Sacrificial photolysis of water on TiO2 fine powders prepared by the hydrothermal method

The often discussed role of surface hydroxylation of TiO2 particles as an essential characterestics for their photocatalytic activity can be verified by preparing TiO2 powders by hydrothermal method since hydroxylated surface layers will be better retained on these particles formed in superheated water. Thus, fine powders of TiO2 (rutile) with high degree of crystallinity are formed from titanium oxychloride in the mixed solvent of water and 2-propanol at 160–230°C and 20–120 atm. The anatase phase is produced from the same medium when sulfate ion impurity is present, with Image . TiO2 powders are washed free of anions and 2-propanol by ultrafiltration and are Pt mounted by a photochemical method. Aqueous suspensions of both forms of TiO2 neither as such nor after Pt-loading, do not produce H2 on band gap illumination whereas, H2 is generated in presence of hole scavengers such as EDTA, TEOA, sulfite or hypophosphite. The effects of hole scavenger concentration, Pt : TiO2 ratio, particulate suspension density and the nature of hole scavengers on H2 production are presented. Platinised rutile powders are equally active as anatase in sacrificial systems.

Presence of 2-methylthioribosyl-trans-zeatin in Azotobacter vinelandii tRNA.

Hydroxylated cytokinin, 2-methylthio-N6-(4-hydroxy-3-methylbut-2-enyl) adenosine, was found in the tRNA of Azotobacter vinelandii. This cytokinin had the trans configuration, unlike the cis configuration reported for that from other bacteria. Culture-condition-dependent changes in the content of this thiocytokinin and a few other thionucleosides in the tRNA of this bacterium have been observed.

Influence of Hydrophilic Surface Specificity on the Structural Properties of Confined Water

The influence of chemical specificity of hydrophilic surfaces on the structure of confined water in the subnanometer regime is investigated using grand canonical Monte Carlo Simulations. The structural variations for water confined between hydroxylated silica surfaces are contrasted with water confined between mica surfaces. Although both surfaces are hydrophilic, our Study shows that hydration of potassium ions on the mica surface has a strong influence on the water Structure and solvation force response of confined water. In contrast to the disrupted hydrogen bond network observed for water confined between Mica Surfaces, water between silica surfaces retains its hydrogen bond network displaying bulklike structural features down to surface separations as small as 0.45 nm. Hydrogen bonding of all invariant contact water layer with the surface silanol groups aids in maintaining a constant number of hydrogen bonds per water molecule for the silica surfaces. As a consequence water depletion and rearrangement upon decreasing confinement is a strong function of the hydrophilic surface specificity, particularly at smaller separations. An oscillatory solvation force response is only observed for water confined between Silica surfaces, and bulklike features are observed for both Surfaces above a surface separation of about 1.2 nm. We evaluate and contrast the water density, dipole moment distributions, pi pair correlation functions, and solvation forces as a function of the surface separation.

Proteomics and mass spectrometric studies reveal planktonic growth of Mycobacterium smegmatis in biofilm cultures in the absence of rpoZ

Mycobacterium smegmatis is known to form biofilms and many cell surface molecules like core glycopeptidolipids and short-chain mycolates appear to play important role in the process. However, the involvement of the cell surface molecules in mycobacteria towards complete maturation of biofilms is still not clear. This work demonstrates the importance of the glycopeptidolipid species with hydroxylated alkyl chain and the epoxylated mycolic acids, during the process of biofilm development. In our previous study, we reported the impairment of biofilm formation in rpoZ-deleted M. smegmatis, where rpoZ codes for the ω subunit of RNA polymerase (R. Mathew, R. Mukherjee, R. Balachandar, D. Chatterji, Microbiology 152 (2006) 1741). Here we report the occurrence of planktonic growth in a mc2155 strain which is devoid of rpoZ gene. This strain is deficient in selective incorporation of the hydroxylated glycopeptidolipids and the epoxy mycolates to their respective locations in the cell wall. Hence it forms a mutant biofilm defective in maturation, wherein the cells undertake various alternative metabolic pathways to survive in an environment where oxygen, the terminal electron acceptor, is limiting.

Studies on the ionic transport and structural investigations of La0.5Li0.5TiO3 perovskite synthesized by wet chemical methods and the effect of Ce, Zr substitution at Ti site

La0.5Li0.5TiO3 perovskite was synthesized by various wet chemical methods. By adopting low temperature methods of preparation lithium loss from the material is prevented. La0.5Li0.5TiO3 (LLTO) was formed with cubic symmetry at 1473 K. LLTO was formed at relatively lower temperature by using hydrothermal preparation method. PVA gel-decomposition route yield tetragonal LLTO on annealing the dried gel at 1473 K. By using gel-carbonate route LiTi2O4 minor phase was found to remain even after heat-treatment at 1473 K. The hydroxylation of LLTO was done in deionized water as well as in dilute acetic acid medium. By hydroxylation process incorporation of hydroxyls and leaching out of Li+ was observed from the material. The Li+ concentration of these compositions was examined by AAS. The electrical conductivities of these compositions were measured by dc and ac impedance techniques at elevated temperatures. The activation energies of electrical conduction for these compositions were estimated from the experimental results. The measured activation energy of Li+ conduction is 0.34 eV. Unhydroxylated samples exhibit only Li+ conduction, whereas, the hydroxylated LLTO show proton conductivity at 298-550 K in addition to Li+ conductivity. The effect of Zr or Ce substitution in place of Ti were attempted. La0.5Li0.5ZrO3 Perovskite was not formed; instead pyrochlore phase (La2Zr2O7) along with monoclinic ZrO2 phases was observed above 1173 K; below 1173 K cubic ZrO2 is stable. (La0.5Li0.5)(2)CeO4 solid solution was formed in the case of Ce substitution at Ti sublattice on heat-treatment up to 1673 K. (c) 2005 Springer Science + Business Media, Inc.

Carotenoids In 3 Stages Of Ripening Of Mango

The distribution of carotenoids, both qualitative and quantitative, during 3 stages of ripening of mango has been studied using chromatographic, spectroscopic and chemical methods. There was an increase in content as well as in number of carotenoids during ripening. The present study showed there were 15, 14 and 17 different carotenoids in the unripe, partially ripe and fully ripe mangoes, respectively. Even though phytofluene (39.26%) was the major carotenoid in the partially ripe mango, β-carotene constituted the major carotenoid in the unripe (37.47%) and fully ripe mango (50.64%). cis-β-Carotene was present only in the fully ripe mango. Only the unripe mango contained ζ-carotene, whereas γ-carotene was present in all the 3 stages of ripening. The major xanthophyll present in the unripe mango was mutatoxanthin (9.44%), whereas auroxanthin constituted the major hydroxylated carotenoid of the partially ripe (5.07%) and fully ripe (10.40%) mangoes. The percent of cryptoxanthin dropped to lower levels during ripening. As ripening proceeded, lutein completely is appeared. There were significant quantities of eaxanthin in the partially ripe and fully ripe mango. Epoxy carotenoids such as 5,6-monoepoxy-β-carotene, mutatochrome, cis-violaxanthin, luteoxanthin, mutatoxanthin and auroxanthin were observed in all 3 stages of ripening.

Surface chemical studies on pyrite in the presence of polysaccharide-based flotation depressants

The interaction of dextrin and guar gum with pyrite has been investigated through adsorption, flotation, and electrokinetic measurements. The adsorption densities of the polysaccharides onto pyrite reveal a region of higher adsorption density in the pH range 7.5-11, with a maximum around pH 10 for both polymers. The isotherms exhibit Langmuirian behavior. The adsorption density of guar gum onto pyrite is higher than that of dextrin. Electrokinetic measurements indicate a decrease in the electrophoretic mobility values in proportion to the concentration of the polymer added. Co-precipitation tests confirm polymer-ferric species interaction in the bulk solution, especially in the pH range 5.5-8.5. The pH range for higher adsorption, significant co-precipitation, and appreciable depression of pyrite encompass each other. XPS and FTIR spectroscopic studies provide evidence in support of chemical interaction between hydroxylated pyrite and the hydroxyl groups of the polymeric depressants. (C) 2000 Academic Press.

Biotransformations of α-terpineol in the rat: Its effects on the liver microsomal cytochrome P-450 system

Alpha-Terpineol (I), a monocyclic monoterpene tertiary alcohol, is widely used in the manufacture of perfumes, cosmetics, soaps and antiseptic agents. It was reported earlier (Horning et al. 1976) that this monoterpene alcohol when administered to humans is hydroxylated to p-menth-l,2,8-triol (II). It is not known whether c~-terpineol also produces other metabolites during its metabolism in the mammalian system and if so, the nature of these metabolites.

Transformations of acetates of citronellol, geraniol, and linalool by Aspergillus niger: regiospecific hydroxylation of citronellol by a cell-free system

Incubation of acetates of geraniol, citronellol and linalool with Aspergillus niger resulted in their hydrolysis to corresponding alcohols which were further hydroxylated to their respective 8-hydroxy derivatives. In the case of linalyl acetate, besides linalool and 8-hydroxylinalool, small amounts of geraniol and agr-terpineol were also formed. Microsomes (105 000xg sediment) prepared from induced cells of A. niger were found to convert (1-3H)citronellol to 8-hydroxy citronellol in the presence of NADPH and O2. The pH optimum for the hydroxylase was found to be 7.6.

Studies on the 14α-hydroxylation of progesterone in mucor piriformis

Cell-free extracts with high 14?-hydroxylase activity were prepared from induced vegetative cell cultures of Mucor piriformis by grinding in potassium phosphate buffer (0.05 M, pH 8.0) containing glucose (0.25 M), KCl (1 mM), glutathione (1.0 mM) and glycerol (10%). Although the ideal pH for preparing the cell-free extract from vegetative cells was 8.0, the pH optimum of the hydroxylase was found to be 7.6. Microsomes (2.0 mg) prepared from the crude cell-free extract hydroxylated progesterone to 14?-hydroxyprogesterone in not, vert, similar60% yields in 30 min in the presence of NADPH and O2. Microsomes prepared from the uninduced cells did not contain any 14?-hydroxylase activity. The hydroxylase activity was inhibited to a significant extent by CO and p-chloromercuribenzoate whereas moderate inhibition was noticed in the presence of SKF-525A, metyrapone and N-methylmaleimideindicating the possible involvement of the cytochromeP-450 system in the reaction. The membrane bound hydroxylase was solubilized using Triton X-100 and the solubilized fraction contained nearly 35% of the original hydroxylase activity.

Evidence for the involvement of multiple pathways in the biodegradation of 1- and 2-methylnaphthalene by pseudomonas putida CSV86

Pseudomonas putida CSV86, a soil bacterium, grows on 1- and 2-methylnaphthalene as the sole source of carbon and energy. In order to deduce the pathways for the biodegradation of 1- and 2-methylnaphthalene, metabolites were isolated from the spent medium and purified by thin layer chromatography. Emphasis has been placed on the structural characterisation of isolated intermediates by CC-MS, demonstration of enzyme activities in the cell free extracts and measurement of oxygen uptake by whole cells in the presence of various probable metabolic intermediates. The data obtained from such a study suggest the possibility of occurrence of multiple pathways in the degradation of 1- and 2-methylnaphthalene. We propose that, in one of the pathways, the aromatic ring adjacent to the one bearing the methyl moiety is oxidized leading to the formation of methylsalicylates and methylcatechols. In another pathway the methyl side chain is hydroxylated to -CH2-OH which is further converted to -CHO and -COOH resulting in the formation of naphthoic acid as the end product. In addition to this, 2-hydroxymethylnaphthalene formed by the hydroxylation of the methyl group of 2-methylnaphthalene undergoes aromatic ring hydroxylation. The resultant dihydrodiol is further oxidised by a series of enzyme catalysed reactions to form 4-hydroxymethyl catechol as the end product of the pathway.

Utility of microbes in organic-synthesis - selective transformations of acyclic isoprenoids by aspergillus-niger

Bioconversion of acyclic isoprenoids using a strain of Aspergillus niger results in hydroxylated metabolites with regio- and stereoselectivity. The organism carries out oxidation of the terminal allylic methyl group and the remote double bond in all the compounds tested (I-VII). However, these two activities seem to have preferential structural requirements. When an acyclic isoprenoid with a ketone functionality such as geranylacetone is used as the substrate, the organism also carries out the asymmetric reduction of the keto group. All the metabolites formed have been purified and characterized by conventional spectroscopic methods and quantification has been made by gas chromatographic analyses.

Transformation of 16-dehydroprogesterone and 17?-hydroxyprogesterone by Mucor piriformis

Mucor piriformis was used to study the mode of transformation of 16-dehydroprogesterone (I, pregna-4, 16-diene-3, 20-dione) and 17 alpha-hydroxyprogesterone (II, 17 alpha-hydroxypregn-4-ene-3, 20-dione). Biotransformation products formed from I were 14 alpha-hydroxypregna-4, 16-diene-3, 20-dione (Ia), 7 alpha, 14 alpha-dihydroxypregna-4 16-diene-3, 20-dione (Ib), 3 beta, 7 alpha, 14 alpha-trihydroxy-5 alpha-pregn-16-en-20-one (Ic), and 3 alpha, 7 alpha, 14 alpha-trihydroxy-5 alpha-pregn-16-en-20-one (Id). Metabolites Ic and Id appear to be hitherto unknown. Timecourse studies suggested that the transformation is initiated by hydroxylation at the 14 alpha-position (Ia) followed by hydroxylation at the 7 alpha-position (Ib). Microsomes (105,000 g sediment) prepared from 16-dehydroprogesterone-induced cells hydroxylate I to its 14 alpha-hydroxy derivative (Ia) in the presence of NADPH. Incubation of Ia with the organism resulted in the formation of Ib, Ic and Id. Biotransformation products formed from compound II were 17 alpha, 20 alpha-dihydroxypregn-4-en-3-one (IIa), 7 alpha, 17 alpha-dihydroxypregn-4-ene-3, 20-dione (IIb), 6 beta, 17 alpha, 20 alpha-trihydroxypregn-4-en-3-one (IIc) and 11 alpha, 17 alpha, 20 alpha-trihydroxypregn-4-en-3-one (IId). Time-course studies indicated that IIa is the initial product formed, which is further hydroxylated either at the 6 beta or 11 alpha position. Incubation of IIa with the organism resulted in the formation of IIc and IId. Reduction of the 4-en-3-one system and 20-keto group has not been observed before in organisms of the order Mucorales. In addition, M. piriformis has been shown to carry out hydroxylation at the C-6, C-7, C-11 and C-14 positions in the steroid molecules tested.

Retarding effect of surface hydroxylation on titanium(IV) oxide photocatalyst in the degradation of phenol

Nanosized powders of TiO2 (anatase) were prepared by the hydrothermal method, acid-medium hydrolysis or by vacuum freeze-drying of sols, and annealing at temperatures <700-degrees-C. Photocatalytic activities of these powders in the mineralization of phenol, were evaluated in comparison to that of Degussa P25. Kinetic data indicated that surface hydroxylation had a retarding effect on the degradation of phenol. Formation of stable peroxotitanium species were observed on hydroxylated powders, whereas only V(Ti)-O- hole trap centres were detected by EPR on the heat treated samples. The data supports direct hole oxidation of the substrate preadsorbed on the photocatalyst, which is otherwise blocked by surface hydroxyls.

Cytochrome P4504f, a potential therapeutic target limiting neuroinflammation

Inflammatory processes are involved in the pathogenesis and/or progression of acute central nervous system (CNS) infection, traumatic brain injury and neurodegenerative disorders among others indicating the need for novel strategies to limit neuroinflammation. Eicosanoids including leukotrienes, particularly leukotriene B-4 (LTB4) are principle mediator(s) of inflammatory response, initiating and amplifying the generation of cytokines and chemokines. Cytochrome P450 (Cyp), a family of heme proteins mediate metabolism of xenobiotics and endogenous compounds, such as eicosanoids and leukotrienes. Cytochrome P4504F (Cyp4f) subfamily includes five functional enzymes in mouse. We cloned and expressed the mouse Cyp4f enzymes, assayed their relative expression in brain and examined their ability to hydroxylate the inflammatory cascade prompt LTB4 to its inactive 20-hydroxylated product. We then examined the role of Cyp4fs in regulating inflammatory response in vitro, in microglial cells and in vivo, in mouse brain using lipopolysacharide (LPS), as a model compound to generate inflammatory response. We demonstrate that mouse brain Cyp4fs are expressed ubiquitously in several cell types in the brain, including neurons and microglia, and modulate inflammatory response triggered by LPS, in vivo and in microglial cells, in vitro through metabolism of LTB4 to the inactive 20-hydroxy LTB4. Chemical inhibitor or shRNA to Cyp4fs enhance and inducer of Cyp4fs attenuates inflammatory response. Further, induction of Cyp4f expression lowers LTB4 levels and affords neuroprotection in microglial cells or mice exposed to LPS. Thus, catalytic activity of Cyp4fs is a novel target for modulating neuroinflammation through hydroxylation of LTB4. (C) 2011 Elsevier Inc. All rights reserved.