Hydrogels based on copolymers of N-(2-hydroxyethyl) methacrylamide, 2-hydroxyethyl methacrylate,and 4-t-butyi-2-hydroxycyclohexyl methacrylate

A nonionic, high water content, high-strength hydrogel based on N-(2-hydroxyethyl)methacrylamide (HMA), 2-hydroxyethyl methacrylate (HEMA), and a strengthening agent, 4-t-butyl-2-hydroxycyclohexyl methacrylate (TBCM). The HMA was prepared by the reaction of methacryloyl chloride with ethanol amine. The copolymerization of HMA with varying concentrations of HEMA and TBCM resulted in transparent hydrogel films possessing a wide range of mechanical and physical properties. A copolymer composition of 79 parts HMA, 20.7 parts TBCM, and 0.3 parts ethylene glycol dimethacrylate (EGDMA) gave a transparent, flexible film possessing a water content of 72.6%, a Young's modulus of 0.45 MPa, oxygen permeability of 28 barrers, and a tear strength of 28 N/m. In contrast, a copolymer composition of 40 parts HMA, 59.7 parts TBCM, and 0.3 parts EGDMA gave a hard, transparent film possessing a water content of 33% and a modulus of 504 MPa. © 1993 John Wiley & Sons, Inc.     

Hydrogels based on hydrophilic side-chain siloxanes

Methacrylate end-capped diethylene glycol propyl methyl ether, 5-hexyl-1,2-diol, and 3-propyloxy-1,2-propane diol side-chain siloxanes were evaluated for potential use as hydrogels for contact lens application. The preparation of the methacrylate end-capped ether, hexane diol, and propane diol side-chain siloxanes was accomplished in two relatively simple synthetic steps: The first step consisted of the acid-catalyzed co-ring opening polymerization of octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, and 1-3-bis-methacryloyl-butyltetramethyldisiloxane, followed by a platinum-catalyzed hydrosilation with (in separate experiments) diethylene glycol allyl methyl ether, trimethylsilyl protected 3-allyloxy-1,2-propane diol, and trimethylsilyl protected 5-hexene-1,2-diol. The trimethylsilyl protecting groups was removed using a 10% 0.1N HCl solution in 2-propanol. Radical polymerization of the methacrylate end-capped ether, hexane, and propane diol side-chain siloxanes with hydrophilic monomers, such as dimethylacrylamide, and a strengthening agent, isobornylmethacrylate, resulted in transparent hydrogels possessing a wide range of water contents, high oxygen permeability, and a low modulus of elasticity and, for the propane diol side-chain siloxanes, excellent hydrolytic stability. The ether side-chain siloxane-based hydrogels exhibited poor hydrolytic stability. © 1995 John Wiley & Sons, Inc.     

Die polymeranaloge Bildung von Imidgruppen in Methacrylsäure/Methacrylnitril-Copolymeren

Polymers with glutarimide-units have been prepared by an intramolecular cyclisation by heating of methacrylonitrile-methacrylic-acid-copolymers. The progress of the reaction has been determined by measuring the IR-spectra, the modulus in torsion and the increase of heat resistance. The formation of glutaric anhydride groups in addition to imide groups could be avoided by addition of urea before heating. The mechanical properties of the imid containing polymers as sheets, films and foams have been measured.     

Femtosecond laser micromachining of waveguides in silicone-based hydrogel polymers

By tightly focusing 27 fs laser pulses from a Ti:sapphire oscillator with 1.3 nJ pulse energy at 93 MHz repetition rate, we are able to fabricate optical waveguides inside hydrogel polymers containing approximately 36% water by weight. A tapered lensed fiber is used to couple laser light at a wavelength of 632.8 nm into these waveguides within a water environment. Strong waveguiding is observed due to large refractive index changes. A large waveguide propagation loss is found, and we show that this is caused by surface roughness which can be reduced by optimizing the waveguides.     

Oscillatory CO Oxidation Over Pt/Al2O3 Catalysts Studied by In situ XAS and DRIFTS

Fresh and mildly aged Pt/Al₂O₃ model diesel oxidation catalysts with small and large noble metal particle size have been studied during CO oxidation under lean burn reaction conditions to gain more insight into the structure and oscillatory reaction behaviour. The catalytic performance, CO adsorption characteristics using in situ DRIFTS and oxidation state using in situ XAS were correlated. Stable and pronounced oscillations only occurred over the catalyst with smaller particle sizes. Characteristic for this catalyst are low-coordinated surface Pt sites (more corner and edge atoms) which seem to become oxidized at elevated temperature as evidenced by in situ DRIFTS and in situ XAS. In situ XAS further uncovered that the oxidation of the Pt surface starts from the end of the catalyst bed and the oxidation state oscillates like the catalytic activity.     

Cocaprins, β-Trefoil Fold Inhibitors of Cysteine and Aspartic Proteases from Coprinopsis cinerea

We introduce a new family of fungal protease inhibitors with β-trefoil fold from the mushroom Coprinopsis cinerea, named cocaprins, which inhibit both cysteine and aspartic proteases. Two cocaprin-encoding genes are differentially expressed in fungal tissues. One is highly transcribed in vegetative mycelium and the other in the stipes of mature fruiting bodies. Cocaprins are small proteins (15 kDa) with acidic isoelectric points that form dimers. The three-dimensional structure of cocaprin 1 showed similarity to fungal β-trefoil lectins. Cocaprins inhibit plant C1 family cysteine proteases with K_i in the micromolar range, but do not inhibit the C13 family protease legumain, which distinguishes them from mycocypins. Cocaprins also inhibit the aspartic protease pepsin with K_i in the low micromolar range. Mutagenesis revealed that the β2-β3 loop is involved in the inhibition of cysteine proteases and that the inhibitory reactive sites for aspartic and cysteine proteases are located at different positions on the protein. Their biological function is thought to be the regulation of endogenous proteolytic activities or in defense against fungal antagonists. Cocaprins are the first characterized aspartic protease inhibitors with β-trefoil fold from fungi, and demonstrate the incredible plasticity of loop functionalization in fungal proteins with β-trefoil fold.     

Two-Fraction Electron System on a Thin Helium Film

A systematic theoretical investigation of microwave absorption of 2-dimensional electron systems above a thin helium film in the presence of a cyclotron resonance magnetic field is presented. To explain the measured data, a two-fraction structure of the electron system is introduced. One component corresponds to the free electron motion, the second one takes into account electron localization near the potential minimum caused by the roughness of the substrate. Within this model the general dependence of microwave absorption becomes understandable. The details of the observed cyclotron resonance line-shift are discussed.     

Selective inhibition of hepatic collagen accumulation in experimental liver fibrosis in rats by a new prolyl 4-hydroxylase inhibitor

In order to detect and characterize allergen-specific T cells in the airways of atopic asthmatics, we measured proliferation and cytokine production by bronchoalveolar lavage (BAL) T cells isolated from Dermatophagoides pteronyssinus (Der p)-sensitive asthmatics and nonatopic control subjects, and compared the results with those generated using peripheral blood (PB) T cells. BAL and PB mononuclear cells were collected 24 h after segmental allergen challenge by fibreoptic bronchoscopy and venepuncture, respectively. T cells purified from BAL and PB were stimulated with autologous, irradiated antigen-presenting cells and D. pteronyssinus extract or a control, nonallergen antigen (M. tuberculosis purified protein derivative [PPD]). IL-5 and IFN-gamma concentrations were measured in culture supernatants by ELISA, and T-cell proliferation by 3H-thymidine uptake. D. pteronyssinus-induced proliferation of T cells derived from both BAL and PB was elevated in asthmatics when compared with control subjects (p < 0.05), whereas PPD-induced proliferation was equivalent in both compartments. In the asthmatics, D. pteronyssinus-induced proliferative responses of equivalent numbers of BAL and PB T cells obtained after allergen challenge were statistically equivalent. Nevertheless, BAL T cells stimulated with D. pteronyssinus produced significantly greater amounts of IL-5 than did PB T cells (p < 0.05). Allergen-induced proliferation and IL-5 production by BAL T cells in the asthmatics after segmental allergen challenge correlated with the percentages of eosinophils in the BAL fluid (p < 0.01). Further, BAL T cells from asthmatic patients produced significantly higher amounts of IL-5 than did the same number of cells from nonatopic control subjects (p < 0.05). We conclude that, in D. pteronyssinus-sensitive asthmatics, allergen-specific T cells can be detected in the bronchial lumen after allergen challenge and that allergen-induced proliferation and IL-5 production by these cells correlates with local eosinophil influx. Although bronchial luminal T cells show an equivalent proliferative response to allergen stimulation as compared with PB T cells, they do produce more IL-5, consistent with the hypothesis that local differentiation or priming of these cells within the bronchial mucosal environment results in upregulation of allergen-induced IL-5 secretion.     

Schistosoma mansoni-related morbidity on Ukerewe Island, Tanzania: clinical, ultrasonographical and biochemical parameters

The osmotic responses of isolated human islets were evaluated using a perfusion cryomicroscope device. Individual islet volumes were measured following equilibration with a series of solutions of graded solute concentration. The osmotically inactive volume for human islets was determined to be 25% from a Boyle-van't Hoff plot of these data. A network thermodynamic model was developed via the bond graph method to describe the transport of water and cryoprotective agent in pancreatic islets. The model was curve fit to transient volumetric data for the response of islets to a stepwise exposure to 1 Me2SO at temperatures of 24.0, 3.0, or -3.5 degrees C. Standard membrane transport parameters (Lp, omega, sigma) and interstitial diffusion transport properties (kappa w, kappa p) were calculated from the fitting procedure. The temperature coefficients for membrane transport properties were expressed in terms of activation energies for water (ELp) and Me2SO (E omega). Osmotic challenge experiments conducted with fresh and cryopreserved human islets indicate that frozen/thawed islets exhibit a a slight increase in transport properties.