Electrogenerated chemiluminescence in systems with tetraphenylborate anion as a co-reactant

The study of electrogenerated chemiluminescence (ECL) in aqueous and non-aqueous media with tetraphenylborate anion as a co-reactant is reported. The obtained results indicate that tetraphenylborate acts according to an oxidative reduction scheme and forms a strong reducer after being homogeneously oxidized by a radical cation or dication of luminophore. Spectral measurements prove that light emission originates from the luminophore present in solution and practically no emission occurs when only tetraphenylborate ion is oxidized at the electrode. Since the tetraphenylborate ion is a well known analytical reactant and precipitates a number of metal and organic cations its electrochemiluminescent detection can be used for their assay. It can also be applied as an efficient co-reactant for electrogenerated chemiluminescence excitation both in aqueous and non-aqueous media.     

Synthesis and Reaction of 2-Mercapto-3-Arylpropanoic Acids

Abstract

Two synthetic pathways for the preparation of 2-mercapto-3-arylpropanoic acids were developed. First, by the reaction of arenediazonium bromides with acrylic esters in the presence of CuBr, alkyl (2-bromo-3-aryl)propanoates were formed. Their cyclization with thiourea produced 5-(R-benzyl)-2-imino-4-thiazolidinones, which yielded 3-aryl-2-mercaptopropanoic acids by alkaline hydrolysis. Second, direct Meerwein arylation of acrylates in the presence of S-nucleophile (NaSH) allowed isolation of 3-phenyl-2-mercaptopropanoic acid in 8% yield. Such acids were used for cyclization with cyanoguanidine and phenyl isothiocyanate yielding 1-[5-(R-benzyl)-4-oxo-1,3-thiazolidin-2-ylidene]guanidines and new 5-(R-benzyl)-3-phenyl-2-thioxo-1,3-thiazolidin-4-one (rhodanine) derivatives correspondingly.     

Partial actions and an embedding theorem for inverse semigroups

Periodica Mathematica Hungarica - We give a simple construction involving partial actions which permits us to obtain an easy proof of a weakened version of L. O’Carroll’s...     

Size of the jump and behavior of the absolute maximum for processes with independent increments

For a process with independent increments and negative mean one investigates the asymptotic behavior of the distribution of the absolute maximum and the size of the jump over a positive level. Necessary and sufficient conditions for the existence of a proper distribution of the size of a jump over an infinite level are found.Translated from Ukrainskii Matematicheskii Zhurnal, Vol. 42, No. 4, pp. 451–458, April, 1990.     

Enhancing plasticity of high-strength titanium alloys VT 22 under impact-oscillatory loading

Abstract

The purpose of this paper is to provide new experimental data for high-strength VT 22 titanium α + β-type alloy under impact-oscillatory loading and dynamic non-equilibrium process. Based on the performed experimental studies, it was found that overall plastic deformation of this alloy can be increased by a factor 2.75 compared with its initial state without significant loss of strength. To achieve this goal, a new methodology to study the impact behaviour of materials under non-equilibrium process has been used. Physical research revealed that significant microstructural refinement of the alloy is observed after such type of loading, as the result of which the fine grains are formed with subgrain refinement which takes place within the basis of alloy.     

Homogenization of random elastic networks with non-affine kinematics

This contribution concerns the mechanics of materials with random network microstructures. It develops a general homogenization approach that allows to link the microscopic deformation of fibers in the disordered network with the macroscopic response of the continuous solid. This link is established by a novel micro-macro relation based on the kinematics of maximal advance paths that constrains the unknown microscopic stretch of fibers with respect to the macroscopic strain. This relation accounts for the topology of the network, in particular, its connectivity and takes for the tetrafunctional networks a clearly interpretable tensorial form. In line with the principle of the minimum averaged free energy the elastic response of the network is obtained by the relaxation of the variable fiber stretch subjected to the kinematic constraint. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Manifold dynamic non-covalent interactions for steering molecular assembly and cyclization

Deciphering rich non-covalent interactions that govern many chemical and biological processes is crucial for the design of drugs and controlling molecular assemblies and their chemical transformations. However, real-space characterization of these weak interactions in complex molecular architectures at the single bond level has been a longstanding challenge. Here, we employed bond-resolved scanning probe microscopy combined with an exhaustive structural search algorithm and quantum chemistry calculations to elucidate multiple non-covalent interactions that control the cohesive molecular clustering of well-designed precursor molecules and their chemical reactions. The presence of two flexible bromo-triphenyl moieties in the precursor leads to the assembly of distinct non-planar dimer and trimer clusters by manifold non-covalent interactions, including hydrogen bonding, halogen bonding, C–H⋯π and lone pair⋯π interactions. The dynamic nature of weak interactions allows for transforming dimers into energetically more favourable trimers as molecular density increases. The formation of trimers also facilitates thermally-triggered intermolecular Ullmann coupling reactions, while the disassembly of dimers favours intramolecular cyclization, as evidenced by bond-resolved imaging of metalorganic intermediates and final products. The richness of manifold non-covalent interactions offers unprecedented opportunities for controlling the assembly of complex molecular architectures and steering on-surface synthesis of quantum nanostructures.

A real-space characterization of dynamic non-covalent interactions in molecular assemblies and chemical reactions at the atomic bond level.     

A new strategy for asymmetric synthesis of aminophosphonic acid derivatives: the first enantioselective catalytic reduction of C-phosphorylated imines

The first highly enantioselective catalytic reduction of 1-imino-2,2,2-trifluoroethylphosphonates and the synthesis of enantiomerically enriched biorelevant phosphonotrifluoroalanine is reported.