NMR imaging of the diffusion of water at 310 K into semi-IPNs of PEM and Poly(HEMA-co-THFMA)

Magnetic resonance imaging has been used to monitor the diffusion of water at 310 K into a series of semi-IPNs of poly(ethyl methacrylate), PEM, and copolymers of 2-hydroxyethyl methacrylate, HEMA, and tetrahydrofurfuryl methacrylate, THFMA. The diffusion was found to be well described by a Fickian kinetic model in the early stages of the water sorption process, and the diffusion coefficients were found to be slightly smaller than those for the copolymers of HEMA and THFMA, P(HEMA-co-THFMA), containing the same mole fraction of HEMA in the matrix. A second stage sorption process was identified in the later stage of water sorption by the PEM/PTHFMA semi-IPN and for the systems containing a P(HEMA-co-THFMA) component with a mole fraction HEMA of 0.6 or less. This was characterized by the presence of Water near the surface of the cylinders with a longer NMR T-2 relaxation time, which would be characteristic of mobile water, such as water present in large pores or surface fissures. The presence of the drug chlorhexidine in the polymer matrixes at a concentration of 5.625 wt % was found not to modify the properties significantly, but the diffusion coefficients for the water sorption were systematically smaller when the drug was present.

NMR imaging of the diffusion of water at 310 K into poly[(2-hydroxyethyl methacrylate)-co-(tetrahydrofurfuryl methacrylate)] containing vitamin B12 or aspirin

The ingress of water into copolymers of 2-hydroxyethyl methacrylate (HEMA) and tetrahydrofurfuryl methacrylate (THFMA) loaded with either one of two model drugs, ie vitamin B-12 or aspirin, was studied at 310 K using three-dimensional nuclear magnetic resonance (3D NMR) imaging. The poly(HEMA) was loaded with 5 wt% of the drugs. From the imaging profiles it was observed that incorporation of vitamin B-12 into the polymers rich in HEMA resulted in crack formation at the interface between the rubbery region and the glassy core on sorption of water, although these cracks were 'healed' behind the diffusion front. However, for the copolymers with low HEMA contents and for those containing aspirin, no evidence for similar crack formation was found. For the copolymers loaded with 5 wt% of aspirin or vitamin B-12 the values of the water diffusion coefficients, determined by curve-fitting the relative water concentration profiles from magnetic resonance imaging (MRI) measurements, were found to be smaller than those obtained from a mass uptake study. (C) 2004 Society of Chemical Industry.

Vitamin B-12 release from P(HEMA-co-THFMA) in water and SBF: A model drug release study

A model drug release study on the ingress of water and Kokubo simulated body fluid (SBF) into poly(2-hydroxyethyl methacrylate) (THFMA) and its copolymers with tetrahydrofurfuryl methacrylate (THFMA) loaded with vitamin B-12 was undertaken over the temperature range 298-318 K. The polymers were studied as cylinders and were loaded with either 5 or 10 wt-% of the drug. The drug release from the polymers was found to follow a Fickian diffusion mechanism in the early stages of the drug release, with higher normalized release rates at higher temperatures and higher drug loadings. The normalized release rates were also found to be higher for the SBF solution than for water. The copolymer composition was found to have a significant effect on the rate of release of the drug, with the rate falling rapidly between HEMA mole fractions of 1.0 and 0.8, but for lower mole fractions of HEMA the normalized release rate decreased more slowly. This behaviour followed the trend found for the changes in the equilibrium penetrant contents for the copolymers.

Investigation into the diffusion of water into HEMA-co-MOEP hydrogels

Cross-linked homopolymers and copolymers of 2-hydroxyethyl methacrylate, HEMA, and ethylene glycol methacrylate phosphate, MOEP, have been synthesized, and the diffusion of water into these systems has been investigated. Only polymers with 0-20 mot % MOEP exhibited ideal swelling behavior as extensive fracturing occurred in the systems with greater than 20 mot % MOEP as the polymers began to swell during water sorption. Gravimetric studies were used in conjunction with magnetic resonance imaging of the diffusion front to elucidate the diffusion mechanism for these systems. In the case of the cross-linked HEMA homopolymer gets, the water transport mechanism was determined to be concentration-independent Fickian diffusion. However, as the fraction of MOEP in the network increased, the transport mechanism became increasingly exponentially concentration-dependent but remained Fickian until the polymer consisted of 30 mot % MOEP where the water transport could no longer been described by Fickian diffusion.

Chain scission and branching in irradiated poly(tetrafluoroethylene-co-hexafluoropropylene)

The radiation chemistry of poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP) with a TFE mole fraction of 0.90 has been studied under vacuum using Co-60 gamma-radiation over a range of temperatures and absorbed doses. The radiolysis temperatures were 300, 363, 423, 523 and 543 K. New structure formation in the copolymers was analysed by solid-state F-19 NMR spectroscopy. The new structures formed in the copolymers have been identified and the G-values for the formation of new chemical structures have been investigated at 363 and 523 K. These two temperatures are just above and just below the polymer T-g and T-m, respectively. At the lower temperature, there was no evidence for any chain branching and an estimate of G(S) of 1.0 was obtained. A value of G(S) of 1.3 and a minimum value of G(X)(Y) of 1.3 were obtained at 523 K. (C) 2003 Society of Chemical Industry.

The influence of architecture on degradation and tissue ingrowth into three-dimensional poly(lactic-co-glycolic acid) scaffolds in vitro and in vivo

The in vitro and in vivo degradation properties of poly(lactic-co-glycolic acid) (PLGA) scaffolds produced by two different technologies-therm ally induced phase separation (TIPS), and solvent casting and particulate leaching (SCPL) were compared. Over 6 weeks, in vitro degradation produced changes in SCPL scaffold dimension, mass, internal architecture and mechanical properties. TIPS scaffolds produced far less changes in these parameters providing significant advantages over SCPL. In vivo results were based on a microsurgically created arteriovenous (AV) loop sandwiched between two TIPS scaffolds placed in a polycarbonate chamber under rat groin skin. Histologically, a predominant foreign body giant cell response and reduced vascularity was evident in tissue ingrowth between 2 and 8 weeks in TIPS scaffolds. Tissue death occurred at 8 weeks in the smallest pores. Morphometric comparison of TIPS and SCPL scaffolds indicated slightly better tissue ingrowth but greater loss of scaffold structure in SCPL scaffolds. Although advantageous in vitro, large surface area:volume ratios and varying pore sizes in PLGA TIPS scaffolds mean that effective in vivo (AV loop) utilization will only be achieved if the foreign body response can be significantly reduced so as to allow successful vascularisation, and hence sustained tissue growth, in pores less than 300 mu m. (C) 2005 Elsevier Ltd. All rights reserved.

Mass uptake study of the diffusion of water and SBF into poly(2-hydroxyethyl methacrylate-co-tetrahydrofurfuryI methacrylate) containing aspirin or vitamin B-12

The ingress of water and Kokubo simulated body fluid (SBF) into poly (2-hydroxyethyl methacrylate) (PHEMA), and its co-polymers with tetrahydrofurduryl methacrylate (THFMA), loaded with either one of two model drugs, vitamin 1312 or aspirin, was studied by mass uptake over the temperature range 298-318 K. The polymers were studied as cylinders and were loaded with either 5 wt% or 10 wt% of the drugs. From DSC studies it was observed that vitamin B-12 behaved as a physical cross-linker restricting chain segmental mobility, and so had a small anti-plasticisation effect on PHEMA and the co-polymers rich in HEMA, but almost no effect on the T-g of co-polymers rich in THFMA. On the other hand, aspirin exhibited a plasticising effect on PHEMA and the copolymers. All of the polymers were found to absorb water and SBF according to a Fickian diffusion mechanism. The polymers were all found to swell to a greater extent in SBF than in water, which was attributed to the presence of Tris buffer in the SBF. The sorptions of the two penetrants were found to follow Fickian kinetics in all cases and the diffusion coefficients at 310 K for SBF were found to be smaller than those for water, except for the polymers containing aspirin where the diffusion coefficients were higher than for the other systems. For example, for sorption into PHEMA the diffusion coefficient for water was 1.41 X 10(-11) m(2)/s and for SBF was 0.79 x 10-11 m(2)/s, but in the presence of 5 wt% aspirin the corresponding values were 1.27 x 10(-1)1 m(2)/s and 1.25 x 10(-11) m(2)/s, respectively. The corresponding values for PHEMA loaded with 5 wt% B-12 were 1.25 x 10(-11) m(2)/s and 0.74 x 10(-11) m(2)/s, respectively.

Water diffusion in methacrylate based copolymer hydrogels of 2-hydroxyethyl methacrylate

The diffusion of water into cylinders of polyHEMA and copolymers of HEMA with THFMA, BMA and CHMA were studied over a range of copolymer compositions. The diffusion of water into the polymers was found to follow a Fickian, or case I mechanism. The diffusion coefficients of water were determined from mass measurements and NMR imaging studies. They were found to vary from 1.7 +/- 0.2 x 10(-11) m(2) s(-1) for polyHEMA at 37 degreesC to lower values for the copolymers. The mass of water absorbed at equilibrium relative to the mass of dry polymer varied from 52-58 wt% for polyHEMA to lower values for the copolymers.

Ion beam modification and analysis of metal/polymer bi-layer thin films

A set of varying-thickness Au-films were thermally evaporated onto poly(styrene-co-acrylonitrile) thin film surfaces. The Au/PSA bi-layer targets were then implanted with 50 keV N+ ions to a fluence of 1 × 1016 ions/cm2 to promote metal-to-polymer adhesion and to enhance their mechanical and electrical performance. Electrical conductivity measurements of the implanted Au/PSA thin films showed a sharp percolation behavior versus the pre-implant Au-film thickness with a percolation threshold near the nominal thickness of 44 Å. The electrical conductivity results are discussed along with the film microstructure and the elemental diffusion/mixing within the Au/PSA interface obtained by scanning electron microscopy (SEM) and ion beam analysis techniques (RBS and ERD).

An ESR study of the radiolysis of semi-crystalline ethylene-propylene copolymers containing DOP mobilizer

The radiolysis of a poly(ethylene-co-propylene), Elpro, marketed by Thai Polypropylene Co. Ltd for the manufacture of medical goods has been investigated at 77 K. Calcium stearate was blended with the Elpro as a processing aid; and dioctyl phthalate, DOP, was added in various amounts as a radiation stabilizer. The ESR spectra of Elpro and Elpro+Ca were very similar and characterized principally by the presence of PP a-carbon radicals. The spectra of the samples containing DOP were similar to those for Elpro but with an additional narrow singlet arising from DOP radicals. On annealing the irradiated polymers to higher temperatures, the singlet was lost between 250 and 270 K, and at room temperature the principal radicals remaining were allyl radicals. The G-values for radical formation at 77 K for Elpro and Elpro+Ca at 77 K were 3.0 and 3.2, respectively, but incorporation of DOP resulted in lower G-values, ranging from 1.6 to 1.4 for 0.5 and 2.5 phr DOP, respectively.(c) 2005 Wiley Periodicals, Inc.

A rheology study of high-energy radiolysis of a semicrystalline ethylene-propylene copolymer containing DOP mobilizer

The ractiolysis of a poly(ethylene-co-propylene), Elpro grade P 750 J, marketed by Thai Polypropylene Co. Ltd. for the manufacture of medical goods, was investigated at ambient temperature and melt rheology measured. The roles of calcium stearate, blended with the Elpro as a processing aid, and dioctyl phthalate (DOP), added in various amounts as a radical scavenger, were assessed. Following radiolysis, G' and the viscosity of the polymer melts at 453 K both decreased with increasing radiation dose, even when the mobilizer was present. The results indicated that although the DOP did scavenge radicals, it did not protect the polymer from net chain scission in a low-dose regimen. The value of (G(S) - 4G(X)) was approximately 0.6-0.7. (c) 2006 Wiley Periodicals, Inc.

Systematic selection of solvents for the fabrication of 3D combined macro- and microporous polymeric scaffolds for soft tissue engineering

In this study, we investigate the fabrication of 3D porous poly(lactic-co-glycolic acid) (PLGA) scaffolds using the thermally-induced phase separation technique. The current study focuses on the selection of alternative solvents for this process using a number of criteria, including predicted solubility. toxicity, removability and processability. Solvents were removed via either vacuum freeze-drying or leaching, depending on their physical properties. The residual solvent was tested using gas chromatography-mass spectrometry. A large range of porous, highly interconnected scaffold architectures with tunable pore size and alignment was obtained, including combined macro- and microporous structures and an entirely novel 'porous-fibre' structure. The morphological features of the most promising poly(lactic-co-glycolic acid) scaffolds were analysed via scanning electron microscopy and X-ray micro-computed tomography in both two and three dimensions. The Young's moduli of the scaffolds under conditions of temperature, pH and ionic strength similar to those found in the body were tested and were found to be highly dependent on the architectures.