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Sample records for amphiphilic double-comb diblock

  1. Micellar structure of amphiphilic poly(2-oxazoline) diblock copolymers

    DEFF Research Database (Denmark)

    Papadakis, C.M.; Ivanova, R.; Lüdtke, K.

    2007-01-01

    Amphiphilic diblock copolymers from poly(2-oxazoline)s in aqueous solution can form micelles. By means of small-angle neutron scattering, we have found that poly[(n-nonyl-2-oxazoline)-b-(methyl-2-oxazoline)] {P[(NOx)-b-(MOx)]} diblock copolymers in aqueous solution form micelles of core-shell typ...

  2. Self-assembly of crystalline nanotubes from monodisperse amphiphilic diblock copolypeptoid tiles.

    Science.gov (United States)

    Sun, Jing; Jiang, Xi; Lund, Reidar; Downing, Kenneth H; Balsara, Nitash P; Zuckermann, Ronald N

    2016-04-12

    The folding and assembly of sequence-defined polymers into precisely ordered nanostructures promises a class of well-defined biomimetic architectures with specific function. Amphiphilic diblock copolymers are known to self-assemble in water to form a variety of nanostructured morphologies including spheres, disks, cylinders, and vesicles. In all of these cases, the predominant driving force for assembly is the formation of a hydrophobic core that excludes water, whereas the hydrophilic blocks are solvated and extend into the aqueous phase. However, such polymer systems typically have broad molar mass distributions and lack the purity and sequence-defined structure often associated with biologically derived polymers. Here, we demonstrate that purified, monodisperse amphiphilic diblock copolypeptoids, with chemically distinct domains that are congruent in size and shape, can behave like molecular tile units that spontaneously assemble into hollow, crystalline nanotubes in water. The nanotubes consist of stacked, porous crystalline rings, and are held together primarily by side-chain van der Waals interactions. The peptoid nanotubes form without a central hydrophobic core, chirality, a hydrogen bond network, and electrostatic or π-π interactions. These results demonstrate the remarkable structure-directing influence of n-alkane and ethyleneoxy side chains in polymer self-assembly. More broadly, this work suggests that flexible, low-molecular-weight sequence-defined polymers can serve as molecular tile units that can assemble into precision supramolecular architectures.

  3. Aggregation behavior or amphiphilic poly(2-alkyl-2-oxazoline) diblock copolymers in aqueous solution studied by fluorescence correlation spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Bonné, T. B.; Lüdtke, K.; Jordan, R.; Štěpánek, Petr; Papadakis, C. M.

    2004-01-01

    Roč. 282, č. 12 (2004), s. 833-843 ISSN 0303-402X R&D Projects: GA AV ČR IAA4050403 Keywords : self-diffusion * fluorescence correlation spectroscopy * amphiphilic diblock copolymers Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.110, year: 2004

  4. 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...

  5. Effects of amphiphilic diblock copolymer on drug nanoparticle formation and stability

    Science.gov (United States)

    Zhu, Zhengxi

    2013-01-01

    This study systematically compares the effects of amphiphilic diblock copolymer (di-BCP) on stabilizing hydrophobic drug nanoparticles formed by flash nanoprecipitation (FNP), and provides a guideline on choosing suitable di-BCPs. Four widely used di-BCPs, i.e., polystyrene-block-poly(ethylene glycol) (PS-b-PEG), polycaprolactone-block-poly(ethylene glycol) (PCL-b-PEG), polylactide-block-poly(ethylene glycol) (PLA-b-PEG), and poly(lactic-co-glycolic acid) (PLGA-b-PEG), and β-carotene as a model drug were used. The study showed that PLGA-b-PEG was the most suitable one, whose hydrophobic block was biodegradable and noncrystallizable as well as had relatively high glass transition temperature (Tg) and a right solubility parameter (δ). The molecular weight of PLGA block over the range from 5k to 15k showed an insignificant effect on controlling the particle size. Amorphous drug particles with a high drug loading of over 83 wt% can be achieved. Much remarkable evidence supported the nanoparticles with kinetically frozen and nonequilibrium packing structures of polymer chains rather than either the micelles or micellar nanoparticles with two well segregated polymer blocks. The thermodynamic effects of the drug and BCP on the particle stability, size and structures were discussed by using solubility parameters. PMID:24070569

  6. 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.

  7. Micelle formation of amphiphilic polystyrene-b-poly(N-vinylpyrrolidone) diblock copolymer in methanol and water-methanol binary mixtures.

    Science.gov (United States)

    Hussain, H; Tan, B H; Gudipati, C S; He, C B; Liu, Y; Davis, Thomas P

    2009-05-19

    The micelle formation by the amphiphilic polystyrene-block-poly(N-vinylpyrrolidone) (PS48-b-PNVP99) copolymer is investigated in methanol and water-methanol binary mixtures of various compositions using 1H NMR, fluorescence spectroscopy, static/dynamic light scattering (SLS/DLS), and transmission electron microscopy (TEM). Critical micelle concentrations (cmc) are determined by employing fluorescence spectroscopy and DLS measurements. The cmc of the PS48-b-PNVP99 block copolymer increases with increasing methanol content in the water-methanol binary mixtures, suggesting that methanol is a better solvent for the PS48-b-PNVP99 block copolymer than water-methanol mixtures or pure water. The amphiphilic PS48-b-PNVP99 diblock copolymer forms spherical micelles of Rh approximately 16 nm in pure methanol solution as revealed by DLS measurements. In contrast, significantly larger micelles having higher aggregation numbers are formed in water-methanol binary mixtures. Temperature dependent data reveal an increase in aggregation number and radius of gyration (Rg) concomitantly with temperature (10-40 degrees C). In contrast, the overall size (Rh) of the micelles remains almost constant over the same temperature range. An explanation is tendered that PNVP coronas dehydrate/desolvate at higher temperatures counteracting the increase in micelle size (Rh) caused by increased aggregation numbers (Nagg).

  8. Amphiphilic PEO-b-PBLG diblock and PBLG-b-PEO-b-PBLG triblock copolymer based nanoparticles: doxorubicin loading and in vitro evaluation.

    Science.gov (United States)

    Kakkar, Dipti; Mazzaferro, Silvia; Thevenot, Julie; Schatz, Christophe; Bhatt, Anant; Dwarakanath, Bilikere S; Singh, Harpal; Mishra, Anil K; Lecommandoux, Sebastien

    2015-01-01

    Huisgen's 1,3-dipolar cycloaddition ("Click Chemestry") has been used to prepare amphiphilic PEO-b-PBLG diblock and PBLG-b-PEO-b-PBLG triblock copolymers as potential carriers of anticancer drugs. Spherical and flower shaped micelles (D ≈ 100 nm) were obtained from diblock and triblock copolymers respectively. DOX was effectively encapsulated up to 18 wt.% and 50-60% of it was steadily released from the micelles over a period of 7 d. Flow cytometry and fluorescence microscopy confirmed the effective intracellular uptake as well as the sustained release of DOX from micelles. These results suggest that the diblock as well as triblock copolymers are promising carriers for intra-cellular drug delivery. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Synthesis of amphiphilic diblock copolymer for surface modification of Ethylene-Norbornene copolymers

    DEFF Research Database (Denmark)

    Levinsen, Simon; Svendsen, Winnie Edith; Horsewell, Andy

    2014-01-01

    -norbornene copolymer TOPAS. Through matching of the radius of gyration for the model polymer and TOPAS the miscibility was achieved. The poly(ethylene-1-butene) polymer was synthesized from a hydrogenated anionic polymerized polybutadiene polymer. As hydrophilic block poly(ethylene oxide) was subsequently added also...... consisting of a bulk material compatible block and a hydrophilic block. To utilize the possibility of incorporating diblock copolymers into ethylenenorbornene copolymers, we have in this work developed a model poly(ethylene-1-butene) polymer compatible with the commercial available ethylene...

  10. Pressure induced structure formation in Langmuir monolayers of amphiphilic metallocene diblock copolymers.

    Science.gov (United States)

    Kraska, Martin; Gallei, Markus; Stühn, Bernd; Rehahn, Matthias

    2013-07-02

    We present in situ structural investigations of a metal-containing diblock copolymer on a water surface. Monolayers of poly(vinylferrocene-b-(2-vinylpyridine)) (PVFc-b-P2VP) block copolymers are studied in a wide range of compositions by varying molar masses of P2VP with two different molecular weights of PVFc. We focus on the role of the respective block partners, PVFc and P2VP, when compressing the layer on the water surface. Compression isotherms are presented and interpreted in terms of the classical gaseous, expanded, and condensed phases. We calculate isothermal compressibilities, which reveal a minimum value independent of the molar masses of the respective block partners. We find the isotherms to be dominated by P2VP while PVFc barely contribute to the compression behavior due to its rather compact coil structure. We consider the diblock copolymer monolayers as a two-dimensional model system, which is reflected by two-dimensional scaling behavior in the semi dilute and condensed regime. By X-ray reflectometry (XR), we monitor in situ the monolayer structure change with increasing surface pressure Π and observe the PVFc-b-P2VP separation at high Π.

  11. Micelles from HOOC-PnBA-b-PAA-C12H15 Diblock Amphiphilic Polyelectrolytes as Protein Nanocarriers.

    Science.gov (United States)

    Papagiannopoulos, Aristeidis; Meristoudi, Anastasia; Pispas, Stergios; Radulescu, Aurel

    2016-11-14

    We investigate the potential of self-assembled nanostructures of the PnBA-b-PAA amphiphilic diblock polyelectrolyte as candidates for protein nanocarriers. Three PnBA-b-PAA copolymers with different molecular weights and PnBA/PAA weight ratios are tested. The system with the most well-defined core-shell micellar structure is chosen for complexation with lysozyme. Its solutions are found to contain well-defined core-shell micelles that are stable upon increase in solution salt content to physiological levels. Upon mixing with lysozyme we find that the protein globules accumulate preferably at the outer parts of the hydrated corona of the micelles. Increasing the protein concentration, intermicellar aggregation is enhanced in a controllable way. At high salt content the number of proteins per micelle is lower compared with the low salt content, which points to an interaction of predominantly electrostatic nature. While light scattering is very sensitive to complexation, small-angle neutron scattering is able to distinguish between the contributions from individual micelles and aggregates. This work demonstrates the use of scattering techniques to characterize protein-polymer interactions in multiple hierarchical levels.

  12. The effect of hydrophilic and hydrophobic block length on the rheology of amphiphilic diblock Polystyrene-b-Poly(sodium methacrylate) copolymers prepared by ATRP.

    Science.gov (United States)

    Raffa, Patrizio; Stuart, Marc C A; Broekhuis, Antonius A; Picchioni, Francesco

    2014-08-15

    Following our previous investigation on the effect of molecular architecture on the rheology of Polystyrene-b-Poly(sodium methacrylate) copolymers (PS-b-PMAA), we consider here diblock PS-b-PMAA copolymers characterized by a different length of either the hydrophilic or the hydrophobic block. Various copolymers characterized by different PS or PMAA block length have been prepared by ATRP (kinetics is also discussed) and studied from the point of view of their rheological behaviour in water. To the best of our knowledge, this is the first systematic investigation concerning the effect of block length on the rheology of diblock polyelectrolytes. We found that the hydrophobic block length has small influence on the rheology. Surprisingly, the polymers with shortest PMAA blocks yield the strongest gels at high concentration. A simple model based on the classical theories of self-assembly and percolation of amphiphilic polymers has been here developed in order to explain the observed data. Copyright © 2014 Elsevier Inc. All rights reserved.

  13. Synthesis and self-assembly behavior of amphiphilic diblock copolymer dextran-block-poly(ε-caprolactone (DEX-b-PCL in aqueous media

    Directory of Open Access Journals (Sweden)

    2010-10-01

    Full Text Available An amphiphilic diblock copolymer, dextran-block-poly(ε-caprolactone (DEX-b-PCL, with a series of welldefined chain lengths of each block was prepared by conjugating a dextran chain with a PCL block via aza-Michael addition reaction under mild conditions. For the dextran block, samples with relatively uniform molecular weight, 3.5 and 6.0 kDa, were used, and the PCL blocks were prepared via ring-opening polymerization at defined ratios of ε-caprolactone to initiator in order to give copolymers with mass fraction of dextran (fDEX ranging from 0.16 to 0.45. When these copolymers were allowed to self-assemble in aqueous solution, the morphology of assembled aggregates varied as a function of fDEX when characterized by transmission electron microscope (TEM, fluorescence microscope (FM and dynamic laser scattering (DLS. As fDEX decreases gradually from 0.45 to 0.16, the morphology of the copolymer assembly changes from spherical micelles to worm-like micelles and eventually to polymersomes, together with an increase in particle sizes.

  14. The effect of hydrophilic and hydrophobic block length on the rheology of amphiphilic diblock Polystyrene-b-Poly(sodium methacrylate) copolymers prepared by ATRP

    NARCIS (Netherlands)

    Raffa, Patrizio; Stuart, Marc C.A.; Broekhuis, Antonius A.; Picchioni, Francesco

    2014-01-01

    Following our previous investigation on the effect of molecular architecture on the rheology of Polystyrene-b-Poly(sodium methacrylate) copolymers (PS-b-PMAA), we consider here diblock PS-b-PMAA copolymers characterized by a different length of either the hydrophilic or the hydrophobic block.

  15. Phase-dependent interference between frequency doubled comb lines in a χ(2) phase-matched aluminum nitride microring.

    Science.gov (United States)

    Jung, Hojoong; Guo, Xiang; Zhu, Na; Papp, Scott B; Diddams, Scott A; Tang, Hong X

    2016-08-15

    Nonlinear optical conversion with frequency combs is important for self-referencing and for generating shorter wavelength combs. Here we demonstrate efficient frequency comb doubling through the combination of second-harmonic generation (SHG) and sum-frequency generation (SFG) of an input comb with a high Q, phase-matched χ(2) microring resonator. Phase coherence of the SHG and SFG nonlinear conversion processes is confirmed by sinusoidal phase-dependent interference between frequency doubled comb lines.

  16. Chain length dependence of the helix orientation in Langmuir-Blodgett monolayers of alpha-helical diblock copolypeptides

    NARCIS (Netherlands)

    Nguyen, Le-Thu T.; Ardana, Aditya; Vorenkamp, Eltjo J.; ten Brinke, Gerrit; Schouten, Arend J.

    2010-01-01

    The effect of chain length on the helix orientation of alpha-helical diblock copolypeptides in Langmuir and Langmuir-Blodgett monolayers is reported for the first time. Amphiphilic diblock copolypeptides (PLGA-b-PMLGSLGs) of poly(alpha-L-glutamic acid) (PLGA) and

  17. Preparation of plasmonic vesicles from amphiphilic gold nanocrystals grafted with polymer brushes

    OpenAIRE

    Song, Jibin; Huang, Peng; Chen, Xiaoyuan

    2016-01-01

    Gold nanovesicles contain multiple nanocrystals within a polymeric coating. The strong plasmonic coupling between adjacent nanoparticles in their vesicular shell makes ultrasensitive biosensing and bioimaging possible. In our laboratory, multifunctional plasmonic vesicles are assembled from amphiphilic gold nanocrystals (such as gold nanoparticles and gold nanorods) coated with mixed hydrophilic and hydrophobic polymer brushes or amphiphilic diblock co-polymer brushes. To fulfill the differen...

  18. 'Smart' Diblock Copolymers as Templates for Magnetic-Core Gold-Shell Nanoparticle Synthesis

    International Nuclear Information System (INIS)

    Nash, Michael A.; Lai, James J.; Hoffman, Allan S.; Yager, Paul; Stayton, Partick S.

    2010-01-01

    We report a new strategy for synthesizing temperature-responsive γ-Fe 2 O 3 -core/Au-shell nanoparticles (Au-mNPs) from diblock copolymer micelles. The amphiphilic diblock copolymer chains were synthesized using reversible addition-fragmentation chain-transfer (RAFT) with a thermally responsive 'smart' poly(N-isopropylacrylamide) (pNIPAAm) block and an amine-containing poly(N,N-dimethylaminoethylacrylamide) (DMAEAm) block that acted as a reducing agent during gold shell formation. The Au-mNPs reversibly aggregated upon heating the solution above the transition temperature of pNIPAAm, resulting in a red-shifted localized surface plasmon resonance.

  19. Micelles of a diblock copolymer of styrene and ethylene oxide in mixtures of 2,6-lutidine and water

    Czech Academy of Sciences Publication Activity Database

    Tuzar, Zdeněk; Kadlec, Petr; Štěpánek, Petr; Kříž, Jaroslav; Nallet, F.; Noirez, L.

    2008-01-01

    Roč. 24, č. 24 (2008), s. 13863-13865 ISSN 0743-7463 R&D Projects: GA AV ČR IAA4050403 Institutional research plan: CEZ:AV0Z40500505 Keywords : diblock copolymers * amphiphilic copolymers * light scattering * micellization Subject RIV: CD - Macromolecular Chemistry Impact factor: 4.097, year: 2008

  20. Synthesis, characterization, and utilization of polyol amphiphile molecules

    Science.gov (United States)

    Osenar, Paul

    1998-12-01

    Recent interest in self-organizing systems has led to the development of numerous novel molecules. This work describes the synthesis and characterization of a new type of amphiphile based on polar moieties of oligo(vinyl alcohol). The use of oligomeric moieties allows access to hydroxylated, nonionic amphiphiles beyond those available via the alkylation of various carbohydrates. Two synthetic pathways have been developed based on a precursor diblock structure of a hydrophobe and an oligo(vinyl ether) chain. The first methodology relies on aldol group transfer polymerization of various silyl vinyl ether monomers. In this method, a functionalized initiator was designed based on 4-hydroxybenzaldehyde in order to synthesize oligomers with a phenol terminus. Incorporation of a hydrophobic moiety was then accomplished via esterification to this terminus. A second approach to the precursor diblock was also developed based on direct initiation with a hydrophobe. Here, an aldehyde terminated hydrophobe was converted into an alpha-iodoether by reaction with trimethylsilyl iodide. In the presence of a Lewis acid catalyst, various alkyl vinyl ether oligomers can be grown from the hydrophobe via cationic polymerization techniques. These diblock structures can be converted to polyol amphiphiles by cleaving the ether side groups to yield a chain of hydroxyl groups. In the case of the silyl ethers, cleavage occurs with exposure to hydrofluoric acid; while those based on t-butyl ethers can be converted to silyl ethers with trimethylsilyl iodide and subsequently cleaved with fluoride ion. Polyol amphiphiles were synthesized with various hydroxyl chain lengths and hydrophobic moieties, including oleyl and oligo(styrene). These novel amphiphiles are predictably hygroscopic, forming lyotropic liquid crystals upon exposure to water. The resulting lamellar and hexagonal mesophases were characterized by a variety of techniques including small angle x-ray scattering and polarized optical

  1. Preparation of plasmonic vesicles from amphiphilic gold nanocrystals grafted with polymer brushes.

    Science.gov (United States)

    Song, Jibin; Huang, Peng; Chen, Xiaoyuan

    2016-11-01

    Gold nanovesicles contain multiple nanocrystals within a polymeric coating. The strong plasmonic coupling between adjacent nanoparticles in their vesicular shell makes ultrasensitive biosensing and bioimaging possible. In our laboratory, multifunctional plasmonic vesicles are assembled from amphiphilic gold nanocrystals (such as gold nanoparticles and gold nanorods) coated with mixed hydrophilic and hydrophobic polymer brushes or amphiphilic diblock co-polymer brushes. To fulfill the different requirements of biomedical applications, different polymers that are either pH=responsive, photoactive or biodegradable can be used to form the hydrophobic brush, while the hydrophilicity is maintained by polyethylene glycol (PEG). This protocol covers the preparation, surface functionalization and self-assembly of amphiphilic gold nanocrystals grafted covalently with polymer brushes. The protocol can be completed within 2 d. The preparation of amphiphilic gold nanocrystals, coated with amphiphilic diblock polymer brushes using a 'grafting to' method or mixed hydrophilic and hydrophobic polymer brushes using tandem 'grafting to' and 'grafting from' methods, is described. We also provide detailed procedures for the preparation and characterization of pH-responsive plasmonic gold nanovesicles from amphiphilic gold nanocrystals using a film-rehydration method that can be completed within ∼3 d.

  2. Self-assembled structures of amphiphilic ionic block copolymers: Theory, self-consistent field modeling and experiment

    NARCIS (Netherlands)

    Borisov, O.V.; Zhulina, E.B.; Leermakers, F.A.M.; Muller, A.H.E.

    2011-01-01

    We present an overview of statistical thermodynamic theories that describe the self-assembly of amphiphilic ionic/hydrophobic diblock copolymers in dilute solution. Block copolymers with both strongly and weakly dissociating (pH-sensitive) ionic blocks are considered. We focus mostly on structural

  3. Micellar Structures of Hydrophilic/Lipophilic and Hydrophilic/Fluorophilic Poly(2-oxazoline) Diblock Copolymers in Water

    DEFF Research Database (Denmark)

    Ivanova, Ruzha; Komenda, Thomas; Bonné, Tune B.

    2008-01-01

    Amphiphilic poly(2-alkyl-2-oxazoline) diblock copolymers of 2-methyl-2-oxazoline (MOx) building the hydrophilic block and either 2-nonyl-2-oxazoline (NOx) for the hydrophobic or 2-(1H,1H',2H,2H'-perfluorohexyl)-2-oxazoline (FOx) for the fluorophilic block were synthesized by sequential living cat......, as observed by SANS and TEM. In water, the micelles with fluorophilic and lipophilic cores do not mix, but coexist....

  4. 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.

  5. Polystyrene-Poly(sodium methacrylate) Amphiphilic Block Copolymers by ATRP : Effect of Structure, pH, and Ionic Strength on Rheology of Aqueous Solutions

    NARCIS (Netherlands)

    Raffa, Patrizio; Brandenburg, Piter; Wever, Diego A. Z.; Broekhuis, Antonius A.; Picchioni, Francesco

    2013-01-01

    Three well-defined polystyrene-poly(sodium methacrylate) amphiphilic block copolymers characterized by different molecular architecture (diblock, triblock, and four-arm star) have been synthesized by ATRP. The rheology of their water solutions has been evaluated by measuring dynamic moduli and shear

  6. 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.

  7. 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

  8. Self-assemblies of magnetic nanoparticles and di-block copolymers: Magnetic micelles and vesicles

    International Nuclear Information System (INIS)

    Lecommandoux, S.; Sandre, O.; Checot, F.; Rodriguez-Hernandez, J.; Perzynski, R.

    2006-01-01

    Magnetic nanocomposites are obtained by the self-assembly in water of polypeptide-based di-block copolymers polybutadiene-b-poly(glutamic acid) combined with hydrophobic γ-Fe 2 O 3 nanoparticles. These hybrid supramolecular objects are either-(3D) spherical micelles filled with a hydrophobic ferrofluid at a concentration as high as 45 vol% or-hollow vesicles with a (2D) magnetic membrane. In this last case, the organic amphiphile copolymers are able to confine the hydrophobic nanoparticles within the thin layer of polybutadiene blocks. We probe these objects by atomic force microscopy, by small-angle neutron scattering (SANS) and by light scattering. Furthermore, anisotropic SANS data bring the experimental evidence of the capability to modify the shape of the mineralized membranes in response to a magnetic field intensity as low as 290 G

  9. High-Pressure Micellar Solutions of Symmetric and Asymmetric Styrene?Diene Diblocks in Compressible Near Critical Solvents: Micellization Pressures and Cloud Pressures Respond but Micellar Cloud Pressures Insensitive to Copolymer Molecular Weight, Concentration, and Block Ratio Changes

    Energy Technology Data Exchange (ETDEWEB)

    Winoto, Winoto [University of Wyoming, Laramie; Tan, Sugata [University of Wyoming, Laramie; Shen, Youqin [University of Wyoming, Laramie; Radosz, Maciej [University of Wyoming, Laramie; Hong, Kunlun [ORNL; Mays, Jimmy [ORNL

    2009-01-01

    Micellar solutions of polystyrene-block-polybutadiene and polystyrene-block-polyisoprene in propane are found to exhibit significantly lower cloud pressures than the corresponding hypothetical nonmicellar solutions. Such a cloud-pressure reduction indicates the extent to which micelle formation enhances the apparent diblock solubility in near-critical and hence compressible propane. Concentration-dependent pressure-temperature points beyond which no micelles can be formed, referred to as the micellization end points, are found to depend on the block type, size, and ratio. The cloud-pressure reduction and the micellization end point measured for styrene-diene diblocks in propane should be characteristic of all amphiphilic diblock copolymer solutions that form micelles in compressible solvents.

  10. Morphologies of poly(cyclohexadiene) diblock copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Rajeev [ORNL; Mays, Jimmy [ORNL; Sides, Scott [ORNL; Goswami, Monojoy [ORNL; Sumpter, Bobby G [ORNL; Hong, Kunlun [ORNL; Avgeropoulos, Apostolos [University of Athens, Athens, Greece; Russell, Thomas P [ORNL; Gido, Samuel [University of Massachusetts, Amherst; Tsoukatos, Thodoris [University of Athens, Athens, Greece; Beyer, Fredrick [U.S. Army Research Laboratory, Aberdeen Proving Ground, MD

    2012-01-01

    Concerted experimental and theoretical investigations have been carried out to understand the micro-phase separation in diblock copolymer melts containing poly (1,3-cyclohexadiene), PCHD, as one of the constituents. In particular, we have studied diblock copolymer melts containing polystyrene (PS), polybutadiene (PB), and polyisoprene (PI) as the second block. We have systematically varied the ratio of 1,2- /1,4-microstructures of poly (1,3-cyclohexadiene) to tune the conformational asymmetry between the two blocks and characterized the effects of these changes on the morphologies using transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS). Our experimental investigations reveal that the melts of PCHD-b-PB, PCHD-b-PS and PCHD-b-PI containing nearly equal fractions of each component and high percentage of 1,4-microstructures in the PCHD block form cylindrical rather than lamellar morphologies as expected in symmetric diblock copolymers. In contrast, the morphologies of PCHD-b-PB, PCHD-b-PS and PCHD-b-PI containing PCHD block with higher 1,2-microstructure are found to be disordered at 110 C. The change in the morphological behavior is in good agreement with our numerical calculations using the random phase approximation and self-consistent field theory for conformationally asymmetric diblock copolymer melts. Also, the effects of composition fluctuations are studied by extending the Brazovskii-Leibler-Fredrickson-Helfand (J. Chem. Phys. 87, 697 (1987)) theory to conformationally asymmetric diblock copolymer melts. These results allow the understanding of the underlying self-assembly process that highlights the importance of the conformational asymmetry in tuning the morphologies in block copolymers.

  11. Morphology of diblock copolymers in porous media

    Czech Academy of Sciences Publication Activity Database

    Maniadis, Panagiotis; Tsimpanogiannis, I. N.; Kober, E.M.; Lookman, T.

    2014-01-01

    Roč. 112, č. 17 (2014), s. 2297-2309 ISSN 0026-8976 R&D Projects: GA MŠk(CZ) ED1.1.00/02.0068; GA MŠk(CZ) EE2.3.20.0214 Institutional support: RVO:68081723 Keywords : confinement * diblock copolymers * porous media * self-assembly * self-consistent field theory Subject RIV: BE - Theoretical Physics Impact factor: 1.720, year: 2014

  12. Comparison of complex coacervate core micelles from two diblock copolymers or a single diblock copolymer with a polyelectrolyte.

    NARCIS (Netherlands)

    Hofs, P.S.; Voets, I.K.; Keizer, de A.; Cohen Stuart, M.A.

    2006-01-01

    With light scattering titrations, we show that complex coacervate core micelles (C3Ms) form from a diblock copolymer with a polyelectrolyte block and either an oppositely charged polyelectrolyte, a diblock copolymer with an oppositely charged polyelectrolyte or a mixture of the two. The effect of

  13. Development of Fully Degradable Phosphonium-Functionalized Amphiphilic Diblock Copolymers for Nucleic Acids Delivery.

    Science.gov (United States)

    Borguet, Yannick P; Khan, Sarosh; Noel, Amandine; Gunsten, Sean P; Brody, Steven L; Elsabahy, Mahmoud; Wooley, Karen L

    2018-03-11

    To expand the range of functional polymer materials to include fully hydrolytically degradable systems that bear bioinspired phosphorus-containing linkages both along the backbone and as cationic side chain moieties for packaging and delivery of nucleic acids, phosphonium-functionalized polyphosphoester- block-poly(l-lactide) copolymers of various compositions were synthesized, fully characterized, and their self-assembly into nanoparticles were studied. First, an alkyne-functionalized polyphosphoester- block-poly(l-lactide) copolymer was synthesized via a one pot sequential ring opening polymerization of an alkyne-functionalized phospholane monomer, followed by the addition of l-lactide to grow the second block. Second, the alkynyl side groups of the polyphosphoester block were functionalized via photoinitiated thiol-yne radical addition of a phosphonium-functionalized free thiol. The polymers of varying phosphonium substitution degrees were self-assembled in aqueous buffers to afford formation of well-defined core-shell assemblies with an average size ranging between 30 and 50 nm, as determined by dynamic light scattering. Intracellular delivery of the nanoparticles and their effects on cell viability and capability at enhancing transfection efficiency of nucleic acids (e.g., siRNA) were investigated. Cell viability assays demonstrated limited toxicity of the assembly to RAW 264.7 mouse macrophages, except at high polymer concentrations, where the polymer of high degree of phosphonium functionalization induced relatively higher cytotoxicity. Transfection efficiency was strongly affected by the phosphonium-to-phosphate (P + /P - ) ratios of the polymers and siRNA, respectively. The AllStars Hs Cell Death siRNA complexed to the various copolymers at a P + /P - ratio of 10:1 induced comparable cell death to Lipofectamine. These fully degradable nanoparticles might provide biocompatible nanocarriers for therapeutic nucleic acid delivery.

  14. Preparation and morphology control of amphiphilic block copolymer thin films using mixed solvent vapors

    Energy Technology Data Exchange (ETDEWEB)

    Xie, Chan, E-mail: xiechan@pku.edu.cn [Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871 (China); School of Material Science and Engineering, Nanchang Hangkong University, Jiangxi, Nanchang, 330063 (China); Zhou, Yu; Zhou, Feng; Wu, Hongwei; Zou, Dechun; Fan, Xinghe [Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871 (China); Shen, Zhihao, E-mail: zshen@pku.edu.cn [Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871 (China)

    2014-03-01

    Graphical abstract: A series of well-defined amphiphilic block copolymer (BCP), poly[N,N-(dimethylamino)ethyl methacrylate]-block-polystyrene (PDMAEMA-b-PS), was synthesized using the ARGET ATRP method. Solvent annealing was applied for controlling the thin-film morphologies. A vertical nanocylinder structure forms in the thin film annealed under the vapors of binary mixed solvents from water and tetrahydrofuran which have a strong selectivity for the minority PDMAEMA block. - Highlights: • Well-defined amphiphilic diblock copolymers synthesized. • Systematic study on morphologies in thin films controlled by annealing under vapors of mixed solvents. - Abstract: A well-defined amphiphilic diblock copolymer, poly[N,N-(dimethylamino)ethyl methacrylate]-block-polystyrene (PDMAEMA-b-PS), was synthesized using activators regenerated by electron transfer atom transfer radical polymerization. The formation and transition of morphologies in PDMAEMA-b-PS thin films annealed under the vapors of water, tetrahydrofuran, and their binary mixed solvents were first investigated by using atomic force microscopy and scanning electron microscopy. By changing the composition of the annealing solvent, morphological evolution with increasing vapor preferential affinity was observed. A vertical nanocylinder structure forms in the PDMAEMA-b-PS thin film when it is annealed under a mixed solvent vapor with Δχ ∼ −0.975 having a strong preferential affinity for the minority PDMAEMA block at ambient temperature. The self-assembly of PDMAEMA-b-PS thin films provides a new convenient way to fabricate stimuli-responsive substrates with potential applications in adhesion control, wetting, and binding or release of functional molecules at surfaces.

  15. 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.

  16. 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.

  17. Comparative analysis of nanostructured diblock copolymer films

    International Nuclear Information System (INIS)

    Mueller-Buschbaum, P.; Hermsdorf, N.; Roth, S.V.; Wiedersich, J.; Cunis, S.; Gehrke, R.

    2004-01-01

    Nanostructured polymer films of poly(styrene-block-paramethylstyrene) diblock copolymers P(Sd-b-pMS) on silicon substrates with a native oxide layer are investigated. Resulting from a storage under toluene vapor, a surface structure is installed. The early stages, characterized by the creation of a host structure out of an initially continuous film, are addressed. Grazing incidence small-angle X-ray scattering (GISAXS) experiments were performed as a function of exposure time. Results are compared to modelling of the scattering pattern and other experimental techniques, such as grazing incidence small-angle neutron scattering (GISANS) and atomic force microscopy (AFM) data. Possibilities and limits of the techniques are discussed

  18. 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......(styrene)-b-poly(methacrylic acid) PS-b-PMAA multi-tail ammonium side-chains of (C8)2-, (C8)4- or (C12)2-type were attached at various side-chain grafting densities (X), making it possible to separate effects of the details of the AC-block architecture from effects of the overall volume fraction of the AC block. The micro...

  19. Neutron reflectivity study of adsorbed diblock copolymers

    International Nuclear Information System (INIS)

    Smith, G.S.; Baker, S.M.; Wages, S.; Hamilton, W.; Toprakcioglu, C.; Field, J.B.; Dai, L.

    1994-01-01

    This paper summarizes our cumulative work on neutron reflectivity studies of polystyrene-poly(vinyl-2-pyridine) (PS-PVP) and polystyrenepolyethylene oxide (PS-PEO) adsorbed at a quartz-solvent interface. Deuterated toluene was chosen as the solvent since it is a good solvent for PS and a poor one for either of the other two blocks. In this case, the polystyrene dangles into the solvent while the other block acts as an anchor. The neutron reflectivity studies reveal that the form of the polymer density profile normal to the substrate may be varied from an extended ''brush'' to a condensed ''mushroom'' conformation by manipulating the ratio of the molecular weights of the two blocks. In addition, we present new data on the PS-PEO system in a poor solvent, deuterated cyclohexane, under conditions of shear flow in Poiseuille geometry. We find that when the PS-PEO diblock is absorbed from cyclohexane and is allowed to relax, the PS chain takes on a ''mushroom'' conformation. However, when the shear is applied, the layer shear thickens due to the PS chains extended to nearly twice their original lengths

  20. Formation of nanoscale networks: selectively swelling amphiphilic block copolymers with CO2-expanded liquids.

    Science.gov (United States)

    Gong, Jianliang; Zhang, Aijuan; Bai, Hua; Zhang, Qingkun; Du, Can; Li, Lei; Hong, Yanzhen; Li, Jun

    2013-02-07

    Polymeric films with nanoscale networks were prepared by selectively swelling an amphiphilic diblock copolymer, polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP), with the CO(2)-expanded liquid (CXL), CO(2)-methanol. The phase behavior of the CO(2)-methanol system was investigated by both theoretical calculation and experiments, revealing that methanol can be expanded by CO(2), forming homogeneous CXL under the experimental conditions. When treated with the CO(2)-methanol system, the spin cast compact PS-b-P4VP film was transformed into a network with interconnected pores, in a pressure range of 12-20 MPa and a temperature range of 45-60 °C. The formation mechanism of the network, involving plasticization of PS and selective swelling of P4VP, was proposed. Because the diblock copolymer diffusion process is controlled by the activated hopping of individual block copolymer chains with the thermodynamic barrier for moving PVP segments from one to another, the formation of the network structures is achieved in a short time scale and shows "thermodynamically restricted" character. Furthermore, the resulting polymer networks were employed as templates, for the preparation of polypyrrole networks, by an electrochemical polymerization process. The prepared porous polypyrrole film was used to fabricate a chemoresistor-type gas sensor which showed high sensitivity towards ammonia.

  1. Amphiphilic block copolymer/poly(dimethylsiloxane) (PDMS) blends and nanocomposites for improved fouling-release.

    Science.gov (United States)

    Martinelli, Elisa; Suffredini, Marianna; Galli, Giancarlo; Glisenti, Antonella; Pettitt, Michala E; Callow, Maureen E; Callow, James A; Williams, David; Lyall, Graeme

    2011-05-01

    Amphiphilic diblock copolymers, Sz6 and Sz12, consisting of a poly(dimethylsiloxane) block (average degree of polymerisation = 132) and a PEGylated-fluoroalkyl modified polystyrene block (Sz, average degree of polymerisation = 6, 12) were prepared by atom transfer radical polymerization (ATRP). Coatings were obtained from blends of either block copolymer (1-10 wt%) with a poly(dimethylsiloxane) (PDMS) matrix. The coating surface presented a simultaneous hydrophobic and lipophobic character, owing to the strong surface segregation of the lowest surface energy fluoroalkyl chains of the block copolymer. Surface chemical composition and wettability of the films were affected by exposure to water. Block copolymer Sz6 was also blended with PDMS and a 0.1 wt% amount of multiwall carbon nanotubes (CNT). The excellent fouling-release (FR) properties of these new coatings against the macroalga Ulva linza essentially resulted from the inclusion of the amphiphilic block copolymer, while the addition of CNT did not appear to improve the FR properties.

  2. Pressure and temperature effects in homopolymer blends and diblock copolymers

    DEFF Research Database (Denmark)

    Frielinghaus, H.; Schwahn, D.; Mortensen, K.

    1997-01-01

    Thermal composition fluctuations in homopolymer mer blends and diblock copolymers were studied with SANS in varying pressure and temperature fields. For homopolymers we find a quite consistent behavior: The dominating effect of compressibility or packing leads to a reduction of the entropic...

  3. Relaxation processes in a lower disorder order transition diblock copolymer

    International Nuclear Information System (INIS)

    Sanz, Alejandro; Ezquerra, Tiberio A.; Nogales, Aurora; Hernández, Rebeca; Sprung, Michael

    2015-01-01

    The dynamics of lower disorder-order temperature diblock copolymer leading to phase separation has been observed by X ray photon correlation spectroscopy. Two different modes have been characterized. A non-diffusive mode appears at temperatures below the disorder to order transition, which can be associated to compositional fluctuations, that becomes slower as the interaction parameter increases, in a similar way to the one observed for diblock copolymers exhibiting phase separation upon cooling. At temperatures above the disorder to order transition T ODT , the dynamics becomes diffusive, indicating that after phase separation in Lower Disorder-Order Transition (LDOT) diblock copolymers, the diffusion of chain segments across the interface is the governing dynamics. As the segregation is stronger, the diffusive process becomes slower. Both observed modes have been predicted by the theory describing upper order-disorder transition systems, assuming incompressibility. However, the present results indicate that the existence of these two modes is more universal as they are present also in compressible diblock copolymers exhibiting a lower disorder-order transition. No such a theory describing the dynamics in LDOT block copolymers is available, and these experimental results may offer some hints to understanding the dynamics in these systems. The dynamics has also been studied in the ordered state, and for the present system, the non-diffusive mode disappears and only a diffusive mode is observed. This mode is related to the transport of segment in the interphase, due to the weak segregation on this system

  4. Self-Assembly of Globular Protein-Polymer Diblock Copolymers

    Science.gov (United States)

    Thomas, C. S.; Olsen, B. D.

    2011-03-01

    The self-assembly of globular protein-polymer diblock copolymers into nanostructured phases is demonstrated as an elegant and simple method for structural control in biocatalysis or bioelectronics. In order to fundamentally investigate self-assembly in these complex block copolymer systems, a red fluorescent protein was expressed in E. coli and site-specifically conjugated to a low polydispersity poly(N-isopropyl acrylamide) (PNIPAM) block using thiol-maleimide coupling to form a well-defined model globular protein-polymer diblock. Functional protein materials are obtained by solvent evaporation and solvent annealing above and below the lower critical solution temperature of PNIPAM in order to access different pathways toward self-assembly. Small angle x-ray scattering and microscopy are used to show that the diblock forms lamellar nanostructures and to explore dependence of nanostructure formation on processing conditions. Circular dichroism and UV-vis show that a large fraction of the protein remains in its folded state after conjugation, and wide angle x-ray scattering demonstrates that diblock copolymer self-assembly changes the protein packing symmetry.

  5. Relaxation processes in a lower disorder order transition diblock copolymer

    Energy Technology Data Exchange (ETDEWEB)

    Sanz, Alejandro; Ezquerra, Tiberio A.; Nogales, Aurora, E-mail: aurora.nogales@csic.es [Instituto de Estructura de la Materia, IEM-CSIC. C/ Serrano 121, Madrid 28006 (Spain); Hernández, Rebeca [Instituto de Ciencia y Tecnología de Polímeros, ICTP-CSIC. C/ Juan de la Cierva 3, Madrid 28006 (Spain); Sprung, Michael [Petra III at DESY, Notkestr. 85, 22607 Hamburg (Germany)

    2015-02-14

    The dynamics of lower disorder-order temperature diblock copolymer leading to phase separation has been observed by X ray photon correlation spectroscopy. Two different modes have been characterized. A non-diffusive mode appears at temperatures below the disorder to order transition, which can be associated to compositional fluctuations, that becomes slower as the interaction parameter increases, in a similar way to the one observed for diblock copolymers exhibiting phase separation upon cooling. At temperatures above the disorder to order transition T{sub ODT}, the dynamics becomes diffusive, indicating that after phase separation in Lower Disorder-Order Transition (LDOT) diblock copolymers, the diffusion of chain segments across the interface is the governing dynamics. As the segregation is stronger, the diffusive process becomes slower. Both observed modes have been predicted by the theory describing upper order-disorder transition systems, assuming incompressibility. However, the present results indicate that the existence of these two modes is more universal as they are present also in compressible diblock copolymers exhibiting a lower disorder-order transition. No such a theory describing the dynamics in LDOT block copolymers is available, and these experimental results may offer some hints to understanding the dynamics in these systems. The dynamics has also been studied in the ordered state, and for the present system, the non-diffusive mode disappears and only a diffusive mode is observed. This mode is related to the transport of segment in the interphase, due to the weak segregation on this system.

  6. Morphology diagram of a diblock copolymer - aluminosilicate nanoparticle system

    NARCIS (Netherlands)

    Garcia, B.C.; Kamperman, M.M.G.; Ulrich, R.; Jain, A.; Gruner, S.M.; Wiesner, U.

    2009-01-01

    We explore the morphology space of nanocomposites prepared from poly(isoprene-block-ethylene oxide) (PI-b-PEO) diblock copolymers as structure directing agents for aluminosilicate nanoparticles prepared from (3-glycidyloxypropyl)trimethoxysilane (GLYMO) and aluminum(III) sec-butoxide. The results of

  7. Tough, semiconducting polyethylene-poly(3-hexylthiophene) diblock copolymers

    DEFF Research Database (Denmark)

    Müller, C.; Goffri, S.; Breiby, Dag Werner

    2007-01-01

    Semiconducting diblock copolymers of polyethylene (PE) and regioregular poly(3-hexylthiophene) (P3HT) are demonstrated to exhibit a rich phase behaviour, judicious use of which permitted us to fabricate field-effect transistors that show saturated charge carrier mobilities, mu(FET), as high as 2 x...

  8. 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.

  9. Morphological transformations of diblock copolymers in binary solvents: A simulation study

    Science.gov (United States)

    Wang, Zheng; Yin, Yuhua; Jiang, Run; Li, Baohui

    2017-12-01

    Morphological transformations of amphiphilic AB diblock copolymers in mixtures of a common solvent (S1) and a selective solvent (S2) for the B block are studied using the simulated annealing method. We focus on the morphological transformation depending on the fraction of the selective solvent C S2, the concentration of the polymer C p , and the polymer-solvent interactions ɛ ij ( i = A, B; j = S1, S2). Morphology diagrams are constructed as functions of C p , C S2, and/or ɛ AS2. The copolymer morphological sequence from dissolved → sphere → rod → ring/cage → vesicle is obtained upon increasing C S2 at a fixed C p . This morphology sequence is consistent with previous experimental observations. It is found that the selectivity of the selective solvent affects the self-assembled microstructure significantly. In particular, when the interaction ɛ BS2 is negative, aggregates of stacked lamellae dominate the diagram. The mechanisms of aggregate transformation and the formation of stacked lamellar aggregates are discussed by analyzing variations of the average contact numbers of the A or B monomers with monomers and with molecules of the two types of solvent, as well as the mean square end-to-end distances of chains. It is found that the basic morphological sequence of spheres to rods to vesicles and the stacked lamellar aggregates result from competition between the interfacial energy and the chain conformational entropy. Analysis of the vesicle structure reveals that the vesicle size increases with increasing C p or with decreasing C S2, but remains almost unchanged with variations in ɛ AS2.

  10. PEO-based brush-type amphiphilic macro-RAFT agents and their assembled polyHIPE monolithic structures for applications in separation science.

    Science.gov (United States)

    Khodabandeh, Aminreza; Arrua, R Dario; Mansour, Fotouh R; Thickett, Stuart C; Hilder, Emily F

    2017-08-10

    Polymerized High Internal Phase Emulsions (PolyHIPEs) were prepared using emulsion-templating, stabilized by an amphiphilic diblock copolymer prepared by reversible addition fragmentation chain transfer (RAFT) polymerization. The diblock copolymer consisted of a hydrophilic poly(ethylene glycol) methyl ether acrylate (PEO MA, average Mn 480) segment and a hydrophobic styrene segment, with a trithiocarbonate end-group. These diblock copolymers were the sole emulsifiers used in stabilizing "inverse" (oil-in-water) high internal phase emulsion templates, which upon polymerization resulted in a polyHIPE exhibiting a highly interconnected monolithic structure. The polyHIPEs were characterized by FTIR spectroscopy, BET surface area measurements, SEM, SEM-EDX, and TGA. These materials were subsequently investigated as stationary phase for high-performance liquid chromatography (HPLC) via in situ polymerization in a capillary format as a 'column housing'. Initial separation assessments in reversed-phase (RP) and hydrophilic interaction liquid chromatographic (HILIC) modes have shown that these polyHIPEs are decorated with different microenvironments amongst the voids or domains of the monolithic structure. Chromatographic results suggested the existence of RP/HILIC mixed mode with promising performance for the separation of small molecules.

  11. Synthesis and characterization of diblock copolymer templated iron oxide nanoparticles

    Science.gov (United States)

    Akcora, Pinar

    2005-07-01

    Templating ordered assemblies of magnetic oxide nanoparticles within self-assembled diblock copolymers of varying morphologies is an important problem with a wide applicability such as in electromagnetics, optical devices, metal catalysts, medicine and biology. In this thesis, the effects of different polymer structures on particle ordering and resultant magnetic properties have been investigated using various microstructure and magnetic characterization tools. Ring-opening metathesis polymerization (ROMP) of norbornene and functionalized norbornene monomers has been used to synthesize diblock copolymers of narrow polydispersities using Grubbs' catalyst. These block copolymers can be used as templates to form inorganic nanoparticles. In this research, the structural and physical understanding of the inorganic-copolymer system was studied by small-angle neutron and x-ray scattering techniques and transmission electron microscopy. Synthesis of gamma-Fe2O3 nanoparticles has been achieved within novel block copolymers of (norbornene)-b-(deuterated norbornene dicarboxylic) acid and (norbornene methanol-(norbornene dicarboxylic acid). The polymer morphologies were controlled by varying the volume fractions of the constituent blocks. The pure norbornene based diblock copolymer morphologies were demonstrated by electron microscopy for the first tune. Spherical, cylindrical and lamellar morphologies of these novel diblock copolymers were reported. The block ratios of the synthesized polymers were determined using gel permeation chromatography-light scattering, elemental analysis and UV-VIS spectroscopy. Solution phase doping and submersion of thin films in metal salt solutions were employed as metal doping methods and the observed nanoparticle structures were compared to those of the undoped copolymer morphologies. This project reports on the types of templating structures and dispersion of the nanoparticles. The effects of particle, interactions on the microphase

  12. 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).

  13. Hydrophobic, Hydrophilic, and Amphiphilic Polyglycocarbonates with Linear and Macrocyclic Architectures from Bicyclic Glycocarbonates Derived from CO2 and Glucoside

    KAUST Repository

    Pati, Debasis

    2017-02-09

    Two bicyclic glycocarbonates were synthesized in five steps from α-methyl-d-glucoside without resorting to phosgene or to its derivatives for the first time. The 4- and 6-positions of glucose were modified to introduce a six-membered carbonate ring, using CO as the carbonylating reagent; the 2- and 3-positions of the same glucoside substrate were first transformed into either methyl or triethylene glycol monomethyl ether groups to protect these positions from undesirable reactions and also to impart hydrophobicity in the first case and hydrophilicity in the second. The polymerization behavior of these bicyclic glycocarbonates was then investigated under different conditions. On the one hand, through ring-opening polymerization of the above monomers, linear polyglycocarbonate homopolymers and diblock copolymers were obtained initiated by p-methylbenzyl alcohol using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as catalyst; on the other hand, macrocyclic polyglycocarbonate homopolymers and diblock copolymers were grown using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) which served as zwitterionic initiator. The various architectures derived were all thoroughly characterized by NMR, GPC, and MALDI-tof and shown to exhibit the expected structure. Finally, the self-assembly of linear and macrocyclic amphiphilic copolyglycocarbonates in water was investigated and characterized by cryo-TEM.

  14. Construction Of Micro- And Nanoporous Hydrogels Via Designed Diblock Copolypeptide Self-Assembly And Oligopeptide Self-Assembly

    Science.gov (United States)

    Pochan, Darrin; Deming, Tim; Schneider, Joel

    2002-03-01

    The design, synthesis, and self-assembly of polypeptides as synthetic materials that possess the ability to aggregate and/or “fold” into specifically defined, a priori designed, functional nanostructures is being pursued via two avenues. First, synthetic block copolypeptides will be discussed that are observed to form novel hydrogels with structural and biological properties tailorable by the choice of amino acid (and consequent secondary structure) in the respective blocks. Specifically ionic, amphiphilic diblocks have been designed for tissue engineering hydrogels on assembly in aqueous solution. A bicontinuous morphology is observed at both the nanoscale and microscale. Second, de novo designed oligopeptides that undergo specific folding events triggered by pH, preceding or concurrent with self-assembly, will be discussed. Specifically, the ability of small (20 amino acid residues) molecules to produce relatively very large (approximately 100 micron diameter) spheres and tubes in additino to hydrogels via a hierarchical self-assembly process will be discussed. The assembled oligopeptides have the added design attribute of being responsive to pH, unfolding/disassembling at pH below 6. Both classes of peptide-based self-assembled materials were characterized via laser scanning confocal and cryotransmission electron microscopy combined with small angle neutron and x-ray scattering.

  15. Synthesis of amphiphilic diblock copolymer brushes by successive RAFT polymerization of lauryl methacrylate and PEO-containing macromonomer

    Czech Academy of Sciences Publication Activity Database

    Krivorotova, T.; Udrenaite, E.; Gromadzki, Daniel; Makuška, R.

    2010-01-01

    Roč. 21, č. 1 (2010), s. 63-71 ISSN 0235-7216 Institutional research plan: CEZ:AV0Z40500505 Keywords : RAFT * macromonomer * PEO Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.677, year: 2010 http://www.lmaleidykla.lt/publ/0235-7216/2010/1/63-71.pdf

  16. Influence of diblock copolymer on the morphology and properties of polystyrene/poly(dimethylsiloxane) blends

    DEFF Research Database (Denmark)

    Chuai, Chengzhi; Li, Shu; Almdal, Kristoffer

    2004-01-01

    , the observed morphology of the melt-blended PS/PDMS pair unambiguously supported the interfacial activity of the diblock copolymers. When a few percent of the diblock copolymers blended together with the PS and PDMS homopolymers, the phase size was reduced and the phase dispersion was firmly stabilized against...

  17. Peptide amphiphile self-assembly

    Science.gov (United States)

    Iscen, Aysenur; Schatz, George C.

    2017-08-01

    Self-assembly is a process whereby molecules organize into structures with hierarchical order and complexity, often leading to functional materials. Biomolecules such as peptides, lipids and DNA are frequently involved in self-assembly, and this leads to materials of interest for a wide variety of applications in biomedicine, photonics, electronics, mechanics, etc. The diversity of structures and functions that can be produced provides motivation for developing theoretical models that can be used for a molecular-level description of these materials. Here we overview recently developed computational methods for modeling the self-assembly of peptide amphiphiles (PA) into supramolecular structures that form cylindrical nanoscale fibers using molecular-dynamics simulations. Both all-atom and coarse-grained force field methods are described, and we emphasize how these calculations contribute insight into fiber structure, including the importance of β-sheet formation. We show that the temperature at which self-assembly takes place affects the conformations of PA chains, resulting in cylindrical nanofibers with higher β-sheet content as temperature increases. We also present a new high-density PA model that shows long network formation of β-sheets along the long axis of the fiber, a result that correlates with some experiments. The β-sheet network is mostly helical in nature which helps to maintain strong interactions between the PAs both radially and longitudinally. Contribution to Focus Issue Self-assemblies of Inorganic and Organic Nanomaterials edited by Marie-Paule Pileni.

  18. Lattice Models of Amphiphile and Solvent Mixtures.

    Science.gov (United States)

    Brindle, David

    Available from UMI in association with The British Library. Materials based on amphiphilic molecules have a wide range of industrial applications and are of fundamental importance in the structure of many biological systems. Their importance derives from their behaviour as surface-active agents in solubilization applications and because of their ability to form systems with varying degrees of structural order such as micelles, bilayers and liquid crystal phases. The nature of the molecular ordering is of importance both during the processing of these materials and in their final application. A Monte Carlo simulation of a three dimensional lattice model of an amphiphile and solvent mixture has been developed as an extension of earlier work in two dimensions. In the earlier investigation the simulation was carried out with three segment amphiphiles on a two dimensional lattice and cluster size distributions were determined for a range of temperatures, amphiphile concentrations and intermolecular interaction energies. In the current work, a wider range of structures are observed including micelles, bilayers and a vesicle. The structures are studied as a function of temperature, chain length, amphiphile concentration and intermolecular interaction energies. Clusters are characterised according to their shape, size and surface roughness. A detailed temperature -concentration phase diagram is presented for a system with four segment amphiphiles. The phase diagram shows a critical micelle concentration (c.m.c.) at low amphiphile concentrations and a transition from a bicontinuous to lamellar region at amphiphile concentrations around 50%. At high amphiphile concentrations, there is some evidence for the formation of a gel. The results obtained question the validity of current models of the c.m.c. The Monte Carlo simulations require extensive computing power and the simulation was carried out on a transputer array, where the parallel architecture allows high speed. The

  19. 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

    By a selective complexation between different alkyltrimethylammonium amphiphiles (C8, C12 and C16) and three different diblock copolymer systems of poly(styrene)-b-poly(methacrylic acid) at various grafting densities X (X = number of alkyl chains per acidic group of the poly(methacrylic acid) PMAA...... 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...... show simultaneous microphase (between Linear and AmphComb blocks) and nanophase (within the AmphComb blocks) separations. This leads to the formation of various structure-in-structure two-scale hierarchical self-assemblies, including S-in-SLL, S-in-SBCC, S-in-C, S-in-L and C-in-L, where S, SLL, SBCC, C...

  20. 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

  1. Fabrication of platinum nanoparticles in aqueous solution and solid phase using amphiphilic PB-b-PEO copolymer nanoreactors

    Energy Technology Data Exchange (ETDEWEB)

    Hoda, Numan, E-mail: nhoda@akdeniz.edu.tr [Department of Chemistry, Faculty of Sciences, Akdeniz University, 07058 Antalya (Turkey); Budama, Leyla; Çakır, Burçin Acar; Topel, Önder [Department of Chemistry, Faculty of Sciences, Akdeniz University, 07058 Antalya (Turkey); Ozisik, Rahmi [Department of Materials Science and Engineering and Renssleaer Nanotechnology Center, Rensselaer Polytechnic Institute, Troy, NY 12180 (United States)

    2013-09-01

    Graphical abstract: TEM image of Pt nanoparticles produced by reducing by NaBH{sub 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.

  2. Unexpected phase behavior of an asymmetric diblock copolymer

    DEFF Research Database (Denmark)

    Papadakis, Christine Maria; Almdal, Kristoffer; Mortensen, Kell

    1999-01-01

    We report on measurements of the transmitted depolarized light intensity and on small-angle neutron scattering (SANS) measurements on a compositionally asymmetric poly(ethylene propylene)-poly(dimethylsiloxane) diblock copolymer studied in the bulk. SANS measurements were made both on isotropic...... and on shear oriented samples. Apart from the disordered phase, three different ordered morphologies were identified as a function of temperature: the body-centered cubic structure at the lowest temperature, a noncubic, slightly birefringent intermediate phase, and a cubic high-temperature structure which may...

  3. Predicting inhomogeneous water absorption in an ionic diblock polymer membrane

    Science.gov (United States)

    Herbst, Daniel; Witten, Thomas

    2013-03-01

    Fuel cells convert fuel directly into electrical power. Their performance depends on a permeable (yet strong) membrane to allow ion conduction (while preventing combustion). Anion-exchange membrane fuel-cells are especially economical to produce, but technological hurdles currently limit durability and OH- conductivity of the membrane. One solution to these problems is a diblock morphology. Layers of stiff hydrophobic polymer provide structure, while interspersed layers of polyelectrolyte provide avenues for conduction. Previously, little was known about the structure within the conducting layer. We adapted Scheutjens-Fleer polymer-brush theory to a lamellar geometry. The calculation tells where the polyelectrolytes congregate within a lamella, and hence how conduction occurs. This talk focuses on a new diblock material, PMB-PVBTMA. We show how the features of the material determine the intra-lamellar structure. We conclude that at low humidity, the bulkiness of PVBTMA causes it to adopt a near-uniform distribution within the conducting block. At high humidity, however, a phase separation may induce abrupt water channels. Understanding the architecture within the conducting layer will help guide research into better anion-exchange membranes materials. The authors would like to thank the Army Research Office for support of this research under the MURI #W911NF-10-1-0520.

  4. Polymer Semiflexibility Induces Nonuniversal Phase Transitions in Diblock Copolymers

    Science.gov (United States)

    Mao, Shifan; MacPherson, Quinn; Spakowitz, Andrew J.

    2018-02-01

    The order-disorder phase transition and the associated phase diagrams of semiflexible diblock copolymers are investigated using the wormlike chain model, incorporating concentration fluctuations. The free energy up to quartic order in concentration fluctuations is developed with chain-rigidity-dependent coefficients, evaluated using our exact results for the wormlike chain model, and a one-loop renormalization treatment is used to account for fluctuation effects. The chain length N and the monomer aspect ratio α directly control the strength of immiscibility (defined by the Flory-Huggins parameter χ ) at the order-disorder transition and the resulting microstructures at different chemical compositions fA. When monomers are infinitely thin (i.e., large aspect ratio α ), the finite chain length N lowers the χ N at the phase transition. However, fluctuation effects become important when chains have a finite radius, and a decrease in the chain length N elevates the χ N at the phase transition. Phase diagrams of diblock copolymers over a wide range of N and α are calculated based on our fluctuation theory. We find that both finite N and α enhance the stability of the lamellar phase above the order-disorder transition. Our results demonstrate that polymer semiflexibility plays a dramatic role in the phase behavior, even for large chain lengths (e.g., N ≈100 ).

  5. 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.

  6. Bola-amphiphile self-assembly

    DEFF Research Database (Denmark)

    Svaneborg, Carsten

    2012-01-01

    Bola-amphiphiles are rod-like molecules where both ends of the molecule likes contact with water, while the central part of the molecule dislikes contact with water. What do such molecules do when they are dissolved in water? They self-assemble into micelles. This is a Dissipartive particle...

  7. Fluctuations and structure of amphiphilic films

    International Nuclear Information System (INIS)

    Gourier, CH.

    1996-01-01

    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.)

  8. Amphiphilic copolymers for fouling-release coatings

    DEFF Research Database (Denmark)

    Noguer, Albert Camós; Olsen, Stefan Møller; Hvilsted, Søren

    of the coatings [9,10,11]. This work shows the effect of an amphiphilic copolymer that induces hydrophilicity on the surface of the silicone-based fouling release coatings. The behaviour of these copolymers within the coating upon immersion and the interaction of these surface-active additives with other...

  9. Structure and dynamics of diblock copolymers in selective incompatible solvents

    Science.gov (United States)

    Stepanek, Petr

    2004-03-01

    When a diblock copolymer A-B is dissolved in a partially miscible mixture of two solvents, where one solvent is selective for block A and the other solvent is selective for block B, periodic multilayered anisotropic nanostructures are formed consisting of periodically arranged domains of the two solvents, stabilized by the block copolymer. We studied diblock copolymers where one block is polystyrene and the second is a polydiene or aliphatic chain, in mixtures of dimethylformamide (DMF), a selectively good solvent for polystyrene, and cyclohexane, a selectively good solvent for the other block. The coexistence curve of the solvent mixture has an upper critical temperature at 48 ^oC. We found that the copolymers formed macroscopically homogeneous, ordered or disordered solutions in a wide range of solvent compositions (2-40 concentrations (up to 20 We have investigated these systems using small angle neutron scattering, dynamic light scattering and pulsed-field gradient NMR. Depending on the composition of the mixed solvent the ordered phases formed below the coexistence curve of the neat solvents had a hexagonal or cubic structure. For selected systems validity of dilution laws has been examined. Analysis of the scattered intensity at large wave vectors q shows that the chains at the interface of the two solvents are not stretched. The dynamics of the ordered systems can be followed over 10 orders of magnitude and include these processes: solvent diffusion, internal relaxations, cooperative diffusion, self-diffusion, and viscoelastic relaxation. We acknowledge support of the Grant Agency of the Czech Republic (203/01/536).

  10. Formulation of Diblock Polymeric Nanoparticles through Nanoprecipitation Technique

    Science.gov (United States)

    Karve, Shrirang; Werner, Michael E.; Cummings, Natalie D.; Sukumar, Rohit; Wang, Edina C.; Zhang, Ying-Ao; Wang, Andrew Z.

    2011-01-01

    Nanotechnology is a relatively new branch of science that involves harnessing the unique properties of particles that are nanometers in scale (nanoparticles). Nanoparticles can be engineered in a precise fashion where their size, composition and surface chemistry can be carefully controlled. This enables unprecedented freedom to modify some of the fundamental properties of their cargo, such as solubility, diffusivity, biodistribution, release characteristics and immunogenicity. Since their inception, nanoparticles have been utilized in many areas of science and medicine, including drug delivery, imaging, and cell biology1-4. However, it has not been fully utilized outside of "nanotechnology laboratories" due to perceived technical barrier. In this article, we describe a simple method to synthesize a polymer based nanoparticle platform that has a wide range of potential applications. The first step is to synthesize a diblock co-polymer that has both a hydrophobic domain and hydrophilic domain. Using PLGA and PEG as model polymers, we described a conjugation reaction using EDC/NHS chemistry5 (Fig 1). We also discuss the polymer purification process. The synthesized diblock co-polymer can self-assemble into nanoparticles in the nanoprecipitation process through hydrophobic-hydrophilic interactions. The described polymer nanoparticle is very versatile. The hydrophobic core of the nanoparticle can be utilized to carry poorly soluble drugs for drug delivery experiments6. Furthermore, the nanoparticles can overcome the problem of toxic solvents for poorly soluble molecular biology reagents, such as wortmannin, which requires a solvent like DMSO. However, DMSO can be toxic to cells and interfere with the experiment. These poorly soluble drugs and reagents can be effectively delivered using polymer nanoparticles with minimal toxicity. Polymer nanoparticles can also be loaded with fluorescent dye and utilized for intracellular trafficking studies. Lastly, these polymer

  11. 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.

  12. Cellular recognition of synthetic peptide amphiphiles in supported bioartificial membranes

    Science.gov (United States)

    Pakalns, Teika

    The goal of this study was to demonstrate that lipidated cell adhesion peptides could form well-ordered biomimetic surfaces that were capable of influencing cellular behavior in a controlled and specific manner. The first step taken was to covalently link synthetic dialkyl tails to the amino-termini of the collagen-derived peptide IV-H1 (amino acid sequence GVKGDKGNPGWPGAP) and the well-known tripeptide Arg-Gly-Asp (RGD) to produce amino-coupled peptide amphiphiles. Other spatial orientations of RGD were also generated by coupling tails to the carboxyl-terminus to give carboxyl-coupled RGD amphiphiles and to both the amino- and carboxyl-termini to give looped RGD amphiphiles. The next step taken was to let the peptide amphiphile self-assemble along with methyl ester-capped dialkyl tails into mixed films. It was found that all the peptide amphiphiles formed stable monolayers at the air-water interface in a Langmuir trough. IV-H1 amphiphiles and carboxyl-coupled and looped RGD amphiphiles deposited well as Langmuir-Blodgett mixed films on solid surfaces at all peptide concentrations, but aminocoupled RGD amphiphiles did not deposit well at high RGD concentrations. FT-IR studies of films containing RGD amphiphiles showed that amino-coupled RGD head groups formed the strongest lateral hydrogen bonds. The final step was to study cellular response to mixed films containing IV-H1 or RGD amphiphiles. The spreading of melanoma cells was influenced by both the molar concentration and spatial orientation of the amphiphilic peptides. Cells spread on IV-H1 and looped RGD films in a concentration-dependent manner, but spread indiscriminately on carboxyl-coupled RGD films and did not spread at all on well-deposited amino-coupled RGD films. The specificity of the cellular response to looped RGD amphiphiles was investigated. Control films of looped Arg-Gly-Glu (RGE) amphiphiles inhibited the adhesion and spreading of melanoma and endothelial cells, and antibody inhibition of the

  13. 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.)

  14. Diblock Copolymer/Layered Silicate Nanocomposite Thin Film Stability

    Science.gov (United States)

    Limary, Ratchana; Green, Peter

    2000-03-01

    The stability of thin film symmetric diblock copolymers blended with layered silicate nanocomposites were examined using a combination of optical microscopy, atomic force microscopy (AFM), and X-ray diffraction (XRD). Two cases were examined PS-b-PMMA (polystyrene-b-polymethylacrylate) blended with montmorillonite stoichiometrically loaded with alkyl ammonium ions, OLS(S), and PS-b-PMMA blended with montmorillonite loaded with excess alkyl ammonium ions, OLS(E). XRD spectra show an increase in the gallery spacing of the OLSs, indicating that the copolymer chains have intercalated the layered silicates. AFM images reveal a distinct difference between the two nanocomposite thin films: regions in the vicinity of OLS(S) aggregates were depleted of material, while in the vicinity of OLS(E) aggregates, dewetting of the substrate occurred. We show that the stability of the copolymer/OLS nanocomposite films is determined by the enthalpic driving force associated with intercalation of the copolymer chains into the galleries of the modified OLS layers and by the substrate/organic modifier interactions.

  15. Structural study of symmetric diblock copolymer thin films

    DEFF Research Database (Denmark)

    Gadegaard, Nikolaj

    2000-01-01

    Thin diblock copolymer film have been investigated by x-ray and neutron reflectivity as well as small angle x-ray and neutron scattering. Two model systems have been investigated. PS-PDMS (25 kg/mol-25 kg/mol), which has a glass transition temperature ofca. 100 deg.C for the PS-block. This means...... that the structure can be frozen below that temperature, thus the development of the lamella structure may be follow by reflectivity. It was, however, not possible to reach the expected equilibrium structure. Hence the second model system, deuterateted PEP-PDMS (4.4 kg/mol-4.4 kg/mol) was chosen for its low glass...... transition temperature -56 deg.C. This means that the system spontaneously should form lammela ordered structures at room temperature. This orderingwas studied by neutron reflectivity and small angle neutron scattering in the temperature range from -140 deg.C(below PDMS’ glass transition temperature, -127...

  16. Bionanocomposites: differential effects of cellulose nanocrystals on protein diblock copolymers.

    Science.gov (United States)

    Haghpanah, Jennifer S; Tu, Raymond; Da Silva, Sandra; Yan, Deng; Mueller, Silvana; Weder, Christoph; Foster, E Johan; Sacui, Iulia; Gilman, Jeffery W; Montclare, Jin Kim

    2013-12-09

    We investigate the effects of mixing a colloidal suspension of tunicate-derived cellulose nanocrystals (t-CNCs) with aqueous colloidal suspensions of two protein diblock copolymers, EC and CE, which bear two different self-assembling domains (SADs) derived from elastin (E) and the coiled-coil region of cartilage oligomeric matrix protein (C). The resulting aqueous mixtures reveal improved mechanical integrity for the CE+t-CNC mixture, which exhibits an elastic gel network. This is in contrast to EC+t-CNC, which does not form a gel, indicating that block orientation influences the ability to interact with t-CNCs. Surface analysis and interfacial characterization indicate that the differential mechanical properties of the two samples are due to the prevalent display of the E domain by CE, which interacts more with t-CNCs leading to a stronger network with t-CNCs. On the other hand, EC, which is predominantly C-rich on its surface, does not interact as much with t-CNCs. This suggests that the surface characteristics of the protein polymers, due to folding and self-assembly, are important factors for the interactions with t-CNCs, and a significant influence on the overall mechanical properties. These results have interesting implications for the understanding of cellulose hydrophobic interactions, natural biomaterials and the development of artificially assembled bionanocomposites.

  17. Novel Tripod Amphiphiles for Membrane Protein Analysis

    DEFF Research Database (Denmark)

    Chae, Pil Seok; Kruse, Andrew C; Gotfryd, Kamil

    2013-01-01

    . The use of a detergent or other amphipathic agents is required to overcome the intrinsic incompatibility between the large lipophilic surfaces displayed by the membrane proteins in their native forms and the polar solvent molecules. Here, we introduce new tripod amphiphiles displaying favourable......Integral membrane proteins play central roles in controlling the flow of information and molecules across membranes. Our understanding of membrane protein structures and functions, however, is seriously limited, mainly due to difficulties in handling and analysing these proteins in aqueous solution...

  18. 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.

  19. Shear Alignment of Diblock Copolymers for Patterning Nanowire Meshes

    Energy Technology Data Exchange (ETDEWEB)

    Gustafson, Kyle T. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2016-09-08

    Metallic nanowire meshes are useful as cheap, flexible alternatives to indium tin oxide – an expensive, brittle material used in transparent conductive electrodes. We have fabricated nanowire meshes over areas up to 2.5 cm2 by: 1) mechanically aligning parallel rows of diblock copolymer (diBCP) microdomains; 2) selectively infiltrating those domains with metallic ions; 3) etching away the diBCP template; 4) sintering to reduce ions to metal nanowires; and, 5) repeating steps 1 – 4 on the same sample at a 90° offset. We aligned parallel rows of polystyrene-b-poly(2-vinylpyridine) [PS(48.5 kDa)-b-P2VP(14.5 kDa)] microdomains by heating above its glass transition temperature (Tg ≈ 100°C), applying mechanical shear pressure (33 kPa) and normal force (13.7 N), and cooling below Tg. DiBCP samples were submerged in aqueous solutions of metallic ions (15 – 40 mM ions; 0.1 – 0.5 M HCl) for 30 – 90 minutes, which coordinate to nitrogen in P2VP. Subsequent ozone-etching and sintering steps yielded parallel nanowires. We aimed to optimize alignment parameters (e.g. shear and normal pressures, alignment duration, and PDMS thickness) to improve the quality, reproducibility, and scalability of meshes. We also investigated metals other than Pt and Au that may be patterned using this technique (Cu, Ag).

  20. Crystallization in diblock copolymer thin films at different degrees of supercooling

    DEFF Research Database (Denmark)

    Darko, C.; Botiz, I.; Reiter, G.

    2009-01-01

    The crystalline structures in thin films of polystyrene-b-poly(ethylene oxide) (PS-b-PEO) diblock copolymers were studied in dependence on the degree of supercooling. Atomic force microscopy showed that the crystalline domains (lamellae) consist of grains, which are macroscopic at low...

  1. Preparation of polystyrene-poly(ethylene glycol) diblock copolymer by "living" free radical polymerization

    DEFF Research Database (Denmark)

    Chen, Xianyi; Gao, Bo; Kops, Jørgen

    1998-01-01

    terminated with a TEMPO unit (MPEG-TEMPO), which was further used to prepare the diblock copolymer PS-b-PEG by 'living' free radical polymerisation of styrene. The product was purified and identified by H-1 n.m.r. and GPC. However, large amounts of homopolystyrene was also formed by simultaneous thermal...

  2. Polyion Complex Vesicles with Solvated Phosphobetaine Shells Formed from Oppositely Charged Diblock Copolymers

    Directory of Open Access Journals (Sweden)

    Keita Nakai

    2017-02-01

    Full Text Available Diblock copolymers consisting of a hydrophilic poly(2-(methacryloyloxyethyl phosphorylcholine (PMPC block and either a cationic or anionic block were prepared from (3-(methacrylamidopropyltrimethylammonium chloride (MAPTAC or sodium 2-(acrylamido-2-methylpropanesulfonate (AMPS. Polymers were synthesized via reversible addition-fragmentation chain transfer (RAFT radical polymerization using a PMPC macro-chain transfer agent. The degree of polymerization for PMPC, cationic PMAPTAC, and anionic PAMPS blocks was 20, 190, and 196, respectively. Combining two solutions of oppositely charged diblock copolymers, PMPC-b-PMAPTAC and PMPC-b-PAMPS, led to the spontaneous formation of polyion complex vesicles (PICsomes. The PICsomes were characterized using 1H NMR, static abd dynamic light scattering, transmittance electron microscopy (TEM, and atomic force microscopy. Maximum hydrodynamic radius (Rh for the PICsome was observed at a neutral charge balance of the cationic and anionic diblock copolymers. The Rh value and aggregation number (Nagg of PICsomes in 0.1 M NaCl was 78.0 nm and 7770, respectively. A spherical hollow vesicle structure was observed in TEM images. The hydrodynamic size of the PICsomes increased with concentration of the diblock copolymer solutions before mixing. Thus, the size of the PICsomes can be controlled by selecting an appropriate preparation method.

  3. Anisotropic Lithium Ion Conductivity in Single-Ion Diblock Copolymer Electrolyte Thin Films

    NARCIS (Netherlands)

    Aissou, Karim; Mumtaz, Muhammad; Usluer, Özlem; Pécastaings, Gilles; Portale, Giuseppe; Fleury, Guillaume; Cloutet, Eric; Hadziioannou, Georges

    Well-defined single-ion diblock copolymers consisting of a Li-ion conductive poly(styrenesulfonyllithium(trifluoromethylsulfonyl)imide) (PSLiTFSI) block associated with a glassy polystyrene (PS) block have been synthesized via reversible addition fragmentation chain transfer polymerization.

  4. Di-block co-polymer derived nanoporous polymer liquid core waveguides

    DEFF Research Database (Denmark)

    Christiansen, Mads Brøkner; Gopalakrishnan, Nimi; Sagar, Kaushal Shashikant

    2010-01-01

    Nanoporous liquid core waveguides are fabricated by selectively UV modifying a nanoporous polymer. The starting point is a diblock polymer where 1,2-polybutadiene (PB) molecules are bound to PDMS. When the PB is cross linked it self-assembles into PB with a network of 14 nm diameter PDMS filled...

  5. Synthesis and solution properties of PCL-b-PHPMA diblock copolymers containing stable nitroxyl radicals

    Czech Academy of Sciences Publication Activity Database

    Petrova, Svetlana; Klepac, Damir; Konefal, Rafal; Kereiche, S.; Kováčik, L.; Filippov, Sergey K.

    2016-01-01

    Roč. 49, č. 15 (2016), s. 5407-5417 ISSN 0024-9297 R&D Projects: GA MŠk(CZ) LH15213 Institutional support: RVO:61389013 Keywords : PCL-b-PHPMA diblock copolymers * TEMPO * EPR spectroscodpy Subject RIV: CD - Macromolecular Chemistry Impact factor: 5.835, year: 2016

  6. Dilute solutions and phase behavior of polydisperse A-b-(A-co-B) diblock copolymers

    Czech Academy of Sciences Publication Activity Database

    Gromadzki, Daniel; Lokaj, Jan; Šlouf, Miroslav; Štěpánek, Petr

    2009-01-01

    Roč. 50, č. 11 (2009), s. 2451-2459 ISSN 0032-3861 Institutional research plan: CEZ:AV0Z40500505 Keywords : diblock copolymer * dilute solution properties * microphase separation Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.573, year: 2009

  7. Monte Carlo simulation of diblock copolymer microphases by means of a 'fast' off-lattice model

    DEFF Research Database (Denmark)

    Besold, Gerhard; Hassager, O.; Mouritsen, Ole G.

    1999-01-01

    We present a mesoscopic off-lattice model for the simulation of diblock copolymer melts by Monte Carlo techniques. A single copolymer molecule is modeled as a discrete Edwards chain consisting of two blocks with vertices of type A and B, respectively. The volume interaction is formulated in terms...

  8. NEUTRON REFLECTIVITY STUDY OF END-ADSORBED DIBLOCK COPOLYMERS - CROSS-OVER FROM MUSHROOMS TO BRUSHES

    NARCIS (Netherlands)

    FIELD, JB; TOPRAKCIOGLU, C; DAI, L; HADZIIOANNOU, G; SMITH, G; HAMILTON, W

    1992-01-01

    We report neutron reflectivity data on polystyrene-poly(vinyl-2-pyridine) (PS-PVP) diblock copolymers adsorbed onto quartz from the selective solvent toluene (a good solvent for PS, but a poor one for PVP). The PVP > block adsorbs strongly to form a thin layer on the quartz substrate, while the PS

  9. The lamellar period in symmetric diblock copolymer thin films studied by neutron reflectivity and AFM

    DEFF Research Database (Denmark)

    Gadegaard, N.; Almdal, K.; Larsen, N.B.

    1999-01-01

    The lamellar structure of a symmetric diblock copolymer was studied as a function of temperature. We used dPEP-PDMS with a molecular weight of 8.3 kg/mol as model system. The polymer was dissolved in chloroform and spin-casted on silicon wafers into thin uniform films. The degree and direction...

  10. Adsorption kinetics of diblock copolymers from a micellar solution on silica and titania.

    NARCIS (Netherlands)

    Bijsterbosch, H.D.; Cohen Stuart, M.A.; Fleer, G.J.

    1998-01-01

    The solution and adsorption behavior of a series of diblock copolymers of hydrophobic poly(dimethyl siloxane) and hydrophilic poly(2-ethyl-2-oxazoline) was studied. These block copolymers formed large polydisperse micelles in an aqueous solution. The critical micelle concentration was lower than 2

  11. Poly(4-vinylpyridine)-block-poly(N-acryloylpiperidine) diblock copolymers: synthesis, self-assembly and interaction

    NARCIS (Netherlands)

    Hofman, Anton H.; Alberda van Ekenstein, Gerhard; Woortman, Albert; ten Brinke, Gerrit; Loos, Katja

    2015-01-01

    Controlled radical polymerization of 4-vinylpyridine (4VP) and N-acryloylpiperidine (API) by the RAFT process allowed preparation of well-defined double hydrogen bond accepting P4VP-b-PAPI diblock copolymers. The miscibility of this new monomer pair was studied via a random copolymer blend approach

  12. Associative diblock copolymers of poly(ethylene glycol) and coiled-coil peptides

    Czech Academy of Sciences Publication Activity Database

    Pechar, Michal; Kopečková, P.; Joss, L.; Kopeček, J.

    2002-01-01

    Roč. 2, č. 5 (2002), s. 199-206 ISSN 1616-5187 R&D Projects: GA AV ČR KSK4050111 Institutional research plan: CEZ:AV0Z4050913 Keywords : coiled -coil peptides * diblock copolymers * poly(ethylene glycol) Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.792, year: 2002

  13. Effect of the Molecular Weight of AB Diblock Copolymers on the Lamellar Orientation in Thin Films

    DEFF Research Database (Denmark)

    Potemkin, Igor I.; Busch, Peter; Smilgies, Detlef-M

    2007-01-01

    We propose a theoretical explanation of the parallel and perpendicular lamellar orientations in free surface films of symmetric polystyrene-block-polybutadiene diblock copolymers on silicon substrates (with a native SiOx layer). Two approaches are developed: A correction to the strong segregation...

  14. Toward an equilibrium structure in lamellar diblock copolymer thin films using solvent vapor annealing

    DEFF Research Database (Denmark)

    Sepe, Alessandro; Zhang, Jianqi; Perlich, Jan

    2016-01-01

    Solvent vapor annealing (SVA) is frequently used to improve the ordering in diblock copolymer thin films. An important question is which SVA protocol should be chosen to ensure thermodynamic equilibrium. Here, we investigate two thin films from a low molar-mass, lamellae-forming polystyrene-block-polybutadiene...

  15. Facially amphiphilic thiol capped gold and silver nanoparticles

    Indian Academy of Sciences (India)

    Abstract. A series of bile acid-derived facially amphiphilic thiols have been used to cap sliver and gold nanoparticles. The self-assembling properties of these steroid-capped nanoparticles have been investigated and reported in this article.

  16. SANS, SAXS, rheology and birefringence-strengths and weaknesses in probing phase behaviour of a diblock copolymer

    DEFF Research Database (Denmark)

    Vigild, Martin Etchells; Eskimergen, Rüya; Mortensen, Kell

    2004-01-01

    Asymmetrically composed diblock copolymers exhibit multiphase behaviour and transit the lamellae, gyroid and hexagonal cylindrical phases before reaching the order–disorder temperature, TODT. During a heating experiment towards TODT we observe that birefringence measurements are more sensitive th...

  17. Complex Macrophase-Separated Nanostructure Induced by Microphase Separation in Binary Blends of Lamellar Diblock Copolymer Thin Films

    DEFF Research Database (Denmark)

    Zhang, Jianqi; Posselt, Dorthe; Smilgies, Detlef-M.

    2014-01-01

    in a one-phase state, indicating that the higher molar mass diblock copolymer dominates the lamellar orientation. The lamellar thickness decreases linearly with increasing volume fraction of the low molar mass diblock copolymer. After SVA, well-defined macrophase-separated nanostructures appear, which......The nanostructures of thin films spin-coated from binary blends of compositionally symmetric polystyrene-b-polybutadiene (PS-b-PB) diblock copolymer having different molar masses are investigated by means of atomic force microscopy (AFM) and grazing-incidence small-angle X-ray scattering (GISAXS......) after spin-coating and after subsequent solvent vapor annealing (SVA). In thin films of the pure diblock copolymers having high or low molar mass, the lamellae are perpendicular or parallel to the substrate, respectively. The as-prepared binary blend thin films feature mainly perpendicular lamellae...

  18. Detection of prostate specific antigen (PSA) in human saliva using an ultra-sensitive nanocomposite of graphene nanoplatelets with diblock-co-polymers and Au electrodes.

    Science.gov (United States)

    Khan, M S; Dighe, K; Wang, Z; Srivastava, I; Daza, E; Schwartz-Dual, A S; Ghannam, J; Misra, S K; Pan, D

    2018-02-26

    Prostate-specific antigen (PSA) is a commonly used biomarker for the detection of prostate cancer (PCa) and there are numerous data available for its invasive detection in the serum and whole blood. In this work, an electrochemical sensing method was devised to detect traces of PSA in human saliva using a hybrid nanocomposite of graphene nanoplatelets with diblock co-polymers and Au electrodes (GRP-PS 67 -b-PAA 27 -Au). The pure graphitic composition on filter paper provides significantly high electrical and thermal conductivity while PS 67 -b-PAA 27 makes an amphiphilic bridge between GRP units. The sensor utilizes the binding of an anti-PSA antibody with an antigen-PSA to act as a resistor in a circuit providing an impedance change that in turn allows for the detection and quantification of PSA in saliva samples. A miniaturized electrical impedance analyzer was interfaced with a sensor chip and the data were recorded in real-time using a Bluetooth-enabled module. This fully integrated and optimized sensing device exhibited a wide PSA range of detection from 0.1 pg mL -1 to 100 ng mL -1 (R 2 = 0.963) with a lower limit of detection of 40 fg mL -1 . The performance of the biosensor chip was validated with an enzyme-linked immunosorbent assay technique with a regression coefficient as high as 0.940. The advantages of the newly developed saliva-PSA electrical biosensor over previously reported serum-PSA electrochemical biosensors include a faster response time (3-5 min) to achieve a stable electrical signal for PSA detection, high selectivity, improved sensitivity, no additional requirement of a redox electrolyte for electron exchange and excellent shelf life. The presented sensor is aimed for clinical commercialization to detect PSA in human saliva.

  19. Antiviral activity of cationic amphiphilic drugs.

    Science.gov (United States)

    Salata, Cristiano; Calistri, Arianna; Parolin, Cristina; Baritussio, Aldo; Palù, Giorgio

    2017-05-01

    Emerging and reemerging viral infections represent a major concern for human and veterinary public health and there is an urgent need for the development of broad-spectrum antivirals. Areas covered: A recent strategy in antiviral research is based on the identification of molecules targeting host functions required for infection of multiple viruses. A number of FDA-approved drugs used to treat several human diseases are cationic amphiphilic drugs (CADs) that have the ability to accumulate inside cells affecting several structures/functions hijacked by viruses during infection. In this review we summarized the CADs' chemical properties and effects on the cells and reported the main FDA-approved CADs that have been identified so far as potential antivirals in drug repurposing studies. Expert commentary: Although there have been concerns regarding the efficacy and the possible side effects of the off-label use of CADs as antivirals, they seem to represent a promising starting point for the development of broad-spectrum antiviral strategies. Further knowledge about their mechanism of action is required to improve their antiviral activity and to reduce the risk of side effects.

  20. Selection of Prebiotic Molecules in Amphiphilic Environments

    Directory of Open Access Journals (Sweden)

    Christian Mayer

    2017-01-01

    Full Text Available A basic problem in all postulated pathways of prebiotic chemistry is the low concentration which generally is expected for interesting reactants in fluid environments. Even though compounds, like nucleobases, sugars or peptides, principally may form spontaneously under environmental conditions, they will always be rapidly diluted in an aqueous environment. In addition, any such reaction leads to side products which often exceed the desired compound and generally hamper the first steps of a subsequent molecular evolution. Therefore, a mechanism of selection and accumulation of relevant prebiotic compounds seems to be crucial for molecular evolution. A very efficient environment for selection and accumulation can be found in the fluid continuum circulating in tectonic fault zones. Vesicles which form spontaneously at a depth of approximately 1 km present a selective trap for amphiphilic molecules, especially for peptides composed of hydrophilic and hydrophobic amino acids in a suitable sequence. The accumulation effect is shown in a numeric simulation on a simplified model. Further, possible mechanisms of a molecular evolution in vesicle membranes are discussed. Altogether, the proposed scenario can be seen as an ideal environment for constant, undisturbed molecular evolution in and on cell-like compartments.

  1. Repurposing Cationic Amphiphilic Antihistamines for Cancer Treatment

    Directory of Open Access Journals (Sweden)

    Anne-Marie Ellegaard

    2016-07-01

    Full Text Available Non-small cell lung cancer (NSCLC is one of the deadliest cancers worldwide. In search for new NSCLC treatment options, we screened a cationic amphiphilic drug (CAD library for cytotoxicity against NSCLC cells and identified several CAD antihistamines as inducers of lysosomal cell death. We then performed a cohort study on the effect of CAD antihistamine use on mortality of patients diagnosed with non-localized cancer in Denmark between 1995 and 2011. The use of the most commonly prescribed CAD antihistamine, loratadine, was associated with significantly reduced all-cause mortality among patients with non-localized NSCLC or any non-localized cancer when compared with use of non-CAD antihistamines and adjusted for potential confounders. Of the less frequently described CAD antihistamines, astemizole showed a similar significant association with reduced mortality as loratadine among patients with any non-localized cancer, and ebastine use showed a similar tendency. The association between CAD antihistamine use and reduced mortality was stronger among patients with records of concurrent chemotherapy than among those without such records. In line with this, sub-micromolar concentrations of loratadine, astemizole and ebastine sensitized NSCLC cells to chemotherapy and reverted multidrug resistance in NSCLC, breast and prostate cancer cells. Thus, CAD antihistamines may improve the efficacy of cancer chemotherapy.

  2. Repurposing Cationic Amphiphilic Antihistamines for Cancer Treatment.

    Science.gov (United States)

    Ellegaard, Anne-Marie; Dehlendorff, Christian; Vind, Anna C; Anand, Atul; Cederkvist, Luise; Petersen, Nikolaj H T; Nylandsted, Jesper; Stenvang, Jan; Mellemgaard, Anders; Østerlind, Kell; Friis, Søren; Jäättelä, Marja

    2016-07-01

    Non-small cell lung cancer (NSCLC) is one of the deadliest cancers worldwide. In search for new NSCLC treatment options, we screened a cationic amphiphilic drug (CAD) library for cytotoxicity against NSCLC cells and identified several CAD antihistamines as inducers of lysosomal cell death. We then performed a cohort study on the effect of CAD antihistamine use on mortality of patients diagnosed with non-localized cancer in Denmark between 1995 and 2011. The use of the most commonly prescribed CAD antihistamine, loratadine, was associated with significantly reduced all-cause mortality among patients with non-localized NSCLC or any non-localized cancer when compared with use of non-CAD antihistamines and adjusted for potential confounders. Of the less frequently described CAD antihistamines, astemizole showed a similar significant association with reduced mortality as loratadine among patients with any non-localized cancer, and ebastine use showed a similar tendency. The association between CAD antihistamine use and reduced mortality was stronger among patients with records of concurrent chemotherapy than among those without such records. In line with this, sub-micromolar concentrations of loratadine, astemizole and ebastine sensitized NSCLC cells to chemotherapy and reverted multidrug resistance in NSCLC, breast and prostate cancer cells. Thus, CAD antihistamines may improve the efficacy of cancer chemotherapy. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

  3. Dissolving Microneedle Arrays for Transdermal Delivery of Amphiphilic Vaccines.

    Science.gov (United States)

    An, Myunggi; Liu, Haipeng

    2017-07-01

    Amphiphilic vaccine based on lipid-polymer conjugates is a new type of vaccine capable of self-delivering to the immune system. When injected subcutaneously, amphiphilic vaccines efficiently target antigen presenting cells in the lymph nodes (LNs) via a unique albumin-mediated transport and uptake mechanism and induce potent humoral and cellular immune responses. However, whether this new type of vaccine can be administrated via a safe, convenient microneedle-based transdermal approach remains unstudied. For such skin barrier-disruption systems, a simple application of microneedle arrays (MNs) is desired to disrupt the stratum corneum, and for rapid and pain-free self-administration of vaccines into the skin, the anatomic place permeates with an intricate mesh of lymphatic vessels draining to LNs. Here the microneedle transdermal approach is combined with amphiphilic vaccines to create a simple delivery approach which efficiently traffic molecular vaccines into lymphatics and draining LNs. The rapid release of amphiphilic vaccines into epidermis upon application of dissolving MNs to the skin of mice generates potent cellular and humoral responses, comparable or superior to those elicited by traditional needle-based immunizations. The results suggest that the amphiphilic vaccines delivered by dissolving MNs can provide a simple and safer vaccination method with enhanced vaccine efficacy. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Microelectrode Arrays and the Use of PEG-Functionalized Diblock Copolymer Coatings

    Directory of Open Access Journals (Sweden)

    Sakshi Uppal

    2014-09-01

    Full Text Available PEG-modified diblock copolymer surfaces have been examined for their compatibility with microelectrode array based analytical methods. The use of PEG-modified polymer surfaces on the arrays was initially problematic because the redox couples used in the experiments were adsorbed by the polymer. This led the current measured by cyclic voltammetry for the redox couple to be unstable and increase with time. However, two key findings allow the experiments to be successful. First, after multiple cyclic voltammograms the current associated with the redox couple does stabilize so that a good baseline current can be established. Second, the rate at which the current stabilizes is consistent every time a particular coated array is used. Hence, multiple analytical experiments can be conducted on an array coated with a PEG-modified diblock copolymer and the data obtained is comparable as long as the data for each experiment is collected at a consistent time point.

  5. USANS investigations of solutions of diblock copolymers in partially miscible solvents

    Energy Technology Data Exchange (ETDEWEB)

    Ryukhtin, Vasyl [Nuclear Physics Institute, 25068, Rez (Czech Republic)]. E-mail: Ryukhtin@ujf.cas.cz; Stepanek, Petr [Institute of Macromolecular Chemistry, Heyrovsky Sq. 2, 16206, Prague 6 (Czech Republic); Tuzar, Zdenek [Institute of Macromolecular Chemistry, Heyrovsky Sq. 2, 16206, Prague 6 (Czech Republic); Pranzas, Klaus [GKSS Research Centre, D-21494 Geesthacht (Germany); Bellmann, Dieter [GKSS Research Centre, D-21494 Geesthacht (Germany)

    2006-11-15

    We report the results of ultra-small-angle neutron scattering (USANS) experiments from diblock copolymers A-B dissolved in a mixture of partially compatible solvents a and b. Solvent a is dimethylformamide, which is a good solvent for block A (polystyrene) and a bad solvent for block B poly(ethylene-co-propylene), and vice versa for solvent b, namely, cyclohexan. Such samples are microphase-segragated into a-rich and b-rich domains separated by interfaces covered with diblock copolymer. Our USANS measurements have shown that a long-range periodic structure of these segregations is limited in extend, it consists of grains with mean radius of several microns. Structural characteristics of these grains and kinetics of their formation depending on the temperature were studied by means of USANS for various chemical compositions of the samples.

  6. Considerations in binding diblock copolymers on hydrophilic alginate beads for providing an immunoprotective membrane

    Science.gov (United States)

    Spasojevic, Milica; Bhujbal, Swapnil; Paredes, Genaro; de Haan, Bart J; Schouten, Arend J; de Vos, Paul

    2014-01-01

    Alginate-based microcapsules are being proposed for treatment of many types of diseases. A major obstacle however in the successes is that these capsules are having large lab-to-lab variations. To make the process more reproducible, we propose to cover the surface of alginate capsules with diblock polymers that can form polymer brushes. In the present study, we describe the stepwise considerations for successful application of diblock copolymer of polyethylene glycol (PEG) and poly-l-lysine (PLL) on the surface of alginate beads. Special procedures had to be designed as alginate beads are hydrophilic and most protocols are designed for hydrophobic biomaterials. The successful attachment of diblock copolymer and the presence of PEG blocks on the surface of the capsules were studied by fluorescence microscopy. Longer time periods, that is, 30–60 min, are required to achieve saturation of the surface. The block lengths influenced the strength of the capsules. Shorter PLL blocks resulted in less stable capsules. Adequate permeability of the capsules was achieved with poly(ethylene glycol)-block-poly(l-lysine hydrochloride) (PEG454-b-PLL100) diblock copolymers. The capsules were a barrier for immunoglobulin G. The PEG454-b-PLL100 capsules have similar mechanical properties as PLL capsules. Minor immune activation of nuclear factor κB in THP-1 monocytes was observed with both PLL and PEG454-b-PLL100 capsules prepared from purified alginate. Our results show that we can successfully apply block copolymers on the surface of hydrophilic alginate beads without interfering with the physicochemical properties. PMID:23853069

  7. Self-oscillating AB diblock copolymer developed by post modification strategy

    Energy Technology Data Exchange (ETDEWEB)

    Ueki, Takeshi, E-mail: ueki@cross.t.u-tokyo.ac.jp, E-mail: ryo@cross.t.u-tokyo.ac.jp; Onoda, Michika; Tamate, Ryota; Yoshida, Ryo, E-mail: ueki@cross.t.u-tokyo.ac.jp, E-mail: ryo@cross.t.u-tokyo.ac.jp [Department of Materials Engineering, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); Shibayama, Mitsuhiro [Institute for Solid State Physics, The University of Tokyo, 5-1-5 Kashiwano-ha, Kashiwa, Chiba 277-8581 (Japan)

    2015-06-15

    We prepared AB diblock copolymer composed of hydrophilic poly(ethylene oxide) segment and self-oscillating polymer segment. In the latter segment, ruthenium tris(2,2′-bipyridine) (Ru(bpy){sub 3}), a catalyst of the Belousov-Zhabotinsky reaction, is introduced into the polymer architecture based on N-isopropylacrylamide (NIPAAm). The Ru(bpy){sub 3} was introduced into the polymer segment by two methods; (i) direct random copolymerization (DP) of NIPAAm and Ru(bpy){sub 3} vinyl monomer and (ii) post modification (PM) of Ru(bpy){sub 3} with random copolymer of NIPAAm and N-3-aminopropylmethacrylamide. For both the diblock copolymers, a bistable temperature region (the temperature range; ΔT{sub m}), where the block copolymer self-assembles into micelle at reduced Ru(bpy){sub 3}{sup 2+} state whereas it breaks-up into individual polymer chain at oxidized Ru(bpy){sub 3}{sup 3+} state, monotonically extends as the composition of the Ru(bpy){sub 3} increases. The ΔT{sub m} of the block copolymer prepared by PM is larger than that by DP. The difference in ΔT{sub m} is rationalized from the statistical analysis of the arrangement of the Ru(bpy){sub 3} moiety along the self-oscillating segments. By using the PM method, the well-defined AB diblock copolymer having ΔT{sub m} (ca. 25 °C) large enough to cause stable self-oscillation can be prepared. The periodic structural transition of the diblock copolymer in a dilute solution ([Polymer] = 0.1 wt. %) is closely investigated in terms of the time-resolved dynamic light scattering technique at constant temperature in the bistable region. A macroscopic viscosity oscillation of a concentrated polymer solution (15 wt. %) coupled with the periodic microphase separation is also demonstrated.

  8. Novel Synthesis of Cellulose-Based Diblock Copolymer of Poly(hydroxyethyl methacrylate) by Mechanochemical Reaction

    OpenAIRE

    Ohura, Takeshi; Tsutaki, Yusaku; Sakaguchi, Masato

    2014-01-01

    The mechanical fracture of polymer produces polymeric free radical chain-ends, by which liner block copolymers have been synthesized. A diblock copolymer of microcrystalline cellulose (MCC) and poly 2-hydroxyethyl methacrylate (pHEMA) was produced by the mechanochemical polymerization under vacuum and room temperature. The fraction of pHEMA in MCC-block-pHEMA produced by the mechanochemical polymerization increased up to 21 mol% with increasing fracture time (~6 h). Then, the tacticities of H...

  9. Dynamics and order-disorder transitions in bidisperse diblock copolymer blends

    International Nuclear Information System (INIS)

    Wang Yueqiang; Li Xuan; Tang Ping; Yang Yuliang

    2011-01-01

    We employ the dynamic extension of self-consistent field theory (DSCFT) to study dynamics and order-disorder transitions (ODT) in AB diblock copolymer binary mixtures of two different monodisperse chain lengths by imitating the dynamic storage modulus G' corresponding to any given morphology in the oscillatory shear measurements. The different polydispersity index (PDI) is introduced by binary blending AB diblock copolymers with variations in chain lengths and chain number fractions. The simulation results show that the increase of polydispersity in the minority or symmetric block introduces a decrease in the segregation strength at the ODT, (χN) ODT , whereas the increase of polydispersity in the majority block results in a decrease, then increase and final decrease again in (χN) ODT . To the best of our knowledge, our DSCFT simulations, for the first time, predict an increase in (χN) ODT with the PDI in the majority block, which produces the experimental results. The simulations by previous SCFT, which generally speaking, is capable of describing equilibrium morphologies, however, contradict the experimental data. The polydispersity acquired by properly tuning the chain lengths and number fractions of binary diblock copolymer blends should be a convenient and efficient way to control the microphase separation strength at the ODT. -- Research highlights: → Order-disorder transition in AB diblock copolymer mixtures is investigated using DSCFT. → Microphase separation strength at the ODT increases with PDI in the majority block. → Microphase separation strength at the ODT decreases with PDI in the minority block. → Introduction of polydispersity is efficient to control microphase separation strength at the ODT.

  10. USANS investigations of solutions of diblock copolymers in partially miscible solvents

    Czech Academy of Sciences Publication Activity Database

    Ryukhtin, Vasyl; Štěpánek, Petr; Tuzar, Zdeněk; Pranzas, K.; Bellmann, D.

    2006-01-01

    Roč. 385-386, SI-Part 1 (2006), s. 762-765 ISSN 0921-4526 R&D Projects: GA AV ČR IAA4050403 Institutional research plan: CEZ:AV0Z10480505; CEZ:AV0Z40500505 Keywords : Ultra - small - angle neutron scattering (USANS) * Diblock copolymer solutions Subject RIV: BE - Theoretical Physics Impact factor: 0.872, year: 2006

  11. Investigating self-assembly and metal nanoclusters in aqueous di-block copolymers solutions

    CERN Document Server

    Lo Celso, F; Triolo, R; Triolo, A; Strunz, P; Bronstein, L; Zwanziger, J; Lin, J S

    2002-01-01

    Self-assembling properties of di-block copolymers/ surfactant hybrids in aqueous solution can be exploited to obtain metal nanoparticles stable dispersion. Results will be presented here for polystyrene-block-poly(ethylene oxide) solutions. A SANS structural investigation has been performed over different molecular weights of both hydrophilic and hydrophobic block, by varying temperature and concentration of the copolymer. A SAXS characterization of micellar systems containing Pt nanoparticles is reported. (orig.)

  12. Small-angle neutron scattering from solutions of diblock copolymers in partially miscible solvents

    Czech Academy of Sciences Publication Activity Database

    Štěpánek, Petr; Tuzar, Zdeněk; Nallet, F.; Noirez, L.

    2005-01-01

    Roč. 38, č. 8 (2005), s. 3426-3431 ISSN 0024-9297 R&D Projects: GA ČR GA203/04/0490; GA ČR GA203/02/1262; GA ČR GESON/03/E001 Institutional research plan: CEZ:AV0Z4050913 Keywords : diblock copolymers * small angle neutron scattering * solvents Subject RIV: CD - Macromolecular Chemistry Impact factor: 4.024, year: 2005

  13. Thermoresponsive Self-Assembly of Nanostructures from a Collagen-Like Peptide-Containing Diblock Copolymera

    OpenAIRE

    Luo, Tianzhi; He, Lirong; Theato, Patrick; Kiick, Kristi L.

    2014-01-01

    Temperature-triggered formation of nanostructures with distinct biological activity offers opportunities in selective modification of matrices and in drug delivery. Toward these ends, diblock polymers comprising poly(diethylene glycol methyl ether methacrylate) (PDEGMEMA) conjugated to a triple helix-forming collagen-like peptide (CLP) is produced. The ability of the CLP domain to maintain its triple helix conformation after conjugation with the polymer is confirmed via circular dichroism (CD...

  14. Blending of Diblocks and Triblocks with identical hydrophilic block for multicompartment and multigeometry nanostructures

    Science.gov (United States)

    Zeng, Zheng; Zhu, Jiahua; Chen, Yingchao; Zhang, Shiyi; Pochan, Darrin; Wooley, Karen

    2012-02-01

    Unique micellar morphologies, such as toroids, disks, and helices, have been obtained from a single triblock copolymer PAA-PMA-PS poly(acrylic acid)-b-poly(methyl acrylate)-b-poly(styrene) (PAA-PMA-PS) through a self-assembly process in dilute water/THF(tetrahydrofuran) solvent mixtures in the presense of organic multiamine molecules. Aiming to better understand their formation and explore novel structures, diblock copolymers, e.g. PAA-PMA and PAA-PS, were mixed with PAA-PMA-PS to co-assemble at desired solution conditions to produce known nanostructures (e.g. toroid, disk, helix fomations). By taking advantage of the kinetic pathway of assembly and mulitamine-PAA complexation, the additional diblock copolymers can be trapped in the same micelle with the triblock PAA-PMA-PS. Interesting transitions were found in toroid/disk/helix fomations by changing the amount of the added diblock copolymers. The morphologies of the blended nanoparticles was characterized with cryogenic and conventional transmission electron microscopy, dynamic light scattering, and small angle neutron scattering.

  15. Substrate-bound growth of Au-Pd diblock nanowire and hybrid nanorod-plate

    Science.gov (United States)

    He, Jiating; Wang, Yawen; Fan, Zhanxi; Lam, Zhenhui; Zhang, Hua; Liu, Bin; Chen, Hongyu

    2015-04-01

    We expand the scope of the previously developed Active Surface Growth mode for growing substrate-bound ultrathin Pd (d = 4 nm) and Ag nanowires (d = 30 nm) in aqueous solution under ambient conditions. Using Au nanorods as the seeds, selective growth at the contact line between the rod and the substrate eventually leads to an attached Pd nanoplate. The unique growth mode also allows sequential growth of different materials via a single seed, giving substrate-bound Au-Pd diblock nanowires. The new abilities to use seed shape to pre-define the active sites and to apply sequential growth open windows for new pathways to hybrid nanostructures.We expand the scope of the previously developed Active Surface Growth mode for growing substrate-bound ultrathin Pd (d = 4 nm) and Ag nanowires (d = 30 nm) in aqueous solution under ambient conditions. Using Au nanorods as the seeds, selective growth at the contact line between the rod and the substrate eventually leads to an attached Pd nanoplate. The unique growth mode also allows sequential growth of different materials via a single seed, giving substrate-bound Au-Pd diblock nanowires. The new abilities to use seed shape to pre-define the active sites and to apply sequential growth open windows for new pathways to hybrid nanostructures. Electronic supplementary information (ESI) available: Supporting TEM and SEM images of control experiments with different reaction conditions and another type of diblock nanowires. See DOI: 10.1039/c5nr00361j

  16. Mesomorphic phase behaviour of low molar mass PEP-PDMS diblock copolymers synthesized by anionic polymerization

    International Nuclear Information System (INIS)

    Vigild, M.E.

    1997-10-01

    The phase behaviour of low molar mass poly(ethylene-alt-propylene) -poly(dimethylsiloxane) (PEP-PDMS) is investigated in this thesis by the combination of dynamical mechanical spectroscopy (rheology) to measure phase transition temperatures, and small-angle x-ray scattering to identify the morphology of encountered phases. Samples of PEP-PDMS in the range of 0.2-0.7 in volume fraction of PEP are studied. This diblock copolymer system exhibits the three classical phases of lamellar sandwich structure (LAM), hexagonally packed cylinders (HEX), and spheres arranged on a body centered cubic lattice (BCC). Furthermore the gyroid phase (Ia3d symmetry) of two interpenetrating networks was also identified as a stable phase of the PEP-PDMS system. Time resolved measurements of small-angle neutron scattering in tandem with simultaneous in-situ rheological measurements are performed on samples showing transitions between different ordered phases. The identification of especially the BCC and gyroid phases from scattering experiments is treated. By performing mesoscopic crystallographic measurements using a custom built goniometer it was unambiguously shown that the application of shear to an unoriented powder-like sample introduces uniaxial orientation of the gyroid phase. The orientation of the ordered phase is otherwise random, causing a two-dimensional powder. Finally this dissertation presents a discussion of relevant parameters for the description of diblock copolymer phase behaviour together with descriptions of anionic polymerization for the synthesis of copolymers, and various experimental techniques for the characterization of diblocks. (au)

  17. Effect of sequence dispersity on morphology of tapered diblock copolymers from molecular dynamics simulations.

    Science.gov (United States)

    Levine, William G; Seo, Youngmi; Brown, Jonathan R; Hall, Lisa M

    2016-12-21

    Tapered diblock copolymers are similar to typical AB diblock copolymers but have an added transition region between the two blocks which changes gradually in composition from pure A to pure B. This tapered region can be varied from 0% (true diblock) to 100% (gradient copolymer) of the polymer length, and this allows some control over the microphase separated domain spacing and other material properties. We perform molecular dynamics simulations of linearly tapered block copolymers with tapers of various lengths, initialized from fluids density functional theory predictions. To investigate the effect of sequence dispersity, we compare systems composed of identical polymers, whose taper has a fixed sequence that most closely approximates a linear gradient, with sequentially disperse polymers, whose sequences are created statistically to yield the appropriate ensemble average linear gradient. Especially at high segregation strength, we find clear differences in polymer conformations and microstructures between these systems. Importantly, the statistical polymers are able to find more favorable conformations given their sequence, for instance, a statistical polymer with a larger fraction of A than the median will tend towards the A lamellae. The conformations of the statistically different polymers can thus be less stretched, and these systems have higher overall density. Consequently, the lamellae formed by statistical polymers have smaller domain spacing with sharper interfaces.

  18. Investigation of Universal Behavior in Symmetric Diblock Copolymer Melts

    Science.gov (United States)

    Medapuram, Pavani

    Coarse-grained theories of dense polymer liquids such as block copolymer melts predict a universal dependence of equilibrium properties on a few dimensionless parameters. For symmetric diblock copolymer melts, such theories predict a universal dependence on only chieN and N¯, where chie is an effective interaction parameter, N is the degree of polymerization, and N¯ is a measure of overlap. This thesis focuses on testing the universal behavior hypothesis by comparing results for various properties obtained from different coarse-grained simulation models to each other. Specifically, results from pairs of simulations of different models that have been designed to have matched values of N¯ are compared over a range of values of chiN. The use of vastly different simulation models allows us to cover a vast range of chi eN ≃ 200 - 8000 that includes most of the experimentally relevant range. Properties studied here include collective and single-chain correlations in the disordered phase, block and chain radii of gyration in the disordered phase, the value of chieN at the order-disorder transition (ODT), the free energy per chain, the latent heat of transition, the layer spacing, the composition profile, and compression modulus in the ordered phase. All results strongly support the universal scaling hypothesis, even for rather short chains, confirming that it is indeed possible to give an accurate universal description of simulation models that differ in many details. The underlying universality becomes apparent, however, only if data are analyzed using an adequate estimate of chie, which we obtained by fitting the structure factor S( q) in the disordered state to predictions of the recently developed renormalized one-loop (ROL) theory. The ROL theory is shown to provide an excellent description of the dependence of S(q on chain length and thermodynamic conditions for all models, even for very short chains, if we allow for the existence of a nonlinear dependence of

  19. Tough Amphiphilic Gels for Antifouling Applications

    Science.gov (United States)

    Villada, Laura M.

    Biofouling is the attachment of unwanted organisms on a surface, and it is influenced by a host of variables including the chemistry of the material as well as both the surface and bulk properties, and controlling and understanding the effect of these properties is critical for the development of effective materials to combat biofouling. All surfaces that are submerged in water are subject to the rapid colonization of a wide range of marine organisms. Marine biofouling decreases fuel efficiency, costing the Navy millions of dollars in penalty, as well as having drastic environmental effects. Previous prevention of biofouling in marine systems has been accomplished by the administration of biocides and toxic coatings. In recent years, increased concerns about the impacts of these hazardous compounds into marine ecosystems has spurred efforts to develop cost effective, non-toxic, and durable anti-fouling coatings. Hydrogels, hydrophilic crosslinked networks, are being used to modify silicone marine coatings and have demonstrated potential at combatting biofouling. Understanding the impact of amphiphilic materials, i.e. their structure and properties, on biofouling is of great importance in order to address the need in the industry. In this study, poly(2-hydroxyethyl methacrylate) (HEMA) crosslinked networks were tailored to investigate the influence of their surface and bulk properties on biofouling. Previous research utilizing HEMA-siloxane gels suggested a relationship between molecular weight between crosslinks, M c, and the attachment of soft fouling sporelings of the green algae U. linza and adsorption of the protein bovine serum albumin (BSA), and the initial thrust of this dissertation was aimed at resolving this relationship. Gel composition was modified by varying the siloxane crosslinking agent and the siloxane hydrophobic monomer concentrations. The gels exhibited an increase in elastic modulus from 0.17 to 8.55 MPa that coincided with an increasing

  20. 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

  1. Magnetic Amphiphilic Composites Applied for the Treatment of Biodiesel Wastewaters

    Directory of Open Access Journals (Sweden)

    Bruno R. S. Lemos

    2012-05-01

    Full Text Available In this work, new magnetic amphiphilic composites were prepared by chemical vapor deposition with ethanol on the surface of hydrophilic natural chrysotile matrix containing Fe catalyst. XRD, Raman, Mössbauer and SEM analyses suggest the formation of a complex nanostructured material composed of hydrophobic carbon nanotubes/nanofibers grown on the hydrophilic surface of the MgSi fiber mineral and the presence of Fe metallic nanoparticles coated by carbon. These nanostructured particles show amphiphilic properties and interact very well with both oil and aqueous phases. When added to emulsions the amphiphilic particles locate on the oil/water interface and, under a magnetic field, the oil droplets collapsed leading to the separation of the aqueous and oil phases. Preliminary work showed excellent results on the use of these particles to break wastewater emulsions in the biodiesel process.

  2. Synthesis of silver nanoparticles in melts of amphiphilic polyesters

    Science.gov (United States)

    Vasylyev, S.; Damm, C.; Segets, D.; Hanisch, M.; Taccardi, N.; Wasserscheid, P.; Peukert, W.

    2013-03-01

    The current work presents a one-step procedure for the synthesis of amphiphilic silver nanoparticles suitable for production of silver-filled polymeric materials. This solvent free synthesis via reduction of Tollens’ reagent as silver precursor in melts of amphiphilic polyesters consisting of hydrophilic poly(ethylene glycol) blocks and hydrophobic alkyl chains allows the production of silver nanoparticles without any by-product formation. This makes them especially interesting for the production of medical devices with antimicrobial properties. In this article the influences of the chain length of the hydrophobic block in the amphiphilic polyesters and the process temperature on the particle size distribution (PSD) and the stability of the particles against agglomeration are discussed. According to the results of spectroscopic and viscosimetric investigations the silver precursor is reduced to elemental silver nanoparticles by a single electron transfer process from the poly(ethylene glycol) chain to the silver ion.

  3. Amphiphile Meets Amphiphile: Beyond the Polar-Apolar Dualism in Ionic Liquid/Alcohol Mixtures.

    Science.gov (United States)

    Russina, Olga; Sferrazza, Alessio; Caminiti, Ruggero; Triolo, Alessandro

    2014-05-15

    The mesoscopic morphology of binary mixtures of ethylammonium nitrate (EAN), the protic ionic liquid par excellence, and methanol is explored using neutron/X-ray diffraction and computational techniques. Both compounds are amphiphilic and characterized by an extended hydrogen bonding network: surprisingly, though macroscopically homogeneous, these mixtures turn out to be mesoscopically highly heterogeneous. Our study reveals that even in methanol-rich mixtures, a wide distribution of clusters exists where EAN preserves its bulk, sponge-like morphology. Accordingly methanol does not succeed in fully dissociating the ionic liquid that keeps on organizing in a bulk-like fashion. This behavior represents the premises to the more dramatic phenomenology observed with longer alcohols that eventually phase separate from EAN. These results challenge the commonly accepted polar and apolar moieties segregation in ionic liquids/molecular liquids mixtures and the current understanding of technologically relevant solvation processes.

  4. Drug release from hydrazone-containing peptide amphiphiles.

    Science.gov (United States)

    Matson, John B; Stupp, Samuel I

    2011-07-28

    Hydrolytically-labile hydrazones in peptide amphiphiles were studied as degradable tethers for release of the drug nabumetone from nanofiber gels. On-resin addition of the novel compound tri-Boc-hydrazido adipic acid to a lysine ε-amine allowed for precise placement of a hydrazide in a peptide sequence.

  5. Drug release from hydrazone-containing peptide amphiphiles

    OpenAIRE

    Matson, John B.; Stupp, Samuel I.

    2011-01-01

    Hydrolytically-labile hydrazones in peptide amphiphiles were studied as degradable tethers for drug release from nanofiber gels. On-resin addition of the novel compound tri-Bochydrazido adipic acid to a lysine ε-amine allowed for precise placement of a hydrazide in a peptide sequence. Hydrazone formation and hydrolysis were examined by addition and release of nabumetone froma peptide amphiphilematrix.

  6. Facially amphiphilic thiol capped gold and silver nanoparticles

    Indian Academy of Sciences (India)

    Wintec

    Jawaharlal Nehru Centre for Advanced Scientific Research,. Bangalore 560 064. Facially amphiphilic thiol capped gold and silver nanoparticles. †. SHREEDHAR BHAT a and UDAY MAITRA*. Department of Organic Chemistry, Indian Institute of Science, Bangalore 560 012 a. Current address: ISM, University of Bordeaux, ...

  7. Blends of Amphiphilic, Hyperbranched Polyesters and Different Polyolefins

    NARCIS (Netherlands)

    Schmaljohann, D.; Pötschke, P.; Hässler, R.; Voit, B.I.; Froehling, P.E.; Mostert, B.; Loontjens, J.A.

    1999-01-01

    A hyperbranched polyester based on 3,5-dihydroxybenzoic acid was completely modified with dodecanoyl chloride to result in an amphiphilic, globular polymer, which has a polar core and a nonpolar outer sphere with the ability both to incorporate an organic dye and to interact with a nonpolar matrix.

  8. Photoresponsive Amphiphilic Macrocycles Containing Main-Chain Azobenzene Polymers.

    Science.gov (United States)

    Sun, Yadong; Wang, Zhao; Li, Yiwen; Zhang, Zhengbiao; Zhang, Wei; Pan, Xiangqiang; Zhou, Nianchen; Zhu, Xiulin

    2015-07-01

    Herein, the first example of photosensitive cyclic amphiphilic homopolymers consisting of multiple biphenyl azobenzene chromophores in the cyclic main chain tethered with hydrophilic tetraethylene glycol monomethyl ether units is presented. The synthetic approach involves sequentially performed thermal catalyzed "click" step-growth polymerization in bulk, and Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) intramolecular cyclization from α-alkyne/ω-azide linear precursors. It is observed that such amphiphilic macrocycles exhibit increased glass transition temperatures (Tg ), slightly faster trans-cis-trans photoisomerization, and enhanced fluorescence emission intensity compared with the corresponding linear polymers. In addition, the cyclic amphiphilic homopolymers self-assemble into spherical nanoparticles with smaller sizes which possess slower photoresponsive behaviors in a tetrahydrofuran/water mixture compared with those of the linear ones. All these interesting observations suggest that the cyclic topology has a great influence on the physical properties and self-assembly behavior of these photoresponsive amphiphilic macrocycles in general. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Facially amphiphilic thiol capped gold and silver nanoparticles

    Indian Academy of Sciences (India)

    Wintec

    *For correspondence. Also at the Chemical Biology Unit,. Jawaharlal Nehru Centre for Advanced Scientific Research,. Bangalore 560 064. Facially amphiphilic thiol capped gold and silver nanoparticles. †. SHREEDHAR BHAT a and UDAY MAITRA*. Department of Organic Chemistry, Indian Institute of Science, Bangalore ...

  10. Effects of perfluorinated amphiphiles on backward swimming in Paramecium caudatum

    International Nuclear Information System (INIS)

    Matsubara, Eriko; Harada, Kouji; Inoue, Kayoko; Koizumi, Akio

    2006-01-01

    PFOS and PFOA are ubiquitous contaminants in the environment. We investigated the effects of fluorochemicals on calcium currents in Paramecium caudatum using its behavioral changes. Negatively charged amphiphiles prolonged backward swimming (BWS) of Paramecium. PFOS significantly prolonged BWS, while PFOA was less potent (EC 5 : 29.8 ± 4.1 and 424.1 ± 124.0 μM, respectively). The BWS prolongation was blocked by cadmium, indicating that the cellular calcium conductance had been modified. The positively charged amphiphile FOSAPrTMA shortened BWS (EC 5 : 19.1 ± 17.3). Nonionic amphiphiles did not affect BWS. The longer-chain perfluorinated carboxylates PFNA and PFDA were more potent than PFOA (EC 5 : 98.7 ± 20.1 and 60.4 ± 10.1 μM, respectively). However, 1,8-perfluorooctanedioic acid and 1,10-perfluorodecanedioic acid did not prolong BWS. The critical micelle concentration (CMC) and BWS prolongation for negatively charged amphiphiles showed a clear correlation (r 2 = 0.8008, p < 0.001). In summary, several perfluorochemicals and PFOS and PFOA had similar effects in Paramecium, while chain length, CMC, and electric charge were major determinants of BWS duration

  11. Reinforcement of latex rubber by the incorporation of amphiphilic particles

    Science.gov (United States)

    Latex rubbers are fabricated from latex suspensions. During the fabrication process, latex particles are bound together while water is removed from the suspension. This report shows that the mechanical properties of latex rubbers can be improved by incorporating a small amount of amphiphilic submicr...

  12. Biocompatible Amphiphilic Hydrogel-Solid Dimer Particles as Colloidal Surfactants.

    Science.gov (United States)

    Chen, Dong; Amstad, Esther; Zhao, Chun-Xia; Cai, Liheng; Fan, Jing; Chen, Qiushui; Hai, Mingtan; Koehler, Stephan; Zhang, Huidan; Liang, Fuxin; Yang, Zhenzhong; Weitz, David A

    2017-12-26

    Emulsions of two immiscible liquids can slowly coalesce over time when stabilized by surfactant molecules. Pickering emulsions stabilized by colloidal particles can be much more stable. Here, we fabricate biocompatible amphiphilic dimer particles using a hydrogel, a strongly hydrophilic material, and achieve large contrast in the wetting properties of the two bulbs, resulting in enhanced stabilization of emulsions. We generate monodisperse single emulsions of alginate and shellac solution in oil using a flow-focusing microfluidics device. Shellac precipitates from water and forms a solid bulb at the periphery of the droplet when the emulsion is exposed to acid. Molecular interactions result in amphiphilic dimer particles that consist of two joined bulbs: one hydrogel bulb of alginate in water and the other hydrophobic bulb of shellac. Alginate in the hydrogel compartment can be cross-linked using calcium cations to obtain stable particles. Analogous to surfactant molecules at the interface, the resultant amphiphilic particles stand at the water/oil interface with the hydrogel bulb submerged in water and the hydrophobic bulb in oil and are thus able to stabilize both water-in-oil and oil-in-water emulsions, making these amphiphilic hydrogel-solid particles ideal colloidal surfactants for various applications.

  13. On the slowdown mechanism of water dynamics around small amphiphiles

    NARCIS (Netherlands)

    Homsi Brandeburgo, W.; Thijmen van der Post, S.; Meijer, E.J.; Ensing, B.

    2015-01-01

    Aqueous solvation of small amphiphilic molecules exhibits a unique and complex dynamics, that is only partially understood. A recent series of studies on the hydration of small organic compounds, such as tetramethylurea (TMU), trimethylamine N-oxide (TMAO) and urea, has provided strong evidence of a

  14. Modulated self-organization in complex amphiphilic systems

    NARCIS (Netherlands)

    Sevink, A; Zvelindovsky, A; Fraaije, H

    2000-01-01

    We discuss novel simulation methods for 3D pattern formation in complex amphiphilic systems. The focus is on the supra-molecular or mesoscopic level. The building blocks consist of sequences of dissimilar monomers, connected in copolymer chain molecules. Internal factors such as composition and

  15. Modulated self-organization in complex amphiphilic systems

    NARCIS (Netherlands)

    Fraaije, JGEM; Zvelindovsky, AV; Sevink, GJA; Maurits, NM

    2000-01-01

    We discuss novel simulation methods for 3D pattern formation in complex amphiphilic systems. The focus is on the supra-molecular or mesoscopic level. The building blocks consist of sequences of dissimilar monomers. connected in copolymer chain molecules. Internal factors such as composition and

  16. Nucleic acid amphiphiles : synthesis and self-assembled nanostructures

    NARCIS (Netherlands)

    Kwak, Minseok; Herrmann, Andreas; Clever, Guido; Mao, Chengde; Shionoya, Mitsuhiko; Stulz, Eugen

    2011-01-01

    This review provides an overview of a relatively new class of bio-conjugates, DNA amphiphiles, which consist of oligonucleotides covalently bonded to synthetic hydrophobic units. The reader will find the basic principles for the structural design and preparation methods of the materials. Moreover,

  17. Self-assembly of fibronectin mimetic peptide-amphiphile nanofibers

    Science.gov (United States)

    Rexeisen, Emilie Lynn

    Many therapeutic strategies incorporate peptides into their designs to mimic the natural protein ligands found in vivo. A few examples are the short peptide sequences RGD and PHSRN that mimic the primary and synergy-binding domains of the extracellular matrix protein, fibronectin, which is recognized by the cell surface receptor, alpha5beta 1 integrin. Even though scaffold modification with biomimetic peptides remains one of the most promising approaches for tissue engineering, the use of these peptides in therapeutic tissue-engineered products and drug delivery systems available on the commercial market is limited because the peptides are not easily able to mimic the natural protein. The design of a peptide that can effectively target the alpha5beta1 integrin would greatly increase biomimetic scaffold therapeutic potential. A novel peptide containing both the RGD primary binding domain and PHSRN synergy-binding domain for fibronectin joined with the appropriate linker should bind alpha 5beta1 integrin more efficiently and lead to greater cell adhesion over RGD alone. Several fibronectin mimetic peptides were designed and coupled to dialkyl hydrocarbon tails to make peptide-amphiphiles. The peptides contained different linkers connecting the two binding domains and different spacers separating the hydrophobic tails from the hydrophilic headgroups. The peptide-amphiphiles were deposited on mica substrates using the Langmuir-Blodgett technique. Langmuir isotherms indicated that the peptide-amphiphiles that contained higher numbers of serine residues formed a more tightly packed monolayer, but the increased number of serines also made transferring the amphiphiles to the mica substrate more difficult. Atomic force microscopy (AFM) images of the bilayers showed that the headgroups might be bent, forming small divots in the surface. These divots may help expose the PHSRN synergy-binding domain. Parallel studies undertaken by fellow group members showed that human

  18. Multiple patterns of diblock copolymer confined in irregular geometries with soft surface

    Science.gov (United States)

    Li, Ying; Sun, Min-Na; Zhang, Jin-Jun; Pan, Jun-Xing; Guo, Yu-Qi; Wang, Bao-Feng; Wu, Hai-Shun

    2015-12-01

    The different confinement shapes can induce the formation of various interesting and novel morphologies, which might inspire potential applications of materials. In this paper, we study the directed self-assembly of diblock copolymer confined in irregular geometries with a soft surface by using self-consistent field theory. Two types of confinement geometries are considered, namely, one is the concave pore with one groove and the other is the concave pore with two grooves. We obtain more novel and different structures which could not be produced in other two-dimensional (2D) confinements. Comparing these new structures with those obtained in regular square confinement, we find that the range of ordered lamellae is enlarged and the range of disordered structure is narrowed down under the concave pore confinement. We also compare the different structures obtained under the two types of confinement geometries, the results show that the effect of confinement would increase, which might induce the diblock copolymer to form novel structures. We construct the phase diagram as a function of the fraction of B block and the ratio of h/L of the groove. The simulation reveals that the wetting effect of brushes and the shape of confinement geometries play important roles in determining the morphologies of the system. Our results improve the applications in the directed self-assembly of diblock copolymer for fabricating the irregular structures. Project supported by the Specialized Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20121404110004), the Research Foundation for Excellent Talents of Shanxi Provincial Department of Human Resources and Social Security, China, and the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi Province, China.

  19. Mesomorphic phase behaviour of low molar mass PEP-PDMS diblock copolymers synthesized by anionic polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Vigild, M.E.

    1997-10-01

    The phase behaviour of low molar mass poly(ethylene-alt-propylene) -poly(dimethylsiloxane) (PEP-PDMS) is investigated in this thesis by the combination of dynamical mechanical spectroscopy (rheology) to measure phase transition temperatures, and small-angle x-ray scattering to identify the morphology of encountered phases. Samples of PEP-PDMS in the range of 0.2-0.7 in volume fraction of PEP are studied. This diblock copolymer system exhibits the three classical phases of lamellar sandwich structure (LAM), hexagonally packed cylinders (HEX), and spheres arranged on a body centered cubic lattice (BCC). Furthermore the gyroid phase (Ia3d symmetry) of two interpenetrating networks was also identified as a stable phase of the PEP-PDMS system. Time resolved measurements of small-angle neutron scattering in tandem with simultaneous in-situ rheological measurements are performed on samples showing transitions between different ordered phases. The identification of especially the BCC and gyroid phases from scattering experiments is treated. By performing mesoscopic crystallographic measurements using a custom built goniometer it was unambiguously shown that the application of shear to an unoriented powder-like sample introduces uniaxial orientation of the gyroid phase. The orientation of the ordered phase is otherwise random, causing a two-dimensional powder. Finally this dissertation presents a discussion of relevant parameters for the description of diblock copolymer phase behaviour together with descriptions of anionic polymerization for the synthesis of copolymers, and various experimental techniques for the characterization of diblocks. (au). 9 tabs., 40 ills., 81 refs.

  20. Diblock Polyelectrolytic Copolymers Containing Cationic Iron and Cobalt Sandwich Complexes: Living ROMP Synthesis and Redox Properties.

    Science.gov (United States)

    Gu, Haibin; Ciganda, Roberto; Hernandez, Ricardo; Castel, Patricia; Zhao, Pengxiang; Ruiz, Jaime; Astruc, Didier

    2016-04-01

    Diblock metallopolymer polyelectrolytes containing the two redox-robust cationic sandwich units [CoCp'Cp](+) and [FeCp'(η(6)-C6 Me6)](+) (Cp = η(5)-C5 H5; Cp' = η(5)-C5H4-) as hexafluorophosphate ([PF6](-)) salts are synthesized by ring-opening metathesis polymerization using Grubbs' third generation catalyst. Their electrochemical properties show full chemical and electrochemical reversibilities allowing fine determination of the copolymer molecular weight using Bard-Anson's electrochemical method by cyclic voltammetry. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Novel synthesis of cellulose-based diblock copolymer of poly(hydroxyethyl methacrylate) by mechanochemical reaction.

    Science.gov (United States)

    Ohura, Takeshi; Tsutaki, Yusaku; Sakaguchi, Masato

    2014-01-01

    The mechanical fracture of polymer produces polymeric free radical chain-ends, by which liner block copolymers have been synthesized. A diblock copolymer of microcrystalline cellulose (MCC) and poly 2-hydroxyethyl methacrylate (pHEMA) was produced by the mechanochemical polymerization under vacuum and room temperature. The fraction of pHEMA in MCC-block-pHEMA produced by the mechanochemical polymerization increased up to 21 mol% with increasing fracture time (~6 h). Then, the tacticities of HEMA sequences in MCC-block-pHEMA varied according to the reaction time. In the process of mechanochemical polymerization, cellulose could play the role of a radical polymerization initiator capable of controlling stereoregularity.

  2. 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.

  3. Development of polycationic amphiphilic cyclodextrin nanoparticles for anticancer drug delivery

    Directory of Open Access Journals (Sweden)

    Gamze Varan

    2017-07-01

    Full Text Available Background: Paclitaxel is a potent anticancer drug that is effective against a wide spectrum of cancers. To overcome its bioavailability problems arising from very poor aqueous solubility and tendency to recrystallize upon dilution, paclitaxel is commercially formulated with co-solvents such as Cremophor EL® that are known to cause serious side effects during chemotherapy. Amphiphilic cyclodextrins are favored oligosaccharides as drug delivery systems for anticancer drugs, having the ability to spontaneously form nanoparticles without surfactant or co-solvents. In the past few years, polycationic, amphiphilic cyclodextrins were introduced as effective agents for gene delivery in the form of nanoplexes. In this study, the potential of polycationic, amphiphilic cyclodextrin nanoparticles were evaluated in comparison to non-ionic amphiphilic cyclodextrins and core–shell type cyclodextrin nanoparticles for paclitaxel delivery to breast tumors. Pre-formulation studies were used as a basis for selecting the suitable organic solvent and surfactant concentration for the novel polycationic cyclodextrin nanoparticles. The nanoparticles were then extensively characterized with particle size distribution, polydispersity index, zeta potential, drug loading capacity, in vitro release profiles and cytotoxicity studies.Results: Paclitaxel-loaded cyclodextrin nanoparticles were obtained in the diameter range of 80−125 nm (depending on the nature of the cyclodextrin derivative where the smallest diameter nanoparticles were obtained with polycationic (PC βCDC6. A strong positive charge also helped to increase the loading capacity of the nanoparticles with paclitaxel up to 60%. Interestingly, cyclodextrin nanoparticles were able to stabilize paclitaxel in aqueous solution for 30 days. All blank cyclodextrin nanoparticles were demonstrated to be non-cytotoxic against L929 mouse fibroblast cell line. In addition, paclitaxel-loaded nanoparticles have a

  4. Activated Porous Carbon Spheres with Customized Mesopores through Assembly of Diblock Copolymers for Electrochemical Capacitor.

    Science.gov (United States)

    Tang, Jing; Wang, Jie; Shrestha, Lok Kumar; Hossain, Md Shahriar A; Alothman, Zeid Abdullah; Yamauchi, Yusuke; Ariga, Katsuhiko

    2017-06-07

    A series of porous carbon spheres with precisely adjustable mesopores (4-16 nm), high specific surface area (SSA, ∼2000 m 2 g -1 ), and submicrometer particle size (∼300 nm) was synthesized through a facile coassembly of diblock polymer micelles with a nontoxic dopamine source and a common postactivation process. The mesopore size can be controlled by the diblock polymer, polystyrene-block-poly(ethylene oxide) (PS-b-PEO) templates, and has an almost linear dependence on the square root of the degree of polymerization of the PS blocks. These advantageous structural properties make the product a promising electrode material for electrochemical capacitors. The electrochemical capacitive performance was studied carefully by using symmetrical cells in a typical organic electrolyte of 1 M tetraethylammonium tetrafluoroborate/acetonitrile (TEA BF 4 /AN) or in an ionic liquid electrolyte of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF 4 ), displaying a high specific capacitance of 111 and 170 F g -1 at 1 A g -1 , respectively. The impacts of pore size distribution on the capacitance performance were thoroughly investigated. It was revealed that large mesopores and a relatively low ratio of micropores are ideal for realizing high SSA-normalized capacitance. These results provide us with a simple and reliable way to screen future porous carbon materials for electrochemical capacitors and encourage researchers to design porous carbon with high specific surface area, large mesopores, and a moderate proportion of micropores.

  5. Numerical investigation of the contraction of neutral-charged diblock copolymer brushes in electric fields

    International Nuclear Information System (INIS)

    Chen, Yuwei; Li, Haiming; Zhu, Yuejin; Tong, Chaohui

    2016-01-01

    Using self-consistent field theory (SCFT), the contraction of neutral-charged A-B diblock copolymer brushes in electric fields generated by opposite surface charges on two parallel electrodes has been numerically investigated. The diblock copolymer chains were grafted with the free end of the neutral block to one electrode and immersed in a salt-free solution sandwiched between the two electrodes. The numerical results reveal that the charged monomers, A-B joint segment and the tail exhibit bimodal distributions under external electric fields, which are absent for homopolymer polyelectrolyte brushes. The dependences of the relative populations and peak positions of the two modes on various parameters such as block ratio, grafting density, chain length and strength of the applied electric field were systematically examined and the underlining mechanisms were elucidated. It was found in this study that, if the total amount of surface charges on the grafting electrode is no more than that of the counter-ions in the system, overall charge neutrality is generally maintained inside the brushes when including the contribution of surface charges on the grafting electrode. In such a case, the counter-ions expelled from the brushes are highly enriched in the immediate vicinity of the second electrode and an approximate charge balance between these expelled counter-ions and the opposite surface charges on the second electrode is achieved. (paper)

  6. Nanoscale protein arrays of rich morphologies via self-assembly on chemically treated diblock copolymer surfaces

    International Nuclear Information System (INIS)

    Song Sheng; Milchak, Marissa; Zhou Hebing; Lee, Thomas; Hanscom, Mark; Hahm, Jong-in

    2013-01-01

    Well-controlled assembly of proteins on supramolecular templates of block copolymers can be extremely useful for high-throughput biodetection. We report the adsorption and assembly characteristics of a model antibody protein to various polystyrene-block-poly(4-vinylpyridine) templates whose distinctive nanoscale structures are obtained through time-regulated exposure to chloroform vapor. The strong adsorption preference of the protein to the polystyrene segment in the diblock copolymer templates leads to an easily predictable, controllable, rich set of nanoscale protein morphologies through self-assembly. We also demonstrate that the chemical identities of various subareas within individual nanostructures can be readily elucidated by investigating the corresponding protein adsorption behavior on each chemically distinct area of the template. In our approach, a rich set of intricate nanoscale morphologies of protein arrays that cannot be easily attained through other means can be generated straightforwardly via self-assembly of proteins on chemically treated diblock copolymer surfaces, without the use of clean-room-based fabrication tools. Our approach provides much-needed flexibility and versatility for the use of block copolymer-based protein arrays in biodetection. The ease of fabrication in producing well-defined and self-assembled templates can contribute to a high degree of versatility and simplicity in acquiring an intricate nanoscale geometry and spatial distribution of proteins in arrays. These advantages can be extremely beneficial both for fundamental research and biomedical detection, especially in the areas of solid-state-based, high-throughput protein sensing. (paper)

  7. Diffusion of surface-active amphiphiles in silicone-based fouling-release coatings

    DEFF Research Database (Denmark)

    Noguer, Albert Camós; Olsen, S. M.; Hvilsted, Søren

    2017-01-01

    Amphiphiles (i.e. amphiphilic molecules such as surfactants, block copolymers and similar compounds) are used in small amounts to modify the surface properties of polymeric materials. In silicone fouling-release coatings, PEG-based amphiphiles are added to provide biofouling-resistance. The success...... of the amphiphiles shows a weak dependency on their molecular weight, although this dependency is much less pronounced than for other rubbery polymeric materials. The biofouling-resistance properties in fouling-release coatings were also studied for these amphiphiles. It was found that the diffusion coefficient does...... not have any influence on the biofouling-resistance results for the studied compounds. Instead, the chemistry of the hydrophobic block of the amphiphiles is much more significant, with PEG-PDMS block copolymers showing the best properties among the studied compounds....

  8. Drug release from hydrazone-containing peptide amphiphiles

    Science.gov (United States)

    Matson, John B.; Stupp, Samuel I.

    2012-01-01

    Hydrolytically-labile hydrazones in peptide amphiphiles were studied as degradable tethers for drug release from nanofiber gels. On-resin addition of the novel compound tri-Bochydrazido adipic acid to a lysine ε-amine allowed for precise placement of a hydrazide in a peptide sequence. Hydrazone formation and hydrolysis were examined by addition and release of nabumetone froma peptide amphiphilematrix. PMID:21674107

  9. Magnetic Amphiphilic Composites Applied for the Treatment of Biodiesel Wastewaters

    OpenAIRE

    Bruno R. S. Lemos; Ana Paula C. Teixeira; José D. Ardisson; Waldemar A. A. Macedo; Luis E. Fernandez-Outon; Camila C. Amorim; Flávia C. C. Moura; Rochel M. Lago

    2012-01-01

    In this work, new magnetic amphiphilic composites were prepared by chemical vapor deposition with ethanol on the surface of hydrophilic natural chrysotile matrix containing Fe catalyst. XRD, Raman, Mössbauer and SEM analyses suggest the formation of a complex nanostructured material composed of hydrophobic carbon nanotubes/nanofibers grown on the hydrophilic surface of the MgSi fiber mineral and the presence of Fe metallic nanoparticles coated by carbon. These nanostructured particles show am...

  10. Relation between structure and organisation properties of new amphiphilic cyclodextrins

    International Nuclear Information System (INIS)

    Moutard, Stephane

    2003-01-01

    Since a number of years, special attention and efforts have been made to prepare amphiphilic cyclodextrins (CDs) with the objective to use them to obtain supramolecular assemblies as such or in the presence of preformed lipidic structures. The aim of these investigation is in both cases to combine the size specificity of cyclodextrins for guests and the transport properties of phospho-lipidic structures. The final objects could be of importance to transport or target biologically relevant molecules such as drugs using new galenic formulations. In a first step, a new family of amphiphilic CDs was prepared from a pure phospholipids (DMPE) onto cyclodextrins or methylated derivatives through a spacing arm. The afforded compounds (phospholipidyl-cyclodextrins) were fully characterized by high field NMR and high resolution mass spectrometry. The methylated derivatives were shown to self-organize in water with low CMC to form fluctuating micellar fibers retaining the inclusion capacity of the cyclodextrin cavities. The interactions of these compounds with membrane systems were investigated as black films using X-ray reflectivity and by evaluation of their detergent power towards model DMPC liposomes. Their ability to cross over the Blood Brain Barrier was evidenced by a new approach making use of novel immuno-enzymatic assays. In a second step, a new class of amphiphilic cyclodextrins was considered (peptidolipidyl-cyclodextrins). Although they are structurally similar to phospholipidyl-CDs, their preparation overcomes the tedious steps of the later and lead to a considerable versatility in terms of the number of possible molecules to be prepared. Moreover, the stability problems encountered with phospholipids are avoided. Several examples have been prepared, fully characterized and their organization properties investigated by the determination of CMC and by deuterium NMR on a pure and homogeneous mixed peptidolipidyl-CD / DMPC lamellar phase. This novel class of

  11. Nanorings from the self-assembly of amphiphilic molecular dumbbells.

    Science.gov (United States)

    Kim, Jung-Keun; Lee, Eunji; Huang, Zhegang; Lee, Myongsoo

    2006-11-01

    We have prepared amphiphilic dumbbell molecules consisting of hydrophobic alkyl chains and hydrophilic oligoether dendrons at each end of the rod segment. The molecular dumbbells, in aqueous solution, self-assemble into toroids as an intermediate nanostructure between spherical and long cylindrical micelles. The formation of toroidal structure is likely to originate from side by side connections of discrete bundles through the combination of strong hydrophobic interactions and anisotropic aggregation of rod segments.

  12. Recent Advances in the Chemistry of Glycoconjugate Amphiphiles.

    Science.gov (United States)

    Latxague, Laurent; Gaubert, Alexandra; Barthélémy, Philippe

    2018-01-02

    Glyconanoparticles essentially result from the (covalent or noncovalent) association of nanometer-scale objects with carbohydrates. Such glyconanoparticles can take many different forms and this mini review will focus only on soft materials (colloids, liposomes, gels etc.) with a special emphasis on glycolipid-derived nanomaterials and the chemistry involved for their synthesis. Also this contribution presents Low Molecular Weight Gels (LMWGs) stabilized by glycoconjugate amphiphiles. Such soft materials are likely to be of interest for different biomedical applications.

  13. Preparation and self-folding of amphiphilic DNA origami.

    Science.gov (United States)

    Zhou, Chao; Wang, Dianming; Dong, Yuanchen; Xin, Ling; Sun, Yawei; Yang, Zhongqiang; Liu, Dongsheng

    2015-03-01

    Amphiphilic DNA origami is prepared by dressing multiple hydrophobic molecules on a rectangular single layer DNA origami, which is then folded or coupled in sandwich-like structures with two outer DNA origami layer and one inner hydrophobic molecules layer. The preference to form different kinds of structures could be tailored by rational design of DNA origami. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Collective dynamics and self-diffusion in a diblock copolymer melt in the body-centered cubic phase

    Czech Academy of Sciences Publication Activity Database

    Papadakis, C.; Rittig, F.; Almdal, K.; Mortensen, K.; Štěpánek, Petr

    2004-01-01

    Roč. 15, č. 4 (2004), s. 359-370 ISSN 1292-8941 R&D Projects: GA ČR GA203/02/1262 Keywords : diblock copolymer * small-angle neutron scattering * dynamic light scattering Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.903, year: 2004

  15. Annealing-Induced Changes in Double-Brush Langmuir-Blodgett Films of alpha-Helical Diblock Copolypeptides

    NARCIS (Netherlands)

    Nguyen, Le-Thu T.; Musser, Andrew J.; Vorenkamp, Eltjo J.; Polushkin, Evgeny; ten Brinke, Gerrit; Schouten, Arend J.

    2010-01-01

    The effect of annealing on the structure and the helix orientation in Langmuir-Blodgett (LB) monolayers of diblock copolymers (PLGA-b-PMLGSLGs) of poly(alpha-L-glutamic acid) (PLGA) and poly(gamma-methyl-L-glutamate-ran-gamma-stearyl-L-glutamate) with 30 mol % of stearyl substituents (PMLGSLG) with

  16. Crossover from 3D ising to isotropic Lifshitz critical behavior in a mixture of a homopolymer blend and diblock copolymer

    DEFF Research Database (Denmark)

    Schwahn, D.; Mortensen, K.; Frielinghaus, H.

    1999-01-01

    Thermal composition fluctuations and the associated crossover from the 3D Ising to the isotropic Lifshitz universality class have been studied in a three component mixture made of a critical polymer blend and the corresponding diblock copolymer. The critical exponents were found to be appreciably...

  17. 3D-ising and Lifshitz critical behavior in a mixture of a polymer blend and a corresponding diblock copolymer

    DEFF Research Database (Denmark)

    Schwahn, D.; Mortensen, K.; Frielinghaus, H.

    2000-01-01

    Thermal composition fluctuations and the associated crossover from the 3D-Ising to the isotropic Lifshitz universality class have been studied in a three-component mixture made of a critical polymer blend and the corresponding diblock copolymer. The rather complex phase diagram and the critical...

  18. A pulsed field gradient NMR study of a ternary homopolymer/diblock copolymer blend in the bicontinuous microemulsion phase

    Czech Academy of Sciences Publication Activity Database

    Gröger, S.; Rittig, F.; Stallmach, F.; Almdal, K.; Štěpánek, Petr; Papadakis, C. M.

    2002-01-01

    Roč. 117, č. 1 (2002), s. 396-406 ISSN 0021-9606 R&D Projects: GA AV ČR IAA1050902 Institutional research plan: CEZ:AV0Z4050913 Keywords : polymer blend s * diblock copolymer * dynamic light scattering Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.998, year: 2002

  19. A theoretical and simulation study of the self-assembly of a binary blend of diblock copolymers

    KAUST Repository

    Padmanabhan, Poornima

    2012-01-01

    Pure diblock copolymer melts exhibit a narrow range of conditions at which bicontinuous and cocontinuous phases are stable; such conditions and the morphology of such phases can be tuned by the use of additives. In this work, we have studied a bidisperse system of diblock copolymers using theory and simulation. In particular, we elucidated how a short, lamellar-forming diblock copolymer modifies the phase behavior of a longer, cylinder-forming diblock copolymer. In a narrow range of intermediate compositions, self-consistent field theory predicts the formation of a gyroid phase although particle-based simulations show that three phases compete: the gyroid phase, a disordered cocontinuous phase, and the cylinder phase, all having free energies within error bars of each other. Former experimental studies of a similar system have yielded an unidentified, partially irregular bicontinuous phase, and our simulations suggest that at such conditions the formation of a partially transformed network phase is indeed plausible. Close examination of the spatial distribution of chains reveals that packing frustration (manifested by chain stretching and low density spots) occurs in the majority-block domains of the three competing phases simulated. In all cases, a double interface around the minority-block domains is also detected with the outer one formed by the short chains, and the inner one formed by the longer chains. © 2012 American Institute of Physics.

  20. Durability and Performance of Polystyrene-b-Poly(vinylbenzyl trimethylammonium) Diblock Copolymer and Equivalent Blend Anion Exchange Membranes

    Science.gov (United States)

    2015-01-01

    PS/PVBC, as the diblock copolymer. Film Formation The polymers in a powder form, or beads for PS, were mixed with toluene at a concentration of 0.3 g...mem- branes in 1M sodium bicarbonate solutions for 48 h. Standar- dized silver nitrate solution, 0.0235M, was used to titrate the membrane solutions

  1. Mode-coupling theory of self-diffusion in diblock copolymers. II. Model calculations and experimental comparisons

    International Nuclear Information System (INIS)

    Guenza, M.; Schweizer, K.S.

    1998-01-01

    The predictions of polymer-mode-coupling theory for self-diffusion in entangled structurally and interaction symmetric diblock copolymer fluids are illustrated by explicit numerical calculations. We find that retardation of translational motion emerges near and somewhat below the order endash disorder transition (ODT) in an approximately exponential and/or thermally activated manner. At fixed reduced temperature, suppression of diffusion is enhanced with increasing diblock molecular weight, compositional symmetry, and/or copolymer concentration. At very low temperatures, a new entropic-like regime of mobility suppression is predicted based on an isotropic supercooled liquid description of the copolymer structure. Preliminary generalization of the theory to treat diblock tracer diffusion is also presented. Quantitative applications to recent self and tracer diffusion measurements on compositionally symmetric polyolefin diblock materials have been carried out, and very good agreement between theory and experiment is found. Asymmetry in block local friction constants is predicted to significantly influence mobility suppression, with the largest effects occurring when the minority block is also the high friction species. New experiments to further test the predictions of the theory are suggested. copyright 1998 American Institute of Physics

  2. Synthesis and performance of amphiphilic copolymers for blood cell separation.

    Science.gov (United States)

    Natori, Shizue Hayashi; Gomei, Yumiko; Higuchi, Akon

    2006-08-01

    Three types of amphiphilic copolymers using n-butylmethacrylate (BMA) as a hydrophobic monomer, and each of N,N'-dimethylacrylamide (DMA), N-acryloylmorpholine (AMO), and N-vinylpyrrolidone (VP) as hydrophilic comonomers were synthesized for coating filters used to remove leukocytes. The influence of the amphiphilic property of the resulting filters, which were composed of nonwoven fabrics coated with the above copolymers, on leukocyte removal and platelet permeation through the filters from whole blood was investigated. The platelet permeation ratio through hydrophobic noncoated filters was only 0.2%, because platelets in whole blood adhered easily to the hydrophobic filter material. However, filters coated with poly(AMO-co-BMA) of high AMO content showed a much higher platelet permeation ratio (nearly 90%). Further, the filters coated with poly(DMA-co-BMA) also showed high permeation ratios of platelets (more than 78%) over a broad range of DMA content in the copolymer. On the other hand, the coated filters showed slightly a higher permeation ratio of leukocytes than did the noncoated filters, resulting from the increase in hydrophilicity of the surface of the filters. Moreover, the coating of the amphiphilic copolymers on the surface of the nonwoven fabrics may have affected the pore size of the filters, affecting the permeation ratio of leukocytes more strongly than that of platelets. The coated filters effectively improved platelet permeation through the filters, with a slight increase in the permeation ratio of leukocytes.

  3. Amphiphiles Self-Assembly: Basic Concepts and Future Perspectives of Supramolecular Approaches

    Directory of Open Access Journals (Sweden)

    Domenico Lombardo

    2015-01-01

    Full Text Available Amphiphiles are synthetic or natural molecules with the ability to self-assemble into a wide variety of structures including micelles, vesicles, nanotubes, nanofibers, and lamellae. Self-assembly processes of amphiphiles have been widely used to mimic biological systems, such as assembly of lipids and proteins, while their integrated actions allow the performance of highly specific cellular functions which has paved a way for bottom-up bionanotechnology. While amphiphiles self-assembly has attracted considerable attention for decades due to their extensive applications in material science, drug and gene delivery, recent developments in nanoscience stimulated the combination of the simple approaches of amphiphile assembly with the advanced concept of supramolecular self-assembly for the development of more complex, hierarchical nanostructures. Introduction of stimulus responsive supramolecular amphiphile assembly-disassembly processes provides particularly novel approaches for impacting bionanotechnology applications. Leading examples of these novel self-assembly processes can be found, in fact, in biosystems where assemblies of different amphiphilic macrocomponents and their integrated actions allow the performance of highly specific biological functions. In this perspective, we summarize in this tutorial review the basic concept and recent research on self-assembly of traditional amphiphilic molecules (such as surfactants, amphiphile-like polymers, or lipids and more recent concepts of supramolecular amphiphiles assembly which have become increasingly important in emerging nanotechnology.

  4. Manipulating the surface active and anticoagulant properties of heparin through amphiphilic molecular constructs

    Science.gov (United States)

    Mintz, Rosita Candida

    Cardiovascular devices implanted within the vasculature are subjected to non-specific adsorption of plasma proteins. This initiates the blood coagulation cascade and platelet adhesion and activation, leading to thrombus formation. In this thesis Heparin Alkyl Diblock (HAD) surfactants were developed to improve the blood compatibility of cardiovascular biomaterials. The material designs involved using heparin, a natural anticoagulant, to inhibit coagulation pathway enzymes and mimic the cell glycocalyx to provide a repulsive force field to inhibit non-specific protein adsorption. Type AB linear (HAD Cn, n = 6,10,12,18) and branched (HAD nx 18, n = 2,3,4) heparin surfactants were synthesized by end point coupling primary and secondary alkyl amines to heparin via reductive amination. Surfactant yields (83--4%) and anticoagulant activity (149.8 +/- 3.7--39.6 +/- 0.6 IU/mg) decreased with increased branching and hydrocarbon number. Surfactant adsorption, self assembly and molecular packing of HAD surfactants at the air/liquid and liquid/solid interface were a function of the number of hydrocarbons in the surfactant alkyl segment and the presence or absence of an ionic liquid phase. Increased molecular packing was observed at the air/PBS and PBS/graphite interface, relative to aqueous interfaces, resulting from buffer cations shielding heparin's negatively charged sulfate and carboxyl groups. At the PBS/graphite interface, the surfactant's apparent heparin head group cross section decreased in diameter (1.84 to 1.05 nm) and increased in tilt angle (75.7 to 81.9°) with increasing alkyl carbon number (n = 6 to 18). The heparin head group reached a minimum diameter, equivalent to the surfactant's diameter at the air/PBS interface (0.57 nm) just prior to 36 hydrocarbons in the surfactant. For surfactants with 36 to 78 hydrocarbons, the surfactant's heparin head group oriented normal to the graphite surface and alkyl overlap or interdigitation increased (0.02 to 0.59 nm

  5. Complex and hierarchical micelle architectures from diblock copolymers using living, crystallization-driven polymerizations

    Science.gov (United States)

    Gädt, Torben; Ieong, Nga Sze; Cambridge, Graeme; Winnik, Mitchell A.; Manners, Ian

    2009-02-01

    Block copolymers consist of two or more chemically distinct polymer segments, or blocks, connected by a covalent link. In a selective solvent for one of the blocks, core-corona micelle structures are formed. We demonstrate that living polymerizations driven by the epitaxial crystallization of a core-forming metalloblock represent a synthetic tool that can be used to generate complex and hierarchical micelle architectures from diblock copolymers. The use of platelet micelles as initiators enables the formation of scarf-like architectures in which cylindrical micelle tassels of controlled length are grown from specific crystal faces. A similar process enables the fabrication of brushes of cylindrical micelles on a crystalline homopolymer substrate. Living polymerizations driven by heteroepitaxial growth can also be accomplished and are illustrated by the formation of tri- and pentablock and scarf architectures with cylinder-cylinder and platelet-cylinder connections, respectively, that involve different core-forming metalloblocks.

  6. Molecular Interaction Control in Diblock Copolymer Blends and Multiblock Copolymers with Opposite Phase Behaviors

    Science.gov (United States)

    Cho, Junhan

    2014-03-01

    Here we show how to control molecular interactions via mixing AB and AC diblock copolymers, where one copolymer exhibits upper order-disorder transition and the other does lower disorder-order transition. Linear ABC triblock copolymers possessing both barotropic and baroplastic pairs are also taken into account. A recently developed random-phase approximation (RPA) theory and the self-consistent field theory (SCFT) for general compressible mixtures are used to analyze stability criteria and morphologies for the given systems. It is demonstrated that the copolymer systems can yield a variety of phase behaviors in their temperature and pressure dependence upon proper mixing conditions and compositions, which is caused by the delicate force fields generated in the systems. We acknowledge the financial support from National Research Foundation of Korea and Center for Photofunctional Energy Materials.

  7. Small angle neutron scattering study on star di-block copolymers

    International Nuclear Information System (INIS)

    Ertugrul, O.

    2006-01-01

    Determining structural properties, phase transitions and stability of polymer mixtures is very important to produce new materials with desired and interesting properties. Small Angle Neutron Scattering Technique (SANS) has been one of the most powerful and intensely used methods for the characterization of polymers for last decades, m this study, we use a model based on Gaussian Random Phase Approximation (RPA) to describe Star Di-block Copolymers (SDC) mixtures with homo-polymers. We could able to predict the miscibility and phase transitions of the various mixtures along with their structure factors, producing a thermodynamic picture of the system. Also the results suggest that scattering intensity will be dictated by the structure factor of the core or shell parts of star polymer only, which depends on the homo-polymer type of the mixture

  8. Novel Synthesis of Cellulose-Based Diblock Copolymer of Poly(hydroxyethyl methacrylate by Mechanochemical Reaction

    Directory of Open Access Journals (Sweden)

    Takeshi Ohura

    2014-01-01

    Full Text Available The mechanical fracture of polymer produces polymeric free radical chain-ends, by which liner block copolymers have been synthesized. A diblock copolymer of microcrystalline cellulose (MCC and poly 2-hydroxyethyl methacrylate (pHEMA was produced by the mechanochemical polymerization under vacuum and room temperature. The fraction of pHEMA in MCC-block-pHEMA produced by the mechanochemical polymerization increased up to 21 mol% with increasing fracture time (~6 h. Then, the tacticities of HEMA sequences in MCC-block-pHEMA varied according to the reaction time. In the process of mechanochemical polymerization, cellulose could play the role of a radical polymerization initiator capable of controlling stereoregularity.

  9. Synthesis, Characterization and Photoinduction of Optical Anisotropy in Liquid Crystalline Diblock Azo-Copolymers

    DEFF Research Database (Denmark)

    Forcén, P; Oriol, L; Sánchez, C

    2007-01-01

    Diblock copolymers with polymethyl methacrylate and side chain liquid crystalline WC) azopolymethacrylate blocks were synthesized by atom transfer radical polymerization (ATRP). The azobeazene content in these copolymers ranges from 52 to 7 wt %. For an azo conteat dowri to 20% they exhibit a LC...... anisotropy induced in these films by illumination with linearly polarized 488 nm light was studied and the resuits compared with those of the azo homopolymer and of a random copolymer with a similar composition. The formation of azo aggregates inside the azo blocks is strongly reduced in going from...... the homopolymer to the copolymers. Photoinduced azo orientation perpendicular to the 488 nm light polarization was found in aH the polymers. The orientational order parameter is very similar in the homopolymer and in the block copolymers with an azo content down to 20 wt %, while it is much lower in the random...

  10. Nanopatterning of diblock copolymer directed self-assembly lithography with wet development

    Science.gov (United States)

    Muramatsu, Makoto; Iwashita, Mitsuaki; Kitano, Takahiro; Toshima, Takayuki; Seino, Yuriko; Kawamura, Daisuke; Kanno, Masahiro; Kobayashi, Katsutoshi; Azuma, Tsukasa

    2011-04-01

    We report wet development technique for directed self-assembly lithography pattern. For typical diblock copolymer, poly (styrene-block-methyl methacrylate) (PS-b-PMMA), the PMMA area is removed by O2 plasma. However, O2 plasma attack also etches off PS area simultaneously. As a result, the thickness of residual PS pattern is thinner and it causes degradation of PS mask performance. PS thickness loss in the device integration is not desirable as etching mask role. In this work, we applied wet development technique which could be higher selectivity to keep PS film thickness after pattern formation. Especially, we propose the method using low pressure mercury lamp and conventional TMAH (2.38%) as developer. It is expected to accomplish pattern formation in one track with coating, baking, exposure and development.

  11. Synthesis of Diblock Copolymer Consisting of Poly(4-butyltriphenylamine and Morphological Control in Photovoltaic Application

    Directory of Open Access Journals (Sweden)

    Malee Songeun

    2011-07-01

    Full Text Available The diblock copolymer PTPA-b-PS consisting of poly(4-butyltripheneylamine (PTPA and polystyrene was prepared by atom transfer radical polymerization followed by C–N coupling polymerization. Three types of block copolymers with different contents of polystyrene segment were prepared. The formation of block copolymer was confirmed by 1H NMR spectra and gel permeation chromatography (GPC profiles. Time of flight (TOF measurement revealed that the block copolymer showed higher hole mobility up to 1.3 × 10−4 cm2/Vs compared with PTPA homopolymer. The surface morphology of block copolymer films blended with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM was investigated by Atomic force microscopy (AFM. Introduction of polystyrene segment provided microphase-separated structures with domain sizes of around 20 nm. The photovoltaic device based on PTPA-b-PS, PTPA, and PCBM exhibited higher efficiency than that of homopolymer blend system.

  12. Selective Solvent Induced Reversible Surface Reconstruction of Diblock Copolymer Thin Films

    Energy Technology Data Exchange (ETDEWEB)

    Xu, T.; Misner, M.J.; Kim, S.; Sievert, J.D.; Gang, O.; Ocko, B.; Russell, T.P. (UMASS, Amherst); (BNL)

    2006-03-08

    Through the use of a selective solvent a reversible surface reconstruction of diblock copolymer thin films was observed. The solvent selectivity and solubility of the minor component block were found to be crucial to generate nanoporous films with pores that penetrate through entire film thickness. The process was shown to be reversible by thermal annealing and was easily monitored using in-situ grazing incidence small angle x-ray scattering and scanning force microscopy. At temperatures of 60-90 C, only a small fraction of the nanopores relaxed to regenerate the original nanotemplate. However, by heating to 90-100 C, the original nanotemplate was completely regenerated. Even though the bulk mobility of PS and PMMA is low at these temperatures, the local mobility required to regenerate the template was sufficient.

  13. Micelle Formation of Diblock Copolymers in Thin Film Homopolymers and Homopolymer Blends

    Science.gov (United States)

    Chen, Chelsea; Green, Peter

    2010-03-01

    A-b-B diblock copolymers, at very small concentrations, form micelles in a melt of homopolymer chains of type A or B. In the bulk, the critical micelle concentration, φcmc, is a function of the symmetry of the copolymer chain and exhibits a strong dependence on χN, where χ is the interaction parameter and N is the degree of polymerization of the copolymer. We examined micelle formation in thin film mixtures of: (1) polystyrene-b-poly(2-vinylpyridine) (PS-b-PVP)/polystyrene (PS); (2) PS-b-PVP/ blend of PS and tetramethyl bisphenol-A polycarbonate (TMPC); and (3) polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA)/PS. The critical micelle concentration is found to be orders of magnitude larger than the bulk; it is a strong function of film thickness, the substrate/chain segment interactions and the interactions between the different polymeric segments in the system.

  14. Thermoresponsive self-assembly of nanostructures from a collagen-like peptide-containing diblock copolymer.

    Science.gov (United States)

    Luo, Tianzhi; He, Lirong; Theato, Patrick; Kiick, Kristi L

    2015-01-01

    Temperature-triggered formation of nanostructures with distinct biological activity offers opportunities in selective modification of matrices and in drug delivery. Toward these ends, diblock polymers comprising poly(diethylene glycol methyl ether methacrylate) (PDEGMEMA) conjugated to a triple helix-forming collagen-like peptide were produced. Triggered by the collapse of the thermoresponsive domain above its LCST, the conjugate undergoes a reversible transition in aqueous solution to form well-defined nanovesicles with diameters of approximately 100 nm, with a transition temperature of 37 °C. The incorporation of CLP domains in these nanostructures may offer opportunities for the selective targeting of collagen-containing matrices. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. A Quantitative Study of Tethered Chains in Various Solution Conditions Using Langmuir Diblock Copolymer Monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Kent, Michael S.

    1999-08-13

    This article summarizes our investigations of tethered chain systems using Langmuir monolayer of polydimethysiloxane-poly styrene (PDMS-PS) diblock copolymers on organic liquids. In this system, the PDMS block adsorbs to the air surface while the PS block dangles into the subphase liquid. The air surface can be made either repulsive or attractive for the tethered PS chain segments by choosing a subphase liquid which has a surface tension lower or greater than that of PS, respectively. The segment profile of the PS block is determined by neutron reflection as a function of the surface density, the molecular weights of the PS and PDMS blocks, and the solution conditions. We cover the range of reduced surface density (SIGMA) characteristic of the large body of data in the literature for systems of chains tethered onto solid surfaces from dilute solution in good or theta solvent conditions (SIGMA < 12). We emphasize quantitative comparisons with analytical profile forms and scaling predictions. We find that the strong-stretching limit invoked in analytical SCF and scaling theories is not valid over this Z range. On the other hand, over a large portion of this range (SIGMA < 5) tethered layers are well described by a renormalization group theory addressing weakly interacting or noninteracting chains. Simultaneous with the study of the profile form, the free energy of the chains is examined through the surface tension. A strong increase in the surface pressure is observed with increasing surface density which determines the maximum surface density which can be achieved. This apparently nonequilibrium effect is attributed to steric interactions and limited lateral interpenetration. This effect may explain several outstanding discrepancies regarding the adsorption of end-functionalized chains and diblock copolymers onto solid surfaces.

  16. TOPICAL REVIEW: Nanofabrication of III-V semiconductors employing diblock copolymer lithography

    Science.gov (United States)

    Kuech, Thomas F.; Mawst, Luke J.

    2010-05-01

    To fully exploit the potential advantages of ideal quantum dots (QDs) (i.e. full 3D carrier confinement), elimination of the wetting layer and a uniform monomodal QD size distribution is needed. Nanopatterning with selective metalorganic chemical vapour deposition (MOCVD) QD growth has potential for achieving a higher degree of control over the QD formation, compared with the conventional Stranski-Krastanov (SK) self-assembly growth process. QD formation employing large surface area patterning prepared by dense nano-scale (20-30 nm diameter) diblock copolymer lithography is described. The resulting pattern consists of perpendicularly ordered cylindrical domain formed as part of a self-organizing diblock copolymer, such as polystyrene-block-poly(methylmethacrylate) (PS-b-PMMA). This pattern can be transferred to an underlying substrate or dielectric layer. Selective MOCVD growth of the QDs is achieved by employing the nanopatterned template mask. The resulting QD densities of 5 × 1010 cm-2 are comparable to densities achieved using the SK self-assembly growth mode. Nanopatterned growth yields a nearly monomodal QD size distribution. Variable temperature photoluminescence has been used to characterize the optical properties of capped InGaAs QDs on GaAs (λ ~ 1.1 µm) and InP (λ ~ 1.5 µm) substrates and preliminary results on the incorporation of such materials into diode laser structures are discussed. The extension of nanopatterned growth, beyond the pseudomorphic limit in the case of growth of strained-layer epitaxy, can lead to defect reduction and an improved morphology when compared with non-patterned growth.

  17. 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.

  18. Composition and method for self-assembly and mineralization of peptide amphiphiles

    Science.gov (United States)

    Stupp, Samuel I [Chicago, IL; Beniash, Elia [Newton, MA; Hartgerink, Jeffrey D [Houston, TX

    2009-06-30

    The present invention is directed to a composition useful for making homogeneously mineralized self assembled peptide-amphiphile nanofibers and nanofiber gels. The composition is generally a solution comprised of a positively or negatively charged peptide-amphiphile and a like signed ion from the mineral. Mixing this solution with a second solution containing a dissolved counter-ion of the mineral and/or a second oppositely charged peptide amphiphile, results in the rapid self assembly of the peptide-amphiphiles into a nanofiber gel and templated mineralization of the ions. Templated mineralization of the initially dissolved mineral cations and anions in the mixture occurs with preferential orientation of the mineral crystals along the fiber surfaces within the nanofiber gel. One advantage of the present invention is that it results in homogenous growth of the mineral throughout the nanofiber gel. Another advantage of the present invention is that the nanofiber gel formation and mineralization reactions occur in a single mixing step and under substantially neutral or physiological pH conditions. These homogeneous nanostructured composite materials are useful for medical applications especially the regeneration of damaged bone in mammals. This invention is directed to the synthesis of peptide-amphiphiles with more than one amphiphilic moment and to supramolecular compositions comprised of such multi-dimensional peptide-amphiphiles. Supramolecular compositions can be formed by self assembly of multi-dimensional peptide-amphiphiles by mixing them with a solution comprising a monovalent cation.

  19. Composition and method for self-assembly and mineralization of peptide-amphiphiles

    Science.gov (United States)

    Stupp, Samuel I [Chicago, IL; Beniash, Elia [Newton, MA; Hartgerink, Jeffrey D [Pearland, TX

    2012-02-28

    The present invention is directed to a composition useful for making homogeneously mineralized self assembled peptide-amphiphile nanofibers and nanofiber gels. The composition is generally a solution comprised of a positively or negatively charged peptide-amphiphile and a like signed ion from the mineral. Mixing this solution with a second solution containing a dissolved counter-ion of the mineral and/or a second oppositely charged peptide amphiphile, results in the rapid self assembly of the peptide-amphiphiles into a nanofiber gel and templated mineralization of the ions. Templated mineralization of the initially dissolved mineral cations and anions in the mixture occurs with preferential orientation of the mineral crystals along the fiber surfaces within the nanofiber gel. One advantage of the present invention is that it results in homogenous growth of the mineral throughout the nanofiber gel. Another advantage of the present invention is that the nanofiber gel formation and mineralization reactions occur in a single mixing step and under substantially neutral or physiological pH conditions. These homogeneous nanostructured composite materials are useful for medical applications especially the regeneration of damaged bone in mammals. This invention is directed to the synthesis of peptide-amphiphiles with more than one amphiphilic moment and to supramolecular compositions comprised of such multi-dimensional peptide-amphiphiles. Supramolecular compositions can be formed by self assembly of multi-dimensional peptide-amphiphiles by mixing them with a solution comprising a monovalent cation.

  20. Amphiphile regulation of ion channel function by changes in the bilayer spring constant

    DEFF Research Database (Denmark)

    Lundbæk, Jens August; Koeppe, R.E.; Andersen, Oluf Sten

    2010-01-01

    effect of amphiphiles, at concentrations often used in biological research, on the bilayer elastic response to a change in the hydrophobic length of an embedded protein. The effects of structurally diverse amphiphiles can be described by changes in a phenomenological bilayer spring constant (H...

  1. Trapping of polycyclic aromatic hydrocarbons by amphiphilic cyclodextrin functionalized polypropylene nonwovens

    DEFF Research Database (Denmark)

    Lumholdt, Ludmilla; Nielsen, Ronnie Bo Højstrup; Larsen, Kim Lambertsen

    of the textile fibers. In this study we present the ability of amphiphilic CD coated polypropylene nonwovens to trap 8 different polycyclic aromatic hydrocarbons/endocrine disruptors from aqueous solutions thus demonstrating the potential of using the amphiphilic cyclodextrins for water purification....

  2. Supra-amphiphiles: a new bridge between colloidal science and supramolecular chemistry.

    Science.gov (United States)

    Kang, Yuetong; Liu, Kai; Zhang, Xi

    2014-06-03

    In addition to conventional amphiphiles, an emerging research area is supra-amphiphiles, which are constructed on the basis of noncovalent interactions and dynamic covalent bonds. In this feature article, we have provided a general introduction to the concept, design principles, and topologies of supra-amphiphiles, starting from some rationally tailored building blocks. In addition, we highlight some progress in the functional assembly of supra-amphiphiles, such as responsive nanoscale carriers, antibacterial and antitumor agents, fluorescent-based chemical sensors, and enzyme mimics. The supra-amphiphile is a new bridge between colloidal science and supramolecular chemistry, and it is a field where we can make full use of our imaginative power.

  3. Exploring single chain amphiphile self-assembly and their possible roles in light transduction

    DEFF Research Database (Denmark)

    Monnard, Pierre-Alain

    2011-01-01

    amphiphiles on the early Earth seems reasonably well-documented either by exo-terrestrial delivery or endogeneous syntheses, a fact that singles them out as potential building blocks of primitive membranes. These studies have highlighted two important aspects of the self-assembly of single chain amphiphiles......Self-assembled structures of single-chain amphiphiles have been used as hosts for biochemical, and chemical reactions. Their use as models for protocells (i.e., precursors to the first biological cells) has been extensively researched by various groups because the availability of single chain...... source studied to date can supply one single type of amphiphile at concentrations conducive to self-assembly. Mixtures of single-chain amphiphiles were therefore proposed to better model primitive membranes and potentially enhance their structural integrity1-3. Recently, we have established that complex...

  4. Vesicles from Amphiphilic Dumbbells and Janus Dendrimers: Bioinspired Self-Assembled Structures for Biomedical Applications

    Directory of Open Access Journals (Sweden)

    Soraya Taabache

    2017-07-01

    Full Text Available The current review focuses on vesicles obtained from the self-assembly of two types of dendritic macromolecules, namely amphiphilic Janus dendrimers (forming dendrimersomes and amphiphilic dumbbells. In the first part, we will present some synthetic strategies and the various building blocks that can be used to obtain dendritic-based macromolecules, thereby showing their structural versatility. We put our focus on amphiphilic Janus dendrimers and amphiphilic dumbbells that form vesicles in water but we also encompass vesicles formed thereof in organic solvents. The second part of this review deals with the production methods of these vesicles at the nanoscale but also at the microscale. Furthermore, the influence of various parameters (intrinsic to the amphiphilic JD and extrinsic—from the environment on the type of vesicle formed will be discussed. In the third part, we will review the numerous biomedical applications of these vesicles of nano- or micron-size.

  5. 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

  6. 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.

  7. Structural Evolution of Low-Molecular-Weight Poly(ethylene oxide-block-polystyrene Diblock Copolymer Thin Film

    Directory of Open Access Journals (Sweden)

    Hui Wu

    2013-01-01

    Full Text Available The structural evolution of low-molecular-weight poly(ethylene oxide-block-polystyrene (PEO-b-PS diblock copolymer thin film with various initial film thicknesses on silicon substrate under thermal annealing was investigated by atomic force microscopy, optical microscopy, and contact angle measurement. At film thickness below half of the interlamellar spacing of the diblock copolymer (6.2 nm, the entire silicon is covered by a polymer brush with PEO blocks anchored on the Si substrate due to the substrate-induced effect. When the film is thicker than 6.2 nm, a dense polymer brush which is equal to half of an interlamellar layer was formed on the silicon, while the excess material dewet this layer to form droplets. The droplet surface was rich with PS block and the PEO block crystallized inside the bigger droplet to form spherulite.

  8. A self-consistent field study of diblock copolymer/charged particle system morphologies for nanofiltration membranes

    International Nuclear Information System (INIS)

    Zhang, Bo; Ye, Xianggui; Edwards, Brian J.

    2013-01-01

    A combination of self-consistent field theory and density functional theory was used to examine the stable, 3-dimensional equilibrium morphologies formed by diblock copolymers with a tethered nanoparticle attached either between the two blocks or at the end of one of the blocks. Both neutral and interacting particles were examined, with and without favorable/unfavorable energetic potentials between the particles and the block segments. The phase diagrams of the various systems were constructed, allowing the identification of three types of ordered mesophases composed of lamellae, hexagonally packed cylinders, and spheroids. In particular, we examined the conditions under which the mesophases could be generated wherein the tethered particles were primarily located within the interface between the two blocks of the copolymer. Key factors influencing these properties were determined to be the particle position along the diblock chain, the interaction potentials of the blocks and particles, the block copolymer composition, and molecular weight of the copolymer

  9. Highly-Ordered Magnetic Nanostructures on Self-Assembled α-Al2O3 and Diblock Copolymer Templates

    International Nuclear Information System (INIS)

    Erb, Denise

    2015-08-01

    This thesis shows the preparation of nanostructured systems with a high degree of morphological uniformity and regularity employing exclusively selfassembly processes, and documents the investigation of these systems by means of atomic force microscopy (AFM), grazing incidence small angle X-ray scattering (GISAXS), and nuclear resonant scattering of synchrotron radiation (NRS). Whenever possible, the X-ray scattering methods are applied in-situ and simultaneously in order to monitor and correlate the evolution of structural and magnetic properties of the nanostructured systems. The following systems are discussed, where highly-ordered magnetic nanostructures are grown on α-Al 2 O 3 substrates with topographical surface patterning and on diblock copolymer templates with chemical surface patterning: - Nanofaceted surfaces of α-Al 2 O 3 - Magnetic nanostructures on nanofaceted α-Al 2 O 3 substrates - Thin films of microphase separated diblock copolymers - Magnetic nanostructures on diblock copolymer thin film templates The fact that the underlying self-assembly processes can be steered by external factors is utilized to optimize the degree of structural order in the nanostructured systems. The highly-ordered systems are well-suited for investigations with X-ray scattering methods, since due to their uniformity the inherently averaged scattered signal of a sample yields meaningful information on the properties of the contained nanostructures: By means of an in-situ GISAXS experiment at temperatures above 1000 C, details on the facet formation on α-Al 2 O 3 surfaces are determined. A novel method, merging in-situ GISAXS and NRS, shows the evolution of magnetic states in a system with correlated structural and magnetic inhomogeneity with lateral resolution. The temperature-dependence of the shape of Fe nanodots growing on diblock copolymer templates is revealed by in-situ GISAXS during sputter deposition of Fe. Combining in-situ GISAXS and NRS, the magnetization

  10. A Molecular Simulation Approach to the Prediction of the Morphology of Self-Assembled Nanoparticles in Diblock Copolymers

    Czech Academy of Sciences Publication Activity Database

    Posocco, P.; Posel, Z.; Fermeglia, M.; Lísal, Martin; Pricl, S.

    2010-01-01

    Roč. 20, č. 46 (2010), s. 10511-10520 ISSN 0959-9428 R&D Projects: GA ČR GA203/08/0094; GA AV ČR KAN400720701 Grant - others:EC(XE) TD0802/OC10053 Institutional research plan: CEZ:AV0Z40720504 Keywords : diblock copolymers * nanoparticles * computer simulation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.101, year: 2010

  11. Mesoscale Simulation of Polymer Reaction Equilibrium: Combining Dissipative Particle Dynamics with Reaction Ensemble Monte Carlo. II. Supramolecular Diblock Copolymers

    Czech Academy of Sciences Publication Activity Database

    Lísal, Martin; Brennan, J.K.; Smith, W.R.

    2009-01-01

    Roč. 130, č. 10 (2009), 104902-1-104902-15 ISSN 0021-9606 R&D Projects: GA ČR GA203/08/0094; GA AV ČR 1ET400720507; GA AV ČR KAN400720701 Institutional research plan: CEZ:AV0Z40720504 Keywords : mesoscale simulation s * supramolecular diblock copolymers * reaction equilibrium Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.093, year: 2009

  12. Amphiphilic photosensitive dextran-g-poly(o-nitrobenzyl acrylate) glycopolymers.

    Science.gov (United States)

    Soliman, Soliman Mehawed Abdellatif; Colombeau, Ludovic; Nouvel, Cécile; Babin, Jérôme; Six, Jean-Luc

    2016-01-20

    Among all photosensitive monomers reported in the literature, o-nitrobenzyl acrylate (NBA) was selected in this present study. Two strategies were compared to produce azido-terminated poly(o-nitrobenzyl acrylate) (PNBA) using controlled Single Electron Transfer-Living Radical Polymerization (SET-LRP). In a parallel way, dextran (Dex) was modified by the introduction of several alkynyl-terminated hydrophobic chains. Finally, an Huisgen-type Copper (I)-catalyzed Azide-Alkyne Cycloaddition (CuAAC) click-chemistry was carried out to produce amphiphilic Dex-g-PNBA glycopolymers with different number and length of PNBA grafts. 2D DOSY (1)H NMR was used to prove the formation of such glycopolymers. Preliminary study on Dex-g-PNBA self-assembly was done by measuring the critical water content (CWC) above which Dex-g-PNBA started to auto-organize themselves to produce nano-objects. Finally, under UV irradiation, PNBA grafts turn into poly(acrylic acid) ones giving light-sensitive properties to such amphiphilic Dex-g-PNBA. Such properties were evaluated and compared with those of PNBA. Copyright © 2015 Elsevier Ltd. All rights reserved.

  13. Amphiphilic Silane Modified Multifunctional Nanoparticles for Magnetically Targeted Photodynamic Therapy.

    Science.gov (United States)

    Sun, Xueke; Dong, Biao; Xu, Hongwei; Xu, Shihan; Zhang, Xinran; Lin, Yanxia; Xu, Lin; Bai, Xue; Zhang, Shuang; Song, Hongwei

    2017-04-05

    Efficient targeting is a major challenge in practical photodynamic therapy (PDT). Though the "enhanced permeability and retention" (EPR) effect is a widely used tumor targeting method, magnetic targeting strategy is more promising considering the issue of high targeting efficiency and reducing concentration-dependent toxicity. Herein, magnetic targeting and highly effective Fe 3 O 4 @Ce6/C6@silane NPs are reported as a class of precisely controlled photosensitizers (PS) for PDT. On the basis of the amphiphilic silane encapsulation, PS chlorin e6 (Ce6) and Coumarin 6 (C6) as well as Fe 3 O 4 NPs were coloaded into the inside hydrophobic environment of amphiphilic silane, forming a theranostic agent for dual-mode imaging guided and magnetic targeting enhanced in vivo PDT agent. To solve the problem of over-irradiation, the coloaded design of C6 and Ce6 molecules can afford the real time PDT monitoring by ratio emissions with same excitation wavelength. When Fe 3 O 4 @Ce6/C6@silane and Ce6/C6@silane NPs are compared in in vitro and in vivo experiments, the introduction of Fe 3 O 4 in the composite does not affect the PDT efficiency, whereas, in contrast, it brings MRI imaging and magnetic targeting functions. Fe 3 O 4 @Ce6/C6@silane injection followed with magnetic field (MF) and light irradiation is important in generating an effective PDT process, showing great potential in tumor therapy.

  14. Lyotropic Phase Behavior of Poly(ethylene oxide)-Poly(butadiene) Diblock Copolymers: Evolution of the Random Network Morphology

    Energy Technology Data Exchange (ETDEWEB)

    Jain, Sumeet; Dyrdahl, Mitchell H.E.; Gong, Xiaobo; Scriven, L.E.; Bates, Frank S. (UMM)

    2008-10-24

    The phase behavior of poly(ethylene oxide)-poly(butadiene) (PEO-PB) diblock copolymers mixed with water was studied using small-angle X-ray scattering (SAXS), cryogenic scanning electron microscopy (cryo-SEM), cryogenic transmission electron microscopy (cryo-TEM), and dynamic mechanical spectroscopy. Two sets of diblocks were synthesized by adding different lengths of PEO to hydroxy terminated PB with degrees of polymerization N{sub PB} = 46 and 170. Two-component mixtures were investigated as a function of block composition and copolymer molecular weight, between 1 and 100 wt % polymer content. Melt phase behavior is consistent with established theory and known experimental behavior for diblock copolymers. Various lyotropic liquid crystalline structures, notably lamellae (L), hexagonally packed cylinders (H), and spheres (S) arranged on cubic (body-centered cubic, face-centered cubic) lattices, were documented as a function of water content. At the higher molecular weights (N{sub PB} = 170), a random network phase (N) was identified over a sizable portion of the phase portrait, located between hexagonally ordered cylinders and ordered lamellae. This new structure, along with branching of cylindrical micelles in the dilute limit, bear a striking similarity to experimentally observed and theoretically predicted phase behavior in certain ternary water/oil/surfactant systems. These findings demonstrate that block copolymer surfactants are characterized by at least four structural building blocks -- spheres, cylinders, bilayers, and branched cylinders -- above a threshold molecular weight.

  15. Diblock copolymers of polystyrene-b-poly(1,3-cyclohexadiene) exhibiting unique three-phase microdomain morphologies

    KAUST Repository

    Misichronis, Konstantinos

    2016-03-31

    The synthesis and molecular characterization of a series of conformationally asymmetric polystyrene-block-poly(1,3-cyclohexadiene) (PS-b-PCHD) diblock copolymers (PCHD: ∼90% 1,4 and ∼10% 1,2), by sequential anionic copolymerization high vacuum techniques, is reported. A wide range of volume fractions (0.27≤ϕPS≤0.91) was studied by transmission electron microscopy and small-angle X-ray scattering in order to explore in detail the microphase separation behavior of these flexible/semiflexible diblock copolymers. Unusual morphologies, consisting of PCHD core(PCHD-1,4)-shell(PCHD-1,2) cylinders in PS matrix and three-phase (PS, PCHD-1,4, PCHD-1,2) four-layer lamellae, were observed suggesting that the chain stiffness of the PCHD block and the strong dependence of the interaction parameter χ on the PCHD microstructures are important factors for the formation of this unusual microphase separation behavior in PS-b-PCHD diblock copolymers. © 2016 Wiley Periodicals, Inc.

  16. Atomic force microscopy assessment of mechanically induced scratch damage in polypropylenes and ethylene-propylene di-block copolymers

    International Nuclear Information System (INIS)

    Dasari, A.; Rohrmann, J.; Misra, R.D.K.

    2003-01-01

    Atomic force microscopy (AFM) in tapping mode has been used to determine the extent of surface damage induced during a scratch test in different grades of polypropylenes (PPs) and ethylene-propylene (EP) di-block copolymers. The surface damage is examined for long chain polymeric materials and their respective short chains. The extent of surface damage is evaluated in terms of average surface height of the plastically deformed region, depth of the scratch tracks, and thickness and density of the scratch tracks. The ability of the polymeric materials to resist scratch deformation under identical conditions of scratch test follows the sequence (from maximum resistance to minimum resistance): high crystallinity PPs>low crystallinity PPs>EP di-block copolymers. Also, short chain polymeric materials have greater resistance to scratch deformation than their respective long chain polymers. The scratch tracks are zigzag in PPs and parabolic in EP di-block copolymers with localized plastic flow involving voids. It is interpreted that modulus and yield strength are the determining factors that dictate the scratch resistance of polymeric materials

  17. Synthesis and characterization of a novel water-soluble cationic diblock copolymer with star conformation by ATRP

    Energy Technology Data Exchange (ETDEWEB)

    Li, Shuzhao [Department of Chemical Engineering, University of New Brunswick, Fredericton, NB E3B 5A3 (Canada); School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 (China); Xiao, Miaomiao [Department of Chemical Engineering, University of New Brunswick, Fredericton, NB E3B 5A3 (Canada); Zheng, Anna [School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 (China); Xiao, Huining, E-mail: hxiao@unb.ca [Department of Chemical Engineering, University of New Brunswick, Fredericton, NB E3B 5A3 (Canada)

    2014-10-01

    A water-soluble cationic diblock copolymer, CD-PAM-b-PMeDMA, was synthesized through atom transfer radical polymerization (ATRP) from a β-cyclodextrin (CD) macroinitiator with 10-active sites (10Br-β-CD). In order to reduce the cytotoxicity of the CD-PAM-b-PMeDMA, biocompatible polyacrylamide (PAM) was first introduced onto the surface of β-CD as a scaffold structure by ATRP using the 10Br-β-CD as a macroinitiator. The reaction conditions of AM were explored and optimized. The ATRP of [2-(methacryloyloxy)ethyl] trimethyl ammonium chloride (MeDMA) was also performed to synthesize the second cationic block using the resulting CD-PAM as a macroinitiator. The resulting diblock copolymer shows an increased hydrodynamic radius in aqueous solution with a pretty low concentration compared with β-CD. In addition, it appears a near-uniform coniform after being deposited on mica ascribed to the presence of an asymmetric 10-arm structure. - Highlights: • A 10-arm diblock polymer was prepared by ATRP for the potential use as a non-viral gene delivery. • PAM was first synthesized in a controlled manner considering its biocompatibility. • The hydrodynamic radius of the copolymer in aqueous solution increase to 130 nm from 7.5 nm of CD. • The copolymer appears coniform after deposited on mica surface due to the charge attraction.

  18. Sulfate-based anionic diblock copolymer nanoparticles for efficient occlusion within zinc oxide

    Science.gov (United States)

    Ning, Y.; Fielding, L. A.; Andrews, T. S.; Growney, D. J.; Armes, S. P.

    2015-04-01

    Occlusion of copolymer particles within inorganic crystalline hosts not only provides a model for understanding the crystallisation process, but also may offer a direct route for the preparation of novel nanocomposite materials with emergent properties. In the present paper, a series of new well-defined anionic diblock copolymer nanoparticles are synthesised by polymerisation-induced self-assembly (PISA) via reversible addition-fragmentation chain transfer (RAFT) aqueous emulsion polymerisation and then evaluated as crystal habit modifiers for the in situ formation of ZnO in aqueous solution. Systematic studies indicate that both the chemical nature (i.e. whether sulfate-based or carboxylate-based) and the mean degree of polymerisation (DP) of the anionic stabiliser block play vital roles in determining the crystal morphology. In particular, sulfate-functionalised nanoparticles are efficiently incorporated within the ZnO crystals whereas carboxylate-functionalised nanoparticles are excluded, thus anionic character is a necessary but not sufficient condition for successful occlusion. Moreover, the extent of nanoparticle occlusion within the ZnO phase can be as high as 23% by mass depending on the sulfate-based nanoparticle concentration. The optical properties, chemical composition and crystal structure of the resulting nanocomposite crystals are evaluated and an occlusion mechanism is proposed based on the observed evolution of the ZnO morphology in the presence of sulfate-based anionic nanoparticles. Finally, controlled deposition of a 5 nm gold sol onto porous ZnO particles (produced after calcination of the organic nanoparticles) significantly enhances the rate of photocatalytic decomposition of a model rhodamine B dye on exposure to a relatively weak UV source.Occlusion of copolymer particles within inorganic crystalline hosts not only provides a model for understanding the crystallisation process, but also may offer a direct route for the preparation of novel

  19. Asymmetric and symmetric bolaform supra-amphiphiles: formation of imine bond influenced by aggregation.

    Science.gov (United States)

    Wang, Guangtong; Wu, Guanglu; Wang, Zhiqiang; Zhang, Xi

    2014-02-18

    A series of bolaform supra-amphilphiles with different symmetries were fabricated through dynamic benzoic imine bond formation. The pH dependence of imine formations of these supra-amphiphiles were characterazied. We found that the extent of the imine formation of these supra-amphiphies were different. The supra-amphiphiles with a poorer symmetry always exhibited a lower imine formation at a given pH. Therefore, the varied extent of imine bond formation indicate the different aggregations of these supra-amphilphiles, which are controlled by the molecular symmetry of the supra-amphiphiles.

  20. Stable Vesicles Composed of Mono- or Dicarboxylic Fatty Acids and Trimethylammonium Amphiphiles

    DEFF Research Database (Denmark)

    Caschera, Filippo; Bernardino de la Serna, Jorge; Löffler, Philipp M. G.

    2011-01-01

    shown to be more stable than those formed by pure fatty acids. Those containing bola-amphiphile even showed encapsulation of a small hydrophilic solute (8-hydroxypyrene-1,3,6-trisulfonic-acid) suggesting a denser packing of the amphiphiles. Compression and kinetics analysis of monolayers composed...... of these amphiphiles mixtures at the air/water interface suggest that the stabilization of the structures can be attributed to two main interactions between headgroups, predominantly the formation of hydrogen bonds between protonated and deprotonated acids and then the additional electrostatic interactions between...

  1. (CryoTransmission Electron Microscopy of Phospholipid Model Membranes Interacting with Amphiphilic and Polyphilic Molecules

    Directory of Open Access Journals (Sweden)

    Annette Meister

    2017-10-01

    Full Text Available Lipid membranes can incorporate amphiphilic or polyphilic molecules leading to specific functionalities and to adaptable properties of the lipid bilayer host. The insertion of guest molecules into membranes frequently induces changes in the shape of the lipid matrix that can be visualized by transmission electron microscopy (TEM techniques. Here, we review the use of stained and vitrified specimens in (cryoTEM to characterize the morphology of amphiphilic and polyphilic molecules upon insertion into phospholipid model membranes. Special emphasis is placed on the impact of novel synthetic amphiphilic and polyphilic bolalipids and polymers on membrane integrity and shape stability.

  2. Amphiphile replacement on carbon nanotube surfaces: Effect of aromatic groups on the interaction strength

    Energy Technology Data Exchange (ETDEWEB)

    Bluemmel, Pascal; Setaro, Antonio; Reich, Stephanie [Institut fuer Experimentalphysik, Freie Universitaet Berlin, Arnimallee 14, 14195 Berlin (Germany); Popeney, Chris S.; Trappmann, Britta; Haag, Rainer [Institut fuer Chemie und Biochemie, Freie Universitaet Berlin, Takustrasse 3, 14195 Berlin (Germany)

    2011-11-15

    Carbon nanotubes (CNTs) were solubilized using akyl/polyglycerol amphiphiles. Similar cosurfactants, bearing different aromatic moieties between head and tail, were added to these samples. The interaction strength between these amphiphiles and CNTs changes depending on the inserted aromatic moieties. The insertion of a phenyl ring allows the amphiphile to replace the starting one indicating a higher interaction strength, while the insertion of a triazol pentagon does not, suggesting that the interaction strength is lower. The replacement was monitored via PLE mapping. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  3. Synthesis and Application of a New Amphiphilic Antioxidant.

    Science.gov (United States)

    Soliman, Hanaa M; Arafat, Shaker M; Basuny, Amany M; Shattory, Y El-

    2017-11-01

    A new amphiphilic antioxidant (tannyl stearate) derived from reaction of tannic acid with stearic acid was synthesized in order to improve tannic acid solubility in lipid materials. This reaction gives many products having different degree of esterification (tannyl mono, di, tri, tetra, penta, hexa, hepta……stearate) which were separated using silica gel column chromatography and tentative identification was carried out using thin layer chromatography (TLC). The intrinsic viscosities (η) were used to differentiate between the different molecular weight of the produced esters 1) . Tannyl penta stearate is assumed to be the most suitable amphiphilic antioxidant derivative, where those derivatives with less degree of esterification would be less soluble in fat, and those of higher degree of esterification would exhaust more hydroxyl group that cause decreases of antioxidant activity. The structure of tannyl penta stearate was approved depending on its chemical analysis and spectral data (IR, H 1 NMR,). The emulsification power of tannyl penta stearate was then determined according to method described by El-Sukkary et al. 2) , in order to prove its amphiphilic property. Then tannyl penta stearate was tested for its antioxidant and radical scavenging activities in three different manners, those are, lipid oxidation in sunflower oil using Rancimat, (DPPH) free radical scavenging and total antioxidant activity. {Pure tannic acid (T), butylhydroxyanisol (BHA) and butylhydroxytoluene (BHT) were used as reference antioxidant radical saving compounds}. Then tannyl penta stearate was added to sunflower oil, frying process was carried out and all physicochemical parameters of the oil were considered, and compared to other reference antioxidant in order to study the effect of this new antioxidant toward oil stability. Acute oral toxicity of the tannyl penta stearate was carried out using albino mice of 21-25 g body weight to determine its safety according to the method

  4. Durability and performance of polystyrene- b -poly(vinylbenzyl trimethylammonium) diblock copolymer and equivalent blend anion exchange membranes

    Energy Technology Data Exchange (ETDEWEB)

    Vandiver, Melissa A. [Department of Chemical and Biological Engineering, Colorado School of Mines, Golden Colorado 80401; Caire, Benjamin R. [Department of Chemical and Biological Engineering, Colorado School of Mines, Golden Colorado 80401; Poskin, Zach [Department of Chemical and Biological Engineering, Colorado School of Mines, Golden Colorado 80401; Li, Yifan [Department of Chemistry and Geochemistry, Colorado School of Mines, Golden Colorado 80401; Seifert, Sönke [X-Ray Science Division, Argonne National Laboratory, Argonne Illinois 60439; Knauss, Daniel M. [Department of Chemistry and Geochemistry, Colorado School of Mines, Golden Colorado 80401; Herring, Andrew M. [Department of Chemical and Biological Engineering, Colorado School of Mines, Golden Colorado 80401; Liberatore, Matthew W. [Department of Chemical and Biological Engineering, Colorado School of Mines, Golden Colorado 80401

    2014-11-01

    Anion exchange membranes (AEM) are solid polymer electrolytes that facilitate ion transport in fuel cells. In this study, a polystyrene-b-poly(vinylbenzyl trimethylammonium) diblock copolymer was evaluated as potential AEM and compared with the equivalent homopolymer blend. The diblock had a 92% conversion of reactive sites with an IEC of 1.72 ± 0.05 mmol g-1, while the blend had a 43% conversion for an IEC of 0.80 ± 0.03 mmol g-1. At 50°C and 95% relative humidity, the chloride conductivity of the diblock was higher, 24–33 mS cm-1, compared with the blend, 1–6 mS cm-1. The diblock displayed phase separation on the length scale of 100 nm, while the blend displayed microphase separation (~10 μm). Mechanical characterization of films from 40 to 90 microns thick found that elasticity and elongation decreased with the addition of cations to the films. At humidified conditions, water acted as a plasticizer to increase film elasticity and elongation. While the polystyrene-based diblock displayed sufficient ionic conductivity, the films' mechanical properties require improvement, i.e., greater elasticity and strength, before use in fuel cells. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41596.

  5. Poly(phenylene ether Based Amphiphilic Block Copolymers

    Directory of Open Access Journals (Sweden)

    Edward N. Peters

    2017-09-01

    Full Text Available Polyphenylene ether (PPE telechelic macromonomers are unique hydrophobic polyols which have been used to prepare amphiphilic block copolymers. Various polymer compositions have been synthesized with hydrophilic blocks. Their macromolecular nature affords a range of structures including random, alternating, and di- and triblock copolymers. New macromolecular architectures can offer tailored property profiles for optimum performance. Besides reducing moisture uptake and making the polymer surface more hydrophobic, the PPE hydrophobic segment has good compatibility with polystyrene (polystyrene-philic. In general, the PPE contributes to the toughness, strength, and thermal performance. Hydrophilic segments go beyond their affinity for water. Improvements in the interfacial adhesion between polymers and polar substrates via hydrogen bonding and good compatibility with polyesters (polyester-philic have been exhibited. The heterogeneity of domains in these PPE based block copolymer offers important contributions to diverse applications.

  6. Structure and reactivity in amphiphile-water micelles

    International Nuclear Information System (INIS)

    Chevalier, Yves

    1985-01-01

    Following a review of the general properties of micelles, this report contains two parts: - A structural study of octylphosphate micelles. Important structural changes have been evidenced by mean of small angle neutron scattering as the electrical charge of the interface is varied. The NMR relaxation study of the conformation of the hydrocarbon chains has shown that the micellar core is disordered in contrast with the interface which is rather structured. The diffusion motions in the interface and the segmental motions of the chains are fast. - Studies on the reactivity in micelles have been carried out. A large micellar effect on the complexation of transition ions by amphiphilic ligands is evidenced. The problem of solute localization in micelles is developed with few examples. (author) [fr

  7. Interaction of amphiphilic drugs with human and bovine serum albumins.

    Science.gov (United States)

    Khan, Abbul Bashar; Khan, Javed Masood; Ali, Mohd Sajid; Khan, Rizwan Hasan; Kabir-Ud-Din

    2012-11-01

    To know the interaction of amphiphilic drugs nortriptyline hydrochloride (NOT) and promazine hydrochloride (PMZ) with serum albumins (i.e., human serum albumin (HSA) and bovine serum albumin (BSA)), techniques of UV-visible, fluorescence, and circular dichroism (CD) spectroscopies are used. The binding affinity is more in case of PMZ with both the serum albumins. The quenching rate constant (k(q)) values suggest a static quenching process for all the drug-serum albumin interactions. The UV-visible results show that the change in protein conformation of PMZ-serum albumin interactions are more prominent as compared to NOT-serum albumin interactions. The CD results also explain the conformational changes in the serum albumins on binding with the drugs. The increment in %α-helical structure is slightly more for drug-BSA complexes as compared to drug-HSA complexes. Copyright © 2012 Elsevier B.V. All rights reserved.

  8. 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.

  9. Adsorption of sub-micron amphiphilic dumbbells to fluid interfaces.

    Science.gov (United States)

    Isa, Lucio; Samudrala, Niveditha; Dufresne, Eric R

    2014-05-13

    We investigate the adsorption of submicrometer bulk-synthesized polymer dumbbells to oil-water interfaces using freeze-fracture, shadow-casting (FreSCa) cryo-scanning electron microscopy. We find that the dumbbells are amphiphilic and adsorb to the interface with a preferred orientation. Most particles adsorb in a tilted configuration, with the polar and apolar lobes intersecting the interface and pointing toward the water and oil, respectively. Some particles adsorb with only one lobe attached to the interface. Moreover, we find that each lobe has a preferred angle of contact with the interface, identical in all observed configurations. A simple geometrical calculation using these contact angles accurately predicts the dominant configuration of particles at the interface. This calculation provides insight into how the shape and composition of dumbbells can be tuned to stand upright and pack efficiently on curved interfaces.

  10. Antifungal amphiphilic aminoglycoside K20: bioactivities and mechanism of action

    Directory of Open Access Journals (Sweden)

    Sanjib K. Shrestha

    2014-12-01

    Full Text Available K20 is a novel amphiphilic antifungal aminoglycoside that is synthetically derived from the antibiotic kanamycin A. Reported here are investigations of K20’s antimicrobial activities, cytotoxicity, and fungicidal mechanism of action. In vitro growth inhibitory activities against a variety of human and plant pathogenic yeasts, filamentous fungi, and bacteria were determined using microbroth dilution assays and time-kill curve analyses, and hemolytic and animal cell cytotoxic activities were determined. Effects on Cryptococcus neoformans H-99 infectivity were determined with a preventive murine lung infection model. The antifungal mechanism of action was studied using intact fungal cells, yeast lipid mutants, and small unilamellar lipid vesicles. K20 exhibited broad-spectrum in vitro antifungal activities but not antibacterial activities. Pulmonary, single dose-administration of K20 reduced C. neoformans lung infection rates 4-fold compared to controls. Hemolysis and half-maximal cytotoxicities of mammalian cells occurred at concentrations that were 10 to 32-fold higher than fungicidal MICs. With fluorescein isothiocyanate, 20 to 25 mg/L K20 caused staining of >95% of C. neoformans and Fusarium graminearum cells and at 31.3 mg/L caused rapid leakage (30 to 80% in 15 min of calcein from preloaded small unilamellar lipid vesicles. K20 appears to be a broad-spectrum fungicide, capable of reducing the infectivity of C. neoformans, and exhibits low hemolytic activity and mammalian cell toxicity. It perturbs the plasma membrane by mechanisms that are lipid modulated. K20 is a novel amphiphilic aminoglycoside amenable to scalable production and a potential lead antifungal for therapeutic and crop protection applications.

  11. Tailoring peptide amphiphiles and their assemblies for biomedical applications

    Science.gov (United States)

    Lin, Brian

    Peptide amphiphiles (PAs) are molecules composed of a peptide conjugated to a hydrophobic moiety, commonly a fatty acid. They closely resemble the structure of naturally occurring lipopeptides, produced by microbes as signaling and antimicrobial agents. The amphiphilic nature of PAs in concert with the large number of discovered functional peptides inspired scientists to exploit this molecular architecture for producing synthetic self-assembled bioactive materials. PA assemblies are sought after for a wide breadth of applications including disease therapy, regenerative medicine, and catalysis. However, with PAs, the peptide chemistry is a double-edged sword. The peptide component contributes significantly to both the activity and self-assembly. The physiochemical properties of different PAs lead to unique aggregation stability and morphological characteristics which are unpredictable, a priori. Therefore it is challenging to design bioactive PAs and control their self-assembly, simultaneously. This limitation slows the development of PAs for medical use. In this dissertation, methods to control the self-assembly of PAs and the effects of acylating a functional peptide will be discussed. In one part, efforts to direct the self-assembly of PAs into small spherical aggregates, a morphology infrequently observed, will be described. In another section, a strategy to control the stability of PA assemblies will be discussed. In the last section, a pH-responsive membrane perturbing peptide was modified with fatty acid tails and the properties of the resulting PAs will be presented. This dissertation provides some fundamental insight for the use and design of PA self-assemblies.

  12. 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.

  13. Bimetallic PdAg nanoparticle arrays from monolayer films of diblock copolymer micelles

    Science.gov (United States)

    Ehret, E.; Beyou, E.; Mamontov, G. V.; Bugrova, T. A.; Prakash, S.; Aouine, M.; Domenichini, B.; Cadete Santos Aires, F. J.

    2015-07-01

    The self-assembly technique provides a highly efficient route to generate well-ordered structures on a nanometer scale. In this paper, well-ordered arrays of PdAg alloy nanoparticles on flat substrates with narrow distributions of particle size (6-7 nm) and interparticle spacing (about 60 nm) were synthesized by the block copolymer micelle approach. A home-made PS-b-P4VP diblock copolymer was prepared to obtain a micellar structure in toluene. Pd and Ag salts were then successfully loaded in the micellar core of the PS-b-P4VP copolymer. A self-assembled monolayer of the loaded micelles was obtained by dipping the flat substrate in the solution. At this stage, the core of the micelles was still loaded with the metal precursor rather than with a metal. Physical and chemical reducing methods were used to reduce the metal salts embedded in the P4VP core into PdAg nanoparticles. HRTEM and EDX indicated that Pd-rich PdAg alloy nanoparticles were synthesized by chemical or physical reduction; UV-visible spectroscopy observations confirmed that metallic PdAg nanoparticles were quickly formed after chemical reduction; XPS measurements revealed that the PdAg alloy nanoparticles were in a metallic state after a short time of exposure to O2 plasma and after hydrazine reduction.

  14. Lyotropic Phase Behavior of Polybutadiene-Poly(ethylene oxide) Diblock Copolymers in Ionic Liquids

    Energy Technology Data Exchange (ETDEWEB)

    Simone, Peter M.; Lodge, Timothy P. (UMM)

    2008-08-26

    The lyotropic phase behavior of three poly(1,2-butadiene-b-ethylene oxide) diblock copolymers (PB-PEO) with different monomer volume fractions has been studied in two different ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMI][TFSI]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([BMI][PF{sub 6}]), across the complete concentration range. The ordered microstructures present in the solutions were characterized via small-angle X-ray scattering (SAXS). The phase diagrams for the PB-PEO/ionic liquid solutions include regions corresponding to the classical copolymer microstructures: body-centered-cubic lattices of spheres, hexagonally ordered cylinders, and lamellae. Additionally, the phase diagrams also include wide regions of coexisting microstructures and regions apparently corresponding to a disordered network microstructure. The phase behavior of the PB-PEO copolymers in both ionic liquids was comparable to their previously reported aqueous solution behavior. The temperature dependence of the phase diagrams was very modest, indicative of a highly segregated system. The level of solvent selectivity was also investigated via cryogenic transmission electron microscopy (cryo-TEM) on dilute solutions. On the basis of the morphology of the dilute solution copolymer aggregate structures in the ionic liquid solvents, and on the structural length scales of the concentrated solutions, it was concluded that for PB-PEO [BMI][PF{sub 6}] behaves as a more selective solvent than [EMI][TFSI].

  15. Incorporation of Amphipathic Diblock Copolymer in Lipid Bilayer for Improving pH Responsiveness

    Directory of Open Access Journals (Sweden)

    Tian Xia

    2016-01-01

    Full Text Available Diblock copolymers (mPEG-b-PDPA, which were designed to possess pH-sensitivity as well as amphipathy, were used as an intelligent lock in the liposomal membrane. The so-called pH-sensitive liposomes were prepared by simple mixing of the synthesized mPEG-b-PDPA with phospholipids and cholesterol. Fluorescence polarization at pH 7.4 showed that the membrane stability of the hybrid liposome was significantly increased compared with the pure liposome. Therefore, in the neutral environment, the leakage of doxorubicin (DOX was inhibited. However, when pH decreased to 6.0, DOX release rate increased by 60% due to the escape of copolymer. The effects of the membrane composition and the PDPA segment length on bilayer membrane functions were investigated. These results revealed that the synthesized copolymers increased the difference in DOX cumulative release between pH 7.4 and 6.0, that is, improved the pH-controllability of the drug release from hybrid liposomes.

  16. Magnetic field alignment of coil-coil diblock copolymers and blends via intrinsic chain anisotropy

    Science.gov (United States)

    Rokhlenko, Yekaterina; Majewski, Pawel; Larson, Steven; Yager, Kevin; Gopalan, Padma; Avgeropoulos, Apostolos; Chan, Edwin; Osuji, Chinedum

    Magnetic fields can control alignment of self-assembled soft materials such as block copolymers provided there is a suitably large magnetic susceptibility anisotropy present in the system. Recent results have highlighted the existence of a non-trivial intrinsic anisotropy in coil-coil diblock copolymers, specifically in lamellar-forming PS-b-P4VP, which enables alignment at field strengths of a few tesla in systems lacking mesogenic components. Alignment is predicated on correlation in the orientation of end-end vectors implied by the localization of block junctions at the microdomain interface and is observed on cooling across the order-disorder transition in the presence of the field. For appropriate combinations of field strength and grain size, we can leverage intrinsic chain anisotropy to magnetically direct self-assembly of many non-mesogenic systems, including other coil-coil BCPs like PS-b-PDMS and PS-b-PMMA, blends of BCPs of disparate morphologies and MWs, and blends of BCPs with homopolymers. This is noteworthy as blends of PS-b-P4VP with PEO provide a route to form functional materials such as nanoporous films by dissolution of PEO, or aligned ion conduction materials. We survey these various systems using TEM and in-situ X-ray scattering to study the phase behavior and temperature-, time- and field- dependent dynamics of alignment.

  17. Oxidized potato starch based thermoplastic films : Effect of combination of hydrophilic and amphiphilic plasticizers

    NARCIS (Netherlands)

    Niazi, Muhammad Bilal Khan; Broekhuis, Antonius A.

    Different combinations of hydrophilic (glycerol and water) and amphiphilic (isoleucine) plasticizers were studied in the production of thermoplastic starch (TPS) powders and films from oxidized potato starch. All powder samples had an irregular and shrivelled morphology. In all mixtures containing

  18. Amphiphilic heteroarm star polymer synthesized by RAFT dispersion polymerization in water/ethanol solution.

    Science.gov (United States)

    Shi, Xiaofang; Zhou, Wei; Qiu, Qian; An, Zesheng

    2012-07-28

    Well-defined amphiphilic heteroarm core cross-linked star (CCS) polymer was efficiently synthesized by RAFT-mediated arm-first strategy in dispersion polymerization, and its direct self-assembly in water was demonstrated.

  19. Self-assembly and headgroup effect in nanostructured organogels via cationic amphiphile-graphene oxide composites.

    Directory of Open Access Journals (Sweden)

    Tifeng Jiao

    Full Text Available Self-assembly of hierarchical graphene oxide (GO-based nanomaterials with novel functions has received a great deal of attentions. In this study, nanostructured organogels based on cationic amphiphile-GO composites were prepared. The gelation behaviors of amphiphile-GO composites in organic solvents can be regulated by changing the headgroups of amphiphiles. Ammonium substituted headgroup in molecular structures in present self-assembled composites is more favorable for the gelation in comparison to pyridinium headgroup. A possible mechanism for headgroup effects on self-assembly and as-prepared nanostructures is proposed. It is believed that the present amphiphile-GO self-assembled system will provide an alternative platform for the design of new GO nanomaterials and soft matters.

  20. Self-assembling peptide amphiphiles and related methods for growth factor delivery

    Science.gov (United States)

    Stupp, Samuel I [Chicago, IL; Donners, Jack J. J. M.; Silva, Gabriel A [Chicago, IL; Behanna, Heather A [Chicago, IL; Anthony, Shawn G [New Stanton, PA

    2009-06-09

    Amphiphilic peptide compounds comprising one or more epitope sequences for binding interaction with one or more corresponding growth factors, micellar assemblies of such compounds and related methods of use.

  1. Study of structural morphologies of thermoresponsive diblock AB and triblock BAB copolymers (A = poly(N-isopropylacrylamide), B = polystyrene)

    Science.gov (United States)

    Rodríguez-Hidalgo, María del Rosario; Soto-Figueroa, César; Vicente, Luis

    2018-03-01

    Structural morphologies of diblock AB and triblock BAB copolymers (A = poly(N-isopropylacrylamide), B = polystyrene) in aqueous environment have been investigated by dissipative particle dynamics (DPD). In triblock copolymers insoluble PS blocks contract while soluble pNIPAM blocks stay at the periphery forming looped chains as corona. As the temperature is increased there is a continuous morphological transition and micelles form ellipsoidal structures with segregated polymer zones. The phase transition of looped pNIPAM chains occurs at lower temperature than for linear chains and within broader temperature range. It is discussed how the chain topology of pNIPAM affects the phase transition.

  2. On the relationship between the local segmental dynamics and the tagged monomer dynamics in lamellar phases of diblock copolymers

    Science.gov (United States)

    Sethuraman, Vaidyanathan; Ganesan, Venkat

    2017-09-01

    In this brief article, we present results from coarse-grained molecular dynamics simulations which probed the relationship between the local segmental dynamics and the tagged monomer dynamics in lamellar phases of diblock copolymers. Our results demonstrate that monomer relaxation times do not provide directly a quantitatively accurate measure of the spatial variations in segmental dynamics. However, a convolution of the monomer density distributions with their corresponding relaxation times is shown to provide an approximate, but accurate, quantitative characterization of the average local segmental dynamics.

  3. Collective dynamics and self-diffusion in a diblock copolymer melt in the body-centered cubic phase

    DEFF Research Database (Denmark)

    Papadakis, C.M.; Rittig, F.; Almdal, K.

    2004-01-01

    The structure and dynamics of a strongly asymmetric poly(ethylene propylene)poly (dimethylsiloxane) (PEP-PDMS) diblock copolymer in the melt have been studied over a wide temperature range. Small-angle neutron scattering reveals that the sample exhibits two stable phases in this temperature range......: Above the order-to-disorder transition temperature, it is disordered, whereas the domain structure is body-centered cubic (bcc) below, being stable down to the lowest temperatures measured. In the disordered state, dynamic light scattering (DLS) in the polarized geometry reveals the heterogeneity mode...

  4. Molecular Dynamics Study of Polystyrene-b-poly(ethylene oxide) Asymmetric Diblock Copolymer Systems.

    Science.gov (United States)

    Dobies, M; Makrocka-Rydzyk, M; Jenczyk, J; Jarek, M; Spontak, R J; Jurga, S

    2017-09-12

    Two polystyrene-b-poly(ethylene oxide) (PS-b-PEO) diblock copolymers differing in molecular mass (49 and 78 kDa) but possessing the same PEO cylindrical morphology are examined to elucidate their molecular dynamics. Of particular interest here is the molecular motion of the PEO blocks involved in the rigid amorphous fraction (RAF). An analysis of complementary thermal calorimetry and X-ray scattering data confirms the presence of microphase-separated morphology as well as semicrystalline structure in each copolymer. Molecular motion within the copolymer systems is monitored by dielectric and nuclear magnetic resonance spectroscopies. The results reported herein reveal the existence of two local Arrhenius-type processes attributed to the noncooperative local motion of PEO segments involved in fully amorphous and rigid amorphous PEO microphases. In both systems, two structural relaxations governed by glass-transition phenomena are identified and assigned to cooperative segmental motion in the fully amorphous phase (the α process) and the RAF (the α c process). We measure the temperature dependence of the dynamics associated with all of the processes mentioned above and propose that these local processes are associated with corresponding cooperative segmental motion in both copolymer systems. In marked contrast to the thermal activation of the α process as discerned in both copolymers, the α c process appears to be a sensitive probe of the copolymer nanostructure. That is, the copolymer with shorter PEO blocks exhibits more highly restricted cooperative dynamics of PEO segments in the RAF, which can be explained in terms of the greater constraint imposed by the glassy PS matrix on the PEO blocks comprising smaller cylindrical microdomains.

  5. Bicontinuous Phases in Diblock Copolymer/Homopolymer Blends: Simulation and Self-Consistent Field Theory

    KAUST Repository

    Martínez-Veracoechea, Francisco J.

    2009-03-10

    A combination of particle-based simulations and self-consistent field theory (SCFT) is used to study the stabilization of multiple ordered bicontinuous phases in blends of a diblock copolymer (DBC) and a homopolymer. The double-diamond phase (DD) and plumber\\'s nightmare phase (P) were spontaneously formed in the range of homopolymer volume fraction simulated via coarse-grained molecular dynamics. To the best of our knowledge, this is the first time that such phases have been obtained in continuum-space molecular simulations of DBC systems. Though tentative phase boundaries were delineated via free-energy calculations, macrophase separation could not be satisfactorily assessed within the framework of particle-based simulations. Therefore, SCFT was used to explore the DBC/homopolymer phase diagram in more detail, showing that although in many cases two-phase coexistence of a DBC-rich phase and a homopolymer-rich phase does precede the stability of complex bicontinuous phases the DD phase can be stable in a relatively wide region of the phase diagram. Whereas the P phase was always metastable with respect to macrophase separation under the thermodynamic conditions explored with SCFT, it was sometimes nearly stable, suggesting that full stability could be achieved in other unexplored regions of parameter space. Moreover, even the predicted DD- and P-phase metastability regions were located significantly far from the spinodal line, suggesting that these phases could be observed in experiments as "long-lived" metastable phases under those conditions. This conjecture is also consistent with large-system molecular dynamics simulations that showed that the time scale of mesophase formation is much faster than that of macrophase separation. © 2009 American Chemical Society.

  6. Tailorable Exciton Transport in Doped Peptide–Amphiphile Assemblies

    Energy Technology Data Exchange (ETDEWEB)

    Solomon, Lee A. [Center; Sykes, Matthew E. [Center; Wu, Yimin A. [Center; Schaller, Richard D. [Center; Department; Wiederrecht, Gary P. [Center; Fry, H. Christopher [Center

    2017-08-29

    Light-harvesting biomaterials are an attractive target in photovoltaics, photocatalysis, and artificial photosynthesis. Through peptide self-assembly, complex nanostructures can be engineered to study the role of chromophore organization during light absorption and energy transport. To this end, we demonstrate the one-dimensional transport of excitons along naturally occurring, light-harvesting, Zn-protoporphyrin IX chromophores within self-assembled peptide-amphiphile nanofibers. The internal structure of the nanofibers induces packing of the porphyrins into linear chains. We find that this peptide assembly can enable long-range exciton diffusion, yet it also induces the formation of excimers between adjacent molecules, which serve as exciton traps. Electronic coupling between neighboring porphyrin molecules is confirmed by various spectroscopic methods. The exciton diffusion process is then probed through transient photoluminescence and absorption measurements and fit to a model for one-dimensional hopping. Because excimer formation impedes exciton hopping, increasing the interchromophore spacing allows for improved diffusivity, which we control through porphyrin doping levels. We show that diffusion lengths of over 60 nm are possible at low porphyrin doping, representing an order of magnitude improvement over the highest doping fractions.

  7. Effect of Amphiphiles on the Rheology of Triglyceride Networks

    Science.gov (United States)

    Seth, Jyoti

    2014-11-01

    Networks of aggregated crystallites form the structural backbone of many products from the food, cosmetic and pharmaceutical industries. Such materials are generally formulated by cooling a saturated solution to yield the desired solid fraction. Crystal nucleation and growth followed by aggregation leads to formation of a space percolating fractal-network. It is understood that microstructural hierarchy and particle-particle interactions determine material behavior during processing, storage and use. In this talk, rheology of suspensions of triglycerides (TAG, like tristearin) will be explored. TAGs exhibit a rich assortment of polymorphs and form suspensions that are evidently sensitive to surface modifying additives like surfactants and polymers. Here, a theoretical framework will be presented for suspensions containing TAG crystals interacting via pairwise potentials. The work builds on existing models of fractal aggregates to understand microstructure and its correlation with material rheology. Effect of amphiphilic additives is derived through variation of particle-particle interactions. Theoretical predictions for storage modulus will be compared against experimental observations and data from the literature and micro structural predictions against microscopy. Such a theory may serve as a step towards predicting short and long-term behavior of aggregated suspensions formulated via crystallization.

  8. Modification of nanofibrillated cellulose using amphiphilic block-structured galactoglucomannans.

    Science.gov (United States)

    Lozhechnikova, Alina; Dax, Daniel; Vartiainen, Jari; Willför, Stefan; Xu, Chunlin; Österberg, Monika

    2014-09-22

    Nanofibrillated cellulose (NFC) and hemicelluloses have shown to be highly promising renewable components both as barrier materials and in novel biocomposites. However, the hydrophilic nature of these materials restricts their use in some applications. In this work, the usability of modified O-acetyl galactoglucomannan (GGM) for modification of NFC surface properties was studied. Four GGM-block-structured, amphiphilic derivatives were synthesized using either fatty acids or polydimethylsiloxane as hydrophobic tails. The adsorption of these GGM derivatives was consecutively examined in aqueous solution using a quartz crystal microbalance with dissipation monitoring (QCM-D). It was found that the hydrophobic tails did not hinder adsorption of the GGM derivatives to cellulose, which was concluded to be due to the presence of the native GGM-block with high affinity to cellulose. The layer properties of the adsorbed block-co-polymers were discussed and evaluated. Self-standing NFC films were further prepared and coated with the GGM derivatives and the effect of the surface modification on wetting properties and oxygen permeability (OP) of the modified films was assessed. Copyright © 2014 Elsevier Ltd. All rights reserved.

  9. Redox-switched amphiphilic ionic liquid behavior in aqueous solution.

    Science.gov (United States)

    Chamiot, Bénédicte; Rizzi, Cécile; Gaillon, Laurent; Sirieix-Plénet, Juliette; Lelièvre, Joël

    2009-02-03

    A new redox amphiphilic ionic liquid (AIL) containing ferrocene as a redox-active group was synthesized, 1-(11-ferrocenylundecyl)-3-methylimidazolium bromide (Fc11MIm+). Adsorption and aggregation of both reduced and oxidized forms of this ferrocenated AIL in aqueous solution were studied by surface tension measurements. The micellization was favored for the reduced ferrocenated AIL (Fc11MIm+) as compared with the oxidized ferrocenated AIL (Fc+11MIm+). Minimum areas at the air/aqueous solution interface were identical whereas limiting surface tensions were slightly different. This corroborated the formation of an expanded monolayer of redox active AIL at the interface. The electrochemical behavior of redox active AIL was investigated. The electrochemical responses of Fc11MIm+ aqueous solution interestingly differed, depending on its concentration. Below the cmc, the electrochemical reaction was dominated by ferrocenated AIL adsorbed onto the electrode surface; then above the cmc, it was controlled by the Fc11MIm+ diffusing to the electrode. For the latter, the electrochemical mechanism was suggested to couple with the disruption reaction of the reduced form micelles.

  10. High-Performance Field-Effect Transistors Based on Polystyrene-b-Poly(3-hexylthiophene) Diblock Copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Geohegan, David B [ORNL; Sumpter, Bobby G [ORNL; Hong, Kunlun [ORNL; Xiao, Kai [ORNL; Lavrik, Nickolay V [ORNL; Yu, Xiang [ORNL; Chen, Jihua [ORNL

    2011-01-01

    Polystyrene-b-poly(3-hexylthiophene) (PS-b-P3HT) block copolymers with fixed PS block length have been synthesized by combined atom transfer radical polymerization (ATRP) and Grignard metathesis (GRIM) polymerization. The self-assembled structures of these diblock copolymer thin films based on PS-b-P3HT have been studied by TEM, SAED, GIXD, AFM, and additionally by first principles modeling and simulation. These block copolymers undergo microphase separation and form nanostructured spheres, lamellae, nanofibers, or nanoribbons in the films dictated by the molecular weight of the P3HT block. Within the diblock copolymer thin film, PS blocks segregate to form amorphous domains, and the covalently bonded conjugated P3HT blocks exist as highly ordered crystalline domains through intermolecular packing with their alkyl side chains aligned normal to the substrate while the thiophene rings align parallel to the substrate through stacking. The conjugated PS-b-P3HT block copolymers exhibited significant improvements in organic field-effect transistor (OFET) performance and environmental stability as compared to P3HT homopolymers, with up to a factor of 2 increase in measured mobility (0.08 cm2/(V 3 s)) for the P4 (85 wt % P3HT). Overall, this work demonstrates that the high degree of molecular order induced by block copolymer phase separation can improve the transport properties and stability of conjugating polymers, which are critical for high-performance OFETs and other organic electronics.

  11. The effect of particle size on the morphology and thermodynamics of diblock copolymer/tethered-particle membranes

    International Nuclear Information System (INIS)

    Zhang, Bo; Edwards, Brian J.

    2015-01-01

    A combination of self-consistent field theory and density functional theory was used to examine the effect of particle size on the stable, 3-dimensional equilibrium morphologies formed by diblock copolymers with a tethered nanoparticle attached either between the two blocks or at the end of one of the blocks. Particle size was varied between one and four tenths of the radius of gyration of the diblock polymer chain for neutral particles as well as those either favoring or disfavoring segments of the copolymer blocks. Phase diagrams were constructed and analyzed in terms of thermodynamic diagrams to understand the physics associated with the molecular-level self-assembly processes. Typical morphologies were observed, such as lamellar, spheroidal, cylindrical, gyroidal, and perforated lamellar, with the primary concentration region of the tethered particles being influenced heavily by particle size and tethering location, strength of the particle-segment energetic interactions, chain length, and copolymer radius of gyration. The effect of the simulation box size on the observed morphology and system thermodynamics was also investigated, indicating possible effects of confinement upon the system self-assembly processes

  12. Tetragonal phase of cylinders self-assembled from binary blends of AB diblock and (A'B)nstar copolymers.

    Science.gov (United States)

    Jiang, Wenbo; Qiang, Yicheng; Liu, Meijiao; Li, Weihua; Qiu, Feng; Shi, An-Chang

    2017-09-27

    The phase behavior of binary blends composed of AB diblock and (A'B) n star copolymers is studied using the polymeric self-consistent field theory, focusing on the formation and stability of the stable tetragonal phase of cylinders. In general, cylindrical domains self-assembled from AB-type block copolymers are packed into a hexagonal array, although a tetragonal array of cylinders could be more favourable for lithography applications in microelectronics. The polymer blends are designed such that there is an attractive interaction between the A and A' blocks, which increases the compatibility between the two copolymers and thus suppresses the macroscopic phase separation of the blends. With an appropriate choice of system parameters, a considerable stability window for the targeted tetragonal phase is identified in the blends. Importantly, the transition mechanism between the hexagonal and tetragonal phases is elucidated by examining the distribution of the two types of copolymers in the unit cell of the structure. The results reveal that the short (A'B) n star copolymers are preferentially located in the bonding area connecting two neighboring domains in order to reduce extra stretching, whereas the long AB diblock copolymers are extended to further space of the unit cell.

  13. Controllable Self-Assembly of Amphiphilic Zwitterionic PBI Towards Tunable Surface Wettability of the Nanostructures.

    Science.gov (United States)

    Ye, Yong; Lü, Baozhong; Cheng, Wenyu; Wu, Zhen; Wei, Jie; Yin, Meizhen

    2017-05-04

    Amphiphilic molecules have received wide attention as they possess both hydrophobic and hydrophilic properties, and can form diverse nanostructures in selective solvents. Herein, we report an asymmetric amphiphilic zwitterionic perylene bisimide (AZP) with an octyl chain and a zwitterionic group on the opposite imide positions of perylene tetracarboxylic dianhydride. The controllable nanostructures of AZP with tunable hydrophilic/hydrophobic surface have been investigated through solvent-dependent amphiphilic self-assembly as confirmed by SEM, TEM, and contact angle measurements. The planar perylene core of AZP contributes to strong π-π stacking, while the amphiphilic balance of asymmetric AZP adjusts the self-assembly property. Additionally, due to intermolecular π-π stacking and solvent-solute interactions, AZP could self-assemble into hydrophilic microtubes in a polar solvent (acetone) and hydrophobic nanofibers in an apolar solvent (hexane). This facile method provides a new pathway for controlling the surface properties based on an asymmetric amphiphilic zwitterionic perylene bisimide. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. pH-responsive diblock copolymers with two different fluorescent labels for simultaneous monitoring of micellar self-assembly and degree of protonation

    DEFF Research Database (Denmark)

    Madsen, Jeppe; Madden, George; Themistou, Efrosyni

    2018-01-01

    be correlated to changes in PDPA protonation. Diblock copolymer self-assembly to form PDPA-core aggregates occurs under these conditions, leading to pyrene fluorescence at an excitation wavelength of 405 nm. This allows direct measurement of chain aggregation, whereas using pH-responsive dyes is simply ameasure...

  15. Temperature and pressure dependence of the order parameter fluctuations, conformational compressibility, and the phase diagram of the PEP-PDMS diblock copolymer

    DEFF Research Database (Denmark)

    Schwahn, D.; Frielinghaus, H.; Mortensen, K.

    1996-01-01

    The structure factor of a poly(ethylene-propylene)-poly(dimethylsiloxane) diblock copolymer has been measured by small-angle neutron scattering as a function of temperature and pressure. The conformational compressibility exhibits a pronounced maximum at the order-disorder phase transition. The p...

  16. Mechanical properties of weakly segregated block copolymers : 1. Synergism on tensile properties of poly(styrene-b-n-butylmethacrylate) diblock copolymers

    NARCIS (Netherlands)

    Weidisch, R.; Michler, G.H.; Fischer, H.; Arnold, M.; Hofmann, S.; Stamm, M.

    1999-01-01

    Mechanical properties of poly(styrene-b-n-butylmethacrylate) diblock copolymers, PS-b-PBMA, with different lengths of the polystyrene block were investigated. The copolymers display a composition range where the tensile strength of the block copolymers exceeds the values of the corresponding

  17. Immunotheranostic Polymersomes Modularly Assembled from Tetrablock and Diblock Copolymers with Oxidation-Responsive Fluorescence.

    Science.gov (United States)

    Du, Fanfan; Liu, Yu-Gang; Scott, Evan Alexander

    2017-10-01

    Intracellular delivery is a key step for many applications in medicine and for investigations into cellular function. This is particularly true for immunotherapy, which often requires controlled delivery of antigen and adjuvants to the cytoplasm of immune cells. Due to the complex responses generated by the stimulation of diverse immune cell populations, it is critical to monitor which cells are targeted during treatment. To address this issue, we have engineered an immunotheranostic polymersome delivery system that fluorescently marks immune cells following intracellular delivery. N -(3-bromopropyl)phthalimide end-capped poly(ethylene glycol)-bl-poly(propylene sulfide) (PEG-PPS-PI) was synthesized by anionic ring opening polymerization and linked with PEG-PPS-NH 2 via a perylene bisimide (PBI) bridge to form a tetrablock copolymer (PEG-PPS-PBI-PPS-PEG). Block copolymers were assembled into polymersomes by thin film hydration in phosphate buffered saline and characterized by dynamic light scattering, cryogenic electron microscopy and fluorescence spectroscopy. Polymersomes were injected subcutaneously into the backs of mice, and draining lymph nodes were extracted for flow cytometric analysis of cellular uptake and disassembly. Modular self-assembly of tetrablock / diblock copolymers in aqueous solutions induced π-π stacking of the PBI linker that both red-shifted and quenched the PBI fluorescence. Reactive oxygen species within the endosomes of phagocytic immune cell populations oxidized the PPS blocks, which disassembled the polymersomes for dequenching and shifting of the PBI fluorescence from 640 nm to 550 nm emission. Lymph node resident macrophages and dendritic cells were found to increase in 550 nm emission over the course of 3 days by flow cytometry. Immunotheranostic polymersomes present a versatile platform to probe the contributions of specific cell populations during the elicitation of controlled immune responses. Flanking PBI with two oxidation

  18. A bioengineered peripheral nerve construct using aligned peptide amphiphile nanofibers

    Science.gov (United States)

    Yalom, Anisa; Berns, Eric J.; Stephanopoulos, Nicholas; McClendon, Mark T.; Segovia, Luis A.; Spigelman, Igor; Stupp, Samuel I.; Jarrahy, Reza

    2014-01-01

    Peripheral nerve injuries can result in lifelong disability. Primary coaptation is the treatment of choice when the gap between transected nerve ends is short. Long nerve gaps seen in more complex injuries often require autologous nerve grafts or nerve conduits implemented into the repair. Nerve grafts, however, cause morbidity and functional loss at donor sites, which are limited in number. Nerve conduits, in turn, lack an internal scaffold to support and guide axonal regeneration, resulting in decreased efficacy over longer nerve gap lengths. By comparison, peptide amphiphiles (PAs) are molecules that can self-assemble into nanofibers, which can be aligned to mimic the native architecture of peripheral nerve. As such, they represent a potential substrate for use in a bioengineered nerve graft substitute. To examine this, we cultured Schwann cells with bioactive PAs (RGDS-PA, IKVAV-PA) to determine their ability to attach to and proliferate within the biomaterial. Next, we devised a PA construct for use in a peripheral nerve critical sized defect model. Rat sciatic nerve defects were created and reconstructed with autologous nerve, PLGA conduits filled with various forms of aligned PAs, or left unrepaired. Motor and sensory recovery were determined and compared among groups. Our results demonstrate that Schwann cells are able to adhere to and proliferate in aligned PA gels, with greater efficacy in bioactive PAs compared to the backbone-PA alone. In vivo testing revealed recovery of motor and sensory function in animals treated with conduit/PA constructs comparable to animals treated with autologous nerve grafts. Functional recovery in conduit/PA and autologous graft groups was significantly faster than in animals treated with empty PLGA conduits. Histological examinations also demonstrated increased axonal and Schwann cell regeneration within the reconstructed nerve gap in animals treated with conduit/PA constructs. These results indicate that PA nanofibers may

  19. Colloidosomes formed by nonpolar/polar/nonpolar nanoball amphiphiles

    International Nuclear Information System (INIS)

    Chang, Hung-Yu; Sheng, Yu-Jane; Tu, Sheng-Hung; Tsao, Heng-Kwong

    2014-01-01

    Fullerene-based amphiphiles are able to form bilayer vesicles in aqueous solution. In this study, the self-assembly behavior of polymer-tethered nanoballs (NBs) with nonpolar/polar/nonpolar (n-p-n ′ ) motif in a selective solvent is investigated by dissipative particle dynamics. A model NB bears two hydrophobic polymeric arms (n ′ -part) tethered on an extremely hydrophobic NB (n-part) with hydrophilic patch (p-part) patterned on its surface. Dependent on the hydrophobicity and length of tethered arms, three types of aggregates are exhibited, including NB vesicle, core-shell micelle, and segmented-worm. NB vesicles are developed for a wide range of hydrophobic arm lengths. The presence of tethered arms perturbs the bilayer structure formed by NBs. The structural properties including the order parameter, membrane thickness, and area density of the inner leaflet decrease with increasing the arm length. These results indicate that for NBs with longer arms, the extent of interdigitation in the membrane rises so that the overcrowded arms in the inner corona are relaxed. The transport and mechanical properties are evaluated as well. As the arm length grows, the permeability increases significantly because the steric bulk of tethered arms loosens the packing of NBs. By contrast, the membrane tension decreases owing to the reduction of NB/solvent contacts by the polymer corona. Although fusion can reduce membrane tension, NB vesicles show strong resistance to fusion. Moreover, the size-dependent behavior observed in small liposomes is not significant for NB vesicles due to isotropic geometry of NB. Our simulation results are consistent with the experimental findings

  20. Colloidosomes formed by nonpolar/polar/nonpolar nanoball amphiphiles

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Hung-Yu; Sheng, Yu-Jane, E-mail: yjsheng@ntu.edu.tw, E-mail: hktsao@cc.ncu.edu.tw [Department of Chemical Engineering, National Taiwan University, Taipei 106, Taiwan (China); Tu, Sheng-Hung [Department of Chemical and Materials Engineering, National Central University, Jhongli 320, Taiwan (China); Tsao, Heng-Kwong, E-mail: yjsheng@ntu.edu.tw, E-mail: hktsao@cc.ncu.edu.tw [Department of Chemical and Materials Engineering and Department of Physics, National Central University, Jhongli 320, Taiwan (China)

    2014-08-07

    Fullerene-based amphiphiles are able to form bilayer vesicles in aqueous solution. In this study, the self-assembly behavior of polymer-tethered nanoballs (NBs) with nonpolar/polar/nonpolar (n-p-n{sup ′}) motif in a selective solvent is investigated by dissipative particle dynamics. A model NB bears two hydrophobic polymeric arms (n{sup ′}-part) tethered on an extremely hydrophobic NB (n-part) with hydrophilic patch (p-part) patterned on its surface. Dependent on the hydrophobicity and length of tethered arms, three types of aggregates are exhibited, including NB vesicle, core-shell micelle, and segmented-worm. NB vesicles are developed for a wide range of hydrophobic arm lengths. The presence of tethered arms perturbs the bilayer structure formed by NBs. The structural properties including the order parameter, membrane thickness, and area density of the inner leaflet decrease with increasing the arm length. These results indicate that for NBs with longer arms, the extent of interdigitation in the membrane rises so that the overcrowded arms in the inner corona are relaxed. The transport and mechanical properties are evaluated as well. As the arm length grows, the permeability increases significantly because the steric bulk of tethered arms loosens the packing of NBs. By contrast, the membrane tension decreases owing to the reduction of NB/solvent contacts by the polymer corona. Although fusion can reduce membrane tension, NB vesicles show strong resistance to fusion. Moreover, the size-dependent behavior observed in small liposomes is not significant for NB vesicles due to isotropic geometry of NB. Our simulation results are consistent with the experimental findings.

  1. Synthetic cationic amphiphilic α-helical peptides as antimicrobial agents.

    Science.gov (United States)

    Wiradharma, Nikken; Khoe, Ulung; Hauser, Charlotte A E; Seow, See Voon; Zhang, Shuguang; Yang, Yi-Yan

    2011-03-01

    Antimicrobial peptides (AMPs) secreted by the innate immune system are prevalent as the effective first-line of defense to overcome recurring microbial invasions. They have been widely accepted as the blueprints for the development of new antimicrobial agents for the treatment of drug resistant infections. However, there is also a growing concern that AMPs with a sequence that is too close to the host organism's AMP may inevitably compromise its own natural defense. In this study, we design a series of synthetic (non-natural) short α-helical AMPs to expand the arsenal of the AMP families and to gain further insights on their antimicrobial activities. These cationic and amphiphilic peptides have a general sequence of (XXYY)(n) (X: hydrophobic residue, Y: cationic residue, and n: the number of repeat units), and are designed to mimic the folding behavior of the naturally-occurring α-helical AMPs. The synthetic α-helical AMPs with 3 repeat units, (FFRR)(3), (LLRR)(3), and (LLKK)(3), are found to be more selective towards microbial cells than rat red blood cells, with minimum inhibitory concentration (MIC) values that are more than 10 times lower than their 50% hemolytic concentrations (HC(50)). They are effective against Gram-positive B. subtilis and yeast C. albicans; and the studies using scanning electron microscopy (SEM) have elucidated that these peptides possess membrane-lytic activities against microbial cells. Furthermore, non-specific immune stimulation assays of a typical peptide shows negligible IFN-α, IFN-γ, and TNF-α inductions in human peripheral blood mononuclear cells, which implies additional safety aspects of the peptide for both systemic and topical use. Therefore, the peptides designed in this study can be promising antimicrobial agents against the frequently-encountered Gram-positive bacteria- or yeast-induced infections. Copyright © 2010 Elsevier Ltd. All rights reserved.

  2. Soft/Hard-Coupled Amphiphilic Polymer Nanospheres for Water Lubrication.

    Science.gov (United States)

    Li, Zhaoxia; Ma, Shuanhong; Zhang, Ga; Wang, Daoai; Zhou, Feng

    2018-03-14

    Amphiphilic polymer nanospheres of poly(3-sulfopropyl methacrylate potassium salt- co-styrene) [P(SPMA- co-St)] were prepared by a simple soap-free emulsion polymerization method and used as efficient water lubrication additives to enhance the antiwear behaviors of the Ti 6 Al 4 V alloy. The monodisperse and flexible P(SPMA- co-St) bicomponent copolymer nanospheres were synthesized with a controllable manner by adjusting the mass fraction ratio of the monomers, with the hydrophobic polystyrene (PSt) as the hard skeletal carrier component and the hydrophilic PSPMA with a hydration layer structure as the soft lubrication layer in the course of friction. The influences of the monomer concentration, the copolymer nanosphere additive content, the load, and the frequency of the friction conditions on their tribological properties were studied in detail, and a probable antiwear mechanism of the soft/hard-coupled copolymer nanospheres under water lubrication was also proposed. The results show that compared with pure PSt, the P(SPMA- co-St) polymer nanospheres exhibited better antiwear property as an additive for water lubrication, and the friction coefficient and the wear volume first decreased and then increased with the increase of the SPMA content, indicating that the hydrophilic SPMA has a significant effect on lubrication properties owing to its hydration performance. Furthermore, with the increase of polymer nanosphere concentration, the friction coefficient and wear amount also decreased to a stable and low value at a saturation concentration of 1 wt %. The flexible polymer nanospheres with a hydrophilic soft SPMA shell and a rigid PSt core exhibited good friction-reduction and antiwear performance as lubrication additives, indicating their promising and potential applications in water lubrication and biological lubrication.

  3. 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.

  4. Where surface physics and fluid dynamics meet: rupture of an amphiphile layer by fluid flow.

    Science.gov (United States)

    Bandi, M M; Goldburg, W I; Cressman, J R; Kellay, H

    2006-03-14

    We investigate the fluctuating pattern created by a jet of fluid impingent upon an amphiphile-covered surface. This microscopically thin layer is initially covered with 50 microm floating particles so that the layer can be visualized. A vertical jet of water located below the surface and directed upward drives a hole in this layer. The hole is particle-free and is surrounded by the particle-laden amphiphile region. The jet ruptures the amphiphile layer creating a particle-free region that is surrounded by the particle-covered surface. The aim of the experiment is to understand the (fluctuating) shape of the ramified interface between the particle-laden and particle-free regions.

  5. Magnetic amphiphilic hybrid carbon nanotubes containing N-doped and undoped sections: powerful tensioactive nanostructures

    Science.gov (United States)

    Purceno, Aluir D.; Machado, Bruno F.; Teixeira, Ana Paula C.; Medeiros, Tayline V.; Benyounes, Anas; Beausoleil, Julien; Menezes, Helvecio C.; Cardeal, Zenilda L.; Lago, Rochel M.; Serp, Philippe

    2014-11-01

    In this work, unique amphiphilic magnetic hybrid carbon nanotubes (CNTs) are synthesized and used as tensioactive nanostructures in different applications. These CNTs interact very well with aqueous media due to the hydrophilic N-doped section, whereas the undoped hydrophobic one has strong affinity for organic molecules. The amphiphilic character combined with the magnetic properties of these CNTs opens the door to completely new and exciting applications in adsorption science and catalysis. These amphiphilic N-doped CNTs can also be used as powerful tensioactive emulsification structures. They can emulsify water/organic mixtures and by a simple magnetic separation the emulsion can be easily broken. We demonstrate the application of these CNTs in the efficient adsorption of various molecules, in addition to promoting biphasic processes in three different reactions, i.e. transesterification of soybean oil, quinoline extractive oxidation with H2O2 and a metal-catalyzed aqueous oxidation of heptanol with molecular oxygen.In this work, unique amphiphilic magnetic hybrid carbon nanotubes (CNTs) are synthesized and used as tensioactive nanostructures in different applications. These CNTs interact very well with aqueous media due to the hydrophilic N-doped section, whereas the undoped hydrophobic one has strong affinity for organic molecules. The amphiphilic character combined with the magnetic properties of these CNTs opens the door to completely new and exciting applications in adsorption science and catalysis. These amphiphilic N-doped CNTs can also be used as powerful tensioactive emulsification structures. They can emulsify water/organic mixtures and by a simple magnetic separation the emulsion can be easily broken. We demonstrate the application of these CNTs in the efficient adsorption of various molecules, in addition to promoting biphasic processes in three different reactions, i.e. transesterification of soybean oil, quinoline extractive oxidation with H2O2 and

  6. Catalytic Y-tailed amphiphilic homopolymers - aqueous nanoreactors for high activity, low loading SCS pincer catalysts.

    Science.gov (United States)

    Patterson, Joseph P; Cotanda, Pepa; Kelley, Elizabeth G; Moughton, Adam O; Lu, Annhelen; Epps, Thomas H; O'Reilly, Rachel K

    2013-01-01

    A new amphiphilic homopolymer bearing an SCS pincer palladium complex has been synthesized by reversible addition fragmentation chain transfer polymerization. The amphiphile has been shown to form spherical and worm-like micelles in water by cryogenic transmission electron microscopy and small angle neutron scattering. Segregation of reactive components within the palladium containing core results in increased catalytic activity of the pincer compound compared to small molecule analogues. This allows carbon-carbon bond forming reactions to be performed in water with reduced catalyst loadings and enhanced activity.

  7. The effect of amphiphilic polymers with a continuous amphiphilicity profile on the membrane properties in a bicontinuous microemulsions studied by neutron scattering

    Science.gov (United States)

    Klemmer, Helge F. M.; Frielinghaus, Henrich; Allgaier, Jürgen; Ohl, Michael; Holderer, Olaf

    2017-06-01

    Microemulsion systems consisting of oil, water and surfactant have been studied with neutron scattering techniques. The amount of surfactant needed to form a microemulsion can be dramatically reduced by the addition of small amounts of amphiphilic block copolymers (boosting effect). Here, we studied the influence of block copolymers with gradually changing amphiphilicity from hydrophilic to hydrophobic. Small angle neutron scattering (SANS), neutron spin echo spectroscopy (NSE) and phase diagram measurements in combination give access to the elastic properties of the membrane. The underlying NSE experiments for this interpretation rely on smallest changes of the relaxation curves (of ca. 1% steps) for still small changes of the bending rigidity (of ca. 10% steps). This high reliability of the experiments conducted at the SNS-NSE displays the accuracy of the instrument itself and the latest developments of the evaluation software, which were necessary to interpret such tiny changes of the bending rigidity reliably.

  8. The Plumber’s Nightmare Phase in Diblock Copolymer/Homopolymer Blends. A Self-Consistent Field Theory Study.

    KAUST Repository

    Martinez-Veracoechea, Francisco J.

    2009-11-24

    Using self-consistent field theory, the Plumber\\'s Nightmare and the double diamond phases are predicted to be stable in a finite region of phase diagrams for blends of AB diblock copolymer (DBC) and A-component homopolymer. To the best of our knowledge, this is the first time that the P phase has been predicted to be stable using self-consistent field theory. The stabilization is achieved by tuning the composition or conformational asymmetry of the DBC chain, and the architecture or length of the homopolymer. The basic features of the phase diagrams are the same in all cases studied, suggesting a general type of behavior for these systems. Finally, it is noted that the homopolymer length should be a convenient variable to stabilize bicontinuous phases in experiments. © 2009 American Chemical Society.

  9. Effect of solvent quality and chain density on normal and frictional forces between electrostatically anchored thermoresponsive diblock copolymer layers

    DEFF Research Database (Denmark)

    An, Junxue; Liu, Xiaoyan; Dedinaite, Andra

    2017-01-01

    and a thermoresponsive block of poly(2-isopropyl-2-oxazoline), PIPOZ. We find that at a given temperature different polymer chain densities at the silica surface are achieved depending on the previous temperature history. We explore how this affects surface and friction forces between such layers using the atomic force......Equilibration in adsorbing polymer systems can be very slow, leading to different physical properties at a given condition depending on the pathway that was used to reach this state. Here we explore this phenomenon using a diblock copolymer consisting of a cationic anchor block....... The friction forces decrease in the cooling stage due to rehydration of the PIPOZ chain. A consequence of the adsorption hysteresis is that the friction forces measured at 25 °C are significantly lower after exposure to a temperature of 40 °C than prior to heating, which is due to higher polymer chain density...

  10. Morphology and mechanical behavior of blends and diblock copolymers of 1,2 and 1,4 polybutadiene

    Energy Technology Data Exchange (ETDEWEB)

    Cohen, R.E.; Wilfong, D.E.

    1981-02-25

    The structure and mechanical properties of a series of polymer blends and block copolymers comprised of medium cis 1,4-polybutadiene and 99% 1,2-polybutadiene have been investigated. Thermal properties (DSC) were determined at two levels of radiation crosslinking and for various sample preparation procedures (solvent and thermal history). Dynamic mechanical spectra (3.5 Hz) were measured over temperature range from 180 to 310K. Transmission electron microscopy was also used for establishing the number phases and the domain size and geometry in the heterogeneous materials. Stress-strain curves were determined for the various samples as a function of crosslink density and casting solvent. Equilibrium swelling ratios were measured for each specimen at the same radiation dose in a good solvent. Swelling values were also obtained in a series of solvents for the parent homopolymers and for a diblock copolymer containing 45% 1,2 polybutadiene.

  11. Ordered, microphase-separated, noncharged-charged diblock copolymers via the sequential ATRP of styrene and styrenic imidazolium monomers

    Energy Technology Data Exchange (ETDEWEB)

    Shi, ZX; Newell, BS; Bailey, TS; Gin, DL

    2014-12-15

    A series of imidazolium-based noncharged-charged diblock copolymers (1) was synthesized by the direct, sequential ATRP of styrene and styrenic imidazolium bis(trifluoromethyl)sulfonamide monomers with methyl, n-butyl, and n-decyl side-chains. Small-angle X-ray scattering studies on initial examples of 1 with a total of 50 repeat units and styrene:imidazolium-styrene repeat unit ratios of 25:25, 20:30, and 15:35 showed that their ability to form ordered nanostructures (i.e., sphere and cylinder phases) in their neat states depends on both the block ratio and the length of the alkyl side-chain on the imidazolium monomer. To our knowledge, the synthesis of imidazolium-based BCPs that form ordered, phase-separated nanostructures via direct ATRP of immiscible co-monomers is unprecedented. (C) 2014 Elsevier Ltd. All rights reserved.

  12. Charge-Transfer Supra-Amphiphiles Built by Water-Soluble Tetrathiafulvalenes and Viologen-Containing Amphiphiles: Supramolecular Nanoassemblies with Modifiable Dimensions.

    Science.gov (United States)

    Lv, Zhong-Peng; Chen, Bin; Wang, Hai-Ying; Wu, Yue; Zuo, Jing-Lin

    2015-08-05

    In this study, multidimensional nanoassemblies with various morphologies such as nanosheets, nanorods, and nanofibers are developed via charge-transfer interaction and supra-amphiphile self-assembling in aqueous phase. The charge-transfer interactions between tetrathiafulvalene derivatives (TTFs) and methyl viologen derivatives (MVs) have been confirmed by the characteristic charger-transfer absorption. (1) H NMR and electrospray ionizsation mass spectrometry (ESI-MS) analyses also indicate supra-amphiphiles are formed by the combination of TTFs and MVs head group through charge-transfer interaction and Coulombic force. X-ray single crystal structural studies, transmission electron microscopy (TEM), and scanning electron microscopy (SEM) reveal that both linkage pattern of TTFs in hydrophilic part and alkane chain structure in hydrophobic part have significant influence on nanoassemblies morphology and microstructure. Moreover, gold nanoparticles (AuNPs) are introduced in the above supramolecular nanoassemblies to construct a supra-amphiphile-driven organic-AuNPs assembly system. AuNPs could be assembled into 1D-3D structures by adding different amount of MVs. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Ordering of anisotropic nanoparticles in diblock copolymer lamellae: Simulations with dissipative particle dynamics and a molecular theory.

    Science.gov (United States)

    Berezkin, Anatoly V; Kudryavtsev, Yaroslav V; Gorkunov, Maxim V; Osipov, Mikhail A

    2017-04-14

    Local distribution and orientation of anisotropic nanoparticles in microphase-separated symmetric diblock copolymers has been simulated using dissipative particle dynamics and analyzed with a molecular theory. It has been demonstrated that nanoparticles are characterized by a non-trivial orientational ordering in the lamellar phase due to their anisotropic interactions with isotropic monomer units. In the simulations, the maximum concentration and degree of ordering are attained for non-selective nanorods near the domain boundary. In this case, the nanorods have a certain tendency to align parallel to the interface in the boundary region and perpendicular to it inside the domains. Similar orientation ordering of nanoparticles located at the lamellar interface is predicted by the molecular theory which takes into account that the nanoparticles interact with monomer units via both isotropic and anisotropic potentials. Computer simulations enable one to study the effects of the nanorod concentration, length, stiffness, and selectivity of their interactions with the copolymer components on the phase stability and orientational order of nanoparticles. If the volume fraction of the nanorods is lower than 0.1, they have no effect on the copolymer transition from the disordered state into a lamellar microstructure. Increasing nanorod concentration or nanorod length results in clustering of the nanorods and eventually leads to a macrophase separation, whereas the copolymer preserves its lamellar morphology. Segregated nanorods of length close to the width of the diblock copolymer domains are stacked side by side into smectic layers that fill the domain space. Thus, spontaneous organization and orientation of nanorods leads to a spatial modulation of anisotropic composite properties which may be important for various applications.

  14. A synthetic strategy for novel nonsymmetrical bola amphiphiles based on carbohydrates

    NARCIS (Netherlands)

    Schuur, B; Wagenaar, Anno; Heeres, Andre; Heeres, Erik H. J.

    2004-01-01

    A number of novel nonionic bolaform amphiphiles with nonidentical aldityl head groups, 1-(1-deoxy-D-galactitol-l-ylamino)-6-(1-deoxy-D- galactitol-1-ylamino)hexane (4a), 1-(1-deoxy-D-mannitol-1-ylamino)-6-(1-deoxy-D-glucitol-1-ylamino)hexane (4b). and

  15. Functionalized surfaces of polylactide modified by Langmuir-Blodgett films of amphiphilic block copolymers

    Czech Academy of Sciences Publication Activity Database

    Kubies, Dana; Machová, Luďka; Brynda, Eduard; Lukáš, Jaromír; Rypáček, František

    2003-01-01

    Roč. 14, č. 2 (2003), s. 143-149 ISSN 0957-4530 R&D Projects: GA ČR GA203/99/0576 Institutional research plan: CEZ:AV0Z4050913 Keywords : polylactide * Langmuir - Blodgett films * amphiphilic block copolymers Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.930, year: 2003

  16. Fabrication of Propeller-Shaped Supra-amphiphile for Construction of Enzyme-Responsive Fluorescent Vesicles.

    Science.gov (United States)

    Li, Jie; Liu, Kaerdun; Han, Yuchun; Tang, Ben Zhong; Huang, Jianbin; Yan, Yun

    2016-10-04

    Propeller-shaped molecules have been recognized to display fantastic AIE (aggregation induced emission), but they can hardly self-assemble into nanostructures. Herein, we for the first time report that ionic complexation between a water-soluble tetrapheneyl derivative and an enzyme substrate in aqueous media produces a propeller-shaped supra-amphiphile that self-assembles into enzyme responsive fluorescent vesicles. The supra-amphiphile was fabricated upon complexation between a water-soluble propeller-shaped AIE luminogen TPE-BPA and myristoylcholine chloride (MChCl) in aqueous media. MChCl filled in the intramolecular voids of propeller-shaped TPE-BPA upon supra-amphiphile formation, which endows the supra-amphiphile superior self-assembling ability to the component molecules thus leading to the formation of fluorescent vesicles. Because MChCl is the substrate of cholinesterases, the vesicles dissemble in the presence of cholinesterases, and the fluorescent intensity can be correlated to the level of enzymes. The resulting fluorescent vesicles may be used to recognize the site of Alzheimer's disease, to encapsulate the enzyme inhibitor, and to release the inhibitor at the disease site.

  17. Anti-Biofouling Properties of Comblike Block Copolymers with Amphiphilic Side Chains

    International Nuclear Information System (INIS)

    Krishnan, S.; Ayothi, R.; Hexemer, A.; Finlay, J.; Sohn, K.; Perry, R.; Ober, C.; Kramer, E.; Callow, M.

    2006-01-01

    Surfaces of novel block copolymers with amphiphilic side chains were studied for their ability to influence the adhesion of marine organisms. The surface-active polymer, obtained by grafting fluorinated molecules with hydrophobic and hydrophilic blocks to a block copolymer precursor, showed interesting bioadhesion properties. Two different algal species, one of which adhered strongly to hydrophobic surfaces, and the other, to hydrophilic surfaces, showed notably weak adhesion to the amphiphilic surfaces. Both organisms are known to secrete adhesive macromolecules, with apparently different wetting characteristics, to attach to underwater surfaces. The ability of the amphiphilic surface to undergo an environment-dependent transformation in surface chemistry when in contact with the extracellular polymeric substances is a possible reason for its antifouling nature. Near-edge X-ray absorption fine structure spectroscopy (NEXAFS) was used, in a new approach based on angle-resolved X-ray photoelectron spectroscopy (XPS), to determine the variation in chemical composition within the top few nanometers of the surface and also to study the surface segregation of the amphiphilic block. A mathematical model to extract depth-profile information from the normalized NEXAFS partial electron yield is developed

  18. The encapsulation of an amphiphile into polystyrene microspheres of narrow size distribution

    Directory of Open Access Journals (Sweden)

    Pellach Michal

    2011-12-01

    Full Text Available Abstract Encapsulation of compounds into nano- or microsized organic particles of narrow size distribution is of increasing importance in fields of advanced imaging and diagnostic techniques and drug delivery systems. The main technology currently used for encapsulation of molecules within uniform template particles while retaining their size distribution is based on particle swelling methodology, involving penetration of emulsion droplets into the particles. The swelling method, however, is efficient for encapsulation only of hydrophobic compounds within hydrophobic template particles. In order to be encapsulated, the molecules must favor the hydrophobic phase of an organic/aqueous biphasic system, which is not easily achieved for molecules of amphiphilic character. The following work overcomes this difficulty by presenting a new method for encapsulation of amphiphilic molecules within uniform hydrophobic particles. We use hydrogen bonding of acid and base, combined with a pseudo salting out effect, for the entrapment of the amphiphile in the organic phase of a biphasic system. Following the entrapment in the organic phase, we demonstrated, using fluorescein and (antibiotic tetracycline as model molecules, that the swelling method usually used only for hydrophobes can be expanded and applied to amphiphilic molecules.

  19. Novel self-associative and multiphase nanostructured soft carriers based on amphiphilic hyaluronic acid derivatives

    DEFF Research Database (Denmark)

    Eenschooten, Corinne; Vaccaro, Andrea; Delie, Florence

    2012-01-01

    The purpose of the present study was to investigate the physicochemical properties in aqueous media of amphiphilic hyaluronic acid (HA) derivatives obtained by reaction of HA’s hydroxyl groups with octenyl succinic anhydride (OSA). The self-associative properties of the resulting octenyl succinic...

  20. The encapsulation of an amphiphile into polystyrene microspheres of narrow size distribution.

    Science.gov (United States)

    Pellach, Michal; Margel, Shlomo

    2011-12-06

    Encapsulation of compounds into nano- or microsized organic particles of narrow size distribution is of increasing importance in fields of advanced imaging and diagnostic techniques and drug delivery systems. The main technology currently used for encapsulation of molecules within uniform template particles while retaining their size distribution is based on particle swelling methodology, involving penetration of emulsion droplets into the particles. The swelling method, however, is efficient for encapsulation only of hydrophobic compounds within hydrophobic template particles. In order to be encapsulated, the molecules must favor the hydrophobic phase of an organic/aqueous biphasic system, which is not easily achieved for molecules of amphiphilic character.The following work overcomes this difficulty by presenting a new method for encapsulation of amphiphilic molecules within uniform hydrophobic particles. We use hydrogen bonding of acid and base, combined with a pseudo salting out effect, for the entrapment of the amphiphile in the organic phase of a biphasic system. Following the entrapment in the organic phase, we demonstrated, using fluorescein and (antibiotic) tetracycline as model molecules, that the swelling method usually used only for hydrophobes can be expanded and applied to amphiphilic molecules.

  1. Amphiphilic derivatives of (3β,17β)-3-hydroxyandrost-5-ene-17-carboxylic acid

    Czech Academy of Sciences Publication Activity Database

    Özdemir, Zülal; Bildziukevich, Uladzimir; Šaman, David; Havlíček, Libor; Rárová, L.; Navrátilová, L.; Wimmer, Zdeněk

    2017-01-01

    Roč. 128, DEC (2017), s. 58-67 ISSN 0039-128X R&D Projects: GA MŠk LD15012 Institutional support: RVO:61389030 ; RVO:61388963 Keywords : Amphiphile * Antimicrobial activity * Cytotoxicity * Diamine * Polyamine * Steroid Subject RIV: CC - Organic Chemistry; CC - Organic Chemistry (UOCHB-X) OBOR OECD: Organic chemistry Impact factor: 2.282, year: 2016

  2. Self-assembly of aromatic-derivatized amphiphiles: Phenyl, biphenyl, and terphenyl fatty acids and phospholipids

    Energy Technology Data Exchange (ETDEWEB)

    Geiger, H.C.; Perlstein, J.; Lachicotte, R.J.; Wyrozebski, K.; Whitten, D.G. [Univ. of Rochester, NY (United States)]|[Los Alamos National Lab., NM (United States). Chemical Science and Technology Div.

    1999-08-17

    This paper reports the synthesis of a series of amphiphiles (fatty acids and phosphatidylcholine derivatives) containing phenyl, biphenyl, and terphenyl chromophores inserted in the hydrocarbon chain and a study of their self-assembly in Langmuir-Blodgett films and aqueous dispersions. As observed and reported earlier for amphiphiles containing trans-stilbene, styrylthiophene, or azobenzene chromophores, several of the biphenyl and terphenyl derivatives show strong evidence of ground state association to form H aggregates characterized by a blue shift in absorption and a structured, red-shifted fluorescence. The phenyl amphiphiles show different behavior, suggesting that, even for pure films or bilayers, there is very little or no ground state association. For the biphenyl and terphenyl phospholipids, aqueous suspensions obtained by sonication are closed bilayer vesicles similar in size to those formed from the corresponding saturated phospholipids. The overall results of the present study indicate that biphenyl and terphenyl amphiphiles undergo aggregation processes to form compact arrays formally similar to those observed with stilbenen tolan, azobenzene, and squaraine derivatives but that the aromatic-aromatic interactions are considerably weaker than those for the more extended aromatics and lead to less distortion of the assembly structure.

  3. H-aggregation of azobenzene-substituted amphiphiles in vesicular membranes

    NARCIS (Netherlands)

    Kuiper, JM; Engberts, JBFN

    2004-01-01

    Photochemical switching has been studied of double-tailed phosphate amphiphiles containing azobenzene units in both tails in aqueous vesicular dispersions and in mixed vesicular systems with 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC). Since the ease of switching depends on the strength of the

  4. Platform Approach to Produce Polymer Nanoparticles with Modular Functionality from Amphiphilic Block Copolymer Stabilizers

    Science.gov (United States)

    2014-04-01

    Bonilla, A.; Herk, A. M.; Heuts , J. P. A. Preparation of hairy particles and antifouling films using brush-type amphiphilic block copolymer...surfactants in emulsion polymerization. Macromolecules 2010, 43 (6), 2721–2731. 5. Muñoz-Bonilla, A.; Herk, A. M.; Heuts , J. P. A. Adding stimuli

  5. Investigating the Structure of Aggregates of an Amphiphilic Cyanine Dye with Molecular Dynamics Simulations

    NARCIS (Netherlands)

    Haverkort, Frank; Stradomska, Anna; de Vries, Alex H.; Knoester, Jasper

    2013-01-01

    We perform molecular dynamics (MD) simulations of the self-assembly process of pseudoisocyanine dye molecules with amphiphilic substituents (amphi-PIC). The spontaneous aggregation of cyanine molecules into large molecular J-aggregates with optical functionality has drawn attention for many decades

  6. One-pot synthesis of isocyanate and methacrylate multifunctionalized polyisobutylene and polyisobutylene-based amphiphilic networks

    Czech Academy of Sciences Publication Activity Database

    Toman, Luděk; Janata, Miroslav; Spěváček, Jiří; Dvořánková, B.; Látalová, Petra; Vlček, Petr; Sikora, Antonín; Michálek, Jiří; Pekárek, Michal

    2006-01-01

    Roč. 44, č. 9 (2006), s. 2891-2900 ISSN 0887-624X R&D Projects: GA ČR GA203/04/1050 Institutional research plan: CEZ:AV0Z40500505 Keywords : amphiphilic networks * cationic copolymerization * 2-hydroxyethyl methacrylate isobutylene Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.405, year: 2006

  7. Generation dependent mesophase behavior in extended amphiphilic dendrons in the shape of macromolecular dumbbells.

    Science.gov (United States)

    Cho, Byoung-Ki; Jain, Anurag; Gruner, Sol M; Wiesner, Ulrich

    2005-04-28

    Small angle X-ray scattering studies of 2nd and 3rd generation based extended amphiphilic dendrons in the shape of macromolecular dumbbells with identical hydrophilic volume fractions suggest 2-D hexagonal columnar and Pm3n micellar cubic mesophases, respectively, elucidating the role of shape induced interface curvature in mesophase formation.

  8. Influence of corona structure on binding of an ionic surfactant in oppositely charged amphiphilic polyelectrolyte micelles

    Czech Academy of Sciences Publication Activity Database

    Delisavva, F.; Uchman, M.; Škvarla, J.; Wozniak, E.; Pavlova, Ewa; Šlouf, Miroslav; Garamus, V. M.; Procházka, K.; Štěpánek, M.

    2016-01-01

    Roč. 32, č. 16 (2016), s. 4059-4065 ISSN 0743-7463 R&D Projects: GA TA ČR(CZ) TE01020118; GA MŠk(CZ) LO1507 Institutional support: RVO:61389013 Keywords : amphiphilic polymers * polyelectrolyte * corona structure Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.833, year: 2016

  9. Non-amphiphilic carbohydrate liquid crystals containing an intact monosaccharide moiety

    NARCIS (Netherlands)

    Smits, E; Engberts, J.B.F.N.; Kellogg, R.M; van Doren, H.A.

    1995-01-01

    A chiral rigid moiety which forms the basis of a new class of non-amphiphilic carbohydrate liquid crystals has been developed. This moiety contains a fully intact glucopyranose ring embedded in a trans-decalin structure. The original carbohydrate is substituted so that only two hydroxyl groups are

  10. Totally Organic Redox-Active pH-Sensitive Nanoparticles Stabilized by Amphiphilic Aromatic Polyketones

    NARCIS (Netherlands)

    Araya-Hermosilla, Esteban; Catalán-Toledo, José; Muñoz-Suescun, Fabian; Oyarzun-Ampuero, Felipe; Raffa, Patrizio; Polgar, Lorenzo Massimo; Picchioni, Francesco; Moreno-Villoslada, Ignacio

    2018-01-01

    Amphiphilic aromatic polymers have been synthesized by grafting aliphatic polyketones with 4-(aminomethyl)benzoic acid at different molar ratios via the Paal-Knorr reaction. The resulting polymers, showing diketone conversion degree of 16, 37, 53, and 69 %, have been complexed with the redox-active

  11. Synthesis of amphiphilic copolymers by ATRP initiated with a bifunctional initiator containing trichlomethyl groups

    Czech Academy of Sciences Publication Activity Database

    Ritz, Pavel; Látalová, Petra; Janata, Miroslav; Toman, Luděk; Kříž, Jaroslav; Genzer, J.; Vlček, Petr

    2007-01-01

    Roč. 67, č. 10 (2007), s. 1027-1039 ISSN 1381-5148 R&D Projects: GA MŠk 1P05ME753 Institutional research plan: CEZ:AV0Z40500505 Keywords : ATRP * block copolymer * polyhalogenated initiator * amphiphilic copolymer Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.720, year: 2007

  12. Structural properties and elasticity of amphiphilics on water

    Science.gov (United States)

    Daillant, J.; Bosio, L.; Harzallah, B.; Benattar, J. J.

    1991-02-01

    Monolayers of amphiphilic molecules adsorbed at the air-water interface have been studied using X-ray reflectivity. This technique allows an accurate and independent determination of thicknesses (by the measurement of fringes of equal inclination) as well as densities and roughnesses (since this is an absolute intensity measurement); therefore a complete electron density profile can be obtained. The surface roughness is due to thermally excited capillary waves, and is thus related to the dynamics of the interface, which are conditionned by the elastic constants of the layer. The phase diagrams of the C{15}, C{21} and C{29} fatty acids and of the phospholipid L-α-DPPC have been investigated using this method, and an analysis of the phase transitions has been performed. From the structural point of view, a general feature of this class of compounds adsorbed on water is an unchanging aliphatic medium density within the liquid and solid phases. If follows that the pressure vs. film thickness curves mimic the pressure area curves. In particular evidence for the liquid-expanded to liquid-condensed transition is given by an abrupt increase of the aliphatic medium thickness. The data suggest that this transition should involve conformational changes. Furthermore the decrease in molecular area within the liquid condensed phase is revealed by a decreasing molecular tilt angle. The structure of this phase is also shown to be independent of the temperature and of the nature of the polar head-group. A transition to a multilayer structure is observed with the longest chain compound. We show that the dynamics of the interface are consistent in the liquid phases with a simple capillary wave model, with no adjustable parameter. A strong drop in the roughness at the transition to the solid state reveals the onset of a rigidity against bending. The high values of the rigidity modulus obtained (on the order of 100 k_B T) are sensitive to the aliphatic chain length and can be

  13. Sulfonated amphiphilic block copolymers : synthesis, self-assembly in water, and application as stabilizer in emulsion polymerization

    Science.gov (United States)

    Jiguang Zhang; Matthew R. Dubay; Carl J. Houtman; Steven J. Severtson

    2009-01-01

    Described is the synthesis of diblock copolymers generated via sequential atom transfer radical polymerization (ATRP) of poly(n-butyl acrylate) (PnBA) followed by chain augmentation with either sulfonated poly(2-hydroxyethyl methacrylate) (PHEMA) or poly(2-hydroxyethyl acrylate) (PHEA) blocks. ATRP of PHEMA or PHEA from PnBA macroinitiator was conducted in acetone/...

  14. Novel poly(ethylene oxide monomethyl ether)-b-poly(.epsilon.-caprolactone) diblock copolymers containing a pH-acid labile ketal group as a block linkage

    Czech Academy of Sciences Publication Activity Database

    Petrova, Svetlana; Jäger, Eliezer; Konefal, Rafal; Jäger, Alessandro; Venturini, Cristina Garcia; Spěváček, Jiří; Pavlova, Ewa; Štěpánek, Petr

    2014-01-01

    Roč. 5, č. 12 (2014), s. 3884-3893 ISSN 1759-9954 R&D Projects: GA ČR GAP208/10/1600; GA TA ČR TE01020118 Institutional support: RVO:61389013 Keywords : MPOE-b-PCL diblock copolymers * ring-opening polymerization * "click" chemistry Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.520, year: 2014

  15. Effect of temperature on the interfacial behavior of a polystyrene-b-poly(methyl methacrylate) diblock copolymer at the air/water interface.

    Science.gov (United States)

    Seo, Yongsok; Cho, Chung Yeon; Hwangbo, Minyoung; Choi, Hyoung Jin; Hong, Soon Man

    2008-03-18

    Monolayers of a polystyrene-poly(methyl methacrylate) (PS-PMMA) diblock copolymer at the air-water interface were studied by measuring the surface pressure-area isotherms at several temperatures. Langmuir film balance experiments and atomic force microscopy showed that the diblock copolymer molecules formed surface micelles. In the plot of the surface pressure versus surface area per repeating unit, the monolayer changed from the gas phase to the liquid expanded phase at lower surface pressure for systems at low temperature compared to those at high temperature. In addition, a plateau, corresponding to the transition from the liquid expanded to liquid condensed phase, appeared in that plot at lower surface pressure for systems with a higher subphase (water) temperature. Hysteresis was observed in the compression-expansion cycle process. Increasing the subphase temperature alleviated this hyteresis gap, especially at low surface pressures. The minimum in the plot of the surface pressure versus surface area per repeating unit in the expansion process (which arises from the transition) and the transition plateau appeared more vividly at higher water temperature. These dynamic experimental results show that PS-PMMA diblock copolymers, in which both blocks are insoluble in water, do not form complicated entanglements in two-dimensional space. Although higher water temperature provided more entropy to the chains, and thus more conformational freedom, it did not change the surface morphology of the condensed film because both blocks of PS-PMMA are insoluble in water.

  16. Adsorption of phthalic acid esters (PAEs) by amphiphilic polypropylene nonwoven from aqueous solution: the study of hydrophilic and hydrophobic microdomain.

    Science.gov (United States)

    Zhou, Xiangyu; Wei, Junfu; Zhang, Huan; Liu, Kai; Wang, Han

    2014-05-30

    A kind of amphiphilic polypropylene nonwoven with hydrophilic and hydrophobic microdomain was prepared through electron beam induced graft polymerization and subsequent ring opening reaction and then utilized in the adsorption of phthalic acid esters (PAEs). To elucidate the superiority of such amphiphilic microdomain, a unique structure without hydrophilic part was constructed as comparison. In addition, the adsorption behaviors including adsorption kinetics, isotherms and pH effect were systematically investigated. The result indicated that the amphiphilic structure and the synergy between hydrophilic and hydrophobic microdomain could considerably improve the adsorption capacities, rate and affinity. Particularly the existence of hydrophilic microdomain could reduce the diffusion resistance and energy barrier in the adsorption process. These adsorption results showed that the amphiphilic PP nonwoven have the potential to be used in environmental application. Copyright © 2014 Elsevier B.V. All rights reserved.

  17. 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

  18. Photophysical and photochemical studies of a novel amphiphilic zinc phthalocyanine and its interaction with calf thymus DNA

    Science.gov (United States)

    Yuan, Linxin; Gui, Li; Wang, Yue; Zhang, Quanquan; Zhou, Lin; Wei, Shaohua

    2016-04-01

    β-tetra (aminophenoxy) sulfonic substituted zinc phthalocyanines (SNZnPc), a novel amphiphilic zinc phthalocyanine (Pc), was synthesized. The photophysical, photochemical, and photobiology properties were studied. Results indicated that the synthesized SNZnPc has good amphiphilic property and high reactive oxygen species (ROSs) generation ability. Furthermore, SNZnPc has strong affinity to calf thymus DNA (CT-DNA) through intercalation ways and can effectively cleavage CT-DNA after irradiation by light with appropriate wavelength.

  19. Catalytic Y-tailed amphiphilic homopolymers – aqueous nanoreactors for high activity, low loading SCS pincer catalysts

    OpenAIRE

    Patterson, Joseph P.; Cotanda, Pepa; Kelley, Elizabeth G.; Moughton, Adam O.; Lu, Annhelen; Epps, Thomas H.; O’Reilly, Rachel K.

    2013-01-01

    A new amphiphilic homopolymer bearing an SCS pincer palladium complex has been synthesized by reversible addition fragmentation chain transfer polymerization. The amphiphile has been shown to form spherical and worm-like micelles in water by cryogenic transmission electron microscopy and small angle neutron scattering. Segregation of reactive components within the palladium containing core results in increased catalytic activity of the pincer compound compared to small molecule analogues. Thi...

  20. Adsorption of phthalic acid esters (PAEs) by amphiphilic polypropylene nonwoven from aqueous solution: The study of hydrophilic and hydrophobic microdomain

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Xiangyu [State Key Laboratory of Hollow Fiber Membrane Materials and Processes, Tianjin Polytechnic University, Tianjin 300387 (China); School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387 (China); Wei, Junfu, E-mail: weijunfu1963@163.com [State Key Laboratory of Hollow Fiber Membrane Materials and Processes, Tianjin Polytechnic University, Tianjin 300387 (China); School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387 (China); Zhang, Huan; Liu, Kai; Wang, Han [State Key Laboratory of Hollow Fiber Membrane Materials and Processes, Tianjin Polytechnic University, Tianjin 300387 (China); School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387 (China)

    2014-05-01

    Highlights: • Amphiphilic PP-g-GMA-OA nonwoven was prepared and characterized. • Synergy between hydrophilic and hydrophobic microdomain was elucidated. • The effects of hydrophilic microdomain on diffusion resistance and energy barrier were elucidated. • Adsorbent material with amphiphilic structures showed faster adsorption rate and lager adsorption capacity. - Abstract: A kind of amphiphilic polypropylene nonwoven with hydrophilic and hydrophobic microdomain was prepared through electron beam induced graft polymerization and subsequent ring opening reaction and then utilized in the adsorption of phthalic acid esters (PAEs). To elucidate the superiority of such amphiphilic microdomain, a unique structure without hydrophilic part was constructed as comparison. In addition, the adsorption behaviors including adsorption kinetics, isotherms and pH effect were systematically investigated. The result indicated that the amphiphilic structure and the synergy between hydrophilic and hydrophobic microdomain could considerably improve the adsorption capacities, rate and affinity. Particularly the existence of hydrophilic microdomain could reduce the diffusion resistance and energy barrier in the adsorption process. These adsorption results showed that the amphiphilic PP nonwoven have the potential to be used in environmental application.

  1. 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.

  2. Molecular dynamics simulations of membrane deformation induced by amphiphilic helices of Epsin, Sar1p, and Arf1

    Science.gov (United States)

    Li, Zhen-Lu

    2018-03-01

    The N-terminal amphiphilic helices of proteins Epsin, Sar1p, and Arf1 play a critical role in initiating membrane deformation. The interactions of these amphiphilic helices with the lipid membranes are investigated in this study by combining the all-atom and coarse-grained simulations. In the all-atom simulations, the amphiphilic helices of Epsin and Sar1p are found to have a shallower insertion depth into the membrane than the amphiphilic helix of Arf1, but remarkably, the amphiphilic helices of Epsin and Sar1p induce higher asymmetry in the lipid packing between the two monolayers of the membrane. The insertion depth of amphiphilic helix into the membrane is determined not only by the overall hydrophobicity but also by the specific distributions of polar and non-polar residues along the helix. To directly compare their ability to deform the membrane, the coarse-grained simulations are performed to investigate the membrane deformation under the insertion of multiple helices. Project supported by the National Natural Science Foundation of China (Grant Nos. 91427302 and 11474155).

  3. Enhancing the protein resistance of silicone via surface-restructuring PEO-silane amphiphiles with variable PEO length.

    Science.gov (United States)

    Rufin, M A; Gruetzner, J A; Hurley, M J; Hawkins, M L; Raymond, E S; Raymond, J E; Grunlan, M A

    2015-04-14

    Silicones with superior protein resistance were produced by bulk-modification with poly(ethylene oxide) (PEO)-silane amphiphiles that demonstrated a higher capacity to restructure to the surface-water interface versus conventional non-amphiphilic PEO-silanes. The PEO-silane amphiphiles were prepared with a single siloxane tether length but variable PEO segment lengths: α-(EtO) 3 Si(CH 2 ) 2 -oligodimethylsiloxane 13 - block -poly(ethylene oxide) n -OCH 3 ( n = 3, 8, and 16). Conventional PEO-silane analogues ( n = 3, 8 and 16) as well as a siloxane tether-silane (i.e. no PEO segment) were prepared as controls. When surface-grafted onto silicon wafer, PEO-silane amphiphiles produced surfaces that were more hydrophobic and thus more adherent towards fibrinogen versus the corresponding PEO-silane. However, when blended into a silicone, PEO-silane amphiphiles exhibited rapid restructuring to the surface-water interface and excellent protein resistance whereas the PEO-silanes did not. Silicones modified with PEO-silane amphiphiles of PEO segment lengths n = 8 and 16 achieved the highest protein resistance.

  4. Adsorption of phthalic acid esters (PAEs) by amphiphilic polypropylene nonwoven from aqueous solution: The study of hydrophilic and hydrophobic microdomain

    International Nuclear Information System (INIS)

    Zhou, Xiangyu; Wei, Junfu; Zhang, Huan; Liu, Kai; Wang, Han

    2014-01-01

    Highlights: • Amphiphilic PP-g-GMA-OA nonwoven was prepared and characterized. • Synergy between hydrophilic and hydrophobic microdomain was elucidated. • The effects of hydrophilic microdomain on diffusion resistance and energy barrier were elucidated. • Adsorbent material with amphiphilic structures showed faster adsorption rate and lager adsorption capacity. - Abstract: A kind of amphiphilic polypropylene nonwoven with hydrophilic and hydrophobic microdomain was prepared through electron beam induced graft polymerization and subsequent ring opening reaction and then utilized in the adsorption of phthalic acid esters (PAEs). To elucidate the superiority of such amphiphilic microdomain, a unique structure without hydrophilic part was constructed as comparison. In addition, the adsorption behaviors including adsorption kinetics, isotherms and pH effect were systematically investigated. The result indicated that the amphiphilic structure and the synergy between hydrophilic and hydrophobic microdomain could considerably improve the adsorption capacities, rate and affinity. Particularly the existence of hydrophilic microdomain could reduce the diffusion resistance and energy barrier in the adsorption process. These adsorption results showed that the amphiphilic PP nonwoven have the potential to be used in environmental application

  5. A theoretical study of colloidal forces near an amphiphilic polymer brush

    Science.gov (United States)

    Wu, Jianzhong

    2011-03-01

    Polymer-based ``non-stick'' coatings are promising as the next generation of effective, environmentally-friendly marine antifouling systems that minimize nonspecific adsorption of extracellular polymeric substances (EPS). However, design and development of such systems are impeded by the poor knowledge of polymer-mediated interactions of biomacromolecules with the protected substrate. In this work, a polymer density functional theory (DFT) is used to predict the potential of mean force between spherical biomacromolecules and amphiphilic copolymer brushes within a coarse-grained model that captures essential nonspecific interactions such as the molecular excluded volume effects and the hydrophobic energies. The relevance of theoretical results for practical control of the EPS adsorption is discussed in terms of the efficiency of different brush configurations to prevent biofouling. It is shown that the most effective antifouling surface may be accomplished by using amphiphilic brushes with a long hydrophilic backbone and a hydrophobic end at moderate grafting density.

  6. Efficient size control of amphiphilic cyclodextrin nanoparticles through a statistical mixture design methodology.

    Science.gov (United States)

    Choisnard, Luc; Géze, Annabelle; Bigan, Muriel; Putaux, Jean-Luc; Wouessidjewe, Denis

    2005-12-06

    the aim of the study was to investigate size control of amphiphilic beta-cyclodextrin nanoparticles obtained by solvent displacement technique. An experimental design methodology for mixture design was undertaken using D-optimal approach with the following technique variables: water fraction X1 (40-70% v/v), acetone fraction X2 (0-60% v/v) and ethanol fraction X3 (0-60% v/v). The resulting quadratic model obtained after logarithmic transformation of data and partial least-square regression was statistically validated and experimentally checked. Also, the morphology of the colloidal nanoparticles from selected experiments was observed by cryo-transmission electron microscopy. This experimental design approach allowed to produce interesting amphiphilic beta-cyclodextrin nanoparticles with a predicted mean size varying from 60 to 400 nm.

  7. Amphiphilic block copolymers as efficiency boosters in microemulsions a SANS investigation of the role of polymers

    CERN Document Server

    Endo, H; Mihailescu, M; Monkenbusch, M; Gompper, G; Richter, D; Jakobs, B; Sottmann, T; Strey, R

    2002-01-01

    The effect of amphiphilic block copolymers on ternary microemulsions (water, oil and non-ionic surfactant) is investigated. Small amounts of PEP-PEO block copolymer lead to a dramatic expansion of the one-phase region where water and oil can be solubilized by the mediation of surfactant molecules. Small-angle neutron-scattering experiments employing a high-precision two-dimensional contrast-variation technique demonstrate that the polymer is distributed uniformly on the surfactant membrane, where it modifies the membrane curvature elasticity. Furthermore, a new approach to determine the bending rigidity of an amphiphilic membrane is proposed, which is precise enough to measure the logarithmic scale dependence of the bending rigidity and its universal prefactor in bicontinuous microemulsions. (orig.)

  8. Synthesis of amphiphilic aminated inulin via 'click chemistry' and evaluation for its antibacterial activity.

    Science.gov (United States)

    Dong, Fang; Zhang, Jun; Yu, Chunwei; Li, Qing; Ren, Jianming; Wang, Gang; Gu, Guodong; Guo, Zhanyong

    2014-09-15

    Inulins are a group of abundant, water-soluble, renewable polysaccharides, which exhibit attractive bioactivities and natural properties. Improvement such as chemical modification of inulin is often performed prior to further utilization. We hereby presented a method to modify inulin at its primary hydroxyls to synthesize amphiphilic aminated inulin via 'click chemistry' to facilitate its chemical manipulation. Additionally, its antibacterial property against Staphylococcus aureus (S. aureus) was also evaluated and the best inhibitory index against S. aureus was 58% at 1mg/mL. As the amphiphilic aminated inulin is easy to prepare and exhibits improved bioactivity, this material may represent as an attractive new platform for chemical modifications of inulin. Copyright © 2014 Elsevier Ltd. All rights reserved.

  9. Terpene and dextran renewable resources for the synthesis of amphiphilic biopolymers.

    Science.gov (United States)

    Alvès, Marie-Hélène; Sfeir, Huda; Tranchant, Jean-François; Gombart, Emilie; Sagorin, Gilles; Caillol, Sylvain; Billon, Laurent; Save, Maud

    2014-01-13

    The present work shows the synthesis of amphiphilic polymers based on the hydrophilic dextran and the hydrophobic terpenes as renewable resources. The first step concerns the synthesis of functional terpene molecules by thiol-ene addition chemistry involving amino or carboxylic acid thiols and dihydromyrcenol terpene. The terpene-modified polysaccharides were subsequently synthesized by coupling the functional terpenes with dextran. A reductive amination step produced terpene end-modified dextran with 94% of functionalization, while the esterification step produced three terpene-grafted dextrans with a number of terpene units per dextran of 1, 5, and 10. The amphiphilic renewable grafted polymers were tested as emulsifiers for the stabilization of liquid miniemulsion of terpene droplets dispersed in an aqueous phase. The average hydrodynamic diameter of the stable droplets was observed at about 330 nm.

  10. Reverse self-assemblies based on amphiphilic polyphosphazenes for encapsulation of water-soluble molecules

    Science.gov (United States)

    Qiu, Liyan; Zhang, Jianxiang; Yan, Meiqiu; Jin, Yi; Zhu, Kangjie

    2007-11-01

    A novel series of amphiphilic polyphosphazenes (PNIPAm/AA-PPP) containing hydrophilic oligo-(N-isopropylacrylamide) (oligo-NIPAm) and various hydrophobic aliphatic amines as co-substitutes was synthesized via a two-step substitution reaction. The extraction and solubilization of water-soluble substances such as fluorescein sodium and trypan blue from an aqueous phase into the chloroform phase were supposed to result from the formation of polyphosphazene reverse self-assemblies in the organic phase. A field emission scanning electronic microscope was adopted to characterize the morphology of reverse assemblies in chloroform. Additionally, a significant improvement of encapsulation and release profiles of water-soluble substances was found for poly(lactic-co-glycolic acid) (PLGA) microparticles in the presence of amphiphilic copolymers, which was associated with the chemical structure of copolymers as well as the content of copolymer in the microparticles.

  11. Polyaniline Nanofibers: Their Amphiphilicity and Uses for Pickering Emulsions and On-Demand Emulsion Separation.

    Science.gov (United States)

    Zhou, Ping; Li, Jing; Yang, Wenwen; Zhu, Lihua; Tang, Heqing

    2018-02-27

    The wetting property of nanomaterials is of great importance to both fundamental understanding and potential applications. However, the study on the intrinsic wetting property of nanomaterials is interfered by organic capping agents, which are often used to lower the surface energy of nanomaterials and avoid their irreversible agglomeration. In this work, the wetting property of the nanostructured polyaniline that requires no organic capping agents is investigated. Compared to hydrophilic granular particulates, polyaniline nanofibers are amphiphilic and have an excellent capability of creating Pickering emulsions at a wide range of pH. It is suggested that polyaniline nanofibers can be easily wetted by water and oil. Furthermore, the amphiphilic polyaniline nanofibers as building blocks can be used to construct filtration membranes with a small pore size. The wetting layer of the continuous phase of emulsions in the porous nanochannels efficiently prevents the permeation of the dispersed phase, realizing high-efficiency on-demand emulsion separation.

  12. 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...... in physiological salt concentration. This is indebted from “dilution” of the charges along the grafted chains by balancing neutral/charged repeating units to minimize the accumulated charge repulsion on neutral surface. Improved lubricating properties of the graft copolymers compared to the block copolymer...

  13. Amphiphilic Cellulose Ethers Designed for Amorphous Solid Dispersion via Olefin Cross-Metathesis.

    Science.gov (United States)

    Dong, Yifan; Mosquera-Giraldo, Laura I; Taylor, Lynne S; Edgar, Kevin J

    2016-02-08

    The design of cellulose ether-based amphiphiles has been difficult and limited because of the harsh conditions typically required for appending ether moieties to cellulose. Olefin cross-metathesis recently has been shown to be a valuable approach for appending a variety of functional groups to cellulose ethers and esters, provided that an olefin handle for metathesis can be attached. This synthetic pathway gives access to these functional derivatives under very mild conditions and at high efficiency. Modification of ethyl cellulose by metathesis to prepare useful derivatives, for example, for solubility and bioavailability enhancement of drugs by amorphous solid dispersion (ASD), has been limited by the low DS(OH) of commercial ethyl cellulose derivatives. This is problematic because ethyl cellulose is otherwise a very attractive substrate for synthesis of amphiphilic derivatives by olefin metathesis. Herein we explore two methods for opening up this design space for ether-based amphiphiles, for example, permitting synthesis of more hydrophilic derivatives. One approach is to start with the more hydrophilic commercial methyl cellulose, which contains much higher DS(OH) and therefore is better suited for introduction of high DS of olefin metathesis "handles". In another approach, we explored a homogeneous one-pot synthesis methodology from cellulose, where controlled DS of ethyl groups was introduced at the same time as the ω-unsaturated alkyl groups, thereby permitting complete control of DS(OH), DS(Et), and ultimately DS of the functional group added by metathesis. We describe the functionalized derivatives available by these successful approaches. In addition, we explore new methods for reduction of the unsaturation in initial metathesis products to provide robust methods for enhancing product stability against further radical-catalyzed reactions. We demonstrate initial evidence that the products show strong promise as amphiphilic matrix polymers for amorphous

  14. Immunochemically identical hydrophilic and amphiphilic forms of the bovine adrenomedullary dopamine beta-hydroxylase

    DEFF Research Database (Denmark)

    Bjerrum, Ole Jannik; Helle, K B; Bock, Elisabeth Marianne

    1979-01-01

    . The dopamine beta-hydroxylases of the buffer and membrane fractions were antigenically identical, but differed in their amphiphilicity, as demonstrated by the change in precipitation patterns on removal of Triton X-100 from the gel, on charge-shift crossed immunoelectrophoresis and on crossed hydrophobic...... interaction immunoelectrophoresis with phenyl-Sepharose. Furthermore, immunoelectrophoretic analysis in the presence of Triton X-100 plus the cationic detergent cetyltrimethylammonium bromide indicates additional heterogeneity of the membrane-bound dopamine-beta-hydroxylase. By limited proteolysis...

  15. Protein resistance efficacy of PEO-silane amphiphiles: Dependence on PEO-segment length and concentration.

    Science.gov (United States)

    Rufin, Marc A; Barry, Mikayla E; Adair, Paige A; Hawkins, Melissa L; Raymond, Jeffery E; Grunlan, Melissa A

    2016-09-01

    In contrast to modification with conventional PEO-silanes (i.e. no siloxane tether), silicones with dramatically enhanced protein resistance have been previously achieved via bulk-modification with poly(ethylene oxide) (PEO)-silane amphiphiles α-(EtO)3Si(CH2)2-oligodimethylsiloxane13-block-PEOn-OCH3 when n=8 and 16 but not when n=3. In this work, their efficacy was evaluated in terms of optimal PEO-segment length and minimum concentration required in silicone. For each PEO-silane amphiphile (n=3, 8, and 16), five concentrations (5, 10, 25, 50, and 100μmol per 1g silicone) were evaluated. Efficacy was quantified in terms of the modified silicones' abilities to undergo rapid, water-driven surface restructuring to form hydrophilic surfaces as well as resistance to fibrinogen adsorption. Only n=8 and 16 were effective, with a lower minimum concentration in silicone required for n=8 (10μmol per 1g silicone) versus n=16 (25μmol per 1g silicone). Silicone is commonly used for implantable medical devices, but its hydrophobic surface promotes protein adsorption which leads to thrombosis and infection. Typical methods to incorporate poly(ethylene oxide) (PEO) into silicones have not been effective due to the poor migration of PEO to the surface-biological interface. In this work, PEO-silane amphiphiles - comprised of a siloxane tether (m=13) and variable PEO segment lengths (n=3, 8, 16) - were blended into silicone to improve its protein resistance. The efficacy of the amphiphiles was determined to be dependent on PEO length. With the intermediate PEO length (n=8), water-driven surface restructuring and resulting protein resistance was achieved with a concentration of only 1.7wt%. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  16. Recursive Alterations of the Relationship between Simple Membrane Geometry and Insertion of Amphiphilic Motifs

    DEFF Research Database (Denmark)

    Madsen, Kenneth Lindegaard; Herlo, Rasmus

    2017-01-01

    The shape and composition of a membrane directly regulate the localization, activity, and signaling properties of membrane associated proteins. Proteins that both sense and generate membrane curvature, e.g., through amphiphilic insertion motifs, potentially engage in recursive binding dynamics......, where the recruitment of the protein itself changes the properties of the membrane substrate. Simple geometric models of membrane curvature interactions already provide prediction tools for experimental observations, however these models are treating curvature sensing and generation as separated...

  17. Small yet effective: The Ethylene-responsive element binding factor-associated Amphiphilic Repression (EAR) motif

    OpenAIRE

    Kagale, Sateesh; Rozwadowski, Kevin

    2010-01-01

    The Ethylene-responsive element binding factor-associated Amphiphilic Repression (EAR) motif is a small yet distinct regulatory motif that is conserved in many plant transcriptional regulator (TR) proteins associated with diverse biological functions. We have previously established a list of high-confidence Arabidopsis EAR repressors, the EAR repressome, comprising 219 TRs belonging to 21 different TR families. This class of proteins and the sequence context of the EAR motif exhibited a high ...

  18. Vortex-Induced Alignment of a Water Soluble Supramolecular Nanofiber Composed of an Amphiphilic Dendrimer

    Directory of Open Access Journals (Sweden)

    Akihiko Tsuda

    2013-06-01

    Full Text Available We have synthesized a novel amphiphilic naphthalene imide bearing a cationic dendrimer wedge (NID. NID molecules in water self-assemble to form a two-dimensional ribbon, which further coils to give a linear supramolecular nanofiber. The sample solution showed linear dichroism (LD upon stirring of the solution, where NID nanofibers dominantly align at the center of vortex by hydrodynamic interaction with the downward torsional flows.

  19. Amphiphilic carbon dots for sensitive detection, intracellular imaging of Al{sup 3+}

    Energy Technology Data Exchange (ETDEWEB)

    Kong, Depeng [State Key Laboratory of Separation Membranes and Membrane Processes, School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387 (China); Yan, Fanyong, E-mail: yanfanyong@tjpu.edu.cn [State Key Laboratory of Separation Membranes and Membrane Processes, School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387 (China); Luo, Yunmei [Department of Pharmacology/Key Laboratory for Basic Pharmacology of Ministry of Education, Zunyi Medical College, Guizhou 563000 (China); Ye, Qianghua; Zhou, Siyushan [State Key Laboratory of Separation Membranes and Membrane Processes, School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387 (China); Chen, Li, E-mail: Chenlis@tjpu.edu.cn [State Key Laboratory of Separation Membranes and Membrane Processes, School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387 (China)

    2017-02-08

    In this paper, a simple and effective method was designed to synthesize hydrophobic carbon dots. Subsequently, amphiphilic fluorescent carbon dots (A-CDs) were synthesized by further surface modification. The result A-CDs show excellent optical properties with a quantum yield of 16.9%. It was interestingly found that morin (MR) and its fluorescent metal-ion complex (MR-Al{sup 3+}) can successfully coordinate on the surface of A-CDs, the emission of A-CDs completely overlapped the absorption peak of MR-Al{sup 3+}. Thus, the prepared A-CDs can be used as an effective fluorescent probe for Al{sup 3+} based on a fluorescence resonance energy transfer process. The sensing platform can realize real-time detection of Al{sup 3+} within 0.5 min. The fluorescence signals of the system were linearly correlated with the concentration of Al{sup 3+} over a range of 8–20 μM, with a detection limit of 0.113 μM. The method was also successfully applied to image the distribution of Al{sup 3+} in Human Umbilical Vein Endothelial Cells. - Highlights: • Amphiphilic carbon dots were obtained by simply modifying hydrophobic carbon dots. • Amphiphilic carbon dots/morin-Al{sup 3+} was used as a selective turn-on probe for Al{sup 3+}. • The method was employed to intracellular imaging Al{sup 3+} in living cells.

  20. Intrinsically disordered amphiphilic peptides as potential targets in drug delivery vehicles.

    Science.gov (United States)

    Vincenzi, Marian; Accardo, Antonella; Costantini, Susan; Scala, Stefania; Portella, Luigi; Trotta, Annamaria; Ronga, Luisa; Guillon, Jean; Leone, Marilisa; Colonna, Giovanni; Rossi, Filomena; Tesauro, Diego

    2015-11-01

    Intrinsically disordered proteins/peptides play a crucial role in many physiological and pathological events and may assume a precise conformation upon binding to a specific target. Recently, we have described the conformational and functional properties of two linear ester peptides provided with the following sequences: Y-G-E-C-P-C-K-OAllyl (PepK) and Y-G-E-C-P-C-E-OAllyl (PepE). Both peptides are characterized by the presence of the "CPC" motif together with a few amino acids able to promote disorder. The CPC sequence is a binding motif for the CXCR4 receptor that represents a well-known target for cancer therapies. In this paper, we report on synthetic amphiphilic peptides that consist of lipophilic derivatives of PepE and PepK bearing two stearic alkyl chains and/or an ethoxylic spacer. These peptide amphiphiles form stable supramolecular aggregates; they present conformational features that are typical of intrinsically disordered molecules as shown by CD spectroscopy. Solution fluorescence and DLS studies have been performed to evaluate Critical Micellar Concentrations and the dimension of supramolecular aggregates. Moreover, preliminary in vitro cell-based assays have been conducted to investigate the molecular recognition processes involving the CXCR4 receptor. In the end, the results obtained have been compared with the previous data generated by the corresponding non-amphiphilic peptides (PepE and PepK).

  1. Beyond amphiphiles: coarse-grained simulations of star-polyphile liquid crystalline assemblies.

    Science.gov (United States)

    Kirkensgaard, Jacob Judas Kain; Hyde, Stephen

    2009-03-28

    We have simulated the self-assembly of a novel class of three-arm molecules, ABC star-architecture polyphiles, using coarse-grained bead simulations. A number of topologically complex liquid crystalline mesostructures arise that can be related to the better-known bicontinuous mesophases of lyotropic amphiphilic systems. The simulations reveal 3D self-assemblies whose structural variations follow those expected assuming a simple steric molecular packing model as a function of star polyphile splay and relative volumes of each arm in the polyphile. The splay of each arm, characterised by the 3D wedge-shape emanating from the core of each molecule to its exterior induces torsion of the interfaces along the triple lines, whereas differences in the relative volumes of arms induce curvature of the triple lines. Three distinct mesostructures are described, characterised by their micro-domain topologies, which are unknown in simpler amphiphilic systems, but resemble in some respects bicontinuous mesophases. These three- (or more) arm polyphilic systems offer an interesting extension to the better-known self-assembly of (two-arm) amphiphiles in solution.

  2. Morphological Evolution of Self-Assembled Structures Induced by the Molecular Architecture of Supra-Amphiphiles.

    Science.gov (United States)

    Wang, Juan; Li, Boxuan; Wang, Xing; Yang, Fei; Shen, Hong; Wu, Decheng

    2016-12-27

    A series of telechelic supramolecular amphiphiles [POSS-Azo 8 @(β-CD-PDMAEMA) 1→8 ] was accomplished by orthogonally coupling the multiarm host polymer β-cyclodextrin-poly(dimethylaminoethyl methacrylate) (β-CD-PDMAEMA) with an octatelechelic guest molecule azobenzene modified-polyhedral oligomeric silsesquioxanes (POSS-Azo 8 ) under different host-guest ratios. These telechelic supramolecular amphiphiles possess a rigid core and flexible corona. Increasing the multiarm host polymer coupled onto the rigid POSS core made the molecular architecture tend to be symmetrical and spherical. POSS-Azo 8 @[β-CD-PDMAEMA] 1→8 could self-assemble into diverse morphologies evolving from spherical micelles, wormlike micelles, and branched aggregates to bowl-shaped vesicles. Distinct from the traditional linear amphiphilic polymers, we discovered that the self-assembly of POSS-Azo 8 @[β-CD-PDMAEMA] 1→8 was dominantly regulated by their molecular architectures instead of hydrophilicity, which has also been verified using computer simulation results.

  3. Physical deposition behavior of stiff amphiphilic polyelectrolytes in an external electric field

    Science.gov (United States)

    Hu, Dongmei; Zuo, Chuncheng; Cao, Qianqian; Chen, Hongli

    2017-08-01

    Coarse-grained molecular dynamics simulations are conducted to study the physical deposition behavior of stiff amphiphilic polyelectrolytes (APEs) in an external electric field. The effects of chain stiffness, the charge distribution of a hydrophilic block, and electric field strength are investigated. Amphiphilic multilayers, which consist of a monolayer of adsorbed hydrophilic monomers (HLMs), a hydrophobic layer, and another hydrophilic layer, are formed in a selective solvent. All cases exhibit locally ordered hydrophilic monolayers. Two kinds of hydrophobic micelles are distinguished based on local structures. Stripe and network hydrophobic patterns are formed in individual cases. Increasing the chain stiffness decreases the thickness of the deposited layer, the lateral size of the hydrophobic micelles, and the amount of deposition. Increasing the number of positively charged HLMs in a single chain has the same effect as increasing chain stiffness. Moreover, when applied normally to the substrate, the electric field compresses the deposited structures and increases the amount of deposition by pulling more PEs toward the substrate. A stronger electric field also facilitates the formation of a thinner and more ordered hydrophilic adsorption layer. These estimates help us explore how to tailor patterned nano-surfaces, nano-interfaces, or amphiphilic nanostructures by physically depositing semi-flexible APEs which is of crucial importance in physical sciences, life sciences and nanotechnology.

  4. Cylindrical micelles of a POSS amphiphilic dendrimer as nano-reactors for polymerization.

    Science.gov (United States)

    Weng, Jing-Ting; Yeh, Tso-Fan; Samuel, Ashok Zachariah; Huang, Yi-Fan; Sie, Jyun-Hao; Wu, Kuan-Yi; Peng, Chi-How; Hamaguchi, Hiro-O; Wang, Chien-Lung

    2018-02-15

    A low generation amphiphilic dendrimer, POSS-AD, which has a POSS core and eight amphiphilic arms, was synthesized and used as a nano-reactor to produce well-defined polymer nano-cylinders. Confirmed by small-angle X-ray scattering (SAXS), Raman and NMR spectrometry, monodispersed cylindrical micelles that contain a hydrophilic cavity with a diameter of 2.09 nm and a length of 4.26 nm were produced via co-assembling POSS-AD with hydrophilic liquids, such as H 2 O and HEMA in hydrophobic solvents. Taking the HEMA/POSS-AD cylindrical micelles as nano-reactors, polymerization of HEMA within the micelles results in polymer nano-cylinders (POSS-ADNPs) with a diameter of 2.24 nm and a length of 5.02 nm. The study confirmed that despite the inability to maintain specific shape in solution, low generation dendrimers form well-defined nano-containers or nano-reactors, which relies on co-assembling with hydrophilic guest molecules. These nano-reactors are robust enough to maintain their shape during the polymerization of the guest molecules. Polymer nano-cylinders with dimensions less than 10 nm can thus be produced from the HEMA/POSS-AD micelles. Since the chemical structure of low-generation dendrimers and the contents of the co-assembled nano-reactors can be easily adjusted, the concept holds the potential for the further developments of low-generation amphiphilic dendrimers.

  5. 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.

  6. The effect of amphiphilic siloxane oligomers on fibroblast and keratinocyte proliferation and apoptosis.

    Science.gov (United States)

    Lynam, Emily C; Xie, Yan; Loli, Bree; Dargaville, Tim R; Leavesley, David I; George, Graeme A; Upton, Zee

    2010-11-01

    The formation of hypertrophic scars (HSF) is a frequent medical outcome of wound repair and often requires further therapy with treatments such as silicone gel sheets (SGS) or apoptosis-inducing agents, including bleomycin. Although widely used, knowledge regarding SGS and their mode of action is limited. Preliminary research has shown that small amounts of amphiphilic silicone present in SGS have the ability to move into skin during treatment. We demonstrate herein that a commercially available analogue of these amphiphilic siloxane species, the rake copolymer GP226, decreases collagen synthesis on exposure to cultures of fibroblasts derived from HSF. By size exclusion chromatography, GP226 was found to be a mixture of siloxane species, containing five fractions of different molecular weight. By studies of collagen production, cell viability and proliferation, it was revealed that a low molecular weight fraction (fraction IV) was the most active, reducing the number of viable cells present after treatment and thereby reducing collagen production as a result. On exposure of fraction IV to human keratinocytes, viability and proliferation were also significantly affected. HSF undergoing apoptosis after application of fraction IV were also detected via real-time microscopy and by using the TUNEL assay. Taken together, these data suggests that these amphiphilic siloxanes could be potential non-invasive substitutes to apoptotic-inducing chemical agents that are currently used as scar treatments.

  7. A calorimetric evaluation of the interaction of amphiphilic prodrugs of idebenone with a biomembrane model.

    Science.gov (United States)

    Pignatello, R; Intravaia, V D; Puglisi, G

    2006-07-15

    Lipoamino acids (LAA) are useful promoieties to modify physicochemical properties of drugs, namely lipophilicity and amphiphilicity. The resulting membrane-like character of drug-LAA conjugates can increase the absorption profile of drugs through cell membranes and biological barriers. To show the role of amphiphilicity with respect to lipophilicity in the interaction of drugs with biomembranes, in the present study we evaluated the mode of such an interaction of lipophilic conjugates of LAA with the antioxidant drug idebenone (IDE). DSC analysis and transfer kinetic studies were carried out using dimyristoylphosphatidylcholine (DMPC) multilamellar liposomes (MLVs) as a model. For comparison, two esters of IDE with alkanoic acids were synthesized and included in the analysis. The experimental results indicate that based on their different structure, IDE-LAA conjugates interacted at different levels with respect to pure IDE with DMPC bilayers. In particular, a progressive penetration inside the vesicles was observed upon incubation of IDE-LAA compounds with empty liposomes. The enhanced amphiphilicity of the drug due to the LAA moieties caused more complex interactions with DMPC bilayers, compared to those registered with the native drug or IDE alkanoate esters.

  8. 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.

  9. Self-Assembly of Discrete Metal Complexes in Aqueous Solution via Block Copolypeptide Amphiphiles

    Directory of Open Access Journals (Sweden)

    Timothy J. Deming

    2013-01-01

    Full Text Available The integration of discrete metal complexes has been attracting significant interest due to the potential of these materials for soft metal-metal interactions and supramolecular assembly. Additionally, block copolypeptide amphiphiles have been investigated concerning their capacity for self-assembly into structures such as nanoparticles, nanosheets and nanofibers. In this study, we combined these two concepts by investigating the self-assembly of discrete metal complexes in aqueous solution using block copolypeptides. Normally, discrete metal complexes such as [Au(CN2]−, when molecularly dispersed in water, cannot interact with one another. Our results demonstrated, however, that the addition of block copolypeptide amphiphiles such as K183L19 to [Au(CN2]− solutions induced one-dimensional integration of the discrete metal complex, resulting in photoluminescence originating from multinuclear complexes with metal-metal interactions. Transmission electron microscopy (TEM showed a fibrous nanostructure with lengths and widths of approximately 100 and 20 nm, respectively, which grew to form advanced nanoarchitectures, including those resembling the weave patterns of Waraji (traditional Japanese straw sandals. This concept of combining block copolypeptide amphiphiles with discrete coordination compounds allows the design of flexible and functional supramolecular coordination systems in water.

  10. Synthesis and characterization of amorphous mesoporous silica using TEMPO-functionalized amphiphilic templates

    Energy Technology Data Exchange (ETDEWEB)

    Vries, Wilke de [Institute of Organic Chemistry, Westfälische Wilhelms-Universität Münster, Corrensstrasse 40, 48149 Münster (Germany); Doerenkamp, Carsten; Zeng, Zhaoyang [Institut für Physikalische Chemie, Westfälische Wilhelms-Universität Münster, Corrensstrasse 28/30, 48149 Münster (Germany); Oliveira, Marcos de [Instituto de Física em Sao Paulo, Universidade de Sao Paulo, Av. Trabalhador Saocarlense 400, Sao Carlos, S.P. 13560 590 (Brazil); Niehaus, Oliver; Pöttgen, Rainer [Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Corrensstrasse 28/30, 48149 Münster (Germany); Studer, Armido, E-mail: studer@uni-muenster.de [Institute of Organic Chemistry, Westfälische Wilhelms-Universität Münster, Corrensstrasse 40, 48149 Münster (Germany); Eckert, Hellmut, E-mail: eckerth@uni-muenster.de [Institut für Physikalische Chemie, Westfälische Wilhelms-Universität Münster, Corrensstrasse 28/30, 48149 Münster (Germany); Instituto de Física em Sao Paulo, Universidade de Sao Paulo, Av. Trabalhador Saocarlense 400, Sao Carlos, S.P. 13560 590 (Brazil)

    2016-05-15

    Inorganic–organic hybrid materials based on amorphous mesoporous silica containing organized nitroxide radicals within its mesopores have been prepared using the micellar self-assembly of TEOS solutions containing the nitroxide functionalized amphiphile (4-(N,N-dimethyl-N-hexadecylammonium)-2,2,6, 6-tetramethyl-piperidin-N-oxyl-iodide) (CAT-16). This template has been used both in its pure form and in various mixtures with cetyl trimethylammonium bromide (CTAB). The samples have been characterized by chemical analysis, N{sub 2} sorption studies, magnetic susceptibility measurements, and various spectroscopic methods. While electron paramagnetic resonance (EPR) spectra indicate that the strength of the intermolecular spin–spin interactions can be controlled via the CAT-16/CTAB ratio, nuclear magnetic resonance (NMR) data suggest that these interactions are too weak to facilitate cooperative magnetism. - Graphical abstract: The amphiphilic radical CAT-16 is used as a template for the synthesis of amorphous mesoporous silica. The resulting paramagnetic hybrid materials are characterized by BET, FTIR, NMR, EPR and magnetic susceptibility studies. - Highlights: • Amphiphilic CAT-16 as a template for mesoporous silica. • Comprehensive structural characterization by BET, FTIR; EPR and NMR. • Strength of radical-radical interactions tuable within CAT-16/CTAB mixtures.

  11. Design and application of cationic amphiphilic β-cyclodextrin derivatives as gene delivery vectors

    Science.gov (United States)

    Wan, Ning; Huan, Meng-Lei; Ma, Xi-Xi; Jing, Zi-Wei; Zhang, Ya-Xuan; Li, Chen; Zhou, Si-Yuan; Zhang, Bang-Le

    2017-11-01

    The nano self-assembly profiles of amphiphilic gene delivery vectors could improve the density of local cationic head groups to promote their DNA condensation capability and enhance the interaction between cell membrane and hydrophobic tails, thus increasing cellular uptake and gene transfection. In this paper, two series of cationic amphiphilic β-cyclodextrin (β-CD) derivatives were designed and synthesized by using 6-mono-OTs-β-CD (1) as the precursor to construct amphiphilic gene vectors with different building blocks in a selective and controlled manner. The effect of different type and degree of cationic head groups on transfection and the endocytic mechanism of β-CD derivatives/DNA nanocomplexes were also investigated. The results demonstrated that the designed β-cyclodextrin derivatives were able to compact DNA to form stable nanocomplexes and exhibited low cytotoxicity. Among them, PEI-1 with PEI head group showed enhanced transfection activity, significantly higher than commercially available agent PEI25000 especially in the presence of serum, showing potential application prospects in clinical trials. Moreover, the endocytic uptake mechanism involved in the gene transfection of PEI-1 was mainly through caveolae-mediated endocytosis, which could avoid the lysosomal degradation of loaded gene, and had great importance for improving gene transfection activity.

  12. Supramolecular Assemblies from Poly(styrene-block-poly(4-vinylpyridine Diblock Copolymers Mixed with 6-Hydroxy-2-naphthoic Acid

    Directory of Open Access Journals (Sweden)

    Jean-François Gohy

    2013-06-01

    Full Text Available Supramolecular assemblies involving interaction of a small organic molecule, 2-hydroxy-6-Naphthoic acid (HNA, with poly(styrene-block-poly(4-vinylpyridine (PS-b-P4VP diblock copolymers are utilized to obtain micellar structures in solution, nanostructured thin films on flat substrates and, finally, nanoporous thin films. The formation of hydrogen bonds between HNA and the poly(4-vinylpyridine (P4VP blocks is confirmed by spectroscopic measurements. The accordingly P4VP/HNA hydrogen-bonded complexes are poorly soluble in 1,4-dioxane, resulting in the formation of micellar structures with a P4VP/HNA core and a polystyrene (PS corona. Those micelles have been spin-coated onto silicon wafers, resulting in nanostructured thin films consisting of P4VP/HNA dot-like features embedded in a PS matrix. The morphology of those films has been tuned by solvent annealing. Selective dissolution of HNA by methanol results in the formation of a nanoporous thin film. The P4VP/HNA nanodomains have been also cross-linked by borax, and the thin films have been further dissolved in a good solvent for PS, leading to micelles with a structure reminiscent of the thin films.

  13. Functionalization of Cellulose Nanocrystals with PEG-Metal-Chelating Diblock Copolymers via Controlled Conjugation in Aqueous Medium

    Science.gov (United States)

    Guo, Melinda

    The surface of cellulose nanocrystals (CNCs) was successfully functionalized with metal chelating diblock copolymers via HyNic-4FB conjugation. Two types of PEG-metal-chelating block polymers with hydrazinonicotinate acetone hydrazine (HyNic) end groups were synthesized: mPEG-PGlu(DTPA) 18-HyNic and mPEG-PGlu(DTPA)25-HyNic. These two polymers both had a methoxy PEG (M ˜ 2000 Da) block that differed in the mean degree of polymerization of the metal-chelating block. They were characterized by 1H NMR spectroscopy and gel-permeation chromatography (GPC). 4-Formylbenzamide (4FB) groups were introduced onto the surface of CNCs and quantified through their reaction with 2-hydrazinopyridine. The polymers were grafted onto the surface of CNCs via bis-aryl hydrazone bond formation, and the kinetics of this reaction was explored by UV/Vis spectroscopy. The CNCs were also labeled with rhodamine and Alexa FluorRTM 488 dyes. Students in our collaborator's group in Pharmacy are examining applications of these materials as radiotherapeutic agents for cancer treatment.

  14. Phase Behavior and Ionic Conductivity of Concentrated Solutions of Polystyrene-Poly(ethylene oxide) Diblock Copolymers in an Ionic Liquid

    Energy Technology Data Exchange (ETDEWEB)

    Simone, Peter M.; Lodge, Timothy P.; (UMM)

    2010-03-16

    Concentrated solutions of poly(styrene-b-ethylene oxide) (PS-PEO) diblock copolymers were prepared using the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [EMI][TFSI] as the solvent. The self-assembled microstructures adopted by the copolymer solutions have been characterized using small-angle X-ray scattering. Lyotropic mesophase transitions were observed, with a progression from hexagonally packed cylinders of PEO, to lamellae, to hexagonally packed cylinders of PS upon increasing [EMI][TFSI] content. The change in lamellar domain spacing with ionic liquid concentration was found to be comparable to that reported for other block copolymers in strongly selective solvents. The ionic conductivity of the concentrated PS-PEO/[EMI][TFSI] solutions was measured via impedance spectroscopy, and ranged from 1 x 10{sup -7} to 1 x 10{sup -3} S/cm at temperatures from 25-100 C. Additionally, the ionic conductivity of the solutions was found to increase with both ionic liquid concentration and molecular weight of the PEO blocks. The ionic conductivity of PEO homopolymer/[EMI][TFSI] solutions was also measured in order to compare the conductivity of the PS-PEO solutions to the expected limit for a lamellar sample with randomly oriented microstructure grains.

  15. Conformation and structural changes of diblock copolymers with octopus-like micelle formation in the presence of external stimuli

    Science.gov (United States)

    Dammertz, K.; Saier, A. M.; Marti, O.; Amirkhani, M.

    2014-04-01

    External stimuli such as vapours and electric fields can be used to manipulate the formation of AB-diblock copolymers on surfaces. We study the conformational variation of PS-b-PMMA (polystyrene-block-poly(methyl methacrylate)), PS and PMMA adsorbed on mica and their response to saturated water or chloroform atmospheres. Using specimens with only partial polymer coverage, new unanticipated effects were observed. Water vapour, a non-solvent for all three polymers, was found to cause high surface mobility. In contrast, chloroform vapour (a solvent for all three polymers) proved to be less efficient. Furthermore, the influence of an additional applied electric field was investigated. A dc field oriented parallel to the sample surface induces the formation of polymer islands which assemble into wormlike chains. Moreover, PS-b-PMMA forms octopus-like micelles (OLMs) on mica. Under the external stimuli mentioned above, the wormlike formations of OLMs are able to align in the direction of the external electric field. In the absence of an electric field, the OLMs disaggregate and exhibit phase separated structures under chloroform vapour.

  16. Conformation and structural changes of diblock copolymers with octopus-like micelle formation in the presence of external stimuli

    International Nuclear Information System (INIS)

    Dammertz, K; Saier, A M; Marti, O; Amirkhani, M

    2014-01-01

    External stimuli such as vapours and electric fields can be used to manipulate the formation of AB-diblock copolymers on surfaces. We study the conformational variation of PS-b-PMMA (polystyrene-block-poly(methyl methacrylate)), PS and PMMA adsorbed on mica and their response to saturated water or chloroform atmospheres. Using specimens with only partial polymer coverage, new unanticipated effects were observed. Water vapour, a non-solvent for all three polymers, was found to cause high surface mobility. In contrast, chloroform vapour (a solvent for all three polymers) proved to be less efficient. Furthermore, the influence of an additional applied electric field was investigated. A dc field oriented parallel to the sample surface induces the formation of polymer islands which assemble into wormlike chains. Moreover, PS-b-PMMA forms octopus-like micelles (OLMs) on mica. Under the external stimuli mentioned above, the wormlike formations of OLMs are able to align in the direction of the external electric field. In the absence of an electric field, the OLMs disaggregate and exhibit phase separated structures under chloroform vapour. (paper)

  17. PEG-b-PPS diblock copolymer aggregates for hydrophobic drug solubilization and release: cyclosporin A as an example.

    Science.gov (United States)

    Velluto, Diana; Demurtas, Davide; Hubbell, Jeffrey A

    2008-01-01

    Micelles formed from amphiphilic block copolymers have been explored in recent years as carriers for hydrophobic drugs. In an aqueous environment, the hydrophobic blocks form the core of the micelle, which can host lipophilic drugs, while the hydrophilic blocks form the corona or outer shell and stabilize the interface between the hydrophobic core and the external medium. In the present work, mesophase behavior and drug encapsulation were explored in the AB block copolymeric amphiphile composed of poly(ethylene glycol) (PEG) as a hydrophile and poly(propylene sulfide) PPS as a hydrophobe, using the immunosuppressive drug cyclosporin A (CsA) as an example of a highly hydrophobic drug. Block copolymers with a degree of polymerization of 44 on the PEG and of 10, 20 and 40 on the PPS respectively (abbreviated as PEG44-b-PPS10, PEG44-b-PPS20, PEG44-b-PPS40) were synthesized and characterized. Drug-loaded polymeric micelles were obtained by the cosolvent displacement method as well as the remarkably simple method of dispersing the warm polymer melt, with drug dissolved therein, in warm water. Effective drug solubility up to 2 mg/mL in aqueous media was facilitated by the PEG- b-PPS micelles, with loading levels up to 19% w/w being achieved. Release was burst-free and sustained over periods of 9-12 days. These micelles demonstrate interesting solubilization characteristics, due to the low glass transition temperature, highly hydrophobic nature, and good solvent properties of the PPS block.

  18. Comparison of the pharmacological and biological properties of HPMA copolymer-pirarubicin conjugates: A single-chain copolymer conjugate and its biodegradable tandem-diblock copolymer conjugate

    Czech Academy of Sciences Publication Activity Database

    Etrych, Tomáš; Tsukigawa, K.; Nakamura, H.; Chytil, Petr; Fang, J.; Ulbrich, Karel; Otagiri, M.; Maeda, H.

    2017-01-01

    Roč. 106, 30 August (2017), s. 10-19 ISSN 0928-0987 R&D Projects: GA ČR(CZ) GA15-02986S; GA MŠk(CZ) LQ1604; GA MŠk(CZ) ED1.1.00/02.0109 Grant - others:AV ČR,Japan Society for the Promotion of Science(CZ) JSPS-16-05 Program:Bilaterální spolupráce Institutional support: RVO:61389013 Keywords : pirarubicin * PHPMA conjugate * tandem-diblock PHPMA conjugate Subject RIV: FR - Pharmacology ; Medidal Chemistry OBOR OECD: Pharmacology and pharmacy Impact factor: 3.756, year: 2016

  19. Rapid and systematic access to quasi-diblock copolymer libraries covering a comprehensive composition range by sequential RAFT polymerization in an Automated synthesizer.

    Science.gov (United States)

    Haven, Joris J; Guerrero-Sanchez, Carlos; Keddie, Daniel J; Moad, Graeme

    2014-02-01

    A versatile, cost-effective approach to the rapid, fully unattended preparation of systematic quasi-diblock copolymer libraries via sequential RAFT polymerization in an automated synthesizer is reported. The procedure is demonstrated with the synthesis of a 23 member library of low dispersity poly(butyl methacrylate)-quasiblock-poly(methyl methacrylate) covering a wide (fivefold) range of molar mass for the second block in a one-pot, sequential, RAFT polymerization. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Separation of parent homopolymers from diblock copolymers by liquid chromatography under limiting conditions of desorption 4. Role of eluent and temperature.

    Science.gov (United States)

    Berek, Dušan

    2010-11-01

    Liquid chromatography under limiting conditions of desorption (LC LCD) enables fast, base-line discrimination of both parent homopolymers from various diblock copolymers in one single step. The low molecular admixtures are fully separated, as well. General rules are discussed in detail for selection of mobile phases and temperature applied in LC LCD of block copolymers. Typical practical separation examples are presented. It is shown that both the composition of the well-selected LC LCD mobile phase and the temperature of experiment may vary in a broad range without affecting the basics of method. This implies that the method is robust and user friendly.

  1. Synthesis of Diblock copolymer poly-3-hydroxybutyrate -block-poly-3-hydroxyhexanoate [PHB-b-PHHx] by a β-oxidation weakened Pseudomonas putida KT2442

    DEFF Research Database (Denmark)

    Tripathi, Lakshmi; Wu, Lin-Ping; Chen, Jinchun

    2012-01-01

    BACKGROUND: Block polyhydroxyalkanoates (PHA) were reported to be resistant against polymer aging that negatively affects polymer properties. Recently, more and more attempts have been directed to make PHA block copolymers. Diblock copolymers PHB-b-PHHx consisting of poly-3-hydroxybutyrate (PHB...... structural related mechanical properties.......) block covalently bonded with poly-3-hydroxyhexanoate (PHHx) block were for the first time produced successfully by a recombinant Pseudomonas putida KT2442 with its β-oxidation cycle deleted to its maximum. RESULTS: The chloroform extracted polymers were characterized by nuclear magnetic resonance (NMR...

  2. Electric field effects on alignment of lamellar structures in diblock copolymer thin films studied by neutron scattering

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Xiuli

    2006-12-07

    We investigated the lamellar orientation in thin films of a diblock copolymer P(S-b-MMA), under competing effects of surface interactions and an electric field applied perpendicular to the substrate. The surface effects tend to align the lamellae parallel to the substrate while the electric field tends to align the lamellae perpendicular to the substrate. Using neutron reflectivity, neutron diffuse scattering, and neutron small-angle scattering, we achieved a quantitative analysis of the internal structure of the films. Film thickness was found to play a non-trivial role in determining the structure of the films. A complete alignment by the surface effects was observed in the thinner films by annealing. The parallel orientation remains stable even if an electric field as strong as 40 V/{mu}m is applied. In the thicker films, a mixed orientation with boundary layers parallel and the central part partially perpendicular to the substrate was observed after annealing. The mixed orientation becomes unstable under a small compressive stress, and will be converted into a completely parallel orientation. The parallel orientation induced by the compressive stress remains stable as long as the electric field is weaker than several ten V/{mu}m. Only a field of about 40 V/{mu}m is able to stabilize the above mentioned mixed orientation. A fully perpendicular orientation was never observed in our experiments. Diffuse scattering shows a mosaic structure in the absence of an electric field, whose mosaicity will be increased by the torque exerted by an electric field. The lateral correlation length of the lamellar domains is estimated as 1-2 {mu}m. Limited by the small q{sub x}-range we have used, a clear statement on the existence of the electric-field-induced structural undulations predicted by the Onuki's theory cannot be made from our experiments. (orig.)

  3. Nanostructure of polyplexes formed between cationic diblock copolymer and antisense oligodeoxynucleotide and its influence on cell transfection efficiency.

    Science.gov (United States)

    Zhao, Xiubo; Pan, Fang; Zhang, ZhuoQi; Grant, Colin; Ma, YingHua; Armes, Steven P; Tang, YiQing; Lewis, Andrew L; Waigh, Thomas; Lu, Jian R

    2007-11-01

    Although various cationic polymers have been used to condense anionically charged DNA to improve their transfection efficiency, there is still a lack of fundamental understanding about how to control the nanostructure and charge of the polyplexes formed and how to relate such information to cell transfection efficiency. In this work, we have synthesized a weak cationic and phosphorylcholine-containing diblock copolymer and used it as a model vector to deliver an antisense oligodeoxynucleotide (ODN) into HeLa cells. Small angle neutron scattering (SANS) was used to determine the copolymer/ODN polyplex structure. The SANS data revealed the formation of polyplex nanocylinders at high copolymer (N)/ODN (P) charge ratios, where N symbolizes the amine groups on the copolymer and P symbolizes the phosphate groups. However, the cylindrical lengths remained constant, indicating that the ODN binding over this region did not alter the cylindrical shape of the copolymer in solution. As the N/P ratio decreased and became close to unity the polyplex diameters remained constant, but their lengths increased substantially, suggesting the end-to-end bridging by ODN binding between copolymer cylinders. As the N/P ratios went below unity (with ODN in excess), the polyplex diameters increased substantially, indicating different ODN bridging to bundle the small polyplexes together. Transfection studies from HeLa cells indicated a steady increase in transfection efficiency with increasing cationic charge and decreasing polyplex size. Cell growth inhibition assay showed significant growth inhibition by the polyplexes coupled with weak cytotoxicity, indicating effective ODN delivery. While this study has confirmed the overall charge effect, it has also revealed progressive structural changes of the polyplexes against varying charge ratio, thereby providing useful insight into the mechanistic process behind the ODN delivery.

  4. Electric field effects on alignment of lamellar structures in diblock copolymer thin films studied by neutron scattering

    International Nuclear Information System (INIS)

    Jiang, Xiuli

    2006-01-01

    We investigated the lamellar orientation in thin films of a diblock copolymer P(S-b-MMA), under competing effects of surface interactions and an electric field applied perpendicular to the substrate. The surface effects tend to align the lamellae parallel to the substrate while the electric field tends to align the lamellae perpendicular to the substrate. Using neutron reflectivity, neutron diffuse scattering, and neutron small-angle scattering, we achieved a quantitative analysis of the internal structure of the films. Film thickness was found to play a non-trivial role in determining the structure of the films. A complete alignment by the surface effects was observed in the thinner films by annealing. The parallel orientation remains stable even if an electric field as strong as 40 V/μm is applied. In the thicker films, a mixed orientation with boundary layers parallel and the central part partially perpendicular to the substrate was observed after annealing. The mixed orientation becomes unstable under a small compressive stress, and will be converted into a completely parallel orientation. The parallel orientation induced by the compressive stress remains stable as long as the electric field is weaker than several ten V/μm. Only a field of about 40 V/μm is able to stabilize the above mentioned mixed orientation. A fully perpendicular orientation was never observed in our experiments. Diffuse scattering shows a mosaic structure in the absence of an electric field, whose mosaicity will be increased by the torque exerted by an electric field. The lateral correlation length of the lamellar domains is estimated as 1-2 μm. Limited by the small q x -range we have used, a clear statement on the existence of the electric-field-induced structural undulations predicted by the Onuki's theory cannot be made from our experiments. (orig.)

  5. Construction of amphiphilic segments on polypropylene nonwoven surface and its application in removal of endocrine disrupting compounds (EDCs) from aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Kai [State Key Laboratory of Hollow Fiber Membrane Materials and Processes, Tianjin Polytechnic University, Tianjin 300160 (China); School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300160 (China); Wei, Junfu, E-mail: junfuwei1963@163.com [State Key Laboratory of Hollow Fiber Membrane Materials and Processes, Tianjin Polytechnic University, Tianjin 300160 (China); School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300160 (China); Zhou, Xiangyu [State Key Laboratory of Hollow Fiber Membrane Materials and Processes, Tianjin Polytechnic University, Tianjin 300160 (China); School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300160 (China); School of Materials Science and Engineering, Tianjin Polytechnic University, Tianjin 300160 (China); Liu, Nana [State Key Laboratory of Hollow Fiber Membrane Materials and Processes, Tianjin Polytechnic University, Tianjin 300160 (China); School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300160 (China)

    2015-05-15

    Highlights: • The amphiphilic segments on polypropylene nonwoven surface were constructed successfully. • The adsorption behavior for EDCs of the amphiphilic adsorption materials was systematically studied. • The novel amphiphilic adsorption materials have broad application prospects in EDCs removal from aqueous solution. - Abstract: The amphiphilic segments on polypropylene nonwoven (PP nonwoven) surface were constructed using the ultraviolet (UV) irradiation graft polymerization for the removal of endocrine disrupting compounds (EDCs) with different polarity from aqueous solution. The stearyl acrylate (SA) as hydrophobic functional monomer was introduced onto the surface of PP nonwoven fabric at first stage and then the hydroxyethyl acrylate (HEA) as hydrophilic functional monomer was introduced subsequently. The effect of functional monomer concentration and UV irradiation time on grafting ratio was studied and discussed. The novel amphiphilic structure was designed and constructed based on adsorption capacity for the target micropollutants. The structure and composition of the amphiphilic adsorption materials were characterized by Fourier transform infrared spectrometer (FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and contact angle (CA). The adsorption behaviors for EDCs of the amphiphilic adsorption materials were studied and the results indicated that the adsorption capacity and adsorption rate were superior to single SA grafted PP nonwoven (PP-g-SA) and single HEA grafted PP nonwoven (PP-g-HEA). The novel amphiphilic adsorption material was efficient for the removal of EDCs with different polarity and could be utilized as a potential adsorption material for removing EDCs from aqueous solution.

  6. Construction of amphiphilic segments on polypropylene nonwoven surface and its application in removal of endocrine disrupting compounds (EDCs) from aqueous solution

    International Nuclear Information System (INIS)

    Liu, Kai; Wei, Junfu; Zhou, Xiangyu; Liu, Nana

    2015-01-01

    Highlights: • The amphiphilic segments on polypropylene nonwoven surface were constructed successfully. • The adsorption behavior for EDCs of the amphiphilic adsorption materials was systematically studied. • The novel amphiphilic adsorption materials have broad application prospects in EDCs removal from aqueous solution. - Abstract: The amphiphilic segments on polypropylene nonwoven (PP nonwoven) surface were constructed using the ultraviolet (UV) irradiation graft polymerization for the removal of endocrine disrupting compounds (EDCs) with different polarity from aqueous solution. The stearyl acrylate (SA) as hydrophobic functional monomer was introduced onto the surface of PP nonwoven fabric at first stage and then the hydroxyethyl acrylate (HEA) as hydrophilic functional monomer was introduced subsequently. The effect of functional monomer concentration and UV irradiation time on grafting ratio was studied and discussed. The novel amphiphilic structure was designed and constructed based on adsorption capacity for the target micropollutants. The structure and composition of the amphiphilic adsorption materials were characterized by Fourier transform infrared spectrometer (FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and contact angle (CA). The adsorption behaviors for EDCs of the amphiphilic adsorption materials were studied and the results indicated that the adsorption capacity and adsorption rate were superior to single SA grafted PP nonwoven (PP-g-SA) and single HEA grafted PP nonwoven (PP-g-HEA). The novel amphiphilic adsorption material was efficient for the removal of EDCs with different polarity and could be utilized as a potential adsorption material for removing EDCs from aqueous solution

  7. Synthesis of Thermoresponsive Amphiphilic Polyurethane Gel as a New Cell Printing Material near Body Temperature.

    Science.gov (United States)

    Tsai, Yi-Chun; Li, Suming; Hu, Shiaw-Guang; Chang, Wen-Chi; Jeng, U-Ser; Hsu, Shan-hui

    2015-12-23

    Waterborne polyurethane (PU) based on poly(ε-caprolactone) (PCL) diol and a second oligodiol containing amphiphilic blocks was synthesized in this study. The microstructure was characterized by dynamic light scattering (DLS), small-angle X-ray scattering (SAXS), and rheological measurement of the PU dispersion. The surface hydrophilicity measurement, infrared spectroscopy, wide-angle X-ray diffraction, mechanical and thermal analyses were conducted in solid state. It was observed that the presence of a small amount of amphiphilic blocks in the soft segment resulted in significant changes in microstructure. When 90 mol % PCL diol and 10 mol % amphiphilic blocks of poly(l-lactide)-poly(ethylene oxide) (PLLA-PEO) diol were used as the soft segment, the synthesized PU had a water contact angle of ∼24° and degree of crystallinity of ∼14%. The dispersion had a low viscosity below room temperature. As the temperature was raised to body temperature (37 °C), the dispersion rapidly (∼170 s) underwent sol-gel transition with excellent gel modulus (G' ≈ 6.5 kPa) in 20 min. PU dispersions with a solid content of 25-30% could be easily mixed with cells in sol state, extruded by a 3D printer, and deposited layer by layer as a gel. Cells remained alive and proliferating in the printed hydrogel scaffold. We expect that the development of novel thermoresponsive PU system can be used as smart injectable hydrogel and applied as a new type of bio-3D printing ink.

  8. Emergent properties arising from the assembly of amphiphiles. Artificial vesicle membranes as reaction promoters and regulators.

    Science.gov (United States)

    Walde, Peter; Umakoshi, Hiroshi; Stano, Pasquale; Mavelli, Fabio

    2014-09-14

    This article deals with artificial vesicles and their membranes as reaction promoters and regulators. Among the various molecular assemblies which can form in an aqueous medium from amphiphilic molecules, vesicle systems are unique. Vesicles compartmentalize the aqueous solution in which they exist, independent on whether the vesicles are biological vesicles (existing in living systems) or whether they are artificial vesicles (formed in vitro from natural or synthetic amphiphiles). After the formation of artificial vesicles, their aqueous interior (the endovesicular volume) may become - or may be made - chemically different from the external medium (the exovesicular solution), depending on how the vesicles are prepared. The existence of differences between endo- and exovesicular composition is one of the features on the basis of which biological vesicles contribute to the complex functioning of living organisms. Furthermore, artificial vesicles can be formed from mixtures of amphiphiles in such a way that the vesicle membranes become molecularly, compositionally and organizationally highly complex, similarly to the lipidic matrix of biological membranes. All the various properties of artificial vesicles as membranous compartment systems emerge from molecular assembly as these properties are not present in the individual molecules the system is composed of. One particular emergent property of vesicle membranes is their possible functioning as promoters and regulators of chemical reactions caused by the localization of reaction components, and possibly catalysts, within or on the surface of the membranes. This specific feature is reviewed and highlighted with a few selected examples which range from the promotion of decarboxylation reactions, the selective binding of DNA or RNA to suitable vesicle membranes, and the reactivation of fragmented enzymes to the regulation of the enzymatic synthesis of polymers. Such type of emergent properties of vesicle membranes may

  9. A Review of the Role of Amphiphiles in Biomass to Ethanol Conversion

    Directory of Open Access Journals (Sweden)

    William Gibbons

    2013-04-01

    Full Text Available One of the concerns for economical production of ethanol from biomass is the large volume and high cost of the cellulolytic enzymes used to convert biomass into fermentable sugars. The presence of acetyl groups in hemicellulose and lignin in plant cell walls reduces accessibility of biomass to the enzymes and makes conversion a slow process. In addition to low enzyme accessibility, a rapid deactivation of cellulases during biomass hydrolysis can be another factor contributing to the low sugar recovery. As of now, the economical reduction in lignin content of the biomass is considered a bottleneck, and raises issues for several reasons. The presence of lignin in biomass reduces the swelling of cellulose fibrils and accessibility of enzyme to carbohydrate polymers. It also causes an irreversible adsorption of the cellulolytic enzymes that prevents effective enzyme activity and recycling. Amphiphiles, such as surfactants and proteins have been found to improve enzyme activity by several mechanisms of action that are not yet fully understood. Reduction in irreversible adsorption of enzyme to non-specific sites, reduction in viscosity of liquid and surface tension and consequently reduced contact of enzyme with air-liquid interface, and modifications in biomass chemical structure are some of the benefits derived from surface active molecules. Application of some of these amphiphiles could potentially reduce the capital and operating costs of bioethanol production by reducing fermentation time and the amount of enzyme used for saccharification of biomass. In this review article, the benefit of applying amphiphiles at various stages of ethanol production (i.e., pretreatment, hydrolysis and hydrolysis-fermentation is reviewed and the proposed mechanisms of actions are described.

  10. Effective lubrication of articular cartilage by an amphiphilic hyaluronic acid derivative.

    Science.gov (United States)

    Schiavinato, Antonella; Whiteside, Robert A

    2012-06-01

    Intra-articular injection of hyaluronic acid based therapies is gaining popularity as a treatment option for non-operative management of patients with symptomatic osteoarthritis. Although there is an abundance of evidence for both biological and mechanical mechanisms of joint protection by hyaluronic acid, one clear intention of viscosupplementation is to reduce friction and wear by providing an extrinsic lubricant. We tested the in vitro friction response of a novel hyaluronic acid derivative that presents amphiphilic features to promote adhesion to the cartilage surface and thereby improve cartilage lubrication. Migrating Contact Area and Static Contact Area friction tests were conducted on bovine articular cartilage to assess the efficacy of two lubricants, a chemically modified amphiphilic hyaluronic acid and synovial fluid from a healthy joint, as well as a phosphate buffered saline negative control. No differences in lubrication (P=0.34) were evident between the three test articles during the Migrating Contact Area test, which represents articulation of healthy articular cartilage. The modified hyaluronic acid presented an equilibrium friction coefficient 2.8 times less than that of the synovial fluid (P ≤ 0.0005) and five times less than that of the PBS control (P ≤ 0.0001) during the Static Contact Area test, representing a mixed lubrication condition. The present study demonstrated that a chemically modified amphiphilic hyaluronic acid can provide equivalent lubrication to synovial fluid during articulation of loaded healthy articular cartilage and can provide superior lubrication as indicated by a lower coefficient of friction than synovial fluid under loading conditions potentially associated with cartilage wear. Copyright © 2011 Elsevier Ltd. All rights reserved.

  11. Nanostructures by self-assembling peptide amphiphile as potential selective drug carriers.

    Science.gov (United States)

    Accardo, Antonella; Tesauro, Diego; Mangiapia, Gaetano; Pedone, Carlo; Morelli, Giancarlo

    2007-01-01

    The self-assembling behavior, at physiological pH, of the amphiphile peptide (C18)(2)L5CCK8 in nanostructures is reported. Stable aggregates presenting a critical micellar concentration of 2 x 10(-6) mol kg(-1), and characterized by water exposed CCK8 peptide in beta-sheet conformation, are obtained. Small angle neutron scattering experiments are indicative for a 3D structure with dimensions > or =100 nm. AFM images confirm the presence of nanostructures. Fluorescence experiments indicating the sequestration of pyrene, chosen as drug model, and the anticancer Doxorubicin within the nanostructures are reported.

  12. Small angle neutron scattering study of the micelle structure of amphiphilic block copolymers

    International Nuclear Information System (INIS)

    Yamaoka, H.; Matsuoka, H.; Sumaru, K.; Hanada, S.

    1994-01-01

    The amphiphilic block copolymers of vinyl ether were prepared by living cationic polymerization. The partially deuterated copolymers for SANS experiments were especially synthesized by introducing deuterated phenyl units in the hydrophobic chain. SANS measurements were performed for aqueous solutions of these copolymers by changing H 2 O/D 2 O ratios. The SANS profiles indicate that the micelles in the present system exhibit a core-shell structure and that the size and shape of micelles are largely dependent on the length of hydrophobic chain. The micelle of shorter hydrophobic chain was found to be nearly spherical, whereas the micelle of longer hydrophobic chain was confirmed to have an ellipsoidal shape

  13. Interactions between colloidal particles in the presence of an ultrahighly charged amphiphilic polyelectrolyte.

    Science.gov (United States)

    Yu, Danfeng; Yang, Hui; Wang, Hui; Cui, Yingxian; Yang, Guang; Zhang, Jian; Wang, Jinben

    2014-12-09

    A novel amphiphilic polyelectrolyte denoted as PAGC8 and a traditional amphiphilic polyelectrolyte denoted as PASC8 were prepared. PAGC8 consisted of gemini-type surfactant segment based on 1,3-bis (N,N-dimethyl-N-octylammonium)-2-propyl acrylate dibromide, while PASC8 incorporated acryloyloxyethyl-N,N-dimethyl-N-dodecylammonium bromide as single chain surfactant units within its repeat unit structure. Turbidity, stability, and zeta potential measurements were performed in the presence of PAGC8 and PASC8, respectively, to evaluate their effectiveness in inducing solid/liquid separations. It was found that the maximum transmittance was observed before the zeta potential values reached the isoelectric point, implying that not only charge neutralization but also charge-patch mechanism contributed to the separation process. Colloid probe atomic force microscopy technique was introduced to directly determine the interactions between surfaces in the presence of ultrahighly charged amphiphilic polyelectrolyte. On the basis of the AFM results, we have successfully interpreted the influence of the charge density of the polyelectrolytes on the phase stability. Electrostatic interaction played the dominant role in the flocculation processes, although both electrostatic interaction and hydrophobic effect provided contributions to the colloidal dispersions. The attractions upon surfaces approach in the case of PAGC8 were significantly larger than that of PASC8 due to the higher charge density. The strong peeling events upon retraction in the presence of PAGC8 implied that the hydrophobic effect was stronger than that of PASC8, which displayed the loose pulling events. A strong attraction was identified at shorter separation distances for both systems. However, these interactions cannot be successfully described by the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory of colloid stability due to the participation of charge-patch and strong hydrophobic effect. To account for the

  14. Synthesis of Novel Amphiphilic Azobenzenes and X-ray Scattering Studies of Their Langmuir Monolayers

    DEFF Research Database (Denmark)

    Sørensen, Thomas Just; Kjær, Kristian; Breiby, Dag Werner

    2008-01-01

    . At the air-water interface, the amphiphilic azobenzenes form noncrystalline but stable Langmuir films that display an unusual reversible monolayer collapse close to 35 mN/m. The structures and phase transitions were studied by X-ray reflectivity (XR) and grazing-incidence X-ray diffraction, both utilizing...... synchrotron radiation. Compression beyond the collapse point does not change the XR data, showing that the film is unchanged at the molecular level, even at areas less than half of that of the collapse. This leads to the conclusion that few macroscopic collapse sites are responsible for reversibly removing...

  15. Macroscopic alignment of graphene stacks by Langmuir-Blodgett deposition of amphiphilic hexabenzocoronenes

    DEFF Research Database (Denmark)

    Laursen, B.W.; Nørgaard, K.; Reitzel, N.

    2004-01-01

    e present structural studies of Langmuir V and Langmuir-Blodgett (LB) films of new amphiphilic hexa-peri-hexabenzocoronene (HBC) discotics, carrying five branched alkyl side chains and one polar group. The polar group is either a carboxylic acid moiety or an electron acceptor moiety (anthraquinone...... and tilted relative to the water surface. The intercolumnar distance is 20 A. The HBCs are confined to a layer lying on top of the layer of polar groups that are in contact with the water subphase. Efficient transfer of the monolayer of the anthraquinone-substituted HBC derivative to hydrophobic quartz...

  16. A spectroscopic method to estimate the binding potency of amphiphile assemblies

    Czech Academy of Sciences Publication Activity Database

    Gauger, D. R.; Andrushchenko, Valery; Bouř, Petr; Pohle, W.

    2010-01-01

    Roč. 398, č. 2 (2010), s. 1109-1123 ISSN 1618-2642 R&D Projects: GA ČR GA203/06/0420; GA ČR GA202/07/0732; GA ČR GAP208/10/0559; GA AV ČR IAA400550702; GA AV ČR IAA400550701 Institutional research plan: CEZ:AV0Z40550506 Keywords : miccels * amphiphile assemblies * molecular dynamics * infrared spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.841, year: 2010

  17. Catalytic Y-tailed amphiphilic homopolymers – aqueous nanoreactors for high activity, low loading SCS pincer catalysts

    Science.gov (United States)

    Patterson, Joseph P.; Cotanda, Pepa; Kelley, Elizabeth G.; Moughton, Adam O.; Lu, Annhelen; Epps, Thomas H.; O’Reilly, Rachel K.

    2013-01-01

    A new amphiphilic homopolymer bearing an SCS pincer palladium complex has been synthesized by reversible addition fragmentation chain transfer polymerization. The amphiphile has been shown to form spherical and worm-like micelles in water by cryogenic transmission electron microscopy and small angle neutron scattering. Segregation of reactive components within the palladium containing core results in increased catalytic activity of the pincer compound compared to small molecule analogues. This allows carbon-carbon bond forming reactions to be performed in water with reduced catalyst loadings and enhanced activity. PMID:23539324

  18. Broadband pH-Sensing Organic Transistors with Polymeric Sensing Layers Featuring Liquid Crystal Microdomains Encapsulated by Di-Block Copolymer Chains.

    Science.gov (United States)

    Seo, Jooyeok; Song, Myeonghun; Jeong, Jaehoon; Nam, Sungho; Heo, Inseok; Park, Soo-Young; Kang, Inn-Kyu; Lee, Joon-Hyung; Kim, Hwajeong; Kim, Youngkyoo

    2016-09-14

    We report broadband pH-sensing organic field-effect transistors (OFETs) with the polymer-dispersed liquid crystal (PDLC) sensing layers. The PDLC layers are prepared by spin-coating using ethanol solutions containing 4-cyano-4'-pentyl-biphenyl (5CB) and a diblock copolymer (PAA-b-PCBOA) that consists of LC-philic block [poly(4-cyano-biphenyl-4-oxyundecyl acrylate) (PCBOA)] and acrylic acid block [poly(acrylic acid) (PAA)]. The spin-coated sensing layers feature of 5CB microdomains (OFETs (PDLC-i-OFETs) can detect precisely and reproducibly a wide range of pH with only small amounts (10-40 μL) of analyte solutions in both static and dynamic perfusion modes. The positive drain current change is measured for acidic solutions (pH 7) result in the negative change of drain current. The drain current trend in the present PDLC-i-OFET devices is explained by the shrinking-expanding mechanism of the PAA chains in the diblock copolymer layers.

  19. Mechanical Properties of Weakly Segregated Block Copolymers. 3. Influence of Strain Rate and Temperature on Tensile Properties of Poly(styrene-b-butyl methacrylate) Diblock Copolymers with Different Morphologies

    NARCIS (Netherlands)

    Weidisch, R.; Stamm, M.; Michler, G.H.; Fischer, H.R.; Jérôme, R.

    1999-01-01

    Poly(styrene-b-butyl methacrylate) diblock copolymers, PS-6-PBMA, with different morphologies are investigated with respect to the influence of strain rate and temperature on tensile properties. In the first part the mechanical properties of bicontinuous and perforated lamellar structure are

  20. The non-peptidic part determines the internalization mechanism and intracellular trafficking of peptide amphiphiles.

    Science.gov (United States)

    Missirlis, Dimitris; Teesalu, Tambet; Black, Matthew; Tirrell, Matthew

    2013-01-01

    Peptide amphiphiles (PAs) are a class of amphiphilic molecules able to self-assemble into nanomaterials that have shown efficient in vivo targeted delivery. Understanding the interactions of PAs with cells and the mechanisms of their internalization and intracellular trafficking is critical in their further development for therapeutic delivery applications. PAs of a novel, cell- and tissue-penetrating peptide were synthesized possessing two different lipophilic tail architectures and their interactions with prostate cancer cells were studied in vitro. Cell uptake of peptides was greatly enhanced post-modification. Internalization occurred via lipid-raft mediated endocytosis and was common for the two analogs studied. On the contrary, we identified the non-peptidic part as the determining factor of differences between intracellular trafficking and retention of PAs. PAs composed of di-stearyl lipid tails linked through poly(ethylene glycol) to the peptide exhibited higher exocytosis rates and employed different recycling pathways compared to ones consisting of di-palmitic-coupled peptides. As a result, cell association of the former PAs decreased with time. Control over peptide intracellular localization and retention is possible by appropriate modification with synthetic hydrophobic tails. We propose this as a strategy to design improved peptide-based delivery systems.

  1. The non-peptidic part determines the internalization mechanism and intracellular trafficking of peptide amphiphiles.

    Directory of Open Access Journals (Sweden)

    Dimitris Missirlis

    Full Text Available BACKGROUND: Peptide amphiphiles (PAs are a class of amphiphilic molecules able to self-assemble into nanomaterials that have shown efficient in vivo targeted delivery. Understanding the interactions of PAs with cells and the mechanisms of their internalization and intracellular trafficking is critical in their further development for therapeutic delivery applications. METHODOLOGY/PRINCIPAL FINDINGS: PAs of a novel, cell- and tissue-penetrating peptide were synthesized possessing two different lipophilic tail architectures and their interactions with prostate cancer cells were studied in vitro. Cell uptake of peptides was greatly enhanced post-modification. Internalization occurred via lipid-raft mediated endocytosis and was common for the two analogs studied. On the contrary, we identified the non-peptidic part as the determining factor of differences between intracellular trafficking and retention of PAs. PAs composed of di-stearyl lipid tails linked through poly(ethylene glycol to the peptide exhibited higher exocytosis rates and employed different recycling pathways compared to ones consisting of di-palmitic-coupled peptides. As a result, cell association of the former PAs decreased with time. CONCLUSIONS/SIGNIFICANCE: Control over peptide intracellular localization and retention is possible by appropriate modification with synthetic hydrophobic tails. We propose this as a strategy to design improved peptide-based delivery systems.

  2. Synthesis of an amphiphilic rhodamine derivative and characterization of its solution and thin film properties

    Energy Technology Data Exchange (ETDEWEB)

    Aviv, Hagit [Department of Chemistry, Bar-Ilan University, Ramat-Gan (Israel); Bar-Ilan University Institute for Nanotechnology and Advanced Materials, Ramat-Gan (Israel); Harazi, Sivan [Department of Chemistry, Bar-Ilan University, Ramat-Gan (Israel); Department of Physics, Bar-Ilan University, Ramat-Gan (Israel); Bar-Ilan University Institute for Nanotechnology and Advanced Materials, Ramat-Gan (Israel); Schiff, Dillon [Department of Chemistry, Bar-Ilan University, Ramat-Gan (Israel); Bar-Ilan University Institute for Nanotechnology and Advanced Materials, Ramat-Gan (Israel); Ramon, Yoni [Department of Chemistry, Bar-Ilan University, Ramat-Gan (Israel); Department of Physics, Bar-Ilan University, Ramat-Gan (Israel); Bar-Ilan University Institute for Nanotechnology and Advanced Materials, Ramat-Gan (Israel); Tischler, Yaakov R., E-mail: yrt@biu.ac.il [Department of Chemistry, Bar-Ilan University, Ramat-Gan (Israel); Bar-Ilan University Institute for Nanotechnology and Advanced Materials, Ramat-Gan (Israel)

    2014-08-01

    Here we present characterization of solution and thin film properties of Lissamine rhodamine B sulfonyl didodecyl amine (LRSD), an amphiphilic derivative of rhodamine. LRSD was synthesized by functionalizing Lissamine rhodamine B sulfonyl chloride (LRSC) with didodecylamine via a straightforward sulfonylation reaction. LRSD's long alkane chains make it highly soluble in chloroform, with a marked increase in brightness compared to the starting material. LRSD is shown to form well-defined robust micelles in water, without the addition of a co-surfactant and stable monolayers at the air–water interface. The greater lipophilicity of LRSD also enables doping into non-polar polymeric host matrices such as polystyrene with less aggregation and hence higher fluorescence quantum yield than LRSC or even rhodamine B. The monolayers of LRSD were prepared via Langmuir–Blodgett deposition and showed shifts in the photoluminescence peak from 575 nm to 595 nm, as the surface pressure is varied from 3 mN/m to 11 mN/m. - Highlights: • Lissamine rhodamine B sulfonyl didodecyl amine (LRSD) is soluble in chloroform. • LRSD shows robust quantum yield in solution and as a dopant in thin film. • LRSD is an amphiphilic rhodamine dye that forms compact fluorescent micelles. • LRSD forms a stable isotherm when spread at the air–water interface.

  3. Dynamic stability of nano-fibers self-assembled from short amphiphilic A6D peptides

    Science.gov (United States)

    Nikoofard, Narges; Maghsoodi, Fahimeh

    2018-04-01

    Self-assembly of A6D amphiphilic peptides in explicit water is studied by using coarse-grained molecular dynamics simulations. It is observed that the self-assembly of randomly distributed A6D peptides leads to the formation of a network of nano-fibers. Two other simulations with cylindrical nano-fibers as the initial configuration show the dynamic stability of the self-assembled nano-fibers. As a striking feature, notable fluctuations occur along the axes of the nano-fibers. Depending on the number of peptides per unit length of the nano-fiber, flat-shaped bulges or spiral shapes along the nano-fiber axis are observed at the fluctuations. Analysis of the particle distribution around the nano-fiber indicates that the hydrophobic core and the hydrophilic shell of the nano-structure are preserved in both simulations. The size of the deformations and their correlation times are different in the two simulations. This study gives new insights into the dynamics of the self-assembled nano-structures of short amphiphilic peptides.

  4. Controlled synthesis of CeO2 nanoparticles using novel amphiphilic cerium complex precursors

    International Nuclear Information System (INIS)

    Yan Bing; Zhu Hongxia

    2008-01-01

    Maleic anhydride was grafted by long-chain alcohols (1-hexadecanol, 1-octadecanol) to amphiphilic mono-L cis-butene dicarboxylates (L = hexadecyl, octadecyl), i.e., MAH, MAO, respectively. Subsequently, corresponding amphiphilic cerium complexes with these two mono-L cis-butene dicarboxylate ligands (Ce(L') 3 , L'= MAH, MAO) were synthesized and behaved as the precursors to prepare CeO 2 nanoparticles for both of which can form nanosized micelle-like aggregates by special self-assembly in the wet chemical process. The nanoparticles were further characterized by Fourier transform-infrared spectroscopy (FTIR), Diffuse reflectance ultraviolet-visible spectra (DRUVS), scanning electron microscope (SEM), transmission electron microscope (TEM), and x-ray diffraction (XRD). Both the CeO 2 nanoparticles are in a cubic fluorite structure and present regular and well-dispersion club-like morphology with average particle size in the range of 40-70 nm. Besides, the strong ultraviolet-visible absorption for these CeO 2 nanoparticles can be found at the long-wavelength ultraviolet to visible region of 200-500 nm.

  5. Macromolecules with amphiphilic monomer units at interface of two immiscible liquids

    Science.gov (United States)

    Glagoleva, A. A.; Vasilevskaya, V. V.

    2017-11-01

    The adsorption of macromolecules with amphiphilic monomer units at the liquid-liquid interface was studied. The amphiphilic structure of monomer units with groups selectively interacting with α and β liquids was described by the A-graft-B dumbbell model. The calculations were performed for the symmetrical interaction of A and B groups with liquids, different selectivity parameters ξ and degree of polymerization N. The simulations indicate a three-step adsorption scenario, including non-adsorbed, weak and strong localization states. It was shown that the adsorption of (A-graft-B)N macromolecules obeys scaling laws developed to describe the adsorption of the alternating (AB)N copolymer at the liquid-liquid interface with critical selectivity parameter ξc of transition into the weak localization state depending on the degree of polymerization as N-1/5; critical selectivity parameter ξ∞ of transition to the strong localization regime non-depending on the degree of polymerization; and relative change of perpendicular Rz radius of gyration varying as a power function of ξN1/5: Rz(ξ)/Rz(0) ˜ (ξN1/5)ρ and ρ = -2ν/(1 - v). Meanwhile, (A-graft-B)N macromolecules have much lower ξc and ξ∞ values and thus are more prospective for practical applications.

  6. 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.

  7. Polydispersity-Driven Block Copolymer Amphiphile Self-Assembly into Prolate-Spheroid Micelles

    Energy Technology Data Exchange (ETDEWEB)

    Schmitt, Andrew L.; Repollet-Pedrosa, Milton H.; Mahanthappa, Mahesh K. (UW)

    2013-09-26

    The aqueous self-assembly behavior of polydisperse poly(ethylene oxide-b-1,4-butadiene-b-ethylene oxide) (OBO) macromolecular triblock amphiphiles is examined to discern the implications of continuous polydispersity in the hydrophobic block on the resulting aqueous micellar morphologies of otherwise monodisperse polymer surfactants. The chain length polydispersity and implicit composition polydispersity of these samples furnishes a distribution of preferred interfacial curvatures, resulting in dilute aqueous block copolymer dispersions exhibiting coexisting spherical and rod-like micelles with vesicles in a single sample with a O weight fraction, w{sub O}, of 0.18. At higher w{sub O} = 0.51-0.68, the peak in the interfacial curvature distribution shifts and we observe the formation of only American football-shaped micelles. We rationalize the formation of these anisotropically shaped aggregates based on the intrinsic distribution of preferred curvatures adopted by the polydisperse copolymer amphiphiles and on the relief of core block chain stretching by chain-length-dependent intramicellar segregation.

  8. Coating of reverse osmosis membranes with amphiphilic copolymers for biofouling control

    KAUST Repository

    Bucs, Szilard

    2017-05-30

    Surface coating of membranes may be a promising option to control biofilm development and biofouling impact on membrane performance of spiral-wound reverse osmosis (RO) systems. The objective of this study was to investigate the impact of an amphiphilic copolymer coating on biofilm formation and biofouling control. The coating was composed of both hydrophilic and hydrophobic monomers hydroxyethyl methacrylate (HEMA) and perfluorodecyl acrylate (PFA), respectively. Commercial RO membranes were coated with HEMA-PFA copolymer film. Long and short term biofouling studies with coated and uncoated membranes and feed spacer were performed using membrane fouling simulators (MFSs) operated in parallel, fed with water containing nutrients. For the long-term studies pressure drop development in time was monitored and after eight days the MFSs were opened and the accumulated biofilm on the membrane and spacer sheets was quantified and characterized. The presence of the membrane coating was determined using X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). Results showed that the amphiphilic coating (i) delayed biofouling (a lower pressure drop increase by a factor of 3 and a lower accumulated active biomass amount by a factor of 6), (ii) influenced the biofilm composition (23% lower polysaccharides and 132% higher protein content) and (iii) was still completely present on the membrane at the end of the biofouling study, showing that the coating was strongly attached to the membrane surface. Using coated membranes and feed spacers in combination with advanced cleaning strategies may be a suitable way to control biofouling.

  9. Amphiphilic nanosheet self-assembly at the water/oil interface: computer simulations.

    Science.gov (United States)

    Xiang, Wenjun; Zhao, Shuangliang; Song, Xianyu; Fang, Shenwen; Wang, Fen; Zhong, Cheng; Luo, Zhaoyang

    2017-03-15

    In this paper, dissipative particle dynamics simulations are performed to study the interfacial and emulsion stabilizing properties of various systems of amphiphilic nanosheets (ANs) self-assembled at the oil/water (O/W) interface. The ANs have a dimensional symmetry structure that encompasses a triangular-plate at the center and two soft comb-like shells constructed with hydrophilic and hydrophobic polymers. As the simulation results show, the AN molecules are highly oriented in interfacial films with their triangular nanosheets parallel to the O/W interface, while their hydrophobic and hydrophilic segments attempt to immerse into the oil phase and aqueous phase, respectively. These results reveal that the rotation of ANs at oil/water interfaces is greatly restricted, meanwhile, their nanosheet (or planar) configuration facilitates their favorable orientation thereby, thus making the emulsion more stable. At higher concentrations, a wrapped-like or micelle morphology is observed. The O/W emulsions stabilized by ANs were also simulated, and it is interesting to find AN 'patches' at the O/W interface which resembles the leather patches on a football. By introducing the "amphiphilic nanosheet balance" concept, the hydrophilic-lipophilic balance (HLB) values of ANs were calculated. Due to their properties of two-dimensional symmetry, the HLB values of ANs tend to approximately 1 which reveals a stronger stability for emulsions.

  10. Dilational rheology of oil/water interfaces covered by amphiphilic polysaccharides derived from dextran.

    Science.gov (United States)

    Desbrières, Jacques; López-Gonzalez, Edeluc; Aguilera-Miguel, Antonio; Sadtler, Véronique; Marchal, Philippe; Castel, Christophe; Choplin, Lionel; Durand, Alain

    2017-12-01

    This work studied the adsorption at dodecane/water interface of amphiphilic polysaccharides derived from dextran (a nonionic bacterial polysaccharide) by random attachment of phenoxy groups along the chains (between 10 and 20 attached phenoxy groups per 100 glucose repeat units). The long-time kinetics of interfacial tension decrease was satisfactorily described assuming diffusion-limited adsorption of hydrophobic units (over 4h). Dilational rheology of dodecane/water interface was studied for the first time with that kind of amphiphilic polysaccharides and evidenced a significant elastic component. For all dextran derivatives, experimental results were conveniently described using Lucassen-van den Tempel model which assumed diffusion-limited of surface active species. The characteristic frequency increased with the number of attached phenoxy groups and its order of magnitude (10 -3 -10 -2 rad.s -1 ) was consistent with estimations based on the previous model. Experimental results were compared to those obtained with commercial stabilizers like Pluronics (L64, P105, F68 and F127) and Tween 80. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Amphiphilic copolymers reduce aggregation of unfolded lysozyme more effectively than polyethylene glycol

    Science.gov (United States)

    Chin, Jaemin; Mustafi, Devkumar; Poellmann, Michael J.; Lee, Raphael C.

    2017-02-01

    Certain amphiphilic block copolymers are known to prevent aggregation of unfolded proteins. To better understand the mechanism of this effect, the optical properties of heat-denatured and dithiothreitol reduced lysozyme were evaluated with respect to controls using UV-Vis spectroscopy, transmission electron microscopy (TEM) and circular dichroism (CD) measurements. Then, the effects of adding Polyethylene Glycol (8000 Da), the triblock surfactant Poloxamer 188 (P188), and the tetrablock copolymer Tetronic 1107 (T1107) to the lysozyme solution were compared. Overall, T1107 was found to be more effective than P188 in inhibiting aggregation, while PEG exhibited no efficacy. TEM imaging of heat-denatured and reduced lysozymes revealed spherical aggregates with on average 250-450 nm diameter. Using CD, more soluble lysozyme was recovered with T1107 than P188 with β-sheet secondary structure. The greater effectiveness of the larger T1107 in preventing aggregation of unfolded lysozyme than the smaller P188 and PEG points to steric hindrance at play; signifying the importance of size match between the hydrophobic region of denatured protein and that of amphiphilic copolymers. Thus, our results corroborate that certain multi-block copolymers are effective in preventing heat-induced aggregation of reduced lysozymes and future studies warrant more detailed focus on specific applications of these copolymers.

  12. Photoisomerization of amphiphilic azobenzene derivatives in Langmuir Blodgett films prepared as polyion complexes, using ionic polymers

    Energy Technology Data Exchange (ETDEWEB)

    Shembekar, Vishakha R. [Department of Chemistry, Indian Institute of Technology, Bombay, Mumbai-400 076 (India); Contractor, A.Q. [Department of Chemistry, Indian Institute of Technology, Bombay, Mumbai-400 076 (India); Major, S.S. [Department of Physics, Indian Institute of Technology, Bombay, Mumbai-400 076 (India); Talwar, S.S. [Department of Physics, Indian Institute of Technology, Bombay, Mumbai-400 076 (India)]. E-mail: chsstia@phy.iitb.ac.in.z

    2006-07-03

    Polyion complexation in mixed Langmuir and Langmuir Blodgett (LB) films of photochromic amphiphilic azobenzene carboxylic acids, 11-[4-(4-hexylphenyl)azo] phenoxyundecanoic acid, 11-(4-phenylazo)phenoxyundecanoic acid, and diamine grafted poly(methylmethaacrylate) polymers has been studied. Monolayer behaviour of the pure components and mixed films was studied through pressure-area isotherms and LB films were characterized by spectroscopic, X-ray diffraction and Atomic force microscopy techniques. Aggregation (H-type), often observed in LB films of pure amphiphilic azo acids, was partly avoided in the mixed LB films as indicated by absorption spectral studies. Photoisomerization of the polyion complexed LB films was also studied. The results altogether demonstrate that amine grafted polymer enter into a polyion complexation with azo acid carboxylate group. LB films could be obtained by transfer of the composite monolayers and these LB films exhibited different levels of aggregation of the azo acids. Reversible photoisomerization was observed in LB films with unaggregated azo acid.

  13. Amphiphilic nanoparticles suppress droplet break-up in a concentrated emulsion flowing through a narrow constriction.

    Science.gov (United States)

    Gai, Ya; Kim, Minkyu; Pan, Ming; Tang, Sindy K Y

    2017-05-01

    This paper describes the break-up behavior of a concentrated emulsion comprising drops stabilized by amphiphilic silica nanoparticles flowing in a tapered microchannel. Such geometry is often used in serial droplet interrogation and sorting processes in droplet microfluidics applications. When exposed to high viscous stresses, drops can undergo break-up and compromise their physical integrity. As these drops are used as micro-reactors, such compromise leads to a loss in the accuracy of droplet-based assays. Here, we show droplet break-up is suppressed by replacing the fluoro-surfactant similar to the one commonly used in current droplet microfluidics applications with amphiphilic nanoparticles as droplet stabilizer. We identify parameters that influence the break-up of these drops and demonstrate that break-up probability increases with increasing capillary number and confinement, decreasing nanoparticle size, and is insensitive to viscosity ratio within the range tested. Practically, our results reveal two key advantages of nanoparticles with direct applications to droplet microfluidics. First, replacing surfactants with nanoparticles suppresses break-up and increases the throughput of the serial interrogation process to 3 times higher than that in surfactant system under similar flow conditions. Second, the insensitivity of break-up to droplet viscosity makes it possible to process samples having different composition and viscosities without having to change the channel and droplet geometry in order to maintain the same degree of break-up and corresponding assay accuracy.

  14. Preparation and Microbiological Evaluation of Amphiphilic Kanamycin-Lipoamino Acid Ion-Pairs

    Directory of Open Access Journals (Sweden)

    Rosario Pignatello

    2014-05-01

    Full Text Available Amphiphilic ion-pairs of kanamycin (KAN were prepared by evaporation of a water-ethanol co-solution of KAN base and a lipoamino acid bearing a 12-carbon atoms alkyl side chain (LAA12, at different molar ratios. Infrared spectroscopy confirmed the structure of ion-pairs, while differential scanning calorimetry (DSC and powder X-ray diffractometry (PXRD studies supported the formation of new saline species with a different crystalline structure than the starting components. The solubility pattern shown in a range of both aqueous and organic solvents confirmed that the ion-pairs possess an amphiphilic character. The LAA12 counter-ion showed not to improve the antibacterial activity of KAN, suggesting that such chemical strategy is not able to favor the penetration of this drug inside the bacteria cells. Nevertheless, a slight improving, i.e., a one-fold dilution, was observed in E. coli. The present study can also serve as the basis for a further evaluation of LAA ion-pairing of antibiotics, as a means to improve the loading of hydrophilic drugs into lipid-based nanocarriers.

  15. Amphiphilic self-assembled polymeric copper catalyst to parts per million levels: click chemistry.

    Science.gov (United States)

    Yamada, Yoichi M A; Sarkar, Shaheen M; Uozumi, Yasuhiro

    2012-06-06

    Self-assembly of copper sulfate and a poly(imidazole-acrylamide) amphiphile provided a highly active, reusable, globular, solid-phase catalyst for click chemistry. The self-assembled polymeric Cu catalyst was readily prepared from poly(N-isopropylacrylamide-co-N-vinylimidazole) and CuSO(4) via coordinative convolution. The surface of the catalyst was covered with globular particles tens of nanometers in diameter, and those sheetlike composites were layered to build an aggregated structure. Moreover, the imidazole units in the polymeric ligand coordinate to CuSO(4) to give a self-assembled, layered, polymeric copper complex. The insoluble amphiphilic polymeric imidazole Cu catalyst with even 4.5-45 mol ppm drove the Huisgen 1,3-dipolar cycloaddition of a variety of alkynes and organic azides, including the three-component cyclization of a variety of alkynes, organic halides, and sodium azide. The catalytic turnover number and frequency were up to 209000 and 6740 h(-1), respectively. The catalyst was readily reused without loss of catalytic activity to give the corresponding triazoles quantitatively.

  16. Removal of volatile organic compounds using amphiphilic cyclodextrin-coated polypropylene

    Directory of Open Access Journals (Sweden)

    Ludmilla Lumholdt

    2014-11-01

    Full Text Available Polypropylene nonwovens were functionalised using a self-assembled, amphiphilic cyclodextrin coating and the potential for water purification by removal of pollutants was studied. As benzene is one of the problematic compounds in the Water Framework Directive, six volatile organic compounds (benzene and five benzene-based substances were chosen as model compounds. The compounds were tested as a mixture in order to provide a more realistic situation since the wastewater will be a complex mixture containing multiple pollutants. The volatile organic compounds are known to form stable inclusion complexes with cyclodextrins. Six different amphiphilic cyclodextrin derivatives were synthesised in order to elucidate whether or not the uptake abilities of the coating depend on the structure of the derivative. Headspace gas chromatography was used for quantification of the uptake exploiting the volatile nature of benzene and its derivatives. The capacity was shown to increase beyond the expected stoichiometries of guest–host complexes with ratios of up to 16:1.

  17. 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.

  18. Amphiphilic DNA tiles for controlled insertion and 2D assembly on fluid lipid membranes: the effect on mechanical properties.

    Science.gov (United States)

    Dohno, Chikara; Makishi, Shingo; Nakatani, Kazuhiko; Contera, Sonia

    2017-03-02

    Future lipid membrane-associated DNA nanostructures are expected to find applications ranging from synthetic biology to nanomedicine. Here we have designed and synthesized DNA tiles and modified them with amphiphilic covalent moieties. dod-DEG groups, which consist of a hydrophilic diethylene glycol (DEG) and a hydrophobic dodecyl group, are introduced at the phosphate backbone to create amphiphilic DNA strands which are subsequently introduced into one face of the DNA tiles. In this way the tile becomes able to stably bind to lipid membranes by insertion of the hydrophobic groups inside the bilayer core. The functionalized tiles do not aggregate in solution. Our results show that these amphiphilic DNA tiles can bind and assemble into 2D lattices on both gel and fluid lipid bilayers. The binding of the DNA structures to membranes is dependent on the lipid phase of the membrane, the concentration of Mg 2+ cations, the length of the amphiphilic modifications to the DNA as well as on the density of the modifications within the tile. Atomic force microscopy-based force spectroscopy is used to investigate the effect of the inserted DNA tiles on the mechanical properties of the lipid membranes. The results indicate that the insertion of DNA tiles produces an approx. 20% increase of the bilayer breakthrough force.

  19. Adamantane-based amphiphiles (ADAs) for membrane protein study: importance of a detergent hydrophobic group in membrane protein solubilisation.

    Science.gov (United States)

    Chae, Pil Seok; Bae, Hyoung Eun; Das, Manabendra

    2014-10-21

    We prepared adamantane-containing amphiphiles and evaluated them using a large membrane protein complex in terms of protein solubilisation and stabilization efficacy. These agents were superior to conventional detergents, especially in terms of the membrane protein solubilisation efficiency, implying a new detergent structure-property relationship.

  20. 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

  1. Preparation and structural characterisation of novel and versatile amphiphilic octenyl succinic anhydride-modified hyaluronic acid derivatives

    DEFF Research Database (Denmark)

    Eenschooten, Corinne Diane; Guillaumie, Fanny; Kontogeorgis, Georgios

    2010-01-01

    The purpose of the present study was to prepare amphiphilic hyaluronic acid (HA) derivatives and to study the influence of a selection of reaction parameters on the degree of substitution (DS) of the derivatives. Octenyl succinic anhydride (OSA)–modified HA (OSA–HA) derivatives were prepared...

  2. Amphiphilic hollow porous shell encapsulated Au@Pd bimetal nanoparticles for aerobic oxidation of alcohols in water

    KAUST Repository

    Zou, Houbing

    2015-01-01

    © The Royal Society of Chemistry 2015. This work describes the design, synthesis and analysis of an amphiphilic hollow mesoporous shell encapsulating catalytically active Au@Pd bimetal nanoparticles. The particles exhibited excellent catalytic activity and stability in the aerobic oxidation of primary and secondary alcohols to their corresponding aldehydes or ketones in water when using air as an oxidizing agent under atmospheric pressure.

  3. Amphiphilic triblock copolymers with PEGylated hydrocarbon structures as environmentally friendly marine antifouling and fouling-release coatings.

    Science.gov (United States)

    Zhou, Zhaoli; Calabrese, David R; Taylor, Warren; Finlay, John A; Callow, Maureen E; Callow, James A; Fischer, Daniel; Kramer, Edward J; Ober, Christopher K

    2014-01-01

    The ideal marine antifouling (AF)/fouling-release (FR) coating should be non-toxic, while effectively either resisting the attachment of marine organisms (AF) or significantly reducing their strength of attachment (FR). Many recent studies have shown that amphiphilic polymeric materials provide a promising solution to producing such coatings due to their surface dual functionality. In this work, poly(ethylene glycol) (PEG) of different molecular weights (Mw = 350, 550) was coupled to a saturated difunctional alkyl alcohol to generate amphiphilic surfactants (PEG-hydrocarbon-OH). The resulting macromolecules were then used as side chains to covalently modify a pre-synthesized PS8 K-b-P(E/B)25 K-b-PI10 K (SEBI or K3) triblock copolymer, and the final polymers were applied to glass substrata through an established multilayer surface coating technique to prepare fouling resistant coatings. The coated surfaces were characterized with AFM, XPS and NEXAFS, and evaluated in laboratory assays with two important fouling algae, Ulva linza (a green macroalga) and Navicula incerta, a biofilm-forming diatom. The results suggest that these polymer-coated surfaces undergo surface reconstruction upon changing the contact medium (polymer/air vs polymer/water), due to the preferential interfacial aggregation of the PEG segment on the surface in water. The amphiphilic polymer-coated surfaces showed promising results as both AF and FR coatings. The sample with longer PEG chain lengths (Mw = 550 g mol(-1)) exhibited excellent properties against both algae, highlighting the importance of the chemical structures on ultimate biological performance. Besides reporting synthesis and characterization of this new type of amphiphilic surface material, this work also provides insight into the nature of PEG/hydrocarbon amphiphilic coatings, and this understanding may help in the design of future generations of fluorine-free, environmentally friendly AF/FR polymeric coatings.

  4. A Water-Soluble Cyclotriveratrylene-Based Supra-amphiphile: Synthesis, pH-Responsive Self-Assembly in Water, and Its Application in Controlled Drug Release.

    Science.gov (United States)

    Xia, Danyu; Li, Yang; Jie, Kecheng; Shi, Bingbing; Yao, Yong

    2016-06-17

    A new water-soluble cyclotriveratrylene (WCTV) was designed and synthesized, and benzyldimethyldodecylammonium chloride (G) was chosen as the guest molecule to construct a supra-amphiphile by the host-guest interaction between WCTV and G in water, which is pH responsive. The supra-amphiphiles self-assembled into vesicles in water. When the pH of the solution was below 7.0, the supra-amphiphile disassociated, and the vesicles collapsed. Then, the pH-responsive self-assembly system was utilized for controlled drug release.

  5. Synthesis and Self-Assembly of Amphiphilic Triblock Terpolymers with Complex Macromolecular Architecture

    KAUST Repository

    Polymeropoulos, George

    2015-11-25

    Two star triblock terpolymers (PS-b-P2VP-b-PEO)3 and one dendritic-like terpolymer [PS-b-P2VP-b-(PEO)2]3 of PS (polystyrene), P2VP (poly(2-vinylpyridine)), and PEO (poly(ethylene oxide)), never reported before, were synthesized by combining atom transfer radical and anionic polymerizations. The synthesis involves the transformation of the -Br groups of the previously reported Br-terminated 3-arm star diblock copolymers to one or two -OH groups, followed by anionic polymerization of ethylene oxide to afford the star or dendritic structure, respectively. The well-defined structure of the terpolymers was confirmed by static light scattering, size exclusion chromatography, and NMR spectroscopy. The self-assembly in solution and the morphology in bulk of the terpolymers, studied by dynamic light scattering and transmission electron microscopy, respectively, reveal new insights in the phase separation of these materials with complex macromolecular architecture. © 2015 American Chemical Society.

  6. Sugar-based amphiphilic polymers for biomedical applications: from nanocarriers to therapeutics.

    Science.gov (United States)

    Gu, Li; Faig, Allison; Abdelhamid, Dalia; Uhrich, Kathryn

    2014-10-21

    Various therapeutics exhibit unfavorable physicochemical properties or stability issues that reduce their in vivo efficacy. Therefore, carriers able to overcome such challenges and deliver therapeutics to specific in vivo target sites are critically needed. For instance, anticancer drugs are hydrophobic and require carriers to solubilize them in aqueous environments, and gene-based therapies (e.g., siRNA or pDNA) require carriers to protect the anionic genes from enzymatic degradation during systemic circulation. Polymeric micelles, which are self-assemblies of amphiphilic polymers (APs), constitute one delivery vehicle class that has been investigated for many biomedical applications. Having a hydrophobic core and a hydrophilic shell, polymeric micelles have been used as drug carriers. While traditional APs are typically comprised of nondegradable block copolymers, sugar-based amphiphilic polymers (SBAPs) synthesized by us are comprised of branched, sugar-based hydrophobic segments and a hydrophilic poly(ethylene glycol) chain. Similar to many amphiphilic polymers, SBAPs self-assemble into polymeric micelles. These nanoscale micelles have extremely low critical micelle concentrations offering stability against dilution, which occurs with systemic administration. In this Account, we illustrate applications of SBAPs for anticancer drug delivery via physical encapsulation within SBAP micelles and chemical conjugation to form SBAP prodrugs capable of micellization. Additionally, we show that SBAPs are excellent at stabilizing liposomal delivery systems. These SBAP-lipid complexes were developed to deliver hydrophobic anticancer therapeutics, achieving preferential uptake in cancer cells over normal cells. Furthermore, these complexes can be designed to electrostatically complex with gene therapies capable of transfection. Aside from serving as a nanocarrier, SBAPs have also demonstrated unique bioactivity in managing atherosclerosis, a major cause of cardiovascular

  7. Hydrophobic cotton textile surfaces using an amphiphilic graphene oxide (GO) coating

    International Nuclear Information System (INIS)

    Tissera, Nadeeka D.; Wijesena, Ruchira N.; Perera, J. Rangana; Nalin de Silva, K.M.; Amaratunge, Gehan A.J.

    2015-01-01

    Graphical abstract: - Highlights: • Different GO dispersions were prepared by sonicating different amounts of GO in water. Degree of exfoliation of these GO sheets in water was analyzed using Atomic Force Microscopy (AFM). • AFM results obtained showed higher the GO concentration on water more the size of GO sheets and lesser the degree of exfoliation. • GO with different amounts was deposited on cotton fabric using simple dyeing method. • High GO loading on cotton increase the surface area coverage of the textile fibers with GO sheets. This led to less edge to mid area ratio of grafted GO sheets. • As contribution of mid area of GO increase on fiber surface cotton fabric becomes more hydrophobic. • Amphiphilic property of GO sheets was used to lower the surface energy of the cotton fibers leading to hydrophobic property. - Abstract: We report for the first time hydrophobic properties on cotton fabric successfully achieved by grafting graphene oxide on the fabric surface, using a dyeing method. Graphite oxide synthesized by oxidizing natural flake graphite employing improved Hummer's method showed an inter layer spacing of ∼1 nm from XRD. Synthesized graphite oxide was exfoliated in water using ultrasound energy to obtain graphene oxide (GO). AFM data obtained for the graphene oxide dispersed in an aqueous medium revealed a non-uniform size distribution. FTIR characterization of the synthesized GO sheets showed both hydrophilic and hydrophobic functional groups present on the nano sheets giving them an amphiphilic property. GO flakes of different sizes were successfully grafted on to a cotton fabric surface using a dip dry method. Loading different amounts of graphene oxide on the cotton fiber surface allowed the fabric to demonstrate different degrees of hydrophobicity. The highest observed water contact angle was at 143° with the highest loading of graphene oxide. The fabric surfaces grafted with GO also exhibits adhesive type hydrophobicity

  8. Diblock copolymer of bacterial cellulose and poly(methyl methacrylate) initiated by chain-end-type radicals produced by mechanical scission of glycosidic linkages of bacterial cellulose.

    Science.gov (United States)

    Sakaguchi, Masato; Ohura, Takeshi; Iwata, Tadahisa; Takahashi, Shuhei; Akai, Shuji; Kan, Toshiyuki; Murai, Hisao; Fujiwara, Motoyasu; Watanabe, Osamu; Narita, Mamiko

    2010-11-08

    Bacterial cellulose (BC) was mechanically fractured in vacuum at 77 K; this resulted in the scission of the β-1,4 glycosidic linkages of BC. The chain-end-type radicals (mechanoradicals) generated from the scissions were assigned by electron spin resonance (ESR) spectral analyses. A diblock copolymer of BC and poly(methyl methacrylate) (BC-block-PMMA) was produced by the mechanical fracture of BC with MMA (methyl methacrylate) in vacuum at 77 K. Radical polymerization of MMA was initiated by the mechanoradicals located on the BC surface. The BC surface was fully covered with the PMMA chains of the BC-block-PMMA. Novel modification of the BC surface with the BC-block-PMMA was confirmed by spectral analyses of ESR, Fourier-transform infrared, (1)H NMR, and gel permeation chromatography.

  9. Single-component solid lipid nanocarriers prepared with ultra-long chain amphiphilic lipids

    DEFF Research Database (Denmark)

    Wei, Wei; Lu, Xiaonan; Wang, Zegao

    2017-01-01

    HYPOTHESIS: Synthetic sugar alcohol mono-behenates with high melting points, surface activity and resistance to enzymatic lipolysis, are expected to form stable single-component solid lipid nanocarriers (SC-SLNs). The preparation methods and the polar head group of the molecules should affect...... the smallest mean size (∼100nm with PdI of 0.26). In addition, they displayed high entrapment efficiency of fenofibrate (95%) and long term drug release. Nanocarriers prepared by emulsification-diffusion method entrapped fenofibrate into lipid bilayers. In contrast, Nanocarriers prepared by melting......-probe sonication method had a micelle structure with fenofibrate incorporated into a lipid monolayer. This study provides an insight into the systematic development of novel amphiphilic lipids for solid lipid-based drug delivery system....

  10. The Osteogenic Differentiation Effect of the FN Type 10-Peptide Amphiphile on PCL Fiber

    Directory of Open Access Journals (Sweden)

    Ye-Rang Yun

    2018-01-01

    Full Text Available The fibronectin type 10-peptide amphiphile (FNIII10-PA was previously genetically engineered and showed osteogenic differentiation activity on rat bone marrow stem cells (rBMSCs. In this study, we investigated whether FNIII10-PA demonstrated cellular activity on polycaprolactone (PCL fibers. FNIII10-PA significantly increased protein production and cell adhesion activity on PCL fibers in a dose-dependent manner. In cell proliferation results, there was no effect on cell proliferation activity by FNIII10-PA; however, FNIII10-PA induced the osteogenic differentiation of MC3T3-E1 cells via upregulation of bone sialoprotein (BSP, collagen type I (Col I, osteocalcin (OC, osteopontin (OPN, and runt-related transcription factor 2 (Runx2 mitochondrial RNA (mRNA levels; it did not increase the alkaline phosphatase (ALP mRNA level. These results indicate that FNIII10-PA has potential as a new biomaterial for bone tissue engineering applications.

  11. pH-Sensitive Amphiphilic Block-Copolymers for Transport and Controlled Release of Oxygen

    KAUST Repository

    Patil, Yogesh Raghunath

    2017-05-31

    Saturated fluorocarbons, their derivatives and emulsions are capable of dissolving anomalously high amounts of oxygen and other gases. The mechanistic aspects of this remarkable effect remain to be explored experimentally. Here, the synthesis of a library of amphiphilic fluorous block-copolymers incorporating different fluorinated monomers is described, and the capacity of these copolymers for oxygen transport in water is systematically investigated. The structure of the fluorous monomer employed was found to have a profound effect on both the oxygen-carrying capacity and the gas release kinetics of the polymer emulsions. Furthermore, the release of O2 from the polymer dispersions could be triggered by changing the pH of the solution. This is the first example of a polymer-based system for controlled release of a non-polar, non-covalently entrapped respiratory gas.

  12. Supramolecular self-assembly of nonlinear amphiphilic and double hydrophilic block copolymers in aqueous solutions.

    Science.gov (United States)

    Ge, Zhishen; Liu, Shiyong

    2009-09-17

    Supramolecular self-assembly of block copolymers in aqueous solution has received ever-increasing interest over the past few decades due to diverse biological and technological applications in drug delivery, imaging, sensing and catalysis. In addition to relative block lengths, molecular weights and solution conditions, chain architectures of block copolymers can also dramatically affect their self-assembling properties in selective solvents. This feature article mainly focuses on recent developments in the field of supramolecular self-assembly of amphiphilic and double hydrophilic block copolymers (DHBCs) possessing nonlinear chain topologies, including miktoarm star polymers, dendritic-linear block copolymers, cyclic block copolymers and comb-shaped copolymer brushes. Copyright © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Biphasic catalysis using amphiphilic polyphenols-chelated noble metals as highly active and selective catalysts

    Science.gov (United States)

    Mao, Hui; Yu, Hong; Chen, Jing; Liao, Xuepin

    2013-01-01

    In the field of catalysis, it is highly desired to develop novel catalysts that combine the advantages of both homogeneous and heterogeneous catalysts. Here we disclose that the use of plant pholyphenol as amphiphilic large molecule ligand/stabilizer allows for the preparation of noble metal complex and noble metal nanoparticle catalysts. These catalysts are found to be highly selective and active in aqueous-organic biphasic catalysis of cinnamaldehyde and quinoline, and can be reused at least 3 times without significant loss of activity. Moreover, the catalytic activity and reusability of the catalysts can be rationally controlled by simply adjusting the content of polyphenols in the catalysts. Our strategy may be extended to design a wide range of aqueous-organic biphasic catalysis system. PMID:23863916

  14. Biphasic catalysis using amphiphilic polyphenols-chelated noble metals as highly active and selective catalysts.

    Science.gov (United States)

    Mao, Hui; Yu, Hong; Chen, Jing; Liao, Xuepin

    2013-01-01

    In the field of catalysis, it is highly desired to develop novel catalysts that combine the advantages of both homogeneous and heterogeneous catalysts. Here we disclose that the use of plant polyphenol as amphiphilic large molecule ligand/stabilizer allows for the preparation of noble metal complex and noble metal nanoparticle catalysts. These catalysts are found to be highly selective and active in aqueous-organic biphasic catalysis of cinnamaldehyde and quinoline, and can be reused at least 3 times without significant loss of activity. Moreover, the catalytic activity and reusability of the catalysts can be rationally controlled by simply adjusting the content of polyphenols in the catalysts. Our strategy may be extended to design a wide range of aqueous-organic biphasic catalysis system.

  15. Salt Effect on the Cloud Point Phenomenon of Amphiphilic Drug-Hydroxypropylmethyl Cellulose System

    Directory of Open Access Journals (Sweden)

    Mohd. Sajid Ali

    2014-01-01

    Full Text Available Effect of two amphiphilic drugs (tricyclic antidepressant, nortriptyline hydrochloride (NORT, and nonsteroidal anti-inflammatory drug, sodium salt of ibuprofen (IBF on the cloud point of biopolymer hydroxypropylmethyl cellulose (HPMC was studied. Effect of NaCl was also seen on the CP of HPMC-drug system. CP of HPMC increases uniformly on increasing the (drug. Both drugs, though one being anionic (IBF and other cationic (NORT, affect the CP in almost the same manner but with different extent implying the role of hydrophobicity in the interaction between drug and polymer. Salt affects the CP of the drug in a dramatic way as low concentration of salt was only able to increase the value of the CP, though not affecting the pattern. However, in presence of high concentration of salts, minimum was observed on CP versus (drug plots. Various thermodynamic parameters were evaluated and discussed on the basis of the observed results.

  16. 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.

  17. 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.

  18. Novel fluorescent amphiphilic block copolymers: photophysics behavior and interactions with DNA

    Directory of Open Access Journals (Sweden)

    2007-06-01

    Full Text Available In this study, novel amphiphilic fluorescent copolymers poly(N-vinylpyrrolidone-b-poly(N-methacryloyl-N'-(α-naphthylthiourea (PVP-b-PNT were synthesized via ATRP with poly(N-vinylpyrrolidone-Cl as macroinitiator and N-methacryloyl-N'-α-naphthylthiourea (NT as hydrophobic segment. PVP-b-PNT copolymers were characterized by 1H NMR, GPC-MALLS and fluorescence measurements. The aggregation behavior of PVP-b-PNT in water was investigated by transmission electron microscope (TEM and dynamic light scattering (DLS measurement. The photophysics behavior of PVP-b-PNT showed that block copolymer formed strong excimer. The interaction of DNA with the block copolymer made the excimer of block copolymer quench. The cytotoxicity result of PVP-b-PNT in cell culture in vitro indicated that this copolymer PVP-b-PNT had good biocompatibility.

  19. Linear-g-hyperbranched and cyclodextrin-based amphiphilic block copolymer as a multifunctional nanocarrier

    Directory of Open Access Journals (Sweden)

    Yamei Zhao

    2014-11-01

    Full Text Available In this paper, a novel, multifunctional polymer nanocarrier was designed to provide adequate volume for high drug loading, to afford a multiregion encapsulation ability, and to achieve controlled drug release. An amphiphilic, triblock polymer (ABC with hyperbranched polycarbonsilane (HBPCSi and β-cyclodextrin (β-CD moieties were first synthesized by the combination of a two-step reversible addition-fragmentation transfer polymerization into a pseudo-one-step hydrosilylation and quaternization reaction. The ABC then self-assembled into stable micelles with a core–shell structure in aqueous solution. These resulting micelles are multifunctional nanocarriers which possess higher drug loading capability due to the introduction of HBPCSi segments and β-CD moieties, and exhibit controlled drug release based on the diffusion release mechanism. The novel multifunctional nanocarrier may be applicable to produce highly efficient and specialized delivery systems for drugs, genes, and diagnostic agents.

  20. Reduction of the Inflammatory Responses against Alginate-Poly-L-Lysine Microcapsules by Anti-Biofouling Surfaces of PEG-b-PLL Diblock Copolymers

    Science.gov (United States)

    Spasojevic, Milica; Paredes-Juarez, Genaro A.; Vorenkamp, Joop; de Haan, Bart J.; Schouten, Arend Jan; de Vos, Paul

    2014-01-01

    Large-scale application of alginate-poly-L-lysine (alginate-PLL) capsules used for microencapsulation of living cells is hampered by varying degrees of success, caused by tissue responses against the capsules in the host. A major cause is proinflammatory PLL which is applied at the surface to provide semipermeable properties and immunoprotection. In this study, we investigated whether application of poly(ethylene glycol)-block-poly(L-lysine hydrochloride) diblock copolymers (PEG-b-PLL) can reduce the responses against PLL on alginate-matrices. The application of PEG-b-PLL was studied in two manners: (i) as a substitute for PLL or (ii) as an anti-biofouling layer on top of a proinflammatory, but immunoprotective, semipermeable alginate-PLL100 membrane. Transmission FTIR was applied to monitor the binding of PEG-b-PLL. When applied as a substitute for PLL, strong host responses in mice were observed. These responses were caused by insufficient binding of the PLL block of the diblock copolymers confirmed by FTIR. When PEG-b-PLL was applied as an anti-biofouling layer on top of PLL100 the responses in mice were severely reduced. Building an effective anti-biofouling layer required 50 hours as confirmed by FTIR, immunocytochemistry and XPS. Our study provides new insight in the binding requirements of polyamino acids necessary to provide an immunoprotective membrane. Furthermore, we present a relatively simple method to mask proinflammatory components on the surface of microcapsules to reduce host responses. Finally, but most importantly, our study illustrates the importance of combining physicochemical and biological methods to understand the complex interactions at the capsules' surface that determine the success or failure of microcapsules applicable for cell-encapsulation. PMID:25347191

  1. Sequentially Different AB Diblock and ABA Triblock Copolymers as P3HT:PCBM Interfacial Compatibilizers for Bulk-Heterojunction Photovoltaics.

    Science.gov (United States)

    Fujita, Hiroyuki; Michinobu, Tsuyoshi; Fukuta, Seijiro; Koganezawa, Tomoyuki; Higashihara, Tomoya

    2016-03-02

    The P3HT:PCBM (P3HT = poly(3-hexylthiophene, PCBM = phenyl-C61-butyric acid methyl ester) bulk-heterojunction (BHJ) organic photovoltaic (OPV) cells using the AB diblock and ABA triblock copolymers (A = polystyrene derivative with donor-acceptor units (PTCNE) and B = P3HT) as compatibilizers were fabricated. Under the optimized blend ratio of the block copolymer, the power conversion efficiency (PCE) was enhanced. This PCE enhancement was clearly related to the increased short-circuit current (J(sc)) and fill factor (FF). The incident photon to current efficiency (IPCE) measurement suggested that the P3HT crystallinity was improved upon addition of the block copolymers. The increased P3HT crystallinity was consistent with the increased photovoltaic parameters, such as J(sc), FF, and consequently the PCE. The surface energies of these block copolymers suggested their thermodynamically stable location at the interface of P3HT:PCBM, showing the efficient compatibilizing performance, resulting in enlarging and fixing the interfacial area and suppressing the recombination of the generated carriers. Grazing incidence X-ray scattering (GIXS) results confirmed the superior compatibilizing performance of the ABA triblock copolymer when compared to the AB diblock copolymer by the fact that, after blending the ABA triblock copolymer in the P3HT:PCBM system, the enhanced crystallinity of matrix P3HT was observed in the excluded areas of the less-aggregated PCBM domains, changing the P3HT crystalline domain orientation from "edge-on" to "isotropic". This is, to the best of our knowledge, the first sequential effect (AB vs ABA) of the block copolymers on the compatibilizing performances based on BHJ OPV device systems.

  2. A new formulation of curcumin using poly (lactic-co-glycolic acid)—polyethylene glycol diblock copolymer as carrier material

    International Nuclear Information System (INIS)

    Tuyen Dao, Thi Phuong; Nguyen, To Hoai; To, Van Vinh; Ho, Thanh Ha; Nguyen, Tuan Anh; Dang, Mau Chien

    2014-01-01

    The aim of this study is to fabricate a nanoparticle formulation of curcumin using a relatively new vehicle as the matrix polymer: poly(lactic-co-glycolic acid) (PLGA)- polyethylene glycol (PEG) diblock copolymer, and to investigate the effects of the various processing parameters on the characteristics of nanoparticles (NPs). We successfully synthesized the matrix polymer of PLGA-PEG by conjugation of PLGA copolymer with a carboxylate end group to a heterobifunctional amine-PEG-methoxy using N-(3-dimethylaminopropyl)-N’-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide as conjugation crosslinkers. The composition of the formed product (PLGA-PEG) was characterized with 500 MHz 1 H nuclear magnetic resonance (NMR). The conjugation of PLGA-PEG was confirmed using Fourier transform infrared (FTIR) spectrum study. This diblock copolymer was then used to prepare the curcumin-loaded NPs through nanoprecipitation technique. With this method, we found that the size distribution depends on the type of solvent, the concentration of polymer and the concentration of surfactant. The particle size and size distribution were measured by dynamic light scattering (DLS). Transmission electron microscope (TEM) and scanning electron microscope (SEM) were used to confirm the size, structure and morphology of the successfully prepared NPs. All of our results showed that they are spherical and quite homologous with mean diameter around of 100–300 nm. Further, we evaluated encapsulation efficiency and some characteristics of NPs through high performance liquid chromatography (HPLC) analyses, zeta-potential measurements and x-ray diffraction studies. The HPLC analyses were performed to determine the amount of curcumin entrapped in NPs. The zeta-potential measurements confirmed the stability of NPs and the successful encapsulation of curcumin within NPs and the x-ray diffraction patterns showed the disordered-crystalline phase of curcumin inside the polymeric matrix. (paper)

  3. Synthesis of Diblock copolymer poly-3-hydroxybutyrate -block-poly-3-hydroxyhexanoate [PHB-b-PHHx] by a β-oxidation weakened Pseudomonas putida KT2442.

    Science.gov (United States)

    Tripathi, Lakshmi; Wu, Lin-Ping; Chen, Jinchun; Chen, Guo-Qiang

    2012-04-05

    Block polyhydroxyalkanoates (PHA) were reported to be resistant against polymer aging that negatively affects polymer properties. Recently, more and more attempts have been directed to make PHA block copolymers. Diblock copolymers PHB-b-PHHx consisting of poly-3-hydroxybutyrate (PHB) block covalently bonded with poly-3-hydroxyhexanoate (PHHx) block were for the first time produced successfully by a recombinant Pseudomonas putida KT2442 with its β-oxidation cycle deleted to its maximum. The chloroform extracted polymers were characterized by nuclear magnetic resonance (NMR), thermo- and mechanical analysis. NMR confirmed the existence of diblock copolymers consisting of 58 mol% PHB as the short chain length block with 42 mol% PHHx as the medium chain length block. The block copolymers had two glass transition temperatures (Tg) at 2.7°C and -16.4°C, one melting temperature (Tm) at 172.1°C and one cool crystallization temperature (Tc) at 69.1°C as revealed by differential scanning calorimetry (DSC), respectively. This is the first microbial short-chain-length (scl) and medium-chain-length (mcl) PHA block copolymer reported. It is possible to produce PHA block copolymers of various kinds using the recombinant Pseudomonas putida KT2442 with its β-oxidation cycle deleted to its maximum. In comparison to a random copolymer poly-3-hydroxybutyrate-co-3-hydroxyhexanoate (P(HB-co-HHx)) and a blend sample of PHB and PHHx, the PHB-b-PHHx showed improved structural related mechanical properties.

  4. Self assembly of amphiphilic C60 fullerene derivatives into nanoscale supramolecular structures

    Directory of Open Access Journals (Sweden)

    Casscells S Ward

    2007-08-01

    Full Text Available Abstract Background The amphiphilic fullerene monomer (AF-1 consists of a "buckyball" cage to which a Newkome-like dendrimer unit and five lipophilic C12 chains positioned octahedrally to the dendrimer unit are attached. In this study, we report a novel fullerene-based liposome termed 'buckysome' that is water soluble and forms stable spherical nanometer sized vesicles. Cryogenic electron microscopy (Cryo-EM, transmission electron microscopy (TEM, and dynamic light scattering (DLS studies were used to characterize the different supra-molecular structures readily formed from the fullerene monomers under varying pH, aqueous solvents, and preparative conditions. Results Electron microscopy results indicate the formation of bilayer membranes with a width of ~6.5 nm, consistent with previously reported molecular dynamics simulations. Cryo-EM indicates the formation of large (400 nm diameter multilamellar, liposome-like vesicles and unilamellar vesicles in the size range of 50–150 nm diameter. In addition, complex networks of cylindrical, tube-like aggregates with varying lengths and packing densities were observed. Under controlled experimental conditions, high concentrations of spherical vesicles could be formed. In vitro results suggest that these supra-molecular structures impose little to no toxicity. Cytotoxicity of 10–200 μM buckysomes were assessed in various cell lines. Ongoing studies are aimed at understanding cellular internalization of these nanoparticle aggregates. Conclusion In this current study, we have designed a core platform based on a novel amphiphilic fullerene nanostructure, which readily assembles into supra-molecular structures. This delivery vector might provide promising features such as ease of preparation, long-term stability and controlled release.

  5. In vitro evaluation of anticancer nanomedicines based on doxorubicin and amphiphilic Y-shaped copolymers

    Directory of Open Access Journals (Sweden)

    Li D

    2012-05-01

    Full Text Available Di Li,1,2,* Jian Xun Ding,1,3,* Zhao Hui Tang,1 Hai Sun,1 Xiu Li Zhuang,1 Jing Zhe Xu,2 Xue Si Chen1 1Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 2Department of Chemistry, Yanbian University, Yanji, 3Graduate University of Chinese Academy of Sciences, Beijing, China *These authors contributed equally to this workAbstract: Four monomethoxy poly(ethylene glycol-poly(L-lactide-co-glycolide2 (mPEG-P(LA-co-GA2 copolymers were synthesized by ring-opening polymerization of L-lactide and glycolide with double hydroxyl functionalized mPEG (mPEG-(OH2 as macroinitiator and stannous octoate as catalyst. The copolymers self-assembled into nanoscale micellar/vesicular aggregations in phosphate buffer at pH 7.4. Doxorubicin (DOX, an anthracycline anticancer drug, was loaded into the micellar/vesicular nanoparticles, yielding micellar/vesicular nanomedicines. The in vitro release behaviors could be adjusted by content of hydrophobic polyester and pH of the release medium. In vitro cell experiments showed that the intracellular DOX release could be adjusted by content of P(LA-co-GA, and the nanomedicines displayed effective proliferation inhibition against Henrietta Lacks’s cells with different culture times. Hemolysis tests indicated that the copolymers were hemocompatible, and the presence of copolymers could reduce the hemolysis ratio of DOX significantly. These results suggested that the novel anticancer nanomedicines based on DOX and amphiphilic Y-shaped copolymers were attractive candidates as tumor tissular and intracellular targeting drug delivery systems in vivo, with enhanced stability during circulation and accelerated drug release at the target sites.Keywords: amphiphilic Y-shaped copolymer, anticancer nanomedicine, cellular proliferation inhibition, doxorubicin

  6. Screening Nylon-3 Polymers, a New Class of Cationic Amphiphiles, for siRNA Delivery

    Science.gov (United States)

    2015-01-01

    Amphiphilic nucleic acid carriers have attracted strong interest. Three groups of nylon-3 copolymers (poly-β-peptides) possessing different cationic/hydrophobic content were evaluated as siRNA delivery agents in this study. Their ability to condense siRNA was determined in SYBR Gold assays. Their cytotoxicity was tested by MTT assays, their efficiency of delivering Alexa Fluor-488-labeled siRNA intracellularly in the presence and absence of uptake inhibitors was assessed by flow cytometry, and their transfection efficacies were studied by luciferase knockdown in a cell line stably expressing luciferase (H1299/Luc). Endosomal release was determined by confocal laser scanning microscopy and colocalization with lysotracker. All polymers efficiently condensed siRNA at nitrogen-to-phosphate (N/P) ratios of 5 or lower, as reflected in hydrodynamic diameters smaller than that at N/P 1. Although several formulations had negative zeta potentials at N/P 1, G2C and G2D polyplexes yielded >80% uptake in H1299/Luc cells, as determined by flow cytometry. Luciferase knockdown (20–65%) was observed after transfection with polyplexes made of the high molecular weight polymers that were the most hydrophobic. The ability of nylon-3 polymers to deliver siRNA intracellularly even at negative zeta potential implies that they mediate transport across cell membranes based on their amphiphilicity. The cellular uptake route was determined to strongly depend on the presence of cholesterol in the cell membrane. These polymers are, therefore, very promising for siRNA delivery at reduced surface charge and toxicity. Our study identified nylon-3 formulations at low N/P ratios for effective gene knockdown, indicating that nylon-3 polymers are a new, promising type of gene delivery agent. PMID:25437915

  7. Facile synthesis and characterization of novel biodegradable amphiphilic block copolymers bearing pendant hydroxyl groups

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Gaicen; Fan, Xiaoshan; Xu, Bingcan; Zhang, Delong; Hu, Zhiguo, E-mail: zghu@htu.cn

    2014-10-01

    Novel amphiphilic block copolymers bearing pendant hydroxyl groups polylactide-b–poly(3,3-bis(Hydroxymethyl–triazolylmethyl) oxetane)-b–polylactide (PLA-b–PHMTYO-b–PLA) were synthesized via a facile and efficient method. First, the block copolymer intermediates polylactide-b–poly(3,3-Diazidomethyloxetane)-b–polylactide (PLA-b–PBAMO-b–PLA) were synthesized through ring-opening polymerization of lactide using PBAMO as a macroinitiator. Following “Click” reaction of PLA-b–PBAMO-b–PLA with propargyl alcohol provided the targeted amphiphilic block copolymers PLA-b–PHMTYO-b–PLA with pendant hydroxyl groups. The composition and structure of prepared copolymers were characterized by {sup 1}H nuclear magnetic resonance ({sup 1}H NMR) spectroscopy, Fourier transform infrared (FT-IR) and gel permeation chromatography (GPC). The self-assembly behavior of the copolymers in water was investigated by transmission electron microscope (TEM), dynamic light scattering (DLS) and static light scattering (SLS). The results showed that the novel copolymers PLA-b–PHMTYO-b–PLA self-assembled into spherical micelles with diameters ranging from 100 nm to 200 nm in aqueous solution. These copolymers also exhibited low critical micellar concentrations (CMC: 6.9 × 10{sup −4} mg/mL and 3.9 × 10{sup −5} mg/mL, respectively). In addition, the in vitro cytotoxicity of these copolymers was determined in the presence of L929 cells. The results showed that the block copolymers PLA-b–PHMTYO-b–PLA exhibited better biocompatibility. Therefore, these well-defined copolymers are expected to find some applications in drug delivery or tissue engineering. - Highlights: • The method to synthesize PLA-b–PHMTYO-b–PLA is relatively facile and efficient. • PLA-b–PHMTYO-b–PLA self-assembles into spherical micelles with low CMC in water. • PLA-b–PHMTYO-b–PLA exhibits better biocompatibility and biodegradability.

  8. Screening nylon-3 polymers, a new class of cationic amphiphiles, for siRNA delivery.

    Science.gov (United States)

    Nadithe, Venkatareddy; Liu, Runhui; Killinger, Bryan A; Movassaghian, Sara; Kim, Na Hyung; Moszczynska, Anna B; Masters, Kristyn S; Gellman, Samuel H; Merkel, Olivia M

    2015-02-02

    Amphiphilic nucleic acid carriers have attracted strong interest. Three groups of nylon-3 copolymers (poly-β-peptides) possessing different cationic/hydrophobic content were evaluated as siRNA delivery agents in this study. Their ability to condense siRNA was determined in SYBR Gold assays. Their cytotoxicity was tested by MTT assays, their efficiency of delivering Alexa Fluor-488-labeled siRNA intracellularly in the presence and absence of uptake inhibitors was assessed by flow cytometry, and their transfection efficacies were studied by luciferase knockdown in a cell line stably expressing luciferase (H1299/Luc). Endosomal release was determined by confocal laser scanning microscopy and colocalization with lysotracker. All polymers efficiently condensed siRNA at nitrogen-to-phosphate (N/P) ratios of 5 or lower, as reflected in hydrodynamic diameters smaller than that at N/P 1. Although several formulations had negative zeta potentials at N/P 1, G2C and G2D polyplexes yielded >80% uptake in H1299/Luc cells, as determined by flow cytometry. Luciferase knockdown (20-65%) was observed after transfection with polyplexes made of the high molecular weight polymers that were the most hydrophobic. The ability of nylon-3 polymers to deliver siRNA intracellularly even at negative zeta potential implies that they mediate transport across cell membranes based on their amphiphilicity. The cellular uptake route was determined to strongly depend on the presence of cholesterol in the cell membrane. These polymers are, therefore, very promising for siRNA delivery at reduced surface charge and toxicity. Our study identified nylon-3 formulations at low N/P ratios for effective gene knockdown, indicating that nylon-3 polymers are a new, promising type of gene delivery agent.

  9. Nanotoxicity comparison of four amphiphilic polymeric micelles with similar hydrophilic or hydrophobic structure.

    Science.gov (United States)

    Zhao, Bo; Wang, Xue-Qing; Wang, Xiao-You; Zhang, Hua; Dai, Wen-Bing; Wang, Jun; Zhong, Zhen-Lin; Wu, Hou-Nan; Zhang, Qiang

    2013-10-03

    Nanocarriers represent an attractive means of drug delivery, but their biosafety must be established before their use in clinical research. Four kinds of amphiphilic polymeric (PEG-PG-PCL, PEEP-PCL, PEG-PCL and PEG-DSPE) micelles with similar hydrophilic or hydrophobic structure were prepared and their in vitro and in vivo safety were evaluated and compared. In vitro nanotoxicity evaluations included assessments of cell morphology, cell volume, inflammatory effects, cytotoxicity, apoptosis and membrane fluidity. An umbilical vein cell line (Eahy.926) and a kind of macrophages (J774.A1) were used as cell models considering that intravenous route is dominant for micelle delivery systems. In vivo analyses included complete blood count, lymphocyte subset analysis, detection of plasma inflammatory factors and histological observations of major organs after intravenous administration to KM mice. All the micelles enhanced inflammatory molecules in J774.A1 cells, likely resulting from the increased ROS levels. PEG-PG-PCL and PEEP-PCL micelles were found to increase the J774.A1 cell volume. This likely correlated with the size of PEG-PG-PCL micelles and the polyphosphoester structure in PEEP-PCL. PEG-DSPE micelles inhibited the growth of Eahy.926 cells via inducing apoptosis. This might relate to the structure of DSPE, which is a type of phospholipid and has good affinity with cell membrane. No evidence was found for cell membrane changes after treatment with these micelles for 24 h. In the in vivo study, during 8 days of 4 time injection, each of the four nanocarriers altered the hematic phase differently without changes in inflammatory factors or pathological changes in target organs. These results demonstrate that the micelles investigated exhibit diverse nanotoxicity correlated with their structures, their biosafety is different in different cell model, and there is no in vitro and in vivo correlation found. We believe that this study will certainly provide more

  10. Novel amphiphiles with preorganized functionalities-formation of Langmuir-films and efficiency in mineral flotation.

    Science.gov (United States)

    Müller, P U; Akpo, C C; Stöckelhuber, K W; Weber, E

    2005-06-30

    Based on the principle of supramolecular preorganization, three different types of new oligofunctional surfactants have been designed and prepared differing in both the degree of conformational flexibility and the hydrophilic-lipophilic balance of their structures due to the chosen building blocks including rather rigid and shape-persistent backbones or a dendritic subunit. Surface-active properties of the oligofunctional surfactants involving critical micellization concentration, surface tension at cmc, effectiveness of surface tension reduction, and the efficiency of adsorption were determined by use of the surface tension isotherms, respectively. In particular the amino-acid-based amphiphiles show remarkable surface-active properties with the adsorption at the air/water interface and also the aggregation to micelles starting at very low concentration. By analysis of the surface pressure-surface area isotherms interesting information on the packing behavior and orientation of the amphiphilic molecules in relation to the molecular structure could be obtained. Moreover, limiting area and collapse pressure of the Langmuir-films were determined. Morphological observation of the dynamic process of monolayer compression at the air/water interface was carried out by Brewster angle microscopy illustrating several phase states visualized as snap shots. Furthermore, the effectiveness of the new surfactants acting as collecting agents in the process of flotation using the model mineral fluorite was studied. A surprisingly high recovery of the mineral was obtained for the surfactants with constricted flexibility. The flotation plots clearly manifest that bundling of surfactant subunits by tethering to an aromatic core or by dendritic branching is profitable, indicating that effects of preorganization of the oligofunctional surfactant molecules are important.

  11. High-throughput development of amphiphile self-assembly materials: fast-tracking synthesis, characterization, formulation, application, and understanding.

    Science.gov (United States)

    Mulet, Xavier; Conn, Charlotte E; Fong, Celesta; Kennedy, Danielle F; Moghaddam, Minoo J; Drummond, Calum J

    2013-07-16

    Amphiphile self-assembly materials, which contain both a hydrophilic and a hydrophobic domain, have great potential in high-throughput and combinatorial approaches to discovery and development. However, the materials chemistry community has not embraced these ideas to anywhere near the extent that the medicinal chemistry community has. While this situation is beginning to change, extracting the full potential of high-throughput approaches in the development of self-assembling materials will require further development in the synthesis, characterization, formulation, and application domains. One of the key factors that make small molecule amphiphiles prospective building blocks for next generation multifunctional materials is their ability to self-assemble into complex nanostructures through low-energy transformations. Scientists can potentially tune, control, and functionalize these structures, but only after establishing their inherent properties. Because both robotic materials handling and customized rapid characterization equipment are increasingly available, high-throughput solutions are now attainable. These address traditional development bottlenecks associated with self-assembling amphiphile materials, such as their structural characterization and the assessment of end-use functional performance. A high-throughput methodology can help streamline materials development workflows, in accord with existing high-throughput discovery pipelines such as those used by the pharmaceutical industry in drug discovery. Chemists have identified several areas that are amenable to a high-throughput approach for amphiphile self-assembly materials development. These allow an exploration of not only a large potential chemical, compositional, and structural space, but also material properties, formulation, and application variables. These areas of development include materials synthesis and preparation, formulation, characterization, and screening performance for the desired end

  12. Synthesis and evaluation of amphiphilic peptides as nanostructures and drug delivery tools

    Science.gov (United States)

    Sayeh, Naser Ali

    conjugates although one limitation lies in the effort of controlling the rate of drug release. The encapsulated or complexed drugs tend to be released rapidly (before reaching the target site) and in the dendrimer--drug conjugates, it is the chemical linkage that controls the drug release. Thus, future studies in this field are urgently required to create more efficient and stable biomaterials. Peptides are considered as efficient vectors for achieving optimal cellular uptake. The potential use of peptides as drug delivery vectors received much attention by the discovery of several cell-penetrating peptides (CPPs). The first CPPs discovered in 1988, that were sequences from HIV-1 encoded TAT protein, TAT (48--60), and penetrated very efficiently through cell membranes of cultured mammalian cells. CPPs are a class of diverse peptides, typically with 8--25 amino acids, and unlike most peptides, they can cross the cellular membrane with more efficiency. CPPs have also shown to undergo self-assembly and generate nanostructures. The generation of self-assembled peptides and nanostructures occur through various types of interactions between functional groups of amino acid residues, such as electrostatic, hydrophobic, and hydrogen bonding. Appropriate design and functionalization of peptides are critical for generating nanostructures. Chemically CPPs are classified into two major groups: linear and cyclic peptides. It has been previously reported that linear peptides containing hydrophilic and hydrophobic amino acids could act as membrane protein stabilizers. These compounds are short hydrophilic or amphiphilic peptides that have positively charged amino acids, such as arginine, lysine or histidine, which can interact with the negative charge phospholipids layer on the cell membrane and translocate the cargo into the cells. Conjugation to cationic linear CPPs, such as TAT, penetratin, or oligoarginine efficiently improves the cellular uptake of large hydrophilic molecules, but the

  13. Internalization of p53(14-29) peptide amphiphiles and subsequent endosomal disruption results in SJSA-1 cell death.

    Science.gov (United States)

    Missirlis, Dimitris; Krogstad, Daniel V; Tirrell, Matthew

    2010-12-06

    In vivo peptide inhibition of tumor suppressor p53 binding to the protein MDM2 is hampered by inefficient delivery of the peptide. Our approach to couple a hydrophobic lipid-like tail on the inhibitory peptide p53(14-29) allowed its intracellular delivery in vitro, in a panel of different cell lines. The constructed chimeric molecules, termed peptide amphiphiles, further self-assembled into supramolecular structures, identified as elongated wormlike micelles. Internalization of peptides occurred following micelle disassembly, partly via clathrin-mediated endocytosis of monomers. Incubation of SJSA-1 cells in hypertonic culture media, aimed to disrupt endocytic vesicles, resulted in peptide amphiphile-mediated cell death. Our results provide the basis for the construction of novel therapeutic supramolecular nanoparticles and suggest hydrophobic modification of peptides as a promising strategy for enhancing delivery of impermeable peptides.

  14. Ga(III) chelates of amphiphilic DOTA-based ligands: synthetic route and in vitro and in vivo studies

    Energy Technology Data Exchange (ETDEWEB)

    Fontes, Andre [Centro de Quimica, Campus de Gualtar, Universidade do Minho, 4710-057, Braga (Portugal); Prata, M. Isabel M. [IBILI, Faculdade de Medicina, Universidade de Coimbra, 3548, Coimbra (Portugal); Geraldes, Carlos F.G.C. [Departamento de Ciencias da Vida, Faculdade de Ciencias e Tecnologia, Universidade de Coimbra, 3001-401, Coimbra (Portugal); Centro de Neurociencias e Biologia Celular, Universidade de Coimbra, 3001-401, Coimbra (Portugal); Andre, Joao P., E-mail: jandre@quimica.uminho.p [Centro de Quimica, Campus de Gualtar, Universidade do Minho, 4710-057, Braga (Portugal)

    2011-04-15

    In this work, we report on a synthetic strategy using amphiphilic DOTA (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid)-based chelators bearing a variable-sized {alpha}-alkyl chain at one of the pendant acetate arms (from 6 to 14 carbon atoms), compatible with their covalent coupling to amine-bearing biomolecules. The amphiphilic behavior of the micelles-forming Ga(III) chelates (critical micellar concentration), their stability in blood serum and their lipophilicity (logP) were investigated. Biodistribution studies with the {sup 67}Ga-labeled chelates were performed in Wistar rats, which showed a predominant liver uptake with almost no traces of the radiochelates in the body after 24 h.

  15. Graphene oxide-enhanced sol-gel transition sensitivity and drug release performance of an amphiphilic copolymer-based nanocomposite

    Science.gov (United States)

    Hu, Huawen; Wang, Xiaowen; Lee, Ka I; Ma, Kaikai; Hu, Hong; Xin, John H.

    2016-01-01

    We report the fabrication of a highly sensitive amphiphilic copolymer-based nanocomposite incorporating with graphene oxide (GO), which exhibited a low-intensity UV light-triggered sol-gel transition. Non-cytotoxicity was observed for the composite gels after the GO incorporation. Of particular interest were the microchannels that were formed spontaneously within the GO-incorporated UV-gel, which expedited sustained drug release. Therefore, the present highly UV-sensitive, non-cytotoxic amphiphilic copolymer-based composites is expected to provide enhanced photothermal therapy and chemotherapy by means of GO’s unique photothermal properties, as well as through efficient passive targeting resulting from the sol-gel transition characteristic of the copolymer-based system with improved sensitivity, which thus promises the enhanced treatment of patients with cancer and other diseases. PMID:27539298

  16. One-Pot Synthesis of (+-Nootkatone via Dark Singlet Oxygenation of Valencene: The Triple Role of the Amphiphilic Molybdate Catalyst

    Directory of Open Access Journals (Sweden)

    Bing Hong

    2016-11-01

    Full Text Available Efficient one-pot catalytic synthesis of (+-nootkatone was performed from (+-valencene using only hydrogen peroxide and amphiphilic molybdate ions. The process required no solvent and proceeded in three cascade reactions: (i singlet oxygenation of valencene according to the ene reaction; (ii Schenck rearrangement of one hydroperoxide into the secondary β-hydroperoxide; and (iii dehydration of the hydroperoxide into the desired (+-nootkatone. The solvent effect on the hydroperoxide rearrangement is herein discussed. The amphiphilic dimethyldioctyl ammonium molybdate, which is also a balanced surfactant, played a triple role in this process, as molybdate ions catalyzed at both Step 1 and Step 3 and it allowed the rapid formation of a three-phase microemulsion system that highly facilitates product recovery. Preparative synthesis of the high added value (+-nootkatone was thus performed at room temperature with an isolated yield of 46.5%. This is also the first example of a conversion of allylic hydroperoxides into ketones catalyzed by molybdate ions.

  17. Highly ordered self-assembly of one-dimensional nanoparticles in amphiphilic molecular systems

    International Nuclear Information System (INIS)

    Kim, Tae Hwan

    2009-02-01

    Two kinds of one-dimensional (1D) nanoparticles, stable rod-like nanoparticles with highly controlled surface charge density (cROD) and non-covalently functionalized isolated single wall carbon nanotubes (p-SWNT) that were readily redispersible in water, have been developed. Using these 1D nanoparticles, various highly ordered superstructures of 1D nanoparticles by molecular self-assembling based on electrostatic interaction in amphiphilic molecular systems (two different cationic liposome systems) have been investigated. To our knowledge, this is the first demonstration of highly ordered self-assembly of 1D nanoparticles based on electrostatic interaction between 1D nanoparticles and amphiphilic molecules. The cRODs have been developed by free radical polymerization of a mixture of polymerizable cationic surfactant, cetyltrimethylammonium 4-vinylbenzoate (CTVB), and hydrotropic salt sodium 4-styrenesulfonate (NaSS) in aqueous solution. The surface charge of the cROD was controlled by varying the NaSS concentration during the polymerization process and the charge variation was interpreted in terms of the overcharging effect in colloidal systems. The small angle neutron scattering (SANS) measurements showed that the diameter of cROD is constant at 4 nm and the particle length ranges from 20 nm to 85 nm, depending on the NaSS concentration. The cRODs are longest when the NaSS concentration is 5 mol % which corresponds to the charge inversion or neutral point. The SANS and zeta potential measurements showed that the Coulomb interactions between the particles are strongly dependent on the NaSS concentration and the zeta potential of the cRODs changes from positive to negative (+ 12.8 mV ∼ - 44.2 mV) as the concentration of NaSS increases from 0 mol % to 40 mol %. As the NaSS concentration is further increased, the zeta potential is saturated at approximately - 50 mV. The p-SWNTs have been developed by 1) dispersing single wall carbon nanotubes (SWNTs) in water using

  18. A molecular model for membrane fusion based on solution studies of an amphiphilic peptide from HIV gp41.

    OpenAIRE

    Fujii, G.; Horvath, S.; Woodward, S.; Eiserling, F.; Eisenberg, D.

    1992-01-01

    The mechanism of protein-mediated membrane fusion and lysis has been investigated by solution-state studies of the effects of peptides on liposomes. A peptide (SI) corresponding to a highly amphiphilic C-terminal segment from the envelope protein (gp41) of the human immunodeficiency virus (HIV) was synthesized and tested for its ability to cause lipid membranes to fuse together (fusion) or to break open (lysis). These effects were compared to those produced by the lytic and fusogenic peptide ...

  19. Biocompatible Soft Nanoparticles with Multiple Morphologies Obtained from Nanoprecipitation of Amphiphilic Graft Copolymers in a Backbone-Selective Solvent.

    Science.gov (United States)

    Le Fer, Gaëlle; Le Cœur, Clémence; Guigner, Jean-Michel; Amiel, Catherine; Volet, Gisèle

    2017-03-21

    Stealth nanocarriers are a promising technology for the treatment of diseases. However, the preparation and characterization of well-defined soft nanoparticulate systems remain challenging. Here we describe a platform of amphiphilic graft copolymers leading to nanoparticles with multiple morphologies and the role of the hydrophilic backbone in their interaction with a model protein. The amphiphilic graft copolymers platform was composed of hydrophilic backbone poly(2-methyl-2-oxazoline-co-2-pentyl-2-oxazoline) (P(MeOx-co-PentOx)), prepared via cationic ring-opening polymerization. Hydrophobic poly(d,l-lactide) (PLA) chains were grafted on the backbone via Huisgen 1,3-dipolar cycloaddition. The "click" copper-catalyzed cycloaddition reactions of azides with alkynes (CuAAC) were successfully carried out, and a series of amphiphilic copolymers were prepared containing a backbone with a number-average molecular weight of 14.2 × 10 3 g mol -1 and different hydrophobic PLA grafts with various molecular weights (2.8 × 10 3 -12.4 × 10 3 g mol -1 ). These original architectures of copolymers, when nanoprecipitated in water, the backbone-selective solvent, allowed us to obtain various structures of nanoparticles with a hydrodynamic diameter in the range of 65-99 nm. More interestingly, a plurality of morphologies going from unilamellar, multilamellar, and large compound vesicles to core-shell nanoparticles and depending on the PLA molecular weights were evidenced by combining cryo-transmission electron microscopy (cryo-TEM) and small-angle neutron scattering (SANS) studies. A first evaluation of their stealthiness by studying the stability and the interaction of these nano-objects with a model protein revealed the role played by the P(MeOx-co-PentOx) in these interactions, demonstrating the utility of this amphiphilic graft copolymers platform with well-defined architectures for the design of nanocarriers in drug delivery applications.

  20. New amphiphilic glycopolypeptide conjugate capable of self-assembly in water into reduction-sensitive micelles for triggered drug release

    International Nuclear Information System (INIS)

    Yang, Hui-Kang; Zhang, Li-Ming

    2014-01-01

    For the development of biomimetic carriers for stimuli-sensitive delivery of anticancer drugs, a novel amphiphilic glycopolypeptide conjugate containing the disulfide bond was prepared for the first time by the ring-opening polymerization of benzyl glutamate N-carboxy anhydride in the presence of (propargyl carbamate)ethyl dithio ethylamine and then click conjugation with α-azido dextran. Its structure was characterized by Fourier-transform infrared spectroscopy and nuclear magnetic resonance analyses. Owing to its amphiphilic nature, such a conjugate could self assemble into nanosize micelles in aqueous medium, as confirmed by fluorometry, transmission electron microscopy and dynamic light scattering. For the resultant micelles, it was found to encapsulate poorly water-soluble anticancer drug (methotrexate, MTX) with the loading efficiency of 45.2%. By the in vitro drug release tests, the release rate of encapsulated MTX was observed to be accelerated significantly in the presence of 10 mM 1,4-dithio-DL-threitol (DTT), analogous to the intracellular redox potential. - Graphical abstract: New amphiphilic glycopolypeptide conjugate containing the disulfide bond could self-assemble in aqueous solution into reduction-sensitive micelles for triggered release of an anticancer drug (methotrexate, MTX) in the presence of 10 mM 1,4-dithio-DL-threitol (DTT). - Highlights: • Amphiphilic glycopolypeptide conjugate containing disulfide bond was prepared. • Such a conjugate self assembled in aqueous solution into nanosize micelles. • The resultant micelles could encapsulate effectively methotrexate drug. • The drug-loaded micelles showed a reduction-sensitive drug release behavior

  1. One-Pot Synthesis of (+)-Nootkatone via Dark Singlet Oxygenation of Valencene: The Triple Role of the Amphiphilic Molybdate Catalyst

    OpenAIRE

    Bing Hong; Raphaël Lebeuf; Stéphanie Delbaere; Paul L. Alsters; Véronique Nardello-Rataj

    2016-01-01

    Efficient one-pot catalytic synthesis of (+)-nootkatone was performed from (+)-valencene using only hydrogen peroxide and amphiphilic molybdate ions. The process required no solvent and proceeded in three cascade reactions: (i) singlet oxygenation of valencene according to the ene reaction; (ii) Schenck rearrangement of one hydroperoxide into the secondary β-hydroperoxide; and (iii) dehydration of the hydroperoxide into the desired (+)-nootkatone. The solvent effect on the hydroperoxide rearr...

  2. Self-Assembly of Amphiphilic Block Copolypeptoids with C 2 -C 5 Side Chains in Aqueous Solution

    KAUST Repository

    Fetsch, Corinna

    2014-12-22

    © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Nowadays, amphiphilic molecules play an important role in our life. In medical applications, amphiphilic block copolymers have attracted much attention as excipients in drug delivery systems. Here, the polymers are used as emulsifiers, micelles, or polymersomes with a hydrophilic corona block and a hydrophobic core or membrane. The aggregation behavior in aqueous solutions of a series of different amphiphilic block copolypeptoids comprising polysarcosine as a hydrophilic part is here reported. The formation of aggregates is investigated with 1H NMR spectroscopy and dynamic light scattering, and the determination of the critical micelle concentration (cmc) is performed using pyrene fluorescence spectroscopy. For the different block copolypeptoids cmc values ranging from 0.6 × 10-6 M to 0.1 × 10-3 M are found. The tendency to form micelles increases with increasing hydrophobicity at the nitrogen side chain in the hydrophobic moiety. Furthermore, in the case of the same hydrophobic side chain, a decreasing hydrophilic/lipophilic balance leads to the formation of larger aggregates. The aggregates formed in the buffer are able to solubilize the hydrophobic model compounds Reichardt\\'s dye and pyrene, and exhibit versatile microenvironments. Final investigations about the cytotoxicity reveal that the block copolypeptoids are well tolerated by mammalian cells up to high concentrations.

  3. Host-Guest Interaction between Corona[n]arene and Bisquaternary Ammonium Derivatives for Fabricating Supra-Amphiphile.

    Science.gov (United States)

    Zeng, Lingda; Guo, Qing-Hui; Feng, Yuanning; Xu, Jiang-Fei; Wei, Yuhan; Li, Zhibo; Wang, Mei-Xiang; Zhang, Xi

    2017-06-13

    The interactions between a host, water-soluble corona[n]arene (S6-CAP), and a series of guests, bisquaternary ammonium derivatives (CnDAs), in water, were investigated. The host and guest can form 1:1 host-guest complex. Their binding constants decrease as the alkyl length of CnDAs increases, which can be tunable ranging from 10 3 to 10 6 M -1 . The binding processes are mainly entropy-driven, while the enthalpy changes also play an important role in enhancing the host-guest interactions. In addition, a supra-amphiphile was fabricated with S6-CAP and a normal surfactant bearing bisquaternary ammonium (C4R). The S6-CAP·C4R complex forms micellar aggregates in water, and the system possesses better assembling activity and dilution stability than its building block C4R. This study enriches the families of supra-amphiphiles with a new architecture, and employing such a supra-amphiphile in biofunctional materials is highly anticipated.

  4. 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.

  5. Adsorption of poly(ethylene oxide)-containing amphiphilic polymers on solid-liquid interfaces: Fundamentals and applications.

    Science.gov (United States)

    Bodratti, Andrew M; Sarkar, Biswajit; Alexandridis, Paschalis

    2017-06-01

    The adsorption of amphiphilic molecules of varying size on solid-liquid interfaces modulates the properties of colloidal systems. Nonionic, poly(ethylene oxide) (PEO)-based amphiphilic molecules are particularly useful because of their graded hydrophobic-hydrophilic nature, which allows for adsorption on a wide array of solid surfaces. Their adsorption also results in other useful properties, such as responsiveness to external stimuli and solubilization of hydrophobic compounds. This review focuses on the adsorption properties of PEO-based amphiphiles, beginning with a discussion of fundamental concepts pertaining to the adsorption of macromolecules on solid-liquid interfaces, and more specifically the adsorption of PEO homopolymers. The main portion of the review highlights studies on factors affecting the adsorption and surface self-assembly of PEO-PPO-PEO block copolymers, where PPO is poly(propylene oxide). Block copolymers of this type are commercially available and of interest in several fields, due to their low toxicity and compatibility in aqueous systems. Examples of applications relevant to the interfacial behavior of PEO-PPO-PEO block copolymers are paints and coatings, detergents, filtration, and drug delivery. The methods discussed herein for manipulating the adsorption properties of PEO-PPO-PEO are emphasized for their ability to shed light on molecular interactions at interfaces. Knowledge of these interactions guides the formulation of novel materials with useful mesoscale organization and micro- and macrophase properties. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. 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.

  7. 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).

  8. Cationic, amphiphilic copolymer micelles as nucleic acid carriers for enhanced transfection in rat spinal cord.

    Science.gov (United States)

    Gwak, So-Jung; Nice, Justin; Zhang, Jeremy; Green, Benjamin; Macks, Christian; Bae, Sooneon; Webb, Ken; Lee, Jeoung Soo

    2016-04-15

    Spinal cord injury commonly leads to permanent motor and sensory deficits due to the limited regenerative capacity of the adult central nervous system (CNS). Nucleic acid-based therapy is a promising strategy to deliver bioactive molecules capable of promoting axonal regeneration. Branched polyethylenimine (bPEI: 25kDa) is one of the most widely studied nonviral vectors, but its clinical application has been limited due to its cytotoxicity and low transfection efficiency in the presence of serum proteins. In this study, we synthesized cationic amphiphilic copolymers, poly (lactide-co-glycolide)-graft-polyethylenimine (PgP), by grafting low molecular weight PLGA (4kDa) to bPEI (25kDa) at approximately a 3:1 ratio as an efficient nonviral vector. We show that PgP micelle is capable of efficiently transfecting plasmid DNA (pDNA) and siRNA in the presence of 10% serum in neuroglioma (C6) cells, neuroblastoma (B35) cells, and primary E8 chick forebrain neurons (CFN) with pDNA transfection efficiencies of 58.8%, 75.1%, and 8.1%, respectively. We also show that PgP provides high-level transgene expression in the rat spinal cord in vivo that is substantially greater than that attained with bPEI. The combination of improved transfection and reduced cytotoxicity in vitro in the presence of serum and in vivo transfection of neural cells relative to conventional bPEI suggests that PgP may be a promising nonviral vector for therapeutic nucleic acid delivery for neural regeneration. Gene therapy is a promising strategy to overcome barriers to axonal regeneration in the injured central nervous system. Branched polyethylenimine (bPEI: 25kDa) is one of the most widely studied nonviral vectors, but its clinical application has been limited due to cytotoxicity and low transfection efficiency in the presence of serum proteins. Here, we report cationic amphiphilic copolymers, poly (lactide-co-glycolide)-graft-polyethylenimine (PgP) that are capable of efficiently transfecting reporter

  9. Formation and Mechanism of Superhydrophobic/Hydrophobic Surfaces Made from Amphiphiles through Droplet-Mediated Evaporation-Induced Self-Assembly.

    Science.gov (United States)

    Dong, Fangyuan; Zhang, Mi; Tang, Wai-Wa; Wang, Yi

    2015-04-23

    Superhydrophobic/hydrophobic surfaces have attracted wide attention because of their broad applications in various regions, including coating, textile, packaging, electronic devices, and bioengineering. Many studies have been focused on the fabrication of superhydrophobic/hydrophobic surfaces using natural materials. In this paper, superhydrophobic/hydrophobic surfaces were formed by an amphiphilic natural protein, zein, using electrospinning. Water contact angle (WCA) and scanning electron microscopy (SEM) were used to characterize the hydrophobicity and surface morphology of the electrospun structures. The highest WCA of the zein electrospun surfaces could reach 155.5 ± 1.4°. To further understand the mechanism of superhydrophobic surface formation from amphiphiles using electrospinning, a synthetic amphiphilic polymer was selected, and also, a method similar to electrospinning, spray drying, was tried. The electrospun amphiphilic polymer surface showed a high hydrophobicity with a WCA of 141.4 ± 0.7°. WCA of the spray-dried zein surface could reach 125.3 ± 2.1°. The secondary structures of the zein in the electrospun film and cast-dried film were studied using ATR-FTIR, showing that α-helix to β-sheet transformation happened during the solvent evaporation in the cast drying process but not in the electrospinning process. A formation mechanism was proposed on the basis of the orientation of the amphiphiles during the solvent evaporation of different fabrication methods. The droplet-based or jet-based evaporation during electrospinning and spray drying led to the formation of the superhydrophobic/hydrophobic surface by the accumulation of the hydrophobic groups of the amphiphiles on the surface, while the surface-based evaporation during cast drying led to the formation of the hydrophilic surface by the accumulation of the hydrophilic groups of the amphiphiles on the surface.

  10. Amphiphilic Lipopeptide-Mediated Transport of Insulin and Cell Membrane Penetration Mechanism

    Directory of Open Access Journals (Sweden)

    Yu Zhang

    2015-12-01

    Full Text Available Arginine octamer (R8 and its derivatives were developed in this study for the enhanced mucosal permeation of insulin. R8 was substituted with different aminos, then modified with stearic acid (SA. We found that the SAR6EW-insulin complex had stronger intermolecular interactions and higher complex stability. The amphiphilic lipopeptide (SAR6EW was significantly more efficient for the permeation of insulin than R8 and R6EW both in vitro and in vivo. Interestingly, different cellular internalization mechanisms were observed for the complexes. When the effectiveness of the complexes in delivering insulin in vivo was examined, it was found that the SAR6EW-insulin complex provided a significant and sustained (six hours reduction in the blood glucose levels of diabetic rats. The improved absorption could be the comprehensive result of stronger intermolecular interactions, better enzymatic stability, altered internalization pathways, and increased transportation efficacy. In addition, no sign of toxicity was observed after consecutive administrations of SAR6EW. These results demonstrate that SAR6EW is a promising epithelium permeation enhancer for insulin and suggest that the chemical modification of cell-penetrating peptides is a feasible strategy to enhance their potential.

  11. In vitro evaluation of anticancer nanomedicines based on doxorubicin and amphiphilic Y-shaped copolymers

    Science.gov (United States)

    Li, Di; Ding, Jian Xun; Tang, Zhao Hui; Sun, Hai; Zhuang, Xiu Li; Xu, Jing Zhe; Chen, Xue Si

    2012-01-01

    Four monomethoxy poly(ethylene glycol)-poly(L-lactide-co-glycolide)2 (mPEG-P( LA-co-GA)2) copolymers were synthesized by ring-opening polymerization of L-lactide and glycolide with double hydroxyl functionalized mPEG (mPEG-(OH)2) as macroinitiator and stannous octoate as catalyst. The copolymers self-assembled into nanoscale micellar/vesicular aggregations in phosphate buffer at pH 7.4. Doxorubicin (DOX), an anthracycline anticancer drug, was loaded into the micellar/vesicular nanoparticles, yielding micellar/vesicular nanomedicines. The in vitro release behaviors could be adjusted by content of hydrophobic polyester and pH of the release medium. In vitro cell experiments showed that the intracellular DOX release could be adjusted by content of P(LA-co-GA), and the nanomedicines displayed effective proliferation inhibition against Henrietta Lacks’s cells with different culture times. Hemolysis tests indicated that the copolymers were hemocompatible, and the presence of copolymers could reduce the hemolysis ratio of DOX significantly. These results suggested that the novel anticancer nanomedicines based on DOX and amphiphilic Y-shaped copolymers were attractive candidates as tumor tissular and intracellular targeting drug delivery systems in vivo, with enhanced stability during circulation and accelerated drug release at the target sites. PMID:22701317

  12. Self-assembly of amphiphilic Janus dendrimers into mechanically robust supramolecular hydrogels for sustained drug release.

    Science.gov (United States)

    Nummelin, Sami; Liljeström, Ville; Saarikoski, Eve; Ropponen, Jarmo; Nykänen, Antti; Linko, Veikko; Seppälä, Jukka; Hirvonen, Jouni; Ikkala, Olli; Bimbo, Luis M; Kostiainen, Mauri A

    2015-10-05

    Compounds that can gelate aqueous solutions offer an intriguing toolbox to create functional hydrogel materials for biomedical applications. Amphiphilic Janus dendrimers with low molecular weights can readily form self-assembled fibers at very low mass proportion (0.2 wt %) to create supramolecular hydrogels (G'≫G'') with outstanding mechanical properties and storage modulus of G'>1000 Pa. The G' value and gel melting temperature can be tuned by modulating the position or number of hydrophobic alkyl chains in the dendrimer structure; thus enabling exquisite control over the mesoscale material properties in these molecular assemblies. The gels are formed within seconds by simple injection of ethanol-solvated dendrimers into an aqueous solution. Cryogenic TEM, small-angle X-ray scattering, and SEM were used to confirm the fibrous structure morphology of the gels. Furthermore, the gels can be efficiently loaded with different bioactive cargo, such as active enzymes, peptides, or small-molecule drugs, to be used for sustained release in drug delivery. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Amphiphilic PA-induced three-dimensional graphene macrostructure with enhanced removal of heavy metal ions.

    Science.gov (United States)

    Tan, Bing; Zhao, Huimin; Zhang, Yaobin; Quan, Xie; He, Zehao; Zheng, Wenting; Shi, Bingyu

    2018-02-15

    Phytic acid (PA) induced graphene macrostructures were synthesized and investigated for the sorption characteristics and mechanisms of mercury. The as-synthesized graphene foam possessed large specific surface area and amphiphilicity. FTIR and XPS analysis revealed that the as-prepared graphene macrostructure retained oxygen-containing functional groups after hydrothermal reduction and also captured new phosphorus-containing groups because of the introduction of PA. Different experimental parameters, such as pH, PA fractions and contact time were applied to probe into the Hg(II) adsorption performance of as-synthesized macrostructure. Pseudo-second-order kinetic model and Langmuir isotherm model fitted well to the obtained sorption kinetic and isothermal data. The maximum adsorption capacity at pH = 7.2 for mercury was 361.01 mg/g. The dominant mechanisms for mercury removal were mainly ion exchange and surface complexation. Real application in river water and seawater exhibited very promising results, indicating its broad prospect in water purification. Copyright © 2017 Elsevier Inc. All rights reserved.

  14. Amphiphilic nanoparticles suppress droplet break-up and increase serial droplet interrogation rate

    Science.gov (United States)

    Kim, Minkyu; Gai, Ya; Pan, Ming; Tang, Sindy K. Y.

    2017-11-01

    We describe the break-up behavior of a concentrated emulsion comprising drops stabilized by amphiphilic silica nanoparticles (`NPs') flowing in a tapered microchannel. Such channel geometry is commonly used in droplet serial interrogation and assay. We focus on concentrated emulsions as they often form after the droplet incubation. Unlike solid wells in their multi-well plate counterpart, drops are prone to interfacial instability. Droplet break-up ruins assay accuracy. The rate at which break-up occurs sets the limit for assay throughput. Previously, we have studied the break-up of surfactant-stabilized drops in a concentrated emulsion. The key motivation for replacing surfactants with NPs is that NPs can mitigate inter-drop transport of small molecules. Our results show replacing surfactant with NPs as droplet stabilizers has an additional advantage of reducing droplet break-up, thereby increasing the droplet interrogation rate. Such result can be attributed to the increased interfacial viscoelasticity. We examine the effect of channel confinement, viscosity ratio, and size of NPs on the break-up behavior of drops. We find the break-up is dependent on confinement and size of NPs, while insensitive to viscosity ratio within the tested range. Our results have immediate practical use in increasing the throughput limit of droplet-based applications such as serial assay and interrogation.

  15. Beta-cyclodextrin-centered star-shaped amphiphilic polymers for doxorubicin delivery.

    Science.gov (United States)

    Qiu, Li Yan; Wang, Rong Juan; Zheng, Cheng; Jin, Yi; Jin, Le Qun

    2010-02-01

    Delivery of doxorubicin could be achieved by a novel micellar system based on beta-cyclodextrin-centered star-shaped amphiphilic polymers (sPEL/CD). This study specifically explored the effect of polylactide segments in sPEL/CD on various micelle properties, such as the critical micelle concentration, size, drug loading, cytotoxicity and drug resistance reversing effect. The sPEL/CD was synthesized by the arm-first method. The critical micelle concentrations of polymeric micelles were determined by fluorescence spectrophotometry using pyrene as a probe. The oil/water method was applied to prepare doxorubicin-loaded micelles. 3-(4,5-dimethylthi-azol-2-yl)-2,5-diphenyltetrazolium bromide, confocal laser-scanning microscopy and flow cytometry were used to examine cell cytotoxicity and cellular uptake of the doxorubicin-loaded micelles. Finally, rhodamine-123 cellular uptake was determined to evaluate the polymer action on MCF-7 and MCF-7/ADR cells. All polymers exhibited low cytotoxicity and their micelles had a desirable release-acceleration pH (pH 5.0) for cytoplasmic drug delivery. With the introduction of polylactide into the polymer, the micelle critical micelle concentration can be effectively decreased and the drug-loading content was enhanced. Most importantly, the drug resistance of MCF-7/ADR cells was significantly reversed via the interaction between polymer and Pgp. Therefore, this type of polymer has potential superiority for cancer therapy.

  16. Cathepsin-Mediated Cleavage of Peptides from Peptide Amphiphiles Leads to Enhanced Intracellular Peptide Accumulation

    Energy Technology Data Exchange (ETDEWEB)

    Acar, Handan [Institute; Department; Samaeekia, Ravand [Institute; Department; Schnorenberg, Mathew R. [Institute; Department; Medical; Sasmal, Dibyendu K. [Institute; Huang, Jun [Institute; Tirrell, Matthew V. [Institute; Institute; LaBelle, James L. [Department

    2017-08-24

    Peptides synthesized in the likeness of their native interaction domain(s) are natural choices to target protein protein interactions (PPIs) due to their fidelity of orthostatic contact points between binding partners. Despite therapeutic promise, intracellular delivery of biofunctional peptides at concentrations necessary for efficacy remains a formidable challenge. Peptide amphiphiles (PAs) provide a facile method of intracellular delivery and stabilization of bioactive peptides. PAs consisting of biofunctional peptide headgroups linked to hydrophobic alkyl lipid-like tails prevent peptide hydrolysis and proteolysis in circulation, and PA monomers are internalized via endocytosis. However, endocytotic sequestration and steric hindrance from the lipid tail are two major mechanisms that limit PA efficacy to target intracellular PPIs. To address these problems, we have constructed a PA platform consisting of cathepsin-B cleavable PAs in which a selective p53-based inhibitory peptide is cleaved from its lipid tail within endosomes, allowing for intracellular peptide accumulation and extracellular recycling of the lipid moiety. We monitor for cleavage and follow individual PA components in real time using a resonance energy transfer (FRET)-based tracking system. Using this platform, components in real time using a Forster we provide a better understanding and quantification of cellular internalization, trafficking, and endosomal cleavage of PAs and of the ultimate fates of each component.

  17. Polypeptoids from N -Substituted Glycine N -Carboxyanhydrides: Hydrophilic, Hydrophobic, and Amphiphilic Polymers with Poisson Distribution

    KAUST Repository

    Fetsch, Corinna

    2011-09-13

    Preparation of defined and functional polymers has been one of the hottest topics in polymer science and drug delivery in the recent decade. Also, research on (bio)degradable polymers gains more and more interest, in particular at the interface of these two disciplines. However, in the majority of cases, combination of definition, functionality and degradability, is problematic. Here we present the preparation and characterization (MALDI-ToF MS, NMR, GPC) of nonionic hydrophilic, hydrophobic, and amphiphilic N-substituted polyglycines (polypeptoids), which are expected to be main-chain degradable and are able to disperse a hydrophobic model compound in aqueous media. Polymerization kinetics suggest that the polymerization is well controlled with strictly linear pseudo first-order kinetic plots to high monomer consumption. Moreover, molar mass distributions of products are Poisson-type and molar mass can be controlled by the monomer to initiator ratio. The presented polymer platform is nonionic, backbone degradable, and synthetically highly flexible and may therefore be valuable for a broad range of applications, in particular as a biomaterial. © 2011 American Chemical Society.

  18. Amphiphilic polymers formed from ring-opening polymerization: a strategy for the enhancement of gene delivery.

    Science.gov (United States)

    Zhang, Yi-Mei; Huang, Zheng; Zhang, Ji; Wu, Wan-Xia; Liu, Yan-Hong; Yu, Xiao-Qi

    2017-03-28

    Cationic liposomes and polymers are both important candidates for use as non-viral gene vectors. However, both of them have special shortcomings and application limits. This work is devoted to the combination of advantages of liposomes and polymers. The ring-opening polymerization strategy was used for the preparation of amphiphilic polymers from cyclen-based cationic small lipids. The non-hydrophobic polymer and the corresponding lipids were also prepared for performing structure-activity relationship studies. Gel electrophoresis results reveal that both the lipopolymers and liposomes could effectively condense DNA into nanoparticles and protect DNA from degradation. Compared to polymers, the DNA binding ability of liposomes is more affected by hydrophobic tails. Under the same dosage, the synthetic polymers have stronger DNA binding ability than the liposomes. In vitro transfection experiments show that the polymers could give better transfection efficiency, which was much higher than those of the corresponding liposomes and non-hydrophobic polymer. The oleyl moiety is suitable for lipidic vectors, but things were different for polymers. Under optimized conditions, up to 14.2 times higher transfection efficiency than that for 25 kDa bPEI could be obtained. More importantly, the lipopolymers showed much better serum tolerance, which was further confirmed by protein adsorption, gel electrophoresis, flow cytometry, and CLSM assays. The results indicate that ring-opening polymerization is a promising strategy for the enhancement of the gene delivery efficiency and biocompatibility of cationic lipids.

  19. Shear Alignment of Bola-Amphiphilic Arginine-Coated Peptide Nanotubes.

    Science.gov (United States)

    Hamley, Ian W; Burholt, Samuel; Hutchinson, Jessica; Castelletto, Valeria; da Silva, Emerson Rodrigo; Alves, Wendel; Gutfreund, Philipp; Porcar, Lionel; Dattani, Rajeev; Hermida-Merino, Daniel; Newby, Gemma; Reza, Mehedi; Ruokolainen, Janne; Stasiak, Joanna

    2017-01-09

    The bola-amphiphilic arginine-capped peptide RFL 4 RF self-assembles into nanotubes in aqueous solution. The nanostructure and rheology are probed by in situ simultaneous rheology/small-angle scattering experiments including rheo-SAXS, rheo-SANS, and rheo-GISANS (SAXS: small-angle X-ray scattering, SANS: small-angle neutron scattering, GISANS: grazing incidence small-angle neutron scattering). Nematic alignment of peptide nanotubes under shear is observed at sufficiently high shear rates under steady shear in either Couette or cone-and-plate geometry. The extent of alignment increases with shear rate. A shear plateau is observed in a flow curve measured in the Couette geometry, indicating the presence of shear banding above the shear rate at which significant orientation is observed (0.1-1 s -1 ). The orientation under shear is transient and is lost as soon as shear is stopped. GISANS shows that alignment at the surface of a cone-and-plate cell develops at sufficiently high shear rates, very similar to that observed in the bulk using the Couette geometry. A small isotope effect (comparing H 2 O/D 2 O solvents) is noted in the CD spectra indicating increased interpeptide hydrogen bonding in D 2 O, although this does not influence nanotube self-assembly. These results provide new insights into the controlled alignment of peptide nanotubes for future applications.

  20. Synthesis and bioactivities study of new antibacterial peptide mimics: The dialkyl cationic amphiphiles.

    Science.gov (United States)

    Zhang, En; Bai, Peng-Yan; Cui, De-Yun; Chu, Wen-Chao; Hua, Yong-Gang; Liu, Qin; Yin, Hai-Yang; Zhang, Yong-Jie; Qin, Shangshang; Liu, Hong-Min

    2018-01-01

    The emergence of infectious diseases caused by pathogenic bacteria is widespread. Therefore, it is urgently required to enhance the development of novel antimicrobial agents with high antibacterial activity and low cytotoxicity. A series of novel dialkyl cationic amphiphiles bearing two identical length lipophilic alkyl chains and one non-peptidic amide bond were synthesized and tested for antimicrobial activities against both Gram-positive and Gram-negative bacteria. Particular compounds synthesized showed excellent antibacterial activity toward drug-sensitive bacteria such as S. aureus, E. faecalis, E. coli and S. enterica, and clinical isolates of drug-resistant species such as methicillin-resistant S. aureus (MRSA), KPC-producing and NDM-1-producing carbapenem-resistant Enterobacteriaceae (CRE). For example, the MIC values of the best compound 4g ranged from 0.5 to 2 μg/mL against all these strains. Moreover, these small molecules acted rapidly as bactericidal agents, and functioned primarily by permeabilization and depolarization of bacterial membranes. Importantly, these compounds were difficult to induce bacterial resistance and can potentially combat drug-resistant bacteria. Thus, these compounds can be developed into a new class of antibacterial peptide mimics against Gram-positive and Gram-negative bacteria, including drug-resistant bacterial strains. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  1. Design and synthesis of short amphiphilic cationic peptidomimetics based on biphenyl backbone as antibacterial agents.

    Science.gov (United States)

    Kuppusamy, Rajesh; Yasir, Muhammad; Berry, Thomas; Cranfield, Charles G; Nizalapur, Shashidhar; Yee, Eugene; Kimyon, Onder; Taunk, Aditi; Ho, Kitty K K; Cornell, Bruce; Manefield, Mike; Willcox, Mark; Black, David StC; Kumar, Naresh

    2018-01-01

    Antimicrobial peptides (AMPs) and their synthetic mimics have received recent interest as new alternatives to traditional antibiotics in attempts to overcome the rise of antibiotic resistance in many microbes. AMPs are part of the natural defenses of most living organisms and they also have a unique mechanism of action against bacteria. Herein, a new series of short amphiphilic cationic peptidomimetics were synthesized by incorporating the 3'-amino-[1,1'-biphenyl]-3-carboxylic acid backbone to mimic the essential properties of natural AMPs. By altering hydrophobicity and charge, we identified the most potent analogue 25g that was active against both Gram-positive Staphylococcus aureus (MIC = 15.6 μM) and Gram-negative Escherichia coli (MIC = 7.8 μM) bacteria. Cytoplasmic permeability assay results revealed that 25g acts primarily by depolarization of lipids in cytoplasmic membranes. The active compounds were also investigated for their cytotoxicity to human cells, lysis of lipid bilayers using tethered bilayer lipid membranes (tBLMs) and their activity against established biofilms of S. aureus and E. coli. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  2. Aggregation of amphiphilic polymers in the presence of adhesive small colloidal particles.

    Science.gov (United States)

    Baulin, Vladimir A; Johner, Albert; Avalos, Josep Bonet

    2010-11-07

    The interaction of amphiphilic polymers with small colloids, capable to reversibly stick onto the chains, is studied. Adhesive small colloids in solution are able to dynamically bind two polymer segments. This association leads to topological changes in the polymer network configurations, such as looping and cross-linking, although the reversible adhesion permits the colloid to slide along the chain backbone. Previous analyses only consider static topologies in the chain network. We show that the sliding degree of freedom ensures the dominance of small loops, over other structures, giving rise to a new perspective in the analysis of the problem. The results are applied to the analysis of the equilibrium between colloidal particles and star polymers, as well as to block copolymer micelles. The results are relevant for the reversible adsorption of silica particles onto hydrophilic polymers, used in the process of formation of mesoporous materials of the type SBA or MCM, cross-linked cyclodextrin molecules threading on the polymers and forming the structures known as polyrotaxanes. Adhesion of colloids on the corona of the latter induce micellization and growth of larger micelles as the number of colloids increase, in agreement with experimental data.

  3. Fusion and fission of molecular assemblies of amphiphilic polypeptides generating small vesicles from nanotubes.

    Science.gov (United States)

    Watabe, Naoki; Joo Kim, Cheol; Kimura, Shunsaku

    2017-03-01

    Three amphiphilic block polypeptides, (sarcosine) m -b-(l- or d-Leu-Aib) n (L16, D16, D14), having different helical chain lengths or helicity are synthesized. A mixture of L16, D16, and D14 generates vesicles of diameters more than ca. 130 nm by injecting the ethanol solution into water and heating at 90°C for 1 h. On the other hand, when nanotubes composed of L16 and D14 having ca. 50 nm diameter are mixed with nanosheets composed of D16, smaller and homogeneous vesicles of ca. 60 nm diameter are obtained with the heat treatment. The time lapse TEM image analysis of the mixtures revealed some transient structures of nanotubes sticking a nanosheet or a vesicle at the open end of nanotubes. The precise size control of vesicles is therefore attainable by using nanotubes as a structural template regulating the size of vesicles near to the nanotube diameter upon the membrane fission processes. © 2016 Wiley Periodicals, Inc.

  4. Nanospheres and nanocapsules of amphiphilic copolymers constituted by methoxypolyethylene glycol cyanoacrylate and hexadecyl cyanoacrylate units

    Directory of Open Access Journals (Sweden)

    J. Puiggali

    2013-01-01

    Full Text Available Nanospheres and nanocapsules of an amphiphilic copolymer having methylated polyethylene glycol and hexadecyl lateral groups were prepared by the solvent displacement method and using confined impinging jet mixers. Degradation, thermal properties and crystalline structure were investigated. Interestingly, pegylated chains hydrolyzed through ester bond cleavage, whereas the more hydrophobic hexadecyl ester groups were resistant to degradation in aqueous media. The copolymer crystallized from the melt, giving rise to spherulites with a negative birefringence and domains corresponding to crystallization of the different lateral groups. Size distribution and morphology of nanoparticles were mainly evaluated by electron microscopy. Nanocapsules were characterized by a stable membrane with a thickness close to 5 nm that allowed efficient encapsulation of a triglyceride oil. Triclosan was selected as an example of a hydrophobic drug to be loaded in both nanospheres and nanocapsules. The release behavior of these dosage forms was clearly different. Thus, the Burst effect was practically suppressed when using nanocapsules; in addition, these showed a sustained, controlled release over a greater time period. Antimicrobial activity of triclosan loaded nanospheres and nanocapsules was evaluated using Gram-negative and Gram-positive bacteria. The former were highly sensitive to the released triclosan whereas the latter strongly depended on the number of particles in the culture medium.

  5. Preparation and Performance of Amphiphilic Random Copolymer Noncovalently Modified MWCNTs/Epoxy Composite

    Directory of Open Access Journals (Sweden)

    MA Qiang

    2016-09-01

    Full Text Available An amphiphilic random copolymer of polyglycidyl methacrylate-co-N-vinyl carbazole P(GMA-co-NVC was synthesized by free radical polymerization and was used to noncovalently modify multi-walled carbon nanotubes (MWCNTs. The obtained P(GMA-co-NVC/MWCNTs was mixed with epoxy resin and used to reinforce epoxy resin. Polymer modified carbon nanotubes/epoxy resin composites were prepared by a casting molding method. Tensile test, electrical resistivity test and differential scanning calorimeter(DSC analysis were used to study the effect of polymer modified carbon nanotubes on the mechanical, electrical, and thermal properties of epoxy resin. The results show that the epoxy composite reinforced with P(GMA-co-NVC/MWCNTs shows a remarkable enhancement in both tensile strength and elongation at break compared to either the pure epoxy or the pristine MWCNTs/epoxy composites. In addition, the electrical conductivity of epoxy is significantly improved and the volume resistivity decreases from 1014Ω·m to 106Ω·m with 0.25% mass fraction loading of P(GMA-co-NVC/MWCNTs. Moreover, glass transition temperature of the epoxy composite also increases from 144℃ to 149℃.

  6. A thermodynamic study of the amphiphilic phenothiazine drug thioridazine hydrochloride in water/ethanol solvent

    International Nuclear Information System (INIS)

    Cheema, Mohammad Arif; Barbosa, Silvia; Taboada, Pablo; Castro, Emilio; Siddiq, Mohammad; Mosquera, Victor

    2006-01-01

    The thermodynamic properties of aqueous solutions of the tricyclic antidepressant amphiphilic phenothiazine drug thioridazine hydrochloride in the temperature range 20-50 deg. C and in the presence of ethanol have been measured. The phenothiazine tranquillizing drugs have interesting association characteristics that derive from their rigid, tricyclic hydrophobic groups. Thioridazine hydrochloride is a drug used in treatment of mental illness that shows side effects. Therefore, it is interesting to study the change of its physico-chemical properties with temperature and with the surrounding environment to understand the action mechanism of the drug. Densities, conductivities, and surface tension were measured to obtain surface and bulk solution properties. Critical concentrations, cc, at different temperatures and in the presence of ethanol, and partition coefficients, K, have been calculated, the latter using an indirect method based in the pseudophase model with the help of apparent molar volume data. This method has the advantage that allows calculating the distribution coefficients at solubilizate concentrations below the saturation. Conductivity data show two critical concentrations. The second critical concentration is not clear by density data. The effect of the alcohol is to decrease the first critical concentration due to a decrease in headgroup repulsion. The molar apparent volumes at infinite dilution and in the aggregate in water and in presence of ethanol have been also obtained

  7. The Assembly of DNA Amphiphiles at Liquid Crystal-Aqueous Interface

    Directory of Open Access Journals (Sweden)

    Jingsheng Zhou

    2016-12-01

    Full Text Available In this article, we synthesized a type of DNA amphiphiles (called DNA-lipids and systematically studied its assembly behavior at the liquid crystal (LC—aqueous interface. It turned out that the pure DNA-lipids at various concentrations cannot trigger the optical transition of liquid crystals from planar anchoring to homeotropic anchoring at the liquid crystal—aqueous interface. The co-assembly of DNA-lipid and l-dilauroyl phosphatidylcholine (l-DLPC indicated that the DLPC assembled all over the LC-aqueous interface, and DNA-lipids prefer to couple with LC in certain areas, particularly in polarized and fluorescent image, forming micron sized net-like structures. The addition of DNA complementary to DNA-lipids forming double stranded DNA-lipids caused de-assembly of DNA-lipids from LC-aqueous interface, resulting in the disappearance of net-like structures, which can be visualized through polarized microscope. The optical changes combined with DNA unique designable property and specific interaction with wide range of target molecules, the DNA-lipids decorated LC-aqueous interface would provide a new platform for biological sensing and diagnosis.

  8. Efficient cytosolic delivery mediated by polymersomes facilely prepared from a degradable, amphiphilic, and amphoteric copolymer.

    Science.gov (United States)

    Huang, Zhonghui; Teng, Wei; Liu, Longshan; Wang, Lichun; Wang, Qinmei; Dong, Yugang

    2013-07-05

    To solve problems in polymersome preparation caused by liposolubility of copolymers and to improve the cytosolic delivery efficiency of polymersomes to drugs, a lipopolysaccharide-amine (LPSA) copolymer with amphotericity and amphiphilicity is developed. LPSA contains two hydrophilic oppositely charged blocks (anionic oxidized alginate (OA), cationic polyethyleneimine (PEI 1.8 k)) and one hydrophobic block (cholesteryl), where OA is the backbone and cholesteryl-grafted PEI is the side chain. The two hydrophilic blocks first guarantee that LPSA will dissolve in water, and then help polymersome formation via electrostatic interactions to generate water insoluble interpolyelectrolyte complexes, which supplement the hydrophobic part to reach the right hydrophilicity/hydrophobicity ratio, and thus realize a one-step self-assembly of polymersomes in water. Our results show LPSA nanopolymersomes (LNPs) have low cytotoxicity and degradability, and an excellent ability to enter cells. TEM observation demonstrates that LNPs are entrapped in endosomes after endocytosis, and are then released to cytosols because of their strong endosomal escape capacity. As an example of cytosolic delivery to bioactive molecules, pDNA is delivered in mesenchymal stem cells, and more than 95% of cells express a large target protein, indicating that LNPs have high cytosolic delivery efficiency. Our study provides a novel, easy, and universal method to design copolymers for the preparation of polymersomes as efficient cytosolic delivery nanocarriers.

  9. Aggregation behaviour of amphiphilic drug and bile salt mixtures at different compositions and temperatures

    International Nuclear Information System (INIS)

    Rub, Malik Abdul; Sheikh, Mohmad Shafi; Asiri, Abdullah M.; Azum, Naved; Khan, Anish; Khan, Aftab Aslam Parwaz; Khan, Sher Bahadar; Kabir-ud-Din

    2013-01-01

    Highlights: • Aggregation behavior of promethazine hydrochloride-bile salt mixtures has been investigated. • The negative β values indicate attractive interactions between the components. • For PMT/PMT-bile salt systems, ΔH m ∘ values change from negative to positive with temperature. • The ΔS m ∘ values are positive, their magnitude being more at T = 298.15 K and above. • The results have applicability in drug delivery. -- Abstract: The micellization and adsorption behaviour of the amphiphilic drug promethazine hydrochloride (PMT – a phenothiazine) and bile salts mixtures were analyzed at different compositions in pure and mixed states in aqueous solutions. By using regular solution theory (RST) and Rosen’s model different physicochemical properties such as critical micellar concentration (cmc), micellar composition, surface excess concentration (Γ max ), minimum area per molecule (A min ), interaction parameters (β m , β σ ), energetic parameters of micellization as well as other micellar and surface properties have been determined. The values of interaction parameters (β) and activity coefficients f 1 and f 2 (for both, in mixed monolayer as well as in mixed micelles) indicate the synergistic behaviour. The thermodynamic parameters propose release of water from the hydrophobic portion of the drug at higher temperatures

  10. Synthesis of Amphiphilic Hyperbranched AIE-active Fluorescent Organic Nanoparticles and Their Application in Biological Application.

    Science.gov (United States)

    Lv, Qiulan; Wang, Ke; Xu, Dazhuang; Liu, Meiying; Wan, Qing; Huang, Hongye; Liang, Shangdong; Zhang, Xiaoyong; Wei, Yen

    2016-02-01

    Aggregation-induced emission (AIE) dyes have recently attracted much attention for biomedical applications for their remarkable AIE properties. However, the hydrophobic nature of AIE dyes made them difficult to be dispersed in physiological solution and problematic for biomedical application directly. Great efforts have been made to overcome this problem, and different strategies for preparation of water dispersible AIE based nanoprobes had been explored previously. However, a facile and effective strategy is still highly desirable and of great importance for the biomedical applications of AIE dye based on nanoprobes. In this work, the fabrication of amphiphilic hyperbranched fluorescent organic nanoparticles with a core-shell structure based on an AIE dye [tetraphenylethene acrylate (TPE-O-E)] and a hyperbranched polyamino compound [polyethylene imine (PEI)] through Michael addition reaction is described for the first time. The AIE dye as well as the final product PEI-TPE-O-E was characterized in detail by a number of techniques. To test their biomedical application potential, the cell viability as well as cell imaging properties of the PEI-TPE-O-E was also examined. The results showed that the PEI-TPE-O-E organic nanoparticles presented high water dispersiblity, ultrabright fluroerescence, low cytotoxicity and excellent biocompatibility, making them promising for biological imaging and gene delivery applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Design amphiphilic dipolar π-systems for stimuli-responsive luminescent materials using metastable states.

    Science.gov (United States)

    Yagai, Shiki; Okamura, Satoru; Nakano, Yujiro; Yamauchi, Mitsuaki; Kishikawa, Keiki; Karatsu, Takashi; Kitamura, Akihide; Ueno, Akira; Kuzuhara, Daiki; Yamada, Hiroko; Seki, Tomohiro; Ito, Hajime

    2014-06-05

    π-Conjugated compounds that exhibit tunable luminescence in the solid state under external mechanical stimuli have potential applications in sensors and imaging devices. However, no rational designs have been proposed that impart these mechano-responsive luminescent properties to π-conjugated compounds. Here we demonstrate a strategy for mechano-responsive luminescent materials by imparting amphiphilic and dipolar characteristics to a luminescent π-conjugated system. The oligo(p-phenylenevinylene) luminophore with a didodecylamino group at one end and a tri(ethylene glycol) ester group at the other end yields segregated solid structures by separately aggregating its hydrophobic and hydrophilic moieties. The segregated structures force the molecules to align in the same direction, thereby generating a conflict between the side-chain aggregation and dipolar stabilization of the π-system. Consequently, these metastable solid structures can be transformed through mechanical stimulation to a more stable structure, from a π-π stacked aggregate to a liquid crystal and further to a crystalline phase with variable luminescence.

  12. A thermodynamic study of the amphiphilic phenothiazine drug thioridazine hydrochloride in water/ethanol solvent

    Energy Technology Data Exchange (ETDEWEB)

    Cheema, Mohammad Arif [Laboratorio de Fisica de Coloides y Polimeros, Grupo de Sistemas Complejos, Departamento de Fisica de la Materia Condensada, Facultad de Fisica, Universidad de Santiago de Compostela, E-15782, Santiago de Compostela (Spain); Department of Chemistry, Quaid-i-Azam University, Islamabad 45320 (Pakistan); Barbosa, Silvia [Laboratorio de Fisica de Coloides y Polimeros, Grupo de Sistemas Complejos, Departamento de Fisica de la Materia Condensada, Facultad de Fisica, Universidad de Santiago de Compostela, E-15782, Santiago de Compostela (Spain)], E-mail: fmsilvia@usc.es; Taboada, Pablo [Laboratorio de Fisica de Coloides y Polimeros, Grupo de Sistemas Complejos, Departamento de Fisica de la Materia Condensada, Facultad de Fisica, Universidad de Santiago de Compostela, E-15782, Santiago de Compostela (Spain); Castro, Emilio [Laboratorio de Fisica de Coloides y Polimeros, Grupo de Sistemas Complejos, Departamento de Fisica de la Materia Condensada, Facultad de Fisica, Universidad de Santiago de Compostela, E-15782, Santiago de Compostela (Spain); Siddiq, Mohammad [Department of Chemistry, Quaid-i-Azam University, Islamabad 45320 (Pakistan); Mosquera, Victor [Laboratorio de Fisica de Coloides y Polimeros, Grupo de Sistemas Complejos, Departamento de Fisica de la Materia Condensada, Facultad de Fisica, Universidad de Santiago de Compostela, E-15782, Santiago de Compostela (Spain)], E-mail: fmvictor@usc.es

    2006-09-29

    The thermodynamic properties of aqueous solutions of the tricyclic antidepressant amphiphilic phenothiazine drug thioridazine hydrochloride in the temperature range 20-50 deg. C and in the presence of ethanol have been measured. The phenothiazine tranquillizing drugs have interesting association characteristics that derive from their rigid, tricyclic hydrophobic groups. Thioridazine hydrochloride is a drug used in treatment of mental illness that shows side effects. Therefore, it is interesting to study the change of its physico-chemical properties with temperature and with the surrounding environment to understand the action mechanism of the drug. Densities, conductivities, and surface tension were measured to obtain surface and bulk solution properties. Critical concentrations, cc, at different temperatures and in the presence of ethanol, and partition coefficients, K, have been calculated, the latter using an indirect method based in the pseudophase model with the help of apparent molar volume data. This method has the advantage that allows calculating the distribution coefficients at solubilizate concentrations below the saturation. Conductivity data show two critical concentrations. The second critical concentration is not clear by density data. The effect of the alcohol is to decrease the first critical concentration due to a decrease in headgroup repulsion. The molar apparent volumes at infinite dilution and in the aggregate in water and in presence of ethanol have been also obtained.

  13. Bio-fabrication and physiological self-release of tissue equivalents using smart peptide amphiphile templates.

    Science.gov (United States)

    Gouveia, Ricardo M; Hamley, Ian W; Connon, Che J

    2015-10-01

    In this study we applied a smart biomaterial formed from a self-assembling, multi-functional synthetic peptide amphiphile (PA) to coat substrates with various surface chemistries. The combination of PA coating and alignment-inducing functionalised substrates provided a template to instruct human corneal stromal fibroblasts to adhere, become aligned and then bio-fabricate a highly-ordered, multi-layered, three-dimensional tissue by depositing an aligned, native-like extracellular matrix. The newly-formed corneal tissue equivalent was subsequently able to eliminate the adhesive properties of the template and govern its own complete release via the action of endogenous proteases. Tissues recovered through this method were structurally stable, easily handled, and carrier-free. Furthermore, topographical and mechanical analysis by atomic force microscopy showed that tissue equivalents formed on the alignment-inducing PA template had highly-ordered, compact collagen deposition, with a two-fold higher elastic modulus compared to the less compact tissues produced on the non-alignment template, the PA-coated glass. We suggest that this technology represents a new paradigm in tissue engineering and regenerative medicine, whereby all processes for the bio-fabrication and subsequent self-release of natural, bio-prosthetic human tissues depend solely on simple template-tissue feedback interactions.

  14. Long circulating micelles of an amphiphilic random copolymer bearing cell outer membrane phosphorylcholine zwitterions.

    Science.gov (United States)

    Zhao, Jing; Chai, Yu-Dong; Zhang, Jing; Huang, Peng-Fei; Nakashima, Kenichi; Gong, Yong-Kuan

    2015-04-01

    Polymeric micelles with cell outer membrane mimetic structure were prepared in water from amphiphilic random copolymers bearing both the hydrophilic phosphorylcholine zwitterions and hydrophobic octadecyl side chains of cell outer membrane. The polymeric micelles showed sizes ranging from 80 nm to 120 nm in hydrodynamic diameter and zeta-potentials from -6.4 mV to -2.4 mV by dynamic light scattering measurements. The micelles loaded with 6-coumarin as a fluorescence probe were stable to investigate their blood circulation and biodistribution. The in vitro phagocytosis results using murine peritoneal macrophages showed 10-fold reduction compared with a reference micelle. The in vivo blood circulation half-life of the polymeric micelles following intravenous administration in New Zealand Rabbits was increased from 0.55 h to 90.5h. More interestingly, tissue distribution results showed that the concentration of the micelles in the kidney is 4-fold higher than that in the liver and other organs 48 h after administration. The results of this work show great promise for designing more effective stealth drug carriers that can minimize reticuloendothelial system clearance and circulate for long time to reach target by using simple cell membrane mimetic random copolymer micelles. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  15. Radiation-induced graft polymerization of amphiphilic monomers with different polymerization characteristics onto hydrophobic polysilane

    Energy Technology Data Exchange (ETDEWEB)

    Tanaka, Hidenori; Iwasaki, Isao; Kunai, Yuichiro [Research Reactor Institute, Kyoto University, Asashironishi 2-1010, Kumatori-cho, Sennan-gun, Osaka 590-0494 (Japan); Sato, Nobuhiro, E-mail: sato-n@rri.kyoto-u.ac.j [Research Reactor Institute, Kyoto University, Asashironishi 2-1010, Kumatori-cho, Sennan-gun, Osaka 590-0494 (Japan); Matsuyama, Tomochika [Research Reactor Institute, Kyoto University, Asashironishi 2-1010, Kumatori-cho, Sennan-gun, Osaka 590-0494 (Japan)

    2011-08-15

    The structures of poly(methyl-n-propylsilane) (PMPrS) amphiphilically modified through {gamma}-ray-induced graft polymerization were investigated with {sup 1}H NMR measurement. By the use of methyl methacrylate (MMA) or diethyl fumarate (DEF) as monomers for the graft polymerization, grafting yield rose with increasing total absorption dose and monomer concentrations, but decreased with increasing dose rate. This result means that grafting yield of modified PMPrS can be controlled by changing irradiation conditions. However, the number of PMMA or PDEF graft chains per PMPrS chain was estimated to be less than 1.0 by analysis of {sup 1}H NMR spectra, and this value was lower than that we had expected. To improve graft density, maleic anhydride (MAH), which is known as a non-homopolymerizable monomer in radical polymerization, was used as a monomer for grafting. As a result, high density grafting (one MAH unit for 4.2 silicon atoms) was attained. It demonstrates that the structure of {gamma}-ray-modified polysilane strongly depends on the polymerization characteristics of grafted monomers.

  16. 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.

  17. Design and optimization of novel paclitaxel-loaded folate-conjugated amphiphilic cyclodextrin nanoparticles.

    Science.gov (United States)

    Erdoğar, Nazlı; Esendağlı, Güneş; Nielsen, Thorbjorn T; Şen, Murat; Öner, Levent; Bilensoy, Erem

    2016-07-25

    As nanomedicines are gaining momentum in the therapy of cancer, new biomaterials emerge as alternative platforms for the delivery of anticancer drugs with bioavailability problems. In this study, two novel amphiphilic cyclodextrins (FCD-1 and FCD-2) conjugated with folate group to enable active targeting to folate positive breast tumors were introduced. The objective of this study was to develop and characterize new folated-CD nanoparticles via 3(2) factorial design for optimal final parameters. Full physicochemical characterization studies were performed. Blank and paclitaxel loaded FCD-1 and FCD-2 nanoparticles remained within the range of 70-275nm and 125-185nm, respectively. Zeta potential values were neutral and -20mV for FCD-1 and FCD-2 nanoparticles, respectively. Drug release studies showed initial burst release followed by a longer sustained release. Blank nanoparticles had no cytotoxicity against L929 cells. T-47D and ZR-75-1 human breast cancer cells with different levels of folate receptor expression were used to assess anti-cancer efficacy. Through targeting the folate receptor, these nanoparticles were efficiently engulfed by the breast cancer cells. Additionally, breast cancer cells became more sensitive to cytotoxic and/or cytostatic effects of PCX delivered by FCD-1 and FCD-2. In conclusion, these novel folate-conjugated cyclodextrin nanoparticles can therefore be considered as promising alternative systems for safe and effective delivery of paclitaxel with a folate-dependent mechanism. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. Synthesis and characterization of an amphiphilic cyclodextrin, a micelle with two recognition sites.

    Science.gov (United States)

    Silva, O Fernando; Fernández, Mariana A; Pennie, Sarah L; Gil, Roberto R; de Rossi, Rita H

    2008-04-15

    A cyclodextrin derivative (Mod-CD) was synthesized through the monoesterification of beta-cyclodextrin (beta-CD) with 3-((E)-dec-2-enyl)-dihydrofuran-2,5-dione. The compound is an interesting surfactant that can form large aggregates not only through the interaction of the hydrophobic tails as in common amphiphilic compounds but also through the inclusion of the alkenyl chain into the cavity of another Mod-CD molecule. The self-inclusion of the chain in the cavity of cyclodextrin as well as the intermolecular inclusion was demonstrated by 1H NMR measurements that were able to detect methyl groups in three different environments. Besides, in the aggregates of Mod-CD, the cavity is available to interact with external guests such as phenolphthalein, 1-amino adamantane, and Prodan. Phenolphthalein has the same binding constant with Mod-CD and beta-CD, but the equilibrium constant for the interaction with Prodan is about 2 times larger for Mod-CD than for beta-CD. The latter result is attributed to the fact that this probe interacts with the micelle in two binding sites: the cavity of the cyclodextrin and the apolar heart of the micelle as evidenced by the spectrofluorimetric behavior of Prodan in solutions containing different concentrations of Mod-CD.

  19. Amphiphilic ligand exchange reaction-induced supercapacitor electrodes with high volumetric and scalable areal capacitances

    Science.gov (United States)

    Nam, Donghyeon; Heo, Yeongbeom; Cheong, Sanghyuk; Ko, Yongmin; Cho, Jinhan

    2018-05-01

    We introduce high-performance supercapacitor electrodes with ternary components prepared from consecutive amphiphilic ligand-exchange-based layer-by-layer (LbL) assembly among amine-functionalized multi-walled carbon nanotubes (NH2-MWCNTs) in alcohol, oleic acid-stabilized Fe3O4 nanoparticles (OA-Fe3O4 NPs) in toluene, and semiconducting polymers (PEDOT:PSS) in water. The periodic insertion of semiconducting polymers within the (OA-Fe3O4 NP/NH2-MWCNT)n multilayer-coated indium tin oxide (ITO) electrode enhanced the volumetric and areal capacitances up to 408 ± 4 F cm-3 and 8.79 ± 0.06 mF cm-2 at 5 mV s-1, respectively, allowing excellent cycling stability (98.8% of the initial capacitance after 5000 cycles) and good rate capability. These values were higher than those of the OA-Fe3O4 NP/NH2-MWCNT multilayered electrode without semiconducting polymer linkers (volumetric capacitance ∼241 ± 4 F cm-3 and areal capacitance ∼1.95 ± 0.03 mF cm-2) at the same scan rate. Furthermore, when the asymmetric supercapacitor cells (ASCs) were prepared using OA-Fe3O4 NP- and OA-MnO NP-based ternary component electrodes, they displayed high volumetric energy (0.36 mW h cm-3) and power densities (820 mW cm-3).

  20. Promoting siRNA delivery via enhanced cellular uptake using an arginine-decorated amphiphilic dendrimer

    Science.gov (United States)

    Liu, Xiaoxuan; Liu, Cheng; Zhou, Jiehua; Chen, Chao; Qu, Fanqi; Rossi, John J.; Rocchi, Palma; Peng, Ling

    2015-02-01

    RNA interference (RNAi) with small interfering RNA (siRNA) is expected to offer an attractive means to specifically and efficiently silence disease-associated genes for treating various diseases provided that safe and efficient delivery systems are available. In this study, we have established an arginine-decorated amphiphilic dendrimer composed of a hydrophobic alkyl chain and a hydrophilic PAMAM dendron bearing arginine terminals as nonviral vector for siRNA delivery. Indeed, this dendrimer proved to be very effective at delivering siRNAs in human prostate cancer PC-3 cells and in human hematopoietic CD34+ stem cells, leading to improved gene silencing compared to the corresponding nonarginine decorated dendrimer. Further investigation confirmed that this dendrimer was granted with the capacity to form stable nanoparticles with siRNA and significantly enhance cellular uptake of siRNA. In addition, this dendrimer revealed no discernible cytotoxicity. All these findings demonstrate that decoration of the dendrimer surface with arginine residues is indeed a useful strategy to improve the delivery ability of dendrimers.

  1. Interface interaction within nanopores in thin films of an amphiphilic block copolymer and CTAB.

    Science.gov (United States)

    Wang, Chengyin; Wang, Deyan; Hu, Xiaoya; Wang, Guoxiu

    2011-02-01

    With water droplets as sacrificed templates at a particular humidity, micro-porous solid thin films were successfully fabricated by self-assembly using an amphiphilic block polymer, polystyrene-b-polyacrylic acid (PS-b-PAA). Interface interactions between the micro-porous thin film and a cationic surfactant, cetyltrimethylammonium bromide (CTAB), are investigated by in-situ AFM in aqueous solutions. An interesting phenomenon was observed in water and CTAB solution, which the dimensions of the micropores are remarkably larger than the dimensions of those in air. The solid thin films exhibit different surface morphologies in response to stimulus by different concentrations of CTAB. These observations were explained by positing that the PAA chains in the micropores stretch and contract with interface interactions between PAA and CTAB. A promising electrochemical application of this film is suggested. This study is aimed at strategies for the functionalization of stimulus-responsive micro-porous solid thin films with tunable surface morphologies, and exploring new smart materials. Copyright © 2010 Elsevier Inc. All rights reserved.

  2. Luminescent Langmuir-Blodgett film of a new amphiphilic Eu3+ β-diketonate

    International Nuclear Information System (INIS)

    Gomes, Luciano F.; Oliveira, Kleber T. de; Neri, Claudio R.; Sousa Filho, Paulo C. de; Bianco, Marcos J. dal; Ramos, Ana P.; Zaniquelli, Maria E.D.; Serra, Osvaldo A.

    2008-01-01

    This work reports on the synthesis and characterization of the ligand 3-hexadecylpentane-2,4-dione (Hhdacac) and its Eu 3+ complexes Eu(hdacac) 6 .2H 2 O, Eu(hdacac) 6 .phen and Eu(hdacac) 6 .tta, where phen and tta denote 1,10-phenanthroline and thenoyltrifluoroacetone, respectively. These new compounds present long carbon chains and their expected miscibility into non-polar ambients is confirmed by the emission spectra of Eu(hdacac) 6 .tta in hexane. Moreover, the amphiphilic properties of Eu(hdacac) 6 complexes allow the obtainment of thin luminescent films by the Langmuir-Blodgett technique. In both cases (solids and films), the typical antenna effect of β-diketonates is observed. The alluring characteristics of these compounds raise great interest in many fields of Materials Science, like photo- and electro-luminescent materials (mainly thin 'organic' films), metal catalysts or probes in non-polar solutions, and Langmuir-Blodgett films of several compositions. For the characterization of these products, nuclear magnetic resonance spectroscopy ( 1 H NMR), thermogravimetric analysis, elementary analyses (C, H), scanning electron microscopy (energy dispersive X-ray spectroscopy), absorption (UV-vis/FT-IR) and photoluminescence spectroscopies were used

  3. Searching for low percolation thresholds within amphiphilic polymer membranes: The effect of side chain branching

    Science.gov (United States)

    Dorenbos, G.

    2015-06-01

    Percolation thresholds for solvent diffusion within hydrated model polymeric membranes are derived from dissipative particle dynamics in combination with Monte Carlo (MC) tracer diffusion calculations. The polymer backbones are composed of hydrophobic A beads to which at regular intervals Y-shaped side chains are attached. Each side chain is composed of eight A beads and contains two identical branches that are each terminated with a pendant hydrophilic C bead. Four types of side chains are considered for which the two branches (each represented as [C], [AC], [AAC], or [AAAC]) are splitting off from the 8th, 6th, 4th, or 2nd A bead, respectively. Water diffusion through the phase separated water containing pore networks is deduced from MC tracer diffusion calculations. The percolation threshold for the architectures containing the [C] and [AC] branches is at a water volume fraction of ˜0.07 and 0.08, respectively. These are much lower than those derived earlier for linear architectures of various side chain length and side chain distributions. Control of side chain architecture is thus a very interesting design parameter to decrease the percolation threshold for solvent and proton transports within flexible amphiphilic polymer membranes.

  4. Self-assembling of poly(ε-caprolactone)-b-poly(ethylene oxide) diblock copolymers in aqueous solution and at the silica-water interface

    International Nuclear Information System (INIS)

    Leyh, B.; Vangeyte, P.; Heinrich, M.; Auvray, L.; De Clercq, C.; Jerome, R.

    2004-01-01

    Small-angle neutron scattering is used to investigate the self-assembling behaviour of poly(ε-caprolactone)-b-poly(ethylene oxide) diblock copolymers with various block lengths (i) in aqueous solution, (ii) in aqueous solution with the addition of sodium dodecyl sulphate (SDS) and (iii) at the silica-water interface. Micelles are observed under our experimental conditions due to the very small critical micellar concentration of these copolymers (0.01 g/l). The poly(ε-caprolactone) core is surrounded by a poly(ethylene oxide) corona. The micellar form factors have been measured at low copolymer concentrations (0.2 wt%) under selected contrast matching conditions. The data have been fitted to various analytical models to extract the micellar core and corona sizes. SDS is shown to induce partial micelle disruption together with an increase of the poly(ethylene oxide) corona extension from 25% (without SDS) to 70% (with SDS) of a completely extended PEO 114 chain. Our data at the silica-water interface are compatible with the adsorption of micelles

  5. Acetal-Linked Paclitaxel Polymeric Prodrug Based on Functionalized mPEG-PCL Diblock Polymer for pH-Triggered Drug Delivery

    Directory of Open Access Journals (Sweden)

    Yinglei Zhai

    2017-12-01

    Full Text Available The differences in micro-environment between cancer cells and the normal ones offer the possibility to develop stimuli-responsive drug-delivery systems for overcoming the drawbacks in the clinical use of anticancer drugs, such as paclitaxel, doxorubicin, and etc. Hence, we developed a novel endosomal pH-sensitive paclitaxel (PTX prodrug micelles based on functionalized poly(ethylene glycol-poly(ε-caprolactone (mPEG-PCL diblock polymer with an acid-cleavable acetal (Ace linkage (mPEG-PCL-Ace-PTX. The mPEG-PCL-Ace-PTX5 with a high drug content of 23.5 wt % was self-assembled in phosphate buffer (pH 7.4, 10 mM into nanosized micelles with an average diameter of 68.5 nm. The in vitro release studies demonstrated that mPEG-PCL-Ace-PTX5 micelles was highly pH-sensitive, in which 16.8%, 32.8%, and 48.2% of parent free PTX was released from mPEG-PCL-Ace-PTX5 micelles in 48 h at pH 7.4, 6.0, and 5.0, respectively. Thiazolyl Blue Tetrazolium Bromide (MTT assays suggested that the pH-sensitive PTX prodrug micelles displayed higher therapeutic efficacy against MCF-7 cells compared with free PTX. Therefore, the PTX prodrug micelles with acetal bond may offer a promising strategy for cancer therapy.

  6. Barriers to defect melting in chemo-epitaxial directed self-assembly of lamellar-forming diblock copolymer/homopolymer blends

    Science.gov (United States)

    Izumi, Kenichi; Kim, Bongkeun; Laachi, Nabil; Delaney, Kris T.; Carilli, Michael; Fredrickson, Glenn H.

    2015-03-01

    We investigate energy barriers and minimum energy paths (MEPs) for transitions from dislocation-pair defects to perfect lamellae in self-assembly of AB-diblock copolymer plus A- or B-homopolymer blends using self-consistent field theory (SCFT) and the numerical string method. For neutral substrates, all minimum energy paths discovered by the string method show two successive energy barriers. The two-barrier qualitative nature of the MEPs appears not to depend on the presence or absence of small amounts of homopolymer. For the first energy barrier, the barrier height shows pronounced increase with addition of A-homopolymer due to localization of A-homopolymer on the T-junction core of the dislocation. For chemo-epitaxially patterned substrates (stripes of A-attractive substrate alternating with neutral substrate), the presence of A-attractive stripes helps draw the system towards a perfect lamellar configuration, and energy barriers along the MEP are reduced, in some cases disappearing entirely. Our findings provide guidance on how the presence of homopolymer and chemo-epitaxial prepatterns affect the stability of defective morphologies.

  7. 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.

  8. Nanopatterning via Self-Assembly of a Lamellar-Forming Polystyrene-block-Poly(dimethylsiloxane Diblock Copolymer on Topographical Substrates Fabricated by Nanoimprint Lithography

    Directory of Open Access Journals (Sweden)

    Dipu Borah

    2018-01-01

    Full Text Available The self-assembly of a lamellar-forming polystyrene-block-poly(dimethylsiloxane (PS-b-PDMS diblock copolymer (DBCP was studied herein for surface nanopatterning. The DBCP was synthesized by sequential living anionic polymerization of styrene and hexamethylcyclotrisiloxane (D3. The number average molecular weight (Mn, polydispersity index (Mw/Mn and PS volume fraction (φps of the DBCP were MnPS = 23.0 kg mol−1, MnPDMS = 15.0 kg mol−1, Mw/Mn = 1.06 and φps = 0.6. Thin films of the DBCP were cast and solvent annealed on topographically patterned polyhedral oligomeric silsesquioxane (POSS substrates. The lamellae repeat distance or pitch (λL and the width of the PDMS features (dL are ~35 nm and ~17 nm, respectively, as determined by SEM. The chemistry of the POSS substrates was tuned, and the effects on the self-assembly of the DBCP noted. The PDMS nanopatterns were used as etching mask in order to transfer the DBCP pattern to underlying silicon substrate by a complex plasma etch process yielding sub-15 nm silicon features.

  9. Exclusive Stereocomplex Crystallization of Linear and Multiarm Star-Shaped High-Molecular-Weight Stereo Diblock Poly(lactic acid)s.

    Science.gov (United States)

    Han, Lili; Shan, Guorong; Bao, Yongzhong; Pan, Pengju

    2015-11-05

    Linear, 3-arm, and 6-arm star-shaped stereo diblock copolymers of l- and d-lactic acid (PLLA-b-PDLA) with high molecular weights (MWs) were synthesized via two-step ring-opening polymerization (ROP) with 1-dodechanol, glycerol, and d-sorbitol as the initiators, respectively. The chemical structure, nonisothermal and isothermal crystallization kinetics, crystalline structure, lamellar morphology, and mechanical thermal properties of PLLA-b-PDLAs with different macromolecular topologies were investigated. Compared to the high-molecular-weight (MW) poly(l-lactic acid)/poly(d-lactic acid) (PLLA/PDLA) racemic blends, PLLA-b-PDLAs exhibit faster crystallization upon cooling and isothermal melt crystallization; they crystallize exclusively in stereocomplex (sc) crystallites under all of the conditions investigated. This is attributable to the enhanced interactions between enantiomeric blocks linked covalently. Macromolecular topology influences the crystallization kinetics and crystalline structure of PLLA-b-PDLAs significantly. The crystallization temperature upon cooling, melting temperature, degree of crystallinity, spherulitic growth rate, crystallite size, long period, and crystalline layer thickness of PLLA-b-PDLA decrease with increasing branching number because of the retarding effect of branching on the crystallization rate and crystallizability. Because of the formation of high-melting-point sc crystallites, both the linear and star-shaped PLLA-b-PDLAs exhibit better thermal resistance and higher storage moduli at high temperature than does homocrystalline PLLA.

  10. Exploring Poly(ethylene glycol-Polyzwitterion Diblock Copolymers as Biocompatible Smart Macrosurfactants Featuring UCST-Phase Behavior in Normal Saline Solution

    Directory of Open Access Journals (Sweden)

    Noverra M. Nizardo

    2018-03-01

    Full Text Available Nonionic-zwitterionic diblock copolymers are designed to feature a coil-to-globule collapse transition with an upper critical solution temperature (UCST in aqueous media, including physiological saline solution. The block copolymers that combine presumably highly biocompatible blocks are synthesized by chain extension of a poly(ethylene glycol (PEG macroinitiator via atom transfer radical polymerization (ATRP of sulfobetaine and sulfabetaine methacrylates. Their thermoresponsive behavior is studied by variable temperature turbidimetry and 1H NMR spectroscopy. While the polymers with polysulfobetaine blocks exhibit phase transitions in the physiologically interesting window of 30–50 °C only in pure aqueous solution, the polymers bearing polysulfabetaine blocks enabled phase transitions only in physiological saline solution. By copolymerizing a pair of structurally closely related sulfo- and sulfabetaine monomers, thermoresponsive behavior can be implemented in aqueous solutions of both low and high salinity. Surprisingly, the presence of the PEG blocks can affect the UCST-transitions of the polyzwitterions notably. In specific cases, this results in “schizophrenic” thermoresponsive behavior displaying simultaneously an UCST and an LCST (lower critical solution temperature transition. Exploratory experiments on the UCST-transition triggered the encapsulation and release of various solvatochromic fluorescent dyes as model “cargos” failed, apparently due to the poor affinity even of charged organic compounds to the collapsed state of the polyzwitterions.

  11. 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

  12. Creating a stem cell niche in the inner ear using self-assembling peptide amphiphiles

    Science.gov (United States)

    Sayed, Zafar A.; Stephanopoulos, Nicholas; Berns, Eric J.; Wadhwani, Anil R.; Morrissey, Zachery D.; Chadly, Duncan M.; Kobayashi, Shun; Edelbrock, Alexandra N.; Mashimo, Tomoji; Miller, Charles A.; McGuire, Tammy L.; Stupp, Samuel I.; Kessler, John A.

    2017-01-01

    The use of human embryonic stem cells (hESCs) for regeneration of the spiral ganglion will require techniques for promoting otic neuronal progenitor (ONP) differentiation, anchoring of cells to anatomically appropriate and specific niches, and long-term cell survival after transplantation. In this study, we used self-assembling peptide amphiphile (PA) molecules that display an IKVAV epitope (IKVAV-PA) to create a niche for hESC-derived ONPs that supported neuronal differentiation and survival both in vitro and in vivo after transplantation into rodent inner ears. A feature of the IKVAV-PA gel is its ability to form organized nanofibers that promote directed neurite growth. Culture of hESC-derived ONPs in IKVAV-PA gels did not alter cell proliferation or viability. However, the presence of IKVAV-PA gels increased the number of cells expressing the neuronal marker beta-III tubulin and improved neurite extension. The self-assembly properties of the IKVAV-PA gel allowed it to be injected as a liquid into the inner ear to create a biophysical niche for transplanted cells after gelation in vivo. Injection of ONPs combined with IKVAV-PA into the modiolus of X-SCID rats increased survival and localization of the cells around the injection site compared to controls. Human cadaveric temporal bone studies demonstrated the technical feasibility of a transmastoid surgical approach for clinical intracochlear injection of the IKVAV-PA/ONP combination. Combining stem cell transplantation with injection of self-assembling PA gels to create a supportive niche may improve clinical approaches to spiral ganglion regeneration. PMID:29284013

  13. Creating a stem cell niche in the inner ear using self-assembling peptide amphiphiles.

    Directory of Open Access Journals (Sweden)

    Akihiro J Matsuoka

    Full Text Available The use of human embryonic stem cells (hESCs for regeneration of the spiral ganglion will require techniques for promoting otic neuronal progenitor (ONP differentiation, anchoring of cells to anatomically appropriate and specific niches, and long-term cell survival after transplantation. In this study, we used self-assembling peptide amphiphile (PA molecules that display an IKVAV epitope (IKVAV-PA to create a niche for hESC-derived ONPs that supported neuronal differentiation and survival both in vitro and in vivo after transplantation into rodent inner ears. A feature of the IKVAV-PA gel is its ability to form organized nanofibers that promote directed neurite growth. Culture of hESC-derived ONPs in IKVAV-PA gels did not alter cell proliferation or viability. However, the presence of IKVAV-PA gels increased the number of cells expressing the neuronal marker beta-III tubulin and improved neurite extension. The self-assembly properties of the IKVAV-PA gel allowed it to be injected as a liquid into the inner ear to create a biophysical niche for transplanted cells after gelation in vivo. Injection of ONPs combined with IKVAV-PA into the modiolus of X-SCID rats increased survival and localization of the cells around the injection site compared to controls. Human cadaveric temporal bone studies demonstrated the technical feasibility of a transmastoid surgical approach for clinical intracochlear injection of the IKVAV-PA/ONP combination. Combining stem cell transplantation with injection of self-assembling PA gels to create a supportive niche may improve clinical approaches to spiral ganglion regeneration.

  14. Biphasic Peptide Amphiphile Nanomatrix Embedded with Hydroxyapatite Nanoparticles for Stimulated Osteoinductive Response

    Science.gov (United States)

    Anderson, Joel M.; Patterson, Jessica L.; Vines, Jeremy B.; Javed, Amjad; Gilbert, Shawn R.; Jun, Ho-Wook

    2013-01-01

    Formation of the native bone extracellular matrix (ECM) provides an attractive template for bone tissue engineering. The structural support and biological complexity of bone ECM are provided within a composite microenvironment that consists of an organic fibrous network reinforced by inorganic hydroxyapatite (HA) nanoparticles. Recreating this biphasic assembly, a bone ECM analogous scaffold comprised of self-assembling peptide amphiphile (PA) nanofibers and interspersed HA nanoparticles was investigated. PAs were endowed with biomolecular ligand signaling using a synthetically inscribed peptide sequence (i.e. RGDS) and integrated with HA nanoparticles to form a biphasic nanomatrix hydrogel. It was hypothesized the biphasic hydrogel would induce osteogenic differentiation of human mesenchymal stem cells (hMSCs) and improve bone healing as mediated by RGDS ligand signaling within PA nanofibers and embedded HA mineralization source. Viscoelastic stability of the biphasic PA hydrogels was evaluated with different weight concentrations of HA for improved gelation. After demonstrating initial viability, long-term cellularity and osteoinduction of encapsulated hMSCs in different PA hydrogels were studied in vitro. Temporal progression of osteogenic maturation was assessed by gene expression of key markers. A preliminary animal study demonstrated bone healing capacity of the biphasic PA nanomatrix under physiological conditions using a critical size femoral defect rat model. The combination of RGDS ligand signaling and HA nanoparticles within the biphasic PA nanomatrix hydrogel demonstrated the most effective osteoinduction and comparative bone healing response. Therefore, the biphasic PA nanomatrix establishes a well-organized scaffold with increased similarity to natural bone ECM with the prospect for improved bone tissue regeneration. PMID:22077993

  15. Azobenzene-aminoglycoside: Self-assembled smart amphiphilic nanostructures for drug delivery.

    Science.gov (United States)

    Deka, Smriti Rekha; Yadav, Santosh; Mahato, Manohar; Sharma, Ashwani Kumar

    2015-11-01

    Here, we have designed and synthesized a novel cationic amphiphilic stimuli-responsive azobenzene-aminoglycoside (a small molecule) conjugate, Azo-AG 5, and characterized it by UV and FTIR. Light responsive nature of Azo-AG 5 was assessed under UV-vis light. Self- assembly of Azo-AG 5 in aqueous solutions into nanostructures and their ability to act as drug carrier were also investigated. The nanostructures of Azo-AG 5 showed average hydrodynamic diameter of ∼ 255 nm with aminoglycoside moiety (neomycin) and 4-dimethylaminoazobenzene forming hydrophilic shell and hydrophobic core, respectively. In the hydrophobic core, eosin and aspirin were successfully encapsulated. Dynamic light scattering (DLS) measurements demonstrated that the nanoassemblies showed expansion and contraction on successive UV and visible light irradiations exhibiting reversible on-off switch for controlling the drug release behavior. Similar behavior was observed when these nanostructures were subjected to pH-change. In vitro drug release studies showed a difference in UV and visible light-mediated release pattern. It was observed that the release rate under UV irradiation was comparatively higher than that observed under visible light. Further, azoreductase-mediated cleavage of the azo moiety in Azo-AG 5 nanoassemblies resulted in the dismantling of the structures into aggregated microstructures. Azo-AG 5 nanostructures having positive surface charge (+9.74 mV) successfully interacted with pDNA and retarded its mobility on agarose gel. Stimuli responsiveness of nanostructures and their on-off switch like behavior ensure the great potential as controlled drug delivery systems and in other biomedical applications such as colon-specific delivery and gene delivery. Copyright © 2015 Elsevier B.V. All rights reserved.

  16. Effect of sequence on the ionization behavior of a series of amphiphilic polypeptides.

    Science.gov (United States)

    Fowler, Michael; Siddique, Bushra; Duhamel, Jean

    2013-04-09

    The behavior of five polypeptides made of hydrophilic and pH-responsive aspartic acid (Asp) and hydrophobic phenylalanine (Phe), which had been prepared by stitching together short well-defined sequences of Asp and Phe, was studied as a function of pH. The effect of pH on these polypeptides referred to as (Asp3Phe1)n, (Asp2Phe1)n, (Asp1Phe1)n, (Asp1Phe2)n, and (Asp1Phe3)n varied dramatically depending on their constituting sequence. The more hydrophobic polypeptides (Asp1Phe2)n and (Asp1Phe3)n behaved as if the Asp's were isolated from each other and showed an apparent pKa (pKa(app)) that remained constant with level of ionization (α = [Asp(-)]/[Asp]total) and equaled 5.4 and 6.4, respectively. The more hydrophilic polypeptides (Asp3Phe1)n and (Asp2Phe1)n behaved like weak polyacids showing a linear increase in pKa(app) with increasing α. The pKa(app) of (Asp1Phe1)n showed a trend as a function of α intermediate between the Asp-rich and Phe-rich polypeptides, behaving as if the Asp's were isolated at low α values (0.35). The effect that α, and thus the charge density of the polypeptides, had on the collapse and aggregation of the polypeptides was characterized by conducting static light scattering and fluorescence measurements. Static light scattering measurements demonstrated that all polypeptides precipitated and aggregated in solution at a critical charge density of 0.2. Fluorescence measurements with pyrene indicated that this behavior was due to the formation of Phe aggregates in water. Together, these experiments provide a complete description of how pH affects the behavior of a series of unique amphiphilic polypeptides designed with a well-defined sequence.

  17. Study on the interaction between amphiphilic drug and bovine serum albumin: A thermodynamic and spectroscopic description

    Energy Technology Data Exchange (ETDEWEB)

    Rub, Malik Abdul, E-mail: malikrub@gmail.com [Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah-21589 (Saudi Arabia); Khan, Javed Masood [Interdisciplinary Biotechnology Unit, Aligarh Muslim University, Aligarh 202002 (India); Asiri, Abdullah M. [Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah-21589 (Saudi Arabia); Center of Excellence for Advanced Materials Research, King Abdulaziz University, Jeddah-21589 (Saudi Arabia); Khan, Rizwan Hasan, E-mail: rizwanhkhan1@gmail.com [Interdisciplinary Biotechnology Unit, Aligarh Muslim University, Aligarh 202002 (India); Kabir-ud-Din [Department of Applied Chemistry, Aligarh Muslim University, Aligarh-202002 (India)

    2014-11-15

    Herein we report the interaction of amphiphilic drug clomipramine hydrochloride (CLP—a tricyclic antidepressant) with bovine serum albumin (BSA) studied by fluorescence, UV–vis, and circular dichroism (CD) spectroscopic techniques. Clomipramine hydrochloride is used to treat a variety of mental health problems. The quenching rate constant (k{sub q}) values, calculated according to the fluorescence data, decrease with increase in temperature indicating the static quenching procedure for the CLP–BSA interaction. The association binding constants (K{sub A}), evaluated at different conditions, and the thermodynamic parameters (free energy, enthalpy and entropy changes) indicate that the hydrophobic forces play a major role in the binding interaction of drug. The interaction of BSA with CLP was further confirmed by UV absorption spectra. Blue shift of position was detected due to the complex formation between the BSA–CLP. The molecular distance, r{sub 0}, between donor (BSA) and acceptor (CLP) was estimated by fluorescence resonance energy transfer (FRET) whose value (4.47 nm) suggests high probability of static quenching interaction. The CD results prove the conformational changes in the BSA on binding with the drug. Thus, the results supply qualitative and quantitative understanding of the binding of BSA to CLP, which is important in understanding their effect as therapeutic agents. - Highlights: • BSA can be considered as a good carrier for transportation of CLP in vivo. • The fluorescence results indicated the presence of static quenching mechanism in the binding process. • CD spectra showed the change in molecular conformation of BSA in the presence of CLP. • The results have applicability in model drug delivery.

  18. Covalent Functionalization of NiTi Surfaces with Bioactive Peptide Amphiphile Nanofibers

    Science.gov (United States)

    Sargeant, Timothy D.; Rao, Mukti S.; Koh, Chung-Yan

    2009-01-01

    Surface modification enables the creation of bioactive implants using traditional material substrates without altering the mechanical properties of the bulk material. For applications such as bone plates and stents, it is desirable to modify the surface of metal alloy substrates to facilitate cellular attachment, proliferation, and possibly differentiation. In this work we present a general strategy for altering the surface chemistry of nickel-titanium shape memory alloy (NiTi) in order to covalently attach self-assembled peptide amphiphile (PA) nanofibers with bioactive functions. Bioactivity in the systems studied here includes biological adhesion and proliferation of osteoblast and endothelial cell types. The optimized surface treatment creates a uniform TiO2 layer with low levels of Ni on the NiTi surface, which is subsequently covered with an aminopropylsilane coating using a novel, lower temperature vapor deposition method. This method produces an aminated surface suitable for covalent attachment of PA molecules containing terminal carboxylic acid groups. The functionalized NiTi surfaces have been characterized by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectroscopy (ToF-SIMS), and atomic force microscopy (AFM). These techniques offer evidence that the treated metal surfaces consist primarily of TiO2 with very little Ni, and also confirm the presence of the aminopropylsilane overlayer. Self-assembled PA nanofibers presenting the biological peptide adhesion sequence Arg-Gly-Asp-Ser are capable of covalently anchoring to the treated substrate, as demonstrated by spectrofluorimetry and AFM. Cell culture and scanning electron microscopy (SEM) demonstrate cellular adhesion, spreading, and proliferation on these functionalized metal surfaces. Furthermore, these experiments demonstrate that covalent attachment is crucial for creating robust PA nanofiber coatings, leading to confluent cell monolayers. PMID:18083225

  19. Salt effects on the sol-gel transitions of aqueous peptide-amphiphile solutions

    Science.gov (United States)

    Yamamoto, Masashi; Maeda, Tomoki; Hotta, Atsushi

    A hydrogel made of a peptide amphiphile (PA) is an interesting soft material especially in the biomedical fields due to its controllable nanoscale structures with excellent biocompatibility. To extend the practical use of PA, a comprehensive study of the sol-gel transitions of PA is necessary to be used as e.g. a biomedical material. The effects of the types of salts in our body or in medicinal agents on the physical properties of the PA solution are not fully understood. In this study, different types of salt with various negative ions were added to a PA (C16-W3K) solution. The salt effects on the rheological properties, the pH, and the zeta potentials of the PA solutions were studied. From the rheological testing, it was found that the C16-W3K solutions could not gelate in the presence of Na2CO3 or Na3PO4, which could be caused by the aggregation of the wormlike micelles made of C16-W3K. pH-wise, the sol-gel transitions could be observed only when the PA solutions were relatively acidic (the Zeta potential was positive) instead of basic (the Zeta potential was very negative) . It was therefore concluded that the sol-gel transitions of the PA solution could be effectively controlled by the types of salt. This work was supported by a Grant-in-Aid for Scientific Research (A) (No. 15H02298 to A.H.) and a Grant-in-Aid for Research Activity Start-up (No.15H06586 to T.M.) from JSPS: KAKENHI.

  20. Yolk–shell Fe3O4@SiO2@PMO: amphiphilic magnetic nanocomposites as an adsorbent and a catalyst with high efficiency and recyclability

    KAUST Repository

    Dai, Jinyu

    2017-01-20

    This study describes the preparation of a multifunctional adsorptive catalyst by the incorporation of ligand groups within the channels of magnetic amphiphilic nanocomposites and attached with Pd nanoparticles. It was clearly demonstrated that Pd2+ was adsorbed by ligand-functionalized materials in water, and then Pd2+ was coordinated with ligand groups. Finally, the Pd nanoparticles were produced via an in situ reduction of Pd2+ by ligand groups through a simple hydrothermal process. Moreover, amphiphilic nanomaterials are viewed as excellent collectors of hydrophobic contaminants in water. The immobilized catalytic active sites with ligand-functionalized nanocomposites were allowed for maximal exposure to the reactants with minimal leaching of the Pd nanoparticles. The unique amphiphilic nanocomposites enabled selective oxidation of alcohols to proceed efficiently in water under aerobic conditions. Moreover, this nanocomposite catalyst could be completely recovered using an external magnet due to the superparamagnetic behavior of Fe3O4 and can be recycled with sustained selectivity and activity.

  1. Effect of ionizing radiation exposure in the morphology of modified HDPE with amphiphilic particles; Efeito da exposicao a radiacao ionizante na morfologia de PEAD modificado com particulas anfifilicas

    Energy Technology Data Exchange (ETDEWEB)

    Saldanha, Ana Luiza M. [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil); Vivas, Viviane; Zylberberg, Marcel P.; Silva, Tamara I.; Cardoso, Andre Luis V.; Pereira, Iaci M., E-mail: iacipere@gmail.com [Centro Tecnologico do Exercito (CTEx), Rio de Janeiro, RJ (Brazil); Patricio, Patricia S.O. [Centro Federal de Educacao Tecnologica de Minas Gerias (CEFET), Belo Horizonte, MG (Brazil)

    2015-07-01

    One of the techniques used to improve the properties of high performance polymers is the addition of hybrid particles in the polymer. In this context, amphiphilic particles were synthesized in order to provide surface characteristics that enhance the interaction of the interface with the polymeric matrix of high density polyethylene (HDPE). The amphiphilic particles were added to matrix of HDPE and the modified polymer composites were exposed to ionizing radiation (x-rays) for different times. The changes caused by exposure to ionizing radiation in the composite morphology was observed through the small angle x-ray technique. The results suggest that the addition of amphiphilic particles increased the stability of the composite to degradation by radiation. (author)

  2. "Bottom-Up" Construction of Hyperbranched Poly(prodrug-co-photosensitizer) Amphiphiles Unimolecular Micelles for Chemo-Photodynamic Dual Therapy.

    Science.gov (United States)

    Sun, Pei; Wang, Nan; Jin, Xin; Zhu, Xinyuan

    2017-10-25

    Despite the great advantages of chemo-photodynamic combination therapy, tedious synthesis steps and laborious purification procedures make the fabrication of chemo-photodynamic combined therapeutic platforms rather difficult. In this study, we develop a facile "bottom-up" strategy to fabricate hyperbranched poly(prodrug-co-photosensitizer) amphiphiles, h-P(CPTMA-co-BYMAI)-b-POEGMA (hPCBE), for chemo-photodynamic dual therapy. The easily prepared hPCBE possess a bottom-up-constructed hydrophobic core h-P(CPTMA-co-BYMAI) (hPCB) direct copolymerized from reduction-responsive CPT prodrug monomer (CPTMA) and boron dipyrromethene-based photosensitizer monomer (BYMAI), as well as a biocompatible shell polymerized from hydrophilic monomers. Because of the covalently interconnected core-shell structure, hPCBE exists as unimolecular micelles in aqueous solution and exhibits excellent structural stability under dilution condition. The hPCBE micelles can be effectively internalized by MCF-7 cells and release CPT triggered by the reductive milieu. In addition, photosensitizer moieties embedded in the hPCB core could generate singlet oxygen ( 1 O 2 ) effectively under irradiation, endowing hPCBE with the boosting of chemotherapeutic efficacy. As compared to the single chemotherapy of hyperbranched polyprodrug amphiphiles h-PCPTMA-b-POEGMA (hPCE) and photodynamic therapy of hyperbranched polyphotosensitizer amphiphiles h-PBYMAI-b-POEGMA (hPBE), hPCBE shows higher in vitro cytotoxicity. We expect that our approach will further boost research on the design of multifunctional drug delivery systems via the facile "bottom-up" strategy.

  3. Multicompartment micellar aggregates of linear ABC amphiphiles in solvents selective for the C block: A Monte Carlo simulation

    KAUST Repository

    Zhu, Yutian

    2012-01-01

    In the current study, we applied the Monte Carlo method to study the self-assembly of linear ABC amphiphiles composed of two solvophobic A and B blocks and a solvophilic C block. A great number of multicompartment micelles are discovered from the simulations and the detailed phase diagrams for the ABC amphiphiles with different block lengths are obtained. The simulation results reveal that the micellar structure is largely controlled by block length, solvent quality, and incompatibility between the different block types. When the B block is longer than or as same as the terminal A block, a rich variety of micellar structures can be formed from ABC amphiphiles. By adjusting the solvent quality or incompatibility between the different block types, multiple morphological transitions are observed. These morphological sequences are well explained and consistent with all the previous experimental and theoretical studies. Despite the complexity of the micellar structures and morphological transitions observed for the self-assembly of ABC amphiphiles, two important common features of the phase behavior are obtained. In general, the micellar structures obtained in the current study can be divided into zero-dimensional (sphere-like structures, including bumpy-surfaced spheres and sphere-on-sphere structures), one-dimensional (cylinder-like structures, including rod and ring structures), two-dimensional (layer-like structures, including disk, lamella and worm-like and hamburger structures) and three-dimensional (vesicle) structures. It is found that the micellar structures transform from low- to high- dimensional structures when the solvent quality for the solvophobic blocks is decreased. In contrast, the micellar structures transform from high- to low-dimensional structures as the incompatibility between different block types increases. Furthermore, several novel micellar structures, such as the CBABC five-layer vesicle, hamburger, CBA three-layer ring, wormlike shape with

  4. Detection of a new 'nematic-like' phase in liquid crystal-amphiphile mixture by differential scanning calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Dan, Kaustabh, E-mail: kaustabhdan@gmail.com; Roy, Madhusudan, E-mail: kaustabhdan@gmail.com; Datta, Alokmay, E-mail: kaustabhdan@gmail.com [Surface Physics and Materials Science Division, Saha Institute of Nuclear Physics, 1/AF Bidhannagar Block, Sector 1, Kolkata-700064 (India)

    2014-04-24

    Differential Scanning Calorimetry (DSC) studies on phase transitions of the pure liquid crystalline material N-4-methoxybenzylidene-4-butylaniline (MBBA) and mixtures of MBBA and the amphiphile Stearic Acid (StA) show significant changes in the behavior of mixture from pure MBBA, as regards the nematic-isotropic (N-I) transition temperature (T{sub c}) and other thermodynamic parameters like enthalpy, specific heat and activation energy with concentration of StA. In particular, the convexity of the Arrhenius plot in pure MBBA vanishes with StA concentration pointing to the formation of a new, perhaps 'nematic-like', phase in the mixtures.

  5. Amphiphilic copolymer derived from tamarind gum and poly (methyl methacrylate) via ATRP towards selective removal of toxic dyes.

    Science.gov (United States)

    Pal, Aniruddha; Pal, Sagar

    2017-03-15

    Herein an amphiphilic graft copolymer has been synthesized from tamarind gum and poly (methyl methacrylate) (g-TKP/pMMA) using atom transfer radical polymerization (ATRP) in presence of CuBr/bpy catalyst. Structural and surface properties of the copolymer have been investigated using 1 H NMR and FTIR spectra, DLS, TGA and FESEM analyses. The controlled and living nature of polymerization reaction has been explored using GPC analysis, while the gel characteristics of the copolymer has been analysed by rheological study. Finally, the copolymer demonstrates excellent pH triggered selective adsorption efficacy towards removal of toxic cationic/anionic dyes. Copyright © 2016 Elsevier Ltd. All rights reserved.

  6. Surface-based molecular self-assembly: Langmuir-Blodgett films of amphiphilic Ln(III) complexes.

    Science.gov (United States)

    Wales, Dominic J; Kitchen, Jonathan A

    2016-01-01

    The unique photophysical properties of the Ln(III) series has led to significant research efforts being directed towards their application in sensors. However, for "real-life" applications, these sensors should ideally be immobilised onto surfaces without loss of function. The Langmuir-Blodgett (LB) technique offers a promising method in which to achieve such immobilisation. This mini-review focuses on synthetic strategies for film formation, the effect that film formation has on the physical properties of the Ln(III) amphiphile, and concludes with examples of Ln(III) LB films being used as sensors.

  7. Synthesis of Hydrophilic and Amphiphilic Acryl Sucrose Monomers and Their Copolymerisation with Styrene, Methylmethacrylate and α- and β-Pinenes

    Directory of Open Access Journals (Sweden)

    Maria Teresa Barros

    2010-04-01

    Full Text Available Herein, we report the synthesis of monomethacryloyl sucrose esters, and their successful free radical homo- and co-polymerisation with styrene, methylmethacrylate, α- and β-pinene. The chemical, physical, structural and surface chemical properties of these polymers, containing a hydrophobic olefin backbone and hydrophilic sugar moieties as side chains, have been investigated. Biodegradation tests of the copolymer samples by a microbial fungal culture (Aspergillus niger method showed good biodegradability. The chemical structure and surface chemistry of the synthesized homo- and co-polymers demonstrate their potential technological relevance as amphiphilic and biodegradable polymers.

  8. Synthesis and antioxidant efficiency of a new amphiphilic spin-trap derived from PBN and lipoic acid.

    Science.gov (United States)

    Durand, G; Polidori, A; Salles, J P; Prost, M; Durand, P; Pucci, B

    2003-08-18

    The synthesis of a new amphiphilic antioxidant called PBNLP and derived from both alpha-phenyl-N-tert-butyl nitrone (PBN) and lipoic acid was described. Grafting a lactobionamide moiety onto the aromatic group of the PBN provided the water solubility of this compound. In vitro preliminary biological evaluations of its antioxidant capacity were performed using the KRL biological test based on free radical-induced hemolysis. The PBNLP induces a protection of erythrocytes against exogenous free radicals higher than that measured with lipoic acid or PBN alone or with lipoic acid or PBN derivatives in admixtures.

  9. Nucleobase-mediated, photocatalytic production of amphiphiles to promote the self-assembly of a simple self-replicating protocell.

    Science.gov (United States)

    Monnard, Pierre-Alain; Maurer, Sarah, E.; Albertsen, Anders, N.; Boncella, James, M.; Cape, Jonathan, L.

    Living cells are in many respects the ultimate nanoscale chemical system. Within a very small volume they can produce highly specific useful products by extracting resources and free energy from the environment. They are also self-organized, self-controlled, and capable of self-repair and self-replication. Designing artificial chemical systems (artificial cells or protocells) that would be endowed with these powerful capabilities has been investigated extensively in the recent years. Chemical systems usually studied were based on the encapsulation of a set of genes along with catalytic protein machinery within the self-assembled boundaries of liposome/vesicles. The generated systems have many of the characteristics of a living system, but lack the regulation by genetic information of all protocell functions. Departing from these encapsulated models, we have been attempting to implement a simple, chemical system in which the regulation of the metabolism is truly mediated by information molecules. Our proposed system is composed of a chemical mixture composed of fatty acids that form bilayers (compartment), amphiphilic information molecules (nucleic acids -NA), and metabolic complexes (photosensitizers). Due to the intrinsic properties of all its components, a chemical system will self-assemble into aqueous, colloid mixtures that will be conducive to the metabolic steps, the non-enzymatic polymerization of the information, and the photochemical fatty acid production from its oil-like precursor. The reaction products (e.g., the container molecules) will in turn promote system growth and replication. In this scheme, the NA acts as an information molecule mediating the metabolic catalysis (electron donor/relay system) with a ruthenium metal complex as a cofactor and sensitizer, which is used to convert the hydrophobic precursor container molecules into amphiphiles, thus directly linking protocell metabolism with information. In a first experimental design, NA has been

  10. Tuning of thermally induced sol-to-gel transitions of moderately concentrated aqueous solutions of doubly thermosensitive hydrophilic diblock copolymers poly(methoxytri(ethylene glycol) acrylate)-b-poly(ethoxydi(ethylene glycol) acrylate-co-acrylic acid).

    Science.gov (United States)

    Jin, Naixiong; Zhang, Hao; Jin, Shi; Dadmun, Mark D; Zhao, Bin

    2012-03-15

    We report in this article a method to tune the sol-to-gel transitions of moderately concentrated aqueous solutions of doubly thermosensitive hydrophilic diblock copolymers that consist of two blocks exhibiting distinct lower critical solution temperatures (LCSTs) in water. A small amount of weak acid groups is statistically incorporated into the lower LCST block so that its LCST can be tuned by varying solution pH. Well-defined diblock copolymers, poly(methoxytri(ethylene glycol) acrylate)-b-poly(ethoxydi(ethylene glycol) acrylate-co-acrylic acid) (PTEGMA-b-P(DEGEA-co-AA)), were prepared by reversible addition-fragmentation chain transfer polymerization and postpolymerization modification. PTEGMA and PDEGEA are thermosensitive water-soluble polymers with LCSTs of 58 and 9 °C, respectively, in water. A 25 wt % aqueous solution of PTEGMA-b-P(DEGEA-co-AA) with a molar ratio of DEGEA to AA units of 100:5.2 at pH = 3.24 underwent multiple phase transitions upon heating, from a clear, free-flowing liquid (sol-to-gel transition temperature (T(sol-gel)) shifted to higher values, while the gel-to-sol transition (T(gel-sol)) and the clouding temperature (T(clouding)) of the sample remained essentially the same. These transitions and the tunability of T(sol-gel) originated from the thermosensitive properties of two blocks of the diblock copolymer and the pH dependence of the LCST of P(DEGEA-co-AA), which were confirmed by dynamic light scattering and differential scanning calorimetry studies. Using the vial inversion test method, we mapped out the C-shaped sol-gel phase diagrams of the diblock copolymer in aqueous buffers in the moderate concentration range at three different pH values (3.24, 5.58, and 5.82, all measured at ~0 °C). While the upper temperature boundaries overlapped, the lower temperature boundary shifted upward and the critical gelation concentration increased with the increase of pH. The AA content in PTEGMA-b-P(DEGEA-co-AA) was found to have a significant

  11. Synthesis of biodegradable amphiphilic Y-shaped block co-polymers via ring-opening polymerization for drug delivery.

    Science.gov (United States)

    Jia, Lin; Yan, Lifeng; Li, Yang

    2011-01-01

    A series of novel Y-shaped biodegradable block co-polymers of poly(ε-caprolactone) (PCL) and poly(ethyl ethylene phosphate) (PEEP) (PCL-(PEEP)2) were synthesized via ring-opening polymerization (ROP) of EEP with bis-hydroxy-functional ROP initiator (init-PCL-(OH)2). The init-PCL-(OH)2 was synthesized by ROP of CL using 4-hydroxybutyl acrylate (HBA) as initiator and L-tartaric acid as catalyst in bulk, and subsequently the resulting vinyl-terminated PCL was end-capped by acetyl chloride, followed by Michael addition using excess diethanolamine. The Y-shaped co-polymers and their intermediates were characterized by (1)H-, (13)C-, (31)P-NMR, FT-IR and gel-permeation chromatography. The results indicated that the molecular weight of the Y-shaped co-polymers increased with the increasing of the molar ratios of EEP to init-PCL-(OH)2 in the feed, while the PCL chain length was kept constant. The amphiphilic block co-polymers could self-assemble into micelles in aqueous solution, which was demonstrated by dynamic light scattering, (1)H-NMR and atomic force microscopy. A study of controlled release of indomethacin indicated that the amphiphilic block co-polymers could potentially provide novel vehicles for drug delivery.

  12. Novel high relaxivity colloidal particles based on the specific phase organisation of amphiphilic gadolinium chelates with cholesterol.

    Science.gov (United States)

    Gløgård, Christian; Stensrud, Gry; Klaveness, Jo

    2003-03-06

    To obtain high T(1)-relaxivity colloidal particles with a simultaneously high loading of amphiphilic Gd-chelates, a novel drug dosage form based on the phase organisation of amphiphilic gadolinium chelates with cholesterol was developed. In order to find a formulation, which exhibit both high T(1)-relaxivity and gives small particles a D-optimal mixture design (experimental design) was applied. Gadolinium 1,4,7-tris(carboxymethyl)-10-(2-hydroxyhexadecyl)-1,4,7,10-tetraazacyclododecane (Gd-HHD-DO3A) and cholesterol at approximately equimolar ratio proved to form thermodynamic stable disc-like colloidal particles as seen by cryo-electron micrographs. T(1)-relaxivity of these particles was typically around 20mM(-1)s(-1) and the size below 100 nm (photon correlation spectroscopy (PCS)). The particles do most probably not interact with blood components as no change in T(1)-relaxivity was observed when the particles were mixed with whole blood. The particles were stable at room temperature for at least 6 months.

  13. A molecular model for membrane fusion based on solution studies of an amphiphilic peptide from HIV gp41.

    Science.gov (United States)

    Fujii, G; Horvath, S; Woodward, S; Eiserling, F; Eisenberg, D

    1992-11-01

    The mechanism of protein-mediated membrane fusion and lysis has been investigated by solution-state studies of the effects of peptides on liposomes. A peptide (SI) corresponding to a highly amphiphilic C-terminal segment from the envelope protein (gp41) of the human immunodeficiency virus (HIV) was synthesized and tested for its ability to cause lipid membranes to fuse together (fusion) or to break open (lysis). These effects were compared to those produced by the lytic and fusogenic peptide from bee venom, melittin. Other properties studied included the changes in visible absorbance and mean particle size, and the secondary structure of peptides as judged by CD spectroscopy. Taken together, the observations suggest that protein-mediated membrane fusion is dependent not only on hydrophobic and electrostatic forces but also on the spatial arrangement of the amino acid residues to form an amphiphilic structure that promotes the mixing of the lipids between membranes. A speculative molecular model is proposed for membrane fusion by alpha-helical peptides, and its relationship to the forces involved in protein-membrane interactions is discussed.

  14. Photo-switching of a non-ionic azobenzene amphiphile in Langmuir and Langmuir-Blodgett films.

    Science.gov (United States)

    Piosik, Emilia; Kotkowiak, Michał; Korbecka, Izabela; Galewski, Zbigniew; Martyński, Tomasz

    2017-08-30

    The concept of programmable and reconfigurable soft matter has emerged in science in the last few decades and can be realized by photoisomerization of azobenzene derivatives. This possibility results in great application potential of these compounds in optical storage devices, molecular junctions of electronic devices, command layers of liquid crystal displays or holographic gratings. In this paper, we present the results of a study on the organization and isomerization of the non-ionic and amphiphilic methyl 4-[(E)-2-[4-(nonyloxy)phenyl]diazen-1-yl]benzoate (LCA) in a 2D layer architecture of Langmuir and Langmuir-Blodgett (LB) films supported by spectroscopic studies on LCA chloroform solutions. Our investigation has shown a significantly different molecular organization of LCA depending on the ratio of trans and cis isomers in the monolayers. Taking advantage of a relatively low packing density and aggregation strength in the cis-LCA monolayer, we demonstrated the reversible isomerization in the LB film initially formed of LCA molecules in the cis form, while in the trans-LCA monolayer this effect was not observed. Our approach allows the formation of a switchable monolayer made of the amphiphilic LCA showing liquid crystalline properties without introducing an ionic group into the molecule structure, mixing with another compound or changing the subphase pH to provide free space for the molecules' isomerization.

  15. Self-Assembly of Calix[4]arene-Based Amphiphiles Bearing Polyethylene Glycols: Another Example of "Platonic Micelles".

    Science.gov (United States)

    Yoshida, Kenta; Fujii, Shota; Takahashi, Rintaro; Matsumoto, Sakiko; Sakurai, Kazuo

    2017-09-12

    The aggregation number of classical micelles exhibits a certain distribution, which is a recognizable feature of conventional micelles. However, we recently identified perfectly monodisperse calix[4]arene-based micelles whose aggregation numbers agree with the vertex numbers of regular polyhedra, that is, Platonic solids, and thus they are named "Platonic micelles". Regarding our hypothesis of the formation mechanism of Platonic micelles, both repulsive interactions including steric hindrance and electrostatic repulsions among the headgroups are important for determining their aggregation number; however, neither of these is necessarily needed to consider. In this study, we employed polyethylene glycols (PEGs) as the nonionic headgroup of calix[4]arene-based amphiphiles to study the effects of only repulsive interactions caused by steric hindrance on the formation of Platonic micelles. The amphiphiles containing relatively low-molecular-weight PEGs (550 or 1000 g mol -1 ) form dodecamer or octamer micelles, respectively, with no variation in the aggregation number. However, relatively high-molecular-weight PEGs (2000 g mol -1 ) produce polydispersed micelles with a range of aggregation number. PEG 2000 exhibits a greater affinity for water than PEG 550 and 1000, resulting in fewer hydrophobic interactions in micelle formation, as indicated by the drastic increase of the critical micelle concentration (CMC) value in the PEG 2000 system. The instability of the structure of PEG 2k CaL5 micelles might contribute to the higher mobility of PEG in the micellar shell, resulting in a non-Platonic aggregation number with polydispersity.

  16. Self-consistent field theoretic simulations of amphiphilic triblock copolymer solutions: Polymer concentration and chain length effects

    Directory of Open Access Journals (Sweden)

    X.-G. Han

    2014-06-01

    Full Text Available Using the self-consistent field lattice model, polymer concentration φP and chain length N (keeping the length ratio of hydrophobic to hydrophilic blocks constant the effects on temperature-dependent behavior of micelles are studied, in amphiphilic symmetric ABA triblock copolymer solutions. When chain length is increased, at fixed φP, micelles occur at higher temperature. The variations of average volume fraction of stickers φcos and the lattice site numbers Ncols at the micellar cores with temperature are dependent on N and φP, which demonstrates that the aggregation of micelles depends on N and φP. Moreover, when φP is increased, firstly a peak appears on the curve of specific heat CV for unimer-micelle transition, and then in addition a primary peak, the secondary peak, which results from the remicellization, is observed on the curve of CV. For a long chain, in intermediate and high concentration regimes, the shape of specific heat peak markedly changes, and the peak tends to be a more broad peak. Finally, the aggregation behavior of micelles is explained by the aggregation way of amphiphilic triblock copolymer. The obtained results are helpful in understanding the micellar aggregation process.

  17. Co-assembly of Peptide Amphiphiles and Lipids into Supramolecular Nanostructures Driven by Anion-π Interactions

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Zhilin; Erbas, Aykut; Tantakitti, Faifan; Palmer, Liam C.; Jackman, Joshua A.; Olvera de la Cruz, Monica; Cho, Nam-Joon; Stupp, Samuel I. (Nanyang); (NWU)

    2017-06-01

    Co-assembly of binary systems driven by specific non-covalent interactions can greatly expand the structural and functional space of supramolecular nanostructures. We report here on the self-assembly of peptide amphiphiles and fatty acids driven primarily by anion-π interactions. The peptide sequences investigated were functionalized with a perfluorinated phenylalanine residue to promote anion-π interactions with carboxylate headgroups in fatty acids. These interactions were verified here by NMR and circular dichroism experiments as well as investigated using atomistic simulations. Positioning the aromatic units close to the N-terminus of the peptide backbone near the hydrophobic core of cylindrical nanofibers leads to strong anion-π interactions between both components. With a low content of dodecanoic acid in this position, the cylindrical morphology is preserved. However, as the aromatic units are moved along the peptide backbone away from the hydrophobic core, the interactions with dodecanoic acid transform the cylindrical supramolecular morphology into ribbon-like structures. Increasing the ratio of dodecanoic acid to PA leads to either the formation of large vesicles in the binary systems where the anion-π interactions are strong, or a heterogeneous mixture of assemblies when the peptide amphiphiles associate weakly with dodecanoic acid. Our findings reveal how co-assembly involving designed specific interactions can drastically change supramolecular morphology and even cross from nano to micro scales.

  18. Synthesis of amphiphilic macrocyclic molecules from family of aza-porphyrins and study in Langmuir-Blodgett films

    International Nuclear Information System (INIS)

    Palacin, Serge

    1988-01-01

    The cellular automata, also called formal neurons, directly inspired by the knowledge concerning the nervous system, are able to mimic some basic processes of brain, as shape recognition, connecting memory, information sorting... This work aims to build a molecular structure able to fit the working rules of a bidimensional cellular automata. So, amphiphilic molecules belonging to the aza-porphyrin family are synthesized and organized into a planar paving by the Langmuir-Blodgett technique. The regular structure of the outcoming ultra-thin films is studied by linear dichroism and anisotropic electron spin resonance. The physico-chemical behaviour of the amphiphilic molecules is studied and brings about an explanation of the redox phenomena which are observed on the monomolecular film on the water surface. So are we able to outline the future chemical addressing ways of the bidimensional cellular automata. In the end of this dissertation, different ways likely to insure covalent bindings between the active sites and allow the transfer of information within the cellular network are discussed. (author) [fr

  19. Photosensitizer enhanced disassembly of amphiphilic micelle for ROS-response targeted tumor therapy in vivo.

    Science.gov (United States)

    Dai, Liangliang; Yu, Yonglin; Luo, Zhong; Li, Menghuan; Chen, Weizhen; Shen, Xinkun; Chen, Feng; Sun, Qiang; Zhang, Qingfeng; Gu, Hao; Cai, Kaiyong

    2016-10-01

    This study reports a reactive oxygen species (ROS) sensitive drug delivery system based on amphiphilic polymer of poly(propylene sulfide)-polyethylene glycol-serine-folic acid (PPS-mPEG-Ser-FA). The polymer could form homogeneous micelles with an average diameter of around 80 nm through self-assembly, which would then be loaded with the singlet oxygen-generating photosensitizer of zinc phthalocyanine (ZNPC) and anti-cancer drug of DOX. The disassembly of micelles could be triggered by the hydrophobic to hydrophilic transition of the PPS core in response to ROS-induced oxidation in vitro. ZNPC molecules are capable of producing ROS under laser irradiation, which results in the rapid disassembly of micelles and releasing of the anti-tumor drug for tumor therapy under physiological condition otherwise. Moreover, the excessive ROS production deriving from ZNPC synergically induces cells apoptosis. Furthermore, the DOX loaded amphiphilic micelles could be internalized by tumor cells via FA receptor-mediated endocytosis to effectively inhibit the tumor growth in vivo, while with only minimal toxic side effects. The results in vitro and in vivo consistently demonstrate that the light-responsive micelle is a promising biodegradable nanocarrier for on-command drug release and targeted tumor therapy. Copyright © 2016 Elsevier Ltd. All rights reserved.

  20. Synthesis of amphiphilic alternating polyesters with oligo(ethylene glycol) side chains and potential use for sustained release drug delivery.

    Science.gov (United States)

    Wang, Wei; Ding, Jianxun; Xiao, Chunsheng; Tang, Zhaohui; Li, Di; Chen, Jie; Zhuang, Xiuli; Chen, Xuesi

    2011-07-11

    Novel amphiphilic alternating polyesters, poly((N-phthaloyl-l-glutamic anhydride)-co-(2-(2-(2-methoxyethoxy)ethoxy)methyl)oxirane) (P(PGA-co-ME(2)MO)), were synthesized by alternating copolymerization of PGA and ME(2)MO. The structures of the synthesized polyesters were characterized by (1)H NMR, (13)C NMR, FT-IR, and GPC analyses. Because of the presence of oligo(ethylene glycol) (OEG) side chains, the polyesters could self-assemble into thermosensitive micelles. Dynamic light scattering (DLS) showed that these micelles underwent thermoinduced size decrease without intermicellar aggregation. In vitro methyl thiazolyl tetrazolium (MTT) assay demonstrated that the polyesters were biocompatible to Henrietta Lacks (HeLa) cells, rendering their potential for drug delivery applications. Two hydrophobic drugs, rifampin and doxorubicin (DOX), were loaded into the polyester micelles and observed to be released in a zero-order sustained manner. The sustained release could be accelerated in lower pH or in the presence of proteinase K, due to the degradation of the polyester under these conditions. Remarkably, in vitro cell experiments showed that the polyester micelles accomplished fast release of DOX inside cells and higher anticancer efficacy as compared with the free DOX. With enhanced stability during circulation condition and accelerated drug release at the target sites (e.g., low pH or enzyme presence), these novel polyesters with amphiphilic structures are promising to be used in sustained release drug delivery systems.

  1. Supramolecular Self-Assembly and Dual-Switch Vapochromic, Vapoluminescent, and Resistive Memory Behaviors of Amphiphilic Platinum(II) Complexes.

    Science.gov (United States)

    Li, Yongguang; Chen, Ling; Ai, Yeye; Hong, Eugene Yau-Hin; Chan, Alan Kwun-Wa; Yam, Vivian Wing-Wah

    2017-10-04

    A series of amphiphilic platinum(II) complexes with tridentate N-donor ligands has been synthesized and characterized. Different supramolecular architectures are constructed using the amphiphilic molecules as the building blocks through the formation of Pt···Pt and π-π stacking interactions in aqueous media. The aggregation-deaggregation-aggregation self-assembly behavior together with obvious spectroscopic changes could be fine-tuned by the addition of THF in aqueous media. More interestingly, one of the complexes is found to show fast response and high selectivity toward alcohol and water vapors with good reversibility, leading to drastic color and luminescence changes, and hence unique dual switching behavior, with the water molecules readily displaced by the alcohol vapor. Rapid writing and erasure have been realized via the control of a jet or a stream of alcohol vapor flow. In addition, it has been employed as active materials in the fabrication of small-molecule solution-processable resistive memory devices, exhibiting stable and promising binary memory performance with threshold voltages of ca. 3.4 V, high ON/OFF ratios of up to 10 5 and long retention times of over 10 4 s. The vapochromic and vapoluminescent materials are demonstrated to have potential applications in chemosensing, logic gates, VOC monitoring, and memory functions.

  2. Synthesis of Fluorinated Amphiphilic Block Copolymers Based on PEGMA, HEMA, and MMA via ATRP and CuAAC Click Chemistry

    Directory of Open Access Journals (Sweden)

    Fatime Eren Erol

    2014-01-01

    Full Text Available Synthesis of fluorinated amphiphilic block copolymers via atom transfer radical polymerization (ATRP and Cu(I catalyzed Huisgen 1,3-dipolar cycloaddition (CuAAC was demonstrated. First, a PEGMA and MMA based block copolymer carrying multiple side-chain acetylene moieties on the hydrophobic segment for postfunctionalization was carried out. This involves the synthesis of a series of P(HEMA-co-MMA random copolymers to be employed as macroinitiators in the controlled synthesis of P(HEMA-co-MMA-block-PPEGMA block copolymers by using ATRP, followed by a modification step on the hydroxyl side groups of HEMA via Steglich esterification to afford propargyl side-functional polymer, alkyne-P(HEMA-co-MMA-block-PPEGMA. Finally, click coupling between side-chain acetylene functionalities and 2,3,4,5,6-pentafluorobenzyl azide yielded fluorinated amphiphilic block copolymers. The obtained polymers were structurally characterized by 1H-NMR, 19F-NMR, FT-IR, and GPC. Their thermal characterizations were performed using DSC and TGA.

  3. Hierarchical Self-Assembly of Peptide Amphiphiles: Form and Function at Multiple Length Scales

    Science.gov (United States)

    Zha, Runye Helen

    Hierarchical self-assembly, the organization of molecules into supramolecular structures of increasing size and complexity, is a potent tool for materials synthesis and requires understanding the connections of structure across multiple length scales. Herein, self-assembly of peptide amphiphiles (PAs) into nanoscopic and macroscopic materials is explored, and their anti-cancer applications are investigated. First, nanoscale assembly is examined in the context of an anti-angiogenic PA bearing the G-helix motif of maspin, a tumor suppressor protein. Assembly of this maspin-mimetic PA (MMPA) stabilizes the native G-helix conformation and improves binding to endothelial cells. Furthermore, PA nanostructures significantly increase cell adhesion to fibronectin as compared to G-helix peptide alone. Combined with its inhibitory effect on cell migration, MMPA nanostructures thus show anti-angiogenic activity on par with maspin protein in vitro and in vivo. Second, assembly of cationic PAs with hyaluronic acid (HA), an anionic polyelectrolyte, into macroscopic membranes is explored using PAs with identical formal charge but systematically varied self-assembly domains. Results suggest that membrane formation is dictated by the initial moments of component aggregation and is highly sensitive to PA molecular structure via nanoscale assembly. Specifically, PAs with beta-sheet forming residues are nanofibrous and have high surface charge density, leading to robust membranes with aligned-fiber microstructure. PAs without beta-sheet forming residues are nanospherical and have low surface charge density, leading to weak membranes with non-fibrous finger-like microstructure. Lastly, the principles of PA-HA membrane assembly are applied towards development of anti-cancer therapeutic biomaterials. Here, cytotoxic PAs bearing the epitope (KLAKLAKbeta)2 are co-assembled with non-bioactive cationic PA in order to achieve varying nanoscale morphology. These nanostructures are then

  4. Synthesis of nonionic reduced-sugar based bola amphiphiles and gemini surfactants with an alpha,omega-diamino-(oxa)alkyl spacer

    NARCIS (Netherlands)

    Wagenaar, Anno; Engberts, Jan B. F. N.

    2007-01-01

    Reduced-sugar based gemini surfactants with an alpha,omega-diamino-(oxa) alkyl spacer exhibit a rich pH-dependent aggregation behavior and are efficient DNA carriers in gene transfection. Herein, we describe an improved synthetic procedure for these amphiphiles. First, a series of novel nonionic

  5. Regulation of sodium channel function by bilayer elasticity: the importance of hydrophobic coupling. Effects of Micelle-forming amphiphiles and cholesterol

    DEFF Research Database (Denmark)

    Lundbæk, Jens August; Birn, Pia; Hansen, Anker J

    2004-01-01

    , Triton X-100, and reduced Triton X-100) that make lipid bilayers less "stiff", as measured using gA channels, shift the voltage dependence of sodium channel inactivation toward more hyperpolarized potentials. At low amphiphile concentration, the magnitude of the shift is linearly correlated to the change...

  6. 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

  7. 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.

  8. Amphiphilic copolymers based on polyoxazoline and grape seed vegetable oil derivatives: self-assemblies and dynamic light scattering

    Energy Technology Data Exchange (ETDEWEB)

    Travelet, Christophe, E-mail: Christophe.Travelet@cermav.cnrs.fr [Universite Joseph Fourier (UJF), Institut de Chimie Moleculaire de Grenoble (ICMG-FR 2607 CNRS), PolyNat Carnot institute, Arcane LabEx, domaine universitaire de Grenoble, Centre de Recherches sur les Macromolecules Vegetales - CERMAV-UPR 5301 CNRS (France); Stemmelen, Mylene; Lapinte, Vincent [Universite de Montpellier II, Institut Charles Gerhardt Montpellier (UMR 5253 CNRS-UM2-UM1-ENSCM), equipe ingenierie et architectures macromoleculaires (France); Dubreuil, Frederic [Universite Joseph Fourier (UJF), Institut de Chimie Moleculaire de Grenoble (ICMG-FR 2607 CNRS), PolyNat Carnot institute, Arcane LabEx, domaine universitaire de Grenoble, Centre de Recherches sur les Macromolecules Vegetales - CERMAV-UPR 5301 CNRS (France); Robin, Jean-Jacques [Universite de Montpellier II, Institut Charles Gerhardt Montpellier (UMR 5253 CNRS-UM2-UM1-ENSCM), equipe ingenierie et architectures macromoleculaires (France); and others

    2013-06-15

    The self-assembly in solution of original structures of amphiphilic partially natural copolymers based on polyoxazoline [more precisely poly(2-methyl-2-oxazoline) (POx)] and grape seed vegetable oil derivatives (linear, T-, and trident-structure) is investigated. The results show that such systems are found, using dynamic light scattering (DLS), to spontaneously self-organize into monomodal, narrow-size, and stable nanoparticles in aqueous medium. The obtained hydrodynamic diameters (D{sub h}) range from 8.6 to 32.5 nm. Specifically, such size increases strongly with increasing natural block (i.e., lipophilic species) length due to higher hydrophobic interactions (from 10.1 nm for C{sub 19} to 19.2 nm for C{sub 57}). Furthermore, increasing the polyoxazoline (i.e., hydrophilic block) length leads to a moderate linear increase of the D{sub h}-values. Therefore, the first-order size effect comes from the natural lipophilic block, whereas the characteristic size can be tuned more finely (i.e., in a second-order) by choosing appropriately the polyoxazoline length. The DLS results in terms of characteristic size are corroborated using nanoparticle tracking analysis (NTA), and also by atomic force microscopy (AFM) and transmission electron microscopy (TEM) imaging where well-defined spherical and individual nanoparticles exhibit a very good mechanical resistance upon drying. Moreover, changing the lipophilic block architecture from linear to T-shape, while keeping the same molar mass, generates a branching and thus a shrinking by a factor of 2 of the nanoparticle volume, as observed by DLS. In this paper, it is clearly shown that the self-assemblies of amphiphilic block copolymer obtained from grape seed vegetable oil derivatives (sustainable renewable resources) as well as their tunability are of great interest for biomass valorization at the nanoscale level [continuation of the article by Stemmelen et al. (Polym Chem 4:1445-1458, 2013)].Graphical AbstractAmphiphilic

  9. Cationic Amphiphilic Tris-Cyclometalated Iridium(III) Complexes Induce Cancer Cell Death via Interaction with Ca2+-Calmodulin Complex.

    Science.gov (United States)

    Hisamatsu, Yosuke; Suzuki, Nozomi; Masum, Abdullah-Al; Shibuya, Ai; Abe, Ryo; Sato, Akira; Tanuma, Sei-Ichi; Aoki, Shin

    2017-02-15

    In our previous paper, we reported on the preparation of some cationic amphiphilic Ir complexes (2c, 2d) containing KKGG peptides that induce and detect cell death of Jurkat cells. Mechanistic studies suggest that 2c interacts with anionic molecules and/or membrane receptors on the cell surface to trigger an intracellular Ca 2+ response, resulting in the induction of cell death, accompanied by membrane disruption. We have continued the studies of cell death of Jurkat cells induced by 2c and found that xestospongin C, a selective inhibitor of an inositol 1,4,5-trisphosphate receptor located on the endoplasmic reticulum (ER), reduces the cytotoxicity of 2c, suggesting that 2c triggers the release of Ca 2+ from the ER, leading to an increase in the concentration of cytosolic Ca 2+ , thus inducing cell death. Moreover, we synthesized a series of new amphiphilic cationic Ir complexes 5a-c containing photoreactive 3-trifluoromethyl-3-phenyldiazirine (TFPD) groups, in an attempt to identify the target molecules of 2c. Interestingly, it was discovered that a TFPD group functions as a triplet quencher of Ir complexes. It was also found that 5b is useful as a turn-on phosphorescent probe of acidic proteins such as bovine serum albumin (BSA) (pI = 4.7) and their complexation was confirmed by luminescence titrations and SDS-PAGE of photochemical products between them. These successful results allowed us to carry out photoaffinity labeling of the target biomolecules of 5b (2c and analogues thereof) in Jurkat cells. A proteomic analysis of the products obtained by the photoirradiation of 5b with Jurkat cells suggests that the Ca 2+ -binding protein "calmodulin (CaM)" is one of target proteins of the Ir complexes. Indeed, 5b was found to interact with the Ca 2+ -CaM complex, as evidenced by luminescence titrations and the results of photochemical reactions of 5b with CaM in the presence of Ca 2+ (SDS-PAGE). A plausible mechanism for cell death induced by a cationic amphiphilic Ir

  10. An approach to the construction of tailor-made amphiphilic peptides that strongly and selectively bind to hairpin RNA targets.

    Science.gov (United States)

    Lee, Su Jin; Hyun, Soonsil; Kieft, Jeffrey S; Yu, Jaehoon

    2009-02-18

    The hairpin RNA motif is one of the most frequently observed secondary structures and is often targeted by therapeutic agents. An amphiphilic peptide with seven lysine and eight leucine residues and its derivatives were designed for use as ligands against RNA hairpin motifs. We hypothesized that variations in both the hydrophobic leucine-rich and hydrophilic lysine-rich spheres of these amphiphilic peptides would create extra attractive interactions with hairpin RNA targets. A series of alanine-scanned peptides were probed to identify the most influential lysine residues in the hydrophilic sphere. The binding affinities of these modified peptides with several hairpins, such as RRE, TAR from HIV, a short hairpin from IRES of HCV, and a hairpin from the 16S A-site stem from rRNA, were determined. Since the hairpin from IRES of HCV was the most susceptible to the initial series of alanine-scanned peptides, studies investigating how further variations in the peptides effect binding employed the IRES hairpin. Next, the important Lys residues were substituted by shorter chain amines, such as ornithine, to place the peptide deeper into the hairpin groove. In a few cases, a 70-fold improved binding was observed for peptides that contained the specifically located shorter amine side chains. To further explore changes in binding affinities brought about by alterations in the hydrophobic sphere, tryptophan residues were introduced in place of leucine. A few peptides with tryptophan in specific positions also displayed 70-fold improved binding affinities. Finally, double mutant peptides incorporating both specifically located shorter amine side chains in the hydrophilic region and tryptophan residues in the hydrophobic region were synthesized. The binding affinities of peptides containing the simple double modification were observed to be 80 times lower, and their binding specificities were increased 40-fold. The results of this effort provide important information about

  11. Amphiphilic core shell nanoparticles containing dense polyethyleneimine shells for efficient delivery of microRNA to Kupffer cells

    Directory of Open Access Journals (Sweden)

    Liu Z

    2016-06-01

    Full Text Available Zuojin Liu,1,* Dechao Niu,2,3,* Junyong Zhang,1 Wenfeng Zhang,1 Yuan Yao,2 Pei Li,2 Jianping Gong1 1Department of Hepatobiliary Surgery, The Second Affiliated Hospital of Chongqing Medical University, Chongqing, 2Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, 3Lab of Low-Dimensional Materials Chemistry, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai, People’s Republic of China *These authors contributed equally to this work Abstract: Efficient and targeted delivery approach to transfer exogenous genes into macrophages is still a great challenge. Current gene delivery methods often result in low cellular uptake efficiency in vivo in some types of cells, especially for the Kupffer cells (KCs. In this article, we demonstrate that amphiphilic core–shell nanoparticles (NPs consisting of well-defined hydrophobic poly(methyl methacrylate (PMMA cores and branched polyethyleneimine (PEI shells (denoted as PEI@PMMA NPs are efficient nanocarriers to deliver microRNA (miRNA-loaded plasmid to the KCs. Average hydrodynamic diameter of PEI@PMMA NPs was 279 nm with a narrow size distribution. The NPs also possessed positive surface charges up to +30 mV in water, thus enabling effective condensation of negatively charged plasmid DNA. Gel electrophoresis assay showed that the resultant PEI@PMMA NPs were able to completely condense miRNA plasmid at a weight ratio of 25:1 (N/P ratio equal to 45:1. The Cell Counting Kit-8 assay and flow cytometry results showed that the PEI@PMMA/miRNA NPs displayed low cytotoxicity and cell apoptosis activity against the KCs. The maximum cell transfection efficiency reached 34.7% after 48 hours, which is much higher than that obtained by using the commercial Lipofectamine™ 2000 (1.7%. Bio-transmission electron microscope observation revealed that the PEI@PMMA NPs were mainly distributed in

  12. Self-assembly of an amphiphilic macromolecule under spherical confinement: An efficient route to generate hollow nanospheres

    Science.gov (United States)

    Glagoleva, A. A.; Vasilevskaya, V. V.; Yoshikawa, K.; Khokhlov, A. R.

    2013-12-01

    In general, bio-macromolecules are composed of hydrophilic and hydrophobic moieties and are confined within small cavities, such as cell membranes and intracellular organelles. Here, we studied the self-organization of macromolecules having groups with different affinities to solvents under spherical nano-scale confinement by means of computer modeling. It is shown that depending on the interaction parameters of monomer units composed of side- and main-chain monomer groups along a single linear macromolecule and on cavity size, such amphiphilic polymers undergo the conformational transitions between hollow nanospheres, rod-like and folded cylindrical structures, and a necklace conformation with and without a particular ordering of beads. The diagram of the conformations in the variables the incompatibility parameter of monomer units and the cavity radius is constructed.

  13. Influence Of Magnetic Iron Oxide Nanoparticles And Perfluoroalkylated Amphiphilic Phosphates On Red Blood Cells And Caco-2 Cells

    Science.gov (United States)

    Moersdorf, Daniel; Hugounenq, Pierre; Phuoc, Lai Truonc; Mamlouk-Chaouachi, Hind; Nikolova, Gergana; Krafft, Marie Pierre; Waton, Gilles; Felder-Flesch, Delphine; Begin-Colin, Sylvie; Pourroy, Geneviève; Bernhardt, Ingolf

    2010-10-01

    The interactions of two types of cells (red blood cells (RBCs), Caco-2 cells) with magnetic iron oxide nanoparticles (non-grafted, citrate-grafted, dendrimer-grafted) of 11 nm in size, and with three perfluoroalkylated amphiphilic phosphates varying in chain length and number of fluorine atoms have been investigated. We focused on two important physiological parameters of the cells, the intracellular pH and the intracellular Ca2+ content. The results show that the nanoparticles do not have a significant influence on the pH and Ca2+ content of Caco-2 cells. The Ca2+ content of RBCs is also not affected but the intracellular pH is slightly reduced. In addition, the perfluoroalkylated phosphates do not affect the Caco-2 cells. However, these molecules have a small effect on the intracellular pH of RBCs. Furthermore, they influence significantly the Ca2+ content of a subpopulation of the RBCs.

  14. An amphiphilic graft copolymer-based nanoparticle platform for reduction-responsive anticancer and antimalarial drug delivery

    Science.gov (United States)

    Najer, Adrian; Wu, Dalin; Nussbaumer, Martin G.; Schwertz, Geoffrey; Schwab, Anatol; Witschel, Matthias C.; Schäfer, Anja; Diederich, François; Rottmann, Matthias; Palivan, Cornelia G.; Beck, Hans-Peter; Meier, Wolfgang

    2016-08-01

    Medical applications of anticancer and antimalarial drugs often suffer from low aqueous solubility, high systemic toxicity, and metabolic instability. Smart nanocarrier-based drug delivery systems provide means of solving these problems at once. Herein, we present such a smart nanoparticle platform based on self-assembled, reduction-responsive amphiphilic graft copolymers, which were successfully synthesized through thiol-disulfide exchange reaction between thiolated hydrophilic block and pyridyl disulfide functionalized hydrophobic block. These amphiphilic graft copolymers self-assembled into nanoparticles with mean diameters of about 30-50 nm and readily incorporated hydrophobic guest molecules. Fluorescence correlation spectroscopy (FCS) was used to study nanoparticle stability and triggered release of a model compound in detail. Long-term colloidal stability and model compound retention within the nanoparticles was found when analyzed in cell media at body temperature. In contrast, rapid, complete reduction-triggered disassembly and model compound release was achieved within a physiological reducing environment. The synthesized copolymers revealed no intrinsic cellular toxicity up to 1 mg mL-1. Drug-loaded reduction-sensitive nanoparticles delivered a hydrophobic model anticancer drug (doxorubicin, DOX) to cancer cells (HeLa cells) and an experimental, metabolically unstable antimalarial drug (the serine hydroxymethyltransferase (SHMT) inhibitor (+/-)-1) to Plasmodium falciparum-infected red blood cells (iRBCs), with higher efficacy compared to similar, non-sensitive drug-loaded nanoparticles. These responsive copolymer-based nanoparticles represent a promising candidate as smart nanocarrier platform for various drugs to be applied to different diseases, due to the biocompatibility and biodegradability of the hydrophobic block, and the protein-repellent hydrophilic block.Medical applications of anticancer and antimalarial drugs often suffer from low aqueous

  15. Determination of the cationic amphiphilic drug-DNA binding mode and DNA-assisted fluorescence resonance energy transfer amplification

    Science.gov (United States)

    Yaseen, Zahid; Banday, Abdul Rouf; Hussain, Mohammed Aamir; Tabish, Mohammad; Kabir-ud-Din

    2014-03-01

    Understanding the mechanism of drug-DNA binding is crucial for predicting the potential genotoxicity of drugs. Agarose gel electrophoresis, absorption, steady state fluorescence, and circular dichroism have been used in exploring the interaction of cationic amphiphilic drugs (CADs) such as amitriptyline hydrochloride (AMT), imipramine hydrochloride (IMP), and promethazine hydrochloride (PMT) with calf thymus or pUC19 DNA. Agarose gel electrophoresis assay, along with absorption and steady state fluorescence studies, reveal interaction between the CADs and DNA. A comparative study of the drugs with respect to the effect of urea, iodide induced quenching, and ethidium bromide (EB) exclusion assay reflects binding of CADs to the DNA primarily in an intercalative fashion. Circular dichroism data also support the intercalative mode of binding. Besides quenching, there is fluorescence exchange energy transfer (FRET) in between CADs and EB using DNA as a template.

  16. Partitioning of small amphiphiles at surfactant bilayer/water interfaces: an avoided level crossing muon spin resonance study.

    Science.gov (United States)

    Scheuermann, Robert; Tucker, Ian M; Dilger, Herbert; Staples, Ed J; Ford, Gary; Fraser, Stuart B; Beck, Bettina; Roduner, Emil

    2004-03-30

    The temperature-dependent variation of local environment and reorientation dynamics of the small amphiphile 2-phenylethanol in lamellar phase dispersions of the dichain cationic surfactants, 2,3-diheptadecyl ester ethoxypropyl-1,1,1-trimethylammonium chloride (DHTAC) and dioctadecyldimethylammonium chloride (DODMAC), and the nonionic surfactant, tetra(ethylene glycol) n-dodecyl ether (C12E4), have been determined using avoided level crossing muon spin resonance spectroscopy (ALC-muSR). For cosurfactant radicals the hydrophobic or hydrophilic character of the surrounding media can be determined from their magnetic resonance signatures. Comparison of the three different bilayer-forming surfactant systems shows that the ALC-muSR technique is able to distinguish both major and subtle differences in the partitioning of the cosurfactant radicals between the different systems.

  17. Optimum design of amphiphilic polymers bearing hydrophobic groups for both cell surface ligand presentation and intercellular cross-linking.

    Science.gov (United States)

    Takeo, Masafumi; Li, Cuicui; Matsuda, Masayoshi; Nagai, Hiroko; Hatanaka, Wataru; Yamamoto, Tatsuhiro; Kishimura, Akihiro; Mori, Takeshi; Katayama, Yoshiki

    2015-01-01

    Amphiphilic polymers bearing hydrophobic alkyl groups are expected to be applicable for both ligand presentation on the cell surface and intercellular crosslinking. To explore the optimum design for each application, we synthesized eight different acyl-modified dextrans with varying molecular weight, alkyl length, and alkyl modification degree. We found that the behenate-modified polymers retained on the cell surface longer than the palmitate-modified ones. Since the polymers were also modified with biotin, streptavidin can be presented on the cell surface through biotin-streptavidin recognition. The duration of streptavidin on the cell surface is longer in the behenate-modified polymer than the palmitate-modified one. As for the intercellular crosslinking, the palmitate-modified polymers were more efficient than the behenate-modified polymers. The findings in this research will be helpful to design the acyl-modified polymers for the cell surface engineering.

  18. π-π interaction of aromatic groups in amphiphilic molecules directing for single-crystalline mesostructured zeolite nanosheets

    Science.gov (United States)

    Xu, Dongdong; Ma, Yanhang; Jing, Zhifeng; Han, Lu; Singh, Bhupendra; Feng, Ji; Shen, Xuefeng; Cao, Fenglei; Oleynikov, Peter; Sun, Huai; Terasaki, Osamu; Che, Shunai

    2014-06-01

    One of the challenges in material science has been to prepare macro- or mesoporous zeolite. Although examples of their synthesis exist, there is a need for a facile yet versatile approach to such hierarchical structures. Here we report a concept for designing a single quaternary ammonium head amphiphilic template with strong ordered self-assembling ability through π-π stacking in hydrophobic side, which stabilizes the mesostructure to form single-crystalline mesostructured zeolite nanosheets. The concept is demonstrated for the formation of a new type of MFI (zeolite framework code by International Zeolite Association) nanosheets joined with a 90° rotational boundary, which results in a mesoporous zeolite with highly specific surface area even after calcination. Low binding energies for this self-assembling system are supported by a theoretical analysis. A geometrical matching between the arrangement of aromatic groups and the zeolitic framework is speculated for the formation of single-crystalline MFI nanosheets.

  19. Polymerization Induced Self-Assembly of Alginate Based Amphiphilic Graft Copolymers Synthesized by Single Electron Transfer Living Radical Polymerization.

    Science.gov (United States)

    Kapishon, Vitaliy; Whitney, Ralph A; Champagne, Pascale; Cunningham, Michael F; Neufeld, Ronald J

    2015-07-13

    Alginate-based amphiphilic graft copolymers were synthesized by single electron transfer living radical polymerization (SET-LRP), forming stable micelles during polymerization induced self-assembly (PISA). First, alginate macroinitiator was prepared by partial depolymerization of native alginate, solubility modification and attachment of initiator. Depolymerized low molecular weight alginate (∼12 000 g/mol) was modified with tetrabutylammonium, enabling miscibility in anhydrous organic solvents, followed by initiator attachment via esterification yielding a macroinitiator with a degree of substitution of 0.02, or 1-2 initiator groups per alginate chain. Then, methyl methacrylate was polymerized from the alginate macroinitiator in mixtures of water and methanol, forming poly(methyl methacrylate) grafts, prior to self-assembly, of ∼75 000 g/mol and polydispersity of 1.2. PISA of the amphiphilic graft-copolymer resulted in the formation of micelles with diameters of 50-300 nm characterized by light scattering and electron microscopy. As the first reported case of LRP from alginate, this work introduces a synthetic route to a preparation of alginate-based hybrid polymers with a precise macromolecular architecture and desired functionalities. The intended application is the preparation of micelles for drug delivery; however, LRP from alginate can also be applied in the field of biomaterials to the improvement of alginate-based hydrogel systems such as nano- and microhydrogel particles, islet encapsulation materials, hydrogel implants, and topical applications. Such modified alginates can also improve the function and application of native alginates in food and agricultural applications.

  20. Molecular Differentiated Initiator Reactivity in the Synthesis of Poly(caprolactone-Based Hydrophobic Homopolymer and Amphiphilic Core Corona Star Polymers

    Directory of Open Access Journals (Sweden)

    Eileen Deng

    2015-11-01

    Full Text Available Macromolecules that possess three-dimensional, branched molecular structures are of great interest because they exhibit significantly differentiated application performance compared to conventional linear (straight chain polymers. This paper reports the synthesis of 3- and 4-arm star branched polymers via ring opening polymerisation (ROP utilising multi-functional hydroxyl initiators and Sn(Oct2 as precatalyst. The structures produced include mono-functional hydrophobic and multi-functional amphiphilic core corona stars. The characteristics of the synthetic process were shown to be principally dependent upon the physical/dielectric properties of the initiators used. ROP’s using initiators that were more available to become directly involved with the Sn(Oct2 in the “in-situ” formation of the true catalytic species were observed to require shorter reaction times. Use of microwave heating (MWH in homopolymer star synthesis reduced reaction times compared to conventional heating (CH equivalents, this was attributed to an increased rate of “in-situ” catalyst formation. However, in amphiphilic core corona star formation, the MWH polymerisations exhibited slower propagation rates than CH equivalents. This was attributed to macro-structuring within the reaction medium, which reduced the potential for reaction. It was concluded that CH experiments were less affected by this macro-structuring because it was disrupted by the thermal currents/gradients caused by the conductive/convective heating mechanisms. These gradients are much reduced/absent with MWH because it selectively heats specific species simultaneously throughout the entire volume of the reaction medium. These partitioning problems were overcome by introducing additional quantities of the species that had been determined to selectively heat.