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Sample records for abundant hydroxyl groups

  1. Column abundance measurements of atmospheric hydroxyl at 45 deg S

    NASA Technical Reports Server (NTRS)

    Wood, S. W.; Keep, D. J.; Burnett, C. R.; Burnett, E. B.

    1994-01-01

    The first Southern Hemisphere measurements of the vertical column abundance of atmospheric hydroxyl (OH) have been obtained at Lauder, New Zealand (45 deg S) with a PEPSIOS instrument measuring the absorption of sunlight at 308 nm. The variation of column OH with solar zenith angle is similar to that measured at other sites. However average annual abundances of OH are about 20% higher than those found by similar measurements at 40 deg N. Minimum OH abundances about 10% less than average levels at 40 deg N, are observed during austral spring. The OH abundance abruptly increases by 30% in early summer and remains at the elevated level until late the following winter.

  2. Rapeseed lecithin hydroxylation by chlorine replacing with hydroxyl groups in chlorinated phospholipids.

    PubMed

    Górecki, Michał; Sosada, Marian; Boryczka, Monika; Fraś, Pawel; Pasker, Beata

    2012-01-01

    Rapeseed lecithin ethanol soluble fraction (LESF) was hydroxylated with 30% hydrogen peroxide in the presence of acetic acid. The product was compared to the one obtained by method based on nucleophilic substitution reaction of phospholipids chlorine derivatives. In this approach, hydrogen chloride was added to double bonds in unsaturated acyl groups of phospholipids. Next, chlorine was replaced with hydroxyl groups via the alkaline hydrolysis of chlorine derivatives. The surface active properties of the products obtained with the usage of two methods of rapeseed LESF hydroxylation were determined. The minimal surface tension (eta(min), mN/m) and the critical micelle concentration (CMC, g/L) of LESF hydroxylated with hydrogen peroxide (20.2 mN/m, 6.0 g/L) and obtained by chlorine replacing with hydroxyl groups in chlorinated phospholipids (25.0 mN/m, 9.8 g/L) were compared to LESF (31.8 mN/m, 17.8 g/L). Hydroxylated LESF obtained by lecithin chlorination and chlorine replacing with hydroxyl groups in the chlorine derivatives has no peroxides and the good surface active properties. The product as an effective emulsifier can be used in pharmacy and cosmetics.

  3. Hashish. Importance of the phenolic hydroxyl group in tetrahydrocannabinols.

    PubMed

    Uliss, D B; Dalzell, H C; Handrick, G R; Howes, J F; Razdan, R K

    1975-02-01

    Optically active delta-3- and delta-8-tetrahydrocannabinols (THC's), cannabidiol and racemic delta-9-cis-THC, and their corresponding analogs (1b yields 4b) in which the positions of the phenolic hydroxyl group and the n-C5 side chain have been interchanged are compared in selected pharmacological tests in mice. the results indicate that the phenolic hydroxyl group in the 1 position in THC's is very important for eliciting activity and that cannabidiol and delta-9-cis-THC possess weak CNS depressant properties.

  4. Ground-based column abundance measurements of atmospheric hydroxyl

    NASA Technical Reports Server (NTRS)

    Burnett, Clyde R.

    1988-01-01

    The preliminary results of ground-based OH column abundance measurements from Truk, Federated States of Micronesia, are contained. These are the first OH column measurements from the tropics, and constitute a signficcant contribution to the OH data base. Comparisons of tropical OH behavior with the extensive mid-latitude observations serve as a critical test of the current understanding of the HO (sub x) photochemistry and its relationship to the other major chemical families. The quasi-biennial oscillation (QBO) in tropical stratospheric winds exerts a major influence on the Hadley cell vertical transport. Related QBOs in total O3 and in stratospheric H2O were identified, but QBO effects on other stratospheric species are still unknown. The solar tide in the tropics produces a diurnal surface pressure variation of 2 to 3 mb; its effect on OH photochemistry in the stratosphere may be significant.

  5. Ground-based column abundance measurements of atmospheric hydroxyl

    NASA Astrophysics Data System (ADS)

    Burnett, Clyde R.

    1988-04-01

    The preliminary results of ground-based OH column abundance measurements from Truk, Federated States of Micronesia, are contained. These are the first OH column measurements from the tropics, and constitute a signficcant contribution to the OH data base. Comparisons of tropical OH behavior with the extensive mid-latitude observations serve as a critical test of the current understanding of the HO (sub x) photochemistry and its relationship to the other major chemical families. The quasi-biennial oscillation (QBO) in tropical stratospheric winds exerts a major influence on the Hadley cell vertical transport. Related QBOs in total O3 and in stratospheric H2O were identified, but QBO effects on other stratospheric species are still unknown. The solar tide in the tropics produces a diurnal surface pressure variation of 2 to 3 mb; its effect on OH photochemistry in the stratosphere may be significant.

  6. A ribozyme that triphosphorylates RNA 5′-hydroxyl groups

    PubMed Central

    Moretti, Janina E.; Müller, Ulrich F.

    2014-01-01

    The RNA world hypothesis describes a stage in the early evolution of life in which RNA served as genome and as the only genome-encoded catalyst. To test whether RNA world organisms could have used cyclic trimetaphosphate as an energy source, we developed an in vitro selection strategy for isolating ribozymes that catalyze the triphosphorylation of RNA 5′-hydroxyl groups with trimetaphosphate. Several active sequences were isolated, and one ribozyme was analyzed in more detail. The ribozyme was truncated to 96 nt, while retaining full activity. It was converted to a trans-format and reacted with rates of 0.16 min−1 under optimal conditions. The secondary structure appears to contain a four-helical junction motif. This study showed that ribozymes can use trimetaphosphate to triphosphorylate RNA 5′-hydroxyl groups and suggested that RNA world organisms could have used trimetaphosphate as their energy source. PMID:24452796

  7. Periodic behaviors in the observed vertical column abundances of atmospheric hydroxyl

    NASA Technical Reports Server (NTRS)

    Burnett, Elizabeth Beaver; Burnett, Clyde R.; Minschwaner, Kenneth R.

    1989-01-01

    The data base for the vertical column abundance of atmospheric hydroxyl (OH) for Fritz Peak Observatory, Colorado (40 N, 105 W), now extends from 1976 through 1988 and is composed of 8849 independent data sets, averaging about 15 percent uncertainty and 20-minute time resolution each. The dominant solar zenith angle (chi) dependence of the OH abundance is characterized by an empirical curve, N(88), which has been updated from N(82) to include all valid data from 1980 through 1988. The chi-dependence of the OH abundance has been, to a first order, removed from the data base by a normalization procedure in which each data point is divided by the N(88,AM) value for the corresponding solar zenith angle. The resulting normalized OH values may then be examined for other systematic effects, particularly for periodic variations. Observations have also been made at Boca Raton, Florida (26 N, 80 W) and at Truk, Federated States of Micronesia (7 N, 152 E). These data bases are much less extensive and, as such, are less amenable to analysis for periodic behaviors. Some comparisons with the Colorado data may be made, however.

  8. Photochemical formation of polybrominated dibenzo-p-dioxins from environmentally abundant hydroxylated polybrominated diphenyl ethers.

    PubMed

    Arnoldsson, Kristina; Andersson, Patrik L; Haglund, Peter

    2012-07-17

    High levels of polybrominated dibenzo-p-dioxins (PBDDs) have been found in Baltic Sea biota, where the toxic load owing to, for example, polychlorinated dibenzo-p-dioxins and other organic pollutants is already high. The levels and geographic pattern of PBDDs suggest biogenic rather than anthropogenic origin, and both biotic and abiotic formation pathways have been proposed. Photochemical formation from hydroxylated polybrominated diphenyl ethers (OH-PBDE) is a proposed pathway for PBDDs in marine environments. Ultraviolet radiation-initiated transformations of OH-BDEs 47, 68, 85, 90, 99, and 123, which all are abundant in the environment, were investigated. It was shown that the most abundant PBDDs in the environment (1,3,7-triBDD and 1,3,8-triBDD) can be formed from the most abundant OH-BDEs (OH-BDE 47 and OH-BDE 68) at high rates and with percentage yields. In fact, most of the PBDDs that have been identified in the Baltic Sea environment were formed with high yield from the six studied OH-PBDE, through initial cyclization and subsequent debromination reactions. The high formation yields point to this route as an important source of PBDDs in biota. However, congeners showing relatively high retention in fish, specifically 1,3,6,8- and 1,3,7,9-tetraBDD, were not formed. These are likely formed by enzymatic coupling of brominated phenols.

  9. Coumestan inhibits radical-induced oxidation of DNA: is hydroxyl a necessary functional group?

    PubMed

    Xi, Gao-Lei; Liu, Zai-Qun

    2014-06-18

    Coumestan is a natural tetracycle with a C═C bond shared by a coumarin moiety and a benzofuran moiety. In addition to the function of the hydroxyl group on the antioxidant activity of coumestan, it is worth exploring the influence of the oxygen-abundant scaffold on the antioxidant activity as well. In this work, seven coumestans containing electron-withdrawing and electron-donating groups were synthesized to evaluate the abilities to trap 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonate) cationic radical (ABTS(•+)), 2,2'-diphenyl-1-picrylhydrazyl radical (DPPH), and galvinoxyl radical, respectively, and to inhibit the oxidations of DNA mediated by (•)OH, Cu(2+)/glutathione (GSH), and 2,2'-azobis(2-amidinopropane hydrochloride) (AAPH), respectively. It was found that all of the coumestans used herein can quench the aforementioned radicals and can inhibit (•)OH-, Cu(2+)/GSH-, and AAPH-induced oxidations of DNA. In particular, substituent-free coumestan exhibits higher ability to quench DPPH and to inhibit AAPH-induced oxidation of DNA than Trolox. In addition, nonsubstituted coumestan shows a similar ability to inhibit (•)OH- and Cu(2+)/GSH-induced oxidations of DNA relative to that of Trolox. The antioxidant effectiveness of the coumestan can be attributed to the lactone in the coumarin moiety and, therefore, a hydroxyl group may not be a necessary functional group for coumestan to be an antioxidant.

  10. Coumarin-fused coumarin: antioxidant story from N,N-dimethylamino and hydroxyl groups.

    PubMed

    Xi, Gao-Lei; Liu, Zai-Qun

    2015-04-01

    Two coumarin skeletons can form chromeno[3,4-c]chromene-6,7-dione by sharing with the C ═ C in lactone. The aim of the present work was to explore the antioxidant effectiveness of the coumarin-fused coumarin via six synthetic compounds containing hydroxyl and N,N-dimethylamino as the functional groups. The abilities to quench 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonate) cationic radical (ABTS(+•)), 2,2'-diphenyl-1-picrylhydrazyl radical (DPPH), and galvinoxyl radical revealed that the rate constant for scavenging radicals was related to the amount of hydroxyl group in the scaffold of coumarin-fused coumarin. But coumarin-fused coumarin was able to inhibit DNA oxidations caused by (•)OH, Cu(2+)/glutathione (GSH), and 2,2'-azobis(2-amidinopropane hydrochloride) (AAPH) even in the absence of hydroxyl group. In particular, a hydroxyl and an N,N-dimethylamino group locating at different benzene rings increased the inhibitory effect of coumarin-fused coumarin on AAPH-induced oxidation of DNA about 3 times higher than a single hydroxyl group, whereas N,N-dimethylamino-substituted coumarin-fused coumarin possessed high activity toward (•)OH-induced oxidation of DNA without the hydroxyl group contained. Therefore, the hydroxyl group together with N,N-dimethylamino group may be a novel combination for the design of coumarin-fused heterocyclic antioxidants.

  11. Monitoring of hydroxyl groups in wood during heat treatment using NIR spectroscopy.

    PubMed

    Mitsui, Katsuya; Inagaki, Tetsuya; Tsuchikawa, Satoru

    2008-01-01

    This paper deals with the evaluation of thermally treated wood by near-infrared (NIR) spectroscopy. In the NIR second derivative spectrum, the absorption band at 6913 cm(-1) appeared with the procession of heat treatment, which conclusively assigned to the phenolic hydroxyl groups due to the lignin in comparison with the spectrum of acetylated spruce wood. As a result of the changes in the ratio of the areal integral calculated from spectral separation in the region of hydroxyl groups (7200-6100 cm(-1)) by the Gauss-Newton method, it was clear that the degradation of hydroxyl group in the cellulose started predominantly from the amorphous region and followed to semicrystalline and crystalline region. There was an obvious correlation between the weight decrement of wood and the decrement of hydroxyl groups in the cellulose by heat treatment.

  12. Reducing the conformational flexibility of carbohydrates: locking the 6-hydroxyl group by cyclopropanes.

    PubMed

    Brand, Christian; Granitzka, Markus; Stalke, Dietmar; Werz, Daniel B

    2011-10-14

    The 6-hydroxyl group of hexopyranosides was stereochemically locked by the spiroannelation of a cyclopropane unit at C-5. The corresponding glucose and mannose derivatives were prepared and their behaviour in glycosidation reactions was studied.

  13. The effect of hydroxyl group on the electronic structure of carbon nanotubes with different diameters

    NASA Astrophysics Data System (ADS)

    Kheirmand, M.

    2016-09-01

    A single hydroxyl group is functionalized on both sides of one ring of several carbon nanotubes (CNT) as CNT-OH. The electronic structure and chemical bonding parameters are studied with the help of quantum theory of atoms in molecules (QTAIM). Anionic states of the CNT-O as deprotonated hydroxyl are studied in order to get insight into the nature of CNT-OH species, considering frozen and relaxed geometries of CNT-O compounds. The results show a significant difference between inside or outside substituted hydroxyl groups; and also complicated behavior of the CNT's diameter, and it can be concluded that hydroxyl group can be used to tune the CNT's properties, effectively, in interesting application of these nanostructures.

  14. Diffusion of hydroxyl groups in silica glass through the binding interface

    NASA Astrophysics Data System (ADS)

    Sato, Naoya; Yamamoto, Takaki; Kuzuu, Nobu; Horikoshi, Hideharu; Niwa, Shohei

    2016-02-01

    Diffusion of hydroxyl groups in silica glass through an interface formed by binding between high-hydroxyl (ca. 1200 wt.ppm) and low-hydroxyl (ca. 130 wt.ppm)-containing silica glasses in the temperature range of 900-1150 °C was investigated. Although the theoretical curve with a hydroxyl-concentration-independent diffusion coefficient deviates from the experimental curve, the diffusion coefficients obtained by fitting to the experimental results by the least squares method coincided with the “effective diffusion coefficients” in the literature, which were obtained from the total absorption change in the IR absorption peak for the hydroxyl group using thin samples. By the analysis considering the hydroxyl concentration dependence of the diffusion coefficient, we showed that the diffusion coefficient is proportional to hydroxyl concentration at each temperature, which is consistent with the model of the diffusion: SiOSi + H2O = 2SiOH. On the basis of this scheme, we tried to evaluate the diffusion coefficients of molecular water using equilibrium constant in the literature.

  15. Role of allyl group in the hydroxyl and peroxyl radical scavenging activity of S-allylcysteine.

    PubMed

    Maldonado, Perla D; Alvarez-Idaboy, J Raúl; Aguilar-González, Adriana; Lira-Rocha, Alfonso; Jung-Cook, Helgi; Medina-Campos, Omar Noel; Pedraza-Chaverrí, José; Galano, Annia

    2011-11-17

    S-Allylcysteine (SAC) is the most abundant compound in aged garlic extracts, and its antioxidant properties have been demonstrated. It is known that SAC is able to scavenge different reactive species including hydroxyl radical (•OH), although its potential ability to scavenge peroxyl radical (ROO•) has not been explored. In this work the ability of SAC to scavenge ROO• was evaluated, as well as the role of the allyl group (-S-CH(2)-CH═CH(2)) in its free radical scavenging activity. Two derived compounds of SAC were prepared: S-benzylcysteine (SBC) and S-propylcysteine (SPC). Their abilities to scavenge •OH and ROO• were measured. A computational analysis was performed to elucidate the mechanism by which these compounds scavenge •OH and ROO•. SAC was able to scavenge •OH and ROO•, in a concentration-dependent way. Such activity was significantly ameliorated when the allyl group was replaced by benzyl or propyl groups. It was shown for the first time that SAC is able to scavenge ROO•.

  16. Use of molecular dynamics to assess the biophysiological role of hydroxyl groups in glycerol dyalkyl glycerol teraethers

    NASA Astrophysics Data System (ADS)

    Huguet, Carme; Costenaro, Lionel; Fietz, Susanne; Daura, Xavier

    2015-04-01

    The cell membrane of some Archaea is constituted by lipids that span the whole membrane width and contain two alkyl chains bound by two glycerol groups (glycerol dyalkyl glycerol teraethers or GDGTs). These lipids confer stability to the membrane in mesophile to extremophile environments. Besides the more frequently studied isoprenoid archaeal lipids, both mono- and dihydroxy-GDGTs (OH-GDGT) have been recently reported to occur in marine sediments (1). OH-GDGTs contain up to two cyclopentane moieties and have been identified in both core and intact forms. In 2013, a correlation between OH-GDGTs and temperature was reported, with higher relative OH-GDGT abundances at high latitudes (2,3). The physiological function of the hydroxyl group in a GDGT is not yet known, but given the field results, it could be linked to an adaptation of the membrane to changes in temperature. For hydroxydiether lipid cores in methanogenic bacteria, it has been postulated that the hydroxyl group may alter the cell membrane properties: either extending the polar head group region or creating a hydrophilic pocket (4). It has also been suggested that the hydroxylation of the biphytany (l) moiety may result in enhanced membrane rigidity (1). To improve our understanding of the effect of the hydroxylation on physical properties of membranes, we performed molecular-dynamics simulations of GDGT membranes presenting and lacking these additional OH groups. This is an approach with a great development potential in the archaea lipid field, especially in relation to proxy validation. Our results indicate that the addition of an OH increases the membrane fluidity, thus providing an advantage in cold environments. We also observe a widening of the polar head group area, which could enhance transport. 1. Liu et al. 2012, GCA 2. Huguet et al. 2013, Org. Geochem 3. Fietz et al. 2013 4. Sprott et al. 1990. J. Biol. Chem. 265, 13735-13740.

  17. Tuning magnetic splitting of zigzag graphene nanoribbons by edge functionalization with hydroxyl groups

    SciTech Connect

    Zhang, Huizhen; Yang, Haifang; Li, Lin; Fu, Huixia; Ma, Wei; Niu, Chunyao; Sun, Jiatao; Meng, Sheng; Gu, Changzhi

    2015-03-21

    The electronic properties and relative stability of zigzag graphene nanoribbons are studied by varying the percentage of hydroxyl radicals for edge saturation using first principle calculations. The passivated structures of zigzag graphene nanoribbon have spin-polarized ground state with antiferromagnetic exchange coupling across the edge and ferromagnetic coupling along the edges. When the edges are specially passivated by hydroxyl, the potentials of spin exchange interaction across the two edges shift accordingly, resulting into a spin-semiconductor. Varying the concentration of hydroxyl groups can alter the maximum magnetization splitting. When the percentage of asymmetrically adsorbed hydroxyl reaches 50%, the magnetization splitting can reach a value as high as 275 meV due to the asymmetrical potential across the nanoribbon edges. These results would favor spintronic device applications based on zigzag graphene nanoribbons.

  18. Chemical modification and structure-activity relationships of pyripyropenes. 1. Modification at the four hydroxyl groups.

    PubMed

    Obata, R; Sunazuka, T; Li, Z; Tian, Z; Harigaya, Y; Tabata, N; Tomoda, H; Omura, S

    1996-11-01

    Four hydroxyl groups of pyripyropenes have been modified and evaluated for their ability to inhibit microsomal acyl-CoA:cholesterol acyltransferase (ACAT) activity in vitro and to lower cholesterol absorption in vivo in a cholesterol-fed hamster. 7-O-n-Valeryl derivative (8c) improved the in vitro ACAT inhibitory activity (IC50 = 13 nM) about 7 times better than pyripyropene A. Introduction of methanesulfonyl group at 11-hydroxyl group (17a) increased both in vitro activity (IC50 = 19 nM) and in vivo efficacy (ED50 = 10 mg/kg). PMID:8982343

  19. Entropy Loss of Hydroxyl Groups of Balanol upon Binding to Protein Kinase A

    NASA Astrophysics Data System (ADS)

    Gidofalvi, Gergely; Wong, Chung F.; McCammon, J. Andrew

    2002-09-01

    This article describes a short project for an undergraduate to learn several techniques for computer-aided drug design. The project involves estimating the loss of the rotational entropy of the hydroxyl groups of balanol upon its binding to the enzyme protein kinase A (PKA), as the entropy loss can significantly influence PKA balanol binding affinity. This work employs semiempirical quantum mechanical techniques for estimating the potential energy curves for the rotation of the hydroxyl groups of balanol in vacuum and in PKA, and solves the Poisson equation to correct the potential energy curves for hydration effects. Statistical mechanical principles are then applied to estimate the desired entropy loss from the potential energy curves. The analysis examines the influence of hydration effects on the rotational preference of the hydroxyl groups and the significance of the rotational entropy in determining binding affinity.

  20. Alkyne Ligation Handles: Propargylation of Hydroxyl, Sulfhydryl, Amino, and Carboxyl Groups via the Nicholas Reaction.

    PubMed

    Wells, Sarah M; Widen, John C; Harki, Daniel A; Brummond, Kay M

    2016-09-16

    The Nicholas reaction has been applied to the installation of alkyne ligation handles. Acid-promoted propargylation of hydroxyl, sulfhydryl, amino, and carboxyl groups using dicobalt hexacarbonyl-stabilized propargylium ions is reported. This method is useful for introduction of propargyl groups into base-sensitive molecules, thereby expanding the toolbox of methods for the incorporation of alkynes for bio-orthogonal reactions. High-value molecules are used as the limiting reagent, and various propargylium ion precursors are compared. PMID:27570975

  1. Organocatalytic chemo- and regioselective oxyarylation of styrenes via a cascade reaction: remote activation of hydroxyl groups.

    PubMed

    Zhang, Yu-Chen; Jiang, Fei; Wang, Shu-Liang; Shi, Feng; Tu, Shu-Jiang

    2014-07-01

    The first organocatalytic oxyarylation of styrenes has been established through a cascade of vinylogous Michael addition/alkoxyl transfer reactions of o- or p-hydroxylstyrenes with quinone imine ketals. The process leads to a highly chemo- and regioselective oxyarylation of styrenes and provides access to m-alkylated anilines in generally high yields and excellent diastereoselectivity (up to 99% yield, >95:5 dr). An investigation of the reaction pathway revealed that the existence and position of the hydroxyl group of styrene played crucial roles in the cascade reaction, suggesting that the two reactants were simultaneously activated by binaphthyl-derived phosphoric acid via hydrogen bonding interactions and long-distance conjugative effects. In addition, the activating group of the hydroxyl functionality in the products can be easily removed or transformed, demonstrating the applicability and utility of this strategy in styrene oxyarylation and in the synthesis of styrene-based compounds.

  2. Interaction of hydrogen with ZnO nanopowders--evidence of hydroxyl group formation.

    PubMed

    Wong, Kester W J; Field, Matthew R; Ou, Jian Zhen; Latham, Kay; Spencer, Michelle J S; Yarovsky, Irene; Kalantar-zadeh, Kourosh

    2012-01-13

    There have been many investigations to reveal the nature of the hydrogen gas and ZnO nanopowder interaction at elevated temperatures, while at present no conclusive description of such an interaction has been confidently reported. In this work, we demonstrate that a hydroxyl group is formed during this interaction, depending on size and relative crystallinity of nanopowders. Our in situ Raman spectroscopy investigations show that the interaction directly affects the intensity of the Raman signal at 483 cm(-1), relative to the peak at 519 cm(-1). Ex situ x-ray diffraction (XRD) and infrared spectroscopy also show extra peaks at 44° and 1618 cm(-1), respectively, after hydrogenation. These peaks were all identified as surface hydroxyl groups, which can be related to the formation of water on the ZnO nanopowder surfaces.

  3. Biosynthesis of polyhydroxyalkanoates containing hydroxyl group from glycolate in Escherichia coli.

    PubMed

    Insomphun, Chayatip; Kobayashi, Shingo; Fujiki, Tetsuya; Numata, Keiji

    2016-12-01

    Polyhydroxyalkanoates (PHAs) containing hydroxyl groups in a side chain were produced in recombinant Escherichia coli JM109 using glycolate as the sole carbon source. The propionate-CoA transferase (pct) gene from Megasphaera elsdenii and the β-ketothiolase (bktB) gene and phaCAB operon from Ralstonia eutropha H16 were introduced into E. coli JM109. A novel monomer containing a hydroxyl group, dihydroxybutyrate (DHBA), was the expected product of the condensation of glycolyl-CoA and acetyl-CoA by BktB. The recombinant strain produced a PHA containing 1 mol% DHBA. The incorporation of DHBA may have been restricted because the expression of phaAB1 competes for acetyl-CoA. The PHA containing DHBA units were evaluated regarding thermal properties, such as melting temperature, glass transition temperature and thermal degradation temperature. The current study demonstrates a potential use of PHA containing hydroxyl groups as renewable resources in biological materials. PMID:27075993

  4. The Juxtaposition of Ribose Hydroxyl Groups: The Root of Biological Catalysis and the RNA World?

    NASA Astrophysics Data System (ADS)

    Bernhardt, Harold S.

    2015-06-01

    We normally think of enzymes as being proteins; however, the RNA world hypothesis suggests that the earliest biological catalysts may have been composed of RNA. One of the oldest surviving RNA enzymes we are aware of is the peptidyl transferase centre (PTC) of the large ribosomal RNA, which joins amino acids together to form proteins. Recent evidence indicates that the enzymatic activity of the PTC is principally due to ribose 2 '-OHs. Many other reactions catalyzed by RNA and/or in which RNA is a substrate similarly utilize ribose 2 '-OHs, including phosphoryl transfer reactions that involve the cleavage and/or ligation of the ribose-phosphate backbone. It has recently been proposed by Yakhnin (2013) that phosphoryl transfer reactions were important in the prebiotic chemical evolution of RNA, by enabling macromolecules composed of polyols joined by phosphodiester linkages to undergo recombination reactions, with the reaction energy supplied by the phosphodiester bond itself. The almost unique juxtaposition of the ribose 2'-hydroxyl and 3'-oxygen in ribose-containing polymers such as RNA, which gives ribose the ability to catalyze such reactions, may have been an important factor in the selection of ribose as a component of the first biopolymer. In addition, the juxtaposition of hydroxyl groups in free ribose: (i) allows coordination of borate ions, which could have provided significant and preferential stabilization of ribose in a prebiotic environment; and (ii) enhances the rate of permeation by ribose into a variety of lipid membrane systems, possibly favouring its incorporation into early metabolic pathways and an ancestral ribose-phosphate polymer. Somewhat more speculatively, hydrogen bonds formed by juxtaposed ribose hydroxyl groups may have stabilized an ancestral ribose-phosphate polymer against degradation (Bernhardt and Sandwick 2014). I propose that the almost unique juxtaposition of ribose hydroxyl groups constitutes the root of both biological

  5. Facile fabrication of novel cyclomatrix-type polyphosphazene nanotubes with active hydroxyl groups via an in situ template approach

    NASA Astrophysics Data System (ADS)

    Fu, Jianwei; Huang, Xiaobin; Zhu, Yan; Huang, Yawen; Tang, Xiaozhen

    2009-02-01

    Novel polyphosphazene nanotubes with active hydroxyl groups were fabricated via an in situ template approach under ultrasonic irradiation. SEM and TEM results indicated that the nanotubes were uniform with length of several micrometers, inner diameter of ca. 20 nm and outer diameter of 60-80 nm. FTIR spectra revealed that the content of the hydroxyl groups on the nanotube surface was dependent on the feed ratio of hexachlorocyclotriphosphazene (HCCP) to 4,4'-sulfonyldiphenol. The successful esterification of polymer nanotubes with benzoxy chloride demonstrated the high reactivity of the hydroxyl groups. The method employed here might provide a simple and effective way to prepare functional nanotubes used for biological applications.

  6. The 4'-hydroxyl group of resveratrol is functionally important for direct activation of PPARα.

    PubMed

    Takizawa, Yoshie; Nakata, Rieko; Fukuhara, Kiyoshi; Yamashita, Hiroshi; Kubodera, Hideo; Inoue, Hiroyasu

    2015-01-01

    Long-term moderate consumption of red wine is associated with a reduced risk of developing lifestyle-related diseases such as cardiovascular disease and cancer. Therefore, resveratrol, a constituent of grapes and various other plants, has attracted substantial interest. This study focused on one molecular target of resveratrol, the peroxisome proliferator activated receptor α (PPARα). Our previous study in mice showed that resveratrol-mediated protection of the brain against stroke requires activation of PPARα; however, the molecular mechanisms involved in this process remain unknown. Here, we evaluated the chemical basis of the resveratrol-mediated activation of PPARα by performing a docking mode simulation and examining the structure-activity relationships of various polyphenols. The results of experiments using the crystal structure of the PPARα ligand-binding domain and an analysis of the activation of PPARα by a resveratrol analog 4-phenylazophenol (4-PAP) in vivo indicate that the 4'-hydroxyl group of resveratrol is critical for the direct activation of PPARα. Activation of PPARα by 5 μM resveratrol was enhanced by rolipram, an inhibitor of phosphodiesterase (PDE) and forskolin, an activator of adenylate cyclase. We also found that resveratrol has a higher PDE inhibitory activity (IC50 = 19 μM) than resveratrol analogs trans-4-hydroxystilbene and 4-PAP (IC50 = 27-28 μM), both of which has only 4'-hydroxyl group, indicating that this 4'-hydroxyl group of resveratrol is not sufficient for the inhibition of PDE. This result is consistent with that 10 μM resveratrol has a higher agonistic activity of PPARα than these analogs, suggesting that there is a feedforward activation loop of PPARα by resveratrol, which may be involved in the long-term effects of resveratrol in vivo. PMID:25798826

  7. Zn(OTf)2-promoted chemoselective esterification of hydroxyl group bearing carboxylic acids.

    PubMed

    Mamidi, Narsimha; Manna, Debasis

    2013-03-15

    Selective esterification of aliphatic and aromatic carboxylic acids with various alcohols is studied using triphenylphosphine, I2, and a catalytic amount of Zn(OTf)2. Use of this catalyst allows the formation of esters at a faster rate with good to excellent yield by activating the in situ generated acyloxyphosphonium ion intermediate. During the esterification process, both their aromatic and aliphatic hydroxyl groups are fully preserved from transesterification. The results show that the bulkiness and the reactivity of this doubly activated intermediate III control the selectivity and the rate of the reaction, respectively. The method is also useful for direct amidation reactions.

  8. A functionalizable polyester with free hydroxyl groups and tunable physiochemical and biological properties

    PubMed Central

    You, Zhengwei; Cao, Haiping; Gao, Jin; Shin, Paul H.; Day, Billy W.; Wang, Yadong

    2010-01-01

    Polyesters with free functional groups allow facile modifications with biomolecules, which can lead to versatile biomaterials that afford controlled interactions with cells and tissues. Efficient synthesis of functionalizable polyesters is still a challenge that greatly limits the availability and widespread applications of biofunctionalized synthetic polymers. Here we report a simple route to prepare a functionalizable polyester, poly(sebacoyl diglyceride) (PSeD) bearing free hydroxyl groups. The key synthetic step is an epoxide ring-opening polymerization, instead of the traditional polycondensation, that produces poly(glycerol sebacate) (PGS) [1]. PSeD has a more defined structure with mostly linear backbone, more free hydroxyl groups, higher molecular weight, and lower polydispersity than PGS. Crosslinking PSeD with sebacic acid yields a polymer five times tougher and more elastic than cured PGS. PSeD exhibits good cytocompatibility in vitro. Furthermore, functionalization by glycine proceeds with high efficiency. This versatile synthetic platform can offer a large family of biodegradable, functionalized polymers with tunable physiochemical and biological properties useful for a wide range of biomedical applications. PMID:20149441

  9. Chemical abundances of massive stars in Local Group galaxies

    NASA Astrophysics Data System (ADS)

    Venn, Kim A.; Kaufer, Andreas; Tolstoy, Eline; Kudritzki, Rolf-Peter; Przybilla, Norbert; Smartt, Stephen J.; Lennon, Daniel J.

    The relative abundances of elements in galaxies can provide valuable information on the stellar and chemical evolution of a galaxy. While nebulae can provide abundances for a variety of light elements, stars are the only way to directly determine the abundances of iron-group and s-process and r-process elements in a galaxy. The new 8m and 10m class telescopes and high-efficiency spectrographs now make high-quality spectral observations of bright supergiants possible in dwarf galaxies in the Local Group. We have been concentrating on elemental abundances in the metal-poor dwarf irregular galaxies, NGC 6822, WLM, Sextants A, and GR 8. Comparing abundance ratios to those predicted from their star formation histories, determined from color-magnitude diagrams, and comparing those ratios between these galaxies can give us new insights into the evolution of these dwarf irregular galaxies. Iron-group abundances also allow us to examine the metallicities of the stars in these galaxies directly, which affects their inferred mass loss rates and predicted stellar evolution properties.

  10. Inhibition of Pseudomonas aeruginosa Swarming Motility by 1-Naphthol and Other Bicyclic Compounds Bearing Hydroxyl Groups

    PubMed Central

    Oura, Hiromu; Tashiro, Yosuke; Toyofuku, Masanori; Ueda, Kousetsu; Kiyokawa, Tatsunori; Ito, Satoshi; Takahashi, Yurika; Lee, Seunguk; Nojiri, Hideaki; Nakajima-Kambe, Toshiaki; Uchiyama, Hiroo; Futamata, Hiroyuki

    2015-01-01

    Many bacteria convert bicyclic compounds, such as indole and naphthalene, to oxidized compounds, including hydroxyindoles and naphthols. Pseudomonas aeruginosa, a ubiquitous bacterium that inhabits diverse environments, shows pathogenicity against animals, plants, and other microorganisms, and increasing evidence has shown that several bicyclic compounds alter the virulence-related phenotypes of P. aeruginosa. Here, we revealed that hydroxyindoles (4- and 5-hydroxyindoles) and naphthalene derivatives bearing hydroxyl groups specifically inhibit swarming motility but have minor effects on other motilities, including swimming and twitching, in P. aeruginosa. Further analyses using 1-naphthol showed that this effect is also associated with clinically isolated hyperswarming P. aeruginosa cells. Swarming motility is associated with the dispersion of cells from biofilms, and the addition of 1-naphthol maintained biofilm biomass without cell dispersion. We showed that this 1-naphthol-dependent swarming inhibition is independent of changes of rhamnolipid production and the intracellular level of signaling molecule cyclic-di-GMP (c-di-GMP). Transcriptome analyses revealed that 1-naphthol increases gene expression associated with multidrug efflux and represses gene expression associated with aerotaxis and with pyochelin, flagellar, and pilus synthesis. In the present study, we showed that several bicyclic compounds bearing hydroxyl groups inhibit the swarming motility of P. aeruginosa, and these results provide new insight into the chemical structures that inhibit the specific phenotypes of P. aeruginosa. PMID:25681177

  11. Substrate specificity of small-intestinal lactase. Assessment of the role of the substrate hydroxyl groups.

    PubMed

    Rivera-Sagredo, A; Cañada, F J; Nieto, O; Jimenez-Barbero, J; Martín-Lomas, M

    1992-10-01

    Lactase-phlorizin hydrolase is a disaccharidase present in the small intestine of mammals. This enzyme has two active sites, one being responsible for the hydrolysis of lactose. Lactase activity is thought to be selective towards glycosides with a hydrophilic aglycon. In this work, we report a systematic study on the importance of each hydroxyl group in the substrate molecule for lactase activity. For this purpose, all of the monodeoxy derivatives of methyl beta-lactoside and other lactose analogues are studied as lactase substrates. With respect to the galactose moiety, it is shown here that HO-3' and HO-2' are necessary for hydrolysis of the substrates by lactase. Using these chemically modified substrates, it has been confirmed that lactase does not behave as a typical beta-galactosidase, since it does not show an absolute selectivity with respect to substitution and stereochemistry at C4' in the galactose moiety of the substrate. However, the glucose moiety, in particular the HO-6, appears to be important for substrate hydrolysis, although none of the hydroxyl groups seemed to be essential. In order to differentiate both activities of the enzyme, a new assay for the phlorizin-hydrolase activity has also been developed.

  12. Inhibition of Pseudomonas aeruginosa swarming motility by 1-naphthol and other bicyclic compounds bearing hydroxyl groups.

    PubMed

    Oura, Hiromu; Tashiro, Yosuke; Toyofuku, Masanori; Ueda, Kousetsu; Kiyokawa, Tatsunori; Ito, Satoshi; Takahashi, Yurika; Lee, Seunguk; Nojiri, Hideaki; Nakajima-Kambe, Toshiaki; Uchiyama, Hiroo; Futamata, Hiroyuki; Nomura, Nobuhiko

    2015-04-01

    Many bacteria convert bicyclic compounds, such as indole and naphthalene, to oxidized compounds, including hydroxyindoles and naphthols. Pseudomonas aeruginosa, a ubiquitous bacterium that inhabits diverse environments, shows pathogenicity against animals, plants, and other microorganisms, and increasing evidence has shown that several bicyclic compounds alter the virulence-related phenotypes of P. aeruginosa. Here, we revealed that hydroxyindoles (4- and 5-hydroxyindoles) and naphthalene derivatives bearing hydroxyl groups specifically inhibit swarming motility but have minor effects on other motilities, including swimming and twitching, in P. aeruginosa. Further analyses using 1-naphthol showed that this effect is also associated with clinically isolated hyperswarming P. aeruginosa cells. Swarming motility is associated with the dispersion of cells from biofilms, and the addition of 1-naphthol maintained biofilm biomass without cell dispersion. We showed that this 1-naphthol-dependent swarming inhibition is independent of changes of rhamnolipid production and the intracellular level of signaling molecule cyclic-di-GMP (c-di-GMP). Transcriptome analyses revealed that 1-naphthol increases gene expression associated with multidrug efflux and represses gene expression associated with aerotaxis and with pyochelin, flagellar, and pilus synthesis. In the present study, we showed that several bicyclic compounds bearing hydroxyl groups inhibit the swarming motility of P. aeruginosa, and these results provide new insight into the chemical structures that inhibit the specific phenotypes of P. aeruginosa. PMID:25681177

  13. Hydration of hydroxyl and amino groups examined by molecular dynamics and neutron scattering.

    PubMed

    Hladílková, Jana; Fischer, Henry E; Jungwirth, Pavel; Mason, Philip E

    2015-05-28

    Neutron diffraction with isotopic substitution was performed on aqueous solutions of isopropyl alcohol and isopropylamine. The difference between these two measurements primarily contains information about the different hydration of the alcohol and amino group. This data is used as a test of the accuracy of molecular dynamic simulations of the same systems. Having established the level of accuracy of the modeling, it is employed as an interpretive tool for the experimental data. Even though the alcohol and the amine possess comparable hydrogen bonding capabilities, consisting respectively of either two hydrogen bond acceptors and one donor, or two hydrogen bond donors and one acceptor, we find significant differences in the hydration of the hydroxyl and amino groups.

  14. Water growth on metals and oxides: binding, dissociation and role of hydroxyl groups

    SciTech Connect

    Salmeron, M.; Bluhm, H.; Tatarkhanov, M.; Ketteler, G.; Shimizu, T.K.; Mugarza, A.; Deng, Xingyi; Herranz, T.; Yamamoto, S.; Nilsson, A.

    2008-09-01

    The authors discuss the role of the presence of dangling H bonds from water or from surface hydroxyl species on the wetting behavior of surfaces. Using Scanning Tunneling and Atomic Force Microscopies, and Photoelectron Spectroscopy, they have examined a variety of surfaces, including mica, oxides, and pure metals. They find that in all cases, the availability of free, dangling H-bonds at the surface is crucial for the subsequent growth of wetting water films. In the case of mica electrostatic forces and H-bonding to surface O atoms determine the water orientation in the first layer and also in subsequent layers with a strong influence in its wetting characteristics. In the case of oxides like TiO{sub 2}, Cu{sub 2}O, SiO{sub 2} and Al{sub 2}O{sub 3}, surface hydroxyls form readily on defects upon exposure to water vapor and help nucleate the subsequent growth of molecular water films. On pure metals, such as Pt, Pd, and Ru, the structure of the first water layer and whether or not it exhibits dangling H bonds is again crucial. Dangling H-bonds are provided by molecules with their plane oriented vertically, or by OH groups formed by the partial dissociation of water. By tying the two II atoms of the water molecules into strong H-bonds with pre-adsorbed O on Ru can also quench the wettability of the surface.

  15. IDENTIFICATION AND QUANTIFICATION OF AEROSOL POLAR OXYGENATED COMPOUNDS BEARING CARBOXYLIC AND/OR HYDROXYL GROUPS. 1. METHOD DEVELOPMENT

    EPA Science Inventory

    In this study, a new analytical technique was developed for the identification and quantification of multi-functional compounds containing simultaneously at least one hydroxyl or one carboxylic group, or both. This technique is based on derivatizing first the carboxylic group(s) ...

  16. Comparing Amino Acid Abundances and Distributions Across Carbonaceous Chondrite Groups

    NASA Technical Reports Server (NTRS)

    Burton, Aaron S.; Callahan, Michael P.; Glavin, Daniel P.; Elsila, Jamie E.; Dworkin, Jason P.

    2012-01-01

    Meteorites are grouped according to bulk properties such as chemical composition and mineralogy. These parameters can vary significantly among the different carbonaceous chondrite groups (CI, CM, CO, CR, CH, CB, CV and CK). We have determined the amino acid abundances of more than 30 primary amino acids in meteorites from each of the eight groups, revealing several interesting trends. There are noticeable differences in the structural diversity and overall abundances of amino acids between meteorites from the different chondrite groups. Because meteorites may have been an important source of amino acids to the prebiotic Earth and these organic compounds are essential for life as we know it, the observed variations of these molecules may have been important for the origins of life.

  17. Facile synthesis and characterization of novel biodegradable amphiphilic block copolymers bearing pendant hydroxyl groups.

    PubMed

    Hu, Gaicen; Fan, Xiaoshan; Xu, Bingcan; Zhang, Delong; Hu, Zhiguo

    2014-10-01

    Novel amphiphilic block copolymers bearing pendant hydroxyl groups polylactide-b-poly(3,3-bis(Hydroxymethyl-triazolylmethyl) oxetane)-b-polylactide (PLA-b-PHMTYO-b-PLA) were synthesized via a facile and efficient method. First, the block copolymer intermediates polylactide-b-poly(3,3-Diazidomethyloxetane)-b-polylactide (PLA-b-PBAMO-b-PLA) were synthesized through ring-opening polymerization of lactide using PBAMO as a macroinitiator. Following "Click" reaction of PLA-b-PBAMO-b-PLA with propargyl alcohol provided the targeted amphiphilic block copolymers PLA-b-PHMTYO-b-PLA with pendant hydroxyl groups. The composition and structure of prepared copolymers were characterized by (1)H nuclear magnetic resonance ((1)H NMR) spectroscopy, Fourier transform infrared (FT-IR) and gel permeation chromatography (GPC). The self-assembly behavior of the copolymers in water was investigated by transmission electron microscope (TEM), dynamic light scattering (DLS) and static light scattering (SLS). The results showed that the novel copolymers PLA-b-PHMTYO-b-PLA self-assembled into spherical micelles with diameters ranging from 100 nm to 200 nm in aqueous solution. These copolymers also exhibited low critical micellar concentrations (CMC: 6.9 × 10(-4)mg/mL and 3.9 × 10(-5)mg/mL, respectively). In addition, the in vitro cytotoxicity of these copolymers was determined in the presence of L929 cells. The results showed that the block copolymers PLA-b-PHMTYO-b-PLA exhibited better biocompatibility. Therefore, these well-defined copolymers are expected to find some applications in drug delivery or tissue engineering. PMID:25175206

  18. Facile synthesis and characterization of novel biodegradable amphiphilic block copolymers bearing pendant hydroxyl groups.

    PubMed

    Hu, Gaicen; Fan, Xiaoshan; Xu, Bingcan; Zhang, Delong; Hu, Zhiguo

    2014-10-01

    Novel amphiphilic block copolymers bearing pendant hydroxyl groups polylactide-b-poly(3,3-bis(Hydroxymethyl-triazolylmethyl) oxetane)-b-polylactide (PLA-b-PHMTYO-b-PLA) were synthesized via a facile and efficient method. First, the block copolymer intermediates polylactide-b-poly(3,3-Diazidomethyloxetane)-b-polylactide (PLA-b-PBAMO-b-PLA) were synthesized through ring-opening polymerization of lactide using PBAMO as a macroinitiator. Following "Click" reaction of PLA-b-PBAMO-b-PLA with propargyl alcohol provided the targeted amphiphilic block copolymers PLA-b-PHMTYO-b-PLA with pendant hydroxyl groups. The composition and structure of prepared copolymers were characterized by (1)H nuclear magnetic resonance ((1)H NMR) spectroscopy, Fourier transform infrared (FT-IR) and gel permeation chromatography (GPC). The self-assembly behavior of the copolymers in water was investigated by transmission electron microscope (TEM), dynamic light scattering (DLS) and static light scattering (SLS). The results showed that the novel copolymers PLA-b-PHMTYO-b-PLA self-assembled into spherical micelles with diameters ranging from 100 nm to 200 nm in aqueous solution. These copolymers also exhibited low critical micellar concentrations (CMC: 6.9 × 10(-4)mg/mL and 3.9 × 10(-5)mg/mL, respectively). In addition, the in vitro cytotoxicity of these copolymers was determined in the presence of L929 cells. The results showed that the block copolymers PLA-b-PHMTYO-b-PLA exhibited better biocompatibility. Therefore, these well-defined copolymers are expected to find some applications in drug delivery or tissue engineering.

  19. Photoremovable hydroxyl group protection. Use of the p-tolylsulfonyl protecting group in. beta. -disaccharide synthesis

    SciTech Connect

    Binkley, R.W.; Koholic, D.J. )

    1989-07-21

    The p-tolylsulfonyl group has been shown to a photoremovable group effective for protection of carbohydrates during disaccharide synthesis. The formation of the versatile, p-tolylsulfonyl-protected disaccharide 13 (methyl 3-O-(4-O-benzoyl-3-O-benzyl-2,6-dideoxy-{beta}-D-arabino-hexopyranosyl)-2,6-dideoxy-4-O-(p-tolylsulfonyl)-{alpha}-D-arabino-hexopyranoside) was accomplished by silver silicate catalyzed coupling of methyl 2,6-dideoxy-4-O-(p-tolylsulfonyl)-{alpha}-D-arabino-hexopyranoside (7) with 4-O-benzyl-2,6-dideoxy-{alpha}-D-arabino-hexopyranosyl bromide (8). Each of the three protecting groups (benzyl, benzoyl, and p-tolylsulfonyl) present in 13 was removed regioselectively under nonacidic conditions.

  20. Lead and uranium group abundances in cosmic rays

    NASA Technical Reports Server (NTRS)

    Yadav, J. S.; Perelygin, V. P.

    1985-01-01

    The importance of Lead and Uranium group abundances in cosmic rays is discussed in understanding their evolution and propagation. The electronic detectors can provide good charge resolution but poor data statistics. The plastic detectors can provide somewhat better statistics but charge resolution deteriorates. The extraterrestrial crystals can provide good statistics but with poor charge resolution. Recent studies of extraterrestrial crystals regarding their calibration to accelerated uranium ion beam and track etch kinetics are discussed. It is hoped that a charge resolution of two charge units can be achieved provided an additional parameter is taken into account. The prospects to study abundances of Lead group, Uranium group and superheavy element in extraterrestrial crystals are discussed, and usefulness of these studies in the light of studies with electronic and plastic detectors is assessed.

  1. Conformational influence of the ribose 2'-hydroxyl group: crystal structures of DNA-RNA chimeric duplexes

    NASA Technical Reports Server (NTRS)

    Egli, M.; Usman, N.; Rich, A.

    1993-01-01

    We have crystallized three double-helical DNA-RNA chimeric duplexes and determined their structures by X-ray crystallography at resolutions between 2 and 2.25 A. The two self-complementary duplexes [r(G)d(CGTATACGC)]2 and [d(GCGT)r(A)d(TACGC)]2, as well as the Okazaki fragment d(GGGTATACGC).r(GCG)d(TATACCC), were found to adopt A-type conformations. The crystal structures are non-isomorphous, and the crystallographic environments for the three chimeras are different. A number of intramolecular interactions of the ribose 2'-hydroxyl groups contribute to the stabilization of the A-conformation. Hydrogen bonds between 2'-hydroxyls and 5'-oxygens or phosphate oxygens, in addition to the previously observed hydrogen bonds to 1'-oxygens of adjacent riboses and deoxyriboses, are observed in the DNA-RNA chimeric duplexes. The crystalline chimeric duplexes do not show a transition between the DNA A- and B-conformations. CD spectra suggest that the Okazaki fragment assumes an A-conformation in solution as well. In this molecule the three RNA residues may therefore lock the complete decamer in the A-conformation. Crystals of an all-DNA strand with the same sequence as the self-complementary chimeras show a morphology which is different from those of the chimera crystals. Moreover, the oligonucleotide does not match any of the sequence characteristics of DNAs usually adopting the A-conformation in the crystalline state (e.g., octamers with short alternating stretches of purines and pyrimidines). In DNA-RNA chimeric duplexes, it is therefore possible that a single RNA residue can drive the conformational equilibrium toward the A-conformation.

  2. SPECTROSCOPIC ABUNDANCES AND MEMBERSHIP IN THE WOLF 630 MOVING GROUP

    SciTech Connect

    Bubar, Eric J.; King, Jeremy R. E-mail: jking2@ces.clemson.ed

    2010-08-15

    The concept of kinematic assemblages evolving from dispersed stellar clusters has remained contentious since Eggen's initial formulation of moving groups in the 1960s. With high-quality parallaxes from the Hipparcos space astrometry mission, distance measurements for thousands of nearby, seemingly isolated stars are currently available. With these distances, a high-resolution spectroscopic abundance analysis can be brought to bear on the alleged members of these moving groups. If a structure is a relic of an open cluster, the members can be expected to be monolithic in age and abundance in as much as homogeneity is observed in young open clusters. In this work, we have examined 34 putative members of the proposed Wolf 630 moving group using high-resolution stellar spectroscopy. The stars of the sample have been chemically tagged to determine abundance homogeneity and confirm the existence of a homogeneous subsample of 19 stars. Fitting the homogeneous subsample with Yale-Yonsei isochrones yields a single evolutionary sequence of {approx}2.7 {+-} 0.5 Gyr. It is concluded that this 19 star subsample of the Wolf 630 moving group sample of 34 stars could represent a dispersed cluster with an ([Fe/H]) = -0.01 {+-} 0.02 and an age of 2.7 {+-} 0.5 Gyr. In addition, chemical abundances of Na and Al in giants are examined for indications of enhancements as observed in field giants of old open clusters; overexcitation/ionization effects are explored in the cooler dwarfs of the sample; and oxygen is derived from the infrared triplet and the forbidden line at {lambda}6300.

  3. Photoluminescence of oxygen vacancies and hydroxyl group surface functionalized SnO2 nanoparticles.

    PubMed

    Bonu, Venkataramana; Das, Arindam; Amirthapandian, S; Dhara, Sandip; Tyagi, Ashok Kumar

    2015-04-21

    We report, for the first time, the luminescence property of the hydroxyl group surface functionalized quantum dots (QDs) and nanoparticles (NPs) of SnO2 using low energy excitations of 2.54 eV (488 nm) and 2.42 eV (514.5 nm). This luminescence is in addition to generally observed luminescence from 'O' defects. The as-prepared SnO2 QDs are annealed at different temperatures under ambient conditions to create NPs with varying sizes. Subsequently, the average size of the NPs is calculated from the acoustic vibrations observed at low frequencies in the Raman spectra and by the transmission electron microscopy measurements. Detailed photoluminescence studies with 3.815 eV (325 nm) excitation reveal the nature of in-plane and bridging 'O' vacancies as well as adsorption and desorption occurring at different annealing temperatures. X-ray photoelectron spectroscopy studies also support this observation. The defect level related to the surface -OH functional groups shows a broad luminescence peak at around 1.96 eV in SnO2 NPs which is elaborated using temperature dependent studies. PMID:25774472

  4. Curable liquid hydrocarbon prepolymers containing hydroxyl groups and process for producing same

    NASA Technical Reports Server (NTRS)

    Rhein, R. A.; Ingham, J. D. (Inventor)

    1978-01-01

    Production of hydroxyl containing curable liquid hydrocarbon prepolymers by ozonizing a high molecular weight saturated hydrocarbon polymer such as polyisobutylene or ethylene propylene rubber is discussed. The ozonized material is reduced using reducing agents, preferably diisobutyl aluminum hydride, to form the hydroxyl containing liquid prepolymers having a substantially lower molecular weight than the parent polymer. The resulting curable liquid hydroxyl containing prepolymers can be poured into a mold and readily cured, with reactants such as toluene diisocyanate, to produce highly stable elastomers having a variety of uses such as binders for solid propellants.

  5. Development of a group contribution method to predict aqueous phase hydroxyl radical (HO*) reaction rate constants.

    PubMed

    Minakata, Daisuke; Li, Ke; Westerhoff, Paul; Crittenden, John

    2009-08-15

    The hydroxyl radical (HO*) is a strong oxidant that reacts with electron-rich sites of organic compounds and initiates complex chain mechanisms. In order to help understand the reaction mechanisms, a rule-based model was previously developed to predict the reaction pathways. For a kinetic model, there is a need to develop a rate constant estimator that predicts the rate constants for a variety of organic compounds. In this study, a group contribution method (GCM) is developed to predict the aqueous phase HO* rate constants for the following reaction mechanisms: (1) H-atom abstraction, (2) HO* addition to alkenes, (3) HO* addition to aromatic compounds, and (4) HO* interaction with sulfur (S)-, nitrogen (N)-, or phosphorus (P)-atom-containing compounds. The GCM hypothesizes that an observed experimental rate constant for a given organic compound is the combined rate of all elementary reactions involving HO*, which can be estimated using the Arrhenius activation energy, E(a), and temperature. Each E(a) for those elementary reactions can be comprised of two parts: (1) a base part that includes a reactive bond in each reaction mechanism and (2) contributions from its neighboring functional groups. The GCM includes 66 group rate constants and 80 group contribution factors, which characterize each HO* reaction mechanism with steric effects of the chemical structure groups and impacts of the neighboring functional groups, respectively. Literature-reported experimental HO* rate constants for 310 and 124 compounds were used for calibration and prediction, respectively. The genetic algorithms were used to determine the group rate constants and group contribution factors. The group contribution factors for H-atom abstraction and HO* addition to the aromatic compounds were found to linearly correlate with the Taft constants, sigma*, and electrophilic substituent parameters, sigma+, respectively. The best calibrations for 83% (257 rate constants) and predictions for 62% (77

  6. Enumeration of sugars and sugar alcohols hydroxyl groups by aqueous-based acetylation and MALDI-TOF mass spectrometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A method is described for enumerating hydroxyl groups on analytes in aqueous media is described, and applied to some common polyalcohols (erythritol, mannitol, and xylitol) and selected carbohydrates. The analytes were derivatized in water with vinyl acetate in presence of sodium phosphate buffer. ...

  7. Synthesis and evaluation of lanthanide ion DOTA-tetraamide complexes bearing peripheral hydroxyl groups

    PubMed Central

    Pasha, Azhar; Lin, Mai; Tircsó, Gyula; Rostollan, Cynthia L.; Woods, Mark; Kiefer, Garry E.; Sherry, A. Dean; Sun, Xiankai

    2009-01-01

    The use of lanthanide-based contrast agents for magnetic resonance imaging (MRI) has become an integral component of this important diagnostic modality. These inert chelates typically possess high thermodynamic stability constants that serve as a predictor for in vivo stability and low toxicity. Recently a new class of contrast agents was reported having a significantly lower degree thermodynamic stability while exhibiting biodistribution profiles indicative of high stability under biological conditions. These observations are suggestive that the nature of contrast agent stability is also dependent upon the kinetics of complex dissociation; a feature of potential importance when contemplating the design of new chelates for in vivo use. In this paper we present a study of the kinetics of acid catalyzed dissociation, thermodynamic stability, serum stability and biodistribution of a series of DOTA-tetraamide complexes that have been substituted with peripheral hydroxyl groups. The data indicate that these non-traditional contrast agents exhibit in vivo stability comparable to agents with much higher log KML values demonstrating the important contribution of kinetic inertness. PMID:19083028

  8. Unique Phase Behaviors in the Gemini Surfactant/EAN Binary System: The Role of the Hydroxyl Group.

    PubMed

    Li, Qintang; Wang, Xudong; Yue, Xiu; Chen, Xiao

    2015-12-22

    The hydroxyl group in the spacer of a cationic Gemini surfactant (12-3OH-12) caused dramatic changes of the phase behaviors in a protic ionic liquid (EAN). Here, the effects of the hydroxyl group on micellization and lyotropic liquid crystal formation were investigated through the surface tension, small-angle X-ray scattering, polarized optical microscopy, and rheological measurements. With the hydroxyl group in the spacer, the critical micellization concentration of 12-3OH-12 was found to be lower than that of the homologue without hydroxyl (12-3-12) and the 12-3OH-12 molecules packed more densely at the air/EAN interface. It was then interesting to observe a coexistence of two separated phases at wide concentration and temperature ranges in this 12-3OH-12/EAN system. Such a micellar phase separation was rarely observed in the ionic surfactant binary system. With the increase of surfactant concentration, the reverse hexagonal and bicontinuous cubic phases appeared in sequence, whereas only a reverse hexagonal phase was found in 12-3-12/EAN system. But, the hexagonal phases formed with 12-3OH-12 exhibited lower viscoelasticity and thermostability than those observed in 12-3-12/EAN system. Such unique changes in phase behaviors of 12-3OH-12 were ascribed to their enhanced solvophilic interactions of 12-3OH-12 and relatively weak solvophobic interactions in EAN.

  9. Bacterial conversion of hydroxylamino aromatic compounds by both lyase and mutase enzymes involves intramolecular transfer of hydroxyl groups.

    PubMed

    Nadeau, Lloyd J; He, Zhongqi; Spain, Jim C

    2003-05-01

    Hydroxylamino aromatic compounds are converted to either the corresponding aminophenols or protocatechuate during the bacterial degradation of nitroaromatic compounds. The origin of the hydroxyl group of the products could be the substrate itself (intramolecular transfer mechanism) or the solvent water (intermolecular transfer mechanism). The conversion of hydroxylaminobenzene to 2-aminophenol catalyzed by a mutase from Pseudomonas pseudoalcaligenes JS45 proceeds by an intramolecular hydroxyl transfer. The conversions of hydroxylaminobenzene to 2- and 4-aminophenol by a mutase from Ralstonia eutropha JMP134 and to 4-hydroxylaminobenzoate to protocatechuate by a lyase from Comamonas acidovorans NBA-10 and Pseudomonas sp. strain 4NT were proposed, but not experimentally proved, to proceed by the intermolecular transfer mechanism. GC-MS analysis of the reaction products formed in H(2)(18)O did not indicate any (18)O-label incorporation during the conversion of hydroxylaminobenzene to 2- and 4-aminophenols catalyzed by the mutase from R. eutropha JMP134. During the conversion of 4-hydroxylaminobenzoate catalyzed by the hydroxylaminolyase from Pseudomonas sp. strain 4NT, only one of the two hydroxyl groups in the product, protocatechuate, was (18)O labeled. The other hydroxyl group in the product must have come from the substrate. The mutase in strain JS45 converted 4-hydroxylaminobenzoate to 4-amino-3-hydroxybenzoate, and the lyase in Pseudomonas strain 4NT converted hydroxylaminobenzene to aniline and 2-aminophenol but not to catechol. The results indicate that all three types of enzyme-catalyzed rearrangements of hydroxylamino aromatic compounds proceed via intramolecular transfer of hydroxyl groups.

  10. Role of hydroxyl groups on the stability and catalytic activity of Au clusters on rutile surface

    SciTech Connect

    Kent, Paul R

    2011-01-01

    Hydroxyls are present as surface terminations of transition metal oxides under ambient conditions and may modify the properties of supported catalysts. We perform first-principles density functional theory calculations to investigate the role of hydroxyls on the catalytic activity of supported gold clusters on TiO{sub 2} (rutile). We find that they have a long-range effect increasing the adhesion of gold clusters on rutile. While hydroxyls make one gold atom more electronegative, a more complex charge-transfer scenario is observed on larger clusters which are important for catalytic applications. This enhances the molecular adsorption and coadsorption energies of CO and O{sub 2}, thereby increasing the catalytic activity of gold clusters for CO oxidation, consistent with reported experiments. Hydroxyls at the interface between gold and rutile surface are most important to this process, even when not directly bound to gold. As such, accurate models of catalytic processes on gold and other catalysts should include the effect of surface hydroxyls.

  11. Anaerobic Activation of p-Cymene in Denitrifying Betaproteobacteria: Methyl Group Hydroxylation versus Addition to Fumarate

    PubMed Central

    Strijkstra, Annemieke; Trautwein, Kathleen; Jarling, René; Wöhlbrand, Lars; Dörries, Marvin; Reinhardt, Richard; Drozdowska, Marta; Golding, Bernard T.; Wilkes, Heinz

    2014-01-01

    The betaproteobacteria “Aromatoleum aromaticum” pCyN1 and “Thauera” sp. strain pCyN2 anaerobically degrade the plant-derived aromatic hydrocarbon p-cymene (4-isopropyltoluene) under nitrate-reducing conditions. Metabolite analysis of p-cymene-adapted “A. aromaticum” pCyN1 cells demonstrated the specific formation of 4-isopropylbenzyl alcohol and 4-isopropylbenzaldehyde, whereas with “Thauera” sp. pCyN2, exclusively 4-isopropylbenzylsuccinate and tentatively identified (4-isopropylphenyl)itaconate were observed. 4-Isopropylbenzoate in contrast was detected with both strains. Proteogenomic investigation of p-cymene- versus succinate-adapted cells of the two strains revealed distinct protein profiles agreeing with the different metabolites formed from p-cymene. “A. aromaticum” pCyN1 specifically produced (i) a putative p-cymene dehydrogenase (CmdABC) expected to hydroxylate the benzylic methyl group of p-cymene, (ii) two dehydrogenases putatively oxidizing 4-isopropylbenzyl alcohol (Iod) and 4-isopropylbenzaldehyde (Iad), and (iii) the putative 4-isopropylbenzoate-coenzyme A (CoA) ligase (Ibl). The p-cymene-specific protein profile of “Thauera” sp. pCyN2, on the other hand, encompassed proteins homologous to subunits of toluene-activating benzylsuccinate synthase (termed [4-isopropylbenzyl]succinate synthase IbsABCDEF; identified subunits, IbsAE) and protein homologs of the benzylsuccinate β-oxidation (Bbs) pathway (termed BisABCDEFGH; all identified except for BisEF). This study reveals that two related denitrifying bacteria employ fundamentally different peripheral degradation routes for one and the same substrate, p-cymene, with the two pathways apparently converging at the level of 4-isopropylbenzoyl-CoA. PMID:25261521

  12. Oxime ether lipids containing hydroxylated head groups are more superior siRNA delivery agents than their nonhydroxylated counterparts

    PubMed Central

    Gupta, Kshitij; Mattingly, Stephanie J; Knipp, Ralph J; Afonin, Kirill A; Viard, Mathias; Bergman, Joseph T; Stepler, Marissa; Nantz, Michael H; Puri, Anu; Shapiro, Bruce A

    2015-01-01

    Aim: To evaluate the structure–activity relationship of oxime ether lipids (OELs) containing modifications in the hydrophobic domains (chain length, degree of unsaturation) and hydrophilic head groups (polar domain hydroxyl groups) toward complex formation with siRNA molecules and siRNA delivery efficiency of resulting complexes to a human breast cancer cell line (MDA-MB-231). Materials & methods: Ability of lipoplex formation between oxime ether lipids with nucleic acids were examined using biophysical techniques. The potential of OELs to deliver nucleic acids and silence green fluorescent protein (GFP) gene was analyzed using MDA-MB-231 and MDA-MB-231/GFP cells, respectively. Results & conclusion: Introduction of hydroxyl groups to the polar domain of the OELs and unsaturation into the hydrophobic domain favor higher transfection and gene silencing in a cell culture system. PMID:26107486

  13. Role of the phenolic hydroxyl group in the biological activities of simplified analogue of aplysiatoxin with antiproliferative activity.

    PubMed

    Yanagita, Ryo C; Kamachi, Hiroaki; Tanaka, Keisuke; Murakami, Akira; Nakagawa, Yu; Tokuda, Harukuni; Nagai, Hiroshi; Irie, Kazuhiro

    2010-10-15

    The 18-deoxy derivative (3) of a simplified analogue (1) of aplysiatoxin with antiproliferative activity was synthesized to examine the role of the phenolic hydroxyl group at position 18 in the biological activities of 1. Compound 3 as well as 1 showed significant affinity for protein kinase Cδ (PKCδ), and the antiproliferative activity of 3 was slightly higher than that of 1. However, the anti-tumor-promoting activity of 3 was less than that of 1 in vitro, suggesting that the phenolic hydroxyl group of 1 is necessary for the anti-tumor-promoting activity but not for the binding of PKCδ and antiproliferative activity. Moreover, PKC isozyme selectivity of 3 was similar to that of 1, suggesting non-PKC receptors for these compounds to play some roles in the anti-tumor-promoting activity of 1.

  14. Synthesis of dendrigraft poly(ϵ-caprolactone)s using side hydroxyl groups for the grafting of branch chains.

    PubMed

    Cheng, Juan; Ling, Xiujun; Zhong, Zhenlin; Zhuo, Renxi

    2011-11-15

    Dendrigraft poly(ϵ-caprolactone)s with high molecular weight and narrow polydispersity are synthesized via a convenient generation-growth approach. Copolymerization of ϵ-caprolactone (CL) and 4-(2-benzoxyethoxy)-ϵ-caprolactone (BECL) with stannous octanoate as a catalyst affords a functionalized poly(ϵ-caprolactone) (PCL) with benzyl-protected hydroxyl side groups. After removal of benzyl groups by palladium-catalyzed hydrogenolysis, the graft copolymerization of CL and BECL onto the hydroxyl-bearing linear polyester (zero-generation) affords the first-generation graft polyester. Further deprotection and graft polymerization cycles led to dendrigraft polyesters. Molecular weights are multiplied in each graft copolymerization. The second-generation dendrigraft poly(ϵ-caprolactone) has an M(w) of 236 000 g·mol(-1) and M(w) /M(n) of 1.53. PMID:21928304

  15. Environmental distribution, abundance and activity of the Miscellaneous Crenarchaeotal Group

    NASA Astrophysics Data System (ADS)

    Lloyd, K. G.; Biddle, J.; Teske, A.

    2011-12-01

    Many marine sedimentary microbes have only been identified by 16S rRNA sequences. Consequently, little is known about the types of metabolism, activity levels, or relative abundance of these groups in marine sediments. We found that one of these uncultured groups, called the Miscellaneous Crenarchaeotal Group (MCG), dominated clone libraries made from reverse transcribed 16S rRNA, and 454 pyrosequenced 16S rRNA genes, in the White Oak River estuary. Primers suitable for quantitative PCR were developed for MCG and used to show that 16S rRNA DNA copy numbers from MCG account for nearly all the archaeal 16S rRNA genes present. RT-qPCR shows much less MCG rRNA than total archaeal rRNA, but comparisons of different primers for each group suggest bias in the RNA-based work relative to the DNA-based work. There is no evidence of a population shift with depth below the sulfate-methane transition zone, suggesting that the metabolism of MCG may not be tied to sulfur or methane cycles. We classified 2,771 new sequences within the SSU Silva 106 database that, along with the classified sequences in the Silva database was used to make an MCG database of 4,646 sequences that allowed us to increase the named subgroups of MCG from 7 to 19. Percent terrestrial sequences in each subgroup is positively correlated with percent of the marine sequences that are nearshore, suggesting that membership in the different subgroups is not random, but dictated by environmental selective pressures. Given their high phylogenetic diversity, ubiquitous distribution in anoxic environments, and high DNA copy number relative to total archaea, members of MCG are most likely anaerobic heterotrophs who are integral to the post-depositional marine carbon cycle.

  16. Elucidation of hydroxyl groups-antioxidant relationship in mono- and dihydroxyflavones based on O-H bond dissociation enthalpies.

    PubMed

    Treesuwan, Witcha; Suramitr, Songwut; Hannongbua, Supa

    2015-06-01

    Radical scavenging potential is the key to anti-oxidation of hydroxyflavones which generally found in fruits and vegetables. The objective of this work was to investigate the influence of hydroxyl group on the O-H bond dissociation enthalpies (BDE) from a series of mono- and dihydroxyflavones. Calculation at the B3LYP/6-31G(d,p) level reveals the important roles of an additional one hydroxyl group to boost the BDE of hydroxyflavones that were a stabilization of the generated radicals through attractive H-bond interactions, an ortho- and para-dihydroxyl effect, and a presence of the 3-OH in dihydroxyflavones. On the other hand, the meta-dihydroxyl effect and range-hydroxyl effect especially associated with the either 5-OH or 8-OH promoted greater BDE. Results did not only confirm that dihydroxyflavones had lower BDE than monohydroxyflavones but also suggest the selective potent hydroxyflavone molecules that are the 6'-hydroxyflavone (for monohydroxyflavone) and the 5',6'-, 7,8- and 3',4'-dihydroxyflavone which the corresponding radical preferable generated at C6'-O•, C8-O• and C4'-O•, respectively. Electron distribution was limited only over the two connected rings of hydroxyflavones while the expansion distribution into C-ring could be enhanced if the radical was formed especially for the 2',3'- and 5',6'dihydroxyflavone radicals. The delocalized bonds were strengthened after radical was generated. However the 5-O• in 5,6-dihydroxyflavone and the 3-O• in 3,6'-dihydroxyflavone increased the bond order at C4-O11 which might interrupt the conjugated delocalized bonds at the keto group.

  17. PGMA-Based Star-Like Polycations with Plentiful Hydroxyl Groups Act as Highly Efficient miRNA Delivery Nanovectors for Effective Applications in Heart Diseases.

    PubMed

    Li, Rui-Quan; Wu, Yina; Zhi, Ying; Yang, Xinchao; Li, Yulin; Xua, Fu-Jian; Du, Jie

    2016-09-01

    Poly(glycidyl methacrylate)-based star-like polycations with rich hydrophilic hydroxyl groups can efficiently transfer miRNA into primary cardiac fibroblasts for effective applications in cardiac diseases, such as inhibition of cardiac fibrosis and hypertrophy.

  18. Synthesis and characterization of unsymmetrical disubstituted ferrocenes possessing hydroxyl group as a new donor/acceptor of hydrogen bond

    NASA Astrophysics Data System (ADS)

    Lapić, Jasmina; Pezerović, Alma; Cetina, Mario; Djaković, Senka; Rapić, Vladimir

    2011-03-01

    The preparation and characterization of heteroannularly disubstituted ferrocene derivatives 2- 8 are described, with a special attention given on the conformation and hydrogen-bonding of compounds 3b, 7a and 8a. Compounds 3 and 8 comprise hydroxyl group as a new hydrogen bond donor/acceptor and are precursors for preparation of organometallics in asymmetric bioconjugates with natural amino acids. Newly prepared compounds are characterized by elemental analysis, FTIR and NMR spectroscopy. The structures of compounds 1, 3b and 6a were also confirmed by X-ray crystal structure analysis.

  19. A functional polyester carrying free hydroxyl groups promotes the mineralization of osteoblast and human mesenchymal stem cell extracellular matrix.

    PubMed

    Bi, Xiaoping; You, Zhengwei; Gao, Jin; Fan, Xianqun; Wang, Yadong

    2014-06-01

    Functional groups can control biointerfaces and provide a simple way to make therapeutic materials. We recently reported the design and synthesis of poly(sebacoyl diglyceride) (PSeD) carrying a free hydroxyl group in its repeating unit. This paper examines the use of this polymer to promote biomineralization for application in bone tissue engineering. PSeD promoted more mineralization of extracellular matrix secreted by human mesenchymal stem cells and rat osteoblasts than poly(lactic-co-glycolic acid) (PLGA), which is currently widely used in bone tissue engineering. PSeD showed in vitro osteocompatibility and in vivo biocompatibility that matched or surpassed that of PLGA, as well as supported the attachment, proliferation and differentiation of rat osteoblasts and human mesenchymal stem cells. This demonstrates the potential of PSeD for use in bone regeneration. PMID:24560799

  20. Investigation of water and hydroxyl groups associated with coal fly ash by thermal desorption and fourier transform infrared photoacoustic spectroscopies

    SciTech Connect

    Seaverson, L.M.; McClelland, J.F.; Burnet, G.; Anderegg, J.W.; Iles, M.K.

    1985-01-01

    Thermal desorption spectrometry (TDS) and Fourier transform infrared photoacoustic spectroscopy (FT-IR/PAS) have been used in combination to analyze the water and hydroxyl groups associated with four coal fly ashes. Measurements using the former technique on these ashes resulted in identification of three water desorption regions in the temperature range from 25/sup 0/ to 1100/sup 0/C. The regions consisted of a small desorption peak at 50/sup 0/, a broad band from 180/sup 0/ to 400/sup 0/, and an intense peak from 400/sup 0/ to 590/sup 0/. No additional water desorption was observed up to 1100/sup 0/. A fourth ash gave a similar spectrum except that it lacked the intense last peak. The TDS spectra together with FT-IR/PAS spectra taken on samples exposed to pre- and post-desorption peak temperatures allowed the first TDS peak to be assigned to the desorption of physically adsorbed water, the broad band to desorption of hydrogenbonded surface hydroxyls, and the intense last peak to the decomposition of Ca(OH)/sub 2/.

  1. A single tyrosine hydroxyl group almost entirely controls the NADPH specificity of Plasmodium falciparum ferredoxin-NADP+ reductase.

    PubMed

    Baroni, Sara; Pandini, Vittorio; Vanoni, Maria Antonietta; Aliverti, Alessandro

    2012-05-01

    Plasmodium falciparum ferredoxin-NADP(+) reductase (FNR) is a FAD-containing enzyme that, in addition to be a promising target of novel antimalarial drugs, represents an excellent model of plant-type FNRs. The cofactor specificity of FNRs depends on differences in both k(cat) and K(m) values for NADPH and NADH. Here, we report that deletion of the hydroxyl group of the conserved Y258 of P. falciparum FNR, which interacts with the 2'-phosphate group of NADPH, selectively decreased the k(cat) of the NADPH-dependent reaction by a factor of 2 to match that of the NADH-dependent one. Rapid-reaction kinetics, active-site titrations with NADP(+), and anaerobic photoreduction experiments indicated that this effect may be the consequence of destabilization of the catalytically competent conformation of bound NADPH. Moreover, because the Y258F replacement increased the K(m) for NADPH 4-fold and decreased that for NADH 3-fold, it led to a drop in the ability of the enzyme to discriminate between the coenzymes from 70- to just 1.5-fold. The impact of the Y258F change was not affected by the presence of the H286Q mutation, which is known to enhance the catalytic activity of the enzyme. Our data highlight the major role played by the Y258 hydroxyl group in determining the coenzyme specificity of P. falciparum FNR. From the general standpoint of engineering the kinetic properties of plant-type FNRs, although P. falciparum FNR is less strictly NADPH-dependent than its homologues, the almost complete abolishment of coenzyme selectivity reported here has never been accomplished before through a single mutation.

  2. Band profile of hydroxyl groups in the infrared spectrum of hydrogen-bonded surface complexes: Ammonia on silicon dioxide

    SciTech Connect

    Pavlov, A.Y.; Tsyganenko, A.A.

    1994-07-01

    Dependences of the band maximum and band half-width of the stretching modes of surface OH and OD groups perturbed by ammonia adsorption on Aerosil were studied as functions of sample temperature, amount of adsorbed ammonia, and thermal treatment in vacuum. The appearance of a low-frequency wing was explained by the formation of polymer chains of OH groups coupled via adsorbed molecules. The latter tend to form a second bond with an oxygen atom of the neighboring OH group in addition to a hydrogen bond with a hydroxyl proton via nitrogen. The wide band at 3250 cm{sup -1} was assigned to NH groups of adsorbed molecules perturbed by H-bonding with oxygen. This band is observed as a shoulder of the coupled-OH group band. The large width of the latter as well as its temperature behavior was explained by differences in the arrangement of OH groups and by anharmonic coupling with the low-frequency vibrational modes of the complex. 14 refs., 4 figs., 4 tabs.

  3. Boron-doped bismuth oxybromide microspheres with enhanced surface hydroxyl groups: Synthesis, characterization and dramatic photocatalytic activity.

    PubMed

    Liu, ZhangSheng; Liu, JinLong; Wang, HaiYang; Cao, Gang; Niu, JiNan

    2016-02-01

    B-doped BiOBr photocatalysts were successfully synthesized via a facile solvothermal method with boric acid used as boron source. As-obtained products consist of novel hierarchical microspheres, whose nanosheet building units were formed by nanoparticles splicing. They showed dramatic photocatalytic efficiency toward the degradation of Rhodamine B (RhB) and phenol under the visible-light irradiation and the highest activity was achieved by 0.075B-BiOBr. The enhanced photocatalytic activity could be attributed to the enriched surface hydroxyl groups on B-doped BiOBr samples, which not only improved the adsorption of pollutant on the photocatalyst but also promoted the separation of photogenerated electron-hole pairs. In addition, it was found that the main reactive species responsible for the degradation of organic pollutant were h(+) and O2(-) radicals, instead of OH radicals. PMID:26590875

  4. Boron-doped bismuth oxybromide microspheres with enhanced surface hydroxyl groups: Synthesis, characterization and dramatic photocatalytic activity.

    PubMed

    Liu, ZhangSheng; Liu, JinLong; Wang, HaiYang; Cao, Gang; Niu, JiNan

    2016-02-01

    B-doped BiOBr photocatalysts were successfully synthesized via a facile solvothermal method with boric acid used as boron source. As-obtained products consist of novel hierarchical microspheres, whose nanosheet building units were formed by nanoparticles splicing. They showed dramatic photocatalytic efficiency toward the degradation of Rhodamine B (RhB) and phenol under the visible-light irradiation and the highest activity was achieved by 0.075B-BiOBr. The enhanced photocatalytic activity could be attributed to the enriched surface hydroxyl groups on B-doped BiOBr samples, which not only improved the adsorption of pollutant on the photocatalyst but also promoted the separation of photogenerated electron-hole pairs. In addition, it was found that the main reactive species responsible for the degradation of organic pollutant were h(+) and O2(-) radicals, instead of OH radicals.

  5. Influence of Hydroxyl Group Position and Temperature on Thermophysical Properties of Tetraalkylammonium Hydroxide Ionic Liquids with Alcohols

    PubMed Central

    Attri, Pankaj; Baik, Ku Youn.; Venkatesu, Pannuru; Kim, In Tae; Choi, Eun Ha

    2014-01-01

    In this work, we have explored the thermophysical properties of tetraalkylammonium hydroxide ionic liquids (ILs) such as tetrapropylammonium hydroxide (TPAH) and tetrabutylammonium hydroxide (TBAH) with isomers of butanol (1-butanol, 2-butanol and 2-methyl-2-propanol) within the temperature range 293.15–313.15 K, with interval of 5 K and over the varied concentration range of ILs. The molecular interactions between ILs and butanol isomers are essential for understanding the function of ILs in related measures and excess functions are sensitive probe for the molecular interactions. Therefore, we calculated the excess molar volume (VE) and the deviation in isentropic compressibility (Δκs) using the experimental values such as densities (ρ) and ultrasonic sound velocities (u) that are measured over the whole compositions range at five different temperatures (293.15, 298.15, 303.15, 308.15 and 313.15 K) and atmospheric pressure. These excess functions were adequately correlated by using the Redlich–Kister polynomial equation. It was observed that for all studied systems, the VE and Δκs values are negative for the whole composition range at 293.15 K. And, the excess function follows the sequence: 2-butanol>1-butanol>2-methyl-2-propanol, which reveals that (primary or secondary or tertiary) position of hydroxyl group influence the magnitude of interactions with ILs. The negative values of excess functions are contributions from the ion-dipole interaction, hydrogen bonding and packing efficiency between the ILs and butanol isomers. Hence, the position of hydroxyl group plays an important role in the interactions with ILs. The hydrogen bonding features between ILs and alcohols were analysed using molecular modelling program by using HyperChem 7. PMID:24489741

  6. Influence of hydroxyl group position and temperature on thermophysical properties of tetraalkylammonium hydroxide ionic liquids with alcohols.

    PubMed

    Attri, Pankaj; Baik, Ku Youn; Venkatesu, Pannuru; Kim, In Tae; Choi, Eun Ha

    2014-01-01

    In this work, we have explored the thermophysical properties of tetraalkylammonium hydroxide ionic liquids (ILs) such as tetrapropylammonium hydroxide (TPAH) and tetrabutylammonium hydroxide (TBAH) with isomers of butanol (1-butanol, 2-butanol and 2-methyl-2-propanol) within the temperature range 293.15-313.15 K, with interval of 5 K and over the varied concentration range of ILs. The molecular interactions between ILs and butanol isomers are essential for understanding the function of ILs in related measures and excess functions are sensitive probe for the molecular interactions. Therefore, we calculated the excess molar volume (V(E) ) and the deviation in isentropic compressibility (Δκs ) using the experimental values such as densities (ρ) and ultrasonic sound velocities (u) that are measured over the whole compositions range at five different temperatures (293.15, 298.15, 303.15, 308.15 and 313.15 K) and atmospheric pressure. These excess functions were adequately correlated by using the Redlich-Kister polynomial equation. It was observed that for all studied systems, the V(E) and Δκs values are negative for the whole composition range at 293.15 K. And, the excess function follows the sequence: 2-butanol>1-butanol>2-methyl-2-propanol, which reveals that (primary or secondary or tertiary) position of hydroxyl group influence the magnitude of interactions with ILs. The negative values of excess functions are contributions from the ion-dipole interaction, hydrogen bonding and packing efficiency between the ILs and butanol isomers. Hence, the position of hydroxyl group plays an important role in the interactions with ILs. The hydrogen bonding features between ILs and alcohols were analysed using molecular modelling program by using HyperChem 7.

  7. Protonated Dipeptide Losses from b 5 and b 4 Ions of Side Chain Hydroxyl Group Containing Pentapeptides

    NASA Astrophysics Data System (ADS)

    Atik, A. Emin; Yalcin, Talat

    2013-10-01

    In this study, C-terminal protonated dipeptide eliminations were reported for both b 5 and b 4 ions of side chain hydroxyl group (-OH) containing pentapeptides. The study utilized the model C-terminal amidated pentapeptides having sequences of XGGFL and AXVYI, where X represents serine (S), threonine (T), glutamic acid (E), aspartic acid (D), or tyrosine (Y) residue. Upon low-energy collision-induced dissociation (CID) of XGGFL (where X = S, T, E, D, and Y) model peptide series, the ions at m/z 279 and 223 were observed as common fragments in all b 5 and b 4 ion (except b 4 ion of YGGFL) mass spectra, respectively. By contrast, peptides, namely SMeGGFL-NH2 and EOMeGGFL-NH2, did not show either the ion at m/z 279 or the ion at m/z 223. It is shown that the side chain hydroxyl group is required for the possible mechanism to take place that furnishes the protonated dipeptide loss from b 5 and b 4 ions. In addition, the ions at m/z 295 and 281 were detected as common fragments in all b 5 and b 4 ion (except b 4 ion of AYVYI) mass spectra, respectively, for AXVYI model peptide series. The MS4 experiments exhibited that the fragment ions at m/z 279, 223, 295, and 281 entirely reflect the same fragmentation behavior of [M + H]+ ion generated from commercial dipeptides FL-OH, GF-OH, YI-OH, and VY-OH. These novel eliminations reported here for b 5 and b 4 ions can be useful in assigning the correct and reliable peptide sequences for high-throughput proteomic studies.

  8. THE ABUNDANCE OF BULLET GROUPS IN ΛCDM

    SciTech Connect

    Fernández-Trincado, J. G.; Forero-Romero, J. E.; Foex, G.; Motta, V.; Verdugo, T. E-mail: je.forero@uniandes.edu.co

    2014-06-01

    We estimate the expected distribution of displacements between the two dominant dark matter (DM) peaks (DM-DM displacements) and between the DM and gaseous baryon peak (DM-gas displacements) in DM halos with masses larger than 10{sup 13} h {sup –1} M {sub ☉}. As a benchmark, we use the observation of SL2S J08544–0121, which is the lowest mass system (1.0 × 10{sup 14} h {sup –1} M {sub ☉}) observed so far, featuring a bi-modal DM distribution with a dislocated gas component. We find that (50 ± 10)% of the DM halos with circular velocities in the range 300-700 km s{sup –1} (groups) show DM-DM displacements equal to or larger than 186 ± 30 h {sup –1} kpc as observed in SL2S J08544–0121. For DM halos with circular velocities larger than 700 km s{sup –1} (clusters) this fraction rises to (70 ± 10)%. Using the same simulation, we estimate the DM-gas displacements and find that 0.1%-1.0% of the groups should present separations equal to or larger than 87 ± 14 h {sup –1} kpc, corresponding to our observational benchmark; for clusters, this fraction rises to (7 ± 3)%, consistent with previous studies of DM to baryon separations. Considering both constraints on the DM-DM and DM-gas displacements, we find that the number density of groups similar to SL2S J08544–0121 is ∼6.0 × 10{sup –7} Mpc{sup –3}, three times larger than the estimated value for clusters. These results open up the possibility for a new statistical test of ΛCDM by looking for DM-gas displacements in low mass clusters and groups.

  9. Heterogeneity of hydroxyl and deuteroxyl groups on the surface of TiO{sub 2} polymorphs

    SciTech Connect

    Contescu, C.; Popa, V.T.; Schwarz, J.A.

    1996-06-01

    Potentiometric titration data from pure rutile, anatase, and a commercial fumed titania (Degussa P25) were analyzed in terms of proton binding isotherms from which proton affinity distributions (PADs) of surface sites were obtained. As-received samples, whose thermal and storage history were not systematically controlled, as well as samples subjected to controlled calcination-rehydration-drying treatments were studied. The results indicated the occurrence of a limited number of surface groups on the two polymorphs. The behavior of pure rutile and anatase could be admixed to simulate the acid-base behavior of the commercial sample; on this basis the surface of fumed titania consists largely of anatase-like structures with a small contribution (7%) of rutile-like groups. The region of {nu}{sub OD} stretching vibrations of isolated -OD groups on extensively dehydroxylated samples was found to correlate with the pK`s determined from PADs. A qualitative assignment of measured pK values based on either the original MUSIC model (Hiemstra, T., de Wit, J.C.M., and Van Riemsdijk, W.H., J. Colloid Interface Sci. 133, 105 (1989)) or a refined version of it is presented.

  10. Short-step chemical synthesis of DNA by use of MMTrS group for protection of 5'-hydroxyl group.

    PubMed

    Shiraishi, Miyuki; Utagawa, Eri; Ohkubo, Akihiro; Sekine, Mitsuo; Seio, Kohji

    2007-01-01

    4-methoxytrithylthio (MMTrS) group was applied for the appropriately protected four canonical nucleosides. We prepared the phosphoroamidite units by use of these nucleosides and developed the synthesis of oligodeoxynucleotides without any acidic treatment. Moreover, the new DNA synthesis protocol was applied to an automated DNA synthesizer for the synthesis of longer oligodeoxynucleotides. PMID:18029620

  11. Oestradiol protects against the harmful effects of fluoride more by increasing thiol group levels than scavenging hydroxyl radicals.

    PubMed

    Dlugosz, Anna; Roszkowska, Anna; Zimmer, Mariusz

    2009-12-01

    The aim of the study was to investigate the role of oestrogens in free radical detoxication upon exposure to fluoride. Interactions between xenobiotics and oestrogens need to be investigated, especially as many chemicals interact with the oestrogen receptor. It is still unknown whether free radical-generating xenobiotics can influence the antioxidative ability of oestradiol (E(2)). In an in vitro examination of human placental mitochondria, thiobarbituric active reagent species (TBARS), hydroxyl radical ((*)OH) generation and protein thiol (-SH) groups were detected. 17beta-E(2) was examined in physiological (0.15-0.73 nM) and experimental (1-10 microM) concentrations and sodium fluoride (NaF) in concentrations of 6-24 microM. E(2) in all the concentrations significantly decreased lipid peroxidation measured as the TBARS level, in contrast to NaF, which increased lipid peroxidation. Lipid peroxidation induced by NaF was decreased by E(2). The influence of E(2) on (*)OH generation was not very significant and depended on the E(2 )concentration. The main mechanism of E(2) protection in NaF exposure appeared to be connected with the influence of E(2 )on thiol group levels, not (*)OH scavenging ability. The E(2) in concentrations 0.44-0.73 nM and 1-10 microM significantly increased the levels of -SH groups, in contrast to NaF, which significantly decreased them. E(2) at every concentration reversed the harmful effects of NaF on -SH group levels. No unfavourable interactions in the influence of E(2) and NaF on TBARS production, (*)OH generation, or -SH group levels were observed. The results suggest that postmenopausal women could be more sensitive to NaF-initiated oxidative stress.

  12. Possible mechanism of structural incorporation of Al into diatomite during the deposition process I. Via a condensation reaction of hydroxyl groups.

    PubMed

    Liu, Dong; Yu, Wenbin; Deng, Liangliang; Yuan, Weiwei; Ma, Lingya; Yuan, Peng; Du, Peixin; He, Hongping

    2016-01-01

    The structural incorporation of aluminium (Al) into diatomite is investigated by preparing several Al-diatomite composites by loading an Al precursor, hydroxyl aluminum polymer (Al13), onto the surface of diatomite and heating at various temperatures. The results indicate that Al was incorporated and implanted into the structure of diatomite by the condensation reaction of the hydroxyl groups of Al13 and diatomite, and the Si-O-Al(OH) groups were formed during the condensation reaction. Al incorporation by the condensation reaction of hydroxyl groups of Al13 with single silanols of diatomite occurred more readily than that with geminal silanols. The Al incorporation increased solid acidity of diatomite after Al incorporation. The acidity improvement was various for different types of acid sites, depending on the preparation temperature of the Al-incorporated diatomite. Both Brønsted and Lewis acid sites increased greatly after heating at 250 and 350 °C, but only L acid sites significantly improved after heating at 500 °C. These results demonstrate that the structural incorporation of Al(3+) ions into diatomite can occur by the condensation reaction of the hydroxyl groups of the Al precursors and diatomite. Moreover, the rich solid acid sites of Al-incorporated diatomite show its promising application as a solid acid catalyst.

  13. Plasma enhanced chemical vapour deposition of silica onto Ti: Analysis of surface chemistry, morphology and functional hydroxyl groups

    PubMed Central

    Szili, Endre J.; Kumar, Sunil; Smart, Roger St. C.; Lowe, Rachel; Saiz, Eduardo; Voelcker, Nicolas H.

    2009-01-01

    Previously, we have developed and characterised a procedure for the deposition of thin silica films by a plasma enhanced chemical vapour deposition (PECVD) procedure using tetraethoxysilane (TEOS) as the main precursor. We have used the silica coatings for improving the corrosion resistance of metals and for enhancing the bioactivity of biomedical metallic implants. Recently, we have been fine-tuning the PECVD method for producing high quality and reproducible PECVD-silica (PECVD-Si) coatings on metals, primarily for biomaterial applications. In order to understand the interaction of the PECVD-Si coatings with biological species (such as proteins and cells), it is important to first analyse the properties of the silica films deposited using the optimised parameters. Therefore, this current investigation was carried out to analyse the characteristic features of PECVD-Si deposited on Ti substrates (PECVD-Si-Ti). We determined that the PECVD-Si coatings on Ti were conformal to the substrate surface, strongly adhered to the underlying substrate and were resistant to delamination. The PECVD-Si surface was composed of stoichiometric SiO2, showed a low carbon content (below 10 at.%) and was very hydrophilic (contact angle <10°). Finally, we also showed that the PECVD-Si coatings contain functional hydroxyl groups. PMID:19809536

  14. Effect of hydroxyl group position on adsorption behavior and corrosion inhibition of hydroxybenzaldehyde Schiff bases: Electrochemical and quantum calculations

    NASA Astrophysics Data System (ADS)

    Danaee, I.; Ghasemi, O.; Rashed, G. R.; Rashvand Avei, M.; Maddahy, M. H.

    2013-03-01

    The corrosion inhibition and adsorption of N,N'-bis(n-hydroxybenzaldehyde)-1,3-propandiimine (n-HBP) Schiff bases has been investigated on steel electrode in 1 M HCl by using electrochemical techniques. The experimental results suggest that the highest inhibition efficiency was obtained for 3-HBP. Polarization curves reveal that all studied inhibitors are mixed type. Density functional theory (DFT) at the B3LYP/6-31G(d,p) and B3LYP/3-21G basis set levels and ab initio calculations using HF/6-31G(d,p) and HF/3-21G methods were performed on three Schiff bases. By studying the effects of hydroxyl groups in ortho-, meta-, para- positions, the best one as inhibitor was found to be meta-position of OH in Schiff base (i.e., 3-HBP). The order of inhibition efficiency obtained was corresponded with the order of most of the calculated quantum chemical parameters. Quantitative structure activity relationship (QSAR) approach has been used and a correlation of the composite index of some of the quantum chemical parameters was performed to characterize the inhibition performance of the Schiff bases studied. The results showed that %IE of the Schiff bases was closely related to some of the quantum chemical parameters but with varying degrees/order. The calculated %IE of the Schiff base studied was found to be close to their experimental corrosion inhibition efficiencies.

  15. Iron-group Abundances in the Metal-poor Main-Sequence Turnoff Star HD~84937

    NASA Astrophysics Data System (ADS)

    Sneden, Christopher; Cowan, John J.; Kobayashi, Chiaki; Pignatari, Marco; Lawler, James E.; Den Hartog, Elizabeth A.; Wood, Michael P.

    2016-01-01

    We have derived new, very accurate abundances of the Fe-group elements Sc through Zn (Z = 21-30) in the bright main-sequence turnoff star HD 84937 based on high-resolution spectra covering the visible and ultraviolet spectral regions. New or recent laboratory transition data for 14 species of seven elements have been used. Abundances from more than 600 lines of non-Fe species have been combined with about 550 Fe lines in HD 84937 to yield abundance ratios of high precision. The abundances have been determined from both neutral and ionized transitions, which generally are in agreement with each other. We find no substantial departures from the standard LTE Saha ionization balance in this [Fe/H] = -2.32 star. Noteworthy among the abundances are [Co/Fe] = +0.14 and [Cu/Fe] = -0.83, in agreement with past studies of abundance trends in this and other low-metallicity stars, and < [{{Sc,Ti,V/Fe}}]> = +0.31, which has not been noted previously. A detailed examination of scandium, titanium, and vanadium abundances in large-sample spectroscopic surveys reveals that they are positively correlated in stars with [Fe/H] < -2 HD 84937 lies at the high end of this correlation. These trends constrain the synthesis mechanisms of Fe-group elements. We also examine the Galactic chemical evolution abundance trends of the Fe-group elements, including a new nucleosynthesis model with jet-like explosion effects.

  16. Measurements of the Fe-group abundance in energetic solar particles

    NASA Technical Reports Server (NTRS)

    Bertsch, D. L.; Fichtel, C. E.; Pellerin, C. J.; Reames, D. V.

    1972-01-01

    The abundance of Fe-group nuclei in the energetic solar particles was measured twice in the 24 January 1971 event and once in the 2 September 1971 event. Including earlier results from the 2 September 1966 event, the Fe-group abundance was found to be in the range from 3% to 6% of the oxygen nuclei in the energy interval from 21 to 50 MeV/nucleon, in those events where the Fe-group abundance could be measured. Fe-nuclei have a different charge-to-mass ratio from that of the C, N, O nuclei, so small variations in the Fe abundance in solar particles are expected. In the three exposures where the statistics were adequate to construct an energy spectrum, the Fe-group nuclei were seen to have an energy/nucleon spectrum similar to that of the C, N, O nuclei; however, the energy/nucleon range was limited. The abundance for the Fe-group nuclei is consistent with the present solar spectroscopic abundance estimates.

  17. Structure-Activity Relationship of Synthetic 2-Phenylnaphthalenes with Hydroxyl Groups that Inhibit Proliferation and Induce Apoptosis of MCF-7 Cancer Cells

    PubMed Central

    Chang, Chi-Fen; Ke, Ci-Yi; Wu, Yang-Chang; Chuang, Ta-Hsien

    2015-01-01

    In this study, six 2-phenylnaphthalenes with hydroxyl groups were synthesized in high yields by the demethylation of the corresponding methoxy-2-phenylnaphthalenes, and one 2-phenylnaphthalene with an amino group was obtained by hydrogenation. All of the 2-phenylnaphthalene derivatives were evaluated for cytotoxicity, and the structure-activity relationship (SAR) against human breast cancer (MCF-7) cells was also determined. The SAR results revealed that cytotoxicity was markedly promoted by the hydroxyl group at the C-7 position of the naphthalene ring. The introduction of hydroxyl groups at the C-6 position of the naphthalene ring and the C-4' position of the phenyl ring fairly enhanced cytotoxicity, but the introduction of a hydroxyl group at the C-3' position of the phenyl ring slightly decreased cytotoxicity. Overall, 6,7-dihydroxy-2-(4'-hydroxyphenyl)naphthalene (PNAP-6h) exhibited the best cytotoxicity, with an IC50 value of 4.8 μM against the MCF-7 cell line, and showed low toxicity toward normal human mammary epithelial cells (MCF-10A). PNAP-6h led to cell arrest at the S phase, most likely due to increasing levels of p21 and p27 and decreasing levels of cyclin D1, CDK4, cyclin E, and CDK2. In addition, PNAP-6h decreased CDK1 and cyclin B1 expression, most likely leading to G2/M arrest, and induced morphological changes, such as nuclear shrinkage, nuclear fragmentation, and nuclear hypercondensation, as observed by Hoechst 33342 staining. PNAP-6h induced apoptosis, most likely by the promotion of Fas expression, increased PARP activity, caspase-7, caspase-8, and caspase-9 expression, the Bax/Bcl-2 ratio, and the phosphorylation of p38, and decreased the phosphorylation of ERK. This study provides the first demonstration of the cytotoxicity of PNAPs against MCF-7 cells and elucidates the mechanism underlying PNAP-induced cytotoxicity. PMID:26492346

  18. The influence of pendant hydroxyl groups on enzymatic degradation and drug delivery of amphiphilic poly[glycidol-block-(epsilon-caprolactone)] copolymers.

    PubMed

    Mao, Jing; Gan, Zhihua

    2009-11-10

    An amphiphilic diblock copolymer PG-b-PCL with well-controlled structure and pendant hydroxyl groups along hydrophilic block was synthesized by sequential anionic ring-opening polymerization. The micellization and drug release of PG-b-PCL copolymers using pyrene as a fluorescence probe were investigated for determining the influences of copolymer composition and lipase concentration on drug loading capacity and controlled release behavior. The biodegradation of PG-b-PCL copolymers was studied with microspheres as research samples. It has been concluded that the polar hydroxyl groups along each repeat unit of hydrophilic PG block in PG-b-PCL copolymer have great influences on drug encapsulation, drug release, and enzymatic degradation of micelles and microspheres.

  19. Control of oxygen atom chirality and chelate ring conformation by protected/free sugar hydroxyl groups in glucose-pendant dipicolylamine-copper(II) complexes.

    PubMed

    Mikata, Yuji; Sugai, Yuko; Yano, Shigenobu

    2004-08-01

    A pair of copper(II) complexes 1 and 2 exhibit an enantiomeric chiral center at the oxygen atom that coordinates to the metal center. The configurations of the oxygen atom chirality and the chelate ring conformation are simply controlled by protected/free hydroxyl groups of the sugar moiety, yielding mirror image CD spectra. In this system, repulsive and attractive forces are used to regulate chirality on the copper-coordinated oxygen atom both in the solid state and in solution.

  20. Surface chemistry of boron-doped SiO{sub 2} CVD: Enhanced uptake of tetraethyl orthosilicate by hydroxyl groups bonded to boron

    SciTech Connect

    Bartram, M.E.; Moffat, H.K.

    1993-12-31

    Insight into how dopants can enhance deposition rates has been obtained by comparing reactivities of tetraethyl orthosilicate (TEOS, Si(OCH{sub 2}CH{sub 3}){sub 4}) with silanol and boranol groups on SiO{sub 2}. This comparison is relevant for boron-doped SiO{sub 2} film growth from TEOS and trimethyl borate (TMB, B(OCH{sub 3}){sub 3}) sources since boranols and silanols are expected to be present on surface during the (CVD). A silica substrate having coadsorbed deuterated silanols (SIOD) and boranols (BOD) was reacted with TEOS in a cold-wall reactor in the mTorr pressure regime at 1000K. Reactions were followed with Fourier transform infrared spectroscopy. Use of deuterated hydroxyls allowed consumption of hydroxyls by TEOS chemisorption to be distinguished from concurrent formation of SIOH and BOH that results from TEOS decomposition. It was found that TEOS reacts with BOD at twice the rate observed for SIOD demonstrating that hydroxyl groups bonded to boron increase the rate of TEOS chemisorption. Surface ethoxy groups produced by chemisorption of TEOS decompose at a slower rate in the presence of TMB decomposition products. Possible dependencies on reactor geometries and other deposition conditions may determine which of these two competing effects will control deposition rates. This may explain (in part) why the rate enhancement effect is not always observed in boron-doped SiO{sub 2} CVD processes.

  1. CHEMICAL ABUNDANCES OF SEVEN IRREGULAR AND THREE TIDAL DWARF GALAXIES IN THE M81 GROUP

    SciTech Connect

    Croxall, Kevin V.; Van Zee, Liese; Lee, Henry; Miller, Bryan W.; Skillman, Evan D.; Lee, Janice C.; Cote, Stephanie; Kennicutt, Robert C. E-mail: vanzee@astro.indiana.ed E-mail: skillman@astro.umn.ed E-mail: stephanie.cote@nrc-cnrc.gc.c E-mail: bmiller@gemini.ed

    2009-11-01

    We have derived nebular abundances for 10 dwarf galaxies belonging to the M81 Group, including several galaxies which do not have abundances previously reported in the literature. For each galaxy, multiple H II regions were observed with GMOS-N at the Gemini Observatory in order to determine abundances of several elements (oxygen, nitrogen, sulfur, neon, and argon). For seven galaxies, at least one H II region had a detection of the temperature sensitive [O III] lambda4363 line, allowing a 'direct' determination of the oxygen abundance. No abundance gradients were detected in the targeted galaxies, and the observed oxygen abundances are typically in agreement with the well-known metallicity-luminosity relation. However, three candidate 'tidal dwarf' galaxies lie well off this relation: UGC 5336, Garland, and KDG 61. The nature of these systems suggests that UGC 5336 and Garland are indeed recently formed systems, whereas KDG 61 is most likely a dwarf spheroidal galaxy which lies along the same line of sight as the M81 tidal debris field. We propose that these H II regions formed from previously enriched gas which was stripped from nearby massive galaxies (e.g., NGC 3077 and M81) during a recent tidal interaction.

  2. Influence of lipids with hydroxyl-containing head groups on Fe2+ (Cu2+)/H2O2-mediated transformation of phospholipids in model membranes.

    PubMed

    Olshyk, Viktoriya N; Melsitova, Inna V; Yurkova, Irina L

    2014-01-01

    Under condition of ROS formation in lipid membranes, free radical reactions can proceed in both hydrophobic (peroxidation of lipids, POL) and polar (free radical fragmentation) parts of the bilayer. Free-radical fragmentation is typical for the lipids containing a hydroxyl group in β-position with respect to an ester or amide bond. The present study has been undertaken to investigate free-radical transformations of phospholipids in model membranes containing lipids able to undergo fragmentation in their polar part. Liposomes from egg yolk lecithin containing saturated or monounsaturated glycero- and sphingolipids were subjected to the action of an HO* - generating system - Fe(2+)(Cu(2+))/H2O2/Asc, and the POL products were investigated. In parallel with this, the effects of monoacylglycerols and scavengers of reactive species on Fe(2+)(Cu(2+))/H2O2/Asc - mediated free-radical fragmentation of phosphatidylglycerols were studied. Hydroxyl-containing sphingolipids and glycerolipids, which undergo free-radical fragmentation under such conditions, manifested antioxidant properties in the model membranes. In the absence of HO groups in the lipid structure, the effect was either pro-oxidant or neutral. Monoacylglycerols slowed down the rate of both peroxidation in the hydrophobic part and free-radical fragmentation in the hydrophilic part of phospholipid membrane. Scavengers of reactive species inhibited the fragmentation of phosphatidylglycerol substantially. Thus, the ability of hydroxyl-containing lipids to undergo free-radical fragmentation in polar part apparently makes a substantial contribution to the mechanism of their protector action. PMID:24189590

  3. Influence of lipids with hydroxyl-containing head groups on Fe2+ (Cu2+)/H2O2-mediated transformation of phospholipids in model membranes.

    PubMed

    Olshyk, Viktoriya N; Melsitova, Inna V; Yurkova, Irina L

    2014-01-01

    Under condition of ROS formation in lipid membranes, free radical reactions can proceed in both hydrophobic (peroxidation of lipids, POL) and polar (free radical fragmentation) parts of the bilayer. Free-radical fragmentation is typical for the lipids containing a hydroxyl group in β-position with respect to an ester or amide bond. The present study has been undertaken to investigate free-radical transformations of phospholipids in model membranes containing lipids able to undergo fragmentation in their polar part. Liposomes from egg yolk lecithin containing saturated or monounsaturated glycero- and sphingolipids were subjected to the action of an HO* - generating system - Fe(2+)(Cu(2+))/H2O2/Asc, and the POL products were investigated. In parallel with this, the effects of monoacylglycerols and scavengers of reactive species on Fe(2+)(Cu(2+))/H2O2/Asc - mediated free-radical fragmentation of phosphatidylglycerols were studied. Hydroxyl-containing sphingolipids and glycerolipids, which undergo free-radical fragmentation under such conditions, manifested antioxidant properties in the model membranes. In the absence of HO groups in the lipid structure, the effect was either pro-oxidant or neutral. Monoacylglycerols slowed down the rate of both peroxidation in the hydrophobic part and free-radical fragmentation in the hydrophilic part of phospholipid membrane. Scavengers of reactive species inhibited the fragmentation of phosphatidylglycerol substantially. Thus, the ability of hydroxyl-containing lipids to undergo free-radical fragmentation in polar part apparently makes a substantial contribution to the mechanism of their protector action.

  4. Can the conformation of flexible hydroxyl groups be constrained by simple NMR crystallography approaches? The case of the quercetin solid forms.

    PubMed

    Filip, Xenia; Filip, Claudiu

    2015-02-01

    Hydrogen atoms in systems with many flexible hydroxyl side-groups are difficult to be exactly located from experimental X-Ray diffraction and/or solid-state NMR data, thus often leading to wrong conclusions with respect to the hydrogen bonding network established in crystal lattice. A simple computational method is proposed in the present work to tackle this problem, which may be readily incorporated in conventional NMR crystallography protocols. The method is based on ranking all possible conformations of the flexible hydroxyls according to their lattice energy in crystalline environments. Its effectiveness is investigated on two distinct solid forms of quercetin, for which only two out of the five hydroxyl side-groups can be well constrained from experimental/theoretical data. For this purpose, first-principle quantum-mechanical computations were combined with calculations at the molecular mechanics (MM) level of theory, and previous ss-NMR and X-Ray diffraction data. To assess accuracy in ranking the identified conformers, tests have been performed first on quercetin dihydrate, for which an X-Ray single-crystal structure is available. The possibility of applying this method in a real NMR crystallography context has been investigated finally on anhydrous quercetin, for which only powder X-Ray crystal structure has been reported so far.

  5. Fe-Group Elements in the Metal-Poor Star HD 84937: Abundances and their Implications

    NASA Astrophysics Data System (ADS)

    Sneden, Chris; Cowan, John J.; Kobayashi, Chiaki; Pignatari, Marco; Lawler, James E.; Den Hartog, Elizabeth; Wood, Michael P.

    2016-01-01

    We have derived accurate relative abundances of the Fe-group elements Sc through Zn in the very metal-poor main-sequence turnoff star HD 84937. For this study we analyzed high resolution, high signal-to-noise HST/STIS and VLT/UVES spectra over a total wavelength range 2300-7000 Å. We employed only recent or newly-applied reliable laboratory transition data for all species. Abundances from more than 600 lines of non-Fe species were combined with about 550 Fe lines in HD 84937 to yield abundance ratios of high precision. From parallel analyses of solar photospheric spectra we also derived new solar abundances of these elements. This in turn yielded internally-consistent relative HD 84937 abundances with respect to the Sun. For seven of the ten Fe-group elements the HD 84937 abundances were from both neutral and ionized transitions. In all of these cases the neutral and ionized species yield the same abundances within the measurement uncertainties. Therefore standard Saha ionization balance appears to hold in the HD 84937 atmosphere. We derived metallicity [Fe/H] = -2.32 with sample standard deviation of 0.06. Solid evidence is seen for departures from the solar abundance mix in HD 84937, for example [Co/Fe] = +0.14, [Cu/Fe] = -0.83, and <[Sc,Ti,V/Fe]> = +0.31. Combining our Sc, Ti, and V abundances for this star with those from large-sample spectroscopic surveys suggests that these elements are positively correlated in stars with [Fe/H] < -2. HD 84937 is unusually enriched in Sc, Ti, and V. Our analysis strongly suggests that different types of supernovae with a large scatter of explosion energies and asymmetries contributed to the creation of the Fe-group elements early in the Galaxy's history.This work has been supported in part by NASA grant NNX10AN93G (J.E.L.), by NSF grants AST-1211055 (J.E.L.), AST-1211585 (C.S.), PHY-1430152 (through JINA, J.J.C. and M.P.), EU MIRGCT-2006-046520 (M.P.), and by the ``Lendlet-2014'' Programme of the Hungarian Academy of

  6. Platinum-group element abundance and distribution in chromite deposits of the Acoje Block, Zambales Ophiolite Complex, Philippines

    USGS Publications Warehouse

    Bacuta, G.C.; Kay, R.W.; Gibbs, A.K.; Lipin, B.R.

    1990-01-01

    Platinum-group elements (PGE) occur in ore-grade concentration in some of the chromite deposits related to the ultramafic section of the Acoje Block of the Zambales Ophiolite Complex. The deposits are of three types: Type 1 - associated with cumulate peridotites at the base of the crust; Type 2 - in dunite pods from the top 1 km of mantle harzburgite; and Type 3 - like Type 2, but in deeper levels of the harzburgite. Most of the deposites have chromite compositions that are high in Cr with Cr/(Cr + Al) (expressed as chromium index, Cr#) > 0.6; high-Al (Cr# Pd, thought to be characteristic of PGE-barren deposits) and positive slope (Ir < Pd, characteristic of PGE-rich deposits). Iridium, Ru and Os commonly occur as micron-size laurite (sulfide) inclusions in unfractured chromite. Laurite and native Os are also found as inclusions in interstitial sulfides. Platinum and Pd occur as alloy inclusions (and possibly as solid solution) in interstitial Ni-Cu sulfides and as tellurobismuthides in serpentine and altered sulfides. Variability of PGE distribution may be explained by alteration, crystal fractionation or partial melting processes. Alteration and metamorphism were ruled out, because PGE contents do not correlate with degree of serpentinization or the abundance and type (hydroxyl versus non-hydroxyl) of silicate inclusions in chromite. Preliminary Os isotopic data do not support crustal contamination as a source of the PGEs in the Acoje deposits. The anomalous PGE concentrations in Type 1 high-Cr chromite deposits are attributed to two stages of enrichment: an early enrichment of their mantle source from previous melting events and a later stage of sulfide segregation accompanying chromite crystallization. High-Al chromite deposits which crystallized from basalts derived from relatively low degrees of melting owe their low PGE content to partitioning of PGEs in sulfides and alloys that remain in the mantle. High-Cr deposits crystallized from melts that were

  7. Dehydration and Stabilization of a Reactive Tertiary Hydroxyl Group in Solid Oral Dosage Forms of BMS-779788.

    PubMed

    Adams, Monica L; Sharma, Vijayata; Gokhale, Madhushree; Huang, Yande; Stefanski, Kevin; Su, Ching; Hussain, Munir A

    2016-04-01

    BMS-779788 contains a reactive tertiary hydroxyl attached to a weakly basic imidazole ring. Propensity of the carbinol toward dehydration to yield the corresponding alkene, BMS-779788-ALK, was evaluated. Elevated levels of BMS-779788-ALK were observed in excipient compatibility samples. Stability studies revealed that BMS-779788 degrades to BMS-779788-ALK in capsules and tablets prepared by both dry and wet granulation processes. An acid-catalyzed dehydration mechanism, in which the heterocyclic core contributes resonance stability to the cationic intermediate via charge transfer to the imidazole ring, was proposed. Therefore, neutralization via a buffered (pH 7.0) granulating solution was used to mitigate dehydration. Solution studies revealed degradation of BMS-779788 to BMS-779788-ALK over the pH range of 1-7.5. Reversibility was confirmed by initiating reactions with BMS-779788-ALK over the same pH range. Accordingly, a simple reversible scheme can be used to describe reactions initiated with either BMS-779788 or BMS-779788-ALK. To eliminate potential for charge delocalization across the heterocycle and probe the degradation mechanism, the imidazole ring of BMS-779788 was methylated (BMS-779788-Me). The propensity for acid-catalyzed dehydration was then evaluated. The acid stability of BMS-779788-Me confirmed that the heterocyclic core contributes to reactivity liability of the tertiary hydroxyl. PMID:26921118

  8. Dehydration and Stabilization of a Reactive Tertiary Hydroxyl Group in Solid Oral Dosage Forms of BMS-779788.

    PubMed

    Adams, Monica L; Sharma, Vijayata; Gokhale, Madhushree; Huang, Yande; Stefanski, Kevin; Su, Ching; Hussain, Munir A

    2016-04-01

    BMS-779788 contains a reactive tertiary hydroxyl attached to a weakly basic imidazole ring. Propensity of the carbinol toward dehydration to yield the corresponding alkene, BMS-779788-ALK, was evaluated. Elevated levels of BMS-779788-ALK were observed in excipient compatibility samples. Stability studies revealed that BMS-779788 degrades to BMS-779788-ALK in capsules and tablets prepared by both dry and wet granulation processes. An acid-catalyzed dehydration mechanism, in which the heterocyclic core contributes resonance stability to the cationic intermediate via charge transfer to the imidazole ring, was proposed. Therefore, neutralization via a buffered (pH 7.0) granulating solution was used to mitigate dehydration. Solution studies revealed degradation of BMS-779788 to BMS-779788-ALK over the pH range of 1-7.5. Reversibility was confirmed by initiating reactions with BMS-779788-ALK over the same pH range. Accordingly, a simple reversible scheme can be used to describe reactions initiated with either BMS-779788 or BMS-779788-ALK. To eliminate potential for charge delocalization across the heterocycle and probe the degradation mechanism, the imidazole ring of BMS-779788 was methylated (BMS-779788-Me). The propensity for acid-catalyzed dehydration was then evaluated. The acid stability of BMS-779788-Me confirmed that the heterocyclic core contributes to reactivity liability of the tertiary hydroxyl.

  9. Population Signatures in Planetary Nebulae from Abundances of Fe-group and Neutron-Capture Elements

    NASA Astrophysics Data System (ADS)

    Dinerstein, Harriet L.; Geballe, Thomas R.; Sterling, N. C.

    2015-08-01

    There are two categories of elements for which abundances are measured in planetary nebulae (PNe). The first are species whose abundances may be modified by nuclear reactions in the star prior to PN formation, such as He, C, N, and nuclei made by slow neutron captures (Karakas & Lattanzio 2014, PASA, 31, 30). In contrast, elements unaffected by evolution should indicate the star’s initial composition. These include S, Ar, Cl, and (with certain exceptions) O and Ne, most of which are alpha species. A long-missing piece of the puzzle has been the abundances of the Fe-group elements. We cannot determine a meaningful elemental abundance from the gas-phase Fe lines seen in PNe, since Fe is heavily depleted into dust. Another approach is to use a different element as a proxy for Fe. Dinerstein & Geballe (2001, ApJ, 562, 515) identified a line at 3.625 μm as due to Zn, the least refractory Fe-group element. Observations of this line in Milky Way PNe yield -1 ≤ [Zn/H] ≤ 0 (Smith, Zijlstra, & Dinerstein 2014, MNRAS, 441, 3161; Dinerstein et al. 2015, in preparation). Substituting Zn for Fe, PNe can be placed in the [alpha/Fe] vs. [Fe/H] diagram used to characterize stellar populations. Dividing our sample into probable thin and thick disk members using the kinematic criterion of Peimbert’s Type II and III classes (1978, IAU Symp. 76, 215), we find that they occupy similar regions in [alpha/Fe] vs. [Fe/H] phase space as the stars of those populations. Elevated [alpha/Fe] values at subsolar [Fe/H], which tend to be higher for thick than thin disk PNe, cause degeneracies that make alpha species ambiguous metallicity indicators. This is important for self-enrichment studies, since if the initial abundance of an element is lower than projected from an alpha species, internal synthesis may be required to produce even a solar final abundance. Low observed abundances of the n-capture element Se suggest that many Type III PNe may have subsolar initial abundances of n

  10. Preparation of hydroxylated polyethylene surfaces.

    PubMed

    Zand, A; Walter, N; Bahu, M; Ketterer, S; Sanders, M; Sikorski, Y; Cunningham, R; Beholz, L

    2008-01-01

    The surfaces of high-density or ultra-high-molecular-weight polyethylenes were hydroxylated using a two-step process. The wetting and wear properties of the untreated (virgin) and surface hydroxylated polyethylenes were compared. The introduction of hydroxyl groups provided an increase in surface hydrophilicity resulting in reduced wear. Hydrophilicity was analyzed by optical analysis of water contact angle. Wear was determined by weight loss under conditions of a reciprocating pin-on-plate apparatus with the panels immersed in water or calf serum. These results suggest that hydroxylation of polyethylene friction-bearing orthopedic surfaces may lead to a longer joint life. PMID:18318959

  11. Variation in optoelectronic properties of azo dye-sensitized TiO2 semiconductor interfaces with different adsorption anchors: carboxylate, sulfonate, hydroxyl and pyridyl groups.

    PubMed

    Zhang, Lei; Cole, Jacqueline M; Dai, Chencheng

    2014-05-28

    The optoelectronic properties of four azo dye-sensitized TiO2 interfaces are systematically studied as a function of a changing dye anchoring group: carboxylate, sulfonate, hydroxyl, and pyridyl. The variation in optoelectronic properties of the free dyes and those in dye/TiO2 nanocomposites are studied both experimentally and computationally, in the context of prospective dye-sensitized solar cell (DSSC) applications. Experimental UV/vis absorption spectroscopy, cyclic voltammetry, and DSSC device performance testing reveal a strong dependence on the nature of the anchor of the optoelectronic properties of these dyes, both in solution and as dye/TiO2 nanocomposites. First-principles calculations on both an isolated dye/TiO2 cluster model (using localized basis sets) and each dye modeled onto the surface of a 2D periodic TiO2 nanostructure (using plane wave basis sets) are presented. Detailed examination of these experimental and computational results, in terms of light harvesting, electron conversion and photovoltaic device performance characteristics, indicates that carboxylate is the best anchoring group, and hydroxyl is the worst, whereas sulfonate and pyridyl groups exhibit competing potential. Different sensitization solvents are found to affect critically the extent of dye adsorption achieved in the dye-sensitization of the TiO2 semiconductor, especially where the anchor is a pyridyl group.

  12. Chemical engineering of the peptidyl transferase center reveals an important role of the 2′-hydroxyl group of A2451

    PubMed Central

    Erlacher, Matthias D.; Lang, Kathrin; Shankaran, Nisha; Wotzel, Brigitte; Hüttenhofer, Alexander; Micura, Ronald; Mankin, Alexander S.; Polacek, Norbert

    2005-01-01

    The main enzymatic reaction of the large ribosomal subunit is peptide bond formation. Ribosome crystallography showed that A2451 of 23S rRNA makes the closest approach to the attacking amino group of aminoacyl-tRNA. Mutations of A2451 had relatively small effects on transpeptidation and failed to unequivocally identify the crucial functional group(s). Here, we employed an in vitro reconstitution system for chemical engineering the peptidyl transferase center by introducing non-natural nucleosides at position A2451. This allowed us to investigate the peptidyl transfer reaction performed by a ribosome that contained a modified nucleoside at the active site. The main finding is that ribosomes carrying a 2′-deoxyribose at A2451 showed a compromised peptidyl transferase activity. In variance, adenine base modifications and even the removal of the entire nucleobase at A2451 had only little impact on peptide bond formation, as long as the 2′-hydroxyl was present. This implicates a functional or structural role of the 2′-hydroxyl group at A2451 for transpeptidation. PMID:15767286

  13. The Hydroxyl at Position C1 of Genipin Is the Active Inhibitory Group that Affects Mitochondrial Uncoupling Protein 2 in Panc-1 Cells

    PubMed Central

    Hou, Jianwei; Ding, Yue; Zhang, Tong; Zhang, Yong; Wang, Jianying; Shi, Chenchen; Fu, Wenwei; Cai, Zhenzhen

    2016-01-01

    Genipin (GNP) effectively inhibits uncoupling protein 2 (UCP2), which regulates the leakage of protons across the inner mitochondrial membrane. UCP2 inhibition may induce pancreatic adenocarcinoma cell death by increasing reactive oxygen species (ROS) levels. In this study, the hydroxyls at positions C10 (10-OH) and C1 (1-OH) of GNP were hypothesized to be the active groups that cause these inhibitory effects. Four GNP derivatives in which the hydroxyl at position C10 or C1 was replaced with other chemical groups were synthesized and isolated. Differences in the inhibitory effects of GNP and its four derivatives on pancreatic carcinoma cell (Panc-1) proliferation were assessed. The effects of GNP and its derivatives on apoptosis, UCP2 inhibition and ROS production were also studied to explore the relationship between GNP’s activity and its structure. The derivatives with 1-OH substitutions, geniposide (1-GNP1) and 1-ethyl-genipin (1-GNP2) lacked cytotoxic effects, while the other derivatives that retained 1-OH, 10-piv-genipin (10-GNP1) and 10-acetic acid-genipin (10-GNP2) exerted biological effects similar to those of GNP, even in the absence of 10-OH. Thus, 1-OH is the key functional group in the structure of GNP that is responsible for GNP’s apoptotic effects. These cytotoxic effects involve the induction of Panc-1 cell apoptosis through UCP2 inhibition and subsequent ROS production. PMID:26771380

  14. The Hydroxyl at Position C1 of Genipin Is the Active Inhibitory Group that Affects Mitochondrial Uncoupling Protein 2 in Panc-1 Cells.

    PubMed

    Yang, Yang; Yang, Yifu; Hou, Jianwei; Ding, Yue; Zhang, Tong; Zhang, Yong; Wang, Jianying; Shi, Chenchen; Fu, Wenwei; Cai, Zhenzhen

    2016-01-01

    Genipin (GNP) effectively inhibits uncoupling protein 2 (UCP2), which regulates the leakage of protons across the inner mitochondrial membrane. UCP2 inhibition may induce pancreatic adenocarcinoma cell death by increasing reactive oxygen species (ROS) levels. In this study, the hydroxyls at positions C10 (10-OH) and C1 (1-OH) of GNP were hypothesized to be the active groups that cause these inhibitory effects. Four GNP derivatives in which the hydroxyl at position C10 or C1 was replaced with other chemical groups were synthesized and isolated. Differences in the inhibitory effects of GNP and its four derivatives on pancreatic carcinoma cell (Panc-1) proliferation were assessed. The effects of GNP and its derivatives on apoptosis, UCP2 inhibition and ROS production were also studied to explore the relationship between GNP's activity and its structure. The derivatives with 1-OH substitutions, geniposide (1-GNP1) and 1-ethyl-genipin (1-GNP2) lacked cytotoxic effects, while the other derivatives that retained 1-OH, 10-piv-genipin (10-GNP1) and 10-acetic acid-genipin (10-GNP2) exerted biological effects similar to those of GNP, even in the absence of 10-OH. Thus, 1-OH is the key functional group in the structure of GNP that is responsible for GNP's apoptotic effects. These cytotoxic effects involve the induction of Panc-1 cell apoptosis through UCP2 inhibition and subsequent ROS production.

  15. The effect of ethanol on hydroxyl and carbonyl groups in biopolyol produced by hydrothermal liquefaction of loblolly pine: (31)P-NMR and (19)F-NMR analysis.

    PubMed

    Celikbag, Yusuf; Via, Brian K; Adhikari, Sushil; Buschle-Diller, Gisela; Auad, Maria L

    2016-08-01

    The goal of this study was to investigate the role of ethanol and temperature on the hydroxyl and carbonyl groups in biopolyol produced from hydrothermal liquefaction of loblolly pine (Pinus spp.) carried out at 250, 300, 350 and 390°C for 30min. Water and water/ethanol mixture (1/1, wt/wt) were used as liquefying solvent in the HTL experiments. HTL in water and water/ethanol is donated as W-HTL and W/E-HTL, respectively. It was found that 300°C and water/ethanol solvent was the optimum liquefaction temperature and solvent, yielding up to 68.1wt.% bio-oil and 2.4wt.% solid residue. (31)P-NMR analysis showed that biopolyol produced by W-HTL was rich in phenolic OH while W/E-HTL produced more aliphatic OH rich biopolyols. Moreover, biopolyols with higher hydroxyl concentration were produced by W/E-HTL. Carbonyl groups were analyzed by (19)F-NMR, which showed that ethanol reduced the concentration of carbonyl groups. PMID:27126078

  16. The effect of ethanol on hydroxyl and carbonyl groups in biopolyol produced by hydrothermal liquefaction of loblolly pine: (31)P-NMR and (19)F-NMR analysis.

    PubMed

    Celikbag, Yusuf; Via, Brian K; Adhikari, Sushil; Buschle-Diller, Gisela; Auad, Maria L

    2016-08-01

    The goal of this study was to investigate the role of ethanol and temperature on the hydroxyl and carbonyl groups in biopolyol produced from hydrothermal liquefaction of loblolly pine (Pinus spp.) carried out at 250, 300, 350 and 390°C for 30min. Water and water/ethanol mixture (1/1, wt/wt) were used as liquefying solvent in the HTL experiments. HTL in water and water/ethanol is donated as W-HTL and W/E-HTL, respectively. It was found that 300°C and water/ethanol solvent was the optimum liquefaction temperature and solvent, yielding up to 68.1wt.% bio-oil and 2.4wt.% solid residue. (31)P-NMR analysis showed that biopolyol produced by W-HTL was rich in phenolic OH while W/E-HTL produced more aliphatic OH rich biopolyols. Moreover, biopolyols with higher hydroxyl concentration were produced by W/E-HTL. Carbonyl groups were analyzed by (19)F-NMR, which showed that ethanol reduced the concentration of carbonyl groups.

  17. Archaea of the Miscellaneous Crenarchaeotal Group are abundant, diverse and widespread in marine sediments

    PubMed Central

    Kubo, Kyoko; Lloyd, Karen G; F Biddle, Jennifer; Amann, Rudolf; Teske, Andreas; Knittel, Katrin

    2012-01-01

    Members of the highly diverse Miscellaneous Crenarchaeotal Group (MCG) are globally distributed in various marine and continental habitats. In this study, we applied a polyphasic approach (rRNA slot blot hybridization, quantitative PCR (qPCR) and catalyzed reporter deposition FISH) using newly developed probes and primers for the in situ detection and quantification of MCG crenarchaeota in diverse types of marine sediments and microbial mats. In general, abundance of MCG (cocci, 0.4 μm) relative to other archaea was highest (12–100%) in anoxic, low-energy environments characterized by deeper sulfate depletion and lower microbial respiration rates (P=0.06 for slot blot and P=0.05 for qPCR). When studied in high depth resolution in the White Oak River estuary and Hydrate Ridge methane seeps, changes in MCG abundance relative to total archaea and MCG phylogenetic composition did not correlate with changes in sulfate reduction or methane oxidation with depth. In addition, MCG abundance did not vary significantly (P>0.1) between seep sites (with high rates of methanotrophy) and non-seep sites (with low rates of methanotrophy). This suggests that MCG are likely not methanotrophs. MCG crenarchaeota are highly diverse and contain 17 subgroups, with a range of intragroup similarity of 82 to 94%. This high diversity and widespread distribution in subsurface sediments indicates that this group is globally important in sedimentary processes. PMID:22551871

  18. The Measurement of Iron-Group Isotopic Abundances in the Cosmic Rays Using the Magpie Detector

    NASA Astrophysics Data System (ADS)

    Yanasak, Nathan Eugene

    This thesis details the analysis of data from the MAGPIE detector, a balloon-borne detector designed to measure cosmic ray isotope abundances between 300 and 900 MeV/a μ in the Fe group. MAGPIE consists of a magnetic spectrometer for measuring particle rigidity, and nine stacks of CR-39 plastic nuclear track detectors for measuring charge and velocity. After an Antarctic flight in December of 1991 during which ~2000 Fe nuclei were collected, damage occurred to the spectrometer during the landing of the balloon payload, limiting the analysis to cosmic ray particles that stop in the plastic stack. This limited the energy range of data to between 100 MeV/a μ and 400 MeV/a μ for Fe group elements. The measurement of Fe group isotopes is an important one. Because nuclei from this group have the highest binding energy of all the elements, they represent the primary products during late stellar nucleosynthesis. This characteristic makes Fe group isotopes unique in their ability to probe the interior environment during the final stages of stellar evolution. In addition, the primary decay channel by e- capture for some of the Ni and Co isotopes makes these isotopes ideal for probing the time delay between production of cosmic rays and their acceleration. Finally, the radioactive isotope 54Mn has a mean lifetime that is comparable to residence time of lighter elements in the galaxy, which has been measured using the 10Be isotopic abundance. Both of these abundances are produced primarily through spallation during propagation, and Mn can measure the average density of the propagation medium and residence time for Fe group elements with isotopic abundance measurements of stable spallation products. After etching, the MAGPIE CR-39 plastic was scanned for tracks using an automated microscope and image processing system. This system offers a data acquisition method that is as efficient and much quicker than techniques using a microscope and reticle. Cosmic ray data were

  19. Mechanistic Insights of Ethanol Steam Reforming over Ni–CeO x (111): The Importance of Hydroxyl Groups for Suppressing Coke Formation

    DOE PAGES

    Liu, Zongyuan; Duchoň, Tomáš; Wang, Huanru; Peterson, Erik W.; Zhou, Yinghui; Luo, Si; Zhou, Jing; Matolín, Vladimir; Stacchiola, Dario J.; Rodriguez, José A.; et al

    2015-07-30

    We have studied the reaction of ethanol and water over Ni–CeO2-x(111) model surfaces to elucidate the mechanistic steps associated with the ethanol steam reforming (ESR) reaction. Our results provide insights about the importance of hydroxyl groups to the ESR reaction over Ni-based catalysts. Systematically, we have investigated the reaction of ethanol on Ni–CeO2-x(111) at varying Ce³⁺ concentrations (CeO1.8–2.0) with absence/presence of water using a combination of soft X-ray photoelectron spectroscopy (sXPS) and temperature-programmed desorption (TPD). Consistent with previous reports, upon annealing, metallic Ni formed on reduced ceria while NiO was the main component on fully oxidized ceria. Ni⁰ is themore » active phase leading to both the C–C and C–H cleavage of ethanol but is also responsible for carbon accumulation or coking. We have identified a Ni₃C phase that formed prior to the formation of coke. At temperatures above 600K, the lattice oxygen from ceria and the hydroxyl groups from water interact cooperatively in the removal of coke, likely through a strong metal–support interaction between nickel and ceria that facilitates oxygen transfer.« less

  20. Preferential adsorption behavior of methylene blue dye onto surface hydroxyl group enriched TiO2 nanotube and its photocatalytic regeneration.

    PubMed

    Natarajan, Thillai Sivakumar; Bajaj, Hari C; Tayade, Rajesh J

    2014-11-01

    The present manuscript focus on the synthesis of surface hydroxyl group enriched titanium dioxide nanotube (TNT) by hydrothermal method for preferential adsorption of methylene blue (MB) dye. The mixture of methylene blue (MB) and rhodamine B (RhB) dye was used to study the preferential adsorption nature of TNT. The synthesized TNT were characterized by various techniques such as powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N2 adsorption, and ammonia-temperature programmed desorption (NH3-TPD) analysis. Result demonstrated that enhancement in the surface area of TNT and higher number of hydroxyl group on the surface of TNT. In the binary mixture, the adsorption of MB dye was 12.9 times higher as compared to RhB dye, which clearly indicated the preferential adsorption of MB dye on TNT surface. The preferential interaction of MB on TNT is due to the electrostatic interaction between the cationic MB and negatively charged TNT surface. The preferential adsorption of MB dye was studied by applying Langmuir, Freundlich and Sips isotherm; pseudo-first and second-order kinetic model. Furthermore, the regeneration of dye adsorbed TNT was carried out by eco-friendly photocatalytic process under the irradiation of ultraviolet light.

  1. Mechanistic Insights of Ethanol Steam Reforming over Ni–CeO x (111): The Importance of Hydroxyl Groups for Suppressing Coke Formation

    SciTech Connect

    Liu, Zongyuan; Duchoň, Tomáš; Wang, Huanru; Peterson, Erik W.; Zhou, Yinghui; Luo, Si; Zhou, Jing; Matolín, Vladimir; Stacchiola, Dario J.; Rodriguez, José A.; Senanayake, Sanjaya D.

    2015-07-30

    We have studied the reaction of ethanol and water over Ni–CeO2-x(111) model surfaces to elucidate the mechanistic steps associated with the ethanol steam reforming (ESR) reaction. Our results provide insights about the importance of hydroxyl groups to the ESR reaction over Ni-based catalysts. Systematically, we have investigated the reaction of ethanol on Ni–CeO2-x(111) at varying Ce³⁺ concentrations (CeO1.8–2.0) with absence/presence of water using a combination of soft X-ray photoelectron spectroscopy (sXPS) and temperature-programmed desorption (TPD). Consistent with previous reports, upon annealing, metallic Ni formed on reduced ceria while NiO was the main component on fully oxidized ceria. Ni⁰ is the active phase leading to both the C–C and C–H cleavage of ethanol but is also responsible for carbon accumulation or coking. We have identified a Ni₃C phase that formed prior to the formation of coke. At temperatures above 600K, the lattice oxygen from ceria and the hydroxyl groups from water interact cooperatively in the removal of coke, likely through a strong metal–support interaction between nickel and ceria that facilitates oxygen transfer.

  2. Photo and Chemical Reduction of Copper onto Anatase-Type TiO2 Nanoparticles with Enhanced Surface Hydroxyl Groups as Efficient Visible Light Photocatalysts.

    PubMed

    Eskandarloo, Hamed; Badiei, Alireza; Behnajady, Mohammad A; Mohammadi Ziarani, Ghodsi

    2015-01-01

    In this study, the photocatalytic efficiency of anatase-type TiO2 nanoparticles synthesized using the sol-gel low-temperature method, were enhanced by a combined process of copper reduction and surface hydroxyl groups enhancement. UV-light-assisted photo and NaBH4 -assisted chemical reduction methods were used for deposition of copper onto TiO2. The surface hydroxyl groups of TiO2 were enhanced with the assistance of NaOH modification. The prepared catalysts were immobilized on glass plates and used as the fixed-bed systems for the removal of phenazopyridine as a model drug contaminant under visible light irradiation. NaOH-modified Cu/TiO2 nanoparticles demonstrated higher photocatalytic efficiency than that of pure TiO2 due to the extending of the charge carriers lifetime and enhancement of the adsorption capacity of TiO2 toward phenazopyridine. The relationship of structure and performance of prepared nanoparticles has been established by using various techniques, such as XRD, XPS, TEM, EDX, XRF, TGA, DRS and PL. The effects of preparation variables, including copper content, reducing agents rate (NaBH4 concentration and UV light intensity) and NaOH concentration were investigated on the photocatalytic efficiency of NaOH-modified Cu/TiO2 nanoparticles.

  3. Hydroxyl speciation in felsic magmas

    NASA Astrophysics Data System (ADS)

    Malfait, Wim J.; Xue, Xianyu

    2014-09-01

    The hydroxyl speciation of hydrous, metaluminous potassium and calcium aluminosilicate glasses was investigated by 27Al-1H cross polarization and quantitative 1H MAS NMR spectroscopy. Al-OH is present in both the potassium and the calcium aluminosilicate glasses and its 1H NMR partial spectrum was derived from the 27Al-1H cross polarization data. For the calcium aluminosilicate glasses, the abundance of Al-OH could not be determined because of the low spectral resolution. For the potassium aluminosilicate glasses, the fraction of Al-OH was quantified by fitting its partial spectrum to the quantitative 1H NMR spectra. The degree of aluminum avoidance and the relative tendency for Si-O-Si, Si-O-Al and Al-O-Al bonds to hydrolyze were derived from the measured species abundances. Compared to the sodium, lithium and calcium systems, potassium aluminosilicate glasses display a much stronger degree of aluminum avoidance and a stronger tendency for the Al-O-Al linkages to hydrolyze. Combining our results with those for sodium aluminosilicate glasses (Malfait and Xue, 2010a), we predict that the hydroxyl groups in rhyolitic and phonolitic magmas are predominantly present as Si-OH (84-89% and 68-78%, respectively), but with a significant fraction of Al-OH (11-16% and 22-32%, respectively). For both rhyolitic and phonolitic melts, the AlOH/(AlOH + SiOH) ratio is likely smaller than the Al/(Al + Si) ratio for the lower end of the natural temperature range but may approach the Al/(Al + Si) ratio at higher temperatures.

  4. Hemiacetal stabilization in a chymotrypsin inhibitor complex and the reactivity of the hydroxyl group of the catalytic serine residue of chymotrypsin.

    PubMed

    Cleary, Jennifer A; Doherty, William; Evans, Paul; Malthouse, J Paul G

    2014-06-01

    The aldehyde inhibitor Z-Ala-Ala-Phe-CHO has been synthesized and shown by (13)C-NMR to react with the active site serine hydroxyl group of alpha-chymotrypsin to form two diastereomeric hemiacetals. For both hemiacetals oxyanion formation occurs with a pKa value of ~7 showing that chymotrypsin reduces the oxyanion pKa values by ~5.6 pKa units and stabilizes the oxyanions of both diastereoisomers by ~32kJmol(-1). As pH has only a small effect on binding we conclude that oxyanion formation does not have a significant effect on binding the aldehyde inhibitor. By comparing the binding of Z-Ala-Ala-Phe-CHO with that of Z-Ala-Ala-Phe-H we estimate that the aldehyde group increases binding ~100 fold. At pH7.2 the effective molarity of the active site serine hydroxy group is ~6000 which is ~7× less effective than with the corresponding glyoxal inhibitor. Using (1)H-NMR we have shown that at both 4 and 25°C the histidine pKa is ~7.3 in free chymotrypsin and it is raised to ~8 when Z-Ala-Ala-Phe-CHO is bound. We conclude that oxyanion formation only has a minor role in raising the histidine pKa and that the aldehyde hydrogen must be replaced by a larger group to raise the histidine pKa>10 and give stereospecific formation of tetrahedral intermediates. The results show that a large increase in the pKa of the active site histidine is not needed for the active site serine hydroxyl group to have an effective molarity of 6000.

  5. Soil type-dependent responses to phenanthrene as revealed by determining the diversity and abundance of polycyclic aromatic hydrocarbon ring-hydroxylating dioxygenase genes by using a novel PCR detection system.

    PubMed

    Ding, Guo-Chun; Heuer, Holger; Zühlke, Sebastian; Spiteller, Michael; Pronk, Geertje Johanna; Heister, Katja; Kögel-Knabner, Ingrid; Smalla, Kornelia

    2010-07-01

    A novel PCR primer system that targets a wide range of polycyclic aromatic hydrocarbon ring-hydroxylating dioxygenase (PAH-RHD(alpha)) genes of both Gram-positive and Gram-negative bacteria was developed and used to study their abundance and diversity in two different soils in response to phenanthrene spiking. The specificities and target ranges of the primers predicted in silico were confirmed experimentally by cloning and sequencing of PAH-RHD(alpha) gene amplicons from soil DNA. Cloning and sequencing showed the dominance of phnAc genes in the contaminated Luvisol. In contrast, high diversity of PAH-RHD(alpha) genes of Gram-positive and Gram-negative bacteria was observed in the phenanthrene-spiked Cambisol. Quantitative real-time PCR based on the same primers revealed that 63 days after phenanthrene spiking, PAH-RHD(alpha) genes were 1 order of magnitude more abundant in the Luvisol than in the Cambisol, while they were not detected in both control soils. In conclusion, sequence analysis of the amplicons obtained confirmed the specificity of the novel primer system and revealed a soil type-dependent response of PAH-RHD(alpha) gene-carrying soil bacteria to phenanthrene spiking.

  6. Life strategies of a ubiquitous and abundant subsurface archaeal group Bathyarchaeota

    NASA Astrophysics Data System (ADS)

    He, Y.; Li, M.; Perumal, V.; Feng, X.; Sievert, S. M.; Wang, F.

    2015-12-01

    Archaea belonging to the Miscellaneous Crenarchaeota Group (MCG, "Candidatus Bathyarchaeota") are widespread and abundant in the deep biosphere, yet their life strategies and ecological roles remain elusive. Metagenomic sequencing of a sample enriched in Bathyarchaeota (up to 74%) that originated from Guaymas Basin deep-sea vent sediments revealed 6 partial to nearly completed Bathyarchaeota genomic bins. ranging ~900kb-3.3Mb. The Bathyarchaeota bin size ranged from approximately 0.9 to 3.3 Mb, with coverage ranging from approximately 10× to 28×. The phylogeny based on 110 concatenated conserved archaeal single copy genes confirmed the placement of Bathyarchaeota into a novel archaeal phylum. Genes encoding for enzymes involved in the degradation of organic polymers such as protein, cellulose, chitin, and aromatic compounds, were identified. In addition, genes encoding glycolysis/gluconeogenesis, beta-oxidation pathways and the tricarboxylic acid cycle (except citrate synthase) were present in all genomic bins highlighting the heterotrophic life style of Bathyarchaeota. The presence of a wide variety of transporters of organic compounds further supports the versatile heterotrophic metabolism of Bathyarchaeota. This study highlights the life strategies of a ubiquitous and abundant subsurface archaeal group that thrives under energy-limited conditions, and expands the metabolic potentials of Archaea that play important roles in carbon cycling in marine sediments.

  7. Density and abundance of badger social groups in England and Wales in 2011-2013

    NASA Astrophysics Data System (ADS)

    Judge, Johanna; Wilson, Gavin J.; MacArthur, Roy; Delahay, Richard J.; McDonald, Robbie A.

    2014-01-01

    In the United Kingdom, European badgers Meles meles are a protected species and an important wildlife reservoir of bovine tuberculosis. We conducted a survey of badger dens (main setts) in 1614 1 km squares across England and Wales, between November 2011 and March 2013. Using main setts as a proxy for badger social groups, the estimated mean density of badger social groups in England and Wales was 0.485 km-2 (95% confidence interval 0.449-0.521) and the estimated abundance of social groups was 71,600 (66,400-76,900). In the 25 years since the first survey in 1985-88, the annual rate of increase in the estimated number of badger social groups was 2.6% (2.2-2.9%), equating to an 88% (70-105%) increase across England and Wales. In England, we estimate there has been an increase of 103% (83-123%) in badger social groups, while in Wales there has been little change (-25 to +49%).

  8. The effect of surfactant-free TiO2 surface hydroxyl groups on physicochemical, optical and self-cleaning properties of developed coatings on polycarbonate

    NASA Astrophysics Data System (ADS)

    Yaghoubi, H.; Dayerizadeh, A.; Han, S.; Mulaj, M.; Gao, W.; Li, X.; Muschol, M.; Ma, S.; Takshi, A.

    2013-12-01

    TiO2 is a prototypical transition metal oxide with physicochemical properties that can be modified more readily through sol-gel synthesis than through other techniques. Herein, we report on the change in the density of the hydroxyl groups on the surface of synthesized surfactant-free TiO2 nanoparticles in water due to varying the pH (7.3, 8.3, 9.3 and 10.3) of the peroxotitanium complex, i.e. the amorphous sol, prior to refluxing. This resulted in colloidal solutions with differing crystallinity, nanoparticle size, optical indirect bandgaps and photocatalytic activity. It was shown that increasing the density of hydroxyl groups on TiO2 particles coupled with low-temperature annealing (90 °C) induced an anatase to rutile transformation. Increasing the pH of the peroxotitanium complex interrupted the formation of anatase phase in crystalline sol, as evidenced by intensity increases of the Raman bands at ˜822 (Ti-O-H) and 906 cm-1 (vibrational Ti-O-H) and an intensity decrease of the band at 150 cm-1 (anatase photonic Eg). Films prepared from higher pH suspensions showed lower roughness. The reaction rate constants for photo-induced self-cleaning activity of TiO2 films prepared from colloidal solutions at pH 7.3, 8.3, 9.3 and 10.3 were estimated at 0.017 s-1, 0.014 s-1, 0.007 s-1 and 0.006 s-1, respectively.

  9. Infrared spectroscopy of OD vibrators in minerals at natural dilution: hydroxyl groups in talc and kaolinite, and structural water in beryl and emerald.

    PubMed

    de Donato, Philippe; Cheilletz, Alain; Barres, Odile; Yvon, Jacques

    2004-05-01

    An infrared (IR) study of natural deuteration is conducted on minerals containing hydroxyl groups (talc and kaolinite) and channel-water-bearing minerals (beryl and emerald). In talc, the OD valence vibration is located at 2710 cm(-1), corresponding to OD groups surrounded by 3 Mg atoms. In kaolinite, the OD valence vibrations are located at 2671 cm(-1) (inner OD group), 2712, 2706, and 2700 cm(-1) (three inner-surface OD groups). In beryl and emerald, natural deuteration of channel water is observed for the first time by infrared microspectroscopy. In beryl from Minas Gerais (Brazil), the OD profiles are characterized by four bands at 2735, 2686, 2672, and 2641 cm(-1). In emeralds from Colombia and Brazil, the OD profiles are characterized by five or four bands, respectively, at 2816, 2737, 2685, 2673, and 2641 cm(-1) (Colombia) and 2730, 2684, 2672, and 2640 cm(-1) (Brazil). The band at 2816 cm(-1) can be assigned to -OD or OD(-), and bands at 2686-2684, 2673-2672, and 2641-2640 cm(-1) can be assigned to type-I and type-II HOD molecules. The band at 2737-2730 cm(-1) is partially disturbed by combination bands of the mineral. Such OD profiles are different from those obtained by artificial deuteration at higher OD dilution. PMID:15165327

  10. Infrared spectroscopy of OD vibrators in minerals at natural dilution: hydroxyl groups in talc and kaolinite, and structural water in beryl and emerald.

    PubMed

    de Donato, Philippe; Cheilletz, Alain; Barres, Odile; Yvon, Jacques

    2004-05-01

    An infrared (IR) study of natural deuteration is conducted on minerals containing hydroxyl groups (talc and kaolinite) and channel-water-bearing minerals (beryl and emerald). In talc, the OD valence vibration is located at 2710 cm(-1), corresponding to OD groups surrounded by 3 Mg atoms. In kaolinite, the OD valence vibrations are located at 2671 cm(-1) (inner OD group), 2712, 2706, and 2700 cm(-1) (three inner-surface OD groups). In beryl and emerald, natural deuteration of channel water is observed for the first time by infrared microspectroscopy. In beryl from Minas Gerais (Brazil), the OD profiles are characterized by four bands at 2735, 2686, 2672, and 2641 cm(-1). In emeralds from Colombia and Brazil, the OD profiles are characterized by five or four bands, respectively, at 2816, 2737, 2685, 2673, and 2641 cm(-1) (Colombia) and 2730, 2684, 2672, and 2640 cm(-1) (Brazil). The band at 2816 cm(-1) can be assigned to -OD or OD(-), and bands at 2686-2684, 2673-2672, and 2641-2640 cm(-1) can be assigned to type-I and type-II HOD molecules. The band at 2737-2730 cm(-1) is partially disturbed by combination bands of the mineral. Such OD profiles are different from those obtained by artificial deuteration at higher OD dilution.

  11. Differential Abundance of Microbial Functional Groups along the Elevation Gradient from the Coast to the Luquillo Mountains

    EPA Science Inventory

    Microbial communities respond to multiple abiotic and biotic factors that change along elevation gradients. We compare changes in microbial community composition in soil and review previous research on differential abundance of microbial functional groups along an elevation gradi...

  12. The Effect of Methyl, Hydroxyl, and Ketone Functional Groups on the Heterogeneous Oxidation of Succinic Acid Aerosol by OH Radicals

    NASA Astrophysics Data System (ADS)

    Chan, M.; Zhang, H.; Wilson, K. R.

    2013-12-01

    The heterogeneous oxidation of atmospheric organic aerosols can influence their effects on climate, human health, and visibility. During oxidation, functionalization occurs when an oxygenated functional group is added to a molecule, leaving the carbon skeleton intact. Fragmentation involves carbon-carbon bond cleavage and produces two products with smaller carbon numbers than the parent compound. To gain better insights into how the molecular structure of more oxygenated organic compounds affects heterogeneous reactivity, succinic acid aerosols are photo-oxidized in an aerosol flow tube reactor, and the reaction products are analyzed using Direct Analysis in Real Time Mass Spectrometry for online chemical analysis. The effect of various functional groups (CH3, OH, C=O) along the carbon backbone on the heterogeneous reaction mechanisms are also investigated using model compounds. For this series of compounds, the formation of more oxygenated products through functionalization can be explained by well-known condensation-phase reactions such as Russell and Bennett and Summers. The number of fragmentation products is found to increase with the presence of OH and CH3 groups. This can be attributed to the increased number of tertiary carbons, enhancing the fragmentation after multiple oxidation steps. Smaller dicaids (oxalic acid and malonic acid) can be formed through the fragmentation processes in the heterogeneous oxidation of succinic acid. The effect of molecular structure on reaction kinetics, volatilization, and the relative importance of functionalization and fragmentation pathways will be discussed.

  13. Adsorption and desorption of DNA tuned by hydroxyl groups in graphite oxides-based solid extraction material.

    PubMed

    Akceoglu, Garbis Atam; Li, Oi Lun; Saito, Nagahiro

    2015-12-01

    The extraction of DNA is the most crucial method used in molecular biology. Up to date silica matrices has been widely applied as solid support for selective DNA adsorption and extraction. However, since adsorption force of SiOH functional groups is much greater than that of desorption force, the DNA extraction efficiency of silica surfaces is limited. In order to increase the DNA extraction yield, a new surface with different functional groups which possess of greater desorption property is required. In this study, we proposed cellulose/graphite oxide (GO) composite as an alternative material for DNA adsorption and extraction. GO/Cellulose composite provides the major adsorption and desorption of DNA by COH, which belongs to alkyl or phenol type of OH functional group. Compared to SiOH, COH is less polarized and reactive, therefore the composite might provide a higher desorption of DNA during the elution process. The GO/cellulose composite were prepared in spherical structure by mixing urea, cellulose, NaOH, Graphite oxide and water. The concentration of GO within the composites were controlled to be 0-4.15 wt.%. The extraction yield of DNA increased with increasing weight percentage of GO. The highest yield was achieved at 4.15 wt.% GO, where the extraction efficiency was reported as 660.4 ng/μl when applying 2M GuHCl as the binding buffer. The absorbance ratios between 260 nm and 280 nm (A260/A280) of the DNA elution was demonstrated as 1.86, indicating the extracted DNA consisted of high purity. The results proved that GO/cellulose composite provides a simple method for selective DNA extraction with high extraction efficiency of pure DNA.

  14. Synthesis and evaluation of antibacterial polyurethane coatings made from soybean oil functionalized with dimethylphenylammonium iodide and hydroxyl groups.

    PubMed

    Bakhshi, Hadi; Yeganeh, Hamid; Mehdipour-Ataei, Shahram

    2013-06-01

    Preparation of antibacterial polyurethane coatings from novel functional soybean oil was considered in this work. First, epoxidized soybean oil (ESBO) as a low price and widely available renewable resource raw material was subjected to the reaction with aniline using an ionic liquid as a green catalyst. The intermediate phenylamine containing polyol (SAP) was then methylated by reaction with methyl iodide to produce a polyol (QAP) with pendant dimethylphenylammonium iodide groups. To regulate the physical and mechanical properties as well as biological characteristics of final coatings, QAP was mixed with different portions of a similar soybean oil-based polyol (MSP) without quaternary ammonium groups. The mixtures were reacted with isophorone diisocyanate to produce crosslinked polyurethane coatings. Evaluation of viscoelastic properties by DMA method revealed single phase structure with Tg in the range of 50-82°C. Stress-strain analysis of the prepared polyurethanes showed initial modulus, tensile strength, and elongation at break in the ranges of 13-299 MPa, 4.5-13.8 MPa, and 16-109%, respectively. Additionally, the coatings showed good adherence to aluminum and PVC substrates. The solvent extracted samples showed excellent biocompatibility as determined by monitoring L929 fibroblast cells morphology and MTT assay. Meanwhile, very promising antibacterial properties against both Gram-positive (S. aureus) and Gram-negative (E. coli) bacteria with bacterial reduction in the range of 83-100% was observed. PMID:23172859

  15. Infrared study of the interaction between Lewis bases and surface hydroxyl groups of {Pt}/{Cab-O-Sil}

    NASA Astrophysics Data System (ADS)

    Sárkány, János

    1997-06-01

    Transmission IR spectroscopic study at 298 K has revealed strong H-bonds between Lewis bases (LBs) containing one, [1-O], or two, [2-O], sp 3 hybridized O atoms and the surface OH groups of Cab-O-Sil. LB [1-O] (10 torr = 1.333 kPa) caused a greater | Δν(OH)| (470-520 cm -1) than did LB [2-O] (385-470 cm -1). In contrast with expectations, the intensity of the OH band at 3660 cm -1 decreased to a greater extent for LB [2-O] than for LB [1-O]. The results were interpreted on the basis of chargetransfer theory. The estimated sequence of electron-donating ability (EDA) was: oxepane > oxane > oxolane > diethyl ether ≥ 1,4-dioxane > 1,3-dioxepane > 1,3-dioxane > 1,3-dioxolane.

  16. Site-specific labeling of RNA at internal ribose hydroxyl groups: terbium-assisted deoxyribozymes at work.

    PubMed

    Büttner, Lea; Javadi-Zarnaghi, Fatemeh; Höbartner, Claudia

    2014-06-01

    A general and efficient single-step method was established for site-specific post-transcriptional labeling of RNA. Using Tb(3+) as accelerating cofactor for deoxyribozymes, various labeled guanosines were site-specifically attached to 2'-OH groups of internal adenosines in in vitro transcribed RNA. The DNA-catalyzed 2',5'-phosphodiester bond formation proceeded efficiently with fluorescent, spin-labeled, biotinylated, or cross-linker-modified guanosine triphosphates. The sequence context of the labeling site was systematically analyzed by mutating the nucleotides flanking the targeted adenosine. Labeling of adenosines in a purine-rich environment showed the fastest reactions and highest yields. Overall, practically useful yields >70% were obtained for 13 out of 16 possible nucleotide (nt) combinations. Using this approach, we demonstrate preparative labeling under mild conditions for up to ~160-nt-long RNAs, including spliceosomal U6 small nuclear RNA and a cyclic-di-AMP binding riboswitch RNA.

  17. The abundance and organization of polypeptides associated with antigens of the Rh blood group system.

    PubMed

    Gardner, B; Anstee, D J; Mawby, W J; Tanner, M J; von dem Borne, A E

    1991-06-01

    Twelve murine monoclonal antibodies, which react with human red cells of common Rh phenotype but give weak or negative reactions with Rh null erythrocytes, were used in quantitative binding assays and competitive binding assays to investigate the abundance and organization of polypeptides involved in the expression of antigens of the Rh blood group system. Antibodies of the R6A-type (R6A, BRIC-69, BRIC-207) and the 2D10-type (MB-2D10, LA18.18, LA23.40) recognize related structures and 100,000-200,000 molecules of each antibody bind maximally to erythrocytes of common Rh phenotype. Antibodies of the BRIC-125 type (BRICs 32, 122, 125, 126, 168, 211) recognize structures that are unrelated to those recognized by R6A-type and 2D10-type antibodies and between 10,000 and 50,000 antibody molecules bind maximally to erythrocytes of the common Rh phenotype. The binding of antibodies of the R6A-type and the 2D10-type, but not of antibodies of the BRIC-125-type could be partially inhibited by human anti-D antibodies (polyclonal and monoclonal) and a murine anti-e-like antibody. These results are consistent with evidence (Moore & Green 1987; Avent et al., 1988b) that the Rh blood group antigens are associated with a complex that comprises two groups of related polypeptides of M(r) 30,000 and M(r) 35,000-100,000, respectively, and suggest that there are 1-2 x 10(5) copies of this complex per erythrocyte. The polypeptide recognized by antibodies of the BRIC-125 type is likely to be associated with this complex. PMID:9259831

  18. The abundance and organization of polypeptides associated with antigens of the Rh blood group system.

    PubMed

    Gardner, B; Anstee, D J; Mawby, W J; Tanner, M J; von dem Borne, A E

    1991-06-01

    Twelve murine monoclonal antibodies, which react with human red cells of common Rh phenotype but give weak or negative reactions with Rh null erythrocytes, were used in quantitative binding assays and competitive binding assays to investigate the abundance and organization of polypeptides involved in the expression of antigens of the Rh blood group system. Antibodies of the R6A-type (R6A, BRIC-69, BRIC-207) and the 2D10-type (MB-2D10, LA18.18, LA23.40) recognize related structures and 100,000-200,000 molecules of each antibody bind maximally to erythrocytes of common Rh phenotype. Antibodies of the BRIC-125 type (BRICs 32, 122, 125, 126, 168, 211) recognize structures that are unrelated to those recognized by R6A-type and 2D10-type antibodies and between 10,000 and 50,000 antibody molecules bind maximally to erythrocytes of the common Rh phenotype. The binding of antibodies of the R6A-type and the 2D10-type, but not of antibodies of the BRIC-125-type could be partially inhibited by human anti-D antibodies (polyclonal and monoclonal) and a murine anti-e-like antibody. These results are consistent with evidence (Moore & Green 1987; Avent et al., 1988b) that the Rh blood group antigens are associated with a complex that comprises two groups of related polypeptides of M(r) 30,000 and M(r) 35,000-100,000, respectively, and suggest that there are 1-2 x 10(5) copies of this complex per erythrocyte. The polypeptide recognized by antibodies of the BRIC-125 type is likely to be associated with this complex.

  19. Role of surface hydroxyl groups in promoting room temperature CO sensing by Pd-modified nanocrystalline SnO 2

    NASA Astrophysics Data System (ADS)

    Marikutsa, Artem V.; Rumyantseva, Marina N.; Yashina, Lada V.; Gaskov, Alexander M.

    2010-10-01

    SnO 2/Pd nanocomposites were synthesized via sol-gel method followed by variable processing procedures. The materials are sensitive to CO gas in the concentration range 2-100 ppm at room operating temperature. It was shown that modification of nanocrystalline tin dioxide by Pd changes the temperature dependence of sensor response, decreasing the temperature of maximal signal. To understand the mechanism of room temperature CO sensitivity, a number of SnO 2/Pd materials were characterized by XRD, TEM, BET, XPS and TPR techniques. From the results of FTIR, impedance and sensing measurements under variable ambient conditions it was concluded that improvement in CO sensitivity for Pd-modified SnO 2 is due to alteration of CO oxidation pathway. The reaction of CO with surface OH-groups at room temperature was proposed, the latter being more reactive than oxygen species due to the possible chain character of the reactions. It was proposed that Pd additive may initiate chain processes at room temperature.

  20. Novel relationship between hydroxyl radical initiation and surface group of ceramic honeycomb supported metals for the catalytic ozonation of nitrobenzene in aqueous solution.

    PubMed

    Zhao, Lei; Sun, Zhizhong; Ma, Jun

    2009-06-01

    Comparative experiments have been performed to investigate the degradation efficiency of nitrobenzene and the removal efficiency of TOC in aqueous solution bythe processes of ceramic honeycomb supported different metals (Fe, Ni, and Zn) catalytic ozonation, indicating that the modification with metals can enhance the activity of ceramic honeycomb for the catalytic ozonation of nitrobenzene, and the loading percentage of metal and the metallicity respectively presents a positive influence on the degradation of nitrobenzene. The degradation efficiency of nitrobenzene is determined by the initiation of hydroxyl radical (*OH) according to a good linear correlation in all the processes of modified ceramic honeycomb catalytic ozonation at the different loading percentages of metals. The modification of ceramic honeycomb with metals results in the conversion of the pH at the point of zero charge (pHpzc) and the evolution of surface groups. Divergence from the conventional phenomenon, the enhancement mechanism of ozone decomposition on the modified ceramic honeycomb with metals is proposed due to the basic attractive forces of electrostatic forces or/and hydrogen bonding. Consequently, a novel relationship between the initiation of *OH and the surface-OH2+ group on the modified catalyst is established based on the synergetic effect between homogeneous and heterogeneous reaction systems.

  1. Oxidation of primary hydroxyl groups in chitooligomer by a laccase-TEMPO system and physico-chemical characterisation of oxidation products.

    PubMed

    Pei, Jicheng; Yin, Yunbei; Shen, Zhenghui; Bu, Xin; Zhang, Fangdong

    2016-01-01

    The aim of this study was to investigate the oxidation of chitooligomer by a laccase-TEMPO system which had not previously been examined. Chitooligomer was treated with laccase and TEMPO in order to evaluate the potential of a laccase-TEMPO system to improve the moisture absorption, moisture retention, and antioxidant abilities of chitooligomer. Chitooligomer was prepared by degradation of high molecular weight chitosan with hydrogen peroxide followed by oxidation using a laccase-TEMPO system. (13)C NMR and carboxylate ion content detection results indicated that the laccase-TEMPO system could selectively oxidise the C6 hydroxyl group of the chitooligomer into carboxyl group; molecular weight distribution changes suggest that the structure of the oxidised product had changed and the molecular size and molecular weight decreased with the molecules in aqueous solution having a compact structure. Oxidation of chitooligomer by a laccase-TEMPO system resulted in a significant improvement in the moisture absorption, moisture retention and antioxidant abilities. The oxidised product has potential application values in the pharmaceutical and cosmetics industries.

  2. Monitoring change in the abundance and distribution of insects using butterflies and other indicator groups

    PubMed Central

    Thomas, J.A

    2005-01-01

    Conservative estimates suggest that 50–90% of the existing insect species on Earth have still to be discovered, yet the named insects alone comprise more than half of all known species of organism. With such poor baseline knowledge, monitoring change in insect diversity poses a formidable challenge to scientists and most attempts to generalize involve large extrapolations from a few well-studied taxa. Butterflies are often the only group for which accurate measures of change can be obtained. Four schemes, used successfully to assess change in British butterflies, that are increasingly being applied across the world are described: Red Data Books (RDB) list the best judgements of experts of the conservation status of species in their field of expertise; mapping schemes plot the changing distributions of species at scales of 1–100 km2; transect monitoring schemes generate time series of changes in abundance in sample populations of species on fixed sites across the UK; and occasional surveys measure the number, boundaries and size of all populations of a (usually RDB) species at intervals of 10–30 years. All schemes describe consistent patterns of change, but if they are to be more generally useful, it is important to understand how well butterflies are representative of other taxa. Comparisons with similarly measured changes in native bird and plant species suggest that butterflies have declined more rapidly that these other groups in Britain; it should soon be possible to test whether this pattern exists elsewhere. It is also demonstrated that extinction rates in British butterflies are similar to those in a range of other insect groups over 100 years once recording bias is accounted for, although probably lower than in aquatic or parasitic taxa. It is concluded that butterflies represent adequate indicators of change for many terrestrial insect groups, but recommended that similar schemes be extended to other popular groups, especially dragonflies

  3. DISTINCTIVE LOCALIZATION OF GROUP 3 LATE EMBRYOGENESIS ABUNDANT SYNTHESIZING CELLS DURING BRINE SHRIMP DEVELOPMENT.

    PubMed

    Kim, Bo Yong; Song, Hwa Young; Kim, Mi Young; Lee, Bong Hee; Kim, Kyung Joo; Jo, Kyung Jin; Kim, Suhng Wook; Lee, Seung Gwan; Lee, Boo Hyung

    2015-07-01

    Despite numerous studies on late embryogenesis abundant (LEA) proteins, their functions, roles, and localizations during developmental stages in arthropods remain unknown. LEA proteins protect crucial proteins against osmotic stress during the development and growth of various organisms. Thus, in this study, fluorescence in situ hybridization was used to determine the crucial regions protected against osmotic stress as well as the distinctive localization of group 3 (G3) LEA(+) cells during brine shrimp development. Several cell types were found to synthesize G3 LEA RNA, including neurons, muscular cells, APH-1(+) cells, and renal cells. The G3 LEA(+) neuronal cell bodies outside of the mushroom body projected their axonal bundles to the central body, but those inside the mushroom body projected their axonal bundles toward the deutocerebrum without innervating the central body. The cell bodies inside the mushroom body received axons of the G3 LEA(+) sensory cells at the medial ventral cup of the nauplius eye. Several glands were found to synthesize G3 LEA RNA during the nauplius stages of brine shrimp, including the sinus, antennal I and II, salt, and three ectodermal glands. This study provides the first demonstration of the formation of G3 LEA(+) sinus glands at the emergence stages of brine shrimp. These results suggest that G3 LEA protein is synthesized in several cell types. In particular, specific glands play crucial roles during the emergence and nauplius stages of brine shrimp. PMID:25781424

  4. The Abundances of the Fe Group Elements in Early B Stars in the Magellanic Clouds and Bridge

    NASA Astrophysics Data System (ADS)

    Peters, Geraldine J.; Adelman, Saul J.

    2016-01-01

    The abundances of three Fe Group elements (V, Cr, and Fe) in 9 early main-sequence band B stars in the LMC, 7 in the SMC , and two in the Magellanic Bridge have been determined from archival FUSE observations and the Hubeny/Lanz NLTE programs TLUSTY/SYNSPEC. Lines from the Fe group elements, except for a few weak multiplets of Fe III, are not observable in the optical spectral region. The best set of lines in the FUSE spectral region are Fe III (UV1), V III 1150 Å, and Cr III 1137 Å. The abundances of these elements in early B stars are a marker for recent SNe Ia activity, as a single exploding white dwarf can deliver 0.5 solar masses of Ni-56 that decays into Fe to the ISM. The Fe group abundances in an older population of stars primarily reflect SNe II activity, in which a single explosion delivers only 0.07 solar masses of Ni-56 to the ISM (the rest remains trapped in the neutron star). The abundances of the Fe group elements in early B stars not only track SNe Ia activity but are also important for computing evolutionary tracks for massive stars. In general, the Fe abundance relative to the sun's value is comparable to the mean abundances for the lighter elements in the Clouds/Bridge but the values of [V,Cr/Fe]sun are smaller. This presentation will discuss the spatial distribution of the Fe Group elements in the Magellanic Clouds, and compare it with our galaxy in which the abundance of Fe declines with radial distance from the center. Support from NASA grants NAG5-13212, NNX10AD66G, STScI HST-GO-13346.22, and USC's Women in Science and Engineering (WiSE) program is greatly appreciated.

  5. The Abundances of the Fe Group Elements in Early B Stars in the Magellanic Clouds and Our Galaxy

    NASA Astrophysics Data System (ADS)

    Peters, Geraldine Joan; Adelman, Saul Joseph

    2015-08-01

    The abundances of the Fe-peak elements (Ti, V, Cr, Mn, Fe, Co, and Ni) are of interest as they are important for assessing opacities for stellar evolution calculations, confirming theoretical calculations of explosive nucleosynthesis, and inferring the past history of supernova activity in a galaxy. FUSE FUV spectra of early B stars in the LMC and SMC and HST/STIS FUV/NUV spectra of nearby B stars in our galaxy are analyzed with the Hubeny/Lanz programs TLUSTY/SYNSPEC to determine abundance for the Fe group elements and produce a map of these abundances in the Magellanic Clouds (MC) and Magellanic Bridge (MB). Except for four weak multiplets of Fe III there are no measurable lines from the Fe group in the optical region. The Fe group species found in the FUV spectra of early B stars are primarily in the second stage of ionization. The best set of lines in the FUSE spectral region are Fe III (UV1), V III 1150 Å, and Cr III 1137 Å. Analysis of the galactic B stars provides a good assessment of the reliability of the atomic parameters that are used for the MC calculations. Twenty-two early B stars in the MC and MB and five in our galaxy were analyzed. In general the Fe group abundances range from solar to slightly below solar in our region of the galaxy. But in the MCs the abundances of V, Cr, and Fe tend to be significantly lower than the mean metal abundances for the galaxy. Maps of the Fe group abundances and their variations in the LMC and SMC, tracers of recent enrichment of the ISM from supernova activity, are shown. Support from NASA grants NAG5-13212, NNX10AD66G, STScI HST-GO-13346.22, and USC’s Women in Science and Engineering (WiSE) program is greatly appreciated.

  6. Cationic Copolymerization of 3,3-Bis(hydroxymethyl)oxetane and Glycidol: Biocompatible Hyperbranched Polyether Polyols with High Content of Primary Hydroxyl Groups.

    PubMed

    Christ, Eva-Maria; Hobernik, Dominika; Bros, Matthias; Wagner, Manfred; Frey, Holger

    2015-10-12

    The cationic ring-opening copolymerization of 3,3-bis(hydroxymethyl)oxetane (BHMO) with glycidol using different comonomer ratios (BHMO content from 25 to 90%) and BF3OEt2 as an initiator has been studied. Apparent molecular weights of the resulting hyperbranched polyether copolymers ranged from 1400 to 3300 g mol(-1) (PDI: 1.21-1.48; method: SEC, linear PEG standards). Incorporation of both comonomers is evidenced by MALDI-TOF mass spectroscopy. All hyperbranched polyether polyols with high content of primary hydroxyl groups portray good solubility in water, which correlates with an increasing content of glycerol units. Detailed NMR characterization was employed to elucidate the copolymer microstructures. Kinetic studies via FTIR demonstrated a weak gradient-type character of the copolymers. MTT assays of the copolymers (up to 100 μg mL(-1)) on HEK and fibroblast cell lines (3T3, L929, WEHI) as well as viability tests on the fibroblast cells were carried out to assess the biocompatibility of the materials, confirming excellent biocompatibility. Transfection efficiency characterization by flow cytometry and confocal laser microscopy demonstrated cellular uptake of the copolymers. Antiadhesive properties of the materials on surfaces were assessed by adhesion assays with fibroblast cells.

  7. Atomic resolution structure of a lysine-specific endoproteinase from Lysobacter enzymogenes suggests a hydroxyl group bound to the oxyanion hole.

    PubMed

    Asztalos, Peter; Müller, Astrid; Hölke, Werner; Sobek, Harald; Rudolph, Markus G

    2014-07-01

    Lysobacter enzymogenes lysyl endoproteinase (LysC) is a trypsin-type serine protease with a high pH optimum that hydrolyses all Lys-Xaa peptide bonds. The high specificity of LysC renders it useful for biotechnological purposes. The K30R variant of a related lysyl endoproteinase from Achromobacter lyticus has favourable enzymatic properties that might be transferrable to LysC. To visualize structural differences in the substrate-binding sites, the crystal structures of wild-type and the K30R variant of LysC were determined. The mutation is located at a distance of 12 Å from the catalytic triad and subtly changes the surface properties of the substrate-binding site. The high pH optimum of LysC can be attributed to electrostatic effects of an aromatic Tyr/His stack on the catalytic aspartate and is a general feature of this enzyme subfamily. LysC crystals in complex with the covalent inhibitor N(α)-p-tosyl-lysyl chloromethylketone yielded data to 1.1 and 0.9 Å resolution, resulting in unprecedented precision of the active and substrate-binding sites for this enzyme subfamily. Error estimates on bond lengths and difference electron density indicate that instead of the expected oxyanion a hydroxyl group binds to the partially solvent-exposed oxyanion hole. Protonation of the alkoxide catalytic intermediate might be a recurring feature during serine protease catalysis.

  8. Cationic Copolymerization of 3,3-Bis(hydroxymethyl)oxetane and Glycidol: Biocompatible Hyperbranched Polyether Polyols with High Content of Primary Hydroxyl Groups.

    PubMed

    Christ, Eva-Maria; Hobernik, Dominika; Bros, Matthias; Wagner, Manfred; Frey, Holger

    2015-10-12

    The cationic ring-opening copolymerization of 3,3-bis(hydroxymethyl)oxetane (BHMO) with glycidol using different comonomer ratios (BHMO content from 25 to 90%) and BF3OEt2 as an initiator has been studied. Apparent molecular weights of the resulting hyperbranched polyether copolymers ranged from 1400 to 3300 g mol(-1) (PDI: 1.21-1.48; method: SEC, linear PEG standards). Incorporation of both comonomers is evidenced by MALDI-TOF mass spectroscopy. All hyperbranched polyether polyols with high content of primary hydroxyl groups portray good solubility in water, which correlates with an increasing content of glycerol units. Detailed NMR characterization was employed to elucidate the copolymer microstructures. Kinetic studies via FTIR demonstrated a weak gradient-type character of the copolymers. MTT assays of the copolymers (up to 100 μg mL(-1)) on HEK and fibroblast cell lines (3T3, L929, WEHI) as well as viability tests on the fibroblast cells were carried out to assess the biocompatibility of the materials, confirming excellent biocompatibility. Transfection efficiency characterization by flow cytometry and confocal laser microscopy demonstrated cellular uptake of the copolymers. Antiadhesive properties of the materials on surfaces were assessed by adhesion assays with fibroblast cells. PMID:26355352

  9. Abundances of Local Group Globular Clusters Using High Resolution Integrated Light Spectroscopy

    NASA Astrophysics Data System (ADS)

    Sakari, Charli; McWilliam, A.; Venn, K.; Shetrone, M. D.; Dotter, A. L.; Mackey, D.

    2014-01-01

    Abundances and kinematics of extragalactic globular clusters provide valuable clues about galaxy and globular cluster formation in a wide variety of environments. In order to obtain such information about distant, unresolved systems, specific observational techniques are required. An Integrated Light Spectrum (ILS) provides a single spectrum from an entire stellar population, and can therefore be used to determine integrated cluster abundances. This dissertation investigates the accuracy of high resolution ILS analysis methods, using ILS (taken with the Hobby-Eberly Telescope) of globular clusters associated with the Milky Way (47 Tuc, M3, M13, NGC 7006, and M15) and then applies the method to globular clusters in the outer halo of M31 (from the Pan-Andromeda Archaeological Survey, or PAndAS). Results show that: a) as expected, the high resolution method reproduces individual stellar abundances for elements that do not vary within a cluster; b) the presence of multiple populations does affect the abundances of elements that vary within the cluster; c) certain abundance ratios are very sensitive to systematic effects, while others are not; and d) certain abundance ratios (e.g. [Ca/Fe]) can be accurately obtained from unresolved systems. Applications of ILABUNDS to the PAndAS clusters reveal that accretion may have played an important role in the formation of M31's outer halo.

  10. Replacement of the carboxylic acid group of prostaglandin F2α with a hydroxyl or methoxy substituent provides biologically unique compounds

    PubMed Central

    Woodward, D F; Krauss, A H-P; Chen, J; Gil, D W; Kedzie, K M; Protzman, C E; Shi, L; Chen, R; Krauss, H A; Bogardus, A; Dinh, H T T; Wheeler, L A; Andrews, S W; Burk, R M; Gac, T; Roof, M B; Garst, M E; Kaplan, L J; Sachs, G; Pierce, K L; Regan, J W; Ross, R A; Chan, M F

    2000-01-01

    Replacement of the carboxylic acid group of PGF2α with the non-acidic substituents hydroxyl (-OH) or methoxy (-OCH3) resulted in an unexpected activity profile.Although PGF2α 1-OH and PGF2α 1-OCH3 exhibited potent contractile effects similar to 17-phenyl PGF2α in the cat lung parenchymal preparation, they were approximately 1000 times less potent than 17-phenyl PGF2α in stimulating recombinant feline and human FP receptors.In human dermal fibroblasts and Swiss 3T3 cells PGF2α 1-OH and PGF2α 1-OCH3 produced no Ca2+ signal until a 1 μM concentration was exceeded. Pretreatment of Swiss 3T3 cells with either 1 μM PGF2α 1-OH or PGF2α 1-OCH3 did not attenuate Ca2+ signal responses produced by PGF2α or fluprostenol. In the rat uterus, PGF2α 1-OH was about two orders of magnitude less potent than 17-phenyl PGF2α whereas PGF2α 1-OCH3 produced only a minimal effect.Radioligand binding studies on cat lung parenchymal plasma membrane preparations suggested that the cat lung parenchyma does not contain a homogeneous population of receptors that equally respond to PGF2α1-OH, PGF2α1-OCH3, and classical FP receptor agonists.Studies on smooth muscle preparations and cells containing DP, EP1, EP2, EP3, EP4, IP, and TP receptors indicated that the activity of PGF2α 1-OH and PGF2α 1-OCH3 could not be ascribed to interaction with these receptors.The potent effects of PGF2α 1-OH and PGF2α 1-OCH3 on the cat lung parenchyma are difficult to describe in terms of interaction with the FP or any other known prostanoid receptor. PMID:10952685

  11. Structure–activity relationship of Au/ZrO2 catalyst on formation of hydroxyl groups and its influence on CO oxidation

    SciTech Connect

    Karwacki, Christopher J.; Ganesh, P.; Kent, Paul R. C.; Gordon, Wesley O.; Peterson, Gregory W.; Niu, Jun Jie; Gogotsi, Yury

    2013-01-01

    The effect of changes in morphology and surface hydroxyl species upon thermal treatment of zirconia on the oxidation activity of Au/ZrO2 catalyst was studied. We observed using transmission fourier transform infrared (FTIR) spectroscopy progressive changes in the presence of monodentate (type I), bidentate (type II) and hydrogen bridged species (type III) for each of the thermally treated (85 to 500 C) supports consisting of bare zirconia and Au/ZrO2 catalysts. Furthermore, structural changes in zirconia were accompanied by an increase in crystal size (7 to 58 nm) and contraction of the supports porosity (SSA 532 to 7 m2/g) with increasing thermal treatment. Deposition of gold nanoparticles under similar preparation conditions on different thermally treated zirconia resulted in changes in the mean gold cluster size, ranging from 3.7 to 5.6 nm. Changes in the surface hydroxyl species, support structure and size of the gold centers are important parameters responsible for the observed decrease (> 90 %) in CO conversion activity for the Au/ZrO2 catalysts. Density functional theory calculations provide evidence of increased CO binding to Au nanoclusters in the presence of surface hydroxyls on zirconia, which increases charge transfer at the perimeter of the gold nanocluster on zirconia support. This further helps in reducing a model CO-oxidation reaction barrier in the presence of surface hydroxyls. This work demonstrates the need to understand the structure-activity relationship of both the support and active particles for the design of catalytic materials.

  12. The Abundances of the Fe Group Elements in Three Early B Stars in the Large Magellanic Cloud

    NASA Astrophysics Data System (ADS)

    Peters, G. J.; Adelman, S. J.

    2005-12-01

    The photospheric abundances of V, Cr, and Fe have been determined for three sharp-lined early B stars in the Large Magellanic Cloud using FUV spectra obtained from the Far Ultraviolet Spectroscopic Explorer (FUSE) and the Kurucz LTE model atmosphere/spectrum synthesis codes ATLAS9/SYNTHE. The program stars include NGC1818/D1, NGC2004/B15, and NGC2004/B30 (star designations are from Robertson 1974, A&AS, 15, 261). The calculations were carried through with model parameters close to those adopted by Korn et al. (2000, A&A, 353, 655). Values of Teff, log g, ξ T, and v sin I are 25000/4.0/0/30, 20000/3.1/6/25, and 23500/3.3/14/30 for NGC1818/D1, NGC2004/B15, and NGC2004/B30, respectively. The abundances quoted below are in sequence for the latter stars. The vanadium abundances, [V/H], determined from V III λ λ 1150,1152 (UV 2), are -0.6, -0.9, and -0.9 dex. Cr was determined from Cr III λ λ 1118,1136. Values of -0.5, -0.8, and -0.7 dex were found. Uncertainties in the V and Cr abundances are ˜0.3 dex. The Fe abundance is primarily from 7 lines of Fe III (UV 1) in the region λ λ 1122-32. Values are -0.8±0.3, ˜-1.1, and -0.4±0.3. Since there is no evidence for N enhancement in the program stars ([N/H] ˜ -0.9, -1.0, and -0.6 from the N III doublet at 1183,1184 Å) the photospheric abundances have probably not been altered by mixing of processed material from the star's interior and the derived abundances represent pristine values for the two young clusters in the LMC. It should be noted that the N and Fe abundances derived for NGC1818/D1 are about 0.5 dex lower than those determined by Korn et al. from much weaker optical lines. We will discuss possible reasons for the discrepancy. The generally low abundances for the Fe group elements in these young cluster B stars imply that supernova activity has been minimal in the regions of the LMC in which the stars were formed. GJP appreciates support from NASA grant NAG5-13212.

  13. Abundance and Relative Distribution of Frankia Host Infection Groups Under Actinorhizal Alnus glutinosa and Non-actinorhizal Betula nigra Trees.

    PubMed

    Samant, Suvidha; Huo, Tian; Dawson, Jeffrey O; Hahn, Dittmar

    2016-02-01

    Quantitative polymerase chain reaction (qPCR) was used to assess the abundance and relative distribution of host infection groups of the root-nodule forming, nitrogen-fixing actinomycete Frankia in four soils with similar physicochemical characteristics, two of which were vegetated with a host plant, Alnus glutinosa, and two with a non-host plant, Betula nigra. Analyses of DAPI-stained cells at three locations, i.e., at a distance of less than 1 m (near stem), 2.5 m (middle crown), and 3-5 m (crown edge) from the stems of both tree species revealed no statistically significant differences in abundance. Frankiae generally accounted for 0.01 to 0.04 % of these cells, with values between 4 and 36 × 10(5) cells (g soil)(-1). In three out of four soils, abundance of frankiae was significantly higher at locations "near stem" and/or "middle crown" compared to "crown edge," while numbers at these locations were not different in the fourth soil. Frankiae of the Alnus host infection group were dominant in all samples accounting for about 75 % and more of the cells, with no obvious differences with distance to stem. In three of the soils, all of these cells were represented by strain Ag45/Mut15. In the fourth soil that was vegetated with older A. glutinosa trees, about half of these cells belonged to a different subgroup represented by strain ArI3. In all soils, the remaining cells belonged to the Elaeagnus host infection group represented by strain EAN1pec. Casuarina-infective frankiae were not found. Abundance and relative distribution of Frankia host infection groups were similar in soils under the host plant A. glutinosa and the non-host plant B. nigra. Results did thus not reveal any specific effects of plant species on soil Frankia populations. PMID:26143359

  14. Abundance and Relative Distribution of Frankia Host Infection Groups Under Actinorhizal Alnus glutinosa and Non-actinorhizal Betula nigra Trees.

    PubMed

    Samant, Suvidha; Huo, Tian; Dawson, Jeffrey O; Hahn, Dittmar

    2016-02-01

    Quantitative polymerase chain reaction (qPCR) was used to assess the abundance and relative distribution of host infection groups of the root-nodule forming, nitrogen-fixing actinomycete Frankia in four soils with similar physicochemical characteristics, two of which were vegetated with a host plant, Alnus glutinosa, and two with a non-host plant, Betula nigra. Analyses of DAPI-stained cells at three locations, i.e., at a distance of less than 1 m (near stem), 2.5 m (middle crown), and 3-5 m (crown edge) from the stems of both tree species revealed no statistically significant differences in abundance. Frankiae generally accounted for 0.01 to 0.04 % of these cells, with values between 4 and 36 × 10(5) cells (g soil)(-1). In three out of four soils, abundance of frankiae was significantly higher at locations "near stem" and/or "middle crown" compared to "crown edge," while numbers at these locations were not different in the fourth soil. Frankiae of the Alnus host infection group were dominant in all samples accounting for about 75 % and more of the cells, with no obvious differences with distance to stem. In three of the soils, all of these cells were represented by strain Ag45/Mut15. In the fourth soil that was vegetated with older A. glutinosa trees, about half of these cells belonged to a different subgroup represented by strain ArI3. In all soils, the remaining cells belonged to the Elaeagnus host infection group represented by strain EAN1pec. Casuarina-infective frankiae were not found. Abundance and relative distribution of Frankia host infection groups were similar in soils under the host plant A. glutinosa and the non-host plant B. nigra. Results did thus not reveal any specific effects of plant species on soil Frankia populations.

  15. Water concentrations and hydrogen isotope compositions of alkaline basalt-hosted clinopyroxene megacrysts and amphibole clinopyroxenites: the role of structural hydroxyl groups and molecular water

    NASA Astrophysics Data System (ADS)

    Kovács, István; Demény, Attila; Czuppon, György; Lécuyer, Christophe; Fourel, Francois; Xia, Qun-Ke; Liu, Jia; Pintér, Zsanett; Király, Edit; Török, Kálmán; Szabó, Ábel; Deloule, Etienne; Falus, György; Fancsik, Tamás; Zajacz, Zoltán; Sándorné Kovács, Judit; Udvardi, Beatrix

    2016-05-01

    The aim of this study was to determine both `water' contents (as OH- and H2O) and δD values of several clinopyroxene samples from alkaline basalts. These parameters were first obtained from five clinopyroxene samples using both the classical `off-line' vacuum extraction technique and the `on-line' high-temperature pyrolysis technique. Blanks measured with the `on-line' gas extraction techniques were low enough to prevent any contamination by atmospheric water vapour. The comparison of data has revealed that our `on-line' procedure is more effective for the extraction of `water' from clinopyroxenes and, consequently, this `on-line' technique was applied to ten additional clinopyroxene samples. Sample δD values cover a similar range from -95 to -45 ‰ (VSMOW) regardless of the studied locations, whereas the total `water' content varies from ~115 to ~2570 ppm. The structural hydroxyl content of clinopyroxene samples measured by micro-FTIR spectrometry varies from ~0 to 476 ppm expressed in molecular water equivalent. The total `water' concentrations determined by mass spectrometry differ considerably from structural hydroxyl contents constrained by micro-FTIR, thus indicating that considerable proportion of the `water' may be present in (nano)-inclusions. The structural hydroxyl concentration—apart from clinopyroxenes separated from amphibole clinopyroxenite xenoliths—correlates positively with the δD values of clinopyroxene megacrysts for each locality, indicating that structurally bond hydrogen in clinopyroxenes may have δD values higher than molecular water in inclusions. This implies that there may be a significant hydrogen isotope fractionation for structural hydroxyl during crystallization of clinopyroxene, while for molecular water there may be no or only negligible isotope fractionation.

  16. Relative abundance of water-group ions in Saturn's inner magnetosphere

    NASA Astrophysics Data System (ADS)

    Perry, Mark E.; Cravens, Thomas; Tokar, Robert; Smith, Howard T.; Perryman, Rebecca; Waite, J. Hunter; McNutt, Ralph L.

    2016-10-01

    At nineteen different times over seven years, the Cassini Ion Neutral Mass Spectrometer (INMS) measured the relative fractions of water-group ions in the inner magnetosphere of Saturn near the equatorial plane between 3.8 and 6.5 Saturn radii (RS). INMS samples only a small portion of velocity space in any one measurement, but the measurements span a broad range of velocity space. The data show that H2O+ comprises the bulk of the ions near 4.0 RS, and that its fraction decreases with increasing distance from 4.0 RS, the source of neutral water at Enceladus. At 4.0 RS, the fraction of H2O+ ranges from 60% to 100%, with an average of 80%. At 6.5 RS, the three main water-group constituents, H2O+, OH+, and O+, are nearly equal. H3O+, which dominates the water-group ion fractions in the Enceladus plume, is 10% or less in Saturn's magnetosphere outside the plume. The relative ion fractions show other variations that are not clearly linked to any of the studied parameters including velocity, density, and the orbit-phase-dependent activity of Enceladus.

  17. The radiocarbon hydroxyl technique

    NASA Technical Reports Server (NTRS)

    Campbell, Malcolm J.; Sheppard, John C.

    1994-01-01

    The Radiocarbon Technique depends upon measuring the rate of oxidation of CO in an essentially unperturbed sample of air. The airborne technique is slightly different. Hydroxyl concentrations can be calculated directly; peroxyl concentrations can be obtained by NO doping.

  18. The Group Abundance Fraction: A statistically robust measure of particle composition and of spatial structure in images

    NASA Astrophysics Data System (ADS)

    Roelof, Edmond C.

    2015-01-01

    When two processes (A and B) are measured by counting instruments, we wish to present the results as an "abundance" along with an associated uncertainty. When the number of individual counts of either component is low, the usual ratio (A/B) is statistically ill-defined because there is a finite probability of zero counts in the denominator. However, the "Group Abundance Fraction" (F), e.g., A/(A+B), is a statistically robust parameter (under the condition that there must be at least one total count between A and B in order to constitute a measurement). We rigorously derive expectation values (over a conditional Poisson statistical ensemble) for and its standard deviation σF that are valid for all values of total counts greater than one. We then derive useful estimators for these ensemble expectation values in terms of simple algebraic functions of the actual observed accumulated counts. We also incorporate the practical effects of instrument response functions and background rates. The results are not restricted to particle species composition (or spectra), but are also applicable when A and B represent counts in adjacent "pixels" of spatial images formed by the particles.

  19. Solenicola setigera is the first characterized member of the abundant and cosmopolitan uncultured marine stramenopile group MAST-3.

    PubMed

    Gómez, Fernando; Moreira, David; Benzerara, Karim; López-García, Purificación

    2011-01-01

    Culture-independent molecular methods based on the amplification, cloning and sequencing of small-subunit (SSU) rRNA genes are a powerful tool to study the diversity of prokaryotic and eukaryotic microorganisms for which morphological features are not conspicuous. In recent years, molecular data from environmental surveys have revealed several clades of protists lacking cultured and/or described members. Among them are various clades of marine stramenopiles (heterokonts), which are thought to play an essential ecological role as grazers, being abundant and distributed in oceans worldwide. In this work, we show that Solenicola setigera, a distinctive widespread colonial marine protist, is a member of the environmental clade MArine STramenopile 3 (MAST-3). Solenicola is generally considered as a parasite or an epiphyte of the diatom Leptocylindrus mediterraneus. So far, the ultrastructural, morphological and ecological data available were insufficient to elucidate its phylogenetic position, even at the division or class level. We determined SSU rRNA gene sequences of S. setigera specimens sampled from different locations and seasons in the type locality, the Gulf of Lions, France. They were closely related, though not identical, which, together with morphological differences under electron microscopy, suggest the occurrence of several species. Solenicola sequences were well nested within the MAST-3 clade in phylogenetic trees. Since Solenicola is the first identified member of this abundant marine clade, we propose the name Solenicolida for the MAST-3 phylogenetic group.

  20. Annual trend patterns of phytoplankton species abundance belie homogeneous taxonomical group responses to climate in the NE Atlantic upwelling.

    PubMed

    Bode, Antonio; Estévez, M Graciela; Varela, Manuel; Vilar, José A

    2015-09-01

    Phytoplankton is a sentinel of marine ecosystem change. Composed by many species with different life-history strategies, it rapidly responds to environment changes. An analysis of the abundance of 54 phytoplankton species in Galicia (NW Spain) between 1989 and 2008 to determine the main components of temporal variability in relation to climate and upwelling showed that most of this variability was stochastic, as seasonality and long term trends contributed to relatively small fractions of the series. In general, trends appeared as non linear, and species clustered in 4 groups according to the trend pattern but there was no defined pattern for diatoms, dinoflagellates or other groups. While, in general, total abundance increased, no clear trend was found for 23 species, 14 species decreased, 4 species increased during the early 1990s, and only 13 species showed a general increase through the series. In contrast, series of local environmental conditions (temperature, stratification, nutrients) and climate-related variables (atmospheric pressure indices, upwelling winds) showed a high fraction of their variability in deterministic seasonality and trends. As a result, each species responded independently to environmental and climate variability, measured by generalized additive models. Most species showed a positive relationship with nutrient concentrations but only a few showed a direct relationship with stratification and upwelling. Climate variables had only measurable effects on some species but no common response emerged. Because its adaptation to frequent disturbances, phytoplankton communities in upwelling ecosystems appear less sensitive to changes in regional climate than other communities characterized by short and well defined productive periods.

  1. Annual trend patterns of phytoplankton species abundance belie homogeneous taxonomical group responses to climate in the NE Atlantic upwelling.

    PubMed

    Bode, Antonio; Estévez, M Graciela; Varela, Manuel; Vilar, José A

    2015-09-01

    Phytoplankton is a sentinel of marine ecosystem change. Composed by many species with different life-history strategies, it rapidly responds to environment changes. An analysis of the abundance of 54 phytoplankton species in Galicia (NW Spain) between 1989 and 2008 to determine the main components of temporal variability in relation to climate and upwelling showed that most of this variability was stochastic, as seasonality and long term trends contributed to relatively small fractions of the series. In general, trends appeared as non linear, and species clustered in 4 groups according to the trend pattern but there was no defined pattern for diatoms, dinoflagellates or other groups. While, in general, total abundance increased, no clear trend was found for 23 species, 14 species decreased, 4 species increased during the early 1990s, and only 13 species showed a general increase through the series. In contrast, series of local environmental conditions (temperature, stratification, nutrients) and climate-related variables (atmospheric pressure indices, upwelling winds) showed a high fraction of their variability in deterministic seasonality and trends. As a result, each species responded independently to environmental and climate variability, measured by generalized additive models. Most species showed a positive relationship with nutrient concentrations but only a few showed a direct relationship with stratification and upwelling. Climate variables had only measurable effects on some species but no common response emerged. Because its adaptation to frequent disturbances, phytoplankton communities in upwelling ecosystems appear less sensitive to changes in regional climate than other communities characterized by short and well defined productive periods. PMID:26283032

  2. Sniffing for Clues to the Dinosaurs Demise: Measurement of Osmium Isotope Compositions and Platinum Group Element Abundances in Volcanic Emissions

    NASA Astrophysics Data System (ADS)

    Sims, K. W.; Peucker-Ehrenbrink, B.; Mather, T.; Pyle, D.; Martin, R.; Gauthier, P.; Aiuppa, A.

    2005-12-01

    Platinum Group Elements (PGE: Os, Ir, Rh, Ru, Pt, Pd) and osmium isotopes measured in marine and terrestrial sediment, snow and ice records are important paleo-tracers of riverine, hydrothermal, extraterrestrial, volcanic and anthropogenic inputs into the global surficial environment. For instance, the marine Os isotope record across the Cretaceous-Tertiary Boundary (KTB) indicates that the onset of the main phase of Deccan volcanism and the transient late Maastrichtian warming preceded the large extraterrestrial impact and the related KTB mass extinction by several hundred thousand years [Ravizza and Peucker-Ehrenbrink, 2003]. Distinguishing extraterrestrial from volcanic PGE sources has been difficult due to the similarity in Os isotopic compositions, complex PGE fractionations, and our lack of knowledge of the Os isotopic composition and PGE abundances in volcanic aerosols. These difficulties have fueled vigorous debate about extraterrestrial vs. volcanic triggers of mass extinctions in the geologic record. To assess the volcanic contribution to the global Re-Os-PGE cycle we have initiated a study of Os isotopic compositions and PGE abundances in volcanic emissions from volcanoes around the globe. Here we report preliminary data on PGE abundances and Os isotopes measured in gas and aerosol filter samples from Vulcan Masaya, Nicaragua and Mt Etna, Italy. Samples were analyzed by ID-ICPMS (ThermoFinnigan ELEMENT 2 and NEPTUNE) at the Woods Hole Oceanographic Institution. Osmium isotope compositions of the filters are unradiogenic (0.1272 to 0.187). Osmium concentrations range from 28 to 97 pg/cubic meter and are 3-4 orders of magnitude lower than those measured by Krahenbuhl et al. [1992] during the spring 1984 eruption of Mauna Loa just after the lava fountaining phase. Normalized PGE abundance patterns are fractionated relative to carbonaceous chondrites and two important features distinguish the pattern from other important PGE sources: 1) Os/Ir is much higher

  3. Study of model systems to test the potential function of Artemia group 1 late embryogenesis abundant (LEA) proteins.

    PubMed

    Warner, Alden H; Guo, Zhi-hao; Moshi, Sandra; Hudson, John W; Kozarova, Anna

    2016-01-01

    Embryos of the brine shrimp, Artemia franciscana, are genetically programmed to develop either ovoviparously or oviparously depending on environmental conditions. Shortly upon their release from the female, oviparous embryos enter diapause during which time they undergo major metabolic rate depression while simultaneously synthesize proteins that permit them to tolerate a wide range of stressful environmental events including prolonged periods of desiccation, freezing, and anoxia. Among the known stress-related proteins that accumulate in embryos entering diapause are the late embryogenesis abundant (LEA) proteins. This large group of intrinsically disordered proteins has been proposed to act as molecular shields or chaperones of macromolecules which are otherwise intolerant to harsh conditions associated with diapause. In this research, we used two model systems to study the potential function of the group 1 LEA proteins from Artemia. Expression of the Artemia group 1 gene (AfrLEA-1) in Escherichia coli inhibited growth in proportion to the number of 20-mer amino acid motifs expressed. As well, clones of E. coli, transformed with the AfrLEA-1 gene, expressed multiple bands of LEA proteins, either intrinsically or upon induction with isopropyl-β-thiogalactoside (IPTG), in a vector-specific manner. Expression of AfrLEA-1 in E. coli did not overcome the inhibitory effects of high concentrations of NaCl and KCl but modulated growth inhibition resulting from high concentrations of sorbitol in the growth medium. In contrast, expression of the AfrLEA-1 gene in Saccharomyces cerevisiae did not alter the growth kinetics or permit yeast to tolerate high concentrations of NaCl, KCl, or sorbitol. However, expression of AfrLEA-1 in yeast improved its tolerance to drying (desiccation) and freezing. Under our experimental conditions, both E. coli and S. cerevisiae appear to be potentially suitable hosts to study the function of Artemia group 1 LEA proteins under environmentally

  4. Hydroxyl radicals in indoor environments

    NASA Astrophysics Data System (ADS)

    Sarwar, Golam; Corsi, Richard; Kimura, Yosuke; Allen, David; Weschler, Charles J.

    Indoor hydroxyl radical concentrations were estimated using a new indoor air quality model which employs the SAPRC-99 atmospheric chemistry model to simulate indoor homogenous reactions. Model results indicate that typical indoor hydroxyl radical concentrations are lower than typical outdoor summertime urban hydroxyl radical levels of 5-10×10 6 molecules cm -3; however, indoor levels can be similar to or greater than typical nighttime outdoor hydroxyl radical levels of approximately 5×10 4 molecules cm -3. Effects of selected parameters on indoor hydroxyl radical concentrations are presented herein. Indoor hydroxyl radical concentrations are predicted to increase non-linearly with increasing outdoor ozone concentrations, indoor alkene emission rates, and air exchange rates. Indoor hydroxyl radical concentrations decrease with increasing outdoor nitric oxide concentrations. Indoor temperature and indoor light intensity have moderate impacts on indoor hydroxyl radical concentrations. Outdoor hydroxyl radical concentrations, outdoor nitrate (NO 3rad ) radical concentrations, outdoor hydroperoxy radical concentrations, and hydroxyl radical removal by indoor surfaces are predicted to have no appreciable impact on indoor hydroxyl radical concentrations. Production of hydroxyl radicals in indoor environments appears to be controlled primarily by reactions of alkenes with ozone, and nitric oxide with hydroperoxy radical. Estimated indoor hydroxyl radical levels may potentially affect indoor air quality. Two examples are presented in which reactions of d-limonene and α-pinene with indoor hydroxyl radicals produce aldehydes, which may be of greater concern than the original compounds.

  5. New and extended parameterization of the thermodynamic model AIOMFAC: calculation of activity coefficients for organic-inorganic mixtures containing carboxyl, hydroxyl, carbonyl, ether, ester, alkenyl, alkyl, and aromatic functional groups

    NASA Astrophysics Data System (ADS)

    Zuend, A.; Marcolli, C.; Booth, A. M.; Lienhard, D. M.; Soonsin, V.; Krieger, U. K.; Topping, D. O.; McFiggans, G.; Peter, T.; Seinfeld, J. H.

    2011-05-01

    We present a new and considerably extended parameterization of the thermodynamic activity coefficient model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) at room temperature. AIOMFAC combines a Pitzer-like electrolyte solution model with a UNIFAC-based group-contribution approach and explicitly accounts for interactions between organic functional groups and inorganic ions. Such interactions constitute the salt-effect, may cause liquid-liquid phase separation, and affect the gas-particle partitioning of aerosols. The previous AIOMFAC version was parameterized for alkyl and hydroxyl functional groups of alcohols and polyols. With the goal to describe a wide variety of organic compounds found in atmospheric aerosols, we extend here the parameterization of AIOMFAC to include the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkenyl, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon. Thermodynamic equilibrium data of organic-inorganic systems from the literature are critically assessed and complemented with new measurements to establish a comprehensive database. The database is used to determine simultaneously the AIOMFAC parameters describing interactions of organic functional groups with the ions H+, Li+, Na+, K+, NH4+, Mg2+, Ca2+, Cl-, Br-, NO3-, HSO4-, and SO42-. Detailed descriptions of different types of thermodynamic data, such as vapor-liquid, solid-liquid, and liquid-liquid equilibria, and their use for the model parameterization are provided. Issues regarding deficiencies of the database, types and uncertainties of experimental data, and limitations of the model, are discussed. The challenging parameter optimization problem is solved with a novel combination of powerful global minimization algorithms. A number of exemplary calculations for systems containing atmospherically relevant aerosol components are shown. Amongst others, we discuss aqueous mixtures of ammonium sulfate with

  6. New and extended parameterization of the thermodynamic model AIOMFAC: calculation of activity coefficients for organic-inorganic mixtures containing carboxyl, hydroxyl, carbonyl, ether, ester, alkenyl, alkyl, and aromatic functional groups

    NASA Astrophysics Data System (ADS)

    Zuend, A.; Marcolli, C.; Booth, A. M.; Lienhard, D. M.; Soonsin, V.; Krieger, U. K.; Topping, D. O.; McFiggans, G.; Peter, T.; Seinfeld, J. H.

    2011-09-01

    We present a new and considerably extended parameterization of the thermodynamic activity coefficient model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) at room temperature. AIOMFAC combines a Pitzer-like electrolyte solution model with a UNIFAC-based group-contribution approach and explicitly accounts for interactions between organic functional groups and inorganic ions. Such interactions constitute the salt-effect, may cause liquid-liquid phase separation, and affect the gas-particle partitioning of aerosols. The previous AIOMFAC version was parameterized for alkyl and hydroxyl functional groups of alcohols and polyols. With the goal to describe a wide variety of organic compounds found in atmospheric aerosols, we extend here the parameterization of AIOMFAC to include the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkenyl, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon. Thermodynamic equilibrium data of organic-inorganic systems from the literature are critically assessed and complemented with new measurements to establish a comprehensive database. The database is used to determine simultaneously the AIOMFAC parameters describing interactions of organic functional groups with the ions H+, Li+, Na+, K+, NH4+, Mg2+, Ca2+, Cl-, Br-, NO3-, HSO4-, and SO42-. Detailed descriptions of different types of thermodynamic data, such as vapor-liquid, solid-liquid, and liquid-liquid equilibria, and their use for the model parameterization are provided. Issues regarding deficiencies of the database, types and uncertainties of experimental data, and limitations of the model, are discussed. The challenging parameter optimization problem is solved with a novel combination of powerful global minimization algorithms. A number of exemplary calculations for systems containing atmospherically relevant aerosol components are shown. Amongst others, we discuss aqueous mixtures of ammonium sulfate with

  7. Modifications of the 7-Hydroxyl Group of the Transthyretin Ligand Luteolin Provide Mechanistic Insights into Its Binding Properties and High Plasma Specificity

    PubMed Central

    Nilsson, Lina; Larsson, Andreas; Begum, Afshan; Iakovleva, Irina; Carlsson, Marcus; Brännström, Kristoffer; Sauer-Eriksson, A. Elisabeth; Olofsson, Anders

    2016-01-01

    Amyloid formation of the plasma protein transthyretin (TTR) has been linked to familial amyloid polyneuropathy and senile systemic amyloidosis. Binding of ligands within its natural hormone binding site can stabilize the tetrameric structure and impair amyloid formation. We have recently shown that the flavonoid luteolin stabilizes TTR in human plasma with a very high selectivity. Luteolin, however, is inactivated in vivo via glucuronidation for which the preferred site is the hydroxy group at position 7 on its aromatic A-ring. We have evaluated the properties of two luteolin variants in which the 7-hydroxy group has been exchanged for a chlorine (7-Cl-Lut) or a methoxy group (7-MeO-Lut). Using an in vitro model, based on human liver microsomes, we verified that these modifications increase the persistence of the drug. Crystal structure determinations show that 7-Cl-Lut binds similarly to luteolin. The larger MeO substituent cannot be accommodated within the same space as the chlorine or hydroxy group and as a result 7-MeO-Lut binds in the opposite direction with the methoxy group in position 7 facing the solvent. Both 7-Cl-Lut and 7-MeO-Lut qualify as high-affinity binders, but in contrast to luteolin, they display a highly non-specific binding to other plasma components. The binding of the two conformations and the key-interactions to TTR are discussed in detail. Taken together, these results show a proof-of-concept that the persistence of luteolin towards enzymatic modification can be increased. We reveal two alternative high-affinity binding modes of luteolin to TTR and that modification in position 7 is restricted only to small substituents if the original orientation of luteolin should be preserved. In addition, the present work provides a general and convenient method to evaluate the efficacy of TTR-stabilizing drugs under conditions similar to an in vivo environment. PMID:27050398

  8. Modifications of the 7-Hydroxyl Group of the Transthyretin Ligand Luteolin Provide Mechanistic Insights into Its Binding Properties and High Plasma Specificity.

    PubMed

    Nilsson, Lina; Larsson, Andreas; Begum, Afshan; Iakovleva, Irina; Carlsson, Marcus; Brännström, Kristoffer; Sauer-Eriksson, A Elisabeth; Olofsson, Anders

    2016-01-01

    Amyloid formation of the plasma protein transthyretin (TTR) has been linked to familial amyloid polyneuropathy and senile systemic amyloidosis. Binding of ligands within its natural hormone binding site can stabilize the tetrameric structure and impair amyloid formation. We have recently shown that the flavonoid luteolin stabilizes TTR in human plasma with a very high selectivity. Luteolin, however, is inactivated in vivo via glucuronidation for which the preferred site is the hydroxy group at position 7 on its aromatic A-ring. We have evaluated the properties of two luteolin variants in which the 7-hydroxy group has been exchanged for a chlorine (7-Cl-Lut) or a methoxy group (7-MeO-Lut). Using an in vitro model, based on human liver microsomes, we verified that these modifications increase the persistence of the drug. Crystal structure determinations show that 7-Cl-Lut binds similarly to luteolin. The larger MeO substituent cannot be accommodated within the same space as the chlorine or hydroxy group and as a result 7-MeO-Lut binds in the opposite direction with the methoxy group in position 7 facing the solvent. Both 7-Cl-Lut and 7-MeO-Lut qualify as high-affinity binders, but in contrast to luteolin, they display a highly non-specific binding to other plasma components. The binding of the two conformations and the key-interactions to TTR are discussed in detail. Taken together, these results show a proof-of-concept that the persistence of luteolin towards enzymatic modification can be increased. We reveal two alternative high-affinity binding modes of luteolin to TTR and that modification in position 7 is restricted only to small substituents if the original orientation of luteolin should be preserved. In addition, the present work provides a general and convenient method to evaluate the efficacy of TTR-stabilizing drugs under conditions similar to an in vivo environment. PMID:27050398

  9. Group 3 late embryogenesis abundant proteins from embryos of Artemia franciscana: structural properties and protective abilities during desiccation.

    PubMed

    Boswell, Leaf C; Menze, Michael A; Hand, Steven C

    2014-01-01

    Group 3 late embryogenesis abundant (LEA) proteins are highly hydrophilic, and their expression is associated with desiccation tolerance in both plants and animals. Here we show that two LEA proteins from embryos of Artemia franciscana, AfrLEA2 and AfrLEA3m, are intrinsically disordered in solution but upon desiccation gain secondary structure, as measured by circular dichroism. Trifluoroethanol and sodium dodecyl sulfate are both shown to induce α-helical structure in AfrLEA2 and AfrLEA3m. Bioinformatic predictions of secondary-structure content for both proteins correspond most closely to conformations measured in the dry state. Because some LEA proteins afford protection to desiccation-sensitive proteins during drying and subsequent rehydration, we tested for this capacity in AfrLEA2 and AfrLEA3m. The protective capacities vary, depending on the target enzyme. For the cytoplasmic enzyme lactate dehydrogenase, neither AfrLEA2 nor AfrLEA3m, with or without trehalose present, was able to afford protection better than that provided by bovine serum albumin (BSA) under the same conditions. However, for another cytoplasmic enzyme, phosphofructokinase, both AfrLEA2 and AfrLEA3m in the presence of trehalose were able to afford protection far greater than that provided by BSA with trehalose. Finally, for the mitochondrial enzyme citrate synthase, 400-μg/mL AfrLEA3m without trehalose provided significantly more protection than the same concentration of either AfrLEA2 or BSA. PMID:25244376

  10. Catalytic selective etherification of hydroxyl groups in 5-hydroxymethylfurfural over H4SiW12O40/MCM-41 nanospheres for liquid fuel production.

    PubMed

    Che, Penghua; Lu, Fang; Zhang, Junjie; Huang, Yizheng; Nie, Xin; Gao, Jin; Xu, Jie

    2012-09-01

    5-Hydroxymethylfurfural (HMF) is an important biomass-derived building block, but production and sustainable utilization of HMF remain challenging due to reactions of the highly reactive functional groups of this compound. H(4)SiW(12)O(40)/MCM-41 nanospheres were developed that exhibit 84.1% selectivity to 5-ethoxymethylfurfural (EMF) when HMF conversion reaches 92.0%, during etherification of 5-hydroxymethylfurfural (HMF) with ethanol under mild conditions. The catalyst could be reused, and its activity remained unaffected over five cycles. The strong acidity of the catalyst significantly enhanced etherification. The acetalized byproducts, 5-(diethoxymethyl)-2-furanmethanol and the HMF-dimer (5,5'(oxy-bis(methylene))bis-2-furfural), can be converted into HMF and then transformed to the main product, EMF, by using this catalyst to shift the reaction equilibrium. PMID:22749371

  11. The Pattern of Change in the Abundances of Specific Bacterioplankton Groups Is Consistent across Different Nutrient-Enriched Habitats in Crete

    PubMed Central

    Fodelianakis, Stilianos; Papageorgiou, Nafsika; Pitta, Paraskevi; Kasapidis, Panagiotis; Karakassis, Ioannis

    2014-01-01

    A common source of disturbance for coastal aquatic habitats is nutrient enrichment through anthropogenic activities. Although the water column bacterioplankton communities in these environments have been characterized in some cases, changes in α-diversity and/or the abundances of specific taxonomic groups across enriched habitats remain unclear. Here, we investigated the bacterial community changes at three different nutrient-enriched and adjacent undisturbed habitats along the north coast of Crete, Greece: a fish farm, a closed bay within a town with low water renewal rates, and a city port where the level of nutrient enrichment and the trophic status of the habitat were different. Even though changes in α-diversity were different at each site, we observed across the sites a common change pattern accounting for most of the community variation for five of the most abundant bacterial groups: a decrease in the abundance of the Pelagibacteraceae and SAR86 and an increase in the abundance of the Alteromonadaceae, Rhodobacteraceae, and Cryomorphaceae in the impacted sites. The abundances of the groups that increased and decreased in the impacted sites were significantly correlated (positively and negatively, respectively) with the total heterotrophic bacterial counts and the concentrations of dissolved organic carbon and/or dissolved nitrogen and chlorophyll α, indicating that the common change pattern was associated with nutrient enrichment. Our results provide an in situ indication concerning the association of specific bacterioplankton groups with nutrient enrichment. These groups could potentially be used as indicators for nutrient enrichment if the pattern is confirmed over a broader spatial and temporal scale by future studies. PMID:24747897

  12. Peptidyl-CCA deacylation on the ribosome promoted by induced fit and the O3′-hydroxyl group of A76 of the unacylated A-site tRNA

    SciTech Connect

    Simonović, Miljan; Steitz, Thomas A.

    2008-11-24

    The last step in ribosome-catalyzed protein synthesis is the hydrolytic release of the newly formed polypeptide from the P-site bound tRNA. Hydrolysis of the ester link of the peptidyl-tRNA is stimulated normally by the binding of release factors (RFs). However, an unacylated tRNA or just CCA binding to the ribosomal A site can also stimulate deacylation under some nonphysiological conditions. Although the sequence of events is well described by biochemical studies, the structural basis of the mechanism underlying this process is not well understood. Two new structures of the large ribosomal subunit of Haloarcula marismortui complexed with a peptidyl-tRNA analog in the P site and two oligonucleotide mimics of unacylated tRNA, CCA and CA, in the A site show that the binding of either CA or CCA induces a very similar conformational change in the peptidyl-transferase center as induced by aminoacyl-CCA. However, only CCA positions a water molecule appropriately to attack the carbonyl carbon of the peptidyl-tRNA and stabilizes the proper orientation of the ester link for hydrolysis. We, thus, conclude that both the ability of the O3'-hydroxyl group of the A-site A76 to position the water and the A-site CCA induced conformational change of the PTC are critical for the catalysis of the deacylation of the peptidyl-tRNA by CCA, and perhaps, an analogous mechanism is used by RFs.

  13. Hydroxylated PBDEs induce developmental arrest in zebrafish

    SciTech Connect

    Usenko, Crystal Y. Hopkins, David C.; Trumble, Stephen J. Bruce, Erica D.

    2012-07-01

    The ubiquitous spread of polybrominated diphenyl ethers (PBDEs) has led to concerns regarding the metabolites of these congeners, in particular hydroxylated PBDEs. There are limited studies regarding the biological interactions of these chemicals, yet there is some concern they may be more toxic than their parent compounds. In this study three hydroxylated PBDEs were assessed for toxicity in embryonic zebrafish: 3-OH-BDE 47, 5-OH-BDE 47, and 6-OH-BDE 47. All three congeners induced developmental arrest in a concentration-dependent manner; however, 6-OH-BDE 47 induced adverse effects at lower concentrations than the other congeners. Furthermore, all three induced cell death; however apoptosis was not observed. In short-term exposures (24–28 hours post fertilization), all hydroxylated PBDEs generated oxidative stress in the region corresponding to the cell death at 5 and 10 ppm. To further investigate the short-term effects that may be responsible for the developmental arrest observed in this study, gene regulation was assessed for embryos exposed to 0.625 ppm 6-OH-BDE 47 from 24 to 28 hpf. Genes involved in stress response, thyroid hormone regulation, and neurodevelopment were significantly upregulated compared to controls; however, genes related to oxidative stress were either unaffected or downregulated. This study suggests that hydroxylated PBDEs disrupt development, and may induce oxidative stress and potentially disrupt the cholinergic system and thyroid hormone homeostasis. -- Highlights: ► OH-PBDEs induce developmental arrest in a concentration-dependent manner. ► Hydroxyl group location influences biological interaction. ► OH-PBDEs induce oxidative stress. ► Thyroid hormone gene regulation was disrupted following exposure. ► To our knowledge, this is the first whole organism study of OH-PBDE toxicity.

  14. Towards a full understanding of the nature of Ni(II) species and hydroxyl groups over highly siliceous HZSM-5 zeolite supported nickel catalysts prepared by a deposition-precipitation method.

    PubMed

    Chen, Bao-Hui; Chao, Zi-Sheng; He, Hao; Huang, Chen; Liu, Ya-Juan; Yi, Wen-Jun; Wei, Xue-Ling; An, Jun-Fang

    2016-02-14

    Highly siliceous HZSM-5 zeolite supported nickel catalysts prepared by a deposition-precipitation (D-P) method were characterized by Fourier transform infrared (FT-IR), hydrogen temperature programmed reduction (H2-TPR), X-ray diffraction (XRD), N2-absorption/desorption, field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), and (27)Al magic-angle nuclear magnetic resonance (MAS NMR) techniques. The results showed that the D-P of nickel species occurred predominantly on the internal surface of highly siliceous HZSM-5 zeolite, in which the internal silanol groups located on the hydroxylated mesopores or nanocavities played a key role. During the D-P process, nickel hydroxide was first deposited-precipitated via olation/polymerization of neutral hydroxoaqua nickel species over the HZSM-5 zeolite. With the progress of the D-P process, 1 : 1 nickel phyllosilicate was formed over the HZSM-5 via the hetero-condensation/polymerization between charged hydroxoaqua nickel species and monomer silicic species generated due to the partial dissolution of the HZSM-5 framework. The 1 : 1 nickel phyllosilicate could also be generated via the hydrolytic adsorption of hydroxoaqua nickel species and their subsequent olation condensation. After calcination, the deposited-precipitated nickel hydroxide was decomposed into nickel oxide, while the 1 : 1 nickel phyllosilicate was transformed into 2 : 1 nickel phyllosilicate. According to the above mechanism, Ni(ii) species were present both in the form of nickel oxide and 2 : 1 nickel phyllosilicate, which were mutually separated from each other, being highly dispersed over HZSM-5 zeolite.

  15. Studies on the selectivity between nickel-catalyzed 1,2-cis-2-amino glycosylation of hydroxyl groups of thioglycoside acceptors with C2-substituted benzylidene N-phenyl trifluoroacetimidates and intermolecular aglycon transfer of the sulfide group.

    PubMed

    Yu, Fei; Nguyen, Hien M

    2012-09-01

    The stereoselective synthesis of saccharide thioglycosides containing 1,2-cis-2-amino glycosidic linkages is challenging. In addition to the difficulties associated with achieving high α-selectivity in the formation of 1,2-cis-2-amino glycosidic bonds, the glycosylation reaction is hampered by undesired transfer of the anomeric sulfide group from the glycosyl acceptor to the glycosyl donor. Overcoming these obstacles will pave the way for the preparation of oligosaccharides and glycoconjugates bearing the 1,2-cis-2-amino glycosidic linkages because the saccharide thioglycosides obtained can serve as donors for another coupling iteration. This approach streamlines selective deprotection and anomeric derivatization steps prior to the subsequent coupling event. We have developed an efficient approach for the synthesis of highly yielding and α-selective saccharide thioglycosides containing 1,2-cis-2-amino glycosidic bonds, via cationic nickel-catalyzed glycosylation of thioglycoside acceptors bearing the 2-trifluoromethylphenyl aglycon with N-phenyl trifluoroacetimidate donors. The 2-trifluoromethylphenyl group effectively blocks transfer of the anomeric sulfide group from the glycosyl acceptor to the C(2)-benzylidene donor and can be easily installed and activated. The current method also highlights the efficacy of the nickel catalyst selectively activating the C(2)-benzylidene imidate group in the presence of the anomeric sulfide group on the glycosyl acceptors. PMID:22838405

  16. THE ABUNDANCES OF HYDROCARBON FUNCTIONAL GROUPS IN THE INTERSTELLAR MEDIUM INFERRED FROM LABORATORY SPECTRA OF HYDROGENATED AND METHYLATED POLYCYCLIC AROMATIC HYDROCARBONS

    SciTech Connect

    Steglich, M.; Jäger, C.; Huisken, F.; Friedrich, M.; Plass, W.; Räder, H.-J.; Müllen, K.; Henning, Th.

    2013-10-01

    Infrared (IR) absorption spectra of individual polycyclic aromatic hydrocarbons (PAHs) containing methyl (-CH{sub 3}), methylene (CH{sub 2}), or diamond-like CH groups and IR spectra of mixtures of methylated and hydrogenated PAHs prepared by gas-phase condensation were measured at room temperature (as grains in pellets) and at low temperature (isolated in Ne matrices). In addition, the PAH blends were subjected to an in-depth molecular structure analysis by means of high-performance liquid chromatography, nuclear magnetic resonance spectroscopy, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Supported by calculations at the density functional theory level, the laboratory results were applied to analyze in detail the aliphatic absorption complex of the diffuse interstellar medium at 3.4 μm and to determine the abundances of hydrocarbon functional groups. Assuming that the PAHs are mainly locked in grains, aliphatic CH {sub x} groups (x = 1, 2, 3) would contribute approximately in equal quantities to the 3.4 μm feature (N {sub CHx}/N {sub H} ≈ 10{sup –5}-2 × 10{sup –5}). The abundances, however, may be two to four times lower if a major contribution to the 3.4 μm feature comes from molecules in the gas phase. Aromatic ≅CH groups seem to be almost absent from some lines of sight, but can be nearly as abundant as each of the aliphatic components in other directions (N{sub ≅CH}/N {sub H} ∼< 2 × 10{sup –5}; upper value for grains). Due to comparatively low binding energies, astronomical IR emission sources do not display such heavy excess hydrogenation. At best, especially in protoplanetary nebulae, CH{sub 2} groups bound to aromatic molecules, i.e., excess hydrogens on the molecular periphery only, can survive the presence of a nearby star.

  17. Interaction of Gold Clusters with a Hydroxylated Surface

    SciTech Connect

    Jiang, Deen; Overbury, Steven {Steve} H; Dai, Sheng

    2011-01-01

    We explore the interaction between gold nanoclusters and a fully hydroxylated surface, Mg(OH){sub 2}'s basal plane, by using a density functional theory-enabled local basin-hopping technique for global-minimum search. We find strong interaction of gold nanoclusters with the surface hydroxyls via a short bond between edge Au atoms and O atoms of the -OH groups. We expect that this strong interaction is ubiquitous on hydroxylated support surfaces and helps the gold nanoclusters against sintering, thereby contributing to their CO-oxidation activity at low temperatures.

  18. a Measurement of Hydroxyl in the Daytime Mesosphere.

    NASA Astrophysics Data System (ADS)

    Cageao, Richard Philip

    Hydroxyl is a very reactive free radical which dominates the odd-hydrogen - odd-oxygen reaction chemistry in the earth's mesosphere. The objective of this thesis was the development of an instrument which would measure the concentration of hydroxyl in the mesosphere and an assessment, based on this data, of the current understanding of mesospheric chemistry. A new instrument, a coupled Ebert-Fastie spectrometer and Fabry-Perot interferometer (UV-FPI), was developed to measure spectroscopically the ultraviolet solar resonance fluorescence emission of hydroxyl. The instrument was designed to observe these emissions in the near-ultraviolet at 3087 A against the bright background of Rayleigh scattered sunlight. The background was suppressed by the high resolution Fabry-Perot interferometer operating over the narrow wavelength region defined by the Ebert -Fastie spectrometer bandpass. The remote measurement of hydroxyl was made from a sounding rocket platform with the instrument viewing the earth's limb for the maximum integrated path length of hydroxyl emission. The sounding rocket payload also carried instruments which made simultaneous in situ and remote sensing measurements of atomic oxygen and temperature, respectively. Although the UV-FPI configuration was not optimum for measurement of the desired hydroxyl emission, upper limits could be set on the hydroxyl concentrations. The hydroxyl concentration inferred from the emission measurements was 50% lower than a previous measurement. Comparison of this result and the data for mesospheric abundances of ozone and atomic oxygen with current chemical models shows that modeled odd-hydrogen activity in the middle mesosphere must be reduced and vertical advection in the upper mesosphere must be increased in order to successfully model the chemical processes occurring in the mesosphere.

  19. A new strategy for integrating abundant oxygen functional groups into carbon felt electrode for vanadium redox flow batteries

    PubMed Central

    Kim, Ki Jae; Lee, Seung-Wook; Yim, Taeeun; Kim, Jae-Geun; Choi, Jang Wook; Kim, Jung Ho; Park, Min-Sik; Kim, Young-Jun

    2014-01-01

    The effects of surface treatment combining corona discharge and hydrogen peroxide (H2O2) on the electrochemical performance of carbon felt electrodes for vanadium redox flow batteries (VRFBs) have been thoroughly investigated. A high concentration of oxygen functional groups has been successfully introduced onto the surface of the carbon felt electrodes by a specially designed surface treatment, which is mainly responsible for improving the energy efficiency of VRFBs. In addition, the wettability of the carbon felt electrodes also can be significantly improved. The energy efficiency of the VRFB cell employing the surface modified carbon felt electrodes is improved by 7% at high current density (148 mA cm−2). Such improvement is attributed to the faster charge transfer and better wettability allowed by surface-active oxygen functional groups. Moreover, this method is much more competitive than other surface treatments in terms of processing time, production costs, and electrochemical performance. PMID:25366060

  20. A new strategy for integrating abundant oxygen functional groups into carbon felt electrode for vanadium redox flow batteries

    NASA Astrophysics Data System (ADS)

    Kim, Ki Jae; Lee, Seung-Wook; Yim, Taeeun; Kim, Jae-Geun; Choi, Jang Wook; Kim, Jung Ho; Park, Min-Sik; Kim, Young-Jun

    2014-11-01

    The effects of surface treatment combining corona discharge and hydrogen peroxide (H2O2) on the electrochemical performance of carbon felt electrodes for vanadium redox flow batteries (VRFBs) have been thoroughly investigated. A high concentration of oxygen functional groups has been successfully introduced onto the surface of the carbon felt electrodes by a specially designed surface treatment, which is mainly responsible for improving the energy efficiency of VRFBs. In addition, the wettability of the carbon felt electrodes also can be significantly improved. The energy efficiency of the VRFB cell employing the surface modified carbon felt electrodes is improved by 7% at high current density (148 mA cm-2). Such improvement is attributed to the faster charge transfer and better wettability allowed by surface-active oxygen functional groups. Moreover, this method is much more competitive than other surface treatments in terms of processing time, production costs, and electrochemical performance.

  1. The Araucaria Project: The Distance to the Sculptor Group Galaxy NGC 55 from a Newly Discovered Abundant Cepheid Population

    NASA Astrophysics Data System (ADS)

    Pietrzyński, Grzegorz; Gieren, Wolfgang; Soszyński, Igor; Udalski, Andrzej; Bresolin, Fabio; Kudritzki, Rolf-Peter; Mennickent, Ronald; Walker, Alistair; Garcia, Alejandro; Szewczyk, Olaf; Szymański, MichaŁ; Kubiak, Marcin; Wyrzykowski, Łukasz

    2006-12-01

    We have detected, for the first time, Cepheid variables in the Sculptor Group SB(s)m galaxy NGC 55. From wide-field images obtained in the optical V and I bands during 77 nights in 2002-2003, we have found 143 Cepheids with periods ranging from 5.6 to 175.9 days; 133 of these objects have periods longer than 10 days, making NGC 55 to date the galaxy with the largest known number of long-period Cepheids in the Sculptor Group. We construct period-luminosity relations from our data and obtain distance moduli corrected for the small foreground reddening to NGC 55 of 26.79+/-0.04 mag (internal error) in V, 26.66+/-0.03 mag in I, and 26.40+/-0.05 mag in the reddening-independent V-I Wesenheit index. The trend of increasing distance moduli with shorter wavelength hints at the existence of significant reddening intrinsic to NGC 55, which affects the measured Cepheid magnitudes. From our data we determine the intrinsic mean reddening of the Cepheids in NGC 55 as E(B-V)=0.102 mag, which brings the distance determinations from the different bands into excellent agreement. Our best distance estimate for NGC 55 from the present optical Cepheid photometry is 26.40+/-0.05 (internal error) +/-0.09 mag (systematic error). This value is tied to an assumed LMC distance of 18.50 mag. Our quoted systematic error of the present NGC 55 Cepheid distance does not take into account the current uncertainty in the distance of the fiducial LMC galaxy itself. Within the small respective uncertainties, the Sculptor Group galaxies NGC 55 and NGC 300 are at the same distance of 1.9 Mpc, strengthening the case for a physical association of these galaxies. Based on observations obtained with the 1.3 m Warsaw telescope at Las Campanas Observatory, Chile.

  2. The Abundances of Hydrocarbon Functional Groups in the Interstellar Medium Inferred from Laboratory Spectra of Hydrogenated and Methylated Polycyclic Aromatic Hydrocarbons

    NASA Astrophysics Data System (ADS)

    Steglich, M.; Jäger, C.; Huisken, F.; Friedrich, M.; Plass, W.; Räder, H.-J.; Müllen, K.; Henning, Th.

    2013-10-01

    Infrared (IR) absorption spectra of individual polycyclic aromatic hydrocarbons (PAHs) containing methyl (\\sbondCH3), methylene (\\protect{\\epsfbox{art/apjs484229un01.eps}}CH2), or diamond-like \\protect{\\epsfbox{art/apjs484229un02.eps}}CH groups and IR spectra of mixtures of methylated and hydrogenated PAHs prepared by gas-phase condensation were measured at room temperature (as grains in pellets) and at low temperature (isolated in Ne matrices). In addition, the PAH blends were subjected to an in-depth molecular structure analysis by means of high-performance liquid chromatography, nuclear magnetic resonance spectroscopy, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Supported by calculations at the density functional theory level, the laboratory results were applied to analyze in detail the aliphatic absorption complex of the diffuse interstellar medium at 3.4 μm and to determine the abundances of hydrocarbon functional groups. Assuming that the PAHs are mainly locked in grains, aliphatic CH x groups (x = 1, 2, 3) would contribute approximately in equal quantities to the 3.4 μm feature (N CHx /N H ≈ 10-5-2 × 10-5). The abundances, however, may be two to four times lower if a major contribution to the 3.4 μm feature comes from molecules in the gas phase. Aromatic \\epsfbox{art/apjs484229un03.eps} CH groups seem to be almost absent from some lines of sight, but can be nearly as abundant as each of the aliphatic components in other directions (N_{\\epsfbox{art/apjs484229un03.eps} CH}/N H lsim 2 × 10-5 upper value for grains). Due to comparatively low binding energies, astronomical IR emission sources do not display such heavy excess hydrogenation. At best, especially in protoplanetary nebulae, \\protect{\\epsfbox{art/apjs484229un01.eps}}CH2 groups bound to aromatic molecules, i.e., excess hydrogens on the molecular periphery only, can survive the presence of a nearby star.

  3. Model-measurement comparison of functional group abundance in α-pinene and 1,3,5-trimethylbenzene secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Ruggeri, Giulia; Bernhard, Fabian A.; Henderson, Barron H.; Takahama, Satoshi

    2016-07-01

    Secondary organic aerosol (SOA) formed by α-pinene and 1,3,5-trimethylbenzene photooxidation under different NOx regimes is simulated using the Master Chemical Mechanism v3.2 (MCM) coupled with an absorptive gas-particle partitioning module. Vapor pressures for individual compounds are estimated with the SIMPOL.1 group contribution model for determining apportionment of reaction products to each phase. We apply chemoinformatic tools to harvest functional group (FG) composition from the simulations and estimate their contributions to the overall oxygen to carbon ratio. Furthermore, we compare FG abundances in simulated SOA to measurements of FGs reported in previous chamber studies using Fourier transform infrared spectroscopy. These simulations qualitatively capture the dynamics of FG composition of SOA formed from both α-pinene and 1,3,5-trimethylbenzene in low-NOx conditions, especially in the first hours after start of photooxidation. Higher discrepancies are found after several hours of simulation; the nature of these discrepancies indicates sources of uncertainty or types of reactions in the condensed or gas phase missing from current model implementation. Higher discrepancies are found in the case of α-pinene photooxidation under different NOx concentration regimes, which are reasoned through the domination by a few polyfunctional compounds that disproportionately impact the simulated FG abundance in the aerosol phase. This manuscript illustrates the usefulness of FG analysis to complement existing methods for model-measurement evaluation.

  4. Selective hydroxylation of alkanes by an extracellular fungal peroxygenase.

    PubMed

    Peter, Sebastian; Kinne, Matthias; Wang, Xiaoshi; Ullrich, René; Kayser, Gernot; Groves, John T; Hofrichter, Martin

    2011-10-01

    Fungal peroxygenases are novel extracellular heme-thiolate biocatalysts that are capable of catalyzing the selective monooxygenation of diverse organic compounds, using only H(2)O(2) as a cosubstrate. Little is known about the physiological role or the catalytic mechanism of these enzymes. We have found that the peroxygenase secreted by Agrocybe aegerita catalyzes the H(2)O(2)-dependent hydroxylation of linear alkanes at the 2-position and 3-position with high efficiency, as well as the regioselective monooxygenation of branched and cyclic alkanes. Experiments with n-heptane and n-octane showed that the hydroxylation proceeded with complete stereoselectivity for the (R)-enantiomer of the corresponding 3-alcohol. Investigations with a number of model substrates provided information about the route of alkane hydroxylation: (a) the hydroxylation of cyclohexane mediated by H(2)(18)(2) resulted in complete incorporation of (18)O into the hydroxyl group of the product cyclohexanol; (b) the hydroxylation of n-hexane-1,1,1,2,2,3,3-D(7) showed a large intramolecular deuterium isotope effect [(k(H)/k(D))(obs)] of 16.0 ± 1.0 for 2-hexanol and 8.9 ± 0.9 for 3-hexanol; and (c) the hydroxylation of the radical clock norcarane led to an estimated radical lifetime of 9.4 ps and an oxygen rebound rate of 1.06 × 10(11) s(-1). These results point to a hydrogen abstraction and oxygen rebound mechanism for alkane hydroxylation. The peroxygenase appeared to lack activity on long-chain alkanes (> C(16)) and highly branched alkanes (e.g. tetramethylpentane), but otherwise exhibited a broad substrate range. It may accordingly have a role in the bioconversion of natural and anthropogenic alkane-containing structures (including alkyl chains of complex biomaterials) in soils, plant litter, and wood. PMID:21812933

  5. Millimeter-scale variations of stable isotope abundances in carbonates from banded iron-formations in the Hamersley Group of Western Australia.

    PubMed

    Baur, M E; Hayes, J M; Studley, S A; Walter, M R

    1985-01-01

    Several diamond drill cores from formations within the Hamersley Group of Western Australia have been studied for evidence of short-range variations in the isotopic compositions of the carbonates. For a set of 32 adjacent microbands analyzed in a specimen from the Marra Mamba Iron Formation, carbon isotope compositions of individual microbands ranged from -2.8 to -19.8 per mil compared to PDB and oxygen isotope compositions ranged from 10.2 to 20.8 per mil compared to SMOW. A pattern of alternating abundances was present, with the average isotopic contrasts between adjacent microbands being 3.0 per mil for carbon and 3.1 per mil for oxygen. Similar results were obtained for a suite of 34 microbands (in four groups) from the Bruno's Band unit of the Mount Sylvia Formation. Difficulties were experienced in preparing samples of single microbands from the Dales Gorge Member of the Brockman Iron Formation, but overall isotopic compositions were in good agreement with values reported by previous authors. Chemical analyses showed that isotopically light carbon and oxygen were correlated with increased concentrations of iron. The preservation of these millimeter-scale variations in isotopic abundances is interpreted as inconsistent with a metamorphic origin for the isotopically light carbon in the BIF carbonates. A biological origin is favored for the correlated variations in 13C and Fe, and it is suggested that the 13C-depleted carbonates may derive either from fermentative metabolism or from anaerobic respiration. A model is presented in which these processes occur near the sediment-water interface and are coupled with an initial oxidative precipitation of the iron. PMID:11539027

  6. Millimeter-scale variations of stable isotope abundances in carbonates from banded iron-formations in the Hamersley Group of Western Australia

    NASA Technical Reports Server (NTRS)

    Baur, M. E.; Hayes, J. M.; Studley, S. A.; Walter, M. R.

    1985-01-01

    Several diamond drill cores from formations within the Hamersley Group of Western Australia have been studied for evidence of short-range variations in the isotopic compositions of the carbonates. For a set of 32 adjacent microbands analyzed in a specimen from the Marra Mamba Iron Formation, carbon isotope compositions of individual microbands ranged from -2.8 to -19.8 per mil compared to PDB and oxygen isotope compositions ranged from 10.2 to 20.8 per mil compared to SMOW. A pattern of alternating abundances was present, with the average isotopic contrasts between adjacent microbands being 3.0 per mil for carbon and 3.1 per mil for oxygen. Similar results were obtained for a suite of 34 microbands (in four groups) from the Bruno's Band unit of the Mount Sylvia Formation. Difficulties were experienced in preparing samples of single microbands from the Dales Gorge Member of the Brockman Iron Formation, but overall isotopic compositions were in good agreement with values reported by previous authors. Chemical analyses showed that isotopically light carbon and oxygen were correlated with increased concentrations of iron. The preservation of these millimeter-scale variations in isotopic abundances is interpreted as inconsistent with a metamorphic origin for the isotopically light carbon in the BIF carbonates. A biological origin is favored for the correlated variations in 13C and Fe, and it is suggested that the 13C-depleted carbonates may derive either from fermentative metabolism or from anaerobic respiration. A model is presented in which these processes occur near the sediment-water interface and are coupled with an initial oxidative precipitation of the iron.

  7. The Unstructured N-terminal Region of Arabidopsis Group 4 Late Embryogenesis Abundant (LEA) Proteins Is Required for Folding and for Chaperone-like Activity under Water Deficit.

    PubMed

    Cuevas-Velazquez, Cesar L; Saab-Rincón, Gloria; Reyes, José Luis; Covarrubias, Alejandra A

    2016-05-13

    Late embryogenesis abundant (LEA) proteins are a conserved group of proteins widely distributed in the plant kingdom that participate in the tolerance to water deficit of different plant species. In silico analyses indicate that most LEA proteins are structurally disordered. The structural plasticity of these proteins opens the question of whether water deficit modulates their conformation and whether these possible changes are related to their function. In this work, we characterized the secondary structure of Arabidopsis group 4 LEA proteins. We found that they are disordered in aqueous solution, with high intrinsic potential to fold into α-helix. We demonstrate that complete dehydration is not required for these proteins to sample ordered structures because milder water deficit and macromolecular crowding induce high α-helix levels in vitro, suggesting that prevalent conditions under water deficit modulate their conformation. We also show that the N-terminal region, conserved across all group 4 LEA proteins, is necessary and sufficient for conformational transitions and that their protective function is confined to this region, suggesting that folding into α-helix is required for chaperone-like activity under water limitation. We propose that these proteins can exist as different conformers, favoring functional diversity, a moonlighting property arising from their structural dynamics. PMID:27006402

  8. The role of the 4''-hydroxyl on motilin agonist potency in the 9-dihydroerythromycin series.

    PubMed

    Liu, Yaoquan; Carreras, Christopher W; Claypool, Mark; Myles, David C; Shaw, Simon J

    2011-06-15

    The role of the erythromycin 4''-hydroxyl group has been explored on the motilin agonist potential in the 9-dihydroerythromycin series of motilides. The compounds show potencies 2- to 4-fold superior to the corresponding hydroxylated compounds. The relationship is maintained when the 9-hydroxyl is alkylated to generate the corresponding 4''-deoxy-9-O-acetamido-9-dihydroerythromycins. However, concomitant with this increase in potency is an increase in hERG inhibition.

  9. Mapping nucleic acid structure by hydroxyl radical cleavage.

    PubMed

    Tullius, Thomas D; Greenbaum, Jason A

    2005-04-01

    Hydroxyl radical footprinting is a widely used method for following the folding of RNA molecules in solution. This method has the unique ability to provide experimental information on the solvent accessibility of each nucleotide in an RNA molecule, so that the folding of all domains of the RNA species can be followed simultaneously at single-nucleotide resolution. In recent work, hydroxyl radical footprinting has been used, often in combination with other global measures of structure, to work out detailed folding pathways and three-dimensional structures for increasingly large and complicated RNA molecules. These include synthetic ribozymes, and group I and group II ribozymes, from yeast, the Azoarcus cyanobacterium and Tetrahymena thermophila. Advances have been made in methods for analysis of hydroxyl radical data, so that the large datasets that result from kinetic folding experiments can be analyzed in a semi-automated and quantitative manner.

  10. A Group 6 Late Embryogenesis Abundant Protein from Common Bean Is a Disordered Protein with Extended Helical Structure and Oligomer-forming Properties*

    PubMed Central

    Rivera-Najera, Lucero Y.; Saab-Rincón, Gloria; Battaglia, Marina; Amero, Carlos; Pulido, Nancy O.; García-Hernández, Enrique; Solórzano, Rosa M.; Reyes, José L.; Covarrubias, Alejandra A.

    2014-01-01

    Late embryogenesis-abundant proteins accumulate to high levels in dry seeds. Some of them also accumulate in response to water deficit in vegetative tissues, which leads to a remarkable association between their presence and low water availability conditions. A major sub-group of these proteins, also known as typical LEA proteins, shows high hydrophilicity and a high percentage of glycine and other small amino acid residues, distinctive physicochemical properties that predict a high content of structural disorder. Although all typical LEA proteins share these characteristics, seven groups can be distinguished by sequence similarity, indicating structural and functional diversity among them. Some of these groups have been extensively studied; however, others require a more detailed analysis to advance in their functional understanding. In this work, we report the structural characterization of a group 6 LEA protein from a common bean (Phaseolus vulgaris L.) (PvLEA6) by circular dichroism and nuclear magnetic resonance showing that it is a disordered protein in aqueous solution. Using the same techniques, we show that despite its unstructured nature, the addition of trifluoroethanol exhibited an intrinsic potential in this protein to gain helicity. This property was also promoted by high osmotic potentials or molecular crowding. Furthermore, we demonstrate that PvLEA6 protein is able to form soluble homo-oligomeric complexes that also show high levels of structural disorder. The association between PvLEA6 monomers to form dimers was shown to occur in plant cells by bimolecular fluorescence complementation, pointing to the in vivo functional relevance of this association. PMID:25271167

  11. Conformation of a Group 2 Late Embryogenesis Abundant Protein from Soybean. Evidence of Poly (l-Proline)-type II Structure1

    PubMed Central

    Soulages, Jose L.; Kim, Kangmin; Arrese, Estela L.; Walters, Christina; Cushman, John C.

    2003-01-01

    Late embryogenesis abundant (LEA) proteins are members of a large group of hydrophilic, glycine-rich proteins found in plants, algae, fungi, and bacteria known collectively as hydrophilins that are preferentially expressed in response to dehydration or hyperosmotic stress. Group 2 LEA (dehydrins or responsive to abscisic acid) proteins are postulated to stabilize macromolecules against damage by freezing, dehydration, ionic, or osmotic stress. However, the structural and physicochemical properties of group 2 LEA proteins that account for such functions remain unknown. We have analyzed the structural properties of a recombinant form of a soybean (Glycine max) group 2 LEA (rGmDHN1). Differential scanning calorimetry of purified rGmDHN1 demonstrated that the protein does not display a cooperative unfolding transition upon heating. Ultraviolet absorption and circular dichroism spectroscopy revealed that the protein is in a largely hydrated and unstructured conformation in solution. However, ultraviolet absorption and circular dichroism measurements collected at different temperatures showed that the protein exists in equilibrium between two extended conformational states: unordered and left-handed extended helical or poly (l-proline)-type II structures. It is estimated that 27% of the residues of rGmDHN1 adopt or poly (l-proline)-type II-like helical conformation at 12°C. The content of extended helix gradually decreases to 15% as the temperature is increased to 80°C. Studies of the conformation of the protein in solution in the presence of liposomes, trifluoroethanol, and sodium dodecyl sulfate indicated that rGmDHN1 has a very low intrinsic ability to adopt α-helical structure and to interact with phospholipid bilayers through amphipathic α-helices. The ability of the protein to remain in a highly extended conformation at low temperatures could constitute the basis of the functional role of GmDHN1 in the prevention of freezing, desiccation, ionic, or osmotic

  12. A group 6 late embryogenesis abundant protein from common bean is a disordered protein with extended helical structure and oligomer-forming properties.

    PubMed

    Rivera-Najera, Lucero Y; Saab-Rincón, Gloria; Battaglia, Marina; Amero, Carlos; Pulido, Nancy O; García-Hernández, Enrique; Solórzano, Rosa M; Reyes, José L; Covarrubias, Alejandra A

    2014-11-14

    Late embryogenesis-abundant proteins accumulate to high levels in dry seeds. Some of them also accumulate in response to water deficit in vegetative tissues, which leads to a remarkable association between their presence and low water availability conditions. A major sub-group of these proteins, also known as typical LEA proteins, shows high hydrophilicity and a high percentage of glycine and other small amino acid residues, distinctive physicochemical properties that predict a high content of structural disorder. Although all typical LEA proteins share these characteristics, seven groups can be distinguished by sequence similarity, indicating structural and functional diversity among them. Some of these groups have been extensively studied; however, others require a more detailed analysis to advance in their functional understanding. In this work, we report the structural characterization of a group 6 LEA protein from a common bean (Phaseolus vulgaris L.) (PvLEA6) by circular dichroism and nuclear magnetic resonance showing that it is a disordered protein in aqueous solution. Using the same techniques, we show that despite its unstructured nature, the addition of trifluoroethanol exhibited an intrinsic potential in this protein to gain helicity. This property was also promoted by high osmotic potentials or molecular crowding. Furthermore, we demonstrate that PvLEA6 protein is able to form soluble homo-oligomeric complexes that also show high levels of structural disorder. The association between PvLEA6 monomers to form dimers was shown to occur in plant cells by bimolecular fluorescence complementation, pointing to the in vivo functional relevance of this association. PMID:25271167

  13. Remote sensing data to classify functional groups of vegetation and their distribution and abundance in a semiarid mountain watershed, Idaho, USA

    NASA Astrophysics Data System (ADS)

    Loughridge, R. E.; Benner, S. G.; McNamara, J. P.; Flores, A. N.

    2012-12-01

    In water-limited montane ecosystems, topography is a significant driver of energy balance and soil moisture and therefore governs the distribution and abundance of terrestrial vegetation. Few studies have made a concerted effort to quantify spatial patterns in vegetation along physiographic gradients that control microclimate such as slope, elevation, and aspect. Furthermore, spectral mixing of different vegetation species within individual visible and near-infrared remote sensing pixels makes it difficult to constrain the temporal growth and senescence of individual plant functional types. We report on a study that seeks to understand the interacting roles of topography, soil moisture, and solar radiation on the distribution of different plant functional types within the Dry Creek Experimental Watershed (DCEW). Boise State University maintains the 27 km2 watershed which is located in the Boise Front Mountains of southwest Idaho. It is qualitatively observed in DCEW that low elevations are dominated by sage-steppe ecosystems and high elevations transition to conifer forests. It is also observed that aspect has a major control in which sage-steppe is evident at high elevations on south facing slopes conversely from north facing slopes. To quantify these trends we measured percent ground cover of functional groups (i.e. forbs, grass, shrubs, etc.) at 77 sites within DCEW spanning a large gradient in the controlling biophysiographic variables. In addition, vegetation water content (VWC) and spectral reflectance from the 325 to 1075 nm wavelengths was collected for specific vegetation types at eight permanent soil moisture monitoring sites contained in DCEW throughout the 2012 green-up/senescence transition. To develop a watershed-wide classification we built a supervised multilayer perceptron (MLP) backpropagating artificial neural network (ANN) using temporal Landsat 5 images to classify 4 major groups: sage-steppe, Douglas fir, ponderosa pine, and deciduous trees

  14. Variations of the relative abundances of He, (C,N,O) and Fe-group nuclei in solar cosmic rays and their relationship to solar particle acceleration

    NASA Technical Reports Server (NTRS)

    Bertsch, D. L.; Biswas, S.; Fichtel, C. E.; Pellerin, C. J.; Reames, D. V.

    1973-01-01

    Measurements of the flux of helium nuclei in the 24 January 1971 event and of helium and (C,N,O) nuclei in the 1 September 1971 event are combined with previous measurements to obtain the relative abundances of helium, (C,N,O), and Fe-group nuclei in these events. These data are then summarized together with previously reported results to show that, even when the same detector system using a dE/dx plus range technique is used, differences in the He/(C,N,O) value in the same energy/nucleon interval are observed in solar cosmic ray events. Further, when the He/(C,N,O) value is lower the He/(Fe-group nuclei) value is also systematically lower in these large events. When solar particle acceleration theory is analyzed, it is seen that the results suggest that, for large events, Coulomb energy loss probably does not play a major role in determining solar particle composition at higher energies (10 MeV). The variations in multicharged nuclei composition are more likely due to partial ionization during the acceleration phase.

  15. Synthesis of Azide-Functionalized Hydroxyl-Terminated Polybutadiene

    NASA Astrophysics Data System (ADS)

    Shekhar Pant, Chandra; Santosh Mada, S. S. N. M.; Mehilal; Banerjee, Shaibal; Khanna, Pawan K.

    2016-10-01

    This article reports ways to functionalize hydroxyl-terminated polybutadiene (HTPB) by azide groups to impart energetic properties to the polymer. Two different synthetic approaches were explored to synthesize azide-functionalized hydroxyl-terminated polybutadiene (azide-HTPB). The functionalized polymer was analyzed for structural confirmation and determination of important physical and thermal properties. Azide-HTPB obtained by azidation of 10% double bonds of HTPB showed viscosity of 11 Pa.s and a glass transition temperature of -66°C.

  16. Hydroxyl radical scavenging reactivity of proton pump inhibitors.

    PubMed

    Simon, Wolfgang Alexander; Sturm, Ernst; Hartmann, Hans-Jürgen; Weser, Ulrich

    2006-04-28

    In addition to the established control of acid secretion of the class of proton pump inhibitors (PPI) reactivity from the pyridyl methyl sulphinyl benzimidazole type a second independent anti-inflammatory reactivity was observed in vitro. This inhibitory reactivity was clearly noticed using three different assays where the aggressive hydroxyl radicals were successfully trapped in a concentration dependent manner. There is unequivocal evidence that the proton pump inhibitors having the sulphoxide group are able to scavenge hydroxyl radicals which are generated during a Fenton reaction. By way of contrast, the corresponding thioethers were substantially less active. No detectable effect was seen in the superoxide radical scavenging system. In conclusion, pantoprazole as well as the other proton pump inhibitors have a pronounced inhibitory reactivity towards hydroxyl radicals.

  17. Hydroxyl radical induced degradation of ibuprofen.

    PubMed

    Illés, Erzsébet; Takács, Erzsébet; Dombi, András; Gajda-Schrantz, Krisztina; Rácz, Gergely; Gonter, Katalin; Wojnárovits, László

    2013-03-01

    Pulse radiolysis experiments were used to characterize the intermediates formed from ibuprofen during electron beam irradiation in a solution of 0.1mmoldm(-3). For end product characterization (60)Co γ-irradiation was used and the samples were evaluated either by taking their UV-vis spectra or by HPLC with UV or MS detection. The reactions of OH resulted in hydroxycyclohexadienyl type radical intermediates. The intermediates produced in further reactions hydroxylated the derivatives of ibuprofen as final products. The hydrated electron attacked the carboxyl group. Ibuprofen degradation is more efficient under oxidative conditions than under reductive conditions. The ecotoxicity of the solution was monitored by Daphnia magna standard microbiotest and Vibrio fischeri luminescent bacteria test. The toxic effect of the aerated ibuprofen solution first increased upon irradiation indicating a higher toxicity of the first degradation products, then decreased with increasing absorbed dose.

  18. Influence of hydroxyl substitution on flavanone antioxidants properties.

    PubMed

    Masek, Anna; Chrzescijanska, Ewa; Latos, Malgorzata; Zaborski, Marian

    2017-01-15

    The aim of our study was to determine the effect of the position of the hydroxyl group on the antioxidant properties of flavonoid derivatives. For this purpose, we performed electrochemical analysis and quantum-mechanical calculations to describe the mechanisms of electrochemical oxidation, and we selected the two methods of ABTS (2,2'-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) and DPPH (2,2-diphenyl-1-picryl-hydrazyl-hydrate), which allowed us to determine the ability to scavenge free radicals. On the basis of the research, we found that the derivatives of flavonoids, which have a hydroxyl group substituted at the R-3 position on the C ring, have outstanding antioxidant activity. Flavone, which had an OH group substituted at the R-6 and R-7 position on the ring A, showed similar antioxidant activity to flavone without -OH groups in the structure and slightly higher activity than the di-substituted flavone on the ring A. PMID:27542504

  19. Determination of hydroxylated thiophenic compounds in a coal liquid

    SciTech Connect

    Nishioka, M.; Lee, M.L.; Kudo, H.; Muchiri, D.R.; Baldwin, L.J.; Pakray, S.; Stuart, J.G.; Castle, R.N.

    1985-06-01

    Hydroxylated thiophenic compounds in a coal liquid were determined by capillary column gas chromatography and gas chromatography/mass spectrometry. Capillary column gas chromatography with two new selective stationary phases, a biphenyl polysiloxane and a smectic liquid crystalline poly-siloxane, were used. Several compounds were positively identified by comparison of their retention times with those of newly synthesized standard compounds. Sulfur-selective flame photometric detection and mass spectrometry were used to verify compound identifications. Two groupings of hydroxylated thiophenic compounds were observed in this sample. The first group is composed of hydroxybenzo-thiophenes and (hydroxyphenyl)thiophenes, while the second group contains hydroxydibenzothiophenes and (hydroxyphenyl)benzothiophenes. 22 references, 2 figures, 1 table.

  20. Generation of hydroxyl radicals from metal-loaded humic acids

    SciTech Connect

    Paciolla, M.D.; Jansen, S.A.; Davies, G.

    1999-06-01

    Humic acids (HAs) are naturally occurring biopolymers that are ubiquitous in the environment. They are most commonly found in the soil, drinking water, and a variety of plants. Pharmacological and therapeutic studies involving humic acids have been reported to some extent. However, when certain transition metals are bound to humic acids, e.g., iron and copper, they can be harmful to biological organisms. For this study, humic acids were extracted from German, Irish, and New Hampshire soils that were selectively chosen because of their reich abundance in humic material. Each sample was treated at room temperature with 0.1 M ferric and cupric solutions for 48 h. The amount of iron and copper adsorbed by humic acid was accurately quantitated using atomic absorption spectroscopy. The authors further demonstrate that these metal-loaded humic acids can produce deleterious oxidizing species such as the hydroxyl radical (HO*) through the metal-driven Fenton reaction. Electron paramagnetic resonance (EPR) employing spin trapping techniques with 5,5-dimethylpyrroline N-oxide (DMPO) is used to confirm the generation of hydroxyl radicals. The DMPO-OH adduct with hyperfine splitting constants A{sub N} = A{sub H} = 14.9 G is observed upon the addition of exogenous hydrogen peroxide. The concentration of hydroxyl radical was determined using 4-hydroxytempo (TEMPO-OH) as a spin standard. The presence of another oxidizing species, Fe{double_bond}O{sup 2+}, is also proposed in the absence of hydrogen peroxide.

  1. Creation of localized spins in graphene by ring-opening of epoxy derived hydroxyl.

    PubMed

    Chen, Jie; Zhang, Weili; Sun, Yuanyuan; Zheng, Yongping; Tang, Nujiang; Du, Youwei

    2016-05-26

    Creation of high-density localized spins in the basal plane of graphene sheet by introduction of sp(3)-type defects is considered to be a potential route for the realization of high-magnetization graphene. Theoretical and experimental studies confirmed that hydroxyl can be an effective sp(3)-type candidate for inducing robust magnetic moment. However, the artificial generation of hydroxyl groups for creating high-density spins on the basal plane of graphene sheet is very scarce. Here we demonstrate that high-content hydroxyl groups can be generated on the basal plane of graphene oxide (GO) sheet by ring opening of epoxy groups. We show that by introduction of 10.74 at.% hydroxyl groups, the density of localized spins of GO can be significantly increased from 0.4 to 5.17 μB/1000 C. Thus, this study provided an effective method to obtain graphene with high-density localized spins.

  2. Creation of localized spins in graphene by ring-opening of epoxy derived hydroxyl

    PubMed Central

    Chen, Jie; Zhang, Weili; Sun, Yuanyuan; Zheng, Yongping; Tang, Nujiang; Du, Youwei

    2016-01-01

    Creation of high-density localized spins in the basal plane of graphene sheet by introduction of sp3-type defects is considered to be a potential route for the realization of high-magnetization graphene. Theoretical and experimental studies confirmed that hydroxyl can be an effective sp3-type candidate for inducing robust magnetic moment. However, the artificial generation of hydroxyl groups for creating high-density spins on the basal plane of graphene sheet is very scarce. Here we demonstrate that high-content hydroxyl groups can be generated on the basal plane of graphene oxide (GO) sheet by ring opening of epoxy groups. We show that by introduction of 10.74 at.% hydroxyl groups, the density of localized spins of GO can be significantly increased from 0.4 to 5.17 μB/1000 C. Thus, this study provided an effective method to obtain graphene with high-density localized spins. PMID:27225991

  3. Hydroxylation of a metal-supported hexagonal boron nitride monolayer by oxygen induced water dissociation.

    PubMed

    Guo, Yufeng; Guo, Wanlin

    2015-07-01

    Hydroxylated hexagonal boron nitride (h-BN) nanosheets exhibit potential application in nanocomposites and functional surface coating. Our first-principles calculations reveal possible hydroxylation of a h-BN monolayer on a Ni substrate by surface O adatom induced spontaneous dissociation of water molecules. Here one H atom is split from a water molecule by bonding with the O adatom on the B atom and the resulting O-H radical then bonds with an adjacent B atom, which leads to two hydroxyl groups formed on h-BN/Ni. Hydroxylation slightly influences the electronic properties of a Ni-supported h-BN layer. Similar water dissociation and hydroxylation can occur on the surface of O functionalized h-BN/Cu depending on the O adsorption configuration. Metal substrates play an important catalytic role in enhancing the chemical reactivity of O adatoms on h-BN with water molecules through transferring additional charges to them. PMID:26051363

  4. Regioselective and stereospecific hydroxylation of GR24 by Sorghum bicolor and evaluation of germination inducing activities of hydroxylated GR24 stereoisomers toward seeds of Striga species.

    PubMed

    Ueno, Kotomi; Ishiwa, Shunsuke; Nakashima, Hitomi; Mizutani, Masaharu; Takikawa, Hirosato; Sugimoto, Yukihiro

    2015-09-15

    Bioconversion of GR24, the most widely used synthetic strigolactone (SL), by hydroponically grown sorghum (Sorghum bicolor) and biological activities of hydroxylated GR24 stereoisomers were studied. Analysis of extracts and exudates of sorghum roots previously fed with a racemic and diastereomeric mixture of GR24, using liquid chromatography-tandem mass spectrometry with multiple reaction monitoring (MRM), confirmed uptake of GR24 and suggested its conversion to mono-hydroxylated products. Two major GR24 metabolites, 7-hydroxy-GR24 and 8-hydroxy-GR24, were identified in the root extracts and exudates by direct comparison of chromatographic behavior with a series of synthetic mono-hydroxylated GR24 analogues. Separate feeding experiments with each of the GR24 stereoisomers revealed that the hydroxylated products were derived from 2'-epi-GR24, an evidence of sterical recognition of the GR24 molecule by sorghum. Trans-4-hydroxy-GR24 isomers derived from all GR24 stereoisomers were detected in the exudates as minor metabolites. The synthetic hydroxy-GR24 isomers induced germination of Striga hermonthica in decreasing order of C-8>C-7>C-6>C-5>C-4. In contrast the stereoisomers having the same configuration of orobanchol, irrespective of position of hydroxylation, induced germination of Striga gesnerioides. The results confirm previous reports on structural requirements of SLs and ascribe a critical role to hydroxylation, but not to the position of the hydroxyl group in the AB part of the molecule, in induction of S. gesnerioides seed germination.

  5. Protein covalent immobilization via its scarce thiol versus abundant amine groups: Effect on orientation, cell binding domain exposure and conformational lability.

    PubMed

    Ba, O M; Hindie, M; Marmey, P; Gallet, O; Anselme, K; Ponche, A; Duncan, A C

    2015-10-01

    Quantity, orientation, conformation and covalent linkage of naturally cell adhesive proteins adsorbed or covalently linked to a surface, are known to influence the preservation of their subsequent long term cell adhesion properties and bioactivity. In the present work, we explore two different strategies for the covalent linking of plasma fibronectin (pFN) - used as a cell adhesive model protein, onto a polystyrene (PS) surface. One is aimed at tethering the protein to the surface in a semi-oriented fashion (via one of the 4 free thiol reactive groups on the protein) with a heterofunctional coupling agent (SSMPB method). The other aims to immobilize the protein in a more random fashion by reaction between the abundant pendant primary amine bearing amino acids of the pFN and activated carboxylic surface functions obtained after glutaric anhydride surface treatment (GA method). The overall goal will be to verify the hypothesis of a correlation between covalent immobilization of a model cell adhesive protein to a PS surface in a semi-oriented configuration (versus randomly oriented) with promotion of enhanced exposure of the protein's cell binding domain. This in turn would lead to enhanced cell adhesion. Ideally the goal is to elaborate substrates exhibiting a long term stable protein monolayer with preserved cell adhesive properties and bioactivity for biomaterial and/or cell adhesion commercial plate applications. However, the initial restrictive objective of this paper is to first quantitatively and qualitatively investigate the reversibly (merely adsorbed) versus covalently irreversibly bound protein to the surface after the immobilization procedure. Although immobilized surface amounts were similar (close to the monolayer range) for all immobilization approaches, covalent grafting showed improved retention and stronger "tethering" of the pFN protein to the surface (roughly 40%) after SDS rinsing compared to that for mere adsorption (0%) suggesting an added value

  6. Bacterial metabolism of hydroxylated biphenyls.

    PubMed Central

    Higson, F K; Focht, D D

    1989-01-01

    Isolates able to grow on 3- or 4-hydroxybiphenyl (HB) as the sole carbon source were obtained by enrichment culture. The 3-HB degrader Pseudomonas sp. strain FH12 used an NADPH-dependent monooxygenase restricted to 3- and 3,3'-HBs to introduce an ortho-hydroxyl. The 4-HB degrader Pseudomonas sp. strain FH23 used either a mono- or dioxygenase to generate a 2,3-diphenolic substitution pattern which allowed meta-fission of the aromatic ring. By using 3-chlorocatechol to inhibit catechol dioxygenase activity, it was found that 2- and 3-HBs were converted by FH23 to 2,3-HB, whereas biphenyl and 4-HB were attacked by dioxygenation. 4-HB was metabolized to 2,3,4'-trihydroxybiphenyl. Neither organism attacked chlorinated HBs. The degradation of 3- and 4-HBs by these strains is therefore analogous to the metabolism of biphenyl, 2-HB, and naphthalene in the requirement for 2,3-catechol formation. PMID:2729993

  7. Deciphering the Positional Influence of the Hydroxyl Group in the Cinnamoyl Part of 3-Hydroxy Flavonoids for Structural Modification and Their Interaction with the Protonated and B Form of Calf Thymus DNA Using Spectroscopic and Molecular Modeling Studies.

    PubMed

    Pradhan, Ankur Bikash; Haque, Lucy; Bhuiya, Sutanwi; Ganguly, Aniruddha; Das, Suman

    2015-06-11

    Studies on the interaction of naturally occurring flavonoids with different polymorphic forms of nucleic acid are helpful for understanding the molecular aspects of binding mode and providing direction for the use and design of new efficient therapeutic agents. However, much less information is available on the interactions of these compounds with different polymorphic forms of DNA at the molecular level. In this report we investigated the interaction of two widely abundant dietary flavonoids quercetin (Q) and morin (M) with calf thymus (CT) DNA. Spectrophotometric, spectropolarimetric, viscosity measurement, and molecular docking simulation methods are used as tools to delineate the binding mode and probable location of the flavonoids and their effects on the stability and conformation of DNA. It is observed that in the presence of the protonated form of DNA the dual fluorescence of Q and M resulting from the excited-state intramolecular proton transfer (ESIPT) is modified significantly. Structural analysis showed Q and M binds weakly to the B form (groove binding) compared to the protonated form of CT DNA (electrostatic interaction). In both cases, Q binds strongly to both forms of DNA compared to M.

  8. Abundances of platinum group elements in native sulfur condensates from the Niuatahi-Motutahi submarine volcano, Tonga rear arc: Implications for PGE mineralization in porphyry deposits

    NASA Astrophysics Data System (ADS)

    Park, Jung-Woo; Campbell, Ian H.; Kim, Jonguk

    2016-02-01

    Some porphyry Cu-Au deposits, which are enriched in Pd, are potentially an economic source of Pd. Magmatic volatile phases are thought to transport the platinum group elements (PGEs) from the porphyry source magma to the point of deposition. However, the compatibilities of the PGEs in magmatic volatile phases are poorly constrained. We report PGE and Re contents in native sulfur condensates and associated altered dacites from the Niuatahi-Motutahi submarine volcano, Tonga rear arc, in order to determine the compatibility of PGEs and Re in magmatic volatile phases, and their mobility during secondary hydrothermal alteration. The native sulfur we analyzed is the condensate of a magmatic volatile phase exsolved from the Niuatahi-Motutahi magma. The PGEs are moderately enriched in the sulfur condensates in comparison to the associated fresh dacite, with enrichment factors of 11-285, whereas Au, Cu and Re are strongly enriched with enrichment factors of ∼20,000, ∼5000 and ∼800 respectively. Although the PGEs are moderately compatible into magmatic volatile phases, their compatibility is significantly lower than that of Au, Cu and Re. Furthermore, the compatibility of PGEs decrease in the order: Ru > Pt > Ir > Pd. This trend is also observed in condensates and sublimates from other localities. PGE mineralization in porphyry Cu-Au deposits is characterized by substantially higher Pd/Pt (∼7-60) and Pd/Ir (∼100-10,500) than typical orthomagmatic sulfide deposits (e.g. Pd/Pt ∼0.6 and Pd/Ir ∼20 for the Bushveld). It has previously been suggested that the high mobility of Pd, relative to the other PGEs, may account for the preferential enrichment of Pd in porphyry Cu-Au deposits. However, the low compatibility of Pd in the volatile phase relative to the other PGEs, shown in this study, invalidates this explanation. We suggest that the PGE geochemistry of Pd-rich Cu-Au deposits is principally derived from the PGE characteristics of the magma from which the ore

  9. A characterization study of a hydroxylated polycrystalline tin oxide surface

    NASA Technical Reports Server (NTRS)

    Hoflund, Gar B.; Grogan, Austin L., Jr.; Asbury, Douglas A.; Schryer, David R.

    1989-01-01

    In this study Auger electron spectroscopy, electron spectroscopy for chemical analysis (ESCA) and electron-stimulated desorption (ESD) have been used to examine a polycrystalline tin oxide surface before and after annealing in vacuum at 500 C. Features due to surface hydroxyl groups are present in both the ESCA and ESD spectra, and ESD shows that several chemical states of hydrogen are present. Annealing at 500 C causes a large reduction in the surface hydrogen concentration but not complete removal.

  10. Surface studies of hydroxylated multi-wall carbon nanotubes

    SciTech Connect

    Bradley, Robert; Cassity, Kelby; Andrews, Rodney; Meier, Mark; Osbeck, Susan; Andreu, Aurik; Johnston, Colin; Crossley, Alison

    2012-01-01

    CVD grown MWCNTs, of typical diameter 5 to 50 nm and with approximately 15-20 concentric graphene layers in the multi-walls, have been surface functionalised using the Fenton hydroxylation reaction. HRTEM reveals little physical difference between the treated and untreated materials; images from both exhibit similar multi-wall structure and contain evidence for some low-level disruption of the very outermost layers. Raman spectra from the two types of nanotubes are almost identical displaying the disorder (D) peaks at approximately 1350 cm{sup -1} and graphite (G) peaks at approximately 1580 cm{sup -1}, characteristic of graphene-based carbon materials, in approximately equal intensity ratios. Equilibrium adsorption data for nitrogen at 77 K leads to BET surface areas of 60.4 m{sup 2} g{sup -1} for the untreated and 71.8 m{sup 2} g{sup -1} for the hydroxylated samples; the increase in area being due to separation of the tube-bundles during functionalization. This is accompanied by a decrease in measured porosity, mostly at high relative pressures of nitrogen, i.e. where larger (meso 2-5 nm and macro >5 nm) pores are being filled, which is consistent with an attendant loss of inter-tube capillarity. X-ray photoelectron spectroscopy (XPS) shows that hydroxylation increases the nanotube surface oxygen level from 4.3 at.% to 22.3 at.%; chemical shift data indicate that approximately 75% of that oxygen is present as hydroxyl (-OH) groups. Water vapour adsorption by the hydroxylated surfaces leads to Type II isotherms which are characteristic of relatively high numbers of hydrogen bonding interactions compared to the untreated materials which exhibit Type III curves. This difference in polar surface energy is confirmed by calorimetric enthalpies of immersion in water which are -54 mJ m{sup -2} for the untreated and -192 mJ m{sup -2} for the hydroxylated materials. The treated materials therefore have significantly increased water wettability/dispersivity and a greater

  11. 3D QSAR studies of hydroxylated polychlorinated biphenyls as potential xenoestrogens.

    PubMed

    Ruiz, Patricia; Ingale, Kundan; Wheeler, John S; Mumtaz, Moiz

    2016-02-01

    Mono-hydroxylated polychlorinated biphenyls (OH-PCBs) are found in human biological samples and lack of data on their potential estrogenic activity has been a source of concern. We have extended our previous in silico 2D QSAR study through the application of advance techniques such as docking and 3D QSAR to gain insights into their estrogen receptor (ERα) binding. The results support our earlier findings that the hydroxyl group is the most important feature on the compounds; its position, orientation and surroundings in the structure are influential for the binding of OH-PCBs to ERα. This study has also revealed the following additional interactions that influence estrogenicity of these chemicals (a) the aromatic interactions of the biphenyl moieties with the receptor, (b) hydrogen bonding interactions of the p-hydroxyl group with key amino acids ARG394 and GLU353, (c) low or no electronegative substitution at para-positions of the p-hydroxyl group, (d) enhanced electrostatic interactions at the meta position on the B ring, and (e) co-planarity of the hydroxyl group on the A ring. In combination the 2D and 3D QSAR approaches have led us to the support conclusion that the hydroxyl group is the most important feature on the OH-PCB influencing the binding to estrogen receptors, and have enhanced our understanding of the mechanistic details of estrogenicity of this class of chemicals. Such in silico computational methods could serve as useful tools in risk assessment of chemicals. PMID:26598992

  12. Ground-state, transition-state, and metal-cation effects of the 2-hydroxyl group on beta-D-galactopyranosyl transfer catalyzed by beta-galactosidase (Escherichia coli, lac Z).

    PubMed

    Richard, John P; McCall, Deborah A; Heo, Christina K; Toteva, Maria M

    2005-09-01

    Substitution of the C2-OH group by C2-H at 4-nitrophenyl-beta-d-galactopyranoside to give 4-nitrophenyl-2-deoxy-beta-d-galactopyranoside causes (1) a change in the rate-determining step for beta-galactosidase-catalyzed sugar hydrolysis from formation to breakdown of a covalent intermediate; (2) a 14 000-fold decrease in the second-order rate constant k(3)/K(d) for enzyme-catalyzed transfer of the beta-d-galactopyranosyl group from the substrate to form a covalent adduct to the enzyme; and (3) a larger 320 000-fold decrease in the first-order rate constant k(s) for hydrolysis of this covalent adduct. Only a small fraction (ca. 7%) of the 2-OH substituent effect is expressed in the ground-state Michaelis complex, so that the (apparent) strong interactions between the enzyme and 2-OH group that stabilize the transition state for beta-d-galactopyranosyl transfer only develop upon moving from the Michaelis complex to the transition state. Mg(2+) activates beta-galactosidase for cleavage of both 4-nitrophenyl-beta-d-galactopyranoside and 4-nitrophenyl-2-deoxy-beta-d-galactopyranoside. This suggests that Mg(2+) activation does not involve interactions with the 2-OH group. The removal of Mg(2+) from beta-galactosidase causes a change in the rate-determining step for enzyme-catalyzed hydrolysis of 4-nitrophenyl-2-deoxy-beta-d-galactopyranoside from breakdown to formation of the covalent intermediate. The observed 2-OH effect would require a very large (10-11 kcal/mol) stabilization of the transition state for beta-d-galactopyranosyl group transfer to water by interactions between beta-galactosidase and the neutral 2-OH group. We suggest that the apparent effect of the neutral substituent is more simply rationalized by ionization of the 2-OH to form a 2-O(-) anion, which provides effective electrostatic stabilization of the cationic transition state for glycoside cleavage at an active site of relatively low dielectric constant.

  13. CNO abundances in H II regions of the Magellanic clouds and the galaxy with implications regarding the nucleosynthesis of the CNO element group

    NASA Technical Reports Server (NTRS)

    Dufour, R. J.; Shields, G. A.

    1982-01-01

    Final abundance results of IUE observations of the UV spectra of three H II regions in the Small Magellanic Cloud and four H II regions in the Large Magellanic Cloud are presented. Calculated yields of carbon and oxygen derived are y(C)=.00063 and y(O)=.0016. The nucleosynthetic origin of nitrogen was evaluated as being predominantly a secondary element produced from carbon as its seed. Plotting log N/C versus log C/H yielded the rather unexpected result that log N/C decreases with lo C/H over the SMC-LMC-Orion range. The cause of this relationship is discussed.

  14. Fatty acid hydroxylation in rat kidney cortex microsomes.

    PubMed

    Ellin, A; Orrenius, S

    1975-08-30

    Rat kidney microsomes have been found to catalyze the hydroxylation of medium-chained fatty acids to the omega- and (omego-1)-hydroxy derivatives. This reaction, which requires NADPH and molecular oxygen, is a function of monooxygenase system present in the kidney microsomes, containing NADPH-cytochrome c reductase and cytochrome P-450K. NADH is about half as effective as an electron donor as NADPH and there is an additive effect in the presence of both nucleotides. Cytochrome P-450K absorbs light maximally at 452-3 nm, when it is reduced and bound to carbon monoxide. The extinction coefficient of this complex is 91 mM(-1) cm(-1). Electrons from NADPH are transferred to cytochrome P-450K via the NADPH-cytochrome c reductase. The reduction rate of cytochrome P-450K is stimulated by added fatty acids and the reduction kinetics reveal the presence of endogenous substrates bound to cytochrome P-450K. Both cytochrome P-450K concentration and fatty acid hydroxylation activity in kidney microsomes are increased by starvation. On the other hand, phenobarbital treatment of the rats has no effect on either the hemoprotein or the overall hydroxylation reaction and 3,4-benzpyrene administration induces a new species of cytochrome P-450K not involved in fatty acid hydroxylation. Cytochrome P-450K shows, in contrast to liver P-450, high substrate specificity. The only substances forming enzyme-substrate complexes with cytochrome P-450K are the medium-chained fatty acids and certain derivatives of these acids. The chemical requirements for substrate binding include a carbon chain of medium length and at the end of the chain a carbonyl group and a free electron pair on a neighbouring atom. The distance between the binding site for the carbonyl group and the active oxygen is suggested to be in the order of 16 A. This distance fixes the ratio of omega- and (omega-1)-hydroxylated products formed from a certain fatty acid by the single species of cytochrome P-450K involved. The

  15. OH vertical column abundance - Tropical measurements

    NASA Astrophysics Data System (ADS)

    Burnett, Clyde R.; Minschwaner, Kenneth R.; Burnett, Elizabeth B.

    1990-09-01

    Measurements of the vertical column abundance of atmospheric hydroxyl (OH) have been made during the period 1987-1989 at the National Weather Service (NWS) station at Moen, Truk, Federated States of Micronesia (7 deg N, 152 deg E). A total of 384 independent data sets was obtained. Tropical OH abundance levels average about 22 percent above corresponding mid-latitude values, with OH levels during late winter and early spring up to 50 percent above those observed at 40 deg N. Stratospheric wind and temperature data obtained from the daily NWS radiosonde data are examined for correlations with the OH results.

  16. OH vertical column abundance - Tropical measurements

    NASA Technical Reports Server (NTRS)

    Burnett, Clyde R.; Minschwaner, Kenneth R.; Burnett, Elizabeth B.

    1990-01-01

    Measurements of the vertical column abundance of atmospheric hydroxyl (OH) have been made during the period 1987-1989 at the National Weather Service (NWS) station at Moen, Truk, Federated States of Micronesia (7 deg N, 152 deg E). A total of 384 independent data sets was obtained. Tropical OH abundance levels average about 22 percent above corresponding mid-latitude values, with OH levels during late winter and early spring up to 50 percent above those observed at 40 deg N. Stratospheric wind and temperature data obtained from the daily NWS radiosonde data are examined for correlations with the OH results.

  17. The effect of heavy metal concentration and soil pH on the abundance of selected microbial groups within ArcelorMittal Poland steelworks in Cracow.

    PubMed

    Lenart, Anna; Wolny-Koładka, Katarzyna

    2013-01-01

    The present study aimed to identify the effect of heavy metal concentration and soil pH on the abundance of the selected soil microorganisms within ArcelorMittal Poland steelworks, Cracow. The analysis included 20 soil samples, where the concentration of Fe, Zn, Cd, Pb, Ni, Cu, Mn, Cr and soil pH were evaluated together with the number of mesophilic bacteria, fungi, Actinomycetes and Azotobacter spp. In the majority of samples soil pH was alkaline. The limits of heavy metals exceeded in eight samples and in one sample, the concentration of Zn exceeded 31-fold. Chromium was the element which most significantly limited the number of bacteria and Actinomycetes.

  18. Identification of a novel hydroxylated metabolite of 2,2',3,5',6-pentachlorobiphenyl formed in whole poplar plants.

    PubMed

    Ma, Cunxian; Zhai, Guangshu; Wu, Huimin; Kania-Korwel, Izabela; Lehmler, Hans-Joachim; Schnoor, Jerald L

    2016-02-01

    Polychlorinated biphenyls (PCBs) are a group of persistent organic pollutants consisting of 209 congeners. Oxidation of several PCB congeners to hydroxylated PCBs (OH-PCBs) in whole poplar plants has been reported before. Moreover, 2,2',3,5',6-pentachlorobiphenyl (PCB95), as a chiral congener, has been previously shown to be atropselectively taken up and transformed in whole poplar plants. The objective of this study was to determine if PCB95 is atropselectively metabolized to OH-PCBs in whole poplar plants. Two hydroxylated PCB95s were detected by high-performance liquid chromatography-mass spectrometry in the roots of whole poplar plants exposed to racemic PCB95 for 30 days. The major metabolite was confirmed to be 4'-hydroxy-2,2',3,5',6-pentachlorobiphenyl (4'-OH-PCB95) by gas chromatography-mass spectrometry (GC-MS) using an authentic reference standard. Enantioselective analysis showed that 4'-OH-PCB95 was formed atropselectively, with the atropisomer eluting second on the Nucleodex β-PM column (E2-4'-OH-PCB95) being slightly more abundant in the roots of whole poplar plants. Therefore, PCB95 can at least be metabolized into 4'-OH-PCB95 and another unknown hydroxylated PCB95 (as a minor metabolite) in whole poplar plants. Both atropisomers of 4'-OH-PCB95 are formed, but E2-4'-OH-PCB95 has greater atropisomeric enrichment in the roots of whole poplar plants. A comparison with mammalian biotransformation studies indicates a distinctively different metabolite profile of OH-PCB95 metabolites in whole poplar plants. Our observations suggest that biotransformation of chiral PCBs to OH-PCBs by plants may represent an important source of enantiomerically enriched OH-PCBs in the environment.

  19. Reduced serum hydroxyl radical scavenging activity in erythropoietin therapy resistant renal anemia.

    PubMed

    Hirayama, Aki; Nagase, Sohji; Gotoh, Michihiro; Ueda, Atsushi; Ishizu, Takashi; Yoh, Keigyou; Aoyagi, Kazumasa; Terao, Junji; Koyama, Akio

    2002-11-01

    Relation between anemia resistant to recombinant human erythropoietin (rHuEPO) therapy and the oxidative stress in hemodialysis (HD) patients was investigated. Stable HD patients who had consistent hemoglobin concentrations on a constant dose of rHuEPO were studied. Patients were excluded if there were factors that might affect hemopoiesis or administration of antioxidant supplements. Patients were classified into three groups: High (9000 U/week), Low (1500-4500 U/week) and No rHuEPO group. Thiobarbituric acid reactive substances (TBARS) of sera and erythrocyte were examined. Serum superoxide and hydroxyl radical scavenging activities were measured using electron spin resonance. TBARS in the erythrocyte was higher in High rHuEPO group compared with No rHuEPO group, though the serum TBARS were similar. A diminution of serum hydroxyl radical scavenging activity was observed in High rHuEPO group. Hydroxyl radical signal intensity showed a strong correlation with the serum ferritin in High rHuEPO group, although ferritin concentrations were not different among the 3 groups. Superoxide scavenging activity showed no differences. These results indicate that increased lipid peroxidation in erythrocyte, raised by decreased serum hydroxyl radical scavenging activity, is one cause of rHuEPO resistant anemia. Serum ferritin may be involved in this hydroxyl radical production.

  20. Electron stimulated hydroxylation of a metal supported silicate film.

    PubMed

    Yu, Xin; Emmez, Emre; Pan, Qiushi; Yang, Bing; Pomp, Sascha; Kaden, William E; Sterrer, Martin; Shaikhutdinov, Shamil; Freund, Hans-Joachim; Goikoetxea, Itziar; Wlodarczyk, Radoslaw; Sauer, Joachim

    2016-02-01

    Water adsorption on a double-layer silicate film was studied by using infrared reflection-absorption spectroscopy, thermal desorption spectroscopy and scanning tunneling microscopy. Under vacuum conditions, small amounts of silanols (Si-OH) could only be formed upon deposition of an ice-like (amorphous solid water, ASW) film and subsequent heating to room temperature. Silanol coverage is considerably enhanced by low-energy electron irradiation of an ASW pre-covered silicate film. The degree of hydroxylation can be tuned by the irradiation parameters (beam energy, exposure) and the ASW film thickness. The results are consistent with a generally accepted picture that hydroxylation occurs through hydrolysis of siloxane (Si-O-Si) bonds in the silica network. Calculations using density functional theory show that this may happen on Si-O-Si bonds, which are either parallel (i.e., in the topmost silicate layer) or vertical to the film surface (i.e., connecting two silicate layers). In the latter case, the mechanism may additionally involve the reaction with a metal support underneath. The observed vibrational spectra are dominated by terminal silanol groups (ν(OD) band at 2763 cm(-1)) formed by hydrolysis of vertical Si-O-Si linkages. Film dehydroxylation fully occurs only upon heating to very high temperatures (∼ 1200 K) and is accompanied by substantial film restructuring, and even film dewetting upon cycling hydroxylation/dehydroxylation treatment.

  1. Structure, electronic properties, and aggregation behavior of hydroxylated carbon nanotubes

    NASA Astrophysics Data System (ADS)

    López-Oyama, A. B.; Silva-Molina, R. A.; Ruíz-García, J.; Gámez-Corrales, R.; Guirado-López, R. A.

    2014-11-01

    We present a combined experimental and theoretical study to analyze the structure, electronic properties, and aggregation behavior of hydroxylated multiwalled carbon nanotubes (OH-MWCNT). Our MWCNTs have average diameters of ˜2 nm, lengths of approximately 100-300 nm, and a hydroxyl surface coverage θ˜0.1. When deposited on the air/water interface the OH-MWCNTs are partially soluble and the floating units interact and link with each other forming extended foam-like carbon networks. Surface pressure-area isotherms of the nanotube films are performed using the Langmuir balance method at different equilibration times. The films are transferred into a mica substrate and atomic force microscopy images show that the foam like structure is preserved and reveals fine details of their microstructure. Density functional theory calculations performed on model hydroxylated carbon nanotubes show that low energy atomic configurations are found when the OH groups form molecular islands on the nanotube's surface. This patchy behavior for the OH species is expected to produce nanotubes having reduced wettabilities, in line with experimental observations. OH doping yields nanotubes having small HOMO-LUMO energy gaps and generates a nanotube → OH direction for the charge transfer leading to the existence of more hole carriers in the structures. Our synthesized OH-MWCNTs might have promising applications.

  2. Structure, electronic properties, and aggregation behavior of hydroxylated carbon nanotubes

    SciTech Connect

    López-Oyama, A. B.; Silva-Molina, R. A.; Ruíz-García, J.; Guirado-López, R. A.; Gámez-Corrales, R.

    2014-11-07

    We present a combined experimental and theoretical study to analyze the structure, electronic properties, and aggregation behavior of hydroxylated multiwalled carbon nanotubes (OH–MWCNT). Our MWCNTs have average diameters of ∼2 nm, lengths of approximately 100–300 nm, and a hydroxyl surface coverage θ∼0.1. When deposited on the air/water interface the OH–MWCNTs are partially soluble and the floating units interact and link with each other forming extended foam-like carbon networks. Surface pressure-area isotherms of the nanotube films are performed using the Langmuir balance method at different equilibration times. The films are transferred into a mica substrate and atomic force microscopy images show that the foam like structure is preserved and reveals fine details of their microstructure. Density functional theory calculations performed on model hydroxylated carbon nanotubes show that low energy atomic configurations are found when the OH groups form molecular islands on the nanotube's surface. This patchy behavior for the OH species is expected to produce nanotubes having reduced wettabilities, in line with experimental observations. OH doping yields nanotubes having small HOMO–LUMO energy gaps and generates a nanotube → OH direction for the charge transfer leading to the existence of more hole carriers in the structures. Our synthesized OH–MWCNTs might have promising applications.

  3. Hydroxyl radical oxidation of feruloylated arabinoxylan.

    PubMed

    Bagdi, Attila; Tömösközi, Sándor; Nyström, Laura

    2016-11-01

    Feruloylated arabinoxylan (AX) has a unique capacity to form covalent gels in the presence of certain oxidizing agents. The present study demonstrates that hydroxyl radical oxidation does not provoke ferulic acid dimerization and thus oxidative gelation. We studied the hydroxyl radical mediated oxidation of an alkali-extracted AX preparation (purity: 92g/100g dry matter) that showed gel-forming capability upon peroxidase/hydrogen peroxide treatment. Hydroxyl radicals were produced with ascorbate-driven Fenton reaction and the radical formation was monitored with electron paramagnetic resonance, using a POBN/EtOH spin trapping system. Oxidation was carried out at different catalytic concentrations of iron (50 and 100μM) and at different temperatures (20°C, 50°C, and 80°C). It was demonstrated that hydroxyl radical oxidation does not provoke gel formation, but viscosity decrease in AX solution, which suggests polymer degradation. Furthermore, it was demonstrated that hydroxyl radical formation in AX solution can be initiated merely by increasing temperature. PMID:27516272

  4. Mechanisms of Innovation Diffusion under Information Abundance and Information Scarcity--On the Contribution of Social Networks in Group vs. Individual Extension Approaches in Semi-Arid Kenya

    ERIC Educational Resources Information Center

    Darr, Dietrich; Pretzsch, Jurgen

    2008-01-01

    Purpose: The objective of this paper is to assess the effectiveness of innovation diffusion under group-oriented and individual-oriented extension. Current theoretical notions of innovation diffusion in social networks shall be briefly reviewed, and the concepts of "search" and "innovation" vis-a-vis "transfer" and "imitation" mechanisms (Hansen,…

  5. Aliphatic peptidyl hydroperoxides as a source of secondary oxidation in hydroxyl radical protein footprinting

    PubMed Central

    Saladino, Jessica; Liu, Mian; Live, David; Sharp, Joshua S.

    2009-01-01

    Hydroxyl radical footprinting is a technique for studying protein structure and binding that entails oxidizing a protein system of interest with diffusing hydroxyl radicals, and then measuring the amount of oxidation of each amino acid. One important issue in hydroxyl radical footprinting is limiting amino acid oxidation by secondary oxidants to prevent uncontrolled oxidation which can cause amino acids to appear more solvent accessible than they really are. Previous work suggested that hydrogen peroxide was the major secondary oxidant of concern in hydroxyl radical footprinting experiments; however, even after elimination of all hydrogen peroxide, some secondary oxidation was still detected. Evidence is presented for the formation of peptidyl hydroperoxides as the most abundant product upon oxidation of aliphatic amino acids. Both reverse phase liquid chromatography and catalase treatment were shown to be ineffective at eliminating peptidyl hydroperoxides. The ability of these peptidyl hydroperoxides to directly oxidize methionine is demonstrated, suggesting the value of methionine amide as an in situ protectant. Hydroxyl radical footprinting protocols require the use of an organic sulfide or similar peroxide scavenger in addition to removal of hydrogen peroxide in order to successfully eradicate all secondary oxidizing species and prevent uncontrolled oxidation of sulfur-containing residues. PMID:19278868

  6. Microbial Hydroxylation of 1,4-Cineole

    PubMed Central

    Rosazza, John P. N.; Steffens, James J.; Sariaslani, F. Sima; Goswami, Animesh; Beale, John M.; Reeg, Scot; Chapman, Robert

    1987-01-01

    Microorganisms were examined for their potential to hydroxylate the oxygenated monoterpene 1,4-cineole. Using gas chromatography and thin-layer chromatography, screening experiments revealed that hydroxylation at position 2 was the most commonly observed microbial transformation reaction. In most microorganisms, the predominant alcohol metabolite was the 2-endo-alcohol isomer. Preparative-scale incubations were conducted in order to isolate and characterize microbial transformation products by comparison of proton nuclear magnetic resonance, mass spectrometry, and chromatography profiles with those of cineole standards. Streptomyces griseus yielded 8-hydroxy-1,4-cineole as the major hydroxylation product together with 2-exo- and 2-endo-hydroxy-1,4-cineoles. PMID:16347465

  7. Neodymium Fluorescence Quenching by Hydroxyl Groups in Phosphate Laser Glasses

    SciTech Connect

    Ehrmann, P R; Carlson, K; Campbell, J H; Click, C A; Brow, R K

    2003-09-02

    Non-radiative losses due to OH fluorescence quenching of the Nd{sup 3+} {sup 4}F{sub 3/2} state are quantified over a range of OH concentrations from 4 x 10{sup 18}/cm{sup 3} to 4 x 10{sup 20}/cm{sup 3} and Nd doping levels from 0.4 to 9 x 10{sup 20}/cm{sup 3} in two K{sub 2}O-MgO-Al{sub 2}O{sub 3}-P{sub 2}O{sub 5} metaphosphate glasses having different K/Mg ratios ({approx}1/1 and 2/1). The quenching rate is found to vary linearly with the Nd and OH concentrations as predicted by Forster-Dexter theory. However, in contrast to theory the OH quenching rate extrapolates to a non-zero value at low Nd{sup 3+} doping levels. It is proposed that at low Nd{sup 3+} concentrations the OH is correlated with Nd sites in the glass. The quenching strength of OH on a per ion basis is found to be weak compared to other common transition metal impurities (e.g. Fe{sup 2+}, Co{sup 2+}, Ni{sup 2+}, Cu{sup 2+}). Nevertheless, OH dominates the Nd quenching in phosphate glass because under most processing conditions OH is present at concentrations 10{sup 2} to 10{sup 3} greater than transition metal ion impurities. A correlation of the quenching strength of OH and common metal impurity ions with the degree of spectral overlap of the impurity absorption bands and the four {sup 4}F{sub 3/2} to {sup 4}I{sub J} transitions shows good agreement.

  8. Abundance of jackfruit (Artocarpus heterophyllus) affects group characteristics and use of space by golden-headed lion tamarins (Leontopithecus chrysomelas) in Cabruca agroforest.

    PubMed

    Oliveira, Leonardo C; Neves, Leonardo G; Raboy, Becky E; Dietz, James M

    2011-08-01

    Cabruca is an agroforest of cacao trees shaded by native forest trees. It is the predominant vegetation type throughout eastern part of the range of the golden-headed lion tamarins, Leontopithecus chrysomelas, an endangered primate endemic to Atlantic Forest. Understanding how lion tamarins use this agroforest is a conservation priority. To address this question, we documented the diet, home range size, group sizes and composition, density, number of litters and body condition of lion tamarins living in cabruca, and other habitats. Jackfruit, Artocarpus heterophyllus, was the most used species used by lion tamarins in cabruca and was widely available and used throughout the year. In cabruca, home range size was the smallest (22-28 ha) and density of lion tamarins was the highest (1.7 ind/ha) reported for the species. Group size averaged 7.4 individuals and was not significantly different among the vegetation types. In cabruca, groups produced one or two litters a year, and all litters were twins. Adult males in cabruca were significantly heavier than males in primary forest. Our study is the first to demonstrate that breeding groups of golden-headed lion tamarins can survive and reproduce entirely within cabruca agroforest. Jackfruit proved to be a keystone resource for lion tamarins in cabruca, and bromeliads were important as an animal prey foraging microhabitat. In cases where cabruca contains concentrated resources, such as jackfruit and bromeliads, lion tamarins may not only survive and reproduce but may fare better than in other forest types, at least for body condition and reproduction.

  9. Abundance of jackfruit (Artocarpus heterophyllus) affects group characteristics and use of space by golden-headed lion tamarins (Leontopithecus chrysomelas) in Cabruca agroforest.

    PubMed

    Oliveira, Leonardo C; Neves, Leonardo G; Raboy, Becky E; Dietz, James M

    2011-08-01

    Cabruca is an agroforest of cacao trees shaded by native forest trees. It is the predominant vegetation type throughout eastern part of the range of the golden-headed lion tamarins, Leontopithecus chrysomelas, an endangered primate endemic to Atlantic Forest. Understanding how lion tamarins use this agroforest is a conservation priority. To address this question, we documented the diet, home range size, group sizes and composition, density, number of litters and body condition of lion tamarins living in cabruca, and other habitats. Jackfruit, Artocarpus heterophyllus, was the most used species used by lion tamarins in cabruca and was widely available and used throughout the year. In cabruca, home range size was the smallest (22-28 ha) and density of lion tamarins was the highest (1.7 ind/ha) reported for the species. Group size averaged 7.4 individuals and was not significantly different among the vegetation types. In cabruca, groups produced one or two litters a year, and all litters were twins. Adult males in cabruca were significantly heavier than males in primary forest. Our study is the first to demonstrate that breeding groups of golden-headed lion tamarins can survive and reproduce entirely within cabruca agroforest. Jackfruit proved to be a keystone resource for lion tamarins in cabruca, and bromeliads were important as an animal prey foraging microhabitat. In cases where cabruca contains concentrated resources, such as jackfruit and bromeliads, lion tamarins may not only survive and reproduce but may fare better than in other forest types, at least for body condition and reproduction. PMID:21079956

  10. Abundance of Jackfruit ( Artocarpus heterophyllus) Affects Group Characteristics and Use of Space by Golden-Headed Lion Tamarins ( Leontopithecus chrysomelas) in Cabruca Agroforest

    NASA Astrophysics Data System (ADS)

    Oliveira, Leonardo C.; Neves, Leonardo G.; Raboy, Becky E.; Dietz, James M.

    2011-08-01

    Cabruca is an agroforest of cacao trees shaded by native forest trees. It is the predominant vegetation type throughout eastern part of the range of the golden-headed lion tamarins, Leontopithecus chrysomelas, an endangered primate endemic to Atlantic Forest. Understanding how lion tamarins use this agroforest is a conservation priority. To address this question, we documented the diet, home range size, group sizes and composition, density, number of litters and body condition of lion tamarins living in cabruca, and other habitats. Jackfruit, Artocarpus heterophyllus, was the most used species used by lion tamarins in cabruca and was widely available and used throughout the year. In cabruca, home range size was the smallest (22-28 ha) and density of lion tamarins was the highest (1.7 ind/ha) reported for the species. Group size averaged 7.4 individuals and was not significantly different among the vegetation types. In cabruca, groups produced one or two litters a year, and all litters were twins. Adult males in cabruca were significantly heavier than males in primary forest. Our study is the first to demonstrate that breeding groups of golden-headed lion tamarins can survive and reproduce entirely within cabruca agroforest. Jackfruit proved to be a keystone resource for lion tamarins in cabruca, and bromeliads were important as an animal prey foraging microhabitat. In cases where cabruca contains concentrated resources, such as jackfruit and bromeliads, lion tamarins may not only survive and reproduce but may fare better than in other forest types, at least for body condition and reproduction.

  11. Horseradish peroxidase catalyzed hydroxylations: mechanistic studies.

    PubMed

    Dordick, J S; Klibanov, A M; Marletta, M A

    1986-05-20

    The hydroxylation of phenol to hydroquinone and catechol in the presence of dihydroxyfumaric acid and oxygen catalyzed by horseradish peroxidase was studied under conditions where the product yield was high and the side reactions were minimal. The reaction is partially uncoupled with a molar ratio of dihydroxyfumaric acid consumed to hydroxylated products of 12:1. Hydrogen peroxide does not participate in the reaction as evidenced by the lack of effect of catalase and by the direct addition of hydrogen peroxide. Conversely, superoxide and hydroxyl radicals are involved as their scavengers are potent inhibitors. Experiments were all consistent with the involvement of compound III (oxygenated ferrous complex) of peroxidase in the reaction. Compound III is stable in the presence of phenol alone but decomposes rapidly in the presence of both phenol and dihydroxyfumaric acid with the concomitant formation of product. Therefore, phenol and dihydroxyfumaric acid must be present with compound III in order for the hydroxylation reaction to occur. A mechanism consistent with the experimental results is proposed. PMID:3718931

  12. Endogenous released ascorbic acid suppresses ethanol-induced hydroxyl radical production in rat striatum.

    PubMed

    Huang, Mei; Liu, Wen; Li, Qiang; Wu, Chun Fu

    2002-07-19

    Previous studies have shown that acute systemic administration of ethanol induced ascorbic acid release in the striatum. However, the pharmacological implications of ethanol-induced striatal ascorbic acid release are unclear. In the present study, ethanol-induced extracellular changes of ascorbic acid and hydroxyl radical levels were detected in rat striatum by using brain microdialysis coupled to high-performance liquid chromatography with electrochemical detection. It was found that both in male and female rats, ethanol (3.0 g/kg, i.p.) increased striatal ascorbic acid release in the first 60 min after ethanol administration. Meanwhile, the extracellular hydroxyl radical levels, detected as 2,3- and 2,5-DHBA, were significantly decreased. However, when the ascorbic acid levels returned to the baseline, hydroxyl radical levels rebounded. Administration of DL-fenfluramine (20 mg/kg, i.p.) had no effect on the basal levels of ascorbic acid and hydroxyl radical, but significantly blocked ethanol-induced ascorbic acid release and increased hydroxyl radical levels significantly. Exogenous administration of ascorbic acid (20 mg/kg, s.c.) increased the extracellular levels of ascorbic acid in the striatum, and inhibited the increase of 2,3- and 2,5-DHBA in DL-fenfluramine plus ethanol group. These results provide first evidence that release of endogenous ascorbic acid in the striatum plays an important role in preventing oxidative stress by trapping hydroxyl radical in the central nervous system.

  13. Mechanism of N-hydroxylation catalyzed by flavin-dependent monooxygenases.

    PubMed

    Badieyan, Somayesadat; Bach, Robert D; Sobrado, Pablo

    2015-02-20

    Aspergillus fumigatus siderophore (SidA), a member of class B flavin-dependent monooxygenases, was selected as a model system to investigate the hydroxylation mechanism of heteroatom-containing molecules by this group of enzymes. SidA selectively hydroxylates ornithine to produce N(5)-hydroxyornithine. However, SidA is also able to hydroxylate lysine with lower efficiency. In this study, the hydroxylation mechanism and substrate selectivity of SidA were systematically studied using DFT calculations. The data show that the hydroxylation reaction is initiated by homolytic cleavage of the O-O bond in the C(4a)-hydroperoxyflavin intermediate, resulting in the formation of an internal hydrogen-bonded hydroxyl radical (HO(•)). As the HO(•) moves to the ornithine N(5) atom, it rotates and donates a hydrogen atom to form the C(4a)-hydroxyflavin. Oxygen atom transfer yields an aminoxide, which is subsequently converted to hydroxylamine via water-mediated proton shuttling, with the water molecule originating from dehydration of the C(4a)-hydroxyflavin. The selectivity of SidA for ornithine is predicted to be the result of the lower energy barrier for oxidation of ornithine relative to that of lysine (16 vs 24 kcal/mol, respectively), which is due to the weaker stabilizing hydrogen bond between the incipient HO(•) and O3' of the ribose ring of NADP(+) in the transition state for lysine.

  14. Synthesis and antioxidant activity of hydroxylated phenanthrenes as cis-restricted resveratrol analogues.

    PubMed

    Ding, De-Jun; Cao, Xiao-Yan; Dai, Fang; Li, Xiu-Zhuang; Liu, Guo-Yun; Lin, Dong; Fu, Xing; Jin, Xiao-Ling; Zhou, Bo

    2012-12-01

    Five hydroxylated phenanthrenes as "cis-configuration-fixed" resveratrol analogues differing in the number and position of the hydroxyl groups were designed and synthesized. Their antioxidant activity was studied by ferric reducing antioxidant power, 2,2-diphenyl-1-picrylhydrazyl free radical-scavenging, and DNA strand breakage-inhibiting assays, corresponding to their electron-donating, hydrogen-transfer and DNA-protecting abilities, respectively. In the above assays, their activity depends significantly on the number and position of the hydroxyl groups, and most of them are more effective than resveratrol. Noticeably, compound 9b (2,4,6-trihydroxyl phenanthrene) with the same hydroxyl group substitutions as resveratrol, is superior to the reference compound, highlighting the importance of extension of the conjugation over multiple aromatic-rings. Similar activity sequences were obtained in different experimental models, but the appreciable differences could contribute detailed insights into antioxidant mechanisms. Based on these results, the hydroxylated phenanthrenes may be considered as a novel type of resveratrol-directed antioxidants.

  15. Platinum-group element abundances and Re-Os isotopic systematics of the upper continental crust through time: Evidence from glacial diamictites

    NASA Astrophysics Data System (ADS)

    Chen, Kang; Walker, Richard J.; Rudnick, Roberta L.; Gao, Shan; Gaschnig, Richard M.; Puchtel, Igor S.; Tang, Ming; Hu, Zhao-Chu

    2016-10-01

    The fine-grained matrix of glacial diamictites, deposited periodically by continental ice sheets over much of Earth history, provides insights into the average composition and chemical evolution of the upper continental crust (UCC) (Gaschnig et al., 2016, and references therein). The concentrations of platinum-group elements (PGEs, including Os, Ir, Ru, Pt and Pd) and the geochemically related Re, as well as 187Re/188Os and 187Os/188Os ratios, are reported here for globally-distributed glacial diamictites that were deposited during the Mesoarchean, Paleoproterozoic, Neoproterozoic and Paleozoic eras. The medians and averages of PGE concentrations of these diamictite composites decrease from the Mesoarchean to the Neoproterozoic, mimicking decreases in the concentrations of first-row transition elements (Sc, V, Cr, Co and Ni). By contrast, Re concentrations are highly variable with no discernable trend, owing to its high solubility. Assuming these diamictites are representative of average UCC through time, the new data are fully consistent with the previous inference that the Archean UCC contained a greater proportion of mafic-ultramafic rocks relative to younger UCC. Linear regressions of PGEs versus Cr and Ni concentrations in all the diamictite composites from the four time periods are used to estimate the following concentrations of the PGEs in the present-day UCC: 0.059 ± 0.016 ng/g Os, 0.036 ± 0.008 ng/g Ir, 0.079 ± 0.026 ng/g Ru, 0.80 ± 0.22 ng/g Pt and 0.80 ± 0.26 ng/g Pd (2σ of 10,000 bootstrapping regression results). These PGE estimates are slightly higher than the estimates obtained from loess samples. We suggest this probably results from loess preferentially sampling younger UCC rocks that have lower PGE concentrations, or PGEs being fractionated during loess formation. A Re concentration of 0.25 ± 0.12 ng/g (2σ) is obtained from a regression of Re versus Mo. From this, time-integrated 187Re/188Os and 187Os/188Os ratios for the UCC are

  16. Tunable photoluminescence and spectrum split from fluorinated to hydroxylated graphene

    NASA Astrophysics Data System (ADS)

    Gong, Peiwei; Wang, Jinqing; Sun, Weiming; Wu, Di; Wang, Zhaofeng; Fan, Zengjie; Wang, Honggang; Han, Xiuxun; Yang, Shengrong

    2014-02-01

    Tunable control over the functionalization of graphene is significantly important to manipulate its structure and optoelectronic properties. Yet the chemical inertness of this noble carbon material poses a particular challenge for its decoration without forcing reaction conditions. Here, a mild, operationally simple and controllable protocol is developed to synthesize hydroxylated graphene (HOG) from fluorinated graphene (FG). We successfully demonstrate that under designed alkali environment, fluorine atoms on graphene framework are programmably replaced by hydroxyl groups via a straightforward substitution reaction pathway. Element constituent analyses confirm that homogeneous C-O bonds are successfully grafted on graphene. Rather different from graphene oxide, the photoluminescence (PL) emission spectrum of the obtained HOG becomes split when excited with UV radiation. More interestingly, such transformation from FG facilitates highly tunable PL emission ranging from greenish white (0.343, 0.392) to deep blue (0.156, 0.094). Additionally, both experimental data and density function theory calculation indicate that the chemical functionalization induced structural rearrangement is more important than the chemical decoration itself in tuning the PL emission band tail and splitting energy gaps. This work not only presents a new way to effectively fabricate graphene derivatives with tunable PL performance, but also provides an enlightening insight into the PL origin of graphene related materials.Tunable control over the functionalization of graphene is significantly important to manipulate its structure and optoelectronic properties. Yet the chemical inertness of this noble carbon material poses a particular challenge for its decoration without forcing reaction conditions. Here, a mild, operationally simple and controllable protocol is developed to synthesize hydroxylated graphene (HOG) from fluorinated graphene (FG). We successfully demonstrate that under designed

  17. Hydroxyl radical formation in skeletal muscle of rats with glucocorticoid-induced myopathy.

    PubMed

    Konno, Shingo

    2005-05-01

    Steroid myopathy is a well-known adverse effect of glucocorticoids that causes muscle weakness and atrophy; however, its pathogenic mechanism is still unclear. Recently, oxidative stress was reported to contribute to steroid myopathy, but there is no report that actually attempts to measure hydroxyl radical. I developed an animal model of steroid myopathy in rat with dexamethasone (9-Fluoro-11beta,17, 21-trihydroxy-16alpha-methylpregna-1,4-diene-3,20-dione), and measured hydroxyl radical using the salicylate trapping method. There was significant dose-dependent relation between both 2,5- and 2,3-dihydroxybenzoic acids and dexamethasone in the treated group, compared to the control group. These results suggest that hydroxyl radical plays a role in the pathogenesis of steroid myopathy.

  18. Comets: production mechanisms of hydroxyl and hydrogen halos.

    PubMed

    Delsemme, A H

    1971-06-11

    The brightness dependence on the heliocentric distance that has been observed for the hydrogen and the hydroxyl halos of comet 1969g can be quantitatively explained by a three-step process: the vaporization of the water snows, the photodissociation of the water molecule into the ground states of hydrogen and hydroxyl, and the photoexcitation of hydrogen and hydroxyl by a fluorescence mechanism.

  19. Hydroxyl radical generation by red tide algae.

    PubMed

    Oda, T; Akaike, T; Sato, K; Ishimatsu, A; Takeshita, S; Muramatsu, T; Maeda, H

    1992-04-01

    The unicellular marine phytoplankton Chattonella marina is known to have toxic effects against various living marine organisms, especially fishes. However, details of the mechanism of the toxicity of this plankton remain obscure. Here we demonstrate the generation of superoxide and hydroxyl radicals from a red tide unicellular organism, C. marina, by using ESR spectroscopy with the spin traps 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) and N-t-butyl-alpha-phenylnitrone (PBN), and by using the luminol-enhanced chemiluminescence response. The spin-trapping assay revealed productions of spin adduct of superoxide anion (O2-) (DMPO-OOH) and that of hydroxyl radical (.OH) (DMPO-OH) in the algal suspension, which was not observed in the ultrasonic-ruptured suspension. The addition of superoxide dismutase (500 U/ml) almost completely inhibited the formation of both DMPO-OOH and DMPO-OH, and carbon-centered radicals were generated with the disappearance of DMPO-OH after addition of 5% dimethyl sulfoxide (Me2SO) and 5% ethanol. Furthermore, the generation of methyl and methoxyl radicals, which are thought to be produced by the reaction of hydroxyl radical and Me2SO under aerobic condition, was identified using spin trapping with a combination of PBN and Me2SO. Luminol-enhanced chemiluminescence assay also supported the above observations. These results clearly indicate that C. marina generates and releases the superoxide radical followed by the production of hydroxyl radical to the surrounding environment. The velocity of superoxide generation by C. marina was about 100 times faster than that by mammalian phagocytes per cell basis. The generation of oxygen radical is suggested to be a pathogenic principle in the toxication of red tide to susceptible aquaculture fishes and may be directly correlated with the coastal pollution by red tide.

  20. A theoretical study of O2 activation by the Au7-cluster on Mg(OH)2: roles of surface hydroxyls and hydroxyl defects.

    PubMed

    Jia, Chuanyi; Fan, Weiliu

    2015-11-11

    Using density functional theory (DFT) calculations, we investigated O2 activation by the Au7-cluster supported on the perfect and hydroxyl defective Mg(OH)2(0001) surface. It is revealed that hydroxyl groups on the perfect Mg(OH)2(0001) surface can not only enhance the stability of the Au7-cluster, but also help the adsorption of the O2 molecule through hydrogen-bonding interactions with the 2nd-layered interfacial Au sites. Density of states (DOS) analysis shows that the d-band centers of the 2nd-layered interfacial Au atoms are very close to the Fermi level, which thereby reduce the Pauli repulsion and promote the O2 adsorption. These two responses make the 2nd-layered interfacial Au atoms favor O2 activation. Interestingly, the surface hydrogen atoms activated by the 1st-layered Au atoms can facilitate the O2 dissociation process as well. Such a process is dynamically favorable and more inclined to occur at low temperatures compared to the direct dissociation process. Meanwhile, the hydroxyl defects of Mg(OH)2(0001) located right under the Au7-cluster can also up-shift the d-band centers of the surrounding Au atoms toward the Fermi level, enhancing its catalytic activity for O2 dissociation. In contrast, the d-band center of Au atoms surrounding the hydroxyl defect near the Au7-cluster exhibits an effective down-shift to lower energies, and therefore holds low activity. These results unveiled the roles of surface hydroxyls and hydroxyl defects on the Au/Mg(OH)2 catalyst in O2 activation and could provide a theoretical guidance for chemists to efficiently synthesize Au/hydroxide catalysts. PMID:26529519

  1. Extraadrenal steroid 21-hydroxylation is not mediated by P450c21.

    PubMed Central

    Mellon, S H; Miller, W L

    1989-01-01

    The 21-hydroxylation of progesterone to deoxycorticosterone (DOC) and of 17-hydroxyprogesterone to 11-deoxycortisol in the human adrenal cortex is mediated by a single enzyme termed P450c21. Extraadrenal tissues can clear circulating progesterone and progesterone sulfate by 21-hydroxylation to DOC and DOC-sulfate. It has previously been established that such extraadrenal 21-hydroxylase activity is widely distributed in adult and fetal tissues, but it has not been known if extra-adrenal 21-hydroxylation is mediated by the same P450c21 enzyme found in the adrenal. We examined human RNA from fetal adrenal, liver, kidney, lung, brain, heart, skin, spleen, testis, and placenta by solution hybridization to human P450c21 probes transcribed from cloned human P450c21 cDNA, followed by nuclease protection and acrylamide gel electrophoresis. No P450c21 mRNA was detectable in any extraadrenal tissue. The sensitivity of the assay would have detected P450c21 mRNA at 0.01% of its abundance in the human fetal adrenal. Similar experiments in rats showed no P450c21 mRNA in brain, heart, kidney, liver, lung, testis, ovary, or uterus. These results clearly demonstrate that one or more enzymes other than the classical adrenal 21-hydroxylase are responsible for human and rat extraadrenal 21-hydroxylation. Images PMID:2808702

  2. Investigating Hydroxyl at Asteroid 951 Gaspra

    NASA Astrophysics Data System (ADS)

    Granahan, James C.

    2015-11-01

    Recent investigations [Granahan, 2011; 2014] of Galileo Near Infrared Mapping Spectrometer (NIMS) observations of asteroid 951 Gaspra have detected an infrared absorption feature near 2.8 micrometers. These were detected in NIMS data acquired by the Galileo spacecraft on October 29, 1991 at wavelengths ranging from 0.7 - 5.2 micrometers [Carlson et al., 1992]. This abstract presents a summary of the investigation to identify the material creating the 2.8 micrometer spectral absorption feature. The current best match for the observed 951 Gaspra feature is the phyllosilicate bound hydroxyl signature present in a thermally desiccated QUE 99038 carbonaceous chondrite as measured by Takir et al. [2013].The 951 Gaspra absorption feature has been compared to a variety of hydroxyl bearing signatures. Many phyllosilicates, hydroxyl bearing minerals, have absorption minima at different positions (2.7 or 2.85 micrometers). It also differs from similar absorptions in a potential R chondrite analog, LAP 04840. The spectra LAP 04840 has a 2.7 micrometer feature due to biotite and a 2.9 micrometer feature due to adsorbed water [Klima et al., 2007]. 2.8 micrometer absorption minima have been found for adsorbed hydroxyl on the Moon [McCord et al., 2011] and various carbonaceous chondrites [Calvin and King, 1997; Takir et al., 2013]. The best match, with a minimum Euclidean distance difference to the 951 Gaspra feature, is found in the spectrum of QUE 99038 [Takir et al., 2013]. This spectrum is the product of an infrared measurement of a sample that had its adsorbed water baked off and removed in a vacuum chamber. The remaining hydroxyl in the sample belongs to a mixture of phyllosilicates dominated by the presence of cronstedtite.References: Calvin, W. M., and T. V. King (1997), Met. Planet. Sci., 32, 693-702. Carlson, R. W., et al. (1992), Bull. American Astro. Soc., 24, 932. Granahan, J. C. (2011), Icarus, 213, 265-272. Granahan, J. C. (2014), 45th LPSC, #1092. Klima, R., C. et

  3. Hydroxyl radical mediated DNA base modification by manmade mineral fibres.

    PubMed Central

    Leanderson, P; Söderkvist, P; Tagesson, C

    1989-01-01

    Manmade mineral fibres (MMMFs) were examined for their ability to hydroxylate 2-deoxyguanosine (dG) to 8-hydroxydeoxyguanosine (8-OH-dG), a reaction that is mediated by hydroxyl radicals. It appeared that (1) catalase and the hydroxyl radical scavengers, dimethylsulphoxide and sodium benzoate, inhibited the hydroxylation, whereas Fe2+ and H2O2 potentiated it; (2) pretreatment of MMMFs with the iron chelator, deferoxamine, or with extensive heat (200-400 degrees C), attenuated the hydroxylation; (3) the hydroxylation obtained by various MMMFs varied considerably; (4) there was no apparent correlation between the hydroxylation and the surface area of different MMMFs, although increasing the surface area of a fibre by crushing it increased its hydroxylating capacity; and (5) there was good correlation between the hydroxylation of dG residues in DNA and the hydroxylation of pure dG in solution for the 16 different MMMFs investigated. These findings indicate that MMMFs cause a hydroxyl radical mediated DNA base modification in vitro and that there is considerable variation in the reactivity of different fibre species. The DNA modifying ability seems to depend on physical or chemical characteristics, or both, of the fibre. PMID:2765416

  4. Development of a Concise Synthesis of Ouabagenin and Hydroxylated Corticosteroid Analogues

    PubMed Central

    2016-01-01

    The natural product ouabagenin is a complex cardiotonic steroid with a highly oxygenated skeleton. This full account describes the development of a concise synthesis of ouabagenin, including the evolution of synthetic strategy to access hydroxylation at the C19 position of a steroid skeleton. In addition, approaches to install the requisite butenolide moiety at the C17 position are discussed. Lastly, methodology developed in this synthesis has been applied in the generation of novel analogues of corticosteroid drugs bearing a hydroxyl group at the C19 position. PMID:25594682

  5. Hydroxyl orientations in cellobiose and other polyhydroxy compounds – modeling versus experiment

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Theoretical and experimental gas-phase studies of carbohydrates show that their hydroxyl groups are located in homodromic partial rings that resemble cooperative hydrogen bonds, albeit with long H…O distances and small O-H…O angles. On the other hand, anecdotal experience with disaccharide crystal ...

  6. DFT STUDY OF ALPHA-MALTOSE: INFLUENCE OF HYDROXYL ORIENTATIONS ON THE GLYCOSIDIC BOND

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The result of DFT geometry optimization of 68 unique alpha-maltose conformers at the B3LYP/6-311++G** level of theory is described. Particular attention is paid to the hydroxyl group rotational positions and their influence on the glycosidic bond dihedral angles. The orientation of lone pair elect...

  7. Aromatic-Hydroxyl Interaction of a Lignin Model Compound on SBA-15, Present at Pyrolysis Temperatures

    SciTech Connect

    Kandziolka, III, Michael V.; Kidder, Michelle; Gill, Lance W.; Wu, Zili; Savara, Aditya Ashi

    2014-07-14

    An aromatic alpha-aryl ether compound (a benzyl phenyl ether analogue) was covalently grafted to mesoporous silica SBA-15, to create BPEa-SBA-15. The BPEa-SBA-15 was subjected to successive heating cycles up to 600 °C, with in situ monitoring by DRIFTS. It was found that the toluene moiety coordinates to SBA-15 surface silanol hydroxyl groups via an aromatic–hydroxyl interaction. This interaction is evidenced by a red-shift of the aromatic C–H stretches, as well as a red-shift and broadening of the surface hydroxyl O–H stretches, which are features characteristic of a hydrogen bond. These features remain present during heating until ~400 °C whereupon the ether linkage of BPEa-SBA-15 is cleaved, accompanied by loss of the toluene moiety.

  8. Aromatic-Hydroxyl Interaction of a Lignin Model Compound on SBA-15, Present at Pyrolysis Temperatures

    DOE PAGES

    Kandziolka, III, Michael V.; Kidder, Michelle; Gill, Lance W.; Wu, Zili; Savara, Aditya Ashi

    2014-07-14

    An aromatic alpha-aryl ether compound (a benzyl phenyl ether analogue) was covalently grafted to mesoporous silica SBA-15, to create BPEa-SBA-15. The BPEa-SBA-15 was subjected to successive heating cycles up to 600 °C, with in situ monitoring by DRIFTS. It was found that the toluene moiety coordinates to SBA-15 surface silanol hydroxyl groups via an aromatic–hydroxyl interaction. This interaction is evidenced by a red-shift of the aromatic C–H stretches, as well as a red-shift and broadening of the surface hydroxyl O–H stretches, which are features characteristic of a hydrogen bond. These features remain present during heating until ~400 °C whereupon themore » ether linkage of BPEa-SBA-15 is cleaved, accompanied by loss of the toluene moiety.« less

  9. Abundances in Sagittarius Stars

    NASA Astrophysics Data System (ADS)

    Bonifacio, P.; Zaggia, S.; Sbordone, L.; Santin, P.; Monaco, L.; Monai, S.; Molaro, P.; Marconi, G.; Girardi, L.; Ferraro, F.; di Marcantonio, P.; Caffau, E.; Bellazzini, M.

    The Sagittarius dwarf spheroidal is a very complex galaxy, which has undergone prolonged star formation. From the very first high resolution chemical analysis of Sgr stars, conducted using spectra obtained during the commissioning of UVES at VLT, it was clear that the star had undergone a high level of chemical processing, at variance with most of the other Local Group dwarf spheroidals. Thanks to FLAMES at VLT we now have accurate metallicities and abundances of alpha-chain elements for about 150 stars, which provide the first reliable metallicity distribution for this galaxy. Besides the already known high metallicity tail the existence of a metal-poor population has also been highlighted, although an assessment of the fraction of Sgr stars which belong to this population requires a larger sample. From our data it is also obvious that Sagittarius is a nucleated galaxy and that the centre of the nucleus coincides with M54, as already shown by Monaco et al.

  10. Hydroxylated ornithine lipids increase stress tolerance in Rhizobium tropici CIAT899

    PubMed Central

    Vences-Guzmán, Miguel Ángel; Guan, Ziqiang; Ormeño-Orrillo, Ernesto; González-Silva, Napoleón; López-Lara, Isabel M.; Martínez-Romero, Esperanza; Geiger, Otto; Sohlenkamp, Christian

    2011-01-01

    Ornithine lipids (OLs) are widespread among gram-negative bacteria. Their basic structure consists of a 3-hydroxy fatty acyl group attached in amide linkage to the α-amino group of ornithine and a second fatty acyl group ester-linked to the 3-hydroxy position of the first fatty acid. OLs can be hydroxylated within the secondary fatty acyl moiety and this modification has been related to increased stress tolerance. Rhizobium tropici, a nodule-forming α-proteobacterium known for its stress tolerance, forms four different OLs. Studies of the function of these OLs have been hampered due to lack of knowledge about their biosynthesis. Here we describe that OL biosynthesis increases under acid stress and that OLs are enriched in the outer membrane. Using a functional expression screen, the OL hydroxylase OlsE was identified, which in combination with the OL hydroxylase OlsC is responsible for the synthesis of modified OLs in R. tropici. Unlike described OL hydroxylations, the OlsE-catalyzed hydroxylation occurs within the ornithine moiety. Mutants deficient in OlsE or OlsC and double mutants deficient in OlsC/OlsE were characterized. R. tropici mutants deficient in OlsC-mediated OL hydroxylation are more susceptible to acid and temperature stress. All three mutants lacking OL hydroxylases are affected during symbiosis. PMID:21205018

  11. Global tropospheric hydroxyl distribution, budget and reactivity

    NASA Astrophysics Data System (ADS)

    Lelieveld, Jos; Gromov, Sergey; Pozzer, Andrea; Taraborrelli, Domenico

    2016-10-01

    The self-cleaning or oxidation capacity of the atmosphere is principally controlled by hydroxyl (OH) radicals in the troposphere. Hydroxyl has primary (P) and secondary (S) sources, the former mainly through the photodissociation of ozone, the latter through OH recycling in radical reaction chains. We used the recent Mainz Organics Mechanism (MOM) to advance volatile organic carbon (VOC) chemistry in the general circulation model EMAC (ECHAM/MESSy Atmospheric Chemistry) and show that S is larger than previously assumed. By including emissions of a large number of primary VOC, and accounting for their complete breakdown and intermediate products, MOM is mass-conserving and calculates substantially higher OH reactivity from VOC oxidation compared to predecessor models. Whereas previously P and S were found to be of similar magnitude, the present work indicates that S may be twice as large, mostly due to OH recycling in the free troposphere. Further, we find that nighttime OH formation may be significant in the polluted subtropical boundary layer in summer. With a mean OH recycling probability of about 67 %, global OH is buffered and not sensitive to perturbations by natural or anthropogenic emission changes. Complementary primary and secondary OH formation mechanisms in pristine and polluted environments in the continental and marine troposphere, connected through long-range transport of O3, can maintain stable global OH levels.

  12. Kinetics of hydrogen peroxide decomposition by catalase: hydroxylic solvent effects.

    PubMed

    Raducan, Adina; Cantemir, Anca Ruxandra; Puiu, Mihaela; Oancea, Dumitru

    2012-11-01

    The effect of water-alcohol (methanol, ethanol, propan-1-ol, propan-2-ol, ethane-1,2-diol and propane-1,2,3-triol) binary mixtures on the kinetics of hydrogen peroxide decomposition in the presence of bovine liver catalase is investigated. In all solvents, the activity of catalase is smaller than in water. The results are discussed on the basis of a simple kinetic model. The kinetic constants for product formation through enzyme-substrate complex decomposition and for inactivation of catalase are estimated. The organic solvents are characterized by several physical properties: dielectric constant (D), hydrophobicity (log P), concentration of hydroxyl groups ([OH]), polarizability (α), Kamlet-Taft parameter (β) and Kosower parameter (Z). The relationships between the initial rate, kinetic constants and medium properties are analyzed by linear and multiple linear regression.

  13. Kinetics of hydrogen peroxide decomposition by catalase: hydroxylic solvent effects.

    PubMed

    Raducan, Adina; Cantemir, Anca Ruxandra; Puiu, Mihaela; Oancea, Dumitru

    2012-11-01

    The effect of water-alcohol (methanol, ethanol, propan-1-ol, propan-2-ol, ethane-1,2-diol and propane-1,2,3-triol) binary mixtures on the kinetics of hydrogen peroxide decomposition in the presence of bovine liver catalase is investigated. In all solvents, the activity of catalase is smaller than in water. The results are discussed on the basis of a simple kinetic model. The kinetic constants for product formation through enzyme-substrate complex decomposition and for inactivation of catalase are estimated. The organic solvents are characterized by several physical properties: dielectric constant (D), hydrophobicity (log P), concentration of hydroxyl groups ([OH]), polarizability (α), Kamlet-Taft parameter (β) and Kosower parameter (Z). The relationships between the initial rate, kinetic constants and medium properties are analyzed by linear and multiple linear regression. PMID:22565543

  14. Ultraviolet irradiation-induced substitution of fluorine with hydroxyl radical for mass spectrometric analysis of perfluorooctane sulfonyl fluoride.

    PubMed

    Wang, Peng; Tang, Xuemei; Huang, Lulu; Kang, Jie; Zhong, Hongying

    2016-01-28

    A rapid and solvent free substitution reaction of a fluorine atom in perfluorooctane sulfonyl fluoride (PFOSF) with a hydroxyl radical is reported. Under irradiation of ultraviolet laser on semiconductor nanoparticles or metal surfaces, hydroxyl radicals can be generated through hole oxidization. Among all fluorine atoms of PFOSF, highly active hydroxyl radicals specifically substitute the fluorine of sulfonyl fluoride functional group. Resultant perfluorooctane sulfonic acid is further ionized through capture of photo-generated electrons that switch the neutral molecules to negatively charged odd electron hypervalent ions. The unpaired electron subsequently initiates α O-H bond cleavage and produces perfluorooctane sulfonate negative ions. Hydroxyl radical substitution and molecular dissociation of PFOSF have been confirmed by masses with high accuracy and resolution. It has been applied to direct mass spectrometric imaging of PFOSF adsorbed on surfaces of plant leaves.

  15. Net proton-hydroxyl permeability of large unilamellar liposomes measured by an acid-base titration technique.

    PubMed

    Nichols, J W; Deamer, D W

    1980-04-01

    The net proton-hydroxyl permeability of large unilamellar liposomes has been measured by an acid-base pulse titration technique and has been determined to be several orders of magnitude greater than that measured for other monovalent ions. This permeability is relatively insensitive to variations in lipid composition. Proton permeability and hydroxyl permeability vary with pH 6 to 8, and this variation can occur in the absence of alterations in surface charge density resulting from titrations of acidic and basic groups on the lipids. In order to account for the exceptionally high proton-hydroxyl permeability with respect to other monovalent ions, we propose that protons or hydroxyls or both interact with clusters of hydrogen-bonded water molecules in the lipid bilayer, such that they are transferred across the bilayer by rearrangement of hydrogen bonds in a manner similar to their transport in water and ice.

  16. Ultraviolet irradiation-induced substitution of fluorine with hydroxyl radical for mass spectrometric analysis of perfluorooctane sulfonyl fluoride.

    PubMed

    Wang, Peng; Tang, Xuemei; Huang, Lulu; Kang, Jie; Zhong, Hongying

    2016-01-28

    A rapid and solvent free substitution reaction of a fluorine atom in perfluorooctane sulfonyl fluoride (PFOSF) with a hydroxyl radical is reported. Under irradiation of ultraviolet laser on semiconductor nanoparticles or metal surfaces, hydroxyl radicals can be generated through hole oxidization. Among all fluorine atoms of PFOSF, highly active hydroxyl radicals specifically substitute the fluorine of sulfonyl fluoride functional group. Resultant perfluorooctane sulfonic acid is further ionized through capture of photo-generated electrons that switch the neutral molecules to negatively charged odd electron hypervalent ions. The unpaired electron subsequently initiates α O-H bond cleavage and produces perfluorooctane sulfonate negative ions. Hydroxyl radical substitution and molecular dissociation of PFOSF have been confirmed by masses with high accuracy and resolution. It has been applied to direct mass spectrometric imaging of PFOSF adsorbed on surfaces of plant leaves. PMID:26755143

  17. Specificity of acceptor binding to Leuconostoc mesenteroides B-512F dextransucrase: binding and acceptor-product structure of alpha-methyl-D-glucopyranoside analogs modified at C-2, C-3, and C-4 by inversion of the hydroxyl and by replacement of the hydroxyl with hydrogen.

    PubMed

    Fu, D T; Slodki, M E; Robyt, J F

    1990-02-01

    The specificity of acceptor binding to the active site of dextransucrase was studied by using alpha-methyl-D-glucopyranoside analogs modified at C-2, C-3, and C-4 positions by (a) inversion of the hydroxyl group and (b) replacement of the hydroxyl group with hydrogen. 2-Deoxy-alpha-methyl-D-glucopyranoside was synthesized from 2-deoxyglucose; 3- and 4-deoxy-alpha-methyl-D-glucopyranosides were synthesized from alpha-methyl-D-glucopyranoside; and alpha-methyl-D-allopyranoside was synthesized from D-glucose. The analogs were incubated with [14C]sucrose and dextransucrase, and the products were separated by thin-layer chromatography and quantitated by liquid scintillation spectrometry. Structures of the acceptor products were determined by methylation analyses and optical rotation. The relative effectiveness of the acceptor analogs in decreasing order were 2-deoxy, 2-inverted, 3-deoxy, 3-inverted, 4-inverted, and 4-deoxy. The enzyme transfers D-glucopyranose to the C-6 hydroxyl of analogs modified at C-2 and C-3, to the C-4 hydroxyl of 4-inverted, and to the C-3 hydroxyl of 4-deoxy analogs of alpha-methyl-D-glucopyranoside. The data indicate that the hydroxyl group at C-2 is not as important for acceptor binding as the hydroxyl groups at C-3 and C-4. The hydroxyl group at C-4 is particularly important as it determines the binding orientation of the alpha-methyl-D-glucopyranoside ring.

  18. Poly(hydroxyl urethane) compositions and methods of making and using the same

    DOEpatents

    Luebke, David; Nulwala, Hunaid; Tang, Chau

    2016-01-26

    Methods and compositions relating to poly(hydroxyl urethane) compounds are described herein that are useful as, among other things, binders and adhesives. The cross-linked composition is achieved through the reaction of a cyclic carbonate, a compound having two or more thiol groups, and a compound having two or more amine functional groups. In addition, a method of adhesively binding two or more substrates using the cross-linked composition is provided.

  19. Poly(hydroxyl urethane) compositions and methods of making and using the same

    DOEpatents

    Luebke, David; Nulwala, Hunaid; Tang, Chau

    2014-12-16

    Methods and compositions relating to poly(hydroxyl urethane) compounds are described herein that are useful as, among other things, binders and adhesives. The cross-linked composition is achieved through the reaction of a cyclic carbonate, a compound having two or more thiol groups, and a compound having two or more amine functional groups. In addition, a method of adhesively binding two or more substrates using the cross-linked composition is provided.

  20. Effects of hydroxylation and silanization on the surface properties of ZnO nanowires.

    PubMed

    García Núñez, C; Sachsenhauser, M; Blashcke, B; García Marín, A; Garrido, Jose A; Pau, Jose L

    2015-03-11

    Silanization is commonly used to form bonds between inorganic materials and biomolecules as a step in the surface preparation of solid-state biosensors. This work investigates the effects of silanization with amino-propyldiethoxymethylsilane on hydroxylated sidewalls of zinc oxide (ZnO) nanowires (NWs). The surface properties and electrical characteristics of NWs are analyzed by different techniques after their hydroxylation and later silanization. Contact angle measurements reveal a stronger hydrophobic behavior after silanization, and X-ray photoelectron spectroscopy (XPS) results show a reduction of the surface dipole induced by the replacement of the hydroxyl group with the amine terminal group. The lower work function obtained after silanization in contact potential measurements corroborates the attenuation of the surface dipole observed in XPS. Furthermore, the surface band bending of NWs is determined from surface photovoltage measurements upon irradiation with UV light, yielding a 0.5 eV energy in hydroxylated NWs, and 0.18 eV, after silanization. From those results, a reduction in the surface state density of 3.1 × 10(11) cm(-2) is estimated after silanization. The current-voltage (I-V) characteristics measured in a silanized single NW device show a reduction of the resistance, due to the enhancement of the conductive volume inside the NW, which also improves the linearity of the I-V characteristic.

  1. Hydroxyl-radical-induced oxidation of 5-methylcytosine in isolated and cellular DNA

    PubMed Central

    Madugundu, Guru S.; Cadet, Jean; Wagner, J. Richard

    2014-01-01

    The methylation and oxidative demethylation of cytosine in CpG dinucleotides plays a critical role in the regulation of genes during cell differentiation, embryogenesis and carcinogenesis. Despite its low abundance, 5-methylcytosine (5mC) is a hotspot for mutations in mammalian cells. Here, we measured five oxidation products of 5mC together with the analogous products of cytosine and thymine in DNA exposed to ionizing radiation in oxygenated aqueous solution. The products can be divided into those that arise from hydroxyl radical (•OH) addition at the 5,6-double bond of 5mC (glycol, hydantoin and imidazolidine products) and those that arise from H-atom abstraction from the methyl group of 5mC including 5-hydroxymethylcytosine (5hmC) and 5-formylcytosine (5fC). Based on the analysis of these products, we show that the total damage at 5mC is about 2-fold greater than that at C in identical sequences. The formation of hydantoin products of 5mC is favored, compared to analogous reactions of thymine and cytosine, which favor the formation of glycol products. The distribution of oxidation products is sequence dependent in specific ODN duplexes. In the case of 5mC, the formation of 5hmC and 5fC represents about half of the total of •OH-induced oxidation products of 5mC. Several products of thymine, cytosine, 5mC, as well as 8-oxo-7,8-dihydroguanine (8oxoG), were also estimated in irradiated cells. PMID:24852253

  2. Hydroxyl-radical-induced oxidation of 5-methylcytosine in isolated and cellular DNA.

    PubMed

    Madugundu, Guru S; Cadet, Jean; Wagner, J Richard

    2014-06-01

    The methylation and oxidative demethylation of cytosine in CpG dinucleotides plays a critical role in the regulation of genes during cell differentiation, embryogenesis and carcinogenesis. Despite its low abundance, 5-methylcytosine (5mC) is a hotspot for mutations in mammalian cells. Here, we measured five oxidation products of 5mC together with the analogous products of cytosine and thymine in DNA exposed to ionizing radiation in oxygenated aqueous solution. The products can be divided into those that arise from hydroxyl radical (•OH) addition at the 5,6-double bond of 5mC (glycol, hydantoin and imidazolidine products) and those that arise from H-atom abstraction from the methyl group of 5mC including 5-hydroxymethylcytosine (5hmC) and 5-formylcytosine (5fC). Based on the analysis of these products, we show that the total damage at 5mC is about 2-fold greater than that at C in identical sequences. The formation of hydantoin products of 5mC is favored, compared to analogous reactions of thymine and cytosine, which favor the formation of glycol products. The distribution of oxidation products is sequence dependent in specific ODN duplexes. In the case of 5mC, the formation of 5hmC and 5fC represents about half of the total of •OH-induced oxidation products of 5mC. Several products of thymine, cytosine, 5mC, as well as 8-oxo-7,8-dihydroguanine (8oxoG), were also estimated in irradiated cells.

  3. Probing the human estrogen receptor-α binding requirements for phenolic mono- and di-hydroxyl compounds: a combined synthesis, binding and docking study.

    PubMed

    McCullough, Christopher; Neumann, Terrence S; Gone, Jayapal Reddy; He, Zhengjie; Herrild, Christian; Wondergem Nee Lukesh, Julie; Pandey, Rajesh K; Donaldson, William A; Sem, Daniel S

    2014-01-01

    Various estrogen analogs were synthesized and tested for binding to human ERα using a fluorescence polarization displacement assay. Binding affinity and orientation were also predicted using docking calculations. Docking was able to accurately predict relative binding affinity and orientation for estradiol, but only if a tightly bound water molecule bridging Arg394/Glu353 is present. Di-hydroxyl compounds sometimes bind in two orientations, which are flipped in terms of relative positioning of their hydroxyl groups. Di-hydroxyl compounds were predicted to bind with their aliphatic hydroxyl group interacting with His524 in ERα. One nonsteroid-based dihdroxyl compound was 1000-fold specific for ERβ over ERα, and was also 25-fold specific for agonist ERβ versus antagonist activity. Docking predictions suggest this specificity may be due to interaction of the aliphatic hydroxyl with His475 in the agonist form of ERβ, versus with Thr299 in the antagonist form. But, the presence of this aliphatic hydroxyl is not required in all compounds, since mono-hydroxyl (phenolic) compounds bind ERα with high affinity, via hydroxyl hydrogen bonding interactions with the ERα Arg394/Glu353/water triad, and van der Waals interactions with the rest of the molecule.

  4. Climate Impacts on Tropospheric Ozone and Hydroxyl

    NASA Technical Reports Server (NTRS)

    Shindell, Drew T.; Bell, N.; Faluvegi, G.

    2003-01-01

    Climate change may influence tropospheric ozone and OH via several main pathways: (1) altering chemistry via temperature and humidity changes, (2) changing ozone and precursor sources via surface emissions, stratosphere-troposphere exchange, and light- ning, and (3) affecting trace gas sinks via the hydrological cycle and dry deposition. We report results from a set of coupled chemistry-climate model simulations designed to systematically study these effects. We compare the various effects with one another and with past and projected future changes in anthropogenic and natural emissions of ozone precursors. We find that white the overall impact of climate on ozone is probably small compared to emission changes, some significant seasonal and regional effects are apparent. The global effect on hydroxyl is quite large, however, similar in size to the effect of emission changes. Additionally, we show that many of the chemistry-climate links that are not yet adequately modeled are potentially important.

  5. Hydroxyl density measurements with resonant holographic interferometry

    SciTech Connect

    Trolinger, J.D.; Hess, C.F.; Yip, B.; Battles, B.; Hanson, R.K. Stanford University, CA )

    1992-01-01

    This paper describes experimentation with a new type of flow diagnostics referred to as Resonant Holographic Interferometry Spectroscopy (RHIS). This technique combines the power of holography with the species selectivity of spectroscopy to provide three-dimensional images of the density profile of selected species in complex flows. The technique is particularly suitable to study mixing processes as well as to measure minor species in combustion processes. The method would allow the measurement of minor species in the presence of major species, as well as major species in a heterogeneous low pressure environment. Both experiments and modeling are being conducted to establish the feasibility of RHIS in measuring the hydroxyl concentrations in combustion processes. It is expected that in addition to the species concentration, the resonant holographic technique has the potential of providing temperature, pressure, and flow velocity. 28 refs.

  6. Hydroxylation and dealkylation reactions catalyzed by hemoglobin.

    PubMed

    Mieyal, J J; Starke, D W

    1994-01-01

    Red blood cells contain many enzymes that are akin to those that catalyze xenobiotic metabolism in liver and other tissues. An obvious exception is the cytochrome P-450 system that is found in virtually all other tissues. In vitro studies, however, have shown that hemoglobin can be a broad monooxygenase catalyst, exhibiting the properties of a monooxygenase enzyme. Thus, catalysis by Hb displays typical Michaelis-Menten kinetics, dependence on the native protein, coupling to NADPH-dependent flavoprotein reductases, and inhibition by carbon monoxide. The reconstituted system containing Hb along with P-450 reductase utilizes NADPH and O2 to catalyze typical monooxygenase reactions, including O- and N-demethylations as well as aromatic and aliphatic hydroxylations, and the catalytic cycle appears to mimic the typical P-450 mechanism. Turnover numbers for aniline hydroxylation are similar for Hb and P-450 reconstituted systems, whereas P-450 systems are more effective for other reactions. Catalysis by Hb seems to be restricted to the beta-heme sites of the tetramer, reflecting more facile substrate access. Overall the similarities and differences between Hb and P-450 provide an opportunity to examine the basis for their differential monooxygenase or peroxidase/peroxygenase activities in a comparative manner. Hb may be especially useful in delineating the early events in the respective reaction schemes, because it can be studied in various stable redox/ligand states, including the oxyferrous form. Similar hemoglobin-catalyzed oxidative biotransformations occur within intact erythrocytes, but apparent turnover numbers are much lower than those with the reconstituted Hb system, suggesting different mechanisms of catalysis. Although Hb-mediated oxidase activity in erythrocytes is low relative to other sites of xenobiotic metabolism, it may contribute to in situ activation of xenobiotics leading to oxidative stress, disruption of sulfhydryl homeostasis in the erythrocytes

  7. Theoretical study on the sequential hydroxylation of C82 fullerene based on Fukui function

    NASA Astrophysics Data System (ADS)

    Rodríguez-Zavala, J. G.; Tenorio, F. J.; Samaniego, Cuauhtemoc; Méndez-Barrientos, C. I.; Peña-Lecona, F. G.; Muñoz-Maciel, J.; Flores-Moreno, R.

    2011-07-01

    In the present work semi-empirical PM3 method and ab initio density-functional theory calculations were performed in carbon systems. The condensed Fukui function was calculated and HOMO-LUMO were visualised in order to study the sequence of hydroxylation of two isomers of C82 fullerene for the low coverage regime, with the formula C82(OH) x where x = 0 - 12. It was found that there was a formation of dangling bonds on structures with an odd number of hydroxyl groups on the fullerene surface, which suggests an enhanced reactivity of these molecules. Nevertheless, the coverings with an even number of groups tend to the reconstruction of π bonds, obtaining less reactive molecular structures. With the adsorption of the first group, a narrow HOMO-LUMO gap (1.28 eV) is observed in comparison with the C82(OH)2 system (1.70 eV), as is found in similar systems, such as C60 fullerenol [E.E. Fileti et al., Nanotechnology 19, 365703 (2008); J.G. Rodríguez-Zavala and R.A. Guirado-López, Phys. Rev. B 69, 075411 (2004)]. Through an analysis of the electronic structure to these coverings, a splitting of electronic energy levels in the structure with one hydroxyl group is observed, which could be one of the factors that causes the narrowing of the energy gap in this structure. On the other hand, with a coverage of 12 hydroxyl groups, the formation of an amphiphilic molecule, where the location of groups in one side of the C82 surface provides an hydrophilic character, is observed, while the uncovered part has an hydrophobic character. This could be important in the formation of Langmuir monolayers. Finally, it is shown that the precise distribution of the OH groups on the fullerene surface plays a crucial role in the electronic structure of the polyhydroxylated fullerenes.

  8. Influences of the size and hydroxyl number of fullerenes/fullerenols on their interactions with proteins.

    PubMed

    Wu, Xian; Yang, Sheng-Tao; Wang, Haifang; Wang, Luyao; Hu, Wenxiang; Cao, Aoneng; Liu, Yuanfang

    2010-10-01

    In this study, we systematically investigated the interaction of fullerenes/fullerenols with model proteins using a widely used computational docking program Autodock 4.0. We found that pi-pi interaction existed in all the proteins-fullerene/fullerenol systems investigated here, and contributed greatly to the overall interaction energy. We also found that with the increase of the carbon cage size, the binding strength between proteins and fullerenes/fullerenols increased constantly. In addition, our results show that functionalization of fullerenes with polar groups, such as hydroxyl groups, decreases the binding between proteins and fullerene derivatives. In other words, the more hydroxyl groups on fullerenols, the weaker binding between proteins and fullerenols.

  9. Hydrated goethite (alpha-FeOOH) (100) interface structure: Ordered water and surface functional groups.

    SciTech Connect

    Ghose, S.K.; Waychunas, G.A.; Trainor, T.P.; Eng, P.J.

    2009-12-15

    Goethite({alpha}-FeOOH), an abundant and highly reactive iron oxyhydroxide mineral, has been the subject of numerous stud-ies of environmental interface reactivity. However, such studies have been hampered by the lack of experimental constraints on aqueous interface structure, and especially of the surface water molecular arrangements. Structural information of this type is crucial because reactivity is dictated by the nature of the surface functional groups and the structure or distribution of water and electrolyte at the solid-solution interface. In this study we have investigated the goethite(100) surface using surface diffraction techniques, and have determined the relaxed surface structure, the surface functional groups, and the three dimensional nature of two distinct sorbed water layers. The crystal truncation rod (CTR) results show that the interface structure consists of a double hydroxyl, double water terminated interface with significant atom relaxations. Further, the double hydroxyl terminated surface dominates with an 89% contribution having a chiral subdomain structure on the(100) cleavage faces. The proposed interface stoichiometry is ((H{sub 2}O)-(H{sub 2}O)-OH{sub 2}-OH-Fe-O-O-Fe-R) with two types of terminal hydroxyls; a bidentate (B-type) hydroxo group and a monodentate (A-type) aquo group. Using the bond-valence approach the protonation states of the terminal hydroxyls are predicted to be OH type (bidentate hydroxyl with oxygen coupled to two Fe{sup 3+} ions) and OH{sub 2} type (monodentate hydroxyl with oxygen tied to only one Fe{sup 3+}). A double layer three dimensional ordered water structure at the interface was determined from refinement of fits to the experimental data. Application of bond-valence constraints to the terminal hydroxyls with appropriate rotation of the water dipole moments allowed a plausible dipole orientation model as predicted. The structural results are discussed in terms of protonation and H-bonding at the interface

  10. Solar abundance of osmium

    PubMed Central

    Jacoby, George; Aller, Lawrence H.

    1976-01-01

    The abundance parameter, log gfA, where g is the statistical weight of the lower level, f is the oscillator strength, and A is the abundance (by numbers of atoms with respect to hydrogen), has been derived for three lines of osmium by a method of spectrum synthesis. An apparent discordance of the derived abundance with that found from the carbonaceous chondrites is probably to be attributed primarily to errors in the f-values, and blending with unknown contributors. PMID:16592314

  11. Cellulose based hybrid hydroxylated adducts for polyurethane foams

    NASA Astrophysics Data System (ADS)

    De Pisapia, Laura; Verdolotti, Letizia; Di Mauro, Eduardo; Di Maio, Ernesto; Lavorgna, Marino; Iannace, Salvatore

    2012-07-01

    Hybrid flexible polyurethane foams (HPU) were synthesized by using a hybrid hydroxilated adduct (HHA) based on renewable resources. In particular the HHA was obtained by dispersing cellulose wastes in colloidal silica at room temperature, pressure and humidity. The colloidal silica was selected for its ability of modifying the cellulose structure, by inducing a certain "destructurization" of the crystalline phase, in order to allow cellulose to react with di-isocyanate for the final synthesis of the polyurethane foam. In fact, cellulose-polysilicate complexes are engaged in the reaction with the isocyanate groups. This study provides evidence of the effects of the colloidal silica on the cellulose structure, namely, a reduction of the microfiber cellulose diameter and the formation of hydrogen bonds between the polysilicate functional groups and the hydroxyl groups of the cellulose, as assessed by IR spectroscopy and solid state NMR. The HHA was added to a conventional polyol in different percentages (between 5 and 20%) to synthesize HPU in presence of catalysts, silicone surfactant and diphenylmethane diisocyanate (MDI). The mixture was expanded in a mold and cured for two hours at room temperature. Thermal analysis, optical microscopy and mechanical tests were performed on the foams. The results highlighted an improvement of thermal stability and a decrease of the cell size with respect neat polyurethane foam. Mechanical tests showed an improvement of the elastic modulus and of the damping properties with increasing HHA amount.

  12. Glutathione conjugation of busulfan produces a hydroxyl radical-trapping dehydroalanine metabolite.

    PubMed

    Peer, Cody J; Younis, Islam R; Leonard, Stephen S; Gannett, Peter M; Minarchick, Valerie C; Kenyon, Allison J; Rojanasakul, Yon; Callery, Patrick S

    2012-12-01

    The Phase 2 drug metabolism of busulfan yields a glutathione conjugate that undergoes a β-elimination reaction. The elimination product is an electrophilic metabolite that is a dehydroalanine-containing tripeptide, γ-glutamyldehydroalanylglycine (EdAG). In the process, glutathione lacks thiol-related redox properties and gains a radical scavenging dehydroalanine group. EdAG scavenged hydroxyl radical generated in the Fenton reaction in a concentration-dependent manner was monitored by electron paramagnetic resonance (EPR) spectroscopy. The apparent rate of hydroxyl radical scavenging was in the same range as published values for known antioxidants, including N-acyl dehydroalanines. A captodatively stabilized carbon-centered radical intermediate was spin trapped in the reaction of EdAG with hydroxyl radical. The proposed structure of a stable product in the Fenton reaction with EdAG was consistent with that of a γ-glutamylserylglycyl dimer. Observation of the hydroxyl trapping properties of EdAG suggests that the busulfan metabolite EdAG may contribute to or mitigate redox-related cytotoxicity associated with the therapeutic use of busulfan, and reaffirms indicators that support a role in free radical biology for dehydroalanine-containing peptides and proteins.

  13. Omega-hydroxylation of phytanic acid in rat liver microsomes: implications for Refsum disease.

    PubMed

    Komen, J C; Duran, M; Wanders, R J A

    2004-07-01

    The 3-methyl-branched fatty acid phytanic acid is degraded by the peroxisomal alpha-oxidation route because the 3-methyl group blocks beta-oxidation. In adult Refsum disease (ARD), peroxisomal alpha-oxidation is defective, which is caused by mutations in the gene coding for phytanoyl-CoA hydroxylase in the majority of ARD patients. As a consequence, phytanic acid accumulates in tissues and body fluids. This study focuses on an alternative route of phytanic acid degradation, omega-oxidation. The first step in omega-oxidation is hydroxylation at the omega-end of the fatty acid, catalyzed by a member of the cytochrome P450 multienzyme family. To study this first step, the formation of hydroxylated intermediates was studied in rat liver microsomes incubated with phytanic acid and NADPH. Two hydroxylated metabolites of phytanic acid were formed, omega- and (omega-1)-hydroxyphytanic acid (ratio of formation, 5:1). The formation of omega-hydroxyphytanic acid was NADPH dependent and inhibited by imidazole derivatives. These results indicate that phytanic acid undergoes omega-hydroxylation in rat liver microsomes and that an isoform of cytochrome P450 catalyzes the first step of phytanic acid omega-oxidation.

  14. Radiation-induced destruction of hydroxyl-containing amino acids and dipeptides

    NASA Astrophysics Data System (ADS)

    Sladkova, А. А.; Sosnovskaya, А. А.; Edimecheva, I. P.; Shadyro, О. I.

    2012-12-01

    The yields of molecular products resulting from radiolysis of hydroxyl-containing amino acids and dipeptides under various conditions were determined. The possibility of a new radiation-induced destruction pathway has been shown for serine and threonine, as well as for the dipeptides having residues of these amino acids at the N-terminal part of the respective molecule. This process includes formation of N-centered radicals from the starting molecules followed by their decomposition with elimination of side substituents. On radiolysis, serine and threonine were also shown to undergo free-radical destruction to form acetaldehyde and acetone, respectively. A mechanism has been proposed including consecutive stages of fragmentation of α-hydroxyl-containing carbon-centered radicals with elimination of ammonia and decomposition of the secondary radicals with elimination of CO2. The yields of CO2 obtained on radiolysis of serine and threonine were significantly higher (except for solutions at pH 12) than those for alanine and valine, which have no hydroxyl groups in their structures. The obtained data indicate that the hydroxyl-containing amino acids occupy a special place among other amino acids as regards the variety of radiation-induced reactions which they may undergo due to their structural features.

  15. Hydroxyl-riched halloysite clay nanotubes serving as substrate of NiO nanosheets for high-performance supercapacitor

    NASA Astrophysics Data System (ADS)

    Liang, Jin; Tan, Hui; Xiao, Chunhui; Zhou, Guijiang; Guo, Shengwu; Ding, Shujiang

    2015-07-01

    Despite the great progress in NiO-based materials for supercapacitors in recent years, the tested specific capacitance of NiO-based materials is usually much lower than its theoretical specific capacitance. Here, a novel hierarchical nickel oxide@halloysite nanocomposite has been synthesized via a simple precipitation reaction. In the resulting structure, halloysite tubes with abundant hydroxyl group are closely assembled with ultrathin and standing NiO nanoflakes. This architecture designed is expected to enrich accessible electroactive sites, faster kinetics of NiO/NiOOH redox pair, as well as enhance participation degree of NiO during the charging/discharging process. As a result, the as-prepared NiO@halloysite nanocomposite exhibits excellent electrochemical properties in terms of high charge storage capacitance (1047.3 F g-1 at 5 A g-1), high rate capability and stable cycling performance (1338 F g-1 after 7200 cycles at a current of 10 A g-1).

  16. Petroleum films exposed to sunlight produce hydroxyl radical.

    PubMed

    Ray, Phoebe Z; Tarr, Matthew A

    2014-05-01

    Sunlight exposed oil films on seawater or pure water produced substantial amounts of hydroxyl radical as a result of irradiation. Oil was collected from the surface of the Gulf of Mexico following the Deepwater Horizon spill and exposed to simulated sunlight in thin films over water. Photochemical production of hydroxyl radical was measured with benzoic acid as a selective chemical probe in the aqueous layer. Total hydroxyl radical formation was studied using high benzoic acid concentrations and varying exposure time. The total amount of hydroxyl radical produced in 24 h irradiations of thin oil films over Gulf of Mexico water and pure water were 3.7×10(-7) and 4.2×10(-7) moles respectively. Steady state concentrations of hydroxyl radical were measured using a competition kinetics approach. Hydroxyl radical concentrations of 1.2×10(-16) to 2.4×10(-16) M were observed for seawater and pure water under oil films. Titanium dioxide (TiO2) nanomaterials were added to the system in an effort to determine if the photocatalyst would enhance oil photodegradation. The addition of TiO2 nanoparticles dramatically changed the observed formation rate of hydroxyl radical in the systems with NP water at pH 3, showing increased formation rate in many cases. With photocatalyst, the steady state concentration of radical decreased, predominantly due to an increase in the hydroxyl radical scavenging rate with oxide present. This study illustrates that oil is a strong and important source of hydroxyl radical when exposed to sunlight. The fate of oil and other dissolved species following oil spills will be heavily dependent on the formation and fate of hydroxyl radical.

  17. Petroleum films exposed to sunlight produce hydroxyl radical.

    PubMed

    Ray, Phoebe Z; Tarr, Matthew A

    2014-05-01

    Sunlight exposed oil films on seawater or pure water produced substantial amounts of hydroxyl radical as a result of irradiation. Oil was collected from the surface of the Gulf of Mexico following the Deepwater Horizon spill and exposed to simulated sunlight in thin films over water. Photochemical production of hydroxyl radical was measured with benzoic acid as a selective chemical probe in the aqueous layer. Total hydroxyl radical formation was studied using high benzoic acid concentrations and varying exposure time. The total amount of hydroxyl radical produced in 24 h irradiations of thin oil films over Gulf of Mexico water and pure water were 3.7×10(-7) and 4.2×10(-7) moles respectively. Steady state concentrations of hydroxyl radical were measured using a competition kinetics approach. Hydroxyl radical concentrations of 1.2×10(-16) to 2.4×10(-16) M were observed for seawater and pure water under oil films. Titanium dioxide (TiO2) nanomaterials were added to the system in an effort to determine if the photocatalyst would enhance oil photodegradation. The addition of TiO2 nanoparticles dramatically changed the observed formation rate of hydroxyl radical in the systems with NP water at pH 3, showing increased formation rate in many cases. With photocatalyst, the steady state concentration of radical decreased, predominantly due to an increase in the hydroxyl radical scavenging rate with oxide present. This study illustrates that oil is a strong and important source of hydroxyl radical when exposed to sunlight. The fate of oil and other dissolved species following oil spills will be heavily dependent on the formation and fate of hydroxyl radical. PMID:24405967

  18. HYDROXYL CATION IN TRANSLUCENT INTERSTELLAR CLOUDS

    SciTech Connect

    Krelowski, J.; Beletsky, Y.; Galazutdinov, G. A. E-mail: ybialets@eso.or

    2010-08-10

    High-quality spectra acquired at the European Southern Observatory enabled us to discover a very weak spectral feature of the OH{sup +} molecule, near 3584 A. The species likely shares environments with another molecular ion, CH{sup +}. Its abundance is by a factor of 30 lower than that of neutral OH.

  19. Plane-wave density functional theory investigation of adsorption of 2,4,6-trinitrotoluene on Al-hydroxylated (0001) surface of (4 × 4) α-alumina.

    PubMed

    Shukla, Manoj K; Hill, Frances

    2014-10-15

    This article reports the results of the theoretical investigation of adsorption of 2,4,6-trinitrotoluene (TNT) on Al-hydroxylated (0001) surface of (4 × 4) α-alumina (α-Al2O3) using plane-wave Density Functional Theory. Sixteen water molecules were used to hydroxylate the alumina surface. The Perdew-Burke-Ernzerhof functional and the recently developed van der Waals functional (vdW-DF2) were used. The interaction of electron with core was accounted using the Vanderbilt ultrasoft pseudopotentials. It was found that hydroxylation has significant influence on the geometry of alumina and such changes are prominent up to few layers from the surface. Particularly, due to the Al-hydroxylation the oxygen layers are decomposed into sublayers and such partitioning becomes progressively weaker for interior layers. Moreover, the nature of TNT adsorption interaction is changed from covalent type on the pristine alumina surface to hydrogen-bonding interaction on the Al-hydroxylated alumina surface. TNT in parallel orientation forms several hydrogen bonds compared to that in the perpendicular orientation with hydroxyl groups of the Al-hydroxylated alumina surface. Therefore, the parallel orientation will be present in the adsorption of TNT on Al-hydroxylated (0001) surface of α-alumina. Further, the vdW-DF2 van der Waals functional was found to be most suitable and should be used for such surface adsorption investigation.

  20. Searching for a One-Step Bioprocess for the Production of Hydroxyl Fatty Acids and Hydroxyl Oils from Soybean Oil

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Soybean oil is produced domestically in large supply, averaging over 20 billion pounds per year with an annual carryover of more than one billion pounds. It is important to find new uses for this surplus soybean oil. Hydroxyl fatty acids and hydroxyl oils are platform materials for specialty chemi...

  1. One-step synthesis and functionalization of hydroxyl-decorated magnetite nanoparticles.

    PubMed

    Mondini, Sara; Cenedese, Simone; Marinoni, Giorgio; Molteni, Giorgio; Santo, Nadia; Bianchi, Claudia L; Ponti, Alessandro

    2008-06-01

    Magnetite nanoparticles covered by a layer of omega-hydroxycarboxylic acid were synthesized in one step by high-temperature decomposition of iron(III) omega-hydroxycarboxylates in tri- and tetra-ethylene glycol. The nanoparticles were characterized by TEM, XRD, IR, XPS and NMR techniques in order to show that they comprise a crystalline magnetite core and actually bear on the outer surface terminal hydroxy groups. The latter ones are convenient "handles" for further functionalization as opposed to the chemically-inert aliphatic chains which cover conventionally synthesized nanoparticles. This was shown by several examples in which the hydroxy groups on the nanoparticle surface were easily transformed in other functional groups or reacted with other molecules. For instance, the hydroxyl-decorated nanoparticles were made water soluble by esterification with a PEGylated acetic acid. The reactive behavior of the surfactant monolayer was monitored by degrading the nanoparticles with aqueous acid and isolating the surfactant for NMR characterization. In general, the reactivity of the terminal hydroxyl groups on the nanoparticle surface parallels that observed in the free surfactants. The reported hydroxyl-decorated magnetite nanoparticles can be thus considered as pro-functional nanoparticles, i.e., a convenient starting material to functionalized magnetic nanoparticles.

  2. Hydroxyl Emission in the Westbrook Nebula

    NASA Astrophysics Data System (ADS)

    Strack, Angelica; Araya, Esteban; Ghosh, Tapasi; Arce, Hector G.; Lebron, Mayra E.; Salter, Christopher J.; Minchin, Robert F.; Pihlstrom, Ylva; Kurtz, Stan; Hofner, Peter; Olmi, Luca

    2016-06-01

    CRL 618, also known as the Westbrook Nebula, is a carbon-rich pre-planetary nebula. Hydroxyl (OH) transitions are typically not detected in carbon-rich late-type stellar objects, however observations conducted with the 305m Arecibo Telescope in 2008 resulted in the detection of 4765 MHz OH emission in CRL 618. We present results of observations carried out a few months after the original detection that confirm the line. This is the first detection of 4765 MHz OH emission (most likely a maser) in a pre-planetary nebula. Follow up observations conducted in 2015 resulted in non-detection of the 4765 MHz OH transition. This behavior is consistent with the high level of variability of excited OH lines that have been detected toward a handful of other pre-planetary nebulae. Our work supports that excited OH masers are short-lived during the pre-planetary nebula phase. We also conducted a search for other OH transitions from 1612 MHz to 8611 MHz with the Arecibo Telescope; we report no other detections at rms levels of ~5 mJy.This work has made use of the computational facilities donated by Frank Rodeffer to the WIU Astrophysics Research Laboratory. We also acknowledge support from M. & C. Wong RISE scholarships and a grant from the WIU College of Arts and Sciences.

  3. Vertical Distribution of Vibrationally Excited Hydroxyl

    NASA Astrophysics Data System (ADS)

    Grygalashvyly, Mykhaylo; Becker, Erich; Sonnemann, Gerd

    2016-04-01

    Knowledge about the vertical distribution of the vibrationally excited states of hydroxyl (OH*) is important for the interpretation of airglow measurements with respect to dynamical processes in the mesopause region. We derive an approximate analytical expression for the distribution of OH* that highlights the dependence on atomic oxygen and temperature. In addition, we use an advanced numerical model for the formation and relaxation of OH* and investigate the distributions of the different vibrationally exited states of OH*. For the production of OH*, the model includes the reaction of atomic hydrogen with ozone, as well as the reaction of atomic oxygen with hydroperoxy radicals. As loss processes we include 1) deactivation by atomic oxygen, molecular oxygen, and molecular nitrogen, 2) spontaneous emission, and 3) loss due to chemical reaction with atomic oxygen. All these processes take the dependence on the vibrational number into account. The quenching by molecular and atomic oxygen is parameterized by a multi-quantum relaxation scheme. This diagnostic model for OH* has been implemented as part of a chemistry-transport model that is driven by the dynamics simulated with the KMCM (Kühlungsborn Mechanistic general Circulation Model). Numerical results confirm that emission from excited states with higher vibrational number is weaker and emanates from higher altitudes. In addition we find that the OH*-peak altitudes depend significantly on season and latitude. This behavior is mainly controlled by the corresponding variations of atomic oxygen and temperature, as is also confirmed by the aforementioned approximate theory.

  4. A pro-chelator triggered by hydrogen peroxide inhibits iron-promoted hydroxyl radical formation.

    PubMed

    Charkoudian, Louise K; Pham, David M; Franz, Katherine J

    2006-09-27

    The synthesis and structural characterization of a new pro-chelating agent, isonicotinic acid [2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-benzylidene]-hydrazide (BSIH), are presented. BSIH only weakly interacts with iron unless hydrogen peroxide (H2O2) is present to remove the boronic ester protecting group to reveal a phenol that is a key metal-binding group of tridentate salicylaldehyde isonicotinoyl hydrazone (SIH). BSIH prevents deoxyribose degradation caused by hydroxyl radicals that are generated from H2O2 and redox-active iron by sequestering Fe3+ and preventing iron-promoted hydroxyl radical formation. The rate-determining step for iron sequestration is conversion of BSIH to SIH, followed by rapid Fe3+ complexation. The pro-chelate approach of BSIH represents a promising strategy for chelating a specific pool of detrimental metal ions without disturbing healthy metal ion distribution.

  5. A pro-chelator triggered by hydrogen peroxide inhibits iron-promoted hydroxyl radical formation.

    PubMed

    Charkoudian, Louise K; Pham, David M; Franz, Katherine J

    2006-09-27

    The synthesis and structural characterization of a new pro-chelating agent, isonicotinic acid [2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-benzylidene]-hydrazide (BSIH), are presented. BSIH only weakly interacts with iron unless hydrogen peroxide (H2O2) is present to remove the boronic ester protecting group to reveal a phenol that is a key metal-binding group of tridentate salicylaldehyde isonicotinoyl hydrazone (SIH). BSIH prevents deoxyribose degradation caused by hydroxyl radicals that are generated from H2O2 and redox-active iron by sequestering Fe3+ and preventing iron-promoted hydroxyl radical formation. The rate-determining step for iron sequestration is conversion of BSIH to SIH, followed by rapid Fe3+ complexation. The pro-chelate approach of BSIH represents a promising strategy for chelating a specific pool of detrimental metal ions without disturbing healthy metal ion distribution. PMID:16984186

  6. Spectral Response and Diagnostics of Biological Activity of Hydroxyl-Containing Aromatic Compounds

    NASA Astrophysics Data System (ADS)

    Tolstorozhev, G. B.; Mayer, G. V.; Bel'kov, M. V.; Shadyro, O. I.

    2016-08-01

    Using IR Fourier spectra and employing quantum-chemical calculations of electronic structure, spectra, and proton-acceptor properties, synthetic derivatives of aminophenol exhibiting biological activity in the suppression of herpes, influenza, and HIV viruses have been investigated from a new perspective, with the aim of establishing the spectral response of biological activity of the molecules. It has been experimentally established that the participation of the aminophenol hydroxyl group in intramolecular hydrogen bonds is characteristic of structures with antiviral properties. A quantum-chemical calculation of the proton-acceptor ability of the investigated aminophenol derivatives has shown that biologically active structures are characterized by a high proton-acceptor ability of oxygen of the hydroxyl group. A correlation that has been obtained among the formation of an intramolecular hydrogen bond, high proton-acceptor ability, and antiviral activity of substituted aminophenols enables us to predict the pharmacological properties of new medical preparations of the given class of compounds.

  7. Hydroxylation of p-substituted phenols by tyrosinase: Further insight into the mechanism of tyrosinase activity

    SciTech Connect

    Munoz-Munoz, Jose Luis; Berna, Jose; Garcia-Molina, Maria del Mar; Garcia-Molina, Francisco; Garcia-Ruiz, Pedro Antonio; Varon, Ramon [Departamento de Quimica-Fisica, Escuela de Ingenieros Industriales de Albacete, Universidad de Castilla la Mancha, Avda. Espana s and others

    2012-07-27

    Highlights: Black-Right-Pointing-Pointer The action the copper complexes and tyrosinase on phenols is equivalent. Black-Right-Pointing-Pointer Isotope effect showed that nucleophilic attack to copper atom may be the slower step. Black-Right-Pointing-Pointer The value of {rho} (Hammett constant) supports an electrophilic aromatic substitution. Black-Right-Pointing-Pointer Data obtained in steady state pH 7 conditions support the mechanism of Scheme 1SM. -- Abstract: A study of the monophenolase activity of tyrosinase by measuring the steady state rate with a group of p-substituted monophenols provides the following kinetic information: k{sub cat}{sup m} and the Michaelis constant, K{sub M}{sup m}. Analysis of these data taking into account chemical shifts of the carbon atom supporting the hydroxyl group ({delta}) and {sigma}{sub p}{sup +}, enables a mechanism to be proposed for the transformation of monophenols into o-diphenols, in which the first step is a nucleophilic attack on the copper atom on the form E{sub ox} (attack of the oxygen of the hydroxyl group of C-1 on the copper atom) followed by an electrophilic attack (attack of the hydroperoxide group on the ortho position with respect to the hydroxyl group of the benzene ring, electrophilic aromatic substitution with a reaction constant {rho} of -1.75). These steps show the same dependency on the electronic effect of the substituent groups in C-4. Furthermore, a study of a solvent deuterium isotope effect on the oxidation of monophenols by tyrosinase points to an appreciable isotopic effect. In a proton inventory study with a series of p-substituted phenols, the representation of k{sub cat}{sup f{sub n}}/k{sub cat}{sup f{sub 0}} against n (atom fractions of deuterium), where k{sub cat}{sup f{sub n}} is the catalytic constant for a molar fraction of deuterium (n) and k{sub cat}{sup f{sub 0}} is the corresponding kinetic parameter in a water solution, was linear for all substrates. These results indicate that

  8. Low-temperature chemistry between water and hydroxyl radicals: H/D isotopic effects

    NASA Astrophysics Data System (ADS)

    Lamberts, T.; Fedoseev, G.; Puletti, F.; Ioppolo, S.; Cuppen, H. M.; Linnartz, H.

    2016-01-01

    Sets of systematic laboratory experiments are presented - combining Ultra High Vacuum cryogenic and plasma-line deposition techniques - that allow us to compare H/D isotopic effects in the reaction of H2O (D2O) ice with the hydroxyl radical OD (OH). The latter is known to play a key role as intermediate species in the solid-state formation of water on icy grains in space. The main finding of our work is that the reaction H2O + OD → OH + HDO occurs and that this may affect the HDO/H2O abundances in space. The opposite reaction D2O + OH → OD + HDO is much less effective, and also given the lower D2O abundances in space not expected to be of astronomical relevance. The experimental results are extended to the other four possible reactions between hydroxyl and water isotopes and are subsequently used as input for Kinetic Monte Carlo simulations. This way we interpret our findings in an astronomical context, qualitatively testing the influence of the reaction rates.

  9. Do carboximide–carboxylic acid combinations form co-crystals? The role of hydroxyl substitution on the formation of co-crystals and eutectics

    PubMed Central

    Kaur, Ramanpreet; Gautam, Raj; Cherukuvada, Suryanarayan; Guru Row, Tayur N.

    2015-01-01

    Carboxylic acids, amides and imides are key organic systems which provide understanding of molecular recognition and binding phenomena important in biological and pharmaceutical settings. In this context, studies of their mutual interactions and compatibility through co-crystallization may pave the way for greater understanding and new applications of their combinations. Extensive co-crystallization studies are available for carboxylic acid/amide combinations, but only a few examples of carboxylic acid/imide co-crystals are currently observed in the literature. The non-formation of co-crystals for carboxylic acid/imide combinations has previously been rationalized, based on steric and computed stability factors. In the light of the growing awareness of eutectic mixtures as an alternative outcome in co-crystallization experiments, the nature of various benzoic acid/cyclic imide combinations is established in this paper. Since an additional functional group can provide sites for new intermolecular inter­actions and, potentially, promote supramolecular growth into a co-crystal, benzoic acids decorated with one or more hydroxyl groups have been systematically screened for co-crystallization with one unsaturated and two saturated cyclic imides. The facile formation of an abundant number of hydroxybenzoic acid/cyclic carboximide co-crystals is reported, including polymorphic and variable stoichiometry co-crystals. In the cases where co-crystals did not form, the combinations are shown invariably to result in eutectics. The presence or absence and geometric disposition of hydroxyl functionality on benzoic acid is thus found to drive the formation of co-crystals or eutectics for the studied carboxylic acid/imide combinations. PMID:25995843

  10. Do carboximide-carboxylic acid combinations form co-crystals? The role of hydroxyl substitution on the formation of co-crystals and eutectics.

    PubMed

    Kaur, Ramanpreet; Gautam, Raj; Cherukuvada, Suryanarayan; Guru Row, Tayur N

    2015-05-01

    Carboxylic acids, amides and imides are key organic systems which provide understanding of molecular recognition and binding phenomena important in biological and pharmaceutical settings. In this context, studies of their mutual interactions and compatibility through co-crystallization may pave the way for greater understanding and new applications of their combinations. Extensive co-crystallization studies are available for carboxylic acid/amide combinations, but only a few examples of carboxylic acid/imide co-crystals are currently observed in the literature. The non-formation of co-crystals for carboxylic acid/imide combinations has previously been rationalized, based on steric and computed stability factors. In the light of the growing awareness of eutectic mixtures as an alternative outcome in co-crystallization experiments, the nature of various benzoic acid/cyclic imide combinations is established in this paper. Since an additional functional group can provide sites for new intermolecular inter-actions and, potentially, promote supramolecular growth into a co-crystal, benzoic acids decorated with one or more hydroxyl groups have been systematically screened for co-crystallization with one unsaturated and two saturated cyclic imides. The facile formation of an abundant number of hydroxybenzoic acid/cyclic carboximide co-crystals is reported, including polymorphic and variable stoichiometry co-crystals. In the cases where co-crystals did not form, the combinations are shown invariably to result in eutectics. The presence or absence and geometric disposition of hydroxyl functionality on benzoic acid is thus found to drive the formation of co-crystals or eutectics for the studied carboxylic acid/imide combinations.

  11. Regioselective alkane hydroxylation with a mutant AlkB enzyme

    DOEpatents

    Koch, Daniel J.; Arnold, Frances H.

    2012-11-13

    AlkB from Pseudomonas putida was engineered using in-vivo directed evolution to hydroxylate small chain alkanes. Mutant AlkB-BMO1 hydroxylates propane and butane at the terminal carbon at a rate greater than the wild-type to form 1-propanol and 1-butanol, respectively. Mutant AlkB-BMO2 similarly hydroxylates propane and butane at the terminal carbon at a rate greater than the wild-type to form 1-propanol and 1-butanol, respectively. These biocatalysts are highly active for small chain alkane substrates and their regioselectivity is retained in whole-cell biotransformations.

  12. The Effect of Hydroxyl Moieties and Their Oxosubstitution on Bile Acid Association Studied in Floating Monolayers

    PubMed Central

    Szekeres, Márta; Viskolcz, Béla; Poša, Mihalj; Csanádi, János; Škorić, Dušan; Illés, Erzsébet; Tóth, Ildikó Y.; Tombácz, Etelka

    2014-01-01

    Bile salt aggregates are promising candidates for drug delivery vehicles due to their unique fat-solubilizing ability. However, the toxicity of bile salts increases with improving fat-solubilizing capability and so an optimal combination of efficient solubilization and low toxicity is necessary. To improve hydrophilicity (and decrease toxicity), we substituted hydroxyl groups of several natural bile acid (BA) molecules for oxogroups and studied their intrinsic molecular association behavior. Here we present the comparative Langmuir trough study of the two-dimensional (2D) association behavior of eight natural BAs and four oxoderivatives (traditionally called keto-derivatives) floated on an aqueous subphase. The series of BAs and derivatives showed systematic changes in the shape of the compression isotherms. Two types of association could be distinguished: the first transition was assigned to the formation of dimers through H-bonding and the second to the hydrophobic aggregation of BA dimers. Hydrophobic association of BA molecules in the films is linked to the ability of forming H-bonded dimers. Both H-bond formation and hydrophobic association weakened with increasing number of hydroxyl groups, decreasing distance between hydroxyl groups, and increasing oxosubstitution. The results also show that the Langmuir trough method is extremely useful in selecting appropriate BA molecules to design drug delivery systems. PMID:25685831

  13. Quantum Chemical Study on the Antioxidation Mechanism of Piceatannol and Isorhapontigenin toward Hydroxyl and Hydroperoxyl Radicals.

    PubMed

    Lu, Yang; Wang, AiHua; Shi, Peng; Zhang, Hui; Li, ZeSheng

    2015-01-01

    A systematic study of the antioxidation mechanisms behind hydroxyl (•OH) and hydroperoxyl (•OOH) radical scavenging activity of piceatannol (PIC) and isorhapontigenin (ISO) was carried out using density functional theory (DFT) method. Two reaction mechanisms, abstraction (ABS) and radical adduct formation (RAF), were discussed. A total of 24 reaction pathways of scavenging •OH and •OOH with PIC and ISO were investigated in the gas phase and solution. The thermodynamic and kinetic properties of all pathways were calculated. Based on these results, we evaluated the antioxidant activity of every active site of PIC and ISO and compared the abilities of PIC and ISO to scavenge radicals. According to our results, PIC and ISO may act as effective •OH and •OOH scavengers in organism. A4-hydroxyl group is a very important active site for PIC and ISO to scavenge radicals. The introducing of -OH or -OCH3 group to the ortho-position of A4-hydroxyl group would increase its antioxidant activity. Meanwhile, the conformational effect was researched, the results suggest that the presence and pattern of intramolecular hydrogen bond (IHB) are considerable in determining the antioxidant activity of PIC and ISO.

  14. Quantum Chemical Study on the Antioxidation Mechanism of Piceatannol and Isorhapontigenin toward Hydroxyl and Hydroperoxyl Radicals

    PubMed Central

    Lu, Yang; Wang, AiHua; Shi, Peng; Zhang, Hui; Li, ZeSheng

    2015-01-01

    A systematic study of the antioxidation mechanisms behind hydroxyl (•OH) and hydroperoxyl (•OOH) radical scavenging activity of piceatannol (PIC) and isorhapontigenin (ISO) was carried out using density functional theory (DFT) method. Two reaction mechanisms, abstraction (ABS) and radical adduct formation (RAF), were discussed. A total of 24 reaction pathways of scavenging •OH and •OOH with PIC and ISO were investigated in the gas phase and solution. The thermodynamic and kinetic properties of all pathways were calculated. Based on these results, we evaluated the antioxidant activity of every active site of PIC and ISO and compared the abilities of PIC and ISO to scavenge radicals. According to our results, PIC and ISO may act as effective •OH and •OOH scavengers in organism. A4-hydroxyl group is a very important active site for PIC and ISO to scavenge radicals. The introducing of -OH or -OCH3 group to the ortho-position of A4-hydroxyl group would increase its antioxidant activity. Meanwhile, the conformational effect was researched, the results suggest that the presence and pattern of intramolecular hydrogen bond (IHB) are considerable in determining the antioxidant activity of PIC and ISO. PMID:26176778

  15. Quantum Chemical Study on the Antioxidation Mechanism of Piceatannol and Isorhapontigenin toward Hydroxyl and Hydroperoxyl Radicals.

    PubMed

    Lu, Yang; Wang, AiHua; Shi, Peng; Zhang, Hui; Li, ZeSheng

    2015-01-01

    A systematic study of the antioxidation mechanisms behind hydroxyl (•OH) and hydroperoxyl (•OOH) radical scavenging activity of piceatannol (PIC) and isorhapontigenin (ISO) was carried out using density functional theory (DFT) method. Two reaction mechanisms, abstraction (ABS) and radical adduct formation (RAF), were discussed. A total of 24 reaction pathways of scavenging •OH and •OOH with PIC and ISO were investigated in the gas phase and solution. The thermodynamic and kinetic properties of all pathways were calculated. Based on these results, we evaluated the antioxidant activity of every active site of PIC and ISO and compared the abilities of PIC and ISO to scavenge radicals. According to our results, PIC and ISO may act as effective •OH and •OOH scavengers in organism. A4-hydroxyl group is a very important active site for PIC and ISO to scavenge radicals. The introducing of -OH or -OCH3 group to the ortho-position of A4-hydroxyl group would increase its antioxidant activity. Meanwhile, the conformational effect was researched, the results suggest that the presence and pattern of intramolecular hydrogen bond (IHB) are considerable in determining the antioxidant activity of PIC and ISO. PMID:26176778

  16. Apoptosis of THP-1 derived macrophages induced by sonodynamic therapy using a new sonosensitizer hydroxyl acetylated curcumin.

    PubMed

    Zheng, Longbin; Sun, Xinyong; Zhu, Xing; Lv, Fengxiang; Zhong, Zhaoyu; Zhang, Feng; Guo, Wenhui; Cao, Wenwu; Yang, Liming; Tian, Ye

    2014-01-01

    Curcumin is extracted from the rhizomes of the traditional Chinese herb Curcuma longa. Our previous study indicated curcumin was able to function as a sonosensitizer. Hydroxyl acylated curcumin was synthesized from curcumin to eliminate the unstable hydroxy perssad in our group. The potential use of Hydroxyl acylated curcumin as a sonosensitizer for sonodynamic therapy (SDT) requires further exploration. This study investigated the sonodynamic effect of Hydroxyl acylated curcumin on THP-1 macrophage. THP-1 macrophages were cultured with Hydroxyl acylated curcumin at a concentration of 5.0 μg/mL for 4 hours and then exposed to pulse ultrasound irradiation (0.5 W/cm2 with 1.0 MHz ) for 5 min, 10 min and 15 min. Six hours later, cell viability decreased significantly by CCK-8 assay. After ultrasound irradiation, the ratio of apoptosis and necrosis in SDT group was higher than that in control, Hydroxyl acylated curcumin alone and ultrasound alone. Moreover, the apoptotic rate was higher than necrotic rate with the flow cytometry analysis. Furthermore, Hydroxyl acylated curcumin-SDT induced reactive oxygen species (ROS) generation in THP-1 macrophages immediately after the ultrasound treatment while ROS generation was reduced significantly with the scavenger of singlet oxygen Sodium azide (NaN3). Hydroxyl acylated curcumin-SDT led to a conspicuous loss of mitochondrial membrane potential (MMP) compared with other groups, while MMP was increased significantly with the scavenger of singlet oxygen Sodium azide (NaN3), ROS inhibitor N-acetyl cysteine (NAC) and Mitochondrial Permeability Transition Pore (MPTP) inhibitor Cyclosporin A (CsA). The cytochrome C, cleaved-Caspase-9, cleaved-Caspase-3 and cleaved-PARP upregulated after SDT through Western blotting. These findings suggested that Hydroxyl acylated curcumin under low-intensity ultrasound had sonodynamic effect on THP-1 macrophages via generation of intracellular singlet oxygen and mitochondria-caspase signaling

  17. Sugars as hydroxyl radical scavengers: proof-of-concept by studying the fate of sucralose in Arabidopsis.

    PubMed

    Matros, Andrea; Peshev, Darin; Peukert, Manuela; Mock, Hans-Peter; Van den Ende, Wim

    2015-06-01

    Substantial formation of reactive oxygen species (ROS) is inevitable in aerobic life forms. Due to their extremely high reactivity and short lifetime, hydroxyl radicals are a special case, because cells have not developed enzymes to detoxify these most dangerous ROS. Thus, scavenging of hydroxyl radicals may only occur by accumulation of higher levels of simple organic compounds. Previous studies have demonstrated that plant-derived sugars show hydroxyl radical scavenging capabilities during Fenton reactions with Fe(2+) and hydrogen peroxide in vitro, leading to formation of less detrimental sugar radicals that may be subject of regeneration to non-radical carbohydrates in vivo. Here, we provide further evidence for the occurrence of such radical reactions with sugars in planta, by following the fate of sucralose, an artificial analog of sucrose, in Arabidopsis tissues. The expected sucralose recombination and degradation products were detected in both normal and stressed plant tissues. Oxidation products of endogenous sugars were also assessed in planta for Arabidopsis and barley, and were shown to increase in abundance relative to the non-oxidized precursor during oxidative stress conditions. We concluded that such non-enzymatic reactions with hydroxyl radicals form an integral part of plant antioxidant mechanisms contributing to cellular ROS homeostasis, and may be more important than generally assumed. This is discussed in relation to the recently proposed roles for Fe(2+) and hydrogen peroxide in processes leading to the origin of metabolism and the origin of life.

  18. Sugars as hydroxyl radical scavengers: proof-of-concept by studying the fate of sucralose in Arabidopsis.

    PubMed

    Matros, Andrea; Peshev, Darin; Peukert, Manuela; Mock, Hans-Peter; Van den Ende, Wim

    2015-06-01

    Substantial formation of reactive oxygen species (ROS) is inevitable in aerobic life forms. Due to their extremely high reactivity and short lifetime, hydroxyl radicals are a special case, because cells have not developed enzymes to detoxify these most dangerous ROS. Thus, scavenging of hydroxyl radicals may only occur by accumulation of higher levels of simple organic compounds. Previous studies have demonstrated that plant-derived sugars show hydroxyl radical scavenging capabilities during Fenton reactions with Fe(2+) and hydrogen peroxide in vitro, leading to formation of less detrimental sugar radicals that may be subject of regeneration to non-radical carbohydrates in vivo. Here, we provide further evidence for the occurrence of such radical reactions with sugars in planta, by following the fate of sucralose, an artificial analog of sucrose, in Arabidopsis tissues. The expected sucralose recombination and degradation products were detected in both normal and stressed plant tissues. Oxidation products of endogenous sugars were also assessed in planta for Arabidopsis and barley, and were shown to increase in abundance relative to the non-oxidized precursor during oxidative stress conditions. We concluded that such non-enzymatic reactions with hydroxyl radicals form an integral part of plant antioxidant mechanisms contributing to cellular ROS homeostasis, and may be more important than generally assumed. This is discussed in relation to the recently proposed roles for Fe(2+) and hydrogen peroxide in processes leading to the origin of metabolism and the origin of life. PMID:25891826

  19. Titration of free hydroxyl and strained siloxane sites on silicon dioxide with fluorescent probes.

    PubMed

    McCrate, Joseph M; Ekerdt, John G

    2013-09-24

    A technique enabling the detection and quantification of low density sites on planar SiO2 surfaces is demonstrated. Fluorescent probes are used to titrate free hydroxyl and strained siloxane sites on the surface of amorphous SiO2 substrates in vacuum. The titration of free hydroxyl sites was performed to validate the method and to provide a reference for the measurement of the strained siloxane site density. Perylene derivatives with different functional groups are chemisorbed onto the surface sites, enabling in situ photoluminescence (PL) measurements of the bound fluorophores. An amine functional group is used to selectively titrate strained siloxane sites, while an alcohol group is used for the titration of free hydroxyl sites. Emission intensity was found to be nonlinear with coverage for bound fluorophore densities greater than 0.1 nm(-2), necessitating the removal of molecules from the surface into a solution to obtain accurate density measurements. For lower densities, the coverage of bound fluorophores can be estimated directly from in situ PL measurements. The measured areal densities of bound fluorophores after titrating free hydroxyl sites are in good agreement with literature values for the densities of such sites on high surface area silica. PL measurements of SiO2 surfaces titrated with an amine derivative of perylene indicate that strained siloxane sites exist for vacuum pretreatment temperatures of 300 °C and increase with increasing pretreatment temperature. Densities of strained siloxane sites on the silica surface are estimated at 0.004-0.02 nm(-2) for pretreatment temperatures of 300-700 °C, demonstrating the sensitivity of this technique.

  20. OXYGEN ABUNDANCES IN CEPHEIDS

    SciTech Connect

    Luck, R. E.; Andrievsky, S. M.; Korotin, S. N.; Kovtyukh, V. V. E-mail: serkor@skyline.od.ua E-mail: scan@deneb1.odessa.ua

    2013-07-01

    Oxygen abundances in later-type stars, and intermediate-mass stars in particular, are usually determined from the [O I] line at 630.0 nm, and to a lesser extent, from the O I triplet at 615.7 nm. The near-IR triplets at 777.4 nm and 844.6 nm are strong in these stars and generally do not suffer from severe blending with other species. However, these latter two triplets suffer from strong non-local thermodynamic equilibrium (NLTE) effects and thus see limited use in abundance analyses. In this paper, we derive oxygen abundances in a large sample of Cepheids using the near-IR triplets from an NLTE analysis, and compare those abundances to values derived from a local thermodynamic equilibrium (LTE) analysis of the [O I] 630.0 nm line and the O I 615.7 nm triplet as well as LTE abundances for the 777.4 nm triplet. All of these lines suffer from line strength problems making them sensitive to either measurement complications (weak lines) or to line saturation difficulties (strong lines). Upon this realization, the LTE results for the [O I] lines and the O I 615.7 nm triplet are in adequate agreement with the abundance from the NLTE analysis of the near-IR triplets.

  1. Interstellar Abundance Standards Revisited

    NASA Astrophysics Data System (ADS)

    Sofia, Ulysses J.; Meyer, David M.

    2001-06-01

    We evaluate the stellar abundances often used to represent the total (gas plus dust) composition of the interstellar medium. Published abundances for B stars, young later type (F and G) stars, and the Sun are compared to the modeled dust-phase and measured gas-phase compositions of the interstellar medium. This study uses abundances for the five most populous elements in dust grains-C, O, Mg, Si, and Fe-and the cosmically abundant element, N. We find that B stars have metal abundances that are too low to be considered valid representations of the interstellar medium. The commonly invoked interstellar standard that is two-thirds of the solar composition is also rejected by recent observations. Young (<=2 Gyr) F and G disk stars and the Sun, however, cannot be ruled out as reliable proxies for the total interstellar composition. If their abundances are valid representations of the interstellar medium, then the apparent underabundance of carbon with respect to that required by dust models, i.e., the carbon crisis, is substantially eased.

  2. Catalytic hydroxylation of benzoic acid by hydrogen peroxide

    SciTech Connect

    Pulippurasseril, C.R.; Filippova, T.Yu.; Dedov, A.G.

    1992-12-31

    An effective catalytic system based on Fe(III) and surfactants is proposed for the hydroxylation of benozic acid by hydrogen peroxide in an aqueous medium at a temperature of 30-80{degrees}C. 8 refs., 1 tab.

  3. Hydroxyl radical production in plasma electrolysis with KOH electrolyte solution

    NASA Astrophysics Data System (ADS)

    Saksono, Nelson; Febiyanti, Irine Ayu; Utami, Nissa; Ibrahim

    2015-12-01

    Plasma electrolysis is an effective technology for producing hydroxyl radical (•OH). This method can be used for waste degradation process. This study was conducted to obtain the influence of applied voltage, electrolyte concentration, and anode depth in the plasma electrolysis system for producing hydroxyl radical. The materials of anode and cathode, respectively, were made from tungsten and stainless steel. KOH solution was used as the solution. Determination of hydroxyl radical production was done by measuring H2O2 amount formed in plasma system using an iodometric titration method, while the electrical energy consumed was obtained by measuring the electrical current throughout the process. The highest hydroxyl radical production was 3.51 mmol reached with 237 kJ energy consumption in the power supply voltage 600 V, 0.02 M KOH, and 0.5 cm depth of anode.

  4. Hydroxyl radical production in plasma electrolysis with KOH electrolyte solution

    SciTech Connect

    Saksono, Nelson; Febiyanti, Irine Ayu Utami, Nissa; Ibrahim

    2015-12-29

    Plasma electrolysis is an effective technology for producing hydroxyl radical (•OH). This method can be used for waste degradation process. This study was conducted to obtain the influence of applied voltage, electrolyte concentration, and anode depth in the plasma electrolysis system for producing hydroxyl radical. The materials of anode and cathode, respectively, were made from tungsten and stainless steel. KOH solution was used as the solution. Determination of hydroxyl radical production was done by measuring H{sub 2}O{sub 2} amount formed in plasma system using an iodometric titration method, while the electrical energy consumed was obtained by measuring the electrical current throughout the process. The highest hydroxyl radical production was 3.51 mmol reached with 237 kJ energy consumption in the power supply voltage 600 V, 0.02 M KOH, and 0.5 cm depth of anode.

  5. How does angiotensin II increase cardiac dopamine-beta-hydroxylation?

    PubMed

    Chevillard, C; Duchene, N; Alexandre, J M

    1975-03-01

    The potent accelerating effect of angiotensin II (Ang II) on caridac dopamine beta-hydroxylation was studied on slices of rat heart. Ang II did not affect the kinetics of beta-hydroxylation but it increased the axonal uptake of dopamine, and, concomitant with the acceleration of biosynthesis, it enhanced the accumulation of dopamine into tissue. Puromycin, in contrast to actinomycin D, antagonized the stimulation of dopamine beta-hydroxylation by Ang II, but did not suppress the rise in cardiac dopamine. Therefore, to promote the acceleration of dopamine beta-hydroxylation, (i) the rise in tissue dopamine available for conversion appeared to be insufficient, (ii) the formation of new proteins by activation of traduction seemed to constitute the basic mechanism of Ang II action.

  6. Development of competitive immunoassays to hydroxyl containing fungicide metabolites.

    PubMed

    Gough, Kevin C; Jarvis, Shila; Maddison, Ben C

    2011-01-01

    This paper describes the isolation of monoclonal antibodies and the development of competitive immunoassays to pesticide metabolites of the fungicides imazalil, carbendazim and thiabendazole. The metabolite specific hydroxyl residues were used as the reactive group with which to link the metabolite to the carrier proteins Keyhole Limpet Haemocyanin (KLH) and Bovine Serum Albumin (BSA). In each case immune responses in mice were raised and monoclonal antibodies were produced. Antibodies were developed into competitive ELISAs to the appropriate metabolite. The antibody raised to a metabolite of imazalil was optimised into a competitive ELISA format which had an assay IC50 of 7.5 μg/L and a limit of detection (LOD) of 1.1 μg/L. A single antibody isolated against the metabolite of carbendazim had assay IC50s of 3.2 and 2.7 μg/L for the metabolites of carbendazim and thiabendazole respectively with an LOD of 0.38 μg/L for both. These sensitive immunoassays may have application in the monitoring of human exposure to these fungicide residues either by occupational or non-occupational routes.

  7. Kinetic of benzotriazole oxidation by ozone and hydroxyl radical.

    PubMed

    Vel Leitner, Nathalie Karpel; Roshani, Babak

    2010-03-01

    Ozonation experiments were performed in batch reactors in order to determine the rate constants for the reaction of molecular ozone and OH radicals with benzotriazole (BT) at different pHs. The first group of ozonation experiments was carried out for the determination of the rate constant for the direct reactions between ozone and BT. Two different kinetic models were used for the determination of kinetic rate constants: (i) the log-reduction of BT with ozone in excess, (ii) the competition kinetic model. The second-order rate constants for BT with molecular ozone were determined to be 36.4+/-3.8M(-1) s(-1) and 18.4+/-0.8M(-1) s(-1) at pH 2 from the two methods respectively. With the competition method, the value at pH 5 was found to be 22.0+/-2.0M(-1) s(-1). In a following stage, the reaction of BT with OH radicals was investigated at pH values ranging from 2 to 10.2. Using a method involving two probe compounds during the ozonation, the second-order rate constants of the BT reaction with hydroxyl radicals were determined. The rate constants were found to vary from 6.2x10(9)M(-1) s(-1) at pH 10.2 to 1.7x10(10)M(-1) s(-1) at pH 2.

  8. Ginsenoside Rb1 directly scavenges hydroxyl radical and hypochlorous acid.

    PubMed

    Lü, Jian-Ming; Weakley, Sarah M; Yang, Zhen; Hu, Ming; Yao, Qizhi; Chen, Changyi

    2012-01-01

    Reactive oxygen species (ROS) have been implicated in a variety of inflammatory diseases including cardiovascular disease (CVD), cancer, diabetes, Alzheimer's disease, autism, cataracts and aging. When endogenous mechanisms for the maintenance of redox homeostasis are overwhelmed, dietary intake of antioxidants contributes substantially to balancing the body's oxidant/antioxidant status. Ginsenosides are thought to be primarily responsible for the pharmacological effect of P. ginseng root extracts on oxidative stress and inflammation. However, little is known about the underlying antioxidant mechanisms of individual ginsenoside; specifically, the reactivity of ginsenoside Rb1 with ROS has not been well studied. We found that Rb1 can significantly and selectively reduce hydroxyl radical (●OH) and hypochlorous acid (HOCl), two of the strongest ROS, with unique molecular mechanisms in a cell-free system. Rb1 directly scavenges the ●OH and protects plasmid DNA from damage induced by ●OH. ●OH likely attacks the double bond on the side chain of Rb1 as well as hydrogen atoms adjacent to the -OH groups, including those of sugar moieties. Rb1 also shows a high reactivity to HOCl and effectively inhibits HOCl-induced tyrosine chlorination in a cell free system. HOCl is added to the double bond of Rb1; the -Cl group and -OH group of HOCl possibly bond at C-24 and C-25 of Rb1 based on the regioselectivity of Markovnikov's Rule. To our knowledge, this is the first demonstration that ginsenoside Rb1 scavenges HOCl and protects tyrosine from HOCl-induced chlorination. Thus, this study reveals unique antioxidant mechanisms of individual ginsenoside Rb1, which may contribute to the pharmacological effect of P. ginseng and to the development of effective strategies for clinical applications of ginsenosides.

  9. Diffusion of hydroxyl ions from calcium hydroxide and Aloe vera pastes.

    PubMed

    Batista, Victor Eduardo de Souza; Olian, Douglas Dáquila; Mori, Graziela Garrido

    2014-01-01

    This study evaluated the diffusion through the dentinal tubules of hydroxyl ions from different calcium hydroxide (CH) pastes containing Aloe vera. Sixty single-rooted bovine teeth were used. The tooth crowns were removed, the root canals were instrumented and the specimens were assigned to 4 groups (n=15) according to the intracanal medication: Group CH/S - CH powder and saline paste; Group CH/P - CH powder and propylene glycol paste; Group CH/A - calcium hydroxide powder and Aloe vera gel paste; Group CH/A/P - CH powder, Aloe vera powder and propylene glycol paste. After placement of the root canal dressings, the teeth were sealed coronally and apically with a two-step epoxy adhesive. The teeth were placed in identified flasks containing deionized water and stored in an oven with 100% humidity at 37 °C. After 3 h, 24 h, 72 h, 7 days, 15 days and 30 days, the deionized water in the flasks was collected and its pH was measured by a pH meter. The obtained data were subjected to statistical analysis at a significance level of 5%. The results demonstrated that all pastes provided diffusion of hydroxyl ions through the dentinal tubules. The combination of Aloe vera and CH (group CH/A) provided a constant release of calcium ions. Group CH/A/P showed the highest pH at 24 and 72 h. In conclusion, the experimental pastes containing Aloe vera were able to enable the diffusion of hydroxyl ions through the dentinal tubules.

  10. Molecular dynamics simulation study of water adsorption on hydroxylated graphite surfaces.

    PubMed

    Picaud, Sylvain; Collignon, B; Hoang, Paul N M; Rayez, J C

    2006-04-27

    In this paper, we present results from molecular dynamic simulations devoted to the characterization of the interaction between water molecules and hydroxylated graphite surfaces considered as models for surfaces of soot emitted by aircraft. The hydroxylated graphite surfaces are modeled by anchoring several OH groups on an infinite graphite plane. The molecular dynamics simulations are based on a classical potential issued from quantum chemical calculations. They are performed at three temperatures (100, 200, and 250 K) to provide a view of the structure and dynamics of water clusters on the model soot surface. These simulations show that the water-OH sites interaction is quite weak compared to the water-water interaction. This leads to the clustering of the water molecules above the surface, and the corresponding water aggregate can only be trapped by the OH sites when the temperature is sufficiently low, or when the density of OH sites is sufficiently high.

  11. Observations and Analysis of Atmospheric Hydroxyl

    NASA Technical Reports Server (NTRS)

    Minschwaner, Ken R.

    1996-01-01

    Ground-based measurements of sunlight absorption at the OH P(sub 1)(l) resonance line at 308 nm have been made on a continuous basis at Fritz Peak, Colorado. The derived OH vertical column abundances show the persistence of a new seasonal regime which began in 1991. The fall minimum has been consistently depressed about 10-15% below the 1980-1990 average fall values. While the initial onset of depressed fall abundances occurred a few months after the Pinatubo eruption, there has been no fall OH recovery correlating with decreased amounts of volcanic aerosol found since spring 1993. The Colorado data also continues to exhibit an AM-PM asymmetry which varies seasonally, approximately in phase with local total ozone. These observations were presented at the Front Range AGU meeting in February 1996 and were published in Geophysical Research Letters in July 1996 (preprint enclosed). An update through the fall of 1996, when morning abundances were found to be extremely low, was presented at the Fall 1996 AGU meeting (abstract attached). A PEPSIOS instrument of identical design is currently operational and has been used since April 1996 for OH column measurements at New Mexico Tech, Socorro, NM. Title for both instruments was transferred from Florida Atlantic University to New Mexico Tech in February of 1996. Comparative measurements from the two instruments for April-July 1996 indicate small differences in OH column abundances, with New Mexico (34 deg N) abundances about 10% above Colorado (40 deg N) values for comparable solar zenith angles. A more detailed comparison will require at least one full year of data from both locations. New Mexico measurements were obtained on June 10, 1996, concurrently with a balloon launch of the NASA STRAT mission from Fort Sumner, New Mexico. We hope to make use of STRAT measurements H2O, CH4, and O3 which are particularly relevant to OH photochemistry. Additional work at New Mexico Tech involves a comparison of P(sub 1)(1) and Q(sub 1

  12. Hydroxyl-Directed Cross-Coupling: A Scalable Synthesis of Debromohamigeran E and Other Targets of Interest.

    PubMed

    Blaisdell, Thomas P; Morken, James P

    2015-07-15

    A hydroxyl functional group positioned β to a pinacol boronate can serve to direct palladium-catalyzed cross-coupling reactions. This feature can be used to control the reaction site in multiply borylated substrates and can activate boronates for reaction that would otherwise be unreactive.

  13. A rigorous description of the energy spectrum of the isopropanol molecule taking into account the internal rotation of hydroxyl

    NASA Astrophysics Data System (ADS)

    Burenin, A. V.

    2016-06-01

    Using the methods of a group chain, a rigorous algebraic model is constructed to describe the energy spectrum of the isopropanol molecule (CH3)2CHOH with an allowance for the internal rotation of hydroxyl. The model is rigorous in the sense that its correctness is limited only by the correctness of a chosen symmetry of internal dynamics of the molecule.

  14. A facile BPO-mediated ortho-hydroxylation and benzoylation of N-alkyl anilines for synthesis of 2-benzamidophenols.

    PubMed

    Zhang, Zhi-Jing; Quan, Xue-Jing; Ren, Zhi-Hui; Wang, Yao-Yu; Guan, Zheng-Hui

    2014-06-20

    A facile benzoyl peroxide (BPO) mediated ortho-hydroxylation and benzoylation of N-alkyl anilines for the synthesis of 2-benzamidophenols has been developed. The reaction tolerates a wide range of functional groups and is a good method for the straightforward synthesis of valuable 2-benzamidophenols in good yields under mild conditions.

  15. Direct Observation of a Nonheme Iron(IV)–Oxo Complex That Mediates Aromatic C–F Hydroxylation

    PubMed Central

    2015-01-01

    The synthesis of a pentadentate ligand with strategically designed fluorinated arene groups in the second coordination sphere of a nonheme iron center is reported. The oxidatively resistant fluorine substituents allow for the trapping and characterization of an FeIV(O) complex at −20 °C. Upon warming of the FeIV(O) complex, an unprecedented arene C–F hydroxylation reaction occurs. Computational studies support the finding that substrate orientation is a critical factor in the observed reactivity. This work not only gives rare direct evidence for the participation of an FeIV(O) species in arene hydroxylation but also provides the first example of a high-valent iron–oxo complex that mediates aromatic C–F hydroxylation. PMID:25246108

  16. Solar abundance of platinum

    PubMed Central

    Burger, Harry; Aller, Lawrence H.

    1975-01-01

    Three lines of neutral platinum, located at λ 2997.98 Å, λ 3064.71 Å, and λ 3301.86 Å have been used to determine the solar platinum abundance by the method of spectral synthesis. On the scale, log A(H) = 12.00, the thus-derived solar platinum abundance is 1.75 ± 0.10, in fair accord with Cameron's value of log A(Pt) = 1.69 derived by Mason from carbonaceous chondrites and calculated on the assumption that log A(Si) = 7.55 in the sun. PMID:16592278

  17. Hydroxyl Radical-Mediated Novel Modification of Peptides: N-Terminal Cyclization through the Formation of α-Ketoamide.

    PubMed

    Lee, Seon Hwa; Kyung, Hyunsook; Yokota, Ryo; Goto, Takaaki; Oe, Tomoyuki

    2015-01-20

    The hydroxyl radical-mediated oxidation of peptides and proteins constitutes a large group of post-translational modifications that can result in structural and functional changes. These oxidations can lead to hydroxylation, sulfoxidation, or carbonylation of certain amino acid residues and cleavage of peptide bonds. In addition, hydroxyl radicals can convert the N-terminus of peptides to an α-ketoamide via abstraction of the N-terminal α-hydrogen and hydrolysis of the ketimine intermediate. In the present study, we identified N-terminal cyclization as a novel modification mediated by a hydroxyl radical. The reaction of angiotensin (Ang) II (DRVYIHPF) and the hydroxyl radical generated by the Cu(II)/ascorbic acid (AA) system or UV/hydrogen peroxide system produced N-terminal cyclized-Ang II (Ang C) and pyruvamide-Ang II (Ang P, CH3COCONH-RVYIHPF). The structure of Ang C was confirmed by mass spectrometry and comparison to an authentic standard. The subsequent incubation of isolated Ang P in the presence of Cu(II)/AA revealed that Ang P was the direct precursor of Ang C. The proposed mechanism involves the formation of a nitrogen-centered (aminyl) radical, which cyclizes to form a five-membered ring containing the alkoxy radical. The subsequent β-scission reaction of the alkoxyl radical results in the cleavage of the terminal CH3CO group. The initial aminyl radical can be stabilized by chelation to the Cu(II) ions. The affinity of Ang C toward the Ang II type 1 receptor was significantly lower than that of Ang II or Ang P. Ang C was not further metabolized by aminopeptidase A, which converts Ang II to Ang III. Hydroxyl radical-mediated N-terminal cyclization was also observed in other Ang peptides containing N-terminal alanine, arginine, valine, and amyloid β 1-11 (DAEFRHDSGYE).

  18. Evolving P450pyr Monooxygenase for Regio- and Stereoselective Hydroxylations.

    PubMed

    Yang, Yi; Li, Zhi

    2015-01-01

    P450pyr monooxygenase from Sphingomonas sp. HXN-200 catalysed the regio- and stereoselective hydroxylation at a non-activated carbon atom, a useful but challenging reaction in classic chemistry, with unique substrate specificity for a number of alicyclic compounds. New P450pyr mutants were developed by directed evolution with improved catalytic performance, thus significantly extending the application of the P450pyr monooxygenase family in biohydroxylation to prepare useful and valuable chiral alcohols. Directed evolution of P450pyr created new enzymes with improved S-enantioselectivity or R-enantioselectivity for the hydroxylation of N-benzyl pyrrolidine, enhanced regioselectivity for the hydroxylation of N-benzyl pyrrolidinone, and increased enantioselectivity for the hydroxylation of N-benzyl piperidinone, respectively. Directed evolution of P450pyr generated also mutants with fully altered regioselectivity (from terminal to subterminal) and newly created excellent S-enantioselectivity for the biohydroxylation of n-octane and propylbenzene, respectively, providing new opportunities for the regio- and enantioselective alkane functionalization. New P450pyr mutants were engineered as the first catalyst for highly selective terminal hydroxylation of n-butanol to 1,4-butanediol. Several novel, accurate, sensitive, simple, and HTS assays based on colorimetric or MS detection for measuring the enantio- and/or regioselectivity of hydroxylation were developed and proven to be practical in directed evolution. The P450pyr X-ray structure was obtained and used to guide the evolution. In silico modelling and substrate docking provided some insight into the influence of several important amino acid mutations of the engineered P450pyr mutants on the altered or enhanced regio- and enantioselectivity as well as new substrate acceptance. The obtained information and knowledge is useful for further engineering of P450pyr for other hydroxylations and oxidations. PMID:26507217

  19. Evolving P450pyr Monooxygenase for Regio- and Stereoselective Hydroxylations.

    PubMed

    Yang, Yi; Li, Zhi

    2015-01-01

    P450pyr monooxygenase from Sphingomonas sp. HXN-200 catalysed the regio- and stereoselective hydroxylation at a non-activated carbon atom, a useful but challenging reaction in classic chemistry, with unique substrate specificity for a number of alicyclic compounds. New P450pyr mutants were developed by directed evolution with improved catalytic performance, thus significantly extending the application of the P450pyr monooxygenase family in biohydroxylation to prepare useful and valuable chiral alcohols. Directed evolution of P450pyr created new enzymes with improved S-enantioselectivity or R-enantioselectivity for the hydroxylation of N-benzyl pyrrolidine, enhanced regioselectivity for the hydroxylation of N-benzyl pyrrolidinone, and increased enantioselectivity for the hydroxylation of N-benzyl piperidinone, respectively. Directed evolution of P450pyr generated also mutants with fully altered regioselectivity (from terminal to subterminal) and newly created excellent S-enantioselectivity for the biohydroxylation of n-octane and propylbenzene, respectively, providing new opportunities for the regio- and enantioselective alkane functionalization. New P450pyr mutants were engineered as the first catalyst for highly selective terminal hydroxylation of n-butanol to 1,4-butanediol. Several novel, accurate, sensitive, simple, and HTS assays based on colorimetric or MS detection for measuring the enantio- and/or regioselectivity of hydroxylation were developed and proven to be practical in directed evolution. The P450pyr X-ray structure was obtained and used to guide the evolution. In silico modelling and substrate docking provided some insight into the influence of several important amino acid mutations of the engineered P450pyr mutants on the altered or enhanced regio- and enantioselectivity as well as new substrate acceptance. The obtained information and knowledge is useful for further engineering of P450pyr for other hydroxylations and oxidations.

  20. Morphology-dependent interplay of reduction behaviors, oxygen vacancies and hydroxyl reactivity of CeO2 nanocrystals.

    PubMed

    Gao, Yuxian; Li, Rongtan; Chen, Shilong; Luo, Liangfeng; Cao, Tian; Huang, Weixin

    2015-12-21

    Reduction behaviors, oxygen vacancies and hydroxyl groups play decisive roles in the surface chemistry and catalysis of oxides. Employing isothermal H2 reduction we simultaneously reduced CeO2 nanocrystals with different morphologies, created oxygen vacancies and produced hydroxyl groups. The morphology of CeO2 nanocrystals was observed to strongly affect the reduction process and the resultant oxygen vacancy structure. The resultant oxygen vacancies are mainly located on the surfaces of CeO2 cubes and rods but in the subsurface/bulk of CeO2 octahedra. The reactivity of isolated bridging hydroxyl groups on CeO2 nanocrystals was found to depend on the local oxygen vacancy concentration, in which they reacted to produce water at low local oxygen vacancy concentrations but to produce both water and hydrogen with increasing local oxygen vacancy concentration. These results reveal a morphology-dependent interplay among the reduction behaviors, oxygen vacancies and hydroxyl reactivity of CeO2 nanocrystals, which deepens the fundamental understanding of the surface chemistry and catalysis of CeO2.

  1. Inhibitory effect of free radical scavenger, MCI-186, in the increase of hydroxyl radical induced by iminodipropionitrile in rats.

    PubMed

    Nomoto, Nobuatsu

    2004-04-15

    Beta,beta'-Iminodipropionitrile (IDPN) is known to produce permanent motor behavioral abnormalities in rats. This behavior syndrome is also termed as "ECC Syndrome", the animal model for Gilles de la Tourette syndrome in humans. Some reports showed that these behavioral abnormalities are caused by monoamine changes. However, there was little research on the relation between IDPN-induced behavioral abnormalities and free radical. 3-Methyl-1-phenyl-2-pyrazolin-5-one (MCI-186), a newly synthesized free radical scavenger, exerts beneficial free radical scavenging and antioxidant characteristics. We investigated that MCI-186 inhibited the process of hydroxyl radical formation induced by IDPN administration in the rat brain. In the group of IDPN administration, hydroxyl radical levels exhibited predominant increase in most parts of the rat brain. In the group of IDPN and MCI-186 administration, hydroxyl radical levels marked significant decrease compared with those in the group of IDPN administration. Therefore, MCI-186 inhibited production of hydroxyl radical and might prove to be effective against ECC syndrome induced by IDPN.

  2. Pulse radiolysis studies on reactions of hydroxyl radicals with selenocystine derivatives.

    PubMed

    Mishra, B; Kumbhare, L B; Jain, V K; Priyadarsini, K I

    2008-04-10

    Reactions of hydroxyl radicals (*OH) with selenocystine (SeCys) and two of its analogues, diselenodipropionic acid (SeP) and selenocystamine (SeA), have been studied in aqueous solutions at pHs of 1, 7, and 10 using the pulse radiolysis technique coupled with absorption detection. All of these diselenides react with *OH radicals with rate constants of approximately 10(10) M(-1) s(-1), producing diselenide radical cations ( approximately 1-5 micros after the pulse), with an absorption maximum at 560 nm, by elimination of H(2)O or OH(-) from hydroxyl radical adducts. Assignment of the 560 nm band to the diselenide radical cation was made by comparing the transient spectra with those produced upon reaction of diselenides with specific one-electron oxidants, Cl(2)(*-) (pH 1) and Br(2)(*-) radicals (pHs of 7 and 10). SeP having a carboxylic acid functionality showed quantitative conversion of hydroxyl radical adducts to radical cations. The compounds SeCys and SeA, having an amino functional group, in addition to the radical cations, produced a new transient with lambda(max) at 460 nm, at later time scales ( approximately 20-40 micros after the pulse). The rate and yield of formation of the 460 nm band increased with increasing concentrations of either SeCys or SeA. In analogy with similar studies reported for analogous disulfides, the 460 nm transient absorption band has been assigned to a triselenide radical adduct. The one-electron reduction potentials of the compounds were estimated to be 0.96, 1.3, and 1.6 V versus NHE, respectively, for SeP, SeCys, and SeA at pH 7. From these studies, it has been concluded that the electron-donating carboxylic acid group decreases the reduction potential and facilitates quantitative conversion of hydroxyl radical adducts to radical cations, while the electron-withdrawing NH(3)(+) group not only increases the reduction potential but also leads to fragmentation of the hydroxyl radical adduct to selenyl radicals, which are converted

  3. Abundances of light elements.

    PubMed Central

    Pagel, B E

    1993-01-01

    Recent developments in the study of abundances of light elements and their relevance to cosmological nucleosynthesis are briefly reviewed. The simplest model, based on standard cosmology and particle physics and assuming homogeneous baryon density at the relevant times, continues to stand up well. PMID:11607388

  4. Lincomycin Biosynthesis Involves a Tyrosine Hydroxylating Heme Protein of an Unusual Enzyme Family

    PubMed Central

    Novotna, Jitka; Olsovska, Jana; Novak, Petr; Mojzes, Peter; Chaloupkova, Radka; Kamenik, Zdenek; Spizek, Jaroslav; Kutejova, Eva; Mareckova, Marketa; Tichy, Pavel; Damborsky, Jiri; Janata, Jiri

    2013-01-01

    The gene lmbB2 of the lincomycin biosynthetic gene cluster of Streptomyces lincolnensis ATCC 25466 was shown to code for an unusual tyrosine hydroxylating enzyme involved in the biosynthetic pathway of this clinically important antibiotic. LmbB2 was expressed in Escherichia coli, purified near to homogeneity and shown to convert tyrosine to 3,4-dihydroxyphenylalanine (DOPA). In contrast to the well-known tyrosine hydroxylases (EC 1.14.16.2) and tyrosinases (EC 1.14.18.1), LmbB2 was identified as a heme protein. Mass spectrometry and Soret band-excited Raman spectroscopy of LmbB2 showed that LmbB2 contains heme b as prosthetic group. The CO-reduced differential absorption spectra of LmbB2 showed that the coordination of Fe was different from that of cytochrome P450 enzymes. LmbB2 exhibits sequence similarity to Orf13 of the anthramycin biosynthetic gene cluster, which has recently been classified as a heme peroxidase. Tyrosine hydroxylating activity of LmbB2 yielding DOPA in the presence of (6R)-5,6,7,8-tetrahydro-L-biopterin (BH4) was also observed. Reaction mechanism of this unique heme peroxidases family is discussed. Also, tyrosine hydroxylation was confirmed as the first step of the amino acid branch of the lincomycin biosynthesis. PMID:24324587

  5. Ab initio dynamics of the cytochrome P450 hydroxylation reaction

    SciTech Connect

    Elenewski, Justin E.; Hackett, John C

    2015-02-14

    The iron(IV)-oxo porphyrin π-cation radical known as Compound I is the primary oxidant within the cytochromes P450, allowing these enzymes to affect the substrate hydroxylation. In the course of this reaction, a hydrogen atom is abstracted from the substrate to generate hydroxyiron(IV) porphyrin and a substrate-centered radical. The hydroxy radical then rebounds from the iron to the substrate, yielding the hydroxylated product. While Compound I has succumbed to theoretical and spectroscopic characterization, the associated hydroxyiron species is elusive as a consequence of its very short lifetime, for which there are no quantitative estimates. To ascertain the physical mechanism underlying substrate hydroxylation and probe this timescale, ab initio molecular dynamics simulations and free energy calculations are performed for a model of Compound I catalysis. Semiclassical estimates based on these calculations reveal the hydrogen atom abstraction step to be extremely fast, kinetically comparable to enzymes such as carbonic anhydrase. Using an ensemble of ab initio simulations, the resultant hydroxyiron species is found to have a similarly short lifetime, ranging between 300 fs and 3600 fs, putatively depending on the enzyme active site architecture. The addition of tunneling corrections to these rates suggests a strong contribution from nuclear quantum effects, which should accelerate every step of substrate hydroxylation by an order of magnitude. These observations have strong implications for the detection of individual hydroxylation intermediates during P450 catalysis.

  6. Histopathology of fathead minnow (Pimephales promelas) exposed to hydroxylated fullerenes.

    PubMed

    Jovanović, Boris; Whitley, Elizabeth M; Palić, Dušan

    2014-11-01

    Hydroxylated fullerenes are reported to be very strong antioxidants, acting to quench reactive oxygen species, thus having strong potential for important and widespread applications in innovative therapies for a variety of disease processes. However, their potential for toxicological side effects is still largely controversial and unknown. Effects of hydroxylated fullerenes C60(OH)24 on the fathead minnow (Pimephales promelas) were investigated microscopically after a 72-hour (acute) exposure by intraperitoneal injection of 20 ppm of hydroxylated fullerenes per gram of body mass. Cumulative, semi-quantitative histopathologic evaluation of brain, liver, anterior kidney, posterior kidney, skin, coelom, gills and the vestibuloauditory system revealed significant differences between control and hydroxylated fullerene-treated fish. Fullerene-treated fish had much higher cumulative histopathology scores. Histopathologic changes included loss of cellularity in the interstitium of the kidney, a primary site of haematopoiesis in fish, and loss of intracytoplasmic glycogen in liver. In the coelom, variable numbers of leukocytes, including many macrophages and fewer heterophils and rodlet cells, were admixed with the nanomaterial. These findings raise concern about in vivo administration of hydroxylated fullerenes in experimental drugs and procedures in human medicine, and should be investigated in more detail.

  7. Degradation pathways of lamotrigine under advanced treatment by direct UV photolysis, hydroxyl radicals, and ozone.

    PubMed

    Keen, Olya S; Ferrer, Imma; Michael Thurman, E; Linden, Karl G

    2014-12-01

    Lamotrigine is recently recognized as a persistent pharmaceutical in the water environment and wastewater effluents. Its degradation was studied under UV and ozone advanced oxidation treatments with reaction kinetics of lamotrigine with ozone (≈4 M(-1)s(-1)), hydroxyl radical [(2.1 ± 0.3) × 10(9)M(-1)s(-1)] and by UV photolysis with low and medium pressure mercury vapor lamps [quantum yields ≈0 and (2.7 ± 0.4)× 10(-4) respectively] determined. All constants were measured at pH 6 and at temperature ≈20°C. The results indicate that lamotrigine is slow to respond to direct photolysis or oxidation by ozone and no attenuation of the contaminant is expected in UV or ozone disinfection applications. The compound reacts rapidly with hydroxyl radicals indicating that advanced oxidation processes would be effective for its treatment. Degradation products were identified under each treatment process using accurate mass time-of-flight spectrometry and pathways of decay were proposed. The main transformation pathways in each process were: dechlorination of the benzene ring during direct photolysis; hydroxyl group addition to the benzene ring during the reaction with hydroxyl radicals; and triazine ring opening after reaction with ozone. Different products that form in each process may be to a varying degree less environmentally stable than the parent lamotrigine. In addition, a novel method of ozone quenching without addition of salts is presented. The new quenching method would allow subsequent mass spectrometry analysis without a solid phase extraction clean-up step. The method involves raising the pH of the sample to approximately 10 for a few seconds and lowering it back and is therefore limited to applications for which temporary pH change is not expected to affect the outcome of the analysis.

  8. Hydroxyl and water molecule orientations in trypsin: Comparison to molecular dynamics structures

    SciTech Connect

    McDowell, R.S.; Kossiakoff, A.A.

    1994-12-31

    A comparison is presented of experimentally observed hydroxyl and water hydrogens in trypsin determined from neutron density maps with the results of a 140ps molecular dynamics (MD) simulation. Experimental determination of hydrogen and deuterium atom positions in molecules as large as proteins is a unique capability of neutron diffraction. The comparison addresses the degree to which a standard force-field approach can adequately describe the local electrostatic and van der Waals forces that determine the orientations of these hydrogens. Neutron densities, derived from 2.1{Angstrom} D{sub 2}O-H{sub 2}O difference Fourier maps, provide a database of 27 well-ordered hydroxyl hydrogens. Most of the simulated hydroxyl orientations are within a standard deviation of the experimentally-observed positions, including several examples in which both the simulation and the neutron density indicate that a hydroxyl group is shifted from a {open_quote}standard{close_quote} rotamer. For the most highly ordered water molecules, the hydrogen distributions calculated from the trajectory were in good agreement with neutron density; simulated water molecules that displayed multiple hydrogen bonding networks had correspondingly broadened neutron density profiles. This comparison was facilitated by development of a method to construct a pseudo 2{Angstrom} density map based on the hydrogen atom distributions from the simulation. The degree of disorder of internal water molecules is shown to result primarily from the electrostatic environment surrounding that water molecule as opposed to the cavity size available to the molecule. A method is presented for comparing the discrete observations sampled in a dynamics trajectory with the time- averaged data obtained from X-ray or neutron diffraction studies. This method is particularly useful for statically-disordered water molecules, in which the average location assigned from a trajectory may represent a site of relatively low occupancy.

  9. Steroid Hydroxylation by Basidiomycete Peroxygenases: a Combined Experimental and Computational Study

    PubMed Central

    Babot, Esteban D.; del Río, José C.; Cañellas, Marina; Sancho, Ferran; Lucas, Fátima; Guallar, Víctor; Kalum, Lisbeth; Lund, Henrik; Gröbe, Glenn; Scheibner, Katrin; Ullrich, René; Hofrichter, Martin; Martínez, Angel T.

    2015-01-01

    The goal of this study is the selective oxyfunctionalization of steroids under mild and environmentally friendly conditions using fungal enzymes. With this purpose, peroxygenases from three basidiomycete species were tested for the hydroxylation of a variety of steroidal compounds, using H2O2 as the only cosubstrate. Two of them are wild-type enzymes from Agrocybe aegerita and Marasmius rotula, and the third one is a recombinant enzyme from Coprinopsis cinerea. The enzymatic reactions on free and esterified sterols, steroid hydrocarbons, and ketones were monitored by gas chromatography, and the products were identified by mass spectrometry. Hydroxylation at the side chain over the steroidal rings was preferred, with the 25-hydroxyderivatives predominating. Interestingly, antiviral and other biological activities of 25-hydroxycholesterol have been reported recently (M. Blanc et al., Immunity 38:106–118, 2013, http://dx.doi.org/10.1016/j.immuni.2012.11.004). However, hydroxylation in the ring moiety and terminal hydroxylation at the side chain also was observed in some steroids, the former favored by the absence of oxygenated groups at C-3 and by the presence of conjugated double bonds in the rings. To understand the yield and selectivity differences between the different steroids, a computational study was performed using Protein Energy Landscape Exploration (PELE) software for dynamic ligand diffusion. These simulations showed that the active-site geometry and hydrophobicity favors the entrance of the steroid side chain, while the entrance of the ring is energetically penalized. Also, a direct correlation between the conversion rate and the side chain entrance ratio could be established that explains the various reaction yields observed. PMID:25862224

  10. Promotional effect of surface hydroxyls on electrochemical reduction of CO2 over SnOx/Sn electrode

    DOE PAGES

    Cui, Chaonan; Han, Jinyu; Zhu, Xinli; Liu, Xiao; Wang, Hua; Mei, Donghai; Ge, Qingfeng

    2016-01-16

    In this study, tin oxide (SnOx) formation on tin-based electrode surfaces during CO2 electrochemical reduction can have a significant impact on the activity and selectivity of the reaction. In the present study, density functional theory (DFT) calculations have been performed to understand the role of SnOx in CO2 reduction using a SnO monolayer on the Sn(112) surface as a model for SnOx. Water molecules have been treated explicitly and considered actively participating in the reaction. The results showed that H2O dissociates on the perfect SnO monolayer into two hydroxyl groups symmetrically on the surface. CO2 energetically prefers to react withmore » the hydroxyl, forming a bicarbonate (HCO3(t)*) intermediate, which can then be reduced to either formate (HCOO*) by hydrogenating the carbon atom or carboxyl (COOH*) by protonating the oxygen atom. Both steps involve a simultaneous Csingle bondO bond breaking. Further reduction of HCOO* species leads to the formation of formic acid in the acidic solution at pH < 4, while the COOH* will decompose to CO and H2O via protonation. Whereas the oxygen vacancy (VO) in the oxide monolayer maybe formed by the reduction, it can be recovered by H2O dissociation, resulting in two embedded hydroxyl groups. The results show that the hydroxylated surface with two symmetric hydroxyls is energetically more favorable for CO2 reduction than the hydroxylated VO surface with two embedded hydroxyls. The reduction potential for the former has a limiting-potential of –0.20 V (RHE), lower than that for the latter (–0.74 V (RHE)). Compared to the pure Sn electrode, the formation of SnOx monolayer on the electrode under the operating conditions promotes CO2 reduction more effectively by forming surface hydroxyls, thereby providing a new channel via COOH* to the CO formation, although formic acid is still the major reduction product.« less

  11. Identification, Synthesis, and Biological Evaluation of Metabolites of the Experimental Cancer Treatment Drugs Indotecan (LMP400) and Indimitecan (LMP776) and Investigation of Isomerically Hydroxylated Indenoisoquinoline Analogues as Topoisomerase I Poisons

    PubMed Central

    Cinelli, Maris A.; Reddy, P.V. Narasimha; Lv, Peng-Cheng; Liang, Jian-Hua; Chen, Lian; Agama, Keli; Pommier, Yves; van Breemen, Richard B.; Cushman, Mark

    2012-01-01

    Hydroxylated analogues of the anticancer topoisomerase I (Top1) inhibitors indotecan (LMP400) and indimitecan (LMP76) have been prepared because: 1) a variety of potent Top1 poisons are known that contain strategically placed hydroxyl groups, which provides a clear rationale for incorporating them in the present case, and 2) the hydroxylated compounds could conceivably serve as synthetic standards for the identification of metabolites. Indeed, incubating LMP400 and LMP776 with human liver microsomes resulted in two major metabolites of each drug, which had HPLC retention times and mass fragmentation patterns identical to the synthetic standards. The hydroxylated indotecan and indimitecan metabolites and analogues were tested as Top1 poisons and for antiproliferative activity in a variety of human cancer cell cultures, and in general were found to be very potent. Differences in activity resulting from the placement of the hydroxyl group are explained by molecular modeling analyses. PMID:23215354

  12. One-step microwave synthesis of N-doped hydroxyl-functionalized carbon dots with ultra-high fluorescence quantum yields.

    PubMed

    Zhang, Yongqiang; Liu, Xingyuan; Fan, Yi; Guo, Xiaoyang; Zhou, Lei; Lv, Ying; Lin, Jie

    2016-08-18

    A one-step microwave synthesis of N-doped hydroxyl-functionalized carbon dots (CDs) with ultra-high fluorescence quantum yields (QYs) of 99% is reported. These ultra-high QY CDs were synthesized using citric acid and amino compound-containing hydroxyls like ethanolamine and tris(hydroxylmethyl)aminomethane. Amino and carboxyl moieties can form amides through dehydration condensation reactions, and these amides act as bridges between carboxyl and hydroxyl groups, and modify hydroxyl groups on the surface of the CDs. The entire reaction can be carried out within 5 min. When the molar ratio of reactants is 1 : 1, the hydroxyl and graphitic nitrogen content is the highest, and the synergy leads to a high ratio between the radiative transition rate and nonradiative transition rate as well as a high QY. The developed pathway to N-doped hydroxyl-functionalized CDs can provide unambiguous and remarkable insights into the design of highly luminescent functionalized carbon dots, and expedite the applications of CDs. PMID:27500530

  13. Biomolecule-biomaterial interaction: a DFT-D study of glycine adsorption and self-assembly on hydroxylated Cr2O3 surfaces.

    PubMed

    Costa, D; Garrain, P-A; Diawara, B; Marcus, P

    2011-03-15

    The adsorption of glycine, the building block of amino acids, on hydroxylated (0001)-Cr2O3 model surfaces, representing the stainless steel passive film surface, was modeled by means of the GGA + U method. The roles of glycine coverage and surface termination (hydroxylated Cr- and O-terminated surfaces) on the adsorption mode and self-assembly properties were explored. The hydroxylated Cr-terminated Cr2O3 surface, which presents two types of (H)OH groups exhibiting different acidic character, is more reactive than the hydroxylated O-terminated surface, where one single type of OH group is present, for all adsorption modes and coverages considered. Outer sphere adsorption occurs in the zwitterion form, stabilized at low coverage through H-bond formation with coadsorbed water molecules, and at the monolayer coverage by glycine self-assembling. The OH substitution by glycinate is favored on the hydroxylated Cr-terminated surface and not on the O-terminated one. The inclusion of dispersion forces does not change the observed tendencies. An atomistic thermodynamics approach suggests that outer sphere adsorption is thermodynamically favored over inner sphere adsorption in the whole domain of glycine concentration. The obtained SAM's free energies of formation are rationalized in a model considering the balance between sublimation and solvation free energies, and extrapolated to other amino acids, to predict the SAMs formation above hydroxylated surfaces. It is found that hydrophobic AA tend to self-assemble at the surface, whereas hydrophilic ones do not.

  14. Effects of hydroxylated carbon nanotubes on the aggregation of Aβ16-22 peptides: a combined simulation and experimental study.

    PubMed

    Xie, Luogang; Lin, Dongdong; Luo, Yin; Li, Huiyu; Yang, Xinju; Wei, Guanghong

    2014-10-21

    The pathogenesis of Alzheimer's disease (AD) is associated with the aggregation of amyloid-β (Aβ) peptides into toxic aggregates with ?-sheet character. In a previous computational study, we showed that pristine single-walled carbon nanotubes (SWCNTs) can inhibit the formation of β-sheet-rich oligomers in the central hydrophobic core fragment of Aβ (Aβ16-22). However, the poor solubility of SWCNTs in water hinders their use in biomedical applications and nanomedicine. Here, we investigate the influence of hydroxylated SWCNT, a water-soluble SWCNT derivative, on the aggregation of Aβ16-22 peptides using all-atom explicit-water replica exchange molecular dynamics simulations. Our results show that hydroxylated SWCNTs can significantly inhibit β-sheet formation and shift the conformations of Aβ16-22 oligomers from ordered β-sheet-rich structures toward disordered coil aggregates. Detailed analyses of the SWCNT-Aβ interaction reveal that the inhibition of β-sheet formation by hydroxylated SWCNTs mainly results from strong electrostatic interactions between the hydroxyl groups of SWCNTs and the positively charged residue K16 of Aβ16-22 and hydrophobic and aromatic stacking interactions between SWCNTs and F19 and F20. In addition, our atomic force microscopy and thioflavin T fluorescence experiments confirm the inhibitory effect of both pristine and hydroxylated SWCNTs on Aβ16-22 fibrillization, in support of our previous and present replica exchange molecular dynamics simulation results. These results demonstrate that hydroxylated SWCNTs efficiently inhibit the aggregation of Aβ16-22; in addition, they offer molecular insight into the inhibition mechanism, thus providing new clues for the design of therapeutic drugs against amyloidosis.

  15. Beta Hydroxylation of Glycolipids from Ustilago maydis and Pseudozyma flocculosa by an NADPH-Dependent β-Hydroxylase▿

    PubMed Central

    Teichmann, Beate; Lefebvre, François; Labbé, Caroline; Bölker, Michael; Linne, Uwe; Bélanger, Richard R.

    2011-01-01

    Flocculosin and ustilagic acid (UA), two highly similar antifungal cellobiose lipids, are respectively produced by Pseudozyma flocculosa, a biocontrol agent, and Ustilago maydis, a plant pathogen. Both glycolipids contain a short-chain fatty acid hydroxylated at the β position but differ in the long fatty acid, which is hydroxylated at the α position in UA and at the β position in flocculosin. In both organisms, the biosynthesis genes are arranged in large clusters. The functions of most genes have already been characterized, but those of the P. flocculosa fhd1 gene and its homolog from U. maydis, uhd1, have remained undefined. The deduced amino acid sequences of these genes show homology to those of short-chain dehydrogenases and reductases (SDR). We disrupted the uhd1 gene in U. maydis and analyzed the secreted UA. uhd1 deletion strains produced UA lacking the β-hydroxyl group of the short-chain fatty acid. To analyze the function of P. flocculosa Fhd1, the corresponding gene was used to complement U. maydis Δuhd1 mutants. Fhd1 was able to restore wild-type UA production, indicating that Fhd1 is responsible for β hydroxylation of the flocculosin short-chain fatty acid. We also investigated a P. flocculosa homolog of the U. maydis long-chain fatty-acid alpha hydroxylase Ahd1. The P. flocculosa ahd1 gene, which does not reside in the flocculosin gene cluster, was introduced into U. maydis Δahd1 mutant strains. P. flocculosa Ahd1 neither complemented the U. maydis Δahd1 phenotype nor resulted in the production of β-hydroxylated UA. This suggests that P. flocculosa Ahd1 is not involved in flocculosin hydroxylation. PMID:21926207

  16. Solar abundance of iridium

    PubMed Central

    Drake, Stephen; Aller, Lawrence H.

    1976-01-01

    By a method of spectrum synthesis, which yields log gfA, where g is the statistical weight of the lower level, f is the oscillator strength, and A is the abundance, an attempt is made to deduce the solar iridium abundance from one relatively unblended, but fairly weak IrI line, λ 3220.78 Å. If the Corliss-Bozman f-value for this line is adopted, we find log A(Ir) = 0.82 on the scale log A(H) = 12.00. The discordance with the value found from carbonaceous chondrites may arise from faulty f-values or from difficulties arising from line blending in this far ultraviolet domain of the solar spectrum. PMID:16578735

  17. The reaction of methyl peroxy and hydroxyl radicals as a major source of atmospheric methanol

    PubMed Central

    Müller, Jean-François; Liu, Zhen; Nguyen, Vinh Son; Stavrakou, Trissevgeni; Harvey, Jeremy N.; Peeters, Jozef

    2016-01-01

    Methyl peroxy, a key radical in tropospheric chemistry, was recently shown to react with the hydroxyl radical at an unexpectedly high rate. Here, the molecular reaction mechanisms are elucidated using high-level quantum chemical methodologies and statistical rate theory. Formation of activated methylhydrotrioxide, followed by dissociation into methoxy and hydroperoxy radicals, is found to be the main reaction pathway, whereas methylhydrotrioxide stabilization and methanol formation (from activated and stabilized methylhydrotrioxide) are viable minor channels. Criegee intermediate formation is found to be negligible. Given the theoretical uncertainties, useful constraints on the yields are provided by atmospheric methanol measurements. Using a global chemistry-transport model, we show that the only explanation for the high observed methanol abundances over remote oceans is the title reaction with an overall methanol yield of ∼30%, consistent with the theoretical estimates given their uncertainties. This makes the title reaction a major methanol source (115 Tg per year), comparable to global terrestrial emissions. PMID:27748363

  18. The reaction of methyl peroxy and hydroxyl radicals as a major source of atmospheric methanol

    NASA Astrophysics Data System (ADS)

    Müller, Jean-François; Liu, Zhen; Nguyen, Vinh Son; Stavrakou, Trissevgeni; Harvey, Jeremy N.; Peeters, Jozef

    2016-10-01

    Methyl peroxy, a key radical in tropospheric chemistry, was recently shown to react with the hydroxyl radical at an unexpectedly high rate. Here, the molecular reaction mechanisms are elucidated using high-level quantum chemical methodologies and statistical rate theory. Formation of activated methylhydrotrioxide, followed by dissociation into methoxy and hydroperoxy radicals, is found to be the main reaction pathway, whereas methylhydrotrioxide stabilization and methanol formation (from activated and stabilized methylhydrotrioxide) are viable minor channels. Criegee intermediate formation is found to be negligible. Given the theoretical uncertainties, useful constraints on the yields are provided by atmospheric methanol measurements. Using a global chemistry-transport model, we show that the only explanation for the high observed methanol abundances over remote oceans is the title reaction with an overall methanol yield of ~30%, consistent with the theoretical estimates given their uncertainties. This makes the title reaction a major methanol source (115 Tg per year), comparable to global terrestrial emissions.

  19. Detection of adsorbed water and hydroxyl on the moon

    USGS Publications Warehouse

    Clark, R.N.

    2009-01-01

    Data from the Visual and Infrared Mapping Spectrometer (VIAAS) on Cassini during its flyby of the AAoon in 1999 show a broad absorption at 3 micrometers due to adsorbed water and near 2.8 micrometers attributed to hydroxyl in the sunlit surface on the AAoon. The amounts of water indicated in the spectra depend on the type of mixing and the grain sizes in the rocks and soils but could be 10 to 1000 parts per million and locally higher. Water in the polar regions may be water that has migrated to the colder environments there. Trace hydroxyl is observed in the anorthositic highlands at lower latitudes.

  20. Detection of adsorbed water and hydroxyl on the Moon.

    PubMed

    Clark, Roger N

    2009-10-23

    Data from the Visual and Infrared Mapping Spectrometer (VIMS) on Cassini during its flyby of the Moon in 1999 show a broad absorption at 3 micrometers due to adsorbed water and near 2.8 micrometers attributed to hydroxyl in the sunlit surface on the Moon. The amounts of water indicated in the spectra depend on the type of mixing and the grain sizes in the rocks and soils but could be 10 to 1000 parts per million and locally higher. Water in the polar regions may be water that has migrated to the colder environments there. Trace hydroxyl is observed in the anorthositic highlands at lower latitudes.

  1. Radiocarbon tracer measurements of atmospheric hydroxyl radical concentrations

    NASA Technical Reports Server (NTRS)

    Campbell, M. J.; Farmer, J. C.; Fitzner, C. A.; Henry, M. N.; Sheppard, J. C.

    1986-01-01

    The usefulness of the C-14 tracer in measurements of atmospheric hydroxyl radical concentration is discussed. The apparatus and the experimental conditions of three variations of a radiochemical method of atmosphere analysis are described and analyzed: the Teflon bag static reactor, the flow reactor (used in the Wallops Island tests), and the aircraft OH titration reactor. The procedure for reduction of the aircraft reactor instrument data is outlined. The problems connected with the measurement of hydroxyl radicals are discussed. It is suggested that the gas-phase radioisotope methods have considerable potential in measuring tropospheric impurities present in very low concentrations.

  2. Accelerated crystallization of zeolites via hydroxyl free radicals.

    PubMed

    Feng, Guodong; Cheng, Peng; Yan, Wenfu; Boronat, Mercedes; Li, Xu; Su, Ji-Hu; Wang, Jianyu; Li, Yi; Corma, Avelino; Xu, Ruren; Yu, Jihong

    2016-03-11

    In the hydrothermal crystallization of zeolites from basic media, hydroxide ions (OH(-)) catalyze the depolymerization of the aluminosilicate gel by breaking the Si,Al-O-Si,Al bonds and catalyze the polymerization of the aluminosilicate anions around the hydrated cation species by remaking the Si,Al-O-Si,Al bonds. We report that hydroxyl free radicals (•OH) are involved in the zeolite crystallization under hydrothermal conditions. The crystallization processes of zeolites-such as Na-A, Na-X, NaZ-21, and silicalite-1-can be accelerated with hydroxyl free radicals generated by ultraviolet irradiation or Fenton's reagent.

  3. Iron-induced hydroxyl radical generation from basaltic volcanic ash

    NASA Astrophysics Data System (ADS)

    Horwell, C. J.; Fenoglio, I.; Fubini, B.

    2007-09-01

    Iron-induced hydroxyl radical generation from the surface of volcanic ash particles is a possible mechanism of respiratory toxicity in addition to crystalline silica induced pathogenicity. Here we show that volcanic ash generates hydroxyl radicals, with greater reactivity in iron-rich, silica-poor samples, such as basaltic ash. Basaltic particles expose at the surface high levels of poorly-coordinated iron ions in both Fe(II) and Fe(III) oxidation states which are likely to be the cause of such reactivity. Hitherto, basaltic ash has been disregarded as a hazard due to the lack of crystalline silica particulate but future hazard assessment should consider its toxic potential.

  4. Hydroxyl radical induced degradation of salicylates in aerated aqueous solution

    NASA Astrophysics Data System (ADS)

    Szabó, László; Tóth, Tünde; Homlok, Renáta; Rácz, Gergely; Takács, Erzsébet; Wojnárovits, László

    2014-04-01

    Ionizing radiation induced degradation of acetylsalicylic acid, its hydrolysis product salicylic acid and a salicylic acid derivative 5-sulpho-salicylic acid, was investigated in dilute aqueous solutions by UV-vis spectrophotometry, HPLC separation and diode-array or MS/MS detection, chemical oxygen demand, total organic carbon content and by Vibrio fischeri toxicity measurements. Hydroxyl radicals were shown to degrade these molecules readily, and first degradation products were hydroxylated derivatives in all cases. Due to the by-products, among them hydrogen peroxide, the toxicity first increased and then decreased with the absorbed dose. With prolonged irradiation complete mineralization was achieved.

  5. Methemoglobinemia Hemotoxicity of Some Antimalarial 8-Aminoquinoline Analogues and Their Hydroxylated Derivatives: Density Functional Theory Computation of Ionization Potentials.

    PubMed

    Ding, Yuanqing; Liu, Haining; Tekwani, Babu L; Nanayakkara, N P Dhammika; Khan, Ikhlas A; Walker, Larry A; Doerksen, Robert J

    2016-07-18

    The administration of primaquine (PQ), an essential drug for the treatment and radical cure of malaria, can lead to methemoglobin formation and life-threatening hemolysis for glucose-6-phosphate dehydrogenase deficient patients. The ionization potential (IP, a quantitative measure of the ability to lose an electron) of the metabolites generated by antimalarial 8-aminoquinoline (8-AQ) drugs like PQ has been believed to be correlated in part to this methemoglobinemia hemotoxicity: the lower the IP of an 8-AQ derivative, the higher the concentration of methemoglobin generated. In this work, demethoxylated primaquine (AQ02) was employed as a model, by intensive computation at the B3LYP-SCRF(PCM)/6-311++G**//B3LYP/6-31G** level in water, to study the effects of hydroxylation at various positions on the ionization potential. Compared to the parent AQ02, the IPs of AQ02's metabolites hydroxylated at N1', C5, and C7 were lower by 61, 30, and 19 kJ/mol, respectively, while differences in the IP relative to PQ were small for hydroxylation at all other positions. The C6 position, at which the IP of the hydroxylated metabolite was greater than that of AQ02, by 2 kJ/mol, was found to be unique. Several literature and proposed 8-AQ analogues were studied to evaluate substituent effects on their potential to generate methemoglobin, with the finding that hydroxylations at N1' and C5 contribute the most to the potential hemotoxicity of PQ-based antimalarials, whereas hydroxylation at C7 has little effect. Phenoxylation at C5 in PQ-based 8-AQs can block the hydroxylation at C5 and reduce the potential for methemoglobin generation, while -CF3 and chlorines attached to the phenolic ring can further reduce the risk. The H-shift at N1' during the cationization of hydroxylated metabolites of 8-AQs sharply decreased their IPs, but this effect can be significantly reduced by the introduction of an electron-withdrawing group to the quinoline core. The results and this approach may be

  6. Bacterial adhesion to hydroxyl- and methyl-terminated alkanethiol self-assembled monolayers.

    PubMed Central

    Wiencek, K M; Fletcher, M

    1995-01-01

    The attachment of bacteria to solid surfaces is influenced by substratum chemistry, but to determine the mechanistic basis of this relationship, homogeneous, well-defined substrata are required. Self-assembled monolayers (SAMs) were constructed from alkanethiols to produce a range of substrata with different exposed functional groups, i.e., methyl and hydroxyl groups and a series of mixtures of the two. Percentages of hydroxyl groups in the SAMs and substratum wettability were measured by X-ray photoelectron spectroscopy and contact angles of water and hexadecane, respectively. SAMs exhibited various substratum compositions and wettabilities, ranging from hydrophilic, hydroxyl-terminated monolayers to hydrophobic, methyl-terminated monolayers. The kinetics of attachment of an estuarine bacterium to these surfaces in a laminar flow chamber were measured over periods of 120 min. The initial rate of net adhesion, the number of cells attached after 120 min, the percentage of attached cells that adsorbed or desorbed between successive measurements, and the residence times of attached cells were quantified by phase-contrast microscopy and digital image processing. The greatest numbers of attached cells occurred on hydrophobic surfaces, because (i) the initial rates of adhesion and the mean numbers of cells that attached after 120 min increased with the methyl content of the SAM and the contact angle of water and (ii) the percentage of cells that desorbed between successive measurements (ca. 2 min) decreased with increasing substratum hydrophobicity. With all surfaces, 60 to 80% of the cells that desorbed during the 120-min exposure period had residence times of less than 10 min, suggesting that establishment of firm adhesion occurred quickly on all of the test surfaces. PMID:7721687

  7. Synthesis, characterization and phytotoxic activity of hydroxylated isobenzofuran-1(3H)-ones

    NASA Astrophysics Data System (ADS)

    Teixeira, R. R.; Pereira, J. L.; Da Silva, S. F.; Guilardi, S.; Paixão, D. A.; Anconi, C. P. A.; De Almeida, W. B.; Ellena, J.; Forlani, G.

    2014-03-01

    Two hydroxylated isobenzofuranones 3 and 4 were synthesized from benzoic acids. The compounds were fully characterized by IR, NMR (1H and 13C), HRMS, and X-ray crystallography. Compounds 3 and 4 crystallized in the space group Pc and P21/n, respectively. DFT calculations were used to confirm undoubtedly their NMR chemical shifts. Biological assays showed that these compounds are capable of interfering with the radicle growth of monocotyledonous and dicotyledonous species, whereas the photosynthetic electron transport chain was substantially unaffected.

  8. Chemoenzymatic collective synthesis of optically active hydroxyl(methyl)tetrahydronaphthalene-based bioactive terpenoids.

    PubMed

    Batwal, Ramesh U; Argade, Narshinha P

    2015-12-14

    Starting from succinic anhydride and 2-methylanisole, a chemoenzymatic collective formal/total synthesis of several optically active tetrahydronaphthalene based bioactive natural products has been presented via advanced level common precursors; the natural product and antipode (-)/(+)-aristelegone B. Regioselective benzylic oxidations, stereoselective introduction of hydroxyl groups at the α-position of ketone moiety in syn-orientation, efficient enzymatic resolutions with high enantiomeric purity, stereoselective reductions, samarium iodide induced deoxygenations and tandem acylation-Wittig reactions without racemization and/or eliminative aromatization were the key features. An attempted diastereoselective synthesis of (±)-vallapin has also been described.

  9. Abundance of field galaxies

    NASA Astrophysics Data System (ADS)

    Klypin, Anatoly; Karachentsev, Igor; Makarov, Dmitry; Nasonova, Olga

    2015-12-01

    We present new measurements of the abundance of galaxies with a given circular velocity in the Local Volume: a region centred on the Milky Way Galaxy and extending to distance ˜10 Mpc. The sample of ˜750 mostly dwarf galaxies provides a unique opportunity to study the abundance and properties of galaxies down to absolute magnitudes MB ≈ -10 and virial masses M_vir= 109{ M_{⊙}}. We find that the standard Λ cold dark matter (ΛCDM) model gives remarkably accurate estimates for the velocity function of galaxies with circular velocities V ≳ 70 kms-1 and corresponding virial masses M_vir≳ 5× 10^{10}{ M_{⊙}}, but it badly fails by overpredicting ˜5 times the abundance of large dwarfs with velocities V = 30-40 kms-1. The warm dark matter (WDM) models cannot explain the data either, regardless of mass of WDM particle. Just as in previous observational studies, we find a shallow asymptotic slope dN/dlog V ∝ Vα, α ≈ -1 of the velocity function, which is inconsistent with the standard ΛCDM model that predicts the slope α = -3. Though reminiscent to the known overabundance of satellite problem, the overabundance of field galaxies is a much more difficult problem. For the standard ΛCDM model to survive, in the 10 Mpc radius of the Milky Way there should be 1000 not yet detected galaxies with virial mass M_vir≈ 10^{10}{ M_{⊙}}, extremely low surface brightness and no detectable H I gas. So far none of this type of galaxies have been discovered.

  10. Late embryogenesis abundant proteins

    PubMed Central

    Olvera-Carrillo, Yadira; Reyes, José Luis

    2011-01-01

    Late Embryogenesis Abundant (LEA) proteins accumulate at the onset of seed desiccation and in response to water deficit in vegetative plant tissues. The typical LEA proteins are highly hydrophilic and intrinsically unstructured. They have been classified in different families, each one showing distinctive conserved motifs. In this manuscript we present and discuss some of the recent findings regarding their role in plant adaptation to water deficit, as well as those concerning to their possible function, and how it can be related to their intrinsic structural flexibility. PMID:21447997

  11. Lysine hydroxylation of collagen in a fibroblast cell culture system

    NASA Technical Reports Server (NTRS)

    Uzawa, Katsuhiro; Yeowell, Heather N.; Yamamoto, Kazushi; Mochida, Yoshiyuki; Tanzawa, Hideki; Yamauchi, Mitsuo

    2003-01-01

    The lysine (Lys) hydroxylation pattern of type I collagen produced by human fibroblasts in culture was analyzed and compared. Fibroblasts were cultured from normal human skin (NSF), keloid (KDF), fetal skin (FDF), and skin tissues of Ehlers-Danlos syndrome type VIA and VIB patients (EDS-VIA and -VIB). The type I collagen alpha chains with or without non-helical telopeptides were purified from the insoluble matrix and analyzed. In comparison with NSFs, KDF and FDF showed significantly higher Lys hydroxylation, particularly in the telopeptide domains of both alpha chains. Both EDS-VIA and -VIB showed markedly lower Lys hydroxylation in the helical domains of both alpha chains whereas that in the telopeptides was comparable with those of NSFs. A similar profile was observed in the tissue sample of the EDS-VIB patient. These results demonstrate that the Lys hydroxylation pattern is domain-specific within the collagen molecule and that this method is useful to characterize the cell phenotypes in normal/pathological connective tissues.

  12. Production of hydroxylated fatty acids in genetically modified plants

    DOEpatents

    Somerville, Chris; Broun, Pierre; van de Loo, Frank

    2001-01-01

    This invention relates to plant fatty acyl hydroxylases. Methods to use conserved amino acid or nucleotide sequences to obtain plant fatty acyl hydroxylases are described. Also described is the use of cDNA clones encoding a plant hydroxylase to produce a family of hydroxylated fatty acids in transgenic plants.

  13. Vanadium promotes hydroxyl radical formation by activated human neutrophils.

    PubMed

    Fickl, Heidi; Theron, Annette J; Grimmer, Heidi; Oommen, Joyce; Ramafi, Grace J; Steel, Helen C; Visser, Susanna S; Anderson, Ronald

    2006-01-01

    This study was undertaken to investigate the effects of vanadium in the +2, +3, +4, and +5 valence states on superoxide generation, myeloperoxidase (MPO) activity, and hydroxyl radical formation by activated human neutrophils in vitro, using lucigenin-enhanced chemiluminescence (LECL), autoiodination, and electron spin resonance with 5,5-dimethyl-l-pyrroline N-oxide as the spin trap, respectively. At concentrations of up to 25 microM, vanadium, in the four different valence states used, did not affect the LECL responses of neutrophils activated with either the chemoattractant, N-formyl-l-methionyl-l-leucyl-l-phenylalanine (1 microM), or the phorbol ester, phorbol 12-myristate 12-acetate (25 ng/ml). However, exposure to vanadium in the +2, +3, and +4, but not the +5, valence states was accompanied by significant augmentation of hydroxyl radical formation by activated neutrophils and attenuation of MPO-mediated iodination. With respect to hydroxyl radical formation, similar effects were observed using cell-free systems containing either hydrogen peroxide (100 microM) or xanthine/xanthine oxidase together with vanadium (+2, +3, +4), while the activity of purified MPO was inhibited by the metal in these valence states. These results demonstrate that vanadium in the +2, +3, and +4 valence states interacts prooxidatively with human neutrophils, competing effectively with MPO for hydrogen peroxide to promote formation of the highly toxic hydroxyl radical.

  14. Sulfur Dioxide Capture by Heterogeneous Oxidation on Hydroxylated Manganese Dioxide.

    PubMed

    Wu, Haodong; Cai, Weimin; Long, Mingce; Wang, Hairui; Wang, Zhiping; Chen, Chen; Hu, Xiaofang; Yu, Xiaojuan

    2016-06-01

    Here we demonstrate that sulfur dioxide (SO2) is efficiently captured via heterogeneous oxidation into sulfate on the surface of hydroxylated manganese dioxide (MnO2). Lab-scale activity tests in a fluidized bed reactor showed that the removal efficiency for a simulated flue gas containing 5000 mg·Nm(-3) SO2 could reach nearly 100% with a GHSV (gas hourly space velocity) of 10000 h(-1). The mechanism was investigated using a combination of experimental characterizations and theoretical calculations. It was found that formation of surface bound sulfate proceeds via association of SO2 with terminal hydroxyls. Both H2O and O2 are essential for the generation of reactive terminal hydroxyls, and the indirect role of O2 in heterogeneous SO2 oxidation at low temperature was also revealed. We propose that the high reactivity of terminal hydroxyls is attributed to the proper surface configuration of MnO2 to adsorb water with degenerate energies for associative and dissociative states, and maintain rapid proton dynamics. Viability analyses suggest that the desulfurization method that is based on such a direct oxidation reaction at the gas/solid interface represents a promising approach for SO2 capture. PMID:27123922

  15. Environmental Implications of Hydroxyl Radicals ((•)OH).

    PubMed

    Gligorovski, Sasho; Strekowski, Rafal; Barbati, Stephane; Vione, Davide

    2015-12-23

    The hydroxyl radical ((•)OH) is one of the most powerful oxidizing agents, able to react unselectively and instantaneously with the surrounding chemicals, including organic pollutants and inhibitors. The (•)OH radicals are omnipresent in the environment (natural waters, atmosphere, interstellar space, etc.), including biological systems where (•)OH has an important role in immunity metabolism. We provide an extensive view on the role of hydroxyl radical in different environmental compartments and in laboratory systems, with the aim of drawing more attention to this emerging issue. Further research on processes related to the hydroxyl radical chemistry in the environmental compartments is highly demanded. A comprehensive understanding of the sources and sinks of (•)OH radicals including their implications in the natural waters and in the atmosphere is of crucial importance, including the way irradiated chromophoric dissolved organic matter in surface waters yields (•)OH through the H2O2-independent pathway, and the assessment of the relative importance of gas-phase vs aqueous-phase reactions of (•)OH with many atmospheric components. Moreover, considering the fact that people spend so much more time in dwellings than outside, the impact of the reactivity of indoor hydroxyl radicals on health and well-being is another emerging research topic of great concern.

  16. Chemical abundance of comets

    NASA Technical Reports Server (NTRS)

    Wyckoff, Susan; Wehinger, Peter

    1988-01-01

    Observations of NH2, (OI) and molecular ion spectra in comets represent virtually all of the volatile fraction of a comet nucleus. Their study leads to the N2, NH3, H2O, CO2, CO content of the nucleus, and thus to important constraints on models of comet formation and chemical processing in the primitive solar nebula. The observations of Comet Halley provide the opportunity for the first comprehensive determination of the abundances in a comet nucleus. The carbon isotope abundance ratio 12 C/13 C = 65 plus or minus 8 has been determined for Comet Halley from resolved rotational line structure in the CN B-X (0,0) band. The ratio is approximately 30 pct lower than the solar system value, 89, indicating either an enhancement of 13CN or a depletion of 12CN in the comet. Scenarios consistent with the observed carbon isotope ratio are: (1) formation of the comet at the periphery of the solar nebula in a fractionation-enriched 13CN region, or hidden from 12CN enrichment sources, and (2) capture of an interestellar comet. Long-slit charge coupled device (CCD) spectra obtained at the time of the spacecraft encounter of Comet Halley have also been analyzed. Scale lengths, production rates and column densities of CH, CN, C2 and NH2 were determined.

  17. Flare Plasma Iron Abundance

    NASA Technical Reports Server (NTRS)

    Dennis, Brian R.; Dan, Chau; Jain, Rajmal; Schwartz, Richard A.; Tolbert, Anne K.

    2008-01-01

    The equivalent width of the iron-line complex at 6.7 keV seen in flare X-ray spectra suggests that the iron abundance of the hottest plasma at temperatures >approx.10 MK may sometimes be significantly lower than the nominal coronal abundance of four times the photospheric value that is commonly assumed. This conclusion is based on X-ray spectral observations of several flares seen in common with the Ramaty High Energy Solar Spectroscopic Imager (RHESSI) and the Solar X-ray Spectrometer (SOXS) on the second Indian geostationary satellite, GSAT-2. The implications of this will be discussed as it relates to the origin of the hot flare plasma - either plasma already in the corona that is directly heated during the flare energy release process or chromospheric plasma that is heated by flare-accelerated particles and driven up into the corona. Other possible explanations of lower-than-expected equivalent widths of the iron-line complex will also be discussed.

  18. Ability of TiO2(110) Surface to Be Fully Hydroxylated and Fully Reduced

    SciTech Connect

    Wang, Zhitao; Garcia, Juan C.; Deskins, N. A.; Lyubinetsky, Igor

    2015-08-06

    Many TiO2 applications (e.g., in heterogeneous catalysis) involve contact with ambient atmosphere and/or water. The resulting hydroxylation can significantly alter its surface properties. While behavior of single, isolated OH species on the model metal oxide surface of rutile TiO2(110) is relatively well understood, much less is known regarding highly-hydroxylated surfaces and/or whether TiO2(110) could be fully-hydroxylated under ultra-high vacuum conditions. Here we report in situ formation of a well-ordered, fully-hydroxylated TiO2(110)-(1 x 1) surface using an enhanced photochemical approach, key parts of which are pre-dosing of water and multi-step dissociative adsorption and subsequent photolysis of the carboxylic (trimethyl acetic) acid. Combining scanning tunneling microscopy, ultra-violet photoelectron spectroscopy and density functional theory results, we show that the attained “super OH” surface is also fully-reduced, as a result of the photochemical trapping of electrons at the OH groups.

  19. A domain swapping approach to elucidate differential regiospecific hydroxylation by geraniol and linalool synthases from perilla.

    PubMed

    Sato-Masumoto, Naoko; Ito, Michiho

    2014-06-01

    Geraniol and linalool are acyclic monoterpenes found in plant essential oils that have attracted much attention for their commercial use and in pharmaceutical studies. They are synthesized from geranyl diphosphate (GDP) by geraniol and linalool synthases, respectively. Both synthases are very similar at the amino acid level and share the same substrate; however, the position of the GDP to which they introduce hydroxyl groups is different. In this study, the mechanisms underlying the regiospecific hydroxylation of geraniol and linalool synthases were investigated using a domain swapping approach and site-directed mutagenesis in perilla. Sequences of the synthases were divided into ten domains (domains I to IV-4), and each corresponding domain was exchanged between both enzymes. It was shown that different regions were important for the formation of geraniol and linalool, namely, domains IV-1 and -4 for geraniol, and domains III-b, III-d, and IV-4 for linalool. These results suggested that the conformation of carbocation intermediates and their electron localization were seemingly to be different between geraniol and linalool synthases. Further, five amino acids in domain IV-4 were apparently indispensable for the formation of geraniol and linalool. According to three-dimensional structural models of the synthases, these five residues seemed to be responsible for the different spatial arrangement of the amino acid at H524 in the case of geraniol synthase, while N526 is the corresponding residue in linalool synthase. These results suggested that the side-chains of these five amino acids, in combination with several relevant domains, localized the positive charge in the carbocation intermediate to determine the position of the introduced hydroxyl group.

  20. Accelerated chemistry in the reaction between the hydroxyl radical and methanol at interstellar temperatures facilitated by tunnelling.

    PubMed

    Shannon, Robin J; Blitz, Mark A; Goddard, Andrew; Heard, Dwayne E

    2013-09-01

    Understanding the abundances of molecules in dense interstellar clouds requires knowledge of the rates of gas-phase reactions between uncharged species. However, because of the low temperatures within these clouds, reactions with an activation barrier were considered too slow to play an important role. Here we show that, despite the presence of a barrier, the rate coefficient for the reaction between the hydroxyl radical (OH) and methanol--one of the most abundant organic molecules in space--is almost two orders of magnitude larger at 63 K than previously measured at ∼200 K. We also observe the formation of the methoxy radical product, which was recently detected in space. These results are interpreted by the formation of a hydrogen-bonded complex that is sufficiently long-lived to undergo quantum-mechanical tunnelling to form products. We postulate that this tunnelling mechanism for the oxidation of organic molecules by OH is widespread in low-temperature interstellar environments.

  1. SERCA overexpression reduces hydroxyl radical injury in murine myocardium.

    PubMed

    Hiranandani, Nitisha; Bupha-Intr, Tepmanas; Janssen, Paul M L

    2006-12-01

    Hydroxyl radicals (*OH) are involved in the pathogenesis of ischemia-reperfusion injury and are observed in clinical situations, including acute heart failure, stroke, and myocardial infarction. Acute transient exposure to *OH causes an intracellular Ca(2+) overload and leads to impaired contractility. We investigated whether upregulation of sarcoplasmic reticulum Ca(2+)-ATPase function (SERCA) can attenuate *OH-induced dysfunction. Small, contracting right ventricular papillary muscles from wild-type (WT) SERCA1a-overexpressing (transgenic, TG) and SERCA2a heterogeneous knockout (HET) mice were directly exposed to *OH. This brief 2-min exposure led to a transient elevation of diastolic force (F(dia)) and depression of developed force (F(dev)). In WT mice, F(dia) increased to 485 +/- 49% and F(dev) decreased to 11 +/- 3%. In sharp contrast, in TG mice F(dia) increased only to 241 +/- 17%, whereas F(dev) decreased only to 51 +/- 5% (P < 0.05 vs. WT). In HET mice, F(dia) rose more than WT (to 597 +/- 20%, P < 0.05), whereas F(dev) was reduced in a similar amount. After approximately 45 min after *OH exposure, a new steady state was reached: F(dev) returned to 37 +/- 6% and 32 +/- 6%, whereas F(dia) came back to 238 +/- 28% and 292 +/- 17% in WT and HET mice, respectively. In contrast, the sustained dysfunction was significantly less in TG mice: F(dia) and F(dev) returned to 144 +/- 20% and 67 +/- 6%, respectively. Before exposure to *OH, there is decrease in phospholamban (PLB) phosphorylation at Ser16 (pPLBSer16) and PLB phosphorylation at Thr17 (pPLBThr17) in TG mice and an increase in pPLBSer16 and pPLBThr17 in HET mice versus WT. After exposure to *OH there is decrease in pPLBSer16 in WT, TG, and HET mice but no significant change in the level of pPLBThr17 in any group. The results indicate that SERCA overexpression can reduce the *OH-induced contractile dysfunction in murine myocardium, whereas a reduced SR Ca(2+)-ATPase activity aggravates this injury. Loss of

  2. Differential Effects of Collagen Prolyl 3-Hydroxylation on Skeletal Tissues

    PubMed Central

    Homan, Erica P.; Lietman, Caressa; Grafe, Ingo; Lennington, Jennifer; Morello, Roy; Napierala, Dobrawa; Jiang, Ming-Ming; Munivez, Elda M.; Dawson, Brian; Bertin, Terry K.; Chen, Yuqing; Lua, Rhonald; Lichtarge, Olivier; Hicks, John; Weis, Mary Ann; Eyre, David; Lee, Brendan H. L.

    2014-01-01

    Mutations in the genes encoding cartilage associated protein (CRTAP) and prolyl 3-hydroxylase 1 (P3H1 encoded by LEPRE1) were the first identified causes of recessive Osteogenesis Imperfecta (OI). These proteins, together with cyclophilin B (encoded by PPIB), form a complex that 3-hydroxylates a single proline residue on the α1(I) chain (Pro986) and has cis/trans isomerase (PPIase) activity essential for proper collagen folding. Recent data suggest that prolyl 3-hydroxylation of Pro986 is not required for the structural stability of collagen; however, the absence of this post-translational modification may disrupt protein-protein interactions integral for proper collagen folding and lead to collagen over-modification. P3H1 and CRTAP stabilize each other and absence of one results in degradation of the other. Hence, hypomorphic or loss of function mutations of either gene cause loss of the whole complex and its associated functions. The relative contribution of losing this complex's 3-hydroxylation versus PPIase and collagen chaperone activities to the phenotype of recessive OI is unknown. To distinguish between these functions, we generated knock-in mice carrying a single amino acid substitution in the catalytic site of P3h1 (Lepre1H662A). This substitution abolished P3h1 activity but retained ability to form a complex with Crtap and thus the collagen chaperone function. Knock-in mice showed absence of prolyl 3-hydroxylation at Pro986 of the α1(I) and α1(II) collagen chains but no significant over-modification at other collagen residues. They were normal in appearance, had no growth defects and normal cartilage growth plate histology but showed decreased trabecular bone mass. This new mouse model recapitulates elements of the bone phenotype of OI but not the cartilage and growth phenotypes caused by loss of the prolyl 3-hydroxylation complex. Our observations suggest differential tissue consequences due to selective inactivation of P3H1 hydroxylase activity

  3. Hydroxylation of ultra-thin films of α-Cr 2O 3(0 0 0 1) formed on Cr(1 1 0)

    NASA Astrophysics Data System (ADS)

    Maurice, V.; Cadot, S.; Marcus, P.

    2001-01-01

    X-ray photoelectron spectroscopy (XPS), thermal desorption spectroscopy (TDS), low energy electron diffraction (LEED) and scanning tunneling microscopy (STM) data on five to six monolayer thick anhydrous films of α-Cr 2O 3(0 0 0 1) epitaxially grown on Cr(1 1 0) single-crystal surfaces and exposed to water vapor at 300 K are reported. The results evidence reversible surface hydroxylation of the thin films resulting from water dissociation. The XP O1s region of the hydroxylated film is characterized by the growth of a higher binding energy peak (531.4 eV) assigned to hydroxide groups in addition to the main peak corresponding to the O 2- anions of the oxide film (530.7 to 530.9 eV). The Cr 2p 3/2 region is characterized by the two peaks corresponding to the substrate Cr(0) atoms (574.4 eV) and the Cr(III) cations (576.5 to 576.7 eV) initially present in the anhydrous oxide film plus a third peak assigned to Cr(III) cations bonded to hydroxide groups (577.2 to 577.4 eV). The STM data show that the terraces and defects of the anhydrous oxide film are equally modified by hydroxylation indicating that the reaction is not defect specific and that water is dissociated on the regular sites of the α-Cr 2O 3(0 0 0 1) terraces. A disordered and corrugated surface is produced by hydroxylation which suggests significant OH-induced surface diffusion and rearrangement of the surface cation and anions planes. The LEED data show that the atomic lattice of the bulk of the oxide film is not modified in the conditions of hydroxylation tested (water doses⩽112.5 L) in agreement with the unmodified nanostructure of the oxide film observed by STM. An atomic layer by atomic layer model of the XPS intensity attenuation can be used to estimate the surface concentration of the hydroxylated surface. With increasing water doses, Cr(III) enrichment is observed at the oxide surface indicating OH-induced oxidation of the metallic substrate. A plateau is reached corresponding to a fully

  4. Inhibitory effects of hydroxylated cinnamoyl esters on lipid absorption and accumulation.

    PubMed

    Imai, Masahiko; Kumaoka, Takaya; Hosaka, Makiko; Sato, Yui; Li, Chuan; Sudoh, Masashi; Tamada, Yoshiko; Yokoe, Hiromasa; Saito, Setsu; Tsubuki, Masayoshi; Takahashi, Noriko

    2015-07-01

    Obesity is a risk factor associated with several lifestyle-related diseases, for example, diabetes, high blood pressure, hyperlipidemia and cancer. Caffeic acid 2-phenylethyl ester (CAPE, 1), a naturally-occurring compound found in various plants and propolis, which exhibits anti-inflammatory, immunomodulatory and cytotoxic activities and inhibits 3T3-L1 differentiation to adipocytes. As part of our efforts to moderate lifestyle-related diseases, we synthesized analogs of 1 and studied their effects on pancreatic lipase activities, lipid absorption, and 3T3-L1 differentiation. We found that catechols 1-4 show inhibitory activities against pancreatic lipase in a dose-dependent manner in vitro. Compounds 1-3 proved to be more potent inhibitors of pancreatic lipase than 5, 6, 8, and 9, which have one hydroxyl group, respectively. Compound 7 has three aromatic hydroxyl groups and restrains greater lipase inhibitory activity than the other compounds. In addition, 7 and 3 significantly suppress a rise in blood triglyceride (TG) levels in mice given corn oil orally. Furthermore, 2 and 3 are more potent at preventing 3T3-L1 differentiation (lipid accumulation) than 1, while 7 is more potent than 3, 8, and 9 in these assays. Compounds 2, 3, and 7 inhibit lipid absorption and accumulation, with new compound 7 being the most potent. These results indicate that 7 may have potential benefits as a health agent with anti-obesity properties. PMID:25910587

  5. Hydroxylated chalcones with dual properties: Xanthine oxidase inhibitors and radical scavengers.

    PubMed

    Hofmann, Emily; Webster, Jonathan; Do, Thuy; Kline, Reid; Snider, Lindsey; Hauser, Quintin; Higginbottom, Grace; Campbell, Austin; Ma, Lili; Paula, Stefan

    2016-02-15

    In this study, we evaluated the abilities of a series of chalcones to inhibit the activity of the enzyme xanthine oxidase (XO) and to scavenge radicals. 20 mono- and polyhydroxylated chalcone derivatives were synthesized by Claisen-Schmidt condensation reactions and then tested for inhibitory potency against XO, a known generator of reactive oxygen species (ROS). In parallel, the ability of the synthesized chalcones to scavenge a stable radical was determined. Structure-activity relationship analysis in conjunction with molecular docking indicated that the most active XO inhibitors carried a minimum of three hydroxyl groups. Moreover, the most effective radical scavengers had two neighboring hydroxyl groups on at least one of the two phenyl rings. Since it has been proposed previously that XO inhibition and radical scavenging could be useful properties for reduction of ROS-levels in tissue, we determined the chalcones' effects to rescue neurons subjected to ROS-induced stress created by the addition of β-amyloid peptide. Best protection was provided by chalcones that combined good inhibitory potency with high radical scavenging ability in a single molecule, an observation that points to a potential therapeutic value of this compound class.

  6. Actinide abundances in ordinary chondrites

    NASA Technical Reports Server (NTRS)

    Hagee, B.; Bernatowicz, T. J.; Podosek, F. A.; Johnson, M. L.; Burnett, D. S.

    1990-01-01

    Measurements of actinide and light REE (LREE) abundances and of phosphate abundances in equilibrated ordinary chondrites were obtained and were used to define the Pu abundance in the solar system and to determine the degree of variation of actinide and LREE abundances. The results were also used to compare directly the Pu/U ratio with the earlier obtained ratio determined indirectly, as (Pu/Nd)x(Nd/U), assuming that Pu behaves chemically as a LREE. The data, combined with high-accuracy isotope-dilution data from the literature, show that the degree of gram-scale variability of the Th, U, and LREE abundances for equilibrated ordinary chondrites is a factor of 2-3 for absolute abundances and up to 50 percent for relative abundances. The observed variations are interpreted as reflecting the differences in the compositions and/or proportions of solar nebula components accreted to ordinary chondrite parent bodies.

  7. Hydroxylated polychlorinated biphenyls in the environment: sources, fate, and toxicities.

    PubMed

    Tehrani, Rouzbeh; Van Aken, Benoit

    2014-05-01

    Hydroxylated polychlorinated biphenyls (OH-PCBs) are produced in the environment by the oxidation of PCBs through a variety of mechanisms, including metabolic transformation in living organisms and abiotic reactions with hydroxyl radicals. As a consequence, OH-PCBs have been detected in a wide range of environmental samples, including animal tissues, water, and sediments. OH-PCBs have recently raised serious environmental concerns because they exert a variety of toxic effects at lower doses than the parent PCBs and they are disruptors of the endocrine system. Although evidence about the widespread dispersion of OH-PCBs in various compartments of the ecosystem has accumulated, little is currently known about their biodegradation and behavior in the environment. OH-PCBs are, today, increasingly considered as a new class of environmental contaminants that possess specific chemical, physical, and biological properties not shared with the parent PCBs. This article reviews recent findings regarding the sources, fate, and toxicities of OH-PCBs in the environment.

  8. Treating ballast water with hydroxyl radical on introduced organisms

    NASA Astrophysics Data System (ADS)

    Zhang, Zhitao; Bai, Mindi; Xiao, Yu; Bai, Mindong; Yang, Bo; Bai, Xiyao

    2006-06-01

    With physical method of micro-gap gas discharge, a large amount of hydroxyl radical can be produced in 20t/h pilot-scale system using the ionization of O2 and H2O. In this paper, the effect of biochemistry of hydroxyl radicals on introduced organisms in ballast water was experimentally investigated. The results indicate that the contents of chlorophyl- a, chlorophyl- b, chlorophyl- c and carotenoid are decreased by 35% 64% within 8.0s and further to the lowest limit of test 5 minutes. In addition, the main reasons of cell death are the lipid peroxidation, the strong destruction to the monose, amylose, protein, DNA and RNA of cell, and damage in CAT, POD and SOD of antioxidant enzyme system.

  9. Exploring Pd adsorption, diffusion, permeation, and nucleation on bilayer SiO2/Ru as a function of hydroxylation and precursor environment: From UHV to catalyst preparation

    NASA Astrophysics Data System (ADS)

    Pomp, Sascha; Kaden, William E.; Sterrer, Martin; Freund, Hans-Joachim

    2016-10-01

    The hydroxylation-dependent permeability of bilayer SiO2 supported on Ru(0001) was investigated by XPS and TDS studies in a temperature range of 100 K to 600 K. For this, the thermal behavior of Pd evaporated at 100 K, which results in surface and sub-surface (Ru-supported) binding arrangements, was examined relative to the extent of pre-hydroxylation. Samples containing only defect-mediated hydroxyls showed no effect on Pd diffusion through the film at low temperature. If, instead, the concentration of strongly bound hydroxyl groups and associated weakly bound water molecules was enriched by an electron-assisted hydroxylation procedure, the probability for Pd diffusion through the film is decreased via a pore-blocking mechanism. Above room temperature, all samples showed similar behavior, reflective of particle nucleation above the film and eventual agglomeration with any metal atoms initially binding beneath the film. When depositing Pd onto the same SiO2/Ru model support via adsorption of [Pd(NH3)4]Cl2 from alkaline (pH 12) precursor solution, we observe notably different adsorption and nucleation mechanisms. The resultant Pd adsorption complexes follow established decomposition pathways to produce model catalyst systems compatible with those created exclusively within UHV despite lacking the ability to penetrate the film due to the increased size of the initial Pd precursor groups.

  10. Formation and Properties of Membrane-Ordered Domains by Phytoceramide: Role of Sphingoid Base Hydroxylation.

    PubMed

    Marquês, Joaquim T; Cordeiro, André M; Viana, Ana S; Herrmann, Andreas; Marinho, H Susana; de Almeida, Rodrigo F M

    2015-09-01

    Phytoceramide is the backbone of major sphingolipids in fungi and plants and is essential in several tissues of animal organisms, such as human skin. Its sphingoid base, phytosphingosine, differs from that usually found in mammals by the addition of a hydroxyl group to the 4-ene, which may be a crucial factor for the different properties of membrane microdomains among those organisms and tissues. Recently, sphingolipid hydroxylation in animal cells emerged as a key feature in several physiopathological processes. Hence, the study of the biophysical properties of phytosphingolipids is also relevant in that context since it helps us to understand the effects of sphingolipid hydroxylation. In this work, binary mixtures of N-stearoyl-phytoceramide (PhyCer) with palmitoyloleoylphosphatidylcholine (POPC) were studied. Steady-state and time-resolved fluorescence of membrane probes, X-ray diffraction, atomic force microscopy, and confocal microscopy were employed. As for other saturated ceramides, highly rigid gel domains start to form with just ∼5 mol % PhyCer at 24 °C. However, PhyCer gel-enriched domains in coexistence with POPC-enriched fluid present additional complexity since their properties (maximal order, shape, and thickness) change at specific POPC/PhyCer molar ratios, suggesting the formation of highly stable stoichiometric complexes with their own properties, distinct from both POPC and PhyCer. A POPC/PhyCer binary phase diagram, supported by the different experimental approaches employed, is proposed with complexes of 3:1 and 1:2 stoichiometries which are stable at least from ∼15 to ∼55 °C. Thus, it provides mechanisms for the in vivo formation of sphingolipid-enriched gel domains that may account for stable membrane compartments and diffusion barriers in eukaryotic cell membranes.

  11. Production of hydroxylated fatty acids in genetically modified plants

    DOEpatents

    Somerville, Chris; Broun, Pierre; van de Loo, Frank; Boddupalli, Sekhar S.

    2011-08-23

    This invention relates to plant fatty acyl hydroxylases. Methods to use conserved amino acid or nucleotide sequences to obtain plant fatty acyl hydroxylases are described. Also described is the use of cDNA clones encoding a plant hydroxylase to produce a family of hydroxylated fatty acids in transgenic plants. In addition, the use of genes encoding fatty acid hydroxylases or desaturases to alter the level of lipid fatty acid unsaturation in transgenic plants is described.

  12. Production of hydroxylated fatty acids in genetically modified plants

    DOEpatents

    Somerville, Chris; Broun, Pierre; van de Loo, Frank; Boddupalli, Sekhar S.

    2005-08-30

    This invention relates to plant fatty acyl hydroxylases. Methods to use conserved amino acid or nucleotide sequences to obtain plant fatty acyl hydroxylases are described. Also described is the use of cDNA clones encoding a plant hydroxylase to produce a family of hydroxylated fatty acids in transgenic plants. In addition, the use of genes encoding fatty acid hydroxylases or desaturases to alter the level of lipid fatty acid unsaturation in transgenic plants is described.

  13. Two Structures of an N-Hydroxylating Flavoprotein Monooxygenase

    PubMed Central

    Olucha, Jose; Meneely, Kathleen M.; Chilton, Annemarie S.; Lamb, Audrey L.

    2011-01-01

    The ornithine hydroxylase from Pseudomonas aeruginosa (PvdA) catalyzes the FAD-dependent hydroxylation of the side chain amine of ornithine, which is subsequently formylated to generate the iron-chelating hydroxamates of the siderophore pyoverdin. PvdA belongs to the class B flavoprotein monooxygenases, which catalyze the oxidation of substrates using NADPH as the electron donor and molecular oxygen. Class B enzymes include the well studied flavin-containing monooxygenases and Baeyer-Villiger monooxygenases. The first two structures of a class B N-hydroxylating monooxygenase were determined with FAD in oxidized (1.9 Å resolution) and reduced (3.03 Å resolution) states. PvdA has the two expected Rossmann-like dinucleotide-binding domains for FAD and NADPH and also a substrate-binding domain, with the active site at the interface between the three domains. The structures have NADP(H) and (hydroxy)ornithine bound in a solvent-exposed active site, providing structural evidence for substrate and co-substrate specificity and the inability of PvdA to bind FAD tightly. Structural and biochemical evidence indicates that NADP+ remains bound throughout the oxidative half-reaction, which is proposed to shelter the flavin intermediates from solvent and thereby prevent uncoupling of NADPH oxidation from hydroxylated product formation. PMID:21757711

  14. Photochemical formation of hydroxyl radical by constituents of natural waters

    SciTech Connect

    Vaughan, P.P.; Blough, N.V.

    1998-10-01

    A new method is employed to determine the rates of photochemical hydroxyl radical (OH) formation in aqueous solutions and in natural waters under both aerobic and anaerobic conditions. Quantum yields for OH formation from the photolysis of nitrate and nitrite obtained by this method are in good agreement with previous measurements. Photolysis of Suwannee River fulvic acid (SRFA) solutions produced the hydroxyl radical under anaerobic conditions in proportion to the SRFA concentration. Under aerobic conditions, the quantum yields for OH formation were slightly higher and exhibited a different wavelength dependence than those obtained under anaerobic conditions. Experiments employing catalase indicate that Fenton chemistry can account for at most 50% of the total signal under aerobic conditions for SRFA irradiated at 310 and 320 nm. These results indicate the presence of a dioxygen-independent pathway of hydroxyl radical production that cannot be assigned to nitrate/nitrite photolysis or to Fenton chemistry. Results from the preliminary application of this method to natural waters are also presented.

  15. Lysyl hydroxylation in collagens from hyperplastic callus and embryonic bones.

    PubMed Central

    Lehmann, H W; Bodo, M; Frohn, C; Nerlich, A; Rimek, D; Notbohm, H; Müller, P K

    1992-01-01

    Tissue from two patients with osteogenesis imperfecta suffering from a hyperplastic callus was studied. Although collagen type I from the compact bone and the skin and fibroblast cultures of these patients showed normal lysyl hydroxylation, collagen types I, II, III and V from the callus tissue were markedly overhydroxylated. Furthermore, the overhydroxylation of lysine residues covered almost equally the entire alpha 1 (I) collagen chain, as demonstrated by the analysis of individual CNBr-derived peptides. In addition, collagen type I was isolated from femoral compact bone of 33 individuals who died between the 16th week of gestational age and 22 years. Lysyl hydroxylation rapidly decreased in both collagen alpha 1 (I) and alpha 2 (I) chains during fetal development, and only little in the postnatal period. The transient increase in lysyl hydroxylation and the involvement of various collagen types in callus tissue argue for a regulatory mechanism that may operate in bone repair and during fetal development. Images Fig. 1. Fig. 3. PMID:1546948

  16. Supercharging by m-NBA Improves ETD-Based Quantification of Hydroxyl Radical Protein Footprinting

    NASA Astrophysics Data System (ADS)

    Li, Xiaoyan; Li, Zixuan; Xie, Boer; Sharp, Joshua S.

    2015-08-01

    Hydroxyl radical protein footprinting (HRPF) is an MS-based technique for analyzing protein structure based on measuring the oxidation of amino acid side chains by hydroxyl radicals diffusing in solution. Spatial resolution of HRPF is limited by the smallest portion of the protein for which oxidation amounts can be accurately quantitated. Previous work has shown electron transfer dissociation (ETD) to be the most reliable method for quantifying the amount of oxidation of each amino acid side chain in a mixture of peptide oxidation isomers, but efficient ETD requires high peptide charge states, which limits its applicability for HRPF. Supercharging reagents have been used to enhance peptide charge state for ETD analysis, but previous work has shown supercharging reagents to enhance charge state differently for different peptides sequences; it is currently unknown if different oxidation isomers will experience different charge enhancement effects. Here, we report the effect of m-nitrobenzyl alcohol ( m-NBA) on the ETD-based quantification of peptide oxidation. The addition of m-NBA to both a defined mixture of synthetic isomeric oxidized peptides and Robo-1 protein subjected to HRPF increased the abundance of higher charge state ions, improving our ability to perform efficient ETD of the mixture. No differences in the reported quantitation by ETD were noted in the presence or absence of m-NBA, indicating that all oxidation isomers were charge-enhanced to a similar extent. These results indicate the utility of m-NBA for residue-level quantification of peptide oxidation in HRPF and other applications.

  17. Inhibitory activity of flavonoids from Prunus davidiana and other flavonoids on total ROS and hydroxyl radical generation.

    PubMed

    Jung, Hyun Ah; Jung, Mee Jung; Kim, Ji Young; Chung, Hae Young; Choi, Jae Sue

    2003-10-01

    Since reactive oxygen species (ROS) and hydroxyl radicals (*OH) play an important role in the pathogenesis of many human degenerative diseases, much attention has focused on the development of safe and effective antioxidants. Preliminary experiments have revealed that the methanol (MeOH) extract of the stem of Prunus davidiana exerts inhibitory/scavenging activities on 1,1-diphenyl-2-picrylhydrazyl (DPPH) radicals, total ROS and peroxynitrites (ONOO-). In the present study, the antioxidant activities of this MeOH extract and the organic solvent-soluble fractions, dichloromethane (CH2Cl2), ethyl acetate (EtOAc), and n-butanol (n-BuOH), and the water layer of P. davidiana stem were evaluated for the potential to inhibit *OH and total ROS generation in kidney homogenates using 2',7'-dichlorodihydrofluorescein diacetate (DCHF-DA), and for the potential to scavenge authentic ONOO-. We also evaluated the inhibitory activity of seven flavonoids isolated from P. davidiana stem, kaempferol, kaempferol 7-O-beta-D-glucoside, (+)-catechin, dihydrokaempferol, hesperetin 5-O-beta-D-glucoside, naringenin and its 7-O-beta-D-glucoside, on the total ROS, *OH and ONOO- systems. For the further elucidation of the structure-inhibitory activity relationship of flavonoids on total ROS and *OH generation, we measured the antioxidant activity of sixteen flavonoids available, including three active flavonoids isolated from P. davidiana, on the total ROS and *OH systems. We found that the inhibitory activity on total ROS generation increases in strength with more numerous hydroxyl groups on their structures. Also, the presence of an ortho-hydroxyl group, whether on the A-ring or B-ring, and a 3-hydroxyl group on the C-ring increased the inhibitory activity on both total ROS and *OH generation.

  18. Hydroxyl, water, ammonia, carbon monoxide and neutral carbon towards the Sgr A complex

    NASA Astrophysics Data System (ADS)

    Karlsson, R.; Sandqvist, Aa.; Hjalmarson, Å.; Winnberg, A.; Fathi, K.; Frisk, U.; Olberg, M.

    2014-05-01

    We observed Hydroxyl, water, ammonia, carbon monoxide and neutral carbon towards the +50 km s-1 cloud (M-0.02-0.07), the circumnuclear disk (CND) and the +20 km s-1 (M-0.13-0.08) cloud in the Sgr A complex with the VLA, Odin and SEST. Strong OH absorption, H2O emission and absorption lines were seen at all three positions. Strong C18O emissions were seen towards the +50 and +20 km s-1 clouds. The CND is rich in H2O and OH, and these abundances are considerably higher than in the surrounding clouds, indicating that shocks, star formation and clump collisions prevail in those objects. A comparison with the literature reveals that it is likely that PDR chemistry including grain surface reactions, and perhaps also the influences of shocks has led to the observed abundances of the observed molecular species studied here. In the redward high-velocity line wings of both the +50 and +20 km s-1 clouds and the CND, the very high H2O abundances are suggested to be caused by the combined action of shock desorption from icy grain mantles and high-temperature, gas-phase shock chemistry. Only three of the molecules are briefly discussed here. For OH and H2O three of the nine observed positions are shown, while a map of the C18O emission is provided. An extensive paper was recently published with Open Access (Karlsson et al. 2013, A&A 554, A141).

  19. A first report of hydroxylated apatite as structural biomineral in Loasaceae - plants' teeth against herbivores.

    PubMed

    Ensikat, Hans-Jürgen; Geisler, Thorsten; Weigend, Maximilian

    2016-01-01

    Biomineralization provides living organisms with various materials for the formation of resilient structures. Calcium phosphate is the main component of teeth and bones in vertebrates, whereas especially silica serves for the protection against herbivores on many plant surfaces. Functional calcium phosphate structures are well-known from the animal kingdom, but had not so far been reported from higher plants. Here, we document the occurrence of calcium phosphate biomineralization in the South-American plant group Loasaceae (rock nettle family), which have stinging trichomes similar to those of the well-known stinging nettles (Urtica). Stinging hairs and the smaller, glochidiate trichomes contained nanocrystalline hydroxylated apatite, especially in their distal portions, replacing the silica found in analogous structures of other flowering plants. This could be demonstrated by chemical, spectroscopic, and diffraction analyses. Some species of Loasaceae contained both calcium phosphate and silica in addition to calcium carbonate. The intriguing discovery of structural hydroxylated apatite in plants invites further studies, e.g., on its systematic distribution across the family, the genetic and cellular control of plant biomineralization, the properties and ultrastructure of calcium phosphate. It may prove the starting point for the development of biomimetic calcium phosphate composites based on a cellulose matrix. PMID:27194462

  20. Electrochemiluminescence of palmatine being oxidized by electrogenerated hydroxyl radical and its analytical application.

    PubMed

    Liang, Yao-Dong; Yu, Chun-Xia; Song, Jun-Feng

    2011-01-01

    A strong electrochemiluminescence (ECL) of palmatine in NaOH medium was observed at a vaseline-impregnated graphite anode. The ECL production could be described as follows: hydroxyl radical (OH(•)) was generated via the oxidation of hydroxyl group (OH(-)) in NaOH medium, and the formed OH(•) subsequently oxidized palmatine base converted from palmatine in NaOH medium to the excited state oxypalmatine (oxypalmatine*). As the oxypalmatine* went back to its ground state, a stronger chemiluminescence was produced. Based on the ECL of palmatine, an ECL method for the determination of palmatine was proposed. An ECL signal of palmatine in NaOH solution was obtained by applying direct current of 15 mA to the vaseline-impregnated graphite anode. The ECL intensity was rectilinear with palmatine concentration in the range of 8.0 × 10(-7) to 2.0 × 10(-5) mol l(-1) and the limit of detection (signal-to-noise = 3) was 3 × 10(-7) mol l(-1) . The proposed method was applied to the determination of palmatine in pharmaceutical preparations.

  1. Making graphene holey. Gold-nanoparticle-mediated hydroxyl radical attack on reduced graphene oxide.

    PubMed

    Radich, James G; Kamat, Prashant V

    2013-06-25

    Graphene oxide (GO) and reduced graphene oxide (RGO) have important applications in the development of new electrode and photocatalyst architectures. Gold nanoparticles (AuNPs) have now been employed as catalyst to generate OH(•) and oxidize RGO via hydroxyl radical attack. The oxidation of RGO is marked by pores and wrinkles within the 2-D network. Nanosecond laser flash photolysis was used in conjunction with competition kinetics to elucidate the oxidative mechanism and calculate rate constants for the AuNP-catalyzed and direct reaction between RGO and OH(•). The results highlight the use of the AuNP-mediated oxidation reaction to tune the properties of RGO through the degree of oxidation and/or functional group selectivity in addition to the nanoporous and wrinkle facets. The ability of AuNPs to catalyze the photolytic decomposition of H2O2 as well as the hydroxyl radical-induced oxidation of RGO raises new issues concerning graphene stability in energy conversion and storage (photocatalysis, fuel cells, Li-ion batteries, etc.). Understanding RGO oxidation by free radicals will aid in maintaining the long-term stability of RGO-based functional composites where intimate contact with radical species is inevitable.

  2. A Preliminary Link between Hydroxylated Metabolites of Polychlorinated Biphenyls and Free Thyroxin in Humans

    PubMed Central

    Dirinck, Eveline; Dirtu, Alin C.; Malarvannan, Govindan; Covaci, Adrian; Jorens, Philippe G.; Van Gaal, Luc F.

    2016-01-01

    Background: Polychlorinated biphenyls (PCBs) and their hydroxylated metabolites (HO-PCBs) interfere with thyroid hormone action both in vitro and in vivo. However, epidemiologic studies on the link between PCB exposure and thyroid function have yielded discordant results, while very few data are available for HO-PCBs. Objectives: Our study aimed at investigating the relationship between clinically available markers of thyroid metabolism and serum levels of both PCBs and HO-PCBs. Subjects and Methods: In a group of 180 subjects, thyroid-stimulating hormone (TSH) and free thyroxin (fT4), 29 PCBs (expressed both in lipid weight and in wet weight) and 18 HO-PCBs were measured in serum. Results: In regression models, adjusted for gender, age, current smoking behavior, BMI and total lipid levels, serum levels of 3HO-PCB118 and 3HO-PCB180, and PCB95lw, PCB99lw and PCB149lw were independent, significant predictors of fT4. A stepwise, multiple regression with gender, age, current smoking behavior, BMI and total lipid levels and all five previously identified significant compounds retained age, BMI, PCB95lw, PCB99lw and 3HO-PCB180 as significant predictors of fT4. TSH levels were not predicted by serum levels of any of the PCBs or HO-PCBs. Conclusions: Our study indicates that in vivo, circulating fT4 levels can be linked to serum levels of several PCBs and hydroxylated PCB metabolites. PMID:27089353

  3. Degradation mechanism of cyanobacterial toxin cylindrospermopsin by hydroxyl radicals in homogeneous UV/H₂O₂ process.

    PubMed

    He, Xuexiang; Zhang, Geshan; de la Cruz, Armah A; O'Shea, Kevin E; Dionysiou, Dionysios D

    2014-04-15

    The degradation of cylindrospermopsin (CYN), a widely distributed and highly toxic cyanobacterial toxin (cyanotoxin), remains poorly elucidated. In this study, the mechanism of CYN destruction by UV-254 nm/H2O2 advanced oxidation process (AOP) was investigated by mass spectrometry. Various byproducts identified indicated three common reaction pathways: hydroxyl addition (+16 Da), alcoholic oxidation or dehydrogenation (-2 Da), and elimination of sulfate (-80 Da). The initiation of the degradation was observed at the hydroxymethyl uracil and tricyclic guanidine groups; uracil moiety cleavage/fragmentation and further ring-opening of the alkaloid were also noted at an extended reaction time or higher UV fluence. The degradation rates of CYN decreased and less byproducts (species) were detected using natural water matrices; however, CYN was effectively eliminated under extended UV irradiation. This study demonstrates the efficiency of CYN degradation and provides a better understanding of the mechanism of CYN degradation by hydroxyl radical, a reactive oxygen species that can be generated by most AOPs and is present in natural water environment.

  4. Reaction Mechanism of the Bicopper Enzyme Peptidylglycine α-Hydroxylating Monooxygenase*

    PubMed Central

    Abad, Enrique; Rommel, Judith B.; Kästner, Johannes

    2014-01-01

    Peptidylglycine α-hydroxylating monooxygenase is a noninteracting bicopper enzyme that stereospecifically hydroxylates the terminal glycine of small peptides for its later amidation. Neuroendocrine messengers, such as oxytocin, rely on the biological activity of this enzyme. Each catalytic turnover requires one oxygen molecule, two protons from the solvent, and two electrons. Despite this enzyme having been widely studied, a consensus on the reaction mechanism has not yet been found. Experiments and theoretical studies favor a pro-S abstraction of a hydrogen atom followed by the rebinding of an OH group. However, several hydrogen-abstracting species have been postulated; because two protons are consumed during the reaction, several protonation states are available. An electron transfer between the copper atoms could play a crucial role for the catalysis as well. This leads to six possible abstracting species. In this study, we compare them on equal footing. We perform quantum mechanics/molecular mechanics calculations, considering the glycine hydrogen abstraction. Our results suggest that the most likely mechanism is a protonation of the abstracting species before the hydrogen abstraction and another protonation as well as a reduction before OH rebinding. PMID:24668808

  5. Making graphene holey. Gold-nanoparticle-mediated hydroxyl radical attack on reduced graphene oxide.

    PubMed

    Radich, James G; Kamat, Prashant V

    2013-06-25

    Graphene oxide (GO) and reduced graphene oxide (RGO) have important applications in the development of new electrode and photocatalyst architectures. Gold nanoparticles (AuNPs) have now been employed as catalyst to generate OH(•) and oxidize RGO via hydroxyl radical attack. The oxidation of RGO is marked by pores and wrinkles within the 2-D network. Nanosecond laser flash photolysis was used in conjunction with competition kinetics to elucidate the oxidative mechanism and calculate rate constants for the AuNP-catalyzed and direct reaction between RGO and OH(•). The results highlight the use of the AuNP-mediated oxidation reaction to tune the properties of RGO through the degree of oxidation and/or functional group selectivity in addition to the nanoporous and wrinkle facets. The ability of AuNPs to catalyze the photolytic decomposition of H2O2 as well as the hydroxyl radical-induced oxidation of RGO raises new issues concerning graphene stability in energy conversion and storage (photocatalysis, fuel cells, Li-ion batteries, etc.). Understanding RGO oxidation by free radicals will aid in maintaining the long-term stability of RGO-based functional composites where intimate contact with radical species is inevitable. PMID:23641756

  6. A first report of hydroxylated apatite as structural biomineral in Loasaceae – plants’ teeth against herbivores

    PubMed Central

    Ensikat, Hans-Jürgen; Geisler, Thorsten; Weigend, Maximilian

    2016-01-01

    Biomineralization provides living organisms with various materials for the formation of resilient structures. Calcium phosphate is the main component of teeth and bones in vertebrates, whereas especially silica serves for the protection against herbivores on many plant surfaces. Functional calcium phosphate structures are well-known from the animal kingdom, but had not so far been reported from higher plants. Here, we document the occurrence of calcium phosphate biomineralization in the South-American plant group Loasaceae (rock nettle family), which have stinging trichomes similar to those of the well-known stinging nettles (Urtica). Stinging hairs and the smaller, glochidiate trichomes contained nanocrystalline hydroxylated apatite, especially in their distal portions, replacing the silica found in analogous structures of other flowering plants. This could be demonstrated by chemical, spectroscopic, and diffraction analyses. Some species of Loasaceae contained both calcium phosphate and silica in addition to calcium carbonate. The intriguing discovery of structural hydroxylated apatite in plants invites further studies, e.g., on its systematic distribution across the family, the genetic and cellular control of plant biomineralization, the properties and ultrastructure of calcium phosphate. It may prove the starting point for the development of biomimetic calcium phosphate composites based on a cellulose matrix. PMID:27194462

  7. Tyrosine Hydroxylation in Betalain Pigment Biosynthesis Is Performed by Cytochrome P450 Enzymes in Beets (Beta vulgaris).

    PubMed

    Sunnadeniya, Rasika; Bean, Alexander; Brown, Matthew; Akhavan, Neda; Hatlestad, Gregory; Gonzalez, Antonio; Symonds, V Vaughan; Lloyd, Alan

    2016-01-01

    Yellow and red-violet betalain plant pigments are restricted to several families in the order Caryophyllales, where betacyanins play analogous biological roles to anthocyanins. The initial step in betalain biosynthesis is the hydroxylation of tyrosine to form L-DOPA. Using gene expression experiments in beets, yeast, and Arabidopsis, along with HPLC/MS analysis, the present study shows that two novel cytochrome P450 (CYP450) enzymes, CYP76AD6 and CYP76AD5, and the previously described CYP76AD1 can perform this initial step. Co-expressing these CYP450s with DOPA 4,5-dioxygenase in yeast, and overexpression of these CYP450s in yellow beets show that CYP76AD1 efficiently uses L-DOPA leading to red betacyanins while CYP76AD6 and CYP76AD5 lack this activity. Furthermore, CYP76AD1 can complement yellow beetroots to red while CYP76AD6 and CYP76AD5 cannot. Therefore CYP76AD1 uniquely performs the beet R locus function and beets appear to be genetically redundant for tyrosine hydroxylation. These new functional data and ancestral character state reconstructions indicate that tyrosine hydroxylation alone was the most likely ancestral function of the CYP76AD alpha and beta groups and the ability to convert L-DOPA to cyclo-DOPA evolved later in the alpha group.

  8. Tyrosine Hydroxylation in Betalain Pigment Biosynthesis Is Performed by Cytochrome P450 Enzymes in Beets (Beta vulgaris).

    PubMed

    Sunnadeniya, Rasika; Bean, Alexander; Brown, Matthew; Akhavan, Neda; Hatlestad, Gregory; Gonzalez, Antonio; Symonds, V Vaughan; Lloyd, Alan

    2016-01-01

    Yellow and red-violet betalain plant pigments are restricted to several families in the order Caryophyllales, where betacyanins play analogous biological roles to anthocyanins. The initial step in betalain biosynthesis is the hydroxylation of tyrosine to form L-DOPA. Using gene expression experiments in beets, yeast, and Arabidopsis, along with HPLC/MS analysis, the present study shows that two novel cytochrome P450 (CYP450) enzymes, CYP76AD6 and CYP76AD5, and the previously described CYP76AD1 can perform this initial step. Co-expressing these CYP450s with DOPA 4,5-dioxygenase in yeast, and overexpression of these CYP450s in yellow beets show that CYP76AD1 efficiently uses L-DOPA leading to red betacyanins while CYP76AD6 and CYP76AD5 lack this activity. Furthermore, CYP76AD1 can complement yellow beetroots to red while CYP76AD6 and CYP76AD5 cannot. Therefore CYP76AD1 uniquely performs the beet R locus function and beets appear to be genetically redundant for tyrosine hydroxylation. These new functional data and ancestral character state reconstructions indicate that tyrosine hydroxylation alone was the most likely ancestral function of the CYP76AD alpha and beta groups and the ability to convert L-DOPA to cyclo-DOPA evolved later in the alpha group. PMID:26890886

  9. Fum3p, a 2-ketoglutarate-dependent dioxygenase required for C-5 hydroxylation of fumonisins in Fusarium verticillioides.

    PubMed

    Ding, Yousong; Bojja, Ravi S; Du, Liangcheng

    2004-04-01

    Fumonisins are polyketide-derived mycotoxins produced by several agriculturally important Fusarium species. The B series fumonisins, FB(1), FB(2), FB(3), and FB(4), are fumonisins produced by wild-type Fusarium verticillioides strains, differing in the number and location of hydroxyl groups attached to the carbon backbone. We characterized the protein encoded by FUM3, a gene in the fumonisin biosynthetic gene cluster. The 33-kDa FUM3 protein (Fum3p) was heterologously expressed and purified from Saccharomyces cerevisiae. Yeast cells expressing the Fum3p converted FB(3) to FB(1), indicating that Fum3p catalyzes the C-5 hydroxylation of fumonisins. This result was verified by assaying the activity of Fum3p purified from yeast cells. The C-5 hydroxylase activity of purified Fum3p required 2-ketoglutarate, Fe(2+), ascorbic acid, and catalase, all of which are required for 2-ketoglutarate-dependent dioxygenases. The protein also contains two His motifs that are highly conserved in this family of dioxygenases. Thus, Fum3p is a 2-ketoglutarate-dependent dioxygenase required for the addition of the C-5 hydroxyl group of fumonisins.

  10. Tyrosine Hydroxylation in Betalain Pigment Biosynthesis Is Performed by Cytochrome P450 Enzymes in Beets (Beta vulgaris)

    PubMed Central

    Sunnadeniya, Rasika; Bean, Alexander; Brown, Matthew; Akhavan, Neda; Hatlestad, Gregory; Gonzalez, Antonio; Symonds, V. Vaughan; Lloyd, Alan

    2016-01-01

    Yellow and red-violet betalain plant pigments are restricted to several families in the order Caryophyllales, where betacyanins play analogous biological roles to anthocyanins. The initial step in betalain biosynthesis is the hydroxylation of tyrosine to form L-DOPA. Using gene expression experiments in beets, yeast, and Arabidopsis, along with HPLC/MS analysis, the present study shows that two novel cytochrome P450 (CYP450) enzymes, CYP76AD6 and CYP76AD5, and the previously described CYP76AD1 can perform this initial step. Co-expressing these CYP450s with DOPA 4,5-dioxygenase in yeast, and overexpression of these CYP450s in yellow beets show that CYP76AD1 efficiently uses L-DOPA leading to red betacyanins while CYP76AD6 and CYP76AD5 lack this activity. Furthermore, CYP76AD1 can complement yellow beetroots to red while CYP76AD6 and CYP76AD5 cannot. Therefore CYP76AD1 uniquely performs the beet R locus function and beets appear to be genetically redundant for tyrosine hydroxylation. These new functional data and ancestral character state reconstructions indicate that tyrosine hydroxylation alone was the most likely ancestral function of the CYP76AD alpha and beta groups and the ability to convert L-DOPA to cyclo-DOPA evolved later in the alpha group. PMID:26890886

  11. Abundance coefficients, a new method for measuring microorganism relative abundance

    USGS Publications Warehouse

    Forester, R.M.

    1977-01-01

    A new method of measuring the relative abundance of microorganisms by using a set of interrelated coefficients, termed 'abundance coefficients' or 'AC', is proposed. These coefficients provide a means of recording abundance for geometric density categories, and each density measurement represents an approximation of the Poisson parameter ??t. The AC is the natural logarithm of a 'characteristic value,' which is a particular number for each geometric density category. The 'characteristic values' are based upon a probabilistic error statement derived from the Poisson formula, and they present evidence for separation of the geometric category boundaries by e = 2.71828. The proposed AC provide a means for recording species abundance in a manner suitable for arithmetic manipulation, for population structure studies, and for the determination of practical limits for defining the presence or absence of a species. Further, these coefficients provide for both intrasample and intersample abundance comparisons. ?? 1977 Plenum Publishing Corporation.

  12. Mucor hiemalis mediated 14α-hydroxylation on steroids: in vivo and in vitro investigations of 14α-hydroxylase activity.

    PubMed

    Kolet, Swati P; Haldar, Saikat; Niloferjahan, Siddiqui; Thulasiram, Hirekodathakallu V

    2014-07-01

    Transformation of testosterone and progesterone into synthetically challenging 14α-hydroxy derivatives was achieved by using fungal strain Mucor hiemalis. Prolonged incubation led to the formation of corresponding 6β/7α,14α-dihydroxy metabolites. The position and stereochemistry of newly introduced hydroxyl group was determined by detailed spectroscopic analyses. The time course experiment indicated that fungal strain initiated transformation by hydroxylation at 14α-position followed by at 6β- or 7α-positions. Studies using cell-free extracts suggest that the 14α-hydroxylase activity is NADPH dependent and belongs to the cytochrome P450 family.

  13. Design, synthesis, and biological evaluation of simplified analogues of (+)-discodermolide. Additional insights on the importance of the diene, the C7 hydroxyl, and the lactone.

    PubMed

    Smith, Amos B; Xian, Ming

    2005-11-10

    [structure: see text] The design, synthesis, and biological evaluation of seven totally synthetic analogues of the antitumor agent (+)-discodermolide are reported. Saturation of the terminal diene system, alteration of the substituents on the lactone, and alkylation of the C7-hydroxyl group reveal significant structure-activity relationships.

  14. Method of making a membrane having hydrophilic and hydrophobic surfaces for adhering cells or antibodies by using atomic oxygen or hydroxyl radicals

    NASA Technical Reports Server (NTRS)

    Koontz, Steven L. (Inventor); Spaulding, Glenn F. (Inventor)

    1994-01-01

    A portion of an organic polymer article such as a membrane is made hydrophilic by exposing a hydrophobic surface of the article to a depth of about 50 to about 5000 angstroms to atomic oxygen or hydroxyl radicals at a temperature below 100C., preferably below 40 C, to form a hydrophilic uniform surface layer of hydrophilic hydroxyl groups. The atomic oxygen and hydroxyl radicals are generated by a flowing afterglow microwave discharge, and the surface is outside of a plasma produced by the discharge. A membrane having both hydrophilic and hydrophobic surfaces can be used in an immunoassay by adhering antibodies to the hydrophobic surface. In another embodiment, the membrane is used in cell culturing where cells adhere to the hydrophilic surface. Prior to adhering cells, the hydrophilic surface may be grafted with a compatibilizing compound. A plurality of hydrophilic regions bounded by adjacent hydrophobic regions can be produced such that a maximum of one cell per each hydrophilic region adheres.

  15. Adsorption and dissociation of NH3 on clean and hydroxylated TiO2 rutile (110) surfaces: a computational study.

    PubMed

    Chang, Jee-Gong; Chen, Hsin-Tsung; Ju, Shin-Pon; Chang, Ching-Sheng; Weng, Meng-Hsiung

    2011-04-30

    The adsorption and dissociation of NH(3) on the clean and hydroxylated TiO(2) rutile (110) surfaces have been investigated by the first-principles calculations. The monodentate adsorbates such as H(3)N-Ti(a), H(2)N-Ti(a), N-Ti(a), H(2)N-O(a), HN-O(a), N-O(a) and H-O(a), as well as the bidentate adsorbate, Ti-N-Ti(a) can be formed on the clean surface. It is found that the hydroxyl group enhances the adsorption of certain adsorbates on the five-fold-coordinated Ti atoms (5c-Ti), namely H(2)N-Ti(a), HN-Ti(a), N-Ti(a) and Ti-N-Ti(a). In addition, the adsorption energy increases as the number of hydroxyl groups increases. On the contrary, the opposite effect is found for those on the two-fold-coordinated O atoms (2c-O). The enhanced adsorption of NH(x) (x = 1-2) on the 5c-Ti is due to the large electronegativity of the OH group, increasing the acidity of the Ti center. This also contributes to diminish the adsorption of NH(x) (x = 1-2) on the two-fold-coordinated O atoms (2c-O) decreasing its basicity. According to potential energy profile, the NH(3) dissociation on the TiO(2) surface is endothermic and the hydroxyl group is found to lower the energetics of H(2)N-Ti(a)+H-O(a) and HN-Ti(a)+2{H-O(a)}, but slightly raise the energetic of Ti-N-Ti(a)+3{H-O(a)} compare to those on the clean surface. However, the dissociation of NH(3) is found to occur on the hydroxylated surface with an overall endothermic by 31.8 kcal/mol and requires a barrier of 37.5 kcal/mol. A comparison of NH(3) on anatase surface has been discussed. The detailed electronic analysis is also carried out to gain insights into the interaction nature between adsorbate and surface.

  16. Future Directions of Structural Mass Spectrometry using Hydroxyl Radical Footprinting

    SciTech Connect

    J Kiselar; M Chance

    2011-12-31

    Hydroxyl radical protein footprinting coupled to mass spectrometry has been developed over the last decade and has matured to a powerful method for analyzing protein structure and dynamics. It has been successfully applied in the analysis of protein structure, protein folding, protein dynamics, and protein-protein and protein-DNA interactions. Using synchrotron radiolysis, exposure of proteins to a 'white' X-ray beam for milliseconds provides sufficient oxidative modification to surface amino acid side chains, which can be easily detected and quantified by mass spectrometry. Thus, conformational changes in proteins or protein complexes can be examined using a time-resolved approach, which would be a valuable method for the study of macromolecular dynamics. In this review, we describe a new application of hydroxyl radical protein footprinting to probe the time evolution of the calcium-dependent conformational changes of gelsolin on the millisecond timescale. The data suggest a cooperative transition as multiple sites in different molecular subdomains have similar rates of conformational change. These findings demonstrate that time-resolved protein footprinting is suitable for studies of protein dynamics that occur over periods ranging from milliseconds to seconds. In this review, we also show how the structural resolution and sensitivity of the technology can be improved as well. The hydroxyl radical varies in its reactivity to different side chains by over two orders of magnitude, thus oxidation of amino acid side chains of lower reactivity are more rarely observed in such experiments. Here we demonstrate that the selected reaction monitoring (SRM)-based method can be utilized for quantification of oxidized species, improving the signal-to-noise ratio. This expansion of the set of oxidized residues of lower reactivity will improve the overall structural resolution of the technique. This approach is also suggested as a basis for developing hypothesis

  17. Erratum: Interstellar Abundance Standards Revisited

    NASA Astrophysics Data System (ADS)

    Sofia, U. J.; Meyer, D. M.

    2001-09-01

    In the Letter ``Interstellar Abundance Standards Revisited'' by U. J. Sofia and D. M. Meyer (ApJ, 554, L221 [2001]), Table 2 and its footnotes contain several typographical errors. The corrected table is shown below. We note that the solar reference standard now implies a positive abundance of nitrogen in halo dust.

  18. Hydroxylated Polychlorinated Biphenyls in the Environment: Sources, Fate, and Toxicities

    PubMed Central

    Tehrani, Rouzbeh; Van Aken, Benoit

    2013-01-01

    Hydroxylated polychlorinated biphenyls (OH-PCBs) are produced in the environment by the oxidation of PCBs through a variety of mechanisms, including metabolic transformation in living organisms and abiotic reactions with hydroxyl radicals. As a consequence, OH-PCBs have been detected in a wide range of environmental samples, including animal tissues, water, and sediments. OH-PCBs have recently raised serious environmental concerns because they exert a variety of toxic effects at lower doses than the parent PCBs and they are disruptors of the endocrine system. Although evidence has accumulated about the widespread dispersion of OH-PCBs in various compartments of the ecosystem, little is currently known about their biodegradation and behavior in the environment. OH-PCBs are today increasingly considered as a new class of environmental contaminants that possess specific chemical, physical, and biological properties not shared with the parent PCBs. This article reviews recent findings regarding the sources, fate, and toxicities of OH-PCBs in the environment. PMID:23636595

  19. Neon and Oxygen Abundances in M33

    NASA Astrophysics Data System (ADS)

    Crockett, N. R.; Garnett, D. R.; Massey, P.; Jacoby, G.

    2004-05-01

    We present new spectroscopic observations of 13 H II regions in the Local Group spiral galaxy M33. The regions observed range in distance between 1 and 7 kpc from the nucleus. Of the 13 H II regions observed, we were able to detect the [O III] 4363 Å line in six regions, and so were able to determine electron temperatures directly from the spectra using the 5007/4363 line ratio. Based on these temperature measurements we computed abundances for O and Ne for the six regions, and derived radial abundance gradients for both elements. We find that our new measurements lead to a shallower oxygen abundance gradient , --0.03±0.02 dex/kpc, than was derived by earlier studies. We attribute the difference partly to the use of uncertain extrapolations of O/H vs. ([O II] + [O III])/Hβ used in earlier studies to derive abundances for nebulae without measured electron temperatures. The shallower O/H gradient is in much better agreement with the Ne/H gradient derived from ISO spectra by Willner and Nelson-Patel, as expected from predictions of stellar nucleosynthesis. We also identify two new He II-emitting H II regions, the first to be discovered in M33.

  20. Ammonia formation from NO reaction with surface hydroxyls on rutile TiO2 (110) - 1×1

    SciTech Connect

    Kim, Boseong; Kay, Bruce D.; Dohnalek, Zdenek; Kim, Yu Kwon

    2015-01-15

    The reaction of NO with hydroxylated rutile TiO2(110)-1×1 surface (h-TiO2) was investigated as a function of NO coverage using temperature-programmed desorption. Our results show that NO reaction with h-TiO2 leads to formation of NH3 which is observed to desorb at ~ 400 K. Interestingly, the amount of NH3 produced depends nonlinearly on the coverage of NO. The yield increases up to a saturation value of ~1.3×1013 NH3/cm2 at a NO dose of 5×1013 NO/cm2, but subsequently decreases at higher NO doses. Preadsorbed H2O is found to have a negligible effect on the NH3 desorption yield. Additionally, no NH3 is formed in the absence of surface hydroxyls (HOb’s) upon coadsorption of NO and H2O on a stoichiometric TiO2(110) (s-TiO2(110)). Based on these observations, we conclude that nitrogen from NO has a strong preference to react with HOb’s on the bridge-bonded oxygen rows (but not with H2O) to form NH3. The absolute NH3 yield is limited by competing reactions of HOb species with titanium-bound oxygen adatoms to form H2O. Our results provide new mechanistic insight about the interactions of NO with hydroxyl groups on TiO2(110) .

  1. Different hydroxyl radical scavenging activity of water-soluble beta-alanine C60 adducts.

    PubMed

    Sun, Tao; Jia, Zhishen; Xu, Zhude

    2004-04-01

    Three C(60) derivatives [C(60) (NHCH(2)CH(2)COONa)(n)(H)(n)], n=1, 5, 9] (A, B, C) with different additional number of beta-alanine were synthesized by the control of relative amount of C(60) and beta-alanine added. Hydroxyl radical scavenging activity of the adducts was evaluated in a copper-catalyzed Haber-Weiss reaction by chemiluminescence technology. The 50% inhibition concentrations (IC(50)'s) of A, B, and C were 147.2 micromol/L, 76.3 micromol/L, and 96.2 micromol/L, respectively. The difference should be closely related to the numbers of residual C=C bonds in C(60), steric effect and electron-withstanding effect of amino group especially.

  2. Unusual hydroxyl migration in the fragmentation of β-alanine dication in the gas phase.

    PubMed

    Piekarski, Dariusz Grzegorz; Delaunay, Rudy; Maclot, Sylvain; Adoui, Lamri; Martín, Fernando; Alcamí, Manuel; Huber, Bernd A; Rousseau, Patrick; Domaracka, Alicja; Díaz-Tendero, Sergio

    2015-07-14

    We present a combined experimental and theoretical study of the fragmentation of doubly positively charged β-alanine molecules in the gas phase. The dissociation of the produced dicationic molecules, induced by low-energy ion collisions, is analysed by coincidence mass spectrometric techniques; the coupling with ab initio molecular dynamics simulations allows rationalisation of the experimental observations. The present strategy gives deeper insights into the chemical mechanisms of multiply charged amino acids in the gas phase. In the case of the β-alanine dication, in addition to the expected Coulomb explosion and hydrogen migration processes, we have found evidence of hydroxyl-group migration, which leads to unusual fragmentation products, such as hydroxymethyl cation, and is necessary to explain some of the observed dominant channels.

  3. Continuous Flow Reactor for Hydroxylation of Benzene to Phenol by Hydrogen Peroxide

    NASA Astrophysics Data System (ADS)

    Zhang, Li; Liu, Hui-hui; Li, Gui-ying; Hu, Chang-wei

    2012-10-01

    The direct hydroxylation of benzene to phenol catalyzed by activated carbon-supported Fe (Fe/AC) in acetonitrile using H2O2 as the oxidant was studied in a continuous flow reactor. Results showed that the continuous operation could obtain high phenol yield of 28.1%, coupled with the turnover frequency of 3 h-1, and high selectivity of 98% under mild condition. The catalyst was characterized by N2 adsorption/desorption, Boehm titration, X-ray photoelectron spectra, and Fourier transform infrared spectroscopy. It was observed that iron may interact with the carboxyl group forming iron-carboxylate like species, which act as the active phase. The apparent activation energy obtained by fitting an Arrhenius model to the experimental data was 13.4 kJ/mol. The reaction order was calculated to be about 1, 0.2 for benzene and 0.7 for H2O2.

  4. The Creation and Physiological Relevance of Divergent Hydroxylation Patterns in the Flavonoid Pathway

    PubMed Central

    Halbwirth, Heidi

    2010-01-01

    Flavonoids and biochemically-related chalcones are important secondary metabolites, which are ubiquitously present in plants and therefore also in human food. They fulfill a broad range of physiological functions in planta and there are numerous reports about their physiological relevance for humans. Flavonoids have in common a basic C6-C3-C6 skeleton structure consisting of two aromatic rings (A and B) and a heterocyclic ring (C) containing one oxygen atom, whereas chalcones, as the intermediates in the formation of flavonoids, have not yet established the heterocyclic C-ring. Flavonoids are grouped into eight different classes, according to the oxidative status of the C-ring. The large number of divergent chalcones and flavonoid structures is from the extensive modification of the basic molecules. The hydroxylation pattern influences physiological properties such as light absorption and antioxidative activity, which is the base for many beneficial health effects of flavonoids. In some cases antiinfective properties are also effected. PMID:20386656

  5. Probing site selective fragmentation of molecules containing hydroxyl group using Velocity Slice Imaging

    NASA Astrophysics Data System (ADS)

    Prabhudesai, Vaibhav S.; Bhargava Ram, N.; Aravind, G.; Rawat, P.; Krishnakumar, E.

    2007-09-01

    Site selective fragmentation is observed at the hydrogen site in small organic molecules like simple carboxylic acids and alcohols in the dissociative attachment (DA) process. We have investigated this site selectivity in the acetic acid and methanol molecules by measuring the kinetic energy and angular distribution of the hydride ions using Velocity Slice Imaging (VSI) technique. The results are explained in terms of the formation of valance excited Feshbach resonances. The kinetic energy and angular distribution measurements also reveal the dynamics associated with the process.

  6. New strategy for expression of recombinant hydroxylated human collagen α1(III) chains in Pichia pastoris GS115.

    PubMed

    He, Jing; Ma, Xiaoxuan; Zhang, Fenglong; Li, Linbo; Deng, Jianjun; Xue, Wenjiao; Zhu, Chenhui; Fan, Daidi

    2015-01-01

    Type III collagen is one of the most abundant proteins in the human body, which forms collagen fibrils and provides the stiff, resilient characteristics of many tissues. In this paper, a new method for secretory expression of recombinant hydroxylated human collagen α1(III) chain in Pichia pastoris GS115 was applied. The gene encoding for full-length human collagen α1(III) chain (COL3A1) without N-terminal propeptide and C-terminal propeptide was cloned in the pPIC9K expression vector. The prolyl 4-hydroxylase (P4H, EC 1.14.11.2) α-subunit (P4Hα) and β-subunit (P4Hβ) genes were cloned in the same expression vector, pPICZB. Fluorogenic quantitative PCR indicates that COL3A1 and P4H genes have been expressed in mRNA level. SDS-PAGE shows that secretory expression of recombinant human collagen α1(III) chain was successfully achieved in P. pastoris GS115. In addition, the result of amino acids composition analysis shows that the recombinant human collagen α1(III) chain contains hydroxyproline by coexpression with the P4H. Furthermore, liquid chromatography coupled with tandem mass spectrometry analysis demonstrates that proline residues of the recombinant human collagen α1(III) chain were hydroxylated in the X or Y positions of Gly-X-Y triplets. PMID:24953863

  7. On-Going Laboratory Efforts to Quantitatively Address Clay Abundance on Mars

    NASA Technical Reports Server (NTRS)

    Roush, Ted L.; Bishop, Janice L.; Brown, Adrian J.; Blake, David F.; Bristow, Thomas F.

    2012-01-01

    Data obtained at visible and near-infrared wavelengths by OMEGA on MarsExpress and CRISM on MRO provide definitive evidence for the presence of phyllosilicates and other hydrated phases on Mars. A diverse range of both Fe/Mg-OH and Al-OH-bearing phyllosilicates were identified including the smectites, nontronite, saponite, and montmorillonite. In order to constrain the abundances of these phyllosilicates spectral analyses of mixtures are needed. We report on our on-going effort to enable the quantitative evaluation of the abundance of hydrated-hydroxylated silicates when they are contained in mixtures. We include two component mixtures of hydrated/hydroxylated silicates with each other and with two analogs for other martian materials; pyroxene (enstatite) and palagonitic soil (an alteration product of basaltic glass). For the hydrated-hydroxylated silicates we include saponite and montmorillonite (Mg- and Al- rich smectites). We prepared three size separates of each end-member for study: 20-45, 63-90, and 125-150 µm. As the second phase of our effort we used scanning electron microscopy imaging and x-ray diffraction to characterize the grain size distribution, and structural nature, respectively, of the mixtures. Visible and near-infrared reflectance spectra of the 63-90 micrometers grain size of the mixture samples are shown in Figure 1. We discuss the results of our measurements of these mixtures.

  8. Mineral Abundance Near Aristarchus Crater

    NASA Astrophysics Data System (ADS)

    Bradford, Alison; Storrs, A.

    2007-12-01

    Mineral Abundance Near Aristarchus Crater Alison Bradford and Alex Storrs Towson University We analyze Hubble Space Telescope (HST) images to determine the abundance of minerals near Aristarchus crater. Following the calibration of Robinson et al. (2007) we present ratio maps of images obtained in August of 2005 showing the abundance of TiO2 and other minerals in this interesting area in the middle of Oceanus Procellarum. A prominent cleft (Schroter's Valley, presumably a collapsed lava tube) makes this region of special interest for analyzing the formation of mare basalts. Reference: Robinson, M.S., et al. (2007): "High resolution mapping of TiO2 abundances on the Moon using the Hubble Space Telescope", GRL 34, L13203

  9. The boron abundance of Procyon

    NASA Technical Reports Server (NTRS)

    Lemke, Michael; Lambert, David L.; Edvardsson, Bengt

    1993-01-01

    The B I 2496.8 A resonance line and HST/GHRS echelle spectra are used with model atmospheres and synthetic spectra to derive the B abundance of the F dwarfs Procyon (Alpha Canis Minoris), Theta Ursae Majoris, and Iota Pegasi. The B abundance of Theta UMa and Iota Peg is similar to that derived by Boesgaard and Heacox (1978) from the B II resonance line in spectra of A- and B-type stars. These two dwarfs show normal abundances of Li, Be, and B. Procyon, which is highly depleted in Li and Be, is depleted in B by a factor of at least 3. Comparison of the spectra of Procyon and the halo dwarf HD 140283 shows that the B abundance assigned by Duncan et al. (1992) to three halo dwarfs is not greatly overestimated as a result of contamination of the B I line by an unidentified line.

  10. Influence of edge on predator prey distribution and abundance

    NASA Astrophysics Data System (ADS)

    Ferguson, Steven H.

    2004-03-01

    I investigated the effect of spatial configuration on distribution and abundance of invertebrate trophic groups by counting soil arthropods under boxes (21 × 9.5 cm) arranged in six different patterns that varied in the amount of edge (137-305 cm). I predicted fewer individuals from the consumer trophic group (Collembola) in box groups with greater amount of edge. This prediction was based on the assumption that predators (mites, ants, spiders, centipedes) select edge during foraging and thereby reduce abundance of the less mobile consumer group under box patterns with greater edge. Consumer abundance (Collembola) was not correlated with amount of edge. Among the predator groups, mite, ant and centipede abundance related to the amount of edge of box groups. However, in contrast to predictions, abundance of these predators was negatively correlated with amount of edge in box patterns. All Collembola predators, with the exception of ants, were less clumped in distribution than Collembola. The results are inconsistent with the view that predators used box edges to predate the less mobile consumer trophic group. Alternative explanations for the spatial patterns other than predator-prey relations include (1) a negative relationship between edge and moisture, (2) a positive relationship between edge and detritus decomposition (i.e. mycelium as food for the consumer group), and (3) a negative relationship between edge and the interstices between adjacent boxes. Landscape patterns likely affect microclimate, food, and predator-prey relations and, therefore, future experimental designs need to control these factors individually to distinguish among alternative hypotheses.

  11. Aerial survey estimates of fallow deer abundance

    USGS Publications Warehouse

    Gogan, Peter J.; Gates, Natalie B.; Lubow, Bruce C.; Pettit, Suzanne

    2012-01-01

    Reliable estimates of the distribution and abundance of an ungulate species is essential prior to establishing and implementing a management program. We used ground surveys to determine distribution and ground and aerial surveys and individually marked deer to estimate the abundance of fallow deer (Dama dama) in north-coastal California. Fallow deer had limited distribution and heterogeneous densities. Estimated post-rut densities across 4 annual surveys ranged from a low of 1.4 (SE=0.2) deer/km2 to a high of 3.3 (se=0.5) deer/km2 in a low density stratum and from 49.0 (SE=8.3) deer/km2 to 111.6 deer/km2 in a high density stratum. Sightability was positively influenced by the presence of white color-phase deer in a group and group size, and varied between airial and ground-based observers and by density strata. Our findings underscore the utility of double-observer surveys and aerial surveys with individually marked deer, both incorporating covariates to model sightability, to estimate deer abundance.

  12. New hydroxylated metabolites of 4-monochlorobiphenyl in whole poplar plants

    PubMed Central

    2011-01-01

    Two new monohydroxy metabolites of 4-monochlorobiphenyl (CB3) were positively identified using three newly synthesized monohydroxy compounds of CB3: 2-hydroxy-4-chlorobiphenyl (2OH-CB3), 3-hydroxy-4-chlorobiphenyl (3OH-CB3) and 4-hydroxy-3-chlorobiphenyl (4OH-CB2). New metabolites of CB3, including 2OH-CB3 and 3OH-CB3, were confirmed in whole poplars (Populus deltoides × nigra, DN34), a model plant in the application of phytoremediation. Furthermore, the concentrations and masses of 2OH-CB3 and 3OH-CB3 formed in various tissues of whole poplar plants and controls were measured. Results showed that 2OH-CB3 was the major product in these two OH-CB3s with chlorine and hydroxyl moieties in the same phenyl ring of CB3. Masses of 2OH-CB3 and 3OH-CB3 in tissues of whole poplar plants were much higher than those in the hydroponic solution, strongly indicating that the poplar plant itself metabolizes CB3 to both 2OH-CB3 and 3OH-CB3. The total yield of 2OH-CB3 and 3OH-CB3, with chlorine and hydroxyl in the same phenyl ring of CB3, was less than that of three previously found OH-CB3s with chlorine and hydroxyl in the opposite phenyl rings of CB3 (2'OH-CB3, 3'OH-CB3, and 4'OH-CB3). Finally, these two newly detected OH-CB3s from CB3 in this work also suggests that the metabolic pathway was via epoxide intermediates. These five OH-CB3s clearly showed the complete metabolism profile from CB3 to monohydroxylated CB3. More importantly, it's the first report and confirmation of 2OH-CB3 and 3OH-CB3 (new metabolites of CB3) in a living organism. PMID:22185578

  13. Suppression of adipogenesis and obesity in high-fat induced mouse model by hydroxylated polymethoxyflavones.

    PubMed

    Lai, Ching-Shu; Ho, Min-Hau; Tsai, Mei-Ling; Li, Shiming; Badmaev, Vladimir; Ho, Chi-Tang; Pan, Min-Hsiung

    2013-10-30

    This study demonstrated that hydroxylated polymethoxyflavones (HPMFs) effectively and dose-dependently suppressed accumulation of lipid droplets in adipocytes by approximately 51-55%. Western blot analysis revealed that HPMFs markedly down-regulated adipogenesis-related transcription factors peroxisome proliferator-activated receptor (PPAR) γ and sterol regulatory element-binding protein (SREBP)-1c as well as downstream target fatty acid binding protein 2 (aP2), fatty acid synthase (FAS), and acetyl-CoA carboxylase (ACC). In addition, HPMFs also activated adenosine monophosphate-activated protein kinase (AMPK) signaling in 3T3-L1 adipocytes. In the early phase of adipogenesis, HPMF-treated preadipocytes displayed a delayed cell cycle entry into G2/M phase at 24 h (35.5% for DMI group and 4.8% for 20 μg/mL HPMFs-treated group) after initiation of adipogenesis. Furthermore, administration of HPMFs (0.25 and 1%) decreased high-fat diet (HFD) induced weight gain (15.3 ± 3.9 g for HFD group, 10.3 ± 0.3 g and 7.9 ± 0.7 g for 0.25 and 1% HPMFs groups, respectively) and relative perigonadal, retroperitoneal, mesenteric fat weight in C57BL/6 mice. Administration of HPMFs reduced serum levels of aspartate aminotransferase (GOT), alanine aminotransferase (GPT), triglycerides (TG), and total cholesterol (T-cho). The results suggested that HPMFs may have a potential benefit in preventing obesity. PMID:24089698

  14. Moringa oleifera Lam. seed extract prevents fat diet induced oxidative stress in mice and protects liver cell-nuclei from hydroxyl radical mediated damage.

    PubMed

    Das, Nilanjan; Ganguli, Debdutta; Dey, Sanjit

    2015-12-01

    High fat diet (HFD) prompts metabolic pattern inducing reactive oxygen species (ROS) production in mitochondria thereby triggering multitude of chronic disorders in human. Antioxidants from plant sources may be an imperative remedy against this disorder. However, it requires scientific validation. In this study, we explored if (i) Moringa oleifera seed extract (MoSE) can neutralize ROS generated in HFD fed mice; (ii) protect cell-nuclei damage developed by Fenton reaction in vitro. Swiss mice were fed with HFD to develop oxidative stress model (HFD group). Other groups were control, seed extract alone treated, and MoSE simultaneously (HS) treated. Treatment period was of 15 days. Antioxidant enzymes with tissue nitrite content (TNC) and lipid peroxidation (LPO) were estimated from liver homogenate. HS group showed significantly higher (P < 0.05) superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx), reduced glutathione (GSH) activity, and ferric reducing antioxidant power (FRAP) compared to only HFD fed group. Further, TNC and LPO decreased significantly (P < 0.05) in HS group compared to HFD fed group. MoSE also protected hepatocytes nuclei from the hydroxyl radicals generated by Fenton reaction. MoSE was found to be polyphenol rich with potent reducing power, free radicals and hydroxyl radicals scavenging activity. Thus, MoSE exhibited robust antioxidant prospective to neutralize ROS developed in HFD fed mice and also protected the nuclei damage from hydroxyl radicals. Hence, it can be used as herbal medication against HFD induced ROS mediated disorders.

  15. Moringa oleifera Lam. seed extract prevents fat diet induced oxidative stress in mice and protects liver cell-nuclei from hydroxyl radical mediated damage.

    PubMed

    Das, Nilanjan; Ganguli, Debdutta; Dey, Sanjit

    2015-12-01

    High fat diet (HFD) prompts metabolic pattern inducing reactive oxygen species (ROS) production in mitochondria thereby triggering multitude of chronic disorders in human. Antioxidants from plant sources may be an imperative remedy against this disorder. However, it requires scientific validation. In this study, we explored if (i) Moringa oleifera seed extract (MoSE) can neutralize ROS generated in HFD fed mice; (ii) protect cell-nuclei damage developed by Fenton reaction in vitro. Swiss mice were fed with HFD to develop oxidative stress model (HFD group). Other groups were control, seed extract alone treated, and MoSE simultaneously (HS) treated. Treatment period was of 15 days. Antioxidant enzymes with tissue nitrite content (TNC) and lipid peroxidation (LPO) were estimated from liver homogenate. HS group showed significantly higher (P < 0.05) superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx), reduced glutathione (GSH) activity, and ferric reducing antioxidant power (FRAP) compared to only HFD fed group. Further, TNC and LPO decreased significantly (P < 0.05) in HS group compared to HFD fed group. MoSE also protected hepatocytes nuclei from the hydroxyl radicals generated by Fenton reaction. MoSE was found to be polyphenol rich with potent reducing power, free radicals and hydroxyl radicals scavenging activity. Thus, MoSE exhibited robust antioxidant prospective to neutralize ROS developed in HFD fed mice and also protected the nuclei damage from hydroxyl radicals. Hence, it can be used as herbal medication against HFD induced ROS mediated disorders. PMID:26742324

  16. Spectroscopy and reaction dynamics of collision complexes containing hydroxyl radicals

    SciTech Connect

    Lester, M.I.

    1993-12-01

    The DOE supported work in this laboratory has focused on the spectroscopic characterization of the interaction potential between an argon atom and a hydroxyl radical in the ground X{sup 2}II and excited A {sup 2}{summation}{sup +} electronic states. The OH-Ar system has proven to be a test case for examining the interaction potential in an open-shell system since it is amenable to experimental investigation and theoretically tractable from first principles. Experimental identification of the bound states supported by the Ar + OH (X {sup 2}II) and Ar + OH(A {sup 2}{summation}{sup +}) potentials makes it feasible to derive realistic potential energy surfaces for these systems. The experimentally derived intermolecular potentials provide a rigorous test of ab initio theory and a basis for understanding the dramatically different collision dynamics taking place on the ground and excited electronic state surfaces.

  17. Kinetics of the reaction of hydroxyl radicals with nitric acid

    NASA Technical Reports Server (NTRS)

    Margitan, J. J.; Watson, R. T.

    1982-01-01

    An extensive study was made of the reaction of hydroxyl radicals with nitric acid in a laser photolysis-resonance fluorescence system. A 266 nm laser was used to photolyze HNO3 in the temperature range 225-415 K at pressures of 20-300 torr. A temperature dependence was detected below room temperature, with a leveling off at 298 K and a wide spread in the rate constants. A pressure dependence was observed over the entire range and was more pronounced at lower temperatures. The results are noted to be in agreement with those of previous investigations. However, the wide range of rate constants are suggested to be a problem for stratospheric HO(x) modeling for anthropogenic effects. No explanation could be given of the varying results obtained by other investigators regarding the kinetics of the reactions.

  18. Crystal structure of tris­(hydroxyl­ammonium) orthophosphate

    PubMed Central

    Leinemann, Malte; Jess, Inke; Boeckmann, Jan; Näther, Christian

    2015-01-01

    The crystal structure of the title salt, ([H3NOH]+)3·[PO4]3−, consists of discrete hydroxyl­ammonium cations and ortho­phos­phate anions. The atoms of the cation occupy general positions, whereas the anion is located on a threefold rotation axis that runs through the phospho­rus atom and one of the phosphate O atoms. In the crystal structure, cations and anions are linked by inter­molecular O—H⋯O and N—H⋯O hydrogen bonds into a three-dimensional network. Altogether, one very strong O—H⋯O, two N—H⋯O hydrogen bonds of medium strength and two weaker bifurcated N—H⋯O inter­actions are observed. PMID:26594525

  19. SPLASH: A Southern Parkes Large Area Survey in Hydroxyl

    NASA Astrophysics Data System (ADS)

    Dawson, Joanne; Caswell, James; Gomez, Jose F.; Mcclure-Griffiths, Naomi; Lo, Nadia; Jones, Paul; Dickey, John; Cunningham, Maria; Green, James; Carretti, Ettore; Ellingsen, Simon; Walsh, Andrew; Purcell, Cormac; Breen, Shari; Hennebelle, Patrick; Imai, Hiroshi; Lowe, Vicki; Gibson, Steven; Brown, Courtney; Krishnan, Vasaant

    2014-04-01

    The OH 18 cm lines are powerful and versatile probes of diffuse molecular gas, that trace a largely unstudied component of the Galactic ISM. SPLASH (the Southern Parkes Large Area Survey in Hydroxyl) is a large, unbiased and fully-sampled survey of OH emission, absorption and masers in the Galactic Plane that will achieve sensitivities an order of magnitude better than previous work. The survey is answering critical questions on the global distribution of diffuse OH, the degree to which it traces ‘hidden’ material caught between the regimes probed by traditional tracers of the neutral ISM, and its role as a probe of molecular cloud formation. As a blind survey for all four ground-state transitions, SPLASH is also detecting many new OH masers, facilitating a broad range of astrophysical studies. This proposal requests 250 hours to complete Phase 1 of the SPLASH project, which is mapping 152 square degrees in the inner Galactic Plane, including the Galactic Centre.

  20. Scavenging effect of melatonin on hydroxyl radicals generated by alloxan.

    PubMed

    Brömme, H J; Mörke, W; Peschke, D; Ebelt, H; Peschke, D

    2000-11-01

    Alloxan can act as a generator of reactive oxygen species (ROS) as long as sufficient suitable reducing agents (e.g. reduced glutathione) and oxygen are available. Using electron spin resonance-spectroscopy and the oxygen-centered spin trap DEPMPO, we demonstrate that hydroxyl radicals (OH.) are formed in vitro by alloxan in the presence of glutathione (GSH) and chelated divalent iron. Furthermore, peroxidation of polyunsaturated fatty acids from phosphatidylcholine-containing liposomes with concomitant formation of malondialdehyde (MDA) was used as a further indicator for a preceding OH. formation. Melatonin, the main secretory product of the pineal gland, is an effective scavenger of OH.. The 50%-inhibitor concentration (IC50-value) for melatonin to scavenge OH. generated from the alloxan/GSH-reaction in the presence of ferrous ions was 23 micromol/L. In contrast to the ability to effectively scavenge OH., the potential of melatonin to prevent lipid peroxidation is considerably less pronounced. PMID:11068942

  1. Balloon-borne spectroscopic observation of the infrared hydroxyl airglow.

    PubMed

    Lowe, R P; Lytle, E A

    1973-03-01

    A balloon-borne grating spectrometer has been used to study the spectrum of the airglow between 1.8 microm and 3.6 microm and its diurnal variation. The principal features identified are the bands of the Deltaupsilon = 2 and Deltaupsilon = 1 sequences of the vibration-rotation spectrum of OH. The brightness of the 1-0 band at night was measured to be in the range 270-400 kR on two flights. A sudden decrease in the intensity of the hydroxyl bands occurred in morning twilight at a solar depression of 4 degrees and is ascribed to the photodissociation of ozone. The temperature, as indicated by the Q/R branch ratio, rose from 170 K at night to 255 K at noon indicating a reduction in the height of the emitting layer during the day.

  2. Effective L-Tyrosine Hydroxylation by Native and Immobilized Tyrosinase

    PubMed Central

    Lewańczuk, Marcin; Koźlecki, Tomasz; Liesiene, Jolanta; Bryjak, Jolanta

    2016-01-01

    Hydroxylation of L-tyrosine to 3,4-dihydroxyphenylalanine (L-DOPA) by immobilized tyrosinase in the presence of ascorbic acid (AH2), which reduces DOPA-quinone to L-DOPA, is characterized by low reaction yields that are mainly caused by the suicide inactivation of tyrosinase by L-DOPA and AH2. The main aim of this work was to compare processes with native and immobilized tyrosinase to identify the conditions that limit suicide inactivation and produce substrate conversions to L-DOPA of above 50% using HPLC analysis. It was shown that immobilized tyrosinase does not suffer from partitioning and diffusion effects, allowing a direct comparison of the reactions performed with both forms of the enzyme. In typical processes, additional aeration was applied and boron ions to produce the L-DOPA and AH2 complex and hydroxylamine to close the cycle of enzyme active center transformations. It was shown that the commonly used pH 9 buffer increased enzyme stability, with concomitant reduced reactivity of 76%, and that under these conditions, the maximal substrate conversion was approximately 25 (native) to 30% (immobilized enzyme). To increase reaction yield, the pH of the reaction mixture was reduced to 8 and 7, producing L-DOPA yields of approximately 95% (native enzyme) and 70% (immobilized). A three-fold increase in the bound enzyme load achieved 95% conversion in two successive runs, but in the third one, tyrosinase lost its activity due to strong suicide inactivation caused by L-DOPA processing. In this case, the cost of the immobilized enzyme preparation is not overcome by its reuse over time, and native tyrosinase may be more economically feasible for a single use in L-DOPA production. The practical importance of the obtained results is that highly efficient hydroxylation of monophenols by tyrosinase can be obtained by selecting the proper reaction pH and is a compromise between complexation and enzyme reactivity. PMID:27711193

  3. Analysis of Hydroxyl Radical Reactivity in the Sierra Nevada Mountains

    NASA Astrophysics Data System (ADS)

    Carlstad, J. M.; Schroeder, J.; Beyersdorf, A. J.; Blake, D. R.

    2015-12-01

    Using the UC Irvine Whole Air Sampler, volatile organic compounds (VOCs) were measured onboard the NASA DC-8 during the Student Airborne Research Program. High levels of ozone were observed near the surface over the Sierra Nevada mountains, and VOC data was used to investigate factors that contributed to ozone production. This was done by calculating the hydroxyl radical reactivity, which can, in proper conditions, be used to predict ozone formation potential. The region was divided into three boxes from east to west, based on wind direction, and the reactivity was analyzed over each region with respect to methane, non-methane alkanes, alkenes, aromatics, and biogenic compounds. In the westernmost box the reactivity was 1.7 ± 0.5 s-1 (1σ), in the middle section it was 1.4 ± 1 s-1, and in the easternmost region it was 0.8 ± 0.3 s-1. The data were compared with a region known to be heavily polluted, the Los Angeles (LA) basin, and it was observed that the reactivity was 1.1 ± 0.6 s-1, lower than in two of the mountainous regions. In the Sierra Nevada mountains a major percentage of the hydroxyl radical reactivity was the result of biogenic influence, at 24% for the western box, 39% for the middle box, and 31% for the easternmost box, in contrast to only 2% biogenic contribution in LA. This indicates that biogenic factors greatly contributed to overall ozone formation in the Sierra Nevada mountains. These mountains are strategically protected, and high pollution levels could lead to health impacts for visitors, vegetation, and wildlife.

  4. Molecular Insights into the Local Anesthetic Receptor within Voltage-Gated Sodium Channels Using Hydroxylated Analogs of Mexiletine.

    PubMed

    Desaphy, Jean-François; Dipalma, Antonella; Costanza, Teresa; Carbonara, Roberta; Dinardo, Maria Maddalena; Catalano, Alessia; Carocci, Alessia; Lentini, Giovanni; Franchini, Carlo; Camerino, Diana Conte

    2012-01-01

    We previously showed that the β-adrenoceptor modulators, clenbuterol and propranolol, directly blocked voltage-gated sodium channels, whereas salbutamol and nadolol did not (Desaphy et al., 2003), suggesting the presence of two hydroxyl groups on the aromatic moiety of the drugs as a molecular requisite for impeding sodium channel block. To verify such an hypothesis, we synthesized five new mexiletine analogs by adding one or two hydroxyl groups to the aryloxy moiety of the sodium channel blocker and tested these compounds on hNav1.4 channels expressed in HEK293 cells. Concentration-response relationships were constructed using 25-ms-long depolarizing pulses at -30 mV applied from an holding potential of -120 mV at 0.1 Hz (tonic block) and 10 Hz (use-dependent block) stimulation frequencies. The half-maximum inhibitory concentrations (IC(50)) were linearly correlated to drug lipophilicity: the less lipophilic the drug, minor was the block. The same compounds were also tested on F1586C and Y1593C hNav1.4 channel mutants, to gain further information on the molecular interactions of mexiletine with its receptor within the sodium channel pore. In particular, replacement of Phe1586 and Tyr1593 by non-aromatic cysteine residues may help in the understanding of the role of π-π or π-cation interactions in mexiletine binding. Alteration of tonic block suggests that the aryloxy moiety of mexiletine may interact either directly or indirectly with Phe1586 in the closed sodium channel to produce low-affinity binding block, and that this interaction depends on the electrostatic potential of the drug aromatic tail. Alteration of use-dependent block suggests that addition of hydroxyl groups to the aryloxy moiety may modify high-affinity binding of the drug amine terminal to Phe1586 through cooperativity between the two pharmacophores, this effect being mainly related to drug lipophilicity. Mutation of Tyr1593 further impaired such cooperativity. In conclusion, these

  5. Nitrogen abundance in Comet Halley

    NASA Technical Reports Server (NTRS)

    Wyckoff, Susan; Tegler, Stephen C.; Engel, Lisa

    1991-01-01

    Data on the nitrogen-containing compounds that observed spectroscopically in the coma of Comet Halley are summarized, and the elemental abundance of nitrogen in the Comet Halley nucleus is derived. It is found that 90 percent of elemental nitrogen is in the dust fraction of the coma, while in the gas fraction, most of the nitrogen is contained in NH3 and CN. The elemental nitrogen abundance in the ice component of the nucleus was found to be deficient by a factor of about 75, relative to the solar photosphere, indicating that the chemical partitioning of N2 into NH3 and other nitrogen compounds during the evolution of the solar nebula cannot account completely for the low abundance ratio N2/NH3 = 0.1, observed in the comet. It is suggested that the low N2/NH3 ratio in Comet Halley may be explained simply by physical fractionation and/or thermal diffusion.

  6. Solar and stellar photospheric abundances

    NASA Astrophysics Data System (ADS)

    Allende Prieto, Carlos

    2016-07-01

    The determination of photospheric abundances in late-type stars from spectroscopic observations is a well-established field, built on solid theoretical foundations. Improving those foundations to refine the accuracy of the inferred abundances has proven challenging, but progress has been made. In parallel, developments on instrumentation, chiefly regarding multi-object spectroscopy, have been spectacular, and a number of projects are collecting large numbers of observations for stars across the Milky Way and nearby galaxies, promising important advances in our understanding of galaxy formation and evolution. After providing a brief description of the basic physics and input data involved in the analysis of stellar spectra, a review is made of the analysis steps, and the available tools to cope with large observational efforts. The paper closes with a quick overview of relevant ongoing and planned spectroscopic surveys, and highlights of recent research on photospheric abundances.

  7. Robust Abundance Estimation in Animal Abundance Surveys with Imperfect Detection

    EPA Science Inventory

    Surveys of animal abundance are central to the conservation and management of living natural resources. However, detection uncertainty complicates the sampling process of many species. One sampling method employed to deal with this problem is depletion (or removal) surveys in whi...

  8. Comparison of fluorescence-based techniques for the quantification of particle-induced hydroxyl radicals

    PubMed Central

    Cohn, Corey A; Simon, Sanford R; Schoonen, Martin AA

    2008-01-01

    Background Reactive oxygen species including hydroxyl radicals can cause oxidative stress and mutations. Inhaled particulate matter can trigger formation of hydroxyl radicals, which have been implicated as one of the causes of particulate-induced lung disease. The extreme reactivity of hydroxyl radicals presents challenges to their detection and quantification. Here, three fluorescein derivatives [aminophenyl fluorescamine (APF), amplex ultrared, and dichlorofluorescein (DCFH)] and two radical species, proxyl fluorescamine and tempo-9-ac have been compared for their usefulness to measure hydroxyl radicals generated in two different systems: a solution containing ferrous iron and a suspension of pyrite particles. Results APF, amplex ultrared, and DCFH react similarly to the presence of hydroxyl radicals. Proxyl fluorescamine and tempo-9-ac do not react with hydroxyl radicals directly, which reduces their sensitivity. Since both DCFH and amplex ultrared will react with reactive oxygen species other than hydroxyl radicals and another highly reactive species, peroxynitite, they lack specificity. Conclusion The most useful probe evaluated here for hydroxyl radicals formed from cell-free particle suspensions is APF due to its sensitivity and selectivity. PMID:18307787

  9. Coronal Abundances and Their Variation

    NASA Technical Reports Server (NTRS)

    Saba, Julia L. R.

    1996-01-01

    This contract supported the investigation of elemental abundances in the solar corona, principally through analysis of high-resolution soft X-ray spectra from the Flat Crystal Spectrometer on NASA's Solar Maximum Mission. The goals of the study were a characterization of the mean values of relative abundances of elements accessible in the FCS data, and information on the extent and circumstances of their variability. This is the Final Report, summarizing the data analysis and reporting activities which occurred during the period of performance, June 1993 - December 1996.

  10. Chemical Abundances of Symbiotic Giants

    NASA Astrophysics Data System (ADS)

    Gałan, C.; Mikołajewska, J.; Hinkle, K. H.; Joyce, R. R.

    2015-12-01

    High resolution (R ˜ 50000), near-IR spectra were used to measure photospheric abundances of CNO and elements around the iron peak for 24 symbiotic giants. Spectrum synthesis was employed using local thermal equilibrium and hydrostatic model atmospheres. The metallicities are distributed in a wide range with maximum around [Fe/H] ˜-0.4 - - 0.3 dex. Enrichment in 14N indicates that all the sample giants have experienced the first dredge-up. The relative abundance of [Ti/Fe] is generally large in red symbiotic systems.

  11. Coronal abundances and their variation

    NASA Technical Reports Server (NTRS)

    Saba, Julia L. R.

    1994-01-01

    This contract supports the investigation of elemental abundances in the solar corona, principally through analysis of high-resolution soft x-ray spectra from the Flat Crystal Spectrometer (FCS) on the Solar Maximum Mission. The goals of the study are a characterization of the mean values of relative abundances of elements accessible in the FCS data, and information on the extent and circumstances of their variability. This report is a summation of the data analysis and reporting activities which occurred during the first ten months of the contract, 15 Jun. 1993 to 15 Apr. 1994.

  12. The solar abundance of beryllium

    NASA Technical Reports Server (NTRS)

    Ross, J. E.; Aller, L. H.

    1974-01-01

    The solar abundance of beryllium is deduced from high-resolution Kitt Peak observations of the 3130.43- and 3131.08-A lines of Be II interpreted by the method of spectrum synthesis. The results are in good agreement with those previously obtained by Grevesse (1968) and by Hauge and Engvold (1968) and indicate that in the photospheric layers, beryllium is depleted below the chondritic value by a factor of about two. It is found that the beryllium abundance is equal to logN(Be)/N(H) + 12 = 1.08 plus or minus 0.05.

  13. SOLAR MODELS WITH REVISED ABUNDANCE

    SciTech Connect

    Bi, S. L.; Li, T. D.; Yang, W. M.; Li, L. H.

    2011-04-20

    We present new solar models in which we use the latest low abundances and further include the effects of rotation, magnetic fields, and extra-mixing processes. We assume that the extra-element mixing can be treated as a diffusion process, with the diffusion coefficient depending mainly on the solar internal configuration of rotation and magnetic fields. We find that such models can well reproduce the observed solar rotation profile in the radiative region. Furthermore, the proposed models can match the seismic constraints better than the standard solar models, also when these include the latest abundances, but neglect the effects of rotation and magnetic fields.

  14. [7alpha-hydroxylation of steroid 5-olefins by mold fungi].

    PubMed

    Andriushina, V G; Druzhinina, A V; Iaderets, V V; Stytsenko, T S; Voĭshvillo, N E

    2010-01-01

    Hydroxylation activity of the mold fungi belonging to the orders Dothideales, Hypocreales, and Mucorales towards delta(5)-3beta-hydroxysteroids was studied. The fungi Bipolaris sorokiniana, Fusarium sp., and Rhizopus nigricans were able to introduce hydroxy group at position 7alpha; however, this ability was detected only at a low substrate load and with a low yield. A 7alpha-hydroxylase activity of the Curvularia lunata VKPM F-981 culture was shown for the first time. It was demonstrated that the studied strain was capable of stereo- and regioselective transformations of androstane 5-olefins at a load not less than 2 g/l. Conversion of pregnane steroids by this culture yielded both 7alpha and 11beta-hydroxy derivatives. The introduction of 7alpha-hydroxy group by this strain occurred concurrently with enzymatic hydrolysis of ester groups, which proceeded under mild conditions to give the corresponding alcohols in the cases of both 3-acetate of delta(5)-androstenes and mono- and triacetates of delta(5)-pregnenes.

  15. Characterization of hydroxyl radical modified GAD65: a potential autoantigen in type 1 diabetes.

    PubMed

    Khan, Mohd Wajid A; Sherwani, Subuhi; Khan, Wahid A; Ali, Rashid

    2009-02-01

    Glutamic acid decarboxylase-65 (GAD(65)) is an immunological marker of type 1 autoimmune diabetes. High titre of autoantibodies against GAD(65) (GAD(65)Abs) have also been detected in some other autoimmune diseases. In search of a potential immunological marker of type 1 diabetes, in vitro GAD(65) was modified by hydroxyl radical followed by the study of structural and conformational perturbed protein by different spectroscopic techniques (UV, fluorescence and CD) and thermal denaturation profile. Binding studies of circulating autoantibodies from diabetic groups (type 1 and type 2) with native and reactive oxygen species (ROS) modified GAD(65), exhibited high recognition of type 1 diabetic serum autoantibodies with modified antigen (p < 0.001) over unmodified GAD(65). Binding specificity of isolated IgG of patients (n = 17) from each diabetic group and control group (n = 10) was checked by inhibition enzyme linked immunosorbent assay (ELISA) and quantitative precipitin titration assay. Relative affinity of ROS-GAD(65)Abs for modified and native GAD(65) was in the order of 1.56 x 10(- 6) and 2.72 x 10(- 7) M, as calculated by Langmuir plot. In coherence, ROS oxidation of GAD(65) causes conformational perturbation, generating highly immunogenic unique neoepitopes that may be one of the factors in antigen-driven induction of type 1 diabetes autoantibodies that can serve as a potential marker in early diagnosis/prognosis of the disease.

  16. Hydroxyl radical scavenging activities of isoquinoline alkaloids isolated from Coptis chinensis.

    PubMed

    Jang, Moon Hee; Kim, Hyun Young; Kang, Ki Sung; Yokozawa, Takako; Park, Jeong Hill

    2009-03-01

    The hydroxyl radical (*OH) scavenging and ferrous ion chelating activities of four isoquinoline alkaloids isolated from Coptis chinensis Franch were studied for the identification of their structural characteristics to scavenge *OH. The *OH was generated via Fe(II)-catalazed Fenton reaction in this study and the reliable measurement of *OH scavenging activities of isoquinoline alkaloids were achieved using electron spin resonance (ESR) spectrometry method. At the 1 mM concentration, berberrubine (85%) showed the strongest *OH scavenging activity and the next were in the decreasing order of coptisine (79%), berberine (23%), and palmatine (22%). The ferrous ion chelating effects of the alkaloids showed similar pattern with their *OH scavenging effects. These results suggest that *OH scavenging effects of the alkaloids were closely related to their ferrous ion chelating activities. In addition, metal chelating functional groups such as hydroxy group at C-9 and methylenedioxy group at C-9 and C-10 were thought to contribute to the *OH scavenging activities of the isoquinoline alkaloids.

  17. Synthetic tripodal receptors for carbohydrates. Pyrrole, a hydrogen bonding partner for saccharidic hydroxyls.

    PubMed

    Francesconi, Oscar; Gentili, Matteo; Roelens, Stefano

    2012-09-01

    The carbohydrate recognition properties of synthetic tripodal receptors relying on H-bonding interactions have highlighted the crucial role played by the functional groups matching saccharidic hydroxyls. Herein, pyrrole and pyridine, which emerged as two of the most effective H-bonding groups, were quantitatively compared through their isostructural substitution within the architecture of a shape-persistent bicyclic cage receptor. NMR and ITC binding studies gave for the pyrrolic receptor a 20-fold larger affinity toward octyl-β-d-glucopyranoside in CDCl(3), demonstrating the superior recognition properties of pyrrole under conditions in which differences would depend on the intrinsic binding ability of the two groups. The three-dimensional structures of the two glucoside complexes in solution were elucidated by combined NMR and molecular mechanics computational techniques, showing that the origin of the stability difference between the two closely similar complex structures resides in the ability of pyrrole to establish shorter/stronger H-bonds with the glucosidic ligand compared to pyridine.

  18. Regulation of Hydroxylation and Nitroreduction Pathways during Metabolism of the Neonicotinoid Insecticide Imidacloprid by Pseudomonas putida.

    PubMed

    Lu, Tian-Qi; Mao, Shi-Yun; Sun, Shi-Lei; Yang, Wen-Long; Ge, Feng; Dai, Yi-Jun

    2016-06-22

    Imidacloprid (IMI) is mainly metabolized via nitroreduction and hydroxylation pathways, which produce different metabolites that are toxic to mammals and insects. However, regulation of IMI metabolic flux between nitroreduction and hydroxylation pathways is still unclear. In this study, Pseudomonas putida was found to metabolize IMI to 5-hydroxy and nitroso IMI and was therefore used for investigating the regulation of IMI metabolic flux. The cell growth time, cosubstrate, dissolved oxygen concentration, and pH showed significant effect on IMI degradation and nitroso and 5-hydroxy IMI formation. Gene cloning and overexpression in Escherichia coli proved that P. putida KT2440 aldehyde oxidase mediated IMI nitroreduction to nitroso IMI, while cytochrome P450 monooxygenase (CYP) failed to improve IMI hydroxylation. Moreover, E. coli cells without CYP could hydroxylate IMI, demonstrating the role of a non-CYP enzyme in IMI hydroxylation. Thus, the present study helps to further understand the environmental fate of IMI and its underlying mechanism. PMID:27230024

  19. Layer by layer H-bonded assembly of P4VP with various hydroxylated PPFS: impact of the donor strength on growth mechanism and surface features.

    PubMed

    Chen, Jing; Duchet, Jannick; Portinha, Daniel; Charlot, Aurélia

    2014-09-01

    Hydrogen bond mediated films made by step by step deposition of poly(4-vinylpyridine) (P4VP) and hydroxylated poly(2,3,4,5,6-pentafluorostyrene) (PPFS) copolymers prepared by thiol para-fluoro coupling, bearing either one (PPFSME) or two (PPFSMPD) hydrogenated hydroxyl groups or a (poly)fluorinated hydroxyl (PPFSOH), respectively, were successfully constructed. The influence of the structural parameters, such as the hydroxyl environment (which dictates the H-bond strength) was in-depth investigated in terms of their impact on (i) growth mechanism, (ii) internal organization, and (iii) surface features. The use of the weaker H-bond donor partner (PPFSME) leads to low quality films composed of irregularly distributed aggregates. While [PPFSMPD/P4VP] multilayer films are comparatively thick and composed of stratified layers with smooth topology, the use of PPFSOH with P4VP yields thin films made of mixed and interpenetrated polymer layers. Playing on the interaction strength appears as a powerful tool to elaborate tailored multilayer films with molecularly tunable properties.

  20. THE SOLAR FLARE IRON ABUNDANCE

    SciTech Connect

    Phillips, K. J. H.; Dennis, B. R. E-mail: Brian.R.Dennis@nasa.gov

    2012-03-20

    The abundance of iron is measured from emission line complexes at 6.65 keV (Fe line) and 8 keV (Fe/Ni line) in RHESSI X-ray spectra during solar flares. Spectra during long-duration flares with steady declines were selected, with an isothermal assumption and improved data analysis methods over previous work. Two spectral fitting models give comparable results, viz., an iron abundance that is lower than previous coronal values but higher than photospheric values. In the preferred method, the estimated Fe abundance is A(Fe) = 7.91 {+-} 0.10 (on a logarithmic scale, with A(H) = 12) or 2.6 {+-} 0.6 times the photospheric Fe abundance. Our estimate is based on a detailed analysis of 1898 spectra taken during 20 flares. No variation from flare to flare is indicated. This argues for a fractionation mechanism similar to quiet-Sun plasma. The new value of A(Fe) has important implications for radiation loss curves, which are estimated.

  1. Abundance estimation and conservation biology

    USGS Publications Warehouse

    Nichols, J.D.; MacKenzie, D.I.

    2004-01-01

    Abundance is the state variable of interest in most population–level ecological research and in most programs involving management and conservation of animal populations. Abundance is the single parameter of interest in capture–recapture models for closed populations (e.g., Darroch, 1958; Otis et al., 1978; Chao, 2001). The initial capture–recapture models developed for partially (Darroch, 1959) and completely (Jolly, 1965; Seber, 1965) open populations represented efforts to relax the restrictive assumption of population closure for the purpose of estimating abundance. Subsequent emphases in capture–recapture work were on survival rate estimation in the 1970’s and 1980’s (e.g., Burnham et al., 1987; Lebreton et al.,1992), and on movement estimation in the 1990’s (Brownie et al., 1993; Schwarz et al., 1993). However, from the mid–1990’s until the present time, capture–recapture investigators have expressed a renewed interest in abundance and related parameters (Pradel, 1996; Schwarz & Arnason, 1996; Schwarz, 2001). The focus of this session was abundance, and presentations covered topics ranging from estimation of abundance and rate of change in abundance, to inferences about the demographic processes underlying changes in abundance, to occupancy as a surrogate of abundance. The plenary paper by Link & Barker (2004) is provocative and very interesting, and it contains a number of important messages and suggestions. Link & Barker (2004) emphasize that the increasing complexity of capture–recapture models has resulted in large numbers of parameters and that a challenge to ecologists is to extract ecological signals from this complexity. They offer hierarchical models as a natural approach to inference in which traditional parameters are viewed as realizations of stochastic processes. These processes are governed by hyperparameters, and the inferential approach focuses on these hyperparameters. Link & Barker (2004) also suggest that our attention

  2. Actinide abundances in ordinary chondrites

    USGS Publications Warehouse

    Hagee, B.; Bernatowicz, T.J.; Podosek, F.A.; Johnson, M.L.; Burnett, D.S.; Tatsumoto, M.

    1990-01-01

    Measurements of 244Pu fission Xe, U, Th, and light REE (LREE) abundances, along with modal petrographic determinations of phosphate abundances, were carried out on equilibrated ordinary chondrites in order to define better the solar system Pu abundance and to determine the degree of variation of actinide and LREE abundances. Our data permit comparison of the directly measured Pu/ U ratio with that determined indirectly as (Pu/Nd) ?? (Nd/U) assuming that Pu behaves chemically as a LREE. Except for Guaren??a, and perhaps H chondrites in general, Pu concentrations are similar to that determined previously for St. Se??verin, although less precise because of higher trapped Xe contents. Trapped 130Xe 136Xe ratios appear to vary from meteorite to meteorite, but, relative to AVCC, all are similar in the sense of having less of the interstellar heavy Xe found in carbonaceous chondrite acid residues. The Pu/U and Pu/Nd ratios are consistent with previous data for St. Se??verin, but both tend to be slightly higher than those inferred from previous data on Angra dos Reis. Although significant variations exist, the distribution of our Th/U ratios, along with other precise isotope dilution data for ordinary chondrites, is rather symmetric about the CI chondrite value; however, actinide/(LREE) ratios are systematically lower than the CI value. Variations in actinide or LREE absolute and relative abundances are interpreted as reflecting differences in the proportions and/or compositions of more primitive components (chondrules and CAI materials?) incorporated into different regions of the ordinary chondrite parent bodies. The observed variations of Th/U, Nd/U, or Ce/U suggest that measurements of Pu/U on any single equilibrated ordinary chondrite specimen, such as St. Se??verin, should statistically be within ??20-30% of the average solar system value, although it is also clear that anomalous samples exist. ?? 1990.

  3. Production of hydroxyl radical by redox active flavonoids

    SciTech Connect

    Kalyanaraman, B.; Hodnick, W.F.; Pardini, R.S.

    1986-05-01

    The authors have previously shown that flavonoids autoxidize and generate superoxide (O/sub 2//sup -/) and hydrogen peroxide (H/sub 2/O/sub 2/), suggesting that hydroxyl radical (OH) could be formed via the metal-ion catalyzed Haber-Weiss reaction. In the presence of ethylenediamine tetraacetic acid (EDTA) and 5,5-dimethyl-1-pyrroline-1-oxide (DMPO), myricetin, quercetagetin and quercetin gave an ESR signal for the DMPO-OH spin adduct, and the DMPO-Eto adduct in the presence of excess ethanol, indicating the production of free OH. The addition of FeCl/sub 3/ to the reaction mixture resulted in a dramatic increase in the DMPO-OH signal. Without chelator (EDTA) there was no signal and the presence of diethylenetriamine-pentaacetic acid (DETAPAC) greatly diminished the signal. The presence of superoxide dismutase (SOD) had no effect on the signal while catalase completely abrogated the signal. The addition of Fe (III)-EDTA to flavonoid solutions under anaerobic conditions produced time dependent auxochromic shifts in their absorption spectra and resulted in the reduction of Fe (III) to Fe (II). These data suggest that the flavonoids autoxidize to produce O/sub 2//sup -/ and H/sub 2/O/sub 2/ by dismutation and in the presence of Fe (III)-EDTA the flavonoid can directly reduce the Fe (III) to Fe (II) resulting in the production of OH through Fenton chemistry.

  4. Hydroxylation of methane through component interactions in soluble methane monooxygenases.

    PubMed

    Lee, Seung Jae

    2016-04-01

    Methane hydroxylation through methane monooxygenases (MMOs) is a key aspect due to their control of the carbon cycle in the ecology system and recent applications of methane gas in the field of bioenergy and bioremediation. Methanotropic bacteria perform a specific microbial conversion from methane, one of the most stable carbon compounds, to methanol through elaborate mechanisms. MMOs express particulate methane monooxygenase (pMMO) in most strains and soluble methane monooxygenase (sMMO) under copper-limited conditions. The mechanisms of MMO have been widely studied from sMMO belonging to the bacterial multicomponent monooxygenase (BMM) superfamily. This enzyme has diiron active sites where different types of hydrocarbons are oxidized through orchestrated hydroxylase, regulatory and reductase components for precise control of hydrocarbons, oxygen, protons, and electrons. Recent advances in biophysical studies, including structural and enzymatic achievements for sMMO, have explained component interactions, substrate pathways, and intermediates of sMMO. In this account, oxidation of methane in sMMO is discussed with recent progress that is critical for understanding the microbial applications of C-H activation in one-carbon substrates.

  5. Two supramolecular microporous frameworks stabilized by hydroxyl anionic water cluster

    NASA Astrophysics Data System (ADS)

    Jian, Fang Fang; Wang, Jing; Huang, Li Hua; Wang, Xian; Xiao, Hai Lian

    2010-06-01

    Two stable supramolecular microporous framework complexes, from the same [MCl(phen) 2] + (M = Cu, Ni), containing chiral hydroxyl anionic water cluster polymer, were synthesized, and their crystal structures were described. These supramolecular frameworks showed very high stability even if they were heated to 300 °C. Thermal analysis and powder X-ray diffraction results indicated that the water molecules were removed when heated from 150 °C to 300 °C without losing the main crystal framework. Water molecules can be reassembled by exposing the dehydrated form to an atmosphere saturated with water vapor. It indicated that the dehydrated form may be utilized as a potential absorbing agent for water and water vapor. The stable dehydrated form, [MCl(phen) 2][(OH)(H 2O)], suggested the stronger anionic H-bonding and intracluster proton transfer process OH -·H 2O → H 2O·OH -. The "anion- π interaction" was found in the crystal lattice of [MCl(phen) 2][(OH)(H 2O)]. This paper reported an example of supramolecular polymer with open channels that could be formed/collapse reversibly upon hydration/dehydration.

  6. SPLASH: A Southern Parkes Large Area Survey in Hydroxyl

    NASA Astrophysics Data System (ADS)

    Dawson, Joanne; Caswell, James; Gomez, Jose F.; Mcclure-Griffiths, Naomi; Lo, Nadia; Jones, Paul; Dickey, John; Cunningham, Maria; Green, James; Carretti, Ettore; Ellingsen, Simon; Walsh, Andrew; Purcell, Cormac; Breen, Shari; Hennebelle, Patrick; Imai, Hiroshi; Lowe, Vicki; Gibson, Steven; Jones, Courtney; Krishnan, Vasaant

    2013-10-01

    The OH 18 cm lines are powerful and versatile probes of diffuse molecular gas, that may trace a largely unstudied component of the Galactic ISM. SPLASH (the Southern Parkes Large Area Survey in Hydroxyl) is a large, unbiased and fully-sampled survey of OH emission, absorption and masers in the Galactic Plane that will achieve sensitivities an order of magnitude better than previous work. The survey will answer critical questions on the global distribution of diffuse OH, the degree to which it traces ‘hidden’ material caught between the regimes probed by traditional tracers of the neutral ISM, and its role as a probe of molecular cloud formation. As a blind survey for all four ground-state transitions, SPLASH will also detect many new OH masers, facilitating a broad range of astrophysical studies. This proposal requests 670 hours spread over two semesters to complete Phase 1 of the SPLASH project, which will map 152 square degrees in the inner Galactic Plane, including the Galactic Centre. Following the ongoing success of the project, we request that its pre-graded status be renewed for a final two semesters.

  7. Hydroxylated Polybrominated Diphenyl Ethers in Paired Maternal and Cord Sera

    PubMed Central

    Chen, Aimin; Park, June-Soo; Linderholm, Linda; Rhee, Alexandra; Petreas, Myrto; DeFranco, Emily A.; Dietrich, Kim N.; Ho, Shuk-mei

    2015-01-01

    Polybrominated diphenyl ethers (PBDEs) were widely used as flame retardants in the past three decades. These compounds are lipophilic and easily cross the placenta from pregnant woman to fetus. It is not clear whether hydroxylated PBDEs (OH-PBDEs), with greater hydrophilicity, have different concentrations in maternal and cord serum samples. We analyzed PBDEs (BDE-28, -47, -99, -100, -153, -154, -209) and OH-PBDEs (6-OH-BDE-47, 5-OH-BDE-47, 4′-OH-BDE-49, 5′-OH-BDE-99) in 20 pairs of maternal and cord serum samples collected in Cincinnati, OH in 2011. The geometric mean concentration of ΣOH-BDEs (the sum of four OH-PBDEs) was 49.76 pg/ml in cord sera, higher than 32.84 pg/ml in maternal sera. Similarly, cord serum total BDEs had a higher geometric mean than maternal serum (45.51 vs. 32.07 ng/g lipid). Equal or higher levels of total OH-BDEs and total BDEs in cord serum were observed in 85% and 80% of the mother-neonate pairs, respectively. The study suggests fetuses might receive higher OH-PBDE and PBDE exposure than their mothers. PMID:23506475

  8. Single vs multi-level quenching of the hydroxyl airglow

    NASA Astrophysics Data System (ADS)

    Franzen, Christoph; Espy, Patrick J.; Hibbins, Robert; Djupvik, Anlaug Amanda

    2016-04-01

    The reaction in the upper mesosphere between atomic hydrogen and ozone results in hydroxyl (OH) that is produced in excited vibrational levels 6 through 9. The vibrationally excited OH radiates in a thin (~8 km thick) layer near 87 km, giving rise to the strong near infrared airglow emission that has been used for remote sensing of the mesopause region. The interpretation of the emission relies on accurate knowledge of the population and quenching of the upper states, and open questions remain as to whether the quenching takes place through single- or multi-quantum deactivation. Here we will demonstrate how high quality spectral observations of OH (9,7) and (8,6) airglow emissions are available as background measurements during standard K-band astronomical observations from the Nordic Optical Telescope (18°W, 29°N). These emissions have been analysed to ascertain the quenching of the upper vibrational populations. Together with a steady-state model of these emissions, an estimate of the ratio of single to multi-quantum quenching efficiency and the impact on the populations of the lower vibrational levels will be presented.

  9. PBDEs, hydroxylated PBDEs and methoxylated PBDEs in bivalves from Beijing markets.

    PubMed

    Liu, Xitao; Jiao, Ying; Lin, Chunye; Sun, Ke; Zhao, Ye

    2014-09-01

    The structural analogues of polybrominated diphenyl ethers (PBDEs), hydroxylated PBDEs (OH-PBDEs) and methoxylated PBDEs (MeO-PBDEs) have been attracting increasing concern in recent years. Five bivalve species (blue mussel, short-necked clam, surf clam, ark shell and razor clam) were collected from Beijing markets, and the concentrations of seven PBDEs, four OH-PBDEs and fourteen MeO-PBDEs in the bivalves were measured. The seasonal variations of these three types of polybrominated compound in blue mussels were also monitored. The results indicate that the levels of ΣPBDEs in this study were comparable to those in short-necked clams from Liaodong Bay, China, with BDE47 as the dominant congener. For the ortho-MeO-PBDEs, 6-MeO-BDE47 was found at higher concentrations than the others, while for the meta- and para-MeO-PBDEs, 4'-MeO-BDE17 was found at higher concentrations. 6-OH-BDE-47 was the most abundant congener among the 4 measured OH-PBDEs, followed by 6-OH-BDE-137 and 6-OH-BDE-85. The levels of OH-PBDEs and MeO-PBDEs in bivalves from Beijing markets were much lower than the corresponding compounds in blue mussels from the Baltic Sea. In the blue mussels collected in April, June and September of 2012, apparent seasonal variations were observed for these three types of polybrominated compounds, but the acidic components displayed different trends from the neutral components, with PBDEs and MeO-PBDEs showing the highest concentrations in June, while OH-PBDEs had the lowest concentrations in June. This difference in seasonal variations between the neutral components and the acidic components may be explained by their different sources and transformation/elimination mechanisms.

  10. Production of hydroxylated polybrominated diphenyl ethers from bromophenols by bromoperoxidase-catalyzed dimerization.

    PubMed

    Lin, Kunde; Gan, Jay; Liu, Weiping

    2014-10-21

    Hydroxylated polybrominated diphenyl ethers (HO-PBDEs) are emerging endocrine-disrupting compounds that are widely present in the marine environment. The origin of HO-PBDEs is generally attributed to metabolism of PBDEs and natural production in the environment. However, it is unclear how HO-PBDEs are produced naturally. Here we report the formation of HO-PBDEs from simple bromophenols (BPs) [e.g., 2,4-dibromophenol (2,4-DBP) and 2,4,6-tribromophenol (2,4,6-TBP)] under the catalysis of bromoperoxidase (BPO) isolated from the common marine red alga Corallina officinalis. Experiments at room temperature showed that BPO readily catalyzes the conversion of 2,4-DBP and 2,4,6-TBP to HO-PBDEs in the presence of Br(-) and H2O2. From analysis of the original forms and their corresponding methylated derivatives, the reaction products were tentatively identified as 2'-HO-BDE-121 and 4'-HO-BDE-121. The formation of HO-PBDEs was likely resulted from the coupling of bromophenoxy radicals generated by the oxidation of BPs via BPO-mediated processes. The presence of Br(-) in the reaction favored the conversion. The production of HO-PBDEs was found to be pH-dependent, and a higher yield was obtained at pH 6.5. In view of the abundance of BPs and C. officinalis in the marine environment, bioconversion of BPs mediated by BPO may be a potential route for the natural production of HO-PBDEs.

  11. Fingerprinting of hydroxyl radical-attacked polysaccharides by N-isopropyl-2-aminoacridone labelling.

    PubMed

    Vreeburg, Robert A M; Airianah, Othman B; Fry, Stephen C

    2014-10-15

    Hydroxyl radicals (•OH) cause non-enzymic scission of polysaccharides in diverse biological systems. Such reactions can be detrimental (e.g. causing rheumatic and arthritic diseases in mammals) or beneficial (e.g. promoting the softening of ripening fruit, and biomass saccharification). Here we present a method for documenting •OH action, based on fluorescent labelling of the oxo groups that are introduced as glycosulose residues when •OH attacks polysaccharides. The method was tested on several polysaccharides, especially pectin, after treatment with Fenton reagents. 2-Aminoacridone plus cyanoborohydride reductively aminated the oxo groups in treated polysaccharides; the product was then reacted with acetone plus cyanoborohydride, forming a stable tertiary amine with the carbohydrate linked to N-isopropyl-2-aminoacridone (pAMAC). Digestion of labelled pectin with 'Driselase' yielded several fluorescent products which on electrophoresis and HPLC provided a useful 'fingerprint' indicating •OH attack. The most diagnostic product was a disaccharide conjugate of the type pAMAC·UA-GalA (UA=unspecified uronic acid), whose UA-GalA bond was Driselase-resistant (product 2A). 2A was clearly distinguishable from GalA-GalA-pAMAC (disaccharide labelled at its reducing end), which was digestible to GalA-pAMAC. The methodology is applicable, with appropriate enzymes in place of Driselase, for detecting natural and artificial •OH attack in diverse plant, animal and microbial polysaccharides.

  12. Fingerprinting of hydroxyl radical-attacked polysaccharides by N-isopropyl-2-aminoacridone labelling

    PubMed Central

    Vreeburg, Robert A. M.; Airianah, Othman B.; Fry, Stephen C.

    2014-01-01

    Hydroxyl radicals (•OH) cause non-enzymic scission of polysaccharides in diverse biological systems. Such reactions can be detrimental (e.g. causing rheumatic and arthritic diseases in mammals) or beneficial (e.g. promoting the softening of ripening fruit, and biomass saccharification). Here we present a method for documenting •OH action, based on fluorescent labelling of the oxo groups that are introduced as glycosulose residues when •OH attacks polysaccharides. The method was tested on several polysaccharides, especially pectin, after treatment with Fenton reagents. 2-Aminoacridone plus cyanoborohydride reductively aminated the oxo groups in treated polysaccharides; the product was then reacted with acetone plus cyanoborohydride, forming a stable tertiary amine with the carbohydrate linked to N-isopropyl-2-aminoacridone (pAMAC). Digestion of labelled pectin with ‘Driselase’ yielded several fluorescent products which on electrophoresis and HPLC provided a useful ‘fingerprint’ indicating •OH attack. The most diagnostic product was a disaccharide conjugate of the type pAMAC·UA-GalA (UA=unspecified uronic acid), whose UA-GalA bond was Driselase-resistant (product 2A). 2A was clearly distinguishable from GalA-GalA–pAMAC (disaccharide labelled at its reducing end), which was digestible to GalA–pAMAC. The methodology is applicable, with appropriate enzymes in place of Driselase, for detecting natural and artificial •OH attack in diverse plant, animal and microbial polysaccharides. PMID:25072268

  13. Hydrogen spillover enhanced hydroxyl formation and catalytic activity toward CO oxidation at the metal/oxide interface.

    PubMed

    Jin, Yuekang; Sun, Guanghui; Xiong, Feng; Ding, Liangbing; Huang, Weixin

    2015-03-01

    H2-promoted catalytic activity of oxide-supported metal catalysts in low-temperature CO oxidation is of great interest but its origin remains unknown. Employing an FeO(111)/Pt(111) inverse model catalyst, we herewith report direct experimental evidence for the spillover of H(a) adatoms on the Pt surface formed by H2 dissociation to the Pt-FeO interface to form hydroxyl groups that facilely oxidize CO(a) on the neighboring Pt surface to produce CO2. Hydroxyl groups and coadsorbed water play a crucial role in the occurrence of hydrogen spillover. These results unambiguously identify the occurrence of hydrogen spillover from the metal surface to the noble metal/metal oxide interface and the resultant enhanced catalytic activity of the metal/oxide interface in low-temperature CO oxidation, which provides a molecular-level understanding of both H2-promoted catalytic activity of metal/oxide ensembles in low-temperature CO oxidation and hydrogen spillover.

  14. A theoretical investigation of the interactions between hydroxyl-functionalized ionic liquid and water/methanol/dimethyl sulfoxide.

    PubMed

    Zhao, Shuang; Tian, XinZhe; Ren, YunLai; Wang, JianJi; Liu, JunNa; Ren, YunLi

    2016-08-01

    Density functional calculations have been used to investigate the interactions of 1-(2-hydroxyethyl)-3-methylimidazolium ([C2OHmim](+))-based ionic liquids (hydroxyl ILs) with water (H2O), methanol (CH3OH), and dimethyl sulfoxide (DMSO). It was found that the cosolvent molecules interact with the anion and cation of each ionic liquid through different atoms, i.e., H and O atoms, respectively. The interactions between the cosolvent molecules and 1-ethyl-3-methylimizolium ([C2mim](+))-based ionic liquids (nonhydroxyl ILs) were also studied for comparison. In the cosolvent-[nonhydroxyl ILs] systems, a furcated H-bond was formed between the O atom of the cosolvent molecule and the C2-H and C6-H, while there were always H-bonds involving the OH group of the cation in the cosolvent-[hydroxyl ILs] systems. Introducing an OH group on the ethyl side of the imidazolium ring may change the order of solubility of the molecular liquids. PMID:27480880

  15. 20-Hydroxylation is the CYP-dependent and retinoid-inducible leukotriene B4 inactivation pathway in human and mouse skin cells

    PubMed Central

    Du, Liping; Yin, Huiyong; Morrow, Jason D.; Strobel, Henry W.; Keeney, Diane S.

    2009-01-01

    Metabolic inactivation of leukotriene B4 (LTB4) is an innate mechanism to resolve tissue inflammation. We studied the nine Cyp4f genes in the mouse genome, measuring cutaneous transcript levels by real-time polymerase chain reaction, and LTB4 metabolism in mouse and human skin. Transcripts arising from Cyp4f13 and 4f16 ranked most abundant, Cyp4f14, 4f17, and 4f37 ranked least abundant, and Cyp4f18 and 4f39 ranked intermediate. Those from Cyp4f15 and Cyp4f40 were highly variable or too low to measure in some animals. Retinoic acid exposure induced microsomal LTB4 hydroxylation activities in mouse and human skin cells. Two NADPH-dependent LTB4 metabolites eluted identically with 20-OH and 20-COOH LTB4 reference standards. Collision induced dissociation of the precursor ion m/z 351 confirmed that LTB4 products from CYP4F3A and human epidermal keratinocytes are identical structurally to 20-OH LTB4. We conclude 20-hydroxylation is the major CYP-dependent LTB4 inactivation pathway in skin; this retinoid-inducible metabolic pathway has capacity to modulate tissue levels of pro-inflammatory lipids. PMID:19467632

  16. Quantitative analysis of the kinetic constant of the reaction of N,N'-propylenedinicotinamide with the hydroxyl radical using dimethyl sulfoxide and deduction of its structure in chloroform.

    PubMed

    Akimoto, T

    2000-04-01

    N,N'-Propylenedinicotinamide (Nicaraven) is presently being developed for the treatment of cerebral stroke including subarachnoid hemorrhage. This drug is promising because some data suggest it to have an ability to scavenge the hydroxyl radical under physiological conditions in vivo, while it also has a high permeability through the blood brain barrier. Using the kinetic constant of the reaction between the hydroxyl radical and dimethyl sulfoxide, the formula derived by Babbs and Griffin (Free Rad. Biol. Med., 6 1989) was applied to obtain the kinetic constant of Nicaraven with the hydroxyl radical using a dimethyl sulfoxide-xanthine oxidase-hypoxanthine-Fe system, and this yielded the kinetic constant 3.4x10(9) M(-1) s(-1) (1 M=1 mol dm(-3)) for Nicaraven. Structurally related compounds were also investigated. The amide group of Nicaraven was thus found to play an important part in the reaction with the hydroxyl radical. Methanesulfinic acid, which was obtained from the reaction between dimethyl sulfoxide and the hydroxyl radical, was found to be stable under this adopted experimental condition and therefore was used to quantify the kinetic constant of Nicaraven. The structure of Nicaraven has also been investigated in CDCl3 using IR spectra, computer calculations and 1H-NMR analysis, and Nicaraven was thus shown to have an intramolecular hydrogen bond which forms a 7-membered ring that resembles a part of the 1H-1,4-benzodiazepines. This structure may play an important role in the penetration through the blood brain barrier.

  17. Development of colorimetric HTS assay of cytochrome p450 for ortho-specific hydroxylation, and engineering of CYP102D1 with enhanced catalytic activity and regioselectivity.

    PubMed

    Choi, Kwon-Young; Jung, Eun-Ok; Yun, Hyungdon; Yang, Yung-Hun; Kazlauskas, Romas J; Kim, Byung-Gee

    2013-07-01

    A current challenge in high-throughput screening (HTS) of hydroxylation reactions by P450 is a fast and sensitive assay for regioselective hydroxylation against millions of mutants. We have developed a solid-agar plate-based HTS assay for screening ortho-specific hydroxylation of daidzein by sensing formaldehyde generated from the O-dealkylation reaction. This method adopts a colorimetric dye, pararosaniline, which has previously been used as an aldehyde-specific probe within cells. The rationale for this method lies in the fact that the hydroxylation activity at ortho-carbon position to COH correlates with a linear relationship to O-dealkylation activity on chemically introduced methoxy group at the corresponding COH. As a model system, a 4',7-dihydroxyisoflavone (daidzein) hydroxylase (CYP102D1 F96V/M246I), which catalyzes hydroxylation at ortho positions of the daidzein A/B-ring, was examined for O-dealklyation activity, by using permethylated daidzein as a surrogate substrate. By using the developed indirect bishydroxylation screening assay, the correlation coefficient between O-dealkylation and bishydroxylation activity for the template enzyme was 0.72. For further application of this assay, saturation mutants at A273/G274/T277 were examined by mutant screening with a permethylated daidzein analogue substrate (A-ring inactivated in order to find enhanced 3'-regioselectiviy). The whole-cell biotransformation of daidzein by final screened mutant G1 (A273H/G274E/T277G) showed fourfold increased conversion yield, with 14.3 mg L(-1) production titer and greatly increased 3'-regioselectiviy (3'/6=11.8). These results show that there is a remarkably high correlation (both in vitro and in vivo), thus suggesting that this assay would be ideal for a primary HTS assay for P450 reactions.

  18. Coronal abundances and their variation

    NASA Technical Reports Server (NTRS)

    Saba, Julia L. R.

    1994-01-01

    This contract supports the investigation of elemental abundances in the solar corona, principally through analysis of high-resolution software X-ray spectra from the Flat Crystal Spectrometer on NASA's Solar Maximum Mission. The goals of the study are a characterization of the mean values of relative abundances of elements accessible in the FCS data, and information on the extent and circumstances of their variability. This report is a summation of the data analysis and reporting activities which occurred since the last report, submitted two months early, in April 1994, to facilitate evaluation of the first year's progress for contract renewal. Hence this report covers the period 15 April 1994 - 15 December 1994. A list of publications resulting from this research is included.

  19. New aerial survey and hierarchical model to estimate manatee abundance

    USGS Publications Warehouse

    Langimm, Cahterine A.; Dorazio, Robert M.; Stith, Bradley M.; Doyle, Terry J.

    2011-01-01

    Monitoring the response of endangered and protected species to hydrological restoration is a major component of the adaptive management framework of the Comprehensive Everglades Restoration Plan. The endangered Florida manatee (Trichechus manatus latirostris) lives at the marine-freshwater interface in southwest Florida and is likely to be affected by hydrologic restoration. To provide managers with prerestoration information on distribution and abundance for postrestoration comparison, we developed and implemented a new aerial survey design and hierarchical statistical model to estimate and map abundance of manatees as a function of patch-specific habitat characteristics, indicative of manatee requirements for offshore forage (seagrass), inland fresh drinking water, and warm-water winter refuge. We estimated the number of groups of manatees from dual-observer counts and estimated the number of individuals within groups by removal sampling. Our model is unique in that we jointly analyzed group and individual counts using assumptions that allow probabilities of group detection to depend on group size. Ours is the first analysis of manatee aerial surveys to model spatial and temporal abundance of manatees in association with habitat type while accounting for imperfect detection. We conducted the study in the Ten Thousand Islands area of southwestern Florida, USA, which was expected to be affected by the Picayune Strand Restoration Project to restore hydrology altered for a failed real-estate development. We conducted 11 surveys in 2006, spanning the cold, dry season and warm, wet season. To examine short-term and seasonal changes in distribution we flew paired surveys 1–2 days apart within a given month during the year. Manatees were sparsely distributed across the landscape in small groups. Probability of detection of a group increased with group size; the magnitude of the relationship between group size and detection probability varied among surveys. Probability

  20. The solar abundance of thulium

    NASA Technical Reports Server (NTRS)

    Ross, J. E.; Aller, L. H.

    1974-01-01

    Consideration of one relatively unblended line of the solar spectrum, namely, the 3131.258-A line of Tm II, which yields a thulium abundance of 0.80 plus or minus 0.10 with the Corliss and Bozman (1962) f-value. The uncertainty of this figure is discussed in conjunction with the contradictory findings of some other investigators. The need for further detailed study of the lanthanides by the method of spectrum synthesis is pointed out.

  1. Hydroxyl radical oxidation of cylindrospermopsin (cyanobacterial toxin) and its role in the photochemical transformation.

    PubMed

    Song, Weihua; Yan, Shuwen; Cooper, William J; Dionysiou, Dionysios D; O'Shea, Kevin E

    2012-11-20

    Cylindrospermopsin (CYN), an alkaloid guanidinium sulfated toxin, is produced by a number of cyanobacteria regularly found in lakes, rivers, and reservoirs. Steady-state and time-resolved radiolysis methods were used to determine reaction pathways and kinetic parameters for the reactions of hydroxyl radical with CYN. The absolute bimolecular reaction rate constant for the reaction of hydroxyl radical with CYN is (5.08 ± 0.16) × 10(9) M(-1) s(-1). Comparison of the overall reaction rate of CYN with hydroxyl radical with the individual reaction rate for addition to the uracil ring in CYN indicate the majority of the hydroxyl radicals (84%) react at the uracil functionality of CYN. Product analyses using liquid chromatography-mass spectrometry indicate the major products from the reaction of hydroxyl radical with CYN involve attack of hydroxyl radical at the uracil ring and hydrogen abstraction from the hydroxy-methine bridge linking the uracil ring to the tricyclic guanidine functionality. The role of hydroxyl radical initiated pathways in the natural organic matter (NOM) photosensitized transformation of CYN were evaluated. Scavenger and trapping experiments indicate that hydroxyl radical mediated transformations account for approximately ~70% of CYN destruction in surface waters under solar irradiation in the presence of NOM. The absence of solvent isotope effect indicates singlet oxygen does not play a significant role in the NOM sensitized transformation of CYN. The primary degradation pathways for HO• mediated and NOM photosensitized destruction of CYN involve destruction of the uracil ring. The fundamental kinetic parameters determined from these studies are critical for the accurate evaluation of hydroxyl-radical based technologies for the remediation of this problematic cyanotoxin in drinking water and important in the assessment of the environmental oxidative transformation of uracil based compounds. PMID:23082747

  2. Hydroxyl PAMAM dendrimer-based gene vectors for transgene delivery to human retinal pigment epithelial cells

    NASA Astrophysics Data System (ADS)

    Mastorakos, Panagiotis; Kambhampati, Siva P.; Mishra, Manoj K.; Wu, Tony; Song, Eric; Hanes, Justin; Kannan, Rangaramanujam M.

    2015-02-01

    Ocular gene therapy holds promise for the treatment of numerous blinding disorders. Despite the significant progress in the field of viral and non-viral gene delivery to the eye, significant obstacles remain in the way of achieving high-level transgene expression without adverse effects. The retinal pigment epithelium (RPE) is involved in the pathogenesis of retinal diseases and is a key target for a number of gene-based therapeutics. In this study, we addressed the inherent drawbacks of non-viral gene vectors and combined different approaches to design an efficient and safe dendrimer-based gene-delivery platform for delivery to human RPE cells. We used hydroxyl-terminated polyamidoamine (PAMAM) dendrimers functionalized with various amounts of amine groups to achieve effective plasmid compaction. We further used triamcinolone acetonide (TA) as a nuclear localization enhancer for the dendrimer-gene complex and achieved significant improvement in cell uptake and transfection of hard-to-transfect human RPE cells. To improve colloidal stability, we further shielded the gene vector surface through incorporation of PEGylated dendrimer along with dendrimer-TA for DNA complexation. The resultant complexes showed improved stability while minimally affecting transgene delivery, thus improving the translational relevance of this platform.Ocular gene therapy holds promise for the treatment of numerous blinding disorders. Despite the significant progress in the field of viral and non-viral gene delivery to the eye, significant obstacles remain in the way of achieving high-level transgene expression without adverse effects. The retinal pigment epithelium (RPE) is involved in the pathogenesis of retinal diseases and is a key target for a number of gene-based therapeutics. In this study, we addressed the inherent drawbacks of non-viral gene vectors and combined different approaches to design an efficient and safe dendrimer-based gene-delivery platform for delivery to human RPE

  3. Hydroxyl concentration and δD to trace weathering from Critical Zones to river sediment in Himalaya

    NASA Astrophysics Data System (ADS)

    Morin, G. P.; France-Lanord, C.; Lupker, M.; Rigaudier, T.; Lavé, J.

    2013-12-01

    One primary consequence of weathering is the hydration of secondary silicate. Combined hydroxyl concentration and its hydrogen isotopic composition can therefore document respectively, intensity and location of weathering in large watersheds. We apply these proxies on source rocks and erosion products i.e. glacier sediments, soil, landslide debris and river suspended and bank sediments from the Narayani basin, that is draining a complete segment of the Himalayan range in central Nepal. This includes daily sampling of suspended sediments of the Narayani river and of one small south flank catchment. Combined hydroxyl concentration [H2O+] and δD analyses were performed on H2 using EA-IRMS coupling an adequate sample preparation and introduction to prevent air moisture contamination. Because H2 is a mixture between hydroxyl and H form organic matter (OM), OM were removed by oxidation in a cold oxygen plasma. This treatment allows to successfully remove organic hydrogen, which is especially important for soils as it can represent 10 times H present in silicate hydroxyls. Because [H2O+] is primarily controlled by the relative abundance of minerals, especially quartz and micas, we compare our data by normalizing to Si and Al. Source rocks define simple correlations between Al/Si and H2O+/Si indicating steady H2O+/Al ratios that depends on geological formations. Soils show very high and variable hydration that is consistent with high weathering intensity. Landslide and glacier sediments only show modest hydration relative to source rocks. River sediments have H2O+/Al ratios increasing with Al/Si indicating that aluminous (i.e. fine grain sediments) are more hydrated or weathered than coarse grain sediments. Secondary hydration typically varies from 0% for sandy bed sediment to ~50% of initial water content for fine suspended sediment. δD data of south flank source rocks, soils and rivers sediments are quite identical around -80 to -90‰ and appear independent of

  4. Chlorine Abundances in Martian Meteorites

    NASA Technical Reports Server (NTRS)

    Bogard, D.D.; Garrison, D.H.; Park, J.

    2009-01-01

    Chlorine measurements made in martian surface rocks by robotic spacecraft typically give Chlorine (Cl) abundances of approximately 0.1-0.8%. In contrast, Cl abundances in martian meteorites appear lower, although data is limited, and martian nakhlites were also subjected to Cl contamination by Mars surface brines. Chlorine abundances reported by one lab for whole rock (WR) samples of Shergotty, ALH77005, and EET79001 range 108-14 ppm, whereas Cl in nakhlites range 73-1900 ppm. Measurements of Cl in various martian weathering phases of nakhlites varied 0.04-4.7% and reveal significant concentration of Cl by martian brines Martian meteorites contain much lower Chlorine than those measured in martian surface rocks and give further confirmation that Cl in these surface rocks was introduced by brines and weathering. It has been argued that Cl is twice as effective as water in lowering the melting point and promoting melting at shallower martian depths, and that significant Cl in the shergottite source region would negate any need for significant water. However, this conclusion was based on experiments that utilized Cl concentrations more analogous to martian surface rocks than to shergottite meteorites, and may not be applicable to shergottites.

  5. The Bliss of Motor Abundance

    PubMed Central

    Latash, Mark L.

    2012-01-01

    Motor control is an area of natural science exploring how the nervous system interacts with other body parts and the environment to produce purposeful, coordinated actions. A central problem of motor control – the problem of motor redundancy – was formulated by Nikolai Bernstein as the problem of elimination of redundant degrees-of-freedom. Traditionally, this problem has been addressed using optimization methods based on a variety of cost functions. This review draws attention to a body of recent findings suggesting that the problem has been formulated incorrectly. An alternative view has been suggested as the principle of abundance, which considers the apparently redundant degrees-of-freedom as useful and even vital for many aspects of motor behavior. Over the past ten years, dozens of publications have provided support for this view based on the ideas of synergic control, computational apparatus of the uncontrolled manifold hypothesis, and the equilibrium-point (referent configuration) hypothesis. In particular, large amounts of “good variance” – variance in the space of elements that has no effect on the overall performance – have been documented across a variety of natural actions. “Good variance” helps an abundant system to deal with secondary tasks and unexpected perturbations; its amount shows adaptive modulation across a variety of conditions. These data support the view that there is no problem of motor redundancy; there is bliss of motor abundance. PMID:22246105

  6. 4'-hydroxylation of flurbiprofen by rat liver microsomes in fasting and feeding conditions.

    PubMed

    Shimizu, Makiko; Matsushita, Reiko; Matsumoto, Yoshiaki; Fukuoka, Masamichi

    2003-10-01

    We examined the 4'-hydroxylation of flurbiprofen in rat hepatocytes and liver microsomes in order to know whether the metabolism of flurbiprofen is changed on its administration to experimental animals after overnight fasting, because starvation and fasting change both the composition of cytochrome P450s (CYPs) and metabolic activity. CYPs involved in the hydroxylation were determined by various CYP inhibitors and inhibitory antibodies against rat CYP2C11 and CYP2E1 using the microsomes in fasting and feeding. The results provided a possibiliy that the 4'-hydroxylation might be regulated by CYP2C11, but not by CYP2E1, at fasting rather than feeding.

  7. Stellar abundances in the solar neighborhood: The Hypatia Catalog

    SciTech Connect

    Hinkel, Natalie R.; Timmes, F.X.; Young, Patrick A.; Pagano, Michael D.; Turnbull, Margaret C.

    2014-09-01

    We compile spectroscopic abundance data from 84 literature sources for 50 elements across 3058 stars in the solar neighborhood, within 150 pc of the Sun, to produce the Hypatia Catalog. We evaluate the variability of the spread in abundance measurements reported for the same star by different surveys. We also explore the likely association of the star within the Galactic disk, the corresponding observation and abundance determination methods for all catalogs in Hypatia, the influence of specific catalogs on the overall abundance trends, and the effect of normalizing all abundances to the same solar scale. The resulting stellar abundance determinations in the Hypatia Catalog are analyzed only for thin-disk stars with observations that are consistent between literature sources. As a result of our large data set, we find that the stars in the solar neighborhood may reveal an asymmetric abundance distribution, such that a [Fe/H]-rich group near the midplane is deficient in Mg, Si, S, Ca, Sc II, Cr II, and Ni as compared to stars farther from the plane. The Hypatia Catalog has a wide number of applications, including exoplanet hosts, thick- and thin-disk stars, and stars with different kinematic properties.

  8. The Abundance of Interstellar Fluorine

    NASA Technical Reports Server (NTRS)

    Lauroesch, James T.

    2005-01-01

    The primary objective of this program was to obtain FUSE observations of the interstellar absorption lines of F I at 951 and 954 Angstroms to derive the abundance of fluorine toward the star HD 164816. The nucleosynthetic source(s) of fluorine are still a matter of debate - the present day abundance of fluorine can potentially constrain models for pulsationally driven dredge-up in asymptotic giant branch stars. An accurate measure for the depletion behavior of fluorine will determine whether it may be detectable in QSO absorption line systems - an unambiguous detection of fluorine at suitably high redshifts would provide the best evidence to date for the neutrino process in massive stars. Furthermore, due to its extreme reactivity, measurement of the gas-phase interstellar fluorine abundance is important for models of grain chemistry. Despite the importance of measuring the interstellar fluorine abundance, at the time of our proposal only one previous detection has been made due to the low relative abundance of fluorine, the lack of lines outside the far-UV, and the blending of the available F I transitions with lines of Hz. The star HD 164816 is associated with the Lagoon nebula (M8), and at a distance of approximately 1.5 kpc probes both distant and local gas. Beginning April 8th, 2004 FUSE FP-Split observations of the star HD 164816 were obtained for this program. This data became available in the FUSE data archive May 21, 2004, and these observations were then downloaded and we began our analysis. Our analysis procedure has involved (1) fitting stellar models to the FUSE spectra, (2) using the multiple lines of Hz and N I at other wavelengths in the FUSE bandpass to derive column densities for the lines of H2 and N I which are blended with the F I features at 951 and 954 angstroms (3) the measurement of the column densities of F I and the species O I and C1 I which are important species for the dis-entangling of dust and nucleosynthetic effects. As discussed in

  9. Endogenous 3, 4- Dihydroxyphenylalanine and Dopaquinone Modifications on Protein Tyrosine: links to mitochondrially derived oxidative stress via hydroxyl radical

    SciTech Connect

    Zhang, Xu; Monroe, Matthew E.; Chen, Baowei; Chin, Mark H.; Heibeck, Tyler H.; Schepmoes, Athena A.; Yang, Feng; Petritis, Brianne O.; Camp, David G.; Pounds, Joel G.; Jacobs, Jon M.; Smith, Desmond J.; Bigelow, Diana J.; Smith, Richard D.; Qian, Weijun

    2010-06-02

    Oxidative modifications of protein tyrosines have been implicated in multiple human diseases. Among these modifications, elevations in levels of 3, 4-dihydroxyphenylalanine (DOPA), a major product of hydroxyl radical addition to tyrosine, has been observed in a number of pathologies. Here we report the first global proteome survey of endogenous site-specific modifications, i.e, DOPA and its further oxidation product dopaquinone (DQ) in mouse brain and heart tissues. Results from LC-MS/MS analyses included 203 and 71 DOPA-modified tyrosine sites identified from brain and heart, respectively, with a false discovery rate of ~1%; while only a few nitrotyrosine containing peptides, a more commonly studied marker of oxidative stress, were detectable, suggesting the much higher abundance for DOPA modification as compared with tyrosine nitration. Moreover, 57 and 29 DQ modified peptides were observed from brain and heart, respectively; nearly half of these peptides were also observed with DOPA modification on the same sites. For both tissues, these modifications are preferentially found in mitochondrial proteins with metal-binding properties, consistent with metal catalyzed hydroxyl radical formation from mitochondrial superoxide and hydrogen peroxide. These modifications also link to a number of mitochondria-associated and other signaling pathways. Furthermore, many of the modification sites were common sites of previously reported tyrosine phosphorylation suggesting potential disruption of signaling pathways. Structural aspects of DOPA-modified tyrosine sequences are distinct from those of nitrotyrosines suggesting that each type of modifications provides a marker for different in vivo reactive chemistries and can be used to predict sensitive protein targets. Collectively, the results suggest that these modifications are linked with mitochondrially-derived oxidative stress, and may serve as sensitive markers for disease pathologies.

  10. Hydroxyl layer: Mean state and trends at midlatitudes

    NASA Astrophysics Data System (ADS)

    Grygalashvyly, M.; Sonnemann, G. R.; Lübken, F.-J.; Hartogh, P.; Berger, U.

    2014-11-01

    Based on an advanced model of excited hydroxyl relaxation we calculate trends of number densities and altitudes of the OH*-layer during the period 1961-2009. The OH*-model takes into account all major chemical processes such as the production by H + O3, deactivation by O, O2, and N2, spontaneous emission, and removal by chemical reactions. The OH*-model is coupled with a chemistry-transport model (CTM). The dynamical part (Leibniz Institute Model of the Atmosphere, LIMA) adapts ECMWF/ERA-40 data in the troposphere-stratosphere. The change of greenhouse gases (GHGs) such as CH4, CO2, O3, and N2O is parameterized in LIMA/CTM. The downward shift of the OH*-layer in geometrical altitudes occurs entirely due to shrinking (mainly in the mesosphere) as a result of cooling by increasing CO2 concentrations. In order to identify the direct chemical effect of GHG changes on OH*-trends under variable solar cycle conditions, we consider three cases: (a) variable GHG and Lyman-α fluxes, (b) variable GHG and constant Lyman-α fluxes, and (c) constant GHG and Lyman-α. At midlatitudes, shrinking of the middle atmosphere descends the OH*-layer by ~ -300 m/decade in all seasons. The direct chemical impact of GHG emission lifts up the OH*-layer by ~15-25 m/decade depending on season. Trends of the thermal and dynamical state within the layer lead to a trend of OH* height by ~ ±100 m/decade, depending on latitude and season. Trends in layer altitudes lead to differences between temperature trends within the layer, at constant pressure, and at constant altitude, respectively, of typically 0.5 to 1 K/decade.

  11. CYP2E1 hydroxylation of aniline involves negative cooperativity.

    PubMed

    Hartman, Jessica H; Knott, Katie; Miller, Grover P

    2014-02-01

    CYP2E1 plays a role in the metabolic activation and elimination of aniline, yet there are conflicting reports on its mechanism of action, and hence relevance, in aniline metabolism. Based on our work with similar compounds, we hypothesized that aniline binds two CYP2E1 sites during metabolism resulting in cooperative reaction kinetics and tested this hypothesis through rigorous in vitro studies. The kinetic profile for recombinant CYP2E1 demonstrated significant negative cooperativity based on a fit of data to the Hill equation (n=0.56). Mechanistically, the data were best explained through a two-binding site cooperative model in which aniline binds with high affinity (K(s)=30 μM) followed by a second weaker binding event (K(ss)=1100 uM) resulting in a threefold increase in the oxidation rate. Binding sites for aniline were confirmed by inhibition studies with 4-methylpyrazole. Inhibitor phenotyping experiments with human liver microsomes validated the central role for CYP2E1 in aniline hydroxylation and indicated minor roles for CYP2A6 and CYP2C9. Importantly, inhibition of minor metabolic pathways resulted in a kinetic profile for microsomal CYP2E1 that replicated the preferred mechanism and parameters observed with the recombinant enzyme. Scaled modeling of in vitro CYP2E1 metabolism of aniline to in vivo clearance, especially at low aniline levels, led to significant deviations from the traditional model based on non-cooperative, Michaelis-Menten kinetics. These findings provide a critical mechanistic perspective on the potential importance of CYP2E1 in the metabolic activation and elimination of aniline as well as the first experimental evidence of a negatively cooperative metabolic reaction catalyzed by CYP2E1.

  12. BIOLUMINESCENCE INHIBITION ASSAY FOR THE DETECTION OF HYDROXYLATED POLYCHLORINATED BIPHENYLS

    PubMed Central

    Hamorsky, Krystal Teasley; Ensor, C. Mark; Dikici, Emre; Pasini, Patrizia; Bachas, Leonidas; Daunert, Sylvia

    2012-01-01

    Hydroxylated polychlorinated biphenyls (OH-PCBs) are an important class of contaminants that mainly originate from polychlorinated biphenyl metabolism. They may conceivably be as dangerous and persistent as the parent compounds; most prominently, OH-PCBs are endocrine disruptors. Due to increasing evidence of the presence of OH-PCBs in the environment and in living organisms, including humans, and of their toxicity, methods of detection for OH-PCBs are needed in the environmental and medical fields. Herein we describe the development and optimization of a protein+based inhibition assay for the quantification of OH-PCBs. Specifically, the photoprotein aequorin was utilized for the detection of OH-PCBs. We hypothesized that OH-PCBs interact with aequorin and we established that OH-PCBs actually inhibit the bioluminescence of aequorin in a dose-dependent manner. We took advantage of this phenomenon to develop an assay that is capable of detecting a wide variety of OH-PCBs with a range of detection limits, the best detection limit being 11 nM for the compound 2-hydroxy-2',3,4',5',6-pentachorobiphenyl. The viability of this system for the screening of OH-PCBs in spiked biological and environmental samples was also established. We envision the implementation of this novel bioluminescence inhibition assay as a rapid, sensitive and cost-effective method for monitoring OH-PCBs. Furthermore, to the best of our knowledge this is the first time aequorin has been employed to detect an analyte by the inhibition of its bioluminescence reaction. Hence, this strategy may prove to be a general approach for the development of a new generation of protein-based inhibition assays. PMID:22908962

  13. Photocatalytic oxidation of arsenic(III): evidence of hydroxyl radicals.

    PubMed

    Dutta, Paritam K; Pehkonen, S O; Sharma, Virender K; Ray, Ajay K

    2005-03-15

    Arsenic contamination has been found in the groundwater of several countries. Photocatalysis can rapidly oxidize arsenite (As(III)) to less labile and less toxic arsenate (As(V)), which then can be removed by adsorption onto photocatalyst surfaces. This study investigates the photocatalytic oxidation of As(III) to As(V) as a function of As(III) concentration, pH, catalyst loading, light intensity, dissolved oxygen concentration, type of TiO2 surfaces, and ferric ions to understand the kinetics and the mechanism of As(III) oxidation in the UV/TiO2 system. Photocatalytic oxidation of As(III) to As(V) takes place in minutes and follows zero-order kinetics. Benzoic acid (BA) was used as a hydroxyl radical (.OH) scavenger to provide evidence for the .OH as the main oxidant for oxidation of As(III). The .OH radical was independently generated by nitrate photolysis, and kinetics of As(III) oxidation by the .OH radical was determined. Formation of salicylic acid (SA) from the oxidation of BA by .OH also demonstrates the involvement of .OH in the mechanism of As(III) oxidation. The effect of Fe(III) on As(III) oxidation at different pH values with and without TiO2 under UV light was examined. The results suggest that .OH is the dominant oxidant for As(III) oxidation. Two commercially available TiO2 suspensions, Degussa P25 and Hombikat UV100, were tested for the removal of arsenic through oxidation of As(III) to As(V) followed by adsorption of As(V) onto TiO2 surfaces. Results showed that complete removal of arsenic below the World Health Organization drinking water limit of 10 microg/L could be achieved.

  14. Development of Hydroxyl Tagging Velocimetry for Low Velocity Flows

    NASA Technical Reports Server (NTRS)

    Andre, Matthieu A.; Bardet, Philippe M.; Burns, Ross A.; Danehy, Paul M.

    2016-01-01

    Hydroxyl tagging velocimetry (HTV) is a molecular tagging technique that relies on the photo-dissociation of water vapor into OH radicals and their subsequent tracking using laser induced fluorescence. Velocities are then obtained from time-of-flight calculations. At ambient temperature in air, the OH species lifetime is relatively short (<50 µs), making it suited for high speed flows. Lifetime and radicals formation increases with temperature, which allows HTV to also probe low-velocity, high-temperature flows or reacting flows such as flames. The present work aims at extending the domain of applicability of HTV, particularly towards low-speed (<10 m/s) and moderate (<500 K) temperature flows. Results are compared to particle image velocimetry (PIV) measurements recorded in identical conditions. Single shot and averaged velocity profiles are obtained in an air jet at room temperature. By modestly raising the temperature (100-200 degC) the OH production increases, resulting in an improvement of the signal-to-noise ratio (SNR). Use of nitrogen - a non-reactive gas with minimal collisional quenching - extends the OH species lifetime (to over 500 µs), which allows probing of slower flows or, alternately, increases the measurement precision at the expense of spatial resolution. Instantaneous velocity profiles are resolved in a 100degC nitrogen jet (maximum jet-center velocity of 6.5 m/s) with an uncertainty down to 0.10 m/s (1.5%) at 68% confidence level. MTV measurements are compared with particle image velocimetry and show agreement within 2%.

  15. Protective effects of hydroxybenzoic acids and their esters on cell damage induced by hydroxyl radicals and hydrogen peroxides.

    PubMed

    Masaki, H; Okamoto, N; Sakaki, S; Sakurai, H

    1997-04-01

    The purpose of this study was to evaluate the hydroxyl radical scavenging activities of hydroxybenzoic acids and their esters from both chemical and biological aspects. These activities of hydroxybenzoic acids and their related compounds were estimated by ESR-spin trapping method, in which 3,4,5-trihydroxybenzoic acid and its ethyl and propyl esters showed the highest activities as estimated by IC50 value (50% inhibition concentration of hydroxyl radicals generated in the system): 78.04 +/- 11.23, 95.95 +/- 2.64, and 86.46 +/- 2.31 microM, respectively. In addition, 3,4,5-trihydroxybenzoic acid (gallic acid) at a concentration of 25 microM, protected against dermal fibroblast cell damage induced by H2O2, and enhanced the survival to 83.8 +/- 3.1%, in which the survival of control was 44.2 +/- 1.0%. Based on these results, the pretreatment effects of 3,4,5-trihydroxybenzoic acid n-alkyl esters on cell damage induced by H2O2 were examined. The survival of fibroblasts pretreated with the esters increased depending on the alkyl chain-length. Both C12 and C16 alkyl esters gave almost complete cell survival of 89.5 +/- 2.0% and 91.3 +/- 1.0%, respectively. The order of the protective effects of the compounds was in good agreement with that of their partition coefficients, suggesting that 3,4,5-trihydroxybenzoic acid alkyl esters are incorporated into fibroblasts, and thus prevent the cells from the toxicity caused by H2O2. In addition, an increase of intracellular peroxide formation in fibroblasts induced by UVA-irradiation, was suppressed to 2.27 +/- 0.41 nmol/10(4) cells by pretreatment with C16 alkyl ester at a concentration of 25 microM. Since 3,4,5-trihydroxybenzoic group has been demonstrated to possess a potent scavenging activity of hydroxyl radicals, this moiety was indicated to be important in preventing cell damage induced by UVA or H2O2: in turn, these produce hydroxyl radicals in the presence of trace metal ions such as iron and copper in cells.

  16. Density functional study of the adsorption of aspirin on the hydroxylated (0 0 1) α-quartz surface

    NASA Astrophysics Data System (ADS)

    Abbasi, A.; Nadimi, E.; Plänitz, P.; Radehaus, C.

    2009-08-01

    In this study the adsorption geometry of aspirin molecule on a hydroxylated (0 0 1) α-quartz surface has been investigated using DFT calculations. The optimized adsorption geometry indicates that both, adsorbed molecule and substrate are strongly deformed. Strong hydrogen bonding between aspirin and surface hydroxyls, leads to the breaking of the original hydroxyl-hydroxyl hydrogen bonds (Hydrogenbridges) on the surface. In this case new hydrogen bonds on the hydroxylated (0 0 1) α-quartz surface appear which significantly differ from those at the clean surface. The 1.11 eV adsorption energy reveals that the interaction of aspirin with α-quartz is an exothermic chemical interaction.

  17. Atmospheric Hydroxyl Radical Production from Electronically Excited NO2 and H2O

    NASA Astrophysics Data System (ADS)

    Li, Shuping; Matthews, Jamie; Sinha, Amitabha

    2008-03-01

    Hydroxyl radicals are often called the “detergent” of the atmosphere because they control the atmosphere’s capacity to cleanse itself of pollutants. Here, we show that the reaction of electronically excited nitrogen dioxide with water can be an important source of tropospheric hydroxyl radicals. Using measured rate data, along with available solar flux and atmospheric mixing ratios, we demonstrate that the tropospheric hydroxyl contribution from this source can be a substantial fraction (50%) of that from the traditional O(1D) + H2O reaction in the boundary-layer region for high solar zenith angles. Inclusion of this chemistry is expected to affect modeling of urban air quality, where the interactions of sunlight with emitted NOx species, volatile organic compounds, and hydroxyl radicals are central in determining the rate of ozone formation.

  18. Polar transition states in reactions of aromatic hydrocarbons with hydroxyl radicals

    SciTech Connect

    Vysotskaya, N.A.; Rekasheva, A.F.; Bortun, L.N.

    1986-07-01

    The mechanism of formation of radical adducts in the radical hydroxylation of aromatic hydrocarbons has been investigated. The analysis of correlations between the logarithms of the rate constants of the radical hydroxylation of substituted benzenes, naphthalenes, and condensed hydrocarbons in aqueous solutions and the sigma/sup +/ constants of the substituents, the ionization potentials, the localization energies of the arenes, and also the quantum-chemical calculations of the surfaces of potential energies of the hydroxylation of benzene and naphthalene leads to the conclusion that an ion pair in the excited state, formed by the cation radical of the hydrocarbon and the hydroxyl anion, can serve as the model for the transition states of the above-mentioned reactions. A decrease in the ionization potential of the arene leads to an increase in the coulombic interaction in this pair, to its stabilization, and to an increase in the reaction rate.

  19. Binding of hydroxylated single-walled carbon nanotubes to two hemoproteins, hemoglobin and myoglobin.

    PubMed

    Wang, Yan-Qing; Zhang, Hong-Mei; Cao, Jian

    2014-12-01

    Herein, we studied the binding interactions between hydroxylated single-walled carbon nanotubes and hemoglobin and myoglobin by the use of multi-spectral techniques and molecular modeling. The ultraviolet-vis absorbance and circular dichroism spectral results indicated that the binding interactions existed between hydroxylated single-walled carbon nanotubes and hemoglobin/myoglobin. These binding interactions partially affected the soret/heme bands of hemoglobin and myoglobin. The secondary structures of hemoproteins were partially destroyed by hydroxylated single-walled carbon nanotubes. Fluorescence studies suggested that the complexes formed between hydroxylated single-walled carbon nanotubes and hemoglobin/myoglobin by hydrogen bonding, hydrophobic, and π-π stacking interactions. In addition, molecular modeling analysis well supported the experimental results.

  20. Crucial enzymes in the hydroxylated triacylglycerol-ricinoleate biosynthesis pathway of castor bean.

    PubMed

    Chen, Yujie; Liu, Lili; Tian, Xun; Di, Jianjun; Su, Yalatu; Huang, Fenglan; Chen, Yongsheng

    2014-01-01

    Castor bean (Ricinus communis L.) is an important oilseed crop for the rich hydroxylated triacylglycerol (TAG)-ricinoleate which is a raw material with wide applications in industry. Hydroxylated TAG synthesis occurs through complicated pathways among multiple subcellular organelles. Some crucial enzymes have been identified in previous studies. After analyzing the available castor tissue-specific transcriptome sequencing data and comparing the classic pathways in other plants, a possible de novo biosynthesis pathway for the hydroxylated TAG has been revealed. In this study, some other crucial enzymes were ascertained and their expression levels were characterized and pinpointed into the pathways in castor. Several key enzymes were analyzed in terms of structure, biofunction prediction and similarity of expression pattern mechanisms, aiming to give an insight on the better understandings of the molecular knowledge for this oil-rich plant and the crucial enzyme performances in the hydroxylated triacylglycerol-ricinoleate biosynthesis pathways.

  1. A new, simple approach to confer permanent antimicrobial properties to hydroxylated surfaces by surface functionalization.

    PubMed

    Bouloussa, Othman; Rondelez, Francis; Semetey, Vincent

    2008-02-28

    A new, simple method to obtain ultrathin polycationic monolayers on hydroxylated surfaces is described which uses a bifunctional copolymer comprising a reactive part (trimethoxysilane) and positive charges (quaternary ammonium salts) to confer antimicrobial properties.

  2. A soluble Bacillus cereus cytochrome P-450cin system catalyzes 1,4-cineole hydroxylations.

    PubMed Central

    Liu, W; Rosazza, J P

    1993-01-01

    A cytochrome P-450-dependent monooxygenase system that catalyzes the stereospecific hydroxylation of the monoterpene substrate 1,4-cineole was demonstrated in cell-free preparations of Bacillus cereus UI-1477. 1,4-Cineole hydroxylations were catalyzed by a 100,000 x g (1-h)-centrifuging soluble, hexane-inducible enzyme that activated and incorporated molecular oxygen into hydroxylated products; required NADH; was inhibited by SKF-525A, imidazole, metyrapone, and octylamine; and displayed a 452-nm peak in the carbon monoxide difference absorption spectrum. The constant 7:1 ratio of endo/exo alcohol products formed when 1,4-cineole was hydroxylated by normal cells, hexane-induced cells, and cell extracts suggested that a single enzyme designated cytochrome P-450cin was responsible for both reactions. PMID:8285692

  3. Atmospheric hydroxyl radical production from electronically excited NO2 and H2O.

    PubMed

    Li, Shuping; Matthews, Jamie; Sinha, Amitabha

    2008-03-21

    Hydroxyl radicals are often called the "detergent" of the atmosphere because they control the atmosphere's capacity to cleanse itself of pollutants. Here, we show that the reaction of electronically excited nitrogen dioxide with water can be an important source of tropospheric hydroxyl radicals. Using measured rate data, along with available solar flux and atmospheric mixing ratios, we demonstrate that the tropospheric hydroxyl contribution from this source can be a substantial fraction (50%) of that from the traditional O(1D) + H2O reaction in the boundary-layer region for high solar zenith angles. Inclusion of this chemistry is expected to affect modeling of urban air quality, where the interactions of sunlight with emitted NOx species, volatile organic compounds, and hydroxyl radicals are central in determining the rate of ozone formation.

  4. Influence of hydroxyl content on selected properties of 45S5 bioactive glass.

    PubMed

    Hall, Matthew M

    2007-12-01

    Numerous material properties may be influenced by the concentration of chemically dissolved hydroxyl species within a glass. A tube furnace connected to a steam generator was used to create hydroxyl-saturated 45S5 glass under 1 atm of water at 1100 degrees C. Selected properties of as-melted and hydroxyl-saturated samples were compared to assess the sensitivity of 45S5 to excess hydroxylation. The glass transition temperature and the peak crystallization temperature of the treated 45S5 glass were reduced in comparison to the as-melted 45S5 glass. In addition, the treated glass exhibited a broad endothermic signal that may be indicative of enhanced viscous flow. A simple dissolution experiment indicated that the treated 45S5 glass was also less durable than the as-melted 45S5 glass. PMID:17559121

  5. Observation of temperature dependence of the IR hydroxyl absorption bands in silica optical fiber

    NASA Astrophysics Data System (ADS)

    Yu, Li; Bonnell, Elizabeth; Homa, Daniel; Pickrell, Gary; Wang, Anbo; Ohodnicki, P. R.; Woodruff, Steven; Chorpening, Benjamin; Buric, Michael

    2016-07-01

    This study reports on the temperature dependent behavior of silica based optical fibers upon exposure to high temperatures in hydrogen and ambient air. The hydroxyl absorption bands in the wavelength range of 1000-2500 nm of commercially available multimode fibers with pure silica and germanium doped cores were examined in the temperature range of 20-800 °C. Two hydroxyl-related infrared absorption bands were observed: ∼2200 nm assigned to the combination of the vibration mode of Si-OH bending and the fundamental hydroxyl stretching mode, and ∼1390 nm assigned to the first overtone of the hydroxyl stretching. The absorption in the 2200 nm band decreased in intensity, while the 1390 nm absorption band shifted to longer wavelengths with an increase in temperature. The observed phenomena were reversible with temperature and suspected to be due, in part, to the conversion of the OH spectral components into each other and structural relaxation.

  6. Atmospheric hydroxyl radical production from electronically excited NO2 and H2O.

    PubMed

    Li, Shuping; Matthews, Jamie; Sinha, Amitabha

    2008-03-21

    Hydroxyl radicals are often called the "detergent" of the atmosphere because they control the atmosphere's capacity to cleanse itself of pollutants. Here, we show that the reaction of electronically excited nitrogen dioxide with water can be an important source of tropospheric hydroxyl radicals. Using measured rate data, along with available solar flux and atmospheric mixing ratios, we demonstrate that the tropospheric hydroxyl contribution from this source can be a substantial fraction (50%) of that from the traditional O(1D) + H2O reaction in the boundary-layer region for high solar zenith angles. Inclusion of this chemistry is expected to affect modeling of urban air quality, where the interactions of sunlight with emitted NOx species, volatile organic compounds, and hydroxyl radicals are central in determining the rate of ozone formation. PMID:18356524

  7. Hydroxylated analogs of mexiletine as tools for structural-requirements investigation of the sodium channel blocking activity.

    PubMed

    Catalano, Alessia; Carocci, Alessia; Cavalluzzi, Maria M; Di Mola, Antonia; Lentini, Giovanni; Lovece, Angelo; Dipalma, Antonella; Costanza, Teresa; Desaphy, Jean-François; Conte Camerino, Diana; Franchini, Carlo

    2010-06-01

    [2-(2-Aminopropoxy)-1,3-phenylene]dimethanol 1 and 4-(2-aminopropoxy)-3-(hydroxymethyl)-5-methylphenol 2, two dihydroxylated analogs of mexiletine - a well known class IB anti-arrhythmic drug - were synthesized and used as pharmacological tools to investigate the blocking-activity requirements of human skeletal muscle, voltage-gated sodium channel. The very low blocking activity shown by newly synthesized compounds corroborates the hypothesis that the presence of a phenolic group in the para-position to the aromatic moiety and/or benzylic hydroxyl groups on the aromatic moiety of local anesthetic-like drugs impairs either the transport to or the interaction with the binding site in the pore of Na(+) channels. PMID:20509146

  8. The solar abundance of Oxygen

    NASA Astrophysics Data System (ADS)

    Grevesse, N.

    2009-07-01

    With Martin Asplund (Max Planck Institute of Astrophysics, Garching) and Jacques Sauval (Observatoire Royal de Belgique, Brussels) I recently published detailed reviews on the solar chemical composition ({Asplund et al. 2005}, {Grevesse et al. 2007}). A new one, with Pat Scott (Stockholm University) as additional co-author, will appear in Annual Review of Astronomy and Astrophysics ({Asplund et al. 2009}). Here we briefly analyze recent works on the solar abundance of Oxygen and recommend a value of 8.70 in the usual astronomical scale.

  9. Abundance measurements in stellar environments

    NASA Astrophysics Data System (ADS)

    Leone, F.

    2014-05-01

    Most of what we know about stars, and systems of stars, is derived from the analysis of their electromagnetic radiation. This lesson is an attempt to describe to Physicists, without any Astrophysical background, the framework to understand the present status of abundance determination in stellar environments and its limit. These notes are dedicated to the recently passed, November 21, 2013, Prof. Dimitri Mihalas who spent his life confuting the 19th century positivist philosopher Auguste Comte who stated that we shall not at all be able to determine the chemical composition of stars.

  10. Abundance measurements in stellar environments

    SciTech Connect

    Leone, F.

    2014-05-09

    Most of what we know about stars, and systems of stars, is derived from the analysis of their electromagnetic radiation. This lesson is an attempt to describe to Physicists, without any Astrophysical background, the framework to understand the present status of abundance determination in stellar environments and its limit. These notes are dedicated to the recently passed, November 21, 2013, Prof. Dimitri Mihalas who spent his life confuting the 19th century positivist philosopher Auguste Comte who stated that we shall not at all be able to determine the chemical composition of stars.

  11. Cooperation between bound waters and hydroxyls in controlling isotope-exchange rates

    NASA Astrophysics Data System (ADS)

    Panasci, Adele F.; McAlpin, J. Gregory; Ohlin, C. André; Christensen, Shauna; Fettinger, James C.; Britt, R. David; Rustad, James R.; Casey, William H.

    2012-02-01

    Mineral oxides differ from aqueous ions in that the bound water molecules are usually attached to different metal centers, or vicinal, and thus separated from one another. In contrast, for most monomeric ions used to establish kinetic reactivity trends, such as octahedral aquo ions (e.g., Al(H 2O) 63+), the bound waters are closely packed, or geminal. Because of this structural difference, the existing literature about ligand substitution in monomer ions may be a poor guide to the reactions of geochemical interest. To understand how coordination of the reactive functional groups might affect the rates of simple water-exchange reactions, we synthesized two structurally similar Rh(III) complexes, [Rh(phen) 2(H 2O) 2] 3+ [ 1] and [Rh(phen) 2(H 2O)Cl] 2+ [ 2] where (phen) = 1,10-phenanthroline. Complex [ 1] has two adjacent, geminal, bound waters in the inner-coordination sphere and [ 2] has a single bound water adjacent to a bound chloride ion. We employed Rh(III) as a trivalent metal rather than a more geochemically relevant metal like Fe(III) or Al(III) to slow the rate of reaction, which makes possible measurement of the rates of isotopic substitution by simple mass spectrometry. We prepared isotopically pure versions of the molecules, dissolved them into isotopically dissimilar water, and measured the rates of exchange from the extents of 18O and 16O exchange at the bound waters. The pH dependency of rates differ enormously between the two complexes. Pseudo-first-order rate coefficients at 298 K for water exchanges from the fully protonated molecules are close: k0298 = 5 × 10 -8(±0.5 × 10 -8) s -1 for [ 1] and k0298 = 2.5 × 10 -9(±1 × 10 -9) for [ 2]. Enthalpy and entropy activation parameters (Δ H‡ and Δ S‡) were measured to be 119(±3) kJ mol -1, and 14(±1) J mol -1 K -1, respectively for [ 1]. The corresponding parameters for the mono-aquo complex, [ 2], are 132(±3) kJ mol -1 and 41.5(±2) J mol -1 K -1. Rates increase by many orders of magnitude

  12. Hydroxyl radical reactions with adenine: reactant complexes, transition states, and product complexes.

    PubMed

    Cheng, Qianyi; Gu, Jiande; Compaan, Katherine R; Schaefer, Henry F

    2010-10-18

    In order to address problems such as aging, cell death, and cancer, it is important to understand the mechanisms behind reactions causing DNA damage. One specific reaction implicated in DNA oxidative damage is hydroxyl free-radical attack on adenine (A) and other nucleic acid bases. The adenine reaction has been studied experimentally, but there are few theoretical results. In the present study, adenine dehydrogenation at various sites, and the potential-energy surfaces for these reactions, are investigated theoretically. Four reactant complexes [A···OH]* have been found, with binding energies relative to A+OH* of 32.8, 11.4, 10.7, and 10.1 kcal mol(-1). These four reactant complexes lead to six transition states, which in turn lie +4.3, -5.4, (-3.7 and +0.8), and (-2.3 and +0.8) kcal mol(-1) below A+OH*, respectively. Thus the lowest lying [A···OH]* complex faces the highest local barrier to formation of the product (A-H)*+H(2)O. Between the transition states and the products lie six product complexes. Adopting the same order as the reactant complexes, the product complexes [(A-H)···H(2)O]* lie at -10.9, -22.4, (-24.2 and -18.7), and (-20.5 and -17.5) kcal mol(-1), respectively, again relative to separated A+OH*. All six A+OH* → (A-H)*+H(2)O pathways are exothermic, by -0.3, -14.7, (-17.4 and -7.8), and (-13.7 and -7.8) kcal mol(-1), respectively. The transition state for dehydrogenation at N(6) lies at the lowest energy (-5.4 kcal mol(-1) relative to A+OH*), and thus reaction is likely to occur at this site. This theoretical prediction dovetails with the observed high reactivity of OH radicals with the NH(2) group of aromatic amines. However, the high barrier (37.1 kcal mol(-1)) for reaction at the C(8) site makes C(8) dehydrogenation unlikely. This last result is consistent with experimental observation of the imidazole ring opening upon OH radical addition to C(8). In addition, TD-DFT computed electronic transitions of the N(6) product around 420 nm

  13. Atropisomeric determination of chiral hydroxylated metabolites of polychlorinated biphenyls using HPLC-MS

    PubMed Central

    2013-01-01

    Background Polychlorinated biphenyls (PCBs) are a group of environmental persistent organic pollutants, which can be metabolized into a series of metabolites, including hydroxylated metabolites (OH-PCBs) in biota. Nineteen of 209 PCB congeners can form chiral stable isomers. However, atropisomeric determination of the hydroxylated metabolites of these chiral PCBs has never been reported by LC methods. In this work, a novel HPLC-MS method was developed to detect five chiral OH-PCBs (4OH-PCB91, 5OH-PCB91, 4OH-PCB95, 5OH-PCB95 and 5OH-PCB149) using HPLC-MS without a derivatization step. Results The influences of column-type, column temperature, flow rate and ratio of the mobile phase on the atropisomeric separation were investigated in detail. In the final method, calibration curves, based on peak areas against concentration, were linear in a range of 1–100 ng mL-1 of five chiral OH-PCBs with correlation coefficients ranging from 0.9996 to 0.9999 for all atropisomers of OH-PCBs. The relative standard deviations measured at the 10.0 ng mL-1 level for atropisomers of five chiral OH-PCBs were in the range of 0.60-7.55% (n = 5). Calculated detection limits (S/N = 3) of five chiral OH-PCBs were between 0.31 and 0.60 ng mL-1 for all OH-PCB atropisomers. Conclusion This HPLC-MS method was developed to detect chiral OH-PCBs and further successfully applied to measure OH-PCB atropisomer levels and enantiomeric fractions (EFs) in rat liver microsomal samples. The results from LC-MS method were highly consistent with those from GC-ECD method. It is the first time to report these OH-PCB atropisomers detected in microsomes by HPLC-MS. The proposed method might be applied also to detect chiral OH-PCBs in environmental samples and for metabolites of PCBs in vivo. PMID:24360245

  14. Hydroxylation and Glycosylation of Phenylpropanoids by Cultured Cells of Phytolacca americana.

    PubMed

    Shimoda, Kei; Kubota, Naoji; Uesugi, Daisuke; Tanigawa, Masato; Hamada, Hiroki

    2016-02-01

    Hydroxylation and glycosylation of cinnamic acid, p-coumaric acid, caffeic acid, and ferulic acid were investigated using cultured plant cells of Phytolacca americana as biocatalysts. Regioselective hydroxylation at the 4-position of cinnamic acid and 3-position of p-coumaric acid was observed. Although cinnamic acid was transformed to mono-glucoside products, di-glycosylation occurred in the case of the biotransformation of p-coumaric acid, caffeic acid, and ferulic acid.

  15. Selective Aromatic C–H Hydroxylation Enabled by η6-Coordination to Iridium(III)

    PubMed Central

    D'Amato, Erica M.; Neumann, Constanze N.; Ritter, Tobias

    2016-01-01

    We report an aromatic C–H hydroxylation protocol in which the arene is activated through η6-coordination to an iridium(III) complex. η6-Coordination of the arene increases its electrophilicity and allows for high positional selectivity of hydroxylation at the site of least electron density. Through investigation of intermediate η5-cyclohexadienyl adducts and arene exchange reactions, we evaluate incorporation of arene π-activation into a catalytic cycle for C–H functionalization. PMID:26877574

  16. Presence of Hydrogen Peroxide, a Source of Hydroxyl Radicals, in Acid Electrolyzed Water

    PubMed Central

    Mokudai, Takayuki; Nakamura, Keisuke; Kanno, Taro; Niwano, Yoshimi

    2012-01-01

    Background Acid electrolyzed water (AEW), which is produced through the electrolysis of dilute sodium chloride (NaCl) or potassium chloride solution, is used as a disinfectant in various fields because of its potent antimicrobial activity. The hydroxyl radical, an oxygen radical species, is often suggested as a putative active ingredient for AEW antimicrobial activity. Methodology/Principal Findings The aim of the present study is to detect hydroxyl radicals in AEW. The hydroxyl radicals in AEW prepared under different conditions were determined using an electron spin resonance (ESR) technique. A signal from 5,5-dimethyl-1-pyrroline N-oxide (DMPO)-OH, an adduct of DMPO and the hydroxyl radical, was detected in AEW prepared by double or triple electrolyses of 1% NaCl but not of 0.1% NaCl solution. Then the presence of hydrogen peroxide as a proposed source of hydroxyl radicals was examined using a combination of ESR and a Fenton reaction. The DMPO-OH signal was clearly detected, even in AEW prepared by single electrolysis of 0.1% NaCl solution, when ferrous sulfate was added to induce a Fenton reaction, indicating the presence of hydrogen peroxide in the AEW. Since sodium formate, a hydroxyl radical scavenger, did not affect the bactericidal activity of AEW, it is concluded that the radical is unlikely to contribute to the antimicrobial activity of AEW, although a small amount of the radical is produced from hydrogen peroxide. Dimethyl sulfoxide, the other hydroxyl radical scavenger used in the present study, canceled the bactericidal activity of AEW, accompanied by complete depletion of free available chlorine, suggesting that hypochlorous acid is probably a major contributor to the antimicrobial activity. Conclusions It is strongly suggested that although hydrogen peroxide is present in AEW as a source of hydroxyl radicals, the antimicrobial activity of AEW does not depend on these radicals. PMID:23029505

  17. Theoretical study on the gas phase reaction of acrylonitrile with a hydroxyl radical.

    PubMed

    Sun, Jingyu; Wang, Rongshun; Wang, Baoshan

    2011-10-01

    The mechanism and kinetics of the reaction of acrylonitrile (CH(2)=CHCN) with hydroxyl (OH) has been investigated theoretically. This reaction is revealed to be one of the most significant loss processes of acrylonitrile. BHandHLYP and M05-2X methods are employed to obtain initial geometries. The reaction mechanism conforms that OH addition to C[double bond, length as m-dash]C double bond or C atom of -CN group to form the chemically activated adducts, 1-IM1(HOCH(2)=CHCN), 2-IM1(CH(2)=HOCHCN), and 3-IM1(CH(2)=CHCOHN) via low barriers, and direct hydrogen abstraction paths may also occur. Temperature- and pressure-dependent rate constants have been evaluated using the Rice-Ramsperger-Kassel-Marcus theory. The calculated rate constants are in good agreement with the experimental data. At atmospheric pressure with N(2) as bath gas, 1-IM1(OHCH(2)=CHCN) formed by collisional stabilization is the major product in the temperature range of 200-1200 K. The production of CH(2)CCN and CHCHCN via hydrogen abstractions becomes dominant at high temperatures (1200-3000 K).

  18. High-throughput SHAPE and hydroxyl radical analysis of RNA structure and ribonucleoprotein assembly.

    PubMed

    McGinnis, Jennifer L; Duncan, Caia D S; Weeks, Kevin M

    2009-01-01

    RNA folds to form complex structures vital to many cellular functions. Proteins facilitate RNA folding at both the secondary and tertiary structure levels. An absolute prerequisite for understanding RNA folding and ribonucleoprotein (RNP) assembly reactions is a complete understanding of the RNA structure at each stage of the folding or assembly process. Here we provide a guide for comprehensive and high-throughput analysis of RNA secondary and tertiary structure using SHAPE and hydroxyl radical footprinting. As an example of the strong and sometimes surprising conclusions that can emerge from high-throughput analysis of RNA folding and RNP assembly, we summarize the structure of the bI3 group I intron RNA in four distinct states. Dramatic structural rearrangements occur in both secondary and tertiary structure as the RNA folds from the free state to the active, six-component, RNP complex. As high-throughput and high-resolution approaches are applied broadly to large protein-RNA complexes, other proteins previously viewed as making simple contributions to RNA folding are also likely to be found to exert multifaceted, long-range, cooperative, and nonadditive effects on RNA folding. These protein-induced contributions add another level of control, and potential regulatory function, in RNP complexes.

  19. Hydroxyl radical generation and oxidative stress in Carassius auratus liver, exposed to pyrene.

    PubMed

    Sun, Yuanyuan; Yin, Ying; Zhang, Jingfei; Yu, Hongxia; Wang, Xiaorong; Wu, Jichun; Xue, Yuqun

    2008-10-01

    This paper studied the hydroxy radical generation and oxidative stress in the liver of goldfish Carassius auratus under the effect of pyrene. Fish were exposed to different concentrations (0.001, 0.005, 0.01, 0.05 and 0.1 mg/L) of pyrene for 10 days, with one group assigned as control. Based on the hyperfine splitting constants and shape of the electron paramagnetic resonance (EPR) spectrum, the free radical which was generated in fish liver was identified as hydroxyl radical ((*)OH). The (*)OH signal intensity showed a significant increase compared with the control. The changes of the activities of catalase (CAT), superoxide dismutase (SOD), and glutathione-S-transferase (GST) were detected. The reduced glutathione (GSH) level decreased significantly while oxidized glutathione (GSSG) level was increased at higher concentration (0.005-0.1 mg/L), resulting in a decreased GSH/GSSG ratio, and the malondialdehyde (MDA) content increased significantly at 0.005-0.1 mg/L pyrene. The results clearly showed that C. auratus was subjected to oxidative stress and damage when exposed to pyrene.

  20. Stereospecificity in hydroxyl radical scavenging activities of four ginsenosides produced by heat processing.

    PubMed

    Kang, Ki Sung; Kim, Hyun Young; Yamabe, Noriko; Yokozawa, Takako

    2006-10-01

    The activity-guided fractionation of sun ginseng (SG, heat processed Panax ginseng C. A. Meyer at 120 degrees C) was carried out to identify its main active hydroxyl radical (*OH) scavenging components. As a result, the n-BuOH fraction mainly consisting of ginsenosides showed the strongest activity. Of several ginsenosides of SG, the *OH scavenging activities of relatively high contents of 20(S)-Rg(3), 20(R)-Rg(3), Rk(1), and Rg(5) were compared. Rg(5) and 20(S)-Rg(3) showed strong *OH scavenging IC(50) values of 0.15 and 0.44 mM, respectively, and these activities were prominently higher than each of their respective isomers. Therefore, stereospecificity exists in the *OH scavenging activities of ginsenosides produced by heat processing. Especially, the double bond at carbon-20(22) or the OH group at carbon-20 geometrically close to OH at carbon-12 is thought to increase the *OH scavenging activity of ginsenosides.

  1. Hydroxyl radical production and oxidative damage induced by cadmium and naphthalene in liver of Carassius auratus.

    PubMed

    Shi, Huahong; Sui, Yunxia; Wang, Xiaorong; Luo, Yi; Ji, Liangliang

    2005-01-01

    Freshwater goldfish (Carassius auratus) were exposed to cadmium (Cd) from 0 to 5 mg/L, and naphthalene (NAP) from 0 to 50 mg/L. Twenty-four hours after the exposure, reactive oxygen species (ROS) was trapped by phenyl-tert-butyl nitrone and detected by electron paramagnetic resonance (EPR). Protein carbonyl (PCO) and lipid peroxidation (LPO) content were determined. The activities of superoxide dismutase (SOD) and catalase (CAT) were also measured. The EPR spectra signals were characterized by prominent six-line spectra, which were defined as hydroxyl radical ((.)OH). As compared to the control group, Cd and NAP significantly induced (.)OH production marked by the intensity of the prominent spectra at higher concentrations. Both xenobiotics also increased LPO content and PCO content, depending on the concentrations. Either LPO or PCO content showed significant relation with (.)OH production. Cd increased the activity of SOD and decreased that of CAT at 5 mg/L, and NAP increased the activities of SOD and CAT at 5 mg/L. The results clearly indicated that these two structurally different non-redox cycling xenobiotics could induce (.)OH generation and result in oxidative damage in liver of C. auratus, and these effects were concentration-dependent.

  2. Laser smoothing of sub-micron grooves in hydroxyl-rich fused silica

    SciTech Connect

    Shen, N; Matthews, M J; Fair, J E; Britten, J A; Nguyen, H T; Cooke, D; Elhadj, S; Yang, S T

    2009-10-30

    Nano- to micrometer-sized surface defects on UV-grade fused silica surfaces are known to be effectively smoothed through the use of high-temperature localized CO{sub 2} laser heating, thereby enhancing optical properties. However, the details of the mass transport and the effect of hydroxyl content on the laser smoothing of defective silica at submicron length scales is still not completely understood. In this study, we examine the morphological evolution of sub-micron, dry-etched periodic surface structures on type II and type III SiO{sub 2} substrates under 10.6 {micro}m CO{sub 2} laser irradiation using atomic force microscopy (AFM). In-situ thermal imaging was used to map the transient temperature field across the heated region, allowing assessment of the T-dependent mass transport mechanisms under different laser-heating conditions. Computational fluid dynamics simulations correlated well with experimental results, and showed that for large effective capillary numbers (N{sub c} > 2), surface diffusion is negligible and smoothing is dictated by capillary action, despite the relatively small spatial scales studied here. Extracted viscosity values over 1700-2000K were higher than the predicted bulk values, but were consistent with the surface depletion of OH groups, which was confirmed using confocal Raman microscopy.

  3. Superficial dopants allow growth of silicone nanofilaments on hydroxyl-free substrates.

    PubMed

    Artus, Georg R J; Bigler, Laurent; Seeger, Stefan

    2014-09-01

    We report new types of silicone nanostructures by a gas-phase reaction of trichloromethylsilane: 1-D silicone nanofilaments with a raveled end and silicone nanoteeth. Filaments with a raveled end are obtained on poly(vinyl chloride), which is superficially doped with the detergent Span 20. Silicone nanoteeth grow on sodium chloride using dibutyl phthalate as superficial dopant. Without dopants, no structures are observed. The dopants are identified by mass spectroscopy and the silicone nanostructures are analyzed by infrared spectroscopy and energy-dispersive analysis of X-rays. The growth of silicone nanostructures on a hydrophobic substrate (poly(vinyl chloride)/Span 20) and a substrate free of hydroxyl groups (sodium chloride/dibutyl phthalate) questions the currently discussed mechanisms for the growth of 1-D silicone nanofilaments, which is discussed. We suggest superficial doping as an alternative pretreatment method to oxidizing activation and prove this principle by the successful coating of copper, which is superficially doped with Span 20. PMID:25111760

  4. Potent and Selective Monoamine Oxidase-B Inhibitory Activity: Fluoro- vs. Trifluoromethyl-4-hydroxylated Chalcone Derivatives.

    PubMed

    Mathew, Bijo; Mathew, Githa Elizabeth; Uçar, Gülberk; Baysal, Ipek; Suresh, Jerad; Mathew, Sincy; Haridas, Abitha; Jayaprakash, Venkatesan

    2016-08-01

    For various neurodegenerative disorders like Alzheimer's and Parkinson's diseases, selective and reversible MAO-B inhibitors have a great therapeutic value. In our previous study, we have shown that a series of methoxylated chalcones with F functional group exhibited high binding affinity toward human monoamine oxidase-B (hMAO-B). In continuation of our earlier study and to extend the understanding of the structure-activity relationships, a series of five new chalcones were studied for their inhibition of hMAO. The results demonstrated that these compounds are reversible and selective hMAO-B inhibitors with a competitive mode of inhibition. The most active compound, (2E)-1-(4-hydroxyphenyl)-3-[4-(trifluoromethyl)phenyl]prop-2-en-1-one, exhibited a Ki value of 0.33 ± 0.01 μm toward hMAO-B with a selectivity index of 26.36. A molecular docking study revealed that the presence of a H-bond network in hydroxylated chalcone with the N(5) atom of FAD is crucial for MAO-B selectivity and potency.

  5. Binding studies of hydroxylated Multi-Walled Carbon Nanotubes to hemoglobin, gamma globulin and transferrin.

    PubMed

    Sekar, Gajalakshmi; Kandiyil, Shirona Thazae; Sivakumar, Amaravathy; Mukherjee, Amitava; Chandrasekaran, Natarajan

    2015-12-01

    Biocompatibility of nanoparticles depends on their binding behavior with biomolecules. Herein, we have reported the interaction of three different biological macromolecules such as hemoglobin, gamma globulin and transferrin with hydroxyl group functionalized Multi-Walled Carbon Nanotubes (OH-MWCNTs). Multiple spectroscopic methods were utilized to identify the binding cum structural changes in biomolecules upon their interaction. Hyperchromic effect observed in the UV-visible spectra, and the quenching behavior from fluorescence emission evidences the existence of bio-nanotube complex formation. Synchronous and three-dimensional fluorescence spectra of biomolecules, in correspondence with Trp and Tyr residues showed the possible disturbance towards their aromatic micro-environment. Changes observed in the FTIR and FT-Raman amide bands, and amino acid residue position of biomolecules upon interaction with CNTs showed the possible effect towards their secondary structure. Further studies with CD spectroscopy indicated the loss of alpha-helical structures quantitatively. The study remains significant in evaluating the biosafety profile of functionalized MWCNTs for their in vivo biomedical applications.

  6. Prolyl 4-hydroxylase activity-responsive transcription factors: From hydroxylation to gene expression and neuroprotection

    PubMed Central

    Siddiq, Ambreena; Aminova, Leila R; Ratan, Rajiv R

    2008-01-01

    Most homeostatic processes including gene transcription occur as a result of deviations in physiological tone that threatens the survival of the organism. A prototypical homeostatic stress response includes changes in gene expression following alterations in oxygen, iron or 2-oxoglutarate levels. Each of these cofactors plays an important role in cellular metabolism. Accordingly, a family of enzymes known as the Prolyl 4-hydroxylase (PHD) enzymes are a group of dioxygenases that have evolved to sense changes in 2-oxoglutarate, oxygen and iron via changes in enzyme activity. Indeed, PHDs are a part of an established oxygen sensor system that regulates transcriptional regulation of hypoxia/stress-regulated genes and thus are an important component of events leading to cellular rescue from oxygen, iron or 2-oxoglutarate deprivations. The ability of PHD activity to regulate homeostatic responses to oxygen, iron or 2-oxoglutarate metabolism has led to the development of small molecule inhibitors of the PHDs as a strategy for activating or augmenting cellular stress responses. These small molecules are proving effective in preclinical models of stroke and Parkinson's disease. However the precise protective pathways engaged by PHD inhibition are only beginning to be defined. In the current review, we summarize the role of iron, 2-oxoglutarate and oxygen in the PHD catalyzed hydroxylation reaction and provide a brief discussion of some of the transcription factors that play an effective role in neuroprotection against oxidative stress as a result of changes in PHD activity. PMID:17981760

  7. Genomic Repeat Abundances Contain Phylogenetic Signal

    PubMed Central

    Dodsworth, Steven; Chase, Mark W.; Kelly, Laura J.; Leitch, Ilia J.; Macas, Jiří; Novák, Petr; Piednoël, Mathieu; Weiss-Schneeweiss, Hanna; Leitch, Andrew R.

    2015-01-01

    A large proportion of genomic information, particularly repetitive elements, is usually ignored when researchers are using next-generation sequencing. Here we demonstrate the usefulness of this repetitive fraction in phylogenetic analyses, utilizing comparative graph-based clustering of next-generation sequence reads, which results in abundance estimates of different classes of genomic repeats. Phylogenetic trees are then inferred based on the genome-wide abundance of different repeat types treated as continuously varying characters; such repeats are scattered across chromosomes and in angiosperms can constitute a majority of nuclear genomic DNA. In six diverse examples, five angiosperms and one insect, this method provides generally well-supported relationships at interspecific and intergeneric levels that agree with results from more standard phylogenetic analyses of commonly used markers. We propose that this methodology may prove especially useful in groups where there is little genetic differentiation in standard phylogenetic markers. At the same time as providing data for phylogenetic inference, this method additionally yields a wealth of data for comparative studies of genome evolution. PMID:25261464

  8. Genomic repeat abundances contain phylogenetic signal.

    PubMed

    Dodsworth, Steven; Chase, Mark W; Kelly, Laura J; Leitch, Ilia J; Macas, Jiří; Novák, Petr; Piednoël, Mathieu; Weiss-Schneeweiss, Hanna; Leitch, Andrew R

    2015-01-01

    A large proportion of genomic information, particularly repetitive elements, is usually ignored when researchers are using next-generation sequencing. Here we demonstrate the usefulness of this repetitive fraction in phylogenetic analyses, utilizing comparative graph-based clustering of next-generation sequence reads, which results in abundance estimates of different classes of genomic repeats. Phylogenetic trees are then inferred based on the genome-wide abundance of different repeat types treated as continuously varying characters; such repeats are scattered across chromosomes and in angiosperms can constitute a majority of nuclear genomic DNA. In six diverse examples, five angiosperms and one insect, this method provides generally well-supported relationships at interspecific and intergeneric levels that agree with results from more standard phylogenetic analyses of commonly used markers. We propose that this methodology may prove especially useful in groups where there is little genetic differentiation in standard phylogenetic markers. At the same time as providing data for phylogenetic inference, this method additionally yields a wealth of data for comparative studies of genome evolution.

  9. Hydroxyl-radical-induced degradative oxidation of beta-lactam antibiotics in water: absolute rate constant measurements.

    PubMed

    Dail, Michelle K; Mezyk, Stephen P

    2010-08-19

    The beta-lactam antibiotics are some of the most prevalent pharmaceutical contaminants currently being detected in aquatic environments. Because the presence of any trace level of antibiotic in water may adversely affect aquatic ecosystems and contribute to the production of antibiotic-resistant bacteria, active removal by additional water treatments, such as using advanced oxidation and reduction processes (AO/RPs), may be required. However, to ensure that any AOP treatment process occurs efficiently and quantitatively, a full understanding of the kinetics and mechanisms of all of the chemical reactions involved under the conditions of use is necessary. In this study, we report on our kinetic measurements for the hydroxyl-radical-induced oxidation of 11 beta-lactam antibiotics obtained using electron pulse radiolysis techniques. For the 5-member ring species, an average reaction rate constant of (7.9 +/- 0.8) x 10(9) M(-1) s(-1) was obtained, slightly faster than for the analogous 6-member ring containing antibiotics, (6.6 +/- 1.2) x 10(9) M(-1) s(-1). The consistency of these rate constants for each group infers a common reaction mechanism, consisting of the partitioning of the hydroxyl radical between addition to peripheral aromatic rings and reaction with the central double-ring core of these antibiotics.

  10. Measurement of Hydroxyl-Radical Formation in the Rat Striatum by In Vivo Microdialysis and GC-MS.

    PubMed

    Nguyen, V; Bonds, D V; Prokai, L

    2008-10-01

    A GC-MS method was developed for measuring hydroxyl-radical capture products of salicylic acid, a common trapping agent for this reactive oxygen species, in samples obtained by in vivo cerebral microdialysis experiments. The assay employed liquid-liquid extraction followed by derivatization of 2,3- and 2,5-dihydroxybenzoic acid, along with 3,5-dihydroxybenzoic acid added as an internal standard. Due to their simple electron ionization mass spectra featuring [M - 57](+) ions through the loss of tertiary alkyl group from the corresponding molecular ions, tert-butyldimethylsilyl (TBDMS) derivatives afforded straightforward method development based on selected-ion monitoring. In addition, tandem mass spectrometry probing collision-induced dissociation of [M - 57](+) ions obtained from the isomeric tert-butyldimethylsilyl derivatives revealed characteristic differences in the resultant product-ion spectra. Our work has demonstrated the applicability of GC-MS for the assay of microdialysates for 2,3- and 2,5-dihydroxybenzoic acid by confirming that local administration of the excitotoxic glutamate into the rat striatum significantly increased in vivo hydroxyl-radical production in this brain region and that subsequent systemic administration of α-phenyl-tert-butylnitrone reversed glutamate-induced oxidative stress.

  11. Detection analysis of surface hydroxyl active sites and simulation calculation of the surface dissociation constants of aqueous diatomite suspensions

    NASA Astrophysics Data System (ADS)

    Ma, Shu-Cui; Wang, Zhi-Gang; Zhang, Ji-Lin; Sun, De-Hui; Liu, Gui-Xia

    2015-02-01

    The surface properties of the diatomite were investigated using nitrogen adsorption/deadsorption isotherms, TG-DSC, FTIR, and XPS, and surface protonation-deprotonation behavior was determined by continuous acid-base potentiometric titration technique. The diatomite sample with porous honeycomb structure has a BET specific surface area of 10.21 m2/g and large numbers of surface hydroxyl functional groups (i.e. tbnd Si-OH, tbnd Fe-OH, and tbnd Al-OH). These surface hydroxyls can be protonated or deprotonated depending on the pH of the suspension. The experimental potentiometric data in two different ionic strength solutions (0.1 and 0.05 mol/L NaCl) were fitted using ProtoFit GUI V2.1 program by applying diffuse double layer model (DLM) with three amphoteric sites and minimizing the sum of squares between a dataset derivative function and a model derivative function. The optimized surface parameters (i.e. surface dissociation constants (log K1, log K2) and surface site concentrations (log C)) of the sample were obtained. Based on the optimized surface parameters, the surface species distribution was calculated using Program-free PHREEQC 3.1.2. Thus, this work reveals considerable new information about surface protonation-deprotonation processes and surface adsorptive behaviors of the diatomite, which helps us to effectively use the cheap and cheerful diatomite clay adsorbent.

  12. Origin of Coverage Dependence in Photoreactivity of Carboxylate on TiO2(110): Hindering by Charged Coadsorbed Hydroxyls

    SciTech Connect

    Wang, Zhitao; Henderson, Michael A.; Lyubinetsky, Igor

    2015-09-30

    The influence of reactant coverage on photochemical activity was explored using scanning tunneling microscopy (STM) and ultraviolet photoelectron spectroscopy (UPS). We observed diminished reactivity of carboxylate species (trimethyl acetate, TMA) on TiO2(110) as a function of increasing coverage. This effect was not linked to intermolecular interactions of TMA but to the accumulation of the coadsorbed bridging hydroxyls (HOb) deposited during (thermal) dissociative adsorption of the parent, trimethylacetic acid (TMAA). Confirmation of the hindering influence of HOb groups was obtained by the observation that HOb species originated from H2O dissociation at O-vacancy sites have a similar hindering effect on TMA photochemistry. Though HOb’s are photoinactive on TiO2(110) under ultrahigh vacuum conditions, UPS results show that these sites trap photoexcited electrons, which in turn likely (electrostatically) attract and neutralize photoexcited holes, thus suppressing the hole-mediated photoreactivity of TMA. This negative influence of surface hydroxyls on hole-mediated photochemistry is likely a major factor in other anaerobic photochemical processes on reducible oxide surfaces.

  13. Solvent-free lipase-catalyzed synthesis of a novel hydroxyl-fatty acid derivative of kojic acid.

    PubMed

    El-Boulifi, Noureddin; Ashari, Siti Efliza; Serrano, Marta; Aracil, Jose; Martínez, Mercedes

    2014-02-01

    The aim of this work was the synthesis of a novel hydroxyl-fatty acid derivative of kojic acid rich in kojic acid monoricinoleate (KMR) which can be widely used in the cosmetic and food industry. The synthesis of KMR was carried out by lipase-catalysed esterification of ricinoleic and kojic acids in solvent-free system. Three immobilized lipases were tested and the best KMR yields were attained with Lipozyme TL IM and Novozym 435. Since Lipozyme TL IM is the cheapest, it was selected to optimize the reaction conditions. The optimal reaction conditions were 80 °C for the temperature, 1:1 for the alcohol/acid molar ratio, 600 rpm for stirring speed and 7.8% for the catalyst concentration. Under these conditions, the reaction was scaled up in a 5×10⁻³ m³ stirred tank reactor. ¹H-¹³C HMBC-NMR showed that the primary hydroxyl group of kojic acid was regioselectively esterified. The KMR has more lipophilicity than kojic acid and showed antioxidant activity that improves the oxidation stability of biodiesel.

  14. Finding synergies in fuels properties for the design of renewable fuels--hydroxylated biodiesel effects on butanol-diesel blends.

    PubMed

    Sukjit, E; Herreros, J M; Piaszyk, J; Dearn, K D; Tsolakis, A

    2013-04-01

    This article describes the effects of hydroxylated biodiesel (castor oil methyl ester - COME) on the properties, combustion, and emissions of butanol-diesel blends used within compression ignition engines. The study was conducted to investigate the influence of COME as a means of increasing the butanol concentration in a stable butanol-diesel blend. Tests were compared with baseline experiments using rapeseed methyl esters (RME). A clear benefit in terms of the trade-off between NOX and soot emissions with respect to ULSD and biodiesel-diesel blends with the same oxygen content was obtained from the combination of biodiesel and butanol, while there was no penalty in regulated gaseous carbonaceous emissions. From the comparison between the biodiesel fuels used in this work, COME improved some of the properties (for example lubricity, density and viscosity) of butanol-diesel blends with respect to RME. The existence of hydroxyl group in COME also reduced further soot emissions and decreased soot activation energy. PMID:23452309

  15. Ratiometric coumarin-neutral red (CONER) nanoprobe for detection of hydroxyl radicals.

    PubMed

    Ganea, Gabriela M; Kolic, Paulina E; El-Zahab, Bilal; Warner, Isiah M

    2011-04-01

    Excessive production of reactive oxygen species can lead to alteration of cellular functions responsible for many diseases including cardiovascular diseases, neurodegenerative diseases, cancer, and aging. Hydroxyl radical is a short-lived radical which is considered very aggressive due to its high reactivity toward biological molecules. In this study, a COumarin-NEutral Red (CONER) nanoprobe was developed for detection of hydroxyl radical based on the ratiometric fluorescence signal between 7-hydroxy coumarin 3-carboxylic acid and neutral red dyes. Biocompatible poly lactide-co-glycolide (PLGA) nanoparticles containing encapsulated neutral red were produced using a coumarin 3-carboxylic acid conjugated poly(sodium N-undecylenyl-Nε-lysinate) (C3C-poly-Nε-SUK) as moiety reactive to hydroxyl radicals. The response of the CONER nanoprobe was dependent on various parameters such as reaction time and nanoparticle concentration. The probe was selective for hydroxyl radicals as compared with other reactive oxygen species including O(2)(•-), H(2)O(2), (1)O(2), and OCl(-). Furthermore, the CONER nanoprobe was used to detect hydroxyl radicals in vitro using viable breast cancer cells exposed to oxidative stress. The results suggest that this nanoprobe represents a promising approach for detection of hydroxyl radicals in biological systems.

  16. Formation of hydroxyl-functionalized stilbenoid molecular sieves at the liquid/solid interface on top of a 1-decanol monolayer

    NASA Astrophysics Data System (ADS)

    Bellec, Amandine; Arrigoni, Claire; Douillard, Ludovic; Fiorini-Debuisschert, Céline; Mathevet, Fabrice; Kreher, David; Attias, André-Jean; Charra, Fabrice

    2014-10-01

    Specific molecular tectons can be designed to form molecular sieves through self-assembly at the solid-liquid interface. After demonstrating a model tecton bearing apolar alkyl chains, we then focus on a modified structure involving asymmetric functionalization of some alkyl chains with polar hydroxyl groups in order to get chemical selectivity in the sieving. As the formation of supramolecular self-assembled networks strongly depends on molecule-molecule, molecule-substrate and molecule-solvent interactions, we compared the tectons’ self-assembly on graphite for two types of solvent. We demonstrate the possibility to create hydroxylated stilbenoid molecular sieves by using 1-decanol as a solvent. Interestingly, with this solvent, the porous network is developed on top of a 1-decanol monolayer.

  17. Late Embryogenesis Abundant (LEA) proteins in legumes.

    PubMed

    Battaglia, Marina; Covarrubias, Alejandra A

    2013-01-01

    Plants are exposed to different external conditions that affect growth, development, and productivity. Water deficit is one of these adverse conditions caused by drought, salinity, and extreme temperatures. Plants have developed different responses to prevent, ameliorate or repair the damage inflicted by these stressful environments. One of these responses is the activation of a set of genes encoding a group of hydrophilic proteins that typically accumulate to high levels during seed dehydration, at the last stage of embryogenesis, hence named Late Embryogenesis Abundant (LEA) proteins. LEA proteins also accumulate in response to water limitation in vegetative tissues, and have been classified in seven groups based on their amino acid sequence similarity and on the presence of distinctive conserved motifs. These proteins are widely distributed in the plant kingdom, from ferns to angiosperms, suggesting a relevant role in the plant response to this unfavorable environmental condition. In this review, we analyzed the LEA proteins from those legumes whose complete genomes have been sequenced such as Phaseolus vulgaris, Glycine max, Medicago truncatula, Lotus japonicus, Cajanus cajan, and Cicer arietinum. Considering their distinctive motifs, LEA proteins from the different groups were identified, and their sequence analysis allowed the recognition of novel legume specific motifs. Moreover, we compile their transcript accumulation patterns based on publicly available data. In spite of the limited information on these proteins in legumes, the analysis and data compiled here confirm the high correlation between their accumulation and water deficit, reinforcing their functional relevance under this detrimental conditions. PMID:23805145

  18. Stronger warming effects on microbial abundances in colder regions

    PubMed Central

    Chen, Ji; Luo, Yiqi; Xia, Jianyang; Jiang, Lifen; Zhou, Xuhui; Lu, Meng; Liang, Junyi; Shi, Zheng; Shelton, Shelby; Cao, Junji

    2015-01-01

    Soil microbes play critical roles in regulating terrestrial carbon (C) cycle and its feedback to climate change. However, it is still unclear how the soil microbial community and abundance respond to future climate change scenarios. In this meta-analysis, we synthesized the responses of microbial community and abundance to experimental warming from 64 published field studies. Our results showed that warming significantly increased soil microbial abundance by 7.6% on average. When grouped by vegetation or soil types, tundras and histosols had the strongest microbial responses to warming with increased microbial, fungal, and bacterial abundances by 15.0%, 9.5% and 37.0% in tundra, and 16.5%, 13.2% and 13.3% in histosols, respectively. We found significant negative relationships of the response ratios of microbial, fungal and bacterial abundances with the mean annual temperature, indicating that warming had stronger effects in colder than warmer regions. Moreover, the response ratios of microbial abundance to warming were positively correlated with those of soil respiration. Our findings therefore indicate that the large quantities of C stored in colder regions are likely to be more vulnerable to climate warming than the soil C stored in other warmer regions. PMID:26658882

  19. Stronger warming effects on microbial abundances in colder regions

    SciTech Connect

    Chen, Ji; Luo, Yiqi; Xia, Jianyang; Jiang, Lifen; Zhou, Xuhui; Lu, Meng; Liang, Junyi; Shi, Zheng; Shelton, Shelby; Cao, Junji

    2015-12-10

    Soil microbes play critical roles in regulating terrestrial carbon (C) cycle and its feedback to climate change. However, it is still unclear how the soil microbial community and abundance respond to future climate change scenarios. In this meta-analysis, we synthesized the responses of microbial community and abundance to experimental warming from 64 published field studies. Our results showed that warming significantly increased soil microbial abundance by 7.6% on average. When grouped by vegetation or soil types, tundras and histosols had the strongest microbial responses to warming with increased microbial, fungal, and bacterial abundances by 15.0%, 9.5% and 37.0% in tundra, and 16.5%, 13.2% and 13.3% in histosols, respectively. We found significant negative relationships of the response ratios of microbial, fungal and bacterial abundances with the mean annual temperature, indicating that warming had stronger effects in colder than warmer regions. Moreover, the response ratios of microbial abundance to warming were positively correlated with those of soil respiration. Our results therefore indicate that the large quantities of C stored in colder regions are likely to be more vulnerable to climate warming than the soil C stored in other warmer regions.

  20. Stronger warming effects on microbial abundances in colder regions

    DOE PAGES

    Chen, Ji; Luo, Yiqi; Xia, Jianyang; Jiang, Lifen; Zhou, Xuhui; Lu, Meng; Liang, Junyi; Shi, Zheng; Shelton, Shelby; Cao, Junji

    2015-12-10

    Soil microbes play critical roles in regulating terrestrial carbon (C) cycle and its feedback to climate change. However, it is still unclear how the soil microbial community and abundance respond to future climate change scenarios. In this meta-analysis, we synthesized the responses of microbial community and abundance to experimental warming from 64 published field studies. Our results showed that warming significantly increased soil microbial abundance by 7.6% on average. When grouped by vegetation or soil types, tundras and histosols had the strongest microbial responses to warming with increased microbial, fungal, and bacterial abundances by 15.0%, 9.5% and 37.0% in tundra,more » and 16.5%, 13.2% and 13.3% in histosols, respectively. We found significant negative relationships of the response ratios of microbial, fungal and bacterial abundances with the mean annual temperature, indicating that warming had stronger effects in colder than warmer regions. Moreover, the response ratios of microbial abundance to warming were positively correlated with those of soil respiration. Our results therefore indicate that the large quantities of C stored in colder regions are likely to be more vulnerable to climate warming than the soil C stored in other warmer regions.« less