Time- and Temperature-Dependent Study in the Three-Component Zinc-Triazolate-Oxybis(benzoate) System: Stabilization of New Topologies

Three new three-dimensional zinc-triazolate-oxybis(benzoate) compounds. [{Zn-3(H2O)(2)}{C12H8O(COO)(2)}(2)-{C2H2N3}(2)]center dot 2H(2)O(I), [Zn-7{C12H8O(COO)(2)}(4){C2H2N3}(6)]center dot H2O, (II), and[{Zn-5(OH)(2)}{C12H8O(COO)(2)}(3){C2H2N3}(2)] (III), synthesized by a hydrothermal reaction of a mixture of Zn(OAc)(2)center dot 2H(2)O, 4,4'-oxybis(benzoic acid), 1,2,4-triazole, NaOH, and water. Compound I has an interpenetrated diamond structure and II and III have pillared-layer related structures. The formation of a hydrated phase (I) at low temperature and a completely dehydrated phase (III) at high temperature suggests the importance of thermodynamic factors in the formation of three compounds. Transformation studies of I in the presence of water shows the formation of a simple Zn-OBA compound, [Zn(OBA)(H2O)] (IV), at 150 and 180 degrees C and compound III at 200 degrees C. The compounds have been characterized by single-crystal X-ray diffraction, powder X-ray diffraction. thermogravimetric analysis, IR, and photoluminescence studies.

The illustrative use of thiosulfate in the formation of new three-dimensional hybrid structures

Examples of 3D cadmium thiosulfate based inorganic-organic hybrid compounds have been shown to be active photocatalysts using sunlight.

Use of Polyazaheterocycles in the Assembly of New Cadmium Sulfate Frameworks: Synthesis, Structure, and Properties

The reaction of cadmium sulfate in the presence of polyazaheterocyclic organic molecules gave rise to a variety of new cadmium sulfate phases in water containing solvothermal reaction. The compounds have two- (I) and three-dimensionally (II-VI) extended structures. All the compounds have structures built up by the connectivity involving the cadmium octahedra and the sulfate tetrahedra in which the heterocyclic organic molecules act as the ligand. The linkages between the Cd2+ and (SO4)2- ions form one- (II), two- (I, III, and IV), and three- (V and VI) dimensionally extended cadmium sulfate phases. The connectivity between Cd2+ ion and the heterocyclic ligand also gives rise to one- and two-dimensional structures. The inter-connectivity between the two units gives rise to the observed structures. The presence of Cd-O-Cd chains and Cd-O-Cd layers in some of the structures is noteworthy. The adsorption/desorption studies suggest that the cadmium sulfate phases adsorb/desorb anionic dyes selectively in the presence of water/ethanol, respectively. The photocatalytic degradation studies on cationic dyes under UV-irradiation indicate modest activity. The cyanosilylation of imines using the present compounds as heterogeneous catalyst indicate good catalytic behavior. The various properties exhibited by the cadmium sulfate phases suggest that these compounds are versatile. All the compounds were characterized by powder X-ray diffraction, thermogravimetric analysis, infrared (IR) and UV-visible studies.

Interannual Variations of Sea Surface Temperature over the Arabian Sea and the Indian Monsoon: A New Perspective

The interannual variation of surface fields over the Arabian Sea and Bay of Bengal are studied using data between 1900 and 1979. It is emphasized that the monthly mean sea surface temperature (SST) over the north Indian Ocean and monsoon rainfall are significantly affected by synoptic systems and other intraseasonal variations. To highlight the interannual signals it is important to remove the large-amplitude high-frequency noise and very low frequency long-term trends, if any. By suitable spatial and temporal averaging of the SST and the rainfall data and by removing the long-term trend from the SST data, we have been able to show that there exists a homogeneous region in the southeastern Arabian Sea over which the March�April (MA) SST anomalies are significantly correlated with the seasonal (June�September) rainfall over India. A potential of this premonsoon signal for predicting the seasonal rainfall over India is indicated. It is shown that the correlation between the SST and the seasonal monsoon rainfall goes through a change of sign from significantly positive with premonsoon SST to very small values with SST during the monsoon season and to significantly negative with SST during the post-monsoon months. For the first time, we have demonstrated that heavy or deficient rainfall years are associated with large-scale coherent changes in the SST (although perhaps of small amplitude) over the north Indian 0cean. We also indicate possible reasons for the apparent lack of persistence of the premonsoon SST anomalies.

Studies on the metabolism of a monoterpene ketone, R-(+)-pulegone-a hepatotoxin in rat: isolation and characterization of new metabolites

1. The metabolic disposition of R-(+)-pulegone (1) was examined in rats following four daily oral doses (250 mg/kg). 2. Six metabolites, namely pulegol (II), 2-hydroxy-2-(1-hydroxy-1-methylethyl)-5-methylcyclohexanone (III), 3,6-dimethyl-7a-hydroxy-5,6,7,7a-tetrahydro-2(4H)-benzofuranone (IV), menthofuran (V), 5-methyl-2-(1-methyl-1-carboxyethylidene)cyclohexanone (VI), and 5-methyl-5-hydroxy-2-(1-hydroxy-1-carboxyethyl)cyclohexanone (VII) have previously been isolated from rat urine, and identified (Moorthy et al. (1989a). Eight new metabolites have now been isolated from rat urine, namely, 5-hydroxy-pulegone (VIII), piperitone (IX), piperitenone (X), 7-hydroxy-piperitone (XI), 8-hydroxy piperitone (XII), p-cresol (XIII), geranic acid (XIV) and neronic acid (XV). These were identified by n.m.r., i.r. and mass spectrometry. 3. Based on these results, metabolic pathways for the biotransformation of R-(+)-pulegone in rat have been proposed.

The Archaeometallurgical Implications of New Findings of Traditional Crafts of Making High Tin ‘Delta’ Bronze Mirrors and ‘Beta’ Bronze Vessels in Kerala State of South India

New metallurgical and ethnographic observations of the traditional manufacture of specular high-tin bronze mirrors in Kerala state of southern India are discussed, which is an exceptional example of a surviving craft practice of metal mirror-making in the world. The manufacturing process has been reconstructed from analytical investigations made by Srinivasan following a visit late in 1991 to a mirror making workshop and from her technical studies of equipment acquired by Glover in March 1992 from another group of mirror makers from Pathanamthita at an exhibition held at Crafts Museum, Delhi. Finished and unfinished mirror from two workshops were of a binary, copper-tin alloy of 33% tin which is close to the composition of pure delta phase, so that these mirrors are referred to here as ‘delta’ bronzes. For the first time, metallurgical and field observations were made by Srinivasan in 1991 of the manufacture of high-tin ‘beta’ bonze vessels from Palghat district, Kerala, i‥e of wrought and quenched 23% tin bronze. This has provided the first metallurgical record for a surviving craft of high-tin bronze bowl making which can be directly related to archaeological finds of high-tin bronze vessels from the Indian subcontinent and Southeast Asia. New analytical investigations are presented of high-tin beta bronzes from the Indian subcontinent which are some of the earliest reported worldwide. These coupled with the archaeometallurgical evidence suggests that these high-tin bronze techniques are part of a long, continuing, and probably indigenous tradition of the use of high-tin bronzes in the Indian subcontinent with finds reported even from Indus Valley sites. While the source of tin has been problematic, new evidence on bronze smelting slags and literary evidence suggests there may have been some sources of tin in South India.

Structures of new crystal forms of Mycobacterium tuberculosis peptidyl-tRNA hydrolase and functionally important plasticity of the molecule

The X-ray structures of new crystal forms of peptidyl-tRNA hydrolase from M.similar to tuberculosis reported here and the results of previous X-ray studies of the enzyme from different sources provide a picture of the functionally relevant plasticity of the protein molecule. The new X-ray results confirm the connection deduced previously between the closure of the lid at the peptide-binding site and the opening of the gate that separates the peptide-binding and tRNA-binding sites. The plasticity of the molecule indicated by X-ray structures is in general agreement with that deduced from the available solution NMR results. The correlation between the lid and the gate movements is not, however, observed in the NMR structure.

Phalangopsidae crickets from the Indian Region (Orthoptera, Grylloidea), with the descriptions of new taxa, diagnoses for genera, and a key to Indian genera

The Indian region is presently the second region after the Neotropics in terms of diversity of phalangopsid crickets. Yet their study is impeded by the lack of necessary taxonomic tools for taxon identification. In the present paper, all generic diagnoses are clarified, using morphological and genitalic characters; female genitalia are described and illustrated for all genera with known females. New taxa are described from southern India: Kempiola flavipunctatus Desutter-Grandcolas n. sp., Opiliosina meridionalis Desutter-Grandcolas n. gen., n. sp., Phalangopsina bolivari Desutter-Grandcolas n. sp., P. chopardi Desutter-Grandcolas n. sp., P. gravelyi Desutter-Grandcolas n. sp., and Speluncasina Desutter-Grandcolas n. gen. The list of phalangopsid crickets from the Indian Region is updated, and a key to phalangopsid genera proposed. A lectotype and a paralectotype are designated to fix the name of Phalangopsina dubia (Bolivar, 1900). Opilionacris annandalei Chopard, 1928, previously transferred to the African genus Phaeophilacris Walker, 1871, is transferred to the genus Speluncasina Desutter-Grandcolas n. gen., while Larandopsis jharnae Bhowmik, 1981 and L. newguineae Bhowmik, 1981 described from New Guinea are transferred to the eneopterine genus Lebinthus Stal, 1877. Finally Luzaropsis confusa Chopard, 1969 is removed from its synonymy with L. ferruginea Walker, 1871.

Design and Synthesis of New Benzimidazole-Carbazole Conjugates for the Stabilization of Human Telomeric DNA, Telomerase Inhibition, and Their Selective Action on Cancer Cells

Cell-permeable small molecules that enhance the stability of the G-quadruplex (G4) DNA structures are currently among the most intensively pursued ligands for inhibition of the telomerase activity. Herein we report the design and syntheses of four novel benzimidazole carbazole conjugates and demonstrate their high binding affinity to G4 DNA. Si nuclease assay confirmed the ligand mediated G-quadruplex DNA protection. Additional evidence from Telomeric Repeat Amplification Protocol (TRAP-LIG) assay demonstrated efficient telomerase inhibition activity by the ligands. Two of the ligands showed IC50 values in the sub-micromolar range in the TRAP-LIG assay, which are the best among the benzimidazole derivatives reported so far. The ligands also exhibited cancer cell selective nuclear internalization, nuclear condensation, fragmentation, and eventually antiproliferative activity in long-term cell viability assays. Annexin V-FITC/PI staining assays confirm that the cell death induced by the ligands follows an apoptotic pathway. An insight into the mode of ligand binding was obtained from the molecular dynamics simulations.