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Crosslinker
Terms modified by Crosslinker Selected AbstractsBiodegradable Polymer Crosslinker: Independent Control of Stiffness, Toughness, and Hydrogel Degradation RateADVANCED FUNCTIONAL MATERIALS, Issue 19 2009Chaenyung Cha Abstract Hydrogels are being increasingly studied for use in various biomedical applications including drug delivery and tissue engineering. The successful use of a hydrogel in these applications greatly relies on a refined control of the mechanical properties including stiffness, toughness, and the degradation rate. However, it is still challenging to control the hydrogel properties in an independent manner due to the interdependency between hydrogel properties. Here it is hypothesized that a biodegradable polymeric crosslinker would allow for decoupling of the dependency between the properties of various hydrogel materials. This hypothesis is examined using oxidized methacrylic alginate (OMA). The OMA is synthesized by partially oxidizing alginate to generate hydrolytically labile units and conjugating methacrylic groups. It is used to crosslink poly(ethylene glycol) methacrylate and poly(N -hydroxymethyl acrylamide) to form three-dimensional hydrogel systems. OMA significantly improves rigidity and toughness of both hydrogels as compared with a small molecule crosslinker, and also controls the degradation rate of hydrogels depending on the oxidation degree, without altering their initial mechanical properties. The protein-release rate from a hydrogel and subsequent angiogenesis in vivo are thus regulated with the chemical structure of OMA. Overall, the results of this study suggests that the use of OMA as a crosslinker will allow the implantation of a hydrogel in tissue subject to an external mechanical loading with a desired protein-release profile. The OMA synthesized in this study will be, therefore, highly useful to independently control the mechanical properties and degradation rate of a wide array of hydrogels. [source] Multi-walled carbon nanotube composites with polyacrylate prepared for open-tubular capillary electrochromatographyELECTROPHORESIS, Issue 19 2010Jian-Lian Chen Abstract A new phase containing immobilized carbon nanotubes (CNTs) was synthesized by in situ polymerization of acid-treated multi-walled CNTs using butylmethacrylate (BMA) as the monomer and ethylene dimethacrylate as the crosslinker on a silanized capillary, forming a porous-layered open-tubular column for CEC. Incorporation of CNT nanomaterials into a polymer matrix could increase the phase ratio and take advantage of the easy preparation of an OT-CEC column. The completed BMA-CNT column was characterized by SEM, ATR-IR, and EOF measurements, varying the pH and the added volume organic modifier. In the multi-walled CNTs structure, carboxylate groups were the major ionizable ligands on the phase surface exerting the EOF having electroosmotic mobility, 4.0×104,cm2,V,1,S,1, in the phosphate buffer at pH 2.8 and RSD values (n=5), 3.2, 4.1, and 4.3%, for three replicate capillaries at pH 7.6. Application of the BMA-CNT column in CEC separations of various samples, including nucleobases, nucleosides, flavonoids, and phenolic acids, proved satisfactory upon optimization of the running buffers. Their optima were found in the borate buffers at pH 9.0/50,mM, pH 9.5/10,mM/50% v/v ACN, and pH 9.5/30,mM/10% v/v methanol, respectively. The separations could also be used to assess the relative contributions of electrophoresis and chromatography to the CEC mechanism by calculating the corresponding velocity and retention factors. Discussions about interactions between the probe solutes and the bonded phase included the ,,, interactions, electrostatic repulsion, and hydrogen bonding. Furthermore, a reversed-phase mode was discovered to be involved in the chromatographic retention. [source] Parameters governing reproducibility of flow properties of porous monoliths photopatterned within microfluidic channelsELECTROPHORESIS, Issue 14 2010Mei He Abstract We report the patternability as well as the reproducibility and stability of flow resistance of polymer monolithic beds photopatterned within microfluidic channels as a function of initial reagent composition and preparation conditions. 2-Hydroxyethyl methacrylate and ethylene dimethacrylate-based polymer monoliths were selectively photopatterned within microchannels and their flow resistance was evaluated using a photobleaching, TOF linear flow rate measurement method developed in our lab. This measurement technique was found to be significantly more informative for columns formed in microfluidic channels compared with bulk monolith characterization by mercury intrusion porosimetry. 1-Octanol was determined to provide sharp bed edge formation and relatively low flow resistance by photopatterning relative to other porogenic solvents. Compared with literature formulations which did not achieve good flow stability and reproducibility from batch to batch, using 2-hydroxyethyl methacrylate, ethylene dimethacrylate and 1-octanol as porogenic solvents, less than 4% RSD was achieved in flow stability over 7 days for monoliths prepared with 60,80% crosslinker(monomer+crosslinker) ratio. Column-to-column variation of 5% RSD was obtained in this composition range. These results demonstrate that photopatterning of uniform polymer monolithic beds, which is critical for applications in multiplexed microfluidic systems, requires careful attention to the parameters that affect reproducibility, specifically the porogenic solvent choice and the crosslinker to monomer ratio. [source] Facile Functionalization and Phase Reduction Route of Magnetic Iron Oxide Nanoparticles for Conjugation of Matrix Metalloproteinase,ADVANCED ENGINEERING MATERIALS, Issue 6 2010Dan Li Abstract A protocol for the simultaneous functionalization and phase reduction route of iron oxide magnetic nanoparticles (MNPs) and its further bioconjugation is presented. It was found that surface functionalization of maghemite (,-Fe2O3) nanoparticles with mercaptopropyltrimethoxysilane (MPTMS) under anoxic environment at above 80,°C promotes in situ conversion to magnetite (Fe3O4). Full conversion to Fe3O4, as probed by Mössbauer spectroscopy, with accompanied increase in the composite saturation magnetization, was achieved at 120,°C. By controlling the MPTMS concentration, the resultant silane-MNPs morphology can be tuned from having homogeneous thin layer (<1,nm) to thick continuous silane with embedded MNP multicores. Likewise the amount of surface distal thiol moieties was dependent on the silanization conditions. The density of distal thiols (i.e., amount of thiol per surface area) and resultant aggregate size have direct impact on the attachment, as well as the activity and reusability of the conjugated matrix metalloproteinase (MMP-2, using sulfo-SMCC as crosslinker). The work has important implication to the field of magneto-chemotherapeutics, where spatial control of conjugated active biomolecules under magnetic field and T2 -weighted MRI contrast can be achieved simultaneously. [source] An X-ray Spectromicroscopy Study of Albumin Adsorption to Crosslinked Polyethylene Oxide Films,ADVANCED ENGINEERING MATERIALS, Issue 5 2010Bonnie O. Leung Abstract Synchrotron-based X-ray photoemission electron microscopy (X-PEEM) is used to characterize the near surface composition of polyethylene oxide (PEO) combined with 1.5, 5, and 10,wt.-% pentaerythritol triacrylate (PETA) crosslinker. It is found that as the concentration of PETA increases, it becomes the dominant component in the top 10,nm of the film surface. The same surfaces are also exposed to human serum albumin (HSA) and the distributions of the protein relative to PEO and PETA measured with X-PEEM. A positive correlation is found between levels of PETA and HSA at the surface. Above PETA concentrations of 5,wt.-%, HSA adsorption is significant, which suggests high levels of PETA (often used to immobilize PEO by crosslinking) can significantly reduce the non-fouling properties of PEO. [source] Surface-Grafted Gel-Brush/Metal Nanoparticle HybridsADVANCED FUNCTIONAL MATERIALS, Issue 6 2010Edmondo M. Benetti Abstract Polymer brushes are classically defined and are to date employed as assemblies of macromolecules tethered at one end to a surface. The concept of preparing surface-grafted gels by crosslinking such brushes is attractive since it gives rise to new opportunities related to the constraints present in this type of structure. Aiming at the development of nanostructured films possessing precisely adjustable chemical, mechanical, and optical properties, the present article describes the preparation of novel grafted layers based on gel-brush/metal nanoparticle hybrids. These films were synthesized by surface-initiated atom transfer radical polymerization of hydroxyethyl methacrylate with a small percentage of a crosslinker. The swelling, morphological, and mechanical properties of the gel-brushes are shown to be highly dependent on the relative amount of crosslinker used. The gel-brushes are subsequently used as matrixes for the controlled synthesis of silver nanoparticles with overall characteristics that are specifically tunable as a function of the macromolecular structure of the brush template. [source] Smart Hydrogels Co-switched by Hydrogen Bonds and ,,, Stacking for Continuously Regulated Controlled-Release SystemADVANCED FUNCTIONAL MATERIALS, Issue 4 2010Fang Li Abstract A series of hydrogels with continuously regulatable release behavior can be achieved by incorporating hydrogen bonding and ,,, stacking co-switches in polymers. A poly(nitrophenyl methacrylate- co -methacrylic acid) hydrogel (NPMAAHG) for control over drug release is fabricated by copolymerizing 4-nitrophenyl methacrylate and methacrylic acid using ethylene glycol dimethacrylate as a crosslinker. The carboxylic acid groups and nitrylphenyl groups form hydrogen bonds and ,,, stacking interactions, respectively, which act as switches to control the release of guest molecules from the polymers. As revealed by the simulated gastrointestinal tract drug release experiments, the as-synthesized NPMAAHG hydrogels can be regulated to release only 4.7% of drugs after 3,h in a simulated stomach and nearly 92.6% within 43,h in the whole digestive tract. The relation between the release kinetics and structures and the mechanism of the smart release control are analyzed in terms of diffusion exponent, swelling interface number, drug diffusion coefficient, and velocity of the swelling interface in detail. The results reveal that the release of guest molecules from the hydrogels can be continuously regulated for systemic administration by controlling the ratio of the hydrophilic hydrogen bonds and the hydrophobic ,,, stacking switches. [source] Radiation Grafted Membranes for Polymer Electrolyte Fuel Cells,FUEL CELLS, Issue 3 2005L. Gubler Abstract The cost of polymer electrolyte fuel cell (PEFC) components is crucial to the commercial viability of the technology. Proton exchange membranes fabricated via the method of radiation grafting offer a cost-competitive option, because starting materials are inexpensive commodity products and the preparation procedure is based on established industrial processes. Radiation grafted membranes have been used with commercial success in membrane separation technology. This review focuses on the application of radiation grafted membranes in fuel cells, in particular the identification of fuel cell relevant membrane properties, aspects of membrane electrode assembly (MEA) fabrication, electrochemical performance and durability obtained in cell or stack tests, and investigation of failure modes and post mortem analysis. The application in hydrogen and methanol fuelled cells is treated separately. Optimized styrene,/,crosslinker grafted and sulfonated membranes show performance comparable to perfluorinated membranes. Some properties, such as methanol permeability, can be tailored to be superior. Durability of several thousand hours at practical operating conditions has been demonstrated. Alternative styrene derived monomers with higher chemical stability offer the prospect of enhanced durability or higher operating temperature. [source] Biodegradable Polymer Crosslinker: Independent Control of Stiffness, Toughness, and Hydrogel Degradation RateADVANCED FUNCTIONAL MATERIALS, Issue 19 2009Chaenyung Cha Abstract Hydrogels are being increasingly studied for use in various biomedical applications including drug delivery and tissue engineering. The successful use of a hydrogel in these applications greatly relies on a refined control of the mechanical properties including stiffness, toughness, and the degradation rate. However, it is still challenging to control the hydrogel properties in an independent manner due to the interdependency between hydrogel properties. Here it is hypothesized that a biodegradable polymeric crosslinker would allow for decoupling of the dependency between the properties of various hydrogel materials. This hypothesis is examined using oxidized methacrylic alginate (OMA). The OMA is synthesized by partially oxidizing alginate to generate hydrolytically labile units and conjugating methacrylic groups. It is used to crosslink poly(ethylene glycol) methacrylate and poly(N -hydroxymethyl acrylamide) to form three-dimensional hydrogel systems. OMA significantly improves rigidity and toughness of both hydrogels as compared with a small molecule crosslinker, and also controls the degradation rate of hydrogels depending on the oxidation degree, without altering their initial mechanical properties. The protein-release rate from a hydrogel and subsequent angiogenesis in vivo are thus regulated with the chemical structure of OMA. Overall, the results of this study suggests that the use of OMA as a crosslinker will allow the implantation of a hydrogel in tissue subject to an external mechanical loading with a desired protein-release profile. The OMA synthesized in this study will be, therefore, highly useful to independently control the mechanical properties and degradation rate of a wide array of hydrogels. [source] Nanoporous Membranes of Hydrogen-bridged Smectic Networks with Nanometer Transverse Pore Dimensions,ADVANCED MATERIALS, Issue 7 2008Carmen Luengo Gonzalez Nanoporous membranes are made based on photoreactive hydrogen-bridged smectic liquid crystal dimers. The self-assembled layered structure is locked by photopolymerization. The hydrogen bridges are reversibly opened by heating or by changing the pH. This forms periodic pores of which the integrity is conserved by a covalent crosslinker, setting the spacing at ca. 1 nm. The pores are covered with carboxylic anions that bind to cations or to amines. [source] Multicolor Polymer Nanocomposites: In Situ Synthesis and Fabrication of 3D Microstructures,ADVANCED MATERIALS, Issue 5 2008Z.-B. Sun The multiphoton polymerization of CdS,polymer nanocomposites is used to fabricate 3D luminescent structures such as the multicolor "microbull" shown in the figure. The CdS nanoparticles are synthesized in situ within the polymer matrices with their size controlled by the amount of added crosslinker. [source] Swelling properties of CMC- g -poly (AAm- co -AMPS) superabsorbent hydrogelJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2009Ali Pourjavadi Abstract A series of biopolymer-based superabsorbent hydrogels based on carboxymethyl cellulose has been prepared by free-radical graft copolymerization of acrylamide and 2-acrylamido-2-methylpropan sulfonic acid (AMPS) in aqueous solution using methylenebisacrylamide as a crosslinking agent and ammonium persulfate as an initiator. The effect of variables on the swelling capacity such as: acrylamide/AMPS weight ratio, reaction temperature, and concentration of the initiator and crosslinker were systematically optimized. The results indicated that with increasing the amount of AMPS, the swelling capacity is increased. FT-IR spectroscopy and scanning electron microscope analysis were used to confirm the hydrogel structure. Swelling measurements of the synthesized hydrogels in different salt solutions indicated considerable swelling capacity. The absorbency under load of the superabsorbent hydrogels was determined by using an absorbency under load tester at various applied pressures. A preliminary swelling and deswelling behaviors of the hydrogels were also studied. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 [source] Properties and application of poly(methacrylic acid- co -dodecyl methacrylate- cl - N,N -methylene bisacrylamide) hydrogel immobilized Bacillus cereus MTCC 8372 lipase for the synthesis of geranyl acetateJOURNAL OF APPLIED POLYMER SCIENCE, Issue 2 2008Madan Lal Verma Abstract A range of fatty acid esters is now being produced commercially with immobilized microbial lipases (glycerol ester hydrolases; EC) in nonaqueous solvents. In this study, a synthetic hydrogel was prepared by the copolymerization of methacrylic acid and dodecyl methacrylate in the presence of a crosslinker, N,N -methylene bisacrylamide. A purified alkaline thermotolerant bacterial lipase from Bacilluscereus MTCC 8372 was immobilized on a poly(methacrylic acid- co -dodecyl methacrylate- cl - N,N -methylene bisacrylamide) hydrogel by an adsorption method. The hydrogel showed a 95% binding efficiency for the lipase. The bound lipase was evaluated for its hydrolytic potential toward various p -nitrophenyl acyl esters with various C chain lengths. The bound lipase showed optimal hydrolytic activity toward p -nitrophenyl palmitate at a pH of 8.5 and a temperature of 55°C. The hydrolytic activity of the hydrogel-bound lipase was enhanced by Hg2+, Fe3+, and NH ions at a concentration of 1 mM. The hydrogel-bound lipase was used to synthesize geranyl acetate from geraniol and acetic acid in n -heptane. The optimization of the reaction conditions, such as catalyst loading, effect of substrate concentration, solvent (n -pentane, n -hexane, n -heptane, n -octane, and n -nonane), reaction time, temperature, molecular sieve (3 Å × 1.5 mm) and scale up (at 50-mL level), was studied. The immobilized lipase (25 mg/mL) was used to perform an esterification in n -alkane(s) that resulted in the synthesis of approximately 82.8 mM geranyl acetate at 55°C in n -heptane under continuous shaking (160 rpm) after 15 h when geraniol and acetic acid were used in a ratio of 100 : 100 mM. The addition of a molecular sieve (3 Å × 1.5 mm) to the reaction system at a concentration of 40 mg/mL in reaction volume (2 mL) resulted in an increase in the conversion of reactants into geranyl acetate (90.0 mM). During the repetitive esterification under optimum conditions, the hydrogel-bound lipase produced ester (37.0 mM) after the eighth cycle of reuse. When the reaction volume was scaled up to 50 mL, the ester synthesized was 58.7 mM under optimized conditions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Effect of glucose crosslinking on thermomechanical properties and shape memory effect of PET-PEG copolymersJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2008Yong-Chan Chung Abstract Poly(ethylene terephthalate) (PET) and poly (ethylene glycol) (PEG) copolymers crosslinked with glucose as a crosslinker are prepared to improve their mechanical and shape memory properties compared to the one without crosslinking. Composition of PEG and glucose is varied to search for the one with the best mechanical and shape memory properties. The highest shape recovery rate is found in the copolymer composed of 25 mol % PEG-200 and 2.0 mol % glucose. The result that crosslinking by glucose improves the shape recovery rate and supports the high shape recovery rate under the repetitive cyclic test conditions, compared to the one without crosslinking, will be discussed in the points of the structure and shape memory mechanism. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Metal ion-imprinted polymer microspheres derived from copper methacrylate for selective separation of heavy metal ionsJOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2008Anh Hoang Dam Abstract Microbeads of metal ion-imprinted polymers (MIIPs) were prepared by a novel precipitation polymerization technique, in which copper methacrylate monomer and ethylene glycol dimethacrylate crosslinker were copolymerized in a rotary evaporator. The prepared microbeads had mono- or narrow size dispersity, and their sizes increased from 1 to 4 ,m with decreasing solvent amount or increasing initiator concentration. The absorption capacity and selectivity of the imprinted polymer for copper ion were determined in the presence of various competitive metal ions. As results, adsorption equilibrium was quickly achieved in about 10 min with high absorbability (about 90%). The effects of pH, initial metallic ion concentration, and MIIP bead size on the absorption capacity were investigated. The Cu(II)-imprinted polymers exhibited extremely high selectivity, which was much higher than that of corresponding blank polymers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008 [source] Effect of the different rigidity of the chiral crosslinker on phase behaviors of side-chain chiral liquid crystalline elastomersJOURNAL OF APPLIED POLYMER SCIENCE, Issue 3 2008Bao-Yan Zhang Abstract In the present work, the phase behaviors of two series of side-chain liquid crystalline elastomers (PI and PII series) derived from the same nematic liquid crystalline monomer and the different rigidity of chiral bisolefinic crosslinking units have been compared and studied extensively, and the effect of the different rigidity of crosslinker on the phase behavior of elastomers has been discussed. The chemical structure of the monomers and polymers obtained were confirmed by FTIR and 1H NMR spectroscopy. The phase behaviors were investigated by differential scanning calorimetry, polarizing optical microscopy measurement, thermogravimetric analyses, and X-ray diffraction measurement. The two series of elastomers showed smectic or cholesteric phases. When the amount of different crosslinking units was less than 15 mol %, both of the elastomers displayed elasticity, reversible phase transition with wide mesophase temperature ranges, and high thermal stability. It is shown that the isotropization temperature values of PII series are higher than those of PI series, and the glass transition temperature values of PII series varied smoothly and that of PI series changed smoothly first and then abruptly with increasing the contents of crosslinkers with different rigidity. In addition, PI series showed an interesting change in LC texture near clearing point, but PII series did not. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Synthesis and characterization superabsorbent-ethanol polyacrylic acid gelsJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2007Zhao Qingchun Abstract In this article, superabsorbent-ethanol polyacrylic acid gels were synthesized by free-radical aqueous polymerization method by using , rays as initiator and varying the concentration of the Zn2+ from 0.1 to 0.3%, which acts as crosslinker. Effect of irradiation dose, monomer concentration, kind, and concentration of the crosslinker on swelling behaviors of polyacrylic acid gels were investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007 [source] Synthesis and properties of carboxymethyl cellulose- graft -poly(acrylic acid- co -acrylamide) as a novel cellulose-based superabsorbentJOURNAL OF APPLIED POLYMER SCIENCE, Issue 3 2007Aili Suo Abstract A new cellulose-based superabsorbent polymer, carboxymethyl cellulose- graft -poly(acrylic acid- co -acrylamide), was prepared by the free-radical grafting solution polymerization of acrylic acid (AA) and acrylamide (AM) monomers onto carboxymethyl cellulose (CMC) in the presence of N,N,-methylenebisacrylamide as a crosslinker with a redox couple of potassium persulfate and sodium metabisulfite as an initiator. The influences of reaction variables such as the initiator content, crosslinker content, bath temperature, molar ratio of AA to AM, and weight ratio of the monomers to CMC on the water absorbency of the carboxymethylcellulose- graft -poly(acrylic acid- co -acrylamide) copolymer were investigated. The copolymer's structures were characterized with Fourier transform infrared spectroscopy. The optimum reaction conditions were obtained as follows: the bath temperature was 50°C; the molar ratio of AA to AM was 3 : 1; the mass ratio of the monomers to CMC was 4 : 1; and the weight percentages of the crosslinker and initiator with respect to the monomers were 0.75 and 1%, respectively. The maximum water absorbency of the optimized product was 920 g/g for distilled water and 85 g/g for a 0.9 wt % aqueous NaCl solution. In addition, the superabsorbent possessed good water retention and salt resistance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1382,1388, 2007 [source] Poly(glutamic acid) poly(ethylene glycol) hydrogels prepared by photoinduced polymerization: Synthesis, characterization, and preliminary release studies of protein drugsJOURNAL OF BIOMEDICAL MATERIALS RESEARCH, Issue 1 2002Zhiqiang Yang Abstract A class of new biodegradable hydrogels based on poly(ethylene glycol) methacrylate-graft-poly(glutamic acid) and poly(ethylene glycol) dimethacrylate was synthesized by photoinduced polymerization. Because all the polymeric constituents were highly hydrophilic, crosslinking could be performed in aqueous solutions. This type of crosslinked hydrogel was prepared by modifying a select number of acidic side-groups on poly(glutamic acid) with poly(ethylene glycol) methacrylate. These modified chains were then crosslinked in the presence of poly(ethylene glycol) dimethacrylate under a photoinduced polymerization at a wavelength of 365 nm. Swelling experiments were conducted to study the crosslinking density, pH-responsive behavior, and degradation of the hydrogel. Results showed that the degree of swelling of this type of hydrogels increased as the crosslinker concentration (or density) was reduced. Because of the presence of acidic side chains on poly(glutamic acid), swelling behavior was found to be pH-responsive, increasing at high pH in response to the increase in the amount of ionized acidic side chains. The degradation rate of these hydrogels also varied with pH. More rapid degradation was observed under stronger alkaline conditions because of the hydrolysis of the ester bonds between the crosslinker and the polymer backbone. Practically useful degradation rates could be achieved for such hydrogels under physiological conditions. Drug release rates from these hydrogels were found to be proportional to the protein molecular weight and the crosslinker density; increasing at lower protein molecular weight or crosslinker density. The preliminary findings presented in this article suggest that this class of biodegradable hydrogels could be an attractive avenue for drug delivery applications. The specific photoinduced crosslinking chemistry used would permit hydrogels to be synthesized in existence of the entrapped macromolecular drugs including peptides, proteins, and cells. In addition, the rapid feature of this polymerization procedure along with the ability to perform hydrogel synthesis and drug loading in an aqueous environment would offer great advantages in retaining drug activity during hydrogel synthesis. © 2002 Wiley Periodicals, Inc. J Biomed Mater Res 62: 14,21, 2002 [source] Characterization of crosslinking effects on the physicochemical and drug diffusional properties of cationic hydrogels designed as bioactive urological biomaterialsJOURNAL OF PHARMACY AND PHARMACOLOGY: AN INTERNATI ONAL JOURNAL OF PHARMACEUTICAL SCIENCE, Issue 10 2005David S. Jones This study examined the effects of concentration and type of crosslinker (tetraethyleneglycol diacrylate, TEGDA; diethyleneglycol dimethacrylate, DEGDMA; and polyethyleneglycol dimethacrylate, PEGDMA) on the mechanical and drug diffusional properties of hydrogels that had been selected as candidate coatings for bioactive medical devices. Hydrogels (dimethylaminoethylmethacrylate-covinylpyrrolidone; 1:1) were prepared by free radical polymerization and characterized using tensile analysis, dynamic contact angle analysis and analysis of swelling at pH 6.0. The release of fusidic acid and chlorhexidine was evaluated using buffered medium at pH 6.0 and, in addition, using dissolution medium that had been buffered to pH 9 in the presence and absence of elevated concentrations of calcium, representative of urinary encrustation. Crosslinker concentration, but not type, affected the advancing and receding contact angles. Conversely, both crosslinker type and concentration affected the mechanical and swelling properties of the hydrogels. Maximum swelling and elongation at break were associated with the PEGDMA-crosslinked hydrogels whereas TEGDA-crosslinked hydrogels exhibited the maximum ultimate tensile strength and Young's modulus. Drug release from all systems occurred by diffusion. The mass of chlorhexidine and fusidic acid released was dependent on crosslinker type and concentration, with hydrogels crosslinked with PEGDMA offering the greatest mass of drug released at each sampling period. The mass of fusidic acid but not chlorhexidine released at pH 9.0 in a calcium augmented medium was lower than that released in the same medium devoid of elevated calcium, due to the formation of the poorly soluble calcium salt. In conclusion, this study has uniquely examined the effects of crosslinker type and concentration on physicochemical and drug release properties essential to the clinical and non-clinical performance of bioactive hydrogels for medical device application. [source] Synthesis of thermosensitive guar-based hydrogels with tunable physico-chemical properties by click chemistryJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 13 2010Morgan Tizzotti Abstract Thermosensitive guar-based hydrogels are obtained in water solutions by copper-catalyzed 1,3-dipolar cycloaddition between alkyne-functionalized guars and ,,,-diazido-poly[(ethylene glycol)- co -(propylene glycol)]. Characterization by TGA, HR-MAS 1H NMR, and rheology have shown that hydrogels with tunable physico-chemical properties, such as crosslinking density, viscoelasticity, swelling ratio, and so forth, could be obtained by varying the guar molar mass, the degree of alkyne functionality, the guar/crosslinker weight ratio, and the reaction temperature. Based on swelling measurements, it has been shown that the thermal sensitiveness of guar-based hydrogels is fast, reversible, and intimately related to the weight fraction of the thermosensitive crosslinker in the network. Finally, the monitoring of doxorubicin hydrochloride release has demonstrated the potential of these hydrogels as temperature-dependent drug release devices. The robust, efficient, and orthogonal approach described herein represents a general approach towards the development of well-controlled guar-based hydrogels using ,,,-diazido crosslinkers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2733,2742, 2010 [source] Water-soluble, thermoresponsive, hyperbranched copolymers based on PEG-methacrylates: Synthesis, characterization, and LCST behaviorJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 13 2010Mario Luzon Abstract A series of water-soluble thermoresponsive hyperbranched copoly(oligoethylene glycol)s were synthesized by copolymerization of di(ethylene glycol) methacrylate (DEG-MA) and oligo(ethylene glycol) methacrylate (OEG-MA, Mw = 475 g/mol), with ethylene glycol dimethacrylate (EGD-MA) used as the crosslinker, via reversible addition fragmentation chain transfer polymerization. Polymers were characterized by size exclusion chromatography and nuclear magnetic resonance analyses. According to the monomer composition, that is, the ratio of OEG-MA: DEG-MA: EGD-MA, the lower critical solution temperature (LCST) could be tuned from 25 °C to 90 °C. The thermoresponsive properties of these hyperbranched copolymers were studied carefully and compared with their linear analogs. It was found that molecular architecture influences thermoresponsive behavior, with a decrease of around 5,10 °C in the LCST of the hyperbranched polymers compared with the LCST of linear chains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2783,2792, 2010 [source] Intrastrand foldamer crosslinking by reductive aminationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 4 2010Ronald A. Smaldone Abstract A series of m -phenylene ethynylene (mPE) foldamers were crosslinked in their helical conformation using a reductive amination-based strategy. This was accomplished by placing aldehyde moieties in the backbone of the oligomer at specific residues, which allowed a diamine crosslinker to covalently link the helical loops together. Three different foldamers with crosslinks placed at different locations in the backbone were synthesized and characterized by mass spectrometry, 1H NMR, and gel permeation chromatography. The effect of the crosslinking on the stability of the folded state was evaluated through solvent denaturation studies. These studies show a reduction in the oligomer's ability to unfold of up to 30% relative to an unmodified mPE oligomer of the same length in solvents that promote unfolding. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 927,935, 2010 [source] Synthesis of hollow crosslinked miktoarm polymer using miniemulsion as templatesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 6 2009De'an Xiong Abstract Hollow crosslinked polymers (HCPs) were synthesized using arm first method via atom transfer radical polymerization. The polymerization process was performed in miniemulsion system, in which the macroinitiator, PEG-Br, was in the water phase, whereas the vinyl-monomer, 4-vinylpyridine (4VP), and the crosslinker, DVB, were in the butanone phase. TEM images and light scattering characterization showed that the resultant polymer contained a hollow space, and the volume of the hollow space could be adjusted by changing the ratio of water to butanone. Also, hollow crosslinked Miktoarm polymers (HCMPs) were synthesized through this method when two different macroinitiators, PEG-Br and PNIPAM-Br, were used to coinitiate the polymerization of the vinyl-monomer, 4VP and DVB. The 1H NMR spectra showed that the hollow polymers contained both PEG arms and PNIPAM arms. The hollow morphologies of the resultant Miktoarm polymers were the same as the HCPs. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1651,1660, 2009 [source] Poly(ethylene glycol)-based amphiphilic model conetworks: Synthesis by RAFT polymerization and characterizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 22 2008Mariliz Achilleos Abstract Poly(ethylene glycol) (PEG)-containing quasi-model amphiphilic polymer conetworks (APCNs) were prepared by reversible addition fragmentation chain transfer (RAFT) polymerization using ,,,-bis(2-cyanoprop-2-yl dithiobenzoate)-PEG as a bifunctional RAFT macrochain transfer agent (macro-CTA) and stepwise additions of a hydrophobic monomer and a crosslinker (crosslinker: macro-CTA = 10:1, reaction time 24 h). Three different types of monomers, methyl methacrylate (MMA), n -butyl acrylate and styrene, were employed as the hydrophobic monomers, whereas ethylene glycol dimethacrylate, ethylene glycol diacrylate and 1,4-divinylbenzene served as the respective crosslinkers. PEG homopolymer hydrophilic quasi-model networks were also prepared by RAFT-polymerizing the three crosslinkers directly onto the two active ends of the PEG-based macro-CTA. From the three ABA triblock copolymers prepared, the MMA-containing one was obtained at the highest polymerization yields. The crosslinking yields of the three ABA triblock copolymers with the corresponding crosslinkers were higher than those of the PEG-based macro-CTA with the same crosslinkers. The degrees of swelling (DSs) of all conetworks were measured in water and in tetrahydrofuran (THF). The DSs of the APCNs in THF were higher than those in water, whereas the reverse was true for the DSs of the hydrophilic homopolymer networks. Finally, the aqueous DSs of the APCNs were lower than those of the corresponding hydrophilic homopolymer networks. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7556,7565, 2008 [source] Thermoresponsive hydrogel of poly(glycidyl methacrylate- co - N -isopropylacrylamide) as a nanoreactor of gold nanoparticlesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 13 2007Xiaowei Jiang Abstract The synthesis of a thermoresponsive hydrogel of poly(glycidyl methacrylate- co - N -isopropylacrylamide) (PGMA- co -PNIPAM) and its application as a nanoreactor of gold nanoparticles are studied. The thermoresponsive copolymer of PGMA- co -PNIPAM is first synthesized by the copolymerization of glycidyl methacrylate and N -isopropylacrylamide using 2,2,-azobis(isobutyronitrile) as an initiator in tetrahydrofuran at 70 °C and then crosslinked with diethylenetriamine to form a thermoresponsive hydrogel. The lower critical solution temperature (LCST) of the thermoresponsive hydrogel is about 50 °C. The hydrogel exists as 280-nm spheres below the LCST. The diameter of the spherical hydrogel gradually decreases to a minimum constant of 113 nm when the temperature increases to 75 °C. The hydrogel can act as a nanoreactor of gold nanoparticles because of the coordination of nitrogen atoms of the crosslinker with gold ions, on which a hydrogel/gold nanocomposite is synthesized. The LCST of the resultant hydrogel/gold nanocomposite is similar to that of the hydrogel. The size of the resultant gold nanoparticles is about 15 nm. The hydrogel/gold nanocomposite can act as a smart and recyclable catalyst. At a temperature below the LCST, the thermoresponsive nanocomposite is a homogeneous and efficient catalyst, whereas at a temperature above the LCST, it becomes a heterogeneous one, and its catalytic activity greatly decreases. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2812,2819, 2007 [source] Synthesis and properties of crosslinked polyvinylformamide and polyvinylamine hydrogels in conjunction with silica particlesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 18 2002Torsten Meyer Abstract Polyvinylamine hydrogels with silica particles encapsulated (PVAm/silica) were produced by a two-step synthesis. In the first step, polyvinylformamide/silica (PVFA/silica) hybrids were synthesized from vinylformamide (VFA) and 1,3-divinylimidazolidin-2-one (1,3-bisvinylethyleneurea, BVU), as the crosslinker, by radical copolymerization in silica/water suspensions using different compositions of VFA/BVU. The target product PVAm/silica was obtained by acidic hydrolysis of the PVFA/silica hydrogels in a second step. The chemical structures of both hydrogels, PVFA/silica and PVAm/silica, respectively, were revealed by solid-state 13C(1H) cross-polarity/magic-angle spinning NMR spectroscopy. Both hydrogels swelled significantly in water. The swelling capacity of the two systems was characterized by the correlation length , (or hydrodynamic blob size) of the network meshes with small-angle neutron scattering experiments. , is significantly larger for PVAm/silica than for PVFA/silica, which corresponds to the observed higher swelling capacity of this polyelectrolyte material. Furthermore, the swelling behavior of the hybrid hydrogels was quantitatively described in terms of free swell capacity, centrifuge-retention capacity, adsorption against pressure, and free swell rate as compared with values of the corresponding copolymer hydrogels. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3144,3152, 2002 [source] Selective enrichment of trace copper(II) from biological and natural water samples by SPE using ion-imprinted polymerJOURNAL OF SEPARATION SCIENCE, JSS, Issue 6-7 2008Yunhui Zhai Abstract A novel Cu(II)-imprinted polymer sorbent was prepared by an ion-imprinted polymer (IIP) technique using (2Z)- N,N,-bis(2-aminoethylic)but-2-enediamide as the functional monomer and pentaerythritol triacylate as a crosslinker. IR, XPS, and elemental analysis techniques were used to confirm the obtained product. Subsequently, when this polymer was used as sorbent in SPE, it exhibited excellent selectivity for template ion from an aqueous solution. Quantitative extraction of Cu(II) was achieved in the pH range of 4,7. The time needed to extract each sample was less than 30 min by the batch method. The distribution ratio (D) values of IIP for Cu(II) were greatly larger than that for other ions. At optimal pH value, the maximum extraction capacity of IIP and nonimprinted polymer (NIP) was found to be 29.8 and 7.0 mg/g, respectively. The adsorption behavior of Cu(II) on the sorbents could be described by Langmuir adsorption isotherm equation. The feasible flow rate of Cu(II)-containing solution for quantitative extraction onto the column packed with IIP was 1,4 mL/min, whereas for elution it was less than 1 mL/min. The developed method was successfully applied to the separation and enrichment of trace Cu(II) in biological and natural water samples with satisfactory results. [source] Characterization of fibronectin assembly by platelets adherent to adsorbed laminin-111JOURNAL OF THROMBOSIS AND HAEMOSTASIS, Issue 5 2006J. CHO Summary.,Background: Various types of laminin (LN) are ubiquitous components of basement membrane and exposed to blood upon localized damage of vascular endothelial cells. Fibronectin is a plasma protein that is insolubilized into fibrils in a regulated fashion by, for example, lysophosphatidic acid (LPA)-stimulated fibroblasts or platelets spread on supportive adhesive ligands. Objective: To study assembly of plasma fibronectin by LPA-activated platelets adherent to LN-111 via ,6,1 integrin. Results: Platelets adherent to LN-111-bound plasma fibronectin or its N-terminal 70 kD fragment in fibrillar arrays at the periphery of spread platelets under static but not shear conditions. Formation of fibronectin arrays under static conditions was inhibited by co-incubation with the N-terminal 70 kD fragment or with a 49-amino acid peptide that binds to the N-terminal region of fibronectin. Approximately 7000 fibronectin dimers bound per adherent platelet with a Kd of 50 nm. Bound 70 kD fragment was readily solubilized with deoxycholate (DOC), whereas bound fibronectin became progressively insoluble. Bound 70 kD fragment became resistant to DOC extraction after treatment with a cell-impermeable, reducible crosslinker. Crosslinked 70 kD fragment was found in a high molecular weight complex. As with fibroblasts, signaling molecules modulating actin cytoskeletal organization controlled expression of binding sites for the N-terminal 70 kD region of fibronectin on adherent platelets. Conclusions: These results indicate that platelets adherent to LN-111 via ,6,1 support subsequent assembly of fibronectin, but possibly only under conditions of intermittent or stagnant blood flow. [source] Correlation between Morphology, Water Uptake, and Proton Conductivity in Radiation-Grafted Proton-Exchange MembranesMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 6 2010Sandor Balog Abstract An SANS investigation of hydrated proton exchange membranes is presented. Our membranes were synthesized by radiation-induced grafting of ETFE with styrene in the presence of a crosslinker, followed by sulfonation of the styrene. The contrast variation method was used to understand the relationship between morphology, water uptake, and proton conductivity. The membranes are separated into two phases. The amorphous phase hosts the water and swells upon hydration, swelling being inversely proportional to the degree of crosslinking. Hydration and proton conductivity exhibit linear dependence on swelling. Proton conductivity and volumetric fraction of water are related by a power law, indicating a percolated network of finely dispersed aqueous pores in the hydrophilic domains. [source] | ||||||||||||||||||||||||||||||||||