A New Mechanism For Ferromagnetism In C-60-TDAE

Based on the topology of C-60 and the resulting non-disjoint nature of the lowest unoccupied molecular orbitals, Ne propose a new model for ferromagnetic exchange in C-60-TDAE. Within the Hubbard model, we find that the ferromagnetic exchange integral is stabilized to first order in the inter-ball transfer integral, while the antiferromagnetic coupling is stabilized only to second order. This difference is adequate to counter the larger phase space available for stabilizing the antiferromagnetic state. Thus, the ground state is found to be ferromagnetic for reasonable inter-ball transfer integrals.

A.c. conductivity studies on the silver molybdo-arsenate glassy system

A new quaternary fast-ion conducting silver molybdo-arsenate [Agl-Ag2O-(MoO3 + As2O5)] (SMA) glassy system has been prepared using the melt-quenching technique for various dopant salt (Agl) concentrations by fixing the formers (MoO3 + As2O5) composition and the modifier (Ag2O) to formers (M/F) ratio. The prepared compounds were characterized by X-ray diffraction. The impedance measurements were made on different Agl compositions of the SMA glasses as a function of frequency (6.5 Hz-65 kHz) and temperature (303-343 K), using the Solatron frequency-response analyser(model 1250). The bulk conductivity and the appropriate physical model (equivalent circuit) of the SMA glass were obtained from the impedance analysis. The a.c. conductivity was calculated for different Agl compositions of SMA glasses at various temperatures and the obtained a.c. conductivity results were analysed using Jonscher's Universal Law. The conduction mechanism for the highest conducting SMA glassy compound has been explained using the diffusion path model.

Topological mimicry and epitope duplication in the guanylyl cyclase C receptor

Guanylyl cyclase C (GCC) is the receptor for the gastrointestinal hormones, guanylin, and uroguanylin, in addition to the bacterial heat-stable enterotoxins, which are one of the major causes of watery diarrhea the world over. GCC is expressed in intestinal cells, colorectal tumor tissue and tumors originating from metastasis of the colorectal carcinoma. We have earlier generated a monoclonal antibody to human GCC, GCC:B10, which was useful for the immunohistochemical localization of the receptor in the rat intestine (Nandi A et al., 1997, J Cell Biochem 66:500-511), and identified its epitope to a 63-amino acid stretch in the intracellular domain of GCC. In view of the potential that this antibody has for the identification of colorectal tumors, we have characterized the epitope for GCC:B10 in this study. Overlapping peptide synthesis indicated that the epitope was contained in the sequence HIPPENIFPLE. This sequence was unique to GCC, and despite a short stretch of homology with serum amyloid protein and pertussis toxin, no cross reactivity was detected. The core epitope was delineated using a random hexameric phage display library, and two categories of sequences were identified, containing either a single, or two adjacent proline residues. No sequence identified by phage display was identical to the epitope present in GCC, indicating that phage sequences represented mimotopes of the native epitope. Alignment of these sequences with HIPPENIFPLE suggested duplication of the recognition motif, which was confirmed by peptide synthesis. These studies allowed us not only to define the requirements of epitope recognition by GCC:B10 monoclonal antibody, but also to describe a novel means of epitope recognition involving topological mimicry and probable duplication of the cognate epitope in the native guanylyl cyclase C receptor sequence.

Facile C-O bond scission in alcohols on Zn surfaces

Interaction of methanol, ethanol, and 2-propanol with polycrystalline as well as (0001) surfaces of Zn has been investigated by photoelectron spectroscopy and vibrational energy loss spectroscopy. All the alcohols show evidence for the condensed species along with the chemisorbed species at 80 K. With increase in temperature to similar to 120 K, the condensed species desorbs, leaving the chemisorbed species which decomposes to give the alkoxy species. The alkoxy species is produced increasingly at lower temperatures as we go from methanol to 2-propanol, the 2-propoxy species occurring even at 80 K. The alkoxy species undergo C-O bond scission giving rise to a hydrocarbon species and oxygen. The C-O bond cleavage occurs at a relatively low temperature of similar to 150 K. The effect of preadsorbed oxygen is to stabilize the methoxy species and prevent C-O bond scission. On the other hand, coadsorption of oxygen with methanol favors the formation of the methoxy species and gives rise to hydrocarbon species arising from the C-O bond scission even at 80 K.

Solid state stacked trimers of 1,10-phenanthroline in a supramolecular tubular motif of C-methyl calix[4]resorcinarene

The self-assembly of bidentate ligand, 1,10-phenanthroline with C-methyl calix[4]resorcinarene (CMCR) in presence of coumarin results in a unique trimer stacking arrangement of phenanthroline molecules in a nanotubular motif generated by the supramolecular assembly of the host.

Guanylyl Cyclase C Receptor: Regulation of Catalytic Activity by ATP

Guanylyl cyclase C (GCC), a member of the family of membrane bound guanylyl cyclases is the receptor for the heat-stable enterotoxin (ST) peptides and the guanylin family of endogenous peptides. GCC is activated upon ligand binding to increase intracellular cGMP levels, which in turn activates other downstream signalling events in the cell. GCC is also activated in vitro by nonionic detergents. We have used the T84 cell line as a model system to investigate the regulation of GCC activity by ATP. Ligand-stimulated GCC activity is potentiated in the presence of ATP, whereas detergent-stimulated activity is inhibited. The potentiation of GCC activity by ATP is dependent on the presence of Mg2+ ions, and is probably brought about by a direct binding of Mg-ATP to GCC. The protein kinase-like domain of GCC, which has earlier been shown to play a critical role in the regulation of GCC activity, may be a possible site for the binding of Mg-ATP to GCC.

Highly efficient C-8 oxidation of substituted xanthines with substitution at the 1-, 3-, and 7- positions using biocatalysts

A bacterial consortium consisting of strains belongings to the genus Klebsiella and Rhodococcus quantitatively converts 1-, 3- and 7-substituted xanthines to their respective 8-oxo compounds.

Synthesis of Unnatural C-2 Amino Acid Nucleosides Using NIS-Mediated Ring Opening of 1,2-Cyclopropane Carboxylated Sugar Derivatives

We have developed a general and efficient method for the stereoselective construction of pyrimidine-based pyranosyl C-2 amino acid nucleosides using NIS-mediated ring opening of 1,2-cyclopropanated sugar derivatives. This methodology has been successfully extended to the synthesis of furanosyl nucleosides, Which have potential applications in the development of novel, nontoxic antifungal therapeutics.

Crystalline A-DNA: The X-Ray Analysis of the Fragment d(G-G-T-A-T-A-C-C)

An A-DNA type double helical conformation was observed in the single crystal X-ray structure of the octamer d(G-G-T-A-T-A-C-C), 1, and its 5-bromouracil-containing analogue, 2. The structure of the isomorphous crystals (space group P61) was solved by a search technique based on packing criteria and R-factor calculations, with use of only low order data. At the present stage of refinement the R factors are 31 % for 1 and 28 % for 2 at a resolution of 2.25 A (0.225 nm). The molecules interact through their minor grooves by hydrogen bonding and base to sugar van der Waals contacts. The stable A conformation observed in the crystal may have some structural relevance to promoter regions where the T-A-T-A sequence is frequently found.

Molecular-Conformation of 1,3-Pyridylphenylureas by H-1 and C-13 NMR-study

1H and 13C NMR spectra are reported for several 1,3-pyridylphenyl ureas. Analysis of the spectra yielded the chemical shifts. The variations in the chemical shifts have been discussed in terms of the molecular conformations.

Cytochrome c oxidase is preferentially synthesized in the rough endoplasmic reticulum--mitochondrion complex in rat liver

The specific activity and content of cytochrome oxidase in the rough endoplasmic reticulum--mitochondrion complex are higher than in the mitochondrial fraction. Radiolabelling studies with the use of hepatocytes and isolated microsomal and rough endoplasmic reticulum--mitochondrion fractions, followed by immunoprecipitation with anti-(cytochrome oxidase) antibody, reveal that the nuclear-coded cytoplasmic subunits of cytochrome oxidase are preferentially synthesized in the latter fraction. The results have a bearing on the mechanism of transport of these subunits into mitochondria.

Left-handed helices for DNA: studies on poly[d(I-C)]

Earlier, we showed that, for the D form (n = 8 and h = 3.03 A, where n is number of nucleotide units per turn and h is height per nucleotide unit) of poly[d(A-T)], both right- and left-handed double helical models are stereochemically satisfactory and give good agreement with the observed fiber diffraction data. It was also noted that the conformations of the right- and left-handed D-DNA models are very similar to those of the right- and left-handed B-DNA models. This observation was consistent with the D leads to B transition in the solid phase. As a continuation of our earlier studies, we have carried out similar experiments with poly[d(I-C)]. We could obtain a crystalline D-form pattern (n = 8, h = 3.13 A) of the fiber at 75% relative humidity (r.h.); the hydrated (r.h. approximately equal to 95%) form of the same fiber gave the classical B-form pattern (n = 10, h = 3.40 A). In the present report, we show that both right- and left-handed double-helical models are consistent with the fiber diffraction data of poly[d(I-C)] in the D-form. Theoretical energy calculations also suggest that the right- and left-handed B- and D-DNA models are almost equally stable. Hence, we conclude that the right- and left-handed double-helical models of poly[d(I-C)] in a given form (B or D) are equally likely and that the fiber diffraction data do not permit discrimination.

Structural Basis of Drug Resistance by Genetic Variants of HIV Type 1 Clade C Protease from India

Using computer modeling of three-dimensional structures and structural information available on the crystal structures of HIV-1 protease, we investigated the structural effects of mutations, in treatment-naive and treatment-exposed individuals from India and postulated mechanisms of resistance in clade C variants. A large number of models (14) have been generated by computational mutation of the available crystal structures of drug bound proteases. Localized energy minimization was carried out in and around the sites of mutation in order to optimize the geometry of interactions present. Most of the mutations result in structural differences at the flap that favors the semiopen state of the enzyme. Some of the mutations were also found to confer resistance by affecting the geometry of the active site. The E35D mutation affects the flap structure in clade B strains and E35N and E35K mutation, seen in our modeled strains, have a more profound effect. Common polymorphisms at positions 36 and 63 in clade C also affected flap structure. Apart from a few other residues Gln-58, Asn-83, Asn-88, and Gln-92 and their interactions are important for the transition from the closed to the open state. Development of protease inhibitors by structure-based design requires investigation of mechanisms operative for clade C to improve the efficacy of therapy.

Retrogressed eclogite (20 kbar, 1020 °C) from the Neoproterozoic Palghat–Cauvery suture zone, southern India

The Palghat–Cauvery suture zone in southern India separates Archaean crustal blocks to the north and the Proterozoic Madurai block to the south. Here we present the first detailed study of a partially retrogressed eclogite (from within the Sittampundi anorthositic complex in the suture zone) that occurs as a 20-cm wide layer in a garnet gabbro layer in anorthosite. The eclogite largely consists of an assemblage of coexisting porphyroblasts of almandine–pyrope garnet and augitic clinopyroxene. However, a few garnets contain inclusions of omphacite. Rims and symplectites composed of Na–Ca amphibole and plagioclase form a retrograde assemblage. Petrographic analysis and calculated phase equilibria indicate that garnet–omphacite–rutile–melt was the peak metamorphic assemblage and that it formed at ca. 20 kbar and above 1000 °C. The eclogite was exhumed on a very tight hairpin-type, anticlockwise P–T path, which we relate to subduction and exhumation in the Palghat–Cauvery suture zone. The REE composition of the minerals suggests a basaltic oceanic crustal protolith metamorphosed in a subduction regime. Geological–structural relations combined with geophysical data from the Palghat–Cauvery suture zone suggest that the eclogite facies metamorphism was related to formation of the suture zone. Closure of the Mozambique Ocean led to development of the suture zone and to its western extension in the Betsimisaraka suture of Madagascar.

Biosynthesis of cytoplasmic subunits of cytochrome C oxidase in rat liver

The biosynthesis of the cytoplasmic subunits of cytochrome oxidase from rat liver has been studied in vitro by translating liver poly (A)-containing RNA in the wheat germ cell-free system and immunoprecipitating the products with anti-cytochrome oxidase antibody. Analysis of the labelled immunoprecipitate on SDS-gels does not reveal the presence of a polyprotein precursor. On the other hand discrete products which are either slightly bigger or closely similar to the mature subunits present in purified cytochrome oxidase have been detected.