery. The article highlights important amphiphilic cyclodextrin applications in the design of novel delivery systems like nanoparticles. Copyright © 2017 Elsevier B.V. All rights reserved.

Morphology-Variable Aggregates Prepared from Cholesterol-Containing Amphiphilic Glycopolymers: Their Protein Recognition/Adsorption and Drug Delivery Applications

Directory of Open Access Journals (Sweden)

Zhao Wang

2018-02-01

Full Text Available In this study, a series of diblock glycopolymers, poly(6-O-methacryloyl-d-galactopyranose-b-poly(6-cholesteryloxyhexyl methacrylate (PMAgala-b-PMAChols, with cholesterol/galactose grafts were prepared through a sequential reversible addition-fragmentation chain transfer (RAFT polymerization and deprotection process. The glycopolymers could self-assemble into aggregates with various morphologies depending on cholesterol/galactose-containing block weight ratios, as determined by transmission electronic microscopy (TEM and dynamic laser light scattering (DLS. In addition, the lectin (Ricinus communis agglutinin II, RCA120 recognition and bovine serum albumin (BSA adsorption of the PMAgala-b-PMAChol aggregates were evaluated. The SK-Hep-1 tumor cell inhibition properties of the PMAgala-b-PMAChol/doxorubicin (DOX complex aggregates were further examined in vitro. Results indicate that the PMAgala-b-PMAChol aggregates with various morphologies showed different interaction/recognition features with RCA120 and BSA. Spherical aggregates (d ≈ 92 nm possessed the highest RCA120 recognition ability and lowest BSA protein adsorption. In addition, the DOX-loaded spherical complex aggregates exhibited a better tumor cell inhibition property than those of nanofibrous complex aggregates. The morphology-variable aggregates derived from the amphiphilic glycopolymers may serve as multifunctional biomaterials with biomolecular recognition and drug delivery features.

Amphiphilic block copolymers for drug delivery.

Science.gov (United States)

Adams, Monica L; Lavasanifar, Afsaneh; Kwon, Glen S

2003-07-01

Amphiphilic block copolymers (ABCs) have been used extensively in pharmaceutical applications ranging from sustained-release technologies to gene delivery. The utility of ABCs for delivery of therapeutic agents results from their unique chemical composition, which is characterized by a hydrophilic block that is chemically tethered to a hydrophobic block. In aqueous solution, polymeric micelles are formed via the association of ABCs into nanoscopic core/shell structures at or above the critical micelle concentration. Upon micellization, the hydrophobic core regions serve as reservoirs for hydrophobic drugs, which may be loaded by chemical, physical, or electrostatic means, depending on the specific functionalities of the core-forming block and the solubilizate. Although the Pluronics, composed of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide), are the most widely studied ABC system, copolymers containing poly(L-amino acid) and poly(ester) hydrophobic blocks have also shown great promise in delivery applications. Because each ABC has unique advantages with respect to drug delivery, it may be possible to choose appropriate block copolymers for specific purposes, such as prolonging circulation time, introduction of targeting moieties, and modification of the drug-release profile. ABCs have been used for numerous pharmaceutical applications including drug solubilization/stabilization, alteration of the pharmacokinetic profile of encapsulated substances, and suppression of multidrug resistance. The purpose of this minireview is to provide a concise, yet detailed, introduction to the use of ABCs and polymeric micelles as delivery agents as well as to highlight current and past work in this area. Copyright 2003 Wiley-Liss, Inc. and the American Pharmacists Association

Novel Anti-Biofouling Soft Contact Lens: l-Cysteine Conjugated Amphiphilic Conetworks via RAFT and Thiol-Ene Click Chemistry.

Science.gov (United States)

Zhang, Chengfeng; Liu, Ziyuan; Wang, Haiye; Feng, Xiaofeng; He, Chunju

2017-07-01

A unique l-cysteine conjugated antifouling amphiphilic conetwork (APCN) is synthesized through end-crosslinking of well-defined triblock copolymers poly(allyl methacrylate)-b-poly(ethylene glycol)-b-poly(allyl methacrylate) via a combination of reversible addition-fragmentation chain transfer (RAFT) polymerization and thiol-ene "click" chemistry. The synthesized poly(ethylene glycol) macro-RAFT agent initiates the polymerization of allyl methacrylate in a controlled manner. The vinyl pendant groups of the precursor partially conjugate with l-cysteine and the rest fully crosslink with mercaptopropyl-containing siloxane via thiol-ene click chemistry under UV irradiation into APCNs, which show distinguished properties, that is, excellent biocompatibility, more than 39.6% water content, 101 barrers oxygen permeability, optimized mechanical properties, and more than 93% visible light transmittance. What's more, the resultant APCNs exhibit eminent resistance to protein adsorption, where the bovine serum albumin and lysozyme adsorption are decreased to 12 and 21 µg cm -2 , respectively. The outstanding properties of APCNs depend on the RAFT controlled method, which precisely designs the hydrophilic/hydrophobic segments and eventually greatly improves the crosslinking efficiency and homogeneity. Meantime, the l-cysteine monolayer can effectively reduce the surface hydrophobicity and prevent protein adsorption, which exhibits the viability for antifouling surface over and under ophthalmic devices, suggesting a promising soft contact lens. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrolytic Degradation and Mechanical Stability of Poly(ε-Caprolactone)/Reduced Graphene Oxide Membranes as Scaffolds for In Vitro Neural Tissue Regeneration.

Science.gov (United States)

Sánchez-González, Sandra; Diban, Nazely; Urtiaga, Ane

2018-03-05

The present work studies the functional behavior of novel poly(ε-caprolactone) (PCL) membranes functionalized with reduced graphene oxide (rGO) nanoplatelets under simulated in vitro culture conditions (phosphate buffer solution (PBS) at 37 °C) during 1 year, in order to elucidate their applicability as scaffolds for in vitro neural regeneration. The morphological, chemical, and DSC results demonstrated that high internal porosity of the membranes facilitated water permeation and procured an accelerated hydrolytic degradation throughout the bulk pathway. Therefore, similar molecular weight reduction, from 80 kDa to 33 kDa for the control PCL, and to 27 kDa for PCL/rGO membranes, at the end of the study, was observed. After 1 year of hydrolytic degradation, though monomers coming from the hydrolytic cleavage of PCL diffused towards the PBS medium, the pH was barely affected, and the rGO nanoplatelets mainly remained in the membranes which envisaged low cytotoxic effect. On the other hand, the presence of rGO nanomaterials accelerated the loss of mechanical stability of the membranes. However, it is envisioned that the gradual degradation of the PCL/rGO membranes could facilitate cells infiltration, interconnectivity, and tissue formation.

Poly (ethylene oxide)-block-poly (n-butyl acrylate)-blockpoly (acrylic acid) triblock terpolymers with highly asymmetric hydrophilic blocks: synthesis and aqueous solution properties

OpenAIRE

Petrov, P. (Petar); Yoncheva, K. (Krassimira); Mokreva, P. (Pavlina); Konstantinov, S. (Spiro); Irache, J.M. (Juan Manuel); Müller, A.H.E. (Axel H.E.)

2013-01-01

The synthesis and aggregation behaviour in aqueous media of novel amphiphilic poly(ethylene oxide)- block-poly(n-butyl acrylate)-block-poly(acrylic acid) (PEO–PnBA–PAA) triblock terpolymers were studied. Terpolymers composed of two highly asymmetric hydrophilic PEO (113 monomer units) and PAA (10–17 units) blocks, and a longer soft hydrophobic PnBA block (163 or 223 units) were synthesized by atom transfer radical polymerisation (ATRP) of n-butyl acrylate and tert-butyl acrylate ...

Synthesis of Well-defined Amphiphilic Block Copolymers by Organotellurium-Mediated Living Radical Polymerization (TERP).

Science.gov (United States)

Kumar, Santosh; Changez, Mohammad; Murthy, C N; Yamago, Shigeru; Lee, Jae-Suk

2011-10-04

Low-molecular weight amphiphilic diblock copolymers, polystyrene-block-poly (2-vinylpyridine) (PS-b-P2VP), and (P2VP-b-PS) with different block ratios were synthesized for the first time via organotellurium-mediated living radical polymerization (TERP). For both the homo- and block copolymerizations, good agreement between the theoretical, and experimental molecular weights was found with nearly 100% yield in every case. The molecular weight distribution for all the samples ranged between 1.10 and 1.24, which is well below the theoretical lower limit of 1.50 for a conventional free radical polymerization. Furthermore, a very simple approach to producing highly dense arrays of titania nanoparticles (TiO2 ) is presented using a site-selective reaction of titanium tetraisopropoxide within the P2VP domains of micellar film of P2VP-b-PS in toluene through the sol-gel method. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Three-dimensional poly (ε-caprolactone)/hydroxyapatite/collagen scaffolds incorporating bone marrow mesenchymal stem cells for the repair of bone defects

International Nuclear Information System (INIS)

Qi, Xin; Huang, Yinjun; Zhang, Jieyuan; Cao, Jiaqing; Jin, Xiangyun; Huang, Jinghuan; Li, Xiaolin; Wang, Ting; Han, Dan

2016-01-01

We previously demonstrated that three-dimensional (3D) hydroxyapatite (HAP)-collagen (COL)-coated poly(ε-caprolactone) (PCL) scaffolds (HAP-COL-PCL) possess appropriate nano-structures, surface roughness, and nutrients, providing a favorable environment for osteogenesis. However, the effect of using 3D HAP-COL-PCL scaffolds incorporating BMSCs for the repair of bone defects in rats has been not evaluated. 3D PCL scaffolds coated with HAP, collagen or HAP/COL and incorporating BMSCs were implanted into calvarial defects. At 12 weeks after surgery, the rats were sacrificed and crania were harvested to assess the bone defect repair using microcomputed tomography (micro-CT), histology, immunohistochemistry and sequential fluorescent labeling analysis. 3D micro-CT reconstructed images and quantitative analysis showed that HAP-COL-PCL groups possessed better bone-forming capacity than HAP-PCL groups or COL-PCL groups. Fluorescent labeling analysis revealed the percentage of tetracycline labeling, alizarin red labeling, and calcein labeling in HAP-COL-PCL groups were all greater than in the other two groups (P  <  0.05), and the result was confirmed by immunohistochemical staining and histological analysis of bone regeneration. This study demonstrates that 3D HAP-COL-PCL scaffolds incorporating BMSCs markedly enhance bone regeneration of bone defects in rats. (paper)

Evaluation of the side effects of poly(epsilon-caprolactone) nanocapsules containing atrazine towards maize plants

Science.gov (United States)

Oliveira, Halley; Stolf-Moreira, Renata; Martinez, Cláudia; Sousa, Gustavo; Grillo, Renato; de Jesus, Marcelo; Fraceto, Leonardo

2015-10-01

Poly(epsilon-caprolactone) (PCL) nanocapsules have been used as a carrier system for the herbicide atrazine, which is commonly applied to maize. We demonstrated previously that these atrazine containing polymeric nanocapsules were ten-fold more effective in the control of mustard plants (a target species), as compared to a commercial atrazine formulation. Since atrazine can have adverse effects on non-target crops, here we analyzed the effect of encapsulated atrazine on growth, physiological and oxidative stress parameters of soil-grown maize plants (Zea mays L.). One day after the post-emergence treatment with PCL nanocapsules containing atrazine (1 mg mL-1), maize plants presented 15 and 21 % decreases in maximum quantum yield of photosystem II and in net CO2 assimilation rate, respectively, as compared to water-sprayed plants. The same treatment led to a 1.8-fold increase in leaf lipid peroxidation in comparison with control plants. However, all of these parameters were unaffected four and eight days after the application of encapsulated atrazine. These results suggested that the negative effects of atrazine were transient, probably due to the ability of maize plants to detoxify the herbicide. When encapsulated atrazine was applied at a ten-fold lower concentration (0.1 mg mL-1), a dosage that is still effective for weed control, no effects were detected even shortly after application. Regardless of the herbicide concentration, neither pre- nor post-emergence treatment with the PCL nanocapsules carrying atrazine resulted in the development of any macroscopic symptoms in maize leaves, and there were no impacts on shoot growth. Additionally, no effects were observed when plants were sprayed with PCL nanocapsules without atrazine. Overall, these results suggested that the use of PCL nanocapsules containing atrazine did not lead to persistent side effects in maize plants, and that the technique could offer a safe tool for weed control without affecting crop growth.

Fabrication of Nanostructured Poly-ε-caprolactone 3D Scaffolds for 3D Cell Culture Technology

KAUST Repository

Schipani, Rossana

2015-04-21

Tissue engineering is receiving tremendous attention due to the necessity to overcome the limitations related to injured or diseased tissues or organs. It is the perfect combination of cells and biomimetic-engineered materials. With the appropriate biochemical factors, it is possible to develop new effective bio-devices that are capable to improve or replace biological functions. Latest developments in microfabrication methods, employing mostly synthetic biomaterials, allow the production of three-dimensional (3D) scaffolds that are able to direct cell-to-cell interactions and specific cellular functions in order to drive tissue regeneration or cell transplantation. The presented work offers a rapid and efficient method of 3D scaffolds fabrication by using optical lithography and micro-molding techniques. Bioresorbable polymer poly-ε-caprolactone (PCL) was the material used thanks to its high biocompatibility and ability to naturally degrade in tissues. 3D PCL substrates show a particular combination in the designed length scale: cylindrical shaped pillars with 10μm diameter, 10μm height, arranged in a hexagonal lattice with spacing of 20μm were obtained. The sidewalls of the pillars were nanostructured by attributing a 3D architecture to the scaffold. The suitability of these devices as cell culture technology supports was evaluated by plating NIH/3T3 mouse embryonic fibroblasts and human Neural Stem Cells (hNSC) on them. Scanning Electron Microscopy (SEM) analysis was carried out in order to examine the micro- and nano-patterns on the surface of the supports. In addition, after seeding of cells, SEM and immunofluorescence characterization of the fabricated systems were performed to check adhesion, growth and proliferation. It was observed that cells grow and develop healthy on the bio-polymeric devices by giving rise to well-interconnected networks. 3D PCL nano-patterned pillared scaffold therefore may have considerable potential as effective tool for

In vivo evaluation of thiolated poly(acrylic acid) as a drug absorption modulator for MRP2 efflux pump substrates.

Science.gov (United States)

Greindl, Melanie; Föger, Florian; Hombach, Juliane; Bernkop-Schnürch, Andreas

2009-08-01

Recently, several polymers have been reported to modulate drug absorption by inhibition of intestinal efflux pumps such as multidrug resistance proteins (MRPs) and P-glycoprotein (P-gp). The aim of the present study was to evaluate the efficiency of thiolated poly(acrylic acid) (PAA-Cys) to act as a drug absorption modulator for MRP2 efflux pump substrates in vivo, using sulforhodamine 101 as representative MRP2 substrate. In vitro, the permeation-enhancing effect of unmodified PAA and PAA(250)-Cys(,) displaying 580 micromol free thiol groups per gram polymer, was evaluated by using freshly excised rat intestinal mucosa mounted in Ussing-type chambers. In comparison to that of the buffer control, the sulforhodamine 101 transport in the presence of 0.5% unmodified PAA(250) and 0.5% (w/v) PAA(250)-Cys was 1.3- and 4.0-fold improved, respectively. In vivo, sulforhodamine 101 solutions containing 4% (w/v) unmodified PAA(250) or 4% (w/v) thiolated PAA(250) were orally given to rats. The PAA(250)-Cys solution increased the area under the plasma concentration-time curve (AUC(0-12)) of sulforhodamine 101 3.8-fold in comparison to control and 2.2-fold in comparison to unmodified PAA(250). This in vivo study revealed that PAA(250)-Cys significantly increased the oral bioavailability of MRP2 substrate sulforhodamine 101.

Modeling of lipase catalyzed ring-opening polymerization of epsilon-caprolactone.

Science.gov (United States)

Sivalingam, G; Madras, Giridhar

2004-01-01

Enzymatic ring-opening polymerization of epsilon-caprolactone by various lipases was investigated in toluene at various temperatures. The determination of molecular weight and structural identification was carried out with gel permeation chromatography and proton NMR, respectively. Among the various lipases employed, an immobilized lipase from Candida antartica B (Novozym 435) showed the highest catalytic activity. The polymerization of epsilon-caprolactone by Novozym 435 showed an optimal temperature of 65 degrees C and an optimum toluene content of 50/50 v/v of toluene and epsilon-caprolactone. As lipases can degrade polyesters, a maximum in the molecular weight with time was obtained due to the competition of ring opening polymerization and degradation by specific chain end scission. The optimum temperature, toluene content, and the variation of molecular weight with time are consistent with earlier observations. A comprehensive model based on continuous distribution kinetics was developed to model these phenomena. The model accounts for simultaneous polymerization, degradation and enzyme deactivation and provides a technique to determine the rate coefficients for these processes. The dependence of these rate coefficients with temperature and monomer concentration is also discussed.

Biodegradable polymersomes as carriers and release systems for paclitaxel using Oregon Green® 488 labeled paclitaxel as a model compound

NARCIS (Netherlands)

Lee, Jung Seok; Feijen, Jan

2012-01-01

Oregon Green® 488 labeled paclitaxel (Flutax) loaded biodegradable polymersomes (Flutax-Ps) based on methoxy poly(ethylene glycol)-b-poly(d,l-lactide) (mPEG-PDLLA), methoxy poly(ethylene glycol)-b-poly(ε-caprolactone) (mPEG-PCL) or a mixture of the block copolymers (50:50, w/w) were prepared

Renewable poly(δ-decalactone based block copolymer micelles as drug delivery vehicle: in vitro and in vivo evaluation

Directory of Open Access Journals (Sweden)

Kuldeep K. Bansal

2018-03-01

Full Text Available Polymers from natural resources are attracting much attention in various fields including drug delivery as green alternatives to fossil fuel based polymers. In this quest, novel block copolymers based on renewable poly(δ-decalactone (PDL were evaluated for their drug delivery capabilities and compared with a fossil fuel based polymer i.e. methoxy-poly(ethylene glycol-b-poly(ε-caprolactone (mPEG-b-PCL. Using curcumin as a hydrophobic drug model, micelles of PDL block copolymers with different orientation i.e. AB (mPEG-b-PDL, ABA (PDL-b-PEG-b-PDL, ABC (mPEG-b-PDL-b-poly(pentadecalactone and (mPEG-b-PCL were prepared by nanoprecipitation method. The size, drug loading and curcumin stability studies results indicated that mPEG-b-PDL micelles was comparable to its counterpart mPEG-b-PCL micelles towards improved delivery of curcumin. Therefore, mixed micelles using these two copolymers were also evaluated to see any change in size, loading and drug release. Drug release studies proposed that sustained release can be obtained using poly(pentadecalactone as crystalline core whereas rapid release can be achieved using amorphous PDL core. Further, mPEG-b-PDL micelles were found to be non-haemolytic, up to the concentration of 40 mg/mL. In vivo toxicity studies on rats advised low-toxic behaviour of these micelles up to 400 mg/kg dose, as evident by histopathological and biochemical analysis. In summary, it is anticipated that mPEG-b-PDL block copolymer micelles could serve as a renewable alternative for mPEG-b-PCL copolymers in drug delivery applications.

Compartmentalization Technologies via Self-Assembly and Cross-Linking of Amphiphilic Random Block Copolymers in Water.

Science.gov (United States)

Matsumoto, Mayuko; Terashima, Takaya; Matsumoto, Kazuma; Takenaka, Mikihito; Sawamoto, Mitsuo

2017-05-31

Orthogonal self-assembly and intramolecular cross-linking of amphiphilic random block copolymers in water afforded an approach to tailor-make well-defined compartments and domains in single polymer chains and nanoaggregates. For a double compartment single-chain polymer, an amphiphilic random block copolymer bearing hydrophilic poly(ethylene glycol) (PEG) and hydrophobic dodecyl, benzyl, and olefin pendants was synthesized by living radical polymerization (LRP) and postfunctionalization; the dodecyl and benzyl units were incorporated into the different block segments, whereas PEG pendants were statistically attached along a chain. The copolymer self-folded via the orthogonal self-assembly of hydrophobic dodecyl and benzyl pendants in water, followed by intramolecular cross-linking, to form a single-chain polymer carrying double yet distinct hydrophobic nanocompartments. A single-chain cross-linked polymer with a chlorine terminal served as a globular macroinitiator for LRP to provide an amphiphilic tadpole macromolecule comprising a hydrophilic nanoparticle and a hydrophobic polymer tail; the tadpole thus self-assembled into multicompartment aggregates in water.

Ultrasound assisted lipase catalyzed synthesis of poly-6-hydroxyhexanoate.

Science.gov (United States)

Gumel, A M; Annuar, M S M; Chisti, Y; Heidelberg, T

2012-05-01

Ultrasonic irradiation greatly improved the Candida antarctica lipase B mediated ring opening polymerization of ε-caprolactone to poly-6-hydroxyhexanoate in the ionic liquid 1-ethyl-3-methylimidazolium tetraflouroborate. Compared to the conventional nonsonicated reaction, sonication improved the monomer conversion by 63% and afforded a polymer product of a narrower molecular weight distribution and a higher degree of crystallinity. Under sonication, the polydispersity index of the product was ~1.44 compared to a value of ~2.55 for the product of the conventional reaction. With sonication, nearly 75% of the monomer was converted to product, but the conversion was only ~16% for the reaction carried out conventionally. Compared to conventional operation, sonication enhanced the rate of polymer propagation by >2-fold and the turnover number of the lipase by >3-fold. Copyright © 2011 Elsevier B.V. All rights reserved.

Amphiphilic graft copolymer based on poly(styrene-co-maleic anhydride) with low molecular weight polyethylenimine for efficient gene delivery

Science.gov (United States)

Duan, Xiaopin; Xiao, Jisheng; Yin, Qi; Zhang, Zhiwen; Mao, Shirui; Li, Yaping

2012-01-01

Background and methods A new amphiphilic comb-shaped copolymer (SP) was synthesized by conjugating poly(styrene-co-maleic anhydride) with low molecular weight polyethyleneimine for gene delivery. Fourier transform infrared spectrum, 1H nuclear magnetic resonance, and gel permeation chromatography were used to characterize the graft copolymer. Results The buffering capability of SP was similar to that of polyethyleneimine within the endosomal pH range. The copolymer could condense DNA effectively to form complexes with a positive charge (13–30 mV) and a small particle size (130–200 nm) at N/P ratios between 5 and 20, and protect DNA from degradation by DNase I. In addition, SP showed much lower cytotoxicity than polyethyleneimine 25,000. Importantly, the gene transfection activity and cellular uptake of SP-DNA complexes were all markedly higher than that of complexes of polyethyleneimine 25,000 and DNA in MCF-7 and MCF-7/ADR cell lines. Conclusion This work highlights the promise of SP as a safe and efficient synthetic vector for DNA delivery. PMID:23028224

Osteogenic differentiation of stem cells from human exfoliated deciduous teeth on poly(ε-caprolactone) nanofibers containing strontium phosphate

Energy Technology Data Exchange (ETDEWEB)

Su, Wen-Ta, E-mail: f10549@ntut.edu.tw [Department of Chemical Engineering and Biotechnology, National Taipei University of Technology, Taipei, Taiwan (China); Wu, Pai-Shuen [Department of Chemical Engineering and Biotechnology, National Taipei University of Technology, Taipei, Taiwan (China); Huang, Te-Yang [Department of Orthopedic Surgery, Mackay Memorial Hospital, Taipei, Taiwan (China)

2015-01-01

Mimicking the architecture of the extracellular matrix is an effective strategy for tissue engineering. Composite nanofibers similar to natural bone structure can be prepared via an electrospinning technique and used in biomedical applications. Stem cells from human exfoliated deciduous teeth (SHEDs) can differentiate into multiple cell lineages, such as cells that are alternative sources of stem cells for tissue engineering. Strontium has important functions in bone remodeling; for example, this element can simulate bone formation and decrease bone resorption. Incorporating strontium phosphate into nanofibers provides a potential material for bone tissue engineering. This study investigated the potential of poly(ε-caprolactone) (PCL) nanofibers coated or blended with strontium phosphate for the osteogenic differentiation of SHEDs. Cellular morphology and MTT assay revealed that nanofibers effectively support cellular attachment, spreading, and proliferation. Strontium-loaded PCL nanofibers exhibited higher expressions of collagen type I, alkaline phosphatase, biomineralization, and bone-related genes than pure PCL nanofibers during the osteogenic differentiation of SHEDs. This study demonstrated that strontium can be an effective inducer of osteogenesis for SHEDs. Understanding the function of bioceramics (such as strontium) is useful in designing and developing strategies for bone tissue engineering. - Highlights: • SHEDs have been considered as alternative sources of adult stem cells in tissue engineering. • Strontium phosphate into nanofibers provides a potential material for bone tissue engineering. • Nanofibers coated or blended with strontium phosphate for the osteogenic differentiation of SHEDs.

Osteogenic differentiation of stem cells from human exfoliated deciduous teeth on poly(ε-caprolactone) nanofibers containing strontium phosphate

International Nuclear Information System (INIS)

Su, Wen-Ta; Wu, Pai-Shuen; Huang, Te-Yang

2015-01-01

Mimicking the architecture of the extracellular matrix is an effective strategy for tissue engineering. Composite nanofibers similar to natural bone structure can be prepared via an electrospinning technique and used in biomedical applications. Stem cells from human exfoliated deciduous teeth (SHEDs) can differentiate into multiple cell lineages, such as cells that are alternative sources of stem cells for tissue engineering. Strontium has important functions in bone remodeling; for example, this element can simulate bone formation and decrease bone resorption. Incorporating strontium phosphate into nanofibers provides a potential material for bone tissue engineering. This study investigated the potential of poly(ε-caprolactone) (PCL) nanofibers coated or blended with strontium phosphate for the osteogenic differentiation of SHEDs. Cellular morphology and MTT assay revealed that nanofibers effectively support cellular attachment, spreading, and proliferation. Strontium-loaded PCL nanofibers exhibited higher expressions of collagen type I, alkaline phosphatase, biomineralization, and bone-related genes than pure PCL nanofibers during the osteogenic differentiation of SHEDs. This study demonstrated that strontium can be an effective inducer of osteogenesis for SHEDs. Understanding the function of bioceramics (such as strontium) is useful in designing and developing strategies for bone tissue engineering. - Highlights: • SHEDs have been considered as alternative sources of adult stem cells in tissue engineering. • Strontium phosphate into nanofibers provides a potential material for bone tissue engineering. • Nanofibers coated or blended with strontium phosphate for the osteogenic differentiation of SHEDs

Amino-Functionalized Multiwalled Carbon Nanotubes Lead to Successful Ring-Opening Polymerization of Poly(ε-caprolactone): Enhanced Interfacial Bonding and Optimized Mechanical Properties.

Science.gov (United States)

Roumeli, Eleftheria; Papageorgiou, Dimitrios G; Tsanaktsis, Vasilios; Terzopoulou, Zoe; Chrissafis, Konstantinos; Avgeropoulos, Apostolos; Bikiaris, Dimitrios N

2015-06-03

In this work, the synthesis, structural characteristics, interfacial bonding, and mechanical properties of poly(ε-caprolactone) (PCL) nanocomposites with small amounts (0.5, 1.0, and 2.5 wt %) of amino-functionalized multiwalled carbon nanotubes (f-MWCNTs) prepared by ring-opening polymerization (ROP) are reported. This method allows the creation of a covalent-bonding zone on the surface of nanotubes, which leads to efficient debundling and therefore satisfactory dispersion and effective load transfer in the nanocomposites. The high covalent grafting extent combined with the higher crystallinity provide the basis for a significant enhancement of the mechanical properties, which was detected in the composites with up to 1 wt % f-MWCNTs. Increasing filler concentration encourages intrinsic aggregation forces, which allow only minor grafting efficiency and poorer dispersion and hence inferior mechanical performance. f-MWCNTs also cause a significant improvement on the polymerization reaction of PCL. Indeed, the in situ polymerization kinetics studies reveal a significant decrease in the reaction temperature, by a factor of 30-40 °C, combined with accelerated the reaction kinetics during initiation and propagation and a drastically reduced effective activation energy.

Atmospheric Pressure Plasma Jet Treatment of Poly-ε-caprolactone Polymer Solutions To Improve Electrospinning.

Science.gov (United States)

Grande, Silvia; Van Guyse, Joachim; Nikiforov, Anton Y; Onyshchenko, Iuliia; Asadian, Mahtab; Morent, Rino; Hoogenboom, Richard; De Geyter, Nathalie

2017-09-27

An atmospheric pressure plasma jet (APPJ) specifically designed for liquid treatment has been used in this work to improve the electrospinnability of a 5 w/v % solution of poly-ε-caprolactone (PCL) in a mixture of chloroform and N,N-dimethylformamide. Untreated PCL solutions were found to result in nonuniform fibers containing a large number of beads, whereas plasma-treated solutions (exposure time of 2-5 min) enabled the generation of beadless, uniform nanofibers with an average diameter of 450 nm. This enhanced electrospinnability was found to be mainly due to the highly increased conductivity of the plasma-modified PCL solutions. Consequently, more stretching of the polymer jet occurred during electrospinning, leading to the generation of bead-free fibers. Plasma treatment also results in an increased viscosity and decreased pH values. To explain these observed changes, optical emission spectroscopy (OES) has been used to examine the excited species present in the APPJ in contact with the PCL solution. This study revealed that the peaks attributed to H, CH, CH 2 , and C 2 species could be responsible for the degradation of solvent molecules and/or PCL structures during the plasma treatment. Size exclusion chromatography and X-ray photoelectron spectroscopy results showed that the molecular weight and the chemical composition of PCL were not significantly affected by the APPJ treatment. Plasma exposure mainly results in the degradation of the solvent molecules instead of modifying the PCL macromolecules, preserving the original polymer as much as possible. A hypothesis for the observed macroscopic changes in viscosity and pH values could be the generation of new chemical species such as HCl and/or HNO 3 . These species are characterized by their high conductivity, low pH values, and strong polarity and could enhance the solvent quality for PCL, leading to the expansion of the polymer coil, which could in turn explain the observed enhanced viscosity after plasma

Uniformly-dispersed nanohydroxapatite-reinforced poly(ε-caprolactone) composite films for tendon tissue engineering application

Energy Technology Data Exchange (ETDEWEB)

Tong, Shi Yun [Department of Mechanical Engineering, National University of Singapore, 9 Engineering Drive 1, Singapore 117 576 (Singapore); Wang, Zuyong, E-mail: zuyong.nus@gmail.com [Department of Mechanical Engineering, National University of Singapore, 9 Engineering Drive 1, Singapore 117 576 (Singapore); Lim, Poon Nian [Department of Mechanical Engineering, National University of Singapore, 9 Engineering Drive 1, Singapore 117 576 (Singapore); Wang, Wilson [Department of Orthopaedic Surgery, National University of Singapore, 5 Lower Kent Ridge Road, Singapore 119 074 (Singapore); Thian, Eng San, E-mail: mpetes@nus.edu.sg [Department of Mechanical Engineering, National University of Singapore, 9 Engineering Drive 1, Singapore 117 576 (Singapore)

2017-01-01

Regeneration of injuries at tendon-to-bone interface (TBI) remains a challenging issue due to the complex tissue composition involving both soft tendon tissues and relatively hard bone tissues. Tissue engineering using polymeric/ceramic composites has been of great interest to generate scaffolds for tissue's healing at TBI. Herein, we presented a novel method to blend polymers and bioceramics for tendon tissue engineering application. A homogeneous composite comprising of nanohydroxyapatite (nHA) particles in poly(ε-caprolactone) (PCL) matrix was obtained using a combination of solvent and mechanical blending process. X-ray diffraction analysis showed that the as-fabricated PCL/nHA composite film retained phase-pure apatite and semi-crystalline properties of PCL. Infrared spectroscopy spectra confirmed that the PCL/nHA composite film exhibited the characteristics functional groups of PCL and nHA, without alteration to the chemical properties of the composite. The incorporation of nHA resulted in PCL/nHA composite film with improved mechanical properties such as Young's Modulus and ultimate tensile stress, which were comparable to that of the native human rotator tendon. Seeding with human tenocytes, cells attached on the PCL/nHA composite film, and after 14 days of culturing, these cells could acquire elongated morphology without induced cytotoxicity. PCL/nHA composite film could also result in increased cell metabolism with prolonged culturing, which was comparable to that of the PCL group and higher than that of the nHA group. All these results demonstrated that the developed technique of combining solvent and mechanical blending could be applied to fabricate composite films with potential for tendon tissue engineering applications. - Highlights: • A novel method fabricating polymeric/nanoceramic composite film was proposed. • The method involved solvent and mechanical blending to form a homogeneous film. • The film retained physicochemical

Amphiphilic copolymers based on PEG-acrylate as surface active water viscosifiers : Towards new potential systems for enhanced oil recovery

NARCIS (Netherlands)

Raffa, Patrizio; Broekhuis, Antonius A.; Picchioni, Francesco

2016-01-01

With the purpose of investigating new potential candidates for enhanced oil recovery (EOR), amphiphilic copolymers based on Poly(ethylene glycol) methyl ether acrylate (PEGA) have been prepared by Atom Transfer Radical Polymerization (ATRP). A P(PEGA) homopolymer, a block copolymer with styrene

Star-shaped poly[(trimethylene carbonate)-co-(epsilon-caprolactone)] and its block copolymers with lactide/glycolide : synthesis, characterization and properties

NARCIS (Netherlands)

Joziasse, CAP; Grablowitz, H; Pennings, AJ

Linear and star-shaped copolymers of trimethylene carbonat/epsilon-caprolactone were synthesized using different polyol initiators and catalysts. Unexpectedly, when dipentaerythritol was used as an initiator cross-linked rubbers were obtained, that swell in chlorofonn. This network formation can be

Vascular Endothelial Growth Factor Improves Physico-Mechanical Properties and Enhances Endothelialization of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/Poly(ε-caprolactone) Small-Diameter Vascular Grafts In vivo.

Science.gov (United States)

Antonova, Larisa V; Sevostyanova, Victoria V; Kutikhin, Anton G; Mironov, Andrey V; Krivkina, Evgeniya O; Shabaev, Amin R; Matveeva, Vera G; Velikanova, Elena A; Sergeeva, Evgeniya A; Burago, Andrey Y; Vasyukov, Georgiy Y; Glushkova, Tatiana V; Kudryavtseva, Yuliya A; Barbarash, Olga L; Barbarash, Leonid S

2016-01-01

The combination of a natural polymer poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and a synthetic hydrophobic polymer poly(ε-caprolactone) (PCL) is promising for the preparation of biodegradable and biocompatible small-diameter vascular grafts for bypass surgery. However, physico-mechanical properties and endothelialization rate of PHBV/PCL grafts are poor. We suggested that incorporation of vascular endothelial growth factor (VEGF) into PHBV/PCL grafts may improve their physico-mechanical properties and enhance endothelialization. Here we compared morphology, physico-mechanical properties, and in vivo performance of electrospun small-diameter vascular grafts prepared from PHBV/PCL with and without VEGF. Structure of the graft surface and physico-mechanical properties were examined by scanning electron microscopy and universal testing machine, respectively. Grafts were implanted into rat abdominal aorta for 1, 3, and 6 months with the further histological, immunohistochemical, and immunofluorescence examination. PHBV/PCL grafts with and without VEGF were highly porous and consisted mostly of nanoscale and microscale fibers, respectively. Mean pore diameter and mean pore area were significantly lower in PHBV/PCL/VEGF compared to PHBV/PCL grafts (1.47 μm and 10.05 μm(2); 2.63 μm and 47.13 μm(2), respectively). Durability, elasticity, and stiffness of PHBV/PCL grafts with VEGF were more similar to internal mammary artery compared to those without, particularly 6 months postimplantation. Both qualitative examination and quantitative image analysis showed that three-fourths of PHBV/PCL grafts with VEGF were patent and had many CD31-, CD34-, and vWF-positive cells at their inner surface. However, all PHBV/PCL grafts without VEGF were occluded and had no or a few CD31-positive cells at the inner surface. Therefore, VEGF enhanced endothelialization and improved graft patency at all the time points in a rat abdominal aorta replacement model. In conclusion, PHBV

Tubular scaffolds of gelatin and poly(ε-caprolactone)-block-poly(γ-glutamic acid) blending hydrogel for the proliferation of the primary intestinal smooth muscle cells of rats

International Nuclear Information System (INIS)

Jwo, Shyh-Chuan; Chiu, Chu-Hua; Hsieh, Ming-Fa; Tang, Shye-Jye

2013-01-01

The proper regeneration of intestinal muscle for functional peristalsis is the most challenging aspect of current small intestine tissue engineering. This study aimed to fabricate a hydrogel scaffold for the proliferation of intestinal smooth muscle cells (ISMCs). Tubular porous scaffolds of 10–20 wt% gelatin and 0.05–0.1 wt% poly(ε-caprolactone)-block-poly(γ-glutamic acid) blending hydrogel were cross-linked by carbodiimide and succinimide in an annular space of a glass mold. The scaffolds with higher gelatin contents degraded slower in the phosphate buffer solution. In rheological measurements, the hydrated scaffolds were elastic (all tangent delta <0.45); they responded differentially to frequency, indicating a complete viscoelastic property that is beneficial for soft tissue regeneration. Isolated rat ISMCs, with the characteristic biomarkers α-SMA, calponin and myh11, were loaded into the scaffolds by using either static or centrifugal methods. The average cell density inside the scaffolds increased in a time-dependent manner in most scaffolds of both seeding groups, although at early time points (seven days) the centrifugal seeding method trapped cells more efficiently and yielded a higher cell density than the static seeding method. The static seeding method increased the cell density from 7.5-fold to 16.3-fold after 28 days, whereas the centrifugal procedure produced a maximum increase of only 2.4-fold in the same period. In vitro degradation data showed that 50–80% of the scaffold was degraded by the 14th day. However, the self-secreted extracellular matrix maintained the integrity of the scaffolds for cell proliferation and spreading for up to 28 days. Confocal microscopic images revealed cell–cell contacts with the formation of a 3D network, demonstrating that the fabricated scaffolds were highly biocompatible. Therefore, these polymeric biomaterials hold great promise for in vivo applications of intestinal tissue engineering. (paper)

Infrared spectral studies of various metal polyacrylates

International Nuclear Information System (INIS)

McCluskey, P.H.; Snyder, R.L.; Condrate, R.A. Sr.

1989-01-01

A new process for the production of high surface area, high reactivity ceramic oxide powders involves the bonding of metal cations to polymeric polyacrylate chains. This process results in the formation of a gelatinous metal polyacrylate precipitate which can be easily removed from the mother liquor, and then calcined to form a high density ceramic oxide. Using FTIR spectroscopy, the nature of the structural arrangements has been studied for metal complexes in the yttrium, lanthanum, aluminum, cerium, copper, and iron polyacrylates. Interpretation of the infrared spectra indicates that two types of metal complex formation occur in these precipitates, involving bidentate or bridging interactions. The type that is observed for a particular metal ion is dependent on its metal ion size

Synthesis of soft shell poly(styrene) colloids for filtration experiments

DEFF Research Database (Denmark)

Hinge, Mogens

Separating a solid from a liquid is an important unit operation in many different industries e.g. mining, chemical, pharmaceutical and food industries. Solid liquid separation can roughly be divided into three groups. 1) Separation by gravity forces e.g. sedimentation, centrifugation, 2) Separation...... consisting of a solid poly(styrene) (PS) core with a water swollen shell have been employed in investigating the effect from varying amounts and type of water swollen material on filtration dewatering properties. Three series of model material have been used in this investigation 1) poly......(styrene-co-acrylic acid) core-shell colloids with varying thickness of the poly(acrylic acid) (PAA) shell. 2) poly(styrene-co-acrylic acid) core-shell colloids with varying diameter of the PS core and 3) poly(styrene-co-N-isopropylacrylamide) core-shell colloids with varying thickness of the poly...

Application of reactive siloxane prepolymers for the synthesis of thermoplastic poly(ester–siloxanes and poly(ester–ether–siloxanes

Directory of Open Access Journals (Sweden)

VESNA V. ANTIC

2007-02-01

Full Text Available Thermoplastic poly(ester–siloxanes (TPES and poly(ester–ether–siloxane s, (TPEES, based on poly(butylene terephthalate (PBT as the hard segment and different siloxane-prepolymers as the soft segments, were prepared. The TPES and TPEES were synthesized by catalyzed two-step transesterification from dimethyl terephthalate, (DMT, 1,4-butanediol, (BD and a siloxane-prepolymer. Incorporation of dicarboxypropyl- or disilanol-terminated poly(dimethylsiloxanes (PDMS into the polar poly(butylene terephthalate chains resulted in rather inhomogeneous TPES copolymers, which was a consequence of a prononuced phase separation of the polar and non-polar reactants during synthesis. Two concepts were employed to avoid or reduce phase separation: 1 the use of siloxane-containing triblock prepolymers with hydrophilic terminal blocks, such as ethylene oxide (EO, poly(propylene oxide (PPO or poly(caprolactone (PLC when the terminal blocks serve as a compatibilizer between the extremely non-polar PDMS and the polar DMT and BD, and 2 the use of a high-boiling solvent (1,2,4-trichlorobenzene during the first phase of the reaction. Homogeneity was significantly improved in the case of copolymers based on PCL–PDMS–PCL.

Preparation by Poly(Acrylic Acid) Sol-Gel Method and Thermoelectric Properties of γ-Na x CoO2 Bulk Materials

Science.gov (United States)

Li, Xiaoyu; Zhang, Li; Tang, Xinfeng

2017-11-01

γ-Na x CoO2 single-phase powders have been synthesized by a poly(acrylic acid) (PAA) sol-gel (SG) method, and γ-Na x CoO2 bulk ceramic fabricated using spark plasma sintering. The effects of the PAA concentration on the sample phase composition and morphology were investigated. The thermoelectric properties of the γ-Na x CoO2 bulk ceramic were also studied. The results show that the PAA concentration did not significantly affect the crystalline phase of the product. However, agglomeration of γ-Na x CoO2 crystals was suppressed by the steric effect of PAA. The Na x CoO2 bulk ceramic obtained using the PAA SG method had higher crystallographic anisotropy, better chemical homogeneity, and higher density than the sample obtained by solid-state reaction (SSR), leading to improved thermoelectric performance. The PAA SG sample had power factor (in-plane PF = σS 2) of 0.61 mW m-1 K-2 and dimensionless figure of merit ( ZT) along the in-plane direction of 0.19 at 900 K, higher than for the SSR sample (in-plane PF = 0.51 mW m-1 K-2, in-plane ZT = 0.17). These results demonstrate that a simple and feasible PAA SG method can be used for synthesis of Na x CoO2 ceramics with improved thermoelectric properties.

An Amylase-Responsive Bolaform Supra-Amphiphile.

Science.gov (United States)

Kang, Yuetong; Cai, Zhengguo; Tang, Xiaoyan; Liu, Kai; Wang, Guangtong; Zhang, Xi

2016-02-01

An amylase-responsive bolaform supra-amphiphile was constructed by the complexation between β-cyclodextrin and a bolaform covalent amphiphile on the basis of host-guest interaction. The bolaform covalent amphiphile could self-assemble in solution, forming sheet-like aggregates and displaying weak fluorescence because of aggregation-induced quenching. The addition of β-cyclodextrin led to the formation of the bolaform supra-amphiphile, prohibiting the aggregation of the bolaform covalent amphiphile and accompanying with the significant recovery of fluorescence. Upon the addition of α-amylase, with the degradation β-cyclodextrin, the fluorescence of the supra-amphiphile would quench gradually and significantly, and the quenching rate linearly correlated to the concentration of α-amylase. This study enriches the field of supra-amphiphiles on the basis of noncovalent interactions, and moreover, it may provide a facile way to estimate the activity of α-amylase.

Nanoparticles based on novel amphiphilic polyaspartamide copolymers

International Nuclear Information System (INIS)

Craparo, Emanuela Fabiola; Teresi, Girolamo; Ognibene, Maria Chiara; Casaletto, Maria Pia; Bondi, Maria Luisa; Cavallaro, Gennara

2010-01-01

In this article, the synthesis of two amphiphilic polyaspartamide copolymers, useful to obtain polymeric nanoparticles without using surfactants or stabilizing agents, is described. These copolymers were obtained starting from α,β-poly-(N-2-hydroxyethyl)-dl-aspartamide (PHEA) by following a novel synthetic strategy. In particular, PHEA and its pegylated derivative (PHEA-PEG 2000 ) were functionalized with poly(lactic acid) (PLA) through 1,1'-carbonyldiimidazole (CDI) activation to obtain PHEA-PLA and PHEA-PEG 2000 -PLA graft copolymers, respectively. These copolymers were properly purified and characterized by 1 H-NMR, FT-IR, and Size Exclusion Chromatography (SEC) analyses, which confirmed that derivatization reactions occurred. Nanoparticles were obtained from PHEA-PLA and PHEA-PEG 2000 -PLA graft copolymers by using the high pressure homogenization-solvent evaporation method, avoiding the use of surfactants or stabilizing agents. Polymeric nanoparticles were characterized by dimensional analysis, before and after freeze-drying process, and Scanning Electron Microscopy (SEM). Zeta potential measurements and X-ray Photoelectron Spectroscopy (XPS) analysis demonstrated the presence of PEG and/or PHEA onto the PHEA-PEG 2000 -PLA and PHEA-PLA nanoparticle surface, respectively.

Manufacturing and characterization of encapsulated microfibers with different molecular weight poly(ε-caprolactone) (PCL) resins using a melt electrospinning technique

International Nuclear Information System (INIS)

Lee, Jason K; Ko, Junghyuk; Jun, Martin B G; Lee, Patrick C

2016-01-01

Encapsulated structures of poly(ε-caprolactone) microfibers were successfully fabricated through two distinct melt electrospinning methods: melt coaxial and melt-blending electrospinning methods. Both methods resulted in encapsulated microfibers, but the resultant microfibers had different morphologies. Melt coaxial electrospinning formed a dual, semi-concentric structure, whereas melt-blending electrospinning resulted in an islands-in-a-sea fiber structure (i.e. a multiple-core structure). The encapsulated microfibers were produced using a custom-designed melt coaxial electrospinning device and the microfibers were characterized using a scanning electron microscope. To analyze the properties of the melt blended encapsulated fibers and coaxial fibers, the microfiber mesh specimens were collected. The mechanical properties of each microfiber mesh were analyzed through a tensile test. The coaxial microfiber meshes were post processed with a femtosecond laser machine to create dog-bone shaped tensile test specimens, while the melt blended microfiber meshes were kept as-fabricated. The tensile experiments undertaken with coaxial microfiber specimens resulted in an increase in tensile strength compared to 10 k and 45 k monolayer specimens. However, melt blended microfiber meshes did not result in an increase in tensile strength. The melt blended microfiber mesh results indicate that by using greater amounts of 45 k PCL resin within the microstructure, the resulting fibers obtain a higher tensile strength. (paper)

Controlled release of metronidazole from composite poly-ε-caprolactone/alginate (PCL/alginate) rings for dental implants.

Science.gov (United States)

Lan, Shih-Feng; Kehinde, Timilehin; Zhang, Xiangming; Khajotia, Sharukh; Schmidtke, David W; Starly, Binil

2013-06-01

Dental implants provide support for dental crowns and bridges by serving as abutments for the replacement of missing teeth. To prevent bacterial accumulation and growth at the site of implantation, solutions such as systemic antibiotics and localized delivery of bactericidal agents are often employed. The objective of this study was to demonstrate a novel method of controlled localized delivery of antibacterial agents to an implant site using a biodegradable custom fabricated ring. The study involved incorporating a model antibacterial agent (metronidazole) into custom designed poly-ε-caprolactone/alginate (PCL/alginate) composite rings to produce the intended controlled release profile. The rings can be designed to fit around the body of any root form dental implants of various diameters, shapes and sizes. In vitro release studies indicate that pure (100%) alginate rings exhibited an expected burst release of metronidazole in the first few hours, whereas Alginate/PCL composite rings produced a medium burst release followed by a sustained release for a period greater than 4 weeks. By varying the PCL/alginate weight ratios, we have shown that we can control the amount of antibacterial agents released to provide the minimal inhibitory concentration (MIC) needed for adequate protection. The fabricated composite rings have achieved a 50% antibacterial agent release profile over the first 48 h and the remaining amount slowly released over the remainder of the study period. The PCL/alginate agent release characteristic fits the Ritger-Peppas model indicating a diffusion-based mechanism during the 30-day study period. The developed system demonstrates a controllable drug release profile and the potential for the ring to inhibit bacterial biofilm growth for the prevention of diseases such as peri-implantitis resulting from bacterial infection at the implant site. Copyright © 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Multi-Composite Bioactive Osteogenic Sponges Featuring Mesenchymal Stem Cells, Platelet-Rich Plasma, Nanoporous Silicon Enclosures, and Peptide Amphiphiles for Rapid Bone Regeneration

Directory of Open Access Journals (Sweden)

Dongmei Fan

2011-06-01

Full Text Available A novel bioactive sponge was created with a composite of type I collagen sponges or porous poly(e-caprolactone (PCL scaffolds, platelet-rich plasma (PRP, BMP2-loaded nanoporous silicon enclosure (NSE microparticles, mineralizing peptide amphiphiles (PA, and mesenchymal stem cells (MSC. Primary MSC from cortical bone (CB  tissue proved to form more and larger colony units, as well as produce more mineral matrix under osteogenic differentiation, than MSC from bone marrow (BM. Coating pre-treatments were optimized for maximum cell adhesion and mineralization, while a PRP-based gel carrier was created to efficiently deliver and retain MSC and  microparticles within a porous scaffold while simultaneously promoting cell recruitment, proliferation, and angiogenesis. Components and composite sponges were evaluated for osteogenic differentiation in vitro. Osteogenic sponges were loaded with MSC, PRP, PA, and NSE and implanted subcutaneously in rats to evaluate the formation of bone tissue and angiogenesis in vivo. It was found that the combination of a collagen sponge with CB MSC, PRP, PA, and the BMP2-releasing NSE formed the most bone and was most vascularized by four weeks compared to analogous composites featuring BM MSC or PCL or lacking PRP, PA, and NSE. This study indicates that CB MSC should be considered as an alternative to marrow as a source of stem cells, while the PRP-PA cell and microparticle delivery system may be utilized for diverse tissue engineering applications.

Novel Nanocomposite Optical Plastics: Dispersion of Titanium in Polyacrylates

Directory of Open Access Journals (Sweden)

Gunjan Suri

2010-01-01

Full Text Available Polyacrylates have become the preferred materials for optical applications replacing the conventionally used glass due to their superior optical clarity. The major disadvantage with polyacrylates is their low (1.40–1.50 refractive index besides their poor impact resistance. The improvements in refractive index as well as mechanical properties can be achieved by way of incorporation of metals or metal compounds in the matrix. A novel methodology for the incorporation of high refractive index metals into low refractive index polymeric materials to improve the refractive index and impact resistance of the latter has been developed. With the in-situ formation of nanoparticles of TiO2, the refractive index of polyacrylates improved from 1.45 to 1.53 and the Abbe number increased from 40 to 57. One of the interesting dimension of this study pertains to the possibility of tailor-making of the two key optical properties of materials by way of varying the amount of TiO2 being formed in-situ. Thermal stability and impact resistance of nano dispersed (4.3% by wt. of Ti polyacrylates are found to be better than the neat polyacrylates. Moreover, TiO2-containing polyacrylate is of light weight. TEM, SEM, and IR analysis confirms the in-situ formation of nanoparticles of TiO2. Gamma irradiation has been used as an eco-friendly technique for polymerization. The developed compositions can be cast polymerized into clear and bubble free material for optical applications.

Controlled swelling and adsorption properties of polyacrylate/montmorillonite composites

Energy Technology Data Exchange (ETDEWEB)

Natkanski, Piotr [Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow (Poland); Kustrowski, Piotr, E-mail: kustrows@chemia.uj.edu.pl [Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow (Poland); Bialas, Anna; Piwowarska, Zofia [Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow (Poland); Michalik, Marek [Institute of Geological Sciences, Jagiellonian University, Oleandry 2a, 30-063 Krakow (Poland)

2012-10-15

A series of novel polyacrylate/montmorillonite composites was synthesized by in situ polymerization in aqueous slurry of clay. Dissociated (obtained by adding ammonium or sodium hydroxide) and undissociated forms of acrylic acid were used as monomers in the hydrogel synthesis. The structure and composition of the samples were studied by powder X-ray diffraction, diffuse reflectance infra-red Fourier transform spectroscopy, thermogravimetry and elemental analysis. It has been found that the kind of monomer influences strongly the location of a polymer chain in the formed composite. Complete intercalation of hydrogel into the interlayer space of montmorillonite was observed for sodium polyacrylate, whereas polyacrylic acid and ammonium polyacrylate mainly occupied the outer surface of the clay. The position of hydrogel determined the swelling and adsorption properties of the studied composites. The important factor influencing the kinetics of Fe(III) cation adsorption was pH. The analysis of adsorption isotherms allowed to propose the mechanism of Fe(III) cation adsorption. Highlights: Black-Right-Pointing-Pointer Polyacrylate hydrogels can be introduced into the interlayers of clay. Black-Right-Pointing-Pointer The position of hydrogel in the composite depends on the polymer type. Black-Right-Pointing-Pointer Ammonium polyacrylate places outside the clay, sodium one is intercalated into it. Black-Right-Pointing-Pointer Swelling and adsorption capacities can be controlled by the polymer position. Black-Right-Pointing-Pointer High adsorption efficiency in Fe(III) removal was observed.

Poly(methacrylic) Acid and g-methacryloxypropyltrimethoxy Silane/Clay Nanocomposites Prepared by In-Situ Polymerization

OpenAIRE

GÜLTEK, Ahmet; SEÇKİN, Turgay

2002-01-01

Poly(methacrylic acid) and poly(acrylic acid) nanocomposites were prepared by in-situ polymerization of g-methacryloxypropyltrimethoxysilane (A174)/clay nanocomposites in which the macromonomer was generated by grafting A-174 onto activated clay samples via hydroxyl groups or via intercalation. In- situ polymerization was carried out in the presence of an initiator. It was found that the structural affinity between the methacrylic or acrylic acid monomers and the amount of clay playe...

Synthesis of Highly Porous Poly(tert-butyl acrylate)-b-polysulfone-b-poly(tert-butyl acrylate) Asymmetric Membranes

KAUST Repository

Xie, Yihui; Moreno Chaparro, Nicolas; Calo, Victor M.; Cheng, Hong; Hong, Pei-Ying; Sougrat, Rachid; Behzad, Ali Reza; Tayouo Djinsu, Russell; Nunes, Suzana Pereira

2016-01-01

For the first time, self-assembly and non-solvent induced phase separation was applied to polysulfone-based linear block copolymers, reaching mechanical stability much higher than other block copolymers membranes used in this method, which were mainly based on polystyrene blocks. Poly(tert-butyl acrylate)-b-polysulfone-b-poly(tert-butyl acrylate) (PtBA30k-b-PSU14k-b-PtBA30k) with a low polydispersity of 1.4 was synthesized by combining step-growth condensation and RAFT polymerization. Various advanced electron microscopies revealed that PtBA30k-b-PSU14k-b-PtBA30k assembles into worm-like cylindrical micelles in DMAc and adopts a “flower-like” arrangement with the PSU central block forming the shell. Computational modeling described the mechanism of micelle formation and morphological transition. Asymmetric nanostructured membranes were obtained with a highly porous interconnected skin layer and a sublayer with finger-like macrovoids. Ultrafiltration tests confirmed a water permeance of 555 L m-2 h-1 bar-1 with molecular weight cut-off of 28 kg/mol. PtBA segments on the membrane surface were then hydrolyzed and complexed with metals, leading to cross-linking and enhancement of antibacterial capability.

Synthesis of Highly Porous Poly(tert-butyl acrylate)-b-polysulfone-b-poly(tert-butyl acrylate) Asymmetric Membranes

KAUST Repository

Xie, Yihui

2016-03-24

For the first time, self-assembly and non-solvent induced phase separation was applied to polysulfone-based linear block copolymers, reaching mechanical stability much higher than other block copolymers membranes used in this method, which were mainly based on polystyrene blocks. Poly(tert-butyl acrylate)-b-polysulfone-b-poly(tert-butyl acrylate) (PtBA30k-b-PSU14k-b-PtBA30k) with a low polydispersity of 1.4 was synthesized by combining step-growth condensation and RAFT polymerization. Various advanced electron microscopies revealed that PtBA30k-b-PSU14k-b-PtBA30k assembles into worm-like cylindrical micelles in DMAc and adopts a “flower-like” arrangement with the PSU central block forming the shell. Computational modeling described the mechanism of micelle formation and morphological transition. Asymmetric nanostructured membranes were obtained with a highly porous interconnected skin layer and a sublayer with finger-like macrovoids. Ultrafiltration tests confirmed a water permeance of 555 L m-2 h-1 bar-1 with molecular weight cut-off of 28 kg/mol. PtBA segments on the membrane surface were then hydrolyzed and complexed with metals, leading to cross-linking and enhancement of antibacterial capability.

Non-surface activity and micellization behavior of cationic amphiphilic block copolymer synthesized by reversible addition-fragmentation chain transfer process.

Science.gov (United States)

Ghosh, Arjun; Yusa, Shin-ichi; Matsuoka, Hideki; Saruwatari, Yoshiyuki

2011-08-02

Cationic amphiphilic diblock copolymers of poly(n-butylacrylate)-b-poly(3-(methacryloylamino)propyl)trimethylammonium chloride) (PBA-b-PMAPTAC) with various hydrophobic and hydrophilic chain lengths were synthesized by a reversible addition-fragmentation chain transfer (RAFT) process. Their molecular characteristics such as surface activity/nonactivity were investigated by surface tension measurements and foam formation observation. Their micelle formation behavior and micelle structure were investigated by fluorescence probe technique, static and dynamic light scattering (SLS and DLS), etc., as a function of hydrophilic and hydrophobic chain lengths. The block copolymers were found to be non-surface active because the surface tension of the aqueous solutions did not change with increasing polymer concentration. Critical micelle concentration (cmc) of the polymers could be determined by fluorescence and SLS measurements, which means that these polymers form micelles in bulk solution, although they were non-surface active. Above the cmc, the large blue shift of the emission maximum of N-phenyl-1-naphthylamine (NPN) probe and the low micropolarity value of the pyrene probe in polymer solution indicate the core of the micelle is nonpolar in nature. Also, the high value of the relative intensity of the NPN probe and the fluorescence anisotropy of the 1,6-diphenyl-1,3,5-hexatriene (DPH) probe indicated that the core of the micelle is highly viscous in nature. DLS was used to measure the average hydrodynamic radii and size distribution of the copolymer micelles. The copolymer with the longest PBA block had the poorest water solubility and consequently formed micelles with larger size while having a lower cmc. The "non-surface activity" was confirmed for cationic amphiphilic diblock copolymers in addition to anionic ones studied previously, indicating the universality of non-surface activity nature.

Healing of Osteochondral Defects Implanted with Biomimetic Scaffolds of Poly(ε-Caprolactone)/Hydroxyapatite and Glycidyl-Methacrylate-Modified Hyaluronic Acid in a Minipig.

Science.gov (United States)

Hsieh, Yi-Ho; Shen, Bo-Yuan; Wang, Yao-Horng; Lin, Bojain; Lee, Hung-Maan; Hsieh, Ming-Fa

2018-04-09

Articular cartilage is a structure lack of vascular distribution. Once the cartilage is injured or diseased, it is unable to regenerate by itself. Surgical treatments do not effectively heal defects in articular cartilage. Tissue engineering is the most potential solution to this problem. In this study, methoxy poly(ethylene glycol)-block-poly(ε-caprolactone) (mPEG-PCL) and hydroxyapatite at a weight ratio of 2:1 were mixed via fused deposition modeling (FDM) layer by layer to form a solid scaffold. The scaffolds were further infiltrated with glycidyl methacrylate hyaluronic acid loading with 10 ng/mL of Transforming Growth Factor-β1 and photo cross-linked on top of the scaffolds. An in vivo test was performed on the knees of Lanyu miniature pigs for a period of 12 months. The healing process of the osteochondral defects was followed by computer tomography (CT). The defect was fully covered with regenerated tissues in the control pig, while different tissues were grown in the defect of knee of the experimental pig. In the gross anatomy of the cross section, the scaffold remained in the subchondral location, while surface cartilage was regenerated. The cross section of the knees of both the control and experimental pigs were subjected to hematoxylin and eosin staining. The cartilage of the knee in the experimental pig was partially matured, e.g., few chondrocyte cells were enclosed in the lacunae. In the knee of the control pig, the defect was fully grown with fibrocartilage. In another in vivo experiment in a rabbit and a pig, the composite of the TGF-β1-loaded hydrogel and scaffolds was found to regenerate hyaline cartilage. However, scaffolds that remain in the subchondral lesion potentially delay the healing process. Therefore, the structural design of the scaffold should be reconsidered to match the regeneration process of both cartilage and subchondral bone.

Healing of Osteochondral Defects Implanted with Biomimetic Scaffolds of Poly(ε-Caprolactone/Hydroxyapatite and Glycidyl-Methacrylate-Modified Hyaluronic Acid in a Minipig

Directory of Open Access Journals (Sweden)

Yi-Ho Hsieh

2018-04-01

Full Text Available Articular cartilage is a structure lack of vascular distribution. Once the cartilage is injured or diseased, it is unable to regenerate by itself. Surgical treatments do not effectively heal defects in articular cartilage. Tissue engineering is the most potential solution to this problem. In this study, methoxy poly(ethylene glycol-block-poly(ε-caprolactone (mPEG-PCL and hydroxyapatite at a weight ratio of 2:1 were mixed via fused deposition modeling (FDM layer by layer to form a solid scaffold. The scaffolds were further infiltrated with glycidyl methacrylate hyaluronic acid loading with 10 ng/mL of Transforming Growth Factor-β1 and photo cross-linked on top of the scaffolds. An in vivo test was performed on the knees of Lanyu miniature pigs for a period of 12 months. The healing process of the osteochondral defects was followed by computer tomography (CT. The defect was fully covered with regenerated tissues in the control pig, while different tissues were grown in the defect of knee of the experimental pig. In the gross anatomy of the cross section, the scaffold remained in the subchondral location, while surface cartilage was regenerated. The cross section of the knees of both the control and experimental pigs were subjected to hematoxylin and eosin staining. The cartilage of the knee in the experimental pig was partially matured, e.g., few chondrocyte cells were enclosed in the lacunae. In the knee of the control pig, the defect was fully grown with fibrocartilage. In another in vivo experiment in a rabbit and a pig, the composite of the TGF-β1-loaded hydrogel and scaffolds was found to regenerate hyaline cartilage. However, scaffolds that remain in the subchondral lesion potentially delay the healing process. Therefore, the structural design of the scaffold should be reconsidered to match the regeneration process of both cartilage and subchondral bone.

Synthesis and self-assembly of four-armed star copolymer based on poly(ethylene brassylate) hydrophobic block as potential drug carries

Energy Technology Data Exchange (ETDEWEB)

Chen, Jiucun, E-mail: chenjc@swu.edu.cn; Li, Junzhi; Liu, Jianhua; Weng, Bo; Xu, Liqun [Southwest University, Institute for Clean Energy & Advanced Materials (China)

2016-05-15

A novel well-defined four-armed star poly(ethylene brassylate)-b-poly(poly(ethylene glycol)methyl ether methacrylate) (s-PEB-b-P(PEGMA)) was synthesized and self-assembled via the combination of ring-opening polymerization and reversible addition-fragmentation chain transfer polymerization (RAFT) in this work. It proceeded firstly with the synthesis of hydrophobic four-armed star homopolymer of ethylene brassylate (EB) via ROP with organic catalyst, followed by the esterification reaction of s-PEB with chain transfer agent. Afterward, RAFT polymerization of PEGMA monomer was initialed using PEB-based macro-RAFT agent, resulting in the target amphiphilic four-armed star copolymer. The obtained s-PEB-b-P(PEGMA) can assemble into micelles with PEB segments as core and P(PEGMA) segments as shell in aqueous solution. The self-assembly behavior was studied by dynamic light scattering and transmission electron microscope. The micelles of s-PEB-b-P(PEGMA) exhibited higher loading capacity of the anticancer drug doxorubicin (DOX). The investigation of DOX release from the micelles demonstrated that the release rate of the hydrophobic drug could be effectively controlled.Graphical Abstract.

Evaluation of the side effects of poly(epsilon-caprolactone nanocapsules containing atrazine towards maize plants

Directory of Open Access Journals (Sweden)

Halley Caixeta Oliveira

2015-10-01

Full Text Available Poly(epsilon-caprolactone (PCL nanocapsules have been used as a carrier system for the herbicide atrazine, which is commonly applied to maize. We demonstrated previously that these atrazine containing polymeric nanocapsules were ten-fold more effective in the control of mustard plants (a target species, as compared to a commercial atrazine formulation. Since atrazine can have adverse effects on non-target crops, here we analyzed the effect of encapsulated atrazine on growth, physiological and oxidative stress parameters of soil-grown maize plants (Zea mays L.. One day after the post-emergence treatment with PCL nanocapsules containing atrazine (1 mg mL-1, maize plants presented 15 and 21 % decreases in maximum quantum yield of photosystem II and in net CO2 assimilation rate, respectively, as compared to water-sprayed plants. The same treatment led to a 1.8-fold increase in leaf lipid peroxidation in comparison with control plants. However, all of these parameters were unaffected four and eight days after the application of encapsulated atrazine. These results suggested that the negative effects of atrazine were transient, probably due to the ability of maize plants to detoxify the herbicide. When encapsulated atrazine was applied at a ten-fold lower concentration (0.1 mg mL-1, a dosage that is still effective for weed control, no effects were detected even shortly after application. Regardless of the herbicide concentration, neither pre- nor post-emergence treatment with the PCL nanocapsules carrying atrazine resulted in the development of any macroscopic symptoms in maize leaves, and there were no impacts on shoot growth. Additionally, no effects were observed when plants were sprayed with PCL nanocapsules without atrazine. Overall, these results suggested that the use of PCL nanocapsules containing atrazine did not lead to persistent side effects in maize plants, and that the technique could offer a safe tool for weed control without affecting

Cefazolin-containing poly(ε-caprolactone sponge pad to reduce pin tract infection rate in rabbits

Directory of Open Access Journals (Sweden)

Hirotaka Mutsuzaki

2014-04-01

Full Text Available In our previous study, a fibroblast growth factor-2 (FGF-2–apatite composite layer coated on titanium screws effectively prevented pin tract infection in rabbits because of enhanced wound healing; however, the FGF-2–apatite composite layers did not completely prevent pin tract infection. Thus, we recently developed a poly(ε-caprolactone (PCL sponge pad embedded with cefazolin sodium (+CEZ, which has a fast-acting bactericidal effect. The pad is placed on the skin around the screws. The purpose of this study was to determine the anti-infective efficacy of the +CEZ pad on the pin–skin interface of the FGF-2–apatite-coated titanium screws. The +CEZ pads were prepared by mixing PCL and CEZ in 1,4-dioxane, followed by freeze-drying and compaction. They were analyzed regarding their surface structure, in vitro CEZ release profile, and bactericidal activity. The FGF-2–apatite-coated screws were implanted percutaneously in bilateral rabbit proximal tibial metaphyses—with and without the +CEZ pad—for 4 weeks (n = 20. The + CEZ pads consisted of a porous matrix of PCL in which CEZ was embedded. The CEZ-release profile showed an initial burst on Day 1 and a sustained release lasting for 30 days. The +CEZ pad retained its bactericidal activity against Staphylococcus aureus after preincubation on an agar plate for 7 days. Based on visual inspection, the pin tract infection rate was successfully reduced from 72.2% to 15.0% with the +CEZ pad (p < 0.05, which reduced the bacterial count, especially S. aureus (p < 0.05. The histological inflammation rate of the soft tissues was also significantly lower with the +CEZ pad than without it (p < 0.05. The pin tract infection rate was reduced to one-fifth with the +CEZ pad. Using it as described improves infection resistance during percutaneous implantation.

Electrochemical Biosensor for Nitrite Based on Polyacrylic-Graphene Composite Film with Covalently Immobilized Hemoglobin

Directory of Open Access Journals (Sweden)

Raja Zaidatul Akhmar Raja Jamaluddin

2018-04-01

Full Text Available A new biosensor for the analysis of nitrite in food was developed based on hemoglobin (Hb covalently immobilized on the succinimide functionalized poly(n-butyl acrylate-graphene [poly(nBA-rGO] composite film deposited on a carbon-paste screen-printed electrode (SPE. The immobilized Hb on the poly(nBA-rGO conducting matrix exhibited electrocatalytic ability for the reduction of nitrite with significant enhancement in the reduction peak at −0.6 V versus Ag/AgCl reference electrode. Thus, direct determination of nitrite can be achieved by monitoring the cathodic peak current signal of the proposed polyacrylic-graphene hybrid film-based voltammetric nitrite biosensor. The nitrite biosensor exhibited a reproducible dynamic linear response range from 0.05–5 mg L−1 nitrite and a detection limit of 0.03 mg L−1. No significant interference was observed by potential interfering ions such as Ca2+, Na+, K+, NH4+, Mg2+, and NO3− ions. Analysis of nitrite in both raw and processed edible bird’s nest (EBN samples demonstrated recovery of close to 100%. The covalent immobilization of Hb on poly(nBA-rGO composite film has improved the performance of the electrochemical nitrite biosensor in terms of broader detection range, lower detection limit, and prolonged biosensor stability.

Light scattering measurement of sodium polyacrylate products

Science.gov (United States)

Lama, Nisha; Norwood, David; Boone, Steven; Massie-Boyer, Valerie

2015-03-01

In the presentation, we will describe the use of a multi-detector HPLC incorporating the DAWN EOS multi-angle laser light scattering (MALLS) detector to measure the properties such as molecular weight, RMS radius, contour and persistence length and polydispersity of sodium polyacrylate products. The samples of sodium polyacrylate are used in various industries as thickening agents, coating dispersants, artificial snow, laundry detergent and disposable diapers. Data and results obtained from the experiment will be presented.

Transport of poly(acrylic acid) coated 2-line ferrihydrite nanoparticles in saturated aquifer sediments for environmental remediation

Science.gov (United States)

Xiang, Aishuang; Zhou, Sheng; Koel, Bruce E.; Jaffé, Peter R.

2014-04-01

Groundwater remediation using iron oxide and zero-valent iron nanoparticles (NPs) can be effective, but is limited in many applications due to the NP strong retention in groundwater-saturated porous media after injection, the passivation of the porous surface, and the high cost of nanomaterials versus macro scale iron. In this study, we investigated transport of bare and polymer-coated 2-line ferrihydrite NPs (30-300 nm) in saturated aquifer sediments. The influence of poly(acrylic acid) (PAA) polymer coatings was studied on the colloidal stability and transport in sediments packed column tests simulating groundwater flow in saturated sediments. In addition, the influence of calcium cations was investigated by transport measurements using sediments with calcium concentrations in the aqueous phase ranging from 0.5 (typical for most sediments) to 2 mM. Measurements were also made of zeta potential, hydrodynamic diameter, polymer adsorption and desorption properties, and bio-availability of PAA-coated NPs. We found that NP transport through the saturated aquifer sediments was improved by PAA coating and that the transport properties could be tuned by adjusting the polymer concentration. We further discovered that PAA coatings enhanced NP transport, compared to bare NPs, in all calcium-containing experiments tested, however, the presence of calcium always exhibited a negative effect on NP transport. In tests of bioavailability, the iron reduction rate of the coated and bare NPs by Geobacter sulfurreducens was the same, which shows that the PAA coating does not significantly reduce NP Fe(III) bioavailability. Our results demonstrate that much improved transport of iron oxide NP can be achieved in saturated aquifer sediments by introducing negatively charged polyelectrolytes and optimizing polymer concentrations, and furthermore, these coated NPs retain their bioavailability that is needed for applications in bio-environmental remediation.

The development and characterization of a primarily mineral calcium phosphate - poly(epsilon-caprolactone) biocomposite

Science.gov (United States)

Dunkley, Ian Robert

Orthopaedic reconstruction often involves the surgical introduction of structural implants that provide for rigid fixation, skeletal stabilization, and bone integration. The high stresses incurred by these implanted devices have historically limited material choices to metallic and select polymeric formulations. While mechanical requirements are achieved, these non-degradable materials do not participate actively in the remodeling of the skeleton and present the possibility of long-term failure or rejection. This is particularly relevant in cervical fusion, an orthopaedic procedure to treat damaged, degenerative or diseased intervertebral discs. A significant improvement on the available synthetic bone replacement/regeneration options for implants to treat these conditions in the cervical spine may be achieved with the development of primarily mineral biocomposites comprised of a bioactive ceramic matrix reinforced with a biodegradable polymer. Such a biocomposite may be engineered to possess the clinically required mechanical properties of a particular application, while maintaining the ability to be remodeled completely by the body. A biocomposite of Si-doped calcium phosphate (Si-CaP) and poly(epsilon-caprolactone) (PCL) was developed for application as such a synthetic bone material for potential use as a fusion device in the cervical spine. In this thesis, a method by which high mineral content Si-CaP/PCL biocomposites with interpenetrating matrices of mineral and polymer phases may be prepared will be demonstrated, in addition to the effects of the various preparation parameters on the biocomposite density, porosity and mechanical properties. This new technique by which dense, primarily ceramic Si-CaP/PCL biocomposites were prepared, allowed for the incorporation of mineral contents ranging between 45-97vol%. Polymer infiltration, accomplished solely by passive capillary uptake over several days, was found to be capable of fully infiltrating the microporosity

Electrically conductive poly-ɛ-caprolactone/polyethylene glycol/multi-wall carbon nanotube nanocomposite scaffolds coated with fibrin glue for myocardial tissue engineering

Science.gov (United States)

Mehdikhani, Mehdi; Ghaziof, Sharareh

2018-01-01

In this research, poly-ɛ-caprolactone (PCL), polyethylene glycol (PEG), multi-wall carbon nanotubes (MWCNTs), and nanocomposite scaffolds containing 0.5 and 1% (w/w) MWCNTs coated with fibrin glue (FG) were prepared via solvent casting and freeze-drying technique for cardiac tissue engineering. Scanning electron microscopy, transmission electron microscopy, Fourier transform-infrared spectroscopy, and X-ray diffraction were used to characterize the samples. Furthermore, mechanical properties, electrical conductivity, degradation, contact angle, and cytotoxicity of the samples were evaluated. Results showed the uniform distribution of the MWCNTs with some aggregates in the prepared nanocomposite scaffolds. The scaffolds containing 1% (w/w) MWCNTs with and without FG coating illustrated optimum modulus of elasticity, high electrical conductivity, and wettability compared with PCL/PEG and PCL/PEG/0.5%(w/w) MWCNTs' scaffolds. FG coating enhanced electrical conductivity and cell response, and increased wettability of the constructs. The prepared scaffolds were degraded significantly after 60 days of immersion in PBS. Meanwhile, the nanocomposite containing 1% (w/w) MWCNTs with FG coating (S3) showed proper spreading and viability of the myoblasts seeded on it after 1, 4, and 7 days of culture. The scaffold containing 1% (w/w) MWCNTs with FG coating demonstrated optimal properties including acceptable mechanical properties, proper wettability, high electrical conductivity, satisfactory degradation, and excellent myoblasts response to it.

Thiolated polymers: evaluation of the influence of the amount of covalently attached L-cysteine to poly(acrylic acid).

Science.gov (United States)

Palmberger, Thomas F; Albrecht, Karin; Loretz, Brigitta; Bernkop-Schnürch, Andreas

2007-06-01

It was the aim of this study to investigate the influence of the amount of thiol groups being covalently attached to poly(acrylic acid) 450 kDa on its properties. Five different PAA(450)-L-cysteine conjugates (PAA(450)-Cys) were synthesized bearing 53.0 (PAA I), 113.4 (PAA II), 288.8 (PAA III), 549.1 (PAA IV) and 767.0 (PAA V) micromol immobilized thiol groups per gram polymer. Mucoadhesion studies utilizing the rotating cylinder method, tensile studies and disintegration studies were performed. Self-crosslinking properties were measured by the increase in viscosity. Permeation studies were performed on rat small intestine and Caco-2 monolayers using sodium fluorescein as model drug. Following residence times on the rotating cylinder could be identified: PAA I 3.1; PAA II 5.2; PAA III 22.0; PAA IV 33.8; PAA V 53.7; control 1.3 [h]. The disintegration time of all PAA(450)-Cys tablets was strongly dependent on the degree of thiolation of the polymer. Self-crosslinking studies showed that the different PAA(450)-Cys conjugates (3% m/v) in phosphate buffer, pH 6.8, formed intramolecular disulfide bonds. In case of Caco-2 monolayer transport studies following P(app)-values could be identified: PAA I 9.8; PAA II 10.1; PAA III 11.1; PAA IV 8.9; PAA V 8.2; control 6.4 [P(app)x10(-6), cms(-1)]. Mucoadhesive and self-crosslinking properties are strongly dependent on the degree of thiolation of the polymer and with respect to transport studies, an optimum amount of covalently attached L-cysteine could be identified.

Interactions between poly(acrylic acid) and sodium dodecyl sulfate: isothermal titration calorimetric and surfactant ion-selective electrode studies.

Science.gov (United States)

Wang, C; Tam, K C

2005-03-24

Interaction between a monodispersed poly(acrylic acid) (PAA) (M(W) = 5670 g/mol, M(w)/M(n) = 1.02) with sodium dodecyl sulfate (SDS) was investigated using isothermal titration calorimetry (ITC), ion-selective electrode (ISE), and dynamic light scattering measurements. Contrary to previous studies, we report for the first time evidence of interaction between SDS and PAA when the degree of neutralization (alpha) of PAA is lower than 0.2. Hydrocarbon chains of SDS cooperatively bind to apolar segments of PAA driven by hydrophobic interaction. The interaction is both enthalpy and entropy favored (deltaH is negative but deltaS is positive). In 0.05 wt % PAA solution, the SDS concentration corresponding to the onset of binding (i.e., CAC) is approximately 2.4 mM and the saturation concentration (i.e., C(S)) is approximately 13.3 mM when alpha = 0. When PAA was neutralized and ionized, the binding was hindered by the enhanced electrostatic repulsion between negatively charged SDS and PAA chains and improved solubility of the polymer. With increasing alpha to 0.2, CAC increases to approximately 6.2 mM, C(S) drops to 8.6 mM, and the interaction is significantly weakened where the amount of bound SDS on PAA is reduced considerably. The values of CAC and C(S) derived from different techniques are in good agreement. The binding results in the formation of mixed micelles on apolar PAA coils, which then expands and dissociates into single PAA chains. The majority of unneutralized PAA molecules exist as single polymer chains stabilized by bound SDS micelles in solution after the saturation concentration.

Amphiphilic Quantum Dots with Asymmetric, Mixed Polymer Brush Layers: From Single Core-Shell Nanoparticles to Salt-Induced Vesicle Formation

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Brian R. Coleman

2018-03-01

Full Text Available A mixed micelle approach is used to produce amphiphilic brush nanoparticles (ABNPs with cadmium sulfide quantum dot (QD cores and surface layers of densely grafted (σ = ~1 chain/nm2 and asymmetric (fPS = 0.9 mixed polymer brushes that contain hydrophobic polystyrene (PS and hydrophilic poly(methyl methacrylate (PMAA chains (PS/PMAA-CdS. In aqueous media, the mixed brushes undergo conformational rearrangements that depend strongly on prior salt addition, giving rise to one of two pathways to fluorescent and morphologically disparate QD-polymer colloids. (A In the absence of salt, centrosymmetric condensation of PS chains forms individual core-shell QD-polymer colloids. (B In the presence of salt, non-centrosymmetric condensation of PS chains forms Janus particles, which trigger anisotropic interactions and amphiphilic self-assembly into the QD-polymer vesicles. To our knowledge, this is the first example of an ABNP building block that can form either discrete core-shell colloids or self-assembled superstructures in water depending on simple changes to the chemical conditions (i.e., salt addition. Such dramatic and finely tuned morphological variation could inform numerous applications in sensing, biolabeling, photonics, and nanomedicine.

The role of sodium-poly(acrylates) with different weight-average molar mass in phosphate-free laundry detergent builder systems

OpenAIRE

Milojević, Vladimir S.; Ilić-Stojanović, Snežana; Nikolić, Ljubiša; Nikolić, Vesna; Stamenković, Jakov; Stojiljković, Dragan

2013-01-01

In this study, the synthesis of sodium-poly(acrylate) was performed by polymerization of acrylic acid in the water solution with three different contents of potassium-persulphate as an initiator. The obtained polymers were characterized by using HPLC and GPC analyses in order to define the purity and average molar mass of poly(acrylic acid). In order to investigate the influence of sodium-poly(acrylate) as a part of carbonate/zeolite detergent builder system, secondary washing characteristics...

Living Polymerization of N -Substituted β-Alanine N -Carboxyanhydrides: Kinetic Investigations and Preparation of an Amphiphilic Block Copoly-β-Peptoid

KAUST Repository

Grossmann, Arlett

2012-07-03

Poly(α-peptoid)s (N-substituted polyglycines) are interesting peptidomimetic biomaterials that have been discussed for many applications. Poly(β-peptoid)s (N-substituted poly-β-alanines), although equally intriguing, have received much less attention. Here we present results that suggest that while N-substituted β-alanine N-carboxyanhydrides can undergo a living nucleophilic ring-opening polymerization, the solubility of poly(β-peptoid)s can be very poor, which contributes to the limited accessibility using other synthetic approaches. The living character of the polymerization was utilized for the preparation of the first polymerized amphiphilic block copoly-β-peptoid. Our results may open a new route towards highly defined functional poly(β-peptoid)s which could represent biomaterials. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Aligned poly(L-lactic-co-e-caprolactone) electrospun microfibers and knitted structure: a novel composite scaffold for ligament tissue engineering.

Science.gov (United States)

Vaquette, Cédryck; Kahn, Cyril; Frochot, Céline; Nouvel, Cécile; Six, Jean-Luc; De Isla, Natalia; Luo, Li-Hua; Cooper-White, Justin; Rahouadj, Rachid; Wang, Xiong

2010-09-15

We developed a novel technique involving knitting and electrospinning to fabricate a composite scaffold for ligament tissue engineering. Knitted structures were coated with poly(L-lactic-co-e-caprolactone) (PLCL) and then placed onto a rotating cylinder and a PLCL solution was electrospun onto the structure. Highly aligned 2-microm-diameter microfibers covered the space between the stitches and adhered to the knitted scaffolds. The stress-strain tensile curves exhibited an initial toe region similar to the tensile behavior of ligaments. Composite scaffolds had an elastic modulus (150 +/- 14 MPa) similar to the modulus of human ligaments. Biological evaluation showed that cells proliferated on the composite scaffolds and they spontaneously orientated along the direction of microfiber alignment. The microfiber architecture also induced a high level of extracellular matrix secretion, which was characterized by immunostaining. We found that cells produced collagen type I and type III, two main components found in ligaments. After 14 days of culture, collagen type III started to form a fibrous network. We fabricated a composite scaffold having the mechanical properties of the knitted structure and the morphological properties of the aligned microfibers. It is difficult to seed a highly macroporous structure with cells, however the technique we developed enabled an easy cell seeding due to presence of the microfiber layer. Therefore, these scaffolds presented attractive properties for a future use in bioreactors for ligament tissue engineering. (c) 2010 Wiley Periodicals, Inc.

Novel Nano composite Optical Plastics: Dispersion of Titanium in Polyacrylates

International Nuclear Information System (INIS)

Suri, G.; Tyagi, M.; Seshadri, G.; Khandal, R.K.; Verma, G.L.

2010-01-01

Polyacrylates have become the preferred materials for optical applications replacing the conventionally used glass due to their superior optical clarity. The major disadvantage with polyacrylates is their low (1.40-1.50) refractive index besides their poor impact resistance. The improvements in refractive index as well as mechanical properties can be achieved by way of incorporation of metals or metal compounds in the matrix. A novel methodology for the incorporation of high refractive index metals into low refractive index polymeric materials to improve the refractive index and impact resistance of the latter has been developed. With the in-situ formation of nanoparticles of TiO 2 , the refractive index of polyacrylates improved from 1.45 to 1.53 and the Abbe number increased from 40 to 57. One of the interesting dimension of this study pertains to the possibility of tailor-making of the two key optical properties of materials by way of varying the amount of TiO 2 being formed in-situ. Thermal stability and impact resistance of nano dispersed (4.3% by wt. of Ti) polyacrylates are found to be better than the neat polyacrylates. Moreover, TiO 2 -containing polyacrylate is of light weight. TEM, SEM, and IR analysis confirms the in-situ formation of nanoparticles of TiO 2 . Gamma irradiation has been used as an eco-friendly technique for polymerization. The developed compositions can be cast polymerized into clear and bubble free material for optical applications.

Comb-like amphiphilic polypeptide-based copolymer nanomicelles for co-delivery of doxorubicin and P-gp siRNA into MCF-7 cells

Energy Technology Data Exchange (ETDEWEB)

Suo, Aili, E-mail: ailisuo@mail.xjtu.edu.cn [Department of Oncology, The First Affiliated Hospital of Xi' an Jiaotong University, Xi' an 710061 (China); Qian, Junmin, E-mail: jmqian@mail.xjtu.edu.cn [State Key Laboratory for Mechanical Behavior of Materials, Xi' an Jiaotong University, Xi' an 710049 (China); Zhang, Yaping; Liu, Rongrong; Xu, Weijun [State Key Laboratory for Mechanical Behavior of Materials, Xi' an Jiaotong University, Xi' an 710049 (China); Wang, Hejing [Department of Oncology, The First Affiliated Hospital of Xi' an Jiaotong University, Xi' an 710061 (China)

2016-05-01

A comb-like amphiphilic copolymer methoxypolyethylene glycol-graft-poly(L-lysine)-block-poly(L-phenylalanine) (mPEG-g-PLL-b-Phe) was successfully synthesized. To synthesize mPEG-g-PLL-b-Phe, diblock copolymer PLL-b-Phe was first synthesized by successive ring-opening polymerization of α-amino acid N-carboxyanhydrides followed by the removal of benzyloxycarbonyl protecting groups, and then mPEG was grafted onto PLL-b-Phe by reductive amination via Schiff's base formation. The chemical structures of the copolymers were identified by {sup 1}H NMR. mPEG-g-PLL-b-Phe copolymer had a critical micelle concentration of 6.0 mg/L and could self-assemble in an aqueous solution into multicompartment nanomicelles with a mean diameter of approximately 78 nm. The nanomicelles could encapsulate doxorubicin (DOX) through hydrophobic and π–π stacking interactions between DOX molecules and Phe blocks and simultaneously complex P-gp siRNA with cationic PLL blocks via electrostatic interactions. The DOX/P-gp siRNA-loaded nanomicelles showed spherical morphology, possessed narrow particle size distribution and had a mean particle size of 120 nm. The DOX/P-gp siRNA-loaded nanomicelles exhibited pH-responsive release behaviors and displayed accelerated release under acidic conditions. The DOX/P-gp siRNA-loaded nanomicelles were efficiently internalized into MCF-7 cells, and DOX released could successfully reach nuclei. In vitro cytotoxicity assay demonstrated that the DOX/P-gp siRNA-loaded nanomicelles showed a much higher cytotoxicity in MCF-7 cells than DOX-loaded nanomicelles due to their synergistic killing effect and that the blank nanomicelles had good biocompatibility. Thus, the novel comb-like mPEG-g-PLL-b-Phe nanomicelles could be a promising vehicle for co-delivery of chemotherapeutic drug and genetic material. - Highlights: • Comb-like amphiphilic copolymer mPEG-g-PLL-b-Phe was successfully synthesized. • Polypeptide-based copolymer could self-assemble into

Molecular modeling studies of interactions between sodium polyacrylate polymer and calcite surface

Energy Technology Data Exchange (ETDEWEB)

Ylikantola, A. [University of Jyväskylä, Department of Chemistry, P.O. Box 35, University of Jyväskylä, FI-40014 (Finland); Linnanto, J., E-mail: juha.m.linnanto@gmail.com [University of Jyväskylä, Department of Chemistry, P.O. Box 35, University of Jyväskylä, FI-40014 (Finland); University of Tartu, Institute of Physics, Riia 142, EE-51014 Tartu (Estonia); Knuutinen, J.; Oravilahti, A. [University of Jyväskylä, Department of Chemistry, P.O. Box 35, University of Jyväskylä, FI-40014 (Finland); Toivakka, M. [Åbo Akademi University, Laboratory of Paper Coating and Converting and Center for Functional Materials, FI-20500 Turku/Åbo (Finland)

2013-07-01

The interactions between calcite pigment and sodium polyacrylate dispersing agent, widely used in papermaking as paper coating components, were investigated using classical force field and quantum chemical approaches. The objective was to understand interactions between the calcite surface and sodium polyacrylate polymer at 300 K using molecular dynamics simulations. A quantum mechanical ab initio Hartree–Fock method was also used to obtain detailed information about the sodium polyacrylate polymer structure. The effect of water molecules (moisture) on the interactions was also examined. Calculations showed that molecular weight, branching and the orientation of sodium polyacrylate polymers influence the interactions between the calcite surface and the polymer. The force field applied, and also water molecules, were found to have an impact on all systems studied. Ab initio Hartree–Fock calculations indicated that there are two types of coordination between sodium atoms and carboxylate groups of the sodium polyacrylate polymer, inter- and intra-carboxylate group coordination. In addition, ab initio Hartree–Fock calculations of the structure of the sodium polyacrylate polymer produced important information regarding interactions between the polymers and carboxylated styrene-butadiene latex particles.

Synthesis and in vitro experiments of carcinoma vascular endothelial targeting polymeric nano-micelles combining small particle size and supermagnetic sensitivity.

Science.gov (United States)

Zhang, Yi; Pan, Jielin; Xu, Qilan; Li, Hao; Wang, Jianhao; Zhang, Chao; Hong, Guobin

2018-01-01

Objective: To construct carcinoma vascular endothelial-targeted polymeric nanomicelles with high magnetic resonance imaging (MRI) sensitivity and to evaluate their biological safety and in vitro tumor-targeting effect, and to monitor their feasibility using clinical MRI scanner. Method: Amphiphilic block copolymer, poly(ethylene glycol)- b -poly(ε-caprolactone) (PEG-PCL) was synthesized via the ring-opening polymerization of ε-caprolactone (CL) initiated by poly(ethylene glycol) (PEG), in which cyclic pentapeptide Arg-Gly-Asp (cRGD) was conjugated with the terminal of hydrophilic PEG block. During the self-assembly of PEG-PCL micelles, superparamagnetic γ-Fe 2 O 3 nanoparticles (11 nm) was loaded into the hydrophobic core. The cRGD-terminated γ-Fe 2 O 3 -loaded polymeric micelles targeting to carcinoma vascular endothelial cells, were characterized in particle size, morphology, loading efficiency and so on, especially high MRI sensitivity in vitro. Normal hepatic vascular endothelial cells (ED25) were incubated with the resulting micelles for assessing their safety. Human hepatic carcinoma vascular endothelial cells (T3A) were cultured with the resulting micelles to assess the micelle uptake using Prussian blue staining and the cell signal intensity using MRI. Results: All the polymeric micelles exhibited ultra-small particle sizes with approximately 50 nm, high relaxation rate, and low toxicity even at high iron concentrations. More blue-stained iron particles were present in the targeting group than the non-targeting and competitive inhibition groups. In vitro MRI showed T 2 WI and T 2 relaxation times were significantly lower in the targeting group than in the other two groups. Conclusion: γ-Fe 2 O 3 -loaded PEG-PCL micelles not only possess ultra-small size and high superparamagnetic sensitivity, also can be actively targeted to carcinoma vascular endothelial cells by tumor-targeted cRGD. It appears to be a promising contrast agent for tumor

From superamphiphobic to amphiphilic polymeric surfaces with ordered hierarchical roughness fabricated with colloidal lithography and plasma nanotexturing.

Science.gov (United States)

Ellinas, K; Tserepi, A; Gogolides, E

2011-04-05

Ordered, hierarchical (triple-scale), superhydrophobic, oleophobic, superoleophobic, and amphiphilic surfaces on poly(methyl methacrylate) PMMA polymer substrates are fabricated using polystyrene (PS) microparticle colloidal lithography, followed by oxygen plasma etching-nanotexturing (for amphiphilic surfaces) and optional subsequent fluorocarbon plasma deposition (for amphiphobic surfaces). The PS colloidal microparticles were assembled by spin-coating. After etching/nanotexturing, the PMMA plates are amphiphilic and exhibit hierarchical (triple-scale) roughness with microscale ordered columns, and dual-scale (hundred nano/ten nano meter) nanoscale texture on the particles (top of the column) and on the etched PMMA surface. The spacing, diameter, height, and reentrant profile of the microcolumns are controlled with the etching process. Following the design requirements for superamphiphobic surfaces, we demonstrate enhancement of both hydrophobicity and oleophobicity as a result of hierarchical (triple-scale) and re-entrant topography. After fluorocarbon film deposition, we demonstrate superhydrophobic surfaces (contact angle for water 168°, compared to 110° for a flat surface), as well as superoleophobic surfaces (153° for diiodomethane, compared to 80° for a flat surface).

Fire and Gas Barrier Properties of Poly(styrene-co-acrylonitrile Nanocomposites Using Polycaprolactone/Clay Nanohybrid Based-Masterbatch

Directory of Open Access Journals (Sweden)

S. Benali

2008-01-01

Full Text Available Exfoliated nanocomposites are prepared by dispersion of poly(ε-caprolactone (PCL grafted montmorillonite nanohybrids used as masterbatches in poly(styrene-co-acrylonitrile (SAN. The PCL-grafted clay nanohybrids with high inorganic content are synthesized by in situ intercalative ring-opening polymerization of ε-caprolactone between silicate layers organomodified by alkylammonium cations bearing two hydroxyl functions. The polymerization is initiated by tin alcoholate species derived from the exchange reaction of tin(II bis(2-ethylhexanoate with the hydroxyl groups borne by the ammonium cations that organomodified the clay. These highly filled PCL nanocomposites (25 wt% in inorganics are dispersed as masterbatches in commercial poly(styrene-co-acrylonitrile by melt blending. SAN-based nanocomposites containing 3 wt% of inorganics are accordingly prepared. The direct blend of SAN/organomodified clay is also prepared for sake of comparison. The clay dispersion is characterized by wide-angle X-ray diffraction (WAXD, atomic force microscopy (AFM, and solid state NMR spectroscopy measurements. The thermal properties are studied by thermogravimetric analysis. The flame retardancy and gas barrier resistance properties of nanocomposites are discussed both as a function of the clay dispersion and of the matrix/clay interaction.

Effects of hydrophobic drug-polyesteric core interactions on drug loading and release properties of poly(ethylene glycol)-polyester-poly(ethylene glycol) triblock core-shell nanoparticles

International Nuclear Information System (INIS)

Khoee, Sepideh; Hassanzadeh, Salman; Goliaie, Bahram

2007-01-01

BAB amphiphilic triblock copolymers consisting of poly(ethylene glycol) (B) (PEG) as the hydrophilic segment and different polyesters (A) as the hydrophobic block were prepared by a polycondensation reaction as efficient model core-shell nanoparticles to assay the effect of interactions between the hydrophobic drug and the polyesteric core in terms of drug loading content and release profile. PEG-poly(hexylene adipate)-PEG (PEG-PHA-PEG) and PEG-poly(butylene adipate)-PEG (PEG-PBA-PEG) to PEG-poly(ethylene adipate)-PEG (PEG-PEA-PEG) core-shell type nanoparticles entrapping quercetin (an anticarcinogenic, allergy inhibitor and antibacterial agent), were prepared by a nanoprecipitation method and characterized by dynamic light scattering (DLS), transmission electron microscopy (TEM) and x-ray diffraction (XRD) techniques. It was found that the obtained nanoparticles showed a smooth surface and spherical shape with controllable sizes in the range of 64-74 nm, while drug loading varied from 7.24% to 19% depending on the copolymer composition and the preparation conditions. The in vitro release behaviour exhibited a sustained release and was affected by the polymer-drug interactions. UV studies revealed the presence of hydrogen bonding as the main existing interaction between quercetin and polyesters in the nanosphere cores

Surface modification of poly(styrene-b-(ethylene-co-butylene)-b-styrene) elastomer via photo-initiated graft polymerization of poly(ethylene glycol)

Energy Technology Data Exchange (ETDEWEB)

Li Xiaomeng [State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Luan Shifang, E-mail: sfluan@ciac.jl.cn [State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Yang Huawei; Shi Hengchong; Zhao Jie; Jin Jing [State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Yin Jinghua, E-mail: yinjh@ciac.jl.cn [State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Stagnaro, Paola [Istituto per Io Studio delle Macromolecole, Consiglio Nazionale delle Ricerche, Via de Marini 6, 16149 Genova (Italy)

2012-01-15

Poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) copolymer biomedical elastomer was covalently grafted with poly(ethylene glycol) methyl ether methacrylate (PEGMA) via a photo-initiated graft polymerization technique. The surface graft polymerization of SEBS with PEGMA was verified by ATR-FTIR and XPS. Effect of graft polymerization parameters, i.e., monomer concentration, UV irradiation time and initiator concentration on the grafting density was investigated. Comparing with the virgin SEBS film, the PEGMA-modified SEBS film presented an enhanced wettability and a larger surface energy. Besides, the surface grafting of PEGMA imparted excellent anti-platelet adhesion and anti-protein adsorption to the SEBS surface.

The Inclusion of Chitosan in Poly-ε-caprolactone Nanoparticles: Impact on the Delivery System Characteristics and on the Adsorbed Ovalbumin Secondary Structure.

Science.gov (United States)

Jesus, Sandra; Fragal, Elizangela H; Rubira, Adley F; Muniz, Edvani C; Valente, Artur J M; Borges, Olga

2018-01-01

This report extensively explores the benefits of including chitosan into poly-ε-caprolactone (PCL) nanoparticles (NPs) to obtain an improved protein/antigen delivery system. Blend NPs (PCL/chitosan NPs) showed improved protein adsorption efficacy (84%) in low shear stress and aqueous environment, suggesting that a synergistic effect between PCL hydrophobic nature and the positive charges of chitosan present at the particle surface was responsible for protein interaction. Additionally, thermal analysis suggested the blend NPs were more stable than the isolated polymers and cytotoxicity assays in a primary cell culture revealed chitosan inclusion in PCL NPs reduced the toxicity of the delivery system. A quantitative 6-month stability study showed that the inclusion of chitosan in PCL NPs did not induce a change in adsorbed ovalbumin (OVA) secondary structure characterized by the increase in the unordered conformation (random coil), as it was observed for OVA adsorbed to chitosan NPs. Additionally, the slight conformational changes occurred, are not expected to compromise ovalbumin secondary structure and activity, during a 6-month storage even at high temperatures (45°C). In simulated biological fluids, PCL/chitosan NPs showed an advantageous release profile for oral delivery. Overall, the combination of PCL and chitosan characteristics provide PCL/chitosan NPs valuable features particularly important to the development of vaccines for developing countries, where it is difficult to ensure cold chain transportation and non-parenteral formulations would be preferred.

Superhydrophobic Bilayer Coating Based on Annealed Electrospun Ultrathin Poly(ε-caprolactone Fibers and Electrosprayed Nanostructured Silica Microparticles for Easy Emptying Packaging Applications

Directory of Open Access Journals (Sweden)

Juliana Lasprilla-Botero

2018-05-01

Full Text Available A coating rendering superhydrophobic properties to low-density polyethylene (LDPE films used in packaging applications was herein generated by means of the electrohydrodynamic processing (EHDP technique. To this end, electrospun ultrathin poly(ε-caprolactone (PCL fibers, followed by electrosprayed nanostructured silica (SiO2 microparticles, were deposited on top of the LDPE film. Various electrospinning and electrospraying times were tested and optimized followed by a thermal post-treatment to provide physical adhesion between the bilayer coating and the LDPE substrate. The morphology, hydrophobicity, permeance to limonene, and thermal stability of the resultant nanostructured coatings were characterized. It was observed that by controlling both the deposition time of the electrospun ultrathin PCL fibers and the electrosprayed SiO2 microparticles, as well as the conditions of the thermal post-treatment, effective superhydrophobic coatings were developed onto the LDPE films. The resultant multilayer presented a hierarchical micro/nanostructured surface with an apparent contact angle of 157° and a sliding angle of 8°. The addition of silica reduced, to some extent, the limonene (aroma barrier, likely due to the increased surface-to-volume ratio, which allowed permeant sorption to occur but improved the thermal stability of the LDPE/PCL film. As a result, the developed multilayer system of LDPE/PCL/SiO2 has significant potential for use in easy-to-empty packaging applications of high water activity products.

Stable and biocompatible genipin-inducing interlayer-crosslinked micelles for sustained drug release

Energy Technology Data Exchange (ETDEWEB)

Dai, Yu; Zhang, Xiaojin, E-mail: zhangxj@cug.edu.cn [China University of Geosciences, Faculty of Materials Science and Chemistry (China)

2017-05-15

To develop the sustained drug release system, here we describe genipin-inducing interlayer-crosslinked micelles crosslinked via Schiff bases between the amines of amphiphilic linear-hyperbranched polymer poly(ethylene glycol)-branched polyethylenimine-poly(ε-caprolactone) (PEG-PEI-PCL) and genipin. The generation of Schiff bases was confirmed by the color changes and UV-Vis absorption spectra of polymeric micelles after adding genipin. The particle size, morphology, stability, in vitro cytotoxicity, drug loading capacity, and in vitro drug release behavior of crosslinked micelles as well as non-crosslinked micelles were characterized. The results indicated that genipin-inducing interlayer-crosslinked micelles had better stability and biocompatibility than non-crosslinked micelles and glutaraldehyde-inducing interlayer-crosslinked micelles. In addition, genipin-inducing interlayer-crosslinked micelles were able to improve drug loading capacity, reduce the initial burst release, and achieve sustained drug release.

ANIONIC SYNTHESIS OF A "CLICKABLE" MIDDLE-CHAIN AZIDEFUNCTIONALIZED POLYSTYRENE AND ITS APPLICATION IN SHAPE AMPHIPHILES

Institute of Scientific and Technical Information of China (English)

Kan Yue; Jinlin He; Chang Liu; Mingjun Huang; Xue-Hui Dong; Kai Guo; Peihong Ni

2013-01-01

"Click chemistry" is,by definition,a general functionalization methodology (GFM) and its marriage with living anionic polymerization is particularly powerful in precise macromolecular synthesis.This paper reports the synthesis of a "clickable" middle-chain azide-functionalized polystyrene (mPS-N3) by anionic polymerization and its application in the preparation of novel shape amphiphiles based on polyhedral oligomeric silsesquioxane (POSS).The mPS-N3 was synthesized by coupling living poly(styryl)lithium chains (PSLi) with 3-chloropropylmethyldichlorosilane and subsequent nucleophilic substitution of the chloro group in the presence of sodium azide.Excess PSLi was end-capped with ethylene oxide to facilitate its removal by flash chromatography.The mPS-N3 was then derived into a giant lipid-like shape amphiphile in two steps following a sequential "click" strategy.The copper(I)-catalyzed azide-alkyne cycloaddition between mPS-N3 and alkyne-functionalized vinyl-substituted POSS derivative (VPOSS-alkyne) ensured quantitative ligation to give polystyrene with VPOSS tethered at the middle of the chain (mPS-VPOSS).The thiol-ene reaction with 1-thioglycerol transforms the vinyl groups on the POSS periphery to hydroxyls,resulting in an amphiphilic shape amphiphile,mPS-DPOSS.This synthetic approach is highly efficient and modular.It demonstrates the "click" philosophy of facile complex molecule construction from a library of simple building blocks and also suggests that mPS-N3 can be used as a versatile "clickable" motif in polymer science for the precise synthesis of complex macromolecules.

Hydration-Induced Phase Separation in Amphiphilic Polymer Matrices and its Influence on Voclosporin Release

Energy Technology Data Exchange (ETDEWEB)

Khan, I. John [The State Univ. of New Jersey, Piscataway, NJ (United States); Murthy, N. Sanjeeva [The State Univ. of New Jersey, Piscataway, NJ (United States); Kohn, Joachim [The State Univ. of New Jersey, Piscataway, NJ (United States)

2015-10-30

Voclosporin is a highly potent, new cyclosporine -- a derivative that is currently in Phase 3 clinical trials in the USA as a potential treatment for inflammatory diseases of the eye. Voclosporin represents a number of very sparingly soluble drugs that are difficult to administer. It was selected as a model drug that is dispersed within amphiphilic polymer matrices, and investigated the changing morphology of the matrices using neutron and x-ray scattering during voclosporin release and polymer resorption. The hydrophobic segments of the amphiphilic polymer chain are comprised of desaminotyrosyl-tyrosine ethyl ester (DTE) and desaminotyrosyl-tyrosine (DT), and the hydrophilic component is poly(ethylene glycol) (PEG). Water uptake in these matrices resulted in the phase separation of hydrophobic and hydrophilic domains that are a few hundred Angstroms apart. These water-driven morphological changes influenced the release profile of voclosporin and facilitated a burst-free release from the polymer. No such morphological reorganization was observed in poly(lactide-co-glycolide) (PLGA), which exhibits an extended lag period, followed by a burst-like release of voclosporin when the polymer was degraded. An understanding of the effect of polymer composition on the hydration behavior is central to understanding and controlling the phase behavior and resorption characteristics of the matrix for achieving long-term controlled release of hydrophobic drugs such as voclosporin.

Hydration-Induced Phase Separation in Amphiphilic Polymer Matrices and its Influence on Voclosporin Release

Directory of Open Access Journals (Sweden)

Joachim Kohn

2012-10-01

Full Text Available Voclosporin is a highly potent, new cyclosporine-A derivative that is currently in Phase 3 clinical trials in the USA as a potential treatment for inflammatory diseases of the eye. Voclosporin represents a number of very sparingly soluble drugs that are difficult to administer. We therefore selected it as a model drug that is dispersed within amphiphilic polymer matrices, and investigated the changing morphology of the matrices using neutron and x-ray scattering during voclosporin release and polymer resorption. The hydrophobic segments of the amphiphilic polymer chain are comprised of desaminotyrosyl-tyrosine ethyl ester (DTE and desaminotyrosyl-tyrosine (DT, and the hydrophilic component is poly(ethylene glycol (PEG. Water uptake in these matrices resulted in the phase separation of hydrophobic and hydrophilic domains that are a few hundred Angstroms apart. These water-driven morphological changes influenced the release profile of voclosporin and facilitated a burst-free release from the polymer. No such morphological reorganization was observed in poly(lactide-co-glycolide (PLGA, which exhibits an extended lag period, followed by a burst-like release of voclosporin when the polymer was degraded. An understanding of the effect of polymer composition on the hydration behavior is central to understanding and controlling the phase behavior and resorption characteristics of the matrix for achieving long-term controlled release of hydrophobic drugs such as voclosporin.

Effect of film thickness on morphological evolution in dewetting and crystallization of polystyrene/poly(ε-caprolactone) blend films.

Science.gov (United States)

Ma, Meng; He, Zhoukun; Yang, Jinghui; Chen, Feng; Wang, Ke; Zhang, Qin; Deng, Hua; Fu, Qiang

2011-11-01

In this Article, the morphological evolution in the blend thin film of polystyrene (PS)/poly(ε-caprolactone) (PCL) was investigated via mainly AFM. It was found that an enriched two-layer structure with PS at the upper layer and PCL at the bottom layer was formed during spinning coating. By changing the solution concentration, different kinds of crystal morphologies, such as finger-like, dendritic, and spherulitic-like, could be obtained at the bottom PCL layer. These different initial states led to the morphological evolution processes to be quite different from each other, so the phase separation, dewetting, and crystalline morphology of PS/PCL blend films as a function of time were studied. It was interesting to find that the morphological evolution of PS at the upper layer was largely dependent on the film thickness. For the ultrathin (15 nm) blend film, a liquid-solid/liquid-liquid dewetting-wetting process was observed, forming ribbons that rupture into discrete circular PS islands on voronoi finger-like PCL crystal. For the thick (30 nm) blend film, the liquid-liquid dewetting of the upper PS layer from the underlying adsorbed PCL layer was found, forming interconnected rim structures that rupture into discrete circular PS islands embedded in the single lamellar PCL dendritic crystal due to Rayleigh instability. For the thicker (60 nm) blend film, a two-step liquid-liquid dewetting process with regular holes decorated with dendritic PCL crystal at early annealing stage and small holes decorated with spherulite-like PCL crystal among the early dewetting holes at later annealing stage was observed. The mechanism of this unusual morphological evolution process was discussed on the basis of the entropy effect and annealing-induced phase separation.

Cationic osteogenic peptide P15-CSP coatings promote 3-D osteogenesis in poly(epsilon-caprolactone) scaffolds of distinct pore size.

Science.gov (United States)

Li, Xian; Ghavidel Mehr, Nima; Guzmán-Morales, Jessica; Favis, Basil D; De Crescenzo, Gregory; Yakandawala, Nandadeva; Hoemann, Caroline D

2017-08-01

P15-CSP is a biomimetic cationic fusion peptide that stimulates osteogenesis and inhibits bacterial biofilm formation when coated on 2-D surfaces. This study tested the hypothesis that P15-CSP coatings enhance 3-D osteogenesis in a porous but otherwise hydrophobic poly-(ɛ-caprolactone) (PCL) scaffold. Scaffolds of 84 µm and 141 µm average pore size were coated or not with Layer-by-Layer polyelectrolytes followed by P15-CSP, seeded with adult primary human mesenchymal stem cells (MSCs), and cultured 10 days in proliferation medium, then 21 days in osteogenic medium. Atomic analyses showed that P15-CSP was successfully captured by LbL. After 2 days of culture, MSCs adhered and spread more on P15-CSP coated pores than PCL-only. At day 10, all constructs contained nonmineralized tissue. At day 31, all constructs became enveloped in a "skin" of tissue that, like 2-D cultures, underwent sporadic mineralization in areas of high cell density that extended into some 141 µm edge pores. By quantitative histomorphometry, 2.5-fold more tissue and biomineral accumulated in edge pores versus inner pores. P15-CSP specifically promoted tissue-scaffold integration, fourfold higher overall biomineralization, and more mineral deposits in the outer 84 µm and inner 141 µm pores than PCL-only (p pore surfaces with 3-D topography. Biomineralization deeper than 150 µm from the scaffold edge was optimally attained with the larger 141 µm peptide-coated pores. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 2171-2181, 2017. © 2017 Wiley Periodicals, Inc.

Effect of in vitro enzymatic degradation on 3D printed poly(ε-caprolactone) scaffolds: morphological, chemical and mechanical properties.

Science.gov (United States)

Ferreira, Joana; Gloria, Antonio; Cometa, Stefania; Coelho, Jorge F J; Domingos, Marco

2017-07-27

In recent years, the tissue engineering (TE) field has significantly benefited from advanced techniques such as additive manufacturing (AM), for the design of customized 3D scaffolds with the aim of guided tissue repair. Among the wide range of materials available to biomanufacture 3D scaffolds, poly(ε-caprolactone) (PCL) clearly arises as the synthetic polymer with the greatest potential, due to its unique properties - namely, biocompatibility, biodegradability, thermal and chemical stability and processability. This study aimed for the first time to investigate the effect of pore geometry on the in vitro enzymatic chain cleavage mechanism of PCL scaffolds manufactured by the AM extrusion process. Methods: Morphological properties of 3D printed PCL scaffolds before and after degradation were evaluated using Scanning Electron Microscopy (SEM) and micro-computed tomography (μ-CT). Differential Scanning Calorimetry (DSC) was employed to determine possible variations in the crystallinity of the scaffolds during the degradation period. The molecular weight was assessed using Size Exclusion Chromatography (SEC) while the mechanical properties were investigated under static compression conditions. Morphological results suggested a uniform reduction of filament diameter, while increasing the scaffolds' porosity. DSC analysis revealed and increment in the crystallinity degree while the molecular weight, evaluated through SEC, remained almost constant during the incubation period (25 days). Mechanical analysis highlighted a decrease in the compressive modulus and maximum stress over time, probably related to the significant weight loss of the scaffolds. All of these results suggest that PCL scaffolds undergo enzymatic degradation through a surface erosion mechanism, which leads to significant variations in mechanical, physical and chemical properties, but which has little influence on pore geometry.

Activity of daptomycin- and vancomycin-loaded poly-epsilon-caprolactone microparticles against mature staphylococcal biofilms

Directory of Open Access Journals (Sweden)

Santos Ferreira I

2015-07-01

Full Text Available Inês Santos Ferreira,1 Ana F Bettencourt,1 Lídia MD Gonçalves,1 Stefanie Kasper,2 Bertrand Bétrisey,3 Judith Kikhney,2 Annette Moter,2 Andrej Trampuz,4 António J Almeida1 1Research Institute for Medicines (iMed.ULisboa, Faculty of Pharmacy, University of Lisbon, Lisbon, Portugal; 2Biofilmcenter, German Heart Institute Berlin, Berlin, Germany; 3Infectious Diseases Service, Department of Medicine, Centre Hospitalier Universitaire Vaudois, Lausanne, Switzerland; 4Center for Musculoskeletal Surgery, Charité – University Medicine Berlin, Berlin, Germany Abstract: The aim of the present study was to develop novel daptomycin-loaded poly-epsilon-caprolactone (PCL microparticles with enhanced antibiofilm activity against mature biofilms of clinically relevant bacteria, methicillin-resistant Staphylococcus aureus (MRSA and polysaccharide intercellular adhesin-positive Staphylococcus epidermidis. Daptomycin was encapsulated into PCL microparticles by a double emulsion-solvent evaporation method. For comparison purposes, formulations containing vancomycin were also prepared. Particle morphology, size distribution, encapsulation efficiency, surface charge, thermal behavior, and in vitro release were assessed. All formulations exhibited a spherical morphology, micro­meter size, and negative surface charge. From a very early time stage, the released concentrations of daptomycin and vancomycin were higher than the minimal inhibitory concentration and continued so up to 72 hours. Daptomycin presented a sustained release profile with increasing concentrations of the drug being released up to 72 hours, whereas the release of vancomycin stabilized at 24 hours. The antibacterial activity of the microparticles was assessed by isothermal microcalorimetry against planktonic and sessile MRSA and S. epidermidis. Regarding planktonic bacteria, daptomycin-loaded PCL microparticles presented the highest antibacterial activity against both strains. Isothermal

Self-assembly behavior of well-defined polymethylene-block-poly(ethylene glycol) copolymers in aqueous solution

KAUST Repository

Alkayal, Nazeeha

2016-09-22

A series of well-defined amphiphilic polymethylene-b-poly(ethylene glycol) (PM-b-PEG) diblock copolymers, with different hydrophobic chain length, were synthesized by combining Diels-Alder reaction with polyhomologation. The successful synthetic procedure was confirmed by size-exclusion chromatography (SEC) and 1H NMR spectroscopy. These block copolymers self-assembled into spherical micelles in aqueous solutions and exhibit low critical micelle concentration (CMC) of 2–4 mg/mL, as determined by fluorescence spectroscopy using pyrene as a probe. Measurements of the micelle hydrodynamic diameters, performed by dynamic light scattering (DLS), cryo-transmission electron microscopy (cryo-TEM) and atomic force microscopy (AFM), revealed a direct dependence of the micelle size from the polymethylene block length.

Preparation of an antibacterial, hydrophilic and photocatalytically active polyacrylic coating using TiO2 nanoparticles sensitized by graphene oxide.

Science.gov (United States)

Nosrati, Rahimeh; Olad, Ali; Shakoori, Sahar

2017-11-01

In recent years more attentions have been paid for preparation of coatings with self-cleaning and antibacterial properties. These properties allow the surface to maintain clean and health over long times without any need to cleaning or disinfection. Acrylic coatings are widely used on various surfaces such as automotive, structural and furniture which their self-cleaning and antibacterial ability is very important. The aim of this work is the preparation of a polyacrylic based self-cleaning and antibacterial coating by the modification of TiO 2 as a coating additive. TiO 2 nanoparticles were sensitized to the visible light irradiation using graphene oxide through the preparation of TiO 2 /graphene oxide nanocomposite. Graphene oxide was prepared via a modified Hummers method. TiO 2 /graphene oxide nanocomposite was used as additive in a polyacrylic coating formulation. Hydrophilicity, photocatalytic and antibacterial activities as well as coating stability were evaluated for TiO 2 /graphene oxide modified polyacrylic coating and compared with that of pristine TiO 2 modified and unmodified polyacrylic coatings. TiO 2 /graphene oxide nanocomposite and polyacrylic coating modified by TiO 2 /graphene oxide additive were characterized using FT-IR, UV-Vis, XRD, and FESEM techniques. The effect of TiO 2 /graphene oxide composition and its percent in the coating formulation was evaluated on the polyacrylic coating properties. Results showed that polyacrylic coating having 3% W TiO 2 /graphene oxide nanocomposite additive with TiO 2 to graphene oxide ratio of 100:20 is the best coating considering most of beneficial features such as high photodecolorization efficiency of organic dye contaminants, high hydrophilicity, and stability in water. According to the results, TiO 2 is effectively sensitized by graphene oxide and the polyacrylic coating modified by TiO 2 /graphene oxide nanocomposite shows good photocatalytic activity under visible light irradiation. Copyright © 2017

Triblock copolymers based on epsilon-caprolactone and trimethylene carbonate for the 3D printing of tissue engineering scaffolds

NARCIS (Netherlands)

Guney, Aysun; Malda, Jos; Dhert, Wouter J. A.; Grijpma, Dirk W.

Background: Biodegradable PCL-b-PTMC-b-PCL triblock copolymers based on trimethylene carbonate (TMC) and epsilon-caprolactone (CL) were prepared and used in the 3D printing of tissue engineering scaffolds. Triblock copolymers of various molecular weights containing equal amounts of TMC and CL were

Triblock copolymers based on ε-caprolactone and trimethylene carbonate for the 3D printing of tissue engineering scaffolds

NARCIS (Netherlands)

Güney, Aysun; Malda, Jos; Dhert, Wouter J A; Grijpma, Dirk W

BACKGROUND: Biodegradable PCL-b-PTMC-b-PCL triblock copolymers based on trimethylene carbonate (TMC) and ε-caprolactone (CL) were prepared and used in the 3D printing of tissue engineering scaffolds. Triblock copolymers of various molecular weights containing equal amounts of TMC and CL were

Triblock copolymers based on ε-caprolactone and trimethylene carbonate for the 3D printing of tissue engineering scaffolds

NARCIS (Netherlands)

Güney, Aysun; Malda, Jos; Dhert, Wouter J.A.; Grijpma, Dirk W.

2017-01-01

Background: Biodegradable PCL-b-PTMC-b-PCL triblock copolymers based on trimethylene carbonate (TMC) and ε-caprolactone (CL) were prepared and used in the 3D printing of tissue engineering scaffolds. Triblock copolymers of various molecular weights containing equal amounts of TMC and CL were

Directed Self-Assembly of Poly(2-vinylpyridine)-b-polystyrene-b-poly(2-vinylpyridine) Triblock Copolymer with Sub-15 nm Spacing Line Patterns Using a Nanoimprinted Photoresist Template.

Science.gov (United States)

Sun, Zhiwei; Chen, Zhenbin; Zhang, Wenxu; Choi, Jaewon; Huang, Caili; Jeong, Gajin; Coughlin, E Bryan; Hsu, Yautzong; Yang, XiaoMin; Lee, Kim Y; Kuo, David S; Xiao, Shuaigang; Russell, Thomas P

2015-08-05

Low molecular weight P2VP-b-PS-b-P2VP triblock copolymer (poly(2-vinlypyridine)-block-polystyrene-block-poly(2-vinylpyridine)] is doped with copper chloride and microphase separated into lamellar line patterns with ultrahigh area density. Salt-doped P2VP-b-PS-b-P2VP triblock copolymer is self-assembled on the top of the nanoimprinted photoresist template, and metallic nanowires with long-range ordering are prepared with platinum-salt infiltration and plasma etching. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sequential crystallization and morphology of triple crystalline biodegradable PEO-b-PCL-b-PLLA triblock terpolymers

KAUST Repository

Palacios, Jordana

2016-01-05

The sequential crystallization of poly(ethylene oxide)-b-poly(e-caprolactone)-b-poly(L-lactide) (PEO-b-PCL-b-PLLA) triblock terpolymers, in which the three blocks are able to crystallize separately and sequentially from the melt, is presented. Two terpolymers with identical PEO and PCL block lengths and two different PLLA block lengths were prepared, thus the effect of increasing PLLA content on the crystallization behavior and morphology was evaluated. Wide angle X-Ray scattering (WAXS) experiments performed on cooling from the melt confirmed the triple crystalline nature of these terpolymers and revealed that they crystallize in sequence: the PLLA block crystallizes first, then the PCL block, and finally the PEO block. Differential scanning calorimetry (DSC) analysis further demonstrated that the three blocks can crystallize from the melt when a low cooling rate is employed. The crystallization process takes place from a homogenous melt as indicated by small angle X-Ray scattering (SAXS) experiments. The crystallization and melting enthalpies and temperatures of both PEO and PCL blocks decrease as PLLA content in the terpolymer increases. Polarized light optical microscopy (PLOM) demonstrated that the PLLA block templates the morphology of the terpolymer, as it forms spherulites upon cooling from the melt. The subsequent crystallization of PCL and PEO blocks occurs inside the interlamellar regions of the previously formed PLLA block spherulites. In this way, unique triple crystalline mixed spherulitic superstructures have been observed for the first time. As the PLLA content in the terpolymer is reduced the superstructural morphology changes from spherulites to a more axialitic-like structure.

Responsive micellar films of amphiphilic block copolymer micelles: control on micelle opening and closing.

Science.gov (United States)

Chen, Zhiquan; He, Changcheng; Li, Fengbin; Tong, Ling; Liao, Xingzhi; Wang, Yong

2010-06-01

We reported the deliberate control on the micelle opening and closing of amphiphilic polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) micellar films by exposing them to selective solvents. We first treated the micellar films with polar solvents including ethanol and water (pH = 4, 8, and 12) that have different affinities to P2VP. We observed opening of the micelles in all the cases. Both the size of opened pores and the opening rate are dependent on the solvency of different solvents for P2VP. We then explored the closing behavior of the opened micelles using solvents having different affinities to PS. We found that the opened micelles were recovered to their initial closed micelle forms. The recovery was accompanied by a slow micelle disassociation process which gradually reduced the micelle size. The rates of the micelle closing and disassociation are also dependent on the solvency of different solvents for PS.

Complex coacervate core micelles with a lysozyme-modified corona

NARCIS (Netherlands)

Danial, Maarten; Klok, Harm-Anton; Norde, Willem; Stuart, Martien A. Cohen

2007-01-01

This paper describes the preparation, characterization, and enzymatic activity of complex coacervate core micelles (C3Ms) composed of poly(acrylic acid) (PAA) and poly(N-methyl-2-vinyl pyridinium iodide)-b-poly(ethylene oxide) (PQ2VP-PEO) to which the antibacterial enzyme lysozyme is end-attached.

Fluctuations and structure of amphiphilic films; Fluctuations et structure de films d`amphiphiles

Energy Technology Data Exchange (ETDEWEB)

Gourier, CH

1996-07-01

This thesis is divided in three parts.The first part exposes in a theoretical point of view, how the fluctuations spectrum of an amphiphilic film is governed by its properties and its bidimensional characteristics.The measurements of fluctuations spectra of an interface are accessible with the measurement of intensity that interface diffuses out of the specular angle, we present in the second chapter the principles of the X rays diffusion by a real interface and see how the diffuse diffusion experiments allow to determine the fluctuations spectrum of an amphiphilic film. The second part is devoted to the different experimental techniques that have allowed to realize the study of fluctuation as well as the structural study.The third part is devoted to experimental results concerning the measurements of fluctuations spectra and to the study of the structure of amphiphilic films. We show that it is possible by using an intense source of X rays (ESRF: European Synchrotron Radiation Facility) to measure the water and amphiphilic films fluctuations spectra until molecular scales. The last chapter is devoted to the structural study and film fluctuations made of di-acetylenic molecules. (N.C.)

Amphiphilic Copolymers Shuttle Drugs Across the Blood-Brain Barrier.

Science.gov (United States)

Clemens-Hemmelmann, Mirjam; Kuffner, Christiane; Metz, Verena; Kircher, Linda; Schmitt, Ulrich; Hiemke, Christoph; Postina, Rolf; Zentel, Rudolf

2016-05-01

Medical treatment of diseases of the central nervous system requires transport of drugs across the blood-brain barrier (BBB). Here, it is extended previously in vitro experiments with a model compound to show that the non-water-soluble and brain-impermeable drug domperidone (DOM) itself can be enriched in the brain by use of an amphiphilic copolymer as a carrier. This carrier consists of poly(N-(2-hydroxypropyl)-methacrylamide), statistically copolymerized with 10 mol% hydrophobic lauryl methacrylate, into whose micellar aggregates DOM is noncovalently absorbed. As tested in a BBB model efficient transport of DOM across, the BBB is achievable over a wide range of formulations, containing 0.8 to 35.5 wt% domperidone per copolymer. In neither case, the polymer itself is translocated across the BBB model. In vivo experiments in mice show that already 10 min after intraperitoneal injection of the polymer/domperidone (PolyDOM) formulation, domperidone can be detected in blood and in the brain. Highest serum and brain levels of domperidone are detected 40 min after injection. At that time point serum domperidone is increased 48-fold. Most importantly, domperidone is exclusively detectable in high amounts in the brain of PolyDOM injected mice and not in mice injected with bare domperidone. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of Rhodamine B Fluorescent Poly(methacrylic acid) Coated Gelatin Nanoparticles

OpenAIRE

Gan, Zhenhai; Ju, Jianhui; Zhang, Ting; Wu, Daocheng

2011-01-01

Poly(methacrylic acid) (PMAA)-coated gelatin nanoparticles encapsulated with fluorescent dye rhodamine B were prepared by the coacervation method with the aim to retard the release of rhodamine B from the gelatin matrix. With sodium sulfate as coacervation reagent for gelatin, a kind of biopolymer with excellent biocompatibility, the formed gelatin nanoparticles were cross-linked by formaldehyde followed by the polymerization of methacrylic acid coating. The fluorescent poly(methacrylic acid)...

Synthesis and Functionalization of Poly(ethylene oxide-b-ethyloxazoline) Diblock Copolymers with Phosphonate Ions

OpenAIRE

Chen, Alfred Yuen-Wei

2013-01-01

Poly(ethylene oxide) (PEO) and poly(2-ethyl-2-oxazoline) (PEOX) are biocompatible polymers that act as hydrophilic "stealth" drug carriers. As block copolymers, the PEOX group offers a wider variety of functionalization. The goal of this project was to synthesize a poly(ethylene oxide)-b-poly(2-ethyl-2-oxazoline) (PEO-b-PEOX) block copolymer and functionalize pendent groups of PEOX with phosphonic acid. This was achieved through cationic ring opening polymerization (CROP) of 2-...

Phase Diagrams of the Aqueous Two-Phase Systems of Poly(ethylene glycol/Sodium Polyacrylate/Salts

Directory of Open Access Journals (Sweden)

Adalberto Pessoa Junior

2011-03-01

Full Text Available Aqueous two-phase systems consisting of polyethylene glycol (PEG, sodium polyacrylate (NaPAA, and a salt have been studied. The effects of the polymer size, salt type (NaCl, Na2SO4, sodium adipate and sodium azelate and salt concentrations on the position of the binodal curve were investigated. The investigated PEG molecules had a molar mass of 2,000 to 8,000 g/mol, while that of NaPAA was 8,000 g/mol. Experimental phase diagrams, and tie lines and calculated phase diagrams, based on Flory-Huggins theory of polymer solutions are presented. Due to strong enthalpic and entropic balancing forces, the hydrophobicity of the added salt has a strong influence on the position of the binodal, which could be reproduced by model calculations.

Synthesis and properties of amphiphilic hyperbranched polyethers as pigment dispersant

Science.gov (United States)

Xu, Q.; Zhou, Y. J.; Long, S. J.; Liu, Y. G.; Li, J. H.

2018-01-01

Hyperbranched polymers possess prominent properties such as low viscosity, good solubility, high rheological property, environmental non-toxic, and so on, which have potential applications in coatings. In this study, the amphiphilic hyperbranched polyethers (AHPs) consisting of hydrophobic hyperbranched polyethers core and hydrophilic poly (ethylene glycol) arms with different degree of branching (DB) under various reaction temperatures was prepared by the cation ring-opening polymerization. Their structures were characterized by IR, 13CNMR and GPC. Their dispersion properties for pigment particles were investigated. The AHP47 with 0.47 DB was found to have good dispersion properties for Yellow HGR. This work would provide experimental data and theoretical foundation for the application of hyperbranched polyethers in environmental protection coating.

A new class of amphiphiles: annelids; Une nouvelle classe d'amphiphiles: les annelides

Energy Technology Data Exchange (ETDEWEB)

Markovitsi, Dimitra

1983-12-14

This research thesis presents annelids, organometallic compounds which may form into organised phases. The author describes the synthesis of an amphipathic ligand of its cobaltic and cupric complexes. The formation of micelles and of thermotropic and lyotropic liquid crystals is highlighted. The copper (II) annelid environment is studied by electronic paramagnetic resonance spectroscopy. The author demonstrates, in micellar phase, the effect of molecular cooperativity on acid-base balance, on metallic ion complexation, on the photo-sensitized electronic transfer, and on the formation of poly-nuclear complexes [French] Les annelides, composes organometalliques susceptibles de former des phases organisees, sont presentes. La synthese d'un ligand amphipathique et de ses complexes cobaltique et cuivrique est decrite. La formation de micelles et de cristaux liquides, thermotropes et lyotropes, a l'aide de ces amphiphiles, est mise en evidence. L'environnement de l'annelide de cuivre (II) est etudie par spectroscopie de resonance paramagnetique electronique. L'effet de la cooperativite moleculaire sur l'equilibre acidobasique, sur la complexation des ions metalliques, sur le transfert electronique photosensibilise et sur la formation des complexes polynucleaires est demontre en phase micellaire. (auteur)

Effect of poly(ethylene oxide) homopolymer and two different poly(ethylene oxide-b-poly(propylene oxide)-b-poly(ethylene oxide) triblock copolymers on morphological, optical, and mechanical properties of nanostructured unsaturated polyester.

Science.gov (United States)

Builes, Daniel H; Hernández-Ortiz, Juan P; Corcuera, Ma Angeles; Mondragon, Iñaki; Tercjak, Agnieszka

2014-01-22

Novel nanostructured unsaturated polyester resin-based thermosets, modified with poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), and two poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) block copolymers (BCP), were developed and analyzed. The effects of molecular weights, blocks ratio, and curing temperatures on the final morphological, optical, and mechanical properties were reported. The block influence on the BCP miscibility was studied through uncured and cured mixtures of unsaturated polyester (UP) resins with PEO and PPO homopolymers having molecular weights similar to molecular weights of the blocks of BCP. The final morphology of the nanostructured thermosetting systems, containing BCP or homopolymers, was investigated, and multiple mechanisms of nanostructuration were listed and explained. By considering the miscibility of each block before and after curing, it was determined that the formation of the nanostructured matrices followed a self-assembly mechanism or a polymerization-induced phase separation mechanism. The miscibility between PEO or PPO blocks with one of two phases of UP matrix was highlighted due to its importance in the final thermoset properties. Relationships between the final morphology and thermoset optical and mechanical properties were examined. The mechanisms and physics behind the morphologies lead toward the design of highly transparent, nanostructured, and toughened thermosetting UP systems.

Enhancement of biodegradation and osseointegration of poly(ε-caprolactone)/calcium phosphate ceramic composite screws for osteofixation using calcium sulfate.

Science.gov (United States)

Wu, Chang-Chin; Hsu, Li-Ho; Tsai, Yuh-Feng; Sumi, Shoichiro; Yang, Kai-Chiang

2016-04-04

Internal fixation devices, which can stabilize and realign fractured bone, are widely used in fracture management. In this paper, a biodegradable composite fixator, composed of poly(ε-caprolactone), calcium phosphate ceramic and calcium sulfate (PCL/CPC/CS), is developed. The composition of CS, which has a high dissolution rate, was expected to create a porous structure to improve osteofixation to the composite fixator. PCL, PCL/CPC, and PCL/CPC/CS samples were prepared and their physical properties were characterized in vitro. In vivo performance of the composite screws was verified in the distal femurs of rabbits. Results showed that the PCL/CPC/CS composite had a higher compressive strength (28.55 ± 3.32 MPa) in comparison with that of PCL (20.64 ± 1.81 MPa) (p < 0.05). A larger amount of apatite was formed on PCL/CPC/CS than on PCL/CPC, while no apatite was found on PCL after simulated body fluid immersion. In addition, PCL/CPC/CS composites also had a faster in vitro degradation rate (13.05 ± 3.42% in weight loss) relative to PCL (1.79 ± 0.23%) and PCL/CPC (4.32 ± 2.18%) (p < 0.001). In animal studies, PCL/CPC/CS screws showed a greater volume loss than that of PCL or PCL/CPC at 24 weeks post-implantation. Under micro-computerized tomography observation, animals with PCL/CPC/CS implants had better osseointegration in terms of the structural parameters of the distal metaphysis, including trabecular number, trabecular spacing, and connectivity density, than the PCL screw. This study reveals that the addition of CS accelerates the biodegradation and enhanced apatite formation of the PCL/CPC composite screw. This osteoconductive PCL/CPC/CS is a good candidate material for internal fixation devices.

Sciatic nerve regeneration in rats by a promising electrospun collagen/poly(ε-caprolactone nerve conduit with tailored degradation rate

Directory of Open Access Journals (Sweden)

Jiang Xinquan

2011-07-01

Full Text Available Abstract Background To cope with the limitations faced by autograft acquisitions particularly for multiple nerve injuries, artificial nerve conduit has been introduced by researchers as a substitute for autologous nerve graft for the easy specification and availability for mass production. In order to best mimic the structures and components of autologous nerve, great efforts have been made to improve the designation of nerve conduits either from materials or fabrication techniques. Electrospinning is an easy and versatile technique that has recently been used to fabricate fibrous tissue-engineered scaffolds which have great similarity to the extracellular matrix on fiber structure. Results In this study we fabricated a collagen/poly(ε-caprolactone (collagen/PCL fibrous scaffold by electrospinning and explored its application as nerve guide substrate or conduit in vitro and in vivo. Material characterizations showed this electrospun composite material which was made of submicron fibers possessed good hydrophilicity and flexibility. In vitro study indicated electrospun collagen/PCL fibrous meshes promoted Schwann cell adhesion, elongation and proliferation. In vivo test showed electrospun collagen/PCL porous nerve conduits successfully supported nerve regeneration through an 8 mm sciatic nerve gap in adult rats, achieving similar electrophysiological and muscle reinnervation results as autografts. Although regenerated nerve fibers were still in a pre-mature stage 4 months postoperatively, the implanted collagen/PCL nerve conduits facilitated more axons regenerating through the conduit lumen and gradually degraded which well matched the nerve regeneration rate. Conclusions All the results demonstrated this collagen/PCL nerve conduit with tailored degradation rate fabricated by electrospinning could be an efficient alternative to autograft for peripheral nerve regeneration research. Due to its advantage of high surface area for cell attachment, it

Determining the mechanical properties of electrospun poly-ε-caprolactone (PCL) nanofibers using AFM and a novel fiber anchoring technique

Energy Technology Data Exchange (ETDEWEB)

Baker, Stephen R.; Banerjee, Soham; Bonin, Keith; Guthold, Martin, E-mail: gutholdm@wfu.edu

2016-02-01

Due to its low cost, biocompatibility and slow bioresorption, poly-ε-caprolactone (PCL) continues to be a suitable material for select biomedical engineering applications. We used a combined atomic force microscopy (AFM)/optical microscopy technique to determine key mechanical properties of individual electrospun PCL nanofibers with diameters between 440–1040 nm. Compared to protein nanofibers, PCL nanofibers showed much lower adhesion, as they slipped on the substrate when mechanically manipulated. We, therefore, first developed a novel technique to anchor individual PCL nanofibers to micrometer-sized ridges on a substrate, and then mechanically tested anchored nanofibers. When held at constant strain, tensile stress relaxed with fast and slow relaxation times of 1.0 ± 0.3 s and 8.8 ± 3.1 s, respectively. The total tensile modulus was 62 ± 26 MPa, the elastic (non-relaxing) component of the tensile modulus was 53 ± 36 MPa. Individual PCL fibers could be stretched elastically (without permanent deformation) to strains of 19–23%. PCL nanofibers are rather extensible; they could be stretched to a strain of at least 98%, and a tensile strength of at least 12 MPa, before they slipped off the AFM tip. PCL nanofibers that had aged for over a month at ambient conditions became stiffer and less elastic. Our technique provides accurate nanofiber mechanical data, which are needed to guide construction of scaffolds for cells and other biomedical devices. - Highlights: • Developed technique to anchor single nanofibers on microridges • Determined mechanical properties of e-spun PCL fibers • E-spun PCL fibers have similar mechanical properties as wet fibrin fibers. • E-spun PCL fiber total elastic modulus is ~ 60 MPa. • E-spun PCL fiber extensibility is > 100%.

Fabrication of nanocomposite mat through incorporating bioactive glass particles into gelatin/poly(ε-caprolactone) nanofibers by using Box–Behnken design

Energy Technology Data Exchange (ETDEWEB)

Gönen, Seza Özge, E-mail: gonens@itu.edu.tr; Erol Taygun, Melek; Aktürk, Ayşen; Küçükbayrak, Sadriye

2016-10-01

The current research was conducted to propose a nanocomposite material, which could be suitable to be used as a scaffold for bone tissue engineering applications. For this purpose, nanocomposite fibers of gelatin, poly(ε-caprolactone) (PCL), and bioactive glass were successfully fabricated via electrospinning process. In this context, response surface methodology based on a three-level, four-variable Box-Behnken design was adopted as an optimization tool to choose the most appropriate parameter settings to obtain the desired fiber diameter. The investigation, based on a second order polynomial model, focused on the analysis of the effect of both solution and processing parameters on the fiber diameter and its standard deviation. In optimum conditions (bioactive glass content of 7.5% (w/v), applied voltage of 25 kV, tip-to-collector distance of 12.5 cm, and flow rate of 1 mL/h), the fiber diameter was found to be 584 ± 337 nm which was in good agreement with the predicted value by the developed models (523 ± 290 nm). Analytical tools such as scanning electron microscopy, X-ray diffraction analysis, Fourier transform infrared spectroscopy, and differential thermal analyzer were used for further evaluation of the optimized nanocomposite mat. The overall results showed that nanocomposite scaffolds could be promising candidates for tissue engineering applications. - Highlights: • Nanocomposite fibers of gelatin, PCL, and bioactive glass were successfully fabricated. • Three-level, four-variable Box-Behnken design was adopted as an optimization tool. • The individual and interactive effects of the electrospinning parameters were determined. • Quadratic models were used to adjust the fiber diameter and its standard deviation.

Fabrication of nanocomposite mat through incorporating bioactive glass particles into gelatin/poly(ε-caprolactone) nanofibers by using Box–Behnken design

International Nuclear Information System (INIS)

Gönen, Seza Özge; Erol Taygun, Melek; Aktürk, Ayşen; Küçükbayrak, Sadriye

2016-01-01

The current research was conducted to propose a nanocomposite material, which could be suitable to be used as a scaffold for bone tissue engineering applications. For this purpose, nanocomposite fibers of gelatin, poly(ε-caprolactone) (PCL), and bioactive glass were successfully fabricated via electrospinning process. In this context, response surface methodology based on a three-level, four-variable Box-Behnken design was adopted as an optimization tool to choose the most appropriate parameter settings to obtain the desired fiber diameter. The investigation, based on a second order polynomial model, focused on the analysis of the effect of both solution and processing parameters on the fiber diameter and its standard deviation. In optimum conditions (bioactive glass content of 7.5% (w/v), applied voltage of 25 kV, tip-to-collector distance of 12.5 cm, and flow rate of 1 mL/h), the fiber diameter was found to be 584 ± 337 nm which was in good agreement with the predicted value by the developed models (523 ± 290 nm). Analytical tools such as scanning electron microscopy, X-ray diffraction analysis, Fourier transform infrared spectroscopy, and differential thermal analyzer were used for further evaluation of the optimized nanocomposite mat. The overall results showed that nanocomposite scaffolds could be promising candidates for tissue engineering applications. - Highlights: • Nanocomposite fibers of gelatin, PCL, and bioactive glass were successfully fabricated. • Three-level, four-variable Box-Behnken design was adopted as an optimization tool. • The individual and interactive effects of the electrospinning parameters were determined. • Quadratic models were used to adjust the fiber diameter and its standard deviation.

Influence of polyacrylic ester and silica fume on the mechanical properties of mortar for repair application

Directory of Open Access Journals (Sweden)

Chaohua Jiang

2016-12-01

Full Text Available Experimental investigations on the influence of different amounts of polyacrylic ester and silica fumes on the mechanical properties of mortar such as the compressive strength, splitting tensile strength, bonding strength, and abrasion resistance are presented in this article. The results show that the compressive and splitting tensile strength of mortar can be improved with the addition of polyacrylic ester and silica fumes. Results obtained from both the direct tensile bond test and flexural bond test indicate that the addition of polyacrylic ester and silica fumes improves the bond strength significantly, and the enhancement is more obvious with polyacrylic ester paste as interfacial adhesives. Furthermore, mortar incorporation of polyacrylic ester and silica fumes shows superior abrasion resistance compared to the control mortar. Therefore, the correct combination of polyacrylic ester and silica fumes to produce mortars has been shown to have synergistic effects, which results in excellent properties including high bond strength and superior abrasion resistance. Mortars containing polyacrylic ester and silica fumes are ideal for repairing concrete especially for hydraulic concrete structure.

Well-defined polyethylene-based graft terpolymers by combining nitroxide-mediated radical polymerization, polyhomologation and azide/alkyne “click” chemistry†

KAUST Repository

Alkayal, Nazeeha; Durmaz, Hakan; Tunca, Umit; Hadjichristidis, Nikolaos

2016-01-01

AAC) “click” chemistry. Three steps were involved in this approach: (i) synthesis of alkyne-terminated polyethylene-b-poly(ε-caprolactone) (PE-b-PCL-alkyne) block copolymers (branches) by esterification of PE-b-PCL-OH with 4-pentynoic acid; the PE

Brittle and ductile adjustable cement derived from calcium phosphate cement/polyacrylic acid composites.

Science.gov (United States)

Chen, Wen-Cheng; Ju, Chien-Ping; Wang, Jen-Chyan; Hung, Chun-Cheng; Chern Lin, Jiin-Huey

2008-12-01

Bone filler has been used over the years in dental and biomedical applications. The present work is to characterize a non-dispersive, fast setting, modulus adjustable, high bioresorbable composite bone cement derived from calcium phosphate-based cement combined with polymer and binding agents. This cement, we hope, will not swell in simulated body fluid and keep the osteogenetic properties of the dry bone and avoid its disadvantages of being brittle. We developed a calcium phosphate cement (CPC) of tetracalcium phosphate/dicalcium phosphate anhydrous (TTCP/DCPA)-polyacrylic acid with tartaric acid, calcium fluoride additives and phosphate hardening solution. The results show that while composite, the hard-brittle properties of 25wt% polyacrylic acid are proportional to CPC and mixing with additives is the same as those of the CPC without polyacrylic acid added. With an increase of polyacrylic acid/CPC ratio, the 67wt% samples revealed ductile-tough properties and 100wt% samples kept ductile or elastic properties after 24h of immersion. The modulus range of this development was from 200 to 2600MPa after getting immersed in simulated body fluid for 24h. The TTCP/DCPA-polyacrylic acid based CPC demonstrates adjustable brittle/ductile strength during setting and after immersion, and the final reaction products consist of high bioresorbable monetite/brushite/calcium fluoride composite with polyacrylic acid.

Biodegradable poly lactone-family polymer and their applications in medical field

International Nuclear Information System (INIS)

Wang, S.; Bei, J.

2005-01-01

Poly lactone-family polymers such as poly lactide, poly glycolide and polycaprolactone are kind aliphatic polyester. Since they can degrade by hydrolysis reaction under all the ph condition and possess biocompatibility, biodegradability and other good properties, especially they included not peptide bond in their molecules, they are non-antigen and non-immunization, as well as have no-toxicity and no-stimulation. So they are interested biomaterials and very useful in medical field. However the properties of all of the homo-poly lactones can not be changed in a large range, the limited properties result in limited applications of these homo-poly lactones. Based on macromolecular design, a series of copolylactones such as poly(lactide-co-glycolide) (PLGA), poly(glycolide-co-lactide-co-caprolactone) tri- component copolymer (PGLC), tri- and multi-block poly lactide/poly(ethylene oxide) copolymer (TPLE and BPLE), as well as polycaprolactone/poly lactide/poly(ethylene oxide) copolymer (PCEL) et al were synthesized by copolymerization among various lactone monomers or lactone monomers with poly(ethylene glycol). These copolylactones have wide range of degradation life from several months to years and different mechanical properties. After plasma treatment the surface property of the copolylactones were improved further and cell affinity of the copolylactones was improved obviously. The applications of these poly lactone-family polymers in medical field for used as drug carrier in drug delivery system, and as cell scaffold in tissue engineering were discussed

Double printing of hyaluronic acid/poly(glycidol) hybrid hydrogels with poly(ϵ-caprolactone) for MSC chondrogenesis

NARCIS (Netherlands)

Stichler, Simone; Böck, Thomas; Paxton, Naomi; Bertlein, Sarah; Levato, Riccardo; Schill, Verena; Smolan, Willi; Malda, Jos; Teßmar, Jörg; Blunk, Torsten; Groll, Jürgen

2017-01-01

This study investigates the use of allyl-functionalized poly(glycidol)s (P(AGE-co-G)) as a cytocompatible cross-linker for thiol-functionalized hyaluronic acid (HA-SH) and the optimization of this hybrid hydrogel as bioink for 3D bioprinting. The chemical cross-linking of gels with 10 wt.% overall

Poly(ester amide-Poly(ethylene oxide Graft Copolymers: Towards Micellar Drug Delivery Vehicles

Directory of Open Access Journals (Sweden)

Gregory J. Zilinskas

2012-01-01

Full Text Available Micelles formed from amphiphilic copolymers are promising materials for the delivery of drug molecules, potentially leading to enhanced biological properties and efficacy. In this work, new poly(ester amide-poly(ethylene oxide (PEA-PEO graft copolymers were synthesized and their assembly into micelles in aqueous solution was investigated. It was possible to tune the sizes of the micelles by varying the PEO content of the polymers and the method of micelle preparation. Under optimized conditions, it was possible to obtain micelles with diameters less than 100 nm as measured by dynamic light scattering and transmission electron microscopy. These micelles were demonstrated to encapsulate and release a model drug, Nile Red, and were nontoxic to HeLa cells as measured by an MTT assay. Overall, the properties of these micelles suggest that they are promising new materials for drug delivery systems.

Nanosilica and Polyacrylate/Nanosilica: A Comparative Study of Acute Toxicity

Directory of Open Access Journals (Sweden)

Ying-Mei Niu

2016-01-01

Full Text Available We compared the acute toxicity of nanosilica and polyacrylate/nanosilica instillation in Wistar rats (n=60. Exposure to nanosilica and polyacrylate/nanosilica showed a 30% mortality rate. When compared with saline-treated rats, animals in both exposure groups exhibited a significant reduction of PO2 (P<0.05 at both 24 and 72 hr. after exposure. Both exposure groups exhibited a significant reduction of neutrophils in arterial blood compared to saline controls (P<0.05 24 hr. after exposure. The levels of blood ALT and LDH in exposed groups were found to be significantly increased (P<0.05 24 hr. following exposure. The exposed groups exhibited various degrees of pleural effusion and pericardial effusion. Our findings indicated respiratory exposure to polyacrylate/nanosilica and nanosilica is likely to cause multiple organ toxicity.

H-shaped supra-amphiphiles based on a dynamic covalent bond.

Science.gov (United States)

Wang, Guangtong; Wang, Chao; Wang, Zhiqiang; Zhang, Xi

2012-10-16

The imine bond, a kind of dynamic covalent bond, is used to bind two bolaform amphiphiles together with spacers, yielding H-shaped supra-amphiphiles. Micellar aggregates formed by the self-assembly of the H-shaped supra-amphiphiles are observed. When pH is tuned down from basic to slightly acidic, the benzoic imine bond can be hydrolyzed, leading to the dissociation of H-shaped supra-amphiphiles. Moreover, H-shaped supra-amphiphiles have a lower critical micelle concentration than their building blocks, which is very helpful in enhancing the stability of the benzoic imine bond being hydrolyzed by acid. The surface tension isotherms of the H-shaped supra-amphiphiles with different spacers indicate their twisty conformation at a gas-water interface. The study of H-shaped supra-amphiphiles can enrich the family of amphiphiles, and moreover, the pH-responsiveness may make them apply to controlled or targetable drug delivery in a biological environment.

Lower critical solution temperature behavior of alpha-substituted poly(acrylic acids)s, cyclopolymerization of N-vinylformamido-methylacrylates, and use of the World-Wide Web in polymer science education

Science.gov (United States)

Michalovic, Mark Stephen

A series of alpha-substituted poly(acrylic acid)s was synthesized and characterized. Their aqueous solution properties were investigated with respect to lower critical solution temperature (LCST) behavior. Poly(alpha-methoxymethylacrylic acid) was found to have a lower critical solution temperature (LCST) of 46°C, poly(alpha-methoxyethoxymethylacrylic acid) showed an LCST of 26.5°C and poly(alpha-methoxyethoxyethoxymethylacrylic acid) showed an LCST of 66°C. The cloud points of the solutions of these polymers were found to be sensitive to pH, and to concentrations of additives such as urea, salts, and surfactants. Because of low molecular weight due to chain transfer, high molecular weight analogs of the ether-linked polymers were synthesized in which ester linkages joined the oligo-oxyethylene segment to the acrylate moiety. Poly(alpha-methoxyethoxyacetoxymethylacrylic acid) was the only one of this series to give an LCST with a value of 52.5°C. Copolymers of t-butyl alpha-methoxymethylacrylate (tBMMA) with alpha-(1H,1H- perfluorooctyloxymethyl)acrylic acid (PFOMA) were synthesized, deprotected and their lower critical solution temperatures (LCSTs) evaluated. At PFOMA feed ratios of 0.25 mol % or less, no observable change in the LCST was observed, while at PFOMA feed ratios of above 0.25 mol % to 1.125 mol %, a large linear decrease in the LCST was observed with increasing fluorocarbon content. t-Butyl alpha-(N-vinylformamidomethyl)acrylate (tBVFA) and ethyl alpha-(N-vinylformamidomethyl)acrylate (EVFA) were synthesized from t-butyl alpha-bromomethylacrylate and ethyl alpha-chloromethylacrylate, respectively. tBVFA was found to cyclopolymerize at 120°C in DMF, DMSO, and 1,2-dichlorobenzene at solvent:monomer ratios of 10:1 vol:wt. Molecular weights for poly(tBVFA) ranged from 10,000 to 13,000 as estimated by size-exclusion chromatography. At lower solvent monomer ratio (1:1), and at lower temperature (71°C), crosslinking occurred. EVFA was found to

Antibacterial performance and in vivo diabetic wound healing of curcumin loaded gum tragacanth/poly(ε-caprolactone) electrospun nanofibers

International Nuclear Information System (INIS)

Ranjbar-Mohammadi, Marziyeh; Rabbani, Shahram; Bahrami, S. Hajir; Joghataei, M.T.; Moayer, F.

2016-01-01

In this study we describe the potential of electrospun curcumin-loaded poly(ε-caprolactone) (PCL)/gum tragacanth (GT) (PCL/GT/Cur) nanofibers for wound healing in diabetic rats. These scaffolds with antibacterial property against methicillin resistant Staphylococcus aureus as gram positive bacteria and extended spectrum β lactamase as gram negative bacteria were applied in two forms of acellular and cell-seeded for assessing their capability in healing full thickness wound on the dorsum of rats. After 15 days, pathological study showed that the application of GT/PCL/Cur nanofibers caused markedly fast wound closure with well-formed granulation tissue dominated by fibroblast proliferation, collagen deposition, complete early regenerated epithelial layer and formation of sweat glands and hair follicles. No such appendage formation was observed in the untreated controls during this duration. Masson's trichrome staining confirmed the increased presence of collagen in the dermis of the nanofiber treated wounds on day 5 and 15, while the control wounds were largely devoid of collagen on day 5 and exhibited less collagen amount on day 15. Quantification analysis of scaffolds on day 5 confirmed that, tissue engineered scaffolds with increased amount of angiogenesis number, granulation tissue area (μ 2 ), fibroblast number, and decreased epithelial gap (μ) can be more effective compared to GT/PCL/Cur nanofibers. - Highlights: • The potential of electrospun curcumin-loaded PCL/gum tragacanth (GT) nanofibers for wound healing in diabetic rats was investigated. • Pathological study showed that the application of GT/PCL/Cur nanofibers caused markedly fast wound closure with well-formed granulation tissue. • Masson’s trichrome staining confirmed the increased presence of collagen in the dermis of the nanofiber treated wounds on day 5 and 15 • Wounds which were treated with cell-seeded scaffolds showed smaller scabs areas in comparison with ones treated with

Antibacterial performance and in vivo diabetic wound healing of curcumin loaded gum tragacanth/poly(ε-caprolactone) electrospun nanofibers

Energy Technology Data Exchange (ETDEWEB)

Ranjbar-Mohammadi, Marziyeh, E-mail: m.ranjbar@bonabu.ac.ir [Textile Group, Engineering Department, University of Bonab, Bonab (Iran, Islamic Republic of); Rabbani, Shahram [Tehran Heart Center, Tehran University of Medical Sciences (Iran, Islamic Republic of); Bahrami, S. Hajir [Textile engineering Department, Amirkabir University of Technology, Tehran (Iran, Islamic Republic of); Joghataei, M.T. [Cellular and Molecular Research Center, Iran University of Medical Science, Tehran (Iran, Islamic Republic of); Moayer, F. [Department of Pathobiology, Faculty of Veterinary Medicine, Karaj Branch, Islamic Azad University, Karaj (Iran, Islamic Republic of)

2016-12-01

In this study we describe the potential of electrospun curcumin-loaded poly(ε-caprolactone) (PCL)/gum tragacanth (GT) (PCL/GT/Cur) nanofibers for wound healing in diabetic rats. These scaffolds with antibacterial property against methicillin resistant Staphylococcus aureus as gram positive bacteria and extended spectrum β lactamase as gram negative bacteria were applied in two forms of acellular and cell-seeded for assessing their capability in healing full thickness wound on the dorsum of rats. After 15 days, pathological study showed that the application of GT/PCL/Cur nanofibers caused markedly fast wound closure with well-formed granulation tissue dominated by fibroblast proliferation, collagen deposition, complete early regenerated epithelial layer and formation of sweat glands and hair follicles. No such appendage formation was observed in the untreated controls during this duration. Masson's trichrome staining confirmed the increased presence of collagen in the dermis of the nanofiber treated wounds on day 5 and 15, while the control wounds were largely devoid of collagen on day 5 and exhibited less collagen amount on day 15. Quantification analysis of scaffolds on day 5 confirmed that, tissue engineered scaffolds with increased amount of angiogenesis number, granulation tissue area (μ{sup 2}), fibroblast number, and decreased epithelial gap (μ) can be more effective compared to GT/PCL/Cur nanofibers. - Highlights: • The potential of electrospun curcumin-loaded PCL/gum tragacanth (GT) nanofibers for wound healing in diabetic rats was investigated. • Pathological study showed that the application of GT/PCL/Cur nanofibers caused markedly fast wound closure with well-formed granulation tissue. • Masson’s trichrome staining confirmed the increased presence of collagen in the dermis of the nanofiber treated wounds on day 5 and 15 • Wounds which were treated with cell-seeded scaffolds showed smaller scabs areas in comparison with ones treated

Comparative analysis of poly-glycolic acid-based hybrid polymer starter matrices for in vitro tissue engineering.

Science.gov (United States)

Generali, Melanie; Kehl, Debora; Capulli, Andrew K; Parker, Kevin K; Hoerstrup, Simon P; Weber, Benedikt

2017-10-01

Biodegradable scaffold matrixes form the basis of any in vitro tissue engineering approach by acting as a temporary matrix for cell proliferation and extracellular matrix deposition until the scaffold is replaced by neo-tissue. In this context several synthetic polymers have been investigated, however a concise systematic comparative analyses is missing. Therefore, the present study systematically compares three frequently used polymers for the in vitro engineering of extracellular matrix based on poly-glycolic acid (PGA) under static as well as dynamic conditions. Ultra-structural analysis was used to examine the polymers structure. For tissue engineering (TE) three human fibroblast cell lines were seeded on either PGA-poly-4-hydroxybutyrate (P4HB), PGA-poly-lactic acid (PLA) or PGA-poly-caprolactone (PCL) patches. These patches were analyzed after 21days of culture qualitative by histology and quantitative by determining the amount of DNA, glycosaminoglycan and hydroxyproline. We found that PGA-P4HB and PGA-PLA scaffolds enhance tissue formation significantly higher than PGA-PCL scaffolds (p<0.05). Polymer remnants were visualized by polarization microscopy. In addition, biomechanical properties of the tissue engineered patches were determined in comparison to native tissue. This study may allow future studies to specifically select certain polymer starter matrices aiming at specific tissue properties of the bioengineered constructs in vitro. Copyright © 2017 Elsevier B.V. All rights reserved.

Fabrication of platinum nanoparticles in aqueous solution and solid phase using amphiphilic PB-b-PEO copolymer nanoreactors

International Nuclear Information System (INIS)

Hoda, Numan; Budama, Leyla; Çakır, Burçin Acar; Topel, Önder; Ozisik, Rahmi

2013-01-01

Graphical abstract: TEM image of Pt nanoparticles produced by reducing by NaBH 4 within PB-b-PEO micelles in aqueous media (scale bar 1 nm). - Highlights: • Pt nanoparticles were synthesized within amphiphilic diblock copolymer micelles. • The effects of reducing agents and precursor dose on Pt np size were investigated. • The effect on fabrication of Pt np by reducing in aqueous and solid phases was compared. • The size of nanoparticles was about 1.4 nm for all doses and reducing agents types. - Abstract: Fabrication of Pt nanoparticles using an amphiphilic copolymer template in aqueous solution was achieved via polybutadiene-block-polyethyleneoxide copolymer micelles, which acted as nanoreactors. In addition, Pt nanoparticles were synthesized using hydrogen gas as the reducing agent in solid state for the first time to compare against solution synthesis. The influences of loaded precursor salt amount to micelles and the type of reducing agent on the size of nanoparticles were investigated through transmission electron microscopy. It was found that increasing the ratio of precursor salt to copolymer and using different type of reducing agent, even in solid phase reduction, did not affect the nanoparticle size. The average size of Pt nanoparticles was estimated to be 1.4 ± 0.1 nm. The reason for getting same sized nanoparticles was discussed in the light of nucleation, growth process, stabilization and diffusion of nanoparticles within micelles

Hydrogels from Amorphous Calcium Carbonate and Polyacrylic Acid: Bio-Inspired Materials for "Mineral Plastics".

Science.gov (United States)

Sun, Shengtong; Mao, Li-Bo; Lei, Zhouyue; Yu, Shu-Hong; Cölfen, Helmut

2016-09-19

Given increasing environmental issues due to the large usage of non-biodegradable plastics based on petroleum, new plastic materials, which are economic, environmentally friendly, and recyclable are in high demand. One feasible strategy is the bio-inspired synthesis of mineral-based hybrid materials. Herein we report a facile route for an amorphous CaCO3 (ACC)-based hydrogel consisting of very small ACC nanoparticles physically cross-linked by poly(acrylic acid). The hydrogel is shapeable, stretchable, and self-healable. Upon drying, the hydrogel forms free-standing, rigid, and transparent objects with remarkable mechanical performance. By swelling in water, the material can completely recover the initial hydrogel state. As a matrix, thermochromism can also be easily introduced. The present hybrid hydrogel may represent a new class of plastic materials, the "mineral plastics". © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorção de poli(acrilamida-b-N,N-dihexilacrilamida sobre arenito: determinação das condições para se atingir o equilíbrio real Poly(acrylamide-b-N,N-dihexylacrylamide adsorption on sandstone: determination of the conditions to reach the real equilibrium

Directory of Open Access Journals (Sweden)

Ana Maria S. Maia

2007-03-01

Full Text Available Durante as últimas décadas, o interesse em polímeros anfifílicos tem aumentado continuamente. Neste trabalho, o comportamento do copolímero hidrofílico/hidrofóbico poli(acrilamida-b-N,N-dihexilacrilamida (PADHA na interface sólido/líquido foi estudado para se quantificar a adsorção quando o equilíbrio do sistema é atingido. Na interface água/arenito, a isoterma de adsorção para a PADHA mostrou uma forma incomum, caracterizada pela ausência de uma região de patamar e um aumento contínuo na quantidade adsorvida com a concentração polimérica. Esta forma de adsorção particular poderia ser explicada pela formação de múltiplas camadas devido a associações hidrofóbicas, através das quais as camadas adsorvidas seriam formadas, em parte, por algumas cadeias que não estão diretamente em contato com a superfície sólida.During the last few decades, interest in amphiphilic polymers has increased steadily. In this work, the behavior of the hydrophilic/hydrophobic copolymer poly(acrylamide-b-N,N-dihexylacrylamide (PADHA at a solid/liquid interface has been studied to quantify adsorption at equilibrium. At the water/sandstone interface, the adsorption isotherm for PADHA show an unusual profile, characterized by the absence of a "plateau" region and a monotonic increase in the adsorbed amount with polymer concentration in the bulk. This particular adsorption profile could be explained by the formation of multiple layers caused by hydrophobic associations, the adsorbed layers being partly formed by chains that are not directly in contact with the surface.

INAA of polyacrylic hydrogels of pharmaceutical grade

International Nuclear Information System (INIS)

Ponta, C.; Salagean, M.; Pantelica, A.; Georgescu, I.I.

1998-01-01

Polyacrylic acid (PA) and its salts are promising biomaterials used in the pharmaceutical industry. They could be used as pharmaceutical additives, as a burn dressing and also in the slow released implants or trans-derma patch formulations. Polyacrylic acid of pharmaceutical grade can be obtained by gamma irradiation polymerization. The influence of the raw materials and of the technological procedure on the final product purity has been investigated by Instrumental Neutron Activation Analysis (INAA) method. The following materials have been analyzed by INAA: 1) acrylic acid of technical grade; 2) acrylic acid purified by double crystallisation; 3) NaOH of analytical grade; 4) CaCl-2·6H 2 O of pharmaceutical grade; 5) CaCl 2 ·2H 2 O of analytical grade; 6) granulated PANa; 7) ungranulated PANa; 8) ungranulated PANaCa; 9) PANaCa granulated by milling in IFIN-HH using the mill nr. 1; 10) PANaCa granulated by milling in Institute of Chemical and Pharmaceutical Research (ICPR); 11) PANaCa granulated by milling in IFIN-HH using the mill nr. 2. The first five samples, marked from 1 to 5, are raw materials and the other six samples, marked from 6 to 11, are the final polyacrylic structures processed by various technological procedures. The samples together with the appropriate reference materials have been irradiated at WWR-S reactor in a neutron flux of 2.5·10 12 cm -2 s -1 and the induced radioactivity was registered by a HPGe detector (EG/G ORTEC) of 30% efficiency and 2.1 keV resolution. The concentrations of As, Br, Ce, Co, Cr, Fe, La, Sb, Sc, Zn have been determined. For the final polyacrylic structures, except for granulated PANa (sample 6), only the elements Co, Cr, Fe, Sc, Zn were found at the following concentration levels: tens of ppm (Co), ppm (Zn), hundreds of ppb (Cr), tens of ppb (Co), ppb (Co, Sc), 10 -1 ppb (Sc). In the granulated PANa, in comparison with the other analyzed final products, similar concentration values were found for Fe, Sc and Zn

Effects of surface modification on the mechanical and structural properties of nanofibrous poly(ε-caprolactone)/forsterite scaffold for tissue engineering applications

Energy Technology Data Exchange (ETDEWEB)

Kharaziha, M., E-mail: Kharaziha.ma@yahoo.com [Biomaterials Research Group, Department of Materials Engineering, Isfahan University of Technology, Isfahan 8415683111 (Iran, Islamic Republic of); Department of Materials Engineering, Isfahan University of Technology, Isfahan 8415683111 (Iran, Islamic Republic of); Fathi, M.H. [Biomaterials Research Group, Department of Materials Engineering, Isfahan University of Technology, Isfahan 8415683111 (Iran, Islamic Republic of); Dental Materials Research Center, Isfahan University of Medical Sciences, Isfahan (Iran, Islamic Republic of); Edris, H. [Biomaterials Research Group, Department of Materials Engineering, Isfahan University of Technology, Isfahan 8415683111 (Iran, Islamic Republic of); Department of Materials Engineering, Isfahan University of Technology, Isfahan 8415683111 (Iran, Islamic Republic of)

2013-12-01

Composite scaffolds consisting of polymers reinforced with ceramic nanoparticles are widely applied for hard tissue engineering. However, due to the incompatible polarity of ceramic nanoparticles with polymers, they tend to agglomerate in the polymer matrix which results in undesirable effects on the integral properties of composites. In this research, forsterite (Mg{sub 2}SiO{sub 4}) nanoparticles was surface esterified by dodecyl alcohol and nanofibrous poly(ε-caprolactone)(PCL)/modified forsterite scaffolds were developed through electrospinning technique. The aim of this research was to investigate the properties of surface modified forsterite nanopowder and PCL/modified forsterite scaffolds, before and after hydrolytic treatment, as well as the cellular attachment and proliferation. Results demonstrated that surface modification of nanoparticles significantly enhanced the tensile strength and toughness of scaffolds upon 1.5- and 4-folds compared to unmodified samples, respectively, due to improved compatibility between matrix and filler. Hydrolytic treatment of scaffolds also modified the bioactivity and cellular attachment and proliferation due to greatly enhanced hydrophilicity of the forsterite nanoparticles after this process compared to surface modified samples. Results suggested that surface modification of forsterite nanopowder and hydrolytic treatment of the developed scaffolds were effective approaches to address the issues in the formation of composite fibers and resulted in development of bioactive composite scaffolds with ideal mechanical and structural properties for bone tissue engineering applications. - Highlights: • Forsterite nanopowder was surface modified with dodecyl alcohol. • Nanofibrous PCL/forsterite scaffolds were developed through electrospinning. • Composite scaffolds were treated in boiled water to remove the dodecyl chains. • Surface modification resulted in improved mechanical properties. • Hydrolytic treatment

Interaction of neptunium(V) with polyacrylic acid

International Nuclear Information System (INIS)

Kubota, Takumi; Tochiyama, Osamu; Yamazaki, Hiromichi; Sato, Nobuharu

1996-01-01

For the quantitative description of the interaction of actinoids with humic substances, it is necessary to clarify the effects of both polyelectrolyte and heterogeneous nature of humic substances. To estimate these effects separately, polyacrylic acid has been selected as representative of well-defined, homogenous polymeric weak acids, and its interaction with Np(V) has been investigated by a solvent extraction method. By expressing the effective concentration of the complexing ligand by the concentration of ionized carboxylate groups, the apparent complex formation constant has been obtained at several pH, ionic strength and average molecular weights. The results indicated that the apparent complex formation constant varied with the degree of ionization(α) of polyacrylic acid and that the manner of variation resembled that of its apparent proton association constant. (author)

Impact of the Formulation Pathway on the Colloidal State and Crystallinity of Poly-ε-caprolactone Particles Prepared by Solvent Displacement.

Science.gov (United States)

Pucci, Carlotta; Cousin, Fabrice; Dole, François; Chapel, Jean-Paul; Schatz, Christophe

2018-02-20

The formulation pathway and/or the mixing method are known to be relevant in many out-of-equilibrium processes. In this work, we studied the effect of the mixing conditions on the physicochemical properties of poly-ε-caprolactone (PCL) particles prepared by solvent displacement. More specifically, water was added in one shot (fast addition) or drop by drop to PCL solution in tetrahydrofuran (THF) to study the impact of the mixing process on particle properties including size, stability, and crystallinity. Two distinct composition maps representing the Ouzo domain characteristic of the presence of metastable nanoparticles have been established for each mixing method. Polymer nanoparticles are formed in the Ouzo domain according to a nucleation and growth (or aggregation) mechanism. The fast addition promotes a larger nucleation rate, thus favoring the formation of small and uniform particles. For the drop-by-drop addition, for which the polymer solubility gradually decreases, the composition trajectories systematically cross an intermediate unstable region between the solubility limit of the polymer and the Ouzo domain. This leads to heterogeneous nucleation as shown by the formation of larger and less stable particles. Particles formed in the Ouzo domain have semi-crystalline properties. The PCL melting point is decreased with the THF fraction trapped in particles in accordance with Flory's theory for melt crystallization. On the other hand, the degree of crystallinity is constant, around 20% regardless of the THF fraction. No difference between fast and slow addition could be detected on the semi-crystalline properties of the particles which emphasize that thermodynamic rather than kinetic factors drive the polymer crystallization in particles. The recovery of bulk PCL crystallinity after the removal of THF from particles tends to confirm this hypothesis.

Comparison of 3D-Printed Poly-ɛ-Caprolactone Scaffolds Functionalized with Tricalcium Phosphate, Hydroxyapatite, Bio-Oss, or Decellularized Bone Matrix.

Science.gov (United States)

Nyberg, Ethan; Rindone, Alexandra; Dorafshar, Amir; Grayson, Warren L

2017-06-01

Three-dimensional (3D)-printing facilitates rapid, custom manufacturing of bone scaffolds with a wide range of material choices. Recent studies have demonstrated the potential for 3D-printing bioactive (i.e., osteo-inductive) scaffolds for use in bone regeneration applications. In this study, we 3D-printed porous poly-ɛ-caprolactone (PCL) scaffolds using a fused deposition modeling (FDM) process and functionalized them with mineral additives that have been widely used commercially and clinically: tricalcium phosphate (TCP), hydroxyapatite (HA), Bio-Oss (BO), or decellularized bone matrix (DCB). We assessed the "print quality" of the composite scaffolds and found that the print quality of PCL-TCP, PCL-BO, and PCL-DCB measured ∼0.7 and was statistically lower than PCL and PCL-HA scaffolds (∼0.8). We found that the incorporation of mineral particles did not significantly decrease the compressive modulus of the graft, which was on the order of 260 MPa for solid blocks and ranged from 32 to 83 MPa for porous scaffolds. Raman spectroscopy revealed the surfaces of the scaffolds maintained the chemical profile of their dopants following the printing process. We evaluated the osteo-inductive properties of each scaffold composite by culturing adipose-derived stromal/stem cells in vitro and assessing their differentiation into osteoblasts. The calcium content (normalized to DNA) increased significantly in PCL-TCP (p  0.05). Collagen 1 expression was 10-fold greater than PCL in PCL-BO and PCL-DCB (p < 0.05) and osteocalcin expression was 10-fold greater in PCL-BO and PCL-DCB (p < 0.05) as measured by quantitative-real time-polymerase chain reaction. This study suggests that PCL-BO and PCL-DCB hybrid material may be advantageous for bone healing applications over PCL-HA or PCL-TCP blends.

SYNTHESIS OF pH-RESPONSIVE AMPHIPHILIC DIBLOCK COPOLYMERS CONTAINING POLYISOBUTYLENE via OXYANION-INITIATED POLYMERIZATION AND THEIR MULTIPLE SELF-ASSEMBLY MORPHOLOGIES

Institute of Scientific and Technical Information of China (English)

Huai-chao Wang; Ming-zu Zhang; Pei-hong Ni; Jin-lin He; Ying Hao; Yi-xian Wu

2013-01-01

Two pH-responsive amphiphilic diblock copolymers,namely polyisobutylene-block-poly[2-(N,N-dimethylamino)ethyl methacrylate] (PIB-b-PDMAEMA) and polyisobutylene-block-poly(metharylic acid) (PIB-b-PMAA),were synthesized via oxyanion-initiated polymerization,and their multiple self-assembly behaviors have been studied.An exo-o1efin-terminated highly reactive polyisobutylene (HRPIB) was first changed to hydroxyl-terminated PIB (PIB-OH) via hydroboration-oxidation of C=C double bond in the chain end,and then reacted with KH to yield a potassium alcoholate of PIB (PIB-O-K+).PIB-O-K+ was immediately used as a macroinitiator to polymerize DMAEMA monomer,resulting in a cationic diblock copolymer PIB-b-PDMAEMA.With the similar synthesis procedure,the anionic diblock copolymer PIB-b-PMAA could be prepared via a combination of oxyanion-initiated polymerization of tert-butyl methacrylate (tBMA) and subsequent hydrolysis of tert-butyl ester groups in PtBMA block.The functional PIB and block copolymers have been fully characterized by 1H-NMR,FT-IR spectroscopy,and gel permeation chromatography (GPC).These samples allowed us to systematically investigate the effects of block composition on the pH responsivity and various self-assembled morphologies of the copolymers in THF/water mixed solvent.Transmission electron microscopy (TEM) images revealed that these diblock copolymers containing small amount of original PIB without exo-olefin-terminated group are able to self-assemble into micelles,vesicles with different particle sizes and cylindrical aggregates,depending on various factors including block copolymer composition,solvent polarity and pH value.

Synthesis, characterization, and property of biodegradable PEG-PCL-PLA terpolymers with miktoarm star and triblock architectures as drug carriers.

Science.gov (United States)

Zhang, Yixin; Luo, Song; Liang, Yan; Zhang, Hai; Peng, Xinyu; He, Bin; Li, Sai

2018-03-01

A series of amphiphilic terpolymers with miktoarm star and triblock architectures of poly(ethylene glycol) (PEG), poly(ε-caprolactone) (PCL) and poly(l-lactide acid) (PLLA) or poly(DL-lactide acid) (PDLLA) terpolymers were synthesized as carriers for drug delivery. The architecture, molecular weight and crystallization behavior of the terpolymers were characterized. Anticancer drug doxorubicin was encapsulated in the micelles to investigate their drug loading properties. The miktoarm star terpolymers exhibited stronger crystallization capability, smaller size and better stability than that of triblock polymeric micelle, owing to the lower CMC values of miktoarm star polymeric micelle. Furthermore, the drug-loaded miktoarm star polymeric micelles showed the cumulative DOX release account of the micelles with PDLLA blocks was 65.3% while the release account of the corresponding micelles containing PLLA blocks was 45.2%. The IC 50 values of drug-loaded miktoarm star polymeric micelle were lower than triblock polymeric micelle. Meanwhile, Confocal laser scanning microscopy (CLSM) and Flow Cytometry results demonstrated that the miktoarm star micelles were more favorable for cellular internalization. The miktoarm star micelles with PDLLA blocks were promising carriers for anticancer drug delivery.

Poly(N-isopropylacrylamide and Copolymers: A Review on Recent Progresses in Biomedical Applications

Directory of Open Access Journals (Sweden)

Sonia Lanzalaco

2017-10-01

Full Text Available The innate ability of poly(N-isopropylacrylamide (PNIPAAm thermo-responsive hydrogel to copolymerize and to graft synthetic polymers and biomolecules, in conjunction with the highly controlled methods of radical polymerization which are now available, have expedited the widespread number of papers published in the last decade—especially in the biomedical field. Therefore, PNIPAAm-based hydrogels are extensively investigated for applications on the controlled delivery of active molecules, in self-healing materials, tissue engineering, regenerative medicine, or in the smart encapsulation of cells. The most promising polymers for biodegradability enhancement of PNIPAAm hydrogels are probably poly(ethylene glycol (PEG and/or poly(ε-caprolactone (PCL, whereas the biocompatibility is mostly achieved with biopolymers. Ultimately, advances in three-dimensional bioprinting technology would contribute to the design of new devices and medical tools with thermal stimuli response needs, fabricated with PNIPAAm hydrogels.