Poly(ethylene oxide) (PEO) polymer, in linear and star form, was covalently grafted to silicon surfaces, and the surfaces were tested for their ability to adsorb proteins. Linear PEG of molecular weight 3400, 10 000, and 20 000 g/mol and star PEO molecules were coupled via their terminal hydroxyl groups activated by tresyl chloride to aminosilane-treated silicon wafers. The amount of PEO coupled to the surface was varied by changing the concentration of the tresyl-PEO solution. The dry PEO thickness on the surface was measured using X-ray photoelectron spectroscopy (XPS) and ellipsometry, from which the grafting density was calculated. The PEO surfaces were exposed to solutions of each of three proteins: cytochrome-c, albumin, and fibronectin. The degree of adsorption of each protein was determined by XPS and ellipsometry and recorded as a function of PEO grafting density. All three proteins were found to reach zero adsorption at the highest grafting densities on all three PEG surfaces, which for all three PEG surfaces was a PEO content of 100 +/- 10 ng/cm2. On both star PEO surfaces, albumin and fibronectin decreased to zero adsorption at intermediate values of grafting density, whereas cytochrome-c continued to adsorb at all grafting densities, although with a decreasing trend. A physical model of the surface helped explain these protein adsorption results in terms of the spacing and degree of overlap of grafted PEO chains.
SynopsisTransparent crosslinked PVA hydrogels were prepared by electron beam irradiation of aqueous solutions under nitrogen. These weak hydrogels, upon swelling a t 30 "C in water, showed low elastic moduli (up to 50 psi), low ultimate tensile strength (up to 4 psi), and low extensibility to break (not higher than 85%). Values of the molecular weight between crosslinks M , were calculated from swelling and from tensile experiments. In fact, two values of M , were calculated for each swelling experiment, (a) allowing for observed variation in the polymer-solvent interaction parameter x1 with concentration, and (b) fixing x1 = 0.494 according to literature data. The correlation of the M,. obtained from tensile data with the M , obtained from swelling data, by (a) or (b), was approximately linear and gave the same per cent agreement.
Aqueous poly(vinyl alcohol) solutions were crosslinked via electron‐beam irradiation to form transparent hydrogels of varying crosslinking densities. Typical crosslinked hydrogels with Mc between 3500 and 8000 were weak, easily shattered, nonextensible materials with very low tensile moduli (up to 70 psi) and tensile strengths at break (less than 10 psi). Reinforcement by induction of partial crystallization was accomplished by a two‐stage drying process, consisting of a slow dehydration stage at room temperature and an annealing stage at elevated temperatures, which was mainly responsible for the introduction of the crystallites. The swollen hydrogels after the annealing process had crystallinities widely varying between 30 and 65% and polymer volume fractions between 30 and 60%, depending on the temperature‐time history of the specimen. These materials showed greatly improved mechanical properties (modulus, ultimate tensile strength, tear strength), as compared to the uncrystallized hydrogels.
Drag reduction caused by dilute, distilled water solutions of five polyethylene oxides, molecular weights from 80,000 to 6,000,000, in turbulent pipe flow was studied experimentally in 0·292 and 3·21 cm ID pipes. It was found that the onset of drag reduction occurs at a well-defined wall shear stress related to the random-coiling effective diameter of the polymer. Laminar to turbulent transition is not, in general, delayed. The extent of drag reduction induced by a homologous series of polymers in a given pipe is a universal function of concentration, flow rate, and molecular weight. The maximum drag reduction possible is limited by an asymptote that is independent of polymer and pipe diameter. Flow structure measurements in a single polymer solution, 1000 ppm of molecular weight 690,000, showed that the mean flow follows an ‘effective slip’ model. In this, the mean velocity profile consists of a ‘Newtonian plug’ convected along at an additional, ‘effective slip’ velocity. The turbulent flow structure follows the ‘effective slip’ model towards the pipe wall, but is significantly different from Newtonian towards the pipe axis; in particular, the inertial subrange observed in isotropic Newtonian turbulence was absent in an energy spectrum taken on the pipe axis in the polymer solution.
SynopsisCrosslinked poly(viny1 alcohol) hydrogels produced via electron beam irradiation of aqueous PVA solutions were crystallized via a two-stage dehydration-annealing process to produce swollen hydrogels of varying degrees of crystallinity. Evaluation of the degree of crystallinity of these hydrogels was done by differential scanning calorimetry (DSC) analysis. The swollen hydrogels had degrees of crystallinities varying between 30% and 50% depending on the temperature-time history of the specimens.
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