Oxepinamides A-C and fumiquinazolines H--I: bioactive metabolites from a marine isolate of a fungus of the genus Acremonium

Three new oxepin-containing natural products (1-3) and two new fumiquinazoline metabolites (4-5) have been isolated from organic extracts of the culture broth and mycelia of an Acremonium sp., a fungus obtained from the surface of the Caribbean tunicate Ecteinascidia turbinata. The structures of the five compounds were determined through extensive analysis of 1D- and 2D-NMR data, and mass spectrometry. Compound 1 exhibited good anti-inflammatory activity in a topical RTX-induced mouse ear edema assay. Compounds 4 and 5 exhibited weak antifungal activity toward Candida albicans in a broth microdilution assay.     

Formation of intermolecular hydrogen bonds in light-sensitive crystals of C-2′-(o-oxyphenyl)vinyl-N-p-methylphenyl nitrone,C-2′-(2″-oxy-5″-bromophenyl)vinyl-N-p-methylphenyl nitrone,C-2′-(2″-oxy-5″-bromophenyl)-vinyl-N-phenyl nitrone,and C-2′-(o-oxyphenyl)vinyl-n-methyl nitrone

This paper studies the crystal structure of new substituted light-sensitive azomethine N-oxides (nitrones): C-2′-(o-oxyphenyl)vinyl-N-p-methylphenyl nitrone (1), C-2′-(2″-oxy-5″-bromophenyl)vinyl-N-p-methylphenyl nitrone (2), C-2′-(2″-oxy-5″-bromophenyl)-vinyl-N-phenyl nitrone (3), and C-2′-(o-oxyphenyl)vinyl-N-methyl nitrone (4). In contrast to the compounds studied earlier [1, 2], C-2′-(β-oxy-α-naphthyl)vinyl-N-p-methylphenyl nitrone (5), C-2′-(β-oxy-α-naphthyl)vinyl-N-phenyl nitrone (6), C-2′-(o-oxyphenyl) vinyl-N-phenyl nitrone (7), and C-2′-(o-oxyphenyl)vinyl-N-p-bromophenyl nitrone (8), the nitrones studies in this work have anti-rather than syn-orientations of the nitrone and hydroxyl groups. Due to this spatial arrangement of the proton-donating hydroxyl and proton-accepting nitrone groups, molecules in crystals 1–4 are bonded by intermolecular hydrogen bonds (IHB) to form chains but not centrosymmetric dimeric associates (CDA). Two types of chain arrangements were revealed: “head-to-tail” and “head-to-tail, tail-to-head”. It is shown that the introduction of an alkyl substituent instead of an aryl one at the nitrogen atom of the nitrone group in 4 leads to a change in the geometry of the IHB in the H-associate. It is proven that the hydroxyl proton can undergo an intermolecular O→O transfer in the chain of hydrogen bonds in crystals 1–4, which can give rise to photochemical transformations in these crystals. Institute of Chemical Physics in Chernogolovka, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 37, No. 2, pp. 349–362, March–April, 1996. Translated by L. Smolina     

Application of Mass Spectrometry and Chromatography–Mass Spectrometry in Drug Analysis

The review is devoted to the use of mass spectrometry and chromatography–mass spectrometry in various areas of pharmaceutical chemistry. The role of the above techniques in the structural identification of impurities in drug preparations and in the determination of the biotransformation behavior of pharmaceuticals in human and animal bodies is shown. The inactivation of drugs under the action of external factors (oxidation by atmospheric oxygen and the effects of moisture, heat, and light) is illustrated. The use of various ionization techniques and the spectra of metastable ions for determining the structures of components of biologically active substances are exemplified.     

Sorption Concentration of Radiocesium on NaX Zeolite Modified with Cu2[Fe(CN)6]

Sorption of ¹³⁷Cs on NaX zeolite modified with Cu₂[Fe(CN)₆] was studied under dynamic conditions.     

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.     

Spectroscopic study of low temperature interactions in metal-organic co-condensates

The results on spectroscopic study of low temperature interactions of metal atoms, small clusters and nanoparticles with different organic and inorganic substances in the temperature range 12-300 K are presented. Complexation and reactions of atoms and clusters of magnesium, samarium and silver with carbon dioxide, ethylene and some mesogenic cyanophenyls were studied by the technique of matrix isolation and low temperature co-condensation of metal and ligand vapors, low temperature UV-Vis, IR- and ESR-spectroscopy in combination with quantum chemistry calculations. It was shown that cryochemical reactions of metal particles of different sizes reflected the system's redundant energy.     

Crystal structure of polymorphous modifications of Tm2S3 and related compounds

The role of symmetry in crystal structure formation is revealed for the polymorphous modifications of Tm₂S₃ and related compounds Tm₁₅S{ib22}, Tm₅S₇, and Tm₈S₁₁ using the procedure of selecting and analyzing closepacked planes with cationic, anionic, and combined motifs. The laws of mutual agreement between the cation and anion matrices determining the size of the unit cells are examined, and relationships between the specific cation volumes and symmetry are traced. Translated fromZhumal Strukturnoi Khimii, Vol. 39, No. 4, pp. 669–675, July–August, 1998.     

Rheology of PVC plastisol--VI: criteria for yielding and fracture of an immobilized layer

PVC plastisol exhibits pseudo-plastic flow in steady shear; that is, viscosity decreases with the increasing shear rate. At higher shear rates viscosity reaches a minimum and then increases, i.e., dilatant behavior. Previously, pseudo-plastic behavior was explained by a mechanism in which the suspended particles partition into an immobilized layer and a mobile phase. The development of the immobilized layer with the increase in shear rate was shown to quantitatively account for pseudo-plastic behavior. In higher shear rates dilatation of the immobilized layer was shown to be the cause of dilatacy. At even higher shear rates the immobilized layer fractures. In this paper the viscosity minimum was interpreted as the yielding of the immobilized layer. Subsequently, data in the literature were analyzed to find criteria for the yielding and fracture of the immobilized layer. Yielding was found to obey Coulomb's criterion, from which the coefficient of friction and the cohesive strength of the immobilized layer were evaluated. These properties were controlled by the nature of particle assembly in the immobilized layer and the plasticizer type had only a minor effect. The value of the coefficient of friction was on the lower side and within the range of values found in the literature for other materials. There were two modes of fracture of the immobilized layer, one with low strength, low strain to break, and the other with high strength, high strain to break. The former is analogous to the brittle fracture of solids and the latter ductile failure. The strength of brittle fracture was somewhat higher than cohesive strength, which was evaluated from yielding data. This is akin to Griffith's criterion for brittle fracture of a solid. Ductile failure occurred when the shear stress exceeded normal stress.     

Vibrational spectra and conformations of 2- and 3-methylbicyclo[4.4.0]decanes

The conformations and heats of formation of all trans(T)- and cis(C)-2- and 3-methyl-substituted T- and Cbicyclo[4.4.0]decanes (BD) were calculated by the MM2 method of molecular mechanics. It was shown that the conformationally mobile T-2-Me-CBD and T-3-Me-CBD can exist in normal conditions as an inseparable mixture of conformers with a different equatorial or axial orientation of the Me groups. The Raman scattering (RS) spectra of TBD and CBD were investigated. RS bands whose frequencies were sensitive to the type of ring linkage and orientation (but not the position) of the Me substituents were detected in the 700–300 cm^–1 region.A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 117912 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 9, pp. 2089–2097, September, 1992.