Spectroscopic studies on the interaction of cinnamic acid and its hydroxyl derivatives with human serum albumin

NASA Astrophysics Data System (ADS)

Min, Jiang; Meng-Xia, Xie; Dong, Zheng; Yuan, Liu; Xiao-Yu, Li; Xing, Chen

2004-04-01

Cinnamic acid and its derivatives possess various biological effects in remedy of many diseases. Interaction of cinnamic acid and its hydroxyl derivatives, p-coumaric acid and caffeic acid, with human serum albumin (HSA), and concomitant changes in its conformation were studied using fluorescence and Fourier transform infrared spectroscopic methods. Fluorescence data revealed the presence of one binding site on HSA for cinnamic acid and its hydroxyl derivatives, and their binding constants ( KA) are caffeic acid> p-coumaric acid> cinnamic acid when Cdrug/ CHSA ranging from 1 to 10. The changes of the secondary structure of HSA after interacting with the three drugs are estimated, respectively by combining the curve-fitting results of amid I and amid III bands. The α-helix structure has a decrease of ≈9, 5 and 3% after HSA interacted with caffeic acid, p-coumaric acid and cinnamic acid, respectively. It was found that the hydroxyls substituted on aromatic ring of the drugs play an important role in the changes of protein's secondary structure. Combining the result of fluorescence quenching and the changes of secondary structure of HSA after interaction with the three drugs, the drug-HSA interaction mode was discussed.

Inactivation of peptidylglycine α-hydroxylating monooxygenase by cinnamic acid analogs

PubMed Central

McIntyre, Neil R.; Lowe, Edward W.; Battistini, Matthew R.; Leahy, James W.; Merkler, David J.

2016-01-01

Peptidylglycine α-amidating monooxygenase (PAM) is a bifunctional enzyme that catalyzes the final reaction in the maturation of α-amidated peptide hormones. Peptidylglycine α-hydroxylating monooxygenase (PHM) is the PAM domain responsible for the copper-, ascorbate- and O2-dependent hydroxylation of a glycine-extended peptide. Peptidylamidoglycolate lyase is the PAM domain responsible for the Zn(II)-dependent dealkylation of the α-hydroxyglycine-containing precursor to the final α-amidated peptide. We report herein that cinnamic acid and cinnamic acid analogs are inhibitors or inactivators of PHM. The inactivation chemistry exhibited by the cinnamates exhibits all the attributes of a suicide-substrate. However, we find no evidence for the formation of an irreversible linkage between cinnamate and PHM in the inactivated enzyme. Our data support the reversible formation of a Michael adduct between an active site nucleophile and cinnamate that leads to inactive enzyme. Our data are of significance given that cinnamates are found in foods, perfumes, cosmetics and pharmaceuticals. PMID:26024288

Potential bile acid metabolites. XV. Synthesis of 4 beta-hydroxylated bile acids; unique bile acids in human fetal bile.

PubMed

Iida, T; Momose, T; Chang, F C; Goto, J; Nambara, T

1989-12-01

The 4 beta-hydroxylated derivatives of lithocholic, deoxycholic, chenodeoxycholic, and cholic acids were synthesized from their respective parent compounds. The principal reactions employed were 1) beta-face cis-dihydroxylation of delta 3 intermediates with osmium tetroxide-N-methylmorpholine N-oxide, 2) selective cathylation of vicinal 3 beta,4 beta-diols followed by oxidation of the resulting 4 beta-monocathylates, or direct selective oxidation at C-3 of 3 beta,4 beta-diols with pyridinium chlorochromate, and 3) stereoselective reduction of the 3-oxo compounds with tert-butylamine-borane complex. The results of analysis of the prepared 4 beta-hydroxylated bile acids with a diequatorial trans-glycol structure and their 3 beta-epimers by proton and carbon-13 nuclear magnetic resonance spectroscopies are briefly discussed along with the mass spectrometric properties.

Markedly Enhanced Surface Hydroxyl Groups of TiO2 Nanoparticles with Superior Water-Dispersibility for Photocatalysis

PubMed Central

Wu, Chung-Yi; Tu, Kuan-Ju; Deng, Jin-Pei; Lo, Yu-Shiu; Wu, Chien-Hou

2017-01-01

The benefits of increasing the number of surface hydroxyls on TiO2 nanoparticles (NPs) are known for environmental and energy applications; however, the roles of the hydroxyl groups have not been characterized and distinguished. Herein, TiO2 NPs with abundant surface hydroxyl groups were prepared using commercial titanium dioxide (ST-01) powder pretreated with alkaline hydrogen peroxide. Through this simple treatment, the pure anatase phase was retained with an average crystallite size of 5 nm and the surface hydroxyl group density was enhanced to 12.0 OH/nm2, estimated by thermogravimetric analysis, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. Especially, this treatment increased the amounts of terminal hydroxyls five- to six-fold, which could raise the isoelectric point and the positive charges on the TiO2 surface in water. The photocatalytic efficiency of the obtained TiO2 NPs was investigated by the photodegradation of sulforhodamine B under visible light irradiation as a function of TiO2 content, pH of solution, and initial dye concentration. The high surface hydroxyl group density of TiO2 NPs can not only enhance water-dispersibility but also promote dye sensitization by generating more hydroxyl radicals. PMID:28772926

Release of free amino acids upon oxidation of peptides and proteins by hydroxyl radicals.

PubMed

Liu, Fobang; Lai, Senchao; Tong, Haijie; Lakey, Pascale S J; Shiraiwa, Manabu; Weller, Michael G; Pöschl, Ulrich; Kampf, Christopher J

2017-03-01

Hydroxyl radical-induced oxidation of proteins and peptides can lead to the cleavage of the peptide, leading to a release of fragments. Here, we used high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) and pre-column online ortho-phthalaldehyde (OPA) derivatization-based amino acid analysis by HPLC with diode array detection and fluorescence detection to identify and quantify free amino acids released upon oxidation of proteins and peptides by hydroxyl radicals. Bovine serum albumin (BSA), ovalbumin (OVA) as model proteins, and synthetic tripeptides (comprised of varying compositions of the amino acids Gly, Ala, Ser, and Met) were used for reactions with hydroxyl radicals, which were generated by the Fenton reaction of iron ions and hydrogen peroxide. The molar yields of free glycine, aspartic acid, asparagine, and alanine per peptide or protein varied between 4 and 55%. For protein oxidation reactions, the molar yields of Gly (∼32-55% for BSA, ∼10-21% for OVA) were substantially higher than those for the other identified amino acids (∼5-12% for BSA, ∼4-6% for OVA). Upon oxidation of tripeptides with Gly in C-terminal, mid-chain, or N-terminal positions, Gly was preferentially released when it was located at the C-terminal site. Overall, we observe evidence for a site-selective formation of free amino acids in the OH radical-induced oxidation of peptides and proteins, which may be due to a reaction pathway involving nitrogen-centered radicals.

[Correlation Between Functional Groups and Radical Scavenging Activities of Acidic Polysaccharides from Dendrobium].

PubMed

Liao, Ying; Yuan, Wen-yu; Zheng, Wen-ke; Luo, Ao-xue; Fan, Yi-jun

2015-11-01

To compare the radical scavenging activity of five different acidic polysaccharides, and to find the correlation with the functional groups. Alkali extraction method and Stepwise ethanol precipitation method were used to extract and concentrate the five Dendrobium polysaccharides, and to determine the contents of sulfuric acid and uronic acid of each kind of acidic polysaccharides, and the scavenging activity to ABTS+ radical and hydroxyl radical. Functional group structures were examined by FTIR Spectrometer. Five kinds of Dendrobium polysaccharides had different ability of scavenging ABTS+ free radical and hydroxyl free radical. Moreover, the study had shown that five kinds of antioxidant activity of acidic polysaccharides had obvious correlation withuronic acid and sulfuric acid. The antioxidant activity of each sample was positively correlated with the content of uronic acid, and negatively correlated with the content of sulfuric acid. Sulfuric acid can inhibit the antioxidant activity of acidic polysaccharide but uronic acid can enhance the free radical scavenging activity. By analyzing the structure characteristics of five acidic polysaccharides, all samples have similar structures, however, Dendrobium denneanum, Dendrobium devonianum and Dendrobium officinale which had β configuration have higher antioxidant activity than Dendrobium nobile and Dendrobium fimbriatum which had a configuration.

Developing cellulosic waste products as platform chemicals: protecting group chemistry of α-glucoisosaccharinic acid.

PubMed

Almond, Michael; Suleiman, Mustapha G; Hawkins, Matthew; Winder, Daniel; Robshaw, Thomas; Waddoups, Megan; Humphreys, Paul N; Laws, Andrew P

2018-01-02

Alpha and beta-glucoisosaccharinic acids ((2S,4S)-2,4,5-trihydroxy-2-(hydroxymethyl)pentanoic acid and (2R,4S)-2,4,5-trihydroxy-2-(hydroxymethyl)pentanoic acid) which are produced when cellulosic materials are treated with aqueous alkali are potentially valuable platform chemicals. Their highly functionalised carbon skeleton, with fixed chirality at C-2 and C-4, makes them ideal starting materials for use in synthesis. In order to assess the potential of these saccharinic acids as platform chemicals we have explored the protecting group chemistry of the lactone form of alpha-glucoisosaccharinic acid (α-GISAL). We report here the use of single and multiple step reaction pathways leading to the regioselective protection of the three different hydroxyl groups of α-GISAL. We report strategies for protecting the three different hydroxyl groups individually or in pairs. We also report the synthesis of a range of tri-O-protected α-GISAL derivatives where a number of the products contain orthogonal protecting groups. Copyright © 2017 Elsevier Ltd. All rights reserved.

Suppression of LPS-induced inflammatory responses by the hydroxyl groups of dexamethasone

PubMed Central

Chuang, Ting-Yun; Cheng, An-Jie; Chen, I-Ting; Lan, Tien-Yun; Huang, I-Hsuan; Shiau, Chung-Wai; Hsu, Chia-Lin; Liu, Ya-Wen; Chang, Zee-Fen; Tseng, Ping-Hui; Kuo, Jean-Cheng

2017-01-01

The innate immune response is a central process that is activated during pathogenic infection in order to maintain physiological homeostasis. It is well known that dexamethasone (Dex), a synthetic glucocorticoid, is a potent immunosuppressant that inhibits the cytokine production induced by bacterial lipopolysaccharides (LPS). Nevertheless, the extent to which the functional groups of Dex control the excessive activation of inflammatory reactions remains unknown. Furthermore, importantly, the role of Dex in the innate immune response remains unclear. Here we explore the mechanism of LPS-induced TNF-α secretion and reveal p38 MAPK signaling as a target of Dex that is involved in control of tumor necrosis factor-α (TNF-α)-converting enzyme (TACE) activity; that later mediates the shedding of TNF-α that allows its secretion. We further demonstrate that the 11-hydroxyl and 21-hydroxyl groups of Dex are the main groups that are involved in reducing LPS-induced TNF-α secretion by activated macrophages. Blockage of the hydroxyl groups of Dex inhibits immunosuppressant effect of Dex during LPS-induced TNF-α secretion and mouse mortality. Our findings demonstrate Dex signaling is involved in the control of innate immunity. PMID:28537905

Bile acid synthesis in man. In vivo activity of the 25-hydroxylation pathway

DOE Office of Scientific and Technical Information (OSTI.GOV)

Duane, W.C.; Pooler, P.A.; Hamilton, J.N.

1988-07-01

During biosynthesis of bile acid, carbons 25-26-27 are removed from the cholesterol side-chain. Side-chain oxidation begins either with hydroxylation at the 26-position, in which case the three-carbon fragment is released as propionic acid, or with hydroxylation at the 25-position, in which case the three-carbon fragment is released as acetone. We have previously shown in the rat that the contribution of the 25-hydroxylation pathway can be quantitated in vivo by measuring production of (/sup 14/C)acetone from (/sup 14/C)26-cholesterol. In the present study, we adapted this method to human subjects. 4 d after oral administration of 100 microCi of (/sup 14/C)26-cholesterol andmore » 1 d after beginning a constant infusion of 16.6 mumol/min unlabeled acetone, three men and two women underwent breath collections. Expired acetone was trapped and purified as the 2,4 dinitrophenylhydrazine derivative. /sup 14/CO/sub 2/ was trapped quantitatively using phenethylamine. Specific activity of breath acetone was multiplied by the acetone infusion rate to calculate production of (/sup 14/C)acetone. (/sup 14/C)Acetone production averaged 4.9% of total release of /sup 14/C from (/sup 14/C)26-cholesterol, estimated by /sup 14/CO2 output. The method was validated by showing that (/sup 14/C)acetone production from (/sup 14/C)isopropanol averaged 86.9% of the (/sup 14/C)-isopropanol infusion rate. We conclude that in man, as in the rat, the 25-hydroxylation pathway accounts for less than 5% of bile acid synthesis.« less

Membrane protein complexes catalyze both 4- and 3-hydroxylation of cinnamic acid derivatives in monolignol biosynthesis

PubMed Central

Chen, Hsi-Chuan; Li, Quanzi; Shuford, Christopher M.; Liu, Jie; Muddiman, David C.; Sederoff, Ronald R.; Chiang, Vincent L.

2011-01-01

The hydroxylation of 4- and 3-ring carbons of cinnamic acid derivatives during monolignol biosynthesis are key steps that determine the structure and properties of lignin. Individual enzymes have been thought to catalyze these reactions. In stem differentiating xylem (SDX) of Populus trichocarpa, two cinnamic acid 4-hydroxylases (PtrC4H1 and PtrC4H2) and a p-coumaroyl ester 3-hydroxylase (PtrC3H3) are the enzymes involved in these reactions. Here we present evidence that these hydroxylases interact, forming heterodimeric (PtrC4H1/C4H2, PtrC4H1/C3H3, and PtrC4H2/C3H3) and heterotrimeric (PtrC4H1/C4H2/C3H3) membrane protein complexes. Enzyme kinetics using yeast recombinant proteins demonstrated that the enzymatic efficiency (Vmax/km) for any of the complexes is 70–6,500 times greater than that of the individual proteins. The highest increase in efficiency was found for the PtrC4H1/C4H2/C3H3-mediated p-coumaroyl ester 3-hydroxylation. Affinity purification-quantitative mass spectrometry, bimolecular fluorescence complementation, chemical cross-linking, and reciprocal coimmunoprecipitation provide further evidence for these multiprotein complexes. The activities of the recombinant and SDX plant proteins demonstrate two protein-complex–mediated 3-hydroxylation paths in monolignol biosynthesis in P. trichocarpa SDX; one converts p-coumaric acid to caffeic acid and the other converts p-coumaroyl shikimic acid to caffeoyl shikimic acid. Cinnamic acid 4-hydroxylation is also mediated by the same protein complexes. These results provide direct evidence for functional involvement of membrane protein complexes in monolignol biosynthesis. PMID:22160716

Novel Enzyme Family Found in Filamentous Fungi Catalyzing trans-4-Hydroxylation of l-Pipecolic Acid

PubMed Central

Hibi, Makoto; Mori, Ryosuke; Miyake, Ryoma; Kawabata, Hiroshi; Kozono, Shoko; Takahashi, Satomi

2016-01-01

Hydroxypipecolic acids are bioactive compounds widely distributed in nature and are valuable building blocks for the organic synthesis of pharmaceuticals. We have found a novel hydroxylating enzyme with activity toward l-pipecolic acid (l-Pip) in a filamentous fungus, Fusarium oxysporum c8D. The enzyme l-Pip trans-4-hydroxylase (Pip4H) of F. oxysporum (FoPip4H) belongs to the Fe(II)/α-ketoglutarate-dependent dioxygenase superfamily, catalyzes the regio- and stereoselective hydroxylation of l-Pip, and produces optically pure trans-4-hydroxy-l-pipecolic acid (trans-4-l-HyPip). Amino acid sequence analysis revealed several fungal enzymes homologous with FoPip4H, and five of these also had l-Pip trans-4-hydroxylation activity. In particular, the homologous Pip4H enzyme derived from Aspergillus nidulans FGSC A4 (AnPip4H) had a broader substrate specificity spectrum than other homologues and reacted with the l and d forms of various cyclic and aliphatic amino acids. Using FoPip4H as a biocatalyst, a system for the preparative-scale production of chiral trans-4-l-HyPip was successfully developed. Thus, we report a fungal family of l-Pip hydroxylases and the enzymatic preparation of trans-4-l-HyPip, a bioactive compound and a constituent of secondary metabolites with useful physiological activities. PMID:26801577

Hydroxyl radical mediated degradation of phenylarsonic acid.

PubMed

Xu, Tielian; Kamat, Prashant V; Joshi, Sachin; Mebel, Alexander M; Cai, Yong; O'Shea, Kevin E

2007-08-16

Phenyl-substituted arsonic acids have been widely used as feed additives in the poultry industry. While very few studies have been reported on the environmental impact of these compounds, they have been introduced into the environment through land application of poultry litter in large quantities (about 10(6) kg/year). Phenylarsonic acid (PA) was used as a model for problematic arsonic acids. Dilute aqueous solutions of PA were subjected to gamma radiolysis under hydroxyl radical generating conditions, which showed rapid degradation of PA. Product studies indicate addition of (.)OH to the phenyl ring forms the corresponding phenols as the primary products. Arsenite, H3As(III)O3, and arsenate, H3As(V)O4, were also identified as products. The optimized structures and relative calculated energies (using GAUSSIAN 98, the B3LYP/6-31G(d) method) of the various transient intermediates are consistent with the product studies. Pulse radiolysis was used to determine the rate constants of PA with (.)OH (k = 3.2 x 10(9) M(-1) s(-1)) and SO4(.-) (k = 1.0 x 10(9) M(-1) s(-1)). PA reacts slower toward O(.-) (k = 1.9 x 10(7) M(-1) s(-1)) and N3(.) (no detectable transient), due to the lower oxidation potential of these two radicals. Our results indicate advanced oxidative processes employing (.)OH and SO4(.-) can be effective for the remediation of phenyl-substituted arsonic acids.

Enhanced electrical properties in solution-processed InGaZnO thin-film transistors by viable hydroxyl group transfer process

NASA Astrophysics Data System (ADS)

Kim, Do-Kyung; Jeong, Hyeon-Seok; Kwon, Hyeok Bin; Kim, Young-Rae; Kang, Shin-Won; Bae, Jin-Hyuk

2018-05-01

We propose a simple hydroxyl group transfer method to improve the electrical characteristics of solution-processed amorphous InGaZnO (IGZO) thin-film transistors (TFTs). Tuned poly(dimethylsiloxane) elastomer, which has a hydroxyl group as a terminal chemical group, was adhered temporarily to an IGZO thin-film during the solidification step to transfer and supply sufficient hydroxyl groups to the IGZO thin-film. The transferred hydroxyl groups led to efficient hydrolysis and condensation reactions, resulting in a denser metal–oxygen–metal network being achieved in the IGZO thin-film compared to the conventional IGZO thin-film. In addition, it was confirmed that there was no morphological deformation, including to the film thickness and surface roughness. The hydroxyl group transferred IGZO based TFTs exhibited enhanced electrical properties (field-effect mobility of 2.21 cm2 V‑1 s‑1, and on/off current ratio of 106) compared to conventional IGZO TFTs (field-effect mobility of 0.73 cm2 V‑1 s‑1 and on/off current ratio of 105).

Quantitative importance of the 25-hydroxylation pathway for bile acid biosynthesis in the rat

DOE Office of Scientific and Technical Information (OSTI.GOV)

Duane, W.C.; Bjoerkhem, I.H.; Hamilton, J.N.

1988-05-01

During biosynthesis of bile acid, carbons 25-26-27 are removed from the cholesterol side chain. Side-chain oxidation begins either with hydroxylation at the 26-position, in which case the three-carbon fragment is released as propionic acid, or with hydroxylation at the 25-position, in which case the three-carbon fragment is released as acetone. In the present study, we have quantitated the relative importance of these two pathways in vivo by measuring production of (14C) acetone from (14C)-26-cholesterol. Four days after intraperitoneal injection of 20 to 40 muCi (14C)-26-cholesterol and 1 day after beginning a constant intravenous infusion of unlabeled acetone at 25 mumolesmore » per kg per min, 6 male and 2 female Sprague-Dawley rats underwent breath collections. Expired acetone was trapped and purified as the 2,4-dinitrophenylhydrazine derivative. 14CO2 was trapped quantitatively using phenethylamine. Specific activity of breath acetone was multiplied times the acetone infusion rate to calculate production of (14C)acetone. (14C) Acetone production averaged 1.7% of total release of 14C from (14C)-26-cholesterol, estimated by 14CO2 output. The method was validated by showing that (14C) acetone production from (14C)isopropanol averaged 111% of the (14C)isopropanol infusion rate. We conclude that, in the normal rat, the 25-hydroxylation pathway accounts for less than 2% of bile acid synthesis.« less

Quantitative importance of the 25-hydroxylation pathway for bile acid biosynthesis in the rat.

PubMed

Duane, W C; Björkhem, I; Hamilton, J N; Mueller, S M

1988-01-01

During biosynthesis of bile acid, carbons 25-26-27 are removed from the cholesterol side chain. Side-chain oxidation begins either with hydroxylation at the 26-position, in which case the three-carbon fragment is released as propionic acid, or with hydroxylation at the 25-position, in which case the three-carbon fragment is released as acetone. In the present study, we have quantitated the relative importance of these two pathways in vivo by measuring production of [14C] acetone from [14C]-26-cholesterol. Four days after intraperitoneal injection of 20 to 40 muCi [14C]-26-cholesterol and 1 day after beginning a constant intravenous infusion of unlabeled acetone at 25 mumoles per kg per min, 6 male and 2 female Sprague-Dawley rats underwent breath collections. Expired acetone was trapped and purified as the 2,4-dinitrophenylhydrazine derivative. 14CO2 was trapped quantitatively using phenethylamine. Specific activity of breath acetone was multiplied times the acetone infusion rate to calculate production of [14C]acetone. [14C] Acetone production averaged 1.7% of total release of 14C from [14C]-26-cholesterol, estimated by 14CO2 output. The method was validated by showing that [14C] acetone production from [14C]isopropanol averaged 111% of the [14C]isopropanol infusion rate. We conclude that, in the normal rat, the 25-hydroxylation pathway accounts for less than 2% of bile acid synthesis.

How does hydroxyl introduction influence the double helical structure: the stabilization of an altritol nucleic acid:ribonucleic acid duplex

PubMed Central

Ovaere, Margriet; Sponer, Jiri; Sponer, Judit E.; Herdewijn, Piet; Van Meervelt, Luc

2012-01-01

Altritol nucleic acids (ANAs) are a promising new tool in the development of artificial small interfering ribonucleic acids (siRNAs) for therapeutical applications. To mimic the siRNA:messenger RNA (mRNA) interactions, the crystal structure of the ANA:RNA construct a(CCGUAAUGCC-P):r(GGCAUUACGG) was determined to 1.96 Å resolution which revealed the hybrid to form an A-type helix. As this A-form is a major requirement in the RNAi process, this crystal structure confirms the potential of altritol-modified siRNAs. Moreover, in the ANA strands, a new type of intrastrand interactions was found between the O2′ hydroxyl group of one residue and the sugar ring O4′ atom of the next residue. These interactions were further investigated by quantum chemical methods. Besides hydration effects, these intrastrand hydrogen bonds may also contribute to the stability of ANA:RNA duplexes. PMID:22638588

Influence of hydroxyl groups on the biological properties of cationic polymethacrylates as gene vectors.

PubMed

Ma, Ming; Li, Feng; Yuan, Zhe-fan; Zhuo, Ren-xi

2010-07-01

In this study poly(aminoethyl methacrylate) (PAEMA), poly(3-amino-2-hydroxypropyl methacrylate) (PAHPMA), poly(2-(2-aminoethylamino)ethyl methacrylate) (PAEAEMA) and poly(3-(2-aminoethylamino) 2-hydroxypropyl methacrylate) (PAEAHPMA) were synthesized using atom transfer radical polymerization to evaluate the effect of hydroxyl groups on the relative properties of cationic polymeric gene vectors. The results of heparin displacement assays showed that PAHPMA possessed a stronger binding capacity than PAEMA. PAHPMA/DNA complexes and PAEAHPMA/DNA complexes had lower zeta potentials than those of PAEMA and PAEAEMA. MTT assay results indicated that PAHPMA and PAEAHPMA exhibited obviously lower cytotoxicities than PAEMA and PAEAEMA. Subsequently, in vitro gene transfection studies in 293T cells without serum showed that PAHPMA exhibited a lower transfection efficiency than PAEMA and PAEAHPMA/DNA complexes possessed a similar transfection efficiency to PAEAEMA/DNA complexes. Moreover, PAHPMA and PAEAHPMA retained similar transfection efficiencies in DMEM with 10% serum, but PAEMA and PAEAEMA showed slightly lower transfection efficiencies than in the absence of serum. The reason for these phenomena might be attributed to the introduction of hydroxyl groups into PAHPMA and PAEAHPMA, i.e. the existence of hydroxyl groups might increase the binding capacity to DNA and at the same time decrease the surface charge of the polymer/DNA complexes due to the formation of hydrogen bonds between the polymers and DNA. Therefore, a lower zeta potential and stronger binding ability may result in a lower gene transfection efficiency. This effect of hydroxyl groups decreased with increasing amino group density on the polymer. Copyright 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Chemisorption of hydrogen atoms and hydroxyl groups on stretched graphene: A coupled QM/QM study

NASA Astrophysics Data System (ADS)

Katin, Konstantin P.; Prudkovskiy, Vladimir S.; Maslov, Mikhail M.

2017-09-01

Using the density functional theory coupled with the nonorthogonal tight-binding model, we analyze the chemisorption of hydrogen atoms and hydroxyl groups on the unstrained and stretched graphene sheets. Drawback of finite cluster model of graphene for the chemisorption energy calculation in comparison with the QM/QM approach applied is discussed. It is shown that the chemisorption energy for the hydroxyl group is sufficiently lower than for hydrogen at stretching up to 7.5%. The simultaneous paired chemisorption of hydrogen and hydroxyl groups on the same hexagon has also been examined. Adsorption of two radicals in ortho and para positions is found to be more energetically favorable than those in meta position at any stretching considered. In addition the energy difference between adsorbent pairs in ortho and para positions decreases as the stretching rises. It could be concluded that the graphene stretching leads to the loss of preferred mutual arrangement of two radicals on its surface.

Hydroxyl group as IR probe to detect the structure of ionic liquid-acetonitrile mixtures

NASA Astrophysics Data System (ADS)

Xu, Jing; Deng, Geng; Zhou, Yu; Ashraf, Hamad; Yu, Zhi-Wu

2018-06-01

Task-specific ionic liquids (ILs) are those with functional groups introduced in the cations or anions of ILs to bring about specific properties for various tasks. In this work, the hydrogen bonding interactions between a hydroxyl functionalized IL 1-(2-hydroxylethyl)-3-methylimidazolium tetrafluoroborate ([C2OHMIM][BF4]) and acetonitrile were investigated in detail by infrared spectroscopy, excess spectroscopy, two-dimensional correlation spectroscopy, combined with hydrogen nuclear magnetic resonance and density functional theory calculations (DFT). The hydroxyl group rather than C2sbnd H is found to be the main interaction site in the cation. And the ν(Osbnd H) is more sensitive than v(C-Hs) to the environment, which has been taken as an intrinsic probe to reflect the structural change of IL. Examining the region of ν(Osbnd H), by combining excess spectroscopy and DFT calculation, a number of species were identified in the mixtures. Other than the hydrogen bond between a cation and an anion, the hydroxyl group allows the formation of a hydrogen bond between two like-charged cations. The Osbnd H⋯O hydrogen bonding interactions in the hydroxyl-mediated cation-cation complexes are cooperative, while Osbnd H⋯F and C2sbnd H⋯F hydrogen bonding interactions in cation-anion complexes are anti-cooperative. These in-depth studies on the properties of the ionic liquid-acetonitrile mixtures may shed light on exploring their applications as mixed solvents and understanding the nature of doubly ionic hydrogen bonds.

Ammonia IRMS-TPD measurements and DFT calculation on acidic hydroxyl groups in CHA-type zeolites.

PubMed

Suzuki, Katsuki; Sastre, German; Katada, Naonobu; Niwa, Miki

2007-12-07

Brønsted acidity of H-chabazite (CHA) zeolites (Si : Al(2) = 4.2) was investigated by means of ammonia infrared-mass spectrometry/temperature-programmed desorption (IRMS-TPD) methods and density functional calculations. Four IR bands were observed at 3644, 3616, 3575 and 3538 cm(-1), and they were ascribable to the acidic OH groups on four nonequivalent oxygen sites in the CHA structure. The absorption band at 3538 cm(-1) was attributed to the O(4)H in the 6-membered ring (MR), and ammonia adsorption energy (DeltaU) of this OH group was the lowest among the 4 kinds of OH groups. The other 3 bands were assigned to the acidic OH groups in 8MR. It was observed that the DeltaU in 8 and 6MR were 131 (+/-3) and 101 kJ mol(-1), respectively. On the other hand, the density functional theory (DFT) calculations within periodic boundary conditions yielded the adsorption energies on these OH groups in 8 and 6MR to be ca. 130 and 110 kJ mol(-1), respectively, in good agreement with the experimentally-observed values.

Cobalt(II) ion as a promoter of hydroxyl radical and possible 'crypto-hydroxyl' radical formation under physiological conditions. Differential effects of hydroxyl radical scavengers.

PubMed

Moorhouse, C P; Halliwell, B; Grootveld, M; Gutteridge, J M

1985-12-13

Co(II) ions react with hydrogen peroxide under physiological conditions to form a 'reactive species' that can hydroxylate aromatic compounds (phenol and salicylate) and degrade deoxyribose to thiobarbituric-acid-reactive material. Catalase decreases the formation of this species but superoxide dismutase or low concentrations of ascorbic acid have little effect. EDTA, present in excess over the Co(II), can accelerate deoxyribose degradation and aromatic hydroxylation. In the presence of EDTA, deoxyribose degradation by the reactive species is inhibited competitively by scavengers of the hydroxyl radical (.OH), their effectiveness being related to their second-order rate constants for reaction with .OH. In the absence of EDTA the scavengers inhibit only at much higher concentrations and their order of effectiveness is changed. It is suggested that, in the presence of EDTA, hydroxyl radical is formed 'in free solution' and attacks deoxyribose or an aromatic molecule. In the absence of EDTA, .OH radical is formed in a 'site-specific' manner and is difficult to intercept by .OH scavengers. The relationship of these results to the proposed 'crypto .OH' radical is discussed.

Formyl-ended heterobifunctional poly(ethylene oxide): synthesis of poly(ethylene oxide) with a formyl group at one end and a hydroxyl group at the other end.

PubMed

Nagasaki, Y; Kutsuna, T; Iijima, M; Kato, M; Kataoka, K; Kitano, S; Kadoma, Y

1995-01-01

Well-defined poly(ethylene oxide) (PEO) with a formyl group at one end and a hydroxyl group at the other terminus was synthesized by the anionic ring opening polymerization of ethylene oxide (EO) with a new organometallic initiator possessing an acetal moiety, potassium 3,3-diethoxypropyl alkoxide. Hydrolysis of the acetal moiety produced a formyl group-terminated heterobifunctional PEO with a hydroxyl group at the other end.

Xylosylation of Phenolic Hydroxyl Groups of the Monomeric Lignin Model Compounds 4-Methylguaiacol and Vanillyl Alcohol by Coriolus versicolor

PubMed Central

Kondo, Ryuichiro; Yamagami, Hikari; Sakai, Kokki

1993-01-01

When 4-methylguaiacol (MeG), a phenolic lignin model compound, was added to a culture that was inoculated with Coriolus versicolor, it was bioconverted into 2-methoxy-4-methylphenyl β-d-xyloside (MeG-Xyl). The phenolic hydroxyl group of vanillyl alcohol was much more extensively xylosylated than the alcoholic hydroxyl group. When a mixture of MeG and commercial UDP-xylose was incubated with cell extracts of mycelia, transformation of UDP-xylose into MeG-Xyl was observed. This result suggested that UDP-xylosyltransferase was involved in the xylosylation of phenolic hydroxyl groups of lignin model compounds. PMID:16348869

Reaction Mechanisms and Structural and Physicochemical Properties of Caffeic Acid Grafted Chitosan Synthesized in Ascorbic Acid and Hydroxyl Peroxide Redox System.

PubMed

Liu, Jun; Pu, Huimin; Chen, Chong; Liu, Yunpeng; Bai, Ruyu; Kan, Juan; Jin, Changhai

2018-01-10

The ascorbic acid (AA) and hydroxyl peroxide (H 2 O 2 ) redox pair induced free radical grafting reaction is a promising approach to conjugate phenolic groups with chitosan (CS). In order to reveal the exact mechanisms of the AA/H 2 O 2 redox pair induced grafting reaction, free radicals generated in the AA/H 2 O 2 redox system were compared with hydroxyl radical ( • OH) produced in the Fe 2+ /H 2 O 2 redox system. Moreover, the structural and physicochemical properties of caffeic acid grafted CS (CA-g-CS) synthesized in these two redox systems were compared. Results showed that only ascorbate radical (Asc •- ) was produced in the AA/H 2 O 2 system. The reaction between Asc •- and CS produced novel carbon-centered radicals, whereas no new free radicals were detected when • OH reacted with CS. Thin layer chromatography, UV-vis, Fourier transform infrared, and nuclear magnetic resonance spectroscopic analyses all confirmed that CA was successfully grafted onto CS through Asc •- . However, CA could be hardly grafted onto CS via • OH. CA-g-CS synthesized through Asc •- exhibited lower thermal stability and crystallinity than the reaction product obtained through • OH. For the first time, our results demonstrated that the synthesis of CA-g-CS in the AA/H 2 O 2 redox system was mediated by Asc •- rather than • OH.

Alpha-Hydroxylation of lignoceric and nervonic acids in the brain. Effects of altered thyroid function on postnatal development of the hydroxylase activity.

PubMed

Murad, S; Strycharz, G D; Kishimoto, Y

1976-09-10

Rat brain postnuclear preparations catalyzed the alpha-hydroxylation of nervonic acid with an apparent Km of 3 muM. Evidence has been presented which suggests that nervonic acid in the brain is hydroxylated by the same enzyme system which hydroxylates lignoceric acid. The hydroxylase activity in brains of normal (euthyroid) rats increased rapidly from a low in the period immediately following birth to a maximum at the 23rd day and then declined to a low level characteristic of the mature brain. Neonatal hypothyroidism retarded the development of the activity and shifted its peak to the 39th day after birth. Conversely, neonatal hyperthyroidism accelerated the entire developmental pattern and shifted the peak to the 16th day after birth. The hydroxylase activity in mouse brain was also increased by thyroid hormone administration from the 13th through the 18th day after birth. Unlike normal mice, the low activity in jimpy mice was not affected by this treatment. It is concluded that thyroid hormones play an important role in the control of brain fatty acid alpha-hydroxylation. The stimulation of alpha-hydroxy fatty acid synthesis in response to hyperthyroidism during the early postnatal period may be one of the major effects of thyroid hormones in accelerating myelination of the central nervous system.

The Unexpected and Exceptionally Facile Chemical Modification of the Phenolic Hydroxyl Group of Tyrosine by Polyhalogenated Quinones under Physiological Conditions.

PubMed

Qu, Na; Li, Feng; Shao, Bo; Shao, Jie; Zhai, Guijin; Wang, Fuyi; Zhu, Ben-Zhan

2016-10-17

The phenolic hydroxyl group of tyrosine residue plays a crucial role in the structure and function of many proteins. However, little study has been reported about its modification by chemical agents under physiological conditions. In this study, we found, unexpectedly, that the phenolic hydroxyl group of tyrosine can be rapidly and efficiently modified by tetrafluoro-1,4-benzoquinone and other polyhalogenated quinones, which are the major genotoxic and carcinogenic quinoid metabolites of polyhalogenated aromatic compounds. The modification was found to be mainly due to the formation of a variety of fluoroquinone-O-tyrosine conjugates and their hydroxylated derivatives via nucleophilic substitution pathway. Analogous modifications were observed for tyrosine-containing peptides. Further studies showed that the blockade of the reactive phenolic hydroxyl group of tyrosine in the substrate peptide, even by very low concentration of tetrafluoro-1,4-benzoquinone, can prevent the kinase catalyzed tyrosine phosphorylation. This is the first report showing the exceptionally facile chemical modification of the phenolic hydroxyl group of tyrosine by polyhalogenated quinones under normal physiological conditions, which may have potential biological and toxicological implications.

A novel amino acid analysis method using derivatization of multiple functional groups followed by liquid chromatography/tandem mass spectrometry.

PubMed

Sakaguchi, Yohei; Kinumi, Tomoya; Yamazaki, Taichi; Takatsu, Akiko

2015-03-21

We have developed a novel amino acid analysis method using derivatization of multiple functional groups (amino, carboxyl, and phenolic hydroxyl groups). The amino, carboxyl, and phenolic hydroxyl groups of the amino acids were derivatized with 1-bromobutane so that the hydrophobicities and basicities of the amino acids were improved. The derivatized amino acids, including amino group-modified amino acids, could be detected with high sensitivity using liquid chromatography/tandem mass spectrometry (LC-MS/MS). In this study, 17 amino acids obtained by hydrolyzing proteins and 4 amino group-modified amino acids found in the human body (N,N-dimethylglycine, N-formyl-L-methionine, L-pyroglutamic acid, and sarcosine) were selected as target compounds. The 21 derivatized amino acids could be separated using an octadecyl-silylated silica column within 20 min and simultaneously detected. The detection limits for the 21 amino acids were 5.4-91 fmol, and the calibration curves were linear over the range of 10-100 nmol L(-1) (r(2) > 0.9984) with good repeatability. A confirmatory experiment showed that our proposed method could be applied to the determination of a protein certified reference material using the analysis of 12 amino acids combined with isotope dilution mass spectrometry. Furthermore, the proposed method was successfully applied to a stable isotope-coded derivatization method using 1-bromobutane and 1-bromobutane-4,4,4-d3 for comparative analysis of amino acids in human serum.

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.

Importance of specific purine amino and hydroxyl groups for efficient cleavage by a hammerhead ribozyme.

PubMed Central

Fu, D J; McLaughlin, L W

1992-01-01

Eight modified ribozymes of 19 residues have been prepared with individual purine amino or hydroxyl groups excised. The modified ribozymes were chemically synthesized with the substitution of a single 2'-deoxyadenosine, 2'-deoxyguanosine, inosine, or purine riboside for residues G10, A11, G13, or A14. Five of the modified ribozymes cleaved the 24-mer substrate with little change in rate as monitored by simple first-order kinetics. However, deletion of the 2-amino group at G10 (replacement with inosine) or deletion of either of the 2'-hydroxyls at G10 or G13 (replacement with 2'-deoxyguanosine) resulted in ribozymes with a drastic decrease in cleavage efficiency. Increasing the concentration of the Mg2+ cofactor from 10 mM to 50 mM significantly enhanced cleavage efficiency by these three derivatives. Steady-state kinetic assays for these three ribozymes indicated that the modifications result in both an increase in Km and a decrease in kcat. These results suggest that the exocyclic amino group at-G10 and the hydroxyls at G10 and G13 are important both for ribozyme-substrate binding and for the Mg(2+)-catalyzed cleavage reaction. PMID:1570323

Analysis of mycolic acids from a group of corynebacteria by capillary gas chromatography and mass spectrometry.

PubMed

Gailly, C; Sandra, P; Verzele, M; Cocito, C

1982-06-15

The cell wall of leprosy-derived corynebacteria (a group of 'diphtheroids' isolated from human leprosy lesions and patients' blood) was previously shown to contain, in addition to peptidoglycan and arabinogalactan, mycolic acids. These alpha-branched beta-hydroxy fatty acids were attributed to the corynomycolic group, according to their RF in monodimensional thin-layer chromatography. In the present work, mycolic acids from leprosy-derived and reference corynebacteria have been fractionated by monodimensional and bidimensional thin-layer chromatography and by gas chromatography. Pyrolyzed mycolic acids have been analyzed on conventional packed columns, whereas intact methyl esters of mycolic acids with free and silylated beta-hydroxyl group have been analyzed on capillary columns, and their structure has been established by mass spectrometry. In all leprosy-derived corynebacteria, some 20 components containing 24-36 carbon atoms and 0-4 double bonds were obtained. The three major groups had 32, 34 and 36 carbons, and the frequency of unsaturated versus saturated chains increased proportionally to the molecular weight. For comparison, the main components of a reference corynebacterium. Corynebacterium diphtheriae PW8, had 30 and 32 carbons, and their hydrocarbon chains were essentially saturated. This work confirms the relative chemical homogeneity of different leprosy-derived corynebacteria and describes some peculiar traits in the chemical structure of this group of organisms. In addition, it shows the complexity of the mycolic acid fraction of corynebacterial cell wall and suggests that the mycolic acid pattern is a sort of fingerprint of each bacterial strain grown under standard conditions. Finally, the fractionation of intact corynomycolic acid methyl esters with free or silylated beta-hydroxyl group by capillary gas chromatography proved to be the best analytical procedure at present available for resolving this complex mixture of corynomycolate isomers

Bacterial Conversion of Hydroxylamino Aromatic Compounds by both Lyase and Mutase Enzymes Involves Intramolecular Transfer of Hydroxyl Groups

PubMed Central

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

2003-01-01

Hydroxylamino aromatic compounds are converted to either the corresponding aminophenols or protocatechuate during the bacterial degradation of nitroaromatic compounds. The origin of the hydroxyl group of the products could be the substrate itself (intramolecular transfer mechanism) or the solvent water (intermolecular transfer mechanism). The conversion of hydroxylaminobenzene to 2-aminophenol catalyzed by a mutase from Pseudomonas pseudoalcaligenes JS45 proceeds by an intramolecular hydroxyl transfer. The conversions of hydroxylaminobenzene to 2- and 4-aminophenol by a mutase from Ralstonia eutropha JMP134 and to 4-hydroxylaminobenzoate to protocatechuate by a lyase from Comamonas acidovorans NBA-10 and Pseudomonas sp. strain 4NT were proposed, but not experimentally proved, to proceed by the intermolecular transfer mechanism. GC-MS analysis of the reaction products formed in H218O did not indicate any 18O-label incorporation during the conversion of hydroxylaminobenzene to 2- and 4-aminophenols catalyzed by the mutase from R. eutropha JMP134. During the conversion of 4-hydroxylaminobenzoate catalyzed by the hydroxylaminolyase from Pseudomonas sp. strain 4NT, only one of the two hydroxyl groups in the product, protocatechuate, was 18O labeled. The other hydroxyl group in the product must have come from the substrate. The mutase in strain JS45 converted 4-hydroxylaminobenzoate to 4-amino-3-hydroxybenzoate, and the lyase in Pseudomonas strain 4NT converted hydroxylaminobenzene to aniline and 2-aminophenol but not to catechol. The results indicate that all three types of enzyme-catalyzed rearrangements of hydroxylamino aromatic compounds proceed via intramolecular transfer of hydroxyl groups. PMID:12732549

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.

Hydroxyl/bile acid exchange. A new mechanism for the uphill transport of cholate by basolateral liver plasma membrane vesicles.

PubMed

Blitzer, B L; Terzakis, C; Scott, K A

1986-09-15

In order to characterize the driving forces for the concentrative uptake of unconjugated bile acids by the hepatocyte, the effects of pH gradients on the uptake of [3H]cholate by rat basolateral liver plasma membrane vesicles were studied. In the presence of an outwardly directed hydroxyl gradient (pH 6.0 outside and pH 7.5 inside the vesicle), cholate uptake was markedly stimulated and the bile acid was transiently accumulated at a concentration 1.5- to 2-fold higher than at equilibrium ("overshoot"). In the absence of a pH gradient (pH 6.0 or 7.5 both inside and outside the vesicle), uptake was relatively slower and no overshoot was seen. Reductions in the magnitude of the transmembrane pH gradient were associated with slower initial uptake rates and smaller overshoots. Cholate uptake under pH gradient conditions was inhibited by furosemide and bumetanide but not by 4, 4'-diisothiocyano-2,2'-disulfonic stilbene (SITS), 4-acetamido-4'-isothiocyanostilbene-2,2'-disulfonic acid (DIDS), or probenecid. In the absence of a pH gradient, an inside-positive valinomycin-induced K+ diffusion potential caused a slight increase in cholate uptake which was insensitive to furosemide. Moreover, in the presence of an outwardly directed hydroxyl gradient, uphill cholate transport was observed even under voltage clamped conditions. These findings suggest that pH gradient-driven cholate uptake was not due to associated electrical potentials. Despite an identical pKa to that of cholate, an outwardly directed hydroxyl gradient did not drive uphill transport of three other unconjugated bile acids (deoxycholate, chenodeoxycholate, ursodeoxycholate), suggesting that a non-ionic diffusion mechanism cannot account for uphill cholate transport. In canalicular vesicles, although cholate uptake was relatively faster in the presence of a pH gradient than in the absence of a gradient, peak uptake was only slightly above that found at equilibrium under voltage clamped conditions. These findings

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) ...

Promotional effect of surface hydroxyls on electrochemical reduction of CO 2 over SnO x/Sn electrode

DOE PAGES

Cui, Chaonan; Han, Jinyu; Zhu, Xinli; ...

2016-01-16

In this study, tin oxide (SnO x) formation on tin-based electrode surfaces during CO 2 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 SnO x in CO 2 reduction using a SnO monolayer on the Sn(112) surface as a model for SnO x. Water molecules have been treated explicitly and considered actively participating in the reaction. The results showed that H 2O dissociates on the perfect SnO monolayer into two hydroxyl groups symmetrically on the surface.more » CO 2 energetically prefers to react with the hydroxyl, forming a bicarbonate (HCO 3(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 H 2O via protonation. Whereas the oxygen vacancy (VO) in the oxide monolayer maybe formed by the reduction, it can be recovered by H 2O dissociation, resulting in two embedded hydroxyl groups. The results show that the hydroxylated surface with two symmetric hydroxyls is energetically more favorable for CO 2 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 SnO x monolayer on the electrode under the operating conditions promotes CO 2 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

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.

Glucuronidation of 6 alpha-hydroxy bile acids by human liver microsomes.

PubMed Central

Radomińska-Pyrek, A; Zimniak, P; Irshaid, Y M; Lester, R; Tephly, T R; St Pyrek, J

1987-01-01

The glucuronidation of 6-hydroxylated bile acids by human liver microsomes has been studied in vitro; for comparison, several major bile acids lacking a 6-hydroxyl group were also investigated. Glucuronidation rates for 6 alpha-hydroxylated bile acids were 10-20 times higher than those of substrates lacking a hydroxyl group in position 6. The highest rates measured were for hyodeoxy- and hyocholic acids, and kinetic analyses were carried out using these substrates. Rigorous product identification by high-field proton nuclear magnetic resonance and by electron impact mass spectrometry of methyl ester/peracetate derivatives revealed that 6-O-beta-D-glucuronides were the exclusive products formed in these enzymatic reactions. These results, together with literature data, indicate that 6 alpha-hydroxylation followed by 6-O-glucuronidation constitutes an alternative route of excretion of toxic hydrophobic bile acids. PMID:3110212

Copper(II)-catalyzed hydroxylation of aryl halides using glycolic acid as a ligand.

PubMed

Xiao, Yan; Xu, Yongnan; Cheon, Hwan-Sung; Chae, Junghyun

2013-06-07

Copper(II)-catalyzed hydroxylation of aryl halides has been developed to afford functionalized phenols. The protocol utilizes the reagent combination of Cu(OH)2, glycolic acid, and NaOH in aqueous DMSO, all of which are cheap, readily available, and easily removable after the reaction. A broad range of aryl iodides and activated aryl bromides were transformed into the corresponding phenols in excellent yields. Moreover, it has been shown that C-O(alkyl)-coupled product, instead of phenol, can be predominantly formed under similar reaction conditions.

Inhibition of hydroxyl radical reaction with aromatics by dissolved natural organic matter

USGS Publications Warehouse

Lindsey, M.E.; Tarr, M.A.

2000-01-01

Reaction of aromatic compounds with hydroxyl radical is inhibited by dissolved natural organic matter (NOM). The degree of inhibition is significantly greater than that expected based on a simple model in which aromatic compound molecules bound to NOM are considered to be unreactive. In this study, hydroxyl radical was produced at steady-state concentrations using Fenton chemistry (H2O2 + Fe2+ ??? Fe3+ + HO- + HO??). Suwannee River fulvic acid and humic acid were used as NOM. The most likely mechanism for the observed inhibition is that hydroxyl radical formation occurs in microenvironmental sites remote from the aromatic compounds. In addition to changes in kinetics, pyrene hydroxyl radical reaction also exhibited a mechanistic change in the presence of fulvic acid. The mechanism changed from a reaction that was apparently firstorder in pyrene to one that was apparently secondorder in pyrene, indicating that pyrene self-reaction may have become the dominant mechanism in the presence of fulvic acid. Dissolved NOM causes significant changes in the rate and mechanism of hydroxyl radical degradation of aromatic compounds. Consequently, literature rate constants measured in pure water will not be useful for predicting the degradation of pollutants in environmental systems. The kinetic and mechanistic information in this study will be useful for developing improved degradation methods involving Fenton chemistry.Reaction of aromatic compounds with hydroxyl radical is inhibited by dissolved natural organic matter (NOM). The degree of inhibition is significantly greater than that expected based on a simple model in which aromatic compounds molecules bounds to NOM are considered to be unreactive. In this study, hydroxyl radical was produced at steady-state concentrations using Fenton chemistry (H2O2 + Fe2+ ??? Fe3+ + HO- + HO??). Suwannee River fulvic acid and humic acid were used as NOM. The most likely mechanisms for the observed inhibition is that hydroxyl radical

Different catalytic effects of a single water molecule: the gas-phase reaction of formic acid with hydroxyl radical in water vapor.

PubMed

Anglada, Josep M; Gonzalez, Javier

2009-12-07

The effect of a single water molecule on the reaction mechanism of the gas-phase reaction between formic acid and the hydroxyl radical was investigated with high-level quantum mechanical calculations using DFT-B3LYP, MP2 and CCSD(T) theoretical approaches in concert with the 6-311+G(2df,2p) and aug-cc-pVTZ basis sets. The reaction between HCOOH and HO has a very complex mechanism involving a proton-coupled electron transfer process (pcet), two hydrogen-atom transfer reactions (hat) and a double proton transfer process (dpt). The hydroxyl radical predominantly abstracts the acidic hydrogen of formic acid through a pcet mechanism. A single water molecule affects each one of these reaction mechanisms in different ways, depending on the way the water interacts. Very interesting is also the fact that our calculations predict that the participation of a single water molecule results in the abstraction of the formyl hydrogen of formic acid through a hydrogen atom transfer process (hat).

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

PubMed

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

2016-04-01

BMS-779788 contains a reactive tertiary hydroxyl attached to a weakly basic imidazole ring. Propensity of the carbinol toward dehydration to yield the corresponding alkene, BMS-779788-ALK, was evaluated. Elevated levels of BMS-779788-ALK were observed in excipient compatibility samples. Stability studies revealed that BMS-779788 degrades to BMS-779788-ALK in capsules and tablets prepared by both dry and wet granulation processes. An acid-catalyzed dehydration mechanism, in which the heterocyclic core contributes resonance stability to the cationic intermediate via charge transfer to the imidazole ring, was proposed. Therefore, neutralization via a buffered (pH 7.0) granulating solution was used to mitigate dehydration. Solution studies revealed degradation of BMS-779788 to BMS-779788-ALK over the pH range of 1-7.5. Reversibility was confirmed by initiating reactions with BMS-779788-ALK over the same pH range. Accordingly, a simple reversible scheme can be used to describe reactions initiated with either BMS-779788 or BMS-779788-ALK. To eliminate potential for charge delocalization across the heterocycle and probe the degradation mechanism, the imidazole ring of BMS-779788 was methylated (BMS-779788-Me). The propensity for acid-catalyzed dehydration was then evaluated. The acid stability of BMS-779788-Me confirmed that the heterocyclic core contributes to reactivity liability of the tertiary hydroxyl. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

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.

Biologically produced acid precipitable polymeric lignin

DOEpatents

Crawford, Don L.; Pometto, III, Anthony L.

1984-01-01

A water soluble, acid precipitable polymeric degraded lignin (APPL), having a molecular weight of at least 12,000 daltons, and comprising, by percentage of total weight, at least three times the number of phenolic hydroxyl groups and carboxylic acid groups present in native lignin. The APPL may be modified by chemical oxidation and reduction to increase its phenolic hydroxyl content and reduce the number of its antioxidant inhibitory side chains, thereby improving antioxidant properties.

Time resolved study of hydroxyl radical oxidation of oleic acid at the air-water interface

NASA Astrophysics Data System (ADS)

Zhang, Xinxing; Barraza, Kevin M.; Upton, Kathleen T.; Beauchamp, J. L.

2017-09-01

The ubiquity of oleic acid (OA) renders it a poster child for laboratory investigations of environmental oxidation chemistry. In the current study, mechanistic details of the oxidation of OA by hydroxyl radicals at the air-water interface are investigated using field-induced droplet ionization mass spectrometry (FIDI-MS). Products from OH oxidation of both unsaturated and saturated carbon atoms are identified, and mechanisms for both types of oxidation processes are proposed. Uptake of oxygen in the interfacial layer increases linearly with time, consistent with Langmuir-Hinshelwood reaction kinetics. These results provide fundamental knowledge relating to OH initiated degradation of fatty acids in atmospheric aerosols.

3 alpha-Hydroxylated bile acid profiles in clinically normal cats, cats with severe hepatic lipidosis, and cats with complete extrahepatic bile duct occlusion.

PubMed

Center, S A; Thompson, M; Guida, L

1993-05-01

Concentrations of 3 alpha-hydroxylated bile acids were measured in serum and urine of clinically normal (healthy) cats (n = 6), cats with severe hepatic lipidosis (n = 9), and cats with complete bile duct occlusion (n = 4). Bile acid concentrations were measured by use of a gradient flow high-performance liquid chromatography procedure with an acetonitrile and ammonium phosphate mobile phase and an in-line postanalytic column containing 3 alpha-hydroxy-steroid dehydrogenase and a fluorescence detector. Specific identification of all bile acid peaks was not completed; unidentified moieties were represented in terms of their elution time (in minutes). Significant differences in serum and urine bile acid concentrations, quantitative and proportional, were determined among groups of cats. Cats with hepatic lipidosis and bile duct occlusion had significantly (P > or = 0.05) greater total serum and urine bile acids concentrations than did healthy cats. The proportion of hydrophobic bile acids in serum, those eluting at > or = 400 minutes, was 1.9% for healthy cats, 3.3% for cats with lipidosis, and 5.4% for bile duct-obstructed cats. Both groups of ill cats had a broader spectrum of unidentified late-eluting serum bile acids than did healthy cats; the largest spectrum developed in bile duct-occluded cats.(ABSTRACT TRUNCATED AT 250 WORDS)

The size of the hydroxyl group and its contribution to the affinity of atropine for muscarine-sensitive acetylcholine receptors.

PubMed Central

Barlow, R. B.; Ramtoola, S.

1980-01-01

1 From measurements of the affinity constants of hydratropyltropine and its methiodide for muscarine-sensitive acetylcholine receptors in the guinea-pig ileum, the increment in log K for the hydroxyl group in atropine is 2.06 and in the methiodide it is 2.16. These effects are slightly bigger than any so far recorded with these receptors. 2 The estimate of the increment in apparent molal volume for the hydroxyl group is 1.1 cm3/mol in atropine and 1.0 cm3/mol in the methobromide. 3 The large effect of the group on affinity may be linked to its small apparent size in water as suggested in the previous paper. PMID:7470742

Microbial hydroxylation and glycosidation of oleanolic acid by Circinella muscae and their anti-inflammatory activities.

PubMed

Yan, Sensen; Lin, Haijun; Huang, Huilian; Yang, Min; Xu, Bohui; Chen, Guangtong

2018-05-29

Biotransformation of oleanolic acid (OA) by Circinella muscae AS 3.2695 was investigated. Nine hydroxylated and glycosylated metabolites (1-9) were obtained. Their structures were elucidated as 3β,7β-dihydroxyolean-12-en-28-oic acid (1), 3β,7β,21β-trihydroxyolean-12-en-28-oic acid (2), 3β,7α,21β-trihydroxyolean-12-en- 28-oic acid (3), 3β,7β,15α-trihydroxyolean-12-en-28-oic acid (4), 7β,15α-dihydroxy- 3-oxo-olean-12-en-28-oic acid (5), 7β-hydroxy-3-oxo-olean-12-en-28-oic acid (6), oleanolic acid-28-O-β-D-glucopyranosyl ester (7), 3β,21β-dihydroxyolean-12-en-28- oic acid-28-O-β-D-glucopyranosyl ester (8), and 3β,7β,15α-trihydroxyolean-12-en- 28-oic acid-28-O-β-D-glucopyranosyl ester (9) by spectroscopic analysis. Among them, compounds 4 and 9 were new compounds. In addition, anti-inflammatory activities were assayed and evaluated for the isolated metabolites. Most of the metabolites exhibited significant inhibitory activities on lipopolysaccharides-induced NO production in RAW 264.7 cells.

Steroid and sterol 7-hydroxylation: ancient pathways.

PubMed

Lathe, Richard

2002-11-01

B-ring hydroxylation is a major metabolic pathway for cholesterols and some steroids. In liver, 7 alpha-hydroxylation of cholesterols, mediated by CYP7A and CYP39A1, is the rate-limiting step of bile acid synthesis and metabolic elimination. In brain and other tissues, both sterols and some steroids including dehydroepiandrosterone (DHEA) are prominently 7 alpha-hydroxylated by CYP7B. The function of extra-hepatic steroid and sterol 7-hydroxylation is unknown. Nevertheless, 7-oxygenated cholesterols are potent regulators of cell proliferation and apoptosis; 7-oxygenated derivatives of DHEA, pregnenolone, and androstenediol can have major effects in the brain and in the immune system. The receptor targets involved remain obscure. It is argued that B-ring modification predated steroid evolution: non-enzymatic oxidation of membrane sterols primarily results in 7-oxygenation. Such molecules may have provided early growth and stress signals; a relic may be found in hydroxylation at the symmetrical 11-position of glucocorticoids. Early receptor targets probably included intracellular sterol sites, some modern steroids may continue to act at these targets. 7-Hydroxylation of DHEA may reflect conservation of an early signaling pathway.

Effect of surface hydroxyl groups on heat capacity of mesoporous silica

NASA Astrophysics Data System (ADS)

Marszewski, Michal; Butts, Danielle; Lan, Esther; Yan, Yan; King, Sophia C.; McNeil, Patricia E.; Galy, Tiphaine; Dunn, Bruce; Tolbert, Sarah H.; Hu, Yongjie; Pilon, Laurent

2018-05-01

This paper quantifies the effect of surface hydroxyl groups on the effective specific and volumetric heat capacities of mesoporous silica. To achieve a wide range of structural diversity, mesoporous silica samples were synthesized by various methods, including (i) polymer-templated nanoparticle-based powders, (ii) polymer-templated sol-gel powders, and (iii) ambigel silica samples dried by solvent exchange at room temperature. Their effective specific heat capacity, specific surface area, and porosity were measured using differential scanning calorimetry and low-temperature nitrogen adsorption-desorption measurements. The experimentally measured specific heat capacity was larger than the conventional weight-fraction-weighted specific heat capacity of the air and silica constituents. The difference was attributed to the presence of OH groups in the large internal surface area. A thermodynamic model was developed based on surface energy considerations to account for the effect of surface OH groups on the specific and volumetric heat capacity. The model predictions fell within the experimental uncertainty.

The 4′-Hydroxyl Group of Resveratrol Is Functionally Important for Direct Activation of PPARα

PubMed Central

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

2015-01-01

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

Function of specific 2'-hydroxyl groups of guanosines in a hammerhead ribozyme probed by 2' modifications.

PubMed Central

Williams, D M; Pieken, W A; Eckstein, F

1992-01-01

The importance of the 2'-hydroxyl group of several guanosine residues for the catalytic efficiency of a hammerhead ribozyme has been investigated. Five ribozymes in which single guanosine residues were substituted with 2'-amino-, 2'-fluoro-, or 2'-deoxyguanosine were chemically synthesized. The comparison of the catalytic activity of the three 2' modifications at a specific position allows conclusions about the functional role of the parent 2'-hydroxyl group. Substitutions of nonconserved nucleotides within the ribozyme caused little alteration in the catalytic activity relative to that obtained with the unmodified ribozyme. In contrast, when either of the guanosines within the single-stranded loop between stem I and stem II of the ribozyme was replaced by 2'-deoxyguanosine or 2'-fluoro-2'-deoxyguanosine, the catalytic activities of the resulting ribozymes were reduced by factors of at least 150. The catalytic activities of the corresponding ribozymes containing 2'-amino-2'-deoxyguanosine substitutions at these positions, however, were both reduced by factors of 15. These effects resulted from decreases in the respective kcat values, whereas variations in the Km values were comparatively small. A different pattern of reactivity of the three 2' modifications was observed at the guanosine immediately 3' to stem II of the ribozyme. Whereas both 2'-deoxyguanosine and 2'-amino-2'-deoxyguanosine at this position showed catalytic activity similar to that of the unmodified ribozyme, the activity of the corresponding 2'-fluoro-2'-deoxyguanosine-containing ribozyme was reduced by a factor of 15. The implications of these substitution-specific reactivities on the functional role of the native 2'-hydroxyl groups are discussed. Images PMID:1736306

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

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

PubMed

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

2016-01-01

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

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

USDA-ARS?s Scientific Manuscript database

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. ...

A polymeric prodrug of 5-fluorouracil-1-acetic acid using a multi-hydroxyl polyethylene glycol derivative as the drug carrier.

PubMed

Li, Man; Liang, Zhen; Sun, Xun; Gong, Tao; Zhang, Zhirong

2014-01-01

Macromolecular prodrugs obtained by covalently conjugating small molecular drugs with polymeric carriers were proven to accomplish controlled and sustained release of the therapeutic agents in vitro and in vivo. Polyethylene glycol (PEG) has been extensively used due to its low toxicity, low immunogenicity and high biocompatibility. However, for linear PEG macromolecules, the number of available hydroxyl groups for drug coupling does not change with the length of polymeric chain, which limits the application of PEG for drug conjugation purposes. To increase the drug loading and prolong the retention time of 5-fluorouracil (5-Fu), a macromolecular prodrug of 5-Fu, 5-fluorouracil-1 acid-PAE derivative (5-FA-PAE) was synthesized and tested for the antitumor activity in vivo. PEG with a molecular weight of 38 kDa was selected to synthesize the multi-hydroxyl polyethylene glycol derivative (PAE) through an addition reaction. 5-fluorouracil-1 acetic acid (5-FA), a 5-Fu derivative was coupled with PEG derivatives via ester bond to form a macromolecular prodrug, 5-FA-PAE. The in vitro drug release, pharmacokinetics, in vivo distribution and antitumor effect of the prodrug were investigated, respectively. The PEG-based prodrug obtained in this study possessed an exceedingly high 5-FA loading efficiency of 10.58%, much higher than the maximum drug loading efficiency of unmodified PEG with the same molecular weight, which was 0.98% theoretically. Furthermore, 5-FA-PAE exhibited suitable sustained release in tumors. This study provides a new approach for the development of the delivery to tumors of anticancer agents with PEG derivatives.

DNA Binding Hydroxyl Radical Probes.

PubMed

Tang, Vicky J; Konigsfeld, Katie M; Aguilera, Joe A; Milligan, Jamie R

2012-01-01

The hydroxyl radical is the primary mediator of DNA damage by the indirect effect of ionizing radiation. It is a powerful oxidizing agent produced by the radiolysis of water and is responsible for a significant fraction of the DNA damage associated with ionizing radiation. There is therefore an interest in the development of sensitive assays for its detection. The hydroxylation of aromatic groups to produce fluorescent products has been used for this purpose. We have examined four different chromophores which produce fluorescent products when hydroxylated. Of these, the coumarin system suffers from the fewest disadvantages. We have therefore examined its behavior when linked to a cationic peptide ligand designed to bind strongly to DNA.

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

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

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

PubMed Central

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

2009-01-01

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

HETEROGENOUS PHOTOREACTION OF FORMALDEHYDE WITH HYDROXYL RADICALS

EPA Science Inventory

Atmospheric heterogeneous photoreactions occur between formaldehyde and hydroxyl radicals to produce formic acid. hese photoreactions not only occur in clouds, but also in other tropospheric hydrometeors such as precipitation and dew droplets. xperiments were performed by irradia...

A domain swapping approach to elucidate differential regiospecific hydroxylation by geraniol and linalool synthases from perilla.

PubMed

Sato-Masumoto, Naoko; Ito, Michiho

2014-06-01

Geraniol and linalool are acyclic monoterpenes found in plant essential oils that have attracted much attention for their commercial use and in pharmaceutical studies. They are synthesized from geranyl diphosphate (GDP) by geraniol and linalool synthases, respectively. Both synthases are very similar at the amino acid level and share the same substrate; however, the position of the GDP to which they introduce hydroxyl groups is different. In this study, the mechanisms underlying the regiospecific hydroxylation of geraniol and linalool synthases were investigated using a domain swapping approach and site-directed mutagenesis in perilla. Sequences of the synthases were divided into ten domains (domains I to IV-4), and each corresponding domain was exchanged between both enzymes. It was shown that different regions were important for the formation of geraniol and linalool, namely, domains IV-1 and -4 for geraniol, and domains III-b, III-d, and IV-4 for linalool. These results suggested that the conformation of carbocation intermediates and their electron localization were seemingly to be different between geraniol and linalool synthases. Further, five amino acids in domain IV-4 were apparently indispensable for the formation of geraniol and linalool. According to three-dimensional structural models of the synthases, these five residues seemed to be responsible for the different spatial arrangement of the amino acid at H524 in the case of geraniol synthase, while N526 is the corresponding residue in linalool synthase. These results suggested that the side-chains of these five amino acids, in combination with several relevant domains, localized the positive charge in the carbocation intermediate to determine the position of the introduced hydroxyl group. Copyright © 2014 Elsevier Ltd. All rights reserved.

The temperature dependence of the rate constant for the reaction of hydroxyl radicals with nitric acid

NASA Technical Reports Server (NTRS)

Kurylo, M. J.; Cornett, K. D.; Murphy, J. L.

1982-01-01

The rate constant for the reaction of hydroxyl radicals with nitric acid in the 225-443 K temperature range has been measured by means of the flash photolysis resonance fluorescence technique. Above 300 K, the rate constant levels off in a way that can only be explained by the occurrence of two reaction channels, of which one, operative at low temperatures, proceeds through the formation of an adduct intermediate. The implications of these rate constant values for stratospheric reaction constants is discussed.

OH-PRED: prediction of protein hydroxylation sites by incorporating adapted normal distribution bi-profile Bayes feature extraction and physicochemical properties of amino acids.

PubMed

Jia, Cang-Zhi; He, Wen-Ying; Yao, Yu-Hua

2017-03-01

Hydroxylation of proline or lysine residues in proteins is a common post-translational modification event, and such modifications are found in many physiological and pathological processes. Nonetheless, the exact molecular mechanism of hydroxylation remains under investigation. Because experimental identification of hydroxylation is time-consuming and expensive, bioinformatics tools with high accuracy represent desirable alternatives for large-scale rapid identification of protein hydroxylation sites. In view of this, we developed a supporter vector machine-based tool, OH-PRED, for the prediction of protein hydroxylation sites using the adapted normal distribution bi-profile Bayes feature extraction in combination with the physicochemical property indexes of the amino acids. In a jackknife cross validation, OH-PRED yields an accuracy of 91.88% and a Matthew's correlation coefficient (MCC) of 0.838 for the prediction of hydroxyproline sites, and yields an accuracy of 97.42% and a MCC of 0.949 for the prediction of hydroxylysine sites. These results demonstrate that OH-PRED increased significantly the prediction accuracy of hydroxyproline and hydroxylysine sites by 7.37 and 14.09%, respectively, when compared with the latest predictor PredHydroxy. In independent tests, OH-PRED also outperforms previously published methods.

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

PubMed

Treesuwan, Witcha; Suramitr, Songwut; Hannongbua, Supa

2015-06-01

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

[Study of scavenging activity of sorghum pigment to hydroxyl free radicals by fluorimetry].

PubMed

Zhang, Hai-rong; Wang, Wen-yan

2007-03-01

A natural product, sorghum pigment, consists of a number of important flavonoid derivatives, occurrs on the seed capsules or in the stems of many sorghums, and is widely applied in different fields of food, cosmetic and dyeing industries, It is important for scavenging hydroxyl free radicals and protection of human healthiness. Scavenging capacities of hydroxyl free radicals with sodium nitrite, quercetin and sorghum pigment were comparatively researched by fluorimetry, and the model of hydroxyl free radicals produced is based on the reaction of Cu2+ -catalyzed oxidation of ascorbic acid in the presence of hydrogen peroxide. The hydroxyl radicals react with benzoic acid, forming a fluorescent product, and the fluorescence intensity was determined by the concentration of hydroxybenzoic acid. The experimental results show that the sodium nitrite, quercetin and sorghum pigment have a quantity-effect relationship for scavenging hydroxyl free radicals, and sodium nitrite and quercetin in comparison with sorghum pigment have high antioxidant capacity. Finally, the quenching mechanisms were explored with sodium nitrite, sorghum pigment, and quercetin respectively. The sorghum pigment and sodium nitrite feature a dynamic quenching processes, while quercetin shows a static quenching processes. A reference method was provided for reasonable exploitation and utilization of sorghum pigment.

A Polymeric Prodrug of 5-Fluorouracil-1-Acetic Acid Using a Multi-Hydroxyl Polyethylene Glycol Derivative as the Drug Carrier

PubMed Central

Sun, Xun; Gong, Tao; Zhang, Zhirong

2014-01-01

Purpose Macromolecular prodrugs obtained by covalently conjugating small molecular drugs with polymeric carriers were proven to accomplish controlled and sustained release of the therapeutic agents in vitro and in vivo. Polyethylene glycol (PEG) has been extensively used due to its low toxicity, low immunogenicity and high biocompatibility. However, for linear PEG macromolecules, the number of available hydroxyl groups for drug coupling does not change with the length of polymeric chain, which limits the application of PEG for drug conjugation purposes. To increase the drug loading and prolong the retention time of 5-fluorouracil (5-Fu), a macromolecular prodrug of 5-Fu, 5-fluorouracil-1 acid-PAE derivative (5-FA-PAE) was synthesized and tested for the antitumor activity in vivo. Methods PEG with a molecular weight of 38 kDa was selected to synthesize the multi-hydroxyl polyethylene glycol derivative (PAE) through an addition reaction. 5-fluorouracil-1 acetic acid (5-FA), a 5-Fu derivative was coupled with PEG derivatives via ester bond to form a macromolecular prodrug, 5-FA-PAE. The in vitro drug release, pharmacokinetics, in vivo distribution and antitumor effect of the prodrug were investigated, respectively. Results The PEG-based prodrug obtained in this study possessed an exceedingly high 5-FA loading efficiency of 10.58%, much higher than the maximum drug loading efficiency of unmodified PEG with the same molecular weight, which was 0.98% theoretically. Furthermore, 5-FA-PAE exhibited suitable sustained release in tumors. Conclusion This study provides a new approach for the development of the delivery to tumors of anticancer agents with PEG derivatives. PMID:25389968

Catalytic Hydroxylation of Polyethylenes

PubMed Central

2017-01-01

Polyolefins account for 60% of global plastic consumption, but many potential applications of polyolefins require that their properties, such as compatibility with polar polymers, adhesion, gas permeability, and surface wetting, be improved. A strategy to overcome these deficiencies would involve the introduction of polar functionalities onto the polymer chain. Here, we describe the Ni-catalyzed hydroxylation of polyethylenes (LDPE, HDPE, and LLDPE) in the presence of mCPBA as an oxidant. Studies with cycloalkanes and pure, long-chain alkanes were conducted to assess precisely the selectivity of the reaction and the degree to which potential C–C bond cleavage of a radical intermediate occurs. Among the nickel catalysts we tested, [Ni(Me4Phen)3](BPh4)2 (Me4Phen = 3,4,7,8,-tetramethyl-1,10-phenanthroline) reacted with the highest turnover number (TON) for hydroxylation of cyclohexane and the highest selectivity for the formation of cyclohexanol over cyclohexanone (TON, 5560; cyclohexanol/(cyclohexanone + ε-caprolactone) ratio, 10.5). The oxidation of n-octadecane occurred at the secondary C–H bonds with 15.5:1 selectivity for formation of an alcohol over a ketone and 660 TON. Consistent with these data, the hydroxylation of various polyethylene materials by the combination of [Ni(Me4Phen)3](BPh4)2 and mCPBA led to the introduction of 2.0 to 5.5 functional groups (alcohol, ketone, alkyl chloride) per 100 monomer units with up to 88% selectivity for formation of alcohols over ketones or chloride. In contrast to more classical radical functionalizations of polyethylene, this catalytic process occurred without significant modification of the molecular weight of the polymer that would result from chain cleavage or cross-linking. Thus, the resulting materials are new compositions in which hydroxyl groups are located along the main chain of commercial, high molecular weight LDPE, HDPE, and LLDPE materials. These hydroxylated polyethylenes have improved wetting

Promotional effect of surface hydroxyls on electrochemical reduction of CO2 over SnOx/Sn electrode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cui, Chaonan; Han, Jinyu; Zhu, Xinli

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, formingmore » 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

Photoactivatable Rhodamine Spiroamides and Diazoketones Decorated with "Universal Hydrophilizer" or Hydroxyl Groups.

PubMed

Roubinet, Benoit; Bischoff, Matthias; Nizamov, Shamil; Yan, Sergey; Geisler, Claudia; Stoldt, Stefan; Mitronova, Gyuzel Y; Belov, Vladimir N; Bossi, Mariano L; Hell, Stefan W

2018-05-11

Photoactivatable rhodamine spiroamides and spirocyclic diazoketones emerged recently as synthetic markers applicable in multicolor superresolution microscopy. However, their applicability in single molecule localization microscopy (SMLM) is often limited by aggregation, unspecific adhesion and low reactivity caused by insufficient solubility and precipitation from aqueous solutions. We report here two synthetic modifications increasing the polarity of compact polycyclic and hydrophobic labels decorated with a reactive group: attachment of 3-sulfo-L-alanyl - beta-alanine dipeptide (a "universal hydrophilizer") or allylic hydroxylation in photosensitive rhodamine diazoketones (and spiroamides). The superresolution images of tubulin and keratin filaments in fixed and living cells exemplify the performance of "blinking" spiroamides derived from N,N,N',N'-tetramethyl rhodamine.

2-Pyridinyl Thermolabile Groups as General Protectants for Hydroxyl, Phosphate, and Carboxyl Functions.

PubMed

Brzezinska, Jolanta; Witkowska, Agnieszka; Kaczyński, Tomasz P; Krygier, Dominika; Ratajczak, Tomasz; Chmielewski, Marcin K

2017-03-02

Application of 2-pyridinyl thermolabile protecting groups (2-PyTPGs) for protection of hydroxyl, phosphate, and carboxyl functions is presented in this unit. Their characteristic feature is a unique removal process following the intramolecular cyclization mechanism and induced only by temperature rise. Deprotection rate of 2-PyTPGs is dependent on certain parameters, such as solvent (aqueous or non-aqueous medium), pH values, and electron distribution in a pyridine ring. The presented approach pertains not only to protecting groups but also to an advanced system of controlling certain properties of 2-pyridinyl derivatives. We improved the "chemical switch" method, allowing us to regulate the protecting group stability by inversing the electron distribution in 2-PyTPG. Together with pH values manipulation, this allows us to regulate the protecting group stability. Moreover, phosphite cyclization to oxazaphospholidine provides a very stable but easily reversible tool for phosphate protection/modifications. For all TPGs we confirmed their utility in a system of protecting groups. This concept can contribute to designing the general protecting group that could be useful in bioorganic chemistry. © 2017 by John Wiley & Sons, Inc. Copyright © 2017 John Wiley & Sons, Inc.

Production of high molecular weight polylactic acid

DOEpatents

Bonsignore, Patrick V.

1995-01-01

A degradable high molecular weight poly(lactic acid). A poly(lactic acid) has a terminal end group of one of carboxyl or hydroxyl groups with low molecular weight poly(lactic acid) units coupled with linking agents of di-isocyanates, bis-epoxides, bis-oxazolines and bis-ortho esters. The resulting high molecular weight poly(lactic acid) can be used for applications taking advantage of the improved physical properties.

Action mechanism of tyrosinase on meta- and para-hydroxylated monophenols.

PubMed

Fenoll, L G; Rodríguez-López, J N; Varón, R; García-Ruiz, P A; García-Cánovas, F; Tudela, J

2000-04-01

The relationship between the structure and activity of meta- and para-hydroxylated monophenols was studied during their tyrosinase-catalysed hydroxylation and the rate-limiting steps of the reaction mechanism were identified. The para-hydroxylated substrates permit us to study the effect of a substituent (R) in the carbon-1 position (C-1) of the benzene ring on the nucleophilic attack step, while the meta group permits a similar study of the effect on the electrophilic attack step. Substrates with a -OCH3 group on C-1, as p-hydroxyanisol (4HA) and m-hydroxyanisol (3HA), or with a -CH2OH group, as p-hydroxybenzylalcohol (4HBA) and m-hydroxybenzylalcohol (3HBA), were used because the effect of the substituent (R) size was assumed to be similar. However, the electron-donating effect of the -OCH3 group means that the carbon-4 position (C-4) is favoured for nucleophilic attack (para-hydroxylated substrates) or for electrophilic attack (meta-hydroxylated substrates). The electron-attracting effect of the -CH2OH group has the opposite effect, hindering nucleophilic (para) or electrophilic (meta) attack of C-4. The experimental data point to differences between the maximum steady-state rate (V(M)Max) of the different substrates, the value of this parameter depends on the nucleophilic and electrophilic attack. However, differences are greatest in the Michaelis constants (K(M)m), with the meta-hydroxylated substrates having very large values. The catalytic efficiency k(M)cat/K(M)m is much greater for thepara-hydroxylated substrates although it varies greatly between one substrate and the other. However, it varies much less in the meta-hydroxylated substrates since this parameter describes the power of the nucleophilic attack, which is weaker in the meta OH. The large increase in the K(M)m of the meta-hydroxylated substrates might suggest that the phenolic OH takes part in substrate binding. Since this is a weaker nucleophil than the para-hydroxylated substrates, the binding

Effect of curcumin against oxidation of biomolecules by hydroxyl radicals.

PubMed

Borra, Sai Krishna; Mahendra, Jaideep; Gurumurthy, Prema; Jayamathi; Iqbal, Shabeer S; Mahendra, Little

2014-10-01

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. 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. 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. 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. These observations suggest the hydroxyl radical scavenging potentials of curcumin and protective actions to prevent the oxidation of biomolecules by hydroxyl radicals.

Production of high molecular weight polylactic acid

DOEpatents

Bonsignore, P.V.

1995-11-28

A degradable high molecular weight poly(lactic acid) is described. The poly(lactic acid) has a terminal end group of one of carboxyl or hydroxyl groups with low molecular weight poly(lactic acid) units coupled with linking agents of di-isocyanates, bis-epoxides, bis-oxazolines and bis-ortho esters. The resulting high molecular weight poly(lactic acid) can be used for applications taking advantage of the improved physical properties.

Formation Of Nitrous Acid In Various Environments And Its Contribution To Hydroxyl Radical Budget

NASA Astrophysics Data System (ADS)

Li, X.; Lu, K.; Liu, Y.; Rohrer, F.; Häseler, R.; Bohn, B.; Fuchs, H.; Hofzumahaus, A.; Wahner, A.; Kiendler-Scharr, A.; Zeng, L.; Zhang, Y.

2017-12-01

Nitrous acid (HONO) is an important trace gas in the atmosphere due to its contribution to the cycles of nitrogen oxides (NOx) and hydrogen oxides (HOx). Yet the formation mechanism of HONO during daytime remains large uncertainty. In the past ten years, we performed ground HONO measurements using the LOPAP technique in different seasons in two major mega-city areas, i.e., North China Plain and Pearl River Delta. Spatial distribution of HONO over different regions in Europe was also observed by the same technique on-board the Zeppelin NT airship in 2012 and 2013. For all field observations, parameters (OH, HO2, NOx, photolysis frequencies, aerosols, etc.) influencing the HONO budget were measured simultaneous, which allows us to investigate the source of HONO and its contribution to the hydroxyl radical budget. In this presentation, we summarize the general features of HONO in the planetary boundary layer in terms of its daytime concentration, spatial distribution, and source strength, and contribution to the primary OH production. Various proposed HONO formation mechanisms have been tested in order to explain the widely exited missing daytime HONO production of 100 - 200 ppt h-1 . We will show that there is not a stand alone mechanism can be used for explaining the HONO formation in various environments. Design of field experiments which effectively separate different physical and chemical processes would be helpful to pin down the major daytime HONO source and to understand its influence on the hydroxyl radical budget.

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

Glycerol dehydratation by the B12-independent enzyme may not involve the migration of a hydroxyl group: a computational study.

PubMed

Feliks, Mikolaj; Ullmann, G Matthias

2012-06-21

A combination of continuum electrostatic and density functional calculations has been employed to study the mechanism of the B(12)-independent glycerol dehydratase, a novel glycyl-radical enzyme involved in the microbial conversion of glycerol to 3-hydroxylpropionaldehyde. The calculations indicate that the dehydratation of glycerol by the B(12)-independent enzyme does not need to involve a mechanistically complicated migration of the middle hydroxyl group to one of the two terminal positions of a molecule, as previously suggested. Instead, the reaction can proceed in three elementary steps. First, a radical transfer from the catalytically active Cys433 to the ligand generates a substrate-related intermediate. Second, a hydroxyl group splits off at the middle position of the ligand and is protonated by the neighboring His164 to form a water molecule. The other active site residue Glu435 accepts a proton from one of the terminal hydroxyl groups of the ligand and a C═O double bond is created. Third, the reaction is completed by a radical back transfer from the product-related intermediate to Cys433. On the basis of our calculations, the catalytic functions of the active site residues have been suggested. Cys433 is a radical relay site; His164 and Glu435 make up a proton accepting/donating system; Asn156, His281, and Asp447 form a network of hydrogen bonds responsible for the electrostatic stabilization of the transition state. A synergistic participation of these residues in the reaction seems to be crucial for the catalysis.

Sphingolipid hydroxylation in mammals, yeast and plants - An integrated view.

PubMed

Marquês, Joaquim Trigo; Susana Marinho, H; de Almeida, Rodrigo Freire Martins

2018-05-07

This review is focused on sphingolipid backbone hydroxylation, a small but widespread structural feature, with profound impact on membrane biophysical properties. We start by summarizing sphingolipid metabolism in mammalian cells, yeast and plants, focusing on how distinct hydroxylation patterns emerge in different eukaryotic kingdoms. Then, a comparison of the biophysical properties in membrane model systems and cellular membranes from diverse organisms is made. From an integrative perspective, these results can be rationalized considering that superficial hydroxyl groups in the backbone of sphingolipids (by intervening in the H-bond network) alter the balance of favorable interactions between membrane lipids. They may strengthen the bonding or compete with other hydroxyl groups, in particular the one of membrane sterols. Different sphingolipid hydroxylation patterns can stabilize/disrupt specific membrane domains or change whole plasma membrane properties, and therefore be important in the control of protein distribution, function and lateral diffusion and in the formation and overtime stability of signaling platforms. The recent examples explored throughout this review unveil a potentially key role for sphingolipid backbone hydroxylation in both physiological and pathological situations, as they can be of extreme importance for the proper organization of cell membranes in mammalian cells, yeast and, most likely, also in plants. Copyright © 2017. Published by Elsevier Ltd.

Protective effects of buckwheat honey on DNA damage induced by hydroxyl radicals.

PubMed

Zhou, Juan; Li, Peng; Cheng, Ni; Gao, Hui; Wang, Bini; Wei, Yahui; Cao, Wei

2012-08-01

To understand the antioxidant properties of buckwheat honeys, we investigated their antioxidant effects on hydroxyl radical-induced DNA breaks in the non-site-specific and site-specific systems, the physicochemical properties, antioxidant activities (1,1-diphenyl-2-picrylhydrazyl (DPPH), hydroxyl radical scavenging activity, chelating, and reducing power assays), total phenolic content and individual phenolic acids were also determined. Total phenolic content of buckwheat honeys ranged from 774 to 1694 mg PA/kg, and p-hydroxybenzoic and p-coumaric acids proved to be the main components in buckwheat honeys. All the buckwheat honey samples possess stronger capability to protect DNA in the non-site-specific systems than in the site-specific systems from being damaged by hydroxyl radicals. In the non-site-specific and site-specific system, buckwheat honeys samples prevented ()OH-induced DNA breaks by 21-78% and 5-31% over control value, respectively. Copyright © 2012 Elsevier Ltd. All rights reserved.

Prolyl hydroxylation regulates protein degradation, synthesis, and splicing in human induced pluripotent stem cell-derived cardiomyocytes

PubMed Central

Stoehr, Andrea; Yang, Yanqin; Patel, Sajni; Evangelista, Alicia M.; Aponte, Angel; Wang, Guanghui; Liu, Poching; Boylston, Jennifer; Kloner, Philip H.; Lin, Yongshun; Gucek, Marjan; Zhu, Jun; Murphy, Elizabeth

2016-01-01

Aims Protein hydroxylases are oxygen- and α-ketoglutarate-dependent enzymes that catalyse hydroxylation of amino acids such as proline, thus linking oxygen and metabolism to enzymatic activity. Prolyl hydroxylation is a dynamic post-translational modification that regulates protein stability and protein–protein interactions; however, the extent of this modification is largely uncharacterized. The goals of this study are to investigate the biological consequences of prolyl hydroxylation and to identify new targets that undergo prolyl hydroxylation in human cardiomyocytes. Methods and results We used human induced pluripotent stem cell-derived cardiomyocytes in combination with pulse-chase amino acid labelling and proteomics to analyse the effects of prolyl hydroxylation on protein degradation and synthesis. We identified 167 proteins that exhibit differences in degradation with inhibition of prolyl hydroxylation by dimethyloxalylglycine (DMOG); 164 were stabilized. Proteins involved in RNA splicing such as serine/arginine-rich splicing factor 2 (SRSF2) and splicing factor and proline- and glutamine-rich (SFPQ) were stabilized with DMOG. DMOG also decreased protein translation of cytoskeletal and sarcomeric proteins such as α-cardiac actin. We searched the mass spectrometry data for proline hydroxylation and identified 134 high confidence peptides mapping to 78 unique proteins. We identified SRSF2, SFPQ, α-cardiac actin, and cardiac titin as prolyl hydroxylated. We identified 29 prolyl hydroxylated proteins that showed a significant difference in either protein degradation or synthesis. Additionally, we performed next-generation RNA sequencing and showed that the observed decrease in protein synthesis was not due to changes in mRNA levels. Because RNA splicing factors were prolyl hydroxylated, we investigated splicing ± inhibition of prolyl hydroxylation and detected 369 alternative splicing events, with a preponderance of exon skipping. Conclusions This study

Enhanced lignin monomer production caused by cinnamic Acid and its hydroxylated derivatives inhibits soybean root growth.

PubMed

Lima, Rogério Barbosa; Salvador, Victor Hugo; dos Santos, Wanderley Dantas; Bubna, Gisele Adriana; Finger-Teixeira, Aline; Soares, Anderson Ricardo; Marchiosi, Rogério; Ferrarese, Maria de Lourdes Lucio; Ferrarese-Filho, Osvaldo

2013-01-01

Cinnamic acid and its hydroxylated derivatives (p-coumaric, caffeic, ferulic and sinapic acids) are known allelochemicals that affect the seed germination and root growth of many plant species. Recent studies have indicated that the reduction of root growth by these allelochemicals is associated with premature cell wall lignification. We hypothesized that an influx of these compounds into the phenylpropanoid pathway increases the lignin monomer content and reduces the root growth. To confirm this hypothesis, we evaluated the effects of cinnamic, p-coumaric, caffeic, ferulic and sinapic acids on soybean root growth, lignin and the composition of p-hydroxyphenyl (H), guaiacyl (G) and syringyl (S) monomers. To this end, three-day-old seedlings were cultivated in nutrient solution with or without allelochemical (or selective enzymatic inhibitors of the phenylpropanoid pathway) in a growth chamber for 24 h. In general, the results showed that 1) cinnamic, p-coumaric, caffeic and ferulic acids reduced root growth and increased lignin content; 2) cinnamic and p-coumaric acids increased p-hydroxyphenyl (H) monomer content, whereas p-coumaric, caffeic and ferulic acids increased guaiacyl (G) content, and sinapic acid increased sinapyl (S) content; 3) when applied in conjunction with piperonylic acid (PIP, an inhibitor of the cinnamate 4-hydroxylase, C4H), cinnamic acid reduced H, G and S contents; and 4) when applied in conjunction with 3,4-(methylenedioxy)cinnamic acid (MDCA, an inhibitor of the 4-coumarate:CoA ligase, 4CL), p-coumaric acid reduced H, G and S contents, whereas caffeic, ferulic and sinapic acids reduced G and S contents. These results confirm our hypothesis that exogenously applied allelochemicals are channeled into the phenylpropanoid pathway causing excessive production of lignin and its main monomers. By consequence, an enhanced stiffening of the cell wall restricts soybean root growth.

Enhanced Lignin Monomer Production Caused by Cinnamic Acid and Its Hydroxylated Derivatives Inhibits Soybean Root Growth

PubMed Central

Lima, Rogério Barbosa; Salvador, Victor Hugo; dos Santos, Wanderley Dantas; Bubna, Gisele Adriana; Finger-Teixeira, Aline; Soares, Anderson Ricardo; Marchiosi, Rogério; Ferrarese, Maria de Lourdes Lucio; Ferrarese-Filho, Osvaldo

2013-01-01

Cinnamic acid and its hydroxylated derivatives (p-coumaric, caffeic, ferulic and sinapic acids) are known allelochemicals that affect the seed germination and root growth of many plant species. Recent studies have indicated that the reduction of root growth by these allelochemicals is associated with premature cell wall lignification. We hypothesized that an influx of these compounds into the phenylpropanoid pathway increases the lignin monomer content and reduces the root growth. To confirm this hypothesis, we evaluated the effects of cinnamic, p-coumaric, caffeic, ferulic and sinapic acids on soybean root growth, lignin and the composition of p-hydroxyphenyl (H), guaiacyl (G) and syringyl (S) monomers. To this end, three-day-old seedlings were cultivated in nutrient solution with or without allelochemical (or selective enzymatic inhibitors of the phenylpropanoid pathway) in a growth chamber for 24 h. In general, the results showed that 1) cinnamic, p-coumaric, caffeic and ferulic acids reduced root growth and increased lignin content; 2) cinnamic and p-coumaric acids increased p-hydroxyphenyl (H) monomer content, whereas p-coumaric, caffeic and ferulic acids increased guaiacyl (G) content, and sinapic acid increased sinapyl (S) content; 3) when applied in conjunction with piperonylic acid (PIP, an inhibitor of the cinnamate 4-hydroxylase, C4H), cinnamic acid reduced H, G and S contents; and 4) when applied in conjunction with 3,4-(methylenedioxy)cinnamic acid (MDCA, an inhibitor of the 4-coumarate:CoA ligase, 4CL), p-coumaric acid reduced H, G and S contents, whereas caffeic, ferulic and sinapic acids reduced G and S contents. These results confirm our hypothesis that exogenously applied allelochemicals are channeled into the phenylpropanoid pathway causing excessive production of lignin and its main monomers. By consequence, an enhanced stiffening of the cell wall restricts soybean root growth. PMID:24312480

Rodlike Supramolecular Nanoassemblies of Degradable Poly(Aspartic Acid) Derivatives and Hydroxyl-Rich Polycations for Effective Delivery of Versatile Tumor-Suppressive ncRNAs.

PubMed

Song, Hai-Qing; Pan, Wenting; Li, Rui-Quan; Yu, Bingran; Liu, Wenjuan; Yang, Ming; Xu, Fu-Jian

2018-03-01

The delivery of tumor-suppressive noncoding RNAs (ncRNAs) including short ncRNAs (i.e., miRNAs) and long ncRNAs (lncRNAs) is put forward to treat tumors. In this work, novel rodlike supramolecular nanoassemblies (CNC @CB[8] @ PGEA) of degradable poly(aspartic acid) (PAsp) derivatives-grafted cellulose nanocrystals (CNCs) and hydroxyl-rich polycations (ethanolamine-functionalized poly(glycidyl methacrylate), PGEA) are proposed via typical cucurbit[8]uril (CB[8])-based host-guest interactions for delivery of different ncRNAs to treat hepatocellular carcinoma (HCC). Spindly CNCs, one kind of natural polysaccharide nanoparticles, possess good biocompatibility and unique physico-chemical properties. PGEA with abundant hydroxyl groups is one promising gene carrier with low cytotoxicity. PAsp can benefit the disassembly and degradability of nanoassemblies within cells. CNC @ CB[8]@PGEA combines the different unique properties of CNC, PGEA, and PAsp. CNC @ CB[8] @ PGEA effectively complexes the expression constructs of miR-101 (plasmid pc3.0-miR-101) and lncRNA MEG3 (plasmid pc3.0-MEG3). CNC @ CB[8] @ PGEA produces much better transfection performances than PGEA-containing assembly units. In addition, the codelivery system of CNC @ CB[8] @ PGEA/(pc3.0-MEG3+pc3.0-miR-101) nanocomplexes demonstrates better efficacy in suppressing HCC than CNC @ CB[8] @ PGEA/pc3.0-MEG3 or CNC @ CB[8] @ PGEA/pc3.0-miR-101 nanocomplexes alone. Such rodlike supramolecular nanoassemblies will provide a promising means to produce efficient delivery vectors of versatile tumor-suppressive nucleic acids. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Exploring the reaction channels between arsine and the hydroxyl radical

NASA Astrophysics Data System (ADS)

Viana, Rommel B.

2017-10-01

The aim of this study was to present the reaction mechanism channels between arsine (AsH3) and hydroxyl (OH) which was evaluated at CCSD(T)/CBS//CCSD/cc-pVTZ level. One potential channel is the hydrogen abstraction pathway (R1), leading to AsH2 and H2O products, which occurs due to the formation of an entrance complex (AsH3OH) followed by a 1,2-hydrogen shift pathway (involving the proton transfer from the arsine group to hydroxyls, with one leading to the products). Additional channels are accessed via H-elimination pathways of the entrance complexes, forming arsinous acid (AsH2OH; R2) and arsine oxide (AsH3O; R3). In this respect, R2 is the only exoergic route of the three exit channels, representing the major branching ratio at 200-1000 K and, after 2000 K, R1 increases gradually becoming the major route of this reaction. In contrast, even at 4000 K, R3 is a highly unfeasible pathway. Therefore, the information predicted here provides new insights into the neutral-neutral chemical reaction dynamics regarding the Group V hydrides. On the other side, the R2 pathway may have some potential to solve the arsine oxidation puzzle as a possible primary pathway to the arsenic-oxygen species formation.

Hydrogen-bond rich ionic liquids with hydroxyl cationic tails

NASA Astrophysics Data System (ADS)

Deng, Li; Shi, Rui; Wang, Yanting; Ou-Yang, Zhong-Can

2013-02-01

To investigate if the amphiphilic feature exhibited in ionic liquids (ILs) with nonpolar cationic tails still exists in ILs with polar tails, by performing molecular dynamics simulations for 1-(8-hydroxyoctyl)-3-methyl-imidazolium nitrate (COH) and 1-octyl-3-methyl-imidazolium nitrate (C8), we found that, in COH, cationic tail groups can no longer aggregate to form separated nonpolar tail domains, instead hydroxyl groups form a rich number of hydrogen bonds with other groups, indicating that the hydroxyl substituent changes the IL system from an amphiphilic liquid to a polar liquid. Due to the large amount of hydrogen bonds, COH has slower dynamics than C8.

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.

Interaction of aromatic alcohols, aldehydes and acids with α-hydroxyl-containing carbon-centered radicals: A steady state radiolysis study

NASA Astrophysics Data System (ADS)

Samovich, S. N.; Brinkevich, S. D.; Shadyro, O. I.

2013-01-01

Benzaldehyde and its derivatives efficaciously oxidize in aqueous solutions α-hydroxyl-containing carbon-centered radicals (α-HCR) of various structures, suppressing thereby the radical recombination and fragmentation reactions. The compounds containing cinnamic moieties are capable of adding α-hydroxyethyl radicals (α-HER) to the carbon-carbon double bonds conjugated with the aromatic system to form molecular products identifiable by mass spectrometry. On radiolysis of aqueous ethanol solutions, reduction of α-HER by aromatic alcohols and acids has been shown to proceed via formation of their adducts with hydrated electron species.

Prolyl hydroxylation regulates protein degradation, synthesis, and splicing in human induced pluripotent stem cell-derived cardiomyocytes.

PubMed

Stoehr, Andrea; Yang, Yanqin; Patel, Sajni; Evangelista, Alicia M; Aponte, Angel; Wang, Guanghui; Liu, Poching; Boylston, Jennifer; Kloner, Philip H; Lin, Yongshun; Gucek, Marjan; Zhu, Jun; Murphy, Elizabeth

2016-06-01

Protein hydroxylases are oxygen- and α-ketoglutarate-dependent enzymes that catalyse hydroxylation of amino acids such as proline, thus linking oxygen and metabolism to enzymatic activity. Prolyl hydroxylation is a dynamic post-translational modification that regulates protein stability and protein-protein interactions; however, the extent of this modification is largely uncharacterized. The goals of this study are to investigate the biological consequences of prolyl hydroxylation and to identify new targets that undergo prolyl hydroxylation in human cardiomyocytes. We used human induced pluripotent stem cell-derived cardiomyocytes in combination with pulse-chase amino acid labelling and proteomics to analyse the effects of prolyl hydroxylation on protein degradation and synthesis. We identified 167 proteins that exhibit differences in degradation with inhibition of prolyl hydroxylation by dimethyloxalylglycine (DMOG); 164 were stabilized. Proteins involved in RNA splicing such as serine/arginine-rich splicing factor 2 (SRSF2) and splicing factor and proline- and glutamine-rich (SFPQ) were stabilized with DMOG. DMOG also decreased protein translation of cytoskeletal and sarcomeric proteins such as α-cardiac actin. We searched the mass spectrometry data for proline hydroxylation and identified 134 high confidence peptides mapping to 78 unique proteins. We identified SRSF2, SFPQ, α-cardiac actin, and cardiac titin as prolyl hydroxylated. We identified 29 prolyl hydroxylated proteins that showed a significant difference in either protein degradation or synthesis. Additionally, we performed next-generation RNA sequencing and showed that the observed decrease in protein synthesis was not due to changes in mRNA levels. Because RNA splicing factors were prolyl hydroxylated, we investigated splicing ± inhibition of prolyl hydroxylation and detected 369 alternative splicing events, with a preponderance of exon skipping. This study provides the first extensive

The gene road to royalty--differential expression of hydroxylating genes in the mandibular glands of the honeybee.

PubMed

Malka, Osnat; Karunker, Iris; Yeheskel, Adva; Morin, Shai; Hefetz, Abraham

2009-10-01

The advances in honeybee sociogenomics have paved the way for the study of social communication processes at the gene level, in particular the expression of caste-specific pheromones. The queen honeybee mandibular pheromone provides an excellent model system, in that biosynthesis of the hydroxylating fatty acid caste-specific pheromone appears to be reduced to a single chemical hydroxylation step of stearic acid. Queens are typified by omega-1-hydroxylation, as opposed to the worker-typical omega-hydroxylation. We hypothesized that this bifurcation is the consequence of differential expression of caste-specific genes that code for fatty acid-hydroxylating enzymes from the cytochrome P450 (CYP) family. Bioinformatics studies disclosed two candidate proteins CYP4AA1 and CYP18A1. We thus investigated the expression of these genes in the mandibular glands of queens, and of queenright (QR) and queenless (QL) workers. The real-time PCR results revealed that CYP4AA1 (omega-hydroxylation) was expressed at high levels in both QR and QL workers, whereas in queens its expression was negligible. The expression of CYP18A1 (omega-1-hydroxylation), on the other hand, was high in the queen's glands and negligible in those of QR workers. In QL workers, however, the expression of CYP18A1 was considerably elevated and significantly greater than in QR workers. Three-dimensional structural models constructed for these enzymes demonstrate differences in the active site between CYP18A1 and CYP4AA1, in line with their differential catalytic specificity. The fact that queen pheromone plasticity can be tracked all the way to gene expression provides a new insight into the process of caste differentiation and the accompanying social communication.

Detection of hydroxyl radicals by D-phenylalanine hydroxylation: a specific assay for hydroxyl radical generation in biological systems.

PubMed

Biondi, R; Xia, Y; Rossi, R; Paolocci, N; Ambrosio, G; Zweier, J L

2001-03-01

Hydroxylation of l-phenylalanine (Phe) by hydroxyl radical (*OH) yields 4-, 3-, and 2-hydroxyl-Phe (para-, meta-, and ortho-tyrosine, respectively). Phe derivative measurements have been employed to detect *OH formation in cells and tissues, however, the specificity of this assay is limited since Phe derivatives also arise from intracellular Phe hydroxylase. d-Phe, the d-type enantiomer, is not hydroxylated by Phe hydroxylase. We evaluate whether d-Phe reacts with *OH as well as l-Phe, providing a more reliable probe for *OH generation in biological systems. With *OH generated by a Fenton reaction or xanthine oxidase, d- and l-Phe equally gave rise to p, m, o-tyr and this could be prevented by *OH scavengers. Resting human neutrophils (PMNs) markedly converted l-Phe to p-tyr, through non-oxidant-mediated reactions, whereas d-Phe was unaffected. In contrast, when PMNs were stimulated in the presence of redox cycling iron the *OH formed resulted in more significant rise of p-tyr from d-Phe (9.4-fold) than l-Phe (3.6-fold) due to the significant background formation of p-tyr from l-Phe. Together, these data indicated that d- and l-Phe were equally hydroxylated by *OH. Using d-Phe instead of l-Phe can eliminate the formation of Phe derivatives from Phe hydroxylase and achieve more specific, sensitive measurement of *OH in biological systems.

Pharmacokinetics and metabolic rates of acetyl salicylic acid and its metabolites in an Otomi ethnic group of Mexico.

PubMed

Lares-Asseff, Ismael; Juárez-Olguín, Hugo; Flores-Pérez, Janett; Guillé-Pérez, Adrian; Vargas, Arturo

2004-05-01

The objective of this study was to determine pharmacokinetic differences of acetyl salicylic acid (ASA) and its metabolites: gentisic acid (GA), salicylic acid (SA) and salicyluric acid (SUA) between Otomies and Mesticians healthy subjects. Design. Ten Otomies and 10 Mesticians were included. After a single dose of aspirin given orally (15 mg/kg), blood and urine samples were collected at different times. Results. Pharmacokinetic parameters of salicylates showed significant differences, except distribution volume of SA, and elimination half-life of SUA. Metabolic rates of ASA showed significant differences for all rates between both groups. On the other hand, percentages of dose excreted were more reduced for SA and SUA for the Otomies than for the Mesticians. Conclusion. Results reflect differences in the hydrolysis way i.e. from ASA to SA and aromatic hydroxylation i.e. from SA to GA, which were slower in Otomies subjects, showing a possible pharmacokinetic differences about the capabilities of ASA biotransformation as a consequence of ethnic differences.

Identifying organic aerosol sources by comparing functional group composition in chamber and atmospheric particles

PubMed Central

Russell, Lynn M.; Bahadur, Ranjit; Ziemann, Paul J.

2011-01-01

Measurements of submicron particles by Fourier transform infrared spectroscopy in 14 campaigns in North America, Asia, South America, and Europe were used to identify characteristic organic functional group compositions of fuel combustion, terrestrial vegetation, and ocean bubble bursting sources, each of which often accounts for more than a third of organic mass (OM), and some of which is secondary organic aerosol (SOA) from gas-phase precursors. The majority of the OM consists of alkane, carboxylic acid, hydroxyl, and carbonyl groups. The organic functional groups formed from combustion and vegetation emissions are similar to the secondary products identified in chamber studies. The near absence of carbonyl groups in the observed SOA associated with combustion is consistent with alkane rather than aromatic precursors, and the absence of organonitrate groups can be explained by their hydrolysis in humid ambient conditions. The remote forest observations have ratios of carboxylic acid, organic hydroxyl, and nonacid carbonyl groups similar to those observed for isoprene and monoterpene chamber studies, but in biogenic aerosols transported downwind of urban areas the formation of esters replaces the acid and hydroxyl groups and leaves only nonacid carbonyl groups. The carbonyl groups in SOA associated with vegetation emissions provides striking evidence for the mechanism of esterification as the pathway for possible oligomerization reactions in the atmosphere. Forest fires include biogenic emissions that produce SOA with organic components similar to isoprene and monoterpene chamber studies, also resulting in nonacid carbonyl groups in SOA. PMID:21317360

Nucleic Acid Detection Methods

DOEpatents

Smith, Cassandra L.; Yaar, Ron; Szafranski, Przemyslaw; Cantor, Charles R.

1998-05-19

The invention relates to methods for rapidly determining the sequence and/or length a target sequence. The target sequence may be a series of known or unknown repeat sequences which are hybridized to an array of probes. The hybridized array is digested with a single-strand nuclease and free 3'-hydroxyl groups extended with a nucleic acid polymerase. Nuclease cleaved heteroduplexes can be easily distinguish from nuclease uncleaved heteroduplexes by differential labeling. Probes and target can be differentially labeled with detectable labels. Matched target can be detected by cleaving resulting loops from the hybridized target and creating free 3-hydroxyl groups. These groups are recognized and extended by polymerases added into the reaction system which also adds or releases one label into solution. Analysis of the resulting products using either solid phase or solution. These methods can be used to detect characteristic nucleic acid sequences, to determine target sequence and to screen for genetic defects and disorders. Assays can be conducted on solid surfaces allowing for multiple reactions to be conducted in parallel and, if desired, automated.

Nucleic acid detection methods

DOEpatents

Smith, C.L.; Yaar, R.; Szafranski, P.; Cantor, C.R.

1998-05-19

The invention relates to methods for rapidly determining the sequence and/or length a target sequence. The target sequence may be a series of known or unknown repeat sequences which are hybridized to an array of probes. The hybridized array is digested with a single-strand nuclease and free 3{prime}-hydroxyl groups extended with a nucleic acid polymerase. Nuclease cleaved heteroduplexes can be easily distinguish from nuclease uncleaved heteroduplexes by differential labeling. Probes and target can be differentially labeled with detectable labels. Matched target can be detected by cleaving resulting loops from the hybridized target and creating free 3-hydroxyl groups. These groups are recognized and extended by polymerases added into the reaction system which also adds or releases one label into solution. Analysis of the resulting products using either solid phase or solution. These methods can be used to detect characteristic nucleic acid sequences, to determine target sequence and to screen for genetic defects and disorders. Assays can be conducted on solid surfaces allowing for multiple reactions to be conducted in parallel and, if desired, automated. 18 figs.

Comparative studies on the interaction of caffeic acid, chlorogenic acid and ferulic acid with bovine serum albumin

NASA Astrophysics Data System (ADS)

Li, Shuang; Huang, Kelong; Zhong, Ming; Guo, Jun; Wang, Wei-zheng; Zhu, Ronghua

2010-10-01

The substitution of the hydrogen on aromatic and esterification of carboxyl group of the phenol compounds plays an important role in their bio-activities. In this paper, caffeic acid (CaA), chlorogenic acid (ChA) and ferulic acid (FA) were selected to investigate the binding to bovine serum albumin (BSA) using UV absorption spectroscopy, fluorescence spectroscopy and synchronous fluorescence spectroscopy. It was found that the methoxyl group substituting for the 3-hydroxyl group of CaA decreased the affinity for BSA and the esterification of carboxyl group of CaA with quinic acid increased the affinities. The affinities of ChA and FA with BSA were more sensitive to the temperature than that of CaA with BSA. Synchronous fluorescence spectroscopy and time-resolved fluorescence indicated that the Stern-Volmer plots largely deviated from linearity at high concentrations and were caused by complete quenching of the tyrosine fluorescence of BSA.

Structure and Dynamics of Hydroxyl-Functionalized Protic Ammonium Carboxylate Ionic Liquids.

PubMed

Thummuru, Dhileep Nagi Reddy; Mallik, Bhabani S

2017-10-26

We performed classical molecular dynamics simulations to investigate the structure and dynamics of protic ionic liquids, 2-hydroxy ethylammonium acetate, ethylammonium hydroxyacetate, and 2-hydroxyethylammonium hydroxyacetate at ambient conditions. Structural properties such as density, radial distribution functions, spatial distribution functions, and structure factors have been calculated. Dynamic properties such as mean square displacements, as well as residence and hydrogen bond dynamics have also been calculated. Hydrogen bond lifetimes and residence times change with the addition of hydroxyl groups. We observe that when a hydroxyl group is present on the cation, dynamics become very slow and it forms a strong hydrogen bond with carboxylate oxygen atoms of the anion. The hydroxyl functionalized ILs show more dynamic diversity than structurally similar ILs.

Proline Hydroxylation in Cell Wall Proteins: Is It Yet Possible to Define Rules?

PubMed

Duruflé, Harold; Hervé, Vincent; Balliau, Thierry; Zivy, Michel; Dunand, Christophe; Jamet, Elisabeth

2017-01-01

Cell wall proteins (CWPs) play critical and dynamic roles in plant cell walls by contributing to developmental processes and response to environmental cues. Since the CWPs go through the secretion pathway, most of them undergo post-translational modifications (PTMs) which can modify their biological activity. Glycosylation is one of the major PTMs of CWPs and refers to N -glycosylation, O -glycosylation and glypiation. Each of these PTMs occurs in different amino acid contexts which are not all well defined. This article deals with the hydroxylation of Pro residues which is a prerequisite for O -glycosylation of CWPs on hydroxyproline (Hyp) residues. The location of Hyp residues is well described in several structural CWPs, but yet rarely described in other CWPs. In this article, it is studied in detail in five Arabidopsis thaliana proteins using mass spectrometry data: one of them (At4g38770, AtPRP4) is a structural CWP containing 32.5% of Pro residues arranged in typical motifs, the others are either rich (27-28%, At1g31580 and At2g10940) or poor (6-8%, At1g09750 and At3g08030) in Pro residues. The known rules of Pro hydroxylation allowed a good prediction of Hyp location in AtPRP4. However, they could not be applied to the other proteins whatever their Pro content. In addition, variability of the Pro hydroxylation patterns was observed within some amino acid motifs in all the proteins and new patterns of Pro hydroxylation are described. Altogether, this work shows that Hyp residues are present in more protein families than initially described, and that Pro hydroxylation patterns could be different in each of them. This work paves the way for completing the existing Pro hydroxylation code.

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

PubMed Central

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

2013-01-01

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

Hypochlorous acid-activated carbon: an oxidizing agent capable of producing hydroxylated polychlorinated biphenyls.

PubMed Central

Voudrias, E A; Larson, R A; Snoeyink, V L; Chen, A S; Stapleton, P L

1986-01-01

Granular activated carbon (GAC), in the presence of dilute aqueous hypochlorite solutions typical of those used in water treatment, was converted to a reagent capable of carrying out free-radical coupling reactions and other oxidations of dilute aqueous solutions of phenols. The products included biphenyls with chlorine and hydroxyl substitution (hydroxylated polychlorinated biphenyls). For example, 2,4-dichlorophenol, a common constituent of wastewaters and also natural waters treated with hypochlorite, was converted to 3,5,5'trichloro-2,4'-dihydroxybiphenyl and several related compounds in significant amounts. It is possible that these products pose more of a health hazard than either the starting phenols or the unhydroxylated polychlorinated biphenyl derivatives. PMID:3028770

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

CINNAMIC ACID HYDROXYLASE IN SPINACH,

DTIC Science & Technology

An acetone precipitate from an extract of spinach leaves catalysed the hydroxylation of trans- cinnamic acid to p-coumaric acid . The enzyme was...and addition of L-phenylalanine inhibited cinnamic acid hydroxylase activity. (Author)...Tetrahydrofolic acid and a reduced pyridine nucleotide coenzyme were necessary for maximum activity. Aminopterin was a potent inhibitor of the hydroxylating

Fragmentation characteristics of hydroxycinnamic acids in ESI-MSn by density functional theory.

PubMed

Yin, Zhi-Hui; Sun, Chang-Hai; Fang, Hong-Zhuang

2017-07-01

This work aims to analyze the electrospray ionization multistage mass spectrometry (ESI-MS n ) fragmentation characteristics of hydroxycinnamic acids (HCAs) in negative ion mode. The geometric parameters, energies, natural bond orbitals and frontier orbitals of fragments were calculated by density functional theory (DFT) to investigate mass spectral fragmentation mechanisms. The results showed that proton transfer always occurred during fragmentation of HCAs; their quasi-molecular ions ([M - H] - ) existed in more than one form and were mainly with the lowest energy. The fragmentation characteristics included the followings: (1) according to the different substitution position of phenolic hydroxyl group, the ring contraction reaction by CO elimination from benzene was in an increasingly difficult order: m-phenolic hydroxyl > p-phenolic hydroxyl > o-phenolic hydroxyl; and (2) ortho effect always occurred in o-dihydroxycinnamic acids (o-diHCAs), i.e. one phenolic hydroxyl group offered H + , which combined with the other one to lose H 2 O. In addition, there was a nucleophilic reaction during ring contraction in diHCAs that oxygen atom attacked the carbon atom binding with the other phenolic hydroxyl to lose CO 2 . The fragmentation characteristics and mechanism of HCAs could be used for analysis and identification of such compounds quickly and effectively, and as reference for structural analogues by ESI-MS. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Synthesis and Proteasome Inhibition of Glycyrrhetinic Acid Derivatives

PubMed Central

Huang, Li; Yu, Donglei; Ho, Phong; Qian, Keduo; Lee, Kuo-Hsiung; Chen, Chin-Ho

2008-01-01

This study discovered that glycyrrhetinic acid inhibited the human 20S proteasome at 22.3 µM. Esterification of the C-3 hydroxyl group on glycyrrhetinic acid with various carboxylic acid reagents yielded a series of analogs with marked improved potency. Among the derivatives, glycyrrhetinic acid 3-O-isophthalate (17) was the most potent compound with IC50 of 0.22 µM, which was approximately 100-fold more potent than glycyrrhetinic acid. PMID:18562200

Unexpectedly high indoor hydroxyl radical concentrations associated with nitrous acid

PubMed Central

Gómez Alvarez, Elena; Amedro, Damien; Afif, Charbel; Gligorovski, Sasho; Schoemaecker, Coralie; Fittschen, Christa; Doussin, Jean-Francois; Wortham, Henri

2013-01-01

The hydroxyl (OH) radical is the most important oxidant in the atmosphere since it controls its self-oxidizing capacity. The main sources of OH radicals are the photolysis of ozone and the photolysis of nitrous acid (HONO). Due to the attenuation of solar radiation in the indoor environment, the possibility of OH formation through photolytic pathways indoors has been ignored up to now. In the indoor air, the ozonolysis of alkenes has been suggested as an alternative route of OH formation. Models and indirect measurements performed up to now according to this hypothesis suggest concentrations of OH radicals on the order of 104–105 molecules per cubic centimeter. Here, we present direct measurements of significant amounts of OH radicals of up to 1.8⋅106 molecules per cubic centimeter during an experimental campaign carried out in a school classroom in Marseille. This concentration is on the same order of magnitude of outdoor OH levels in the urban scenario. We also show that photolysis of HONO is an important source of OH radicals indoors under certain conditions (i.e., direct solar irradiation inside the room). Additionally, the OH concentrations were found to follow a linear dependence with the product J(HONO)⋅[HONO]. This was also supported by using a simple quasiphotostationary state model on the OH radical budget. These findings force a change in our understanding of indoor air quality because the reactivity linked to OH would involve formation of secondary species through chemical reactions that are potentially more hazardous than the primary pollutants in the indoor air. PMID:23898188

Acid-degradable and bioerodible modified polyhydroxylated materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frechet, Jean M. J.; Bachelder, Eric M.; Beaudette, Tristan T.

Compositions and methods of making a modified polyhydroxylated polymer comprising a polyhydroxylated polymer having reversibly modified hydroxyl groups, whereby the hydroxyl groups are modified by an acid-catalyzed reaction between a polydroxylated polymer and a reagent such as acetals, aldehydes, vinyl ethers and ketones such that the modified polyhydroxylated polymers become insoluble in water but freely soluble in common organic solvents allowing for the facile preparation of acid-sensitive materials. Materials made from these polymers can be made to degrade in a pH-dependent manner. Both hydrophobic and hydrophilic cargoes were successfully loaded into particles made from the present polymers using single andmore » double emulsion techniques, respectively. Due to its ease of preparation, processability, pH-sensitivity, and biocompatibility, of the present modified polyhydroxylated polymers should find use in numerous drug delivery applications.« less

Al-based metal-organic gels for selective fluorescence recognition of hydroxyl nitro aromatic compounds

NASA Astrophysics Data System (ADS)

Guo, Mao Xia; Yang, Liu; Jiang, Zhong Wei; Peng, Zhe Wei; Li, Yuan Fang

2017-12-01

The novel class of luminescent Al3 +-based metal-organic gels (Al-MOGs) have been developed by mix 4-[2,2‧:6‧,2″-terpyridine]-4‧-ylbenzoic acid (Hcptpy) with Al3 + under mild condition. The as-prepared Al-MOGs have not only multiple stimuli-responsive properties, but selective recognition of hydroxyl nitro aromatic compounds, which can quench the fluorescence of the Al-MOGs, while other nitro aromatic analogues without hydroxyl substitutes cannot. The fluorescence of Al-MOGs at 467 nm was seriously quenched by picric acid (PA) whose lowest unoccupied molecular orbital (LUMO) energy levels are lower than those of three other hydroxyl nitro aromatic compounds including 4-nitrophenol (4-NP), 3,5-dinitrosalicylic acid (3,5-DNTSA) and 2,4-dinitrophenol (2,4-DNP). Thus, PA was chosen as a model compound under optimal conditions and the relative fluorescence intensity of Al-MOGs was proportional to the concentration of PA in the range of 5.0-320.0 μM with a detection limit of 4.64 μM. Furthermore, the fluorescence quenching mechanism has also been investigated and revealed that the quenching was attributed to inner filter effects (IFEs), as well as electron transfer (ET) between Al-MOGs and PA.

Al-based metal-organic gels for selective fluorescence recognition of hydroxyl nitro aromatic compounds.

PubMed

Guo, Mao Xia; Yang, Liu; Jiang, Zhong Wei; Peng, Zhe Wei; Li, Yuan Fang

2017-12-05

The novel class of luminescent Al 3+ -based metal-organic gels (Al-MOGs) have been developed by mix 4-[2,2':6',2″-terpyridine]-4'-ylbenzoic acid (Hcptpy) with Al 3+ under mild condition. The as-prepared Al-MOGs have not only multiple stimuli-responsive properties, but selective recognition of hydroxyl nitro aromatic compounds, which can quench the fluorescence of the Al-MOGs, while other nitro aromatic analogues without hydroxyl substitutes cannot. The fluorescence of Al-MOGs at 467nm was seriously quenched by picric acid (PA) whose lowest unoccupied molecular orbital (LUMO) energy levels are lower than those of three other hydroxyl nitro aromatic compounds including 4-nitrophenol (4-NP), 3,5-dinitrosalicylic acid (3,5-DNTSA) and 2,4-dinitrophenol (2,4-DNP). Thus, PA was chosen as a model compound under optimal conditions and the relative fluorescence intensity of Al-MOGs was proportional to the concentration of PA in the range of 5.0-320.0μM with a detection limit of 4.64μM. Furthermore, the fluorescence quenching mechanism has also been investigated and revealed that the quenching was attributed to inner filter effects (IFEs), as well as electron transfer (ET) between Al-MOGs and PA. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Biotransformation of fluorophenyl pyridine carboxylic acids by the model fungus Cunninghamella elegans.

PubMed

Palmer-Brown, William; Dunne, Brian; Ortin, Yannick; Fox, Mark A; Sandford, Graham; Murphy, Cormac D

2017-09-01

1. Fluorine plays a key role in the design of new drugs and recent FDA approvals included two fluorinated drugs, tedizolid phosphate and vorapaxar, both of which contain the fluorophenyl pyridyl moiety. 2. To investigate the likely phase-I (oxidative) metabolic fate of this group, various fluorinated phenyl pyridine carboxylic acids were incubated with the fungus Cunninghamella elegans, which is an established model of mammalian drug metabolism. 3.  19 F NMR spectroscopy established the degree of biotransformation, which varied depending on the position of fluorine substitution, and gas chromatography-mass spectrometry (GC-MS) identified alcohols and hydroxylated carboxylic acids as metabolites. The hydroxylated metabolites were further structurally characterised by nuclear magnetic resonance spectroscopy (NMR), which demonstrated that hydroxylation occurred on the 4' position; fluorine in that position blocked the hydroxylation. 4. The fluorophenyl pyridine carboxylic acids were not biotransformed by rat liver microsomes and this was a consequence of inhibitory action, and thus, the fungal model was crucial in obtaining metabolites to establish the mechanism of catabolism.

Enzymatic routes for the synthesis of ursodeoxycholic acid.

PubMed

Eggert, Thorsten; Bakonyi, Daniel; Hummel, Werner

2014-12-10

Ursodeoxycholic acid, a secondary bile acid, is used as a drug for the treatment of various liver diseases, the optimal dose comprises the range of 8-10mg/kg/day. For industrial syntheses, the structural complexity of this bile acid requires the use of an appropriate starting material as well as the application of regio- and enantio-selective enzymes for its derivatization. Most strategies for the synthesis start from cholic acid or chenodeoxycholic acid. The latter requires the conversion of the hydroxyl group at C-7 from α- into β-position in order to obtain ursodeoxycholic acid. Cholic acid on the other hand does not only require the same epimerization reaction at C-7 but the removal of the hydroxyl group at C-12 as well. There are several bacterial regio- and enantio-selective hydroxysteroid dehydrogenases (HSDHs) to carry out the desired reactions, for example 7α-HSDHs from strains of Clostridium, Bacteroides or Xanthomonas, 7β-HSDHs from Clostridium, Collinsella, or Ruminococcus, or 12α-HSDH from Clostridium or from Eggerthella. However, all these bioconversion reactions need additional steps for the regeneration of the coenzymes. Selected multi-step reaction systems for the synthesis of ursodeoxycholic acid are presented in this review. Copyright © 2014 Elsevier B.V. All rights reserved.

[Simple method for precognition of drug interaction between oral iron and phenolic hydroxyl group-containing drugs].

PubMed

Sunagane, Nobuyoshi; Yoshinobu, Etsuko; Murayama, Nobuko; Terawaki, Yasufumi; Kamimura, Naoki; Uruno, Tsutomu

2005-02-01

In the present study, we devised a simple method for detecting the drug interaction between oral iron preparations and phenolic hydroxyl group-containing drugs, using the coloring reaction as indicator, due to the formation of complexes or chelates. In the method, oral iron preparations and test drugs in amounts as much as single dose for adults were added to 10 ml of purified water to make sample suspensions for testing. Thirty minutes after mixing an oral iron suspension and a test drug suspension, the change of color in the mixture was observed macroscopically and graded as 0 to 3, with a marked color change judged as grade 3 and no color change as grade 0. Screening of 14 test drugs commonly used orally was carried out. When using sodium ferrous citrate preparations as oral iron, 5 were classified as grade 3, 2 as grade 2, 4 as grade 1, and 3 as grade 0, respectively. To verify usefulness of the method, the interactions suggested by screening were pharmacokinetically assessed by measuring serum concentrations of the drug in mice. When a levodopa or droxidopa preparation, judged as grade 3 in screening, was concomitantly administered with an iron preparation, a significant reduction in bioavailability of the test drug was observed, indicating possible drug interaction between the test drug and oral iron. Combined administration of an acetaminophen preparation, judged as grade 1, and oral iron preparation showed no influence on the bioavailability of the test drug, implying no detectable interactions between them. In conclusion, the simple method devised in the present study is useful for precognition of drug interactions between oral iron preparations and phenolic hydroxyl group-containing drugs, and the drugs with a higher grade in screening may induce drug interactions with oral iron.

Adsorption behaviour of hydrogarnet for humic acid

NASA Astrophysics Data System (ADS)

Maeda, Hirotaka; Kurosaki, Yuichi; Nakayama, Masanobu; Ishida, Emile Hideki; Kasuga, Toshihiro

2018-04-01

Discharge of humic acid (HA) in aqueous environments is a key health and aesthetic issue. The present work investigates the use of hydrogarnet as a novel adsorbent for HA. Hydrogarnet was hydrothermally synthesized with different solvents to control the chemical composition. Hydrogarnet with three types of chemical compositions had better adsorption properties for HA than hydrogarnet with a single chemical composition. Controlling the chemical composition of hydrogarnet increased the number of hydroxyl groups and the overall binding energy of the system, leading to changes in the zeta potential. The enhancement of these adsorption properties is related to the increased numbers of hydroxyl groups on the surface and their diverse binding energies.

Determination of arrhenius and thermodynamic parameters for the aqueous reaction of the hydroxyl radical with lactic acid.

PubMed

Martin, Leigh R; Mezyk, Stephen P; Mincher, Bruce J

2009-01-08

Lactic acid is a major component of the TALSPEAK process planned for use in the separation of trivalent lanthanide and actinide elements. This acid acts both as a buffer and to protect the actinide complexant from radiolytic damage. However, there is little kinetic information on the reaction of water radiolysis species with lactic acid, particularly under the anticipated process conditions of aerated aqueous solution at pH approximately 3, where oxidizing reactions are expected to dominate. Here we have determined temperature-dependent reaction rate constants for the reactions of the hydroxyl radical with lactic acid and the lactate ion. For lactic acid this rate constant is given by the following equation: ln k(1) = (23.85 +/- 0.19) - (1120 +/- 54)/T, corresponding to an activation energy of 9.31 +/- 0.45 kJ mol(-1) and a room temperature reaction rate constant of (5.24 +/- 0.35) x 10(8) M(-1) s(-1) (24.0 degrees C). For the lactate ion, the temperature-dependent rate constant is given by ln k(2) = (24.83 +/- 0.14) - (1295 +/- 42)/T, for an activation energy of 10.76 +/- 0.35 kJ mol(-1) and a room temperature value of (7.77 +/- 0.50) x 10(8) M(-1) s(-1) (22.2 degrees C). These kinetic data have been combined with autotitration measurements to determine the temperature-dependent behavior of the lactic acid pK(a) value, allowing thermodynamic parameters for the acid dissociation to be calculated as DeltaH(o) = -10.75 +/- 1.77 kJ mol(-1), DeltaS(o) = -103.9 +/- 6.0 J K(-1) mol(-1) and DeltaG(o) = 20.24 +/- 2.52 kJ mol(-1) at low ionic strength.

Determination of Arrhenius and Thermodynamic Parameters for the Aqueous Reaction of the Hydroxyl Radical with Lactic Acid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leigh R. Martin; Stephen P. Mezyk; Bruce J. Mincher

2009-01-01

Lactic acid is a major component of the TALSPEAK process planned for use in the separation of trivalent lanthanide and actinide elements. This acid acts both as a buffer, and also to protect the actinide complexant from radiolytic damage. However, there is little kinetic information on the reaction of water radiolysis species with lactic acid, particularly under the anticipated process conditions of aerated aqueous solution at pH~3, where oxidizing reactions are expected to dominate. Here we have determined temperature-dependent reaction rate constants for the reactions of the hydroxyl radical with lactic acid and the lactate ion. For lactic acid thismore » rate constant is given by the equation: ln k1 = (23.85 ± 0.19) – (1120 ± 54) / T, corresponding to an activation energy of 9.31 ± 0.45 kJ mol-1 and a room temperature reaction rate constant of (5.24 ± 0.09) x 108 M-1 s-1 (24.0oC). For the lactate ion, the temperature-dependent rate constant is given by: ln k2 = (24.83 ± 0.14) – (1295 ± 42) / T, for an activation energy of 10.76 ± 0.35 kJ mol-1 and a room temperature value of (7.77 ± 0.11) x 108 M-1 s-1 (22.2oC). These kinetic data have been combined with autotitration measurements to determine the temperature-dependent behavior of the lactic acid pKa value, allowing thermodynamic parameters for the acid dissociation to be calculated as ?Hº = -10.75 ± 1.77 kJ mol-1, ?Sº = -103.9 ± 6.0 J K-1 mol-1 and ?Gº = 20.24 ± 2.52 kJ mol-1 at low ionic strength.« less

Sources of Nitrous Acid, Formaldehyde, and Hydroxyl Radical in Doha, Qatar.

NASA Astrophysics Data System (ADS)

Ackermann, Luis; Rappenglueck, Bernhard; Ayoub, Mohammed

2017-04-01

One of the most important species in the atmosphere is the hydroxyl radical (OH), due to its role controlling the oxidizing capacity of an air shed. The main formation processes of OH include the photolysis of ozone (O3), nitrous acid (HONO), formaldehyde (HCHO), and the ozonolysis of alkenes. Still, the sources of HONO in the atmosphere are not sufficiently well known, with indications that heterogeneous reactions on surfaces may contribute to the observed concentrations. The city of Doha in Qatar presents a unique opportunity to explore photochemical processes including the effects of high particulates concentrations under extreme weather conditions (high temperatures and humidity) and complex emission sources. Two Intensive Observational Periods (IOP) were conducted in Doha in 2016, one during the winter and the other during the summer. These consisted of meteorological measurements, ozone (O3), nitrous acid (HONO), formaldehyde (HCHO), nitrogen monoxide (NO), direct nitrogen dioxide (NO2), sulfur dioxide (SO2), carbon monoxide (CO), as well as particulate matter with an aerodynamic diameter ≤ 10 μm and 2.5 μm (PM10 and PM2.5). In addition photolysis rates of HONO, HCHO, NO2, and singlet oxygen (O1D) were measured. The photostationary state concentration of OH was calculated from its known sources and sinks. The maximum hourly average concentration of OH was determined to be around 1.1 ppt for summer and 0.5 ppt for winter IOP. For the 24-hr average, the photolysis of HONO was the main precursor for OH production with 54.3 % and 72.7 % (summer and winter IOP), while the photolysis of O3 was responsible for 23.8 % and 19.7 % and the photolysis of HCHO accounted for 21.9 % and 7.6 % (summer and winter IOP, respectively). In this study we present source apportionment analysis for the radical precursors HONO and HCHO during the winter and summer IOP and its diurnal variation and elucidate their impact on OH production. We also infer NOx vs VOC limitation of O3

Heterologous pathway assembly reveals molecular steps of fungal terreic acid biosynthesis.

PubMed

Kong, Chuixing; Huang, Hezhou; Xue, Ying; Liu, Yiqi; Peng, Qiangqiang; Liu, Qi; Xu, Qin; Zhu, Qiaoyun; Yin, Ying; Zhou, Xiangshan; Zhang, Yuanxing; Cai, Menghao

2018-02-01

Terreic acid is a potential anticancer drug as it inhibits Bruton's tyrosine kinase; however, its biosynthetic molecular steps remain unclear. In this work, the individual reactions of terreic acid biosynthesis were determined by stepwise pathway assembly in a heterologous host, Pichia pastoris, on the basis of previous knockout studies in a native host, Aspergillus terreus. Polyketide synthase AtX was found to catalyze the formation of partially reduced polyketide 6-methylsalicylic acid, followed by 3-methylcatechol synthesis by salicylate 1-monooxygenase AtA-mediated decarboxylative hydroxylation of 6-methylsalicylic acid. Our results show that cytochrome P450 monooxygenase AtE hydroxylates 3-methylcatechol, thus producing the next product, 3-methyl-1,2,4-benzenetriol. A smaller putative cytochrome P450 monooxygenase, AtG, assists with this step. Then, AtD causes epoxidation and hydroxyl oxidation of 3-methyl-1,2,4-benzenetriol and produces a compound terremutin, via which the previously unknown function of AtD was identified as cyclooxygenation. The final step involves an oxidation reaction of a hydroxyl group by a glucose-methanol-choline oxidoreductase, AtC, which leads to the final product: terreic acid. Functions of AtD and AtG were determined for the first time. All the genes were reanalyzed and all intermediates and final products were isolated and identified. Our model fully defines the molecular steps and corrects previous results from the literature.

Chemical Isotope Labeling LC-MS for High Coverage and Quantitative Profiling of the Hydroxyl Submetabolome in Metabolomics.

PubMed

Zhao, Shuang; Luo, Xian; Li, Liang

2016-11-01

A key step in metabolomics is to perform accurate relative quantification of the metabolomes in comparative samples with high coverage. Hydroxyl-containing metabolites are an important class of the metabolome with diverse structures and physical/chemical properties; however, many of them are difficult to detect with high sensitivity. We present a high-performance chemical isotope labeling liquid chromatography mass spectrometry (LC-MS) technique for in-depth profiling of the hydroxyl submetabolome, which involves the use of acidic liquid-liquid extraction to enrich hydroxyl metabolites into ethyl acetate from an aqueous sample. After drying and then redissolving in acetonitrile, the metabolite extract is labeled using a base-activated 12 C- or 13 C-dansylation reaction. A fast step-gradient LC-UV method is used to determine the total concentration of labeled metabolites. On the basis of the concentration information, a 12 C-labeled individual sample is mixed with an equal mole amount of a 13 C-labeled pool or control for relative metabolite quantification. The 12 C-/ 13 C-labeled mixtures are individually analyzed by LC-MS, and the resultant peak pairs of labeled metabolites in MS are measured for relative quantification and metabolite identification. A standard library of 85 hydroxyl compounds containing MS, retention time, and MS/MS information was constructed for positive metabolite identification based on matches of two or all three of these parameters with those of an unknown. Using human urine as an example, we analyzed samples of 1:1 12 C-/ 13 C-labeled urine in triplicate with triplicate runs per sample and detected an average of 3759 ± 45 peak pairs or metabolites per run and 3538 ± 71 pairs per sample with 3093 pairs in common (n = 9). Out of the 3093 peak pairs, 2304 pairs (75%) could be positively or putatively identified based on metabolome database searches, including 20 pairs positively identified using the dansylated hydroxyl standards library

A new, major C27 biliary bile acid in the Red-winged tinamou (Rhynchotus rufescens):(25R)-1β,3α,7α-trihydroxy-5β-cholestan-27-oic acid*

PubMed Central

Hagey, Lee R.; Kakiyama, Genta; Muto, Akina; Iida, Takashi; Mushiake, Kumiko; Goto, Takaaki; Mano, Nariyasu; Goto, Junichi; Oliveira, Cleida A.; Hofmann, Alan F.

2009-01-01

The chemical structures of the three major bile acids present in the gallbladder bile of the Red-winged tinamou (Rhynchotus rufescens), an early evolving, ground-living bird related to ratites, were determined. Bile acids were isolated by preparative reversed-phase HPLC. Two of the compounds were identified as the taurine N-acylamidates of (25R)-3α,7α-dihydroxy-5β-cholestan-27-oic acid (constituting 22% of biliary bile acids) and (25R)-3α,7α,12α-trihydroxy-5β-cholestan-27-oic acid (constituting 51%). The remaining compound, constituting 21% of biliary bile acids, was an unknown C27 bile acid. Its structure was elucidated by LC/ESI-MS/MS and NMR and shown to be the taurine conjugate of (25R)-1β,3α,7α-trihydroxy-5β-cholestan-27-oic acid, a C27 trihydroxy bile acid not previously reported. Although C27 bile acids with a 1β-hydroxyl group have been identified as trace bile acids in the alligator, this is the first report of a major biliary C27 bile acid possessing a 1β-hydroxyl group. PMID:19011113

Physiological activities of hydroxyl fatty acids

USDA-ARS?s Scientific Manuscript database

In the search of value-added products from surplus soybean oil, we produced many new hydroxy fatty acids through microbial bioconversion. Hydroxy fatty acids are used in a wide range of industrial products, such as resins, waxes, nylons plastics, lubricants, cosmetics, and additives in coatings and...

Electrochemical formation of hydroxide for enhancing carbon dioxide and acid gas uptake by a solution

DOEpatents

Rau, Gregory Hudson

2014-07-01

A system for forming metal hydroxide from a metal carbonate utilizes a water electrolysis cell having an acid-producing anode and a hydroxyl-producing cathode immersed in a water solution of sufficient ionic content to allow an electric current to pass between the hydroxyl-producing cathode and the acid-producing anode. A metal carbonate is placed in close proximity to the acid-producing anode. A direct current electrical voltage is provided across the acid-producing anode and the hydroxyl-producing cathode sufficient to generate acid at the acid-producing anode and hydroxyl ions at the hydroxyl-producing cathode. The acid dissolves at least part of the metal carbonate into metal and carbonate ions allowing the metal ions to travel toward the hydroxyl-producing cathode and to combine with the hydroxyl ions to form the metal hydroxide. The carbonate ions travel toward the acid-producing anode and form carbonic acid and/or water and carbon dioxide.

Electronic Structure Calculations of Ammonia Adsorption on Graphene and Graphene Oxide with Epoxide and Hydroxyl Groups

NASA Astrophysics Data System (ADS)

Nancy Anna Anasthasiya, A.; Khaneja, Mamta; Jeyaprakash, B. G.

2017-10-01

Ammonia adsorption on graphene (G) and graphene oxide (GO) was investigated through density functional theory calculations. In the GO system, the obtained binding energy, band gap, charge transfer and electronic structure revealed that the epoxide (GO-O) and hydroxyl groups (GO-OH) in GO enhance the NH3 adsorption, which leads to the chemisorption of NH3 on GO. The dissociation of NH3 to NH2 and formation of OH was also observed when the O and H atoms were separated at 0.985 Å, 1.019 Å, 1.035 Å, and 1.044 Å for various GO systems. The maximum charge transfer value was found to be 0.054 |e| with the binding energy of 1.143 eV for GO with a single epoxide (GO-1O) group. The charge transfer from NH3 to G or GO and the bond formation in this study agree with the reported experimental results.

Hydroxylated PBDEs induce developmental arrest in zebrafish

DOE Office of Scientific and Technical Information (OSTI.GOV)

Usenko, Crystal Y., E-mail: Crystal_usenko@baylor.edu; Hopkins, David C.; Trumble, Stephen J., E-mail: Stephen_trumble@baylor.edu

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 notmore » 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.« less

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.

The hydroxylated form of docosahexaenoic acid (DHA-H) modifies the brain lipid composition in a model of Alzheimer's disease, improving behavioral motor function and survival.

PubMed

Mohaibes, Raheem J; Fiol-deRoque, María A; Torres, Manuel; Ordinas, Margarita; López, David J; Castro, José A; Escribá, Pablo V; Busquets, Xavier

2017-09-01

We have compared the effect of the commonly used ω-3 fatty acid, docosahexaenoic acid ethyl ester (DHA-EE), and of its 2-hydroxylated DHA form (DHA-H), on brain lipid composition, behavior and lifespan in a new human transgenic Drosophila melanogaster model of Alzheimer's disease (AD). The transgenic flies expressed human Aβ42 and tau, and the overexpression of these human transgenes in the CNS of these flies produced progressive defects in motor function (antigeotaxic behavior) while reducing the animal's lifespan. Here, we demonstrate that both DHA-EE and DHA-H increase the longer chain fatty acids (≥18C) species in the heads of the flies, although only DHA-H produced an unknown chromatographic peak that corresponded to a non-hydroxylated lipid. In addition, only treatment with DHA-H prevented the abnormal climbing behavior and enhanced the lifespan of these transgenic flies. These benefits of DHA-H were confirmed in the well characterized transgenic PS1/APP mouse model of familial AD (5xFAD mice), mice that develop defects in spatial learning and in memory, as well as behavioral deficits. Hence, it appears that the modulation of brain lipid composition by DHA-H could have remedial effects on AD associated neurodegeneration. This article is part of a Special Issue entitled: Membrane Lipid Therapy: Drugs Targeting Biomembranes edited by Pablo V. Escribá. Copyright © 2017. Published by Elsevier B.V.

Preliminary study on the photoproduction of hydroxyl radicals in aqueous solution with Aldrich humic acid, algae and Fe(III) under high-pressure mercury lamp irradiation.

PubMed

Liu, Xianli; Xu, Dong; Wu, Feng; Liao, Zhenhuan; Liu, Jiantong; Deng, Nansheng

2004-03-01

Under a high-pressure mercury lamp (HPML) and using an exposure time of 4 h, the photoproduction of hydroxyl radicals (*OH) could be induced in an aqueous solution containing humic acid (HA). Hydroxyl radicals were determined by high-performance liquid chromatography using benzene as a probe. The results showed that *OH photoproduction increased from 1.80 to 2.74 microM by increasing the HA concentration from 10 to 40 mg L(-1) at an exposure time of 4 h (pH 6.5). Hydroxyl radical photoproduction in aqueous solutions of HA containing algae was greater than that in the aqueous solutions of HA without algae. The photoproduction of *OH in the HA solution with Fe(III) was greater than that of the solution without Fe(III) at pH ranging from 4.0 to 8.0. The photoproduction of *OH in HA solution with algae with or without Fe(III) under a 250 W HPML was greater than that under a 125 W HPML. The photoproduction of *OH in irradiated samples was influenced by the pH. The results showed that HPML exposure for 4 h in the 4-8 pH range led to the highest *OH photoproduction at pH 4.0.

Quantification of hydroxyl radical produced during phacoemulsification.

PubMed

Gardner, Jonathan M; Aust, Steven D

2009-12-01

To quantitate hydroxyl radicals produced during phacoemulsification with various irrigating solutions and conditions used in cataract surgery. Chemistry and Biochemistry Department, Utah State University, Logan, Utah, USA. All experiments were performed using an Infiniti Vision System phacoemulsifier with irrigation and aspiration. Hydroxyl radicals were quantitated using electron spin resonance spectroscopy and a spectrophotometric assay for malondialdehyde, which is formed by the oxidation of deoxyribose by the hydroxyl radical. Hydroxyl radical production increased during longitudinal-stroking phacoemulsification as power levels were increased in a nonlinear, nonexponential fashion. The detection of hydroxyl radical was reduced in irrigating solutions containing organic molecules (eg, citrate, acetate, glutathione, dextrose) and further reduced in Navstel, an irrigating solution containing a viscosity-modifying agent, hydroxypropyl methylcellulose. Hydroxyl radicals produced in settings representative of those used in phacoemulsification cataract surgery were quantitated using the deoxyribose method. Hydroxyl radical production was dependent on the level of ultrasound power applied and the irrigating solution used. Oxidative stress on the eye during phacoemulsification may be minimized by using irrigating solutions that contain organic molecules, including the viscosity-modifying agent hydroxypropyl methylcellulose, that can compete for reaction with hydroxyl radicals.

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–CeO 2-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–CeO 2-x(111) at varying Ce³⁺ concentrations (CeO 1.8–2.0) 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.more » 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.« less

Prolyl hydroxylation in elastin is not random.

PubMed

Schmelzer, Christian E H; Nagel, Marcus B M; Dziomba, Szymon; Merkher, Yulia; Sivan, Sarit S; Heinz, Andrea

2016-10-01

This study aimed to investigate the prolyl and lysine hydroxylation in elastin from different species and tissues. Enzymatic digests of elastin samples from human, cattle, pig and chicken were analyzed using mass spectrometry and bioinformatics tools. It was confirmed at the protein level that elastin does not contain hydroxylated lysine residues regardless of the species. In contrast, prolyl hydroxylation sites were identified in all elastin samples. Moreover, the analysis of the residues adjacent to prolines allowed the determination of the substrate site preferences of prolyl 4-hydroxylase. It was found that elastins from all analyzed species contain hydroxyproline and that at least 20%-24% of all proline residues were partially hydroxylated. Determination of the hydroxylation degrees of specific proline residues revealed that prolyl hydroxylation depends on both the species and the tissue, however, is independent of age. The fact that the highest hydroxylation degrees of proline residues were found for elastin from the intervertebral disc and knowledge of elastin arrangement in this tissue suggest that hydroxylation plays a biomechanical role. Interestingly, a proline-rich domain of tropoelastin (domain 24), which contains several repeats of bioactive motifs, does not show any hydroxyproline residues in the mammals studied. The results show that prolyl hydroxylation is not a coincidental feature and may contribute to the adaptation of the properties of elastin to meet the functional requirements of different tissues. The study for the first time shows that prolyl hydroxylation is highly regulated in elastin. Copyright © 2016 Elsevier B.V. All rights reserved.

Importance of Unimolecular HO 2 Elimination in the Heterogeneous OH Reaction of Highly Oxygenated Tartaric Acid Aerosol

DOE PAGES

Cheng, Chiu Tung; Chan, Man Nin; Wilson, Kevin R.

2016-07-09

Oxygenated organic molecules are abundant in atmospheric aerosols and are transformed by oxidation reactions near the aerosol surface by gas-phase oxidants such as hydroxyl (OH) radicals. To gain better insights into how the structure of an organic molecule, particularly in the presence of hydroxyl groups, controls the heterogeneous reaction mechanisms of oxygenated organic compounds, this paper investigates the OH-radical initiated oxidation of aqueous tartaric acid (C 4H 6O 6) droplets using an aerosol flow tube reactor. The molecular composition of the aerosols before and after reaction is characterized by a soft atmospheric pressure ionization source (Direct Analysis in Real Time)more » coupled with a high-resolution mass spectrometer. The aerosol mass spectra reveal that four major reaction products are formed: a single C 4 functionalization product (C 4H 4O 6) and three C 3 fragmentation products (C 3H 4O 4, C 3H 2O 4, and C 3H 2O 5). The C 4 functionalization product does not appear to originate from peroxy radical self-reactions but instead forms via an α-hydroxylperoxy radical produced by a hydrogen atom abstraction by OH at the tertiary carbon site. The proximity of a hydroxyl group to peroxy group enhances the unimolecular HO 2 elimination from the α-hydroxylperoxy intermediate. This alcohol-to-ketone conversion yields 2-hydroxy-3-oxosuccinic acid (C 4H 4O 6), the major reaction product. While in general, C–C bond scission reactions are expected to dominate the chemistry of organic compounds with high average carbon oxidation states (OS C), our results show that molecular structure can play a larger role in the heterogeneous transformation of tartaric acid (OS C = 1.5). Finally, these results are also compared with two structurally related dicarboxylic acids (succinic acid and 2,3-dimethylsuccinic acid) to elucidate how the identity and location of functional groups (methyl and hydroxyl groups) alter heterogeneous reaction mechanisms.« less

Differential effects of collagen prolyl 3-hydroxylation on skeletal tissues.

PubMed

Homan, Erica P; Lietman, Caressa; Grafe, Ingo; Lennington, Jennifer; Morello, Roy; Napierala, Dobrawa; Jiang, Ming-Ming; Munivez, Elda M; Dawson, Brian; Bertin, Terry K; Chen, Yuqing; Lua, Rhonald; Lichtarge, Olivier; Hicks, John; Weis, Mary Ann; Eyre, David; Lee, Brendan H L

2014-01-01

Mutations in the genes encoding cartilage associated protein (CRTAP) and prolyl 3-hydroxylase 1 (P3H1 encoded by LEPRE1) were the first identified causes of recessive Osteogenesis Imperfecta (OI). These proteins, together with cyclophilin B (encoded by PPIB), form a complex that 3-hydroxylates a single proline residue on the α1(I) chain (Pro986) and has cis/trans isomerase (PPIase) activity essential for proper collagen folding. Recent data suggest that prolyl 3-hydroxylation of Pro986 is not required for the structural stability of collagen; however, the absence of this post-translational modification may disrupt protein-protein interactions integral for proper collagen folding and lead to collagen over-modification. P3H1 and CRTAP stabilize each other and absence of one results in degradation of the other. Hence, hypomorphic or loss of function mutations of either gene cause loss of the whole complex and its associated functions. The relative contribution of losing this complex's 3-hydroxylation versus PPIase and collagen chaperone activities to the phenotype of recessive OI is unknown. To distinguish between these functions, we generated knock-in mice carrying a single amino acid substitution in the catalytic site of P3h1 (Lepre1(H662A) ). This substitution abolished P3h1 activity but retained ability to form a complex with Crtap and thus the collagen chaperone function. Knock-in mice showed absence of prolyl 3-hydroxylation at Pro986 of the α1(I) and α1(II) collagen chains but no significant over-modification at other collagen residues. They were normal in appearance, had no growth defects and normal cartilage growth plate histology but showed decreased trabecular bone mass. This new mouse model recapitulates elements of the bone phenotype of OI but not the cartilage and growth phenotypes caused by loss of the prolyl 3-hydroxylation complex. Our observations suggest differential tissue consequences due to selective inactivation of P3H1 hydroxylase activity

Variation in Optoelectronic Properties of Azo Dye-Sensitized TiO 2 Semiconductor Interfaces with Different Adsorption Anchors: Carboxylate, Sulfonate, Hydroxyl and Pyridyl Groups

DOE Office of Scientific and Technical Information (OSTI.GOV)

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/TiO 2 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 clustermore » 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.« less

Effects of the Hydroxyl Group on Phenyl Based Ligand/ERRγ Protein Binding

PubMed Central

2015-01-01

Bisphenol-A (4,4′-dihydroxy-2,2-diphenylpropane, BPA, or BPA-A) and its derivatives, when exposed to humans, may affect functions of multiple organs by specific binding to the human estrogen-related receptor γ (ERRγ). We carried out atomistic molecular dynamics (MD) simulations of three ligand compounds including BPA-A, 4-α-cumylphenol (BPA-C), and 2,2-diphenylpropane (BPA-D) binding to the ligand binding domain (LBD) of a human ERRγ to study the structures and energies associated with the binding. We used the implicit Molecular Mechanics/Poisson–Boltzmann Surface Area (MM/PBSA) method to estimate the free energies of binding for the phenyl based compound/ERRγ systems. The addition of hydroxyl groups to the aromatic ring had only a minor effect on binding structures and a significant effect on ligand/protein binding energy in an aqueous solution. Free binding energies of BPA-D to the ERRγ were found to be considerably less than those of BPA-A and BPA-C to the ERRγ. These results are well correlated with those from experiments where no binding affinities were determined in the BPA-D/ERRγ complex. No conformational change was observed for the helix 12 (H-12) of ERRγ upon binding of these compounds preserving an active transcriptional conformation state. PMID:25098505

Mechanistic and structural basis of stereospecific Cbeta-hydroxylation in calcium-dependent antibiotic, a daptomycin-type lipopeptide.

PubMed

Strieker, Matthias; Kopp, Florian; Mahlert, Christoph; Essen, Lars-Oliver; Marahiel, Mohamed A

2007-03-20

Non-ribosomally synthesized lipopeptide antibiotics of the daptomycin type are known to contain unnatural beta-modified amino acids, which are essential for bioactivity. Here we present the biochemical and structural basis for the incorporation of 3-hydroxyasparagine at position 9 in the 11-residue acidic lipopeptide lactone calcium-dependent antibiotic (CDA). Direct hydroxylation of l-asparagine by AsnO, a non-heme Fe(2+)/alpha-ketoglutarate-dependent oxygenase encoded by the CDA biosynthesis gene cluster, was validated by Fmoc derivatization of the reaction product and LC/MS analysis. The 1.45, 1.92, and 1.66 A crystal structures of AsnO as apoprotein, Fe(2+) complex, and product complex, respectively, with (2S,3S)-3-hydroxyasparagine and succinate revealed the stereoselectivity and substrate specificity of AsnO. The comparison of native and product-complex structures of AsnO showed a lid-like region (residues F208-E223) that seals the active site upon substrate binding and shields it from sterically demanding peptide substrates. Accordingly, beta-hydroxylated asparagine is synthesized prior to its incorporation into the growing CDA peptide. The AsnO structure could serve as a template for engineering novel enzymes for the synthesis of beta-hydroxylated amino acids.

SU-F-T-676: Measurement of Hydroxyl Radicals in Radiolized Water Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ouyang, Z; Ngwa, W; Brigham and Women’s Hospital, Dana-Farber Cancer Institute and Harvard Medical School, Boston, MA

2016-06-15

Purpose: Hydroxyl radicals can be produced within tissue by radiation therapy, and they are largely responsible for DNA damage and cell killing. Coumarin-3-carboxylic acid (3-CCA) and crystal violet are reported to react with hydroxyl radicals and can be used for fluorescence and absorbance measurements, respectively. This study assesses the ability of hydroxyl measurement for both 3-CCA and crystal violet in radiolized water systems in order to provide dosimetric information in radiation chemistry and radiation biology experiments. Methods: 3-CCA and crystal violet were both dissolved in phosphate buffered saline (PBS, pH 7.4) with final concentrations 0.5 mg/mL and 0.05 mg/mL. 3-CCAmore » and control solutions (PBS only) were loaded in black bottom 96-well plates. Crystal violet and control solutions were loaded in clear bottom 96-well plates. The prepared solutions were irradiated at 2 Gy using a small animal radiation research platform. Fluorescence reading with 360 nm excitation wavelength and 485 nm emission wavelength was done for 3-CCA, and absorbance reading at wavelength 580 nm was done for crystal violet before and after radiation. Results: 3-CCA showed clear difference in fluorescence before and after radiation, which suggested hydroxyl production during radiation. However, crystal violet absorbance at 580 nm was not changed significantly by radiation. Conclusion: The overall conclusion is that 3-CCA can be used for hydroxyl measurement in radiolized water systems, while crystal violet cannot, although crystal violet is reported widely to react with hydroxyl radicals produced in Fenton reactions. Possible reasons could relate to reaction pH.« less

Theoretical study of chlordecone and surface groups interaction in an activated carbon model under acidic and neutral conditions.

PubMed

Gamboa-Carballo, Juan José; Melchor-Rodríguez, Kenia; Hernández-Valdés, Daniel; Enriquez-Victorero, Carlos; Montero-Alejo, Ana Lilian; Gaspard, Sarra; Jáuregui-Haza, Ulises Javier

2016-04-01

Activated carbons (ACs) are widely used in the purification of drinking water without almost any knowledge about the adsorption mechanisms of the persistent organic pollutants. Chlordecone (CLD, Kepone) is an organochlorinated synthetic compound that has been used mainly as agricultural insecticide. CLD has been identified and listed as a persistent organic pollutant by the Stockholm Convention. The selection of the best suited AC for this type of contaminants is mainly an empirical and costly process. A theoretical study of the influence of AC surface groups (SGs) on CLD adsorption is done in order to help understanding the process. This may provide a first selection criteria for the preparation of AC with suitable surface properties. A model of AC consisting of a seven membered ring graphene sheet (coronene) with a functional group on the edge was used to evaluate the influence of the SGs over the adsorption. Multiple Minima Hypersurface methodology (MMH) coupled with PM7 semiempirical Hamiltonian was employed in order to study the interactions of the chlordecone with SGs (hydroxyl and carboxyl) at acidic and neutral pH and different hydration conditions. Selected structures were re-optimized using CAM-B3LYP to achieve a well-defined electron density to characterize the interactions by the Quantum Theory of Atoms in Molecules approach. The deprotonated form of surface carboxyl and hydroxyl groups of AC models show the strongest interactions, suggesting a chemical adsorption. An increase in carboxylic SGs content is proposed to enhance CLD adsorption onto AC at neutral pH conditions. Copyright © 2016 Elsevier Inc. All rights reserved.

Three Cd(II) MOFs with Different Functional Groups: Selective CO2 Capture and Metal Ions Detection.

PubMed

Wang, Zhong-Jie; Han, Li-Juan; Gao, Xiang-Jing; Zheng, He-Gen

2018-05-07

Three Cd(II) iso-frameworks {[Cd(BIPA)(IPA)]·DMF} n (1), {[Cd(BIPA)(HIPA)]·DMF} n (2), and {[Cd(BIPA)(NIPA)]·2H 2 O} n (3) were synthesized from the self-assembly of the BIPA ligand (BIPA = bis(4-(1 H-imidazol-1-yl)phenyl)amine) and different carboxylic ligands (H 2 IPA = isophthalic acid, H 2 HIPA = 5-hydroxyisophthalic acid, H 2 NIPA = 5-nitroisophthalic acid) with Cd(II), which have amino groups, amino and phenolic hydroxyl groups, and amino and nitro groups, respectively. Both 1 and 2 exhibit CO 2 uptakes of more than 20 wt %, indicating that amino and phenolic hydroxyl functionalized groups are beneficial to CO 2 adsorption. Their applications and mechanisms in detecting metal ions were researched. The results exhibit that 1 and 2 are dual-responsive photoluminescent sensors for Hg 2+ and Pb 2+ ions with low detection concentration and high quenching constant. Besides, like most MOFs, 3 can detect a trace quantity of Fe 3+ and Cu 2+ .

Insights into the catalytic mechanisms of phenylalanine and tryptophan hydroxylase from kinetic isotope effects on aromatic hydroxylation.

PubMed

Pavon, Jorge Alex; Fitzpatrick, Paul F

2006-09-12

Phenylalanine hydroxylase (PheH) and tryptophan hydroxylase (TrpH) catalyze the aromatic hydroxylation of phenylalanine and tryptophan, forming tyrosine and 5-hydroxytryptophan, respectively. The reactions of PheH and TrpH have been investigated with [4-(2)H]-, [3,5-(2)H(2)]-, and (2)H(5)-phenylalanine as substrates. All (D)k(cat) values are normal with Delta117PheH, the catalytic core of rat phenylalanine hydroxylase, ranging from 1.12-1.41. In contrast, for Delta117PheH V379D, a mutant protein in which the stoichiometry between tetrahydropterin oxidation and amino acid hydroxylation is altered, the (D)k(cat) value with [4-(2)H]-phenylalanine is 0.92 but is normal with [3,5-(2)H(2)]-phenylalanine. The ratio of tetrahydropterin oxidation to amino acid hydroxylation for Delta117PheH V379D shows a similar inverse isotope effect with [4-(2)H]-phenylalanine. Intramolecular isotope effects, determined from the deuterium contents of the tyrosine formed from [4-(2)H]-and [3,5(2)H(2)]-phenylalanine, are identical for Delta117PheH and Delta117PheH V379D, suggesting that steps subsequent to oxygen addition are unaffected in the mutant protein. The inverse effects are consistent with the reaction of an activated ferryl-oxo species at the para position of the side chain of the amino acid to form a cationic intermediate. The normal effects on the (D)k(cat) value for the wild-type enzyme are attributed to an isotope effect of 5.1 on the tautomerization of a dienone intermediate to tyrosine with a rate constant 6- to7-fold that for hydroxylation. In addition, there is a slight ( approximately 34%) preference for the loss of the hydrogen originally at C4 of phenylalanine. With (2)H(5)-indole-tryptophan as a substrate for Delta117PheH, the (D)k(cat) value is 0.89, consistent with hydroxylation being rate-limiting in this case. When deuterated phenylalanines are used as substrates for TrpH, the (D)k(cat) values are within error of those for Delta117PheH V379D. Overall, these results

Galloylglucoses of low molecular weight as mordant in electron microscopy. II. The moiety and functional groups possibly involved in the mordanting effect

PubMed Central

1976-01-01

Synthetic pentamonogalloylglucose applied to fixed tissues acts as a mordant, inducing high and diversified contrast similar to that obtained with natural gallotannins of low molecular weight (LMGG). By the separate use of each of the two moieties of the galloylglucose molecule, it was found that gallic acid is the mordanting agent. Glucose may contribute, however, to the effect by increasing the solubility and cross-linking potential of the compound, since the mordanting induced by gallic acid alone is weaker than that produced by its hexose esters. As suggested by results obtained with various phenolics and benzoic acid derivatives, the functional groups required for the mordanting effect of such agents are the carboxyl group, and at least one hydroxyl group concomitantly present on the benzene ring. In the case of galloylglucoses, it is assumed that the effect is due to hydrolysis products (gallic, digallic, or trigallic acids) or to the multiple hydroxyl groups of the intact molecule. Esters of gallic acid (propyl- and methylgallate), as well as pyrogallol, produce a "reversed staining" of all membranes, except for those of communicating (gap) junctions. PMID:783173

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.

Comparison of salicylate and D-phenylalanine for detection of hydroxyl radicals in chemical and biological reactions.

PubMed

Bailey, S M; Fauconnet, A L; Reinke, L A

1997-02-01

Hydroxylation of salicylate and D-phenylalanine was measured to test the usefulness of these compounds for hydroxyl radical (HO(•)) detection in chemical and biological systems. When HO(•) were produced by the photolytic decomposition of hydrogen peroxide, nearly equal amounts of 2,5- and 2,3-dihydroxybenzoic acid (DHBA) were produced from salicylate, with catechol as a minor product. In the photolytic reaction, nearly equal concentrations of p-,m-, and o-tyrosine were formed from D-phenylalanine. When salicylate or D-phenylalanine was present with Fenton reagents or in iron(II) autoxidation systems, the relative proportions of hydroxylated products were similar to those observed after photolysis, although less total products were usually detected. In contrast, when similar experiments were conducted with isolated hepatic microsomes and perfused livers, 2,5-DHBA was the primary product from salicylate, and p-tyrosine was the major product from D-phenylalanine. Cytochrome P-450 enzymes can hydroxylate salicylate to produce 2,5-DHBA, and it is likely that phenylalanine hydroxylase produces most of the p-tyrosine detected in hepatic tissues. Thus, although both salicylate and D-phenylalanine are useful probes for hydroxyl radical formation in chemical systems, hydroxylated products formed from enzymatic reactions complicate interpretation of data from both compounds in vivo.

Synthesis and pH-dependent assembly of isotropic and anisotropic gold nanoparticles functionalized with hydroxyl-bearing amino acids

NASA Astrophysics Data System (ADS)

Swami, Anuradha; Mittal, Sherry; Chopra, Adity; Sharma, Rohit K.; Wangoo, Nishima

2018-03-01

In recent years, the synthesis of gold nanostructures of controllable shapes and dimensions has become a subject of intensive and interesting studies. Especially, anisotropic gold nanostructures such as nanoplates, nanoribbons, nanoprisms and nanorods have attracted much attention due to their striking optical properties and promising applications in electronics, photonics, sensing and biomedicine. Keeping this in mind, in the present report, an unprecedented, facile and one pot synthesis of isotropic (spherical) and anisotropic (triangular, pentagonal, hexagonal, rod shaped) gold nanomaterials via pH controlled shape modulation using hydroxyl moeity containing α-amino acids (Serine, Threonine, Tyrosine) as both reducing and capping agents is reported. The synthesized nanostructures have been further characterized by UV-Vis spectroscopy and transmission electron microscopy. It was deduced from these studies that pH played a key role in the anisotropic growth of gold nanostructures. These gold nanoparticles can be further used for applications in biosensing, plasmonics, and electrocatalysis and others involving surface enhanced raman scattering. This study is therefore, important from the point of view of using amino acids for the synthesis of gold nanoparticles of different shapes and sizes leading towards the development of inventive biosensors and biocompatible nanoconstructs.

Unveiling of novel regio-selective fatty acid double bond hydratases from Lactobacillus acidophilus involved in the selective oxyfunctionalization of mono- and di-hydroxy fatty acids.

PubMed

Kim, Kyoung-Rok; Oh, Hye-Jin; Park, Chul-Soon; Hong, Seung-Hye; Park, Ji-Young; Oh, Deok-Kun

2015-11-01

The aim of this study is the first time demonstration of cis-12 regio-selective linoleate double-bond hydratase. Hydroxylation of fatty acids, abundant feedstock in nature, is an emerging alternative route for many petroleum replaceable products thorough hydroxy fatty acids, carboxylic acids, and lactones. However, chemical route for selective hydroxylation is still quite challenging owing to low selectivity and many environmental concerns. Hydroxylation of fatty acids by hydroxy fatty acid forming enzymes is an important route for selective biocatalytic oxyfunctionalization of fatty acids. Therefore, novel fatty acid hydroxylation enzymes should be discovered. The two hydratase genes of Lactobacillus acidophilus were identified by genomic analysis, and the expressed two recombinant hydratases were identified as cis-9 and cis-12 double-bond selective linoleate hydratases by in vitro functional validation, including the identification of products and the determination of regio-selectivity, substrate specificity, and kinetic parameters. The two different linoleate hydratases were the involved enzymes in the 10,13-dihydroxyoctadecanoic acid biosynthesis. Linoleate 13-hydratase (LHT-13) selectively converted 10 mM linoleic acid to 13S-hydroxy-9(Z)-octadecenoic acid with high titer (8.1 mM) and yield (81%). Our study will expand knowledge for microbial fatty acid-hydroxylation enzymes and facilitate the designed production of the regio-selective hydroxy fatty acids for useful chemicals from polyunsaturated fatty acid feedstocks. © 2015 Wiley Periodicals, Inc.

Formation of Hydroxylamine from Ammonia and Hydroxyl Radicals

NASA Astrophysics Data System (ADS)

Krim, Lahouari; Zins, Emilie-Laure

2014-06-01

In the interstellar medium, as well as in icy comets, ammonia may be a crucial species in the first step toward the formation of amino-acids and other prebiotic molecules such as hydroxylamine (NH2OH). It is worth to notice that the NH3/H2 ratio in the ISM is 3 10-5 compared the H2O/H2 one which is only 7 10-5. Using either electron-UV irradiations of water-ammonia ices or successive hydrogenation of solid nitric oxide, laboratory experiments have already shown the feasibility of reactions that may take place on the surface of ice grains in molecular clouds, and may lead to the formation of this precursor. Herein is proposed a new reaction pathway involving ammonia and hydroxyl radicals generated in a microwave discharge. Experimental studies, at 3 and 10 K, in solid phase as well as in neon matrix have shown that this reaction proceed via a hydrogen abstraction, leading to the formation of NH2 radical, that further recombine with hydroxyl radical to form hydroxylamine, under non-energetic conditions.

Electrochemical formation of hydroxide for enhancing carbon dioxide and acid gas uptake by a solution

DOEpatents

Rau, Gregory Hudson [Castro Valley, CA

2012-05-15

A system is described for forming metal hydroxide from a metal carbonate utilizing a water electrolysis cell having an acid-producing anode and a hydroxyl-producing cathode immersed in a water solution of sufficient ionic content to allow an electric current to pass between the hydroxyl-producing cathode and the acid-producing anode. A metal carbonate, in particular water-insoluble calcium carbonate or magnesium carbonate, is placed in close proximity to the acid-producing anode. A direct current electrical voltage is provided across the acid-producing anode and the hydroxyl-producing cathode sufficient to generate acid at the acid-producing anode and hydroxyl ions at the hydroxyl-producing cathode. The acid dissolves at least part of the metal carbonate into metal and carbonate ions allowing the metal ions to travel toward the hydroxyl-producing cathode and to combine with the hydroxyl ions to form the metal hydroxide. The carbonate ions travel toward the acid-producing anode and form carbonic acid and/or water and carbon dioxide. Among other uses, the metal hydroxide formed can be employed to absorb acid gases such as carbon dioxide from a gas mixture. The invention can also generate hydrogen and oxidative gases such as oxygen or chlorine.

Effects of humic acids with different polarities on the photocatalytic activity of nano-TiO2 at environment relevant concentration.

PubMed

Wu, Wei; Shan, Guoqiang; Xiang, Qian; Zhang, Yinqing; Yi, Shujun; Zhu, Lingyan

2017-10-01

Large volume production and application of nano-TiO 2 make it inevitably release to natural waters and its environmental behaviors would be affected by natural organic matters. In this study, the mechanisms of humic acid (HA) affecting the photocatalytic performance of nano-TiO 2 were elucidated by using three HA fractions from the same source but with different polarities. Bulk HA was fractionated on a silica gel column to get three fractions with polarity increasing in the order of FA, FB and FC. FA was fulvic acid-like while FB and FC were humic acid-like. All the three fractions (at 0.1 mg/L) promoted the generation of hydroxyl radicals (OHs) by nano-TiO 2 , and thus in turn facilitated the photocatalytic degradation of bispheol A (BPA). FA and FC displayed a stronger promotion effect than FB and the bulk HA. Online in situ flow cell ATR-FTIR and XPS analyses indicated that HA fractions could form charge-transfer complex with nano-TiO 2 surface through the phenolic hydroxyl and carboxylic groups, which favored the separation of photogenerated electron-hole pairs. Through step methylation experiments, it was verified that the phenolic hydroxyl and carboxylic groups of HA fractions played important roles in promoting the photocatalytic performance of nano-TiO 2 , and the effect of carboxylic group was more significant than the phenolic hydroxyl group. Copyright © 2017 Elsevier Ltd. All rights reserved.

Structural requirements of the human sodium-dependent bile acid transporter (hASBT): Role of 3- and 7-OH moieties on binding and translocation of bile acids

PubMed Central

González, Pablo M.; Lagos, Carlos F.; Ward, Weslyn C.; Polli, James E.

2014-01-01

Bile acids (BAs) are the end products of cholesterol metabolism. One of the critical steps in their biosynthesis involves the isomerization of the 3β-hydroxyl (-OH) group on the cholestane ring to the common 3α-configuration on BAs. BAs are actively recaptured from the small intestine by the human Apical Sodium-dependent Bile Acid Transporter (hASBT) with high affinity and capacity. Previous studies have suggested that no particular hydroxyl group on BAs is critical for binding or transport by hASBT, even though 3β-hydroxylated BAs were not examined. The aim of this study was to elucidate the role of the 3α-OH group on BAs binding and translocation by hASBT. Ten 3β-hydroxylated BAs (Iso-bile acids, iBAs) were synthesized, characterized, and subjected to hASBT inhibition and uptake studies. hASBT inhibition and uptake kinetics of iBAs were compared to that of native 3α-OH BAs. Glycine conjugates of native and isomeric BAs were subjected to molecular dynamics simulations in order to identify topological descriptors related to binding and translocation by hASBT. Iso-BAs bound to hASBT with lower affinity and exhibited reduced translocation than their respective 3α-epimers. Kinetic data suggests that, in contrast to native BAs where hASBT binding is the rate-limiting step, iBAs transport was rate-limited by translocation and not binding. Remarkably, 7-dehydroxylated iBAs were not hASBT substrates, highlighting the critical role of 7-OH group on BA translocation by hASBT, especially for iBAs. Conformational analysis of gly-iBAs and native BAs identified topological features for optimal binding as: concave steroidal nucleus, 3-OH “on-” or below-steroidal plane, 7-OH below-plane, and 12-OH moiety towards-plane. Our results emphasize the relevance of the 3α-OH group on BAs for proper hASBT binding and transport and revealed the critical role of 7-OH group on BA translocation, particularly in the absence of a 3α-OH group. Results have implications for BA

Future Directions of Structural Mass Spectrometry using Hydroxyl Radical Footprinting

PubMed Central

Kiselar, Janna G.; Chance, Mark R.

2010-01-01

Hydroxyl radical protein footprinting coupled to mass spectrometry has been developed over the last decade and has matured to a powerful method for analyzing protein structure and dynamics. It has been successfully applied in the analysis of protein structure, protein folding, protein dynamics, and protein-protein and protein-DNA interactions. Using synchrotron radiolysis, exposures of proteins to a “white” x-ray beam for milliseconds provide sufficient oxidative modifications to surface amino acid side chains that can be easily detected and quantified by mass spectrometry. Thus, conformational changes in proteins or protein complexes can be examined using a time-resolved approach, which would be a valuable method for the study of macromolecular dynamics. In this review, we describe a new application of hydroxyl radical protein footprinting to probe the time evolution of the calcium-dependent conformational changes of gelsolin on the millisecond timescale. The data suggest a cooperative transition as multiple sites in different molecular sub-domains have similar rates of conformational change. These findings demonstrate that time-resolved protein footprinting is suitable for studies of protein dynamics that occur over periods ranging from milliseconds to seconds. In this review we also show how the structural resolution and sensitivity of the technology can be improved as well. The hydroxyl radical varies in its reactivity to different side chains by over two orders of magnitude, thus oxidation of amino acid side chains of lower reactivity are more rarely observed in such experiments. Here we demonstrate that selected reaction monitoring (SRM)-based method can be utilized for quantification of oxidized species, improving the signal to noise ratio. This expansion of the set of oxidized residues of lower reactivity will improve the overall structural resolution of the technique. This approach is also suggested as a basis for developing hypothesis driven

New insights into the adsorption of 3-(trimethoxysilyl)propylmethacrylate on hydroxylated ZnO nanopowders.

PubMed

Bressy, Christine; Ngo, Van Giang; Ziarelli, Fabio; Margaillan, André

2012-02-14

Functionalization of zinc oxide (ZnO) nano-objects by silane grafting is an attractive method to provide nanostructured materials with a variety of surface properties. Active hydroxyl groups on the oxide surface are one of the causes governing the interfacial bond strength in nanohybrid particles. Here, "as-prepared" and commercially available zinc oxide nanopowders with a wide range of surface hydroxyl density were functionalized by a well-known polymerizable silane coupling agent, i.e., 3-(trimethoxysilyl)propylmethacrylate (MPS). Fourier transform infrared (FTIR) and solid-state (13)C and (29)Si nuclear magnetic resonance (NMR) spectroscopic investigations demonstrated that the silane coupling agent was fully hydrolyzed and linked to the hydroxyl groups already present on the particle surface through covalent and hydrogen bonds. Due to a basic catalyzed condensation of MPS with water, a siloxane layer was shown to be anchored to the nanoparticles through mono- and tridentate structures. Quantitative investigations were performed by thermogravimetric (TGA) and elemental analyses. The amount of silane linked to ZnO particles was shown to be affected by the amount of isolated hydroxyl groups available to react on the particle surface. For as-prepared ZnO nanoparticles, the number of isolated and available hydroxyl groups per square nanometer was up to 3 times higher than the one found on commercially available ZnO nanoparticles, leading to higher amounts of polymerizable silane agent linked to the surface. The MPS molecules were shown to be mainly oriented perpendicular to the oxide surface for all the as-prepared ZnO nanoparticles, whereas a parallel orientation was found for the preheated commercially ZnO nanopowders. In addition, ZnO nanoparticles were shown to be hydrophobized by the MPS treatment with water contact angles higher than 60°.

Application of positive mode atmospheric chemical ionisation to distinguish epimeric oleanolic and ursolic acids.

PubMed

Townley, Chloe; Brettell, Rhea C; Bowen, Richard D; Gallagher, Richard T; Martin, William H C

2015-01-01

A new and more reliable method is reported for distinguishing the equatorial and axial epimers of oleanolic and ursolic acids and related triterpenoids based primarily on the relative abundance of the [M+H](+) and [M+-H(2)O](+) signals in their positive mode atmospheric pressure chemical ionisation mass spectra. The rate of elimination of water, which is the principal primary fragmentation of protonated oleanolic and ursolic acids, depends systematically on the stereochemistry of the hydroxyl group in the 3 position. For the b-epimer, in which the 3-hydroxyl substituent is in an equatorial position,[M+-H(2)O](+) is the base peak. In contrast, for the α-epimer, where the 3-hydroxyl group is axial, [M + H](+) is the base peak. This trend, which is general for a range of derivatives of oleanolic and ursolic acids, including the corresponding methyl esters, allows epimeric triterpenoids in these series to be securely differentiated. Confirmatory information is available from the collision-induced dissociation of the [M+-H(2)O](+) primary fragment ions, which follow different pathways for the species derived from axial and equatorial epimers of oleanolic and ursolic acids. These two pieces of independent spectral information permit the stereochemistry of epimeric oleanolic and ursolic acids (and selected derivatives) to be assigned with confidence without relying either on chromatographic retention times or referring to the spectra or other properties of authentic samples of these triterpenoids.

Reduced levels of hydroxylated, polyunsaturated ultra long-chain fatty acids in the serum of colorectal cancer patients: implications for early screening and detection

PubMed Central

2010-01-01

Background There are currently no accurate serum markers for detecting early risk of colorectal cancer (CRC). We therefore developed a non-targeted metabolomics technology to analyse the serum of pre-treatment CRC patients in order to discover putative metabolic markers associated with CRC. Using tandem-mass spectrometry (MS/MS) high throughput MS technology we evaluated the utility of selected markers and this technology for discriminating between CRC and healthy subjects. Methods Biomarker discovery was performed using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). Comprehensive metabolic profiles of CRC patients and controls from three independent populations from different continents (USA and Japan; total n = 222) were obtained and the best inter-study biomarkers determined. The structural characterization of these and related markers was performed using liquid chromatography (LC) MS/MS and nuclear magnetic resonance technologies. Clinical utility evaluations were performed using a targeted high-throughput triple-quadrupole multiple reaction monitoring (TQ-MRM) method for three biomarkers in two further independent populations from the USA and Japan (total n = 220). Results Comprehensive metabolomic analyses revealed significantly reduced levels of 28-36 carbon-containing hydroxylated polyunsaturated ultra long-chain fatty-acids in all three independent cohorts of CRC patient samples relative to controls. Structure elucidation studies on the C28 molecules revealed two families harbouring specifically two or three hydroxyl substitutions and varying degrees of unsaturation. The TQ-MRM method successfully validated the FTICR-MS results in two further independent studies. In total, biomarkers in five independent populations across two continental regions were evaluated (three populations by FTICR-MS and two by TQ-MRM). The resultant receiver-operator characteristic curve AUCs ranged from 0.85 to 0.98 (average = 0.91 ± 0.04). Conclusions A

Treatability of phenol-production wastewater: Rate constant and pathway of dimethyl phenyl carbinol oxidation by hydroxyl radicals.

PubMed

Boonrattanakij, Nonglak; Joysampao, Atsawin; Pobsuktanasub, Tuksinaiya; Anotai, Jin; Ruangchainikom, Chalermchai

2017-12-15

Phenol-production wastewater is difficult to treat biologically by aerobic processes to meet the effluent standard COD of 120 mg L -1 because it contains several highly refractory aromatic pollutants, particularly dimethyl phenyl carbinol. Pretreatment revealed that dimethyl phenyl carbinol was slowly oxidized by molecular ozone; however, it readily reacted with hydroxyl radicals to yield acetophenone as a primary product. Acetophenone was further oxidized, first through five different pathways to form benzoic acid, phenyl glyoxalic acid, 4-4'-diacetyl biphenyl, and several hydroxylated aromatic compounds, and later to aliphatic carboxylic acids via ring cleavage. Regardless of system configuration (homogeneous vs heterogeneous), operating mode (batch vs continuous), and chemical concentration, the average intrinsic rate constants were 1.05 × 10 10 and 9.29 × 10 9  M -1  s -1 for dimethyl phenyl carbinol and acetophenone, respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

Structural insight into the active site of mushroom tyrosinase using phenylbenzoic acid derivatives.

PubMed

Oyama, Takahiro; Yoshimori, Atsushi; Takahashi, Satoshi; Yamamoto, Tetsuya; Sato, Akira; Kamiya, Takanori; Abe, Hideaki; Abe, Takehiko; Tanuma, Sei-Ichi

2017-07-01

So far, many inhibitors of tyrosinase have been discovered for cosmetic and clinical agents. However, the molecular mechanisms underlying the inhibition in the active site of tyrosinase have not been well understood. To explore this problem, we examined here the inhibitory effects of 4'-hydroxylation and methoxylation of phenylbenzoic acid (PBA) isomers, which have a unique scaffold to inhibit mushroom tyrosinase. The inhibitory effect of 3-PBA, which has the most potent inhibitory activity among the isomers, was slightly decreased by 4'-hydroxylation and further decreased by 4'-methoxylation against mushroom tyrosinase. Surprisingly, 4'-hydroxylation but not methoxylation of 2-PBA appeared inhibitory activity. On the other hand, both 4'-hydroxylation and methoxylation of 4-PBA increased the inhibitory activity against mushroom tyrosinase. In silico docking analyses using the crystallographic structure of mushroom tyrosinase indicated that the carboxylic acid or 4'-hydroxyl group of PBA derivatives could chelate with cupric ions in the active site of mushroom tyrosinase, and that the interactions of Asn260 and Phe264 in the active site with the adequate-angled biphenyl group are involved in the inhibitory activities of the modified PBAs, by parallel and T-shaped π-π interactions, respectively. Furthermore, Arg268 could fix the angle of the aromatic ring of Phe264, and Val248 is supposed to interact with the inhibitors as a hydrophobic manner. These results may enhance the structural insight into mushroom tyrosinase for the creation of novel tyrosinase inhibitors. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

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 is...

Synthesis and properties evaluation of sulfobetaine surfactant with double hydroxyl

NASA Astrophysics Data System (ADS)

Zhou, Ming; Luo, Gang; Zhang, Ze; Li, Sisi; Wang, Chengwen

2017-09-01

A series of sulfobetaine surfactants {N-[(3-alkoxy-2-hydroxyl)propoxy] ethyl-N,N-dimethyl-N-(2-hydroxyl)propyl sulfonate} ammonium chloride were synthesized with raw materials containing linear saturated alcohol, N,N-dimethylethanolamine, sodium 3-chloro-2-hydroxyl propane sulfonic acid and epichlorohydrin. The molecule structures of sulfobetaine surfactants were characterized by FTIR, 1HNMR and elemental analysis. Surface tension measurements can provide us information about the surface tension at the CMC (γCMC), pC20, Γmax and Amin. The pC20 values of sulfobetaine surfactants increase with the hydrophobic chain length increasing. Amin values of the surfactants decrease with increasing hydrophobic chain length from 10 to 14. The critical micelle concentration (CMC) and surface tension (γCMC) values of the sulfobetaine surfactants decrease with increasing hydrophobic chain length from 10 to 16. The lipophilicity of surfactant was enhanced with the increase of the carbon chain, however, the ability of anti-hard water was weakened. The minimum oil/water interfacial tension of four kinds of sulfobetaine surfactants is 10-2-10-3 mN/m magnitude, which indicates that the synthesized bis-hydroxy sulfobetaine surfactants have a great ability to reduce interfacial tension in the surfactant flooding system. The surface tension (γCMC) values of synthesized surfactants were lower compared with conventional anionic surfactant sodium dodecyl sulfonate.

Structure-affinity relationship of the interaction between phenolic acids and their derivatives and β-lactoglobulin and effect on antioxidant activity.

PubMed

Wu, Simin; Zhang, Yunyue; Ren, Fazheng; Qin, Yinghui; Liu, Jiaxin; Liu, Jingwen; Wang, Qingyu; Zhang, Hao

2018-04-15

In this study, 71 phenolic acids and their derivatives were used to investigate the structure-affinity relationship of β-lactoglobulin binding, and the effect of this interaction on antioxidant activity. Based on a fluorescence quenching method, an improved mathematical model was adopted to calculate the binding constants, with a correction for the inner-filter effect. Hydroxylation at the 3-position increased the affinity of the phenolic acids for β-lactoglobulin, while hydroxylation at the 2- or 4-positions had a negative effect. Complete methylation of all hydroxy groups, except at the 3-position, enhanced the binding affinity. Replacing the hydroxy groups with methyl groups at the 2-position also had a positive effect. Hydrogen bonding was one of the binding forces for the interaction. The antioxidant activity of phenolic acid-β-lactoglobulin complexes was higher than that of phenolic acids alone. These findings provide an understanding of the structure-activity relationship of the interaction between β-lactoglobulin and phenolic acids. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of thyme/cumin essential oils and butylated hydroxyl anisole/butylated hydroxyl toluene on physicochemical properties and oxidative/microbial stability of chicken patties.

PubMed

Sariçoban, Cemalettin; Yilmaz, Mustafa Tahsin

2014-02-01

In this study, effects of thyme/cumin essential oils (EO) and butylated hydroxyl anisole (BHA)/butylated hydroxyl toluene (BHT) on physicochemical properties and storage stability of chicken patties were compared in different storage periods (0, 3, 7, 14, 21, and 28 d). It was found that there were significant (P < 0.05) differences between physicochemical properties of patty samples treated with EO and the synthetic antioxidants. The EO showed similar performance to those of BHA and BHT in limiting TBARS values of chicken patty samples. Similarity in performance was also the case for microbial stability (total aerobic mesophilic, psychrotrophic, lactic acid, and coliform bacteria as well as molds and yeasts); namely, their effects were significant (P < 0.05). Effect of thyme EO was significant (P < 0.05) and remarkable, not allowing any coliform bacteria to grow in the samples. Given that EO were obtained from natural sources, the data suggested that the EO might be more useful than their synthetic counterparts, BHA and BHT, as additives for chicken patties to maintain oxidative/microbial stability and increase shelf life.

Limonene dehydrogenase hydroxylates the allylic methyl group of cyclic monoterpenes in the anaerobic terpene degradation by Castellaniella defragrans.

PubMed

Puentes-Cala, Edinson; Liebeke, Manuel; Markert, Stephanie; Harder, Jens

2018-05-01

The enzymatic functionalization of hydrocarbons is a central step in the global carbon cycle initiating the mineralization of methane, isoprene and monoterpenes, the most abundant biologically produced hydrocarbons. Also, terpene-modifying enzymes have found many applications in the energy-economic biotechnological production of fine chemicals. Here we describe a limonene dehydrogenase that was purified from the facultatively anaerobic betaproteobacterium Castellaniella defragrans 65Phen grown on monoterpenes under denitrifying conditions in the absence of molecular oxygen. The purified limonene:ferrocenium oxidoreductase activity hydroxylated the methyl group of limonene (1-methyl-4-(1-methylethenyl)-cyclohex-1-ene) yielding perillyl alcohol ([4-(prop-1-en-2-yl)cyclohex-1-en-1-yl]methanol). The enzyme had a dithiothreitol:perillyl alcohol oxidoreductase activity yielding limonene. Mass spectrometry and molecular size determinations revealed a heterodimeric enzyme comprising CtmA and CtmB. Recently the two proteins had been identified by transposon mutagenesis and proteomics as part of the cyclic terpene metabolism ( ctm ) in Castellaniella defragrans and were annotated as FAD-dependent oxidoreductases of the protein domain family phytoene dehydrogenases and related proteins (COG1233). CtmAB is the first heterodimeric enzyme in this protein superfamily. Flavins in the purified CtmAB are oxidized by ferrocenium and are reduced by limonene. Heterologous expression of CtmA, CtmB and CtmAB in E. coli demonstrated that limonene dehydrogenase activity required both subunits carrying each a flavin cofactor. Native CtmAB oxidized a wide range of monocyclic monoterpenes containing the allylic methyl group motif (1-methyl-cyclohex-1-ene). In conclusion, we have identified CtmAB as a hydroxylating limonene dehydrogenase and the first heteromer in a family of FAD-dependent dehydrogenases acting on allylic methylene or methyl CH-bonds. We suggest a placement in EC 1

Origin of Coverage Dependence in Photoreactivity of Carboxylate on TiO2(110): Hindering by Charged Coadsorbed Hydroxyls

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Zhitao; Henderson, Michael A.; Lyubinetsky, Igor

2015-09-30

The influence of reactant coverage on photochemical activity was explored using scanning tunneling microscopy (STM) and ultraviolet photoelectron spectroscopy (UPS). We observed diminished reactivity of carboxylate species (trimethyl acetate, TMA) on TiO2(110) as a function of increasing coverage. This effect was not linked to intermolecular interactions of TMA but to the accumulation of the coadsorbed bridging hydroxyls (HOb) deposited during (thermal) dissociative adsorption of the parent, trimethylacetic acid (TMAA). Confirmation of the hindering influence of HOb groups was obtained by the observation that HOb species originated from H2O dissociation at O-vacancy sites have a similar hindering effect on TMA photochemistry.more » Though HOb’s are photoinactive on TiO2(110) under ultrahigh vacuum conditions, UPS results show that these sites trap photoexcited electrons, which in turn likely (electrostatically) attract and neutralize photoexcited holes, thus suppressing the hole-mediated photoreactivity of TMA. This negative influence of surface hydroxyls on hole-mediated photochemistry is likely a major factor in other anaerobic photochemical processes on reducible oxide surfaces.« less

Identification and characterization of a novel PPARα-regulated and 7α-hydroxyl bile acid-preferring cytosolic sulfotransferase mL-STL (Sult2a8)[S

PubMed Central

Feng, Lu; Yuen, Yee-Lok; Xu, Jian; Liu, Xing; Chan, Martin Yan-Chun; Wang, Kai; Fong, Wing-Ping; Cheung, Wing-Tai; Lee, Susanna Sau-Tuen

2017-01-01

PPARα has been known to play a pivotal role in orchestrating lipid, glucose, and amino acid metabolism via transcriptional regulation of its target gene expression during energy deprivation. Recent evidence has also suggested that PPARα is involved in bile acid metabolism, but how PPARα modulates the homeostasis of bile acids during fasting is still not clear. In a mechanistic study aiming to dissect the spectrum of PPARα target genes involved in metabolic response to fasting, we identified a novel mouse gene (herein named mL-STL for mouse liver-sulfotransferase-like) that shared extensive homology with the Sult2a subfamily of a superfamily of cytosolic sulfotransferases, implying its potential function in sulfonation. The mL-STL gene expressed predominantly in liver in fed state, but PPARα was required to sustain its expression during fasting, suggesting a critical role of PPARα in regulating the mL-STL-mediated sulfonation during fasting. Functional studies using recombinant His-tagged mL-STL protein revealed its narrow sulfonating activities toward 7α-hydroxyl primary bile acids, including cholic acid, chenodeoxycholic acid, and α-muricholic acid, and thus suggesting that mL-STL may be the major hepatic bile acid sulfonating enzyme in mice. Together, these studies identified a novel PPARα-dependent gene and uncovered a new role of PPARα as being an essential regulator in bile acid biotransformation via sulfonation during fasting. PMID:28442498

Conjugation of bioactive groups to poly(lactic acid) and poly[(lactic acid)-co-(glycolic acid)] films.

PubMed

Prime, Emma L; Cooper-White, Justin J; Qiao, Greg G

2007-12-06

A novel PLA-based polymer containing reactive pendent ketone or hydroxyl groups was synthesized by the copolymerization of L-lactide with epsilon-caprolactone-based monomers. The polymer was activated with NPC, resulting in an amine-reactive polymer which was then cast into thin polymeric films, either alone or as part of a blend with PLGA, before immersion into a solution of the cell adhesion peptide GRGDS in PBS buffer allowed for conjugation of GRGDS to the film surfaces. Subsequent 3T3 fibroblast cell adhesion studies demonstrated an increase in cellular adhesion and spreading over films cast from unmodified PLGA. Hence the new polymer can be used to obtain covalent linkage of amine-containing molecules to polymer surfaces.

Selectivity of substrate binding and ionization of 2-methyl-3-hydroxypyridine-5-carboxylic acid oxygenase.

PubMed

Luanloet, Thikumporn; Sucharitakul, Jeerus; Chaiyen, Pimchai

2015-08-01

2-Methyl-3-hydroxypyridine-5-carboxylic acid (MHPC) oxygenase (EC 1.14.12.4) from Pseudomonas sp. MA-1 is a flavin-dependent monooxygenase that catalyzes a hydroxylation and aromatic ring cleavage reaction. The functional roles of two residues, Tyr223 and Tyr82, located ~ 5 Å away from MHPC, were characterized using site-directed mutagenesis, along with ligand binding, product analysis and transient kinetic experiments. Mutation of Tyr223 resulted in enzyme variants that were impaired in their hydroxylation activity and had Kd values for substrate binding 5-10-fold greater than the wild-type enzyme. Because this residue is adjacent to the water molecule that is located next to the 3-hydroxy group of MHPC, the results indicate that the interaction between Tyr223, H2 O and the 3-hydroxyl group of MHPC are important for substrate binding and hydroxylation. By contrast, the Kd for substrate binding of Tyr82His and Tyr82Phe variants were similar to that of the wild-type enzyme. However, only ~ 40-50% of the substrate was hydroxylated in the reactions of both variants, whereas most of the substrate was hydroxylated in the wild-type enzyme reaction. In free solution, MHPC or 5-hydroxynicotinic acid exists in a mixture of monoanionic and tripolar ionic forms, whereas only the tripolar ionic form binds to the wild-type enzyme. The binding of tripolar ionic MHPC would allow efficient hydroxylation through an electrophilic aromatic substitution mechanism. For the Tyr82His and Tyr82Phe variants, both forms of substrates can bind to the enzymes, indicating that the mutation at Tyr82 abolished the selectivity of the enzyme towards the tripolar ionic form. Transient kinetic studies indicated that the hydroxylation rate constants of both Tyr82 variants are approximately two- to 2.5-fold higher than that of the wild-type enzyme. Altogether, our findings suggest that Tyr82 is important for the binding selectivity of MHPC oxygenase towards the tripolar ionic species, whereas the

PHOTOCHEICAL PRODUCTION OF HYDROXYL RADICAL IN NATURAL WATER - THE ROLE OF IRON AND DISSOLVED ORGANIC MATTER

EPA Science Inventory

Photochemical hydroxyl radical (OH) production was measured in several natural waters to investigate the importance of colored dissolved organic matter (CDOM) and iron-CDOM complexes as sources of OH. High rates of OH photoproduction in highly colored, iron-rich, acidic waters a...

Solar Insolation Effect on the Local Distribution of Lunar Hydroxyl

NASA Astrophysics Data System (ADS)

Kim, Suyeon; Yi, Yu; Hong, Ik-Seon; Sohn, Jongdae

2018-03-01

Moon mineralogy mapper (M3)'s work proved that the moon is not completely dry but has some hydroxyl/water. M3's data confirmed that the amount of hydroxyl on the lunar surface is inversely related to the measured signal brightness, suggesting the lunar surface is sensitive to temperature by solar insolation. We tested the effect of solar insolation on the local distribution of hydroxyl by using M3 data, and we found that most craters had more hydroxyl in shade areas than in sunlit areas. This means that the local distribution of hydroxyl is absolutely influenced by the amount of sunshine. We investigated the factors affecting differences in hydroxyl; we found that the higher the latitude, the larger the difference during daytime. We also measured the pyroxene content and found that pyroxene affects the amount of hydroxyl, but it does not affect the difference in hydroxyl between sunlit and shaded areas. Therefore, we confirmed that solar insolation plays a significant role in the local distribution of hydroxyl, regardless of surface composition.

Antioxidant and antimicrobial activities of cinnamic acid derivatives.

PubMed

Sova, M

2012-07-01

Cinnamic acid is an organic acid occurring naturally in plants that has low toxicity and a broad spectrum of biological activities. In the search for novel pharmacologically active compounds, cinnamic acid derivatives are important and promising compounds with high potential for development into drugs. Many cinnamic acid derivatives, especially those with the phenolic hydroxyl group, are well-known antioxidants and are supposed to have several health benefits due to their strong free radical scavenging properties. It is also well known that cinnamic acid has antimicrobial activity. Cinnamic acid derivatives, both isolated from plant material and synthesized, have been reported to have antibacterial, antiviral and antifungal properties. Acids, esters, amides, hydrazides and related derivatives of cinnamic acid with such activities are here reviewed.

Some reactions of the hydroxyl adduct of adenine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vanhemmen, J.J.

1975-01-01

The chemical reactions of purine derivatives resulting from pulse radiolysis were studied. Some reactions of the hydroxyl adduct of adenine are described and one of these reactions was compared with similar reactions of hydroxyl adducts of other purine derivatives. Evidence is given that in various purines opening of the imidazole ring is due to unimolecular rearrangements of the hydroxyl adducts. (GRA)

Probing Competitive and Co-operative Hydroxyl and Ammonium Hydrogen-Bonding Directed Epoxidations.

PubMed

Brambilla, Marta; Brennan, Méabh B; Csatayová, Kristína; Davies, Stephen G; Fletcher, Ai M; Kennett, Alice M R; Lee, James A; Roberts, Paul M; Russell, Angela J; Thomson, James E

2017-10-06

The diastereoselectivities and rates of epoxidation (upon treatment with Cl 3 CCO 2 H then m-CPBA) of a range of cis- and trans-4-aminocycloalk-2-en-1-ol derivatives (containing five-, six-, and seven-membered rings) have been investigated. In all cases where the two potential directing groups can promote epoxidation on opposite faces of the ring scaffold, evidence of competitive epoxidation pathways, promoted by hydrogen-bonding to either the in situ formed ammonium moiety or the hydroxyl group, was observed. In contrast to the relative directing group abilities already established for the six-membered ring system (NHBn ≫ OH > NBn 2 ), an N,N-dibenzylammonium moiety appeared more proficient than a hydroxyl group at directing the stereochemical course of the epoxidation reaction in a five- or seven-membered system. In the former case, this was rationalized by the drive to minimize torsional strain in the transition state being coupled with assistance from hydrogen-bonding to the ammonium moiety. In the latter case, this was ascribed to the steric bulk of the ammonium moiety disfavoring conformations in which hydrogen-bonding to the hydroxyl group results in direction of the epoxidation to the syn face. In cases where the two potential directing groups can promote epoxidation on the same face of the ring scaffold, an enhancement of epoxidation diastereoselectivity was not observed, while introduction of a second, allylic heteroatom to the substrate results in diminishment of the rate of epoxidation in all cases. Presumably, reduction of the nucleophilicity of the olefin by the second, inductively electron-withdrawing heteroatom is the dominant factor, and any assistance to the epoxidation reaction by the potential to form hydrogen-bonds to two directing groups rather than one is clearly unable to overwhelm it.

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

Salt permeation and exclusion in hydroxylated and functionalized silica pores.

PubMed

Leung, Kevin; Rempe, Susan B; Lorenz, Christian D

2006-03-10

We use combined ab initio molecular dynamics (AIMD), grand canonical Monte Carlo, and molecular dynamics techniques to study the effect of pore surface chemistry and confinement on the permeation of salt into silica nanopore arrays filled with water. AIMD shows that 11.6 A diameter hydroxylated silica pores are relatively stable in water, whereas amine groups on functionalized pore surfaces abstract silanol protons, turning into NH3+. Free energy calculations using an ab initio parametrized force field show that the hydroxylated pores strongly attract Na+ and repel Cl- ions. Pores lined with NH3+ have the reverse surface charge polarity. Finally, studies of ions in carbon nanotubes suggest that hydration of Cl- is more strongly frustrated by pure confinement effects than Na+.

The impact of the hydroxyl radical photochemical sources on the rivastigmine drug transformation in mimic and natural waters.

PubMed

Passananti, Monica; Temussi, Fabio; Iesce, Maria Rosaria; Mailhot, Gilles; Brigante, Marcello

2013-09-15

In this paper we investigated the degradation of the rivastigmine drug induced by hydroxyl radical in synthetic and natural waters focusing on both reactivity and photoproducts identification. The hydroxyl radical formation rate was quantified by using terephthalic acid as trapping molecule and it was related with the rivastigmine degradation rate. The second order rate constant between hydroxyl radical and rivastigmine was estimated to be ≈ 5.8 × 10(9) M(-1) s(-1). Irradiation of rivastigmine in three natural waters (rain, lake and river) and comparison with degradation rates observed in synthetic solutions using nitrite, nitrate and hydrogen peroxide suggest that, in addition to hydroxyl radical, also nitroderived radicals (NO/NO2) are responsible for the pollutant degradation in natural media. In fact, the evaluated degradation rates in three natural waters are greatly higher than those estimated considering only the reactivity with photogenerated hydroxyl radical. Using nitrites and nitrates as photochemical OH source, the rivastigmine degradation cannot be described considering only the hydroxyl radical reactivity suggesting that NO and NO2 radicals could play a key role during indirect degradation. Moreover main degradation products have been identified by means of HPLC-MS. Hydroxylation of the aromatic ring as well as carbamate and amino chain oxidation were suggested as main reaction mechanisms, but also nitroderived compounds were characterized. Finally polychromatic irradiations of three rivastigmine doped natural waters (rain, river and lake) underlined the role of the indirect degradation that needs to be considered when direct degradation of selected pollutants is negligible under environmental-like conditions. Copyright © 2013 Elsevier Ltd. All rights reserved.

Pyrolysis temperature influences ameliorating effects of biochars on acidic soil.

PubMed

Wan, Qing; Yuan, Jin-Hua; Xu, Ren-Kou; Li, Xing-Hui

2014-02-01

The biochars were prepared from straws of canola, corn, soybean, and peanut at different temperatures of 300, 500, and 700 °C by means of oxygen-limited pyrolysis.Amelioration effects of these biochars on an acidic Ultisol were investigated with incubation experiments, and application rate of biochars was 10 g/kg. The incorporation of these biochars induced the increase in soil pH, soil exchangeable base cations, base saturation, and cation exchange capacity and the decrease in soil exchangeable acidity and exchangeable Al. The ameliorating effects of biochars on acidic soil increased with increase in their pyrolysis temperature. The contribution of oxygen-containing functional groups on the biochars to their ameliorating effects on the acidic soil decreased with the rise in pyrolysis temperature, while the contribution from carbonates in the biochars changed oppositely. The incorporation of the biochars led to the decrease in soil reactive Al extracted by 0.5mol/L CuCl2, and the content of reactive Al was decreased with the increase in pyrolysis temperature of incorporated biochars. The biochars generated at 300 °C increased soil organically complexed Al due to ample quantity of oxygen-containing functional groups such as carboxylic and phenolic groups on the biochars, while the biochars generated at 500 and 700 °C accelerated the transformation of soil exchangeable Al to hydroxyl-Al polymers due to hydrolysis of Al at higher pH. Therefore, the crop straw-derived biochars can be used as amendments for acidic soils and the biochars generated at relatively high temperature have great ameliorating effects on the soils.

Effects of ultraviolet irradiation on bonding strength between Co-Cr alloy and citric acid-crosslinked gelatin matrix.

PubMed

Inoue, Motoki; Sasaki, Makoto; Katada, Yasuyuki; Taguchi, Tetsushi

2014-02-01

Novel techniques for creating a strong bond between polymeric matrices and biometals are required. We immobilized polymeric matrices on the surface of biometal for drug-eluting stents through covalent bond. We performed to improve the bonding strength between a cobalt-chromium alloy and a citric acid-crosslinked gelatin matrix by ultraviolet irradiation on the surface of cobalt-chromium alloy. The ultraviolet irradiation effectively generated hydroxyl groups on the surface of the alloy. The bonding strength between the gelatin matrix and the alloy before ultraviolet irradiation was 0.38 ± 0.02 MPa, whereas it increased to 0.48 ± 0.02 MPa after ultraviolet irradiation. Surface analysis showed that the citric acid derivatives occurred on the surface of the cobalt-chromium alloy through ester bond. Therefore, ester bond formation between the citric acid derivatives active esters and the hydroxyl groups on the cobalt-chromium alloy contributed to the enhanced bonding strength. Ultraviolet irradiation and subsequent immobilization of a gelatin matrix using citric acid derivatives is thus an effective way to functionalize biometal surfaces.

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.

Lettuce Costunolide Synthase (CYP71BL2) and Its Homolog (CYP71BL1) from Sunflower Catalyze Distinct Regio- and Stereoselective Hydroxylations in Sesquiterpene Lactone Metabolism*

PubMed Central

Ikezawa, Nobuhiro; Göpfert, Jens Christian; Nguyen, Don Trinh; Kim, Soo-Un; O'Maille, Paul E.; Spring, Otmar; Ro, Dae-Kyun

2011-01-01

Sesquiterpene lactones (STLs) are terpenoid natural products possessing the γ-lactone, well known for their diverse biological and medicinal activities. The occurrence of STLs is sporadic in nature, but most STLs have been isolated from plants in the Asteraceae family. Despite the implication of the γ-lactone group in many reported bioactivities of STLs, the biosynthetic origins of the γ-lactone ring remains elusive. Germacrene A acid (GAA) has been suggested as a central precursor of diverse STLs. The regioselective (C6 or C8) and stereoselective (α or β) hydroxylation on a carbon of GAA adjacent to its carboxylic acid at C12 is responsible for the γ-lactone formation. Here, we report two cytochrome P450 monooxygenases (P450s) capable of catalyzing 6α- and 8β-hydroxylation of GAA from lettuce and sunflower, respectively. To identify these P450s, sunflower trichomes were isolated to generate a trichome-specific transcript library, from which 10 P450 clones were retrieved. Expression of these clones in a yeast strain metabolically engineered to synthesize substrate GAA identified a P450 catalyzing 8β-hydroxylation of GAA, but the STL was not formed by spontaneous lactonization. Subsequently, we identified the closest homolog of the GAA 8β-hydroxylase from lettuce and discovered 6α-hydroxylation of GAA by the recombinant enzyme. The resulting 6α-hydroxy-GAA spontaneously undergoes a lactonization to yield the simplest form of STL, costunolide. Furthermore, we demonstrate the milligram per liter scale de novo synthesis of costunolide using the lettuce P450 in an engineered yeast strain, an important advance that will enable exploitation of STLs. Evolution and homology models of these two P450s are discussed. PMID:21515683

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.

Strong-acid, carboxyl-group structures in fulvic acid from the Suwannee River, Georgia. 1. Minor structures

USGS Publications Warehouse

Leenheer, J.A.; Wershaw, R. L.; Reddy, M.M.

1995-01-01

An investigation of the strong-acid characteristics (pKa 3.0 or less) of fulvic acid from the Suwannee River, Georgia, was conducted. Quantitative determinations were made for amino acid and sulfur-containing acid structures, oxalate half-ester structures, malonic acid structures, keto acid structures, and aromatic carboxyl-group structures. These determinations were made by using a variety of spectrometric (13C-nuclear magnetic resonance, infrared, and ultraviolet spectrometry) and titrimetric characterizations on fulvic acid or fulvic acid samples that were chemically derivatized to indicate certain functional groups. Only keto acid and aromatic carboxyl-group structures contributed significantly to the strong-acid characteristics of the fulvic acid; these structures accounted for 43% of the strong-acid acidity. The remaining 57% of the strong acids are aliphatic carboxyl groups in unusual and/or complex configurations for which limited model compound data are available.

A study of the trypanocidal activity of triterpene acids isolated from Miconia species.

PubMed

Cunha, Wilson Roberto; Crevelin, Eduardo J; Arantes, Glenda M; Crotti, Antonio E Miller; Andrade e Silva, Márcio L; Furtado, Niege A J Cardoso; Albuquerque, Sérgio; Ferreira, Daniele Da Silva

2006-06-01

Triterpene acids, including ursolic acid (1), urjinolic acid (4) and oleanoic acid (5) along with a mixture of 2alpha-hydroxyursolic acid (2) and maslic acid (3) were isolated from methylene chloride extracts of the Miconia sellowiana and M. ligustroides species and their activities against the trypomastigote blood forms of Trypanosoma cruzi were evaluated. The potassium salt derivative of ursolic acid (1a) was also tested. The in vitro assays showed that compounds 1, 5 and 1a were the most active (IC(50) 17.1 microm, 12.8 microm and 8.9 microm, respectively). In contrast, a mixture of 2 plus 3, that exhibit a hydroxyl at C-2 and C-3, is much less potent than a mixture of 1 and 5 (IC(50) 48.5 microm and 11.8 microm, respectively). In the same manner, compound 4, that differs from 5 by two additional hydroxyl groups (at C-2 and C-23) displayed weak trypanocidal activity (IC(50) 76.3 microm) when compared with the other triterpenes. These results suggest that the free hydroxyl at C-3 and the polarity of C-28 are the most influential structural features for determining the in vitro trypanocidal activity of triterpenes. In vivo assays were also undertaken for the most active compounds 1, 1a and the mixture of 1 plus 5. The most significant reduction in parasite number in the parasitemic peak were obtained for compound 1 and its salt derivative 1a (75.7% and 70.4%, respectively). Moreover, the survival time was increased for all the treated animals.

Theoretical study on the interactions between chlordecone hydrate and acidic surface groups of activated carbon under basic pH conditions.

PubMed

Melchor-Rodríguez, Kenia; Gamboa-Carballo, Juan José; Ferino-Pérez, Anthuan; Passé-Coutrin, Nady; Gaspard, Sarra; Jáuregui-Haza, Ulises Javier

2018-05-01

A theoretical study of the influence of acidic surface groups (SG) of activated carbon (AC) on chlordecone hydrate (CLDh) adsorption is presented, in order to help understanding the adsorption process under basic pH conditions. A seven rings aromatic system (coronene) with a functional group in the edge was used as a simplified model of AC to evaluate the influence of SG in the course of adsorption from aqueous solution at basic pH conditions. Two SG were modeled in their deprotonated form: carboxyl and hydroxyl (COO - and O - ), interacting with CLDh. In order to model the solvation process, all systems under study were calculated with up to three water molecules. Multiple Minima Hypersurface (MMH) methodology was employed to study the interactions of CLDh with SG on AC using PM7 semiempirical Hamiltonian, to explore the potential energy surfaces of the systems and evaluate their thermodynamic association energies. The re-optimization of representative structures obtained from MMH was done using M06-2X Density Functional Theory. The Quantum Theory of Atoms in Molecules (QTAIM) was used to characterize the interaction types. As result, the association of CLDh with acidic SG at basic pH conditions preferentially occurs between the two alcohol groups of CLDh with COO - and O - groups and by dispersive interactions of chlorine atoms of CLDh with the graphitic surface. On the other hand, the presence of covalent interactions between the negatively charged oxygen of SG and one hydrogen atom of CLDh alcohol groups (O - ⋯HO interactions) without water molecules, was confirmed by QTAIM study. It can be concluded that the interactions of CLDh with acidic SG of AC under basic pH conditions confirms the physical mechanisms of adsorption process. Copyright © 2018 Elsevier Inc. All rights reserved.

Nature and position of functional group on thiopurine substrates influence activity of xanthine oxidase--enzymatic reaction pathways of 6-mercaptopurine and 2-mercaptopurine are different.

PubMed

Tamta, Hemlata; Kalra, Sukirti; Thilagavathi, Ramasamy; Chakraborti, Asit K; Mukhopadhyay, Anup K

2007-02-01

Xanthine oxidase-catalyzed hydroxylation reactions of the anticancer drug 6-mercaptopurine (6-MP) and its analog 2-mercaptopurine (2-MP) as well as 6-thioxanthine (6-TX) and 2-thioxanthine (2-TX) have been studied using UV-spectroscopy, high pressure liquid chromatography, photodiode array, and liquid chromatography-based mass spectral analysis. It is shown that 6-MP and 2-MP are oxidatively hydroxylated through different pathways. Enzymatic hydroxylation of 6-MP forms 6-thiouric acid in two steps involving 6-TX as the intermediate, whereas 2-MP is converted to 8-hydroxy-2-mercaptopurine as the expected end product in one step. Surprisingly, in contrast to the other thiopurines, enzymatic hydroxylation of 2-MP showed a unique hyperchromic effect at 264 nm as the reaction proceeded. However, when 2-TX is used as the substrate, it is hydroxylated to 2-thiouric acid. The enzymatic hydroxylation of 2-MP is considerably faster than that of 6-MP, while 6-TX and 2-TX show similar rates under identical reaction conditions. The reason why 2-MP is a better substrate than 6-MP and how the chemical nature and position of the functional groups present on the thiopurine substrates influence xanthine oxidase activity are discussed.

Photocatalytic activity of Pt-TiO2 films supported on hydroxylated fly ash cenospheres under visible light

NASA Astrophysics Data System (ADS)

Wang, Bing; Yang, Zewei; An, Hao; Zhai, Jianping; Li, Qin; Cui, Hao

2015-01-01

TiO2 was coated on the surface of hydroxylated fly ash cenospheres (FACs) by the sol-gel method. Platinum (Pt) was then deposited on these TiO2/FAC particles by a photoreduction method to form PTF photocatalyst. The photocatalytic activity of PTF for the degradation of methylene blue (MB) under visible-light irradiation was determined. The PTF sample that was calcined at 450 °C and had a Pt/TiO2 mass ratio of 1.5% exhibited the optimal photocatalytic activity for degradation of MB with a catalyst concentration of 3 g L-1. MB was photodecomposed by PTF in aqueous solution more effectively at alkali pH than at acidic pH, because more MB molecules were adsorbed on the surface of PTF under alkaline conditions than that under acidic. The effect of various inorganic anions (HCO3-, F-, SO42-, NO3-, and Cl-) on the photodegradation of MB by PTF was also investigated. Addition of anions with a concentration of 5 mM enhanced the photocatalytic efficiency of PTF because of the improved adsorption of MB. This effect weakened as the anion concentration was increased, which was attributed to the ability of the anions to scavenge hydroxyl radicals and holes. Our results indicated that the photodegradation of MB took place mainly on the catalyst surface. The generation of hydroxyl radicals in the photocatalytic reaction was measured by the fluorescence method. KI was used to determine the participation of holes in the photocatalytic reaction. Both hydroxyl radicals and valence-band holes were detected in the PTF system. Recycling tests revealed that calcination of the used PTF helped to regain its photocatalytic activity.

A competing, dual mechanism for catalytic direct benzene hydroxylation from combined experimental-DFT studies.

PubMed

Vilella, Laia; Conde, Ana; Balcells, David; Díaz-Requejo, M Mar; Lledós, Agustí; Pérez, Pedro J

2017-12-01

A dual mechanism for direct benzene catalytic hydroxylation is described. Experimental studies and DFT calculations have provided a mechanistic explanation for the acid-free, Tp x Cu-catalyzed hydroxylation of benzene with hydrogen peroxide (Tp x = hydrotrispyrazolylborate ligand). In contrast with other catalytic systems that promote this transformation through Fenton-like pathways, this system operates through a copper-oxyl intermediate that may interact with the arene ring following two different, competitive routes: (a) electrophilic aromatic substitution, with the copper-oxyl species acting as the formal electrophile, and (b) the so-called rebound mechanism, in which the hydrogen is abstracted by the Cu-O moiety prior to the C-O bond formation. Both pathways contribute to the global transformation albeit to different extents, the electrophilic substitution route seeming to be largely favoured.

Hydroxyl radicals' production and ECG parameters during ischemia and reperfusion in rat, guinea pig and rabbit isolated heart.

PubMed

Paulova, Hana; Stracina, Tibor; Jarkovsky, Jiri; Novakova, Marie; Taborska, Eva

2013-06-01

Ischemic and reperfusion injury is a serious condition related to numerous biochemical and electrical abnormalities of the myocardium. It has been repeatedly studied in various animal models. In this study, the production of hydroxyl radicals and electrophysiological parameters were compared in three species. Rat, guinea pig and rabbit isolated hearts were perfused according to Langendorff under strictly identical conditions. The heart rate and arrhythmia were monitored during ischemia and reperfusion periods at defined time intervals; the production of hydroxyl radical was determined by HPLC as 2.5-dihydroxybenzoic acid (2.5-DHBA) formed by salicylic acid hydroxylation. Relationship between arrhythmias and production of 2.5-DHBA was studied. The inter-species differences were observed in timing of arrhythmias onset and their severity, and in the production of 2.5-DHBA in both ischemia and reperfusion. The most considerable changes were observed in rats, where arrhythmias appeared early and with highest severity during ischemia on one side and the regular rhythm was restored early and completely during reperfusion. The corresponding changes in the production of 2.5-DHBA were observed. It can be concluded that rat isolated heart is the most suitable model for evaluation of ischemia/reperfusion injury under given experimental conditions.

Cytochrome P450 family member CYP704B2 catalyzes the {omega}-hydroxylation of fatty acids and is required for anther cutin biosynthesis and pollen exine formation in rice.

PubMed

Li, Hui; Pinot, Franck; Sauveplane, Vincent; Werck-Reichhart, Danièle; Diehl, Patrik; Schreiber, Lukas; Franke, Rochus; Zhang, Ping; Chen, Liang; Gao, Yawei; Liang, Wanqi; Zhang, Dabing

2010-01-01

The anther cuticle and microspore exine act as protective barriers for the male gametophyte and pollen grain, but relatively little is known about the mechanisms underlying the biosynthesis of the monomers of which they are composed. We report here the isolation and characterization of a rice (Oryza sativa) male sterile mutant, cyp704B2, which exhibits a swollen sporophytic tapetal layer, aborted pollen grains without detectable exine, and undeveloped anther cuticle. In addition, chemical composition analysis indicated that cutin monomers were hardly detectable in the cyp704B2 anthers. These defects are caused by a mutation in a cytochrome P450 family gene, CYP704B2. The CYP704B2 transcript is specifically detected in the tapetum and the microspore from stage 8 of anther development to stage 10. Heterologous expression of CYP704B2 in yeast demonstrated that CYP704B2 catalyzes the production of omega -hydroxylated fatty acids with 16 and 18 carbon chains. Our results provide insights into the biosynthesis of the two biopolymers sporopollenin and cutin. Specifically, our study indicates that the omega -hydroxylation pathway of fatty acids relying on this ancient CYP704B family, conserved from moss to angiosperms, is essential for the formation of both cuticle and exine during plant male reproductive and spore development.

Synthesis and radical scavenging activity of 6-hydroxyl-4-methylcoumarin and its derivatives

NASA Astrophysics Data System (ADS)

Jumal, Juliana; Ayomide, Adetunji Fridaos

2018-06-01

Four compounds of coumarin derivatives namely 6-hydroxyl-4-methylcoumarin (I), 6-hydroxyl-4-methyl-5-(p-nitrophenyl azocoumarin) (II), 6-hydroxyl-4-methyl-5,7-(bis-p-nitrophenyl azocoumarin) (III) and 6-hydroxyl-4-methyl-5,7-(bis-p-chlorophenyl azocoumarin) (IV) were successfully synthesized. These compounds were prepared by reacting hydroquinone with ethylacetoacetate and selected anilines which are chloro and nitro aniline. All synthesized compounds were characterized by CHN micro-elemental analysis, 1H Nuclear Magnetic Resonance (NMR) and Fourier Transform Infrared (FTIR) spectroscopic methods. The infrared spectra of these compounds exhibited five important stretching vibrations: ʋ(-OH), ʋ(C=O), ʋ(C=C), ʋ(C-O) and ʋ(C-N) at 3441-3359 cm-1, 1604-1632 cm-1, 1581-1496 cm-1, 1331-1225 cm-1, 1251-1109 cm-1, respectively. 1H NMR spectra of these compounds show the presence of proton aromatic, proton methyl and proton pyrone ring with the chemical shift at δH 7.00-8.70 ppm, δH 2.20-2.50 ppm and δH 6.10-6.90 ppm, respectively. CHN analysis results of all compounds are in good agreement with the calculated values. All the synthesized compounds were evaluated for their antioxidant activity using DPPH method and ascorbic acid used as the standard. UV-Vis spectroscopic technique was used to investigate the absorbance of these compounds. Compound (II) shows high antioxidant activities compared to compound (I), (III) and (IV) which show moderate to low activities.

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. Copyright © 2012 Elsevier Ltd. All rights reserved.

Dimers in α-pinene secondary organic aerosol: effect of hydroxyl radical, ozone, relative humidity and aerosol acidity

NASA Astrophysics Data System (ADS)

Kristensen, K.; Cui, T.; Zhang, H.; Gold, A.; Glasius, M.; Surratt, J. D.

2014-04-01

The formation of secondary organic aerosol (SOA) from both ozonolysis and hydroxyl radical (OH)-initiated oxidation of α-pinene under conditions of high nitric oxide (NO) concentrations with varying relative humidity (RH) and aerosol acidity was investigated in the University of North Carolina dual outdoor smog chamber facility. SOA formation from ozonolysis of α-pinene was enhanced relative to that from OH-initiated oxidation in the presence of initially high-NO conditions. However, no effect of RH on SOA mass was evident. Ozone (O3)-initiated oxidation of α-pinene in the presence of ammonium sulfate (AS) seed coated with organic aerosol from OH-initiated oxidation of α-pinene showed reduced nucleation compared to ozonolysis in the presence of pure AS seed aerosol. The chemical composition of α-pinene SOA was investigated by ultra-performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS), with a focus on the formation of carboxylic acids and high-molecular weight dimers. A total of eight carboxylic acids and four dimers were identified, constituting between 8 and 12% of the total α-pinene SOA mass. OH-initiated oxidation of α-pinene in the presence of nitrogen oxides (NOx) resulted in the formation of highly oxidized carboxylic acids, such as 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA) and diaterpenylic acid acetate (DTAA). The formation of dimers was observed only in SOA produced from the ozonolysis of α-pinene in the absence of NOx, with increased concentrations by a factor of two at higher RH (50-90%) relative to lower RH (30-50%). The increased formation of dimers correlates with an observed increase in new particle formation at higher RH due to nucleation. Increased aerosol acidity was found to have a negligible effect on the formation of the dimers. SOA mass yield did not influence the chemical composition of SOA formed from α-pinene ozonolysis with respect to

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

Ultrasound Assisted Synthesis of Hydroxylated Soybean Lecithin from Crude Soybean Lecithin as an Emulsifier.

PubMed

Chiplunkar, Pranali P; Pratap, Amit P

2017-10-01

Soybean lecithin is a by-product obtained during degumming step of crude soybean oil refining. Crude soybean lecithin (CSL) contains major amount of phospholipids (PLs) along with minor amount of acylglycerols, bioactive components, etc. Due to presence of PLs, CSL can be used as an emulsifier. Crude soybean lecithin (CSL) was utilized to synthesize hydroxylated soybean lecithin (HSL) by hydroxylation using hydrogen peroxide and catalytic amount of lactic acid to enhance the hydrophilicity and emulsifying properties of CSL. To reduce the reaction time and to increase rate of reaction, HSL was synthesized under ultrasound irradiation. The effect of different operating parameters such as lactic acid, hydrogen peroxide, temperature, ultrasonic power and duty cycle in synthesis of HSL were studied and optimized. The surface tension (SFT), interfacial tension (IFT) and the critical micelle concentration (CMC) of the HSL (26.11 mN/m, 2.67 mN/m, 112 mg/L) were compared to CSL (37.53 mN/m, 6.22 mN/m, 291 mg/L) respectively. The HSL has better emulsion stability and low foaming characteristics as compared to CSL. Therefore, the product as an effective emulsifier can be used in food, pharmacy, lubricant, cosmetics, etc.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Munoz-Munoz, Jose Luis; Berna, Jose; Garcia-Molina, Maria del Mar

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 chemicalmore » 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

Detoxification of Fusaric Acid by the Soil Microbe Mucor rouxii.

PubMed

Crutcher, Frankie K; Puckhaber, Lorraine S; Bell, Alois A; Liu, Jinggao; Duke, Sara E; Stipanovic, Robert D; Nichols, Robert L

2017-06-21

Fusarium oxysporum f. sp. vasinfectum race 4 (VCG0114), which causes root rot and wilt of cotton (Gossypium hirsutum and G. barbadense), has been identified recently for the first time in the western hemisphere in certain fields in the San Joaquin Valley of California. This pathotype produces copious quantities of the plant toxin fusaric acid (5-butyl-2-pyridinecarboxylic acid) compared to other isolates of F. oxysporum f. sp. vasinfectum (Fov) that are indigenous to the United States. Fusaric acid is toxic to cotton plants and may help the pathogen compete with other microbes in the soil. We found that a laboratory strain of the fungus Mucor rouxii converts fusaric acid into a newly identified compound, 8-hydroxyfusaric acid. The latter compound is significantly less phytotoxic to cotton than the parent compound. On the basis of bioassays of hydroxylated analogues of fusaric acid, hydroxylation of the butyl side chain of fusaric acid may affect a general detoxification of fusaric acid. Genes that control this hydroxylation may be useful in developing biocontrol agents to manage Fov.

Biotechnological Production of Caffeic Acid by Bacterial Cytochrome P450 CYP199A2

PubMed Central

Arai, Yuka; Kino, Kuniki

2012-01-01

Caffeic acid is a biologically active molecule that has various beneficial properties, including antioxidant, anticancer, and anti-inflammatory activities. In this study, we explored the catalytic potential of a bacterial cytochrome P450, CYP199A2, for the biotechnological production of caffeic acid. When the CYP199A2 enzyme was reacted with p-coumaric acid, it stoichiometrically produced caffeic acid. The crystal structure of CYP199A2 shows that Phe at position 185 is situated directly above, and only 6.35 Å from, the heme iron. This F185 residue was replaced with hydrophobic or hydroxylated amino acids using site-directed mutagenesis to create mutants with novel and improved catalytic properties. In whole-cell assays with the known substrate of CYP199A2, 2-naphthoic acid, only the wild-type enzyme hydroxylated 2-naphthoic acid at the C-7 and C-8 positions, whereas all of the active F185 mutants exhibited a preference for C-5 hydroxylation. Interestingly, several F185 mutants (F185V, F185L, F185I, F185G, and F185A mutants) also acquired the ability to hydroxylate cinnamic acid, which was not hydroxylated by the wild-type enzyme. These results demonstrate that F185 is an important residue that controls the regioselectivity and the substrate specificity of CYP199A2. Furthermore, Escherichia coli cells expressing the F185L mutant exhibited 5.5 times higher hydroxylation activity for p-coumaric acid than those expressing the wild-type enzyme. By using the F185L whole-cell catalyst, the production of caffeic acid reached 15 mM (2.8 g/liter), which is the highest level so far attained in biotechnological production of this compound. PMID:22729547

Characterization and diagenesis of strong-acid carboxyl groups in humic substances

USGS Publications Warehouse

Leenheer, J.A.; Wershaw, R. L.; Brown, G.K.; Reddy, M.M.

2003-01-01

A small fraction of carboxylic acid functional groups in humic substances are exceptionally acidic with pKa values as low as 0.5. A review of acid-group theory eliminated most models and explanations for these exceptionally acidic carboxyl groups. These acidic carboxyl groups in Suwannee River fulvic acid were enriched by a 2-stage fractionation process and the fractions were characterized by elemental, molecular-weight, and titrimetric analyses, and by infrared and 13C- and 1H-nuclear magnetic resonance spectrometry. An average structural model of the most acidic fraction derived from the characterization data indicated a high density of carboxyl groups clustered on oxygen-heterocycle alicyclic rings. Intramolecular H-bonding between adjacent carboxyl groups in these ring structures enhanced stabilization of the carboxylate anion which results in low pKa1 values. The standard, tetrahydrofuran tetracarboxylic acid, was shown to have similar acidity characteristics to the highly acidic fulvic acid fraction. The end products of 3 known diagenetic pathways for the formation of humic substances were shown to result in carboxyl groups clustered on oxygen-heterocycle alicyclic rings.

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

PubMed

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

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.

Hydroxyl radical scavenging assay of phenolics and flavonoids with a modified cupric reducing antioxidant capacity (CUPRAC) method using catalase for hydrogen peroxide degradation.

PubMed

Ozyürek, Mustafa; Bektaşoğlu, Burcu; Güçlü, Kubilay; Apak, Reşat

2008-06-02

Hydroxyl radicals (OH) generated in the human body may play an important role in tissue injury at sites of inflammation in oxidative stress-originated diseases. As a more convenient, efficient, and less costly alternative to HPLC/electrochemical detection techniques and to the nonspecific, low-yield deoxyribose (TBARS) test, we used a salicylate probe for detecting OH generated by the reaction of iron(II)-EDTA complex with H(2)O(2). The produced hydroxyl radicals attack both the salicylate probe and the hydroxyl radical scavengers that are incubated in solution for 10 min. Added radical scavengers compete with salicylate for the OH produced, and diminish chromophore formation from Cu(II)-neocuproine. At the end of the incubation period, the reaction was stopped by adding catalase. With the aid of this reaction, a kinetic approach was adopted to assess the hydroxyl radical scavenging properties of polyphenolics, flavonoids and other compounds (e.g., ascorbic acid, glucose, mannitol). A second-order rate constant for the reaction of the scavenger with OH could be deduced from the inhibition of colour formation due to the salicylate probe. In addition to phenolics and flavonoids, five kinds of herbs were evaluated for their OH scavenging activity using the developed method. The modified CUPRAC (cupric ion reducing antioxidant capacity) assay proved to be efficient for ascorbic acid, gallic acid and chlorogenic acid, for which the deoxyribose assay test is basically nonresponsive. An important contribution of this developed assay is the inhibition of the Fenton reaction with catalase degradation of hydrogen peroxide so that the remaining H(2)O(2) would neither give a CUPRAC absorbance nor involve in redox cycling of phenolic antioxidants, enabling the rapid assay of polyphenolics.

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

USDA-ARS?s Scientific Manuscript database

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 ...

An Experimental and Computational Study of the Gas-Phase Acidities of the Common Amino Acid Amides.

PubMed

Plummer, Chelsea E; Stover, Michele L; Bokatzian, Samantha S; Davis, John T M; Dixon, David A; Cassady, Carolyn J

2015-07-30

Using proton-transfer reactions in a Fourier transform ion cyclotron resonance mass spectrometer and correlated molecular orbital theory at the G3(MP2) level, gas-phase acidities (GAs) and the associated structures for amides corresponding to the common amino acids have been determined for the first time. These values are important because amino acid amides are models for residues in peptides and proteins. For compounds whose most acidic site is the C-terminal amide nitrogen, two ions populations were observed experimentally with GAs that differ by 4-7 kcal/mol. The lower energy, more acidic structure accounts for the majority of the ions formed by electrospray ionization. G3(MP2) calculations predict that the lowest energy anionic conformer has a cis-like orientation of the [-C(═O)NH](-) group whereas the higher energy, less acidic conformer has a trans-like orientation of this group. These two distinct conformers were predicted for compounds with aliphatic, amide, basic, hydroxyl, and thioether side chains. For the most acidic amino acid amides (tyrosine, cysteine, tryptophan, histidine, aspartic acid, and glutamic acid amides) only one conformer was observed experimentally, and its experimental GA correlates with the theoretical GA related to side chain deprotonation.

Cytotoxic effects of polybasic acids, poly(alkenoic acid)s, and the monomers with various functional groups on human pulp fibroblasts.

PubMed

Kurata, Shigeaki; Morishita, Kumiko; Kawase, Toshio; Umemoto, Kozo

2011-01-01

This study evaluated the cytotoxicity of various polybasic acids, poly(alkenoic acid)s, and the monomers with various acidic functional groups such as carboxyl, phosphoryl, and sulfo group. The cell growth of fibroblasts cultivated in medium containing polybasic acids and polymers up to the concentration to 5 mmol/L was not significantly different compared with that of control without their acids. On the other hand, the cell growth fibroblasts cultivated in medium containing 1 mmol/L of the monomers with acryloyloxy and phosphoryl or carboxyl group decreased remarkably compared with that of the control and the cells were probably lifeless. Those exposed to the monomers with a ether bond and a carboxyl group or a amide bond and a sulfo group was not significantly different compared with that of control.

Self-assembly of fatty acids on hydroxylated Al surface and effects of their stability on wettability and nanoscale organization.

PubMed

Liascukiene, Irma; Steffenhagen, Marie; Asadauskas, Svajus J; Lambert, Jean-François; Landoulsi, Jessem

2014-05-27

The self-assembly of fatty acids (FA) on the surfaces of inorganic materials is a relevant way to control their wetting properties. While the mechanism of adsorption on model flat substrate is well described in the literature, interfacial processes remain poorly documented on nanostructured surfaces. In this study, we report the self-assembly of a variety of FA on a hydroxylated Al surface which exhibits a random nanoscale organization. Our results revealed a peculiar fingerprint due to the FA self-assembly which consists in the formation of aligned nanopatterns in a state of hierarchical nanostructuration, regardless of the molecular structure of the FA (chain length, level of unsaturation). After a significant removal of adsorbed FA using UV/O3 treatment, a complete wetting was reached, and a noticeable disturbance of the surface morphology was observed, evidencing the pivotal role of FA molecules to maintain these nanostructures. The origin of wetting properties was investigated prior to and after conditioning of FA-modified samples taking into account key parameters, namely the surface roughness and its composition. For this purpose, the Wenzel roughness, defined as the third moment of power spectral density, was used, as it is sensitive to high spatial frequency and thus to the obtained hierarchical level of nanostructuration. Our results revealed that no correlation can be made between water contact angles (θ(w)) and the Wenzel roughness. By contrast, θ(w) strongly increased with the amount of -CHx- groups exhibited by adsorbed FA. These findings suggest that the main origin of hydrophobization is the presence of self-assembled molecules and that the surface roughness has only a small contribution to the wettability.

Comparison of folic acid levels in schizophrenic patients and control groups

NASA Astrophysics Data System (ADS)

Arthy, C. C.; Amin, M. M.; Effendy, E.

2018-03-01

Folic acid deficiency is a risk factor for schizophrenia through epidemiology, biochemistry and gene-related studies. Compared with healthy people, schizophrenic patients may have high homocysteine plasma values and homocysteine or low levels of folic acid, which seems to correlate with extrapyramidal motor symptoms caused by neuroleptic therapy and with symptoms of schizophrenia. In this present study, we focus on the difference of folic acid level between schizophrenic patient and control group. The study sample consisted of schizophrenic patients and 14 people in the control group and performed blood sampling to obtain the results of folic acid levels. The folic acid level in both groups was within normal range, but the schizophrenic patient group had lower mean folic acid values of 5.00 ng/ml (sb 1.66), compared with the control group with mean folic acid values of 10.75 ng/ml (sb 4.33). there was the group of the control group had a higher value of folic acid than the schizophrenic group.

Influence of metal loading and humic acid functional groups on the complexation behavior of trivalent lanthanides analyzed by CE-ICP-MS.

PubMed

Kautenburger, Ralf; Hein, Christina; Sander, Jonas M; Beck, Horst P

2014-03-13

The complexation behavior of Aldrich humic acid (AHA) and a modified humic acid (AHA-PB) with blocked phenolic hydroxyl groups for trivalent lanthanides (Ln) is compared, and their influence on the mobility of Ln(III) in an aquifer is analyzed. As speciation technique, capillary electrophoresis (CE) was hyphenated with inductively coupled plasma mass spectrometry (ICP-MS). For metal loading experiments 25 mg L(-1) of AHA and different concentrations (cLn(Eu+Gd)=100-6000 μg L(-1)) of Eu(III) and Gd(III) in 10mM NaClO4 at pH 5 were applied. By CE-ICP-MS, three Ln-fractions, assumed to be uncomplexed, weakly and strongly AHA-complexed metal can be detected. For the used Ln/AHA-ratios conservative complex stability constants log βLnAHA decrease from 6.33 (100 μg L(-1) Ln(3+)) to 4.31 (6000 μg L(-1) Ln(3+)) with growing Ln-content. In order to verify the postulated weaker and stronger humic acid binding sites for trivalent Eu and Gd, a modified AHA with blocked functional groups was used. For these experiments 500 μg L(-1) Eu and 25 mg L(-1) AHA and AHA-PB in 10mM NaClO4 at pH-values ranging from 3 to 10 have been applied. With AHA-PB, where 84% of the phenolic OH-groups and 40% of the COOH-groups were blocked, Eu complexation was significantly lower, especially at the strong binding sites. The log β-values decrease from 6.11 (pH 10) to 5.61 at pH 3 (AHA) and for AHA-PB from 6.01 (pH 7) to 3.94 at pH 3. As a potential consequence, particularly humic acids with a high amount of strong binding sites (e.g. phenolic OH- and COOH-groups) can be responsible for a higher metal mobility in the aquifer due to the formation of dissolved negatively charged metal-humate species. Copyright © 2014 Elsevier B.V. All rights reserved.

Growth and Electrophysiological Properties of Rat Embryonic Cardiomyocytes on Hydroxyl- and Carboxyl-Modified Surfaces

PubMed Central

NATARAJAN, ANUPAMA; CHUN, CHANGJU; HICKMAN, JAMES J.; MOLNAR, PETER

2010-01-01

Biodegradable scaffolds such as poly(lactic acid) (PLA), poly(lactic-co-glycolic acid) (PLGA) or poly(glycolic acid) (PGA) are commonly used materials in tissue engineering. The chemical composition of these scaffolds changes during degradation which provides a changing environment for the seeded cells. In this study we have developed a simple and relatively high-throughput method in order to test the physiological effects of this varying chemical environment on rat embryonic cardiac myocytes. In order to model the different degradation stages of the scaffold, glass coverslips were functionalized with 11-mercaptoundecanoic acid (MUA) and 11-mercapto-1-undecanol (MUL) as carboxyl- and hydroxyl-group presenting surfaces and also with trimethoxysilylpropyldiethylenetriamine (DETA) and (3-aminopropyl)triethoxysilane (APTES) as controls. Embryonic cardiac myocytes formed beating islands on all tested surfaces but the number of attached cells and beating patches was significantly lower on MUL compared to any of the other functionalized surfaces. Moreover, whole cell patch clamp experiments showed that the average length of action potentials generated by the beating cardiac myocytes were significantly longer on MUL compared to the other surfaces. Our results, using our simple test system, are in agreement with earlier observations that utilized the complex 3D biodegradable scaffold. Thus, surface functionalization with self-assembled monolayers combined with histological/physiological testing could be a relatively high throughput method for biocompatibility studies and for the optimization of the material/tissue interface in tissue engineering. PMID:18854125

Imino-Oxy Acetic Acid Dealkylation as Evidence for an Inner-Sphere Alcohol Intermediate in the Reaction Catalyzed by Peptidylglycine α-Hydroxylating Monooxygenase (PHM)

PubMed Central

McIntyre, Neil R.; Lowe, Edward W.; Merkler, David J.

2009-01-01

Peptidylglycine α-hydroxylating monooxygenase (PHM, EC 1.14.17.3) catalyzes the stereospecific hydroxylation of a glycyl α-carbon in a reaction that requires O2 and ascorbate. Subsequent dealkylation of the α-hydroxyglycine by another enzyme, peptidylamidoglycolate lyase (PAL. EC 4.3.2.5), yields a bioactive amide and glyoxylate. PHM is a non-coupled, type II dicopper monooxygenase which activates O2 at only a single copper atom, CuM. In this study, the PHM mechanism was probed using a non-natural substrate, benzaldehyde imino-oxy acetic acid (BIAA). PHM catalyzes the O-oxidative dealkylation of BIAA to benzaldoxime and glyoxylate with no involvement of PAL. The minimal kinetic mechanism for BIAA was shown to be steady-state ordered using primary deuterium kinetic isotope effects. The D(V/K)APPARENT, BIAA decreased from 14.7 ± 1.0 as [O2] → 0 to 1.0 ± 0.2 as [O2] → ∞ suggesting the dissociation rate constant from the PHM·BIAA complex decreases as [O2] increases; thereby, reducing the steady-state concentration of [PHM]free. BIAA was further used to differentiate between potential oxidative Cu/O species using a QM/MM reaction coordinate simulation to determine which species could yield product O-dealkylation that matched our experimental data. The results of this study provided compelling evidence for the presence of a covalently linked CuII-alkoxide intermediate with a quartet spin state responsible BIAA oxidation. PMID:19569683

Stereoselectivity of the arene epoxide pathway of mephenytoin hydroxylation in man.

PubMed

Küpfer, A; Lawson, J; Branch, R A

1984-02-01

Stereoselective metabolism of mephenytoin has been investigated in four normal subjects by comparing urinary recoveries of hydroxylated metabolites after administration of racemic RS-mephenytoin (1.4 mmol/day) and R-mephenytoin (0.7 mmol/day) on separate occasions. Gas chromatography-mass spectrometry was employed to measure the urinary recovery of 3-methyl-5-(4-hydroxyphenyl)-5-ethylhydantoin (4-OH-M) and mephenytoin catechol, methylcatechol, and dihydrodiol metabolites. Following a single oral dose of racemic mephenytoin, 4-OH-M, mephenytoin catechol, and methylcatechol metabolites were identified in urine mainly as conjugates, whereas the dihydrodiol metabolite was recovered mainly in its unconjugated form. Urinary elimination of each metabolite was similar on days 1 and 10 of chronic racemic mephenytoin administration. Following R-mephenytoin administration, urinary recoveries of hydroxylated metabolites were five to 10 times smaller than after administration of the racemic drug. This implies substrate-stereoselective hydroxylation of the S-enantiomer of mephenytoin. In one subject with a genetic deficiency of aromatic mephenytoin hydroxylation deficiency, the excretion of each hydroxylated mephenytoin metabolite after RS-mephenytoin administration was decreased to 5-15% of the values found in the four extensively hydroxylating study volunteers. The impaired formation of hydroxylated mephenytoin metabolites in genetic hydroxylation deficiency, in conjunction with stereoselective hydroxylation of S-mephenytoin via an extensive NIH shift in normal man, is consistent with the hypothesis that the formation of the S-mephenytoin arene oxide is under genetic control and represents the initial enzymatic reaction of stereoselective aromatic mephenytoin hydroxylation. The formation of this potentially reactive metabolite of S-mephenytoin may have implications in mephenytoin-induced toxicity.

Two-dimensional correlation spectroscopic analysis on the interaction between humic acids and aluminum coagulant.

PubMed

Jin, Pengkang; Song, Jina; Wang, Xiaochang C; Jin, Xin

2018-02-01

In this study, two-dimensional correlation spectroscopy integrated with synchronous fluorescence and infrared absorption spectroscopy was employed to investigate the interaction between humic acids and aluminum coagulant at slightly acidic and neutral pH. Higher fluorescence quenching was produced for fulvic-like and humic-like fractions at pH5. At pH5, the humic-like fractions originating from the carboxylic acid, carboxyl and polysaccharide compounds were bound to aluminum first, followed by the fulvic-like fractions originating from the carboxyl and polysaccharide compounds. This finding also demonstrated that the activated functional groups of HA were involved in forming the Al-HA complex, which was accompanied by the removal of other groups by co-precipitation. Meanwhile, at pH7, almost no fluorescence quenching occurred, and surface complexation was observed to occur, in which the activated functional groups were absorbed on the amorphous Al(OH) 3 . Two-dimensional FT-IR correlation spectroscopy indicated the sequence of HA structural change during coagulation with aluminum, with IR bands affected in the order of COOH>COO - >NH deformation of amide II>aliphatic hydroxyl COH at pH5, and COO - >aliphatic hydroxyl COH at pH7. This study provides a promising pathway for analysis and insight into the priority of functional groups in the interaction between organic matters and metal coagulants. Copyright © 2017. Published by Elsevier B.V.

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.

Conformational analyses of 2,3-dihydroxypropanoic acid as a function of solvent and ionization state as determined by NMR spectroscopy.

PubMed

Drake, Michael D; Harsha, Alex K; Terterov, Sergei; Roberts, John D

2006-03-01

Vicinal (1)H--(1)H coupling constants were used to determine the conformational preferences of 2,3-dihydroxypropanoic acid (1) (DL-glyceric acid) in various solvents and its different carboxyl ionization states. The stereospecific assignments of J(12) and J(13) were confirmed through the point-group substitution of the C-3 hydrogen with deuterium, yielding rac-(2SR,3RS)-[3-(2)H]-1, and the observation of only J(13) in the (1)H NMR spectra. While hydrogen bonding and steric strain may be expected to drive the conformational equilibrium, their role is overshadowed by a profound gauche effect between the vicinal hydroxyl groups that mimics other substituted ethanes, such as 1,2-ethanediol and 1,2-difluoroethane. At low pH, the conformational equilibrium is heavily weighted toward the gauche-hydroxyl rotamers with a range of 81% in DMSO-d(6) to 92% in tert-butyl alcohol-d(10). At high pH, the equilibrium exhibits a larger dependence upon the polarity and solvating capability of the medium, although the gauche effect still dominates in D(2)O, 1,4-dioxane-d(8), methanol-d(4), and ethanol-d(6) (96, 89, 85, and 83% gauche-hydroxyls respectively). The observed preference for the gauche-hydroxyl rotamers is believed to stem primarily from hyperconjugative sigma(C--H) --> sigma*(C--OH) interactions.

Reactions of clofibric acid with oxidative and reductive radicals-Products, mechanisms, efficiency and toxic effects

NASA Astrophysics Data System (ADS)

Csay, Tamás; Rácz, Gergely; Salik, Ádám; Takács, Erzsébet; Wojnárovits, László

2014-09-01

The degradation of clofibric acid induced by hydroxyl radical, hydrated electron and O2-•/HO2• reactive species was studied in aqueous solutions. Clofibric acid was decomposed more effectively by hydroxyl radical than by hydrated electron or O2-•/HO2•. Various hydroxylated, dechlorinated and fragmentation products have been identified and quantified. A new LC-MS method was developed based on 18O isotope labeling to follow the formation of hydroxylated derivatives of clofibric acid. Possible degradation pathways have been proposed. The overall degradation was monitored by determination of sum parameters like COD, TOC and AOX. It was found that the organic chlorine degrades very effectively prior to complete mineralization. After the treatment no toxic effect was found according to Vibrio fischeri tests. However, at early stages some of the reaction products were more harmful than clofibric acid.

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.

Tyrosinase-catalyzed hydroxylation of hydroquinone, a depigmenting agent, to hydroxyhydroquinone: A kinetic study.

PubMed

García-Molina, María del Mar; Muñoz Muñoz, Jose Luis; Martinez-Ortiz, Francisco; Martinez, José Rodriguez; García-Ruiz, Pedro Antonio; Rodriguez-López, José Neptuno; García-Cánovas, Francisco

2014-07-01

Hydroquinone (HQ) is used as a depigmenting agent. In this work we demonstrate that tyrosinase hydroxylates HQ to 2-hydroxyhydroquinone (HHQ). Oxy-tyrosinase hydroxylates HQ to HHQ forming the complex met-tyrosinase-HHQ, which can evolve in two different ways, forming deoxy-tyrosinase and p-hydroxy-o-quinone, which rapidly isomerizes to 2-hydroxy-p-benzoquinone or on the other way generating met-tyrosinase and HHQ. In the latter case, HHQ is rapidly oxidized by oxygen to generate 2-hydroxy-p-benzoquinone, and therefore, it cannot close the enzyme catalytic cycle for the lack of reductant (HHQ). However, in the presence of hydrogen peroxide, met-tyrosinase (inactive on hydroquinone) is transformed into oxy-tyrosinase, which is active on HQ. Similarly, in the presence of ascorbic acid, HQ is transformed into 2-hydroxy-p-benzoquinone by the action of tyrosinase; however, in this case, ascorbic acid reduces met-tyrosinase to deoxy-tyrosinase, which after binding to oxygen, originates oxy-tyrosinase. This enzymatic form is now capable of reacting with HQ to generate p-hydroxy-o-quinone, which rapidly isomerizes to 2-hydroxy-p-benzoquinone. The formation of HHQ during the action of tyrosinase on HQ is demonstrated by means of high performance liquid chromatography mass spectrometry (HPLC-MS) by using hydrogen peroxide and high ascorbic acid concentrations. We propose a kinetic mechanism for the tyrosinase oxidation of HQ which allows us the kinetic characterization of the process. A possible explanation of the cytotoxic effect of HQ is discussed. Copyright © 2014 Elsevier Ltd. All rights reserved.

Gas phase reaction of nitric acid with hydroxyl radical without and with water. A theoretical investigation.

PubMed

Gonzalez, Javier; Anglada, Josep M

2010-09-02

The gas phase reaction between nitric acid and hydroxyl radical, without and with a single water molecule, has been investigated theoretically using the DFT-B3LYP, MP2, QCISD, and CCSD(T) theoretical approaches with the 6-311+G(2df,2p) and aug-cc-pVTZ basis sets. The reaction without water begins with the formation of a prereactive hydrogen-bonded complex and has several elementary reactions processes. They include proton coupled electron transfer, hydrogen atom transfer, and proton transfer mechanisms, and our kinetic study shows a quite good agreement of the behavior of the rate constant with respect to the temperature and to the pressure with the experimental results from the literature. The addition of a single water molecule results in a much more complex potential energy surface although the different elementary reactions found have the same electronic features that the naked reaction. Two transition states are stabilized by the effect of a hydrogen bond interaction originated by the water molecule, and in the prereactive hydrogen bond region there is a geometrical rearrangement necessary to prepare the HO and HNO(3) moieties to react to each other. This step contributes the reaction to be slower than the reaction without water and explains the experimental finding, pointing out that there is no dependence for the HNO(3) + HO reaction on water vapor.

A Fast and Effective Pyridine-Free Method for the Determination of Hydroxyl Value of Hydroxyl-Terminated Polybutadiene and Other Hydroxy Compounds

NASA Astrophysics Data System (ADS)

Alex, Ancy Smitha; Kumar, Vijendra; Sekkar, V.; Bandyopadhyay, G. G.

2017-07-01

Hydroxyl-terminated polybutadiene (HTPB) is the workhorse propellant binder for launch vehicle and missile applications. Accurate determination of the hydroxyl value (OHV) of HTPB is crucial for tailoring the ultimate mechanical and ballistic properties of the propellant derived. This article describes a fast and effective methodology free of pyridine based on acetic anhydride, N-methyl imidazole, and toluene for the determination of OHV of nonpolar polymers like HTPB and other hydroxyl compounds. This method gives accurate and reproducible results comparable to standard methods and is superior to existing methods in terms of user friendliness, efficiency, and time requirement.

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

DOEpatents

Luebke, David; Nulwala, Hunaid; Tang, Chau

2016-01-26

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

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.

Functional analysis of the gene controlling hydroxylation of festuclavine in the ergot alkaloid pathway of Neosartorya fumigata.

PubMed

Bilovol, Yulia; Panaccione, Daniel G

2016-11-01

Bioactive ergot alkaloids produced by several species of fungi are important molecules in agriculture and medicine. Much of the ergot alkaloid pathway has been elucidated, but a few steps, including the gene controlling hydroxylation of festuclavine to fumigaclavine B, remain unsolved. Festuclavine is a key intermediate in the fumigaclavine branch of the ergot alkaloid pathway of the opportunistic pathogen Neosartorya fumigata and also in the dihydrolysergic acid-based ergot alkaloid pathway of certain Claviceps species. Based on several lines of evidence, the N. fumigata gene easM is a logical candidate to encode the festuclavine-hydroxylating enzyme. To test this hypothesis we disrupted easM function by replacing part of its coding sequences with a hygromycin resistance gene and transforming N. fumigata with this construct. High-pressure liquid chromatography analysis demonstrated that easM deletion mutants were blocked in the ergot alkaloid pathway at festuclavine, and downstream products were eliminated. An additional alkaloid, proposed to be a prenylated form of festuclavine on the basis of mass spectral data, also accumulated to higher concentrations in the easM knockout. Complementation with the wild-type allele of easM gene restored the ability of the fungus to produce downstream compounds. These results indicate that easM encodes an enzyme required for fumigaclavine B synthesis likely by hydroxylating festuclavine. The festuclavine-accumulating strain of N. fumigata may facilitate future investigations of the biosynthesis of dihydrolysergic acid derivatives, which are derived from festuclavine and are the basis for several important drugs.

Lack of correlation between in vitro and in vivo studies on the effects of tangeretin and tangerine juice on midazolam hydroxylation.

PubMed

Backman, J T; Mäenpää, J; Belle, D J; Wrighton, S A; Kivistö, K T; Neuvonen, P J

2000-04-01

Tangeretin is a flavonoid that stimulates the catalytic activity of cytochrome P450 3A4 (CYP3A4) and is found in high levels in tangerine juice. The effect of tangeretin on hydroxylation of midazolam, a CYP3A4 probe, was examined in vitro with human liver microsomes and recombinant CYP3A4. In addition, the effect of tangerine juice on the pharmacokinetics and pharmacodynamics of orally administered midazolam (15 mg) and its active 1'-hydroxymetabolite was studied in a randomized crossover study in eight healthy volunteers. In microsomes from three human livers, tangeretin (1 to 100 micromol/L) increased 1'-hydroxymidazolam formation (12.5 micromol/L midazolam) by up to 212%. In complementary deoxyribonucleic acid-expressed CYP3A4, a 52% stimulation of midazolam 1'-hydroxylation was reached at 50 micromol/L tangeretin with no effect on midazolam 4-hydroxylation. In the pharmacokinetic-pharmacodynamic study, 200 mL tangerine juice reduced the area under the concentration versus time curve to 1.5 hours [AUC(O-1.5h)] of midazolam and 1'-hydroxymidazolam by 39% and 46%, respectively, and prolonged the time to reach peak concentration (P < .05) without affecting the total AUC values, elimination half-life values, or AUC ratios (1'-hydroxymidazolam/midazolam). These findings are consistent with a small delay in the absorption of midazolam and lack of effect on midazolam 1'-hydroxylation. Accordingly, tangerine juice slightly postponed the maximum pharmacodynamic effects of midazolam (P < .05). Tangeretin is a potent regioselective stimulator of midazolam 1'-hydroxylation by human liver microsomes and complementary deoxyribonucleic acid-expressed CYP3A4. However, tangerine juice is unlikely to have any appreciable effect on CYP3A4 in humans. Further studies are required to assess whether in vitro stimulators of CYP3A4 can influence drug metabolism in vivo.

Influence of surface hydroxylation on 3-aminopropyltriethoxysilane growth mode during chemical functionalization of GaN Surfaces: an angle-resolved X-ray photoelectron spectroscopy Study.

PubMed

Arranz, A; Palacio, C; García-Fresnadillo, D; Orellana, G; Navarro, A; Muñoz, E

2008-08-19

A comparative study of the chemical functionalization of undoped, n- and p-type GaN layers grown on sapphire substrates by metal-organic chemical vapor deposition was carried out. Both types of samples were chemically functionalized with 3-aminopropyltriethoxysilane (APTES) using a well-established silane-based approach for functionalizing hydroxylated surfaces. The untreated surfaces as well as those modified by hydroxylation and APTES deposition were analyzed using angle-resolved X-ray photoelectron spectroscopy. Strong differences were found between the APTES growth modes on n- and p-GaN surfaces that can be associated with the number of available hydroxyl groups on the GaN surface of each sample. Depending on the density of surface hydroxyl groups, different mechanisms of APTES attachment to the GaN surface take place in such a way that the APTES growth mode changes from a monolayer to a multilayer growth mode when the number of surface hydroxyl groups is decreased. Specifically, a monolayer growth mode with a surface coverage of approximately 78% was found on p-GaN, whereas the formation of a dense film, approximately 3 monolayers thick, was observed on n-GaN.

Influence of Functional Groups on the Viscosity of Organic Aerosol.

PubMed

Rothfuss, Nicholas E; Petters, Markus D

2017-01-03

Organic aerosols can exist in highly viscous or glassy phase states. A viscosity database for organic compounds with atmospherically relevant functional groups is compiled and analyzed to quantify the influence of number and location of functional groups on viscosity. For weakly functionalized compounds the trend in viscosity sensitivity to functional group addition is carboxylic acid (COOH) ≈ hydroxyl (OH) > nitrate (ONO 2 ) > carbonyl (CO) ≈ ester (COO) > methylene (CH 2 ). Sensitivities to group addition increase with greater levels of prior functionalization and decreasing temperature. For carboxylic acids a sharp increase in sensitivity is likely present already at the second addition at room temperature. Ring structures increase viscosity relative to linear structures. Sensitivities are correlated with analogously derived sensitivities of vapor pressure reduction. This may be exploited in the future to predict viscosity in numerical models by piggybacking on schemes that track the evolution of organic aerosol volatility with age.

Cytochrome P450 Family Member CYP704B2 Catalyzes the ω -Hydroxylation of Fatty Acids and Is Required for Anther Cutin Biosynthesis and Pollen Exine Formation in Rice[W][OA

PubMed Central

Li, Hui; Pinot, Franck; Sauveplane, Vincent; Werck-Reichhart, Danièle; Diehl, Patrik; Schreiber, Lukas; Franke, Rochus; Zhang, Ping; Chen, Liang; Gao, Yawei; Liang, Wanqi; Zhang, Dabing

2010-01-01

The anther cuticle and microspore exine act as protective barriers for the male gametophyte and pollen grain, but relatively little is known about the mechanisms underlying the biosynthesis of the monomers of which they are composed. We report here the isolation and characterization of a rice (Oryza sativa) male sterile mutant, cyp704B2, which exhibits a swollen sporophytic tapetal layer, aborted pollen grains without detectable exine, and undeveloped anther cuticle. In addition, chemical composition analysis indicated that cutin monomers were hardly detectable in the cyp704B2 anthers. These defects are caused by a mutation in a cytochrome P450 family gene, CYP704B2. The CYP704B2 transcript is specifically detected in the tapetum and the microspore from stage 8 of anther development to stage 10. Heterologous expression of CYP704B2 in yeast demonstrated that CYP704B2 catalyzes the production of ω -hydroxylated fatty acids with 16 and 18 carbon chains. Our results provide insights into the biosynthesis of the two biopolymers sporopollenin and cutin. Specifically, our study indicates that the ω -hydroxylation pathway of fatty acids relying on this ancient CYP704B family, conserved from moss to angiosperms, is essential for the formation of both cuticle and exine during plant male reproductive and spore development. PMID:20086189

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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 showmore » 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.« less

Strong-acid, carboxyl-group structures in fulvic acid from the Suwannee River, Georgia. 2. Major structures

USGS Publications Warehouse

Leenheer, J.A.; Wershaw, R. L.; Reddy, M.M.

1995-01-01

Polycarboxylic acid structures that account for the strong-acid characteristics (pKa1 near 2.0) were examined for fulvic acid from the Suwannee River. Studies of model compounds demonstrated that pKa values near 2.0 occur only if the ??-ether or ??-ester groups were in cyclic structures with two to three additional electronegative functional groups (carboxyl, ester, ketone, aromatic groups) at adjacent positions on the ring. Ester linkage removal by alkaline hydrolysis and destruction of ether linkages through cleavage and reduction with hydriodic acid confirmed that the strong carboxyl acidity in fulvic acid was associated with polycarboxylic ??-ether and ??-ester structures. Studies of hypothetical structural models of fulvic acid indicated possible relation of these polycarboxylic structures with the amphiphilic and metal-binding properties of fulvic acid.

Kinetics of surface processes for Mo(CO){sub 6} on partially dehydroxylated alumina and hydroxylated alumina. Observation of Mo(CO){sub 5}(ads)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reddy, K.P.; Brown, T.L.

1995-03-15

The adsorption of Mo(CO){sub 6} on partially dehydroxylated alumina (PDA) and hydroxylated alumina (HA) has been studied using IR and UV-vis spectroscopy. The results from these experiments suggest that the initially physisorbed Mo(CO){sub 6} coordinates to two distinct Lewis acid sites on the surface of PDA, one much more abundant than the other, with an apparent single rate constant 2.3 x 10{sup {minus}3} s{sup {minus}1} at 298 K. The Mo(CO){sub 6}(ads) in turn loses CO reversibly, with an apparent single rate constant 1.8 x 10{sup {minus}4} s{sup {minus}1} at 298 K to form Mo(CO){sub 5}(ads). Upon removal of gas phasemore » CO released in the first step, Mo(CO){sub 5}(ads) loses two additional COs to form Mo(CO){sub 3}(ads). Alternatively, on HA physisorbed Mo(CO){sub 6} undergoes nucleophilic attack by hydroxyl groups, which results in cis-labilization of a carbonyl group, leading in turn to the formation of Mo(CO){sub 5}(L), where L is a surface hydroxyl. The Mo(CO){sub 5}(L) so formed loses additional carbonyls to form a lower subcarbonyl. The decarbonylation process appears to be faster than on PDA. The experimental data indicate that there are no Al{sup 31} exposed on HA. All the observed decarbonylation processes are reversible under CO at room temperature on both HA and PDA. The addition of CO{sub 2} to the subcarbonyl on HA results in the formation of a bicarbonate, with displacement of the subcarbonyls. 24 refs., 11 figs., 1 tab.« less

Optimal Production of 7,10-dihydroxy-8(E)-hexadecenoic Acid from Palmitoleic Acid by Pseudomonas aeruginosa PR3

USDA-ARS?s Scientific Manuscript database

The hydroxylation of unsaturated fatty acids by bacterial strains is one type of value-adding bioconversion process. This process generates new hydroxy fatty acids (HFA) carrying special properties such as higher viscosity and reactivity compared with normal fatty acids. Among microbial strains te...

Hydroxyapatite-phosphonoformic acid hybrid compounds prepared by hydrothermal method

NASA Astrophysics Data System (ADS)

Turki, Thouraya; Othmani, Masseoud; Bantignies, Jean-Louis; Bouzouita, Khaled

2014-01-01

Hydroxyapatites were prepared in the presence of different amounts of phosphonoformic acid (PFA) via the hydrothermal method. The obtained powders were characterized through chemical analysis, XRD, IR, 31P MAS-NMR, TEM, and TG-TDA. The XRD showed that the PFA did not affect the apatite composition. Indeed, only a reduction of the crystallite size was noted. After grafting of PFA, the IR spectroscopy revealed the appearance of new bands belonging to HPO42- and carboxylate groups of the apatite and organic moiety, respectively. Moreover, the 31P MAS-NMR spectra exhibited a peak with a low intensity assigned to the terminal phosphonate group of the organic moiety in addition to that of the apatite. Based on these results, a reaction mechanism involving the surface hydroxyl groups (tbnd Casbnd OH) of the apatite and the carboxyl group of the acid was proposed.

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

specific, and of a higher yield than the classical TBARS assay. The hydroxyl radical scavenging rate constants of ascorbic acid, formate, and hexacyanoferrate(II) that caused interference in other assays could be easily found with the proposed procedure.

Unusual glycosylation of proteins: Beyond the universal sequon and other amino acids.

PubMed

Dutta, Devawati; Mandal, Chhabinath; Mandal, Chitra

2017-12-01

Glycosylation of proteins is the most common, multifaceted co- and post-translational modification responsible for many biological processes and cellular functions. Significant alterations and aberrations of these processes are related to various pathological conditions, and often turn out to be disease biomarkers. Conventional N-glycosylation occurs through the recognition of the consensus sequon, asparagine (Asn)-X-serine (Ser)/threonine (Thr), where X is any amino acid except for proline, with N-acetylglucosamine (GlcNAc) as the first glycosidic linkage. Usually, O-glycosylation adds a glycan to the hydroxyl group of Ser or Thr beginning with N-acetylgalactosamine (GalNAc). Protein glycosylation is further governed by additional diversifications in sequon and structure, which are yet to be fully explored. This review mainly focuses on the occurrence of N-glycosylation in non-consensus motifs, where Ser/Thr at the +2 position is substituted by other amino acids. Additionally, N-glycosylation is also observed in other amide/amine group-containing amino acids. Similarly, O-glycosylation occurs at hydroxyl group-containing amino acids other than serine/threonine. The neighbouring amino acids and local structural features around the potential glycosylation site also play a significant role in determining the extent of glycosylation. All of these phenomena that yield glycosylation at the atypical sites are reported in a variety of biological systems, including different pathological conditions. Therefore, the discovery of more novel sequence patterns for N- and O-glycosylation may help in understanding the functions of complex biological processes and cellular functions. Taken together, all these information provided in this review would be helpful for the biological readers. Copyright © 2017 Elsevier B.V. All rights reserved.

Nucleic acid duplexes incorporating a dissociable covalent base pair

NASA Technical Reports Server (NTRS)

Gao, K.; Orgel, L. E.; Bada, J. L. (Principal Investigator)

1999-01-01

We have used molecular modeling techniques to design a dissociable covalently bonded base pair that can replace a Watson-Crick base pair in a nucleic acid with minimal distortion of the structure of the double helix. We introduced this base pair into a potential precursor of a nucleic acid double helix by chemical synthesis and have demonstrated efficient nonenzymatic template-directed ligation of the free hydroxyl groups of the base pair with appropriate short oligonucleotides. The nonenzymatic ligation reactions, which are characteristic of base paired nucleic acid structures, are abolished when the covalent base pair is reduced and becomes noncoplanar. This suggests that the covalent base pair linking the two strands in the duplex is compatible with a minimally distorted nucleic acid double-helical structure.

Nucleic acid duplexes incorporating a dissociable covalent base pair

PubMed Central

Gao, Kui; Orgel, Leslie E.

1999-01-01

We have used molecular modeling techniques to design a dissociable covalently bonded base pair that can replace a Watson-Crick base pair in a nucleic acid with minimal distortion of the structure of the double helix. We introduced this base pair into a potential precursor of a nucleic acid double helix by chemical synthesis and have demonstrated efficient nonenzymatic template-directed ligation of the free hydroxyl groups of the base pair with appropriate short oligonucleotides. The nonenzymatic ligation reactions, which are characteristic of base paired nucleic acid structures, are abolished when the covalent base pair is reduced and becomes noncoplanar. This suggests that the covalent base pair linking the two strands in the duplex is compatible with a minimally distorted nucleic acid double-helical structure. PMID:10611299

Bile alcohols function as the ligands of membrane-type bile acid-activated G protein-coupled receptor

PubMed Central

Iguchi, Yusuke; Yamaguchi, Masafumi; Sato, Hiroyuki; Kihira, Kenji; Nishimaki-Mogami, Tomoko; Une, Mizuho

2010-01-01

TGR5 is a G protein-coupled receptor that is activated by bile acids, resulting in an increase in cAMP levels and the subsequent modulation of energy expenditure in brown adipose tissue and muscle. Therefore, the development of a TGR5-specific agonist could lead to the prevention and treatment of various metabolic disorders related to obesity. In the present study, we evaluated the ability of bile alcohols, which are structurally and physiologically similar to bile acids and are produced as the end products of cholesterol catabolism in evolutionarily primitive vertebrates, to act as TGR5 agonists. In a cell-based reporter assay and a cAMP production assay performed in vitro, most bile alcohols with a side chain containing hydroxyl group(s) were highly efficacious agonists for TGR5 comparable to its most potent ligand in the naturally occurring bile acid, lithocholic acid. However, the abilities of the bile alcohols to activate TGR5 varied with the position and number of the hydroxyl substituent in the side chain. Additionally, the conformation of the steroidal nucleus of bile alcohols is also important for its activity as a TGR5 agonist. Thus, we have provided new insights into the structure-activity relationships of bile alcohols as TGR5 agonists. PMID:20023205

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.

Hydroxyl Ion Diffusion through Radicular Dentine When Calcium Hydroxide Is Used under Different Conditions

PubMed Central

Cai, Michael; Castro Salgado, Jacqueline

2018-01-01

Calcium hydroxide’s anti-bacterial action relies on high pH. The aim here was to investigate hydroxyl ion diffusion through dentine under different conditions. Teeth were divided into control (n = 4) and four experimental groups (n = 10): Group 1—no medicament; Group 2—Calmix; Group 3—Calmix/Ledermix; Group 4—Calasept Plus/Ledermix; Group 5—Pulpdent/smear layer. Deep (inner dentine) and shallow (outer dentine) cavities were cut into each root. pH was measured in these cavities for 12 weeks. The inner and outer dentine pH in Group 2 was significantly higher than all groups. Inner dentine pH in Group 3 was slightly higher than that in Group 4 initially but subsequently comparable. After Day 2, Group 5 had significantly lower pH than Groups 3 and 4. The outer dentine pH in Group 3 started higher than that in Groups 4 and 5, but by Day 28 the difference was insignificant. The time for the inner dentine to reach maximum pH was one week for Group 2 and four weeks for Groups 3 and 4. The time for the outer dentine to reach maximum pH was eight weeks for all experimental groups. Mixing different Ca(OH)2 formulations with Ledermix gave similar hydroxyl ion release but pH and total diffusion was lower than Ca(OH)2 alone. The smear layer inhibited diffusion. PMID:29342093

Hydroxylation of the herbicide isoproturon by fungi isolated from agricultural soil.

PubMed

Rønhede, Stig; Jensen, Bo; Rosendahl, Søren; Kragelund, Birthe B; Juhler, René K; Aamand, Jens

2005-12-01

Several asco-, basidio-, and zygomycetes isolated from an agricultural field were shown to be able to hydroxylate the phenylurea herbicide isoproturon [N-(4-isopropylphenyl)-N',N'-dimethylurea] to N-(4-(2-hydroxy-1-methylethyl)phenyl)-N',N'-dimethylurea and N-(4-(1-hydroxy-1-methylethyl)phenyl)-N',N'-dimethylurea. Bacterial metabolism of isoproturon has previously been shown to proceed by an initial demethylation to N-(4-isopropylphenyl)-N'-methylurea. In soils, however, hydroxylated metabolites have also been detected. In this study we identified fungi as organisms that potentially play a major role in the formation of these hydroxylated metabolites in soils treated with isoproturon. Isolates of Mortierella sp. strain Gr4, Phoma cf. eupyrena Gr61, and Alternaria sp. strain Gr174 hydroxylated isoproturon at the first position of the isopropyl side chain, yielding N-(4-(2-hydroxy-1-methylethyl)phenyl)-N',N'-dimethylurea, while Mucor sp. strain Gr22 hydroxylated the molecule at the second position, yielding N-(4-(1-hydroxy-1-methylethyl)phenyl)-N',N'-dimethylurea. Hydroxylation was the dominant mode of isoproturon transformation in these fungi, although some cultures also produced traces of the N-demethylated metabolite N-(4-isopropylphenyl)-N'-methylurea. A basidiomycete isolate produced a mixture of the two hydroxylated and N-demethylated metabolites at low concentrations. Clonostachys sp. strain Gr141 and putative Tetracladium sp. strain Gr57 did not hydroxylate isoproturon but N demethylated the compound to a minor extent. Mortierella sp. strain Gr4 also produced N-(4-(2-hydroxy-1-methylethyl)phenyl)-N'-methylurea, which is the product resulting from combined N demethylation and hydroxylation.

Hydroxylation of the Herbicide Isoproturon by Fungi Isolated from Agricultural Soil

PubMed Central

Rønhede, Stig; Jensen, Bo; Rosendahl, Søren; Kragelund, Birthe B.; Juhler, René K.; Aamand, Jens

2005-01-01

Several asco-, basidio-, and zygomycetes isolated from an agricultural field were shown to be able to hydroxylate the phenylurea herbicide isoproturon [N-(4-isopropylphenyl)-N′,N′-dimethylurea] to N-(4-(2-hydroxy-1-methylethyl)phenyl)-N′,N′-dimethylurea and N-(4-(1-hydroxy-1-methylethyl)phenyl)-N′,N′-dimethylurea. Bacterial metabolism of isoproturon has previously been shown to proceed by an initial demethylation to N-(4-isopropylphenyl)-N′-methylurea. In soils, however, hydroxylated metabolites have also been detected. In this study we identified fungi as organisms that potentially play a major role in the formation of these hydroxylated metabolites in soils treated with isoproturon. Isolates of Mortierella sp. strain Gr4, Phoma cf. eupyrena Gr61, and Alternaria sp. strain Gr174 hydroxylated isoproturon at the first position of the isopropyl side chain, yielding N-(4-(2-hydroxy-1-methylethyl)phenyl)-N′,N′-dimethylurea, while Mucor sp. strain Gr22 hydroxylated the molecule at the second position, yielding N-(4-(1-hydroxy-1-methylethyl)phenyl)-N′,N′-dimethylurea. Hydroxylation was the dominant mode of isoproturon transformation in these fungi, although some cultures also produced traces of the N-demethylated metabolite N-(4-isopropylphenyl)-N′-methylurea. A basidiomycete isolate produced a mixture of the two hydroxylated and N-demethylated metabolites at low concentrations. Clonostachys sp. strain Gr141 and putative Tetracladium sp. strain Gr57 did not hydroxylate isoproturon but N demethylated the compound to a minor extent. Mortierella sp. strain Gr4 also produced N-(4-(2-hydroxy-1-methylethyl)phenyl)-N′-methylurea, which is the product resulting from combined N demethylation and hydroxylation. PMID:16332769

Steroid hydroxylation by basidiomycete peroxygenases: a combined experimental and computational study.

PubMed

Babot, Esteban D; Del Río, José C; Cañellas, Marina; Sancho, Ferran; Lucas, Fátima; Guallar, Víctor; Kalum, Lisbeth; Lund, Henrik; Gröbe, Glenn; Scheibner, Katrin; Ullrich, René; Hofrichter, Martin; Martínez, Angel T; Gutiérrez, Ana

2015-06-15

The goal of this study is the selective oxyfunctionalization of steroids under mild and environmentally friendly conditions using fungal enzymes. With this purpose, peroxygenases from three basidiomycete species were tested for the hydroxylation of a variety of steroidal compounds, using H2O2 as the only cosubstrate. Two of them are wild-type enzymes from Agrocybe aegerita and Marasmius rotula, and the third one is a recombinant enzyme from Coprinopsis cinerea. The enzymatic reactions on free and esterified sterols, steroid hydrocarbons, and ketones were monitored by gas chromatography, and the products were identified by mass spectrometry. Hydroxylation at the side chain over the steroidal rings was preferred, with the 25-hydroxyderivatives predominating. Interestingly, antiviral and other biological activities of 25-hydroxycholesterol have been reported recently (M. Blanc et al., Immunity 38:106-118, 2013, http://dx.doi.org/10.1016/j.immuni.2012.11.004). However, hydroxylation in the ring moiety and terminal hydroxylation at the side chain also was observed in some steroids, the former favored by the absence of oxygenated groups at C-3 and by the presence of conjugated double bonds in the rings. To understand the yield and selectivity differences between the different steroids, a computational study was performed using Protein Energy Landscape Exploration (PELE) software for dynamic ligand diffusion. These simulations showed that the active-site geometry and hydrophobicity favors the entrance of the steroid side chain, while the entrance of the ring is energetically penalized. Also, a direct correlation between the conversion rate and the side chain entrance ratio could be established that explains the various reaction yields observed. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Steroid Hydroxylation by Basidiomycete Peroxygenases: a Combined Experimental and Computational Study

PubMed Central

Babot, Esteban D.; del Río, José C.; Cañellas, Marina; Sancho, Ferran; Lucas, Fátima; Guallar, Víctor; Kalum, Lisbeth; Lund, Henrik; Gröbe, Glenn; Scheibner, Katrin; Ullrich, René; Hofrichter, Martin; Martínez, Angel T.

2015-01-01

The goal of this study is the selective oxyfunctionalization of steroids under mild and environmentally friendly conditions using fungal enzymes. With this purpose, peroxygenases from three basidiomycete species were tested for the hydroxylation of a variety of steroidal compounds, using H2O2 as the only cosubstrate. Two of them are wild-type enzymes from Agrocybe aegerita and Marasmius rotula, and the third one is a recombinant enzyme from Coprinopsis cinerea. The enzymatic reactions on free and esterified sterols, steroid hydrocarbons, and ketones were monitored by gas chromatography, and the products were identified by mass spectrometry. Hydroxylation at the side chain over the steroidal rings was preferred, with the 25-hydroxyderivatives predominating. Interestingly, antiviral and other biological activities of 25-hydroxycholesterol have been reported recently (M. Blanc et al., Immunity 38:106–118, 2013, http://dx.doi.org/10.1016/j.immuni.2012.11.004). However, hydroxylation in the ring moiety and terminal hydroxylation at the side chain also was observed in some steroids, the former favored by the absence of oxygenated groups at C-3 and by the presence of conjugated double bonds in the rings. To understand the yield and selectivity differences between the different steroids, a computational study was performed using Protein Energy Landscape Exploration (PELE) software for dynamic ligand diffusion. These simulations showed that the active-site geometry and hydrophobicity favors the entrance of the steroid side chain, while the entrance of the ring is energetically penalized. Also, a direct correlation between the conversion rate and the side chain entrance ratio could be established that explains the various reaction yields observed. PMID:25862224

Characterization of Hydroxyphthioceranoic and Phthioceranoic Acids by Charge-Switch Derivatization and CID Tandem Mass Spectrometry

NASA Astrophysics Data System (ADS)

Hsu, Fong-Fu

2016-04-01

Hydroxyphthioceranoic (HPA) and phthioceranoic (PA) acids are polymethylated long chain fatty acids with and without a hydroxyl group attached to the carbon next to the terminal methyl-branched carbon distal to the carboxylic end of the long-chain fatty acid, respectively. They are the major components of the sulfolipids found in the cell wall of Mycobacterium tuberculosis (M. tuberculosis) strain H37Rv. In this report, I describe CID linear ion-trap MSn mass spectrometric approaches combined with charge-reverse derivatization strategy toward characterization of these complex lipids, which were released from sulfolipids by alkaline hydrolysis and sequentially derivatized to the N-(4-aminomethylphenyl) pyridinium (AMPP) derivatives. This method affords complete characterization of HPA and PA, including the location of the hydroxyl group and the multiple methyl side chains. The study also led to the notion that the hydroxyphthioceranoic acid in sulfolipid consists of two (for hC24) to 12 (for hC52) methyl branches, and among them 2,4,6,8,10,12,14,16-octamethyl-17-hydroxydotriacontanoic acid (hC40) is the most prominent, while phthioceranoic acids are the minor constituents. These results confirm our previous findings that sulfolipid II, a family of homologous 2-stearoyl(palmitoyl)-3,6,6'-tris(hydroxyphthioceranoy1)-trehalose 2'-sulfates is the predominant species, and sulfolipid I, a family of homologous 2-stearoyl(palmitoyl)-3-phthioceranoyl-6,6'-bis(hydroxyphthioceranoy1)-trehalose 2'-sulfates is the minor species in the cell wall of M. tuberculosis.

Anti-allergic Hydroxy Fatty Acids from Typhonium blumei Explored through ChemGPS-NP

PubMed Central

Korinek, Michal; Tsai, Yi-Hong; El-Shazly, Mohamed; Lai, Kuei-Hung; Backlund, Anders; Wu, Shou-Fang; Lai, Wan-Chun; Wu, Tung-Ying; Chen, Shu-Li; Wu, Yang-Chang; Cheng, Yuan-Bin; Hwang, Tsong-Long; Chen, Bing-Hung; Chang, Fang-Rong

2017-01-01

Increasing prevalence of allergic diseases with an inadequate variety of treatment drives forward search for new alternative drugs. Fatty acids, abundant in nature, are regarded as important bioactive compounds and powerful nutrients playing an important role in lipid homeostasis and inflammation. Phytochemical study on Typhonium blumei Nicolson and Sivadasan (Araceae), a folk anti-cancer and anti-inflammatory medicine, yielded four oxygenated fatty acids, 12R-hydroxyoctadec-9Z,13E-dienoic acid methyl ester (1) and 10R-hydroxyoctadec-8E,12Z-dienoic acid methyl ester (2), 9R-hydroxy-10E-octadecenoic acid methyl ester (3), and 12R*-hydroxy-10E-octadecenoic acid methyl ester (4). Isolated compounds were identified by spectroscopic methods along with GC-MS analysis. Isolated fatty acids together with a series of saturated, unsaturated and oxygenated fatty acids were evaluated for their anti-inflammatory and anti-allergic activities in vitro. Unsaturated (including docosahexaenoic and eicosapentaenoic acids) as well as hydroxylated unsaturated fatty acids exerted strong anti-inflammatory activity in superoxide anion generation (IC50 2.14–3.73 μM) and elastase release (IC50 1.26–4.57 μM) assays. On the other hand, in the anti-allergic assays, the unsaturated fatty acids were inactive, while hydroxylated fatty acids showed promising inhibitory activity in A23187- and antigen-induced degranulation assays (e.g., 9S-hydroxy-10E,12Z-octadecadienoic acid, IC50 92.4 and 49.7 μM, respectively). According to our results, the presence of a hydroxy group in the long chain did not influence the potent anti-inflammatory activity of free unsaturated acids. Nevertheless, hydroxylation of fatty acids (or their methyl esters) seems to be a key factor for the anti-allergic activity observed in the current study. Moreover, ChemGPS-NP was explored to predict the structure-activity relationship of fatty acids. The anti-allergic fatty acids formed different cluster distant from

Hydroxylated chalcones with dual properties: xanthine oxidase inhibitors and radical scavengers

PubMed Central

Hofmann, Emily; Webster, Jonathan; Do, Thuy; Kline, Reid; Snider, Lindsey; Hauser, Quintin; Higginbottom, Grace; Campbell, Austin; Ma, Lili; Paula, Stefan

2016-01-01

In this study, we evaluated the abilities of a series of chalcones to inhibit the activity of the enzyme xanthine oxidase (XO) and to scavenge radicals. 20 mono- and polyhydroxylated chalcone derivatives were synthesized by Claisen-Schmidt condensation reactions and then tested for inhibitory potency against XO, a known generator of reactive oxygen species (ROS). In parallel, the ability of the synthesized chalcones to scavenge a stable radical was determined. Structure-activity relationship analysis in conjunction with molecular docking indicated that the most active XO inhibitors carried a minimum of three hydroxyl groups. Moreover, the most effective radical scavengers had two neighboring hydroxyl groups on at least one of the two phenyl rings. Since it has been proposed previously that XO inhibition and radical scavenging could be useful properties for reduction of ROS-levels in tissue, we determined the chalcones’ effects to rescue neurons subjected to ROS-induced stress created by the addition of β-amyloid peptide. Best protection was provided by chalcones that combined good inhibitory potency with high radical scavenging ability in a single molecule, an observation that points to a potential therapeutic value of this compound class. PMID:26762836

Mechanism and kinetics of the atmospheric degradation of 2-formylcinnamaldehyde with O3 and hydroxyl OH radicals - a theoretical study

NASA Astrophysics Data System (ADS)

Thangamani, D.; Shankar, R.; Vijayakumar, S.; Kolandaivel, P.

2016-10-01

In the present investigation, the reaction mechanism and kinetics of 2-formylcinnamaldehyde (2-FC) with O3 and hydroxyl OH radicals were studied. The reaction of 2-FC with O3 radical are initiated by the formation of primary ozonide, whereas the reaction of 2-FC with the hydroxyl OH radical are initiated by two different ways: (1). H-atom abstraction by hydroxyl OH radical from the -CHO and -CH = CHCHO group of 2-FC (2). Hydroxyl OH addition to the -CH = CHCHO group to the ring-opened 2-FC. These reactions lead to the formation of an alkyl radical. The reaction pathways corresponding to the reactions between 2-FC with O3 and hydroxyl OH radicals have been analysed using density functionals of B3LYP and M06-2X level of methods with the 6-31+G(d,p) basis set. Single-point energy calculations for the most favourable reactive species are determined by B3LYP/6-311++G(d,p) and CCSD(T)/6-31+G(d,p) levels of theory. From the obtained results, the hydroxyl OH addition at C8 position of 2-FC are most favourable than the C9 position of 2-FC. The subsequent reactions of the alkyl radicals, formed from the hydroxyl OH addition at C8 position, are analysed in detail. The individual and overall rate constant for the most favourable reactions are calculated by canonical variational transition theory with small-curvature tunnelling corrections over the temperature range of 278-350 K. The calculated theoretical rate constants are in good agreement with the available experimental data. The Arrhenius plot of the rate constants with the temperature are fitted and the atmospheric lifetimes of the 2-FC with hydroxyl OH radical reaction in the troposphere calculate for the first time, which can be applied to the study on the atmospheric implications. The condensed Fukui function has been verified for the most favourable reaction sites. This study can be regarded as an attempt to investigate the O3-initiated and hydroxyl OH-initiated reaction mechanisms of 2-FC in the atmosphere.

Interaction of surface hydroxyls with adsorbed molecules. A quantum-chemical study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Geerlings, P.; Tariel, N.; Botrel, A.

1984-11-08

A study has been conducted to explain the interaction mechanisms of (bridging and terminal) surface hydroxyl groups with molecules, using ab initio, EHT, and CNDO/2-FA quantum-chemical calculations. Bond strength variations and charge shifts were found to be in complete agreement with Gutmann's rules, and provide a basis for the understanding of the Bronsted acid properties of zeolites and amorphous silica-alumina. A quantitative measure of the interaction strength is possible by referring to the experimentally determined donor number (Gutmann) following many molecules, but care should be taken for those molecules for which the donor strength was determined by indirect methods. Onlymore » a few exceptions to Gutmann's rules should exist, e.g., in those cases where the atom interacting with the proton is not the most electronegative of the donor molecule (such as for CO). Individual bonds in a given complex are more susceptible to perturbations (changes in composition and interactions with adsorbing molecules) if the coordination number increases. These rules are in agreement with the observations and apply to all reactions (inter- or intramolecular) involving a change in coordination. 52 references, 6 figures, 4 tables.« less

Occurrence of fatty acid chlorohydrins in jellyfish lipids.

PubMed

White, R H; Hager, L P

1977-11-01

Fatty acid chlorohydrins are characterized as lipid components of an edible jellyfish. The four isomers 9-chloro-10-hydroxypalmitic acid, 10-chloro-9-hydroxypalmitic acid, 9-chloro-10-hydroxystearic acid, and 10-chloro-9-hydroxystearic acid were identified by gas chromatography-mass spectrometry comparison of the methyl esters and their trimethylsilyl derivatives with known synthetic samples. Two additional isomers, 11-chloro-12-hydroxystearic acid and 12-chloro-11-hydroxystearic acid, were also found in the lipid by the identification of the expected mass spectral fragments of the trimethylsilyl (Me3Si) derivative of their methyl esters. These six isomeric compounds represented approximately 1.4% of the total extractable jellyfish lipid and were released from the lipid as methyl esters by boron trifluoride-methanol treatment. These isomers account for only about 30% of the organic chlorine in the lipid. Evidence is given that the remaining organic chlorine is also present as fatty acid chlorohydrins containing more than one hydroxyl group.

Functional analysis of the gene controlling hydroxylation of festuclavine in the ergot alkaloid pathway of Neosartorya fumigata

PubMed Central

Bilovol, Yulia; Panaccione, Daniel G.

2016-01-01

Bioactive ergot alkaloids produced by several species of fungi are important molecules in agriculture and medicine. Much of the ergot alkaloid pathway has been elucidated, but a few steps, including the gene controlling hydroxylation of festuclavine to fumigaclavine B, remain unsolved. Festuclavine is a key intermediate in the fumigaclavine branch of the ergot alkaloid pathway of the opportunistic pathogen Neosartorya fumigata and also in the dihydrolysergic acid-based ergot alkaloid pathway of certain Claviceps species. Based on several lines of evidence, the N. fumigata gene easM is a logical candidate to encode the festuclavine-hydroxylating enzyme. To test this hypothesis we disrupted easM function by replacing part of its coding sequences with a hygromycin resistance gene and transforming N. fumigata with this construct. High pressure liquid chromatography analysis demonstrated that easM deletion mutants were blocked in the ergot alkaloid pathway at festuclavine, and downstream products were eliminated. An additional alkaloid, proposed to be a prenylated form of festuclavine on the basis of mass spectral data, also accumulated to higher concentrations in the easM knockout. Complementation with the wild-type allele of easM gene restored the ability of the fungus to produce downstream compounds. These results indicate that easM encodes an enzyme required for fumigaclavine B synthesis likely by hydroxylating festuclavine. The festuclavine-accumulating strain of N. fumigata may facilitate future investigations of the biosynthesis of dihydrolysergic acid derivatives, which are derived from festuclavine and are the basis for several important drugs. PMID:26972831

Radiation polymerisable compositions containing 3-sorboyloxy-2-hydroxypropyl groups

DOE Office of Scientific and Technical Information (OSTI.GOV)

Green, G.E.

1976-02-03

Compounds having at least three 3-sorboyloxy-2-hydroxypropyl groups directly attached to ether oxygen atoms are polymerised by exposure to actinic radiation, preferably in the presence of a sensitizer such as Michler's ketone or benzoin. The compounds may be obtained by the reaction either of sorbic acid with a substance having at least three glycidyl ether groups or of glycidyl sorbate with a substance having at least three phenolic or alcoholic hydroxyl groups: if desired, not all of the glycidyl groups may be consumed, so that, after actinically induced polymerisation, the epoxide-containing polymer may be cross-linked by reaction with a curing agentmore » for epoxide resins. The compounds are useful in making printed circuits or printing plates for offset printing.« less

Plant fatty acid hydroxylases

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. In addition, the use of genes encoding fatty acid hydroxylases or desaturases to alter the level of lipid fatty acid unsaturation in transgenic plants is described.

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

Utilization of acidic α-amino acids as acyl donors: an effective stereo-controllable synthesis of aryl-keto α-amino acids and their derivatives.

PubMed

Wang, Lei; Murai, Yuta; Yoshida, Takuma; Okamoto, Masashi; Tachrim, Zetryana Puteri; Hashidoko, Yasuyuki; Hashimoto, Makoto

2014-05-16

Aryl-keto-containing α-amino acids are of great importance in organic chemistry and biochemistry. They are valuable intermediates for the construction of hydroxyl α-amino acids, nonproteinogenic α-amino acids, as well as other biofunctional components. Friedel-Crafts acylation is an effective method to prepare aryl-keto derivatives. In this review, we summarize the preparation of aryl-keto containing α-amino acids by Friedel-Crafts acylation using acidic α-amino acids as acyl-donors and Lewis acids or Brönsted acids as catalysts.

Dimer esters in α-pinene secondary organic aerosol: effect of hydroxyl radical, ozone, relative humidity and aerosol acidity

NASA Astrophysics Data System (ADS)

Kristensen, K.; Cui, T.; Zhang, H.; Gold, A.; Glasius, M.; Surratt, J. D.

2013-12-01

The formation of secondary organic aerosol (SOA) from both ozonolysis and hydroxyl radical (OH)-initiated oxidation of α-pinene under conditions of high nitric oxide (NO) concentrations with varying relative humidity (RH) and aerosol acidity was investigated in the University of North Carolina dual outdoor smog chamber facility. SOA formation from ozonolysis of α-pinene was enhanced relative to that from OH-initiated oxidation in the presence of initially high NO conditions. However, no effect of RH on SOA mass was evident. Ozone (O3)-initiated oxidation of α-pinene in the presence of ammonium sulfate (AS) seed coated with organic aerosol from OH-initiated oxidation of α-pinene showed reduced nucleation compared to ozonolysis in the presence of pure AS seed aerosol. The chemical composition of α-pinene SOA was investigated by ultra-performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS), with a focus on the formation of carboxylic acids and high-molecular weight dimer esters. A total of eight carboxylic acids and four dimer esters were identified, constituting between 8 and 12% of the total α-pinene SOA mass. OH-initiated oxidation of α-pinene in the presence of nitrogen oxides (NOx) resulted in the formation of highly oxidized carboxylic acids, such as 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA) and diaterpenylic acid acetate (DTAA). The formation of dimer esters was observed only in SOA produced from the ozonolysis of α-pinene in the absence of NOx, with increased concentrations by a~factor of two at higher RH (50-90%) relative to lower RH (30-50%). The increased formation of dimer esters correlates with an observed increase in new particle formation at higher RH due to nucleation. Increased aerosol acidity was found to have a negligible effect on the formation of the dimer esters. SOA mass yield did not influence the chemical composition of SOA formed from �

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.

Influence of pH, buffers and role of quinolinic acid, a novel iron chelating agent, in the determination of hydroxyl radical scavenging activity of plant extracts by Electron Paramagnetic Resonance (EPR).

PubMed

Fadda, Angela; Barberis, Antonio; Sanna, Daniele

2018-02-01

The Fenton reaction is used to produce hydroxyl radicals for the evaluation of the antioxidant activity of plant extracts. In this paper the parameters affecting the production of hydroxyl radicals and their spin trapping with DMPO were studied. The use of quinolinic acid (Quin) as an Fe(II) ligand was proposed for antioxidant activity determination of Green tea, orange juice and asparagus extracts. Quin, buffers and pH affect the DMPO-OH signal intensity of the EPR spectra. Quin/Fe(II) and low pH enhance the OH generation. Phosphate and Tris-HCl buffers decrease the signal intensity measured in Fe(II)-sulfate and Fe(II)-Quin systems. The extracts were analyzed with Fenton systems containing Fe(II)-sulfate and Fe(II)-Quin with and without buffer. The highest activity was shown with Fe(II)-Quin without buffer, this system being less influenced by pH and chelating agents present in the extracts. This paper will help researchers to better design spin trapping experiments for food matrices. Copyright © 2017 Elsevier Ltd. All rights reserved.

Comparing Amino Acid Abundances and Distributions Across Carbonaceous Chondrite Groups

NASA Technical Reports Server (NTRS)

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

2012-01-01

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

Interactions of Kraft lignin and wheat gluten during biomaterial processing: evidence for the role of phenolic groups.

PubMed

Kaewtatip, Kaewta; Menut, Paul; Auvergne, Remi; Tanrattanakul, Varaporn; Morel, Marie-Helene; Guilbert, Stephane

2010-04-14

The chemical interactions between Kraft lignin and wheat gluten under processing conditions were investigated by determining the extent of the protein network formation. To clarify the role of different chemical functions found in lignin, the effect of Kraft lignin was compared with that of an esterified lignin, in which hydroxyl groups had been suppressed by esterification, and with a series of simple aromatics and phenolic structures with different functionalities (conjugated double bonds, hydroxyl, carboxylic acid, and aldehyde). The protein solubility was determined by using the Kjeldahl method. The role of the hydroxyl function was assessed by the significantly lower effect of esterified lignin. The importance of the phenolic radical scavenging structure is evidenced by the effect of guaiacol, which results in a behavior similar to that of the Kraft lignin. In addition, the significant effect of conjugated double bonds on gluten reactivity, through nucleophilic addition, was demonstrated.

Zwitterionic versus canonical amino acids over the various defects in zeolites: A two-layer ONIOM calculation

PubMed Central

Yang, Gang; Zhou, Lijun

2014-01-01

Defects are often considered as the active sites for chemical reactions. Here a variety of defects in zeolites are used to stabilize zwitterionic glycine that is not self-stable in gas phase; in addition, effects of acidic strengths and zeolite channels on zwitterionic stabilization are demonstrated. Glycine zwitterions can be stabilized by all these defects and energetically prefer to canonical structures over Al and Ga Lewis acidic sites rather than Ti Lewis acidic site, silanol and titanol hydroxyls. For titanol (Ti-OH), glycine interacts with framework Ti and hydroxyl sites competitively, and the former with Lewis acidity predominates. The transformations from canonical to zwitterionic glycine are obviously more facile over Al and Ga Lewis acidic sites than over Ti Lewis acidic site, titanol and silanol hydroxyls. Charge transfers that generally increase with adsorption energies are found to largely decide the zwitterionic stabilization effects. Zeolite channels play a significant role during the stabilization process. In absence of zeolite channels, canonical structures predominate for all defects; glycine zwitterions remain stable over Al and Ga Lewis acidic sites and only with synergy of H-bonding interactions can exist over Ti Lewis acidic site, while automatically transform to canonical structures over silanol and titanol hydroxyls. PMID:25307449

Catabolism of Naphthalenesulfonic Acids by Pseudomonas sp. A3 and Pseudomonas sp. C22

PubMed Central

Brilon, C.; Beckmann, W.; Knackmuss, H.-J.

1981-01-01

Naphthalene and two naphthalenesulfonic acids were degraded by Pseudomonas sp. A3 and Pseudomonas sp. C22 by the same enzymes. Gentisate is a major metabolite. Catabolic activities for naphthalene, 1-naphthalenesulfonic acid, and 2-naphthalenesulfonic acid are induced by growth with naphthalene, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, methylnaphthalene, or salicylate. Gentisate is also an inducer in strain A3. Inhibition kinetics show that naphthalene and substituted naphthalenes are hydroxylated by the same naphthalene dioxygenase. Substrates with nondissociable substituents such as CH3, OCH3, Cl, or NO2 are hydroxylated in the 7,8-position, and 4-substituted salicylates are accumulated. If CO2H, CH2CO2H, or SO3H are substituents, hydroxylation occurs with high regioselectivity in the 1,2-position. Thus, 1,2-dihydroxy-1,2-dihydronaphthalene-2-carboxylic acids are formed quantitatively from the corresponding naphthalenecarboxylic acids. Utilization of naphthalenesulfonic acids proceeds by the same regioselective 1,2-dioxygenation which labilizes the C—SO3− bond and eliminates sulfite. PMID:16345814

Production of Hydroxyl Radical via the Activation of Hydrogen Peroxide by Hydroxylamine.

PubMed

Chen, Liwei; Li, Xuchun; Zhang, Jing; Fang, Jingyun; Huang, Yanmin; Wang, Ping; Ma, Jun

2015-09-01

The production of the hydroxyl radical (HO·) is important in environmental chemistry. This study reports a new source of HO· generated solely from hydrogen peroxide (H2O2) activated by hydroxylamine (HA). Electron paramagnetic resonance analysis and the oxidation of a HO· probe, benzoic acid, were used to confirm the production of HO·. The production of HO· increased with increasing concentrations of either HA or H2O2 as well as decreasing pH. The second-order rate constant for the reaction was (2.2 ± 0.2) × 10(-4) M(-1) s(-1). HO· was probably produced in two steps: the activation of H2O2 by protonated HA and then reaction between the H2O2 and the intermediate protonated aminoxyl radical generated in the first step. Such a two-step oxidation can possibly be ascribed to the ionizable hydroxyl moiety in the molecular structure of HA, as is suggested by comparing the reactivity of a series of HA derivatives in HO· production. The results shed light on a previously unknown source of HO· formation, which broadens the understanding of its role in environmental processes.

Abscisic Acid Metabolism by a Cell-free Preparation from Echinocystis lobata Liquid Endoserum 1

PubMed Central

Gillard, Douglas F.; Walton, Daniel C.

1976-01-01

A cell-free enzyme system capable of metabolizing abscisic acid has been obtained from Eastern Wild Cucumber (Echinocystis lobata Michx.) liquid endosperm. The reaction products were determined to be phaseic acid (PA) and dihydrophaseic acid (DPA) by co-chromatography on thin layer chromatograms as the free acids, methyl esters, and their respective oxidation or reduction products. The crude enzyme preparation was separated by centrifugation into a particulate abscisic acid (ABA)-hydroxylating activity and a soluble PA-reducing activity. The particulate ABA-hydroxylating enzyme showed a requirement for O2 and NADPH, inhibition by CO, and high substrate specificity for (+)-ABA. Acetylation of short term incubation mixtures gave evidence for the presence of 6′-hydroxymethyl-ABA as an intermediate in PA formation. Determinations of endogenous ABA and DPA concentrations suggest that the ABA-hydroxylating and PA-reducing enzymes are extensively metabolizing ABA in the intact E. lobata seed. PMID:16659768

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.

Electrocatalytic Oxidation of Formate with Nickel Diphosphane Dipeptide Complexes. Effect of Ligands Modified with Amino Acids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Galan, Brandon R.; Reback, Matthew L.; Jain, Avijita

2013-09-03

A series of nickel bis-diphosphine complexes with dipeptides appended to the ligands were investigated for the catalytic oxidation of formate. Typical rates of ~7 s -1 were found, similar to the parent complex (~8 s -1), with amino acid size and positioning contributing very little to rate or operating potential. Hydroxyl functionalities did result in lower rates, which were recovered by protecting the hydroxyl group. The results suggest that the overall dielectric introduced by the dipeptides does not play an important role in catalysis, but free hydroxyl groups do influence activity suggesting contributions from intra- or intermolecular interactions. These observationsmore » are important in developing a fundamental understanding of the affect that an enzyme-like outer coordination sphere can have upon molecular catalysts. This work was funded by the US DOE Basic Energy Sciences, Chemical Sciences, Geoscience and Biosciences Division (BRG, AJ, AMA, WJS), the US DOE Basic Energy Sciences, Physical Bioscience program (MLR). Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.« less

Time-Resolved Hydroxyl Radical Footprinting of RNA with X-Rays.

PubMed

Hao, Yumeng; Bohon, Jen; Hulscher, Ryan; Rappé, Mollie C; Gupta, Sayan; Adilakshmi, Tadepalli; Woodson, Sarah A

2018-06-01

RNA footprinting by hydroxyl radical cleavage provides 'snapshots' of RNA tertiary structure or protein interactions that bury the RNA backbone. Generation of hydroxyl radicals with a high-flux synchrotron X-ray beam provides analysis on a short timescale (5-100 msec), which enables the structures of folding intermediates or other transient conformational states to be determined in biochemical solutions or cells. This article provides protocols for using synchrotron beamlines for hydroxyl radical footprinting. © 2018 by John Wiley & Sons, Inc. © 2018 John Wiley & Sons, Inc.

L-Altruronic acid formed by epimerization of D-galacturonic acid methyl esters during saponification of citrus pectin.

PubMed

Zhan, D; Qiu, F; Mort, A J

2001-02-15

While searching for oligosaccharides containing rhamnose residues in the endopolygalacturonase (EPG) digest of saponified citrus pectin, we found several oligomers containing, in addition to galacturonic acid, a sugar previously unreported in pectin. The 1- and 2-D 1H NMR spectra of the oligosaccharides were consistent with the sugar being a uronic acid with its 2- and 3-hydroxyls being axial and 4-hydroxyl being equatorial. MALDI-TOF mass spectrometry indicated that the oligomers consisted solely of uronic acids. Reduction of the uronic acids in the oligosaccharides converted them to galactose and altrose. The altrose was found to be the L enantiomer by comparison of its trimethylsilyl (-)-2-butyl glycosides to those of authentic D-altrose and a racemic mixture. The sugar was not found in oligosaccharides prepared from EPG digestion of citrus pectin deesterified with pectin methylesterase rather than saponification. Thus, it appears that during saponification, a small proportion of the methylesterified galacturonic acid residues in pectins is epimerized at C-5 leading to formation of L-altruronic acid residues.

[Effect of the steroid molecule structure on the direction of its hydroxylation by the fungus Curvularia lunata].

PubMed

Andriushina, V A; Iaderets, V V; Stytsenko, T S; Druzhinina, A V; Voĭshvillo, N E

2013-01-01

The main and side products of hydroxylation by the C. lunata VKPM F-981 mycelium of fourteen delta(4)-3-ketosteroids of the estrane, androstane, and pregnane series and six of their delta(5)-3beta-hydroxy analogues were identified by H1 PMR spectroscopy and comparison with standard samples. The obtained experimental data are considered in terms of the triangular model of the enzyme-substrate interaction. The dependence of the direction of hydroxylation of steroid molecules and the orientation of hydroxy groups on the structure of the initial substrate was revealed.

Ordered hydroxyls on Ca 3Ru 2O 7(001)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Halwidl, Daniel; Mayr-Schmölzer, Wernfried; Fobes, David

As complex ternary perovskite-type oxides are increasingly used in solid oxide fuel cells, electrolysis and catalysis, it is necessary to obtain a better understanding of their surface chemical properties. Here we report a pronounced ordering of hydroxyls on the cleaved (001) surface of the Ruddlesden-Popper perovskite Ca 3Ru 2O 7 upon water adsorption at 105 K and subsequent annealing to room temperature. Density functional theory calculations predict the dissociative adsorption of a single water molecule (E ads = 1.64 eV), forming an (OH) ads group adsorbed in a Ca-Ca bridge site, with an H transferred to a neighboring surface oxygenmore » atom, O surf. Scanning tunneling microscopy images show a pronounced ordering of the hydroxyls with (2 × 1), c(2 × 6), (1 × 3), and (1 × 1) periodicity. The present work demonstrates the importance of octahedral rotation and tilt in perovskites, for influencing surface reactivity, which here induces the ordering of the observed OH overlayers.« less

Ordered hydroxyls on Ca 3Ru 2O 7(001)

DOE PAGES

Halwidl, Daniel; Mayr-Schmölzer, Wernfried; Fobes, David; ...

2017-06-20

As complex ternary perovskite-type oxides are increasingly used in solid oxide fuel cells, electrolysis and catalysis, it is necessary to obtain a better understanding of their surface chemical properties. Here we report a pronounced ordering of hydroxyls on the cleaved (001) surface of the Ruddlesden-Popper perovskite Ca 3Ru 2O 7 upon water adsorption at 105 K and subsequent annealing to room temperature. Density functional theory calculations predict the dissociative adsorption of a single water molecule (E ads = 1.64 eV), forming an (OH) ads group adsorbed in a Ca-Ca bridge site, with an H transferred to a neighboring surface oxygenmore » atom, O surf. Scanning tunneling microscopy images show a pronounced ordering of the hydroxyls with (2 × 1), c(2 × 6), (1 × 3), and (1 × 1) periodicity. The present work demonstrates the importance of octahedral rotation and tilt in perovskites, for influencing surface reactivity, which here induces the ordering of the observed OH overlayers.« less

Reactivity of formic acid (HCOOD and DCOOH) at uranium and UO 2.0 surfaces

NASA Astrophysics Data System (ADS)

Manner, William L.; Lloyd, Jane A.; Paffett, Mark T.

1999-10-01

Interactions of DCOOH and HCOOD with uranium and UO 2.0 surfaces have been examined using surface-specific techniques of thermal desorption mass spectroscopy (TDMS), X-ray photoelectron spectroscopy (XPS), and static secondary ion mass spectroscopy (SSIMS). On the clean uranium surface, formate is the predominant product following formic acid adsorption at 100 K. A wide range of products is observed after annealing to 200 K, including formate, hydroxyl, O ads, and H ads (D ads) groups. Adsorbed formate decomposes by 300 K increasing the concentration of the remaining surface products. Surface-adsorbed carbon following TDMS measurements remains as the carbide, as indicated from XPS and SSIMS measurements. The only gaseous species created in high yields from the clean surface upon annealing are H 2, HD, and D 2. On the oxide surface (UO 2.0), adsorbed formate groups are more stable toward dissociation in comparison with the clean uranium surface. Between 100 and 300 K the predominant species on the UO 2.0 surface are surface formate and hydroxyl groups. Hydroxyl groups react between 300 and 350 K to release water from the surface. Adsorbed formate groups decompose between 400 and 500 K to release CO and H 2CO (D 2CO) groups from the oxide surface. Carbon was not detected on the oxide surface by XPS or SSIMS after annealing to 500 K, indicating that all carbon-containing species either desorb in the form of CO-containing products or migrate into the surface.

Methylation patterns of aquatic humic substances determined by 13C NMR spectroscopy

USGS Publications Warehouse

Thorn, K.A.; Steelink, C.; Wershaw, R. L.

1987-01-01

13C NMR spectroscopy is used to examine the hydroxyl group functionality of a series of humic and fulvic acids from different aquatic environments. Samples first are methylated with 13C-labeled diazomethane. The NMR spectra of the diazomethylated samples allow one to distinguish between methyl esters of carboxylic acids, methyl ethers of phenolic hydroxyls, and methyl ethers of phenolic hydroxyls adjacent to two substituents. Samples are then permethylated with 13C-labeled methyl iodide/NaH. 13C NMR spectra of permethylated samples show that a significant fraction of the hydroxyl groups is not methylated with diazomethane alone. In these spectra methyl ethers of carbohydrate and aliphatic hydroxyls overlap with methyl ethers of phenolic hydroxyls. Side reactions of the methyltion procedure including carbon methylation in the CH3I/NaH procedure, are also examined. Humic and fulvic acids from bog, swamp, groundwater, and lake waters showssome differences in their distribution of hydroxyl groups, mainly in the concentrations of phenolic hydroxyls, which may be attributed to their different biogeochemical origins. ?? 1987.

Tris[(6S)-6-hy-droxy-4-epi-shikimic acid] monohydrate: an enanti-omerically pure hy-droxy-lated shikimic acid derived from methyl shikimate.

PubMed

Griesbeck, Axel G; Miara, Claus; Neudörfl, Jörg-M

2012-11-01

The title compound, 3C(7)H(10)O(6)·H(2)O, is the enanti-omerically pure product of a multi-step synthesis from the enanti-omerically pure natural shikimic acid. The asymmetric unit contains three mol-ecules of the acid and one mol-ecule of water. The cyclo-hexene rings of the acids have half-chair conformations. The carboxyl-ate, the four hydroxide groups and the additional water mol-ecule form a complex three-dimensional hydrogen-bonding network.

Structure-based Mechanism of CMP-2-keto-3-deoxymanno-octulonic Acid Synthetase

PubMed Central

Heyes, Derren J.; Levy, Colin; Lafite, Pierre; Roberts, Ian S.; Goldrick, Marie; Stachulski, Andrew V.; Rossington, Steven B.; Stanford, Deborah; Rigby, Stephen E. J.; Scrutton, Nigel S.; Leys, David

2009-01-01

The enzyme CMP-Kdo synthetase (KdsB) catalyzes the addition of 2-keto-3-deoxymanno-octulonic acid (Kdo) to CTP to form CMP-Kdo, a key reaction in the biosynthesis of lipopolysaccharide. The reaction catalyzed by KdsB and the related CMP-acylneuraminate synthase is unique among the sugar-activating enzymes in that the respective sugars are directly coupled to a cytosine monophosphate. Using inhibition studies, in combination with isothermal calorimetry, we show the substrate analogue 2β-deoxy-Kdo to be a potent competitive inhibitor. The ligand-free Escherichia coli KdsB and ternary complex KdsB-CTP-2β-deoxy-Kdo crystal structures reveal that Kdo binding leads to active site closure and repositioning of the CTP phosphates and associated Mg2+ ion (Mg-B). Both ligands occupy conformations compatible with an Sn2-type attack on the α-phosphate by the Kdo 2-hydroxyl group. Based on strong similarity with DNA/RNA polymerases, both in terms of overall chemistry catalyzed as well as active site configuration, we postulate a second Mg2+ ion (Mg-A) is bound by the catalytically competent KdsB-CTP-Kdo ternary complex. Modeling of this complex reveals the Mg-A coordinated to the conserved Asp100 and Asp235 in addition to the CTP α-phosphate and both the Kdo carboxylic and 2-hydroxyl groups. EPR measurements on the Mn2+-substituted ternary complex support this model. We propose the KdsB/CNS sugar-activating enzymes catalyze the formation of activated sugars, such as the abundant CMP-5-N-acetylneuraminic acid, by recruitment of two Mg2+ to the active site. Although each metal ion assists in correct positioning of the substrates and activation of the α-phosphate, Mg-A is responsible for activation of the sugar-hydroxyl group. PMID:19815542

FTIR and 1H MAS NMR investigations on the correlation between the frequency of stretching vibration and the chemical shift of surface OH groups of solids

NASA Astrophysics Data System (ADS)

Brunner, Eike; Karge, H. G.; Pfeifer, H.

1992-03-01

The study of surface hydroxyl groups of solids, especially of zeolites, belongs to the 'classical' topics of IR spectroscopy since physico-chemical information may be derived from the wavenumber (nu) OH of the stretching vibration of the different hydroxyls. On the other hand, the last decade has seen the development of high resolution solid-state NMR spectroscopy and through the use of the so-called magic-angle-spinning technique (MAS) the signals of different hydroxyl species can be resolved in the 1H NMR spectra of solids. The chemical shift (delta) H describing the position of these lines may be used as well as (nu) OH to characterize quantitatively the strength of acidity of surface OH groups of solids. In a first comparison of (nu) OH with (delta) H for several types of surface OH groups, a linear correlation between them could be found. The aim of this paper was to prove the validity of this correlation for a wide variety of hydroxyls. The IR measurements were carried out on a Perkin-Elmer FTIR spectrometer 1800 at the Fritz Haber Institute of the Max Planck Society, Berlin, and the 1H MAS NMR spectra were recorded on a Bruker MSL- 300 at the University of Leipzig.

Hydroxyl radical production in plasma electrolysis with KOH electrolyte solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saksono, Nelson; Febiyanti, Irine Ayu, E-mail: irine.ayu41@ui.ac.id; Utami, Nissa

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 currentmore » 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.« less

Roles of Copper and a Conserved Aspartic Acid in the Autocatalytic Hydroxylation of a Specific Tryptophan Residue during Cysteine Tryptophylquinone Biogenesis.

PubMed

Williamson, Heather R; Sehanobish, Esha; Shiller, Alan M; Sanchez-Amat, Antonio; Davidson, Victor L

2017-02-21

The first posttranslational modification step in the biosynthesis of the tryptophan-derived quinone cofactors is the autocatalytic hydroxylation of a specific Trp residue at position C-7 on the indole side chain. Subsequent modifications are catalyzed by modifying enzymes, but the mechanism by which this first step occurs is unknown. LodA possesses a cysteine tryptophylquinone (CTQ) cofactor. Metal analysis as well as spectroscopic and kinetic studies of the mature and precursor forms of a D512A LodA variant provides evidence that copper is required for the initial hydroxylation of the precursor protein and that if alternative metals are bound, the modification does not occur and the precursor is unstable. It is shown that the mature native LodA also contains loosely bound copper, which affects the visible absorbance spectrum and quenches the fluorescence spectrum that is attributed to the mature CTQ cofactor. When copper is removed, the fluorescence appears, and when it is added back to the protein, the fluorescence is quenched, indicating that copper reversibly binds in the proximity of CTQ. Removal of copper does not diminish the enzymatic activity of LodA. This distinguishes LodA from enzymes with protein-derived tyrosylquinone cofactors in which copper is present near the cofactor and is absolutely required for activity. Mechanisms are proposed for the role of copper in the hydroxylation of the unactivated Trp side chain. These results demonstrate that the reason that the highly conserved Asp512 is critical for LodA, and possibly all tryptophylquinone enzymes, is not because it is required for catalysis but because it is necessary for CTQ biosynthesis, more specifically to facilitate the initial copper-dependent hydroxylation of a specific Trp residue.

Chain-breaking antioxidant activity of hydroxylated and methoxylated magnolol derivatives: the role of H-bonds.

PubMed

Baschieri, Andrea; Pulvirenti, Luana; Muccilli, Vera; Amorati, Riccardo; Tringali, Corrado

2017-07-26

Chemical modification of magnolol, an uncommon dimeric neolignan contained in Magnolia genus trees, provides a unique array of polyphenols having interesting biological activity potentially related to radical scavenging. The chain-breaking antioxidant activity of four new hydroxylated and methoxylated magnolol derivatives was explored by experimental and computational methods. The measurement of the rate constant of the reaction with ROO˙ radicals (k inh ) in an apolar solvent showed that the introduction of hydroxyl groups ortho to the phenolic OH in magnolol increased the k inh value, being 2.4 × 10 5 M -1 s -1 and 3.3 × 10 5 M -1 s -1 for the mono and the dihydroxy derivatives respectively (k inh of magnolol is 6.1 × 10 4 M -1 s -1 ). The di-methoxylated derivative is less reactive than magnolol (k inh = 1.1 × 10 4 M -1 s -1 ), while the insertion of both hydroxyl and methoxyl groups showed no effect (6.0 × 10 4 M -1 s -1 ). Infrared spectroscopy and theoretical calculations allowed a rationalization of these results and pointed out the crucial role of intramolecular H-bonds. We also show that a correct estimation of the rate constant of the reaction with ROO˙ radicals, by using BDE(OH) calculations, requires that the geometry of the radical is as close as possible to that of the parent phenol.

Detection analysis of surface hydroxyl active sites and simulation calculation of the surface dissociation constants of aqueous diatomite suspensions

NASA Astrophysics Data System (ADS)

Ma, Shu-Cui; Wang, Zhi-Gang; Zhang, Ji-Lin; Sun, De-Hui; Liu, Gui-Xia

2015-02-01

The surface properties of the diatomite were investigated using nitrogen adsorption/deadsorption isotherms, TG-DSC, FTIR, and XPS, and surface protonation-deprotonation behavior was determined by continuous acid-base potentiometric titration technique. The diatomite sample with porous honeycomb structure has a BET specific surface area of 10.21 m2/g and large numbers of surface hydroxyl functional groups (i.e. tbnd Si-OH, tbnd Fe-OH, and tbnd Al-OH). These surface hydroxyls can be protonated or deprotonated depending on the pH of the suspension. The experimental potentiometric data in two different ionic strength solutions (0.1 and 0.05 mol/L NaCl) were fitted using ProtoFit GUI V2.1 program by applying diffuse double layer model (DLM) with three amphoteric sites and minimizing the sum of squares between a dataset derivative function and a model derivative function. The optimized surface parameters (i.e. surface dissociation constants (log K1, log K2) and surface site concentrations (log C)) of the sample were obtained. Based on the optimized surface parameters, the surface species distribution was calculated using Program-free PHREEQC 3.1.2. Thus, this work reveals considerable new information about surface protonation-deprotonation processes and surface adsorptive behaviors of the diatomite, which helps us to effectively use the cheap and cheerful diatomite clay adsorbent.

Genetic analysis of groups of mid-infrared predicted fatty acids in milk.

PubMed

Narayana, S G; Schenkel, F S; Fleming, A; Koeck, A; Malchiodi, F; Jamrozik, J; Johnston, J; Sargolzaei, M; Miglior, F

2017-06-01

The objective of this study was to investigate genetic variability of mid-infrared predicted fatty acid groups in Canadian Holstein cattle. Genetic parameters were estimated for 5 groups of fatty acids: short-chain (4 to 10 carbons), medium-chain (11 to 16 carbons), long-chain (17 to 22 carbons), saturated, and unsaturated fatty acids. The data set included 49,127 test-day records from 10,029 first-lactation Holstein cows in 810 herds. The random regression animal test-day model included days in milk, herd-test date, and age-season of calving (polynomial regression) as fixed effects, herd-year of calving, animal additive genetic effect, and permanent environment effects as random polynomial regressions, and random residual effect. Legendre polynomials of the third degree were selected for the fixed regression for age-season of calving effect and Legendre polynomials of the fourth degree were selected for the random regression for animal additive genetic, permanent environment, and herd-year effect. The average daily heritability over the lactation for the medium-chain fatty acid group (0.32) was higher than for the short-chain (0.24) and long-chain (0.23) fatty acid groups. The average daily heritability for the saturated fatty acid group (0.33) was greater than for the unsaturated fatty acid group (0.21). Estimated average daily genetic correlations were positive among all fatty acid groups and ranged from moderate to high (0.63-0.96). The genetic correlations illustrated similarities and differences in their origin and the makeup of the groupings based on chain length and saturation. These results provide evidence for the existence of genetic variation in mid-infrared predicted fatty acid groups, and the possibility of improving milk fatty acid profile through genetic selection in Canadian dairy cattle. Copyright © 2017 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

The hydroxyl-functionalized magnetic particles for purification of glycan-binding proteins.

PubMed

Sun, Xiuxuan; Yang, Ganglong; Sun, Shisheng; Quan, Rui; Dai, Weiwei; Li, Bin; Chen, Chao; Li, Zheng

2009-12-01

Glycan-protein interactions play important biological roles in biological processes. Although there are some methods such as glycan arrays that may elucidate recognition events between carbohydrates and protein as well as screen the important glycan-binding proteins, there is a lack of simple effectively separate method to purify them from complex samples. In proteomics studies, fractionation of samples can help to reduce their complexity and to enrich specific classes of proteins for subsequent downstream analyses. Herein, a rapid simple method for purification of glycan-binding proteins from proteomic samples was developed using hydroxyl-coated magnetic particles coupled with underivatized carbohydrate. Firstly, the epoxy-coated magnetic particles were further hydroxyl functionalized with 4-hydroxybenzhydrazide, then the carbohydrates were efficiently immobilized on hydroxyl functionalized surface of magnetic particles by formation of glycosidic bond with the hemiacetal group at the reducing end of the suitable carbohydrates via condensation. All conditions of this method were optimized. The magnetic particle-carbohydrate conjugates were used to purify the glycan-binding proteins from human serum. The fractionated glycan-binding protein population was displayed by SDS-PAGE. The result showed that the amount of 1 mg magnetic particles coupled with mannose in acetate buffer (pH 5.4) was 10 micromol. The fractionated glycan-binding protein population in human serum could be eluted from the magnetic particle-mannose conjugates by 0.1% SDS. The methodology could work together with the glycan microarrays for screening and purification of the important GBPs from complex protein samples.

Physical-Mechanical Properties and Micromorphology of Calcium Cements Exposed to Polyacrylic and Phosphoric Acids.

PubMed

de Souza, Gustavo Fernandes; Arrais, Ana Beatriz; Aragão, Cícero Flávio Soares; Ferreira, Isana Alvares; Borges, Boniek Castillo Dutra

2018-01-01

To evaluate if physical and mechanical properties of self-curing calcium hydroxide cements were affected by contact with polyacrylic and phosphoric acids. Resin-containing (Life (LF)) and resin-free (Hydro C (HyC)) materials were subjected to polyacrylic acid conditioning and rinsing (POL); phosphoric acid conditioning and rinsing (PHO); rinsing only; and no treatment ( n = 10). Water sorption/solubility, release of hydroxyl ions (pH), roughness (Ra), and impact resistance were evaluated. Additional samples ( n = 1) were prepared for scanning electron microscopy (SEM) analysis of the surface morphology. Data were analyzed by two-way ANOVA and Tukey post hoc test ( P < 0.05). Water sorption was significantly higher for LF when in contact with PHO and lower for POL ( P < 0.05). The mean solubility was higher with POL for both cements ( P < 0.05). PHO increased the mean surface roughness for HyC ( P < 0.01); a significant decrease was noted for LF after contact with both acids ( P < 0.01). PHO promoted lower release of hydroxyl ions on both cements ( P < 0.05). For LF, rinsing, PHO, and POL presented similar morphology, differing from the control group. For HyC, PHO and POL presented similar morphology, differing from the control group. PHO had a negative effect on the physical properties of the cements tested, except for the solubility test. POL affected roughness and solubility of HyC cement. Clinical procedures that require polyacrylic and phosphoric acid conditioning must be done carefully on self-curing calcium hydroxide cements in order to avoid negative impact on their properties.

Determination of the structure and catalytic mechanism of Sorghum bicolor caffeic acid O-methyltransferase and the structural impact of three brown midrib12 mutations

USDA-ARS?s Scientific Manuscript database

With S-adenosylmethionine (SAM) acting as the methyl donor, caffeic acid O-methyltransferase from Sorghum bicolor (SbCOMT) methylates the 5-hydroxyl group of its preferred substrate, 5-hydroxyconiferaldehyde, to form sinapaldehyde. In order to determine the mechanism of SbCOMT and understand the red...

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.

First principles calculations of interactions of ZrCl4 precursors with the bare and hydroxylated ZrO2 surfaces

NASA Astrophysics Data System (ADS)

Iskandarova, I. M.; Knizhnik, A. A.; Bagatur'yants, A. A.; Potapkin, B. V.; Korkin, A. A.

2004-05-01

First-principles calculations have been performed to determine the structures and relative energies of different zirconium chloride groups chemisorbed on the tetragonal ZrO2(001) surface and to study the effects of the surface coverage with metal chloride groups and the degree of hydroxylation on the adsorption energies of metal precursors. It is shown that the molecular and dissociative adsorption energies of the ZrCl4 precursor on the bare t-ZrO2(001) surface are too small to hold ZrCl4 molecules on the surface during an atomic layer deposition (ALD) cycle at temperatures higher than 300°C. On the contrary, it has been found that molecular adsorption on the fully hydroxylated zirconia surface leads to the formation of a stable adsorbed complex. This strong adsorption of ZrCl4 molecules can lead to a decrease in the film growth rate of the ALD process at lower temperatures (<200°C). The energies of interaction between adsorbed ZrCl4 groups at a 50% surface coverage has been found to be relatively small, which explains the maximum film growth rate observed in the ZrCl4:H2O ALD process. Moreover, we found that the adsorbed ZrCl4 precursors after hydrolysis give rise to very stable hydroxyl groups, which can be responsible for film growth at high temperatures (up to 900°C).

Improved synthesis of 3 alpha, 7 alpha, 12 alpha, 24 = xi-tetrahydroxy-5 beta-cholestan-26-oic acid.

PubMed

Batta, A K; Tint, G S; Dayal, B; Shefer, S; Salen, G

1982-06-01

This paper describes three simple and short methods for the conversion of cholic acid into cholylaldehyde with protected hydroxyl groups. The first method involves lithium aluminum hydride reduction of the tetrahydropyranyl ether of methyl cholate and oxidation of the resulting primary alcohol with pyridinium chlorochromate. The second method employs diborane for the reduction of the -COOH group to the -CH2OH group, while the third method involves the reduction of 3 alpha, 7 alpha, 12 alpha-triformyloxy-5 beta-cholan-24-oic acid (as the acid chloride) directly into 3 alpha, 7 alpha, 12 alpha-triformyloxy-5 beta-cholan-24-al with TMA-ferride (tetramethylammonium hydridoirontetracarbonyl). The aldehyde obtained by any of the above methods underwent smooth Reformatsky reaction with ethyl alpha-bromopropionate to yield 3 alpha, 7 alpha, 12 alpha, 24 xi-tetrahydroxy-5 beta-cholestan-26-oic acid.

Synthesis of positively charged CdTe quantum dots and detection for uric acid

NASA Astrophysics Data System (ADS)

Zhang, Tiliang; Sun, Xiangying; Liu, Bin

2011-09-01

The CdTe dots (QDs) coated with 2-Mercaptoethylamine was prepared in aqueous solution and characterized with fluorescence spectroscopy, UV-Vis absorption spectra, high-resolution transmission electron microscopy and infrared spectroscopy. When the λex = 350 nm, the fluorescence peak of positively charged CdTe quantum dots is at 592 nm. The uric acid is able to quench their fluorescence. Under optimum conditions, the change of fluorescence intensity is linearly proportional to the concentration of uric acid in the range 0.4000-3.600 μmol L -1, and the limit of detection calculated according to IUPAC definitions is 0.1030 μmol L -1. Compared with routine method, the present method determines uric acid in human serum with satisfactory results. The mechanism of this strategy is due to the interaction of the tautomeric keto/hydroxyl group of uric acid and the amino group coated at the CdTe QDs.

Proteomic analysis reveals diverse proline hydroxylation-mediated oxygen-sensing cellular pathways in cancer cells

PubMed Central

Liu, Bing; Gao, Yankun; Ruan, Hai-Bin; Chen, Yue

2016-01-01

Proline hydroxylation is a critical cellular mechanism regulating oxygen-response pathways in tumor initiation and progression. Yet, its substrate diversity and functions remain largely unknown. Here, we report a system-wide analysis to characterize proline hydroxylation substrates in cancer cells using an immunoaffinity-purification assisted proteomics strategy. We identified 562 sites from 272 proteins in HeLa cells. Bioinformatic analysis revealed that proline hydroxylation substrates are significantly enriched with mRNA processing and stress-response cellular pathways with canonical and diverse flanking sequence motifs. Structural analysis indicates a significant enrichment of proline hydroxylation participating in the secondary structure of substrate proteins. Our study identified and validated Brd4, a key transcription factor, as a novel proline hydroxylation substrate. Functional analysis showed that the inhibition of proline hydroxylation pathway significantly reduced the proline hydroxylation abundance on Brd4 and affected Brd4-mediated transcriptional activity as well as cell proliferation in AML leukemia cells. Taken together, our study identified a broad regulatory role of proline hydroxylation in cellular oxygen-sensing pathways and revealed potentially new targets that dynamically respond to hypoxia microenvironment in tumor cells. PMID:27764789

Detection and scavenging of hydroxyl radical via D-phenylalanine hydroxylation in human fluids.

PubMed

Biondi, Roberto; Brancorsini, Stefano; Poli, Giulia; Egidi, Maria Giulia; Capodicasa, Enrico; Bottiglieri, Livio; Gerli, Sandro; Brillo, Eleonora; Renzo, Gian Carlo Di; Cretoiu, Dragos; Micu, Romeo; Suciu, Nicolae

2018-05-01

Hydroxyl radical (.OH) is highly reactive, and therefore very short-lived. Finding new means to accurately detect .OH, and testing the ability of known .OH scavengers to neutralize them in human biological fluids would leverage our ability to more effectively counter oxidative (.OH) stress-mediated damage in human diseases. To achieve this, we pursued the evaluation of secondary products resulting from .OH attack, using a detection system based on Fenton reaction-mediated D-phenylalanine (D-Phe) hydroxylation. This reaction in turn generates o-tyrosine (o-tyr), m-tyrosine (m-tyr) and p-tyrosine (p-tyr). Here, these isomers were separated by HPLC, equipped with fluorescence detectors due to the natural fluorescence of these hydrotyrosines. By extension, we found that, adding radical scavengers competed with D-Phe on .OH attack, thus allowing to determine the .OH quenching capacity of a given compound expressed as inhibition ratio percent (IR%). Using a kinetic approach, we then tested the .OH scavenging capacity (OHSC) of well-known antioxidant molecules. In a test tube, N,N'-dimethylthiourea (DMTU) was the most efficient scavenger as compared to Trolox and N-Acethyl-L-cysteine, with NAC being the less effective. OHSC assay was then applied to biological fluid samples as seminal plasma, human serum from normal subjects and patients undergoing hemodialysis (HD), colostrum and human breast milk from mothers that received daily doses of 30g of chocolate (70% cocoa) during pregnancy. We found that a daily administration of dark chocolate during pregnancy almost doubled OHSC levels in breast milk (1.88 ± 0.12 times, p < 0.01). Furthermore, HD treatment determined a significant reduction of serum OHSC concentration (54.63 ± 2.82%, p < 0.001). Our results provide evidence that Fenton reaction-mediated D-Phe hydroxylation is a suitable method for routine and non-invasive evaluation of .OH detection and its scavenging in human biological fluids. Copyright © 2018 The

Disturbance of mitochondrial functions provoked by the major long-chain 3-hydroxylated fatty acids accumulating in MTP and LCHAD deficiencies in skeletal muscle.

PubMed

Cecatto, Cristiane; Godoy, Kálita Dos Santos; da Silva, Janaína Camacho; Amaral, Alexandre Umpierrez; Wajner, Moacir

2016-10-01

The pathogenesis of the muscular symptoms and recurrent rhabdomyolysis that are commonly manifested in patients with mitochondrial trifunctional protein (MTP) and long-chain 3-hydroxy-acyl-CoA dehydrogenase (LCHAD) deficiencies is still unknown. In this study we investigated the effects of the major long-chain monocarboxylic 3-hydroxylated fatty acids (LCHFA) accumulating in these disorders, namely 3-hydroxytetradecanoic (3HTA) and 3-hydroxypalmitic (3HPA) acids, on important mitochondrial functions in rat skeletal muscle mitochondria. 3HTA and 3HPA markedly increased resting (state 4) and decreased ADP-stimulated (state 3) and CCCP-stimulated (uncoupled) respiration. 3HPA provoked similar effects in permeabilized skeletal muscle fibers, validating the results obtained in purified mitochondria. Furthermore, 3HTA and 3HPA markedly diminished mitochondrial membrane potential, NAD(P)H content and Ca(2+) retention capacity in Ca(2+)-loaded mitochondria. Mitochondrial permeability transition (mPT) induction probably underlie these effects since they were totally prevented by cyclosporin A and ADP. In contrast, the dicarboxylic analogue of 3HTA did not alter the tested parameters. Our data strongly indicate that 3HTA and 3HPA behave as metabolic inhibitors, uncouplers of oxidative phosphorylation and mPT inducers in skeletal muscle. It is proposed that these pathomechanisms disrupting mitochondrial homeostasis may be involved in the muscle alterations characteristic of MTP and LCHAD deficiencies. Copyright © 2016 Elsevier Ltd. All rights reserved.

Improved lignin polyurethane properties with Lewis acid treatment.

PubMed

Chung, Hoyong; Washburn, Newell R

2012-06-27

Chemical modification strategies to improve the mechanical properties of lignin-based polyurethanes are presented. We hypothesized that treatment of lignin with Lewis acids would increase the concentration of hydroxyl groups available to react with diisocyanate monomers. Under the conditions used, hydrogen bromide-catalyzed modification resulted in a 28% increase in hydroxyl group content. Associated increases in hydrophilicity of solvent-cast thin films were also recorded as evidenced by decreases in water contact angle. Polyurethanes were then prepared by first preparing a prepolymer based on mixtures of toluene-2,4-diisocyanate (TDI) and unmodified or modified lignin, then polymerization was completed through addition of polyethylene glycol (PEG), resulting in mass ratios of TDI:lignin:PEG of 43:17:40 in the compositions investigated here. The mixture of TDI and unmodified lignin resulted in a lignin powder at the bottom of the liquid, suggesting it did not react directly with TDI. However, a homogeneous solution resulted when TDI and the hydrogen bromide-treated lignin were mixed, suggesting demethylation indeed increased reactivity and resulted in better integration of lignin into the urethane network. Significant improvements in mechanical properties of modified lignin polyurethanes were observed, with a 6.5-fold increase in modulus, which were attributed to better integration of the modified lignin into the covalent polymer network due to the higher concentration of hydroxyl groups. This research indicates that chemical modification strategies can lead to significant improvements in the properties of lignin-based polymeric materials using a higher fraction of an inexpensive lignin monomer from renewable resources and a lower fraction an expensive, petroleum-derived isocyanate monomer to achieve the required material properties.

Synthesis and characterization of the 6 alpha- and 6 beta-hydroxylated derivatives of corticosterone, 11-dehydrocorticosterone, and 11-deoxycortisol.

PubMed

Kraan, G P; van Wee, K T; Wolthers, B G; van der Molen, J C; Nagel, G T; Drayer, N M; van Leusen, D

1993-10-01

This report describes the synthesis of 6 alpha, 17,21- and 6 beta, 17,21-trihydroxypregn-4-ene-3,20-dione, 6 alpha, 7,21- and 6 beta, 11 beta, 21-trihydroxypregn-4-ene-3,20-dione, and--for the first time--that of 6 alpha, 21- and 6 beta, 21-dihydroxypregn-4-ene-3,11,20-trione. The former four compounds were prepared by 6-hydroxylation of 17,21-trihydroxypregn-4-ene-3,20-dione and 11 beta, 21-dihydroxypregn-4-ene-3,20-dione, respectively. This was achieved by autoxidation or by oxidation with 3-chloroperbenzoic acid, of the 3-methoxy-pregna-3,5-dienes of the latter two steroids. The yield of the 6 beta-hydroxylated steroids, but not of their corresponding 6 alpha-epimers, was higher using autoxidation than the peracid. The two 6-hydroxylated pregnenetriones were prepared from 6 alpha, 21-diacetoxy-11 beta-hydroxypregn-4-ene-3,20-dione and 6 beta, 21-diacetoxy-11 beta-hydroxypregn-4-ene-3,20-dione, respectively, by oxidation with pyridinium chlorochromate. The above-mentioned six steroids were identified and characterized by nuclear magnetic resonance, infrared, ultraviolet, high performance liquid chromatography, gas chromatography, and mass spectrometry.

Single-layer nanosheets with exceptionally high and anisotropic hydroxyl ion conductivity

PubMed Central

Sun, Pengzhan; Ma, Renzhi; Bai, Xueyin; Wang, Kunlin; Zhu, Hongwei; Sasaki, Takayoshi

2017-01-01

When the dimensionality of layered materials is reduced to the physical limit, an ultimate two-dimensional (2D) anisotropy and/or confinement effect may bring about extraordinary physical and chemical properties. Layered double hydroxides (LDHs), bearing abundant hydroxyl groups covalently bonded within 2D host layers, have been proposed as inorganic anion conductors. However, typical hydroxyl ion conductivities for bulk or lamellar LDHs, generally up to 10−3 S cm−1, are considered not high enough for practical applications. We show that single-layer LDH nanosheets exhibited exceptionally high in-plane conductivities approaching 10−1 S cm−1, which were the highest among anion conductors and comparable to proton conductivities in commercial proton exchange membranes (for example, Nafion). The in-plane conductivities were four to five orders of magnitude higher than the cross-plane or cross-membrane values of restacked LDH nanosheets. This 2D superionic transport characteristic might have great promises in a variety of applications including alkaline fuel cells and water electrolysis. PMID:28439551

Evolution of novel O-methyltransferases from the Vanilla planifolia caffeic acid O-methyltransferase.

PubMed

Li, Huaijun Michael; Rotter, David; Hartman, Thomas G; Pak, Fulya E; Havkin-Frenkel, Daphna; Belanger, Faith C

2006-06-01

The biosynthesis of many plant secondary compounds involves the methylation of one or more hydroxyl groups, catalyzed by O-methyltransferases (OMTs). Here, we report the characterization of two OMTs, Van OMT-2 and Van OMT-3, from the orchid Vanilla planifolia Andrews. These enzymes catalyze the methylation of a single outer hydroxyl group in substrates possessing a 1,2,3-trihydroxybenzene moiety, such as methyl gallate and myricetin. This is a substrate requirement not previously reported for any OMTs. Based on sequence analysis these enzymes are most similar to caffeic acid O-methyltransferases (COMTs), but they have negligible activity with typical COMT substrates. Seven of 12 conserved substrate-binding residues in COMTs are altered in Van OMT-2 and Van OMT-3. Phylogenetic analysis of the sequences suggests that Van OMT-2 and Van OMT-3 evolved from the V. planifolia COMT. These V. planifolia OMTs are new instances of COMT-like enzymes with novel substrate preferences.

Uncovering the Design Principle of Amino Acid-Derived Photoluminescent Biodots with Tailor-Made Structure-Properties and Applications for Cellular Bioimaging.

PubMed

Xu, Hesheng Victor; Zheng, Xin Ting; Zhao, Yanli; Tan, Yen Nee

2018-06-13

Natural amino acids possess side chains with different functional groups (R groups), which make them excellent precursors for programmable synthesis of biomolecule-derived nanodots (biodots) with desired properties. Herein, we report the first systematic study to uncover the material design rules of biodot synthesis from 20 natural α-amino acids via a green hydrothermal approach. The as-synthesized amino acid biodots (AA dots) are comprehensively characterized to establish a structure-property relationship between the amino acid precursors and the corresponding photoluminescent properties of AA dots. It was found that the amino acids with reactive R groups, including amine, hydroxyl, and carboxyl functional groups form unique C-O-C/C-OH and N-H bonds in the AA dots which stabilize the surface defects, giving rise to brightly luminescent AA dots. Furthermore, the AA dots were found to be amorphous and the length of the R group was observed to affect the final morphology (e.g., disclike nanostructure, nanowire, or nanomesh) of the AA dots, which in turn influence their photoluminescent properties. It is noteworthy to highlight that the hydroxyl-containing amino acids, that is, Ser and Thr, form the brightest AA dots with a quantum yield of 30.44% and 23.07%, respectively, and possess high photostability with negligible photobleaching upon continuous UV exposure for 3 h. Intriguingly, by selective mixing of Ser or Thr with another amino acid precursor, the resulting mixed AA dots could inherit unique properties such as improved photostability and significant red shift in their emission wavelength, producing enhanced green and red fluorescent intensity. Moreover, our cellular studies demonstrate that the as-synthesized AA dots display outstanding biocompatibility and excellent intracellular uptake, which are highly desirable for imaging applications. We envision that the material design rules discovered in this study will be broadly applicable for the rational

Cupric ion reducing antioxidant capacity assay for antioxidants in human serum and for hydroxyl radical scavengers.

PubMed

Apak, Reşat; Güçlü, Kubilay; Ozyürek, Mustafa; Bektaşoğlu, Burcu; Bener, Mustafa

2010-01-01

Tests measuring the combined antioxidant effect of the nonenzymatic defenses in biological fluids may be useful in providing an index of the organism's capability to counteract reactive species known as pro-oxidants, resist oxidative damage, and combat oxidative stress-related diseases. The selected chromogenic redox reagent for the assay of human serum should be easily accessible, stable, selective, and respond to all types of biologically important antioxidants such as ascorbic acid, alpha-tocopherol, beta-carotene, reduced glutathione (GSH), uric acid, and bilirubin, regardless of chemical type or hydrophilicity. Our recently developed cupric reducing antioxidant capacity (CUPRAC) spectrophotometric method for a number of polyphenols and flavonoids using the copper(II)-neocuproine reagent in ammonium acetate buffer is now applied to a complete series of plasma antioxidants for the assay of total antioxidant capacity of serum, and the resulting absorbance at 450 nm is recorded either directly (e.g., for ascorbic acid, alpha-tocopherol, and glutathione) or after incubation at 50 degrees C for 20 min (e.g., for uric acid, bilirubin, and albumin), quantitation being made by means of a calibration curve. The lipophilic antioxidants, alpha-tocopherol and beta-carotene, are assayed in dichloromethane. Lipophilic antioxidants of serum are extracted with n-hexane from an ethanolic solution of serum subjected to centrifugation. Hydrophilic antioxidants of serum are assayed in the centrifugate after perchloric acid precipitation of proteins. The CUPRAC molar absorptivities, linear ranges, and TEAC (trolox equivalent antioxidant capacity) coefficients of the serum antioxidants are established, and the results are evaluated in comparison with the findings of the ABTS/TEAC reference method. The intra- and inter-assay coefficients of variation (CVs) are 0.7 and 1.5%, respectively, for serum. The CUPRAC assay proved to be efficient for glutathione and thiol-type antioxidants

Sequestering ability of butylated hydroxytoluene, propyl gallate, resveratrol, and vitamins C and E against ABTS, DPPH, and hydroxyl free radicals in chemical and biological systems.

PubMed

Soares, Daniele G; Andreazza, Ana C; Salvador, Mirian

2003-02-12

The antioxidant capacity of butylated hydroxytoluene (BHT; 2,6-di-tert-butyl-p-cresol), propyl gallate (3,4,5-trihydroxybenzoic acid n-propyl ester), resveratrol (trans-3,4',5-trihydroxystilbene), and vitamins C (l-ascorbic acid) and E [(+)-alpha-tocopherol] was studied in chemical and biological systems. The chemical assays evaluated the capacity of these antioxidants to sequester 2,2'-azinobis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS.) and 1,1 diphenyl-2-picrylhydrazyl (DPPH.). A new colorimetric method to determine hydroxyl radical scavenging is also described. The biological tests use the eucaryotic cells of Saccharomyces cerevisiae treated with the antioxidants in the presence of the stressing agents apomorphine, hydrogen peroxide, and paraquat dichloride (methylviologen; 1,1'-dimethyl-4,4'-bipyridinium dichloride). The results in chemical systems showed that all of the antioxidants were able to significantly inhibit the oxidation of beta-carotene by hydroxyl free radicals. The assays in yeast showed that the antioxidant activity of the tested compounds depended on the stressing agent used and the mechanism of action of the antioxidant.

2,3-trans-3,4-trans-3,4-Dihydroxy-L-proline: An amino acid in toxic peptides of Amanita virosa mushrooms

PubMed Central

Buku, A.; Faulstich, H.; Wieland, T.; Dabrowski, J.

1980-01-01

Among the four possible stereoisomers of 3,4-dihydroxy-L-proline,2,3-trans-3,4-trans-3,4-dihydroxy-L-proline (IV) had not been found in nature previously. It has now been detected as a component of virotoxins, toxic peptides of Amanita virosa mushrooms. Because periodate failed to effect an oxidative glycol splitting reaction, the two hydroxyl groups in positions 3 and 4 were expected to be in a trans configuration. Furthermore, the formation of a 4-lactone on treatment with acids pointed to the carboxyl group and the hydroxyl group at position 4 being in a cis configuration. These results are in agreement with structure IV only. Final proof for structure IV was given by NMR spectroscopy and direct comparison with the 2,3-cis-3,4-trans-3,4-dihydroxy-L-proline isomer. PMID:16592813

UVA-induced reset of hydroxyl radical ultradian rhythm improves temporal lipid production in Chlorella vulgaris.

PubMed

Balan, Ranjini; Suraishkumar, G K

2014-01-01

We report for the first time that the endogenous, pseudo-steady-state, specific intracellular levels of the hydroxyl radical (si-OH) oscillate in an ultradian fashion (model system: the microalga, Chlorella vulgaris), and also characterize the various rhythm parameters. The ultradian rhythm in the endogenous levels of the si-OH occurred with an approximately 6 h period in the daily cycle of light and darkness. Further, we expected that the rhythm reset to a shorter period could rapidly switch the cellular redox states that could favor lipid accumulation. We reset the endogenous rhythm through entrainment with UVA radiation, and generated two new ultradian rhythms with periods of approximately 2.97 h and 3.8 h in the light phase and dark phase, respectively. The reset increased the window of maximum lipid accumulation from 6 h to 12 h concomitant with the onset of the ultradian rhythms. Further, the saturated fatty acid content increased approximately to 80% of total lipid content, corresponding to the peak maxima of the hydroxyl radical levels in the reset rhythm. © 2014 American Institute of Chemical Engineers.

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

PubMed Central

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

2009-01-01

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

Genetic correlations of mid-infrared-predicted milk fatty acid groups with milk production traits.

PubMed

Fleming, A; Schenkel, F S; Malchiodi, F; Ali, R A; Mallard, B; Sargolzaei, M; Jamrozik, J; Johnston, J; Miglior, F

2018-05-01

The objective of this research was to estimate the genetic correlations between milk mid-infrared-predicted fatty acid groups and production traits in first-parity Canadian Holsteins. Contents of short-chain, medium-chain, long-chain, saturated, and unsaturated fatty acid groupings in milk samples can be predicted using mid-infrared spectral data for cows enrolled in milk recording programs. Predicted fatty acid group contents were obtained for 49,127 test-day milk samples from 10,029 first-parity Holstein cows in 810 herds. Milk yield, fat and protein yield, fat and protein percentage, fat-to-protein ratio, and somatic cell score were also available for these test days. Genetic parameters were estimated for the fatty acid groups and production traits using multiple-trait random regression test day models by Bayesian methods via Gibbs sampling. Three separate 8- or 9-trait analyses were performed, including the 5 fatty acid groups with different combinations of the production traits. Posterior standard deviations ranged from <0.001 to 0.01. Average daily genetic correlations were negative and similar to each other for the fatty acid groups with milk yield (-0.62 to -0.59) and with protein yield (-0.32 to -0.25). Weak and positive average daily genetic correlations were found between somatic cell score and the fatty acid groups (from 0.25 to 0.36). Stronger genetic correlations with fat yield, fat and protein percentage, and fat-to-protein ratio were found with medium-chain and saturated fatty acid groups compared with those with long-chain and unsaturated fatty acid groups. Genetic correlations were very strong between the fatty acid groups and fat percentage, ranging between 0.88 for unsaturated and 0.99 for saturated fatty acids. Daily genetic correlations from 5 to 305 d in milk with milk, protein yield and percentage, and somatic cell score traits showed similar patterns for all fatty acid groups. The daily genetic correlations with fat yield at the beginning

Versatile Synthesis of Amino Acid Functional Polymers without Protection Group Chemistry.

PubMed

Brisson, Emma R L; Xiao, Zeyun; Franks, George V; Connal, Luke A

2017-01-09

The copolymerization of N-isopropylacrylamide (NiPAm) with aldehyde functional monomers facilitates postpolymerization functionalization with amino acids via reductive amination, negating the need for protecting groups. In reductive amination, the imine formed from the condensation reaction between an amine and an aldehyde is reduced to an amine. In this work, we categorize amino acids into four classes based on the functionality of their side chains (acidic, polar neutral, neutral, and basic) and use their amine groups in condensation reactions with aldehyde functional polymers. The dynamic nature of the imine as well as the versatility of reductive amination to functionalize a polymer with a range of amino acids is highlighted. In this manner, amino acid functional polymers are synthesized without the use of protecting groups with high yields, demonstrating the high functional group tolerance of carbonyl condensation chemistry and the subsequent reduction of the imine. Prior to the reduction of the imine bond, transimination reactions are used to demonstrate dynamic polymers that shuffle from a glycine- to a histidine-functional polymer.

Quenching of fluorescence of phenolic compounds and modified humic acids by cadmium ions.

PubMed

Tchaikovskaya, O N; Nechaev, L V; Yudina, N V; Mal'tseva, E V

2016-08-01

The interaction of a number of phenolic compounds, being 'model fragments' of humic acids, with cadmium ions was investigated. The fluorescence quenching method was used to determine the complexation constants of these compounds with cadmium ions. It was established that bonding of phenolic compounds by cadmium ions at рН 7 is weak and reaches a maximum value of 15% for interaction with resorcinol. It was demonstrated that modification of humic acids by the mechanoactivation method increases by three times bonding of cadmium ions, which is caused by strengthening the acid properties of carboxyl and hydroxyl groups at the aromatic ring. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Plasma acylcarnitine profiling indicates increased fatty acid oxidation relative to tricarboxylic acid cycle capacity in young, healthy low birth weight men.

PubMed

Ribel-Madsen, Amalie; Ribel-Madsen, Rasmus; Brøns, Charlotte; Newgard, Christopher B; Vaag, Allan A; Hellgren, Lars I

2016-10-01

We hypothesized that an increased, incomplete fatty acid beta-oxidation in mitochondria could be part of the metabolic events leading to insulin resistance and thereby an increased type 2 diabetes risk in low birth weight (LBW) compared with normal birth weight (NBW) individuals. Therefore, we measured fasting plasma levels of 45 acylcarnitine species in 18 LBW and 25 NBW men after an isocaloric control diet and a 5-day high-fat, high-calorie diet. We demonstrated that LBW men had higher C2 and C4-OH levels after the control diet compared with NBW men, indicating an increased fatty acid beta-oxidation relative to the tricarboxylic acid cycle flux. Also, they had higher C6-DC, C10-OH/C8-DC, and total hydroxyl-/dicarboxyl-acylcarnitine levels, which may suggest an increased fatty acid omega-oxidation in the liver. Furthermore, LBW and NBW men decreased several acylcarnitine levels in response to overfeeding, which is likely a result of an upregulation of fatty acid oxidation due to the dietary challenge. Moreover, C10-OH/C8-DC and total hydroxyl-/dicarboxyl-acylcarnitine levels tended to be negatively associated with the serum insulin level, and the total hydroxyl-/dicarboxyl-acylcarnitine level additionally tended to be negatively associated with the hepatic insulin resistance index. This indicates that an increased fatty acid omega-oxidation could be a compensatory mechanism to prevent an accumulation of lipid species that impair insulin signaling. © 2016 The Authors. Physiological Reports published by Wiley Periodicals, Inc. on behalf of the American Physiological Society and The Physiological Society.

1,4-Dihydroxy fatty acids: Artifacts by reduction of di- and polyunsaturated fatty acids with sodium borohydride

NASA Astrophysics Data System (ADS)

Thiemt, Simone; Spiteller, Gerhard

1997-01-01

In an effort to detect lipid peroxidation products in human blood plasma, samples were treated with NaBH4 to reduce the reactive hydroperoxides to hydroxy compounds. After saponification of the lipids, the free fatty acid fraction obtained by extraction was methylated and separated by TLC. The fractions containing polar compounds were trimethylsilylated and subjected to gas chromatography-mass spectrometry (GC/MS). Mass spectra allowed us to detect previously unknown 1,4-dihydroxy fatty acids due to their typical fragmentation pattern. If the reduction was carried out with NaBD4 instead of NaBH4, incorporation of two deuterium atoms was observed (appropriate mass shift). The two oxygen atoms of the hydroxyl groups were incorporated from air as shown by an experiment in 18O2 atmosphere. The reaction required the presence of free acids, indicating that BH3 was liberated, added to a 1,4-pentadiene system, and finally produced 1,4-diols by air oxidation.

Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

DOE PAGES

Yu, L.; Smith, J.; Laskin, A.; ...

2014-08-19

Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol and two methoxy-phenols (syringol and guaiacol) with two major aqueous phase oxidants – the triplet excited states of an aromatic carbonyl ( 3C*) and hydroxyl radical (·OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). A large number of oxygenated molecules aremore » identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85–1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than ·OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenol had reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV-vis region, suggesting that aqueous-phase reactions of phenols are likely an important source of brown carbon in the atmosphere, especially in regions influenced by biomass burning.« less

Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

DOE PAGES

Yu, L.; Smith, J.; Laskin, A.; ...

2014-12-23

Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol (compound with formula C 6H 5OH)), guaiacol (2-methoxyphenol), and syringol (2,6-dimethoxyphenol) with two major aqueous-phase oxidants – the triplet excited states of an aromatic carbonyl ( 3C *) and hydroxyl radical (· OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). Amore » large number of oxygenated molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85–1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C * are faster than · OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenolic compound has reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV–visible region, suggesting that aqueous-phase reactions of phenols may contribute to formation of secondary brown carbon in the atmosphere, especially in regions influenced by biomass burning.« less

Impact of 2′-hydroxyl sampling on the conformational properties of RNA: Update of the CHARMM all-atom additive force field for RNA

PubMed Central

Denning, Elizabeth J.; Priyakumar, U. Deva; Nilsson, Lennart; MacKerell, Alexander D.

2011-01-01

Here, we present an update of the CHARMM27 all-atom additive force field for nucleic acids that improves the treatment of RNA molecules. The original CHARMM27 force field parameters exhibit enhanced Watson-Crick (WC) base pair opening which is not consistent with experiment while analysis of MD simulations show the 2′-hydroxyl moiety to almost exclusively sample the O3′ orientation. Quantum mechanical studies of RNA related model compounds indicate the energy minimum associated with the O3′ orientation to be too favorable, consistent with the MD results. Optimization of the dihedral parameters dictating the energy of the 2′-hydroxyl proton targeting the QM data yielded several parameter sets, which sample both the base and O3′ orientations of the 2′-hydroxyl to varying degrees. Selection of the final dihedral parameters was based on reproduction of hydration behavior as related to a survey of crystallographic data and better agreement with experimental NMR J-coupling values. Application of the model, designated CHARMM36, to a collection of canonical and non-canonical RNA molecules reveals overall improved agreement with a range of experimental observables as compared to CHARMM27. The results also indicate the sensitivity of the conformational heterogeneity of RNA to the orientation of the 2′-hydroxyl moiety and support a model whereby the 2′-hydroxyl can enhance the probability of conformational transitions in RNA. PMID:21469161

Reaction mechanisms of DNT with hydroxyl radicals for advanced oxidation processes-a DFT study.

PubMed

Zhou, Yang; Yang, Zhilin; Yang, Hong; Zhang, Chaoyang; Liu, Xiaoqiang

2017-04-01

In advanced oxidation processes (AOPs), the detailed degradation mechanisms of a typical explosive of 2,4-dinitrotoluene (DNT) can be investigated by the density function theory (DFT) method at the SMD/M062X/6-311+G(d) level. Several possible degradation routes for DNT were explored in the current study. The results show that, for oxidation of the methyl group, the dominant degradation mechanism of DNT by hydroxyl radicals (•OH) is a series of sequential H-abstraction reactions, and the intermediates obtained are in good agreement with experimental findings. The highest activation energy barrier is less than 20 kcal mol -1 . Other routes are dominated by an addition-elimination mechanism, which is also found in 2,4,6-trinitrotoluene, although the experiment did not find the corresponding products. In addition, we also eliminate several impossible mechanisms, such as dehydration, HNO 3 elimination, the simultaneous addition of two •OH radials, and so on. The information gained about these degradation pathways is helpful in elucidating the detailed reaction mechanism between nitroaromatic explosives and hydroxyl radicals for AOPs. Graphical Abstract The degradation mechanism of an important explosive, 2,6-dinitrotoluene (DNT), by the hydroxyl radical for advanced oxidation progresses.

Molecular Insights into the Local Anesthetic Receptor within Voltage-Gated Sodium Channels Using Hydroxylated Analogs of Mexiletine

PubMed Central

Desaphy, Jean-François; Dipalma, Antonella; Costanza, Teresa; Carbonara, Roberta; Dinardo, Maria Maddalena; Catalano, Alessia; Carocci, Alessia; Lentini, Giovanni; Franchini, Carlo; Camerino, Diana Conte

2011-01-01

We previously showed that the β-adrenoceptor modulators, clenbuterol and propranolol, directly blocked voltage-gated sodium channels, whereas salbutamol and nadolol did not (Desaphy et al., 2003), suggesting the presence of two hydroxyl groups on the aromatic moiety of the drugs as a molecular requisite for impeding sodium channel block. To verify such an hypothesis, we synthesized five new mexiletine analogs by adding one or two hydroxyl groups to the aryloxy moiety of the sodium channel blocker and tested these compounds on hNav1.4 channels expressed in HEK293 cells. Concentration–response relationships were constructed using 25-ms-long depolarizing pulses at −30 mV applied from an holding potential of −120 mV at 0.1 Hz (tonic block) and 10 Hz (use-dependent block) stimulation frequencies. The half-maximum inhibitory concentrations (IC50) were linearly correlated to drug lipophilicity: the less lipophilic the drug, minor was the block. The same compounds were also tested on F1586C and Y1593C hNav1.4 channel mutants, to gain further information on the molecular interactions of mexiletine with its receptor within the sodium channel pore. In particular, replacement of Phe1586 and Tyr1593 by non-aromatic cysteine residues may help in the understanding of the role of π–π or π–cation interactions in mexiletine binding. Alteration of tonic block suggests that the aryloxy moiety of mexiletine may interact either directly or indirectly with Phe1586 in the closed sodium channel to produce low-affinity binding block, and that this interaction depends on the electrostatic potential of the drug aromatic tail. Alteration of use-dependent block suggests that addition of hydroxyl groups to the aryloxy moiety may modify high-affinity binding of the drug amine terminal to Phe1586 through cooperativity between the two pharmacophores, this effect being mainly related to drug lipophilicity. Mutation of Tyr1593 further impaired such cooperativity. In conclusion

Hydroxyl migration disorders the surface structure of hydroxyapatite nanoparticles

NASA Astrophysics Data System (ADS)

Cheng, Xiajie; Wu, Hong; Zhang, Li; Ma, Xingtao; Zhang, Xingdong; Yang, Mingli

2017-09-01

The surface structure of nano-hydroxyapatite (HAP) was investigated using a combined simulated annealing and molecular dynamics method. The stationary structures of nano-HAP with 4-7 nm in diameter and annealed under different temperatures were analyzed in terms of pair distribution function, structural factor, mean square displacement and atomic coordination number. The particles possess different structures from bulk crystal. A clear radial change in their atomic arrangements was noted. From core to surface the structures change from ordered to disordered. A three-shell model was proposed to describe the structure evolution of nano-HAP. Atoms in the core zone keep their arrangements as in crystal, while atoms in the surface shell are in short-range order and long-range disorder, adopting a typically amorphous structure. Atoms in the middle shell have small displacements and/or deflections but basically retain their original locations as in crystal. The disordered shell is about 1 nm in thickness, in agreement with experimental observations. The disordering mainly stems from hydroxyl migration during which hydroxyls move to the surface and bond with the exposed Ca ions, and their left vacancies bring about a rearrangement of nearby atoms. The disordering is to some extent different for particles unannealed under different temperatures, resulting from fewer number of migrated hydroxyls at lower temperatures. Particles with different sizes have similar surface structures, and their surface energy decreases with increasing size. Moreover, the surface energy is reduced by hydroxyl migration because the exposed Ca ions on the surface are ionically bonded with the migrated hydroxyls. Our calculations proposed a new structure model for nano-HAP, which indicates a surface structure with activities different from those without surface reorganization. This is particularly interesting because most bioactivities of biomaterials are dominated by their surface activity.

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.

Mass spectrometry of analytical derivatives. 2. "Ortho" and "Para" effects in electron ionization mass spectra of derivatives of hydroxy, mercapto and amino benzoic acids.

PubMed

Todua, Nino G; Mikaia, Anzor I

2016-01-01

Derivatives requiring either anhydrous or aqueous reaction conditions were prepared for robust and reliable gas chromatography/mass spectrometry (GC/MS) characterization of hydroxyl, mercapto, and amino benzoic acids Methylation and trialkylsilytation are employed for blocking the acidic function. Alkyl, trimethylsilyl, acetyl, perfluoroacyl and alkoxycarbonyl derivatization groups are introduced to hydroxyl, mercapto and amino functions. The electron ionization induced fragmentation characteristics of corresponding derivatives are explained by comparing the MS 1 spectra of unlabeled compounds to their 2 H and 13 C labeled analogs, and analysis of collision-induced dissociation data from MS 2 spectra. Competing fragmentation alternatives are identified and specific decomposition processes are detailed that characterize (a) ortho isomers due to interaction or vicinal functional substituents and (b) para isomers prone to forming para quinoid type structures. Skeletal and hydrogen rearrangements typical for methyl benzoates and the blocking groups are considered when discussing diagnostically important ions. Characteristic ions produced as a result of rearrangements in ortho isomers are classified, and skeletal rearrangements required to produce para quinoid type ions specific for para isomers are noted. Key ions for structure elucidation and differentiation of isomers for derivatives of substituted benzoic acids by GC/MS are suggested.

Sulfur Dioxide Capture by Heterogeneous Oxidation on Hydroxylated Manganese Dioxide.

PubMed

Wu, Haodong; Cai, Weimin; Long, Mingce; Wang, Hairui; Wang, Zhiping; Chen, Chen; Hu, Xiaofang; Yu, Xiaojuan

2016-06-07

Here we demonstrate that sulfur dioxide (SO2) is efficiently captured via heterogeneous oxidation into sulfate on the surface of hydroxylated manganese dioxide (MnO2). Lab-scale activity tests in a fluidized bed reactor showed that the removal efficiency for a simulated flue gas containing 5000 mg·Nm(-3) SO2 could reach nearly 100% with a GHSV (gas hourly space velocity) of 10000 h(-1). The mechanism was investigated using a combination of experimental characterizations and theoretical calculations. It was found that formation of surface bound sulfate proceeds via association of SO2 with terminal hydroxyls. Both H2O and O2 are essential for the generation of reactive terminal hydroxyls, and the indirect role of O2 in heterogeneous SO2 oxidation at low temperature was also revealed. We propose that the high reactivity of terminal hydroxyls is attributed to the proper surface configuration of MnO2 to adsorb water with degenerate energies for associative and dissociative states, and maintain rapid proton dynamics. Viability analyses suggest that the desulfurization method that is based on such a direct oxidation reaction at the gas/solid interface represents a promising approach for SO2 capture.

Chiral Sugars Drive Enantioenrichment in Prebiotic Amino Acid Synthesis.

PubMed

Wagner, Alexander J; Zubarev, Dmitry Yu; Aspuru-Guzik, Alán; Blackmond, Donna G

2017-04-26

Chiral pentose sugars mediate the enantioselective synthesis of amino acid precursors, with the magnitude of the chiral induction dictated by a subtle cooperativity between sugar hydroxyl groups. Ribose and lyxose give opposite chiral preferences, and theoretical calculations reveal the pseudoenantiomeric nature of transition state structures from the two sugars. Prebiotically plausible mixtures of natural d-sugars lead to enantioenrichment of natural l-amino acid precursors. Temporal monitoring and kinetic modeling of the reaction reveal an unusual dynamic kinetic resolution that shifts toward an enantioselective pathway over time, providing an amplification mechanism for the transfer of chiral information. This work adds to growing evidence for synergy in the etiology of the single chirality of the two most important classes of biological molecules, the sugars that make up DNA and RNA and the amino acids that form proteins.

Chiral Sugars Drive Enantioenrichment in Prebiotic Amino Acid Synthesis

PubMed Central

2017-01-01

Chiral pentose sugars mediate the enantioselective synthesis of amino acid precursors, with the magnitude of the chiral induction dictated by a subtle cooperativity between sugar hydroxyl groups. Ribose and lyxose give opposite chiral preferences, and theoretical calculations reveal the pseudoenantiomeric nature of transition state structures from the two sugars. Prebiotically plausible mixtures of natural d-sugars lead to enantioenrichment of natural l-amino acid precursors. Temporal monitoring and kinetic modeling of the reaction reveal an unusual dynamic kinetic resolution that shifts toward an enantioselective pathway over time, providing an amplification mechanism for the transfer of chiral information. This work adds to growing evidence for synergy in the etiology of the single chirality of the two most important classes of biological molecules, the sugars that make up DNA and RNA and the amino acids that form proteins. PMID:28470050

Aerosol Fragmentation Driven by Coupling of Acid-Base and Free-Radical Chemistry in the Heterogeneous Oxidation of Aqueous Citric Acid by OH Radicals.

PubMed

Liu, Matthew J; Wiegel, Aaron A; Wilson, Kevin R; Houle, Frances A

2017-08-10

A key uncertainty in the heterogeneous oxidation of carboxylic acids by hydroxyl radicals (OH) in aqueous-phase aerosol is how the free-radical reaction pathways might be altered by acid-base chemistry. In particular, if acid-base reactions occur concurrently with acyloxy radical formation and unimolecular decomposition of alkoxy radicals, there is a possibility that differences in reaction pathways impact the partitioning of organic carbon between the gas and aqueous phases. To examine these questions, a kinetic model is developed for the OH-initiated oxidation of citric acid aerosol at high relative humidity. The reaction scheme, containing both free-radical and acid-base elementary reaction steps with physically validated rate coefficients, accurately predicts the experimentally observed molecular composition, particle size, and average elemental composition of the aerosol upon oxidation. The difference between the two reaction channels centers on the reactivity of carboxylic acid groups. Free-radical reactions mainly add functional groups to the carbon skeleton of neutral citric acid, because carboxylic acid moieties deactivate the unimolecular fragmentation of alkoxy radicals. In contrast, the conjugate carboxylate groups originating from acid-base equilibria activate both acyloxy radical formation and carbon-carbon bond scission of alkoxy radicals, leading to the formation of low molecular weight, highly oxidized products such as oxalic and mesoxalic acid. Subsequent hydration of carbonyl groups in the oxidized products increases the aerosol hygroscopicity and accelerates the substantial water uptake and volume growth that accompany oxidation. These results frame the oxidative lifecycle of atmospheric aerosol: it is governed by feedbacks between reactions that first increase the particle oxidation state, then eventually promote water uptake and acid-base chemistry. When coupled to free-radical reactions, acid-base channels lead to formation of low molecular

Production of hydroxyl fatty acids, polyol oils, and diacylglycerol by bioprocess

USDA-ARS?s Scientific Manuscript database

Hydroxy fatty acids (HFA), originally found in plant systems, are good examples of the structurally modified lipids, rendering special properties such as higher viscosity and reactivity compared to normal fatty acids. Based on these properties, HFAs possess high industrial potentials in a wide range...

Adsorption of lactic acid on chiral Pt surfaces—A density functional theory study

NASA Astrophysics Data System (ADS)

Franke, J.-H.; Kosov, D. S.

2013-02-01

The adsorption of the chiral molecule lactic acid on chiral Pt surfaces is studied by density functional theory calculations. First, we study the adsorption of L-lactic acid on the flat Pt(111) surface. Using the optimed PBE - van der Waals (oPBE-vdW) functional, which includes van der Waals forces on an ab initio level, it is shown that the molecule has two binding sites, a carboxyl and the hydroxyl oxygen atoms. Since real chiral surfaces are (i) known to undergo thermal roughening that alters the distribution of kinks and step edges but not the overall chirality and (ii) kink sites and edge sites are usually the energetically most favored adsorption sites, we focus on two surfaces that allow qualitative sampling of the most probable adsorption sites. We hereby consider chiral surfaces exhibiting (111) facets, in particular, Pt(321) and Pt(643). The binding sites are either both on kink sites—which is the case for Pt(321) or on one kink site—as on Pt(643). The binding energy of the molecule on the chiral surfaces is much higher than on the Pt(111) surface. We show that the carboxyl group interacts more strongly than the hydroxyl group with the kink sites. The results indicate the possible existence of very small chiral selectivities of the order of 20 meV for the Pt(321) and Pt(643) surfaces. L-lactic acid is more stable on Pt(321)S than D-lactic acid, while the chiral selectivity is inverted on Pt(643)S. The most stable adsorption configurations of L- and D-lactic acid are similar for Pt(321) but differ for Pt(643). We explore the impact of the different adsorption geometries on the work function, which is important for field ion microscopy.

Synthesis, antimicrobial evaluation and molecular modeling of 5-hydroxyisoquinolinium salt series; the effect of the hydroxyl moiety.

PubMed

Soukup, Ondrej; Dolezal, Rafael; Malinak, David; Marek, Jan; Salajkova, Sarka; Pasdiorova, Marketa; Honegr, Jan; Korabecny, Jan; Nachtigal, Petr; Nachon, Florian; Jun, Daniel; Kuca, Kamil

2016-02-15

In the present paper, we describe the synthesis of a new group of 5-hydroxyisoquinolinium salts with different lengths of alkyl side-chain (C10-C18), and their chromatographic analysis and biological assay for in vitro activity against bacterial and fungal strains. We compare the lipophilicity and efficacy of hydroxylated isoquinolinium salts with the previously published (non-hydroxylated) isoquinolinium salts from the point of view of antibacterial and antifungal versatility and cytotoxic safety. Compound 11 (C18) had to be excluded from the testing due to its low solubility. Compounds 9 and 10 (C14, C16) showed only moderate efficacy against G+ bacteria, notably with excellent potency against Staphyloccocus aureus, but no effect against G- bacteria. In contrast, non-hydroxylated isoquinolinium salts showed excellent antimicrobial efficacy within the whole series, particularly 14 (C14) against G+ strains and 15 (C16) against fungi. The electronic properties and desolvation energies of 5-hydroxyisoquinolinium and isoquinolinium salts were studied by quantum-chemistry calculations employing B3LYP/6-311++G(d,p) method and an implicit water-solvent simulation model (SCRF). Despite the positive mesomeric effect of the hydroxyl moiety reducing the electron density of the quaternary nitrogen, it is probably the higher lipophilicity and lower desolvation energy of isoquinolinium salts, which is responsible for enhanced antimicrobial versatility and efficacy. Copyright © 2016 Elsevier Ltd. All rights reserved.

Synthesis of 3 alpha,7 alpha,12 alpha,25-tetrahydroxy-5 beta-cholestan-24-one, an intermediate in the 25-hydroxylation pathway of cholic acid biosynthesis from cholesterol.

PubMed

Dayal, B; Tint, G S; Batta, A K; Shefer, S; Salen, G; Bose, A K; Pramanik, B N

1983-02-01

This paper describes the chemical synthesis of 3 alpha,7 alpha,12 alpha,25-tetrahydroxy-5 beta-cholestan-24-one via selective oxidation of 5 beta-cholestane-3 alpha,7 alpha,12 alpha, 24 xi,25-pentol with silver carbonate on celite. The structure of this 24-keto bile alcohol was confirmed by gas-liquid chromatography and mass spectrometry. Synthesis of this compound via pyridinium chlorochromate oxidation of the triacetoxy derivative of 5 beta-cholestane-3 alpha,7 alpha,12 alpha,24 xi,25-pentol followed by saponification further established its structure. 3 alpha,7 alpha,12 alpha,25-Tetrahydroxy-5 beta-cholestan-24-one was required for the in vivo and in vitro studies of side-chain oxidation and cleavage in the 25-hydroxylation pathway of cholic acid biosynthesis.

Investigation of Water Dissociation and Surface Hydroxyl Stability on Pure and Ni-Modified CoOOH by Ambient Pressure Photoelectron Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Zhu; Kronawitter, Coleman X.; Waluyo, Iradwikanari

Water adsorption and reaction on pure and Ni-modified CoOOH nanowires were investigated using ambient pressure photoemission spectroscopy (APPES). The unique capabilities of APPES enable us to observe water dissociation and monitor formation of surface species on pure and Ni-modified CoOOH under elevated pressures and temperatures for the first time. Over a large range of pressures (UHV to 1 Torr), water dissociates readily on the pure and Ni-modified CoOOH surfaces at 27 °C. With an increase in H 2O pressure, a greater degree of surface hydroxylation was observed for all samples. At 1 Torr H 2O, ratios of different oxygen speciesmore » indicate a transformation of CoOOH to CoO xH y in pure and Ni-modified CoOOH. In temperature dependent studies, desorption of weakly bound water and surface dehydroxylation were observed with increasing temperature. In conclusion, larger percentages of surface hydroxyl groups at higher temperatures were observed on Ni-modified CoOOH compared to pure CoOOH, which indicates an increased stability of surface hydroxyl groups on these Ni-modified surfaces.« less

Investigation of Water Dissociation and Surface Hydroxyl Stability on Pure and Ni-Modified CoOOH by Ambient Pressure Photoelectron Spectroscopy

DOE PAGES

Chen, Zhu; Kronawitter, Coleman X.; Waluyo, Iradwikanari; ...

2017-09-07

Water adsorption and reaction on pure and Ni-modified CoOOH nanowires were investigated using ambient pressure photoemission spectroscopy (APPES). The unique capabilities of APPES enable us to observe water dissociation and monitor formation of surface species on pure and Ni-modified CoOOH under elevated pressures and temperatures for the first time. Over a large range of pressures (UHV to 1 Torr), water dissociates readily on the pure and Ni-modified CoOOH surfaces at 27 °C. With an increase in H 2O pressure, a greater degree of surface hydroxylation was observed for all samples. At 1 Torr H 2O, ratios of different oxygen speciesmore » indicate a transformation of CoOOH to CoO xH y in pure and Ni-modified CoOOH. In temperature dependent studies, desorption of weakly bound water and surface dehydroxylation were observed with increasing temperature. In conclusion, larger percentages of surface hydroxyl groups at higher temperatures were observed on Ni-modified CoOOH compared to pure CoOOH, which indicates an increased stability of surface hydroxyl groups on these Ni-modified surfaces.« less

How does the axial ligand of cytochrome P450 biomimetics influence the regioselectivity of aliphatic versus aromatic hydroxylation?

PubMed

de Visser, Sam P; Tahsini, Laleh; Nam, Wonwoo

2009-01-01

The catalytic activity of high-valent iron-oxo active species of heme enzymes is known to be dependent on the nature of the axial ligand trans to the iron-oxo group. In a similar fashion, experimental studies on iron-oxo porphyrin biomimetic systems have shown a significant axial ligand effect on ethylbenzene hydroxylation, with an axial acetonitrile ligand leading to phenyl hydroxylation products and an axial chloride anion giving predominantly benzyl hydroxylation products. To elucidate the fundamental factors that distinguish this regioselectivity reversal in iron-oxo porphyrin catalysis, we have performed a series of density functional theory calculations on the hydroxylation of ethylbenzene by [Fe(IV)=O(Por(+.))L] (Por = porphyrin; L = NCCH(3) or Cl(-)), which affords 1-phenylethanol and p-ethylphenol products. The calculations confirm the experimentally determined product distributions. Furthermore, a detailed analysis of the electronic differences between the two oxidants shows that their reversed regioselectivity is a result of differences in orbital interactions between the axial ligand and iron-oxo porphyrin system. In particular, three high-lying orbitals (pi*(xz), pi*(yz) and a(2u)), which are singly occupied in the reactant complex, are stabilised with an anionic ligand such as Cl(-), which leads to enhanced HOMO-LUMO energy gaps. As a consequence, reactions leading to cationic intermediates through the two-electron reduction of the metal centre are disfavoured. The aliphatic hydroxylation mechanism, in contrast, is a radical process in which only one electron is transferred in the rate-determining transition state, which means that the effect of the axial ligand on this mechanism is much smaller.

Ultrasonic-assisted synthesis of polyvinyl alcohol/phytic acid polymer film and its thermal stability, mechanical properties and surface resistivity.

PubMed

Li, Jihui; Li, Yongshen; Song, Yunna; Niu, Shuai; Li, Ning

2017-11-01

In this paper, polyvinyl alcohol/phytic acid polymer (PVA/PA polymer) was synthesized through esterification reaction of PVA and PA in the case of acidity and ultrasound irradiation and characterized, and PVA/PA polymer film was prepared by PVA/PA polymer and characterized, and the influence of dosage of PA on the thermal stability, mechanical properties and surface resistivity of PVA/PA polymer film were researched, and the influence of sonication time on the mechanical properties of PVA/PA polymer film was investigated. Based on those, it was concluded that the hydroxyl group on the chain of PVA and the phosphonic group on PA were connected together in the form of phosphonate bond, and the hydroxyl group on the chain of PVA were connected together in the form of ether bond after the intermolecular dehydration; in the meantime, it was also confirmed that PVA/PA polymer film prepared from 1.20mL of PA not only had the high thermal stability and favorable ductility but also the low surface resistivity in comparison with PVA/PA polymer film with 0.00mL of PA, and the ductility of PVA/PA polymer film was very sensitive to the sonication time. Copyright © 2017. Published by Elsevier B.V.

Non-linear hydroxyl radical formation rate in dispersions containing mixtures of pyrite and chalcopyrite particles

NASA Astrophysics Data System (ADS)

Kaur, Jasmeet; Schoonen, Martin A.

2017-06-01

The formation of hydroxyl radicals was studied in mixed pyrite-chalcopyrite dispersions in water using the conversion rate of adenine as a proxy for hydroxyl radical formation rate. Experiments were conducted as a function of pH, presence of phosphate buffer, surface loading, and pyrite-to-chalcopyrite ratio. The results indicate that hydroxyl radical formation rate in mixed systems is non-linear with respect to the rates in the pure endmember dispersions. The only exception is a set of experiments in which phosphate buffer is used. In the presence of phosphate buffer, the hydroxyl radical formation is suppressed in mixtures and the rate is close to that predicted based on the reaction kinetics of the pure endmembers. The non-linear hydroxyl radical formation in dispersions containing mixtures of pyrite and chalcopyrite is likely the result of two complementary processes. One is the fact that pyrite and chalcopyrite form a galvanic couple. In this arrangement, chalcopyrite oxidation is accelerated, while pyrite passes electrons withdrawn from chalcopyrite to molecular oxygen, the oxidant. The incomplete reduction of molecular oxygen leads to the formation of hydrogen peroxide and hydroxyl radical. The galvanic coupling appears to be augmented by the fact that chalcopyrite generates a significant amount of hydrogen peroxide upon dispersal in water. This hydrogen peroxide is then available for conversion to hydroxyl radical, which appears to be facilitated by pyrite as chalcopyrite itself produces only minor amounts of hydroxyl radical. In essence, pyrite is a ;co-factor; that facilitates the conversion of hydrogen peroxide to hydroxyl radical. This conversion reaction is a surface-mediated reaction. Given that hydroxyl radical is one of the most reactive species in nature, the formation of hydroxyl radicals in aqueous systems containing chalcopyrite and pyrite has implications for the stability of organic molecules, biomolecules, the viability of microbes, and

Release of Reactive Oxygen Intermediates (Superoxide Radicals, Hydrogen Peroxide, and Hydroxyl Radicals) and Peroxidase in Germinating Radish Seeds Controlled by Light, Gibberellin, and Abscisic Acid1

PubMed Central

Schopfer, Peter; Plachy, Claudia; Frahry, Gitta

2001-01-01

Germination of radish (Raphanus sativus cv Eterna) seeds can be inhibited by far-red light (high-irradiance reaction of phytochrome) or abscisic acid (ABA). Gibberellic acid (GA3) restores full germination under far-red light. This experimental system was used to investigate the release of reactive oxygen intermediates (ROI) by seed coats and embryos during germination, utilizing the apoplastic oxidation of 2′,7′-dichlorofluorescin to fluorescent 2′,7′-dichlorofluorescein as an in vivo assay. Germination in darkness is accompanied by a steep rise in ROI release originating from the seed coat (living aleurone layer) as well as the embryo. At the same time as the inhibition of germination, far-red light and ABA inhibit ROI release in both seed parts and GA3 reverses this inhibition when initiating germination under far-red light. During the later stage of germination the seed coat also releases peroxidase with a time course affected by far-red light, ABA, and GA3. The participation of superoxide radicals, hydrogen peroxide, and hydroxyl radicals in ROI metabolism was demonstrated with specific in vivo assays. ROI production by germinating seeds represents an active, developmentally controlled physiological function, presumably for protecting the emerging seedling against attack by pathogens. PMID:11299341

Methemoglobinemia Hemotoxicity of Some Antimalarial 8-Aminoquinoline Analogues and Their Hydroxylated Derivatives: Density Functional Theory Computation of Ionization Potentials.

PubMed

Ding, Yuanqing; Liu, Haining; Tekwani, Babu L; Nanayakkara, N P Dhammika; Khan, Ikhlas A; Walker, Larry A; Doerksen, Robert J

2016-07-18

The administration of primaquine (PQ), an essential drug for the treatment and radical cure of malaria, can lead to methemoglobin formation and life-threatening hemolysis for glucose-6-phosphate dehydrogenase deficient patients. The ionization potential (IP, a quantitative measure of the ability to lose an electron) of the metabolites generated by antimalarial 8-aminoquinoline (8-AQ) drugs like PQ has been believed to be correlated in part to this methemoglobinemia hemotoxicity: the lower the IP of an 8-AQ derivative, the higher the concentration of methemoglobin generated. In this work, demethoxylated primaquine (AQ02) was employed as a model, by intensive computation at the B3LYP-SCRF(PCM)/6-311++G**//B3LYP/6-31G** level in water, to study the effects of hydroxylation at various positions on the ionization potential. Compared to the parent AQ02, the IPs of AQ02's metabolites hydroxylated at N1', C5, and C7 were lower by 61, 30, and 19 kJ/mol, respectively, while differences in the IP relative to PQ were small for hydroxylation at all other positions. The C6 position, at which the IP of the hydroxylated metabolite was greater than that of AQ02, by 2 kJ/mol, was found to be unique. Several literature and proposed 8-AQ analogues were studied to evaluate substituent effects on their potential to generate methemoglobin, with the finding that hydroxylations at N1' and C5 contribute the most to the potential hemotoxicity of PQ-based antimalarials, whereas hydroxylation at C7 has little effect. Phenoxylation at C5 in PQ-based 8-AQs can block the hydroxylation at C5 and reduce the potential for methemoglobin generation, while -CF3 and chlorines attached to the phenolic ring can further reduce the risk. The H-shift at N1' during the cationization of hydroxylated metabolites of 8-AQs sharply decreased their IPs, but this effect can be significantly reduced by the introduction of an electron-withdrawing group to the quinoline core. The results and this approach may be

Electrocatalytic behavior of a nanocomposite of Ni/Pd supported by carbonized PVA nanofibers towards formic acid, ethanol and urea oxidation: A physicochemical and electro-analysis study

NASA Astrophysics Data System (ADS)

Mohamed, Ibrahim M. A.; Yasin, Ahmed S.; Barakat, Nasser A. M.; Song, Seung A.; Lee, Ha Eun; Kim, Seong Su

2018-03-01

A nanocomposite of Ni/Pd supported by carbonized poly-vinyl alcohol (PVA) nanofibers (NFs) was synthesized via electrospinning followed by calcination under an argon atmosphere. The as-synthesized NFs were studied using physicochemical analyses, such as field-emission scanning electron microscopy (FESEM), Transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTsbnd IR) and X-ray photoelectron spectroscopy (XPS), to investigate the morphology, crystallinity, effect of carbonization and surface chemistry of the NFs, respectively. Cyclic voltammetry (CV) and chronoamperometry (CA) were utilized to study the performance of the NFs towards electrooxidation reactions. The designed NFs present superior electrocatalytic behavior in an acid medium towards formic acid oxidation, as well as urea and ethanol oxidation in an alkaline medium. The electrocatalytic performance of the bimetallic NFs appears to arise from the assembly of bimetallic Ni/Pd@NFs based on PVA, which has hydroxyl groups. These hydroxyl groups can decrease the negative processes that occur as a result of metal-metal interactions, such as the aggregation process. This study introduces a novel non-precious electrocatalyst to facilitate the commercialization of fuel cells based on formic acid, urea and ethanol.

Phosphatidic acid in neuronal development: a node for membrane and cytoskeleton rearrangements.

PubMed

Ammar, Mohamed-Raafet; Kassas, Nawal; Bader, Marie-France; Vitale, Nicolas

2014-12-01

Phosphatidic acid (PA) is the simplest phospholipid naturally existing in all-living organisms. It constitutes only a minor fraction of the total cell lipids but has attracted considerable attention being both a lipid second messenger and a modulator of membrane shape. The pleiotropic functions of PA are the direct consequence of its very simple chemical structure consisting of only two acyl chains linked by ester bonds to two adjacent hydroxyl groups of glycerol, whose remaining hydroxyl group is esterified with a phosphomonoester group. Hence the small phosphate head group of PA gives it the shape of a cone providing flexibility and negative curvatures in the context of a lipid bilayer. In addition, the negatively charged phosphomonoester headgroup of PA is unique because it can potentially carry one or two negative charges playing a role in the recruitment of positively charged molecules to biomembranes. In consequence, PA has been proposed to play various key cellular functions. In the brain, a fine balance between cell growth, migration and differentiation, and cell death is required to sculpt the nervous system during development. In this review, we will summarize the various functions that have been proposed for PA in neuronal development. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

[Correlations of bile acids in the bile of rats in conditions of alloxan induced diabetes melitus].

PubMed

Danchenko, N M; Vesel'skyĭ, S P; Tsudzevych, B O

2014-01-01

The ratio of bile acids in the bile of rats with alloxan diabetes was investigated using the method of thin-layer chromatography. Changes of coefficients of conjugation and hydroxylation of bile acids were calculated and analyzed in half-hour samples of bile obtained during the 3-hour experiment. It has been found that the processes of conjugation of cholic acid with glycine and taurine are inhibited in alloxan diabetes. At the same time a significant increase of free threehydroxycholic and dixydroxycholic bile acids and conjugates of the latter ones with taurine has been registered. Coefficients of hydroxylation in alloxan diabetes show the domination of "acidic" pathway in bile acid biosynthesis that is tightly connected with the activity of mitochondrial enzymes.

Measurement of hydroxyl radical production in ultrasonic aqueous solutions by a novel chemiluminescence method.

PubMed

Hu, Yufei; Zhang, Zhujun; Yang, Chunyan

2008-07-01

Measurement methods for ultrasonic fields are important for reasons of safety. The investigation of an ultrasonic field can be performed by detecting the yield of hydroxyl radicals resulting from ultrasonic cavitations. In this paper, a novel method is introduced for detecting hydroxyl radicals by a chemiluminescence (CL) reaction of luminol-hydrogen peroxide (H2O2)-K5[Cu(HIO6)2](DPC). The yield of hydroxyl radicals is calculated directly by the relative CL intensity according to the corresponding concentration of H2O2. This proposed CL method makes it possible to perform an in-line and real-time assay of hydroxyl radicals in an ultrasonic aqueous solution. With flow injection (FI) technology, this novel CL reaction is sensitive enough to detect ultra trace amounts of H2O2 with a limit of detection (3sigma) of 4.1 x 10(-11) mol L(-1). The influences of ultrasonic output power and ultrasonic treatment time on the yield of hydroxyl radicals by an ultrasound generator were also studied. The results indicate that the amount of hydroxyl radicals increases with the increase of ultrasonic output power (< or = 15 W mL(-1)). There is a linear relationship between the time of ultrasonic treatment and the yield of H2O2. The ultrasonic field of an ultrasonic cleaning baths has been measured by calculating the yield of hydroxyl radicals.

Pectin functionalised by fatty acids: Diffuse reflectance infrared Fourier transform (DRIFT) spectroscopic characterisation

NASA Astrophysics Data System (ADS)

Kamnev, Alexander A.; Calce, Enrica; Tarantilis, Petros A.; Tugarova, Anna V.; De Luca, Stefania

2015-01-01

Chemically modified pectin derivatives obtained by partial esterification of its hydroxyl moieties with fatty acids (FA; oleic, linoleic and palmitic acids), as well as the initial apple peel pectin were comparatively characterised using diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. Characteristic changes observed in DRIFT spectra in going from pectin to its FA esters are related to the corresponding chemical modifications. Comparing the DRIFT spectra with some reported data on FTIR spectra of the same materials measured in KBr or NaCl matrices has revealed noticeable shifts of several polar functional groups both in pectin and in its FA-esterified products induced by the halide salts. The results obtained have implications for careful structural analyses of biopolymers with hydrophilic functional groups by means of different FTIR spectroscopic methodologies.

Usefulness of organic acid produced by Exiguobacterium sp. 12/1 on neutralization of alkaline wastewater.

PubMed

Kulshreshtha, Niha Mohan; Kumar, Anil; Bisht, Gopal; Pasha, Santosh; Kumar, Rita

2012-01-01

The aim of this study was to investigate the role of organic acids produced by Exiguobacterium sp. strain 12/1 (DSM 21148) in neutralization of alkaline wastewater emanated from beverage industry. This bacterium is known to be able to grow in medium of pH as high as pH 12.0 and to neutralize alkaline industrial wastewater from pH 12.0 to pH 7.5. The initial investigation on the type of functional groups present in medium, carried out using FT-IR spectroscopy, revealed the presence of peaks corresponding to carbonyl group and hydroxyl group, suggesting the release of carboxylic acid or related metabolic product(s). The identification of specific carboxylic group, carried out using RP-HPLC, revealed the presence of a single peak in the culture supernatant with retention time most similar to formic acid. The concentration of acid produced on different carbon sources was studied as a function of time. Although acid was present in same final concentration, the rate of acid production was highest in case of medium supplemented with sucrose followed by fructose and glucose. The knowledge of metabolic products of the bacterium can be considered as a first step towards realization of its potential for large-scale bioremediation of alkaline wastewater from beverage industry.

Usefulness of Organic Acid Produced by Exiguobacterium sp. 12/1 on Neutralization of Alkaline Wastewater

PubMed Central

Kulshreshtha, Niha Mohan; Kumar, Anil; Bisht, Gopal; Pasha, Santosh; Kumar, Rita

2012-01-01

The aim of this study was to investigate the role of organic acids produced by Exiguobacterium sp. strain 12/1 (DSM 21148) in neutralization of alkaline wastewater emanated from beverage industry. This bacterium is known to be able to grow in medium of pH as high as pH 12.0 and to neutralize alkaline industrial wastewater from pH 12.0 to pH 7.5. The initial investigation on the type of functional groups present in medium, carried out using FT-IR spectroscopy, revealed the presence of peaks corresponding to carbonyl group and hydroxyl group, suggesting the release of carboxylic acid or related metabolic product(s). The identification of specific carboxylic group, carried out using RP-HPLC, revealed the presence of a single peak in the culture supernatant with retention time most similar to formic acid. The concentration of acid produced on different carbon sources was studied as a function of time. Although acid was present in same final concentration, the rate of acid production was highest in case of medium supplemented with sucrose followed by fructose and glucose. The knowledge of metabolic products of the bacterium can be considered as a first step towards realization of its potential for large-scale bioremediation of alkaline wastewater from beverage industry. PMID:22666107

Production of hydroxyl radical by redox active flavonoids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kalyanaraman, B.; Hodnick, W.F.; Pardini, R.S.

1986-05-01

The authors have previously shown that flavonoids autoxidize and generate superoxide (O/sub 2//sup -/) and hydrogen peroxide (H/sub 2/O/sub 2/), suggesting that hydroxyl radical (OH) could be formed via the metal-ion catalyzed Haber-Weiss reaction. In the presence of ethylenediamine tetraacetic acid (EDTA) and 5,5-dimethyl-1-pyrroline-1-oxide (DMPO), myricetin, quercetagetin and quercetin gave an ESR signal for the DMPO-OH spin adduct, and the DMPO-Eto adduct in the presence of excess ethanol, indicating the production of free OH. The addition of FeCl/sub 3/ to the reaction mixture resulted in a dramatic increase in the DMPO-OH signal. Without chelator (EDTA) there was no signal andmore » the presence of diethylenetriamine-pentaacetic acid (DETAPAC) greatly diminished the signal. The presence of superoxide dismutase (SOD) had no effect on the signal while catalase completely abrogated the signal. The addition of Fe (III)-EDTA to flavonoid solutions under anaerobic conditions produced time dependent auxochromic shifts in their absorption spectra and resulted in the reduction of Fe (III) to Fe (II). These data suggest that the flavonoids autoxidize to produce O/sub 2//sup -/ and H/sub 2/O/sub 2/ by dismutation and in the presence of Fe (III)-EDTA the flavonoid can directly reduce the Fe (III) to Fe (II) resulting in the production of OH through Fenton chemistry.« less

Fabrication of calcium phosphate–calcium sulfate injectable bone substitute using hydroxy-propyl-methyl-cellulose and citric acid

PubMed Central

Thai, Van Viet

2010-01-01

In this study, an injectable bone substitute (IBS) consisting of citric acid, chitosan, and hydroxyl propyl methyl cellulose (HPMC) as the liquid phase and tetra calcium phosphate (TTCP), dicalcium phosphate dihydrate (DCPD) and calcium sulfate dehydrate (CSD, CaSO4·2H2O) powders as the solid phase, were fabricated. Two groups were classified based on the percent of citric acid in the liquid phase (20, 40 wt%). In each groups, the HPMC percentage was 0, 2, and 4 wt%. An increase in compressive strength due to changes in morphology was confirmed by scanning electron microscopy images. A good conversion rate of HAp at 20% citric acid was observed in the XRD profiles. In addition, HPMC was not obviously affected by apatite formation. However, both HPMC and citric acid increased the compressive strength of IBS. The maximum compressive strength for IBS was with 40% citric acid and 4% HPMC after 14 days of incubation in 100% humidity at 37°C. PMID:20333539

CYP101J2, CYP101J3, and CYP101J4, 1,8-Cineole-Hydroxylating Cytochrome P450 Monooxygenases from Sphingobium yanoikuyae Strain B2

PubMed Central

Unterweger, Birgit; Bulach, Dieter M.; Scoble, Judith; Midgley, David J.; Greenfield, Paul; Lyras, Dena; Johanesen, Priscilla

2016-01-01

ABSTRACT We report the isolation and characterization of three new cytochrome P450 monooxygenases: CYP101J2, CYP101J3, and CYP101J4. These P450s were derived from Sphingobium yanoikuyae B2, a strain that was isolated from activated sludge based on its ability to fully mineralize 1,8-cineole. Genome sequencing of this strain in combination with purification of native 1,8-cineole-binding proteins enabled identification of 1,8-cineole-binding P450s. The P450 enzymes were cloned, heterologously expressed (N-terminally His6 tagged) in Escherichia coli BL21(DE3), purified, and spectroscopically characterized. Recombinant whole-cell biotransformation in E. coli demonstrated that all three P450s hydroxylate 1,8-cineole using electron transport partners from E. coli to yield a product putatively identified as (1S)-2α-hydroxy-1,8-cineole or (1R)-6α-hydroxy-1,8-cineole. The new P450s belong to the CYP101 family and share 47% and 44% identity with other 1,8-cineole-hydroxylating members found in Novosphingobium aromaticivorans and Pseudomonas putida. Compared to P450cin (CYP176A1), a 1,8-cineole-hydroxylating P450 from Citrobacter braakii, these enzymes share less than 30% amino acid sequence identity and hydroxylate 1,8-cineole in a different orientation. Expansion of the enzyme toolbox for modification of 1,8-cineole creates a starting point for use of hydroxylated derivatives in a range of industrial applications. IMPORTANCE CYP101J2, CYP101J3, and CYP101J4 are cytochrome P450 monooxygenases from S. yanoikuyae B2 that hydroxylate the monoterpenoid 1,8-cineole. These enzymes not only play an important role in microbial degradation of this plant-based chemical but also provide an interesting route to synthesize oxygenated 1,8-cineole derivatives for applications as natural flavor and fragrance precursors or incorporation into polymers. The P450 cytochromes also provide an interesting basis from which to compare other enzymes with a similar function and expand the CYP101

Pulsed corona discharge: the role of ozone and hydroxyl radical in aqueous pollutants oxidation.

PubMed

Preis, S; Panorel, I C; Kornev, I; Hatakka, H; Kallas, J

2013-01-01

Ozone and hydroxyl radical are the most active oxidizing species in water treated with gas-phase pulsed corona discharge (PCD). The ratio of the species dependent on the gas phase composition and treated water contact surface was the objective for the experimental research undertaken for aqueous phenol (fast reaction) and oxalic acid (slow reaction) solutions. The experiments were carried out in the reactor, where aqueous solutions showered between electrodes were treated with 100-ns pulses of 20 kV voltage and 400 A current amplitude. The role of ozone increased with increasing oxygen concentration and the oxidation reaction rate. The PCD treatment showed energy efficiency surpassing that of conventional ozonation.

Mass spectrometry of analytical derivatives. 2. “Ortho” and “Para” effects in electron ionization mass spectra of derivatives of hydroxy, mercapto and amino benzoic acids1

PubMed Central

Todua, Nino G.; Mikaia, Anzor I.

2016-01-01

Derivatives requiring either anhydrous or aqueous reaction conditions were prepared for robust and reliable gas chromatography/mass spectrometry (GC/MS) characterization of hydroxyl, mercapto, and amino benzoic acids Methylation and trialkylsilytation are employed for blocking the acidic function. Alkyl, trimethylsilyl, acetyl, perfluoroacyl and alkoxycarbonyl derivatization groups are introduced to hydroxyl, mercapto and amino functions. The electron ionization induced fragmentation characteristics of corresponding derivatives are explained by comparing the MS1 spectra of unlabeled compounds to their 2H and 13C labeled analogs, and analysis of collision-induced dissociation data from MS2 spectra. Competing fragmentation alternatives are identified and specific decomposition processes are detailed that characterize (a) ortho isomers due to interaction or vicinal functional substituents and (b) para isomers prone to forming para quinoid type structures. Skeletal and hydrogen rearrangements typical for methyl benzoates and the blocking groups are considered when discussing diagnostically important ions. Characteristic ions produced as a result of rearrangements in ortho isomers are classified, and skeletal rearrangements required to produce para quinoid type ions specific for para isomers are noted. Key ions for structure elucidation and differentiation of isomers for derivatives of substituted benzoic acids by GC/MS are suggested. PMID:27891187

Selective hydroxylation of benzene derivatives and alkanes with hydrogen peroxide catalysed by a manganese complex incorporated into mesoporous silica-alumina.

PubMed

Aratani, Yusuke; Yamada, Yusuke; Fukuzumi, Shunichi

2015-03-18

Selective hydroxylation of benzene derivatives and alkanes to the corresponding phenol and alcohol derivatives with hydrogen peroxide was efficiently catalysed by a manganese tris(2-pyridylmethyl)amine (tpa) complex ([(tpa)Mn(II)](2+)) incorporated into mesoporous silica-alumina with highly acidic surfaces in contrast to the reactions in a homogeneous solution where [(tpa)Mn(II)](2+) was converted catalytically to a much less active bis(μ-oxo)dimanganese(III,IV) complex.

Moringa oleifera Lam. seed extract prevents fat diet induced oxidative stress in mice and protects liver cell-nuclei from hydroxyl radical mediated damage.

PubMed

Das, Nilanjan; Ganguli, Debdutta; Dey, Sanjit

2015-12-01

High fat diet (HFD) prompts metabolic pattern inducing reactive oxygen species (ROS) production in mitochondria thereby triggering multitude of chronic disorders in human. Antioxidants from plant sources may be an imperative remedy against this disorder. However, it requires scientific validation. In this study, we explored if (i) Moringa oleifera seed extract (MoSE) can neutralize ROS generated in HFD fed mice; (ii) protect cell-nuclei damage developed by Fenton reaction in vitro. Swiss mice were fed with HFD to develop oxidative stress model (HFD group). Other groups were control, seed extract alone treated, and MoSE simultaneously (HS) treated. Treatment period was of 15 days. Antioxidant enzymes with tissue nitrite content (TNC) and lipid peroxidation (LPO) were estimated from liver homogenate. HS group showed significantly higher (P < 0.05) superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx), reduced glutathione (GSH) activity, and ferric reducing antioxidant power (FRAP) compared to only HFD fed group. Further, TNC and LPO decreased significantly (P < 0.05) in HS group compared to HFD fed group. MoSE also protected hepatocytes nuclei from the hydroxyl radicals generated by Fenton reaction. MoSE was found to be polyphenol rich with potent reducing power, free radicals and hydroxyl radicals scavenging activity. Thus, MoSE exhibited robust antioxidant prospective to neutralize ROS developed in HFD fed mice and also protected the nuclei damage from hydroxyl radicals. Hence, it can be used as herbal medication against HFD induced ROS mediated disorders.

Changes in structural characteristics of antioxidative soy protein hydrolysates resulting from scavenging of hydroxyl radicals.

PubMed

Zhao, Jing; Xiong, Youling L; McNear, Dave H

2013-02-01

Antioxidant activity of soy protein (SP) and its hydrolyzed peptides has been widely reported. During scavenging of radicals, these antioxidative compounds would be oxidatively modified, but their fate is not understood. The objective of this study was to evaluate the structural characteristics of SP hydrolysates (SPHs), compared to intact SP, when used to neutralize hydroxyl radicals (•OH). SPHs with degree of hydrolysis (DH) 1 to 5 were prepared with Alcalase. Antioxidant activity of SPHs was confirmed by lipid oxidation inhibition measured with thiobarbituric acid-reactive substances, ability to scavenge 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) radicals, and ferrous ion chelation capability. Oxidation of SPHs was initiated by reaction with •OH generated from 0.1 mM FeCl(3) , 20 mM H(2) O(2) , and 1.0 mM ascorbate. After oxidative stress, carbonyl content of SPHs increased by 2- to 3-fold and sulfhydryl groups decreased by up to 42% compared to nonoxidized samples (P < 0.05). Methionine, histidine, and lysine residues were significantly reduced as a result of inactivating •OH (P < 0.05). Attenuated total reflectance-Fourier transform infrared and circular dichroism spectroscopy suggested the conversion of helical structure to strands and turns. Oxidatively modified SPHs had a lower intrinsic fluorescence intensity but similar solubility when compared to nonoxidized samples. These structural changes due to •OH stress may impact the ingredient interaction and functionality of SPHs in food products. © 2013 Institute of Food Technologists®

Effector region of the translation elongation factor EF-Tu.GTP complex stabilizes an orthoester acid intermediate structure of aminoacyl-tRNA in a ternary complex.

PubMed Central

Förster, C; Limmer, S; Zeidler, W; Sprinzl, M

1994-01-01

tRNA(Val) from Escherichia coli was aminoacylated with [1-13C]valine and its complex with Thermus thermophilus elongation factor EF-Tu.GTP was analyzed by 13C NMR spectroscopy. The results suggest that the aminoacyl residue of the valyl-tRNA in ternary complex with bacterial EF-Tu and GTP is not attached to tRNA by a regular ester bond to either a 2'- or 3'-hydroxyl group; instead, an intermediate orthoester acid structure with covalent linkage to both vicinal hydroxyls of the terminal adenosine-76 is formed. Mutation of arginine-59 located in the effector region of EF-Tu, a conserved residue in protein elongation factors and the alpha subunits of heterotrimeric guanine nucleotide-binding regulatory proteins (G proteins), abolishes the stabilization of the orthoester acid structure of aminoacyl-tRNA. PMID:8183898

Mechanistic Study of the Validity of Using Hydroxyl Radical Probes To Characterize Electrochemical Advanced Oxidation Processes.

PubMed

Jing, Yin; Chaplin, Brian P

2017-02-21

The detection of hydroxyl radicals (OH • ) is typically accomplished by using reactive probe molecules, but prior studies have not thoroughly investigated the suitability of these probes for use in electrochemical advanced oxidation processes (EAOPs), due to the neglect of alternative reaction mechanisms. In this study, we investigated the suitability of four OH • probes (coumarin, p-chlorobenzoic acid, terephthalic acid, and p-benzoquinone) for use in EAOPs. Experimental results indicated that both coumarin and p-chlorobenzoic acid are oxidized via direct electron transfer reactions, while p-benzoquinone and terephthalic acid are not. Coumarin oxidation to form the OH • adduct product 7-hydroxycoumarin was found at anodic potentials lower than that necessary for OH • formation. Density functional theory (DFT) simulations found a thermodynamically favorable and non-OH • mediated pathway for 7-hydroxycoumarin formation, which is activationless at anodic potentials > 2.10 V/SHE. DFT simulations also provided estimates of E° values for a series of OH • probe compounds, which agreed with voltammetry results. Results from this study indicated that terephthalic acid is the most appropriate OH • probe compound for the characterization of electrochemical and catalytic systems.

A facile preparation of TiO2/ACF with Csbnd Ti bond and abundant hydroxyls and its enhanced photocatalytic activity for formaldehyde removal

NASA Astrophysics Data System (ADS)

Liu, R. F.; Li, W. B.; Peng, A. Y.

2018-01-01

The quantum yields and efficiency(ACF) was prepared via a modified deposition-precipitation method to facilitate its photon absorption and of photogenerated charge carriers have been the major issues for photocatalysis on titania catalyst. The TiO2/ACF catalyst with anatase TiO2 uniformly dispersed on activated carbon fibers electron transfer, thus improve the quantum yields and efficiency of the photogenerated electrons and holes. XPS analysis on the catalyst demonstrates the existence of Ti3+ and Ti2+ species, Csbnd Ti bond and abundant hydroxyls, which are also proved by UV-vis DRS and TG-DSC analysis. It is believed that the acid environment in preparation plays an essential role in the formation of Csbnd Ti bond and surface hydroxyls, which can be tuned by changing hydrothermal synthesis time. The Csbnd Ti bond can improve the electron transfer in the catalyst and the substantial surface hydroxyls lead to high absorption for UV lines and enhanced adsorption of water and formaldehyde, resulting in more active OH free radicals and the outstanding photocatalytic activity of TiO2/ACF, which is much higher than the titania powder for photocatalytic removal of low concentration formaldehyde. The essential role of surface hydroxyls for photocatalytic activity was confirmed surpassing that of chemical bond between carbon and titanium in TiO2-carbon composite for the first time.

OH-radical induced degradation of hydroxybenzoic- and hydroxycinnamic acids and formation of aromatic products—A gamma radiolysis study

NASA Astrophysics Data System (ADS)

Krimmel, Birgit; Swoboda, Friederike; Solar, Sonja; Reznicek, Gottfried

2010-12-01

The OH-radical induced degradation of hydroxybenzoic acids (HBA), hydroxycinnamic acids (HCiA) and methoxylated derivatives, as well as of chlorogenic acid and rosmarinic acid was studied by gamma radiolysis in aerated aqueous solutions. Primary aromatic products resulting from an OH-radical attachment to the ring (hydroxylation), to the position occupied by the methoxyl group (replacement -OCH 3 by -OH) as well as to the propenoic acid side chain of the cinnamic acids (benzaldehyde formations) were analysed by HPLC-UV and LC-ESI-MS. A comparison of the extent of these processes is given for 3,4-dihydroxybenzoic acid, vanillic acid, isovanillic acid, syringic acid, cinnamic acid, 4-hydroxycinnamic acid, caffeic acid, ferulic acid, isoferulic acid, chlorogenic acid, and rosmarinic acid. For all cinnamic acids and derivatives benzaldehydes were significant oxidation products. With the release of caffeic acid from chlorogenic acid the cleavage of a phenolic glycoside could be demonstrated. Reaction mechanisms are discussed.

Synthesis and characterization of a novel hyaluronic acid hydrogel.

PubMed

Zhao, X

2006-01-01

Hyaluronic acid (hyaluronan, HA) has many medical applications as a biomaterial. To enhance its biostability, a novel hydrogel of cross-linked hyaluronic acid was prepared using a double cross-linking process, which involves building cross-linkages between hydroxyl group pairs and carboxyl group pairs. The present study explored a number of cross-linking processes in order to obtain different degrees of cross-linking, which were evaluated by the measurement of water absorption capacity as an index of the gel network density. To gain a better understanding of the stability of the gel, the chemical structure and particularly the rheological behaviour of the cross-linked HA, which included the influences of factors, such as degree of cross-linking, HA concentration and gel particle size, were investigated. The in vitro biostability against hyaluronidase and free radical degradation was tested to show that the cross-linked hydrogel had improved resistance to in vitro hyaluronidase and free radical degradation.

Atmospheric Hydroxyl Radical Production from Electronically Excited NO2 and H2O

NASA Astrophysics Data System (ADS)

Li, Shuping; Matthews, Jamie; Sinha, Amitabha

2008-03-01

Hydroxyl radicals are often called the “detergent” of the atmosphere because they control the atmosphere’s capacity to cleanse itself of pollutants. Here, we show that the reaction of electronically excited nitrogen dioxide with water can be an important source of tropospheric hydroxyl radicals. Using measured rate data, along with available solar flux and atmospheric mixing ratios, we demonstrate that the tropospheric hydroxyl contribution from this source can be a substantial fraction (50%) of that from the traditional O(1D) + H2O reaction in the boundary-layer region for high solar zenith angles. Inclusion of this chemistry is expected to affect modeling of urban air quality, where the interactions of sunlight with emitted NOx species, volatile organic compounds, and hydroxyl radicals are central in determining the rate of ozone formation.

Atmospheric hydroxyl radical production from electronically excited NO2 and H2O.

PubMed

Li, Shuping; Matthews, Jamie; Sinha, Amitabha

2008-03-21

Hydroxyl radicals are often called the "detergent" of the atmosphere because they control the atmosphere's capacity to cleanse itself of pollutants. Here, we show that the reaction of electronically excited nitrogen dioxide with water can be an important source of tropospheric hydroxyl radicals. Using measured rate data, along with available solar flux and atmospheric mixing ratios, we demonstrate that the tropospheric hydroxyl contribution from this source can be a substantial fraction (50%) of that from the traditional O(1D) + H2O reaction in the boundary-layer region for high solar zenith angles. Inclusion of this chemistry is expected to affect modeling of urban air quality, where the interactions of sunlight with emitted NOx species, volatile organic compounds, and hydroxyl radicals are central in determining the rate of ozone formation.

Proline Availability Regulates Proline-4-Hydroxylase Synthesis and Substrate Uptake in Proline-Hydroxylating Recombinant Escherichia coli

PubMed Central

Falcioni, Francesco; Blank, Lars M.; Frick, Oliver; Karau, Andreas; Schmid, Andreas

2013-01-01

Microbial physiology plays a crucial role in whole-cell biotransformation, especially for redox reactions that depend on carbon and energy metabolism. In this study, regio- and enantio-selective proline hydroxylation with recombinant Escherichia coli expressing proline-4-hydroxylase (P4H) was investigated with respect to its interconnectivity to microbial physiology and metabolism. P4H production was found to depend on extracellular proline availability and on codon usage. Medium supplementation with proline did not alter p4h mRNA levels, indicating that P4H production depends on the availability of charged prolyl-tRNAs. Increasing the intracellular levels of soluble P4H did not result in an increase in resting cell activities above a certain threshold (depending on growth and assay temperature). Activities up to 5-fold higher were reached with permeabilized cells, confirming that host physiology and not the intracellular level of active P4H determines the achievable whole-cell proline hydroxylation activity. Metabolic flux analysis revealed that tricarboxylic acid cycle fluxes in growing biocatalytically active cells were significantly higher than proline hydroxylation rates. Remarkably, a catalysis-induced reduction of substrate uptake was observed, which correlated with reduced transcription of putA and putP, encoding proline dehydrogenase and the major proline transporter, respectively. These results provide evidence for a strong interference of catalytic activity with the regulation of proline uptake and metabolism. In terms of whole-cell biocatalyst efficiency, proline uptake and competition of P4H with proline catabolism are considered the most critical factors. PMID:23455348

Thermal Stability of Acetohydroxamic Acid/Nitric Acid Solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rudisill, T.S.

2002-03-13

The transmutation of transuranic actinides and long-lived fission products in spent commercial nuclear reactor fuel has been proposed as one element of the Advanced Accelerator Applications Program. Preparation of targets for irradiation in an accelerator-driven subcritical reactor would involve dissolution of the fuel and separation of uranium, technetium, and iodine from the transuranic actinides and other fission products. The UREX solvent extraction process is being developed to reject and isolate the transuranic actinides in the acid waste stream by scrubbing with acetohydroxamic acid (AHA). To ensure that a runaway reaction will not occur between nitric acid and AHA, an analoguemore » of hydroxyl amine, thermal stability tests were performed to identify if any processing conditions could lead to a runaway reaction.« less

Mucor hiemalis mediated 14α-hydroxylation on steroids: in vivo and in vitro investigations of 14α-hydroxylase activity.

PubMed

Kolet, Swati P; Haldar, Saikat; Niloferjahan, Siddiqui; Thulasiram, Hirekodathakallu V

2014-07-01

Transformation of testosterone and progesterone into synthetically challenging 14α-hydroxy derivatives was achieved by using fungal strain Mucor hiemalis. Prolonged incubation led to the formation of corresponding 6β/7α,14α-dihydroxy metabolites. The position and stereochemistry of newly introduced hydroxyl group was determined by detailed spectroscopic analyses. The time course experiment indicated that fungal strain initiated transformation by hydroxylation at 14α-position followed by at 6β- or 7α-positions. Studies using cell-free extracts suggest that the 14α-hydroxylase activity is NADPH dependent and belongs to the cytochrome P450 family. Copyright © 2014 Elsevier Inc. All rights reserved.

Hepatocellular carcinoma-targeted effect of configurations and groups of glycyrrhetinic acid by evaluation of its derivative-modified liposomes.

PubMed

Sun, Yuqi; Dai, Chunmei; Yin, Meilin; Lu, Jinghua; Hu, Haiyang; Chen, Dawei

2018-01-01

There are abundant glycyrrhetinic acid (GA) receptors on the cellular membrane of hepatocytes and hepatocellular carcinoma (HCC) cells. The receptor binding effect might be related to the structure of the guiding molecule. GA exists in two stereoisomers with C3-hydroxyl and C11-carbonyl active groups. The objective of this study was to investigate the relationship between the HCC-targeted effect and the configurations and groups of GA. Different GA derivatives (18β-GA, 18α-GA, 3-acetyl-18β-GA [3-Ace-GA] and 11-deoxy-18β-GA [11-Deo-GA]) were used to investigate the targeting effect of GA's configurations and groups on HCC cells. The EC 50 values of competition to binding sites and the ratio of specific binding in HepG2 cells showed that 18β-GA and 3-Ace-GA demonstrated significant competitive effect with fluorescein isothiocyanate (FITC)-labeled GA. Then, the GA derivatives were distearoyl-phosphatidylethanolamine (DSPE)-PEGylated. 18β-GA-, 18α-GA-, 3-Ace-GA-and 11-Deo-GA-modified liposomes were prepared and characterized by size, zeta potential, encapsulation efficiency, loading capacity, leakage and membrane stability. Evaluation on the cellular location in vitro and tumor targeting in vivo was carried out. Compared to common long-circulation liposome (PEG-Lip), more 18β-GA- and 3-Ace-GA-modified liposomes aggregated around HepG2 cells in vitro in short time and transferred into HCC tumors in vivo for a longer time. The β-configuration hydrogen atom on C18 position of GA played the most important role on the targeting effect. C11-carbonyl and C3-hydroxy groups of GA have certain and little influence on targeting action to HCC, respectively. In general, GA might be a promising targeting molecule for the research on liver diseases and hepatoma therapy.

Acid-catalyzed conversion of mono- and poly-sugars into platform chemicals: effects of molecular structure of sugar substrate.

PubMed

Hu, Xun; Wu, Liping; Wang, Yi; Song, Yao; Mourant, Daniel; Gunawan, Richard; Gholizadeh, Mortaza; Li, Chun-Zhu

2013-04-01

Hydrolysis/pyrolysis of lignocellulosic biomass always produces a mixture of sugars with distinct structures as intermediates or products. This study tried to elucidate the effects of molecular structure of sugars on their acid-catalyzed conversions in ethanol/water. Location of carbonyl group in sugars (fructose versus glucose) and steric configuration of hydroxyl groups (glucose versus galactose) significantly affected yields of levulinic acid/ester (fructose>glucose>galactose). The dehydration of fructose to 5-(hydroxymethyl)furfural produces much less soluble polymer than that from glucose and galactose, which results in high yields of levulinic acid/ester from fructose. Anhydrate sugar such as levoglucosan tends to undergo the undesirable decomposition to form less levulinic acid/ester. Catalytic behaviors of the poly-sugars (sucrose, maltose, raffinose, β-cyclodextrins) were determined much by their basic units. However, their big molecular sizes create the steric hindrance that significantly affects their followed conversion over solid acid catalyst. Copyright © 2013 Elsevier Ltd. All rights reserved.

The influence of NaCl on hydrophobicity of selected, pharmacologically active bile acids expressed with chromatographic retention index and critical micellar concentration.

PubMed

Posa, Mihalj; Pilipović, Ana; Lalić, Mladena

2010-11-01

Many of bile acids' (BA) physiological properties, as receptor binding, activation of ionic channels, binding to blood proteins, etc. are due to their hydrophobicity. On the other hand, hydrophobicity determines BAs' physico-chemical characteristics as micelle forming and adsorption (surface activity). However, BA hydrophobicity is not determined solely by their structure. Medium composition, especially the concentration of electrolytes has influence on BA hydrophobicity. Thus, the objective of this work was to examine the effect of NaCl on hydrophobicity of selected bile acids. This influence is specified with the retention factor k (reversed phase high pressure liquid chromatography (RPHPLC)) and critical micellar concentration (CMC) determined by non-invasive NMR method. The value of lnk elevates with the increase in mobile phase NaCl concentration i.e. Deltalnk/Deltac(NaCl) depends on the number of water molecules not stabilised by hydrogen bonds in bile acid hydration sheath. For bile acids that contain hydroxyl groups (except those with beta equatorial hydroxyl groups) the value of |DeltalnCMC/Deltac(NaCl)| rises with the increase in the number of non-stabilized water molecules in their hydration sheath. Even though oxo derivatives of cholic acid have similar chromatographic parameters they behave differently when it comes to CMC. In fact with the introduction of oxo groups the value of its |DeltalnCMC/Deltac(NaCl)| elevates but it results in a decrease in the number of non-stabilized water molecules i.e. hydrophobicity falls. Different behaviour of oxo derivatives implicate that, besides "hydrophobic interactions" in their micelles, there are also hydrogen bonds i.e. fiord effect exists. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Effects of surface hydroxylation on adhesion at zinc/silica interfaces.

PubMed

Le, Ha-Linh Thi; Goniakowski, Jacek; Noguera, Claudine; Koltsov, Alexey; Mataigne, Jean-Michel

2018-06-06

The weak interaction between zinc and silica is responsible for the poor performance of anti-corrosive galvanic zinc coatings on modern advanced high-strength steels, which are fundamental in the automotive industry, and important for rail transport, shipbuilding, and aerospace. With the goal of identifying possible methods for its improvement, we report an ab initio study of the effect of surface hydroxylation on the adhesion characteristics of model zinc/β-cristobalite interfaces, representative of various surface hydroxylation/hydrogenation conditions. We show that surface silanols resulting from dissociative water adsorption at the most stable stoichiometric (001) and (111) surfaces prevent strong zinc-silica interactions. However, dehydrogenation of such interfaces produces oxygen-rich zinc/silica contacts with excellent adhesion characteristics. These are due to partial zinc oxidation and the formation of strong iono-covalent Zn-O bonds between zinc atoms and the under-coordinated excess anions, remnant of the hydroxylation layer. Interestingly, these interfaces appear as the most thermodynamically stable in a wide range of realistic oxygen-rich and hydrogen-lean environments. We also point out that the partial oxidation of zinc atoms in direct contact with the oxide substrate may somewhat weaken the cohesion in the zinc deposit itself. This fundamental analysis of the microscopic mechanisms responsible for the improved zinc wetting on pre-hydroxylated silica substrates provides useful guidelines towards practical attempts to improve adhesion.

Electrochemiluminescence sensors for scavengers of hydroxyl radical based on its annihilation in CdSe quantum dots film/peroxide system.

PubMed

Jiang, Hui; Ju, Huangxian

2007-09-01

This work elucidated the detailed electrochemiluminescence (ECL) process of the thioglycolic acid-capped CdSe quantum dots (QDs) film/peroxide aqueous system. The QDs were first electrochemically reduced to form electrons-injected QDs approximately -1.1 V, which then reduced hydrogen peroxide to produce OH* radical. The intermediate OH* radical was a key species for producing holes-injected QDs. The ECL emission with a peak at -1.114 V was demonstrated to come from the 1Se-1Sh transition emission. Using thiol compounds as the model molecules to annihilate the OH* radical, their quenching effects on ECL emission were studied. This effect led to a novel strategy for ECL sensing of the scavengers of hydroxyl radical. The detection results of thiol compounds showed high sensitivity, good precision, and acceptable accuracy, suggesting the promising application of the proposed method for quick detection of both scavengers and generators of hydroxyl radical in different fields.

Side-chain hydroxylation in the metabolism of 8-aminoquinoline antiparasitic agents.

PubMed

Idowu, O R; Peggins, J O; Brewer, T G

1995-01-01

Primaquine, 8-(4-amino-1-methylbutylamino)-6-methoxyquinoline, is an antimalarial 8-aminoquinoline derivative. Although it has been in use since 1952, its metabolism has not been clearly defined. This is due to the instability of the expected aminophenol metabolites and their amphoteric nature, which makes their isolation difficult. Recent studies on the metabolism of WR 238605, a new primaquine analog, has shown that these problems may be solved by extracting the metabolites in the presence of ethyl chloroformate. Subsequent identification of the ethoxycarbonyl derivatives of the metabolites has made it possible to define the in vitro metabolism of primaquine. The primary metabolic pathways of primaquine involved hydroxylation of the phenyl ring of the quinoline nucleus and C-hydroxylation of the 3'-position of the 8-aminoalkylamino side chain. Ring-hydroxylation of primaquine gives rise to 5-hydroxyprimaquine, which on demethylation produces 5-hydroxy-6-demethylprimaquine. Side-chain hydroxylation of primaquine gives rise to 3'-hydroxyprimaquine, which also undergoes O-demethylation to 3'-hydroxy-6-demethylprimaquine. 6-Demethylprimaquine, a putative metabolite of primaquine, also underwent metabolism involving 3'-hydroxylation of the side chain. WR 6026, 8-(6-diethylaminohexylamino)-6-methoxy-4-methylquinoline, is an antileishmanial 8-aminoquinoline derivative. The in vitro metabolism of WR 6026 also results in the formation of side chain-oxygenated metabolites. The present results, together with previous observations on the metabolism of WR 238605 and closely related primaquine analog, suggest that side-chain oxygenation is an important metabolic pathway of antiparasitic 8-aminoquinoline compounds in general.

Organic acids influence iron uptake in the human epithelial cell line Caco-2.

PubMed

Salovaara, Susan; Sandberg, Ann-Sofie; Andlid, Thomas

2002-10-09

It has previously been suggested that organic acids enhance iron absorption. We have studied the effect of nine organic acids on the absorption of Fe(II) and Fe(III) in the human epithelial cell line Caco-2. The effect obtained was dose-dependent, and the greatest increase (43-fold) was observed for tartaric acid (4 mmol/L) on Fe(III) (10 micromol/L). Tartaric, malic, succinic, and fumaric acids enhanced Fe(II) and Fe(III) uptake. Citric and oxalic acid, on the other hand, inhibited Fe(II) uptake but enhanced Fe(III) uptake. Propionic and acetic acid increased the Fe(II) uptake, but had no effect on Fe(III) uptake. Our results show a correlation between absorption pattern and chemical structure; e.g. hydroxyl groups, in addition to carboxyls, were connected with a positive influence. The results may be important for elucidating factors affecting iron bioavailability in the small intestine and for the development of foods with improved iron bioavailability.

Enzymatic modification of chitosan by cinnamic acids: Antibacterial activity against Ralstonia solanacearum.

PubMed

Yang, Caifeng; Zhou, Yu; Zheng, Yu; Li, Changlong; Sheng, Sheng; Wang, Jun; Wu, Fuan

2016-06-01

This study aimed to identify chitosan polymers that have antibacterial activity against the bacterial wilt pathogen. The chitosan polymers were enzymatically synthesized using chitosan and five cinnamic acids (CADs): caffeic acid (CA), ferulic acid (FA), cinnamic acid (CIA), p-coumaric acid (COA) and chlorogenic acid (CHA), using laccase from Pleurotus ostreatus as a catalyst. The reaction was performed in a phosphate buffered solution under heterogenous reaction conditions. The chitosan derivatives (CTS-g-CADs) were characterized by FT-IR, XRD, TGA and SEM. FT-IR demonstrated that the reaction products bound covalently to the free amino groups or hydroxyl groups of chitosan via band of amide I or ester band. XRD showed a reduced packing density for grafted chitosan comparing to original chitosan. TGA demonstrated that CTS-g-CADs have a higher thermostability than chitosan. Additionally, chitosan and its derivatives showed similar antibacterial activity. However, the IC50 value of the chitosan-caffeic acid derivative (CTS-g-CA) against the mulberry bacterial wilt pathogen RS-5 was 0.23mg/mL, which was two-fifths of the IC50 value of chitosan. Therefore, the enzymatically synthesized chitosan polymers can be used to control plant diseases in biotechnological domains. Copyright © 2016 Elsevier B.V. All rights reserved.

Infrared spectroscopy of flavones and flavonols. Reexamination of the hydroxyl and carbonyl vibrations in relation to the interactions of flavonoids with membrane lipids

NASA Astrophysics Data System (ADS)

Baranović, Goran; Šegota, Suzana

2018-03-01

Detailed vibrational assignments for twelve flavonoids (seven flavones (flavone, 3- and 5-hydroxyflavone, chrysin, apigenin, fisetin and luteolin) and five flavonols (galangin, kaempferol, quercetin, morin and myricetin)) have been made based on own and reported experimental data and calculations at the B3LYP/6-31 + G(d,p) level of theory. All the molecules are treated in a uniform way by using the same set of redundancy-free set of internal coordinates. A generalized harmonic mode mixing is used to corroborate the vibrational characteristics of this important class of molecules. Each flavonoid molecule can be treated from the vibrational point of view as made of relatively weakly coupled chromone and phenyl part. It has been shown that the strongest band around 1600 cm- 1 need not be attributable to the Cdbnd O stretching. The way the vibrations of any of the hydroxyl groups are mixed with ring vibrations and vibrations of other neighboring hydroxyl groups is rather involved. This imposes severe limitations on any attempt to describe normal modes of a flavonol in terms of hydroxyl or carbonyl group vibrations. The role of water molecules in the appearance of flavonoid IR spectra is emphasized. Knowing for the great affinity of phosphate groups in lipids towards water, the immediate consequence is a reasonable assumption that flavonoid lipid interactions is mediated by water.

Two choices for the functionalization of silica nanoparticles with gallic acid: characterization of the nanomaterials and their antimicrobial activity against Paenibacillus larvae

NASA Astrophysics Data System (ADS)

Vico, Tamara A.; Arce, Valeria B.; Fangio, María F.; Gende, Liesel B.; Bertran, Celso A.; Mártire, Daniel O.; Churio, María S.

2016-11-01

Silica nanoparticles attached to gallic acid were synthesized from 7-nm diameter fumed silica particles by different functionalization methods involving the condensation of hydroxyl or carboxyl groups. The particles were characterized by thermal analyses and UV-vis, FTIR, NMR, and EPR spectroscopies. In comparison to free gallic acid, enhanced stability and increased antimicrobial activity against Paenibacillus larvae were found for the functionalized nanoparticles. Thus, both derivatization strategies result in improved properties of the natural polyphenol as antimicrobial agent for the treatment of honeybee pathologies.

Infrared spectroscopic studies of the effect of elevated temperature on the association of pyroglutamic acid with clay and other minerals

NASA Technical Reports Server (NTRS)

Macklin, J. W.; White, D. H.

1985-01-01

Fourier transform i.r. measurements of L-pyroglutamic acid dispersed in a matrix of a clay, silica or alumina have been obtained at various temperatures between 25 and 220 degrees C. The i.r. spectrum of L-pyroglutamic acid varies in a manner dependent upon the matrix material and shows considerable change as the temperature of the mixtures is increased. The differences in the spectrum at elevated temperatures are explained in terms of a chemical reaction between hydroxyl groups in the matrix and the carboxylic acid. The i.r. spectra of trimethylsilyl derivatives of L-pyroglutamic acid and aluminum pyroglutamate were also measured to assist the understanding of spectra and interpretation of the spectral changes dependent upon increasing temperature.

Genetics Home Reference: fatty acid hydroxylase-associated neurodegeneration

MedlinePlus

... Certain 2-hydroxylated fatty acids are important in forming normal myelin; myelin is the protective covering that ... C, Alshehhi AA, Proukakis C, Sibtain NA, Maier H, Sharifi R, Patton MA, Bashir W, Koul R, ...

Production of the catalytic core of human peptidylglycine α-hydroxylating monooxygenase (hPHMcc) in Escherichia coli

PubMed Central

Handa, Sumit; Spradling, Tyler J.; Dempsey, Daniel R.; Merkler, David J.

2013-01-01

Most mammalian bioactive peptides possess a C-terminal amino acid amide moiety. The presence of the C-terminal amide is a significant impediment to the recombinant production of α-amidated peptides. α-Amidated peptides are produced in vivo by the enzymatic cleavage of a precursor with a C-terminal glycine residue. Peptidylglycine α-hydroxylating monooxygenase catalyzes the key step in the oxidation of the glycine-extended precursors to the α-amidated peptide. Herein, we detail the production of the catalytic core of human peptidylglycine α-hydroxylating monooxygenase (hPHMcc) in Escherichia coli possessing a N-terminal fusion to thioredoxin (Trx). Trx was fused to hPHMcc to enhance the yield of the resulting 52 kDa protein as a soluble and catalytically active enzyme. The Trx-hPHMcc-His6 fusion was purified to homogeneity and exhibited steady-state kinetic parameters that were similar to purified rat PHMcc. The bacterial production of recombinant hPHMcc will foster efforts to generate α-amidated peptides by the co-expression of hPHMcc and the α-amidated peptide precursors in E. coli or the in vitro amidation of recombinantly expressed α-amidated peptide precursors. PMID:22554821

Organic Acid Production by Filamentous Fungi

DOE Office of Scientific and Technical Information (OSTI.GOV)

Magnuson, Jon K.; Lasure, Linda L.

-scale processes for fungal organic acid production. The second presents a detailed review of current knowledge of the biochemistry and genetic regulation of organic acid biosynthesis. The organic acids considered are limited to polyfunctional acids containing one or more carboxyl groups, hydroxyl groups, or both, that are closely tied to central metabolic pathways. A major objective of the review is to link the biochemistry of organic acid production to the available genomic data.« less

A novel asymmetric chair-like hydroxyl-bridged tetra-copper compound: Synthesis, supramolecular structure and magnetic property

NASA Astrophysics Data System (ADS)

Wang, Xiao-Feng; Du, Ke-Jie; Wang, Hong-Qing; Zhang, Xue-Li; Nie, Chang-Ming

2017-06-01

A new polynuclear Cu(II) compound, [Cu4(bpy)4(OH)4(H2O)(BTC)]NO3·8H2O (1), was prepared by self-assembly from the solution of copper(II) nitrate and two kinds of ligands, 2,2‧-bipyridine (bpy) and benzene-tricarboxylic acid (H3BTC). Single crystal structure analysis reveals that 1 features a rare asymmetric chair-like hydroxyl-bridged tetra-copper cluster: [Cu4(OH)4] core along with one H2O and one BTC3- occupied each terminal coordinated site. In addition, the magnetic property has been investigated.

Regioselective hydroxylation of isoflavones by Streptomyces avermitilis MA-4680.

PubMed

Roh, Changhyun; Seo, Su-Hyun; Choi, Kwon-Young; Cha, Minho; Pandey, Bishnu Prasad; Kim, June-Hyung; Park, Jun-Seong; Kim, Duck Hee; Chang, Ih Seop; Kim, Byung-Gee

2009-07-01

Screening of bacterial whole cells was performed for regioselective hydroxylation of daidzein and genistein. Among the strains examined, Streptomyces avermitilis MA-4680 showed high ortho-dihydroxylation activity to produce 3',4',7-trihydroxyisoflavone and 3',4',5,7-tetrahydroxyisoflavone from daidzein (4',7-dihydroxyisoflavone) and genistein (4',5,7-trihydroxyisoflavone), respectively. Using 100 mg cells (wet wt.) and 1% (v/v) Triton X100 in 1 ml of total reaction volume, where 100 microl of the substrate solution (0.5 mM in 10% (v/v) mixed solvent of DMSO:MeOH = 3:7) was added to 900 microl of potassium phosphate buffer (100 mM, pH 7.2), a 16% molar conversion yield of 3',4',7-trihydroxyisoflavone was obtained from 0.5 mM daidzein after 24 h of reaction time at 28 degrees C and 200 rpm. Ketoconazole significantly (ca. 90%) inhibited the ortho-hydroxylation activity of daidzein, suggesting that cytochrome P450 enzymes putatively play roles in regiospecific daidzein hydroxylation. The analysis of the reaction products was determined by gas chromatography/mass spectrometry (GC/MS) and (1)H NMR.

Monkey liver cytochrome P450 2C19 is involved in R- and S-warfarin 7-hydroxylation.

PubMed

Hosoi, Yoshio; Uno, Yasuhiro; Murayama, Norie; Fujino, Hideki; Shukuya, Mitsunori; Iwasaki, Kazuhide; Shimizu, Makiko; Utoh, Masahiro; Yamazaki, Hiroshi

2012-12-15

Cynomolgus monkeys are widely used as primate models in preclinical studies. However, some differences are occasionally seen between monkeys and humans in the activities of cytochrome P450 enzymes. R- and S-warfarin are model substrates for stereoselective oxidation in humans. In this current research, the activities of monkey liver microsomes and 14 recombinantly expressed monkey cytochrome P450 enzymes were analyzed with respect to R- and S-warfarin 6- and 7-hydroxylation. Monkey liver microsomes efficiently mediated both R- and S-warfarin 7-hydroxylation, in contrast to human liver microsomes, which preferentially catalyzed S-warfarin 7-hydroxylation. R-Warfarin 7-hydroxylation activities in monkey liver microsomes were not inhibited by α-naphthoflavone or ketoconazole, and were roughly correlated with P450 2C19 levels and flurbiprofen 4-hydroxylation activities in microsomes from 20 monkey livers. In contrast, S-warfarin 7-hydroxylation activities were not correlated with the four marker drug oxidation activities used. Among the 14 recombinantly expressed monkey P450 enzymes tested, P450 2C19 had the highest activities for R- and S-warfarin 7-hydroxylations. Monkey P450 3A4 and 3A5 slowly mediated R- and S-warfarin 6-hydroxylations. Kinetic analysis revealed that monkey P450 2C19 had high V(max) and low K(m) values for R-warfarin 7-hydroxylation, comparable to those for monkey liver microsomes. Monkey P450 2C19 also mediated S-warfarin 7-hydroxylation with V(max) and V(max)/K(m) values comparable to those for recombinant human P450 2C9. R-warfarin could dock favorably into monkey P450 2C19 modeled. These results collectively suggest high activities for monkey liver P450 2C19 toward R- and S-warfarin 6- and 7-hydroxylation in contrast to the saturation kinetics of human P450 2C9-mediated S-warfarin 7-hydroxylation. Copyright © 2012 Elsevier Inc. All rights reserved.

Abscisic Acid Biosynthesis in Leaves and Roots of Xanthium strumarium.

PubMed

Creelman, R A; Gage, D A; Stults, J T; Zeevaart, J A

1987-11-01

RESEARCH ON THE BIOSYNTHESIS OF ABSCISIC ACID (ABA) HAS FOCUSED PRIMARILY ON TWO PATHWAYS: (a) the direct pathway from farnesyl pyrophosphate, and (b) the indirect pathway involving a carotenoid precursor. We have investigated which biosynthetic pathway is operating in turgid and stressed Xanthium leaves, and in stressed Xanthium roots using long-term incubations in (18)O(2). It was found that in stressed leaves three atoms of (18)O from (18)O(2) are incorporated into the ABA molecule, and that the amount of (18)O incorporated increases with time. One (18)O atom is incorporated rapidly into the carboxyl group of ABA, whereas the other two atoms are very slowly incorporated into the ring oxygens. The fourth oxygen atom in the carboxyl group of ABA is derived from water. ABA from stressed roots of Xanthium incubated in (18)O(2) shows a labeling pattern similar to that of ABA in stressed leaves, but with incorporation of more (18)O into the tertiary hydroxyl group at C-1' after 6 and 12 hours than found in ABA from stressed leaves. It is proposed that the precursors to stress-induced ABA are xanthophylls, and that a xanthophyll lacking an oxygen function at C-6 (carotenoid numbering scheme) plays a crucial role in ABA biosynthesis in Xanthium roots. In turgid Xanthium leaves, (18)O is incorporated into ABA to a much lesser extent than it is in stressed leaves, whereas exogenously applied (14)C-ABA is completely catabolized within 48 hours. This suggests that ABA in turgid leaves is either (a) made via a biosynthetic pathway which is different from the one in stressed leaves, or (b) has a half-life on the order of days as compared with a half-life of 15.5 hours in water-stressed Xanthium leaves. Phaseic acid showed a labeling pattern similar to that of ABA, but with an additional (18)O incorporated during 8'-hydroxylation of ABA to phaseic acid.

Aspartic acid based nucleoside phosphoramidate prodrugs as potent inhibitors of hepatitis C virus replication.

PubMed

Maiti, Munmun; Maiti, Mohitosh; Rozenski, Jef; De Jonghe, Steven; Herdewijn, Piet

2015-05-14

In view of a persistent threat to mankind, the development of nucleotide-based prodrugs against hepatitis C virus (HCV) is considered as a constant effort in many medicinal chemistry groups. In an attempt to identify novel nucleoside phosphoramidate analogues for improving the anti-HCV activity, we have explored, for the first time, aspartic acid (Asp) and iminodiacetic acid (IDA) esters as amidate counterparts by considering three 2'-C-methyl containing nucleosides, 2'-C-Me-cytidine, 2'-C-Me-uridine and 2'-C-Me-2'-fluoro-uridine. Synthesis of these analogues required protection for the vicinal diol functionality of the sugar moiety and the amino group of the cytidine nucleoside to regioselectively perform phosphorylation reaction at the 5'-hydroxyl group. Anti-HCV data demonstrate that the Asp-based phosphoramidates are ∼550 fold more potent than the parent nucleosides. The inhibitory activity of the Asp-ProTides was higher than the Ala-ProTides, suggesting that Asp would be a potential amino acid candidate to be considered for developing novel antiviral prodrugs.

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

PubMed

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

2015-10-12

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

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.

Photo-Fenton-assisted ozonation of p-Coumaric acid in aqueous solution.

PubMed

Monteagudo, J M; Carmona, M; Durán, A

2005-08-01

The degradation of p-Coumaric acid present in olive oil mill wastewater was investigated as a pretreatment stage to obtain more easily biodegradable molecules, with lower toxicity that facilitates subsequent anaerobic digestion. Thus, photo-Fenton-assisted ozonation has been studied and compared with ozonation at alkaline pH and conventional single ultraviolet (UV) and acid ozonation treatments. In the combined process, the overall kinetic rate constant was split into various components: direct oxidation by UV light, direct oxidation by ozone and oxidation by hydroxyl radicals. Molecular and/or radical ozone reaction was studied by conducting the reaction in the presence and absence of tert-butylalcohol at pHs 2, 7 and 9. Ozone oxidation rate increases with pH or by the addition of Fenton reagent and/or UV radiation due to generation of hydroxyl radicals, *OH. Hydrogen peroxide and ferrous ion play a double role during oxidation since at low concentrations they act as initiators of hydroxyl radicals but at high concentrations they act as radical scavengers. Finally, the additional levels of degradation by formation of hydroxyl radicals have been quantified in comparison to the conventional single processes and an equation is proposed for the reaction rate as a function of studied operating variables.

Generation of hydroxyl radicals and singlet oxygen during oxidation of rhododendrol and rhododendrol-catechol.

PubMed

Miyaji, Akimitsu; Gabe, Yu; Kohno, Masahiro; Baba, Toshihide

2017-03-01

The generation of hydroxyl radicals and singlet oxygen during the oxidation of 4-(4-hydroxyphenyl)-2-butanol (rhododendrol) and 4-(3,4-dihydroxyphenyl)-2-butanol (rhododendrol-catechol) with mushroom tyrosinase in a phosphate buffer (pH 7.4) was examined as the model for the reactive oxygen species generation via the two rhododendrol compounds in melanocytes. The reaction was performed in the presence of 5,5-dimethyl-1-pyrroline- N -oxide (DMPO) spin trap reagents for hydroxyl radical or 2,2,6,6-tetramethyl-4-piperidone (4-oxo-TEMP), an acceptor of singlet oxygen, and their electron spin resonances were measured. An increase in the electron spin resonances signal attributable to the adduct of DMPO reacting with the hydroxyl radical and that of 4-oxo-TEMP reacting with singlet oxygen was observed during the tyrosinase-catalyzed oxidation of rhododendrol and rhododendrol-catechol, indicating the generation of hydroxyl radical and singlet oxygen. Moreover, hydroxyl radical generation was also observed in the autoxidation of rhododendrol-catechol. We show that generation of intermediates during tyrosinase-catalyzed oxidation of rhododendrol enhances oxidative stress in melanocytes.

Physical and structural characterisation of starch/polyester blends with tartaric acid.

PubMed

Olivato, J B; Müller, C M O; Carvalho, G M; Yamashita, F; Grossmann, M V E

2014-06-01

Starch/PBAT blends were produced by reactive extrusion with tartaric acid (TA) as an additive. The effects of TA, glycerol and starch+PBAT on the mechanical, optical and structural properties of the films were evaluated, with formulations based in a constrained mixture design. Tartaric acid acts as a compatibiliser and promotes the acid hydrolysis of starch chains. These two functions explain the observed film resistance and opacity. TA reduced the weight loss in water. Scanning electron microscopy (SEM) images showed that TA reduces the interfacial tension between the polymeric phases, resulting in more homogeneous films. Nuclear magnetic resonance ((13)C CPMAS) and Fourier transform infrared spectroscopy (FT-IR) suggest that tartaric acid is able to react with the hydroxyl groups of the starch by esterification/transesterification reactions, confirming its role as a compatibiliser. The addition of TA results in materials with better properties that are suitable for use in food packaging. Published by Elsevier B.V.

QSPR prediction of the hydroxyl radical rate constant of water contaminants.

PubMed

Borhani, Tohid Nejad Ghaffar; Saniedanesh, Mohammadhossein; Bagheri, Mehdi; Lim, Jeng Shiun

2016-07-01

In advanced oxidation processes (AOPs), the aqueous hydroxyl radical (HO) acts as a strong oxidant to react with organic contaminants. The hydroxyl radical rate constant (kHO) is important for evaluating and modelling of the AOPs. In this study, quantitative structure-property relationship (QSPR) method is applied to model the hydroxyl radical rate constant for a diverse dataset of 457 water contaminants from 27 various chemical classes. The constricted binary particle swarm optimization and multiple-linear regression (BPSO-MLR) are used to obtain the best model with eight theoretical descriptors. An optimized feed forward neural network (FFNN) is developed to investigate the complex performance of the selected molecular parameters with kHO. Although the FFNN prediction results are more accurate than those obtained using BPSO-MLR, the application of the latter is much more convenient. Various internal and external validation techniques indicate that the obtained models could predict the logarithmic hydroxyl radical rate constants of a large number of water contaminants with less than 4% absolute relative error. Finally, the above-mentioned proposed models are compared to those reported earlier and the structural factors contributing to the AOP degradation efficiency are discussed. Copyright © 2016 Elsevier Ltd. All rights reserved.

Enhanced hydroxyl radical production by dihydroxybenzene-driven Fenton reactions: implications for wood biodegradation.

PubMed

Contreras, David; Rodríguez, Jaime; Freer, Juanita; Schwederski, Brigitte; Kaim, Wolfgang

2007-09-01

Brown rot fungi degrade wood, in initial stages, mainly through hydroxyl radicals (.OH) produced by Fenton reactions. These Fenton reactions can be promoted by dihydroxybenzenes (DHBs), which can chelate and reduce Fe(III), increasing the reactivity for different substrates. This mechanism allows the extensive degradation of carbohydrates and the oxidation of lignin during wood biodegradation by brown rot fungi. To understand the enhanced reactivity in these systems, kinetics experiments were carried out, measuring .OH formation by the spin-trapping technique of electron paramagnetic resonance spectroscopy. As models of the fungal DHBs, 1,2-dihydroxybenzene (catechol), 2,3-dihydroxybenzoic acid and 3,4-dihydroxybenzoic acid were utilized as well as 1,2-dihydroxy-3,5-benzenedisulfonate as a non-Fe(III)-reducing substance for comparison. Higher amounts and maintained concentrations of .OH were observed in the driven Fenton reactions versus the unmodified Fenton process. A linear correlation between the logarithms of complex stability constants and the .OH production was observed, suggesting participation of such complexes in the radical production.

Detection of Hydroxyl and Perhydroxyl Radical Generation from Bleaching Agents with Nuclear Magnetic Resonance Spectroscopy.

PubMed

Sharma, Himanshu; Sharma, Divya S

Children/adolescent's orodental structures are different in anatomy and physiology from that of adults, therefore require special attention for bleaching with oxidative materials. Hydroxyl radical (OH . ) generation from bleaching agents has been considered directly related to both its clinical efficacy and hazardous effect on orodental structures. Nonetheless bleaching agents, indirectly releasing hydrogen peroxide (H 2 O 2 ), are considered safer yet clinically efficient. Apart from OH . , perhydroxyl radicals (HO 2 . ) too, were detected in bleaching chemistry but not yet in dentistry. Therefore, the study aims to detect the OH . and HO 2 . from bleaching agents with their relative integral value (RIV) using 31 P nuclear magnetic resonance ( 31 PNMR) spectroscope. Radicals were generated with UV light in 30% H 2 O 2 , 35% carbamide peroxide (CP), sodium perborate tetrahydrate (SPT) and; neutral and alkaline 30% H 2 O 2 . Radicals were spin-trapped with DIPPMPO in NMR tubes for each test agents as a function of time (0, 1, 2, 3min) at their original pH. Peaks were detected for OH . and HO 2 . on NMR spectrograph. RIV were read and compared for individual radicals detected. Only OH . were detected from acidic and neutral bleaching agent (30% acidic and neutral H 2 O 2 , 35%CP); both HO 2 . and OH . from 30% alkaline H 2 O 2 ; while only HO 2 . from more alkaline SPT. RIV for OH . was maximum at 1min irradiation of acidic 30%H 2 O 2 and 35%CP and minimum at 1min irradiation of neutral 30%H 2 O 2 . RIV for HO 2 . was maximum at 0min irradiation of alkaline 30%H 2 O 2 and minimum at 2min irradiation of SPT. The bleaching agents having pH- neutral and acidic were always associated with OH . ; weak alkaline with both OH . and HO 2 . ; and strong alkaline with HO 2 . only. It is recommended to check the pH of the bleaching agents and if found acidic, should be made alkaline to minimize oxidative damage to enamel itself and then to pulp/periodontal tissues. H 2 O 2

Non-hydroxyl radical mediated photochemical processes for dye degradation.

PubMed

Liu, Xitong; Song, Xiaojie; Zhang, Shujuan; Wang, Mengshu; Pan, Bingcai

2014-04-28

Using solar energy for the decontamination of wastewater is a promising solution to the water-energy nexus. Current advanced oxidation processes have an unsatisfactory efficiency in the treatment of dye wastewater due to the non-selectivity of hydroxyl radicals. More efficient photochemical approaches for dye degradation are highly needed. Three diketones, biacetyl, acetylacetone, and acetonylacetone, were proven to be potent activators for the photodecoloration of azo, triarylmethane and anthraquinone dyes. The photodegradation kinetics of Acid Orange 7 in the UV/diketone processes was much faster than that in the UV/H2O2 system. Photo-induced energy and electron transfer were possible mechanisms for dye degradation in the diketone systems. Adducts of dye and acetylacetone were identified, indicating a unique dye degradation route through adduct formation and decomposition. Unlike acting only as the target substrate of ˙OH in advanced oxidation processes, the dyes played vital roles in the UV/diketone processes. The findings here provide new insights for designing more efficient technologies for environmental remediation, based on diketone photochemistry.

Formation of hydroxyl-functionalized stilbenoid molecular sieves at the liquid/solid interface on top of a 1-decanol monolayer.

PubMed

Bellec, Amandine; Arrigoni, Claire; Douillard, Ludovic; Fiorini-Debuisschert, Céline; Mathevet, Fabrice; Kreher, David; Attias, André-Jean; Charra, Fabrice

2014-10-31

Specific molecular tectons can be designed to form molecular sieves through self-assembly at the solid-liquid interface. After demonstrating a model tecton bearing apolar alkyl chains, we then focus on a modified structure involving asymmetric functionalization of some alkyl chains with polar hydroxyl groups in order to get chemical selectivity in the sieving. As the formation of supramolecular self-assembled networks strongly depends on molecule-molecule, molecule-substrate and molecule-solvent interactions, we compared the tectons' self-assembly on graphite for two types of solvent. We demonstrate the possibility to create hydroxylated stilbenoid molecular sieves by using 1-decanol as a solvent. Interestingly, with this solvent, the porous network is developed on top of a 1-decanol monolayer.

Impact of Ti Incorporation on Hydroxylation and Wetting of Fe 3 O 4

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stoerzinger, Kelsey A.; Pearce, Carolyn I.; Droubay, Timothy C.

2017-08-24

Understanding the interaction of water with compositionally tuned metal oxides is central to exploiting their unique catalytic and magnetic properties. However, processes such as hydroxylation, wetting, and resulting changes in electronic structure at ambient conditions are challenging to probe in situ. Here, we examine the hydroxylation and wetting of Fe(3-x)TixO4 epitaxial films directly using ambient pressure X-ray photoelectron spectroscopy under controlled relative humidity. Fe2+ formation promoted by Ti4+ substitution for Fe3+ increases with hydroxylation, commensurate with a decrease in the surface work function or change in the surface dipole. The incorporation of small amounts of Ti (x=0.25) as a bulkmore » dopant dramatically impacts hydroxylation, in part due to surface segregation, leading to coverages closer to that of TiO2 than Fe3O4. However, the Fe(3-x)TixO4 compositional series shows a similar affinity for water physisorption, which begins at notably lower relative humidity than on TiO2. The findings suggest that relative humidity rather than surface hydroxyl density controls wettability. Studies of this kind directly relate to rational design of doped magnetite into more active catalysts for UV/Fenton degradation, the adsorption of contaminants, and the development of spin filters.« less

Physicochemical and Mechanical Properties of Bambara Groundnut Starch Films Modified with Stearic Acid.

PubMed

Oyeyinka, Samson A; Singh, Suren; Amonsou, Eric O

2017-01-01

The physicochemical and mechanical properties of biofilm prepared from bambara starch modified with varying concentrations of stearic acid (0%, 2.5%, 3.5%, 5%, 7%, and 10%) were studied. By scanning electron microscopy, bambara starch films modified with stearic acid (≥3.5%) showed a progressively rough surface compared to those with 2.5% stearic acid and the control. Fourier transform infrared spectroscopy spectra revealed a peak shift of approximately 31 cm -1 , suggesting the promotion of hydrogen bond formation between hydroxyl groups of starch and stearic acid. The addition of 2.5% stearic acid to bambara starch film reduced water vapor permeability by approximately 17%. Bambara starch films modified with higher concentration of stearic acid were more opaque and showed significantly high melting temperatures. However, mechanical properties of starch films were generally negatively affected by stearic acid. Bambara starch film may be modified with 2.5% stearic acid for improved water vapor permeability and thermal stability with minimal effect on tensile strength. © 2016 Institute of Food Technologists®.

Role of oxygen functional groups in reduced graphene oxide for lubrication

PubMed Central

Gupta, Bhavana; Kumar, Niranjan; Panda, Kalpataru; Kanan, Vigneshwaran; Joshi, Shailesh; Visoly-Fisher, Iris

2017-01-01

Functionalized and fully characterized graphene-based lubricant additives are potential 2D materials for energy-efficient tribological applications in machine elements, especially at macroscopic contacts. Two different reduced graphene oxide (rGO) derivatives, terminated by hydroxyl and epoxy-hydroxyl groups, were prepared and blended with two different molecular weights of polyethylene glycol (PEG) for tribological investigation. Epoxy-hydroxyl-terminated rGO dispersed in PEG showed significantly smaller values of the friction coefficient. In this condition, PEG chains intercalate between the functionalized graphene sheets, and shear can take place between the PEG and rGO sheets. However, the friction coefficient was unaffected when hydroxyl-terminated rGO was coupled with PEG. This can be explained by the strong coupling between graphene sheets through hydroxyl units, causing the interaction of PEG with the rGO to be non- effective for lubrication. On the other hand, antiwear properties of hydroxyl-terminated rGO were significantly enhanced compared to epoxy-hydroxyl functionalized rGO due to the integrity of graphene sheet clusters. PMID:28344337

Applying AFM-based nanofabrication for measuring the thickness of nanopatterns: the role of head groups in the vertical self-assembly of omega-functionalized n-alkanethiols.

PubMed

Kelley, Algernon T; Ngunjiri, Johnpeter N; Serem, Wilson K; Lawrence, Steve O; Yu, Jing-Jiang; Crowe, William E; Garno, Jayne C

2010-03-02

Molecules of n-alkanethiols with methyl head groups typically form well-ordered monolayers during solution self-assembly for a wide range of experimental conditions. However, we have consistently observed that, for either carboxylic acid or thiol-terminated n-alkanethiols, under certain conditions nanografted patterns are generated with a thickness corresponding precisely to a double layer. To investigate the role of head groups for solution self-assembly, designed patterns of omega-functionalized n-alkanethiols were nanografted with systematic changes in concentration. Nanografting is an in situ approach for writing patterns of thiolated molecules on gold surfaces by scanning with an AFM tip under high force, accomplished in dilute solutions of desired ink molecules. As the tip is scanned across the surface of a self-assembled monolayer under force, the matrix molecules are displaced from the surface and are immediately replaced with fresh molecules from solution to generate nanopatterns. In this report, side-by-side comparison of nanografted patterns is achieved for different matrix molecules using AFM images. The chain length and head groups (i.e., carboxyl, hydroxyl, methyl, thiol) were varied for the nanopatterns and matrix monolayers. Interactions such as head-to-head dimerization affect the vertical self-assembly of omega-functionalized n-alkanethiol molecules within nanografted patterns. At certain threshold concentrations, double layers were observed to form when nanografting with head groups of carboxylic acid and dithiols, whereas single layers were generated exclusively for nanografted patterns with methyl and hydroxyl groups, regardless of changes in concentration.

Heterogeneous kinetics, products, and mechanisms of ferulic acid particles in the reaction with NO3 radicals

NASA Astrophysics Data System (ADS)

Liu, Changgeng; Zhang, Peng; Wen, Xiaoying; Wu, Bin

2017-03-01

Methoxyphenols, as an important component of wood burning, are produced by lignin pyrolysis and considered to be the potential tracers for wood smoke emissions. In this work, the heterogeneous reaction between ferulic acid particles and NO3 radicals was investigated. Six products including oxalic acid, 4-vinylguaiacol, vanillin, 5-nitrovanillin, 5-nitroferulic acid, and caffeic acid were confirmed by gas chromatography-mass spectrometry (GC-MS). In addition, the reaction mechanisms were proposed and the main pathways were NO3 electrophilic addition to olefin and the meta-position to the hydroxyl group. The uptake coefficient of NO3 radicals on ferulic acid particles was 0.17 ± 0.02 and the effective rate constant under experimental conditions was (1.71 ± 0.08) × 10-12 cm3 molecule-1 s-1. The results indicate that ferulic acid degradation by NO3 can be an important sink at night.

Density functional study of the adsorption of aspirin on the hydroxylated (0 0 1) α-quartz surface

NASA Astrophysics Data System (ADS)

Abbasi, A.; Nadimi, E.; Plänitz, P.; Radehaus, C.

2009-08-01

In this study the adsorption geometry of aspirin molecule on a hydroxylated (0 0 1) α-quartz surface has been investigated using DFT calculations. The optimized adsorption geometry indicates that both, adsorbed molecule and substrate are strongly deformed. Strong hydrogen bonding between aspirin and surface hydroxyls, leads to the breaking of the original hydroxyl-hydroxyl hydrogen bonds (Hydrogenbridges) on the surface. In this case new hydrogen bonds on the hydroxylated (0 0 1) α-quartz surface appear which significantly differ from those at the clean surface. The 1.11 eV adsorption energy reveals that the interaction of aspirin with α-quartz is an exothermic chemical interaction.

Substitution effect on a hydroxylated chalcone: Conformational, topological and theoretical studies

NASA Astrophysics Data System (ADS)

Custodio, Jean M. F.; Vaz, Wesley F.; de Andrade, Fabiano M.; Camargo, Ademir J.; Oliveira, Guilherme R.; Napolitano, Hamilton B.

2017-05-01

The effect of substituents on two hydroxylated chalcones was studied in this work. The first chalcone, with a dimethylamine group (HY-DAC) and the second, with three methoxy groups (HY-TRI) were synthesized and crystallized from ethanol on centrosymmetric space group P21/c. The geometric parameters and supramolecular arrangement for both structures obtained from single crystal X-ray diffraction data were analyzed. The intermolecular interactions were investigated by Hirshfeld surfaces with their respective 2D plot for quantification of each type of contact. Additionally, the observed interactions were characterized by QTAIM analysis, and DFT calculations were applied for theoretical vibrational spectra, localization and quantification of frontier orbitals and potential electrostatic map. The flatness of both structures was affected by the substituents, which led to different monoclinic crystalline packing. The calculated harmonic vibrational frequencies and homo-lumo gap confirmed the stability of the structures, while intermolecular interactions were confirmed by potential electrostatic map and QTAIM analysis.

LABORATORY STUDIES ON THE FORMATION OF FORMIC ACID (HCOOH) IN INTERSTELLAR AND COMETARY ICES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bennett, Chris J.; Kim, Yong Seol; Kaiser, Ralf I.

2011-01-20

Mixtures of water (H{sub 2}O) and carbon monoxide (CO) ices were irradiated at 10 K with energetic electrons to simulate the energy transfer processes that occur in the track of galactic cosmic-ray particles penetrating interstellar ices. We identified formic acid (HCOOH) through new absorption bands in the infrared spectra at 1690 and 1224 cm{sup -1} (5.92 and 8.17 {mu}m, respectively). During the subsequent warm-up of the irradiated samples, formic acid is evident from the mass spectrometer signal at the mass-to-charge ratio, m/z = 46 (HCOOH{sup +}) as the ice sublimates. The detection of formic acid was confirmed using isotopically labeledmore » water-d2 with carbon monoxide, leading to formic acid-d2 (DCOOD). The temporal fits of the reactants, reaction intermediates, and products elucidate two reaction pathways to formic acid in carbon monoxide-water ices. The reaction is induced by unimolecular decomposition of water forming atomic hydrogen (H) and the hydroxyl radical (OH). The dominating pathway to formic acid (HCOOH) was found to involve addition of suprathermal hydrogen atoms to carbon monoxide forming the formyl radical (HCO); the latter recombined with neighboring hydroxyl radicals to yield formic acid (HCOOH). To a lesser extent, hydroxyl radicals react with carbon monoxide to yield the hydroxyformyl radical (HOCO), which recombined with atomic hydrogen to produce formic acid. Similar processes are expected to produce formic acid within interstellar ices, cometary ices, and icy satellites, thus providing alternative processes for the generation of formic acid whose abundance in hot cores such as Sgr-B2 cannot be accounted for solely by gas-phase chemistry.« less

Acid Stress Response Mechanisms of Group B Streptococci

PubMed Central

Shabayek, Sarah; Spellerberg, Barbara

2017-01-01

Group B streptococcus (GBS) is a leading cause of neonatal mortality and morbidity in the United States and Europe. It is part of the vaginal microbiota in up to 30% of pregnant women and can be passed on to the newborn through perinatal transmission. GBS has the ability to survive in multiple different host niches. The pathophysiology of this bacterium reveals an outstanding ability to withstand varying pH fluctuations of the surrounding environments inside the human host. GBS host pathogen interations include colonization of the acidic vaginal mucosa, invasion of the neutral human blood or amniotic fluid, breaching of the blood brain barrier as well as survival within the acidic phagolysosomal compartment of macrophages. However, investigations on GBS responses to acid stress are limited. Technologies, such as whole genome sequencing, genome-wide transcription and proteome mapping facilitate large scale identification of genes and proteins. Mechanisms enabling GBS to cope with acid stress have mainly been studied through these techniques and are summarized in the current review PMID:28936424

Sensitive determination of endogenous hydroxyl radical in live cell by a BODIPY based fluorescent probe.

PubMed

Lei, Kepeng; Sun, Mingtai; Du, Libo; Zhang, Xiaojie; Yu, Huan; Wang, Suhua; Hayat, Tasawar; Alsaedi, Ahmed

2017-08-01

The sensitive and selective fluorescence probe for hydroxyl radical analysis is of significance because hydroxyl radical plays key roles in many physiological and pathological processes. In this work, a novel organic fluorescence molecular probe OHP for hydroxyl radical is synthesized by a two-step route. The probe employs 4-bora-3a,4a-diaza-s-indacene (difluoroboron dipyrromethene, BODIPY) as the fluorophore and possesses relatively high fluorescence quantum yields (77.14%). Hydroxyl radical can rapidly react with the probe and quench the fluorescence in a good linear relationship (R 2 =0.9967). The limit of detection is determined to be as low as 11nM. In addition, it has been demonstrated that the probe has a good stability against pH and light illumination, low cytotoxicity and high biocompatibility. Cell culture experimental results show that the probe OHP is sensitive and selective for imaging and tracking endogenous hydroxyl radical in live cells. Copyright © 2017 Elsevier B.V. All rights reserved.

The effects of hydroxy fatty acids on the hyphal branching of germinated spores of AM fungi.

PubMed

Nagahashi, Gerald; Douds, David D

2011-01-01

Two hydroxy fatty acids, tentatively identified previously in carrot root exudates, were tested for their effects on hyphal growth of the arbuscular mycorrhizal (AM) fungus, Gigaspora gigantea (Nicol. and Gerd.) Gerdemann and Trappe. Best results were achieved with a long-term bioassay (7-8d) with nanomolar concentrations throughout the Petri dish in contrast to the rapid microinjection bioassay (16-24h) in which nanogram quantities were injected near growing hyphal tips. When 5nM 2-hydroxy fatty acids of various chain length were tested, the length of the hydroxyl fatty acid was significant since only 2-hydroxytetradecanoic acid (2OH-TDA) and to a slightly lesser degree, 2-hydroxydodecanoic acid (2OH-DDA) induced a hyphal growth response while 2-hydroxydecanoic acid (2OH-DA) and 2-hydroxyhexadecanoic (2OH-HDA) acid did not. The position of the hydroxyl group was critical since 5nM 3-hydroxytetradecanoic acid (3OH-TDA) had no effect on hyphal growth. The length of the non-hydroxy containing straight chain fatty acid, per se, did not appear significant since none of these fatty acids had an effect on hyphal growth. The morphological growth response promoted by 2OH-TDA consisted of multiple lateral branches, spaced fairly regularly apart, along the primary germ tubes as well as some lateral branch formation off the major secondary hyphae. This growth response was identical to that observed when germinated spores were allowed to grow towards cultured carrot roots in vitro. This response to 2OH-TDA also was observed with an unidentified Gigaspora species but no morphological response was observed with Glomus intraradices Schenck and Smith. The results indicate that 2-hydroxy fatty acids are another putative category of root exudate signals perceived by Gigaspora species, stimulating an increase in elongated lateral branches. Published by Elsevier Ltd.

A Precise Method for Processing Data to Determine the Dissociation Constants of Polyhydroxy Carboxylic Acids via Potentiometric Titration.

PubMed

Huang, Kaixuan; Xu, Yong; Lu, Wen; Yu, Shiyuan

2017-12-01

The thermodynamic dissociation constants of xylonic acid and gluconic acid were studied via potentiometric methods, and the results were verified using lactic acid, which has a known pKa value, as a model compound. Solutions of xylonic acid and gluconic acid were titrated with a standard solution of sodium hydroxide. The determined pKa data were processed via the method of derivative plots using computer software, and the accuracy was validated using the Gran method. The dissociation constants associated with the carboxylic acid group of xylonic and gluconic acids were determined to be pKa 1  = 3.56 ± 0.07 and pKa 1  = 3.74 ± 0.06, respectively. Further, the experimental data showed that the second deprotonation constants associated with a hydroxyl group of each of the two acids were pKa 2  = 8.58 ± 0.12 and pKa 2  = 7.06 ± 0.08, respectively. The deprotonation behavior of polyhydroxy carboxylic acids was altered using various ratios with Cu(II) to form complexes in solution, and this led to proposing a hypothesis for further study.

Damage mechanism of hydroxyl radicals toward adenine—thymine base pair

NASA Astrophysics Data System (ADS)

Tan, Rong-Ri; Wang, Dong-Qi; Zhang, Feng-Shou

2014-02-01

The adenine—thymine base pair was studied in the presence of hydroxyl radicals in order to probe the hydrogen bond effect. The results show that the hydrogen bonds have little effect on the hydroxylation and dehydrogenation happened at the sites, which are not involved in a hydrogen bond, while at the sites involved in hydrogen bond formation in the base pair, the reaction becomes more difficult, both in view of the free energy barrier and the exothermicity. With a 6-311++G(d,p) level of description, both B3LYP and MP2 methods confirm that the C8 site of isolated adenine has the highest possibility to form covalent bond with the hydroxyl radicals, though with different energetics: B3LYP predicts a barrierless pathway, while MP2 finds a transition state with an energy of 106.1 kJ/mol. For the dehydrogenation reactions, B3LYP method predicts that the free energy barrier increases in the order of HN9 < HN61 < HN62 < H2 < H8.

The influence of maternal ethnic group and diet on breast milk fatty acid composition.

PubMed

Su, Lin Lin; S K, Thamarai Chelvi; Lim, Su Lin; Chen, Yuming; Tan, Elizabeth A T; Pai, Namratha Narayan; Gong, Yin Han; Foo, Janie; Rauff, Mary; Chong, Yap Seng

2010-09-01

Breast milk fatty acids play a major role in infant development. However, no data have compared the breast milk composition of different ethnic groups living in the same environment. We aimed to (i) investigate breast milk fatty acid composition of three ethnic groups in Singapore and (ii) determine dietary fatty acid patterns in these groups and any association with breast milk fatty acid composition. This was a prospective study conducted at a tertiary hospital in Singapore. Healthy pregnant women with the intention to breastfeed were recruited. Diet profile was studied using a standard validated 3-day food diary. Breast milk was collected from mothers at 1 to 2 weeks and 6 to 8 weeks postnatally. Agilent gas chromatograph (6870N) equipped with a mass spectrometer (5975) and an automatic liquid sampler (ALS) system with a split mode was used for analysis. Seventy-two breast milk samples were obtained from 52 subjects. Analysis showed that breast milk ETA (Eicosatetraenoic acid) and ETA:EA (Eicosatrienoic acid) ratio were significantly different among the races (P = 0.031 and P = 0.020), with ETA being the highest among Indians and the lowest among Malays. Docosahexaenoic acid was significantly higher among Chinese compared to Indians and Malays. No difference was demonstrated in n3 and n6 levels in the food diet analysis among the 3 ethnic groups. Differences exist in breast milk fatty acid composition in different ethnic groups in the same region, although no difference was demonstrated in the diet analysis. Factors other than maternal diet may play a role in breast milk fatty acid composition.

Abscisic Acid Biosynthesis in Leaves and Roots of Xanthium strumarium1

PubMed Central

Creelman, Robert A.; Gage, Douglas A.; Stults, John T.; Zeevaart, Jan A. D.

1987-01-01

Research on the biosynthesis of abscisic acid (ABA) has focused primarily on two pathways: (a) the direct pathway from farnesyl pyrophosphate, and (b) the indirect pathway involving a carotenoid precursor. We have investigated which biosynthetic pathway is operating in turgid and stressed Xanthium leaves, and in stressed Xanthium roots using long-term incubations in 18O2. It was found that in stressed leaves three atoms of 18O from 18O2 are incorporated into the ABA molecule, and that the amount of 18O incorporated increases with time. One 18O atom is incorporated rapidly into the carboxyl group of ABA, whereas the other two atoms are very slowly incorporated into the ring oxygens. The fourth oxygen atom in the carboxyl group of ABA is derived from water. ABA from stressed roots of Xanthium incubated in 18O2 shows a labeling pattern similar to that of ABA in stressed leaves, but with incorporation of more 18O into the tertiary hydroxyl group at C-1′ after 6 and 12 hours than found in ABA from stressed leaves. It is proposed that the precursors to stress-induced ABA are xanthophylls, and that a xanthophyll lacking an oxygen function at C-6 (carotenoid numbering scheme) plays a crucial role in ABA biosynthesis in Xanthium roots. In turgid Xanthium leaves, 18O is incorporated into ABA to a much lesser extent than it is in stressed leaves, whereas exogenously applied 14C-ABA is completely catabolized within 48 hours. This suggests that ABA in turgid leaves is either (a) made via a biosynthetic pathway which is different from the one in stressed leaves, or (b) has a half-life on the order of days as compared with a half-life of 15.5 hours in water-stressed Xanthium leaves. Phaseic acid showed a labeling pattern similar to that of ABA, but with an additional 18O incorporated during 8′-hydroxylation of ABA to phaseic acid. PMID:16665768

Post-polymerization modification of poly(L-glutamic acid) with D-(+)-glucosamine.

PubMed

Perdih, Peter; Cebašek, Sašo; Možir, Alenka; Zagar, Ema

2014-11-27

Carboxyl functional groups of poly(L-glutamic acid) (PGlu) were modified with a D-(+)-glucosamine (GlcN) by amidation using 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM) as a coupling reagent. The coupling reaction was performed in aqueous medium without protection of hydroxyl functional groups of D-(+)-glucosamine. Poly(L-glutamic acid) and GlcN functionalized polyglutamates (P(Glu-GlcN)) were thoroughly characterized by 1D and 2D NMR spectroscopy and SEC-MALS to gain detailed information on their structure, composition and molar mass characteristics. The results reveal successful functionalization with GlcN through the amide bond and also to a minor extent through ester bond formation in position 1 of GlcN. In addition, a ratio between the α- and β-form of glucosamine substituent coupled to polyglutamate repeating units as well as the content of residual dimethoxy triazinyl active ester moiety in the samples were evaluated.

Effective L-Tyrosine Hydroxylation by Native and Immobilized Tyrosinase

PubMed Central

Lewańczuk, Marcin; Koźlecki, Tomasz; Liesiene, Jolanta; Bryjak, Jolanta

2016-01-01

Hydroxylation of L-tyrosine to 3,4-dihydroxyphenylalanine (L-DOPA) by immobilized tyrosinase in the presence of ascorbic acid (AH2), which reduces DOPA-quinone to L-DOPA, is characterized by low reaction yields that are mainly caused by the suicide inactivation of tyrosinase by L-DOPA and AH2. The main aim of this work was to compare processes with native and immobilized tyrosinase to identify the conditions that limit suicide inactivation and produce substrate conversions to L-DOPA of above 50% using HPLC analysis. It was shown that immobilized tyrosinase does not suffer from partitioning and diffusion effects, allowing a direct comparison of the reactions performed with both forms of the enzyme. In typical processes, additional aeration was applied and boron ions to produce the L-DOPA and AH2 complex and hydroxylamine to close the cycle of enzyme active center transformations. It was shown that the commonly used pH 9 buffer increased enzyme stability, with concomitant reduced reactivity of 76%, and that under these conditions, the maximal substrate conversion was approximately 25 (native) to 30% (immobilized enzyme). To increase reaction yield, the pH of the reaction mixture was reduced to 8 and 7, producing L-DOPA yields of approximately 95% (native enzyme) and 70% (immobilized). A three-fold increase in the bound enzyme load achieved 95% conversion in two successive runs, but in the third one, tyrosinase lost its activity due to strong suicide inactivation caused by L-DOPA processing. In this case, the cost of the immobilized enzyme preparation is not overcome by its reuse over time, and native tyrosinase may be more economically feasible for a single use in L-DOPA production. The practical importance of the obtained results is that highly efficient hydroxylation of monophenols by tyrosinase can be obtained by selecting the proper reaction pH and is a compromise between complexation and enzyme reactivity. PMID:27711193

phzO, a Gene for Biosynthesis of 2-Hydroxylated Phenazine Compounds in Pseudomonas aureofaciens 30-84

PubMed Central

Delaney, Shannon M.; Mavrodi, Dmitri V.; Bonsall, Robert F.; Thomashow, Linda S.

2001-01-01

Certain strains of root-colonizing fluorescent Pseudomonas spp. produce phenazines, a class of antifungal metabolites that can provide protection against various soilborne root pathogens. Despite the fact that the phenazine biosynthetic locus is highly conserved among fluorescent Pseudomonas spp., individual strains differ in the range of phenazine compounds they produce. This study focuses on the ability of Pseudomonas aureofaciens 30-84 to produce 2-hydroxyphenazine-1-carboxylic acid (2-OH-PCA) and 2-hydroxyphenazine from the common phenazine metabolite phenazine-1-carboxylic acid (PCA). P. aureofaciens 30-84 contains a novel gene located downstream from the core phenazine operon that encodes a 55-kDa aromatic monooxygenase responsible for the hydroxylation of PCA to produce 2-OH-PCA. Knowledge of the genes responsible for phenazine product specificity could ultimately reveal ways to manipulate organisms to produce multiple phenazines or novel phenazines not previously described. PMID:11114932

Analysis of acid-base interactions at Al2O3 (11-20) interfaces by means of single molecule force spectroscopy

NASA Astrophysics Data System (ADS)

Mosebach, Bastian; Ozkaya, Berkem; Giner, Ignacio; Keller, Adrian; Grundmeier, Guido

2017-10-01

Single molecule force spectroscopy (SMFS) was employed to investigate the interaction forces between aliphatic amino, hydroxyl and ether groups and aluminum oxide single crystal surfaces in an aqueous electrolyte at pH = 6. The force studies were based on the variation of the terminal group of polyethylene glycol which was bound via a Ssbnd Au bond to the gold coated AFM tip. X-ray Photoelectron Spectroscopy (XPS) was performed to characterize the surface chemistry of the substrate. Force distance curves were measured between the PEG-NH2, sbnd OH and sbnd OCH3 functionalized atomic force microscope (AFM) tip and the non-polar single crystalline Al2O3(11-20) surface. The experimental results exhibit non-equilibrium desorption events which hint at acid-base interactions of the electron donating hydroxyl and amino groups with Al-ions in the surface of the oxide. The observed desorption forces for the sbnd NH2, sbnd OH/Al2O3(11-20) were in the range of 100-200 pN.

Synthesis, characterization and liver targeting evaluation of self-assembled hyaluronic acid nanoparticles functionalized with glycyrrhetinic acid.