Cyclotetrasilazane als precursor für cyclotrisilazane und bis(cyclodisilazan-1-yl)silane

Di-lithiated octamethylcyclotetrasilazane (OMCTS, 1) reacts with halosilanes in different ways. Ring contraction with formation of the isomeric cyclodisilazanes 2, 3 occurs in the reaction with chloro- and fluorotrimethylsilanes. Substitution (6) and ring contraction with formation of the isomeric six-membered ring 7 occurs with chlorodimethylsilane. 2, 3, 6 and 7 are excellent precursors of silyl-bridged, SiH-functional, four-membered ring systems (4, 5, 9–11). The mechanism of the isomerization reactions are discussed.     

Enhanced selectivity in Novozym 435 catalyzed kinetic resolution of secondary alcohols and butanoates caused by the (R)-alcohols

In esterifications of secondary alcohols catalyzed by immobilized lipase B from Candida antarctica (Novozym 435) the E-values decreased during the reaction. Hydrolysis of the corresponding butanoates showed the opposite effect. When an enantiopure (R)-alcohol, related but different, was added to the transesterification reaction, the E-value was significantly enhanced.     

Ethylenic compounds reactivity: bromination—XLI: Relative reactivities of R1CMeCH2 and R1CHCMe2 series as a criterion for distinguishing between bridged and acyclic transition states. Degree of symmetry of the bromonium ion-like transition state

Reactivities of homogeneous series of ethylenic compounds R¹CHCH₂1, trans R¹CHCHMe 2, R¹MeCCH₂3 and R¹CHCMe₂4 have been measured in methanol at 25°C (R¹ Me, Et, n-Pr, -CH₂C₆H₅-CH₂OCOCH₃, -CH₂Cl). The criterion developed to decide between a bridged and a carbonium ion-like transition state is based on an internal comparison of the series and avoids resorting to external structural scales. Even in the case of alkenes 3 and 4 which are very dissymmetric with respect to polarity, the sensitivity to polar effects remains constant and the transition state behaves like a symmetric entity; only a slight secondary effect, attributed to hyperconjugation, is detectable.     

Enhancing the enzymatic hydrolysis of cellulosic materials using simultaneous ball milling

One of the limiting factors restricting the effective and efficient bioconversion of softwood-derived lignocellulosic residues is the recalcitrance of the substrate following pretreatment. Consequently, the ensuing enzymatic process requires relatively high enzyme loadings to produce monomeric carbohydrates that are readily fermentable by ethanologenic microorganisms. In an attempt to circumvent the need for larger enzyme loadings, a simultaneous physical and enzymatic hydrolysis treatment was evaluated. A ball-mill reactor was used as the digestion vessel, and the extent and rate of hydrolysis were monitored. Concurrently, enzyme adsorption profiles and the rate of conversion during the course of hydrolysis were monitored. α-Cellulose, employed as a model substrate, and SO₂-impregnated steam-exploded Douglas-fir wood chips were assessed as the cellulosic substrates. The softwood-derived substrate was further posttreated with water and hot alkaline hydrogen peroxide to remove >90% of the original lignin. Experiments at different reaction conditions were evaluated, including substrate concentration, enzyme loading, reaction volumes, and number of ball beads employed during mechanical milling. It was apparent that the best conditions for the enzymatic hydrolysis of α-cellulose were attained using a higher number of beads, while the presence of air-liquid interface did not seem to affect the rate of saccharification. Similarly, when employing the lignocellulosic substrate, up to 100% hydrolysis could be achieved with a minimum enzyme loading (10 filter paper units/g of cellulose), at lower substrate concentrations and with a greater number of reaction beads during milling. It was apparent that the combined strategy of simultaneous ball milling and enzymatic hydrolysis could improve the rate of saccharification and/or reduce the enzyme loading required to attain total hydrolysis of the carbohydrate moieties.     

Simple diffuse reflectance UV-vis spectroscopic determination of organic pigments (fringelites) in fossils

To screen for organic pigments, like fringelites or porphyrins, in sediments and fossil specimen, a simple diffuse reflectance UV-vis spectroscopic determination was developed. In contrast to common inorganic pigments, like Fe₂O₃, these pigments exhibit well-structured characteristic absorption peaks which allow their recognition. This method was then used to identify fringelite H in a non-crinoidSolenopora species from the Jurassic. Reflectance FTIR spectroscopy proved not to be useful for this purpose.     

Hydrodynamically limited precision of gradient techniques in flow injection analysis

Based on the law of error propagation, a general expression is derived to study theoretically the hydrodynamically limited precision associated with each single element of fluid in a concentration profile in flow injection analysis. Convolution of the injection and residence time distribution functions is used to obtain response functions for a homogeneously stirred mixing chamber and for a straight capillary tube. The effects of stochastic variations on overall precision by sample introduction, pumping and timing are elucidated and compared with experimental findings. Resulting practical implications for the use of these two dispersing elements are outlined.     

Biotinylation: A nonradioactive method for the identification of cell surface antigens in immunoprecipitates

A nonradioactive method was employed to detect different cell membrane antigens on human polymorphonuclear granulocytes, monocytes and platelets. We compared the reactivity of one monoclonal antibody, N1III10, assumed to be FcγRII-specific by functional assays, with other well-characterized monoclonal antibodies and human sera. Intact cells were incubated with biotin N-hydroxysulfosuccinimide ester which preferentially reacts with lysine residues in polypeptides. Biotin-labeled cells were lysed and the antigen was isolated from the cell lysate by immunoprecipitation with the antibody bound to Protein A-Sepharose. The precipitates were separated by sodium dodecyl sulfate-polyacrylamide gel electrophoresis, transferred onto nitrocellulose membrane, and visualized by a streptavidin-alkaline phosphatase system with a suitable substrate. Using this biotin-labeling system we could show that N1III10 detects a 40 kDa antigen on monocytes and platelets, comparable to that expected of FcγRII monoclonal antibodies.     

Effect of halides and alkali cations on the Zn(Hg)/Zn(II) electrode reactions

The title subject has been studied by galvanostatic single-pulse, chronopotentiometric and equilibrium measurements on the Zn(Hg)/Zn(II) electrode in x M KI+(1?x) M KCl (x from 0 to 1), 1 M KBr and 1 M MeCl (Me=Li, Na, K and Cs) solutions of pH 3 at 25°C. Quantitative information about the effect of specifically adsorbed halides on the rates of the Zn(II)/Zn(I) and the Zn(I)/Zn(Hg) steps is obtained separately (for the latter step mainly at potentials near ?1.0 V(SCE)), and the latter step seems to be more influenced than the former by the adsorption. An attempt is made to correlate the adsorption effect on the rate of the Zn(II)/Zn(I) step to double-layer parameters according to recent models for such effects. The extra current observed at potentials where the halides are adsorbed, seems to vary with the surface activity of the specifically adsorbed ion. The lack of any observed kinetic effect of Cs⁺, which is specifically adsorbed at these potentials, is possibly due to the Cs⁺ specific adsorption enhancing the Cl^? specific adsorption and vice versa, so that the decelerating and accelerating effects by these ions may cancel each other.     

Symmetry reductions and exact solutions of shallow water wave equations

In this paper we study symmetry reductions and exact solutions of the shallow water wave (SWW) equation $$u_{xxxt} + \alpha u_x u_{xt} + \beta u_t u_{xx} - u_{xt} - u_{xx} = 0,$$ whereα andβ are arbitrary, nonzero, constants, which is derivable using the so-called Boussinesq approximation. Two special cases of this equation, or the equivalent nonlocal equation obtained by settingu _x =U, have been discussed in the literature. The caseα=2β was discussed by Ablowitz, Kaup, Newell and Segur (Stud. Appl. Math.,53 (1974), 249), who showed that this case was solvable by inverse scattering through a second-order linear problem. This case and the caseα=β were studied by Hirota and Satsuma (J. Phys. Soc. Japan,40 (1976), 611) using Hirota's bi-linear technique. Further, the caseα=β is solvable by inverse scattering through a third-order linear problem. In this paper, a catalogue of symmetry reductions is obtained using the classical Lie method and the nonclassical method due to Bluman and Cole (J. Math. Mech,18 (1969), 1025). The classical Lie method yields symmetry reductions of (1) expressible in terms of the first, third and fifth Painlevé transcendents and Weierstrass elliptic functions. The nonclassical method yields a plethora of exact solutions of (1) withα=β which possess a rich variety of qualitative behaviours. These solutions all like a two-soliton solution fort < 0 but differ radically fort > 0 and may be viewed as a nonlinear superposition of two solitons, one travelling to the left with arbitrary speed and the other to the right with equal and opposite speed. These families of solutions have important implications with regard to the numerical analysis of SWW and suggests that solving (1) numerically could pose some fundamental difficulties. In particular, one would not be able to distinguish the solutions in an initial-value problem since an exponentially small change in the initial conditions can result in completely different qualitative behaviours. We compare the two-soliton solutions obtained using the nonclassical method to those obtained using the singular manifold method and Hirota's bi-linear method. Further, we show that there is an analogous nonlinear superposition of solutions for two (2+1)dimensional generalisations of the SWW Equation (1) withα=β. This yields solutions expressible as the sum of two solutions of the Korteweg-de Vries equation.