5,5′-Diuracilyl Species from Uracil and [AuCl4]−: Nucleobase Dimerization Brought about by a Metal

Not only UV radiation can bring about the dimerization of the pyrimidine nucleobase uracil, a metal ion can as well! The reaction proceeds by a reductive elimination process of two cis-oriented uracil entities, each bonded to Au^III through C5 [Eq. (a)]. R/R′=H/CH₃, CH₃/CH₃, H,C₅H₉O₄     

Water Splitting by Light with Osmocene as Photocatalyst

Last but not least : A simple molecular redox system is used to split water into hydrogen and oxygen photochemically. Two separate photolyses are combined to a cyclic process (see scheme). Osmocene ([Cp₂Os^II] with Cp^?=C₅H₅^?) serves as photocatalyst.

     

Numerical simulation of transversely isotropic material using adaptive FEM

Lightweight construction plays an important role in the global task to save energy. A common approach to reduce the weight of structures is the use of composite materials like fibre reinforced polymers (FRP). FRP can be characterised by transversely isotropic material behaviour, a special case of anisotropy. In our arcticle we present the necessary efforts to include such material behaviour into an existing adaptive FEM code. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Finite element error estimates for Neumann boundary control problems on graded meshes

A specific elliptic linear-quadratic optimal control problem with Neumann boundary control is investigated. The control has to fulfil inequality constraints. The domain is assumed to be polygonal with reentrant corners. The asymptotic behaviour of two approaches to compute the optimal control is discussed. In the first the piecewise constant approximations of the optimal control are improved by a postprocessing step. In the second the control is not discretized; instead the first order optimality condition is used to determine an approximation of the optimal control. Although the quality of both approximations is in general affected by corner singularities a convergence order of 3/2 can be proven provided that the mesh is sufficiently graded.     

A-posteriori error estimates for optimal control problems with state and control constraints

We discuss the full discretization of an elliptic optimal control problem with pointwise control and state constraints. We provide the first reliable a-posteriori error estimator that contains only computable quantities for this class of problems. Moreover, we show, that the error estimator converges to zero if one has convergence of the discrete solutions to the solution of the original problem. The theory is illustrated by numerical tests.     

Dislocations in an Anisotropic Swift-Hohenberg Equation

We study the existence of dislocations in an anisotropic Swift-Hohenberg equation. We find dislocations as traveling or standing waves connecting roll patterns with different wavenumbers in an infinite strip. The proof is based on a bifurcation analysis. Spatial dynamics and center-manifold reduction yield a reduced, coupled-mode system of differential equations. Existence of traveling dislocations is then established by showing that this reduced system possesses robust heteroclinic orbits.     

Acetylene chemistry,part XXII [1, 2]: Synthesis of noracronycine and some of its analogs via Mitsunobu-reaction

Summary The natural product noracronycine as well as some of its analogs were synthesized by Mitsunobu-etherisation, using propinol derivatives.

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Acetylenchemie, 22. Mitt.: Synthese von Noracronycin und einiger Analoga mittels Mitsunobu-Reaktion (Kurze Mitt.)

Zusammenfassung Der Naturstoff Noracronycin sowie einige seiner Analoga konnten durch Mitsunobu-Veretherung unter Verwendung von Propinol-Derivaten synthetisiert werden.

     

Komplexe des Rheniums mit planarer ReN2S2-Fünfringstruktur Synthesen und Kristallstrukturen von AsPh4[ReCl4(N2S2)] und PPh4[ReBr4(N2S2)]

Complexes of Rhenium with Planar ReN₂S₂ Rings. Syntheses and Crystal Structures of AsPh₄[ReCl₄(N₂S₂)] and PPh₄[ReBr₄(N₂S₂)] The complex [ReCl₄(N₂S₂)]^? can be obtained as PPh₄^⊕ or AsPh₄^⊕ salt by the action of S(NSiMe₃)₂ and of diphenylacetylene, respectively, on the chlorothionitrene complex [ReCl₄(NSCl)₂]^?. Another method of synthesis is the reaction of [ReCl₃(NSCl)₂(POCl₃)] with SbPh₃. [ReBr₃(N₂S₂)]₂ is obtained from excess Me₃SiBr and [ReCl₃(NSCl)₂(POCl₃)]. The anionic complex [ReBr₄(N₂S₂)]^? forms from either [ReCl₄(NSCl)₂]^? or [ReCl₄(N₂S₂)]^? with Me₃SiBr. All compounds are black, diamagnetic, and sensitive to moisture; the PPh₄^⊕ and AsPh₄^⊕ salts are soluble in CH₂Cl₂ and CH₂Br₂. The IR spectra are reported. The crystal structures of AsPh,₄[ReCl₄(N₂S₂)] and PPh₄[ReBr₄(N₂S₂)] were determined by X-ray diffraction. AsPh₄[ReCl₄(N₂S₂)]: space group P2/n, Z = 2, a = 1244.5, b = 1429.3, c = 791.1 pm, γ = 96.89° (1715 observed reflexions, R = 0.082). PPh₄[ReBr₄[ReBr₄(N₂S₂)]: space group P2₁/n, Z = 4, a = 961.7, b = 1397.4, c = 2205.7 pm, β = 102.10° (1787 observed reflexions, R = 0.073). In both compounds the [ReX₄(N₂S₂)]? anions have the same type of structure, the Re atoms forming part of planar ReN₂S₂ rings; the bond lengths are ReN 177 pm, NS 152 pm, and SS 259 for the chloro compound and ReN 184 pm, NS 153 pm, and SS 264 pm for the bromo compound. In AsPh₄[ReCl₄(N₂S₂)] the cations are stacked to form columns in the c-direction; in PPh₄[ReBr₄(N₂S₂)], there is considerable distortion form this packing principle.     

Simultaneous determination of preservatives in beverages,vinegar, aqueous sauces,and quasi-drug drinks by stir-bar sorptive extraction (SBSE) and thermal desorption GC-MS

A method for the simultaneous determination of seven preservatives - sorbic acid, benzoic acid, and p-hydroxybenzoic acid ethyl, isopropyl, propyl, isobutyl, and butyl esters - in beverages, vinegar, aqueous sauces, and quasi-drug drinks has been developed using the stir-bar sorptive extraction technique then thermal desorption GC-MS analysis. The extraction conditions - pH, sample volume, extraction temperature, salt addition, and extraction time - were examined. d5-Benzoic acid and p-hydroxybenzoic acid sec-butyl ester were added as surrogate internal standards to compensate for the effect of sample matrix and coexisting analytes on the sorptive extraction. The linearity of the method was good over the concentration range from 1 to 1000 microg mL(-1) for sorbic acid, 10-1000 microg mL(-1) for benzoic acid, and 0.1-100 microg mL(-1) for p-hydroxybenzoic acid ethyl, isopropyl, propyl, isobutyl, and butyl esters, and the correlation coefficients were higher than 0.9984. The limit of detection ranged from 0.015 to 3.3 microg mL(-1). The recoveries (95-105%) and precision (RSD: 0.86-6.0%) of the method were examined by analyzing a sparkling soft drink, white wine, red wine, balsamic vinegar, soy sauce, and quasi-drug drink samples fortified at the 5 to 50 microg mL(-1) level.