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Sample records for alcoholic hydroxyl group

  1. Highly Active Supported Pt Nanocatalysts Synthesized by Alcohol Reduction towards Hydrogenation of Cinnamaldehyde: Synergy of Metal Valence and Hydroxyl Groups.

    PubMed

    Wang, Yanyan; He, Wanhong; Wang, Liren; Yang, Junjiao; Xiang, Xu; Zhang, Bing; Li, Feng

    2015-07-01

    The hydrogenation of α,β-unsaturated aldehydes to allylic alcohols or saturated aldehydes provides a typical example to study the catalytic effect on structure-sensitive reactions. In this work, supported platinum nanocatalysts over hydrotalcite were synthesized by an alcohol reduction method. The Pt catalyst prepared by the reduction with a polyol (ethylene glycol) outperforms those prepared with ethanol and methanol in the hydrogenation of cinnamaldehyde. The selectivity towards the C=O bond is the highest over the former, although its mean size of Pt particles is the smallest. The hydroxyl groups on hydrotalcite could act as an internally accessible promoter to enhance the selectivity towards the C=O bond. The optimal Pt catalyst showed a high activity with an initial turnover frequency (TOF) of 2.314 s(-1). This work unveils the synergic effect of metal valence and in situ promoter on the chemoselective hydrogenation, which could open up a new direction in designing hydrogenation catalysts.

  2. 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

  3. Horseradish peroxidase-catalyzed formation of hydrogels from chitosan and poly(vinyl alcohol) derivatives both possessing phenolic hydroxyl groups.

    PubMed

    Sakai, Shinji; Khanmohammadi, Mehdi; Khoshfetrat, Ali Baradar; Taya, Masahito

    2014-10-13

    Horseradish peroxidase-catalyzed cross-linking was applied to prepare hydrogels from aqueous solutions containing chitosan and poly(vinyl alcohol) derivatives both possessing phenolic hydroxyl groups (denoted as Ph-chitosan and Ph-PVA, respectively). Comparing the hydrogels prepared from the solution of 1.0% (w/v) Ph-chitosan and 3.0% (w/v) Ph-PVA and that of 3.0% (w/v) Ph-chitosan and 1.0% (w/v) Ph-PVA, the gelation time of the former hydrogel was 47 s, while was 10s longer than that of the latter one. The breaking point for the former hydrogel under stretching (114% strain) was approximately twice larger than that for the latter one. The swelling ratio of the former hydrogel in saline was about half of the latter one. Fibroblastic cells did not adhere on the former hydrogel but adhered and spread on the latter one. The growth of Escherichia coli cells was fully suppressed on the latter hydrogel during 48 h cultivation.

  4. 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. ...

  5. Chemoselective Hydroxyl Group Transformation: An Elusive Target‡

    PubMed Central

    Trader, Darci J.; Carlson, Erin E.

    2012-01-01

    The selective reaction of one functional group in the presence of others is not a trivial task. A noteworthy amount of research has been dedicated to the chemoselective reaction of the hydroxyl moiety. This group is prevalent in many biologically important molecules including natural products and proteins. However, targeting the hydroxyl group is difficult for many reasons including its relatively low nucleophilicity in comparison to other ubiquitous functional groups such as amines and thiols. Additionally, many of the developed chemoselective reactions cannot be used in the presence of water. Despite these complications, chemoselective transformation of the hydroxyl moiety has been utilized in the synthesis of complex natural product derivatives, the reaction of tyrosine residues in proteins, the isolation of natural products and is the mechanism of action of myriad drugs. Here, methods for selective targeting of this group, as well as applications of several devised methods, are described. PMID:22695722

  6. Cytotoxic hydroxylated triterpene alcohol ferulates from rice bran.

    PubMed

    Luo, Hong-Feng; Li, Qinglin; Yu, Shanggong; Badger, Thomas M; Fang, Nianbai

    2005-01-01

    Three hydroxylated triterpene alcohol ferulates, (24S)-cycloart-25-ene-3 beta,24-diol-3 beta-trans-ferulate (1), (24R)-cycloart-25-ene-3 beta,24-diol-3 beta-trans-ferulate (2), and cycloart-23Z-ene-3 beta,25-diol-3 beta-trans-ferulate (3), along with known compounds cycloartenol trans-ferulate (4) and 24-methylenecycloartanol trans-ferulate (5) were isolated from rice bran. Their structures were elucidated by means of chemical and spectroscopic analysis. Compounds 2-5 showed moderate cytotoxicity against MCF-7 cells.

  7. Identification and quantification of aerosol polar oxygenated compounds bearing carboxylic or hydroxyl groups. 1. Method development.

    PubMed

    Jaoui, M; Kleindienst, T E; Lewandowski, M; Edney, E O

    2004-08-15

    In this study, a new analytical technique was developed for the identification and quantification of multifunctional compounds containing simultaneously at least one hydroxyl or one carboxylic group, or both. This technique is based on derivatizing first the carboxylic group(s) of the multifunctional compound using an alcohol (e.g., methanol, 1-butanol) in the presence of a relatively strong Lewis acid (BF3) as a catalyst. This esterification reaction quickly and quantitatively converts carboxylic acids to their ester forms. The second step is based on silylation of the ester compounds using bis(trimethylsilyl) trifluoroacetamide (BSTFA) as the derivatizing agent. For compounds bearing ketone groups in addition to carboxylic and hydroxyl groups, a third step was used based on PFBHA derivatization of the carbonyls. Different parameters including temperature, reaction time, and effect due to artifacts were optimized. A GC/MS in EI and in methane-CI mode was used for the analysis of these compounds. The new approach was tested on a number of multifunctional compounds. The interpretation of their EI (70 eV) and CI mass spectra shows that critical information is gained leading to unambiguous identification of unknown compounds. For example, when derivatized only with BF(3)-methanol, their mass spectra comprise primary ions at m/z M.+ + 1, M.+ + 29, and M.+ - 31 for compounds bearing only carboxylic groups and M.+ + 1, M.+ + 29, M.+ - 31, and M+. - 17 for those bearing hydroxyl and carboxylic groups. However, when a second derivatization (BSTFA) was used, compounds bearing hydroxyl and carboxylic groups simultaneously show, in addition to the ions observed before, ions at m/z M.+ + 73, M.+ - 15, M.+ - 59, M.+ - 75, M.+ - 89, and 73. To the best of our knowledge, this technique describes systematically for the first time a method for identifying multifunctional oxygenated compounds containing simultaneously one or more hydroxyl and carboxylic acid groups.

  8. 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

  9. Comparison of Polyurethanes with Polyhydroxyurethanes: Effect of the Hydroxyl Group on Structure-Property Relationships

    NASA Astrophysics Data System (ADS)

    Leitsch, Emily K.; Lombardo, Vince M.; Scheidt, Karl A.; Torkelson, John M.

    2014-03-01

    Polyurethanes (PUs) are commonly synthesized by rapid step-growth polymerization through the reaction of a multifunctional alcohol with a polyisocyanate. PUs can be prepared at ambient conditions utilizing a variety of starting material molecular weights and backbones, resulting in highly tunable thermal and physical properties. The urethane linkages as well as the nanophase separated morphology attainable in PU materials lead to desirable properties including elastomeric character and adhesion. The isocyanate-based monomers used in the synthesis of traditional PUs have come under increasing regulatory pressure and thus inspired the investigation of alternative routes for the formation of PU materials. We examine an alternative route to synthesize PU- the reaction of five-membered cyclic carbonate with amines. This reaction results in the formation of a urethane linkage with an adjacent alcohol group. The effects of this hydroxyl group on the thermal and mechanical properties of the resulting polymer are investigated and compared with an analogous traditional PU system.

  10. Effect of liquefaction temperature on hydroxyl groups of bio-oil from loblolly pine (Pinus taeda).

    PubMed

    Celikbag, Yusuf; Via, Brian K; Adhikari, Sushil; Wu, Yonnie

    2014-10-01

    Loblolly pine was liquefied with ethylene glycol at 100, 150, 200 and 250 °C in order to analyze the effect of liquefaction temperature on hydroxyl groups of bio-oil, and to determine the source and variation of hydroxyl groups. The optimum temperature was found to be 150-200 °C. Hydroxyl number (OHN) of the bio-oil was ranged from 632 to 1430 mg KOH/g. GC-MS analysis showed that 70-90% of OHN was generated from unreacted EG. (31)P NMR analysis showed that the majority of hydroxyl groups were aliphatic, and none of the bio-oil exhibited any detectable hydroxyl groups from phenolic sources. Finally, it was found that all bio-oils were stable in terms of OHN for 2 months when stored at -10 °C.

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

    PubMed

    Xi, Gao-Lei; Liu, Zai-Qun

    2015-04-08

    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.

  12. Isoprenoid Alcohols are Susceptible to Oxidation with Singlet Oxygen and Hydroxyl Radicals.

    PubMed

    Komaszylo Née Siedlecka, Joanna; Kania, Magdalena; Masnyk, Marek; Cmoch, Piotr; Lozinska, Iwona; Czarnocki, Zbigniew; Skorupinska-Tudek, Karolina; Danikiewicz, Witold; Swiezewska, Ewa

    2016-02-01

    Isoprenoids, as common constituents of all living cells, are exposed to oxidative agents--reactive oxygen species, for example, singlet oxygen or hydroxyl radicals. Despite this fact, products of oxidation of polyisoprenoids have never been characterized. In this study, chemical oxidation of isoprenoid alcohols (Prenol-2 and -10) was performed using singlet oxygen (generated in the presence of hydrogen peroxide/molybdate or upon photochemical reaction in the presence of porphyrin), oxygen (formed upon hydrogen peroxide dismutation) or hydroxyl radical (generated by the hydrogen peroxide/sonication, UV/titanium dioxide or UV/hydrogen peroxide) systems. The structure of the obtained products, hydroxy-, peroxy- and heterocyclic derivatives, was studied with the aid of mass spectrometry (MS) and nuclear magnetic resonance (NMR) methods. Furthermore, mass spectrometry with electrospray ionization appeared to be a useful analytical tool to detect the products of oxidation of isoprenoids (ESI-MS analysis), as well as to establish their structure on the basis of the fragmentation spectra of selected ions (ESI-MS/MS analysis). Taken together, susceptibility of polyisoprenoid alcohols to various oxidizing agents was shown for the first time.

  13. Antioxidant effectiveness generated by one or two phenolic hydroxyl groups in coumarin-substituted dihydropyrazoles.

    PubMed

    Xi, Gao-Lei; Liu, Zai-Qun

    2013-10-01

    A cascade operation was designed to synthesize nine coumarin-substituted dihydropyrazoles with only one or two phenolic hydroxyl groups contained. Antioxidant abilities of the obtained compounds were evaluated by inhibiting 2,2'-azobis(2-amidinopropanehydrochloride) (AAPH)-, Cu2+/glutathione (GSH)-, and .OH-induced oxidation of DNA. It was found that less phenolic hydroxyl groups can enhance the abilities of coumarin-substituted dihydropyrazoles to protect DNA against the oxidation. Moreover, these coumarin-substituted dihydropyrazoles were employed to scavenge 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonate) cationic radical (ABTS+.), 2,2'-diphenyl-1-picrylhydrazyl radical (DPPH), and galvinoxyl radical, respectively. It was found that double phenolic hydroxyl groups were more beneficial for enhancing the abilities of coumarin-substituted dihydropyrazoles to quench the aforementioned radicals. Therefore, dihydropyrazole linked with coumarin exhibited powerful antioxidant effectiveness even in the case of less phenolic hydroxyl groups involved.

  14. Catalytic regioselective introduction of allyl alcohol into the nonpolar polyolefins: development of one-pot synthesis of hydroxyl-capped polyolefins mediated by a new metallocene IF catalyst.

    PubMed

    Imuta, Jun-ichi; Kashiwa, Norio; Toda, Yoshihisa

    2002-02-20

    A new catalytic regioselective one-pot synthesis of hydroxyl-capped polyolefins is reported. This synthesis employs a new stereorigid bridged metallocene having an indenyl and a fluorenyl ligand named IF catalyst 1, exhibiting high catalytic performances. Here, we report on (1) the first example of allyl alcohol incorporation into the nonpolar polymer backbone using IF catalyst 1 and methylaluminoxane with high activity, high molecular weight, and high polar monomer uptake at high temperature, and (2) the first example of predominant end-site-selective introduction of an alcohol group into the polyolefins. Moreover, we observed the mixed regioselectivity by the type of alkylaluminum.

  15. 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

  16. Oxidoreduction of different hydroxyl groups in bile acids during their enterohepatic circulation in man

    SciTech Connect

    Bjoerkhem, I.L.; Liljeqvist, L.; Nilsell, K.; Einarsson, K.

    1986-02-01

    The extent of oxidoreduction of the 3 alpha-, 7 alpha- and 12 alpha-hydroxyl groups in bile acids during the enterohepatic circulation in man was studied with the use of (3 beta-/sup 3/H)-labeled deoxycholic acid and cholic acid, (7 beta-/sup 3/H)-labeled cholic acid, and (12 beta-/sup 3/H)-labeled deoxycholic acid and cholic acid. Each (/sup 3/H)-labeled bile acid was given per os to healthy volunteers, together with the corresponding (24-/sup 14/C)-labeled bile acid. The rate of oxidoreduction was calculated from the decrease in the ratio between /sup 3/H and /sup 14/C in the respective bile acid isolated from duodenal contents collected at different time intervals after administration of the labeled bile acids. The mean fractional conversion rate was found to be 0.29 day-1 for the 3 alpha-hydroxyl group in deoxycholic acid (n = 2), 0.18 day-1 for the 12 alpha-hydroxyl group in deoxycholic acid (n = 6), 0.09 day-1 for the 3 alpha-hydroxyl group in cholic acid (n = 3), 0.05 day-1 for the 7 alpha-hydroxyl group in cholic acid (n = 2), and 0.03 day-1 for the 12 alpha-hydroxyl group in cholic acid (n = 2). The extent of oxidoreduction of the 12 alpha-hydroxyl group in (12 beta-/sup 3/H)-labeled deoxycholic acid given to two patients operated with subtotal colectomy and ileostomy was markedly reduced (less than 20% of normal).

  17. Control of selectivity in allylic alcohol oxidation on gold surfaces: the role of oxygen adatoms and hydroxyl species.

    PubMed

    Mullen, Gregory M; Zhang, Liang; Evans, Edward J; Yan, Ting; Henkelman, Graeme; Mullins, C Buddie

    2015-02-14

    Gold catalysts display high activity and good selectivity for partial oxidation of a number of alcohol species. In this work, we discuss the effects of oxygen adatoms and surface hydroxyls on the selectivity for oxidation of allylic alcohols (allyl alcohol and crotyl alcohol) on gold surfaces. Utilizing temperature programmed desorption (TPD), reactive molecular beam scattering (RMBS), and density functional theory (DFT) techniques, we provide evidence to suggest that the selectivity displayed towards partial oxidation versus combustion pathways is dependent on the type of oxidant species present on the gold surface. TPD and RMBS results suggest that surface hydroxyls promote partial oxidation of allylic alcohols to their corresponding aldehydes with very high selectivity, while oxygen adatoms promote both partial oxidation and combustion pathways. DFT calculations indicate that oxygen adatoms can react with acrolein to promote the formation of a bidentate surface intermediate, similar to structures that have been shown to decompose to generate combustion products over other transition metal surfaces. Surface hydroxyls do not readily promote such a process. Our results help explain phenomena observed in previous studies and may prove useful in the design of future catalysts for partial oxidation of alcohols.

  18. Alcohol and aggression in a group interaction.

    PubMed

    Murdoch, D; Pihl, R O

    1985-01-01

    Forty-four volunteer male subjects participated in groups of four along with two experimental confederates in a group interaction after consuming either 1.32 mg/kg of 95% USP alcohol or placebo. According to a balanced-placebo design, subjects were told they were either consuming alcohol or placebo. The task of one confederate was to initiate conversation and distract subjects from monitoring their state of intoxication while the second confederate's role was to antagonize subjects at a prescribed time. Sessions were videotaped and rated for frequency of positive and negative interactions and subjects completed rating scales evaluating each other. The results failed to show an expectancy effect on any measures; however, there was an alcohol effect seen in an increase in negative interactions as well as positive interactions and a significant expectancy X alcohol interaction for negative ratings of the provocative confederate. In those groups where the manipulation matched the expectation, alcohol-told alcohol and placebo-told placebo the confederate was seen more negatively than in the mixed groups. An attributional explanation for the results is offered and the generality of the alcohol-expectancy phenomenon questioned.

  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. Relative impact of 3- and 5-hydroxyl groups of cytosporone B on cancer cell viability.

    PubMed

    Xia, Zebin; Cao, Xihua; Rico-Bautista, Elizabeth; Yu, Jinghua; Chen, Liqun; Chen, Jiebo; Bobkov, Andrey; Wolf, Dieter A; Zhang, Xiao-Kun; Dawson, Marcia I

    2013-02-01

    A novel and the shortest route, thus far, for preparing cytosporone B (Csn-B) is reported. Csn-B and two analogs were used to probe the importance of hydroxyl groups at the 3- and 5-positions of the Csn-B benzene ring in inhibiting the viability of human H460 lung cancer and LNCaP prostate cancer cells, inducing H460 cell apoptosis, and interacting with the NR4A1 (TR3) ligand-binding domain (LBD). These studies indicate that Csn-B and 5-Me-Csn-B, having a phenolic hydroxyl at the 3-position of their aromatic rings, had similar activities in inhibiting cancer cell viability and in inducing apoptosis, whereas 3,5-(Me)2-Csn-B was unable to do so. These results are in agreement with ligand-binding experiments showing that the interaction with the NR4A1 LBD required the presence of the 3-hydroxyl group.

  1. Predicting the acidity constant of a goethite hydroxyl group from first principles

    NASA Astrophysics Data System (ADS)

    Leung, Kevin; Criscenti, Louise J.

    2012-03-01

    Accurate predictions of the acid-base behavior of hydroxyl groups at mineral surfaces are critical for understanding the trapping of toxic and radioactive ions in soil samples. In this work, we apply ab initio molecular dynamics (AIMD) simulations and potential-of-mean-force techniques to calculate the pKa of a doubly protonated oxygen atom bonded to a single Fe atom (FeIOH2) on the goethite (101) surface. Using formic acid as a reference system, pKa = 7.0 is predicted, suggesting that isolated, positively charged groups of this type are marginally stable at neutral pH. Similarities and differences between AIMD and the more empirical multi-site complexation methodology are highlighted, particularly with respect to the treatment of hydrogen bonding with water and proton sharing among surface hydroxyl groups. We also highlight the importance of an electronic structure method that can accurately predict transition metal ion properties for goethite pKa calculations.

  2. XPS study of PBO fiber surface modified by incorporation of hydroxyl polar groups in main chains

    NASA Astrophysics Data System (ADS)

    Zhang, Tao; Hu, Dayong; Jin, Junhong; Yang, Shenglin; Li, Guang; Jiang, Jianming

    2010-01-01

    Dihydroxy poly(p-phenylene benzobisoxazole) (DHPBO), a modified poly(p-phenylene benzoxazole) (PBO) polymer containing double hydroxyl groups in polymer chains, was synthesized by copolymerization of 4,6-diamino resorcinol dihydrochloride (DAR), purified terephthalic acid (TA) and 2,5-dihydroxyterephthalic acid (DHTA). DHPBO fibers were prepared by dry-jet wet-spinning method. The effects of hydroxyl polar groups on the surface elemental compositions of PBO fiber were investigated by X-ray photoelectron spectroscopy (XPS). The results show that the ratio of oxygen/carbon on the surface of DHPBO fibers is higher than that on the surface of PBO fibers, which indicates the content of polar groups on the surface of DHPBO fiber increase compared with PBO fiber.

  3. 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

  4. Relative impact of 3- and 5-hydroxyl groups of cytosporone B on cancer cell viability†

    PubMed Central

    Rico-Bautista, Elizabeth; Yu, Jinghua; Chen, Liqun; Chen, Jiebo; Bobkov, Andrey; Wolf, Dieter A.; Zhang, Xiao-Kun; Dawson, Marcia I.

    2014-01-01

    A novel and the shortest route, thus far, for preparing cytosporone B (Csn-B) is reported. Csn-B and two analogs were used to probe the importance of hydroxyl groups at the 3- and 5-positions of the Csn-B benzene ring in inhibiting the viability of human H460 lung cancer and LNCaP prostate cancer cells, inducing H460 cell apoptosis, and interacting with the NR4A1 (TR3) ligand-binding domain (LBD). These studies indicate that Csn-B and 5-Me-Csn-B, having a phenolic hydroxyl at the 3-position of their aromatic rings, had similar activities in inhibiting cancer cell viability and in inducing apoptosis, whereas 3,5-(Me)2-Csn-B was unable to do so. These results are in agreement with ligand-binding experiments showing that the interaction with the NR4A1 LBD required the presence of the 3-hydroxyl group. PMID:24795803

  5. Structure-affinity relationship of flavones on binding to serum albumins: effect of hydroxyl groups on ring A.

    PubMed

    Xiao, Jianbo; Cao, Hui; Wang, Yuanfeng; Yamamoto, Koichiro; Wei, Xinlin

    2010-07-01

    Four flavones (flavone, 7-hydroxyflavone, chrysin, and baicalein) sharing the same B- and C-ring structure but a different numbers of hydroxyl groups on the A-ring were studied for their affinities for BSA and HSA. The hydroxylation on ring A of flavones increased the binding constants (K(a)) and the number of binding sites (n) between flavones and serum albumins. The affinities of 7-hydroxyflavone for BSA and HSA were about 800 times and 40 times higher than that of flavone, respectively. It appears that the optimal number of hydroxyl groups introduced to the ring A of flavones is one. As more hydroxyl groups were introduced to positions at C-5, C-6, and/or C-7 of flavones, the affinities for serum albumins decrease. The critical energy transfer distances (R(0)) between the hydroxylated flavones (1-3 OH on the ring A) and serum albumins decreased with the increasing affinities for serum albumins.

  6. An Involuntary Therapeutic Group for Alcohol Abusers.

    ERIC Educational Resources Information Center

    O'Connell, David F.; Beck, Terrence

    1984-01-01

    Describes a therapy program for student alcohol abusers conducted by an alcohol treatment specialist. Describes objectives and content of the eight sessions. Follow-up data on the Alcohol Intervention Program suggest it can have positive results. (JAC)

  7. Crystalline structures and mesomorphic properties of gemini diammonium surfactants with a pendant hydroxyl group.

    PubMed

    Wei, Zengbin; Wei, Xilian; Sun, Dezhi; Liu, Jiuqiang; Tang, Xiaojuan

    2011-02-15

    A series of homologous crystals of gemini diammonium surfactants (GDAS) containing one hydroxyl substituted methylene spacer are prepared. The crystal structures of these compounds, namely [C(n)H(2)(n)(+1)-N(+) (CH(3))(2)-CH(2)CH(OH)CH(2)-N(+)(CH(3))(2)-C(n)H(2)(n)(+1)], are determined by single-crystal X-ray diffraction techniques, in order to have a better understanding of the structure relation between the solid and the mesophase. The hydroxyl groups enhance the hydrogen bonding interaction between neighboring compounds, and therefore the packing of GDAS in the solid state is arranged to form a herringbone-like mode. To the best of our knowledge, this is the first GDAS crystal with a herringbone-like structure. Their mesomorphic properties are investigated by differential scanning calorimetry, polarizing optical microscopy, X-ray powder diffraction, and rheological measurement. These compounds have relatively low melting points and form thermotropic mesophases over a broad temperature range, as compared to those without a hydroxyl substituted at the spacer. The rheological behavior of the smectic phases clearly reveals that hydrogen bonds exert a significant effect on the high values of moduli and viscosity. Moreover, the melting point and rheological parameters increase, conforming to the length of alkyl chains.

  8. A first principle study of graphene functionalized with hydroxyl, nitrile, or methyl groups

    NASA Astrophysics Data System (ADS)

    Barhoumi, M.; Rocca, D.; Said, M.; Lebègue, S.

    2017-01-01

    By means of ab initio calculations, we study the functionalization of graphene by different chemical groups such as hydroxyl, nitrile, or methyl. Two extreme cases of functionalization are considered: a single group on a supercell of graphene and a sheet of graphene fully functionalized. Once the equilibrium geometry is obtained by density functional theory, we found that the systems are metallic when a single group is attached to the sheet of graphene. With the exception of the nitrile functionalized boat configuration, a large bandgap is obtained at full coverage. Specifically, by using the GW approximation, our calculated bandgaps are direct and range between 5.0 and 5.5 eV for different configurations of hydroxyl functionalized graphene. An indirect GW bandgap of 6.50 eV was found in nitrile functionalized graphene while the methyl group functionalization leads to a direct bandgap with a value of 4.50 eV. Since in the two limiting cases of minimal and full coverage, the electronic structure changes drastically from a metal to a wide bandgap semiconductor, a series of intermediate states might be expected by tuning the amount of functionalization with these different groups.

  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. Chemoselective methylation of phenolic hydroxyl group prevents quinone methide formation and repolymerization during lignin depolymerization

    DOE PAGES

    Kim, Kwang Ho; Dutta, Tanmoy; Walter, Eric D.; ...

    2017-03-22

    Chemoselective blocking of the phenolic hydroxyl (Ar–OH) group by methylation was found to suppress secondary repolymerization and charring during lignin depolymerization. Methylation of Ar–OH prevents formation of reactive quinone methide intermediates, which are partly responsible for undesirable secondary repolymerization reactions. Instead, this structurally modified lignin produces more relatively low molecular weight products from lignin depolymerization compared to unmodified lignin. This result demonstrates that structural modification of lignin is desirable for production of low molecular weight phenolic products. Finally, this approach could be directed toward alteration of natural lignification processes to produce biomass that is more amenable to chemical depolymerization.

  11. Exchange of carbon-bound hydrogen atoms ortho to the hydroxyl group in tyrosine.

    PubMed

    Martin, R B; Morlino, V J

    1965-10-22

    The carbon-bound hydrogen atoms of tyrosine that exchange with solvent protons in strongly acid solutions at about 100 degrees C are not the methylene hydrogen atoms but a pair on the aromatic ring. Of the two pairs of protons on the aromatic ring, observed in the proton magnetic resonance spectra, the pair at higher field undergoes exchange in 2.4N DCI at 100 degrees C. Other hydrogen atoms, attached either to aliphatic or aromatic carbon atoms, exhibit no noticeable exchange under the same conditions. From a chemicalshift analysis the exchanging protons are assigned as those ortho to the hydroxyl group on the aromatic ring.

  12. 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

  13. 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

  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. New type of trifunctional alcohol

    NASA Technical Reports Server (NTRS)

    Marsh, H. E., Jr.; Hutchison, J. J.

    1972-01-01

    New type of trifunctional alcohol was synthesized from commercially available trimer acid. Trifunctional alcohol is hydrocarbon with widely separated terminal hydroxyl groups, and was expressly developed as crosslinking agent for preparation of polyurethane propellants, binders and case liners.

  16. Influence of Molecular Hydrogen Diffusion on Concentration and Distribution of Hydroxyl Groups in Silica Fibers

    NASA Astrophysics Data System (ADS)

    Plotnichenko, Victor G.; Ivanov, Gennadii A.; Kryukova, Elena B.; Aksenov, Vyacheslav A.; Sokolov, Vyacheslav O.; Isaev, Victor A.

    2005-01-01

    To study the hydroxyl (OH)-group contamination mechanisms in silica-based optical fibers, the transmission spectra of substrate tubes and fiber preforms made from various types of silica glasses ("Suprasil F-300," KS-4V, and KUVI) are measured by the method of infrared Fourier spectroscopy in a wavelength region of 2-5 μm. Due to the intensity of the fundamental OH stretching vibration band, the absorption coefficient, concentration, and a distribution profile of OH groups across the aforesaid samples are calculated. It is found that using an oxyhydrogen burner in the modified chemical vapor deposition (MCVD) process of manufacturing preforms and fiber drawing, the main source of impurity OH groups can be the molecular hydrogen H2 penetrating into glass much deeper than the OH groups diffusing from the substrate tube surface. A simple model explaining the formation and diffusion of OH groups into a fiber core and cladding is proposed. It is shown that heating tubes and preforms in a flame of oxyhydrogen burner during fiber fabrication causes a significant OH-group content growth (almost by two orders of magnitude) near to the outer preform surface. Using substrate tubes made from Suprasil F-300 glass, optical fibers are fabricated having a silica core and fluorosilicate reflecting cladding with optical losses of 0.3 dB/km at 1.55 μm and a refractive-index difference between core and cladding ~ 1 . 10^-2.

  17. 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) ...

  18. Water Contact Angle Dependence with Hydroxyl Functional Groups on Silica Surfaces under CO2 Sequestration Conditions.

    PubMed

    Chen, Cong; Zhang, Ning; Li, Weizhong; Song, Yongchen

    2015-12-15

    Functional groups on silica surfaces under CO2 sequestration conditions are complex due to reactions among supercritical CO2, brine and silica. Molecular dynamics simulations have been performed to investigate the effects of hydroxyl functional groups on wettability. It has been found that wettability shows a strong dependence on functional groups on silica surfaces: silanol number density, space distribution, and deprotonation/protonation degree. For neutral silica surfaces with crystalline structure (Q(3), Q(3)/Q(4), Q(4)), as silanol number density decreases, contact angle increases from 33.5° to 146.7° at 10.5 MPa and 318 K. When Q(3) surface changes to an amorphous structure, water contact angle increases 20°. Water contact angle decreases about 12° when 9% of silanol groups on Q(3) surface are deprotonated. When the deprotonation degree increases to 50%, water contact angle decreases to 0. The dependence of wettability on silica surface functional groups was used to analyze contact angle measurement ambiguity in literature. The composition of silica surfaces is complicated under CO2 sequestration conditions, the results found in this study may help to better understand wettability of CO2/brine/silica system.

  19. Non-exchanging hydroxyl groups on the surface of cellulose fibrils: The role of interaction with water.

    PubMed

    Lindh, Erik L; Bergenstråhle-Wohlert, Malin; Terenzi, Camilla; Salmén, Lennart; Furó, István

    2016-11-03

    The interaction of water with cellulose stages many unresolved questions. Here (2)H MAS NMR and IR spectra recorded under carefully selected conditions in (1)H-(2)H exchanged, and re-exchanged, cellulose samples are presented. It is shown here, by a quantitative and robust approach, that only two of the three available hydroxyl groups on the surface of cellulose fibrils are exchanging their hydrogen with the surrounding water molecules. This finding is additionally verified and explained by MD simulations which demonstrate that the (1)HO(2) and (1)HO(6) hydroxyl groups of the constituting glucose units act as hydrogen-bond donors to water, while the (1)HO(3) groups behave exclusively as hydrogen-bond acceptors from water and donate hydrogen to their intra-chain neighbors O(5). We conclude that such a behavior makes the latter hydroxyl group unreactive to hydrogen exchange with water.

  20. 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.

  1. Regioselective inversion of the hydroxyl group in D-ribo-phytosphingosine via a cyclic sulfate and bis-sulfonate intermediate.

    PubMed

    Lee, Yun Mi; Baek, Dong Jae; Lee, Seokwoo; Kim, Deukjoon; Kim, Sanghee

    2011-01-21

    The selective synthesis of D-xylo- and D-lyxo-phytosphingosines from commercially available D-ribo-phytosphingosine is described. Thermolysis of the N-carbonyl protected cyclic sulfate led to an inversion of configuration of the proximal hydroxyl group to give the xylo-isomer, whereas the corresponding bis-sulfonate resulted in an inversion of configuration of the distal hydroxyl group to give the lyxo-isomer. This study allowed the comparison between a cyclic sulfate and a bis-sulfonate in an intramolecular substitution reaction involving a carbonyl oxygen nucleophile.

  2. Factors of Group Psychotherapy for Adult Alcoholics: A Literature Review.

    ERIC Educational Resources Information Center

    Howard, Jonathan K.

    Research on therapeutic factors of group psychotherapy for adult alcoholics is reviewed. The research in this area has focused on determining whether or not group psychotherapy is an effective treatment modality for alcoholics. This review examines therapeutic factors in three phases of treatment: (1) preadmission, (2) primary intervention, and…

  3. Unique lead adsorption behavior of activated hydroxyl group in two-dimensional titanium carbide.

    PubMed

    Peng, Qiuming; Guo, Jianxin; Zhang, Qingrui; Xiang, Jianyong; Liu, Baozhong; Zhou, Aiguo; Liu, Riping; Tian, Yongjun

    2014-03-19

    The functional groups and site interactions on the surfaces of two-dimensional (2D) layered titanium carbide can be tailored to attain some extraordinary physical properties. Herein a 2D alk-MXene (Ti3C2(OH/ONa)(x)F(2-x)) material, prepared by chemical exfoliation followed by alkalization intercalation, exhibits preferential Pb(II) sorption behavior when competing cations (Ca(II)/Mg(II)) coexisted at high levels. Kinetic tests show that the sorption equilibrium is achieved in as short a time as 120 s. Attractively, the alk-MXene presents efficient Pb(II) uptake performance with the applied sorption capacities of 4500 kg water per alk-MXene, and the effluent Pb(II) contents are below the drinking water standard recommended by the World Health Organization (10 μg/L). Experimental and computational studies suggest that the sorption behavior is related to the hydroxyl groups in activated Ti sites, where Pb(II) ion exchange is facilitated by the formation of a hexagonal potential trap.

  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. Distribution of Hydroxyl Groups in Kukersite Shale Oil: Quantitative Determination Using Fourier Transform Infrared (FT-IR) Spectroscopy.

    PubMed

    Baird, Zachariah Steven; Oja, Vahur; Järvik, Oliver

    2015-05-01

    This article describes the use of Fourier transform infrared (FT-IR) spectroscopy to quantitatively measure the hydroxyl concentrations among narrow boiling shale oil cuts. Shale oil samples were from an industrial solid heat carrier retort. Reference values were measured by titration and were used to create a partial least squares regression model from FT-IR data. The model had a root mean squared error (RMSE) of 0.44 wt% OH. This method was then used to study the distribution of hydroxyl groups among more than 100 shale oil cuts, which showed that hydroxyl content increased with the average boiling point of the cut up to about 350 °C and then leveled off and decreased.

  6. The Expectancy Challenge Alcohol Literacy Curriculum (ECALC): a single session group intervention to reduce alcohol use.

    PubMed

    Fried, Abigail B; Dunn, Michael E

    2012-09-01

    The Expectancy Challenge Alcohol Literacy Curriculum (ECALC) is a single session group-delivered program designed to modify alcohol expectancy processes and reduce alcohol use among children and young adults. The objective of this study was to demonstrate the effectiveness of the ECALC in reducing risky alcohol use among heavy drinking college men. Four fraternities at a large state university were randomly assigned to receive either the single session ECALC or a control presentation (2 fraternity houses per condition, n=250). Alcohol expectancies were assessed before and immediately after program presentation. Results demonstrated significant changes on 5 of the 7 subscales of the Comprehensive Effects of Alcohol Scale (CEOA) among students who received the ECALC when compared with control participants. Alcohol use data were collected for 4 weeks before and 4 weeks after program presentation. Compared with those in the control condition, students who received the ECALC demonstrated significant reductions in all facets of alcohol use measured, including decreased mean and peak blood alcohol content (BAC), decreased mean number of days drinking per week, decreased mean drinks per sitting, and decreased number of binge-drinking episodes per month. This study represents 2 important advances. First is the significant reduction in risky alcohol use produced by a single session group-delivered program. The second important advance is the success in changing expectancy processes without using impractical elements common in previous expectancy challenge methods (e.g., a "barlab" environment and actual alcohol administration).

  7. 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.

  8. Smart materials behavior in phosphates: Role of hydroxyl groups and relevance to antiwear films

    NASA Astrophysics Data System (ADS)

    Shakhvorostov, Dmitry; Müser, Martin H.; Song, Yang; Norton, Peter R.

    2009-07-01

    The elastic properties of materials under high pressure are relevant to the understanding and performance of many systems of current interest, for example, in geology and tribology. Of particular interest is the origin of the dramatic increase in modulus with increasing pressure, a response which is also called "smart materials behavior." In this context, simple phosphate-containing materials have been studied experimentally and theoretically, and the origins of this behavior have been associated with factors such as coordination of the cations and changes in the degree of polymerization and hydrogenation of the phosphate units. In the present paper we extend the former analysis on simple metal phosphate model compounds to so-called thermal films, an intermediate stage in the formation of effective antiwear films. The material was produced by heating a commercial zinc dialkyldithiophosphate (ZDDP), a common antiwear additive in lubricating oils, in poly-α-olefin base oil solutions to 150 °C, a process known to produce the thermal films. Its structure and equation of state were studied by means of x-ray diffraction and IR synchrotron radiation techniques during compression up to 25 GPa in a diamond anvil cell as well as during the subsequent decompression. As is the case for the simple metal phosphates, we find that the thermal films are relatively soft at low pressures but stiffen rapidly and ultimately amorphize irreversibly at high pressure. However, in addition to phase transformations involving cation sites occurring in the metal phosphates studied previously, thermal films undergo displacive transitions associated with instabilities of the hydroxyl groups. These results may imply that ZDDP ligands and those of the transformed materials not only affect ZDDP decomposition rate in engines but also the mechanical properties of the resulting antiwear films.

  9. Smart materials behavior in phosphates: role of hydroxyl groups and relevance to antiwear films.

    PubMed

    Shakhvorostov, Dmitry; Müser, Martin H; Song, Yang; Norton, Peter R

    2009-07-28

    The elastic properties of materials under high pressure are relevant to the understanding and performance of many systems of current interest, for example, in geology and tribology. Of particular interest is the origin of the dramatic increase in modulus with increasing pressure, a response which is also called "smart materials behavior." In this context, simple phosphate-containing materials have been studied experimentally and theoretically, and the origins of this behavior have been associated with factors such as coordination of the cations and changes in the degree of polymerization and hydrogenation of the phosphate units. In the present paper we extend the former analysis on simple metal phosphate model compounds to so-called thermal films, an intermediate stage in the formation of effective antiwear films. The material was produced by heating a commercial zinc dialkyldithiophosphate (ZDDP), a common antiwear additive in lubricating oils, in poly-alpha-olefin base oil solutions to 150 degrees C, a process known to produce the thermal films. Its structure and equation of state were studied by means of x-ray diffraction and IR synchrotron radiation techniques during compression up to 25 GPa in a diamond anvil cell as well as during the subsequent decompression. As is the case for the simple metal phosphates, we find that the thermal films are relatively soft at low pressures but stiffen rapidly and ultimately amorphize irreversibly at high pressure. However, in addition to phase transformations involving cation sites occurring in the metal phosphates studied previously, thermal films undergo displacive transitions associated with instabilities of the hydroxyl groups. These results may imply that ZDDP ligands and those of the transformed materials not only affect ZDDP decomposition rate in engines but also the mechanical properties of the resulting antiwear films.

  10. 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.

  11. Alcohol and immunology: Summary of the 2012 Alcohol and Immunology Research Interest Group (AIRIG) meeting.

    PubMed

    Ippolito, Jill A; Curtis, Brenda J; Choudhry, Mashkoor A; Kovacs, Elizabeth J

    2013-12-01

    On October 27, 2012, the 17th annual Alcohol and Immunology Research Interest Group (AIRIG) meeting was held at the Grand Wailea Hotel in Maui, Hawaii as a satellite meeting to the 2012 Society of Leukocyte Biology conference. This year's meeting focused on the influence of alcohol on signal transduction pathways in various disease and injury models. Three plenary sessions were held where invited speakers shared their research on alcohol-mediated alterations of cell signaling components, immune cell subsets, and inflammation. These studies suggested alcohol has a negative effect on cell signaling machinery and immune cell homeostasis, resulting in disease, disease progression, and increased mortality. Researchers also identified tissue-specific alcohol-linked elevations in markers of inflammation, including cold-shock proteins and microRNAs. Additionally, one study revealed the effects of alcohol on immune cell subsets in a model of allergic asthma.

  12. Synthesis and biological activities of NB-506 analogues: Effects of the positions of two hydroxyl groups at the indole rings.

    PubMed

    Ohkubo, M; Nishimura, T; Honma, T; Nishimura, I; Ito, S; Yoshinari, T; Suda, H A; Morishima, H; Nishimura, S

    1999-12-06

    In the course of a study of 6-N-amino-substituted analogues of NB-506 (1), a more potent anticancer drug, J-109,404 (2), in which the formyl group of NB-506 was replaced with a 1,3-dihydroxypropane group, was reported. A study of further modification in the positions of two hydroxyl groups at the indole rings of 2 resulted in the discovery of a 2,10-dihydroxy analogue, J-107,088 (3), which is a promising anticancer agent with a broader therapeutic window than J-109,404.

  13. Structure-activity relationships of nonisomerizable derivatives of tamoxifen: importance of hydroxyl group and side chain positioning for biological activity.

    PubMed

    Murphy, C S; Parker, C J; McCague, R; Jordan, V C

    1991-03-01

    other substitutions produced either estrogenic compounds or less potent antiestrogens. The hydroxyl group appears to be critical to locate the alkyl aminoethoxy side chain in the correct position in the steroid-binding site to block estrogen action. Novel antiestrogens were identified that could have been predicted based upon earlier drug-receptor models for the ER.

  14. Chain structures of surface hydroxyl groups formed via line oxygen vacancies on TiO2(110) surfaces studied using noncontact atomic force microscopy.

    PubMed

    Namai, Yoshimichi; Matsuoka, Osamu

    2005-12-22

    Structures of surface hydroxyl groups arranged on a reduced TiO2(110) surface that had line oxygen vacancies were studied using noncontact atomic force microscopy (NC-AFM). NC-AFM results revealed that by increasing the density of oxygen vacancies on the TiO2(110) surface, line oxygen vacancies were formed by removal of oxygen atoms in a bridge oxygen row on the TiO2(110) surface. After the TiO2(110) surface with the line oxygen vacancies was exposed to water, the surface showed hydroxyl chain structures that were composed of hydroxyl groups linearly arranged in a form of two rows on the line oxygen vacancies and on a neighboring bridge oxygen row. In-situ NC-AFM measurements of these surfaces exposed to water at room temperature revealed that hydroxyl chain structures were formed at the line oxygen vacancy. Annealing above 500 K was sufficient to remove the hydroxyl chain structures on the TiO2(110) surface and allowed line oxygen vacancies to reappear on the surface. The line oxygen vacancies are active sites for water dissociation. In conclusion, the formation of the hydroxyl chain structure suggests that the surface hydroxyl groups on a TiO2(110) surface can be controlled by preparing oxygen vacancy structures on the surface.

  15. Effect of alkyl chain length and hydroxyl group functionalization on the surface properties of imidazolium ionic liquids.

    PubMed

    Pensado, Alfonso S; Costa Gomes, Margarida F; Canongia Lopes, José N; Malfreyt, Patrice; Pádua, Agílio A H

    2011-08-14

    Properties of the surface of ionic liquids, such as surface tension, ordering, and charge and density profiles, were studied using molecular simulation. Two types of modification in the molecular structure of imidazolium cations were studied: the length of the alkyl side chain and the presence of a polar hydroxyl group at the end of the side chain. Four ionic liquids were considered: 1-ethyl-3-methylimidazolium tetrafluoroborate, [C(2)C(1)im][BF(4)]; 1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate, [C(2)OHC(1)im][BF(4)]; 1-octyl-3-methylimidazolium tetrafluoroborate, [C(8)C(1)im][BF(4)] and 1-(8-hydroxyoctyl)-3-methylimidazolium tetrafluoroborate, [C(8)OHC(1)im][BF(4)]. The surface tension was calculated using both mechanical and thermodynamic definitions, with consistent treatment of the long-range corrections. The simulations reproduce the available experimental values of surface tension with a maximum deviation of ±10%. This energetic characterization of the interface is completed by microscopic structural analysis of orientational ordering at the interface and density profiles along the direction normal to the interface. The presence of the hydroxyl group modifies the local structure at the interface, leading to a less organized liquid phase. The results allow us to relate the surface tension to the structural ordering at the liquid-vacuum interface.

  16. Number of free hydroxyl groups on bile acid phospholipids determines the fluidity and hydration of model membranes.

    PubMed

    Sreekanth, Vedagopuram; Bajaj, Avinash

    2013-10-10

    Interactions of synthetic phospholipids with model membranes determines the drug release capabilities of phospholipid vesicles at diseased sites. We performed 1,6-diphenyl-1,3,5-hexatriene (DPH)-based fluorescence anisotropy, Laurdan-based membrane hydration, and differential scanning calorimetry (DSC) studies to cognize the interactions of three bile acid phospholipids, lithocholic acid-phosphocholine (LCA-PC), deoxycholic acid-phosphocholine (DCA-PC), and cholic acid-phosphocholine (CA-PC) with model membranes. These studies revealed that bile acid phospholipids increases membrane fluidity in DCA-PC > CA-PC > LCA-PC order, indicating that induction of membrane fluidity is contingent on the number and positioning of free hydroxyl groups on bile acids. Similarly, DCA-PC causes maximum membrane perturbations due to the presence of a free hydroxyl group, whereas LCA-PC induces gel phase in membranes due to hydrophobic bile acid acyl chain interactions. These DCA-PC-induced membrane perturbations induce a drastic decrease in phase transition temperature (Tm) as determined by calorimetric studies, whereas doping of LCA-PC causes phase transition broadening without change in Tm. Doping of CA-PC induces membrane perturbations and membrane hydration like DCA-PC but sharpening of phase transition at higher doping suggests self-association of CA-PC molecules. Therefore these differential mode of interactions between bile acid phospholipids and model membranes would help in the future for their use in drug delivery.

  17. Regioselective ω-hydroxylation of medium-chain n-alkanes and primary alcohols by CYP153 enzymes from Mycobacterium marinum and Polaromonas sp. strain JS666.

    PubMed

    Scheps, Daniel; Malca, Sumire Honda; Hoffmann, Helen; Nestl, Bettina M; Hauer, Bernhard

    2011-10-07

    The oxofunctionalization of saturated hydrocarbons is an important goal in basic and applied chemistry. Biocatalysts like cytochrome P450 enzymes can introduce oxygen into a wide variety of molecules in a very selective manner, which can be used for the synthesis of fine and bulk chemicals. Cytochrome P450 enzymes from the CYP153A subfamily have been described as alkane hydroxylases with high terminal regioselectivity. Here we report the product yields resulting from C(5)-C(12) alkane and alcohol oxidation catalyzed by CYP153A enzymes from Mycobacterium marinum (CYP153A16) and Polaromonas sp. (CYP153A P. sp.). For all reactions, byproduct formation is described in detail. Following cloning and expression in Escherichia coli, the activity of the purified monooxygenases was reconstituted with putidaredoxin (CamA) and putidaredoxin reductase (CamB). Although both enzyme systems yielded primary alcohols and α,ω-alkanediols, each one displayed a different oxidation pattern towards alkanes. For CYP153A P. sp. a predominant ω-hydroxylation activity was observed, while CYP153A16 possessed the ability to catalyze both ω-hydroxylation and α,ω-dihydroxylation reactions.

  18. Effects of sex composition on group processes in alcohol prevention groups for teens.

    PubMed

    Garcia, Tracey A; Bacio, Guadalupe A; Tomlinson, Kristin; Ladd, Benjamin O; Anderson, Kristen G

    2015-08-01

    Although most alcohol and other drug prevention programs for adolescents are offered in group settings, little is known about the possible effects of sex composition on group processes and mechanisms of change. Using the Group Actor-Partner Interdependence Model framework, we examined how the sex constellation of adolescent prevention group members influenced youth satisfaction, engagement, and endorsement of healthy behavior during group. Participants in Project Options (N = 379; 61.8% girls; Mage = 16.1; SD = 1.4), a voluntary school-based alcohol prevention program, completed measures of satisfaction at each prevention session and observers rated engagement and change talk for each group. When analyses were oriented toward girls, their personal satisfaction, group-rated satisfaction, and group-level engagement were positively related to having more girls in the group. Similarly, in boys, personal satisfaction, satisfaction of the group as a whole, and engagement in groups improved when groups were composed of more girls. Statements supportive of healthy alcohol/drug-related decision making were unrelated to group composition. The findings suggest that the composition of girls and boys in groups has differential effects on some group processes. This avenue of research has merit for understanding the mechanisms associated with satisfaction and engagement in adolescent substance use prevention programs.

  19. Selected Publications on Teenagers and Alcohol. National Clearinghouse for Alcohol Information Grouped Interest Guide No. 8-5. Cumulative Issue.

    ERIC Educational Resources Information Center

    National Clearinghouse for Alcohol Information (DHEW/PHS), Rockville, MD.

    This Grouped Interest Guide is published by the National Institute on Alcohol Abuse and Alcoholism. Its purpose is to provide the reader with a regularly published set of bibliographic references for recent, topical literature in designated areas. Topics included in this guide are Youth, Children of Alcoholic Parents, and Social Forces. A wide…

  20. Fluoride removal mechanism of bayerite/boehmite nanocomposites: roles of the surface hydroxyl groups and the nitrate anions.

    PubMed

    Jia, Yong; Zhu, Bai-Sheng; Jin, Zhen; Sun, Bai; Luo, Tao; Yu, Xin-Yao; Kong, Ling-Tao; Liu, Jin-Huai

    2015-02-15

    Three-dimensional feather like bayerite/boehmite nanocomposites were synthesized by a facile one-pot hydrothermal method. The obtained nanocomposites were characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, and nitrogen adsorption-desorption isotherms. The removal properties toward fluoride were investigated, including adsorption kinetics, adsorption isotherm, and influences of pH and coexisting anions. The maximal adsorption capacity was 56.80 mg g(-1) at pH 7.0, which is favorable compared to those reported in the literature using other adsorbents. The coexisting of sulfate and bicarbonate inhibited the fluoride removal especially at high concentrations. Furthermore, the removal mechanism was revealed by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The results suggest that both of the surface hydroxyl groups and the nitrate anions were participated in the ion-exchange process.

  1. Study on dermatoses and their prevalence in groups of confirmed alcoholic individuals in comparison to a non-alcoholic group of individuals*

    PubMed Central

    Bruno, Maria Cecilia Teixeira de Carvalho; Vilela, Maria Aparecida Constantino; de Oliveira, Carlos Alberto B. Mendes

    2013-01-01

    BACKGROUND The direct relationship between alcoholism and dermatoses has been evaluated in recent researches. However, there are few objective surveys that demonstrate and prove a direct relationship between alcohol and a specific dermatosis. OBJECTIVES to verify the prevalence of dermatoses in alcoholics, analize the dermatological changes found in these patients and their evolution during alcoholic abstinence. Also, to compare the results obtained with a non-alcoholic control group and with the data found in medical literature. METHODS: the dermatologic conditions of 278 alcoholic patients (250 men, 28 women) were studied over a period of 4 years, and compared to those of a control group of 271 non-alcoholic individuals (249 men, 22 women), members of the Military Police Force. The individuals in both groups were between 20 and 60 years old. RESULTS Pellagra, nummular eczema, purpura pigmentosa chronica (also known as pigmented purpuric dermatosis) and psoriasis were more frequent in the group of alcoholics and, apparently, occurred in parallel with alcoholism that seems to play a role in the evolution of these dermatoses. The dermatopathies were more frequent before the age of forty, regardless of factors such as profession, race or gender. CONCLUSION the association of dermatoses and alcoholism was extremely significant according to the statistical data. Alcoholism can be considered a risk factor for pellagra, psoriasis, nummular eczema and purpura pigmentosa chronica dermatoses, which can, as well, be considered alcoholism indicators. PMID:23793198

  2. Alcoholism and Alcohol Abuse

    MedlinePlus

    ... their drinking causes distress and harm. It includes alcoholism and alcohol abuse. Alcoholism, or alcohol dependence, is a disease that causes ... groups. NIH: National Institute on Alcohol Abuse and Alcoholism

  3. Group Work as Facilitation of Spiritual Development for Drug and Alcohol Abusers.

    ERIC Educational Resources Information Center

    Page, Richard C.; Berkow, Daniel N.

    1998-01-01

    Describes group work designed to promote spiritual development with drug and alcohol abusers. Provides a definition of spirituality. Discusses research that relates to the spiritual development of members of drug and alcohol groups. Compares the ways that group work and Alcoholics Anonymous promote spiritual development. (Author/MKA)

  4. Structure-activity relationships among the kanamycin aminoglycosides: role of ring I hydroxyl and amino groups.

    PubMed

    Salian, Sumantha; Matt, Tanja; Akbergenov, Rashid; Harish, Shinde; Meyer, Martin; Duscha, Stefan; Shcherbakov, Dmitri; Bernet, Bruno B; Vasella, Andrea; Westhof, Eric; Böttger, Erik C

    2012-12-01

    The kanamycins form an important subgroup of the 4,6-disubstituted 2-deoxystreptamine aminoglycoside antibiotics, comprising kanamycin A, kanamycin B, tobramycin, and dibekacin. These compounds interfere with protein synthesis by targeting the ribosomal decoding A site, and they differ in the numbers and locations of amino and hydroxy groups of the glucopyranosyl moiety (ring I). We synthesized kanamycin analogues characterized by subtle variations of the 2' and 6' substituents of ring I. The functional activities of the kanamycins and the synthesized analogues were investigated (i) in cell-free translation assays on wild-type and mutant bacterial ribosomes to study drug-target interaction, (ii) in MIC assays to assess antibacterial activity, and (iii) in rabbit reticulocyte translation assays to determine activity on eukaryotic ribosomes. Position 2' forms an intramolecular H bond with O5 of ring II, helping the relative orientations of the two rings with respect to each other. This bond becomes critical for drug activity when a 6'-OH substituent is present.

  5. An Iminium Salt Organocatalyst for Selective Aliphatic C-H Hydroxylation.

    PubMed

    Wang, Daoyong; Shuler, William G; Pierce, Conor J; Hilinski, Michael K

    2016-08-05

    The first examples of catalysis of aliphatic C-H hydroxylation by an iminium salt are presented. The method allows the selective organocatalytic hydroxylation of unactivated 3° C-H bonds at room temperature using hydrogen peroxide as the terminal oxidant. Hydroxylation of an unactivated 2° C-H bond is also demonstrated. Furthermore, improved functional group compatibility over other catalytic methods is reported in the form of selectivity for aliphatic C-H hydroxylation over alcohol oxidation. On the basis of initial mechanistic studies, an oxaziridinium species is proposed as the active oxidant.

  6. Stabilization of hydroxyl-group-terminated SERS-marker molecules on microAg particles by silanization.

    PubMed

    Xia, Lixin; Kim, Nam Hoon; Kim, Kwan

    2007-02-01

    Micrometer-sized Ag (microAg) powders are very efficient substrates for both the infrared and Raman spectroscopic characterization of molecular adsorbates assembled on silver. In particular, the Raman spectrum of organic monolayers on microAg powders is a surface-enhanced Raman scattering (SERS) spectrum. To use microAg powders as a core material for constructing molecular sensing/recognition units operating via SERS, it is first necessary to stabilize the SERS-marker molecules that are directly in contact with the microAg powders. One promising strategy is the fabrication of silica shells onto SERS-marker molecules, and herein we demonstrate its feasibility by choosing 4-mercaptophenol (4-MPH) as a model SERS-marker molecule. Due to the presence of the hydroxyl group of 4-MPH, silica was readily deposited onto microAg particles by the base-catalyzed hydrolysis of tetraethyl orthosilicate, and its subsequent condensation, to form a cagelike structure. The formation of silica shells was confirmed with infrared, Raman, and X-ray photoelectron spectroscopy, coupled with field emission scanning electron microscopy. We were able to tune the thickness of silica shells simply by varying the silanization reaction time.

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

    PubMed

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

    2008-07-15

    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 SiO(2), 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.

  8. 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.

  9. Energies and 2'-Hydroxyl Group Orientations of RNA Backbone Conformations. Benchmark CCSD(T)/CBS Database, Electronic Analysis, and Assessment of DFT Methods and MD Simulations.

    PubMed

    Mládek, Arnošt; Banáš, Pavel; Jurečka, Petr; Otyepka, Michal; Zgarbová, Marie; Šponer, Jiří

    2014-01-14

    Sugar-phosphate backbone is an electronically complex molecular segment imparting RNA molecules high flexibility and architectonic heterogeneity necessary for their biological functions. The structural variability of RNA molecules is amplified by the presence of the 2'-hydroxyl group, capable of forming multitude of intra- and intermolecular interactions. Bioinformatics studies based on X-ray structure database revealed that RNA backbone samples at least 46 substates known as rotameric families. The present study provides a comprehensive analysis of RNA backbone conformational preferences and 2'-hydroxyl group orientations. First, we create a benchmark database of estimated CCSD(T)/CBS relative energies of all rotameric families and test performance of dispersion-corrected DFT-D3 methods and molecular mechanics in vacuum and in continuum solvent. The performance of the DFT-D3 methods is in general quite satisfactory. The B-LYP-D3 method provides the best trade-off between accuracy and computational demands. B3-LYP-D3 slightly outperforms the new PW6B95-D3 and MPW1B95-D3 and is the second most accurate density functional of the study. The best agreement with CCSD(T)/CBS is provided by DSD-B-LYP-D3 double-hybrid functional, although its large-scale applications may be limited by high computational costs. Molecular mechanics does not reproduce the fine energy differences between the RNA backbone substates. We also demonstrate that the differences in the magnitude of the hyperconjugation effect do not correlate with the energy ranking of the backbone conformations. Further, we investigated the 2'-hydroxyl group orientation preferences. For all families, we conducted a QM and MM hydroxyl group rigid scan in gas phase and solvent. We then carried out set of explicit solvent MD simulations of folded RNAs and analyze 2'-hydroxyl group orientations of different backbone families in MD. The solvent energy profiles determined primarily by the sugar pucker match well with the

  10. The Hispanic Americans Baseline Alcohol Survey (HABLAS): Alcoholic beverage preference across Hispanic national groups

    PubMed Central

    Caetano, Raul; Vaeth, Patrice A. C.; Ramisetty-Mikler, Suhasini; Rodriguez, Lori A.

    2009-01-01

    Background U.S. Hispanics come from many countries in Latin America, which can lead to different beverage preferences in the U.S. This paper examines choice for drinking wine, beer, and liquor across 4 Hispanic national groups: Mexican Americans, Puerto Ricans, Cuban Americans, and South/Central Americans. Methods A sample of 5,224 individuals 18 years of age and older was selected using multistage cluster procedures from the household population in 5 metropolitan areas of the U.S.: Miami, New York, Philadelphia, Houston, and Los Angeles. The survey weighted response rate was 76%. Face-to-face interviews lasting 1 hour on average were conducted in the respondents’ homes either in English or Spanish. Results Among men, beer drinkers consume the highest mean number of drinks per week in all national groups. Among women, this is true only of Puerto Ricans and Mexican Americans. Among men who drink beer, beer drinking constitutes 52% to 72% of total alcohol consumption. Among women who drink beer, beer consumption is associated with 32% to 64% of total consumption. Beer is the beverage most associated with binge drinking among Puerto Rican and Mexican American women, while among Cuban American and South/Central American this is seen for wine. Regression analyses showed no significant differences by national group in the likelihood of drinking 2 or fewer drinks (versus no drinks) of wine, beer, or liquor. Puerto Ricans were more likely (OR=1.47; 95% CI=1.00–2.14) than Cuban Americans to drink 3 or more drinks (compared to no drinks) of beer. There was no association between the likelihood of binge drinking and Hispanic national group. Conclusions Beverage preference across Hispanic national groups is similar. Beer is the preferred beverage. Alcohol control policies such as taxation and control of sales availability should apply equally to beer, liquor, and wine. Prevention interventions directed at different Hispanic national groups in the U.S. can be relatively

  11. A Collegiate Group for the Sons and Daughters of Alcoholics.

    ERIC Educational Resources Information Center

    Donovan, Bruce E.

    1981-01-01

    In a university setting, children of alcoholics met for a series of sessions to discuss their similar backgrounds and to identify coping mechanisms. The students received information on treatment for the alcoholic parent and for themselves in the event that they should become alcoholics. (JN)

  12. Alcohol and group formation: a multimodal investigation of the effects of alcohol on emotion and social bonding.

    PubMed

    Sayette, Michael A; Creswell, Kasey G; Dimoff, John D; Fairbairn, Catharine E; Cohn, Jeffrey F; Heckman, Bryan W; Kirchner, Thomas R; Levine, John M; Moreland, Richard L

    2012-08-01

    We integrated research on emotion and on small groups to address a fundamental and enduring question facing alcohol researchers: What are the specific mechanisms that underlie the reinforcing effects of drinking? In one of the largest alcohol-administration studies yet conducted, we employed a novel group-formation paradigm to evaluate the socioemotional effects of alcohol. Seven hundred twenty social drinkers (360 male, 360 female) were assembled into groups of 3 unacquainted persons each and given a moderate dose of an alcoholic, placebo, or control beverage, which they consumed over 36 min. These groups' social interactions were video recorded, and the duration and sequence of interaction partners' facial and speech behaviors were systematically coded (e.g., using the facial action coding system). Alcohol consumption enhanced individual- and group-level behaviors associated with positive affect, reduced individual-level behaviors associated with negative affect, and elevated self-reported bonding. Our results indicate that alcohol facilitates bonding during group formation. Assessing nonverbal responses in social contexts offers new directions for evaluating the effects of alcohol.

  13. University Students from Homes with Alcoholic Parents: Considerations for Therapy Groups.

    ERIC Educational Resources Information Center

    Harman, Marsha J.; Withers, Larry

    1992-01-01

    Presents descriptive data collected during 1988-89 academic year from three adult children of alcoholics groups offered by a university counseling center. Describes group members, structured group activities, and recommendations for therapy groups for young adult children of alcoholics. (Author/NB)

  14. Hydroxyl ionic liquids: the differentiating effect of hydroxyl on polarity due to ionic hydrogen bonds between hydroxyl and anions.

    PubMed

    Zhang, Shiguo; Qi, Xiujuan; Ma, Xiangyuan; Lu, Liujin; Deng, Youquan

    2010-03-25

    The polarity of a series of ionic liquids (ILs) based on hydroxyethyl-imidazolium moiety with various anions ([PF(6)], [NTf(2)], [ClO(4)], [DCA], [NO(3)], [AC], and [Cl]) and their corresponding nonhydroxyl ILs was investigated by solvatochromic dyes and fluorescence probe molecules. Most of the nonhydroxyl ILs exhibit anion-independent polarity with similar E(T)(30) in the narrow range of 50.7-52.6 kcal/mol, except [EMIm][AC] (49.7 kcal/mol). However, the polarity of the hydroxyl ILs covers a rather wide range (E(T)(30) = 51.2-61.7 kcal/mol) and is strongly anion-dependent. According to their E(T)(30) or E(T)(33) values, the hydroxyl ILs can be further classified into the following three groups: (Iota) acetate-based hydroxyl ILs [HOEMIm][AC] exhibit polarity scale (E(T)(30) = 51.2 kcal/mol) similar to short chain alcohol and fall in the range of the nonhydroxyl ILs; (II) Hydroxyl ILs containing anions [NO(3)], [DCA], and [Cl] exhibit comparable polarity (E(T)(30) = 55.5-56.9 kcal/mol), moderately higher than those of their nonhydroxyl ILs; (III) Hydroxyl ILs containing anions [PF(6)], [NTf(2)], and [ClO(4)] possess unusual "hyperpolarity" (E(T)(30) = 60.3-61.7 kcal/mol) close to protic ILs and water. Kamlet-Taft parameters and density functional theory calculations indicated that the greatly expanded range of polarity of hydroxyl ILs is correlated to an intramolecular synergistic solvent effect of the ionic hydrogen-bonded HBD/HBA complexes generated by intrasolvent HBD/HBA association between the anions and the hydroxyl group on cations, wherein hydroxyl group exhibits a significant differentiating effect on the strength of H-bonding and thus the polarity. Spiropyran-merocyanine equilibrium acted as a model polarity-sensitive reaction indeed shows obviously polarity-dependent solvatochromism, photochromism, and thermal reversion in hydroxyl ILs.

  15. Effect of replacing a hydroxyl group with a methyl group on arsenic (V) species adsorption on goethite (alpha-FeOOH).

    PubMed

    Zhang, J S; Stanforth, R S; Pehkonen, S O

    2007-02-01

    Arsenate and methylated arsenicals, such as dimethylarsinate (DMA) and monomethylarsonate (MMA), are being found with increasing frequency in natural water systems. The mobility and bioavailability of these arsenic species in the environment are strongly influenced by their interactions with mineral surface, especially iron and aluminum oxides. Goethite (alpha-FeOOH), one of the most abundant ferric (hydr)oxides in natural systems, has a high retention capacity for arsenic species. Unfortunately, the sorption mechanism for the species is not completely understood, which limits our ability to model their behavior in natural systems. The purpose of this study is to investigate the effect of replacing a hydroxyl group with a methyl group on the adsorption behaviors of arsenic (V) species using adsorption edges, the influence of the background electrolyte on arsenic adsorption, and their effect on the zeta potential of goethite. The affinity of the three species to the goethite surface decreases in the order of AsO4=MMA>DMA. The uptake of DMA and MMA is independent of the concentration of background electrolyte, indicating that both species form inner-sphere complexes on the goethite surface and the most charge of adsorbed DMA and MMA locates at the surface plane. Arsenate uptake increases with increasing concentrations of background electrolyte at pH above 4, possibly due to that the charge of adsorbed arsenate is distributed between the surface plane and another electrostatic plane. DMA and lower concentrations of MMA have small effect on the zeta potential, whereas the zeta potential of goethite decreases in the presence of arsenate. The small effect on zeta potential of DMA or MMA adsorption suggests that the sorption sites for the anions is not important in controlling the surface charge. This observation is inconsistent with most adsorption models that postulate a singly coordinated hydroxyls contributing to both the adsorption and the surface charge, but

  16. Stabilization of organometal halide perovskite films by SnO2 coating with inactive surface hydroxyl groups on ZnO nanorods

    NASA Astrophysics Data System (ADS)

    Wang, Peng; Zhao, Jinjin; Liu, Jinxi; Wei, Liyu; Liu, Zhenghao; Guan, Lihao; Cao, Guozhong

    2017-01-01

    Perovskite solar cells have advanced rapid in the last few years, however the thermal instability of perovskite film on ZnO nanorods (NRs) remains a big challenge limiting its commercialization. The present work demonstrated effective suppression of the decomposition of CH3NH3PbI3 perovskite through inserting a thin tin oxide (SnO2) passivation layer between ZnO NRs and perovskite films. Although X-ray photoelectron spectroscopy (XPS) results showed no distinct difference in the amount of hydroxyl groups and oxygen vacancies on the surface of ZnO NRs and ZnO@SnO2 NRs, Raman spectra suggested the hydroxyl groups might be trapped in oxygen vacancies on SnO2 surface, preventing the decomposition of CH3NH3PbI3 perovskite through reacting with the hydroxyl groups. The power conversion efficiency of perovskite solar cells was significantly increased from 6.92% to 12.17% and became hysteresis-free by applying SnO2 passivating layer between perovskite and ZnO layers.

  17. Reducing Alcohol Risk in Adjudicated Male College Students: Further Validation of a Group Motivational Enhancement Intervention

    ERIC Educational Resources Information Center

    LaBrie, Joseph W.; Cail, Jessica; Pedersen, Eric R.; Migliuri, Savannah

    2011-01-01

    This study examined the effectiveness of a single-session group motivational enhancement alcohol intervention on adjudicated male college students. Over two sequential academic years, 230 students sanctioned by the university for alcohol-related infractions attended a 60- to 75-minute group intervention. The intervention consisted of a timeline…

  18. Interaction of water, hydrogen and their mixtures with SnO2 based materials: the role of surface hydroxyl groups in detection mechanisms.

    PubMed

    Pavelko, Roman G; Daly, Helen; Hardacre, Christopher; Vasiliev, Alexey A; Llobet, Eduard

    2010-03-20

    DRIFTS, TGA and resistance measurements have been used to study the mechanism of water and hydrogen interaction accompanied by a resistance change (sensor signal) of blank and Pd doped SnO(2). It was found that a highly hydroxylated surface of blank SnO(2) reacts with gases through bridging hydroxyl groups, whereas the Pd doped materials interact with hydrogen and water through bridging oxygen. In the case of blank SnO(2) the sensor signal maximum towards H(2) in dry air (R(0)/R(g)) is observed at approximately 345 degrees C, and towards water, at approximately 180 degrees C, which results in high selectivity to hydrogen in the presence of water vapors (minor humidity effect). In contrast, on doping with Pd the response to hydrogen in dry air and to water occurred in the same temperature region (ca. 140 degrees C) leading to low selectivity with a high effect of humidity. An increase in water concentration in the gas phase changes the hydrogen interaction mechanism of Pd doped materials, while that of blank SnO(2) is unchanged. The interaction of hydrogen with the catalyst doped SnO(2) occurs predominantly through hydroxyl groups when the volumetric concentration of water in the gas phase is higher than that of H(2) by a factor of 1000.

  19. 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.

  20. The presence of a hydroxyl group at the C-1 atom of the transketolase substrate molecule is necessary for the enzyme to perform the transferase reaction.

    PubMed

    Meshalkina, L E; Neef, H; Tjaglo, M V; Schellenberger, A; Kochetov, G A

    1995-11-20

    Transketolase catalyzes the transfer of an aldehyde residue from keto sugars to aldo sugars. The intermediate product is dihydroxyethylthiamine pyrophosphate (DHETPP). In the absence of an acceptor substrate, the reaction is stopped at this stage and DHETPP does not undergo subsequent transformations. Pyruvate decarboxylase catalyses pyruvate decarboxylation to yield free aldehyde. The intermediate product is hydroxyethylthiamine pyrophosphate (HETPP). It differs from DHETPP only in that it has no hydroxyl at the C-2 atom of the aldehyde residue. We have shown that transketolase can bind HETPP and split the aldehyde residue from it. This fact suggests that the path of the reaction is determined by the absence (in HETPP) or presence (in DHETPP) of a hydroxyl group. In the former case the reaction will yield free aldehyde, in the latter the aldehyde residue will be transferred onto an acceptor substrate.

  1. Summary of the 2014 Alcohol and Immunology Research Interest Group (AIRIG) meeting

    PubMed Central

    Hammer, Adam M.; Morris, Niya L.; Cannon, Abigail R.; Shults, Jill A.; Curtis, Brenda; Casey, Carol A.; Sueblinvong, Viranuj; Persidsky, Yuri; Nixon, Kimberly; Brown, Lou Ann; Waldschmidt, Thomas; Mandrekar, Pranoti; Kovacs, Elizabeth J.; Choudhry, Mashkoor A.

    2015-01-01

    On November 21, 2014 the 19th annual Alcohol and Immunology Research Interest Group (AIRIG) meeting was held at Loyola University Chicago Health Sciences Campus in Maywood, Illinois. The meeting focused broadly on inflammatory cell signaling responses in the context of alcohol and alcohol use disorders, and was divided into four plenary sessions focusing on the gut and liver, lung infections, general systemic effects of alcohol, and neuro-inflammation. One common theme amongst many talks was the differential roles of macrophages following both chronic and acute alcohol intoxication. Macrophages were shown to play significant roles in regulating inflammation, oxidative stress, and viral infection following alcohol exposure in the liver, lungs, adipose tissue, and brain. Other work examined the role of alcohol on disease progression in a variety of pathologies including psoriasis, advanced stage lung disease, and cancer. PMID:26520175

  2. 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.

  3. Role of diaxial versus diequatorial hydroxyl groups in the tumorigenic activity of a benzo[a]pyrene bay-region diol epoxide.

    PubMed Central

    Chang, R L; Wood, A W; Conney, A H; Yagi, H; Sayer, J M; Thakker, D R; Jerina, D M; Levin, W

    1987-01-01

    Tumorigenic activities of the (7R,8S,9S,10R)-7,8-dihydroxy-9,10-epoxy-7,8,9,10-tetrahydro derivatives of benzo[a]pyrene [(+)-B[a]P diol epoxide-2] and 6-fluorobenzo[a]pyrene (6-FB[a]P diol epoxide-2) were evaluated in newborn CD-1 mice. A total dose of 14 nmol of either diol epoxide was administered to preweanling mice, and tumorigenic activity was determined when the mice were 32 to 36 weeks old. At the termination of the study, 13% of solvent-treated control mice had developed lung tumors with an average of 0.19 tumor per mouse. No other tumors were observed in control animals. (+)-B[a]P diol epoxide-2 induced pulmonary tumors in 60% of the mice with an average of 1.9 tumors per mouse, and 14% of the male mice developed hepatic tumors with an average of 0.18 tumor per mouse. In contrast, 6-FB[a]P diol epoxide-2 had no significant tumorigenic activity at the 14-nmol dose. Although both bay-region diol epoxides have the same absolute configuration, (7R,8S,9S,10R), the hydroxyl groups of (+)-B[a]P diol epoxide-2 prefer the pseudoequatorial conformation whereas the hydroxyl groups of 6-FB[a]P diol epoxide-2 prefer the pseudoaxial conformation. The tumorigenicity results reported here are the first direct demonstration that conformation of the hydroxyl groups in a bay-region diol epoxide, in addition to the documented effect of absolute configuration, is an important determinant in the tumorigenic activity of these ultimate carcinogens. PMID:3479808

  4. The Hispanic Americans Baseline Alcohol Survey (HABLAS): Acculturation, Birthplace and Alcohol-Related Social Problems across Hispanic National Groups

    ERIC Educational Resources Information Center

    Caetano, Raul; Vaeth, Patrice A. C.; Rodriguez, Lori A.

    2012-01-01

    The purpose of this study was to examine the association between acculturation, birthplace, and alcohol-related social problems across Hispanic national groups. A total of 5,224 Hispanic adults (18+ years) were interviewed using a multistage cluster sample design in Miami, New York, Philadelphia, Houston, and Los Angeles. Multivariate analysis…

  5. 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

  6. 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.

  7. Residues of the human nuclear vitamin D receptor that form hydrogen bonding interactions with the three hydroxyl groups of 1alpha,25-dihydroxyvitamin D3.

    PubMed

    Reddy, Madhuri D; Stoynova, Ludmilla; Acevedo, Alejandra; Collins, Elaine D

    2007-03-01

    Most of the biological effects of 1,25-dihydroxyvitamin D(3) (hormone D) are mediated through the nuclear vitamin D receptor (VDR). Hormone binding induces conformational changes in VDR that enable the receptor to activate gene transcription. It is known that residues S237 and R274 form hydrogen bonds with the 1-hydroxyl group of hormone D, while residues Y143 and S278, and residues H305 and H397 form hydrogen bonds with the 3-hydroxyl and the 25-hydroxyl groups of the hormone. A series of VDR mutations were constructed (S237A, R274A, R274Q, Y143F, Y143A, S278A, H305A, and H397F; double mutants: S237A/R274A, Y143F/S278A, Y143A/S278A, and H305A/H397F). The relative binding affinities of the wild-type and variant VDRs were assessed. All of the mutants except H397F resulted in lower binding affinity compared to wild-type VDR. Binding to hormone was barely detectable in Y143F, H305A, and H305A/H397F mutants, and undetectable in mutants R274A, R274Q, Y143A, S237A/R274A, and Y143A/S278A, indicating the importance of these residues. Ability to activate gene transcription was also assessed. All of the VDR mutants, except the single mutant S278A, required higher doses of hormone D for half-maximal response. Defining the role of hormone D-VDR binding will lead to a better understanding of the vitamin D signal transduction pathway.

  8. 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; ...

    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

  9. 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.

  10. 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.

  11. Solid-state MAS NMR, TEM, and TGA studies of structural hydroxyl groups and water in nanocrystalline apatites prepared by dry milling.

    PubMed

    Pajchel, Lukasz; Kolodziejski, Waclaw

    2013-01-01

    A series of nanocrystalline calcium hydroxyapatites was prepared by dry milling and characterized using proton and (31)P MAS NMR, TEM, and TGA methods. The samples contained stubby rod-shaped crystals, which length and width varied in the 130-30 and 95-20 nm ranges, respectively. It was confirmed that concentration of structural hydroxyl groups in nanocrystalline apatites decreases with the decreasing crystal size. In the series of the studied apatites, the decrease was from 86 to ca. 50 % in reference to stoichiometric apatite. Water was found in the surface hydrated layer and in the c-axis channels, in which compartments existed as adsorbed and structural, respectively. Molecules of the adsorbed water were capable of moving from the crystal surface into the lattice c-axis channels of apatite. This process introduced considerable structural disorder within and around those channels and reduced the content of the structural hydroxyl groups, particularly in the region underneath the apatite crystal surface.

  12. 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.

  13. Alcohol

    MedlinePlus

    ... that's how many accidents occur. continue What Is Alcoholism? What can be confusing about alcohol is that ... develop a problem with it. Sometimes, that's called alcoholism (say: al-kuh-HOL - ism) or being an ...

  14. Alcohol

    MedlinePlus

    If you are like many Americans, you drink alcohol at least occasionally. For many people, moderate drinking ... risky. Heavy drinking can lead to alcoholism and alcohol abuse, as well as injuries, liver disease, heart ...

  15. Alcohol

    MedlinePlus

    ... de los dientes Video: Getting an X-ray Alcohol KidsHealth > For Kids > Alcohol Print A A A What's in this article? ... What Is Alcoholism? Say No en español El alcohol Getting the Right Message "Hey, who wants a ...

  16. Alcohol Habits in Patients with Long-Term Musculoskeletal Pain: Comparison with a Matched Control Group from the General Population

    ERIC Educational Resources Information Center

    Thelin Bronner, Kerstin Birgitta; Wennberg, Peter; Kallmen, Hakan; Schult, Marie-Louise Birgitta

    2012-01-01

    This prospective study aimed to describe alcohol habits in patients with chronic pain compared with those in a matched control group from the general Swedish population. In total, 100 consecutive patients enrolled were matched against 100 individuals in a control group on the basis of age and sex. Alcohol habits were measured using the Alcohol Use…

  17. Epidemiology of drinking, alcohol use disorders, and related problems in US ethnic minority groups.

    PubMed

    Caetano, Raul; Vaeth, Patrice A C; Chartier, Karen G; Mills, Britain A

    2014-01-01

    This chapter reviews selected epidemiologic studies on drinking and associated problems among US ethnic minorities. Ethnic minorities and the White majority group exhibit important differences in alcohol use and related problems, including alcohol use disorders. Studies show a higher rate of binge drinking, drinking above guidelines, alcohol abuse, and dependence for major ethnic and racial groups, notably, Blacks, Hispanics, and American Indians/Alaskan Natives. Other problems with a higher prevalence in certain minority groups are, for example, cancer (Blacks), cirrhosis (Hispanics), fetal alcohol syndrome (Blacks and American Indians/Alaskan Natives), drinking and driving (Hispanics, American Indians/Alaskan Natives). There are also considerable differences in rates of drinking and problems within certain ethnic groups such as Hispanics, Asian Americans, and American Indians/Alaskan Natives. For instance, among Hispanics, Puerto Ricans and Mexican Americans drink more and have higher rates of disorders such as alcohol abuse and dependence than Cuban Americans. Disparities also affect the trajectory of heavy drinking and the course of alcohol dependence among minorities. Theoretic accounts of these disparities generally attribute them to the historic experience of discrimination and to minority socioeconomic disadvantages at individual and environmental levels.

  18. Proton-bridge motions in amine conjugate acid ions having intramolecular hydrogen bonds to hydroxyl and amine groups.

    PubMed

    Ung, Hou U; Moehlig, Aaron R; Khodagholian, Sevana; Berden, Giel; Oomens, Jos; Morton, Thomas Hellman

    2013-02-14

    Vibrational spectra of two gaseous cations having NH···O intramolecular ionic hydrogen bonds and of nine protonated di- and polyamines having NH···N internal proton bridges, recorded using IR Multiple Photon Dissociation (IRMPD) of mass-selected ions, are reported. The band positions of hydroxyl stretching frequencies do not shift when a protonated amine becomes hydrogen bonded to oxygen. In three protonated diamines, lower frequency bands (550-650 cm(-1)) disappear upon isotopic substitution, as well as several bands in the 1100-1350 cm(-1) region. By treating the internal proton bridge as a linear triatomic, theory assigns the lowest frequency bands to N-H···N asymmetric stretches. A 2-dimensional model, based on quantization on a surface fit to points calculated using a double hybrid functional B2-P3LYP/cc-pVTZ//B3LYP/6-31G**, predicts their positions accurately. In at least one case, the conjugate acid of 1,5-cis-bis(dimethylamino)cyclooctane, a N-H···N bend shows up in the domain predicted by DFT normal mode calculations, but in most other cases the observed bands have frequencies 20-25% lower than expected for bending vibrations. Protonated Me(2)NCH(2)CMe(2)CH(2)CH(2)CH(2)NMe(2) shows three well-resolved bands at 620, 1200, and 1320 cm(-1), of which the lowest can be assigned to the asymmetric stretch. Other ions observed include doubly protonated 1,2,4,5-(Me(2)NCH(2))(4)-benzene and 1,2,4-(Me(2)NCH(2))(3)-benzene-5-CH(2)OH. Apart from the aforementioned rigid ion derived from the alicyclic diamine, the other ions enjoy greater conformational mobility, and coupling to low-frequency C-C bond torsions may account for the shift of vibrations with N-H···N character to lower frequencies. Low-barrier hydrogen bonding (LBHB) accounts for the fact that N-H···N asymmetric stretching vibrations of near linear proton bridges occur at frequencies below 650 cm(-1).

  19. Family History of Alcohol Abuse Moderates Effectiveness of a Group Motivational Enhancement Intervention in College Women

    PubMed Central

    LaBrie, Joseph W.; Feres, Nashla; Kenney, Shannon R.; Lac, Andrew

    2012-01-01

    This study examined whether a self-reported family history of alcohol abuse (FH+) moderated the effects of a female-specific group motivational enhancement intervention with first-year college women. First-year college women (N= 287) completed an initial questionnaire and attended an intervention (n=161) or control (n=126) group session, of which 118 reported FH+. Repeated measures ANCOVA models were estimated to investigate whether the effectiveness of the intervention varied as a function of one’s reported family history of alcohol abuse. Results revealed that family history of alcohol abuse moderated intervention efficacy. Although the intervention was effective in producing less risky drinking relative to controls, among those participants who received the intervention, FH+ women drank less across five weeks of follow-up than FH− women. The current findings provide preliminary support for the differential effectiveness of motivational enhancement interventions with FH+ women. Keywords: college women, intervention, alcohol abuse, family history, motivational interviewing PMID:19162406

  20. Close friend and group influence on adolescent cigarette smoking and alcohol use.

    PubMed

    Urberg, K A; Değirmencioğlu, S M; Pilgrim, C

    1997-09-01

    The relative influence of adolescents closest friends and their friendship group on their cigarette smoking and alcohol use was investigated in a short-term, longitudinal study of 1,028 students in the 6th, 8th, and 10th grades in 2 school systems. The amount of influence over the school year was modest in magnitude and came from the closest friend for initiation of cigarette and alcohol use. Only the friendship group use predicted transition into current cigarette use, whereas only the close friend use predicted transition into current alcohol use. Both group and close friends independently contributed to the prediction of adolescents' drinking to intoxication. No difference in the amount of influence, was found between stable and unstable close friendships or friendship groups; neither grade nor gender of the adolescents related to the amount of influence.

  1. Effect of hydroxyl and amino groups on electrochemiluminescence activity of tertiary amines at low tris(2,2'-bipyridyl)ruthenium(II) concentrations.

    PubMed

    Han, Shuang; Niu, Wenxin; Li, Haijuan; Hu, Lianzhe; Yuan, Yali; Xu, Guobao

    2010-04-15

    ECL of several amines containing different numbers of hydroxyl and amino groups was investigated. N-butyldiethanolamine is found to be more effective than 2-(dibutylamino)ethanol at gold and platinum electrodes, and is the most effective coreactant reported until now. Surprisingly, ECL intensities of monoamines, such as 2-(dibutylamino)ethanol and N-butyldiethanolamine, are much stronger than that of diamines including N,N,N',N'-tetrakis-(2-hydroxyethyl)-ethylenediamine and N,N,N',N'-tetrakis-(2-hydroxypropyl)ethlenediamine. The striking contrast between ECL signals of the investigated monoamines and diamines may result from more significant side reactions of diamines, such as the intramolecular side reactions between oxidative amine cation radicals and reductive amine free radicals.

  2. The influence of surface oxygen and hydroxyl groups on the dehydrogenation of ethylene, acetic acid and hydrogenated vinyl acetate on pure Pd(1 0 0): A DFT study

    NASA Astrophysics Data System (ADS)

    Huang, Yanping; Dong, Xiuqin; Yu, Yingzhe; Zhang, Minhua

    2016-12-01

    On the basis of a Langmuir-Hinshelwood-type mechanism, the dehydrogenation of ethylene, acetic acid and hydrogenated vinyl acetate (VAH) on pure Pd(1 0 0) with surface oxygen atoms (Os) and hydroxyl groups (OHs) was studied with density functional theory (DFT) method. Our calculation results show that both Os and OHs can consistently reduce the activation energies of dehydrogenation of ethylene, acetic acid and VAH to some degree with only one exception that OHs somehow increase the activation energy of VAH. Based on Langmuir-Hinshelwood mechanism, the three dehydrogenation reactions in presence of surface Os and OHs are almost consistently favored, compared with the corresponding processes on clean Pd(1 0 0) surfaces, and thus a Langmuir-Hinshelwood-type mechanism may not be excluded beforehand when investigating the microscopic performance of the oxygen-assisted vinyl acetate synthesis on Pd(1 0 0) catalysts.

  3. The dimensionality and measurement properties of alcohol outcome expectancies across Hispanic national groups.

    PubMed

    Mills, Britain; Caetano, Raul; Ramisetty-Mikler, Suhasini; Bernstein, Ira H

    2012-03-01

    This study examines the psychometric properties of alcohol expectancies among Hispanic subgroups. Face-to-face interviews were conducted as part of the 2006 Hispanic Americans Baseline Alcohol Survey (HABLAS), which employed a multistage cluster sample design. A total of 5224 individuals (18+ years of age) representing four Hispanic national groups (Puerto Ricans, Cuban Americans, Mexican Americans, and South/Central Americans) were selected at random from the household population in five metropolitan areas (Miami, New York, Philadelphia, Houston, and Los Angeles). Alcohol expectancies included 18 items covering positive (e.g., laugh more, become more talkative) and negative dimensions (e.g., become aggressive, lose control) when alcohol is consumed. Confirmatory factor models replicated a previously proposed three-factor dimensional structure with a substantial majority of items exhibiting measurement invariance across Hispanic national group and gender. Items covering social extroversion were an exception, showing a lack of invariance for female Cuban and South/Central Americans. Latent mean differences across groups were detected for expectancies concerning emotional fluidity, and the pattern of differences largely mirrored known differences in alcohol consumption patterns. Results suggest that caution should be exercised in interpreting differences in expectancies concerning social extroversion across Hispanic groups, and additional work is needed to identify indices of this construct with invariant measurement properties. However, measures of emotional/behavioral impairment and emotional fluidity expectancies can be validly compared across gender and Hispanic national groups.

  4. The Hispanic Americans Baseline Alcohol Survey (HABLAS): Acculturation, Birthplace and Alcohol-Related Social Problems Across Hispanic National Groups.

    PubMed

    Caetano, Raul; Vaeth, Patrice A C; Rodriguez, Lori A

    2012-02-01

    OBJECTIVE: To examine the association between acculturation, birthplace, and alcohol-related social problems across Hispanic national groups. METHOD: 5,224 Hispanic adults (18+ years) were interviewed using a multistage cluster sample design in Miami, New York, Philadelphia, Houston, and Los Angeles. RESULTS: Multivariate analysis shows no association between acculturation and problems among men or women. Birthplace is a risk factor for social problems among both genders. Among men, Mexican Americans, Puerto Ricans, and South/Central Americans are more likely to report social problems than Cuban Americans. Other risk factors for men are unemployment, a higher volume of drinking, and a higher frequency of binge drinking. Among women, Mexican American origin and binge drinking are also risk factors for reporting problems. CONCLUSIONS: U.S.-born Hispanics may experience stress and other detrimental effects to health because of their minority status, which may increase the likelihood of more drinking and the development of alcohol-related problems.

  5. 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.

  6. Alcohol

    MedlinePlus

    ... parents and other adults use alcohol socially — having beer or wine with dinner, for example — alcohol seems ... besides just hanging out in someone's basement drinking beer all night. Plan a trip to the movies, ...

  7. 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.

  8. Alcoholism.

    ERIC Educational Resources Information Center

    Caliguri, Joseph P., Ed.

    This extensive annotated bibliography provides a compilation of documents retreived from a computerized search of the ERIC, Social Science Citation Index, and Med-Line databases on the topic of alcoholism. The materials address the following areas of concern: (1) attitudes toward alcohol users and abusers; (2) characteristics of alcoholics and…

  9. The Tridimensional Personality Questionnaire as a predictor of relapse in detoxified alcohol dependents. The European Fluvoxamine in Alcoholism Study Group.

    PubMed

    Meszaros, K; Lenzinger, E; Hornik, K; Füreder, T; Willinger, U; Fischer, G; Schönbeck, G; Aschauer, H N

    1999-03-01

    Personality traits have been found as strong predictors for treatment response in different psychiatric disorders. We administered the Tridimensional Personality Questionnaire, which measures the three personality dimensions: novelty seeking, harm avoidance (HA), and reward dependence, as introduced by Cloninger in a multicenter study (11 centers in the United Kingdom, Eire, Switzerland, and Austria) with detoxified alcohol-dependent patients (n = 521). The objective of this study was to evaluate a possible predictive value of these three dimensions on relapse over 1 -year follow up. A logistic regression analysis showed that novelty seeking is a strong predictor for relapse in detoxified male alcoholics (p = 0.0007; p values adjusted for treatment), but not in females. In both sexes, HA and reward dependence were of no predictive value. However, we found a trend for significance of HA for predicting "early" relapse (4 weeks) in females (p = 0.074). Our results show that Tridimensional Personality Questionnaire personality traits have direct clinical applications for prediction of relapse in detoxified alcohol dependents and indicate the necessity of additional therapeutic treatment in risk groups.

  10. Oxidation of amino groups by hydroxyl radicals in relation to the oxidation degree of the alpha-carbon.

    PubMed

    Leitner, N Karpel Vel; Berger, P; Legube, B

    2002-07-15

    Nitrogen organic compounds constitute a large class of aqueous pollutants. These compounds include not only azoic structures, nitrogen heterocycles, and nitrous groups but also amides and amines. This work consisted in studying the OH* induced oxidation of simple primary amines in dilute aqueous solution with special attention to mineralization of the nitrogen group as a function of the nature of the alpha-carbon. H2O2/UV and gamma-irradiation processes were used for the production of OH* radicals, and the molecules studied were one alpha-amino acid i.e., glycine (HOOCCH2NH2), and two primary amides i.e., acetamide (CH3CONH2) and oxamic acid (HOOCCONH2). It was shown that the oxidation of glycine leads to the formation of ammonia, whereas the acetamide molecule is first oxidized into oxamic acid ending in complete mineralization with production of nitrates. Reaction mechanisms are proposed which account for the observed inorganic nitrogen end product depending on the oxidation degree of the carbon atoms of the molecules. It follows that the present study will allow for prediction of the fate of nitrogen resulting from the oxidation of primary amino groups by OH* radicals.

  11. 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.

  12. 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.

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

    PubMed

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

    2014-06-04

    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.

  14. Proceedings of the 2010 annual meeting of the Fetal Alcohol Spectrum Disorders Study Group.

    PubMed

    Kane, Cynthia J M; Smith, Susan M; Miranda, Rajesh C; Kable, Julie

    2012-02-01

    The annual meeting of the Fetal Alcohol Spectrum Disorders Study Group (FASDSG) was held on June 26, 2010 in San Antonio, TX, as a satellite of the Research Society on Alcoholism meeting. The FASDSG membership includes clinical, basic, and social scientists who meet to discuss recent advances and issues in Fetal Alcohol Spectrum Disorder (FASD) research. The central theme of the meeting was "Glia and Neurons: Teamwork in Pathology and Therapy." Alcohol disruption of neuron development and alcohol-induced neurodegeneration is central to the pathology and clinical expression of FASD. The active role of glia as perpetrator, victim, or bystander in neurotoxicology and neurodegenerative processes has emerged at the forefront of adult central nervous system (CNS) disorders and therapy. Glia- and neuron-glial interactions hold the potential to elucidate causes and offer treatment of FASD as well. Growing evidence indicates that neurons and glia are direct targets of alcohol, but may also be vulnerable to molecules produced in peripheral systems as a result of alcohol exposure. Diagnostics and therapies can take advantage of these processes and biomarkers, and these may be applicable to CNS pathology in FASD. Two keynote speakers, Howard E. Gendelman, M.D., and Ernest M. Graham, M.D, addressed the role of glia and neuroinflammation in brain development and neurodegeneration. The invited speakers and FASDSG members discussed new paradigms in CNS development and discuss new strategies for understanding and treating neurodegenerative disease. Members of the FASDSG provided updates on new findings through presentation of breaking research in the FASt data sessions. Representatives of national agencies provided updates on programs, activities, and funding priorities. The Henry Rosett Award was presented to R. Louise Floyd, R.N., D.S.N., for her career contributions to the field of fetal alcohol research. The Student and Postdoctoral Fellow Research Merit Award was presented to

  15. Effect of substituted hydroxyl groups in the changes of solution turbidity in the oxidation of aromatic contaminants.

    PubMed

    Villota, N; Jm, Lomas; Lm, Camarero

    2017-01-01

    This paper deals with the changes of turbidity that are generated in aqueous solutions of phenol when they are oxidized by using different Fenton technologies. Results revealed that if the Fenton reaction was promoted with UV light, the turbidity that was generated in the water doubled. Alternatively, the use of ultrasonic waves produced an increase in turbidity which initially proceeded slowly, reaching intensities eight times higher than in the conventional Fenton treatment. As well, the turbidity showed a high dependence on pH. It is therefore essential to control acidity throughout the reaction. The maximum turbidity was generated when operating at pH = 2.0, and it slowly decreased with increasing to a value of pH = 3.0, at which the turbidity was the lowest. This result was a consequence of the presence of ferric ions in solution. At pH values greater than 3.5, the turbidity increased almost linearly until at pH = 5.0 reached its maximum intensity. In this range, ferrous ions may generate an additional contribution of radicals that promote the degradation of the phenol species that produce turbidity. Turbidity was enhanced at ratios R = 4.0 mol H2O2/mol C6H6O. This value corresponds to the stoichiometric ratio that leads to the production of turbidity-precursor species. Therefore, muconic acid would be a species that generate high turbidity in solution according to its isomerism. Also, the results revealed that the turbidity is not a parameter to which species contribute additively since interactions may occur among species that would enhance their individual contributions to it. Analyzing the oxidation of phenol degradation intermediates, the results showed that meta-substituted compounds (resorcinol) generate high turbidity in the wastewater. The presence of polar molecules, such as muconic acid, would provide the structural features that are necessary for resorcinol to act as a clip between two carboxylic groups, thus establishing directional

  16. Hydroxyl end groups influence in vibrational and transport properties in polymer/monomer solutions: the PEO/EG case

    NASA Astrophysics Data System (ADS)

    Crupi, V.; Faraone, A.; Majolino, D.; Migliardo, P.; Venuti, V.; Villari, V.

    A study has been made of vibrational properties in ethylene glycol (EG; H(OCH2CH2)OH) and EG monomethyl ether (EGmE; CH3(OCH2CH2)OH) in solution together with poly(ethylene oxide) (PEO; H(OCH2CH2)nOH) at different concentrations, performed by Fourier transform infrared absorbance (FT-IR) spectroscopy. The results ae compared with previous viscometry and photon correlation spectroscopy (PCS) studies, using EG dimethyl ether (EGdE; CH3(OCH2CH2)OCH3) as solvent as well. These homologous systems differ from each other in the number of OH end groups, in particular two for EG, one for EgmE and zero for EGdE. Combining analysis of the vibrational and transport properties of EG, EGmE and EGdE in solution with PEO over a wide range of concentration made it possible to check the quality (good theta or poor) of these three different solvents and the role played by the hydrogen bond in the various solute-solvent interaction mechanisms, resulting in the well known de Gennes scaling law.

  17. Catalytic conversion of aliphatic alcohols on carbon nanomaterials: The roles of structure and surface functional groups

    NASA Astrophysics Data System (ADS)

    Tveritinova, E. A.; Zhitnev, Yu. N.; Chernyak, S. A.; Arkhipova, E. A.; Savilov, S. V.; Lunin, V. V.

    2017-03-01

    Carbon nanomaterials with the structure of graphene and different compositions of the surface groups are used as catalysts for the conversion of C2-C4 aliphatic alcohols. The conversions of ethanol, propanol- 1, propanol-2, butanol-1, butanol-2, and tert-butanol on carbon nanotubes, nanoflakes, and nanoflakes doped with nitrogen are investigated. Oxidized and nonoxidized multiwalled carbon nanotubes, nanoflakes, and nanoflakes doped with nitrogen are synthesized. X-ray diffraction analysis, X-ray photoelectron spectroscopy, scanning and transmission electronic microscopies, Brunauer-Emmett-Teller method, derivatographic analyses, and the pulsed microcatalytic method are used to characterize comprehensively the prepared catalysts. It was established that all of the investigated carbon nanomaterials (with the exception of nondoped carbon nanoflakes) are bifunctional catalysts for the conversion of aliphatic alcohols, and promote dehydration reactions with the formation of olefins and dehydrogenation reactions with the formation of aldehydes or ketones. Nanoflakes doped with nitrogen are inert with respect to secondary alcohols and tert-butanol. The role of oxygen-containing and nitrogen-containing surface groups, and of the geometrical structure of the carbon matrix of graphene nanocarbon materials in the catalytic conversion of aliphatic alcohols, is revealed. Characteristics of the conversion of aliphatic alcohols that are associated with their structure are identified.

  18. 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.

  19. 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.

  20. A Group Motivational Interviewing Intervention Reduces Drinking and Alcohol-Related Consequences in Adjudicated College Students

    ERIC Educational Resources Information Center

    LaBrie, Joseph W.; Lamb, Toby F.; Pedersen, Eric R.; Quinlan, Thomas

    2006-01-01

    This study examines the effectiveness of a single-session group motivational enhancement intervention with college students adjudicated for violation of alcohol policy. The intervention consisted of a timeline Followback assessment of drinking, social norms re-education, decisional balance for behavior change, relapse prevention, expectancy…

  1. Alcoholism - resources

    MedlinePlus

    Resources - alcoholism ... The following organizations are good resources for information on alcoholism : Alcoholics Anonymous -- www.aa.org Al-Anon Family Groups www.al-anon.org National Institute on Alcohol ...

  2. Proceedings of the 2010 Annual Meeting of the Fetal Alcohol Spectrum Disorders Study Group

    PubMed Central

    Kane, Cynthia J. M.; Smith, Susan M.; Miranda, Rajesh C.; Kable, Julie

    2011-01-01

    The annual meeting of the Fetal Alcohol Spectrum Disorders Study Group (FASDSG) was held on June 26, 2010 in San Antonio, TX, as a satellite of the Research Society on Alcoholism meeting. The FASDSG membership includes clinical, basic and social scientists who meet to discuss recent advances and issues in FASD research. The central theme of the meeting was “Glia and Neurons: Teamwork in Pathology and Therapy.” Alcohol disruption of neuron development and alcohol-induced neurodegeneration is central to the pathology and clinical expression of FASD. The active role of glia as perpetrator, victim, or bystander in neurotoxicology and neurodegenerative processes has emerged at the forefront of adult CNS disorders and therapy. Glia and neuron-glial interactions hold the potential to elucidate causes and offer treatment of FASD as well. Growing evidence indicates that neurons and glia are direct targets of alcohol, but may also be vulnerable to molecules produced in peripheral systems as a result of alcohol exposure. Diagnostics and therapies can take advantage of these processes and biomarkers, and these may be applicable to CNS pathology in FASD. Two keynote speakers, Howard E. Gendelman, M.D., and Ernest M. Graham, M.D, addressed the role of glia and neuroinflammation in brain development and neurodegeneration. The invited speakers and FASDSG members discussed new paradigms in CNS development and discuss new strategies for understanding and treating neurodegenerative disease. Members of the FASDSG provided updates on new findings through presentation of breaking research in the FASt Data Sessions. Representatives of national agencies provided updates on programs, activities, and funding priorities. The Henry Rosett Award was presented to R. Louise Floyd, R.N., D.S.N. for her career contributions to the field of fetal alcohol research. The Student and Postdoctoral Fellow Research Merit Award was presented to Shonagh O’Leary-Moore, Ph.D. for her contributions to

  3. Neuropsychological comparison of children with heavy prenatal alcohol exposure and an IQ-matched comparison group.

    PubMed

    Vaurio, Linnea; Riley, Edward P; Mattson, Sarah N

    2011-05-01

    An objective in current research on children with fetal alcohol spectrum disorders (FASD) is to determine neurobehavioral profiles to identify affected individuals. Deficits observed when children with FASD are compared to typically developing controls may be confounded by lower IQ scores in the subjects with FASD. To determine if prenatal alcohol exposure is associated with neurobehavioral deficits after controlling for IQ differences, multivariate analyses were conducted to compare alcohol-exposed (ALC) subjects to a comparison group closely matched on IQ (IQC). The initial analysis included a broad neuropsychological battery with measures of language, executive function, visual-motor integration, motor ability, and academic achievement. Additional, in depth comparisons focused on visual sustained attention, verbal learning and memory and parent/guardian-reported behavior problems. Group differences (ALC < IQC) were found on verbal learning and parent-rated behavior problems. Group differences were marginally significant (measures within the broad neuropsychological comparison) or not significant (visual attention, retention of verbal material) on the remaining comparisons. Therefore, some deficits (e.g., verbal learning and behavior problems) in children with heavy prenatal alcohol exposure cannot be explained by the lower FSIQ observed in the population. These areas of relative weakness could be useful in distinguishing children with FASD from other children with lowered IQ.

  4. Fetal alcohol syndrome related knowledge assessment and comparison in New Jersey health professional groups.

    PubMed

    Brimacombe, M; Nayeem, A; Adubato, S; Dejoseph, M; Zimmerman-Bier, B

    2008-01-01

    BACKGROUND There is a need to educate health professionals in regard to Fetal Alcohol Syndrome and Fetal Alcohol Spectrum Disorders across many health and allied health fields. OBJECTIVE Conduct evaluations of educational programs designed to assess knowledge, attitudes and beliefs in relation to Fetal Alcohol Spectrum Disorders (FASD) among health and allied health professionals in the northeastern United States. METHODS FASD related educational efforts were carried out and evaluated in New Jersey for various health-related professional groups over a four-month period using a common set of materials. Pre and post-test evaluation comprised 20 questions on FASD recognition, diagnosis, treatment, and prevention. Groups surveyed included nurses, social workers, counselors, therapists, clinicians and allied health professionals comprising physician assistants, dieticians, physical therapists, occupational therapists. RESULTS Results showed that a majority of health care professionals in New Jersey possess basic knowledge related to FASD and the effects of alcohol on a child in utero. They also had significant awareness of the importance of early diagnosis and the importance of reducing secondary disabilities. The study did however reveal areas for improvement in some professional groups. CONCLUSIONS FASD is the most important preventable cause of mental retardation. Health professionals attending workshops typically had a good basic understanding of FASD, though with some weaknesses specific to their discipline. Educational efforts in regard to FASD should be sensitive to the various health professionals engaged in preventing, diagnosing and treating FASD.

  5. Proceedings of the 2013 Annual Meeting of the Fetal Alcohol Spectrum Disorders Study Group

    PubMed Central

    Kable, Julie A.; Reynolds, James N.; Valenzuela, C. Fernando; Medina, Alexandre E.

    2014-01-01

    The 2013 Fetal Alcohol Spectrum Disorders Study Group (FASDSG) meeting was held in Orlando (Grand Cypress), FL with the theme “Developing Brain-Based Interventions for Individuals with Fetal Alcohol Spectrum Disorders”. Children with fetal alcohol spectrum disorders have significant impairments in cognitive functioning and behavioral regulation skills, which lead to a lifetime of challenges for themselves and their families; thus, developing interventions that remediate or compensate for these deficits is of great importance. The conference included 2 keynote presentations, FASt data talks, award presentations, and updates by government agencies. In addition, a lively panel discussion addressed the challenges faced by FASDSG researchers in the translation of intervention strategies developed in preclinical studies to clinical trials and, ultimately, to clinical practice. PMID:25224492

  6. Experimental and theoretical study of hydroxyquinolines: hydroxyl group position dependent dipole moment and charge-separation in the photoexcited state leading to fluorescence

    NASA Astrophysics Data System (ADS)

    Singh Mehata, Mohan; Singh, Ajay K.; Sinha, Ravindra Kumar

    2016-12-01

    Optical absorption and fluorescence (FL) spectra of 2-, 6-, 7-, 8-hydroxyquinolines (2-,6-,7- and 8-HQs) have been measured at room temperature in the wide range of solvents of different polarities, dielectric constant and refractive index. The ground state dipole moment (µ g) and excited state dipole moment (µ e) of 2-, 6-, 7- and 8-HQs were obtained using solvatochromic shift (SS) methods and microscopic solvent polarity parameters (MSPP). Change in the dipole moment (Δµ) between the ground and photo-excited states was estimated from SS and MSPP methods. DFT and TDDFT based theoretical calculations were performed for the ground and excited states dipole moments, and for vertical transitions. A significant enhancement in the excited state dipole moment was observed following photo-excitation. The large value of Δµ clearly indicates to the charge-separation in the photo-excited states, which in turn depends on the position of the hydroxyl group in the ring.

  7. Experimental and theoretical study of hydroxyquinolines: hydroxyl group position dependent dipole moment and charge-separation in the photoexcited state leading to fluorescence.

    PubMed

    Mehata, Mohan Singh; Singh, Ajay K; Sinha, Ravindra Kumar

    2016-11-17

    Optical absorption and fluorescence (FL) spectra of 2-, 6-, 7-, 8-hydroxyquinolines (2-,6-,7- and 8-HQs) have been measured at room temperature in the wide range of solvents of different polarities, dielectric constant and refractive index. The ground state dipole moment (µ g) and excited state dipole moment (µ e) of 2-, 6-, 7- and 8-HQs were obtained using solvatochromic shift (SS) methods and microscopic solvent polarity parameters (MSPP). Change in the dipole moment (Δµ) between the ground and photo-excited states was estimated from SS and MSPP methods. DFT and TDDFT based theoretical calculations were performed for the ground and excited states dipole moments, and for vertical transitions. A significant enhancement in the excited state dipole moment was observed following photo-excitation. The large value of Δµ clearly indicates to the charge-separation in the photo-excited states, which in turn depends on the position of the hydroxyl group in the ring.

  8. [PhSiO1.5]8,10,12 as nanoreactors for non-enzymatic introduction of ortho, meta or para-hydroxyl groups to aromatic molecules.

    PubMed

    Bahrami, Mozhgan; Zhang, Xingwen; Ehsani, Morteza; Jahani, Yousef; Laine, Richard M

    2017-03-20

    Traditional electrophilic bromination follows long established "rules": electron-withdrawing substituents cause bromination selective for meta positions, whereas electron-donating substituents favor ortho and para bromination. In contrast, in the [PhSiO1.5]8,10,12 silsesquioxanes, the cages act as bulky, electron withdrawing groups equivalent to CF3; yet bromination under mild conditions, without a catalyst, greatly favors ortho substitution. Surprisingly, ICl iodination without a catalyst favors (>90%) para substitution [p-IC6H4SiO1.5]8,10,12. Finally, nitration and Friedel-Crafts acylation and sulfonylation are highly meta selective, >80%. In principle, the two halogenation formats coupled with the traditional electrophilic reactions provide selective functionalization at each position on the aromatic ring. Furthermore, halogenation serves as a starting point for the synthesis of two structural isomers of practical utility, i.e. in drug prospecting. The o-bromo and p-iodo compounds are easily modified by catalytic cross-coupling to append diverse functional groups. Thereafter, F(-)/H2O2 treatment cleaves the Si-C bonds replacing Si with OH. This represents a rare opportunity to introduce hydroxyl groups to aromatic rings, a process not easily accomplished using traditional organic synthesis methods. The as-produced phenol provides additional opportunities for modification. Each cage can be considered a nanoreactor generating 8-12 product molecules. Examples given include syntheses of 4,2'-R,OH-stilbenes and 4,4'-R,OH-stilbenes (R = Me, CN). Unoptimized cleavage of the Br/I derivatives yields 55-85% phenol. Unoptimized cleavage of the stilbene derivatives yields 35-40% (3-5 equivalents of phenol) in the preliminary studies presented here. In contrast, meta R-phenol yields are 80% (7-10 mol per cage).

  9. Precipitating Circumstances of Suicide and Alcohol Intoxication among U.S. Ethnic Groups

    PubMed Central

    Caetano, Raul; Kaplan, Mark S.; Huguet, Nathalie; Conner, Kenneth; McFarland, Bentson H.; Giesbrecht, Norman; Nolte, Kurt B.

    2015-01-01

    Background To assess the prevalence of nine different types of precipitating circumstances among suicide decedents, and examine the association between circumstances and post-mortem blood alcohol content (BAC ≥ 0.08 g/dl.) across U.S. ethnic groups. Methods Data come from the restricted 2003-2011 National Violent Death Reporting System (NVDRS), with post-mortem information on 59,384 male and female suicide decedents for 17 states of the U.S. Results Among men, precipitating circumstances statistically associated with a BAC ≥ 0.08 g/dl were physical health and job problems for Blacks, and experiencing a crisis, physical health problems and intimate partner problem for Hispanics. Among women, the only precipitating circumstance associated with a BAC ≥ 0.08 g/dl was substance abuse problems other than alcohol for Blacks. The number of precipitating circumstances present before the suicide was negatively associated with a BAC ≥ 0.08 g/dl for Whites, Blacks and Hispanics. Conclusions Selected precipitating circumstances were associated with a BAC ≥ 0.08 g/dl, and the strongest determinant of this level of alcohol intoxication prior to suicide among all ethnic groups was the presence of an alcohol problem. PMID:26173709

  10. Alcohol

    MedlinePlus

    ... created when grains, fruits, or vegetables are fermented . Fermentation is a process that uses yeast or bacteria ... change the sugars in the food into alcohol. Fermentation is used to produce many necessary items — everything ...

  11. Alcohol.

    ERIC Educational Resources Information Center

    Schibeci, Renato

    1996-01-01

    Describes the manufacturing of ethanol, the effects of ethanol on the body, the composition of alcoholic drinks, and some properties of ethanol. Presents some classroom experiments using ethanol. (JRH)

  12. Advocates, interest groups and Australian news coverage of alcohol advertising restrictions: content and framing analysis

    PubMed Central

    2012-01-01

    Background Legislating restrictions on alcohol advertising is a cost-effective measure to reduce consumption of alcohol. Yet Australia relies upon industry self-regulation through voluntary codes of practice regarding the content, timing and placement of alcohol advertising. Ending industry self-regulation was recommended by the National Preventative Health Taskforce; a suggestion contested by the drinks industry. Debates about emerging alcohol-control policies regularly play out in the news media, with various groups seeking to influence the discussion. This paper examines news coverage of recommendations to restrict alcohol advertising to see how supporters and opponents frame the debate, with a view to providing some suggestions for policy advocates to advance the discussion. Methods We used content and framing analyses to examine 329 Australian newspaper items mentioning alcohol advertising restrictions over 24 months. All items were coded for mentions of specific types of advertising and types of advertising restrictions, the presence of news frames that opposed or endorsed advertising restrictions, statements made within each frame and the news-actors who appeared. Results Restrictions were the main focus in only 36% of 329 items. Alcohol advertising was conceived of as television (47%) and sport-related (56%). Restrictions were mentioned in non-specific terms (45%), or specified as restrictions on timing and placement (49%), or content (22%). Public health professionals (47%) appeared more frequently than drinks industry representatives (18%). Five supportive news frames suggested the policy is a sensible public health response, essential to protect children, needed to combat the drinks industry, required to stop pervasive branding, or as only an issue in sport. Four unsupportive frames positioned restrictions as unnecessary for a responsible industry, an attack on legitimate commercial activities, ineffective and ‘nannyist’, or inessential to government

  13. The Hispanic Americans Baseline Alcohol Survey (HABLAS): the association between acculturation, birthplace and alcohol consumption across Hispanic national groups.

    PubMed

    Vaeth, Patrice A C; Caetano, Raul; Rodriguez, Lori A

    2012-09-01

    Acculturation to U.S. society has been associated with an increase in drinking and binge drinking among Hispanics. This paper examines the association between acculturation and three drinking-related outcomes: average number of drinks consumed, binge drinking, and drinking 12 drinks or more in a single day in four major Hispanic national groups. The 2006 Hispanic Americans Baseline Alcohol Survey used a multistage cluster sample design to interview 5224 adult Hispanics (18+ years) in five selected U.S. metropolitan areas: Miami, New York, Philadelphia, Houston, and Los Angeles. The four national groups interviewed were: Puerto Ricans, Cuban Americans, Mexican Americans, and South/Central Americans. The survey response rate was 76%. Data on drinking behavior were collected and the analyses include bivariate and multivariate regression techniques. Multivariate analysis did not show an association between acculturation and volume of drinking, binge drinking, or drinking 12 or more drinks in a single day among men. Acculturation stress, however, was associated with drinking 12 or more in a day among men. Among women, high acculturation was associated with a higher volume of drinking, and it also interacted with national group to increase the likelihood of binge drinking. Acculturation does not have a homogeneous effect on drinking across gender and Hispanic national groups. The results confirm that acculturation has a more consistent association with increased drinking and binge drinking among women than among men. The effect of acculturation is therefore gender-specific. This heterogeneity across Hispanic national groups must be considered in future research, treatment, and prevention efforts.

  14. Proceedings of the 2014 Annual Meeting of the Fetal Alcohol Spectrum Disorders Study Group

    PubMed Central

    Reynolds, James N.; Valenzuela, C. Fernando; Medina, Alex E.; Wozniak, Jeffrey R.

    2015-01-01

    The 2014 Fetal Alcohol Spectrum Disorders Study Group (FASDSG) meeting focused on the dual themes of the risks associated with low to moderate alcohol exposure during pregnancy and knowledge translation practices to enhance the impact of scientific research. The meeting theme was titled “Low drinking versus no drinking: Matching science with policy and public perception”. Despite decades of basic science and clinical evidence that has documented the risks associated with prenatal alcohol exposure, there still exists confusion and uncertainty on the part of health professionals and the public regarding the question of whether or not there is a “safe” level of alcohol consumption during pregnancy. The first keynote presentation reviewed the data obtained from large-scale epidemiological studies that have attempted to address the question of relative risk associated with low to moderate alcohol exposure during pregnancy. This presentation was followed by an expert panel discussion of the state of scientific evidence obtained from clinical and basic science investigations concerning this question, and strategies for moving research evidence into policy and practice. The second keynote presentation presented a framework for knowledge translation and mobilization to move research discoveries toward implementation. The conference also featured updates by government agencies, FASt data talks that highlighted new and innovative findings in FASD research, and award presentations, including a lifetime achievement award presented to Dr. Kenneth Warren to acknowledge his longstanding support for FASD research. A highlight of the meeting was the presentation of the 2014 Henry Rosett award to Dr. Philip May in recognition of his substantial contributions to epidemiological studies on FASD. PMID:25979530

  15. The Hispanic Americans Baseline Alcohol Survey (HABLAS):Predictive invariance of Demographic Characteristics on Attitudes towards Alcohol across Hispanic National Groups.

    PubMed

    Mills, Britain A; Caetano, Raul; Bernstein, Ira H

    2010-01-01

    This study compares the demographic predictors of items assessing attitudes towards drinking across Hispanic national groups. Data were from the 2006 Hispanic Americans Baseline Alcohol Survey (HABLAS), which used a multistage cluster sample design to interview 5,224 individuals randomly selected from the household population in Miami, New York, Philadelphia, Houston, and Los Angeles. Predictive invariance of demographic predictors of alcohol attitudes over four Hispanic national groups (Puerto Rican, Cuban, Mexican, and South/Central Americans) was examined using multiple-group seemingly unrelated probit regression. The analyses examined whether the influence of various demographic predictors varied across the Hispanic national groups in their regression coefficients, item intercepts, and error correlations. The hypothesis of predictive invariance was supported. Hispanic groups did not differ in how demographic predictors related to individual attitudinal items (regression slopes were invariant). In addition, the groups did not differ in attitudinal endorsement rates once demographic covariates were taken into account (item intercepts were invariant). Although Hispanic groups have different attitudes about alcohol, the influence of multiple demographic characteristics on alcohol attitudes operates similarly across Hispanic groups. Future models of drinking behavior in adult Hispanics need not posit moderating effects of group on the relation between these background characteristics and attitudes.

  16. Novel approach to the preparation of hemisuccinates of steroids bearing tertiary alcohol group.

    PubMed

    Longin, Ondřej; Černý, Ivan; Drašar, Pavel

    2015-05-01

    17β-O-Hemisuccinates of typical representatives of Anabolic-Androgenic Steroids, 17β-hydroxy-17-methylandrostan-4-en-3-one, 17β-hydroxy-17-methyl-2-oxa-5α-androstan-3-one, 17β-hydroxy-17-methyl-5α-androstano-[3,2-c]pyrazole, were prepared. Several methods for the hemisuccinate preparation were tested. The indirect method using 1-ethyl-3-(dimethylaminopropyl)carbodiimide coupling reagent to form an ester bond of steroid with 2-(trimethylsilyl)ethyl hydrogen butanedioate was finally applied. Using the selectively removable protecting group, the desired hemisuccinates of steroids bearing tertiary alcohol group were obtained.

  17. 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.

  18. Structure-activity relationship of Au-ZrO2 catalyst on formation of hydroxyl groups and its influence on CO oxidation

    SciTech Connect

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

    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 1) 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.

  19. Alcohol Consumption, Dating Relationships, and Preliminary Sexual Outcomes in Collegiate Natural Drinking Groups.

    PubMed

    Devos-Comby, Loraine; Daniel, Jason; Lange, James E

    2013-12-01

    This study tested the effects of committed relationships and presence of dates on alcohol consumption and preliminary sexual outcomes in natural drinking groups (NDGs). Undergraduate drinkers (N = 302) answered an online questionnaire on their most recent participation in a NDG. The interaction between relationship commitment and presence of a date on alcohol consumption was significant. Among students not in committed relationships, those dating within their NDG reported heavier drinking than those not dating. Students in committed relationships drank less than those who were not committed only when their partners were present. The positive correlation between drinking and sexual contact was significant only for those who were not in committed relationships. Implications for future research and interventions are discussed.

  20. The effects of alcohol on the emotional displays of Whites in interracial groups.

    PubMed

    Fairbairn, Catharine E; Sayette, Michael A; Levine, John M; Cohn, Jeffrey F; Creswell, Kasey G

    2013-06-01

    Discomfort during interracial interactions is common among Whites in the U.S. and is linked to avoidance of interracial encounters. While the negative consequences of interracial discomfort are well-documented, understanding of its causes is still incomplete. Alcohol consumption has been shown to decrease negative emotions caused by self-presentational concern but increase negative emotions associated with racial prejudice. Using novel behavioral-expressive measures of emotion, we examined the impact of alcohol on displays of discomfort among 92 White individuals interacting in all-White or interracial groups. We used the Facial Action Coding System and comprehensive content-free speech analyses to examine affective and behavioral dynamics during these 36-min exchanges (7.9 million frames of video data). Among Whites consuming nonalcoholic beverages, those assigned to interracial groups evidenced more facial and speech displays of discomfort than those in all-White groups. In contrast, among intoxicated Whites there were no differences in displays of discomfort between interracial and all-White groups. Results highlight the central role of self-presentational concerns in interracial discomfort and offer new directions for applying theory and methods from emotion science to the examination of intergroup relations.

  1. The Effects of Alcohol on the Emotional Displays of Whites in Interracial Groups

    PubMed Central

    Fairbairn, Catharine E.; Sayette, Michael A.; Levine, John M.; Cohn, Jeffrey F.; Creswell, Kasey G.

    2017-01-01

    Discomfort during interracial interactions is common among Whites in the U.S. and is linked to avoidance of interracial encounters. While the negative consequences of interracial discomfort are well-documented, understanding of its causes is still incomplete. Alcohol consumption has been shown to decrease negative emotions caused by self-presentational concern but increase negative emotions associated with racial prejudice. Using novel behavioral-expressive measures of emotion, we examined the impact of alcohol on displays of discomfort among 92 White individuals interacting in all-White or interracial groups. We used the Facial Action Coding System and comprehensive content-free speech analyses to examine affective and behavioral dynamics during these 36-minute exchanges (7.9 million frames of video data). Among Whites consuming nonalcoholic beverages, those assigned to interracial groups evidenced more facial and speech displays of discomfort than those in all-White groups. In contrast, among intoxicated Whites there were no differences in displays of discomfort between interracial and all-White groups. Results highlight the central role of self-presentational concerns in interracial discomfort and offer new directions for applying theory and methods from emotion science to the examination of intergroup relations. PMID:23356562

  2. Effects of hydroxyl group numbers on the B-ring of 5,7-dihydroxyflavones on the differential inhibition of human CYP 1A and CYP1B1 enzymes.

    PubMed

    Kim, Hyun-Jung; Lee, Sang Bum; Park, Song-Kyu; Kim, Hwan Mook; Park, Young In; Dong, Mi-Sook

    2005-10-01

    Flavonoids are polyphenols composed of two aromatic rings (A, B) and a heterocyclic ring (C). In order to determine the effects of the number of hydroxyl groups in the B-ring of the flavonoids on human cytochrome P450 (CYP) 1 family enzymes, we evaluated the inhibition of CYP1A-dependent 7-ethoxyresorufin omicron-deethylation activity by chrysin, apigenin and luteolin, using bacterial membranes that co-express human CYP1A1, CYP1A2, or CYP1B1 with human NADPH-cytochrome P450 reductase. Chrysin, which possesses no hydroxyl groups in its B-ring, exhibited the most pronounced inhibitory effects on CYP1A2-dependent EROD activity, followed by apigenin and luteolin. On the contrary, CYP1A1-mediated EROD activity was most potently inhibited by luteolin, which is characterized by two hydroxyl groups in its B-ring, followed by apigenin and chrysin. However, all of the 5,7-dihydroxyflavones were determined to similarly inhibit CYP1B1 activity. Chrysin, apigenin, and luteolin exhibited a mixed-type mode of inhibition with regard to CYP1A2, CYP1B1, and CYP1A1, with apparent Ki values of 2.4, 0.5, and 2.0 microM, respectively. These findings suggested that the number of hydroxyl groups in the B-ring of 5,7-dihydroxyflavone might have some influence on the degree to which CYP1A enzymes were inhibited, but not on the degree to which CYP1B1 enzymes were inhibited.

  3. The Hispanic Americans Baseline Alcohol Survey (HABLAS): Rates and predictors of DUI across Hispanic national groups.

    PubMed

    Caetano, Raul; Ramisetty-Mikler, Suhasini; Rodriguez, Lori A

    2008-03-01

    This paper examines rates of self-reported driving under the influence (DUI) of alcohol and 12-month and lifetime DUI arrest rates among Mexican Americans, Puerto Ricans, Cuban Americans and South/Central Americans in the U.S. population. Using a multistage cluster sample design, a total of 5224 individuals 18 years of age and older were selected from the household population in five metropolitan areas of the U.S.: Miami, New York, Philadelphia, Houston and Los Angeles. The survey weighted response rate was 76%. Among men, 21% of Mexican Americans, 19.9% of South/Central Americans, 11.6% of Puerto Ricans and 6.9% of Cuban Americans reported DUI. Rates were lower among women, ranging from 9.7% for Mexican Americans to 1.3% for Cuban Americans. Mexican American men had the highest 12-month arrest rate (1.6%) and the highest lifetime arrest rate (11.2%). Drinkers who reported DUI were heavier drinkers than those not reporting DUI according to a variety of indicators. However, most DUI incidents involved non-alcohol-dependent drivers. Mexican Americans and South Central/Americans, men, younger drivers, those with less than high school education, those with higher income and higher alcohol consumption were more likely to report DUI and DUI arrests. These findings show that Hispanic national groups in the U.S. are diverse regarding drinking and DUI-related experiences.

  4. Polyvinyl alcohol cross-linked with two aldehydes

    NASA Technical Reports Server (NTRS)

    Sheibley, D. W.; Rieker, L. L.; Hsu, L. C.; Manzo, M. A. (Inventor)

    1982-01-01

    A film forming polyvinyl alcohol resin is admixed, in aqueous solution, with a dialdehyde crosslinking agent which is capable of crosslinking the polyvinyl alcohol resin and a water soluble acid aldehyde containing a reactive aldehyde group capable of reacting with hydroxyl groups in the polyvinyl alcohol resin and an ionizable acid hydrogen atom. The dialdehyde is present in an amount sufficient to react with from 1 to 20% by weight of the theoretical amount required to react with all of the hydroxyl groups of the polyvinyl alcohol. The amount of acid aldehyde is from 1 to 50% by weight, same basis, and is sufficient to reduce the pH of the aqueous admixture to 5 or less. The admixture is then formed into a desired physical shape, such as by casting a sheet or film, and the shaped material is then heated to simultaneously dry and crosslink the article.

  5. Discovery of pyrazine carboxamide CB1 antagonists: the introduction of a hydroxyl group improves the pharmaceutical properties and in vivo efficacy of the series.

    PubMed

    Ellsworth, Bruce A; Wang, Ying; Zhu, Yeheng; Pendri, Annapurna; Gerritz, Samuel W; Sun, Chongqing; Carlson, Kenneth E; Kang, Liya; Baska, Rose A; Yang, Yifan; Huang, Qi; Burford, Neil T; Cullen, Mary Jane; Johnghar, Susan; Behnia, Kamelia; Pelleymounter, Mary Ann; Washburn, William N; Ewing, William R

    2007-07-15

    Structure-activity relationships for a series of pyrazine carboxamide CB1 antagonists are reported. Pharmaceutical properties of the series are improved via inclusion of hydroxyl-containing sidechains. This structural modification sufficiently improved ADME properties of an orally inactive series such that food intake reduction was achieved in rat feeding models. Compound 35 elicits a 46% reduction in food intake in ad libidum fed rats 4-h post-dose.

  6. Reaction of aromatic compounds with nucleophilic reagents in liquid ammonia. VIII. The origin of the oxygen atom of the hydroxy group in the products from the hydroxylation of 1-nitronaphthalene with alkali and molecular oxygen

    SciTech Connect

    Malykhin, E.V.; Shteingarts, V.D.

    1987-10-20

    In the reaction of 1-nitronaphthalene with K/sup 18/OH and /sup 16/O/sub 2/ in liquid ammonia 1-nitro-2- and 4-nitro-1-naphthols labeled with the /sup 18/O isotope in the hydroxyl group are formed. The ratio of the isomers and the content of the /sup 18/O isotope depend on the ratio of 1-nitronaphthalene and alkali, on the temperature, and on the presence of moisture in the ammonia. The amount of the /sup 18/O isotope in the hydroxylation products indicates that in contrast to the analogous reaction of nitrobenzene and its derivatives the hydroxy function of the products in this case is formed not only from the alkali but also to a significant degree form the oxygen of the O/sub 2/.

  7. Target marketing of tobacco and alcohol-related products to ethnic minority groups in the United States.

    PubMed

    Moore, D J; Williams, J D; Qualls, W J

    1996-01-01

    This paper examines whether increased consumption of tobacco and alcohol products by minority groups is a function of the target marketing campaigns directed at these groups by marketers, and whether such contributes to the perpetuation of racism. First, a description of the tobacco and alcohol consumption rates of blacks and Hispanics compared to whites is presented, including a comparative analysis of the health effects and mortality rates resulting from the consumption of tobacco and alcohol. Second, the paper examines specific marketing strategies of targeting tobacco and alcohol products to ethnic minority consumers. This is followed by a discussion of whether these practices are a deliberate strategy driven by racism or just the pursuit of profit. A framework for answering the question is provided. Finally, the paper assesses the prospects for change in the future, and analyzes specific needs for future research.

  8. Personality and alcohol/substance-use disorder patient relapse and attendance at self-help group meetings.

    PubMed

    Janowsky, D S; Boone, A; Morter, S; Howe, L

    1999-01-01

    This study evaluated the role of personality in the short-term outcome of alcohol/substance-use disorder patients. Detoxifying alcohol/substance-use disorder patients were administered the Myers-Briggs Type Indicator (MBTI), the Tridimensional Personality Questionnaire (TPQ), the Michigan Alcohol Screening Test (MAST), the CAGE Questionnaire, and the Beck Depression Inventory (BDI). These patients were subsequently evaluated over a 1-month period for relapse and attendance at self-help group meetings. High TPQ Persistence scale scores predicted abstinence. When the Thinking and Feeling groups were considered separately, and when these two groups were combined into a single group, high scores for the individual groups and the combined group (i.e. Thinking and Feeling types together) predicted abstinence. High TPQ Persistence scale scores and low Shyness with Strangers and Fear of Uncertainty subscale scores predicted attendance at self-help group meetings. High MBTI Extroversion and high MBTI Thinking scores also predicted attendance at self-help group meetings. When the Extroverted and Introverted types and the Thinking and Feeling types respectively were combined, as with abstinence, high scores predicted attendance at self-help group meetings. Age, gender, CAGE, MAST, and BDI scores did not predict outcome. The above information suggests that specific personality variables may predict abstinence and attendance at self-help group meetings in recently detoxified alcoholics, and this may have prognostic and therapeutic significance.

  9. The tridimensional personality model: influencing variables in a sample of detoxified alcohol dependents. European Fluvoxamine in Alcoholism Study Group.

    PubMed

    Meszaros, K; Willinger, U; Fischer, G; Schönbeck, G; Aschauer, H N

    1996-01-01

    C.R. Cloninger proposed a biosocial model for personality, linking personality traits to patterns of responses to various external stimuli, including alcohol. The Tridimensional Personality Questionnaire (TPQ) was administered in a multicenter study to detoxified alcohol-dependent patients (N = 521). The objectives of the study were to evaluate (1) the expression of the three personality dimensions, novelty-seeking (NS), harm avoidance (HA), and reward dependence (RD), of the TPQ in this sample, and (2) the influence of different variables on these personality dimensions. The following variables were selected for a multiple and a stepwise regression analysis: sex, family history for major psychiatric disorders, marital status, occupation, age at study enrollment, age of onset of alcoholism, serum cholesterol level, intake of neuroleptics or benzodiazepines for detoxification, and severity of depression and anxiety. In comparison to Austrian normative data, both sexes of detoxified alcohol addicts scored higher in HA. The variables examined explain 23% of the variance of NS and 35% of HA. Only one variable, namely age of onset, is significantly influencing NS (19% explained variance). HA is significantly influenced by three variables: anxiety state, anxiety trait, and sex (32% explained variance). RD is not influenced by any of the variables examined.

  10. Referent Group Proximity, Social Norms, and Context: Alcohol Use in a Low-Use Environment

    ERIC Educational Resources Information Center

    Cox, Jared M.; Bates, Scott C.

    2011-01-01

    Objective: The purpose of this study was to investigate the relationship between perceived normative use of alcohol and reported consumption in an environment where relatively little alcohol use occurs. Participants: A total of 585 undergraduate students completed an online survey on alcohol use in March 2006. Methods: Participants reported…

  11. Selected Publications on Teenagers and Alcohol. Grouped Interest Guide No. 8-2.

    ERIC Educational Resources Information Center

    National Inst. on Alcohol Abuse and Alcoholism (DHEW/PHS), Rockville, MD.

    This brief bibliography is part of a series produced by the Current Awareness Services of the National Clearinghouse for Alcohol Information, and informational service of the National Institute on Alcohol Abuse and Alcoholism. The publications provide readers with regularly codified bibliographic references to recent, topical literature in…

  12. Proceedings of a Symposium on the Use of Group Procedures in the Prevention and Treatment of Drug and Alcohol Addiction.

    ERIC Educational Resources Information Center

    Gazda, George M., Ed.

    The theme of the fifth annual Symposium on Group Procedures was "The Use of Group Procedures in the Prevention and Treatment of Drug and Alcohol Addiction." Symposium participants included professionals in counseling; clinical, school, and educational psychology, psychiatry, and social work. In addition, invitations were sent to members of…

  13. The Hispanic Americans Baseline Alcohol Survey (HABLAS): the association between birthplace, acculturation and alcohol abuse and dependence across Hispanic national groups.

    PubMed

    Caetano, Raul; Ramisetty-Mikler, Suhasini; Rodriguez, Lori A

    2009-01-01

    Hispanics are heterogeneous in national origin, evidenced by wide ranges of alcohol abuse and dependence rates across different Hispanic national groups. This paper examines associations between 12-month rates of DSM-IV alcohol abuse and dependence with birthplace and acculturation. The 2006 Hispanic Americans Baseline Alcohol Survey, using a multistage cluster sample design, interviewed 5224 adults (18+ years) in five selected U.S. metropolitan areas: Miami, New York, Philadelphia, Houston, and Los Angeles. Comprehensive data on drinking behavior were collected and the analyses include bivariate and multivariate regression techniques. Alcohol abuse and dependence rates were higher among U.S.-born Puerto Ricans and South/Central Americans compared to their foreign-born counterparts, while no such differences were found for Cuban and Mexican Americans. Overall, those with higher acculturation report higher rates of abuse and dependence (statistically significant only for abuse among Puerto Ricans). Risk factors for abuse include being male and being in the high acculturation group. Risk factors for dependence include being male, being Puerto Rican or Mexican American, having less than a college education, and being U.S.-born. Hispanics were found to share several common risk factors with the larger U.S. population for abuse and dependence, such as male gender, lower education, and lower income.

  14. Proceedings of the 2015 Annual Meeting of the Fetal Alcohol Spectrum Disorders Study Group.

    PubMed

    Valenzuela, C Fernando; Medina, Alexandre E; Wozniak, Jeffrey R; Klintsova, Anna Y

    2016-02-01

    The 2015 Fetal Alcohol Spectrum Disorders Study Group (FASDSG) meeting was titled "Basic Mechanisms and Translational Implications." Despite decades of basic science and clinical research, our understanding of the mechanisms by which ethanol affects fetal development is still in its infancy. The first keynote presentation focused on the role of heat shock protein pathways in the actions of ethanol in the developing brain. The second keynote presentation addressed the use of magnetoencephalography to characterize brain function in children with FASD. The conference also included talks by representatives from several government agencies, short presentations by junior and senior investigators that showcased the latest in FASD research, and award presentations. An important part of the meeting was the presentation of the 2015 Henry Rosett award to Dr. Michael Charness in honor of his achievements in research on FASD.

  15. Proceedings of the 2015 Annual Meeting of the Fetal Alcohol Spectrum Disorders Study Group

    PubMed Central

    Valenzuela, C. Fernando; Medina, Alexandre E.; Wozniak, Jeffrey; Klintsova, Anna

    2015-01-01

    The 2015 Fetal Alcohol Spectrum Disorders Study Group (FASDSG) meeting was titled “Basic Mechanisms and Translational Implications”. Despite decades of basic science and clinical research, our understanding of the mechanisms by which ethanol affects fetal development is still in its infancy. The first keynote presentation focused on the role of heat shock protein pathways in the actions of ethanol in the developing brain. The second keynote presentation addressed the use of magnetoencephalography to characterize brain function in children with FASD. The conference also included talks by representatives from several government agencies, short presentations by junior and senior investigators that showcased the latest in FASD research, and award presentations. An important part of the meeting was the presentation of the 2015 Henry Rosett award to Dr. Michael Charness in honor of his achievements in research on FASD. PMID:26695590

  16. 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.

  17. Number of Hydroxyl Groups on the B-Ring of Flavonoids Affects Their Antioxidant Activity and Interaction with Phorbol Ester Binding Site of PKCδ C1B Domain: In Vitro and in Silico Studies.

    PubMed

    Kongpichitchoke, Teeradate; Hsu, Jue-Liang; Huang, Tzou-Chi

    2015-05-13

    Although flavonoids have been reported for their benefits and nutraceutical potential use, the importance of their structure on their beneficial effects, especially on signal transduction mechanisms, has not been well clarified. In this study, three flavonoids, pinocembrin, naringenin, and eriodictyol, were chosen to determine the effect of hydroxyl groups on the B-ring of flavonoid structure on their antioxidant activity. In vitro assays, including DPPH scavenging activity, ROS quantification by flow cytometer, and proteins immunoblotting, and in silico analysis by molecular docking between the flavonoids and C1B domain of PKCδ phorbol ester binding site were both used to complete this study. Eriodictyol (10 μM), containing two hydroxyl groups on the B-ring, exhibited significantly higher (p < 0.05) antioxidant activity than pinocembrin and naringenin. The IC50 values of eriodictyol, naringenin, and pinocembrin were 17.4 ± 0.40, 30.2 ± 0.61, and 44.9 ± 0.57 μM, respectively. In addition, eriodictyol at 10 μM remarkably inhibited the phosphorylation of PKCδ at 63.4% compared with PMA-activated RAW264.7, whereas pinocembrin and naringenin performed inhibition activity at 76.8 and 72.6%, respectively. According to the molecular docking analysis, pinocembrin, naringenin, and eriodictyol showed -CDOCKER_energy values of 15.22, 16.95, and 21.49, respectively, reflecting that eriodictyol could bind with the binding site better than the other two flavonoids. Interestingly, eriodictyol had a remarkably different pose to bind with the kinase as a result of the two hydroxyl groups on its B-ring, which consequently contributed to greater antioxidant activity over pinocembrin and naringenin.

  18. Alcohol and Emotional Contagion: An Examination of the Spreading of Smiles in Male and Female Drinking Groups

    PubMed Central

    Fairbairn, Catharine E.; Sayette, Michael A.; Aalen, Odd O.; Frigessi, Arnoldo

    2014-01-01

    Researchers have hypothesized that men gain greater reward from alcohol than women. However, alcohol-administration studies testing participants drinking alone have offered weak support for this hypothesis. Research suggests that social processes may be implicated in gender differences in drinking patterns. We examined the impact of gender and alcohol on “emotional contagion”—a social mechanism central to bonding and cohesion. Social drinkers (360 male, 360 female) consumed alcohol, placebo, or control beverages in groups of three. Social interactions were video recorded, and both Duchenne and non-Duchenne smiling were continuously coded using the Facial Action Coding System. Results revealed that Duchenne smiling (but not non-Duchenne smiling) contagion correlated with self-reported reward and typical drinking patterns. Importantly, Duchenne smiles were significantly less “infectious” among sober male versus female groups, and alcohol eliminated these gender differences in smiling contagion. Findings identify new directions for research exploring social-reward processes in the etiology of alcohol problems. PMID:26504673

  19. People with gambling disorder and risky alcohol habits benefit more from motivational interviewing than from cognitive behavioral group therapy

    PubMed Central

    Carlbring, Per; Forsberg, Lars; Rosendahl, Ingvar

    2016-01-01

    Background. Effective psychological treatment, including cognitive behavioral therapy and motivational interviewing (MI), is available for people with problematic gambling behaviors. To advance the development of treatment for gambling disorder, it is critical to further investigate how comorbidity impacts different types of treatments. The purpose of this study was to investigate whether screening for risky alcohol habits can provide guidance on whether people with gambling disorder should be recommended cognitive behavioral group therapy (CBGT) or MI. Methods. The present study is a secondary analysis of a previous randomized controlled trial that compared the effects of CBGT, MI and a waitlist control group in the treatment of disordered gambling. Assessment and treatment was conducted at an outpatient dependency clinic in Stockholm, Sweden, where 53 trial participants with gambling disorder began treatment. A modified version of the National Opinion Research Centre DSM-IV Screen for gambling problems was used to assess gambling disorder. The Alcohol Use Disorders Identification Test (AUDIT) was used to screen for risky alcohol habits. Results. The interaction between treatment and alcohol habits was significant and suggests that patients with gambling disorder and risky alcohol habits were better helped by MI, while those without risky alcohol habits were better helped by CBGT. Conclusions. The results support a screening procedure including the AUDIT prior to starting treatment for gambling disorder because the result of the screening can provide guidance in the choice of treatment. Patients with gambling disorder and risky alcohol habits are likely to be best helped if they are referred to MI, while those without risky alcohol habits are likely to be best helped if they are referred to CBGT. PMID:27069823

  20. Hydroxyl radical scavengers inhibit lymphocyte mitogenesis.

    PubMed Central

    Novogrodsky, A; Ravid, A; Rubin, A L; Stenzel, K H

    1982-01-01

    Agents that are known to be scavengers of hydroxyl radicals inhibit lymphocyte mitogenesis induced by phorbol myristate acetate (PMA) to a greater extent than they inhibit mitogenesis induced by concanavalin A or phytohemagglutinin. These agents include dimethyl sulfoxide, benzoate, thiourea, dimethylurea, tetramethylurea, L-tryptophan, mannitol, and several other alcohols. Their inhibitory effect is not associated with cytotoxicity. The hydroxyl radical scavengers do not inhibit PMA-dependent amino acid transport in T cells or PMA-induced superoxide production by monocytes. Thus, they do not inhibit the primary interaction of PMA with responding cells. Treatment of peripheral blood mononuclear cells with PMA increased cellular guanylate cyclase in most experiments, and dimethyl sulfoxide tended to inhibit this increase. In addition to inhibition of PMA-induced mitogenesis, hydroxyl radical scavengers markedly inhibited the activity of lymphocyte activating factor (interleukin 1). The differential inhibition of lymphocyte mitogenesis induced by different mitogens appears to be related to the differential macrophage requirements of the mitogens. The data suggest that hydroxyl radicals may be involved in mediating the triggering signal for lymphocyte activation. Some of the hydroxyl radical scavengers are inducers of cellular differentiation,. nd it is possible that their differentiating activity is related to their ability to scavenge free radicals. PMID:6122209

  1. Traditional low-alcoholic and non-alcoholic fermented beverages consumed in European countries: a neglected food group.

    PubMed

    Baschali, Aristea; Tsakalidou, Effie; Kyriacou, Adamantini; Karavasiloglou, Nena; Matalas, Antonia-Leda

    2017-01-24

    Fermented beverages hold a long tradition and contribution to the nutrition of many societies and cultures worldwide. Traditional fermentation has been empirically developed in ancient times as a process of raw food preservation and at the same time production of new foods with different sensorial characteristics, such as texture, flavour and aroma, as well as nutritional value. Low-alcoholic fermented beverages (LAFB) and non-alcoholic fermented beverages (NAFB) represent a subgroup of fermented beverages that have received rather little attention by consumers and scientists alike, especially with regard to their types and traditional uses in European societies. A literature review was undertaken and research articles, review papers and textbooks were searched in order to retrieve data regarding the dietary role, nutrient composition, health benefits and other relevant aspects of diverse ethnic LAFB and NAFB consumed by European populations. A variety of traditional LAFB and NAFB consumed in European regions, such as kefir, kvass, kombucha and hardaliye, are presented. Milk-based LAFB and NAFB are also available on the market, often characterised as 'functional' foods on the basis of their probiotic culture content. Future research should focus on elucidating the dietary role and nutritional value of traditional and 'functional' LAFB and NAFB, their potential health benefits and consumption trends in European countries. Such data will allow for LAFB and NAFB to be included in national food composition tables.

  2. Exclusion of linkage between alcoholism and the MNS blood group region on chromosome 4q in multiplex families

    SciTech Connect

    Neiswanger, K.; Kaplan, B.; Hill, S.Y.

    1995-02-27

    Polymorphic DNA markers on the long arm of chromosome 4 were used to examine linkage to alcoholism in 20 multiplex pedigrees. Fifteen loci were determined for 124 individuals. Lod scores were calculated assuming both dominant and recessive disease modes of inheritance, utilizing incidence data by age and gender that allow for correction for variable age of onset and frequency of the disorder by gender. Under the assumption that alcoholism is homogeneous in this set of pedigrees, and that a recessive mode with age and gender correction is the most appropriate, the total lod scores for all families combined were uniformly lower than -2.0. This suggests an absence of linkage between the putative alcoholism susceptibility gene and markers in the region of the MNS blood group (4q28-31), a region for which we had previously found suggestive evidence of linkage to alcoholism. The 100 cM span of chromosome 4 studied includes the class I alcohol dehydrogenase (ADH) loci. Using the recessive mode, no evidence for linkage to alcoholism was found for the markers tested, which spanned almost the entire long arm of chromosome 4. Under the dominant mode, no evidence for linkage could be found for several of the markers. 36 refs., 1 fig., 3 tabs.

  3. Fetal alcohol spectrum disorders: Clinical phenotype among a high-risk group of children and adolescents in Korea.

    PubMed

    Lee, Hyun-Seung; Jones, Kenneth Lyons; Lee, Hae Kook; Chambers, Christina D

    2016-01-01

    Little is known about the prevalence and phenotype of fetal alcohol syndrome (FAS) or spectrum disorders (FASD) in Korea. This study was performed to describe the distribution of alcohol-related physical features in a genetically homogeneous sample of children and adolescents in institutional settings in Korea. Children and adolescents receiving services in one of seven institutions in Seoul, Korea were screened for growth deficiency. Those who screened positive were assessed using a structured protocol for the key cardinal features of FAS, and for 11 additional alcohol-related dysmorphologic features. Based on these findings, children and adolescents were categorized as FAS, Deferred (some characteristic features of FAS), and No FAS. Groups were compared on the prevalence of specific additional features and number of additional features, stratified by gender and age. Of 307 children and adolescents screened, 87 received the dysmorphology evaluation. Thirteen were classified as FAS, 44 Deferred, and 30 No FAS. The frequency of 10 of the 11 additional alcohol-related features did not differ significantly by FAS category. Palmar crease abnormalities were more common in FAS (53.8%) than in the Deferred category (25.0%) or the No FAS category (6.7%) (P = 0.003). A high prevalence across all groups was found for midfacial hypoplasia and epicanthal folds, whereas only one child exhibited ptosis. This study suggests that an FASD phenotype variant related to ethnic differences in the range of defects specific to prenatal alcohol exposure may be present in the Korean population.

  4. Attitudes Toward Alcoholism and Drug Abuse Among a Group of High School Students

    ERIC Educational Resources Information Center

    Hart, Larry

    1975-01-01

    High school students (N=81) were surveyed regarding their attitudes on nine factors regarding the alcoholic and his alcoholism, and the drug abuser and his drug abuse. Analysis of the data indicated that on eight of the nine factors the students tended to view the two pathologies in essentially the same way. (Author)

  5. The Use of a Modified Marathon in Conjunction with Group Counseling in Short-term Treatment of Alcoholics

    ERIC Educational Resources Information Center

    Gazda, G. M.; And Others

    1971-01-01

    Two conclusions drawn from the application of the modified marathon to a short term treatment center were that the modified marathon had the advantages of holding" alcoholics for treatment once they were sober and it enhanced the quality of typical group counseling and therapy treatment. (Author)

  6. Where It's at! The Role of Best Friends and Peer Group Members in Young Adults' Alcohol Use

    ERIC Educational Resources Information Center

    Overbeek, Geertjan; Bot, Sander M.; Meeus, Wim H. J.; Sentse, Miranda; Knibbe, Ronald A.; Engels, Rutger

    2011-01-01

    We examined the hypothesis that best friends and members from a broader peer group would not differ in the amount of influence they have on young adults' alcohol consumption and that what counts would be the mere presence of drinking peers in a given context--irrespective of the type of relationship such peers would have with the target young…

  7. The β-Silyl Effect on the Memory of Chirality in Friedel-Crafts Alkylation Using Chiral α-Aryl Alcohols.

    PubMed

    Nokami, Toshiki; Yamane, Yu; Oshitani, Shunsuke; Kobayashi, Jun-ka; Matsui, Shin-ichiro; Nishihara, Takashi; Uno, Hidemitsu; Hayase, Shuichi; Itoh, Toshiyuki

    2015-06-19

    Iron salt-catalyzed Friedel-Crafts alkylation of chiral α-aryl alcohols with a trimethylsilyl group was found to proceed with retention of the configuration of the hydroxyl group as a leaving group. The memory of chirality of this system stems from the β-silyl effect of the trimethylsilyl group on the carbocation intermediate.

  8. Superlubricity achieved with mixtures of polyhydroxy alcohols and acids.

    PubMed

    Li, Jinjin; Zhang, Chenhui; Luo, Jianbin

    2013-04-30

    In the present work, we show that the superlubricity can be achieved when the polyhydroxy alcohol solutions are mixed with acid solutions. The lowest friction coefficients between 0.003 and 0.006 are obtained on a traditional tribometer with a high pressure under the lubrication of these mixtures. Experimental results indicate that the superlubricity mechanism is in accordance with that under the lubrication of the mixture of glycerol and acid solutions in the study by Li et al. (Li , J. J.; Zhang, C. H.; Ma, L. R.; Liu, Y. H.; Luo, J. B. Superlubricity achieved with mixtures of acids and glycerol. Langmuir 2013, 29, 271-275). It is also found that the superlubricity is closely dependent upon the concentration of polyhydroxy alcohol and the number of hydroxyl groups in the molecular structure of polyhydroxy alcohol. However, the number of carbon atoms and the arrangement of hydroxyl groups in the molecular structure almost have no effect on superlubricity.

  9. Are lifetime abstainers the best control group in alcohol epidemiology? On the stability and validity of reported lifetime abstention.

    PubMed

    Rehm, J; Irving, H; Ye, Y; Kerr, W C; Bond, J; Greenfield, T K

    2008-10-15

    Lifetime abstainers have often been recommended as the comparison group in alcohol epidemiology. The objective of this study was to provide insight into the validity and stability of lifetime abstention by using data derived from the National Alcohol Survey, a national probability survey of US households conducted in 1984, and its 2 follow-up surveys conducted in 1990 and 1992. Results indicated that more than half (52.9%; all proportions were weighted to represent the US population) of those who reported never having a drink of any alcoholic beverage in the 1992 survey reported drinking in previous surveys. Depending on assumptions, this difference may result in an underestimation of alcohol-attributable mortality of 2%-15% in men and 2%-22% in women. Sociodemographic factors differentiated those who consistently reported lifetime abstention across surveys from the rest of the study population. Results suggest that using reported lifetime abstainers as a sole comparison group is problematic, especially if reporting is based on 1 measurement only. Establishing multiple measurement points and including irregular lifetime light drinkers with lifetime abstainers as the comparison group are recommended for future epidemiologic studies.

  10. Alcohol and pregnancy

    MedlinePlus

    Drinking alcohol during pregnancy; Fetal alcohol syndrome - pregnancy; FAS - fetal alcohol syndrome ... group of defects in the baby known as fetal alcohol syndrome. Symptoms can include: Behavior and attention problems Heart ...

  11. Cerium(III), europium(III), and ytterbium(III) complexes with alcohol donor groups as chemical exchange saturation transfer agents for MRI.

    PubMed

    Huang, Ching-Hui; Morrow, Janet R

    2009-08-03

    Lanthanide(III) complexes of macrocycles 1,4,7,10-tetrakis(2-hydroxyethyl)-1,4,7,10-tetraazacyclododecane (THED) and (1S,4S,7S,10S)-1,4,7,10-tetrakis(2-hydroxypropyl)-1,4,7,10-tetraazacyclododecane (S-THP) were studied as chemical exchange saturation transfer (CEST) agents for magnetic resonance imaging (MRI) applications. The four hyperfine-shifted alcohol protons of these Ln(III) complexes gave rise to a single (1)H resonance in wet d(3)-acetonitrile that was separated from the bulk water resonance (Delta omega) by 8 ppm (Ce), 2 ppm (Nd), 7 ppm (Eu), or 17 ppm (Yb). A CEST peak corresponding to the alcohol protons was observed for all Ln(THED)(3+) or Ln(S-THP)(3+) complexes except Nd(III) at low water concentrations (<1%). In 100% aqueous buffered solutions, the CEST hydroxyl peak is observed for the Eu(III), Ce(III), and Yb(III) complexes over a range of pH values. The optimal pH range for the CEST effect of each complex is related to the pK(a) of the hydroxyl/water ligands of the complex. Optimum pH values for the CEST effect from alcohol proton exchange are pH = 6.0 for Ce(S-THP)(3+), pH = 4.5 for Eu(THED)(3+), and pH = 3.0 for Yb(S-THP)(3+).

  12. A new method for immediate derivatization of hydroxyl groups by fluoroalkyl chloroformates and its application for the determination of sterols and tocopherols in human serum and amniotic fluid by gas chromatography-mass spectrometry.

    PubMed

    Řimnáčová, L; Hušek, P; Šimek, P

    2014-04-25

    A new method has been described for efficient derivatization of secondary alicyclic hydroxyl groups in steroids by alkyl chloroformates (RCFs). Cholesterol, an essential human sterol and a steroid precursor in eukaryotic cells, was used as a model for treatment with various RCFs in an aqueous and non-aqueous environment. While the cholesterol hydroxyl group did not react completely with any of the tested RCFs reagents in the former case, trifluoroethyl chloroformate (TFECF) or heptafluorobutyl chloroformate (HFBCF) fully converts cholesterol and related metabolites into the corresponding mixed carbonates under anhydrous conditions in seconds. The acylation reaction was combined with liquid-liquid microextraction (LLME) between isooctane and acetonitrile phase. The sample preparation requires just a stepwise addition of 50μl isooctane with 5μl of a pyridine catalyst, 100μl acetonitrile and 100μl isooctane with dissolved 5μl of the fluoroalkyl chloroformate reagent to a dried sample. The protocol developed in this study was successfully tested for GC-MS analysis of 12 important model steroids and four main tocopherols. Each analyte provided a single peak with excellent GC separation properties, well defined EI spectra containing diagnostic fragment ions suitable for their identification and quantitation. The new method was further validated for the determination of six diagnostic non-cholesterol sterols and four main tocopherols in human serum and in amniotic fluid. Satisfactory data were obtained in terms of calibration, quantitation limits (for sterols and tocopherols, 0.05 and 0.15μg/ml, respectively), within-run precision (0.9-19.5%) and between-run precision (0.2-19.0%), accuracy (82-115%) and recovery (90-110%). The validated method was successfully applied to GC-MS analysis of the analytes in woman sera and amniotic fluids and the results are well-comparable with those reported by other authors. The presented work demonstrates for the first time

  13. The role of hydroxyl group acidity on the activity of silica-supported secondary amines for the self-condensation of n-butanal.

    PubMed

    Shylesh, Sankaranarayanapillai; Hanna, David; Gomes, Joseph; Canlas, Christian G; Head-Gordon, Martin; Bell, Alexis T

    2015-02-01

    The catalytic activity of secondary amines supported on mesoporous silica for the self-condensation of n-butanal to 2-ethylhexenal can be altered significantly by controlling the Brønsted acidity of M--OH species present on the surface of the support. In this study, M--OH (M=Sn, Zr, Ti, and Al) groups were doped onto the surface of SBA-15, a mesoporous silica, prior to grafting secondary propyl amine groups on to the support surface. The catalytic activity was found to depend critically on the synthesis procedure, the nature and amount of metal species introduced and the spatial separation between the acidic sites and amine groups. DFT analysis of the reaction pathway indicates that, for weak Brønsted acid groups, such as Si--OH, the rate-limiting step is C--C bond formation, whereas for stronger Brønsted acid groups, such as Ti and Al, hydrolysis of iminium species produced upon C--C bond formation is the rate-limiting step. Theoretical analysis shows further that the apparent activation energy decreases with increasing Brønsted acidity of the M--OH groups, consistent with experimental observation.

  14. LINE-1 gene hypomethylation and p16 gene hypermethylation in HepG2 cells induced by low-dose and long-term triclosan exposure: The role of hydroxyl group.

    PubMed

    Zeng, Liudan; Ma, Huimin; Pan, Shangxia; You, Jing; Zhang, Gan; Yu, Zhiqing; Sheng, Guoying; Fu, Jiamo

    2016-08-01

    Triclosan (TCS), a frequently used antimicrobial agent in pharmaceuticals and personal care products, exerts liver tumor promoter activities in mice. Previous work showed high-dose TCS (1.25-10μM) induced global DNA hypomethylation in HepG2 cells. However, whether or how tumor suppressor gene methylation changed in HepG2 cells after low-dose and long-term TCS exposure is still unknown. We investigate here the effects and mechanisms of DNA methylation of global DNA(GDM), repetitive genes, and liver tumor suppressor gene (p16) after exposing HepG2 cells to low-dose TCS (0.625-5nM)for two weeks using HPLC-MS/MS, Methylight, Q-MSP, Pyrosequencing, and Massarray methods. We found that low-dose TCS exposure decreased repetitive elements LINE-1 methylation levels, but not global DNA methylation, through down-regulating DNMT1 (DNA methyltransferase 1) and MeCP2 (methylated DNA binding domain) expression, and up-regulating 8-hydroxy-2-deoxyguanosine (8-OHdG) levels. Interestingly, low-dose TCS elevated p16 gene methylation and inhibited p16 expression, which were not observed in high-dose (10μM) group. Meanwhile, methyl-triclosan could not induce these two types of DNA methylation changes, suggesting the involvement of hydroxyl in TCS-mediated DNA methylation changes. Collectively, our results suggested low concentrations of TCS adversely affected HepG2 cells through DNA methylation dysregulation, and hydroxyl group in TCS played an important role in the effects. This study provided a better understanding on hepatotoxicity of TCS at environmentally relevant concentrations through epigenetic pathway.

  15. Effect of an alcoholic diet on dental caries and on Streptococcus of the mutans group. Study in rats.

    PubMed

    Kantorski, Karla Zanini; de Souza, Daniela Martins; Yujra, Verônica Quispe; Junqueira, Juliana Campos; Jorge, Antonio Olavo Cardoso; da Rocha, Rosilene Fernandes

    2007-01-01

    The objective of this study was to evaluate the effects of an alcohol diet on Streptococcus of the mutans group and on dental caries in the oral cavity of rats. Forty animals were divided into 3 groups according to the following liquid diets: 20% ethanol solution (Alcohol Group, AG), 27% sucrose solution (Isocaloric Group, IG), and water (Control Group, CG). After 56 days, samples were collected and plated on Mitis Salivarius Bacitracin agar to assess the number of colony forming units (CFU/mL) of Streptococcus of the mutans group. The animals were sacrificed and the jaws were removed in order to assess the occurrence of dental caries on the smooth and occlusal surfaces using stereomicroscopy. The data were submitted to ANOVA and Tukey test. The average numbers of CFU/mL (10(3)) were: 8.17 (AG), 9.78 (IG), and 5.63 (CG). There was no significant difference among the groups for the occurrence of occlusal caries. Regarding smooth surface caries, in the upper jaw, the caries number in the IG (1.58) was similar to that in the AG (2.06) and in the CG (1.14), and the number of caries in the AG was higher than in the CG; in the lower jaw there was significant difference among the 3 groups: AG (1.14), IG (2.00) and CG (0.43). The diets with the alcohol and sucrose solutions presented a tendency of increasing the colonization by Streptococcus of the mutans group and of increasing the occurrence of smooth surface dental caries in rat molars when compared to the control diet.

  16. Social Anxiety and Alcohol Use across the University Years: Adaptive and Maladaptive Groups

    ERIC Educational Resources Information Center

    Brook, Christina A.; Willoughby, Teena

    2016-01-01

    University/college can be a challenging time as students face developmental tasks such as building new social networks and achieving academically. Social anxiety may be disadvantageous in this setting given that social situations often include drinking and individuals with social anxiety tend to self-medicate through alcohol use. However, findings…

  17. What Do Adolescents Exposed to Alcoholic Anonymous Think about 12-Step Groups?

    ERIC Educational Resources Information Center

    Kelly, John F.; Myers, Mark G.; Rodolico, John

    2008-01-01

    Objectives: Referral to Alcoholics Anonymous (AA) and Narcotics Anonymous (NA) is a common continuing care recommendation. Evidence suggests some youth benefit, yet, despite referrals, youth participation is low. Little is known about adolescents' experiences of AA/NA. Greater knowledge would inform and help tailor aftercare recommendations.…

  18. Anger-Control Group Counseling for Women Recovering from Alcohol or Drug Addiction

    ERIC Educational Resources Information Center

    Gonzalez-Prendes, A. Antonio

    2008-01-01

    Two experimental conditions, a manualized cognitive-behavioral anger-control treatment incorporating empowerment strategies and a relapse-prevention treatment without the anger-control component, were compared to assess their impact on levels of trait anger and attributional styles of women recovering from alcohol and drug addiction. Participants…

  19. Parenting, identity development, internalizing symptoms, and alcohol use: a cross-sectional study in a group of Italian adolescents

    PubMed Central

    Pellerone, Monica; Tolini, Giacomo; Polopoli, Caterina

    2016-01-01

    Background Literature has demonstrated the adaptive function of identity development and parenting toward manifestation of problem behaviors in adolescence. These dimensions act on both internalizing and externalizing symptoms. Methods The objective is to investigate the relationship between identity status, parenting, and adolescent problems, which may manifest through internalized (phobias, obsessions, depression, eating disorders, entropy) and externalized modes (alcohol use and school discomfort). The research involved 198 Italian students (104 males and 94 females) in the 4th year (mean =16.94 years, standard deviation =0.35) and 5th year (mean =17.94 years, standard deviation =0.43) of senior secondary schools, who live in Caltanissetta, a town located in Sicily, Italy. The research lasted for 1 school year. The general group consisted of 225 students with a mortality rate of 12%. They completed an anamnestic questionnaire to provide 1) basic information, 2) alcohol consumption attitude in the past 30 days, and 3) their beliefs about alcohol; the “Ego Identity Process Questionnaire” to investigate identity development; the “Parental Bonding Instrument” to measure the perception of parenting during childhood; and the “Constraints of Mind” to value the presence of internalizing symptoms. Results Data show that identity status influences alcohol consumption. Low-profile identity and excessive maternal control affect the relational dependence and the tendency to perfectionism in adolescents. Among the predictors of alcohol use, there are socioeconomic status, parental control, and the presence of internalizing symptoms. Conclusion Family is the favored context of learning beliefs, patterns, and values that affect the broader regulatory social environment, and for this reason, it is considered the privileged context on which to intervene to reduce the adolescents’ behavior problems. This deviance could be an external manifestation of the difficulty

  20. Alcohol-Related Problems in High-Risk Groups. EURO Reports and Studies 109. Report on a WHO Study.

    ERIC Educational Resources Information Center

    Plant, Martin, Ed.

    Alcohol consumption has risen dramatically in many countries since the Second World War. Accompanying this rise has been a rise in alcohol-related problems, including liver cirrhosis mortality, alcohol dependence, and alcohol-related crimes and accidents. Alcohol misuse presents huge health, social, and legal problems throughout most of Europe and…

  1. Change over time in alcohol consumption in control groups in brief intervention studies: systematic review and meta-regression study.

    PubMed

    Jenkins, Richard J; McAlaney, John; McCambridge, Jim

    2009-02-01

    Reactivity to assessment has attracted recent attention in the brief alcohol intervention literature. This systematic review sought to examine the nature of change in alcohol consumption over time in control groups in brief intervention studies. Primary studies were identified from existing reviews published in English language, peer-reviewed journals between 1995 and 2005. Change in alcohol consumption and selected study-level characteristics for each primary study were extracted. Consumption change data were pooled in random effects models and meta-regression was used to explore predictors of change. Eleven review papers reported the results of 44 individual studies. Twenty-six of these studies provided data suitable for quantitative study. Extreme heterogeneity was identified and the extent of observed reduction in consumption over time was greater in studies undertaken in Anglophone countries, with single gender study participants, and without special targeting by age. Heterogeneity was reduced but was still substantial in a sub-set of 15 general population studies undertaken in English language countries. The actual content of the control group procedure itself was not predictive of reduction in drinking, nor were a range of other candidate variables including setting, the exclusion of dependent drinkers, the collection of a biological sample at follow-up, and duration of study. Further investigations may yield novel insights into the nature of behaviour change with potential to inform brief interventions design.

  2. Oxalates as Activating Groups for Alcohols in Visible Light Photoredox Catalysis: Formation of Quaternary Centers by Redox-Neutral Fragment Coupling

    PubMed Central

    MacMillan, David W. C.; Overman, Larry E.

    2015-01-01

    Alkyl oxalates are new bench-stable alcohol-activating groups for radical generation under visible light photoredox conditions. Using these precursors, the first net redox-neutral coupling of tertiary and secondary alcohols with electron-deficient alkenes is achieved. PMID:26322524

  3. Group III alcohol dehydrogenase from Pectobacterium atrosepticum: insights into enzymatic activity and organization of the metal ion-containing region.

    PubMed

    Elleuche, Skander; Fodor, Krisztian; von der Heyde, Amélie; Klippel, Barbara; Wilmanns, Matthias; Antranikian, Garabed

    2014-05-01

    NAD(P)(+)-dependent alcohol dehydrogenases (ADH) are widely distributed in all phyla. These proteins can be assigned to three nonhomologous groups of isozymes, with group III being highly diverse with regards to catalytic activity and primary structure. Members of group III ADHs share a conserved stretch of amino acid residues important for cofactor binding and metal ion coordination, while sequence identities for complete proteins are highly diverse (<20 to >90 %). A putative group III ADH PaYqhD has been identified in BLAST analysis from the plant pathogenic enterobacterium Pectobacterium atrosepticum. The PaYqhD gene was expressed in the heterologous host Escherichia coli, and the recombinant protein was purified in a two-step purification procedure to homogeneity indicating an obligate dimerization of monomers. Four conserved amino acid residues involved in metal ion coordination were substituted with alanine, and their importance for catalytic activity was confirmed by circular dichroism spectrum determination, in vitro, and growth experiments. PaYqhD exhibits optimal activity at 40 °C with short carbon chain aldehyde compounds and NADPH as cofactor indicating the enzyme to be an aldehyde reductase. No oxidative activities towards alcoholic compounds were detectable. EDTA completely inhibited catalytic activity and was fully restored by the addition of Co(2+). Activity measurements together with sequence alignments and structure analysis confirmed that PaYqhD belongs to the butanol dehydrogenase-like enzymes within group III of ADHs.

  4. Study of adjuvant effect of model surfactants from the groups of alkyl sulfates, alkylbenzene sulfonates, alcohol ethoxylates and soaps.

    PubMed

    Clausen, S K; Sobhani, S; Poulsen, O M; Poulsen, L K; Nielsen, G D

    2000-11-01

    The sodium salts of representatives of anionic surfactants, dodecylbenzene sulfonate (SDBS), dodecyl sulfate (SDS) and coconut oil fatty acids, and a nonionic surfactant, dodecyl alcohol ethoxylate, were studied for adjuvant effect on the production of specific IgE antibodies in mice. The surfactants were injected subcutaneously (sc) in concentrations of 1000, 100, 10 or 1 mg/l, respectively, together with 1 microg of ovalbumin (OVA). In addition, groups of mice received OVA in saline (control group) or in Al(OH)(3) (positive adjuvant control group). After the primary immunization the mice were boosted up to three times with OVA (0.1 microg sc) in saline. OVA-specific IgE antibodies were determined by the heterologous mouse rat passive cutaneous anaphylaxis test. The results were confirmed by a specific ELISA method. After the first booster, the Al(OH)(3) group and the 10 mg/l SDS group showed a statistically significant increase in OVA specific IgE levels. After two boosters, a statistically significant suppression in OVA-specific IgE production occurred with SDS (1000 mg/l), SDBS (1000 and 100 mg/l), coconut soap (1000 mg/l) and the alcohol ethoxylate (10 mg/l). This study suggests that a limited number of surfactants possess an adjuvant effect whereas all surfactants at certain levels can suppress specific IgE production.

  5. Maternal prenatal cigarette, alcohol and illicit drug use and risk of infant leukaemia: a report from the Children's Oncology Group.

    PubMed

    Slater, Megan E; Linabery, Amy M; Blair, Cindy K; Spector, Logan G; Heerema, Nyla A; Robison, Leslie L; Ross, Julie A

    2011-11-01

    Several case-control studies have evaluated associations between maternal smoking, alcohol consumption and illicit drug use during pregnancy and risk of childhood leukaemia. Few studies have specifically focused on infants (<1 year) with leukaemia, a group that is biologically and clinically distinct from older children. We present data from a Children's Oncology Group case-control study of 443 infants diagnosed with acute leukaemia [including acute lymphoblastic leukaemia (ALL) and acute myeloid leukaemia (AML)] between 1996 and 2006 and 324 population controls. Mothers were queried about their cigarette, alcohol and illicit drug use 1 year before and throughout pregnancy. Odds ratios (ORs) and 95% confidence intervals [CI] were calculated using adjusted unconditional logistic regression models. Maternal smoking (>1 cigarette/day) and illicit drug use (any amount) before and/or during pregnancy were not significantly associated with infant leukaemia. Alcohol use (>1 drink/week) during pregnancy was inversely associated with infant leukaemia overall [OR = 0.64; 95% CI 0.43, 0.94], AML [OR = 0.49; 95% CI 0.28, 0.87], and leukaemia with mixed lineage leukaemia gene rearrangements ('MLL+') [OR = 0.59; 95% CI 0.36, 0.97]. While our results agree with the fairly consistent evidence that maternal cigarette smoking is not associated with childhood leukaemia, the data regarding alcohol and illicit drug use are not consistent with prior reports and are difficult to interpret. It is possible that unhealthy maternal behaviours during pregnancy, some of which carry potential legal consequences, may not be adequately measured using only self-report. Future case-control studies of childhood leukaemia that pursue these exposures may benefit from incorporation of validated instruments and/or biomarkers when feasible.

  6. Niosomes containing hydroxyl additives as percutaneous penetration enhancers: effect on the transdermal delivery of sulfadiazine sodium salt.

    PubMed

    Muzzalupo, Rita; Tavano, Lorena; Lai, Francesco; Picci, Nevio

    2014-11-01

    The aim of this study was to improve the transdermal permeation of sulfadiazine sodium, employing synergistic combination of surfactants (in the form of niosomes) and additives with different number of hydroxylic groups, (following referred to as "alcohol"), as component of the bilayer. In particular the effect of different concentration of each alcohol (ethanol, propylene glycol or glycerol, from 5%, to 40% v/v) on niosomes size and distribution, drug entrapment efficiencies and ex vivo drug percutaneous permeation were evaluated, identifying formulations giving the best performances. The findings revealed that the presence of alcohol critically affect the physico-chemical properties of niosomes, with regards to dimensions, drug encapsulation and permeation. Vesicular size increased with the amount of alcohol and at the same alcohol concentration, follow the sequence ethanol>propylene glycol>glycerol. Loaded niosomes were larger than empty ones. Low E% values were found for ethanol, even less in propylene glycol and glycerol based samples, confirming that the chemical structure of the alcohol and its physico-chemical properties, affected the sulfadiazine entrapment efficiency. The comparative evaluation of percutaneous permeation profiles showed that the cumulative amount of permeated drug increases with alcohol concentration up to 20% v/v. Higher concentration (40% v/v) resulted in a strong decrease of the potential skin permeation. Best performances were obtained with glycerol. In all cases ex vivo sulfadiazine percutaneous permeations are controlled and improved respect to the corresponding free drug solutions and traditional niosomes used as controls.

  7. Dynamics of the OH group and the electronic structure of liquid alcohols

    PubMed Central

    Schreck, Simon; Pietzsch, Annette; Kunnus, Kristjan; Kennedy, Brian; Quevedo, Wilson; Miedema, Piter S.; Wernet, Philippe; Föhlisch, Alexander

    2014-01-01

    In resonant inelastic soft x-ray scattering (RIXS) from molecular and liquid systems, the interplay of ground state structural and core-excited state dynamical contributions leads to complex spectral shapes that partially allow for ambiguous interpretations. In this work, we dissect these contributions in oxygen K-edge RIXS from liquid alcohols. We use the scattering into the electronic ground state as an accurate measure of nuclear dynamics in the intermediate core-excited state of the RIXS process. We determine the characteristic time in the core-excited state until nuclear dynamics give a measurable contribution to the RIXS spectral profiles to τdyn = 1.2 ± 0.8 fs. By detuning the excitation energy below the absorption resonance we reduce the effective scattering time below τdyn, and hence suppress these dynamical contributions to a minimum. From the corresponding RIXS spectra of liquid methanol, we retrieve the “dynamic-free” density of states and find that it is described solely by the electronic states of the free methanol molecule. From this and from the comparison of normal and deuterated methanol, we conclude that the split peak structure found in the lone-pair emission region at non-resonant excitation originates from dynamics in the O–H bond in the core-excited state. We find no evidence that this split peak feature is a signature of distinct ground state structural complexes in liquid methanol. However, we demonstrate how changes in the hydrogen bond coordination within the series of linear alcohols from methanol to hexanol affect the split peak structure in the liquid alcohols. PMID:26798783

  8. Examining the Efficacy of a Brief Group Protective Behavioral Strategies Skills Training Alcohol Intervention With College Women

    PubMed Central

    Kenney, Shannon R.; Napper, Lucy E.; LaBrie, Joseph W.; Martens, Matthew P.

    2015-01-01

    College students’ use of protective behavioral strategies (PBS; e.g., determining not to exceed a set number of drinks, avoiding drinking games) is related to lower levels of alcohol consumption and problems. The present study evaluated the efficacy of a novel brief, single-session group PBS skills training intervention aimed at increasing college students’ use of PBS and reducing risky drinking and consequences. Participants (N = 226) were heavy-drinking incoming first-year college women randomized to either a PBS skills training intervention or study skills control condition. Participants attended a 45-min group session and completed online surveys pre- and postintervention (1 month and 6 months). We conducted a series of 2 × 2 × 3 repeated-measures ANCOVAs with condition and baseline mental health (anxiety/depression) as the between-subjects factors and time as the within-subjects factor. Intervention participants, relative to controls, reported significantly greater increases in PBS use and reductions in both heavy episodic drinking and alcohol consequences. The intervention was particularly effective in increasing PBS use at 1 month among participants with high anxiety. Further, tests of moderated mediation showed a significant conditional indirect effect of condition on 1-month consequences through PBS use among participants with high levels of anxiety. Findings provide preliminary support for a brief PBS-specific group intervention to reduce alcohol risk among college women, particularly anxious women. Future research is needed to strengthen the long-term effectiveness of the present approach and further explore the moderating effects of mental health. PMID:25347024

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

    PubMed

    Simonović, Miljan; Steitz, Thomas A

    2008-11-01

    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.

  10. 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.

  11. 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.

  12. Rehabilitation of the Alcoholic. A Training Guide. A Report from the Study Group on Rehabilitation of the Alcoholic and Public Offender. Rehabilitation Services Series Number 69-11.

    ERIC Educational Resources Information Center

    Rehabilitation Services Administration (DHEW), Washington, DC.

    The many difficulties involved in diagnosing, classifying and treating alcoholics comprise the bulk of the report's content. The very specific social and medical needs of the alcoholic, coupled with personal, social and treatment agency barriers, are viewed as the major feasibility (for treatment outcome) factors. The report recommends six major…

  13. Medical cost-offset following treatment referral for alcohol and other drug use disorders in a group model HMO.

    PubMed

    Polen, Michael R; Freeborn, Donald K; Lynch, Frances L; Mullooly, John P; Dickinson, Daniel M

    2006-07-01

    The purpose of this study was to determine whether specialty alcohol and other drug (AOD) treatment is associated with reduced subsequent medical care costs. AOD treatment costs and medical costs in a group model health maintenance organization (HMO) were collected for up to 6 years on 1,472 HMO members who were recommended for specialty AOD treatment, and on 738 members without AOD diagnoses or treatment. Addiction Severity Index measures were also obtained from a sample of 293 of those recommended for treatment. Changes in medical costs did not differ between treatment and comparison groups. Nor did individuals with improved treatment outcomes have greater reductions in medical costs. AOD treatment costs were not inversely related to subsequent medical costs, except for a subgroup with recent AOD treatment. In the interviewed sample, better treatment outcomes did not predict lower subsequent medical costs. Multiple treatment episodes may hold promise for producing cost-offsets.

  14. Hydrogen-bond acidity of OH groups in various molecular environments (phenols, alcohols, steroid derivatives, and amino acids structures): experimental measurements and density functional theory calculations.

    PubMed

    Graton, Jérôme; Besseau, François; Brossard, Anne-Marie; Charpentier, Eloïse; Deroche, Arnaud; Le Questel, Jean-Yves

    2013-12-12

    The hydrogen-bond (H-bond) donating strengths of a series of 36 hydroxylic H-bond donors (HBDs) with N-methylpyrrolidinone have been measured in CCl4 solution by FTIR spectrometry. These data allow the definition of a H-bond acidity scale named pKAHY covering almost three pK units, corresponding to 16 kJ mol(-1). These results are supplemented by equilibrium constants determined in CH2Cl2 for one-third of the data set to study compounds showing a poor solubility in CCl4. A systematic comparison of these experimental results with theoretical data computed in the gas phase using DFT (density functional theory) calculations has also been carried out. Quantum electrostatic parameters appear to accurately describe the H-bond acidity of the hydroxyl group, whereas partial atomic charges according to the Merz-Singh-Kollman and CHelpG schemes are not suitable for this purpose. A substantial decrease of the H-bond acidity of the OH group is pointed out when the hydroxyl moiety is involved in intramolecular H-bond interactions. In such situations, the interactions are further characterized through AIM and NBO analyses, which respectively allow localizing the corresponding bond critical point and the quantification of a significant charge transfer from the available lone pair to the σ*OH antibonding orbital. Eventually, the H-bond ability of the hydroxyl groups of steroid derivatives and of lateral chains of amino acids are evaluated on the basis of experimental and/or theoretical data.

  15. 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.

  16. 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.

  17. Doctors and alcohol. The responses of a self-selected group of general practitioners to patients with alcohol-related problems.

    PubMed

    Casswell, S; McPherson, M

    1982-07-14

    A postal survey of New Zealand general practitioners gathered information from a self-selected sample about their response to alcohol problems. Responses to a series of attitude statements measured the extent to which doctors held traditional beliefs about alcoholism as a disease, the management of which requires abstinence; emerging concepts of alcohol dependence and more moralistic attitudes. General practitioners who responded to the survey were found to be largely in sympathy with the disease concept of alcohol problems though some of the more recently emerging concepts were also widely accepted. The majority reported that they felt they did have an active role to play in connection with the alcohol problems of their patients, both in terms of treatment or advice giving, and referral to specialist agencies. Over half of the respondents requested guidelines for treatment and advice giving. Only a small proportion of general practitioners reported pessimism about their personal role in relation to their patients' alcohol problems. The results are discussed in the context of recent research evidence showing the relative efficacy of a structured advice-counseling session of the type in which general practitioners might engage.

  18. Depressive symptoms in people with and without alcohol abuse: factor structure and measurement invariance of the Beck Depression Inventory (BDI-II) across groups.

    PubMed

    Skule, Cecilie; Ulleberg, Pål; Dallavara Lending, Hilde; Berge, Torkil; Egeland, Jens; Brennen, Tim; Landrø, Nils Inge

    2014-01-01

    This study explored differences in the factor structure of depressive symptoms in patients with and without alcohol abuse, and differences in the severity of depressive symptoms between the two groups. In a sample of 358 patients without alcohol problems and 167 patients with comorbid alcohol problems, confirmatory factor analysis revealed that the same factor structures, Beck et al.'s two-factor Somatic Affective-Cognitive (SA-C) model, and Buckley et al.'s three-factor Cognitive-Affective- Somatic (C-A-S) model, demonstrated the best fit to the data in both groups. The SA-C model was preferred due to its more parsimonious nature. Evidence for strict measurement invariance across the two groups for the SA-C model was found. MIMIC (multiple-indicator-multiple-cause) modeling showed that the level of depressive symptoms was found to be highest on both factors in the group with comorbid alcohol problems. The magnitude of the differences in latent mean scores suggested a moderate difference in the level of depressive symptoms between the two groups. It is argued that patients with comorbid depression and alcohol abuse should be offered parallel and adequate treatment for both conditions.

  19. Linear propargylic alcohol functionality attached to the indazole-7-carboxamide as a JAK1-specific linear probe group.

    PubMed

    Kim, Mi Kyoung; Shin, Heerim; Cho, Seo Young; Chong, Youhoon

    2014-02-01

    Selective inhibition of JAK1 has recently been proposed as an appropriate therapeutic rationale for the treatment of inflammatory diseases such as rheumatoid arthritis (RA). In this study, through pairwise comparison and 3D alignment of the JAK isozyme structures bound to the same inhibitor molecule, we reasoned that an alkynol functionality would serve as an isozyme-specific probe group, which would enable the resulting inhibitor to differentiate the ATP-binding site of JAK1 from those of other isozymes. The 3-alkynolyl-5-(4'-indazolyl)indazole-7-carboxamide derivatives were thus prepared, and in vitro evaluation of their inhibitory activity against the JAK isozymes revealed that the propargyl alcohol functionality endowed the 5-(4'-indazolyl)indazole-7-carboxamide scaffold with JAK1 selectivity over other JAK isozymes, particularly JAK2.

  20. Association between Copy Number Variation Losses and Alcohol Dependence across African American and European American Ethnic Groups

    PubMed Central

    Ulloa, Alvaro Emilio; Chen, Jiayu; Vergara, Victor Manuel; Calhoun, Vince; Liu, Jingyu

    2014-01-01

    Background Copy number variations (CNVs) are structural genetic mutations consisting of segmental gains or losses in DNA sequence. Although CNVs contribute substantially to genomic variation, few genetic and imaging studies report association of CNVs with alcohol dependence (AD). Our purpose is to find evidence of this association across ethnic populations and genders. This work is the first AD-CNV study across ethnic groups and the first to include the African American population. Methods This study considers two CNV datasets, one for discovery (2,345 samples) and the other for validation (239 samples), both including subjects with AD and healthy controls of European and African ancestry. Our analysis assesses the association between AD and CNV losses across ethnic groups and gender by examining the effect of overall losses across the whole genome, collective losses within individual cytogenetic bands and specific losses in CNV regions. Results Results from the discovery dataset showed an association between CNV losses within 16q12.2 and AD diagnosis (p = 4.53x10−3). An overlapping CNV region from the validation dataset exhibited the same direction of effect with respect to AD (p = 0.051). This CNV region affects the genes CES1p1 and CES1, which are members of the carboxylesterase (CES) family. The enzyme encoded by CES1 is a major liver enzyme that typically catalyzes the decomposition of ester into alcohol and carboxylic acid and is involved in drug or xenobiotics, fatty acid and cholesterol metabolisms. In addition, the most significantly associated CNV region was located at 9p21.2 (p = 1.9×10−3) in our discovery dataset. Although not observed in the validation dataset, probably due to small sample size, this result might hold potential connection to AD given its connection with neuronal death. In contrast, we did not find any association between AD and the overall total losses or the collective losses within individual cytogenetic bands. Conclusions

  1. A site-holding effect of TiO2 surface hydroxyl in the photocatalytic direct synthesis of 1,1-diethoxyethane from ethanol.

    PubMed

    Zhang, Hongxia; Zhang, Wenqin; Zhao, Min; Yang, Pengju; Zhu, Zhenping

    2017-01-26

    To understand the mechanism of the photocatalytic direct synthesis of 1,1-diethoxyethane (DEE) from ethanol is vital for enhancing the reaction efficiency. Based on photocatalytic data of different phase TiO2 and F-TiO2 catalysts, radical trapping data, and GC-MS data, we proposed a photocatalytic mechanism for the preparation of both DEE in neat ethanol and 2,3-butanediol (2,3-BD) in ethanol-H2O using photocatalytic methods. In neat ethanol, hydroxyl isn't involved in the catalytic cyclic process but hydroxyl has an indirect site-holding effect, thus leading to more hydroxyl groups with higher activity. In ethanol-H2O, although the strong oxidant ˙OH radical is involved, fewer OH groups lead to higher selectivity of 2,3-BD. The interaction of the reactant/solvent with the surface group of the catalyst is important in the activity and selectivity of photocatalytic reactions. This finding gives fundamental insight into the role of TiO2 surface hydroxyl in the photocatalytic dehydrogenation process of alcohols and opens a promising path to obtaining both high selectivity and high conversion in TiO2-based photocatalytic activity.

  2. Acute Alcohol Intoxication and Suicide Among U.S. Ethnic/Racial Groups: Findings from the National Violent Death Reporting System

    PubMed Central

    Caetano, Raul; Kaplan, Mark S.; Huguet, Nathalie; McFarland, Bentson H.; Conner, Kenneth; Giesbrecht, Norman; Nolte, Kurt B.

    2012-01-01

    Background To assess the prevalence and sociodemographic correlates of suicide involving acute alcohol intoxication among U.S. ethnic minorities. Methods Data were derived from the restricted 2003–2009 National Violent Death Reporting System (NVDRS). The study focused on the sociodemographic and toxicological information of 59,384 male and female suicide decedents for 16 states of the U.S. Acute alcohol intoxication was defined as having a blood alcohol content (BAC) ≥ 0.08 g/dl. Overall, 76% of decedents were tested for the presence of alcohol. Results The proportion of suicide decedents with a positive BAC ranged from 47% among American Indians/Alaska Natives (AIs/ANs) to 23% among Asians/Pacific Islanders (PIs). Average BAC was highest among AIs/ANs. Among those who were tested for BAC, the proportion of decedents legally intoxicated prior to suicide was: Blacks, 15%; AIs/ANs, 36%; Asians/PIs, 13%; Hispanics, 28%. Bivariate associations showed that most suicide decedents who were legally intoxicated were male, younger than 30 years of age, with a high school education, not married, non-veterans, lived in metropolitan areas, and used a firearm to complete suicide. However, with the exception of Whites, most of these associations became not statistically significant in multivariate analysis. Conclusions Alcohol use and legal intoxication prior to completing suicide are common among U.S. ethnic groups, especially among males and those who are younger than 30 years of age. The AI/AN group had the highest mean BAC, the highest rate of legal intoxication and decedents who were particularly young. Suicide prevention strategies should address alcohol use as a risk factor. Alcohol problems prevention strategies should focus on suicide as a consequence of alcohol use, especially among AI/AN youth and young adults. PMID:23384174

  3. 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.

  4. Transferable force field for alcohols and polyalcohols.

    PubMed

    Ferrando, Nicolas; Lachet, Véronique; Teuler, Jean-Marie; Boutin, Anne

    2009-04-30

    A new force field has been developed for alcohol and polyalcohol molecules. Based on the anisotropic united-atom force field AUA4 developed for hydrocarbons, it only introduces one new anisotropic united atom corresponding to the hydroxyl group OH. In the case of polyalcohols and complex molecules, the calculation of the intramolecular electrostatic energy is revisited. These interactions are calculated between charges belonging to the different local dipoles of the molecule, one dipole being defined as a group of consecutive charges globally neutral. This new method allows avoiding the use of empirical scaling parameters commonly introduced to calculate 1-4 electrostatic interactions. The transferability of the proposed potential is demonstrated through the simulation of a wide variety of alcohol families: primary alcohols (methanol, ethanol, propan-1-ol, hexan-1-ol, octan-1-ol), secondary alcohols (propan-2-ol), tertiary alcohols (2-methylpropan-2-ol), phenol, and diols (1,2-ethanediol, 1,3-propanediol, 1,5-pentanediol). Monte Carlo simulations carried out in the Gibbs ensemble lead to a good agreement between calculated and experimental data for the thermodynamic properties along the liquid/vapor saturation curve, for the critical point coordinates and for the liquid structure at room temperature. Additional simulations were performed on the methanol + n-butane system showing the capability of the proposed potential to reproduce the azeotropic behavior of such mixtures with a good agreement.

  5. An Analysis of the Role of Preexisting Internal Factors in Collegiate Alcohol Abuse within Membership of Social Groups/Organizations

    ERIC Educational Resources Information Center

    Fusilier, Kristy D.

    2013-01-01

    This study utilized the administration of the CORE Drug and Alcohol Survey long form, with the inclusion of 10 additional questions to assess prior history of behaviors, social organization membership status, and reasons for utilization of alcohol, to a representative sample of 2500 college students within a single university in order to determine…

  6. Mixed Abuse of Alcohol and Drugs in Teenagers in Sweden vs. a Group from the General Population.

    ERIC Educational Resources Information Center

    Mutzell, Sture

    1995-01-01

    Examined the subsequent life and development of teenagers under probation who abused alcohol and drugs. Suggests that regardless of the social environment in which they grow up, children, both boys and girls, are in a risk zone if they use alcohol and drugs, and there is an enormous gap in their social adjustment compared with children that do…

  7. How effective are brief interventions in reducing alcohol consumption: do the setting, practitioner group and content matter? Findings from a systematic review and metaregression analysis

    PubMed Central

    Platt, Lucy; Melendez-Torres, G J; O'Donnell, Amy; Bradley, Jennifer; Newbury-Birch, Dorothy; Kaner, Eileen; Ashton, Charlotte

    2016-01-01

    Background While the efficacy and effectiveness of brief interventions for alcohol (ABI) have been demonstrated in primary care, there is weaker evidence in other settings and reviews do not consider differences in content. We conducted a systematic review to measure the effect of ABIs on alcohol consumption and how it differs by the setting, practitioner group and content of intervention. Methods We searched MEDLINE, EMBASE, PsycINFO; CINAHL, Social Science Citation Index, Cochrane Library and Global Health up to January 2015 for randomised controlled trials that measured effectiveness of ABIs on alcohol consumption. We grouped outcomes into measures of quantity and frequency indices. We used multilevel meta-analysis to estimate pooled effect sizes and tested for the effect of moderators through a multiparameter Wald test. Stratified analysis of a subset of quantity and frequency outcomes was conducted as a sensitivity check. Results 52 trials were included contributing data on 29 891 individuals. ABIs reduced the quantity of alcohol consumed by 0.15 SDs. While neither the setting nor content appeared to significantly moderate intervention effectiveness, the provider did in some analyses. Interventions delivered by nurses had the most effect in reducing quantity (d=−0.23, 95% CI (−0.33 to −0.13)) but not frequency of alcohol consumption. All content groups had statistically significant mean effects, brief advice was the most effective in reducing quantity consumed (d=−0.20, 95% CI (−0.30 to −0.09)). Effects were maintained in the stratified sensitivity analysis at the first and last assessment time. Conclusions ABIs play a small but significant role in reducing alcohol consumption. Findings show the positive role of nurses in delivering interventions. The lack of evidence on the impact of content of intervention reinforces advice that services should select the ABI tool that best suits their needs. PMID:27515753

  8. Activation of Group II Metabotropic Glutamate Receptors Inhibits the Discriminative Stimulus Effects of Alcohol via Selective Activity Within the Amygdala

    PubMed Central

    Cannady, Reginald; Grondin, Julie JM; Fisher, Kristen R; Hodge, Clyde W; Besheer, Joyce

    2011-01-01

    Metabotropic glutamate receptor subtypes (mGlu2/3) regulate a variety of alcohol-associated behaviors, including alcohol reinforcement, and relapse-like behavior. To date, the role of mGlu2/3 receptors in modulating the discriminative stimulus effects of alcohol has not been examined. Given that the discriminative stimulus effects of drugs are determinants of abuse liability and can influence drug seeking, we examined the contributions of mGlu2/3 receptors in modulating the discriminative stimulus effects of alcohol. In male Long-Evans rats trained to discriminate between alcohol (1 g/kg, IG) and water, the mGlu2/3 agonist LY379268 (0.3–10 mg/kg) did not produce alcohol-like stimulus effects. However, pretreatment with LY379268 (1 and 3 mg/kg; in combination with alcohol) inhibited the stimulus effects of alcohol (1 g/kg). Systemic LY379268 (3 mg/kg, i.p.) was associated with increases in neuronal activity within the amygdala, but not the nucleus accumbens, as assessed by c-Fos immunoreactivity. Intra-amygdala activation of mGlu2/3 receptors by LY379268 (6 μg) inhibited the discriminative stimulus effects of alcohol, without altering response rate. In contrast, intra-accumbens LY379268 (3 μg) profoundly reduced response rate; however, at lower LY379268 doses (0.3, 1 μg), the discriminative stimulus effects of alcohol and response rate were not altered. These data suggest that amygdala mGlu2/3 receptors have a functional role in modulating the discriminative stimulus properties of alcohol and demonstrate differential motor sensitivity to activation of mGlu2/3 receptors in the amygdala and the accumbens. Understanding the neuronal mechanisms that underlie the discriminative stimulus effects of alcohol may prove to be important for future development of pharmacotherapies for treating alcoholism. PMID:21734651

  9. Low-temperature IR and NMR studies of the interaction of group 8 metal dihydrides with alcohols.

    PubMed

    Gutsul, Evgenii I; Belkova, Natalia V; Sverdlov, Maria S; Epstein, Lina M; Shubina, Elena S; Bakhmutov, Vladimir I; Gribanova, Tatiana N; Minyaev, Ruslan M; Bianchini, Claudio; Peruzzini, Maurizio; Zanobini, Fabrizio

    2003-05-23

    The reactions of the octahedral dihydrido complexes [MH(2)(PP(3))] [M=Fe, Ru, Os; PP(3)=P(CH(2)CH(2)PPh(2))(3)] with a variety of weak ROH acids have been studied by IR and NMR methods in either CH(2)Cl(2) or THF in the temperature range from 190 to 290 K. This study has allowed the determination of the spectral and thermodynamic properties associated with the formation of dihydrogen bonds (DHB) between the terminal hydrides and the OH group. Both the DHB enthalpy values and the hydride basicity factors (E(j)) have been found to increase in the order Fe < Ru < Os. The proton transfer process, leading to the DHB complexes, and eventually to eta(2)-H(2) products, has been found to depend on the acidic strength of the alcohol as well as the nature of the solvent. Low temperature IR and NMR techniques have been used to trace the complete energy profile of the proton transfer process involving the osmium complex [OsH(2)(PP(3))] with trifluoroethanol.

  10. Alcoholism & depression.

    PubMed

    Hall, Mellisa

    2012-10-01

    One out of 2 Americans report drinking on a routine basis, making the excessive consumption of alcohol the third leading cause of preventable death in America (). Alcoholism and depression are common comorbidities that home healthcare professionals frequently encounter. To achieve the best patient outcomes, alcoholism should be addressed initially. Although all age groups are at risk, alcoholism and depression occur in more than 8 percent of older adults. Prevention through identifying alcohol use early in adolescence is vital to reduce the likelihood of alcohol dependence. This article provides an overview of the long-term effects of alcohol abuse, including alcoholic cirrhosis and hepatic encephalopathy. The diagnostic criteria for substance dependence and ideas for nonthreatening screening questions to use with patients who are adolescent or older are discussed. While providing patient care, home healthcare nurses share the patient's intimate home environment. This environment is perceived as a safe haven by the patient and home care nurses can take advantage of counseling and treatment opportunities in this nonthreatening environment.

  11. “Like Throwing a Bowling Ball at a Battle Ship” Audience Responses to Australian News Stories about Alcohol Pricing and Promotion Policies: A Qualitative Focus Group Study

    PubMed Central

    Fogarty, Andrea S.; Chapman, Simon

    2013-01-01

    Introduction Policies affecting alcohol’s price and promotion are effective measures to reduce harms. Yet policies targeting populations are unpopular with the public, whose views can be influenced by news framings of policy narratives. In Australia, alcohol taxation receives high news coverage, while advertising restrictions have not until recently, and narratives are highly contested for each. However, research specifically examining how audiences respond to such news stories is scant. We sought to explore audience understanding of news reports about two alcohol policy proposals. Method From June to August 2012, 46 participants were recruited for 8 focus groups in age-brackets of young people aged 18–25 years, parents of young people, and adults aged 25 or older. Groups were split by education. Participants were asked their prior knowledge of alcohol policies, before watching and discussing four news stories about alcohol taxation and advertising. Results Participants were clear that alcohol poses problems, yet thought policy solutions were ineffective in a drinking culture they viewed as unamenable to change and unaffected by alcohol’s price or promotion. Without knowledge of its actual effect on consumption, they cited the 2008 alcopops tax as a policy failure, blaming cheaper substitution. Participants had low knowledge of advertising restrictions, yet were concerned about underage exposure. They offered conditional support for restrictions, while doubting its effectiveness. There was marked distrust of statistics and news actors in broadcasts, yet discussions matched previous research findings. Conclusions News coverage has resulted in strong audience understanding of alcohol related problems but framed solutions have not always provided clear messages, despite audience support for policies. Future advocacy will need to continue recent moves to address the links between alcohol’s price and promotion with the drinking culture, as well as facilitate

  12. Alcohol conversion

    DOEpatents

    Wachs, Israel E.; Cai, Yeping

    2002-01-01

    Preparing an aldehyde from an alcohol by contacting the alcohol in the presence of oxygen with a catalyst prepared by contacting an intimate mixture containing metal oxide support particles and particles of a catalytically active metal oxide from Groups VA, VIA, or VIIA, with a gaseous stream containing an alcohol to cause metal oxide from the discrete catalytically active metal oxide particles to migrate to the metal oxide support particles and to form a monolayer of catalytically active metal oxide on said metal oxide support particles.

  13. {zeta}-potentials of silica in water-alcohol mixtures

    SciTech Connect

    Kosmulski, M.; Matijevic, E.

    1992-04-01

    Two effects of 1-alcohols (up to 30% w/w) on electrokinetic properties of silica in the presence of different concentrations of KCl (1 x 10{sup -3}-1 x 1-{sup -1} mol dm{sup -3}) are described. The isoelectric point shifts toward more basic pH, while the negative {zeta}-potentials decrease with higher concentrations of the alcohol and the electrolyte. The change in the pH{sub iep} is explained in terms of the complexation of protonated surface hydroxyl groups by alcohol molecules. The lower negative {zeta}-potentials are due to an increase in cation activity in mixed solvents and, thus, an enhanced counterion adsorption in the Stern layer. 15 refs., 8 figs., 1 tab.

  14. [Ethanol elimination rate (beta60, beta-slope) in different age groups after intake of a moderate or high dose of alcohol].

    PubMed

    Barinskaia, T O; Smirnov, A V; Salomatin, E M; Shaev, A I

    2009-01-01

    Ethanol elimination rate (beta60) was measured in different age groups of men and women following its single intake at a dose of 0.8 g/kg body weight (experiment 1) and 2 g/kg (experiment 2). Samples of capillary blood were collected 20, 40, 60, 90, 120, and 300 min (experiment 1) or 360 min after the termination of the intake (experiment 2). The phase of alcohol elimination was deduced from the kinetic curve. Each alcohol dose was consumed during 1-2 minutes or 1-1.5 hours (experiments 1 and 2 respectively). The value of (beta60) in experiment 1 was estimated at 0.17 +/- 0.04 per thousand/hour in young men aged between 18-26 years, 0.22 per thousand/hour in adult men of 32-48 years, and 0.21 per thousand/hour in women aged between 19-41 years. The difference between alcohol elimination rates in young and adult men on the one hand and between young men and women on the other hand was statistically significant (p < 0.01 and p < 0.05 respectively). In the second experiment, ethanol elimination rate was practically identical in men of the above age groups (0.16 +/- 0. 02 per thousand/hour) and significantly higher than in 64-66 year-old men (0.14 +/- 0.03 per thousand/hour). The values of ethanol elimination rate in men of group 2 calculated by the Weedmark formula proved underestimated by 17 +/- 5% regardless of their age. Men of both age groups included in experiment 1 showed an alcohol excretion rate overestimated by 8 +/- 5% and 31 +/- 6% respectively compared with 10 +/- 7% in women. It is suggested that a single intake of alcohol may lead to an instantaneous rise in the hepatic concentration of ethanol unrelated to the consumed amount that however affects its metabolic rate. It is concluded that the duration of ethanol intake has greater effect on the rate of its elimination from the body than the amount of consumed alcohol, especially in alcohol-tolerant subjects.

  15. 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.

  16. Enantiodivergent Fluorination of Allylic Alcohols: Data Set Design Reveals Structural Interplay between Achiral Directing Group and Chiral Anion.

    PubMed

    Neel, Andrew J; Milo, Anat; Sigman, Matthew S; Toste, F Dean

    2016-03-23

    Enantioselectivity values represent relative rate measurements that are sensitive to the structural features of the substrates and catalysts interacting to produce them. Therefore, well-designed enantioselectivity data sets are information rich and can provide key insights regarding specific molecular interactions. However, if the mechanism for enantioselection varies throughout a data set, these values cannot be easily compared. This premise, which is the crux of free energy relationships, exposes a challenging issue of identifying mechanistic breaks within multivariate correlations. Herein, we describe an approach to addressing this problem in the context of a chiral phosphoric acid catalyzed fluorination of allylic alcohols using aryl boronic acids as transient directing groups. By designing a data set in which both the phosphoric and boronic acid structures were systematically varied, key enantioselectivity outliers were identified and analyzed. A mechanistic study was executed to reveal the structural origins of these outliers, which was consistent with the presence of several mechanistic regimes within the data set. While 2- and 4-substituted aryl boronic acids favored the (R)-enantiomer with most of the studied catalysts, meta-alkoxy substituted aryl boronic acids resulted in the (S)-enantiomer when used in combination with certain (R)-phosphoric acids. We propose that this selectivity reversal is the result of a lone pair-π interaction between the substrate ligated boronic acid and the phosphate. On the basis of this proposal, a catalyst system was identified, capable of producing either enantiomer in high enantioselectivity (77% (R)-2 to 92% (S)-2) using the same chiral catalyst by subtly changing the structure of the achiral boronic acid.

  17. Structure-guided unravelling: Phenolic hydroxyls contribute to reduction of acrylamide using multiplex quantitative structure-activity relationship modelling.

    PubMed

    Zhang, Yu; Huang, Mengmeng; Wang, Qiao; Cheng, Jun

    2016-05-15

    We reported a structure-activity relationship study on unravelling phenolic hydroxyls instead of alcoholic hydroxyls contribute to the reduction of acrylamide formation by flavonoids. The dose-dependent study shows a close correlation between the number of phenolic hydroxyls of flavonoids and their reduction effects. In view of positions of hydroxyls, the 3',4'(ortho)-dihydroxyls in B cycle, 3-hydroxyl or hydroxyls of 3-gallate in C cycle, and 5,7(meta)-dihydroxyls in A cycle of flavonoid structures play an important role in the reduction of acrylamide. Flavone C-glycosides are more effective at reducing the formation of acrylamide than flavone O-glycosides when sharing the same aglycone. The current multiplex quantitative structure-activity relationship (QSAR) equations effectively predict the inhibitory rates of acrylamide using selected chemometric parameters (R(2): 0.835-0.938). This pioneer study opens a broad understanding on the chemoprevention of acrylamide contaminants on a structural basis.

  18. Development and Implementation of CHOICES Group to Reduce Drinking, Improve Contraception, and Prevent Alcohol-Exposed Pregnancies in American Indian Women.

    PubMed

    Hanson, Jessica D; Ingersoll, Karen; Pourier, Susan

    2015-12-01

    Public health officials assert that prevention of alcohol-exposed pregnancies (AEP) should begin before conception, by reducing alcohol consumption in women at-risk for or planning pregnancy, and/or preventing pregnancy in women who are drinking at risky levels. One such effort is the Oglala Sioux Tribe (OST) CHOICES Program. While the OST CHOICES Program has been successfully implemented, a community-based needs assessment determined that the OST CHOICES intervention should expand and be delivered in a group setting using group motivational interviewing (MI) techniques. After extensive group MI and CHOICES group trainings, recruitment for CHOICES Group began and within a ten month period, a total of twelve groups with non-pregnant American Indian women were held for this pilot intervention. Evaluations completed by participants indicated that CHOICES Group sessions positively engaged members, had low levels of anger or tension, and had average levels of avoidance of personal responsibility. An evaluation of the CHOICES Group leaders indicated strengths in certain MI skills, although improvement is needed in some core MI and group leadership skills. This is an important expansion of a successful AEP prevention program (CHOICES), as well as a novel application of MI, and recommendations and future plans for this intervention are outlined.

  19. Development and Implementation of CHOICES Group to Reduce Drinking, Improve Contraception, and Prevent Alcohol-Exposed Pregnancies in American Indian Women

    PubMed Central

    Ingersoll, Karen; Pourier, Susan

    2015-01-01

    Public health officials assert that prevention of alcohol-exposed pregnancies (AEP) should begin before conception, by reducing alcohol consumption in women at-risk for or planning pregnancy, and/or preventing pregnancy in women who are drinking at risky levels. One such effort is the Oglala Sioux Tribe (OST) CHOICES Program. While the OST CHOICES Program has been successfully implemented, a community-based needs assessment determined that the OST CHOICES intervention should expand and be delivered in a group setting using group motivational interviewing (MI) techniques. After extensive group MI and CHOICES group trainings, recruitment for CHOICES Group began and within a ten month period, a total of twelve groups with non-pregnant American Indian women were held for this pilot intervention. Evaluations completed by participants indicated that CHOICES Group sessions positively engaged members, had low levels of anger or tension, and had average levels of avoidance of personal responsibility. An evaluation of the CHOICES Group leaders indicated strengths in certain MI skills, although improvement is needed in some core MI and group leadership skills. This is an important expansion of a successful AEP prevention program (CHOICES), as well as a novel application of MI, and recommendations and future plans for this intervention are outlined. PMID:26265591

  20. Diverse sp3 C-H functionalization through alcohol β-sulfonyloxylation

    NASA Astrophysics Data System (ADS)

    Xu, Yan; Yan, Guobing; Ren, Zhi; Dong, Guangbin

    2015-10-01

    Site-selective C-H functionalization has emerged as an attractive tool for derivatizing complex synthetic intermediates, but its use for late-stage diversification is limited by the functional groups that can be introduced, especially at unactivated sp3-hybridized positions. To overcome this, we introduce a strategy that directly installs a sulfonyloxy group at a β-C-H bond of a masked alcohol and subsequently employs nucleophilic substitution reactions to prepare various derivatives. Hydroxyl groups are widely found in bioactive molecules and are thus readily available as synthetic handles. A directing group is easily added (and subsequently removed) from the alcohols such that a formal site-selective β-C-H sulfonyloxylation of these alcohols is achieved. Substitution reactions with carbon, nitrogen, oxygen and other nucleophiles then lead to diverse functionalizations that may help to streamline the synthesis of complex analogues for drug discovery.

  1. Cross-linked polyvinyl alcohol and method of making same

    NASA Technical Reports Server (NTRS)

    Hsu, L. C.; Sheibley, D. W.; Philipp, W. H. (Inventor)

    1981-01-01

    A film-forming polyvinyl alcohol polymer is mixed with a polyaldehyde-polysaccharide cross-linking agent having at least two monosaccharide units and a plurality of aldehyde groups per molecule, perferably an average of at least one aldehyde group per monosaccharide units. The cross-linking agent, such as a polydialdehyde starch, is used in an amount of about 2.5 to 20% of the theoretical amount required to cross-link all of the available hydroxyl groups of the polyvinyl alcohol polymer. Reaction between the polymer and cross-linking agent is effected in aqueous acidic solution to produce the cross-linked polymer. The polymer product has low electrical resistivity and other properties rendering it suitable for making separators for alkaline batteries.

  2. Tobacco and alcohol use during pregnancy and risk of oral clefts. Occupational Exposure and Congenital Malformation Working Group.

    PubMed Central

    Lorente, C; Cordier, S; Goujard, J; Aymé, S; Bianchi, F; Calzolari, E; De Walle, H E; Knill-Jones, R

    2000-01-01

    OBJECTIVES: This study examined the relationship between maternal tobacco and alcohol consumption during the first trimester of pregnancy and oral clefts. METHODS: Data were derived from a European multicenter case-control study including 161 infants with oral clefts and 1134 control infants. RESULTS: Multivariate analyses showed an increased risk of cleft lip with or without cleft palate associated with smoking (odds ratio [OR] = 1.79, 95% confidence interval [CI] = 1.07, 3.04) and an increased risk of cleft palate associated with alcohol consumption (OR = 2.28, 95% CI = 1.02, 5.09). The former risk increased with the number of cigarettes smoked. CONCLUSIONS: This study provides further evidence of the possible role of prevalent environmental exposures such as tobacco and alcohol in the etiology of oral clefts. PMID:10705862

  3. Fetal alcohol syndrome

    MedlinePlus

    ... resources for information on alcoholism: Alcoholics Anonymous -- www.aa.org Al-Anon Family Groups -- www.al-anon. ... exposures to the fetus. In: Martin RJ, Fanaroff AA, Walsh MC, eds. Fanaroff and Martin's Neonatal-Perinatal ...

  4. Age at First Drink, Drinking, Binge Drinking and DSM-5 Alcohol Use Disorder among Hispanic National Groups in the U.S.

    PubMed Central

    Caetano, Raul; Mills, Britain A.; Vaeth, Patrice A. C.; Reingle, Jennifer

    2014-01-01

    Background This paper examines age at first drink and adult drinking, binge drinking and DSM-5 alcohol use disorder (AUD) among U.S. Hispanic national groups. Methods Respondents come from two independent studies. The Hispanic Americans Baseline Alcohol Survey used a multistage cluster sample design to interview 5,224 individuals 18 years of age and older selected from the household population in: Miami, New York, Philadelphia, Houston and Los Angeles. Respondents in the border area (N=1,307) constituted a household probability sample of Mexican Americans living on U.S. counties that border Mexico. In both surveys, data were collected during computer assisted interviews conducted in respondents' homes. The HABLAS and the border sample response rates were 76% and 67%, respectively. Results U.S. born Hispanics begin drinking at a younger age than those who are foreign born, independent of national group. Among foreign born Hispanics, age of arrival in the U.S. is not associated with age at first drink. Results support the hypothesis that a younger age at first drink is associated with a higher mean volume of drinking, a higher probability of bingeing and a higher probability of DSM-5 AUD. But the results do not show a clear pattern by which a particular national group would consistently show no associations or stronger associations between age at first drink and the alcohol-related outcomes under consideration. Conclusions An earlier age at first drinking is positively associated with heavier drinking patterns among U.S. Hispanics. However, as in other areas of alcohol epidemiology, here too there is considerable variation in age at first drink and drinking across Hispanic national groups. PMID:24689445

  5. Copper-Catalyzed Hydroxylation of (Hetero)aryl Halides under Mild Conditions.

    PubMed

    Xia, Shanghua; Gan, Lu; Wang, Kailiang; Li, Zheng; Ma, Dawei

    2016-10-05

    The combination of Cu(acac)2 and N,N'-bis(4-hydroxyl-2,6-dimethylphenyl)oxalamide (BHMPO) provides a powerful catalytic system for hydroxylation of (hetero)aryl halides. A wide range of (hetero)aryl chlorides bearing either electron-donating or -withdrawing groups proceeded well at 130 °C, delivering the corresponding phenols and hydroxylated heteroarenes in good to excellent yields. When more reactive (hetero)aryl bromides and iodides were employed, the hydroxylation reactions completed at relatively low temperatures (80 and 60 °C, respectively) at low catalytic loadings (0.5 mol % Cu).

  6. Butyric acid esterification kinetics over Amberlyst solid acid catalysts: the effect of alcohol carbon chain length.

    PubMed

    Pappu, Venkata K S; Kanyi, Victor; Santhanakrishnan, Arati; Lira, Carl T; Miller, Dennis J

    2013-02-01

    The liquid phase esterification of butyric acid with a series of linear and branched alcohols is examined. Four strong cation exchange resins, Amberlyst™ 15, Amberlyst™ 36, Amberlyst™ BD 20, and Amberlyst™ 70, were used along with para-toluenesulfonic acid as a homogeneous catalyst. The effect of increasing alcohol carbon chain length and branching on esterification rate at 60°C is presented. For all catalysts, the decrease in turnover frequency (TOF) with increasing carbon chain length of the alcohol is described in terms of steric hindrance, alcohol polarity, and hydroxyl group concentration. The kinetics of butyric acid esterification with 2-ethylhexanol using Amberlyst™ 70 catalyst is described with an activity-based, pseudo-homogeneous kinetic model that includes autocatalysis by butyric acid.

  7. Alcohol drinking increases the dopamine-stimulating effects of ethanol and reduces D2 auto-receptor and group II metabotropic glutamate receptor function within the posterior ventral tegmental area of alcohol preferring (P) rats.

    PubMed

    Ding, Zheng-Ming; Ingraham, Cynthia M; Rodd, Zachary A; McBride, William J

    2016-10-01

    Repeated local administration of ethanol (EtOH) sensitized the posterior ventral tegmental area (pVTA) to the local dopamine (DA)-stimulating effects of EtOH. Chronic alcohol drinking increased nucleus accumbens (NAC) DA transmission and pVTA glutamate transmission in alcohol-preferring (P) rats. The objectives of the present study were to determine the effects of chronic alcohol drinking by P rats on the (a) sensitivity and response of the pVTA DA neurons to the DA-stimulating actions of EtOH, and (b) negative feedback control of DA (via D2 auto-receptors) and glutamate (via group II mGlu auto-receptors) release in the pVTA. EtOH (50 or 150 mg%) or the D2/3 receptor antagonist sulpiride (100 or 200 μM) was microinjected into the pVTA while DA was sampled with microdialysis in the NAC shell (NACsh). The mGluR2/3 antagonist LY341495 (1 or 10 μM) was perfused through the pVTA via reverse microdialysis and local extracellular glutamate and DA levels were measured. EtOH produced a more robust increase of NACsh DA in the 'EtOH' than 'Water' groups (e.g., 150 mg% EtOH: to ∼ 210 vs 150% of baseline). In contrast, sulpiride increased DA release in the NACsh more in the 'Water' than 'EtOH' groups (e.g., 200 μM sulpiride: to ∼ 190-240 vs 150-160% of baseline). LY341495 (at 10 μM) increased extracellular glutamate and DA levels in the 'Water' (to ∼ 150-180% and 180-230% of baseline, respectively) but not the 'EtOH' groups. These results indicate that alcohol drinking enhanced the DA-stimulating effects of EtOH, and attenuated the functional activities of D2 auto-receptors and group II mGluRs within the pVTA.

  8. NMR spectroscopy of hydroxyl protons in aqueous solutions of peptides and proteins.

    PubMed

    Liepinsh, E; Otting, G; Wüthrich, K

    1992-09-01

    Hydroxyl groups of serine and threonine, and to some extent also tyrosine are usually located on or near the surface of proteins. NMR observations of the hydroxyl protons is therefore of interest to support investigations of the protein surface in solution, and knowledge of the hydroxyl NMR lines is indispensable as a reference for studies of protein hydration in solution. In this paper, solvent suppression schemes recently developed for observation of hydration water resonances were used to observe hydroxyl protons of serine, threonine and tyrosine in aqueous solutions of small model peptides and the protein basic pancreatic trypsin inhibitor (BPTI). The chemical shifts of the hydroxyl protons of serine and threonine were found to be between 5.4 and 6.2 ppm, with random-coil shifts at 4 degrees C of 5.92 ppm and 5.88 ppm, respectively, and those of tyrosine between 9.6 and 10.1 ppm, with a random-coil shift of 9.78 ppm. Since these spectral regions are virtually free of other polypeptide 1H NMR signals, cross peaks with the hydroxyl protons are usually well separated even in homonuclear two-dimensional 1H NMR spectra. To illustrate the practical use of hydroxyl proton NMR in polypeptides, the conformations of the side-chain hydroxyl groups in BPTI were characterized by measurements of nuclear Overhauser effects and scalar coupling constants involving the hydroxyl protons. In addition, hydroxyl proton exchange rates were measured as a function of pH, where simple first-order rate processes were observed for both acid- and base-catalysed exchange of all but one of the hydroxyl-bearing residues in BPTI. For the conformations of the individual Ser, Thr and Tyr side chains characterized in the solution structure with the use of hydroxyl proton NMR, both exact coincidence and significant differences relative to the corresponding BPTI crystal structure data were observed.

  9. Molecular dynamics study of nanoscale organization and hydrogen bonding in binary mixtures of butylammonium nitrate ionic liquid and primary alcohols.

    PubMed

    Shrivastav, Gourav; Gupta, Aditya; Rastogi, Aman; Dhabal, Debdas; Kashyap, Hemant K

    2017-02-14

    Molecular dynamics simulations are utilized here to explore the nanoscale morphology and the nature of hydrogen bonding in the equimolar mixtures of butylammonium nitrate protic ionic liquid with ethanol, propanol, and butanol. The X-ray scattering experimental study of Greaves et al. [Phys. Chem. Chem. Phys. 13, 13 501 (2011)] has evidenced that alkylammonium nitrate plus alcohol mixtures possess nanoscale structural order which becomes more pronounced as the chain length of the alcohol increases. Our analysis carried out using simulated total and partial X-ray scattering structure functions quantifies the basis of these observations. The partial structure functions highlight the off-phase density correlations of alcohol with both cation and anion in the low-q region. We demonstrate that the chain lengthening of alcohols offers significant variation in the structuring of the polar and apolar moieties in the mixtures. The inspection based on radial distribution functions manifests the non-linear hydrogen bonds of cations with nitrate anions as well as alcohol molecules. The alcohol's hydroxyl group prefers to form linear hydrogen bonds with anions and with other alcohol molecules. Incremented chain length of alcohol improves the extent of hydrogen bonding but does not alter their geometry. Spatial distribution functions delineate similar preferences. It shows stronger directional preferences of the hydroxyl group of alcohols than cation in the vicinity of an anion. Enhanced pair correlations associated with the terminal methyl carbons suggest aggregation of butanol chains in apolar domains. Triplet correlation functions (TCFs) are also used to evaluate the orientational preferences of the present polar moieties in the mixtures. Information based on TCFs for distribution of polar head group of cations and anions unveils the dominance of equilateral configurations over the less frequent isosceles configurations in all the three mixtures.

  10. Molecular dynamics study of nanoscale organization and hydrogen bonding in binary mixtures of butylammonium nitrate ionic liquid and primary alcohols

    NASA Astrophysics Data System (ADS)

    Shrivastav, Gourav; Gupta, Aditya; Rastogi, Aman; Dhabal, Debdas; Kashyap, Hemant K.

    2017-02-01

    Molecular dynamics simulations are utilized here to explore the nanoscale morphology and the nature of hydrogen bonding in the equimolar mixtures of butylammonium nitrate protic ionic liquid with ethanol, propanol, and butanol. The X-ray scattering experimental study of Greaves et al. [Phys. Chem. Chem. Phys. 13, 13 501 (2011)] has evidenced that alkylammonium nitrate plus alcohol mixtures possess nanoscale structural order which becomes more pronounced as the chain length of the alcohol increases. Our analysis carried out using simulated total and partial X-ray scattering structure functions quantifies the basis of these observations. The partial structure functions highlight the off-phase density correlations of alcohol with both cation and anion in the low-q region. We demonstrate that the chain lengthening of alcohols offers significant variation in the structuring of the polar and apolar moieties in the mixtures. The inspection based on radial distribution functions manifests the non-linear hydrogen bonds of cations with nitrate anions as well as alcohol molecules. The alcohol's hydroxyl group prefers to form linear hydrogen bonds with anions and with other alcohol molecules. Incremented chain length of alcohol improves the extent of hydrogen bonding but does not alter their geometry. Spatial distribution functions delineate similar preferences. It shows stronger directional preferences of the hydroxyl group of alcohols than cation in the vicinity of an anion. Enhanced pair correlations associated with the terminal methyl carbons suggest aggregation of butanol chains in apolar domains. Triplet correlation functions (TCFs) are also used to evaluate the orientational preferences of the present polar moieties in the mixtures. Information based on TCFs for distribution of polar head group of cations and anions unveils the dominance of equilateral configurations over the less frequent isosceles configurations in all the three mixtures.

  11. Protonated alcohols are examples of complete charge-shift bonds.

    PubMed

    Anderson, Peter; Petit, Alban; Ho, Junming; Mitoraj, Mariusz Pawel; Coote, Michelle L; Danovich, David; Shaik, Sason; Braïda, Benoît; Ess, Daniel H

    2014-11-07

    Accurate gas-phase and solution-phase valence bond calculations reveal that protonation of the hydroxyl group of aliphatic alcohols transforms the C-O bond from a principally covalent bond to a complete charge-shift bond with principally "no-bond" character. All bonding in this charge-shift bond is due to resonance between covalent and ionic structures, which is a different bonding mechanism from that of traditional covalent bonds. Until now, charge-shift bonds have been previously identified in inorganic compounds or in exotic organic compounds. This work showcases that charge-shift bonds can occur in common organic species.

  12. From protein denaturant to protectant: Comparative molecular dynamics study of alcohol/protein interactions

    NASA Astrophysics Data System (ADS)

    Shao, Qiang; Fan, Yubo; Yang, Lijiang; Qin Gao, Yi

    2012-03-01

    It is well known that alcohols can have strong effects on protein structures. For example, monohydric methanol and ethanol normally denature, whereas polyhydric glycol and glycerol protect, protein structures. In a recent combined theoretical and NMR experimental study, we showed that molecular dynamics simulations can be effectively used to understand the molecular mechanism of methanol denaturing protein. In this study, we used molecular dynamics simulations to investigate how alcohols with varied hydrophobicity and different numbers of hydrophilic groups (hydroxyl groups) exert effects on the structure of the model polypeptide, BBA5. First, we showed that methanol and trifluoroethanol (TFE) but not glycol or glycerol disrupt hydrophobic interactions. The latter two alcohols instead protect the assembly of the α- and β-domains of the polypeptide. Second, all four alcohols were shown to generally increase the stability of secondary structures, as revealed by the increased number of backbone hydrogen bonds formed in alcohol/water solutions compared to that in pure water, although individual hydrogen bonds can be weakened by certain alcohols, such as TFE. The two monohydric alcohols, methanol and TFE, display apparently different sequence-dependence in affecting the backbone hydrogen bond stability: methanol tends to enhance the stability of backbone hydrogen bonds of which the carbonyl groups are from polar residues, whereas TFE tends to stabilize those involving non-polar residues. These results demonstrated that subtle differences in the solution environment could have distinct consequences on protein structures.

  13. Ice Nucleation Efficiency of Hydroxylated Organic Surfaces Is Controlled by Their Structural Fluctuations and Mismatch to Ice.

    PubMed

    Qiu, Yuqing; Odendahl, Nathan; Hudait, Arpa; Mason, Ryan; Bertram, Allan K; Paesani, Francesco; DeMott, Paul J; Molinero, Valeria

    2017-03-01

    Heterogeneous nucleation of ice induced by organic materials is of fundamental importance for climate, biology, and industry. Among organic ice-nucleating surfaces, monolayers of long chain alcohols are particularly effective, while monolayers of fatty acids are significantly less so. As these monolayers expose to water hydroxyl groups with an order that resembles the one in the basal plane of ice, it was proposed that lattice matching between ice and the surface controls their ice-nucleating efficiency. Organic monolayers are soft materials and display significant fluctuations. It has been conjectured that these fluctuations assist in the nucleation of ice. Here we use molecular dynamic simulations and laboratory experiments to investigate the relationship between the structure and fluctuations of hydroxylated organic surfaces and the temperature at which they nucleate ice. We find that these surfaces order interfacial water to form domains with ice-like order that are the birthplace of ice. Both mismatch and fluctuations decrease the size of the preordered domains and monotonously decrease the ice freezing temperature. The simulations indicate that fluctuations depress the freezing efficiency of monolayers of alcohols or acids to half the value predicted from lattice mismatch alone. The model captures the experimental trend in freezing efficiencies as a function of chain length and predicts that alcohols have higher freezing efficiency than acids of the same chain length. These trends are mostly controlled by the modulation of the structural mismatch to ice. We use classical nucleation theory to show that the freezing efficiencies of the monolayers are directly related to their free energy of binding to ice. This study provides a general framework to relate the equilibrium thermodynamics of ice binding to a surface and the nonequilibrium ice freezing temperature and suggests that these could be predicted from the structure of interfacial water.

  14. Alcoholism, Alcohol, and Drugs

    ERIC Educational Resources Information Center

    Rubin, Emanuel; Lieber, Charles S.

    1971-01-01

    Describes research on synergistic effects of alcohol and other drugs, particularly barbiturates. Proposes biochemical mechanisms to explain alcoholics' tolerance of other drugs when sober, and increased sensitivity when drunk. (AL)

  15. Disordered gambling among racial and ethnic groups in the US: Results from the National Epidemiologic Survey on Alcohol and Related Conditions

    PubMed Central

    Alegría, Analucía A.; Petry, Nancy M.; Hasin, Deborah S.; Liu, Shang-Min; Grant, Bridget F.; Blanco, Carlos

    2009-01-01

    Introduction Prior research suggests that racial minority groups in the US are more vulnerable to develop a gambling disorder than Whites. However, no national survey on gambling disorders exists that has focused on ethnic differences. Methods Analyses of this study were based on the National Epidemiologic Survey on Alcohol and Related Conditions (NESARC), a large (n=43,093) nationally representative survey of the adult (18+ years) population residing in households during 2001–2002 period. DSM-IV diagnoses of pathological gambling, mood, anxiety, drug use and personality disorders were based on the Alcohol Use Disorder and Associated Disabilities Interview Schedule-DSM-IV Version (AUDADIS-IV). Results Prevalence rates of disordered gambling among Blacks (2.2%) and Native/Asian Americans (2.3%) were higher than that of Whites (1.2%). Demographic characteristics and psychiatric comorbidity differed among Black, Hispanic and White disordered gamblers. However, all racial and ethnic groups evidenced similarities with respect to symptom patterns, time course and treatment seeking for pathological gambling. Conclusions The prevalence of disordered gambling, but not its onset or course of symptoms, varies by racial and ethnic group. These varying prevalence rates may reflect, at least in part, cultural differences in gambling and its acceptability and accessibility. These data may inform the need for targeted prevention strategies for high-risk racial and ethnic groups. PMID:19407710

  16. Sporadic Retinoblastoma and Parental Smoking and Alcohol Consumption before and after Conception: A Report from the Children’s Oncology Group

    PubMed Central

    Azary, Saeedeh; Ganguly, Arupa; Bunin, Greta R.; Lombardi, Christina; Park, Andrew S.; Ritz, Beate; Heck, Julia E.

    2016-01-01

    Background Retinoblastoma is the most frequent tumor of the eye in children and very little is known about the etiology of non-familial (sporadic) retinoblastoma. In this study we examined whether parental tobacco smoking or alcohol consumption (pre- or post-conception) contribute to the two phenotypes (bilateral or unilateral) of sporadic retinoblastoma. Methods Two large multicenter case-control studies identified 488 cases through eye referral centers in the United States and Canada or through the Children’s Oncology Group. Controls (n = 424) were selected from among friends and relatives of cases and matched by age. Risk factor information was obtained via telephone interview. We employed multivariable logistic regression to estimate the effects of parental tobacco smoking and alcohol consumption on retinoblastoma. Findings Maternal smoking before and during pregnancy contributed to unilateral retinoblastoma risk in the child: year before pregnancy conditional Odds Ratio (OR), 8.9; 95% confidence interval (CI) 1.5–51, and unconditional OR, 2.4; 95% CI, 1.3–4.7; month before or during pregnancy, conditional OR, 3.3; 95% CI, 0.5–20.8, and unconditional OR, 2.8; 95% CI, 1.1–7.0. No association was found for maternal or paternal alcohol consumption. Conclusion The results of this study indicate that maternal active smoking during pregnancy may be a risk factor for sporadic retinoblastoma. Our study supports a role for tobacco exposures in embryonal tumors. PMID:26991078

  17. The interaction of catalytic metal ions and ionizing groups in equilibrium studies and in transient intermediates of metal-substituted alcohol dehydrogenases.

    PubMed

    Maret, W; Gerber, M; Zeppezauer, M; Dunn, M F

    1985-01-01

    The step of ternary complex interconversion in the reaction catalyzed by horse liver alcohol dehydrogenase has been resolved into five distinct molecular species with the aid of metal-substitution studies in combination with rapid-scanning spectrophotometry. A correlation with electronic absorption spectra at equilibrium provides structural insights into these intermediates. In contrast to NADH, NAD+ only leads to a conformational change of the protein when a negative charge has been created in the vicinity of the catalytic metal ion. This paper presents also a reevaluation of previous assignments of catalytically important groups in the light of some recent results.

  18. First examples of oxidizing secondary alcohols to ketones in the presence of the disulfide functional group: synthesis of novel diketone disulfides.

    PubMed

    Fang, X; Bandarage, U K; Wang, T; Schroeder, J D; Garvey, D S

    2001-06-01

    The disulfide functionality is present in a number of organic compounds of interest in the fields of both chemistry and biology. Because the disulfide group is known to be highly susceptible to further oxidation by a wide range of agents, performing a chemoselective oxidation without further oxidizing the disulfide moiety poses a synthetic challenge. Reported herein are the first examples of such a chemoselective oxidation in which a series of novel secondary alcohol disulfides 2a-f have been converted to the corresponding symmetrical diketones 3a-f utilizing a modified Swern oxidation.

  19. Generation of hydroxyl radicals during ascites experimentally induced in broilers.

    PubMed

    Arab, H A; Jamshidi, R; Rassouli, A; Shams, G; Hassanzadeh, M H

    2006-04-01

    Increased metabolic rates, pulmonary hypertension and cardiac dysfunction are the most important features of the ascites syndrome in broiler chickens. However, the mechanism of cell injury causing the pathogenesis of the syndrome is not clearly understood. Our study aimed to examine the generation of hydroxyl radicals (OH*) in broiler chickens experiencing ascites. The hundred and fifty 1-d-old chickens were purchased from a local hatchery and reared in an open poultry house for 46 d. They were divided at random into three groups and ascites was induced in two groups by exposing them to low temperature or administration of triiodothyronine (T(3)). The third group served as control and was reared normally. Haematological, biochemical and pathological tests were used to determine the incidence of ascites: including total red blood cell (RBC), packed cell volume (PCV), release of alanine transaminase (ALT) and aspartate transaminase (AST) and ratio of right ventricular weight to total ventricular weight (RV/TV). A salicylate hydroxylation method was used to examine the generation of hydroxyl radicals (OH*) in treated groups. TWo hydroxylated salicylic acid metabolites, 2,3- and 2,5-dihydroxy benzoic acid (2,3- and 2,5-DHBA), were measured by HPLC to detect the generation of OH*. An ascites syndrome was observed in T(3) and low-temperature treated groups, as shown by necropsy changes and increases in f RBC, PCV, ALT, AST and the ratio of RV/TV. Concentrations of 2,3- and 2,5-DHBA were increased in groups experiencing ascites compared to control group. It is suggested that reactive oxygen species that is OH* ions, may be involved in the pathogenesis of the ascites syndrome in broiler chickens.

  20. 21 CFR 172.814 - Hydroxylated lecithin.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... HUMAN CONSUMPTION (CONTINUED) FOOD ADDITIVES PERMITTED FOR DIRECT ADDITION TO FOOD FOR HUMAN CONSUMPTION Multipurpose Additives § 172.814 Hydroxylated lecithin. The food additive hydroxylated lecithin may be safely used as an emulsifier in foods in accordance with the following conditions: (a) The additive...

  1. [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.

  2. Alcohol Alert

    MedlinePlus

    ... Us You are here Home » Alcohol Alert Alcohol Alert The NIAAA Alcohol Alert is a quarterly bulletin that disseminates important research ... text. To order single copies of select Alcohol Alerts, see ordering Information . To view publications in PDF ...

  3. Alcoholic neuropathy

    MedlinePlus

    Neuropathy - alcoholic; Alcoholic polyneuropathy ... The exact cause of alcoholic neuropathy is unknown. It likely includes both a direct poisoning of the nerve by the alcohol and the effect of poor nutrition ...

  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. 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

  6. Do drug users use less alcohol than non-drug users? A comparison of ethyl glucuronide concentrations in hair between the two groups in medico-legal cases.

    PubMed

    Paul, Richard; Kingston, Robert; Tsanaclis, Lolita; Berry, Anthony; Guwy, Alan

    2008-03-21

    Two groups were selected from the remainder of hair samples that had been tested for drugs at TrichoTech for medico-legal cases: samples that tested negative (drug-negative group; N=42, age 33.4+/-7.2 years) and samples that tested positive for drugs (drug-positive group; N=57, age 32.5+/-8.8 years). A rapid, simple method to detect the ethanol metabolite, ethyl glucuronide (EtG) in hair has been developed. The hair samples were sectioned, and then submitted to overnight sonication in water. Samples then underwent SPE using anion exchange cartridges, followed by derivatisation with N,O-bis[trimethylsilyl]trifluoroacetamide (BSTFA), before confirmation by GC-MS/MS. The assay produced excellent linearity and sensitivity over the calibration range 0.02-1.0 ng/mg, assuming a 10 mg hair sample. The mean age of the two groups was not statistically different (p=0.575, Student t-test), indicating a homogeneous group. Twelve of the 57 (21.0%) hair samples of the drug-positive group tested positive for EtG, and 17 of the 42 (40.5%) hair samples of the drug-negative group tested positive for EtG. The mean concentration of EtG in the drug-positive group was 0.011 ng/mg compared to 0.107 ng/mg in the drug-negative group. When the full results of this study were subjected to statistical analysis it was shown that EtG levels in the drug-negative group were statistically higher than those found in the drug-positive group (p<0.05). This preliminary finding may be of use in the study of addiction and adds valuable data to previous studies regarding the use of EtG as a valuable marker for alcohol levels in hair.

  7. 75 FR 10293 - National Institute on Alcohol Abuse and Alcoholism; Notice of Closed Meeting

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-03-05

    ... National Institute on Alcohol Abuse and Alcoholism; Notice of Closed Meeting Pursuant to section 10(d) of... Institute on Alcohol Abuse and Alcoholism, Initial Review Group Neuroscience Review Subcommittee. Date: June... Buzas, PhD. Scientific Review Officer, National Institute on Alcohol Abuse and Alcoholism,...

  8. 75 FR 10291 - National Institute on Alcohol Abuse and Alcoholism; Notice of Closed Meeting

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-03-05

    ... National Institute on Alcohol Abuse and Alcoholism; Notice of Closed Meeting Pursuant to section 10(d) of... Institute on Alcohol Abuse and Alcoholism, Initial Review Group, Epidemiology, Prevention and Behavior... Institute on Alcohol Abuse and Alcoholism, Office of Extramural Activities, Extramural Project Review...

  9. 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

  10. Molybdoenzyme That Catalyzes the Anaerobic Hydroxylation of a Tertiary Carbon Atom in the Side Chain of Cholesterol*

    PubMed Central

    Dermer, Juri; Fuchs, Georg

    2012-01-01

    Cholesterol is a ubiquitous hydrocarbon compound that can serve as substrate for microbial growth. This steroid and related cyclic compounds are recalcitrant due to their low solubility in water, complex ring structure, the presence of quaternary carbon atoms, and the low number of functional groups. Aerobic metabolism therefore makes use of reactive molecular oxygen as co-substrate of oxygenases to hydroxylate and cleave the sterane ring system. Consequently, anaerobic metabolism must substitute oxygenase-catalyzed steps by O2-independent hydroxylases. Here we show that one of the initial reactions of anaerobic cholesterol metabolism in the β-proteobacterium Sterolibacterium denitrificans is catalyzed by an unprecedented enzyme that hydroxylates the tertiary C25 atom of the side chain without molecular oxygen forming a tertiary alcohol. This steroid C25 dehydrogenase belongs to the dimethyl sulfoxide dehydrogenase molybdoenzyme family, the closest relative being ethylbenzene dehydrogenase. It is a heterotrimer, which is probably located at the periplasmic side of the membrane and contains one molybdenum cofactor, five [Fe-S] clusters, and one heme b. The draft genome of the organism contains several genes coding for related enzymes that probably replace oxygenases in steroid metabolism. PMID:22942275

  11. Alcohol Alert: Genetics of Alcoholism

    MedlinePlus

    ... 84 Alcohol Alert Number 84 Print Version The Genetics of Alcoholism Why can some people have a ... to an increased risk of alcoholism. Cutting-Edge Genetic Research in Alcoholism Although researchers already have made ...

  12. 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.

  13. Evaluation and Optimization of TSNCO Method for Hydroxyl Analysis

    DTIC Science & Technology

    1985-01-01

    containing materials. The method involves the reaction of the hydroxyl group with toluenesulfonyl isocyanate and subsequent •acidimetric titrotion of the... reaction product in a nonuqueous solution. The method is rapid, selecti•., yields reproducible results, and in qIdely applicable INTRODUCTION The... reaction with p-tolupaesulfonyl isocyanate (TSNCO). Acetylation and phthalation have been used for a number of years and have been fairly well-characterized

  14. 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

  15. Anticancer effect of linalool via cancer-specific hydroxyl radical generation in human colon cancer

    PubMed Central

    Iwasaki, Kenichi; Zheng, Yun-Wen; Murata, Soichiro; Ito, Hiromu; Nakayama, Ken; Kurokawa, Tomohiro; Sano, Naoki; Nowatari, Takeshi; Villareal, Myra O; Nagano, Yumiko N; Isoda, Hiroko; Matsui, Hirofumi; Ohkohchi, Nobuhiro

    2016-01-01

    AIM To investigate the anticancer mechanisms of the monoterpenoid alcohol linalool in human colon cancer cells. METHODS The cytotoxic effect of linalool on the human colon cancer cell lines and a human fibroblast cell line was examined using the WST-8 assay. The apoptosis-inducing effect of linalool was measured using the terminal deoxynucleotidyl transferase dUTP nick-end labeling assay and flow cytometry with Annexin V. Oxidative stress was investigated by staining for diphenyl-1-pyrenylphosphine, which is a cellular lipid peroxidation marker, and electron spin resonance spectroscopy. Sixteen SCID mice xenografted with human cancer cells were randomized into 3 groups for in vivo analysis: control and low-dose and high-dose linalool groups. The control group was administered tap water orally every 3 d. The linalool treatment groups were administered 100 or 200 μg/kg linalool solution orally for the same period. All mice were sacrificed under anesthesia 21 d after tumor inoculation, and tumors and organs were collected for immunohistochemistry using an anti-4-hydroxynonenal antibody. Tumor weights were measured and compared between groups. RESULTS Linalool induced apoptosis of cancer cells in vitro, following the cancer-specific induction of oxidative stress, which was measured based on spontaneous hydroxyl radical production and delayed lipid peroxidation. Mice in the high-dose linalool group exhibited a 55% reduction in mean xenograft tumor weight compared with mice in the control group (P < 0.05). In addition, tumor-specific lipid peroxidation was observed in the in vivo model. CONCLUSION Linalool exhibited an anticancer effect via cancer-specific oxidative stress, and this agent has potential for application in colon cancer therapy. PMID:27956800

  16. Molecular Interaction Study of N-Benzylformamide with 1-ALCOHOLS Using X-Band Microwave

    NASA Astrophysics Data System (ADS)

    Manjunath, M. S.; Sannappa, J.

    The secondary amide unit is a subject of particular interest, because of its occurrence in peptides and proteins. Molecular interaction between N-benzylformamide (NBF) with 1-alcohols (1-propanol, 1-butanol, 1-pentanol) has been studied in carbon tetrachloride by using X-band microwave bench at 936 GHz. Dielectric constant (ɛ') and dielectric loss (ɛ″) of alcohol and NBF and their binary mixture for different mole fractions of NBF have been determined. Dielectric relaxation time (τ) of the binary system is obtained by both Higasi's method and the Gopalakrishna single-frequency concentration variational method. The results show that the most likely interaction between alcohols and NBF is 1:1 complex for binary mixture through the free hydroxyl group of the alcohol and the carbonyl group of NBF. The alkyl chain-length of both alcohol and amide plays an important role in the determination of the strength of hydrogen bond (O-H: C=O) formed. The variation of relaxation time of NBF+1-alcohol mixtures in CCl4 indicates a weak solute-solvent type of molecular association. The result shows that as the relaxation time of the proton acceptor increases, the donating ability of the solute environment increase.

  17. First Impressions on the Scene: The Influence of the Immediate Reference Group on Incoming First-Year Students' Alcohol Behavior and Attitudes

    ERIC Educational Resources Information Center

    Hummer, Justin F.; LaBrie, Joseph W.; Pedersen, Eric R.

    2012-01-01

    This study examined incoming first-year students' normative perceptions of alcohol use and alcohol-related attitudes of other students of the same gender living on their residence hall floor. Male and female residents overestimated the alcohol use behavior and related attitudes among their floormates. Results also showed that perceived norms were…

  18. Engineering a Monolignol 4-O-Methyltransferase with High Selectivity for the Condensed Lignin Precursor Coniferyl Alcohol*

    PubMed Central

    Cai, Yuanheng; Bhuiya, Mohammad-Wadud; Shanklin, John; Liu, Chang-Jun

    2015-01-01

    Lignin, a rigid biopolymer in plant cell walls, is derived from the oxidative polymerization of three monolignols. The composition of monolignol monomers dictates the degree of lignin condensation, reactivity, and thus the degradability of plant cell walls. Guaiacyl lignin is regarded as the condensed structural unit. Polymerization of lignin is initiated through the deprotonation of the para-hydroxyl group of monolignols. Therefore, preferentially modifying the para-hydroxyl of a specific monolignol to deprive its dehydrogenation propensity would disturb the formation of particular lignin subunits. Here, we test the hypothesis that specific remodeling the active site of a monolignol 4-O-methyltransferase would create an enzyme that specifically methylates the condensed guaiacyl lignin precursor coniferyl alcohol. Combining crystal structural information with combinatorial active site saturation mutagenesis and starting with the engineered promiscuous enzyme, MOMT5 (T133L/E165I/F175I/F166W/H169F), we incrementally remodeled its substrate binding pocket by the addition of four substitutions, i.e. M26H, S30R, V33S, and T319M, yielding a mutant enzyme capable of discriminately etherifying the para-hydroxyl of coniferyl alcohol even in the presence of excess sinapyl alcohol. The engineered enzyme variant has a substantially reduced substrate binding pocket that imposes a clear steric hindrance thereby excluding bulkier lignin precursors. The resulting enzyme variant represents an excellent candidate for modulating lignin composition and/or structure in planta. PMID:26378240

  19. Engineering a monolignol 4-O-methyltransferase with high selectivity for the condensed lignin precursor coniferyl alcohol.

    PubMed

    Cai, Yuanheng; Bhuiya, Mohammad-Wadud; Shanklin, John; Liu, Chang-Jun

    2015-10-30

    Lignin, a rigid biopolymer in plant cell walls, is derived from the oxidative polymerization of three monolignols. The composition of monolignol monomers dictates the degree of lignin condensation, reactivity, and thus the degradability of plant cell walls. Guaiacyl lignin is regarded as the condensed structural unit. Polymerization of lignin is initiated through the deprotonation of the para-hydroxyl group of monolignols. Therefore, preferentially modifying the para-hydroxyl of a specific monolignol to deprive its dehydrogenation propensity would disturb the formation of particular lignin subunits. Here, we test the hypothesis that specific remodeling the active site of a monolignol 4-O-methyltransferase would create an enzyme that specifically methylates the condensed guaiacyl lignin precursor coniferyl alcohol. Combining crystal structural information with combinatorial active site saturation mutagenesis and starting with the engineered promiscuous enzyme, MOMT5 (T133L/E165I/F175I/F166W/H169F), we incrementally remodeled its substrate binding pocket by the addition of four substitutions, i.e. M26H, S30R, V33S, and T319M, yielding a mutant enzyme capable of discriminately etherifying the para-hydroxyl of coniferyl alcohol even in the presence of excess sinapyl alcohol. The engineered enzyme variant has a substantially reduced substrate binding pocket that imposes a clear steric hindrance thereby excluding bulkier lignin precursors. The resulting enzyme variant represents an excellent candidate for modulating lignin composition and/or structure in planta.

  20. Adamantyl-Substituted Retinoid-Derived Molecules That Interact with the Orphan Nuclear Receptor Small Heterodimer Partner: Effects of Replacing the 1-Adamantyl or Hydroxyl Group on Inhibition of Cancer Cell Growth, Induction of Cancer Cell Apoptosis, and Inhibition of Src Homology 2 Domain-Containing Protein Tyrosine Phosphatase-2 Activity

    PubMed Central

    Dawson, Marcia I.; Xia, Zebin; Jiang, Tao; Ye, Mao; Fontana, Joseph A.; Farhana, Lulu; Patel, Bhaumik; Xue, Li Ping; Bhuiyan, Mohammad; Pellicciari, Roberto; Macchiarulo, Antonio; Nuti, Roberto; Zhang, Xiao-Kun; Han, Young-Hoon; Tautz, Lutz; Hobbs, Peter D.; Jong, Ling; Waleh, Nahid; Chao, Wan-ru; Feng, Gen-Sheng; Pang, Yuhong; Su, Ying

    2014-01-01

    (E)-4-[3-(1-Adamantyl)-4′-hydroxyphenyl]-3-chlorocinnamic acid (3-Cl-AHPC) induces the cell-cycle arrest and apoptosis of leukemia and cancer cells. Studies demonstrated that 3-Cl-AHPC bound to the atypical orphan nuclear receptor small heterodimer partner (SHP). Although missing a DNA-binding domain, SHP heterodimerizes with the ligand-binding domains of other nuclear receptors to repress their abilities to induce or inhibit gene expression. 3-Cl-AHPC analogues having the 1-adamantyl and phenolic hydroxyl pharmacophoric elements replaced with isosteric groups were designed, synthesized, and evaluated for their inhibition of proliferation and induction of human cancer cell apoptosis. Structure–anticancer activity relationship studies indicated the importance of both groups to apoptotic activity. Docking of 3-Cl-AHPC and its analogues to an SHP computational model that was based on the crystal structure of ultraspiracle complexed with 1-stearoyl-2-palmitoylglycero-3-phosphoethanolamine suggested why these 3-Cl-AHPC groups could influence SHP activity. Inhibitory activity against Src homology 2 domain-containing protein tyrosine phosphatase 2 (Shp-2) was also assessed. The most active Shp-2 inhibitor was found to be the 3′-(3,3-dimethylbutynyl) analogue of 3-Cl-AHPC. PMID:18759424

  1. Alcohol- and water-soluble bis(tpy)quaterthiophenes with phosphonium side groups: new conjugated units for metallo-supramolecular polymers.

    PubMed

    Štenclová, P; Šichová, K; Šloufová, I; Zedník, J; Vohlídal, J; Svoboda, J

    2016-01-21

    Bis(tpy)quaterthiophenes with symmetrically distributed two and four 6-bromohexyl side groups were prepared and modified by the reaction with triethylphosphine to give the corresponding ionic species. Both ionic and non-ionic bis(tpy)quaterthiophenes (unimers) were assembled with Zn(2+) and Fe(2+) ions to conjugated metallo-supramolecular polymers (MSPs), of which the ionic ones are soluble in alcohols and those derived from tetrasubstituted unimers are soluble even in water. The differences in assembly are specified between systems with (i) ionic and non-ionic unimers, (ii) Zn(2+) and Fe(2+) ion couplers, and (iii) methanol and water solvents. A substantial decrease in the stability of Fe-MSPs and a surprisingly high red shift of the luminescence band of Zn-MSPs were observed on going from methanol to aqueous solutions.

  2. Propranolol hydroxylation and N-desisopropylation by cytochrome P4502D6: studies using the yeast-expressed enzyme and NADPH/O2 and cumene hydroperoxide-supported reactions.

    PubMed

    Bichara, N; Ching, M S; Blake, C L; Ghabrial, H; Smallwood, R A

    1996-01-01

    We have studied the enantioselectivity and regioselectivity of ring-hydroxylation and N-desisopropylation of R(+)- and S(-)-propranolol in microsomes from yeast expressing cytochrome P4502D6 (CYP2D6), using both NADPH and molecular oxygen (NADPH/O2) and cumene hydroperoxide-supported reactions. With NADPH/O2-supported reactions, CYP2D6 catalyzed 4- and 5-ring-hydroxylation, as well as N-desisopropylation of propranolol, although Vmax was considerably greater for ring-hydroxylation, compared with N-desisopropylation. The R/S ratios for KM and Vmax were less than unity for all three pathways. In contrast, using cumene hydroperoxide-supported reactions, CYP2D6 catalyzed 4- and 5-ring-hydroxylation, and there was negligible N-desisopropylation of propranolol. The R/S ratio for KM was less than unity, but the R/S ratio for Vmax was close to unity. The cumyl group of cumene hydroperoxide did not seem to be a selective inhibitor of N-desisopropylation, because i) cumyl alcohol (a nonalkylhydroperoxide analog of cumene hydroperoxide) did not inhibit N-desisopropylation in NADPH/O2-supported reactions, and ii) the use of t-butyl hydroperoxide (a noncumyl alkylhydroperoxide) to support CYP2D6 catalysis resulted in ring-hydroxylation, but not N-desisopropylation. At a propranolol concentration near KM, quinidine inhibited both ring-hydroxylation and N-desisopropylation in an equipotent manner in NADPH/O2-supported reactions. However, in cumene hydroperoxide-supported reactions, the IC50 of inhibition of ring-hydroxylation by quinidine was an order of magnitude less potent than in NADPH/O2-supported reactions. Our study shows that recombinant CYP2D6 cannot only catalyze 4- and 5-ring-hydroxylation of propranolol, but also N-desisopropylation. The lack of propranolol N-desisopropylation observed in cumene hydroperoxide-supported reactions highlights the need for caution when using alkyhydroperoxides to study CYP2D6 catalysis.

  3. Rotational Spectrum of Ar...PROPARGYL Alcohol Complex

    NASA Astrophysics Data System (ADS)

    Mani, Devendra; Shahi, Abhishek; Arunan, E.

    2012-06-01

    Pure rotational spectrum for Ar...Propargyl alcohol complex has been observed and fitted. Fitted rotational constants for the complex are : A=4346.17307(90) MHz, B=1617.15317(19)MHz and C= 1245.42065(15) MHz. These rotational constants are very close to the ab-initio rotational constants for the geometry, in which propargyl alcohol exists in gauche conformation and Ar interacts with both, the hydroxyl group and the acetylenic group of propargyl alcohol. Rotational spectrum of deuterated isotopologue (-OD) of the complex further confirms the existence of the above mentioned geometry. In previous studies tunneling frequency corresponding to -OH tunneling motion in propargyl alocohol monomer was determined to be 652.4 GHz and for -OD tunneling motion in mono-deuterated species, it was 213.5 GHz. In Ar...Propargyl alcohol complex also, a-type and c-dipole transitions show tunneling splitting. In the parent complex, for a-type transitions, tunneling splitting was 10 KHz and for c-type transitions (c-dipole of the complex is in the same direction as in propargyl alcohol monomer, and it is antisymmetric with respect to OH tunneling motion in both monomer and the complex), it was 2.59 MHz. In deuterated complex (OD) splitting was not resolvable for a-type transitions while for c-type it reduces to 900 KHz. Search for C-13 isotopologues is in progress. Moreover, propargyl alcohol offers several possibilities for H-bonding and we are planning to study its complexes with water in near future. Results will be presented in the talk. E. Hirota,J. Mol. Spectrosc. 26 (1968) 335-350. J.C. Pearson, B.J. Drouin, J. Mol. Spectrosc. 234 (2005) 149-156.

  4. Mechanism of alcohol-enhanced lucigenin chemiluminescence in alkaline solution.

    PubMed

    Chi, Quan; Chen, Wanying; He, Zhike

    2015-11-01

    The chemiluminescence (CL) of lucigenin (Luc(2+)) can be enhanced by different alcohols in alkaline solution. The effect of different fatty alcohols on the CL of lucigenin was related to the carbon chain length and the number of hydroxyl groups. Glycerol provides the greatest enhancement. UV/Vis absorption spectra and fluorescence spectra showed that N-methylacridone (NMA) was produced in the CL reaction in the presence of different alcohols. The peak of the CL spectrum was located at 470 nm in all cases, indicating that the luminophore was always the excited-state NMA. The quenching of lucigenin CL by superoxide dismutase (SOD) and the electron spin resonance (ESR) results with the spin trap of 5,5-dimethyl-1-pyrroline N-oxide (DMPO) demonstrated that superoxide anions (O2 (•-)) were generated from dissolved oxygen in the CL reaction and that glycerol and dihydroxyacetone (DHA) can promote O2 (•-) production by the reduction of dissolved oxygen in alkaline solution. It was assumed that the enhancement provided by different alcohols was related to the solvent effect and reducing capacity. Glycerol and DHA can also reduce Luc(2+) into lucigenin cation radicals (Luc(•+) ), which react with O2 (•-) to produce CL, and glycerol can slowly transform into DHA, which is oxidized quickly in alkaline solution.

  5. Hydroxyl radical oxidation of feruloylated arabinoxylan.

    PubMed

    Bagdi, Attila; Tömösközi, Sándor; Nyström, Laura

    2016-11-05

    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.

  6. 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.

  7. 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

    2016-02-07

    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.

  8. Gold(I)-catalyzed intramolecular amination of allylic alcohols with alkylamines.

    PubMed

    Mukherjee, Paramita; Widenhoefer, Ross A

    2011-03-18

    A 1:1 mixture of (1)AuCl [1 = P(t-Bu)(2)o-biphenyl] and AgSbF(6) catalyzes the intramolecular amination of allylic alcohols with alkylamines to form substituted pyrrolidine and piperidine derivatives. Gold(I)-catalyzed cyclization of (R,Z)-8-(N-benzylamino)-3-octen-2-ol (96% ee, 95% de) led to isolation of (R,E)-1-benzyl-2-(1-propenyl)piperidine in 99% yield with 96% ee, consistent with the net syn addition of the amine relative to the departing hydroxyl group.

  9. [Does acamprosate diminish the appetite for alcohol in weaned alcoholics?].

    PubMed

    Roussaux, J P; Hers, D; Ferauge, M

    1996-01-01

    A population of 127 alcoholics of both sexes, hospitalized and weaned (DSM III diagnose: Alcohol Abuse and Alcohol Dependence) received Acamprosate (n = 63) or placebo (n = 64) in a double blind randomized therapeutic trail. The patients were followed during three months and anamnestic as well as biological data were recorded. It appeared no significant differences between the two groups of patients. This negative result could perhaps be explained by the heaviness of the pathology of this hospitalized alcoholic population.

  10. Adsorption properties of polyvinyl-alcohol-grafted particles toward genistein driven by hydrogen-bond interaction.

    PubMed

    Zhang, Yanyan; Gao, Baojiao; Xu, Zeqing

    2013-05-09

    The adsorption properties of polyvinyl alcohol (PVA)-grafted silica gel particles PVA/SiO2 toward genistein are researched in this paper. The effects of the main factors on the adsorption properties are investigated, the adsorption mechanism is explored in depth, and the adsorption thermodynamics is researched. The experimental results show that the conventional hydrogen bond is formed between the hydroxyl groups with high density on the surfaces of PVA/SiO2 and the phenolic hydroxyl groups in genistein, while π-type hydrogen bond is formed between the hydroxyl groups of PVA/SiO2 and the conjugated aromatic rings. It is the two types of hydrogen bond that make the functional composite particles PVA/SiO2 produce very strong physical adsorption toward genistein. The competitive adsorption of the solvent can have severe negative impact on the adsorption capacity of genistein. Increasing temperature will weaken the hydrogen-bond interaction between PVA/SiO2 particles and genistein. The existence of electrolytes in the protic solvent will affect the adsorption negatively. The adsorption process of PVA/SiO2 particles toward genistein is exothermic and driven by enthalpy. The adsorption isotherm data matches the Langmuir model.

  11. Hydroxylated PBDEs induce developmental arrest in zebrafish.

    PubMed

    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.

  12. 21 CFR 172.814 - Hydroxylated lecithin.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... label of the food additive container shall bear, in addition to the other information required by the... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Hydroxylated lecithin. 172.814 Section 172.814 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED)...

  13. Alcohol Calorie Calculator

    MedlinePlus

    ... Alcohol Calorie Calculator Weekly Total 0 Calories Alcohol Calorie Calculator Find out the number of beer and ... Calories College Alcohol Policies Interactive Body Calculators Alcohol Calorie Calculator Alcohol Cost Calculator Alcohol BAC Calculator Alcohol ...

  14. Targeted acylation for all the hydroxyls of (+)-catechin and evaluation of their individual contribution to radical scavenging activity.

    PubMed

    Hong, Shan; Liu, Songbai

    2016-04-15

    The reactivity profile of all the hydroxyl groups in (+)-catechin towards acylation and their respective contribution to radical scavenging activity were systematically explored in this work. Selective acylation of the hydroxyls on different rings was carried out employing either a basic or acidic activation strategy. Monoacylation of B ring was achieved effectively with the aid of dimethyltin dichloride. Monoacylation of A ring was accomplished by sequential protection and deprotection of B and C rings. Based on specific acylation of all the individual hydroxyls of (+)-catechins, the structure radical scavenging activity relationship of each hydroxyl of (+)-catechin was established. It was demonstrated that the vicinal phenolic hydroxyls on B ring played the most important role in the ABTS radical scavenging activity and those on A and C rings made a much smaller contribution. This study has laid solid groundwork for further modification of the catechins and improvement of their properties.

  15. Hydroxyl-directed stereoselective diboration of alkenes.

    PubMed

    Blaisdell, Thomas P; Caya, Thomas C; Zhang, Liang; Sanz-Marco, Amparo; Morken, James P

    2014-07-02

    An alkoxide-catalyzed directed diboration of alkenyl alcohols is described. This reaction occurs in a stereoselective fashion and is demonstrated with cyclic and acyclic homoallylic and bishomoallylic alcohol substrates. After oxidation, the reaction generates 1,2-diols such that the process represents a method for the stereoselective directed dihydroxylation of alkenes.

  16. Inhibition of membrane lipid peroxidation by a radical scavenging mechanism: a novel function for hydroxyl-containing ionophores.

    PubMed

    Grijalba, M T; Andrade, P B; Meinicke, A R; Castilho, R F; Vercesi, A E; Schreier, S

    1998-03-01

    In the present study we show that K+/H+ hydroxyl-containing ionophores lasalocid-A (LAS) and nigericin (NIG) in the nanomolar concentration range, inhibit Fe2+-citrate and 2,2'-azobis(2-amidinopropane) dihydrochloride (ABAP)-induced lipid peroxidation in intact rat liver mitochondria and in egg phosphatidylcholine (PC) liposomes containing negatively charged lipids--dicetyl phosphate (DCP) or cardiolipin (CL)--and KCl as the osmotic support. In addition, monensin (MON), a hydroxyl-containing ionophore with higher affinity for Na+ than for K+, promotes a similar effect when NaCl is the osmotic support. The protective effect of the ionophores is not observed when the osmolyte is sucrose. Lipid peroxidation was evidenced by mitochondrial swelling, antimycin A-insensitive O2 consumption, formation of thiobarbituric acid-reactive substances (TBARS), conjugated dienes, and electron paramagnetic resonance (EPR) spectra of an incorporated lipid spin probe. A time-dependent decay of spin label EPR signal is observed as a consequence of lipid peroxidation induced by both inductor systems in liposomes. Nitroxide destruction is inhibited by butylated hydroxytoluene, a known antioxidant, and by the hydroxyl-containing ionophores. In contrast, valinomycin (VAL), which does not possess alcoholic groups, does not display this protective effect. Effective order parameters (Seff), determined from the spectra of an incorporated spin label are larger in the presence of salt and display a small increase upon addition of the ionophores, as a result of the increase of counter ion concentration at the negatively charged bilayer surface. This condition leads to increased formation of the ion-ionophore complex, the membrane binding (uncharged) species. The membrane-incorporated complex is the active species in the lipid peroxidation inhibiting process. Studies in aqueous solution (in the absence of membranes) showed that NIG and LAS, but not VAL, decrease the Fe2+-citrate-induced production

  17. Determination of surface-accessible acidic hydroxyls and surface area of lignin by cationic dye adsorption.

    PubMed

    Sipponen, Mika Henrikki; Pihlajaniemi, Ville; Littunen, Kuisma; Pastinen, Ossi; Laakso, Simo

    2014-10-01

    A new colorimetric method for determining the surface-accessible acidic lignin hydroxyl groups in lignocellulose solid fractions was developed. The method is based on selective adsorption of Azure B, a basic dye, onto acidic hydroxyl groups of lignin. Selectivity of adsorption of Azure B on lignin was demonstrated using lignin and cellulose materials as adsorbents. Adsorption isotherms of Azure B on wheat straw (WS), sugarcane bagasse (SGB), oat husk, and isolated lignin materials were determined. The maximum adsorption capacities predicted by the Langmuir isotherms were used to calculate the amounts of surface-accessible acidic hydroxyl groups. WS contained 1.7-times more acidic hydroxyls (0.21 mmol/g) and higher surface area of lignin (84 m(2)/g) than SGB or oat husk materials. Equations for determining the amount of surface-accessible acidic hydroxyls in solid fractions of the three plant materials by a single point measurement were developed. A method for high-throughput characterization of lignocellulosic materials is now available.

  18. Chronic intermittent alcohol disrupts the GluN2B-associated proteome and specifically regulates group I mGlu receptor-dependent long-term depression.

    PubMed

    Wills, Tiffany A; Baucum, Anthony J; Holleran, Katherine M; Chen, Yaoyi; Pasek, Johanna G; Delpire, Eric; Tabb, David L; Colbran, Roger J; Winder, Danny G

    2017-03-01

    N-Methyl-d-aspartate receptors (NMDARs) are major targets of both acute and chronic alcohol, as well as regulators of plasticity in a number of brain regions. Aberrant plasticity may contribute to the treatment resistance and high relapse rates observed in alcoholics. Recent work suggests that chronic alcohol treatment preferentially modulates both the expression and subcellular localization of NMDARs containing the GluN2B subunit. Signaling through synaptic and extrasynaptic GluN2B-NMDARs has already been implicated in the pathophysiology of various other neurological disorders. NMDARs interact with a large number of proteins at the glutamate synapse, and a better understanding of how alcohol modulates this proteome is needed. We employed a discovery-based proteomic approach in subcellular fractions of hippocampal tissue from chronic intermittent alcohol (CIE)-exposed C57Bl/6J mice to gain insight into alcohol-induced changes in GluN2B signaling complexes. Protein enrichment analyses revealed changes in the association of post-synaptic proteins, including scaffolding, glutamate receptor and PDZ-domain binding proteins with GluN2B. In particular, GluN2B interaction with metabotropic glutamate (mGlu)1/5 receptor-dependent long-term depression (LTD)-associated proteins such as Arc and Homer 1 was increased, while GluA2 was decreased. Accordingly, we found a lack of mGlu1/5 -induced LTD while α1 -adrenergic receptor-induced LTD remained intact in hippocampal CA1 following CIE. These data suggest that CIE specifically disrupts mGlu1/5 -LTD, representing a possible connection between NMDAR and mGlu receptor signaling. These studies not only demonstrate a new way in which alcohol can modulate plasticity in the hippocampus but also emphasize the utility of this discovery-based proteomic approach to generate new hypotheses regarding alcohol-related mechanisms.

  19. Ego Identity of Adolescent Children of Alcoholics

    ERIC Educational Resources Information Center

    Gavriel-Fried, Belle; Teichman, Meir

    2007-01-01

    The study examines the issue of ego identity among adolescent sons of alcoholic fathers. Forty-four adolescent sons of alcoholic fathers, age of 15-18, constituted the sample. They were drawn from public alcohol treatment center in Israel. The control group included 60 adolescents none of their parents is known as an alcoholic, sampled from…

  20. How Do Underage College Students Get Alcohol?

    ERIC Educational Resources Information Center

    Fabian, Lindsey E. A.; Toomey, Traci L.; Lenk, Kathleen M.; Erickson, Darin J.

    2008-01-01

    Alcohol consumption and related problems are common among underage college students, yet qualitative, in-depth information on how/where these students obtain alcohol is limited. We conducted focus groups pertaining to access to alcohol and related issues with 19 underage college students. They reported that alcohol is easy to obtain from a variety…

  1. Validity of Five MMPI Alcoholism Scales.

    ERIC Educational Resources Information Center

    Holmes, Cooper B.; And Others

    1982-01-01

    Assessed five alcoholism scales derived from the Minnesota Multiphasic Personality Inventory for their ability to classify accurately alcoholics and non-alcoholic psychiatric patients. The alcoholic group was divided into self-committed and court-committed. Depending on how the data were treated, found only one, or none of the scales accurate.…

  2. Alcoholic hepatitis: current management.

    PubMed

    Spengler, Erin K J; Dunkelberg, Jeffrey; Schey, Ron

    2014-10-01

    Alcoholic hepatitis is an acute manifestation of alcoholic liver disease with mortality as high as 40-50% in severe cases. Patients usually have a history of prolonged alcohol abuse with or without a known history of liver disease. Although there is significant range in severity at presentation, patients with severe alcoholic hepatitis typically present with anorexia, fatigue, fever, jaundice, and ascites. The use of either pentoxifylline or corticosteroids in those with severe disease (Maddrey's discriminate function >32) has significant mortality benefit. The addition of N-acetylcysteine to corticosteroids decreases the incidences of hepatorenal syndrome, infection, and short-term mortality, but does not appear to significantly affect 6-month mortality. Nutritional support with high-calorie, high-protein diet is recommended in all patients screening positive for malnutrition. Liver transplantation for a highly selected group of patients with severe alcoholic hepatitis may be an option in the future, but is not currently recommended or available at most transplant institutions.

  3. Photoreactivity of hydroxylated multi-walled carbon nanotubes and its effects on the photodegradation of atenolol in water.

    PubMed

    Zhang, Ya; Zhou, Lei; Zeng, Chao; Wang, Qi; Wang, Zunyao; Gao, Shixiang; Ji, Yuefei; Yang, Xi

    2013-11-01

    In spite of the increasing concerns about the fate of pharmaceuticals and personal care products (PPCPs) and the nanomaterial pollution in aquatic ecosystem, the effects of carbon nanotubes on the photochemical transformation of PPCPs are less considered. In this study, the photochemical production of reactive oxygen species (ROS) were examined in colloidal dispersions of hydroxylated multi-walled carbon nanotubes (MWNT-OH) under simulated solar irradiation using a Xenon lamp. Two kinds of ROS, (1)O2 and OH, were confirmed by their molecular probes, furfuryl alcohol (FFA) and p-chlorobenzoic acid (PCBA). The steady-state concentrations of (1)O2 and OH were calculated as 1.30×10(-14) M and 5.02×10(-16) M, respectively. The effects of MWNT-OH on photodegradation of atenolol (ATL) were investigated in the presence of natural water components, i.e., dissolved organic matters (DOMs), nitrate (NO3(-)) and ferric ions (Fe(3+)). Photoproducts of atenolol were identified by solid phase extraction-liquid chromatography-mass spectrometry (SPE-LC-MS) analysis techniques. Three potential photochemical pathways of atenolol, including the hydroxylation on aromatic ring, the loss of amide group and the cleavage of ether oxygen bond as well as di-polymerization of reaction intermediates were tentatively proposed. Using the radical quenching method, reaction with OH was determined as the major photolysis pathway of atenolol in irradiated MWNT-OH suspensions. These findings of the production of ROS and their effects on the photodegradation of organic contaminants provided useful information for assessing environmental risk of MWNT-OH.

  4. Efficient degradation of atrazine by magnetic porous copper ferrite catalyzed peroxymonosulfate oxidation via the formation of hydroxyl and sulfate radicals.

    PubMed

    Guan, Ying-Hong; Ma, Jun; Ren, Yue-Ming; Liu, Yu-Lei; Xiao, Jia-Yue; Lin, Ling-qiang; Zhang, Chen

    2013-09-15

    Magnetic porous copper ferrite (CuFe2O4) showed a notable catalytic activity to peroxymonosulfate (PMS). More than 98% of atrazine was degraded within 15 min at 1 mM PMS and 0.1 g/L CuFe2O4. In contrast, CuFe2O4 exhibited no obvious catalytic activity to peroxodisulfate or H2O2. Several factors affecting the catalytic performance of PMS/CuFe2O4 were investigated. Results showed that the catalytic degradation efficiency of atrazine increased with PMS and CuFe2O4 doses, but decreased with the increase of natural organic matters concentration. The catalytic oxidation also showed a dependence on initial pH. The presence of bicarbonate stimulated atrazine degradation by PMS/CuFe2O4 at low concentrations but inhibited the degradation at high concentrations. Furthermore, the reactive species for atrazine degradation in PMS/CuFe2O4 system were identified as hydroxyl radical (HO) and sulfate radical (SO4(·-)) through competition reactions of atrazine and nitrobenzene, instead of commonly used alcohol scavenging, which was not a reliable method in metal oxide catalyzed oxidation. Surface hydroxyl groups of CuFe2O4 were a critical part in radical generation and the copper on CuFe2O4 surface was an active site to catalyze PMS. The catalytic degradation of atrazine by PMS/CuFe2O4 was also effective under the background of actual waters.

  5. In-situ cross linking of polyvinyl alcohol. [application to battery separator films

    NASA Technical Reports Server (NTRS)

    Philipp, W. H.; Hsu, L. C.; Sheibley, D. W. (Inventor)

    1981-01-01

    A method of producing a crosslinked polyvinyl alcohol structure, such as a battery separator membrane or electrode envelope is described. An aqueous solution of a film-forming polyvinyl alcohol is admixed with an aldehyde crosslinking agent a basic pH to inhibit crosslinking. The crosslinking agent, perferably a dialdehyde such as glutaraldehyde, is used in an amount of from about 1/2 to about 20% of the theoretical amount required to crosslink all of the hydroxyl groups of the polymer. The aqueous admixture is formed into a desired physical shape, such as by casting a sheet of the solution. The sheet is then dried to form a self-supporting film. Crosslinking is then effected by immersing the film in aqueous acid solution. The resultant product has excellent properties for use as a battery separator.

  6. Molecular dynamics simulation study of the effect of glycerol dialkyl glycerol tetraether hydroxylation on membrane thermostability.

    PubMed

    Huguet, Carme; Fietz, Susanne; Rosell-Melé, Antoni; Daura, Xavier; Costenaro, Lionel

    2017-02-16

    Archaeal tetraether membrane lipids span the whole membrane width and present two C40 isoprenoid chains bound by two glycerol groups (or one glycerol and calditol). These lipids confer stability and maintain the membrane fluidity in mesophile to extremophile environments, making them very attractive for biotechnological applications. The isoprenoid lipid composition in archaeal membranes varies with temperature, which has placed these lipids in the focus of paleo-climatological studies for over a decade. Non-hydroxylated isoprenoid archaeal lipids are typically used as paleo-thermometry proxies, but recently identified hydroxylated (OH) derivatives have also been proposed as temperature proxies. The relative abundance of hydroxylated lipids increases at lower temperatures, but the physiological function of the OH moiety remains unknown. Here we present molecular dynamics simulations of membranes formed by the acyclic glycerol-dialkyl-glycerol-tetraether caldarchaeol (GDGT-0), the most widespread archaeal core lipid, and its mono-hydroxylated variant (OH-GDGT-0) to better understand the physico-chemical properties conferred to the membrane by this additional moiety. The molecular dynamics simulations indicate that the additional OH group forms hydrogen bonds mainly with the sugar moieties of neighbouring lipids and with water molecules, effectively increasing the size of the polar headgroups. The hydroxylation also introduces local disorder that propagates along the entire alkyl chains, resulting in a slightly more fluid membrane. These changes would help to maintain trans-membrane transport in cold environments, explaining why the relative abundance of hydroxylated Archaea lipids increases at lower temperatures. The in silico approach aids to understand the underlying physiological mechanisms behind the hydroxylated lipid based paleo-thermometer recently proposed.

  7. Selective Aromatic Hydroxylation with Dioxygen and Simple Copper Imine Complexes.

    PubMed

    Becker, Jonathan; Gupta, Puneet; Angersbach, Friedrich; Tuczek, Felix; Näther, Christian; Holthausen, Max C; Schindler, Siegfried

    2015-08-10

    The formation of a bis(μ-oxido)dicopper complex with the ligand 2-(diethylaminoethyl)-6-phenylpyridine (PPN) and its subsequent hydroxylation of the pendant phenyl group (studied earlier by Holland et al., Angew. Chem. Int. Ed.- 1999, 38, 1139-1142) has been reinvestigated to gain a better understanding of such systems in view of the development of new synthetic applications. To this end, we prepared a simple copper imine complex system that also affords selective o-hydroxylation of aromatic aldehydes by using dioxygen as the oxidant: Applying the ligand N'-benzylidene-N,N-diethylethylenediamine (BDED), salicylaldehyde was prepared in good yields and we show that this reaction also occurs through an intermediate bis-μ-oxido copper complex. The underlying reaction mechanism for the PPN-supported complex was studied at the BLYP-D/TZVP level of density functional theory and the results for representative stationary points along reaction paths of the BDED-supported complex reveal a closely related mechanistic scenario. The results demonstrate a new facile synthetic way to introduce OH groups into aromatic aldehydes.

  8. Alcohol Consumption in Demographic Subpopulations

    PubMed Central

    Delker, Erin; Brown, Qiana; Hasin, Deborah S.

    2016-01-01

    Alcohol consumption is common across subpopulations in the United States. However, the health burden associated with alcohol consumption varies across groups, including those defined by demographic characteristics such as age, race/ethnicity, and gender. Large national surveys, such as the National Epidemiologic Survey on Alcohol and Related Conditions and the National Survey on Drug Use and Health, found that young adults ages 18–25 were at particularly high risk of alcohol use disorder and unintentional injury caused by drinking. These surveys furthermore identified significant variability in alcohol consumption and its consequences among racial/ethnic groups. White respondents reported the highest prevalence of current alcohol consumption, whereas alcohol abuse and dependence were most prevalent among Native Americans. Native Americans and Blacks also were most vulnerable to alcohol-related health consequences. Even within ethnic groups, there was variability between and among different subpopulations. With respect to gender, men reported more alcohol consumption and binge drinking than women, especially in older cohorts. Men also were at greater risk of alcohol abuse and dependence, liver cirrhosis, homicide after alcohol consumption, and drinking and driving. Systematic identification and measurement of the variability across demographics will guide prevention and intervention efforts, as well as future research. PMID:27159807

  9. 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.

  10. STM and HREELS investigation of gas phase silanization on hydroxylated Si(100)

    NASA Astrophysics Data System (ADS)

    Fan, C.; Lopinski, G. P.

    2010-06-01

    The gas phase anhydrous reaction of glycidoxypropyldimethylethoxysilane (GPDMES) with a model hydroxylated surface has been investigated using high-resolution electron energy loss spectroscopy (HREELS) and scanning tunneling microscopy (STM). Water dissociation on the clean reconstructed (2 × 1)-Si(100) surface was used to create an atomically flat surface with ~ 0.5 ML of hydroxyl groups. Exposure of this surface to GPDMES at room temperature under vacuum was found to lead to formation of covalent Si-O-Si bonds although high exposures (6 × 10 8 L) were required for saturation. STM images at the early stages of reaction indicate that the reaction occurs randomly on the surface with no apparent clustering. The STM images together with semi-empirical (AM1) calculations provide evidence for hydrogen bonding interactions between the oxygen atoms in the molecule and surface hydroxyl groups at low coverage.

  11. Probing RNA folding by hydroxyl radical footprinting.

    PubMed

    Costa, Maria; Monachello, Dario

    2014-01-01

    In recent years RNA molecules have emerged as central players in the regulation of gene expression. Many of these noncoding RNAs possess well-defined, complex, three-dimensional structures which are essential for their biological function. In this context, much effort has been devoted to develop computational and experimental techniques for RNA structure determination. Among available experimental tools to investigate the higher-order folding of structured RNAs, hydroxyl radical probing stands as one of the most informative and reliable ones. Hydroxyl radicals are oxidative species that cleave the nucleic acid backbone solely according to the solvent accessibility of individual phosphodiester bonds, with no sequence or secondary structure specificity. Therefore, the cleavage pattern obtained directly reflects the degree of protection/exposure to the solvent of each section of the molecule under inspection, providing valuable information about how these different sections interact together to form the final three-dimensional architecture. In this chapter we describe a robust, accurate and very sensitive hydroxyl radical probing method that can be applied to any structured RNA molecule and is suitable to investigate RNA folding and RNA conformational changes induced by binding of a ligand.

  12. Identification of hydroxylated metabolites of hexabromocyclododecane in wildlife and 28-days exposed Wistar rats.

    PubMed

    Brandsma, Sicco H; Van der Ven, Leo T M; De Boer, Jacob; Leonards, Pim E G

    2009-08-01

    We studied the presence of hydroxylated metabolites of hexabromocyclododecane (HBCD) in three wildlife species (tern egg, seal, and flounder) and in Wistar rats exposed to 30 and 100 mg HBCD/kg bw/day for 28 days. A nondestructive extraction, fractionation, and cleanup method was developed to separate the hydroxylated HBCD metabolites from the biotic sample matrix. Four different groups of hydroxylated HBCD metabolites were identified in rat adipose, liver, lung, and muscle tissues by liquid and gas chromatography (LC and GC) combined with mass spectrometry (MS): monohydroxy metabolites of HBCD, pentabromocyclododecene (PBCDe), tetrabromocyclododecene (TBCDe), and dihydroxy-HBCD. Dihydroxy-PBCDe was identified by GC-MS but could not be confirmed by LCMS. Debromination of HBCD to PBCDe was another metabolic pathway observed. In tern eggs from the Western Scheldt the monohydroxy-HBCD was found and in the blubber of harbor seal (Wadden Sea) the monohydroxy metabolites of HBCD and PBCDe were found. No hydroxylated metabolites were detected in the tissue of flounder (Wadden Sea). To our knowledge, this is the first study to identify different hydroxylated metabolite groups of HBCD in rat and wildlife samples.

  13. Regioselective monochloro substitution in carbohydrates and non-sugar alcohols via Mitsunobu reaction: applications in the synthesis of reboxetine.

    PubMed

    Dar, Abdul Rouf; Aga, Mushtaq A; Kumar, Brijesh; Yousuf, Syed Khalid; Taneja, Subhash Chandra

    2013-09-28

    A regioselective high yielding monochloro substitution (chlorohydrin formation) via Mitsunobu reaction is reported. In carbohydrates and sterically hindered non-sugars, only the primary hydroxyl group is chlorinated, whereas in the non-sugar 1,2- and 1,3-alcohols, predominantly the secondary chloride substitution occurs. The versatile methodology provides indirect access to epoxides with the retention of configuration, as against conventional Mitsunobu reaction which generates epoxides with inversion. The methodology was successfully used as a key step in the synthesis of optically active diastereoisomers of the antidepressant drug reboxetine from (R)-2,3-O-cyclohexylidene-d-glyceraldehyde in ∼43% overall yields.

  14. National Institute on Alcohol Abuse and Alcoholism

    MedlinePlus

    ... Alcohol Awareness Month April is Alcohol Awareness Month Biosensor Challenge Learn more College Drinking Learn More Alcohol Dependence Get the facts Alcohol Awareness Month Biosensor Challenge College Drinking Alcohol Dependence Latest News New & ...

  15. 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

  16. Alcohols toxicology

    SciTech Connect

    Wimer, W.W.; Russell, J.A.; Kaplan, H.L.

    1984-01-01

    A comprehensive reference volume which summarizes literature reports of the known consequences of human and animal contact with alcohols and alcohol-derived substances is presented. Following a discussion of alcohol nomenclature and a brief history of alcohols, the authors have provided detailed chapters on the toxicology of methanol, ethanol, normal and isopropanol, and the butanols. Properties of these alcohols are compared; industrial hygiene and exposure limits are discussed. Additional sections are included covering processing and production technology and exhaust emissions studies. Of particular interest are the section containing abstracts and synopses of principal works and the extensive bibliography of studies dating from the 1800s. 331 references, 26 figures, 56 tables

  17. The Aging and Alcohol Abuse.

    ERIC Educational Resources Information Center

    Brody, Jacob A.

    Demographic data suggest that alcohol abuse among the elderly will increase in proportion to the population growth of that group. Four factors which may cause the elderly to be a highly susceptible group for alcohol problems are: (1) retirement and its boredom, role changes, and financial problems; (2) increased concern with death and losses of…

  18. Alcohol-binding sites in distinct brain proteins: the quest for atomic level resolution.

    PubMed

    Howard, Rebecca J; Slesinger, Paul A; Davies, Daryl L; Das, Joydip; Trudell, James R; Harris, R Adron

    2011-09-01

    Defining the sites of action of ethanol on brain proteins is a major prerequisite to understanding the molecular pharmacology of this drug. The main barrier to reaching an atomic-level understanding of alcohol action is the low potency of alcohols, ethanol in particular, which is a reflection of transient, low-affinity interactions with their targets. These mechanisms are difficult or impossible to study with traditional techniques such as radioligand binding or spectroscopy. However, there has been considerable recent progress in combining X-ray crystallography, structural modeling, and site-directed mutagenesis to define the sites and mechanisms of action of ethanol and related alcohols on key brain proteins. We review such insights for several diverse classes of proteins including inwardly rectifying potassium, transient receptor potential, and neurotransmitter-gated ion channels, as well as protein kinase C epsilon. Some common themes are beginning to emerge from these proteins, including hydrogen bonding of the hydroxyl group and van der Waals interactions of the methylene groups of ethanol with specific amino acid residues. The resulting binding energy is proposed to facilitate or stabilize low-energy state transitions in the bound proteins, allowing ethanol to act as a "molecular lubricant" for protein function. We discuss evidence for characteristic, discrete alcohol-binding sites on protein targets, as well as evidence that binding to some proteins is better characterized by an interaction region that can accommodate multiple molecules of ethanol.

  19. Three methods for in situ cross-linking of polyvinyl alcohol films for application as ion-conducting membranes in potassium hydroxide electrolyte. [battery separators

    NASA Technical Reports Server (NTRS)

    Philipp, W. H.; Hsu, L. C.

    1979-01-01

    Three methods of in situ cross-linking polyvinyl alcohol films are presented. They are: (1) acetalization with a dialdehyde such as glutaraldehyde, (2) acetalization with aldehyde groups formed by selective oxidative cleaving of the few percent of 1,2 diol units present in polyvinyl alcohol, and (3) cross-linking by hydrogen abstraction by reaction with hydrogen atoms and hydroxyl radicals from irradiated water. For the third method, improvement in film conductivity in KOH solution at the expense of mechanical strength is obtained by the presence of polyacrylic acid in the polyvinyl alcohol films. Resistivities in 45 percent KOH are given for in situ cross-linked films prepared by each of the three methods.

  20. Photobiomodulation on alcohol induced dysfunction

    NASA Astrophysics Data System (ADS)

    Yang, Zheng-Ping; Liu, Timon C.; Zhang, Yan; Wang, Yan-Fang

    2007-05-01

    Alcohol, which is ubiquitous today, is a major health concern. Its use was already relatively high among the youngest respondents, peaked among young adults, and declined in older age groups. Alcohol is causally related to more than 60 different medical conditions. Overall, 4% of the global burden of disease is attributable to alcohol, which accounts for about as much death and disability globally as tobacco and hypertension. Alcohol also promotes the generation of reactive oxygen species (ROS) and/or interferes with the body's normal defense mechanisms against these compounds through numerous processes, particularly in the liver. Photobiomodulation (PBM) is a cell-specific effect of low intensity monochromatic light or low intensity laser irradiation (LIL) on biological systems. The cellular effects of both alcohol and LIL are ligand-independent so that PBM might rehabilitate alcohol induced dysfunction. The PBM on alcohol induced human neutrophil dysfunction and rat chronic atrophic gastritis, the laser acupuncture on alcohol addiction, and intravascular PBM on alcoholic coma of patients and rats have been observed. The endonasal PBM (EPBM) mediated by Yangming channel, autonomic nervous systems and blood cells is suggested to treat alcohol induced dysfunction in terms of EPBM phenomena, the mechanism of alcohol induced dysfunction and our biological information model of PBM. In our opinion, the therapeutic effects of PBM might also be achieved on alcoholic myopathy.

  1. 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

  2. Hydroxylation of organic polymer surface: method and application.

    PubMed

    Yang, Peng; Yang, Wantai

    2014-03-26

    It may be hardly believable that inert C-H bonds on a polymeric material surface could be quickly and efficiently transformed into C-OH by a simple and mild way. Thanks to the approaches developed recently, it is now possible to transform surface H atoms of a polymeric substrate into monolayer OH groups by a simple/mild photochemical reaction. Herein the method and application of this small-molecular interfacial chemistry is highlighted. The existence of hydroxyl groups on material surfaces not only determines the physical and chemical properties of materials but also provides effective reaction sites for postsynthetic sequential modification to fulfill the requirements of various applications. However, organic synthetic materials based on petroleum, especially polyolefins comprise mainly C and H atoms and thus present serious surface problems due to low surface energy and inertness in reactivity. These limitations make it challenging to perform postsynthetic surface sequential chemical derivatization toward enhanced functionalities and properties and also cause serious interfacial problems when bonding or integrating polymer substrates with natural or inorganic materials. Polymer surface hydroxylation based on direct conversion of C-H bonds on polymer surfaces is thus of significant importance for academic and practical industrial applications. Although highly active research results have reported on small-molecular C-H bond activation in solution (thus homogeneous), most of them, featuring the use of a variety of transition metals as catalysts, present a slow reaction rate, a low atom economy and an obvious environmental pollution. In sharp contrast to these conventional C-H activation strategies, the present Spotlight describes a universal confined photocatalytic oxidation (CPO) system that is able to directly convert polymer surface C-H bonds to C-OSO3(-) and, subsequently, to C-OH through a simple hydrolysis. Generally speaking, these newly implanted hydroxyl

  3. Alcohol Use Disorders

    MedlinePlus

    ... Search Alcohol & Your Health Overview of Alcohol Consumption Alcohol's Effects on the Body Alcohol Use Disorder Fetal Alcohol ... less effect than before? Found that when the effects of alcohol were wearing off, you had withdrawal symptoms, such ...

  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. Highly efficient synthesis of phenols by copper-catalyzed hydroxylation of aryl iodides, bromides, and chlorides.

    PubMed

    Yang, Kai; Li, Zheng; Wang, Zhaoyang; Yao, Zhiyi; Jiang, Sheng

    2011-08-19

    8-Hydroxyquinolin-N-oxide was found to be a very efficient ligand for the copper-catalyzed hydroxylation of aryl iodides, aryl bromides, or aryl chlorides under mild reaction conditions. This methodology provides a direct transformation of aryl halides to phenols and to alkyl aryl ethers. The inexpensive catalytic system showed great functional group tolerance and excellent selectivity.

  7. 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...

  8. 77 FR 54919 - National Institute on Alcohol Abuse and Alcoholism; Notice of Closed Meeting

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-09-06

    ... HUMAN SERVICES National Institutes of Health National Institute on Alcohol Abuse and Alcoholism; Notice... personal privacy. Name of Committee: National Institute on Alcohol Abuse and Alcoholism Initial Review Group Neuroscience Review Subcommittee. Date: November 2, 2012. Time: 8 a.m. to 5 p.m. Agenda: To...

  9. 76 FR 44600 - National Institute on Alcohol Abuse and Alcoholism; Notice of Closed Meeting

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-07-26

    ... HUMAN SERVICES National Institutes of Health National Institute on Alcohol Abuse and Alcoholism; Notice... personal privacy. Name of Committee: National Institute on Alcohol Abuse and Alcoholism Initial Review Group; Neuroscience Review Subcommittee. Date: November 10, 2011. Time: 8 a.m. to 8 p.m. Agenda:...

  10. 77 FR 54919 - National Institute on Alcohol Abuse and Alcoholism; Notice of Closed Meeting

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-09-06

    ... HUMAN SERVICES National Institutes of Health National Institute on Alcohol Abuse and Alcoholism; Notice... personal privacy. Name of Committee: National Institute on Alcohol Abuse and Alcoholism Initial Review Group Biomedical Research Review Subcommittee. Date: October 16, 2012. Time: 8 a.m. to 5 p.m. Agenda:...

  11. Differences among Nonclinical College Women with Alcoholic Mothers, Alcoholic Fathers, and Nonalcoholic Parents.

    ERIC Educational Resources Information Center

    Stout, M. Lisa; Mintz, Laurie B.

    1996-01-01

    Examines the uniformity myth surrounding adult children of alcoholics by exploring differences among nonclinical college females with alcoholic fathers, alcoholic mothers, and no alcoholic parents. Results indicate no group differences in eating-disorder symptomatology. Differences were found in terms of distress arising from interpersonal…

  12. 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.; ...

    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

  13. 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.

  14. Plutonium Uptake By Brucite And Hydroxylated Periclase

    SciTech Connect

    Farr, J.D.; Neu, M.P.; Schulze, R.K.; Honeyman, B.D.

    2009-06-02

    Batch adsorption experiments and spectroscopic investigations consistently show that aqueous Pu(IV) is quickly removed from solution and becomes incorporated in a brucite or hydroxylated MgO surface to a depth of at least 50 nm, primarily as Pu(IV) within a pH range of 8.5--12.5, and is unaffected by the presence of the organic ligand, citrate. X-ray photoelectron spectroscopy (XPS), X-ray absorption fine structure (XAFS) and Rutherford backscattering spectroscopy (RBS) were used to estimate Pu penetration depth and provide information about its chemical state.

  15. Hepatic alcohol dehydrogenase activity in alcoholic subjects with and without liver disease.

    PubMed Central

    Vidal, F; Perez, J; Morancho, J; Pinto, B; Richart, C

    1990-01-01

    Alcohol dehydrogenase activity was measured in samples of liver tissue from a group of alcoholic and non-alcoholic subjects to determine whether decreased liver alcohol dehydrogenase activity is a consequence of ethanol consumption or liver damage. The alcoholic patients were classified further into the following groups: control subjects with no liver disease (group 1), subjects with non-cirrhotic liver disease (group 2), and subjects with cirrhotic liver disease (group 3). The non-alcoholic subjects were also divided, using the same criteria, into groups 4, 5, and 6, respectively. The analysis of the results showed no significant differences when mean alcohol dehydrogenase activities of alcoholic and non-alcoholic patients with similar degrees of liver pathology were compared (groups 1 v 4, 2 v 5, and 3 v 6. Alcohol dehydrogenase activity was, however, severely reduced in patients with liver disease compared with control subjects. Our findings suggest that alcohol consumption does not modify hepatic alcohol dehydrogenase activity. The reduction in specific alcohol dehydrogenase activity in alcoholic liver disease is a consequence of liver damage. PMID:2379876

  16. Recombinant expression of hydroxylated human collagen in Escherichia coli.

    PubMed

    Rutschmann, Christoph; Baumann, Stephan; Cabalzar, Jürg; Luther, Kelvin B; Hennet, Thierry

    2014-05-01

    Collagen is the most abundant protein in the human body and thereby a structural protein of considerable biotechnological interest. The complex maturation process of collagen, including essential post-translational modifications such as prolyl and lysyl hydroxylation, has precluded large-scale production of recombinant collagen featuring the biophysical properties of endogenous collagen. The characterization of new prolyl and lysyl hydroxylase genes encoded by the giant virus mimivirus reveals a method for production of hydroxylated collagen. The coexpression of a human collagen type III construct together with mimivirus prolyl and lysyl hydroxylases in Escherichia coli yielded up to 90 mg of hydroxylated collagen per liter culture. The respective levels of prolyl and lysyl hydroxylation reaching 25 % and 26 % were similar to the hydroxylation levels of native human collagen type III. The distribution of hydroxyproline and hydroxylysine along recombinant collagen was also similar to that of native collagen as determined by mass spectrometric analysis of tryptic peptides. The triple helix signature of recombinant hydroxylated collagen was confirmed by circular dichroism, which also showed that hydroxylation increased the thermal stability of the recombinant collagen construct. Recombinant hydroxylated collagen produced in E. coli supported the growth of human umbilical endothelial cells, underlining the biocompatibility of the recombinant protein as extracellular matrix. The high yield of recombinant protein expression and the extensive level of prolyl and lysyl hydroxylation achieved indicate that recombinant hydroxylated collagen can be produced at large scale for biomaterials engineering in the context of biomedical applications.

  17. 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.

  18. Effect of low molecular weight aliphatic alcohols and related compounds on platelet factor 4 subunit association.

    PubMed

    Yang, Y; Barker, S; Chen, M J; Mayo, K H

    1993-05-05

    Titration of platelet factor 4 (PF4) with increasing concentrations of various low molecular weight aliphatic alcohols disrupts dimer and tetramer quaternary structure while preserving tertiary structural integrity. Normally observed slow subunit exchange (1H NMR time scale) is shifted into the fast chemical exchange regime. The order of effectiveness is butanol > 2-propanol > propanol > ethanol > methanol. Fluorination of ethanol (trifluoroethanol) and 2-propanol (hexafluoro-2-propanol) increases effectiveness by approximately 2 orders of magnitude. Oxidation to 2-propanone or trifluoro-2-propanone produces a less effective compound, suggesting a mechanistic role for the hydroxyl group. Increasing the number of hydroxyls to three, as in glycerol, however, is relatively ineffective in disrupting aggregate states or modifying subunit exchange rates. While 19F NMR studies indicate that these alcohols specifically interact with PF4, binding alone can not explain their mechanism of action. Dimethyl sulfoxide, structurally similar to 2-propanol, disrupts PF4 aggregation by direct binding, but does not shift subunit exchange kinetics into the NMR fast-exchange regime. Although not fully understood, the effectiveness of these compounds appears to be related to the colligative properties of the solution.

  19. Reversible catalytic dehydrogenation of alcohols for energy storage

    PubMed Central

    Bonitatibus, Peter J.; Chakraborty, Sumit; Doherty, Mark D.; Siclovan, Oltea; Jones, William D.; Soloveichik, Grigorii L.

    2015-01-01

    Reversibility of a dehydrogenation/hydrogenation catalytic reaction has been an elusive target for homogeneous catalysis. In this report, reversible acceptorless dehydrogenation of secondary alcohols and diols on iron pincer complexes and reversible oxidative dehydrogenation of primary alcohols/reduction of aldehydes with separate transfer of protons and electrons on iridium complexes are shown. This reactivity suggests a strategy for the development of reversible fuel cell electrocatalysts for partial oxidation (dehydrogenation) of hydroxyl-containing fuels. PMID:25588879

  20. Does comparing alcohol use along a single dimension obscure within-group differences? Investigating men's hazardous drinking by sexual orientation and race/ethnicity

    PubMed Central

    Gilbert, Paul A.; Daniel-Ulloa, Jason; Conron, Kerith J.

    2015-01-01

    Background Some studies have found that gay, bisexual, and other men who have sex with men (MSM) have higher odds of alcohol abuse and dependence than heterosexual men, but others have found no differences. We investigated whether the association between sexual orientation and hazardous drinking varied by race/ethnicity. Methods We estimated the odds of past-year heavy daily, heavy weekly, and binge drinking by sexual orientation and race/ethnicity among non-Latino White, non-Latino Black, and Latino (any race) men (n=9,689) who reported current alcohol use in the 2004-2005 National Epidemiological Survey of Alcohol and Related Conditions (NESARC). Interaction terms were included in multivariable logistic regression models to evaluate possible effect modification. Results In most comparisons, sexual minority men reported equivalent or lower levels of hazardous drinking than heterosexual peers. There was no association between sexual orientation and heavy daily drinking. Sexual minority Black men had lower odds of heavy weekly drinking and binge drinking than both heterosexual White men and heterosexual Black men. Among Latinos, the odds of heavy weekly drinking were higher for sexual minority men than heterosexuals; there was no difference by sexual orientation for binge drinking among Latinos. Conclusions With one exception, sexual minority men were at equivalent or lower risk of hazardous drinking than heterosexual men. The Black-White advantage observed in other alcohol studies was observed in our study and was heightened among sexual minority men, suggesting the presence of protective factors that curb hazardous drinking. Additional research is necessary to identify the mechanisms responsible for these patterns. PMID:25835229

  1. Alcohol Use and Firearm Violence

    PubMed Central

    Branas, Charles C.; Han, SeungHoon; Wiebe, Douglas J.

    2016-01-01

    Although the misuse of firearms is necessary to the occurrence of firearm violence, there are other contributing factors beyond simply firearms themselves that might also be modified to prevent firearm violence. Alcohol is one such key modifiable factor. To explore this, we undertook a 40-year (1975–2014) systematic literature review with meta-analysis. One large group of studies showed that over one third of firearm violence decedents had acutely consumed alcohol and over one fourth had heavily consumed alcohol prior to their deaths. Another large group of studies showed that alcohol was significantly associated with firearm use as a suicide means. Two controlled studies showed that gun injury after drinking, especially heavy drinking, was statistically significant among self-inflicted firearm injury victims. A small group of studies investigated the intersection of alcohol and firearms laws and alcohol outlets and firearm violence. One of these controlled studies found that off-premise outlets selling takeout alcohol were significantly associated with firearm assault. Additional controlled, population-level risk factor and intervention studies, including randomized trials of which only 1 was identified, are needed. Policies that rezone off-premise alcohol outlets, proscribe blood alcohol levels and enhance penalties for carrying or using firearms while intoxicated, and consider prior drunk driving convictions as a more precise criterion for disqualifying persons from the purchase or possession of firearms deserve further study. PMID:26811427

  2. Alcohol Use and Firearm Violence.

    PubMed

    Branas, Charles C; Han, SeungHoon; Wiebe, Douglas J

    2016-01-01

    Although the misuse of firearms is necessary to the occurrence of firearm violence, there are other contributing factors beyond simply firearms themselves that might also be modified to prevent firearm violence. Alcohol is one such key modifiable factor. To explore this, we undertook a 40-year (1975-2014) systematic literature review with meta-analysis. One large group of studies showed that over one third of firearm violence decedents had acutely consumed alcohol and over one fourth had heavily consumed alcohol prior to their deaths. Another large group of studies showed that alcohol was significantly associated with firearm use as a suicide means. Two controlled studies showed that gun injury after drinking, especially heavy drinking, was statistically significant among self-inflicted firearm injury victims. A small group of studies investigated the intersection of alcohol and firearms laws and alcohol outlets and firearm violence. One of these controlled studies found that off-premise outlets selling takeout alcohol were significantly associated with firearm assault. Additional controlled, population-level risk factor and intervention studies, including randomized trials of which only 1 was identified, are needed. Policies that rezone off-premise alcohol outlets, proscribe blood alcohol levels and enhance penalties for carrying or using firearms while intoxicated, and consider prior drunk driving convictions as a more precise criterion for disqualifying persons from the purchase or possession of firearms deserve further study.

  3. Preferential hydration of bovine serum albumin in polyhydric alcohol-water mixtures.

    PubMed

    Gekko, K; Morikawa, T

    1981-07-01

    The preferential solvent interaction with bovine serum albumin in aqueous solution of polyhydric alcohols (ethylene glycol, glycerol, xylitol, sorbitol, mannitol, and inositol) was investigated by a densimetric method with the application of multicomponent theory. This proteins was preferentially hydrated in all solvent systems examined: the extent depended on the number and the steric configuration of the hydroxyl groups of alcohols. The absolute interactions of these alcohols with the protein were estimated by assuming that the amount of hydration of protein at every solvent composition used is identical with that in pure water. The preferential hydration of the protein in 30% aqueous solutions of glycerol and sorbitol was found to decrease as the temperature was increased, indicating that the increase in chemical potential of protein on transferring it from water to both aqueous solvents is generated by a large positive enthalpy change, sufficient to compensate for the positive entropy change in the transfer process. On the basis of these results, and mechanism of stabilization of protein structure by these alcohols was discussed from the viewpoint of the solvation of protein.

  4. Evidence for hydroxyl radical generation during lipid (linoleate) peroxidation.

    PubMed

    Frenette, Mathieu; Scaiano, Juan C

    2008-07-30

    The autoxidation of methyl linoleate in benzene at 37 degrees C by peroxyl radicals was found to generate hydroxyl radicals (.OH) from a secondary oxidation mechanism. The yield of hydroxyl radicals (approximately 2%) was determined by trapping these reactive radicals with benzene to give phenol. We propose that alphaC-H hydrogen abstraction from lipid hydroperoxides, the main autoxidation products, is the source of hydroxyl radicals.

  5. Alcohol project

    SciTech Connect

    Not Available

    1980-12-01

    It is reported that Savannah Foods and Industries, in a joint venture with United States Sugar Corporation have applied for a loan guarantee for the production of alcohol from agricultural commodities. The two phase program calls for research and development, before a prototype plant will be built for the conversion of cellulosic compounds found in bagasse into alcohol for use as a fuel.

  6. Alcohol Facts

    MedlinePlus

    ... Families? Why Is It So Hard to Quit Drugs? Effects of Drugs Drug Use Hurts Other People Drug Use Hurts ... This Section Signs of Alcohol Abuse and Addiction Effects of Alcohol on Brains and Bodies Previous ... Treatment Work? Treatment and Rehab Resources About the ...

  7. 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.

  8. Evidence that phenylalanine hydroxylation rates are overestimated in neonatal subjects receiving total parenteral nutrition with a high phenylalanine content.

    PubMed

    House, J D; Thorpe, J M; Wykes, L J; Pencharz, P B; Ball, R O

    1998-04-01

    Recent publications have indicated that the parenterally fed neonate has a substantial ability to hydroxylate phenylalanine. Examination of these data suggests that, at high phenylalanine intakes, estimated rates of hydroxylation exceed rates of intake. This implies significant net tissue breakdown. However, the quantitative validity of the estimates of phenylalanine hydroxylation cannot be assessed without nitrogen balance data. We have recently developed a parenterally fed neonatal piglet model and have used this to study aromatic amino acid metabolism in piglets fed different amino acid solutions. Reappraisal of the data from these studies has allowed us to estimate both phenylalanine hydroxylation and tissue protein accretion. Piglets were parenterally fed Vamin [292 micromol of Phe x kg(-1) x h(-1), 26 micromol of Tyr x kg(-1) x h(-1)], Vaminolact + Phe [VLP, 277 micromol of Phe x kg(-1) x h(-1), 26 micromol Tyr x kg(-1) x h(-1)], or Vaminolact + glycyl-L-tyrosine [VLGT, 152 micromol of Phe x kg(-1) x h(-1), 159 micromol of Tyr x kg(-1) x h(-1)] for 8 d. Nitrogen balance was measured over the last 5 study d, and aromatic amino acid kinetics were determined using a primed continuous infusion of L-[1-4C]phenylalanine on d 8. Average body protein gain, derived from nitrogen balance, was 11 g x kg(-1) x d(-1). For the Vamin and VLP groups, the rates of phenylalanine hydroxylation were estimated to be 139 and 90% of intake, respectively. However, phenylalanine hydroxylation was only 16% of intake for the VLGT group. In view of the tissue protein accretion data, it appears that the rate of phenylalanine hydroxylation may be overestimated in neonates fed high phenylalanine parenteral nutrition. The extent to which the parenterally fed neonate can adapt to a high phenylalanine intake, by increasing the rate of phenylalanine hydroxylation, remains to be determined.

  9. Novel spectroscopic sensor for the hydroxyl radical scavenging activity measurement of biological samples.

    PubMed

    Bekdeşer, Burcu; Özyürek, Mustafa; Güçlü, Kubilay; Apak, Reşat

    2012-09-15

    A novel spectroscopic sensor was developed and validated for hydroxyl radical scavenging (HRS) activity estimation using terephthalate (TP) as probe. This sensor was designed by electrostatic immobilization of the chromogenic oxidizing agent of the CUPric Reducing Antioxidant Capacity (CUPRAC) method, Cu(II)-Neocuproine (Cu(II)-Nc) complex, on a Nafion cation-exchange membrane, and the spectrophotometric assay developed in aqueous-alcoholic solutions was integrated to the CUPRAC sensor. Hydroxyl radicals ((•)OH) generated from an equivalent mixture of Fe(II)+EDTA with hydrogen peroxide attacked both the probe and the (•)OH scavengers in 37 °C-incubated solutions for 1/2h. The HRS activity was measured using the decrease in CUPRAC absorbance at 450 nm - arising from the reduction of Cu(II)-Nc reagent to the Cu(I)-neocuproine chelate - of the hydroxylated probe (TP) undergoing radical attack in the presence of (•)OH scavengers. The HRS activity was evaluated as the second-order rate constants of biologically active compounds for (•)OH scavenging and also as the percentage scavenging of a measured compound or sample relative to a reference compound. Using this reaction, a kinetic approach was adopted to assess the HRS activity of amino acids, plasma- and thiol-antioxidants. This assay, applicable to small molecule antioxidants and tissue homogenates, proved to be efficient for serine and albumin for which the widely used TBARS (thiobarbituric acid-reactive substances) test is nonresponsive. Under optimal conditions, about half of the probe (TP) was converted into 2-hydroxyterephthalate (hTP), and this monohydroxylated derivative, being the only product of hydroxylation, was a more specific marker of (•)OH than the non-specific malondialdehyde end-product of the TBARS test. The sensor gave a linear response to scavenger concentration in the competition kinetic equation.

  10. Hydroxylation of progesterone by some Trichoderma species.

    PubMed

    El-Kadi, I A; Mostafa, M Eman

    2004-01-01

    Thirty-three isolates belonging to six species of the genus Trichoderma were tested for the ability to hydroxylate progesterone to 11alpha-, 11beta-, 11alpha,17alpha- and 6beta, 17alpha-derivatives, and epicortisol. T. aureoviride, T. harzianum, T. polysporum and T. pseudokoningii produced 11alpha-hydroxyprogesterone. T. harzianum and T. hamatum can form only the 11beta-isomer. T. koningii and T. hamatum produced 11alpha-, 11beta-, 11alpha,17alpha- and 6beta,11alpha-hydroxy derivatives. 11alpha, 11beta, 6beta,11alpha- and 11alpha,17alpha-hydroxyprogesterones and epicortisol are produced by T. aureoviride and T. pseudokoningii. Cortisol was produced only when the medium was fortified by 10 g/L peptone. This is the first record of conversion of progesterone to mono-, di- and trihydroxyprogesterones by these Trichoderma species.

  11. 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.

  12. 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.

  13. An NADPH and FAD dependent enzyme catalyzes hydroxylation of flavonoids in position 8.

    PubMed

    Halbwirth, Heidrun; Stich, Karl

    2006-06-01

    Yellow flavonols contribute to flower pigmentation in Asteraceae. In contrast to common flavonols, they show additional hydroxyl groups in position 6 and/or 8 of the aromatic A-ring in addition to the basic 5,7-hydroxylation pattern. An enzyme introducing a hydroxyl group in position 8 of flavonols and flavones was demonstrated for the first time with enzyme preparations from petals of Chrysanthemum segetum. Flavanones, dihydroflavonols and glucosylated flavonols and flavones were not accepted as substrates. The enzyme was localized in the microsomal fraction and uses NADPH and FAD as cofactors. Experiments with carbon monoxide/blue light and with antibodies specific for cytochrome P450 reductase did not indicate the involvement of a classical cytochrome P450 dependent monooxygenase in the reaction. Thus, the flavonoid 8-hydroxylase represents a novel type of hydroxylating enzyme in the flavonoid pathway. Apart from flavonoid 8-hydroxylase activity, the presence of all enzymes involved in the formation of flavonoid 7-O-glucosides in C. segetum was demonstrated. The pathway leading to 8-hydroxyflavonoids in C. segetum has been derived from enzyme activities and substrate specificities observed.

  14. 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.

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

    SciTech Connect

    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.

  16. Coping with an Alcoholic Parent

    MedlinePlus

    ... also use other drugs. Despite what happens, most children of alcoholics love their parents and worry about something bad happening to them. ... there are lots of support groups to help children of alcoholics cope with the problem. What If a Parent Doesn't See a Problem? Drinking too much ...

  17. Gender Commitment and Alcohol Consumption.

    ERIC Educational Resources Information Center

    Rabow, Jerome; And Others

    1992-01-01

    Categorized 179 college students as masculine, feminine, androgynous, or undifferentiated. Found gender orientations related to overall quantity-frequency index of alcohol consumption and beverage type. Androgynous respondents consumed less total alcohol than other groups; undifferentiated subjects drank more than feminine or androgynous subjects;…

  18. Children of Alcoholics: School Intervention.

    ERIC Educational Resources Information Center

    McAndrew, Judith A.

    1985-01-01

    Discusses the influences of parental alcoholism on children's daily lives, generally, and learning problems, absenteeism, and adjustment problems, specifically. Suggests that schools are one of the most promising settings for identifying and intervening with children of alcoholics as a target group. (DST)

  19. Liver Disease in the Alcoholic

    PubMed Central

    Szilagyi, Andrew

    1986-01-01

    The problem of liver damage in alcoholic patients is widespread. This review discusses hepatic damage on the basis of a histologic classification of increasing severity. In the early stages, or with compensated cirrhosis, clinical and laboratory findings may not accurately reflect hepatic involvement. Furthermore, there exists a group of alcoholic patients in whom liver disease may be caused by factors other than alcohol. Nevertheless, in most patients with liver disease, certain biochemical features help to establish an alcoholic etiology. These features and the use of liver biopsy are discussed, and a practical guideline for diagnosis and follow-up is offered. PMID:21267299

  20. Alcohol Energy Drinks

    MedlinePlus

    ... Home / About Addiction / Alcohol / Alcohol Energy Drinks Alcohol Energy Drinks Read 24059 times font size decrease font size increase font size Print Email Alcohol energy drinks (AEDs) or Caffeinated alcoholic beverages (CABs) are ...

  1. Alcohol during Pregnancy

    MedlinePlus

    ... Home > Pregnancy > Is it safe? > Alcohol during pregnancy Alcohol during pregnancy E-mail to a friend Please ... and fetal alcohol spectrum disorders. How does drinking alcohol during pregnancy affect your baby's health? Drinking alcohol ...

  2. Drugs of abuse and alcohol consumption among different groups of population on the Greek Island of Lesvos through sewage-based epidemiology.

    PubMed

    Gatidou, Georgia; Kinyua, Juliet; van Nuijs, Alexander L N; Gracia-Lor, Emma; Castiglioni, Sara; Covaci, Adrian; Stasinakis, Athanasios S

    2016-09-01

    The occurrence of 22 drugs of abuse, their metabolites, and the alcohol metabolite ethyl sulphate was investigated in raw sewage samples collected during the non-touristic season from three sewage treatment plants (STPs), which serve different sizes and types of population in the Greek island of Lesvos. Using the sewage-based epidemiology approach, the consumption of these substances was estimated. Five target analytes, cocaine (COC), benzoylecgonine (BE), 3,4-methylenedioxymethamphetamine (MDMA), 11-nor-9-carboxy-delta-9-tetrahydrocannabinol (THC-COOH) and ethyl sulphate (EtS) were detected at concentrations above their limit of quantification, whereas the rest eighteen target compounds were not detected. THC-COOH was detected in most of the samples with concentrations ranging between <20 and 90ngL(-1), followed by EtS (range <1700-12,243ngL(-1)). COC, BE, and MDMA were present only in the STP that serves Mytilene (the main city of the island), at mean concentrations of 3.9ngL(-1) for COC (95% CI: 1.7-6.1), 9.4ngL(-1) for BE (95% CI: -1.6-23) and 3.2ngL(-1) for MDMA (95% CI: 1.2-5.1). Back-calculations to an amount of used substance indicated more intense use of drugs among city population than rural and University population with average values of 9.5 and 1.2mgday(-1) per 1000 inhabitants for COC (95% CI: -1.43-20.4) and MDMA (95% CI: 0.52-1.85), respectively, and 2.8gday(-1) per 1000 inhabitants for tetrahydrocannabinol (THC) (95% CI: 2.4-3.1), the active ingredient of cannabis. Alcohol consumption was observed to be higher in the city population (5.4mL pure alcohol per day per inhabitant) than in the rural population (3.4mL pure alcohol per day per inhabitant), but the difference was not statistically significant. Consumption of THC differed significantly among the three STPs.

  3. Alcohol use, alcohol problems, and problem behavior engagement among students at two schools in northern Mexico

    PubMed Central

    Mancha, Brent E.; Rojas, Vanessa C.; Latimer, William W.

    2012-01-01

    This study examined the association between alcohol use problem severity, defined by number of DSM-IV alcohol Abuse and Dependence symptoms and frequency of alcohol use, and problem behavior engagement among Mexican students. A confidential survey was administered to 1229 students in grades 7–12 at two schools in a northern border city in Mexico. Youths were categorized into five groups based on their alcohol use frequency and symptoms of DSM-IV alcohol Abuse and Dependence, specifically: no lifetime alcohol use, lifetime alcohol use but none in the past year, past year alcohol use, one or two alcohol Abuse or Dependence symptoms, and three or more alcohol Abuse or Dependence symptoms. The association between five levels of alcohol use problem severity and three problem behaviors, lifetime marijuana use, lifetime sexual intercourse, and past year arrest/law trouble, was examined using chi-square or Fisher’s exact tests. Several alcohol use problem severity categories were significantly different with respect to rates of lifetime marijuana use, lifetime sexual intercourse, and past year arrest/law trouble. Higher alcohol use problem severity was associated with greater endorsement of problem behaviors. Knowing about variations in adolescent alcohol use and alcohol problems may be instrumental in determining if youths are also engaging in a range of other risk behaviors. Considering varying levels of alcohol use and alcohol problems is important for effective targeted prevention and treatment interventions. PMID:22840814

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

    PubMed Central

    McCullough, Christopher; Neumann, Terrence S.; Gone, Jayapal Reddy; He, Zhengjie; Herrild, Christian; Wondergem, 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. PMID:24315190

  5. Etiologic heterogeneity in alcoholism.

    PubMed

    Gilligan, S B; Reich, T; Cloninger, C R

    1987-01-01

    Etiologic heterogeneity in alcohol abuse was evaluated in 195 extended pedigrees, comprising 288 nuclear families of 140 male and 55 female Caucasian American hospitalized alcoholics. Previous adoption studies in Sweden demonstrated differential heritability of two patterns of alcohol abuse in men: type-2 alcoholism exhibited early onset of abuse associated with criminal behavior, while type-1 abuse began at a later age, uncomplicated by antisocial traits. Alcohol abuse in female Swedish adoptees was relatively homogeneous and similar to the late-onset, type-1 abuse. The notion of etiologic heterogeneity, as suggested by the Stockholm Adoption Studies, was examined in the American pedigrees by contrasting the models of familial transmission of susceptibility to alcoholism obtained via segregation analyses of families of male versus female probands. Families of male probands demonstrated significant familial resemblance, accounted for by a multifactorial-polygenic background in addition to a major (gene) effect. In contrast, familial resemblance in the pedigrees of female probands was attributed solely to a multifactorial-polygenic effect. We considered whether some families of male alcoholics were similar to families of female probands, who expressed type-1 abuse predominantly. Pedigrees of male probands were separated in two groups: (1) "female-like" families had a better likelihood for the model obtained for families of female probands than the one for families of all male probands, (2) "male-like" families had a better likelihood for the model of familial transmission describing families of all male probands. A statistically significant difference in the pattern of familial transmission was observed between the "male-like" and "female-like" groups. Discriminant function analysis of alcohol-related symptoms showed that the familial subtypes differed in clinical features as well. Alcohol abuse by male relatives in "male-like" families was characterized by the

  6. Structure of solvated Fe(CO)5: complex formation during solvation in alcohols.

    PubMed

    Lessing, Joshua; Li, Xiaodi; Lee, Taewoo; Rose-Petruck, Christoph G

    2008-03-20

    The equilibrium structure of iron pentacarbonyl, Fe(CO)5, solvated in various alcohols has been investigated by Fourier transform infrared (FTIR) measurements and density functional theory calculations. This system was studied because it is prototypical of a larger class of monometallic systems, which are electronically saturated but not sterically crowded. Upon solvation, the Fe(CO)5 is not just surrounded by a solvation shell. Instead, solute-solvent complexes are formed with the oxygen of the alcohol oriented toward an axial ligand of the Fe(CO)5 giving a formation energy on the order of -5 kJ/mol. This complexation is not a chemical reaction but rather a "preassembly" of the solute molecules with a single solvent molecule. For instance, at room temperature the interaction between Fe(CO)5 and ethanol results in 87% of all Fe(CO)5 molecules being complexated with a single ethanol molecule. This complexation was found in all the alcohol systems studied in this paper. The stability of these complexes was found to depend on the alcohol chain length and branching. The observed complexation mechanism is accompanied by an electron density shift from the complexed alcohol molecule toward Fe(CO)5 where it induces a dipole moment. The finding that Fe(CO)5 forms a complex with the hydroxyl group of a single solvent molecule might have significant implications for ligand substitution reactions. This implies that ligand substitution reactions do not have to proceed via a dissociative mechanism. Instead, the reaction might proceed through a concerted mechanism with the leaving CO simultaneously being replaced by the incoming alcohol that was complexed to Fe(CO)5 prior to the photoexcitation.

  7. Fluorinated alcohol, the third group of cosolvents that stabilize the molten-globule state relative to a highly denatured state of cytochrome c.

    PubMed Central

    Konno, T.; Iwashita, J.; Nagayama, K.

    2000-01-01

    The effects of 1,1,1,3,3,3-hexafluoro-isopropanol (HFIP) on the conformation of cytochrome c (cyt c) at pH 1.9 were studied using a combination of spectroscopic and physical methods. Analysis varying the HFIP concentration showed that a compact denatured conformation (M(HF)) accumulates in a low concentration range of HFIP in the middle of structural transition from the highly unstructured acid-denatured state to the highly helical alcohol-denatured state of cyt c. This contrasts clearly with the effect of isopropanol (IP), in which no compact conformation accompanied with the transition. Analysis varying concentrations of HFIP and NaCl concurrently showed that the M(HF) state of cyt c is essentially identical to the salt-induced molten-globule (M(G)) state, and the M(G) state in the presence of salt was also stabilized by a low concentration of HFIP. Furthermore, 2,2,2-trifluoroethanol stabilized M(HF) similarly to HFIP, supporting the proposition that the specific effect observed for HFIP is caused by fluorination of alcohol. The mechanism stabilizing compact conformation by HFIP remains unclear, but is probably distinct from that of salts and polyols, which are also known to stabilize the M(G)-like state. PMID:10752618

  8. Immunostimulating activity of polyhydric alcohol isolated from Taxus cuspidata.

    PubMed

    Lee, Choon Guen; Lee, Jisun; Lee, Da Gyung; Kim, Joo Won; Alnaeeli, Mawadda; Park, Yong Il; Park, Jae Kweon

    2016-04-01

    A polyhydric alcohol (PAL) was isolated from Taxus cuspidata and its immunostimulatory activities were assessed. The primary monosaccharide composition of the PAL was determined to be glucose, where HPAEC analysis showed no significant amount of any other sugars. However, glycerol and xylitol were identified as the main sugar alcohols. Fourier-transform infrared (FT-IR) analysis indicated that the purified PAL is a complex glycitol, which structurally contains significant amount of hydroxyl groups. MALDI-TOF mass spectroscopy also demonstrated that PAL is a complex glycitol built in hexose polymerization. Enzyme linked immunosorbent assay showed that the PAL stimulates the release of the proinflammatory cytokines TNF-α and IL-6 in a dose-dependent manner. Furthermore, treatment of RAW 264.7 cells with PAL for 24h remarkably increased the phosphorylation levels of ERK, p38 and JNK in a dose-dependent manner, whereas the total protein levels of ERK (t-ERK), p38 (t-p38) and JNK (t-JNK) remained unchanged. These results clearly demonstrate that PAL stimulates the immune response in RAW 264.7 cells through the activation of MAPKs (ERK, p38 and JNK) signaling pathway. To the best of our knowledge, this is the first study to demonstrate the primary structure and immune-stimulating activities of PAL from the fruit of T. cuspidata.

  9. [Prevention of alcohol dependence].

    PubMed

    Trova, A C; Paparrigopoulos, Th; Liappas, I; Ginieri-Coccossis, M

    2015-01-01

    With the exception of cardiovascular diseases, no other medical condition causes more serious dysfunction or premature deaths than alcohol-related problems. Research results indicate that alcohol dependent individuals present an exceptionally poor level of quality of life. This is an outcome that highlights the necessity of planning and implementing preventive interventions on biological, psychological or social level, to be provided to individuals who make alcohol abuse, as well as to their families. Preventive interventions can be considered on three levels of prevention: (a) primary prevention, which is focused on the protection of healthy individuals from alcohol abuse and dependence, and may be provided on a universal, selective or indicated level, (b) secondary prevention, which aims at the prevention of deterioration regarding alcoholic dependence and relapse, in the cases of individuals already diagnosed with the condition and (c) tertiary prevention, which is focused at minimizing deterioration of functioning in chronically sufferers from alcoholic dependence. The term "quaternary prevention" can be used for the prevention of relapse. As for primary prevention, interventions focus on assessing the risk of falling into problematic use, enhancing protective factors and providing information and health education in general. These interventions can be delivered in schools or in places of work and recreation for young people. In this context, various programs have been applied in different countries, including Greece with positive results (Preventure, Alcolocks, LST, SFP, Alcohol Ignition Interlock Device). Secondary prevention includes counseling and structured help with the delivery of programs in schools and in high risk groups for alcohol dependence (SAP, LST). These programs aim at the development of alcohol refusal skills and behaviors, the adoption of models of behaviors resisting alcohol use, as well as reinforcement of general social skills. In the

  10. Personality Characteristics of Adolescents with Alcoholic Parents.

    ERIC Educational Resources Information Center

    Tomori, Martina

    1994-01-01

    Study examined the psychodynamic pathways and social processes which place children of alcoholics at risk. Assessments of 63 adolescents in families with at least 1 alcoholic parent were compared to a control group taken from non-alcoholic families. Differences were found in anxiety variables, self-image variables, and aggression variables. (RJM)

  11. Experimental evidence for efficient hydroxyl radical regeneration in isoprene oxidation

    NASA Astrophysics Data System (ADS)

    Fuchs, H.; Hofzumahaus, A.; Rohrer, F.; Bohn, B.; Brauers, T.; Dorn, H.-P.; Häseler, R.; Holland, F.; Kaminski, M.; Li, X.; Lu, K.; Nehr, S.; Tillmann, R.; Wegener, R.; Wahner, A.

    2013-12-01

    Most pollutants in the Earth's atmosphere are removed by oxidation with highly reactive hydroxyl radicals. Field measurements have revealed much higher concentrations of hydroxyl radicals than expected in regions with high loads of the biogenic volatile organic compound isoprene. Different isoprene degradation mechanisms have been proposed to explain the high levels of hydroxyl radicals observed. Whether one or more of these mechanisms actually operates in the natural environment, and the potential impact on climate and air quality, has remained uncertain. Here, we present a complete set of measurements of hydroxyl and peroxy radicals collected during isoprene-oxidation experiments carried out in an atmospheric simulation chamber, under controlled atmospheric conditions. We detected significantly higher concentrations of hydroxyl radicals than expected based on model calculations, providing direct evidence for a strong hydroxyl radical enhancement due to the additional recycling of radicals in the presence of isoprene. Specifically, our findings are consistent with the unimolecular reactions of isoprene-derived peroxy radicals postulated by quantum chemical calculations. Our experiments suggest that more than half of the hydroxyl radicals consumed in isoprene-rich regions, such as forests, are recycled by these unimolecular reactions with isoprene. Although such recycling is not sufficient to explain the high concentrations of hydroxyl radicals observed in the field, we conclude that it contributes significantly to the oxidizing capacity of the atmosphere in isoprene-rich regions.

  12. Alcoholism and Elder Abuse.

    ERIC Educational Resources Information Center

    Anetzberger, Georgia J.; And Others

    1994-01-01

    A comparison group study of abusing and nonabusing caregivers suggested a correlation between alcohol use and violence against elderly parents. Findings reveal that abusers were more likely than nonabusers to drink, to become intoxicated, and to be identified as having a drinking problem. Policy and practice implications are discussed. (Author)

  13. 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.

  14. Alcoholics Anonymous

    MedlinePlus

    ... Help What's New Read Daily Reflections Make a Contribution Go to Online Bookstore Welcome to Alcoholics Anonymous ® ... and Twelve & Twelve | 75th Anniversary Edition | Make a contribution | Self-Support Press/Media | Archives & History | A.A. ...

  15. Alcohol Intolerance

    MedlinePlus

    ... or other preservatives Chemicals, grains or other ingredients Histamine, a byproduct of fermentation or brewing In some ... in some people, possibly as a result of histamines contained in some alcoholic beverages. Your immune system ...

  16. Alcoholic ketoacidosis

    MedlinePlus

    Tests may include: Arterial blood gases (measure the acid/base balance and oxygen level in blood) Blood alcohol ... PA: Elsevier Saunders; 2013:chap 161. Seifter JL. Acid-Base disorders. In: Goldman L, Schafer AI, eds. Goldman's ...

  17. Alcohol withdrawal

    MedlinePlus

    ... Seeing or feeling things that aren't there (hallucinations) Seizures Severe confusion ... alcohol withdrawal. You will be watched closely for hallucinations and other signs of delirium tremens. Treatment may ...

  18. Influence of Fluorination on the Conformational Properties and Hydrogen-Bond Acidity of Benzyl Alcohol Derivatives

    PubMed Central

    Bogdan, Elena; Compain, Guillaume; Mtashobya, Lewis; Le Questel, Jean-Yves; Besseau, François; Galland, Nicolas; Linclau, Bruno; Graton, Jérôme

    2015-01-01

    The effect of fluorination on the conformational and hydrogen-bond (HB)-donating properties of a series of benzyl alcohols has been investigated experimentally by IR spectroscopy and theoretically with quantum chemical methods (ab initio (MP2) and DFT (MPWB1K)). It was found that o-fluorination generally resulted in an increase in the HB acidity of the hydroxyl group, whereas a decrease was observed upon o,o′-difluorination. Computational analysis showed that the conformational landscapes of the title compounds are strongly influenced by the presence of o-fluorine atoms. Intramolecular interaction descriptors based on AIM, NCI and NBO analyses reveal that, in addition to an intramolecular OH⋅⋅⋅F interaction, secondary CH⋅⋅⋅F and/or CH⋅⋅⋅O interactions also occur, contributing to the stabilisation of the various conformations, and influencing the overall HB properties of the alcohol group. The benzyl alcohol HB-donating capacity trends are properly described by an electrostatic potential based descriptor calculated at the MPWB1K/6-31+G(d,p) level of theory, provided solvation effects are taken into account for these flexible HB donors. PMID:26130594

  19. Hospital-Admitted Injury Attributable to Alcohol

    PubMed Central

    Miller, Ted R.; Spicer, Rebecca S.

    2013-01-01

    Background Primary data collection has established that alcohol causes injuries treated in the emergency department. No comparable data exist for injuries admitted to hospital. Data on the injury risks of heavy drinkers relative to other drinkers also are sparse. Methods We estimated (1) whether regular heavy drinkers have higher hospitalized injury risks than other people when alcohol negative and (2) how much hospitalized injury risk of regular heavy drinkers and other drinkers rises when alcohol positive. We combined national alcohol consumption data with alcohol metabolism rates to estimate hours spent alcohol positive versus alcohol negative during a year for heavy drinkers versus other people. A literature review provided hospitalized non-fatal injury rates for these groups by alcohol involvement. Results Relative to other alcohol-negative people aged 18 and older, heavy drinkers have an estimated relative risk of hospitalized injury of 1.4 when alcohol negative and 4.3 when alcohol positive. Others have an estimated relative risk of 1.0 when alcohol negative and 6.8 when alcohol positive. Thus alcohol greatly raises injury risk. The excess risk patterns persist for a wide range of sensitivity analysis values. Of hospitalized injuries, an estimated 21% are alcohol attributable including 36% of assaults. Conclusions Drinking alcohol is a major cause of hospitalized injury. Heavy drinkers lead risky lifestyles. They tolerate alcohol better than most drinkers but their injury risks still triple when they drink. Our approach to attribution is a valuable complement to more costly, more precise approaches that rely heavily on primary data collection. It works for any severity of injury. Applying it only requires an existing alcohol consumption survey plus data on alcohol involvement in targeted injuries. PMID:22004026

  20. The effect of structural modifications on the solution and interfacial properties of straight and branched aliphatic alcohols: the role of hydrophobic effects.

    PubMed

    Fong, Celesta; Greaves, Tamar L; Healy, Thomas W; Drummond, Calum J

    2015-07-01

    The effect of structural modifications, such as branching of the hydrocarbon chain on the solution and interfacial properties of short-chain aliphatic alcohols has been investigated. Surface tension measurements have been used to study the adsorption of the alcohols at the aqueous solution/air interface from water/alcohol mixtures, and to determine the aqueous solubilities of the alcohols. The related process of the partitioning behaviour of the alcohols between two immiscible phases has also been studied. Standard free energies of adsorption at the aqueous solution/air interface, standard free energies of transfer between water and hexane, and standard free energies of solution were obtained for the alcohols. A linear "Traube" relationship, an elegant demonstration of the hydrophobic effect, was found to exist between the various free energies for the normal alcohols and the number of carbon atoms in the alcohol molecule. The free energies showed that structurally modified alcohols have less negative free energy of adsorption, transfer or solution compared to the normal alcohol with the same number of carbon atoms. We assign effective numbers of carbon atoms for each branched alcohol for each transfer process. The position of the hydroxyl group relative to the branched part of the molecule was found to be a factor which influences the hydrophobic contribution to the free energy of each transfer process. An attempt has been made to ascertain whether there is a correlation between the molecular surface area, or the molecular volume, and the interfacial and solution thermodynamic properties of an alcohol in aqueous solution. The standard free energies of some of the branched alcohols have been found to be inconsistent with the values expected from the energetic of the adsorption and the water/hexane transfer processes. This is thought to reflect the different modes of association of the branched and normal alcohols in the liquid state as revealed by small and wide

  1. 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.

  2. 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.

  3. Glutathione--hydroxyl radical interaction: a theoretical study on radical recognition process.

    PubMed

    Fiser, Béla; Jójárt, Balázs; Csizmadia, Imre G; Viskolcz, Béla

    2013-01-01

    Non-reactive, comparative (2 × 1.2 μs) molecular dynamics simulations were carried out to characterize the interactions between glutathione (GSH, host molecule) and hydroxyl radical (OH(•), guest molecule). From this analysis, two distinct steps were identified in the recognition process of hydroxyl radical by glutathione: catching and steering, based on the interactions between the host-guest molecules. Over 78% of all interactions are related to the catching mechanism via complex formation between anionic carboxyl groups and the OH radical, hence both terminal residues of GSH serve as recognition sites. The glycine residue has an additional role in the recognition of OH radical, namely the steering. The flexibility of the Gly residue enables the formation of further interactions of other parts of glutathione (e.g. thiol, α- and β-carbons) with the lone electron pair of the hydroxyl radical. Moreover, quantum chemical calculations were carried out on selected GSH/OH(•) complexes and on appropriate GSH conformers to describe the energy profile of the recognition process. The relative enthalpy and the free energy changes of the radical recognition of the strongest complexes varied from -42.4 to -27.8 kJ/mol and from -21.3 to 9.8 kJ/mol, respectively. These complexes, containing two or more intermolecular interactions, would be the starting configurations for the hydrogen atom migration to quench the hydroxyl radical via different reaction channels.

  4. The effect of hydroxylation on CNT to form Chitosan-CNT composites: A DFT study

    NASA Astrophysics Data System (ADS)

    Yu, Rui; Ran, Maofei; Wen, Jie; Sun, Wenjing; Chu, Wei; Jiang, Chengfa; He, Zhiwei

    2015-12-01

    The effect of types of CNTs (pristine and hydroxylated) on the synthesis of Chitosan-CNT (CS-CNT) composites was investigated theoretically. The adsorption energy (Eads) of CS on the pristine CNT and hydroxylated CNTs (CNT-OHn, n = 1-6) as well as the structural and electronic properties of said composites have been investigated. Results show that the adsorption of CS on CNT and CNT-OHn is thermodynamically favored. The Eads of CS on CNTs was calculated to be -20.387 kcal/mol from electrostatic interactions. For CS adsorbed into CNT-OHn, Eads ranges from -20.612 to -37.567 kcal/mol. Hydroxyl groups on CNT are the main adsorption sites for CS loading onto CNT-OHn via hydrogen-bond interactions. The CS-CNT-OH3 is the most sable composite among tested complexes. The energy gap (ΔEgap) of CS-CNT-OH3 was calculated less than pristine CNT and CNT-OH3, indicative of the composites being more reactive than that of pristine CNTs and CNT-OH3. It was proved that CS can transfer electron to the hydroxylated CNTs, thus overcoming the drawbacks of CNTs being chemically inert.

  5. Glutathione – Hydroxyl Radical Interaction: A Theoretical Study on Radical Recognition Process

    PubMed Central

    Fiser, Béla; Jójárt, Balázs; Csizmadia, Imre G.; Viskolcz, Béla

    2013-01-01

    Non-reactive, comparative (2×1.2 μs) molecular dynamics simulations were carried out to characterize the interactions between glutathione (GSH, host molecule) and hydroxyl radical (OH•, guest molecule). From this analysis, two distinct steps were identified in the recognition process of hydroxyl radical by glutathione: catching and steering, based on the interactions between the host-guest molecules. Over 78% of all interactions are related to the catching mechanism via complex formation between anionic carboxyl groups and the OH radical, hence both terminal residues of GSH serve as recognition sites. The glycine residue has an additional role in the recognition of OH radical, namely the steering. The flexibility of the Gly residue enables the formation of further interactions of other parts of glutathione (e.g. thiol, α- and β-carbons) with the lone electron pair of the hydroxyl radical. Moreover, quantum chemical calculations were carried out on selected GSH/OH• complexes and on appropriate GSH conformers to describe the energy profile of the recognition process. The relative enthalpy and the free energy changes of the radical recognition of the strongest complexes varied from −42.4 to −27.8 kJ/mol and from −21.3 to 9.8 kJ/mol, respectively. These complexes, containing two or more intermolecular interactions, would be the starting configurations for the hydrogen atom migration to quench the hydroxyl radical via different reaction channels. PMID:24040010

  6. Diagnosis and management of non-alcoholic fatty liver disease and related metabolic disorders: consensus statement from the Study Group of Liver and Metabolism, Chinese Society of Endocrinology.

    PubMed

    Gao, Xin; Fan, Jian-Gao

    2013-12-01

    Non-alcoholic fatty liver disease (NAFLD) is the most common liver disease in Western countries, affecting 20%-33% of the general population. Large population-based surveys in China indicate a prevalence of approximately 15%-30%. Worldwide, including in China, the prevalence of NAFLD has increased rapidly in parallel with regional trends of obesity, type 2 diabetes and metabolic syndrome. In addition, NAFLD has contributed significantly to increased overall, as well as cardiovascular and liver-related, mortality in the general population. In view of rapid advances in research into NAFLD in recent years, this consensus statement provides a brief update on the progress in the field and suggests preferred approaches for the comprehensive management of NAFLD and its related metabolic diseases.

  7. Summation solute hydrogen bonding acidity values for hydroxyl substituted flavones determined by NMR spectroscopy.

    PubMed

    Whaley, William L; Okoso-amaa, Ekua M; Womack, Cody L; Vladimirova, Anna; Rogers, Laura B; Risher, Margaret J; Abraham, Michael H

    2013-01-01

    The flavonoids are a structurally diverse class of natural products that exhibit a broad spectrum of biochemical activities. The flavones are one of the most studied flavonoid subclasses due to their presence in dietary plants and their potential to protect human cells from reactive oxygen species (ROS). Several flavone compounds also mediate beneficial actions by direct binding to protein receptors and regulatory enzymes. There is current interest in using Quantitative Structure Activity Relationships (QSARs) to guide drug development based on flavone lead structures. This approach is most informative when it involves the use of accurate physical descriptors. The Abraham summation solute hydrogen bonding acidity (A) is a descriptor in the general solvation equation. It defines the tendency of a molecule to act as a hydrogen bond donor, or acid, when surrounded by solvent molecules that are hydrogen bonding acceptors, or bases. As a linear free energy relationship, it is useful for predicting the absorption and uptake of drug molecules. A previously published method, involving nuclear magnetic resonance (NMR) spectroscopy, was used to evaluate A for the monohydroxyflavones (MHFs). Values of A ranged from 0.02, for 5-hydroxyflavone, to 0.69 for 4'-hydroxyflavone. The ability to examine separate NMR signals for individual hydroxyl groups allowed the investigation of intramolecular interactions between functional groups. The value of A for the position 7 hydroxyl group of 7-hydroxyflavone was 0.67. The addition of a position 5 hydroxyl group (in 5,7-dihydroxyflavone) increased the value of A for the position 7 hydroxyl group to 0.76. Values of A for MHFs were also calculated by the program ACD-Absolve and these agreed well with values measured by NMR. These results should facilitate more accurate estimation of the values of A for structurally complex flavones with pharmacological activities.

  8. 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.

  9. 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.

  10. A novel metabolic pathway for degradation of 4-nonylphenol environmental contaminants by Sphingomonas xenophaga Bayram: ipso-hydroxylation and intramolecular rearrangement.

    PubMed

    Gabriel, Frédéric L P; Heidlberger, Andy; Rentsch, Daniel; Giger, Walter; Guenther, Klaus; Kohler, Hans-Peter E

    2005-04-22

    Several nonylphenol isomers with alpha-quaternary carbon atoms serve as growth substrates for Sphingomonas xenophaga Bayram, whereas isomers containing hydrogen atoms at the alpha-carbon do not. Three metabolites of 4-(1-methyloctyl)-phenol were isolated in mg quantities from cultures of strain Bayram supplemented with the growth substrate isomer 4-(1-ethyl-1,4-dimethyl-pentyl)-phenol. They were unequivocally identified as 4-hydroxy-4-(1-methyl-octyl)-cyclohexa-2,5-dienone, 4-hydroxy-4-(1-methyl-octyl)-cyclohex-2-enone, and 2-(1-methyl-octyl)-benzene-1,4-diol by high pressure liquid chromatography-mass spectrometry and nuclear magnetic resonance spectroscopy. Furthermore, two metabolites originating from 4-n-nonylphenol were identified as 4-hydroxy-4-nonyl-cyclohexa-2,5-dienone and 4-hydroxy-4-nonyl-cyclohex-2-enone by high pressure liquid chromatography-mass spectrometry. We conclude that nonylphenols were initially hydroxylated at the ipso-position forming 4-alkyl-4-hydroxy-cyclohexa-2,5-dienones. Dienones originating from growth substrate nonylphenol isomers underwent a rearrangement that involved a 1,2-C,O shift of the alkyl moiety as a cation to the oxygen atom of the geminal hydroxy group yielding 4-alkoxyphenols, from which the alkyl moieties can be easily detached as alcohols by known mechanisms. Dienones originating from nongrowth substrates did not undergo such a rearrangement because the missing alkyl substituents at the alpha-carbon atom prevented stabilization of the putative alpha-carbocation. Instead they accumulated and subsequently underwent side reactions, such as 1,2-C,C shifts and dihydrogenations. The ipso-hydroxylation and the proposed 1,2-C,O shift constitute key steps in a novel pathway that enables bacteria to detach alpha-branched alkyl moieties of alkylphenols for utilization of the aromatic part as a carbon and energy source.

  11. Mesler entrainment in alcohols

    NASA Astrophysics Data System (ADS)

    Sundberg-Anderson, R. K.; Saylor, J. R.

    2014-01-01

    Mesler entrainment has been studied extensively in water and, more recently, in silicone oils. Studies of Mesler entrainment in liquids other than these are rare. The extant experimental results in water show significant irreproducibility both in the qualitative characteristics of Mesler entrainment and in the existence or nonexistence of Mesler entrainment when, for example, drops of the same diameter are released from the same height. In contrast, in silicone oils, Mesler entrainment is highly reproducible, essentially occurring either all of the time, or none of the time for a given set of conditions. A goal of the present work was to determine which of these two behaviors is the "standard" behavior—that is, to determine whether Mesler entrainment is typically repeatable or not. The experimental studies presented herein were conducted in three liquids that have not been the subject of detailed investigation to date: ethyl alcohol, isopropyl alcohol, and methyl alcohol. All of these alcohol results showed behavior very similar to that observed in silicone oils, suggesting that Mesler entrainment is typically repeatable and that water is an atypical fluid, causing irreproducible results. Additionally, we present data obtained in silicone oils and combine that with the alcohol data in an attempt to develop a combination of dimensionless groups that predicts the boundaries within which Mesler entrainment occurs for liquids other than water.

  12. 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.

  13. 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.

  14. Deciding to quit drinking alcohol

    MedlinePlus

    ... Alcohol abuse - quitting drinking; Quitting drinking; Quitting alcohol; Alcoholism - deciding to quit ... pubmed/23698791 . National Institute on Alcohol Abuse and Alcoholism. Alcohol and health. www.niaaa.nih.gov/alcohol- ...

  15. Neuropathology of alcoholism.

    PubMed

    Harper, C G; Kril, J J

    1990-01-01

    There are wide ranging effects of alcohol on the nervous system. Some interfere with physiological and neurochemical functions but ultimately structural damage occurs. During life one of the most impressive changes is brain shrinkage which can be visualized using neuroradiological imaging techniques. This article reviews the pathological explanations for brain shrinkage and addresses the question of the pathogenesis of the reversible component of this damage in relation to prolonged abstinence from alcohol. This shrinkage seems to relate to a loss of white matter. However, the cortex is also abnormal in that there is a loss of neurones from the frontal region. In this and other regions of the cortex examined there is shrinkage of the neuronal soma. This is reflected in a retraction of the neuronal dendritic arbor which plays a crucial role in cell-to-cell communication. In addition, the cerebellum appears to be vulnerable in alcoholic patients although it may well be that associated nutritional deficiencies play an important role. The Wernicke-Korsakoff syndrome is another important deficiency disorder which is seen most frequently in alcoholic patients. Two important population groups which are considered in this review are females and moderate ('social') drinkers. Females are thought to be more susceptible to the damaging effects of alcohol than males and this is examined in the light of the scant data available. Similarly, there are few neuropathological data on people who drink 30-80 grams of alcohol per day. In order to assess so-called 'safe levels of drinking' this is an important group to study.

  16. 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

  17. Parental alcohol involvement and adolescent alcohol expectancies predict alcohol involvement in male adolescents.

    PubMed

    Cranford, James A; Zucker, Robert A; Jester, Jennifer M; Puttler, Leon I; Fitzgerald, Hiram E

    2010-09-01

    Current models of adolescent drinking behavior hypothesize that alcohol expectancies mediate the effects of other proximal and distal risk factors. This longitudinal study tested the hypothesis that the effects of parental alcohol involvement on their children's drinking behavior in mid-adolescence are mediated by the children's alcohol expectancies in early adolescence. A sample of 148 initially 9-11 year old boys and their parents from a high-risk population and a contrast group of community families completed measures of drinking behavior and alcohol expectancies over a 6-year interval. We analyzed data from middle childhood (M age = 10.4 years), early adolescence (M age = 13.5 years), and mid-adolescence (M age = 16.5 years). The sample was restricted only to adolescents who had begun to drink by mid-adolescence. Results from zero-inflated Poisson regression analyses showed that 1) maternal drinking during their children's middle childhood predicted number of drinking days in middle adolescence; 2) negative and positive alcohol expectancies in early adolescence predicted odds of any intoxication in middle adolescence; and 3) paternal alcoholism during their children's middle childhood and adolescents' alcohol expectancies in early adolescence predicted frequency of intoxication in middle adolescence. Contrary to predictions, child alcohol expectancies did not mediate the effects of parental alcohol involvement in this high-risk sample. Different aspects of parental alcohol involvement, along with early adolescent alcohol expectancies, independently predicted adolescent drinking behavior in middle adolescence. Alternative pathways for the influence of maternal and paternal alcohol involvement and implications for expectancy models of adolescent drinking behavior were discussed.

  18. Metal-free oxidative hydroxyalkylarylation of activated alkenes by direct sp3 C-H functionalization of alcohols.

    PubMed

    Meng, Yuan; Guo, Li-Na; Wang, Hua; Duan, Xin-Hua

    2013-09-04

    A metal-free tandem radical addition/cyclization reaction of activated alkenes and alcohols has been developed. The process provides an efficient and atom economical access to various valuable hydroxyl-containing oxindoles through the direct sp(3) C-H functionalization of alcohols.

  19. Alcohol consumption and household expenditure on alcohol in a rural district in Vietnam

    PubMed Central

    Giang, Kim Bao; Van Minh, Hoang; Allebeck, Peter

    2013-01-01

    Introduction Alcohol use and alcohol-related problems are on the rise in low- and middle-income countries. Expenditure on alcohol is an important problem for families and communities and needs to be assessed. Aim This study examines level of alcohol consumption and expenditure on alcohol in a district in Vietnam. Methods A cross-sectional survey was conducted in a rural district in northern Vietnam. Multi-stage sampling was employed to randomly select participants from 20 communities and a town in the same district. One thousand five hundred and sixty-four adults (765 males and 799 females) aged 18–60 years were interviewed. Information about alcohol use as well as expenditure on alcohol consumption four weeks prior to the interview was gathered. Non-parametric tests and log-linear regression were employed to compare expenditure on alcohol consumption across socioeconomic groups. Results The prevalence of alcohol use one month prior to interview was 35% (66% among men and 5% among women). The median alcohol consumption among those who reported use of alcohol in the week prior to the interview was 7.9 standard drinks. Excessive drinking (more than 14 standard drinks per week for men and more than seven standard drinks per week for women) occurred among 35% of those who used alcohol. Median expenditure for alcohol consumption during one month by those who drank alcohol was USD 3.5, accounting for 4.6% of household food expenditure, 2.7% of total household expenditure, and 1.8% of household income. The differences in alcohol consumption and expenditure between sexes and between socioeconomic groups are also presented. Conclusion Our study confirms that alcohol consumption and alcohol-related problems are common among men in Vietnam. The share of alcohol expenditure in total household expenditure is substantial, especially among poor households. This should be considered an important public health issue, which needs to be taken into account in the alcohol policy

  20. Oxygenase-catalyzed ribosome hydroxylation occurs in prokaryotes and humans.

    PubMed

    Ge, Wei; Wolf, Alexander; Feng, Tianshu; Ho, Chia-hua; Sekirnik, Rok; Zayer, Adam; Granatino, Nicolas; Cockman, Matthew E; Loenarz, Christoph; Loik, Nikita D; Hardy, Adam P; Claridge, Timothy D W; Hamed, Refaat B; Chowdhury, Rasheduzzaman; Gong, Lingzhi; Robinson, Carol V; Trudgian, David C; Jiang, Miao; Mackeen, Mukram M; McCullagh, James S; Gordiyenko, Yuliya; Thalhammer, Armin; Yamamoto, Atsushi; Yang, Ming; Liu-Yi, Phebee; Zhang, Zhihong; Schmidt-Zachmann, Marion; Kessler, Benedikt M; Ratcliffe, Peter J; Preston, Gail M; Coleman, Mathew L; Schofield, Christopher J

    2012-12-01

    The finding that oxygenase-catalyzed protein hydroxylation regulates animal transcription raises questions as to whether the translation machinery and prokaryotic proteins are analogously modified. Escherichia coli ycfD is a growth-regulating 2-oxoglutarate oxygenase catalyzing arginyl hydroxylation of the ribosomal protein Rpl16. Human ycfD homologs, Myc-induced nuclear antigen (MINA53) and NO66, are also linked to growth and catalyze histidyl hydroxylation of Rpl27a and Rpl8, respectively. This work reveals new therapeutic possibilities via oxygenase inhibition and by targeting modified over unmodified ribosomes.

  1. 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.

  2. 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

  3. Describing Temperature-Dependent Self-Diffusion Coefficients and Fluidity of 1- and 3-Alcohols with the Compensated Arrhenius Formalism.

    PubMed

    Fleshman, Allison M; Forsythe, Grant E; Petrowsky, Matt; Frech, Roger

    2016-09-22

    The location of the hydroxyl group in monohydroxy alcohols greatly affects the temperature dependence of the liquid structure due to hydrogen bonding. Temperature-dependent self-diffusion coefficients, fluidity (the inverse of viscosity), dielectric constant, and density have been measured for several 1-alcohols and 3-alcohols with varying alkyl chain lengths. The data are modeled using the compensated Arrhenius formalism (CAF). The CAF follows a modified transition state theory using an Arrhenius-like expression to describe the transport property, which consists of a Boltzmann factor containing an energy of activation, Ea, and an exponential prefactor containing the temperature-dependent solution dielectric constant, εs(T). Both 1- and 3-alcohols show the Ea of diffusion coefficients (approximately 43 kJ mol(-1)) is higher than the Ea of fluidity (approximately 35 kJ mol(-1)). The temperature dependence of the exponential prefactor in these associated liquids is explained using the dielectric constant and the Kirkwood-Frölich correlation factor, gk. It is argued that the dielectric constant must be used to account for the additional temperature dependence due to variations in the liquid structure (e.g., hydrogen bonding) for the CAF to accurately model the transport property.

  4. Alcoholic sialosis.

    PubMed

    Kastin, B; Mandel, L

    2000-01-01

    Sialosis (sialadenosis) is a term used to describe a disorder that involves both secretory and parenchymal changes of the major salivary glands, most commonly the parotid. Seen often in a dental office, it is recognized as an indolent, bilateral, non-inflammatory, non-neoplastic, soft, symmetrical, painless and persistent enlargement of the parotid glands. Four major entities have commonly been associated with this disorder. They are alcoholism, endocrinopathy (particularly diabetes mellitus), maLnutrition and idiopathic. We are reporting a case of alcoholic sialosis with its clinical and diagnostic aspects. It is important for the dental practitioner to recognize sialosis, because it often indicates the existence of an unsuspected systemic disease.

  5. Alcohol and Hepatitis

    MedlinePlus

    ... Home » Living with Hepatitis » Daily Living: Alcohol Viral Hepatitis Menu Menu Viral Hepatitis Viral Hepatitis Home For ... Alcohol for Veterans and the Public Alcohol and Hepatitis: Entire Lesson Overview Alcohol is one of the ...

  6. Alcohol and Hepatitis

    MedlinePlus

    ... code here Enter ZIP code here Daily Living: Alcohol for Veterans and the Public Alcohol and Hepatitis: Entire Lesson Overview Alcohol is one ... related to choices you make about your lifestyle . Alcohol and fibrosis Fibrosis is the medical term for ...

  7. Production of hydroxyl radicals by copper-containing metallothionein: roles as prooxidant.

    PubMed

    Suzuki, K T; Rui, M; Ueda, J; Ozawa, T

    1996-11-01

    Production of hydroxyl radicals by copper (Cu)-containing metallothionein (MT) and its relation to zinc (Zn) bound to MT were studied in vitro with reference to the mechanism of the Cu toxicity in the liver of LEC rats. Zn-MT prepared from the liver of Zn-injected rats was reacted with cupric ions at various Cu/Zn ratios, and the concentrations of the two metals bound to MT and in the solution, valence states of Cu in the solution, production of hydroxyl radicals were determined. Cupric ions replaced Zn in MT after being reduced by thiol groups, and MT, worked as an antioxidant. Cupric ions added to MT that did not contain Zn were reduced to cuprous ions by thiol groups in Cu-MT, and the Cu bound to MT was liberated in a form of cuprous ions. Hydroxyl radicals were produced in the presence of hydrogen peroxide in proportion to the amount of cuprous ions liberated from MT. Cu-containing MT was proposed to work as a prooxidant until all thiol groups in MT were oxidized when Zn was not present in MT. The results indicate that MT works as an antioxidant as long as Zn is present in Cu-containing MT, while it works as a prooxidant when Zn is not present by liberating 1.5 M equivalents of cuprous ions relative to cupric ions added, and hydroxyl radicals are produced in the presence of hydrogen peroxide. On the other hand, MT not bound by Cu does not work as a prooxidant throughout.

  8. Hydroxyl radical-mediated conversion of morphine to morphinone.

    PubMed

    Kumagai, Y; Ikeda, Y; Toki, S

    1992-05-01

    1. The hydroxyl radical-mediated conversion of morphine to morphinone (MO) was examined as an alternative to the enzymic reaction. 2. Hydroxyl radicals were generated by autoxidation of ascorbate in the presence of iron and EDTA. This system oxidized morphine to MO which was identified by h.p.l.c. and t.l.c. The reaction was dependent on the concentration of added Fe2+ and required the addition of ascorbate when Fe3+ was used. 3. Catalase inhibited production of MO whereas superoxide dismutase (SOD) had no effect. Addition of a large amount of H2O2 to the system resulted in a significant decrease in production of MO. No MO production was initiated by H2O2 itself. The oxidation of morphine was inhibited by typical hydroxyl radical-scavenging agents. These results indicate that morphine undergoes oxidation to MO by hydroxyl radical.

  9. Effect of Curcumin Against Oxidation of Biomolecules by Hydroxyl Radicals

    PubMed Central

    Mahendra, Jaideep; Gurumurthy, Prema; Jayamathi; Iqbal, Shabeer S; Mahendra, Little

    2014-01-01

    Background: Among various reactive oxygen species, hydroxyl radicals have the strongest chemical activity, which can damage a wide range of essential biomolecules such as lipids, proteins, and DNA. Objective: The objective of this study was to investigate the beneficial effects of curcumin on prevention of oxidative damage of biomolecules by hydroxyl radicals generated in in vitro by a Fenton like reaction. Materials and Methods: We have incubated the serum, plasma and whole blood with H2O2/Cu2+/ Ascorbic acid system for 4 hours at 37 0C and observed the oxidation of biomolecules like albumin, lipids, proteins and DNA. Results: Curcumin at the concentrations of 50,100 and 200 μmoles, prevented the formation of ischemia modified albumin, MDA, protein carbonyls, oxidized DNA and increased the total antioxidant levels and GSH significantly. Conclusion: These observations suggest the hydroxyl radical scavenging potentials of curcumin and protective actions to prevent the oxidation of biomolecules by hydroxyl radicals. PMID:25478334

  10. 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.

  11. 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.

  12. C-H stretching vibrations of methyl, methylene and methine groups at the vapor/alcohol (N = 1-8) interfaces.

    PubMed

    Lu, Rong; Gan, Wei; Wu, Bao-hua; Zhang, Zhen; Guo, Yuan; Wang, Hong-fei

    2005-07-28

    In IR and Raman spectral studies, the congestion of the vibrational modes in the C-H stretching region between 2800 and 3000 cm(-1) has complicated spectral assignment, conformational analysis, and structural and dynamics studies, even with quite a few of the simplest molecules. To resolve these issues, polarized spectra measurement on a well aligned sample is generally required. Because the liquid interface is generally ordered and molecularly thin, and sum frequency generation vibrational spectroscopy (SFG-VS) is an intrinsically coherent polarization spectroscopy, SFG-VS can be used for discerning details in vibrational spectra of the interfacial molecules. Here we show that, from systematic molecular symmetry and SFG-VS polarization analysis, a set of polarization selection rules could be developed for explicit assignment of the SFG vibrational spectra of the C-H stretching modes. These polarization selection rules helped assignment of the SFG-VS spectra of vapor/alcohol (n = 1-8) interfaces with unprecedented details. Previous approach on assignment of these spectra relied on IR and Raman spectral assignment, and they were not able to give such detailed assignment of the SFG vibrational spectra. Sometimes inappropriate assignment was made, and consequently misleading conclusions on interfacial structure, conformation and even dynamics were reached. With these polarization rules in addition to knowledge from IR and Raman studies, new structural information and understanding of the molecular interactions at these interfaces were obtained, and some new spectral features for the C-H stretching modes were also identified. Generally speaking, these new features can be applied to IR and Raman spectroscopic studies in the condensed phase. Therefore, the advancement on vibrational spectra assignment may find broad applications in the related fields using IR and Raman as vibrational spectroscopic tools.

  13. Moderate alcohol consumption--need for intervention programs in pregnancy?

    PubMed

    Meberg, A; Halvorsen, B; Holter, B; Ek, I J; Askeland, A; Gaaserud, W; Steinsvåg, J

    1986-01-01

    Consumption of alcohol was investigated in two groups of pregnant women: an intervention group (n = 58) (two structured interviews during pregnancy including counseling focused on reduction of alcohol consumption and potential benefits to the fetus, and interview after delivery), and a control group (n = 74) (interview after delivery). Prepregnancy 80% of the women were light or moderate alcohol consumers, and 20% teetotalers. Pregnancy considerably reduced alcohol consumption in both groups. 66% abstained from alcohol during pregnancy, and use of liquor nearly ceased. The changes in alcohol consumption occurred independently to the intervention program. Strategy for reducing alcohol consumption during pregnancy should include a structured alcohol anamnesis at the first ante-natal visit, accompanied by counseling focused on reduction of alcohol consumption. More extensive intervention programs may be reserved for pregnancies at higher risk (high-consumers, abusers).

  14. Hyperglycemia induces apoptosis in rat liver through the increase of hydroxyl radical: new insights into the insulin effect.

    PubMed

    Francés, Daniel E; Ronco, María T; Monti, Juan A; Ingaramo, Paola I; Pisani, Gerardo B; Parody, Juan P; Pellegrino, José M; Sanz, Paloma Martín; Carrillo, María C; Carnovale, Cristina E

    2010-05-01

    In this study, we analyzed the contribution of hydroxyl radical in the liver apoptosis mediated by hyperglycemia through the Bax-caspase pathway and the effects of insulin protection against the apoptosis induced by hyperglycemia. Male adult Wistar rats were randomized in three groups: control (C) (sodium citrate buffer, i.p.), streptozotocin (STZ)-induced diabetic (SID) (STZ 60 mg/kg body weight, i.p.), and insulin-treated SID (SID+I; 15 days post STZ injection, SID received insulin s.c., twice a day, 15 days). Rats were autopsied on day 30. In liver tissue, diabetes promoted a significant increase in hydroxyl radical production which correlated with lipid peroxidation (LPO) levels. Besides, hyperglycemia significantly increased mitochondrial BAX protein expression, cytosolic cytochrome c levels, and caspase-3 activity leading to an increase in apoptotic index. Interestingly, the treatment of diabetic rats with desferoxamine or tempol (antioxidants/hydroxyl radical scavengers) significantly attenuated the increase in both hydroxyl radical production and in LPO produced by hyperglycemia, preventing apoptosis by reduction of mitochondrial BAX and cytosolic cytochrome c levels. Insulin treatment showed similar results. The finding that co-administration of antioxidants/hydroxyl radical scavengers together with insulin did not provide any additional benefit compared with those obtained using either inhibitors or insulin alone shows that it is likely that insulin prevents oxidative stress by reducing the effects of hydroxyl radicals. Importantly, insulin significantly increased apoptosis inhibitor protein expression by induction of its mRNA. Taken together, our studies support that, at least in part, the hydroxyl radical acts as a reactive intermediate, which leads to liver apoptosis in a model of STZ-mediated hyperglycemia. A new anti-apoptosis signal for insulin is shown, given by an increase of apoptosis inhibitor protein.

  15. Alcoholism and Minority Populations.

    ERIC Educational Resources Information Center

    Watts, Thomas D.; Wright, Roosevelt, Jr.

    1991-01-01

    Briefly discusses some aspects of the role of the state and the position of minorities in respect to alcoholism policies and services. Includes case study of a Black alcoholic. Refers readers to studies on Black alcoholism, Native American alcoholism, Hispanic alcoholism, and Asian-American alcoholism. (Author/NB)

  16. Propargyl alcohol

    Integrated Risk Information System (IRIS)

    Propargyl alcohol ; CASRN 107 - 19 - 7 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic

  17. Allyl alcohol

    Integrated Risk Information System (IRIS)

    Allyl alcohol ; CASRN 107 - 18 - 6 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Eff

  18. Isobutyl alcohol

    Integrated Risk Information System (IRIS)

    Isobutyl alcohol ; CASRN 78 - 83 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic E

  19. Tuning optical and three photon absorption properties in graphene oxide-polyvinyl alcohol free standing films

    NASA Astrophysics Data System (ADS)

    Karthikeyan, B.; Udayabhaskar, R.; Hariharan, S.

    2016-07-01

    We report the optical and nonlinear optical properties of graphene oxide (GO)-polyvinyl alcohol (PVA) free standing films. The composite polymer films were prepared in ex-situ method. The variation in optical absorption spectra and optical constants with the amount of GO loading was noteworthy from the optical absorption spectroscopic studies. Nonlinear optical studies done at 532 nm using 5 ns laser pulses show three photon absorption like behaviour. Both steady state and time resolved fluorescence studies reveal that the GO was functioning as a pathway for the decay of fluorescence from PVA. This is attributed to the energy level modifications of GO through hydroxyl groups with PVA. Raman spectroscopy also supports the interaction between GO and PVA ions through OH radicals.

  20. Ab initio studies of hyperconjugation effects on charge distribution in tetracyclododecane alcohols

    NASA Astrophysics Data System (ADS)

    Tostes, J. Glauco R.; Seidl, Peter Rudolf; Soto, M. M.; De M. Carneiro, J. W.; Lie, S. K.; Taft, C. A.; Brown, W.; Lester, W. A., Jr.

    1995-05-01

    Ab initio calculations using the STO-3G, 6-31G, and 6-31G ∗∗ basis sets are used to investigate charge distribution in tetracyclododecane alcohols. The calculated net atomic charges using fully optimized geometries indicate that certain carbon and hydrogen atoms in the proximity of a nonbonding oxygen lone pair are more negatively charged and the carbon-carbon and carbon-hydrogen bonds are longer. Analysis of these charges and bond lengths as well as atomic orbital populations suggests that the differences between charge distribution on carbon and hydrogen atoms adjacent to the hydroxyl group and their corresponding carbon-carbon and carbon-hydrogen bond lengths can be explained in terms of hyperconjugation.

  1. Lignosulfonate as reinforcement in polyvinyl alcohol film: Mechanical properties and interaction analysis.

    PubMed

    Ye, De-zhan; Jiang, Li; Hu, Xiao-qin; Zhang, Ming-hua; Zhang, Xi

    2016-02-01

    Recently, there has been a growing research interest on renewable composite due to sustainability concerns. This work demonstrated the possibility of using eucalyptus lignosulfonate calcium (HLS) particles as reinforcement in polyvinyl alcohol (PVA) matrix. 41% and 384.7% improvement of pure PVA tensile strength and Young's modulus were achieved with incorporation of 5 wt% HLS. The above results were ascribed to specific intermolecular interactions between HLS and PVA, suggested by the increasing PVA glass transition and crystalline relaxations temperature, depression of melting point with HLS incorporation. Moreover, this interaction was quantitatively determined by q value of -62.4±10.0 in Kwei equation. Additionally, the remarkable red shift of wavenumber corresponding to hydroxyl group also indicated the formation of strong hydrogen bond in HLS/PVA blend. SEM characterization confirmed that HLS/PVA blends are at least miscible.

  2. Impact of hydrogen bonding on dynamics of hydroxyl-terminated polydimethylsiloxane

    SciTech Connect

    Xing, Kunyue; Chatterjee, Sabornie; Saito, Tomonori; Gainaru, Catalin P.; Sokolov, Alexei P.

    2016-04-06

    Dielectric spectroscopy, rheology, and differential scanning calorimetry were employed to study the effect of chain-end hydrogen bonding on the dynamics of hydroxylterminated polydimethylsiloxane. We demonstrate that hydrogen bonding has a strong influence on both segmental and slower dynamics in the systems with low molecular weights. In particular, the decrease in the chain length leads to an increase of the glass transition temperature, viscosity, and fragility index, at variance with the usual behavior of nonassociating polymers. The supramolecular association of hydroxylterminated chains leads to the emergence in dielectric and mechanical relaxation spectra of the so-called Debye process traditionally observed in monohydroxy alcohols. Our analysis suggests that the hydroxyl-terminated PDMS oligomers may associate in brush-like or chain-like structures, depending on the size of their covalent chains. Finally, the effective length of the linear-associated chains was estimated from the rheological measurements.

  3. Impact of hydrogen bonding on dynamics of hydroxyl-terminated polydimethylsiloxane

    DOE PAGES

    Xing, Kunyue; Chatterjee, Sabornie; Saito, Tomonori; ...

    2016-04-06

    Dielectric spectroscopy, rheology, and differential scanning calorimetry were employed to study the effect of chain-end hydrogen bonding on the dynamics of hydroxylterminated polydimethylsiloxane. We demonstrate that hydrogen bonding has a strong influence on both segmental and slower dynamics in the systems with low molecular weights. In particular, the decrease in the chain length leads to an increase of the glass transition temperature, viscosity, and fragility index, at variance with the usual behavior of nonassociating polymers. The supramolecular association of hydroxylterminated chains leads to the emergence in dielectric and mechanical relaxation spectra of the so-called Debye process traditionally observed in monohydroxymore » alcohols. Our analysis suggests that the hydroxyl-terminated PDMS oligomers may associate in brush-like or chain-like structures, depending on the size of their covalent chains. Finally, the effective length of the linear-associated chains was estimated from the rheological measurements.« less

  4. Dynamics of Alkane Hydroxylation at the Non-Heme Diiron Center in Methane Monooxygenase

    SciTech Connect

    Guallar, Victor; Gherman, Benjamin F.; Lippard, Stephen J.; Friesner, Richard A.

    2002-03-12

    Semiclassical molecular dynamics simulations have been combined with quantum chemistry calculations to provide detailed modeling of the methane and ethane hydroxylation reactions catalyzed by the hydroxylase enzymes of the soluble methane monooxygenase system. The experimental distribution of enantiomeric alcohols in the reaction of ethanes made chiral by the use of hydrogen isotopes is quantitatively reproduced and explained. The reaction dynamics involve a mixture of concerted and bound radical trajectories, and we characterize each of these reactive channels in detail. Diffusion of the bound radical intermediate at the active site core determines the global rate constant. The results also provide a qualitative rationale for the lack of ring-opened products derived from certain radical clock substrate probes and for the relative rate constants and kinetic isotope effects exhibited by a variety of substrates.

  5. New strategy for expression of recombinant hydroxylated human-derived gelatin in Pichia pastoris KM71.

    PubMed

    Duan, Huiming; Umar, Sirajo; Xiong, Runsong; Chen, Jinchun

    2011-07-13

    Gelatin is a well-known biopolymer, and it has a long history of use mainly as a gelling agent in the food industry. This paper reports a new method for producing recombinant hydroxylated human-derived gelatin in Pichia pastoris KM71. Three independent expression cassettes encoding for specific length of gelatin, prolyl 4-hydroxylase (P4H, EC 1.14.11.2), α-subunit (αP4H), and protein-disulfide isomerase (PDI) were individually cloned in one expression vector, pPIC9K. The modified gelatin gene and two subunit genes of P4H were under the control of two different inducible promoters, namely, alcohol oxidase 1 promoter (PAOX1) and formaldehyde dehydrogenase 1 promoter (PFLD1), respectively. The results of sodium dodecylsulfate-polyacrylamide gel electrophoresis show that a recombinant gelatin was successfully expressed in P. pastoris KM71 by methanol induction. Liquid chromatography coupled with tandem mass spectrometry analysis indicates that the expressed gelatin was hydroxylated with approximately 66.7% of proline residues in the Y positions of Gly-X-Y triplets. The results of nuclear magnetic resonance spectroscopy of recombinant gelatin test show that the (1)H and (13)C spectra have many corresponding characteristic displacement peaks, and amino acids composition analysis shows that it contains hydroxyproline and its UV absorption is consistent with the characteristics of gelatin.

  6. Adenine oxidation by pyrite-generated hydroxyl radicals.

    PubMed

    Cohn, Corey A; Fisher, Shawn C; Brownawell, Bruce J; Schoonen, Martin Aa

    2010-04-26

    Cellular exposure to particulate matter with concomitant formation of reactive oxygen species (ROS) and oxidization of biomolecules may lead to negative health outcomes. Evaluating the particle-induced formation of ROS and the oxidation products from reaction of ROS with biomolecules is useful for gaining a mechanistic understanding of particle-induced oxidative stress. Aqueous suspensions of pyrite particles have been shown to form hydroxyl radicals and degrade nucleic acids. Reactions between pyrite-induced hydroxyl radicals and nucleic acid bases, however, remain to be determined. Here, we compared the oxidation of adenine by Fenton-generated (i.e., ferrous iron and hydrogen peroxide) hydroxyl radicals to adenine oxidation by hydroxyl radicals generated in pyrite aqueous suspensions. Results show that adenine oxidizes in the presence of pyrite (without the addition of hydrogen peroxide) and that the rate of oxidation is dependent on the pyrite loading. Adenine oxidation was prevented by addition of either catalase or ethanol to the pyrite/adenine suspensions, which implies that hydrogen peroxide and hydroxyl radicals are causing the adenine oxidation. The adenine oxidation products, 8-oxoadenine and 2-hydroxyadenine, were the same whether hydroxyl radicals were generated by Fenton or pyrite-initiated reactions. Although nucleic acid bases are unlikely to be directly exposed to pyrite particles, the formation of ROS in the vicinity of cells may lead to oxidative stress.

  7. The hydroxyl radical in plants: from seed to seed.

    PubMed

    Richards, Siân L; Wilkins, Katie A; Swarbreck, Stéphanie M; Anderson, Alexander A; Habib, Noman; Smith, Alison G; McAinsh, Martin; Davies, Julia M

    2015-01-01

    The hydroxyl radical (OH(•)) is the most potent yet short-lived of the reactive oxygen species (ROS) radicals. Just as hydrogen peroxide was once considered to be simply a deleterious by-product of oxidative metabolism but is now acknowledged to have signalling roles in plant cells, so evidence is mounting for the hydroxyl radical as being more than merely an agent of destruction. Its oxidative power is harnessed to facilitate germination, growth, stomatal closure, reproduction, the immune response, and adaptation to stress. It features in plant cell death and is a key tool in microbial degradation of plant matter for recycling. Production of the hydroxyl radical in the wall, at the plasma membrane, and intracellularly is facilitated by a range of peroxidases, superoxide dismutases, NADPH oxidases, and transition metal catalysts. The spatio-temporal activity of these must be tightly regulated to target substrates precisely to the site of radical production, both to prevent damage and to accommodate the short half life and diffusive capacity of the hydroxyl radical. Whilst research has focussed mainly on the hydroxyl radical's mode of action in wall loosening, studies now extend to elucidating which proteins are targets in signalling systems. Despite the difficulties in detecting and manipulating this ROS, there is sufficient evidence now to acknowledge the hydroxyl radical as a potent regulator in plant cell biology.

  8. Hemibonding of hydroxyl radical and halide anion in aqueous solution.

    PubMed

    Yamaguchi, Makoto

    2011-12-29

    Molecular geometries and properties of the possible reaction products between the hydroxyl radical and the halide anions in aqueous solution were investigated. The formation of two-center three-electron bonding (hemibonding) between the hydroxyl radical and halide anions (Cl, Br, I) was examined by density functional theory (DFT) calculation with a range-separated hybrid (RSH) exchange-correlation functional. The long-range corrected hybrid functional (LC-ωPBE), which have given quantitatively satisfactory results for odd electron systems and excited states, was examined by test calculations for dihalogen radical anions (X(2)(-); X = Cl, Br, I) and hydroxyl radical-water clusters. Equilibrium geometries with hemibonding between the hydroxyl radical and halide anions were located by including four hydrogen-bonded water molecules. Excitation energies and oscillator strengths of σ-σ* transitions calculated by the time-dependent DFT method showed good agreement with observed values. Calculated values of the free energy of reaction on the formation of hydroxyl halide radical anion from the hydroxyl radical and halide anion were endothermic for chloride but exothermic for bromide and iodide, which is consistent with experimental values of equilibrium constants.

  9. Relationship between phenytoin and tolbutamide hydroxylations in human liver microsomes.

    PubMed Central

    Doecke, C J; Veronese, M E; Pond, S M; Miners, J O; Birkett, D J; Sansom, L N; McManus, M E

    1991-01-01

    1. The metabolic interaction of phenytoin and tolbutamide in human liver microsomes was investigated. 2. Phenytoin 4-hydroxylation (mean Km 29.6 microM, n = 3) was competitively inhibited by tolbutamide (mean Ki 106.2 microM, n = 3) and tolbutamide methylhydroxylation (mean Km 85.6 microM, n = 3) was competitively inhibited by phenytoin (mean Ki 22.6 microM, n = 3). 3. A significant correlation was obtained between phenytoin and tolbutamide hydroxylations in microsomes from 18 human livers (rs = 0.82, P less than 0.001). 4. Sulphaphenazole was a potent inhibitor of both phenytoin and tolbutamide hydroxylations with IC50 values of 0.4 microM and 0.6 microM, respectively. 5. Mephenytoin was a poor inhibitor of both phenytoin and tolbutamide hydroxylations with IC50 values greater than 400 microM for both reactions. 6. Anti-rabbit P450IIC3 IgG inhibited both phenytoin and tolbutamide hydroxylations in human liver microsomes by 62 and 68%, respectively. 7. These in vitro studies are consistent with phenytoin 4-hydroxylation and tolbutamide methylhydroxylation being catalysed by the same cytochrome P450 isozyme(s) in human liver microsomes. PMID:2049228

  10. Specific solvent effects of hydroxylic solvents on the emission properties of ruthenium(ii)tris(2,2'-bipyridyl) chloride.

    PubMed

    Hartmann, P; Leiner, M J; Lippitsch, M E

    1995-06-01

    The excited state of Ru(II)[bpy]3 (2+) dissolved in hydroxylic solvents is subject to specific solvent effects, which were hitherto not understood on a quantitative basis. We determined the solvent effects of linear monovalent alcohols on the energy gap law of internal conversion with the help of lifetime and intensity measurements. An on-line method for measurement of the temperature dependence of quantum efficiencies was introduced. A modified Franck-Condon analysis of emission spectra by taking into account the shape of a Morse potential of the involved states was applied to compute excited-state energies.

  11. Effects of monohydric alcohols and polyols on the thermal stability of a protein

    NASA Astrophysics Data System (ADS)

    Murakami, Shota; Kinoshita, Masahiro

    2016-03-01

    The thermal stability of a protein is lowered by the addition of a monohydric alcohol, and this effect becomes larger as the size of hydrophobic group in an alcohol molecule increases. By contrast, it is enhanced by the addition of a polyol possessing two or more hydroxyl groups per molecule, and this effect becomes larger as the number of hydroxyl groups increases. Here, we show that all of these experimental observations can be reproduced even in a quantitative sense by rigid-body models focused on the entropic effect originating from the translational displacement of solvent molecules. The solvent is either pure water or water-cosolvent solution. Three monohydric alcohols and five polyols are considered as cosolvents. In the rigid-body models, a protein is a fused hard spheres accounting for the polyatomic structure in the atomic detail, and the solvent is formed by hard spheres or a binary mixture of hard spheres with different diameters. The effective diameter of cosolvent molecules and the packing fractions of water and cosolvent, which are crucially important parameters, are carefully estimated using the experimental data of properties such as the density of solid crystal of cosolvent, parameters in the pertinent cosolvent-cosolvent interaction potential, and density of water-cosolvent solution. We employ the morphometric approach combined with the integral equation theory, which is best suited to the physical interpretation of the calculation result. It is argued that the degree of solvent crowding in the bulk is the key factor. When it is made more serious by the cosolvent addition, the solvent-entropy gain upon protein folding is magnified, leading to the enhanced thermal stability. When it is made less serious, the opposite is true. The mechanism of the effects of monohydric alcohols and polyols is physically the same as that of sugars. However, when the rigid-body models are employed for the effect of urea, its addition is predicted to enhance the

  12. Effects of monohydric alcohols and polyols on the thermal stability of a protein.

    PubMed

    Murakami, Shota; Kinoshita, Masahiro

    2016-03-28

    The thermal stability of a protein is lowered by the addition of a monohydric alcohol, and this effect becomes larger as the size of hydrophobic group in an alcohol molecule increases. By contrast, it is enhanced by the addition of a polyol possessing two or more hydroxyl groups per molecule, and this effect becomes larger as the number of hydroxyl groups increases. Here, we show that all of these experimental observations can be reproduced even in a quantitative sense by rigid-body models focused on the entropic effect originating from the translational displacement of solvent molecules. The solvent is either pure water or water-cosolvent solution. Three monohydric alcohols and five polyols are considered as cosolvents. In the rigid-body models, a protein is a fused hard spheres accounting for the polyatomic structure in the atomic detail, and the solvent is formed by hard spheres or a binary mixture of hard spheres with different diameters. The effective diameter of cosolvent molecules and the packing fractions of water and cosolvent, which are crucially important parameters, are carefully estimated using the experimental data of properties such as the density of solid crystal of cosolvent, parameters in the pertinent cosolvent-cosolvent interaction potential, and density of water-cosolvent solution. We employ the morphometric approach combined with the integral equation theory, which is best suited to the physical interpretation of the calculation result. It is argued that the degree of solvent crowding in the bulk is the key factor. When it is made more serious by the cosolvent addition, the solvent-entropy gain upon protein folding is magnified, leading to the enhanced thermal stability. When it is made less serious, the opposite is true. The mechanism of the effects of monohydric alcohols and polyols is physically the same as that of sugars. However, when the rigid-body models are employed for the effect of urea, its addition is predicted to enhance the

  13. Synthesis and antioxidant capacities of hydroxyl derivatives of cinnamoylphenethylamine in protecting DNA and scavenging radicals.

    PubMed

    Yang, Yang; Song, Zhi-Guang; Liu, Zai-Qun

    2011-04-01

    Cinnamoylphenethylamine (CNPA) derivatives including feruloylphenethylamine (FRPA), caffeoylphenethylamine (CFPA), cinnamoyltyramine (CNTA), feruloyltyramine (FRTA) and caffeoyltyramine (CFTA) were synthesized in order to investigate the influence of the number and position of hydroxyl group on Cu(2+)/glutathione (GSH) and 2,2'-azobis(2-amidinopropane hydrochloride) (AAPH)-induced oxidation of DNA. The radical-scavenging properties of these CNPA derivatives were also evaluated by trapping 2,2'-azinobis(3-ethylbenzothiazoline-6-sulphonate) cationic radical (ABTS(+•)), 2,2'-diphenyl-1-picrylhydrazyl radical (DPPH) and galvinoxyl radical. In addition, these CNPA derivatives were tested by linoleic acid (LH)-β-carotene-bleaching experiment. The chemical kinetic was employed to treat the results from AAPH-induced oxidation of DNA and gave the order of antioxidant ability as CFTA > CFPA > FRTA > FRPA. CFTA and CFPA also possessed high abilities to inhibit Cu²(+)/GSH-mediated degradation of DNA, whereas FRPA and FRTA can protect LH against the auto-oxidation efficiently. Finally, CFPA and FRPA exhibited high activity in trapping ABTS(+•), DPPH and galvinoxyl radicals. Therefore, the cinnamoyl group bearing ortho-dihydroxyl or hydroxyl with ortho-methoxyl benefited for CNPA derivatives to protect DNA, while hydroxyl in tyramine cannot enhance the radical-scavenging abilities of CNPA derivatives.

  14. ipso-Hydroxylation and Subsequent Fragmentation: a Novel Microbial Strategy To Eliminate Sulfonamide Antibiotics

    PubMed Central

    Ricken, Benjamin; Cichocka, Danuta; Parisi, Martina; Lenz, Markus; Wyss, Dominik; Martínez-Lavanchy, Paula M.; Müller, Jochen A.; Shahgaldian, Patrick; Tulli, Ludovico G.; Kohler, Hans-Peter E.; Kolvenbach, Boris A.

    2013-01-01

    Sulfonamide antibiotics have a wide application range in human and veterinary medicine. Because they tend to persist in the environment, they pose potential problems with regard to the propagation of antibiotic resistance. Here, we identified metabolites formed during the degradation of sulfamethoxazole and other sulfonamides in Microbacterium sp. strain BR1. Our experiments showed that the degradation proceeded along an unusual pathway initiated by ipso-hydroxylation with subsequent fragmentation of the parent compound. The NADH-dependent hydroxylation of the carbon atom attached to the sulfonyl group resulted in the release of sulfite, 3-amino-5-methylisoxazole, and benzoquinone-imine. The latter was concomitantly transformed to 4-aminophenol. Sulfadiazine, sulfamethizole, sulfamethazine, sulfadimethoxine, 4-amino-N-phenylbenzenesulfonamide, and N-(4-aminophenyl)sulfonylcarbamic acid methyl ester (asulam) were transformed accordingly. Therefore, ipso-hydroxylation with subsequent fragmentation must be considered the underlying mechanism; this could also occur in the same or in a similar way in other studies, where biotransformation of sulfonamides bearing an amino group in the para-position to the sulfonyl substituent was observed to yield products corresponding to the stable metabolites observed by us. PMID:23835177

  15. 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.

  16. Novel hydroxyl radical scavenging antioxidant activity assay for water-soluble antioxidants using a modified CUPRAC method.

    PubMed

    Bektaşoğlu, Burcu; Esin Celik, Saliha; Ozyürek, Mustafa; Güçlü, Kubilay; Apak, Reşat

    2006-07-07

    Reactive oxygen species (ROS) such as superoxide anion, hydroxyl ((*)OH), peroxyl, and alkoxyl radicals may attack biological macromolecules giving rise to oxidative stress-originated diseases. Since (*)OH is very short-lived, secondary products resulting from (*)OH attack to various probes are measured. Although the measurement of aromatic hydroxylation with HPLC/electrochemical detection is more specific than the low-yield TBARS test, it requires sophisticated instrumentation. As a more convenient and less costly alternative, we used p-aminobenzoate, 2,4- and 3,5-dimethoxybenzoate probes for detecting hydroxyl radicals generated from an equivalent mixture of Fe(II)+EDTA with hydrogen peroxide. The produced hydroxyl radicals attacked both the probe and the water-soluble antioxidants in 37 degrees C-incubated solutions for 2h. The CUPRAC (i.e., our original method for total antioxidant capacity assay) absorbance of the ethylacetate extract due to the reduction of Cu(II)-neocuproine reagent by the hydroxylated probe decreased in the presence of (*)OH scavengers, the difference being proportional to the scavenging ability of the tested compound. A rate constant for the reaction of the scavenger with hydroxyl radical can be deduced from the inhibition of color formation. The second-order rate constants of the scavengers were determined with competition kinetics by means of a linear plot of A(0)/A as a function of C(scavenger)/C(probe), where A(0) and A are the CUPRAC absorbances of the system in the absence and presence of scavenger, respectively, and C is the molar concentration of relevant species. The 2,4- and 3,5-dimethoxybenzoates were the best probes in terms of linearity and sensitivity. Iodide, metabisulfite, hexacyanoferrate(II), thiourea, formate, and dimethyl sulfoxide were shown by the modified CUPRAC assay to be more effective scavengers than mannitol, glucose, lysine, and simple alcohols, as in the TBARS assay. The developed method is less lengthy, more

  17. Trajectories of Alcohol Consumption Following Liver Transplantation

    PubMed Central

    DiMartini, Andrea; Dew, Mary Amanda; Day, Nancy; Fitzgerald, Mary Grace; Jones, Bobby L.; deVera, Michael; Fontes, Paulo

    2010-01-01

    Any use of alcohol in the years following liver transplantation (LTX) approaches 50% of patients transplanted for alcoholic liver disease (ALD). We collected detailed prospective data on alcohol consumption following LTX for ALD to investigate ongoing patterns of use. Using trajectory modeling we identified four distinct alcohol use trajectories. One group had minimal use over time. Two other groups developed early onset moderate to heavy consumption and one group developed late onset moderate use. These trajectories demonstrate that alcohol use varies based on timing of onset, quantity, and duration. Using discriminant function analysis, we examine characteristics of recipient’s pre-LTX alcohol histories and early post-LTX psychological stressors to identify the profile of those at risk for these specific trajectories. We discuss the relevance of these findings to clinical care and preliminarily to outcomes. PMID:20726963

  18. Demonstration of hydroxyl radical generation in stunned' myocardium of intact dogs using aromatic hydroxylation of phenylalanine

    SciTech Connect

    Bolli, R.; Kaur, H.; Li, X.Y.; Triana, J.F.; Halliwell, B. Univ. of California, Davis King's College, London )

    1991-03-11

    Numerous studies have shown that postischemic myocardial dysfunction is attenuated by scavengers of hydroxyl ({sup {sm bullet}}OH) radicals and by iron chelators, suggesting an important pathogenetic role of {sup {sm bullet}}OH. However, the evidence provided by these studies is indirect. Since phenyl-alanine (PH) has been shown to react with {sup {sm bullet}}OH to form o-, m-, and p-tyrosines (TYR), the authors used aromatic hydroxylation of PH to detect {sup {sm bullet}}OH in stunned myocardium. Open-chest dogs underwent a 15-min coronary occlusion (O) followed by reperfusion (R). PH was infused i.v. starting 5 min pre-O and ending 10 min after R (n = 3) or starting at R and ending 10 min later (n = 8). TYR concentration in local coronary venous effluent plasma was measured using HPLC with electrochemical detection. No appreciable production of TYR was observed before or during O. After R, however, in all dogs there was a dramatic increase in myocardial production of o-, m-, and p-TYR which peaked at 1-3 min and ceased after 10 min. In 5 control dogs, infusion of PH without O/R did not result in any TYR production. These results provide evidence that the highly reactive {sup {sm bullet}}OH radical is produced after brief regional ischemia in the intact animal and indicate that PH may be a useful probe for measuring this species. The findings support the hypothesis that {sup {sm bullet}}OH contributes to myocardial stunning.'

  19. A fourier transform infrared spectroscopy (FTIR) based assay for Candida parapsilosis ATCC 7330 mediated oxidation of aryl alcohols.

    PubMed

    Sudhakara, Sneha; Chadha, Anju

    2015-09-10

    We present an FTIR based assay to monitor the whole cell mediated oxidation of aryl alcohols by measuring the characteristic IR absorption of the hydroxyl group [OH] of the substrate and the carbonyl group [CO] of the corresponding oxidized product. This method expedites the analysis of whole cell mediated catalysis which is usually done by GC and/or HPLC. The FTIR assay had linearity with R(2)≥0.980 and sensitivity up to 10μM. The accuracy and precision of FTIR assay was found ≥81% and ≥94%, respectively. This assay was validated by GC which exhibited ≥82% accuracy and ≥79% precision. The time of analysis taken by this assay was 2-3min per sample in comparison with 20-40min by GC.

  20. [Causes of the people death from drunkenness and alcoholism].

    PubMed

    Erokhin, Iu A; Paukov, V S; Kirillov, Iu A

    2012-01-01

    We analyzed causes of 1008 people death, who abused by alcohol. Among them 2 groups were separated out: people died due to drunkenness and due to alcoholism. The structure of the death was similar in the both groups, however depended on alcoholism stages. The major cause of the death in group of drunkenness people was acute heart insufficiency, less commonly--lung pathology, and very rarely--brain vessels pathology and liver cirrhosis. In group of people, who died due to alcoholism, lung pathology was the major cause of these deaths, acute heart insufficiency was occurred less commonly, and very rare brain pathology because of delirium tremens or alcohol withdrawal syndrome, as so liver cirrhosis with complications. Hemorrhagic pancreonecrosis after alcoholic excess was found out in both groups, but it was more often in people, who died due to drunkenness. Obtained results show importance of chronic alcoholism identification as a disease with several stages including drunkenness and alcoholism.

  1. [Treatment processes of pre-alcoholism and alcohol dependence targeted towards drinking reduction].

    PubMed

    Yoshimura, Atsushi; Maesato, Hitoshi; Hisatomi, Nobuko; Higuchi, Susumu

    2013-02-01

    Since the 1990s, we have suggested the concept of pre-alcoholism which encompasses patients who have drunk a great deal of alcohol leading to alcohol related problems such as health issues, domestic violence, drunken driving and black-outs. Pre-alcoholism excludes alcohol-dependent patients who have experienced continuous drinking or withdrawal symptoms. We have treated many outpatients with pre-alcoholism for several years. Our regimen demands that the patients must be abstinent for half a year at the beginning of their treatment. After half a year they can choose whether they will continue to be abstinent or they will resume drinking with the aim of reducing their total alcohol consumption. The study clarified the character of pre-alcoholism by investigation of the patients' background and re-diagnosis of the patients based on the International Classification of Diseases, 10th Revision (ICD-10). A remarkable ratio of pre-alcoholic patients was diagnosed with alcohol dependence under ICD-10. We classified pre-alcoholic patients into two groups, one diagnosed as having ICD-10-classed alcohol dependence and the other which did not fulfill the ICD-10 diagnostic criteria of alcohol dependence, and examined the therapeutic processes of the two groups. It was shown that most pre-alcoholic patients could finally take required courses of treatment by themselves without regard to diagnosis under ICD-10, even if they chose any treatment and made alcohol related mistakes on the way. Our findings suggested that pre-alcoholic patients, a portion of whom may have exhibited mild alcohol dependence, could select drinking reduction as a primary goal of treatment after a certain period of abstinence.

  2. Underage Alcohol Use

    PubMed Central

    Brown, Sandra A.; McGue, Matthew; Maggs, Jennifer; Schulenberg, John; Hingson, Ralph; Swartzwelder, Scott; Martin, Christopher; Chung, Tammy; Tapert, Susan F.; Sher, Kenneth; Winters, Ken C.; Lowman, Cherry; Murphy, Stacia

    2009-01-01

    Late adolescence (i.e., the age-group between 16 and 20 years) is characterized by significant changes in neurological and cognitive processes, behavioral and social functioning, and relational and physical contexts as the individual moves toward adulthood. In this age-group, major role transitions affect almost every aspect of life. Moreover, brain development continues—and with it the development of cognitive functions, working memory, emotional and behavioral self-regulation, and decisionmaking. The adolescent’s social and emotional development also continues to evolve, affecting interactions with parents, siblings, peers, and first romantic relationships. All of these changes impact drinking behavior during late adolescence, and, in fact, alcohol use, binge drinking, and heavy drinking are particularly prevalent in youth ages 16–20. Determining the common trajectories of drinking behavior in this age–group is important for understanding how adolescent alcohol use helps shape adult outcomes and for identifying risk and protective factors. It also is important to study the short- and long-term consequences of adolescent alcohol use and abuse, including alcohol’s effects on the developing adolescent brain and accomplishment of important developmental tasks of this age. PMID:23104446

  3. Alcohol use and safe drinking

    MedlinePlus

    ... to alcohol use Get into trouble with the law, family members, friends, school, or dates because of alcohol THE EFFECTS OF ALCOHOL Alcoholic drinks have different amounts of alcohol in them. Beer is about 5% alcohol, although some beers can ...

  4. Interstellar Alcohols

    NASA Technical Reports Server (NTRS)

    Charnley, S. B.; Kress, M. E.; Tielens, A. G. G. M.; Millar, T. J.

    1995-01-01

    We have investigated the gas-phase chemistry in dense cores where ice mantles containing ethanol and other alcohols have been evaporated. Model calculations show that methanol, ethanol, propanol, and butanol drive a chemistry leading to the formation of several large ethers and esters. Of these molecules, methyl ethyl ether (CH3OC2H5) and diethyl ether (C2H5)2O attain the highest abundances and should be present in detectable quantities within cores rich in ethanol and methanol. Gas-phase reactions act to destroy evaporated ethanol and a low observed abundance of gas-phase C,H,OH does not rule out a high solid-phase abundance. Grain surface formation mechanisms and other possible gas-phase reactions driven by alcohols are discussed, as are observing strategies for the detection of these large interstellar molecules.

  5. 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).

  6. Monte Carlo Simulation of Aqueous Dilute Solutions of Polyhydric Alcohols

    NASA Astrophysics Data System (ADS)

    Lilly, Arnys Clifton, Jr.

    In order to investigate the details of hydrogen bonding and solution molecular conformation of complex alcohols in water, isobaric-isothermal Monte Carlo simulations were carried out on several systems. The solutes investigated were ethanol, ethylene glycol, 1,2-propylene glycol, 1,3 -propylene glycol and glycerol. In addition, propane, which does not hydrogen bond but does form water hydrates, was simulated in aqueous solution. The complex alcohol-water systems are very nonideal in their behavior as a function of solute concentration down to very dilute solutions. The water model employed was TIP4P water^1 and the intermolecular potentials employed are of the Jorgensen type^2 in which the interactions between the molecules are represented by interaction sites usually located on nuclei. The interactions are represented by a sum of Coulomb and Lennard-Jones terms between all intermolecular pairs of sites. Intramolecular rotations in the solute are modeled by torsional potential energy functions taken from ethanol, 1-propanol and 2-propanol for C-O and C-C bond rotations. Quasi-component pair correlation functions were used to analyze the hydrogen bonding. Hydrogen bonds were classified as proton acceptor and proton donor bonds by analyzing the nearest neighbor pair correlation function between hydroxyl oxygen and hydrogen and between solvent-water hydrogen and oxygen. The results obtained for partial molar heats of solution are more negative than experimental values by 3.0 to 14 kcal/mol. In solution, all solutes reached a contracted molecular geometry with the OH groups generally on one side of the molecule. There is a tendency for the solute OH groups to hydrogen bond with water, with more proton acceptor bonds than proton donor bonds. The water -solute binding energies correlate with experimental measurements of the water-binding properties of the solute. ftn ^1Jorgensen, W. L. et al, J. Chem. Phys., 79, 926 (1983). ^2Jorgensen, W. L., J. Phys Chem., 87, 5304

  7. 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.

  8. Is local alcohol outlet density related to alcohol-related morbidity and mortality in Scottish cities?

    PubMed Central

    Richardson, E.A.; Hill, S.E.; Mitchell, R.; Pearce, J.; Shortt, N.K.

    2015-01-01

    Alcohol consumption may be influenced by the local alcohol retailing environment. This study is the first to examine neighbourhood alcohol outlet availability (on- and off-sales outlets) and alcohol-related health outcomes in Scotland. Alcohol-related hospitalisations and deaths were significantly higher in neighbourhoods with higher outlet densities, and off-sales outlets were more important than on-sales outlets. The relationships held for most age groups, including those under the legal minimum drinking age, although were not significant for the youngest legal drinkers (18–25 years). Alcohol-related deaths and hospitalisations were higher in more income-deprived neighbourhoods, and the gradient in deaths (but not hospitalisations) was marginally larger in neighbourhoods with higher off-sales outlet densities. Efforts to reduce alcohol-related harm should consider the potentially important role of the alcohol retail environment. PMID:25840352

  9. Alcohol Dehydrogenase from Methylobacterium organophilum

    PubMed Central

    Wolf, H. J.; Hanson, R. S.

    1978-01-01

    The alcohol dehydrogenase from Methylobacterium organophilum, a facultative methane-oxidizing bacterium, has been purified to homogeneity as indicated by sodium dodecyl sulfate-gel electrophoresis. It has several properties in common with the alcohol dehydrogenases from other methylotrophic bacteria. The active enzyme is a dimeric protein, both subunits having molecular weights of about 62,000. The enzyme exhibits broad substrate specificity for primary alcohols and catalyzes the two-step oxidation of methanol to formate. The apparent Michaelis constants of the enzyme are 2.9 × 10−5 M for methanol and 8.2 × 10−5 M for formaldehyde. Activity of the purified enzyme is dependent on phenazine methosulfate. Certain characteristics of this enzyme distinguish it from the other alcohol dehydrogenases of other methylotrophic bacteria. Ammonia is not required for, but stimulates the activity of newly purified enzyme. An absolute dependence on ammonia develops after storage of the purified enzyme. Activity is not inhibited by phosphate. The fluorescence spectrum of the enzyme indicates that it and the cofactor associated with it may be chemically different from the alcohol dehydrogenases from other methylotrophic bacteria. The alcohol dehydrogenases of Hyphomicrobium WC-65, Pseudomonas methanica, Methylosinus trichosporium, and several facultative methylotrophs are serologically related to the enzyme purified in this study. The enzymes of Rhodopseudomonas acidophila and of organisms of the Methylococcus group did not cross-react with the antiserum prepared against the alcohol dehydrogenase of M. organophilum. Images PMID:80974

  10. Lethal hydroxyl radical accumulation by a lactococcal bacteriocin, lacticin Q.

    PubMed

    Li, Mengqi; Yoneyama, Fuminori; Toshimitsu, Nayu; Zendo, Takeshi; Nakayama, Jiro; Sonomoto, Kenji

    2013-08-01

    The antimicrobial mechanism of a lactococcal bacteriocin, lacticin Q, can be described by the toroidal pore model without any receptor. However, lacticin Q showed different degrees of activity (selective antimicrobial activity) against Gram-positive bacteria even among related species. The ability of lacticin Q to induce pore formation in liposomes composed of lipids from different indicator strains indicated that its selective antimicrobial activity could not be attributed only to membrane lipid composition. We investigated the accumulation of deleterious hydroxyl radicals after exposure to lacticin Q as a contributing factor to cell death in the indicator strains. When lacticin Q of the same concentration as the MIC or minimum bactericidal concentration was added to the indicator cultures, high levels of hydroxyl radical accumulation were detected. Treatment with hydroxyl radical scavengers, thiourea and 2,2'-bipyridyl, decreased the levels of hydroxyl radical accumulation and recovered cell viability. These results suggest that, with or without pore formation, the final antimicrobial mechanism of lacticin Q is the accumulation of hydroxyl radicals, which varies by strain, resulting in the selective antimicrobial activity of lacticin Q.

  11. Ab initio dynamics of the cytochrome P450 hydroxylation reaction

    PubMed Central

    Elenewski, Justin E.; Hackett, John C

    2015-01-01

    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. PMID:25681906

  12. Lethal Hydroxyl Radical Accumulation by a Lactococcal Bacteriocin, Lacticin Q

    PubMed Central

    Li, Mengqi; Yoneyama, Fuminori; Toshimitsu, Nayu; Zendo, Takeshi; Nakayama, Jiro

    2013-01-01

    The antimicrobial mechanism of a lactococcal bacteriocin, lacticin Q, can be described by the toroidal pore model without any receptor. However, lacticin Q showed different degrees of activity (selective antimicrobial activity) against Gram-positive bacteria even among related species. The ability of lacticin Q to induce pore formation in liposomes composed of lipids from different indicator strains indicated that its selective antimicrobial activity could not be attributed only to membrane lipid composition. We investigated the accumulation of deleterious hydroxyl radicals after exposure to lacticin Q as a contributing factor to cell death in the indicator strains. When lacticin Q of the same concentration as the MIC or minimum bactericidal concentration was added to the indicator cultures, high levels of hydroxyl radical accumulation were detected. Treatment with hydroxyl radical scavengers, thiourea and 2,2′-bipyridyl, decreased the levels of hydroxyl radical accumulation and recovered cell viability. These results suggest that, with or without pore formation, the final antimicrobial mechanism of lacticin Q is the accumulation of hydroxyl radicals, which varies by strain, resulting in the selective antimicrobial activity of lacticin Q. PMID:23733459

  13. 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.

  14. Pre-pregnancy alcohol experience attenuates typical decrease in gestational alcohol consumption in mice.

    PubMed

    Becker, H C; Randall, C L; Anton, R F

    1986-01-01

    The influence of pre-pregnancy alcohol consumption on alcohol self-selection during pregnancy and lactation was examined in C57BL mice. One group of animals was given a two-bottle choice between water and a 10% w/v ethanol solution for three weeks prior to breeding, throughout pregnancy, and during lactation, while a second group was given the alcohol-water choice beginning on the first day of pregnancy. Relative alcohol intake (g ethanol/kg body weight) as well as alcohol "preference" decreased below pre-pregnancy levels during both pregnancy and lactation. That is, voluntary alcohol consumption was attenuated in pregnant and lactating mice, regardless of strain-typical pre-pregnancy high consumption. However, mice given a choice between alcohol and water prior to pregnancy did not decrease their alcohol consumption during pregnancy as much as mice not given the pre-pregnancy alcohol choice. There was no correlation between pre-pregnancy alcohol consumption and subsequent intake. The mechanism underlying decreased voluntary alcohol consumption during pregnancy remains to be elucidated, but it is clear that prior experience with alcohol influences the phenomenon.

  15. [Out of addictions: Alcohol, or alcohol to alcohol].

    PubMed

    Simmat-Durand, L; Vellut, N; Lejeune, C; Jauffret-Roustide, M; Mougel, S; Michel, L; Planche, M

    2016-06-29

    Pathways from alcoholism to recovery are documented; less often are those from drug addiction to alcoholism. Biographical approaches allow analyzing how people change their uses and talk about their trajectories of recovery.

  16. Reactivity of aqueous phase hydroxyl radical with halogenated carboxylate anions: experimental and theoretical studies.

    PubMed

    Minakata, Daisuke; Song, Weihua; Crittenden, John

    2011-07-15

    With concerns about emerging contaminants increasing, advanced oxidation processes have become attractive technologies because of potential mineralization of these contaminants via radical involved reactions that are induced by highly reactive hydroxyl radical. Considering the expensive and time-consuming experimental studies of degradation intermediates and byproduct, there is a need to develop a first-principles computer-based kinetic model that predict reaction pathways and associated reaction rate constants. In this study, we measured temperature-dependent hydroxyl radical reaction rate constants for a series of haloacetate ions and obtained their Arrhenius kinetic parameters. We found a linear correlation between these reaction rate constants and theoretically calculated aqueous-phase free energies of activation. To understand the quantitative effects on entropy of solvation due to solvent water molecules, we calculate each portion of the entropic energies that contribute to the overall aqueous phase entropy of activation; cavity formation is a dominant portion. For the series of reactions of hydroxyl radical with carboxylate ions, the increase in the entropy of activation during the solvation process is approximately 10-15 cal mol(-1)K(-1) because of interactions with solvent water molecules and the transition state. Finally, charge distribution analysis for the aqueous-phase reactions of hydroxyl radical with acetate/haloacetate ions reveals that in the aqueous phase, the degree of polarizability at the transition state is less substantial than those that are in the gaseous phase resulting in a high charge density. In the presence of electronegative halogenated functional groups, the transition state is less polarized and hydrogen bonding interactions are expected to be weaker.

  17. 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.

  18. Enantioselective aliphatic hydroxylations of racemic 1-hydroxy-3-methylcholanthrene by rat liver microsomes.

    PubMed

    Shou, M G; Yang, S K

    1990-01-01

    Enantiomeric pairs of 1-hydroxy-3-hydroxymethylcholanthrene (1-OH-3-OHMC), 3-methylcholanthrene (3MC) trans- and cis-1,2-diols, and 1-hydroxy-3-methylcholanthrene (1-OH-3MC) were resolved by HPLC using a covalently bonded (R)-N-(3,5-dinitrobenzoyl)phenylglycine chiral stationary phase (Pirkle type 1A) column. The absolute configuration of an enantiomeric 3MC trans-1,2-diol was established by the exciton chirality CD method following conversion to a bis-p-N,N-dimethylaminobenzoate. Incubation of an enantiomeric 1-OH-3MC with rat liver microsomes resulted in the formation of enantiomeric 3MC trans- and cis-1,2-diols; the absolute configurations of the enantiomeric 1-OH-3MC and 3MC cis-1,2-diol were established on the basis of the absolute configuration of an enantiomeric 3MC trans-1,2-diol. Absolute configurations of enantiomeric 1-OH-3-OHMC were determined by comparing their CD spectra with those of enantiomeric 1-OH-3MC. The relative amount of three aliphatic hydroxylation products formed by rat liver microsomal metabolism of racemic 1-OH-3MC was 1-OH-3-OHMC greater than 3MC cis-1,2-diol greater than 3MC trans-1,2-diol. Enzymatic hydroxylation at C2 of racemic 1-OH-3MC was enantioselective toward the 1S-enantiomer over the 1R-enantiomer (approximately 3/1); hydroxylation at the C3-methyl group was enantioselective toward the 1R-enantiomer over the 1S-enantiomer (approximately 58/42). Rat liver microsomal C2-hydroxylation of racemic 1-OH-3MC resulted in a 3MC trans-1,2-diol with a (1S,2S)/(1R,2R) ratio of 63/37 and a 3MC cis-1,2-diol with a (1S,2R)/(1R,2S) ratio of 12/88, respectively.

  19. 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.

  20. [Hepatitis C virus infection and alcohol].

    PubMed

    Campollo, Octavio

    2002-10-01

    It was thought that HCV infection was very frequent among alcoholics; some even though that this disease affected nearly 35% of this group. Now there seems to be a consensus among the main investigator groups that the correlation of hepatitis C and alcohol increases the risk of complications, cirrhosis and liver cancer included. Moreover, it's now certain that among patients with HCV infection, alcohol consumption increases the risk of death from live diseases during the first 10 years of the disease. Alcoholism is also considered a predisposing factor for HCV infection, but not for hepatitis B virus infection. Prospective studies about post-transfusional hepatitis C showed the risk of cirrhosis increases from 7.8 to 31.1 times if the patient consumed significant amounts of alcohol (> 80 g a day). One of the recommendations for every patient with HCV infection is to abstain from drinking alcohol.

  1. Regio- and stereoselectivity of P450-catalysed hydroxylation of steroids controlled by laboratory evolution

    NASA Astrophysics Data System (ADS)

    Kille, Sabrina; Zilly, Felipe E.; Acevedo, Juan P.; Reetz, Manfred T.

    2011-09-01

    A current challenge in synthetic organic chemistry is the development of methods that allow the regio- and stereoselective oxidative C-H activation of natural or synthetic compounds with formation of the corresponding alcohols. Cytochrome P450 enzymes enable C-H activation at non-activated positions, but the simultaneous control of both regio- and stereoselectivity is problematic. Here, we demonstrate that directed evolution using iterative saturation mutagenesis provides a means to solve synthetic problems of this kind. Using P450 BM3(F87A) as the starting enzyme and testosterone as the substrate, which results in a 1:1 mixture of the 2β- and 15β-alcohols, mutants were obtained that are 96-97% selective for either of the two regioisomers, each with complete diastereoselectivity. The mutants can be used for selective oxidative hydroxylation of other steroids without performing additional mutagenesis experiments. Molecular dynamics simulations and docking experiments shed light on the origin of regio- and stereoselectivity.

  2. Regio- and stereoselectivity of P450-catalysed hydroxylation of steroids controlled by laboratory evolution.

    PubMed

    Kille, Sabrina; Zilly, Felipe E; Acevedo, Juan P; Reetz, Manfred T

    2011-08-14

    A current challenge in synthetic organic chemistry is the development of methods that allow the regio- and stereoselective oxidative C-H activation of natural or synthetic compounds with formation of the corresponding alcohols. Cytochrome P450 enzymes enable C-H activation at non-activated positions, but the simultaneous control of both regio- and stereoselectivity is problematic. Here, we demonstrate that directed evolution using iterative saturation mutagenesis provides a means to solve synthetic problems of this kind. Using P450 BM3(F87A) as the starting enzyme and testosterone as the substrate, which results in a 1:1 mixture of the 2β- and 15β-alcohols, mutants were obtained that are 96-97% selective for either of the two regioisomers, each with complete diastereoselectivity. The mutants can be used for selective oxidative hydroxylation of other steroids without performing additional mutagenesis experiments. Molecular dynamics simulations and docking experiments shed light on the origin of regio- and stereoselectivity.

  3. Promotional effect of surface hydroxyls on electrochemical reduction of CO2 over SnOx/Sn electrode

    DOE PAGES

    Cui, Chaonan; Han, Jinyu; Zhu, Xinli; ...

    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

  4. Promotional effect of surface hydroxyls on electrochemical reduction of CO2 over SnOx/Sn electrode

    SciTech Connect

    Cui, Chaonan; Han, Jinyu; Zhu, Xinli; Liu, Xiao; Wang, Hua; Mei, Donghai; Ge, Qingfeng

    2016-11-01

    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 with 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 C-O 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 monolayer maybe formed by the reduction of the monolayer, it can be recovered by H2O dissociation, resulting in two embedded hydroxyl groups. However, 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. The work was supported in part by National Natural Sciences Foundation of China (Grant #21373148 and #21206117). The High Performance Computing

  5. Hydroxyl radical-induced formation of highly oxidized organic compounds

    NASA Astrophysics Data System (ADS)

    Berndt, Torsten; Richters, Stefanie; Jokinen, Tuija; Hyttinen, Noora; Kurtén, Theo; Otkjær, Rasmus V.; Kjaergaard, Henrik G.; Stratmann, Frank; Herrmann, Hartmut; Sipilä, Mikko; Kulmala, Markku; Ehn, Mikael

    2016-12-01

    Explaining the formation of secondary organic aerosol is an intriguing question in atmospheric sciences because of its importance for Earth's radiation budget and the associated effects on health and ecosystems. A breakthrough was recently achieved in the understanding of secondary organic aerosol formation from ozone reactions of biogenic emissions by the rapid formation of highly oxidized multifunctional organic compounds via autoxidation. However, the important daytime hydroxyl radical reactions have been considered to be less important in this process. Here we report measurements on the reaction of hydroxyl radicals with α- and β-pinene applying improved mass spectrometric methods. Our laboratory results prove that the formation of highly oxidized products from hydroxyl radical reactions proceeds with considerably higher yields than previously reported. Field measurements support these findings. Our results allow for a better description of the diurnal behaviour of the highly oxidized product formation and subsequent secondary organic aerosol formation in the atmosphere.

  6. Hydroxyl radical-induced formation of highly oxidized organic compounds

    PubMed Central

    Berndt, Torsten; Richters, Stefanie; Jokinen, Tuija; Hyttinen, Noora; Kurtén, Theo; Otkjær, Rasmus V.; Kjaergaard, Henrik G.; Stratmann, Frank; Herrmann, Hartmut; Sipilä, Mikko; Kulmala, Markku; Ehn, Mikael

    2016-01-01

    Explaining the formation of secondary organic aerosol is an intriguing question in atmospheric sciences because of its importance for Earth's radiation budget and the associated effects on health and ecosystems. A breakthrough was recently achieved in the understanding of secondary organic aerosol formation from ozone reactions of biogenic emissions by the rapid formation of highly oxidized multifunctional organic compounds via autoxidation. However, the important daytime hydroxyl radical reactions have been considered to be less important in this process. Here we report measurements on the reaction of hydroxyl radicals with α- and β-pinene applying improved mass spectrometric methods. Our laboratory results prove that the formation of highly oxidized products from hydroxyl radical reactions proceeds with considerably higher yields than previously reported. Field measurements support these findings. Our results allow for a better description of the diurnal behaviour of the highly oxidized product formation and subsequent secondary organic aerosol formation in the atmosphere. PMID:27910849

  7. Rotational Spectrum of Neopentyl Alcohol, (CH_3)_3CCH_2OH

    NASA Astrophysics Data System (ADS)

    Kisiel, Zbigniew; Pszczołkowski, Lech; Xue, Zhifeng; Suhm, Martin A.

    2012-06-01

    The rotational spectrum of neopentyl alcohol (2,2-dimethyl-1-propanol, (CH_3)_3CCH_2OH) has been investigated for the first time. This molecule differs from ethanol only in having the ^tBu group instead of the methyl group, and is likewise anticipated to exhibit two spectroscopic species, with trans and gauche hydroxyl orientation. Quantum chemistry computations predict the trans to be the more stable species. Rotational transitions of both species have now been assigned in supersonic expansion cm-wave FTMW experiment and in room temperature, mm-wave spectra up to 280 GHz. The supersonic expansion measurements with Ar carrier gas confirm that trans is the global minimum species. The trans spectrum is predominantly b-type, while the gauche is predominantly a-type and the frequencies of rotational transitions in both species appear to be perturbed in different ways. The results from effective and from coupled Hamiltonian fits for neopentyl alcohol are presented, and are compared with predictions from ab initio calculations.

  8. Communication: Hydrogen bonding interactions in water-alcohol mixtures from X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Lam, Royce K.; Smith, Jacob W.; Saykally, Richard J.

    2016-05-01

    While methanol and ethanol are macroscopically miscible with water, their mixtures exhibit negative excess entropies of mixing. Despite considerable effort in both experiment and theory, there remains significant disagreement regarding the origin of this effect. Different models for the liquid mixture structure have been proposed to address this behavior, including the enhancement of the water hydrogen bonding network around the alcohol hydrophobic groups and microscopic immiscibility or clustering. We have investigated mixtures of methanol, ethanol, and isopropanol with water by liquid microjet X-ray absorption spectroscopy on the oxygen K-edge, an atom-specific probe providing details of both inter- and intra-molecular structure. The measured spectra evidence a significant enhancement of hydrogen bonding originating from the methanol and ethanol hydroxyl groups upon the addition of water. These additional hydrogen bonding interactions would strengthen the liquid-liquid interactions, resulting in additional ordering in the liquid structures and leading to a reduction in entropy and a negative enthalpy of mixing, consistent with existing thermodynamic data. In contrast, the spectra of the isopropanol-water mixtures exhibit an increase in the number of broken alcohol hydrogen bonds for mixtures containing up to 0.5 water mole fraction, an observation consistent with existing enthalpy of mixing data, suggesting that the measured negative excess entropy is a result of clustering or micro-immiscibility.

  9. Alcohol misuse and depression in women criminals.

    PubMed

    Martin, R L; Cloninger, C R; Guze, S B

    1985-01-01

    The interaction of alcohol misuse and major depressive syndromes was examined in 66 convicted women felons. At an initial (index) evaluation and during a 6-yr follow-up, alcohol misuse and depression, although both highly prevalent, were not significantly related. Alcohol misusing and nonmisusing depressives had similar rates of treatment for depression. Follow-up alcohol misuse, occurring in one-quarter of those reinterviewed, was not predicted by an index history of depression even among index alcohol misusers. Nonsignificant trends did suggest some association between the two symptom groups. Depressive subjects with a history of alcohol misuse had a greater rate of depression during follow-up than nonmisusing index depressives. Follow-up misusers had a greater rate of follow-up depression than nonmisusers. Alcohol-related depression could not be discounted simply as a consequence of alcohol misuse. Depression in the context of alcohol misuse was highly predictive of future depression and suicide attempts. The relative independence of alcohol misuse and depression in this group underscores the complexity of their interaction, especially in a population with multiple disorders such as women criminals. The contention that phenomenologically defined major depressive disorders are heterogeneous is supported.

  10. Alcohol fuels program technical review

    SciTech Connect

    1981-07-01

    The last issue of the Alcohol Fuels Process R/D Newsletter contained a work breakdown structure (WBS) of the SERI Alcohol Fuels Program that stressed the subcontracted portion of the program and discussed the SERI biotechnology in-house program. This issue shows the WBS for the in-house programs and contains highlights for the remaining in-house tasks, that is, methanol production research, alcohol utilization research, and membrane research. The methanol production research activity consists of two elements: development of a pressurized oxygen gasifier and synthesis of catalytic materials to more efficiently convert synthesis gas to methanol and higher alcohols. A report is included (Finegold et al. 1981) that details the experimental apparatus and recent results obtained from the gasifier. The catalysis research is principally directed toward producing novel organometallic compounds for use as a homogeneous catalyst. The utilization research is directed toward the development of novel engine systems that use pure alcohol for fuel. Reforming methanol and ethanol catalytically to produce H/sub 2/ and CO gas for use as a fuel offers performance and efficiency advantages over burning alcohol directly as fuel in an engine. An application of this approach is also detailed at the end of this section. Another area of utilization is the use of fuel cells in transportation. In-house researchers investigating alternate electrolyte systems are exploring the direct and indirect use of alcohols in fuel cells. A workshop is being organized to explore potential applications of fuel cells in the transportation sector. The membrane research group is equipping to evaluate alcohol/water separation membranes and is also establishing cost estimation and energy utilization figures for use in alcohol plant design.

  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. Hydroxyl Radical Dosimetry for High Flux Hydroxyl Radical Protein Footprinting Applications Using a Simple Optical Detection Method.

    PubMed

    Xie, Boer; Sharp, Joshua S

    2015-11-03

    Hydroxyl radical protein footprinting (HRPF) by fast photochemical oxidation of proteins (FPOP) is a powerful benchtop tool used to probe protein structure, interactions, and conformational changes in solution. However, the reproducibility of all HRPF techniques is limited by the ability to deliver a defined concentration of hydroxyl radicals to the protein. This ability is impacted by both the amount of radical generated and the presence of radical scavengers in solution. In order to compare HRPF data from sample to sample, a hydroxyl radical dosimeter is needed that can measure the effective concentration of radical that is delivered to the protein, after accounting for both differences in hydroxyl radical generation and nonanalyte radical consumption. Here, we test three radical dosimeters (Alexa Fluor 488, terepthalic acid, and adenine) for their ability to quantitatively measure the effective radical dose under the high radical concentration conditions of FPOP. Adenine has a quantitative relationship between UV spectrophotometric response, effective hydroxyl radical dose delivered, and peptide and protein oxidation levels over the range of radical concentrations typically encountered in FPOP. The simplicity of an adenine-based dosimeter allows for convenient and flexible incorporation into FPOP applications, and the ability to accurately measure the delivered radical dose will enable reproducible and reliable FPOP across a variety of platforms and applications.

  13. Enzymatic hydration activity assessed by selective spectrophotometric detection of alcohols: a novel screening assay using oleate hydratase as a model enzyme.

    PubMed

    Hiseni, Aida; Medici, Rosario; Arends, Isabel W C E; Otten, Linda G

    2014-06-01

    Hydroxy fatty acids (HFAs) are high-added-value compounds, which are incorporated in polymers, lubricants, emulsifiers and stabilizers and have potential medicinal use. In nature, HFAs are regio-specifically synthesized by several enzymes, including P450 monooxygenases, lipoxygenases, hydratases, 12-hydroxylases, and diol synthases. The growing demand for HFAs warrants the development of simple and efficient analytical methods that enable high-throughput detection of the hydroxylated product in the presence of its unsaturated precursor. Herein a novel high-throughput assay for the detection of alcohols is described using oleate hydratase (OHase, EC 4.2.1.53) from Elizabethkingia meningoseptica as the model enzyme. The developed assay is based on the selective spectrophotometric detection of alkyl nitrites formed upon the reaction between the hydroxyl group and nitrous acid. The assay proved to discriminate between unsaturated fatty acids as well as small cyclic and acyclic unsaturated alkenes and their corresponding alcohols. Lower detection limits were 1.5-3 mM with excellent Z'-factors. Enzymatic reactions using OHase with oleic acid resulted in somewhat lower Z-factors for various enzyme preparations. This small scale assay can enable fast discovery of new microorganisms or improved enzymes from mutant libraries and will be useful for biocatalytic strategies involving fatty acid (de)hydrating enzymes.

  14. Mechanisms of hydroxyl radical-induced contraction of rat aorta.

    PubMed

    Li, Jianfeng; Li, Wenyan; Liu, Weimin; Altura, Bella T; Altura, Burton M

    2004-09-19

    The present study was designed to investigate the effects of hydroxyl radicals (*OH), generated via the Fe2+-mediated Fenton reaction, on isolated rat aortic rings with and without endothelium. In the absence of any vasoactive agent, generation of *OH alone elicited an endothelium-independent contraction in rat aortic rings in a concentration-dependent manner. Hydroxyl radical-induced contractions of denuded rat aortic rings appeared, however, to be slightly stronger than those on intact rat aortic rings. The contractile responses to *OH were neither reversible nor reproducible in the same ring; even small concentrations of *OH radicals resulted in tachyphylaxis. Removal of extracellular calcium ions (Ca2+) or buffering intracellular Ca2+ with 10 microM acetyl methyl ester of bis(o-aminophenoxy) ethane-N,N,N',N',-tetraacetic acid (BAPTA-AM) significantly attenuated the contractile actions of *OH radicals. The presence of 1 microM staurosporine, 1 microM bisindolylmaleimide I, 1 microM Gö6976 [inhibitor of protein kinase C (PKC)], 2 microM PD-980592 (inhibitor of ERK), 10 microM genistein, and 1 microM wortmannin significantly inhibited the contractions induced by *OH. Proadifen (10 microM), on the other hand, significantly potentiated the hydroxyl radical-induced contractions. Exposure of primary cultured aortic smooth muscle cells to *OH produced significant, rapid rises of intracellular free Ca2+ ([Ca2+]i). Several, specific antagonists of possible endogenously formed vasoconstrictors did not inhibit or attenuate either hydroxyl radical-induced contractions or the elevation of [Ca2+]i. Our new results suggest that hydroxyl radical-triggered contractions on rat aortic rings are Ca2+-dependent. Several intracellular signal transduction systems seem to play some role in hydroxyl radical-induced vasoconstriction of rat aortic rings.

  15. Genetic markers in alcoholic liver cirrhosis.

    PubMed

    Lareu, M V; Alvarez-Prechous, A; Pardiñas, C; Concheiro, L; Carracedo, A

    1992-01-01

    11 genetic markers were typed in 157 individuals suffering from alcoholic cirrhosis, and compared with a random sample of healthy individuals. No significant differences were found for transferrin, specific group component, orosomucoid, esterase D, phosphogluconate dehydrogenase and adenylate kinase. Strong associations between alcoholic cirrhosis and alpha-1-antitrypsin PI*Z allele, haptoglobin HP*1 allele and acid phosphatase ACP AC phenotype were observed. The biological significance of these associations and their relationships with the development of alcoholic cirrhosis are also discussed.

  16. 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

  17. 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.

  18. 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.

  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. 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.

  1. Arabidopsis CYP98A3 Mediating Aromatic 3-Hydroxylation. Developmental Regulation of the Gene, and Expression in Yeast1

    PubMed Central

    Nair, Ramesh B.; Xia, Qun; Kartha, Cyril J.; Kurylo, Eugen; Hirji, Rozina N.; Datla, Raju; Selvaraj, Gopalan

    2002-01-01

    The general phenylpropanoid pathways generate a wide array of aromatic secondary metabolites that range from monolignols, which are ubiquitous in all plants, to sinapine, which is confined to crucifer seeds. The biosynthesis of these compounds involves hydroxylated and methoxylated cinnamyl acid, aldehyde, or alcohol intermediates. Of the three enzymes originally proposed to hydroxylate the 4-, 3-, and 5-positions of the aromatic ring, cinnamate 4-hydroxylase (C4H), which converts trans-cinnamic acid to p-coumaric acid, is the best characterized and is also the archetypal plant P450 monooxygenase. Ferulic acid 5-hydroxylase (F5H), a P450 that catalyzes 5-hydroxylation, has also been studied, but the presumptive 3-hydroxylase converting p-coumarate to caffeate has been elusive. We have found that Arabidopsis CYP98A3, also a P450, could hydroxylate p-coumaric acid to caffeic acid in vivo when expressed in yeast (Saccharomyces cerevisiae) cells, albeit very slowly. CYP98A3 transcript was found in Arabidopsis stem and silique, resembling both C4H and F5H in this respect. CYP98A3 showed further resemblance to C4H in being highly active in root, but differed from F5H in this regard. In transgenic Arabidopsis, the promoters of CYP98A3 and C4H showed wound inducibility and a comparable developmental regulation throughout the life cycle, except in seeds, where the CYP98A3 promoter construct was inactive while remaining active in silique walls. Within stem and root tissue, the gene product and the promoter activity of CYP98A3 were most abundant in lignifying cells. Collectively, these studies show involvement of CYP98A3 in the general phenylpropanoid metabolism, and suggest a downstream function for CYP98A3 relative to the broader and upstream role of C4H. PMID:12226501

  2. Identification of hydroxyl protons, determination of their exchange dynamics, and characterization of hydrogen bonding in a microcrystallin protein.

    PubMed

    Agarwal, Vipin; Linser, Rasmus; Fink, Uwe; Faelber, Katja; Reif, Bernd

    2010-03-10

    Heteronuclear correlation experiments employing perdeuterated proteins enable the observation of all hydroxyl protons in a microcrystalline protein by MAS solid-state NMR. Dipolar-based sequences allow magnetization transfers that are >50 times faster compared to scalar-coupling-based sequences, which significantly facilitates their assignment. Hydroxyl exchange rates were measured using EXSY-type experiments. We find a biexponential decay behavior for those hydroxyl groups that are involved in side chain-side chain C-O-H...O horizontal lineC hydrogen bonds. The quantification of the distances between the hydroxyl proton and the carbon atoms in the hydrogen-bonding donor as well as acceptor group is achieved via a REDOR experiment. In combination with X-ray data and isotropic proton chemical shifts, availability of (1)H,(13)C distance information can aid in the quantitative description of the geometry of these hydrogen bonds. Similarly, correlations between backbone amide proton and carbonyl atoms are observed, which will be useful in the analysis of the registry of beta-strand arrangement in amyloid fibrils.

  3. Older Adults and Alcohol

    MedlinePlus

    ... Alcohol Exposure Support & Treatment Alcohol Policy Special Populations & Co-occurring Disorders Publications & Multimedia Brochures & Fact Sheets NIAAA ... are here Home » Alcohol & Your Health » Special Populations & Co-occurring Disorders » Older Adults In this Section Underage ...

  4. Fetal Alcohol Syndrome

    MedlinePlus

    ... The diagnosis of fetal alcohol syndrome. Deutsches Arztebaltt International. 2013;110:703. Ungerer M, et al. In utero alcohol exposure, epigenetic changes and their consequences. Alcohol Research: Current Reviews. 2013;35:37. Coriale G, et al. ...

  5. Fetal Alcohol Syndrome

    MedlinePlus

    ... Conditions Frequently Asked Questions Español Condiciones Chinese Conditions Fetal Alcohol Syndrome Read in Chinese What is Fetal Alcohol Syndrome (FAS)? Fetal Alcohol Syndrome (FAS) describes changes in ...

  6. Alcoholic liver disease

    MedlinePlus

    Liver disease due to alcohol; Cirrhosis or hepatitis - alcoholic; Laennec's cirrhosis ... Alcoholic liver disease occurs after years of heavy drinking. Over time, scarring and cirrhosis can occur. Cirrhosis is the ...

  7. Sum Frequency Vibrational Spectroscopy (SFVS) of Water and Hydroxyls on the Corundum (1-102) surface: Acid-base properties from direct observation of protonation states

    NASA Astrophysics Data System (ADS)

    Waychunas, G.; Sung, J.; Shen, R.

    2010-12-01

    SFVS is a powerful tool for quantitative measurement of protonated functional groups on mineral surfaces. We demonstrate this for the Corundum (1-102) interface where the orientation and nature of surface hydroxyls on the dry neutral surface can be obtained and compared with Crystal Truncation Rod (CTR) models for the surface termination and most likely functional groups, effectively allowing testing of such models. A scheme for describing the hydrogen bonding among these protonated groups is found to be consistent with surface symmetry and the particular vibrational frequencies observed. The addition of water to the interface alters the hydrogen bonding of the hydroxyls and introduces water-functional group hydrogen bonding. Direct measurement of the SFVS hydroxyl and water band amplitudes can be used to test expected pKa values, and hence link acid-base properties to precise molecular surface entities. The analysis methodology can be applied to analogous nanoparticle surfaces, though with some limitations.

  8. Monoamine oxidases and alcoholism: studies in unrelated alcoholics, normal controls and alcoholic families.

    PubMed

    Parsian, A; Suarez, B K; Tabakoff, B; Hoffman, P; Ovchinnikova, L; Fisher, L; Cloninger, C R

    1994-01-01

    Monoamine oxidases (A and B) are of great interest in connection with alcoholism. Low MAO activity has been found in the brains and the platelets of alcoholics and their relatives supporting the hypothesis that low MAO activity is a biological marker for vulnerability to misuse. In order to determine the role of the MAO genes in alcoholism we have measured MAO-B activity and typed two simple sequence repeats (one in the MAO-A gene and one in the MAO-B gene) in a sample of 133 unrelated alcoholics, 300 subjects from 30 two- and three-generation pedigrees ascertained through an alcoholic proband, and 92 normal controls. The unrelated alcoholic group did not differ in MAO-B activity from normal controls nor were there significant differences between subtypes. We did, however, find significant differences between alcoholic males and females (t = 2.836, p = .005), a difference that was not present in controls. A two-way analysis of variance of MAO-B activity as a function of the allelic variation of each marker locus and diagnosis among male subjects was performed. There was no evidence for mean differences in activity levels for different alleles. The distribution of MAO-A and MAO-B "alleles" in the alcoholic sample differed from that of the control sample. Affected sib pair linkage analysis of MAO genes and alcoholism showed no evidence for an excess of concordant affected sib pairs suggesting that this region of the X-chromosome does not harbor a susceptibility locus.

  9. 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

  10. Alcohol-involved Assault: Associations with posttrauma alcohol use, consequences, and expectancies

    PubMed Central

    Bedard-Gilligan, Michele; Kaysen, Debra; Desai, Sruti; Lee, Christine M.

    2011-01-01

    Victim alcohol consumption is common prior to sexual assault, and a burgeoning literature suggests that victims who were intoxicated during assault may differ in post-assault adjustment compared to those who were not impaired. Less is known about potential relationships between experiencing an alcohol-involved assault (AIA) and later drinking behavior. In this study, we examined the relationships between sexual assault, subsequent drinking behavior and consequences, and alcohol expectancies in a sample of 306 undergraduate women who reported current alcohol use and reported either no trauma history (n = 53), non-AIA (n = 69), or AIA (n = 184). Differences emerged for alcohol use (F(2, 298) = 12.78, p < .001), peak blood alcohol content (F(2, 298) = 9.66, p < .001), consequences (F(2, 296) = 7.38, p < .005), and positive alcohol expectancies (F(14, 796) = 1.93, p < .05). In particular, women with an AIA reported greater alcohol use and positive expectancies compared to women with no trauma history and women with a non-alcohol influenced assault. In addition, both assault groups reported greater drinking consequences than women with no trauma history. Findings suggest that it is the women who are assaulted while under the influence of alcohol who evidence more alcohol use and alcohol-related problems following assault. PMID:21813246

  11. Reactions of hydroxyl radicals with alkenes in low-temperature matrices

    NASA Astrophysics Data System (ADS)

    Feltham, Emma J.; Almond, Matthew J.; Marston, George; Wiltshire, Karen S.; Goldberg, Nicola

    2000-11-01

    The reactions of hydroxyl radicals with a number of stable alkenes have been studied in low-temperature matrices. The reactions were initiated by broad band UV-visible irradiation of matrices containing H 2O 2 and the alkene under investigation. The hydroxyalkyl radical products were identified principally by comparison of their spectra with the spectra of corresponding stable alcohols. Accordingly, IR spectra were recorded for the following series of alcohols isolated in argon matrices — methanol, ethanol, ethanol- d6, propan-1-ol, propan-2-ol, butan-2-ol, 2-methylpropan-1-ol ( iso-butyl alcohol), 2-methylpropan-2-ol ( tert-butyl alcohol), 2-methylbutan-2-ol ( tert-amyl alcohol), 3-methylbutan-2-ol and 2,3-dimethylbutan-2-ol. The hydroxyalkyl radicals, which appear to be formed from the alkenes studied were as follows — from ethene, 2-hydroxyethyl radical; from cis- or trans-but-2-ene, 1-methyl-2-hydroxypropyl radical; from propene, 1-methyl-2-hydroxyethyl and 2-hydroxypropyl radicals; from but-1-ene, 1-hydroxymethylpropyl and 2-hydroxybutyl radicals; from 2-methylpropene ( iso-butene), 1,1-dimethyl-2-hydroxyethyl and 2-methyl-2-hydroxypropyl radicals; the radical products from buta-1,3-diene and isoprene could not be identified. In the cases, where two radical products were possible, i.e. when propene, but-1-ene or 2-methylpropene were the substrates, it was found that the concentration of the secondary or tertiary radical always exceeded that of the primary radical. However, the relative concentration of these radicals appears to be determined by subsequent photolysis to give carbonyl compounds. There seems, therefore, to be little preference for the secondary and tertiary radicals over the primary radicals in the primary addition process. Comments on the mechanism of the transformation from radical to carbonyl compound based upon identification of intermediates within the matrix and isotopic substitution experiments are made. The characterisation of the 2

  12. Effects of forced alcohol drinking on alcohol-water choice in three pairs of rat lines selectively bred for differences in alcohol preference.

    PubMed

    Timberlake, William; Leffel, Joseph K; Chester, Julia A; Froehlich, Janice C

    2009-03-01

    Three pairs of Indiana University rat lines (inbred alcohol-preferring and nonpreferring rat lines [P/NPs], high- and low-alcohol-drinking rat lines [HAD/LAD1s and HAD/LAD2s]) were bred in the School of Medicine colony to drink high versus low daily amounts of a 10% vol/vol alcohol test solution (>5.0 g/kg body weight vs. <1.5 g/kg body weight), and a high versus low proportion of alcohol to water (>2:1 vs. <0.5:1) by the end of a 3-week alcohol-water choice condition. This choice phase was always preceded by four days of a forcing procedure with alcohol as the only fluid. The present study examined the contribution of the forcing procedure to the alcohol intake of animals in each pair of lines by comparing daily alcohol intake of rats housed in experimental chambers in a forced group (4 days with only alcohol solution to drink followed by 22 choice days) versus a choice group (both alcohol and water available all 26 days). As expected, under the initial alcohol exposure, high-drinking line rats drank more alcohol than low-drinking line rats, and all forced groups drank more alcohol than choice groups. At the start of the choice phase, all low-drinking line forced groups immediately dropped their alcohol intake to the level of their choice groups. In contrast, all high-drinking line forced groups maintained a high level of alcohol intake under choice, whereas all high-drinking line choice groups slowly increased average alcohol intake across the 22-day choice phase, ending near the average intake of their forced groups. However, a small subset of each high-drinking line choice animals failed to increase alcohol intake until subsequently forced with alcohol for 4 days and tested again in choice. These results indicate that the alcohol-forcing procedure used in deriving these lines resulted in the selection of more than one pathway to a high-drinking phenotype. In addition, high-drinking line animals appeared more sensitive to the differences between laboratory- and

  13. Purification and properties of methyl formate synthase, a mitochondrial alcohol dehydrogenase, participating in formaldehyde oxidation in methylotrophic yeasts.

    PubMed Central

    Murdanoto, A P; Sakai, Y; Konishi, T; Yasuda, F; Tani, Y; Kato, N

    1997-01-01

    Methyl formate synthase, which catalyzes methyl formate formation during the growth of methylotrophic yeasts, was purified to homogeneity from methanol-grown Candida boidinii and Pichia methanolica cells. Both purified enzymes were tetrameric, with identical subunits with molecular masses of 42 to 45 kDa, containing two atoms of zinc per subunit. The enzymes catalyze NAD(+)-linked dehydrogenation of the hydroxyl group of the hemiacetal adduct [CH2(OH)OCH3] of methanol and formaldehyde, leading to the formation of a stoichiometric amount of methyl formate. Although neither methanol nor formaldehyde alone acted as a substrate for the enzymes, they showed simple NAD(+)-linked alcohol dehydrogenase activity toward aliphatic long-chain alcohols such as octanol, showing that they belong to the class III alcohol dehydrogenase family. The methyl formate synthase activity of C. boidinii was found in the mitochondrial fraction in subcellular fractionation experiments, suggesting that methyl formate synthase is a homolog of Saccharomyces cerevisiae Adh3p. These results indicate that formaldehyde could be oxidized in a glutathione-independent manner by methyl formate synthase in methylotrophic yeasts. The significance of methyl formate synthase in both formaldehyde resistance and energy metabolism is also discussed. PMID:9143107

  14. Size distribution of associated clusters in liquid alcohols: Interpretation of simulation results in the frame of SAFT approach

    NASA Astrophysics Data System (ADS)

    Janeček, Jiří; Paricaud, Patrice

    2013-11-01

    The size distribution and topology of associated clusters for primary alcohols is studied using molecular dynamics simulations. Liquid ethanol, propanol, butanol, hexanol, and octanol are simulated at pressure P = 1 bar and temperatures T = 300 K, T = 350 K, and T = 400 K. The fractions of molecules with different sets of hydrogen bonded partners, the size of associated cluster and the site-site distribution functions between atoms participating on hydrogen bonding are extracted from simulated trajectories. For all alcohols longer than ethanol, the length of the alkyl chain has only a marginal effect on the association. Consequently, related properties like coordination numbers of hydroxyl group, size distribution of associates, or fractions of differently coordinated alcohol molecules are independent on the molecular size. Although we employed a force-field without involved polarizability, we observe a positive cooperativity of hydrogen bonding simply as a consequence of steric and electrostatic interactions. The size and topology of associates is analyzed within the frame of 3B model of statistical association fluid theory. Although this approach enables good thermodynamic description of systems containing associating compounds, several insufficiencies appear in the description at molecular level.

  15. Hydroxyl radical Thymine adduct induced DNA damages

    NASA Astrophysics Data System (ADS)

    Schyman, Patric; Eriksson, Leif A.; Zhang, Ru bo; Laaksonen, Aatto

    2008-06-01

    DNA damages caused by a 5-hydroxy-5,6-dihydrothymine-6-yl radical (5-OHT-6yl) abstracting a C2‧ hydrogen from a neighboring sugar (inter-H abstraction) have been theoretically investigated using hybrid DFT in gas phase and in water solution. The inter-H abstraction was here shown to be comparable in energy (24 kcal mol-1) with the intra-H abstraction in which the 5-OHT-6yl abstracts a C2‧ hydrogen from its own sugar. The effect of a neutrally or a negatively charged phosphate group was also studied and the results show no significant impact on the activation energy of the hydrogen abstraction whereas base release and strand break reactions are affected.

  16. 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.

  17. Hydroxyl radical reactivity at the air-ice interface

    NASA Astrophysics Data System (ADS)

    Kahan, T. F.; Zhao, R.; Donaldson, D. J.

    2010-01-01

    Hydroxyl radicals are important oxidants in the atmosphere and in natural waters. They are also expected to be important in snow and ice, but their reactivity has not been widely studied in frozen aqueous solution. We have developed a spectroscopic probe to monitor the formation and reactions of hydroxyl radicals in situ. Hydroxyl radicals are produced in aqueous solution via the photolysis of nitrite, nitrate, and hydrogen peroxide, and react rapidly with benzene to form phenol. Similar phenol formation rates were observed in aqueous solution and bulk ice. However, no reaction was observed at air-ice interfaces, or when bulk ice samples were crushed prior to photolysis to increase their surface area. We also monitored the heterogeneous reaction between benzene present at air-water and air-ice interfaces with gas-phase OH produced from HONO photolysis. Rapid phenol formation was observed on water surfaces, but no reaction was observed at the surface of ice. Under the same conditions, we observed rapid loss of the polycyclic aromatic hydrocarbon (PAH) anthracene at air-water interfaces, but no loss was observed at air-ice interfaces. Our results suggest that the reactivity of hydroxyl radicals toward aromatic organics is similar in bulk ice samples and in aqueous solution, but is significantly suppressed in the quasi-liquid layer (QLL) that exists at air-ice interfaces.

  18. Hydroxyl radical reactivity at the air-ice interface

    NASA Astrophysics Data System (ADS)

    Kahan, T. F.; Zhao, R.; Donaldson, D. J.

    2009-10-01

    Hydroxyl radicals are important oxidants in the atmosphere and in natural waters. They are also expected to be important in snow and ice, but their reactivity has not been widely studied in frozen aqueous solution. We have developed a spectroscopic probe to monitor the formation and reactions of hydroxyl radicals in situ. Hydroxyl radicals are produced in aqueous solution via the photolysis of nitrite, nitrate, and hydrogen peroxide, and react rapidly with benzene to form phenol. Similar phenol formation rates were observed in aqueous solution and bulk ice. However, no reaction was observed at the air-ice interface, or when bulk ice samples were crushed prior to photolysis to increase their surface area. We also monitored the heterogeneous reaction between benzene present at air-water and air-ice interfaces with gas-phase OH produced from HONO photolysis. Rapid phenol formation was observed on water surfaces, but no reaction was observed at the surface of ice. Under the same conditions, we observed rapid loss of the polycyclic aromatic hydrocarbon (PAH) anthracene at the air-water interface, but no loss was observed at the air-ice interface. Our results suggest that the reactivity of hydroxyl radicals toward aromatic organics is similar in bulk ice samples and in aqueous solution, but is significantly suppressed in the quasi-liquid layer (QLL) that exists at the air-ice interface.

  19. 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.

  20. Hydroxyl Radical and Its Scavengers in Health and Disease

    PubMed Central

    Lipinski, Boguslaw

    2011-01-01

    It is generally believed that diseases caused by oxidative stress should be treated with antioxidants. However, clinical trials with such antioxidants as ascorbic acid and vitamin E, failed to produce the expected beneficial results. On the other hand, important biomolecules can be modified by the introduction of oxygen atoms by means of non-oxidative hydroxyl radicals. In addition, hydroxyl radicals can reduce disulfide bonds in proteins, specifically fibrinogen, resulting in their unfolding and scrambled refolding into abnormal spatial configurations. Consequences of this reaction are observed in many diseases such as atherosclerosis, cancer and neurological disorders, and can be prevented by the action of non-reducing substances. Moreover, many therapeutic substances, traditionally classified as antioxidants, accept electrons and thus are effective oxidants. It is described in this paper that hydroxyl radicals can be generated by ferric ions without any oxidizing agent. In view of the well-known damaging effect of poorly chelated iron in the human body, numerous natural products containing iron binding agents can be essential in the maintenance of human health. However, beneficial effects of the great number of phytochemicals that are endowed with hydroxyl radical scavenging and/or iron chelating activities should not be considered as a proof for oxidative stress. PMID:21904647

  1. 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.

  2. 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.

  3. ALCOHOL. . . .NARCOTICS EDUCATION, A HANDBOOK FOR TEACHERS.

    ERIC Educational Resources Information Center

    CHRISTIAN, FLOYD T.

    THIS HANDBOOK WHICH THE TEACHER MAY USE IN PLANNING COURSES OF STUDY IS INTENDED TO SUPPLY FACTUAL DATA IN REGARD TO THE USES OF ALCOHOL AND NARCOTICS. THE INFORMATION IS APPLICABLE TO ANY GROUP OR GRADE LEVEL, BUT IT IS PRIMARILY DIRECTED FOR K-12 PROGRAMS. THE HANDBOOK IS IN THREE SECTIONS. THE FIRST INCLUDES FACTS ABOUT BEVERAGE ALCOHOL.…

  4. Career Indecision in Adult Children of Alcoholics.

    ERIC Educational Resources Information Center

    Skorupa, Jessica; Agresti, Albert A.

    1998-01-01

    Utilizes a sample of community college students to investigate differences in career indecision of adult children of alcoholics (ACOAs) and adult children of non-alcoholics. Although both groups were similar in their overall levels of career indecision, there were significant relationships among irrational thinking, trait anxiety, and career…

  5. [Nicotine abusing in adult children of alcoholics].

    PubMed

    Suwała, Małgorzata

    2010-01-01

    Adult Children of Alcoholics (ACA) are people who were raised in families abusing alcohol where one of the parents (or both) was addicted to alcohol and where alcohol was the main problem affecting all areas of life. It is estimated that in Poland adult population consists of ACA in 35-40%. Those people represent higher risk of addiction to psychoactive substances, most of all alcohol, but also nicotine. Higher addiction propensity among ACA is a result of their personality's features consisting so called "ACA syndrome". The goal of the study was to determine nicotine addiction frequency and assessment of self-propensity to addiction in chosen ACA group, gathered in three abstinent clubs for alcoholics in Warsaw. Nicotine addiction frequency among the study group members was 58.4% and alcohol addiction frequency was 21.2%. Strong nicotine addiction represented 49.2% of smokers. Men more often than women were addicted to nicotine (0.67 vs. 0.52), on the other hand women were more often than men alcohol addicts (0.18 vs. 0.15). All smokers and nicotine addicts (assessment by HIS test) were aware of their addiction. In relation to initial addiction diagnosis by CAGE test regarded higher percentage of people than it resulted from study group self-assessment (21.2% vs. 16.8). Professional psychotherapy for ACA did not influence substantially the nicotine addiction frequency in the study group.

  6. Trajectories of alcohol and drug use and dependence from adolescence to adulthood: the effects of familial alcoholism and personality.

    PubMed

    Chassin, Laurie; Fora, David B; King, Kevin M

    2004-11-01

    This study describes trajectories of substance use and dependence from adolescence to adulthood. Identified consumption groups include heavy drinking/heavy drug use, moderate drinking/experimental drug use, and light drinking/rare drug use. Dependence groups include alcohol only, drug only, and comorbid groups. The heavy drinking/heavy drug use group was at risk for alcohol and drug dependence and persistent dependence and showed more familial alcoholism, negative emotionality, and low constraint. The moderate drinking/experimental drug use group was at risk for alcohol dependence but not comorbid or persistent dependence and showed less negative emotionality and higher constraint. Familial alcoholism raised risk for alcohol and drug use and dependence in part because children from alcoholic families were more impulsive and lower in agreeableness.

  7. Topographic quantitative EEG amplitude in recovered alcoholics.

    PubMed

    Pollock, V E; Schneider, L S; Zemansky, M F; Gleason, R P; Pawluczyk, S

    1992-05-01

    Topographic measures of electroencephalographic (EEG) amplitude were used to compare recovered alcoholics (n = 14) with sex- and age-matched control subjects. Delta, alpha, and beta activity did not distinguish the groups, but regional differences in theta distribution did. Recovered alcoholics showed more uniform distributions of theta amplitudes in bilateral anterior and posterior regions compared with controls. Because a minimum of 5 years had elapsed since the recovered alcoholic subjects fulfilled DSM-III-R criteria for alcohol abuse or dependence, it is unlikely these EEG theta differences reflect the effects of withdrawal.

  8. Congener-specific numbering systems for the environmentally relevant C4 through C8 perfluorinated homologue groups of alkyl sulfonates, carboxylates, telomer alcohols, olefins, and acids, and their derivatives.

    PubMed

    Rayne, Sierra; Forest, Kaya; Friesen, Ken J

    2008-10-01

    We introduce a congener-specific numbering system for the C4 through C8 perfluorinated homologue groups of alkyl sulfonates, carboxylates, telomer alcohols, olefins, and acids, and their derivatives. Increasing length of the carbon chain beyond C3 leads to a corresponding rapid increase in the number of potential isomers (C4 = 4, C5 = 8, C6 = 17, C7 = 39, and C8 = 89 congeners). There is a need for clear and unambiguous chemical shorthand to ensure accuracy and consistency in the future perfluorinated alkyl substance (PFA) literature, and to correct previous misconceptions that may have restricted research efforts into developing full-congener PFA analysis. If adopted by the research community, introduction of a numbering system at this relatively early stage of investigations into the congener-specific analysis, environmental behavior, and toxicology of PFAs would not require an arduous and difficult reassignment of historical structures and naming conventions presented in the prior art. Many PFA congeners are chiral, necessitating a consideration of their enantiospecific environmental behavior and toxicology.

  9. Stereospecific alkane hydroxylation by non-heme iron catalysts: mechanistic evidence for an Fe(V)=O active species.

    PubMed

    Chen, K; Que, L

    2001-07-04

    High-valent iron-oxo species have frequently been invoked in the oxidation of hydrocarbons by both heme and non-heme enzymes. Although a formally Fe(V)=O species, that is, [(Por(*))Fe(IV)=O](+), has been widely accepted as the key oxidant in stereospecific alkane hydroxylation by heme systems, it is not established that such a high-valent state can be accessed by a non-heme ligand environment. Herein we report a systematic study on alkane oxidations with H(2)O(2) catalyzed by a group of non-heme iron complexes, that is, [Fe(II)(TPA)(CH(3)CN)(2)](2+) (1, TPA = tris(2-pyridylmethyl)amine) and its alpha- and beta-substituted analogues. The reactivity patterns of this family of Fe(II)(TPA) catalysts can be modulated by the electronic and steric properties of the ligand environment, which affects the spin states of a common Fe(III)-OOH intermediate. Such an Fe(III)-peroxo species is high-spin when the TPA ligand has two or three alpha-substituents and is proposed to be directly responsible for the selective C-H bond cleavage of the alkane substrate. The thus-generated alkyl radicals, however, have relatively long lifetimes and are susceptible to radical epimerization and trapping by O(2). On the other hand, 1 and the beta-substituted Fe(II)(TPA) complexes catalyze stereospecific alkane hydroxylation by a mechanism involving both a low-spin Fe(III)-OOH intermediate and an Fe(V)=O species derived from O-O bond heterolysis. We propose that the heterolysis pathway is promoted by two factors: (a) the low-spin iron(III) center which weakens the O-O bond and (b) the binding of an adjacent water ligand that can hydrogen bond to the terminal oxygen of the hydroperoxo group and facilitate the departure of the hydroxide. Evidence for the Fe(V)=O species comes from isotope-labeling studies showing incorporation of (18)O from H(2)(18)O into the alcohol products. (18)O-incorporation occurs by H(2)(18)O binding to the low-spin Fe(III)-OOH intermediate, its conversion to a cis-H(18)O

  10. Loss of flexibility in alcohol-taking rats: promoting factors.

    PubMed

    Turyabahika-Thyen, Katja; Wolffgramm, Jochen

    2006-01-01

    Alcohol consumption in humans can move from a flexible pattern of intake to an inflexible (addictive) one. Several endogenous and exogenous factors are discussed to be involved in this transition. The purpose of this study was to examine factors that might promote the development of inflexibility. Over a period of 52 weeks (long-term) rats had continuously free choice between differently concentrated alcohol solutions and tap water (four-bottle paradigm). After 4 months of alcohol deprivation, a retest with free choice of alcohol was performed. Bitter-taste conditions were used to test the flexibility of alcohol taking. In the retest alcohol-experienced rats revealed a much higher alcohol intake than previously alcohol-naive ones. Part of the alcohol-experienced animals showed impairment of flexibility in alcohol taking. During long-term choice, some groups were submitted to experimental interventions that might affect addiction development (stress, withdrawal, limited access, adverse consequences). Rats with limited access to alcohol at the end of the long-term choice period took more alcohol and were less flexible in the retest than any other group. It is suggested that an unsatisfied urge for alcohol leads to impairment of control over alcohol drinking.

  11. Strengthening the Canadian alcohol advertising regulatory system.

    PubMed

    Heung, Carly M; Rempel, Benjamin; Krank, Marvin

    2012-05-24

    Research evidence points to harmful effects from alcohol advertising among children and youth. In particular, exposure to alcohol advertising has been associated with adolescents drinking both earlier and heavier. Although current federal and provincial guidelines have addressed advertising practices to prevent underage drinking, practice has not been supported by existing policy. While protective measures such as social marketing campaigns have the potential for counteracting the effects from alcohol advertising, the effectiveness of such measures can be easily drowned out with increasing advertising activities from the alcohol industry, especially without effective regulation. Research reviewed by the European Focus on Alcohol Safe Environment (FASE) Project has identified a set of key elements that are necessary to make alcohol advertising policy measures effective at protecting children and youth from the harmful effects of alcohol marketing. Using these key elements as an evaluation framework, there are critical components in the Canadian alcohol advertising regulatory system that clearly require strengthening. To protect impressionable children and youth against the harmful effects of alcohol advertising, 13 recommendations to strengthen current alcohol advertising regulations in Canada are provided for Canadian policy-makers, advertising standard agencies, and public health groups.

  12. Biological role of prolyl 3-hydroxylation in type IV collagen.

    PubMed

    Pokidysheva, Elena; Boudko, Sergei; Vranka, Janice; Zientek, Keith; Maddox, Kerry; Moser, Markus; Fässler, Reinhard; Ware, Jerry; Bächinger, Hans Peter

    2014-01-07

    Collagens constitute nearly 30% of all proteins in our body. Type IV collagen is a major and crucial component of basement membranes. Collagen chains undergo several posttranslational modifications that are indispensable for proper collagen function. One of these modifications, prolyl 3-hydroxylation, is accomplished by a family of prolyl 3-hydroxylases (P3H1, P3H2, and P3H3). The present study shows that P3H2-null mice are embryonic-lethal by embryonic day 8.5. The mechanism of the unexpectedly early lethality involves the interaction of non-3-hydroxylated embryonic type IV collagen with the maternal platelet-specific glycoprotein VI (GPVI). This interaction results in maternal platelet aggregation, thrombosis of the maternal blood, and death of the embryo. The phenotype is completely rescued by producing double KOs of P3H2 and GPVI. Double nulls are viable and fertile. Under normal conditions, subendothelial collagens bear the GPVI-binding sites that initiate platelet aggregation upon blood exposure during injuries. In type IV collagen, these sites are normally 3-hydroxylated. Thus, prolyl 3-hydroxylation of type IV collagen has an important function preventing maternal platelet aggregation in response to the early developing embryo. A unique link between blood coagulation and the ECM is established. The newly described mechanism may elucidate some unexplained fetal losses in humans, where thrombosis is often observed at the maternal/fetal interface. Moreover, epigenetic silencing of P3H2 in breast cancers implies that the interaction between GPVI and non-3-hydroxylated type IV collagen might also play a role in the progression of malignant tumors and metastasis.

  13. Redox regulation of protein tyrosine phosphatase activity by hydroxyl radical.

    PubMed

    Meng, Fan-Guo; Zhang, Zhong-Yin

    2013-01-01

    Substantial evidence suggests that transient production of reactive oxygen species (ROS) such as hydrogen peroxide (H(2)O(2)) is an important signaling event triggered by the activation of various cell surface receptors. Major targets of H(2)O(2) include protein tyrosine phosphatases (PTPs). Oxidation of the active site Cys by H(2)O(2) abrogates PTP catalytic activity, thereby potentially furnishing a mechanism to ensure optimal tyrosine phosphorylation in response to a variety of physiological stimuli. Unfortunately, H(2)O(2) is poorly reactive in chemical terms and the second order rate constants for the H(2)O(2)-mediated PTP inactivation are ~10M(-1)s(-1), which is too slow to be compatible with the transient signaling events occurring at the physiological concentrations of H(2)O(2). We find that hydroxyl radical is produced from H(2)O(2) solutions in the absence of metal chelating agent by the Fenton reaction. We show that the hydroxyl radical is capable of inactivating the PTPs and the inactivation is active site directed, through oxidation of the catalytic Cys to sulfenic acid, which can be reduced by low molecular weight thiols. We also show that hydroxyl radical is a kinetically more efficient oxidant than H(2)O(2) for inactivating the PTPs. The second-order rate constants for the hydroxyl radical-mediated PTP inactivation are at least 2-3 orders of magnitude higher than those mediated by H(2)O(2) under the same conditions. Thus, hydroxyl radical generated in vivo may serve as a more physiologically relevant oxidizing agent for PTP inactivation. This article is part of a Special Issue entitled: Chemistry and mechanism of phosphatases, diesterases and triesterases.

  14. Mechanisms of hyponatraemia in alcohol patients.

    PubMed

    Liamis, G L; Milionis, H J; Rizos, E C; Siamopoulos, K C; Elisaf, M S

    2000-01-01

    Hyponatraemia is commonly reported in chronic alcoholic patients. However, the underlying pathogenetic mechanisms are not well delineated. In the current study, we analysed the possible pathophysiological mechanisms of hyponatraemia in a group of alcoholic patients (n = 127) admitted to our hospital for causes related to alcohol misuse. Hyponatraemia (serum sodium <134 mmol/l) was found in 22 patients (17.3%). The most common cause of hyponatraemia in our cohort was hypovolaemia (12 patients); pseudohyponatraemia was diagnosed in six patients with alcohol-induced severe hypertriglyceridaemia. It is of interest that two patients fulfilled the criteria of the so-called 'beer potomania' syndrome, while in two others, hyponatraemia was due to reset osmostat or to cerebral salt wasting syndrome, not previously described in alcoholic patients. It is concluded that hyponatraemia is a frequently observed electrolyte disorder in hospitalized alcoholic patients and is related to various pathophysiological mechanisms.

  15. Associations Between Socioeconomic Factors and Alcohol Outcomes.

    PubMed

    Collins, Susan E

    2016-01-01

    Socioeconomic status (SES) is one of the many factors influencing a person's alcohol use and related outcomes. Findings have indicated that people with higher SES may consume similar or greater amounts of alcohol compared with people with lower SES, although the latter group seems to bear a disproportionate burden of negative alcohol-related consequences. These associations are further complicated by a variety of moderating factors, such as race, ethnicity, and gender. Thus, among individuals with lower SES, members of further marginalized communities, such as racial and ethnic minorities and homeless individuals, experience greater alcohol-related consequences. Future studies are needed to more fully explore the underlying mechanisms of the relationship between SES and alcohol outcomes. This knowledge should be applied toward the development of multilevel interventions that address not only individual-level risks but also economic disparities that have precipitated and maintained a disproportionate level of alcohol-related consequences among more marginalized and vulnerable populations.

  16. Supercharging by m-NBA Improves ETD-Based Quantification of Hydroxyl Radical Protein Footprinting.

    PubMed

    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. 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.

  18. Synthesis of Silver Nanoparticles Using Hydroxyl Functionalized Ionic Liquids and Their Antimicrobial Activity

    PubMed Central

    Dorjnamjin, Demberelnyamba; Ariunaa, Maamaa; Shim, Young Key

    2008-01-01

    We report a new one phase method for the synthesis of uniform monodisperse crystalline Ag nanoparticles in aqueous systems that has been developed by using newly synthesized mono and dihydroxylated ionic liquids and cationic surfactants based on 1,3-disubstituted imidazolium cations and halogens anions. The hydroxyl functionalized ionic liquids (HFILs) and hydroxyl functionalized cationic surfactants (HFCSs) also simultaneously acts both as the reductant and protective agent. By changing the carbon chain length, alcohol structure and anion of the 1,3-imidazolium based HFILs and HFCSs the particle size, uniform and dispersibility of nanoparticles in aqueous solvents could be controlled. Transmission electron microscopy (TEM), electron diffraction, UV-Vis and NMR, were used for characterization of HFILs, HFCSs and silver nanoparticles. TEM studies on the solution showed representative spherical silver nanoparticles with average sizes 2–8 nm, particularly 2.2 nm and 4.5 nm in size range and reasonable narrow particle size distributions (SD-standard distribution) 0.2 nm and 0.5 nm respectively. The all metal nanoparticles are single crystals with face centered cubic (fcc) structure. The silver nanoparticles surface of plasmon resonance band (λmax) around 420 nm broadened and little moved to the long wavelength region that indicating the formation of silver nanoparticles dispersion with broad absorption around infrared (IR) region. Silver complexes of these HFILs as well as different silver nanoparticles dispersions have been tested in vitro against several gram positive and gram negative bacteria and fungus. The silver nanoparticles providing environmentally friendly and high antimicrobial activity agents. PMID:19325785

  19. Synthesis of silver nanoparticles using hydroxyl functionalized ionic liquids and their antimicrobial activity.

    PubMed

    Dorjnamjin, Demberelnyamba; Ariunaa, Maamaa; Shim, Young Key

    2008-05-01

    We report a new one phase method for the synthesis of uniform monodisperse crystalline Ag nanoparticles in aqueous systems that has been developed by using newly synthesized mono and dihydroxylated ionic liquids and cationic surfactants based on 1,3-disubstituted imidazolium cations and halogens anions. The hydroxyl functionalized ionic liquids (HFILs) and hydroxyl functionalized cationic surfactants (HFCSs) also simultaneously acts both as the reductant and protective agent. By changing the carbon chain length, alcohol structure and anion of the 1,3-imidazolium based HFILs and HFCSs the particle size, uniform and dispersibility of nanoparticles in aqueous solvents could be controlled. Transmission electron microscopy (TEM), electron diffraction, UV-Vis and NMR, were used for characterization of HFILs, HFCSs and silver nanoparticles. TEM studies on the solution showed representative spherical silver nanoparticles with average sizes 2-8 nm, particularly 2.2 nm and 4.5 nm in size range and reasonable narrow particle size distributions (SD-standard distribution) 0.2 nm and 0.5 nm respectively. The all metal nanoparticles are single crystals with face centered cubic (fcc) structure. The silver nanoparticles surface of plasmon resonance band (lambda(max)) around 420 nm broadened and little moved to the long wavelength region that indicating the formation of silver nanoparticles dispersion with broad absorption around infrared (IR) region. Silver complexes of these HFILs as well as different silver nanoparticles dispersions have been tested in vitro against several gram positive and gram negative bacteria and fungus. The silver nanoparticles providing environmentally friendly and high antimicrobial activity agents.

  20. Formation of long-lived hydroxyl free radical adducts of proline and hydroxyproline in a Fenton reaction.

    PubMed

    Floyd, R A; Nagy, I

    1984-10-09

    Proline and hydroxyproline when exposed to the hydroxyl free radical generating system of ADP-Fe(II)-H2O2 yielded long-lived free radicals. An analysis of the electron paramagnetic resonance spectra of the long-lived hydroxyl free radical adducts of proline and hydroxyproline is consistent with a free electron on a nitroxyl group interacting with the nitrogen atom as well as with three separate protons. In the case of proline, nitroxide formation was observed under the influence of tert-butyl-hydroperoxide, giving a similar EPR spectrum (Lin, J.S., Tom, T.C. and Olcott, H.S. (1974) J. Agr. Food Chem. 22, 526-528); however, the hydroxyl free radical adduct of hydroxyproline has not been described yet. In the case of the proline nitroxide radical, two of the three protons involved interact with the free electron equivalently. The coupling constants for the hydroxyl free radical adduct of proline are AN = 1.58 mT, AH1 beta = AH2 beta = 2.13 mT, AH3 beta = 1.77 mT and for hydroxyproline are AN = 1.54 mT, AH1 beta = 2.56 mT, AH2 beta = 2.03 and AH3 beta = 1.51. The data are consistent with the amine nitrogen of proline and hydroxyproline being oxidized to a nitroxyl group and the free electron of the nitroxyl interacting with the beta-protons of these amino acid hydroxyl free radical adducts.