A New Method to Prepare Porous Silk Fibroin Membranes Suitable for Tissue Scaffolding Applications

A new method to prepare porous silk fibroin (SF) membranes without dialysis proposed. Silk fibers were degummed to remove sericin and the resultant fibroin was dissolved in a CaCl(2)-CH(3)CH(2)OH-H(2)O ternary solvent. Rather than undergoing dialysis, a fibroin salty solution was diluted in water and then submitted to a mechanical agitation that led to a phase separation through foam formation on the solution surface. This foam was continually collected and then compacted between plates to remove the excess of water. The membranes presented large pores with diameters of greater than 100 pm (as shown by scanning electron microscopy - SEM), porosity of 68% and water content of 91% w/w. X-ray diffraction (XRD) and infrared spectroscopy (FTIR-ATR) indicated that the membranes present SF in a beta-sheet structure even before the ethanol treatment. A typical elastic deformation profile and degradation under temperature were observed using calorimetric analysis (DSC), thermal gravimetric analysis (TGA) and mechanical tests. As indicated by the in vitro cytotoxicity tests, these membranes present potential for use as scaffolds. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 114: 617-623, 2009

Structural characterization of exopolysaccharides from biofilm of a cariogenic streptococci

Soluble (EPS-SOL), as well as insoluble extracellular polysaccharide (EPS-INSOL), extracted from biofilm of Streptococcus mutans, were analyzed by nuclear magnetic resonance spectroscopy, methylation analysis, and a controlled Smith degradation. EPS-SOL was a branched alpha-glucan containing a (1 -> 6)-and (1 -> 3)-linkages. EPS-INSOL was a branched alpha-glucan with similar linkages, but with a (1 -> 3)-linked main-chain partially substituted at O-6 with Glcp-(1 -> 6)-Glcp-side chains. Biofilm EPS had a distinct chemical structure compared with those synthesized by plankton cells or by purified enzymes from S. mutans, which could indicate different mechanisms for its degradation. (C) 2011 Published by Elsevier Ltd.

NMR study of the radiation-induced cross-linking of poly(tetrafluoroethylene-co-perfluoromethyl vinyl ether)

The gamma-radiolysis of poly(tetrafluoroethylene-co-perfuoromethyl vinyl ether) (TFE/PMVE) was investigated using solid state F-19 and C-13 NMR spectroscopy. Chain scission products identified in the polymer were saturated chain ends -CF2CF3 (G = 1.0), methyl ether end groups -CF2OCF3 (G = 0.9), acid end groups -CF2COOH (G = 0.5), and a small amount of terminal unsaturation -CF=CF2 (G = 0.2). A mechanism for the formation of these scission products was proposed and the G value for main chain scission, G(S), was determined to be 1.4. Cross-linking of TFE/PMVE was found to proceed via a Y-linking mechanism. The G value for cross-linking, G(X), was determined to be 0.9. A maximum of 0.2 mol % cross-links were formed under the experimental conditions.

The crosslinking mechanism in gamma irradiation of polyarylsulfone: Evidence for Y-links

Measurements of molecular weights, soluble fractions and examination of NMR spectra of bisphenol-A polysulfone, after gamma irradiation in vacuum at 150 degrees C were used to elucidate the mechanism of crosslinking. Excellent agreement was obtained between G(S) and G(X) determined from measurements above and below the gel dose when a Y-linking mechanism was assumed, whereas poor agreement was obtained when an H-link mechanism was assumed, which is the mechanism normally believed to be responsible for crosslinking. New resonances were observed in the C-13 NMX spectra of the irradiated polymer which were consistent with the formation of Y-links involving phenylene units in the backbone chain. (C) 1998 John Wiley & Sons, Ltd.

An ESR and NMR study of the gamma radiolysis of a bisphenol-A based polycarbonate and a phthalic acid ester

A study of the gamma-radiolysis of the commercial polymers U-polymer, UP (Unitake) and polycarbonate, PC, (Aldrich) has been undertaken using ESR spectroscopy. The G-value of radical formation at 77 K has been found to be 0.31 +/- 0.01 for UP and 0.5 +/- 0.02 for PC. By using thermal annealing and spectral subtraction, the paramagnetic species formed on irradiation has been assigned. The effect of radiation on the chemical structure of UP and PC has been investigated at ambient temperature and at 423 K. The NMR results show that a new phenol type chain end is formed in the polymers on exposure to gamma-radiation. The G-value of formation of the new phenol ends was estimated to be 0.7 for PC (423 K) and 0.4 for UP (300 K). (C) 1998 John Wiley & Sons, Ltd.

Free volume and water uptake in a copolymer hydrogel series

A copolymer of X-hydroxyethyl methacrylate (HEMA) with 2-ethoxy ethyl methacrylate (EEMA) was synthesized and the molecular mobility, free volume, and density properties examined as a function of composition. These properties were correlated with the equilibrium water uptake in order to determine which of the properties were most influential in causing high water sorption, as these materials are suitable candidates for hydrogel systems. It was found that the polar HEMA repeat unit results in a rigid, glassy sample at room temperature due to the high degree of hydrogen bonding between chains whereas high EEMA content leads to rubbery samples with subambient glass transition temperatures. The free volume properties on the molecular scale measured by positron annihilation Lifetime spectroscopy (PALS) showed that higher HEMA content led to smaller, fewer holes and a lower free volume fraction than EEMA. Therefore the high water uptake of HEEMA-containing copolymers is largely related to the high polarity of the HEMA unit compared to EEMA, despite the low content of free volume into which the water can initially diffuse. Trends in density with copolymer composition, as measured on a macroscopic level, differs to that seen by PALS and indicates that the two techniques are measuring different scales of packing. (C) 1998 John Wiley & Sons, Inc.

The use of crosslinking promoters in the gamma-radiolysis of poly(tetrafluoroethylene-co-perfluoromethylvinyl ether). I

Incorporation of 1 wt % of triallyl isocyanurate (TAIC) significantly enhanced the radiation crosslinking of the perfluoroelastomer, poly(tetrafluoroethylene-co-perfluoromethylvinyl ether) (TFE/PMVE). The dose for gelation was lowered by 70% with the presence of TAIC. The additive also improved the tensile properties of TFE/ PMVE both before and after crosslinking by irradiation. Higher radical yields were obtained with the presence of TAIC at 77 K, indicating the crosslinking promoter was acting as a radical trap. ESR studies showed that radiolysis of TAIC and subsequent photobleaching cleaved an allyl branch from the ring structure. Upon thermal annealing, an allyl radical on the TAIC molecule was observed. (C) 1999 John Wiley & Sons, Inc.

Miscibility and specific interactions in blends of poly(4-vinylphenol) and poly(2-ethoxyethyl methacrylate)

The properties of the hydrogen-bonded polymer blends of poly(4-vinylphenol) and poly(2-ethoxyethyl methacrylate) are presented. Spectroscopic techniques such as C-13 solid-state NMR and FT-IR are used to probe specific interactions of the blends at various compositions. Spectral features from both techniques revealed that site-specific interactions are present, consistent with a significant degree of mixing of the blend components. Changes in chemical shift and line shape of the phenolic carbon and carbonyl resonances in the C-13 CPMAS spectra of the blends as a function of composition are interpreted as resulting from changes in the relative intensities of two closely overlapped signals. A quantitative measure of hydrogen-bonded carbonyl groups using C-13 NMR has been obtained which agreed well with the results from FT-IR analyses. It is also shown that C-13 NMR can be used to measure the fraction of hydroxyl groups associated with carbonyl groups, which was not possible previously using FT-IR due to extensive overlapping of bands in the hydroxyl stretching region. The results of measurements of H-1 T-1 and 1H T-1 rho indicate that PVPh and PEEMA are intimately mixed on a scale less than 2-3 nm.

A comparative study of the effects of UV- and gamma-radiation on copolymers of acrylonitrile/butadiene

The radiolysis of nitrile rubbers with different acrylonitrile/butadiene composition and the homopolymers, poly(butadiene) (PBD) and poly(acrylonitrile) (PAN) has been investigated and compared with the photolysis of the same polymers. A significantly different mechanism of degradation was found for the two types of radiation. The results obtained by ESR, FTIR and measurements of soluble fractions of irradiated samples, indicated that the acrylonitrile units of the nitrile rubbers are more sensitive units to gamma-radiation, with the effects of irradiation increasing with the acrylonitrile content. The reactions observed were consumption of double bonds, crosslinking, and cyclization with the formation of conjugated double bonds. No chain-scission reactions were detected. In contrast to gamma-irradiation, the effects of photolysis were centred at the butadiene units, and increases in the acrylonitrile content resulted in a proportional decrease in the sensitivity of the copolymers. Crosslinking and chain scission were identified as the main effects of photolysis of NBR rubbers. (C) 1999 Society of Chemical Industry.

Effect of temperature and a crosslinking promoter on the gamma-radiolysis of a perfluoroelastomer

Methods of promoting the radiation-induced cross linking of poly(tetrafluoro-ethylene-co-perfluoromethyl vinyl ether) (TFE/PMVE) have been investigated. Greater control of the crosslinking and chain-scission reactions was achieved by varying the radiolysis temperature. This was attributed to temperature affecting the mobilities of reactive species such as polymeric free radicals. These reactive species are precursors to radiation-induced cross links and chain-ends. Analysis of the sol/gel behaviour, tensile properties and FTIR indicated that the optimum temperature for the radiation crosslinking of TFE/PMVE, at a dose of 150 kGy, was 263 K. This temperature was 10 K below the glass transition temperature. Incorporation of 1 wt% triallyl isocyanurate (TAIC) greatly amplified the radiation crosslinking of TFE/PMVE, The dose for gelation was decreased by 70%, and the additive imparted superior mechanical properties compared to the neat irradiated TFE/PMVE. Electron spin resonance (ESR) measurements showed higher radical yields at 77 K with the 1 wt% TAIC, indicating that the crosslinking promoter was acting as a radical trap. (C) 1999 Society of Chemical Industry.

Water diffusion in hydroxyethyl methacrylate (HEMA)-based hydrogels formed by gamma-radiolysis

Polymer hydrogels based upon methacrylates are used extensively in the pharmaceutical industry, particularly as controlled release drug delivery systems. These materials are generally prepared by chemically initiated polymerization, but this can lead to the presence of unwanted initiator fragments in the polymer matrix. In the present work, initiation of polymerization by gamma-irradiation of hydroxyethyl methacrylate, with and without added crosslinkers, has been investigated, and the diffusion coefficients for water in the resulting polymers have been measured through mass uptake by the polymers. The diffusion of water in poly(hydroxyethyl methacrylate) at 310 K was found to be Fickian, with a diffusion coefficient of 1.96 +/- 0.1 x 10(11) m(2) s(-1) and an equilibrium water content of 58%, NMR imaging analyses confirmed the adherance to a Fickian model of the diffusion of water into polymer cylinders. The incorporation of small amounts (0.2-0.5 wt%) of added ethyleneglycol-dimethacrylate-based crosslinkers was found to have only a small effect on the diffusion coefficient and the equilibrium water content for the copolymers. (C) 1999 Society of Chemical Industry.

Polymerization of diglycidyl ether of bisphenol A/diaminodiphenyl sulfone epoxy resins using radio frequency fields

Curing of diglycidyl ether of bisphenol A/diaminodiphenyl sulfone (DGEBA/DDS) epoxy resin has been effected by heating with radio frequency (RF) radiation at frequencies of 30-99 MHz. The epoxy resins can be cured rapidly at low RF power levels. Comparison of the kinetics of the RF curing with thermal curing while maintaining the same curing temperature revealed no differences. Previous differences in rates of thermal and microwave curing are believed to be due to lack of temperature control during microwave curing. For RF curing,the rate of cure, at constant power level, increases at lower RF frequency, thus emphasizing one of the principal advantages of RF curing over microwave curing. (C) 1999 John Wiley & Sons, Inc.

Copolymer hydrogels of 2-hydroxyethyl methacrylate with n-butyl methacrylate and cyclohexyl methacrylate: synthesis, characterization and uptake of water

The bulk free radical copolymerizations of 2-hydroxyethyl methacrylate (HEMA) with n-butyl methacrylate (BMA) or cyclohexyl methacrylate (CHMA) were studied over the composition mole fraction interval of 0-1 for HEMA in the monomer feed. The C-13 NMR (125 MHz) spectra of the copolymers were analysed to determine the copolymer composition and the stereochemical configuration of the copolymers. The terminal model reactivity ratios of HEMA and BMA were found to be r(HEMA) = 1.73 and r(BMA) = 0.65 and for HEMA and CHMA, r(HEMA) = 1.26 and r(CHMA) = 0.31. The BMA and CHMA homopolymers were found to be predominantly syndiotactic with isotacticity parameters of theta(BB) = 0.18 and theta(CC) = 0.19, respectively. The copolymers were also found to be predominantly syndiotactic, indicating a strong tendency for racemic additions of the monomers in the formation of the copolymers. The diffusion of water into cylinders of poly(HEMA-co-BMA) and poly(HEMA-co-CHMA) was studied over a range of copolymer compositions and was found to be Fickian. The diffusion coefficients of water at 37 degrees C were determined from swelling measurements and were found to vary from 1.72 x 10(-11) m(2) s(-1) for polyHEMA to 0.97 x 10(-11) m(2) s(-1) for poly(HEMA-co-BMA) having a mole fraction F-HEMA = 0.80 and to 0.91 x 10(-11) m(2) s(-1) for a poly(HEMA-co-CHMA) also having F-HEMA = 0.80. The mass of water absorbed at equilibrium relative to the mass of dry polymer varied from 58.8 for polyHEMA to 27.2% for poly(HEMA-co-BMA) having F-HEMA = 0.85 and to 21.3% for poly(HEMA-co-CHMA) having F-HEMA = 0.80. (C) 1999 Elsevier Science Ltd. All rights reserved.

Thermal and radiation curing of phenylethynyl terminated macromers

The thermal and gamma-irradiation induced curing of two phenylethynyl terminated composite resin systems, DFB/BPF and PETI5A, was investigated. Thermal curing of these matrix resin samples was performed at a temperature of 360 degrees C, gamma irradiation of the samples was conducted at 300 degrees C at a dose rate of 2.2 kGy h(-1). The reaction and subsequent loss of ethynyl groups in the resins for both cure methods was demonstrated by observing the decrease of the 2215 cm(-1) peak in the Raman spectra of the resins. Fully cured resin samples were found to have glass transition temperatures of 244-246 degrees C and 278-280 degrees C for DFB/BPF and PETI5A respectively. Similar relationships between T-g and fractional conversion were observed in both resins. The apparent polymerization rate, R-p, for thermal cure at 360 degrees C, was found to be 4.79 x 10(-2)% s(-1) in PETI5A and 3.22 x 10(-2)% s(-1) in DFB/BPF. Catastrophic degradation under nitrogen was observed to commence near 450 degrees C and 530 degrees C, with 5% weight losses occurring at 455 degrees C and 540 degrees C for DFB/BPF and PETI5A respectively. Gamma radiation induced cure at 300 degrees C was shown to be feasible, with full cure being reached with doses of 40 kGy for DFB/BPF and 100 kGy for PETI5A.

Effect of additives on gelatinization, rheological properties and biodegradability of thermoplastic starch

Effect of additives on the starch gelatinization was governed by the processing conditions. The order-disorder transition of starch in water can occur in more than one way and the effect of polar additives on gelatinization can also be in more than one way. The additives appear to be plasticising thermoplastic starches, resulting in improving rheological properties. The thermoplastic starches with the additives are all biodegradable although the rates of biodegradability are slightly different.