Correlation between 29Si-15N spin-spin coupling constants and the 15N-NMR chemical shifts in silatranes

A nonlinear correlation has been found between the ²⁹Si-¹⁵N spin-spin coupling constants and the ¹⁵N-NMR chemical shifts in silatranes. The dependence has been used to calculate corrections to the spin-spin coupling constant for the electronegativity of a substituent on the silicon atom. This has allowed the previously obtained data on the length and order of the N Si coordinate bond for silatranes in solutions to be refined.Translated from Khimiya Geterotisiklicheskikh Soedinenii, No. 5, pp. 701–703, May, 1989.     

THE PHOTOMORPHOGENETIC CONTROL OF THE DEVELOPMENT OF PLASTID GLYCERALDEHYDE-PHOSPHATE DEHYDROGENASE AND PHOSPHORIBULOKINASE ACTIVITIES IN COTYLEDONS OF MUSTARD SEEDLINGS

The plastid glyceraldehyde-phosphate dehydrogenase and phosphoribulokinase of mustard cotyledon extracts were activated by preincubation with ATP and with ATP and dithiothreitol respectively. By in vitro activation prior to assay, it was possible to determine the potential activities, which appear to have been directly proportional to the amount of each enzyme protein present. In this way it was possible to deduce the net synthesis of these two enzymes. The induction of synthesis of glyceraldehyde-phosphate dehydrogenase and phosphoribulokinase, by continuous far red or white light were similar hut net synthesis in continuous far red continued longer for glyceraldehyde-phosphate dehydrogenase than for phosphoribulokinase. The kinetics of the development of the glyceraldehyde-phosphate dehydrogenase potential activity were very close to those reported by Bruning et al. (1975) for this enzyme. The data do not permit elimination of either the single switch or multiple switches hypotheses for the action of phytochrome. Continuous white illumination gave results similar to those for continous far red for the net synthesis of the two enzymes but it was more effective than far-red in bringing about enzyme activation in vivo.     

Ion-pair extraction of pentacaine from biological materials

Simple and rapid extraction method for quantitative and selective isolation of the new local anesthetic pentacaine from biological materials is proposed. The technique of ion-pair formation was found to be more effective than usual access using the extraction of the nonionized species. The extraction yield of the unchanged molecule³H-pentacaine after double extraction and single scrubbing was found to be more than 90%. The radiochemical purity was over 90%. The method appears suitable for pharmacokinetic studies in the animal body.     

Oxidation of 3,5-disubstituted 6-methyl-1,2,4-triazines

The corresponding substituted 1,2,4-triazine-6-carboxylic acids were obtained by oxidation of 3,5-disubstituted 6-methyl-1,2,4-triazines with hydrogen peroxide in an acidic medium. It is shown that the nature of the substituents does not affect the course of the process.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1271–1273, September, 1982.     

Identification of inhibitors for UDP-galactopyranose mutase

The flavoenzyme uridine 5'-diphosphate (UDP)-galactopyranose mutase (UGM) plays a key role in the cell wall biosynthesis of many pathogens, including Mycobacterium tuberculosis. Using a synthetic fluorescent ligand, we screened 16 000 compounds in a fluorescence polarization assay. Effective inhibitors of UGM were identified.     

Experimental and computational studies of the structure and vibrational spectra of pyridinium-betaine of squaric acid

The FTIR spectra of pyridinium-betaine of squaric acid in 4000-100 cm(-1) frequency region in solid state were measured. In addition, the structure and harmonic vibrational frequencies of this molecule were theoretically evaluated using restricted Hartree-Fock and B3LYP density functional methods. The computed vibrational frequencies are used to determine the types of molecular motions associated with each of the experimental bands observed. Comparison with the experimental spectra provides important information about the ability of these computational methods to describe the vibrational modes in these highly polar strained ring compounds.     

New Tricyclic Amides. Synthesis,Structure, and Oxidation with Peroxyphthalic Acid

4-Azatricyclo[5.2.1.0^2,6]dec-8-ene was synthesized and brought into reactions with benzoyl, o-chlorobenzoyl, p-bromobenzoyl, p-, m-, and o-nitrobenzoyl, and bicyclo[2.2.1]hept-2-ene-endo-5,endo-6-dicarboximidoacetyl chlorides in chloroform in the presence of pyridine. The tricyclic amides thus obtained were epoxidated with peroxyphthalic acid prepared in situ by reaction of phthalic anhydride with a 35% aqueous solution of hydrogen peroxide. The structure of newly synthesized compounds was confirmed by IR and ¹H and ¹³C NMR spectroscopy and mass spectrometry. Their NMR spectra were compared with those of previously synthesized N-arylsulfonyl-4-azatricyclo[5.2.1.0^2,6]dec-8-enes on the basis of conformational composition of the corresponding p-nitrophenyl-substituted derivatives, which was determined by PM3 semi-empirical quantum-chemical calculations.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 6, 2005, pp. 837–845.Original Russian Text Copyright © 2005 by L. Kas’yan, Okovityi, Tarabara, A. Kas’yan, Bondarenko.     

Biomimetic dyes as affinity chromatography tools in enzyme purification

Affinity adsorbents based on immobilized triazine dyes offer important advantages circumventing many of the problems associated with biological ligands. The main drawback of dyes is their moderate selectivity for proteins. Rational attempts to tackle this problem are realized through the biomimetic dye concept according to which new dyes, the biomimetic dyes, are designed to mimic natural ligands. Biomimetic dyes are expected to exhibit increased affinity and purifying ability for the targeted proteins. Biocomputing offers a powerful approach to biomimetic ligand design. The successful exploitation of contemporary computational techniques in molecular design requires the knowledge of the three-dimensional structure of the target protein, or at least, the amino acid sequence of the target protein and the three-dimensional structure of a highly homologous protein. From such information one can then design, on a graphics workstation, the model of the protein and also a number of suitable synthetic ligands which mimic natural biological ligands of the protein. There are several examples of enzyme purifications (trypsin, urokinase, kallikrein, alkaline phosphatase, malate dehydrogenase, formate dehydrogenase, oxaloacetate decarboxylase and lactate dehydrogenase) where synthetic biomimetic dyes have been used successfully as affinity chromatography tools.     

Synthesis and stereochemistry of (−)-(10s)-6,10-dimethyl-6-aza-δ1,9-octahydroquinoline

Enantiomericalfy pure (–)-(10S)-6,10-dimethyl-6-am-^1,9-octahydroquinoline, which has been obtained from optically pure (3S)-1,3-dimethyl-3-(2-cyanoethyl)piperid-4-one, is a chiral intermediate for the preparation of novel biologically active compounds and an analog of piperidine and decahydroquinoline alkaloids. The chiroptical properties of the synthesized 6-azaoctahydroquinoline are examined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1379–1383, October, 1992.