Modular material system for the microfabrication of biocompatible hydrogels based on thiol–ene‐modified poly(vinyl alcohol)

Novel modifications of the synthetic polymer poly(vinyl alcohol) (PVA) were developed for application in the field of biomedical engineering. PVA was modified with allyl succinic anhydride, norbornene anhydride as well as with γ‐thiobutyrolactone to produce macromers with reactive ene and thiol groups, respectively. Cytotoxicity studies have shown that the material exhibits almost no cell‐toxicity, when used in concentrations of 1 and 0.1 wt % for 24 h. The obtained macromers were photocrosslinked via thiol–ene chemistry. Storage stability of the macromer mixtures with different concentrations of pyrogallol as stabilizer were investigated. Photorheometry was employed to optimize mixtures concerning reactivity based on their thiol‐to‐ene ratio, photoinitiator concentration, and macromer content. The crosslinked hydrogels were studied concerning their swellability. To form hydrogels with cellular structure two‐photon‐polymerization (2PP) was employed. Processing windows for 2PP of selected mixtures were determined. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2060–2070     

Approximation of the hydrostatic Navier–Stokes system for density stratified flows by a multilayer model: Kinetic interpretation and numerical solution

We present a multilayer Saint-Venant system for the numerical simulation of free surface density-stratified flows over variable topography. The proposed model formally approximates the hydrostatic Navier–Stokes equations with a density that varies depending on the spatial and temporal distribution of a transported quantity such as temperature or salinity. The derivation of the multilayer model is obtained by a Galerkin-type vertical discretization of the Navier–Stokes system with piecewise constant basis functions. In contrast with classical multilayer models in the literature that assume immiscible fluids, we allow here for mass exchange between layers. We show that the multilayer system admits a kinetic interpretation, and we use this result to formulate a robust finite volume scheme for its numerical approximation. Several numerical experiments are presented, including simulations of wind-driven stratified flows.     

Five-coordinate Pd(II) orthometallated triarylphosphite complexes

The reaction of the orthopalladated triarylphosphite complexes [{Pd(mu-Cl){kappa(2)-P,C-P(OC(6)H(2)-2,4-R(2))(OC(6)H(3)-2,4-R(2))}(2)] (R = H, (t)Bu) with bis(2-diphenylphosphinoethyl)phenylphosphine leads to a five-coordinate palladium(II) (R = H) and a mixture containing four-and five-coordinate species (R = (t)Bu). The crystal structure of the five-coordinate species [Pd{kappa(2)-P,C-(P(OC(6)H(4))(OC(6)H(5))(2)}{bis(2-diphenylphosphinoethyl)phenylphosphine}][SbF(6)] is presented. This complex reacts with hydrogen peroxide or [AuCl(tht)] to give four-coordinate complexes in which the displaced phosphine residue is either oxidised or coordinated to gold chloride; this demonstrates that the five-coordinate complexes are labile in solution. By contrast, the reactions of the dimeric precursors with 1,1,1-tris(diphenylphosphinomethyl)ethane give four-coordinate complexes in the solid state, although evidence is presented that the smaller phosphite-containing system is five-coordinate at room temperature or higher in solution.     

Synthesis of thiacrown and azacrown ethers based on a spiroacetal framework

A novel class of thiacrown and azacrown ethers incorporating the 1,7-dioxaspiro[5.5]undecane spiroacetal ring system was prepared by reaction of ditosylate 5 with the appropriate dithiols 9a-c or protected diamine 12a. Spiroacetal ditosylate 5 in turn, was prepared from diol 3 via ozonolysis of bisallyl ether 7 followed by tosylation of the derived diol 8.     

Electric-field-induced g/u mixing of the E0g+(3P2) and D0u+(3P2) ion-pair states of jet-cooled I2 observed using optical triple resonance

Electric-field-induced electronic state g/u mixing of nearly isoenergetic rovibrational levels of the E0g+(3P2) and D0u+(3P2) ion-pair states of I2 has been observed using optical triple resonance combined with resonance ionization. Detectable mixing with applied fields of 1 kV/cm occurs over a range of energy level separations of < or = 0.3 cm(-1).     

Separation and quantitation of human plasma acid stable trypsin inhibitors by RP-HPLC

Summary Human plasma contains acid stable trypsin inhibitors (ASTIs) which are present in small quantities and are bound tightly but reversibly to the enzyme. For the analysis of such endogenous inhibitors a procedure has been proposed analogous to that described by us for urinary trypsin inhibitors (UTIs). This chromatographic procedure allows a direct measurement of such substances and avoids the remarkable losses which, as a rule, are connected with the isolation methods so far used. Two ASTIs are selectively isolated by affinity chromatography on immobilized trypsin and separated by RP-HPLC when an acidified plasma sample (1 ml) is treated. These ASTIs have apparent m.w. of ca. 72000 and 18000 daltons, respectively. A third ASTI, having apparent m.w. of ca. 6000 daltons, is evidenced when at least 20 ml of plasma sample were processed with an unusual procedure which avoids the adsorption on the protein precipitate formed in acid treatment. For each ASTI determination, reproducibility, linearity range, recovery (95%) and detection limit are reported.

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Trennung und quantitative Bestimmung von säurebeständigen Trypsininhibitoren des menschlichen Plasmas durch RP-HPLC

     

Influence of the chemorheology of toughened epoxy matrices on the processing behavior of high performance composites

The rheological and kinetic behavior of a new commercial toughened epoxy matrix is characterized through a complete experimental program. The kinetic behavior of the thermosetting resin is described by applying a new empirical model, accounting for autocatalytic and difussion control effects. The rheological model uses the kinetic information and describes the matrix viscosity as a function of temperature and degree of reaction using only three fitting parameters. The complete model is verified through calorimetric and rheological tests performed at different temperatures (isotherms) or heating rates (dynamic tests); or under more complex conditions simulating the processing conditions during autoclave lamination. Finally the chemo-rheological model is considered as a part of a master model describing the complete processing behavior of thermoset matrix composites. The use of the master model in control and optimization algorithms is also illustrated.