Stoichiometric and catalytic methods of asymmetric synthesis of nonproteinogenic α-and β-amino acids via transition metal coordination compounds

The complexes of glycine, -alanine, and -alanine with (S)-[N-(N-benzylprolyl)amino] benzophenone formed by Ni(II) and Cu(II) ions and Schiff bases enter into different nucleophilic and electrophilic reactions with the formation of diastereoisomeric complexes which decompose into proteinogenic and nonproteinogenic L-amino acids with a high chemical yield and elevated optical purity (70–90%). Optically pure amino acids can be obtained from diastereoisomerically pure complexes after the complexes are separated by recrystallization of the mixture of diastereoisomeric complexes formed. A new type of interphase catalysts of C-alkylation of achiral Schiff bases was proposed. The catalysts are positively charged Ni(II) and Cu(II) complexes of Schiff bases of chiral diamines. In some cases, these complexes have a higher activity and capacity to execute asymmetric alkylation than traditional chiral interphase catalysts based on cinchonidine.Based on materials in the section report by Yu. N. Belokon' to the 7th European Symposium on Organic Chemistry, ESOC-7.A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1106–1127, May, 1992.     

Convexlike and concavelike conditions in alternative,minimax, and minimization theorems

Convexlike and concavelike conditions are of interest for extensions of the Von Neumann minimax theorem. Since the beginning of the 80's, these conditions also play a certain role in deriving generalized alternative theorems of the Gordan, Motzkin, and Farkas type and Lagrange multiplier results for constrained minimization problems.In this paper, we study various known convexlike conditions for vector-valued functions on a set and investigate convexlike and concavelike conditions for real-valued functions on a product setC×D, where we are mainly interested in the relationships between these conditions. At the end of the paper, we point out several conclusions from our results for the above-mentioned mathematical fields.The author is indebted to Dr. R. Reemtsen and Dr. V. Jeyakumar for their helpful comments during the preparations of this paper.     

X-ray and IR spectroscopic studies of specific intermolecular interactions inN′-substituted isonicotinohydrazides

_N-Thenylidene- andN-(o-nitrobenzylidene)hydrazides of isonicotinic acid have been studied by X-ray structural analysis and IR spectroscopy. In the crystalline state, these molecules are linked through intermolecular N—H ... Np_y hydrogen bonds. Carbonyl groups are not involved in intermolecular hydrogen bonds. However, it was found that the C=O group participates in an attractive interaction with the sulfur atom of the thiophene group. The energy of this interaction is comparable with the energies of intermolecular C=O ... H—N hydrogen bonds in amides.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 896–900, April, 1996.     

Thermal Decomposition of Bi(III), Cd(II), Pb(II) and Cu(II) Thiocyanates

Thermal decomposition of Bi(SCN)₃, Cd(SCN)₂, Pb(SCN)₂ and Cu(SCN)₂ has been studied. The thermal analysis curves and the diffraction patterns of the solid intermediate and final products of the pyrolysis are presented. The gaseous products of the decomposition (SO₂ and CO₂) were detected and quantitatively determined. Thermal, X-ray and chemical analyses have been used to establish the nature of the reactions occurring at each stage in the decomposition.This revised version was published online in November 2005 with corrections to the Cover Date.     

Determination of acidic sites and binding toxic metal ions on cumin surface using nonideal competitive adsorption model

A fundamental study of the application of cumin biomass in the recovery of Cu and Zn metal ion uptake from food and drinks is carried out at different pH's and at fixed ionic strength. The chemical characteristics of protein in cumin seeds were investigated. Results showed that cumin contains 18.25% crude protein, which includes 18 amino acids. The main reactive groups on protein cumin are amino and carboxylic groups of dicarboxylic amino acids, leading to a pH-dependent charge. Therefore, the cumin surface is considered as a heterogeneous system. To describe protonation behavior in a heterogeneous cumin biomass (cumin/0.1 M NaNO(3)) system, acid-base titrations have been performed with conductometric and potentiometric titration. Measurement of the reactivity of cumin surface in the adsorption of Cu and Zn metal ions and determination of metal binding at different pH's were also carried out. To solve broad and ill-defined titration curves, a simplified version of nonideal competitive analysis (NICA) by Plette et al.) was applied. The results show that the sorption of the bivalent metal ions onto the whole surface of cumin could be attributed to a monodentate binding to one site mainly carboxylic-type site.     

Supercritical Propanol-Water Synthesis and Comprehensive Size Characterisation of Highly Crystalline anatase TiO2 Nanoparticles

Highly crystalline anatase TiO₂ nanoparticles have been synthesised in less than 1 min in a supercritical propanol-water mixture using a continuous flow reactor. The synthesis parameter space (T, P, concentration) has been explored and the average particle size can be accurately controlled within 10-18 nm with narrow size distributions (2-3 nm). At subcritical conditions amorphous products are obtained, whereas a broad range of T and P in the supercritical regime gives 11-14 nm particles. At high temperature and pressure, the particles size increase to 18 nm. The nanoparticles have been extensively characterised with powder X-ray diffraction (PXRD), transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) with excellent agreement on size and size distribution parameters. The SAXS analysis suggests disk-shaped particles with diameters that are approximately double the height. For comparison, a series of conventional autoclave sol-gel syntheses have been carried out. These also produce phase-pure anatase nanoparticles, but with much broader size distributions and at much longer synthesis times (hours). The study demonstrates that synthesis in supercritical fluids is a very promising method for manipulating the size and size distribution of nanoparticles, thus removing one of the key limitations in many applications of nanomaterials.     

Thermal decomposition of cobalt nitrato compounds: Preparation of anhydrous cobalt(II)nitrate and its characterisation by Infrared and Raman spectra

The thermal decomposition of Co(NO₃)₂·6H₂O (1) as well as that one of NO[Co(NO₃)₃] (Co(NO₃)₂·N₂O₄) (2) was followed by thermogravimetric (TG) measurements, X-ray recording and Raman and IR spectra. The stepwise decomposition reactions of 1 and 2 leading to anhydrous cobalt(II)nitrate (3) were established. In N₂ atmosphere, cobalt oxides are finally formed whereas in H₂/N₂ (10% H₂) cobalt metal is produced. Rapid heating of cobalt(II)nitrate hexahydrate causes melting (formation of a hydrate melt) and therefore side reactions in the hydrate melt by incoupled reactions and evolution/evaporation of different species as, e.g., HNO₃, NO₂, etc. In case of larger amounts in dense packing in the sample container, the formation of oxo(hydoxo)nitrates is possible at higher temperature. For 2, its thermal decomposition to 3 was followed and its decomposition mechanism is proposed.     

Qualitative evaluation of aromatic herbs by direct headspace GC analysis. Applications of the method and comparison with the traditional analysis of essential oils

GC headspace analyses of various aromatizing herbs have been compared with those relating to the essential oils, obtained by steam distillation, of the same plants. In this way it was possible to establish the most significant differences between the composition of a herb flavor and that of its essential oil. In particular, we observed some very volatile compounds in the headspace samples which were absent from the essential oil; these components may make an important contribution to the herb flavor. The identification of these substances is still in progress.     

Partial molal volumes of ions in organic solvents from ultrasonic vibration potential and density measurements. III. Dimethylsulfoxide

The partial molal volumes of Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Cl^–, Br^–, I^–, and NO ₃ ^- in DMSO at 25°C have been determined from ultrasonic vibration potential data and density data for solutions of uni-univalent electrolytes. Hepler's semiemprirical equation has been used to split ionic partial molal volumes into geometric and electrostrictive contributions. The results obtained in this work confirm the conclusion of our previous studies, namely, that the contribution of electrostriction is essentially determined by the properties of that layer of atoms, 0.3 to 0.4 nm thick, in contact with the ion and by the degree of steric hindrance of the poles of the dipole of the solvent molecule. On the other hand, the geometric contribution depends on the size of the solvent molecule and also on the arrangement of the solvent molecules about the ions. It is shown that the geometric contribution to the partial molal volume of ions is largely increased when ions cannot come close enough to the poles of the solvent-molecule dipole, owing to steric hindrance.