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Swelling Experiments (swelling + experiment)
Selected AbstractsFunctional Chromium Wheel-Based Hybrid Organic,Inorganic Materials for Dielectric ApplicationsADVANCED FUNCTIONAL MATERIALS, Issue 20 2009Vito Di Noto Abstract The first example of organic,inorganic hybrid materials based on the embedding of a chromium,nickel wheel cluster {[(n-C3H7)2NH2]- [Cr7NiF8(O2C4H5)16]} (Cr7Ni) into poly(methyl methacrylate) (PMMA) and the characterization of the dielectric properties of the obtained material is described. By an optimized copolymerization of the methacrylate-functionalized chromium,nickel wheel with methyl methacrylate in a cluster/monomer 1:200 molar mixture, a homogeneous hybrid material CrNi_MMA200 is obtained. The electrical responses of the non-doped PMMA and of the hybrid material were studied by broadband dielectric spectroscopy (BDS) from 0.01,Hz to 10,MHz and over the temperature range of 5,115,°C. The permittivity profiles reveal two relaxation peaks in the materials, which correspond to the , and , relaxation modes of the PMMA matrix. The position of these modes shifts toward higher frequencies as temperature increases. BDS is a powerful tool revealing the intimate miscibility of the various components of the hybrid material, thus indicating that, on a molecular scale, the material proposed is a homogeneous system. Finally, a value of the dielectric constant of 2.9 at 25,°C and 1,kHz is determined. This value is noticeably lower than the value of 3.2 obtained for pristine PMMA prepared following the same synthesis protocol. Thus, these results classify the hybrid CrNi_MMA200 as an appealing starting material for the development of dielectric polymeric layers for the development of innovative capacitors, transistors, and other microelectronic devices. The vibrational properties of the hybrid materials are investigated by Fourier-transform infrared (FT-IR) and Raman spectroscopy, whereas the thermal behavior is analyzed by thermogravimetric analysis (TGA). Swelling experiments are used to qualitatively evaluate the crosslinking density of the hybrid materials. The integrity of the wheels once embedded in the macromolecular backbone is confirmed by extended X-ray absorption fine structure (EXAFS) and electron spin resonance (EPR) spectroscopic measurements. [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] A new composite sorbent for water and dye uptake: Highly swollen acrylamide/2-acrylamido-2-methyl-1-propanesulfonic acid/clay hydrogels crosslinked by 1,4-butanediol dimethacrylatePOLYMER COMPOSITES, Issue 1 2009Semiha Kundakci A novel type of highly swollen hydrogels based on acrylamide (AAm) with 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and clay such as bentonite (Bent) crosslinked by 1,4-butanediol dimethacrylate (BDMA) was prepared by free radical solution polymerization in aqueous media. Water uptake and dye sorption properties of polyelectrolyte AAm/AMPS hydrogels and AAm/AMPS/Bent composite hydrogels were investigated as a function of composition to find materials with swelling and sorption properties. FTIR analyses were made. Swelling experiments were performed in water and dye solution at 25°C, gravimetrically. Highly swollen AAm/AMPS and AAm/AMPS/Bent hydrogels were used in experiments on sorption of water-soluble monovalent cationic dye such as Lauths violet "LV, (Thionin)." Swelling of AAm/AMPS hydrogels was increased up to 1,920,9,222% in water and 867,4,644% in LV solutions, while AAm hydrogels swelled 905% in water and swelling of AAm/AMPS/Bent hydrogels was increased up to 2,756,10,422% in water and 1,200,3,332% in LV solutions, while AAm/Bent hydrogels swelled 849% in water. Some swelling kinetic and diffusional parameters were found. Water and LV diffusion into hydrogels was found to be non-Fickian in character. For sorption of cationic dye, LV into AAm/AMPS and AAm/AMPS/Bent hydrogel was studied by batch sorption technique at 25°C. The amount of the dye sorbed per unit mass removal effiency and partition coefficient of the hydrogels was investigated. The influence of AMPS content in the hydrogels to sorption was examined. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers [source] Metal ion permeation properties of silk fibroin/chitosan blend membranesPOLYMER INTERNATIONAL, Issue 4 2006Chun-Hui Du Abstract Silk fibroin/chitosan (SF/CS) blend membranes were prepared and characterized by infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and scanning electron microscopy. It was found that SF and CS were compatible in the blend membranes and that the membranes were dense without microscopic phase separation. Swelling experiments showed that the swelling ratio of the blend membranes increased with CS content and reached the highest value when CS content was 70 wt%. Experiments indicated that the permeability coefficient of K+ through the blend membrane was 2,4 times higher than that of pure CS membrane, and 10 times higher than that of pure SF membrane. The permeation rate of K+ increased linearly with CS content in the blend membrane for the lower concentration feeding solution. For different metal ions, the permeability through SF/CS blend membranes was in the sequence K+ > Ca2+ > Cd2+ > Pb2+ > Cu2+ > Ni2+. Copyright © 2006 Society of Chemical Industry [source] Fast transient fluorescence technique for studying swelling of gels made at various crosslinker contents and exposed to organic vapourPOLYMER INTERNATIONAL, Issue 9 2002M Erdo Abstract Fast transient fluorescence technique (FTRF) was employed for studying swelling of disc-shaped poly(methyl methacrylate) (PMMA) gels, which were prepared by free radical copolymerization of methyl methacrylate (MMA) using various ethylene glycol dimethacrylate (EGDM) contents at 60,°C. Pyrene (P) was introduced as a fluorescence probe during polymerization. Swelling experiments were performed by using P-doped PMMA gels under chloroform vapor. Decay curves of P were measured during in situ swelling experiments. Exponential fits were performed to measure pyrene lifetimes, ,, inside the PMMA gels. It was observed that , values decreased as swelling proceeded. An equation is derived for low quenching efficiencies to interpret the behaviour of P lifetimes during swelling. The Li,Tanaka equation was used to determine the cooperative diffusion coefficients, Dc, for the gels made at various crosslinker contents. It is observed that Dc values decrease as the crosslinker content is increased. © 2002 Society of Chemical Industry [source] Proteolytically Degradable Photo-Polymerized Hydrogels Made From PEG,Fibrinogen Adducts,ADVANCED ENGINEERING MATERIALS, Issue 6 2010Daniel Dikovsky Abstract We develop a biomaterial based on protein,polymer conjugates where poly(ethylene glycol) (PEG) polymer chains are covalently linked to multiple thiols on denatured fibrinogen. We hypothesize that conjugation of large diacrylate-functionalized linear PEG chains to fibrinogen could govern the molecular architecture of the polymer network via a unique protein,polymer interaction. The hypothesis is explored using carefully designed shear rheometry and swelling experiments of the hydrogels and their precursor PEG/fibrinogen conjugate solutions. The physical properties of non-cross-linked and UV cross-linked PEGylated fibrinogen having PEG molecular weights ranging from 10 to 20,kDa are specifically investigated. Attaching multiple hydrophilic, functionalized PEG chains to the denatured fibrinogen solubilizes the denatured protein and enables a rapid free-radical polymerization cross-linking reaction in the hydrogel precursor solution. As expected, the conjugated protein-polymer macromolecular complexes act to mediate the interactions between radicals and unsaturated bonds during the free-radical polymerization reaction, when compared to control PEG hydrogels. Accordingly, the cross-linking kinetics and stiffness of the cross-linked hydrogel are highly influenced by the protein,polymer conjugate architecture and molecular entanglements arising from hydrophobic/hydrophilic interactions and steric hindrances. The proteolytic degradation products of the protein,polymer conjugates proves to be were different from those of the non-conjugated denatured protein degradation products, indicating that steric hindrances may alter the proteolytic susceptibility of the PEG,protein adduct. A more complete understanding of the molecular complexities associated with this type of protein-polymer conjugation can help to identify the full potential of a biomaterial that combines the advantages of synthetic polymers and bioactive proteins. [source] Properties of amylopectin/montmorillonite composite films containing a coupling agentJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2007D. Nordqvist Abstract The addition of clay to polymers has the combined effects of enhancing both the strength/stiffness and the barrier properties. This investigation presents a novel approach to further enhance the strength/stiffness of cast plasticized amylopectin (AP)/Na+ -montmorillonite clay films using a water-soluble coupling agent, poly[(isobutylene- alt -maleic acid, ammonium salt)- co -(isobutylene- alt -maleic anhydride)], between the filler and the matrix. The addition of clay increased the strength and stiffness of the film and the addition of 0.4 parts of a coupling agent per 1 part clay further increased these properties. The trends were the same after each treatment, and there were always significant differences in stiffness and strength between the films without clay and with clay with 0.4 parts of the coupling agent. The increase in stiffness/strength in the presence of a small amount of the coupling agent suggested that it had a bridging effect, presumably through strong secondary bonds to the clay and to the matrix. Infrared spectroscopy and moisture swelling experiments indicated that ester bonds were formed between the coupling agent and AP. X-ray spectroscopy and transmission electron microscopy revealed that the clay-particle/polymer structure was qualitatively independent of the presence of the coupling agent showing a mixture of intercalated clay stacks and exfoliated platelets. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4160,4167, 2007 [source] Redundancy in the function of mitochondrial phosphate transport in Saccharomyces cerevisiae and Arabidopsis thalianaMOLECULAR MICROBIOLOGY, Issue 2 2004Patrice Hamel Summary Most cellular ATP is produced within the mitochondria from ADP and Pi which are delivered across the inner-membrane by specific nuclearly encoded polytopic carriers. In Saccharomyces cerevisiae, some of these carriers and in particular the ADP/ATP carrier, are represented by several related isoforms that are distinct in their pattern of expression. Until now, only one mitochondrial Pi carrier (mPic) form, encoded by the MIR1 gene in S. cerevisiae, has been described. Here we show that the gene product encoded by the YER053C ORF also participates in the delivery of phosphate to the mitochondria. We have called this gene PIC2 for Pi carrier isoform 2. Overexpression of PIC2 compensates for the mitochondrial defect of the double mutant ,mir1 ,pic2 and restores phosphate transport activity in mitochondria swelling experiments. The existence of two isoforms of mPic does not seem to be restricted to S. cerevisiae as two Arabidopsis thaliana cDNAs encoding two different mPic-like proteins are also able to complement the double mutant ,mir1 ,pic2. Finally, we demonstrate that Pic2p is a mitochondrial protein and that its steady state level increases at high temperature. We propose that Pic2p is a minor form of mPic which plays a role under specific stress conditions. [source] Fast transient fluorescence technique for studying swelling of gels made at various crosslinker contents and exposed to organic vapourPOLYMER INTERNATIONAL, Issue 9 2002M Erdo Abstract Fast transient fluorescence technique (FTRF) was employed for studying swelling of disc-shaped poly(methyl methacrylate) (PMMA) gels, which were prepared by free radical copolymerization of methyl methacrylate (MMA) using various ethylene glycol dimethacrylate (EGDM) contents at 60,°C. Pyrene (P) was introduced as a fluorescence probe during polymerization. Swelling experiments were performed by using P-doped PMMA gels under chloroform vapor. Decay curves of P were measured during in situ swelling experiments. Exponential fits were performed to measure pyrene lifetimes, ,, inside the PMMA gels. It was observed that , values decreased as swelling proceeded. An equation is derived for low quenching efficiencies to interpret the behaviour of P lifetimes during swelling. The Li,Tanaka equation was used to determine the cooperative diffusion coefficients, Dc, for the gels made at various crosslinker contents. It is observed that Dc values decrease as the crosslinker content is increased. © 2002 Society of Chemical Industry [source] Networks for recognition of biomolecules: molecular imprinting and micropatterning poly(ethylene glycol)- Containing films,POLYMERS FOR ADVANCED TECHNOLOGIES, Issue 10-12 2002Mark E. Byrne Abstract Engineering the molecular design of biomaterials by controlling recognition and specificity is the first step in coordinating and duplicating complex biological and physiological processes. Studies of protein binding domains reveal molecular architectures with specific chemical moieties that provide a framework for selective recognition of target biomolecules in aqueous environment. By matching functionality and positioning of chemical residues, we have been successful in designing biomimetic polymer networks that specifically bind biomolecules in aqueous environments. Our work addresses the preparation, behavior, and dynamics of the three-dimensional structure of biomimetic polymers for selective recognition via non-covalent complexation. In particular, the synthesis and characterization of recognitive gels for the macromolecular recognition of D -glucose is highlighted. Novel copolymer networks containing poly(ethylene glycol) (PEG) and functional monomers such as acrylic acid, 2-hydroxyethyl methacrylate, and acrylamide were synthesized in dimethyl sulfoxide (polar, aprotic solvent) and water (polar, protic solvent) via UV-free radical polymerization. Polymers were characterized by single and competitive equilibrium and kinetic binding studies, single and competitive fluorescent and confocal microscopy studies, dynamic network swelling studies, and ATR-FTIR. Results qualitatively and quantitatively demonstrate effective glucose-binding polymers in aqueous solvent. Owing to the presence of template, the imprinting process resulted in a more macroporous structure as exhibited by dynamic swelling experiments and confocal microscopy. Polymerization kinetic studies suggest that the template molecule has more than a dilution effect on the polymerization, and the effect of the template is related strongly to the rate of propagation. In addition, PEG containing networks were micropatterned to fabricate microstructures, which would be the basis for micro-diagnostic and tissue engineering devices. Utilizing photolithography techniques, polymer micropatterns of a variety of shapes and dimensions have been created on polymer and silicon substrates using UV free-radical polymerizations with strict spatial control. Micropatterns were characterized using optical microscopy, SEM, and profilometry. The processes and analytical techniques presented are applicable to other stimuli-sensitive and recognitive networks for biomolecules, in which hydrogen bonding, hydrophobic, or ionic contributions will direct recognition. Further developments are expected to have direct impact on applications such as analyte controlled and modulated drug and protein delivery, drug and biological elimination, drug targeting, tissue engineering, and micro- or nano-devices. This work is supported by NSF Grant DGE-99-72770. Copyright © 2003 John Wiley & Sons, Ltd. [source] | ||||||||||||||||||||||