Electrodeposition of Ni–Fe alloy from a choline chloride-containing ionic liquid

Journal of Solid State Electrochemistry - The electrochemical deposition of a nickel–iron alloy from a plating solution based on a deep eutectic solvent (a eutectic mixture of ethylene glycol...     

Kinetic Analysis of the Hydrolysis of Pentose-1-phosphates through Apparent Nucleoside Phosphorolysis Equilibrium Shifts**

Herein, we report an addition to the toolbox for the monitoring and quantification of the hydrolytic decay of pentose-1-phosphates, which are known to be elusive and difficult to quantify. This communication describes how apparent equilibrium shifts of a nucleoside phosphorolysis reaction can be employed to calculate hydrolytic loss of pentose-1-phosphates based on the measurement of post-hydrolysis equilibrium concentrations of a nucleoside and a nucleobase. To demonstrate this approach, we assessed the stability of the relatively stable ribose-1-phosphate at 98 °C and found half-lives of 1.8–11.7 h depending on the medium pH. This approach can be extended to other sugar phosphates and related reaction systems to quantify the stability of UV-inactive and hard-to-detect reaction products and intermediates.     

Et2Zn-mediated stoichiometric C(sp)-H silylation of 1-alkynes and chlorosilanes

A first example of an Et₂Zn mediated silylation of 1-aklynes is reported. A series of functional groups are tolerated in this reaction. Mechanistic studies support Zn alkynilides as intermediates in the reaction. This reaction protocol provides a practical method for the preparation of alkynylsilanes and expands the application of organometallic zinc in organic synthesis.     

Zur Theorie der Liniencomplexe des ersten und zweiten Grades

Ohne Zusammenfassung     

Biopolymers for biocatalysis: Structure and catalytic mechanism of hydroxynitrile lyases

Hydroxynitrile lyases catalyze the reversible cleavage of α-cyanohydrins to yield hydrocyanic acid and the corresponding aldehyde or ketone. Besides its biological interest, this class of enzymes is also of relevance in industrial biocatalysis for the enantioselective condensation of HCN with a variety of aldehydes and ketones. Several distinctly different types of hydroxynitrile lyases (HNLs) are known, which must have originated through convergent evolution from different ancestral proteins. Three-dimensional structural data are known for three classes of hydroxynitrile lyases. Insights into the reaction mechanisms emerged from a combination of structural, enzyme kinetic, spectroscopic, and molecular modeling data. For all three types of HNLs, mechanisms involving acid–base catalysis were proposed. In members belonging to the α,β-hydrolase type, the amino acid residues of the catalytic triad presumably act as general acid/base, whereas for flavine adenine dinucleotide (FAD)-dependent HNLs a single histidine residue fulfills this function. In the third type of HNL—which is related to carboxypeptidase—acid–base catalysis involves the carboxylate of the C-terminal residue. The catalytic relevance of a positive electrostatic potential in the active site was suggested in some of the mechanistic proposals. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 479–486, 2004     

On the Second Law of Thermodynamics and the Piston Problem

The piston problem is investigated in the case where the length of the cylinder is infinite (on both sides) and the ratio m/M is a very small parameter, where m is the mass of one particle of the gaz and M is the mass of the piston. Introducing initial conditions such that the stochastic motion of the piston remains in the average at the origin (no drift), it is shown that the time evolution of the fluids, analytically derived from Liouville equation in a previous work, agrees with the Second Law of thermodynamics. We thus have a non equilibrium microscopical model whose evolution can be explicitly shown to obey the two laws of thermodynamics.     

Stability of translating solutions to mean curvature flow

We prove stability of rotationally symmetric translating solutions to mean curvature flow. For initial data that converge spatially at infinity to such a soliton, we obtain convergence for large times to that soliton without imposing any decay rates. The authors are members of SFB 647/B3 “Raum – Zeit – Materie: Singularity Structure, Long-time Behaviour and Dynamics of Solutions of Non-linear Evolution Equations”.     

Realization of 2-solvable nilpotent groups as groups of classes of homotopy self-equivalences

Let X be a 1-connected CW-complex of finite type and ε_?(X) be the group of homotopy classes of self-equivalences of X which induce the identity on homotopy groups. In this paper, we prove that every finitely generated 2-solvable rational nilpotent group is realizable as ε_?(X) where X is the rationalization of a 1-connected CW-complex of finite type.     

Spectral theory and L∞-time decay estimates for Klein–Gordon equations on two half axes with transmission: The tunnel effect

Consider two copies N₁, N₂ of the interval [0, ∞]. Consider Klein-Gordon equations with (different) constant coefficients on ? × N_j ( = time × space). Assume the coincidence of the values of the solution at the boundary points of the N_j for all times and a transmission condition relating its first (one-sided) space derivatives at these points. Under a symmetry condition, we extend the spatial part of the equation and the transmission conditions to a self-adjoint operator (by Friedrichs extension) and reformulate our problem in terms of an abstract wave equation in a suitable Hilbert space. We derive an expansion of the solution in generalized eigenfunctions of this self-adjoint extension and show, that the L^∞-norms (in space) of the solution and its first k space derivatives at the time t decay for t → ∞ at least as const. t^¼, if the initial conditions satisfy a compatibility condition of order k derived in this paper. The loss of decay rate in comparison with the full line case (const. t^?½, cf. [28]) is caused by the tunnel effect. Further we show that an abstract wave equation in a Hilbert space with a Friedrichs extension as spatial part can always be derived from a stationarity principle for an associated action-type functional. This yields a physical legitimation of our model by the principle of stationary action and moreover a criterion for the physical interpretability of all models created by the linear interaction concept [4, 6, 8, 10], in particular for the coupling of media of different dimension (alternative to [13, 16] for similar models).