Studies in sesquiterpenes—XXVI : Synthesis of 2,2,6-trimethyl-3-oxo-1-carbomethoxybicyclo[0,3,3]octane, a degradation product of patchouli alcohol

The synthesis of the title compound is described and results of some experiments on the degradation of patchouli alcohol are reported.

X-ray Crystallographic Analysis of the Complexes of Enoyl Acyl Carrier Protein Reductase of Plasmodium falciparum with Triclosan Variants to Elucidate the Importance of Different Functional Groups in Enzyme Inhibition

Triclosan, a well-known inhibitor of Enoyl Acyl Carrier Protein Reductase (ENR) from several pathogenic organisms, is a promising lead compound to design effective drugs. We have solved the X-ray crystal structures of Plasmodium falciparum ENR in complex with triclosan variants having different substituted and unsubstituted groups at different key functional locations. The structures revealed that 4 and 2' substituted compounds have more interactions with the protein, cofactor, and solvents when compared with triclosan. New water molecules were found to interact with some of these inhibitors. Substitution at the 2' position of triclosan caused the relocation of a conserved water molecule, leading to an additional hydrogen bond with the inhibitor. This observation can help in conserved water-based inhibitor design. 2' and 4' unsubstituted compounds showed a movement away from the hydrophobic pocket to compensate for the interactions made by the halogen groups of triclosan. This compound also makes additional interactions with the protein and cofactor which compensate for the lost interactions due to the unsubstitution at 2' and 4'. In cell culture, this inhibitor shows less potency, which indicates that the chlorines at 2' and 4' positions increase the ability of the inhibitor to cross multilayered membranes. This knowledge helps us to modify the different functional groups of triclosan to get more potent inhibitors. (C) 2010 IUBMB IUBMB Life, 62(6): 467-476.

Low Temperature Synthesis of Nano-Crystalline CaCu3Ti4O12 Through aFuel Mediated Auto-Combustion Pathway

A novel, cost effective,environment-friendly and energetically beneficial alternative method for the synthesis of giant dielectric pseudo-perovskite material CaCu3Ti4O12 (CCTO) is presented. The method involved auto-combustion of an aqueous precursor solution in oxygen atmosphere with the help of external fuels and is capable of producing high amount of CCTO at ultra-low temperature, in the combustion residue itself. The amount of phase generated was observed to be highly dependent on the combustion process i.e. on the nature and amount of external-fuels added for combustion. Two successful fuel combinations capable of producing reasonably higher amount of the desired compound were investigated. On a structural characterization grain size was observed to decrease drastically to nano-dimension compared to submicron-size that was obtained in a traditional sol-gel combustion and subsequent cacination method. Therefore, the method reported can produce nano-crystalline CaCu3Ti4O12 ceramic matrix at an ultra-low temperature and is expected to be applicable for other multifunctional perovskite oxide materials.

An association model for the solubilities of pharmaceuticals in supercritical carbon dioxide

The equilibrium solubility of a pharmaceutical compound. 1,5-dimethy1-2-phenyl-4-propan-2-ylpyrazol-3-one (propyphenazone, isopropylantipyrine) in supercritical carbon dioxide (SCCO2) was experimentally determined by a saturation method at 308, 318 and 328 K. over the pressure range of 9.0-19.0 MPa. The solubility data satisfied the self-consistency test, proposed by Mendez-Santiago and Teja. A new association model was derived to correlate the solubilities of pharmaceutical compounds in SCCO2. Solubility data from 54 different pharmaceutical compounds including steroids, antibiotics, anti-inflammatory, antioxidants, statins and specific functional drugs were collected from literature. The model successfully correlated the experimental results for the solubilities of all these compounds in SCCO2 within 12% AARD. (C) 2010 Elsevier B.V. All rights reserved.

Tyrphostin-A47 inhibitable tyrosine phosphorylation of flagellar proteins is associated with distinct alteration of motility pattern in hamster spermatozoa

To acquire fertilizing potential, mammalian spermatozoa must undergo capacitation and acrosome reaction. Our earlier work showed that pentoxifylline (0.45 mM), a sperm motility stimulant, induced an early onset of hamster sperm capacitation associated with tyrosine phosphorylation of 45-80 kDa proteins, localized to the mid-piece of the sperm tail. To assess the role of protein tyrosine phosphorylation in sperm capacitation, we used tyrphostin-A47 (TP-47), a specific protein tyrosine kinase inhibitor. The dose-dependent (0.1-0.5 mM) inhibition of tyrosine phosphorylation by TP-47 was associated with inhibition of hyperactivated motility and 0.5 mM TP-47-treated spermatozoa exhibited a distinct circular motility pattern. This was accompanied by hypo-tyrosine phosphorylation of 45-60 kDa proteins, localized to the principal piece of the intact-sperm and the outer dense fiber-like structures in detergent treated-sperm. Sperm kinematic analysis (by CASA) of spermatozoa, exhibiting circular motility (at 1st hr), showed lower values of straight line velocity, curvilinear velocity and average path velocity, compared to untreated controls. Other TP-47 analogues, tyrphostin-AG1478 and -AG1296, had no effect either on kinematic parameters or sperm protein tyrosine phosphorylation. These studies indicate that TP-47-induced circular motility of spermatozoa is compound-specific and that the tyrosine phosphorylation status of 45-60 kDa flagellum-localized proteins could be key regulators of sperm flagellar bending pattern, associated with the hyperactivation of hamster spermatozoa.

Synthetic, spectroscopic, magnetic, and x-ray structural studies on a vitamin B6-amino acid Schiff base complex, aqua(5'-phosphopyridoxylidenetyrosinato)copper(II) tetrahydrate

A Schiff base metal complex, [Cu(II)(PLP-DL-tyrosinato)(H2O)].4H2O (PLP = pyridoxal phosphate), with the molecular formula CuC17O13N2H27P has been prepared and characterized by magnetic, spectral, and X-ray structural studies. The compound crystallizes in the triclinic space group P1BAR with a = 8.616 (2) angstrom, b = 11.843 (3) angstrom, c = 12.177 (3) angstrom, alpha = 103.40 (2)degrees, beta = 112.32 (2)degrees, gamma = 76.50 (1)degrees, and Z = 2. The structure was solved by the heavy-atom method and refined by least-squares techniques to a final R value of 0.057 for 3132 independent reflections. The coordination geometry around Cu(II) is distorted square pyramidal with phenolic oxygen, imino nitrogen, and carboxylate oxygen from the Schiff base ligand and water oxygen as basal donor atoms. The axial site is occupied by a phosphate oxygen from a neighboring molecule, thus resulting in a one-dimensional polymer. The structure reveals pi-pi interaction of the aromatic side chain of the amino acid with the pyridoxal pi system. A comparative study is made of this complex with similar Schiff base complexes. The variable-temperature magnetic behavior of this compound shows a weak antiferromagnetic interaction.

Crystal and Molecular Structure of N-acetyl-L-glutamine

The crystal and molecular structure of the title compound has been determined by direct methods from diffractometer data. Crystals are orthorhombic, with Z= 4 in a unit cell of dimensions : a= 13.811 (10), b= 5.095(5), c= 12.914(10)Å, space group P212121. The structure was refined by least-squares to R 3.31% for 868 observed reflections. There is significant non-planarity of the peptide group and its nitrogen atom is significantly pyramidal. There is no correlation between the double-bond character and reactivity of the C–N bond of the terminal amide group in glutamine and acetamide

Effect of hole localization on Madelung potential of YBa2Cu3O7

The Madelung potential and formation energy of the superconducting compound YBa2Cu3O7 have been computed for hole localization at different sites in the crystal. The cases considered include Cu3+ ion at Cu(1) and Cu(2) sites, O− ion at O(1), O(2), O(3) and O(4) sites and combinations of O− and Cu3+ ions at O(4) and Cu(1) and O(2,3) and Cu(2) sites. The two lowest-energy configurations correspond to Cu3+ ion at Cu(1) site and O− ion at O(4) site. The difference in formation energy between those configurations is relatively small. The next preferred configuration corresponds to simultaneous partial localization of the hole at Cu (1) site and O(1) site. Other configurations are much less stable. The results suggest a resonating or fluctuating valence model for YBa2Cu3O7.

Crystal and Molecular Structure of Sclerophytin F Methyl Ether from the Soft Coral Cladiella krempfi

new cembranoid diterpene was isolated from the soft coral Ckdiella h p f ifrom Minicoy Island (India), and its structure was established by X-ray crystallography to be sclerophytin F methyl ether (21 with the R absolute configuration at all six epimeric centers,assuming a configuration similar to that of sclerophytin C. Compound 2 may be an artifact of the isolation process.

Dye sensitized visible light degradation of phenolic compounds

The present research work reports the eosin Y (EY) and fluorescein (FL) sensitized visible light degradation of phenol, 4-chlorophenol (CP), 2,4-dichlorophenol (DCP) and 2,4,6-trichlorophenol (TCP) using combustion synthesized nano-TiO2 (CS TiO2). The rate of degradation of the phenolic compounds was higher in the presence of EY/CS TiO2 compared to FL/CS TiO2 system. A detailed mechanism of sensitized degradation was proposed and a mechanistic model for the rate of degradation of the phenolic compound was derived using the pyramidal network reduction technique. It was found that at low initial dye concentrations, the rate of degradation of the phenolic compound is first order in the concentration of the dye, while at high initial dye concentrations, the rate is first order in the concentration of the phenolic compound. The order of degradation of the different phenolic compounds follows: CP > TCP > DCP > phenol. The different phenolic and dye intermediates that were formed during the degradation were identified by liquid chromatography-mass spectrometry (LC-MS) and the most probable pathway of degradation is proposed. (C) 2010 Elsevier B.V. All rights reserved.

Synthesis of 5,5-Dimethyl-7-methoxy 4-oxatricyclo [4,3,1,03,7]decan-2-ones

Two new synthetic routes for the preparation of the title compound and its 3-substituted derivatives, a novel ring system present in morellin and other related natural products, are reported from the readily available dihydroanisoles.

A pathway for biodegradation of 1-naphthoic acid by Pseudomonas maltophilia CSV89

Pseudomonas maltophilia CSV89, a bacterium isolated from soil in our laboratory, grows on 1-naphthoic acid as the sole source of carbon and energy. To elucidate the pathway for degradation of 1-naphthoic acid, the metabolites were isolated from spent medium, purified by TLC, and characterized by gas chromatography-mass spectrometry. The involvement of various metabolites as intermediates in the pathway was established by demonstrating relevant enzyme activities in cell-free extracts, oxygen uptake and transformation of metabolites by the whole cells. The results obtained from such studies suggest that the degradation of 1-naphthoic acid is initiated by double hydroxylation of the aromatic ring adjacent to the one bearing the carboxyl group, resulting in the formation of 1,2-dihydroxy-8-carboxynaphthalene. The resultant diol was oxidized via 3-formyl salicylate, 2-hydroxyisophthalate, salicylate and catechol to TCA cycle intermediates.

Linear electro-optic effect and temperature coefficient of birefringence in 4-nitro-4script-methylbenzylidene aniline single crystals

A study of the linear electro?optic effect in single crystals of the organic compound, 4?nitro�4??methylbenzylidene aniline is reported. The reduced half?wave voltages have been found to have values 2.8, 1.3, and 1.1 kV at 632.8, 514.5, and 488.0 nm, respectively and the corresponding values of the largest linear electro?optic coefficient have been calculated. The thermal variation of the birefringence has also been investigated and the temperature variation of the refractive index difference is found to have the value, d?n/dT = 15.8 × 10?5 K?1.

Combustion synthesis of yttria

Fine-particle, sinter-active yttria has been prepared by combustion of a redox compound, Y(N2H3COO)3·3H2O and mixtures of Y(N2H3COO)3·3H2O�NH4NO3 or NH4ClO4 as well as yttrium nitrate and hydrazine-based fuels. The fineparticle nature of the combustion-derived yttria has been investigated using powder density, particle size and BET surface area measurements. The uniaxially, cold-pressed fine-particle yttria when sintered at 1450�1500 °C achieved 98% theoretical density and showed a fine-grain (1�2 µm) microstructure.

Structure of 7-ethylamino-6-methyl-4-trifluoromethylcoumarin

C13H12F3NO2, M(r) = 271.2, triclinic, P1BAR, a = 5.029 (2), b = 7.479 (2), c = 17.073 (5) angstrom, alpha = 97.98 (2), beta = 95.54 (3), gamma = 103.62 (3)-degrees, V = 612.4 (4) angstrom 3, Z = 2, D(m) = 1.463, D(x) = 1.471 g cm-3, lambda(Mo K-alpha) = 0.71069 angstrom, mu = 1.23 cm-1, F(000) = 280, T = 298 K, final R value is 0.041 for 2047 observed reflections with \F(omicron)\ greater-than-or-equal-to 6-sigma(\F(omicron)\). The N-C(sp2) bond length is 1.356 (2) angstrom. The N and C atoms of the ethylamino group deviate by < 0.15 angstrom from the plane of the aromatic ring. Short intramolecular contacts, C(3)...F(17) 2.668 (3) angstrom [H(3)...F(17) 2.39 (2) angstrom, C(3)-H(C3)...F(17) 98 (1)-degrees], C(5)...F(18) 3.074 (3) and C(5)...F(19) 3.077 (3) angstrom exist in the structure. The crystal structure is stabilized by intermolecular N-H...O hydrogen bonds with N(12)-H(N12) 0.79 (3), H(N12)...O(11)' 2.36 (3), N(12)...O(11)' (x - 1, y + 1, z) 3.105 (3) angstrom and N(12)-H(N12)...O(11)' 155 (2)-degrees.