A Nanoparticle Approach towards Morphology Controlled Organic Photovoltaics (OPV)

DEFF Research Database (Denmark)

Andersen, Thomas Rieks; Yan, Quanxiang; Larsen-Olsen, Thue Trofod

2012-01-01

Silicon nano-particles grafted with two different organic oligomers were prepared; the oligomers used were a phenylene-vinylene (PV) oligomer and a 3,3'''-didodecylquaterthiophene. The graftings were performed by the use of two different functional groups, the PV oligomer was grafted by a hydroxy...

Au-nanoparticles grafted on plasma treated PE

International Nuclear Information System (INIS)

Svorcik, V.; Chaloupka, A.; Rezanka, P.; Slepicka, P.; Kolska, Z.; Kasalkova, N.; Hubacek, T.; Siegel, J.

2010-01-01

Polyethylene (PE) surface was treated with Ar plasma. Activated surface was grafted from methanol solution of 1,2-ethanedithiol. Then the sample was immersed into freshly prepared colloid solution of Au-nanoparticles. Finally Au layer was sputtered on the samples. Properties of the modified PE were studied using various methods: AFM, EPR, RBS and nanoindentation. It was shown that the plasma treatment results in degradation of polymer chain (AFM) and creation of free radicals by EPR. After grafting with dithiol, the concentration of free radicals declines. The presence of Au and S in the surface layer after the coating with Au-nanoparticles was proved by RBS. Plasma treatment changes PE surface morphology and increases surface roughness, too. Another significant change in surface morphology and roughness was observed after deposition of Au-nanoparticles. Nanoindentation measurements show that the grafting with Au-nanoparticles increases adhesion of subsequently sputtered Au layer.

Structure of Solvent-Free Nanoparticle−Organic Hybrid Materials

KAUST Repository

Yu, Hsiu-Yu

2010-11-16

We derive the radial distribution function and the static structure factor for the particles in model nanoparticleorganic hybrid materials composed of nanoparticles and attached oligomeric chains in the absence of an intervening solvent. The assumption that the oligomers form an incompressible fluid of bead-chains attached to the particles that is at equilibrium for a given particle configuration allows us to apply a density functional theory for determining the equilibrium configuration of oligomers as well as the distribution function of the particles. A quasi-analytic solution is facilitated by a regular perturbation analysis valid when the oligomer radius of gyration R g is much greater than the particle radius a. The results show that the constraint that each particle carries its own share of the fluid attached to itself yields a static structure factor that approaches zero as the wavenumber approaches zero. This result indicates that each particle excludes exactly one other particle from its neighborhood. © 2010 American Chemical Society.

Solvent-mediated pathways to gelation and phase separation in suspensions of grafted nanoparticles

KAUST Repository

Anyfantakis, Manos; Bourlinos, Athanasios; Vlassopoulos, Dimitris; Fytas, George; Giannelis, Emmanuel; Kumar, Sanat K.

2009-01-01

, rheology and visual observations, and different routes to gelation, depending on the solvent used. In agreement with earlier works, the solvent quality for the grafted chains at a given temperature controls the balance between attractions and repulsions

Effects of solvents on the radiation grafting reaction of vinyl compounds on poly (3-hydroxybutyrate)

International Nuclear Information System (INIS)

Torres, Maykel González; Talavera, José Rogelio Rodríguez; Muñoz, Susana Vargas; Pérez, Manuel González; Castro, Ma. Pilar. Carreón.; Cortes, Jorge Cerna

2015-01-01

Vinyl Acetate was grafted onto poly (3-hydroxybutyrate) by the simultaneous gamma irradiation method using different types of solvents and in bulk (solvent free), at 10 kGy and 1.62 kGy/h dose and dose rate respectively. Subsequent complete hydrolysis allowed the conversion of grafted chains from poly (vinyl acetate) to poly (vinyl alcohol). The aim of this study is to determine the effect of solvent through the estimation of the dependence of the degree of grafting with the choice of solvent, the calculation of the degree of crystallinity, and to study the biodegradation of the products. The results showed a greater degree of grafting in bulk, while the more suitable solvent was hexane. Characterization of the grafted copolymer indicated that crystallinity percentage decreased by an increase in grafting, while the biodegradability was promoted by the increment in poly (vinyl alcohol) grafted. - Highlights: • PHB was indirectly grafted with PVA, by complete hydrolysis of grafted PVAc. • The effect of solvents on the grafting, crystallinity and biodegradation was studied. • The characterizations of the products were obtained by SEM, TGA, and DSC

Effects of solvent polarity on mutual polypropylene grafting by electron beam irradiation

International Nuclear Information System (INIS)

Geraldo, A.B.C.; Moura, E.; Somessari, E.S.R.; Silveira, C.G.; Paes, H.A.; Souza, C.A.; Fernandes, W.; Manzoli, J.E.

2011-01-01

Complete text of publication follows. Copolymerization by grafting is a process largely known and the advantages of modifying polymers by radiation includes superimposition of properties related to the backbone and the grafted chains in the absence of an initiator. This process produces low byproduct levels, costs and hazards. Since polypropylene is applied in many industrial and commercial sectors, the grafting process is an alternative to improve some of its physical and chemical properties. The aim of this work was to verify the effect of distinct organic solvents on polypropylene grafting process by mutual irradiation applying absorbed doses from 30 kGy to 100 kGy at dose rates of 2.2 kGy/s and 22.4 kGy/s. All process were performed in atmosphere air presence. Styrene was the monomer grafted on polymer substrate and some non-polar and polar organic solvents, like toluene, xylene, acetone, methanol and its homologous, were used at distinct concentrations. The grafted samples were evaluated by degree of styrene grafting (gravimetric determination) and the Mid-FTIR spectrophotometry. As a general behavior, the degree of grafting increases when absorbed dose values increase in a specific solvent until a maximum dose value (50-70 kGy), after this, the degree of grafting decreases. Moreover, the grafting process have high yields when protic polar solvents are used. These results suggest the grafting process does not have dependence of substrate swelling, that is expected when a non-polar substrate and a non-polar media are in contact. The grafting, in this case, can be related to the free radical generation at protic polar solvents in a first step of process mechanism; these reactive specimens start the reaction on substrate surface to allow the accessibility of monomer species to active sites. Some reaction mechanisms are proposed.

Solvent-Free Synthesis of Silver-Nanoparticles and their Use as Additive in Poly (Dicyclopentadiene)

International Nuclear Information System (INIS)

Abbas, M.; Kienberger, J.

2013-01-01

A solvent-free environmentally benign synthesis of oleylamine capped silver nanoparticles is presented. Upon heating 10 equivalents of oleylamine and silver nitrate at 165 degree C for 30 min followed by a precipitation step using ethanol as the precipitant particles characterized by an Z-average diameter of 63 nm were obtained. Dried particles can be easily redispersed in unpolar solvents or monomers, which pave the way for using them as an antimicrobial additive in polymeric materials. In particular, newly prepared Ag-particles were dispersed in dicyclopentadiene and the mixture was cured using ring opening metathesis polymerization yielding an antimicrobially equipped duroplastic material. (author)

Steady State and Time-Resolved Fluorescence Dynamics of Triphenylamine Based Oligomers with Phenylene/Thiophene/Furan in Solvents

International Nuclear Information System (INIS)

Qi, Zeng; Ying-Liang, Liu; Kang, Meng; Xiang-Jie, Zhao; Shu-Feng, Wang; Qi-Huang, Gong

2009-01-01

We investigate the photo-physical properties of a series of triphenylamine-based oligomers by steady-state and picosecond transient fluorescence measurements in solvents. The oligomers are composed alternatively with triphenylamine and phenylene/thiophene/furan group, bridged by vinyl group (PNB/PNT/PNF). Their fluorescence spectra show bathochromic phenomenon with solvent polarity and viscosity increasing. The fluorescence decays are bi-exponential for PNB and PNT, and tri-exponential for PNF in THF and aniline. The strong viscosity dependence suggests conformational relaxation along the PNF chain after photo excitation. (condensed matter: electronicstructure, electrical, magnetic, and opticalproperties)

Facile and solvent-free routes for the synthesis of size-controllable Fe3O4 nanoparticles

International Nuclear Information System (INIS)

Ngo, Thanh Hieu; Tran, Dai Lam; Do, Hung Manh; Le, Van Hong; Nguyen, Xuan Phuc; Tran, Vinh Hoang

2010-01-01

Magnetite nanoparticles are one of the most important materials that are widely used in both medically diagnostic and therapeutic research. In this paper, we present some facile and non-toxic synthetic approaches for size-controllable preparations of magnetite nanoparticles, which are appropriate for biomedical applications, namely (i) co-precipitation; (ii) reduction–precipitation and (iii) oxidation–precipitation. Magnetic characterizations of the obtained nanoparticles have been studied and discussed. The oxidation precipitation route was chosen for investigation of the dependence of kinetic driven activation energy and that of coercive force on particle size (and temperature) during the course of the reaction. The structural–magnetic behavior was also correlated. Being solvent and surfactant-free, these methods are advantageous for synthesis and further functionalization towards biomedical applications

Using solvent-free sample preparation to promote protonation of poly(ethylene oxide)s with labile end-groups in matrix-assisted laser desorption/ionisation.

Science.gov (United States)

Mazarin, Michael; Phan, Trang N T; Charles, Laurence

2008-12-01

Protonation is usually required to observe intact ions during matrix-assisted laser desorption/ionization (MALDI) of polymers containing fragile end-groups while cation adduction induces chain-end degradation. These polymers, generally obtained via living free radical polymerization techniques, are terminated with a functionality in which a bond is prone to homolytic cleavage, as required by the polymerization process. A solvent-free sample preparation method was used here to avoid salt contaminant from the solvent traditionally used in the dried-droplet MALDI procedure. Solvent-based and solvent-free sample preparations were compared for a series of three poly(ethylene oxide) polymers functionalized with a labile end-group in a nitroxide-mediated polymerization reaction, using 2,4,6-trihydroxyacetophenone (THAP) as the matrix without any added salt. Intact oligomer ions could only be produced as protonated molecules in solvent-free MALDI while sodium adducts of degraded polymers were formed from the dried-droplet samples. Although MALDI analysis was performed at the laser threshold, fragmentation of protonated macromolecules was still observed to occur. However, in contrast to sodiated molecules, dissociation of protonated oligomers does not involve the labile C--ON bond of the end-group. As the macromolecule size increased, protonation appeared to be less efficient and sodium adduction became the dominant ionization process, although no sodium salt was added in the preparation. Formation of sodiated degraded macromolecules would be dictated by increasing cation affinity as the size of the oligomers increases and would reveal the presence of salts at trace levels in the MALDI samples.

Tumor delivery of antisense oligomer using trastuzumab within a streptavidin nanoparticle

Energy Technology Data Exchange (ETDEWEB)

Wang, Yi [University of Massachusetts Medical School, Division of Nuclear Medicine, Department of Radiology, Worcester, MA (United States); Yale University, Yale PET Center, Department of Diagnostic Radiology, New Haven, CT (United States); Liu, Xinrong; Chen, Ling; Cheng, Dengfeng; Rusckowski, Mary [University of Massachusetts Medical School, Division of Nuclear Medicine, Department of Radiology, Worcester, MA (United States); Hnatowich, Donald J. [University of Massachusetts Medical School, Division of Nuclear Medicine, Department of Radiology, Worcester, MA (United States); Umass Medical School, Department of Radiology, Worcester, MA (United States)

2009-12-15

Trastuzumab (Herceptin trademark) is often internalized following binding to Her2+ tumor cells. The objective of this study was to investigate whether trastuzumab can be used as a specific carrier to deliver antisense oligomers into Her2+ tumor cells both in vitro and in vivo. A biotinylated MORF oligomer antisense to RhoC mRNA and its biotinylated sense control were labeled with either lissamine for fluorescence detection or {sup 99m}Tc for radioactivity detection and were linked to biotinylated trastuzumab via streptavidin. The nanoparticles were studied in SUM190 (RhoC+, Her2+) study and SUM149 (RhoC+, Her2-) control cells in culture and as xenografts in mice. As evidence of unimpaired Her2+ binding of trastuzumab within the nanoparticle, accumulations were clearly higher in SUM190 compared to SUM149 cells and, by whole-body imaging, targeting of SUM190 tumor was similar to that expected for a radiolabeled trastuzumab. As evidence of internalization, fluorescence microscopy images of cells grown in culture and obtained from xenografts showed uniform cytoplasm distribution of the lissamine-MORF. An invasion assay showed decreased RhoC expression in SUM190 cells when incubated with the antisense MORF nanoparticles at only 100 nM. Both in cell culture and in animals, the nanoparticle with trastuzumab as specific carrier greatly improved tumor delivery of the antisense oligomer against RhoC mRNA into tumor cells overexpressing Her2 and may be of general utility. (orig.)

Optical characterization of CdS nanoparticles embedded into the comb-type amphiphilic graft copolymer

Science.gov (United States)

Kalaycı, Özlem A.; Duygulu, Özgür; Hazer, Baki

2013-01-01

This study refers to the synthesis and characterization of a novel organic/inorganic hybrid nanocomposite material containing cadmium sulfide (CdS) nanoparticles. For this purpose, a series of polypropylene (PP)-g-polyethylene glycol (PEG), PP-g-PEG comb-type amphiphilic graft copolymers were synthesized. PEGs with Mn = 400, 2000, 3350, and 8000 Da were used and the graft copolymers obtained were coded as PPEG400, PPEG2000, PPEG3350, and PPEG8000. CdS nanoparticles were formed in tetrahydrofuran solution of PP-g-PEG amphiphilic comb-type copolymer by the reaction between aqueous solutions of Na2S and Cd(CH3COO)2 simultaneously. Micelle formation of PPEG2000 comb-type amphiphilic graft copolymer in both solvent/non-solvent (petroleum ether-THF) by transmission electron microscopy (TEM). The optical characteristics, size morphology, phase analysis, and dispersion of CdS nanoparticles embedded in PPEG400, PPEG2000, PPEG3350, and PPEG8000 comb-type amphiphilic graft copolymer micelles were determined by high resolution TEM (HRTEM), energy dispersive spectroscopy, UV-vis spectroscopy, and fluorescence emission spectroscopy techniques. The aggregate size of PPEG2000-CdS is between 10 and 50 nm; however, in the case of PPEG400-CdS, PPEG3350-CdS, and PPEG8000-CdS samples, it is up to approximately 100 nm. The size of CdS quantum dots in the aggregates for PPEG2000 and PPEG8000 samples was observed as 5 nm by HRTEM analysis, and this result was also supported by UV-vis absorbance spectra and fluorescence emission spectra.

Optical characterization of CdS nanoparticles embedded into the comb-type amphiphilic graft copolymer

Energy Technology Data Exchange (ETDEWEB)

Kalayc Latin-Small-Letter-Dotless-I , Oezlem A. [Bulent Ecevit University, Department of Physics (Turkey); Duygulu, Oezguer [TUBITAK Marmara Research Center, Materials Institute (Turkey); Hazer, Baki, E-mail: bkhazer@karaelmas.edu.tr [Bulent Ecevit University, Department of Chemistry (Turkey)

2013-01-15

This study refers to the synthesis and characterization of a novel organic/inorganic hybrid nanocomposite material containing cadmium sulfide (CdS) nanoparticles. For this purpose, a series of polypropylene (PP)-g-polyethylene glycol (PEG), PP-g-PEG comb-type amphiphilic graft copolymers were synthesized. PEGs with Mn = 400, 2000, 3350, and 8000 Da were used and the graft copolymers obtained were coded as PPEG400, PPEG2000, PPEG3350, and PPEG8000. CdS nanoparticles were formed in tetrahydrofuran solution of PP-g-PEG amphiphilic comb-type copolymer by the reaction between aqueous solutions of Na{sub 2}S and Cd(CH{sub 3}COO){sub 2} simultaneously. Micelle formation of PPEG2000 comb-type amphiphilic graft copolymer in both solvent/non-solvent (petroleum ether-THF) by transmission electron microscopy (TEM). The optical characteristics, size morphology, phase analysis, and dispersion of CdS nanoparticles embedded in PPEG400, PPEG2000, PPEG3350, and PPEG8000 comb-type amphiphilic graft copolymer micelles were determined by high resolution TEM (HRTEM), energy dispersive spectroscopy, UV-vis spectroscopy, and fluorescence emission spectroscopy techniques. The aggregate size of PPEG2000-CdS is between 10 and 50 nm; however, in the case of PPEG400-CdS, PPEG3350-CdS, and PPEG8000-CdS samples, it is up to approximately 100 nm. The size of CdS quantum dots in the aggregates for PPEG2000 and PPEG8000 samples was observed as 5 nm by HRTEM analysis, and this result was also supported by UV-vis absorbance spectra and fluorescence emission spectra.

Optical characterization of CdS nanoparticles embedded into the comb-type amphiphilic graft copolymer

International Nuclear Information System (INIS)

Kalaycı, Özlem A.; Duygulu, Özgür; Hazer, Baki

2013-01-01

This study refers to the synthesis and characterization of a novel organic/inorganic hybrid nanocomposite material containing cadmium sulfide (CdS) nanoparticles. For this purpose, a series of polypropylene (PP)-g-polyethylene glycol (PEG), PP-g-PEG comb-type amphiphilic graft copolymers were synthesized. PEGs with Mn = 400, 2000, 3350, and 8000 Da were used and the graft copolymers obtained were coded as PPEG400, PPEG2000, PPEG3350, and PPEG8000. CdS nanoparticles were formed in tetrahydrofuran solution of PP-g-PEG amphiphilic comb-type copolymer by the reaction between aqueous solutions of Na 2 S and Cd(CH 3 COO) 2 simultaneously. Micelle formation of PPEG2000 comb-type amphiphilic graft copolymer in both solvent/non-solvent (petroleum ether–THF) by transmission electron microscopy (TEM). The optical characteristics, size morphology, phase analysis, and dispersion of CdS nanoparticles embedded in PPEG400, PPEG2000, PPEG3350, and PPEG8000 comb-type amphiphilic graft copolymer micelles were determined by high resolution TEM (HRTEM), energy dispersive spectroscopy, UV–vis spectroscopy, and fluorescence emission spectroscopy techniques. The aggregate size of PPEG2000-CdS is between 10 and 50 nm; however, in the case of PPEG400-CdS, PPEG3350-CdS, and PPEG8000-CdS samples, it is up to approximately 100 nm. The size of CdS quantum dots in the aggregates for PPEG2000 and PPEG8000 samples was observed as 5 nm by HRTEM analysis, and this result was also supported by UV–vis absorbance spectra and fluorescence emission spectra.

Development and Modeling of a Novel Self-Assembly Process for Polymer and Polymeric Composite Nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Sumpter, Bobby G. [ORNL; Carrillo, Jan-Michael Y. [ORNL; Ahn, Suk-Kyun [ORNL; Barnes, Mike D. [University of Massachusetts, Amherst; Shelton, William A. [Pacific Northwest National Laboratory (PNNL); Harrison, Robert J. [Stony Brook University (SUNY); W. Noid, Donald [Retired

2017-10-01

Extensive computational simulations and experiments have been used to investigate the structure, dynamics and resulting photophysical properties of a number para-phenylenevinylene (PPV) based polymers and oligomers. These studies have shown how the morphology and structure are controlled to a large extent by the nature of the solute-solvent interactions in the initial solution phase preparation. A good solvent such as dichloromethane generates non-compact structures with more of a defect-extended chain like morphology while a bad solvent such as toluene leads to compact organized and folded structures with rod-like morphologies. Secondary structural organization is induced by using the solution phase structures to generate solvent-free single molecule nanoparticles. These nanoparticles are very compact and rod shaped, consisting of near-cofacial ordering of the conjugated PPV chain backbones between folds located at tetrahedral defects (sp3 C-C bonds). The resulting photophysical properties exhibit a significant enhancement in the photoluminescence quantum yield, lifetime, and stability. In addition, the single molecule nanoparticles have Gaussian-like emission spectra with discrete center frequencies that are correlated to a conjugation length, allowing the design of nanoparticles which luminesces at a particular frequency. We followed a similar approach and applied a comparable methodology in our recent work on polythiophenes in order to study the effect of polymer architecture on nanoscale assembly. Unlike linear chains of comparable size, we observed aggregation of the bottlebrush architecture of poly(norbornene)-g-poly(3-hexylthiophene) (PNB-g-P3HT) after the freeze-drying and dissolution processes. The behavior can be attributed to a significant enhancement in the number of π-π interactions between grafted P3HT side chains.

Polyaspartamide-Polylactide Graft Copolymers with Tunable Properties for the Realization of Fluorescent Nanoparticles for Imaging.

Science.gov (United States)

Craparo, Emanuela Fabiola; Porsio, Barbara; Mauro, Nicolò; Giammona, Gaetano; Cavallaro, Gennara

2015-08-01

Here, the synthesis and the characterization of novel amphiphilic graft copolymers with tunable properties, useful in obtaining polymeric fluorescent nanoparticles for application in imaging, are described. These copolymers are obtained by chemical conjugation of rhodamine B (RhB) moieties, polylactic acid (PLA), and O-(2-aminoethyl)-O'-methyl poly(ethylene glycol) (PEG) on α,β-poly(N-2-hydroxyethyl)-D,L-aspartamide (PHEA). In particular, PHEA is first functionalized with RhB to obtain PHEA-RhB with a derivatization degree in RhB (DDRhB ) equal to 0.55 mol%. By varying the reaction conditions, different amounts of PLA are grafted on PHEA-RhB to obtain PHEA-RhB-PLA with DDPLA equal to 1.9, 4.0, and 6.2 mol%. Then, PEG chains are grafted on PHEA-RhB-PLA derivatives to obtain PHEA-RhB-PLA-PEG graft copolymers. The preparation of polymeric fluorescent nanoparticles with tunable properties and spherical shape is described by using PHEA-RhB-PLA-PEG with DD in PLA and PEG equal to 4.0 and 4.9 mol%, by following easily scaling up processes, such as emulsion-solvent evaporation and high pressure homogenization (HPH)-solvent evaporation techniques. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solvent-free formation of hydroxyapatite coated biodegradable particles via nanoparticle-stabilized emulsion route

International Nuclear Information System (INIS)

Okada, Masahiro; Fujii, Syuji; Nishimura, Taiki; Nakamura, Yoshinobu; Takeda, Shoji; Furuzono, Tsutomu

2012-01-01

Highlights: ► Hydroxyapatite (HAp) nanoparticles stabilized polymer melt-in-water emulsions without any molecular surfactants. ► Interaction between polymer and HAp played a crucial role. ► HAp-coated polymer particles were obtained from the emulsions without any organic solvents. - Abstract: Hydroxyapatite (HAp) nanoparticle-coated biodegradable polymer particles were fabricated from a nanoparticle-stabilized emulsion in the absence of any molecular surfactants or organic solvents. First, a polymer melt-in-water emulsion was prepared by mixing a water phase containing nanosized HAp particles as a particulate emulsifier and an oil phase consisting of poly(ε-caprolactone) (PCL) or poly(L-lactide-co-ε-caprolactone) (P(LLA-CL)) above its melting point. It was clarified that the interaction between ester/carboxyl groups of the polymers and the HAp nanoparticles at the polymer–water interface played a crucial role to prepare the nanoparticle-stabilized emulsion. The HAp nanoparticle-coated biodegradable polymer particle (a polymer solid-in-water emulsion) was fabricated by cooling the emulsion. The particle morphology and particle size were evaluated using scanning electron microscope.

Equilibrium shift in solution: molecular shape recognition and precipitation of a synthetic double helix using helicene-grafted silica nanoparticles.

Science.gov (United States)

Miyagawa, Masamichi; Ichinose, Wataru; Yamaguchi, Masahiko

2014-01-27

Chiral silica nanoparticles (70 nm) grafted with (P)-helicene recognized the molecular shape of double helix and random coil (P)-ethynylhelicene oligomers in solution. A mixture of the (P)-nanoparticles and double helix precipitated much faster than a mixture of the (P)-nanoparticles and random coil, and the precipitate contained only the double helix. The mixture of the (P)-nanoparticles and (P)-ethynylhelicene pentamer reversibly dispersed in trifluoromethylbenzene upon heating at 70 °C and precipitated upon cooling at 25 °C. When a 10:90 equilibrium mixture of the double helix and random coil in solution was treated with the (P)-nanoparticles, the double helix was precipitated in 53% yield and was accompanied by equilibrium shift. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoparticle for delivery of antisense γPNA oligomers targeting CCR5.

Science.gov (United States)

Bahal, Raman; McNeer, Nicole Ali; Ly, Danith H; Saltzman, W Mark; Glazer, Peter M

2013-01-01

The development of a new class of peptide nucleic acids (PNAs), i.e., gamma PNAs (γPNAs), creates the need for a general and effective method for its delivery into cells for regulating gene expression in mammalian cells. Here we report the antisense activity of a recently developed hydrophilic and biocompatible diethylene glycol (miniPEG)-based gamma peptide nucleic acid called MPγPNAs via its delivery by poly(lactide-co-glycolide) (PLGA)-based nanoparticle system. We show that MPγPNA oligomers designed to bind to the selective region of chemokine receptor 5 (CC R5) transcript, induce potent and sequence-specific antisense effects as compared with regular PNA oligomers. In addition, PLGA nanoparticle delivery of MPγPNAs is not toxic to the cells. The findings reported in this study provide a combination of γPNA technology and PLGA-based nanoparticle delivery method for regulating gene expression in live cells via the antisense mechanism.

Electrografting of conductive oligomers and polymers using diazonium electroreduction

International Nuclear Information System (INIS)

Lacroix, Jean Christophe; Trippe-Allard, Gaelle; Ghilane, Jalal; Martin, Pascal

2014-01-01

This paper describes the attachment of conjugated oligomers onto electrode surface through the reduction of diazonium compounds. In this connection some properties of conjugated oligomers and of layers grafted through diazonium electroreduction will first be briefly presented. The electrochemical behavior of conjugated oligomers grafted on a surface using diazonium electroreduction will then be discussed. (paper)

Electrografting of conductive oligomers and polymers using diazonium electroreduction

Science.gov (United States)

Lacroix, Jean Christophe; Trippe-Allard, Gaelle; Ghilane, Jalal; Martin, Pascal

2014-03-01

This paper describes the attachment of conjugated oligomers onto electrode surface through the reduction of diazonium compounds. In this connection some properties of conjugated oligomers and of layers grafted through diazonium electroreduction will first be briefly presented. The electrochemical behavior of conjugated oligomers grafted on a surface using diazonium electroreduction will then be discussed.

Antioxidant Activity of Hispidin Oligomers from Medicinal Fungi: A DFT Study

Directory of Open Access Journals (Sweden)

El Hassane Anouar

2014-03-01

Full Text Available Hispidin oligomers are styrylpyrone pigments isolated from the medicinal fungi Inonotus xeranticus and Phellinus linteus. They exhibit diverse biological activities and strong free radical scavenging activity. To rationalize the antioxidant activity of a series of four hispidin oligomers and determine the favored mechanism involved in free radical scavenging, DFT calculations were carried out at the B3P86/6-31+G (d, p level of theory in gas and solvent. The results showed that bond dissociation enthalpies of OH groups of hispidin oligomers (ArOH and spin density delocalization of related radicals (ArO• are the appropriate parameters to clarify the differences between the observed antioxidant activities for the four oligomers. The effect of the number of hydroxyl groups and presence of a catechol moiety conjugated to a double bond on the antioxidant activity were determined. Thermodynamic and kinetic studies showed that the PC-ET mechanism is the main mechanism involved in free radical scavenging. The spin density distribution over phenoxyl radicals allows a better understanding of the hispidin oligomers formation.

Sorption behaviour of polystyrene grafted sago starch in various solvents

International Nuclear Information System (INIS)

Janarthanan, P.; Yunus, W.M.Z.W.; Ahmed, M.B.; Rahman, M.Z.; Haron, M.J.; Silong, S.

2001-01-01

This paper describes swelling properties of polystyrene grafted sago starch in dimethyl sulfoxide (DMSO); chloroform (CHCl/sub 3/), water, acetone carbon tetrachloride (CCl/sub 4/) cyclohexanone and toluene. The copolymer for this study was prepared by grafting styrene onto sago starch using ceric ammonium nitrate as a redox initiator. Solvent uptake of the copolymer with respect to time was obtained by soaking the samples in chosen solvents for various time intervals at 25+-1 degree centigrade. The results obtained from swelling of polystyrene grafted sago starch in polar and non polar solvents showed that the percentage of swelling at equilibrium and the swelling rate coefficient decreased in the following order: DMSO > water > acetone cyclohexanone approx. CHCl/sub 3/ > toluene approx. CCl/sub 4/. Dimethyl sulfoxide showed the highest percentage of swelling at equilibrium that is 765%. Diffusions of the solvents onto the polymers were found to be of a Fickian only for DMSO. (author)

Synthesis and characterization of solvent-free ionic molybdenum disulphide (MoS2) nanofluids

International Nuclear Information System (INIS)

Gu, Shu-Ying; Gao, Xie-Feng; Zhang, Yi-Han

2015-01-01

A development of the novel and stable solvent-free ionic MoS 2 nanofluids by a facile and scalable hydrothermal method is presented. The nanofluids were synthesized by surface functionalizing nanoscale MoS 2 from hydrothermal synthesis with a charged corona, and ionically tethering with oligomeric chains as a canopy. The structures and properties of the nanofluids were characterized by Fourier transform infrared (FTIR), nuclear magnetic resonance (NMR, 1 H), differential scanning calorimeter (DSC), thermogravimetric analysis (TGA) and ARES rheometer. The obtained solvent-free nanofluids are homogeneous, stable amber-like fluids with no evidence of phase separation. The nanofluids could be easily dispersed in both aqueous and organic solvents to form transparent and stable liquids due to the ionic nature and the presence of oligomeric polymer chains. It was found that the solvent-free nanofluids with up to 32 wt% inorganic content show Newtonian rheological behaviors due to the high graft density and uniform dispersion of inorganic cores, indicating that the nanofluids would have a stable lubricating performance. As reported in our previous communication, the nanofluids showing lower, more stable friction coefficients of less than 0.1 with self-healing lubricating behaviors. For deeper understanding of the nanofluids, the details of synthesis, chemical structures, rheological behaviors and molecular dynamics of the nanofluids were investigated in details. The rheological behaviors can be tailored by varying the grafting density of the canopy. Dynamic results of the canopy of the MoS 2 nanofluids show that inorganic MoS 2 cores have hindrance effect on the canopy segmental motions above 253 K due to their effect to the mobility of anions and the departing-recombining motions between the paired cations and anions. - Highlights: • A development of the novel synthesis of solvent-free MoS 2 nanofluids is presented. • The rheological behaviors can be tailored by

Effects of organic solvents on hyaluronic acid nanoparticles obtained by precipitation and chemical crosslinking.

Science.gov (United States)

Bicudo, Rafaela Costa Souza; Santana, Maria Helena Andrade

2012-03-01

Hyaluronic acid is a hydrophilic mucopolysaccharide composed of alternating units of D-glucuronic acid and N-acetylglucosamine. It is used in many medical, pharmaceutical, and cosmetic applications, as sponges, films, or particle formulations. Hyaluronic acid nanoparticles can be synthesized free of oil and surfactants by nanoprecipitation in organic solvents, followed by chemical crosslinking. The organic solvent plays an important role in particles size and structure. Therefore, this study aimed to investigate the influence of acetone, ethanol, and isopropyl alcohol on the synthesis and physico-chemical properties of hyaluronic acid nanoparticles. Particles were crosslinked with adipic hydrazide and chloride carbodiimide under controlled conditions. The nanoparticles obtained with all three studied solvents were moderately electrostatically stable. Experiments with acetone produced the smallest particle size (120.44 nm) and polydispersity (0.27). The size and polydispersity of hyaluronic acid nanoparticles correlated with the surface tension between water and the organic solvents, not with the thermodynamic affinity of water for the organic solvents.

Grafting of gold nanoparticles on polyethyleneterephthalate using dithiol interlayer

International Nuclear Information System (INIS)

Reznickova, A.; Kolska, Z.; Zaruba, K.; Svorcik, V.

2014-01-01

Two different procedures of grafting of polyethyleneterephthalate (PET), modified by plasma treatment, with gold nanoparticles (nanospheres) are studied. In the first procedure the PET foil was grafted with biphenyl-4,4′-dithiol and subsequently with gold nanoparticles. In the second one the PET foil was grafted with gold nanoparticles previously coated by the same dithiol. X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and electrokinetic analysis were used for characterization of the polymer surface at different modification steps. Gold nanoparticles were characterized by ultraviolet–visible spectroscopy. The first procedure was found to be more effective. It was proved that the dithiol was chemically bonded to the surface of the plasma activated PET and it mediates subsequent grafting of the gold nanoparticles. - Highlights: • Two different techniques were used for coating of PET with gold nanoparticles. • Grafted GNPs were characterized by XPS, FTIR, UV–vis, zeta potential, AFM. • More effective coating is achieved by deposition of GNPs earlier grafted with thiol. • The studied structures may have potential application in electronics or biomedicine

Synthesis of ligand-free CZTS nanoparticles via a facile hot injection route

DEFF Research Database (Denmark)

Mirbagheri, Naghmehalsadat; Engberg, Sara Lena Josefin; Crovetto, Andrea

2016-01-01

and toxic solvents that otherwise could hinder grain growth and limit the deposition techniques. In addition the synthesis route presented here results in nanoparticles of a large size compared to other ligand-free CZTS nanoparticles, due to the high boiling point of the solvents selected. Large particle...

Enthalpies of solvation of ethylene oxide oligomers CH{sub 3}O(CH{sub 2}CH{sub 2}O){sub n}CH{sub 3} (n = 1 to 4) in different H-bonding solvents: Methanol, chloroform, and water. Group contribution method as applied to the polar oligomers

Energy Technology Data Exchange (ETDEWEB)

Barannikov, Vladimir P., E-mail: vpb@isc-ras.ru [Institute of Solution Chemistry, Russian Academy of Sciences, Academicheskaya Str. 1, Ivanovo 153045 (Russian Federation); Guseynov, Sabir S.; Vyugin, Anatoliy I. [Institute of Solution Chemistry, Russian Academy of Sciences, Academicheskaya Str. 1, Ivanovo 153045 (Russian Federation)

2011-12-15

Highlights: > Solvation enthalpy is found for ethylene oxide oligomers in chloroform and methanol. > Coefficients of solute-solute interaction are determined for oligomers in methanol. > Enthalpies of hydrogen bonding of oligomers with chloroform and water are estimated. > Additivity scheme is developed for describing enthalpies of solvation of oligomers. - Abstract: The enthalpies of solution and solvation of ethylene oxide oligomers CH{sub 3}O(CH{sub 2}CH{sub 2}O){sub n}CH{sub 3} (n = 1 to 4) in methanol and chloroform have been determined from calorimetric measurements at T = 298.15 K. The enthalpic coefficients of pairwise solute-solute interaction for methanol solutions have been calculated. The enthalpic characteristics of the oligomers in methanol, chloroform, water and tetrachloromethane have been compared. The hydrogen bonding of the oligomers with chloroform and water molecules is exhibited in the values of solvation enthalpy and coefficient of solute-solute interaction. This effect is not observed for methanol solvent. The thermochemical data evidence an existence of multi-centred hydrogen bonds in associates of polyethers with the solvent molecules. Enthalpies of hydrogen bonding of the oligomers with chloroform and water have been estimated. The additivity scheme has been developed to describe the enthalpies of solvation of ethylene oxide oligomers, unbranched monoethers and n-alkanes in chloroform, methanol, water, and tetrachloromethane. The correction parameters for contribution of repeated polar groups and correction term for methoxy-compounds have been introduced. The obtained group contributions permit to describe the enthalpies of solvation of unbranched monoethers and ethylene oxide oligomers in the solvents with standard deviation up to 0.6 kJ . mol{sup -1}. The values of group contributions and corrections are strongly influenced by solvent properties.

Effect of solubility parameter of solvents on electron beam induced graft-polymerization onto polyethylene films

International Nuclear Information System (INIS)

Mori, Koji; Koshiishi, Kenji; Masuhara, Ken-ichi

1992-01-01

Electron beam induced graft-polymerization by the mutual irradiation technique of methyl methacrylate (MMA) and methacrylic acid (MAAc) blended with solvents, which have different solubility parameters δ, onto high density polyethylene films (PE) were investigated at high dose rates (25 Mrad per second). Graft-polymerization mechanisms were discussed on the basis of grafting rates, surface tensions, atomic rations on the surface by XPS, and SEM images of the grafted films. Grafting rates decreased with increasing δ of solvents, and grafting rates for MMA were larger than those for MAAc. Graft chain contents on the surface, which were evaluated in terms of surface tensions and atomic ratios on the surface, increased with increasing δ of solvents, and graft chain contents on the surface of MAAc grafted PE were higher than those of MMA grafted PE. It is assumed that mutual solubility of PE and solvents (monomer solutions), i.e., infiltration of monomer solutions into PE during graft-polymerization, influenced grafting rates and graft sites in films. In case of high mutual solubility, grafting rates were large and graft sites spread from the surface into bulk. On the other hand, in case of low mutual solubility, grafting rates were small and graft sites localized on the surface of films. (author)

PHEA-PLA biocompatible nanoparticles by technique of solvent evaporation from multiple emulsions.

Science.gov (United States)

Cavallaro, Gennara; Craparo, Emanuela Fabiola; Sardo, Carla; Lamberti, Gaetano; Barba, Anna Angela; Dalmoro, Annalisa

2015-11-30

Nanocarriers of amphiphilic polymeric materials represent versatile delivery systems for poorly water soluble drugs. In this work the technique of solvent evaporation from multiple emulsions was applied to produce nanovectors based on new amphiphilic copolymer, the α,β-poly(N-2-hydroxyethyl)-DL-aspartamide-polylactic acid (PHEA-PLA), purposely synthesized to be used in the controlled release of active molecules poorly soluble in water. To this aim an amphiphilic derivative of PHEA, a hydrophilic polymer, was synthesized by derivatization of the polymeric backbone with hydrophobic grafts of polylactic acid (PLA). The achieved copolymer was thus used to produce nanoparticles loaded with α tocopherol (vitamin E) adopted as lipophilic model molecule. Applying a protocol based on solvent evaporation from multiple emulsions assisted by ultrasonic energy and optimizing the emulsification process (solvent selection/separation stages), PHEA-PLA nanostructured particles with total α tocopherol entrapment efficiency (100%), were obtained. The drug release is expected to take place in lower times with respect to PLA due to the presence of the hydrophilic PHEA, therefore the produced nanoparticles can be used for semi-long term release drug delivery systems. Copyright © 2015 Elsevier B.V. All rights reserved.

Solvent influence during radiation induced grafting of styrene in PVDF

International Nuclear Information System (INIS)

Ferreira, Henrique P.; Parra, Duclerc F.; Lugao, Ademar B.

2013-01-01

Radiation-induced grafting was studied to produce styrene grafted poly(vinylidene fluoride) (PVDF) membranes. PVDF films with 0.125 mm thickness were irradiated at doses between 5 and 20 kGy in the presence of styrene/N,N-dimethylformamide (DMF), styrene/acetone or styrene/toluene solutions (1:1, v/v) at dose rate of 5 kGy h -1 by simultaneous method, using gamma rays from a Co-60, under nitrogen atmosphere and at room temperature. The films were characterized before and after modification by grafting yield (GY %), infrared spectroscopy (FT-IR), scanning electron microscopy (SEM and EDS), differential scanning calorimetry (DSC) and thermogravimetry (TG/DTG). GY results shows that grafting increases with dose and toluene hinders the grafting, leading to a small GY comparing to DMF and acetone. It was possible to confirm the grafting of styrene by FT-IR due to the new characteristics peaks and by the TG and DSC due to changes in thermal behavior of the grafted material. SEM and EDS show surface and cross-section distribution of the grafting, which takes place on the surface and heterogeneously with toluene as solvent and homogeneously and penetrating into the inner layers of the matrix using DMF and acetone as solvent. (author)

Solvent influence during radiation induced grafting of styrene in PVDF

Energy Technology Data Exchange (ETDEWEB)

Ferreira, Henrique P.; Parra, Duclerc F.; Lugao, Ademar B., E-mail: hp.ferreira@usp.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

2013-07-01

Radiation-induced grafting was studied to produce styrene grafted poly(vinylidene fluoride) (PVDF) membranes. PVDF films with 0.125 mm thickness were irradiated at doses between 5 and 20 kGy in the presence of styrene/N,N-dimethylformamide (DMF), styrene/acetone or styrene/toluene solutions (1:1, v/v) at dose rate of 5 kGy h{sup -1} by simultaneous method, using gamma rays from a Co-60, under nitrogen atmosphere and at room temperature. The films were characterized before and after modification by grafting yield (GY %), infrared spectroscopy (FT-IR), scanning electron microscopy (SEM and EDS), differential scanning calorimetry (DSC) and thermogravimetry (TG/DTG). GY results shows that grafting increases with dose and toluene hinders the grafting, leading to a small GY comparing to DMF and acetone. It was possible to confirm the grafting of styrene by FT-IR due to the new characteristics peaks and by the TG and DSC due to changes in thermal behavior of the grafted material. SEM and EDS show surface and cross-section distribution of the grafting, which takes place on the surface and heterogeneously with toluene as solvent and homogeneously and penetrating into the inner layers of the matrix using DMF and acetone as solvent. (author)

Synthesis of Citric-Acrylate Oligomer and its in-Situ Reaction with Chrome Tanned Collagen (hide powder)

International Nuclear Information System (INIS)

Haroun, A.A.; Masoud, R.A.; Bronco, S.; Ciardelli, F.

2005-01-01

The purpose of this study was to formulate the new combined system of acrylic and citric acids, which has been prepared by free radical polymerization and esterification reaction at the same time to form citric acrylate (CAC) oligomer through ester linkage and low molecular weight (Mw 2241), in compared with polyacrylic acid. The chemical structure and the reaction mechanism of this oligomer were confirmed by different spectroscopic tools (1 H , 13 C-NMR, ATR-IR), gel permeation chromatography and thermogravimetric analysis (TGA/DTA). The problem of the effect of the masking agents in the chrome tanning of the collagen and the pickling of the hide has been approached from the study of the hydrothermal and mechanical properties, using this new eco-friendly oligomer, which was carried out in-situ treated/grafted chrome tanned collagen (hide powder), and pickled hide. The microemulsion grafting copolymerization of (CAC) using 2.2-azo-bis isobutyronitrile (ABIN), via direct coupling reaction, onto the chrome tanned collagen showed that the free amino groups of the collagen were considered to be a potential site for the in-situ reaction with (CAC) oligomer. Also, using of citric-acrylate (CAC) oligomer, during chrome tanning of leather, instead of the traditional strong acids (sulfuric, hydrochloric and formic) resulted in significant improvement in chrome exhaustion and physical properties

Molecular structures of (3-aminopropyl)trialkoxysilane on hydroxylated barium titanate nanoparticle surfaces induced by different solvents and their effect on electrical properties of barium titanate based polymer nanocomposites

International Nuclear Information System (INIS)

Fan, Yanyan; Wang, Guanyao; Huang, Xingyi; Bu, Jing; Sun, Xiaojin; Jiang, Pingkai

2016-01-01

Graphical abstract: - Highlights: • The silanization on the surface of hydroxylated barium titanate nanoparticles was introduced by using two kinds of trialkoxysilanes with different solvents (toluene and ethanol), respectively. • Solvents have more remarkable impact on the dielectric properties of the subsequent BT/PVDF nanocomposites than the types of silanes. • The solvents used for BT nanoparticle surface modification exhibit a significant effect on the breakdown strength of the nanocomposites. - Abstract: Surface modification of nanoparticles by grafting silane coupling agents has proven to be a significant approach to improve the interfacial compatibility between inorganic filler and polymer matrix. However, the impact of grafted silane molecular structure after the nanoparticle surface modification, induced by the utilized solvents and the silane alkoxy groups, on the electrical properties of the corresponding nanocomposites, has been seldom investigated. Herein, the silanization on the surface of hydroxylated barium titanate (BT-OH) nanoparticles was introduced by using two kinds of trialkoxysilane, 3-aminopropyltriethoxysilane (AMEO) and 3-aminopropyltrimethoxysilane (AMMO), with different solvents (toluene and ethanol), respectively. Solid-state 13 C, 29 Si nuclear magnetic resonance (NMR) spectroscopy and high-resolution X-ray photoelectron spectroscopy (XPS) were employed to validate the structure differences of alkoxysilane attachment to the nanoparticles. The effect of alkoxysilane structure attached to the nanoparticle surface on the dielectric properties of the BT based poly(vinylidene fluoride) (PVDF) nanocomposites were investigated. The results reveal that the solvents used for BT nanoparticle surface modification exhibit a significant effect on the breakdown strength of the nanocomposites. Nevertheless, the alkoxy groups of silane show a marginal influence on the dielectric properties of the nanocomposites. These research results provide

Molecular structures of (3-aminopropyl)trialkoxysilane on hydroxylated barium titanate nanoparticle surfaces induced by different solvents and their effect on electrical properties of barium titanate based polymer nanocomposites

Science.gov (United States)

Fan, Yanyan; Wang, Guanyao; Huang, Xingyi; Bu, Jing; Sun, Xiaojin; Jiang, Pingkai

2016-02-01

Surface modification of nanoparticles by grafting silane coupling agents has proven to be a significant approach to improve the interfacial compatibility between inorganic filler and polymer matrix. However, the impact of grafted silane molecular structure after the nanoparticle surface modification, induced by the utilized solvents and the silane alkoxy groups, on the electrical properties of the corresponding nanocomposites, has been seldom investigated. Herein, the silanization on the surface of hydroxylated barium titanate (BT-OH) nanoparticles was introduced by using two kinds of trialkoxysilane, 3-aminopropyltriethoxysilane (AMEO) and 3-aminopropyltrimethoxysilane (AMMO), with different solvents (toluene and ethanol), respectively. Solid-state 13C, 29Si nuclear magnetic resonance (NMR) spectroscopy and high-resolution X-ray photoelectron spectroscopy (XPS) were employed to validate the structure differences of alkoxysilane attachment to the nanoparticles. The effect of alkoxysilane structure attached to the nanoparticle surface on the dielectric properties of the BT based poly(vinylidene fluoride) (PVDF) nanocomposites were investigated. The results reveal that the solvents used for BT nanoparticle surface modification exhibit a significant effect on the breakdown strength of the nanocomposites. Nevertheless, the alkoxy groups of silane show a marginal influence on the dielectric properties of the nanocomposites. These research results provide important insights into the fabrication of advanced polymer nanocomposites for dielectric applications.

Hydrophobic lapatinib encapsulated dextran-chitosan nanoparticles using a toxic solvent free method: fabrication, release property & in vitro anti-cancer activity

Energy Technology Data Exchange (ETDEWEB)

Mobasseri, Rezvan [Department of Nanobiotechnology, Faculty of Biological Sciences, Tarbiat Modares University, Tehran (Iran, Islamic Republic of); Center for Nanofibers & Nanotechnology, Department of Mechanical Engineering, National University of Singapore, 117576 (Singapore); Karimi, Mahdi [Department of Nanobiotechnology, Faculty of Biological Sciences, Tarbiat Modares University, Tehran (Iran, Islamic Republic of); Tian, Lingling, E-mail: lingling_tian@nus.edu.sg [Center for Nanofibers & Nanotechnology, Department of Mechanical Engineering, National University of Singapore, 117576 (Singapore); Naderi-Manesh, Hossein, E-mail: naderman@modares.ac.ir [Department of Nanobiotechnology, Faculty of Biological Sciences, Tarbiat Modares University, Tehran (Iran, Islamic Republic of); Department of Biophysics, Faculty of Biological Sciences, Tarbiat Modares University, Tehran (Iran, Islamic Republic of); Ramakrishna, Seeram [Center for Nanofibers & Nanotechnology, Department of Mechanical Engineering, National University of Singapore, 117576 (Singapore); Guangdong-Hongkong-Macau Institute of CNS Regeneration (GHMICR), Jinan University, Guangzhou 510632 (China)

2017-05-01

Dextran sulfate-chitosan (DS-CS) nanoparticles, which possesses properties such as nontoxicity, biocompatibility and biodegradability have been employed as drug carriers in cancer therapy. In this study, DS-CS nanoparticles were synthesized and their sizes were controlled by a modification of the divalent cations cross-linkers (Ca{sup 2+}, Zn{sup 2+} or Mg{sup 2+}). Based on the optimized processing parameters, lapatinib encapsulated nanoparticles were developed and characterized by Dynamics Light Scattering (DLS) measurements, Fourier Transform Infrared Spectroscopy (FT-IR) and Scanning Electron Microscopy (SEM). Calcium chloride (CaCl{sub 2}) facilitated the formation of bare (100.3 ± 0.80 nm) and drug-loaded nanoparticles (134.3 ± 1.3 nm) with narrow size distributions being the best cross-linker. The surface potential of drug-loaded nanoparticles was − 16.8 ± 0.47 mV and its entrapment and loading efficiency were 76.74 ± 1.73% and 47.36 ± 1.27%, respectively. Cellular internalization of nanoparticles was observed by fluorescence microscopy and MTT (3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide) assay was used to determine cytotoxicity of bare and drug-loaded nanoparticles in comparison to the free drug lapatinib. The MTT assay showed that drug-loaded nanoparticles had comparable anticancer activity to free drug within a duration of 48 h. The aforementioned results showed that the DS-CS nanoparticles were able to entrap, protect and release the hydrophobic drug, lapatinib in a controlled pattern and could further serve as a suitable drug carrier for cancer therapy. - Highlights: • The best condition to prepare best size (about 100 nm) dextran-chitosan nanoparticles is proposed. • Divalent cationic cross-linker can act as hardener and compress the particles. • Drug/dextran mixing in a toxic solvent free method provides hydrophobic drug encapsulation within a hydrophilic system. • High entrapment efficiency of Lapatinib in polymeric

Synthesis and characterization of solvent-free ionic molybdenum disulphide (MoS{sub 2}) nanofluids

Energy Technology Data Exchange (ETDEWEB)

Gu, Shu-Ying, E-mail: gushuying@tongji.edu.cn [School of Materials Science and Engineering, Tongji University, Shanghai 201804 (China); Key Laboratory of Advanced Civil Engineering Materials, Ministry of Education, School of Materials Science and Engineering, Tongji University, Shanghai 201804 (China); Gao, Xie-Feng; Zhang, Yi-Han [School of Materials Science and Engineering, Tongji University, Shanghai 201804 (China)

2015-01-15

A development of the novel and stable solvent-free ionic MoS{sub 2} nanofluids by a facile and scalable hydrothermal method is presented. The nanofluids were synthesized by surface functionalizing nanoscale MoS{sub 2} from hydrothermal synthesis with a charged corona, and ionically tethering with oligomeric chains as a canopy. The structures and properties of the nanofluids were characterized by Fourier transform infrared (FTIR), nuclear magnetic resonance (NMR, {sup 1}H), differential scanning calorimeter (DSC), thermogravimetric analysis (TGA) and ARES rheometer. The obtained solvent-free nanofluids are homogeneous, stable amber-like fluids with no evidence of phase separation. The nanofluids could be easily dispersed in both aqueous and organic solvents to form transparent and stable liquids due to the ionic nature and the presence of oligomeric polymer chains. It was found that the solvent-free nanofluids with up to 32 wt% inorganic content show Newtonian rheological behaviors due to the high graft density and uniform dispersion of inorganic cores, indicating that the nanofluids would have a stable lubricating performance. As reported in our previous communication, the nanofluids showing lower, more stable friction coefficients of less than 0.1 with self-healing lubricating behaviors. For deeper understanding of the nanofluids, the details of synthesis, chemical structures, rheological behaviors and molecular dynamics of the nanofluids were investigated in details. The rheological behaviors can be tailored by varying the grafting density of the canopy. Dynamic results of the canopy of the MoS{sub 2} nanofluids show that inorganic MoS{sub 2} cores have hindrance effect on the canopy segmental motions above 253 K due to their effect to the mobility of anions and the departing-recombining motions between the paired cations and anions. - Highlights: • A development of the novel synthesis of solvent-free MoS{sub 2} nanofluids is presented. • The rheological

Relating Structure to Efficiency in Surfactant-Free Polymer/Fullerene Nanoparticle-Based Organic Solar Cells.

Science.gov (United States)

Gärtner, Stefan; Clulow, Andrew J; Howard, Ian A; Gilbert, Elliot P; Burn, Paul L; Gentle, Ian R; Colsmann, Alexander

2017-12-13

Nanoparticle dispersions open up an ecofriendly route toward printable organic solar cells. They can be formed from a variety of organic semiconductors by using miniemulsions that employ surfactants to stabilize the nanoparticles in dispersion and to prevent aggregation. However, whenever surfactant-based nanoparticle dispersions have been used to fabricate solar cells, the reported performances remain moderate. In contrast, solar cells from nanoparticle dispersions formed by precipitation (without surfactants) can exhibit power conversion efficiencies close to those of state-of-the-art solar cells processed from blend solutions using chlorinated solvents. In this work, we use small-angle neutron scattering measurements and transient absorption spectroscopy to investigate why surfactant-free nanoparticles give rise to efficient organic solar cells. We show that surfactant-free nanoparticles comprise a uniform distribution of small semiconductor domains, similar to that of bulk-heterojunction films formed using traditional solvent processing. This observation differs from surfactant-based miniemulsion nanoparticles that typically exhibit core-shell structures. Hence, the surfactant-free nanoparticles already possess the optimum morphology for efficient energy conversion before they are assembled into the photoactive layer of a solar cell. This structural property underpins the superior performance of the solar cells containing surfactant-free nanoparticles and is an important design criterion for future nanoparticle inks.

Kinetic investigations of emulsion- and solvent-mediated radiation induced graft copolymerization of glycidyl methacrylate onto nylon-6 fibres

International Nuclear Information System (INIS)

Teo Ming Ting; Paveswari Sithambaranathan

2017-01-01

Kinetic behaviour of graft copolymerisation of glycidyl methacrylate onto nylon-6 fibres in solvent- and emulsion- media was investigated. The order for the dependence of the initial rate of grafting on the monomer concentration for solvent and emulsion grafting systems were found to be 1.65 and 1.57, respectively. The order of dependence of the initial rate of grafting on the absorbed dose was found to be 1.55 for solvent and 0.62 emulsion grafting systems. The results showed that grafting in both systems is controlled by diffusion mechanism and the degree of grafting can be effectively tuned by variation of the grafting parameters. (author)

Interaction forces between nanoparticles in Lennard-Jones (L-J) solvents

International Nuclear Information System (INIS)

Sinha, Indrajit; Mukherjee, Ashim K

2014-01-01

Molecular simulations, such as Monte Carlo (MC) and molecular dynamics (MD) have been recently used for understanding the forces between colloidal nanoparticles that determine the dispersion and stability of nanoparticle suspensions. Herein we review the current status of research in the area of nanoparticles immersed in L-J solvents. The first study by Shinto et al. used large smooth spheres to depict nanoparticles in L-J and soft sphere solvents. The nanoparticles were held fixed at a particular interparticle distance and only the solvents were allowed to equilibrate. Both Van-der-waals and solvation forces were computed at different but fixed interparticle separation. Later Qin and Fitchthorn improved on this model by considering the nanoparticles as collection of molecules, thus taking into the account the effect of surface roughness of nanoparticles. Although the inter particle distance was fixed, the rotation of such nanoparticles with respect to each other was also investigated. Recently, in keeping with the experimental situation, we modified this model by allowing the nanoparticles to move and rotate freely. Solvophilic, neutral and solvophobic interactions between the solvent atoms and those that make up the nanoparticles were modelled. While neutral and solvophobic nanoparticles coalesce even at intermediate distances, solvophilic nanoparticles are more stable in solution due to the formation of a solvent shield

Solvent effect on post-irradiation grafting of styrene onto poly(ethylene-alt-tetrafluoroethylene) (ETFE) films

Science.gov (United States)

Napoleão Geraldes, Adriana; Augusto Zen, Heloísa; Ribeiro, Geise; Fernandes Parra, Duclerc; Benévolo Lugão, Ademar

2013-03-01

Radiation-induced grafting of styrene onto ETFE films in different solvent was investigated after simultaneous irradiation (in post-irradiation condition) using a 60Co source. Grafting of styrene followed by sulfonation onto poly(ethylene-alt-tetrafluoroethylene) (ETFE) are currently studied for synthesis of ion exchange membranes. The ETFE films were immersed in styrene/toluene, styrene/methanol and styrene/isopropyl alcohol and irradiated at 20 and 100 kGy doses at room temperature. The post-irradiation time was established at 14 day and the grafting degree was evaluated. The grafted films were sulfonated using chlorosulfonic acid and 1,2-dichloroethane 20:80 (v/v) at room temperature for 5 h. The degree of grafting (DOG) was determined gravimetrically and physical or chemical changes were evaluated by differential scanning calorimeter analysis (DSC), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The ion exchange capacity (IEC) values showed the best performance of sulfonation for ETFE membranes grafted in toluene solvent. Surface images of the grafted films by SEM technique have presented a strong effect of the solvents on the films morphology.

Norfloxacin release from surfactant-free nanoparticles of poly (DL-lactide-co-glycolide) and biodegradation

Energy Technology Data Exchange (ETDEWEB)

Kweon, J.K. [Chosun College of Science and Technology, Gwangju (Korea); Jeong, Y.I. [Chonnam National University, Gwangju (Korea); Jang, M.K. [Suncheon National University, Suncheon (Korea); Lee, C.H. [Korea Food and Drug Administration, Seoul (Korea); Nah, J.W. [Suncheon National University, Suncheon (Korea)

2002-07-01

We have prepared the surfactant-free nanoparticles of poly(DL- lactide-co-glycolide)(PLGA) by dialysis method and their physicochemical properties such as particle size and drug contents were investigated against various solvent. The size of PLGA nanoparticles prepared by using dimethylacetamide (DMAc), dimethylformamide (DMF), and dimethylsulfoxide (DMSO) was smaller than that from acetone. Also, the order of drug contents was DMAc>DMF>DMSO=acetone. These phenomena could be expected from the fact that solvent affects the size of nanoparticles and drug contents. The PLGA nanoparticles have a good spherical shapes as observed from scanning electron microscopy (SEM) and transmission electron microscopy (TEM), Also, surfactant-free nanoparticles entrapping norfloxacin (NFx) have a good drug loading capacity without free-drug on the surface of nanoparticles confirmed by the analysis of X-ray powder diffraction. Release kinetics of NFx used as a model drug was governed not only by drug contents but also by particle size. Also, the biodegradation rate of PLGA nanoparticles prepared from DMF was faster than that prepared from acetone, indicating that the biodegradation of PLGA nanoparticles is size-dependent. (author). 25 refs., 3 tabs., 5 figs.

Molecular imaging of banknote and questioned document using solvent-free gold nanoparticle-assisted laser desorption/ionization imaging mass spectrometry.

Science.gov (United States)

Tang, Ho-Wai; Wong, Melody Yee-Man; Chan, Sharon Lai-Fung; Che, Chi-Ming; Ng, Kwan-Ming

2011-01-01

Direct chemical analysis and molecular imaging of questioned documents in a non/minimal-destructive manner is important in forensic science. Here, we demonstrate that solvent-free gold-nanoparticle-assisted laser desorption/ionization mass spectrometry is a sensitive and minimal destructive method for direct detection and imaging of ink and visible and/or fluorescent dyes printed on banknotes or written on questioned documents. Argon ion sputtering of a gold foil allows homogeneous coating of a thin layer of gold nanoparticles on banknotes and checks in a dry state without delocalizing spatial distributions of the analytes. Upon N(2) laser irradiation of the gold nanoparticle-coated banknotes or checks, abundant ions are desorbed and detected. Recording the spatial distributions of the ions can reveal the molecular images of visible and fluorescent ink printed on banknotes and determine the printing order of different ink which may be useful in differentiating real banknotes from fakes. The method can also be applied to identify forged parts in questioned documents, such as number/writing alteration on a check, by tracing different writing patterns that come from different pens.

Spray-coated ligand-free Cu2ZnSnS4 nanoparticle thin films

DEFF Research Database (Denmark)

Engberg, Sara Lena Josefin; Murthy, Swathi; Kofod, Guggi

We have fabricated Cu2ZnSnS4 (CZTS) thin films from spray-coating ligand-free nanoparticle inks. The as-synthesized CZTS nanoparticles were inherently ligand-free [1], which allows the use of polar solvents, such as water and ethanol. Another advantage of these particles is that user- and environ......We have fabricated Cu2ZnSnS4 (CZTS) thin films from spray-coating ligand-free nanoparticle inks. The as-synthesized CZTS nanoparticles were inherently ligand-free [1], which allows the use of polar solvents, such as water and ethanol. Another advantage of these particles is that user......- and environmentally-friendly alkali metal chloride salts can be directly dissolved in controllable amounts. The homogeneous distribution of alkali metals in the ink allows uniform grain growth within the deposited absorber layer as a result of liquid phase assisted sintering. We find that particularly beneficial...... as an unquantifiable amount of ZnS. A Sono-tek spray-coating system is used which utilizes ultrasonic atomization. We investigate the effect of different binders, ink concentration, and spray-coating conditions, i.e. spray power, flow rate from syringe pump, distance between spray nozzle and the substrate, and time...

Selective amyloid β oligomer assay based on abasic site-containing molecular beacon and enzyme-free amplification.

Science.gov (United States)

Zhu, Linling; Zhang, Junying; Wang, Fengyang; Wang, Ya; Lu, Linlin; Feng, Chongchong; Xu, Zhiai; Zhang, Wen

2016-04-15

Amyloid-beta (Aβ) oligomers are highly toxic species in the process of Aβ aggregation and are regarded as potent therapeutic targets and diagnostic markers for Alzheimer's disease (AD). Herein, a label-free molecular beacon (MB) system integrated with enzyme-free amplification strategy was developed for simple and highly selective assay of Aβ oligomers. The MB system was constructed with abasic site (AP site)-containing stem-loop DNA and a fluorescent ligand 2-amino-5,6,7-trimethyl-1,8-naphyridine (ATMND), of which the fluorescence was quenched upon binding to the AP site in DNA stem. Enzyme-free amplification was realized by target-triggered continuous opening of two delicately designed MBs (MB1 and MB2). Target DNA hybridization with MB1 and then MB2 resulted in the release of two ATMND molecules in one binding event. Subsequent target recycling could greatly amplify the detection sensitivity due to the greatly enhanced turn-on emission of ATMND fluorescence. Combining with Aβ oligomers aptamers, the strategy was applied to analyze Aβ oligomers and the results showed that it could quantify Aβ oligomers with high selectivity and monitor the Aβ aggregation process. This novel method may be conducive to improve the diagnosis and pathogenic study of Alzheimer's disease. Copyright © 2015 Elsevier B.V. All rights reserved.

Effect of solvent on the synthesis of SnO_2 nanoparticles

International Nuclear Information System (INIS)

Kumar, Virender; Singh, Karamjit; Singh, Kulwinder; Kumar, Akshay; Kumari, Sudesh; Thakur, Anup

2016-01-01

Tin oxide (SnO_2) nanoparticles have been synthesized by co-precipitation method. The synthesized nanoparticles have been characterized by X-ray diffraction (XRD) and Ultraviolet-Visible spectroscopy (UV-VIS). XRD analysis confirmed the formation of single phase of SnO_2 nanoparticles. It has been found that solvents played important role in controlling the crystallite size of SnO_2 nanoparticles. The XRD analysis showed well crystallized tetragonal SnO_2 nanoparticles. The crystallite size of SnO_2 nanoparticles varies with the solvent. Tauc plot showed that optical band gap was also tailored by controlling the solvent during synthesis.

Shape Engineering of Biomass-Derived Nanoparticles from Hollow Spheres to Bowls via Solvent-Induced Buckling.

Science.gov (United States)

Chen, Chunhong; Li, Xuefeng; Jiang, Deng; Wang, Zhe; Wang, Yong

2018-06-19

To realize the asymmetry for the hollow carbonaceous nanostructures remains to be a great challenge, especially when biomass is chosen as the carbon resource via hydrothermal carbonization (HTC). Herein, a simple and straightforward solvent induced buckling strategy is demonstrated for the synthesis of asymmetric spherical and bowllike carbonaceous nanomaterials. The formation of the bowllike morphology was attributed to the buckling of the spherical shells induced by the dissolution of the oligomers. The bowllike particles made by this solvent-driven approach demonstrated a well-controlled morphology and a uniform particle size of ~360 nm. The obtained nanospheres and nanobowls can be loaded with CoS2 nanoparticles to act as novel heterogeneous catalysts for the selective hydrogenation of aromatic nitro compounds. With the bowllike structure in hand, as expected, the CoS2/nanobowls catalyst showed good tolerance to a wide scope of reducible groups and afforded both high activity and selectivity in almost all the tested substrates (14). © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoparticle for delivery of antisense γPNA oligomers targeting CCR5

OpenAIRE

Bahal, Raman; McNeer, Nicole Ali; Ly, Danith H.; Saltzman, W. Mark; Glazer, Peter M.

2013-01-01

The development of a new class of peptide nucleic acids (PNAs), i.e., gamma PNAs (γPNAs), creates the need for a general and effective method for its delivery into cells for regulating gene expression in mammalian cells. Here we report the antisense activity of a recently developed hydrophilic and biocompatible diethylene glycol (miniPEG)-based gamma peptide nucleic acid called MPγPNAs via its delivery by poly(lactide-co-glycolide) (PLGA)-based nanoparticle system. We show that MPγPNA oligome...

Preparation of Candesartan and Atorvastatin Nanoparticles by Solvent Evaporation

Directory of Open Access Journals (Sweden)

Josef Jampilek

2012-11-01

Full Text Available The solubility, absorption and distribution of a drug are involved in the basic aspects of oral bioavailability Solubility is an essential characteristic and influences the efficiency of the drug. Over the last ten years, the number of poorly soluble drugs has steadily increased. One of the progressive ways for increasing oral bioavaibility is the technique of nanoparticle preparation, which allows many drugs to thus reach the intended site of action. Candesartan cilexetil and atorvastatin, belonging to class II of the biopharmaceutical classification system, were chosen as model active pharmaceutical ingredients in this study. Forty samples were prepared either by antisolvent precipitation/solvent evaporation method or by the emulsion/solvent evaporation technique with various commonly used surface-active excipients as nanoparticle stabilizers. All samples were analyzed by means of dynamic light scattering. The particle size of the determined 36 nanoparticle samples was to 574 nm, whereas 32 samples contained nanoparticles of less than 200 nm. Relationships between solvents and excipients used and their amount are discussed. Based on the results the investigated solvent evaporation methods can be used as an effective and an affordable technique for the preparation of nanoparticles.

Polyethyleneimine-modified superparamagnetic Fe3O4 nanoparticles for lipase immobilization: Characterization and application

International Nuclear Information System (INIS)

Khoobi, Mehdi; Motevalizadeh, Seyed Farshad; Asadgol, Zahra; Forootanfar, Hamid; Shafiee, Abbas; Faramarzi, Mohammad Ali

2015-01-01

Magnetically separable nanospheres consisting of polyethyleneimine (PEI) and succinated PEI grafted on silica coated magnetite (Fe 3 O 4 ) were prepared and characterized using Fourier transform infrared spectroscopy, thermogravimetric analysis, X-ray diffraction, vibrating sample magnetometer, scanning electron microscopy and transmission electron microscopy. The prepared magnetic nanoparticles were then applied for physical adsorption or covalent attachment of Thermomyces lanuginosa lipase (TLL) via glutaraldehyde or hexamethylene diisocyanate. The reusability, storage, pH and thermal stabilities of the immobilized enzymes compared to that of free lipase were examined. The obtained results showed that the immobilized lipase on MNPs@PEI-GLU was the best biocatalyst which retained 80% of its initial activity after 12 cycles of application. The immobilized lipase on the selected support (MNPs@PEI-GLU) was also applied for the synthesis of ethyl valerate. Following 24 h incubation of the immobilized lipase on the selected support in n-hexane and solvent free media, the esterification percentages were 72.9% and 28.9%, respectively. - Graphical abstract: A schematic of the preparation of PEI- and succinated PEI-grafted Fe 3 O 4 MNPs (MNPs@PEI) and the immobilization of lipase by covalent bonding and adsorption. - Highlights: • Functionalized polyethylenimine-grafted magnetic nanoparticles were synthesized. • The prepared supports were fully characterized by various analysis methods. • Lipase was immobilized on the nanostructures by adsorption and covalent attachment. • Immobilized lipase produced ethyl valerate in solvent free medium

Self-Assembly of Block and Graft Copolymers in Organic Solvents: An Overview of Recent Advances

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Leonard Ionut Atanase

2018-01-01

Full Text Available This review is an attempt to update the recent advances in the self-assembly of amphiphilic block and graft copolymers. Their micellization behavior is highlighted for linear AB, ABC triblock terpolymers, and graft structures in non-aqueous selective polar and non-polar solvents, including solvent mixtures and ionic liquids. The micellar characteristics, such as particle size, aggregation number, and morphology, are examined as a function of the copolymers’ architecture and molecular characteristics.

Porous asymmetric SiO2-g-PMMA nanoparticles produced by phase inversion

KAUST Repository

Munirasu, Selvaraj

2014-07-22

A new kind of asymmetric organic-inorganic porous structure has been proposed. Asymmetric lattices of polymer grafted silica nanoparticles were manufactured by casting and phase inversion in water. Silica nanoparticles were first functionalized with 3-(dimethylethoxysilyl)propyl-2-bromoisobutyrate, followed by grafting of poly(methylmethacrylate) (PMMA) segments, performed by atom-transfer radical polymerization. Mechanically stable self-standing films were prepared by casting a dispersion of functionalized nanoparticles in different solvents and immersion in water. The resulting asymmetrically porous morphology and nanoparticle assembly was characterized by scanning electron and atomic force microscopy. The PMMA functionalized SiO2 hybrid material in acetone or acetone/dioxane led to the best-assembled structures. Porous asymmetric membranes were prepared by adding free PMMA and PMMA terminated with hydrophilic hydroxyl group. Nitrogen flow of 2800 L m-2 h -1 was measured at 1.3 bar demonstrating the porosity and potential application for membrane technology. © 2014 Springer Science+Business Media New York.

Grafting and curing

International Nuclear Information System (INIS)

Garnett, J.L.; Loo-Teck Ng; Visay Viengkhou

1998-01-01

Progress in radiation grafting and curing is briefly reviewed. The two processes are shown to be mechanistically related. The parameters influencing yields are examined particularly for grafting. For ionising radiation grafting systems (EB and gamma ray) these include solvents, substrate and monomer structure, dose and dose-rate, temperature and more recently role of additives. In addition, for UV grafting, the significance of photoinitiators is discussed. Current applications of radiation grafting and curing are outlined. The recent development of photoinitiator free grafting and curing is examined as well as the potential for the new excimer laser sources. The future application of both grafting and curing is considered, especially the significance of the occurrence of concurrent grafting during cure and its relevance in environmental considerations

Polyethyleneimine-modified superparamagnetic Fe{sub 3}O{sub 4} nanoparticles for lipase immobilization: Characterization and application

Energy Technology Data Exchange (ETDEWEB)

Khoobi, Mehdi; Motevalizadeh, Seyed Farshad [Department of Medicinal Chemistry, Faculty of Pharmacy and Pharmaceutical Sciences Research Center, Tehran University of Medical Sciences, Tehran 1417614411 (Iran, Islamic Republic of); Asadgol, Zahra [Department of Pharmaceutical Biotechnology, Faculty of Pharmacy and Biotechnology Research Center, Tehran University of Medical Sciences, P.O. Box 14155-6451, Tehran 1417614411 (Iran, Islamic Republic of); Forootanfar, Hamid [Department of Pharmaceutical Biotechnology, Faculty of Pharmacy, Kerman University of Medical Sciences, Kerman (Iran, Islamic Republic of); Shafiee, Abbas, E-mail: ashafiee@ams.ac.ir [Department of Medicinal Chemistry, Faculty of Pharmacy and Pharmaceutical Sciences Research Center, Tehran University of Medical Sciences, Tehran 1417614411 (Iran, Islamic Republic of); Faramarzi, Mohammad Ali, E-mail: faramarz@tums.ac.ir [Department of Pharmaceutical Biotechnology, Faculty of Pharmacy and Biotechnology Research Center, Tehran University of Medical Sciences, P.O. Box 14155-6451, Tehran 1417614411 (Iran, Islamic Republic of)

2015-01-15

Magnetically separable nanospheres consisting of polyethyleneimine (PEI) and succinated PEI grafted on silica coated magnetite (Fe{sub 3}O{sub 4}) were prepared and characterized using Fourier transform infrared spectroscopy, thermogravimetric analysis, X-ray diffraction, vibrating sample magnetometer, scanning electron microscopy and transmission electron microscopy. The prepared magnetic nanoparticles were then applied for physical adsorption or covalent attachment of Thermomyces lanuginosa lipase (TLL) via glutaraldehyde or hexamethylene diisocyanate. The reusability, storage, pH and thermal stabilities of the immobilized enzymes compared to that of free lipase were examined. The obtained results showed that the immobilized lipase on MNPs@PEI-GLU was the best biocatalyst which retained 80% of its initial activity after 12 cycles of application. The immobilized lipase on the selected support (MNPs@PEI-GLU) was also applied for the synthesis of ethyl valerate. Following 24 h incubation of the immobilized lipase on the selected support in n-hexane and solvent free media, the esterification percentages were 72.9% and 28.9%, respectively. - Graphical abstract: A schematic of the preparation of PEI- and succinated PEI-grafted Fe{sub 3}O{sub 4} MNPs (MNPs@PEI) and the immobilization of lipase by covalent bonding and adsorption. - Highlights: • Functionalized polyethylenimine-grafted magnetic nanoparticles were synthesized. • The prepared supports were fully characterized by various analysis methods. • Lipase was immobilized on the nanostructures by adsorption and covalent attachment. • Immobilized lipase produced ethyl valerate in solvent free medium.

Toward transparent nanocomposites based on polystyrene matrix and PMMA-grafted CeO2 nanoparticles.

Science.gov (United States)

Parlak, Onur; Demir, Mustafa M

2011-11-01

The association of transparent polymer and nanosized pigment particles offers attractive optical materials for various potential and existing applications. However, the particles embedded into polymers scatter light due to refractive index (RI) mismatch and reduce transparency of the resulting composite material. In this study, optical composites based on polystyrene (PS) matrix and poly(methyl methacrylate) (PMMA)-grafted CeO(2) hybrid particles were prepared. CeO(2) nanoparticles with an average diameter of 18 ± 8 nm were precipitated by treating Ce(NO(3))·6H(2)O with urea in the presence of a polymerizable surfactant, 3-methacyloxypropyltrimethoxy silane. PMMA chains were grafted on the surface of the nanoparticles upon free radical in situ solution polymerization. While blending of unmodified CeO(2) particles with PS resulted in opaque films, the transparency of the composite films was remarkably enhanced when prepared by PMMA-grafted CeO(2) hybrid particles, particularly those having a PMMA thickness of 9 nm. The improvement in transparency is presumably due to the reduction in RI mismatch between CeO(2) particles and the PS matrix when using PMMA chains at the interface.

Surface modification of cation exchange membranes by graft polymerization of PAA-co-PANI/MWCNTs nanoparticles

International Nuclear Information System (INIS)

Nemati, Mahsa; Hosseini, Sayed Mohsen; Bagheripour, Ehsan; Madaeni, Sayed Siavash

2016-01-01

Surface modification of polyvinylchloride based heterogeneous cation exchange membrane was performed by graft polymerization of PAA and PAA-co-PANI/MWCNTs nanoparticles. The ion exchange membranes were prepared by solution casting technique. Spectra analysis confirmed graft polymerization clearly. SEM images illustrated that graft polymerization covers the membranes by simple gel network entanglement. The membrane water content was decreased by graft polymerization of PAA-co-PANI/MWCNTs nanoparticles on membrane surface. Membrane transport number and selectivity declined initially by PAA graft polymerization and then began to increase by utilizing of composite nanoparticles in modifier solution. The sodium and barium flux was improved sharply by PAA and PAAco- 0.01%wt PANI/MWCNTs graft polymerization on membrane surface and then decreased again by more increase of PANI/MWCNTs nanoparticles content ratio in modifier solution. The electrodialysis experiment results in laboratory scale showed higher dialytic rate in heavy metals removal for grafted-PAA and grafted-PAA-co-PANI/MWCNTs modified membrane compared to pristine one. Membrane areal electrical resistance was also decreased by introducing graft polymerization of PAA and PAA-co-PANI/MWCNTs NPs on membrane surface.

Effect of solvents on properties of Bombyx mori silk grafted by methyl methacrylate (MMA and methacrylamide (MAA

Directory of Open Access Journals (Sweden)

Wattana Klairatsamee

2005-11-01

Full Text Available Mulberry silks were chemically modified in order to increase weight gain, resulting from degumming process using graft copolymerisation technique with vinyl monomers, i.e. MMA, MAA and MMA/MAA. Due to the appearance of PMMA homopolymer granules adhered on the MMA- and MMA/MAA-grafted silk surfaces resulting in surface roughness when silk was grafted by MMA in water, the influence of grafting solvents was examined, using different water/ethanol volume ratios of 100/0, 75/25, 50/50, 25/75 and 0/100. FTIR spectra of the grafted silks presented the absorption bands of the vinyl monomers used for the grafting process. In addition, high values of % polymer add-on were obtained for all of the grafted silks. It was also found that the suitable solvents were 25/75 water/ethanol for the silk grafted by MMA and MMA/MAA, and water for the silk grafted by MAA, in order to get the smooth grafted silk surface and high polymer add-on. Moreover, all the grafted silks showed slightly greater stiffness, as indicated by the increase of Young's modulus and the decrease of elongation.

Self-Suspended Suspensions of Covalently Grafted Hairy Nanoparticles

KAUST Repository

Choudhury, Snehashis

2015-03-17

© 2015 American Chemical Society. Dispersions of small particles in liquids have been studied continuously for almost two centuries for their ability to simultaneously advance understanding of physical properties of fluids and their widespread use in applications. In both settings, the suspending (liquid) and suspended (solid) phases are normally distinct and uncoupled on long length and time scales. In this study, we report on the synthesis and physical properties of a novel family of covalently grafted nanoparticles that exist as self-suspended suspensions with high particle loadings. In such suspensions, we find that the grafted polymer chains exhibit unusual multiscale structural transitions and enhanced conformational stability on subnanometer and nanometer length scales. On mesoscopic length scales, the suspensions display exceptional homogeneity and colloidal stability. We attribute this feature to steric repulsions between grafted chains and the space-filling constraint on the tethered chains in the single-component self-suspended materials, which inhibits phase segregation. On macroscopic length scales, the suspensions exist as neat fluids that exhibit soft glassy rheology and, counterintuitively, enhanced elasticity with increasing temperature. This feature is discussed in terms of increased interpenetration of the grafted chains and jamming of the nanoparticles. (Chemical Presented).

Separation of xylose oligomers using centrifugal partition chromatography with a butanol-methanol-water system.

Science.gov (United States)

Lau, Ching-Shuan; Clausen, Edgar C; Lay, Jackson O; Gidden, Jennifer; Carrier, Danielle Julie

2013-01-01

Xylose oligomers are the intermediate products of xylan depolymerization into xylose monomers. An understanding of xylan depolymerization kinetics is important to improve the conversion of xylan into monomeric xylose and to minimize the formation of inhibitory products, thereby reducing ethanol production costs. The study of xylan depolymerization requires copious amount of xylose oligomers, which are expensive if acquired commercially. Our approach consisted of producing in-house oligomer material. To this end, birchwood xylan was used as the starting material and hydrolyzed in hot water at 200 °C for 60 min with a 4 % solids loading. The mixture of xylose oligomers was subsequently fractionated by a centrifugal partition chromatography (CPC) with a solvent system of butanol:methanol:water in a 5:1:4 volumetric ratio. Operating in an ascending mode, the butanol-rich upper phase (the mobile phase) eluted xylose oligomers from the water-rich stationary phase at a 4.89 mL/min flow rate for a total fractionation time of 300 min. The elution of xylose oligomers occurred between 110 and 280 min. The yields and purities of xylobiose (DP 2), xylotriose (DP 3), xylotetraose (DP 4), and xylopentaose (DP 5) were 21, 10, 14, and 15 mg/g xylan and 95, 90, 89, and 68 %, respectively. The purities of xylose oligomers from this solvent system were higher than those reported previously using tetrahydrofuran:dimethyl sulfoxide:water in a 6:1:3 volumetric ratio. Moreover, the butanol-based solvent system improved overall procedures by facilitating the evaporation of the solvents from the CPC fractions, rendering the purification process more efficient.

Reconstruction of large upper eyelid defects with a free tarsal plate graft and a myocutaneous pedicle flap plus a free skin graft.

Science.gov (United States)

Toft, Peter B

2016-01-01

To review and present the results of a one-step method employing a free tarsal plate graft and a myocutaneous pedicle flap plus a free skin graft for reconstruction of large upper eyelid defects after tumour surgery. This was a retrospective case-series of 8 patients who underwent reconstruction of the upper eyelid after tumour removal. The horizontal defect involved 50-75% of the lid (3 pts.), more than 75% (3 pts.), and more than 75% plus the lateral canthus (2 pts.). The posterior lamella was reconstructed with contralateral upper eyelid tarsal plate. The anterior lamella was reconstructed with a laterally based myocutaneous pedicle flap in 7 patients, leaving a raw surface under the brow which was covered with a free skin graft. In 1 patient with little skin left under the brow, the anterior lamella was reconstructed with a bi-pedicle orbicularis muscle flap together with a free skin graft. All patients healed without necrosis, did not suffer from lagophthalmos, achieved reasonable cosmesis, and did not need lubricants. In one patient, a contact lens was necessary for three weeks because of corneal erosion. One patient still needs a contact lens 3 months after excision to avoid eye discomfort. Large upper eyelid defects can be reconstructed with a free tarsal plate graft and a laterally based myocutaneous pedicle flap in combination with a free skin graft. Two-step procedures can probably be avoided in most cases.

Dendritic brushes under theta and poor solvent conditions

Science.gov (United States)

Gergidis, Leonidas N.; Kalogirou, Andreas; Charalambopoulos, Antonios; Vlahos, Costas

2013-07-01

The effects of solvent quality on the internal stratification of polymer brushes formed by dendron polymers up to third generation were studied by means of molecular dynamics simulations with Langevin thermostat. The distributions of polymer units, of the free ends, the radii of gyration, and the back folding probabilities of the dendritic spacers were studied at the macroscopic states of theta and poor solvent. For high grafting densities we observed a small decrease in the height of the brush as the solvent quality decreases. The internal stratification in theta solvent was similar to the one we found in good solvent, with two and in some cases three kinds of populations containing short dendrons with weakly extended spacers, intermediate-height dendrons, and tall dendrons with highly stretched spacers. The differences increase as the grafting density decreases and single dendron populations were evident in theta and poor solvent. In poor solvent at low grafting densities, solvent micelles, polymeric pinned lamellae, spherical and single chain collapsed micelles were observed. The scaling dependence of the height of the dendritic brush at high density brushes for both solvents was found to be in agreement with existing analytical results.

Solvent and irradiation doses effects on the ion exchange capacity of sulfonated styrene grafted PVDF

International Nuclear Information System (INIS)

Ferreira, Henrique P.; Parra, Duclerc F.; Lugao, Ademar B.

2011-01-01

Polymers exhibiting ion exchange capacity are studied for many years due to their application in several fields, such as membranes for proton exchange fuel cells, filtration membranes, heavy ions recovery and artificial muscles and sensors. Radiation induced grafting followed by sulfonation is a well-known way to obtain ion exchange polymers. Fluorinated polymers are frequently used as polymeric matrix for grafting due to their excellent physicochemical properties. Radiation induced grafting of styrene into poly (vinylidene fluoride) (PVDF) by simultaneous method in 1:1 styrene/toluene or styrene/N,N-dimethylformamide solutions was studied. Irradiations were performed under nitrogen atmosphere, room temperature and at doses of 5, 10 and 20 kGy with dose rate of 5 kGy.h -1 from a 60 Co gamma source. After washing, grafted materials were sulfonated in 10% chlorosulfonic acid/1,2-dichloroethane solutions for 4 h at room temperature. Characterization shows that increasing irradiation dose corresponds to increases in the grafting yield (GY %) gravimetrically calculated and these different solvents shows different grafting behaviors. Toluene allows no more than 3 % of grafting while DMF allows up to 55 % of grafting in the same condition. Grafting in toluene solution occurs on the surface and in DMF solution it occurs in the bulk, as confirmed by SEM. Both irradiation doses and solvent used have direct effects in the ion exchange capacities (calculated after titrations). FT-IR spectra exhibit new peaks after grafting and after sulfonation, attributed to grafted monomer and sulfonic groups attached to the styrene. DSC shows differences in thermal behavior of the polymer before and after each step. (author)

Solvent and irradiation doses effects on the ion exchange capacity of sulfonated styrene grafted PVDF

Energy Technology Data Exchange (ETDEWEB)

Ferreira, Henrique P.; Parra, Duclerc F.; Lugao, Ademar B. [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

2011-07-01

Polymers exhibiting ion exchange capacity are studied for many years due to their application in several fields, such as membranes for proton exchange fuel cells, filtration membranes, heavy ions recovery and artificial muscles and sensors. Radiation induced grafting followed by sulfonation is a well-known way to obtain ion exchange polymers. Fluorinated polymers are frequently used as polymeric matrix for grafting due to their excellent physicochemical properties. Radiation induced grafting of styrene into poly (vinylidene fluoride) (PVDF) by simultaneous method in 1:1 styrene/toluene or styrene/N,N-dimethylformamide solutions was studied. Irradiations were performed under nitrogen atmosphere, room temperature and at doses of 5, 10 and 20 kGy with dose rate of 5 kGy.h{sup -1} from a {sup 60}Co gamma source. After washing, grafted materials were sulfonated in 10% chlorosulfonic acid/1,2-dichloroethane solutions for 4 h at room temperature. Characterization shows that increasing irradiation dose corresponds to increases in the grafting yield (GY %) gravimetrically calculated and these different solvents shows different grafting behaviors. Toluene allows no more than 3 % of grafting while DMF allows up to 55 % of grafting in the same condition. Grafting in toluene solution occurs on the surface and in DMF solution it occurs in the bulk, as confirmed by SEM. Both irradiation doses and solvent used have direct effects in the ion exchange capacities (calculated after titrations). FT-IR spectra exhibit new peaks after grafting and after sulfonation, attributed to grafted monomer and sulfonic groups attached to the styrene. DSC shows differences in thermal behavior of the polymer before and after each step. (author)

Atomistic simulation of CO 2 solubility in poly(ethylene oxide) oligomers

KAUST Repository

Hong, Bingbing

2013-10-02

We have performed atomistic molecular dynamics simulations coupled with thermodynamic integration to obtain the excess chemical potential and pressure-composition phase diagrams for CO2 in poly(ethylene oxide) oligomers. Poly(ethylene oxide) dimethyl ether, CH3O(CH 2CH2O)nCH3 (PEO for short) is a widely applied physical solvent that forms the major organic constituent of a class of novel nanoparticle-based absorbents. Good predictions were obtained for pressure-composition-density relations for CO2 + PEO oligomers (2 ≤ n ≤ 12), using the Potoff force field for PEO [J. Chem. Phys. 136, 044514 (2012)] together with the TraPPE model for CO2 [AIChE J. 47, 1676 (2001)]. Water effects on Henrys constant of CO2 in PEO have also been investigated. Addition of modest amounts of water in PEO produces a relatively small increase in Henrys constant. Dependence of the calculated Henrys constant on the weight percentage of water falls on a temperature-dependent master curve, irrespective of PEO chain length. © 2013 Taylor & Francis.

Solvent Annealing Induced Perpendicular Orientation of Cylindrical Microdomains in Polystyrene-b-poly(4-hydroxyl styrene)/PEG Oligomer Blend Thin Film Made by Spin-coating from Selective Solvent

Energy Technology Data Exchange (ETDEWEB)

Matsutani, Taito; Yamamoto, Katsuhiro, E-mail: yamamoto.katsuhiro@nitech.ac.jp [Department of Materials Science and Technology, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555 (Japan)

2011-01-01

The microphase separated structure of PS-b-PHS/PEG blend thin film with thickness of 500 {approx} 600 nm was investigated by grazing incidence small angle X-ray scattering. The thin film was obtained by two different solutions; one was THF which was common good solvent for all components of polymers used here. The other is toluene which was selective solvent for PS and poor-solvent for PHS and PEG. The equilibrium morphology of the block copolymer and blend sample was hexagonally packed cylinder in the bulk and thin film. The structure in the thin film obtained by spin cast from toluene solution was non-equilibrium. After THF vopar annealing of the thin film (cast from toluene), the highly ordered and perpendicular oriented cylindrical structure was obtained. Perpendicular orientation was failure when the thin film sample made by spin cast from THF solution and subsequent THF vapor annealing. The perpendicular nano-holes were fabricated after removing PEG oligomer by washing with water.

Radiation induced ionic polymerisation and grafting of vinyl monomers

International Nuclear Information System (INIS)

Stannett, V.T.

1981-01-01

Some special aspects of the radiation induced ionic polymerisation and grafting of vinyl monomers will be described. In particular the effects of solvents on the cationic polymerisation of the vinyl ethers will be discussed in detail. The unequivocal free ion nature of the polymerisation makes such information of considerable general interest. Estimates of the propagation rate constants with free cation polymerisation in solvents of different dielectric constants and solvation powers will be presented. Finally, some observations on the radiation induced graft polymerisation of ethyl vinyl ether to poly(vinyl chloride) and to polypropylene will be presented. (author)

Structural fingerprints and their evolution during oligomeric vs. oligomer-free amyloid fibril growth.

Science.gov (United States)

Foley, Joseph; Hill, Shannon E; Miti, Tatiana; Mulaj, Mentor; Ciesla, Marissa; Robeel, Rhonda; Persichilli, Christopher; Raynes, Rachel; Westerheide, Sandy; Muschol, Martin

2013-09-28

Deposits of fibrils formed by disease-specific proteins are the molecular hallmark of such diverse human disorders as Alzheimer's disease, type II diabetes, or rheumatoid arthritis. Amyloid fibril formation by structurally and functionally unrelated proteins exhibits many generic characteristics, most prominently the cross β-sheet structure of their mature fibrils. At the same time, amyloid formation tends to proceed along one of two separate assembly pathways yielding either stiff monomeric filaments or globular oligomers and curvilinear protofibrils. Given the focus on oligomers as major toxic species, the very existence of an oligomer-free assembly pathway is significant. Little is known, though, about the structure of the various intermediates emerging along different pathways and whether the pathways converge towards a common or distinct fibril structures. Using infrared spectroscopy we probed the structural evolution of intermediates and late-stage fibrils formed during in vitro lysozyme amyloid assembly along an oligomeric and oligomer-free pathway. Infrared spectroscopy confirmed that both pathways produced amyloid-specific β-sheet peaks, but at pathway-specific wavenumbers. We further found that the amyloid-specific dye thioflavin T responded to all intermediates along either pathway. The relative amplitudes of thioflavin T fluorescence responses displayed pathway-specific differences and could be utilized for monitoring the structural evolution of intermediates. Pathway-specific structural features obtained from infrared spectroscopy and Thioflavin T responses were identical for fibrils grown at highly acidic or at physiological pH values and showed no discernible effects of protein hydrolysis. Our results suggest that late-stage fibrils formed along either pathway are amyloidogenic in nature, but have distinguishable structural fingerprints. These pathway-specific fingerprints emerge during the earliest aggregation events and persist throughout the

Structural fingerprints and their evolution during oligomeric vs. oligomer-free amyloid fibril growth

Science.gov (United States)

Foley, Joseph; Hill, Shannon E.; Miti, Tatiana; Mulaj, Mentor; Ciesla, Marissa; Robeel, Rhonda; Persichilli, Christopher; Raynes, Rachel; Westerheide, Sandy; Muschol, Martin

2013-09-01

Deposits of fibrils formed by disease-specific proteins are the molecular hallmark of such diverse human disorders as Alzheimer's disease, type II diabetes, or rheumatoid arthritis. Amyloid fibril formation by structurally and functionally unrelated proteins exhibits many generic characteristics, most prominently the cross β-sheet structure of their mature fibrils. At the same time, amyloid formation tends to proceed along one of two separate assembly pathways yielding either stiff monomeric filaments or globular oligomers and curvilinear protofibrils. Given the focus on oligomers as major toxic species, the very existence of an oligomer-free assembly pathway is significant. Little is known, though, about the structure of the various intermediates emerging along different pathways and whether the pathways converge towards a common or distinct fibril structures. Using infrared spectroscopy we probed the structural evolution of intermediates and late-stage fibrils formed during in vitro lysozyme amyloid assembly along an oligomeric and oligomer-free pathway. Infrared spectroscopy confirmed that both pathways produced amyloid-specific β-sheet peaks, but at pathway-specific wavenumbers. We further found that the amyloid-specific dye thioflavin T responded to all intermediates along either pathway. The relative amplitudes of thioflavin T fluorescence responses displayed pathway-specific differences and could be utilized for monitoring the structural evolution of intermediates. Pathway-specific structural features obtained from infrared spectroscopy and Thioflavin T responses were identical for fibrils grown at highly acidic or at physiological pH values and showed no discernible effects of protein hydrolysis. Our results suggest that late-stage fibrils formed along either pathway are amyloidogenic in nature, but have distinguishable structural fingerprints. These pathway-specific fingerprints emerge during the earliest aggregation events and persist throughout the

Position transitions of polymer-grafted nanoparticles in diblock-copolymer nanocomposites

Directory of Open Access Journals (Sweden)

2011-04-01

Full Text Available Self-assembly of block copolymer/nanoparticle blends has promising applications in the design and fabrication of novel functional nanomaterials. Precise control of the spatial positions of nanoparticles within block copolymer-based nanomaterials is crucial to achieve some special physical properties and functions. Here, we employ the self-consistent field method to theoretically investigate the self-assembly of polymer grafted-nanoparticles in a diblock copolymer. It is found that by varying the size and selectivity of nanoparticles, one can not only produce various self-assembled nanostructures but also modulate the spatial positions of the nanoparticles, either at the copolymer interfaces or in the center of one copolymer phase, within the nanostructures. A denser grafted polymer brush plays a role of shielding effect on nanoparticles and can position them into the center of one copolymer phase. The nanostructural transition we observed is dictated by the competition between entropy and enthalpy. On the basis of a number of simulations, two phase diagrams of self-assembled nanostructures are constructed. This study may be helpful for optimal design of advanced materials with desired nanostructures and enhanced performance.

Computational Design of High-χ Block Oligomers for Accessing 1 nm Domains.

Science.gov (United States)

Chen, Qile P; Barreda, Leonel; Oquendo, Luis E; Hillmyer, Marc A; Lodge, Timothy P; Siepmann, J Ilja

2018-05-22

Molecular dynamics simulations are used to design a series of high-χ block oligomers (HCBOs) that can self-assemble into a variety of mesophases with domain sizes as small as 1 nm. The exploration of these oligomers with various chain lengths, volume fractions, and chain architectures at multiple temperatures reveals the presence of ordered lamellae, perforated lamellae, and hexagonally packed cylinders. The achieved periods are as small as 3.0 and 2.1 nm for lamellae and cylinders, respectively, which correspond to polar domains of approximately 1 nm. Interestingly, the detailed phase behavior of these oligomers is distinct from that of either solvent-free surfactants or block polymers. The simulations reveal that the behavior of these HCBOs is a product of an interplay between both "surfactant factors" (headgroup interactions, chain flexibility, and interfacial curvature) and "block polymer factors" (χ, chain length N, and volume fraction f). This insight promotes the understanding of molecular features pivotal for mesophase formation at the sub-5 nm length scale, which facilitates the design of HCBOs tailored toward particular desired morphologies.

Free and microvascular bone grafting in the irradiated dog mandible

International Nuclear Information System (INIS)

Altobelli, D.E.; Lorente, C.A.; Handren, J.H. Jr.; Young, J.; Donoff, R.B.; May, J.W. Jr.

1987-01-01

Microvascular and free rib grafts were placed in 4.5 cm defects in an edentate mandibular body defect 18 to 28 days after completion of 50 Gy of irradiation from a 60 Co source. The animals were sacrificed from two to forty weeks postoperatively and evaluated clinically, radiographically, and histologically. There was a marked difference in the alveolar mucosal viability with the two grafts. Mucosal dehiscence was not observed over any of the microvascular grafts, but was present in seven-eighths of the free grafts. Union of the microvascular bone graft to the host bone occurred within six weeks. In contrast, after six weeks the free graft was sequestered in all the animals. An unexpected finding with both types of graft was the marked subperiosteal bone formation. This bone appeared to be derived from the host bed, stabilizing and bridging the defects bilaterally. The results suggest that radiated periosteum may play an important role in osteogenesis

Process to prepare stable trifluorostyrene containing compounds grafted to base polymers using a solvent/water mixture

Science.gov (United States)

Roelofs, Mark Gerrit; Yang, Zhen-Yu; Han, Amy Qi

2010-06-15

A fluorinated ion exchange polymer is prepared by grafting at least one grafting monomer derived from trifluorostyrene on to at least one base polymer in a organic solvent/water mixture. These ion exchange polymers are useful in preparing catalyst coated membranes and membrane electrode assemblies used in fuel cells.

A sensitive and selective electrochemical biosensor for the determination of beta-amyloid oligomer by inhibiting the peptide-triggered in situ assembly of silver nanoparticles

Directory of Open Access Journals (Sweden)

Xing Y

2017-04-01

Full Text Available Yun Xing,1,2 Xiao-Zhen Feng,2 Lipeng Zhang,1 Jiating Hou,2 Guo-Cheng Han,2 Zhencheng Chen2 1Henan Province of Key Laboratory of New Optoelectronic Functional Materials, College of Chemistry and Chemical Engineering, Anyang Normal University, Anyang, 2School of Life and Environmental Sciences, Guilin University of Electronic Technology, Guilin, Guangxi, People’s Republic of China Abstract: Soluble beta-amyloid (Aβ oligomer is believed to be the most important toxic species in the brain of Alzheimer’s disease (AD patients. Thus, it is critical to develop a simple method for the selective detection of Aβ oligomer with low cost and high sensitivity. In this paper, we report an electrochemical method for the detection of Aβ oligomer with a peptide as the bioreceptor and silver nanoparticle (AgNP aggregates as the redox reporters. This strategy is based on the conversion of AgNP-based colorimetric assay into electrochemical analysis. Specifically, the peptide immobilized on the electrode surface and presented in solution triggered together the in situ formation of AgNP aggregates, which produced a well-defined electrochemical signal. However, the specific binding of Aβ oligomer to the immobilized peptide prevented the in situ assembly of AgNPs. As a result, a poor electrochemical signal was observed. The detection limit of the method was found to be 6 pM. Furthermore, the amenability of this method for the analysis of Aβ oligomer in serum and artificial cerebrospinal fluid (aCSF samples was demonstrated. Keywords: electrochemical biosensors, Alzheimer’s disease, beta-amyloid oligomer, peptide, silver nanoparticles

Interactions between Nanoparticles and Polymer Brushes: Molecular Dynamics Simulations and Self-consistent Field Theory Calculations

Science.gov (United States)

Cheng, Shengfeng; Wen, Chengyuan; Egorov, Sergei

2015-03-01

Molecular dynamics simulations and self-consistent field theory calculations are employed to study the interactions between a nanoparticle and a polymer brush at various densities of chains grafted to a plane. Simulations with both implicit and explicit solvent are performed. In either case the nanoparticle is loaded to the brush at a constant velocity. Then a series of simulations are performed to compute the force exerted on the nanoparticle that is fixed at various distances from the grafting plane. The potential of mean force is calculated and compared to the prediction based on a self-consistent field theory. Our simulations show that the explicit solvent leads to effects that are not captured in simulations with implicit solvent, indicating the importance of including explicit solvent in molecular simulations of such systems. Our results also demonstrate an interesting correlation between the force on the nanoparticle and the density profile of the brush. We gratefully acknowledge the support of NVIDIA Corporation with the donation of the Tesla K40 GPU used for this research.

Chemical approach to solvent removal during nanoencapsulation: its application to preparation of PLGA nanoparticles with non-halogenated solvent

Energy Technology Data Exchange (ETDEWEB)

Lee, Youngme [Ewha Womans University, College of Pharmacy (Korea, Republic of); Sah, Eric [University of Notre Dame, College of Science (United States); Sah, Hongkee, E-mail: hsah@ewha.ac.kr [Ewha Womans University, College of Pharmacy (Korea, Republic of)

2015-11-15

The objective of this study was to develop a new oil-in-water emulsion-based nanoencapsulation method for the preparation of PLGA nanoparticles using a non-halogenated solvent. PLGA (60–150 mg) was dissolved in 3 ml of methyl propionate, which was vortexed with 4 ml of a 0.5–4 % polyvinyl alcohol solution. This premix was sonicated for 2 min, added into 30 ml of the aqueous polyvinyl alcohol solution, and reacted with 3 ml of 10 N NaOH. Solvent removal was achieved by the alkaline hydrolysis of methyl propionate dissolved in an aqueous phase into water-soluble methanol and sodium propionate. It was a simple but effective technique to quickly harden nanoemulsion droplets into nanoparticles. The appearing PLGA nanoparticles were recovered by ultracentrifugation and/or dialysis, lyophilized with trehalose, and redispersed by water. This nanoencapsulation technique permitted a control of their mean diameters over 151.7 ± 3.8 to 440.2 ± 22.2 nm at mild processing conditions. When the aqueous polyvinyl alcohol concentration was set at ≥1 %, nanoparticles showed uniform distributions with polydispersity indices below 0.1. There were no significant changes in their mean diameters and size distribution patterns before and after lyophilization. When mestranol was encapsulated into nanoparticles, the drug was completely nanoencapsulated: depending on experimental conditions, their encapsulation efficiencies were determined to be 99.4 ± 7.2 to 105.8 ± 6.3 %. This simple, facile nanoencapsulation technique might have versatile applications for the preparation of polymeric nanoparticulate dosage forms.Graphical AbstractSchematic illustration of an innovative chemical approach to solvent removal during nanoencapsulation. Methyl propionate present in the aqueous continuous phase reacts with sodium hydroxide, thereby producing methanol and sodium propionate. Its alkaline hydrolysis allows the continuous extraction of the solvent out of nanoemulsion

Chemical approach to solvent removal during nanoencapsulation: its application to preparation of PLGA nanoparticles with non-halogenated solvent

International Nuclear Information System (INIS)

Lee, Youngme; Sah, Eric; Sah, Hongkee

2015-01-01

The objective of this study was to develop a new oil-in-water emulsion-based nanoencapsulation method for the preparation of PLGA nanoparticles using a non-halogenated solvent. PLGA (60–150 mg) was dissolved in 3 ml of methyl propionate, which was vortexed with 4 ml of a 0.5–4 % polyvinyl alcohol solution. This premix was sonicated for 2 min, added into 30 ml of the aqueous polyvinyl alcohol solution, and reacted with 3 ml of 10 N NaOH. Solvent removal was achieved by the alkaline hydrolysis of methyl propionate dissolved in an aqueous phase into water-soluble methanol and sodium propionate. It was a simple but effective technique to quickly harden nanoemulsion droplets into nanoparticles. The appearing PLGA nanoparticles were recovered by ultracentrifugation and/or dialysis, lyophilized with trehalose, and redispersed by water. This nanoencapsulation technique permitted a control of their mean diameters over 151.7 ± 3.8 to 440.2 ± 22.2 nm at mild processing conditions. When the aqueous polyvinyl alcohol concentration was set at ≥1 %, nanoparticles showed uniform distributions with polydispersity indices below 0.1. There were no significant changes in their mean diameters and size distribution patterns before and after lyophilization. When mestranol was encapsulated into nanoparticles, the drug was completely nanoencapsulated: depending on experimental conditions, their encapsulation efficiencies were determined to be 99.4 ± 7.2 to 105.8 ± 6.3 %. This simple, facile nanoencapsulation technique might have versatile applications for the preparation of polymeric nanoparticulate dosage forms.Graphical AbstractSchematic illustration of an innovative chemical approach to solvent removal during nanoencapsulation. Methyl propionate present in the aqueous continuous phase reacts with sodium hydroxide, thereby producing methanol and sodium propionate. Its alkaline hydrolysis allows the continuous extraction of the solvent out of nanoemulsion

Reconstruction of large upper eyelid defects with a free tarsal plate graft and a myocutaneous pedicle flap plus a free skin graft

DEFF Research Database (Denmark)

Toft, Peter B

2016-01-01

skin graft. RESULTS: All patients healed without necrosis, did not suffer from lagophthalmos, achieved reasonable cosmesis, and did not need lubricants. In one patient, a contact lens was necessary for three weeks because of corneal erosion. One patient still needs a contact lens 3 months after...... excision to avoid eye discomfort. CONCLUSION: Large upper eyelid defects can be reconstructed with a free tarsal plate graft and a laterally based myocutaneous pedicle flap in combination with a free skin graft. Two-step procedures can probably be avoided in most cases....

Nanocrystalline copper(II oxide-catalyzed one-pot four- component synthesis of polyhydroquinoline derivativesunder solvent-free conditions

Directory of Open Access Journals (Sweden)

J. Safaei-Ghomi

2011-07-01

Full Text Available The efficient and environmentally friendly method for the one-pot synthesis of polyhydroquinolines has been developed in the presence of CuO nanoparticles. The multi-component reactions of aldehydes, dimedone, ethyl acetoacetate andammonium acetate were carried out under solvent-free conditions to afford some polyhydroquinoline derivatives. This method provides several advantages including high yields, low reaction times and little catalyst loading.

Water-soluble PEGylated silicon nanoparticles and their assembly into swellable nanoparticle aggregates

International Nuclear Information System (INIS)

Xu, Zejing; Li, Yejia; Zhang, Boyu; Purkait, Tapas; Alb, Alina; Mitchell, Brian S.; Grayson, Scott M.; Fink, Mark J.

2015-01-01

Water-soluble silicon nanoparticles were synthesized by grafting PEG polymers onto functionalized silicon nanoparticles with distal alkyne or azide moieties. The surface-functionalized silicon nanoparticles were produced in one step from the reactive high-energy ball milling (RHEBM) of silicon wafers with a mixture of either 5-chloro-1-pentyne in 1-pentyne or 1,7 octadiyne in 1-hexyne to afford air and water-stable chloroalkyl or alkynyl-terminated nanoparticles, respectively. Nanoparticles with the ω-chloroalkyl substituents were easily converted to ω-azidoalkyl groups through the reaction of the Si nanoparticles with sodium azide in DMF. The azido-terminated nanoparticles were then grafted with mono-alkynyl-PEG polymers using a copper-catalyzed alkyne-azide cycloaddition (CuAAC) reaction to afford core–shell silicon nanoparticles with a covalently attached PEG shell. Covalently linked Si nanoparticle clusters were synthesized via the CuAAC “click” reaction of functional Si NPs with α,ω-functional PEG polymers of various lengths. Dynamic light scattering studies show that the flexible globular nanoparticle aggregates undergo a solvent-dependent change in volume (ethanol > dichloromethane > toluene) similar in behavior to hydrogel nanocomposites

Preparation and Characterization of Astaxanthin Nanoparticles by Solvent-Diffusion Technique

International Nuclear Information System (INIS)

Anarjan, N.; Tan, C.P.

2011-01-01

In this work, astaxanthin nanoparticles were prepared in aqueous media using solvent-diffusion technique. Sodium caseinate, gelatin, Polysorbate 20 and gum Arabic were selected as different food grade surface active molecules for the stabilization of the produced nanoparticles. Results showed that among produced astaxanthin nanoparticles, the Polysorbate 20-stabilized nanoparticles showed the smallest particle size; gum Arabic-stabilized nanoparticles had the smallest polydispersity index and highest physical stability in simulated gastric fluid (SGF); and those stabilized using gelatin had the highest zeta potential. Sodium caseinate stabilized nanoparticles had the highest astaxanthin content in fresh samples as compared to other prepared nano dispersions. (author)

"Living" free radical photopolymerization initiated from surface-grafted iniferter monolayers

NARCIS (Netherlands)

de Boer, B.; Simon, H.K.; Werts, M.P L; van der Vegte, E.W.; Hadziioannou, G

2000-01-01

A method for chemically modifying a surface with grafted monolayers of initiator groups, which can be used for a "living" free radical photopolymerization, is described. By using "living" free radical polymerizations, we were able to control the length of the grafted polymer chains and therefore the

Prednisolone multicomponent nanoparticle preparation by aerosol solvent extraction system.

Science.gov (United States)

Moribe, Kunikazu; Fukino, Mika; Tozuka, Yuichi; Higashi, Kenjirou; Yamamoto, Keiji

2009-10-01

Prednisolone nanoparticles were prepared in the presence of a hydrophilic polymer and a surfactant by the aerosol solvent extraction system (ASES). A ternary mixture of prednisolone, polyethylene glycol (PEG), and sodium dodecyl sulfate (SDS) dissolved in methanol was sprayed through a nozzle into the reaction vessel filled with supercritical carbon dioxide. After the ASES process was repeated, precipitates of the ternary components were obtained by depressurizing the reaction vessel. When a methanolic solution of prednisolone/PEG 4000/SDS at a weight ratio of 1:6:2 was sprayed under the optimized ASES conditions, the mean particle size of prednisolone obtained after dispersing the precipitates in water was observed to be ca. 230 nm. Prednisolone nanoparticles were not obtained by the binary ASES process for prednisolone, in the presence of either PEG or SDS. Furthermore, ternary cryogenic cogrinding, as well as solvent evaporation, was not effective for the preparation of prednisolone nanoparticles. As the ASES process can be conducted under moderate temperature conditions, the ASES process that was applied to the ternary system appeared to be one of the most promising methods for the preparation of drug nanoparticles using the multicomponent system.

Efficient self-assembly of DNA-functionalized fluorophores and gold nanoparticles with DNA functionalized silicon surfaces: the effect of oligomer spacers

Science.gov (United States)

Milton, James A.; Patole, Samson; Yin, Huabing; Xiao, Qiang; Brown, Tom; Melvin, Tracy

2013-01-01

Although strategies for the immobilization of DNA oligonucleotides onto surfaces for bioanalytical and top-down bio-inspired nanobiofabrication approaches are well developed, the effect of introducing spacer molecules between the surface and the DNA oligonucleotide for the hybridization of nanoparticle–DNA conjugates has not been previously assessed in a quantitative manner. The hybridization efficiency of DNA oligonucleotides end-labelled with gold nanoparticles (1.4 or 10 nm diameter) with DNA sequences conjugated to silicon surfaces via hexaethylene glycol phosphate diester oligomer spacers (0, 1, 2, 6 oligomers) was found to be independent of spacer length. To quantify both the density of DNA strands attached to the surfaces and hybridization with the surface-attached DNA, new methodologies have been developed. Firstly, a simple approach based on fluorescence has been developed for determination of the immobilization density of DNA oligonucleotides. Secondly, an approach using mass spectrometry has been created to establish (i) the mean number of DNA oligonucleotides attached to the gold nanoparticles and (ii) the hybridization density of nanoparticle–oligonucleotide conjugates with the silicon surface–attached complementary sequence. These methods and results will be useful for application with nanosensors, the self-assembly of nanoelectronic devices and the attachment of nanoparticles to biomolecules for single-molecule biophysical studies. PMID:23361467

Double-layered collagen graft to the radial forearm free flap donor sites without skin graft.

Science.gov (United States)

Park, Tae-Jun; Kim, Hong-Joon; Ahn, Kang-Min

2015-12-01

Radial forearm free flap is the most reliable flap for intraoral soft tissue reconstruction after cancer ablation surgery. However, unesthetic scar of the donor site and the need for a second donor site for skin graft are major disadvantages of the forearm flap. The purpose of this study was to report the clinical results of double-layered collagen graft to the donor site of the forearm free flap without skin graft. Twenty-two consecutive patients who underwent oral cancer ablation and forearm reconstruction between April 2010 and November 2013 were included in this study. Male to female ratio was 12:10, and average age was 61.0 years old (27-84). Double-layered collagen was grafted to the donor site of the forearm free flap and healed for secondary intention. Upper silicone had been trimmed at the periphery during secondary intention, and dry dressing was used. Postoperative scar healing and esthetic results and function were evaluated. An average follow-up period was 34.9 months. The scar area was decreased to 63.9 % in average. The complete healing was obtained between 1.5 and 3 months according to the defect size. There was no functional defect or impairment 3 months after operation. All patients were satisfied with the esthetic results. Three patients died of recurred cancer. Double-layered collagen graft was successfully performed in this study. Without the thigh skin graft, patients had experienced less painful postoperative healing periods and discomfort.

Free epidural fat-grafting after lumbar laminectomy using MRI

International Nuclear Information System (INIS)

Ohtsubo, Yoshimasa; Fujita, Masaaki; Motokawa, Satoru; Nakamura, Satoshi; Narabayashi, Yoko

1994-01-01

Free epidural fat-grafting was performed to prevent adhesion between scar tissue of the epidural space and dura and nerve root after lumbar laminectomy. The results were evaluated using MRI. Fifteen cases were operated upon with an average follow-up period of 7.5 months. MRI was recorded and the findings were classified into four types as follow: I, equally high signal case; II, slight fibrosis case; III, severe fibrosis case; IV, high signal disappeared case. The results showed 3 cases of type I, 7 cases of type II, 3 cases of type III, and 2 cases of type IV. According to MRI findings, free epidural fat is supposed to be still viable and alive, although slightly fibroses but the dural side remains a high signal area. Free epidural fat-grafting was useful for preventing adhesion around the epidural space. There was high relationship to age and sex with regard to viability of the free fat graft. (author)

Investigating the Formation Process of Sn-Based Lead-Free Nanoparticles with a Chemical Reduction Method

International Nuclear Information System (INIS)

Zhang, W.; Zhao, B.; Gao, Y.; Zhang, W.; Zhao, B.; Zou, Ch.; Zhai, Q.; Gao, Y.; Gao, Y.; Acquah, S.F.A.

2013-01-01

Nanoparticles of a promising lead-free solder alloy (Sn 3.5 Ag (wt.%, Sn Ag) and Sn 3.0 Ag 0.5 Cu (wt.%, SAC)) were synthesized through a chemical reduction method by using anhydrous ethanol and 1,10-phenanthroline as the solvent and surfactant, respectively. To illustrate the formation process of Sn-Ag alloy based nanoparticles during the reaction, X-ray diffraction (XRD) was used to investigate the phases of the samples in relation to the reaction time. Different nucleation and growth mechanisms were compared on the formation process of the synthesized nanoparticles. The XRD results revealed different reaction process compared with other researchers. There were many contributing factors to the difference in the examples found in the literature, with the main focus on the formation mechanism of crystal nuclei, the solubility and ionizability of metal salts in the solvent, the solid solubility of Cu in Ag nuclei, and the role of surfactant on the growth process. This study will help define the parameters necessary for the control of both the composition and size of the nanoparticles

Electron beam curing of acrylic oligomers

International Nuclear Information System (INIS)

Seto, J.; Arakawa, S.; Ishimoto, C.; Miyashita, M.; Nagai, T.; Noguchi, T.; Shibata, A.

1984-01-01

The electron-beam curing process of acrylic oligomers, with and without γ-Fe 2 O 3 pigment filler and blended linear polymer, was investigated in terms of molecular structure and reaction mechanism. The polymerized fraction of trimethylolpropane-triacrylate (TMPTA) oligomers increases with increasing total dose, and is independent of the dose rate. Since the reaction rate is linearly dependent on the dose rate, the reaction mechanism involves monomolecular termination. The reaction rate does not depend on the number of functional groups of the oligomer at low doses, but above 0.3 Mrad the rate is slower for oligomers of higher functionality. A gel is formed more readily upon curing of a polyfunctional than a monofunctional oligomer, especially at high conversion to polymer; the resulting loss of flexibility of the polymer chains slows the reaction. Decrease of the molecular weight per functional group results in lower conversion; this is also due to the loss of chain flexibility, which is indicated as well by a higher glass-transition temperature. Modification of the acrylate oligomers with urethane results in more effective cross-linking reactions because of the more rigid molecular chains. Addition of γ-Fe 2 O 3 pigment reduces the reaction rate very little, but has the effect of providing added structural integrity, as indicated by the decrease of solvent-extractable material and the improvement of anti-abrasion properties. However, the flexibility of the coating and its adhesion to a PET base film are diminished. To increase the flexibility, linear polyvinylchloride and/or polyurethane were added to the acrylic oligomers. Final conversion to polymer was nearly 100 percent, and a higher elastic modulus and better antiabrasion properties were realized

Polyacrylamide grafting of modified graphene oxides by in situ free radical polymerization

Energy Technology Data Exchange (ETDEWEB)

Tang, Mingyi [Department of Applied Chemistry, School of Science, Tianjin University of Commerce, Tianjin 300134 (China); Xu, Xiaoyang, E-mail: xiaoyangxu2012@163.com [School of Science, Tianjin University, Tianjin 30072 (China); Wu, Tao [School of Science, Tianjin University, Tianjin 30072 (China); Zhang, Sai; Li, Xianxian [Department of Applied Chemistry, School of Science, Tianjin University of Commerce, Tianjin 300134 (China); Li, Yi, E-mail: liyi@tju.edu.cn [School of Science, Tianjin University, Tianjin 30072 (China)

2014-12-15

Highlights: • Graphene oxide (GO) was modified by chemical reactions to functionalized GO (FGO). • The FGOs and the GO were then subjected to in situ free radical polymerization. • Hydroxyl groups of GO were the most reactive grafting sites. - Abstract: Graphene oxide (GO) was modified using chemical reactions to obtain three types of functionalized GO sheets (FGO). The FGO sheets and the GO were then subjected to in situ free radical polymerization in order to study the grafting polymerization. The FGO and grafted-.FGO were analyzed with Fourier transform infrared spectroscopy, scanning electronic microscopy, thermo-gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The grafting percentages in the materials were calculated using the TGA and XPS results. The FGO sheets with different functional groups exhibited different grafting abilities, and hydroxyl groups were proven to be the most reactive grafting sites for the in situ free radical grafting polymerization of polyacrylamide.

Polyacrylamide grafting of modified graphene oxides by in situ free radical polymerization

International Nuclear Information System (INIS)

Tang, Mingyi; Xu, Xiaoyang; Wu, Tao; Zhang, Sai; Li, Xianxian; Li, Yi

2014-01-01

Highlights: • Graphene oxide (GO) was modified by chemical reactions to functionalized GO (FGO). • The FGOs and the GO were then subjected to in situ free radical polymerization. • Hydroxyl groups of GO were the most reactive grafting sites. - Abstract: Graphene oxide (GO) was modified using chemical reactions to obtain three types of functionalized GO sheets (FGO). The FGO sheets and the GO were then subjected to in situ free radical polymerization in order to study the grafting polymerization. The FGO and grafted-.FGO were analyzed with Fourier transform infrared spectroscopy, scanning electronic microscopy, thermo-gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The grafting percentages in the materials were calculated using the TGA and XPS results. The FGO sheets with different functional groups exhibited different grafting abilities, and hydroxyl groups were proven to be the most reactive grafting sites for the in situ free radical grafting polymerization of polyacrylamide

Bimetallic Nanoparticles in Alternative Solvents for Catalytic Purposes

Directory of Open Access Journals (Sweden)

Trung Dang-Bao

2017-07-01

Full Text Available Bimetallic nanoparticles represent attractive catalytic systems thanks to the synergy between both partners at the atomic level, mainly induced by electronic effects which in turn are associated with the corresponding structures (alloy, core-shell, hetero-dimer. This type of engineered material can trigger changes in the kinetics of catalyzed processes by variations on the electrophilicity/nucleophilicity of the metal centers involved and also promote cooperative effects to foster organic transformations, including multi-component and multi-step processes. Solvents become a crucial factor in the conception of catalytic processes, not only due to their environmental impact, but also because they can preserve the bimetallic structure during the catalytic reaction and therefore increase the catalyst life-time. In this frame, the present review focuses on the recent works described in the literature concerning the synthesis of bimetallic nanoparticles in non-conventional solvents, i.e., other than common volatile compounds, for catalytic applications.

ODC-Free Solvent Implementation Issues for Vulcanized Rubber and Bond Systems

Science.gov (United States)

Hodgson, James R.; McCool, Alex (Technical Monitor)

2001-01-01

Thiokol Propulsion has worked extensively to replace 1,1,1-trichloroethane (TCA) with ozone depleting chemicals (ODC)-free solvents for use in the manufacture of the Reusable Solid Rocket Motor (RSRM) for the Space Shuttle Program. As Thiokol has transitioned from sub-scale to full-scale testing and implementation of these new solvents, issues have been discovered which have required special attention. The original intent of Thiokol's solvent replacement strategy was to replace TCA with a single drop-in solvent for all equivalent applications. We have learned that a single candidate does not exist for replacing TCA. Solvent incompatibility with process materials has caused us to seek for niche solvents and/or processing changes that provide an ODC-free solution for special applications. This paper addresses some of the solvent incompatibilities, which have lead to processes changes and possible niche solvent usage. These incompatibilities were discovered during full-scale testing of ODC-free solvents and relate to vulcanized rubber and bond systems in the RSRM. Specifically, the following items are presented: (1) Cure effects of d-limonene based solvents on Silica Filled Ethylene Propylene Diene Monomer (SF-EPDM) rubber. During full-scale test operations, Thiokol discovered that d-limonene (terpene) based solvents inhibit the cure of EPDM rubber. Subsequent testing showed the same issue with Nitrile Butadiene Rubber (NBR). Also discussed are efforts to minimize uncured rubber exposure to solvents; and (2) Cured bond system sensitivity to ODC-free solvents. During full scale testing it was discovered that a natural rubber to steel vulcanized bond could degrade after prolonged exposure to ODC-free solvents. Follow on testing showed that low vapor pressure and residence time seemed to be most likely cause for failure.

Magnetic amine-functionalized graphene oxide as a novel and recyclable bifunctional nanocatalyst for solvent-free synthesis of pyrano[3,2-c]pyridine derivatives

Directory of Open Access Journals (Sweden)

Shahnaz Rostamizadeh

2017-01-01

Full Text Available The new magnetic amine-functionalized graphene oxide (Fe3O4-GO-NH2 nanocatalyst was prepared through the reaction of 3-aminopropyltriethoxysilane (APTES with magnetic graphene oxide (Fe3O4-GO. It was characterized by XRD, TEM, SEM, FT-IR and EDX techniques. The intrinsic carboxylic acids on the edges of Fe3O4-GO along with the amine groups post grafted to the surface of Fe3O4-GO led to preparation of an acid-base bifunctional magnetically recyclable nanocatalyst. It proved to be efficient nanocatalyst for solvent-free synthesis of pyrano[3,2-c]pyridine derivatives under mild reaction conditions with good to excellent yields. This heterogeneous catalyst also exhibited higher activities than acid or base functionalized mesoporous silica, magnetic GO or basic Al2O3 an even higher than some basic homogeneous catalysts such as triethylamine and piperazine. More importantly, due to the loaded iron oxide nanoparticles, this catalyst could be easily recovered from the reaction mixture using an external magnet and reused without significant decrease in activity even after 7 runs.

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

Directory of Open Access Journals (Sweden)

Zhou WJ

2013-09-01

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

Preparation of Candesartan and Atorvastatin Nanoparticles by Solvent Evaporation

Czech Academy of Sciences Publication Activity Database

Vaculíková, E.; Grünwaldová, Veronika; Král, V.; Dohnal, J.; Jampílek, J.

2012-01-01

Roč. 17, č. 11 (2012), s. 13221-13234 ISSN 1420-3049 Institutional support: RVO:61388980 Keywords : candesartan cilexetil * atorvastatin * nanoparticles * solvent evaporation * excipients * dynamic light scattering Subject RIV: CA - Inorganic Chemistry Impact factor: 2.428, year: 2012

Connecting free energy surfaces in implicit and explicit solvent: an efficient method to compute conformational and solvation free energies.

Science.gov (United States)

Deng, Nanjie; Zhang, Bin W; Levy, Ronald M

2015-06-09

The ability to accurately model solvent effects on free energy surfaces is important for understanding many biophysical processes including protein folding and misfolding, allosteric transitions, and protein–ligand binding. Although all-atom simulations in explicit solvent can provide an accurate model for biomolecules in solution, explicit solvent simulations are hampered by the slow equilibration on rugged landscapes containing multiple basins separated by barriers. In many cases, implicit solvent models can be used to significantly speed up the conformational sampling; however, implicit solvent simulations do not fully capture the effects of a molecular solvent, and this can lead to loss of accuracy in the estimated free energies. Here we introduce a new approach to compute free energy changes in which the molecular details of explicit solvent simulations are retained while also taking advantage of the speed of the implicit solvent simulations. In this approach, the slow equilibration in explicit solvent, due to the long waiting times before barrier crossing, is avoided by using a thermodynamic cycle which connects the free energy basins in implicit solvent and explicit solvent using a localized decoupling scheme. We test this method by computing conformational free energy differences and solvation free energies of the model system alanine dipeptide in water. The free energy changes between basins in explicit solvent calculated using fully explicit solvent paths agree with the corresponding free energy differences obtained using the implicit/explicit thermodynamic cycle to within 0.3 kcal/mol out of ∼3 kcal/mol at only ∼8% of the computational cost. We note that WHAM methods can be used to further improve the efficiency and accuracy of the implicit/explicit thermodynamic cycle.

“Living” Free Radical Photopolymerization Initiated from Surface-Grafted Iniferter Monolayers

NARCIS (Netherlands)

Boer, B. de; Simon, H.K.; Werts, M.P.L.; Vegte, E.W. van der; Hadziioannou, G.

2000-01-01

A method for chemically modifying a surface with grafted monolayers of initiator groups, which can be used for a “living” free radical photopolymerization, is described. By using “living” free radical polymerizations, we were able to control the length of the grafted polymer chains and therefore the

Chronologic changes of free fat graft in rabbit using CT

International Nuclear Information System (INIS)

Kondo, Norihiro; Kurita, Kenichi; Yajima, Tetsuya; Izumi, Masahiro

2008-01-01

Free fat grafts are now used for preventing osteal readhesion, filling dead space, and protecting grafted nerves and vessels. However, it is reported that grafted fat tissue is unstable resulting in high risk of cicatrization and infection. We grafted free fat to a rabbit's back and observed the chronologic change using CT. Ten adult male Japanese white rabbits (3.5 kg) were used. In five rabbits, fat tissue was obtained from the back under general anaesthesia, and transplanted into the back about 50 mm posterior from the donor site. CT was taken in the fixed scan condition five times (preoperation, immediate postoperation, postoperative 1-month, 2-month, and 3-month). In the remaining five rabbits, only CT scan was taken three times as a control. It was observed that we compared preoperative fat volume with the postoperative volume using RealINTAGE. Grafted fat tissue decreased postoperatively at 1-month and completely disappeared at 3-months. We were able to prove that CT scan is effective to observe the chronologic change of grafted fat tissue. Techniques of tissue engineering are necessary for survival of grafted fat tissue. (author)

Preparation of Multifunctional Fe@Au Core-Shell Nanoparticles with Surface Grafting as a Potential Treatment for Magnetic Hyperthermia.

Science.gov (United States)

Chung, Ren-Jei; Shih, Hui-Ting

2014-01-24

Iron core gold shell nanoparticles grafted with Methotrexate (MTX) and indocyanine green (ICG) were synthesized for the first time in this study, and preliminarily evaluated for their potential in magnetic hyperthermia treatment. The core-shell Fe@Au nanoparticles were prepared via the microemulsion process and then grafted with MTX and ICG using hydrolyzed poly(styrene-alt-maleic acid) (PSMA) to obtain core-shell Fe@Au-PSMA-ICG/MTX nanoparticles. MTX is an anti-cancer therapeutic, and ICG is a fluorescent dye. XRD, TEM, FTIR and UV-Vis spectrometry were performed to characterize the nanoparticles. The data indicated that the average size of the nanoparticles was 6.4 ± 09 nm and that the Au coating protected the Fe core from oxidation. MTX and ICG were successfully grafted onto the surface of the nanoparticles. Under exposure to high frequency induction waves, the superparamagnetic nanoparticles elevated the temperature of a solution in a few minutes, which suggested the potential for an application in magnetic hyperthermia treatment. The in vitro studies verified that the nanoparticles were biocompatible; nonetheless, the Fe@Au-PSMA-ICG/MTX nanoparticles killed cancer cells (Hep-G2) via the magnetic hyperthermia mechanism and the release of MTX.

Cytocompatibility of amine functionalized carbon nanoparticles grafted on polyethylene

Energy Technology Data Exchange (ETDEWEB)

Žáková, Pavlína, E-mail: pavlina.zakova@vscht.cz [Department of Solid State Engineering, University of Chemistry and Technology, 166 28 Prague 6 (Czech Republic); Slepičková Kasálková, Nikola [Department of Solid State Engineering, University of Chemistry and Technology, 166 28 Prague 6 (Czech Republic); Kolská, Zdeňka [Faculty of Science, J. E. Purkyně University, Ústí nad Labem (Czech Republic); Leitner, Jindřich [Department of Solid State Engineering, University of Chemistry and Technology, 166 28 Prague 6 (Czech Republic); Karpíšková, Jana; Stibor, Ivan [Institute for Nanomaterials, Advanced Technologies and Innovation, Technical University of Liberec (Czech Republic); Slepička, Petr; Švorčík, Václav [Department of Solid State Engineering, University of Chemistry and Technology, 166 28 Prague 6 (Czech Republic)

2016-03-01

Five types of amide–amine Carbon Nano-Particles (CNPs) were prepared by functionalization of CNPs and characterized by several analytical methods. The successful grafting of amines on CNPs was verified by X-ray photoelectron spectroscopy (XPS), organic elemental analysis and electrokinetic analysis. The size and morphology of CNPs were determined from transmission electron microscopy. The surface area and porosity of CNPs were examined by adsorption and desorption isotherms. Differential scanning calorimetry was used to investigate thermal stability of CNPs. The amount of bonded amine depends on its dimensionality arrangement. Surface area and pore volumes of CNPs decrease several times after individual amino-compound grafting. Selected types of functionalized CNPs were grafted onto a plasma activated surface of HDPE. The successful grafting of CNPs on the polymer surface was verified by XPS. Wettability was determined by contact angle measurements. Surface morphology and roughness were studied by atomic force microscopy. A dramatic decrease of contact angle and surface morphology was observed on CNP grafted polymer surface. Cytocompatibility of modified surfaces was studied in vitro, by determination of adhesion, proliferation and viability of vascular smooth muscle cells (VSMCs). Grafting of CNPs onto the polymer surface has a positive effect on the adhesion, proliferation and viability of VSMCs. - Highlights: • Amine functionalized CNPs were successfully grafted on HDPE surface. • Significant change to the positive zeta potential for grafted CNPs was induced. • Grafting of CNPs significantly enhanced cell cytocompatibility and viability. • Homogeneous distribution of cells with correct size was achieved.

Particle localization and hyperuniformity of polymer-grafted nanoparticle materials

Energy Technology Data Exchange (ETDEWEB)

Chremos, Alexandros [Materials Science and Engineering Division, National Institute of Standards and Technology, Gaithersburg, MD (United States); Douglas, Jack F.

2017-05-15

The properties of materials largely reflect the degree and character of the localization of the molecules comprising them so that the study and characterization of particle localization has central significance in both fundamental science and material design. Soft materials are often comprised of deformable molecules and many of their unique properties derive from the distinct nature of particle localization. We study localization in a model material composed of soft particles, hard nanoparticles with grafted layers of polymers, where the molecular characteristics of the grafted layers allow us to ''tune'' the softness of their interactions. Soft particles are particular interesting because spatial localization can occur such that density fluctuations on large length scales are suppressed, while the material is disordered at intermediate length scales; such materials are called ''disordered hyperuniform''. We use molecular dynamics simulation to study a liquid composed of polymer-grafted nanoparticles (GNP), which exhibit a reversible self-assembly into dynamic polymeric GNP structures below a temperature threshold, suggesting a liquid-gel transition. We calculate a number of spatial and temporal correlations and we find a significant suppression of density fluctuations upon cooling at large length scales, making these materials promising for the practical fabrication of ''hyperuniform'' materials. (copyright 2017 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Tunable solvation effects on the size-selective fractionation of metal nanoparticles in CO2 gas-expanded solvents.

Science.gov (United States)

Anand, Madhu; McLeod, M Chandler; Bell, Philip W; Roberts, Christopher B

2005-12-08

This paper presents an environmentally friendly, inexpensive, rapid, and efficient process for size-selective fractionation of polydisperse metal nanoparticle dispersions into multiple narrow size populations. The dispersibility of ligand-stabilized silver and gold nanoparticles is controlled by altering the ligand tails-solvent interaction (solvation) by the addition of carbon dioxide (CO2) gas as an antisolvent, thereby tailoring the bulk solvent strength. This is accomplished by adjusting the CO2 pressure over the liquid, resulting in a simple means to tune the nanoparticle precipitation by size. This study also details the influence of various factors on the size-separation process, such as the types of metal, ligand, and solvent, as well as the use of recursive fractionation and the time allowed for settling during each fractionation step. The pressure range required for the precipitation process is the same for both the silver and gold particles capped with dodecanethiol ligands. A change in ligand or solvent length has an effect on the interaction between the solvent and the ligand tails and therefore the pressure range required for precipitation. Stronger interactions between solvent and ligand tails require greater CO2 pressure to precipitate the particles. Temperature is another variable that impacts the dispersibility of the nanoparticles through changes in the density and the mole fraction of CO2 in the gas-expanded liquids. Recursive fractionation for a given system within a particular pressure range (solvent strength) further reduces the polydispersity of the fraction obtained within that pressure range. Specifically, this work utilizes the highly tunable solvent properties of organic/CO2 solvent mixtures to selectively size-separate dispersions of polydisperse nanoparticles (2 to 12 nm) into more monodisperse fractions (+/-2 nm). In addition to providing efficient separation of the particles, this process also allows all of the solvent and

Dorsal free graft urethroplasty for urethral stricture by ventral sagittal urethrotomy approach.

Science.gov (United States)

Asopa, H S; Garg, M; Singhal, G G; Singh, L; Asopa, J; Nischal, A

2001-11-01

To explore the feasibility of applying a dorsal free graft to treat urethral stricture by the ventral sagittal urethrotomy approach without mobilizing the urethra. Twelve patients with long or multiple strictures of the anterior urethra were treated by a dorsal free full-thickness preputial or buccal mucosa graft. The urethra was not separated from the corporal bodies and was opened in the midline over the stricture. The floor of the urethra was incised, and an elliptical raw area was created over the tunica on which a free full-thickness graft of preputial or buccal mucosa was secured. The urethra was retubularized in one stage. After a follow-up of 8 to 40 months, one recurrence developed and required dilation. The ventral sagittal urethrotomy approach for dorsal free graft urethroplasty is not only feasible and successful, but is easy to perform.

Solvent-free Hydrodeoxygenation of Bio-oil Model Compounds Cyclopentanone and Acetophenone over Flame-made Bimetallic Pt-Pd/ZrO2 Catalysts

Science.gov (United States)

Jiang, Yijiao; Büchel, Robert; Huang, Jun; Krumeich, Frank; Pratsinis, Sotiris E.; Baiker, Alfons

2013-01-01

Bimetallic Pt-Pd/ZrO2 catalysts with different Pt/Pd atomic ratio and homogeneous dispersion of the metal nanoparticles were prepared in a single step by flame-spray pyrolysis. The catalysts show high activity and tuneable product selectivity for the solvent-free hydrodeoxygenation of the bio-oil model compounds cyclopentanone and acetophenone. PMID:22674738

Preparation and characterization of β-cyclodextrin grafted N-maleoyl chitosan nanoparticles for drug delivery

Directory of Open Access Journals (Sweden)

Xinyu Hou

2017-11-01

Full Text Available β-cyclodextrin (CD grafted N-maleoyl chitosan (CD-g-NMCS with two different degrees of substitution (DS of N-maleoyl (DS = 21.2% and 30.5% were synthesized from maleic anhydride and chitosan bearing pendant cyclodextrin (CD-g-CS. CD-g-NMCS based nanoparticles were prepared via an ionic gelation method together with chitosan and CD-g-CS nanoparticles. The size and zeta potential of prepared CD-g-NMCS nanoparticles were 179.2~274.0 nm and 36.2~42.4 mV, respectively. In vitro stability test indicated that CD-g-NMCS nanoparticles were more stable in phosphate-buffered saline compared with chitosan nanoparticles. Moreover, a poorly water-soluble drug, ketoprofen (KTP, was selected as a model drug to study the obtained nanoparticle's potentials as drug delivery carriers. The drug loading efficiency of CD-g-NMCS20 nanoparticles were 14.8% for KTP. MTT assay showed that KTP loaded CD-g-NMCS nanoparticles were safe drug carriers. Notably, in vitro drug release studies showed that KTP was released in a sustained-release manner for the nanoparticles. The pharmacokinetic of drug loaded CD-g-NMCS20 nanoparticles were evaluated in rats after intravenous administration. The results of studies revealed that, compared with free KTP, KTP loaded CD-g-NMCS20 nanoparticles exhibited a significant increase in AUC0→24h and mean residence time by 6.6-fold and 2.9-fold, respectively. Therefore, CD-g-NMCS nanoparticles could be used as a novel promising nanoparticle-based drug delivery system for sustained release of poorly water-soluble drugs. The carboxylic acid groups of the CD-g-NMCS molecule provide convenient sites for further structural modifications including introduction of tissue- or disease- specific targeting groups.

Kinetics of (3-aminopropyl)triethoxylsilane (APTES) silanization of superparamagnetic iron oxide nanoparticles.

Science.gov (United States)

Liu, Yue; Li, Yueming; Li, Xue-Mei; He, Tao

2013-12-10

Silanization of magnetic ironoxide nanoparticles with (3-aminopropyl)triethoxylsilane (APTES) is reported. The kinetics of silanization toward saturation was investigated using different solvents including water, water/ethanol (1/1), and toluene/methanol (1/1) at different reaction temperature with different APTES loading. The nanoparticles were characterized by Fourier transform infrared spectroscopy, vibrating sample magnetometry, transmission electron microscopy, and thermal gravimetric analysis (TGA). Grafting density data based on TGA were used for the kinetic modeling. It is shown that initial silanization takes place very fast but the progress toward saturation is very slow, and the mechanism may involve adsorption, chemical sorption, and chemical diffusion processes. The highest equilibrium grafting density of 301 mg/g was yielded when using toluene/methanol mixture as the solvent at a reaction temperature of 70 °C.

Red fluorescent chitosan nanoparticles grafted with poly(2-methacryloyloxyethyl phosphorylcholine) for live cell imaging.

Science.gov (United States)

Wang, Ke; Fan, Xingliang; Zhang, Xiaoyong; Zhang, Xiqi; Chen, Yi; Wei, Yen

2016-08-01

Poly(2-methacryloyloxyethyl phosphorylcholine) conjugated red fluorescent chitosan nanoparticles (GCC-pMPC) were facilely fabricated by "grafting from" method via surface initiated atom transfer radical polymerization (ATRP). Firstly, glutaraldehyde crosslinked red fluorescent chitosan nanoparticles (GCC NPs) with many amino groups and hydroxyl groups on their surface were prepared, which were then reacted with 2-bromoisobutyryl bromide to form GCC-Br; subsequently, poly(MPC) (pMPC) brushes were grafted onto GCC NPs surface using GCC-Br as initiator via ATRP. Compared with PEGylated nanoparticles, zwitterionic polymers modified nanoparticles demonstrated better performance in their cellular uptake. Moreover, the obtained GCC-pMPC demonstrated excellent water-dispersibility, biocompatibility, and photostability, which made them highly potential for long-term tracing applications. Importantly, the successful live cell imaging of GCC-pMPC would remarkably advance the research of their further bioapplications. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis, fractionation, and thin film processing of nanoparticles using the tunable solvent properties of carbon dioxide gas expanded liquids

Science.gov (United States)

Anand, Madhu

Nanoparticles have received significant attention because of their unusual characteristics including high surface area to volume ratios. Materials built from nanoparticles possess unique chemical, physical, mechanical and optical properties. Due to these properties, they hold potential in application areas such as catalysts, sensors, semiconductors and optics. At the same time, CO 2 in the form of supercritical fluid or CO2 gas-expanded liquid mixtures has gained significant attention in the area of processing nanostructures. This dissertation focuses on the synthesis and processing of nanoparticles using CO2 tunable solvent systems. Nanoparticle properties depend heavily on their size and, as such, the ability to finely control the size and uniformity of nanoparticles is of utmost importance. Solution based nanoparticle formation techniques are attractive due to their simplicity, but they often result in the synthesis of particles with a wide size range. To address this limitation, a post-synthesis technique has been developed in this dissertation to fractionate polydisperse nanoparticles ( s . = 30%) into monodisperse fractions ( s . = 8%) using tunable physicochemical properties of CO 2 expanded liquids, where CO2 is employed as an antisolvent. This work demonstrates that by controlling the addition of CO2 (pressurization) to an organic dispersion of nanoparticles, the ligand stabilized nanoparticles can be size selectively precipitated within a novel high pressure apparatus that confines the particle precipitation to a specified location on a surface. Unlike current techniques, this CO2 expanded liquid approach provides faster and more efficient particle size separation, reduction in organic solvent usage, and pressure tunable size selection in a single process. To improve our fundamental understanding and to further refine the size separation process, a detailed study has been performed to identify the key parameters enabling size separation of various

Tailoring magnetic nanoparticle for transformers application.

Science.gov (United States)

Morais, P C; Silva, A S; Leite, E S; Garg, V K; Oliveira, A C; Viali, W R; Sartoratto, P P C

2010-02-01

In this study photoacoustic spectroscopy was used to investigate the effect of dilution of an oil-based magnetic fluid sample on the magnetic nanoparticle surface-coating. Changes of the photoacoustic signal intensity on the band-L region (640 to 830 nm) upon dilution of the stock magnetic fluid sample were discussed in terms of molecular surface desorption. The model proposed here assumes that the driving force taking the molecules out from the nanoparticle surface into the bulk solvent is the gradient of osmotic pressure. This gradient of osmotic pressure is established between the nanoparticle surface and the bulk suspension. It is further assumed that the photoacoustic signal intensity (area under the photoacoustic spectra) scales linearly with the number of coating molecules (surface grafting) at the nanoparticle surface. This model picture provides a non-linear analytical description for the reduction of the surface grafting coefficient upon dilution, which was successfully-used to curve-fit the photoacoustic experimental data.

Preparation of Multifunctional Fe@Au Core-Shell Nanoparticles with Surface Grafting as a Potential Treatment for Magnetic Hyperthermia

Directory of Open Access Journals (Sweden)

Ren-Jei Chung

2014-01-01

Full Text Available Iron core gold shell nanoparticles grafted with Methotrexate (MTX and indocyanine green (ICG were synthesized for the first time in this study, and preliminarily evaluated for their potential in magnetic hyperthermia treatment. The core-shell Fe@Au nanoparticles were prepared via the microemulsion process and then grafted with MTX and ICG using hydrolyzed poly(styrene-alt-maleic acid (PSMA to obtain core-shell Fe@Au-PSMA-ICG/MTX nanoparticles. MTX is an anti-cancer therapeutic, and ICG is a fluorescent dye. XRD, TEM, FTIR and UV-Vis spectrometry were performed to characterize the nanoparticles. The data indicated that the average size of the nanoparticles was 6.4 ± 09 nm and that the Au coating protected the Fe core from oxidation. MTX and ICG were successfully grafted onto the surface of the nanoparticles. Under exposure to high frequency induction waves, the superparamagnetic nanoparticles elevated the temperature of a solution in a few minutes, which suggested the potential for an application in magnetic hyperthermia treatment. The in vitro studies verified that the nanoparticles were biocompatible; nonetheless, the Fe@Au-PSMA-ICG/MTX nanoparticles killed cancer cells (Hep-G2 via the magnetic hyperthermia mechanism and the release of MTX.

Breakdown of the Stokes-Einstein Relation for the Rotational Diffusivity of Polymer Grafted Nanoparticles in Polymer Melts.

Science.gov (United States)

Maldonado-Camargo, Lorena; Rinaldi, Carlos

2016-11-09

We report observations of breakdown of the Stokes-Einstein relation for the rotational diffusivity of polymer-grafted spherical nanoparticles in polymer melts. The rotational diffusivity of magnetic nanoparticles coated with poly(ethylene glycol) dispersed in poly(ethylene glycol) melts was determined through dynamic magnetic susceptibility measurements of the collective rotation of the magnetic nanoparticles due to imposed time-varying magnetic torques. These measurements clearly demonstrate the existence of a critical molecular weight for the melt polymer, below which the Stokes-Einstein relation accurately describes the rotational diffusivity of the polymer-grafted nanoparticles and above which the Stokes-Einstein relation ceases to apply. This critical molecular weight was found to correspond to a chain contour length that approximates the hydrodynamic diameter of the nanoparticles.

Avoiding secondary skin graft donor site morbidity in the fibula free flap harvest.

Science.gov (United States)

Kim, Paul D; Fleck, Terry; Heffelfinger, Ryan; Blackwell, Keith E

2008-12-01

To compare donor site morbidity in patients who have undergone fibula free flap reconstruction in which the skin graft was taken from the expected cutaneous paddle of the fibula with the known complications of the popular technique of obtaining a split-thickness skin graft (STSG) from a secondary donor site. Cohort study. The tertiary care centers at Loma Linda University Medical Center and University of California, Los Angeles, Medical Center. From September 1, 2006, to March 30, 2007, 30 patients underwent fibula free flap harvest by 2 surgeons at separate tertiary care centers. Twenty-one of those procedures took place at the University of California, Los Angeles, and 9 at Loma Linda University. Patients included 15 men (50%) and 15 women (50%), with a mean age of 58 (range, 19-88) years. All 30 patients underwent fibula free flap harvest with a split-thickness skin graft (graft thickness, 0.04 cm), obtained from osteocutaneous paddle using a 5.1-cm-wide dermatome, as well as oral cavity and oropharyngeal reconstruction with the de-epithelialized skin paddle. Measures of donor site morbidity, including graft failure and wound breakdown, and measures of recipient site morbidity, including flap failure, hardware complications, intraoral complications, and the need for additional surgery. Of the 30 patients who underwent this procedure, 4 had partial skin graft failures, for a complete skin graft survival of 87%. There were no complete skin graft losses. Regarding the fibula osteocutaneous free flap, there were no complete flap losses, 1 skin paddle necrosis that required debridement, 2 postoperative orocutaneous fistulas, 1 case of infected/extruded hardware, and 1 adhesion formation that required additional surgery for lysis of adhesion and placement of the split-thickness skin graft. The outlined novel technique has similar rates of free flap survival and skin graft take compared with previously described methods. Harvesting the skin graft over the expected

Solvent-free functionalization of silicone rubber and efficacy of PAAm brushes grafted from an amino-PPX layer against bacterial adhesion

NARCIS (Netherlands)

Fundeanu, Irina; Klee, Doris; Schouten, Arend J.; Busscher, Henk J.; van der Mei, Henny C.

Silicone rubber is a frequently employed biomaterial that is prone to bacterial adhesion and biofilm formation. In this study, the surface of silicone rubber was solvent-free functionalized by chemical vapor deposition (CVD) of poly(o-amino-p-xylylene-co-p-xylylene (amino-PPX). Subsequently, the

Supported Silver Nanoparticle and Near-Interface Solution Dynamics in a Deep Eutectic Solvent

Energy Technology Data Exchange (ETDEWEB)

Hammons, Joshua A.; Ustarroz, Jon; Muselle, Thibault; Torriero, Angel A. J.; Terryn, Herman; Suthar, Kamlesh; Ilavsky, Jan

2016-01-28

Type III deep eutectic solvents (DES) have attracted significant interest as both environmentally friendly and functional solvents that are, in some ways, advantageous to traditional aqueous systems. While these solvents continue to produce remarkable thin films and nanoparticle assemblies, their interactions with metallic surfaces are complex and difficult to manipulate. In this study, the near-surface region (2–600 nm) of a carbon surface is investigated immediately following silver nanoparticle nucleation and growth. This is accomplished, in situ, using a novel grazing transmission small-angle X-ray scattering approach with simultaneous voltammetry and electrochemical impedance spectroscopy. With this physical and electrochemical approach, the time evolution of three distinct surface interaction phenomena is observed: aggregation and coalescence of Ag nanoparticles, multilayer perturbations induced by nonaggregated Ag nanoparticles, and a stepwise transport of dissolved Ag species from the carbon surface. The multilayer perturbations contain charge-separated regions of positively charged choline-ethylene and negatively charged Ag and Cl species. Both aggregation-coalescence and the stepwise decrease in Ag precursor near the surface are observed to be very slow (~2 h) processes, as both ion and particle transport are significantly impeded in a DES as compared to aqueous electrolytes. Finally, altogether, this study shows how the unique chemistry of the DES changes near the surface and in the presence of nanoparticles that adsorb the constituent species.

Structure and transport properties of polymer grafted nanoparticles

KAUST Repository

Goyal, Sushmit; Escobedo, Fernando A.

2011-01-01

We perform molecular dynamics simulations on a bead-spring model of pure polymer grafted nanoparticles (PGNs) and of a blend of PGNs with a polymer melt to investigate the correlation between PGN design parameters (such as particle core concentration, polymer grafting density, and polymer length) and properties, such as microstructure, particle mobility, and viscous response. Constant strain-rate simulations were carried out to calculate viscosities and a constant-stress ensemble was used to calculate yield stresses. The PGN systems are found to have less structural order, lower viscosity, and faster diffusivity with increasing length of the grafted chains for a given core concentration or grafting density. Decreasing grafting density causes depletion effects associated with the chains leading to close contacts between some particle cores. All systems were found to shear thin, with the pure PGN systems shear thinning more than the blend; also, the pure systems exhibited a clear yielding behavior that was absent in the blend. Regarding the mechanism of shear thinning at the high shear rates examined, it was found that the shear-induced decrease of Brownian stresses and increase in chain alignment, both correlate with the reduction of viscosity in the system with the latter being more dominant. A coupling between Brownian stresses and chain alignment was also observed wherein the non-equilibrium particle distribution itself promotes chain alignment in the direction of shear. © 2011 American Institute of Physics.

Structural and functional features of self-assembling protein nanoparticles produced in endotoxin-free Escherichia coli.

Science.gov (United States)

Rueda, Fabián; Céspedes, María Virtudes; Sánchez-Chardi, Alejandro; Seras-Franzoso, Joaquin; Pesarrodona, Mireia; Ferrer-Miralles, Neus; Vázquez, Esther; Rinas, Ursula; Unzueta, Ugutz; Mamat, Uwe; Mangues, Ramón; García-Fruitós, Elena; Villaverde, Antonio

2016-04-08

Production of recombinant drugs in process-friendly endotoxin-free bacterial factories targets to a lessened complexity of the purification process combined with minimized biological hazards during product application. The development of nanostructured recombinant materials in innovative nanomedical activities expands such a need beyond plain functional polypeptides to complex protein assemblies. While Escherichia coli has been recently modified for the production of endotoxin-free proteins, no data has been so far recorded regarding how the system performs in the fabrication of smart nanostructured materials. We have here explored the nanoarchitecture and in vitro and in vivo functionalities of CXCR4-targeted, self-assembling protein nanoparticles intended for intracellular delivery of drugs and imaging agents in colorectal cancer. Interestingly, endotoxin-free materials exhibit a distinguishable architecture and altered size and target cell penetrability than counterparts produced in conventional E. coli strains. These variant nanoparticles show an eventual proper biodistribution and highly specific and exclusive accumulation in tumor upon administration in colorectal cancer mice models, indicating a convenient display and function of the tumor homing peptides and high particle stability under physiological conditions. The observations made here support the emerging endotoxin-free E. coli system as a robust protein material producer but are also indicative of a particular conformational status and organization of either building blocks or oligomers. This appears to be promoted by multifactorial stress-inducing conditions upon engineering of the E. coli cell envelope, which impacts on the protein quality control of the cell factory.

Controlling the morphology and properties of solvothermal synthesized Cu2ZnSnS4 nanoparticles by solvent type

International Nuclear Information System (INIS)

Bahramzadeh, Saeid; Abdizadeh, Hossein; Golobostanfard, Mohammad Reza

2015-01-01

Highlights: • CZTS nanoparticles are fabricated by solvothermal method with different solvents. • Different morphologies are achieved by EDA, TETA, EG, and OA solvents. • Property and chelating ability of the solvents have a key role on nanoparticles formation. • TETA and OA are strongly recommended for solar cell applications. - Abstract: The copper–zinc–tin sulfide Cu 2 ZnSnS 4 (CZTS) semiconductors are recently considered as one of the favorable materials for application as absorber layers in solar cells due to their appropriate direct band gap energy and high optical absorption coefficient. In this study, the effect of solvent type on properties of solvothermal synthesized CZTS nanoparticles has been investigated. Ethylenediamine (EDA), triethylenetetramine (TETA), ethylene glycol (EG), and oleic acid (OA) have been used as the solvent. X-ray diffraction technique and Raman spectroscopy confirmed the formation of crystalline CZTS nanoparticles with kesterite crystal structure in these solvents with the exception of EDA, which forms wurtzite crystal structure. Morphological characterizations show that several distinct morphologies including spherical (70–160 nm), nanoplates (∼45 nm thickness and more than 1 μm length), peculiar flower-like particles (with diameter of ∼0.4–1.5 μm), truncated hexagonal disks, irregular particles, and hexagonal microdisks are obtained by varying the solvent type. Optical studies revealed broad absorption of the CZTS particles in the visible region. Compared with other solvents, OA synthesized CZTS particles show higher absorption in the visible region. However, CZTS nanoparticles synthesized by TETA solvent show the most appropriate properties for application as an absorber materials in solar cells due to high crystallinity, low impurity phases, suitable size, and proper band gap energy

Purification of Drug Loaded PLGA Nanoparticles Prepared by Emulsification Solvent Evaporation Using Stirred Cell Ultrafiltration Technique.

Science.gov (United States)

Paswan, Suresh K; Saini, T R

2017-12-01

The emulsifiers in an exceedingly higher level are used in the preparation of drug loaded polymeric nanoparticles prepared by emulsification solvent evaporation method. This creates great problem to the formulator due to their serious toxicities when it is to be administered by parenteral route. The final product is therefore required to be freed from the used surfactants by the conventional purification techniques which is a cumbersome job. The solvent resistant stirred cell ultrafiltration unit (Millipore) was used in this study using polyethersulfone ultrafiltration membrane (Biomax®) having pore size of NMWL 300 KDa as the membrane filter. The purification efficiency of this technique was compared with the conventional centrifugation technique. The flow rate of ultrafiltration was optimized for removal of surfactant (polyvinyl alcohol) impurities to the acceptable levels in 1-3.5 h from the nanoparticle dispersion of tamoxifen prepared by emulsification solvent evaporation method. The present investigations demonstrate the application of solvent resistant stirred cell ultrafiltration technique for removal of toxic impurities of surfactant (PVA) from the polymeric drug nanoparticles (tamoxifen) prepared by emulsification solvent evaporation method. This technique offers added benefit of producing more concentrated nanoparticles dispersion without causing significant particle size growth which is observed in other purification techniques, e.g., centrifugation and ultracentrifugation.

Determination of oligomers in virgin and recycled polyethylene terephthalate (PET) samples by UPLC-MS-QTOF.

Science.gov (United States)

Ubeda, Sara; Aznar, Margarita; Nerín, Cristina

2018-03-01

An oligomer is a molecule that consists of a few monomer units. It can be formed during polymer manufacturing and also due to polymer degradation processes or even during use conditions. Since oligomers are not included in chemical databases, their identification is a complex process. In this work, the oligomers present in 20 different PET pellet samples have been determined. Two different sample treatment procedures, solvent extraction and total dissolution, were applied in order to select the most efficient one. The analyses were carried out by UPLC-MS-QTOF. The use of high resolution mass spectrometry allowed the structural elucidation of these compounds and their correct identification. The main oligomers identified were cyclic as well as lineal from the first, second, and third series. All of them were composed of terephthalic acid (TPA), diethylene glycol (DEG), and ethylene glycol (EG). Quantitative values were very different in both procedures. In total dissolution of PET samples, the concentration of oligomers was always, at least, 10 times higher than in solvent extraction; some of the compounds were only detected when total dissolution was used. Results showed that the oligomers with the highest concentration values were dimers and trimers, cyclic, as well as lineal, from the first and second series. The oligomer with the maximum concentration value was TPA 2 -EG-DEG that was found in all the samples in a concentration range from 2493 to 19,290 ng/g PET. No differences between virgin and recycled PET were found. Migration experiments were performed in two PET bottles, and results showed the transference of most of these oligomers to a fat food simulant (ethanol 95%). Graphical abstract Graphical abstract of the two procedures developd and optimized for identifying oligomers in PET pellets and in migration form PET bottles.

Tuning the Mechanical Properties of Polymer Nanocomposites Filled with Grafted Nanoparticles by Varying the Grafted Chain Length and Flexibility

Directory of Open Access Journals (Sweden)

Zixuan Wang

2016-08-01

Full Text Available By employing coarse-grained molecular dynamics simulation, we simulate the spatial organization of the polymer-grafted nanoparticles (NPs in homopolymer matrix and the resulting mechanical performance, by particularly regulating the grafted chain length and flexibility. The morphologies ranging from the agglomerate, cylinder, sheet, and string to full dispersion are observed, by gradually increasing the grafted chain length. The radial distribution function and the total interaction energy between NPs are calculated. Meanwhile, the stress–strain behavior of each morphology and the morphological evolution during the uniaxial tension are simulated. In particular, the sheet structure exhibits the best mechanical reinforcement compared to other morphologies. In addition, the change of the grafted chain flexibility to semi-flexibility leads to the variation of the morphology. We also find that at long grafted chain length, the stress–strain behavior of the system with the semi-flexible grafted chain begins to exceed that of the system with the flexible grafted chain, attributed to the physical inter-locking interaction between the matrix and grafted polymer chains. A similar transition trend is as well found in the presence of the interfacial chemical couplings between grafted and matrix polymer chains. In general, this work is expected to help to design and fabricate high performance polymer nanocomposites filled with grafted NPs with excellent and controllable mechanical properties.

Free Energy, Enthalpy and Entropy from Implicit Solvent End-Point Simulations.

Science.gov (United States)

Fogolari, Federico; Corazza, Alessandra; Esposito, Gennaro

2018-01-01

Free energy is the key quantity to describe the thermodynamics of biological systems. In this perspective we consider the calculation of free energy, enthalpy and entropy from end-point molecular dynamics simulations. Since the enthalpy may be calculated as the ensemble average over equilibrated simulation snapshots the difficulties related to free energy calculation are ultimately related to the calculation of the entropy of the system and in particular of the solvent entropy. In the last two decades implicit solvent models have been used to circumvent the problem and to take into account solvent entropy implicitly in the solvation terms. More recently outstanding advancement in both implicit solvent models and in entropy calculations are making the goal of free energy estimation from end-point simulations more feasible than ever before. We review briefly the basic theory and discuss the advancements in light of practical applications.

Free Energy, Enthalpy and Entropy from Implicit Solvent End-Point Simulations

Directory of Open Access Journals (Sweden)

Federico Fogolari

2018-02-01

Full Text Available Free energy is the key quantity to describe the thermodynamics of biological systems. In this perspective we consider the calculation of free energy, enthalpy and entropy from end-point molecular dynamics simulations. Since the enthalpy may be calculated as the ensemble average over equilibrated simulation snapshots the difficulties related to free energy calculation are ultimately related to the calculation of the entropy of the system and in particular of the solvent entropy. In the last two decades implicit solvent models have been used to circumvent the problem and to take into account solvent entropy implicitly in the solvation terms. More recently outstanding advancement in both implicit solvent models and in entropy calculations are making the goal of free energy estimation from end-point simulations more feasible than ever before. We review briefly the basic theory and discuss the advancements in light of practical applications.

Green synthesis, characterization and catalytic activity of natural bentonite-supported copper nanoparticles for the solvent-free synthesis of 1-substituted 1H-1,2,3,4-tetrazoles and reduction of 4-nitrophenol

Directory of Open Access Journals (Sweden)

Akbar Rostami-Vartooni

2015-12-01

Full Text Available In this study, Cu nanoparticles were immobilized on the surface of natural bentonite using Thymus vulgaris extract as a reducing and stabilizing agent. The natural bentonite-supported copper nanoparticles (Cu NPs/bentonite were characterized by FTIR spectroscopy, X-ray diffraction (XRD, X-ray fluorescence (XRF, field emission scanning electron microscopy (FE-SEM, energy dispersive X-ray spectroscopy (EDS, transmission electron microscopy (TEM, selected area electron diffraction (SAED and Brunauer–Emmett–Teller (BET analysis. Afterward, the catalytic performance of the prepared catalyst was investigated for the solvent-free synthesis of 1-substituted 1H-1,2,3,4-tetrazoles and reduction of 4-nitrophenol (4-NP in water. It was found that the Cu NPs/bentonite is a highly active and recyclable catalyst for related reactions.

Cluster synthesis of monodisperse rutile-TiO2 nanoparticles and dielectric TiO2-vinylidene fluoride oligomer nanocomposites

International Nuclear Information System (INIS)

Balasubramanian, Balamurugan; Kraemer, Kristin L; Valloppilly, Shah R; Ducharme, Stephen; Sellmyer, David J

2011-01-01

The embedding of oxide nanoparticles in polymer matrices produces a greatly enhanced dielectric response by combining the high dielectric strength and low loss of suitable host polymers with the high electric polarizability of nanoparticles. The fabrication of oxide-polymer nanocomposites with well-controlled distributions of nanoparticles is, however, challenging due to the thermodynamic and kinetic barriers between the polymer matrix and nanoparticle fillers. In the present study, monodisperse TiO 2 nanoparticles having an average particle size of 14.4 nm and predominant rutile phase were produced using a cluster-deposition technique without high-temperature thermal annealing and subsequently coated with uniform vinylidene fluoride oligomer (VDFO) molecules using a thermal evaporation source, prior to deposition as TiO 2 -VDFO nanocomposite films on suitable substrates. The molecular coatings on TiO 2 nanoparticles serve two purposes, namely to prevent the TiO 2 nanoparticles from contacting each other and to couple the nanoparticle polarization to the matrix. Parallel-plate capacitors made of TiO 2 -VDFO nanocomposite film as the dielectric exhibit minimum dielectric dispersion and low dielectric loss. Dielectric measurements also show an enhanced effective dielectric constant in TiO 2 -VDFO nanocomposites as compared to that of pure VDFO. This study demonstrates for the first time a unique electroactive particle coating in the form of a ferroelectric VDFO that has high-temperature stability as compared to conventionally used polymers for fabricating dielectric oxide-polymer nanocomposites.

Palladium nanoparticles immobilized on multifunctional ‎hyperbranched polyglycerol-grafted magnetic nanoparticles as a ‎sustainable and efficient catalyst for C-C coupling reactions

Directory of Open Access Journals (Sweden)

Mina Amini

2016-07-01

Full Text Available This study offers an exclusive class of magnetic nanoparticles supported hyperbranched polyglycerol (MNP/HPG that was functionalized with citric acid (MNP/HPG-CA as a host immobilization of palladium nanoparticles. The MNP/HPG-CA/Pd catalyst was fully characterized using some different techniques such as thermogravimetric analysis (TGA, x-ray diffraction (XRD, transmission electron microscopy (TEM, scanning electron microscopy (SEM, energy-dispersive x-ray spectroscopy (EDX, inductively coupled plasma (ICP and x-ray photoelectron spectroscopy (XPS. The new catalytic system showed high activity for the Suzuki–Miyaura cross-coupling and Heck reaction under mild and green conditions. Besides, the MNP/HPG-CA/Pd was found to be a convenient catalyst for copper-free Sonogashira coupling reaction in water as a green solvent at room temperature. Moreover, the catalyst could be recovered easily and reused several times without significant loss of reactivity. Ease of preparation, oxygen insensitive, phosphine-free, air- and moisture-stable, and high reusability of this immobilized palladium catalyst are the noteworthy advantages of this catalytic system.

Surface modification of silica nanoparticles by UV-induced graft polymerization of methyl methacrylate.

Science.gov (United States)

Kim, Sooyeon; Kim, Eunhye; Kim, Sungsoo; Kim, Woosik

2005-12-01

In this study we modified the surface of silica nanoparticles with methyl methacrylate by UV-induced graft polymerization. It is a surface-initiated polymerization reaction induced by ultraviolet irradiation. The resulting organic-inorganic nanocomposites were near-monodisperse and fabricated without homopolymerization of the monomer. Substantial increase in mean particle size was observed by SEM image analysis after UV-induced grafting of methyl methacrylate onto pure silica particles. FT-Raman spectroscopy and X-ray photoelectron spectroscopy studies of these materials revealed the successful grafting of methyl methacrylate onto the silica surface. The formation of a covalent bond between the grafted PMMA chains and silica surface was indicated by FT-Raman spectra. Thermogravimetric analysis of the PMMA-grafted silica particles indicated the polymer contents in good agreement with SEM photographs.

Interpenetrating polymer networks based on cyanate ester and fluorinated ethynyl-terminated imide oligomers

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Y. Wen

2017-12-01

Full Text Available Highly soluble fluorinated ethynyl-terminated imide (FETI oligomers were prepared via a conventional one-step method in m-cresol, using 4, 4′-(hexafluoroisopropylidene diphthalic anhydride and 2, 2′-bis(trifluoromethyl benzidine as the monomers, and ethynylphthalic anhydride as the end-capper; then interpenetrating polymer networks (IPN were formulated from FETI oligomers and bisphenol A dicyanate ester (BADCy through a solvent-free procedure, and their thermal, mechanical, and dielectric properties were fully characterized. The curing mechanism was studied by model reactions using nitrogen nuclear magnetic resonance. As evidenced by differential scanning calorimetry analysis and rheological measurements, the FETI/BADCy blends exhibited lower curing temperature and shorter gelation time in comparison with pure BADCy due to the catalytic effects of ethynyl and residue amic acid groups. The properties of IPNs were fully compared with those of polycyanurate, and the results revealed that the incorporation of FETI into cyanate ester resins could significantly improve the toughness, glass transition temperatures, mechanical and dielectric properties of the resultant IPNs.

Polyether-polyester graft copolymer

Science.gov (United States)

Bell, Vernon L. (Inventor)

1987-01-01

Described is a polyether graft polymer having improved solvent resistance and crystalline thermally reversible crosslinks. The copolymer is prepared by a novel process of anionic copolymerization. These polymers exhibit good solvent resistance and are well suited for aircraft parts. Previous aromatic polyethers, also known as polyphenylene oxides, have certain deficiencies which detract from their usefulness. These commercial polymers are often soluble in common solvents including the halocarbon and aromatic hydrocarbon types of paint thinners and removers. This limitation prevents the use of these polyethers in structural articles requiring frequent painting. In addition, the most popular commercially available polyether is a very high melting plastic. This makes it considerably more difficult to fabricate finished parts from this material. These problems are solved by providing an aromatic polyether graft copolymer with improved solvent resistance and crystalline thermally reversible crosslinks. The graft copolymer is formed by converting the carboxyl groups of a carboxylated polyphenylene oxide polymer to ionic carbonyl groups in a suitable solvent, reacting pivalolactone with the dissolved polymer, and adding acid to the solution to produce the graft copolymer.

Green Michael addition of thiols to electron deficient alkenes using KF/alumina and recyclable solvent or solvent-free conditions

Energy Technology Data Exchange (ETDEWEB)

Lenardao, Eder J.; Trecha, Danusia O.; Ferreira, Patricia da C.; Jacob, Raquel G.; Perin, Gelson [Universidade Federal de Pelotas (UFPEL), Pelotas, RS (Brazil). Inst. de Quimica e Geociencias. Lab. de Sintese Organica Limpa (LASOL)]. E-mail: lenardao@ufpel.edu.br

2009-07-01

A general, clean and easy method for the conjugated addition of thiols to citral promoted by KF/Al{sub 2}O{sub 3} under solvent-free or using glycerin as recyclable solvent at room temperature is described. It was found that the solvent-free protocol is applicable to the direct reaction of thiophenol with the essential oil of lemon grass (Cymbopogon citratus) to afford directly 3,7-dimethyl-3-(phenylthio)oct-6-enal, a potential bactericide agent. The method was extended to other electron-poor alkenes with excellent results. For the solvent-free protocol, the use of microwave irradiation facilitated the procedure and accelerates the reaction. The catalytic system and glycerin can be reused up to three times without previous treatment with comparable activity. (author)

Facile phase transfer of hydrophobic nanoparticles with poly(ethylene glycol) grafted hyperbranched poly(amido amine)

International Nuclear Information System (INIS)

Ji Minglei; Yang Wuli; Ren Qingguang; Lu Daru

2009-01-01

In order to enhance the dispersion ability of hydrophobic nanoparticles in water while maintaining their unique properties, we utilized poly(ethylene glycol) grafted hyperbranched poly(amido amine) (h-PAMAM-g-PEG) to modify three types of hydrophobic nanoparticle, CdSe, Au, and Fe 3 O 4 , and transferred them into water to extend their applications in biology. Considering the large amounts of amino groups in hyperbranched poly(amido amine) (h-PAMAM) polymer, complexation interaction between h-PAMAM-g-PEG copolymer and nanoparticles was achieved and ligand exchange between the copolymers and original small molecules ligands occurred. The transferred nanoparticles could be easily dispersed in water with better stability, and their unique properties, such as fluorescence, surface plasmon resonance, and superparamagnetism, were well maintained in the ligand exchange process. In addition, increasing the number of grafted PEG showed a negative effect on the ligand exchange process. Due to the existence of h-PAMAM-g-PEG ligands, the stabilized nanoparticles have improved stability in aqueous and ionic solutions. In the case of CdSe nanoparticles, the h-PAMAM-g-PEG layer leads to a lower cytotoxicity when compared with bare CdSe particles, and they could be directly used in bioimaging.

Thermodynamic stability and kinetic inertness of a Gd-DTPA bisamide complex grafted onto gold nanoparticles.

Science.gov (United States)

Mogilireddy, Vijetha; Déchamps-Olivier, Isabelle; Alric, Christophe; Laurent, Gautier; Laurent, Sophie; Vander Elst, Luce; Muller, Robert; Bazzi, Rana; Roux, Stéphane; Tillement, Olivier; Chuburu, Françoise

2015-01-01

Gold nanoparticles coated by gadolinium (III) chelates (Au@DTDTPA) where DTDTPA is a dithiolated bisamide derivative of diethylenetriamine-N,N,N',N'',N''-pentaacetic acid (DTPA), constituted contrast agents for both X-ray computed tomography and magnetic resonance imaging. In an MRI context, highly stable Gd(3+) complexes are needed for in vivo applications. Thus, knowledge of the thermodynamic stability and kinetic inertness of these chelates, when grafted onto gold nanoparticles, is crucial since bisamide DTPA chelates are usually less suited for Gd(3+) coordination than DTPA. Therefore, these parameters were evaluated by means of potentiometric titrations and relaxivity measurements. The results showed that, when the chelates were grafted onto the nanoparticle, not only their thermodynamic stability but also their kinetic inertness were improved. These positive effects were correlated to the chelate packing at the nanoparticle surface that stabilized the corresponding Gd(3+) complexes and greatly enhanced their kinetic inertness. Copyright © 2014 John Wiley & Sons, Ltd.

Size control in the synthesis of 1-6 nm gold nanoparticles via solvent-controlled nucleation.

Science.gov (United States)

Song, Jieun; Kim, Dukhan; Lee, Dongil

2011-11-15

We report a facile synthetic route for size-controlled preparation of gold nanoparticles. Nearly monodisperse gold nanoparticles with core diameters of 1-6 nm were obtained by reducing AuP(Phenyl)(3)Cl with tert-butylamine borane in the presence of dodecanethiol in the solvent mixture of benzene and CHCl(3). Mechanism studies have shown that the size control is achieved by the solvent-controlled nucleation in which the nuclei concentration increases with increasing the fraction of CHCl(3), leading to smaller particles. It was also found that, following the solvent-controlled nucleation, particle growth occurs via ligand replacement of PPh(3) on the nuclei by Au(I)thiolate generated by the digestive etching of small particles. This synthetic strategy was successfully demonstrated with other alkanethiols of different chain length with which size-controlled, monodisperse gold nanoparticles were prepared in remarkable yield without requiring any postsynthesis treatments.

Evolution of different morphologies of CdS nanoparticles by thermal decomposition of bis(thiourea)cadmium chloride in various solvents

International Nuclear Information System (INIS)

Gaur, Rama; Jeevanandam, P.

2015-01-01

CdS nanoparticles with different morphologies have been synthesized by thermal decomposition of bis(thiourea)cadmium chloride in different solvents without the use of any ligand/surfactant. CdS nanoparticles with pyramid, sponge-like and hexagonal disc-like morphologies were obtained in diphenyl ether (DPE), 1-octadecene (ODE) and ethylene glycol (EG), respectively. In addition, CdS nanoparticles with unique morphologies were obtained when the decomposition of the complex was carried out in mixed solvents (DPE–EG and ODE–EG). Extensive characterization of the CdS nanoparticles was carried out using powder X-ray diffraction, FT-IR spectroscopy, thermal analysis, field-emission scanning electron microscopy, diffuse reflectance spectroscopy and photoluminescence spectroscopy, and detailed mechanism of the formation of CdS nanoparticles with different morphologies in various solvents has been proposed

Chitosan-Graft-Polyethylenimine/DNA Nanoparticles as Novel Non-Viral Gene Delivery Vectors Targeting Osteoarthritis

Science.gov (United States)

Lv, Lulu; Zhao, Huiqing

2014-01-01

The development of safe and efficient gene carriers is the key to the clinical success of gene therapy. The present study was designed to develop and evaluate the chitosan-graft-polyethylenimine (CP)/DNA nanoparticles as novel non-viral gene vectors for gene therapy of osteoarthritis. The CP/DNA nanoparticles were produced through a complex coacervation of the cationic polymers with pEGFP after grafting chitosan (CS) with a low molecular weight (Mw) PEI (Mw = 1.8 kDa). Particle size and zeta potential were related to the weight ratio of CP:DNA, where decreases in nanoparticle size and increases in surface charge were observed as CP content increased. The buffering capacity of CP was significantly greater than that of CS. The transfection efficiency of CP/DNA nanoparticles was similar with that of the Lipofectamine™ 2000, and significantly higher than that of CS/DNA and PEI (25 kDa)/DNA nanoparticles. The transfection efficiency of the CP/DNA nanoparticles was dependent on the weight ratio of CP:DNA (w/w). The average cell viability after the treatment with CP/DNA nanoparticles was over 90% in both chondrocytes and synoviocytes, which was much higher than that of PEI (25 kDa)/DNA nanoparticles. The CP copolymers efficiently carried the pDNA inside chondrocytes and synoviocytes, and the pDNA was detected entering into nucleus. These results suggest that CP/DNA nanoparticles with improved transfection efficiency and low cytotoxicity might be a safe and efficient non-viral vector for gene delivery to both chondrocytes and synoviocytes. PMID:24392152

Comparison of mesencephalic free-floating tissue culture grafts and cell suspension grafts in the 6-hydroxydopamine-lesioned rat

DEFF Research Database (Denmark)

Meyer, Morten; Widmer, H R; Wagner, B

1998-01-01

of grafted dopaminergic neurons and to correlate that with the behavioral effects. Additional cultures and acutely prepared explants were also fixed and stored for histological investigation in order to estimate the loss of dopaminergic neurons in culture and after transplantation. Similar behavioral...... numbers of TH-immunoreactive (TH-ir) neurons in grafts of cultured tissue (775 +/- 98, mean +/- SEM) and grafts of fresh, dissociated cell suspension (806 +/- 105, mean +/- SEM). Cell counts in fresh explants, 7-day-old cultures, and grafted cultures revealed a 68.2% loss of TH-ir cells 7 days after......Ventral mesencephalon (VM) of fetal rat and human origin grown as free-floating roller-tube (FFRT) cultures can survive subsequent grafting to the adult rat striatum. To further explore the functional efficacy of such grafts, embryonic day 13 ventral mesencephalic tissue was grafted either after 7...

High Rate Micromechanical Behavior of Grafted Polymer Nanoparticle Films

Science.gov (United States)

Thomas, Edwin

We report the ultra high strain rate behavior of films comprised of polymer grafted nanoparticles (NPs) and compare the results to homopolymer films. The films are formed by flow coating a suspension of polystyrene (PS) chains of 230 kg/mol grafted to 16nm diameter SiO2\\ at a graft density of 0.6 chains/nm2 resulting a film with 1 vol % SiO2. Films of 267 kg/mol PS were also flow coated and both films were impacted at velocities 350-700 ms-1 using 3.7 micron SiO2\\ projectiles to achieve increments in kinetic energy (KE) of 1:2:4. The KE of the projectiles before and after penetration was measured to determine the penetration energy. TEM and SEM suggest the projectile initially induces plastic flow due to the adiabatic temperature rise from impact. As the projectile deforms the film, the lower magnitude, biaxial stress state in the peripherial regions causes material microvoid formation and initiation of craze growth in the radial and tangential directions. The anchoring of the grafted polymer chains to the NPs increases the penetration energy relative to the pure homopolymer by 50% and the films capacity to delocalize the impact by 200%. These results suggest that highly grafted NP films may be useful in lightweight protection systems. In collaboration with Omri Fried, Olawale Lawal, Yang Jiao, Victor Hsaio, Thevamaran Ramathasan, Mujin Zhou, Richard Vaia.

Cytocompatibility of polyethylene grafted with triethylenetetramine functionalized carbon nanoparticles

Science.gov (United States)

Žáková, Pavlína; Slepičková Kasálková, Nikola; Slepička, Petr; Kolská, Zdeňka; Karpíšková, Jana; Stibor, Ivan; Švorčík, Václav

2017-11-01

Various carbon nanostructures are widely researched as scaffolds for tissue engineering. We evaluated the surface properties and cell-substrate interactions of carbon nanoparticles functionalized with triethylenetetramine (CNPs) grafted polymer film. Two forms of polyethylene (HDPE, LDPE) were treated in an inert argon plasma discharge and, subsequently, grafted with CNPs. The surface properties were studied using multiple methods, including Raman spectroscopy, goniometry, atomic force microscopy, X-ray photoelectron spectroscopy and electrokinetic analysis. Cell-substrate interactions were determined in vitro by studying adhesion, proliferation and viability of vascular smooth muscle cells (VSMCs) from the aorta of a rat. Cell-substrate interactions on pristine and modified substrates were compared to standard tissue culture polystyrene. Our results show that CNPs affect surface morphology and wettability and therefore adhesion, proliferation and viability of cultured muscle cells.

Microwave-assisted synthesis of CuInSe{sub 2} nanoparticles in low-absorbing solvents

Energy Technology Data Exchange (ETDEWEB)

Oleksak, Richard P.; Flynn, Brendan T.; Herman, Gregory S. [School of Chemical, Biological and Environmental Engineering, Oregon State University, Corvallis, OR (United States); Schut, David M. [Voxtel Inc., Eugene, OR (United States)

2014-01-15

Copper indium diselenide (CIS) nanoparticles were synthesized using a microwave-assisted one-pot solvothermal approach. For these studies high microwave-absorbing precursors were used in combination with low microwave absorbing solvents tri-n-octylphosphine (TOP) and oleic acid (OA) to investigate the effect of selective heating of the precursors on nanoparticle synthesis. High-resolution transmission electron microscopy (TEM) results indicated that the nanoparticles were spherical, crystalline and 4-5 nm in diameter. X-ray diffraction (XRD) results indicated that the nanoparticles had a body-centered tetragonal structure with planar defects that decreased in concentration with increasing reaction temperature and reaction time. The nanoparticle compositions varied depending on the reaction conditions and the compositions were found to approach stoichiometry for increased reaction times. Fourier transform infrared (FTIR) spectroscopy indicated both solvents adsorbed to the nanoparticle surface and energy dispersive spectroscopy indicated that these ligands became chlorinated during the reaction. The uniform temperature profile offered by the microwave heating allowed for highly reproducible batch-to-batch reactions, allowing for tight control over composition and defect concentration. (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

GRINDING SOLVENT-FREE PAAL-KNORR PYRROLE SYNTHESIS ...

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Paal-Knorr pyrrole synthesis on smectites as recyclable and green catalysts. Bull. Chem. Soc. .... 1-Propyl-2,5-dimethyl-1H-pyrrole (8a). Oil (reported as oil .... of pyrroles catalyzed by zirconium chloride under solvent-free conditions . Ultrason.

Synthetic oligomer analysis using atmospheric pressure photoionization mass spectrometry at different photon energies

International Nuclear Information System (INIS)

Desmazières, Bernard; Legros, Véronique; Giuliani, Alexandre; Buchmann, William

2014-01-01

Graphical abstract: Atmospheric pressure photoIonization mass spectra of synthetic oligomers were recorded in the negative mode by varying the photon energy using synchrotron radiation. Photon energy required for an efficient ionization of the polymer was correlated to ionization potential of the solvent (for example 9.4 eV for tetrahydrofuran). -- Highlights: •Atmospheric pressure photoionization was performed using synchrotron radiation. •Photoionization of oligomers in THF with 10% CH 2 Cl 2 produces intact [M + Cl] − ions. •The photon energy required corresponds to ionization potential of the solvent. •Polymer distributions depend on source parameters such T °C and applied voltages. •Liquid chromatography was coupled to MS using an APPI interface for polymer analysis. -- Abstract: Atmospheric pressure photoionization (APPI) followed by mass spectrometric detection was used to ionize a variety of polymers: polyethylene glycol, polymethyl methacrylate, polystyrene, and polysiloxane. In most cases, whatever the polymer or the solvent used (dichloromethane, tetrahydrofuran, hexane, acetone or toluene), only negative ion mode produced intact ions such as chlorinated adducts, with no or few fragmentations, in contrast to the positive ion mode that frequently led to important in-source fragmentations. In addition, it was shown that optimal detection of polymer distributions require a fine tuning of other source parameters such as temperature and ion transfer voltage. Series of mass spectra were recorded in the negative mode, in various solvents (dichloromethane, tetrahydrofuran, hexane, toluene, and acetone), by varying the photon energy from 8 eV up to 10.6 eV using synchrotron radiation. To these solvents, addition of a classical APPI dopant (toluene or acetone) was not necessary. Courtesy of the synchrotron radiation, it was demonstrated that the photon energy required for an efficient ionization of the polymer was correlated to the ionization energy

Synthetic oligomer analysis using atmospheric pressure photoionization mass spectrometry at different photon energies

Energy Technology Data Exchange (ETDEWEB)

Desmazières, Bernard [Global Bioenergies, 5 rue Henri Desbruyeres, 91030 Evry (France); Legros, Véronique [CNRS, UMR8587, Université d’Evry-Val-d’Essonne, Laboratoire Analyse et Modélisation pour la Biologie et l’Environnement, F-91025 Evry (France); Giuliani, Alexandre [Synchrotron SOLEIL, L’Orme des Merisiers, Saint-Aubin, 91192 Gif-sur-Yvette (France); UAR1008, CEPIA, INRA, Rue de la Geraudiere, F-44316 Nantes (France); Buchmann, William, E-mail: william.buchmann@univ-evry.fr [CNRS, UMR8587, Université d’Evry-Val-d’Essonne, Laboratoire Analyse et Modélisation pour la Biologie et l’Environnement, F-91025 Evry (France)

2014-01-15

Graphical abstract: Atmospheric pressure photoIonization mass spectra of synthetic oligomers were recorded in the negative mode by varying the photon energy using synchrotron radiation. Photon energy required for an efficient ionization of the polymer was correlated to ionization potential of the solvent (for example 9.4 eV for tetrahydrofuran). -- Highlights: •Atmospheric pressure photoionization was performed using synchrotron radiation. •Photoionization of oligomers in THF with 10% CH{sub 2}Cl{sub 2} produces intact [M + Cl]{sup −} ions. •The photon energy required corresponds to ionization potential of the solvent. •Polymer distributions depend on source parameters such T °C and applied voltages. •Liquid chromatography was coupled to MS using an APPI interface for polymer analysis. -- Abstract: Atmospheric pressure photoionization (APPI) followed by mass spectrometric detection was used to ionize a variety of polymers: polyethylene glycol, polymethyl methacrylate, polystyrene, and polysiloxane. In most cases, whatever the polymer or the solvent used (dichloromethane, tetrahydrofuran, hexane, acetone or toluene), only negative ion mode produced intact ions such as chlorinated adducts, with no or few fragmentations, in contrast to the positive ion mode that frequently led to important in-source fragmentations. In addition, it was shown that optimal detection of polymer distributions require a fine tuning of other source parameters such as temperature and ion transfer voltage. Series of mass spectra were recorded in the negative mode, in various solvents (dichloromethane, tetrahydrofuran, hexane, toluene, and acetone), by varying the photon energy from 8 eV up to 10.6 eV using synchrotron radiation. To these solvents, addition of a classical APPI dopant (toluene or acetone) was not necessary. Courtesy of the synchrotron radiation, it was demonstrated that the photon energy required for an efficient ionization of the polymer was correlated to the

Formation of silk fibroin nanoparticles in water-miscible organic solvent and their characterization

Science.gov (United States)

Zhang, Yu-Qing; Shen, Wei-De; Xiang, Ru-Li; Zhuge, Lan-Jian; Gao, Wei-Jian; Wang, Wen-Bao

2007-10-01

When Silk fibre derived from Bombyx mori, a native biopolymer, was dissolved in highly concentrated neutral salts such as CaCl2, the regenerated liquid silk, a gradually degraded peptide mixture of silk fibroin, could be obtained. The silk fibroin nanoparticles were prepared rapidly from the liquid silk by using water-miscible protonic and polar aprotonic organic solvents. The nanoparticles are insoluble but well dispersed and stable in aqueous solution and are globular particles with a range of 35-125 nm in diameter by means of TEM, SEM, AFM and laser sizer. Over one half of the ɛ-amino groups exist around the protein nanoparticles by using a trinitrobenzenesulfonic acid (TNBS) method. Raman spectra shows the tyrosine residues on the surface of the globules are more exposed than those on native silk fibers. The crystalline polymorph and conformation transition of the silk nanoparticles from random-coil and α-helix form (Silk I) into anti-parallel β-sheet form (Silk II) are investigated in detail by using infrared, fluorescence and Raman spectroscopy, DSC, 13C CP-MAS NMR and electron diffraction. X-ray diffraction of the silk nanoparticles shows that the nanoparticles crystallinity is about four fifths of the native fiber. Our results indicate that the degraded peptide chains of the regenerated silk is gathered homogeneously or heterogeneously to form a looser globular structure in aqueous solution. When introduced into excessive organic solvent, the looser globules of the liquid silk are rapidly dispersed and simultaneously dehydrated internally and externally, resulting in the further chain-chain contact, arrangement of those hydrophobic domains inside the globules and final formation of crystalline silk nanoparticles with β-sheet configuration. The morphology and size of the nanoparticles are relative to the kinds, properties and even molecular structures of organic solvents, and more significantly to the looser globular substructure of the degraded silk

Formation of silk fibroin nanoparticles in water-miscible organic solvent and their characterization

International Nuclear Information System (INIS)

Zhang Yuqing; Shen Weide; Xiang Ruli; Zhuge Lanjian; Gao Weijian; Wang Wenbao

2007-01-01

When Silk fibre derived from Bombyx mori, a native biopolymer, was dissolved in highly concentrated neutral salts such as CaCl 2 , the regenerated liquid silk, a gradually degraded peptide mixture of silk fibroin, could be obtained. The silk fibroin nanoparticles were prepared rapidly from the liquid silk by using water-miscible protonic and polar aprotonic organic solvents. The nanoparticles are insoluble but well dispersed and stable in aqueous solution and are globular particles with a range of 35-125 nm in diameter by means of TEM, SEM, AFM and laser sizer. Over one half of the ε-amino groups exist around the protein nanoparticles by using a trinitrobenzenesulfonic acid (TNBS) method. Raman spectra shows the tyrosine residues on the surface of the globules are more exposed than those on native silk fibers. The crystalline polymorph and conformation transition of the silk nanoparticles from random-coil and α-helix form (Silk I) into anti-parallel β-sheet form (Silk II) are investigated in detail by using infrared, fluorescence and Raman spectroscopy, DSC, 13 C CP-MAS NMR and electron diffraction. X-ray diffraction of the silk nanoparticles shows that the nanoparticles crystallinity is about four fifths of the native fiber. Our results indicate that the degraded peptide chains of the regenerated silk is gathered homogeneously or heterogeneously to form a looser globular structure in aqueous solution. When introduced into excessive organic solvent, the looser globules of the liquid silk are rapidly dispersed and simultaneously dehydrated internally and externally, resulting in the further chain-chain contact, arrangement of those hydrophobic domains inside the globules and final formation of crystalline silk nanoparticles with β-sheet configuration. The morphology and size of the nanoparticles are relative to the kinds, properties and even molecular structures of organic solvents, and more significantly to the looser globular substructure of the degraded silk

Formation of silk fibroin nanoparticles in water-miscible organic solvent and their characterization

Energy Technology Data Exchange (ETDEWEB)

Zhang Yuqing, E-mail: yqzhang@public1.sz.js.cn; Shen Weide; Xiang Ruli [Soochow University, Silk Biotechnol. Lab., School of Life Science (China); Zhuge Lanjian; Gao Weijian; Wang Wenbao [Soochow University, Analytical Center (China)

2007-10-15

When Silk fibre derived from Bombyx mori, a native biopolymer, was dissolved in highly concentrated neutral salts such as CaCl{sub 2}, the regenerated liquid silk, a gradually degraded peptide mixture of silk fibroin, could be obtained. The silk fibroin nanoparticles were prepared rapidly from the liquid silk by using water-miscible protonic and polar aprotonic organic solvents. The nanoparticles are insoluble but well dispersed and stable in aqueous solution and are globular particles with a range of 35-125 nm in diameter by means of TEM, SEM, AFM and laser sizer. Over one half of the {epsilon}-amino groups exist around the protein nanoparticles by using a trinitrobenzenesulfonic acid (TNBS) method. Raman spectra shows the tyrosine residues on the surface of the globules are more exposed than those on native silk fibers. The crystalline polymorph and conformation transition of the silk nanoparticles from random-coil and {alpha}-helix form (Silk I) into anti-parallel {beta}-sheet form (Silk II) are investigated in detail by using infrared, fluorescence and Raman spectroscopy, DSC, {sup 13}C CP-MAS NMR and electron diffraction. X-ray diffraction of the silk nanoparticles shows that the nanoparticles crystallinity is about four fifths of the native fiber. Our results indicate that the degraded peptide chains of the regenerated silk is gathered homogeneously or heterogeneously to form a looser globular structure in aqueous solution. When introduced into excessive organic solvent, the looser globules of the liquid silk are rapidly dispersed and simultaneously dehydrated internally and externally, resulting in the further chain-chain contact, arrangement of those hydrophobic domains inside the globules and final formation of crystalline silk nanoparticles with {beta}-sheet configuration. The morphology and size of the nanoparticles are relative to the kinds, properties and even molecular structures of organic solvents, and more significantly to the looser globular

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KEYWORDS: Solvent free, Maleanilic acids, Maleic anhydride, Aniline derivatives ... associated with the carboxylic group between 3275-2877 cm-1, the weak –NH .... Chemical shifts (σ/ppm) relative to TMS*. O-H N-H Ha. Hb. Hc. Hd. He. Hf.

Injerto libre braquial medial Free medial arm graft

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P. Martos Díaz

2007-12-01

Full Text Available Introducción. Entre las reconstrucciones de defectos titulares de cabeza y cuello, el injerto libre microvascularizado braquial medial no ha adquirido mucha popularidad debido a las variaciones anatómicas que se reflejan en la vascularización de éste. Nuestro objetivo es realizar una descripción de la anatomía y técnica quirúrgica, así como una revisión de la literatura describiendo las ventajas y desventajas de este tipo de injerto. Material y método. Presentamos el caso de una paciente con carcinoma epidermoide de mucosa yugal izquierda con afectación ganglionar ipsilateral. Se procedió a su resección con márgenes más disección cervical funcional. La reconstrucción del defecto se llevó a cabo mediante un injerto libre microvascularizado braquial medial de brazo izquierdo. Discusión. Pensamos que el injerto libre braquial medial de brazo se trata de una opción más segura a la hora de la reconstrucción de defectos cervicofaciales, aportando una serie de ventajas entre las que destacan: no sacrificio de una arteria terminal, cierre primario de la zona donante, mínimo defecto estético, y poseer una piel fina, elástica y sin vello.Introduction. Free medial microvascularized arm grafts have not become very popular for the reconstruction of head and neck defects due to anatomic variations in their vascularization. Our objective was to describe the anatomy and surgical technique and to review the literature on the advantages and disadvantages of free medial arm grafts. Material and methods. We report the case of a patient with squamous cell carcinoma of the left jugal mucosa with same-side lymph node involvement. The tumor was resected with margins and a functional cervical dissection was performed. The defect was reconstructed using a free medial microvascularized graft from the left arm. Discussion. We believe that free medial arm grafts are a safer option for the reconstruction of cervicofacial defects and that they offer

Nanoparticles based on novel amphiphilic polyaspartamide copolymers

International Nuclear Information System (INIS)

Craparo, Emanuela Fabiola; Teresi, Girolamo; Ognibene, Maria Chiara; Casaletto, Maria Pia; Bondi, Maria Luisa; Cavallaro, Gennara

2010-01-01

In this article, the synthesis of two amphiphilic polyaspartamide copolymers, useful to obtain polymeric nanoparticles without using surfactants or stabilizing agents, is described. These copolymers were obtained starting from α,β-poly-(N-2-hydroxyethyl)-dl-aspartamide (PHEA) by following a novel synthetic strategy. In particular, PHEA and its pegylated derivative (PHEA-PEG 2000 ) were functionalized with poly(lactic acid) (PLA) through 1,1'-carbonyldiimidazole (CDI) activation to obtain PHEA-PLA and PHEA-PEG 2000 -PLA graft copolymers, respectively. These copolymers were properly purified and characterized by 1 H-NMR, FT-IR, and Size Exclusion Chromatography (SEC) analyses, which confirmed that derivatization reactions occurred. Nanoparticles were obtained from PHEA-PLA and PHEA-PEG 2000 -PLA graft copolymers by using the high pressure homogenization-solvent evaporation method, avoiding the use of surfactants or stabilizing agents. Polymeric nanoparticles were characterized by dimensional analysis, before and after freeze-drying process, and Scanning Electron Microscopy (SEM). Zeta potential measurements and X-ray Photoelectron Spectroscopy (XPS) analysis demonstrated the presence of PEG and/or PHEA onto the PHEA-PEG 2000 -PLA and PHEA-PLA nanoparticle surface, respectively.

Strongly Iridescent Hybrid Photonic Sensors Based on Self-Assembled Nanoparticles for Hazardous Solvent Detection

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Ayaka Sato

2018-03-01

Full Text Available Facile detection and the identification of hazardous organic solvents are essential for ensuring global safety and avoiding harm to the environment caused by industrial wastes. Here, we present a simple method for the fabrication of silver-coated monodisperse polystyrene nanoparticle photonic structures that are embedded into a polydimethylsiloxane (PDMS matrix. These hybrid materials exhibit a strong green iridescence with a reflectance peak at 550 nm that originates from the close-packed arrangement of the nanoparticles. This reflectance peak measured under Wulff-Bragg conditions displays a 20 to 50 nm red shift when the photonic sensors are exposed to five commonly employed and highly hazardous organic solvents. These red-shifts correlate well with PDMS swelling ratios using the various solvents, which suggests that the observable color variations result from an increase in the photonic crystal lattice parameter with a similar mechanism to the color modulation of the chameleon skin. Dynamic reflectance measurements enable the possibility of clearly identifying each of the tested solvents. Furthermore, as small amounts of hazardous solvents such as tetrahydrofuran can be detected even when mixed with water, the nanostructured solvent sensors we introduce here could have a major impact on global safety measures as innovative photonic technology for easily visualizing and identifying the presence of contaminants in water.

Ni2+ supported on hydroxyapatite-core@shell γ-Fe2O3 nanoparticles as new and green catalyst for the synthesis of 3,4-dihydropyrimidin-2(1H-ones under solvent-free condition

Directory of Open Access Journals (Sweden)

Eshagh Rezaee Nezhad

2013-10-01

Full Text Available The aim of this research is to study Ni2+ supported on hydroxyapatite-core-shell magnetic γ-Fe2O3 nanoparticles (γ-Fe2O3@HAp-Ni2+ as a green and recyclable catalyst for the Biginelli reaction under solvent-free conditions. One-pot multi-component condensation of 1,3-dicarbonyl compounds, urea and aldehydes at 80 oC affords the corresponding compounds in high yields and in short reaction times using γ-Fe2O3@HAp-Ni2+. The catalyst can be readily isolated using an external magnet and no obvious loss of activity was observed when the catalyst was reused in seven consecutive runs. The mean size and the surface morphology of the nanoparticles were characterized by transmission electron microscopy, scanning electron microscope, vibrating sample magnetometry, X-ray powder diffraction and Fourier transform infrared techniques.

Polyether/Polyester Graft Copolymers

Science.gov (United States)

Bell, Vernon L., Jr.; Wakelyn, N.; Stoakley, D. M.; Proctor, K. M.

1986-01-01

Higher solvent resistance achieved along with lower melting temperature. New technique provides method of preparing copolymers with polypivalolactone segments grafted onto poly (2,6-dimethyl-phenylene oxide) backbone. Process makes strong materials with improved solvent resistance and crystalline, thermally-reversible crosslinks. Resulting graft copolymers easier to fabricate into useful articles, including thin films, sheets, fibers, foams, laminates, and moldings.

Surface free energy of alkali and transition metal nanoparticles

International Nuclear Information System (INIS)

Aqra, Fathi; Ayyad, Ahmed

2014-01-01

Graphical abstract: Size dependent surface free energy of spherical, cubic and disk Au nanoparticles. - Highlights: • A model to account for the surface free energy of metallic nanoparticles is described. • The model requires only the cohesive energy of the nanoparticle. • The surface free energy of a number of metallic nanoparticles has been calculated, and the obtained values agree well with existing data. • Surface energy falls down very fast when the number of atoms is less than hundred. • The model is applicable to any metallic nanoparticle. - Abstract: This paper addresses an interesting issue on the surface free energy of metallic nanoparticles as compared to the bulk material. Starting from a previously reported equation, a theoretical model, that involves a specific term for calculating the cohesive energy of nanoparticle, is established in a view to describe the behavior of surface free energy of metallic nanoparticles (using different shapes of particle: sphere, cube and disc). The results indicate that the behavior of surface energy is very appropriate for spherical nanoparticle, and thus, it is the most realistic shape of a nanoparticle. The surface energy of copper, silver, gold, platinum, tungsten, molybdenum, tantalum, paladium and alkali metallic nanoparticles is only prominent in the nanoscale size, and it decreases with the decrease of nanoparticle size. Thus, the surface free energy plays a more important role in determining the properties of nanoparticles than in bulk materials. It differs from shape to another, and falls down as the number of atoms (nanoparticle size) decreases. In the case of spherical nanoparticles, the onset of the sharp decrease in surface energy is observed at about 110 atom. A decrease of 16% and 45% in surface energy is found by moving from bulk to 110 atom and from bulk to 5 atom, respectively. The predictions are consistent with the reported data

Additive effects in radiation grafting and curing

International Nuclear Information System (INIS)

Viengkhou, V.; Ng, L.

1996-01-01

Full text: Detailed studies on the accelerative effect of novel additives in radiation grafting and curing using acrylated monomer/oligomer systems have been performed in the presence of ionising radiation and UV as sources. Methyl methacrylate (MMA) is used as typical monomer for these grafting studies in the presence of the additives with model backbone polymers, cellulose and propropylene. Additives which have been found to accelerate these grafting processes are: mineral acid, occlusion compounds like urea, thermal initiators and photoinitiators as well as multifunctional monomers such as multifunctional acrylates. The results from irradiation with gamma rays have also been compared with irradiation from a 90W UV lamp. The role of the above additives in accelerating the analogous process of radiation curing has been investigated. Acrylated urethanes, epoxies and polyesters are used as oligomers together with acrylated monomers in this work with uv lamps of 300 watts/inch as radiation source. In the UV curing process bonding between film and substrate is usually due to physical forces. In the present work the presence of additives are shown to influence the occurrence of concurrent grafting during cure thus affecting the nature of the bonding of the cured film. The conditions under which concurrent grafting with UV can occur will be examined. A mechanism for accelerative effect of these additives in both grafting and curing processes has been proposed involving radiation effects and partitioning phenomena

Donor-acceptor-donor thienyl/bithienyl-benzothiadiazole/quinoxaline model oligomers: experimental and theoretical studies.

Science.gov (United States)

Pina, João; de Melo, J Seixas; Breusov, D; Scherf, Ullrich

2013-09-28

A comprehensive spectral and photophysical investigation of four donor-acceptor-donor (DAD) oligomers consisting of electron-deficient 2,1,3-benzothiadiazole or quinoxaline moieties linked to electron-rich thienyl or bithienyl units has been undertaken. Additionally, a bis(dithienyl) substituted naphthalene was also investigated. The D-A-D nature of these oligomers resulted in the presence of an intramolecular charge transfer (ICT) state, which was further substantiated by solvatochromism studies (analysis with the Lippert-Mataga formalism). Hereby, significant differences have been obtained for the fluorescence quantum yields of the oligomers in the non-polar solvent methylcyclohexane vs. the polar ethanol. The study was further complemented with the determination of the optimized ground-state molecular geometries for the oligomers together with the prediction of the lowest vertical one-electron excitation energy and the relevant molecular orbital contours using DFT calculations. The electronic transitions show a clear HOMO to LUMO charge-transfer character. In contrast to the thiophene oligomers (the oligothiophenes with n = 1-7), where the intersystem crossing (ISC) yield decreases with n, the studied DAD oligomers were found to show an increase in the ISC efficiency with the number of (donor) thienyl units.

Antibacterial activity of silver nanoparticles stabilized on tannin-grafted collagen fiber

Energy Technology Data Exchange (ETDEWEB)

He Li [National Engineering Laboratory for Clean Technology of Leather Manufacture, Sichuan University, Chengdu 610065 (China); Gao Siying; Wu Hao [Department of Biomass Chemistry and Engineering, Sichuan University, Chengdu 610065 (China); Liao Xuepin, E-mail: xpliao@scu.edu.cn [Department of Biomass Chemistry and Engineering, Sichuan University, Chengdu 610065 (China); He Qiang [National Engineering Laboratory for Clean Technology of Leather Manufacture, Sichuan University, Chengdu 610065 (China); Shi Bi, E-mail: sibitannin@vip.163.com [National Engineering Laboratory for Clean Technology of Leather Manufacture, Sichuan University, Chengdu 610065 (China) and Department of Biomass Chemistry and Engineering, Sichuan University, Chengdu 610065 (China)

2012-07-01

Bayberry tannin (BT), a typical plant polyphenol, was grafted on collagen fiber (CF) in different mass ratios. Subsequently, the BT-grafted CF (BT-CF) was used as carrier and stabilizer to prepare BT-CF stabilized silver nanoparticles (BT-CF-AgNPs). Scanning Electron Microscopy image of BT-CF-AgNPs showed that the BT-CF-AgNPs was in ordered fibrous state. X-ray Diffraction patterns and Transmission Electron Microscopy images offered evidence that the Ag nanoparticles were well dispersed on BT-CF. Fourier Transform-Infrared Spectroscopy (FTIR) and X-ray Photoelectron Spectroscopy (XPS) investigations revealed that the Ag NPs were stabilized by the phenolic hydroxyls and quinones of BT on CF through electron donation/acception interaction. Antibacterial experiments demonstrated that BT-CF-AgNPs exhibited high antibacterial activity. When cell suspensions of Escherichia coli and Staphylococcus aureus (10{sup 4}-10{sup 5} cfu/mL) were contacted with BT{sub 0.19}-CF-AgNPs (mass ratio of BT to CF = 0.19, conc. of Ag = 8 {mu}g/mL) at 310 K under constant shaking, the number of cells went down to zero within 2 h. In addition, the minimal inhibitory concentration of BT{sub 0.19}-CF-AgNPs against Escherichia coli, Staphylococcus aureus, Penicillium glaucum and Saccharomyces cerevisiae was 2 {mu}g/mL, 4 {mu}g/mL, 6 {mu}g/mL and 12 {mu}g/mL Ag, respectively. During recycling use, the antibacterial activity of BT{sub 0.19}-CF-AgNPs against Escherichia coli can last for 5 cycles. These facts suggest that BT-CF-AgNPs can be used as a new and effective antibacterial agent. - Highlights: Black-Right-Pointing-Pointer Bayberry tannin-grafted collagen fiber can be acted as carrier and stabilizer for the preparation of nano-silver (AgNPs) with different particle size. Black-Right-Pointing-Pointer Bayberry tannin-grafted collagen fiber stabilized silver nanoparticles (BT-CF-AgNPs) were characterized by SEM, XRD, TEM, FTIR and XPS. Black-Right-Pointing-Pointer BT-CF-AgNPs has the

Solvent Free Preparation of p-Cymene from Limonene Using Vietnamese Montmorillonite

DEFF Research Database (Denmark)

Nguyen, Thao-Tran Thi; Duus, Fritz; Le, Thach Ngoc

2013-01-01

p-Cymene, an important intermediate in industrial chemistry, has been prepared in good yields by thermally induced dehydrogenation of limonene under solvent-free reaction conditions using Vietnamese montmorillonite as an efficient green catalyst.......p-Cymene, an important intermediate in industrial chemistry, has been prepared in good yields by thermally induced dehydrogenation of limonene under solvent-free reaction conditions using Vietnamese montmorillonite as an efficient green catalyst....

Physico-chemical properties of Pd nanoparticles produced by Pulsed Laser Ablation in different organic solvents

International Nuclear Information System (INIS)

Cristoforetti, Gabriele; Pitzalis, Emanuela; Spiniello, Roberto; Ishak, Randa; Giammanco, Francesco; Muniz-Miranda, Maurizio; Caporali, Stefano

2012-01-01

Palladium nanoparticles are arousing an increasing interest because of their strong activity in heterogeneous catalysis in a wide range of reactions. Driven by the interest of producing Pd nanoparticles to be deposited for catalysis over hydrophobic supports, we investigated their synthesis via Pulsed Laser Ablation in Liquid in several organic solvents, as acetone, ethanol, 2-propanol, toluene, n-hexane. The colloids were produced by using a Nd:YAG ns laser and without the addition of surfactant agents. The morphology, composition, stability and oxidation state of the obtained nanoparticles were investigated by TEM-EDS analysis, UV-vis spectroscopy, X-ray Photoelectron Spectroscopy and micro-Raman spectroscopy. The results evidence that the nature of the solvent influences both the yield and the physico-chemical properties of the produced nanoparticles. While in acetone and alcohols spheroidal, non aggregated and stable particles are obtained, in case of toluene and n-hexane few unstable particles surrounded by a gel-like material are produced. Raman/XPS measurements suggest the presence of amorphous or graphitic carbon onto crystalline Pd nanoparticles, which could have hindered their growth and determined the observed smaller sizes if compared to nanoparticles produced in water. The stability of Pd colloids obtained in acetone and alcohols was attributed to adsorbed anions like enolates or alcoholates; non polar solvents like toluene and n-hexane, unable to give rise to adsorbed anionic species, cannot provide any stabilization to the palladium nanoparticles. XPS analyses also evidenced a partial oxidation of particles surface, with a ratio Pd 2+ :Pd 0 of 1:2.5 and 1:4 in acetone and ethanol, respectively.

Nanoparticle albumin-bound paclitaxel: a novel Cremphor-EL-free formulation of paclitaxel.

Science.gov (United States)

Stinchcombe, Thomas E

2007-08-01

Standard formulation paclitaxel requires the use of solvents, such as Cremphor-EL, which contribute to some of the toxicities commonly associated with paclitaxel-based therapy. Nanoparticle albumin-bound paclitaxel (nab-paclitaxel) is a novel solvent-free formulation of paclitaxel. The formulation is prepared by high-pressure homogenization of paclitaxel in the presence of serum albumin into a nanoparticle colloidal suspension. The human albumin-stabilized paclitaxel particles have an average size of 130 nm. Nab-paclitaxel has several practical advantages over Cremphor-EL-paclitaxel, including a shorter infusion time (30 min) and no need for premedications for hypersensitivity reactions. The nab-paclitaxel formulation eliminates the impact of Cremphor-EL on paclitaxel pharmacokinetics and utilizes the endogenous albumin transport mechanisms to concentrate nab-paclitaxel within the tumor. A recent Phase III trial compared nab- and Cremphor-EL-paclitaxel in patients with metastatic breast cancer. Patients treated with nab-paclitaxel experienced a higher response, longer time to tumor progression and, in patients receiving second-line or greater therapy, a longer median survival. Patients treated with nab-paclitaxel had a significantly lower rate of severe neutropenia and a higher rate of sensory neuropathy. The preclinical and clinical data indicate that the nab-paclitaxel formulation has significant advantages over Cremphor-EL-paclitaxel.

First-Row-Transition Ion Metals(II-EDTA Functionalized Magnetic Nanoparticles as Catalysts for Solvent-Free Microwave-Induced Oxidation of Alcohols

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Nuno M. R. Martins

2017-11-01

Full Text Available A series of first-row transition-metals combined with ethylenediamine tetraacetic acid (EDTA, as metal-based N,O-chelating ligands, at the surface of ferrite magnetic nanoparticles (MNPs was prepared by a co-precipitation method. Those EDTA functionalized MNPs with general formula Fe3O4@EDTA-M2+ [M = Mn2+ (1, Fe2+ (2, Co2+ (3, Ni2+ (4, Cu2+ (5 or Zn2+ (6] were characterized by FTIR (Fourier Transform Infrared spectroscopy, powder XRD (X-ray Diffraction, SEM (Scanning Electron Microscope, EDS (Energy Dispersive Spectrometer, VSM (Vibrating Sample Magnetometer and TGA (Thermal Gravity Analysis. The application of the magnetic NPs towards the microwave-assisted oxidation of several alcohol substrates in a solvent-free medium was evaluated. The influence of reaction parameters such as temperature, time, type of oxidant, and presence of organic radicals was investigated. This study demonstrates that these MNPs can act as efficient catalysts for the conversion of alcohols to the corresponding ketones or aldehydes with high selectivity and yields up to 99% after 2 h of reaction at 110 °C using t-BuOOH as oxidant. Moreover, they have the advantage of being magnetically recoverable catalysts that can be easily recycled in following runs.

Radiation-induced grafting onto wool

International Nuclear Information System (INIS)

Muller-Schulte, D.

1979-10-01

Radiation-induced grafting tests were done on single wool fibres. Different vinyl monomers were used for this purpose and they were grafted in twenty different solvents which were selected for their swelling effiency and solvent parameters. The tests were done once with and once without the addition of water. The presence of water causes the polymer uptake to increase considerably. Formic acid/methanol and methanol were found to be the most suitable solvent systems, as they have the highest hydrogen-bond interaction effiency. The moisture uptake of wool depends on the hydrophily and hydrophoby of the grafted polymers. The single-fibre tests serve as a basis for analogous grafting tests on wool fabrics. The permanent- press was improved by graftng with hydrophoric polymers and polymers with a high glass-transition temperature [af

Influence of the type of solvent on the development of superhydrophobicity from silane-based solution containing nanoparticles

Science.gov (United States)

Pantoja, M.; Abenojar, J.; Martinez, M. A.

2017-03-01

Superhydrophobic surfaces are very appealing for numerous industrial applications due to their self-cleaning capacity. Although there are different methods to manufacture superhydrophobic surfaces, some of them do not keep the aesthetic appearance of the neat surface. Sol-gel processes are a valid alternative when transparent coatings are desired. The main goal of this research is to study the viability of this method by making superhydrophobic coatings from silane-based solution containing SiO2 nanoparticles. The effect of using different solvents is investigated, as well as the role played by the different components of the solution (silane, nanoparticles and solvent). Solutions of methyltrimethoxisilane (MTS) and tetraethoxysilane (TEOS) and 1% of SiO2 (%wt) were prepared with different solvents (ethanol, ethanol/water and white spirit). The hydrophobicity of the developed coatings is studied using contact angle measurements, while the aesthetic appearance is evaluated with gloss and color measurements. Also, infrared spectroscopy, dynamic light scattering (DSL), and surface tension measurements are used to study the silane solutions. The results show that the capacity of solvents to promote the dispersion of the nanoparticles is crucial to ensuring superhydrophobicity, since these agglomerates provide the micro- and nano- surface roughness required to get a hierarchical structure. However, the combined use of silanes and nanoparticles is key to make a superhydrophobic surface because physical (the surface roughness provided by nanoparticles) and chemical characteristics (hydrophobicity provided by silanes) are coupled.

Microwave-assisted silica-promoted solvent-free synthesis of ...

Indian Academy of Sciences (India)

method using microwave irradiation with an excellent yield. The newly ... Table 1. Silica promoted microwave-assisted solvent-free synthesis of quinazolinone ... Time (min). Yield (%)a ..... thanks SC/ST cell of Bangalore University for research.

A free vein graft cap influences neuroma formation after nerve transection.

Science.gov (United States)

Galeano, Mariarosaria; Manasseri, Benedetto; Risitano, Giovanni; Geuna, Stefano; Di Scipio, Federica; La Rosa, Paola; Delia, Gabriele; D'Alcontres, Francesco Stagno; Colonna, Michele R

2009-01-01

: Neuroma formation is a major problem in nerve surgery and consensus about its prevention has not been reached. It has been suggested that vein covering can reduce neuroma formation in transected nerves. In this article, the Authors propose an easy and novel method of covering by nerve stump capping with a free vein graft. : Neuroma-like lesions were created on the rat thigh sectioning the femoral nerve above its division in 16 animals. The proximal nerve stump was invaginated into the lumen of a 1.5 cm long femoral free vein graft on the right side, and the vein was closed on itself by microsurgical sutures to form a cap for the nerve stump. On the left side acting as the control neuroma, the nerve was cut and left uncovered. Histological and immunohistochemical assessment was used to quantify the degree of neuroma formation. : Significant differences were found in both neuroma size and axon-glia organization between the treated and control sides indicating that free vein graft capping reduced neuroma formation in comparison to uncovered nerve stumps. : Our results confirm that vein-covering of a transected nerve stump can be effective in reducing neuroma formation. Moreover, unlike previous works that buried the nerve into an adjacent vein left in place, our experiments showed that also the use of a free vein graft cap can hinder neuroma formation. Although translation of rat experiments to the clinics should be dealt with caution, our data suggest a careful clinical use of the technique. (c) 2009 Wiley-Liss, Inc. Microsurgery, 2009.

Additives in UV and ionising radiation grafting and curing processes

International Nuclear Information System (INIS)

Garnett, J.L.; Ng, L.T.; Viengkhou, V.

1998-01-01

Full text: Curing of polymers induced by both UV and ionising radiation are now established technologies. Currently both systems are predominantly based on acrylate chemistry. UV processes use photoinitiators to achieve fast polymerisation. In the proposed paper the significance of the occurrence of concurrent grafting with cure will be examined. particularly with respect to the recycling of finished product. Basic studies on grafting initiated by UV and ionising radiation will be discussed. Polar methyl methacrylate (MMA) and non-polar styrene will be used as representative monomers with cellulose and propylene typifying the backbone polymers. The additives chosen for examination in this study are predominantly components used in radiation curing formulations since grafting and curing are known to be mechanically related. The additives used were mineral acid, photoinitiators, vinyl ethers, oligomers, polyfunctional monomers including multifunctional acrylates (MFAs) and methacrylates (MFMAs). For the first time the use of charge transfer complexes in the Mulliken sense as additives in radiation grafting will be discussed. The CT complexes themselves, being monomers, have also been grafted to the above polymers. Recent developments with excimer laser sources for initiating these processes will be discussed, especially the use of non-acrylate chemistry. Excimer laser sources are shown to complement conventional UV and ionising radiation and are photoinitiator free. Mechanisms for the above grafting and curing processes will be outlined

Combretastatin A4/poly(L-glutamic acid-graft-PEG conjugates self-assembled to nanoparticles

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Yang Ou

2018-03-01

Full Text Available Combretastatin A4 (CA4 possesses varying ability to cause vascular disruption in tumors, while the short half-life, low water solubility and deactivation of many CA4 analogs during storage limited its antitumor efficacy and drug stability. A novel macromolecular conjugate of CA4 (CA4-PL was synthesized by covalent bonding of CA4 onto poly(L-glutamic acid-graft-polyethylene glycol (PLG-g-PEG via Yamaguchi reaction. The obtained CA4-PL was characterized by 1H NMR, GPC, and UV methods, and the properties of the nanoparticles composed of CA4-PL, including critical aggregation concentration, size and size distribution, and morphology, were investigated. CA4-PL can self-assemble to form micelle-like nanoparticles of 80~120 nm in diameter, which may have potential to improve the blood circulation period as well as the targetability of CA4, and find applications to treat various tumors when combined with traditional chemotherapy or radio therapy. Keywords: Combretastatin A4, Macromolecular conjugate, Poly(L-glutamic acid-graft-polyethylene glycol, Self-assemble, Nanoparticles

Quantitative study of fluctuation effects by fast lattice Monte Carlo simulations: Compression of grafted homopolymers

International Nuclear Information System (INIS)

Zhang, Pengfei; Wang, Qiang

2014-01-01

Using fast lattice Monte Carlo (FLMC) simulations [Q. Wang, Soft Matter 5, 4564 (2009)] and the corresponding lattice self-consistent field (LSCF) calculations, we studied a model system of grafted homopolymers, in both the brush and mushroom regimes, in an explicit solvent compressed by an impenetrable surface. Direct comparisons between FLMC and LSCF results, both of which are based on the same Hamiltonian (thus without any parameter-fitting between them), unambiguously and quantitatively reveal the fluctuations/correlations neglected by the latter. We studied both the structure (including the canonical-ensemble averages of the height and the mean-square end-to-end distances of grafted polymers) and thermodynamics (including the ensemble-averaged reduced energy density and the related internal energy per chain, the differences in the Helmholtz free energy and entropy per chain from the uncompressed state, and the pressure due to compression) of the system. In particular, we generalized the method for calculating pressure in lattice Monte Carlo simulations proposed by Dickman [J. Chem. Phys. 87, 2246 (1987)], and combined it with the Wang-Landau–Optimized Ensemble sampling [S. Trebst, D. A. Huse, and M. Troyer, Phys. Rev. E 70, 046701 (2004)] to efficiently and accurately calculate the free energy difference and the pressure due to compression. While we mainly examined the effects of the degree of compression, the distance between the nearest-neighbor grafting points, the reduced number of chains grafted at each grafting point, and the system fluctuations/correlations in an athermal solvent, the θ-solvent is also considered in some cases

Preparation of Risedronate Nanoparticles by Solvent Evaporation Technique

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Eliska Vaculikova

2014-11-01

Full Text Available One approach for the enhancement of oral drug bioavailability is the technique of nanoparticle preparation. Risedronate sodium (Biopharmaceutical Classification System Class III was chosen as a model compound with high water solubility and low intestinal permeability. Eighteen samples of risedronate sodium were prepared by the solvent evaporation technique with sodium dodecyl sulfate, polysorbate, macrogol, sodium carboxymethyl cellulose and sodium carboxymethyl dextran as nanoparticle stabilizers applied in three concentrations. The prepared samples were characterized by dynamic light scattering and scanning electron microscopy. Fourier transform mid-infrared spectroscopy was used for verification of the composition of the samples. The particle size of sixteen samples was less than 200 nm. Polysorbate, sodium carboxymethyl dextran and macrogol were determined as the most favourable excipients; the particle size of the samples of risedronate with these excipients ranged from 2.8 to 10.5 nm.

Grafting of allylimidazole and n-vinylcaprolactam as a thermosensitive polymer onto magnetic nano-particles for the extraction and determination of celecoxib in biological samples.

Science.gov (United States)

Morovati, Atefeh; Ahmad Panahi, Homayon; Yazdani, Farzaneh

2016-11-20

In this research, a novel method is reported for the surface grafting of n-vinylcaprolactam as a thermosensitive agent and allylimidazole with affinity toward celecoxib onto magnetic nano-particles. The grafted nano-particles were characterized by Fourier transform infrared spectroscopy, elemental analysis, and thermogravimetric analysis. The surface morphology was studied using Scanning Electron Microscopy. The resulting grafted nano-particles were used for the determination of trace celecoxib in biological human fluids and pharmaceutical samples. The profile of celecoxib uptake by the modified magnetic nano-particles indicated good accessibility of the active sites in the grafted copolymer. It was found that the adsorption behavior could be fitted by the Langmuir adsorption isotherm model. Solid phase extraction for biological fluids such as urine and serum were investigated. In this study, urine extraction recovery of more than 95% was obtained. Copyright © 2016 Elsevier B.V. All rights reserved.

Treatment of Desquamative Gingivitis with Free Gingival Graft: A Case Report

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Mehdi Vatankhah

2010-03-01

Full Text Available Recalcitrant gingival erythematous lichen planus lesions comprise a considerable therapeutic problem. This case of chronic desquamative gingivitis in a 25-year-old woman with erosive oral lichen planus was treated with topical and systemic corticosteroid administration, followed by placement of a free gingival graft on right upper quadrant. Although recurrence of the lesions was observed following both treatment modalities, free gingival graft despite being an aggressive therapy, proved more effective and with fewer side effects compared with topical or systemic steroid therapy, and seems to be a promising treatment modality with the benefit of more stable results, among others.

Solvent-free microwave extraction of essential oil from Melaleuca leucadendra L.

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Widya Ismanto Aviarina

2018-01-01

Full Text Available Cajuput (Melaleuca leucadendra L. oil is one of potential commodity that provides an important role for the country’s foreign exchange but the extraction of these essential oil is still using conventional method such as hydrodistillation which takes a long time to produce essential oil with good quality. Therefore it is necessary to optimize the extraction process using a more effective and efficient method. So in this study the extraction is done using solvent-free microwave extraction method that are considered more effective and efficient than conventional methods. The optimum yield in the extraction of cajuput oil using solvent-free microwave extraction method is 1.0674%. The optimum yield is obtained on the feed to distiller (F/D ratio of 0.12 g/mL with microwave power of 400 W. In the extraction of cajuput oil using solvent-free microwave extraction method is performed first-order and second-order kinetics modelling. Based on kinetics modelling that has been done, it can be said that the second-order kinetic model (R2 = 0.9901 can be better represent experimental results of extraction of cajuput oil that using solvent-free microwave extraction method when compared with the first-order kinetic model (R2 = 0.9854.

Enhanced specific heat capacity of molten salt-based nanomaterials: Effects of nanoparticle dispersion and solvent material

International Nuclear Information System (INIS)

Jo, Byeongnam; Banerjee, Debjyoti

2014-01-01

This study investigated the effect of nanoparticle dispersion on the specific heat capacity for carbonate salt mixtures doped with graphite nanoparticles. The effect of the solvent material was also examined. Binary carbonate salt mixtures consisting of lithium carbonate and potassium carbonate were used as the base material for the graphite nanomaterial. The different dispersion uniformity of the nanoparticles was created by employing two distinct synthesis protocols for the nanomaterial. Different scanning calorimetry was employed to measure the specific heat capacity in both solid and liquid phases. The results showed that doping the molten salt mixture with the graphite nanoparticles significantly raised the specific heat capacity, even in minute concentrations of graphite nanoparticles. Moreover, greater enhancement in the specific heat capacity was observed from the nanomaterial samples with more homogeneous dispersion of the nanoparticles. A molecular dynamics simulation was also performed for the nanomaterials used in the specific heat capacity measurements to explain the possible mechanisms for the enhanced specific heat capacity, including the compressed layering and the species concentration of liquid solvent molecules

Grafting of 4-aminomethylbenzensulfonamide-lipoic acid conjugate on gold nanoparticles

Science.gov (United States)

Stiti, M.; Bouzit, H.; Abdaoui, M.; Winum, J. Y.

2012-02-01

In this paper, we describe the synthesis of goldnanoparticles bearing aminomethylbenzensulfonamide via a lipoyl moiety. The resulting stable nanoparticles with an average size of 4.0 nm have been achieved by a facile and high-yielding one phase method, by the action of 4-aminomethylbenzensulfonamide-lipoic acid bioconjugate on chloroauric acide, using dimethylsulfoxide (DMSO) as the solvent and sodium tetrahydridoborate (NaBH4) as the reducing agent. UV-vis absorption, transmission electron microscopy (TEM) and X-ray diffraction were used to analyse the morphology and the structure of the obtained nanoparticles. Preliminary study shows that these new nanoparticles are endowed with highly and specific inhibitory activity for the isoform (IX) of carbonic anhydrase over expressed in many cancers, and are therefore attractive candidate to be used both in diagnosis and in treatment of tumours.

Bone scintigraphy in evaluating the viability of composite bone grafts revascularized by microvascular anastomoses, conventional autogenous bone grafts, and free non-revascularized periosteal grafts

International Nuclear Information System (INIS)

Berggren, A.; Weiland, A.J.; Ostrup, L.T.

1982-01-01

Researchers studied the value of bone scintigraphy in the assessment of anastomotic patency and bone-cell viability in free bone grafts revascularized by microvascular anastomoses in twenty-seven dogs. The dogs were divided into three different groups, and scintigraphy was carried out using technetium-labeled methylene diphosphonate in composite bone grafts revascularized by microvascular anastomoses, conventional autogenous bone grafts, and periosteal grafts placed in different recipient beds. The viability of the grafts were evaluated by histological examination and fluorescence microscopy after triple labeling with oxytetracycline on the first postoperative day, alizarin complexone on the fourth postoperative day, and DCAF on the eleventh postoperative day. A positive scintiscan within the first week following surgery indicated patent microvascular anastomoses, and histological study and fluorescence microscopy confirmed that bone throughout the graft was viable. A positive scintiscan one week after surgery or later does not necessarily indicate microvascular patency or bone-cell survival, because new bone formed by creeping substitution on the surface of a dead bone graft can result in this finding

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

Cell adhesion and proliferation on polyethylene grafted with Au nanoparticles

Czech Academy of Sciences Publication Activity Database

Kasálková-Slepičková, N.; Slepička, P.; Kolská, Z.; Sajdl, P.; Bačáková, Lucie; Rimpelová, S.; Švorčík, V.

2012-01-01

Roč. 272, FEB 1 (2012), s. 391-395 ISSN 0168-583X. [International Conference on Ion Beam Modification of Materials /17./. Montreal, 22.08.2010-27.08.2010] R&D Projects: GA ČR(CZ) GAP108/10/1106; GA AV ČR(CZ) KAN400480701 Institutional research plan: CEZ:AV0Z50110509 Keywords : polyenthyne * gold nanoparticles * grafting * cell proliferation Subject RIV: EI - Biotechnology ; Bionics Impact factor: 1.266, year: 2012

Calculation of the surface free energy of fcc copper nanoparticles

International Nuclear Information System (INIS)

Jia Ming; Lai Yanqing; Tian Zhongliang; Liu Yexiang

2009-01-01

Using molecular dynamics simulations with the modified analytic embedded-atom method we calculate the Gibbs free energy and surface free energy for fcc Cu bulk, and further obtain the Gibbs free energy of nanoparticles. Based on the Gibbs free energy of nanoparticles, we have investigated the heat capacity of copper nanoparticles. Calculation results indicate that the Gibbs free energy and the heat capacity of nanoparticles can be divided into two parts: bulk quantity and surface quantity. The molar heat capacity of the bulk sample is lower compared with the molar heat capacity of nanoparticles, and this difference increases with the decrease in the particle size. It is also observed that the size effect on the thermodynamic properties of Cu nanoparticles is not really significant until the particle is less than about 20 nm. It is the surface atoms that decide the size effect on the thermodynamic properties of nanoparticles

Postoperative irradiation after reconstructive surgery: comparative study of radiosensitivity between free-skin grafts and skin flaps

International Nuclear Information System (INIS)

Sumi, Y.; Ueda, M.; Kaneda, T.; Oka, T.; Torii, S.; Sakuma, S.

1984-01-01

Radiation effects after reconstructive surgery (free-skin grafts and skin flaps) were studied in the rat, and the optimum time for irradiation was determined. The radiosensitivity of both free-skin grafts and skin flaps showed the same trend depending on time of irradiation after operation. The grafts or flaps irradiated in the hypervascular stage showed severe reactions to irradiation, whereas those irradiated in the hypovascular stage showed milder reactions in gross and microangiographic observation. Vascular damage should be given primary consideration when deciding the proper time for irradiation after reconstructive surgery. In general, free-skin grafts showed more severe reactions than skin flaps, especially in the grafts irradiated in the early stage after operation. The experimental results of this study cannot be readily transferred to a clinical setting, but they suggest that postoperative irradiation could be begun 3 to 4 weeks after operation with respect to graft or flap survival, and the results of the clinical cases almost coincide with these experimental results

Significance of grafting in radiation curing reactions. Comparison of ionising radiation and UV systems

International Nuclear Information System (INIS)

Zilic, E.; Ng, L.; Viengkhou, V.; Garnett, J.L.

1998-01-01

Full text: Radiation curing is now an accepted commercial technology where both ionising radiation (electron beam) and ultra violet light (UV) sources are used. Grafting is essentially the copolymerisation of a monomer/oligomer to a backbone polymer whereas curing is the rapid polymerisation of a monomer/oligomer mixture onto the surface of the substrate. There is no time scale theoretically associated with grafting processes which can occur in minutes or hours whereas curing reactions are usually very rapid, occurring within a fraction of a second. An important difference between grafting and curing is the nature of the bonding occurring in each process. In grafting covalent carbon-carbon bonds are formed, whereas in curing, bonding usually involves weaker Van der Waals or London dispersion forces. The bonding properties of the systems are important in determining their use commercially. Thus the possibility that concurrent grafting during curing could occur in a system is important since if present, grafting would not only minimise delamination of the coated product but could also, in some circumstances, render difficulties recycling of the finished product especially if it were cellulosic. Hence the conditions for observing the occurrence of concurrent grafting during radiation curing are important. In the present paper, this problem has been studied by examining the effect that the components used in radiation curing exert on a typical reaction. Instead of electron beam sources, the spent fuel element facility at Lucas Heights is used to simulate such ionising radiation sources. The model system utilised is the grafting of a typical methacrylate to cellulose. This is the generic chemistry used in curing systems. The effect of typical additives from curing systems including polyfunctional monomer and oligomers in the grafting reactions have been studied. The ionising radiation results have been compared with analogous data from UV experiments. The significance

Collagen fiber with surface-grafted polyphenol as a novel support for Pd(0) nanoparticles: Synthesis, characterization and catalytic application

International Nuclear Information System (INIS)

Wu Hao; Wu Chao; He Qiang; Liao Xuepin; Shi Bi

2010-01-01

The aim of this study is to use collagen fiber (CF) as a natural polymeric support to synthesize a novel palladium (Pd) nanoparticle catalyst. To achieve a stable immobilization of Pd on CF support, epigallocatechin-3-gallate (EGCG), a typical plant polyphenol, was grafted onto CF surface, acting both as dispersing and stabilizing agent for Pd nanoparticles. Scanning electron microscopy showed that this catalyst was in ordered fibrous state with high flexibility. The presence of EGCG grafted on CF and the interaction mechanism of Pd ions with support was investigated by X-ray photoelectron spectroscopy. X-ray diffraction and transmission electron microscopy offered evidence that the well-dispersed Pd nanoparticles were generated on the outer surface of CF. By using the hydrogenation of allyl alcohol as a model reaction, the synthesized catalyst presented remarkably improved activity, selectivity and reusability as compared with the Pd catalyst supported by CF without grafting of EGCG.

Perlite-SO3H nanoparticles as an efficient and reusable catalyst for one-pot three-component synthesis of 1,2-dihydro-1-aryl-naphtho[1,2-e][1,3]oxazine-3-one derivatives under both microwave-assisted and thermal solvent-free conditions: Single crystal X-ray structure analysis and theoretical study

Directory of Open Access Journals (Sweden)

Ali Ramazani

2016-01-01

Full Text Available A general synthetic route for the synthesis of 1,2-dihydro-1-aryl-naphtho[1,2-e][1,3]oxazine-3-one derivatives has been developed using perlite-SO3H nanoparticles as efficient catalyst under both microwave-assisted and thermal solvent-free conditions. The combination of 2-naphthol, aldehyde and urea enabled the synthesis of 1,2-dihydro-1-aryl-naphtho[1,2-e][1,3]oxazine-3-one derivatives in the presence of perlite-SO3H nanoparticles in good to excellent yields. This method provides several advantages like simple work-up, environmentally benign, and shorter reaction times along with high yields. In order to explore the recyclability of the catalyst, the perlite-SO3H nanoparticles in solvent-free conditions were used as catalyst for the same reaction repeatedly and the change in their catalytic activity was studied. It was found that perlite-SO3H nanoparticles could be reused for four cycles with negligible loss of their activity. Single crystal X-ray structure analysis and theoretical studies also were investigated for 4i product. The electronic properties of the compound have been analyzed using DFT calculations (B3LYP/6-311+G*. The FMO analysis suggests that charge transfer takes place within the molecule and the HOMO is localized mainly on naphthalene and oxazinone rings whereas the LUMO resides on the naphthalene ring.

Defect-rich Ni-Ti layered double hydroxide as a highly efficient support for Au nanoparticles in base-free and solvent-free selective oxidation of benzyl alcohol.

Science.gov (United States)

Liu, Mengran; Fan, Guoli; Yu, Jiaying; Yang, Lan; Li, Feng

2018-04-17

Tuning the surface properties of supported metal catalysts is of vital importance for governing their catalytic performances in nanocatalysis. Here, we report highly dispersed nanometric gold nanoparticles (NPs) supported on Ni-Ti layered double hydroxides (NiTi-LDHs), which were employed in solvent-free and base-free selective oxidation of benzyl alcohol. A series of characterization techniques demonstrated that defect-rich NiTi-LDHs could efficiently stabilize Au NPs and decrease surface electron density of Au NPs. The as-formed Au/NiTi-LDH catalyst with a Ni/Ti molar ratio of 3 : 1 and an Au loading of 0.71 wt% yielded the highest turnover frequency value of ∼4981 h-1 at 120 °C among tested Au/NiTi-LDH catalysts with different Ni/Ti molar ratios, along with a high benzaldehyde selectivity of 98%. High catalytic efficiency of the catalyst was mainly correlated with surface cooperation between unique defects (i.e. defective Ti3+ species and oxygen vacancies) and abundant hydroxyl groups on the brucite-like layers of the NiTi-LDH support, which could lead to the preferential adsorption and activation of an alcohol hydroxyl moiety in benzyl alcohol and oxygen molecule, as well as the formation of more electron-deficient Ni3+ and Au0 species on the catalyst surface. Furthermore, the present Au/NiTi-LDH catalyst tolerated the oxidation of a wide variety of substrate structures into the corresponding aldehydes, acids or ketones. Our primary results illustrate that defect-rich NiTi-LDHs are promising supports which can efficiently modify surface structure and electronic properties of supported metal catalysts and consequently improve their catalytic performances.

Response of Fibroblasts MRC-5 to Flufenamic Acid-Grafted MCM-41 Nanoparticles

Directory of Open Access Journals (Sweden)

Giovanna Gomes Lara

2018-01-01

Full Text Available Recently, flufenamic acid (FFA was discovered among fenamates as a free radical scavenger and gap junction blocker; however, its effects have only been studied in cancer cells. Normal cells in the surroundings of a tumor also respond to radiation, although they are not hit by it directly. This phenomenon is known as the bystander effect, where response molecules pass from tumor cells to normal ones, through communication channels called gap junctions. The use of the enhanced permeability and retention effect, through which drug-loaded nanoparticles smaller than 200 nm may accumulate around a tumor, can prevent the local side effect upon controlled release of the drug. The present work, aimed at functionalizing MCM-41 (Mobil Composition of Matter No. 41 silica nanoparticles with FFA and determining its biocompatibility with human fibroblasts MRC-5 (Medical Research Council cell strain 5. MCM-41, was synthesized and characterized structurally and chemically, with multiple techniques. The biocompatibility assay was performed by Live/Dead technique, with calcein and propidium–iodide. MRC-5 cells were treated with FFA-grafted MCM-41 for 48 h, and 98% of cells remained viable, without signs of necrosis or morphological changes. The results show the feasibility of MCM-41 functionalization with FFA, and its potential protection of normal cells, in comparison to the role of FFA in cancerous ones.

Response of Fibroblasts MRC-5 to Flufenamic Acid-Grafted MCM-41 Nanoparticles.

Science.gov (United States)

Lara, Giovanna Gomes; Cipreste, Marcelo Fernandes; Andrade, Gracielle Ferreira; Silva, Wellington Marcos da; Sousa, Edésia Martins Barros de

2018-01-09

Recently, flufenamic acid (FFA) was discovered among fenamates as a free radical scavenger and gap junction blocker; however, its effects have only been studied in cancer cells. Normal cells in the surroundings of a tumor also respond to radiation, although they are not hit by it directly. This phenomenon is known as the bystander effect, where response molecules pass from tumor cells to normal ones, through communication channels called gap junctions. The use of the enhanced permeability and retention effect, through which drug-loaded nanoparticles smaller than 200 nm may accumulate around a tumor, can prevent the local side effect upon controlled release of the drug. The present work, aimed at functionalizing MCM-41 (Mobil Composition of Matter No. 41) silica nanoparticles with FFA and determining its biocompatibility with human fibroblasts MRC-5 (Medical Research Council cell strain 5). MCM-41, was synthesized and characterized structurally and chemically, with multiple techniques. The biocompatibility assay was performed by Live/Dead technique, with calcein and propidium-iodide. MRC-5 cells were treated with FFA-grafted MCM-41 for 48 h, and 98% of cells remained viable, without signs of necrosis or morphological changes. The results show the feasibility of MCM-41 functionalization with FFA, and its potential protection of normal cells, in comparison to the role of FFA in cancerous ones.

Colorimetric detection of riboflavin by silver nanoparticles capped with β-cyclodextrin-grafted citrate.

Science.gov (United States)

Ma, Qi; Song, Jinping; Zhang, Sufang; Wang, Meifang; Guo, Yong; Dong, Chuan

2016-12-01

β-Cyclodextrin-grafted citrate was used for the first time as a stabilizer and reducer to prepare silver nanoparticles (AgNPs). The as-synthesized AgNPs were further characterized by UV-vis absorption spectroscopy, powder X-ray diffraction spectroscopy, and transmission electron microscopy. The results show that the presence of riboflavin caused severe aggregation of the nanoparticles, thereby inducing a colour change from yellow to red. 1 H NMR further verified the formation of non-inclusion complexes between riboflavin and β-cyclodextrin-grafted citrate. Hydrogen bond was considered the main driving force of the interaction between the riboflavin and external rim of β-cyclodextrin. Based on these observations, the as-synthesized AgNPs were utilized to develop a novel colorimetric sensor for riboflavin detection. This colorimetric probe showed excellent selectivity and high sensitivity for riboflavin with a detection limit of 167nM. Copyright © 2016 Elsevier B.V. All rights reserved.

Radiation-induced grafting of styrene onto poly-vinylidene fluoride) film by simultaneous method with two different solvents

International Nuclear Information System (INIS)

Ferreira, H.P.; Parra, D.F.; Lugao, A.B.

2011-01-01

Complete text of publication follows. Radiation-induced grafting to create membranes with ion exchange capacity in fluorinated polymers has been studied for applications such as fuel cells, filtration and waste treatment and polymeric actuators due to their good physical and chemical properties. In this work, radiation-induced grafting of styrene into poly(vinylidene fluoride) (PVDF) films with 0.125 mm thickness at doses of 1 and 2.5 kGy in the presence of a styrene/N,N- dimethylformamide (DMF) solution (1:1, v/v) and at doses of 20, 40 and 80 kGy in presence of a styrene/toluene solution (1:1, v/v) at dose rate of 5 kGy h-1 was carried out by simultaneous method under nitrogen atmosphere and at room temperature, using gamma-rays form a Co-60. The films were characterized before and after modification by the grafting yield (GY), infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetry (TG/DTG). GY results shows that grafting increases with dose, and it was possible to confirm the grafting of styrene by FT-IR due to the new characteristics peaks and by the TG and DSC due to changes in thermal behavior of the grafted material. Results showed that the system allows the homogeneous grafting of styrene into PVDF using gamma irradiation at doses as low as 1 kGy when DMF is used and heterogeneous grafting when toluene is used, showing the importance of the solvent nature during the simultaneous method.

Stability of anti-reflection coatings via the self-assembly encapsulation of silica nanoparticles by diazo-resins

Science.gov (United States)

Metzman, Jonathan S.; Ridley, Jason I.; Khalifa, Moataz B.; Heflin, James R.

2015-12-01

A modified silica nanoparticle (MSNP) solution was formed by the encapsulation of negatively charged silica nanoparticles by the UV-crosslinkable polycation oligomer diazo-resin (DAR). Appropriate DAR encapsulation concentrations were determined by use of zeta-potential and dynamic light scattering measurements. The MSNPs were used in conjunction with poly(styrene sulfonate) (PSS) to grow homogenous ionic self-assembled multilayer anti-reflection coatings. Stability was induced within the films by the exposure of UV-irradiation that allowed for crosslinking of the DAR and PSS. The films were characterized by UV/vis/IR spectroscopy and field emission scanning electron microscopy. The transmission and reflection levels were >98.5% and <0.05%, respectively. The refractive indices resided in the 1.25-1.26 range. The solvent stability was tested by sonication of the films in a ternary solvent (H2O/DMF/ZnCl2 3:5:2 w/w/w).

Recent Advances in Anhydrous Solvents for CO2 Capture: Ionic Liquids, Switchable Solvents, and Nanoparticle Organic Hybrid Materials

International Nuclear Information System (INIS)

Park, Youngjune; Lin, Kun-Yi Andrew; Park, Ah-Hyung Alissa; Petit, Camille

2015-01-01

CO 2 capture by amine scrubbing, which has a high CO 2 capture capacity and a rapid reaction rate, is the most employed and investigated approach to date. There are a number of recent large-scale demonstrations including the Boundary Dam Carbon Capture Project by SaskPower in Canada that have reported successful implementations of aqueous amine solvent in CO 2 capture from flue gases. The findings from these demonstrations will significantly advance the field of CO 2 capture in the coming years. While the latest efforts in aqueous amine solvents are exciting and promising, there are still several drawbacks to amine-based CO 2 capture solvents including high volatility and corrosiveness of the amine solutions as well as the high parasitic energy penalty during the solvent regeneration step. Thus, in a parallel effort, alternative CO 2 capture solvents, which are often anhydrous, have been developed as the third-generation CO 2 capture solvents. These novel classes of liquid materials include ionic liquids, CO 2 -triggered switchable solvents (i.e., CO 2 -binding organic liquids, reversible ionic liquids), and nanoparticle organic hybrid materials. This paper provides a review of these various anhydrous solvents and their potential for CO 2 capture. Particular attention is given to the mechanisms of CO 2 absorption in these solvents, their regeneration and their processability – especially taking into account their viscosity. While not intended to provide a complete coverage of the existing literature, this review aims at pointing the major findings reported for these new classes of CO 2 capture media.

Influence of solvents on the changes in structure, purity, and in vitro characteristics of green-synthesized ZnO nanoparticles from Costus igneus

Science.gov (United States)

Nandhini, G.; Suriyaprabha, R.; Maria Sheela Pauline, W.; Rajendran, V.; Aicher, Wilhelm Karl; Awitor, Oscar Komla

2018-05-01

The present study is intended to produce high-purity zinc oxide nanoparticles from the leaves of Costus igneus and zinc acetate precursor via sustainable methods by the tribulation with three different solvents (hot water, methanol, and acetone) for the extraction of plant compounds. While examining the physico-chemical characteristics of ZnO nanoparticles incurred by the catalysis of plant bioactive compounds extracted from different solvents, the hot water extract-based green synthesis process yields higher purity (99.89%) and smaller particle size (94 nm) than other solvents. The optimization of the solvents used for the green synthesis of nanoparticles renders key identification in appropriate extraction of bioactive compounds suitable for the nucleation/production of nanoparticles in addition to annealing temperature. The impregnable usage of ZnO nanoparticles in clinical applications is further confirmed based on the treatment of particles (1-10 mg ml-1) against Gram-positive (S. aureus and S. epidermis) and Gram-negative bacteria (E. coli and K. pneumoniae) with respect to their growth inhibition. An in-force growth inhibition against particular S. aureus and S. epidermis imparted by the low concentration of ZnO nanoparticles signifies the utilization and consumption of green-synthesized high-purity nanoparticles for therapeutic and cosmetic applications.

Surface functionalization of SBA-15 by the solvent-free method

International Nuclear Information System (INIS)

Wang Yimeng; Zheng Yingwu; Zhu Jianhua

2004-01-01

A solvent-free technique was employed for fast modification of mesoporous materials. Copper, chromium and iron oxide species could be highly dispersed in SBA-15 by manually grinding the corresponding precursor salts and the host, followed by calcinations for the first time. This method is more effective to spontaneously disperse oxide species onto SBA-15 than impregnation, probably forming monolayer or submonolayer dispersion of salts or oxides. Besides, Cr(VI) species dominate in the mixing sample while Cr(III) species dominate in the impregnation one. In the temperature programmed surface reaction of nitrosamines, the sample prepared by solvent-free method showed a higher catalytic activity than the impregnation one

Liquid Quinones for Solvent-Free Redox Flow Batteries.

Science.gov (United States)

Shimizu, Akihiro; Takenaka, Keisuke; Handa, Naoyuki; Nokami, Toshiki; Itoh, Toshiyuki; Yoshida, Jun-Ichi

2017-11-01

Liquid benzoquinone and naphthoquinone having diethylene glycol monomethyl ether groups are designed and synthesized as redox active materials that dissolve supporting electrolytes. The Li-ion batteries based on the liquid quinones using LiBF 4 /PC show good performance in terms of voltage, capacity, energy efficiency, and cyclability in both static and flow modes. A battery is constructed without using intentionally added organic solvent, and its high energy density (264 W h L -1 ) demonstrates the potential of solvent-free organic redox flow batteries using liquid active materials. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of solvent-free ambient mass spectrometry for green chemistry applications.

Science.gov (United States)

Liu, Pengyuan; Forni, Amanda; Chen, Hao

2014-04-15

Green chemistry minimizes chemical process hazards in many ways, including eliminating traditional solvents or using alternative recyclable solvents such as ionic liquids. This concept is now adopted in this study for monitoring solvent-free reactions and analysis of ionic liquids, solids, and catalysts by mass spectrometry (MS), without using any solvent. In our approach, probe electrospray ionization (PESI), an ambient ionization method, was employed for this purpose. Neat viscous room-temperature ionic liquids (RTILs) in trace amounts (e.g., 25 nL) could be directly analyzed without sample carryover effect, thereby enabling high-throughput analysis. With the probe being heated, it can also ionize ionic solid compounds such as organometallic complexes as well as a variety of neat neutral solid chemicals (e.g., amines). More importantly, moisture-sensitive samples (e.g., [bmim][AlCl4]) can be successfully ionized. Furthermore, detection of organometallic catalysts (including air-sensitive [Rh-MeDuPHOS][OTf]) in ionic liquids, a traditionally challenging task due to strong ion suppression effect from ionic liquids, can be enabled using PESI. In addition, PESI can be an ideal approach for monitoring solvent-free reactions. Using PESI-MS, we successfully examined the alkylation of amines by alcohols, the conversion of pyrylium into pyridinium, and the condensation of aldehydes with indoles as well as air- and moisture-sensitive reactions such as the oxidation of ferrocene and the condensation of pyrazoles with borohydride. Interestingly, besides the expected reaction products, the reaction intermediates such as the monopyrazolylborate ion were also observed, providing insightful information for reaction mechanisms. We believe that the presented solvent-free PESI-MS method would impact the green chemistry field.

Solvent-free, catalyst-free aza-Michael addition of cyclohexylamine to diethyl maleate: reaction mechanism and kinetics

Czech Academy of Sciences Publication Activity Database

Bláha, Michal; Trhlíková, Olga; Podešva, Jiří; Abbrent, Sabina; Steinhart, Miloš; Dybal, Jiří; Dušková-Smrčková, Miroslava

2018-01-01

Roč. 74, č. 1 (2018), s. 58-67 ISSN 0040-4020 Institutional support: RVO:61389013 Keywords : Aza-Michael addition * solvent-free * catalyst-free Subject RIV: CD - Macromolecular Chemistry OBOR OECD: Polymer science Impact factor: 2.651, year: 2016

Synthesis of soybean oil-based thiol oligomers.

Science.gov (United States)

Wu, Jennifer F; Fernando, Shashi; Weerasinghe, Dimuthu; Chen, Zhigang; Webster, Dean C

2011-08-22

Industrial grade soybean oil (SBO) and thiols were reacted to generate thiol-functionalized oligomers via a thermal, free radical initiated thiol-ene reaction between the SBO double bond moieties and the thiol functional groups. The effect of the reaction conditions, including thiol concentration, catalyst loading level, reaction time, and atmosphere, on the molecular weight and the conversion to the resultant soy-thiols were examined in a combinatorial high-throughput fashion using parallel synthesis, combinatorial FTIR, and rapid gel permeation chromatography (GPC). High thiol functionality and concentration, high thermal free radical catalyst concentration, long reaction time, and the use of a nitrogen reaction atmosphere were found to favor fast consumption of the SBO, and produced high molecular weight products. The thiol conversion during the reaction was inversely affected by a high thiol concentration, but was favored by a long reaction time and an air reaction atmosphere. These experimental observations were explained by the initial low affinity of the SBO and thiol, and the improved affinity between the generated soy-thiol oligomers and unreacted SBO during the reaction. The synthesized soy-thiol oligomers can be used for renewable thiol-ene UV curable materials and high molecular solids and thiourethane thermal cure materials. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recent Advances in Anhydrous Solvents for CO2 Capture: Ionic Liquids, Switchable Solvents, and Nanoparticle Organic Hybrid Materials

Directory of Open Access Journals (Sweden)

YOUNGJUNE ePARK

2015-10-01

Full Text Available CO2 capture by amine scrubbing, which has a high CO2 capture capacity and a rapid reaction rate, is the most employed and investigated approach to date. There are a number of recent large-scale demonstrations including the Boundary Dam Carbon Capture Project by SaskPower in Canada that have reported successful implementations of aqueous amine solvent in CO2 capture from flue gases. The findings from these demonstrations will significantly advance the field of CO2 capture in the coming years. While the latest efforts in aqueous amine solvents are exciting and promising, there are still several drawbacks to amine-based CO2 capture solvents including high volatility and corrosiveness of the amine solutions, as well as the high parasitic energy penalty during the solvent regeneration step. Thus, in a parallel effort, alternative CO2 capture solvents, which are often anhydrous, have been developed as the third-generation CO2 capture solvents. These novel classes of liquid materials include: Ionic Liquids (ILs, CO2-triggered switchable solvents (i.e., CO2 Binding Organic Liquids (CO2BOLs, Reversible Ionic Liquids (RevILs, and Nanoparticle Organic Hybrid Materials (NOHMs. This paper provides a review of these various anhydrous solvents and their potential for CO2 capture. Particular attention is given to the mechanisms of CO2 absorption in these solvents, their regeneration and their processability – especially taking into account their viscosity. While not intended to provide a complete coverage of the existing literature, this review aims at pointing the major findings reported for these new classes of CO2 capture media.

Synthesis of Monodispersed Gold Nanoparticles with Exceptional Colloidal Stability with Grafted Polyethylene Glycol-g-polyvinyl Alcohol

Directory of Open Access Journals (Sweden)

Alaaldin M. Alkilany

2015-01-01

Full Text Available Herein, we report the synthesis of spherical gold nanoparticles with tunable core size (23–79 nm in the presence of polyethylene glycol-g-polyvinyl alcohol (PEG-g-PVA grafted copolymer as a reducing, capping, and stabilizing agent in a one-step protocol. The resulted PEG-g-PVA-capped gold nanoparticles are monodispersed with an exceptional colloidal stability against salt addition, repeated centrifugation, and extensive dialysis. The effect of various synthesis parameters and the kinetic/mechanism of the nanoparticle formation are discussed.

Surface nanostructuring of thin film composite membranes via grafting polymerization and incorporation of ZnO nanoparticles

Science.gov (United States)

Isawi, Heba; El-Sayed, Magdi H.; Feng, Xianshe; Shawky, Hosam; Abdel Mottaleb, Mohamed S.

2016-11-01

A new approach for modification of polyamid thin film composite membrane PA(TFC) using synthesized ZnO nanoparticles (ZnO NPs) was shown to enhance the membrane performances for reverse osmosis water desalination. First, active layer of synthesis PA(TFC) membrane was activated with an aqueous solution of free radical graft polymerization of hydrophilic methacrylic acid (MAA) monomer onto the surface of the PA(TFC) membrane resulting PMAA-g-PA(TFC). Second, the PA(TFC) membrane has been developed by incorporation of ZnO NPs into the MAA grafting solution resulting the ZnO NPs modified PMAA-g-PA(TFC) membrane. The surface properties of the synthesized nanoparticles and prepared membranes were investigated using the FTIR, XRD and SEM. Morphology studies demonstrated that ZnO NPs have been successfully incorporated into the active grafting layer over PA(TFC) composite membranes. The zinc leaching from the ZnO NPs modified PMAA-g-PA(TFC) was minimal, as shown by batch tests that indicated stabilization of the ZnO NPs on the membrane surfaces. Compared with the a pure PA(TFC) and PMAA-g-PA(TFC) membranes, the ZnO NPs modified PMAA-g-PA(TFC) was more hydrophilic, with an improved water contact angle (∼50 ± 3°) over the PMAA-g-PA(TFC) (63 ± 2.5°). The ZnO NPs modified PMAA-g-PA(TFC) membrane showed salt rejection of 97% (of the total groundwater salinity), 99% of dissolved bivalent ions (Ca2+, SO42-and Mg2+), and 98% of mono valent ions constituents (Cl- and Na+). In addition, antifouling performance of the membranes was determined using E. coli as a potential foulant. This demonstrates that the ZnO NPs modified PMAA-g-PA(TFC) membrane can significantly improve the membrane performances and was favorable to enhance the selectivity, permeability, water flux, mechanical properties and the bio-antifouling properties of the membranes for water desalination.

Predicting the activity coefficients of free-solvent for concentrated globular protein solutions using independently determined physical parameters.

Directory of Open Access Journals (Sweden)

Devin W McBride

Full Text Available The activity coefficient is largely considered an empirical parameter that was traditionally introduced to correct the non-ideality observed in thermodynamic systems such as osmotic pressure. Here, the activity coefficient of free-solvent is related to physically realistic parameters and a mathematical expression is developed to directly predict the activity coefficients of free-solvent, for aqueous protein solutions up to near-saturation concentrations. The model is based on the free-solvent model, which has previously been shown to provide excellent prediction of the osmotic pressure of concentrated and crowded globular proteins in aqueous solutions up to near-saturation concentrations. Thus, this model uses only the independently determined, physically realizable quantities: mole fraction, solvent accessible surface area, and ion binding, in its prediction. Predictions are presented for the activity coefficients of free-solvent for near-saturated protein solutions containing either bovine serum albumin or hemoglobin. As a verification step, the predictability of the model for the activity coefficient of sucrose solutions was evaluated. The predicted activity coefficients of free-solvent are compared to the calculated activity coefficients of free-solvent based on osmotic pressure data. It is observed that the predicted activity coefficients are increasingly dependent on the solute-solvent parameters as the protein concentration increases to near-saturation concentrations.

Structure and Dynamics of Polymer/Polymer grafted nanoparticle composite

Science.gov (United States)

Archer, Lynden

Addition of nanoparticles to polymers is a well-practiced methodology for augmenting various properties of the polymer host, including mechanical strength, thermal stability, barrier properties, dimensional stability and wear resistance. Many of these property changes are known to arise from nanoparticle-induced modification of polymer structure and chain dynamics, which are strong functions of the dispersion state of the nanoparticles' and on their relative size (D) to polymer chain dimensions (e.g. Random coil radius Rg or entanglement mesh size a) . This talk will discuss polymer nanocomposites (PNCs) comprised of Polyethylene Glycol (PEG) tethered silica nanoparticles (SiO2-PEG) dispersed in polymers as model systems for investigating phase stability and dynamics of PNCs. On the basis of small-angle X-ray Scattering, it will be shown that favorable enthalpic interactions between particle-tethered chains and a polymer host provides an important mechanism for creating PNCs in which particle aggregation is avoided. The talk will report on polymer and particle scale dynamics in these materials and will show that grafted nanoparticles well dispersed in a polymer host strongly influence the host polymer relaxation dynamics on all timescales and the polymers in turn produce dramatic changes in the nature (from diffusive to hyperdiffusive) and speed of nano particle decorrelation dynamics at the polymer entanglement threshold. A local viscosity model capable of explaining these observations is discussed and the results compared with scaling theories for NP motions in polymers This material is based on work supported by the National Science Foundation Award Nos. DMR-1609125 and CBET-1512297.

In-situ formation of silver nanoparticles on poly (lactic acid) film by γ-radiation induced grafting of N-vinyl pyrrolidone

Energy Technology Data Exchange (ETDEWEB)

Wang, Jingxia; Chen, Hao; Chen, Zhuping; Chen, Yuheng; Guo, Dan; Ni, Maojun; Liu, Siyang; Peng, Chaorong, E-mail: pengchaorong_siae@163.com

2016-06-01

A fast, easy and novel method for preparing biodegradable polymer films with silver nanoparticles was investigated to endow the material with excellent biocompatibility and antibacterial property. Silver nanoparticles (Ag NPs) were immobilized on the surface of polylactic acid (PLA) film by gamma radiation induced grafting of N-vinyl pyrrolidone (NVP). In this method, poly (N-vinyl pyrrolidone) (PVP) was produced and grafted onto the surface of PLA film by gamma radiation polymerization of NVP. PVP acted as both a bridge to connect the Ag NPs with the PLA film, and a stabilizer to protect the Ag NPs from agglomeration. The effect of various reaction parameters, including NVP/Ag mole ratio and radiation dose, on the fabrication of PLA-g-NVP/Ag film was demonstrated. Moreover, the interaction between PVP and Ag NPs was studied by X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy, that revealed the Ag NPs coordinated through the oxygen atom on the carbonyl group of PVP at 15 kGy radiation dose, but through the nitrogen atom and the oxygen atom of the amide group of PVP at 1 kGy dose. - Highlights: • PLA-graft-NVP/Ag film was produced by a simple one-step method. • Ag nanoparticles were immobilized on PLA film by gamma radiation grafting technology. • PVP acted as a bridge to connect Ag nanoparticles and PLA film. • Different content and size of Ag NPs can be reached by varying radiation dose.

In-situ formation of silver nanoparticles on poly (lactic acid) film by γ-radiation induced grafting of N-vinyl pyrrolidone

International Nuclear Information System (INIS)

Wang, Jingxia; Chen, Hao; Chen, Zhuping; Chen, Yuheng; Guo, Dan; Ni, Maojun; Liu, Siyang; Peng, Chaorong

2016-01-01

A fast, easy and novel method for preparing biodegradable polymer films with silver nanoparticles was investigated to endow the material with excellent biocompatibility and antibacterial property. Silver nanoparticles (Ag NPs) were immobilized on the surface of polylactic acid (PLA) film by gamma radiation induced grafting of N-vinyl pyrrolidone (NVP). In this method, poly (N-vinyl pyrrolidone) (PVP) was produced and grafted onto the surface of PLA film by gamma radiation polymerization of NVP. PVP acted as both a bridge to connect the Ag NPs with the PLA film, and a stabilizer to protect the Ag NPs from agglomeration. The effect of various reaction parameters, including NVP/Ag mole ratio and radiation dose, on the fabrication of PLA-g-NVP/Ag film was demonstrated. Moreover, the interaction between PVP and Ag NPs was studied by X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy, that revealed the Ag NPs coordinated through the oxygen atom on the carbonyl group of PVP at 15 kGy radiation dose, but through the nitrogen atom and the oxygen atom of the amide group of PVP at 1 kGy dose. - Highlights: • PLA-graft-NVP/Ag film was produced by a simple one-step method. • Ag nanoparticles were immobilized on PLA film by gamma radiation grafting technology. • PVP acted as a bridge to connect Ag nanoparticles and PLA film. • Different content and size of Ag NPs can be reached by varying radiation dose.

In Vitro Antioxidant-Activity Evaluation of Gallic-Acid-Grafted Chitosan Conjugate Synthesized by Free-Radical-Induced Grafting Method.

Science.gov (United States)

Hu, Qiaobin; Wang, Taoran; Zhou, Mingyong; Xue, Jingyi; Luo, Yangchao

2016-07-27

The major objective of this work was to develop a green and facile process to prepare gallic acid-chitosan conjugate and comprehensively evaluate the physicochemical properties and biological activities of an as-prepared water-soluble chitosan derivative. A free-radical-induced grafting approach using an ascorbic acid-hydrogen peroxide redox pair was adopted. The obtained conjugate was characterized by Fourier transform infrared spectroscopy, UV-vis, X-ray diffraction, and pKa analysis. The antioxidant activities were evaluated by 2,2-diphenyl-1-picrylhydrazyl (DPPH), 2,2'-azino-bis(3-ethylbenzothiazoline-6)-sulphonic acid (ABTS), reducing power, and oxygen-radical antioxidant-capacity assays. The results showed that the mass ratio of gallic acid to chitosan played a vital role in determining the grafting degree and ζ potential of the conjugates, with the ratio of 0.5:1 being the optimal ratio that resulted in the highest grafting degree. The antioxidant assays demonstrated that conjugation significantly improved the antioxidant activities, being dramatically higher than that of free chitosan. It was notable that the DPPH- and ABTS-scavenging activities of conjugate at 0.4 mg/mL reached the same level as the free gallic acid at the equivalent concentration. Our study demonstrated a green and facile synthesis approach to preparing a novel water-soluble chitosan derivative that may have promising potentials in the food industry.

Roles of ethylene glycol solvent and polymers in preparing uniformly distributed MgO nanoparticles

Directory of Open Access Journals (Sweden)

Chunxi Hai

2017-06-01

Full Text Available This study focus on specifying the roles of solvent ethylene glycol (EG and polymers for synthesis of uniformly distributed magnesium oxide (MgO nanoparticles with average crystallite size of around 50 nm through a modified polyol method. Based on different characterization results, it was concluded that, Mg2+ ions was precipitated by the −OH and CO32− ions decomposed from urea in ethylene glycol (EG medium (CO(NH22 → NH3 + HNCO, HNCO + H2O → NH3 + CO2, thus forming well crystallized Mg5(CO34(OH2 (H2O4 precursor which could be converted to MgO by calcination. Surface protectors PEG and PVP have no obvious influences on cyrtsal structure, morphology and size uniformity of as-prepared precursors and target MgO nanoparticles. In comparison with polymers PEG and PVP, solvent EG plays an important role in controlling the morphology and diameter uniformity of MgO nanoparticles.

Solvent-free functionalization of silicone rubber and efficacy of PAAm brushes grafted from an amino-PPX layer against bacterial adhesion.

Science.gov (United States)

Fundeanu, Irina; Klee, Doris; Schouten, Arend J; Busscher, Henk J; van der Mei, Henny C

2010-11-01

Silicone rubber is a frequently employed biomaterial that is prone to bacterial adhesion and biofilm formation. In this study, the surface of silicone rubber was solvent-free functionalized by chemical vapor deposition (CVD) of poly(o-amino-p-xylylene-co-p-xylylene (amino-PPX). Subsequently, the amino groups of the amino-PPX layer were used to introduce the initiator from a vapor phase for atom transfer radical polymerization of acrylamide to form polyacrylamide (PAAm) brushes. The modification steps were verified by means of X-ray photoelectron spectroscopy and attenuated total reflection-Fourier transform infrared spectroscopy. Adhesion of Staphylococcus aureus ATCC 12600 and Escherichia coli 3.14 to an amino-PPX-PAAm brush coating in a parallel plate flow chamber was strongly reduced with respect to non-coated silicone rubber - by 93% and 99%, respectively. For E. coli 3.14, this reduction is larger than that obtained for solvent functionalization of γ-aminopropyltriethoxysilane-PAAm brushes due to the higher density of amino groups introduced by the CVD of amino-PPX. Copyright © 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Magnetic iron oxide nanoparticles grafted N-isopropylacrylamide/chitosan copolymer for the extraction and determination of letrozole in human biological samples.

Science.gov (United States)

Khalaj Moazen, Mercede; Ahmad Panahi, Homayon

2017-03-01

Magnetic iron oxide nanoparticles are used for the extraction of a drug from an aqueous solution. In the current study, the magnetic iron oxide nanoparticles were synthesized via a facile coprecipitation approach, and then modified by (3-mercaptopropyl)trimethoxysilane followed by grafting thermosensitive polymer N-isopropylacrylamide and biopolymer chitosan. Structure, morphology, size, thermal resistance, specific surface area, and magnetic properties of the grafted nanosorbent were characterized by using Fourier transform infrared spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, elemental analysis, thermogravimetric analysis, specific surface area analysis and vibrating sample magnetometry. The effective parameters on sorption/desorption of letrozole on grafted magnetic nanosorbent were evaluated. The best sorption of letrozole via the grafted nanosorbent occurred at 20°C at an optimum pH of 7. The extraction of trace letrozole in human biological fluids is investigated and revealed 89.1 and 97.8% recovery in plasma and urine, respectively. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of MgO Nanoparticles by Solvent Mixed Spray Pyrolysis Technique for Optical Investigation

OpenAIRE

Nemade, K. R.; Waghuley, S. A.

2014-01-01

Solvent mixed spray pyrolysis technique has attracted a global interest in the synthesis of nanomaterials since reactions can be run in liquid state without further heating. Magnesium oxide (MgO) is a category of the practical semiconductor metal oxides, which is extensively used as catalyst and optical material. In the present study, MgO nanoparticles were successfully synthesized using a solvent mixed spray pyrolysis. The X-ray diffraction pattern confirmed the formation of MgO phase with a...

Macrocyclic 2,7-Anthrylene Oligomers.

Science.gov (United States)

Yamamoto, Yuta; Wakamatsu, Kan; Iwanaga, Tetsuo; Sato, Hiroyasu; Toyota, Shinji

2016-05-06

A macrocyclic compound consisting of six 2,7-anthrylene units was successfully synthesized by Ni-mediated coupling of the corresponding dibromo precursor as a novel π-conjugated compound. This compound was sufficiently stable and soluble in organic solvents due to the presence of mesityl groups. X-ray analysis showed that the molecule had a nonplanar and hexagonal wheel-shaped framework of approximately S6 symmetry. The dynamic process between two S6 structures was observed by using the dynamic NMR technique, the barrier being 58 kJ mol(-1) . The spectroscopic properties of the hexamer were compared with those of analogous linear oligomers. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bringing Catalysis with Gold Nanoparticles in Green Solvents to Graduate Level Students

Science.gov (United States)

Raghuwanshi, Vikram Singh; Wendt, Robert; O'Neill, Maeve; Ochmann, Miguel; Som, Tirtha; Fenger, Robert; Mohrmann, Marie; Hoell, Armin; Rademann, Klaus

2017-01-01

We demonstrate here a novel laboratory experiment for the synthesis of gold nanoparticles (AuNPs) by using a low energy gold-sputtering method together with a modern, green, and biofriendly deep eutectic solvent (DES). The strategy is straightforward, economical, ecofriendly, rapid, and clean. It yields uniform AuNPs of 5 nm in diameter with high…

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

Science.gov (United States)

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

2017-01-01

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

Molybdenum carbide nanoparticles as catalysts for oil sands upgrading: Dynamics and free-energy profiles

International Nuclear Information System (INIS)

Liu, Xingchen; Salahub, Dennis R.

2015-01-01

There is no doubt that a huge gap exists in understanding heterogeneous catalysis between a cluster model of a few atoms and a bulk model of periodic slabs. Nanoparticles, which are crucial in heterogeneous catalysis in industry, lie in the middle of the gap. We present here our work on the computational modelling of molybdenum carbide nanoparticles (MCNPs) as the catalysts for the upgrading of oil sands in the in-situ environment, using benzene hydrogenation as a model reaction. With a cluster model, efforts were first made to understand the mechanism of the reaction with a density functional theory (DFT) study on the adsorption of benzene and its hydrogenation product – cyclohexane, as well as the cyclic hydrogenation reaction intermediates on the Mo 2 C(0001) surface. From the thermodynamic data, along with literature information, it was found that the benzene hydrogenation reaction on molybdenum carbide happens most likely through a Langmuir-Hinshelwood mechanism with the gradual lifting up of the benzene molecule. The electron localization function (ELF) was then used to help understand the nature of the interactions between the MCNPs, identifying strong multi-center interactions between the adsorbates and the MCNPs. To enable the treatment of larger nanoparticles, a fast semi-empirical density functional tight-binding (DFTB) method was parameterized. With this method, the potential energy profiles of benzene hydrogenation reactions on different sizes of MCNPs are calculated. The study was then extended to consider a MCNP embedded in solvent (benzene), using a quantum mechanical (DFTB) / molecular mechanical approach. Calculations on the free energies profiles with the umbrella sampling method show that the entropy of the MCNPs and the solvent are essential in understanding the catalytic activity of the transition metal related nanoparticles for solid/liquid heterogeneous catalysis

Molybdenum carbide nanoparticles as catalysts for oil sands upgrading: Dynamics and free-energy profiles

Energy Technology Data Exchange (ETDEWEB)

Liu, Xingchen; Salahub, Dennis R. [Department of Chemistry, Institute for Quantum Science and Technology, and Centre for Molecular Simulation, University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada T2N 1N4 (Canada)

2015-12-31

There is no doubt that a huge gap exists in understanding heterogeneous catalysis between a cluster model of a few atoms and a bulk model of periodic slabs. Nanoparticles, which are crucial in heterogeneous catalysis in industry, lie in the middle of the gap. We present here our work on the computational modelling of molybdenum carbide nanoparticles (MCNPs) as the catalysts for the upgrading of oil sands in the in-situ environment, using benzene hydrogenation as a model reaction. With a cluster model, efforts were first made to understand the mechanism of the reaction with a density functional theory (DFT) study on the adsorption of benzene and its hydrogenation product – cyclohexane, as well as the cyclic hydrogenation reaction intermediates on the Mo{sub 2}C(0001) surface. From the thermodynamic data, along with literature information, it was found that the benzene hydrogenation reaction on molybdenum carbide happens most likely through a Langmuir-Hinshelwood mechanism with the gradual lifting up of the benzene molecule. The electron localization function (ELF) was then used to help understand the nature of the interactions between the MCNPs, identifying strong multi-center interactions between the adsorbates and the MCNPs. To enable the treatment of larger nanoparticles, a fast semi-empirical density functional tight-binding (DFTB) method was parameterized. With this method, the potential energy profiles of benzene hydrogenation reactions on different sizes of MCNPs are calculated. The study was then extended to consider a MCNP embedded in solvent (benzene), using a quantum mechanical (DFTB) / molecular mechanical approach. Calculations on the free energies profiles with the umbrella sampling method show that the entropy of the MCNPs and the solvent are essential in understanding the catalytic activity of the transition metal related nanoparticles for solid/liquid heterogeneous catalysis.

Recent Advances in Anhydrous Solvents for CO{sub 2} Capture: Ionic Liquids, Switchable Solvents, and Nanoparticle Organic Hybrid Materials

Energy Technology Data Exchange (ETDEWEB)

Park, Youngjune [School of Environmental Science and Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju (Korea, Republic of); Lin, Kun-Yi Andrew [Department of Environmental Engineering, National Chung Hsing University, Taichung City (China); Park, Ah-Hyung Alissa, E-mail: ap2622@columbia.edu [Department of Earth and Environmental Engineering, Lenfest Center for Sustainable Energy, Columbia University, New York, NY (United States); Department of Chemical Engineering, Lenfest Center for Sustainable Energy, Columbia University, New York, NY (United States); Petit, Camille, E-mail: ap2622@columbia.edu [Department of Chemical Engineering, Imperial College London, London (United Kingdom)

2015-10-01

CO{sub 2} capture by amine scrubbing, which has a high CO{sub 2} capture capacity and a rapid reaction rate, is the most employed and investigated approach to date. There are a number of recent large-scale demonstrations including the Boundary Dam Carbon Capture Project by SaskPower in Canada that have reported successful implementations of aqueous amine solvent in CO{sub 2} capture from flue gases. The findings from these demonstrations will significantly advance the field of CO{sub 2} capture in the coming years. While the latest efforts in aqueous amine solvents are exciting and promising, there are still several drawbacks to amine-based CO{sub 2} capture solvents including high volatility and corrosiveness of the amine solutions as well as the high parasitic energy penalty during the solvent regeneration step. Thus, in a parallel effort, alternative CO{sub 2} capture solvents, which are often anhydrous, have been developed as the third-generation CO{sub 2} capture solvents. These novel classes of liquid materials include ionic liquids, CO{sub 2}-triggered switchable solvents (i.e., CO{sub 2}-binding organic liquids, reversible ionic liquids), and nanoparticle organic hybrid materials. This paper provides a review of these various anhydrous solvents and their potential for CO{sub 2} capture. Particular attention is given to the mechanisms of CO{sub 2} absorption in these solvents, their regeneration and their processability – especially taking into account their viscosity. While not intended to provide a complete coverage of the existing literature, this review aims at pointing the major findings reported for these new classes of CO{sub 2} capture media.

Effect of phenolic oligomer on adhesion of poly (ethylene terephthalate) film laminated steel sheets by Electron Beam Curing method

International Nuclear Information System (INIS)

Masuhara, Kenichi; Mori, Koji; Koshiishi, Kenji; Sasaki, Takashi.

1995-01-01

Adhesion of poly (ethylene terephthalate) film by Electron Beam Curing (EBC) method which can be thought as an energy-saving process was studied for the purpose of bestowing economically design and distinctness of image on thermosetting high molecular weight polyester precoated steel sheets. Adhesion of EB curable resins onto metal is generally poor. In this report, addition of EB curable phenolic resole oligomer with bifunctional acrylates to the top coat used for precoated steel was studied in order to increase the adhesion of an EB curable adhesive, and it was found that the phenolic oligomer is tremendously effective for the improvement of adhesion. The reasons why the phenolic oligomer provides excellent adhesion were 1) elongation at break of the top coat to which the phenolic oligomer is added is little decreased by EB irradiation, and the formability does not reduce. 2) As the phenolic oligomer is unevenly distributed to the surface layer of the top coat, it is suggested that the contact frequency of the phenolic oligomer to the EB curable adhesive is so high that graft polymerization between them is liable to occur. (author)

Guanidine-based polymer brushes grafted onto silica nanoparticles as efficient artificial phosphodiesterases.

Science.gov (United States)

Savelli, Claudia; Salvio, Riccardo

2015-04-07

Polymer brushes grafted to the surface of silica nanoparticles were fabricated by atom-transfer radical polymerization (ATRP) and investigated as catalysts in the cleavage of phosphodiesters. The surfaces of silica nanoparticles were functionalized with an ATRP initiator. Surface-initiated ATRP reactions, in varying proportions, of a methacrylate moiety functionalized with a phenylguanidine moiety and an inert hydrophilic methacrylate species afforded hybrid nanoparticles that were characterized with potentiometric titrations, thermogravimetric analysis, and SEM. The activity of the hybrid nanoparticles was tested in the transesterification of the RNA model compound 2-hydroxypropyl para-nitrophenylphosphate (HPNP) and diribonucleoside monophosphates. A high catalytic efficiency and a remarkable effective molarity, thus overcoming the effective molarities previously observed for comparable systems, indicate the existence of an effective cooperation of the guanidine/guanidinium units and a high level of preorganization in the nanostructure. The investigated system also exhibits a marked and unprecedented selectivity for the diribonucleoside sequence CpA. The results presented open up the way for a novel and straightforward strategy for the preparation of supramolecular catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Graft copolymers of polypropylene films. 1. radiation induced grafting of mixed monomers. Vol. 3

International Nuclear Information System (INIS)

El-Salmawi, K.M.; El-Naggar, A.M.; Said, H.M.; Zahran, A.H.

1996-01-01

Radiation graft copolymerization of co monomer mixtures of acrylic acid (AAC), and styrene (S) onto polypropylene (PP) film by mutual method has been investigated. The effects of different factors that may affect the grafting yield such as inhibitor concentration (Mohr's salt), solvent composition (MeOH and H 2 O), radiation dose and dose rate were considered. It was found that the role of Mohr's salt is very effective when the ratio of AAC in the co monomer mixtures was at lower values. However, the addition of 1.25 Wt% of Mohr's salt reduced the homo polymer formation and enhances the grafting process. Graft copolymerization in presence of solvent mixture composed of methanol and water was found to afford higher grafting than in pure methanol regardless of the composition of the co monomer mixture used. However, the highest degree of grafting was obtained at a solvent composition of 20% H 2 O:80%MeOH and a co monomer mixture of 20%AAC:80%sty. An attempt was made to determine each PAAC and PS fractions in the total graft yield obtained. Two methods of analysis based on using the reactivity ratios reported in literature, elemental analysis and IR spectroscopy. The determination of poly (acrylic acid) and polystyrene fractions by elemental analysis is believed more accurate than these by reactivity ratio. The precise results obtained by elemental analysis with respect to the chemical structure of known polymer prepared under identical conditions. The results obtained by IR measurements go well with that obtained with the reactivity ratio methods. 5 figs., 3 tabs

Solvent density inhomogeneities and solvation free energies in supercritical diatomic fluids: a density functional approach.

Science.gov (United States)

Husowitz, B; Talanquer, V

2007-02-07

Density functional theory is used to explore the solvation properties of a spherical solute immersed in a supercritical diatomic fluid. The solute is modeled as a hard core Yukawa particle surrounded by a diatomic Lennard-Jones fluid represented by two fused tangent spheres using an interaction site approximation. The authors' approach is particularly suitable for thoroughly exploring the effect of different interaction parameters, such as solute-solvent interaction strength and range, solvent-solvent long-range interactions, and particle size, on the local solvent structure and the solvation free energy under supercritical conditions. Their results indicate that the behavior of the local coordination number in homonuclear diatomic fluids follows trends similar to those reported in previous studies for monatomic fluids. The local density augmentation is particularly sensitive to changes in solute size and is affected to a lesser degree by variations in the solute-solvent interaction strength and range. The associated solvation free energies exhibit a nonmonotonous behavior as a function of density for systems with weak solute-solvent interactions. The authors' results suggest that solute-solvent interaction anisotropies have a major influence on the nature and extent of local solvent density inhomogeneities and on the value of the solvation free energies in supercritical solutions of heteronuclear molecules.

Minimum free-energy paths for the self-organization of polymer brushes.

Science.gov (United States)

Gleria, Ignacio; Mocskos, Esteban; Tagliazucchi, Mario

2017-03-22

A methodology to calculate minimum free-energy paths based on the combination of a molecular theory and the improved string method is introduced and applied to study the self-organization of polymer brushes under poor solvent conditions. Polymer brushes in a poor solvent cannot undergo macroscopic phase separation due to the physical constraint imposed by the grafting points; therefore, they microphase separate forming aggregates. Under some conditions, the theory predicts that the homogeneous brush and the aggregates can exist as two different minima of the free energy. The theoretical methodology introduced in this work allows us to predict the minimum free-energy path connecting these two minima as well as the morphology of the system along the path. It is shown that the transition between the homogeneous brush and the aggregates may involve a free-energy barrier or be barrierless depending on the relative stability of the two morphologies and the chain length and grafting density of the polymer. In the case where a free-energy barrier exists, one of the morphologies is a metastable structure and, therefore, the properties of the brush as the quality of the solvent is cycled are expected to display hysteresis. The theory is also applied to study the adhesion/deadhesion transition between two opposing surfaces modified by identical polymer brushes and it is shown that this process may also require surpassing a free-energy barrier.

β-Cyclodextrin/thermosensitive containing polymer brushes grafted onto magnetite nano-particles for extraction and determination of venlafaxine in biological and pharmaceutical samples.

Science.gov (United States)

Ahmad Panahi, Homayon; Alaei, Haniyeh Sadat

2014-12-10

In this paper, a novel nano-sorbent is fabricated by the surface grafting of poly[β-CD/allylamine-co-N-isopropylacrylamide] onto modified magnetite nano-particles by 3-mercaptopropyltrimethoxysilane. The polymer grafted magnetite nano-particles was characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, elemental analysis, scanning electron microscopy, and transmission electron microscopy. The feasibility of employing this nano-sorbent for extraction of trace venlafaxine in pharmaceutical samples and human biological fluids are investigated. The effect of various parameters such as pH, reaction temperature, and contact time was evaluated. The result revealed that the best sorption of venlafaxine by the magnetite nano-sorbent occurred at 35 °C at an optimum pH of 5. The kinetics of the venlafaxine shows accessibility of active sites in the grafted polymer onto the drug. The equilibrium data of venlafaxine by grafted magnetite nano-sorbent are well represented by the Langmuir and Freundlich isotherm models. The adsorption capacity of venlafaxine is found 142.8 mg g(-1) and indicated the homogeneous sites onto polymer grafted magnetite nano-sorbent surface. Nearly 80% of venlafaxine was released in simulated intestinal fluid, pH 7.4, in 30 h and 90% in simulated gastric fluid, pH 1.2, in 1 h. The venlafaxine loaded-polymer grafted magnetite nano-particles were successfully applied for the extraction in urine and pharmaceutical samples. Copyright © 2014 Elsevier B.V. All rights reserved.

Self-assembly of core-polyethylene glycol-lipid shell (CPLS) nanoparticles and their potential as drug delivery vehicles

Science.gov (United States)

Shen, Zhiqiang; Loe, David T.; Awino, Joseph K.; Kröger, Martin; Rouge, Jessica L.; Li, Ying

2016-08-01

Herein a new multifunctional formulation, referred to as a core-polyethylene glycol-lipid shell (CPLS) nanoparticle, has been proposed and studied in silico via large scale coarse-grained molecular dynamics simulations. A PEGylated core with surface tethered polyethylene glycol (PEG) chains is used as the starting configuration, where the free ends of the PEG chains are covalently bonded with lipid molecules (lipid heads). A complete lipid bilayer is formed at the surface of the PEGylated particle core upon addition of free lipids, driven by the hydrophobic properties of the lipid tails, leading to the formation of a CPLS nanoparticle. The self-assembly process is found to be sensitive to the grafting density and molecular weight of the tethered PEG chains, as well as the amount of free lipids added. At low grafting densities the assembly of CPLS nanoparticles cannot be accomplished. As demonstrated by simulations, a lipid bud/vesicle can be formed on the surface when an excess amount of free lipids is added at high grafting density. Therefore, the CPLS nanoparticles can only be formed under appropriate conditions of both PEG and free lipids. The CPLS nanoparticle has been recognized to be able to store a large quantity of water molecules, particularly with high molecular weight of PEG chains, indicating its capacity for carrying hydrophilic molecules such as therapeutic biomolecules or imaging agents. Under identical size and surface chemistry conditions of a liposome, it has been observed that the CPLS particle can be more efficiently wrapped by the lipid membrane, indicating its potential for a greater efficiency in delivering its hydrophilic cargo. As a proof-of-concept, the experimental realization of CPLS nanoparticles is explicitly demonstrated in this study. To test the capacity of the CPLS to store small molecule cargo a hydrophilic dye was successfully encapsulated in the particles' water soluble layer. The results of this study show the power and

[Reconstruction of the hypopharynx and cervical esophagus using a free jejunal graft].

Science.gov (United States)

Pesko, P; Bumbasirević, M; Knezević, J; Dunjić, M; Djukić, V; Simić, A; Stojakov, D; Sabljak, P; Bjelović, M; Janković, Z; Micev, M; Saranović, D

2000-01-01

Extensive malignant tumors of the hypopharynx and cervical esophagus continue to challenge surgeons in respect to both type and extent of resection as well as type of reconstruction. In the period between November 1st, 1996 and November 1st, 1998, at our Department, five patients have been operated due to squamocellular carcinoma of the hypopharynx using a free jejunal graft reconstruction method. The first free jejunal graft operation due to hypopharyngeal carcinoma, at the same time the first operation of this kind ever done in our Country, was performed on November 13th, 1998. There were 4 female and one male patient, average age 47.75 years. Disfagia for solid foods was a leading symptom in all patients (mean duration of 3.5 months) and was always accompanied with weight loss (average of 8 kg for two months). In all patients barium swallow, endoscopy, CT as well as intraoperative endoscopy was performed. Radical surgical procedure was always accompanied with the bilateral modified lympf node neck dissection. As a arterial donor vessel superior thyroid artery was used in all patients. As a venous drainage in three patients a external jugular vein was used and in two facial vein. Reconstruction using a free jejunal graft of approximately 25 cm long was performed in all patients creating upper, oropharingeal, anastomosis end to side and distal, esophageal, end to end (in only one patients side to end) using 3/0 apsorbable sutures. Mean duration of the operation was six hours. The postoperative course in all patients was uneventful. On the 9th postoperative day gastrografin and three days later barium swallow radiography was performed as a standard control study. Regular check ups were done on three, six, nine months, year and two years. On all controls all patients were symptom free and feeling well. It is our opinion that in the patients with isolated carcinoma of the hypopharynx due to low morbidity and mortality rate, free jejunal graft method is the surgical

Tribological and mechanical investigation of acrylic-based nanocomposite coatings reinforced with PMMA-grafted-MWCNT

Energy Technology Data Exchange (ETDEWEB)

Al-Kawaz, A. [UPR22/CNRS, Institut Charles Sadron, Université de Strasbourg, 23 Rue du Loess, BP 84047, F-67034 Strasbourg Cedex 2 (France); Rubin, A., E-mail: anne.rubin@ics-cnrs.unistra.fr [UPR22/CNRS, Institut Charles Sadron, Université de Strasbourg, 23 Rue du Loess, BP 84047, F-67034 Strasbourg Cedex 2 (France); Badi, N.; Blanck, C.; Jacomine, L. [UPR22/CNRS, Institut Charles Sadron, Université de Strasbourg, 23 Rue du Loess, BP 84047, F-67034 Strasbourg Cedex 2 (France); Janowska, I.; Pham-Huu, C. [Institute of Chemistry and Processes for Energy, Environment and Health (UMR 7515) CNRS - University of Strasbourg, 25 Rue Becquerel Strasbourg, 67087 Cedex 08 (France); Gauthier, C. [UPR22/CNRS, Institut Charles Sadron, Université de Strasbourg, 23 Rue du Loess, BP 84047, F-67034 Strasbourg Cedex 2 (France)

2016-06-01

The chemical functionalization of carbon nanotubes (CNTs) could improve their chemical compatibility. Poly(methyl methacrylate) (PMMA)-functionalized multi-walled carbon nanotubes (MWCNTs) are prepared by in situ atom transfer radical polymerization (ATRP) using a “grafting from” approach. It allows the control of the thickness of the polymer layer grafted on MWCNTs from two parameters: the feed ratio of MMA to MWCNT, the volume fraction of solvent to MMA. This work compared the effect of several PMMA-grafted-MWNCT fillers embedded into a PMMA matrix, PMMA-grafted-MWCNT/PMMA, and obtained by solution mixing technique. We studied the tribological performances of 20 μm coatings of these nanocomposites deposited on neat PMMA. The percentage of embedded fillers is kept low to maintain the transparency of the PMMA. The coefficient of friction was found to relatively decrease with the increase of the weight fraction of polymer grafted to the surface of MWCNT. Moreover the elastic modulus also increased with increasing the weight fraction of PMMA coated MWCNT. - Highlights: • Synthesis of MWCNT-PMMA nanoparticles by ATRP “grafting from” approach. • PMMA-grafted-MWCNT/PMMA coatings with good mechanical properties. • High tribological performance of PMMA-grafted-MWCNT/PMMA coatings.

Preparation and optical properties of indium tin oxide/epoxy nanocomposites with polyglycidyl methacrylate grafted nanoparticles.

Science.gov (United States)

Tao, Peng; Viswanath, Anand; Schadler, Linda S; Benicewicz, Brian C; Siegel, Richard W

2011-09-01

Visibly highly transparent indium tin oxide (ITO)/epoxy nanocomposites were prepared by dispersing polyglycidyl methacrylate (PGMA) grafted ITO nanoparticles into a commercial epoxy resin. The oleic acid stabilized, highly crystalline, and near monodisperse ITO nanoparticles were synthesized via a nonaqueous synthetic route with multigram batch quantities. An azido-phosphate ligand was synthesized and used to exchange with oleic acid on the ITO surface. The azide terminal group allows for the grafting of epoxy resin compatible PGMA polymer chains via Cu(I) catalyzed alkyne-azide "click" chemistry. Transmission electron microscopy (TEM) observation shows that PGMA grafted ITO particles were homogeneously dispersed within the epoxy matrix. Optical properties of ITO/epoxy nanocomposites with different ITO concentrations were studied with an ultraviolet-visible-near-infrared (UV-vis-NIR) spectrometer. All the ITO/epoxy nanocomposites show more than 90% optical transparency in the visible light range and absorption of UV light from 300 to 400 nm. In the near-infrared region, ITO/epoxy nanocomposites demonstrate low transmittance and the infrared (IR) transmission cutoff wavelength of the composites shifts toward the lower wavelength with increased ITO concentration. The ITO/epoxy nanocomposites were applied onto both glass and plastic substrates as visibly transparent and UV/IR opaque optical coatings.

Unraveling the Role of Π - Conjugation in Thiophene Oligomers for Optoelectronic Properties by DFT/TDDFT Approach

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Gajalakshmi

Full Text Available ABSTRACT Thiophene oligomer has been investigated using DFT/TDDFT calculations with an aim to check its suitability for opto electronic applications and also to analyse the influence of π-bridge. Our results revealed that thiophene oligomers have excellent π-conjugation throughout. FMO analysis give an estimate of band gap of thiophene oligomer and further revealed HOMO are localized on π - bridge, donor group and LUMO are localized on π - bridge and acceptor group. A TDDFT calculation has been performed to understand the absorption properties of them in gas phase and solvent phase. PCM calculations convey that absorption maxima show positive solvatochromism. Among the designed candidates, the one with more π - bridge show higher wavelength of absorption maxima and would be a choice for better optoelectronic materials. NBO analysis provides support for complete delocalization in these systems. It is interesting to note that oligomer with more π-bridge display an enhanced optoelectronic properties than with less π - bridge.

Polymer crowding and shape distributions in polymer-nanoparticle mixtures

Energy Technology Data Exchange (ETDEWEB)

Lim, Wei Kang; Denton, Alan R., E-mail: alan.denton@ndsu.edu [Department of Physics, North Dakota State University, Fargo, North Dakota 58108-6050 (United States)

2014-09-21

Macromolecular crowding can influence polymer shapes, which is important for understanding the thermodynamic stability of polymer solutions and the structure and function of biopolymers (proteins, RNA, DNA) under confinement. We explore the influence of nanoparticle crowding on polymer shapes via Monte Carlo simulations and free-volume theory of a coarse-grained model of polymer-nanoparticle mixtures. Exploiting the geometry of random walks, we model polymer coils as effective penetrable ellipsoids, whose shapes fluctuate according to the probability distributions of the eigenvalues of the gyration tensor. Accounting for the entropic cost of a nanoparticle penetrating a larger polymer coil, we compute the crowding-induced shift in the shape distributions, radius of gyration, and asphericity of ideal polymers in a theta solvent. With increased nanoparticle crowding, we find that polymers become more compact (smaller, more spherical), in agreement with predictions of free-volume theory. Our approach can be easily extended to nonideal polymers in good solvents and used to model conformations of biopolymers in crowded environments.

Polymer crowding and shape distributions in polymer-nanoparticle mixtures

International Nuclear Information System (INIS)

Lim, Wei Kang; Denton, Alan R.

2014-01-01

Macromolecular crowding can influence polymer shapes, which is important for understanding the thermodynamic stability of polymer solutions and the structure and function of biopolymers (proteins, RNA, DNA) under confinement. We explore the influence of nanoparticle crowding on polymer shapes via Monte Carlo simulations and free-volume theory of a coarse-grained model of polymer-nanoparticle mixtures. Exploiting the geometry of random walks, we model polymer coils as effective penetrable ellipsoids, whose shapes fluctuate according to the probability distributions of the eigenvalues of the gyration tensor. Accounting for the entropic cost of a nanoparticle penetrating a larger polymer coil, we compute the crowding-induced shift in the shape distributions, radius of gyration, and asphericity of ideal polymers in a theta solvent. With increased nanoparticle crowding, we find that polymers become more compact (smaller, more spherical), in agreement with predictions of free-volume theory. Our approach can be easily extended to nonideal polymers in good solvents and used to model conformations of biopolymers in crowded environments

Grafting study of polysulfone polymeric membranes by gamma ray irradiation

International Nuclear Information System (INIS)

Furtado Filho, Acacio A.M.; Gomes, Ailton de S.

2011-01-01

Radiation-induced grafting of styrene poli sulfone films were investigated by simultaneous method in solution using gamma-ray from a radio nuclide 60 Co source. The gamma-ray energy of high intensity induced breaking of chemical bonds leading to free radical formation. The radical start a conventional polymerization sequence comparable with that obtained with a chemical catalyst acting as initiator. The effects of grafting conditions such as irradiation total dose, dose rate and addition of cross linking agent, were studied by means of morphology analysis, thermal degradation and crystallinity. After the grafting reaction, the membranes were submitted to an exhaustive extraction with solvent to remove the polystyrene homopolymer formed. The degree of grafting (DOG) was analyzed by percentage of weight increase. As a result, the reaction always follows the same pattern: DOG increases rapidly initially whilst propagation is the main reaction, then more slowly as termination becomes more frequent. (author)

Comparison of mesencephalic free-floating tissue culture grafts and cell suspension grafts in the 6-hydroxydopamine-lesioned rat

DEFF Research Database (Denmark)

Meyer, Morten; Widmer, H R; Wagner, B

1998-01-01

days in culture or directly as dissociated cell suspensions, and compared with regard to neuronal survival and ability to normalize rotational behavior in adult rats with unilateral 6-hydroxydopamine (6-OHDA) lesions. Other lesioned rats received injections of cell-free medium and served as controls...... of grafted dopaminergic neurons and to correlate that with the behavioral effects. Additional cultures and acutely prepared explants were also fixed and stored for histological investigation in order to estimate the loss of dopaminergic neurons in culture and after transplantation. Similar behavioral...... improvements in terms of significant reductions in amphetamine-induced rotations were observed in rats grafted with FFRT cultures (127%) and rats grafted with cell suspensions (122%), while control animals showed no normalization of rotational behavior. At 84 days after transplantation, there were similar...

Solvent-free Oxidation of Alcohols and Mild Catalytic Deprotection of ...

African Journals Online (AJOL)

tetrabromobenzene- 1,3-disulphonamide (TBBDA) can be used for solvent-free oxidation of primary and secondary alcohols to the corresponding carbonyl compounds without over-oxidation, and efficient catalytic deprotection of various silyl ...

Grinding solvent-free Paal-Knorr pyrrole synthesis on smectites as ...

African Journals Online (AJOL)

Journal Home > Vol 32, No 1 (2018) > ... An environmentally benign method for the synthesis of N-substituted pyrroles from one-pot solvent-free ... conditions make this protocol practical, environmentally friendly and economically attractive.

Radiation-induced grafting of vinylbenzyl chloride onto a poly(ether ether ketone) film

International Nuclear Information System (INIS)

Hwang, Mi-Lim; Song, Ju-Myung; Ko, Beom-Seok; Sohn, Joon-Yong; Nho, Young-Chang; Shin, Junhwa

2012-01-01

In this study, the effects of various irradiation conditions including solvent, monomer concentration, total dose, and dose rate on the radiation grafting of a VBC monomer onto a PEEK aromatic hydrocarbon film for the preparation of a PVBC-grafted PEEK (PEEK-g-PVBC) film were investigated. The results show that the desired PVBC-grafted PEEK film can be prepared using a simultaneous irradiation grafting method, and that the degree of grafting (DOG) of the film is largely influenced by the irradiation conditions. Among the applied solvents, halogenated solvents, dichloromethane and chloroform, were found to be suitable for grafting. The successful preparation of the grafted film was confirmed using analytical instruments such as FT-IR, TGA, and SEM-EDX.

Thermosensitive polymer-grafted iron oxide nanoparticles studied by in situ dynamic light backscattering under magnetic hyperthermia

Science.gov (United States)

Hemery, Gauvin; Garanger, Elisabeth; Lecommandoux, Sébastien; Wong, Andrew D.; Gillies, Elizabeth R.; Pedrono, Boris; Bayle, Thomas; Jacob, David; Sandre, Olivier

2015-12-01

Thermometry at the nanoscale is an emerging area fostered by intensive research on nanoparticles (NPs) that are capable of converting electromagnetic waves into heat. Recent results suggest that stationary gradients can be maintained between the surface of NPs and the bulk solvent, a phenomenon sometimes referred to as ‘cold hyperthermia’. However, the measurement of such highly localized temperatures is particularly challenging. We describe here a new approach to probing the temperature at the surface of iron oxide NPs and enhancing the understanding of this phenomenon. This approach involves the grafting of thermosensitive polymer chains to the NP surface followed by the measurement of macroscopic properties of the resulting NP suspension and comparison to a calibration curve built up by macroscopic heating. Superparamagnetic iron oxide NPs were prepared by the coprecipitation of ferrous and ferric salts and functionalized with amines, then azides using a sol-gel route followed by a dehydrative coupling reaction. Thermosensitive poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) with an alkyne end-group was synthesized by controlled radical polymerization and was grafted using a copper assisted azide-alkyne cycloaddition reaction. Measurement of the colloidal properties by dynamic light scattering (DLS) indicated that the thermosensitive NPs exhibited changes in their Zeta potential and hydrodynamic diameter as a function of pH and temperature due to the grafted PDMAEMA chains. These changes were accompanied by changes in the relaxivities of the NPs, suggesting application as thermosensitive contrast agents for magnetic resonance imaging (MRI). In addition, a new fibre-based backscattering setup enabled positioning of the DLS remote-head as close as possible to the coil of a magnetic heating inductor to afford in situ probing of the backscattered light intensity, hydrodynamic diameter, and temperature. This approach provides a promising platform for

Innovative polymeric system (IPS) for solvent-free lipophilic drug transdermal delivery via dissolving microneedles.

Science.gov (United States)

Dangol, Manita; Yang, Huisuk; Li, Cheng Guo; Lahiji, Shayan Fakhraei; Kim, Suyong; Ma, Yonghao; Jung, Hyungil

2016-02-10

Lipophilic drugs are potential drug candidates during drug development. However, due to the need for hazardous organic solvents for their solubilization, these drugs often fail to reach the pharmaceutical market, and in doing so highlight the importance of solvent free systems. Although transdermal drug delivery systems (TDDSs) are considered prospective safe drug delivery routes, a system involving lipophilic drugs in solvent free or powder form has not yet been described. Here, we report, for the first time, a novel approach for the delivery of every kind of lipophilic drug in powder form based on an innovative polymeric system (IPS). The phase transition of powder form of lipophilic drugs due to interior chemical bonds between drugs and biodegradable polymers and formation of nano-sized colloidal structures allowed the fabrication of dissolving microneedles (DMNs) to generate a powerful TDDS. We showed that IPS based DMN with powder capsaicin enhances the therapeutic effect for treatment of the rheumatic arthritis in a DBA/1 mouse model compared to a solvent-based system, indicating the promising potential of this new solvent-free platform for lipophilic drug delivery. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis and characterization of thiolated carboxymethyl chitosan-graft-cyclodextrin nanoparticles as a drug delivery vehicle for albendazole.

Science.gov (United States)

Alamdarnejad, Ghazaleh; Sharif, Alireza; Taranejoo, Shahrouz; Janmaleki, Mohsen; Kalaee, Mohammad Reza; Dadgar, Mohsen; Khakpour, Mazyar

2013-08-01

A new strategy for the synthesis of thiolated carboxymethyl chitosan-g-cyclodextrin nanoparticles by an ionic-gelation method is presented. The synthetic approach was based on the utilization of 1,6-hexamethylene diisocyanate during cyclodextrin grafting onto carboxymethyl chitosan. The use of the 1,6-hexamethylene diisocyanate resulted in reactions between cyclodextrin and active sites at the C6-position of chitosan, and preserved amino groups of chitosan for subsequent reactions with thioglycolic acid, as the thiolating agent, and tripolyphosphate, as the gelling counterion. Various methods such as scanning electron microscopy, rheology and in vitro release studies were employed to exhibit significant features of the nanoparticles for mucosal albendazole delivery applications. It was found that the thiolated carboxymethyl chitosan-g-cyclodextrin nanoparticles prepared using an aqueous solution containing 1 wt% of tripolyphosphate and having 115.65 (μmol/g polymer) of grafted thiol groups show both the highest mucoadhesive properties and the highest albendazole entrapment efficiency. The latter was confirmed theoretically by calculating the enthalpy of mixing of albendazole in the above thiolated chitosan polymer.

Formation of unimer nanoparticles by controlling the self-association of hydrophobically modified poly(amino acid)s.

Science.gov (United States)

Akagi, Takami; Piyapakorn, Phassamon; Akashi, Mitsuru

2012-03-20

Amphiphilic block or graft copolymers have been demonstrated to form a variety of self-assembled nano/microstructures in selective solvents. In this study, the self-association behavior of biodegradable graft copolymers composed of poly(γ-glutamic acid) (γ-PGA) as the hydrophilic segment and L-phenylalanine (Phe) as the hydrophobic segment in aqueous solution was investigated. The association behavior and unimer nanoparticle formation of these γ-PGA-graft-Phe (γ-PGA-Phe) copolymers in aqueous solution were characterized with a focus on the effect of the Phe grafting degree on the intra- and interpolymer association of γ-PGA-Phe. The particle size and number of polymer aggregates (N(agg)) in one particle of the γ-PGA-Phe depended on the Phe grafting degree. The size of γ-PGA-Phe with 12, 27, 35, or 42% Phe grafting (γ-PGA-Phe-12, -27, -35, or -42) was about 8-14 nm and the N(agg) was about 1, supporting the presence of a unimolecular graft copolymer in PBS. The pyrene fluorescence data indicated that γ-PGA-Phe-35 and -42 have hydrophobic domains formed by the intrapolymer association of Phe attached to γ-PGA. These results suggest that the Phe grafting degree is critical to the association behavior of γ-PGA-Phe and that γ-PGA-Phe-35 and -42 could form unimer nanoparticles. Moreover, when γ-PGA-Phe-42 dissolved in DMSO was added to various concentrations of NaCl solution, the particle size and N(agg) could be easily controlled by changing the NaCl concentration during the formation of the particles. These results suggest that biodegradable γ-PGA-Phe is useful for the fabrication of very small nanoparticles. It is expected that γ-PGA-Phe nanoparticles, including unimer particles, will have great potential as multifunctional carriers for pharmaceutical and biomedical applications, such as drug and vaccine delivery systems.

Graft copolymers of polypropylene films. 1. radiation induced grafting of mixed monomers. Vol. 3

Energy Technology Data Exchange (ETDEWEB)

El-Salmawi, K M; El-Naggar, A M; Said, H M; Zahran, A H [Radiation Chemistry Department, National Center for Radiation Research and Technology, Atomic Energy Authority, Cairo, (Egypt)

1996-03-01

Radiation graft copolymerization of co monomer mixtures of acrylic acid (AAC), and styrene (S) onto polypropylene (PP) film by mutual method has been investigated. The effects of different factors that may affect the grafting yield such as inhibitor concentration (Mohr`s salt), solvent composition (MeOH and H{sub 2} O), radiation dose and dose rate were considered. It was found that the role of Mohr`s salt is very effective when the ratio of AAC in the co monomer mixtures was at lower values. However, the addition of 1.25 Wt% of Mohr`s salt reduced the homo polymer formation and enhances the grafting process. Graft copolymerization in presence of solvent mixture composed of methanol and water was found to afford higher grafting than in pure methanol regardless of the composition of the co monomer mixture used. However, the highest degree of grafting was obtained at a solvent composition of 20% H{sub 2} O:80%MeOH and a co monomer mixture of 20%AAC:80%sty. An attempt was made to determine each PAAC and PS fractions in the total graft yield obtained. Two methods of analysis based on using the reactivity ratios reported in literature, elemental analysis and IR spectroscopy. The determination of poly (acrylic acid) and polystyrene fractions by elemental analysis is believed more accurate than these by reactivity ratio. The precise results obtained by elemental analysis with respect to the chemical structure of known polymer prepared under identical conditions. The results obtained by IR measurements go well with that obtained with the reactivity ratio methods. 5 figs., 3 tabs.

Small angle neutron scattering study of polyelectrolyte brushes grafted to well-defined gold nanoparticle interfaces.

Science.gov (United States)

Jia, Haidong; Grillo, Isabelle; Titmuss, Simon

2010-05-18

Small angle neutron scattering (SANS) has been used to study the conformations, and response to added salt, of a polyelectrolyte layer grafted to the interfaces of well-defined gold nanoparticles. The polyelectrolyte layer is prepared at a constant coverage by grafting thiol-functionalized polystyrene (M(w) = 53k) to gold nanoparticles of well-defined interfacial curvature (R(c) = 26.5 nm) followed by a soft-sulfonation of 38% of the segments to sodium polystyrene sulfonate (NaPSS). The SANS profiles can be fit by Fermi-Dirac distributions that are consistent with a Gaussian distribution but are better described by a parabolic distribution plus an exponential tail, particularly in the high salt regime. These distributions are consistent with the predictions and measurements for osmotic and salted brushes at interfaces of low curvature. When the concentration of added salt exceeds the concentration of counterions inside the brush, there is a salt-induced deswelling, but even at the highest salt concentration the brush remains significantly swollen due to a short-ranged excluded volume interaction. This is responsible for the observed resistance to aggregation of these comparatively high concentration polyelectrolyte stabilized gold nanoparticle dispersions even in the presence of a high concentration of added salt.

Synthesis and Characterization of Fe3O4 Magnetic Nanoparticles Coated with Carboxymethyl Chitosan Grafted Sodium Methacrylate

Directory of Open Access Journals (Sweden)

S. Asgari

2014-01-01

Full Text Available N-sodium acrylate-O-carboxymethyl chitosan [CMCH-g-PAA(Na] bound Fe3O4 nanoparticles were developed as a novel magnetic nanoparticles with an ionic structure that can be potentially used in many fields. CMCH-g-PAA (Na was obtained by grafting of sodium polyacrylate on O-carboxymethyl chitosan, which is an amphiphilic polyelectrolyte with the biocompatibility and biodegradability properties. According to the great interest for improving the stability of Fe3O4 nanoparticles, CMCH-g-PAA (Na was used as a stabilizer to prepare a well dispersed suspension of magnetic nanoparticle According to the results,the presence of CMCH-g-PAA(Na could eliminate agglomeration of magnetic nanoparticles without destroying the superparamagnetic  properties

Biomechanical Evaluation of Glenoid Reconstruction With an Implant-Free J-Bone Graft for Anterior Glenoid Bone Loss.

Science.gov (United States)

Pauzenberger, Leo; Dyrna, Felix; Obopilwe, Elifho; Heuberer, Philipp R; Arciero, Robert A; Anderl, Werner; Mazzocca, Augustus D

2017-10-01

The anatomic restoration of glenoid morphology with an implant-free J-shaped iliac crest bone graft offers an alternative to currently widely used glenoid reconstruction techniques. No biomechanical data on the J-bone grafting technique are currently available. To evaluate (1) glenohumeral contact patterns, (2) graft fixation under cyclic loading, and (3) the initial stabilizing effect of anatomic glenoid reconstruction with the implant-free J-bone grafting technique. Controlled laboratory study. Eight fresh-frozen cadaveric shoulders and J-shaped iliac crest bone grafts were used for this study. J-bone grafts were harvested, prepared, and implanted according to a previously described, clinically used technique. Glenohumeral contact patterns were measured using dynamic pressure-sensitive sensors under a compressive load of 440 N with the humerus in (a) 30° of abduction, (b) 30° of abduction and 60° of external rotation, (c) 60° of abduction, and (d) 60° of abduction and 60° of external rotation. Using a custom shoulder-testing system allowing positioning with 6 degrees of freedom, a compressive load of 50 N was applied, and the peak force needed to translate the humeral head 10 mm anteriorly at a rate of 2.0 mm/s was recorded. All tests were performed (1) for the intact glenoid, (2) after the creation of a 30% anterior osseous glenoid defect parallel to the longitudinal axis of the glenoid, and (3) after anatomic glenoid reconstruction with an implant-free J-bone graft. Furthermore, after glenoid reconstruction, each specimen was translated anteriorly for 5 mm at a rate of 4.0 mm/s for a total of 3000 cycles while logging graft protrusion and mediolateral bending motions. Graft micromovements were recorded using 2 high-resolution, linear differential variable reluctance transducer strain gauges placed in line with the long leg of the graft and the mediolateral direction, respectively. The creation of a 30% glenoid defect significantly decreased glenohumeral

Method to produce water-soluble sugars from biomass using solvents containing lactones

Science.gov (United States)

Dumesic, James A.; Luterbacher, Jeremy S.

2017-08-08

A process to produce an aqueous solution of carbohydrates that contains C6-sugar-containing oligomers, C6 sugar monomers, C5-sugar-containing oligomers, C5 sugar monomers, or any combination thereof is presented. The process includes the steps of reacting biomass or a biomass-derived reactant with a solvent system including a lactone and water, and an acid catalyst. The reaction yields a product mixture containing water-soluble C6-sugar-containing oligomers, C6-sugar monomers, C5-sugar-containing oligomers, C5-sugar monomers, or any combination thereof. A solute is added to the product mixture to cause partitioning of the product mixture into an aqueous layer containing the carbohydrates and a substantially immiscible organic layer containing the lactone.

High Sensitivity and High Detection Specificity of Gold-Nanoparticle-Grafted Nanostructured Silicon Mass Spectrometry for Glucose Analysis.

Science.gov (United States)

Tsao, Chia-Wen; Yang, Zhi-Jie

2015-10-14

Desorption/ionization on silicon (DIOS) is a high-performance matrix-free mass spectrometry (MS) analysis method that involves using silicon nanostructures as a matrix for MS desorption/ionization. In this study, gold nanoparticles grafted onto a nanostructured silicon (AuNPs-nSi) surface were demonstrated as a DIOS-MS analysis approach with high sensitivity and high detection specificity for glucose detection. A glucose sample deposited on the AuNPs-nSi surface was directly catalyzed to negatively charged gluconic acid molecules on a single AuNPs-nSi chip for MS analysis. The AuNPs-nSi surface was fabricated using two electroless deposition steps and one electroless etching step. The effects of the electroless fabrication parameters on the glucose detection efficiency were evaluated. Practical application of AuNPs-nSi MS glucose analysis in urine samples was also demonstrated in this study.

Microwave-Assisted Solvent-Free Synthesis of Zeolitic Imidazolate Framework-67

Directory of Open Access Journals (Sweden)

Heng Zhang

2016-01-01

Full Text Available A microporous metal-organic framework (MOF, cobalt-based zeolitic imidazolate framework-67 (ZIF-67, was synthesized by the combination of solvent-free hand-mill and microwave irradiation, without any organic solvent and within 30 minutes. The hand-milling process can mix the reactants well by the virtue of high moisture/water absorption capacity of reactants. In addition, the outstanding electromagnetic wave absorption capability of cobalt leads to efficient conversion to MOF structures before carbonization. The obtained ZIF-67 possesses high surface area and micropore volume.

Hydrophobic matrix-free graphene-oxide composites with isotropic and nematic states

Science.gov (United States)

Wåhlander, Martin; Nilsson, Fritjof; Carlmark, Anna; Gedde, Ulf W.; Edmondson, Steve; Malmström, Eva

2016-08-01

We demonstrate a novel route to synthesise hydrophobic matrix-free composites of polymer-grafted graphene oxide (GO) showing isotropic or nematic alignment and shape-memory effects. For the first time, a cationic macroinitiator (MI) has been immobilised on anionic GO and subsequently grafted with hydrophobic polymer grafts. Dense grafts of PBA, PBMA and PMMA with a wide range of average graft lengths (MW: 1-440 kDa) were polymerised by surface-initiated controlled radical precipitation polymerisation from the statistical MI. The surface modification is designed similarly to bimodal graft systems, where the cationic MI generates nanoparticle repulsion, similar to dense short grafts, while the long grafts offer miscibility in non-polar environments and cohesion. The state-of-the-art dispersions of grafted GO were in the isotropic state. Transparent and translucent matrix-free GO-composites could be melt-processed directly using only grafted GO. After processing, birefringence due to nematic alignment of grafted GO was observed as a single giant Maltese cross, 3.4 cm across. Permeability models for composites containing aligned 2D-fillers were developed, which were compared with the experimental oxygen permeability data and found to be consistent with isotropic or nematic states. The storage modulus of the matrix-free GO-composites increased with GO content (50% increase at 0.67 wt%), while the significant increases in the thermal stability (up to 130 °C) and the glass transition temperature (up to 17 °C) were dependent on graft length. The tuneable matrix-free GO-composites with rapid thermo-responsive shape-memory effects are promising candidates for a vast range of applications, especially selective membranes and sensors.We demonstrate a novel route to synthesise hydrophobic matrix-free composites of polymer-grafted graphene oxide (GO) showing isotropic or nematic alignment and shape-memory effects. For the first time, a cationic macroinitiator (MI) has been

Dispersing surface-modified imogolite nanotubes in polar and non-polar solvents

Science.gov (United States)

Li, Ming; Brant, Jonathan A.

2018-02-01

Furthering the development of nanocomposite structures, namely membranes for water treatment applications, requires that methods be developed to ensure nanoparticle dispersion in polar and non-polar solvents, as both are widely used in associated synthesis techniques. Here, we report on a two-step method to graft polyvinylpyrrolidone (PVP), and a one-step method for octadecylphosphonic acid (OPA), onto the outer surfaces of imogolite nanotubes. The goal of these approaches was to improve and maintain nanotube dispersion in polymer compatible polar and non-polar solvents. The PVP coating modified the imogolite surface charge from positive to weakly negative at pH ≤ 9; the OPA made it weakly positive at acidic pH values to negative at pH ≥ 7. The PVP surface coating stabilized the nanotubes through steric hindrance in polar protic, dipolar aprotic, and chloroform. In difference to the PVP, the OPA surface coating allowed the nanotubes to be dispersed in n-hexane and chloroform, but not in the polar solvents. The lack of miscibility in the polar solvents, as well as the better dispersion in n-hexane, was attributed to the stronger hydrophobicity of the OPA polymer relative to the PVP. [Figure not available: see fulltext.

Alveolar Ridge Contouring with Free Connective Tissue Graft at Implant Placement: A 5-Year Consecutive Clinical Study.

Science.gov (United States)

Hanser, Thomas; Khoury, Fouad

2016-01-01

This study evaluated volume stability after alveolar ridge contouring with free connective tissue grafts at implant placement in single-tooth gaps. A total of 52 single-tooth gaps with labial volume deficiencies in the maxilla (incisors, canines, and premolars) were consecutively treated with implants and concomitant free palatal connective tissue grafts in 46 patients between 2006 and 2009. Implants had to be covered with at least 2 mm peri-implant local bone after insertion. At implant placement, a free connective tissue graft from the palate was fixed inside a labial split-thickness flap to form an existing concave buccal alveolar ridge contour due to tissue volume deficiency into a convex shape. Standardized volumetric measurements of the labial alveolar contour using a template were evaluated before connective tissue grafting and at 2 weeks, 1 year, and 5 years after implantprosthetic incorporation. Tissue volume had increased significantly (P tissue contour of the implant before connective tissue grafting to baseline (2 weeks after implant-prosthetic incorporation). Statistically, 50% of the reference points (P > .05) kept their volume from baseline to 1 year after prosthetic incorporation and from baseline to 5 years after prosthetic incorporation, respectively, whereas reference points located within the area of the implant sulcus showed a significant (P connective tissue grafting appears to be an appropriate long-term means to contour preexisting buccal alveolar volume deficiencies in single implants.

Magnetic Nanoparticle Immobilized N-Propylsulfamic Acid as a Recyclable and Efficient Nanocatalyst for the Synthesis of 2H-indazolo[2,1-b]phthalazine-triones in Solvent-Free Conditions: Comparison with Sulfamic Acid

Energy Technology Data Exchange (ETDEWEB)

Rostami, Amin; Tahmasbi, Bahman; Yari, Ako [Univ. of Kurdistan, Sanandaj (Iran, Islamic Republic of)

2013-05-15

N-Propylsulfamic acid supported onto magnetic Fe{sub 3}O{sub 4} nanoparticles (MNPs-PSA) was used as an efficient and magnetically recoverable catalyst for synthesis of 2H-Indazolo[2,1-b]phthalazine-1,6,11(13H)-trione derivatives from the three-component, one-pot condensation reaction of phthalhydrazide, aromatic aldehydes and cyclic 1,3-diones, in good to excellent yields at 100 .deg. C under solvent-free conditions. The catalyst was easily separated with the assistance of an external magnetic field from the reaction mixture and reused for several consecutive runs without significant loss of its catalytic efficiency. In order to compare, the synthesis of 2H-Indazolo[2,1-b]phthalazine-1,6,11(13H)-trione derivatives in the presence of catalytic amount of sulfamic acid (SA) under same reaction condition was also reported.

Videoradiography of free jejunal grafts for rehabilitation of speech in laryngectomized patients

International Nuclear Information System (INIS)

Pokieser, P.; Grasl, M.C.; Schima, W.; Uranitsch, K.; Piza-Katzer, H.; Niederle, B.; Ehrenberger, K.; Ekberg, O.; Tscholakoff, D.

1995-01-01

In laryngectomized patients a tracheo-esophageal artificial fistula can be used to achieve air flow from the trachea to the esophagus during speech. A one-way plastic valve is often used for the fistula. A free jejunal graft between the trachea and the esophagus can also be used. To avoid aspiration the transplant is attached to the submental area giving the graft a siphon-like shape. We performed 23 videoradiographic examinations using high-density barium in 14 such patients. The aim was to evaluate the protective function of these grafts against aspiration. Penetration of the bolus and a small amount of residual contrast material in the ascending limb of the graft was a normal finding. If the standard barium bolus reached the descending limb at any time during the examination, this was a sign of aspiration hazard. To avoid aspiration, the vertex of the speech siphon should be higher than the level of the hypopharyngeal anastomosis. (orig.)

An efficient synthesis of quinolines under solvent-free conditions

Indian Academy of Sciences (India)

Unknown

An efficient synthesis of quinolines under solvent-free conditions. 201 was then irradiated with microwaves in a microwave oven (Samsung model# CE118KF) at 1050W (70% of total power) for 5 minutes (3 + 2 with an inter- mission of 5 minutes). The reaction mixture was cooled at room temperature and rendered basic (pH.

Novel phosphate-grafted ePTFE copolymers for optimum in vitro mineralization

International Nuclear Information System (INIS)

Wentrup-Byrne, Edeline; Suzuki, Shuko; Groendahl, Lisbeth; Suwanasilp, Juthakarn Jessica

2010-01-01

Surface modification via graft copolymerization is an attractive method for optimizing polymers used in biomedical applications. We developed a novel method using a mixed solvent system (either water and dichloromethane (DCM) or water, methanol and DCM) consisting of two solvent phases for grafting 2-(methacryloyloxy)ethyl phosphate onto expanded polytetrafluoroethylene (ePTFE). This new method resulted in the fabrication of grafted membranes with greater grafting extents (GEs) (as evaluated from x-ray photoelectron spectroscopy (XPS)) in the organic phase than those obtained when grafting was carried out in a single phase. It also made it possible to graft in the aqueous phase, a process that is otherwise inhibited by the concomitant formation of large amounts of highly crystalline homopolymer. Thorough characterization of the grafted membranes using gravimetric, XPS and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) not only permitted evaluation of the grafting outcomes but also made it possible to analyze their dependence on monomer concentration and solvent composition. A selection of membranes was tested for their in vitro mineralization capacity using simulated body fluid. It was found that an 'ideal' mineralization outcome, i.e. a uniform coating of carbonated hydroxyapatite (cHAP) formed on the sample grafted in the aqueous phase of the water/DCM two-phase solvent system. A detailed discussion bringing together these results, as well as results from a series of earlier studies, allows conclusions regarding polymer chemistry and the topology necessary for cHAP mineralization.

Photo-triggered solvent-free metamorphosis of polymeric materials.

Science.gov (United States)

Honda, Satoshi; Toyota, Taro

2017-09-11

Liquefaction and solidification of materials are the most fundamental changes observed during thermal phase transitions, yet the design of organic and polymeric soft materials showing isothermal reversible liquid-nonliquid conversion remains challenging. Here, we demonstrate that solvent-free repeatable molecular architectural transformation between liquid-star and nonliquid-network polymers that relies on cleavage and reformation of a covalent bond in hexaarylbiimidazole. Liquid four-armed star-shaped poly(n-butyl acrylate) and poly(dimethyl siloxane) with 2,4,5-triphenylimidazole end groups were first synthesized. Subsequent oxidation of the 2,4,5-triphenylimidazoles into 2,4,5-triphenylimidazoryl radicals and their coupling with these liquid star polymers to form hexaarylbiimidazoles afforded the corresponding nonliquid network polymers. The resulting nonliquid network polymers liquefied upon UV irradiation and produced liquid star-shaped polymers with 2,4,5-triphenylimidazoryl radical end groups that reverted to nonliquid network polymers again by recoupling of the generated 2,4,5-triphenylimidazoryl radicals immediately after terminating UV irradiation.The design of organic and polymeric soft materials showing isothermal reversible liquid-nonliquid conversion is challenging. Here, the authors show solvent-free repeatable molecular architectural transformation between liquid-star and non-liquid-network polymers by the cleavage and reformation of covalent bonds in the polymer chain.

Reducing Postoperative Pterygium Recurrence: Comparison of Free Conjunctival Auto-Graft and Conjunctival Rotation Flap Techniques

International Nuclear Information System (INIS)

Akhter, W.; Tayyab, A.; Kausar, A.; Masrur, A.

2014-01-01

Objective: To compare the recurrence of pterygium between free conjunctival auto-graft and conjunctival rotation flap following simple surgical excision of pterygium. Study Design: Quasi-experimental study. Place and Duration of Study: Shifa Foundation Community Health Clinic, Shifa College of Medicine, Islamabad, from January to November 2012. Methodology: Fifty seven cases aged above 18 years, with a pterygium corneal encroachment of 2 mm which was responsible for visual disability or was cosmetically undesirable were recruited for the study and randomly assigned to conjunctival auto-graft group and conjunctival rotation flap group. Cases with a history of glaucoma or glaucoma suspect, prior pterygium surgery, pterygium with concurrent ocular surface and lid disease, conjunctival inflammation and scarring, pseudo-pterygium or collagen vascular disease were excluded. After simple pterygium excision conjunctival auto-graft group (n=26) cases received a free conjunctival flap was transplanted, while conjunctival rotation flap group (n=31) cases received a conjunctival rotation flap. All cases were followed-up for 6 months after surgery for recurrence and complications. Frequency distribution and significance of association of recurrence using Fisher's exact test and Mann- Whitney U-test was carried out using Statistical Package for Social Sciences (SPSS) version 20. Results: The median (and inter-quartile range) age and surgery duration in conjunctival auto-graft group and conjunctival rotation flap group were 60 (51.50 - 63.00) and 57 (45.00 - 60.00) years, 28.50 (27.00 - 30.50) and 16.00 (15.00 - 17.00) minutes respectively. Recurrence was seen in 2 (7.96%) and 3 (9.76%) cases in auto-graft and rotation flap groups respectively. No significant difference was seen in postoperative complications between the two groups (p=0.60). Conclusion: The surgical time for conjunctival rotation flap procedure is less as compared to free auto-graft, while their recurrence and

Investigation of the charge-transfer in photo-excited nanoparticles for CO2 reduction in non-aqueous media

Directory of Open Access Journals (Sweden)

Dimitrijević Nada M.

2013-01-01

Full Text Available Photoinduced charge separation in TiO2 and Cu2O semiconductor nanoparticles was examined using Electron Paramagnetic Resonance spectroscopy in order to get insight into the photocatalytic reduction of CO2 in nonaqueous media. For dissolution/grafting of CO2 we have used carboxy-PEG4-amine, and as a solvent poly(ethylene glycol 200. We have found that, in this system, reduction of CO2 starts at potential of -0.5 V vs Ag/AgCl, which is significantly more positive than the potential for electrochemical reduction of CO2 in most organic solvents and water (-2.0 V vs. Ag/AgCl. The electron transfer from excited nanoparticles to CO2 is governed both by thermodynamic and kinetic parameters, namely by the redox potential of conduction band electrons and adsorption/binding of CO2 on the surface of nanoparticles.

Silver deposited carboxymethyl chitosan-grafted magnetic nanoparticles as dual action deliverable antimicrobial materials.

Science.gov (United States)

Vo, Duc-Thang; Sabrina, Sabrina; Lee, Cheng-Kang

2017-04-01

Carboxymethyl chitosan (CMCS) was known to have a much better antimicrobial activity than chitosan due to the increased cationic -NH 3 + groups resulted from the intra- and intermolecular interactions between the carboxyl and amino groups. CMCS was grafted onto the surface of silica coated magnetic nanoparticles (MNPs) to obtain magnetically retrievable and deliverable antimicrobial nanoparticles (MNPs@CMCS). The presence of carboxylate groups in CMCS not only enhanced antimicrobial activity but also enabled Ag ions chelating ability to induce the in situ formation of Ag nanoparticles (AgNPs). The deposition of AgNPs on the surface of MNPs@CMCS could significantly increase its antimicrobial activity against planktonic cells due to the dual action of CMCS and AgNPs. Due to its high magnetism, the as-prepared MNPs@CMCS-Ag could be efficiently delivered into an existing biofilm under the guidance of an applied magnetic field. Without direct contact, the Ag ions and/or radical oxygen species (ROS) released from the deposited Ag nanoparticles could effectively kill the bacteria embedded in the extracellular polymeric substances (EPS) matrix of biofilm. Copyright © 2016 Elsevier B.V. All rights reserved.

Free Diced Cartilage: A New Application of Diced Cartilage Grafts in Primary and Secondary Rhinoplasty.

Science.gov (United States)

Kreutzer, Christian; Hoehne, Julius; Gubisch, Wolfgang; Rezaeian, Farid; Haack, Sebastian

2017-09-01

Irregularities or deformities of the nasal dorsum after hump reduction account for a significant number of revision rhinoplasties. The authors therefore developed a technique of meticulously dicing and exactly placing free diced cartilage grafts, harvested from septum, rib, or ear cartilage. The cartilage paste is used for smoothening, augmentation, or camouflaging of the nasal dorsum in primary or revision rhinoplasties. A retrospective analysis of multisurgeon consecutive open approach rhinoplasties from January to December of 2014 was conducted at a single center. The authors compared the outcome of three different techniques to augment or cover the nasal dorsum after an observation period of 7 months. In group I, 325 patients with free diced cartilage grafts as the only onlay were included. In group II, consisting of 73 patients, the dorsal onlay was either fascia alone or in combination with free diced cartilage grafts. Forty-eight patients in group III received a dorsal augmentation with the classic diced cartilage in fascia technique. Four hundred forty-six patients undergoing primary and secondary rhinoplasties in which one of the above-mentioned diced cartilage techniques was used were included in the study. The authors found revision rates for dorsal irregularities within the 7-month postoperative observation period of 5.2, 8.2, and 25 percent for groups I, II, and III, respectively. The authors' findings strongly support their clinical experience that the free diced cartilage graft technique presents an effective and easily reproducible method for camouflage and augmentation in aesthetic and reconstructive rhinoplasty.

Structure of solvent-free grafted nanoparticles: Molecular dynamics and density-functional theory

KAUST Repository

Chremos, Alexandros; Panagiotopoulos, Athanassios Z.; Yu, Hsiu-Yu; Koch, Donald L.

2011-01-01

with decreasing particle volume fraction to fill the interstitial space. At higher temperatures, the simulations reveal effects that differ from the theory and are likely caused by steric repulsions of the expanded corona chains. © 2011 American Institute

Polyethyleneglycol grafting of γ-alumina membranes for solvent resistant nanofiltration

NARCIS (Netherlands)

Tanardi, Cheryl; Catana, Romina; Barboiu, Mihai; Ayral, André; Vankelecom, Ivo F.J.; Nijmeijer, Arian; Winnubst, Aloysius J.A.

2016-01-01

A method is presented for grafting mesoporous g-alumina (pore size 5 nm), supported on an a-alumina ceramic membrane, with polyethylene glycols (PEG). The grafting performance of g-Al2O3 powders with various PEG grafting agents, having different molecular weights, alkoxy groups, and ureido

Oligoquinolines under Solvent-free Microwave Irradiation

Energy Technology Data Exchange (ETDEWEB)

Park, Kwi-Jeon; Kwon, Tae-Woo [Kyungsung University, Busan (Korea, Republic of)

2015-01-15

Quinolines are thermally stable and can be used as an excellent n-type semiconducting materials. Since quinolines are also known to be electron acceptor molecules, combination of various electron donor building blocks can be utilized in photonic and electronic organic light-emitting diode (OLED) applications. For example, donor.acceptor systems with phenothiazine (or carbazole) molecules as electron donors and the phenylquinoline group as an electron acceptor provide an efficient approach for the design of new materials exhibiting highly efficient charge-transfer photophysics and electroluminescence in OLEDs. We have described the Friedlander quinoline synthesis between aminobenzophenones and symmetrical diacetyl compounds having phenothiazine, carbazole, biphenyl, and phenyl moieties under solvent-free microwave irradiation in 12.98% isolated yields.

Solvent-Free Wittig Reaction: A Green Organic Chemistry Laboratory Experiment

Science.gov (United States)

Leung, Sam H.; Angel, Stephen A.

2004-01-01

Some Wittig reactions can be carried out by grinding the reactants in a mortar with a pestle for about 20 minutes, as per investigation. A laboratory experiment involving a solvent-free Wittig reaction that can be completed in a three-hour sophomore organic chemistry laboratory class period, are developed.

PIPERIDINE OLIGOMERS AND COMBINATORIAL LIBRARIES THEREOF

DEFF Research Database (Denmark)

1999-01-01

The present invention relates to piperidine oligomers, methods for the preparation of piperidine oligomers and compound libraries thereof, and the use of piperidine oligomers as drug substances. The present invention also relates to the use of combinatorial libraries of piperidine oligomers...... in libraries (arrays) of compounds especially suitable for screening purposes....

Role of block copolymer adsorption versus bimodal grafting on nanoparticle self-assembly in polymer nanocomposites.

Science.gov (United States)

Zhao, Dan; Di Nicola, Matteo; Khani, Mohammad M; Jestin, Jacques; Benicewicz, Brian C; Kumar, Sanat K

2016-09-14

We compare the self-assembly of silica nanoparticles (NPs) with physically adsorbed polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) copolymers (BCP) against NPs with grafted bimodal (BM) brushes comprised of long, sparsely grafted PS chains and a short dense carpet of P2VP chains. As with grafted NPs, the dispersion state of the BCP NPs can be facilely tuned in PS matrices by varying the PS coverage on the NP surface or by changes in the ratio of the PS graft to matrix chain lengths. Surprisingly, the BCP NPs are remarkably better dispersed than the NPs tethered with bimodal brushes at comparable PS grafting densities. We postulate that this difference arises because of two factors inherent in the synthesis of the NPs: In the case of the BCP NPs the adsorption process is analogous to the chains being "grafted to" the NP surface, while the BM case corresponds to "grafting from" the surface. We have shown that the "grafted from" protocol yields patchy NPs even if the graft points are uniformly placed on each particle. This phenomenon, which is caused by chain conformation fluctuations, is exacerbated by the distribution function associated with the (small) number of grafts per particle. In contrast, in the case of BCP adsorption, each NP is more uniformly coated by a P2VP monolayer driven by the strongly favorable P2VP-silica interactions. Since each P2VP block is connected to a PS chain we conjecture that these adsorbed systems are closer to the limit of spatially uniform sparse brush coverage than the chemically grafted case. We finally show that the better NP dispersion resulting from BCP adsorption leads to larger mechanical reinforcement than those achieved with BM particles. These results emphasize that physical adsorption of BCPs is a simple, effective and practically promising strategy to direct NP dispersion in a chemically unfavorable polymer matrix.

Preparation of Ultra-fine Calcium Carbonate by a Solvent-free ...

African Journals Online (AJOL)

The treatment of calcium chloride with sodium carbonate under solvent-free conditions with a supersonic airflow and at a low heating temperature leads to the synthesis of ultra-fine calcium carbonate. The reaction not only involves mild conditions, a simple operation, and high yields but also gives a high conversion rate.

Sulphamic acid-functionalized magnetic Fe3O4 nanoparticles as ...

Indian Academy of Sciences (India)

as recyclable catalyst for synthesis of imidazoles under microwave irradiation ... functionalized magnetic Fe3O4 nanoparticles (SA–MNPs) as a novel solid acid catalyst under solvent-free classical heating ..... green chemistry approach.

One-pot synthesis of stable colloidal solutions of MFe2O4 nanoparticles using oleylamine as solvent and stabilizer

International Nuclear Information System (INIS)

Pérez-Mirabet, Leonardo; Solano, Eduardo; Martínez-Julián, Fernando; Guzmán, Roger; Arbiol, Jordi; Puig, Teresa; Obradors, Xavier; Pomar, Alberto; Yáñez, Ramón; Ros, Josep; Ricart, Susagna

2013-01-01

Highlights: ► One-pot synthesis of ferrite magnetic nanoparticles ( 3 and M(acac) 2 (M = Co, Mn, Cu and Zn) in oleylamine, which also acts as a capping ligand, by producing stable colloidal dispersions of nanoparticles in non-polar solvents. The properties of the nanoparticles have been studied via different techniques, such as transmission electron microscopy, which shows that nanoparticles are monocrystallines and a narrow dispersion in size; magnetic analyses have demonstrated that the resulting ferrite nanoparticles show high saturation values and superparamagnetic behavior at room temperature; X-ray diffraction has also been performed, and it confirms that the synthesized nanoparticles have a spinel structure. Complementarily, ligand exchange has been also carried out in order to produce dispersions of the synthesized nanoparticles in polar media

Solvent-free porous framework resulted from 3D entanglement of 1D zigzag coordination polymer

KAUST Repository

Kole, Goutam Kumar Umar; Cairns, Amy J.; Eddaoudi, Mohamed; Vittal, Jagadese J.

2010-01-01

A solvent-free porous metal organic framework is constructed by the 3D entanglement of 1D zigzag coordination polymeric chains. The role of solvents and the effect of reaction conditions on such unique entanglement are addressed. © 2010 The Royal

Synthesis and functionalization of magnetite nanoparticles with different amino-functional alkoxysilanes

International Nuclear Information System (INIS)

Bini, Rafael A.; Marques, Rodrigo Fernando C.; Santos, Francisco J.; Chaker, Juliano A.; Jafelicci, Miguel

2012-01-01

Superparamagnetic iron oxide (SPIO) nanoparticles show great promise for many biotechnological applications. This paper addresses the synthesis and characterization of SPIO nanoparticles grafted with three different alkoxysilanes: 3-aminopropyl-triethoxysilane (APTES), 3-aminopropyl-ethyl-diethoxysilane (APDES) and 3-aminopropyl-diethy-ethoxysilane (APES). SPIO nanoparticles with an average particle diameter of 10 nm were prepared by chemical sonoprecipitation. As confirmed by Fourier transform infrared (FTIR) spectroscopy, silylation of these nanoparticles occurs through a two-step process. Decreasing the number of alkoxide groups reduced the concentration of free amino groups on the SPIO surface ([SPIO-NH 2 ]-APTES>APDES>APES). This phenomenon results from steric contributions and the formation of H-bonded amines provided by the ethyl groups present in the APDES and APES molecules. A simulation of SPIO nanoparticles in a saline physiologic solution shows that the ethyl groups impart larger steric stability onto the ferrofluids, which reduces aggregation. The magnetization (M) versus magnetic field (H) curves show that the synthesized iron oxide nanoparticles display superparamagnetic behavior. The zero-field cooling (ZFC) and field cooling (FC) curves show that the changes in the blocking temperature depend on the alkoxysilane-functionalized particle surface. - Highlights: → Superparamagnetic iron oxide nanoparticles were grafted with different alkoxysilanes. → The decrease of alkoxide group number reduced the concentration of free amino group. → We correlate the influence of the amino and ethyl groups with their colloidal property. → Inter-particles aggregation analyzed by magnetic measurement.

Nafion®/ODF-silica composite membranes for medium temperature proton exchange membrane fuel cells

KAUST Repository

Treekamol, Yaowapa; Schieda, Mauricio; Robitaille, Lucie; MacKinnon, Sean M.; Mokrini, Asmae; Shi, Zhiqing; Holdcroft, Steven; Schulte, Karl I.; Nunes, Suzana Pereira

2014-01-01

A series of composite membranes were prepared by dispersing fluorinated polyoxadiazole oligomer (ODF)-functionalized silica nanoparticles in a Nafion matrix. Both melt-extrusion and solvent casting processes were explored. Ion exchange capacity

Solvent-assisted in situ synthesis of cysteamine-capped silver nanoparticles

Science.gov (United States)

Oliva, José M.; Ríos de la Rosa, Julio M.; Sayagués, María J.; Sánchez-Alcázar, José A.; Merkling, Patrick J.; Zaderenko, Ana P.

2018-03-01

Silver nanoparticles offer a huge potential for biomedical applications owing to their exceptional properties and small size. Specifically, cysteamine-capped silver nanoparticles could form the basis for new anticancer therapies combining the cytotoxic effect of the silver core with the inherent antitumor activity of cysteamine, which inhibit cancer cell proliferation and suppress invasion and metastasis. In addition, the capability of the cysteamine coating monolayer to couple a variety of active principles and targeting (bio)molecules of interest proves key to the tailoring of this platform in order to exploit the pathophysiology of specific tumor types. Nevertheless, the chain length and conformational flexibility of cysteamine, together with its ability to attach to the surface of silver nanoparticles via both the thiol and the amine group, have made the in situ synthesis of these particles an especially challenging task. Herein we report a solvent-assisted in situ synthesis method that solves this problem. The obtained nanoparticles have been fully characterized by UV-visible absorption spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscopy, electron diffraction measurement, high resolution transmission electron microscopy, scanning transmission electron microscopy, energy dispersive x-ray spectroscopy nanoanalysis, and dynamic light scattering measurement. Our synthesis method achieves extremely high yield and surface coating ratio, and colloidal stability over a wide range of pH values including physiological pH. Additionally, we have demonstrated that cysteamine-capped nanoparticles obtained by this method can be conjugated to an antibody for active targeting of the epidermal growth factor receptor, which plays an important role in the pathogenesis and progression of a wide variety of tumors, and induce cell death in human squamous carcinoma cells. We believe this method can be readily extended to combinations of noble

Spectroscopic Investigation of the Canopy Configurations in Nanoparticle Organic Hybrid Materials of Various Grafting Densities during CO 2 Capture

KAUST Repository

Petit, Camille; Park, Youngjune; Lin, Kun-Yi Andrew; Park, Ah-Hyung Alissa

2012-01-01

Novel liquid-like nanoparticle organic hybrid materials (NOHMs) made of polyetheramine chains tethered onto functionalized silica nanoparticles were synthesized and characterized before and after exposure to CO 2 using NMR, Raman, and ATR FT-IR spectroscopies in order to investigate the effect of the grafting densities on the NOHM canopy structure. Considering the promising tunable properties for CO 2 capture of NOHMs, this study was conducted to provide important structural information to better design NOHMs for CO 2 capture. In order to minimize the CO 2 absorption via enthalpic effect and provide a more accurate assessment of the structural effects, the NOHMs were synthesized without task-specific groups. A greater chain ordering and decreased intermolecular interactions were observed in NOHMs compared to the unbound polymer. This was attributed to the specific structural arrangement of the frustrated canopy. The distinct configuration of grafted polymer chains caused different CO 2 packing and CO 2-induced swelling behaviors between the NOHMs and the unbound polymer. The grafting density influenced the ordering and coupling of the polymer chains and CO 2-induced swelling. Its effect on the CO 2 packing behavior was less pronounced. © 2011 American Chemical Society.

Spectroscopic Investigation of the Canopy Configurations in Nanoparticle Organic Hybrid Materials of Various Grafting Densities during CO 2 Capture

KAUST Repository

Petit, Camille

2012-01-12

Novel liquid-like nanoparticle organic hybrid materials (NOHMs) made of polyetheramine chains tethered onto functionalized silica nanoparticles were synthesized and characterized before and after exposure to CO 2 using NMR, Raman, and ATR FT-IR spectroscopies in order to investigate the effect of the grafting densities on the NOHM canopy structure. Considering the promising tunable properties for CO 2 capture of NOHMs, this study was conducted to provide important structural information to better design NOHMs for CO 2 capture. In order to minimize the CO 2 absorption via enthalpic effect and provide a more accurate assessment of the structural effects, the NOHMs were synthesized without task-specific groups. A greater chain ordering and decreased intermolecular interactions were observed in NOHMs compared to the unbound polymer. This was attributed to the specific structural arrangement of the frustrated canopy. The distinct configuration of grafted polymer chains caused different CO 2 packing and CO 2-induced swelling behaviors between the NOHMs and the unbound polymer. The grafting density influenced the ordering and coupling of the polymer chains and CO 2-induced swelling. Its effect on the CO 2 packing behavior was less pronounced. © 2011 American Chemical Society.

Grafting poly ethylene glycol chains for antifouling purposes using supercritical CO2

DEFF Research Database (Denmark)

Lokanathan, Arcot R.

2011-01-01

solvent in processes involving PEG grafting for antifouling purposes. Significant chemical efficiency and extremely low surface tension makes scCO2 an apt solvent for Grafting PEG brushes into three dimensional micro or nano porous scaffolds related to tissue engineering. References: 1. Peter Kingshott...

Synthetic oligomer analysis using atmospheric pressure photoionization mass spectrometry at different photon energies.

Science.gov (United States)

Desmazières, Bernard; Legros, Véronique; Giuliani, Alexandre; Buchmann, William

2014-01-15

Atmospheric pressure photoionization (APPI) followed by mass spectrometric detection was used to ionize a variety of polymers: polyethylene glycol, polymethyl methacrylate, polystyrene, and polysiloxane. In most cases, whatever the polymer or the solvent used (dichloromethane, tetrahydrofuran, hexane, acetone or toluene), only negative ion mode produced intact ions such as chlorinated adducts, with no or few fragmentations, in contrast to the positive ion mode that frequently led to important in-source fragmentations. In addition, it was shown that optimal detection of polymer distributions require a fine tuning of other source parameters such as temperature and ion transfer voltage. Series of mass spectra were recorded in the negative mode, in various solvents (dichloromethane, tetrahydrofuran, hexane, toluene, and acetone), by varying the photon energy from 8eV up to 10.6eV using synchrotron radiation. To these solvents, addition of a classical APPI dopant (toluene or acetone) was not necessary. Courtesy of the synchrotron radiation, it was demonstrated that the photon energy required for an efficient ionization of the polymer was correlated to the ionization energy of the solvent. As commercial APPI sources typically use krypton lamps with energy fixed at 10eV and 10.6eV, the study of the ionization of polymers over a wavelength range allowed to confirm and refine the previously proposed ionization mechanisms. Moreover, the APPI source can efficiently be used as an interface between size exclusion chromatography or reverse phase liquid chromatography and MS for the study of synthetic oligomers. However, the photoionization at fixed wavelength of polymer standards with different molecular weights showed that it was difficult to obtain intact ionized oligomers with molecular weights above a few thousands. Copyright © 2013 Elsevier B.V. All rights reserved.

Synthesis and characterization of poly[N-isopropylacrylamide-co-1-(N,N-bis-carboxymethyl)amino-3-allylglycerol] grafted to magnetic nano-particles for the extraction and determination of fluvoxamine in biological and pharmaceutical samples.

Science.gov (United States)

Panahi, Homayon Ahmad; Tavanaei, Yasamin; Moniri, Elham; Keshmirizadeh, Elham

2014-06-06

In this research, a novel method is reported for the surface grafting of N-isopropylacrylamide as a thermosensitive agent and 1-(N,N-bis-carboxymethyl)amino-3-allylglycerol with an affinity toward fluvoxamine onto magnetic nano-particles modified by 3-mercaptopropyltrimethoxysilane. The grafted nano-particles were characterized by Fourier transform infrared spectroscopy, elemental analysis, and thermogravimetric analysis. The surface morphology was studied with scanning electron microscopy and transmission electron microscopy. The resulting grafted nano-particles were used in solid phase extraction and determining of trace fluvoxamine in biological human fluids and pharmaceutical samples. The profile of the fluvoxamine uptake by the modified magnetic nano-particles indicated good accessibility of the active sites in the grafted copolymer. It was found that the adsorption behavior could be fitted by the Freundlich adsorption isotherm model. It was observed that a maximum amount of fluvoxamine was released at a temperature above the lower critical solution temperature of the polymer. Copyright © 2014 Elsevier B.V. All rights reserved.

Backbone conformation affects duplex initiation and duplex propagation in hybridisation of synthetic H-bonding oligomers.

Science.gov (United States)

Iadevaia, Giulia; Núñez-Villanueva, Diego; Stross, Alexander E; Hunter, Christopher A

2018-06-06

Synthetic oligomers equipped with complementary H-bond donor and acceptor side chains form multiply H-bonded duplexes in organic solvents. Comparison of the duplex forming properties of four families of oligomers with different backbones shows that formation of an extended duplex with three or four inter-strand H-bonds is more challenging than formation of complexes that make only two H-bonds. The stabilities of 1 : 1 complexes formed between length complementary homo-oligomers equipped with either phosphine oxide or phenol recognition modules were measured in toluene. When the backbone is very flexible (pentane-1,5-diyl thioether), the stability increases uniformly by an order of magnitude for each additional base-pair added to the duplex: the effective molarities for formation of the first intramolecular H-bond (duplex initiation) and subsequent intramolecular H-bonds (duplex propagation) are similar. This flexible system is compared with three more rigid backbones that are isomeric combinations of an aromatic ring and methylene groups. One of the rigid systems behaves in exactly the same way as the flexible backbone, but the other two do not. For these systems, the effective molarity for formation of the first intramolecular H-bond is the same as that found for the other two backbones, but additional H-bonds are not formed between the longer oligomers. The effective molarities are too low for duplex propagation in these systems, because the oligomer backbones cannot adopt conformations compatible with formation of an extended duplex.

Durable and Washable Antibacterial Copper Nanoparticles Bridged by Surface Grafting Polymer Brushes on Cotton and Polymeric Materials

Directory of Open Access Journals (Sweden)

Chufeng Sun

2018-01-01

Full Text Available To increase the durability of antibacterial coating on cotton and polymeric substrates, surface initiated grafting polymer brushes are introduced onto the substrates surface to bridge copper nanoparticles coatings and substrate. The morphologies of the composites consisting of the copper nanoparticles and polymer brushes were characterized with scanning electron microscopy (SEM. It was found that copper nanoparticles were uniformly and firmly distributed on the surfaces of the substrates by the polymer brushes; meanwhile, the reinforced concrete-like structures were formed in the composite materials. The substrates coated by the copper nanoparticles showed the efficient antibacterial activity against Staphylococcus aureus (S. aureus and Escherichia coli (E. coli even after washing by 30 cycles. The copper nanoparticles were tethered on the substrates by the strong chemical bonds, which led to the excellent washable fitness and durability. The change of the phase structure of the copper was analyzed to investigate the release mechanism of copper ions.

Pre-irradiation induced emulsion graft polymerization of acrylonitrile onto polyethylene nonwoven fabric

International Nuclear Information System (INIS)

Liu Hanzhou; Yu Ming; Deng Bo; Li Linfan; Jiang Haiqing; Li Jingye

2012-01-01

Acrylonitrile has been widely used in the modification of polymers by graft polymerization. In the present work, pre-irradiation induced emulsion graft polymerization method is used to introduce acrylonitrile onto PE nonwoven fabric instead of the traditional reaction in organic solvents system. The degree of grafting (DG) is measured by gravimetric method and the kinetics of the graft polymerization is studied. The existence of the graft chains is proven by Fourier transform infrared spectroscopy (FT-IR) analysis. Thermal stability of the grafted polymer is measured by Thermogravimetric analysis (TGA). - Highlights: → Acrylonitrile is grafted onto pre-irradiated polyethylene (PE) nonwoven fabrics. → Emulsion system is applied, for the graft polymerization avoids organic solvent. → Kinetic of the pre-irradiation induced graft polymerization is studied. → Optimal condition is determined at the temperature below the b.p. of acrylonitrile.

The Role of Solvent Polarity on Low-Temperature Methanol Synthesis Catalyzed by Cu Nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Ahoba-Sam, Christian [Department of Process, Energy and Environmental Technology, University College of Southeast Norway, Porsgrunn (Norway); Olsbye, Unni [Department of Chemistry, University of Oslo, Oslo (Norway); Jens, Klaus-Joachim, E-mail: Klaus.J.Jens@usn.no [Department of Process, Energy and Environmental Technology, University College of Southeast Norway, Porsgrunn (Norway)

2017-07-14

Methanol syntheses at low temperature in a liquid medium present an opportunity for full syngas conversion per pass. The aim of this work was to study the role of solvents polarity on low-temperature methanol synthesis reaction using eight different aprotic polar solvents. A “once through” catalytic system, which is composed of Cu nanoparticles and sodium methoxide, was used for methanol synthesis at 100°C and 20 bar syngas pressure. Solvent polarity rather than the 7–10 nm Cu (and 30 nm Cu on SiO{sub 2}) catalyst used dictated trend of syngas conversion. Diglyme with a dielectric constant (ε) = 7.2 gave the highest syngas conversion among the eight different solvents used. Methanol formation decreased with either increasing or decreasing solvent ε value of diglyme (ε = 7.2). To probe the observed trend, possible side reactions of methyl formate (MF), the main intermediate in the process, were studied. MF was observed to undergo two main reactions; (i) decarbonylation to form CO and MeOH and (ii) a nucleophilic substitution to form dimethyl ether and sodium formate. Decreasing polarity favored the decarbonylation side reaction while increasing polarity favored the nucleophilic substitution reaction. In conclusion, our results show that moderate polarity solvents, e.g., diglyme, favor MF hydrogenolysis and, hence, methanol formation, by retarding the other two possible side reactions.

Polypropylene fibers modified by plasma treatment for preparation of Ag nanoparticles.

Science.gov (United States)

Tseng, Chun-Hao; Wang, Cheng-Chien; Chen, Chuh-Yung

2006-03-09

A novel method for preparing poly(propylene-graft-2-methacrylic acid 3-(bis-carboxymethylamino)-2-hydroxy-propyl ester)-silver fibers (PPG-IAg fibers) by plasma-induced grafting polymerization is presented in this study. The chelating groups, -N(CH2COO-)2 (GMA-IDA), on the surface of the PPG-I fibers are the coordination sites for chelating silver ions. At these sites, Ag nanoparticles were grown first by reduction with UV light with a wavelength of 366 nm, and second, through immersion in a 24% formaldehyde solution with pH values set variously at 2, 5, 8, and 11. The characteristics of the PPG-I fibers with differing durations of plasma treatment were monitored by using a Fourier transform infrared (FT-IR) spectroscope. Scanning electronic microscopy (SEM) and elemental analysis show that the percentage of GMA-IDA grafted onto PP fiber reaches a maximum when the plasma treatment time is 3 min. Plasma treatment time beyond a certain length of time results in an abundance of free radicals and causes considerable cross-linking on the fiber surface which thus decreases the extent of grafting. Moreover, the crystalline phase of Ag nanoparticles is identified by using X-ray diffraction (XRD). When the PPG-I fibers are reduced by the UV light method, SEM and TEM microscopes reveal that the size of the Ag nanoparticles on the fiber surface decreases significantly with the increase of pH values in aqueous solutions. Notably, in the reduction of formaldehyde solution, the particle size of Ag nanoparticles reaches a minimum at the lowest pH value. The TEM observations show that Ag nanoparticles are distributed both in the exterior and interior of the grafting layer. In addition, under high pH values the distribution of the Ag nanoparticles permeate more deeply in the GMA-IDA grafting layer due to the swelling effect of the GMA-IDA polymer.

Reconstruction of the Upper Eyelid with Flaps and Free Grafts after Excision of Basal Cell Carcinoma

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Alessandro Guido Actis

2011-11-01

Full Text Available Purpose: To describe a reconstructive technique of the superior eyelid with flaps and free grafts after excision of a basal cell carcinoma. Methods: Single case report of a 79-year-old woman who presented to our hospital with a basal cell carcinoma of the upper eyelid margin with initial erosion. Results: A large and full-thickness excision of the carcinoma was performed. The reconstruction technique should be customized to the individual patient. In this case, the use of a full-thickness tarsal graft from the contralateral upper eyelid, followed by an ipsilateral bipedicled flap and finally by a skin graft, was an effective surgical procedure, performed in one stage, without complications, and with good functional and esthetic results. Conclusions: Malignant neoplasms represent the leading cause of plastic reconstruction in the orbital region. Surgical techniques must be individualized for each patient and for each type of carcinoma. Reconstructive techniques with free grafts and flaps yield excellent results in the orbital region, particularly when some advice and a few fundamental rules are followed, namely accurate hemostasis of the receiving graft bed by moderate use of diathermy, careful suturing of the edges, and application of a compressive dressing for at least 4 days. Postoperative complications are very rare.

Murine pluripotent stem cells derived scaffold-free cartilage grafts from a micro-cavitary hydrogel platform.

Science.gov (United States)

He, Pengfei; Fu, Jiayin; Wang, Dong-An

2016-04-15

By means of appropriate cell type and scaffold, tissue-engineering approaches aim to construct grafts for cartilage repair. Pluripotent stem cells especially induced pluripotent stem cells (iPSCs) are of promising cell candidates due to the pluripotent plasticity and abundant cell source. We explored three dimensional (3D) culture and chondrogenesis of murine iPSCs (miPSCs) on an alginate-based micro-cavity hydrogel (MCG) platform in pursuit of fabricating synthetic-scaffold-free cartilage grafts. Murine embryonic stem cells (mESCs) were employed in parallel as the control. Chondrogenesis was fulfilled using a consecutive protocol via mesoderm differentiation followed by chondrogenic differentiation; subsequently, miPSC and mESC-seeded constructs were further respectively cultured in chondrocyte culture (CC) medium. Alginate phase in the constructs was then removed to generate a graft only comprised of induced chondrocytic cells and cartilaginous extracellular matrix (ECMs). We found that from the mESC-seeded constructs, formation of intact grafts could be achieved in greater sizes with relatively fewer chondrocytic cells and abundant ECMs; from miPSC-seeded constructs, relatively smaller sized cartilaginous grafts could be formed by cells with chondrocytic phenotype wrapped by abundant and better assembled collagen type II. This study demonstrated successful creation of pluripotent stem cells-derived cartilage/chondroid graft from a 3D MCG interim platform. By the support of materials and methodologies established from this study, particularly given the autologous availability of iPSCs, engineered autologous cartilage engraftment may be potentially fulfilled without relying on the limited and invasive autologous chondrocytes acquisition. In this study, we explored chondrogenic differentiation of pluripotent stem cells on a 3D micro-cavitary hydrogel interim platform and creation of pluripotent stem cells-derived cartilage/chondroid graft via a consecutive

Microwave-assisted clean synthesis of amides via aza-wittig reaction under solvent-free condition

Energy Technology Data Exchange (ETDEWEB)

Sathishkumar, Murugan; Nagarajan, Sangaraiah; Velan, Poovan Shanmuga; Dinesh, Murugan; Ponnuswamy, Alagusundaram [Department of Organic Chemistry, School of Chemistry, Madurai Kamaraj University, Tamilnadu (India)

2011-09-15

A solvent-free microwave-assisted coupling of phosphazenes with acyl chlorides or carboxylic anhydrides in presence of triethylphosphite has been accomplished resulting in a clean synthesis of amides in good yields. Unlike the prevailing time-consuming solution phase methodologies employing chlorinated solvents, benzene (carcinogenic), etc, the present protocol is an eco friendly, rapid and simple approach. (author)

Solvent-Free Synthesis of Quaternary Metal Sulfide Nanoparticles Derived from Thiourea

KAUST Repository

Bhunia, Manas Kumar

2017-08-09

The synthesis of metal sulfide (MS) materials with sizes in the sub-10 nm regime often requires capping agents with long hydrocarbon chains that affect their structures and properties. Herein, this study presents a molten-state synthesis method for a series of transition-MS nanoparticles using thiourea as a reactive precursor without capping agents. This study also reports the synthesis of MS with single metals (Fe, Co, Ni, Cu, and Zn) and quaternary CuGa2In3S8 using the same synthesis protocol. Thiourea first melts to form a molten-state condition to serve as the reaction medium at a relatively low temperature (<200 °C), followed by its thermal decomposition to induce a reaction with the metal precursor to form different MS. This synthesis protocol, owing to its dynamic characteristics, involves the formation of a variety of organic carbon nitride polymeric complexes around the MS particles. Dynamic nuclear polarization surface-enhanced nuclear magnetic resonance spectroscopy is effective to identify the polymeric compositions and structures as well as their interactions with the MS. These results provided thorough structural descriptions of the MS nanoparticles surrounded by the carbon nitride species derived from thiourea, which may find various applications, including photocatalytic water splitting.

Multicomponent One-Pot Synthesis of Substituted Hantzsch Thiazole Derivatives Under Solvent Free Conditions

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Bhaskar S. Dawane

2009-01-01

Full Text Available Thiazole derivatives were prepared by one-pot procedure by the reaction of α-haloketones, thiourea and substituted o-hydroxybenzaldehyde under environmentally solvent free conditions.

studies on solvent extraction of free hydrogen cyanide from river water

African Journals Online (AJOL)

A method for free and strongly complexed cyanide measurement in river water was developed. Recovery tests from solution with and without river water, using various solvent combinations and background control were investigated to obtain an accurate and precise extraction method for the measurement of hydrogen ...

Preparation of poly(vinyl alcohol) membranes grafted with N-vinyl imidazole/acrylic acid binary monomers

International Nuclear Information System (INIS)

Ajji, Zaki; Ali, Ali

2006-01-01

Poly(vinyl alcohol) films were grafted with two monomers using gamma radiation, acrylic acid and N-vinyl imidazole. The influence of different parameters on the grafting yield was investigated as: type of solvent and solvent composition, comonomer concentration and composition, addition of mineral acids, and irradiation dose. Water uptake in respect to the grafting yield was also evaluated. The ability of the grafted films to adsorb copper ions was elaborated and discussed for different grafting yields and ph values of the solution. (authors)

Use of Chitosan-PVA Hydrogels with Copper Nanoparticles to Improve the Growth of Grafted Watermelon.

Science.gov (United States)

González Gómez, Homero; Ramírez Godina, Francisca; Ortega Ortiz, Hortensia; Benavides Mendoza, Adalberto; Robledo Torres, Valentín; Cabrera De la Fuente, Marcelino

2017-06-22

Modern agriculture requires alternative practices that improve crop growth without negatively affecting the environment, as resources such as water and arable land grow scarcer while the human population continues to increase. Grafting is a cultivation technique that allows the plant to be more efficient in its utilization of water and nutrients, while nanoscale material engineering provides the opportunity to use much smaller quantities of consumables compared to conventional systems but with similar or superior effects. On those grounds, we evaluated the effects of chitosan-polyvinyl alcohol hydrogel with absorbed copper nanoparticles (Cs-PVA-nCu) on leaf morphology and plant growth when applied to grafted watermelon cultivar 'Jubilee' plants. Stomatal density (SD), stomatal index (SI), stoma length (SL), and width (SW) were evaluated. The primary stem and root length, the stem diameter, specific leaf area, and fresh and dry weights were also recorded. Our results demonstrate that grafting induces modifications to leaf micromorphology that favorably affect plant growth, with grafted plants showing better vegetative growth in spite of their lower SD and SI values. Application of Cs-PVA-nCu was found to increase stoma width, primary stem length, and root length by 7%, 8% and 14%, respectively. These techniques modestly improve plant development and growth.

Use of Chitosan-PVA Hydrogels with Copper Nanoparticles to Improve the Growth of Grafted Watermelon

Directory of Open Access Journals (Sweden)

Homero González Gómez

2017-06-01

Full Text Available Modern agriculture requires alternative practices that improve crop growth without negatively affecting the environment, as resources such as water and arable land grow scarcer while the human population continues to increase. Grafting is a cultivation technique that allows the plant to be more efficient in its utilization of water and nutrients, while nanoscale material engineering provides the opportunity to use much smaller quantities of consumables compared to conventional systems but with similar or superior effects. On those grounds, we evaluated the effects of chitosan-polyvinyl alcohol hydrogel with absorbed copper nanoparticles (Cs-PVA-nCu on leaf morphology and plant growth when applied to grafted watermelon cultivar ‘Jubilee’ plants. Stomatal density (SD, stomatal index (SI, stoma length (SL, and width (SW were evaluated. The primary stem and root length, the stem diameter, specific leaf area, and fresh and dry weights were also recorded. Our results demonstrate that grafting induces modifications to leaf micromorphology that favorably affect plant growth, with grafted plants showing better vegetative growth in spite of their lower SD and SI values. Application of Cs-PVA-nCu was found to increase stoma width, primary stem length, and root length by 7%, 8% and 14%, respectively. These techniques modestly improve plant development and growth.

DNA base pair resolution measurements using resonance energy transfer efficiency in lanthanide doped nanoparticles.

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Aleksandra Delplanque

Full Text Available Lanthanide-doped nanoparticles are of considerable interest for biodetection and bioimaging techniques thanks to their unique chemical and optical properties. As a sensitive luminescence material, they can be used as (bio probes in Förster Resonance Energy Transfer (FRET where trivalent lanthanide ions (La3+ act as energy donors. In this paper we present an efficient method to transfer ultrasmall (ca. 8 nm NaYF4 nanoparticles dispersed in organic solvent to an aqueous solution via oxidation of the oleic acid ligand. Nanoparticles were then functionalized with single strand DNA oligomers (ssDNA by inducing covalent bonds between surface carboxylic groups and a 5' amine modified-ssDNA. Hybridization with the 5' fluorophore (Cy5 modified complementary ssDNA strand demonstrated the specificity of binding and allowed the fine control over the distance between Eu3+ ions doped nanoparticle and the fluorophore by varying the number of the dsDNA base pairs. First, our results confirmed nonradiative resonance energy transfer and demonstrate the dependence of its efficiency on the distance between the donor (Eu3+ and the acceptor (Cy5 with sensitivity at a nanometre scale.

DNA base pair resolution measurements using resonance energy transfer efficiency in lanthanide doped nanoparticles.

Science.gov (United States)

Delplanque, Aleksandra; Wawrzynczyk, Dominika; Jaworski, Pawel; Matczyszyn, Katarzyna; Pawlik, Krzysztof; Buckle, Malcolm; Nyk, Marcin; Nogues, Claude; Samoc, Marek

2015-01-01

Lanthanide-doped nanoparticles are of considerable interest for biodetection and bioimaging techniques thanks to their unique chemical and optical properties. As a sensitive luminescence material, they can be used as (bio) probes in Förster Resonance Energy Transfer (FRET) where trivalent lanthanide ions (La3+) act as energy donors. In this paper we present an efficient method to transfer ultrasmall (ca. 8 nm) NaYF4 nanoparticles dispersed in organic solvent to an aqueous solution via oxidation of the oleic acid ligand. Nanoparticles were then functionalized with single strand DNA oligomers (ssDNA) by inducing covalent bonds between surface carboxylic groups and a 5' amine modified-ssDNA. Hybridization with the 5' fluorophore (Cy5) modified complementary ssDNA strand demonstrated the specificity of binding and allowed the fine control over the distance between Eu3+ ions doped nanoparticle and the fluorophore by varying the number of the dsDNA base pairs. First, our results confirmed nonradiative resonance energy transfer and demonstrate the dependence of its efficiency on the distance between the donor (Eu3+) and the acceptor (Cy5) with sensitivity at a nanometre scale.

In situ ultra-small-angle X-ray scattering study under uniaxial stretching of colloidal crystals prepared by silica nanoparticles bearing hydrogen-bonding polymer grafts

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Ryohei Ishige

2016-05-01

Full Text Available A molded film of single-component polymer-grafted nanoparticles (SPNP, consisting of a spherical silica core and densely grafted polymer chains bearing hydrogen-bonding side groups capable of physical crosslinking, was investigated by in situ ultra-small-angle X-ray scattering (USAXS measurement during a uniaxial stretching process. Static USAXS revealed that the molded SPNP formed a highly oriented twinned face-centered cubic (f.c.c. lattice structure with the [11−1] plane aligned nearly parallel to the film surface in the initial state. Structural analysis of in situ USAXS using a model of uniaxial deformation induced by rearrangement of the nanoparticles revealed that the f.c.c. lattice was distorted in the stretching direction in proportion to the macroscopic strain until the strain reached 35%, and subsequently changed into other f.c.c. lattices with different orientations. The lattice distortion and structural transition behavior corresponded well to the elastic and plastic deformation regimes, respectively, observed in the stress–strain curve. The attractive interaction of the hydrogen bond is considered to form only at the top surface of the shell and then plays an effective role in cross-linking between nanoparticles. The rearrangement mechanism of the nanoparticles is well accounted for by a strong repulsive interaction between the densely grafted polymer shells of neighboring particles.

On the addition of conducting ceramic nanoparticles in solvent-free ionic liquid electrolyte for dye-sensitized solar cells

KAUST Repository

Lee, Chuan-Pei

2009-08-01

Titanium carbide (TiC) is an extremely hard conducting ceramic material often used as a coating for titanium alloys as well as steel and aluminum components to improve their surface properties. In this study, conducting ceramic nanoparticles (CCNPs) have been used, for the first time, in dye-sensitized solar cells (DSSCs), and the incorporation of TiC nanoparticles in a binary ionic liquid electrolyte on the cell performance has been investigated. Cell conversion efficiency with 0.6 wt% TiC reached 1.68%, which was higher than that without adding TiC (1.18%); however, cell efficiency decreased when the TiC content reached 1.0 wt%. The electrochemical impedance spectroscopy (EIS) technique was employed to analyze the interfacial resistance in DSSCs, and it was found that the resistance of the charge-transfer process at the Pt counter electrode (Rct1) decreased when up to 1.0 wt% TiC was added. Presumably, this was due to the formation of the extended electron transfer surface (EETS) which facilitates electron transfer to the bulk electrolyte, resulting in a decrease of the dark current, whereby the open-circuit potential (VOC) could be improved. Furthermore, a significant increase in the fill factor (FF) for all TiC additions was related to the decrease in the series resistance (RS) of the DSSCs. However, at 1.0 wt% TiC, the largest charge-transfer resistance at the TiO2/dye/electrolyte interface was observed and resulted from the poor penetration of the electrolyte into the porous TiO2. The long-term stability of DSSCs with a binary ionic liquid electrolyte, which is superior to that of an organic solvent-based electrolyte, was also studied. © 2009 Elsevier B.V. All rights reserved.

The Effect of Solvents, Acetone, Water, and Ethanol, on the Morphological and Optical Properties of ZnO Nanoparticles Prepared by Microwave

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Phindile B. Khoza

2012-01-01

Full Text Available HDA-capped ZnO nanoparticles were prepared by solvothermal method using solvents of different polarities. A number of parameters were kept constant such as temperature, pressure, time, and pH while solvents were varied, that is, water, ethanol, and acetone. The TEM was used for the structural properties and morphologies such as spheres, mixture of rods, and spheres and stars were obtained in ethanol, acetone, and water, respectively, in a given reaction time of 15 minutes. Both ethanol and acetone gave rods with high aspect ratio primarily because of the lengths of the rods. Water and ethanol have the hydroxyl groups which interact with nanoparticles from nucleation, growth, and termination giving rise to nonspherical shapes. The hydroxyl group promotes growth in a nonuniform way resulting in stars and rods. The optical features were typical of ZnO nanoparticles with excitonic peaks in the range 368 to 374 nm from their absorption spectra. The XRD patterns of the particles gave the most stable form of ZnO which is the hexagonal phase, with high degree of crystallinity and with the 101 plane predominant in all solvents.

Ester-free Thiol-X Resins: New Materials with Enhanced Mechanical Behavior and Solvent Resistance.

Science.gov (United States)

Podgórski, Maciej; Becka, Eftalda; Chatani, Shunsuke; Claudino, Mauro; Bowman, Christopher N

A series of thiol-Michael and radical thiol-ene network polymers were successfully prepared from ester-free as well as ester-containing monomer formulations. Polymerization reaction rates, dynamic mechanical analysis, and solvent resistance experiments were performed and compared between compositions with varied ester loading. The incorporation of ester-free alkyl thiol, vinyl sulfone and allylic monomers significantly improved the mechanical properties when compared with commercial, mercaptopropionate-based thiol-ene or thiol-Michael networks. For polymers with no hydrolytically degradable esters, glass transition temperatures (T g 's) as high as 100 °C were achieved. Importantly, solvent resistance tests demonstrated enhanced stability of ester-free formulations over PETMP-based polymers, especially in concentrated basic solutions. Kinetic analysis showed that glassy step-growth polymers are readily formed at ambient conditions with conversions reaching 80% and higher.

Amyloid oligomer structure characterization from simulations: A general method

Energy Technology Data Exchange (ETDEWEB)

Nguyen, Phuong H., E-mail: phuong.nguyen@ibpc.fr [Laboratoire de Biochimie Théorique, UPR 9080, CNRS Université Denis Diderot, Sorbonne Paris Cité IBPC, 13 rue Pierre et Marie Curie, 75005 Paris (France); Li, Mai Suan [Institute of Physics, Polish Academy of Sciences, Al. Lotnikow 32/46, 02-668 Warsaw (Poland); Derreumaux, Philippe, E-mail: philippe.derreumaux@ibpc.fr [Laboratoire de Biochimie Théorique, UPR 9080, CNRS Université Denis Diderot, Sorbonne Paris Cité IBPC, 13 rue Pierre et Marie Curie, 75005 Paris (France); Institut Universitaire de France, 103 Bvd Saint-Germain, 75005 Paris (France)

2014-03-07

Amyloid oligomers and plaques are composed of multiple chemically identical proteins. Therefore, one of the first fundamental problems in the characterization of structures from simulations is the treatment of the degeneracy, i.e., the permutation of the molecules. Second, the intramolecular and intermolecular degrees of freedom of the various molecules must be taken into account. Currently, the well-known dihedral principal component analysis method only considers the intramolecular degrees of freedom, and other methods employing collective variables can only describe intermolecular degrees of freedom at the global level. With this in mind, we propose a general method that identifies all the structures accurately. The basis idea is that the intramolecular and intermolecular states are described in terms of combinations of single-molecule and double-molecule states, respectively, and the overall structures of oligomers are the product basis of the intramolecular and intermolecular states. This way, the degeneracy is automatically avoided. The method is illustrated on the conformational ensemble of the tetramer of the Alzheimer's peptide Aβ{sub 9−40}, resulting from two atomistic molecular dynamics simulations in explicit solvent, each of 200 ns, starting from two distinct structures.

Nano crystalline ZnO catalyzed one pot three-component synthesis of 7-alkyl-6H,7H- naphtho[1',2':5,6]pyrano[3,2-c] chromen-6-ones under solvent-free conditions

Directory of Open Access Journals (Sweden)

M. J. Piltan

2016-08-01

Full Text Available In the present paper, an efficient one-pot synthesis of 7-alkyl-6H,7H-naphtho[1',2':5,6]pyrano[3,2-c]chromen-6-ones is described by three-component reaction of β-naphthol, aromatic aldehydes and 4-hydroxycoumarin using ZnO nanoparticles under solvent-free conditions. The present method provides a novel and efficient procedure for the synthesis of chromene derivatives with some advantageous such as short reaction times, easy workup, high yields, wide range of products, reusability of the catalyst, little catalyst loading and green conditions in the presence of ZnO nanoparticles (7 mol% at 110 ºC.

A facile metal-free "grafting-from" route from acrylamide-based substrate toward complex macromolecular combs

KAUST Repository

Zhao, Junpeng

2013-01-01

High-molecular-weight poly(N,N-dimethylacrylamide-co-acrylamide) was used as a model functional substrate to investigate phosphazene base (t-BuP 4)-promoted metal-free anionic graft polymerization utilizing primary amide moieties as initiating sites. The (co)polymerization of epoxides was proven to be effective, leading to macromolecular combs with side chains being single- or double-graft homopolymer, block copolymer and statistical copolymer. © 2013 The Royal Society of Chemistry.

Enzymatic functionalization of cork surface with antimicrobial hybrid biopolymer/silver nanoparticles.

Science.gov (United States)

Francesko, Antonio; Blandón, Lucas; Vázquez, Mario; Petkova, Petya; Morató, Jordi; Pfeifer, Annett; Heinze, Thomas; Mendoza, Ernest; Tzanov, Tzanko

2015-05-13

Laccase-assisted assembling of hybrid biopolymer-silver nanoparticles and cork matrices into an antimicrobial material with potential for water remediation is herein described. Amino-functional biopolymers were first used as doping agents to stabilize concentrated colloidal dispersions of silver nanoparticles (AgNP), additionally providing the particles with functionalities for covalent immobilization onto cork to impart a durable antibacterial effect. The solvent-free AgNP synthesis by chemical reduction was carried out in the presence of chitosan (CS) or 6-deoxy-6-(ω-aminoethyl) aminocellulose (AC), leading to simultaneous AgNP biofunctionalization. This approach resulted in concentrated hybrid NP dispersion stable to aggregation and with hydrodynamic radius of particles of about 250 nm. Moreover, laccase enabled coupling between the phenolic groups in cork and amino moieties in the biopolymer-doped AgNP for permanent modification of the material. The antibacterial efficiency of the functionalized cork matrices, aimed as adsorbents for wastewater treatment, was evaluated against Escherichia coli and Staphylococcus aureus during 5 days in conditions mimicking those in constructed wetlands. Both intrinsically antimicrobial CS and AC contributed to the bactericidal effect of the enzymatically grafted on cork AgNP. In contrast, unmodified AgNP were easily washed off from the material, confirming that the biopolymers potentiated a durable antibacterial functionalization of the cork matrices.

An Expedient Method for the Synthesis of Thiosemicarbazones under Microwave Irradiation in Solvent-free Medium

Institute of Scientific and Technical Information of China (English)

LI, Jian-Ping; ZHENG, Peng-Zhi; ZHU, Jun-Ge; LIU, Rui-Jie; QU, Gui-Rong

2006-01-01

A simple, efficient and eco-friendly method for the synthesis of thiosemicarbazones from thiosemicarbazides and aldehyde under microwave irradiation has been reported, and no solvent and catalyst were used. And the technique of microwave irradiation coupled with solvent-free condition proved to be a quite valuable method in the organic synthesis.

Stabilization of gold nanoparticles by 6-mercaptopurine monolayers. Effects of the solvent properties.

Science.gov (United States)

Viudez, Alfonso J; Madueño, Rafael; Pineda, Teresa; Blázquez, Manuel

2006-09-14

6-Mercaptopurine-coated gold nanoparticles (6MP-AuNPs) have been prepared by modification of the nanoparticle surface with 6MP upon displacement of the protective layer of citrate anions. The modification has been studied by UV-vis and FTIR spectroscopies. A study of the stability of these 6MP-AuNPs in aqueous solutions as a function of ionic strength and pH has shown the importance of the charges on the stabilization. The protonation of N9 of the 6MP molecules brings about a sudden flocculation phenomenon. However, the flocculation is reversible upon changing the pH to values where the molecules become newly charged. Evidence of the competence between the interaction of capping solvent molecules and the attractive forces between particles is also shown in this paper.

PVC/carbon nanotubes nanocomposites: evaluation of electrical resistivity and the residual solvent effect over the thermal properties of nanocomposites; Nanocompositos PVC/nanotubos de carbono: avaliacao da resistividade eletrica e efeito do solvente utilizado na obtencao dos nanocompositos nas propriedades termicas

Energy Technology Data Exchange (ETDEWEB)

Araujo, Rogerio Gomes [Instituto Superior Tupy (UNISOCIESC), Joinville, SC (Brazil); Pires, Alfredo T.N., E-mail: araujo@sociesc.org.br [Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil)

2013-07-01

The procedure for obtaining nanocomposite by dispersing the nanoparticles in matrix polymer in solution with subsequent elimination of the solvent has been widely used, considering better efficiency in obtaining homogeneity of the final product. However, the presence of residual solvent may affect the nanocomposites in micro-and macroscopic properties of the product. The aim of this study was to evaluate the thermal properties of nanocomposites of poly(vinylchloride)/multi-walled carbon nanotube obtained from the polymer solution and dispersion of carbon nanotubes in tetrahydrofuran (THF), as well as the electrical resistivity of nanocomposites and the influence of residual solvent. The presence of residual tetrahydrofuran reduces the glass transition temperature (Tg) up to 26 °C, being independent of the amount of carbon nanotubes. The total elimination of the solvent is an important factor that does not induce changes in the properties of the polymeric matrix. The graft-COOH groups in the structure of the nanotubes leads to a considerable reduction of the electrical resistivity in ten orders of magnitude, from 0.4 %wt of nanotubes in the nanocomposite composition. (author)

Ultrathin free-standing close-packed gold nanoparticle films: Conductivity and Raman scattering enhancement

Science.gov (United States)

Yu, Qing; Huang, Hongwen; Peng, Xinsheng; Ye, Zhizhen

2011-09-01

A simple filtration technique was developed to prepare large scale free-standing close-packed gold nanoparticle ultrathin films using metal hydroxide nanostrands as both barrier layer and sacrificial layer. As thin as 70 nm, centimeter scale robust free-standing gold nanoparticle thin film was obtained. The thickness of the films could be easily tuned by the filtration volumes. The electronic conductivities of these films varied with the size of the gold nanoparticles, post-treatment temperature, and thickness, respectively. The conductivity of the film prepared from 20 nm gold nanoparticles is higher than that of the film prepared from 40 nm gold nanoparticle by filtering the same filtration volume of their solution, respectively. Their conductivities are comparable to that of the 220 nm thick ITO film. Furthermore, these films demonstrated an average surface Raman scattering enhancement up to 6.59 × 105 for Rhodamine 6 G molecules on the film prepared from 40 nm gold nanoparticles. Due to a lot of nano interspaces generated from the close-packed structures, two abnormal enhancements and relative stronger intensities of the asymmetrical vibrations at 1534 and 1594 cm-1 of R6G were observed, respectively. These robust free-standing gold nanoparticle films could be easily transferred onto various solid substrates and hold the potential application for electrodes and surface enhanced Raman detectors. This method is applicable for preparation of other nanoparticle free-standing thin films.A simple filtration technique was developed to prepare large scale free-standing close-packed gold nanoparticle ultrathin films using metal hydroxide nanostrands as both barrier layer and sacrificial layer. As thin as 70 nm, centimeter scale robust free-standing gold nanoparticle thin film was obtained. The thickness of the films could be easily tuned by the filtration volumes. The electronic conductivities of these films varied with the size of the gold nanoparticles, post

Suspensions of polymer-grafted nanoparticles with added polymers-Structure and effective pair-interactions.

Science.gov (United States)

Chandran, Sivasurender; Saw, Shibu; Kandar, A K; Dasgupta, C; Sprung, M; Basu, J K

2015-08-28

We present the results of combined experimental and theoretical (molecular dynamics simulations and integral equation theory) studies of the structure and effective interactions of suspensions of polymer grafted nanoparticles (PGNPs) in the presence of linear polymers. Due to the absence of systematic experimental and theoretical studies of PGNPs, it is widely believed that the structure and effective interactions in such binary mixtures would be very similar to those of an analogous soft colloidal material-star polymers. In our study, polystyrene-grafted gold nanoparticles with functionality f = 70 were mixed with linear polystyrene (PS) of two different molecular weights for obtaining two PGNP:PS size ratios, ξ = 0.14 and 2.76 (where, ξ = Mg/Mm, Mg and Mm being the molecular weights of grafting and matrix polymers, respectively). The experimental structure factor of PGNPs could be modeled with an effective potential (Model-X), which has been found to be widely applicable for star polymers. Similarly, the structure factor of the blends with ξ = 0.14 could be modeled reasonably well, while the structure of blends with ξ = 2.76 could not be captured, especially for high density of added polymers. A model (Model-Y) for effective interactions between PGNPs in a melt of matrix polymers also failed to provide good agreement with the experimental data for samples with ξ = 2.76 and high density of added polymers. We tentatively attribute this anomaly in modeling the structure factor of blends with ξ = 2.76 to the questionable assumption of Model-X in describing the added polymers as star polymers with functionality 2, which gets manifested in both polymer-polymer and polymer-PGNP interactions especially at higher fractions of added polymers. The failure of Model-Y may be due to the neglect of possible many-body interactions among PGNPs mediated by matrix polymers when the fraction of added polymers is high. These observations point to the need for a new framework to

Solvent-free porous framework resulted from 3D entanglement of 1D zigzag coordination polymer

KAUST Repository

Kole, Goutam Kumar Umar

2010-01-01

A solvent-free porous metal organic framework is constructed by the 3D entanglement of 1D zigzag coordination polymeric chains. The role of solvents and the effect of reaction conditions on such unique entanglement are addressed. © 2010 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.

Catalyst-free and solvent-free Michael addition of 1,3-dicarbonyl compounds to nitroalkenes by a grinding method

Science.gov (United States)

Xie, Zong-Bo; Wu, Ming-Yu; He, Ting; Le, Zhang-Gao

2012-01-01

Summary An environmentally benign, fast and convenient protocol has been developed for the Michael addition of 1,3-dicarbonyl compounds to β-nitroalkenes in good to excellent yields by a grinding method under catalyst- and solvent-free conditions. PMID:22563352

The γ-radiation induced grafting of unsaturated segmented polyurethanes with N-vinyl pyrrolidone

International Nuclear Information System (INIS)

Egboh, S.H.; George, M.H.; Barrie, J.A.

1984-01-01

Linear unsaturated segmented polyurethanes have been modified by hydrophilic grafting at 40 deg C with N-vinyl pyrrolidone, in N,N-dimethylformamide as solvent, using 60 Cobalt γ-irradiation. Graft copolymers were isolated from homopolymers by selective solvent extraction using a Soxhlet apparatus. The effects of reaction time, total dose, temperature and monomer concentration, on the graft yields have been examined. Relatively high irradiation doses were avoided during the grafting experiments to prevent possible degradation of the segmented polyurethanes and gelation of the homopolymer, poly(N-vinyl pyrrolidone). The ungrafted and grafted copolymers were characterized, and the graft copolymers were shown to be more thermally stable than the original polyurethanes, by thermogravimetric analysis. An explanation for the observed variation of the graft yields with some of the experimental variables is suggested. (author)

Harvesting the free fibular graft: A modified approach

Directory of Open Access Journals (Sweden)

Amitava Narayan Mukherjee

2011-01-01

Full Text Available Background: The conventional technique of free non-vascularized fibular grafting is attended with some amount of morbidity and a long scar. We report a technique with little interference to the surrounding soft tissues to harvest more than one-third of whole length fibula. Patients and Methods: Thirty four patients of average age 23.5 years (range 8 to 51 years having various pathologies like simple bone cysts (n=9, fibrous dysplasias (n=6, giant cell tumors (n=7, fracture non-union (n=10 and aneurysmal bone cysts (n=2 were taken up for the study. The fibula were harvested by two separate incisions, 1 cm each at proximal and distal extent of proposed donor site for taking out of graft after elevating the periosteum circumferentially using a periosteum stripper. Compression bandage and above knee plaster immobilization was applied to reduce the dead space collection . Results: The mean followup is 34 months. The patients were evaluated clinicoradiology. Thirty three patients showed good results. One patient had fair result due to delayed wound healing from hematoma which was treated surgically. Conclusion: The approach of harvesting fibula suggested by author reduces donor site morbidity and is safer than conventional approach.

The extraction of essential oil from patchouli leaves (Pogostemon cablin Benth) using microwave hydrodistillation and solvent-free microwave extraction methods

Science.gov (United States)

Putri, D. K. Y.; Kusuma, H. S.; Syahputra, M. E.; Parasandi, D.; Mahfud, M.

2017-12-01

Patchouli plant (Pogostemon cablin Benth) is one of the important essential oil-producing plant, contributes more than 50% of total exports of Indonesia’s essential oil. However, the extraction of patchouli oil that has been done in Indonesia is generally still used conventional methods that require enormous amount of energy, high solvent usage, and long time of extraction. Therefore, in this study, patchouli oil extraction was carried out by using microwave hydrodistillation and solvent-free microwave extraction methods. Based on this research, it is known that the extraction of patchouli oil using microwave hydrodistillation method with longer extraction time (240 min) only produced patchouli oil’s yield 1.2 times greater than solvent-free microwave extraction method which require faster extraction time (120 min). Otherwise the analysis of electric consumption and the environmental impact, the solvent-free microwave extraction method showed a smaller amount when compared with microwave hydrodistillation method. It is conclude that the use of solvent-free microwave extraction method for patchouli oil extraction is suitably method as a new green technique.

Synthesis of calix[4]arene-grafted magnetite nanoparticles and Evaluation of their arsenate as well as dichromate removal efficiency

Energy Technology Data Exchange (ETDEWEB)

Sayin, Serkan; Ozcan, Fatih; Yilmaz, Mustafa; Cengeloglu, Yunus [Department of Chemistry, Selcuk University, Konya (Turkey); Tor, Ali [Department of Environmental Engineering, Selcuk University, Konya (Turkey); Memon, Shahabuddin [National Center of Excellence in Analytical Chemistry, University of Sindh, Jamshoro (Pakistan)

2010-07-15

In this study, 5,17-bis-[(4-benzylpiperidine)methyl]-25,26,27,28-tetrahydroxy-calix[4]arene (3) has been prepared by the treatment of calix[4]arene with a secondary amine (4-benzylpiperidine) and formaldehyde by means of Mannich reaction. The prepared Mannich base (3) has been grafted onto [3-(2,3-epoxypropoxy)-propyl]-trimethoxysilane-modified Fe{sub 3}O{sub 4} magnetite nanoparticles (EPPTMS-MN) in order to obtain 5,17-bis-[(4-benzylpiperidine)methyl]-25,26,27,28-tetrahydroxy calix[4]arene-grafted EPPTMS-MN (BP-calix[4]arene-grafted Fe{sub 3}O{sub 4}). All new compounds were characterized by a combination of FTIR and {sup 1}H-NMR analyses. The morphology of the magnetic nanoparticles was examined by transmission electron microscopy. Moreover, the studies regarding the removal of arsenate and dichromate ions from the aqueous solutions were also carried out by using 5,17-bis-[(4-benzylpiperidine)methyl]-25,26,27,28-tetrahydroxy-calix[4]arene in liquid-liquid extraction and BP-calix[4]arene-grafted Fe{sub 3}O{sub 4} (4) in solid-liquid extraction experiments. The extraction results indicated that 3 is protonated at proton-switchable binding sites in acidic conditions. Hence, facilitating binding of arsenate and dichromate is resulted from both electrostatic interactions and hydrogen bonding. To understand the selectivity of 3, the retention of dichromate anions in the presence of Cl{sup -}, NO{sub 3}{sup -}, and SO{sub 4}{sup 2-} anions at pH 1.5 was also examined. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

Novel multi-biotin grafted poly(lactic acid) and its self-assembling nanoparticles capable of binding to streptavidin

Science.gov (United States)

Yan, Hao; Jiang, Weimin; Zhang, Yinxing; Liu, Ying; Wang, Bin; Yang, Li; Deng, Lihong; Singh, Gurinder K; Pan, Jun

2012-01-01

Targeted drug delivery requires novel biodegradable, specific binding systems with longer circulation time. The aim of this study was to prepare biotinylated poly(lactic acid) (PLA) nanoparticles (NPs) which can meet regular requirements as well conjugate more biotins in the polymer to provide better binding with streptavidin. A biotin-graft-PLA was synthesized based on previously published biodegradable poly(ethylene glycol) (PEG)-graft-PLA, with one polymer molecule containing three PEG molecules. Newly synthesized biotin-graft-PLA had three biotins per polymer molecule, higher than the previous biotinylated PLA (≤1 biotin per polymer molecule). A PEG with a much lower molecular weight (MW ~1900) than the previous biotinylated PLA (PEG MW ≥ 3800), and thus more biocompatible, was used which supplied good nonspecific protein-resistant property compatible to PEG-graft-PLA, suggesting its possible longer stay in the bloodstream. Biotin-graft-PLA specifically bound to streptavidin and self-assembled into NPs, during which naproxen, a model small molecule (MW 230 Da) and hydrophobic drug, was encapsulated (encapsulation efficiency 51.88%). The naproxen-loaded NPs with particle size and zeta potential of 175 nm and −27.35 mV realized controlled release within 170 hours, comparable to previous studies. The biotin-graft-PLA NPs adhered approximately two-fold more on streptavidin film and on biotin film via a streptavidin arm both in static and dynamic conditions compared with PEG-graft-PLA NPs, the proven nonspecific protein-resistant NPs. The specific binding of biotin-graft-PLA NPs with streptavidin and with biotin using streptavidin arm, as well as its entrapment and controlled release for naproxen, suggest potential applications in targeted drug delivery. PMID:22334778

Do stress fractures induce hypertrophy of the grafted fibula? A report of three cases received free vascularized fibular graft treatment for tibial defects.

Science.gov (United States)

Qi, Yong; Sun, Hong-Tao; Fan, Yue-Guang; Li, Fei-Meng; Lin, Zhou-Sheng

2016-06-01

The presence of large segmental defects of the diaphyseal bone is challenging for orthopedic surgeons. Free vascularized fibular grafting (FVFG) is considered to be a reliable reconstructive procedure. Stress fractures are a common complication following this surgery, and hypertrophy is the main physiological change of the grafted fibula. The exact mechanism of hypertrophy is not completely known. To the best of our knowledge, no studies have examined the possible relationship between stress fractures and hypertrophy. We herein report three cases of patients underwent FVFG. Two of them developed stress fractures and significant hypertrophy, while the remaining patient developed neither stress fractures nor significant hypertrophy. This phenomenon indicates that a relationship may exist between stress fractures and hypertrophy of the grafted fibula, specifically, that the presence of a stress fracture may initiate the process of hypertrophy.

Development of a new solvent-free flow efficiency coating for natural gas pipelines

Energy Technology Data Exchange (ETDEWEB)

Fogg, Graham A.; Morse, Jennifer [Bredero Shaw, Houston, TX (United States)

2005-07-01

Pipeline design engineers have traditionally considered external anti-corrosion coatings for the protection of gas transmission pipelines, with less consideration given to the benefits of internal flow efficiency coatings. This paper reviews the benefits of using a traditional solvent-based flow efficiency coating, and the relationship between the internal surface roughness of a pipe, the pressure drop across the pipeline, and the maximum flow rate of gas through the pipeline. To improve upon existing solvent-based flow efficiency coatings, a research program was undertaken to develop a solvent-free coating. The stages in the development of this coating are discussed, resulting in the plant application of the coating and final qualification to API RP 5L2. (author)

Free radical induced grafting of acrylonitrile on pre-treated rice straw for enhancing its durability and flame retardancy

Directory of Open Access Journals (Sweden)

Aparna Mukherjee

2017-01-01

Full Text Available The present investigation highlights the feasibility of a polymer grafting process to enhance the durability and flame retardancy of rice straw towards application as a low cost roofing material. The success of this grafting methodology was perceived to depend upon a bi-step pre-treatment process encompassing delignification and inorganic salts dispersion. Subsequently free radical polymer grafting of acrylonitrile onto rice straw was implemented by immersion mechanism initiated by oxalic acid-potassium permanganate initiator. The percentage of grafting, limiting oxygen index (LOI, biodegradability of the grafted rice straw and grafting yield percentage was estimated to be 57%, 27%, 0.02% and 136.67%, respectively. The weight loss of polymer grafted rice straw implied its less biodegradability over raw straw. Thus, the process of grafting contrived in the present analysis can be a promising and reliable technique for the efficient utilization of rice straw as an inexpensive roofing element through the augmentation of its durability and flame retardancy.

Synthesis of halide- and solvent free metal borohydrides

DEFF Research Database (Denmark)

Grinderslev, Jakob; Møller, Kasper Trans; Richter, Bo

have challenges due to their high desorption kinetics and limited reversibility at moderate conditions.[2],[3],[4] In this work, we present a new approach to synthesize halide- and solvent free metal borohydrides starting from the respective metal hydride. The synthetic strategy ensures that no metal...... to the metal. Hence, the powdered M(BH4)3∙DMS is heated to 140 °C for 4 hours to obtain pure M(BH4)3. The rare-earth metal borohydrides have been investigated by infrared spectroscopy and thermal analysis (TGA-DSC-MS). Furthermore, the structural trends are investigated by synchrotron radiation powder X...

Effect of solvent medium on the structural, morphological and optical properties of ZnO nanoparticles synthesized by the sol–gel method

Energy Technology Data Exchange (ETDEWEB)

Ungula, J., E-mail: ungulaj@qwa.ufs.ac.za; Dejene, B.F.

2016-01-01

ZnO nanoparticles were synthesized using a sol–gel method. The effect of solvent medium on the structural, morphological and optical properties of ZnO nanoparticles were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence spectroscopy (PL), UV–vis spectroscopy (UV–vis) and Energy-dispersive X-ray spectroscopy ( EDS). The XRD patterns showed single phase hexagonal structure. The crystallite size of as prepared ZnO nanoparticles was found to decrease from 28.1 nm to 10.8 nm with the increase in volume ratio of ethanol in the solvent as peak intensities and sharpness increase with corresponding increase in volume ratio of water. SEM micrographs showed that samples prepared in water medium are fairly spherical which turned to tiny rods with increasing volume ratios of ethanol. A sharp ultraviolet (UV) emission peak centred about 385 nm and a broad green–yellow emission at about 550 nm are observed with PL measurements. The band gap of ZnO decreased from 3.31 to 3.17 eV with an increase in the ethanol composition in the solvent, implying that the optical properties of these materials are clearly affected by the synthesis medium.

A Highly Efficient Solvent-Free Acetalization of Aldehydes to 1,1 ...

African Journals Online (AJOL)

1,1-Diacetates are prepared in excellent yields from aldehydes and acetic anhydride under solvent-free conditions at room temperature in short reaction times using catalytic amount of sulfonic acid functionalized silica (SiO2-Pr-SO3H) which could be easily handled and removed from the mixture of reaction. Keywords: 1 ...

USE OF CORTICAL BONE FENESTRATION, AUTOGENOUS FREE SKIN GRAFT, AND THERMOGRAPHY FOR WOUND TREATMENT AND MONITORING IN A RED WOLF (CANIS RUFUS GREGORYI).

Science.gov (United States)

Hurley-Sanders, Jennifer L; Sladky, Kurt K; Nolan, Elizabeth C; Loomis, Michael R

2015-09-01

A 2-yr-old female red wolf (Canis rufus gregoryi) sustained a degloving injury to the left thoracic limb while in a display habitat. Initial attempts to resolve the extensive wound by using conservative measures were unsuccessful. Subsequent treatment using a free skin graft consisted first of establishment of an adequate granulation bed via cortical bone fenestration. After establishment of a healthy granulation bed was achieved, free skin graft was harvested and transposed over the bed. To monitor viability and incorporation of the graft, serial thermographic imaging was performed. Thermography noninvasively detects radiant heat patterns and can be used to assess vascularization of tissue, potentially allowing early detection of graft failure. In this case, thermography documented successful graft attachment.

Method to produce biomass-derived compounds using a co-solvent system containing gamma-valerolactone

Science.gov (United States)

Dumesic, James A.; Motagamwala, Ali Hussain

2017-06-27

A method to produce an aqueous solution of carbohydrates containing C5- and/or C6-sugar-containing oligomers and/or C5- and/or C6-sugar monomers in which biomass or a biomass-derived reactant is reacted with a solvent system having an organic solvent, and organic co-solvent, and water, in the presence of an acid. The method produces the desired product, while a substantial portion of any lignin present in the reactant appears as a precipitate in the product mixture.

Ultrafast Photoinduced Electron Transfer in a π-Conjugated Oligomer/Porphyrin Complex

KAUST Repository

Aly, Shawkat Mohammede

2014-10-02

Controlling charge transfer (CT), charge separation (CS), and charge recombination (CR) at the donor-acceptor interface is extremely important to optimize the conversion efficiency in solar cell devices. In general, ultrafast CT and slow CR are desirable for optimal device performance. In this Letter, the ultrafast excited-state CT between platinum oligomer (DPP-Pt(acac)) as a new electron donor and porphyrin as an electron acceptor is monitored for the first time using femtosecond (fs) transient absorption (TA) spectroscopy with broad-band capability and 120 fs temporal resolution. Turning the CT on/off has been shown to be possible either by switching from an organometallic oligomer to a metal-free oligomer or by controlling the charge density on the nitrogen atom of the porphyrin meso unit. Our time-resolved data show that the CT and CS between DPP-Pt(acac) and cationic porphyrin are ultrafast (approximately 1.5 ps), and the CR is slow (ns time scale), as inferred from the formation and the decay of the cationic and anionic species. We also found that the metallic center in the DPP-Pt(acac) oligomer and the positive charge on the porphyrin are the keys to switching on/off the ultrafast CT process.

Surface properties of calcium and magnesium oxide nanopowders grafted with unsaturated carboxylic acids studied with inverse gas chromatography.

Science.gov (United States)

Maciejewska, Magdalena; Krzywania-Kaliszewska, Alicja; Zaborski, Marian

2012-09-28

Inverse gas chromatography (IGC) was applied at infinite dilution to evaluate the surface properties of calcium and magnesium oxide nanoparticles and the effect of surface grafted unsaturated carboxylic acid on the nanopowder donor-acceptor characteristics. The dispersive components (γ(s)(D)) of the free energy of the nanopowders were determined by Gray's method, whereas their tendency to undergo specific interactions was estimated based on the electron donor-acceptor approach presented by Papirer. The calcium and magnesium oxide nanoparticles exhibited high surface energies (79 mJ/m² and 74 mJ/m², respectively). Modification of nanopowders with unsaturated carboxylic acids decreased their specific adsorption energy. The lowest value of γ(s)(D) was determined for nanopowders grafted with undecylenic acid, approximately 55 mJ/m². The specific interactions were characterised by the molar free energy (ΔG(A)(SP)) and molar enthalpy (ΔH(A)(SP)) of adsorption as well as the donor and acceptor interaction parameters (K(A), K(D)). Copyright © 2012 Elsevier B.V. All rights reserved.

Synthetic surfactant- and cross-linker-free preparation of highly stable lipid-polymer hybrid nanoparticles as potential oral delivery vehicles.

Science.gov (United States)

Wang, Taoran; Xue, Jingyi; Hu, Qiaobin; Zhou, Mingyong; Chang, Chao; Luo, Yangchao

2017-06-05

The toxicity associated with concentrated synthetic surfactants and the poor stability at gastrointestinal condition are two major constraints for practical applications of solid lipid nanoparticles (SLN) as oral delivery vehicles. In this study, a synthetic surfactant-free and cross-linker-free method was developed to fabricate effective, safe, and ultra-stable lipid-polymer hybrid nanoparticles (LPN). Bovine serum albumin (BSA) and dextran varying in molecular weights were first conjugated through Maillard reaction and the conjugates were exploited to emulsify solid lipid by a solvent diffusion and sonication method. The multilayer structure was formed by self-assembly of BSA-dextran micelles to envelope solid lipid via a pH- and heating-induced facile process with simultaneous surface deposition of pectin. The efficiency of different BSA-dextran conjugates was systematically studied to prepare LPN with the smallest size, the most homogeneous distribution and the greatest stability. The molecular interactions were characterized by Fourier transform infrared and fluorescence spectroscopies. Both nano spray drying and freeze-drying methods were tested to produce spherical and uniform pectin-coated LPN powders that were able to re-assemble nanoscale structure when redispersed in water. The results demonstrated the promise of a synthetic surfactant- and cross-linker-free technique to prepare highly stable pectin-coated LPN from all natural biomaterials as potential oral delivery vehicles.

PVC/carbon nanotubes nanocomposites: evaluation of electrical resistivity and the residual solvent effect over the thermal properties of nanocomposites

International Nuclear Information System (INIS)

Araujo, Rogerio Gomes; Pires, Alfredo T.N.

2013-01-01

The procedure for obtaining nanocomposite by dispersing the nanoparticles in matrix polymer in solution with subsequent elimination of the solvent has been widely used, considering better efficiency in obtaining homogeneity of the final product. However, the presence of residual solvent may affect the nanocomposites in micro-and macroscopic properties of the product. The aim of this study was to evaluate the thermal properties of nanocomposites of poly(vinylchloride)/multi-walled carbon nanotube obtained from the polymer solution and dispersion of carbon nanotubes in tetrahydrofuran (THF), as well as the electrical resistivity of nanocomposites and the influence of residual solvent. The presence of residual tetrahydrofuran reduces the glass transition temperature (Tg) up to 26 °C, being independent of the amount of carbon nanotubes. The total elimination of the solvent is an important factor that does not induce changes in the properties of the polymeric matrix. The graft-COOH groups in the structure of the nanotubes leads to a considerable reduction of the electrical resistivity in ten orders of magnitude, from 0.4 %wt of nanotubes in the nanocomposite composition. (author)

Self-assembled fluorescent organic nanoparticles for live cell imaging

NARCIS (Netherlands)

Fischer, I.; Petkau, K.; Dorland, Y.L.; Schenning, A.P.H.J.; Brunsveld, L.

2013-01-01

Fluorescent, cell-permeable, organic nanoparticles based on self-assembled p-conjugated oligomers with high absorption cross-sections and high quantum yields have been developed. The nanoparticles are generated with a tuneable density of amino groups for charge-mediated cellular uptake by a

Effect of solvent medium on the structural, morphological and optical properties of ZnS nanoparticles synthesized by solvothermal route

Energy Technology Data Exchange (ETDEWEB)

Mendil, R., E-mail: radia.mendil@yahoo.fr [Laboratoire de Physique des Matériaux et des Nanomatériaux appliquée à l' Environnement, Université de Gabès, Faculté des Sciences de Gabès, Cité Erriadh Manara Zrig, 6072 Gabès (Tunisia); Ben Ayadi, Z. [Laboratoire de Physique des Matériaux et des Nanomatériaux appliquée à l' Environnement, Université de Gabès, Faculté des Sciences de Gabès, Cité Erriadh Manara Zrig, 6072 Gabès (Tunisia); Djessas, K. [Laboratoire Procédés, Matériaux et Energie Solaire (PROMES-CNRS), TECNOSUD, Rambla de la thermodynamique, 66100 Perpignan (France); Université de Perpignan Via Domitia, 52 avenue Paul Alduy, 68860, Perpignan Cedex9 (France)

2016-09-05

Different morphologies of ZnS have been synthesized by a facile solvothermal approach in a mixed solvent made of Ethylenediamine (EN) and distilled water. The effect of solvent medium on the structural, morphological and optical properties of ZnS nanoparticles were investigated. The formation mechanism of different morphologies was proposed based on the experiment results. The as-prepared samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive spectrometer (EDS), Raman spectroscopy and UV-Vis-IR spectrophotometer. The results show that phase transformation is easily induced and there is a strong correlation between morphology and structure of the ZnS nanocrystals by changing the solvent. The results also show that we have successfully produced hexagonal phase ZnS nanorods with mixed solvent. The grain sizes in the range of 17–22 nm were obtained according to elaboration conditions. Raman spectra show the intense peak at 346 cm{sup −1}, which is a typical Raman peak of bulk ZnS crystal, no signature of secondary phases. The band gap of ZnS increased from 3.49 to 3.74 eV with an increase in the EN composition in the solvent, implying that the optical properties of these materials are clearly affected by the synthesis medium. - Highlights: • ZnS was prepared at low temperature using solvothermal method. • The phase transformation and shape evolution processes were studied. • The role of solvent (EN/W) has been discussed for formation of ZnS nanostructures with different morphology. • The properties and growth mechanism of ZnS nanoparticles were investigated. • Optical band gap of ZnS powder were investigated using UV vis spectroscopy.

Solvent and stabilizer free growth of Ag and Pd nanoparticles using metallic salts/cyclotriphosphazenes mixtures

Energy Technology Data Exchange (ETDEWEB)

Díaz Valenzuela, C. [Departamento de Química, Facultad de Química, Universidad de Chile, La Palmeras 3425, Nuñoa, Casilla 653, Santiago de Chile (Chile); Valenzuela, M.L., E-mail: mlvalenzuela@unab.cl [Universidad Andres Bello, Departamento de Ciencias Química, Facultad de Ciencias Exactas, Av. Republica 275, Santiago (Chile); Caceres, S.; Diaz, R. [Departamento de Química, Facultad de Química, Universidad de Chile, La Palmeras 3425, Nuñoa, Casilla 653, Santiago de Chile (Chile); O' Dwyer, C. [Applied Nanoscience Group, Department of Chemistry, University College Cork, Cork (Ireland); Micro and Nanoelectronics Centre, Tyndall National Institute, Lee Maltings, Cork (Ireland)

2013-12-16

Cyclotriphosphazene is used as a sacrificial solid-state template to synthesize a range of Ag and Pd nanoparticles with diverse geometries by thermal treatment using MLn/N{sub 3}P{sub 3}(O{sub 2}C{sub 12}H{sub 8}){sub 3} mixtures. The Pd and Ag nanoparticles are synthesized by solid-state pyrolysis of AgPPh{sub 3}[CF{sub 3}SO{sub 3}]/N{sub 3}P{sub 3}(O{sub 2}C{sub 12}H{sub 8}){sub 3} and PdCl{sub 2}/N{sub 3}P{sub 3}(O{sub 2}C{sub 12}H{sub 8}){sub 3} mixtures with molar relationships of 1:1, 1:5 and 1:10 respectively, in air and at 800 °C. The morphology of the as-prepared nanoparticles is found to depend on the molar ratio of the precursor mixture, the preparation method and of the nature of the metal. Ag and Pd, microcrystals were thermally grown on Si from the respective 1:1 precursors while that metal foams were grown from 1:5 ratios precursors on SiO{sub 2} wafers. High resolution transmission electron microscopy investigations reveal in most cases small crystals of Pd. HRSTEM measurements indicate that the formation of the Pd and Ag nanoparticles occurs through a phase demixing and dewetting mechanism. This approach has potential to be a useful and facile method to prepare metallic nanoparticles without requiring solutions or surfactants for application in electronic, catalytic and sensor materials and devices. - Highlights: • Pyrolysis MLn/N{sub 3}P{sub 3}(O{sub 2}C{sub 12}H{sub 8}){sub 3} mixtures under air, give Pd and Ag nanoparticles. • AgPPh{sub 3}[CF{sub 3}SO{sub 3}] and PdCl{sub 2} in molar ratios 1:1 and 1:5 were used. • Metal foams were obtained from 1:5 ratios when deposited on SiO{sub 2.} • Using crucible supporting in 1:1 metal/trimer <2 nm Pd nanoparticles were obtained. • The probable mechanism involves a dewetting, nucleation and ripening crystallization.

Modeling polymer-induced interactions between two grafted surfaces: comparison between interfacial statistical associating fluid theory and self-consistent field theory.

Science.gov (United States)

Jain, Shekhar; Ginzburg, Valeriy V; Jog, Prasanna; Weinhold, Jeffrey; Srivastava, Rakesh; Chapman, Walter G

2009-07-28

The interaction between two polymer grafted surfaces is important in many applications, such as nanocomposites, colloid stabilization, and polymer alloys. In our previous work [Jain et al., J. Chem. Phys. 128, 154910 (2008)], we showed that interfacial statistical associating fluid density theory (iSAFT) successfully calculates the structure of grafted polymer chains in the absence/presence of a free polymer. In the current work, we have applied this density functional theory to calculate the force of interaction between two such grafted monolayers in implicit good solvent conditions. In particular, we have considered the case where the segment sizes of the free (sigma(f)) and grafted (sigma(g)) polymers are different. The interactions between the two monolayers in the absence of the free polymer are always repulsive. However, in the presence of the free polymer, the force either can be purely repulsive or can have an attractive minimum depending upon the relative chain lengths of the free (N(f)) and grafted polymers (N(g)). The attractive minimum is observed only when the ratio alpha = N(f)/N(g) is greater than a critical value. We find that these critical values of alpha satisfy the following scaling relation: rho(g) square root(N(g)) beta(3) proportional to alpha(-lambda), where beta = sigma(f)/sigma(g) and lambda is the scaling exponent. For beta = 1 or the same segment sizes of the free and grafted polymers, this scaling relation is in agreement with those from previous theoretical studies using self-consistent field theory (SCFT). Detailed comparisons between iSAFT and SCFT are made for the structures of the monolayers and their forces of interaction. These comparisons lead to interesting implications for the modeling of nanocomposite thermodynamics.

Fe–Al/clay as an efficient heterogeneous catalyst for solvent-free ...

Indian Academy of Sciences (India)

SiO2,27 amberlyst-15,28 etc. ... tometer, using Ni-filtered Cu Ka (0.15418 nm) radia- ... The spectral data of some ... C).29 1H NMR ... 3.99(q, j = 7.1 Hz, 2H), 5.12 (s,1H), 7.23 (d, j = 8.35 .... Recyclability was studied in both solvent-free and.

Synthesis and characterization of poly[1-(N,N-bis-carboxymethyl)amino-3-allylglycerol-co-dimethylacrylamide] grafted to magnetic nano-particles for extraction and determination of letrozole in biological and pharmaceutical samples.

Science.gov (United States)

Ahmad Panahi, Homayon; Soltani, Elham Reza; Moniri, Elham; Tamadon, Atefeh

2013-12-15

In this paper, a new method is reported for the surface grafting of poly[1-(N,N-bis-carboxymethyl)amino-3-allylglycerol-co-dimethylacrylamide] onto magnetic nano-particles modified by 3-mercaptopropyltrimethoxysilane. The grafted nano-sorbent was characterized by Fourier transform infrared spectroscopy, elemental analysis, thermogravimetric analysis, and scanning electron microscopy. Agglomerated nano-particles with multi-pores were used for extraction and determination of trace letrozole in human biological fluids and pharmaceutical samples. The profile of the letrozole uptake by the magnetic nano-sorbent reflected good accessibility of the active sites in the grafted polymer. Scatchard analysis revealed that the sorption capacity of the functionalized nano-sorbent was 6.27 µmol g(-1) at an optimum pH of 4. The equilibrium adsorption data of letrozole by grafted magnetic nano-sorbent were analyzed by Langmuir, Freundlich, Temkin and Redlich-Peterson models. Conformation of the experimental data in the Langmuir isotherm model indicated the homogeneous binding site of functional polymer-grafted magnetic nano-sorbent surface. Nearly 89% of letrozole was released in simulated gastric fluid, pH 1.2, in 2h and 79% in simulated intestinal fluid, pH 7.4, in 30 h. These results show the utility of the letrozole loaded- polymer grafted magnetite nano-particles for enteric drug delivery. © 2013 Elsevier B.V. All rights reserved.

Silica nanoparticles as a highly efficient catalyst for the one-pot ...

African Journals Online (AJOL)

Silica nanoparticles as a highly efficient catalyst for the one-pot synthesis of sterically congested ... Bulletin of the Chemical Society of Ethiopia ... 42 nm) as a catalyst under solvent free conditions at room temperature is described. The ease of ...

Sulfonated hydrocarbon graft architectures for cation exchange membranes

DEFF Research Database (Denmark)

Nielsen, Mads Møller; Jankova Atanasova, Katja; Hvilsted, Søren

2013-01-01

A synthetic strategy to hydrocarbon graft architectures prepared from a commercial polysulfone and aimed as ion exchange membrane material is proposed. Polystyrene is grafted from a polysulfone macroinitiator by atom transfer radical polymerization, and subsequently sulfonated with acetyl sulfate...... to various degrees. Series of grafting densities and graft lengths are prepared, and membranes are solvent cast from DMSO. The membrane properties in aqueous environments are evaluated from their water swelling behavior, and their thermal properties and stability are investigated by thermogravimetric...

Development of Highly Efficient Grafting Technique and Synthesis of Natural Polymer-Based Graft Adsorbent

Energy Technology Data Exchange (ETDEWEB)

Ueki, Y; Seko, N; Tamada, M [Japan Atomic Energy Agency, Quantum Beam Science Directorate, Takasaki (Japan)

2012-09-15

In the framework of the CRP, Japan has focused on the development of fibrous adsorbents for removal of toxic metal ions and recovery of significant metal ions from industrial wastewater and streaming water. Graft polymerization was carried out by using gamma irradiation facility and electron beam accelerator. Emulsion grafting is a novel topic for synthesis of metal ion adsorbents which are prepared from fibrous trunk polymers such as polyethylene fibre and biodegradable nonwoven fabrics. The emulsion grafting, where monomer micelles are dispersed in water in the presence of surfactant, is a highly efficient and economic grafting technique as compared to general organic solvent system. The resultant cotton-based adsorbent has high adsorption efficiency and high adsorption capacity for Hg, besides, it is biodegradable. Polylactic acid can also be used as a trunk material for the grafting. (author)

Improving Pullulanase Catalysis via Reversible Immobilization on Modified Fe3O4@Polydopamine Nanoparticles.

Science.gov (United States)

Wang, Jianfeng; Liu, Zhongmei; Zhou, Zhemin

2017-08-01

To improve the catalysis of pullulanase from Anoxybacillus sp.WB42, Fe 3 O 4 @polydopamine nanoparticles (Fe 3 O 4 @PDA) were prepared and modified with functional groups for immobilization of pullulanases via covalent binding or ionic adsorption. Immobilized pullulanases had lower thermal stability than that of free pullulanase, whereas their catalysis depended on the surface characteristics of nanoparticles. As for covalent immobilization of pullulanases onto Fe 3 O 4 @PDA derivatives, the spacer grafted onto Fe 3 O 4 @PDA made the catalytic efficiency of pullulanase increase up to the equivalence of free enzyme but dramatically reduced the pullulanase thermostability. In contrast, pullulanases bounded ionically to Fe 3 O 4 @PDA derivatives had higher activity recovery and catalytic efficiency, and their catalytic behaviors varied with the modifier grafted onto Fe 3 O 4 @PDA. Among these immobilized pullulanases, ionic adsorption of pullulanase on Fe 3 O 4 @PDA-polyethyleneimine-glycidyltrimethylammonium gave a high-performance and durable catalyst, which displayed not only 1.5-fold increase in catalytic efficiency compared to free enzyme but also a significant improvement in operation stability with a half of initial activity after 27 consecutive cycles with a total reaction time of 13.5 h, and was reversible, making this nanoparticle reusable for immobilization.

Side-chain degradation of ultrapure π-conjugated oligomers: implications for organic electronics

NARCIS (Netherlands)

Abbel, R.J.; Wolffs, M.; Bovee, R.A.A.; Dongen, van J.L.J.; Lou, X.W.; Henze, O.; Feast, W.J.; Meijer, E.W.; Schenning, A.P.H.J.

2009-01-01

The degrdn. of two defect-free pi-conjugated oligomers and the participation of their solubilizing side chains in the process are studied in unprecedented detail. The detected intermediate products reveal a mechanism of successive shortening of alkyl and oligo(ethylene glycol) substituents.

Comparison of microwave hydrodistillation and solvent-free microwave extraction of essential oil from Melaleuca leucadendra Linn

Science.gov (United States)

Ismanto, A. W.; Kusuma, H. S.; Mahfud, M.

2017-12-01

The comparison of solvent-free microwave extraction (SFME) and microwave hydrodistillation (MHD) in the extraction of essential oil from Melaleuca leucadendra Linn. was examined. Dry cajuput leaves were used in this study. The purpose of this study is also to determine optimal condition (microwave power). The relative electric consumption of SFME and MHD methods are both showing 0,1627 kWh/g and 0,3279 kWh/g. The results showed that solvent-free microwave extraction methods able to reduce energy consumption and can be regarded as a green technique for extraction of cajuput oil.

HDPE/clay hybrids: the effect of clay modified with poly(diphenyl siloxanes) on thermal and rheological properties

Energy Technology Data Exchange (ETDEWEB)

Monasterio, Fernanda E.; Carrera, Maria C.; Erdmann, Eleonora; Destefanis, Hugo A., E-mail: ferelenakq@gmail.co [Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET), Buenos Aires (Argentina). Inst. de Investigaciones para la Industria Quimica; Pita, Victor J.R.R.; Dias, Marcos L. [Universidade Federal do Rio de Janeiro (IMA/UFRJ), RJ (Brazil). Inst. de Macromoleculas Profa. Eloisa Mano

2009-07-01

Poly(diphenyl siloxanes) (PDPhS) were synthesized in presence of organophilic clay in order to modify its nano structure. Two silane monomers were used: dimethoxydiphenylsilane and dichlorodiphenylsilane. The following characterizations were performed for all clays: XRD, FTIR and TGA/DTG. These siloxane-modified clays were more hydrophobic and had enhanced thermal stability. Solvent extraction was carried out in the siloxane-modified clays and the PDPhS soluble fraction analyzed according the molecular weight via GPC. The presence of free and grafted oligomers on clay surface was identified. The modified clays were added to HDPE by melt processing to obtain HDPE/clay hybrids which exhibited marked differences in the rheological behavior when compared with neat HDPE. (author)

HDPE/clay hybrids: the effect of clay modified with poly(diphenyl siloxanes) on thermal and rheological properties

International Nuclear Information System (INIS)

Monasterio, Fernanda E.; Carrera, Maria C.; Erdmann, Eleonora; Destefanis, Hugo A.; Pita, Victor J.R.R.; Dias, Marcos L.

2009-01-01

Poly(diphenyl siloxanes) (PDPhS) were synthesized in presence of organophilic clay in order to modify its nano structure. Two silane monomers were used: dimethoxydiphenylsilane and dichlorodiphenylsilane. The following characterizations were performed for all clays: XRD, FTIR and TGA/DTG. These siloxane-modified clays were more hydrophobic and had enhanced thermal stability. Solvent extraction was carried out in the siloxane-modified clays and the PDPhS soluble fraction analyzed according the molecular weight via GPC. The presence of free and grafted oligomers on clay surface was identified. The modified clays were added to HDPE by melt processing to obtain HDPE/clay hybrids which exhibited marked differences in the rheological behavior when compared with neat HDPE. (author)

Synthesis of polyaniline (PANI) and functionalized polyaniline (F-PANI) nanoparticles with controlled size by solvent displacement method. Application in fluorescence detection and bacteria killing by photothermal effect

Science.gov (United States)

Bongiovanni Abel, Silvestre; Yslas, Edith I.; Rivarola, Claudia R.; Barbero, Cesar A.

2018-03-01

Polyaniline nanoparticles (PANI-NPs) were easily obtained applying the solvent displacement method by using N-methylpyrrolidone (NMP) as good solvent and water as poor solvent. Different polymers such as polyvinylpyrrolidone (PVP), chondroitin sulfate (ChS), polyvinyl alcohol (PVA), and polyacrylic acid (PAA) were used as stabilizers. Dynamic light scattering and scanning electron microscopy corroborated the size and morphology of the formed NPs. It was demonstrated that the size of nanoparticles could be controlled by setting the concentration of PANI in NMP, the NMP to water ratio, and the stabilizer’s nature. The functionalization and fluorescence of NPs were checked by spectroscopic techniques. Since polyaniline show only weak intrinsic luminescence, fluorescent groups were linked to the polyaniline chains prior to the nanoparticle formation using a linker. Polyaniline chains were functionalized by nucleophilic addition of cysteamine trough the thiol group thereby incorporating pendant primary aliphatic amine groups to the polyaniline backbone. Then, dansyl chloride (DNS-Cl), which could act as an extrinsic chromophore, was conjugated to the amine pendant groups. Later, the functionalized polyaniline was used to produce nanoparticles by solvent displacement. The optical and functional properties of fluorescent nanoparticles (F-PANI-NPs) were determined. F-PANI-NPs in the conductive state (pH causes bacterial death. Therefore, the F-PANI-NPs could be tracked and applied to inhibit different diseases caused by pathogenic microorganisms and resistant to antibiotics as well as a new disinfection method to surgical materials.

Piper-betle-shaped nano-S-catalyzed synthesis of 1-amidoalkyl-2-naphthols under solvent-free reaction condition: a greener "nanoparticle-catalyzed organic synthesis enhancement" approach.

Science.gov (United States)

Das, Vijay K; Borah, Madhurjya; Thakur, Ashim J

2013-04-05

Nano-S prepared by an annealing process showed excellent catalytic activity for the synthesis of 1-amidoalkyl-2-naphthols under solvent-free reaction condition at 50 °C. The catalyst could be reused up to the fifth cycle without loss in its action. The green-ness of the present protocol was also measured using green metrics drawing its superiority.

History of free skin grafting. Knowledge of empiricism?

OpenAIRE

Klasen, Hendrik Jan

1981-01-01

In the course of more than a hundred years, skin grafting has become a standard procedure in surgery. The indications for the several types of grafting have become rather uniform.The technical aids at the operations only differ in details. Especially the vast experience gained in World War II provided the opportunity to develop the technique of skin grafting and so the evolution of present day plastics surgery. However, virtually every step in the field of indications, selection of grafts, te...

Highly efficient isocyanate-free microwave-assisted synthesis of [6]-oligourea

KAUST Repository

Qaroush, Abdussalam K.

2013-01-01

A new eco-friendly, isocyanate-free, energy-saving method for the production of [6]-oligourea, utilizing a green carbonylating agent, viz. propylene carbonate, is reported. It comprises an organocatalyzed, microwave-assisted, solvent-free synthesis. Two modes of microwave-assisted synthesis, viz. dynamic and fixed energy modes, were applied. Upon optimization, the dynamic mode gave 79% yields of [6]-oligourea. On the other hand, almost quantitative yields were obtained using the fixed mode, within 20 min, at 10 W and with the same catalyst loading. Combination of both organocatalysis and microwave energy input appears to be a key issue for the efficiency of the reaction, with the fixed energy mode being best suited. It should be noted that all data reported are reproducible (due to the homogeneous microwave technology used by CEM Discover S-Class of microwave reactors). To the best of our knowledge, this is the best eco-friendly synthetic approach for the preparation of the title oligomers. It paves the way for using more of the biorenewable and sustainable chemicals as a feedstock for the production of polyureas. The oligomer produced was analyzed by EA, ATR-FTIR, XRD, 1H and 13CNMR. Furthermore, thermal properties of the resulting [6]-oligourea were analyzed using TGA and DSC. © The Royal Society of Chemistry 2013.

Formation of coffee-stain patterns at the nanoscale: The role of nanoparticle solubility and solvent evaporation rate.

Science.gov (United States)

Zhang, Jianguo; Milzetti, Jasmin; Leroy, Frédéric; Müller-Plathe, Florian

2017-03-21

When droplets of nanoparticle suspension evaporate from surfaces, they leave behind a deposit of nanoparticles. The mechanism of evaporation-induced pattern formation in the deposit is studied by molecular dynamics simulations for sessile nanodroplets. The influence of the interaction between nanoparticles and liquid molecules and the influence of the evaporation rate on the final deposition pattern are addressed. When the nanoparticle-liquid interaction is weaker than the liquid-liquid interaction, an interaction-driven or evaporation-induced layer of nanoparticles appears at the liquid-vapor interface and eventually collapses onto the solid surface to form a uniform deposit independently of the evaporation rate. When the nanoparticle-liquid and liquid-liquid interactions are comparable, the nanoparticles are dispersed inside the droplet and evaporation takes place with the contact line pinned at a surface defect. In such a case, a pattern with an approximate ring-like shape is found with fast evaporation, while a more uniform distribution is observed with slower evaporation. When the liquid-nanoparticle interaction is stronger than the liquid-liquid interaction, evaporation always occurs with receding contact line. The final deposition pattern changes from volcano-like to pancake-like with decreasing evaporation rate. These findings might help to design nanoscale structures like nanopatterns or nanowires on surface through controlled solvent evaporation.

PEGylation on mixed monolayer gold nanoparticles: Effect of grafting density, chain length, and surface curvature.

Science.gov (United States)

Lin, Jiaqi; Zhang, Heng; Morovati, Vahid; Dargazany, Roozbeh

2017-10-15

PEGylation on nanoparticles (NPs) is widely used to prevent aggregation and to mask NPs from the fast clearance system in the body. Understanding the molecular details of the PEG layer could facilitate rational design of PEGylated NPs that maximize their solubility and stealth ability without significantly compromising the targeting efficiency and cellular uptake. Here, we use molecular dynamics (MD) simulation to understand the structural and dynamic the PEG coating of mixed monolayer gold NPs. Specifically, we modeled gold NPs with PEG grafting densities ranging from 0-2.76chain/nm 2 , chain length with 0-10 PEG monomers, NP core diameter from 5nm to 500nm. It is found that the area accessed by individual PEG chains gradually transits from a "mushroom" to a "brush" conformation as NP surface curvature become flatter, whereas such a transition is not evident on small NPs when grafting density increases. It is shown that moderate grafting density (∼1.0chain/nm 2 ) and short chain length are sufficient enough to prevent NPs from aggregating in an aqueous medium. The effect of grafting density on solubility is also validated by dynamic light scattering measurements of PEGylated 5nm gold NPs. With respect to the shielding ability, simulations predict that increase either grafting density, chain length, or NP diameter will reduce the accessibility of the protected content to a certain size molecule. Interestingly, reducing NP surface curvature is estimated to be most effective in promoting shielding ability. For shielding against small molecules, increasing PEG grafting density is more effective than increasing chain length. A simple model that includes these three investigated parameters is developed based on the simulations to roughly estimate the shielding ability of the PEG layer with respect to molecules of different sizes. The findings can help expand our current understanding of the PEG layer and guide rational design of PEGylated gold NPs for a particular

Effects of Extraction Solvents on the Quantification of Free Amino Acids in Lyophilised Brewer’s Yeast

Directory of Open Access Journals (Sweden)

Andreea STĂNILĂ

2018-05-01

Full Text Available The aim of this work was to test some solvents in order to improve the free amino acids extraction from lyophilised brewer’s yeast. The brewer’ yeast was treated with four types of extraction solvents: Solvent I – acetonitrile 25%/HCl 0.01M (ACN; Solvent II – ethanol 80%; solvent III – HCl 0.05M/deionized water (1/1 volume; Solvent IV – HCl 0.05M/ethanol 80% (1/1 volume. The supernatants were analysed by HPLC-DAD-ESI-MS method. Acetonitrile provided the less quantities and number of amino acids extracted due to its weaker polarity. Solvent II and IV (ethanol, respectively acidified ethanol, which have an increased polarity, extracted 15 amino acids due to the addition of HCl in solvent IV. Solvent III (acidified water proved to be the best extraction solvent for the amino acids from brewer’s yeast providing the separation of 17 compounds: GLN, ASN, SER, GLY, ALA, ORN, PRO, HIS, LYS, GLU, TRP, LEU, PHE, ILE, AAA, HPHE, TYR.

Overcoming acquired drug resistance in colorectal cancer cells by targeted delivery of 5-FU with EGF grafted hollow mesoporous silica nanoparticles

Science.gov (United States)

Chen, Lijue; She, Xiaodong; Wang, Tao; He, Li; Shigdar, Sarah; Duan, Wei; Kong, Lingxue

2015-08-01

Acquired drug resistance (ADR) can be developed in colorectal cancer cells after 5-fluorouracil (5-FU) treatment and diminish the effectiveness of chemotherapy. In this work, acquired 5-FU resistance in the colorectal cancer cell line SW480 was obtained with the up-regulation of dihydropyrimidine dehydrogenase (DPYD) gene expression which can convert 5-FU to its inactive metabolite. To overcome ADR in colorectal cancer, hollow mesoporous silica nanoparticles (HMSNs) grafted with epidermal growth factor (EGF) were used as nanocarriers to deliver 5-FU to colorectal cancer cells with acquired drug resistance. The effect and mechanism of 5-FU loaded EGF grafted HMSNs (EGF-HMSNs-5-FU) in overcoming acquired drug resistance in SW480/ADR cells were studied. The EGF-HMSNs were demonstrated to be specifically internalized in EGFR overexpressed SW480/ADR cells via a receptor-mediated endocytosis and can escape from endo-lysosomes. The EGF-HMSNs-5-FU exhibited much higher cytotoxicity on SW480/ADR cells than HMSNs-5-FU and free 5-FU while the plain HMSNs did not show significant cytotoxicity. The mechanism of EGF-HMSNs-5-FU in overcoming drug resistance in SW480/ADR cells could be attributed to the specific internalization of EGF-HMSNs-5-FU in EGFR overexpressed cells which can lead to high intracellular drug accumulation and cause cell death through S phase arrest.Acquired drug resistance (ADR) can be developed in colorectal cancer cells after 5-fluorouracil (5-FU) treatment and diminish the effectiveness of chemotherapy. In this work, acquired 5-FU resistance in the colorectal cancer cell line SW480 was obtained with the up-regulation of dihydropyrimidine dehydrogenase (DPYD) gene expression which can convert 5-FU to its inactive metabolite. To overcome ADR in colorectal cancer, hollow mesoporous silica nanoparticles (HMSNs) grafted with epidermal growth factor (EGF) were used as nanocarriers to deliver 5-FU to colorectal cancer cells with acquired drug resistance. The

Synthesis, characterization and in vitro studies of doxorubicin-loaded magnetic nanoparticles grafted to smart copolymers on A549 lung cancer cell line.

Science.gov (United States)

Akbarzadeh, Abolfazl; Samiei, Mohammad; Joo, Sang Woo; Anzaby, Maryam; Hanifehpour, Younes; Nasrabadi, Hamid Tayefi; Davaran, Soodabeh

2012-12-18

The aim of present study was to develop the novel methods for chemical and physical modification of superparamagnetic iron oxide nanoparticles (SPIONs) with polymers via covalent bonding entrapment. These modified SPIONs were used for encapsulation of anticancer drug doxorubicin. At first approach silane-grafted magnetic nanoparticles was prepared and used as a template for polymerization of the N-isopropylacrylamide (NIPAAm) and methacrylic acid (MAA) via radical polymerization. This temperature/pH-sensitive copolymer was used for preparation of DOX-loaded magnetic nanocomposites. At second approach Vinyltriethoxysilane-grafted magnetic nanoparticles were used as a template to polymerize PNIPAAm-MAA in 1, 4 dioxan and methylene-bis-acrylamide (BIS) was used as a cross-linking agent. Chemical composition and magnetic properties of Dox-loaded magnetic hydrogel nanocomposites were analyzed by FT-IR, XRD, and VSM. The results demonstrate the feasibility of drug encapsulation of the magnetic nanoparticles with NIPAAm-MAA copolymer via covalent bonding. The key factors for the successful prepardtion of magnetic nanocomposites were the structure of copolymer (linear or cross-linked), concentration of copolymer and concentration of drug. The influence of pH and temperature on the release profile of doxorubicin was examined. The in vitro cytotoxicity test (MTT assay) of both magnetic DOx-loaded nanoparticles was examined. The in vitro tests showed that these systems are no toxicity and are biocompatible. IC50 of DOx-loaded Fe3O4 nanoparticles on A549 lung cancer cell line showed that systems could be useful in treatment of lung cancer.

ZnO nanostructure fabrication in different solvents transforms physio-chemical, biological and photodegradable properties

Energy Technology Data Exchange (ETDEWEB)

Ali, Attarad; Ambreen, Sidra; Javed, Rabia; Tabassum, Saira [Department of Biotechnology, Quaid-i-Azam University, Islamabad 45320 (Pakistan); Ul Haq, Ihsan [Department of Pharmacy, Quaid-i-Azam University, Islamabad 45320 (Pakistan); Zia, Muhammad, E-mail: ziachaudhary@gmail.com [Department of Biotechnology, Quaid-i-Azam University, Islamabad 45320 (Pakistan)

2017-05-01

Zinc oxide (ZnO) nanostructures are synthesized in various organic solvents (acetone, chloroform, ethyl acetate, ethanol and methanol) and water via coprecipitation process using zinc acetate as precursor. The resultant ZnO nanoparticles, nano rods and nano sheets are characterized by UV–vis spectrophotometric analysis, scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transmission infrared spectroscopy (FTIR), and energy dispersive X-ray spectroscopy (EDX). The variable size and geometry of nanoparticles depend upon medium used for synthesis. The synthesized ZnO nanostructures exhibit minor to moderate antioxidative (DPPH based free radical scavenging activity, total antioxidative potential and total reducing power) response. Mild to moderate antibacterial and antifungal activities, excellent antileishmanial potential (IC50 up to 3.76), and good cytotoxic perspective (LD50 up to 49.4) is also observed by the synthesized ZnO NPs. The nanoparticles also exhibit moderate α-amylase inhibition response. Furthermore the nanostructures are evaluated for methylene blue photodegradation response within 60 min time period. It is found that organic solvent alters shape, size and other physio-chemical properties of ZnO that ultimately modulate the biological, chemical, and environmental properties. - Highlights: • Zinc oxide nanoparticles are fabricated in different solvents using co-precipitation method • SEM, XRD and FTIR analysis confirms variation in physical and chemical characteristics of synthesized ZnO NPs • The synthesized ZnO demonstrates variation in biological, phytochemical and photodegradable properties.

ZnO nanostructure fabrication in different solvents transforms physio-chemical, biological and photodegradable properties

International Nuclear Information System (INIS)

Ali, Attarad; Ambreen, Sidra; Javed, Rabia; Tabassum, Saira; Ul Haq, Ihsan; Zia, Muhammad

2017-01-01

Zinc oxide (ZnO) nanostructures are synthesized in various organic solvents (acetone, chloroform, ethyl acetate, ethanol and methanol) and water via coprecipitation process using zinc acetate as precursor. The resultant ZnO nanoparticles, nano rods and nano sheets are characterized by UV–vis spectrophotometric analysis, scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transmission infrared spectroscopy (FTIR), and energy dispersive X-ray spectroscopy (EDX). The variable size and geometry of nanoparticles depend upon medium used for synthesis. The synthesized ZnO nanostructures exhibit minor to moderate antioxidative (DPPH based free radical scavenging activity, total antioxidative potential and total reducing power) response. Mild to moderate antibacterial and antifungal activities, excellent antileishmanial potential (IC50 up to 3.76), and good cytotoxic perspective (LD50 up to 49.4) is also observed by the synthesized ZnO NPs. The nanoparticles also exhibit moderate α-amylase inhibition response. Furthermore the nanostructures are evaluated for methylene blue photodegradation response within 60 min time period. It is found that organic solvent alters shape, size and other physio-chemical properties of ZnO that ultimately modulate the biological, chemical, and environmental properties. - Highlights: • Zinc oxide nanoparticles are fabricated in different solvents using co-precipitation method • SEM, XRD and FTIR analysis confirms variation in physical and chemical characteristics of synthesized ZnO NPs • The synthesized ZnO demonstrates variation in biological, phytochemical and photodegradable properties.

[Free tissue transfers with lengthening of vascular pedicle using interpositional vein grafts. About 10 cases].

Science.gov (United States)

Yeo, S; Perrot, P; Duteille, F

2010-04-01

The realization of free flaps with lack of reliable vessels nearby the loss of substance is a difficult problem for plastic surgeons. We report 10 cases of free tissue transfers with a one-stage technique lengthening the vascular pedicle of the free flap with interpositional vein grafts. Taking into consideration the good results and the low rate of morbidity, the authors emphasize the use of this technique rather than a two-stage procedure. Copyright 2009 Elsevier Masson SAS. All rights reserved.

Solvent-free synthesis of nanosized hierarchical sodalite zeolite with a multi-hollow polycrystalline structure

KAUST Repository

Zeng, Shangjing; Wang, Runwei; Li, Ang; Huang, Weiwei; Zhang, Zongtao; Qiu, Shilun

2016-01-01

A solvent-free route is developed for preparing nanoscale sodalite zeolite with a multi-hollow structure. Furthermore, the synthesis of nanosized hollow sodalite polycrystalline aggregates with a mesoporous structure and high crystallinity

Production of starch nanoparticles by dissolution and non-solvent precipitation for use in food-grade Pickering emulsions.

Science.gov (United States)

Saari, Hisfazilah; Fuentes, Catalina; Sjöö, Malin; Rayner, Marilyn; Wahlgren, Marie

2017-02-10

The aim of this study was to investigate non-solvent precipitation of starch to produce nanoparticles that could be used in Pickering emulsions. The material used was waxy maize, modified with octenyl succinic anhydride. Different methods of non-solvent precipitation were investigated, and a method based on direct mixing of an 8% starch solution and ethanol (ratio 1:1) was found to produce the smallest particles. The particle size was measured using AFM and AF4, and was found to be in the range 100-200nm. However, both larger particles and aggregates of nanoparticles were observed. The emulsion produced using the precipitated starch particles had a droplet size that between 0.5 and 45μm, compared to emulsions produced from waxy maize granules, in which had a size of 10-100μm. The drop in size contributed to increased stability against creaming. The amount of starch used for emulsion stabilization could also be substantially reduced. Copyright © 2016 The Author(s). Published by Elsevier Ltd.. All rights reserved.

xanthen-11-ones by ZnO Nanoparticles Catalyzed Three Co

African Journals Online (AJOL)

NICO

Highly effective zinc oxide nanoparticles catalyzed solvent-free synthesis of some tetrahydrobenzo[a]xanthen-11-one derivatives ... efficient, green and simple method for the preparation of ... Characterization of ZnO NPs structure was continued by SEM ... catalysts may be related to higher surface area available for.

Graft-copolymerization onto carbon black

International Nuclear Information System (INIS)

Nakase, Yoshiaki; Nishii, Masanobu; Kijima, Toshiyuki; Kato, Hiroshi.

1988-07-01

Radiation-induced graft copolymerization of vinyl monomer onto carbon black was performed. During the γ-ray- and electron beam-induced polymerization (In-source), or the electron beam post-polymerization, the graft-copolymerization behavior was affected by the kinds of both carbon blacks and monomers, i.e. the smaller the size of carbon black particles, the higher the apparent grafted fraction. Homopolymer in the grafted carbon black samples was washed out by the solvent of the polymer, and the extracted polymer seemed to be dimer or trimer of the used monomer. In the case of the post-polymerization with the pre-irradiation doses of 50 Mrad, homopolymer was hardly observed. The polymer sheets of plastics or rubbers with grafted carbon black had an electrical conductivity unalterable considerably by the heating cycles. The particles of grafted carbon black in the sheet might be kept much more at the surface layer within 100 nm depth than at the inner layer. (author)

(BDMCA) Nanoparticles

African Journals Online (AJOL)

Erah

Available online at http://www.tjpr.org. Research Article ... Methods: Nanoparticle formulations were fabricated by a double emulsion solvent evaporation technique using .... Characterization of BDMCA nanoparticles. The nanoparticle ...

Radiation-induced grafting of TMPM onto polypropylene

International Nuclear Information System (INIS)

Wang Huiliang; Li Hong; Chen Wenxiu

1995-01-01

The gamma radiation-induced graft copolymerization of 2,2,6,6-tetramethyl-4-piperidinyl-methacrylate (TMPM), a very effective hindered amine light stabilizer (HALS), onto polypropylene was investigated by simultaneous- irradiation technique. The various synthesis conditions on the graft content was studied. It was found that benzene, CCl 4 and petroleum ether are more effective than other solvents, the percent grafting reached 7.1% for benzene. The percent grafting is higher when graft copolymerization is carried out in argon atmosphere than those in air. For all the grafting copolymerization carried out in benzene and CCl 4 , percent grafting increase linearly from 1 to 5 Mrad and beyond 5 Mrad, a tendency to level off appeared. At a constant dose, the percent grafting was found to be higher at high dose rate until 228 rad/s. Percent grafting also increased continuously with increasing monomer concentration up to 2.85 mol/L, but significant increase in grafting was observed only up to 1.14 mol/L

Parallel array of nanochannels grafted with polymer-brushes-stabilized Au nanoparticles for flow-through catalysis.

Science.gov (United States)

Liu, Jianxi; Ma, Shuanhong; Wei, Qiangbing; Jia, Lei; Yu, Bo; Wang, Daoai; Zhou, Feng

2013-12-07

Smart systems on the nanometer scale for continuous flow-through reaction present fascinating advantages in heterogeneous catalysis, in which a parallel array of straight nanochannels offers a platform with high surface area for assembling and stabilizing metallic nanoparticles working as catalysts. Herein we demonstrate a method for finely modifying the nanoporous anodic aluminum oxide (AAO), and further integration of nanoreactors. By using atomic transfer radical polymerization (ATRP), polymer brushes were successfully grafted on the inner wall of the nanochannels of the AAO membrane, followed by exchanging counter ions with a precursor for nanoparticles (NPs), and used as the template for deposition of well-defined Au NPs. The membrane was used as a functional nanochannel for novel flow-through catalysis. High catalytic performance and instantaneous separation of products from the reaction system was achieved in reduction of 4-nitrophenol.

Parallel array of nanochannels grafted with polymer-brushes-stabilized Au nanoparticles for flow-through catalysis

Science.gov (United States)

Liu, Jianxi; Ma, Shuanhong; Wei, Qiangbing; Jia, Lei; Yu, Bo; Wang, Daoai; Zhou, Feng

2013-11-01

Smart systems on the nanometer scale for continuous flow-through reaction present fascinating advantages in heterogeneous catalysis, in which a parallel array of straight nanochannels offers a platform with high surface area for assembling and stabilizing metallic nanoparticles working as catalysts. Herein we demonstrate a method for finely modifying the nanoporous anodic aluminum oxide (AAO), and further integration of nanoreactors. By using atomic transfer radical polymerization (ATRP), polymer brushes were successfully grafted on the inner wall of the nanochannels of the AAO membrane, followed by exchanging counter ions with a precursor for nanoparticles (NPs), and used as the template for deposition of well-defined Au NPs. The membrane was used as a functional nanochannel for novel flow-through catalysis. High catalytic performance and instantaneous separation of products from the reaction system was achieved in reduction of 4-nitrophenol.

Efficient synthesis of sulfonamide derivatives on solid supports catalyzed using solvent-free and microwave-assisted methods

Energy Technology Data Exchange (ETDEWEB)

Camargo-Ordonez, Argelia; Moreno-Reyes, Christian; Olazaran-Santibanez, Fabian; Martinez-Hernandez, Sheila; Bocanegra-Garcia, Virgilio; Rivera, Gildardo [Universidad Autonoma de Tamaulipas, Reynosa (Mexico). Dep. de Farmacia y Quimica Medicinal

2011-07-01

In this work we report the synthesis of sulfonamide derivatives using a conventional procedure and with solid supports, such as silica gel, florisil, alumina, 4A molecular sieves, montmorillonite KSF, and montmorillonite K10 using solvent-free and microwave-assisted methods. Our results show that solid supports have a catalytic activity in the formation of sulfonamide derivatives. We found that florisil, montmorillonite KSF, and K10 could be used as inexpensive alternative catalysts that are easily separated from the reaction media. Additionally, solvent-free and microwave-assisted methods were more efficient in reducing reaction time and in increasing yield. (author)

Efficient synthesis of sulfonamide derivatives on solid supports catalyzed using solvent-free and microwave-assisted methods

International Nuclear Information System (INIS)

Camargo-Ordonez, Argelia; Moreno-Reyes, Christian; Olazaran-Santibanez, Fabian; Martinez-Hernandez, Sheila; Bocanegra-Garcia, Virgilio; Rivera, Gildardo

2011-01-01

In this work we report the synthesis of sulfonamide derivatives using a conventional procedure and with solid supports, such as silica gel, florisil, alumina, 4A molecular sieves, montmorillonite KSF, and montmorillonite K10 using solvent-free and microwave-assisted methods. Our results show that solid supports have a catalytic activity in the formation of sulfonamide derivatives. We found that florisil, montmorillonite KSF, and K10 could be used as inexpensive alternative catalysts that are easily separated from the reaction media. Additionally, solvent-free and microwave-assisted methods were more efficient in reducing reaction time and in increasing yield. (author)

Characteristics of tau oligomers

Directory of Open Access Journals (Sweden)

Yan eRen

2013-07-01

Full Text Available In Alzheimer disease (AD and other tauopathies, microtubule-associated protein tau becomes hyperphosphorylated, undergoes conformational changes, aggregates, eventually becoming neurofibrillary tangles (NFTs. As accumulating evidence suggests that NFTs themselves may not be toxic, attention is now turning toward the role of intermediate tau oligomers in AD pathophysiology. Sarkosyl extraction is a standard protocol for investigating insoluble tau aggregates in brains. There is a growing consensus that sarkosyl-insoluble tau correlates with the pathological features of tauopathy. While sarkosyl-insoluble tau from tauopathy brains has been well characterized as a pool of filamentous tau, other dimers, multimers, and granules of tau are much less well understood. There are protocols for identifying these tau oligomers. In this mini review, we discuss the characteristics of tau oligomers isolated via different methods and materials.

Grafting

Energy Technology Data Exchange (ETDEWEB)

Garnett, J L [New South Wales Univ., Kensington (Australia). School of Chemistry

1979-01-01

The unique value of ionizing radiation for the initiation of grafting to backbone polymers is discussed. The principles of the technique are briefly reviewed. The conditions under which free radicals and ions participate in these reactions are examined. Examples of representative grafting processes are considered to illustrate where the technique can be of potential commercial value to a wide range of industries. The general principles of these grafting reactions are shown to be applicable to radiation induced rapid cure technology such as is provided by electron beam processing facilities. Grafting reactions initiated by UV are also treated and shown to be of importance because of the many similarities in properties of the ionizing radiation and UV systems, also the rapid industrial exploitation of EB and sensitized UV processing technology. Possible future trends in radiation grafting are outlined.

Surface interaction forces of cellulose nanocrystals grafted with thermoresponsive polymer brushes.

Science.gov (United States)

Zoppe, Justin O; Osterberg, Monika; Venditti, Richard A; Laine, Janne; Rojas, Orlando J

2011-07-11

The colloidal stability and thermoresponsive behavior of poly(N-isopropylacrylamide) brushes grafted from cellulose nanocrystals (CNCs) of varying graft densities and molecular weights was investigated. Indication of the grafted polymer brushes was obtained after AFM imaging of CNCs adsorbed on silica. Also, aggregation of the nanoparticles carrying grafts of high degree of polymerization was observed. The responsiveness of grafted CNCs in aqueous dispersions and as an ultrathin film was evaluated by using light scattering, viscosimetry, and colloidal probe microscopy (CPM). Light transmittance measurements showed temperature-dependent aggregation originating from the different graft densities and molecular weights. The lower critical solution temperature (LCST) of grafted poly(NiPAAm) brushes was found to decrease with the ionic strength, as is the case for free poly(NiPAAm) in aqueous solution. Thermal responsive behavior of grafted CNCs in aqueous dispersions was observed by a sharp increase in dispersion viscosity as the temperature approached the LCST. CPM in liquid media for asymmetric systems consisting of ultrathin films of CNCs and a colloidal silica probe showed the distinctive effects of the grafted polymer brushes on interaction and adhesive forces. The origin of such forces was found to be mainly electrostatic and steric in the case of bare and grafted CNCs, respectively. A decrease in the onset of attractive and adhesion forces of grafted CNCs films were observed with the ionic strength of the aqueous solution. The decreased mobility of polymer brushes upon partial collapse and decreased availability of hydrogen bonding sites with higher electrolyte concentration were hypothesized as the main reasons for the less prominent polymer bridging between interacting surfaces.

Magnetic resonance imaging of mouse islet grafts labeled with novel chitosan-coated superparamagnetic iron oxide nanoparticles.

Directory of Open Access Journals (Sweden)

Jyuhn-Huarng Juang

Full Text Available To better understand the fate of islet isografts and allografts, we utilized a magnetic resonance (MR imaging technique to monitor mouse islets labeled with a novel MR contrast agent, chitosan-coated superparamagnetic iron oxide (CSPIO nanoparticles.After being incubated with and without CSPIO (10 µg/ml, C57BL/6 mouse islets were examined under transmission electron microscope (TEM and their insulin secretion was measured. Cytotoxicity was examined in α (αTC1 and β (NIT-1 and βTC cell lines as well as islets. C57BL/6 mice were used as donors and inbred C57BL/6 and Balb/c mice were used as recipients of islet transplantation. Three hundred islets were transplanted under the left kidney capsule of each mouse and then MR was performed in the recipients periodically. At the end of study, the islet graft was removed for histology and TEM studies.After incubation of mouse islets with CSPIO (10 µg/mL, TEM showed CSPIO in endocytotic vesicles of α- and β-cells at 8 h. Incubation with CSPIO did not affect insulin secretion from islets and death rates of αTC1, NIT-1 and βTC cell lines as well as islets. After syngeneic and allogeneic transplantation, grafts of CSPIO-labeled islets were visualized on MR scans as persistent hypointense areas. At 8 weeks after syngeneic transplantation and 31 days after allogeneic transplantation, histology of CSPIO-labeled islet grafts showed colocalized insulin and iron staining in the same areas but the size of allografts decreased with time. TEM with elementary iron mapping demonstrated CSPIO distributed in the cytoplasm of islet cells, which maintained intact ultrastructure.Our results indicate that after syngeneic and allogeneic transplantation, islets labeled with CSPIO nanoparticles can be effectively and safely imaged by MR.

Antimicrobial nanocapsules: from new solvent-free process to in vitro efficiency

Directory of Open Access Journals (Sweden)

Steelandt J

2014-09-01

Full Text Available Julie Steelandt,1 Damien Salmon,1,2 Elodie Gilbert,1 Eyad Almouazen,3 François NR Renaud,4 Laurène Roussel,1 Marek Haftek,5 Fabrice Pirot1,2 1University Claude Bernard Lyon 1, Faculty of Pharmacy, Fundamental, Clinical and Therapeutic Aspects of Skin Barrier Function, FRIPharm, Laboratoire de Pharmacie Galénique Industrielle, 2Hospital Pharmacy, FRIPharm, Hospital Edouard Herriot, Hospices Civils de Lyon, 3Laboratoire d’Automatique et de Génie des Procédés, University Claude Bernard Lyon 1, 4University Claude Bernard Lyon 1, UMR CNRS 5510/MATEIS, 5University Claude Bernard Lyon 1, Faculty of Pharmacy, Fundamental, Clinical and Therapeutic Aspects of Skin Barrier Function, FRIPharm, Laboratoire de Dermatologie, Lyon, France Abstract: Skin and mucosal infections constitute recurrent pathologies resulting from either inappropriate antiseptic procedures or a lack of efficacy of antimicrobial products. In this field, nanomaterials offer interesting antimicrobial properties (eg, long-lasting activity; intracellular and tissular penetration as compared to conventional products. The aim of this work was to produce, by a new solvent-free process, a stable and easily freeze-dryable chlorhexidine-loaded polymeric nanocapsule (CHX-NC suspension, and then to assess the antimicrobial properties of nanomaterials. The relevance of the process and the physicochemical properties of the CHX-NCs were examined by the assessment of encapsulation efficiency, stability of the nanomaterial suspension after 1 month of storage, and by analysis of granulometry and surface electric charge of nanocapsules. In vitro antimicrobial activities of the CHX-NCs and chlorhexidine digluconate solution were compared by measuring the inhibition diameters of two bacterial strains (Escherichia coli and Staphylococcus aureus and one fungal strain (Candida albicans cultured onto appropriate media. Based on the findings of this study, we report a new solvent-free process for the

Modeling Loop Reorganization Free Energies of Acetylcholinesterase: A Comparison of Explicit and Implicit Solvent Models

National Research Council Canada - National Science Library

Olson, Mark

2004-01-01

... screening of charge-charge interactions. This paper compares different solvent models applied to the problem of estimating the free-energy difference between two loop conformations in acetylcholinesterase...

Novel free paclitaxel-loaded poly(L-γ-glutamylglutamine–paclitaxel nanoparticles

Directory of Open Access Journals (Sweden)

Danbo Yang

2011-01-01

Full Text Available Danbo Yang1, Sang Van2, Xinguo Jiang3, Lei Yu1,21Biomedical Engineering and Technology Institute, Institutes for Advanced Interdisciplinary Research, East China Normal University, Shanghai, People's Republic of China; 2Biomedical Group, Nitto Denko Technical Corporation, Oceanside, CA, USA; 3School of Pharmacy, Fudan University, Shanghai, People's Republic of ChinaAbstract: The purpose of this study was to develop a novel formulation of paclitaxel (PTX that would improve its therapeutic index. Here, we combined a concept of polymer–PTX drug conjugate with a concept of polymeric micelle drug delivery to form novel free PTX-loaded poly(L-γ-glutamylglutamine (PGG–PTX conjugate nanoparticles. The significance of this drug formulation emphasizes the simplicity, novelty, and flexibility of the method of forming nanoparticles that contain free PTX and conjugated PTX in the same drug delivery system. The results of effectively inhibiting tumor growth in mouse models demonstrated the feasibility of the nanoparticle formulation. The versatility and potential of this dual PTX drug delivery system can be explored with different drugs for different indications. Novel and simple formulations of PTX-loaded PGG–PTX nanoparticles could have important implications in translational medicines.Keywords: paclitaxel, polymeric micelle, poly(L-γ-glutamylglutamine–paclitaxel, nanoconjugate, nanoparticles

Tuning of Activated Carbon for Solvent-Free Oxidation of Cyclohexane

Directory of Open Access Journals (Sweden)

Mohammad Sadiq

2017-01-01

Full Text Available Activated carbon (AC was prepared from carbonization of phosphoric acid soaked peanut shell at 380°C under inert atmosphere followed by activation with hydrogen peroxide. The AC was characterized by SEM, EDX, FTIR, TGA, and BET surface area and pore size analyzer. The potential of AC as a catalyst for solvent-free oxidation of cyclohexane to cyclohexanol and cyclohexanone (the mixture is known as KA oil in the presence of molecular oxygen at moderate temperature was investigated in a self-designed double-walled three-necked batch reactor. The effect of different reaction parameters/additive was optimized. The maximum productivity value (2.14 mmolg−1 h−1, without base, and 4.85 mmolg−1 h−1, with 0.2 mmol NaOH of the desired product was achieved under optimal reaction parameters: vol 12.5 mL, cat 0.4 g, time 14 h, oxygen flow 40 mL/min (pO2 760 Torr, stirring 1100 rpm, and temp 75°C. The AC shows recyclability for multiple runs without any significant loss in activity. Thus, the AC can be an efficient catalyst, due to low cost, ease of synthesis, easy recovery, nonleaching, and recyclability for multiple uses for the solvent-free oxidation of cyclohexane.

Reduced intensity haplo plus single cord transplant compared to double cord transplant: improved engraftment and graft-versus-host disease-free, relapse-free survival

Science.gov (United States)

van Besien, Koen; Hari, Parameswaran; Zhang, Mei-Jie; Liu, Hong-Tao; Stock, Wendy; Godley, Lucy; Odenike, Olatoyosi; Larson, Richard; Bishop, Michael; Wickrema, Amittha; Gergis, Usama; Mayer, Sebastian; Shore, Tsiporah; Tsai, Stephanie; Rhodes, Joanna; Cushing, Melissa M.; Korman, Sandra; Artz, Andrew

2016-01-01

Umbilical cord blood stem cell transplants are commonly used in adults lacking HLA-identical donors. Delays in hematopoietic recovery contribute to mortality and morbidity. To hasten recovery, we used co-infusion of progenitor cells from a partially matched related donor and from an umbilical cord blood graft (haplo-cord transplant). Here we compared the outcomes of haplo-cord and double-cord transplants. A total of 97 adults underwent reduced intensity conditioning followed by haplo-cord transplant and 193 patients received reduced intensity conditioning followed by double umbilical cord blood transplantation. Patients in the haplo-cord group were more often from minority groups and had more advanced malignancy. Haplo-cord recipients received fludarabine-melphalan-anti-thymocyte globulin. Double umbilical cord blood recipients received fludarabine-cyclophosphamide and low-dose total body irradiation. In a multivariate analysis, haplo-cord had faster neutrophil (HR=1.42, P=0.007) and platelet (HR=2.54, Pdisease (HR=0.26, Pdisease (HR=0.06, Pdisease-free, relapse-free survival was superior with haplo-cord (HR 0.63, P=0.002) but not overall survival (HR=0.97, P=0.85). Haplo-cord transplantation using fludarabine-melphalan-thymoglobulin conditioning hastens hematopoietic recovery with a lower risk of relapse relative to double umbilical cord blood transplantation using the commonly used fludarabine-cyclophosphamide-low-dose total body irradiation conditioning. Graft-versus-host disease-free and relapse-free survival is significantly improved. Haplo-cord is a readily available graft source that improves outcomes and access to transplant for those lacking HLA-matched donors. Trials registered at clinicaltrials.gov identifiers 00943800 and 01810588. PMID:26869630

Ester-free Thiol-X Resins: New Materials with Enhanced Mechanical Behavior and Solvent Resistance

OpenAIRE

Podgórski, Maciej; Becka, Eftalda; Chatani, Shunsuke; Claudino, Mauro; Bowman, Christopher N.

2015-01-01

A series of thiol-Michael and radical thiol-ene network polymers were successfully prepared from ester-free as well as ester-containing monomer formulations. Polymerization reaction rates, dynamic mechanical analysis, and solvent resistance experiments were performed and compared between compositions with varied ester loading. The incorporation of ester-free alkyl thiol, vinyl sulfone and allylic monomers significantly improved the mechanical properties when compared with commercial, mercapto...

Synthesis and Self-Assembly of Chiral Cylindrical Molecular Complexes: Functional Heterogeneous Liquid-Solid Materials Formed by Helicene Oligomers

Directory of Open Access Journals (Sweden)

Nozomi Saito

2018-01-01

Full Text Available Chiral cylindrical molecular complexes of homo- and hetero-double-helices derived from helicene oligomers self-assemble in solution, providing functional heterogeneous liquid-solid materials. Gels and liotropic liquid crystals are formed by fibril self-assembly in solution; molecular monolayers and fibril films are formed by self-assembly on solid surfaces; gels containing gold nanoparticles emit light; silica nanoparticles aggregate and adsorb double-helices. Notable dynamics appears during self-assembly, including multistep self-assembly, solid surface catalyzed double-helix formation, sigmoidal and stairwise kinetics, molecular recognition of nanoparticles, discontinuous self-assembly, materials clocking, chiral symmetry breaking and homogeneous-heterogeneous transitions. These phenomena are derived from strong intercomplex interactions of chiral cylindrical molecular complexes.

Grafting functional antioxidants on highly crosslinked polyethylene

Science.gov (United States)

Al-Malaika, S.; Riasat, S.; Lewucha, C.

2016-05-01

The problem of interference of antioxidants, such as hindered phenols, with peroxide-initiated crosslinking of polyethylene was addressed through the use of functional (reactive) graftable antioxidants (g-AO). Reactive derivatives of hindered phenol and hindered amine antioxidants were synthesised, characterised and used to investigate their grafting reactions in high density polyethylene; both non-crosslinked (PE) and highly peroxide-crosslinked (PEXa). Assessment of the extent of in-situ grafting of the antioxidants, their retention after exhaustive solvent extraction in PE and PEXa, and the stabilising performance of the grafted antioxidants (g-AO) in the polymer were examined and benchmarked against conventionally stabilised crosslinked & non-crosslinked polyethylene. It was shown that the functional antioxidants graft to a high extent in PEXa, and that the level of interference of the g-AOs with the polymer crosslinking process was minimal compared to that of conventional antioxidants which bear the same antioxidant function. The much higher level of retention of the g-AOs in PEXa after exhaustive solvent extraction, compared to that of the corresponding conventional antioxidants, accounts for their superior long-term thermal stabilising performance under severe extractive conditions.

Effects of Solvent and Temperature on Free Radical Formation in Electronic Cigarette Aerosols.

Science.gov (United States)

Bitzer, Zachary T; Goel, Reema; Reilly, Samantha M; Foulds, Jonathan; Muscat, Joshua; Elias, Ryan J; Richie, John P

2018-01-16

The ever-evolving market of electronic cigarettes (e-cigarettes) presents a challenge for analyzing and characterizing the harmful products they can produce. Earlier we reported that e-cigarette aerosols can deliver high levels of reactive free radicals; however, there are few data characterizing the production of these potentially harmful oxidants. Thus, we have performed a detailed analysis of the different parameters affecting the production of free radical by e-cigarettes. Using a temperature-controlled e-cigarette device and a novel mechanism for reliably simulating e-cigarette usage conditions, including coil activation and puff flow, we analyzed the effects of temperature, wattage, and e-liquid solvent composition of propylene glycol (PG) and glycerol (GLY) on radical production. Free radicals in e-cigarette aerosols were spin-trapped and analyzed using electron paramagnetic resonance. Free radical production increased in a temperature-dependent manner, showing a nearly 2-fold increase between 100 and 300 °C under constant-temperature conditions. Free radical production under constant wattage showed an even greater increase when going from 10 to 50 W due, in part, to higher coil temperatures compared to constant-temperature conditions. The e-liquid PG content also heavily influenced free radical production, showing a nearly 3-fold increase upon comparison of ratios of 0:100 (PG:GLY) and 100:0 (PG:GLY). Increases in PG content were also associated with increases in aerosol-induced oxidation of biologically relevant lipids. These results demonstrate that the production of reactive free radicals in e-cigarette aerosols is highly solvent dependent and increases with an increase in temperature. Radical production was somewhat dependent on aerosol production at higher temperatures; however, disproportionately high levels of free radicals were observed at ≥100 °C despite limited aerosol production. Overall, these findings suggest that e-cigarettes can be

A facile and flexible process of β-cyclodextrin grafted on Fe3O4 magnetic nanoparticles and host-guest inclusion studies

International Nuclear Information System (INIS)

Zhu Jie; He Jiang; Du Xiaoyan; Lu Ruihua; Huang Lizhen; Ge Xia

2011-01-01

In this study, a kind of novel surface-functionalized magnetic nanoparticles was fabricated by the Fe 3 O 4 nanoparticles surface modification with mono-6-deoxy-6-(p-tolylsulfonyl)-cyclodextrin (6-TsO-β-CD), which were employed to interact with uric acid and their behavior was investigated by electrochemical methods. The architecture has been characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectra (FT-IR), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA), which confirmed that cyclodextrins have been effectively functionalized on the surface of Fe 3 O 4 nanoparticles. The analyses of vibration sample magnetometer (VSM) verified that the nanoparticles owned good magnetic property. The grafted β-cyclodextrin on the Fe3O4 nanoparticles contributed to as a modified electrode for detecting uric acid with cyclic voltammograms. Electrochemical results revealed that the new materials could exhibit excellent molecules recognition ability and show high electrochemical response. The new nanoparticles simultaneously had unique properties of magnetic nanoparticles and cyclodextrins through combining their individual distinct advantages.

Nanoscale Organic Hybrid Electrolytes

KAUST Repository

Nugent, Jennifer L.

2010-08-20

Nanoscale organic hybrid electrolytes are composed of organic-inorganic hybrid nanostructures, each with a metal oxide or metallic nanoparticle core densely grafted with an ion-conducting polyethylene glycol corona - doped with lithium salt. These materials form novel solvent-free hybrid electrolytes that are particle-rich, soft glasses at room temperature; yet manifest high ionic conductivity and good electrochemical stability above 5V. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoscale Organic Hybrid Electrolytes

KAUST Repository

Nugent, Jennifer L.; Moganty, Surya S.; Archer, Lynden A.

2010-01-01

Nanoscale organic hybrid electrolytes are composed of organic-inorganic hybrid nanostructures, each with a metal oxide or metallic nanoparticle core densely grafted with an ion-conducting polyethylene glycol corona - doped with lithium salt. These materials form novel solvent-free hybrid electrolytes that are particle-rich, soft glasses at room temperature; yet manifest high ionic conductivity and good electrochemical stability above 5V. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An extended study of the phase separation between phospholipids and grafted polymers on a bilayer biomembrane

Energy Technology Data Exchange (ETDEWEB)

Benhamou, M; Joudar, I; Kaidi, H; Elhasnaoui, K; Ridouane, H; Qamar, H, E-mail: benhamou.mabrouk@gmail.com [Laboratoire de Physique des Polymeres et Phenomenes Critiques, Faculte des Sciences, Ben M' sik, PO Box 7955, Casablanca (Morocco)

2011-06-01

We re-examine here the phase separation between phospholipids and adsorbed polymer chains on a fluid membrane with a change in some suitable parameter (temperature). Our purpose is to quantify the significant effects of the solvent quality and of the polydispersity of adsorbed loops formed by grafted polymer chains on the segregation phenomenon. To this end, we elaborate on a theoretical model that allows us to derive the expression for the mixing free energy. From this, we extract the phase diagram shape in the composition-temperature plane. Our main conclusion is that the polymer chain condensation is very sensitive to the solvent quality and to the polydispersity of loops of adsorbed chains.

Development of silane grafted ZnO core shell nanoparticles loaded diglycidyl epoxy nanocomposites film for antimicrobial applications.

Science.gov (United States)

Suresh, S; Saravanan, P; Jayamoorthy, K; Ananda Kumar, S; Karthikeyan, S

2016-07-01

In this article a series of epoxy nanocomposites film were developed using amine functionalized (ZnO-APTES) core shell nanoparticles as the dispersed phase and a commercially available epoxy resin as the matrix phase. The functional group of the samples was characterized using FT-IR spectra. The most prominent peaks of epoxy resin were found in bare epoxy and in all the functionalized ZnO dispersed epoxy nanocomposites (ZnO-APTES-DGEBA). The XRD analysis of all the samples exhibits considerable shift in 2θ, intensity and d-spacing values but the best and optimum concentration is found to be 3% ZnO-APTES core shell nanoparticles loaded epoxy nanocomposites supported by FT-IR results. From TGA measurements, 100wt% residue is obtained in bare ZnO nanoparticles whereas in ZnO core shell nanoparticles grafted DGEBA residue percentages are 37, 41, 45, 46 and 52% for 0, 1, 3, 5 and 7% ZnO-APTES-DGEBA respectively, which is confirmed with ICP-OES analysis. From antimicrobial activity test, it was notable that antimicrobial activity of 7% ZnO-APTES core shell nanoparticles loaded epoxy nanocomposite film has best inhibition zone effect against all pathogens under study. Copyright © 2016 Elsevier B.V. All rights reserved.

Modification of the surface of superparamagnetic iron oxide nanoparticles to enable their safe application in humans.

Science.gov (United States)

Strehl, Cindy; Maurizi, Lionel; Gaber, Timo; Hoff, Paula; Broschard, Thomas; Poole, A Robin; Hofmann, Heinrich; Buttgereit, Frank

Combined individually tailored methods for diagnosis and therapy (theragnostics) could be beneficial in destructive diseases, such as rheumatoid arthritis. Nanoparticles are promising candidates for theragnostics due to their excellent biocompatibility. Nanoparticle modifications, such as improved surface coating, are in development to meet various requirements, although safety concerns mean that modified nanoparticles require further review before their use in medical applications is permitted. We have previously demonstrated that iron oxide nanoparticles with amino-polyvinyl alcohol (a-PVA) adsorbed on their surfaces have the unwanted effect of increasing human immune cell cytokine secretion. We hypothesized that this immune response was caused by free-floating PVA. The aim of the present study was to prevent unwanted immune reactions by further surface modification of the a-PVA nanoparticles. After cross-linking of PVA to nanoparticles to produce PVA-grafted nanoparticles, and reduction of their zeta potential, the effects on cell viability and cytokine secretion were analyzed. PVA-grafted nanoparticles still stimulated elevated cytokine secretion from human immune cells; however, this was inhibited after reduction of the zeta potential. In conclusion, covalent cross-linking of PVA to nanoparticles and adjustment of the surface charge rendered them nontoxic to immune cells, nonimmunogenic, and potentially suitable for use as theragnostic agents.

Grafting of acrylamide onto synthetic co polyamide by gamma irradiation

Energy Technology Data Exchange (ETDEWEB)

Hamoud, M R; Qamhieyh, E A [Chemistry Dept., College of Ibn Al-Haitham Baghdad university-Adhamiyah-Baghdad- (Iraq)

1995-10-01

Grafted copolymer was prepared by using gamma irradiation to graft acrylamide onto polymeric molecule prepared by interfacial condensation between two diamine molecules like 1,2 diamino propane and 1,6 diamino-hexane in aqueous layer with sebacoyl chloride in organic layer. The resulted co polyamide was grafted with acrylamide using gamma irradiation. The optimum conditions of grafting reaction were found, also various factors such as the effect of solvents, redox systems and the role water on the radiochemical grafting were studied. Many techniques were used in the characterization of the copolymer before and after grafting. 8 figs.,.

Development of solid lipid nanoparticles for enhanced solubility of poorly soluble drugs

DEFF Research Database (Denmark)

Potta, Sriharsha Gupta; Minemi, Sriharsha; Nukala, Ravi Kumar

2010-01-01

Cyclosporine (CyA) solid lipid nanoparticles were prepared by using a solvent free high pressure homogenization process. CyA was incorporated into SLNs that consisted of stearic acid, trilaurin or tripalmitin lipid solid cores in order to enhance drug solubility. The process was conducted...

[Reconstruction of ankle and foot with combination of free perforator flaps and skin graft].

Science.gov (United States)

Yin, Lu; Gong, Ketong; Yin, Zhonggang; Zhang, Bo; Xu, Jianhua

2017-03-01

To evaluate the clinical outcomes of free perforator flaps combined with skin graft for reconstruction of ankle and foot soft tissue defects. Between June 2014 and October 2015, 20 cases of ankle and foot soft tissue defects were treated. There were 16 males and 4 females, aged from 19 to 61 years (mean, 43.3 years). Injury was caused by traffic accident in 7 cases, by crashing in 9 cases, and machine twist in 4 cases. The locations were the ankle in 6 cases, the heel in 3 cases, the dorsum pedis in 4 cases, and the plantar forefoot in 7 cases of avulsion injury after toes amputation. The size of wound ranged from 15 cm×10 cm to 27 cm×18 cm. The time from injury to treatment was from 11 to 52 days (mean, 27 days). The anterolateral thigh perforator flap was used in 11 cases, thoracodorsal antery perforator flap in 3 cases, medial sural artery perforator flap in 4 cases, deep inferior epigastric perforator flap in 1 case, and anteromedial thigh perforator flap in 1 case, including 5 chimeric perforator flaps, 5 polyfoliate perforator flaps, 3 flow-through perforator flaps, and 3 conjoined perforator flaps. The size of the perforator flap ranged from 10.0 cm×6.5 cm to 36.0 cm×8.0 cm, the size of skin graft from 5 cm×3 cm to 18 cm×12 cm. Venous crisis occurred in 2 flaps which survived after symptomatic treatment; 18 flaps survived successfully and skin grafting healed well. The follow-up time ranged 4-18 months (mean, 8.3 months). The flaps had good appearance, texture and color, without infection. The patients could walk normally and do daily activities. Only linear scars were observed at the donor sites. Free perforator flap can be used to reconstruct defects in the ankle and foot, especially in the weight-bearing area of the plantar forefoot. A combination of free perforator flap and skin graft is ideal in reconstruction of great soft tissue defects in the ankle and foot.

Surfactant-free synthesis of nickel nanoparticles in near-critical water

International Nuclear Information System (INIS)

Hald, Peter; Bremholm, Martin; Iversen, Steen Brummerstedt; Iversen, Bo Brummerstedt

2008-01-01

Nickel nanoparticles have been produced by combining two well-tested methods: (i) the continuous flow supercritical reactor and (ii) the reduction of a nickel salt with hydrazine. The normal precipitation of a nickel-hydrazine complex, which would complicate pumping and mixing of the precursor, was controlled by the addition of ammonia to the precursor solution, and production of nickel nanoparticles with average sizes from 40 to 60 nm were demonstrated. The method therefore provides some size control and enables the production of nickel nanoparticles without the use of surfactants. The pure nickel nanoparticles can be easily isolated using a magnet. - Graphical abstract: A surfactant-free synthesis route to nickel nanoparticles has been successfully transferred to near-critical water conditions reducing synthesis times from hours to seconds. Nickel nanoparticles in the 40-60 nm range have been synthesised from an ammonia stabilised hydrazine complex with the average size controlled by reaction temperature

Control of the electrical conductivity of composites of antimony doped tin oxide (ATO) nanoparticles and acrylate by grafting of 3-methacryloxpropyltrimethoxysilane (MPS)

NARCIS (Netherlands)

Posthumus, W.; Laven, J.; With, de G.; Linde, van der R.

2006-01-01

The effect of the addition of antimony doped tin oxide (ATO) nanoparticles on the electrical conductivity of acrylate films is described. To enable dispersing of ATO in acrylate matrices, 3-methacryloxypropyltrimethoxysilane (MPS) was grafted on the surface of the filler. The amount of MPS used for

Modification of polyetherurethane for biomedical application by radiation induced grafting. II. Water sorption, surface properties, and protein adsorption of grafted films

International Nuclear Information System (INIS)

Jansen, B.; Ellinghorst, G.

1984-01-01

A series of polyetherurethane films grafted by means of gamma radiation with hydrophilic or reactive monomers (2-hydroxyethyl methacrylate, 2,3-epoxypropyl methacrylate, 2,3-dihydroxypropyl methacrylate, and acrylamide) and partially chemically modified were subjected to various physico-chemical investigation methods involving water sorption, contact angle, and protein adsorption measurements. From contact angle data the interfacial free energy gamma sw between grafted films and water was calculated. It was found that the water uptake of grafted films increases with grafting yield or, in the case of grafted and afterwards chemically modified films, with reaction yield; the diffusion coefficient of water in the modified films also increases with grafting yield. Contact angle studies revealed all grafted films to have surfaces more hydrophilic than the ungrafted trunk polymer. The degree of hydrophilicity--especially of HEMA-grafted films--strongly depends on grafting conditions. For some grafted samples with high surface hydrophilicity very low interfacial free energies approaching zero were measured. The study of the competitive adsorption of bovine serum albumin, gamma-globulin, and fibrinogen from a synthetic protein solution onto modified films showed that the adsorption of albumin increases markedly with increasing grafting yields, whereas the fibrinogen and gamma-globulin adsorption only slightly increases. A correlation between interfacial free energy and protein adsorption in the sense of the minimum interfacial free energy hypothesis was found only for samples with grafting yields below 5%. At higher grafting yields the increased surface area complicates the analysis

Synthesis and characterization of thermally stable oligomer-metal ...

African Journals Online (AJOL)

The thermal stabilities of the oligomer-metal complexes were compared by thermogravimetric (TG) and differential thermal (DTA) analyses. According to TG, oligomer-metal complexes were stable against to temperature and thermooxidative decomposition. The weight losses of oligomer-metal complexes were found to be 5 ...

Magnetic solid-phase extraction of protein with deep eutectic solvent immobilized magnetic graphene oxide nanoparticles.

Science.gov (United States)

Xu, Kaijia; Wang, Yuzhi; Ding, Xueqin; Huang, Yanhua; Li, Na; Wen, Qian

2016-01-01

As a new type of green solvent, four kinds of choline chloride (ChCl)-based deep eutectic solvents (DESs) have been synthesized, and then a core-shell structure magnetic graphene oxide (Fe3O4-NH2@GO) nanoparticles have been prepared and coated with the ChCl-based DESs. Magnetic solid-phase extraction (MSPE) based Fe3O4-NH2@GO@DES was studied for the first time for the extraction of proteins. The characteristic results of vibrating sample magnetometer (VSM), X-ray diffraction (XRD), Fourier transform infrared spectrometry (FT-IR), thermal gravimetric analysis (TGA) and field emission scanning electron microscopy (FESEM) indicated the successful preparation of Fe3O4-NH2@GO@DES. The concentrations of proteins in studies were determined by a UV-vis spectrophotometer. The advantages of Fe3O4-NH2@GO@DES in protein extraction were compared with Fe3O4-NH2@GO and Fe3O4-NH2, and Fe3O4-NH2@GO@ChCl-glycerol was selected as the suitable extraction solvent. The influence factors of the extraction process such as the pH value, the temperature, the extraction time, the concentration of protein and the amount of Fe3O4-NH2@GO@ChCl-glycerol were evaluated. Desorption experimental result showed 98.73% of BSA could be eluted from the solid extractant with 0.1 mol/L Na2HPO4 solution contained 1 mol/L NaCl. Besides, the conformation of BSA was not changed during the elution by the investigation of circular dichromism (CD) spectra. Furthermore, the analysis of real sample demonstrated that the prepared magnetic nanoparticles did have extraction ability on proteins in bovine whole blood. Copyright © 2015 Elsevier B.V. All rights reserved.

Solvent-free preparation of co-crystals of phenazine and acridine with vanillin

Energy Technology Data Exchange (ETDEWEB)

Braga, Dario, E-mail: dario.braga@unibo.it [Dipartimento di Chimica ' G.Ciamician' , Universita degli studi di Bologna, Via Selmi 2, 40126 Bologna (Italy); Grepioni, Fabrizia; Maini, Lucia; Mazzeo, Paolo P.; Rubini, Katia [Dipartimento di Chimica ' G.Ciamician' , Universita degli studi di Bologna, Via Selmi 2, 40126 Bologna (Italy)

2010-08-10

Co-crystals of phenazine and acridine with vanillin have been obtained by solvent-free reaction or thermal treatment of the solid reactants: their structures, thermal behaviour and eutectic formation have been investigated via single crystal X-ray diffraction, differential scanning calorimetry (DSC), variable temperature X-ray powder diffraction and hot-stage microscopy (HSM). Polymorph screening of the reagents has also been carried out.

Solvent-free preparation of co-crystals of phenazine and acridine with vanillin

International Nuclear Information System (INIS)

Braga, Dario; Grepioni, Fabrizia; Maini, Lucia; Mazzeo, Paolo P.; Rubini, Katia

2010-01-01

Co-crystals of phenazine and acridine with vanillin have been obtained by solvent-free reaction or thermal treatment of the solid reactants: their structures, thermal behaviour and eutectic formation have been investigated via single crystal X-ray diffraction, differential scanning calorimetry (DSC), variable temperature X-ray powder diffraction and hot-stage microscopy (HSM). Polymorph screening of the reagents has also been carried out.

Polyurethane coating from prepolymers and Crambe oil polyesters in oxygenates and green solvents

International Nuclear Information System (INIS)

Pinto, Elaine R.P.; Messaddeq, Younes; Polito, Wagner Luiz; Matinelli, Marcia

2015-01-01

The PU coatings are extremely used in areas that require high-performance. For several applications PU resin, the solvent base is commonly used, the problem is the solvents with high content of volatile organic compounds (VCO) like: toluene, xylene, benzene, etc.. In this work, we were synthesized and characterized four kinds of prepolymers with low-VCO from renewable sources such as castor oil and crambe oil with oxygenate and green solvents. The PU prepolymers had been synthesized in the proportions NCO/OH 2:1 and 3:1. The curing process was carried out with atmospheric moisture in the films. Characterization was made from prepolymers, oligomers and polyesters and PU films by FTIR, TGA / DTA, NMR, GPC and GC-FID, besides this the coatings were applied on aluminum and glass plates and, subjected to analysis chamber saline, hardness and adhesion. The results indicated that the reaction occurred between the prepolymers with oligomers or polyesters, because disappearance of the NCO band at 2270 cm"-"1. The PU films showed good thermal stability (> 270 °C), high tensile strength and deformation. Surround the formulations, the PU films with HDI prepolymers showed the best results with polyesters from crambe oil (PEC 02 and PEC 03). (author)

Use of Autologous Scleral Graft in Ahmed Glaucoma Valve Surgery.

Science.gov (United States)

Wolf, Alvit; Hod, Yair; Buckman, Gila; Stein, Nili; Geyer, Orna

2016-04-01

To compare the efficacy of an autoscleral free-flap graft versus an autoscleral rotational flap graft in Ahmed glaucoma valve (AGV) surgery. Medical records (2005 to 2012) of 51 consecutive patients (51 eyes) who underwent AGV surgery with the use of either an autoscleral free-flap graft or an autoscleral rotational flap graft to cover the external tube at the limbus were retrieved for review. The main outcome measure was the incidence of tube exposure associated with each surgical approach. Twenty-seven consecutive patients (27 eyes) received a free-flap graft and 24 consecutive patients (24 eyes) received a rotational flap graft. The mean follow-up time was 55.6 ± 18.3 months for the former and 24.2± 5 .0 months for the latter (P<0.0001). Two patients in the free-flap group (8.9%) developed tube exposure at 24 and 55 months postoperatively compared with none of the patients in the rotational flap group. Graft thinning without evidence of conjunctival erosion was observed in 15 patients (55%) in the free-flap group and in 7 patients (29.1%) in the rotational flap group. The use of an autoscleral rotational flap graft is an efficacious technique for primary tube patch grafting in routine AGV surgery, and yielded better results than an autoscleral free-flap graft. Its main advantages over donor graft material are availability and lower cost.

Diclofenac sodium-loaded solid lipid nanoparticles prepared by emulsion/solvent evaporation method

Energy Technology Data Exchange (ETDEWEB)

Liu Dongfei; Jiang Sunmin [Nanjing Medical University, School of Pharmacy (China); Shen Hong [Nanjing Brain Hospital Affiliated to Nanjing Medical University, Neuro-Psychiatric Institute (China); Qin Shan; Liu Juanjuan; Zhang Qing; Li Rui, E-mail: chongloutougao@gmail.com; Xu Qunwei, E-mail: qunweixu@163.com [Nanjing Medical University, School of Pharmacy (China)

2011-06-15

The preparation of solid lipid nanoparticles (SLNs) suffers from the drawback of poor incorporation of water-soluble drugs. The aim of this study was therefore to assess various formulation and process parameters to enhance the incorporation of a water-soluble drug (diclofenac sodium, DS) into SLNs prepared by the emulsion/solvent evaporation method. Results showed that the entrapment efficiency (EE) of DS was increased to approximately 100% by lowering the pH of dispersed phase. The EE of DS-loaded SLNs (DS-SLNs) had been improved by the existence of cosurfactants and increment of PVA concentration. Stabilizers and their combination with PEG 400 in the dispersed phase also resulted in higher EE and drug loading (DL). EE increased and DL decreased as the phospholipid/DS ratio became greater, while the amount of DS had an opposite effect. Ethanol turned out to be the ideal solvent making DS-SLNs. EE and DL of DS-SLNs were not affected by either the stirring speed or the viscosity of aqueous and dispersed phase. According to the investigations, drug solubility in dispersion medium played the most important role in improving EE.

Solvent-free ZnO dye-sensitised solar cells

Energy Technology Data Exchange (ETDEWEB)

Guillen, E.; Anta, J.A. [Departamento de Sistemas Fisicos, Quimicos y Naturales, Universidad Pablo de Olavide, 41013 Sevilla (Spain); Fernandez-Lorenzo, C.; Alcantara, R.; Martin-Calleja, J. [Departamento de Quimica Fisica, Universidad de Cadiz, Cadiz (Spain)

2009-10-15

Dye-sensitised solar cells (DSSC) based on commercial nanostructured zinc oxide combined with imidazolium-based room temperature ionic-liquid electrolytes are characterized. The electrolytes are based on a binary mixture of two ionic liquids, one of them used as source of iodide ions. The composition of this solvent-free electrolyte is optimized with respect to the concentration of iodine and iodide and the effect of additives such as lithium and tert-butylpyridine (TBP) on the photovoltaic performance and the recombination rate is analyzed and discussed. A maximum photoconversion efficiency of 3.4% at 1 sun illumination has been obtained for cells of 0.64 cm{sup 2} active area with the best performing compositions. Diffusion limitations due to slow transport processes are analyzed and discussed. (author)

Fibril specific, conformation dependent antibodies recognize a generic epitope common to amyloid fibrils and fibrillar oligomers that is absent in prefibrillar oligomers

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Rasool Suhail

2007-09-01

Full Text Available Abstract Background Amyloid-related degenerative diseases are associated with the accumulation of misfolded proteins as amyloid fibrils in tissue. In Alzheimer disease (AD, amyloid accumulates in several distinct types of insoluble plaque deposits, intracellular Aβ and as soluble oligomers and the relationships between these deposits and their pathological significance remains unclear. Conformation dependent antibodies have been reported that specifically recognize distinct assembly states of amyloids, including prefibrillar oligomers and fibrils. Results We immunized rabbits with a morphologically homogeneous population of Aβ42 fibrils. The resulting immune serum (OC specifically recognizes fibrils, but not random coil monomer or prefibrillar oligomers, indicating fibrils display a distinct conformation dependent epitope that is absent in prefibrillar oligomers. The fibril epitope is also displayed by fibrils of other types of amyloids, indicating that the epitope is a generic feature of the polypeptide backbone. The fibril specific antibody also recognizes 100,000 × G soluble fibrillar oligomers ranging in size from dimer to greater than 250 kDa on western blots. The fibrillar oligomers recognized by OC are immunologically distinct from prefibrillar oligomers recognized by A11, even though their sizes overlap broadly, indicating that size is not a reliable indicator of oligomer conformation. The immune response to prefibrillar oligomers and fibrils is not sequence specific and antisera of the same specificity are produced in response to immunization with islet amyloid polypeptide prefibrillar oligomer mimics and fibrils. The fibril specific antibodies stain all types of amyloid deposits in human AD brain. Diffuse amyloid deposits stain intensely with anti-fibril antibody although they are thioflavin S negative, suggesting that they are indeed fibrillar in conformation. OC also stains islet amyloid deposits in transgenic mouse models of type

β-cyclodextrin functionalized poly (5-amidoisophthalicacid) grafted Fe{sub 3}O{sub 4} magnetic nanoparticles: A novel biocompatible nanocomposite for targeted docetaxel delivery

Energy Technology Data Exchange (ETDEWEB)

Tarasi, Roghayeh [Department of Chemistry, University of Zanjan, P.O. Box 45195-313, Zanjan (Iran, Islamic Republic of); Khoobi, Mehdi [Department of Pharmaceutical Biomaterials and Medical Biomaterials Research Center, Faculty of Pharmacy, Tehran University of Medical Sciences, Tehran (Iran, Islamic Republic of); Department of Medicinal Chemistry, Faculty of Pharmacy and Pharmaceutical Sciences Research Center, Tehran University of Medical Sciences, Tehran (Iran, Islamic Republic of); Niknejad, Hassan [Department of Tissue Engineering, School of Advanced Technologies in Medicine, Shahid Beheshti University of Medical Sciences, Tehran (Iran, Islamic Republic of); Ramazani, Ali [Department of Chemistry, University of Zanjan, P.O. Box 45195-313, Zanjan (Iran, Islamic Republic of); Ma’mani, Leila [Department of Nanotechnology, Agricultural Biotechnology Research Institute of Iran (ABRII), Agricultural Research, Education and Extension Organization (AREEO), Karaj (Iran, Islamic Republic of); Bahadorikhalili, Saeed [Department of Medicinal Chemistry, Faculty of Pharmacy and Pharmaceutical Sciences Research Center, Tehran University of Medical Sciences, Tehran (Iran, Islamic Republic of); Shafiee, Abbas, E-mail: ashafiee@ams.ac.ir [Department of Medicinal Chemistry, Faculty of Pharmacy and Pharmaceutical Sciences Research Center, Tehran University of Medical Sciences, Tehran (Iran, Islamic Republic of)

2016-11-01

Thiol-lactam initiated radical polymerization (TLIRP) was successfully employed to prepare poly-N−5-acrylamidoisophthalicacid grafted onto Fe{sub 3}O{sub 4} magnetic nanoparticles (MNPs@PAIP). β-Cyclodextrin (CD) was then conjugated to the carboxylic groups of the prepared MNPs via carbodiimide activation. Subsequently, tumor-targeting folic acid (FA) was attached to the hydroxyl groups of CD on the surface of the latter MNPs to increase the site-specific intracellular delivery. The prepared MNPs were fully characterized by FTIR, VSM, TGA, XRD, FE-SEM and TEM. Docetaxel (DTX) as hydrophobic anticancer drug was loaded via host-guest inclusion complexation with CD and the release profile of the system was studied at different pH. The effect of MNPs on the cell viability was evaluated for the human embryonic kidney normal cell line (HEK293) as well as HeLa and MDA-MB-231 cancerous cell lines and the results did not show any apparent cytotoxic effect. In comparison, DTX loaded MNPs reduced the growth of HeLa and MDA-MB-231 cells more than free DTX. Intracellular uptake ability of DTX loaded MNPs was also studied using fluorescent microscopy and showed cellular uptake about 90% after 4 h treatment. - Highlights: • MNPs@PAIP-CD-FA nanoparticles as a carrier of Doctexal have excellent physical properties. • These nanoparticles are superparamagnetic, biocompatible and non-toxic. • The constructed nanocarrier showed suitable loading capacity and entrapment efficiency.

Synthesis of Fuel Cell Membrane: Copolymerization of Styrene on ETFE Film by Grafted pre-Irradiation

Directory of Open Access Journals (Sweden)

Yohan Yohan

2010-10-01

Full Text Available Preirradiation Grafting styrene monomer on ETFE  film has been prepared. Research has been  performed by γ-ray radiation at various total dose from 2.5 - 12.5 kGy and various dose rate from 1.3 - 1.9 kGy/hour. Irradiated copolymer is then grafted by styrene monomer in various solvent: ethanol, 2-propanol, and toluene, various concentration from 20 - 70% volume, various temperature from 50 - 90oC, and various grafting time from 2 - 12 hours. The results showed that percent of grafting is increase with increase of total dose and decrease of  rate dose. The optimum experiment conditions are obtained at total dose 10 kGy, dose rate 1,9 kGy/hour, 2-propanol solvent, 40% volume styrene, 4 hours grafting time, and 70oC grafting temperature.

Solvent-Free Synthesis of Aryl Iodide Using Nano SiO2/HIO4 as a Reusable Acid Catalyst

Directory of Open Access Journals (Sweden)

A. Bamoniri

2014-07-01

Full Text Available An efficient and environmentally benign   method for the synthesis of aryl iodides have been developed by diazotization of aromatic amines with NaNO2 and nanosilica periodic acid (nano-SPIA as a green catalyst via grinding followed by a sandmeyer iodination by KI under solvent-free conditions at room temperature. The ensuing aryl diazonium salts supported on nano-SPIA were sufficiently stable to be kept at room temperature in the dry state. This method is a novel, efficient, eco-friendly route for solvent-free synthesis of aryl iodides.