40 CFR 721.1731 - Poly(oxy-1,2-ethanediyl), α-methyl-ω-hydroxy, ester with boric acid (H3BO3).

Code of Federal Regulations, 2012 CFR

2012-07-01

...-hydroxy, ester with boric acid (H3BO3). 721.1731 Section 721.1731 Protection of Environment ENVIRONMENTAL..., ester with boric acid (H3BO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as poly(oxy-1,2-ethanediyl), α-methyl-ω-hydroxy, ester with boric...

40 CFR 721.1731 - Poly(oxy-1,2-ethanediyl), α-methyl-ω-hydroxy, ester with boric acid (H3BO3).

Code of Federal Regulations, 2010 CFR

2010-07-01

...-hydroxy, ester with boric acid (H3BO3). 721.1731 Section 721.1731 Protection of Environment ENVIRONMENTAL..., ester with boric acid (H3BO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as poly(oxy-1,2-ethanediyl), α-methyl-ω-hydroxy, ester with boric...

40 CFR 721.1731 - Poly(oxy-1,2-ethanediyl), α-methyl-ω-hydroxy, ester with boric acid (H3BO3).

Code of Federal Regulations, 2011 CFR

2011-07-01

...-hydroxy, ester with boric acid (H3BO3). 721.1731 Section 721.1731 Protection of Environment ENVIRONMENTAL..., ester with boric acid (H3BO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as poly(oxy-1,2-ethanediyl), α-methyl-ω-hydroxy, ester with boric...

40 CFR 721.1731 - Poly(oxy-1,2-ethanediyl), α-methyl-ω-hydroxy, ester with boric acid (H3BO3).

Code of Federal Regulations, 2013 CFR

2013-07-01

...-hydroxy, ester with boric acid (H3BO3). 721.1731 Section 721.1731 Protection of Environment ENVIRONMENTAL..., ester with boric acid (H3BO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as poly(oxy-1,2-ethanediyl), α-methyl-ω-hydroxy, ester with boric...

40 CFR 721.1730 - Poly(oxy-1,2-ethanediyl), α-butyl-ω-hydroxy, ester with boric acid (H3BO3).

Code of Federal Regulations, 2012 CFR

2012-07-01

...-hydroxy, ester with boric acid (H3BO3). 721.1730 Section 721.1730 Protection of Environment ENVIRONMENTAL..., ester with boric acid (H3BO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as poly(oxy-1,2-ethanediyl), α-butyl-ω-hydroxy, ester with boric...

40 CFR 721.1731 - Poly(oxy-1,2-ethanediyl), α-methyl-ω-hydroxy, ester with boric acid (H3BO3).

Code of Federal Regulations, 2014 CFR

2014-07-01

...-hydroxy, ester with boric acid (H3BO3). 721.1731 Section 721.1731 Protection of Environment ENVIRONMENTAL..., ester with boric acid (H3BO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as poly(oxy-1,2-ethanediyl), α-methyl-ω-hydroxy, ester with boric...

MX [3-Chloro-4-(Dichloromethyl)-5-Hydroxy-2[5H]-Furanone], A Drinking-Water Carcinogen, Does Not Induce Mutations in the Liver of Cii Transgenic Medaka (Oryzias latipes)

EPA Science Inventory

Mutagenicity assays with Salmonella have shown that 3-chloro-4-(dichloromethyl)-5-hydroxy-2[5H]-furanone (MX), a drinking water disinfection by-product is a potent mutagen, accounting for about one third of the mutagenic potency/potential of chlorinated drinking water. The abilit...

Benzophenone-type UV filters in surface waters: An assessment of profiles and ecological risks in Shanghai, China.

PubMed

Wu, Ming-Hong; Xie, Deng-Guo; Xu, Gang; Sun, Rui; Xia, Xiao-Yu; Liu, Wen-Long; Tang, Liang

2017-07-01

Benzophenone-type UV filters (BP-UV filters) are frequently introduced into aquatic environment from several sources. The occurrence and fate of select BP-UV filters and their metabolites were investigated in this study. All target compounds were detected in water samples, except for 2, 3, 4-trihydroxybenzophenone (2, 3, 4-OH-BP). The concentration reached up 131ngL -1 for 5-benzoyl-4-hydroxy-2-ethoxybenzenesulfonic acid (BP-4), 30.0ngL -1 for 2-hydroxy-4-methoxybenzophenone (BP-3), and mean value of 158ngL -1 for benzophenone (BP). Concentrations of BP-UV filters were not related to recreational waters but with high population frequencies. In addition, five BP-UV filters, namely 2,2',4,4'-tetrahydroxybenzophenone (BP-2), 2,3,4-OH-BP, 2,4-dihydroxybenzophenone (BP-1), 4-hydroxybenzophenone (4-OH-BP) and BP were investigated for probable sources, and found that they originate from BP-3 metabolism. There is a similar source for BP-3, BP-4, BP-1, 4-OH-BP and BP. Environmental risk assessment (ERA) showed that risk quotients (RQs) of BP-4, BP-3 and BP were 2.7, 0.8 and 0.5, respectively. Copyright © 2017 Elsevier Inc. All rights reserved.

Occurrence and metabolism of 7-hydroxy-2-indolinone-3-acetic acid in Zea mays

NASA Technical Reports Server (NTRS)

Lewer, P.; Bandurski, R. S.

1987-01-01

7-Hydroxy-2-indolinone-3-acetic acid was identified as a catabolite of indole-3-acetic acid in germinating kernels of Zea mays and found to be present in amounts of ca 3.1 nmol/kernel. 7-Hydroxy-2-indolinone-3-acetic acid was shown to be a biosynthetic intermediate between 2-indolinone-3-acetic acid and 7-hydroxy-2-indolinone-3-acetic acid-7'-O-glucoside in both kernels and roots of Zea mays. Further metabolism of 7-hydroxy-2-[5-3H]-indolinone-3-acetic acid-7'-O-glucoside occurred to yield tritiated water plus, as yet, uncharacterized products.

Polarizable continuum model associated with the self-consistent-reaction field for molecular adsorbates at the interface.

PubMed

Wang, Jing-Bo; Ma, Jian-Yi; Li, Xiang-Yuan

2010-01-07

In this work, a new procedure has been developed in order to realize the self-consistent-reaction field computation for interfacial molecules. Based on the extension of the dielectric polarizable continuum model, the quantum-continuum calculations for interfacial molecules have been carried out. This work presents an investigation into how the molecular structure influences the adsorbate-solvent interaction and consequently alters the orientation angle at the air/water interface. Taking both electrostatic and non-electrostatic energies into account, we investigate the orientation behavior of three interfacial molecules, 2,6-dimethyl-4-hydroxy-benzonitrile, 3,5-dimethyl-4-hydroxy-benzonitrile and p-cyanophenol, at the air/water interface. The results show that the hydrophilic hydroxyl groups in 2,6-dimethyl-4-hydroxy-benzonitrile and in p-cyanophenol point from the air to the water side, but the hydroxyl group in 3,5-dimethyl-4-hydroxy-benzonitrile takes the opposite direction. Our detailed analysis reveals that the opposite orientation of 3,5-dimethyl-4-hydroxy-benzonitrile results mainly from the cavitation energy. The different orientations of the hydrophilic hydroxyl group indicate the competition of electrostatic and cavitation energies. The theoretical prediction gives a satisfied explanation of the most recent sum frequency generation measurement for these molecules at the interface.

40 CFR 721.5293 - Poly(oxy-1,2-ethanediyl), alpha-(9Z)-9-octadecenyl-.omega.-hydroxy-, phosphate, ammonium salt.

Code of Federal Regulations, 2010 CFR

2010-07-01

... ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.5293 Poly(oxy-1,2-ethanediyl), alpha-(9Z)-9-octadecenyl-.omega.-hydroxy-, phosphate, ammonium salt. (a) Chemical substance and significant...

Effect of Temperature on Viscosity of S-Substituted Triazinothiocarbamides in 60% Dioxane Water Mixture

NASA Astrophysics Data System (ADS)

Kshirsagar, A. M.; Tayade, D. T.

2012-10-01

S-triazine and thiocarbamide group containing drug create their own identity in the drug, pharmaceutical and medicinal sciences in last four decades. Hence, the viscometric measurements of recently synthesized drugs viz. 1-(4-hydroxy-6-methyl)-S-triazino-3-phenylthiocarbamide (L1) and 1-(4-hydroxy-6-methyl)-S-triazino-3-methylthiocarbamide (L2), were carried out at 60% various percentage of solvent to investigate effect of structure, on group of S-triazinothiocarbamides. The result obtained during this investigation directly through light on the dipole association of compound, intermolecular attraction between solute and solvent, dielectric constant of medium, polarizability and mutual compensation of dipoles and useful for drug absorption, transmission, stability, activity and effect of drug. %K 1-(4-hydroxy-6-methyl)-S-triazino-3-phenylthiocarbamide (L1) and 1-(4-hydroxy-6-methyl)-S-triazino-3-methylthiocarbamide (L2), dioxane-water mixture, viscometric measurements.

CHARACTERISTICS AND TOXICITY OF THE DRINKING WATER DISINFECTION BY-PRODUCT 3-CHLORO-4(DICHLOROMETHYL)-5-HYDROXY-2[5H]-FURANONE (MX) TO MEDAKA (ORYZIAS LATIPES)

EPA Science Inventory

The compound 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone, also known as MX, is a by-product of wood pulp manufacture and a contaminant of chlorinated drinking and sewage water. MX has recently been shown to be carcinogenic to rodents. However, no data exist for its effec...

40 CFR 721.5253 - 2-Naphthalenecarboxylic acid, 4,4′-methylenebis [3-hydroxy-, strontium salt.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false 2-Naphthalenecarboxylic acid, 4,4â²-methylenebis [3-hydroxy-, strontium salt. 721.5253 Section 721.5253 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific...

40 CFR 721.5252 - 2-Naphthalenecarboxylic acid, 4,4′-methylenebis [3-hydroxy-, zinc salt.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false 2-Naphthalenecarboxylic acid, 4,4â²-methylenebis [3-hydroxy-, zinc salt. 721.5252 Section 721.5252 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical...

40 CFR 721.5252 - 2-Naphthalenecarboxylic acid, 4,4′-methylenebis [3-hydroxy-, zinc salt.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false 2-Naphthalenecarboxylic acid, 4,4â²-methylenebis [3-hydroxy-, zinc salt. 721.5252 Section 721.5252 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical...

40 CFR 721.5252 - 2-Naphthalenecarboxylic acid, 4,4′-methylenebis [3-hydroxy-, zinc salt.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false 2-Naphthalenecarboxylic acid, 4,4â²-methylenebis [3-hydroxy-, zinc salt. 721.5252 Section 721.5252 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical...

CHARACTERISTICS AND TOXICITY OF THE CHLORINATED DRINKING WATER DISINFECTION BY-PRODUCT 3-CHLORO-4-(DICHLOROMETHYL)-5-HYDROXY-2[5H]-FURANONE (MX) TO MEDAKA (ORYZIAS LATIPES)

EPA Science Inventory

The compound 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone, also know as MX, is a by-product of wood pulp manufacture and a contaminant of chlorinated drinking and sewage water. MX has recently been shown to be a multi-site carcinogen in rodents. We investigated the acute...

Synthesis, characterization and application of two-dimensional layered metal hydroxides for environmental remediation purposes

NASA Astrophysics Data System (ADS)

Machingauta, Cleopas

Two-dimensional layered nano composites, which include layered double hydroxides (LDHs), hydroxy double salts (HDSs) and layered hydroxide salts (LHSs) are able to intercalate different molecular species within their gallery space. These materials have a tunable structural composition which has made them applicable as fire retardants, adsorbents, catalysts, catalyst support materials, and ion exchangers. Thermal treatment of these materials results in destruction of the layers and formation of mixed metal oxides (MMOs) and spinels. MMOs have the ability to adsorb anions from solution and may also regenerate layered structures through a phenomenon known as memory effect. Zinc-nickel hydroxy nitrate was used for the uptake of a series of halogenated acetates (HAs). HAs are pollutants introduced into water systems as by-products of water chlorination and pesticide degradation; their sequestration from water is thus crucial. Optimization of layered materials for controlled uptake requires an understanding of their ion-exchange kinetics and thermodynamics. Exchange kinetics of these anions was monitored using ex-situ PXRD, UV-vis, HPLC and FTIR. It was revealed that exchange rates and uptake efficiencies are related to electronic spatial extents and the charge on carboxyl-oxygen atoms. In addition, acetate and nitrate-based HDSs were used to explore how altering the hydroxide layer affects uptake of acetate/nitrate ions. Changing the metal identities affects the interaction of the anions with the layers. From FTIR, we observed that nitrates coordinate in a D3h and Cs/C 2v symmetry; the nitrates in D3h symmetry were easily exchangeable. Interlayer hydrogen bonding was also revealed to be dependent on metal identity. Substituting divalent cations with trivalent cations produces materials with a higher charge density than HDSs and LHSs. A comparison of the uptake efficiency of zinc-aluminum, zinc-gallium and zinc-nickel hydroxy nitrates was performed using trichloroacetic acid as target anion. Uptake efficiency was better for LDHs than HDS, and between the LDHs, zinc-aluminum hydroxy nitrate was the best material for the uptake of tClAc. Calcined LDHs were applied for the uptake of methyl-orange, model azo-dye. The ability to regenerate the layered structures was helpful for improving adsorption efficiency. It has been reveal that calcined LDHs are also better adsorbents than calcined HDSs.

Determination of microbial colonisation in water-damaged buildings using chemical marker analysis by gas chromatography-mass spectrometry.

PubMed

Szponar, B; Larsson, L

2000-03-01

Gas chromatography-mass spectrometry was used to determine the microbial contents of building materials subjected to water damage in a laboratory experiment and of materials collected from houses affected by water during the flood in Klodzko in south-western Poland, July 1997. The samples were examined for 3-hydroxy fatty acids, markers of bacterial endotoxin, and ergosterol, marker of fungal biomass. The amounts of both 3-hydroxy fatty acids and ergosterol were higher in materials that had been exposed to water than in unexposed ones. All markers were stable in the building materials for at least 6 weeks at room temperature and could thus be used to reveal microbial contamination even when cultivation results for bacteria and fungi were negative. Direct measurement of 3-hydroxy fatty acids and ergosterol in human environments could be a useful method, e.g. in monitoring indoor air as regards presence of potentially harmful microorganisms and microbial constituents.

Antibiotics degradation in soil: A case of clindamycin, trimethoprim, sulfamethoxazole and their transformation products.

PubMed

Koba, Olga; Golovko, Oksana; Kodešová, Radka; Fér, Miroslav; Grabic, Roman

2017-01-01

Twelve different soil types that represent the soil compartments of the Czech Republic were fortified with three antibiotics (clindamycin (CLI), sulfamethoxazole (SUL), and trimethoprim (TRI)) to investigate their fate. Five metabolites (clindamycin sulfoxide (CSO), hydroxy clindamycin sulfoxide (HCSO), S-(SDC) and N-demethyl clindamycin (NDC), N 4 -acetyl sulfamethoxazole (N 4 AS), and hydroxy trimethoprim (HTR)) were detected and identified using HPLC/HRMS and HRPS in the soil matrix in this study. The identities of CSO and N 4 AS were confirmed using commercially available reference standards. The parent compounds degraded in all soils. Almost all of the metabolites have been shown to be persistent in soils, with the exception of N 4 AS, which was formed and degraded completely within 23 days of exposure. The rate of degradation mainly depended on the soil properties. The PCA results showed a high dependence between the soil type and behaviour of the pharmaceutical metabolites. The mentioned metabolites can be formed in soils, and the most persistent ones may be transported to the ground water and environmental water bodies. Because no information on the effects of those metabolites on living organism are available, more studies should be performed in the future to predict the risk to the environment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Experimental Study of Hydroxy Gas (HHO) Production with Variation in Current, Voltage and Electrolyte Concentration

NASA Astrophysics Data System (ADS)

Alam, Noor; Pandey, K. M.

2017-08-01

In this paper, work has been carried out experimentally for the investigation of the effects of variation incurrent, voltage, temperature, chemical concentration and reaction time on the amount of hydroxy gas produced. Further effects on the overall electrolysis efficiency of advance alkaline water is also studied. The hydroxy gas (HHO) has been produced experimentally by the electrolysis of alkaline water with parallel plate electrode of 316L-grade stainless steel. The electrode has been selected on the basis of corrosion resistance and inertness with respect to electrolyte (KOH). The process used for the production of HHO is conventional as compared to the other production processes because of reduced energy consumption, less maintenance and low setup cost. From the experimental results, it has been observed that with increase in voltage, temperature and electrolyte concentration of alkaline solution, the production of hydroxy gas has increased about 30 to 40% with reduction in electrical energy consumption.

7 CFR 205.603 - Synthetic substances allowed for use in organic livestock production.

Code of Federal Regulations, 2011 CFR

2011-01-01

... Water Act. (i) Calcium hypochlorite. (ii) Chlorine dioxide. (iii) Sodium hypochlorite. (8) Electrolytes... additives. (1) DL-Methionine, DL-Methionine—hydroxy analog, and DL-Methionine—hydroxy analog calcium (CAS... following maximum levels of synthetic methionine per ton of feed: laying chickens—4 pounds; broiler chickens...

7 CFR 205.603 - Synthetic substances allowed for use in organic livestock production.

Code of Federal Regulations, 2012 CFR

2012-01-01

... Water Act. (i) Calcium hypochlorite. (ii) Chlorine dioxide. (iii) Sodium hypochlorite. (8) Electrolytes... additives. (1) DL-Methionine, DL-Methionine—hydroxy analog, and DL-Methionine—hydroxy analog calcium (CAS... following maximum levels of synthetic methionine per ton of feed: laying chickens—4 pounds; broiler chickens...

7 CFR 205.603 - Synthetic substances allowed for use in organic livestock production.

Code of Federal Regulations, 2014 CFR

2014-01-01

... Water Act. (i) Calcium hypochlorite. (ii) Chlorine dioxide. (iii) Sodium hypochlorite. (8) Electrolytes.... (1) DL-Methionine, DL-Methionine-hydroxy analog, and DL-Methionine-hydroxy analog calcium (CAS #'s 59... maximum levels of synthetic methionine per ton of feed: Laying and broiler chickens—2 pounds; turkeys and...

7 CFR 205.603 - Synthetic substances allowed for use in organic livestock production.

Code of Federal Regulations, 2013 CFR

2013-01-01

... Water Act. (i) Calcium hypochlorite. (ii) Chlorine dioxide. (iii) Sodium hypochlorite. (8) Electrolytes.... (1) DL-Methionine, DL-Methionine-hydroxy analog, and DL-Methionine-hydroxy analog calcium (CAS #'s 59... maximum levels of synthetic methionine per ton of feed: Laying and broiler chickens—2 pounds; turkeys and...

Evaluation of Environmentally Benign New Chemical Rust Removing Agent- Hydroxy Ethane Diphosphonic Acid (HEDPA)

DTIC Science & Technology

2012-12-15

Removing Agent – Hydroxy Ethane Diphosphonic Acid (HEDPA) 1, A. Sarada Rao, 2, A. Yashodhara Rao, 3, Appajosula S. Rao Naval Surface Warfare...Abstract------------------------------------------------------------ In order to evaluate the adaptability of hydroxyethane diphosphonic acid (HEDPA...function of acid concentration in the range 2-20 vol. % and at different temperatures in the temperature range 23 o C -55°C. The results suggest

Optically active antifungal azoles. XII. Synthesis and antifungal activity of the water-soluble prodrugs of 1-[(1R,2R)-2-(2,4-difluorophenyl)-2-hydroxy-1-methyl-3-(1H-1,2,4-triazol-1-yl)propyl]-3-[4-(1H-1-tetrazolyl)phenyl]-2-imidazolidinone.

PubMed

Ichikawa, T; Kitazaki, T; Matsushita, Y; Yamada, M; Hayashi, R; Yamaguchi, M; Kiyota, Y; Okonogi, K; Itoh, K

2001-09-01

1-[(1R,2R)-2-(2,4-Difluorophenyl)-2-hydroxy-1-methyl-3-(1H-1,2,4-triazol-1-yl)propyl]-3-[4-(1H-1-tetrazolyl)phenyl]-2-imidazolidinone (1: TAK-456) was selected as a candidate for clinical trials, but since its water-solubility was insufficient for an injectable formulation, the quaternary triazolium salts 2 were designed as water-soluble prodrugs. Among the prodrugs prepared, 4-acetoxymethyl-1-[(2R,3R)-2-(2,4-difluorophenyl)-2-hydroxy-3-[2-oxo-3-[4-(1H-1-terazolyl)phenyl]-1-imidazolidinyl]butyl]-1H-1,2,4-triazolium chloride (2a: TAK-457) was selected as an injectable candidate for clinical trials based on the results of evaluations on solubility, stability, hemolytic effect and in vivo antifungal activities.

Sensitive assay, based on hydroxy fatty acids from lipopolysaccharide lipid A, for Gram-negative bacteria in sediments.

PubMed Central

Parker, J H; Smith, G A; Fredrickson, H L; Vestal, J R; White, D C

1982-01-01

Biochemical measures have provided insight into the biomass and community structure of sedimentary microbiota without the requirement of selection by growth or quantitative removal from the sediment grains. This study used the assay of the hydroxy fatty acids released from the lipid A of the lipopolysaccharide in sediments to provide an estimate of the gram-negative bacteria. The method was sensitive to picomolar amounts of hydroxy fatty acids. The recovery of lipopolysaccharide hydroxy fatty acids from organisms added to sediments was quantitative. The lipids were extracted from the sediments with single-phase chloroform-methanol extraction. The lipid-extraction residue was hydrolyzed in 1 N HCl, and the hydroxy fatty acids of the lipopolysaccharide were recovered in chloroform for analysis by gas-liquid chromatography. This method proved to be about fivefold more sensitive than the classical phenol-water or trichloroacetic acid methods when applied to marine sediments. By examination of the patterns of hydroxy fatty acids, it was also possible to help define the community structure of the sedimentary gram-negative bacteria. PMID:6817712

Halogenated solvent remediation

DOEpatents

Sorenson, Jr., Kent S.

2008-11-11

Methods for enhancing bioremediation of ground water contaminated with nonaqueous halogenated solvents are disclosed. An illustrative method includes adding an electron donor for microbe-mediated anaerobic reductive dehalogenation of the halogenated solvents, which electron donor enhances mass transfer of the halogenated solvents from residual source areas into the aqueous phase of the ground water. Illustrative electron donors include C.sub.2-C.sub.4 carboxylic acids and hydroxy acids, salts thereof, esters of C.sub.2-C.sub.4 carboxylic acids and hydroxy acids, and mixtures thereof, of which lactic acid, salts of lactic acid--such as sodium lactate, lactate esters, and mixtures thereof are particularly illustrative. The microbes are either indigenous to the ground water, or such microbes can be added to the ground water in addition to the electron donor.

Structural and thermal properties of inorganic-organic montmorillonite: Implications for their potential environmental applications.

PubMed

Rathnayake, Suramya I; Xi, Yunfei; Frost, Ray L; Ayoko, Godwin A

2015-12-01

Inorganic-organic clays (IOCs), clays intercalated with both organic cations such as cationic surfactants and inorganic cations such as metal hydroxy polycations have the properties of both organic and pillared clays, and thereby the ability to remove both inorganic and organic contaminants from water simultaneously. In this study, IOCs were synthesised using three different methods with different surfactant concentrations. Octadecyltrimethylammonium bromide (ODTMA) and hydroxy aluminium ([Al13O4(OH)24(H2O)12](7+) or Al13) are used as the organic and inorganic modifiers (intercalation agents). According to the results, the interlayer distance, the surfactant loading amount and the Al/Si ratio of IOCs strictly depend on the intercalation method and the intercalation agent ratio. Interlayers of IOCs synthesised by intercalating ODTMA before Al13 and IOCs synthesised by simultaneous intercalation of ODTMA and Al13 were increased with increasing the ODTMA concentration used in the synthesis procedure and comparatively high loading amounts could be observed in them. In contrast, Al/Si decreased with increasing ODTMA concentration in these two types of IOCs. The results suggest that Al-pillars can be fixed within the interlayers by calcination and any increment in the amount of ODTMA used in the synthesis procedure did not affect the interlayer distance of the IOCs. Overall the study provides valuable insights into the structure and properties of the IOCs and their potential environmental applications. Copyright © 2015 Elsevier Inc. All rights reserved.

Geometrical behavior of hydrogen bonding patterns in the alpha-dodecyl-omega-hydroxy-tris(oxyethylene)-water system monitored by near infrared spectroscopy.

PubMed

Ohno, Keiichi; Takao, Hiroshi; Katsumoto, Yukiteru

2006-03-01

Changes in the geometry of hydrogen bonding patterns in the alpha-dodecyl-omega-hydroxy-tris(oxyethylene) (C(12)E(3))-water system have been investigated by near infrared (NIR) spectroscopy. In the 5,300-4,600 cm(-1) region, the characteristic bands for C(12)E(3) and water can be separately investigated, since the combination bands of the OH stretching and its COH bending of alcohols are observed at 5,000-4,650 cm(-1), whereas the combination bands of the OH stretching and its HOH bending of water, at 5,300-5,000 cm(-1). The NIR result has revealed that the addition of water to C(12)E(3) promotes the formation of the OHcdots, three dots, centeredOHcdots, three dots, centeredO hydrogen bonds.

Studies on the precursors of strong mutagen [3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone]MX by chlorination of fractions from different waters.

PubMed

Xu, X; Liang, L; Zou, H; Liu, Y; Wang, L; Zhang, J

1997-10-01

The strong mutagen, [3-chloro-4-(dichloromethyl)-5-hydroxy- 2(5H)-furanone] MX, was found to be one of the most potent mutagens in drinking water. In this study, dissolved organic matters from river water and lake water were separated into several compound classes by sorbtion on a series of resin absorbents. After chlorine treatment of the fractions, MX was determined with GC/MS in the selected ion monitoring mode. Humic substances produced more MX on a TOC-basis than other fractions and contributed more to MX formation in the chlorinated natural waters. Some phenols were detected in the oxidation products of humic substances and therefore formation of MX may occur when some phenolic precursor structures in humic substances are treated with chlorine.

Halogenated solvent remediation

DOEpatents

Sorenson, Kent S.

2004-08-31

Methods for enhancing bioremediation of ground water contaminated with nonaqueous halogenated solvents are disclosed. A preferred method includes adding a composition to the ground water wherein the composition is an electron donor for microbe-mediated reductive dehalogenation of the halogenated solvents and enhances mass transfer of the halogenated solvents from residual source areas into the aqueous phase of the ground water. Illustrative compositions effective in these methods include surfactants such as C.sub.2 -C.sub.4 carboxylic acids and hydroxy acids, salts thereof, esters of C.sub.2 -C.sub.4 carboxylic acids and hydroxy acids, and mixtures thereof. Especially preferred compositions for use in these methods include lactic acid, salts of lactic acid, such as sodium lactate, lactate esters, and mixtures thereof. The microbes are either indigenous to the ground water, or such microbes can be added to the ground water in addition to the composition.

NHC-Catalyzed Asymmetric Benzoin Reaction in Water.

PubMed

Yan, Jun; Sun, Rong; Shi, Kuangxi; Li, Kai; Yang, Limin; Zhong, Guofu

2018-06-11

A chiral NHC-catalyzed benzoin condensation reaction in water was developed, thereby affording α-hydroxy ketones in good to high yields and high enantioselectivities. Water was proposed as a proton shuttle in the aqueous asymmetric condensation reaction.

Method of removing and detoxifying a phosphorus-based substance

DOEpatents

Vandegrift, George F.; Steindler, Martin J.

1989-01-01

A method of removing organic phosphorus-based poisonous substances from water contaminated therewith and of subsequently destroying the toxicity of the substance is disclosed. Initially, a water-immiscible organic is immobilized on a supported liquid membrane. Thereafter, the contaminated water is contacted with one side of the supported liquid membrane to selectively dissolve the phosphorus-based substance in the organic extractant. At the same time, the other side of the supported liquid membrane is contacted with a hydroxy-affording strong base to react the phosphorus-based substance dissolved by the organic extractant with a hydroxy ion. This forms a non-toxic reaction product in the base. The organic extractant can be a water-insoluble trialkyl amine, such as trilauryl amine. The phosphorus-based substance can be phosphoryl or a thiophosphoryl.

The synthesis and characterization of environmentally-responsive water-swellable and water-soluble polymers for wastewater remediation

NASA Astrophysics Data System (ADS)

Armentrout, Rodney Scott

The primary research goal is the development of new polymeric materials that demonstrate the environmentally-responsive sequestration of common water foulants, including surfactants and oils. Water-swellable and water-soluble polymers have been synthesized, structurally characterized, and their physical properties have been determined. In addition, the ability of the materials to sequester model water foulants has been evaluated. Anionic crosslinked polymer networks of 2-acrylamido-2-methyl-1-propanesulfonic acid, acrylamide, and methylene bisacrylamide have been synthesized and characterized by determining the equilibrium water contents as a function of ionic content of the polymer network. The molar ratio of bound surfactant to ionic group was determined to be less than one for all hydrogels studied, indicating an ion-exchange binding mechanism with minimal hydrophobic interactions between bound and unbound surfactant molecules is responsible for surfactant binding. Cationic crosslinked cyclopolymer networks of N,N-diallyl- N-methyl amine (DAMA) and N,N,N,N-tetraallyl ammonium chloride (TAAC) have been synthesized and characterized by determining the equilibrium water content as a function of pH. A maximum in the equilibrium water content is observed for pH-6 when the polymer is fully ionized. The solubilization of a model water foulant, p-cresol, by the polymeric surfactant, Pluronic F127, has been studied via equilibrium dialysis, dynamic light scattering and ultrafiltration experiments. It has been shown that at 25°C p-cresol is readily solubilized by F127 since the polymeric surfactant exists in a multimer conformation. Ultrafiltration experiments have demonstrated that the polymer-foulant binding interactions are largely unaffected by shear in a hollow fiber membrane. Copolymers of the zwitterionic monomer, 3-(N,N-diallyl- N-methyl ammonio) propane sulfonate (DAMAPS) and N,N-diallyl- N,N-dimethylammonium chloride (DADMAC) (the DADS series) or the pH-responsive hydrophobic monomer, N,N-diallyl-N-methyl amine (DAMA) (the DAMS series) have been prepared in a 0.5 M NaCl aqueous solution using 2-hydroxy-1-[4-(hydroxy-ethoxy)phenyl]-2-methyl-1-propanone (Irgacure 2959) as the free-radical photoinitiator. 13C NMR data indicate that the resulting polymers maintain the five-membered ring structure in the cis conformation common to diallylammonium salts. Equilibrium dialysis experiments demonstrate that pH-responsive hydrophobic microdomain formation may be utilized to control the solubilization of the organic solute, p-cresol. Ultrafiltration experiments have demonstrated that the polymer-foulant binding interactions are largely unaffected by shear in a hollow fiber membrane. Macromolecular aggregates of the poly( N,N-diallyl-N-methyl amine)/p-cresol complexes lead to fouling of the ultrafiltration membrane. However, incorporation of the sulfobetaine moiety hinders the formation of the macroscopic structures and higher permeate flux rates are achieved. (Abstract shortened by UMI.)

Effects of adding liquid DL-methionine hydroxy analogue-free acid to drinking water on growth performance and small intestinal morphology of nursery pigs.

PubMed

Kaewtapee, C; Krutthai, N; Poosuwan, K; Poeikhampha, T; Koonawootrittriron, S; Bunchasak, C

2010-06-01

This study was conducted to evaluate the effect of adding liquid DL-methionine hydroxy analogue free acid (LMA) to drinking water on growth performance, small intestinal morphology and volatile fatty acids in the caecum of nursery pigs. Twenty-four crossbred pigs (Large White x Landrace, BW approximately 18 kg) were divided into three groups with four replications of two piglets each. The piglets received drinking water without (control), with 0.05 or 0.10% LMA. The results indicated that adding LMA at 0.10% to drinking water significantly increased their weight gain, average daily feed intake (p < 0.05) and tended to improve the feed conversion ratio. Adding LMA to drinking water significantly increased their water intake and significantly reduced the pH of drinking water (p < 0.01), thus total plate count (p < 0.01) and Escherichia coli in drinking water was reduced (p < 0.05), while the total number of bacteria in the caecum was not significantly affected. Liquid DL-methionine hydroxy analogue free acid supplementation in drinking water tended to decrease pH in the stomach, duodenum, jejunum, colon and rectum. Furthermore, adding LMA at 0.10% significantly increased villous height in the duodenum, jejunum and ileum (p < 0.05), and the villous height:crypt depth ratio in the jejunum and ileum (p < 0.01) was higher, whereas acetic acid concentration in the caecum was significantly lower than in the control group. It could be concluded that adding LMA to drinking water improved growth performance of the nursery pigs because of high water quality and high nutrient utilization caused by an improvement of small intestinal morphology (not from nutritional effect of methionine source).

Antibacterial activity of sulfamethoxazole transformation products (TPs): general relevance for sulfonamide TPs modified at the para position.

PubMed

Majewsky, Marius; Wagner, Danny; Delay, Markus; Bräse, Stefan; Yargeau, Viviane; Horn, Harald

2014-10-20

Sulfonamide antibiotics undergo transformation in the aquatic environment through biodegradation, photolysis, or hydrolysis. In this study, the residual antibacterial activity of 11 transformation products (TPs) of sulfamethoxazole (SMX) was investigated with regard to their in vitro growth and luminescence inhibition on Vibrio fischeri (30 min and 24 h exposure). Two transformation products, 4-hydroxy-SMX and N(4)-hydroxy-acetyl-SMX, were synthesized in-house and confirmed by nuclear magnetic resonance and high-resolution mass spectrometry. Results of individual compound experiments showed that TPs modified at the para amino group still exhibit clear antibacterial effects, whereas TPs resulting from breakdown of the SMX structure lost this mechanism of action. 4-NO2- and 4-OH-SMX were found to inhibit growth to a clearly greater extent than the parent compound, SMX. In contrast, the N(4)-acetyl- and N(4)-hydroxy-acetyl-derivatives retain less than 10 and 5% of the effect of SMX on growth and luminescence inhibition, respectively. The effect of a mixture of para-modified TPs was observed to be additive. Considering the homologous series of sulfa drugs widely prescribed and their common mechanism of action, the potential environmental impact must consider the total amount of sulfonamide antibiotics and their derivative TPs, which might end up in a water body. Extrapolating the results obtained here for the para TPs of SMX to other sulfa drugs and determining the persistence and occurrence of these compounds in the aquatic environment is required for improved risk assessment.

Use of time-of-flight mass spectrometry for large screening of organic pollutants in surface waters and soils from a rice production area in Colombia.

PubMed

Hernández, F; Portolés, T; Ibáñez, M; Bustos-López, M C; Díaz, R; Botero-Coy, A M; Fuentes, C L; Peñuela, G

2012-11-15

The irrigate district of Usosaldaña, an important agricultural area in Colombia mainly devoted to rice crop production, is subjected to an intensive use of pesticides. Monitoring these compounds is necessary to know the impact of phytosanitary products in the different environmental compartments. In this work, surface water and soil samples from different sites of this area have been analyzed by applying an analytical methodology for large screening based on the use of time-of-flight mass spectrometry (TOF MS) hyphenated to liquid chromatography (LC) and gas chromatography (GC). Several pesticides were detected and unequivocally identified, such as the herbicides atrazine, diuron or clomazone. Some of their main metabolites and/or transformation products (TPs) like deethylatrazine (DEA), deisopropylatrazine (DIA) and 3,4-dichloroaniline were also identified in the samples. Among fungicides, carbendazim, azoxystrobin, propiconazole and epoxiconazole were the most frequently detected. Insecticides such as thiacloprid, or p,p'-DDT metabolites (p,p'-DDD and p,p'-DDE) were also found. Thanks to the accurate-mass full-spectrum acquisition in TOF MS it was feasible to widen the number of compounds to be investigated to other families of contaminants. This allowed the detection of emerging contaminants, such as the antioxidant 3,5-di-tertbutyl-4-hydroxy-toluene (BHT), its metabolite 3,5-di-tert-butyl-4-hydroxy-benzaldehyde (BHT-CHO), or the solar filter benzophenone, among others. Copyright © 2012 Elsevier B.V. All rights reserved.

Microbial Community-Level Physiological Profiles (CLPP) and herbicide mineralization potential in groundwater affected by agricultural land use

NASA Astrophysics Data System (ADS)

Janniche, Gry Sander; Spliid, Henrik; Albrechtsen, Hans-Jørgen

2012-10-01

Diffuse groundwater pollution from agricultural land use may impact the microbial groundwater community, which was investigated as Community-Level Physiological Profiles (CLPP) using EcoPlate™. Water was sampled from seven piezometers and a spring in a small agricultural catchment with diffuse herbicide and nitrate pollution. Based on the Shannon-Wiener and Simpson's diversity indices the diversity in the microbial communities was high. The response from the EcoPlates™ showed which substrates support groundwater bacteria, and all 31 carbon sources were utilized by organisms from at least one water sample. However, only nine carbon sources were utilized by all water samples: D-Mannitol, N-acetyl-D-glucosamine, putrescine, D-galacturonic acid, itaconic acid, 4-hydroxy benzoic acid, tween 40, tween 80, and L-asparagine. In all water samples the microorganisms preferred D-mannitol, D-galacturonic acid, tween 40, and 4-hydroxy benzoic acid as substrates, whereas none preferred 2-hydroxy benzoic acid, α-D-lactose, D,L-α-glycerol phosphate, α-ketobutyric acid, L-threonine and glycyl-L-glutamic acid. Principal Component Analysis of the CLPP's clustered the most agriculturally affected groundwater samples, indicating that the agricultural land use affects the groundwater microbial communities. Furthermore, the ability to mineralize atrazine and isoproturon, which have been used in the catchment, was also associated with this cluster.

Super-hydrophilicity of hydroxy modified poly(m-phenylenediamine) aerogel for separation of oil/water and biocompatibility

NASA Astrophysics Data System (ADS)

Wang, Gang; Liu, Zhiduo; Zhang, Nan; Li, Jiurong; Xu, Anli; Xiang, Pengcheng; Hu, Xurui; Guo, Qinglei; Chen, Da

2018-04-01

We demonstrate the ultra-light weight and super-hydrophilic hydroxyl modified poly (m-phenylenediamine) (Hy-PmPD) aerogel by utilizing simple oxygen plasma treatment. The average pore size and specific surface area are obtained as 5.21 nm and 671 m2 g‑1, respectively. Due to the large amount of oxygen-containing groups (e.g., C–OH and N–OH), the contact angle of Hy-PmPD for water is about 7.2°, which indicates the super-hydrophilic ability of Hy-PmPD. The large surface area and super-hydrophilic nature of ultra- light weight Hy-PmPD aerogel conclusively certify that high absorption capacities and ultrafast absorption rate for water. As a result, the Hy-PmPD aerogel enables to separate crude oil and water. Additionally, the Hy-PmPD aerogel indicates good biocompatibility that can be implanted as the bio-platform for monitoring the cell culture behavior. This work may provide a facile and effective strategy for the applications in the absorption or removal of organics, particularly in environmental protection, pollution control, as well as noninvasive to the microflora.

Environmentally friendly chemoselective oxidation of primary aliphatic amines by using a biomimetic electrocatalytic system.

PubMed

Largeron, Martine; Chiaroni, Angèle; Fleury, Maurice-Bernard

2008-01-01

Environmentally friendly oxidation of primary aliphatic amines to imines has been successfully achieved, under metal-free conditions, by the use of diverse electrogenerated o-azaquinone mediators. High catalytic performance, together with high chemoselectivity, were observed with electron-poor o-azaquinone catalysts generated from 2-aminoresorcinol derivatives. Similar to copper amine oxidase enzymes, these mediators exhibited lower reactivity toward alpha-branched primary amines and no reactivity toward secondary amines. In the case of 3,4-aminophenol derivatives lacking a 2-hydroxy group, the generated o-azaquinone species failed to catalyze the oxidation of the amine to the corresponding imine. Further mechanistic considerations allowed a rationalization of the crucial role of the 2-hydroxy group in converting a catalytically inert species into a highly effective biomimetic catalyst.

MUTAGENIC AND CLASTOGENIC PROPERTIES OF 3-CHLORO-4-(DICHLOROMETHYL)-5-HYDROXY-2(5H)-FURANONE: A POTENT BACTERIAL MUTAGEN IN DRINKING WATER

EPA Science Inventory

3-Chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) was found to be a direct-acting mutagen in the Ames test for strains TA1535, TA1538, TA92, TA97, TA98, TA100 and TA102. The highest mutagenic response (approximately 13,000 revertants/nmol) was seen in strain TA100. The TA...

Antifouling activity of green-synthesized 7-hydroxy-4-methylcoumarin.

PubMed

Pérez, Miriam; García, Mónica; Ruiz, Diego; Autino, Juan Carlos; Romanelli, Gustavo; Blustein, Guillermo

2016-02-01

In the search for new environmental-friendly antifoulants for replace metallic biocides, 7-hydroxy-4-methylcoumarin was synthesized according to green chemistry procedures. This compound was characterized by current organic analysis and its antifouling properties were firstly evaluated on the bivalve Mytilus edulis platensis in the laboratory. In the second stage, a soluble matrix antifouling coating formulated with this compound was assayed in marine environment. Laboratory experiments showed that 7-hydroxy-4-methylcoumarin was effective in inhibiting both the settlement as well as the byssogenesis of mussels. In addition, after exposure time in the sea, painted panels containing this compound showed strong antifouling effect on conspicuous species of the fouling community of Mar el Plata harbor. In conclusion, green-synthesized coumarin could be a suitable antifoulant candidate for marine protective coatings. Copyright © 2015 Elsevier Ltd. All rights reserved.

Determination of trace levels of herbicides and their degradation products in surface and ground waters by gas chromatography/ion-trap mass spectrometry

USGS Publications Warehouse

Pereira, W.E.; Rostad, C.E.; Leiker, T.J.

1990-01-01

A rapid, specific and highly sensitive method is described for the determination of several commonly used herbicides and their degradation products in surface and ground waters by using gas chromatography/ion-trap mass spectrometry. The compounds included atrazine, and its degradation products desethylatrazine and desisopropylatrazine; Simazine; Cyanazine; Metolachlor; and alachlor and its degradation products, 2-chloro-2', 6'-diethylacetanilide, 2-hydroxy-2', 6'-diethylacetanilide and 2,6-diethylaniline. The method was applied to surface-water samples collected from 16 different stations along the lower Mississippi River and its major tributaries, and ground-water samples beneath a cornfield in central Nebraska. Average recovery of a surrogate herbicide, terbuthylazine, was greater than 99%. Recoveries of the compounds of interest from river water spiked at environmental levels are also presented. Full-scan mass spectra of these compounds were obtained on 1 ng or less of analyte. Data were collected in the full-scan acquisition mode. Quantitation was based on a single characteristic ion for each compound. The detection limit was 60 pg with a signal-to-noise ratio of greater than 10:1.

Detection of the anaerobic dechlorinating microorganism Desulfomonile tiedjei in environmental matrices by its signature lipopolysacchride branched-long-chain hydroxy fatty acids

USGS Publications Warehouse

Ringleberg, D.B.; Townsend, G.T.; DeWeerd, K.A.; Suflita, J.M.; White, D.C.

1994-01-01

Desulfomonile tiedjei is a Gram-negative sulfate-reducing bacterium capable of catalyzing aryl reductive dehalogenation reactions. Since many toxic and persistent contaminants in the subsurface are halogenated aromatic compounds, the detection and enumeration of dehalogenating microorganisms in the environment may be a useful tool for planning and evaluating bioremediation efforts. In this study, we show that D. tiedjei contains unique lipopolysaccharide branched 3-hydroxy fatty acids, unknown as yet in other bacteria, and that it is possible to detect the bacterium in inoculated aquifer sediments based on these signature lipid biomarkers. The detection of D. tiedjeiand other dehalogenating microorganisms possessing similar cellular properties in environmental matrices may be possible by this technique. Additionally, the effect of such inoculation on dehalogenation activity is examined.

Separator for alkaline electric batteries and method of making

NASA Technical Reports Server (NTRS)

Pfluger, H. L. (Inventor); Hoyt, H. E.

1970-01-01

Battery separator membranes of high electrolytic conductivity comprising a cellulose ether and a compatible metallic salt of water soluble aliphatic acids and their hydroxy derivatives are described. It was found that methyl cellulose can be modified by another class of materials, nonpolymeric in nature, to form battery separator membranes of low electrolytic resistance but which have the flexibility of membranes made of unmodified methyl cellulose, and which in many cases enhance flexibility over membranes made with unmodified methyl cellulose. Separator membranes for electrochemical cells comprising a cellulose ether and a modified selected from the group consisting of metallic salts of water soluble alphatic acids and their hydroxy derivatives and to electrochemical cells utilizing said membranes are described.

Identification of keto- and hydroxy-dicarboxylic acids in remote marine aerosols from the western North Pacific: GC and GC/TOF-MS measurements

NASA Astrophysics Data System (ADS)

Vani, D.; Kawamura, K.; Tachibana, E.; Boreddy, S. K. R.

2015-12-01

Dicarboxylic acids (diacids) are dominant components of organic aerosols in the atmosphere. They contribute significantly to the total aerosol mass and have a serious impacts on global climate changes. However, studies on keto- and hydroxy-diacids in marine aerosols are limited. Compare to diacids, keto- and hydroxy-diacids are more hygroscopic due to the additional polar groups (OH and CO) and, hence, acts as cloud condensation nuclei (CCN). Molecular characterization of these compounds provides insight into organic aerosols sources and transformation pathways. We collected marine aerosols from remote Chichijima Island in the western North Pacific from December 2010 to November 2011 and studied for water-soluble keto- and hydroxy-diacids. Carboxyl groups were derivatized to dibutyl esters with 14% boron trifluoride/n-butanol, whereas hydroxyl groups were derivatized to trimethylsilyl ethers using N,O-Bis (trimethylsilyl) trifluoroacetamide (BSTFA). After two-step derivatization, samples were injected to GC, GC/MS and GC/TOF-MS. In the GC chromatogram, we detected several new peaks after BSTFA derivatization of dibutyl ester fraction. Based on mass spectral interpretation, we found these peaks as homologues series of hydroxy-diacids and keto-diacids. Some of these hydroxy-diacids have been individually reported in literature in the laboratory photo-oxidation experiments and forest environments samples. But, there are no evidences to prove their sources and formation mechanism in the atmosphere. Here, we report for the first time homologous series of hydroxy-diacids (hC3di-hC6di) and keto-diacid (oxaloacetic acid, enol and keto forms) in remote marine atmosphere. Molecular distributions of hydroxy-diacids generally showed the predominance of malic acid followed by tartronic acid. Both hydroxy- and keto-diacids show significant positive correlation with oxalic acid and SO42-, suggesting that they are generated in the atmosphere and play an important role in the formation of smaller diacids through aqueous phase photo-oxidation.

GENOTOXIC AND CARCINOGENIC PROPERTIES OF CHLORINATED FURANONES - IMPORTANT BY-PRODUCTS OF WATER CHLORINATION

EPA Science Inventory

The widespread presence of genotoxins in drinking water can be directly linked to the chlorination stage of water treatment. ecent studies in Finland, the United States and Great Britain have shown that a single compound, 3-chloro-4-(dichlo-romethyl)-5-hydroxy-2(5H)-furanone (MX)...

p-Nitrophenol and glutathione response in medaka (Oryzias latipes)exposed to MX, a drinking water carcinogen

EPA Science Inventory

When chlorine is introduced into public drinking water for disinfection, it can react with organic compounds in surface waters to form toxic by-products such as 3-chloro-4-(dichloromethyl)-5-hydroxy-2[5H]-furanone (MX). We investigated the effect of exposure to MX on cytochrome ...

P-NITROPHENOL AND GLUTATHIONE RESPONSE IN MEDAKA (ORYZIAS LATIPES) EXPOSED TO MX, A DRINKING WATER CARCINOGEN.

EPA Science Inventory

When chlorine is introduced into public drinking water for disinfection, it can react with organic compounds in surface waters to form toxic by-products such as 3-chloro-4- (dichloromethyl)-5-hydroxy-2[5H]-furanone (MX). We investigated the effect of exposure to MX on cytochr...

Oxidative metabolism of BDE-47, BDE-99, and HBCDs by cat liver microsomes: Implications of cats as sentinel species to monitor human exposure to environmental pollutants.

PubMed

Zheng, Xiaobo; Erratico, Claudio; Luo, Xiaojun; Mai, Bixian; Covaci, Adrian

2016-05-01

The in vitro oxidative metabolism of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), 2,2',4,4',5-pentabromodiphenyl ether (BDE-99), and individual α-, β- and γ-hexabromocyclododecane (HBCD) isomers catalyzed by cytochrome P450 (CYP) enzymes was screened using cat liver microsomes (CLMs). Six hydroxylated metabolites, namely 4-hydroxy-2,2',3,4'-tetrabromodiphenyl ether (4-OH-BDE-42), 3-hydroxy-2,2',4,4'-tetrabromodiphenyl ether (3-OH-BDE-47), 5-hydroxy-2,2',4,4'-tetrabromodiphenyl ether (5-OH-BDE-47), 6-hydroxy-2,2',4,4'-tetrabromodiphenyl ether (6-OH-BDE-47), 4'-hydroxy-2,2',4,5'- tetrabromodiphenyl ether (4'-OH-BDE-49), and 2'-hydroxy-2,3',4,4'-tetrabromodiphenyl ether (2'-OH-BDE-66), were identified and quantified after incubation of BDE-47. A di-OH-tetra-BDE was also found as metabolite of BDE-47 with CLMs. 5-OH-BDE-47 was the major metabolite formed. Five hydroxylated metabolites (3'-hydroxy-2,2',4,4',5-pentabromodiphenyl ether (3'-OH-BDE-99), 5'-hydroxy-2,2',4,4',5-pentabromodiphenyl ether (5'-OH-BDE-99), 6-hydroxy-2,2',4,4',5-pentabromodiphenyl ether (6-OH-BDE-99), 6'-hydroxy-2,2',4,4',5-pentabromodiphenyl ether (6'-OH-BDE-99), and 4'-hydroxy-2,2',4,5,5'-pentabromodiphenyl ether (4'-OH-BDE-101) were formed from BDE-99 incubated with CLMs. Concentrations of BDE-99 metabolites were lower than those of BDE-47. Four or more mono-hydroxylated HBCD (OH-HBCDs), four or more di-hydroxylated HBCD (di-OH-HBCDs), five or more mono-hydroxylated pentabromocyclododecanes (OH-PBCDs), and five or more di-hydroxylated pentabromocyclododecenes (di-OH-PBCDs) were detected after incubation of α-, β-, or γ-HBCD with CLMs. No diastereoisomeric or enantiomeric enzymatic isomerisation was observed incubating α-, β- or γ-HBCD with CLMs. Collectively, our data suggest that (i) BDE-47 is metabolized at a faster rate than BDE-99 by CLMs, (ii) OH-HBCDs are the major hydroxylated metabolites of α-, β- and γ-HBCD produced by CLMs, and (iii) the oxidative metabolism of BDE-47 and BDE-99 is different by cat and human liver microsomes. This suggests that cats are not a suitable sentinel to represent internal exposure of PBDEs for humans, but is likely a promising sentinel for internal HBCDs exposure for humans. Copyright © 2016 Elsevier Ltd. All rights reserved.

A short and facile synthesis of 2-(1Z)-(3-hydroxy-3,7-dimethylocta-1,6-dienyl)-1,4-benzenediol and 1-(3'-methoxypropanoyl)-2,4,5-trimethoxybenzene isolated from Cordia alliodora.

PubMed

Kaur, Sukhbir; Singh, Vasundhara; Kumar, Gulshan; Kad, G L; Singh, Jasvinder

2010-03-01

A novel synthesis of 2-(1Z)-(3-hydroxy-3,7-dimethylocta-1,6-dienyl)-1,4-benzenediol and 1-(3'-methoxypropanoyl)-2,4,5-trimethoxybenzene has been carried out by making use of an easily available starting material, acceleration by MW irradiation and the use of water as a green solvent in the key steps.

rac-6-Hydroxy-2,5,7,8-tetramethylchroman-2-carboxamide from synchrotron data

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

Brzezinski, Krzysztof; Dauter, Zbigniew; Baj, Aneta

2012-05-29

The crystal structure of the title water-soluble analogue of vitamin E, trolox amide, C{sub 14}H{sub 19}NO{sub 3}, solved and refined against synchrotron diffraction data, contains two molecules in the asymmetric unit. In both molecules, the heterocyclic ring is in a half-chair conformation. The crystal packing features a herring-bone pattern generated by N-H...O hydrogen bonds between the hydroxy and amide groups. O-H...O hydrogen bonds also occur.

Photolysis of the herbicide bispyribac sodium in aqueous medium under the influence of UV and sunlight in presence or absence of sensitizers.

PubMed

Kanrar, Bappaditya; Bhattacharyya, Anjan

2009-11-01

The photolysis of a rice herbicide Bispyribac sodium (Sodium 2, 6-bis [(4, 6-dimethoxypyrimidin-2-yl) oxy] benzoate) has been studied in different aqueous medium (distilled water, pond water and Irrigation water) under the influence of UV (lambda max > or = 250 nm) and sunlight in presence or absence of sensitizers (TiO(2) and KNO(3)). The study was conducted under laboratory simulated condition which made it possible to evaluate the contribution of different factors viz. source of irradiation, solvent and sensitizers towards the photolysis of bispyribac sodium. The photodegradation proceeds via first order reaction Kinetics in all the cases. Five photo metabolites (M(1)-M(5)) were isolated in pure form by column chromatographic method from the irradiation system under UV influenced and TiO(2) as sensitizer. From the different spectral data (IR, NMR, UV-VIS, Mass) the structure of these five metabolites were assigned as M(1) (Phenol), M(2) [2, 6-Dihydroxy benzoic acid], M(3) [2, 6-bis [(4, 6 dimethoxypyrimidin-2yl) oxy] benzoic acid], M(4) [2-(3-Hydroxy-phenoxy)-pyrimidine-4, 6-diol] and M(5) as [2,4-Dihydroxy-3, 5-dimethoxy-6-(4-methoxy pyrimidine-2-yloxy)-benzoic acid]. Moreover, another six photometabolites (M(6)-M(11)) were identified from the different irradiation system on the basis of Micromass analysis. On the basis of MS/MS data analysis, the structure of these six photometabolites were assigned as M(6) [2-(4, 6-Dimethoxy-pyrimidin-2-yloxy)-6-hydroxy-benzoic acid], M(7) [2-Hydroxy-6-(4-hydroxy-6-methoxy-pyrimidin-2-yloxy)-benzoic acid], M(8) [4, 6-Dimethoxy-pyrimidin-2-ol], M(9) [6-Methoxy-pyrimidine-2, 4-diol], M(10) [2-Hydroxy-6-(pyrimidin-2-yloxy)-benzoic acid] and M(11) [2, 4, 6-Trimethoxy-pyrimidine]. The plausible Photodegradation pathways of bispyribac sodium in the present investigation were portrayed which proceeds via hydrolysis, hydrolytic cleavage, O-dealkylation, decarboxylation, dehydroxylation, O-alkylation and hydroxylation.

Gadolinium-loaded gel scintillators for neutron and antineutrino detection

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

Riddle, Catherine Lynn; Akers, Douglas William; Demmer, Ricky Lynn

A gadolinium (Gd) loaded scintillation gel (Gd-ScintGel) compound allows for neutron and gamma-ray detection. The unique gel scintillator encompasses some of the best features of both liquid and solid scintillators, yet without many of the disadvantages associated therewith. Preferably, the gel scintillator is a water soluble Gd-DTPA compound and water soluble fluorophores such as: CdSe/ZnS (or ZnS) quantum dot (Q-dot) nanoparticles, coumarin derivatives 7-hydroxy-4-methylcoumarin, 7-hydroxy-4-methylcoumarin-3-acetic acid, 7-hydroxycoumarin-3-carboxylic acid, and Alexa Fluor 350 as well as a carbostyril compound, carbostyril 124 in a stable water-based gel, such as methylcellulose or polyacrylamide polymers. The Gd-loaded ScintGel allows for a homogenious distribution ofmore » the Gd-DTPA and the fluorophores, and yields clean fluorescent emission peaks. A moderator, such as deuterium or a water-based clear polymer, can be incorporated in the Gd-ScintGel. The gel scintillators can be used in compact detectors, including neutron and antineutrino detectors.« less

Crystal structure of tetra-kis-(μ3-2-{[1,1-bis-(hy-droxy-meth-yl)-2-oxidoeth-yl]imino-meth-yl}phenolato)tetra-copper(II) ethanol monosolvate 2.5-hydrate.

PubMed

Wang, Weilun; Ran, Jingwen

2015-05-01

The title compound, [Cu4(C11H13NO4)4]·CH3CH2OH·2.5H2O, is an electronically neutral tetra-nuclear copper(II) complex with a cubane-like Cu4O4 core. The complete molecule has point group symmetry 2. The phenol hy-droxy group and one of the three alcohol hy-droxy groups of each 2-{[tris-(hy-droxy-meth-yl)meth-yl]imino-meth-yl}phenol ligand are depro-ton-ated, while the secondary amine and the other two hy-droxy groups remain unchanged. The Cu(II) atoms in the Cu4O4 core are connected by four μ3-O atoms from the deprotonated alcohol hy-droxy groups. Each of the penta-coordinated Cu(II) ions has an NO4 distorted square-pyramidal environment through coordination to the tridentate Schiff base ligands. The Cu-N/O bond lengths span the range 1.902 (4)-1.955 (4) Å, similar to values reported for related structures. There are O-H⋯O hydrogen-bond inter-actions between the complex molecules and the ethanol and water solvent molecules, leading to the formation of a three-dimensional network. The ethanol solvent molecule is disordered about a twofold rotation axis. One of the two independent water molecules is also located on this twofold rotation axis and shows half-occupancy.

Hydroxy fatty acids in snow pit samples from Mount Tateyama in central Japan: Implications for atmospheric transport of microorganisms and plant waxes associated with Asian dust

NASA Astrophysics Data System (ADS)

Tyagi, Poonam; Kawamura, Kimitaka; Bikkina, Srinivas; Mochizuki, Tomoki; Aoki, Kazuma

2016-11-01

We report here the source apportionment of atmospheric soil microorganisms and higher plant metabolites based on chemical markers (hydroxy fatty acids: FAs) in the snowpack samples collected from Mount Tateyama in central Japan during spring 2009 (N = 6) and 2011 (N = 7). A homologous series of β-hydroxy FAs (C9-C20), constituents of Gram-negative bacteria (GNB), in snowpacks clearly suggest a long-range atmospheric transport of dust-associated bacteria followed by scavenging by snowflakes. Similarly, higher atmospheric abundances of α-(C16-C32) and ω-(C9-C30)-hydroxy FAs in the snow layers containing Asian dust revealed contributions from soil microbes and higher plant epicuticular waxes. Moreover, covariation between the concentrations of hydroxy FAs and water-soluble Ca2+ (dust tracer), together with calculated air mass backward trajectories, demonstrated their source regions such as the Taklamakan Desert, Gobi Desert, and Loess Plateau. A close match of molecular distributions of hydroxy FAs (with the predominance of ω- and β-isomers) is noteworthy between snowpack (present study) and springtime aerosols from Chichijima Island in the western North Pacific (WNP). This observation suggests a "below-cloud scavenging" of transported dust particles and associated soil microbes in the East Asian outflow by snowflakes. These distributions are, however, contrary to those observed in the fresh snow samples from Sapporo, northern Japan (predominance of α-hydroxy FAs), which could be explained by "in-cloud" microbial oxidation processes. This comparison, therefore, provides additional insights regarding the aeolian transport of soil microbes in the East Asian outflow to the WNP, which has not been available.

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.

Synthesis and identification of major metabolites of environmental pollutant dibenzo[c,mno]chrysene.

PubMed

Sharma, Arun K; Amin, Shantu

2005-09-01

Dibenzo[c,mno]chrysene commonly known as naphtho[1,2-a]pyrene (N[1,2-a]P) is an environmental pollutant, recently identified in coal tar extract, in air-borne particulate matter, in marine sediment, and in cigarette-smoke condensate. We recently reported an efficient synthesis of N[1,2-a]P and examined its in vitro metabolism by male Sprague Dawley rat liver S9 fraction, which resulted in a number of dihydrodiol and phenolic metabolites. The synthesis of 10-hydroxy-N[1,2-a]P and fjord region N[1,2-a]P trans-9,10-dihydrodiol, which were identified among the various metabolites, was assigned earlier by comparing with the synthetic standards. The other major metabolites were separated by HPLC and, based on the 1H NMR analysis, were tentatively suggested to be the two K-region dihydrodiols, that is, N[1,2-a]P trans-4,5-dihydrodiol (6) and N[1,2-a]P trans-7,8-dihydrodiol (7), and the hydroxy derivatives of N[1,2-a]P. To unequivocally assign the structure to each of the peaks and to have them in larger amounts for toxicological studies, we have now synthesized the two K-region dihydrodiols and the 1-/3-hydroxy-N[1,2-a]P, short-listed based on the proton NMR of the collected peaks. The K-region dihydrodiols 6 and 7 were prepared by the treatment of N[1,2-a]P with OsO(4) to give a mixture of cis dihydrodiols 2 and 3, followed by pyridinium chlorochromate-assisted oxidation to quinones 4 and 5, and finally reduction with NaBH(4) to afford the dihydrodiols 6 and 7 with the desired trans stereochemistry. The 1-hydroxy-N[1,2-a]P (22) and 3-hydroxy-N[1,2-a]P (23) were synthesized using a photochemical approach. As expected, all the synthesized dihydrodiol and phenolic derivatives of N[1,2-a]P identified with those obtained from in vitro metabolism enabling the assignment of all the major metabolites.

Comparative cytotoxic and genotoxic potential of 13 drinking water disinfection by-products using a microplate-based cytotoxicity assay and a developed SOS/umu assay.

PubMed

Zhang, Shao-Hui; Miao, Dong-Yue; Tan, Li; Liu, Ai-Lin; Lu, Wen-Qing

2016-01-01

The implications of disinfection by-products (DBPs) present in drinking water are of public health concern because of their potential mutagenic, carcinogenic and other toxic effects on humans. In this study, we selected 13 main DBPs found in drinking water to quantitatively analyse their cytotoxicity and genotoxicity using a microplate-based cytotoxicity assay and a developed SOS/umu assay in Salmonella typhimurium TA1535/pSK1002. With the developed SOS/umu test, eight DBPs: 3-chloro-4-(dichloromethyl)-5-hydroxy-2[5H]-fura3-chloro-4-(dichloromethyl)-5-hydroxy-2-[5H]-furanone (MX), dibromoacetonitrile (DBN), iodoacetic acid (IA), bromochloroacetonitrile (BCN), bromoacetic acid (BA), trichloroacetonitrile (TCN), dibromoacetic acid (DBA) and dichloroacetic acid (DCA) were significantly genotoxic to S. typhimurium. Three DBPs: chloroacetic acid (CA), trichloroacetic acid (TCA) and dichloroacetonitrile (DCN) were weakly genotoxic, whereas the remaining DBPs: chloroacetonitrile (CN) and chloral hydrate (CH) were negative. The rank order in decreasing genotoxicity was as follows: MX > DBN > IA > BCN > BA > TCN > DBA > DCA > CA, TCA, DCN > CN, CH. MX was approximately 370 000 times more genotoxic than DCA. In the microplate-based cytotoxicity assay, cytotoxic potencies of the 13 DBPs were compared and ranked in decreasing order as follows: MX > IA > DBN > BCN > BA > TCN > DCN > CA > DCA > DBA > CN > TCA > CH. MX was approximately 19 200 times more cytotoxic than CH. A statistically significant correlation was found between cytotoxicity and genotoxicity of the 13 DBPs in S. typhimurium. Results suggest that microplate-based cytotoxicity assay and the developed SOS/umu assay are feasible tools for analysing the cytotoxicity and genotoxicity of DBPs, particularly for comparing their toxic intensities quantitatively. © The Author 2015. Published by Oxford University Press on behalf of the UK Environmental Mutagen Society. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Carboxylic Acids as Indicators of Parent Body Conditions

NASA Technical Reports Server (NTRS)

Lerner N. R.; Chang, Sherwood (Technical Monitor)

1995-01-01

Alpha-hydroxy and alpha-amino carboxylic acids found on the Murchison meteorite are deuterium enriched. It is postulated that they arose from a common interstellar scurce: the reaction of carbonyl compounds in an aqueous mixture containing HCN and NH3. Carbonyl compounds react with HCN to form alpha-hydroxy nitriles, RR'CO + HCN right and left arrow RR'C(OH)CN. If ammonia is also present, the alpha-hydroxy nitriles will exist in equilibrium with the alpha-amino nitriles, RR'C(OH)CN + NH3 right and left arrow - RRCNH2CN + H2O. Both nitrites are hydrolyzed by water to form carboxylic acids: RR'C(OH)CN + H2O yields RR'C(OH)CO2H and RR'C(NH2)CN + H2O yields RR'C(NH2)CO2H.

Theoretical investigation of gas-phase molecular complex formation between 2-hydroxy thiophenol and a water molecule.

PubMed

Kumar Deb, Debojit; Sarkar, Biplab

2017-01-18

The torsional potential of OH and SH rotations in 2-hydroxy thiophenol is systematically studied using the MP2 ab initio method. The outcome of state-of-the-art calculations is used in the investigation of the structures and conformational preferences of 2-hydroxy thiophenol and aims at further interaction studies with a gas phase water molecule. SCS-MP2 and CCSD(T) complete basis set (CBS) limit interaction energies for these complexes are presented. The SCS-MP2/CBS limit is achieved using various two-point extrapolation methods with aug-cc-pVDZ and aug-cc-pVTZ basis sets. The CCSD(T) correction term is determined as the difference between CCSD(T) and SCS-MP2 interaction energies calculated using a smaller basis set. The effect of counterpoise correction on the extrapolation to the CBS limit is discussed. The performance of DFT based wB97XD, M06-2X and B3LYP-D3 functionals is tested against the benchmark energy from ab initio calculations. Hydrogen bond interactions are characterized by carrying out QTAIM, NCIPLOT, NBO and SAPT analyses.

Physical and monolayer film properties of potential fatty ester biolubricants

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

Yao, Linxing; Hammond, Earl G; Wang, Tong

2014-04-03

The desire to replace petroleum-based lubricants with alternatives that are environmentally friendly and made from sustainable sources has encouraged the development of biolubricants based on vegetable oils. To be good lubricants, the materials should have low melting points, appropriate viscosity and oxidative stability. In this paper, we report the melting point and viscosity of oleate esters of ethylene glycol, 1,2-propanediol, 2,3-butanediol, and pentaerythritol as well as the decanoate esters of 2,3-butanediol and the 12-methyltetradecanoate esters of 1,2-propanediol. Polyol esters that have a free hydroxy group had lower melting points than the completely esterified polyols, but the completely esterified polyol estersmore » exhibited less change in viscosity with temperature than those having a free hydroxy group. 2, 3-Butanediol monooleate, which melted at -48.6°C shows promise as a biolubricant, but its viscosity index was estimated to be 100. Pentaerythritol oleate esters, with melting points below -10°C and viscosity indices in the range of 170–197, may be suitable candidates as biolubricants. The behavior of esters spread as a monomolecular film at air/water interface may provide insight into the way they behave when spread on metal or polar surfaces, so the pressure-area isotherms of 2,3-butanediol monoleate and selected esters are also reported.« less

Trace analysis of 61 natural and synthetic progestins in river water and sewage effluents by ultra-high performance liquid chromatography-tandem mass spectrometry.

PubMed

Shen, Xiaoyan; Chang, Hong; Sun, Dezhi; Wang, Linxia; Wu, Fengchang

2018-04-15

A broad number of natural and synthetic progestins are widely used in human and veterinary therapies. Although progestins exhibit adverse effects in aquatic organisms, information about environmental occurrence and fate have been limited to several compounds, hampering the accuracy of risk assessments of the compounds. In this study, a selective and sensitive analytical method was established to simultaneously determine 19 natural and 42 synthetic progestins in environmental waters, and the synthetic progestins included 19-nortestosterone, 17α-hydroxyprogesterone and progesterone derivatives. All of the target compounds were effectively separated using an HSS T3 column, and the recoveries for effluent and river samples were 80-115% and 75-105%, respectively. The detection limits for the 61 analytes were in the range of 0.05-0.60 ng/L and 0.03-0.40 ng/L for the effluent and river samples, respectively. The developed method is applied to analyze the target progestogens in sewage effluent and river water samples from Beijing. The detected concentrations of natural progesterone metabolites (3α-hydroxy-5β-tetrahydroprogesterone) were up to 63 times higher than those of the parent compound. Of the three groups of synthetic progestins, the progesterone derivatives were detected for the first time and had the highest concentrations followed by the 19-nortestosterone and 17α-hydroxyprogesterone derivatives. In contrast to previous studies, the predominant derivative compounds of 19-nortestosterone were found to be 19-nortestosterone, gestodene and mifepristone, and those of 17α-hydroxyprogesterone were 6-epi-medroxy progesterone 17-acetate and melengestrol acetate. The toxicities and environmental risk of these emerging progestins deserves more attention in the future. Copyright © 2018 Elsevier Ltd. All rights reserved.

Development of a monoclonal antibody-based, congener-specific and solvent-tolerable direct enzyme-linked immunosorbgent assay for the detection of 2,2',4,4'-tetrabromodiphenyl ether in environmental samples

USDA-ARS?s Scientific Manuscript database

A sensitive direct enzyme-linked immunosorbent assay (ELISA) for the detection of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) in environmental samples was developed. A hapten mimicking the whole structure of BDE-47 was synthesized by introducing a butyric acid spacer to 5-hydroxy-BDE-47 and coupled ...

Development and validation of a sensitive liquid chromatographic-tandem mass spectrometric method for the simultaneous analysis of granisetron and 7-hydroxy granisetron in human plasma and urine samples: application in a clinical pharmacokinetic study in pregnant subject.

PubMed

Zhao, Yang; Chen, Hui-Jun; Caritis, Steve; Venkataramanan, Raman

2016-02-01

A liquid chromatography-tandem mass spectrometric method for the quantification of granisetron and its major metabolite, 7-hydroxy granisetron in human plasma and urine samples was developed and validated. Respective stable isotopically labeled granisetron and 7-hydroxy granisetron were used as internal standards (IS). Chromatography was performed using an Xselect HSS T3 analytical column with a mobile phase of 20% acetonitrile in water (containing 0.2 mM ammonium formate and 0.14% formic acid, pH 4) delivered in an isocratic mode. Tandem mass spectrometry operating in positive electrospray ionization mode with multiple reaction monitoring was used for quantification. The standard curves were linear in the concentration ranges of 0.5-100 ng/mL for granisetron and 0.1-100 ng/mL for 7-hydroxy granisetron in human plasma samples, and 2-2000 ng/mL for granisetron and 2-1000 ng/mL for 7-hydroxy granisetron in human urine samples, respectively. The accuracies were >85% and the precision as determined by the coefficient of variations was <10%. No significant matrix effects were observed for granisetron or 7-hydroxy granisetron in either plasma or urine samples. Granisetron was stable under various storage and experimental conditions. This validated method was successfully applied to a pharmacokinetic study after intravenous administration of 1 mg granisetron to a pregnant subject. Copyright © 2015 John Wiley & Sons, Ltd.

A novel three-component reaction for the synthesis of 1,3-benzoxazines in water.

PubMed

Rostami-Charati, Faramarz

2013-12-01

A simple and proficient method for the synthesis of 1,3-benzoxazine derivatives via three-component reaction of isocyanide and isoquinoline with 1-(6-hydroxy-2-isopropenyl-1-benzofuran-yl)-1-ethanone or 4-hydroxycumarine in water in the presence of piperidine at 70°C is reported.

[Effects of environmental stress on secondary metabolites of Aspergillus ochraceus LCJ11-102 associated with the coral Dichotella gemmacea].

PubMed

Zhou, Yalin; Wang, Yi; Liu, Peipei; Wang, Zhiying; Zhu, Weiming

2010-08-01

To explore the secondary metabolites of fungus Aspergillus ochraceus LCJ11-102 associated with the coral Dichotella gemmacea under environmental stress and to obtain characteristic compounds with biological activities. A nutrient-deprived culture medium (biomimetic culture) and a high salt culture medium were used for fermentation. Fingerprints of HPLC of the fermentation broth were used to investigate the diversity of secondary metabolites. Compounds were isolated by column chromatography on silica gel, Sephadex LH-20, and preparative HPLC. Their structures were identified by spectroscopic analyses and the modified Mosher's method. Different secondary metabolites were produced by A. ochraceus LCJ11-102 under two different culture conditions. (R)-mellein (1), (5,6-trans, 8,9-threo-) -9-chloro-8-hydroxy-8, 9-deoxyaspyrone (2), (5,6-erythro-, 8,9-threo-) -9-chloro-8-hydroxy-8, 9-deoxyasperlactone (3), and (5S, 6R, 9S)-dihydroaspyrone (4) were identified from the biomimetic cultures, and R (+) -semi-vioxanthin (5) was identified from the high salt cultures, respectively. Environmental stress obviously induces microbes to produce different secondary metabolites. And biomimetic culture is an effective approach to obtain active chloro compounds from marine microorganisms.

Selective and sensitive optical chemosensor for detection of Ag(I) ions based on 2(4-hydroxy pent-3-en-2-ylideneamine) phenol in aqueous samples

NASA Astrophysics Data System (ADS)

Mirzaei, Mohammad; Saeed, Jaber

2011-11-01

A selective and sensitive chemosensor, based on the 2(4-hydroxy pent-3-en-2-ylideneamine) phenol (HPYAP) as chromophore, has been developed for colorimetric and visual detection of Ag(I) ions. HPYAP shows a considerable chromogenic behavior toward Ag(I) ions by changing the color of the solution from pale-yellow to very chromatic-yellow, which can be easily detected with the naked-eye. The chemosensor exhibited selective absorbance enhancement to Ag(I) ions in water samples over other metal ions at 438 nm, with a linear range of 0.4-500 μM ( r2 = 0.999) and a limit of detection 0.07 μM of Ag(I) ions with UV-vis spectrophotometer detection. The relative standard deviation (RSD) for 100 μM Ag(I) ions was 2.05% ( n = 7). The proposed method was applied for the determination Ag(I) ions in water and waste water samples.

Immobilized humic substances and immobilized aggregates of humic substances as sorbent for solid phase extraction.

PubMed

Erny, Guillaume L; Gonçalves, Bruna M; Esteves, Valdemar I

2013-09-06

In this work, humic substances (HS) immobilized, as a thin layer or as aggregates, on silica gel were tested as material for solid phase extraction. Some triazines (simazine, atrazine, therbutylazine, atrazine-desethyl-desisopropyl-2-hydroxy, ametryn and terbutryn), have been selected as test analytes due to their environmental importance and to span a large range of solubility and octanol/water partition coefficient (logP). The sorbent was obtained immobilizing a thin layer of HS via physisorption on a pre-coated silica gel with a cationic polymer (polybrene). While the sorbent could be used as it is, it was demonstrated that additional HS could be immobilized, via weak interactions, to form stable humic aggregates. However, while a higher quantity of HS could be immobilized, no significant differences were observed in the sorption parameters. This sorbent have been tested for solid phase extraction to concentrate triazines from aqueous matrixes. The sorbent demonstrated performances equivalent to commercial alternatives as a concentration factor between 50 and 200, depending on the type of triazines, was obtained. Moreover the low cost and the high flow rate of sample through the column allowed using high quantity of sorbent. The analytical procedure was tested with different matrixes including tap water, river water and estuarine water. Copyright © 2013 Elsevier B.V. All rights reserved.

Using MOF-74 for Hg{sup 2+} removal from ultra-low concentration aqueous solution

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

Xiong, Yang Yang; Li, Jian Qiang; Gong, Le Le

Mercury (Hg{sup 2+}) ions have very high toxicity and widely spread as environmental pollutants. At present, many efforts have been taken to remove the hazardous materials of mercury(II) by adsorption, and it is highly desirable to develop a novel adsorbent with high adsorptive capacities. However it is still a big challenge to remove the ultra-low-concentration mercury ions from water. In this paper, MOF-74-Zn is explored for such function, showing high removal rate of Hg(II) from water without any pretreatment, especially for the ultra-trace Hg(II) ions in the ppb magnitude with the removal rate reaching to 54.48%, 69.71%, 72.26% when themore » initial concentration of Hg(II) is 20ppb, 40ppb, 50ppb, respectively. - Graphical abstract: The absorption of mercury ions on MOF-74-Zn is due to somewhat weak interactions between MOF skeleton that is composed of carboxylate and hydroxy group and Hg2+ ions. - Highlights: • MOF-74-Zn shows high removal rate of Hg(II) from water without any pretreatment. • The MOF-74-Zn has a notable performance at ultra-low concentration of Hg(II). • MOF-74-Zn shows the potential for Hg(II) removal from industrial waste water.« less

3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX): toxicological properties and risk assessment in drinking water.

PubMed

Hirose, A; Nishikawa, A; Kinae, N; Hasegawa, R

1999-01-01

MX (3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone), one of the byproducts formed during the chlorine disinfection process of drinking water, shows strong mutagenic activity for Salmonella strains in the Ames test. In several countries, the contribution of MX to the total mutagenicity of drinking water is estimated to range from 7% to 67%. To assess the risk of MX for human health, we summarized the toxicological properties of MX and estimated the tolerable daily intake (TDI) or tolerable concentration in drinking water. MX is genotoxic in cultured mammalian cells and causes in vivo DNA damage in several tissues. MX is carcinogenic for rodents in addition to possessing skin and gastric promotion activities. From these toxicological profiles of MX, we estimated the virtual safety dose (VSD) for genotoxic action as 5 ng/kg/d and the TDI for non-genotoxic action of MX as 40 ng/kg/d. We assumed a tolerable MX concentration of 150 ng/L in drinking water. Because of the uncertainty about human genotoxicity, however, and the lack of information on reproductive or developmental toxicity, the estimated tolerable dose level may be provisional.

Use of multi-coil parallel-gap resonators for co-registration EPR/NMR imaging

NASA Astrophysics Data System (ADS)

Kawada, Yuuki; Hirata, Hiroshi; Fujii, Hirodata

2007-01-01

This article reports experimental investigations on the use of RF resonators for continuous-wave electron paramagnetic resonance (cw-EPR) and proton nuclear magnetic resonance (NMR) imaging. We developed a composite resonator system with multi-coil parallel-gap resonators for co-registration EPR/NMR imaging. The resonance frequencies of each resonator were 21.8 MHz for NMR and 670 MHz for EPR. A smaller resonator (22 mm in diameter) for use in EPR was placed coaxially in a larger resonator (40 mm in diameter) for use in NMR. RF magnetic fields in the composite resonator system were visualized by measuring a homogeneous 4-hydroxy-2,2,6,6-tetramethyl-piperidinooxy (4-hydroxy-TEMPO) solution in a test tube. A phantom of five tubes containing distilled water and 4-hydroxy-TEMPO solution was also measured to demonstrate the potential usefulness of this composite resonator system in biomedical science. An image of unpaired electrons was obtained for 4-hydroxy-TEMPO in three tubes, and was successfully mapped on the proton image for five tubes. Technical problems in the implementation of a composite resonator system are discussed with regard to co-registration EPR/NMR imaging for animal experiments.

pH at the micellar interface: synthesis of pH probes derived from salicylic acid, acid-base dissociation in sodium dodecyl sulfate micelles, and Poisson-Boltzmann simulation.

PubMed

Souza, T P; Zanette, D; Kawanami, A E; de Rezende, L; Ishiki, H M; do Amaral, A T; Chaimovich, H; Agostinho-Neto, A; Cuccovia, I M

2006-05-01

The study of the H+ concentration at the micellar interface is a convenient system for modeling the distribution of H+ at interfaces. We have synthesized salicylic acid derivatives to analyze the proton dissociation of both the carboxylic and phenol groups of the probes, determining spectrophotometrically the apparent pK(a)'s (pK(ap)) in sodium dodecyl sulfate, SDS, micelles with and without added salt. The synthesized probes were 2-hydroxy-5-(2-trimethylammoniumacetyl)benzoate; 2-hydroxy-5-(2-dimethylhexadecylammoniumacetyl)benzoate; 2-hydroxy-5-(2-dimethylhexadecylammoniumhexanoyl)benzoate; 2-hydroxy-5-(2-dimethylhexadecylammoniumundecanoyl)benzoate; 2-hydroxy-5-acetylbenzoic acid; and 2-hydroxy-5-dodecanoylbenzoic acid. Upon incorporation into SDS micelles the pK(ap)'s of both carboxylic and phenol groups increased by ca. 3 pH units and NaCl addition caused a decrease in the probe-incorporated pK(ap). The experimental results were fitted with a cell model Poisson-Boltzmann (P-B) equation taking in consideration the effect of salt on the aggregation number of SDS and using the distance of the dissociating group as a parameter. The conformations of the probes were analyzed theoretically using two dielectric constants, e.g., 2 and 78. Both the P-B analysis and conformation calculations can be interpreted by assuming that the acid groups dissociate very close to, or at, the interface. Our results are consistent with the assumption that the intrinsic pK(a)'s of both carboxylic and phenol groups of the salicylic acid probes used here can be taken as those in water. Using this assumption the micellar and salt effects on the pK(ap)'s of the (trialkylammonium)benzoate probes were described accurately using a cell model P-B analysis.

Thermal formation of hydroxynitriles, precursors of hydroxyacids in astrophysical ice analogs: Acetone ((CH3)2Cdbnd O) and hydrogen cyanide (HCN) reactivity

NASA Astrophysics Data System (ADS)

Fresneau, Aurélien; Danger, Grégoire; Rimola, Albert; Duvernay, Fabrice; Theulé, Patrice; Chiavassa, Thierry

2015-11-01

Reactivity in astrophysical environments is still poorly understood. In this contribution, we investigate the thermal reactivity of interstellar ice analogs containing acetone ((CH3)2CO), ammonia (NH3), hydrogen cyanide (HCN) and water (H2O) by means of infrared spectroscopy and mass spectrometry techniques, complemented by quantum chemical calculations. We show that no reaction occurs in H2O:HCN:(CH3)2CO ices. Nevertheless, HCN does indeed react with acetone once activated by NH3 into CN- to form 2-hydroxy-2-methylpropanenitrile (HOsbnd C(CH3)2sbnd CN), with a calculated activation energy associated with the rate determining step of about 51 kJ mol-1. This reaction inhibits the formation of 2-aminopropan-2-ol (HOsbnd C(CH3)2sbnd NH2) from acetone and NH3, even in the presence of water, which is the first step of the Strecker synthesis to form 2-aminoisobutyric acid (NH2C(CH3)2COOH). However, HOsbnd C(CH3)2sbnd CN formation could be part of an alternative chemical pathway leading to 2-hydroxy-2-methyl-propanoic acid (HOC(CH3)2COOH), which could explain the presence of hydroxy acids in some meteorites.

α-Glucosylated 6-gingerol: chemoenzymatic synthesis using α-glucosidase from Halomonas sp. H11, and its physical properties.

PubMed

Ojima, Teruyo; Aizawa, Kenta; Saburi, Wataru; Yamamoto, Takeshi

2012-06-01

6-Gingerol [(S)-5-hydroxy-1-(4-hydroxy-3-methoxyphenyl)decan-3-one] is a biologically active compound and is abundant in the rhizomes of ginger (Zingiber officinale). It has some beneficial functions in healthcare, but its use is limited because of its insolubility in water and its heat-instability. To improve these physical properties, the glucosylation of 6-gingerol was investigated using α-glucosidases (EC. 3.2.1.20) from Aspergillus niger, Aspergillus nidulans ABPU1, Acremonium strictum, Halomonas sp. H11, and Saccharomyces cerevisiae, and cyclodextrin glucanotransferases (CGTase, EC. 2.4.1.19) from Bacillus coagulans, Bacillus sp. No. 38-2, Bacillus clarkii 7364, and Geobacillus stearothermophilus. Among these, only α-glucosidase from Halomonas sp. H11 (HaG) transferred a glucosyl moiety to 6-gingerol, and produced glucosylated compounds. The chemical structure of the reaction product, determined by nuclear magnetic resonance spectroscopy and mass spectrometry, was (S)-5-(O-α-D-glucopyranosyl)-1-(4-hydroxy-3-methoxyphenyl)decan-3-one (5-α-Glc-gingerol). Notably, the regioisomer formed by glucosylation of the phenolic OH was not observed at all, indicating that HaG specifically transferred the glucose moiety to the 5-OH of the β-hydroxy keto group in 6-gingerol. Almost 60% of the original 6-gingerol was converted into 5-α-Glc-gingerol by the reaction. In contrast to 6-gingerol, 5-α-Glc-gingerol, in the form of an orange powder prepared by freeze-drying, was water-soluble and stable at room temperature. It was also more stable than 6-gingerol under acidic conditions and to heat. Copyright © 2012 Elsevier Ltd. All rights reserved.

QUANTITATION OF ESTROGENS IN GROUND WATER AND SWINE LAGOON SAMPLE USING SOLID PHASE EXTRACTION, PENTAFLUROBENZYL/TRIMETHYLSILYL DERIVATIZATIONS AND GAS CHROMATOGRAPHY NEGATIVE ION CHEMICAL IONIZATION/MASS SPECTROMETRY/MASS SPECTROMETRY

EPA Science Inventory

A method was developed for the confirmed identification and quantitation of 17B-estradiol, estrone, 17B-ethynylestrodial and 16a-hydroxy-17B-estradiol (estriol) in ground water and swine lagoon samples. Centrifuged and filtered samples were extracted using solid phase extraction...

Methylene-bridged bis(benzimidazolium) salt as a highly efficient catalyst for the benzoin reaction in aqueous media.

PubMed

Iwamoto, Ken-ichi; Kimura, Hitomi; Oike, Masaaki; Sato, Masayuki

2008-03-07

Benzoin reactions are catalyzed effectively by a methylene-bridged bis(benzimidazolium) salt to yield alpha-hydroxy ketones, and the reactions proceed in water as the aqueous medium under mild conditions.

75 FR 46924 - Notice of Receipt of Several Pesticide Petitions Filed for Residues of Pesticide Chemicals in or...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-08-04

... high and adverse human health impacts or environmental effects from exposure to the pesticides... regulator, trinexapac-ethyl: 4-(cyclopropyl-[alpha]-hydroxy-methylene)- 3,5-dioxo-cyclohexanecarboxylic acid...,5-dioxo-cyclohexanecarboxylic acid, in or on grass, forage, grown for seed at 1.60 ppm; grass, hay...

78 FR 69414 - Toxic Substances Control Act Chemical Testing; Receipt of Test Data

Federal Register 2010, 2011, 2012, 2013, 2014

2013-11-19

... Chemical Testing; Receipt of Test Data AGENCY: Environmental Protection Agency (EPA). ACTION: Notice. SUMMARY: This notice announces EPA's receipt of test data on 1- propanesulfonic acid, 2-hydroxy-3-(2-propen-1-yloxy)-, sodium salt (1:1). These data were submitted pursuant to a test rule issued by EPA...

Current progress towards the metabolic engineering of plant oil for hydroxy fatty acids production

USDA-ARS?s Scientific Manuscript database

Vegetable oil is not only edible but also can be used for industrial purposes. The industrial demand for vegetable oil will increase with the future depletion of fossil fuels and environmental problems such as climate change, caused by increased carbon dioxide in the air. Some plants accumulate high...

Beta-hydroxy-beta-methylbutyrate (HMB) ameliorates age-related deficits in water maze performance, especially in male rats.

PubMed

Kougias, Daniel G; Hankosky, Emily R; Gulley, Joshua M; Juraska, Janice M

2017-03-01

Beta-hydroxy-beta-methylbutyrate (HMB) is commonly supplemented to maintain muscle in elderly and clinical populations and has potential as a nootropic. Previously, we have shown that in both male and female rats, long-term HMB supplementation prevents age-related dendritic shrinkage within the medial prefrontal cortex (mPFC) and improves cognitive flexibility and working memory performance that are both age- and sex-specific. In this study, we further explore the cognitive effects by assessing visuospatial learning and memory with the Morris water maze. Female rats were ovariectomized at 11months of age to model human menopause. At 12months of age, male and female rats received relatively short- or long-term (1- or 7-month) dietary HMB (450mg/kg/dose) supplementation twice a day prior to testing. Spatial reference learning and memory was assessed across four days in the water maze with four trials daily and a probe trial on the last day. Consistent with previous work, there were age-related deficits in water maze performance in both sexes. However, these deficits were ameliorated in HMB-treated males during training and in both sexes during probe trial performance. Thus, HMB supplementation prevented the age-related decrement in water maze performance, especially in male rats. Copyright © 2016 Elsevier Inc. All rights reserved.

Environmentally benign process for the preparation of antimicrobial α-methylene-β-hydroxy-γ-butyrolactone (tulipalin B) from tulip biomass.

PubMed

Nomura, Taiji; Hayashi, Emiko; Kawakami, Shohei; Ogita, Shinjiro; Kato, Yasuo

2015-01-01

Tulipalin B (α-methylene-β-hydroxy-γ-butyrolactone, PaB) is an antimicrobial natural product occurring in tulip (Tulipa gesneriana). PaB is directly formed from the precursor glucose ester 6-tuliposide B (PosB) by endogenous Pos-converting enzyme (TCE). Despite the potential usefulness of antibacterial PaB in various industrial applications, lack of facile synthetic schemes hampers its practical use. Herein, we describe an environmentally benign and facile process for the preparation of PaB using tulip biomass materials based on one-step enzyme reaction catalyzed by TCE without the use of petroleum-derived solvents. By screening 115 tulip cultivars, we found three elite cultivars, which accumulated PosB almost exclusively in flower tissues. The flower extracts with aqueous ethanol were partially purified with activated charcoal and subjected to the enzyme reaction with reusable immobilized TCE prepared from bulb crude extracts. The reaction was completed in a few hours at room temperature, and PaB was purified with activated charcoal and ethanol in a batch-wise manner.

Thermodynamic Parameters of the Dissolution of 4-Hydroxy-L-Proline and L-Phenylalanine in Mixed Aqueous Solvents at 298 K

NASA Astrophysics Data System (ADS)

Smirnov, V. I.; Badelin, V. G.

2018-01-01

The enthalpies of solution of 4-hydroxy-L-proline and L-phenylalanine in binary mixed aqueous solvents containing acetonitrile (AN), 1,4-dioxane (1,4-DO), or acetone (AC) at mole fractions of 0 to 0.25 are determined at T = 298.15 K via isothermal calorimetry. The standard enthalpies of solution (Δsol H°) and transfer (Δtr H°) of 4-hydroxy-L-proline and L-phenylalanine from water to mixed aqueous solvents are calculated using the experimental calorimetric data, as are the enthalpy coefficients of paired interactions ( h xy ) between the molecules of the investigated amino acids and the organic solvents. The effects the mixed aqueous solvent composition and the structure of the organic solvent molecules have on the enthalpies of solution and transfer for the investigated amino acids are considered. The correlation between the enthalpy of solution of the amino acids and the electron-donating properties of the organic solvents in the mixed aqueous solvent systems is established.

Results of analyses of the fungicide Chlorothalonil, its degradation products, and other selected pesticides at 22 surface-water sites in five Southern states, 2003-04

USGS Publications Warehouse

Scribner, Elisabeth A.; Orlando, James L.; Battaglin, William A.; Sandstrom, Mark; Kuivila, Kathryn; Meyer, Michael T.

2006-01-01

In accordance with the mission of the U.S. Geological Survey (USGS) Toxic Substances Hydrology Program, a pesticide study was conducted during 2003-04 to determine the occurrence of the fungicide chlorothalonil and its degradation products at 22 surface-water sites in five Southern States. Water-quality samples were collected during the peanut-growing season (June-September) in 2003. During the peanut-growing season in 2004, samples were collected after large storms. An analytical method was developed at the USGS Organic Geochemistry Research Laboratory in Lawrence, Kansas, to measure chlorothalonil and its degradation products by liquid chromatography/mass spectrometry (LC/MS). Chlorothalonil was detected in 4 of the 113 surface-water samples. The primary degradation product of chlorothalonil, 4-hydroxy-chlorothalonil, was detected in 26 of the 113 samples with concentrations ranging from 0.002 to 0.930 microgram per liter. The chlorothalonil degradation products, 1-amide-4-hydroxy-chorothalonil and 1,3-diamide-chlorothalonil, were detected in one water sample each at 0.020 and 0.161 microgram per liter, respectively. The USGS Methods and Research Development Group, Lakewood, Colorado, developed a custom method for chlorothalonil using gas chromatography/mass spectrometry (GC/MS) in an effort to achieve a lower laboratory reporting level (LRL) than the USGS National Water-Quality Laboratory (NWQL) schedule 2060, which analyzes the compound chlorothalonil at a LRL of 0.035 ?g/L. The group succeeded in achieving a lower GC/MS reporting level of 0.01 ?g/L. Chlorothalonil was detected in 5 of 68 water samples analyzed using the custom GC/MS method, whereas chlorothalonil was detected in 2 of 21 water samples analyzed using NWQL schedule 2060. In addition to analysis of chlorothalonil and its degradation products, samples were analyzed using the USGS NWQL schedules 2001 and 2060 for about 114 pesticides and their degradation products. Samples also were analyzed for dissolved organic carbon, suspended sediment, and percentage of silt- and clay-sized particles. Overall, it was found that chlorothalonil was detected only infrequently and at relatively low concentrations. Chlorothalonil's major degradation product, 4-hydroxy-chlorothalonil, was detected most frequently, occurred generally at higher concentrations in water samples than did the parent fungicide, and the data from this study reaffirmed that it is the dominant degradation product of chlorothalonil in the peanut-growing environment.

Exploring the Potential of a Global Emerging Contaminant Early Warning Network through the Use of Retrospective Suspect Screening with High-Resolution Mass Spectrometry.

PubMed

Alygizakis, Nikiforos A; Samanipour, Saer; Hollender, Juliane; Ibáñez, María; Kaserzon, Sarit; Kokkali, Varvara; van Leerdam, Jan A; Mueller, Jochen F; Pijnappels, Martijn; Reid, Malcolm J; Schymanski, Emma L; Slobodnik, Jaroslav; Thomaidis, Nikolaos S; Thomas, Kevin V

2018-05-01

A key challenge in the environmental and exposure sciences is to establish experimental evidence of the role of chemical exposure in human and environmental systems. High resolution and accurate tandem mass spectrometry (HRMS) is increasingly being used for the analysis of environmental samples. One lauded benefit of HRMS is the possibility to retrospectively process data for (previously omitted) compounds that has led to the archiving of HRMS data. Archived HRMS data affords the possibility of exploiting historical data to rapidly and effectively establish the temporal and spatial occurrence of newly identified contaminants through retrospective suspect screening. We propose to establish a global emerging contaminant early warning network to rapidly assess the spatial and temporal distribution of contaminants of emerging concern in environmental samples through performing retrospective analysis on HRMS data. The effectiveness of such a network is demonstrated through a pilot study, where eight reference laboratories with available archived HRMS data retrospectively screened data acquired from aqueous environmental samples collected in 14 countries on 3 different continents. The widespread spatial occurrence of several surfactants (e.g., polyethylene glycols ( PEGs ) and C12AEO-PEGs ), transformation products of selected drugs (e.g., gabapentin-lactam, metoprolol-acid, carbamazepine-10-hydroxy, omeprazole-4-hydroxy-sulfide, and 2-benzothiazole-sulfonic-acid), and industrial chemicals (3-nitrobenzenesulfonate and bisphenol-S) was revealed. Obtaining identifications of increased reliability through retrospective suspect screening is challenging, and recommendations for dealing with issues such as broad chromatographic peaks, data acquisition, and sensitivity are provided.

Deacylation transition states of a bacterial DD-peptidase.

PubMed

Adediran, S A; Kumar, I; Pratt, R F

2006-10-31

Beta-lactam antibiotics restrict bacterial growth by inhibiting DD-peptidases. These enzymes catalyze the final transpeptidation step in bacterial cell wall biosynthesis. Although much structural information is now available for these enzymes, the mechanism of the actual transpeptidation reaction has not been studied in detail. The reaction is known to involve a double-displacement mechanism with an acyl-enzyme intermediate, which can be attacked by water, specific amino acids, peptides, and other acyl acceptors. We describe in this paper an investigation of acyl acceptor specificity and assess the need for general base catalysis in the deacylation transition state of the Streptomyces R61 DD-peptidase. We show, by the criterion of solvent deuterium kinetic isotope effect measurements and proton inventories, that the transition states of specific and nonspecific substrates are very similar, at least with respect to proton motion. The transition states for attack (tetrahedral intermediate formation) by d-amino acids and Gly-l-Xaa dipeptides do not include a general base catalyst, while such catalysis is essential for reaction with water and d-alpha-hydroxy acids. D-Alpha-hydroxy acids act as acyl acceptors for glycyl substrates but not for more specific d-alanyl substrates; hydroxy acids actually behave, more generally, as mixed inhibitors of the DD-peptidase. The structural and mechanistic bases of these observations are discussed; they should inform transition state analogue design.

Synthesis and properties of hydroxy acrylic resin with high solid content

NASA Astrophysics Data System (ADS)

Yu, Zhen; Hu, Mingguang; Cui, Han; Xiao, Jijun

2017-10-01

Manufacturers of automotive repair finishes are tending to reduce more and more the level of volatile organic compounds in their paints in order to comply with increasingly strict environmental legislation. A high solid hydroxy acrylic resin was synthesised using CARDURA E10 and a type of hydroxyacrylic acid resin, its' acid value, hydroxylvalue, viscosity, structure, morphology was measured and film-forming properties after curing were characterised. The results show that the addition of CARDURA E10 in the copolymer composition significantly reduced the viscosity of the polymer system, improved the solid content of the resin and the physical properties of the coating. The hydroxyl acrylate resin with solid content of 90% and excellent comprehensive performance were successfully prepared by controlling the initiator dosage, polymerization temperature and monomer ratio.

Determination of the bioavailability of selected pharmaceutical residues in fish plasma using liquid chromatography coupled to tandem mass spectrometry.

PubMed

Poirier Larabie, S; Houde, M; Gagnon, C

2017-11-03

Aquatic systems near major urban centers are constantly contaminated with effluent from wastewater treatment plants. Pharmaceuticals are part of the contamination and several classes of drugs have been detected in surface waters in the last decade. To better understand the impact of those pharmaceuticals in ecosystems, the exposure to aquatic species needs to be investigated. This study presents a new simple and rugged quantitative method for the determination of several classes of drugs using 100μL of plasma from fish environmentally exposed to a major but highly diluted urban effluent. Six common drugs (i.e., diclofenac, ibuprofen, naproxen, salbutamol, sulfamethoxazole and trimethoprim) and one major metabolite (2-hydroxy-ibuprofen), present in significant amount in impacted waterways have been selected for the development and validation of the method. First, all drugs were extracted using cation exchange solid phase extraction (SPE) and eluted with two solvent mixtures. Then, the extracts were analyzed using a reverse-phase analytical column Waters ® CORTECS C 18 + (150×2.1mm, 2.7μm) within 14min. MS/MS was performed with an electrospray (ESI) interface in positive ion mode, with multiple reaction monitoring (MRM) experiment acquiring two product ions per drugs. Quantification has been made with standard curves for each analyte using isotopically labeled internal standards. This method has high sensitivity with limits of quantification of 1ngmL -1 for each drug, except for ibuprofen and its metabolite 2-hydroxy-ibuprofen at 2ngmL -1 . The precision of the method was below 11%, the accuracy between 94 and 105% and overall recovery between 94 and 111% for all drugs, with high selectivity. Application of the method to plasma samples from wild northern pike inhabiting the St. Lawrence River collected over a three-year period showed the presence of naproxen, diclofenac, trimethoprim and salbutamol at very low concentrations (around 1ngmL -1 ). Crown Copyright © 2017. Published by Elsevier B.V. All rights reserved.

Molecular evidence for a microbial role in ooid formation and preservation of molecular biosignatures in ancient oolite

NASA Astrophysics Data System (ADS)

Mariotti, G.; O'Reilly, S. S.; Winter, A.; Newman, S. A.; Pruss, S. B.; Bosak, T.; Klepac-Ceraj, V.; McDermott, F. P.; Summons, R. E.

2015-12-01

Ooids are concentrically laminated carbonate grains, occurring in a limited number of modern shallow marine and lacustrine settings. Oolitic sedimentary rocks (oolite) are common in the geological record, particularly in the Precambrian, and subsequent to some mass extinction events. Despite their significance, controversy remains about processes that form and shape ooids. Abiotic models typically favour carbonate precipitation in suspension in supersaturated, agitated water while biotic models emphasise microbial benthic contribution to ooid carbonate precipitation in relatively low turbulence waters. While various interpretations of ooids in the geological record have been made, the ongoing formation debate, together with post-depositional diagenesis, hinders our ability to interpret and utilize ooids to reconstruct Earth's past environments and biodiversity. Recently, Neoproterozoic oolitic carbonates have been shown to preserve C-isotopic records of environmental change and carbon cycle anomalies. This prompts the question whether molecular organic biosignatures can be found in well-preserved oolite. Here, lipid biomarker analysis and Illumina sequencing of modern ooids at Pigeon Cay, the Bahamas, revealed colonization of ooids by biofim-producing α-proteobacteria and diatoms, sulfate-reducing bacteria, anoxygenic phototrophs, as well as some cyanobacteria, in calm waters adjacent to the surf zone. These were comparable to communities associated with microbially-cemented grapestones. Relict lipids bound within ooid carbonate were also dominated by bacterial fatty acids, hydroxy acids and hopanoids. This indicates that a common, bacteria-dominated, microbial community is directly involved in carbonate precipitation of ooids and grapestones, likely by autotrophic metabolism and organomineralization of biofilms. Analysis of oolites as old as Jurassic in age revealed the preservation of hydrocarbons, as well as appreciable amounts of fatty acids, and emphasises the potential utility of oolites to preserve organic biosignatures. Further comparison of biomarkers from ooids from different environmental conditions and preservation state will provide insight into syngenetic molecular signals of environmental conditions and biological diversity in ancient oolite.

40 CFR 721.3152 - Ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl...

Code of Federal Regulations, 2010 CFR

2010-07-01

... must incorporate this new information, and any information on methods for protecting against such risk....3152 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT... significant new use of this substance is any manner or method of manufacture, import, or processing associated...

Environmental optimization for production of 7, 10-dihydroxy-8(E)-octadecenoic acid from olive oil by Pseudomonas aeruginosa PR3

USDA-ARS?s Scientific Manuscript database

Microbial conversions of free unsaturated fatty acids often generate novel hydroxy fatty acids (HFA), which are known to have special properties such as higher viscosity and reactivity. Among microbial strains known to produce HFAs, Pseudomonas aeruginosa PR3 has been well studied to produce 7,10-d...

Synthesis, structural, thermal and optical studies of 1-ethyl-2,6-dimethyl-4-hydroxy pyridinium halides.

PubMed

Dhanuskodi, S; Manivannan, S; Kirschbaum, K

2006-05-15

1-Ethyl-2,6-dimethyl-4-hydroxy pyridinium chloride dihydrate and bromide dihydrate salts have been synthesized and their single crystals were grown by the slow evaporation of aqueous solution at 30 degrees C. The grown crystals were characterized by elemental analysis, FT-NMR and FT-IR techniques to confirm the formation of the expected compound. Optical transmittance window in aqueous solution was found to be 275-1100 nm by UV-vis-NIR technique. Thermogravimetric and differential thermal analyses reveal thermal stability and the presence of two water molecules in the crystal lattices. The crystal structure of chloride salt was also determined by X-ray diffraction method.

Diclofenac Salts. V. Examples of Polymorphism among Diclofenac Salts with Alkyl-hydroxy Amines Studied by DSC and HSM

PubMed Central

Fini, Adamo; Cavallari, Cristina; Ospitali, Francesca

2010-01-01

Nine diclofenac salts prepared with alkyl-hydroxy amines were analyzed for their properties to form polymorphs by DSC and HSM techniques. Thermograms of the forms prepared from water or acetone are different in most cases, suggesting frequent examples of polymorphism among these salts. Polymorph transition can be better highlighted when analysis is carried out by thermo-microscopy, which in most cases made it possible to observe the processes of melting of the metastable form and re-crystallization of the stable one. Solubility values were qualitatively related to the crystal structure of the salts and the molecular structure of the cation. PMID:27721347

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

Samskog, P.; Kispert, L.D.; Lund, A.

Three different radicals were identified by EPR in x-ray irradiated single crystals of trehalose at 3 K. The species are the trapped electron, a hydroxy alkyl radical, and an alkoxy radical. The electron is trapped in an intermolecular site formed by two hydroxyl groups, one on the carbohydrate and the other on a water molecule as evidenced by the anisotropic proton hyperfine couplings. A geometric model for the trapping site is presented. The trapped electron decays by cleavage of an OH bond and the liberated hydrogen atom abstracts another hydrogen atom from an adjacent carbon atom forming a hydroxy alkylmore » radical. The site of the alkoxy radical has been identified. The primary reaction mechanism is discussed.« less

Development and validation of an ultra high performance liquid chromatography-electrospray tandem mass spectrometry method using selective derivatisation, for the quantification of two reactive aldehydes produced by lipid peroxidation, HNE (4-hydroxy-2(E)-nonenal) and HHE (4-hydroxy-2(E)-hexenal) in faecal water.

PubMed

Chevolleau, S; Noguer-Meireles, M-H; Jouanin, I; Naud, N; Pierre, F; Gueraud, F; Debrauwer, L

2018-04-15

Red or processed meat rich diets have been shown to be associated with an elevated risk of colorectal cancer (CRC). One major hypothesis involves dietary heme iron which induces lipid peroxidation. The quantification of the resulting reactive aldehydes (e.g. HNE and HHE) in the colon lumen is therefore of great concern since these compounds are known for their cytotoxic and genotoxic properties. UHPLC-ESI-MS/MS method has been developed and validated for HNE and HHE quantification in rat faeces. Samples were derivatised using a brominated reagent (BBHA) in presence of pre-synthesized deuterated internal standards (HNE-d11/HHE-d5), extracted by solid phase extraction, and then analysed by LC-positive ESI-MS/MS (MRM) on a TSQ Vantage mass spectrometer. The use of BBHA allowed the efficient stabilisation of the unstable and reactive hydroxy-alkenals HNE and HHE. The MRM method allowed selective detection of HNE and HHE on the basis of characteristic transitions monitored from both the 79 and 81 bromine isotopic peaks. This method was validated according to the European Medicines Agency (EMEA) guidelines, by determining selectivity, sensitivity, linearity, carry-over effect, recovery, matrix effect, repeatability, trueness and intermediate precision. The performance of the method enabled the quantification of HNE and HHE in concentrations 0.10-0.15 μM in faecal water. Results are presented on the application to the quantification of HNE and HHE in different faecal waters obtained from faeces of rats fed diets with various fatty acid compositions thus corresponding to different pro-oxidative features. Copyright © 2018 Elsevier B.V. All rights reserved.

Annual West Coast Theoretical Chemistry/Statistical Mechanics Conference (14th), held at Los Angeles, California on 17-19 June 1993

DTIC Science & Technology

1993-06-19

of California, Los Angles, CA AB-INITIO STUDIES OF WATER CLUSTERSt Sotris S. Xantheas and Thorn H. Dunning Jr. Molecular Theory Group, Molecular...mechanics, of the solvation properties of a chlorine ion in polarizable water . In these studies , we employed the polarizable water model developed recently by...acetaldehyde, hydrogen sulfide with 2-hydroxy-3-methylbutan-2-yl, and lithium hydride with methyl isopropyl ketone . The largest system studied . 1. contains

Comparative oxidative metabolism of BDE-47 and BDE-99 by rat hepatic microsomes.

PubMed

Erratico, Claudio A; Moffatt, Sarah C; Bandiera, Stelvio M

2011-09-01

Polybrominated diphenyl ethers (PBDEs) are flame-retardant chemicals that have become ubiquitous environmental pollutants. 2,2',4,4'-Tetrabromodiphenyl ether (BDE-47) and 2,2',4,4',5-pentabromodiphenyl ether (BDE-99) are among the most prevalent PBDEs detected in humans, wildlife, and abiotic environmental matrices. The purpose of this study was to investigate the oxidative metabolism of BDE-47 and BDE-99 in rat hepatic microsomes by comparing metabolite formation rates, kinetic parameters associated with metabolite formation, and the effects of prototypical cytochrome P450 (CYP) inducers. The CYP enzymes involved were also identified. Incubation of BDE-47 with hepatic microsomes from phenobarbital-treated rats generated a total of five hydroxylated (OH-BDE) metabolites, among which 4'-hydroxy-2,2',4,5'-tetrabromodiphenyl ether (4'-OH-BDE-49) and 3-hydroxy-2,2',4,4'-tetrabromodiphenyl ether (3-OH-BDE-47) were the major metabolites, as identified using authentic standards and quantified by liquid chromatography/mass spectrometry. Incubations of BDE-99 with hepatic microsomes from dexamethasone-treated rats produced a total of seven hydroxylated metabolites, among which 4-hydroxy-2,2',3,4',5-pentabromodiphenyl ether (4-OH-BDE-90) and 6'-hydroxy-2,2',4,4',5-pentabromodiphenyl ether (6'-OH-BDE-99) were the major metabolites. Although the overall rate of oxidative metabolism of BDE-99 by hepatic microsomes was greater than that of BDE-47, para-hydroxylation involving a National Institutes of Health shift mechanism represented a major metabolic pathway for both PBDE congeners. Among the rat recombinant CYP enzymes tested, CYP2A2 and CYP3A1 were the most active in BDE-47 and BDE-99 metabolism, respectively. However, CYP1A1 exhibited the highest activity for 4'-OH-BDE-49 and 6'-OH-BDE-99 formation, and CYP3A1 exhibited the highest activity for 3-OH-BDE-47 and 4-OH-BDE-90 formation. Collectively, the results demonstrate that oxidative metabolism of BDE-47 and BDE-99 is mediated by distinct but overlapping sets of CYP enzymes and represents a key process that determines the bioaccumulation of BDE-47 and BDE-99 in mammals.

Occurrence of Chlorothalonil, Its Transformation Products, and Selected Other Pesticides in Texas and Oklahoma Streams, 2003-2004

USGS Publications Warehouse

Battaglin, William A.; Kuivila, Kathryn; Winton, Kim; Meyer, Michael

2008-01-01

The primary purpose of the study described in this report was to determine if the fungicide chlorothalonil (2,4,5,6-tetrachloroisophthalonitrile), three of its transformation products, or selected other pesticides are transported to surface water after use on peanuts or other crops in Texas and Oklahoma. The results summarized here are part of a larger study that includes data from sites in Alabama, Florida, and Georgia. Chlorothalonil is classified as a probable carcinogen, and the 4-hydroxy of chlorothalonil transformation product is more soluble, more stable, and, for some species, more toxic than its parent compound. In 2003, water samples were collected from three surface-water sites in Texas and two surface-water sites in Oklahoma; in 2004, samples were collected from the two Oklahoma sites. Chlorothalonil was not detected in any of the 20 samples analyzed. The 4-hydroxy of chlorothalonil transformation product was detected in three samples collected in 2004, with a maximum concentration of 0.018 microgram per liter (?g/L); the other two transformation products (diamide chlorothalonil and 1-amide-4-hydroxy chlorothalonil) were not detected in any sample. In addition, 19 samples were analyzed for as many as 109 other pesticides and transformation products. Atrazine was detected in 13 samples and had a maximum concentration of 0.122 ?g/L. Deethylatrazine was detected in 10 samples and had a maximum concentration of 0.04 ?g/L. Metolachlor was detected in eight samples and had a maximum concentration of 0.019 ?g/L. Fifteen other pesticides or pesticide transformation products also were detected. In general, concentrations of pesticides were less than concentrations that are commonly observed in Midwestern streams. The results indicate that the use of chlorothalonil on peanut crops has not resulted in substantial contamination of the studied streams in Texas and Oklahoma.

Formation and Survival of Amino Acids in Space

NASA Technical Reports Server (NTRS)

Bernstein, M. P.; Sandford, S. A.; Allamandola, L. J.

2003-01-01

The detection of deuterium enrichments in meteoritic hydroxy and amino acids demonstrates that there is a connection between organic material in the interstellar medium and in piimitive meteorites. It has generally been assumed that such molecules formed via reactions of small deuterium enriched insterstellar precursors in liquid water on a large asteroidal or cometary parent body. We have recently show that the W photolysis of interstellar/presolar ices can produce the amino acids alanine, serine, and glycine, as well as hydroxy acids, and glycerol, all of which have been extracted from the Murchison meteorite. Thus, some of the probiologically interesting organic compounds compounds found in meteorites may have formed in presolar ice and have not solely been a product of parent body liquid water chemistry. We will report on our isotopic labeling studies of the mechanism of formation of these inteiesting compounds, and on astrophysically relevant kinetic studies UV photo-decomposition of amino acid precursors in the solid state. This is our first year of exobiology funding on this project.

Formation and Survival of Amino Acids in Space

NASA Technical Reports Server (NTRS)

Bernstein, M. P.; Sandford, S. A.; Allamandola, L. J.

2003-01-01

The detection of deuterium enrichments in meteoritic hydroxy and amino acids demonstrates that there is a connection between organic material in the interstellar medium and in primitive meteorites. It has generally been assumed that such molecules formed via reactions of small deuterium enriched insterstellar precursors in liquid water on a large asteroidal or cometary parent body. We have recently show that the W photolysis of interstellar/presolar ices can produce the amino acids alanine, serine, and glycine, as well as hydroxy acids, and glycerol, all of which have been extracted from the Murchison meteorite. Thus, some of the probiologically interesting organic compounds, compounds found in meteorites may have formed in presolar ice and have not solely been a product of parent body liquid water chemistry. We will report on our isotopic labeling studies of the mechanism of formation of these interesting compounds, and on astrophysically relevant kinetic studies UV photodecomposition of amino acid precursors in the solid state. This is our first year of exobiology funding on this project.

Effects of water-soluble natural antioxidants on photosensitized oxidation of conjugated linoleic acid in an oil-in-water emulsion system.

PubMed

Liu, T-T; Yang, T-S

2008-05-01

The effect of photosensitized oxidation of conjugated linoleic acid in an oil-in-water (o/w) emulsion system was studied. Water-soluble natural antioxidants, including apple polyphenols from apple extract, green tea extract, 4-hydroxy-2(or 5)-ethyl-5(or2)-methyl-3(2H)-furanone(HEMF), 4-hydroxy-2,5-dimethyl-3(2H)-furanone (HDMF), and ascorbic acid, were tested for antioxidant activity in this system. The green tea extract showed the highest antioxidant activity followed by ascorbic acid. Apple polyphenols did not give significant antioxidant activity. HEMF and HDMF exhibited a prooxidant effect. The antioxidant activity of tea catechins was also investigated. Of them, EGCG and ECG exhibited antioxidant activity at 50 ppm, but the antioxidant activity between them was not significantly different (P < 0.05). Comparatively, EC, EGC, and GCG showed no significant antioxidative effect at 50 ppm. When the concentration increased to 100 ppm, the antioxidant activity of ECG and EGCG significantly increased compared with that at 50 ppm, and EGCG had higher antioxidant activity than ECG. GCG also showed significant antioxidant activity at 100 ppm. EGCG exhibited the highest antioxidant activity among the tea catechins in the emulsion system at 100 ppm.

40 CFR 721.5288 - Chromate(2-), [3-hydroxy-4-[(2-hydroxy-1-naphthenyl)azo]-7-nitro-1-substituted][N-[7-hydroxy-8...

Code of Federal Regulations, 2010 CFR

2010-07-01

... (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.5288 Chromate(2-), [3-hydroxy-4-[(2-hydroxy-1-naphthenyl)azo]-7-nitro-1-substituted][N-[7-hydroxy-8-[(2-hydroxy-5-nitrophenyl)azo]-1-substituted]-, salt (generic). (a) Chemical...

Synthesis, spectral characterization and biological studies of some organotin(IV) complexes of L-proline, trans-hydroxy- L-proline and L-glutamine

NASA Astrophysics Data System (ADS)

Nath, Mala; Jairath, Ruchi; Eng, George; Song, Xueqing; Kumar, Ashok

2005-12-01

New organotin(IV) complexes of the general formula R 3Sn(L) (where R = Me, n-Bu and HL = L-proline; R = Me, Ph and HL = trans-hydroxy- L-proline and L-glutamine) and R 2Sn(L) 2 (where R = n-Bu, Ph and HL = L-proline; R = Ph, HL = trans-hydroxy- L-proline) have been synthesized by the reaction of R nSnCl 4- n (where n = 2 or 3) with sodium salt of the amino acid (HL). n-Bu 2Sn(Pro) 2 was synthesized by the reaction of n-Bu 2SnO with L-proline under azeotropic removal of water. The bonding and coordination behavior in these complexes have been discussed on the basis of IR and 119Sn Mössbauer spectroscopic studies in the solid-state. Their coordination behavior in solution has been discussed with the help of multinuclear ( 1H, 13C and 119Sn) NMR spectral studies. The 119Sn Mössbauer and IR studies indicate that L-proline and trans-hydroxy- L-proline show similar coordination behavior towards organotin(IV) compounds. Pentacoordinate trigonal-bipyramidal and hexacoordinate octahedral structures, respectively, have been proposed for the tri- and diorganotin(IV) complexes of L-proline and trans-hydroxy- L-proline, in which the carboxylate group acts as bidentate group. L-Glutamine shows different coordination behavior towards organotin(IV) compounds, it acts as monoanionic bidentate ligand coordinating through carboxylate and amino group. The triorganotin(IV) complexes of L-glutamine have been proposed to have trigonal-bipyramidal environment around tin. The newly synthesized complexes have been tested for their antiinflammatory and cardiovascular activities. Their LD 50 values are >1000 mg kg -1.

Effect of 4-hydroxy-2-nonenal on myoglobin-mediated lipid oxidation when varying histidine content and hemin affinity.

PubMed

Grunwald, Eric W; Tatiyaborworntham, Nantawat; Faustman, Cameron; Richards, Mark P

2017-07-15

The compound 4-hydroxy-2-nonenal (HNE) dissolved in water was examined to remove potential effects of using ethanol to solubilize the aldehyde such as altering protein structure or redox properties of myoglobin (Mb). HNE became covalently bound to sperm whale Mb at up to five sites based on ESI-MS analysis. Adducted Mb promoted lipid oxidation in washed muscle more effectively than non-adducted Mb. Alkylation of P88H/Q152HMb with HNE accelerated metMb formation and subsequent lipid oxidation. P88H/Q152HMb exposed to HNE enhanced lipid oxidation compared to wild-type Mb exposed to HNE. Results using H97A Mb suggested that the combination of HNE and low hemin affinity facilitated rapid decomposition of preformed lipid hydroperoxides to secondary lipid oxidation products. HNE and HHE (4-hydroxy-2-hexenal) facilitated Mb-mediated lipid oxidation similarly. The potential mechanisms by which Mb binding of α,β-unsaturated aldehydes affect Mb oxidation and the onset of lipid oxidation are discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Synthesis of 4-hydroxy-3-methylchalcone from Reimer-Tiemann reaction product and its antibacterial activity test

NASA Astrophysics Data System (ADS)

Hapsari, M.; Windarti, T.; Purbowatiningrum; Ngadiwiyana; Ismiyarto

2018-04-01

A 4-hydroxy-3-methylchalcone has been synthesized from 4-hydroxy-3-methylbenzaldehyde as the Reimer-Tiemann reaction product. This research consists of three steps involve synthesize of 4-hydroxy-3-methylbenzaldehyde from ortho-cresol, synthesize of chalcone derivatives from 4-hydroxy-3-methylbenzaldehyde and 4-hydroxy-3-methoxybenzaldehyde or vanillin for the comparison, the last is antibacterial activity test of both chalcone derivatives against Escherichia coli (negative gram) and Staphylococcus aureus (positive gram) bacteria using disc diffusion method. Results of Reimer-Tiemann reaction is 4-hydroxy-3-methylbenzaldehyde compound in an orange colour solid form which has 43% yields and melting point 110-114°C. A 4-hydroxy-3-methylbenzaldehyde then reacted with acetophenone in a base condition and form 4-hydroxy-3-methylchalcone compound in a yellow colour solid form which has 40% yields and melting point 83-86°C. The antibacterial activity of the 4-hydroxy-3-methylchalcone against gram-positive bacteria Staphylococcus aureus is better than the 4-hydroxy-3-methoxychalcone.

Facile synthesis of "green" gold nanocrystals using cynarin in an aqueous solution

NASA Astrophysics Data System (ADS)

Katircioğlu, Zeynep; Şakalak, Hüseyin; Ulaşan, Mehmet; Gören, Ahmet Ceyhan; Yavuz, Mustafa Selman

2014-11-01

Herein we describe a water-based protocol that generates Au nanoparticles (AuNPs) by mixing aqueous solutions of HAuCl4 and cynarin (a natural product extract from artichoke leaf). Based on the observations from 1H NMR spectrum of AuNPs, a polyol oxidation mechanism by metal ions which eventually results in AuNPs formation, is proposed. Basically, the aromatic alcohol groups (1,2-benzenediol) of cynarin are oxidized to α-hydroxy ketone intermediate product, and then further oxidized to the vicinal diketone final product while the Au3+ ions are reduced to its atomic form (Au0) which leads the generation of Au nanoparticles. This new protocol has also been employed to prepare multiply twinned Pd nanoparticles and Ag cubical aggregates. Due to exclusion of organic solvent, surfactant, or stabilizer for all these synthesis, this protocol may provide a simple, versatile, and environmentally benign route to fabricate noble-metal nanoparticles having various compositions and morphologies.

Method of removing and detoxifying a phosphorus-based substance

DOEpatents

Vandegrift, G.F.; Steindler, M.J.

1985-05-21

A method of removing a phosphorus-based poisonous substance from water contaminated is presented. In addition, the toxicity of the phosphorus-based substance is also subsequently destroyed. A water-immiscible organic solvent is first immobilized on a supported liquid membrane before the contaminated water is contacted with one side of the supported liquid membrane to absorb the phosphorus-based substance in the organic solvent. The other side of the supported liquid membrane is contacted with a hydroxy-affording strong base to react with phosphorus-based solvated species to form a non-toxic product.

Optimal production of 7,10-dihydroxy-8(E)-hexadecenoic acid from palmitoleic acid by Pseudomonas aeruginosa PR3.

PubMed

Bae, Jae-Han; Suh, Min-Jung; Kim, Beom-Soo; Hou, Ching T; Lee, In-Jung; Kim, In-Hwan; Kim, Hak-Ryul

2010-09-30

The hydroxylation of unsaturated fatty acids by bacterial strains is one type of value-adding bioconversion processes. 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 tested for HFA production, Pseudomonas aeruginosa PR3 is well known to utilize various unsaturated fatty acids to produce mono-, di- and tri-hydroxy fatty acids. Previously we reported that strain PR3 could produce a novel value-added hydroxy fatty acid 7,10-dihydroxy-8(E)-hexadecenoic acid (DHD) from palmitoleic acid (Bae et al. (2007) Appl. Microbiol. Biotechnol. 75, 435-440). In this study, we focused on the development of the optimal nutritional and environmental conditions for DHD production from palmitoleic acid by PR3. Optimal carbon and nitrogen sources for DHD production were fructose and yeast extract, respectively. Optimal initial medium pH and incubation temperature were pH 8.0 and 30 degrees C and magnesium ion was essentially required for DHD production. Substrate concentration and time of substrate addition were also optimized. Under optimized conditions, maximal DHD production was 1600mg/l representing 26.7% conversion yield. Copyright 2009 Elsevier B.V. All rights reserved.

Multicomponent hydrogen-bonding organic solids constructed from 6-hydroxy-2-naphthoic acid and N-heterocycles: Synthesis, structural characterization and synthon discussion

NASA Astrophysics Data System (ADS)

Zong, Yingxia; Shao, Hui; Pang, Yanyan; Wang, Debao; Liu, Kang; Wang, Lei

2016-07-01

Seven novel multicomponent crystals involving various substituted organic amine molecules and 6-hydroxy-2-naphthoic acid were prepared and characterized by using single crystal X-ray diffraction, infrared and thermogravimetric analyses (TGA). Crystal structures with 1,4-bis(imidazol) butane (L1) 1, 1,4-bis(imidazol-1-ylmethyl)benzene (L2) 2, 1-phenyl piperazine 3, 2-amino-4-hydroxy-6-methyl pyrimidine 4, 4,4'-bipyridine 5, 5,5'-dimethyl-2,2'-dipyridine 6, 2-amino-4,6-dimethyl pyrimidine 7 were determined. Among the seven molecular complexes, total proton transfer from 6-hydroxy-2-naphthoic acid to coformer has occurred in crystals 1-4, while the remaining were cocrystals. X-ray single-crystal structures of these complexes reveal that strong hydrogen bonding O-H···O/N-H···O/O-H···N and weak C-H···O/C-H···π/π···π intermolecular interactions direct the packing modes of molecular crystals together. The analysis of supramolecular synthons in the present structures shows that some classical supramolecular synthons like pyridine-carboxylic acid heterosynthon R22 (7) and aminopyridine-carboxylic acid heterosynthon R22 (8), are again observed in constructing the hydrogen-bonding networks in this paper. Besides, we noticed that water molecules act as a significant hydrogen-bonding connector in constructing supramolecular architectures of 3, 4, 6, and 7.

Characterization of the key aroma compounds in soy sauce using approaches of molecular sensory science.

PubMed

Steinhaus, Petra; Schieberle, Peter

2007-07-25

Application of aroma extract dilution analysis (AEDA) to the volatiles isolated from a commercial Japanese soy sauce revealed 30 odor-active compounds in the flavor dilution (FD) factor range of 8-4096, among which 2-phenylethanol showed the highest FD factor of 4096, followed by 3-(methylsulfanyl)propanal (methional), the tautomers 4-hydroxy-5-ethyl-2-methyl- and 4-hydroxy-2-ethyl-5-methyl-3(2H)-furanone (4-HEMF), 4-hydroxy-2,5-dimethyl-3(2H)-furanone (4-HDF), and 3-hydroxy-4,5-dimethyl-2(5H)-furanone (sotolone), all showing FD factors of 1024. Thirteen odorants were quantified by stable isotope dilution assays, and their odor activity values (OAVs) were calculated as ratio of their concentrations and odor thresholds in water. Among them, 3-methylbutanal (malty), sotolone (seasoning-like), 4-HEMF (caramel-like), 2-methylbutanal (malty), methional (cooked potato), ethanol (alcoholic), and ethyl 2-methylpropanoate (fruity) showed the highest OAVs (>200). An aqueous model aroma mixture containing 13 odorants, which had been identified with the highest OAVs, in concentrations that occur in the soy sauce showed a good similarity with the overall aroma of the soy sauce itself. Heat treatment of the soy sauce resulted in a clear change of the overall aroma. Quantitation of selected odorants revealed a significant decrease in sotolone and, in particular, increases in 2-acetyl-1-pyrroline, 4-HDMF, and 4-HEMF induced by heating.

Arabidopsis Deficient in Cutin Ferulate Encodes a Transferase Required for Feruloylation of ω-Hydroxy Fatty Acids in Cutin Polyester1[W][OA

PubMed Central

Rautengarten, Carsten; Ebert, Berit; Ouellet, Mario; Nafisi, Majse; Baidoo, Edward E.K.; Benke, Peter; Stranne, Maria; Mukhopadhyay, Aindrila; Keasling, Jay D.; Sakuragi, Yumiko; Scheller, Henrik Vibe

2012-01-01

The cuticle is a complex aliphatic polymeric layer connected to the cell wall and covers surfaces of all aerial plant organs. The cuticle prevents nonstomatal water loss, regulates gas exchange, and acts as a barrier against pathogen infection. The cuticle is synthesized by epidermal cells and predominantly consists of an aliphatic polymer matrix (cutin) and intracuticular and epicuticular waxes. Cutin monomers are primarily C16 and C18 unsubstituted, ω-hydroxy, and α,ω-dicarboxylic fatty acids. Phenolics such as ferulate and p-coumarate esters also contribute to a minor extent to the cutin polymer. Here, we present the characterization of a novel acyl-coenzyme A (CoA)-dependent acyl-transferase that is encoded by a gene designated Deficient in Cutin Ferulate (DCF). The DCF protein is responsible for the feruloylation of ω-hydroxy fatty acids incorporated into the cutin polymer of aerial Arabidopsis (Arabidopsis thaliana) organs. The enzyme specifically transfers hydroxycinnamic acids using ω-hydroxy fatty acids as acyl acceptors and hydroxycinnamoyl-CoAs, preferentially feruloyl-CoA and sinapoyl-CoA, as acyl donors in vitro. Arabidopsis mutant lines carrying DCF loss-of-function alleles are devoid of rosette leaf cutin ferulate and exhibit a 50% reduction in ferulic acid content in stem insoluble residues. DCF is specifically expressed in the epidermis throughout all green Arabidopsis organs. The DCF protein localizes to the cytosol, suggesting that the feruloylation of cutin monomers takes place in the cytoplasm. PMID:22158675

Arabidopsis Deficient in Cutin Ferulate encodes a transferase required for feruloylation of ω-hydroxy fatty acids in cutin polyester.

PubMed

Rautengarten, Carsten; Ebert, Berit; Ouellet, Mario; Nafisi, Majse; Baidoo, Edward E K; Benke, Peter; Stranne, Maria; Mukhopadhyay, Aindrila; Keasling, Jay D; Sakuragi, Yumiko; Scheller, Henrik Vibe

2012-02-01

The cuticle is a complex aliphatic polymeric layer connected to the cell wall and covers surfaces of all aerial plant organs. The cuticle prevents nonstomatal water loss, regulates gas exchange, and acts as a barrier against pathogen infection. The cuticle is synthesized by epidermal cells and predominantly consists of an aliphatic polymer matrix (cutin) and intracuticular and epicuticular waxes. Cutin monomers are primarily C(16) and C(18) unsubstituted, ω-hydroxy, and α,ω-dicarboxylic fatty acids. Phenolics such as ferulate and p-coumarate esters also contribute to a minor extent to the cutin polymer. Here, we present the characterization of a novel acyl-coenzyme A (CoA)-dependent acyl-transferase that is encoded by a gene designated Deficient in Cutin Ferulate (DCF). The DCF protein is responsible for the feruloylation of ω-hydroxy fatty acids incorporated into the cutin polymer of aerial Arabidopsis (Arabidopsis thaliana) organs. The enzyme specifically transfers hydroxycinnamic acids using ω-hydroxy fatty acids as acyl acceptors and hydroxycinnamoyl-CoAs, preferentially feruloyl-CoA and sinapoyl-CoA, as acyl donors in vitro. Arabidopsis mutant lines carrying DCF loss-of-function alleles are devoid of rosette leaf cutin ferulate and exhibit a 50% reduction in ferulic acid content in stem insoluble residues. DCF is specifically expressed in the epidermis throughout all green Arabidopsis organs. The DCF protein localizes to the cytosol, suggesting that the feruloylation of cutin monomers takes place in the cytoplasm.

40 CFR 721.10107 - Naphthalenedisulfonic acid, [amino-hydroxy-[(substituted)azo-sulfo-naphthaleneyl]azo]-hydroxy...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Naphthalenedisulfonic acid, [amino... Specific Chemical Substances § 721.10107 Naphthalenedisulfonic acid, [amino-hydroxy-[(substituted)azo-sulfo... naphthalenedisulfonic acid, [amino-hydroxy-[(substituted)azo-sulfo-naphthaleneyl]azo]-hydroxy-[(methoxy-sulfophenyl)azo...

40 CFR 721.10107 - Naphthalenedisulfonic acid, [amino-hydroxy-[(substituted)azo-sulfo-naphthaleneyl]azo]-hydroxy...

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Naphthalenedisulfonic acid, [amino... Specific Chemical Substances § 721.10107 Naphthalenedisulfonic acid, [amino-hydroxy-[(substituted)azo-sulfo... naphthalenedisulfonic acid, [amino-hydroxy-[(substituted)azo-sulfo-naphthaleneyl]azo]-hydroxy-[(methoxy-sulfophenyl)azo...

Formation of Light Absorbing Soluble Secondary Organics and Insoluble Polymeric Particles from the Dark Reaction of Catechol and Guaiacol with Fe(III).

PubMed

Slikboer, Samantha; Grandy, Lindsay; Blair, Sandra L; Nizkorodov, Sergey A; Smith, Richard W; Al-Abadleh, Hind A

2015-07-07

Transition metals such as iron are reactive components of environmentally relevant surfaces. Here, dark reaction of Fe(III) with catechol and guaiacol was investigated in an aqueous solution at pH 3 under experimental conditions that mimic reactions in the adsorbed phase of water. Using UV-vis spectroscopy, liquid chromatography, mass spectrometry, elemental analysis, dynamic light scattering, and electron microscopy techniques, we characterized the reactants, intermediates, and products as a function of reaction time. The reactions of Fe(III) with catechol and guaiacol produced significant changes in the optical spectra of the solutions due to the formation of light absorbing secondary organics and colloidal organic particles. The primary steps in the reaction mechanism were shown to include oxidation of catechol and guaiacol to hydroxy- and methoxy-quinones. The particles formed within a few minutes of reaction and grew to micron-size aggregates after half an hour reaction. The mass-normalized absorption coefficients of the particles were comparable to those of strongly absorbing brown carbon compounds produced by biomass burning. These results could account for new pathways that lead to atmospheric secondary organic aerosol formation and abiotic polymer formation on environmental surfaces mediated by transition metals.

Evaluation of lot-to-lot repeatability and effect of assay media choice in the recombinant Factor C assay.

PubMed

McKenzie, Jennifer Helen; Alwis, K Udeni; Sordillo, Joanne E; Kalluri, Kesava Srinivas; Milton, Donald Kirby

2011-06-01

Measurement of environmental endotoxin exposures is complicated by variability encountered using current biological assay methods arising in part from lot-to-lot variability of the Limulus-amebocyte lysate (LAL) reagents. Therefore, we investigated the lot-to-lot repeatability of commercially available recombinant Factor C (rFC) kits as an alternative to LAL. Specifically, we compared endotoxin estimates obtained from rFC assay of twenty indoor dust samples, using four different extraction and assay media, to endotoxin estimates previously obtained by Limulus amebocyte lysate (LAL) assay and amounts of 3-hydroxy fatty acids (3-OHFA) in lipopolysaccharide (LPS) using gas-chromatography mass spectroscopy (GC-MS). We found that lot-to-lot variability of the rFC assay kits does not significantly alter endotoxin estimates in house dust samples when performed using three of the four assay media tested and that choice of assay media significantly altered endotoxin estimates obtained by rFC assay of house dust samples. Our findings demonstrate lot-to-lot reproducibility of rFC assay of environmental samples and suggest that use of rFC assay performed with Tris buffer or water as the extraction and assay medium for measurement of endotoxin in dust samples may be a suitable choice for developing a standardized methodology.

Bioconjugatable Porphyrins Bearing a Compact Swallowtail Motif for Water Solubility

PubMed Central

Borbas, K. Eszter; Mroz, Pawel; Hamblin, Michael R.; Lindsey, Jonathan S.

2011-01-01

A broad range of applications requires access to water-soluble, bioconjugatable porphyrins. Branched alkyl groups attached at the branching site to the porphyrin meso position are known to impart high organic solubility. Such “swallowtail” motifs bearing a polar group (hydroxy, dihydroxyphosphoryl, dihydroxyphosphoryloxy) at the terminus of each branch have now been incorporated at a meso site in trans-AB-porphyrins. The incorporation of the swallowtail motif relies on rational synthetic methods whereby a 1,9-bis(N-propylimino)dipyrromethane (bearing a bioconjugatable tether at the 5-position) is condensed with a dipyrromethane (bearing a protected 1,5-dihydroxypent-3-yl unit at the 5-position). The two hydroxy groups in the swallowtail motif of each of the resulting zinc porphyrins can be transformed to the corresponding diphosphate or diphosphonate product. A 4-(carboxymethyloxy)phenyl group provides the bioconjugatable tether. The six such porphyrins reported here are highly water-soluble (≥20 mM at room temperature in water at pH 7) as determined by visual inspection, UV–vis absorption spectroscopy, or 1H NMR spectroscopy. Covalent attachment was carried out in aqueous solution with the unprotected porphyrin diphosphonate and a monoclonal antibody against the T-cell receptor CD3ε. The resulting conjugate performed comparably to a commercially available fluorescein isothiocyanate-labeled antibody with Jurkat cells in flow cytometry and fluorescence microscopy assays. Taken together, this work enables preparation of useful quantities of water-soluble, bioconjugatable porphyrins in a compact architecture for applications in the life sciences. PMID:16704201

An ultra performance liquid chromatography-tandem MS assay for tamoxifen metabolites profiling in plasma: first evidence of 4'-hydroxylated metabolites in breast cancer patients.

PubMed

Dahmane, E; Mercier, T; Zanolari, B; Cruchon, S; Guignard, N; Buclin, T; Leyvraz, S; Zaman, K; Csajka, C; Decosterd, L A

2010-12-15

There is increasing evidence that the clinical efficacy of tamoxifen, the first and most widely used targeted therapy for estrogen-sensitive breast cancer, depends on the formation of the active metabolites 4-hydroxy-tamoxifen and 4-hydroxy-N-desmethyl-tamoxifen (endoxifen). Large inter-individual variability in endoxifen plasma concentrations has been observed and related both to genetic and environmental (i.e. drug-induced) factors altering CYP450s metabolizing enzymes activity. In this context, we have developed an ultra performance liquid chromatography-tandem mass spectrometry method (UPLC-MS/MS) requiring 100 μL of plasma for the quantification of tamoxifen and three of its major metabolites in breast cancer patients. Plasma is purified by a combination of protein precipitation, evaporation at room temperature under nitrogen, and reconstitution in methanol/20 mM ammonium formate 1:1 (v/v), adjusted to pH 2.9 with formic acid. Reverse-phase chromatographic separation of tamoxifen, N-desmethyl-tamoxifen, 4-hydroxy-tamoxifen and 4-hydroxy-N-desmethyl-tamoxifen is performed within 13 min using elution with a gradient of 10 mM ammonium formate and acetonitrile, both containing 0.1% formic acid. Analytes quantification, using matrix-matched calibration samples spiked with their respective deuterated internal standards, is performed by electrospray ionization-triple quadrupole mass spectrometry using selected reaction monitoring detection in the positive mode. The method was validated according to FDA recommendations, including assessment of relative matrix effects variability, as well as tamoxifen and metabolites short-term stability in plasma and whole blood. The method is precise (inter-day CV%: 2.5-7.8%), accurate (-1.4 to +5.8%) and sensitive (lower limits of quantification comprised between 0.4 and 2.0 ng/mL). Application of this method to patients' samples has made possible the identification of two further metabolites, 4'-hydroxy-tamoxifen and 4'-hydroxy-N-desmethyl-tamoxifen, described for the first time in breast cancer patients. This UPLC-MS/MS assay is currently applied for monitoring plasma levels of tamoxifen and its metabolites in breast cancer patients within the frame of a clinical trial aiming to assess the impact of dose increase on tamoxifen and endoxifen exposure. Copyright © 2010 Elsevier B.V. All rights reserved.

The zebra mussel (Dreissena polymorpha), a new pest in North America: reproductive mechanisms as possible targets of control strategies

USGS Publications Warehouse

Ram, Jeffrey L.; Fong, Peter; Croll, Roger P.; Nichols, Susan J.; Wall, Darcie

1992-01-01

The zebra mussel (Dreissena polymorpha) has spread rapidly in temperate fresh waters of North America since its introduction into the Great Lakes in 1985 or 1986. It attaches to hard substrates, forming layers, occluding water intakes, encrusting and killing native mussels, filtering algae in competition with other planktivores, and possibly interfering with fish spawning. It reproduces prolifically, suggesting that an approach to its control may be by controlling its reproduction. Previous literature suggests that spawning in bivalves is regulated by both environmental and internal chemical cues. A suggested sequence is that phytoplankton chemicals initially trigger spawning; chemicals associated with gametes provide a species-specific pheromonal positive feedback for spawning; and the response to environmental chemicals is mediated internally by serotonin (5-HT). The role of 5-HT in zebra mussels is under investigation. Both males and females can be induced to spawn by either injection or external application of 5-HT. The response can also be activated by 8-hydroxy-2-(di-n-propylamino)-tetralin, an agonist at 5-HT1A receptors. HPLC analysis has detected 5-HT as the major biogenic amine in both male and female gonads. 5-HT immunocytochemistry demonstrates nerves containing serotonergic fibers innervating gonads of both males and females, with prominent varicosities surrounding the follicles in both sexes. A role of 5-HT in mediating spawning responses in zebra mussels is thus strongly supported. These studies have shown that reproductive behavior of zebra mussels can be modified by outside chemicals, a property that may be exploited for purposes of control.

The stereospecific removal of a C-19 hydrogen atom in oestrogen biosynthesis

PubMed Central

Skinner, S. J. M.; Akhtar, M.

1969-01-01

1. The synthesis of a number of 19-substituted androgens is described. 2. A method for the partially stereospecific introduction of a tritium label at C-19 in 19-hydroxyandrost-5-ene-3β,17β-diol was developed. The 19-3H-labelled triol produced by reduction of 19-oxoandrost-5-ene-3β,17β-diol with tritiated sodium borohydride is tentatively formulated as 19-hydroxy[(19-R)-19-3H]androst-5-ene-3β,17β-diol and the 19-3H-labelled triol produced by reduction of 19-oxo[19-3H]-androst-5-ene-3β,17β-diol with sodium borohydride as 19-hydroxy[(19-S)-19-3H]-androst-5-ene-3β,17β-diol. 3. In the conversion of the (19-R)-19-3H-labelled compound into oestrogen by a microsomal preparation from human term placenta more radioactivity was liberated in formic acid (61·6%) than in water (38·4%). In a parallel experiment with the (19-S)-19-3H-labelled compound the order of radioactivity was reversed: formic acid (23·4%), water (76·2%). 4. These observations are interpreted in terms of the removal of the 19-S-hydrogen atom in the conversion of a 19-hydroxy androgen into a 19-oxo androgen during oestrogen biosynthesis. 5. It is suggested that the removal of C-19 in oestrogen biosynthesis occurs compulsorily at the oxidation state of a 19-aldehyde with the liberation of formic acid. PMID:5810071

Prodrug and covalent linker strategies for the solubilization of dual-action antioxidants/iron chelators.

PubMed

Bebbington, David; Dawson, Claire E; Gaur, Suneel; Spencer, John

2002-11-18

Water soluble prodrugs of hybrid free radical scavenger/iron chelating molecules, based on 3,5-disubstituted-4-hydroxyphenyl derivatives and 3-hydroxy-2-methyl-4(1H)-pyridinone (deferiprone), have been prepared. Related hybrid molecules containing a covalent poly(ethylene)glycol or an amine linker were also synthesized.

Identification of Furosemide Photodegradation Products in Water-Acetonitrile Mixture.

PubMed

Katsura, Shinji; Yamada, Nobuo; Nakashima, Atsushi; Shiraishi, Sumihiro; Furuishi, Takayuki; Ueda, Haruhisa

2015-01-01

The aim of this study was to identify the chemical structure of the photodegradation products of furosemide in a water-acetonitrile mixture (1 : 1). Furosemide solution was irradiated with a D65 fluorescent lamp and the products were isolated by preparative HPLC. The fractions were evaporated to dryness in vacuo. The purity of the photodegradation products was measured by HPLC. The purity of products 1, 3, and 4 was greater than 90%, whereas that of product 2 was 13%, therefore, photodegradation product 2 was unstable. We identified photodegradation products 1 and 3 as 4-chloro-5-sulfamoylanthranilic acid and 4-hydroxy-N-furfuryl-5-sulfamoylanthranilic acid, respectively, by LC/MS and NMR. Additionally, we assumed that photodegradation product 4 was methyl 2-((furan-2-ylmethyl)amino)-4-hydroxy-3-(methyleneamino)-5-sulfamoylbenzoate by LC/MS and NMR. This showed that furosemide underwent hydrolysis and substitution, and reacted with the acetonitrile under the light of a D65 fluorescent lamp. We were furthermore able to determine the elution times of the photodegradation products of furosemide by applying the Japanese Pharmacopoeia chromatographic method for related substances to the isolated products.

Selective degradation of ibuprofen and clofibric acid in two model river biofilm systems.

PubMed

Winkler, M; Lawrence, J R; Neu, T R

2001-09-01

A field survey indicated that the Elbe and Saale Rivers were contaminated with both clofibric acid and ibuprofen. In Elbe River water we could detect the metabolite hydroxy-ibuprofen. Analyses of the city of Saskatoon sewage effluent discharged to the South Saskatchewan river detected clofibric acid but neither ibuprofen nor any metabolite. Laboratory studies indicated that the pharmaceutical ibuprofen was readily degraded in a river biofilm reactor. Two metabolites were detected and identified as hydroxy- and carboxy-ibuprofen. Both metabolites were observed to degrade in the biofilm reactors. However, in human metabolism the metabolite carboxy-ibuprofen appears and degrades second whereas the opposite occurs in biofilm systems. In biofilms the pharmacologically inactive stereoisomere of ibuprofen is degraded predominantly. In contrast, clofibric acid was not biologically degraded during the experimental period of 21 days. Similar results were obtained using biofilms developed using waters from either the South Saskatchewan or Elbe River. In a sterile reactor no losses of ibuprofen were observed. These results suggested that abiotic losses and adsorption played only a minimal role in the fate of the pharmaceuticals in the river biofilm reactors.

Computational study of antimalarial pyrazole alkaloids from Newbouldia laevis.

PubMed

Mammino, Liliana; Bilonda, Mireille K

2014-11-01

Six pyrazole alkaloids of natural origin (isolated from Newbouldia laevis in DR Congo) that exhibit antimalarial activity-namely withasomnine, newbouldine, and their para-hydroxy and -methoxy derivatives-were investigated theoretically. The nitro derivatives of withasomnine and para-hydroxywithasomnine, which show enhanced antimalarial activity, were also studied in this manner. A thorough conformational study was performed in vacuo and in three solvents (chloroform, acetonitrile, and water) at different levels of theory (HF, DFT/B3LYP, and MP2) using different basis sets. Adducts with explicit water molecules were calculated at the HF level. Due to the rigidity of the pyrazole system and the benzene ring, the only factor that influences the energies of withasomnine and newbouldine is the relative orientation of the two ring systems; two orientations are equally preferred. The para-hydroxy and -methoxy derivatives show a preference for a planar orientation of the OH and OC bonds. The main stabilizing influence on the nitro derivative of para-hydroxywithasomnine is the intramolecular hydrogen bond between the two consecutive functional groups. The calculated adducts show the preferred arrangements of water molecules in the vicinity of the N atoms of the pyrazole system and, for the derivatives, also in the vicinity of the substituents on the benzene ring.

4-Hydroxy cinnamic acid as mushroom preservation: Anti-tyrosinase activity kinetics and application.

PubMed

Hu, Yong-Hua; Chen, Qing-Xi; Cui, Yi; Gao, Huan-Juan; Xu, Lian; Yu, Xin-Yuan; Wang, Ying; Yan, Chong-Ling; Wang, Qin

2016-05-01

Tyrosinase is a key enzyme in post-harvest browning of fruit and vegetable. To control and inhibit its activity is the most effective method for delaying the browning and extend the shelf life. In this paper, the inhibitory kinetics of 4-hydroxy cinnamic acid on mushroom tyrosinase was investigated using the kinetics method of substrate reaction. The results showed that the inhibition of tyrosinase by 4-hydroxy cinnamic acid was a slow, reversible reaction with fractional remaining activity. The microscopic rate constants were determined for the reaction on 4-hydroxy cinnamic acid with tyrosinase. Furthermore, the molecular docking was used to simulate 4-hydroxy cinnamic acid dock with tyrosinase. The results showed that 4-hydroxy cinnamic acid interacted with the enzyme active site mainly through the hydroxy competed with the substrate hydroxy group. The cytotoxicity study of 4-hydroxy cinnamic acid indicated that it had no effects on the proliferation of normal liver cells. Moreover, the results of effects of 4-hydroxy cinnamic acid on the preservation of mushroom showed that it could delay the mushroom browning. These results provide a comprehensive underlying the inhibitory mechanisms of 4-hydroxy cinnamic acid and its delaying post-harvest browning, that is beneficial for the application of this compound. Copyright © 2016 Elsevier B.V. All rights reserved.

Analysis of 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) and its brominated analogues in chlorine-treated water by gas chromatography coupled to triple quadrupole tandem mass spectrometry (GC-QqQ-MS/MS).

PubMed

Planas, Carles; Ventura, Francesc; Caixach, Josep; Martín, Jordi; Boleda, M Rosa; Paraira, Miquel

2015-11-01

A simple, selective and sensitive method for the analysis of the strong mutagen 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) and its brominated analogues (BMXs) in chlorine-treated water has been developed. The method is based on gas chromatography coupled to triple quadrupole tandem mass spectrometry (GC-QqQ-MS/MS), previous liquid-liquid extraction (LLE) of a smaller sample volume compared to other methods and on-line derivatization with a silylation reactive. GC-QqQ-MS/MS has been raised as an alternative easier to perform than gas chromatography coupled to high resolution mass spectrometry (GC-HRMS) for the analysis of MX and BMXs, and it allows to achieve low LODs (0.3 ng/L for MX and 0.4-0.9 ng/L for BMXs). This technique had not been previously described for the analysis of MX and BMXs. Quality parameters were calculated and real samples related to 3 drinking water treatment plants (DWTPs), tap water and both untreated and chlorinated groundwater were analyzed. Concentrations of 0.3-6.6 ng/L for MX and 1.0-7.3 ng/L for BMXs were detected. Results were discussed according to five of the main factors affecting MX and BMXs formation in chlorine-treated water (organic precursors, influence of bromide ions, evolution of MX and BMXs in the drinking water distribution system, groundwater chlorination and infiltration of water coming from chlorination processes in groundwater). Copyright © 2015 Elsevier B.V. All rights reserved.

Simultaneous Determination of Oxysterols, Cholesterol and 25-Hydroxy-Vitamin D3 in Human Plasma by LC-UV-MS

PubMed Central

Narayanaswamy, Rohini; Iyer, Vignesh; Khare, Prachi; Bodziak, Mary Lou; Badgett, Darlene; Zivadinov, Robert; Weinstock-Guttman, Bianca; Rideout, Todd C.; Ramanathan, Murali; Browne, Richard W.

2015-01-01

Background Oxysterols are promising biomarkers of neurodegenerative diseases that are linked with cholesterol and vitamin D metabolism. There is an unmet need for methods capable of sensitive, and simultaneous quantitation of multiple oxysterols, vitamin D and cholesterol pathway biomarkers. Methods A method for simultaneous determination of 5 major oxysterols, 25-hydroxy vitamin D3 and cholesterol in human plasma was developed. Total oxysterols were prepared by room temperature saponification followed by solid phase extraction from plasma spiked with deuterated internal standards. Oxysterols were resolved by reverse phase HPLC using a methanol/water/0.1% formic acid gradient. Oxysterols and 25-hydroxy vitamin D3 were detected with atmospheric pressure chemical ionization mass spectrometry in positive ion mode; in-series photodiode array detection at 204nm was used for cholesterol. Method validation studies were performed. Oxysterol levels in 220 plasma samples from healthy control subjects, multiple sclerosis and other neurological disorders patients were quantitated. Results Our method quantitated 5 oxysterols, cholesterol and 25-hydroxy vitamin D3 from 200 μL plasma in 35 minutes. Recoveries were >85% for all analytes and internal standards. The limits of detection were 3-10 ng/mL for oxysterols and 25-hydroxy vitamin D3 and 1 μg/mL for simultaneous detection of cholesterol. Analytical imprecision was <10 %CV for 24(S)-, 25-, 27-, 7α-hydroxycholesterol (HC) and cholesterol and ≤15 % for 7-keto-cholesterol. Multiple Sclerosis and other neurological disorder patients had lower 27-hydroxycholesterol levels compared to controls whereas 7α-hydroxycholesterol was lower specifically in Multiple Sclerosis. Conclusion The method is suitable for measuring plasma oxysterols levels in human health and disease. Analysis of human plasma indicates that the oxysterol, bile acid precursors 7α-hydroxycholesterol and 27-hydroxycholesterol are lower in Multiple Sclerosis and may serve as potential biomarkers of disease. PMID:25875771

Occurrence, source analysis and risk assessment of androgens, glucocorticoids and progestagens in the Hailing Bay region, South China Sea.

PubMed

Liu, Shan; Chen, Hui; Zhou, Guang-Jie; Liu, Shuang-Shuang; Yue, Wei-Zhong; Yu, Shen; Sun, Kai-Feng; Cheng, Hefa; Ying, Guang-Guo; Xu, Xiang-Rong

2015-12-01

The occurrence and spatial distribution of 40 steroids in the environmental matrices of the Hailing Bay region, South China Sea, were investigated by rapid resolution liquid chromatography-tandem mass spectrometry (RRLC-MS/MS). Seventeen, 14 and 11 of 40 steroids were detected with the concentrations ranging from 0.04 (testosterone) to 40.00 ng/L (prednisolone), 1.33 (4-hydroxy-androst-4-ene-17-dione) to 1855 ng/L (androsta-1,4-diene-3,17-dione) and <0.19 (androsta-1,4-diene-3,17-dione) to 2.37 ng/g (progesterone) in the seawater, the municipal sewage discharged effluent and the sediment samples, respectively. The concentrations and risk quotients (RQs) of the steroids detected in the water samples decreased in the order of municipal sewage discharge site>wharves~aquaculture zones~tourism areas>offshore areas. The distribution of steroids in the marine environment was significantly correlated with the levels of chemical oxygen demand (COD) and ammonium nitrogen (NH4-N). Source analysis indicated that untreated municipal sewage was the main source of steroids in the marine environment. Furthermore, progesterone was found to be a reliable chemical indicator to surrogate different steroids in both the water and sediment phases based on the correlation analysis. Copyright © 2015 Elsevier B.V. All rights reserved.

Characterization of the key aroma compounds in pink guava (Psidium guajava L.) by means of aroma re-engineering experiments and omission tests.

PubMed

Steinhaus, Martin; Sinuco, Diana; Polster, Johannes; Osorio, Coralia; Schieberle, Peter

2009-04-08

Seventeen aroma-active volatiles, previously identified with high flavor dilution factors in fresh, pink Colombian guavas (Psidium guajava L.), were quantified by stable isotope dilution assays. On the basis of the quantitative data and odor thresholds in water, odor activity values (OAV; ratio of concentration to odor threshold) were calculated. High OAVs were determined for the green, grassy smelling (Z)-3-hexenal and the grapefruit-like smelling 3-sulfanyl-1-hexanol followed by 3-sulfanylhexyl acetate (black currant-like), hexanal (green, grassy), ethyl butanoate (fruity), acetaldehyde (fresh, pungent), trans-4,5-epoxy-(E)-2-decenal (metallic), 4-hydroxy-2,5-dimethyl-3(2H)-furanone (caramel, sweet), cinnamyl alcohol (floral), methyl (2S,3S)-2-hydroxy-3-methylpentanoate (fruity), cinnamyl acetate (floral), methional (cooked potato-like), and 3-hydroxy-4,5-dimethyl-2(5H)-furanone (seasoning-like). Studies on the time course of odorant formation in guava puree or cubes, respectively, showed that (Z)-3-hexenal was hardly present in the intact fruits, but was formed very quickly during crushing. The aroma of fresh guava fruit cubes, which showed a very balanced aroma profile, was successfully mimicked in a reconstitute consisting of 13 odorants in their naturally occurring concentrations. Omission tests, in which single odorants were omitted from the entire aroma reconstitute, revealed (Z)-3-hexenal, 3-sulfanyl-1-hexanol, 4-hydroxy-2,5-dimethyl-3(2H)-furanone, 3-sulfanylhexyl acetate, hexanal, ethyl butanoate, cinnamyl acetate, and methional as the key aroma compounds of pink guavas.

MUTATIONAL AND TRANSCRIPTIONAL RESPONSES OF SAMMONELLA TO MX: CORRELATION OF MUTATIONAL DOSE RESPONSE TO CHANGES IN GENE EXPRESSION

EPA Science Inventory

We measured the mutational and transcriptional response of Salmonella TA 100 to 3 concentrations of a drinking water mutagen -chloro-4-(dichloromethyl)-5-hydroxy2(5H)-furanone (MX). The mutagenicity of MX in strain TA100 was evaluated in a 30min suspension assay, and the mutageni...

The fluorescent property of 3-[(2-hydroxy-1-naphthyl) methylideneamino]benzoic acid and its application as fluorescent chemosensor for Hg2 + and Al3 + ions

NASA Astrophysics Data System (ADS)

Sun, Changyan; Sun, Jiayi; Qiu, Fazheng; Li, Wenjun; Chang, Zhidong; Zhang, Lijun

2018-01-01

This manuscript studies the fluorescent property of 3-[(2-hydroxy-1-naphthyl)methylideneamino]benzoic acid (H2L). Fluorescent spectra show that in different solvents, H2L displays different fluorescent properties, which can be attributed to the interaction between the solvents and H2L. Further study indicates that H2L exhibits a highly selective and sensitive recognition for Hg2 + ions in dimethylsulfoxide (DMSO), Al3 + ions in methanol and N,N‧-dimethylformamide/water (DMF/H2O, 1/1, v/v). The bonding modes and bonding ratio of H2L and metal ions in different solvents are explored by Job's plot, 1H NMR titration, and electrospray ionization mass spectrometry (ESI-MS). The probable mechanisms were discussed.

Drastic nickel ion removal from aqueous solution by curcumin-capped Ag nanoparticles

NASA Astrophysics Data System (ADS)

Bettini, S.; Pagano, R.; Valli, L.; Giancane, G.

2014-08-01

A completely green synthesis protocol has been adopted to obtain silver nanoaggregates capped by the natural compound (1E, 6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-diene), also known as curcumin. The synthesis has been monitored by infrared, Raman, visible and fluorescence spectroscopies. Characterization confirms that curcumin reduces and caps the nanoparticles, and such a procedure allows its solubility in water and drastically increases curcumin stability. Silver nanoparticles (AgNPs)/curcumin complex has been dispersed in a water solution containing a known nickel ion concentration. After three days, a grey precipitate is observed and nickel concentration in the solution is reduced by about 70%.A completely green synthesis protocol has been adopted to obtain silver nanoaggregates capped by the natural compound (1E, 6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-diene), also known as curcumin. The synthesis has been monitored by infrared, Raman, visible and fluorescence spectroscopies. Characterization confirms that curcumin reduces and caps the nanoparticles, and such a procedure allows its solubility in water and drastically increases curcumin stability. Silver nanoparticles (AgNPs)/curcumin complex has been dispersed in a water solution containing a known nickel ion concentration. After three days, a grey precipitate is observed and nickel concentration in the solution is reduced by about 70%. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr02583k

Bromination of Marine Dissolved Organic Matter following Full Scale Electrochemical Ballast Water Disinfection.

PubMed

Gonsior, Michael; Mitchelmore, Carys; Heyes, Andrew; Harir, Mourad; Richardson, Susan D; Petty, William Tyler; Wright, David A; Schmitt-Kopplin, Philippe

2015-08-04

An extensively diverse array of brominated disinfection byproducts (DBPs) were generated following electrochemical disinfection of natural coastal/estuarine water, which is one of the main treatment methods currently under consideration for ballast water treatment. Ultra-high-resolution mass spectrometry revealed 462 distinct brominated DBPs at a relative abundance in the mass spectra of more than 1%. A brominated DBP with a relative abundance of almost 22% was identified as 2,2,4-tribromo-5-hydroxy-4-cyclopentene-1,3-dione, which is an analogue to several previously described 2,2,4-trihalo-5-hydroxy-4-cyclopentene-1,3-diones in drinking water. Several other brominated molecular formulas matched those of other known brominated DBPs, such as dibromomethane, which could be generated by decarboxylation of dibromoacetic acid during ionization, dibromophenol, dibromopropanoic acid, dibromobutanoic acid, bromohydroxybenzoic acid, bromophenylacetic acid, bromooxopentenoic acid, and dibromopentenedioic acid. Via comparison to previously described chlorine-containing analogues, bromophenylacetic acid, dibromooxopentenoic acid, and dibromopentenedioic acid were also identified. A novel compound at a 4% relative abundance was identified as tribromoethenesulfonate. This compound has not been previously described as a DBP, and its core structure of tribromoethene has been demonstrated to show toxicological implications. Here we show that electrochemical disinfection, suggested as a candidate for successful ballast water treatment, caused considerable production of some previously characterized DBPs in addition to novel brominated DBPs, although several hundred compounds remain structurally uncharacterized. Our results clearly demonstrate that electrochemical and potentially direct chlorination of ballast water in estuarine and marine systems should be approached with caution and the concentrations, fate, and toxicity of DBP need to be further characterized.

Formation of brominated disinfection byproducts during Chloramination of drinking water: new polar species and overall kinetics.

PubMed

Zhai, Hongyan; Zhang, Xiangru; Zhu, Xiaohu; Liu, Jiaqi; Ji, Min

2014-01-01

The formation of brominated disinfection byproducts (Br-DBPs), which are generally significantly more cytotoxic and genotoxic than their chlorinated analogues, in chloramination has not been fully examined. In this work, the formation of new polar Br-DBPs in simulated drinking waters was examined using state-of-the-art ultraperformance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry. As many as 29 aliphatic, aromatic, or nitrogenous polar Br-DBPs were detected in chloramination, and five of them (including 2,4,6-tribromoresorcinol, 2,6-dibromo-4-nitrophenol, 2,2,4-tribromo-5-hydroxy-4-cyclopentene-1,3-dione, 2,2,4-dibromochloro-5-hydroxy-4-cyclopentene-1,3-dione, and 2,2,4-bromodichloro-5-hydroxy-4-cyclopentene-1,3-dione) were tentatively identified. Unlike chlorination, chloramination favored the formation of aromatic and nitrogenous polar Br-DBPs and was mild enough to allow polar intermediate Br-DBPs to accumulate. To further explore the formation mechanism of Br-DBPs in chloramination, a quantitative empirical model involving 33 major reactions was developed to describe the overall kinetics. According to the modeling results, bromochloramine and monobromamine were the major species responsible for 54.2-58.1% and 41.7-45.7%, respectively, of the formed Br-DBPs, while hypobromous acid accounted for only 0.2% of the formed Br-DBPs; direct reactions between monochloramine and natural organic matter accounted for the majority of the formed chlorinated DBPs (93.7-95.1%); hypochlorous acid and hypobromous acid in the chloramination were at ng/L or subng/L levels, which were not enough to cause polar intermediate Br-DBPs to decompose.

A novel use of bio-based natural fibers, polymers, and rubbers for composite materials

NASA Astrophysics Data System (ADS)

Modi, Sunny Jitendra

The composites, materials, and packaging industries are searching for alternative materials to attain environmental sustainability. Bio-plastics are highly desired and current microbially-derived bio-plastics, such as PHA (poly-(hydroxy alkanoate)), PHB (poly-(hydroxybutyrate)), and PHBV (poly-(beta-hydroxy butyrate-co-valerate)) could be engineered to have similar properties to conventional thermoplastics. Poly-(hydroxybutyrate) (PHB) is a bio-degradable aliphatic polyester that is produced by a wide range of microorganisms. Basic PHB has relatively high glass transition and melting temperatures. To improve flexibility for potential packaging applications, PHB is synthesized with various co-polymers such as Poly-(3-hydroxyvalerate) (HV) to decrease the glass and melting temperatures and, since there is improved melt stability at lower processing temperatures, broaden the processing window. However, previous work has shown that this polymer is too brittle, temperature-sensitive, and hydrophilic to meet packaging material physical requirements. Therefore, the proposed work focuses on addressing the needs for bio-derived and bio-degradable materials by creating a range of composite materials using natural fibers as reinforcement agents in bio-polymers and bio- plastic-rubber matrices. The new materials should possess properties lacking in PHBV and broaden the processing capabilities, elasticity, and improve the mechanical properties. The first approach was to create novel composites using poly-(beta-hydroxy butyrate-co-valerate) (PHBV) combined with fibers from invasive plants such as common reed (Phragmites australis), reed canary grass (Phalaris arundinacea), and water celery ( Vallisneria americana). The composites were manufactured using traditional processing techniques of extrusion compounding followed by injection molding of ASTM type I parts. The effects of each bio-fiber at 2, 5, and 10% loading on the mechanical, morphological, rheological, and thermal properties of PHBV were investigated. Many of the composites showed miscible blends between the fibers and PHBV. The SEM analysis showed finely dispersed water celery bio-fibers into the PHBV matrix indicating compatibility between this fiber and the PHBV matrix. The finely ground water celery fibers increased the fiber-matrix interactions without the use of additives or compatibilizers. When the mechanical properties of the composites were compared to pure PHBV, the composites showed improvements in the tensile modulus, while limited changes were observed in the tensile strength and elongation at break. Also, improvements in the viscosity at 170¨¬C over pure PHBV were observed with the addition of 10% by weight bio-fibers due to fiber-fiber and fiber-matrix interactions. With these improvements in the melt stability, the composites can be processed above the melting temperature of 165-170°C, a marked benefit over pure PHBV. The brittle nature of PHBV and its relatively high water transmission rates making it unsuitable for packaging applications. New blends of PHBV with high molecular weight natural rubber of matched viscosity were developed. The mechanical, rheological, and thermal properties of the blends with 5, 10, 15, and 25% by weight high molecular weight natural rubber (HMW-NR) were characterized; in addition, the water vapor transmission rates of these blends was determined. The results showed increased thermal stability and more uniform melting peaks for the blends compared to pure PHBV. The water permeation decreased with the addition of HMW-NR, and the permeation rates were similar to that of traditional thermoplastics. The addition of rubber increased the elongation at break without adversely affecting the Young's modulus for the blends. The complex viscosity of the blends was improved by one log over pure PHBV at 170ºC suggesting improved thermal stability of the blends. During creep and recovery testing, higher compliance values of the blends suggest increased entanglements network of PHBV and rubber micro-fibrils preventing the blends from developing permanent deformation. Therefore, these blends can potentially be used in-place of transitional thermoplastics in casting sheets and thermoforming.

40 CFR 721.6485 - Hydroxy terminated polyester.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Hydroxy terminated polyester. 721.6485... Substances § 721.6485 Hydroxy terminated polyester. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a hydroxy terminated polyester...

40 CFR 721.6485 - Hydroxy terminated polyester.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Hydroxy terminated polyester. 721.6485... Substances § 721.6485 Hydroxy terminated polyester. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a hydroxy terminated polyester...

Circulating neuroactive C21- and C19-steroids in young men before and after ejaculation.

PubMed

Stárka, L; Hill, M; Havlíková, H; Kancheva, L; Sobotka, V

2006-01-01

Twelve neuroactive and neuroprotective steroids, androgens and androgen precursors i.e. 3alpha,17beta-dihydroxy-5alpha-androstane, 3alpha-hydroxy-5alpha-androstan-17-one, 3alpha-hydroxy-5beta-androstan-17-one, androst-5-ene-3beta,17beta-diol, 3beta,17alpha-dihydroxy-pregn-5-en-20-one (17alpha-hydroxy-pregnenolone), 3beta-hydroxy-androst-5-en-17-one (dehydroepiandrosterone, DHEA), testosterone, androst-4-ene-3,17-dione (androstenedione), 3alpha-hydroxy-5alpha-pregnan-20-one (allopregnanolone), 3beta-hydroxy-pregn-5-en-20-one (pregnenolone), 7alpha-hydroxy-DHEA, and 7beta-hydroxy-DHEA were measured using the GC-MS system in young men before and after ejaculation provoked by masturbation. The circulating level of 17alpha-hydroxypregnenolone increased significantly, whereas the other circulating steroids were not changed at all. This fact speaks against the hypothesis that a drop in the level of neuroactive steroids, e.g. allopregnanolone may trigger the orgasm-related increase of oxytocin, reported by other authors.

Effect of changes in the deuterium content of drinking water on the hydrogen isotope ratio of urinary steroids in the context of sports drug testing.

PubMed

Piper, Thomas; Degenhardt, Karoline; Federherr, Eugen; Thomas, Andreas; Thevis, Mario; Saugy, Martial

2013-03-01

The hydrogen isotope ratio (HIR) of body water and, therefore, of all endogenously synthesized compounds in humans, is mainly affected by the HIR of ingested drinking water. As a consequence, the entire organism and all of its synthesized substrates will reflect alterations in the isotope ratio of drinking water, which depends on the duration of exposure. To investigate the effect of this change on endogenous urinary steroids relevant to doping-control analysis the hydrogen isotope composition of potable water was suddenly enriched from -50 to 200 ‰ and maintained at this level for two weeks for two individuals. The steroids under investigation were 5β-pregnane-3α,20α-diol, 5α-androst-16-en-3α-ol, 3α-hydroxy-5α-androstan-17-one (ANDRO), 3α-hydroxy-5β-androstan-17-one (ETIO), 5α-androstane-3α,17β-diol, and 5β-androstane-3α,17β-diol (excreted as glucuronides) and ETIO, ANDRO and 3β-hydroxyandrost-5-en-17-one (excreted as sulfates). The HIR of body water was estimated by determination of the HIR of total native urine, to trace the induced changes. The hydrogen in steroids is partly derived from the total amount of body water and cholesterol-enrichment could be calculated by use of these data. Although the sum of changes in the isotopic composition of body water was 150 ‰, shifts of approximately 30 ‰ were observed for urinary steroids. Parallel enrichment in their HIR was observed for most of the steroids, and none of the differences between the HIR of individual steroids was elevated beyond recently established thresholds. This finding is important to sports drug testing because it supports the intended use of this novel and complementary methodology even in cases where athletes have drunk water of different HIR, a plausible and, presumably, inevitable scenario while traveling.

Soft-Templating Synthesis of Mesoporous Silica-Based Materials for Environmental Applications

NASA Astrophysics Data System (ADS)

Gunathilake, Chamila Asanka

Dissertation research is mainly focus on: 1) the development of mesoporous silica materials with organic pendant and bridging groups (isocyanurate, amidoxime, benzene) and incorporated metal (aluminum, zirconium, calcium, and magnesium) species for high temperature carbon dioxide (CO2) sorption, 2) phosphorous-hydroxy functionalized mesoporous silica materials for water treatment, and 3) amidoxime-modified ordered mesoporous silica materials for uranium sorption under seawater conditions. The goal is to design composite materials for environmental applications with desired porosity, surface area, and functionality by selecting proper metal oxide precursors, organosilanes, tetraethylorthosilicate, (TEOS), and block copolymer templates and by adjusting synthesis conditions. The first part of dissertation presents experimental studies on the merge of aluminum, zirconium, calcium, and magnesium oxides with mesoporous silica materials containing organic pendant (amidoxime) and bridging groups (isocyanurate, benzene) to obtain composite sorbents for CO2 sorption at ambient (0-25 °C) and elevated (60-120 °C) temperatures. These studies indicate that the aforementioned composite sorbents are fairly good for CO2 capture at 25 °C via physisorption mechanism and show a remarkably high affinity toward CO2 chemisorption at 60-120 °C. The second part of dissertation is devoted to silica-based materials with organic functionalities for removal of heavy metal ions such as lead from contaminated water and for recovery of metal ions such as uranium from seawater. First, ordered mesoporous organosilica (OMO) materials with diethylphosphatoethyl and hydroxyphosphatoethyl surface groups were examined for Pb2+ adsorption and showed unprecedented adsorption capacities up to 272 mg/g and 202 mg/g, respectively However, the amidoxime-modified OMO materials were explored for uranium extraction under seawater conditions and showed remarkable capacities reaching 57 mg of uranium per gram of adsorbent.

Photodegradation of fluorene in aqueous solution: Identification and biological activity testing of degradation products.

PubMed

Kinani, Said; Souissi, Yasmine; Kinani, Aziz; Vujović, Svetlana; Aït-Aïssa, Sélim; Bouchonnet, Stéphane

2016-04-15

Degradation of fluorene under UV-vis irradiation in water was investigated and structural elucidation of the main photoproducts was achieved using gas chromatography coupled with mass spectrometry. Twenty-six photoproducts were structurally identified, mainly on the basis of electron ionization mass spectra interpretation. The main generated transformation products are hydroxy derivatives. Some secondary photoproducts including fluorenone, hydroxy fluorenone, 2-biphenyl carboxylic acid, biphenylene, methanol fluorene congeners and hydroxy fluorene dimers were also observed. A photodegradation pathway was suggested on the basis of the chemical structures of photoproducts. Fluorene as well as its main photoproducts for which chemical standards were commercially available were tested for their ability to elicit cytotoxic, estrogenic and dioxin-like activity by using in vitro cell-based bioassays. None of the tested compounds was cytotoxic at concentrations up to 100 μM. However, 2-hydroxyfluorene and 3-hydroxyfluorene exerted significant estrogenic and dioxin-like activity on a concentration range of 3-30 μM, while fluorene and 9-hydroxyfluorene were weakly or not active, respectively, in our assays. This supports the view that photodegradation processes can generate by-products of higher toxicological concern than the parent compound and strengthens the need to further identify transformation products in the aquatic environment. Copyright © 2016 Elsevier B.V. All rights reserved.

Metabolism of Ibuprofen by Phragmites australis: Uptake and Phytodegradation

PubMed Central

2017-01-01

This study explores ibuprofen (IBP) uptake and transformation in the wetland plant species Phragmites australis and the underlying mechanisms. We grew P. australis in perlite under greenhouse conditions and treated plants with 60 μg/L of IBP. Roots and rhizomes (RR), stems and leaves (SL), and liquid samples were collected during 21 days of exposure. Results show that P. australis can take up, translocate, and degrade IBP. IBP was completely removed from the liquid medium after 21 days with a half-life of 2.1 days. IBP accumulated in RR and was partly translocated to SL. Meanwhile, four intermediates were detected in the plant tissues: hydroxy-IBP, 1,2-dihydroxy-IBP, carboxy-IBP and glucopyranosyloxy-hydroxy-IBP. Cytochrome P450 monooxygenase was involved in the production of the two hydroxy intermediates. We hypothesize that transformation of IBP was first catalyzed by P450, and then by glycosyltransferase, followed by further storage or metabolism in vacuoles or cell walls. No significant phytotoxicity was observed based on relative growth of plants and stress enzyme activities. In conclusion, we demonstrated for the first time that P. australis degrades IBP from water and is therefore a suitable species for application in constructed wetlands to clean wastewater effluents containing IBP and possibly also other micropollutants. PMID:28346781

Distribution of six anticancer drugs and a variety of other pharmaceuticals, and their sorption onto sediments, in an urban Japanese river.

PubMed

Azuma, Takashi; Arima, Natsumi; Tsukada, Ai; Hirami, Satoru; Matsuoka, Rie; Moriwake, Ryogo; Ishiuchi, Hirotaka; Inoyama, Tomomi; Teranishi, Yusuke; Yamaoka, Misato; Ishida, Mao; Hisamatsu, Kanae; Yunoki, Ayami; Mino, Yoshiki

2017-08-01

The distributions of 31 pharmaceuticals grouped into nine therapeutic classes, including six anticancer drugs, were investigated in the waters and sediments of an urban river in Japan. The coefficients of sorption (logK d ) to the river sediments were also determined from the results of a field survey and laboratory-scale experiment. Three anticancer drugs-bicalutamide, doxifluridine, and tamoxifen-were detected in the river sediments at maximum concentrations of 391, 392, and 250 ng/kg, respectively. In addition, the transformation products of psychotropic carbamazepine (2-hydroxy carbamazepine, acridine, and acridone) were detected in the range of 108 ng/kg (2-hydroxy carbamazepine) to 2365 ng/kg (acridine), and the phytoestrogen glycitein was detected in the range of N.D. to 821 ng/kg. The logK d values of the targeted pharmaceuticals in river sediments in the field survey ranged from 0.5 (theophylline) to 3.3 (azithromycin). These results were in accord with those of the laboratory-scale sorption experiment. To the best of our knowledge, this is the first report of the detection of the anticancer drugs bicalutamide and tamoxifen, the transformation products of carbamazepine (2-hydroxy carbamazepine, acridine, and acridone), and the phytoestrogen genistein in river sediments.

Analysis of benzo[a]pyrene metabolites formed by rat hepatic microsomes using high pressure liquid chromatography: optimization of the method

PubMed Central

Moserová, Michaela; Kotrbová, Věra; Aimová, Dagmar; Šulc, Miroslav; Frei, Eva; Stiborová, Marie

2009-01-01

A simple and sensitive method was developed to separate the carcinogenic polycyclic aromatic hydrocarbon (PAH), benzo[a]pyrene (BaP), and six of its oxidation metabolites generated by rat hepatic microsomes enriched with cytochrome P450 (CYP) 1A1, by high pressure liquid chromatography (HPLC). The HPLC method, using an acetonitrile/water gradient as mobile phase and UV detection, provided appropriate separation and detection of both mono- and di-hydroxylated metabolites of BaP as well as BaP diones formed by rat hepatic microsomes and the parental BaP. In this enzymatic system, 3-hydroxy BaP, 9-hydroxy BaP, BaP-4,5-dihydrodiol, BaP-7,8-dihydrodiol, BaP-9,10-dihydrodiol and BaP-dione were generated. Among them the mono-hydroxylated BaP metabolite, 3-hydroxy BaP followed by di-hydroxylated BaP products, BaP-7,8-dihydrodiol and BaP-9,10-dihydrodiol, predominated, while BaP-dione was a minor metabolite. This HPLC method will be useful for further defining the roles of the CYP1A1 enzyme with both in vitro and in vivo models in understanding its real role in activation and detoxification of BaP. PMID:21217860

Extractive biotransformation for production of metabolites of poorly soluble compounds: synthesis of 32-hydroxy-rifalazil.

PubMed

Mozhaev, Vadim V; Mozhaeva, Lyudmila V; Michels, Peter C; Khmelnitsky, Yuri L

2008-10-01

A novel reaction system was developed for the production of metabolites of poorly water-soluble parent compounds using mammalian liver microsomes. The system includes the selection and use of an appropriate hydrophobic polymeric resin as a reservoir for the hydrophobic parent compounds and its metabolites. The utility of the extractive biotransformation approach was shown for the production of a low-yielding, synthetically challenging 32-hydroxylated metabolite of the antibiotic rifalazil using mouse liver microsomes. To address the low solubility and reactivity of rifalazil in the predominantly aqueous microsomal catalytic system, a variety of strategies were tested for the enhanced delivery of hydrophobic substrates, including the addition of mild detergents, polyvinylpyrrolidone, glycerol, bovine serum albumin, and hydrophobic polymeric resins. The latter strategy was identified as the most suitable for the production of 32-hydroxy-rifalazil, resulting in up to 13-fold enhancement of the volumetric productivity compared with the standard aqueous system operating at the solubility limit of rifalazil. The production process was optimized for a wide range of reaction parameters; the most important for improving volumetric productivity included the type and amount of the polymeric resin, cofactor recycling system, concentrations of the biocatalyst and rifalazil, reaction temperature, and agitation rate. The optimized extractive biotransformation system was used to synthesize 32-hydroxy-rifalazil on a multimilligram scale.

Determination of aluminium in groundwater samples by GF-AAS, ICP-AES, ICP-MS and modelling of inorganic aluminium complexes.

PubMed

Frankowski, Marcin; Zioła-Frankowska, Anetta; Kurzyca, Iwona; Novotný, Karel; Vaculovič, Tomas; Kanický, Viktor; Siepak, Marcin; Siepak, Jerzy

2011-11-01

The paper presents the results of aluminium determinations in ground water samples of the Miocene aquifer from the area of the city of Poznań (Poland). The determined aluminium content amounted from <0.0001 to 752.7 μg L(-1). The aluminium determinations were performed using three analytical techniques: graphite furnace atomic absorption spectrometry (GF-AAS), inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The results of aluminium determinations in groundwater samples for particular analytical techniques were compared. The results were used to identify the ascent of ground water from the Mesozoic aquifer to the Miocene aquifer in the area of the fault graben. Using the Mineql+ program, the modelling of the occurrence of aluminium and the following aluminium complexes: hydroxy, with fluorides and sulphates was performed. The paper presents the results of aluminium determinations in ground water using different analytical techniques as well as the chemical modelling in the Mineql+ program, which was performed for the first time and which enabled the identification of aluminium complexes in the investigated samples. The study confirms the occurrence of aluminium hydroxy complexes and aluminium fluoride complexes in the analysed groundwater samples. Despite the dominance of sulphates and organic matter in the sample, major participation of the complexes with these ligands was not stated based on the modelling.

Chitosan impregnation with biologically active tryaryl imidazoles in supercritical carbon dioxide.

PubMed

Cherkasova, Anastasia V; Glagolev, Nikolay N; Shienok, Andrey I; Demina, Tatiana S; Kotova, Svetlana L; Zaichenko, Natalia L; Akopova, Tatiana A; Timashev, Peter S; Bagratashvili, Victor N; Solovieva, Anna B

2016-09-01

The presented paper is focused on impregnation of chitosan and its derivatives with a biologically active triaryl imidazole model compound ((2-2-hydroxyphenyl)-4.5-diphenyl-1H-imidazole) in the supercritical carbon dioxide medium. Since initial chitosan represents a polycation-exchange resin and does not swell in supercritical carbon dioxide, the impregnation was carried out in the presence of water (0.15-3.0 vol%). The maximum 2-2-hydroxyphenyl)-4.5-diphenyl-1H-imidazole concentration in a chitosan film was achieved at the ~5 × 10(-3) g/cm(3) water content in the reactor. We also used hydroxy carboxylic acid derivatives of chitosan and its copolymer with polylactide as matrices for introduction of hydrophobic 2-2-hydroxyphenyl)-4.5-diphenyl-1H-imidazole. We have shown that unmodified chitosan contains the greatest amount of 2-2-hydroxyphenyl)-4.5-diphenyl-1H-imidazole, as compared with its hydrophobic derivatives. The kinetics of 2-2-hydroxyphenyl)-4.5-diphenyl-1H-imidazole diffusion from a chitosan matrix was studied in acidified water with pH 1.6. We found that the complete release of 2-2-hydroxyphenyl)-4.5-diphenyl-1H-imidazole into the aqueous phase from unmodified chitosan films occurred in 48 h, while its complete release from chitosan modified with hydroxy carboxylic acids occurred in 5 min or less.

MUTATIONAL AND TRANSCRIPTIONAL RESPONSE OF SALMONELLA TO MX: CORRELATION OF MUTATIONAL DOSE RESPONSE TO CHANGES IN GENE EXPRESSION

EPA Science Inventory

We measured the mutational and transcriptional response of Salmonella TA100 to 3 concentrations of the drinking water mutagen 3-chloro-4-(dichloromethyl)-5-hydroxy2(5H)-furanone (MX). The mutagenicity of MX in strain TA100 was evaluated in a 30min suspension assay, and the mutage...

MUTATIONAL AND TRANSCRIPTIONAL RESPONSES OF STATIONARY- AND LOGARITHMIC-PHASE SALMONELLA TO MX: CORRELATION OF MUTATIONAL RESPONSE TO CHANGES IN GENE EXPRESSION

EPA Science Inventory

We measured the mutational and transcriptional response of stationary-phase and logarithmic-phase S. typhimurium TA100 to 3 concentrations of the drinking water mutagen 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX). The mutagenicity of MX in strain TA100 was evaluated...

Mechanistic insights into the decomposition of fructose to hydroxy methyl furfural in neutral and acidic environments using high-level quantum chemical methods.

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

Assary, R. S.; Redfern, P. C.; Greeley, J.

2011-03-28

Efficient catalytic chemical transformation of fructose to hydroxy methyl furfural (HMF) is one of the key steps for attaining industrial level conversion of biomass to useful chemicals. We report an investigation of the reaction mechanisms for the decomposition of fructose to HMF in both neutral and acidic environments at the Gaussian-4 level of theory including calculation of enthalpies, free energies, and effective solvation interactions. In neutral water solvent, the transformation of fructose to HMF involves a four step reaction sequence with four transition states. The effective activation energy relative to fructose in neutral water at 298 K is very large,more » about 74 kcal/mol, so that transformation in neutral media around this temperature is unlikely. In contrast, the computed potential energy surface is much more favorable for the transformation in acidic media at 498 K, as the effective activation barrier is about 39 kcal/mol. The transformation in acidic media is a much more complex mechanism involving dehydration and hydrogen transfer steps, which are more favorable when protonated intermediates are involved.« less

Mechanistic Insights into the Decomposition of Fructose to Hydroxy Methyl Furfural in Neutral and Acidic Environments Using High-Level Quantum Chemical Methods

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

Assary, Rajeev S.; Redfern, Paul C.; Greeley, Jeffrey P.

2011-04-21

Efficient catalytic chemical transformation of fructose to hydroxy methyl furfural (HMF) is one of the key steps for attaining industrial level conversion of biomass to useful chemicals. We report an investigation of the reaction mechanisms for the decomposition of fructose to HMF in both neutral and acidic environments at the Gaussian-4 level of theory including calculation of enthalpies, free energies, and effective solvation interactions. In neutral water solvent, the transformation of fructose to HMF involves a four step reaction sequence with four transition states. The effective activation energy relative to fructose in neutral water at 298 K is very large,more » about 74 kcal/mol, so that transformation in neutral media around this temperature is unlikely. In contrast, the computed potential energy surface is much more favorable for the transformation in acidic media at 498 K, as the effective activation barrier is about 39 kcal/mol. The transformation in acidic media is a much more complex mechanism involving dehydration and hydrogen transfer steps, which are more favorable when protonated intermediates are involved.« less

Mechanistic Insights into the Decomposition of Fructose to Hydroxy Methyl Furfural in Neutral and Acidic Environments Using High-Level Quantum Chemical Methods

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

Assary, Rajeev S.; Redfern, Paul C.; Greeley, Jeffrey

2011-03-28

Efficient catalytic chemical transformation of fructose to hydroxy methyl furfural (HMF) is one of the key steps for attaining industrial level conversion of biomass to useful chemicals. We report an investigation of the reaction mechanisms for the decomposition of fructose to HMF in both neutral and acidic environments at the Gaussian-4 level of theory including calculation of enthalpies, free energies, and effective solvation interactions. In neutral water solvent, the transformation of fructose to HMF involves a four step reaction sequence with four transition states. The effective activation energy relative to fructose in neutral water at 298 K is very large,more » about 74 kcal/mol, so that transformation in neutral media around this temperature is unlikely. In contrast, the computed potential energy surface is much more favorable for the transformation in acidic media at 498 K, as the effective activation barrier is about 39 kcal/mol. The transformation in acidic media is a much more complex mechanism involving dehydration and hydrogen transfer steps, which are more favorable when protonated intermediates are involved.« less

On the structural intricacies of a metabolic precursor: Direct spectroscopic detection of water-induced conformational reshaping of mevalonolactone

NASA Astrophysics Data System (ADS)

Domingos, Sérgio R.; Pérez, Cristóbal; Schnell, Melanie

2017-09-01

We use high-resolution rotational spectroscopy to investigate the structural intricacies of the lactone form of mevalonic acid, precursor of the mevalonate pathway. By combining microwave spectroscopy with supersonic expansions and quantum-chemical calculations, we determine the two most stable conformations of the precursor. Complementary micro-solvation studies reveal that aggregation of the first water molecule induces a substantial structural rearrangement comprising a hydroxy rotation and an endocyclic core torsion to create a favourable geometry to accommodate the water molecule. We discuss the conformational aspects of the precursor in isolation and under micro-hydrated conditions.

21 CFR 582.5477 - Methionine hydroxy analog and its calcium salts.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Methionine hydroxy analog and its calcium salts... Nutrients and/or Dietary Supplements 1 § 582.5477 Methionine hydroxy analog and its calcium salts. (a) Product. Methionine hydroxy analog and its calcium salts. (b) [Reserved] (c) Limitations, restrictions, or...

21 CFR 582.5477 - Methionine hydroxy analog and its calcium salts.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Methionine hydroxy analog and its calcium salts... Nutrients and/or Dietary Supplements 1 § 582.5477 Methionine hydroxy analog and its calcium salts. (a) Product. Methionine hydroxy analog and its calcium salts. (b) [Reserved] (c) Limitations, restrictions, or...

40 CFR 721.10164 - Benzenecarboximidamide, N-hydroxy-4-nitro-.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Benzenecarboximidamide, N-hydroxy-4... Specific Chemical Substances § 721.10164 Benzenecarboximidamide, N-hydroxy-4-nitro-. (a) Chemical substance... benzenecarboximidamide, N-hydroxy-4-nitro- (PMN P-08-36; CAS No. 1613-86-1) is subject to reporting under this section...

40 CFR 721.10164 - Benzenecarboximidamide, N-hydroxy-4-nitro-.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Benzenecarboximidamide, N-hydroxy-4... Specific Chemical Substances § 721.10164 Benzenecarboximidamide, N-hydroxy-4-nitro-. (a) Chemical substance... benzenecarboximidamide, N-hydroxy-4-nitro- (PMN P-08-36; CAS No. 1613-86-1) is subject to reporting under this section...

Metabolism of 4-N-Hydroxy-Cytidine in Escherichia coli

PubMed Central

Trimble, R. B.; Maley, Frank

1971-01-01

4-N-hydroxy-cytidine was found to substitute for uridine as a pyrimidine supplement for the growth of Escherichia coli Bu−. Measurement of the incorporation of 4-N-hydroxy-cytidine-2-14C into ribonucleic acid and deoxyribonucleic acid revealed that this compound was converted to cytidine or uridine before utilization. Two pathways for metabolism were considered: (i) the reduction of 4-N-hydroxy-cytidine to cytidine followed by deamination, (ii) the direct hydrolysis of hydroxylamine from 4-N-hydroxy-cytidine to yield uridine. A threefold increase in cytidine (deoxycytidine) deaminase (EC 3.5.4.5) activity, when the cells were grown on 4-N-hydroxy-cytidine, suggested the involvement of this enzyme. More direct proof was obtained by purifying the deaminase 185-fold and finding that it released hydroxylamine from 4-N-hydroxy-cytidine at one-fiftieth the rate at which ammonia was removed from cytidine. This result is consistent with the slower rate of growth of the Bu− cells on 4-N-hydroxy-cytidine than cytidine and suggests that the second pathway is the major route for utilization of this compound. PMID:4941553

A novel unsaturated fatty acid hydratase toward C16 to C22 fatty acids from Lactobacillus acidophilus

PubMed Central

Hirata, Akiko; Kishino, Shigenobu; Park, Si-Bum; Takeuchi, Michiki; Kitamura, Nahoko; Ogawa, Jun

2015-01-01

Hydroxy FAs, one of the gut microbial metabolites of PUFAs, have attracted much attention because of their various bioactivities. The purpose of this study was to identify lactic acid bacteria with the ability to convert linoleic acid (LA) to hydroxy FAs. A screening process revealed that a gut bacterium, Lactobacillus acidophilus NTV001, converts LA mainly into 13-hydroxy-cis-9-octadecenoic acid and resulted in the identification of the hydratase responsible, fatty acid hydratase 1 (FA-HY1). Recombinant FA-HY1 was purified, and its enzymatic characteristics were investigated. FA-HY1 could convert not only C18 PUFAs but also C20 and C22 PUFAs. C18 PUFAs with a cis carbon-carbon double bond at the Δ12 position were converted into the corresponding 13-hydroxy FAs. Arachidonic acid and DHA were converted into the corresponding 15-hydroxy FA and 14-hydroxy FA, respectively. To the best of our knowledge, this is the first report of a bacterial FA hydratase that can convert C20 and C22 PUFAs into the corresponding hydroxy FAs. These novel hydroxy FAs produced by using FA-HY1 should contribute to elucidating the bioactivities of hydroxy FAs. PMID:25966711

Hydrophilic interaction liquid chromatography/positive ion electrospray ionization mass spectrometry method for the quantification of alprazolam and α-hydroxy-alprazolam in human plasma.

PubMed

Kalogria, Eleni; Pistos, Constantinos; Panderi, Irene

2013-12-30

A hydrophilic interaction liquid chromatography/positive ion electrospray-mass spectrometry (HILIC-ESI/MS) has been developed and fully validated for the quantification of alprazolam and its main metabolite, α-hydroxy-alprazolam, in human plasma. The assay is based on 50μL plasma samples, following liquid-liquid extraction. All analytes and the internal standard (tiamulin) were separated by hydrophilic interaction liquid chromatography using an X-Bridge-HILIC analytical column (150.0mm×2.1mm i.d., particle size 3.5μm) under isoscratic elution. The mobile phase was composed of a 7% 10mM ammonium formate water solution in acetonitrile and pumped at a flow rate of 0.20mLmin(-1). Running in positive electrospray ionization and selected ion monitoring (SIM) the mass spectrometer was set to analyze the protonated molecules [M+H](+) at m/z 309, 325 and 494 for alprazolam, α-hydroxy-alprazolam and tiamulin (ISTD) respectively. The assay was linear over the concentration range of 2.5-250ngmL(-1) for alprazolam and 2.5-50ngmL(-1) for α-hydroxy alprazolam. Intermediate precision was less than 4.1% over the tested concentration ranges. The method is the first reported application of HILIC in the analysis benzodiazepines in human plasma. With a small sample size (50μL human plasma) and a run time less than 10.0min for each sample the method can be used to support a wide range of clinical studies concerning alprazolam quantification. Copyright © 2013 Elsevier B.V. All rights reserved.

Antioxidant activity and inhibitory effects of 2-hydroxy-3-methylcyclopent-2-enone isolated from ribose-histidine Maillard reaction products on aldose reductase and tyrosinase.

PubMed

Hwang, Seung Hwan; Wang, Zhiqiang; Suh, Hong-Won; Lim, Soon Sung

2018-03-01

This study aimed to better understand the functional properties of ribose and 20 amino acid Maillard reaction products (MRPs). The ABTS + radical scavenging ability of the ribose-20 amino acid MRPs was evaluated. Among the MRPs, ribose-histidine MRPs (RH-MRPs) showed the highest inhibitory activities on the ABTS + radical scavenging ability, aldose reductase (AR), and tyrosinase compared to other MRPs. Functional compounds with antioxidant and AR inhibitory activities have been recognized as an important strategy in the prevention and treatment of diabetic complications, and the search for tyrosinase inhibitors is important for the treatment of hyperpigmentation, development of skin-whitening agents, and use as preservatives in the food industry. On this basis, we sought to isolate and identify compounds with inhibitory activities against AR and tyrosinase. RH-MRPs were heated at 120 °C for 2 h and fractionated using four solvents: methylene chloride (MC), ethyl acetate, n-butanol, and water. The highest inhibitions were found in the MC fraction. The two compounds from this fraction were purified by silica gel column and preparative thin layer chromatography, and identified as 2-hydroxy-3-methylcyclopent-2-enone and furan-3-carboxylic acid. AR inhibition, tyrosinase inhibition, and ABTS + scavenging (IC 50 ) of 2-hydroxy-3-methylcyclopent-2-enone were 4.47, 721.91 and 9.81 μg mL -1 , respectively. In this study, inhibitory effects of 2-hydroxy-3-methylcyclopent-2-enone isolated from RH-MRP were demonstrated on AR, tyrosinase, and its antioxidant activity for the first time. RH-MRP and its constituents can be developed as beneficial functional food sources and cosmetic materials and should be investigated further as potential functional food sources.

Products of the Strecker Synthesis as Indicators of Parent Body Conditions of the Murchison Meteorite

NASA Technical Reports Server (NTRS)

Lerner, Narcinda R.; Cooper, George W.; Chang, Sherwood (Technical Monitor)

1996-01-01

The Strecker synthesis, R2C=O + HCN + NH3 yields R2C(NH2)CN + H2O yields R2C(NH2)CO2H has been proposed as a source of amino acids in meteorites. The detection of carbonlyl compounds, the precursors of the amino acids in the Strecker synthesis, and a-hydroxy acids, important by-products of the Strecker synthesis, in the Murchison meteorite supports this conjecture. However, the following observations raise questions about the Strecker synthesis as the source of a-amino and a-hydroxy acids in Murchison: a) Imino acetic acids are also important by-products of the Strecker synthesis and have not been reported in Murchison. b) a-aminisobutyric acid (AIBA) is one of the most abundant amino acids in Murchison but the Strecker synthesis conducted at room temperature produced only small amounts of AIBA relative to other amino acids. c) If the a-amino and a-hydroxy acids observed in Murchison arose from a common precursor this ought to be reflected in their relative abundances, but the straight chain a-hydroxy acids appeared to be relatively abundant compared with the analogous a-amino acids. In order to address question a) we have examined a non-hydrolyzed aqueous extract of the Murchison meteorite. Imino di acetic acid, Imino propionic acetic acid and Imino butyric acetic acid (both isomers) have been identified in this fraction. The relative abundances of amino acids and imino acetic acids in this fraction are consistent with a Strecker synthesis at low temperature (263 K) as a origin of both the amino acids and the imino acetic acids found on Murchison. To deal with questions b) and c) we have carried out laboratory simulations of the Strecker synthesis. The starting concentrations for carbonlyl compounds used were based on estimates of what these concentrations might have been on the parent body. for the carbonyl compounds this estimate was determined by the amount of carbonyl compound found on Murchison plus the amounts of the corresponding amino acid and hydroxy acid found on Murchison and the rock to water ratio estimated by Clayton and Mayeda (1984). The cyanide concentration was that estimated by Peltzer et al. (1984). The ammonia concentration and pH were varied. We studied these mixtures at 298 K and 263 K. We found that high relative abundances of AIBA were produced at 263 K but not at 298 K. We only produced a-methyl a-amino hydroxy acids at 263 K with no initial ammonia. The abundances of a-amino acids, a-hydroxy acids and imino acids found on Murchison are consistent with a Strecker synthesis which took place at low temperature and with a low concentration of ammonia.

Investigation of hydrazide derivatives inhibitory effect on peroxidase enzyme purified from turnip roots

NASA Astrophysics Data System (ADS)

Almaz, Züleyha; Öztekin, Aykut; Özdemir, Hasan

2017-04-01

Peroxidases (EC: 1.11.1.7) are haem proteins and contain iron (III) protoporphyrin IX (ferriprotoporphyrin IX) as the prosthetic group [1]. They are found in all cells and play a critical role in many biological processes, such as the host-defense mechanism [2]. Peroxidases (PODs) are widely used in clinical biochemistry, enzyme immunoassays, synthesis of various aromatic chemicals, treatment of waste water containing phenolic compounds [3, 4]. In this study, peroxidase enzyme was purified with Para amino benzohydrazide (PABH)-L-Tyrosine Sepharose 4B affinity chromatography to investigate the inhibitory effect of hydrazide derivatives on Turnip (Brassica rapa L.). IC50 values and Ki constants were calculated for the molecules of 6-Amino nicotinic hydrazide, 6-Amino-5-bromo nicotinic hydrazide, 2-Amino-5-hydroxy benzohydrazide, 4-Amino-3-hydroxy benzohydrazide on purified enzyme and inhibition type of these molecules were determined.

Identification of 3-hydroxy-3-methylglutaric acid (HMG) as a hypoglycemic principle of Spanish moss (Tillandsia usneoides).

PubMed

Witherup, K M; McLaughlin, J L; Judd, R L; Ziegler, M H; Medon, P J; Keller, W J

1995-08-01

Bioactivity-directed fractionation, using brine shrimp lethality and murine hypoglycemia, of an ethanol extract prepared from Tillandsia usneoides, led to the isolation of four apparently bioactive compounds from the water-soluble fraction. The compounds were identified as citric acid, succinic acid, 3-hydroxy-3-methylglutaric acid (HMG), and 3,6,3',5'-tetramethoxy-5,7,4'-trihydroxyflavone-7-O-beta-D-g lucoside. The brine shrimp lethality of the acids was simply due to acidity; however, HMG elicited significant hypoglycemic responses in fasting normal mice. Ethyl and methyl esters of citric acid were prepared and tested in the murine hypoglycemic assay. Five of the predominant sugars were identified by tlc. Free thymidine was also isolated. Further evaluation of HMG and other potential inhibitors of HMG CoA lyase, in the treatment of symptoms of diabetes mellitus, is suggested.

A synthesis of 4-hydroxy-2-trans-nonenal and 4-(3H) 4-hydroxy-2-trans-nonenal.

PubMed

Chandra, A; Srivastava, S K

1997-07-01

4-Hydroxy-2-trans-nonenal, the most abundant and toxic unsaturated aldehyde generated during membrane lipid peroxidation, was synthesized starting from fumaraldehyde dimethyl acetal. In the first step of the synthesis, the fumaraldehyde dimethyl acetal was partially hydrolyzed using amberlyst catalyst to obtain the monoacetal. The 4-hydroxy-2-trans-nonenal was synthesized by the Grignard reaction of the fumaraldehyde monoacetal with 1-bromopentane. 4-Hydroxy-2-trans-nonenal, obtained as its dimethylacetal, was oxidized to its corresponding 4-keto derivative using pyridinium chlorochromate buffered with sodium acetate as the oxidizing agent. 4-(3H) 4-Hydroxy-2-trans-nonenal was obtained in one step by the sodium borotriteride reduction of the 4-keto derivative.

Co-precipitation of dissolved organic matter by calcium carbonate in Pyramid Lake, Nevada

USGS Publications Warehouse

Leenheer, Jerry A.; Reddy, Michael M.

2008-01-01

Our previous research has demonstrated that dissolved organic matter (DOM) influences calcium carbonate mineral formation in surface and ground water. To better understand DOM mediation of carbonate precipitation and DOM co-precipitation and/or incorporation with carbonate minerals, we characterized the content and speciation of DOM in carbonate minerals and in the lake water of Pyramid Lake, Nevada, USA. A 400-gram block of precipitated calcium carbonate from the Pyramid Lake shore was dissolved in 8 liters of 10% acetic acid. Particulate matter not dissolved by acetic acid was removed by centrifugation. DOM from the carbonate rock was fractionated into nine portions using evaporation, dialysis, resin adsorption, and selective precipitations to remove acetic acid and inorganic constituents. The calcium carbonate rock contained 0.23% DOM by weight. This DOM was enriched in polycarboxylic proteinaceous acids and hydroxy-acids in comparison with the present lake water. DOM in lake water was composed of aliphatic, alicyclic polycarboxylic acids. These compound classes were found in previous studies to inhibit calcium carbonate precipitation. DOM fractions from the carbonate rock were 14C-age dated at about 3,100 to 3,500 years before present. The mechanism of DOM co-precipitation and/or physical incorporation in the calcium carbonate is believed to be due to formation of insoluble calcium complexes with polycarboxylic proteinaceous acids and hydroxy-acids that have moderately large stability constants at the alkaline pH of the lake. DOM co-precipitation with calcium carbonate and incorporation in precipitated carbonate minerals removes proteinaceous DOM, but nearly equivalent concentrations of neutral and acidic forms of organic nitrogen in DOM remain in solution. Calcium carbonate precipitation during lime softening pretreatment of drinking water may have practical applications for removal of proteinaceous disinfection by-product precursors.

Evaluation of hepatic biotransformation of polybrominated diphenyl ethers in the polar bear (Ursus maritimus).

PubMed

Krieger, Lisa K; Szeitz, András; Bandiera, Stelvio M

2016-03-01

Polar bears are at the top of the Arctic marine food chain and are subject to exposure and bioaccumulation of environmental chemicals of concern such as polybrominated diphenyl ethers (PBDEs), which were widely used as flame retardants. The aim of the present study was to evaluate the in vitro oxidative metabolism of 2,2',4,4'-tetrabrominated diphenyl ether (BDE-47) and 2,2',4,4',5-pentabrominated diphenyl ether (BDE-99) by polar bear liver microsomes. The identification and quantification of the hydroxy-brominated diphenyl ethers formed were assessed using an ultra-high performance liquid chromatography-tandem mass spectrometry-based method. Incubation of BDE-47 with archived individual liver microsomes, prepared from fifteen polar bears from northern Canada, produced a total of eleven hydroxylated metabolites, eight of which were identified using authentic standards. The major metabolites were 4'-hydroxy-2,2',4,5'-tetrabromodiphenyl ether and 5'-hydroxy-2,2',4,4'-tetrabromodiphenyl ether. Incubation of BDE-99 with polar bear liver microsomes produced a total of eleven hydroxylated metabolites, seven of which were identified using authentic standards. The major metabolites were 2,4,5-tribromophenol and 4-hydroxy-2,2',3,4',5-pentabromodiphenyl ether. Among the CYP specific antibodies tested, anti-rat CYP2B was found to be the most active in inhibiting the formation of hydroxylated metabolites of both BDE-47 and BDE-99, indicating that CYP2B was the major CYP enzyme involved in the oxidative biotransformation of these two congeners. Our study shows that polar bears are capable of forming multiple hydroxylated metabolites of BDE-47 and BDE-99 in vitro and demonstrates the role of CYP2B in the biotransformation and possibly in the toxicity of BDE-47 and BDE-99 in polar bears. Copyright © 2015 Elsevier Ltd. All rights reserved.

Comparison of hydroxy naphthoquinone from North Qinglongyi with different storage times

NASA Astrophysics Data System (ADS)

Xin, G. S.; Ji, Y. B.; Wei, C.

2017-12-01

Objective: To determine the appropriate solvent for the extraction of hydroxy naphthoquinone, and to establish a method for the determination of the content of hydroxy naphthoquinone in the North Qinglongyi, and compare the changes of the content of hydroxy naphthoquinone in North Qinglongyi with different storage times. Methods: According to the nature of hydroxy naphthoquinone in alkaline solution will be discolored, so this experiment for Juglone as the standard reagent, 5% KOH solution as a developer, and the absorbance was measured by UV-spectrophotometry at the wavelength of 515 nm. The content of hydroxy naphthoquinone in North Qinglongyi was determined by colorimetric method, and the contents of hydroxy naphthoquinone in North Qinglongyi of different storage times were compared. Results: The optimum extraction solvent was ethyl acetate. The recoveries were 97.73%±1.11% and the RSD was 1.14% (n = 6). The contents of hydroxy naphthoquinone in the North Qinglunyi were 0.0141%, 0.0104% and 0.0073%, respectively, for one year, two years and three years. The content of hydroxy naphthoquinone decreased with the storage time prolonged. Conclusion This experimental method was stability, high recovery rate, simple and reliable. According to the results of this experiment, we can see that the storage time of North Qinglunyi should not be too long. Should try to choose this year’s North Qinglunyi for experimental research.

Studies on the potent bacterial mutagen, 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone: aqueous stability, XAD recovery and analytical determination in drinking water and in chlorinated humic acid solutions.

PubMed

Meier, J R; Knohl, R B; Coleman, W E; Ringhand, H P; Munch, J W; Kaylor, W H; Streicher, R P; Kopfler, F C

1987-12-01

3-Chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) was detected by gas chromatography/mass spectrometry in drinking water samples from 3 locations in the U.S.A., and also in a chlorinated humic acid solution. MX appears to account for a significant proportion of the mutagenicity of these samples, as measured in the Ames test using strain TA100 without metabolic activation. Studies on recovery of MX from spiked water samples by XAD-2/8 resin adsorption/acetone elution indicated that sample acidification prior to resin adsorption was essential to the effective recovery of MX. The stability of MX in aqueous solution was pH and temperature dependent. At 23 degrees C the order of stability, based on persistence of mutagenic activity was found to be: pH 2 greater than pH 4 greater than pH 8 greater than pH 6. The half-life at pH 8 and 23 degrees C was 4.6 days. One of the degradation products has been tentatively identified as 2-chloro-3-(dichloromethyl)-4-oxo-2-butenoic acid, an open form of MX which appears to be in the "E" configuration. Overall, these results suggest that MX is formed during water chlorination as a result of reaction of chlorine with humic substances, and that a substantial fraction of the MX formed is likely to persist throughout the distribution system.

Role of 3-Hydroxy Fatty Acid-Induced Hepatic Lipotoxicity in Acute Fatty Liver of Pregnancy

PubMed Central

Ibdah, Jamal A.

2018-01-01

Acute fatty liver of pregnancy (AFLP), a catastrophic illness for both the mother and the unborn offspring, develops in the last trimester of pregnancy with significant maternal and perinatal mortality. AFLP is also recognized as an obstetric and medical emergency. Maternal AFLP is highly associated with a fetal homozygous mutation (1528G>C) in the gene that encodes for mitochondrial long-chain hydroxy acyl-CoA dehydrogenase (LCHAD). The mutation in LCHAD results in the accumulation of 3-hydroxy fatty acids, such as 3-hydroxy myristic acid, 3-hydroxy palmitic acid and 3-hydroxy dicarboxylic acid in the placenta, which are then shunted to the maternal circulation leading to the development of acute liver injury observed in patients with AFLP. In this review, we will discuss the mechanistic role of increased 3-hydroxy fatty acid in causing lipotoxicity to the liver and in inducing oxidative stress, mitochondrial dysfunction and hepatocyte lipoapoptosis. Further, we also review the role of 3-hydroxy fatty acids in causing placental damage, pancreatic islet β-cell glucolipotoxicity, brain damage, and retinal epithelial cells lipoapoptosis in patients with LCHAD deficiency. PMID:29361796

Study on the binding characteristics of hydroxylated polybrominated diphenyl ethers and thyroid transporters using the multispectral technique and computational simulation.

PubMed

Wei, Yuchen; Yi, Zhongsheng; Xu, Jie; Yang, Wu; Yang, Lulu; Liu, Hongyan

2018-04-24

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) are a class of toxic environmental pollutants that are persistent, bioaccumulative, and difficult to degrade. Their structure is very similar to the thyroid hormone (T4) and uses the body's thyroid transporter (TTR) binding to interfere with the endocrine balance, disrupting the body's normal physiological activity. According to Fourier transform infrared spectroscopy and dynamics simulation of do_dssp module analysis, there are three kinds of OH-PBDEs that can induce TTR secondary structural changes. Fluorescence spectra and UV-Vis spectra show that for the three kinds of OH-PBDEs for TTR, the main methods of quenching are static quenching and non-radiative energy transfer. According to thermodynamic analysis, ΔG < 0, ΔH > 0, and ΔS > 0 combine to show that the hydrophobic interaction is the main driving force of the combination. From the molecular docking analysis, it was found that 4'-hydroxy-2,2',4,5'- tetrabromodiphenyl ether (4'-OH-BDE49) and 4 hydroxy-2,2',3,4',5,6,6'- heptabromodiphenyl ether (4-OH-BDE188) had a cationic-π interaction with TTR, whereas 4 hydroxy-2,2',3,4,5,5',6- heptabromodiphenyl ether (4-OH-BDE187) was bonded to TTR by hydrogen bonds to form stable complexes. In this paper, we highlight the consistency of spectroscopic experiments and computer simulations so as to provide a reliable analytical method for the toxicological properties of small molecule contaminants.

Biotransformation of 2-Benzoxazolinone and 2-Hydroxy-1,4-Benzoxazin-3-one by Endophytic Fungi Isolated from Aphelandra tetragona

PubMed Central

Zikmundová, M.; Drandarov, K.; Bigler, L.; Hesse, M.; Werner, C.

2002-01-01

The biotransformation of the phytoanticipins 2-benzoxazolinone (BOA) and 2-hydroxy-1,4-benzoxazin-3-one (HBOA) by four endophytic fungi isolated from Aphelandra tetragona was studied. Using high-performance liquid chromatography-mass spectrometry, several new products of acylation, oxidation, reduction, hydrolysis, and nitration were identified. Fusarium sambucinum detoxified BOA and HBOA to N-(2-hydroxyphenyl)malonamic acid. Plectosporium tabacinum, Gliocladium cibotii, and Chaetosphaeria sp. transformed HBOA to 2-hydroxy-N-(2-hydroxyphenyl)acetamide, N-(2-hydroxyphenyl)acetamide, N-(2-hydroxy-5-nitrophenyl)acetamide, N-(2-hydroxy-3-nitrophenyl)acetamide, 2-amino-3H-phenoxazin-3-one, 2-acetylamino-3H-phenoxazin-3-one, and 2-(N-hydroxy)acetylamino-3H-phenoxazin-3-one. BOA was not degraded by these three fungal isolates. Using 2-hydroxy-N-(2-hydroxyphenyl)[13C2]acetamide, it was shown that the metabolic pathway for HBOA and BOA degradation leads to o-aminophenol as a key intermediate. PMID:12324332

Proline derivatives in fruits of bergamot (Citrus bergamia Risso et Poit): presence of N-methyl-L-proline and 4-hydroxy-L-prolinebetaine.

PubMed

Servillo, Luigi; Giovane, Alfonso; Balestrieri, Maria Luisa; Cautela, Domenico; Castaldo, Domenico

2011-01-12

The content of proline and various compounds deriving from its metabolism (4-hydroxy-L-proline, N-methyl-L-proline, N,N-dimethylproline, and 4-hydroxy-L-prolinebetaine) was determined in fruits and seeds of Bergamot (Citrus bergamia Risso et Poit), growing in the Calabria region (South Italy). A HPLC-ESI-tandem mass spectrometry method, which allowed rapid determination of L-proline, 4-hydroxy-L-proline, N-methyl-L-proline, N,N-dimethylproline, and 4-hydroxy-L-prolinebetaine in juice and extracts of bergamot fruit with minimum sample preparation and short analysis time (about 10 min), is presented. Proline and 4-hydroxy-L-proline levels in the samples were also determined by HPLC analysis with fluorescence detection and the results compared to those obtained with HPLC-ESI-tandem mass spectrometry. For the first time, the presence of N-methyl-L-proline and 4-hydroxy-L-prolinebetaine in the fruits of a plant of the Citrus genus is reported.

A novel S-enantioselective amidase acting on 3,3,3-trifluoro-2-hydroxy-2-methylpropanamide from Arthrobacter sp. S-2.

PubMed

Fuhshuku, Ken-ichi; Watanabe, Shunsuke; Nishii, Tetsuro; Ishii, Akihiro; Asano, Yasuhisa

2015-01-01

A novel S-enantioselective amidase acting on 3,3,3-trifluoro-2-hydroxy-2-methylpropanamide was purified from Arthrobacter sp. S-2. The enzyme acted S-enantioselectively on 3,3,3-trifluoro-2-hydroxy-2-methylpropanamide to yield (S)-3,3,3-trifluoro-2-hydroxy-2-methylpropanoic acid. Based on the N-terminal amino acid sequence of this amidase, the gene coding S-amidase was cloned from the genomic DNA of Arthrobacter sp. S-2 and expressed in an Escherichia coli host. The recombinant S-amidase was purified and characterized. Furthermore, the purified recombinant S-amidase with the C-His6-tag, which was expressed in E. coli as the C-His6-tag fusion protein, was used in the kinetic resolution of (±)-3,3,3-trifluoro-2-hydroxy-2-methylpropanamide to obtain (S)-3,3,3-trifluoro-2-hydroxy-2-methylpropanoic acid and (R)-3,3,3-trifluoro-2-hydroxy-2-methylpropanamide.

Occurrence of Theaspirane and its Odorant Degradation Products in Hop and Beer.

PubMed

Scholtes, Caroline; Nizet, Sabrina; Massart, Hadrien; Gerbaux, Pascal; Collin, Sonia

2015-09-23

In model oxidized media, six theaspirane-derived compounds were identified by gas chromatography-high resolution mass spectrometry: 4-hydroxy-7,8-dihydro-β-ionone, 6-hydroxy-7,8-dihydro-α-ionone, dihydrodehydro-β-ionone, two monoepoxides, and a derived alcohol. Only 4-hydroxy-7,8-dihydro-β-ionone and dihydrodehydro-β-ionone have been described previously in the literature. Investigation of hop revealed five of these compounds in free form together with theaspirane (especially in the Mosaic variety), while the Citra and Amarillo hop varieties emerged as very interesting for the release of theaspirane, 4-hydroxy-7,8-dihydro-β-ionone, and dihydrodehydro-β-ionone from glucoside precursors. For the first time, theaspirane, 4-hydroxy-7,8-dihydro-β-ionone, 6-hydroxy-7,8-dihydro-α-ionone, and both monoepoxides were found in a fresh commercial top fermentation beer (only theaspirane, 4-hydroxy-7,8-dihydro-β-ionone, and dihydrodehydro-β-ionone have recently been mentioned as Gueuze constituents).

21 CFR 184.1033 - Citric acid.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Citric acid. 184.1033 Section 184.1033 Food and....1033 Citric acid. (a) Citric acid (C6H8O7, CAS Reg. No. 77-92-9) is the compound 2-hydroxy-1,2,3... crystals or a white powder and may be anhydrous or contain one mole of water per mole of citric acid...

40 CFR 721.10050 - Disubstituted-N′- hydroxy-benzenecarboximidamide (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... Specific Chemical Substances § 721.10050 Disubstituted-N′- hydroxy-benzenecarboximidamide (generic). (a... generically as disubstituted-N′- hydroxy-benzenecarboximidamide (PMN P-02-929) is subject to reporting under...

40 CFR 721.10050 - Disubstituted-N′- hydroxy-benzenecarboximidamide (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... Specific Chemical Substances § 721.10050 Disubstituted-N′- hydroxy-benzenecarboximidamide (generic). (a... generically as disubstituted-N′- hydroxy-benzenecarboximidamide (PMN P-02-929) is subject to reporting under...

Metabolism of amosulalol hydrochloride in man: quantitative comparison with laboratory animals.

PubMed

Kamimura, H; Sasaki, H; Kawamura, S

1985-05-01

The metabolism of amosulalol hydrochloride, (+/-)-5-[1-hydroxy-2-[[2-(o-methoxyphenoxy)ethyl]amino]ethyl]-2- methylbenzenesulphonamide hydrochloride, was studied in man and laboratory animals. Humans excreted 30.1% of dose as unchanged drug, and the sulphate conjugate of a 5-hydroxy metabolite, (+/-)-5-[1-hydroxy-2-[[2-(5-hydroxy-2-methoxyphenoxy)ethyl]-amino] ethyl]-2-methylbenzenesulphonamide, was the major metabolite. Amosulalol hydrochloride was extensively metabolized in animals with 10% or less excreted as unchanged drug. Hydroxylation of the 2-methyl group and O-demethylation of the o-methoxyphenoxy group were preferred in rats, and oxidative C-N cleavage yielding o-methoxyphenoxyacetic acid (M-5) preceded other reactions in dogs. Monkeys excreted almost equal amounts of the 5-hydroxy and 4-hydroxy metabolites as well as M-5.

Iso-branched 2- and 3-hydroxy fatty acids as characteristic lipid constituents of some gliding bacteria.

PubMed Central

Fautz, E; Rosenfelder, G; Grotjahn, L

1979-01-01

The fatty acids present in the total hydrolysates of several gliding bacteria (Myxococcus fulvus, Stigmatella aurantiaca, Cytophaga johnsonae, Cytophaga sp. strain samoa and Flexibacter elegans) were analyzed by combined gas-liquid chromatography and mass spectrometry. In addition to 13-methyl-tetradecanoic acid, 15-methyl-hexadecanoic acid, hexadecanoic acid, and hexadecenoic acid, 2- and 3-hydroxy fatty acids comprised up to 50% of the total fatty acids. The majority was odd-numbered and iso-branched. Small amounts of even-numbered and unbranched fatty acids were also present. Whereas 2-hydroxy-15-methyl hexadecanoic acid was characteristic for myxobacteria, 2-hydroxy-13-methyl-tetradecanoic acid, 3-hydroxy-13-methyl-tetradecanoic acid, and 3-hydroxy-15-methyl-hexadecanoic acid were dominant in the Cytophaga-Flexibacter group. PMID:118159

Study on environmental stability of a Zn based metal chelate organic small molecule in powder and thin films

NASA Astrophysics Data System (ADS)

Shukla, Vivek Kumar; Maitra, Jaya

2013-06-01

The organic small molecules like Bis (8-hydroxy quinoline) Zinc, (Znq2), used in organic light emitting diodes (OLEDs) are sensitive to environment species like moisture and air. Using characterization tools like photoluminescence (PL), FTIR and DSC, we investigated that as deposited films of Znq2 have a significant component of Znq2 tetramer and less dihydrate component. The stability of films deposited at higher deposition rates may be due to higher component of tetramer.

Seasonal variations of low molecular weight hydroxy-dicarboxylic acids and oxaloacetic acid in remote marine aerosols from Chichijima Island in the western North Pacific (December 2010-November 2011)

NASA Astrophysics Data System (ADS)

Gowda, Divyavani; Kawamura, Kimitaka

2018-05-01

Concentrations of homologous hydroxy-dicarboxylic acids (diacids) (hC3-hC6) and keto-diacid (oxaloacetic acid) were measured in the atmospheric aerosols collected at Chichijima Island (27.04° N, 142.13° E) in the western North Pacific from December 2010 to November 2011. The monthly averaged concentrations of hydroxy-diacids and oxaloacetic acid were significantly higher in spring followed by winter and autumn. Molecular distributions of hydroxy-diacids demonstrated that malic acid was the most abundant species in all four seasons, followed by tartronic acid in winter and spring and 3- and 2-hydroxyglutaric acids in summer and autumn. Hydroxy-diacids and keto-diacid maximized in spring and winter when air masses originated from the Asian continent with westerly winds. The concentrations of total hydroxy-diacids and oxaloacetic acid ranged from 0.1 to 27.3 ng m-3 and <0.005 to 2 ng m-3, respectively. The enhanced concentrations of diacids and their intermediates in winter and spring are associated with a long-range atmospheric transport of pollutants from East Asia to remote Chichijima Island followed by photochemical processing of organic aerosols. Seasonal molecular distribution of hydroxy-diacids and oxaloacetic acid was found to be dependent on the source strengths and plausible photochemical processing to form smaller diacids. Moderate to strong correlations among hydroxy-diacids, oxaloacetic acid and low molecular weight (LMW) diacids suggest that hydroxy-diacids and oxaloacetic acid are the intermediates in the photochemical oxidation of LMW diacid. Hence, photochemical formation of the most abundant LMW diacids, i.e., oxalic acid, could be produced from hydroxy- and keto-diacid as intermediates.

Relationship between Vitamin D Status and Autonomic Nervous System Activity

PubMed Central

Burt, Morton G.; Mangelsdorf, Brenda L.; Stranks, Stephen N.; Mangoni, Arduino A.

2016-01-01

Vitamin D deficiency is associated with increased arterial stiffness. However, the mechanisms underlying this association have not been clarified. The aim was to investigate whether changes in autonomic nervous system activity could underlie an association between 25 hydroxy vitamin D and arterial stiffness. A total of 49 subjects (age = 60 ± 8 years, body mass index = 26.7 ± 4.6 kg/m2, 25 hydroxy vitamin D = 69 ± 22 nmol/L) underwent measurements of pulse wave velocity (PWV) and augmentation index (AIx), spontaneous baroreflex sensitivity, plasma metanephrines and 25 hydroxy vitamin D. Subjects with 25 hydroxy vitamin D ≤ 50 nmol/L were restudied after 200,000 International Units 25 hydroxy vitamin D. Plasma metanephrine was positively associated with AIx (p = 0.02) independent of age, sex, smoking and cholesterol and negatively associated with 25 hydroxy vitamin D (p = 0.002) independent of age, sex and season. In contrast, there was no association between baroreflex sensitivity and 25 hydroxy vitamin D (p = 0.54). Treatment with vitamin D increased 25 hydroxy vitamin D from 43 ± 5 to 96 ± 24 nmol/L (p < 0.0001) but there was no significant change in plasma metanephrine (115 ± 25 vs. 99 ± 39 pmol/L, p = 0.12). We conclude that as plasma metanephrine was negatively associated with 25 hydroxy vitamin D and positively with AIx, it could mediate an association between these two variables. This hypothesis should be tested in larger interventional studies. PMID:27649235

Efficient enzymatic production of hydroxy fatty acids by linoleic acid Δ9 hydratase from Lactobacillus plantarum AKU 1009a.

PubMed

Takeuchi, M; Kishino, S; Park, S-B; Hirata, A; Kitamura, N; Saika, A; Ogawa, J

2016-05-01

This study aims to produce hydroxy fatty acids efficiently. Escherichia coli overexpressing linoleic acid Δ9 hydratase from Lactobacillus plantarum AKU 1009a was employed to produce hydroxy fatty acids with industrial potential. We found that 280 g l(-1) of linoleic acid (1 mol l(-1)) was converted into (S)-10-hydoxy-cis-12-octadecenoic acid (HYA) with a high conversion rate of 98% (mol/mol) and more than 99·9% enantiomeric excess (e.e.) by recombinant E. coli cells in the presence of FAD and NADH. In the same way, many kinds of C18 unsaturated fatty acids with Δ9 carbon double bond (280 g l(-1)) were converted into corresponding 10-hydroxy fatty acids with the conversion rates over 95% (mol/mol). We also produced HYA at a high rate of accumulation (289 g l(-1) ) with a high yield (97 mol%) in a reaction mixture that contained glucose instead of NADH. We developed a process for producing several types of hydroxy fatty acids with high accumulation rates and high yields. Hydroxy fatty acids are important materials for the chemical, food, cosmetic and pharmaceutical industries, and thus they have recently attracted much interest in a variety of research fields. However, the mass production of hydroxy fatty acids has been limited. This method of hydroxy fatty acids production will facilitate the widespread application of hydroxy fatty acids in various industries. © 2016 The Society for Applied Microbiology.

Regiospecific and stereoselective hydroxylation of 1-indanone and 2-indanone by naphthalene dioxygenase and toluene dioxygenase.

PubMed Central

Resnick, S M; Torok, D S; Lee, K; Brand, J M; Gibson, D T

1994-01-01

The biotransformation of 1-indanone and 2-indanone to hydroxyindanones was examined with bacterial strains expressing naphthalene dioxygenase (NDO) and toluene dioxygenase (TDO) as well as with purified enzyme components. Pseudomonas sp. strain 9816/11 cells, expressing NDO, oxidized 1-indanone to a mixture of 3-hydroxy-1-indanone (91%) and 2-hydroxy-1-indanone (9%). The (R)-3-hydroxy-1-indanone was formed in 62% enantiomeric excess (ee) (R:S, 81:19), while the 2-hydroxy-1-indanone was racemic. The same cells also formed 2-hydroxy-1-indanone from 2-indanone. Purified NDO components oxidized 1-indanone and 2-indanone to the same products produced by strain 9816/11. P. putida F39/D cells, expressing TDO, oxidized 2-indanone to (S)-2-hydroxy-1-indanone of 76% ee (R:S, 12:88) but did not oxidize 1-indanone efficiently. Purified TDO components also oxidized 2-indanone to (S)-2-hydroxy-1-indanone of 90% ee (R:S, 5:95) and failed to oxidize 1-indanone. Oxidation of 1- and 2-indanone in the presence of [18O]oxygen indicated that the hydroxyindanones were formed by the incorporation of a single atom of molecular oxygen (monooxygenation) rather than by the dioxygenation of enol tautomers of the ketone substrates. As alternatives to chemical synthesis, these biotransformations represent direct routes to 3-hydroxy-1-indanone and 2-hydroxy-1-indanone as the major products from 1-indanone and 2-indanone, respectively. PMID:7944365

Regiospecific and stereoselective hydroxylation of 1-indanone and 2-indanone by naphthalene dioxygenase and toluene dioxygenase.

PubMed

Resnick, S M; Torok, D S; Lee, K; Brand, J M; Gibson, D T

1994-09-01

The biotransformation of 1-indanone and 2-indanone to hydroxyindanones was examined with bacterial strains expressing naphthalene dioxygenase (NDO) and toluene dioxygenase (TDO) as well as with purified enzyme components. Pseudomonas sp. strain 9816/11 cells, expressing NDO, oxidized 1-indanone to a mixture of 3-hydroxy-1-indanone (91%) and 2-hydroxy-1-indanone (9%). The (R)-3-hydroxy-1-indanone was formed in 62% enantiomeric excess (ee) (R:S, 81:19), while the 2-hydroxy-1-indanone was racemic. The same cells also formed 2-hydroxy-1-indanone from 2-indanone. Purified NDO components oxidized 1-indanone and 2-indanone to the same products produced by strain 9816/11. P. putida F39/D cells, expressing TDO, oxidized 2-indanone to (S)-2-hydroxy-1-indanone of 76% ee (R:S, 12:88) but did not oxidize 1-indanone efficiently. Purified TDO components also oxidized 2-indanone to (S)-2-hydroxy-1-indanone of 90% ee (R:S, 5:95) and failed to oxidize 1-indanone. Oxidation of 1- and 2-indanone in the presence of [18O]oxygen indicated that the hydroxyindanones were formed by the incorporation of a single atom of molecular oxygen (monooxygenation) rather than by the dioxygenation of enol tautomers of the ketone substrates. As alternatives to chemical synthesis, these biotransformations represent direct routes to 3-hydroxy-1-indanone and 2-hydroxy-1-indanone as the major products from 1-indanone and 2-indanone, respectively.

Simultaneous quantification of epoxy and hydroxy fatty acids as oxidation products of triacylglycerols in edible oils.

PubMed

Xia, Wei; Budge, Suzanne M

2018-02-16

Epoxy and hydroxy fatty acids are important intermediates during lipid oxidation; quantification of both structures may help evaluate the extent of competition among various lipid oxidation pathways. This article describes a method to simultaneously determine saturated- and unsaturated- epoxy and hydroxy fatty acids derived from oxidation of vegetable oils. The experimental procedures employed transesterification with sodium methoxide, separation of epoxy and hydroxy fatty acid methyl esters (FAME) using solid-phase extraction (SPE), and trimethylsilyl (TMS) derivatization of hydroxy groups. GC-MS was used to identify the epoxy and hydroxy FAME in two different SPE fractions, while GC-flame ionization detection (GC-FID) was used to determine their quantities. Epoxy-octadecanoate/octadecenoate and hydroxy-octadecanoate/octadecenoate/octadecadienoate were determined as lipid oxidation products generated from oxidation of sunflower and canola oils. An isomer of methyl 13-hydroxyoctadeca-9,11-dienoate (13-HODE) TMS ether co-eluted with methyl 15-hydroxyoctadeca-9,12-dienoate TMS ether, which was only present in canola oil; thus, GC-MS-selected ion monitoring (GC-MS-SIM) was used to determine the concentration of 13-HODE. The proposed method has been successfully applied to monitor epoxy and hydroxy fatty acids in sunflower oil and canola oil oxidized at 40 °C. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

[Study on water-soluble chemical constituents of Taraxacum mongolicum].

PubMed

Liu, Hua-qing; Wang, Tian-lin

2014-06-01

To study the water-soluble chemical constituents of Taraxacum mongolicum. The chemical constituents were isolated and purified by means of several chromatographic techniques and their structures were elucidated by spectroscopic methods. Nine compounds were isolated and identified as trans-p-coumaryl alcohol(1), trans-p-coumaryl aldehyde(2),p- hydroxybenzoate (3) , p-hydroxyphenyl-propionic acid (4) , 4-hydroxy-2, 6-dimethoxyphenol-1 -O-β-D-glucopyranoside (5) , protocate- chuic aldehyde(6) ,rutin(7) ,quercetin(8) ,kaempferal-3-O-α-L-rhamnopyranosyl-( 1-6) -β-D-glucopyranoside(9). Com pounds 1-6 are isolated from this plant for the first time.

Further investigation into maple syrup yields 3 new lignans, a new phenylpropanoid, and 26 other phytochemicals.

PubMed

Li, Liya; Seeram, Navindra P

2011-07-27

Maple syrup is made by boiling the sap collected from certain maple ( Acer ) species. During this process, phytochemicals naturally present in tree sap are concentrated in maple syrup. Twenty-three phytochemicals from a butanol extract of Canadian maple syrup (MS-BuOH) had previously been reported; this paper reports the isolation and identification of 30 additional compounds (1-30) from its ethyl acetate extract (MS-EtOAc) not previously reported from MS-BuOH. Of these, 4 compounds are new (1-3, 18) and 20 compounds (4-7, 10-12, 14-17, 19, 20, 22-24, 26, and 28-30) are being reported from maple syrup for the first time. The new compounds include 3 lignans and 1 phenylpropanoid: 5-(3″,4″-dimethoxyphenyl)-3-hydroxy-3-(4'-hydroxy-3'-methoxybenzyl)-4-(hydroxymethyl)dihydrofuran-2-one (1), (erythro,erythro)-1-[4-[2-hydroxy-2-(4-hydroxy-3-methoxyphenyl)-1-(hydroxymethyl)ethoxy]-3,5-dimethoxyphenyl]-1,2,3-propanetriol (2), (erythro,threo)-1-[4-[2-hydroxy-2-(4-hydroxy-3-methoxyphenyl)-1-(hydroxymethyl)ethoxy]-3,5-dimethoxyphenyl]-1,2,3-propanetriol (3), and 2,3-dihydroxy-1-(3,4- dihydroxyphenyl)-1-propanone (18), respectively. In addition, 25 other phenolic compounds were isolated including (threo,erythro)-1-[4-[(2-hydroxy-2-(4-hydroxy-3-methoxyphenyl)-1-(hydroxymethyl)ethoxy]-3-methoxyphenyl]-1,2,3-propanetriol (4), (threo,threo)-1-[4-[(2-hydroxy-2-(4-hydroxy-3-methoxyphenyl)-1-(hydroxymethyl)ethoxy]-3-methoxyphenyl]-1,2,3-propanetriol (5), threo-guaiacylglycerol-β-O-4'-dihydroconiferyl alcohol (6), erythro-1-(4-hydroxy-3-methoxyphenyl)-2-[4-(3-hydroxypropyl)-2,6-dimethoxyphenoxy]-1,3-propanediol (7), 2-[4-[2,3-dihydro-3-(hydroxymethyl)-5-(3-hydroxypropyl)-7-methoxy-2-benzofuranyl]-2,6-dimethoxyphenoxy]-1-(4-hydroxy-3-methoxyphenyl)-1,3-propanediol (8), acernikol (9), leptolepisol D (10), buddlenol E (11), (1S,2R)-2-[2,6-dimethoxy-4-[(1S,3aR,4S,6aR)-tetrahydro-4-(4-hydroxy-3,5-dimethoxyphenyl)-1H,3H-furo[3,4-c]furan-1-yl]phenoxy]-1-(4-hydroxy-3-methoxyphenyl)-1,3-propanediol (12), syringaresinol (13), isolariciresinol (14), icariside E4 (15), sakuraresinol (16), 1,2-diguaiacyl-1,3-propanediol (17), 2,3-dihydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)-1-propanone (19), 3-hydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)propan-1-one (20), dihydroconiferyl alcohol (21), 4-acetylcatechol (22), 3',4',5'-trihydroxyacetophenone (23), 3,4-dihydroxy-2-methylbenzaldehyde (24), protocatechuic acid (25), 4-(dimethoxymethyl)pyrocatechol (26), tyrosol (27), isofraxidin (28), and 4-hydroxycatechol (29). One sesquiterpene, phaseic acid (30), which is a known metabolite of the phytohormone abscisic acid, was also isolated from MS-EtOAc. The antioxidant activities of MS-EtOAc (IC(50) = 75.5 μg/mL) and the pure isolates (IC(50) ca. 68-3000 μM) were comparable to that of vitamin C (IC(50) = 40 μM) and the synthetic commercial antioxidant butylated hydroxytoluene (IC(50) = 3000 μM), in the diphenylpicrylhydrazyl radical scavenging assay. The current study advances scientific knowledge of maple syrup constituents and suggests that these diverse phytochemicals may impart potential health benefits to this natural sweetener.

Further Investigation Into Maple Syrup Yields Three New Lignans, a New Phenylpropanoid, and Twenty-Six Other Phytochemicals

PubMed Central

LI, LIYA; SEERAM, NAVINDRA P.

2011-01-01

Maple syrup is made by boiling the sap collected from certain maple (Acer) species. During this process, phytochemicals naturally present in tree sap are concentrated in maple syrup. We previously reported 23 phytochemicals from a butanol extract of Canadian maple syrup (MS-BuOH). Here we report the isolation and identification of 30 additional compounds (1–30) from its ethyl acetate extract (MS-EtOAc) not previously reported from MS-BuOH. Of these, 4 compounds are new (1–3, 18) and 20 compounds (4–7, 10–12, 14–17, 19–20, 22–24, 26, 28–30) are being reported from maple syrup for the first time. The new compounds include 3 lignans and 1 phenylpropanoid: 5-(3″,4″-dimethoxyphenyl)-3-hydroxy-3-(4′-hydroxy-3′-methoxybenzyl)-4-hydroxymethyl-dihydrofuran-2-one (1), (erythro, erythro)-1-[4-[2-hydroxy-2-(4-hydroxy-3-methoxyphenyl)-1-(hydroxymethyl)ethoxy]-3,5-dimethoxyphenyl]-1,2,3-propanetriol (2), (erythro, threo)-1-[4-[2-hydroxy-2-(4-hydroxy-3-methoxyphenyl)-1-(hydroxymethyl)ethoxy]-3,5-dimethoxyphenyl]-1,2,3-propanetriol (3) and 2,3-dihydroxy-1-(3,4-dihydroxyphenyl)-1-propanone (18), respectively. In addition, 25 other phenolic compounds were isolated including (threo, erythro)-1-[4-[(2-hydroxy-2-(4-hydroxy-3-methoxyphenyl)-1-(hydroxymethyl)ethoxy]-3-methoxyphenyl]-1,2,3-propanetriol (4), (threo, threo)-1-[4-[(2-hydroxy-2-(4-hydroxy-3-methoxyphenyl)-1-(hydroxymethyl)ethoxy]-3-methoxyphenyl]-1,2,3-propanetriol (5), threo-guaiacylglycerol-β-O-4′-dihydroconiferyl alcohol (6), erythro-1-(4-hydroxy-3-methoxyphenyl)-2-[4-(3-hydroxypropyl)-2,6-dimethoxyphenoxy]-1,3-propanediol (7), 2-[4-[2,3-dihydro-3-(hydroxymethyl)-5-(3-hydroxypropyl)-7-methoxy-2-benzofuranyl]-2,6-dimethoxyphenoxy]-1-(4-hydroxy-3-methoxyphenyl)-1,3-propanediol (8), acernikol (9), leptolepisol D (10), buddlenol E (11), (1S,2R)-2-[2,6-dimethoxy-4-[(1S,3aR,4S,6aR)-tetrahydro-4-(4-hydroxy-3,5-dimethoxyphenyl)-1H,3H-furo[3,4-c]furan-1-yl]phenoxy]-1-(4-hydroxy-3-methoxyphenyl)-1,3-propanediol (12), syringaresinol (13), isolariciresinol (14), icariside E4 (15), sakuraresinol (16), 1,2-diguaiacyl-1,3-propanediol (17), 2,3-dihydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)-1-propanone (19), 3-hydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)propan-1-one (20), dihydroconiferyl alcohol (21), 4-acetylcatechol (22), 3′,4′,5′-trihydroxyacetophenone (23), 3,4-dihydroxy-2-methylbenzaldehyde (24), protocatechuic acid (25), 4-(dimethoxymethyl)-pyrocatechol (26), tyrosol (27), isofraxidin (28) and 4-hydroxycatechol (29). One sesquiterpene, phaseic acid (30), which is a known metabolite of the phytohormone, abscisic acid, was also isolated from MS-EtOAc. The antioxidant activities of MS-EtOAc (IC50 = 75.5 μg/mL), and the pure isolates (IC50 ca. 68–3000 μM) were comparable to vitamin C (IC50 = 40 μM) and the synthetic commercial antioxidant, butylated hydroxytoluene (IC50 = 3000 μM), in the diphenylpicrylhydrazyl radical scavenging assay. The current study advances scientific knowledge of maple syrup constituents and suggest that these diverse phytochemicals may impart potential health benefits to this natural sweetener. PMID:21675726

Subcellular distribution of delta 5-3 beta-hydroxy steroid dehydrogenase in the granulosa cells of the domestic fowl (Gallus domesticus).

PubMed Central

Armstrong, D G

1979-01-01

1. The distribution of 3 beta-hydroxy steroid dehydrogenase was examined in the subcellular fractions of granulosa cells collected from the ovary of the domestic fowl. 2. 3 beta-hydroxy steroid dehydrogenase activity was observed in the mitochondrial (4000g for 20min) and microsomal (105 000g for 120min) fractions. 3. Approximately three times more 3 beta-hydroxy steroid dehydrogenase activity was associated with the cytochrome oxidase activity (a mitochondrial marker enzyme) in anteovulatory-follicle granulosa cells than with that of the postovulatory follicle. 4. Comparison of the latent properties of mitochondrial 3 beta-hydroxy steroid dehydrogenase with those of cytochrome oxidase and isocitrate dehydrogenase indicated that 3 beta-hydroxy steroid dehydrogenase is located extramitochondrially. 5. This apparent distribution of 3 beta-hydroxy steroid dehydrogenase is explained on the basis that the mitochondrial activity is either an artefact caused by a redistribution in the subcellular location of the enzyme, occurring during homogenization, or by the existence of a functionally heterogeneous endoplasmic reticulum that yields particles of widely differing sedimentation properties. PMID:518548

A novel pyrimidine derivative as a fluorescent chemosensor for highly selective detection of Aluminum (III) in aqueous media

NASA Astrophysics Data System (ADS)

Suryawanshi, Vishwas D.; Gore, Anil H.; Dongare, Pravin R.; Anbhule, Prashant V.; Patil, Shivajirao R.; Kolekar, Govind B.

2013-10-01

An efficient fluorescent chemosensor Al3+ receptor based on pyrimidine derivative,2-amino-6-hydroxy-4-(4-N,N-dimethylaminophenyl)-pyrimidine-5-carbonitrile (DMAB), has been synthesized by three-component condensation of aromatic aldehyde, ethyl cyanoacetate and guanidine hydrochloride in ethanol under alkaline medium. High selectivity and sensitivity of DMAB towards Aluminum ion (Al3+) in water: ethanol and acetate buffer at pH 4.0 makes it suitable to detect Al3+ with steady-state UV-vis and fluorescence spectroscopy. Method shows good selectivity towards Al3+ over other coexisting metal ions tested, viz. Fe2+, Ni2+, Cu2+, Co2+, Pb2+, Sb3+, Na+, Ca2+, Mg2+, Zn2+, Hg2+, Ba2+, Cd2+ and K+. A good linearity between the Stern-Volmer plots of F0/F versus concentration of Al3+ was observed over the range from 10 to 60 μg mL-1 with correlation coefficient of 0.991. The accuracy and reliability of the method were further confirmed by recovery studies via standard addition method with percent recoveries in the range of 101.03-103.44% and lowest detection limit (LOD = 7.35 μg mL-1) for Al3+ was established. This method may offer a new cost-effective, rapid, and simple key to the inspection of Al3+ ions in water samples in the presence of a complex matrix and can be capable of evaluating the exceeding standard of Al3+ in environmental water samples. The probable mechanism for fluorescence quenching was also discussed.

40 CFR 721.10556 - Poly(oxy-1,2-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-15-alkyl ethers.

Code of Federal Regulations, 2013 CFR

2013-07-01

....- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers (PMN P-06-452; CAS No. 675869-05-3...-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-15-alkyl ethers. 721.10556 Section 721.10556 Protection of...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-15-alkyl ethers. (a) Chemical substance...

40 CFR 721.10556 - Poly(oxy-1,2-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-15-alkyl ethers.

Code of Federal Regulations, 2014 CFR

2014-07-01

....- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers (PMN P-06-452; CAS No. 675869-05-3...-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-15-alkyl ethers. 721.10556 Section 721.10556 Protection of...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-15-alkyl ethers. (a) Chemical substance...

40 CFR 721.10558 - Poly(oxy-1,2-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers.

Code of Federal Regulations, 2013 CFR

2013-07-01

....- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers (PMN P-06-452; CAS No. 675869-05-3...-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers. 721.10558 Section 721.10558 Protection of...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers. (a) Chemical substance...

40 CFR 721.10557 - Poly(oxy-1,2-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C10-16-alkyl ethers.

Code of Federal Regulations, 2014 CFR

2014-07-01

....- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers (PMN P-06-452; CAS No. 675869-05-3...-methyl-2-propen-1-yl) -.omega.-hydroxy-,C10-16-alkyl ethers. 721.10557 Section 721.10557 Protection of...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C10-16-alkyl ethers. (a) Chemical substance...

40 CFR 721.10558 - Poly(oxy-1,2-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers.

Code of Federal Regulations, 2014 CFR

2014-07-01

....- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers (PMN P-06-452; CAS No. 675869-05-3...-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers. 721.10558 Section 721.10558 Protection of...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers. (a) Chemical substance...

40 CFR 721.10557 - Poly(oxy-1,2-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C10-16-alkyl ethers.

Code of Federal Regulations, 2013 CFR

2013-07-01

....- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers (PMN P-06-452; CAS No. 675869-05-3...-methyl-2-propen-1-yl) -.omega.-hydroxy-,C10-16-alkyl ethers. 721.10557 Section 721.10557 Protection of...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C10-16-alkyl ethers. (a) Chemical substance...

Bio-plastic (poly-hydroxy-alkanoate) production from municipal sewage sludge in the Netherlands: a technology push or a demand driven process?

PubMed

Bluemink, E D; van Nieuwenhuijzen, A F; Wypkema, E; Uijterlinde, C A

Valorisation of components from municipal 'waste' water and sewage sludge gets more and more attention in order to come to a circular economy by developing an efficient 'waste' to value concept. On behalf of the transition team 'Grondstoffenfabriek' ('Resource factory') a preliminary research was performed for all the Dutch water boards to assess the technical and economical feasibility of poly-hydroxy-alkanoate (PHA)-production from sewage sludge, a valuable product to produce bio-plastics. This study reveals that the production of bio-plastics from sewage sludge is feasible based on technical aspects, but not yet economically interesting, even though the selling price is relatively close to the actual PHA market price. (Selling price is in this particular case the indicative cost effective selling price. The cost effective selling price covers only the total production costs of the product.) Future process optimization (maximizing the volatile fatty acids production, PHA storage capacity, etc.) and market developments are needed and will result in cost reductions of the various sub-processes. PHA-production from sewage sludge at this stage is just a technology; every further research is needed to incorporate the backward integration approach, taking into account the market demand including associated product quality aspects.

The Relative Amounts and Identification of Some 2,4-Dichlorophenoxyacetic Acid Metabolites Isolated from Soybean Cotyledon Callus Cultures 1

PubMed Central

Feung, Chao-Shieung; Hamilton, Robert H.; Witham, Francis H.; Mumma, Ralph O.

1972-01-01

Soybean (Glycine max L.) cotyledon callus grown on radioactive 2,4-dichlorophenoxyacetic acid (2,4-D-1-14C) as an auxin produced 2,4-D metabolites, which qualitatively and quantitatively changed with time. Water soluble fractions from the tissue exhibited a steady increase in radioactivity during the course of 24 days. Following β-glucosidase treatment, at least eight aglycones were obtained from the water soluble fraction of the tissue after 8 days. The metabolite, 4-hydroxy-2,5-dichlorophenoxyacetic acid was the most abundant aglycone during the entire 32 day growth period while 4-hydroxy-2,3-dichlorophenoxyacetic acid was detected as a minor metabolite. Radioactivity in the ether soluble acidic fractions reached a maximum of 82% of the total in the tissue after 2 days. The level then decreased to 44% by the end of 24 days. A total of seven ether soluble components were detected. In addition to 2,4-D glutamic acid, which was detected in high amounts after 24 hours, 2,4-D aspartic acid was found to be the most abundant ether soluble metabolite after longer time periods. Mass spectral data and a fragmentation pattern are presented for 2,4-D aspartic acid. PMID:16658138

CYP109E1 is a novel versatile statin and terpene oxidase from Bacillus megaterium.

PubMed

Putkaradze, Natalia; Litzenburger, Martin; Abdulmughni, Ammar; Milhim, Mohammed; Brill, Elisa; Hannemann, Frank; Bernhardt, Rita

2017-12-01

CYP109E1 is a cytochrome P450 monooxygenase from Bacillus megaterium with a hydroxylation activity for testosterone and vitamin D3. This study reports the screening of a focused library of statins, terpene-derived and steroidal compounds to explore the substrate spectrum of this enzyme. Catalytic activity of CYP109E1 towards the statin drug-precursor compactin and the prodrugs lovastatin and simvastatin as well as biotechnologically relevant terpene compounds including ionones, nootkatone, isolongifolen-9-one, damascones, and β-damascenone was found in vitro. The novel substrates induced a type I spin-shift upon binding to P450 and thus permitted to determine dissociation constants. For the identification of conversion products by NMR spectroscopy, a B. megaterium whole-cell system was applied. NMR analysis revealed for the first time the ability of CYP109E1 to catalyze an industrially highly important reaction, the production of pravastatin from compactin, as well as regioselective oxidations generating drug metabolites (6'β-hydroxy-lovastatin, 3'α-hydroxy-simvastatin, and 4″-hydroxy-simvastatin) and valuable terpene derivatives (3-hydroxy-α-ionone, 4-hydroxy-β-ionone, 11,12-epoxy-nootkatone, 4(R)-hydroxy-isolongifolen-9-one, 3-hydroxy-α-damascone, 4-hydroxy-β-damascone, and 3,4-epoxy-β-damascone). Besides that, a novel compound, 2-hydroxy-β-damascenone, produced by CYP109E1 was identified. Docking calculations using the crystal structure of CYP109E1 rationalized the experimentally observed regioselective hydroxylation and identified important amino acid residues for statin and terpene binding.

Synthesis of 7-hydroxy-4'-methoxyflavanone and 7-hydroxy-4'-methoxyflavone as a candidate anticancer against cervical (HeLa) cancer cell and colon (WiDr) cancer cell by in vitro

NASA Astrophysics Data System (ADS)

Matsjeh, Sabirin; Anwar, Chairil; Solikhah, Eti Nurwening; Farah, Harra Ismi; Nurfitria, Kurnia

2017-03-01

The compound 7-hydroxy-4'-methoxyflavanone and 7-hydroxy-4'-methoxyflavone have been synthesized through cyclization reaction of 2 ', 4'-dihydroxy-4-methoxychalcone (1,3-diphenyl-2-propene-1-one). The 2 ', 4'-dihydroxy-4-methoxychalcone were synthesized through Claisen-Schmidt condensation from 2,4-dihydroxyacetophenone and 4-methoxybenzaldehyde (anisaldehyde) in aqueous KOH as a catalyst in ethanol. The 7-hydroxy-4'-methoxyflavanone has been synthesized through cyclization reaction of 2 ', 4'-dihydroxy-4-methoxychalcone by Oxa-Michael addition reaction with sulfuric acid as a catalyst in ethanol. The 7-hydroxy-4'-methoxyflavone has been synthesized through oxidative cyclization reaction of 2 ', 4'-dihydroxy-4-methoxychalcone using I2 in DMSO as a catalyst with a mole ratio (1: 1) mol. All these producets were characterized by FT-IR, GC-MS, and 1H-NMR and 13C-NMR spectrometer. Both of these compounds were tested citotoxycity activity as an anticancer against cervical and colon cancer cells (HeLa and WiDr cell lines) using MTT assay in vitro. Dose series given test solution concentration on HeLa and WiDr cells starting from 0,78; 1,56; 3,12; 6,25; 12,50; 25; 50 and 100 µg/mL with a long incubation treatment for 24 hours. The results study showed that the 7-hydroxy-4'-methoxyflavanone as bright yellow crystals with a melting point 172-174 ° C and a yield of 56.67% and the 7-hydroxy-4'-methoxyflavone as bright yellow crystals with a yield of 88, 31%, and a melting point of 263-265 ° C. The test results cytotoxic 7-hydroxy-4-methoxyflavone showed active against HeLa cells with IC50 value of 25.73 µg/mL and was quite active in the WiDr cells with IC50 value of 83.75 µg/mL. The result of the activity of 7-hydroxy-4-methoxyflavanone show active cytotoxic activity against HeLa and WiDr cell growth with IC50 value of 40.13 µg/mL and 37.85 µg/mL. IC50 value indicated that 7-hydroxy-4'-methoxyflavone and 7-hydroxy-4'-methoxyflavanone potential as inhibitors in HeLa and WiDr. cells

Analysis of chlorothalonil and three degradates in sediment and soil

USGS Publications Warehouse

Hladik, M.L.; Kuivila, K.M.

2008-01-01

A method has been developed for the simultaneous extraction of chlorothalonil and three of its degradates (4-hydroxy-2,5,6- trichloroisophthalonitrile, 1-carbamoyl-3-cyano-4-hydroxy-2,5,6- trichlorobenzene, and 1,3-dicarbamoyl-2,4,5,6-tetrachlorobenzene) from soils and sediments; the compounds were extracted using sonication with acetone and isolation of the parent compound and matrix interferences from the degradates by solid phase extraction (SPE). The chlorothalonil fraction underwent further coextracted matrix interference removal with Florisil. The degradates were derivatized with N,O-bis(trimethylsilyl) trifluoroacetamide (BSTFA) and chlorotrimethylsilane (TMCS). All compounds were analyzed by gas chromatography-mass spectrometry (GC-MS). Recoveries on a spiked (20 and 200 ??g kg-1) sediment ranged from 80% to 91% with calculated limits of detection of 1-5 ??g kg-1 dry weight sediment. An additional 20 sediment samples were collected in watersheds from the Southeastern United States where chlorothalonil is used widely on peanuts and other crops. None of the target compounds were detected. Laboratory fortified recoveries of chlorothalonil and its degradates in these environmental sediment samples ranged from 75% to 89%.

Airborne environmental endotoxin: a cross-validation of sampling and analysis techniques.

PubMed Central

Walters, M; Milton, D; Larsson, L; Ford, T

1994-01-01

A standard method for measurement of airborne environmental endotoxin was developed and field tested in a fiberglass insulation-manufacturing facility. This method involved sampling with a capillary-pore membrane filter, extraction in buffer using a sonication bath, and analysis by the kinetic-Limulus assay with resistant-parallel-line estimation (KLARE). Cross-validation of the extraction and assay method was performed by comparison with methanolysis of samples followed by 3-hydroxy fatty acid (3-OHFA) analysis by gas chromatography-mass spectrometry. Direct methanolysis of filter samples and methanolysis of buffer extracts of the filters yielded similar 3-OHFA content (P = 0.72); the average difference was 2.1%. Analysis of buffer extracts for endotoxin content by the KLARE method and by gas chromatography-mass spectrometry for 3-OHFA content produced similar results (P = 0.23); the average difference was 0.88%. The source of endotoxin was gram-negative bacteria growing in recycled washwater used to clean the insulation-manufacturing equipment. The endotoxin and bacteria become airborne during spray cleaning operations. The types of 3-OHFAs in bacteria cultured from the washwater, present in the washwater and in the air, were similar. Virtually all of the bacteria cultured from air and water were gram negative composed mostly of two species, Deleya aesta and Acinetobacter johnsonii. Airborne countable bacteria correlated well with endotoxin (r2 = 0.64). Replicate sampling showed that results with the standard sampling, extraction, and Limulus assay by the KLARE method were highly reproducible (95% confidence interval for endotoxin measurement +/- 0.28 log10). These results demonstrate the accuracy, precision, and sensitivity of the standard procedure proposed for airborne environmental endotoxin. PMID:8161191

Commercially processed dry ginger (Zingiber officinale): composition and effects on LPS-stimulated PGE2 production.

PubMed

Jolad, Shivanand D; Lantz, R Clark; Chen, Guan Jie; Bates, Robert B; Timmermann, Barbara N

2005-07-01

Using techniques previously employed to identify ginger constituents in fresh organically grown Hawaiian white and yellow ginger varieties, partially purified fractions derived from the silica gel column chromatography and HPLC of a methylene chloride extract of commercially processed dry ginger, Zingiber officinale Roscoe, Zingiberaceae, which demonstrated remarkable anti-inflammatory activity, were investigated by gas chromatography-mass spectrometry. In all, 115 compounds were identified, 88 with retention times (R(t)) >21 min and 27 with <21 min. Of those 88 compounds, 45 were previously reported by us from fresh ginger, 12 are cited elsewhere in the literature and the rest (31) are new: methyl [8]-paradol, methyl [6]-isogingerol, methyl [4]-shogaol, [6]-isoshogaol, two 6-hydroxy-[n]-shogaols (n=8 and 10), 6-dehydro-[6]-gingerol, three 5-methoxy-[n]-gingerols (n=4, 8 and 10), 3-acetoxy-[4]-gingerdiol, 5-acetoxy-[6]-gingerdiol (stereoisomer), diacetoxy-[8]-gingerdiol, methyl diacetoxy-[8]-gingerdiol, 6-(4'-hydroxy-3'-methoxyphenyl)-2-nonyl-2-hydroxytetrahydropyran, 3-acetoxydihydro-[6]-paradol methyl ether, 1-(4'-hydroxy-3'-methoxyphenyl)-2-nonadecen-1-one and its methyl ether derivative, 1,7-bis-(4'-hydroxy-3'-methoxyphenyl)-5-methoxyheptan-3-one, 1,7-bis-(4'-hydroxy-3'-methoxyphenyl)-3-hydroxy-5-acetoxyheptane, acetoxy-3-dihydrodemethoxy-[6]-shogaol, 5-acetoxy-3-deoxy-[6]-gingerol, 1-hydroxy-[6]-paradol, (2E)-geranial acetals of [4]- and [6]-gingerdiols, (2Z)-neral acetal of [6]-gingerdiol, acetaldehyde acetal of [6]-gingerdiol, 1-(4-hydroxy-3-methoxyphenyl)-2,4-dehydro-6-decanone and the cyclic methyl orthoesters of [6]- and [10]-gingerdiols. Of the 27 R(t)<21 min compounds, we had found 5 from fresh ginger, 20 others were found elsewhere in the literature, and two are new: 5-(4'-hydroxy-3'-methoxyphenyl)-pent-2-en-1-al and 5-(4'-hydroxy-3'-methoxyphenyl)-3-hydroxy-1-pentanal. Most of the short R(t) compounds are probably formed by thermal degradation during GC (which mimics cooking) and/or commercial drying. The concentrations of gingerols, the major constituents of fresh ginger, were reduced slightly in dry ginger, while the concentrations of shogaols, the major gingerol dehydration products, increased.

Biomonitoring of polycyclic aromatic hydrocarbon exposure in pregnant women in Trujillo, Peru — Comparison of different fuel types used for cooking☆

PubMed Central

Adetona, Olorunfemi; Li, Zheng; Sjödin, Andreas; Romanoff, Lovisa C.; Aguilar-Villalobos, Manuel; Needham, Larry L.; Hall, Daniel B.; Cassidy, Brandon E.; Naeher, Luke P.

2016-01-01

Women and children in developing countries are often exposed to high levels of air pollution including polycyclic aromatic hydrocarbons (PAHs), which may negatively impact their health, due to household combustion of biomass fuel for cooking and heating. We compared creatinine adjusted hydroxy-PAH (OH-PAH) concentrations in pregnant women in Trujillo, Peru who cook with wood to levels measured in those who cook with kerosene, liquefied petroleum gas or a combination of fuels. Seventy-nine women were recruited for the study between May and July 2004 in the first trimester of their pregnancy. Urine samples were collected from the subjects in the first, second and third trimesters for OH-PAH analyses. The concentrations of the OH-PAHs were compared across the type of fuel used for cooking and pregnancy trimesters. The relationships between OH-PAHs levels in the first trimester and concurrently measured personal exposures to PM2.5, carbon monoxide and nitrogen dioxide together with their indoor and outdoor air concentrations were also investigated. Women cooking with wood or kerosene had the highest creatinine adjusted OH-PAH concentrations compared with those using gas, coal briquette or a combination of fuels. Concentrations of creatinine adjusted 2-hydroxy-fluorene, 3-hydroxy-fluorene, 1-hydroxy-fluorene, 2-hydroxy-phenanthrene and 4-hydroxy-phenanthrene were significantly higher (p<0.05) in women who used wood or kerosene alone compared with women who used liquefied petroleum gas (LPG), coal briquette or a combination of fuels. An increase in the concentrations of creatinine adjusted 9-hydroxy-fluorene, 1-hydroxy-phenanthrene, 2-hydroxy-phenanthrene, 4-hydroxy-phenanthrene and 1-hydroxy-pyrene in the third trimesters was also observed. Weak positive correlation (Spearman correlation coefficient, ρ<0.4; p<0.05) was observed between all first trimester creatinine adjusted OH-PAHs and indoor (kitchen and living room), and personal 48-h TWA PM2.5. Women who cooked exclusively with wood or kerosene had higher creatinine adjusted OH-PAH levels in their urine samples compared to women who cooked with LPG or coal briquette. PMID:23314038

Biomarkers in fish as a measure of the state of marine environment of Kuwait.

PubMed

Beg, M U; Butt, S A; Al-Dufaileej, S; Karam, Q; Al-Sharrah, T K; Saeed, T

2018-05-04

The health of a marine ecosystem can effectively be monitored by studying the levels of biomarkers in a representative species. A change in background level of a biomarker indicates exposure to a specific type of pollutants. It also identifies bioavailability and the organism response to the causative agent among the compounds present in the surrounding water body. Yellowfin seabream (Acanthopagrus latus), a local variety of fish, was examined for parent PAHs in the liver, its metabolites in bile by the GC-MS method as exposure biomarkers and cytochrome P4501A1 by assay of ethoxyresorufin-o-deethylase (EROD) in the liver as an effect biomarker. A comparison was made between fish collected in 2015 with the fish collected in 2005-2006 and stored at - 80 °C in the fish bank. The objective was to examine the extent of changes in the environmental quality of the Kuwait marine area and the status of fish health concerning oil-related pollutants since Arabian Gulf is surrounded by oil-producing countries. Interestingly, insignificant differences between the liver PAH content and EROD activity were observed in fish over the sampling periods. The fish efficiently metabolized PAHs and excreted hydroxy-metabolites in bile. The study suggested that environmental quality of the Kuwait marine area was not deteriorated to any serious extent in the last decade and biomarkers can be used effectively in assessing the thrust of sub-optimal levels of various contaminants present in the marine area on the resident biota.

Determination of hydroxy metabolites of cocaine from hair samples and comparison with street cocaine samples.

PubMed

Franz, Thomas; Scheufler, Frank; Stein, Klaus; Uhl, Michael; Dame, Torsten; Schwarz, Gerlinde; Sachs, Hans; Skopp, Gisela; Musshoff, Frank

2018-07-01

Drugs which are commonly smoked or sniffed (e.g. cocaine), can contaminate hair through smoke or dust; therefore testing for metabolites, especially hydroxy metabolites, is highly recommended. The presence of hydroxy metabolites in street-cocaine (COC) has been discussed. To check if detection of hydroxy metabolites definitely proves ingestion, the presence of these metabolites in street COC samples has to be checked. It is expected that the more hydrophilic hydroxy metabolites of COC are incorporated into the hair-matrix to a lesser extent. For this study 576 COC positive hair samples (≥0.1ng COC/mg hair) were analysed by LC-MS/MS for benzoylecgonine (BE), norcocaine (NC), cocaethylene (CE), ortho-, meta- and para-hydroxy COC (o-, m-, p-OH-COC), meta- and para-hydroxy BE (m-, p-OH-BE), and meta- and para-hydroxy NC (m-, p-OH-NC). The results were compared with the respective metabolite/COC concentration ratios in 146 street COC samples, confiscated by the Bavarian police. Peak areas were used to estimate BE/COC, NC/COC, CE/COC and hydroxy metabolites/COC. Similar metabolic ratios were found for o-OH-COC in 88% of the samples, but for p-OH-COC and m-OH-COC only in 5.1% and 6.8%, respectively. Notably, p- and m-OH-BE as well as p- and m-OH-NC could not be identified from seized samples. We propose that area ratios exceeding the ratios of street COC more than twice or identification of OH-BE and OH-NC enable to differentiate COC consumption from contamination. Using these criteria, consumption of the drug could be proven in 92% of COC positive samples. As detection of meta- and para-hydroxy metabolites using the above mentioned criteria is a reliable tool to distinguish between ingestion and external contamination, it is recommended to implement their measurement into daily routine work. Copyright © 2018 Elsevier B.V. All rights reserved.

Pyrrolizidine alkaloids from Lithospermum canescens Lehm.

PubMed

Wiedenfeld, Helmut; Pietrosiuk, Agnieszka; Furmanowa, Miroslava; Roeder, Erhard

2003-01-01

Seven pyrrolizidine alkaloids (PAs) have been isolated from Lithospermum canescens and their structures determined by spectroscopical methods. Besides the known lycopsamine, O7-acetyl-lycopsamine and O7-acetylintermedine four new PAs were found. Their structures are O7-(3-hydroxy-3-methyl-butanoyl)-O9-(+)-trachelanthoyl-heliotridine (= O7-(3-hydroxy-3-methyl-butanoyl)-rinderine = canescine), O7-(3-hydroxy-3-methyl-butanoyl)-O9-(-)-viridifloryl-heliotridine (= O7-(3-hydroxy-3-methyl-butanoyl)-echinatine = canescenine and their O13-acetyl-derivatives (= acetylcanescine; acetylcanescenine).

Solvatochromicity of 3-hydroxy-4-(1-(2,4-dihydroxyphenyl)-2-hydroxy-2,2-diphenylethylidene)cyclohexa-2,5-dienone for screening of solvents

NASA Astrophysics Data System (ADS)

Babu, D. Suresh; Singh, W. Marjit; Kalita, Dipjyoti; Baruah, Jubaraj B.

2010-01-01

The quinonic compound 3-hydroxy-4-(1-(2,4-dihydroxyphenyl)-2-hydroxy-2,2-diphenylethylidene)cyclohexa-2,5-dienone ( I) is synthesised by the reaction of benzil with 1,3-dihydroxybenzene in basic medium. Solution of this compound shows visibly distinct colour differences in different solvents. From the different absorption maxima of the compound in visible spectra it can be used as an excellent analytical reagent to screen different solvents.

Two biflavonoids from Ouratea flava stem bark.

PubMed

Mbing, Joséphine Ngo; Pegnyemb, Dieudonné Emmanuel; Tih, Raphael Ghogomu; Sondengam, Beibam Lucas; Blond, Alain; Bodo, Bernard

2003-06-01

In a chemical investigation on the stem bark of Ouratea flava, two biflavonoids: 1-[3-(2,4-dihydroxy-benzoyl)-4,5,6-trihydroxy-2-(4-hydroxy-phenyl)-benzofuran-7-yl] -3-(4-hydroxy-phenyl) -propenone (flavumone A) and 3-(2,4-dihydroxy-benzoyl)-4-hydroxy-2,7-bis-(4-hydroxy-phenyl) -7,8- dihydro-furo[2,3-f]chromen-9-on (flavumone B) were isolated along with five known flavonoids. Their structures were established by various analyses including 2D-NMR spectroscopy.

Crystal and molecular structures of 3-amino-4-hydroxy benzenesulfonamide and its hydrochloride: Quantum-chemical study of their tautomerism

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

Kovalchukova, O. V., E-mail: okovalchukova@mail.ru; Strashnova, S. B.; Romashkina, E. P.

2013-03-15

3-amino-4-hydroxy benzenesulfonamide and its hydrochloride have been isolated in the crystalline state. Their crystal and molecular structures are determined by X-ray diffraction. The equilibrium between neutral tautomeric forms of the 3-amino-4-hydroxy benzenesulfonamide molecule is studied within the approximation of density functional theory (B3LYP/aug-cc-pVDZ). The constants of acid-base equilibrium of 3-amino-4-hydroxy benzenesulfonamide are deter-mined using spectrophotometry.

Monitoring benzo(a)pyrene exposure using laser-excited Shpol'skii spectroscopy of benzo(a)pyrene metabolites

NASA Astrophysics Data System (ADS)

Ariese, Freek; Kok, S. J.; Verkaik, M.; Hoornweg, Gerard P.; Gooijer, Cees; Velthorst, Nel H.; Hofstraat, Johannes W.

1993-03-01

Exposure to polycyclic aromatic hydrocarbons (PAHs) is considered a serious threat to the health of animals and humans and should be thoroughly monitored. Next to chemical analysis of PAHs in the various environmental compartments, PAH metabolites in body fluids (e.g., bile and urine) could be measured to determine the actual uptake. Although pyrene is not considered particularly toxic, its metabolite 1-hydroxy pyrene is often used as a biomarker because it is usually found at considerable concentrations and the analysis is relatively simple. As the result of differences in volatility and/or solubility, the uptake of more relevant carcinogens like benzo(a)pyrene may be some orders of magnitude lower and is far more difficult to measure. Determination of benzo(a)pyrene metabolites requires a very selective and sensitive method, and so far these compounds could only be detected after exposure to heavy pollution. In this paper it will be shown how several hydroxy benzo(a)pyrene metabolites are selectively determined using Shpol'skii spectroscopy. With this method, highly resolved fluorescence spectra are obtained upon cooling the sample in a suitable solvent to cryogenic temperatures. When a tunable laser system is employed as an excitation source, sub- femtomole amounts can be detected. Applications of the technique to marine monitoring (benzo(a)pyrene metabolites in fish bile) and to occupational hygienics (benzo(a)pyrene metabolites in workers' urine) are discussed. The data will be compared with 1-hydroxy pyrene concentrations to evaluate the routine use of the latter compound as a biomarker.

Benz[a]anthracene Biotransformation and Production of Ring Fission Products by Sphingobium sp. Strain KK22

PubMed Central

Kunihiro, Marie; Ozeki, Yasuhiro; Nogi, Yuichi; Hamamura, Natsuko

2013-01-01

A soil bacterium, designated strain KK22, was isolated from a phenanthrene enrichment culture of a bacterial consortium that grew on diesel fuel, and it was found to biotransform the persistent environmental pollutant and high-molecular-weight polycyclic aromatic hydrocarbon (PAH) benz[a]anthracene. Nearly complete sequencing of the 16S rRNA gene of strain KK22 and phylogenetic analysis revealed that this organism is a new member of the genus Sphingobium. An 8-day time course study that consisted of whole-culture extractions followed by high-performance liquid chromatography (HPLC) analyses with fluorescence detection showed that 80 to 90% biodegradation of 2.5 mg liter−1 benz[a]anthracene had occurred. Biodegradation assays where benz[a]anthracene was supplied in crystalline form (100 mg liter−1) confirmed biodegradation and showed that strain KK22 cells precultured on glucose were equally capable of benz[a]anthracene biotransformation when precultured on glucose plus phenanthrene. Analyses of organic extracts from benz[a]anthracene biodegradation by liquid chromatography negative electrospray ionization tandem mass spectrometry [LC/ESI(−)-MS/MS] revealed 10 products, including two o-hydroxypolyaromatic acids and two hydroxy-naphthoic acids. 1-Hydroxy-2- and 2-hydroxy-3-naphthoic acids were unambiguously identified, and this indicated that oxidation of the benz[a]anthracene molecule occurred via both the linear kata and angular kata ends of the molecule. Other two- and single-aromatic-ring metabolites were also documented, including 3-(2-carboxyvinyl)naphthalene-2-carboxylic acid and salicylic acid, and the proposed pathways for benz[a]anthracene biotransformation by a bacterium were extended. PMID:23686261

Reduction of N-hydroxy-sulfonamides, including N-hydroxy-valdecoxib, by the molybdenum-containing enzyme mARC.

PubMed

Havemeyer, Antje; Grünewald, Sanja; Wahl, Bettina; Bittner, Florian; Mendel, Ralf; Erdélyi, Péter; Fischer, János; Clement, Bernd

2010-11-01

Purification of the mitochondrial enzyme responsible for reduction of N-hydroxylated amidine prodrugs led to the identification of two newly discovered mammalian molybdenum-containing proteins, the mitochondrial amidoxime reducing components mARC-1 and mARC-2 (Gruenewald et al., 2008). These 35-kDa proteins represent a novel group of molybdenum proteins in eukaryotes as they form a molybdenum cofactor-dependent enzyme system consisting of three separate proteins (Havemeyer et al., 2006). Each mARC protein reduces N-hydroxylated compounds after reconstitution with the electron transport proteins cytochrome b(5) and b(5) reductase. In continuation of our drug metabolism investigations (Havemeyer et al., 2006; Gruenewald et al., 2008), we present data from reconstituted enzyme systems with recombinant human and native porcine enzymes showing the reduction of N-hydroxy-sulfonamides (sulfohydroxamic acids) to sulfonamides: the N-hydroxy-sulfonamide N-hydroxy-valdecoxib (N-hydroxy-4-[5-methyl-3-phenyl-4-isoxazolyl]-benzenesulfonamide) represents a novel cyclooxygenase (COX)-2 inhibitor and is therefore a drug candidate in the treatment of diseases associated with rheumatic inflammation, pain, and fever. It was synthesized as an analog of the known COX-2 inhibitor valdecoxib (4-[5-methyl-3-phenyl-4-isoxazolyl]-benzenesulfonamide) (Talley et al., 2000). N-Hydroxy-valdecoxib had low in vitro COX-2 activity but showed significant analgesic activity in vivo and a prolonged therapeutic effect compared with valdecoxib (Erdélyi et al., 2008). In this report, we demonstrate that N-hydroxy-valdecoxib is enzymatically reduced to its pharmacologically active metabolite valdecoxib. Thus, N-hydroxy-valdecoxib acts as prodrug that is activated by the molybdenum-containing enzyme mARC.

Non-methylene interrupted and hydroxy fatty acids in polar lipids of the alga Grateloupia turuturu over the four seasons.

PubMed

Kendel, Melha; Barnathan, Gilles; Fleurence, Joël; Rabesaotra, Vony; Wielgosz-Collin, Gaëtane

2013-05-01

Phospholipids (PL) and glycolipids (GL) FA in the edible Rhodophyta Grateloupia turuturu, from Brittany, France, were investigated over four seasons. The major lipid class was GL in all seasons (around 45 %). More than 80 FA occurred in polar lipids, with chains from C12 to C26, identified as methyl esters and N-acyl pyrrolidides by gas chromatography-mass spectrometry (GC-MS). PUFA occurred at up to 47.1 % (summer) in PL, and up to 43.6 % (summer) in GL. The major PUFA were 20:5n-3 (12.2 % in PL and 29.0 % in GL) and 20:4n-6 (25.6 % in PL and 10.4 % in GL). The unusual 18:3n-7 acid was identified in PL up to 2.2 %. Several minor unsaturated FA were identified in PL and are previously unreported in seaweeds, namely 14-tricosenoic, 15-tetracosenoic, 5,11-octadecadienoic and 5,9-nonadecadienoic. Also unprecedented in seaweeds, ten 2-hydroxy and three 3-hydroxy FA occurred mainly in PL, 13.9 % in spring with the 3-hydroxyhexadecanoic acid as the major one (8.1 % winter). Three n-9 monounsaturated 2-hydroxy FA occurred in PL. The 2-hydroxy-15-tetracosenoic acid was characterized as the dimethyl disulfide adduct of its methyl ester. The 2-hydroxy-16-pentacosenoic and 2-hydroxy-17-hexacosenoic acids were identified by comparison of mass spectra and GC mobilities with those of the 2-hydroxy-15-tetracosenoic acid, and of other homogeneous FA series. These rare n-9 monounsaturated 2-hydroxy FA are unprecedented in seaweeds.

Oxidation of C18 Hydroxy-Polyunsaturated Fatty Acids to Epoxide or Ketone by Catalase-Related Hemoproteins Activated with Iodosylbenzene.

PubMed

Teder, Tarvi; Boeglin, William E; Brash, Alan R

2017-07-01

Small catalase-related hemoproteins with a facility to react with fatty acid hydroperoxides were examined for their potential mono-oxygenase activity when activated using iodosylbenzene. The proteins tested were a Fusarium graminearum 41 kD catalase hemoprotein (Fg-cat, gene FGSG_02217), a Pseudomonas fluorescens Pfl01 catalase (37.5 kD, accession number WP_011333788.1), and a Mycobacterium avium ssp. paratuberculosis 33 kD catalase (gene MAP-2744c). 13-Hydroxy-octadecenoic acids (which are normally unreactive) were selected as substrates because these enzymes react specifically with the corresponding 13S-hydroperoxides (Pakhomova et al. 18:2559-2568, 5; Teder et al. 1862:706-715, 14). In the presence of iodosylbenzene Fg-cat converted 13S-hydroxy-fatty acids to two products: the 15,16-double bond of 13S-hydroxy α-linolenic acid was oxidized stereospecifically to the 15S,16R-cis-epoxide or the 13-hydroxyl was oxidized to the 13-ketone. Products were identified by UV, HPLC, LC-MS, NMR and by comparison with authentic standards prepared for this study. The Pfl01-cat displayed similar activity. MAP-2744c oxidized 13S-hydroxy-linoleic acid to the 13-ketone, and epoxidized the double bonds to form the 9,10-epoxy-13-hydroxy, 11,12-epoxy-13-hydroxy, and 9,10-epoxy-13-keto derivatives; equivalent transformations occurred with 9S-hydroxy-linoleic acid as substrate. In parallel incubations in the presence of iodosylbenzene, human catalase displayed no activity towards 13S-hydroxy-linoleic acid, as expected from the highly restricted access to its active site. The results indicated that with suitable transformation to Compound I, monooxygenase activity can be demonstrated by these catalase-related hemoproteins with tyrosine as the proximal heme ligand.

1,4-hydroxycarbonyl products of the OH radical initiated reactions of C5-C8 n-alkanes in the presence of NO.

PubMed

Reisen, Fabienne; Aschmann, Sara M; Atkinson, Roger; Arey, Janet

2005-06-15

Alkanes account for approximately 50% of nonmethane organic compounds present in urban atmospheres. Previous studies have shown that hydroxycarbonyls are important products ofthe OH radical initiated reactions of > or = C5 n-alkanes, but isomer-specific identifications and quantifications of these products have not been carried out. In this work, we have used solid-phase microextraction fibers precoated with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine for on-fiber derivatization of carbonyl-containing compounds with subsequent analyses by combined gas chromatography-mass spectrometry (GC-MS) and GC with flame ionization detection (GC-FID). GC-MS analyses showed the presence of the oximes of 5-hydroxy-2-pentanone and 4-hydroxypentanal from the n-pentane reaction; 5-hydroxy-2-hexanone, 6-hydroxy-3-hexanone, and 4-hydroxyhexanal from the n-hexane reaction; 5-hydroxy-2-heptanone, 6-hydroxy-3-heptanone, 1-hydroxy-4-heptanone, and 4-hydroxyheptanal from the n-heptane reaction; and 5-hydroxy-2-octanone, 6-hydroxy-3-octanone, 7-hydroxy-4-octanone, and 4-hydroxyoctanal from the n-octane reaction. The formation yields of these 1,4-hydroxycarbonyls were determined from GC-FID analyses. By use of the yields of 1,4-hydroxycarbonyls formed from n-hexane, n-heptane, and n-octane at 50% relative humidity (and those from n-pentane at both 5 and 50% relative humidity), then formation of 1,4-hydroxycarbonyls accounts for 54% of the reaction products from n-pentane, 57% from n-hexane, 51% from n-heptane, and 53% from n-octane. Combined with previously measured yields of carbonyls, alkyl nitrates, and hydroxyalkyl nitrates, we can now accountfor approximately 74-118% of the products formed from the n-pentane through n-octane reactions.

Process for the synthesis of unsaturated alcohols

DOEpatents

Maughon, Bob R.; Burdett, Kenneth A.; Lysenko, Zenon

2007-02-13

A process of preparing an unsaturated alcohol (olefin alcohol), such as, a homo-allylic mono-alcohol or homo-allylic polyol, involving protecting a hydroxy-substituted unsaturated fatty acid or fatty acid ester, such as methyl ricinoleate, derived from a seed oil, to form a hydroxy-protected unsaturated fatty acid or fatty acid ester; homo-metathesizing or cross-metathesizing the hydroxy-protected unsaturated fatty acid or fatty acid ester to produce a product mixture containing a hydroxy-protected unsaturated metathesis product; and deprotecting the hydroxy-protected unsaturated metathesis product under conditions sufficient to prepare the unsaturated alcohol. Preferably, methyl ricinoleate is converted by cross-metathesis or homo-metathesis into the homo-allylic mono-alcohol 1-decene-4-ol or the homo-allylic polyol 9-octadecene-7,12-diol, respectively.

Use of polyurethane foam and 3-hydroxy-7,8-benzo-1,2,3,4-tetrahydroquinoline for determination of nitrite by diffuse reflectance spectroscopy and colorimetry.

PubMed

Apyari, V V; Dmitrienko, S G; Ostrovskaya, V M; Anaev, E K; Zolotov, Y A

2008-07-01

Polyurethane foam (PUF) has been suggested as a solid polymeric reagent for determination of nitrite. The determination is based on the diazotization of end toluidine groups of PUF with nitrite in acidic medium followed by coupling of polymeric diazonium cation with 3-hydroxy-7,8-benzo-1,2,3,4-tetrahydroquinoline. The intensely colored polymeric azodye formed in this reaction can be used as a convenient analytic form for the determination of nitrite by diffuse reflectance spectroscopy (c (min) = 0.7 ng mL(-1)). The possibility of using a desktop scanner, digital camera, and computer data processing for the numerical evaluation of the color intensity of the polymeric azodye has been investigated. A scanner and digital camera can be used for determination of nitrite with the same sensitivity and reproducibility as with diffuse reflectance spectroscopy. The approach developed was applied for determination of nitrite in river water and human exhaled breath condensate.

Cr6+-containing phases in the system CaO-Al2O3-CrO42--H2O at 23 °C

NASA Astrophysics Data System (ADS)

Pöllmann, Herbert; Auer, Stephan

2012-01-01

Synthesis and investigation of lamellar calcium aluminium hydroxy salts was performed to study the incorporation of chromate ions in the interlayer of lamellar calcium aluminium hydroxy salts. Different AFm-phases (calcium aluminate hydrate with alumina, ferric oxide, mono-anion phase) containing chromate were synthesized. These AFm-phases belong to the group of layered double hydroxides (LDHs). 3CaO·Al2O3·CaCrO4·nH2O and C3A·1/2Ca(OH)2·1/2CaCrO4·12H2O were obtained as pure phases and their different distinct interlayer water contents and properties determined. Solid solution of chromate-containing phases and tetracalcium-aluminate-hydrate (TCAH) were studied. The uptake of chromate into TCAH from solutions was proven. Chromate contents in solution decrease to <0.2 mg/l.

Chiral lyotropic chromonic liquid crystals composed of disodium cromoglycate doped with water-soluble chiral additives.

PubMed

Shirai, Tatsuya; Shuai, Min; Nakamura, Keita; Yamaguchi, Akihiro; Naka, Yumiko; Sasaki, Takeo; Clark, Noel A; Le, Khoa V

2018-02-28

We investigated the pitches of cholesteric liquid crystals prepared by mixing disodium cromoglycate (DSCG) in water with 5 different water-soluble chiral additives. The measurements are based on the Grandjean-Cano wedge cell method. Overall, the twisting effect is weak, and the shortest pitch of 2.9 ± 0.2 μm is obtained using trans-4-hydroxy-l-proline, by which the cholesteric sample is iridescent at certain viewing angles. Freeze-fracture transmission electron microscopy (FFTEM) was also performed for the first time on both the nematic and cholesteric phases, revealing that stacked chromonic aggregates are very long, up to a few hundred nm, which explains why cholesteric chromonic liquid crystals hardly have pitches in the visible wavelength region.

Preservation of commonly applied fluorescent tracers in complex water samples

NASA Astrophysics Data System (ADS)

Cao, Viet; Schaffer, Mario; Jin, Yulan; Licha, Tobias

2017-06-01

Water sample preservation and pre-treatment are important steps for achieving accurate and reproductive results from tracer tests. However, this is particularly challenging for complex water mixtures prior to fluorescence analysis. In this study, the interference of iron and calcium precipitation with nine commonly applied conservative tracers, uranine, eosin, 1-naphthalene sulfonate, 1,5-naphthalene disulfonate, 2,6-naphthalene disulfonate, 4-amino-1-naphthalene sulfonate, 6-hydroxy-2-naphthalene sulfonate, 1,3,6-naphthalene trisulfonate, and 1,3,6,8-pyrene tetrasulfonate, was investigated in batch experiments. In general, the observed results are influenced by precipitates. A technique consisting of pH adjustment and centrifugation is described for preserving samples and avoiding the impact of these precipitates on the tracer test results.

Poly-3-hydroxy butyric acid interaction with the transgenic flax fibers: FT-IR and Raman spectra of the composite extracted from a GM flax

NASA Astrophysics Data System (ADS)

Wróbel-Kwiatkowska, Magdalena; Żuk, Magdalena; Szopa, Jan; Dymińska, Lucyna; Mączka, Mirosław; Hanuza, Jerzy

2009-07-01

The FT-IR and FT-Raman studies have been performed on commercial 3-hydroxy-butyric acid, commercial poly-3-hydroxy butyric acid as well as poly-3-hydroxy butyric acid (PHB) produced by bacteria. The data were compared to those obtained for poly-3-hydroxy butyric acid extracted from natural and genetically modified flax. Genetically modified flax was generated by expression of three bacterial genes coding for synthesis of poly-3-hydroxy butyric acid. Thus transgenic flaxes were enhanced with different amount of the PHB. The discussion of polymer structure and vibrational properties has been done in order to get insight into differences among these materials. The interaction between the cellulose of flax fibers and embedded poly-3-hydroxybutyric acid has been also discussed. The spectroscopic data provide evidences for structural changes in cellulose and in PHB when synthesized in fibers. Based on this data it is suggesting that cellulose and PHB interact by hydrogen and ester bonds.

Genotoxicity and cytotoxicity reduction of the polluted urban river after ecological restoration: a field-scale study of Jialu River in northern China.

PubMed

Sun, Jie; Zhang, Rui; Qin, Long; Zhu, Haixiao; Huang, Yu; Xue, Yingang; An, Shuqing; Xie, Xianchuan; Li, Aimin

2017-03-01

To further treat the reclaimed municipal wastewater and rehabilitate the aquatic ecosystem of polluted urban rivers, an 18.5-km field-scale ecological restoration project was constructed along Jialu River, a polluted urban river which receives only reclaimed municipal wastewater from Zhengzhou City without natural upland water dilution. This study investigated the potential efficiency of water quality improvement, as well as genotoxicity and cytotoxicity reduction along the ecological restoration project of this polluted urban river. Results showed that the chemical oxygen demand (COD) and ammonia nitrogen (NH 3 -N) of the reclaimed municipal effluent were reduced by more than 45 and 70%, respectively, meeting the Chinese surface water environmental quality standard level IV, while the total phosphorus and metal concentrations had no significant reduction along the restoration project, and Pb concentrations in all river water samples exceeded permissible limit in drinking water set by WHO (2006) and China (GB5749-2006). The in vitro SOS/umu assay showed 4-nitroquinoline-1-oxide equivalent (4-NQO-EQ) values of reclaimed municipal wastewater of 0.69 ± 0.05 μg/L in April and 0.68 ± 0.06 μg/L in December, respectively, indicating the presence of genotoxic compounds. The results of 8-hydroxy-2'-deoxyguanosine (8-OHdG) and hepatic cell apoptosis in zebrafish after a chorionic long-term (21 days) in vivo exposure also demonstrated that the reclaimed municipal wastewater caused significant DNA oxidative damage and cytotoxicity. After the ecological purification of 18.5-km field-scale restoration project, the genotoxicity assessed by in vitro assay was negligible, while the DNA oxidative damage and cytotoxicity in exposed fish were still significantly elevated. The mechanisms of DNA oxidative damage and cytotoxicity caused by the reclaimed municipal wastewater need further study.

40 CFR 721.10484 - Siloxanes and Silicones, Me vinyl, hydroxy-terminated, reaction products with...

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Siloxanes and Silicones, Me vinyl... Substances § 721.10484 Siloxanes and Silicones, Me vinyl, hydroxy-terminated, reaction products with...) The chemical substance identified as Siloxanes and Silicones, Me vinyl, hydroxy-terminated, reaction...

40 CFR 721.10484 - Siloxanes and Silicones, Me vinyl, hydroxy-terminated, reaction products with...

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Siloxanes and Silicones, Me vinyl... Substances § 721.10484 Siloxanes and Silicones, Me vinyl, hydroxy-terminated, reaction products with...) The chemical substance identified as Siloxanes and Silicones, Me vinyl, hydroxy-terminated, reaction...

75 FR 51382 - Alkyl Alcohol Alkoxylate Phosphate Derivatives; Exemption from the Requirement of a Tolerance

Federal Register 2010, 2011, 2012, 2013, 2014

2010-08-20

... branched, saturated and or unsaturated)-[omega]-hydroxypolyoxyethylene polymer with or without...), [alpha]-tridecyl- [omega] -hydroxy-, phosphate (9046-01-9); Poly(oxy-1 ,2-ethanediyl), [alpha]-dodecyl-[omega]-hydroxy-, phosphate (39464-66- 9); Poly(oxy-1 ,2-ethanediyl), [alpha]-hexadecyl-[omega]-hydroxy...

Distinctive EPR signals provide an understanding of the affinity of bis-(3-hydroxy-4-pyridinonato) copper(II) complexes for hydrophobic environments.

PubMed

Rangel, Maria; Leite, Andreia; Silva, André M N; Moniz, Tânia; Nunes, Ana; Amorim, M João; Queirós, Carla; Cunha-Silva, Luís; Gameiro, Paula; Burgess, John

2014-07-07

In this work we report the synthesis and characterization of a set of 3-hydroxy-4-pyridinone copper(ii) complexes with variable lipophilicity. EPR spectroscopy was used to characterize the structure of copper(ii) complexes in solution, and as a tool to gain insight into solvent interactions. EPR spectra of solutions of the [CuL2] complexes recorded in different solvents reveal the presence of two copper species whose ratio depends on the nature of the solvent. Investigation of EPR spectra in the pure solvents methanol, dimethylsulfoxide, dichloromethane and their 50% (v/v) mixtures with toluene allowed the characterization of two types of copper signals (gzz = 2.30 and gzz = 2.26) whose spin-Hamiltonian parameters are consistent with solvated and non-solvated square-planar copper(ii) complexes. Regarding the potential biological application of ligands and complexes and to get insight into the partition properties in water-membrane interfaces, EPR spectra were also obtained in water-saturated octanol, an aqueous solution buffered at pH = 7.4 and liposome suspensions, for three compounds representative of different hydro-lipophilic balances. Analysis of the EPR spectra obtained in liposomes allowed establishment of the location of the complexes in the water and lipid phases. In view of the results of this work we put forward the use of EPR spectroscopy to assess the affinity of copper(ii) complexes for a hydrophobic environment and also to obtain indirect information about the lipophilicity of the ligands and similar EPR silent complexes.

Towards Solvation of a Chiral Alpha-Hydroxy Ester: Broadband Chirp and Narrow Band Cavity Fouirier Transform Microwave Spectroscopy of Methyl Lactate-Water Clusters

NASA Astrophysics Data System (ADS)

Thomas, Javix; Sukhorukov, Oleksandr; Jaeger, Wolfgang; Xu, Yunjie

2013-06-01

Methyl lactate (ML), a chiral alpha-hydroxy ester, has attracted much attention as a prototype system in studies of chirality transfer,[1] solvation effects on chiroptical signatures,[2] and chirality recognition.[3] It has multiple functional groups which can serve both as a hydrogen donor and acceptor. By applying rotational spectroscopy and high level ab initio calculations, we examine the delicate competition between inter- and intramolecular hydrogen-bonding in the ML-water clusters. Broadband rotational spectra obtained with a chirp Fourier transform microwave (FTMW) spectrometer, reveal that the insertion conformations are the most favourable ones in the binary and ternary solvated complexes. In the insertion conformations, the water molecule(s) inserts itself (themselves) into the existing intramolecular hydrogen-bonded ring formed between the alcoholic hydroxyl group and the oxygen of the carbonyl group of ML. The final frequency measurements have been carried out using a cavity based FTMW instrument where internal rotation splittings due to the ester methyl group have also been detected. A number of insertion conformers with subtle structural differences for both the binary and ternary complexes have been identified theoretically. The interconversion dynamics of these conformers and the identification of the most favorable conformers will be discussed. 1. C. Merten, Y. Xu, Angew. Chem. Int. Ed., 2013, 52, 2073 -2076. 2. M. Losada, Y. Xu, Phys. Chem. Chem. Phys., 2007, 9, 3127-3135; Y. Liu, G. Yang, M. Losada, Y. Xu, J. Chem. Phys., 2010, 132, 234513/1-11. 3. A. Zehnacker, M. Suhm, Angew. Chem. Int. Ed. 2008, 47, 6970 - 6992.

Hepatic microsomal metabolism of BDE-47 and BDE-99 by lesser snow geese and Japanese quail.

PubMed

Krieger, Lisa K; Szeitz, András; Bandiera, Stelvio M

2017-09-01

In the present study, we investigated the oxidative biotransformation of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) and 2,2',4,4',5-pentabromodiphenyl ether (BDE-99) by liver microsomes from wild lesser snow geese (Chen caerulescens caerulescens) and domesticated Japanese quail (Coturnix japonica). Formation of hydroxy-metabolites was analyzed using an ultra-high performance liquid chromatography-tandem mass spectrometry-based method. Incubation of BDE-47 with avian liver microsomes produced sixteen hydroxy-metabolites, eight of which were identified using authentic standards. The major metabolites formed by liver microsomes from individual lesser snow geese were 4-hydroxy-2,2',3,4'-tetrabromodiphenyl ether (4-OH-BDE-42), 3-hydroxy-2,2',4,4'-tetrabromodiphenyl ether (3-OH-BDE-47), and 4'-hydroxy-2,2',4,5'-tetrabromodiphenyl ether (4'-OH-BDE-49). By comparison, 4-OH-BDE-42 and 4'-OH-BDE-49, but not 3-OH-BDE-47, were major metabolites of Japanese quail liver microsomes. Unidentified metabolites included monohydroxy- and dihydroxy-tetrabromodiphenyl ethers. Incubation of BDE-99 with avian liver microsomes produced seventeen hydroxy-metabolites, twelve of which were identified using authentic standards. The major metabolites formed by lesser snow goose liver microsomes were 2,4,5-tribromophenol, 3-OH-BDE-47, 4'-OH-BDE-49, 4-hydroxy-2,2',3,4',5-pentabromodiphenyl ether (4-OH-BDE-90), and 5'-hydroxy-2,2',4,4',5-pentabromodiphenyl ether (5'-OH-BDE-99). By comparison, the major metabolites produced by liver microsomes from Japanese quail included 6-hydroxy-2,2',4,4'-tetrabromodiphenyl ether (6-OH-BDE-47) and 2-hydroxy-2',3,4,4',5-pentabromodiphenyl ether (2-OH-BDE-123), but not 3-OH-BDE-47. Unidentified metabolites consisted of monohydroxy-pentabromodiphenyl ethers, monohydroxy-tetrabromodiphenyl ethers and dihydroxy-tetrabromodiphenyl ethers. Another difference between the two species was that formation rates of BDE-47 and BDE-99 metabolites were greater with liver microsomes from male than female Japanese quail, but a sex difference was not observed with lesser snow geese. Copyright © 2017 Elsevier Ltd. All rights reserved.

Biotransformation of nitroso aromatic compounds and 2-oxo acids to N-hydroxy-N-arylacylamides by thiamine-dependent enzymes in rat liver.

PubMed

Yoshioka, T; Uematsu, T

1998-07-01

The formation of N-hydroxy-N-arylacylamides from nitroso aromatic compounds and 2-oxo acids was investigated using rat liver subcellular fractions. Activities were found in both mitochondria and cytosol, except for activities for phenylpyruvate and glyoxylate; the former did not produce N-hydroxy-N-phenylphenylacetamide and the latter nonenzymatically produced N-hydroxy-N-phenylformamide with nitrosobenzene (NOB). The cytosolic activity of N-hydroxy-N-phenylglycolamide formation was indicated to be due to transketolase, which utilized hydroxypyruvate as a glycolic aldehyde donor to NOB. With mitochondria, 2-oxo acids (including hydroxypyruvate) served as substrates for the biotransformation of NOB to the corresponding N-hydroxy-N-phenylacylamides. The substrate preference was 2-oxobutyrate > pyruvate > 2-oxoisovalerate > 2-oxoisocaproate > 2-oxovalerate > 2-oxo-3-methylvalerate, judging from Vmax/half-saturating concentration for mitochondria values. The half-saturating concentrations for NOB were nearly constant. The mitochondrial activity was due to pyruvate dehydrogenase complex and branched-chain 2-oxo acid dehydrogenase complex (BCDHC). By using partially purified BCDHC, pyruvate and 2-oxobutyrate were found to be common substrates for both of the enzymes, and 2-oxoisovalerate was shown to be the most effective substrate for BCDHC. Analysis by the Taft equation indicated that the polar effects, rather than the steric effects, of the alkyl groups of 2-oxo acids are important for BCDHC-catalyzed formation of N-hydroxy-N-phenylacylamides. A positive Hammett constant obtained for the formation of N-hydroxy-N-arylisobutyramides indicates that an electron-withdrawing substituent makes the nitroso compounds susceptible to BCDHC-catalyzed biotransformation.

Hybrid MC/QC simulations of water-assisted proton transfer in nucleosides. Guanosine and its analog acyclovir.

PubMed

Markova, Nadezhda; Pejov, Ljupco; Stoyanova, Nina; Enchev, Venelin

2017-05-01

To provide an in-depth insight into the molecular basis of spontaneous tautomerism in DNA and RNA base pairs, a hybrid Monte Carlo (MC)-quantum chemical (QC) methodology is implemented to map two-dimensional potential energy surfaces along the reaction coordinates of solvent-assisted proton transfer processes in guanosine and its analog acyclovir in aqueous solution. The solvent effects were simulated by explicit inclusion of water molecules that model the relevant part of the first hydration shell around the solute. The position of these water molecules was estimated by carrying out a classical Metropolis Monte Carlo simulation of dilute water solutions of the guanosine (Gs) and acyclovir (ACV) and subsequently analyzing solute-solvent intermolecular interactions in the statistically-independent MC-generated configurations. The solvent-assisted proton transfer processes were further investigated using two different ab initio MP2 quantum chemical approaches. In the first one, potential energy surfaces of the 'bare' finite solute-solvent clusters containing Gs/ACV and four water molecules (MP2/6-31+G(d,p) level) were explored, while within the second approach, these clusters were embedded in 'bulk' solvent treated as polarizable continuum (C-PCM/MP2/6-31+G(d,p) level of theory). It was found that in the gas phase and in water solution, the most stable tautomer for guanosine and acyclovir is the 1H-2-amino-6-oxo form followed by the 2-amino-6-(sZ)-hydroxy form. The energy barriers of the water-assisted proton transfer reaction in guanosine and in acyclovir are found to be very similar - 11.74 kcal mol -1 for guanosine and 11.16 kcal mol -1 for acyclovir, and the respective rate constants (k = 1.5 × 10 1 s -1 , guanosine and k = 4.09 × 10 1 s -1 , acyclovir), are sufficiently large to generate the 2-amino-6-(sZ)-hydroxy tautomer. The analysis of the reaction profiles in both compounds shows that the proton transfer processes occur through the asynchronous concerted mechanism.

Antiprotozoal and antimicrobial compounds from the plant pathogen Septoria pistaciarum

USDA-ARS?s Scientific Manuscript database

Four new 1,4-dihydroxy-5-phenyl-2-pyridinone alkaloids, 17-hydroxy-N-(O-methyl)septoriamycin A (1), 17-acetoxy-N-(O-methyl)septoriamycin A (2), 13-(S)-hydroxy-N-(O-methyl)septoriamycin A (3) and 13-(R)-hydroxy-N-(O-methyl)septoriamycin A (4), together with the known compounds (+)-cercosporin (5), ...

Lipase catalyzed methanolysis of tri-(12-hydroxy stearoyl)-glycerol in organic solvents

USDA-ARS?s Scientific Manuscript database

Castor oil is the source of numerous products and is the only commercial source of the fatty acid ricinoleate, 12-hydroxy-oleate. Hydrogenated castor oil is similarly useful as the source of 12-hydroxy-stearic acid, best known as a component of lithium grease. Mono- and diacylglycerols derived from ...

Mass spectrometry of the lithium adducts of diacylglycerols containing hydroxy FA in castor oil and two normal FA

USDA-ARS?s Scientific Manuscript database

Castor oil can be used in industry. The molecular species of triacylglycerols containing hydroxy fatty acids (FA) in castor oil have been identified. We report here the identification of twelve diacylglycerols (DAG) containing hydroxy FA in castor oil using positive ion electrospray ionization mass ...

40 CFR 721.5280 - 2,7-Naphthalenedisulfonic acid, 4-amino-5-hydroxy-, coupled with diazotized 4-butylbenzenamine...

Code of Federal Regulations, 2011 CFR

2011-07-01

... reporting. (1) The chemical substance identified as 2,7-naphthalenedisulfonic acid, 4-amino-5-hydroxy... 40 Protection of Environment 31 2011-07-01 2011-07-01 false 2,7-Naphthalenedisulfonic acid, 4-amino-5-hydroxy-, coupled with diazotized 4-butylbenzenamine, diazotized 4,4â²-cyclohexylidenebis...

40 CFR 721.5280 - 2,7-Naphthalenedisulfonic acid, 4-amino-5-hydroxy-, coupled with diazotized 4-butylbenzenamine...

Code of Federal Regulations, 2010 CFR

2010-07-01

... reporting. (1) The chemical substance identified as 2,7-naphthalenedisulfonic acid, 4-amino-5-hydroxy... 40 Protection of Environment 30 2010-07-01 2010-07-01 false 2,7-Naphthalenedisulfonic acid, 4-amino-5-hydroxy-, coupled with diazotized 4-butylbenzenamine, diazotized 4,4â²-cyclohexylidenebis...

40 CFR 721.5280 - 2,7-Naphthalenedisulfonic acid, 4-amino-5-hydroxy-, coupled with diazotized 4-butylbenzenamine...

Code of Federal Regulations, 2014 CFR

2014-07-01

... reporting. (1) The chemical substance identified as 2,7-naphthalenedisulfonic acid, 4-amino-5-hydroxy...-amino-5-hydroxy-, coupled with diazotized 4-butylbenzenamine, diazotized 4,4â²-cyclohexylidenebis[benzenamine] and m-phenylenediamine, sodium salt. 721.5280 Section 721.5280 Protection of Environment...

Fate of pesticides added to the soil in northeast of Santa Fe Province, Argentina.

NASA Astrophysics Data System (ADS)

Vidal, Claudia; Aparicio, Virginia; De Geronimo, Eduardo; Costa, Jose Luis

2017-04-01

The use of pesticides in crop production has increased in the Northeast Santa Fe Province. This region has predominance of argiudolls, hapludalf and natracualf soils, with silt loam texture and 1.5 % of organic matter content. The main crops are sunflower, maize, cotton and sorghum. There are also extensive livestock production systems. The objective of this work was to study the presence and environmental fate of pesticides used in the agricultural systems of the Northeast Santa Fe Province. Different environmental matrices (soil, surface water and sediment) were sampled during the 2014-2015 cropping season in an area of about 180,000 ha of the "Arroyo el Rey" basin. Soil samples were collected at 0-5 cm depth in sunflower, sorghum, soybean and cotton cultivated fields. A total of 12 field plots were sampled, with glyphosate application and without glyphosate application. Water samples were collected at three locations: upper basin, medium basin, and lower basin in polypropylene bottles and stored at -20 °C until analysis. Glyphosate and AMPA was extracted from filtered water samples with a buffer solution (100 mM Na2B4O7•10H2O/100 mM K3PO4, pH=9) and derivatized with 9-fluorenylmethylchloroformate (1 mg mL-1 in acetonitrile). Afterwards samples were analyzed using liquid chromatography coupled to a tandem mass spectrometer (UPLC-MS/MS). A multi-residue determination of pesticides other than glyphosate and AMPA was used to detect pesticides in soil, water and sediment. Hydroxy atrazine (Atz-OH) (a degradation product of atrazine) and AMPA (a degradation product of glyphosate) were founded in the 100% of the soil samples. Below 70% of occurrence frequency were detected molecules such as Imidaclopyr (63%), Glyphosate (63%), Diethyltuolamide (61%), Atrazine (22%), Fluorocloridone (13%), Imazethapyr and Acetochlor To 1%). In water samples taken during 2014 the pesticides that exceeded the threshold of 0.1 μg.L-1 per molecule (European Economic Community) were AMPA (range: 0.7-0.3 μg.L-1), Atrazine (range : 0,201-0,1 μg.L-1), Atz-OH (range: 0.1598-0.135 μg.L-1). Also in some cases, the 0.5 μg.L-1 value (maximum for sum of EEC molecules) was exceeded, with ranges from 0.845 to 0.104 μg.L-1. In the water taken during 2015 the concentrations of AMPA and Glyphosate were greater than in 2014 (ranges: 6,6-0,5 μg.L-1 and 4.5-0,2 μg.L-1, respectively). This preliminary information indicates the need to study processes such as retention, degradation and vertical transport of pesticides to understand the mechanisms by which they are present in the different environmental matrices. In addition, it is important to reduce the input of pesticides added to the environment to produce grains and fibers in this region.

Quantitation of immunoadsorbed flavoprotein oxidases by luminol-mediated chemiluminescence.

PubMed

Hinkkanen, A; Maly, F E; Decker, K

1983-04-01

The detection of the flavoenzymes 6-hydroxy-L-nicotine oxidase and 6-hydroxy-D-nicotine oxidase at the sub-femtomol level was achieved by coupling the reaction of the immunoadsorbed proteins to the peroxidase-catalysed oxidation of luminol. The H2O2-producing oxidases retained their full activity when bound to the respective immobilized antibodies. This fact allowed the concentration of the enzymes from very dilute solutions and the quantitative assay of their activities in the microU range. Due to strict stereoselectivity and the absence of immunological cross-reactivity, the two flavoproteins could be determined in the same solution. This method was used to measure the 6-hydroxy-D-nicotine oxidase and 6-hydroxy-L-nicotine oxidase activities in Escherichia coli RR1 and different Arthrobacter strains cultured under non-inducing conditions. The same activity ratio of 6-hydroxy-L-nicotine oxidase/6-hydroxy-D-nicotine oxidase as in D L-nicotine-induced cells of A. oxidans was observed in non-induced wild type and in riboflavin-requiring (rf-) mutant cells of this aerob.

Fluorometric detection of nitroaromatics by fluorescent lead complexes: A spectroscopic assessment of detection mechanism

NASA Astrophysics Data System (ADS)

Chattopadhyay, Tanmay; Chatterjee, Sourav; Majumder, Ishani; Ghosh, Soumen; Yoon, Sangee; Sim, Eunji

2018-04-01

Three Schiff base ligands such as 2-[(2-Hydroxy-3-methoxy-benzylidene)-amino]-2-hydroxymethyl-propane-1,3-diol (HL1), 2-[(2-Hydroxy-benzylidene)-amino]-2-hydroxymethyl-propane-1,3-diol (HL2), 2-[(3,5-Dichloro-2-hydroxy-benzylidene)-amino]-2-hydroxymethyl-propane-1,3-diol (HL3) have been synthesized by condensation of aldehydes (such as 3,5-Dichloro-2-hydroxy benzaldehyde, 2-Hydroxy-benzaldehyde, and 2-Hydroxy-3-methoxy-benzaldehyde) with Tris-(hydroxymethyl)amino methane and characterized by IR, UV-vis and 1H NMR spectroscopy. Then all these three ligands have been used to prepare Pb(II) complexes by reaction with lead(II) acetate tri-hydrate in methanol. In view of analytical and spectral (IR, UV-vis and Mass) studies, it has been concluded that, except HL2, other two ligands form 1:1 metal complexes (1 and 3) with lead. Between two complexes, complex 3 is highly fluorescent and this property has been used to identify the pollutant nitroaromatics. Finally, the quenching mechanism has been established by means of spectroscopic investigation.

Dehalogenation of Chlorinated Hydroxybiphenyls by Fungal Laccase

PubMed Central

Schultz, Asgard; Jonas, Ulrike; Hammer, Elke; Schauer, Frieder

2001-01-01

We have investigated the transformation of chlorinated hydroxybiphenyls by laccase produced by Pycnoporus cinnabarinus. The compounds used were transformed to sparingly water-soluble colored precipitates which were identified by gas chromatography-mass spectrometry as oligomerization products of the chlorinated hydroxybiphenyls. During oligomerization of 2-hydroxy-5-chlorobiphenyl and 3-chloro-4-hydroxybiphenyl, dechlorinated C—C-linked dimers were formed, demonstrating the dehalogenation ability of laccase. In addition to these nonhalogenated dimers, both monohalogenated and dihalogenated dimers were identified. PMID:11526052

Pyrene-nucleobase conjugates: synthesis, oligonucleotide binding and confocal bioimaging studies.

PubMed

Jabłoński, Artur; Fritz, Yannic; Wagenknecht, Hans-Achim; Czerwieniec, Rafał; Bernaś, Tytus; Trzybiński, Damian; Woźniak, Krzysztof; Kowalski, Konrad

2017-01-01

Fluorescent pyrene-linker-nucleobase (nucleobase = thymine, adenine) conjugates with carbonyl and hydroxy functionalities in the linker were synthesized and characterized. X-ray single-crystal structure analysis performed for the pyrene-C(O)CH 2 CH 2 -thymine ( 2 ) conjugate reveals dimers of molecules 2 stabilized by hydrogen bonds between the thymine moieties. The photochemical characterization showed structure-dependent fluorescence properties of the investigated compounds. The conjugates bearing a carbonyl function represent weak emitters as compared to compounds with a hydroxy function in the linker. The self-assembly properties of pyrene nucleobases were investigated in respect to their binding to single and double strand oligonucleotides in water and in buffer solution. In respect to the complementary oligothymidine T 10 template in water, compounds 3 and 5 both show a self-assembling behavior according to canonical base-base pairing. However, in buffer solution, derivative 5 was much more effective than 3 in binding to the T 10 template. Furthermore the adenine derivative 5 binds to the double-stranded (dA) 10 -T 10 template with a self-assembly ratio of 112%. Such a high value of a self-assembly ratio can be rationalized by a triple-helix-like binding, intercalation, or a mixture of both. Remarkably, compound 5 also shows dual staining pattern in living HeLa cells. Confocal microscopy confirmed that 5 predominantly stains mitochondria but it also accumulates in the nucleoli of the cells.

Field evaluation of 3-hydroxy-2-hexanone and ethanol as attractants for the cerambycid beetle pest of vineyards, Xylotrechus arvicola.

PubMed

Rodríguez-González, Álvaro; Sánchez-Maíllo, Esteban; Peláez, Horacio J; González-Núñez, Manuel; Hall, David R; Casquero, Pedro A

2017-08-01

The beetle Xylotrechus arvicola (Coleoptera: Cerambycidae) is a serious pest of vineyards in the Iberian Peninsula. In previous work, the male beetles, but not females, were shown to produce (R)-3-hydroxy-2-hexanone, and female beetles were attracted to this compound in a laboratory bioassay. In this study, release rates of 3-hydroxy-2-hexanone from different dispensers were measured in the laboratory, and the attractiveness of these to X. arvicola adults was determined in trapping tests in three traditional wine-growing regions in Spain. As a result of laboratory experiments, for field experiments 3-hydroxy-2-hexanone was formulated as 100 μL in a polyethylene sachet (50 mm × 50 mm × 250 µm), and ethanol was formulated as 1 mL in a polyethylene press-seal bag (76 mm × 57 mm ×50 µm). Field catches were similar at all three study sites. Catches in traps baited with 3-hydroxy-2-hexanone alone were not significantly different from those in unbaited control traps, but catches in traps baited with 3-hydroxy-2-hexanone and ethanol in separate sachets, with 3-hydroxy-2-hexanone and ethanol in the same sachet or with ethanol alone were significantly greater than those in control traps. These results confirm that the beetles are attracted to ethanol, and the addition of 3-hydroxy-2-hexanone does not seem to make any difference. Attraction of females for the male-produced compound (R)-3-hydroxy-2-hexanone has been observed in laboratory but not in field experiments. Traps baited with ethanol are highly attractive to both sexes of adults of X. arvicola, and these can be used for improved monitoring of the adult emergence and for population control by mass trapping. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Gestational exposure to inorganic arsenic (iAs3+) alters glutamate disposition in the mouse hippocampus and ionotropic glutamate receptor expression leading to memory impairment.

PubMed

Nelson-Mora, Janikua; Escobar, Martha L; Rodríguez-Durán, Luis; Massieu, Lourdes; Montiel, Teresa; Rodríguez, Verónica M; Hernández-Mercado, Karina; Gonsebatt, María E

2018-03-01

Early life exposure to environmental pollutants and toxic chemicals has been linked to learning and behavioral alterations in children. iAs exposure is associated with different types neurological disorders such as memory and learning impairment. iAs is methylated in the brain by the arsenic III-methyltransferase in a process that requires glutathione (GSH). The xCT-antiporter cell membrane transporter participates in the influx of cystine for GSH synthesis in exchange for glutamate in a 1:1 ratio. In CD-1 mice gestationally exposed to 20 ppm of sodium arsenite in drinking water, we have previously observed up-regulation of xCT in the male mouse hippocampus which caused glutamatergic synapse alterations affecting learning and memory processes. Here, we used the same gestational iAs exposure model to investigate whether the up-regulation of xCT and down-regulation of GLT-1 transporters were associated with higher levels of extracellular glutamate and changes in the expression of the α-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid (AMPA) glutamate receptor, responsible for excitatory fast synaptic transmission. The induction of LTP in the perforant-dentate gyrus pathway (PP-DG) of the hippocampus was also studied, as well as learning and memory formation using the water maze test. Changes in GSH levels were also tested in the hippocampus of animals exposed to iAs. Results showed increased GSH synthesis (p < 0.05), associated with significantly higher extracellular glutamate levels in iAs exposed mice. Exposure was also significantly associated with AMPA subunits down-regulation, deficient LTP induction, and lower excitability of the PP-DG pathway. In addition, animals showed deficient learning and memory in the Morris Water Maze test.

A novel pyrimidine derivative as a fluorescent chemosensor for highly selective detection of aluminum (III) in aqueous media.

PubMed

Suryawanshi, Vishwas D; Gore, Anil H; Dongare, Pravin R; Anbhule, Prashant V; Patil, Shivajirao R; Kolekar, Govind B

2013-10-01

An efficient fluorescent chemosensor Al(3+) receptor based on pyrimidine derivative,2-amino-6-hydroxy-4-(4-N,N-dimethylaminophenyl)-pyrimidine-5-carbonitrile (DMAB), has been synthesized by three-component condensation of aromatic aldehyde, ethyl cyanoacetate and guanidine hydrochloride in ethanol under alkaline medium. High selectivity and sensitivity of DMAB towards Aluminum ion (Al(3+)) in water: ethanol and acetate buffer at pH 4.0 makes it suitable to detect Al(3+) with steady-state UV-vis and fluorescence spectroscopy. Method shows good selectivity towards Al(3+) over other coexisting metal ions tested, viz. Fe(2+), Ni(2+), Cu(2+), Co(2+), Pb(2+), Sb(3+), Na(+), Ca(2+), Mg(2+), Zn(2+), Hg(2+), Ba(2+), Cd(2+) and K(+). A good linearity between the Stern-Volmer plots of F0/F versus concentration of Al(3+) was observed over the range from 10 to 60 μg mL(-1) with correlation coefficient of 0.991. The accuracy and reliability of the method were further confirmed by recovery studies via standard addition method with percent recoveries in the range of 101.03-103.44% and lowest detection limit (LOD=7.35 μg mL(-1)) for Al(3+) was established. This method may offer a new cost-effective, rapid, and simple key to the inspection of Al(3+) ions in water samples in the presence of a complex matrix and can be capable of evaluating the exceeding standard of Al(3+) in environmental water samples. The probable mechanism for fluorescence quenching was also discussed. Copyright © 2013 Elsevier B.V. All rights reserved.

Novel enaminones as non-cytotoxic compounds with mild antibacterial activity: Synthesis and structure-activity correlations

NASA Astrophysics Data System (ADS)

Cindrić, Marina; Rubčić, Mirta; Hrenar, Tomica; Pisk, Jana; Cvijanović, Danijela; Lovrić, Jasna; Vrdoljak, Višnja

2018-02-01

Six non-symmetric enaminones 4-[(2-hydroxy-5-methylphenyl)amino]pent-3-en-2-one (H2L1), 4-[(2-hydroxy-4-methylphenyl)amino]pent-3-en-2-one (H2L2), 4-[(4-hydroxy-2-methylphenyl)amino)]pent-3-en-2-one (H2L3), 3-[(2-hydroxy-5-methylphenyl)amino]-1-phenylbut-2-en-1-one (H2L4), 3-[(2-hydroxy-4-methylphenyl)amino]-1-phenylbut-2-en-1-one (H2L5) and 3-[(4-hydroxy-2-methylphenyl)amino]-1-phenylbut-2-en-1-one (H2L6) have been prepared by solution based method. The enaminones were characterized by elemental and DSC analysis, NMR and IR spectroscopy. Crystal and molecular structures of H2L1, H2L2, H2L4 and H2L6 were determined via single crystal X-ray analysis. The prepared enaminones were screened against THP-1 and HepG2 cells, and Staphylococcus aureus, Enterococcus faecalis, Escherichia coli and Moraxella catarrhalis bacteria to assess their cytotoxic and antibacterial activity, respectively. All compounds proved to be non-cytotoxic and showed mild or no antibacterial activity. Quantum mechanical calculations suggest that the presence of hydroxy group in ortho position, combined with the methyl group on the same aromatic ring, has a significant impact on the biological activities.

Binary ferrihydrite catalysts

DOEpatents

Huffman, Gerald P.; Zhao, Jianmin; Feng, Zhen

1996-01-01

A method of preparing a catalyst precursor comprises dissolving an iron salt and a salt of an oxoanion forming agent, in water so that a solution of the iron salt and oxoanion forming agent salt has a ratio of oxoanion/Fe of between 0.0001:1 to 0.5:1. Next is increasing the pH of the solution to 10 by adding a strong base followed by collecting of precipitate having a binary ferrihydrite structure. A binary ferrihydrite catalyst precursor is also prepared by dissolving an iron salt in water. The solution is brought to a pH of substantially 10 to obtain ferrihydrite precipitate. The precipitate is then filtered and washed with distilled water and subsequently admixed with a hydroxy carboxylic acid solution. The admixture is mixed/agitated and the binary ferrihydrite precipitate is then filtered and recovered.

40 CFR 721.10483 - Siloxanes and Silicones, di-Me, Me vinyl, hydroxy-terminated, reaction products with...

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Siloxanes and Silicones, di-Me, Me... Substances § 721.10483 Siloxanes and Silicones, di-Me, Me vinyl, hydroxy-terminated, reaction products with...) The chemical substance identified as Siloxanes and Silicones, di-Me, Me vinyl, hydroxy-terminated...

40 CFR 721.10483 - Siloxanes and Silicones, di-Me, Me vinyl, hydroxy-terminated, reaction products with...

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Siloxanes and Silicones, di-Me, Me... Substances § 721.10483 Siloxanes and Silicones, di-Me, Me vinyl, hydroxy-terminated, reaction products with...) The chemical substance identified as Siloxanes and Silicones, di-Me, Me vinyl, hydroxy-terminated...

Rapid Stabilization/Polymerization of Wet Clay Soils; Literature Review

DTIC Science & Technology

2009-01-15

known as lime, and potassium hydroxide (KOH) were found to increase shear strength, and decrease expansive properties of Diablo clay. The lime...Publication Date: 1991 Purpose of Stabilizer: Control High Swell Potential Stabilizers Tested: Lime, potassium phosphate, potassium chloride...Date: 1988 Purpose of Stabilizer: Stabilizer Stabilizers Tested: Hydroxy-aluminum, hydroxy-aluminum and potassium chloride, hydroxy-aluminum

Characterization, Function, and Transcriptional Profiling Analysis of 3-Hydroxy-3-methylglutaryl-CoA Synthase Gene (GbHMGS1) towards Stresses and Exogenous Hormone Treatments in Ginkgo biloba.

PubMed

Meng, Xiangxiang; Song, Qiling; Ye, Jiabao; Wang, Lanlan; Xu, Feng

2017-10-12

3-Hydroxy-3-methylglutaryl-CoA synthase (HMGS) is one of the rate-limiting enzymes in the mevalonate pathway as it catalyzes the condensation of acetoacetyl-CoA to form 3-hydroxy-3-methylglutaryl-CoA. In this study, A HMGS gene (designated as GbHMGS1 ) was cloned from Ginkgo biloba for the first time. GbHMGS1 contained a 1422-bp open-reading frame encoding 474 amino acids. Comparative and bioinformatics analysis revealed that GbHMGS1 was extensively homologous to HMGSs from other plant species. Phylogenetic analysis indicated that the GbHMGS1 belonged to the plant HMGS superfamily, sharing a common evolutionary ancestor with other HMGSs, and had a further relationship with other gymnosperm species. The yeast complement assay of GbHMGS1 in HMGS -deficient Saccharomyces cerevisiae strain YSC6274 demonstrated that GbHMGS1 gene encodes a functional HMGS enzyme. The recombinant protein of GbHMGS1 was successfully expressed in E. coli . The in vitro enzyme activity assay showed that the k cat and K m values of GbHMGS1 were 195.4 min -1 and 689 μM, respectively. GbHMGS1 was constitutively expressed in all tested tissues, including the roots, stems, leaves, female flowers, male flowers and fruits. The transcript accumulation for GbHMGS1 was highest in the leaves. Expression profiling analyses revealed that GbHMGS1 expression was induced by abiotic stresses (ultraviolet B and cold) and hormone treatments (salicylic acid, methyl jasmonate, and ethephon) in G. biloba , indicating that GbHMGS1 gene was involved in the response to environmental stresses and plant hormones.

Multimolecular tracers of terrestrial carbon transfer across the pan-Arctic: 14C characteristics of sedimentary carbon components and their environmental controls

NASA Astrophysics Data System (ADS)

Feng, Xiaojuan; Gustafsson, Örjan; Holmes, R. Max; Vonk, Jorien E.; van Dongen, Bart E.; Semiletov, Igor P.; Dudarev, Oleg V.; Yunker, Mark B.; Macdonald, Robie W.; Wacker, Lukas; Montluçon, Daniel B.; Eglinton, Timothy I.

2015-11-01

Distinguishing the sources, ages, and fate of various terrestrial organic carbon (OC) pools mobilized from heterogeneous Arctic landscapes is key to assessing climatic impacts on the fluvial release of carbon from permafrost. Through molecular 14C measurements, including novel analyses of suberin- and/or cutin-derived diacids (DAs) and hydroxy fatty acids (FAs), we compared the radiocarbon characteristics of a comprehensive suite of terrestrial markers (including plant wax lipids, cutin, suberin, lignin, and hydroxy phenols) in the sedimentary particles from nine major arctic and subarctic rivers in order to establish a benchmark assessment of the mobilization patterns of terrestrial OC pools across the pan-Arctic. Terrestrial lipids, including suberin-derived longer-chain DAs (C24,26,28), plant wax FAs (C24,26,28), and n-alkanes (C27,29,31), incorporated significant inputs of aged carbon, presumably from deeper soil horizons. Mobilization and translocation of these "old" terrestrial carbon components was dependent on nonlinear processes associated with permafrost distributions. By contrast, shorter-chain (C16,18) DAs and lignin phenols (as well as hydroxy phenols in rivers outside eastern Eurasian Arctic) were much more enriched in 14C, suggesting incorporation of relatively young carbon supplied by runoff processes from recent vegetation debris and surface layers. Furthermore, the radiocarbon content of terrestrial markers is heavily influenced by specific OC sources and degradation status. Overall, multitracer molecular 14C analysis sheds new light on the mobilization of terrestrial OC from arctic watersheds. Our findings of distinct ages for various terrestrial carbon components may aid in elucidating fate of different terrestrial OC pools in the face of increasing arctic permafrost thaw.

Regioselective Acylation of Diols and Triols: The Cyanide Effect.

PubMed

Peng, Peng; Linseis, Michael; Winter, Rainer F; Schmidt, Richard R

2016-05-11

Central topics of carbohydrate chemistry embrace structural modifications of carbohydrates and oligosaccharide synthesis. Both require regioselectively protected building blocks that are mainly available via indirect multistep procedures. Hence, direct protection methods targeting a specific hydroxy group are demanded. Dual hydrogen bonding will eventually differentiate between differently positioned hydroxy groups. As cyanide is capable of various kinds of hydrogen bonding and as it is a quite strong sterically nondemanding base, regioselective O-acylations should be possible at low temperatures even at sterically congested positions, thus permitting formation and also isolation of the kinetic product. Indeed, 1,2-cis-diols, having an equatorial and an axial hydroxy group, benzoyl cyanide or acetyl cyanide as an acylating agent, and DMAP as a catalyst yield at -78 °C the thermodynamically unfavorable axial O-acylation product; acyl migration is not observed under these conditions. This phenomenon was substantiated with 3,4-O-unproteced galacto- and fucopyranosides and 2,3-O-unprotected mannopyranosides. Even for 3,4,6-O-unprotected galactopyranosides as triols, axial 4-O-acylation is appreciably faster than O-acylation of the primary 6-hydroxy group. The importance of hydrogen bonding for this unusual regioselectivity could be confirmed by NMR studies and DFT calculations, which indicate favorable hydrogen bonding of cyanide to the most acidic axial hydroxy group supported by hydrogen bonding of the equatorial hydroxy group to the axial oxygen. Thus, the "cyanide effect" is due to dual hydrogen bonding of the axial hydroxy group which enhances the nucleophilicity of the respective oxygen atom, permitting an even faster reaction for diols than for mono-ols. In contrast, fluoride as a counterion favors dual hydrogen bonding to both hydroxy groups leading to equatorial O-acylation.

Identification of light-independent inhibition of human immunodeficiency virus-1 infection through bioguided fractionation of Hypericum perforatum

PubMed Central

Maury, Wendy; Price, Jason P; Brindley, Melinda A; Oh, ChoonSeok; Neighbors, Jeffrey D; Wiemer, David F; Wills, Nickolas; Carpenter, Susan; Hauck, Cathy; Murphy, Patricia; Widrlechner, Mark P; Delate, Kathleen; Kumar, Ganesh; Kraus, George A; Rizshsky, Ludmila; Nikolau, Basil

2009-01-01

Background Light-dependent activities against enveloped viruses in St. John's Wort (Hypericum perforatum) extracts have been extensively studied. In contrast, light-independent antiviral activity from this species has not been investigated. Results Here, we identify the light-independent inhibition of human immunodeficiency virus-1 (HIV-1) by highly purified fractions of chloroform extracts of H. perforatum. Both cytotoxicity and antiviral activity were evident in initial chloroform extracts, but bioassay-guided fractionation produced fractions that inhibited HIV-1 with little to no cytotoxicity. Separation of these two biological activities has not been reported for constituents responsible for the light-dependent antiviral activities. Antiviral activity was associated with more polar subfractions. GC/MS analysis of the two most active subfractions identified 3-hydroxy lauric acid as predominant in one fraction and 3-hydroxy myristic acid as predominant in the other. Synthetic 3-hydroxy lauric acid inhibited HIV infectivity without cytotoxicity, suggesting that this modified fatty acid is likely responsible for observed antiviral activity present in that fraction. As production of 3-hydroxy fatty acids by plants remains controversial, H. perforatum seedlings were grown sterilely and evaluated for presence of 3-hydroxy fatty acids by GC/MS. Small quantities of some 3-hydroxy fatty acids were detected in sterile plants, whereas different 3-hydroxy fatty acids were detected in our chloroform extracts or field-grown material. Conclusion Through bioguided fractionation, we have identified that 3-hydroxy lauric acid found in field grown Hypericum perforatum has anti-HIV activity. This novel anti-HIV activity can be potentially developed into inexpensive therapies, expanding the current arsenal of anti-retroviral agents. PMID:19594941

Cyp7b, a novel brain cytochrome P450, catalyzes the synthesis of neurosteroids 7α-hydroxy dehydroepiandrosterone and 7α-hydroxy pregnenolone

PubMed Central

Rose, Ken A.; Stapleton, Genevieve; Dott, Karin; Kieny, Marie Paule; Best, Ruth; Schwarz, Margrit; Russell, David W.; Björkhem, Ingemar; Seckl, Jonathan; Lathe, Richard

1997-01-01

Steroids produced locally in brain (neurosteroids), including dehydroepiandrosterone (DHEA), influence cognition and behavior. We previously described a novel cytochrome P450, Cyp7b, strongly expressed in rat and mouse brain, particularly in hippocampus. Cyp7b is most similar to steroidogenic P450s and potentially could play a role in neurosteroid metabolism. To examine the catalytic activity of the enzyme mouse Cyp7b cDNA was introduced into a vaccinia virus vector. Extracts from cells infected with the recombinant showed NADPH-dependent conversion of DHEA (Km, 13.6 μM) and pregnenolone (Km, 4.0 μM) to slower migrating forms on thin layer chromatography. The expressed enzyme was less active against 25-hydroxycholesterol, 17β-estradiol and 5α-androstane-3β,17β-diol, with low to undetectable activity against progesterone, corticosterone, and testosterone. On gas chromatography and mass spectrometry of the Cyp7b metabolite of DHEA the retention time and fragmentation patterns were identical to those obtained with authentic 7α-hydroxy DHEA. The reaction product also comigrated on thin layer chromatography with 7α-hydroxy DHEA but not with 7β-hydroxy DHEA; when [7α-3H]pregnenolone was incubated with Cyp7b extracts the extent of release of radioactivity into the medium suggested that hydroxylation was preferentially at the 7α position. Brain extracts also efficiently liberated tritium from [7α-3H]pregnenolone and converted DHEA to a product with a chromatographic mobility indistinguishable from 7α-hydroxy DHEA. We conclude that Cyp7b is a 7α-hydroxylase participating in the synthesis, in brain, of neurosteroids 7α-hydroxy DHEA, and 7α-hydroxy pregnenolone. PMID:9144166

Hydroxy fatty acids in marine aerosols as microbial tracers: 4-year study on β- and ω-hydroxy fatty acids from remote Chichijima Island in the western North Pacific

NASA Astrophysics Data System (ADS)

Tyagi, Poonam; Ishimura, Yutaka; Kawamura, Kimitaka

2015-08-01

To better understand the long-range atmospheric transport of microbial aerosols from Asia to the western North Pacific, marine aerosols were collected from Chichijima Island (27°04‧N; 142°13‧E) on a biweekly basis during 1990-1993. These samples were investigated for β- and ω-hydroxy fatty acids (FAs) as terrestrial biomarkers of Gram-negative bacteria (GNB) and higher plants, respectively. The average concentrations of β-hydroxy (C8-C31) and ω-hydroxy (C11-C28) FAs show pronounced seasonal variability with maxima in spring (300 ± 70 pg m-3) and winter (650 ± 330 pg m-3), respectively. Airmass back trajectories clearly indicate the continental outflow from Asia during winter to spring, whereas maritime airmasses dominate in summer to autumn over Chichijima. It is noteworthy that atmospheric abundances of β-hydroxy FAs and, thus, the estimated mass concentration of GNB have not been significantly varied between polluted (continental) and pristine (oceanic) airmasses during the study period. However, the relative source strength observed from cluster analysis of β-hydroxy FAs in the polluted continental airmassess vary significantly among seasons (winter: 98%, spring: 63%, summer; 11%, autumn: 26%). In addition, there were distinguishable differences between polluted continental and pristine maritime airmasses with regard to C-number predominance. The even C-number predominance of β- and ω-hydroxy FAs (∼80 and 98% of total mass concentration, respectively) in marine aerosols could be due to their significant contribution from GNB, terrestrial plants and soil microorganisms. These results have implications towards assessing the atmospheric transport of bacterial and plant lipids in the continental outflow over the open ocean.

40 CFR 721.3320 - Ethanol, 2-amino-, com-pound with N-hydroxy-N-nitro-soben-zena-mine (1:1).

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Ethanol, 2-amino-, com-pound with N... Significant New Uses for Specific Chemical Substances § 721.3320 Ethanol, 2-amino-, com-pound with N-hydroxy-N...) The chemical substance identified as ethanol, 2-amino-, compound with N-hydroxy-N-nitrosobenzenamine...

40 CFR 721.3320 - Ethanol, 2-amino-, com-pound with N-hydroxy-N-nitro-soben-zena-mine (1:1).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Ethanol, 2-amino-, com-pound with N... Significant New Uses for Specific Chemical Substances § 721.3320 Ethanol, 2-amino-, com-pound with N-hydroxy-N...) The chemical substance identified as ethanol, 2-amino-, compound with N-hydroxy-N-nitrosobenzenamine...

40 CFR 721.3320 - Ethanol, 2-amino-, com-pound with N-hydroxy-N-nitro-soben-zena-mine (1:1).

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Ethanol, 2-amino-, com-pound with N... Significant New Uses for Specific Chemical Substances § 721.3320 Ethanol, 2-amino-, com-pound with N-hydroxy-N...) The chemical substance identified as ethanol, 2-amino-, compound with N-hydroxy-N-nitrosobenzenamine...

40 CFR 721.3320 - Ethanol, 2-amino-, com-pound with N-hydroxy-N-nitro-soben-zena-mine (1:1).

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Ethanol, 2-amino-, com-pound with N... Significant New Uses for Specific Chemical Substances § 721.3320 Ethanol, 2-amino-, com-pound with N-hydroxy-N...) The chemical substance identified as ethanol, 2-amino-, compound with N-hydroxy-N-nitrosobenzenamine...

40 CFR 721.3320 - Ethanol, 2-amino-, com-pound with N-hydroxy-N-nitro-soben-zena-mine (1:1).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Ethanol, 2-amino-, com-pound with N... Significant New Uses for Specific Chemical Substances § 721.3320 Ethanol, 2-amino-, com-pound with N-hydroxy-N...) The chemical substance identified as ethanol, 2-amino-, compound with N-hydroxy-N-nitrosobenzenamine...

Identification of hydroxy fatty acid and triacylglycerol metabolism-related genes in lesquerella through seed transcriptome analysis

USDA-ARS?s Scientific Manuscript database

Background: Castor oil is the only commercial source of hydroxy fatty acid which has industrial value. The production of castor oil is hampered by the presence of the toxin ricin in its seed. Lesquerella seed also accumulates hydroxy fatty acid and is free of ricin, thus it is being developed as a n...

40 CFR 721.10283 - Poly[oxy(methyl-1,2-ethanediyl)], .alpha.-sulfo-.omega.-hydroxy-, C12-13-branched and linear...

Code of Federal Regulations, 2013 CFR

2013-07-01

...)], .alpha.-sulfo-.omega.-hydroxy-, C12-13-branched and linear alkyl ethers, sodium salts. 721.10283 Section... Substances § 721.10283 Poly[oxy(methyl-1,2-ethanediyl)], .alpha.-sulfo-.omega.-hydroxy-, C12-13-branched and.... (1) The chemical substance identified as poly[oxy(methyl-1,2-ethanediyl)], .alpha.-sulfo-.omega...

40 CFR 721.10284 - Poly[oxy(methyl-1,2-ethanediyl)], .alpha.-sulfo-.omega.-hydroxy-, C14-15-branched and linear...

Code of Federal Regulations, 2012 CFR

2012-07-01

...)], .alpha.-sulfo-.omega.-hydroxy-, C14-15-branched and linear alkyl ethers, sodium salts. 721.10284 Section... Substances § 721.10284 Poly[oxy(methyl-1,2-ethanediyl)], .alpha.-sulfo-.omega.-hydroxy-, C14-15-branched and.... (1) The chemical substance identified as poly[oxy(methyl-1,2-ethanediyl)], .alpha.-sulfo-.omega...

40 CFR 721.10284 - Poly[oxy(methyl-1,2-ethanediyl)], .alpha.-sulfo-.omega.-hydroxy-, C14-15-branched and linear...

Code of Federal Regulations, 2014 CFR

2014-07-01

...)], .alpha.-sulfo-.omega.-hydroxy-, C14-15-branched and linear alkyl ethers, sodium salts. 721.10284 Section... Substances § 721.10284 Poly[oxy(methyl-1,2-ethanediyl)], .alpha.-sulfo-.omega.-hydroxy-, C14-15-branched and.... (1) The chemical substance identified as poly[oxy(methyl-1,2-ethanediyl)], .alpha.-sulfo-.omega...

40 CFR 721.10283 - Poly[oxy(methyl-1,2-ethanediyl)], .alpha.-sulfo-.omega.-hydroxy-, C12-13-branched and linear...

Code of Federal Regulations, 2012 CFR

2012-07-01

...)], .alpha.-sulfo-.omega.-hydroxy-, C12-13-branched and linear alkyl ethers, sodium salts. 721.10283 Section... Substances § 721.10283 Poly[oxy(methyl-1,2-ethanediyl)], .alpha.-sulfo-.omega.-hydroxy-, C12-13-branched and.... (1) The chemical substance identified as poly[oxy(methyl-1,2-ethanediyl)], .alpha.-sulfo-.omega...

40 CFR 721.10284 - Poly[oxy(methyl-1,2-ethanediyl)], .alpha.-sulfo-.omega.-hydroxy-, C14-15-branched and linear...

Code of Federal Regulations, 2013 CFR

2013-07-01

...)], .alpha.-sulfo-.omega.-hydroxy-, C14-15-branched and linear alkyl ethers, sodium salts. 721.10284 Section... Substances § 721.10284 Poly[oxy(methyl-1,2-ethanediyl)], .alpha.-sulfo-.omega.-hydroxy-, C14-15-branched and.... (1) The chemical substance identified as poly[oxy(methyl-1,2-ethanediyl)], .alpha.-sulfo-.omega...

40 CFR 721.10283 - Poly[oxy(methyl-1,2-ethanediyl)], .alpha.-sulfo-.omega.-hydroxy-, C12-13-branched and linear...

Code of Federal Regulations, 2014 CFR

2014-07-01

...)], .alpha.-sulfo-.omega.-hydroxy-, C12-13-branched and linear alkyl ethers, sodium salts. 721.10283 Section... Substances § 721.10283 Poly[oxy(methyl-1,2-ethanediyl)], .alpha.-sulfo-.omega.-hydroxy-, C12-13-branched and.... (1) The chemical substance identified as poly[oxy(methyl-1,2-ethanediyl)], .alpha.-sulfo-.omega...

The Ethylene Ketal Protecting Group Revisited: The Synthesis of 4-Hydroxy-4, 4-Diphenyl-2-Butanone

ERIC Educational Resources Information Center

Baar, Marsha R.; Russell, Charles E.; Wusthoiz, Kristen L.

2005-01-01

An experiment to demonstrate the use of ethylene ketal as a protecting group, one that can be completed in four lab periods, is described. The hydroxy ketone like 4-hydroxy-4, 4-diphenyl-2-butanone formed during the reaction can be identified by its melting point, IR, and (super 1)H NMR.

Deuterium Enrichment of Amino and Hydroxy Acids Found in the Murchison Meteorite: Constraints on Parent Body Conditions

NASA Technical Reports Server (NTRS)

Lerner, Narcinda R.; Chang, Sherwood (Technical Monitor)

1997-01-01

The alpha-amino and alpha-hydroxy acids found in the Murchison carbonaceous chondrite are deuterium enriched. These compounds are thought to have originated from common deuterium enriched carbonyl precursors, by way of a Strecker synthesis which took place in a solution of HCN, NH3, and carbonyl compounds during the period of aqueous alteration of the meteorite parent body. However, the hydroxy acids found on Murchison are less deuterium enriched than the amino acids. With the objective of determining if the discrepancy in deuterium enrichment between the amino acids and the hydroxy acids found on Murchison is consistent with their formation in a Strecker synthesis, we have measured the deuterium content of alpha-amino and alpha-hydroxy acids produced in solutions of deuterated carbonyl compounds, KCN and NH4Cl, and also in mixtures of such solutions and Allende dust at 263 K and 295 K. Retention of the isotopic signature of the starting carbonyl by both alpha amino acids and alpha hydroxy acids is more dependent upon temperature, concentration and pH than upon the presence of meteorite dust in the solution. The constraints these observations place on Murchison parent body conditions will be discussed.

CO 2 Hydrogenation Catalysts with Deprotonated Picolinamide Ligands

DOE PAGES

Kanega, Ryoichi; Onishi, Naoya; Szalda, David J.; ...

2017-08-21

In an effort to design concepts for highly active catalysts for the hydrogenation of CO 2 to formate in basic water, we have prepared in this paper several catalysts with picolinic acid, picolinamide, and its derivatives, and we investigated their catalytic activity. The CO 2 hydrogenation catalyst having a 4-hydroxy-N-methylpicolinamidate ligand exhibited excellent activity even under ambient conditions (0.1 MPa, 25 °C) in basic water, exhibiting a TON of 14700, a TOF of 167 h –1, and producing a 0.64 M formate concentration. Finally, its high catalytic activity originates from strong electron donation by the anionic amide moiety in additionmore » to the phenolic O – functionality.« less

[Study on the chemical constituents of flavones from corn silk].

PubMed

Zhang, Hui-en; Xu, De-ping

2007-02-01

The three flavones were isolated from water extracts of corn silk by chromatography on macroporous resin, polyamide, ODS and Sephadex LH-20. Three compounds were identified as formononetin (7-hydroxy-4'-methoxyisoflavone) ( I ) ,2"-O-alpha-L-rham-nosyl-6-C-( 3-deoxyglucosyl) -3 '-methoxyluteolin( II ) ,2"-O-alpha-L-rhamnosyl-6-C-( 6-deoxy-ax-5-methyl-xylo-hexos-4-ulosyl) -3'-methoxyluteolin( II ). Compounds ( I ) and ( II ) were isolated from the corn silk for the first time.

Spectrodensitometric Quantitative Determination of Trichothecenes in Water: Application to T-2 Toxin and T-2 Tetraol

DTIC Science & Technology

1984-10-01

3-hydroxy-8-( 3-methybutyryloxy)-1 2,13-epoxytrichothec- *. 9-ene] (la) is an important member of the 12,13-epoxytrichochecene class of mycotoxins ...produced in nat by a number of genera of fungi and recognized increasingly since the late .960’s as responsible for toxic effects in live- stock... poultry , and humans from consumption of contaminated food grains. 1 More recently, since 1981, the issue of possible use of these toxins as " chemical

Design and Conformational Analysis of Peptoids Containing N-Hydroxy Amides Reveals a Unique Sheet-Like Secondary Structure

PubMed Central

Crapster, J. Aaron; Stringer, Joseph R.; Guzei, Ilia A.; Blackwell, Helen E.

2011-01-01

N-hydroxy amides can be found in many naturally occurring and synthetic compounds and are known to act as both strong proton donors and chelators of metal cations. We have initiated studies of peptoids, or N-substituted glycines, that contain N-hydroxy amide side chains to investigate the potential effects of these functional groups on peptoid backbone amide rotamer equilibria and local conformations. We reasoned that the propensity of these functional groups to participate in hydrogen bonding could be exploited to enforce intramolecular or intermolecular interactions that yield new peptoid structures. Here, we report the design, synthesis, and detailed conformational analysis of a series of model N-hydroxy peptoids. These peptoids were readily synthesized, and their structures were analyzed in solution by 1D and 2D NMR and in the solid-state by X-ray crystallography. The N-hydroxy amides were found to strongly favor trans conformations with respect to the peptoid backbone in chloroform. More notably, unique sheet-like structures held together via intermolecular hydrogen bonds were observed in the X-ray crystal structures of an N-hydroxy amide peptoid dimer, which to our knowledge represent the first structure of this type reported for peptoids. These results suggest that the N-hydroxy amide can be utilized to control both local backbone geometries and longer-range intermolecular interactions in peptoids, and represents a new functional group in the peptoid design toolbox. PMID:22180908

Sensory-guided decomposition of roasted cocoa nibs (Theobroma cacao) and structure determination of taste-active polyphenols.

PubMed

Stark, Timo; Bareuther, Sabine; Hofmann, Thomas

2005-06-29

Sequential application of solvent extraction, gel permeation chromatography, and RP-HPLC in combination with taste dilution analyses, followed by LC-MS and 1D/2D-NMR experiments and thiolytic degradation, revealed that, besides theobromine and caffeine, the flavan-3-ols epicatechin, catechin, procyanidin B-2, procyanidin B-5, procyanidin C-1, [epicatechin-(4beta-->8)](3)-epicatechin, and [epicatechin-(4beta-->8)](4)-epicatechin were among the key compounds contributing to the bitter taste as well as the astringent mouthfeel imparted upon consumption of roasted cocoa. In addition, a series of quercetin, naringenin, luteolin, and apigenin glycopyranosides as well as a family of not previously identified amino acid amides, namely, (+)-N-[4'-hydroxy-(E)-cinnamoyl]-L-aspartic acid, (+)-N-[3',4'-dihydroxy-(E)-cinnamoyl]-L-aspartic acid, (-)-N-[3',4'-dihydroxy-(E)-cinnamoyl]-L-glutamic acid, (-)-N-[4'-hydroxy-(E)-cinnamoyl]-L-glutamic acid, (-)-N-[4'-hydroxy-(E)-cinnamoyl]-3-hydroxy-L-tyrosine, (+)-N-[4'-hydroxy-3'-methoxy-(E)-cinnamoyl]-L-aspartic acid, and (+)-N-(E)-cinnamoyl-L-aspartic acid, have been identified as key astringent compounds of roasted cocoa. Furthermore, (-)-N-[3',4'-dihydroxy-(E)-cinnamoyl]-3-hydroxy-l-tyrosine (clovamide), (-)-N-[4'-hydroxy-(E)-cinnamoyl]-L-tyrosine (deoxyclovamide), and (-)-N-[3',4'-dihydroxy-(E)-cinnamoyl]-L-tyrosine, reported previously as antioxidants, have been found as contributors of cocoa's astringent taste. By means of the half-tongue test, the taste thresholds of flavan-3-ols and glycosides have been determined.

Unrecognized vitamin D3 deficiency is common in Parkinson disease: Harvard Biomarker Study.

PubMed

Ding, Hongliu; Dhima, Kaltra; Lockhart, Kaitlin C; Locascio, Joseph J; Hoesing, Ashley N; Duong, Karen; Trisini-Lipsanopoulos, Ana; Hayes, Michael T; Sohur, U Shivraj; Wills, Anne-Marie; Mollenhauer, Brit; Flaherty, Alice W; Hung, Albert Y; Mejia, Nicte; Khurana, Vikram; Gomperts, Stephen N; Selkoe, Dennis J; Schwarzschild, Michael A; Schlossmacher, Michael G; Hyman, Bradley T; Sudarsky, Lewis R; Growdon, John H; Scherzer, Clemens R

2013-10-22

To conclusively test for a specific association between the biological marker 25-hydroxy-vitamin D3, a transcriptionally active hormone produced in human skin and liver, and the prevalence and severity of Parkinson disease (PD). We used liquid chromatography/tandem mass spectrometry to establish an association specifically between deficiency of 25-hydroxy-vitamin D3 and PD in a cross-sectional and longitudinal case-control study of 388 patients (mean Hoehn and Yahr stage of 2.1 ± 0.6) and 283 control subjects free of neurologic disease nested in the Harvard Biomarker Study. Plasma levels of 25-hydroxy-vitamin D3 were associated with PD in both univariate and multivariate analyses with p values = 0.0034 and 0.047, respectively. Total 25-hydroxy-vitamin D levels, the traditional composite measure of endogenous and exogenous vitamin D, were deficient in 17.6% of patients with PD compared with 9.3% of controls. Low 25-hydroxy-vitamin D3 as well as total 25-hydroxy-vitamin D levels were correlated with higher total Unified Parkinson's Disease Rating Scale scores at baseline and during follow-up. Our study reveals an association between 25-hydroxy-vitamin D3 and PD and suggests that thousands of patients with PD in North America alone may be vitamin D-deficient. This finding has immediate relevance for individual patients at risk of falls as well as public health, and warrants further investigation into the mechanism underlying this association.

Unrecognized vitamin D3 deficiency is common in Parkinson disease

PubMed Central

Ding, Hongliu; Dhima, Kaltra; Lockhart, Kaitlin C.; Locascio, Joseph J.; Hoesing, Ashley N.; Duong, Karen; Trisini-Lipsanopoulos, Ana; Hayes, Michael T.; Sohur, U. Shivraj; Wills, Anne-Marie; Mollenhauer, Brit; Flaherty, Alice W.; Hung, Albert Y.; Mejia, Nicte; Khurana, Vikram; Gomperts, Stephen N.; Selkoe, Dennis J.; Schwarzschild, Michael A.; Schlossmacher, Michael G.; Hyman, Bradley T.; Sudarsky, Lewis R.; Growdon, John H.

2013-01-01

Objective: To conclusively test for a specific association between the biological marker 25-hydroxy-vitamin D3, a transcriptionally active hormone produced in human skin and liver, and the prevalence and severity of Parkinson disease (PD). Methods: We used liquid chromatography/tandem mass spectrometry to establish an association specifically between deficiency of 25-hydroxy-vitamin D3 and PD in a cross-sectional and longitudinal case-control study of 388 patients (mean Hoehn and Yahr stage of 2.1 ± 0.6) and 283 control subjects free of neurologic disease nested in the Harvard Biomarker Study. Results: Plasma levels of 25-hydroxy-vitamin D3 were associated with PD in both univariate and multivariate analyses with p values = 0.0034 and 0.047, respectively. Total 25-hydroxy-vitamin D levels, the traditional composite measure of endogenous and exogenous vitamin D, were deficient in 17.6% of patients with PD compared with 9.3% of controls. Low 25-hydroxy-vitamin D3 as well as total 25-hydroxy-vitamin D levels were correlated with higher total Unified Parkinson’s Disease Rating Scale scores at baseline and during follow-up. Conclusions: Our study reveals an association between 25-hydroxy-vitamin D3 and PD and suggests that thousands of patients with PD in North America alone may be vitamin D–deficient. This finding has immediate relevance for individual patients at risk of falls as well as public health, and warrants further investigation into the mechanism underlying this association. PMID:24068787

Hydroxy nitrate production in the OH-initiated oxidation of alkenes

NASA Astrophysics Data System (ADS)

Teng, A. P.; Crounse, J. D.; Lee, L.; St. Clair, J. M.; Cohen, R. C.; Wennberg, P. O.

2014-03-01

Alkenes generally react rapidly by addition of OH and subsequently O2 to form beta hydroxy peroxy radicals. These peroxy radicals react with NO to form beta hydroxy nitrates with a branching ratio α. We quantify α for C2-C8 alkenes at 296 K ±3 and 993 hPa. The branching ratio can be expressed as α = (0.042 ± 0.008) × N - (0.11 ± 0.04) where N is the number of heavy atoms (excluding the peroxy moiety), and listed errors are 2σ. These branching ratios are larger than previously reported and are similar to those for peroxy radicals formed from H abstraction from alkanes. We find the isomer distributions of beta hydroxy nitrates formed under NO-dominated peroxy radical chemistry to be similar to the isomer distribution of hydroxy hydroperoxides produced under HO2-dominated peroxy radical chemistry. With the assumption of unity yield for the hydroperoxides, this implies that the branching ratio to form beta hydroxy nitrates from primary, secondary, and tertiary RO2 are similar. Deuterium substitution enhances the branching ratio to form hydroxy nitrates in both propene and isoprene by a factor of ~1.5. These observations provide further evidence for importance of the ROONO lifetime in determining the branching ratio to form alkyl nitrates. We use these measurements to re-evaluate the role of alkene chemistry in the Houston region. We find that small alkenes play a larger role in oxidant formation than previously recognized.

Hydroxy nitrate production in the OH-initiated oxidation of alkenes

NASA Astrophysics Data System (ADS)

Teng, A. P.; Crounse, J. D.; Lee, L.; St. Clair, J. M.; Cohen, R. C.; Wennberg, P. O.

2015-04-01

Alkenes are oxidized rapidly in the atmosphere by addition of OH and subsequently O2 leading to the formation of β-hydroxy peroxy radicals. These peroxy radicals react with NO to form β-hydroxy nitrates with a branching ratio α. We quantify α for CM2-C8 alkenes at 295 K ± 3 and 993 hPa. The branching ratio can be expressed as α = (0.045 ± 0.016) × N - (0.11 ± 0.05) where N is the number of heavy atoms (excluding the peroxy moiety), and listed errors are 2σ. These branching ratios are larger than previously reported and are similar to those for peroxy radicals formed from H abstraction from alkanes. We find the isomer distributions of β-hydroxy nitrates formed under NO-dominated peroxy radical chemistry to be different than the isomer distribution of hydroxy hydroperoxides produced under HO2-dominated peroxy radical chemistry. Assuming unity yield for the hydroperoxides implies that the branching ratio to form β-hydroxy nitrates increases with substitution of RO2. Deuterium substitution enhances the branching ratio to form hydroxy nitrates in both propene and isoprene by a factor of ~ 1.5. The role of alkene chemistry in the Houston region is re-evaluated using the RONO2 branching ratios reported here. Small alkenes are found to play a significant role in present-day oxidant formation more than a decade (2013) after the 2000 Texas Air Quality Study identified these compounds as major contributors to photochemical smog in Houston.

Bioplastics from microorganisms.

PubMed

Luengo, José M; García, Belén; Sandoval, Angel; Naharro, Germán; Olivera, Elías R

2003-06-01

The term 'biomaterials' includes chemically unrelated products that are synthesised by microorganisms (or part of them) under different environmental conditions. One important family of biomaterials is bioplastics. These are polyesters that are widely distributed in nature and accumulate intracellularly in microorganisms in the form of storage granules, with physico-chemical properties resembling petrochemical plastics. These polymers are usually built from hydroxy-acyl-CoA derivatives via different metabolic pathways. Depending on their microbial origin, bioplastics differ in their monomer composition, macromolecular structure and physical properties. Most of them are biodegradable and biocompatible, which makes them extremely interesting from the biotechnological point of view.

Monitoring system for the study of autotrophic biofilms in bioremediation of polyaromatic compounds

NASA Astrophysics Data System (ADS)

Alarie, Jean P.; Bruttig, A.; Miller, Gordon H.; Hill, Walter; Vo-Dinh, Tuan

1999-02-01

Bacterial and other natural materials such as plants and algae have received increasing interest for bioremediation efforts. The identificatIon of materials capable of biodegrading or sequestering environmental pollutants offers an attractive alternative to chemical or physical means of remediation. A number of bacteria capable of biodegrAding organic or reducing metal pollutants have received great interest. Similarly, the use of natural plants to absorb pollutants from soil anD liquid samples is another potential approach. Our interest lies in identification of naturally occurring algae and their ability to absorb polyaromatic compounds (PAC) from groundwater sources (i.e. streams). These algae could serve as natural water filters for streams contaminated with Polyaromatic hydrocarbons. Polycyclic aromatic compounds, which comprise a complex class of condensed multi-ring benzenoid compounds, are important environmental pollutants originating from a wide variety of natural and anthropogenic sources. PACs are generally formed during incomplete combustion or pyrolysis of organic matter containing carbon and hydrogen. Because combustion of organic materials is involved in countless natural processes or human activities, PACs are omnipresent and abundant pollutants in air, soil and water. Among energy-related products, fossil fuels are the major sources of PACs. The primary sources of airborne PACs are associated with combustion, coal coking, and petroleum catalytic cracking. Coal and shale conversion also contribute to production of PACs. Production, transportation and, use of synthetic fuels and petroleum products provide emission sources for PACs. In urban environments an significant source of PACs is diesel exhaust. Food cooking and cigarette smoking activities contribute to PAC occurrence in indoor environments. Chemical analysis of PACs is of great environmental and toxicological interest because many of them have been shown to be mutagens and/or potent carcinogens in laboratory animal assays. The parent homocyclic species, which contain only carbon and hydrogen, are the familiar polyaromatic hydrocarbon (PAH) compounds. In addition to the PAH compounds, there are thousands of substituted compounds that could have various substituent groups, such as alkyl, amino, chloro, cyano, hydroxy, oxy, or thio groups. In this study we investigate anthracene and pyrene as PAH model systems. A portable fiberoptic instrument capable of real-time measurements has been developed for field screening these PAHs in surface water and natural algae systems. Our preliminary studies investigated the detection limits of anthracene and pyrene and the adsorption properties of two algae using fluorescence monitoring. An exposure study of the algae to 5 ppb anthracene was performed to investigate the ability of the algae to adsorb PAHs.

Apoplastic polyesters in Arabidopsis surface tissues--a typical suberin and a particular cutin.

PubMed

Franke, Rochus; Briesen, Isabel; Wojciechowski, Tobias; Faust, Andrea; Yephremov, Alexander; Nawrath, Christiane; Schreiber, Lukas

2005-11-01

Cutinized and suberized cell walls form physiological important plant-environment interfaces as they act as barriers limiting water and nutrient loss and protect from radiation and invasion by pathogens. Due to the lack of protocols for the isolation and analysis of cutin and suberin in Arabidopsis, the model plant for molecular biology, mutants and transgenic plants with a defined altered cutin or suberin composition are unavailable, causing that structure and function of these apoplastic barriers are still poorly understood. Transmission electron microscopy (TEM) revealed that Arabidopsis leaf cuticle thickness ranges from only 22 nm in leaf blades to 45 nm on petioles, causing the difficulty in cuticular membrane isolation. We report the use of polysaccharide hydrolases to isolate Arabidopsis cuticular membranes, suitable for depolymerization and subsequent compositional analysis. Although cutin characteristic omega-hydroxy acids (7%) and mid-chain hydroxylated fatty acids (8%) were detected, the discovery of alpha,omega-diacids (40%) and 2-hydroxy acids (14%) as major depolymerization products reveals a so far novel monomer composition in Arabidopsis cutin, but with chemical analogy to root suberin. Histochemical and TEM analysis revealed that suberin depositions were localized to the cell walls in the endodermis of primary roots and the periderm of mature roots of Arabidopsis. Enzyme digested and solvent extracted root cell walls when subjected to suberin depolymerization conditions released omega-hydroxy acids (43%) and alpha,omega-diacids (24%) as major components together with carboxylic acids (9%), alcohols (6%) and 2-hydroxyacids (0.1%). This similarity to suberin of other species indicates that Arabidopsis roots can serve as a model for suberized tissue in general.

Characterization and evaluation of an oral microemulsion containing the antitumor diterpenoid compound ent-11alpha-hydroxy-15-oxo-kaur-16-en-19-oic-acid.

PubMed

Lu, Yingnian; Wu, Kefeng; Li, Li; He, Yuhui; Cui, Liao; Liang, Nianci; Mu, Bozhong

2013-01-01

The objective of this study was to develop an oral microemulsion formulation of the antitumor diterpenoid agent, ent-11α-hydroxy-15-oxo-kaur-16-en-19-oic-acid (henceforth referred to as 5F), to enhance its bioavailability and evaluate its hepatotoxicity. Pseudoternary phase diagrams showed that the optimal microemulsion formulation contained 45% water, 10% castor oil as the oil phase, 15% Cremophor EL as the surfactant, and 30% as a cosurfactant mixture of 1,2-propanediol and polyethylene glycol (PEG)-400 (2:1, w/w). The microemulsion preparation was characterized and its droplet diameter was within 50 nm. Release of 5F in vitro from the microemulsion was slightly increased compared with a suspension containing the same amount of active drug. Pharmacokinetic parameters in vivo indicated that bioavailability was markedly improved, with the relative bioavailability being 616.15% higher for the microemulsion than for the suspension. Toxicity tests showed that the microemulsion had no hepatotoxicity in mice. These results suggest the potential for 5F microemulsion to be administered by the oral route.

Effect of chitosan, O-carboxymethyl chitosan, and N-[(2-hydroxy-3-N,N-dimethylhexadecyl ammonium)propyl] chitosan chloride on overweight and insulin resistance in a murine diet-induced obesity.

PubMed

Liu, Xiaofei; Zhi, Xiaona; Liu, Yunfei; Wu, Bo; Sun, Zhong; Shen, Jun

2012-04-04

Two water-soluble chitosan derivatives, O-carboxymethyl chitosan (O-CM-chitosan) and N-[(2-hydroxy-3-N,N-dimethylhexadecyl ammonium)propyl] chitosan chloride (N-CQ-chitosan), were prepared, and the therapeutic effects of chitosan, O-CM-chitosan, and N-CQ-chitosan on insulin resistance were simultaneously evaluated by rats fed on a high-fat diet. The parameters of high-fat diet-induced rats indicated that chitosan and its two derivatives not only have low cytotoxicity but can control overnutrition by fat and achieve insulin resistance therapy. However, the results in experiment in vivo showed that the therapeutic degree varied by the molecular weight and surface charge of chitosan, O-CM-chitosan, and N-CQ-chitosan. N-CQ-chitosan with a MW of 5 × 10(4) decreased body weight, the ratio of fat to body weight, triglyceride, fasting plasma glucose, fasting plasma insulin, free fatty acid, and leptin by 11, 17, 44, 46, 44, 87, and 64% and increased fecal lipid by 95%, respectively.

Bis{2-meth­oxy-6-[tris­(hydroxy­meth­yl)methyl­imino­meth­yl]phenolato-κ3 O,N,O′}manganese(II) dimethanol solvate hemihydrate

PubMed Central

Zhang, Xiutang; Wei, Peihai; Dou, Jianmin; Li, Bin; Hu, Bo

2009-01-01

In the title complex, [Mn(C12H16NO5)2]·2CH3OH·0.5H2O, the MnII atom has a distorted octa­hedral coordination geometry in which two N atoms from two 6-meth­oxy-2-[tris­(hydroxy­meth­yl)methyl­imino­meth­yl]phenolate ligands adopt a trans arrangement. The Mn—O(H) bonds (mean length 2.134 Å) are significantly longer than the Mn—O and Mn—N bonds (mean length 2.011 and 2.027 Å, respectively), and the dihedral angle between the mean planes through the aromatic rings of the two ligands is 76.8 (1)°. A complex network of O—H⋯O hydrogen bonds is formed between the complexes and the uncoordinated methanol and water mol­ecules. The C and O atoms of one C—OH group are disordered with equal occupancies. PMID:21582076

Evaluation of 8-Hydroxyquinoline Derivatives as Hits for Antifungal Drug Design.

PubMed

Pippi, Bruna; Reginatto, Paula; Machado, Gabriella da Rosa Monte; Bergamo, Vanessa Zafaneli; Lana, Daiane Flores Dalla; Teixeira, Mario Lettieri; Franco, Lucas Lopardi; Alves, Ricardo José; Andrade, Saulo Fernandes; Fuentefria, Alexandre Meneghello

2017-10-01

Clioquinol is an 8-hydroxyquinoline derivative that was widely used from the 1950s to 1970s as an oral antiparasitic agent. In 1970, the oral forms were withdrawn from the market due to reports of toxicity, but topical formulations for antifungal treatment remained available. Thus, the purpose of this study was to evaluate the toxicity, anti-Candida and antidermatophyte activity and to determine pharmacodynamic characteristics of clioquinol and other 8-hydroxyquinoline derivatives (8-hydroxy-5-quinolinesulfonic acid and 8-hydroxy-7-iodo-5-quinolinesulfonic acid). Antifungal activity was tested by broth microdilution and the fungicidal or fungistatic effect was checked by a time-kill assay. Permeation and histopathological evaluation were performed in Franz diffusion cells with ear skin of pigs and examined under light microscopy. An HET-CAM test was used to determine the potential irritancy. The three compounds were active against all isolates showing anti-Candida and antidermatophyte activity, with MIC ranges of 0.031-2 μg/ml, 1-512 μg/ml, and 2-1024 μg/ml for clioquinol, 8-hydroxy-5-quinolinesulfonic acid, and 8-hydroxy-7-iodo-5-quinolinesulfonic acid, respectively. All compounds showed fungistatic effect for Candida, 8-hydroxy-5-quinolinesulfonic acid, and 8-hydroxy-7-iodo-5-quinolinesulfonic acid showed a fungicidal effect for M. canis and T. mentagrophytes, and clioquinol showed a fungicidal effect only for T. mentagrophytes. Furthermore, they presented a fungicidal effect depending on the time and concentration. The absence of lesions was observed in histopathological evaluation and no compound was irritating. Moreover, clioquinol and 8-hydroxy-5-quinolinesulfonic acid accumulated in the epithelial tissue, and 8-hydroxy-7-iodo-5-quinolinesulfonic acid had a high degree of permeation. In conclusion, 8-hydroxyquinoline derivatives showed antifungal activity and 8-hydroxy-5-quinolinesulfonic acid demonstrated the potential for antifungal drug design. © The Author 2017. Published by Oxford University Press on behalf of The International Society for Human and Animal Mycology. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Comparison of salting-out and sugaring-out liquid-liquid extraction methods for the partition of 10-hydroxy-2-decenoic acid in royal jelly and their co-extracted protein content.

PubMed

Tu, Xijuan; Sun, Fanyi; Wu, Siyuan; Liu, Weiyi; Gao, Zhaosheng; Huang, Shaokang; Chen, Wenbin

2018-01-15

Homogeneous liquid-liquid extraction (h-LLE) has been receiving considerable attention as a sample preparation method due to its simple and fast partition of compounds with a wide range of polarities. To better understand the differences between the two h-LLE extraction approaches, salting-out assisted liquid-liquid extraction (SALLE) and sugaring-out assisted liquid-liquid extraction (SULLE), have been compared for the partition of 10-hydroxy-2-decenoic acid (10-HDA) from royal jelly, and for the co-extraction of proteins. Effects of the amount of phase partition agents and the concentration of acetonitrile (ACN) on the h-LLE were discussed. Results showed that partition efficiency of 10-HDA depends on the phase ratio in both SALLE and SULLE. Though the partition triggered by NaCl and glucose is less efficient than MgSO 4 in the 50% (v/v) ACN-water mixture, their extraction yields can be improved to be similar with that in MgSO 4 SALLE by increasing the initial concentration of ACN in the ACN-water mixture. The content of co-extracted protein was correlated with water concentration in the obtained upper phase. MgSO 4 showed the largest protein co-extraction at the low concentration of salt. Glucose exhibited a large protein co-extraction in the high phase ratio condition. Furthermore, NaCl with high initial ACN concentration is recommended because it produced high extraction yield for 10-HDA and the lowest amount of co-extracted protein. These observations would be valuable for the sample preparation of royal jelly. Copyright © 2017 Elsevier B.V. All rights reserved.

3-hydroxy-2(1H)-pyridinone chelating agents

DOEpatents

Raymond, K.N.; Xu, J.

1997-04-29

Disclosed is a series of improved metal chelating agents, which are highly effective upon both injection and oral administration; several of the most effective are of low toxicity. These chelating agents incorporate within their structure 1-hydroxy-2-pyridinone (1,2-HOPO) and 3-hydroxy-2-pyridinone (3,2-HOPO) moieties with a substituted carbamoyl group ortho to the hydroxy or oxo groups of the hydroxypyridinone ring. The electron-withdrawing carbamoyl group increases the acidity of the hydroxypyridinones. In the metal complexes of the chelating agents, the amide protons form very strong hydrogen bonds with its adjacent HOPO oxygen donor, making these complexes very stable at physiological conditions. The terminal N-substituents provides a certain degree of lipophilicity to the 3,2-HOPO, increasing oral activity. Also disclosed is a method of making the chelating agents and a method of producing a known compound, 3-hydroxy-1-alkyl-2(1H)pyridinone, used as a precursor to the chelating agent, safely and in large quantities. 2 figs.

3-hydroxy-2(1H)-pyridinone chelating agents

DOEpatents

Raymond, Kenneth N.; Xu, Jide

1997-01-01

Disclosed is a series of improved metal chelating agents, which are highly effective upon both injection and oral administration; several of the most effective are of low toxicity. These chelating agents incorporate within their structure 1-hydroxy-2-pyridinone (1,2-HOPO) and 3-hydroxy-2-pyridinone (3,2-HOPO) moieties with a substituted carbamoyl group ortho to the hydroxy or oxo groups of the hydroxypyridinone ring. The electron-withdrawing carbamoyl group increases the acidity of the hydroxypyridinones. In the metal complexes of said chelating agents, the amide protons form very strong hydrogen bonds with its adjacent HOPO oxygen donor, making these complexes very stable at physiological conditions. The terminal N-substituents provides a certain degree of lipophilicity to said 3,2-HOPO, increasing oral activity. Also disclosed is a method of making the chelating agents and a method of producing a known compound, 3-hydroxy-1-alkyl-2(1H)pyridinone, used as a precursor to the chelating agent, safely and in large quantities.

Process for the preparation of benozotriazoles and their polymers, and 2(2-hydroxy-5-isopropenylphenyl)2H-benzotriazole produced thereby

DOEpatents

Vogl, Otto; Nir, Zohar

1989-03-14

The compound 2(2-hydroxy-5-isopropenylphenyl)2H-benzotriazole (2H5P) is produced by azo coupling of o-nitrophenyl diazonium chloride with p-hydroxyacetophenone, subjecting the resulting isolated azo compound to reductive cyclization with zinc in the presence of sodium hydroxide at a temperature of about 50.degree.-70.degree. C., acidifying the resulting mixture so as to produce (2(2-hydroxy-5-acetylphenyl)2H-benzotriazole (2H5A), acetylating the isolated 2(2-hydroxy-5-acetylphenyl)2H-benzotriazole (2H5A), so as to produce 2(2-acetoxy-5-acetylphenyl)2H-benzotriazole (2A5A), methylating the isolated 2(2-acetoxy-5-acetylphenyl(2H-benzotriazole (2A5A) with a methyl Grignard reagent and dehydrating the isolated reaction product with potassium hydrogen sulfate so as to produce 2(2-hydroxy-5-isopropenylphenyl)2H-benzotriazole (2H5P). The compound is used as a polymerizable ultra violet light stabilizer.

Tautomerism in N-(2-hydroxy-1-naphthylidene)amino acids and the search for an answer to the difficult question about where the proton belongs

NASA Astrophysics Data System (ADS)

Warncke, Gisela; Fels, Sabine; Brendler, Erica; Böhme, Uwe

2016-08-01

N-(2-hydroxy-1-naphthylidene)-L-valine 1, N-(2-hydroxy-1-naphthylidene)-L-phenylalanine 2, and N-(2-hydroxy-1-naphthylidene)-L-threonine 3 were prepared and characterized with spectroscopic methods, elemental analyses, and values of optical rotation. Compound 1 undergoes a solid state order-disorder phase transition at 231 K. The X-ray structures of the high and low temperature phase of 1 have been determined. Single crystal X-ray structures of 2 and 3 have been determined as well. The tautomerism of N-(2-hydroxy-1-naphthylidene)amino acid derivatives is discussed controversial in the literature. A bond lengths statistical analysis shows that all three compounds exist uniformly in the keto-amine form in the solid state. Quantum chemical calculations, NMR, and UV-Vis spectroscopy were used to obtain further insight into the existence of phenol-imine and keto-amine structures in this class of compounds.

Binary ferrihydrite catalysts

DOEpatents

Huffman, G.P.; Zhao, J.; Feng, Z.

1996-12-03

A method of preparing a catalyst precursor comprises dissolving an iron salt and a salt of an oxoanion forming agent, in water so that a solution of the iron salt and oxoanion forming agent salt has a ratio of oxoanion/Fe of between 0.0001:1 to 0.5:1. Next is increasing the pH of the solution to 10 by adding a strong base followed by collecting of precipitate having a binary ferrihydrite structure. A binary ferrihydrite catalyst precursor is also prepared by dissolving an iron salt in water. The solution is brought to a pH of substantially 10 to obtain ferrihydrite precipitate. The precipitate is then filtered and washed with distilled water and subsequently admixed with a hydroxy carboxylic acid solution. The admixture is mixed/agitated and the binary ferrihydrite precipitate is then filtered and recovered. 3 figs.

Comparison of availability and plasma clearance rates of β-hydroxy-β-methylbutyrate delivery in the free acid and calcium salt forms.

PubMed

Fuller, John C; Sharp, Rick L; Angus, Hector F; Khoo, Paul Y; Rathmacher, John A

2015-11-14

β-Hydroxy-β-methylbutyrate (HMB), a leucine metabolite, has long been supplemented as a Ca salt (Ca-HMB) to increase strength and performance gains with exercise and to reduce recovery time. Recently, the free acid form of HMB (HMB-FA) has become commercially available in capsule form (gelcap). The current study was conducted to compare the bioavailability of HMB using the two commercially available capsule forms of HMB-FA and Ca-HMB. We also compared the pharmacokinetics of each form when administered mixed in water. Ten human subjects (five male and five female) were studied in a randomised crossover design. There was no significant sex by treatment interaction for any of the pharmacokinetic parameters measured. HMB-FA administered in capsules was more efficient than Ca-HMB capsule at HMB delivery with a 37 % increase in plasma clearance rate (74·8 (sem 4·0) v. 54·5 (sem 3·2) ml/min, P<0·0001) and a 76 % increase in peak plasma HMB concentration (270·2 (sem 17·8) v. 153·9 (sem 17·9) μmol/l, P<0·006), which was reached in one-third the time (P<0·009). When HMB-FA and Ca-HMB were administered in water, the differences still favoured HMB-FA, albeit to a lesser degree. Plasma HMB with HMB-FA administered in water was greater during the early phase of absorption (up to 45 min postadministration, P<0·05); this resulted in increased AUC during the first 60 min after administration, when compared with Ca-HMB mixed in water (P<0·03). In conclusion, HMB-FA in capsule form improves clearance rate and availability of HMB compared with Ca-HMB in capsule form.

40 CFR 721.3152 - Ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl...

Code of Federal Regulations, 2013 CFR

2013-07-01

...-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates (salts). 721.3152 Section 721... Ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates... ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates...

40 CFR 721.3152 - Ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl...

Code of Federal Regulations, 2014 CFR

2014-07-01

...-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates (salts). 721.3152 Section 721... Ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates... ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates...

40 CFR 721.3152 - Ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl...

Code of Federal Regulations, 2012 CFR

2012-07-01

...-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates (salts). 721.3152 Section 721... Ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates... ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates...

40 CFR 721.1550 - Benzenediazonium, 4-(di-methyl-amino)-, salt with 2-hy-droxy-5-sul-fo-benzoic acid (1:1).

Code of Federal Regulations, 2011 CFR

2011-07-01

...-amino)-, salt with 2-hy-droxy-5-sul-fo-benzoic acid (1:1). (a) Chemical substance and significant new... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Benzenediazonium, 4-(di-methyl-amino)-, salt with 2-hy-droxy-5-sul-fo-benzoic acid (1:1). 721.1550 Section 721.1550 Protection of Environment...

Production of 10(S)-hydroxy-8(E)-octadecenoic and 7,10(S,S)-hydroxy-8(E)-octadecenoic ethyl esters by Novozym 435 in solvent-free media

USDA-ARS?s Scientific Manuscript database

Novozym 435, lipase B from Candida antarctica, was used in this study for the production of ethyl esters. For the first time, trans-hydroxy-fatty acid ethyl esters were synthesized in vitro in solvent-free media. We studied the effects of the substrate–ethanol molar ratio and enzyme synthetic stabil...

40 CFR 721.1730 - Poly(oxy-1,2-ethanediyl), α-butyl-ω-hydroxy, ester with boric acid (H3BO3).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Poly(oxy-1,2-ethanediyl), α-butyl-Ï... Significant New Uses for Specific Chemical Substances § 721.1730 Poly(oxy-1,2-ethanediyl), α-butyl-ω-hydroxy...) The chemical substance identified as poly(oxy-1,2-ethanediyl), α-butyl-ω-hydroxy, ester with boric...

40 CFR 721.1730 - Poly(oxy-1,2-ethanediyl), α-butyl-ω-hydroxy, ester with boric acid (H3BO3).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Poly(oxy-1,2-ethanediyl), α-butyl-Ï... Significant New Uses for Specific Chemical Substances § 721.1730 Poly(oxy-1,2-ethanediyl), α-butyl-ω-hydroxy...) The chemical substance identified as poly(oxy-1,2-ethanediyl), α-butyl-ω-hydroxy, ester with boric...

40 CFR 721.8100 - Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy...

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. 721.8100...-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. (a) Chemical substances and significant new use subject to...

40 CFR 721.8100 - Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. 721.8100...-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. (a) Chemical substances and significant new use subject to...

40 CFR 721.8100 - Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy...

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. 721.8100...-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. (a) Chemical substances and significant new use subject to...

40 CFR 721.8100 - Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy...

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. 721.8100...-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. (a) Chemical substances and significant new use subject to...

40 CFR 721.8100 - Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy...

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Potassium N,N-bis (hydroxy-ethyl) cocoamine oxide phosphate, and potassium N,N-bis (hy-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. 721.8100...-droxy-ethyl) tal-lo-wa-mine oxide phos-phate. (a) Chemical substances and significant new use subject to...

Neuroprotective 2-(2-phenylethyl)chromones of Imperata cylindrica.

PubMed

Yoon, Jeong Seon; Lee, Mi Kyeong; Sung, Sang Hyun; Kim, Young Choong

2006-02-01

Bioactivity-guided fractionation of the methanolic extract of the rhizomes of Imperata cylindrica afforded a new compound, 5-hydroxy-2-(2-phenylethyl)chromone (1), together with three known compounds, 5-hydroxy-2-[2-(2-hydroxyphenyl)ethyl]chromone (2), flidersiachromone (3), and 5-hydroxy-2-styrylchromone (4). Among these four compounds, 1 and 2 showed significant neuroprotective activity against glutamate-induced neurotoxicity in primary cultures of rat cortical cells.

40 CFR 721.3152 - Ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl...

Code of Federal Regulations, 2011 CFR

2011-07-01

...-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates (salts). 721.3152 Section 721... Ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates... ethanaminium, N-ethyl-2-hydroxy-N,N-bis(2-hydroxyethyl)-, diester with C12-18 fatty acids, ethyl sulfates...

Comparison of alpha- and beta-hydroxy acid chemical peels in the treatment of mild to moderately severe facial acne vulgaris.

PubMed

Kessler, Edward; Flanagan, Katherine; Chia, Christina; Rogers, Cynthia; Glaser, Dee Anna

2008-01-01

Chemical peels are used as adjuvants for treatment of facial acne. No well-controlled studies have compared alpha- and beta-hydroxy acid peels in the treatment of mild to moderately severe facial acne. To compare the efficacy of alpha- and beta-hydroxy acid chemical peels in the treatment of mild to moderately severe facial acne vulgaris. Twenty patients were recruited in this split-face, double-blind, randomized, controlled study. An alpha-hydroxy acid (30% glycolic acid) was applied to one-half of the face and a beta-hydroxy acid peel (30% salicylic acid) was applied contralaterally every 2 weeks for a total of six treatments. A blinded evaluator performed quantitative assessment of papules and pustules. Both chemical peels were significantly effective by the second treatment (p<.05) and there were no significant differences in effectiveness between the two peels. At 2 months posttreatment, the salicylic acid peel had sustained effectiveness. More adverse events were reported with the glycolic acid peel after the initial treatment. The glycolic acid and salicylic acid peels were similarly effective. The salicylic acid peel had sustained effectiveness and fewer side effects. Alpha- and beta-hydroxy acid peels both offer successful adjunctive treatment of facial acne vulgaris.

Preparation of 7-hydroxy-2-oxoindolin-3-ylacetic acid and its [13C2], [5-n-3H], and [5-n-3H]-7-O-glucosyl analogues for use in the study of indol-3-ylacetic acid catabolism

NASA Technical Reports Server (NTRS)

Lewer, P.; Bandurski, R. S. (Principal Investigator)

1987-01-01

An improved synthesis of 7-hydroxy-2-oxoindolin-3-ylacetic acid via the base-induced condensation reaction between oxalate esters and 7-benzyloxyindolin-2-one is described. 7-Benzyloxyindolin-2-one was prepared in four steps and 50% overall yield from 3-hydroxy-2-nitrotoluene. The yield of the title compound from 7-benzyloxyindolin-2-one was 56%. This route was used to prepare 7-hydroxy-2-oxoindolin-3-yl[13C2]acetic acid in 30% yield from [13C2]oxalic acid dihydrate. The method could not be extended to the preparation of the corresponding [14C2]-compound. However, an enzyme preparation from Zea mays roots catalysed the conversion of carrier-free [5-n-3H]indol-3-ylacetic acid with a specific activity of 16.7 Ci mmol-1 to a mixture of 7-hydroxy-2-oxo[5-n-3H]indolin-3-ylacetic acid and its [5-n-3H]-7-O-glucoside in ca. 3 and 40% radiochemical yield respectively. The glucoside was converted into the 7-hydroxy compound in 80% yield by means of beta-glucosidase.

Effects of vitamin D and calcium supplementation on side effects profile in patients of breast cancer treated with letrozole.

PubMed

Arul Vijaya Vani, S; Ananthanarayanan, P H; Kadambari, D; Harichandrakumar, K T; Niranjjan, R; Nandeesha, H

2016-08-01

Vitamin D deficiency (<10ng/mL) and insufficiency (10-30ng/mL) may contribute to musculoskeletal symptoms observed in patients taking letrozole. This study was undertaken to assess the vitamin D status in breast cancer patients who received letrozole for >2months and to see the effects of vitamin D3 and calcium supplementation on them. Eighty-two breast cancer patients were included. Baseline serum 25-hydroxy vitamin D concentrations were assayed and standard questionnaire was completed. They were given vitamin D3 and calcium supplementation (2000IU/1000 mg and 4000IU/1000mg) based on their baseline serum 25-hydroxy vitamin D concentration for 12weeks. Baseline serum 25-hydroxy vitamin D concentrations showed that 13.4% of patients were deficient and 73.2% of patients were insufficient in 25-hydroxy vitamin D. There was an increase in the concentrations of calcium, phosphorus and decrease in the concentrations of parathyroid hormone, alkaline phosphatase as the concentration of serum 25-hydroxy vitamin D increases. Patients who received letrozole for a longer duration had a low concentration of serum 25 (OH) vitamin D. Vitamin D3 and calcium supplementation increased the concentrations of calcium, phosphorous and decreased the concentrations of parathyroid hormone and alkaline phosphatase. Patients who had low serum 25-hydroxy vitamin D concentrations had more musculoskeletal symptoms which was improved following supplementation (9.14 vs 8.10 p=0.000). Vitamin D3 supplementation significantly improved serum 25-hydroxy vitamin D concentrations and decreased letrozole-induced arthralgia. Copyright © 2016 Elsevier B.V. All rights reserved.

The Functionality of Surface Hydroxy Groups on the Selectivity and Activity of Carbon Dioxide Reduction over Cuprous Oxide in Aqueous Solutions.

PubMed

Yang, Piaoping; Zhao, Zhi-Jian; Chang, Xiaoxia; Mu, Rentao; Zha, Shenjun; Zhang, Gong; Gong, Jinlong

2018-06-25

Carbon dioxide (CO 2 ) reduction in aqueous solutions is an attractive strategy for carbon capture and utilization. Cuprous oxide (Cu 2 O) is a promising catalyst for CO 2 reduction as it can convert CO 2 into valuable hydrocarbons and suppress the side hydrogen evolution reaction (HER). However, the nature of the active sites in Cu 2 O remains under debate because of the complex surface structure of Cu 2 O under reducing conditions, leading to limited guidance in designing improved Cu 2 O catalysts. This paper describes the functionality of surface-bonded hydroxy groups on partially reduced Cu 2 O(111) for the CO 2 reduction reaction (CO 2 RR) by combined density functional theory (DFT) calculations and experimental studies. We find that the surface hydroxy groups play a crucial role in the CO 2 RR and HER, and a moderate coverage of hydroxy groups is optimal for promotion of the CO 2 RR and suppression of the HER simultaneously. Electronic structure analysis indicates that the charge transfer from hydroxy groups to coordination-unsaturated Cu (Cu CUS ) sites stabilizes surface-adsorbed COOH*, which is a key intermediate during the CO 2 RR. Moreover, the CO 2 RR was evaluated over Cu 2 O octahedral catalysts with {111} facets and different surface coverages of hydroxy groups, which demonstrates that Cu 2 O octahedra with moderate coverage of hydroxy groups can indeed enhance the CO 2 RR and suppress the HER. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Antinociceptive effect of 7-hydroxy-3,4-dihydrocadalin isolated from Heterotheca inuloides: role of peripheral 5-HT₁ serotonergic receptors.

PubMed

Rocha-González, Héctor Isaac; Blaisdell-López, Everardo; Granados-Soto, Vinicio; Navarrete, Andrés

2010-12-15

The purpose of this study was to investigate the possible antinociceptive effect of Heterotheca inuloides in inflammatory pain and to identify the main compounds involved in this effect. Dose-response curves were obtained for hexane, dichlorometane, ethyl acetate and methanol extracts from Heterotheca inuloides inflorescences in the formalin test. Hexane extract was more potent and effective than other extracts. Bio-guided fractionation was performed to determine the main antinociceptive compounds of the plant. Gas chromatography-mass spectrometry technique demonstrated the composition of the most active fraction from hexane extract revealing the presence of caryophyllene oxide, cedrene, 7-hydroxy-3,4-dihydrocadalin, 7-hydroxycadalene and a compound not identified. The isolated compounds were individually evaluated in the formalin test in a preliminary dose of 100 μg/paw and only 7-hydroxy-3,4-dihydrocadalin showed a significant antinociceptive effect. Dose-response curves were then obtained for 7-hydroxy-3,4-dihydrocadalin and diclofenac, a prototypical analgesic drug. Both drugs were equieffective and equipotent in the second phase of the formalin test, but 7-hydroxy-3,4-dihydrocadalin was more effective and potent in the first phase than diclofenac. In addition, 7-hydroxy-3,4-dihydrocadalin reduced carrageenan-induced mechanical hyperalgesia and inflammation in a dose-dependent manner. Finally, in mechanistic studies, the antinociceptive effect of 7-hydroxy-3,4-dihydrocadalin in the formalin test was prevented by methiothepin, WAY100635, SB224289 and BRL15572 but not by naltrexone. Results support the use of H. inuloides inflorescences as analgesic in the Mexican traditional medicine. Moreover, data indicate that 7-hydroxy-3,4-dihydrocadalin is partly responsible of this pharmacological activity, and suggest that 5-HT(1A), 5-HT(1B), and 5-HT(1D) serotonergic, but not opioid, receptors participate in the antinociceptive effect of this drug. Copyright © 2010 Elsevier B.V. All rights reserved.

Comprehensive Analysis of Tiamulin Metabolites in Various Species of Farm Animals Using Ultra-High-Performance Liquid Chromatography Coupled to Quadrupole/Time-of-Flight.

PubMed

Sun, Feifei; Yang, Shupeng; Zhang, Huiyan; Zhou, Jinhui; Li, Yi; Zhang, Jinzhen; Jin, Yue; Wang, Zhanhui; Li, Yanshen; Shen, Jianzhong; Zhang, Suxia; Cao, Xingyuan

2017-01-11

Tiamulin is an antimicrobial widely used in veterinary practice to treat dysentery and pneumonia in pigs and poultry. However, knowledge about the metabolism of tiamulin is very limited in farm animals. To better understand the biotransformation of tiamulin, in the present study, in vitro and in vivo metabolites of tiamulin in rats, chickens, swine, goats, and cows were identified and elucidated using ultra-high performance liquid chromatography coupled to quadrupole/time-of-flight. As a result, a total of 26 metabolites of tiamulin, identified in vitro and in vivo, and majority of metabolites were revealed for the first time. In all farm animals, tiamulin undergoes phase I metabolic routes of hydroxylation in the mutilin part (the ring system), S-oxidation and N-deethylation on side chain, and no phase II metabolite was detected. Among these, 2β- and 8α-hydroxylation and N-deethylation were the main metabolic pathways of tiamulin in farm animals. In addition, we have put forward that 8a-hydroxy-tiamulin and 8a-hydroxy-N-deethyl-tiamulin could be hydroxylated into 8a-hydroxy-mutilin, the marker residue of tiamulin in swine. Furthermore, a significant interspecies difference was observed on the metabolism of tiamulin among various farm animals. The possible marker residues for tiamulin in swine were 8α-hydroxy-tiamulin, N-deethyl-tiamulin, and 8α-hydroxy-N-deethyl-tiamulin, which were consistent with the hypothesis proposed by the European Agency for the Evaluation of Medicinal Products. However, results in present study indicated that three metabolites (2β-hydroxy-tiamulin, N-deethyl-tiamulin, and 2β-hydroxy-N-deethyl-tiamulin) of tiamulin in chickens had larger yields, which implied that 2β-hydroxy-mutilin or N-deethyl-tiamulin was more likely to be regarded as the potential marker residue of tiamulin in chickens.

A key role for green rust in the Precambrian oceans and the genesis of iron formations

NASA Astrophysics Data System (ADS)

Halevy, I.; Alesker, M.; Schuster, E. M.; Popovitz-Biro, R.; Feldman, Y.

2017-01-01

Iron formations deposited in marine settings during the Precambrian represent large sinks of iron and silica, and have been used to reconstruct environmental conditions at the time of their formation. However, the observed mineralogy in iron formations, which consists of iron oxides, silicates, carbonates and sulfides, is generally thought to have arisen from diagenesis of one or more mineral precursors. Ferric iron hydroxides and ferrous carbonates and silicates have been identified as prime candidates. Here we investigate the potential role of green rust, a ferrous-ferric hydroxy salt, in the genesis of iron formations. Our laboratory experiments show that green rust readily forms in early seawater-analogue solutions, as predicted by thermodynamic calculations, and that it ages into minerals observed in iron formations. Dynamic models of the iron cycle further indicate that green rust would have precipitated near the iron redoxcline, and it is expected that when the green rust sank it transformed into stable phases within the water column and sediments. We suggest, therefore, that the precipitation and transformation of green rust was a key process in the iron cycle, and that the interaction of green rust with various elements should be included in any consideration of Precambrian biogeochemical cycles.

Pyrene–nucleobase conjugates: synthesis, oligonucleotide binding and confocal bioimaging studies

PubMed Central

Jabłoński, Artur; Fritz, Yannic; Wagenknecht, Hans-Achim; Czerwieniec, Rafał; Bernaś, Tytus; Trzybiński, Damian; Woźniak, Krzysztof

2017-01-01

Fluorescent pyrene–linker–nucleobase (nucleobase = thymine, adenine) conjugates with carbonyl and hydroxy functionalities in the linker were synthesized and characterized. X-ray single-crystal structure analysis performed for the pyrene–C(O)CH2CH2–thymine (2) conjugate reveals dimers of molecules 2 stabilized by hydrogen bonds between the thymine moieties. The photochemical characterization showed structure-dependent fluorescence properties of the investigated compounds. The conjugates bearing a carbonyl function represent weak emitters as compared to compounds with a hydroxy function in the linker. The self-assembly properties of pyrene nucleobases were investigated in respect to their binding to single and double strand oligonucleotides in water and in buffer solution. In respect to the complementary oligothymidine T10 template in water, compounds 3 and 5 both show a self-assembling behavior according to canonical base–base pairing. However, in buffer solution, derivative 5 was much more effective than 3 in binding to the T10 template. Furthermore the adenine derivative 5 binds to the double-stranded (dA)10–T10 template with a self-assembly ratio of 112%. Such a high value of a self-assembly ratio can be rationalized by a triple-helix-like binding, intercalation, or a mixture of both. Remarkably, compound 5 also shows dual staining pattern in living HeLa cells. Confocal microscopy confirmed that 5 predominantly stains mitochondria but it also accumulates in the nucleoli of the cells. PMID:29259662

Mechanism of oxidation of 3-hydroxy-2,7-naphthalenedisulfonic acid disodium salt with oxygen in subcritical water.

PubMed

Imbierowicz, Mirosław

2017-06-01

The article presents the results of studies on the oxidation mechanism of 3-hydroxy-2,7-naphthalenedisulfonic acid disodium salt (R-salt) with oxygen in subcritical water. To this aim, a series of experiments were carried out which showed that at a temperature of 413 K and pH > 9 the oxidation reaction of a substrate with oxygen was relatively quick and after approximately 40 min the R-salt oxidation yield exceeded 95%. In an acidic medium (pH < 7), the rate of R-salt oxidation is small. In order to identify the mechanism of R-salt oxidation, experiments were carried out at 413-569 K in solutions with pH = 10.0 and at partial oxygen pressure p O2  = 1.73 MPa. As a result of these experiments, a stable oxidation product was isolated from the reaction mixture and subjected to spectroscopic analysis. The analysis of H NMR of this product proved that a stable intermediate product of R-salt oxidation was 4-sulfophthalic acid sodium salt. The results of the experiments have shown that destructive oxidation of R-salt can easily be obtained at a temperature of 413 K, but satisfactory reduction of TOC in wastewater containing this substrate requires the use of very high temperature: at 569 K only 60% reduction of TOC was achieved. Copyright © 2017 Elsevier Ltd. All rights reserved.

Adsorption of bis(2-hydroxy-3-chloropropyl) dodecylamine on quartz surface and its implication on flotation

NASA Astrophysics Data System (ADS)

Liu, Wengang; Liu, Wenbao; Dai, Shujuan; Wang, Benying

2018-06-01

In order to clarify the effect of polar group modification on flotation performance of amine collector, flotation properties of quartz and hematite using bis(2-hydroxy-3-chloropropyl) dodecylamine (N23) as a collector were investigated. And the adsorption mechanism of N23 on quartz surface was established by zeta potential measurements, SEM/EDS measurements, and molecular structure analysis. Single mineral flotation results indicated that N23 showed stronger collecting ability on quartz and hematite than DDA-CH3COOH. However, starch could depress the flotation of hematite. Flotation recovery of 98.10% for quartz could be achieved, when N23 concentration was 43.33 mg/L and starch concentration was 16.67 mg/L at natural slurry pH. Separation of artificially mixed minerals of hematite and quartz was achieved effectively using N23 as the collector. The optimized separation result with 66.29% iron grade and 90.06% iron recovery in concentrate was obtained when slurry pH was 7.34 with 43.33 mg/L N23 and 23.33 mg/L starch. The interaction energies of N23 with mineral surface also showed well consistency with flotation results. SEM/EDS analyses and zeta potential measurements revealed that N23 could absorb on quartz surface in the forms of strong electrostatic and hydrogen bonding interaction. Compared with DDA, N23 had a higher HLB value and better water-solubility, which resulted in better dispersion in water and stronger adsorption on mineral surface.

Carbamoyl anion-initiated cascade reaction for stereoselective synthesis of substituted α-hydroxy-β-amino amides.

PubMed

Lin, Chao-Yang; Ma, Peng-Ju; Sun, Zhao; Lu, Chong-Dao; Xu, Yan-Jun

2016-01-18

A carbamoyl anion-initiated cascade reaction with acylsilanes and imines has been used to rapidly construct substituted α-hydroxy-β-amino amides. The Brook rearrangement-mediated cascade allows the formation of two C-C bonds and one O-Si bond in a single pot. Using this approach, a range of α-aryl α-hydroxy-β-amino amides has been synthesized in high yields with excellent diastereoselectivities.

40 CFR 721.10175 - 1-Propanaminium, N-(3-aminopropyl)-2-hydroxy-N,N-dimethyl-3-sulfo-, N-(C12-18 and C18-unsatd...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false 1-Propanaminium, N-(3-aminopropyl)-2... 1-Propanaminium, N-(3-aminopropyl)-2-hydroxy-N,N-dimethyl-3-sulfo-, N-(C12-18 and C18-unsatd. acyl... chemical substance identified as 1-Propanaminium, N-(3-aminopropyl)-2-hydroxy-N,N-dimethyl-3-sulfo-, N-(C12...

Efficient Domino Hydroformylation/Benzoin Condensation: Highly Selective Synthesis of α-Hydroxy Ketones.

PubMed

Dong, Kaiwu; Sang, Rui; Soule, Jean-Francois; Bruneau, Christian; Franke, Robert; Jackstell, Ralf; Beller, Matthias

2015-12-07

An improved domino hydroformylation/benzoin condensation to give α-hydroxy ketones has been developed. Easily available olefins are smoothly converted into the corresponding α-hydroxy ketones in high yields with excellent regioselectivities. Key to success is the use of a specific catalytic system consisting of a rhodium/phosphine complex and the CO2 adduct of an N-heterocyclic carbene. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of 2-Amino-3-hydroxy-3H-indoles via Palladium-Catalyzed One-Pot Reaction of Isonitriles, Oxygen, and N-Tosylhydrazones Derived from 2-Acylanilines.

PubMed

Chu, Haoke; Dai, Qiang; Jiang, Yan; Cheng, Jiang

2017-08-04

A cyanide-free one-pot procedure was developed to access 2-amino-3-hydroxy-3H-indoles, which involved: (1) in situ formation of ketenimines by the reaction of N'-(1-(2-aminophenyl)ethylidene)-p-tosylhydrazones with isonitriles; (2) the intramolecular nucleophilic attack of ketenimines by the amino in phenyl furnishing the ring closure leading to 2-aminoindoles; (3) the oxidation of 2-aminoindoles by O 2 leading to 2-amino-3-hydroxy-3H-indoles. This strategy represents not only a key compliment to the sporadic synthetic methods toward 2-amino-3-hydroxy-3H-indoles but also progress in N-tosylhydrazone, isonitrile, and ketenimine chemistry.

Characteristics and formation of amino acids and hydroxy acids of the Murchison meteorite

NASA Technical Reports Server (NTRS)

Cronin, J. R.; Cooper, G. W.; Pizzarello, S.

1995-01-01

Eight characteristics of the unique suite of amino acids and hydroxy acids found in the Murchison meteorite can be recognized on the basis of detailed molecular and isotopic analyses. The marked structural correspondence between the alpha-amino acids and alpha-hydroxy acids and the high deuterium/hydrogen ratio argue persuasively for their formation by aqueous phase Strecker reactions in the meteorite parent body from presolar, i.e., interstellar, aldehydes, ketones, ammonia, and hydrogen cyanide. The characteristics of the meteoritic suite of amino acids and hydroxy acids are briefly enumerated and discussed with regard to their consonance with this interstellar-parent body formation hypothesis. The hypothesis has interesting implications for the organic composition of both the primitive parent body and the presolar nebula.

Separation of cyclic lipopeptide puwainaphycins from cyanobacteria by countercurrent chromatography combined with polymeric resins and HPLC.

PubMed

Cheel, José; Urajová, Petra; Hájek, Jan; Hrouzek, Pavel; Kuzma, Marek; Bouju, Elodie; Faure, Karine; Kopecký, Jiří

2017-02-01

Puwainaphycins are a recently described group of β-amino fatty acid cyclic lipopeptides of cyanobacterial origin that possess interesting biological activities. Therefore, the development of an efficient method for their isolation from natural sources is necessary. Following the consecutive adsorption of the crude extract on Amberlite XAD-16 and XAD-7 resins, countercurrent chromatography (CCC) was applied to separate seven puwainaphycin variants from a soil cyanobacterium (Cylindrospermum alatosporum CCALA 988). The resin-enriched extract was first fractionated by CCC into fractions I and II with use of the n-hexane-ethyl acetate-ethanol-water (1:5:1:5, v/v/v/v) system at a flow rate of 2 mL min -1 and a rotational speed of 1400 rpm. The CCC separation of fraction I, with use of the ethyl acetate-ethanol-water (5:1:5, v/v/v) system, afforded compounds 1 and 2. The CCC separation of fraction II, with use of the n-hexane-ethyl acetate-ethanol-water (1:5:1:5, v/v/v/v) system, afforded compounds 3-7. In both cases, the lower phases were used as mobile phases at a flow rate of 1 mL min -1 with a rotational speed of 1400 rpm and a temperature of 28 °C. The CCC target fractions obtained were repurified by semipreparative high-performance liquid chromatography (HPLC), leading to compounds 1-7 with purities of 95 %, 95 %, 99 %, 99 %, 95 %, 99 %, and 90 % respectively, as determined by HPLC-electrospray ionization high-resolution mass spectrometry (ESI-HRMS). The chemical identity of the isolated puwainaphycins (compounds 1-7) was confirmed by ESI-HRMS and NMR analyses. Three new puwainaphycin variants (compounds 1, 2, and 5) are reported for the first time. This study provides a new approach for the isolation of puwainaphycins from cyanobacterial biomass. Graphical Abstract Separation of cyclic lipopeptide puwainaphycins from cyanobacteria by countercurrent chromatography combined with polymeric resins and HPLC. Compounds 1 (12-hydroxy-4-methyl-Ahtea-Puw-F), 2 (11-chloro-4-methyl-Ahdoa-Puw-F), 3 (4-methyl-Ahdoa-Puw-F), 4 (4-methyl-Ahdoa-Puw-G), 5 (12-chloro-4-methyl-Ahtea-Puw-F), 6 (4-methyl-Ahtea-Puw-F) and 7 (4-methyl-Ahtea-Puw-G). Ahtea: 3-amino-2-hydroxy tetradecanoic acid. Ahdoa: 3-amino-2-hydroxy dodecanoic acid.

Chitin based polyurethanes using hydroxyl terminated polybutadiene, part III: surface characteristics.

PubMed

Zia, Khalid Mahmood; Zuber, Mohammad; Saif, Muhammad Jawwad; Jawaid, Mohammad; Mahmood, Kashif; Shahid, Muhammad; Anjum, Muhammad Naveed; Ahmad, Mirza Nadeem

2013-11-01

Hydroxy terminated polybutadiene (HTPB)-chitin based polyurethanes (PUs) with controlled hydrophobicity were synthesized using HTPB and toluene diisocyanate (TDI). The prepolymer was extended with different mass ratios of chitin and 1,4-butane diol (BDO). The effect of chitin contents in chain extender (CE) proportions on surface properties was studied and investigated. Incorporation of chitin contents into the final PU showed decrease in contact angle value of water drop, water absorption (%) and swelling behavior. The antibacterial activity of the prepared samples was affected by varying the chitin contents in the chemical composition of the final PU. The results demonstrated that the use of prepared material can be suggested as non-absorbable suture. Copyright © 2013 Elsevier B.V. All rights reserved.

A 3-hydroxy β-end group in xanthophylls is preferentially oxidized to a 3-oxo ε-end group in mammals.

PubMed

Nagao, Akihiko; Maoka, Takashi; Ono, Hiroshi; Kotake-Nara, Eiichi; Kobayashi, Miyuki; Tomita, Mie

2015-02-01

We previously found that mice fed lutein accumulated its oxidative metabolites (3'-hydroxy-ε,ε-caroten-3-one and ε,ε-carotene-3,3'-dione) as major carotenoids, suggesting that mammals can convert xanthophylls to keto-carotenoids by the oxidation of hydroxyl groups. Here we elucidated the metabolic activities of mouse liver for several xanthophylls. When lutein was incubated with liver postmitochondrial fraction in the presence of NAD(+), (3'R,6'R)-3'-hydroxy-β,ε-caroten-3-one and (6RS,3'R,6'R)-3'-hydroxy-ε,ε-caroten-3-one were produced as major oxidation products. The former accumulated only at the early stage and was assumed to be an intermediate, followed by isomerization to the latter. The configuration at the C3' and C6' of the ε-end group in lutein was retained in the two oxidation products. These results indicate that the 3-hydroxy β-end group in lutein was preferentially oxidized to a 3-oxo ε-end group via a 3-oxo β-end group. Other xanthophylls such as β-cryptoxanthin and zeaxanthin, which have a 3-hydroxy β-end group, were also oxidized in the same manner as lutein. These keto-carotenoids, derived from dietary xanthophylls, were confirmed to be present in plasma of normal human subjects, and β,ε-caroten-3'-one was significantly increased by the ingestion of β-cryptoxanthin. Thus, humans as well as mice have oxidative activity to convert the 3-hydroxy β-end group of xanthophylls to a 3-oxo ε-end group. Copyright © 2015 by the American Society for Biochemistry and Molecular Biology, Inc.

A 3-hydroxy β-end group in xanthophylls is preferentially oxidized to a 3-oxo ε-end group in mammals[S

PubMed Central

Nagao, Akihiko; Maoka, Takashi; Ono, Hiroshi; Kotake-Nara, Eiichi; Kobayashi, Miyuki; Tomita, Mie

2015-01-01

We previously found that mice fed lutein accumulated its oxidative metabolites (3′-hydroxy-ε,ε-caroten-3-one and ε,ε-carotene-3,3′-dione) as major carotenoids, suggesting that mammals can convert xanthophylls to keto-carotenoids by the oxidation of hydroxyl groups. Here we elucidated the metabolic activities of mouse liver for several xanthophylls. When lutein was incubated with liver postmitochondrial fraction in the presence of NAD+, (3′R,6′R)-3′-hydroxy-β,ε-caroten-3-one and (6RS,3′R,6′R)-3′-hydroxy-ε,ε-caroten-3-one were produced as major oxidation products. The former accumulated only at the early stage and was assumed to be an intermediate, followed by isomerization to the latter. The configuration at the C3′ and C6′ of the ε-end group in lutein was retained in the two oxidation products. These results indicate that the 3-hydroxy β-end group in lutein was preferentially oxidized to a 3-oxo ε-end group via a 3-oxo β-end group. Other xanthophylls such as β-cryptoxanthin and zeaxanthin, which have a 3-hydroxy β-end group, were also oxidized in the same manner as lutein. These keto-carotenoids, derived from dietary xanthophylls, were confirmed to be present in plasma of normal human subjects, and β,ε-caroten-3′-one was significantly increased by the ingestion of β-cryptoxanthin. Thus, humans as well as mice have oxidative activity to convert the 3-hydroxy β-end group of xanthophylls to a 3-oxo ε-end group. PMID:25502844

A systems approach for discovering linoleic acid derivatives that potentially mediate pain and itch

PubMed Central

Ramsden, Christopher E.; Domenichiello, Anthony F.; Yuan, Zhi-Xin; Sapio, Matthew R.; Keyes, Gregory S.; Mishra, Santosh K.; Gross, Jacklyn R.; Majchrzak-Hong, Sharon; Zamora, Daisy; Horowitz, Mark S.; Davis, John M.; Sorokin, Alexander V.; Dey, Amit; LaPaglia, Danielle M.; Wheeler, Joshua J.; Vasko, Michael R.; Mehta, Nehal N.; Mannes, Andrew J.; Iadarola, Michael J.

2018-01-01

Chronic pain and itch are common hypersensitivity syndromes that are affected by endogenous mediators. We applied a systems-based, translational approach to predict, discover, and characterize mediators of pain and itch that are regulated by diet and inflammation. Profiling of tissue-specific precursor abundance and biosynthetic gene expression predicted that inflamed skin would be abundant in four previously unknown 11-hydroxy-epoxy-or 11-keto-epoxy-octadecenoate linoleic acid derivatives and four previously identified 9- or 13-hydroxy-epoxy- or 9- or 13-keto-epoxy-octadecenoate linoleic acid derivatives. All of these mediators were confirmed to be abundant in rat and human skin by mass spectrometry. However, only the two 11-hydroxy-epoxy-octadecenoates sensitized rat dorsal root ganglion neurons to release more calcitonin gene–related peptide (CGRP), which is involved in pain transmission, in response to low pH (which mimics an inflammatory state) or capsaicin (which activates ion channels involved in nociception). The two 11-hydroxy-epoxy-octadecenoates share a 3-hydroxy-Z-pentenyl-E-epoxide moiety, thus suggesting that this substructure could mediate nociceptor sensitization. In rats, intradermal hind paw injection of 11-hydroxy-12,13-trans-epoxy-(9Z)-octadecenoate elicited C-fiber–mediated sensitivity to thermal pain. In a randomized trial testing adjunctive strategies to manage refractory chronic headaches, reducing the dietary intake of linoleic acid was associated with decreases in plasma 11-hydroxy-12,13-trans-epoxy-(9Z)-octadecenoate, which correlated with clinical pain reduction. Human psoriatic skin had 30-fold higher 9-keto-12,13-trans-epoxy-(10E)-octadecenoate compared to control skin, and intradermal injection of this compound induced itch-related scratching behavior in mice. Collectively, these findings define a family of endogenous mediators with potential roles in pain and itch. PMID:28831021

3'-hydroxy-ε,ε-caroten-3-one inhibits the differentiation of 3T3-L1 cells to adipocytes.

PubMed

Kotake-Nara, Eiichi; Hase, Megumi; Kobayashi, Miyuki; Nagao, Akihiko

2016-01-01

An oxidative metabolite of lutein, 3'-hydroxy-ε,ε-caroten-3-one, inhibited the differentiation of 3T3-L1 cells to adipocytes and the subsequent triacylglycerol production, but lutein did not. The α,β-unsaturated carbonyl structure of 3'-hydroxy-ε,ε-caroten-3-one was considered to participate in the inhibitory effect, suggesting that this lutein metabolite has the potential to prevent metabolic syndrome.

40 CFR 721.9663 - Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis...

Code of Federal Regulations, 2012 CFR

2012-07-01

..., alphaâ²-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. 721... Substances § 721.9663 Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega...′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis(C11-15 and C11-15-isoalkyl) ethers (PMN P-97-497...

40 CFR 721.9663 - Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis...

Code of Federal Regulations, 2014 CFR

2014-07-01

..., alphaâ²-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. 721... Substances § 721.9663 Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega...′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis(C11-15 and C11-15-isoalkyl) ethers (PMN P-97-497...

40 CFR 721.9663 - Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis...

Code of Federal Regulations, 2013 CFR

2013-07-01

..., alphaâ²-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. 721... Substances § 721.9663 Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega...′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis(C11-15 and C11-15-isoalkyl) ethers (PMN P-97-497...

40 CFR 721.9663 - Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis...

Code of Federal Regulations, 2011 CFR

2011-07-01

..., alphaâ²-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. 721... Substances § 721.9663 Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega...′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis(C11-15 and C11-15-isoalkyl) ethers (PMN P-97-497...

40 CFR 721.9663 - Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis...

Code of Federal Regulations, 2010 CFR

2010-07-01

..., alphaâ²-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. 721... Substances § 721.9663 Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega...′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis(C11-15 and C11-15-isoalkyl) ethers (PMN P-97-497...

A mechanistic model for mercury capture with in situ-generated titania particles: role of water vapor.

PubMed

Rodríguez, Sylian; Almquist, Catherine; Lee, Tai Gyu; Furuuchi, Masami; Hedrick, Elizabeth; Biswas, Pratim

2004-02-01

A mechanistic model to predict the capture of gas-phase mercury (Hg) species using in situ-generated titania nanosize particles activated by UV irradiation is developed. The model is an extension of a recently reported model for photochemical reactions by Almquist and Biswas that accounts for the rates of electron-hole pair generation, the adsorption of the compound to be oxidized, and the adsorption of water vapor. The role of water vapor in the removal efficiency of Hg was investigated to evaluate the rates of Hg oxidation at different water vapor concentrations. As the water vapor concentration is increased, more hydroxy radical species are generated on the surface of the titania particle, increasing the number of active sites for the photooxidation and capture of Hg. At very high water vapor concentrations, competitive adsorption is expected to be important and reduce the number of sites available for photooxidation of Hg. The predictions of the developed phenomenological model agreed well with the measured Hg oxidation rates in this study and with the data on oxidation of organic compounds reported in the literature.

New cryptotanshinone derivatives with anti-influenza A virus activities obtained via biotransformation by Mucor rouxii.

PubMed

He, Wenni; Li, Yao; Qin, Yuejie; Tong, Xiaomei; Song, Zhijun; Zhao, Yu; Wei, Ran; Li, Li; Dai, Huanqin; Wang, Wenzhao; Luo, Houwei; Ye, Xin; Zhang, Lixin; Liu, Xueting

2017-08-01

This paper provides an efficient platform to diversify the structure and pharmaceutical potentials of known natural products. Seven metabolites were obtained via the biotransformation of cryptotanshinone by the fungus Mucor rouxii AS 3.3447, and assigned as 13R-14R-hydroxy-anhydride of 16R-cryptotanshinone (1), 1S-hydroxy-anhydride of 16R-cryptotanshinone (2), 1R-hydroxy-anhydride of 16R-cryptotanshinone (3), 3S-hydroxy-epicryptoacetalide (4), 3S-hydroxy-cryptoacetalide (5), epicryptoacetalide (6), and cryptoacetalide (7). Among these compounds, 1-5 are novel. The ortho-naphthoquinone chromophore of cryptotanshinone was degraded and rearranged by M. rouxii. 1 and 3 showed good anti-influenza A virus activities with the reduced cytotoxic activities compared to the parent substrate cryptotanshinone (8). The structures of all the new compounds were determined on the basis of HRESIMS (high-resolution electrospray ionization mass spectroscopy) spectrometry, NMR (nuclear magnetic resonance) spectroscopy, ECD (electronic circular dichroism) calculations, and the CD (circular dichroism) of "in situ" method with [Rh 2 (OCOCF 3 ) 4 ].

Hydroxy fatty acids in fresh snow samples from northern Japan: long-range atmospheric transport of Gram-negative bacteria by Asian winter monsoon

NASA Astrophysics Data System (ADS)

Tyagi, P.; Yamamoto, S.; Kawamura, K.

2015-08-01

Hydroxy fatty acids (FAs) in fresh snow from Sapporo, one of the heaviest snowfall regions in the world, have been studied to ascertain the airborne bacterial endotoxin concentrations and their biomass. The presence of β-hydroxy FAs (C9-C28), constituents of Gram-negative bacteria (GNB), suggests long-range transport of soil microbes. Likewise, the occurrence of α- and ω-hydroxy FAs (C9-C30 and C9-C28, respectively) in snow reveals their contribution from epicuticular waxes and soil microorganisms. Estimated endotoxin and GNB mass can aid in assessing their possible impacts on the diversity and functioning of aquatic and terrestrial ecosystems, as well as lethal effects on pedestrians through dispersal of microbes. Air mass back trajectories together with hydroxy FAs unveil their sources from Siberia, Russian Far East and North China by the Asian monsoon. This study highlights the role of fresh snow that reduces the human health risk of GNB and endotoxin by scavenging from the air.

Hydroxy fatty acids in fresh snow samples from northern Japan: long-range atmospheric transport of Gram-negative bacteria by Asian winter monsoon

NASA Astrophysics Data System (ADS)

Tyagi, P.; Yamamoto, S.; Kawamura, K.

2015-12-01

Hydroxy fatty acids (FAs) in fresh snow from Sapporo, one of the heaviest snowfall regions in the world, have been studied to ascertain the airborne bacterial endotoxin concentrations and their biomass. The presence of β-hydroxy FAs (C9-C28), constituents of the Gram-negative bacterium (GNB), suggests long-range transport of soil microbes. Likewise, the occurrence of α- and ω-hydroxy FAs (C9-C30 and C9-C28, respectively) in snow reveals their contribution from epicuticular waxes and soil microorganisms. Estimated endotoxin and GNB mass can aid in assessing their possible impacts on the diversity and functioning of aquatic and terrestrial ecosystems, as well as lethal effects on pedestrians through dispersal of microbes. Air mass back trajectories together with hydroxy FAs reveal their sources from Siberia, the Russian Far East and northern China by the Asian monsoon. This study highlights the role of fresh snow that reduces the human health risk of GNB and endotoxin by the scavenging from air.

Synthesis and Biological Evaluation of 2-Hydroxy-3-[(2-aryloxyethyl)amino]propyl 4-[(Alkoxycarbonyl)amino]benzoates

PubMed Central

Tengler, Jan; Kapustíková, Iva; Peško, Matúš; Keltošová, Stanislava; Mokrý, Petr; Kollár, Peter; O'Mahony, Jim; Král'ová, Katarína; Jampílek, Josef

2013-01-01

A series of twenty substituted 2-hydroxy-3-[(2-aryloxyethyl)amino]propyl 4-[(alkoxycarbonyl)amino]benzoates were prepared and characterized. As similar compounds have been described as potential antimycobacterials, primary in vitro screening of the synthesized carbamates was also performed against two mycobacterial species. 2-Hydroxy-3-[2-(2,6-dimethoxyphenoxy)ethylamino]-propyl 4-(butoxycarbonylamino)benzoate hydrochloride, 2-hydroxy-3-[2-(4-methoxyphenoxy)ethylamino]-propyl 4-(butoxycarbonylamino)benzoate hydrochloride, and 2-hydroxy-3-[2-(2-methoxyphenoxy)ethylamino]-propyl 4-(butoxycarbonylamino)benzoate hydrochloride showed higher activity against M. avium subsp. paratuberculosis and M. intracellulare than the standards ciprofloxacin, isoniazid, or pyrazinamide. Cytotoxicity assay of effective compounds was performed using the human monocytic leukaemia THP-1 cell line. Compounds with predicted amphiphilic properties were also tested for their effects on the rate of photosynthetic electron transport (PET) in spinach (Spinacia oleracea L.) chloroplasts. All butyl derivatives significantly stimulated the rate of PET, indicating that the compounds can induce conformational changes in thylakoid membranes resulting in an increase of their permeability and so causing uncoupling of phosphorylation from electron transport. PMID:24288475

Isolation and Pharmacological Evaluation of Minor Cannabinoids from High-Potency Cannabis sativa.

PubMed

Radwan, Mohamed M; ElSohly, Mahmoud A; El-Alfy, Abir T; Ahmed, Safwat A; Slade, Desmond; Husni, Afeef S; Manly, Susan P; Wilson, Lisa; Seale, Suzanne; Cutler, Stephen J; Ross, Samir A

2015-06-26

Seven new naturally occurring hydroxylated cannabinoids (1-7), along with the known cannabiripsol (8), have been isolated from the aerial parts of high-potency Cannabis sativa. The structures of the new compounds were determined by 1D and 2D NMR spectroscopic analysis, GC-MS, and HRESIMS as 8α-hydroxy-Δ(9)-tetrahydrocannabinol (1), 8β-hydroxy-Δ(9)-tetrahydrocannabinol (2), 10α-hydroxy-Δ(8)-tetrahydrocannabinol (3), 10β-hydroxy-Δ(8)-tetrahydrocannabinol (4), 10α-hydroxy-Δ(9,11)-hexahydrocannabinol (5), 9β,10β-epoxyhexahydrocannabinol (6), and 11-acetoxy-Δ(9)-tetrahydrocannabinolic acid A (7). The binding affinity of isolated compounds 1-8, Δ(9)-tetrahydrocannabinol, and Δ(8)-tetrahydrocannabinol toward CB1 and CB2 receptors as well as their behavioral effects in a mouse tetrad assay were studied. The results indicated that compound 3, with the highest affinity to the CB1 receptors, exerted the most potent cannabimimetic-like actions in the tetrad assay, while compound 4 showed partial cannabimimetic actions. Compound 2, on the other hand, displayed a dose-dependent hypolocomotive effect only.

Thermodynamic Signature of DNA Damage: Characterization of DNA with a 5-Hydroxy-2'-deoxycytidine•2'-Deoxyguanosine Base Pair

PubMed Central

Ganguly, Manjori; Szulik, Marta W.; Donahue, Patrick S.; Clancy, Kate; Stone, Michael P.; Gold, Barry

2012-01-01

Oxidation of DNA due to exposure to reactive oxygen species is a major source of DNA damage. One of the oxidation lesions formed, 5-hydroxy-2'-deoxycytidine, has been shown to miscode by some replicative DNA polymerases but not by error prone polymerases capable of translesion synthesis. The 5-hydroxy-2'-deoxycytidine lesion is repaired by DNA glycosylases that require the 5-hydroxycytidine base to be extrahelical so it can enter into the enzyme's active site where it is excised off the DNA backbone to afford an abasic site. The thermodynamic and NMR results presented herein, describe the effect of a 5-hydroxy-2'-deoxycytidine•2'-deoxyguanosine base pair on the stability of two different DNA duplexes. The results demonstrate that the lesion is highly destabilizing and that the energy barrier for the unstacking of 5-hydroxy-2'-deoxycytidine from the DNA duplex may be low. This could provide a thermodynamic mode of adduct identification by DNA glycosylases that require the lesion to be extrahelical. PMID:22332945

Iron- and 4-hydroxy-2-alkylquinoline-containing periplasmic inclusion bodies of Pseudomonas aeruginosa: A chemical analysis

USGS Publications Warehouse

Royt, P.W.; Honeychuck, R.V.; Pant, R.R.; Rogers, M.L.; Asher, L.V.; Lloyd, J.R.; Carlos, W.E.; Belkin, H.E.; Patwardhan, S.

2007-01-01

Dark aggregated particles were seen on pellets of iron-rich, mid-logarithmic phase Pseudomonas aeruginosa. Transmission electron microscopy of these cells showed inclusion bodies in periplasmic vacuoles. Aggregated particles isolated from the spent medium of these cells contained iron as indicated by atomic absorption spectroscopy and by electron paramagnetic resonance spectroscopy that revealed Fe3+. Scanning electron microscopy/energy dispersive X-ray analysis of whole cells revealed the presence of iron-containing particles beneath the surface of the cell, indicating that the isolated aggregates were the intracellular inclusion bodies. Collectively, mass spectroscopy and nuclear magnetic resonance spectroscopy of the isolated inclusion bodies revealed the presence of 3,4-dihydroxy-2-heptylquinoline which is the Pseudomonas quinolone signaling compound (PQS) and an iron chelator; 4-hydroxy-2-heptylquinoline (pseudan VII), which is an iron chelator, antibacterial compound and precursor of PQS; 4-hydroxy-2-nonylquinoline (pseudan IX) which is an iron chelator and antibacterial compound; 4-hydroxy-2-methylquinoline (pseudan I), and 4-hydroxy-2-nonylquinoline N-oxide. ?? 2006 Elsevier Inc. All rights reserved.

Rapid identification of triterpenoid sulfates and hydroxy fatty acids including two new constituents from Tydemania expeditionis by LC-MS

PubMed Central

Zhang, Jian-Long; Kubanek, Julia; Hay, Mark E.; Aalbersberg, William; Ye, Wen-Cai; Jiang, Ren-Wang

2011-01-01

Tydemania expeditionis Weber-van Bosse (Udoteaceae) is a weakly calcified green alga. In the present paper, liquid chromatography coupled with photodiode array detection and electrospray mass spectrometry was developed to identify the fingerprint components. A total of four triterpenoid sulfates and three hydroxy fatty acids in the ethyl acetate fraction of the crude extract were structurally characterized on the basis of retention time, online UV spectrum and mass fragmentation pattern. Furthermore, detailed LC-MS analysis revealed two new hydroxy fatty acids, which were then prepared and characterized by extensive NMR analyses. The proposed method provides a scientific and technical platform for the rapid identification of triterpenoid sulfates and hydroxy fatty acids in similar marine algae and terrestrial plants. PMID:21915955

Corticosteroidogenesis in the toad Bufo arenarum H: evidence for a precursor role for an aldosterone 3 beta-hydroxy-5-ene analogue (3 beta, 11 beta, 21-trihydroxy-20-oxo-5-pregnen-18-al).

PubMed Central

Ceballos, N R; Shackleton, C H; Harnik, M; Cozza, E N; Gros, E G; Lantos, C P

1993-01-01

A material isolated following pregnenolone incubations with toad (Bufo arenarum) inter-renal tissue at 28 degrees C has been identified as a 3 beta-hydroxy-5-ene analogue of aldosterone (3 beta, 11 beta, 21-trihydroxy-20-oxo-5-pregnen-18-al). The initial identification was made by enzymic and m.s. methods, and structural confirmation was achieved through comparison with chemically synthesized authentic material. The relative efficacy of corticosterone, 18-hydroxycorticosterone and the 3 beta-hydroxy-5-ene aldosterone analogue as aldosterone precursors was evaluated. In the in vitro situation studied, the 3 beta-hydroxy-5-ene steroid was by far the best precursor. PMID:8503841

Corticosteroidogenesis in the toad Bufo arenarum H: evidence for a precursor role for an aldosterone 3 beta-hydroxy-5-ene analogue (3 beta, 11 beta, 21-trihydroxy-20-oxo-5-pregnen-18-al).

PubMed

Ceballos, N R; Shackleton, C H; Harnik, M; Cozza, E N; Gros, E G; Lantos, C P

1993-05-15

A material isolated following pregnenolone incubations with toad (Bufo arenarum) inter-renal tissue at 28 degrees C has been identified as a 3 beta-hydroxy-5-ene analogue of aldosterone (3 beta, 11 beta, 21-trihydroxy-20-oxo-5-pregnen-18-al). The initial identification was made by enzymic and m.s. methods, and structural confirmation was achieved through comparison with chemically synthesized authentic material. The relative efficacy of corticosterone, 18-hydroxycorticosterone and the 3 beta-hydroxy-5-ene aldosterone analogue as aldosterone precursors was evaluated. In the in vitro situation studied, the 3 beta-hydroxy-5-ene steroid was by far the best precursor.

Stereochemical Consequences of Vinylpyruvate Hydratase-Catalyzed Reactions.

PubMed

Johnson, William H; Stack, Tyler M M; Taylor, Stephanie M; Burks, Elizabeth A; Whitman, Christian P

2016-07-26

A stereochemical analysis has been carried out on two vinylpyruvate hydratases (VPH), which convert 2-hydroxy-2,4-pentadienoate to 2-keto-4S-hydroxypentanoate in meta-fission pathways. Bacterial strains with this pathway can use aromatic compounds as sole sources of energy and carbon. The analysis was carried out using the 5-methyl and 5-chloro derivatives of 2-hydroxy-2,4-pentadienoate with the enzymes from Pseudomonas putida mt-2 (Pp) and Leptothrix cholodnii SP-6 (Lc). In both organisms, VPH is in a complex with the preceding enzyme in the pathway, 4-oxalocrotonate decarboxylase (4-OD). In D2O, a deuteron is incorporated stereospecifically at the C-3 and C-5 positions of product by both Pp and Lc enzymes. Accordingly, the complexes generate (3S,5S)-3,5-[di-D]-2-keto-4S-hydroxyhexanoate and (3S,5R)-3,5-[di-D]-2-keto-4R-hydroxy-5-chloropentanoate (4R and 5R due to a priority numbering change). The substitution at C-5 (CH3 or Cl) or the source of the enzyme (Pp or Lc) does not change the stereochemical outcome. One mechanism that can account for the results is the ketonization of the 5-substituted dienol to the α,β-unsaturated ketone (placing a deuteron at C-5 in D2O), followed by the conjugate addition of water (placing a deuteron at C-3). The stereochemical outcome for VPH (from Pp and Lc) is the same as that reported for a related enzyme, 2-oxo-hept-4-ene-1,7-dioate hydratase, from Escherichia coli C. The combined observations suggest similar mechanisms for these three enzymes that could possibly be common to this group of enzymes.

Trace elements are associated with urinary 8-hydroxy-2'-deoxyguanosine level: a case study of college students in Guangzhou, China.

PubMed

Lu, Shaoyou; Ren, Lu; Fang, Jianzhang; Ji, Jiajia; Liu, Guihua; Zhang, Jianqing; Zhang, Huimin; Luo, Ruorong; Lin, Kai; Fan, Ruifang

2016-05-01

Many trace heavy elements are carcinogenic and increase the incidence of cancer. However, a comprehensive study of the correlation between multiple trace elements and DNA oxidative damage is still lacking. The aim of this study is to investigate the relationships between the body burden of multiple trace elements and DNA oxidative stress in college students in Guangzhou, China. Seventeen trace elements in urine samples were determined by inductively coupled plasma-mass spectrometry (ICP-MS). Urinary 8-hydroxy-2'-deoxyguanosine (8-OHdG), a biomarker of DNA oxidative stress, was also measured using liquid chromatography tandem mass spectrometer (LC-MS/MS). The concentrations of six essential elements including manganese (Mn), copper (Cu), nickel (Ni), selenium (Se), strontium (Sr), and molybdenum (Mo), and five non-essential elements including arsenic (As), cadmium (Cd), aluminum (Al), stibium (Sb), and thallium (Tl), were found to be significantly correlated with urinary 8-OHdG levels. Moreover, urinary levels of Ni, Se, Mo, As, Sr, and Tl were strongly significantly correlated with 8-OHdG (P < 0.01) concentration. Environmental exposure and dietary intake of these trace elements may play important roles in DNA oxidative damage in the population of Guangzhou, China.

Construction of a new Cu2+ coated wire ion selective electrode based on 2-((2-(2-(2-(2-hydroxy-5-methoxybenzylidene amino)phenyl)disufanyl)phenylimino)methyl)-4-methoxyphenol Schiff base.

PubMed

Shokrollahi, A; Abbaspour, A; Ghaedi, M; Haghighi, A Naghashian; Kianfar, A H; Ranjbar, M

2011-03-15

In this article a new coated platinum Cu(2+) ion selective electrode based on 2-((2-(2-(2-(2-hydroxy-5-methoxybenzylideneamino)phenyl)disufanyl)phenylimino) methyl)-4-methoxyphenol Schiff base (L(1)) as a new ionophore is described. This sensor has a wide linear range of concentration (1.2 × 10(-7)-1.0 × 10(-1) mol L(-1)) and a low detection limit of 9.8 × 10(-8) mol L(-1)of Cu(NO(3))(2). It has a Nernstian response with slope of 29.54 ± 1.62 mV decade(-1) and it is applicable in the pH range of 4.0-6.0 without any divergence in potential. The coated electrode has a short response time of approximately 9s and is stable at least for 3.5 months. The electrode shows a good selectivity for Cu(2+) ion toward a wide variety of metal ions. The proposed sensor was successfully applied for the determination of Cu(2+) ion in different real and environmental samples and as indicator electrode for potentiometric titration of Cu(2+) ion with EDTA. Copyright © 2010 Elsevier B.V. All rights reserved.

Quantification of four major metabolites of embryotoxic N-methyl- and N-ethyl-2-pyrrolidone in human urine by cooled-injection gas chromatography and isotope dilution mass spectrometry.

PubMed

Schindler, Birgit K; Koslitz, Stephan; Meier, Swetlana; Belov, Vladimir N; Koch, Holger M; Weiss, Tobias; Brüning, Thomas; Käfferlein, Heiko U

2012-04-17

N-Methyl- and N-ethyl-2-pyrollidone (NMP and NEP) are frequently used industrial solvents and were shown to be embryotoxic in animal experiments. We developed a sensitive, specific, and robust analytical method based on cooled-injection (CIS) gas chromatography and isotope dilution mass spectrometry to analyze 5-hydroxy-N-ethyl-2-pyrrolidone (5-HNEP) and 2-hydroxy-N-ethylsuccinimide (2-HESI), two newly identified presumed metabolites of NEP, and their corresponding methyl counterparts (5-HNMP, 2-HMSI) in human urine. The urine was spiked with deuterium-labeled analogues of these metabolites. The analytes were separated from urinary matrix by solid-phase extraction and silylated prior to quantification. Validation of this method was carried out by using both, spiked pooled urine samples and urine samples from 56 individuals of the general population with no known occupational exposure to NMP and NEP. Interday and intraday imprecision was better than 8% for all metabolites, while the limits of detection were between 5 and 20 μg/L depending on the analyte. The high sensitivity of the method enables us to quantify NMP and NEP metabolites at current environmental exposures by human biomonitoring.

A novel reaction-based fluorescent probe for the detection of cysteine in milk and water samples.

PubMed

Wang, Jialin; Wang, Hao; Hao, Yanfeng; Yang, Shaoxiang; Tian, Hongyu; Sun, Baoguo; Liu, Yongguo

2018-10-01

A novel fluorescent probe 3'-hydroxy-3-oxo-3H-spiro [isobenzofuran-1,9'-xanthene]-6'-yl-2,4-dinitrobenzenesulfonate (probe 1) was designed and synthesized as a visual sensor for the detection of cysteine levels in milk and water samples. The addition of cysteine to the solution of probe 1 resulted in an increase in fluorescence intensity and color change, from light yellow to yellow-green. The distinct color response indicated that probe 1 could be used as a visual sensor for cysteine. Cysteine can be detected quantitatively at concentrations between 0 and 400 μM and the detection limit of the fluorescence response to the probe was 6.5 μM. This suggests that probe 1 could be used as a signaling tool to determine the cysteine levels in samples, such as milk and water. Copyright © 2018 Elsevier Ltd. All rights reserved.

Hydration states of AFm cement phases

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

Baquerizo, Luis G., E-mail: luis.baquerizoibarra@holcim.com; Matschei, Thomas; Scrivener, Karen L.

2015-07-15

The AFm phase, one of the main products formed during the hydration of Portland and calcium aluminate cement based systems, belongs to the layered double hydrate (LDH) family having positively charged layers and water plus charge-balancing anions in the interlayer. It is known that these phases present different hydration states (i.e. varying water content) depending on the relative humidity (RH), temperature and anion type, which might be linked to volume changes (swelling and shrinkage). Unfortunately the stability conditions of these phases are insufficiently reported. This paper presents novel experimental results on the different hydration states of the most important AFmmore » phases: monocarboaluminate, hemicarboaluminate, strätlingite, hydroxy-AFm and monosulfoaluminate, and the thermodynamic properties associated with changes in their water content during absorption/desorption. This data opens the possibility to model the response of cementitious systems during drying and wetting and to engineer systems more resistant to harsh external conditions.« less

40 CFR 180.1281 - S-Abscisic Acid, (S)-5-(1-hydroxy-2,6,6-trimethyl-4-oxo-1-cyclohex-2-enyl)-3-methyl-penta-(2Z,4E...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 23 2010-07-01 2010-07-01 false S-Abscisic Acid, (S)-5-(1-hydroxy-2,6... Exemptions From Tolerances § 180.1281 S-Abscisic Acid, (S)-5-(1-hydroxy-2,6,6-trimethyl-4-oxo-1-cyclohex-2... from the requirement of a tolerance is established for residues of S-Abscisic Acid in or on all food...

Two new compounds from an endophytic fungus Pestalotiopsis heterocornis.

PubMed

Xing, Jian-Guang; Deng, Hui-Ying; Luo, Du-Qiang

2011-12-01

Two new compounds, 7-hydroxy-5-methoxy-4,6-dimethyl-7-O-α-L-rhamnosyl-phthalide and 7-hydroxy-5-methoxy-4,6-dimethyl-7-O-β-D-glucopyranosyl-phthalide, along with one known and related metabolite 7-hydroxy-5-methoxy-4,6-dimethylphthalide were isolated from the EtOAc extract of fermentation broth of an endophytic fungus Pestalotiopsis heterocornis. The structures of these compounds were elucidated on the basis of spectroscopic methods (UV, IR, HR-ESI-MS, 1D NMR, and 2D NMR).

Method for preparation of 7-hydroxy-1,2,3,4-tetrahydroquinoline from 1,2,3,4-tetrahydroquinoline

DOEpatents

Field, G.; Hammond, P.R.

1994-02-01

Methods for the efficient preparation of 7-hydroxy-1,2,3,4-tetrahydroquinoline include a first method in which the acylation of m-aminophenol obtains a lactam which is reduced to give the desired quinoline and a second method in which tetrahydroquinoline is nitrated and hydrogenated and then hydrolyzed to obtain the desire quinoline. 7-hydroxy-1,2,3,4-tetrahydroquinoline is used in the efficient synthesis of four lasing dyes of the rhodamine class.

2-Oxo promoted hydrophosphonylation & aerobic intramolecular nucleophilic displacement reaction.

PubMed

Battula, Satyanarayana; Battini, Narsaiah; Singh, Deepika; Ahmed, Qazi Naveed

2015-08-28

Highly efficient catalyst free methods for the synthesis of α-hydroxy-β-oxophosphonates and α-oxoesters have been described. The existence of a 2-oxo group in α-oxoaldehydes is a key factor in promoting the reaction of the tervalent phosphite form towards 2-oxoaldehydes in the synthesis of α-hydroxy-β-oxophosphonates. The in situ activated α-C-H atom of α-hydroxy-β-oxophosphonates sustains aerobic intramolecular nucleophilic displacement in a curious way to produce α-oxoester.

Method for preparation of 7-hydroxy-1,2,3,4-tetrahydroquinoline from 1,2,3,4-tetrahydroquinoline

DOEpatents

Field, George; Hammond, Peter R.

1994-01-01

Methods for the efficient preparation of 7-hydroxy-1,2,3,4-tetrahydroquinoline include a first method in which the acylation of m-aminophenol obtains a lactam which is reduced to give the desired quinoline and a second method in which tetrahydroquinoline is nitrated and hydrogenated and then hydrolyzed to obtain the desire quinoline. 7-hydroxy-1,2,3,4-tetrahydroquinoline is used in the efficient synthesis of four lasing dyes of the rhodamine class.

Process for the preparation of benozotriazoles and their polymers, and 2(2-hydroxy-5-isopropenylphenyl)2H-benzotriazole produced thereby

DOEpatents

Vogl, O.; Nir, Z.

1983-09-29

This invention relates to a process for the production of substituted benzotriazoles, particularly for the production of such substituted benzotriazoles which are useful as polymerizable ultraviolet light absorbers. The invention also relates to a new benzotriazole, 2(2-hydroxy-5-isopropenylphenyl)2H-benzotriazole, which is polymerizable ultraviolet light absorber, and its preparation, and to the preparation of 2(2-hydroxy-5-vinylphenyl)2H-benzotriazole, another polymerizable ultraviolet light absorber.

Hydroxylation of 10-deoxoartemisinin by Cunninghamella elegans.

PubMed

Parshikov, Igor A; Muraleedharan, Kannoth M; Miriyala, Bruhaspathy; Avery, Mitchell A; Williamson, John S

2004-09-01

The microbial metabolism of 10-deoxoartemisinin (1), a derivative of the antimalarial drug artemisinin, was investigated. Various strains of fungi were investigated for their ability to transform 1. Of these microorganisms, only Cunninghamella elegans was capable of transforming 1 to 5beta-hydroxy-10-deoxoartemisinin (2), 4alpha-hydroxy-1,10-deoxoartemisinin (3), and 7beta-hydroxy-10-deoxoartemisinin (4). The metabolites 2 and 4 retained an intact peroxide group and are therefore useful scaffolds for synthetic modification in the search for new antimalarial agents.

A library synthesis of 4-hydroxy-3-methyl-6-phenylbenzofuran-2-carboxylic acid ethyl ester derivatives as anti-tumor agents.

PubMed

Hayakawa, Ichiro; Shioya, Rieko; Agatsuma, Toshinori; Furukawa, Hidehiko; Naruto, Shunji; Sugano, Yuichi

2004-09-06

As a result of a hit-to-lead program using a technique of solution-phase parallel synthesis, a highly potent (2,4-dimethoxyphenyl)-[6-(3-fluorophenyl)-4-hydroxy-3-methylbenzofuran-2-yl]methanone (15b) was synthesized as an optimized derivative of 4-hydroxy-3-methyl-6-phenylbenzofuran-2-carboxylic acid ethyl ester (1), which was discovered as a screening hit from small-molecule libraries and exhibited selective cytotoxicity against a tumorigenic cell line.

Kinetic Resolution of α-Hydroxy-Substituted Oxime Ethers by Enantioselective Cu-H-Catalyzed Si-O Coupling.

PubMed

Dong, Xichang; Kita, Yuji; Oestreich, Martin

2018-04-12

A catalyst-controlled enantioselective alcohol silylation by Cu-H-catalyzed dehydrogenative Si-O coupling of hydroxy groups α to an oxime ether and simple hydrosilanes is reported. The selectivity factors reached in this kinetic resolution are generally high (s≈50), and these reactions thereby provide reliable access to highly enantioenriched α-hydroxy-substituted oxime ethers. The synthetic usefulness of these compounds is also demonstrated. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sleep-inducing N-alkyl-5-[m-(trifluoromethyl)phenyl]-5-hydroxy-2-pyrrolidinones and N-alkyl-3-(trifluoromethyl)cinnamamides.

PubMed

Houlihan, W J; Gogerty, J H; Ryan, E A; Schmitt, G

1985-01-01

A series of N-alkyl-3-[m-(trifluoromethyl)phenyl]-5-hydroxy-2-pyrrolidinones and N-alkyl-3-(trifluoromethyl)-cinnamamides were prepared and screened in a series of tests designed to detect potential sleep inducers. The more active members of the series were evaluated for their ability to induce sleep in Cebus monkeys. The most active compound, N-methyl-5-[m-(trifluoromethyl)phenyl]-5-hydroxy-2-pyrrolidinone, was equal to methaqualone.

A novel therapeutic effect of statins on nephrogenic diabetes insipidus

PubMed Central

Bonfrate, Leonilde; Procino, Giuseppe; Wang, David Q-H; Svelto, Maria; Portincasa, Piero

2015-01-01

Statins competitively inhibit hepatic 3-hydroxy-3-methylglutaryl-coenzyme A reductase, resulting in reduced plasma total and low-density lipoprotein cholesterol levels. Recently, it has been shown that statins exert additional ‘pleiotropic’ effects by increasing expression levels of the membrane water channels aquaporin 2 (AQP2). AQP2 is localized mainly in the kidney and plays a critical role in determining cellular water content. This additional effect is independent of cholesterol homoeostasis, and depends on depletion of mevalonate-derived intermediates of sterol synthetic pathways, i.e. farnesylpyrophosphate and geranylgeranylpyrophosphate. By up-regulating the expression levels of AQP2, statins increase water reabsorption by the kidney, thus opening up a new avenue in treating patients with nephrogenic diabetes insipidus (NDI), a hereditary disease that yet lacks high-powered and limited side effects therapy. Aspects related to water balance determined by AQP2 in the kidney, as well as standard and novel therapeutic strategies of NDI are discussed. PMID:25594563

Amelioration of oxidative stress-induced phenotype loss of parvalbumin interneurons might contribute to the beneficial effects of environmental enrichment in a rat model of post-traumatic stress disorder.

PubMed

Sun, Xiao R; Zhang, Hui; Zhao, Hong T; Ji, Mu H; Li, Hui H; Wu, Jing; Li, Kuan Y; Yang, Jian J

2016-10-01

Post-traumatic stress disorder (PTSD) is a common psychiatric disease following exposure to a severe traumatic event or physiological stress, which is characterized by anxiety- and depression-like behaviors and cognitive impairment. However, the underlying mechanisms remain elusive. Parvalbumin (PV) interneurons that are susceptible to oxidative stress are a subset of inhibitory GABAergic neurons regulating the excitability of pyramidal neurons, while dysfunction of PV interneurons is casually linked to many mental disorders including PTSD. We therefore hypothesized that environmental enrichment (EE), a method of enhanced cognitive, sensory and motor stimulation, can reverse the behavioral impairments by normalizing PV interneurons in a rat model of PTSD induced by inescapable foot shocks (IFS). Behavioral changes were determined by the open field, elevated plus maze, fear conditioning, and Morris water maze tests. The levels of nicotinamide adenosine dinucleotide phosphate (NADPH) oxidase 2 (NOX2), NOX4, PV, glutamic acid decarboxylase 67 (GAD-67), and 8-hydroxy-2-deoxyguanosine (8-OH-dG) in the hippocampus and prefrontal cortex were determined. Our results showed that in this PTSD model, rats displayed the anxiety-like behavior, enhanced fear learning behavior, and hippocampus- dependent spatial memory deficit, which were accompanied by the up-regulation of NOX2, 8-OH-dG, and down-regulation of PV and GAD-67. Notably, EE reversed all these abnormalities. These results suggest that restoration of PV interneurons by inhibiting oxidative stress in the hippocampus and prefrontal cortex might represent a mechanism through which EE reverses the behavioral impairments in a rat model of PTSD induced by IFS. Copyright © 2016 Elsevier B.V. All rights reserved.

One-Step Cationic Grafting of 4-Hydroxy-TEMPO and its Application in a Hybrid Redox Flow Battery with a Crosslinked PBI Membrane.

PubMed

Chang, Zhenjun; Henkensmeier, Dirk; Chen, Ruiyong

2017-08-24

By using a one-step epoxide ring-opening reaction between 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (4-hydroxy-TEMPO) and glycidyltrimethylammonium cation (GTMA + ), we synthesized a cation-grafted TEMPO (g + -TEMPO) and studied its electrochemical performance against a Zn 2+ /Zn anode in a hybrid redox flow battery. To conduct Cl - counter anions, a crosslinked methylated polybenzimidazole (PBI) membrane was prepared and placed between the catholyte and anolyte. Compared to 4-hydroxy-TEMPO, the positively charged g + - TEMPO exhibits enhanced reaction kinetics. Moreover, flow battery tests with g + -TEMPO show improved Coulombic, voltage, and energy efficiencies and cycling stability over 140 cycles. Crossover of active species through the membrane was not detected. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spiroborate Ester-Mediated Asymmetric Synthesis of β-Hydroxy Ethers and its Conversion to Highly Enantiopure β-Amino Ethers

PubMed Central

Huang, Kun; Ortiz-Marciales, Margarita; Correa, Wildeliz; Pomales, Edgardo; López, Xaira Y.

2009-01-01

Borane-mediated reduction of aryl and alkyl ketones with α-aryl- and α-pyridyloxy groups affords β-hydroxy ethers in high enantiomeric purity (up to 99% ee) and in good yield, using as catalyst 10 mol % of spiroborate ester 1 derived from (S)-diphenylprolinol. Representative β-hydroxy ethers are successfully converted to β-amino ethers, with minor epimerization, by phthalimide substitution under Mitsunobu’s conditions followed by hydrazinolysis, to obtain primary amino ethers or by imide reduction with borane to afford β-2,3-dihydro-1H-isoindol ethers. Non-racemic Mexiletine and nAChR analogues with potential biological activity are also synthesized in excellent yield by mesylation of key β-hydroxy pyridylethers and substitution with 5, 6 and 7 member ring heterocyclic amines. PMID:19413288

Simultaneous determination of four 5-hydroxy polymethoxyflavones by reversed-phase high performance liquid chromatography with electrochemical detection.

PubMed

Dong, Ping; Qiu, Peiju; Zhu, Yi; Li, Shiming; Ho, Chi-Tang; McClements, David Julian; Xiao, Hang

2010-01-29

Accumulating evidence has suggested the potential health-promoting effects of 5-hydroxy polymethoxyflavones (5-OH-PMFs) naturally existing in citrus genus. However, research efforts are hampered by the lack of reliable and sensitive methods for their determination in plant materials and biological samples. Using reversed-phase high performance liquid chromatography (HPLC) equipped with electrochemical (EC) detection, we have developed a fast and highly sensitive method for quantification of four 5-OH-PMFs, namely 5-hydroxy-6,7,8,3',4'-pentamethoxyflavone, 5-hydroxy-3,6,7,8,3',4'-hexamethoxyflavone, 5-hydroxy-6,7,4'-trimethoxyflavone, and 5-hydroxy-6,7,8,4'-tetramethoxyflavone. The method was fully validated in terms of linearity, accuracy and precision. The limit of detection (LOD) was determined as being between 0.65 and 1.8ng/mL (ppb), demonstrating an over 160 times higher sensitivity in comparison with the previously reported method using UV detection. The recovery rate of the method was between 96.17% and 110.82%, and the precision for the retention times and peak areas was all below 13%. The method was successfully used to quantify 5-OH-PMFs with a wide range of abundance in the citrus products and preparations, such as orange juice, citrus peel, and dried tangerine peel. The quantification method for 5-OH-PMFs developed herein could be useful for the nutritional and pharmacological studies of these compounds in future. Copyright (c) 2009 Elsevier B.V. All rights reserved.

A novel identification approach for discovery of 5-HydroxyTriptamine 2A antagonists: combination of 2D/3D similarity screening, molecular docking and molecular dynamics.

PubMed

Kumar, Rakesh; Jade, Dhananjay; Gupta, Dinesh

2018-03-05

5-HydroxyTriptamine 2A antagonists are potential targets for treatment of various cerebrovascular and cardiovascular disorders. In this study, we have developed and performed a unique screening pipeline for filtering ZINC database compounds on the basis of similarities to known antagonists to determine novel small molecule antagonists of 5-HydroxyTriptamine 2A. The screening pipeline is based on 2D similarity, 3D dissimilarity and a combination of 2D/3D similarity. The shortlisted compounds were docked to a 5-HydroxyTriptamine 2A homology-based model, and complexes with low binding energies (287 complexes) were selected for molecular dynamics (MD) simulations in a lipid bilayer. The MD simulations of the shortlisted compounds in complex with 5-HydroxyTriptamine 2A confirmed the stability of the complexes and revealed novel interaction insights. The receptor residues S239, N343, S242, S159, Y370 and D155 predominantly participate in hydrogen bonding. π-π stacking is observed in F339, F340, F234, W151 and W336, whereas hydrophobic interactions are observed amongst V156, F339, F234, V362, V366, F340, V235, I152 and W151. The known and potential antagonists shortlisted by us have similar overlapping molecular interaction patterns. The 287 potential 5-HydroxyTriptamine 2A antagonists may be experimentally verified.

Mechanism of atropine-resistant contraction induced by Dai-kenchu-to in guinea pig ileum.

PubMed

Satoh, K; Hashimoto, K; Hayakawa, T; Ishige, A; Kaneko, M; Ogihara, S; Kurosawa, S; Yakabi, K; Nakamura, T

2001-05-01

To clarify the contractile mechanism of Dai-kenchu-to, the effects of hydroxy beta-sanshool (an ingredient of Zanthoxylum fruit), Zanthoxylum fruit (a constituent herb of Dai-kenchu-to) and Dai-kenchu-to were studied in mucosa-free longitudinal muscle of guinea pig ileum. Hydroxy beta-sanshool at 10(-7)-10(-5) g/ml induced dose-related contractions accompanied by autonomous contraction and produced an initial contraction at a concentration of 10(-4) g/ml or more. The contraction induced by hydroxy beta-sanshool (10(-5) g/ml) was significantly inhibited by tetrodotoxin or the capsaicin-receptor antagonist capsazepine. Although atropine or the substance P antagonist spantide tended to inhibit the contraction, a combination of atropine and spantide almost abolished the contraction by hydroxy beta-sanshool. The P2-purinoceptor antagonist pyridoxal-phosphate-6-azophenyl-2',4'-disulphonic acid did not affect hydroxy beta-sanshool-induced contraction in the presence or absence of spantide. The tonic contractions by Zanthoxylum fruit (2 x 10(-4) g/ml) and Dai-kenchu-to (10(-3) g/ml) were significantly inhibited or tended to be inhibited by atropine, spantide, tetrodotoxin or capsazepine and were remarkably suppressed by the combination of atropine and spantide. These results suggested that acetylcholine release from intrinsic cholinergic nerves and tachykinins from sensory neurons are involved in the contractions induced by hydroxy beta-sanshool and that tachykinins may be involved in the atropine-resistant contraction by Dai-kenchu-to.

Newly-synthesized chalcones-inhibition of adherence and biofilm formation of methicillin-resistant Staphylococcus aureus

PubMed Central

Bozic, Dragana D.; Milenkovic, Marina; Ivkovic, Branka; Cirkovic, Ivana

2014-01-01

Biofilm formation and adherence of bacteria to host tissue are one of the most important virulence factors of methicillin-resistant strains of Staphylococcus aureus (MRSA). The number of resistant strains is seriously increasing during the past years and bacteria have become resistant, not only to methicillin, but also to other commonly used antistaphylococcal antibiotics. There is a great need for discovering a novel antimicrobial agent for the treatment of staphylococcal infections. One of the most promising groups of compounds appears to be chalcones. In present study we evaluated the in vitro effect of three newly synthesized chalcones: 1,3- Bis-(2-hydroxy-phenyl)-propenone, 3-(3-Hydroxy-phenyl)-1-(2-hydroxy-phenyl)-propenone and 3-(4-Hydroxy-phenyl)-1-(2-hydroxy-phenyl)-propenone on glycocalyx production, biofilm formation and adherence to human fibronectin of clinical isolates and laboratory control strain of MRSA (ATCC 43300). Subinhibitory concentrations of the tested compounds reduced the production of glycocalyx, biofilm formation and adherence to human fibronectin of all MRSA strains. Inhibition of biofilm formation was dose dependent and the most effective was 1,3- Bis-(2-hydroxy-phenyl)-propenone. In our study we demonstrated that three newly-synthesized chalcones exhibited significant effect on adherence and biofilm formation of MRSA strains. Chalcones may be considered as promising new antimicrobial agents that can be used for prevention of staphylococcal infections or as adjunct to antibiotics in conventional therapy. PMID:24948943

In vitro metabolism of a novel synthetic cannabinoid, EAM-2201, in human liver microsomes and human recombinant cytochrome P450s.

PubMed

Kim, Ju Hyun; Kim, Hee Seung; Kong, Tae Yeon; Lee, Joo Young; Kim, Jin Young; In, Moon Kyo; Lee, Hye Suk

2016-02-05

In vitro metabolism of a new synthetic cannabinoid, EAM-2201, has been investigated with human liver microsomes and major cDNA-expressed cytochrome P450 (CYP) isozymes using liquid chromatography-high resolution mass spectrometry (LC-HRMS). Incubation of EAM-2201 with human liver microsomes in the presence of NADPH resulted in the formation of 37 metabolites, including nine hydroxy-EAM-2201 (M1-M9), five dihydroxy-EAM-2201 (M10-M14), dihydrodiol-EAM-2201 (M15), oxidative defluorinated EAM-2201 (M16), two hydroxy-M16 (M17 and M18), three dihydroxy-M16 (M19-M21), N-dealkyl-EAM-2201 (M22), two hydroxy-M22 (M23 and M24), dihydroxy-M22 (M25), EAM-2201 N-pentanoic acid (M26), hydroxy-M26 (M27), dehydro-EAM-2201 (M28), hydroxy-M28 (M29), seven dihydroxy-M28 (M30-M36), and oxidative defluorinated hydroxy-M28 (M37). Multiple CYPs, including CYP1A2, 2B6, 2C8, 2C9, 2C19, 2D6, 2J2, 3A4, and 3A5, were involved in the metabolism of EAM-2201. In conclusion, EAM-2201 is extensively metabolized by CYPs and its metabolites can be used as an indicator of EAM-2201 abuse. Copyright © 2015 Elsevier B.V. All rights reserved.

Degradation of phenanthrene by Burkholderia sp. C3: initial 1,2- and 3,4-dioxygenation and meta- and ortho-cleavage of naphthalene-1,2-diol.

PubMed

Seo, Jong-Su; Keum, Young-Soo; Hu, Yuting; Lee, Sung-Eun; Li, Qing X

2007-02-01

Burkholderia sp. C3 was isolated from a polycyclic aromatic hydrocarbon (PAH)-contaminated site in Hilo, Hawaii, USA, and studied for its degradation of phenanthrene as a sole carbon source. The initial 3,4-C dioxygenation was faster than 1,2-C dioxygenation in the first 3-day culture. However, 1-hydroxy-2-naphthoic acid derived from 3,4-C dioxygenation degraded much slower than 2-hydroxy-1-naphthoic acid derived from 1,2-C dioxygenation. Slow degradation of 1-hydroxy-2-naphthoic acid relative to 2-hydroxy-1-naphthoic acid may trigger 1,2-C dioxygenation faster after 3 days of culture. High concentrations of 5,6- and 7,8-benzocoumarins indicated that meta-cleavage was the major degradation mechanism of phenanthrene-1,2- and -3,4-diols. Separate cultures with 2-hydroxy-1-naphthoic acid and 1-hydroxy-2-naphthoic acid showed that the degradation rate of the former to naphthalene-1,2-diol was much faster than that of the latter. The two upper metabolic pathways of phenanthrene are converged into naphthalene-1,2-diol that is further metabolized to 2-carboxycinnamic acid and 2-hydroxybenzalpyruvic acid by ortho- and meta-cleavages, respectively. Transformation of naphthalene-1,2-diol to 2-carboxycinnamic acid by this strain represents the first observation of ortho-cleavage of two rings-PAH-diols by a Gram-negative species.

Biological and nonbiological modifications of carbamates

PubMed Central

Knaak, James B.

1971-01-01

Methylcarbamate insecticides undergo hydrolysis, oxidation, dealkylation, and conjugation in animals, plants, and insects to form similar or identical products. Carbaryl is hydroxylated in biological systems to form hydroxy, dihydro-dihydroxy, and N-hydroxymethyl carbaryl and is hydrolysed to form 1-naphthol. The products are conjugated, stored, or excreted. Carbofuran is hydroxylated at the 3 position and propoxur at the 5 position to form hydroxylated derivatives. N-hydroxymethyl derivatives of these two carbamates may also be formed. Hydrolysis appears to be the major metabolic pathway of carbofuran in the animal. Aldicarb is oxidized to its sulfoxide and then hydrolysed to the oxime sulfoxide in animals and plants. Plants hydrolyse the oxime sulfoxide to form the corresponding aldehyde, which is an intermediate in the formation of 2-methyl-2-(methyl-sulfinyl)propanol. Methomyl, which is structurally similar to aldicarb, is metabolized in plants to acetonitrile, carbon dioxide, and methylamine. Bux and Meobal undergo hydrolysis and hydroxylation to form N-hydroxy methylcarbamates, as well as hydroxybutylphenyl and hydroxymethylphenyl methylcarbamates. Zectran, which contains a dimethylamino group, is converted to the methylamino, amino, and methylformamido derivatives by insects and plants. In soil and water, methylcarbamate insecticides are hydrolysed to their respective phenols or oximes. PMID:4999481

Characterization and evaluation of an oral microemulsion containing the antitumor diterpenoid compound ent-11alpha-hydroxy-15-oxo-kaur-16-en-19-oic-acid

PubMed Central

Lu, Yingnian; Wu, Kefeng; Li, Li; He, Yuhui; Cui, Liao; Liang, Nianci; Mu, Bozhong

2013-01-01

The objective of this study was to develop an oral microemulsion formulation of the antitumor diterpenoid agent, ent-11α-hydroxy-15-oxo-kaur-16-en-19-oic-acid (henceforth referred to as 5F), to enhance its bioavailability and evaluate its hepatotoxicity. Pseudoternary phase diagrams showed that the optimal microemulsion formulation contained 45% water, 10% castor oil as the oil phase, 15% Cremophor EL as the surfactant, and 30% as a cosurfactant mixture of 1,2-propanediol and polyethylene glycol (PEG)-400 (2:1, w/w). The microemulsion preparation was characterized and its droplet diameter was within 50 nm. Release of 5F in vitro from the microemulsion was slightly increased compared with a suspension containing the same amount of active drug. Pharmacokinetic parameters in vivo indicated that bioavailability was markedly improved, with the relative bioavailability being 616.15% higher for the microemulsion than for the suspension. Toxicity tests showed that the microemulsion had no hepatotoxicity in mice. These results suggest the potential for 5F microemulsion to be administered by the oral route. PMID:23690685

Crystal structures of monoamine oxidase B in complex with four inhibitors of the N-propargylaminoindan class.

PubMed

Binda, Claudia; Hubálek, Frantisek; Li, Min; Herzig, Yaacov; Sterling, Jeffrey; Edmondson, Dale E; Mattevi, Andrea

2004-03-25

Monoamine oxidase B (MAO B) is an outer mitochondrial membrane enzyme that catalyzes the oxidation of arylalkylamine neurotransmitters. The crystal structures of MAO B in complex with four of the N-propargylaminoindan class of MAO covalent inhibitors (rasagiline, N-propargyl-1(S)-aminoindan, 6-hydroxy-N-propargyl-1(R)-aminoindan, and N-methyl-N-propargyl-1(R)-aminoindan) have been determined at a resolution of better than 2.1 A. Rasagiline, 6-hydroxy-N-propargyl-1(R)-aminoindan, and N-methyl-N-propargyl-1(R)-aminoindan adopt essentially the same conformation with the extended propargyl chain covalently bound to the flavin and the indan ring located in the rear of the substrate cavity. N-Propargyl-1(S)-aminoindan binds with the indan ring in a flipped conformation with respect to the other inhibitors, which causes a slight movement of the Tyr326 side chain. Four ordered water molecules are an integral part of the active site and establish H-bond interactions to the inhibitor atoms. These structural studies may guide future drug design to improve selectivity and efficacy by introducing appropriate substituents on the rasagiline molecular scaffold.

Identification of novel orosensory active molecules in cured vanilla Beans (Vanilla planifolia).

PubMed

Schwarz, Bernd; Hofmann, Thomas

2009-05-13

Sequential application of solvent extraction, gel permeation chromatography, and HPLC in combination with taste dilution analyses, followed by LC-MS and 1D/2D NMR experiments, led to the discovery of seven velvety mouth-coating molecules in cured beans of Vanilla planifolia . Among these, 5-(4-hydroxybenzyl)vanillin, 4-(4-hydroxybenzyl)-2-methoxyphenol, 4-hydroxy-3-(4-hydroxy-3-methoxybenzyl)-5-methoxybenzaldehyde, (1-O-vanilloyl)-(6-O-feruloyl)-beta-d-glucopyranoside, americanin A, and 4',6'-dihydroxy-3',5-dimethoxy-[1,1'-biphenyl]-3-carboxaldehyde were previously not reported in vanilla beans. Sensory studies revealed human recognition thresholds for the velvety mouth-coating sensation between 1.0 and 5.0 mumol/kg (water). Interestingly, the biphenyl derivatives were found to enhance the perception of creaminess and fatty body of sweetened skim milk, among which 4',6'-dihydroxy-3',5-dimethoxy-[1,1'-biphenyl]-3-carboxaldehyde showed the lowest threshold level of 5 mumol/kg. Quantitative analysis of these compounds in cured vanilla beans from different origins as well as in noncured beans revealed that, with the exception of americanin A, all of the other taste compounds are not present in the green vanilla beans and are formed during the bean curing process.

Biodegradation improvement of poly(3-hydroxy-butyrate) films by entomopathogenic fungi and UV-assisted surface functionalization.

PubMed

Kessler, Felipe; Marconatto, Leticia; Rodrigues, Roberta da Silva Bussamara; Lando, Gabriela Albara; Schrank, Augusto; Vainstein, Marilene Henning; Weibel, Daniel Eduardo

2014-01-05

Ultraviolet (UV)-assisted surface modification in the presence of oxygen was used as initial step to achieve controlled degradation of poly(3-hydroxy-butyrate), PHB, films by entomopathogenic fungi. Treated surfaces were investigated by surface analysis techniques (water contact angle, Fourier Transformed Infrared Spectroscopy in Attenuated Total Reflectance mode, X-ray Photoelectron Spectroscopy, Near-edge X-ray Absorption Fine Structure, Gel Permeation Chromatography, Optical Microscopy, Scanning Electron Microscopy, and weight loss). After the UV-assisted treatments, new carbonyl groups in new chemical environments were detected by XPS and NEXAFS spectroscopy. The oxidizing atmosphere did not allow the formation of CC bonds, indicating that Norrish Type II mechanism is suppressed during or by the treatments. The higher hydrophilicity and concentration of oxygenated functional groups at the surface of the treated films possibly improved the biodegradation of the films. It was observed a clear increase in the growth of this fungus when oxygenated groups were grafted on the polymers surfaces. This simple methodology can be used to improve and control the degradation rate of PHB films in applications that require a controllable degradation rate. Copyright © 2013 Elsevier B.V. All rights reserved.

Water resources on and near the Nottawaseppi Huron band of Potawatomi indian tribal lands, Calhoun County, Michigan, 2000-03

USGS Publications Warehouse

Weaver, T.L.; Healy, D.; Sabin, T.G.

2005-01-01

The Nottawaseppi Huron Band of Potawatomi Indians in Calhoun County, Michigan is concerned about the water quality and quantity of streams in and around tribal lands and of shallow ground water. The tribe wanted to establish a database that included streamflow, stage, and water quality of local streams and quality of ground water from wells belonging to the tribe and its members. Concerned about the effects of long-term agricultural activity and increasing numbers of singlefamily dwellings being constructed within the watershed both on and off the reservation, the tribe wants to develop a water-resources management plan.U.S. Geological Survey (USGS) measured streamflow and installed staff gages tied into local datum on three tributaries of the St. Joseph River that cross tribal lands. Water-quality samples were collected from the sites under a variety of flow regimes from spring to fall during 2000-03. Stage-streamflow rating curves were constructed for Pine Creek and Athens & Indian Creek Drain after a number of discharge measurements were made and a thorough basin analysis was completed. Daily streamflow for Pine Creek near Athens was estimated for the period from May 2000 through September 2003.USGS collected 12 water samples at Pine Creek near Athens, Athens & Indian Creek Drain, and an unnamed tributary to Pine Creek during October 2000 through September 2003. Physical properties were measured, and the streams were sampled for major ions, nutrients, trace elements, caffeine, and herbicides/pesticides and their breakdown products (degradates). The tribe also measured physical properties weekly at the three sites during each growing season for the study period. Surface water at the three sites can be classified as hard, with calcium carbonate concentrations exceeding 180 milligrams per liter (mg/L). Concentrations of calcium, magnesium, chloride, and dissolved solids are typical of the area. There were 68 detections of 17 pesticides, degradates, and caffeine. Atrazine and metolachlor were detected in all samples, and the atrazine degradate deethylatrazine was detected in all samples from Pine Creek and Athens & Indian Creek Drain. Another atrazine degradate (2-hydroxy-atrazine, or OIET) was detected five of the six times that it was included in the analyses. A single sample collected from Athens & Indian Creek Drain in May 2001 had relatively higher concentrations of acetochlor, atrazine, CIAT (deethylatrazine), and diuron than the other sampling sites did during the study. Analysis for various species of mercury was completed on samples collected at Pine Creek and Athens & Indian Creek Drain in July 2003, and results were similar to those typical of unimpaired streams in the Midwest. None of the surface-water sites had major ion, nutrient, or trace-element concentrations that exceeded Michigan Department of Environmental Quality standards for nonpotable surface water.USGS also collected 11 ground-water samples from 7 wells on or adjacent to the traditional reservation in 2003. Two wells were sampled twice, and a single well was sampled three times, in order to document any chemical changes that might have occurred as a result of aquifer recharge, which most typically occurs in late winter to spring in the southern Lower Peninsula of Michigan. Samples were analyzed for 184 pesticides and degradates and caffeine. There were five detections of four pesticides or degradates, but none of the detected chemicals are included in current U.S. Environmental Protection Agency drinking-water standards. The remaining 181 analytes were below laboratory reporting limits.

The influence of CYP2B6, CYP2C9 and CYP2D6 genotypes on the formation of the potent antioestrogen Z-4-hydroxy-tamoxifen in human liver.

PubMed

Coller, Janet K; Krebsfaenger, Niels; Klein, Kathrin; Endrizzi, Karin; Wolbold, Renzo; Lang, Thomas; Nüssler, Andreas; Neuhaus, Peter; Zanger, Ulrich M; Eichelbaum, Michel; Mürdter, Thomas E

2002-08-01

To investigate in a large panel of 50 human liver samples the contribution of CYP2C9, CYP2D6, and CYP3A4 to the overall formation of the potent antioestrogen Z-4-hydroxy-tamoxifen, and how various genotypes affect its formation from tamoxifen. The formation of Z-4-hydroxy-tamoxifen from 10 microm tamoxifen was studied in human liver microsomes (n=50), characterized for CYP2B6, CYP2C9, CYP2D6 and CYP3A4 expression, and CYP2B6, CYP2C9 and CYP2D6 genotype. The effect of chemical and monoclonal antibody inhibitors, and the formation in supersomes expressing recombinant CYP isoforms was also investigated. Z-4-hydroxy-tamoxifen was quantified using LC-MS analysis. Z-4-hydroxy-tamoxifen was formed by supersomes expressing CYP2B6, CYP2C9, CYP2C19 and CYP2D6, but not CYP3A4. In agreement with these data, the mean formation of Z-4-hydroxy-tamoxifen was inhibited 49% by sulphaphenazole (P=0.001), 38% by quinidine (P<0.05) and 13% by monoclonal antibody against CYP2B6 (MAB-2B6, P<0.05). Furthermore, Z-4-hydroxy-tamoxifen formation significantly correlated with both CYP2C9 expression (r(s)=0.256, P<0.05) and CYP2D6 expression (r(s)=0.309, P<0.05). Genotypes of CYP2D6, CYP2B6 and CYP2C9 had an effect on metabolite formation in such a way that samples with two nonfunctional CYP2D6, or two variant CYP2C9 or CYP2B6 alleles, showed lower enzyme activity compared with those with two functional or wild-type alleles, (5.0 vs 9.9 pmol mg(-1) protein min(-1), P=0.046, 5.1 vs 9.9 pmol mg(-1) protein min(-1), P=0.053, and 6.8 vs 9.4 pmol mg(-1) protein min(-1), P=0.054, respectively). CYP2D6 and CYP2C9 contribute on average 45 and 46%, respectively, to the overall formation of Z-4-hydroxy-tamoxifen. CYP2B6, CYP2C9 and CYP2D6 genotypes all affected Z-4-hydroxy-tamoxifen formation and can predict individual ability to catalyse this reaction.

In vitro metabolism of BDE-47, BDE-99, and α-, β-, γ-HBCD isomers by chicken liver microsomes.

PubMed

Zheng, Xiaobo; Erratico, Claudio; Abdallah, Mohamed Abou-Elwafa; Negreira, Noelia; Luo, Xiaojun; Mai, Bixian; Covaci, Adrian

2015-11-01

The in vitro oxidative metabolism of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), 2,2',4,4',5-pentabromodiphenyl ether (BDE-99), and the individual α-, β- and γ-hexabromocyclododecane (HBCD) isomers catalyzed by cytochrome P450 (CYP) enzymes was studied using chicken liver microsomes (CLMs). Metabolites were identified using a liquid chromatography-tandem mass spectrometry method and authentic standards for the oxidative metabolites of BDE-47 and BDE-99. Six hydroxylated tetra-BDEs, namely 4-hydroxy-2,2',3,4'-tetrabromodiphenyl ether (4-OH-BDE-42), 3-hydroxy-2,2',4,4'-tetrabromodiphenyl ether (3-OH-BDE-47), 5-hydroxy-2,2',4,4'-tetrabromodiphenyl ether (5-OH-BDE-47), 6-hydroxy-2,2',4,4'-tetrabromodiphenyl ether (6-OH-BDE-47), 4'-hydroxy-2,2',4,5'- tetrabromodiphenyl ether (4'-OH-BDE-49), and 2'-hydroxy-2,3',4,4'-tetrabromodiphenyl ether (2'-OH-BDE-66), were identified and quantified after incubation of BDE-47 with CLMs. 4'-OH-BDE-49 was the major metabolite formed. Three hydroxylated penta-BDEs (5'-hydroxy-2,2',4,4',5-pentabromodiphenyl ether (5'-OH-BDE-99), 6'-hydroxy-2,2',4,4',5- pentabromodiphenyl ether (6'-OH-BDE-99), and 4'-hydroxy-2,2',4,5,5'-pentabromodiphenyl ether, 4'-OH-BDE-101, were formed incubating BDE-99 with CLMs. Concentrations of BDE-99 metabolites were lower than those of BDE-47. More than four mono-hydroxylated HBCD (OH-HBCD), more than four di-hydroxylated HBCD (di-OH-HBCD), more than five mono-hydroxylated pentabromocyclododecenes (OH-PBCD), and more than five di-hydroxylated pentabromocyclododecenes (di-OH-PBCD) were detected when α-, β-, or γ-HBCD were individually incubated with CLMs. Response values (the ratio between the peak areas of the target compound and its internal standard) for OH-HBCD were 1-3 orders of magnitude higher than those for OH-PBCD, di-OH-HBCD, and di-OH-PBCD, suggesting that OH-HBCD might be the major metabolites of α-, β- and γ-HBCD produced by CLMs. No diastereoisomeric or enantiomeric bioisomerisation was observed incubating α-, β- or γ-HBCD with CLMs. Collectively, our data suggest that (i) BDE-47 is metabolized at a faster rate than BDE-99 by CLMs, (ii) OH-HBCD are the major hydroxylated metabolites of α-, β- and γ-HBCD produced by CLMs and (iii) the diastereoisomeric or enantiomeric bioisomerisation of α-, β- and γ-HBCD is not mediated by chicken CYP enzymes. Copyright © 2015 Elsevier Inc. All rights reserved.

UVA Photoirradiation of Oxygenated Benz[a]anthracene and 3-Methylcholanthene - Generation of Singlet Oxygen and Induction of Lipid Peroxidation

PubMed Central

Yin, Jun-Jie; Xia, Qingsu; Cherng, Shu-Hui; Tang, I-Wah; Fu, Peter P.; Lin, Ge; Yu, Hongtao; Herreño Sáenz, Diógenes

2008-01-01

Polycyclic aromatic hydrocarbons (PAHs) are widespread genotoxic environmental pollutants and potentially pose a health risk to humans. Although the biological and toxicological activities, including metabolism, mutagenicity, and carcinogenicity, of PAHs have been thoroughly studied, their phototoxicity and photo-induced biological activity have not been well examined. We have long been interested in phototoxicity of PAHs and their derivatives induced by irradiation with UV light. In this paper we report the photoirradiation of a series of oxygenated benz[a]anthracene (BA) and 3-methylcholanthene (3-MC) by UVA light in the presence of a lipid, methyl linoleate. The studied PAHs include 2-hydroxy-BA (2-OH-BA), 3-hydroxy-BA (3-OH-BA), 5-hydroxymethyl-BA (5-CH2OH-BA), 7-hydroxymethyl-BA (7-CH2OH-BA), 12-hydroxymethyl-BA (12-CH2OH-BA), 7-hydroxymethyl-12-methyl-BA (7-CH2OH-12-MBA), 5-formyl-BA (5-CHO-BA), BA 5,6-cis-dihydrodiol (BA 5,6-cis-diol), 1-hydroxy-3-methylcholanthene (1-OH-3-MC), 1-keto-3-methylcholanthene (1-keto-3-MC), and 3-MC 1,2-diol. The results indicate that upon photoirradiation by UVA at 7 and 21 J/cm2, respectively all these compounds induced lipid peroxidation and exhibited a relationship between the dose of the light and the level of lipid peroxidation induced. To determine whether or not photoirradiation of these compounds by UVA light produces ROS, an ESR spin-trap technique was employed to provide direct evidence. Photoirradiation of 3-keto-3-MC by UVA (at 389 nm) in the presence of 2,2,6,6-tetramethylpiperidine (TEMP), a specific probe for singlet oxygen, resulted in the formation of TEMPO, indicating that singlet oxygen was generated. These overall results suggest that UVA photoirradiation of oxygenated BA and 3-methylcholanthrene generates singlet oxygen, one of the reactive oxygen species (ROS), which induce lipid peroxidation. PMID:18441402

Lysine and novel hydroxylysine lipids in soil bacteria: amino acid membrane lipid response to temperature and pH in Pseudopedobacter saltans

PubMed Central

Moore, Eli K.; Hopmans, Ellen C.; Rijpstra, W. Irene C.; Sánchez-Andrea, Irene; Villanueva, Laura; Wienk, Hans; Schoutsen, Frans; Stams, Alfons J. M.; Sinninghe Damsté, Jaap S.

2015-01-01

Microbial decomposition of organic matter is an essential process in the global carbon cycle. The soil bacteria Pseudopedobacter saltans and Flavobacterium johnsoniae are both able to degrade complex organic molecules, but it is not fully known how their membrane structures are adapted to their environmental niche. The membrane lipids of these species were extracted and analyzed using high performance liquid chromatography-electrospray ionization/ion trap/mass spectrometry (HPLC-ESI/IT/MS) and high resolution accurate mass/mass spectrometry (HRAM/MS). Abundant unknown intact polar lipids (IPLs) from P. saltans were isolated and further characterized using amino acid analysis and two dimensional nuclear magnetic resonance (NMR) spectroscopy. Ornithine IPLs (OLs) with variable (hydroxy) fatty acid composition were observed in both bacterial species. Lysine-containing IPLs (LLs) were also detected in both species and were characterized here for the first time using HPLC-MS. Novel LLs containing hydroxy fatty acids and novel hydroxylysine lipids with variable (hydroxy) fatty acid composition were identified in P. saltans. The confirmation of OL and LL formation in F. johnsoniae and P. saltans and the presence of OlsF putative homologs in P. saltans suggest the OlsF gene coding protein is possibly involved in OL and LL biosynthesis in both species, however, potential pathways of OL and LL hydroxylation in P. saltans are still undetermined. Triplicate cultures of P. saltans were grown at three temperature/pH combinations: 30°C/pH 7, 15°C/pH 7, and 15°C/pH 9. The fractional abundance of total amino acid containing IPLs containing hydroxylated fatty acids was significantly higher at higher temperature, and the fractional abundance of lysine-containing IPLs was significantly higher at lower temperature and higher pH. These results suggest that these amino acid-containing IPLs, including the novel hydroxylysine lipids, could be involved in temperature and pH stress response of soil bacteria. PMID:26175720

Exocyclic Deoxyadenosine Adducts of 1,2,3,4-Diepoxybutane: Synthesis, Structural Elucidation, and Mechanistic Studies

PubMed Central

Seneviratne, Uthpala; Antsypovich, Sergey; Goggin, Melissa; Dorr, Danae Quirk; Guza, Rebecca; Moser, Adam; Thompson, Carrie; York, Darrin M.; Tretyakova, Natalia

2009-01-01

1,2,3,4-Diepoxybutane (DEB)1 is considered the ultimate carcinogenic metabolite of 1,3-butadiene, an important industrial chemical and environmental pollutant present in urban air. Although it preferentially modifies guanine within DNA, DEB induces a large number of A → T transversions, suggesting that it forms strongly mispairing lesions at adenine nucleobases. We now report the discovery of three potentially mispairing exocyclic adenine lesions of DEB: N6,N6-(2,3-dihydroxybutan-1,4-diyl)-2′-deoxyadenosine (compound 2), 1,N6-(2-hydroxy-3-hydroxymethylpropan-1,3-diyl)-2′-deoxyadenosine (compound 3), and 1,N6-(1-hydroxymethyl-2-hydroxypropan-1,3-diyl)-2′-deoxyadenosine (compound 4). The structures and stereochemistry of the novel DEB-dA adducts were determined by a combination of UV and NMR spectroscopy, tandem mass spectrometry, and independent synthesis. We found that synthetic N6-(2-hydroxy-3,4-epoxybut-1-yl)-2′-deoxyadenosine (compound 1) representing the product of N6-adenine alkylation by DEB spontaneously cyclizes to form 3 under aqueous conditions or 2 under anhydrous conditions in the presence of organic base. Compound 3 can be interconverted with 4 by a reversible unimolecular pericyclic reaction favoring 4 as a more thermodynamically stable product. Both 3 and 4 are present in double stranded DNA treated with DEB in vitro and in liver DNA of laboratory mice exposed to 1,3-butadiene by inhalation. We propose that in DNA under physiological conditions, DEB alkylates the N-1 position of adenine in DNA to form N1-(2-hydroxy-3,4-epoxybut-1-yl)-adenine adducts, which undergo an SN2-type intramolecular nucleophilic substitution and rearrangement to give 3 (minor) and 4 (major). Formation of exocyclic DEB-adenine lesions following exposure to 1,3-butadiene provides a possible mechanism of mutagenesis at the A:T base pairs. PMID:19883087

Urinary Concentrations of Phthalates in Couples Planning Pregnancy and Its Association with 8-Hydroxy-2′-deoxyguanosine, a Biomarker of Oxidative Stress: Longitudinal Investigation of Fertility and the Environment Study

PubMed Central

2015-01-01

Oxidative stress has been recognized as one of the most important contributors to infertility in both males and females. Exposure to many environmental chemicals, such as phthalates, has been shown to induce oxidative stress. In a longitudinal study designed to assess exposure to environmental chemicals and fecundity in couples who were planning pregnancy, 894 urine samples were collected from 469 couples from Michigan and Texas during 2005–2009. The concentrations of 14 phthalate metabolites and a marker of oxidative stress, 8-hydroxy-2′-deoxyguanosine (8-OHdG), were determined in these samples. Concentrations, profiles, and estimated daily intakes (DIs) of phthalates were positively associated with 8-OHdG. The median concentrations of monomethyl phthalate (mMP), monoethyl phthalate (mEP), mono(3-carboxypropyl) phthalate (mCPP), mono-n-butyl phthalate (mBP), mono(2-isobutyl) phthalate (miBP), monobenzyl phthalate (mBzP), Σ5mEHP (sum of five metabolites of di(2-ethylhexyl) phthalate (DEHP)) and Σ14phthalates (sum of 14 urinary phthalate metabolites) were 0.48, 85.2, 4.50, 7.66, 4.36, 3.80, 54.8, and 249 μg/g creatinine, respectively. The estimated DI values for DEHP in 39 individuals were above the U.S. Environmental Protection Agency’s (EPA) reference dose (RfD) of 20 μg/kg-bw/day. The mean and median concentrations of 8-OHdG were 6.02 and 3.13 μg/g creatinine, respectively, which were significantly higher in females than in males. Statistically significant associations were found between 8-OHdG and urinary concentrations of mEP, and Σ5mEHP for females. Similarly, a significant association was found between 8-OHdG and DIs estimated for select phthalates. Our results suggested that phthalate exposure increases oxidative stress, which can be a mechanism for the diminished fertility observed in couples who were highly exposed to select phthalates. PMID:25068827

Hydroxy-fipronil is a new urinary biomarker of exposure to fipronil

PubMed Central

Vasylieva, Natalia; Barnych, Bogdan; Wan, Debin; El-Sheikh, El-Sayed A.; Nguyen, Hai M.; Wulff, Heike; McMahen, Rebecca; Strynar, Mark; Gee, Shirley J.; Hammock, Bruce D.

2017-01-01

Occupational medical surveillance is highly desirable in manufacturing facilities where exposure to chemicals is significant. The insecticide fipronil is generally considered safe for humans but with increasing use, exposure to fipronil is of concern. Identification of urinary metabolites of fipronil may allow development of affordable, cheap and rapid procedures for human exposure evaluation. In this study we developed a fast and easy approach for synthesis of hydroxy-fipronil, a potential urinary metabolite of fipronil. This standard was used to develop a sensitive analytical LC-MS/MS method with a limit of quantification (LOQ) of 0.4 ng/mL. Fipronil sulfone, a known metabolite, and hydroxy-fipronil were quantified in urine samples from rats treated with a fipronil containing diet. Fipronil sulfone concentration centered around 20 ng/mL, while the concentration of hydroxy-fipronil was dose-dependent ranging in 10–10 000 ng/mL and thus being a more sensitive marker of fipronil exposure. A fipronil immunoassay with cross-reactivity to hydroxy-fipronil showed a good correlation in signal intensity with LC-MS data. It was also used to demonstrate the applicability of the method for sample screening in the evaluation of exposure levels. PMID:28343720

Production of 10S-hydroxy-8(E)-octadecenoic acid from oleic acid by whole recombinant Escherichia coli cells expressing 10S-dioxygenase from Nostoc punctiforme PCC 73102 with the aid of a chaperone.

PubMed

Kim, Min-Ji; Seo, Min-Ju; Shin, Kyung-Chul; Oh, Deok-Kun

2017-01-01

To increase the production of 10S-hydroxy-8(E)-octadecenoic acid from oleic acid by whole recombinant Escherichia coli cells expressing Nostoc punctiforme 10S-dioxygenase with the aid of a chaperone. The optimal conditions for 10S-hydroxy-8(E)-octadecenoic acid production by recombinant cells co-expressing chaperone plasmid were pH 9, 35 °C, 15 % (v/v) dimethyl sulfoxide, 40 g cells l -1 , and 10 g oleic acid l -1 . Under these conditions, recombinant cells co-expressing chaperone plasmid produced 7.2 g 10S-hydroxy-8(E)-octadecenoic acid l -1 within 30 min, with a conversion yield of 72 % (w/w) and a volumetric productivity of 14.4 g l -1 h -1 . The activity of recombinant cells expressing 10S-dioxygenase was increased by 200 % with the aid of a chaperone, demonstrating the first biotechnological production of 10S-hydroxy-8(E)-octadecenoic acid using recombinant cells expressing 10S-dioxygenase.

Crystal structure of the tri-ethyl-ammonium salt of 3-[(4-hy-droxy-3-meth-oxy-phen-yl)(4-hy-droxy-2-oxo-2H-chromen-3-yl)meth-yl]-2-oxo-2H-chromen-4-olate.

PubMed

Ikram, Muhammad; Rehman, Sadia; Khan, Afzal; Schulzke, Carola

2018-03-01

The reaction between 3,3'-[(3-meth-oxy-4-hy-droxy-phen-yl)methanedi-yl]bis-(4-hy-droxy-2 H -chromen-2-one) and tri-ethyl-amine in methanol yielded the title compound tri-ethyl-ammonium 3-[(4-hy-droxy-3-meth-oxy-phen-yl)(4-hy-droxy-2-oxo-2 H -chromen-3-yl)meth-yl]-2-oxo-2 H -chromen-4-olate, C 6 H 16 N + ·C 26 H 17 O 8 - or (NHEt 3 ) + (C 26 H 17 O 8 ) - , which crystallized directly from its methano-lic mother liquor. The non-deprotonated coumarol substituent shares its H atom with the deprotonated coumarolate substituent in a short negative charge-assisted hydrogen bond in which the freely refined H atom is moved from its parent O atom towards the acceptor O atom, elongating the covalent O-H bond to 1.18 (3) Å. The respective H atom can therefore be described as being shared by two alcohol O atoms, culminating in the formation of an eight-membered ring.

Characterization of Bacillus thuringiensis l-Isoleucine Dioxygenase for Production of Useful Amino Acids▿†

PubMed Central

Hibi, Makoto; Kawashima, Takashi; Kodera, Tomohiro; Smirnov, Sergey V.; Sokolov, Pavel M.; Sugiyama, Masakazu; Shimizu, Sakayu; Yokozeki, Kenzo; Ogawa, Jun

2011-01-01

We determined the enzymatic characteristics of an industrially important biocatalyst, α-ketoglutarate-dependent l-isoleucine dioxygenase (IDO), which was found to be the enzyme responsible for the generation of (2S,3R,4S)-4-hydroxyisoleucine in Bacillus thuringiensis 2e2. Depending on the amino acid used as the substrate, IDO catalyzed three different types of oxidation reactions: hydroxylation, dehydrogenation, and sulfoxidation. IDO stereoselectively hydroxylated several hydrophobic aliphatic l-amino acids, as well as l-isoleucine, and produced (S)-3-hydroxy-l-allo-isoleucine, 4-hydroxy-l-leucine, (S)-4-hydroxy-l-norvaline, 4-hydroxy-l-norleucine, and 5-hydroxy-l-norleucine. The IDO reaction product of l-isoleucine, (2S,3R,4S)-4-hydroxyisoleucine, was again reacted with IDO and dehydrogenated into (2S,3R)-2-amino-3-methyl-4-ketopentanoate, which is also a metabolite found in B. thuringiensis 2e2. Interestingly, IDO catalyzed the sulfoxidation of some sulfur-containing l-amino acids and generated l-methionine sulfoxide and l-ethionine sulfoxide. Consequently, the effective production of various modified amino acids would be possible using IDO as the biocatalyst. PMID:21821743

SPECTROPHOTOMETRIC DETERMINATION OF CALCIUM WITH GLYOXAL BIS (2-HYDROXY- ANIL)

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

Florence, T.M.; Morgan, J.

1961-03-01

A selective method is described for the spectrophotometric determination of calcium using glyoxal bis(2hydroxy-anil) as the chromogenic agent. A comprehensive study of interferences and reagent variables was made. (auth)

Physiological performance of two contrasting rice varieties under water stress.

PubMed

Khan, Furqan; Upreti, Priyanka; Singh, Ruchi; Shukla, Pradeep Kumar; Shirke, Pramod Arvind

2017-01-01

Two rice varieties PR-115 and Super-7 were imposed to water stress and different physiological traits were monitored to evaluate the performance of these varieties under drought. Under water stress condition although the relative water content, osmotic potential, chlorophyll content, photosynthesis rate, carbon discrimination and biomass decreased in both the varieties however, the reduction was more pronounced in Super-7 variety. Oryzanol a trans-ester of ferulic acid functions as antioxidant and it increased along with total phenolic and anthocyanin content in both the varieties under drought stress. However, gallic acid, 4 hydroxy benzoic acid, syringic acid and chlorogenic acid showed differential pattern in both of the varieties under water limiting conditions. Under drought, grain yield was penalized by 17 and 54% in PR-115 and Super-7 varieties, respectively in comparison to watered plants. Super-7 variety showed pronounced electrolyte leakage and MDA enhancement under water stress condition. High non photochemical quenching and reduction in Y(NO) and Y(II) indicated balanced energy management in tolerant PR-115 variety. The studies showed that PR-115 is a drought tolerant variety while Super-7 is drought sensitive in nature.

Exploring the Scope of Asymmetric Synthesis of β-Hydroxy-γ-lactams via Noyori-type Reductions.

PubMed

Lynch, Denis; Deasy, Rebecca E; Clarke, Leslie-Ann; Slattery, Catherine N; Khandavilli, U B Rao; Lawrence, Simon E; Maguire, Anita R; Magnus, Nicholas A; Moynihan, Humphrey A

2016-10-07

Enantio- and diastereoselective hydrogenation of β-keto-γ-lactams with a ruthenium-BINAP catalyst, involving dynamic kinetic resolution, has been employed to provide a general, asymmetric approach to β-hydroxy-γ-lactams, a structural motif common to several bioactive compounds. Full conversion to the desired β-hydroxy-γ-lactams was achieved with high diastereoselectivity (up to >98% de) by addition of catalytic HCl and LiCl, while β-branching of the ketone substituent demonstrated a pronounced effect on the modest to excellent enantioselectivity (up to 97% ee) obtained.

Production of alpha-hydroxy carboxylic acids and esters from higher sugars using tandem catalyst systems

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

Orazov, Marat; Davis, Mark E.

The present disclosure is directed to methods and composition used in the preparation of alpha-hydroxy carboxylic acids and esters from higher sugars using a tandem catalyst system comprising retro-aldol catalysts and Lewis acid catalysts. In some embodiments, these alpha-hydroxy carboxylic acids may be prepared from pentoses and hexoses. The retro-aldol and Lewis catalysts may be characterized by their respective ability to catalyze a 1,2-carbon shift reaction and a 1,2-hydride shift reaction on an aldose or ketose substrate.

4-Hydroxy-3-methyl-6-phenylbenzofuran-2-carboxylic acid ethyl ester derivatives as potent anti-tumor agents.

PubMed

Hayakawa, Ichiro; Shioya, Rieko; Agatsuma, Toshinori; Furukawa, Hidehiko; Naruto, Shunji; Sugano, Yuichi

2004-01-19

Based on the structure of 4-hydroxy-3-methyl-6-phenylbenzofuran-2-carboxylic acid ethyl ester (1), which exhibits selective cytotoxicity against a tumorigenic cell line, (2,4-dimethoxyphenyl)-(4-hydroxy-3-methyl-6-phenylbenzofuran-2-yl)-methanone (18m) was designed and synthesized as a biologically stable derivative containing no ester group. Although the potency of 18m was almost the same as our initial hit compound 1, 18m is expected to last longer in the human body as an anticancer agent.

A new isocoumarin from Cajanus cajan (Fabaceae).

PubMed

Rodrigues, Virginia F; Oliveira, Rodrigo R; Vega, Maria Raquel G

2014-04-01

A new isocoumarin, 3-phenyl-8-hydroxy-6-methoxy-5-gamma,gamma-dimethylallyl-isocoumarin, named cajavilmina (1) and eight known compounds: a-amirenone (2), beta-amirenone (3), lupenone (4), 5-hydroxy-7-methoxydihydroflavone (5), longistilin C (6), 3-hydroxy-5-methoxystilbene (7), beta-sitosterol (8) and stigmasterol (9) were identified in a dichloromethane fraction from Cajanus cajan leaves. Structures were elucidated by analysis of spectral data, mainly those afforded by 1H, NOEDIFF and 13C NMR (1D and 2D NMR HMQC, HMBC and COSY) and mass spectra.

Chain decomposition of aqueous triethanolamine. [Gamma Radiation

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

Schwarz, H.A.

A radiation-induced chain decomposition of aqueous triethanolamine into acetaldehyde and diethanolamine is reported. Chain lengths over 1000 have been observed, depending on pH, concentration, and radiation intensity. The chain propagation steps include OH group migration in the 2-hydroxy-1-(diethanolamino)ethyl radical and NR/sub 2/ migration in 1-hydroxy-2(diethanolamine)ethyl radical, each producing a 2-hydroxy-2-(diethanolamine)ethyl radical. Free-radical spectra and rate constants are given. Studies of diethanolamine and diethylethanolamine solutions gave similar free-radical spectra but much shorter chains.

Preparation of ω-hydroxy pelargonic acid

NASA Astrophysics Data System (ADS)

Hadi, Siti Faieza Abd; Salimon, Jumat

2018-04-01

Utilization of plant oil as renewable raw material for monomers and polymers in bioplastic industry has a great potential to replace conventional petroleum-based plastic usage especially in packaging and adhesive applications. One of useful monomer is ω-hydroxy pelargonic acid that can be polymerizing as biodegradable polyester. In this study, the aim is to synthesis ω-hydroxy pelargonic acid from oleic acid based on oxidation/ esterification/ saponification and reduction methodology. The yield obtained after aqueous workup is 53% and the compound structure is determined by FT-IR and 1H and 13C NMR.

Preparation of 4-amino-2,4-dioxobutanoic acid

DOEpatents

Unkefer, Pat J.; Martinez, Rodolfo A.; Glass, David R.

2016-03-22

A process for synthesizing 4-amino-2,4-dioxobutanoic acid involves reacting diethyl oxalate with an alkoxide in ethanol to form a reaction mixture, and afterward adding ethyl cyanoacetate to the reaction mixture and allowing a reaction to proceed under conditions suitable to form a first reaction product of the formula diethyl 2-cyano-3-hydroxy-butenedioate, and then isolating the diethyl 2-cyano-3-hydroxy-butenedioate, and afterward reacting the diethyl-2-cyano-3-hydroxy-butenedioate with an aqueous hydroxide under conditions suitable to form 4-amino-2,4-dioxobutanoic acid.

Sensitive method for the determination of different S(IV) species in cloud and fog water.

PubMed

Lammel, G

1996-08-01

Suppressed ion chromatography has been applied to the determination of S(IV) species in cloud and fog water in the range 0.012-2.4 mg S(IV)-S/L. The samples have been preserved prior to storage and S(IV) species have been determined as hydroxy methanesulfonate (HMS) together with the low molecular weight carboxylic acid anions, formate and acetate. Samples have been divided and treated differently such that total S(IV) as well as the non-oxidizable fraction of S(IV) (as given by the reactivity with H(2)O(2), added in surplus) could be determined. The difference between the two corresponds to the S(IV) fraction subjected to oxididation, which is of paramount interest in cloud and fogwater chemistry.

Hydrolysis and nucleophilic substitution of model and ultimate carcinogens

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

Helmick, J.S.

1992-01-01

The hydrolysis reaction of the Model Carcinogen O-pivaloyl-N-(4-chlorophenyl)hydroxylamine in aqueous buffer (pH 7.0-10.0) proceeds by was of a nitrenium ion intermediate. The products formed from this process are predominately 2,4-dichloroaniline, and 2-hydroxy-4-chloro-pivalanilide. At pH 10-13 the rate becomes dependent upon hydroxide. The product that is formed is 4-chlorophenylhydroxylamine. 4-Chlorophenyl-hydroxylamine is formed by basic ester hydrolysis determined by an [sup 18]O GC-MS experiment. The reaction of O-pivaloyl-N-(4-chlorophenyl)hydroxylamine in an aqueous diethylamine (pH 11.3) buffer gave 4-chlorophenyl-N,N-diethylhydrazine as the substitution product in a 16% yield. The reaction of O-pivaloyl-N-(4-methylphenyl)hydroxylamine with diethylamine gave a 1% yield of the hydrazine product. The reaction ofmore » N,N-dimethylanline and aniline with ring-substituted O-pivaloyl-N-arylhydroxylamines in MeOH generates products of nucleophilic attack on the nitrogen of the hydroxylamine derivative. The hydrolysis of the ultimate carcinogen N-(sulfonatooxy)-N-4-aminobiphenyl proceeds by two consecutive pseudo-first-order processes and generates predominately a product of nucleophilic attack by chloride ion at the ortho position of the aromatic ring. A labile intermediate identified as N-acetypl-4-hydroxy-4-phenyl-2,5-cyclohexadienone imine has been detected by NMR. This intermediate rearranges to form 4-hydroxy-3-phenylacetanilide. The hydrolysis of N-benzoyl-4-hydroxy-4-hydroxy-4-phenyl-2,5-cyclohexadienone imine proceeds by way of two consecutive pseudo-first-order processes. The hydrolysis of N-benzoyl-4-methoxy-4-phenyl-2,5-cyclohexadienone imine also proceeds by two consecutive pseudo-first-order processes. Spectroscopic evidence of two diastereomeric intermediates formed from the hydrolysis of the N-benzoyl imines were tentatively identified as N-benzoyl-N-hydroxy-4-hydroxy-4-phenyl-2,5-cyclohexadienone imine.« less

Reduction of the 20-Carbonyl Group of C-21 Steroids by Spores of Fusarium solani and Other Microorganisms. I. Side-Chain Degradation, Epoxide Cleavage, and Substrate Specificity

PubMed Central

Plourde, Rosaire; El-Tayeb, Ossama M.; Hafez-Zedan, Hamdallah

1972-01-01

The spores of Fusarium solani reduced the C2-carbonyl group, 1-dehydrogenated ring „A” and cleaved the side chain of 16α, 17α-oxidopregn-4-ene-3, 20-dione (16α, 17α-oxidoprogesterone)(I) to give the following products: 20α-hydroxy-16α, 17α-oxidopregn-4-en-3-one(II); 20α-hydroxy-16α, 17α-oxidopregna-1, 4-dien-3-one(III); 16α-hydroxy-17a-oxa-androsta-1, 4-diene-3, 17-dione (16α-hydroxy-1-dehydrotestololactone)(IV); and 16α, 17β-dihydroxy-androsta-1, 4-dien-3-one (16α-hydroxy-1-dehydrotestosterone)(V). When II was used as a substrate, it was metabolized into III, IV, and V at a slower rate than I. Furthermore, 16α-hydroxy-androst-4-ene-3, 17-dione (16α-hydroxyandrostenedione)(X) was transformed into IV and V. Pregn-4-ene-3, 20-dione (progesterone)(XII) was transformed into androsta-1, 4-diene-3, 17-dione (androstadienedione)(VIII) and 17a-oxa-androsta-1, 4-diene-3, 17-dione (1-dehydrotestololactone)(IX), while 17α-hydroxy-pregn-4-ene-3, 20-dione (17α-hydroxyprogesterone)(VI) was converted into its 1-dehydro analogue (VII) without accumulation of any 20-dihydro compounds. Substrate specificity in the 20-reductase system of F. solani, Cylindrocarpon radicicola, Septomyxa affinis, Bacillus lentus, and three strains of B. sphaericus are demonstrated. The 20-reductase is active only on steroids having the 16α, 17α-oxido, and Δ4-3-keto functions. Evidence of competition between side-chain degrading enzymes and the 20-reductase for the steroid molecule and evidence of side-chain degradation followed by epoxide cleavage (and not the reverse) are presented. A mechanism for the epoxide opening by nongerminating spores of F. solani is postulated. PMID:5021973

Antiviral Evaluation of Octadecyloxyethyl Esters of (S)-3-Hydroxy-2-(phosphonomethoxy)propyl Nucleosides Against Herpesviruses and Orthopoxviruses≠

PubMed Central

Valiaeva, Nadejda; Prichard, Mark N.; Buller, R. Mark; Beadle, James R.; Hartline, Caroll B.; Keith, Kathy A.; Schriewer, Jill; Trahan, Julissa; Hostetler, Karl Y.

2009-01-01

Our previous studies showed that esterification of (S)-3-hydroxy-2-(phosphono-methoxy)propyl]adenine (HPMPA) or 1-(S)-[3-hydroxy-2-(phosphonomethoxy)-propyl]cytosine (HPMPC) with alkoxyalkyl groups such as hexadecyloxypropyl (HDP) or octadecyloxyethyl (ODE) resulted in large increases in antiviral activity and oral bioavailability. The HDP- and ODE- esters of HPMPA were shown to be active in cells infected with human immunodeficiency virus, type 1 (HIV-1), while HPMPA itself was virtually inactive. To explore this approach in greater detail, we synthesized four new compounds in this series, the ODE esters of 9-(S)-[3-hydroxy-2-(phosphonomethoxy)-propyl]guanine (HPMPG), 1-(S)-[3-hydroxy-2-(phosphono-methoxy)propyl]thymine (HPMPT), 9-(S)-[3-hydroxy-2-(phosphonomethoxy)propyl]-2,6-diaminopurine (HPMPDAP) and 9-(S)-[3-hydroxy-2-(phosphonomethoxy)propyl]-2-amino-6-cyclopropylaminopurine. (HPMP-cPrDAP) and evaluated their antiviral activity against herpes simplex virus, type 1 (HSV-1), human cytomegalovirus (HCMV), and vaccinia, cowpox and ectromelia. Against HSV-1, subnanomolar EC50 values were observed with ODE-HPMPA and ODE-HPMPC while ODE-HPMPG had intermediate antiviral activity with an EC50 of 40 nanomolar. In HFF cells infected with HCMV, the lowest EC50 values were observed with ODE-HPMPC, 0.9 nanomolar. ODE -HPMPA was highly active with an EC50 of 3 nanomolar, while ODE-HPMPG and ODE-HPMPDAP were also highly active with EC50s of 22 and 77 nanomolar, respectively. Against vaccinia and cowpox viruses, ODE-HPMPG and ODE-HPMPDAP were the most active and selective compounds with EC50 values of 20 to 60 nanomolar and selectivity index values of 600 to 3,500. ODE-HPMPG was also active against ectromelia virus with an EC50 value of 410 nanomolar and a selectivity index value of 166. ODE-HPMPG and ODE-HPMPDAP are proposed for further preclinical evaluation as possible candidates for treatment of HSV, HCMV or orthopoxvirus diseases. PMID:19800369

A validated LC-MS/MS method for the determination of tolterodine and its metabolite in rat plasma and application to pharmacokinetic study.

PubMed

Shaik, Rihana Parveen; Puttagunta, Srinivasa Babu; Kothapalli, Chandrasekhar Bannoth; Awen, Bahlul Zayed Sh; Challa, B R

2013-12-01

Liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was used for simultaneous quantification of tolterodine and its metabolite 5-hydroxy methyl tolterodine in rat plasma. Tolterodine-d6 and 5-hydroxy methyl tolterodine-d14 were used as internal standards (IS). Chromatographic separation was performed on Ascentis Express RP amide (50 mm×4.6 mm, 2.7 μm) column with an isocratic mobile phase composed of 10 mM ammonium acetate and acetonitrile in the ratio of 20:80 (v/v), at a flow-rate of 0.5 mL/min. Tolterodine, tolterodine-d6, 5-hydroxy methyl tolterodine and 5-hydroxy methyl tolterodine-d14 were detected with proton adducts at m / z 326.1→147.1, 332.3→153.1, 342.2→223.1 and 356.2→223.1 in multiple reaction monitoring (MRM) positive mode respectively. The drug, metabolite and internal standards were extracted by liquid-liquid extraction method. The method was validated over a linear concentration range of 20.00-5000.00 pg/mL for tolterodine and 20.00-5000.00 pg/mL for 5-hydroxy methyl tolterodine. This method demonstrated intra- and inter-day precision of 0.62-6.36% and 1.73-4.84% for tolterodine, 1.38-4.22% and 1.62-4.25% for 5-hydroxy methyl tolterodine respectively. This method also demonstrated intra- and inter-day accuracy of 98.75-103.56% and 99.20-104.40% for tolterodine, 98.08-104.67% and 98.73-103.06% for 5-hydroxy methyl tolterodine respectively. Both analytes were found to be stable throughout freeze-thaw cycles, bench top and postoperative stability studies. This method was successfully applied for the pharmacokinetic analysis of rat plasma samples following i.v. administration.

Association of atmospheric concentrations of polycyclic aromatic hydrocarbons with their urinary metabolites in children and adolescents.

PubMed

Poursafa, Parinaz; Amin, Mohammad Mehdi; Hajizadeh, Yaghoub; Mansourian, Marjan; Pourzamani, Hamidreza; Ebrahim, Karim; Sadeghian, Babak; Kelishadi, Roya

2017-07-01

This study aims to determine the atmospheric concentrations of particulate matter 2.5 (PM 2.5 )-bounded polycyclic aromatic hydrocarbons (PAHs) and their association with their urinary metabolites in children and adolescents. This study was conducted from October 2014 to March 2016 in Isfahan, Iran. We measured 16 species of PAHs bounded to PM 2.5 by gas chromatography mass spectrometry (GC/MS) from 7 parts of the city. Moreover, PAH urinary metabolites were measured in 186 children and adolescents, randomly selected from households. Urinary metabolites consisted of 1-hydroxy naphthalene (1-naphthol), 2-hydroxy naphthalene (2-naphthol), 9-hydroxy phenanthrene (9-phenanthrol), and 1-hydroxy pyrene using GC/MS. Considering the short half-lives of PAHs, we measured the metabolites twice with 4 to 6 months of time interval. We found that the ambient concentrations of PAHs were significantly associated with their urinary metabolites. 1-hydroxy naphthalene and 2-hydroxy naphthalene concentrations showed an increase of 1.049 (95% CI: 1.030, 1.069) and 1.047 (95% CI: 1.025, 1.066) for each unit increase (1 ng/m 3 ) in ambient naphthalene. Similarly, 1-hydroxy pyrene showed an increase of 1.009 (95% CI: 1.006-1.011) for each unit increase (1 ng/m 3 ) in ambient pyrene concentration after adjustment for body mass index, physical activity level, urinary creatinine, age, and sex. The association of urinary 9-hydroxyphenanthrene and ambient phenantherene was significant in the crude model; however after adjustment for the abovementioned covariates, it was no more significant. We found significant correlations between exposure to ambient PM 2.5 -bounded PAHs and their urinary excretion. Considering the adverse health effects of PAHs in the pediatric age group, biomonitoring of PAHs should be underscored; preventive measures need to be intensified.

Metabolism of two new antiepileptic drugs and their principal metabolites S(+)- and R(-)-10,11-dihydro-10-hydroxy carbamazepine.

PubMed

Hainzl, D; Parada, A; Soares-da-Silva, P

2001-05-01

BIA 2-093 and BIA 2-059 are two stereoisomers under development as new antiepileptic drugs. They act as prodrugs for the corresponding hydroxy derivatives (S(+)- or R(-)-10,11-dihydro-10-hydroxy carbamazepine, respectively) which are known to be the active metabolites of the antiepileptic drug oxcarbazepine (OXC). The purpose of this study was to define the metabolic pathway especially in terms of stereoselectivity, and to estimate the possibility of racemization in humans. For in vivo studies, the rat, mouse and rabbit were chosen as models in order to cover a broad spectrum of metabolic activity. In addition, incubations with liver microsomes from these three species plus dog and monkey were compared to results obtained with human liver microsomes. It was found that both drugs were almost instantly hydrolysed to the corresponding 10-hydroxy compounds in mice, rats and rabbits. Mice and rabbits were not able to oxidize the 10-hydroxy compounds to OXC in significant amounts. In the rat, BIA 2-093 also gave origin to OXC, whereas BIA 2-059 resulted in the formation of OXC and the trans-diol metabolite in equal amounts. It could be shown that the rat is able to reduce the formed OXC in liver to S(+)-10-hydroxy metabolite, resulting in a loss of enantiomeric purity after treatment with BIA 2-059 rather than in the case of BIA 2-093. Human liver microsomes hydrolysed BIA 2-093 and BIA 2-059 to their corresponding 10-hydroxy compounds and to OXC in a very small extent with BIA 2-093 only. Therefore, BIA 2-093 and BIA 2-059 seem to be preferable drugs over OXC since they most likely exhibit a 'cleaner' metabolism. From a therapeutic point of view BIA 2-059 would be less appropriate than BIA 2-093 for the purpose of treating epileptic patients due to its propensity to undergo inactivation to the trans-diol.

Biocontrol of Aspergillus Species on Peanut Kernels by Antifungal Diketopiperazine Producing Bacillus cereus Associated with Entomopathogenic Nematode

PubMed Central

Kumar, Sasidharan Nishanth; Sreekala, Sreerag Ravikumar; Chandrasekaran, Dileep; Nambisan, Bala; Anto, Ruby John

2014-01-01

The rhabditid entomopathogenic nematode associated Bacillus cereus and the antifungal compounds produced by this bacterium were evaluated for their activity in reducing postharvest decay of peanut kernels caused by Aspergillus species in in vitro and in vivo tests. The results showed that B. cereus had a significant effect on biocontrol effectiveness in in vitro and in vivo conditions. The antifungal compounds produced by the B. cereus were purified using silica gel column chromatography and their structure was elucidated using extensive spectral analyses. The compounds were identified as diketopiperazines (DKPs) [cyclo-(L-Pro-Gly), cyclo(L-Tyr-L-Tyr), cyclo-(L-Phe-Gly) and cyclo(4-hydroxy-L-Pro-L-Trp)]. The antifungal activities of diketopiperazines were studied against five Aspergillus species and best MIC of 2 µg/ml was recorded against A. flavus by cyclo(4-hydroxy-L-Pro-L-Trp). To investigate the potential application of cyclo(4-hydroxy-L-Pro-L-Trp) to eliminate fungal spoilage in food and feed, peanut kernels was used as a food model system. White mycelia and dark/pale green spores of Aspergillus species were observed in the control peanut kernels after 2 days incubation. However the fungal growth was not observed in peanut kernels treated with cyclo(4-hydroxy-L-Pro-L-Trp). The cyclo(4-hydroxy-L-Pro-L-Trp) was nontoxic to two normal cell lines [fore skin (FS) normal fibroblast and African green monkey kidney (VERO)] up to 200 µg/ml in MTT assay. Thus the cyclo(4-hydroxy-L-Pro-L-Trp) identified in this study may be a promising alternative to chemical preservatives as a potential biopreservative agent which prevent fungal growth in food and feed. To the best of our knowledge, this is the first report demonstrating that the entomopathogenic nematode associated B. cereus and cyclo(4-hydroxy-L-Pro-L-Trp) could be used as a biocontrol agents against postharvest fungal disease caused by Aspergillus species. PMID:25157831

Inert Reassessment Document for 2-(2'-Hydroxy-5'-methylpheny)benzotriazole

EPA Pesticide Factsheets

2-(2'-Hydroxy-5'-methylphenyl)benzotriazole commonly known as Drometrizole is most commonly used as an UV light absorber helping to stabilizeand protect plastics, polyesters, celluloses, acrylates, dyes, rubber, synthetic and natural fibers, waxes,

Genetics Home Reference: 3-hydroxy-3-methylglutaryl-CoA lyase deficiency

MedlinePlus

... Targets Orphanet: 3-hydroxy-3-methylglutaric aciduria Screening, Technology, and Research in Genetics Virginia Department of Health (PDF) Patient Support and Advocacy Resources (3 links) Children Living with Inherited Metabolic Diseases (CLIMB) (UK) FOD ( ...

Rapid identification of triterpenoid sulfates and hydroxy fatty acids including two new constituents from Tydemania expeditionis by liquid chromatography-mass spectrometry.

PubMed

Zhang, Jian-Long; Kubanek, Julia; Hay, Mark E; Aalbersberg, William; Ye, Wen-Cai; Jiang, Ren-Wang

2011-09-01

Tydemania expeditionis Weber-van Bosse (Udoteaceae) is a weakly calcified green alga. In the present paper, liquid chromatography coupled with photodiode array detection and electrospray mass spectrometry was developed to identify the fingerprint components. A total of four triterpenoid sulfates and three hydroxy fatty acids in the ethyl acetate fraction of the crude extract were structurally characterized on the basis of retention time, online UV spectrum, and mass fragmentation pattern. Furthermore, a detailed liquid chromatography-mass spectrometry analysis revealed two new hydroxy fatty acids, which were then prepared and characterized by extensive nuclear magnetic resonance (NMR) analyses. The proposed method provides a scientific and technical platform for the rapid identification of triterpenoid sulfates and hydroxy fatty acids in similar marine algae and terrestrial plants. Copyright © 2011 John Wiley & Sons, Ltd.

Short- and long-term consequences on biochemical markers after fundectomy in pigs supplemented with 3-hydroxy-3-methylbutyrate and alpha-ketoglutarate.

PubMed

Sliwa, Ewa; Adaszek, Łukasz; Tatara, Marcin; Dobrowolski, Piotr

2010-01-01

The aim of this study was to investigate short-term 4 and 14 weeks after fundectomy) and long-term (at the age of 8 months) postoperative effects of 3-hydroxy-3-methylbutyrate and/or alpha-ketoglutarate on selected serum biochemical markers in fundectomized pigs. Experimental fundectomy was performed in 30 castrated male pigs of the Puławska breed who received placebo or 3-hydroxy-3-methylbutyrate and/or alpha-ketoglutarate up to the age of 8 months. Plasma amino acid concentrations and selected blood parameters were analyzed. Main vital organs were weighed. Our study showed that the supplementations with alpha-ketoglutarate and/or 3-hydroxy-3-methylbutyrate to fundectomized pigs significantly prevented the reduction of stomach, liver and spleen weights. However, results of this study, either positive or negative, cannot categorically establish a beneficial effect of AKG and HMB nutritional support after fundectomy in pigs.

(E)-3-[3,4-Bis(meth-oxy-methoxy)phen-yl]-1-(7-hy-droxy-5-meth-oxy-2,2-dimethyl-chroman-8-yl)prop-2-en-1-one.

PubMed

Hashim, Nur Athirah; Ahmad, Farediah; Basar, Norazah; Awang, Khalijah; Ng, Seik Weng

2011-09-01

The reaction of 5,6-(2,2-dimethyl-chroman-yl)-2-hy-droxy-4-meth-oxy-acetophenone and 3,4-bis-(meth-oxy-meth-yloxy)benzaldehyde affords the intense orange title chalcone derivative, C(25)H(30)O(8). The two benzene rings are connected through a -C(=O)-CH=CH- (propenone) unit, which is in an E conformation; the ring with the hy-droxy substitutent is aligned at 19.5 (2)° with respect to this unit, whereas the ring with the meth-oxy-meth-yloxy substituent is aligned at 9.3 (3)°. The dihedral angle between the rings is 19.38 (10)°. The hy-droxy group engages in an intra-molecular O-H⋯O hydrogen bond with the carbonyl O atom of the propenone unit, generating an S(5) ring.

Grafting of 2 (2-hydroxy-5-vinylphenyl) 2H-benzotriazole onto polymers with aliphatic groups. Synthesis and polymerization of 2 (2-hydroxy-5-isopropenylphenyl) 2H-benzotriazole and a new synthesis of 2 (2-hydroxy-5-vinylphenyl) 2H-benzotriazole

NASA Technical Reports Server (NTRS)

Pradellok, W.; Nir, Z.; Vogl, O.

1981-01-01

Successful grafting of 2(2-hydroxy-5-vinylphenyl)2H-benzotriazole onto saturated aliphatic C-H groups of polymers has been accomplished. When the grafting reaction was carried out in chlorobenzene at 150 C = 160 C with di-tertiarybutylperoxide as the grafting initiator, grafts as high as 20 percent - 30 percent at a grafting efficiency of 50 percent and 80 percent have readily been obtained. The grafting reaction was carried out in tubes sealed under high vacuum since trace amounts of oxygen cause complete inhibition of the grafting reaction by the phenolic monomer. On a variety of different polymers including atactic polypropylene, ethylene/vinyl acetate copolymer, poly(methyl methacrylate), poly(butyl acrylate), and polycarbonate were used.

Prenylated chalcones, flavone and other constituents of the twigs of Dorstenia angusticornis and Dorstenia barteri var. subtriangularis.

PubMed

Ngadjui, Bonaventure T; Watchueng, Jean; Keumedjio, Felix; Ngameni, Bathélémy; Simo, Ingrid K; Abegaz, Berhanu M

2005-03-01

The twigs of Dorstenia angusticornis and Dorstenia barteri var. subtriangularis yielded 16 compounds. Two novel diprenylated chalcones: 3,5'-di-(2-hydroxy-3-methylbut-3-enyl)-4,2',4'-trihydroxychalcone, 3, 4-(2,2-dimethylpyrano)-3'-(2-hydroxy-3-methylbut-3-enyl)-2',4'-dihydroxychalcone and the known stipulin were isolated from both species. 3-(2-Hydroxy-3-methylbut-3-enyl)-5'-(3,3-dimethylallyl)-4,2',4'-trihydroxychalcone and the known compounds: 4-hydroxylonchocarpin, kanzonol B, bartericins A, B, C and 3'-(2-hydroxy -3-methylbut-3-enyl)-4,2',4'-trihydroxychalcone were isolated from D. barteri while the known compounds: gancaonin Q, paratocarpins C, F, and lupeol were obtained from Dorstenia angusticornis. beta-Sitosterol and its beta-d-glucopyranoside were isolated from both species. Structures of these secondary metabolites were established using spectroscopic analysis, especially, NMR spectra in conjunction with 2D experiments, COSY, HMQC and HMBC.

Antimicrobial activity of α-(2-hydroxy-2-methylpropyl)-ω-(2-hydroxy-3-methylbut-2-en-1-yl) polymethylene from caesalpinia bonducella (L.) Flem

PubMed Central

Sagar, Kavitha; Vidyasagar, G. M.

2010-01-01

The compound, α-(2-hydroxy-2-methylpropyl)-ω-(2-hydroxy-3-methylbut-2-en-1-yl)polymethylene, isolated from ethyl acetate leaf extract of Caesalpinia bonducella (L.) Flem. was evaluated for antimicrobial activity against clinical isolates, Proteus vulgaris, Pseudomonas aeruginosa, Klebsiella sp., Staphylococcus citrus, Staphylococcus aureus, Escherichia coli, Candida albicans and Rhodotorula sp. using agar diffusion method. The compound exerted inhibitory zone at all concentrations and revealed the concentration-dependent activity against all tested bacterial and yeast strains comparable to standards streptomycin sulphate and gentamycin for bacteria and fluconazole and griseofulvin for Candida albicans and Rhodotorula sp. The inhibition zones were wider and clear for C. albicans and Rhodotorula sp. (IZ >20 mm) and for Pseudomonas aeruginosa, P. vulgaris and E. coli zones were greater than standards tested, whereas, zones for Klebsiella sp. and S. aureus were similar to standards. PMID:21218063

Sono-activated persulfate oxidation of diclofenac: Degradation, kinetics, pathway and contribution of the different radicals involved.

PubMed

Monteagudo, J M; El-Taliawy, H; Durán, A; Caro, G; Bester, K

2018-06-20

Degradation of a diclofenac aqueous solution was performed using persulfate anions activated by ultrasound. The objective of this study was to analyze different parameters affecting the diclofenac (DCF) removal reaction by the ultrasonic persulfate (US/PS) process and to evaluate the role played by various intermediate oxidative species such as hydroxyl- and sulfate radicals, superoxide radical anion or singlet oxygen in the removal process as well as to determine a possible reaction pathway. The effects of pH, initial persulfate anion concentration, ultrasonic amplitude and temperature on DCF degradation were examined. Sulfate and hydroxyl radicals were involved in the main reaction pathway of diclofenac. Diclofenac amide and three hydroxy-diclofenac isomers (3´-hydroxy diclofenac, 4´-hydroxy diclofenac and 5-hydroxy diclofenac) were identified as reaction intermediates. Copyright © 2018 Elsevier B.V. All rights reserved.

Aliphatic C-C Bond Cleavage in α-Hydroxy Ketones by a Dioxygen-Derived Nucleophilic Iron-Oxygen Oxidant.

PubMed

Bhattacharya, Shrabanti; Rahaman, Rubina; Chatterjee, Sayanti; Paine, Tapan K

2017-03-17

A nucleophilic iron-oxygen oxidant, formed in situ in the reaction between an iron(II)-benzilate complex and O 2 , oxidatively cleaves the aliphatic C-C bonds of α-hydroxy ketones. In the cleavage reaction, α-hydroxy ketones without any α-C-H bond afford a 1:1 mixture of carboxylic acid and ketone. Isotope labeling studies established that one of the oxygen atoms from dioxygen is incorporated into the carboxylic acid product. Furthermore, the iron(II) complex cleaves an aliphatic C-C bond of 17-α-hydroxyprogesterone affording androstenedione and acetic acid. The O 2 -dependent aliphatic C-C bond cleavage of α-hydroxy ketones containing no α-C-H bond bears similarity to the lyase activity of the heme enzyme, cytochrome P450 17A1 (CYP17A1). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

When private water rights become a public asset: Stakeholder perspectives on the fairness of environmental water management

NASA Astrophysics Data System (ADS)

Lukasiewicz, Anna; Dare, Melanie (Lain)

2016-05-01

This paper explores environmental water management as a social process of navigating conflicting interests through a distributive justice lens. Environmental water management can achieve substantial ecological outcomes and address ongoing river degradation caused by past management and climate change; however it also causes specific and substantial burdens and benefits to different groups of stakeholders. Given that in most developed countries the majority of land is under private tenure, environmental watering must have active cooperation of private landholders to achieve its ecological outcomes and thus it must effectively deal with an array of vested interests. Australia's reforms aimed at reallocating water from production to the environment have resulted in significant considerable volumes of environmental water. In the state of New South Wales, this water is managed by the state and national governments with the help of five Environmental Water Advisory Groups made up of a wide representation of interests. In this paper, we explore the perceptions of environmental, government, irrigator and grazing representatives, which demonstrate conflicting principles over how environmental water should be distributed. We detail how government water managers reconcile competing distributive principles of equity (ensuring that no one is disproportionally affected or benefits unduly), need (achieving environmental outcomes) and efficiency (prioritizing operational feasibility) in order to maintain the social acceptability of environmental water.

Phototransformation of the sunlight filter benzophenone-3 (2-hydroxy-4-methoxybenzophenone) under conditions relevant to surface waters.

PubMed

Vione, Davide; Caringella, Rosalinda; De Laurentiis, Elisa; Pazzi, Marco; Minero, Claudio

2013-10-01

The UV filter benzophenone-3 (BP3) has UV photolysis quantum yield ΦBP3=(3.1±0.3)·10(-5) and the following second-order reaction rate constants: with (•)OH, k(BP3,(•)OH)=(2.0±0.4)·10(10) M(-1) s(-1); with the triplet states of chromophoric dissolved organic matter ((3)CDOM*), K(BP3,(3)CDOM*)=(1.1±0.1)·10(9) M(-1) s(-1); with (1)O2, k(BP3,(1)O2)=(2.0±0.1)·10(5) M(-1) s(-1), and with CO3(-•), k(BP3,CO3(-•))<5·10(7) M(-1) s(-1). These data allow the modelling of BP3 photochemical transformation, which helps filling the knowledge gap about the environmental persistence of this compound. Under typical surface-water conditions, direct photolysis and reactions with (•)OH and (3)CDOM* would be the main processes of BP3 phototransformation. Reaction with (•)OH would prevail at low DOC, direct photolysis at intermediate DOC (around 5 mg C L(-1)), and reaction with (3)CDOM* at high DOC. If the reaction rate constant with CO3(-•) is near the upper limit of experimental measures (5·10(7) M(-1) s(-1)), the CO3(-•) degradation process could be somewhat important for DOC<1 mg C L(-1). The predicted half-life time of BP3 in surface waters under summertime conditions would be of some weeks, and it would increase with increasing depth and DOC. BP3 transformation intermediates were detected upon reaction with (•)OH. Two methylated derivatives were tentatively identified, and they were probably produced by reaction between BP3 and fragments arising from photodegradation. The other intermediates were benzoic acid (maximum concentration ~10% of initial BP3) and benzaldehyde (1%). Copyright © 2013 Elsevier B.V. All rights reserved.

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.

78 FR 18562 - Economic and Environmental Principles and Requirements for Water and Related Land Resources...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-03-27

... COUNCIL ON ENVIRONMENTAL QUALITY Economic and Environmental Principles and Requirements for Water... ``Economic and Environmental Principles and Guidelines for Water and Related Land Resources Implementation... Secretary of the Army to revise the ``Economic and Environmental Principles and Guidelines for Water and...

78 FR 18562 - Economic and Environmental Principles and Guidelines for Water and Related Land Resources...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-03-27

... COUNCIL ON ENVIRONMENTAL QUALITY Economic and Environmental Principles and Guidelines for Water... the Army to revise the ``Economic and Environmental Principles and Guidelines for Water and Related... Army to revise the ``Economic and Environmental Principles and Guidelines for Water and Related Land...

Photoprotectant improves photostability and bioactivity of abscisic acid under UV radiation.

PubMed

Gao, Fei; Hu, Tanglu; Tan, Weiming; Yu, Chunxin; Li, Zhaohu; Zhang, Lizhen; Duan, Liusheng

2016-05-01

Photosensitivity causes serious drawback for abscisic acid (ABA) application, but preferable methods to stabilize the compound were not found yet. To select an efficient photoprotectant for the improvement of photostability and bioactivity of ABA when exposed to UV light, we tested the effects of a photostabilizer bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (HS-770) and two UV absorbers 2-hydroxy-4-n-octoxy-benzophenone (UV-531) and 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (BP-4) with or without HS-770 on the photodegradation of ABA. Water soluble UV absorber BP-4 and oil soluble UV absorber UV-531 showed significant photo-stabilizing capability on ABA, possibly due to competitive energy absorption of UVB by the UV absorbers. The two absorbers showed no significant difference. Photostabilizer HS-770 accelerated the photodegradation of ABA and did not improve the photo-stabilizing capability of BP-4, likely due to no absorption in UVB region and salt formation with ABA and BP-4. Approximately 26% more ABA was kept when 280mg/l ABA aqueous solution was irradiated by UV light for 2h in the presence of 200mg/l BP-4. What's more, its left bioactivity on wheat seed (JIMAI 22) germination was greatly kept by BP-4, comparing to that of ABA alone. The 300 times diluent of 280mg/l ABA plus 200mg/l BP-4 after 2h irradiation showed more than 13% inhibition on shoot and root growth of wheat seed than that of ABA diluent alone. We concluded that water soluble UV absorber BP-4 was an efficient agent to keep ABA activity under UV radiation. The results could be used to produce photostable products of ABA compound or other water soluble agrichemicals which are sensitive to UV radiation. The frequencies and amounts of the agrichemicals application could be thereafter reduced. Copyright © 2016 Elsevier B.V. All rights reserved.

A Simple and Sensitive LC-MS/MS Method for the Determination of Free 8-Hydroxy-2'-Deoxyguanosine in Human Urine

NASA Technical Reports Server (NTRS)

Wang, Zuwei; Smith, Scott M.

2016-01-01

Urinary free 8-hydroxy-2'-deoxyguanosine (8OHdG), an oxidized product of DNA, and is frequently chosen as a biomarker of oxidative stress in humans, including studies of oxidative DNA damage during space flight. It is challenging to accurately and efficiently quantify urinary free 8OHdG in large scale human studies. LC-MS/MS is emerging as a preferable analytical technique owing its high sensitivity, selectivity and efficiency, compared to some traditional methods such as ELISA and HPLC. A simple and sensitive LC-MS/MS method has been developed for the determination of free 8OHdG in human urine. Sample preparation was done by solid phase extraction with a Waters Oasis HLB 96 well plate. A Waters Alliance 2795 HT Separation Module combined with a Quattro Micro tandem mass spectrometer was used as the LC-MS/MS system. The runtime of one injection can be less than 5 minutes using a reversed phase C18 column and an isocratic flow of methanol/water. ESI positive ions were quantified in the multiple reaction modes (MRM) using m/z 284 yields 168 for 8OHdG and m/z 289 yields173 for stable isotope labeled internal standard [(15)N5] 8OHdG. With this method for 8OHdG, a lower limit of quantitation of 1.0 nM (0.28 ng/mL) has been achieved using 100 microliter urine sample. The analytical range is between 1.0 and 100 nM with a correlation coefficient greater than or equal to 0.99. Good reproducibility can be obtained with intra-assay and inter-assay CVs less than or equal to 10% for 8OHdG spiked urine QC samples. This method can be used in high-throughput routine analysis of free 8OHdG in human urine.

Increased urinary 8-hydroxy-2'-deoxyguanosine levels in workers exposed to di-(2-ethylhexyl) phthalate in a waste plastic recycling site in China.

PubMed

Wang, Qian; Wang, Li; Chen, Xi; Rao, Kai Min; Lu, Shao You; Ma, Sheng Tao; Jiang, Pu; Zheng, Dan; Xu, Shun Qing; Zheng, Hong Yan; Wang, Jian Shu; Yu, Zhi Qiang; Zhang, Rong; Tao, Yong; Yuan, Jing

2011-07-01

Di-(2-ethylhexyl) phthalate (DEHP) is a common plasticizer used in industrial and diverse consumer products. Animal studies indicate DEHP caused developmental, reproductive, and hepatic toxicities. However, human studies of the potential effects of DEHP are limited. The exposed site with a history of over 20 years of waste plastic recycling was located in Hunan Province, China. The reference site without known DEHP pollution source was about 50 km far away from the exposed site. In this study, 181 workers working in plastic waste recycling and 160 gender-age matched farmers were recruited. DEHP concentrations in water and cultivated soil samples, serum thyroid-stimulating hormone, malondialdehyde (MDA), superoxide dismutase (SOD), urinary 8-hydroxy-2'-deoxyguanosine (8-OHdG), and micronuclei frequency in human capillary blood lymphocytes were analyzed. Mean levels of DEHP were greater in environment at the recycling site than at reference site (industry wastewater for the exposed: 42.43 μg/l; well water: 14.20 vs. 0.79 μg/l, pond water: 135.68 vs. 0.37 μg/l, cultivated soil: 13.07 vs. 0.81 mg/kg, p < 0.05 for all). The workers had higher median levels of MDA (3.80 vs. 3.14 nmol/ml) and urinary 8-OHdG (340.37 vs. 268.18 μmol/mol creatinine) and decreased SOD activities (112.15 vs. 123.82 U/ml) than the reference group (p < 0.01 for all). Multivariate analysis revealed that the history of working in waste plastic recycling was an independent risk factor for the increased urinary 8-OHdG levels in the male workers (p < 0.01). The occupational DEHP exposure might contribute to oxidative deoxyribonucleic acid damage in the male workers.

Effects of β-hydroxy-β-methylbutyrate free acid and cold water immersion on expression of CR3 and MIP-1β following resistance exercise.

PubMed

Gonzalez, Adam M; Fragala, Maren S; Jajtner, Adam R; Townsend, Jeremy R; Wells, Adam J; Beyer, Kyle S; Boone, Carleigh H; Pruna, Gabriel J; Mangine, Gerald T; Bohner, Jonathan D; Fukuda, David H; Stout, Jeffrey R; Hoffman, Jay R

2014-04-01

The inflammatory response to muscle-damaging exercise requires monocyte mobilization and adhesion. Complement receptor type 3 (CR3) and macrophage inflammatory protein (MIP)-1β enables monocyte recruitment, adhesion, and subsequent infiltration into damaged muscle tissue. The purpose of this study was to examine the effects of cold water immersion (CWI) and/or β-hydroxy-β-methylbutyrate free acid (HMB-FA) on CR3 expression and MIP-1β concentration after four sets of up to 10 repetitions of squat, dead lift, and split squat exercises at 70-80% 1-repetition maximum. Thirty-nine resistance-trained men (22.2 ± 2.5 yr) were randomly divided into four groups: 1) placebo (PL), 2) HMB-FA, 3) HMB-FA-CWI, and 4) PL-CWI. The HMB-FA groups ingested 3 g/day, and CWI groups were submersed into 10-12°C water for 10 min after exercise. Blood was sampled at baseline (PRE), immediately post- (IP), 30 min post- (30P), 24 h post- (24P), and 48 h post (48P)-exercise. Circulating MIP-1β was assayed and CR3 expression on CD14+ monocytes was measured by flow cytometry. Without treatment, CR3 expression significantly elevated at 30P compared with other time points (P = 0.030-0.047). HMB-FA significantly elevated the percentage of monocytes expressing CR3 between IP and 24P (P = 0.046) and between IP and 48P (P = 0.046). No time effect was observed for MIP-1β concentration. The recovery modalities showed to attenuate the rise in CR3 following exercise. Additionally, supplementation with HMB-FA significantly elevated the percentage of monocytes expressing CR3 during recovery. Although the time course that inflammatory responses are most beneficial remains to be determined, recovery modalities may alter immune cell mobilization and adhesion mechanisms during tissue recovery.

Profiling ABA metabolites in Nicotiana tabacum L. leaves by ultra-performance liquid chromatography-electrospray tandem mass spectrometry.

PubMed

Turecková, Veronika; Novák, Ondrej; Strnad, Miroslav

2009-11-15

We have developed a simple method for extracting and purifying (+)-abscisic acid (ABA) and eight ABA metabolites--phaseic acid (PA), dihydrophaseic acid (DPA), neophaseic acid (neoPA), ABA-glucose ester (ABAGE), 7'-hydroxy-ABA (7'-OH-ABA), 9'-hydroxy-ABA (9'-OH-ABA), ABAaldehyde, and ABAalcohol--before analysis by a novel technique for these substances, ultra-performance liquid chromatography-electrospray ionisation tandem mass spectrometry (UPLC-ESI-MS/MS). The procedure includes addition of deuterium-labelled standards, extraction with methanol-water-acetic acid (10:89:1, v/v), simple purification by Oasis((R)) HLB cartridges, rapid chromatographic separation by UPLC, and sensitive, accurate quantification by MS/MS in multiple reaction monitoring modes. The detection limits of the technique ranged between 0.1 and 1 pmol for ABAGE and ABA acids in negative ion mode, and 0.01-0.50 pmol for ABAGE, ABAaldehyde, ABAalcohol and the methylated acids in positive ion mode. The fast liquid chromatographic separation and analysis of ABA and its eight measured derivatives by UPLC-ESI-MS/MS provide rapid, accurate and robust quantification of most of the substances, and the low detection limits allow small amounts of tissue (1-5mg) to be used in quantitative analysis. To demonstrate the potential of the technique, we isolated ABA and its metabolites from control and water-stressed tobacco leaf tissues then analysed them by UPLC-ESI-MS/MS. Only ABA, PA, DPA, neoPA, and ABAGE were detected in the samples. PA was the most abundant analyte (ca. 1000 pmol/g f.w.) in both the control and water-stressed tissues, followed by ABAGE and DPA, which were both present at levels ca. 5-fold lower. ABA levels were at least 100-fold lower than PA concentrations, but they increased following the water stress treatment, while ABAGE, PA, and DPA levels decreased. Overall, the technique offers substantial improvements over previously described methods, enabling the detailed, direct study of diverse ABA metabolites in small amounts of plant tissue.

A New Group of Disinfection Byproducts in Drinking Water: Trihalo-hydroxy-cyclopentene-diones.

PubMed

Pan, Yang; Li, Wenbin; Li, Aimin; Zhou, Qing; Shi, Peng; Wang, Ying

2016-07-19

We report the detection, synthesis, preparative isolation, structure characterization and identification, and formation of a new group of drinking water disinfection byproducts (DBPs): trihalo-hydroxy-cyclopentene-diones (trihalo-HCDs). With ultra performance liquid chromatography (UPLC)/electrospray ionization-triple quadruple mass spectrometry analyses (full scans, multiple reaction monitoring, and product ion scans) and high-resolution mass spectrometry analyses (full scans), the new group of DBPs was identified with formulae and proposed with structures. However, due to a lack of commercially available standard compounds, structure identification of this new group of DBPs was challenging. 2,4,6-Trihydroxybenzaldehyde was found to be a good precursor for the synthesis of the tribromo species (m/z 345/347/349/351) in the new group of DBPs by reacting with bromine at a 2,4,6-trihydroxybenzaldehyde-to-bromine molar ratio of 1:8. With UPLC/photodiode array analysis (simultaneous 2- and 3-dimensional operations), the new DBP was determined to have a maximum UV absorption at the wavelength of 280 nm. Through isolation with high performance liquid chromatography/UV-triggered collections followed by lyophilization, the pure standard of the new DBP was obtained. Characterized with Fourier transform infrared spectroscopy, the pure standard of the new DBP was finally identified to be tribromo-HCD, and thus the new group of DBPs was identified to be trihalo-HCDs. On the basis of the disclosed structure, formation pathways of tribromo-HCD through reactions of three different precursors and bromine were proposed and partially verified. Moreover, increasing the bromide level in source water shifted the formation of trihalo-HCDs from being more chlorinated to being more brominated; with an increase in the contact time from 1 h to 5 d, the formation of trihalo-HCDs kept increasing in chloramination, whereas they kept decreasing in chlorination; with an increase in the pH from 6.0 to 8.5, the formation of trihalo-HCDs was decreased by ∼80%. Notably, the concentrations of tribromo-HCD in eight Chinese tap water samples were from below the detection limit to 0.53 μg/L.

Involvement of Cholinergic Dysfunction and Oxidative Damage in the Effects of Simulated Weightlessness on Learning and Memory in Rats

PubMed Central

Wang, Qiong; Lv, Ke; Wang, Tingmei; Wang, Yanli; Ji, Guohua; Cao, Hongqing; Kan, Guanghan

2018-01-01

The present study aimed to determine how the learning and memory gradually change with the prolonged hindlimb unloading (HU) treatment in rats. Different HU durations (7 d, 14 d, 21 d, and 28 d) in Sprague-Dawley (SD) rats were implemented. Cognitive function was assessed using the Morris water maze (MWM) and the shuttle box test. Additionally, parameters about cholinergic activity and oxidative stress were tested. Results showed that longer-than-14 d HU led to the inferior performances in the behavioral tasks. Besides, acetylcholine esterase (AChE) activity, malondialdehyde (MDA) level in brain, reactive oxygen species (ROS), and 8-hydroxy-2-deoxyguanosine (8-OHdG) concentrations of HU rats were significantly increased. Furthermore, choline acetyltransferase (ChAT), superoxide dismutase (SOD), and catalase (CAT) activity in brain were notably attenuated. Most of these effects were more pronounced after longer exposure (21 d and 28 d) to HU, although some indicators had their own characteristics of change. These results indicate that cholinergic dysfunction and oxidative damage were involved in the learning and memory impairments induced by longer-than-14 d HU. Moreover, the negative effects of HU tend to be augmented as the HU duration becomes longer. The results may be helpful to present possible biochemical targets for countermeasures development regarding the memory deficits under extreme environmental conditions. PMID:29581965

Microbiology, chemistry and biofilm development in a pilot drinking water distribution system with copper and plastic pipes.

PubMed

Lehtola, Markku J; Miettinen, Ilkka T; Keinänen, Minna M; Kekki, Tomi K; Laine, Olli; Hirvonen, Arja; Vartiainen, Terttu; Martikainen, Pertti J

2004-10-01

We studied the changes in water quality and formation of biofilms occurring in a pilot-scale water distribution system with two generally used pipe materials: copper and plastic (polyethylene, PE). The formation of biofilms with time was analysed as the number of total bacteria, heterotrophic plate counts and the concentration of ATP in biofilms. At the end of the experiment (after 308 days), microbial community structure, viable biomass and gram-negative bacterial biomass were analysed via lipid biomarkers (phospholipid fatty acids and lipopolysaccharide 3-hydroxy fatty acids), and the numbers of virus-like particles and total bacteria were enumerated by SYBR Green I staining. The formation of biofilm was slower in copper pipes than in the PE pipes, but after 200 days there was no difference in microbial numbers between the pipe materials. Copper ion led to lower microbial numbers in water during the first 200 days, but thereafter there were no differences between the two pipe materials. The number of virus-like particles was lower in biofilms and in outlet water from the copper pipes than PE pipes. Pipe material influenced also the microbial and gram-negative bacterial community structure in biofilms and water.

Structure of aureobasidin A.

PubMed

Ikai, K; Takesako, K; Shiomi, K; Moriguchi, M; Umeda, Y; Yamamoto, J; Kato, I; Naganawa, H

1991-09-01

Aureobasidin A, a new antifungal antibiotic, was isolated from the culture medium of Aureobasidium pullulans R106. Aureobasidin A was a cyclic depsipeptide consisting of eight alpha-amino acid units and one hydroxy acid unit. The structures of the units were found by acid hydrolysis of the antibiotic to be 2(R)-hydroxy-3(R)-methylpentanoic acid, beta-hydroxy-N-methyl-L-valine, N-methyl-L-valine, L-proline, allo-L-isoleucine, N-methyl-L-phenylalanine, L-leucine, and L-phenyl-alanine. The sequence of the units was identified by NMR and FAB-MS of the products from the alkaline hydrolysis of aureobasidin A.

Structure elucidation of two triterpenoid saponins from rhizome of Anemone raddeana Regel.

PubMed

Lu, Jincai; Xu, Beibei; Gao, Song; Fan, Li; Zhang, Hongfen; Liu, Runxiang; Kodama, Hiroyuki

2009-09-01

Two new 27-hydroxy-oleanolic acid type triterpenoid saponins, raddeanoside 20 (1) and raddeanoside 21(2) were isolated from the rhizome of Anemone raddeana Regel. The structures of the two compounds were elucidated as 27-hydroxy-oleanolic acid 3-O-alpha-L-rhamnopyranosyl(1-->2) [beta-D-glucopyranosyl (1-->4)]-alpha-L-arabinopyranoside (1) and 3-O-alpha-L-rhamnopyranosyl (1-->2)-alpha-L-arabinopyranosyl-27-hydroxy-oleanolic acid 28-O-alpha-L-rhamnopyranosyl(1-->4)-beta-D-glucopyranosyl (1-->6)-beta-D-glucopyranoside (2) on the basis of chemical and spectral evidence.

[Studies on flavonoids of Oxytropis falcata].

PubMed

Lu, Fang; Xu, Xiao-Jie

2007-02-01

To investigate the flavonoids of Oxytropisfalcata. Compounds were isolated by column chromatography using silica gel, Sephadex LH -20 and ODS as the adsorbents. Their structures were elucidated by NMR and MS spectroscopic data. Eight compounds were isolated and elucidated as 2', 4'-dihydroxy-4-methoxy chalcone (1), 2', 4'-dihydroxy chalcone (2), 5,7-dihydroxy-4'-methoxy flavonol (3), 7-hydroxy-4'-methoxy flavanones (4), 3', 7-dihydroxy-2',4'-dimethoxy isoflavan (5), 2'-hydroxy-4'-methoxy chalcone (6), 2'-methoxy-4'-hydroxy chalcone (7), 2',4'-dihydroxy dihydrochalcone (8). All compounds were obtained from O. falcata for the first time.

Gibberellins in shoots and developing capsules of Populus species.

PubMed

Pearce, David W; Hutt, Oliver E; Rood, Stewart B; Mander, Lewis N

2002-03-01

Extracts of stems of growing shoots of Populus deltoides and P. trichocarpa, and developing capsules of P. deltoides were analysed for gibberellins (GAs) by gas chromatography-mass spectrometry. The following known GAs were identified by comparison of their Kovats retention indices (KRIs) and mass spectra with those of standards: GA1, GA8, GA9, GA19, GA20, 16 beta,17-dihydro-17-hydroxy GA20, GA23, GA28, GA29, GA34, GA44, and GA97. Several of these have not been previously reported from Populus. In addition, two new GAs were identified as 12 beta-hydroxy GA53 (GA127) and 16 beta,17-dihydro-17-hydroxy GA53 and their structures were confirmed by partial synthesis. Evidence was found of 16,17-dihydro-16,17-dihydroxy GA9, 16,17-dihydro-16,17-dihydroxy GA12, 12-hydroxy GA14, and GA34-catabolite by comparison of mass spectra and KRIs with published data. Several putative GAs (hydroxy- and dihydroxy-GA12-like) were also found. The catabolites of active GAs or of key precursors, hydroxylated at C-2 in stems and either C-2, C-12, C-17, or C-16,17 in capsules, were the major proportion of the GAs.

[Homoisoflavanones and stilbenes from fresh bulb of Scilla scilloides].

PubMed

Wang, Yan-Min; Fan, Meng-Yang; Li, Juan; Wang, Zhi-Min; Gao, Hui-Min

2014-10-01

Mian-Zao-Er was collected from the bulbs of Scilla scilloides (Lindl. ) Druce, belonging to the Hyacinthaceae family. 17 compounds were obtained using various column chromatographies on macroporus resin (HPD100), silica gel, Sephadex LH-20 and ODS, as well as semi-preparative HPLC. Their structures were elucidated on the basis of physicochemical properties and spectral data as 2-hydroxy-7-methoxyscillascillin (1), scillascillin (2), 5,7-dihydroxy-3',4'-dimethoxyspiro 2H-1-benzopyran-7'-bicyclo[4.2.0 ] octa [1,3,5 ] -trien } -4-one (3), socialinone (4), 4-methylresveratrol (5), (E)-resveratrol (6), scillavoneA (7), 3,9-di- hydroeucomnalin (8), 3-(3-hydroxy-4-methoxybenzyl) -5,7-dihydroxychroman-4-one (9), (3R)-5,7,3'-trihydroxy-4'-methoxyspiro (2H-1-benzopyran-7'-bicyclo[4, 2, 0] octa [1, 3, 5]-trien} -4-one (10), scillabene A (11), 2-hydroxyscillascillin (12), 3-(4-hydroxybenzyl) -5,7-dihydroxychroman-4-one (13), 3-( 4-hydroxybenzylidene) -5, 7-dihydroxychroman-4-one (14), 3-( 4-hydroxybenzyl) -5-hydroxy-7,8-dimethoxychroman-4-one (15), 3-(4-hydroxybenzyl) -5-hydroxy-6, 7-dimethoxychroman-4-one (16), and 3-(4-hydroxybenzyl)-5,8-hydroxy-7-methoxychroman-4-one (17). Among them, compounds 3, 4, 6, 9, 13 and 15-17 were isolated from this plant for the first time.

Structure-Activity Studies of Semiochemicals from the Spider Orchid Caladenia plicata for Sexual Deception.

PubMed

Bohman, Bjorn; Karton, Amir; Flematti, Gavin R; Scaffidi, Adrian; Peakall, Rod

2018-05-01

Sexually deceptive orchids attract specific pollinators by mimicking insect sex pheromones. Normally this mimicry is very specific and identical compounds have been identified from orchids and matching females of the pollinators. In this study, we conduct a detailed structure-activity investigation on isomers of the semiochemicals involved in the sexual attraction of the male pollinator of the spider orchid Caladenia plicata. This orchid employs an unusual blend of two biosynthetically unrelated compounds, (S)-β-citronellol and 2-hydroxy-6-methylacetophenone, to lure its Zeleboria sp. thynnine wasp pollinator. We show that the blend is barely attractive when (S)-β-citronellol is substituted with its enantiomer, (R)-β-citronellol. Furthermore, none of the nine-possible alternative hydroxy-methylacetophenone regioisomers of the natural semiochemical are active when substituted for the natural 2-hydroxy-6-methylacetophenone. Our results were surprising given the structural similarity between the active compound and some of the analogues tested, and results from previous studies in other sexually deceptive orchid/wasp systems where substitution with analogues was possible. Interestingly, high-level ab initio and density functional theory calculations of the hydroxy-methylacetophenones revealed that the active natural isomer, 2-hydroxy-6-methylacetophenone, has the strongest intramolecular hydrogen bond of all regioisomers, which at least in part may explain the specific activity.

Vitamin D levels in acne vulgaris patients treated with oral isotretinoin.

PubMed

El-Hamd, Mohammed Abu; El Taieb, Moustafa A; Ibrahim, Hassan M; Aly, Sanaa S

2018-02-20

Acne vulgaris is a common inflammatory skin disease. Vitamin D deficiency plays a role in many inflammatory skin diseases. It may play a role in pathogenesis of acne vulgaris. This study aimed to assess serum levels of 25 hydroxy vitamin D in patients with acne vulgaris before and after treatment with isotretinoin and its relation with acne vulgaris severity. Ninety patients with acne vulgaris and 60 age-sex matched healthy subject as controls have been recruited in this study. Patients were treated with 0.75 mg/kg/d isotretinoin for 3 months. Serum level of 25 hydroxy vitamin D has been measured at baseline and after treatment. Serum levels of 25 hydroxy vitamin D were significantly higher in patients with acne vulgaris than healthy controls (P = .001). There was a significant inverse relation between level of 25 hydroxy vitamin D and severity of acne vulgaris before treatment (P = .001). Serum levels of 25 hydroxy vitamin D were significantly increased after isotretinoin treatment in patients with acne vulgaris (P = .001). This study concluded that vitamin D may play a potential role in pathogenesis of acne vulgaris or acne vulgaris may have a negative effect on vitamin D synthesis. Further studies are needed to confirm these potential relations. © 2018 Wiley Periodicals, Inc.

γ-Dodecelactone production from safflower oil via 10-hydroxy-12(Z)-octadecenoic acid intermediate by whole cells of Candida boidinii and Stenotrophomonas nitritireducens.

PubMed

Jo, Ye-Seul; An, Jung-Ung; Oh, Deok-Kun

2014-07-16

Candida boidinii was selected as a γ-dodecelactone producer because of the highest production of γ-dodecelactone from 10-hydroxy-12(Z)-octadecenoic acid among the 11 yeast strains tested. Under the reaction conditions of pH 5.5 and 25 °C with 5 g/L 10-hydroxy-12(Z)-octadecenoic acid and 30 g/L cells, whole C. boidinii cells produced 2.1 g/L γ-dodecelactone from 5 g/L 10-hydroxy-12(Z)-octadecenoic acid after 6 h, with a conversion yield of 64% (mol/mol) and a volumetric productivity of 350 mg/L/h. The production of γ-dodecelactone from safflower oil was performed by lipase hydrolysis reaction and two-step whole-cell biotransformation using Stenotrophomonas nitritireducens and C. boidinii. γ-Dodecelactone at 1.88 g/L was produced from 7.5 g/L safflower oil via 5 g/L 10-hydroxy-12(Z)-octadecenoic acid intermediate by these reactions after 8 h of reaction time, with a volumetric productivity of 235 mg/L/h and a conversion yield of 25% (w/w). To the best of the authors' knowledge, this is the highest volumetric productivity and conversion yield reported to date for the production of γ-lactone from natural oils.

Study on the structures and anti-hepatic fibrosis activity of stilbenoids from Arundina graminifolia (D. Don) Hochr.

NASA Astrophysics Data System (ADS)

Liu, Qingqing; Wang, Huiting; Lin, Fankai; Dai, Rongji; Yu, Deng lin; Lv, Fang

2017-12-01

A phytochemical study was performed on Arundina graminifolia (D.Don) Hochr. by silica gel column and semi-preparative HPLC, and ten stilbenoids were obtained. Their structures were elucidated by NMR and MS spectra and identified as 7-hydroxy-2,4-dimethoxy-9,10-dihydrophenanthrene (1), 4,7-dihydroxy-2-methoxy-9,10-dihydrophenanthrene (2), 2,7-dihydroxy-4-methoxy-9,10-dihydrophenanthrene (3), 3,3’-dihydroxy-5-methoxy-bibenzyl (4), 7-hydroxy-2,8-dimethoxy-phenanthrene-1,4-dione (5), 7-hydroxy-2,10-dimethoxy-phenanthre-ne-1,4-dione (6), 7-dihydroxy-2-methoxy-9,10-dihydrophenanthrene-1,4-dione (7), 7-hydroxy-2-methoxy-phenanthrene-1,4-dione (8), 7-hydroxy-1-(p-hydroxybenzyl)-2,4-dimethoxy-9,10-dihydroxy-phenanthrene (9), 2,7-dihydroxy-1-(p-hydroxybenzyl)-4-methoxy-9,10-dihydroxy-phenanthrene (10). Compounds 5 and 6 were isolated from this plant for the first time. The isolated compounds were examined for their anti-hepatic fibrosis activity against HSC-T6 cells in vitro. The results showed that compounds 4 and 5 exhibited moderate growth inhibitory effects with IC50 61.9 μg/mL and 52.7 μg/mL, respectively.

Production and identification of a novel compound, 7,10-dihydroxy-8(E)-hexadecenoic acid from palmitoleic acid by Pseudomonas aeruginosa PR3.

PubMed

Bae, Jae-Han; Kim, Deuk-Soo; Suh, Min-Jung; Oh, Sei-Ryang; Lee, In-Jung; Kang, Sun-Chul; Hou, Ching T; Kim, Hak-Ryul

2007-05-01

Hydroxy fatty acids are considered as important value-added product for industrial application because of their special properties such as higher viscosity and reactivity. Microbial production of the hydroxy fatty acids from various fatty acid substrates have been actively studied using several microorganisms. The new bacterial isolate Pseudomonas aeruginosa (PR3) had been reported to produce mono-, di-, and tri-hydroxy fatty acids from different unsaturated fatty acids. Of those, 7,10-dihydroxy-8(E)-octadecenoic acid (DOD) and 7,10,12-trihydroxy-8(E)-octadecenoic acid (TOD) were produced from oleic acid and ricinoleic acid, respectively. Based on the postulated common metabolic pathway involved in DOD and TOD formation by PR3, it was assumed that palmitoleic acid containing a singular 9-cis double bond, common structural property sharing with oleic acid and ricinoleic acid, could be utilized by PR3 to produce hydroxy fatty acid. In this study, we tried to use palmitoleic acid as substrate for production of hydroxy fatty acid by PR3 and firstly confirmed that PR3 could produce 7,10-dihydroxy-8(E)-hexadecenoic acid (DHD) with 23% yield from palmitoleic acid. DHD production was peaked at 72 h after the substrate was added to the 24-h-culture.

40 CFR 136.3 - Identification of test procedures.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Environment, Water, and Wastes. Environmental Monitoring and Support Laboratory, U.S. Environmental Protection... Water and Wastes,” Environmental Protection Agency, Environmental Monitoring Systems Laboratory....3 Section 136.3 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) WATER PROGRAMS...

40 CFR 136.3 - Identification of test procedures.

Code of Federal Regulations, 2011 CFR

2011-07-01

... Environment, Water, and Wastes. Environmental Monitoring and Support Laboratory, U.S. Environmental Protection... Water and Wastes,” Environmental Protection Agency, Environmental Monitoring Systems Laboratory....3 Section 136.3 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) WATER PROGRAMS...

Phytoextraction, phytotransformation and rhizodegradation of ibuprofen associated with Typha angustifolia in a horizontal subsurface flow constructed wetland.

PubMed

Li, Yifei; Zhang, Jiefeng; Zhu, Guibing; Liu, Yu; Wu, Bing; Ng, Wun Jern; Appan, Adhityan; Tan, Soon Keat

2016-10-01

Widespread occurrence of trace pharmaceutical residues in aquatic environments is of great concerns due to the potential chronic toxicity of certain pharmaceuticals including ibuprofen on aquatic organisms even at environmental levels. In this study, the phytoextraction, phytotransformation and rhizodegradation of ibuprofen associated with Typha angustifolia were investigated in a horizontal subsurface flow constructed wetland system. The experimental wetland system consisted of a planted bed with Typha angustifolia and an unplanted bed (control) to treat ibuprofen-loaded wastewater (∼107.2 μg L(-1)). Over a period of 342 days, ibuprofen was accumulated in leaf sheath and lamina tissues at a mean concentration of 160.7 ng g(-1), indicating the occurrence of the phytoextraction of ibuprofen. Root-uptake ibuprofen was partially transformed to ibuprofen carboxylic acid, 2-hydroxy ibuprofen and 1-hydroxy ibuprofen which were found to be 1374.9, 235.6 and 301.5 ng g(-1) in the sheath, respectively, while they were 1051.1, 693.6 and 178.7 ng g(-1) in the lamina. The findings from pyrosequencing analysis of the rhizosphere bacteria suggest that the Dechloromonas sp., the Clostridium sp. (e.g. Clostridium saccharobutylicum), the order Sphingobacteriales, and the Cytophaga sp. in the order Cytophagales were most probably responsible for the rhizodegradation of ibuprofen. Copyright © 2016 Elsevier Ltd. All rights reserved.

Patch tests with fragrance mix II and its components.

PubMed

Pónyai, Györgyi; Németh, Ilona; Altmayer, Anita; Nagy, Gabriella; Irinyi, Beatrix; Battyáni, Zita; Temesvári, Erzsébet

2012-01-01

Fragrance mix II (FM II) was initiated to detect contact hypersenstitivity (CH) to fragrances that could not have been identified previously. The aim of this multicenter study was to map the frequency of CH to FM II and its components in Hungary. Six centers participated in the survey from 2009 to 2010. A total off 565 patients (434 women and 131 men) with former skin symptoms provoked by scented products were patch tested. The tests were performed with Brial GmbH D-Greven allergens. In the environmental patch test series, FM II, FM I, Myroxylon pereirae, colophonium, wood-tar mix, propolis, and sesquiterpene lactone mix were tested as fragrance allergens. The FM II components (citral, farnesol, coumarin, citronellol, α-hexyl-cinnamaldehyde, and hydroxy-isohexyl-3-cyclohexene-carboxaldehyde [Lyral]) were also tested. Contact hypersenstitivity to any fragrances was detected in 28.8%, to FM II in 17.2% of the patients. Contact hypersenstitivity to hydroxy-isohexyl-3-cyclohexene-carboxaldehyde was observed in 7.3%, to coumarin in 5.1%, to α-hexyl-cinnamaldehyde in 3.5%, to citral in 3.4%, to farnesol in 2.5%, and to citronellol in 1.2%. Of the FM II-positive cases, 48.4% showed isolated CH reaction. The frequency of CH to FM II is 17.2% in the tested, selected Hungarian population. The CH to FM II and its components could not have been revealed without the present test materials.

The Spatial Distributions and Variations of Water Environmental Risk in Yinma River Basin, China.

PubMed

Di, Hui; Liu, Xingpeng; Zhang, Jiquan; Tong, Zhijun; Ji, Meichen

2018-03-15

Water environmental risk is the probability of the occurrence of events caused by human activities or the interaction of human activities and natural processes that will damage a water environment. This study proposed a water environmental risk index (WERI) model to assess the water environmental risk in the Yinma River Basin based on hazards, exposure, vulnerability, and regional management ability indicators in a water environment. The data for each indicator were gathered from 2000, 2005, 2010, and 2015 to assess the spatial and temporal variations in water environmental risk using particle swarm optimization and the analytic hierarchy process (PSO-AHP) method. The results showed that the water environmental risk in the Yinma River Basin decreased from 2000 to 2015. The risk level of the water environment was high in Changchun, while the risk levels in Yitong and Yongji were low. The research methods provide information to support future decision making by the risk managers in the Yinma River Basin, which is in a high-risk water environment. Moreover, water environment managers could reduce the risks by adjusting the indicators that affect water environmental risks.

Preparation of highly fluorinated diols containing ether linkages.

NASA Technical Reports Server (NTRS)

Rochow, S. E.; Stump, E. C., Jr.

1970-01-01

Hydroxy-terminated perfluoroethers and polyurethane resins derived from ethers have outstanding chemical resistance and good thermal properties. They can be used as potting compounds, coatings, and seals. The hydroxy-terminated ethers serve as intermediates in the synthesis of highly fluorinated elastomers and adhesives.

Iron Hydroxy Carbonate Formation in Zerovalent Iron Permeable Reactive Barriers: Characterization and Evaluation of Phase Stability

EPA Science Inventory

Predicting the long-term potential of permeable reactive barriers for treating contaminated groundwater relies on understanding the endpoints of biogeochemical reactions between influent groundwater and the reactive medium. Iron hydroxy carbonate (chukanovite) is frequently obs...

SOLVENT-FREE FACILE SYNTHESIS OF NOVEL α-TOSYLOXY β-KETO SULFONES USING [HYDROXY(TOSYLOXY)IODO]BENZENE

EPA Science Inventory

A facile, general and high yielding protocol for the synthesis of novel α-tosyloxy β-keto sulfones is described utilizing relatively non-toxic, [hydroxy(tosyloxy)iodo]benzene, under solvent-free conditions at room temperature.

Effects of combined maternal administration with alpha-ketoglutarate (AKG) and β-hydroxy-β-methylbutyrate (HMB) on prenatal programming of skeletal properties in the offspring.

PubMed

Tatara, Marcin R; Krupski, Witold; Tymczyna, Barbara; Studziński, Tadeusz

2012-05-11

Nutritional manipulations during fetal growth may induce long-term metabolic effects in postnatal life. The aim of the study was to test whether combined treatment of pregnant sows with alpha-ketoglutarate and β-hydroxy-β-methylbutyrate induces additive long-term effects on skeletal system properties in the offspring. The study was performed on 290 pigs obtained from 24 sows divided into 4 equal groups and subjected to experimental treatment during two weeks before delivery. The first group consisted of control sows, while the second group received alpha-ketoglutarate. The third group was treated with β-hydroxy-β-methylbutyrate and the fourth group underwent combined administration of alpha-ketoglutarate and β-hydroxy-β-methylbutyrate. Piglets obtained from sows were reared until slaughter age to perform morphometric, densitometric and mechanical analyses of femur. Serum evaluations of growth hormone, insulin-like growth factor-1, bone-specific alkaline phosphatase and osteocalcin were performed in newborns and 90-day old piglets; additionally, plasma amino acid concentration was measured in newborns. Maternal treatment with alpha-ketoglutarate and β-hydroxy-β-methylbutyrate significantly reduced fattening time and increased birth body weight, daily body weight gain, bone weight, volumetric bone mineral density, geometrical parameters and mechanical endurance of femur. These effects were associated with increased serum concentrations of growth hormone, insulin-like growth factor-1, bone-specific alkaline phosphatase and osteocalcin. Furthermore, alpha-ketoglutarate and β-hydroxy-β-methylbutyrate administered solely or in combination significantly increased plasma level of 19 amino acids. Hormonal and amino acid evaluations in pigs indicate additive effects of AKG and HMB on systemic growth and development; however, determination of bone properties has not shown such phenomenon.

Effects of combined maternal administration with alpha-ketoglutarate (AKG) and β-hydroxy-β-methylbutyrate (HMB) on prenatal programming of skeletal properties in the offspring

PubMed Central

2012-01-01

Background Nutritional manipulations during fetal growth may induce long-term metabolic effects in postnatal life. The aim of the study was to test whether combined treatment of pregnant sows with alpha-ketoglutarate and β-hydroxy-β-methylbutyrate induces additive long-term effects on skeletal system properties in the offspring. Methods The study was performed on 290 pigs obtained from 24 sows divided into 4 equal groups and subjected to experimental treatment during two weeks before delivery. The first group consisted of control sows, while the second group received alpha-ketoglutarate. The third group was treated with β-hydroxy-β-methylbutyrate and the fourth group underwent combined administration of alpha-ketoglutarate and β-hydroxy-β-methylbutyrate. Piglets obtained from sows were reared until slaughter age to perform morphometric, densitometric and mechanical analyses of femur. Serum evaluations of growth hormone, insulin-like growth factor-1, bone-specific alkaline phosphatase and osteocalcin were performed in newborns and 90-day old piglets; additionally, plasma amino acid concentration was measured in newborns. Results Maternal treatment with alpha-ketoglutarate and β-hydroxy-β-methylbutyrate significantly reduced fattening time and increased birth body weight, daily body weight gain, bone weight, volumetric bone mineral density, geometrical parameters and mechanical endurance of femur. These effects were associated with increased serum concentrations of growth hormone, insulin-like growth factor-1, bone-specific alkaline phosphatase and osteocalcin. Furthermore, alpha-ketoglutarate and β-hydroxy-β-methylbutyrate administered solely or in combination significantly increased plasma level of 19 amino acids. Conclusions Hormonal and amino acid evaluations in pigs indicate additive effects of AKG and HMB on systemic growth and development; however, determination of bone properties has not shown such phenomenon. PMID:22578071

Location of fluorescent probes (2'-hydroxy derivatives of 2,5-diaryl-1,3-oxazole) in lipid membrane studied by fluorescence spectroscopy and molecular dynamics simulation.

PubMed

Posokhov, Yevgen; Kyrychenko, Alexander

2018-04-01

2'-Hydroxy derivatives of 2,5-diaryl-1,3-oxazole are known as environment-sensitive ratiometric excited-state intramolecular proton transfer (ESIPT) fluorescent probes, which are used to monitor physicochemical properties of lipid membranes. However, because of their heterogeneous membrane distribution, accurate experimental determination of the probe position is difficult. To estimate the location of the ESIPT probes in lipid membranes we have performed fluorescence measurements and molecular dynamics (MD) simulations. In the series composed of 2-(2'-hydroxy-phenyl)-5-phenyl-1,3-oxazole (1), 2-(2'-hydroxy-phenyl)-5-(4'-biphenyl)-1,3-oxazole (2), and 2-(2'-hydroxy-phenyl)-phenanthro[9,10-d]-1,3-oxazole (3), the structure of the ESIPT-moiety of 2-(2'-hydroxy-phenyl)-oxazole was varied by either aromatic ring substitution or annealing, leading to the systematical increase in the hydrophobic character of the probes. The comparison of the fluorescence behavior of probes 1-3 in a wide variety of solvents with those in phospholipid vesicles revealed that all three probes prefer to reside inside a membrane. Our MD results demonstrate that the probes locate from the glycerol residues and the polar carbonyl groups of phospholipids up to hydrophobic acyl chain units. It has been found that the probe location correlates well with the size of the aromatic moiety, being gradually shifted from 11.1 Å to 7.6 Å from the bilayer center for probes 1 to 3, respectively. Our results may be useful for the design of novel fluorescent probes for fluorescence sensing of specific regions within a lipid membrane. Copyright © 2018 Elsevier B.V. All rights reserved.

Metabolism of the Synthetic Progestogen Norethynodrel by Human Ketosteroid Reductases of the Aldo-Keto Reductase Superfamily

PubMed Central

Jin, Yi; Duan, Ling; Chen, Mo; Penning, Trevor M; Kloosterboer, Helenius J.

2012-01-01

Human ketosteroid reductases of the aldo-keto reductase (AKR) superfamily, i.e. AKR1C1-4, are implicated in the biotransformation of synthetic steroid hormones. Norethynodrel (NOR, 17α-ethynyl-17β-hydroxy-estra-5(10)-en-3-one), the progestin component of the first marketed oral contraceptive, is known to undergo rapid and extensive metabolism to 3α- and 3β-hydroxy metabolites. The ability of the four human AKR1C enzymes to catalyze the metabolism of NOR has now been characterized. AKR1C1 and AKR1C2 almost exclusively converted NOR to 3β-hydroxy NOR, while AKR1C3 gave 3β-hydroxy NOR as the main product and AKR1C4 predominantly formed 3α-hydroxy NOR. Individual AKR1C enzymes also displayed distinct kinetic properties in the reaction of NOR. In contrast, norethindrone (NET), the Δ4-isomer of NOR and the most commonly used synthetic progestin, was not a substrate for the AKR1C enzymes. NOR is also structurally identical to the hormone replacement therapeutic tibolone (TIB), except TIB has a methyl group at the 7α-position. Product profiles and kinetic parameters for the reduction of NOR catalyzed by each individual AKR1C isoform were identical to those for the reduction of TIB catalyzed by the respective isoform. These data suggest that the presence of the 7α-methyl group has a minimal effect on the stereochemical outcome of the reaction and kinetic behavior of each enzyme. Results indicate a role of AKR1C in the hepatic and peripheral metabolism of NOR to 3α- and 3β-hydroxy NOR and provide insights into the differential pharmacological properties of NOR, NET and TIB. PMID:22210085

Synthesis, DNA binding and cytotoxic activity of pyrimido[4',5':4,5]thieno(2,3-b)quinoline with 9-hydroxy-4-(3-diethylaminopropylamino) and 8-methoxy-4-(3-diethylaminopropylamino) substitutions.

PubMed

KiranKumar, Hulihalli N; RohitKumar, Heggodu G; Advirao, Gopal M

2018-01-01

Two new derivatives of pyrimido[4',5';4,5]thieno(2,3-b)quinoline (PTQ), 9-hydroxy-4-(3-diethylaminopropylamino)pyrimido[4',5';4,5]thieno(2,3-b)quinoline (Hydroxy-DPTQ) and 8-methoxy-4-(3-diethylaminopropylamino)pyrimido[4',5';4,5]thieno(2,3-b)quinoline (Methoxy-DPTQ) were synthesized and their DNA binding ability was analyzed using spectroscopy (UV-visible, fluorescence and circular dichroism), ethidium bromide dye displacement assay, melting temperature (T m ) analysis and computational docking studies. The hypochromism in UV-visible spectrum and increased fluorescence emission of Hydroxy-DPTQ and Methoxy-DPTQ in the presence of DNA suggested the molecule-DNA interaction. The association constants calculated from UV-visible and spectral titrations were of the order 10 4 to 10 6 M -1 . Circular dichroism studies corroborated the induced conformational changes in DNA upon addition of molecules. The change in the ellipticity was observed both in negative and positive peak of DNA, thus, suggesting the intercalation of molecules. The observed displacement of ethidium bromide from the DNA and increased T m , upon addition of DNA confirmed the intercalative mode of binding. This was further validated by computational docking, which showed clear intercalation of molecules into the d(GpC)-d(CpG) site of the receptor DNA. Anticancer activities of these molecules are evaluated by using MTT assay. Both molecules showed antiproliferative activity against all the three cancer cells studied, with Hydroxy-DPTQ being more potential molecule among the two. IC 50 value of Hydroxy-DPTQ and Methoxy-DPTQ were in the range of 3-5μM and 130-250μM, respectively. Copyright © 2017 Elsevier B.V. All rights reserved.

Steroid catechol degradation: disecoandrostane intermediates accumulated by Pseudomonas transposon mutant strains.

PubMed

Leppik, R A

1989-07-01

Eleven transposon mutant strains affected in bile acid catabolism were each found to form yellow, muconic-like intermediates from bile acids. To characterize these unstable intermediates, media from the growth of one of these mutants with deoxycholic acid was treated with ammonia, then the crude product was methylated with diazomethane. Four compounds were subsequently isolated; spectral evidence suggested that they were methyl 12 alpha-hydroxy-3-oxo-23,24-dinorchola-1,4-dien-22-oate, methyl 4-aza-12 beta-hydroxy-9(10)-secoandrosta-1,3,5-triene-9,17-dione-3-carboxyl ate, 4-aza-9 alpha, 12 beta-dihydroxy-9(10)-secoandrosta-1,3,5-trien-17-one-3- methyl carboxylate and 4 alpha-[3'-propionic acid]-5-amino-7 beta-hydroxy-7 alpha beta-methyl- 3a alpha, 4,7,7a-tetrahydro-1-indanone-delta-lactam. It is proposed that the mutants are blocked in the utilization of such muconic-like compounds as the 3,12 beta-dihydroxy-5,9,17-trioxo-4(5),9(10)- disecoandrostal (10),2-dien-4-oic acid formed from deoxycholic acid. A further mutant was examined, which converted deoxycholic acid to 12 alpha-hydroxyandrosta-1,4-dien-3,17-dione, but accumulated yellow products from steroids which lacked a 12 alpha-hydroxy function, such as chenodeoxycholic acid. The products from the latter acid were treated as above; spectral evidence suggested that the two compounds isolated were methyl 4-aza-7-hydroxy-9(10)-secoandrosta-1,3,5- triene-9,17-dione-3-carboxylate and 4 alpha-[1'alpha-hydroxy-3'-propionic acid]-5-amino-7a beta-methyl-3a alpha,4,7,7a-tetrahydro-1-indanone-delta-lactam.

Monitoring And Modeling Environmental Water Quality To Support Environmental Water Purchase Decision-making

NASA Astrophysics Data System (ADS)

Null, S. E.; Elmore, L.; Mouzon, N. R.; Wood, J. R.

2016-12-01

More than 25 million cubic meters (20,000 acre feet) of water has been purchased from willing agricultural sellers for environmental flows in Nevada's Walker River to improve riverine habitat and connectivity with downstream Walker Lake. Reduced instream flows limit native fish populations, like Lahontan cutthroat trout, through warm daily stream temperatures and low dissolved oxygen concentrations. Environmental water purchases maintain instream flows, although effects on water quality are more varied. We use multi-year water quality monitoring and physically-based hydrodynamic and water quality modeling to estimate streamflow, water temperature, and dissolved oxygen concentrations with alternative environmental water purchases. We simulate water temperature and dissolved oxygen changes from increased streamflow to prioritize the time periods and locations that environmental water purchases most enhance trout habitat as a function of water quality. Monitoring results indicate stream temperature and dissolved oxygen limitations generally exist in the 115 kilometers upstream of Walker Lake (about 37% of the study area) from approximately May through September, and this reach acts as a water quality barrier for fish passage. Model results indicate that low streamflows generally coincide with critically warm stream temperatures, water quality refugia exist on a tributary of the Walker River, and environmental water purchases may improve stream temperature and dissolved oxygen conditions for some reaches and seasons, especially in dry years and prolonged droughts. This research supports environmental water purchase decision-making and allows water purchase decisions to be prioritized with other river restoration alternatives.

Spatial and Temporal Distribution of Particulate Organic Carbon in the Winisk River, Northern Ontario

NASA Astrophysics Data System (ADS)

Glasauer, S.; Smith, P.; Smith, R. W.

2016-12-01

The Winisk River begins in the Precambrian rock of the Canadian Shield in Ontario and traverses the Hudson Bay Lowlands before terminating in Hudson Bay. It drains an area of 67,300 km2that is sparsely populated, with remote communities that depend on natural resources. Accelerated decomposition of organic carbon (OC) in the area due to climate change is supported by higher inputs of particulate and dissolved OC to surface waters (Amon et al, 2012). The Winisk River is a particularly important source of OC to Hudson Bay, shown by high rates of lignin accumulation near the mouth of the river (Kuzyk et al., 2008). Webequie First Nation (WFN) is a small community located on Eastwood Island in Winisk Lake. It is the closest community to the proposed massive development of the "Ring of Fire" chromite and other mineral deposits in the James Bay Lowlands. Mine-related developments can be expected to impact water flows, water chemistry, and carbon cycling in the region. We sampled water and sediment at the major inlets to the lake and at the northern outlet within the territorial boundaries to characterize water chemistry, relate lignin compositional patterns to C and N isotopic signatures, and interpret temporal patterns in advance of development and future climate change. Organic C in the sediments ranged from around 1% to around 30%. Samples were analyzed for lignin compounds using a CuO digestion method coupled to GC-MS to identify lignin-phenol monomers, benzoic acids, and p-hydroxy acid. Ratios of 3,5-dihydroxybenzoic acid, P-hydroxy phenols and cinnamyl phenols to total vanillyl phenols indicate that gymnosperm wood and sphagnum peat dominate the OC pool, although the proportions of gymnosperm- and sphagnum-derived material vary between sites. Stable isotope analysis (δ13C, δ15N) suggests that other inputs of OC may be present that are consistent with OM derived from the erosion of older marine sediments. The results support that the proportion of sphagnum mosses and the total particulate OC will increase as warming continues, in accordance with climate change predictions for the region. Amon RMW et al. 2012. Geochim. Cosmochim. Acta 94, 217. Kurzyk ZZA, Goni MA, Stern GA and Macdonald RW. 2008. Marine Chem. 112, 215.

Effects of the Deslagging Process on some Physicochemical Parameters of Honey

PubMed Central

Ranjbar, Ali Mohammad; Sadeghpour, Omid; Khanavi, Mahnaz; Shams Ardekani, Mohammad Reza; Moloudian, Hamid; Hajimahmoodi, Mannan

2015-01-01

Some physicochemical parameters of honey have been introduced by the International Honey Commission to evaluate its quality and origin but processes such as heating and filtering can affect these parameters. In traditional Iranian medicine, deslagging process involves boiling honey in an equal volume of water and removing the slag formed during process. The aim of this study was to determine the effects of deslagging process on parameters of color intensity, diastase evaluation, electrical conductivity, pH, free acidity, refractive index, hydroxy methyl furfural (HMF), proline and water contents according to the International Honey Committee (IHC) standards. The results showed that deslagged honey was significantly different from control honey in terms of color intensity, pH, diastase number, HMF and proline content. It can be concluded that the new standards are needed to regulate deslagged honey. PMID:25901175

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...

Interaction of phenolic acids and their derivatives with human serum albumin: Structure-affinity relationships and effects on antioxidant activity.

PubMed

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

2018-02-01

In this study, 111 phenolic acids and their derivatives were chosen to investigate their structure-affinity relationships when binding to human serum albumin (HSA), and effects on their antioxidant activity. A comprehensive mathematical model was employed to calculate the binding constants, using a fluorescence quenching method, and this was corrected for the inner-filter effect to improve accuracy. We found that a hydroxy group at the 2-position of the benzene ring exerted a positive effect on the affinities, while a 4-hydroxy substituent had a negative influence. Both methylation of the hydroxy groups and replacing the hydroxy groups with methyl groups at the 3- and 4-positions of the benzene ring enhanced the binding affinities. Hydrophobic force and hydrogen bonding were binding forces for the phenolic acids, and their methyl esters, respectively. The antioxidant activity of the HSA-phenolic acid interaction compounds was higher than that of the phenolic acids alone. Copyright © 2017. Published by Elsevier Ltd.

Production of ω-hydroxy octanoic acid with Escherichia coli.

PubMed

Kirtz, Marko; Klebensberger, Janosch; Otte, Konrad B; Richter, Sven M; Hauer, Bernhard

2016-07-20

The present proof-of-concept study reports the construction of a whole-cell biocatalyst for the de novo production of ω-hydroxy octanoic acid. This was achieved by hijacking the natural fatty acid cycle and subsequent hydroxylation using a specific monooxygenase without the need for the additional feed of alkene-like precursors. For this, we used the model organism Escherichia coli and increased primarily the release of the octanoic acid precursors by overexpressing the plant thioesterase FatB2 from Cuphea hookeriana in a β-oxidation deficient strain, which lead to the production of 2.32mM (8.38mggcww(-1)) octanoic acid in 24h. In order to produce the corresponding ω-hydroxy derivative, we additionally expressed the engineered self-sufficient monooxygenase fusion protein CYP153AMaq(G307A)-CPRBM3 within the octanoic acid producing strain. With this, we finally produced 234μM (0.95mggcww(-1)) ω-hydroxy octanoic acid in a 20h fed-batch set-up. Copyright © 2016 Elsevier B.V. All rights reserved.

Complete structural characterization of ceramides as [M – H]− ions by multiple-stage linear ion trap mass spectrometry

PubMed Central

Hsu, Fong-Fu

2016-01-01

Ceramide is a huge lipid family consisting of diversified structures including various modifications in the fatty acyl chain and the long chain base (LCB). In this contribution, negative-ion ESI linear ion-trap multiple-stage mass spectrometric method (LIT MSn) towards complete structural determination of ceramides in ten major families characterized as the [M – H]− ions is described. Multiple sets of fragment ions reflecting the fatty acyl chain and LCB were observed in the CID MS2 spectrum, while the sequential MS3 and MS4 spectra contain structural information for locating the double bond and the functional groups, permitting realization of the fragmentation processes. Thereby, differentiation of ceramide molecules varied by chain length, the LCB (sphingosine, phytosphigosine, 6-hydroxy-sphingosine), and by the modification (α-hydroxy-, β-hydroxy-, ω-hydroxy-FA) can be achieved; and many isomeric structures in the biological specimen can be revealed in detail. PMID:27523779

Identification of sinensetin metabolites in rat urine by an isotope-labeling method and ultrahigh-performance liquid chromatography-electrospray ionization mass spectrometry.

PubMed

Wei, Guor-Jien; Sheen, Jenn-Feng; Lu, Wen-Chien; Hwang, Lucy Sun; Ho, Chi-Tang; Lin, Ching-I

2013-05-29

Sinensetin (SIN), one of the major polymethoxyflavones (PMFs) contained mainly in the citrus peels, has been reported to possess various bioactivities, including antifungal, antimutagenic, anticancer, and anti-inflammatory activities. Although the biotransformation of SIN in fungi and insects has been reported, the information about the metabolism of SIN in mammals is still unclear. In this study, formation of SIN metabolites in rats was investigated. Four isotope-labeled SINs ([4'-D3]SIN, [3'-D3]SIN, [5-D3]SIN, and [6-D3]SIN) were synthesized and administered to rat. The urine samples were collected and main metabolites were monitored by ultrahigh-performance liquid chromatography-electrospray ionization mass spectrometry. The administered compound and four SIN metabolites were detected in rat urine. These metabolites were identified as 4'-hydroxy-5,6,7,3'-tetramethoxyflavone, 5-hydroxy-6,7,3',4'-tetramethoxyflavone, 6-hydroxy-5,7,3',4'-tetramethoxyflavone, and 7-hydroxy-5,6,3',4'-tetramethoxyflavone sulfate.

7 CFR 1700.30 - Water and Environmental Programs.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 7 Agriculture 11 2011-01-01 2011-01-01 false Water and Environmental Programs. 1700.30 Section..., DEPARTMENT OF AGRICULTURE GENERAL INFORMATION Agency Organization and Functions § 1700.30 Water and Environmental Programs. RUS, through the Water and Environmental Programs, provides loan and grant funds for...

7 CFR 1700.30 - Water and Environmental Programs.

Code of Federal Regulations, 2014 CFR

2014-01-01

... 7 Agriculture 11 2014-01-01 2014-01-01 false Water and Environmental Programs. 1700.30 Section..., DEPARTMENT OF AGRICULTURE GENERAL INFORMATION Agency Organization and Functions § 1700.30 Water and Environmental Programs. RUS, through the Water and Environmental Programs, provides loan and grant funds for...

7 CFR 1700.30 - Water and Environmental Programs.

Code of Federal Regulations, 2012 CFR

2012-01-01

... 7 Agriculture 11 2012-01-01 2012-01-01 false Water and Environmental Programs. 1700.30 Section..., DEPARTMENT OF AGRICULTURE GENERAL INFORMATION Agency Organization and Functions § 1700.30 Water and Environmental Programs. RUS, through the Water and Environmental Programs, provides loan and grant funds for...

7 CFR 1700.30 - Water and Environmental Programs.

Code of Federal Regulations, 2013 CFR

2013-01-01

... 7 Agriculture 11 2013-01-01 2013-01-01 false Water and Environmental Programs. 1700.30 Section..., DEPARTMENT OF AGRICULTURE GENERAL INFORMATION Agency Organization and Functions § 1700.30 Water and Environmental Programs. RUS, through the Water and Environmental Programs, provides loan and grant funds for...

Individual organic compounds in water extracts from podzolic soils of the Komi Republic

NASA Astrophysics Data System (ADS)

Shamrikova, E. V.; Punegov, V. V.; Gruzdev, I. V.; Vanchikova, E. V.; Vetoshkina, A. A.

2012-10-01

The contents of organic compounds in water extracts from organic horizons of loamy soils with different water contents from the medium taiga zone of the Komi Republic were determined by gas-liquid chromatography and chromatography-mass spectrometry. The mass concentration of organic carbon in the extracts was in the range of 290-330 mg/dm3; the mass fraction of the carbon from the identified compounds was 0.5-1.9%. Hydrocarbons made up about 60% of the total identified compounds; acids and their derivatives composed less than 40%. Most of the acids (40-70%) were aliphatic hydroxy acids. The tendencies in the formation of different classes of organic compounds were revealed depending on the degree of the soil hydromorphism. The acid properties of the water-soluble compounds were studied by pK spectroscopy. Five groups of compounds containing acid groups with similar pKa values were revealed. The compounds containing groups with pKa < 4.0 were predominant. The increase in the surface wetting favored the formation of compounds with pKa 3.2-4.0 and 7.4-8.4.

Adsorption of multilamellar tubes with a temperature tunable diameter at the air/water interface.

PubMed

Fameau, Anne-Laure; Douliez, Jean-Paul; Boué, François; Ott, Frédéric; Cousin, Fabrice

2011-10-15

The ethanolamine salt of 12-hydroxy stearic acid is known to form tubes having a temperature tunable diameter. Here, we study the behavior of those tubes at the air/water interface by using Neutron Reflectivity. We observed that tubes indeed adsorbed at this interface below a fatty acid monolayer and exhibit the same temperature behavior as in bulk. There is however a peculiar behavior at around 50 °C for which the increase of the diameter of the tubes at the interface yields an unfolding of those tubes into a multilamellar layer. Upon further heating, the tubes re-fold and their diameter re-decreases after which they melt into micelles as observed in the bulk. All structural transitions at the interface are nevertheless reversible. This provides to the system a high interest for its interfacial properties because the structure at the air/water interface can be tuned easily by the temperature. Copyright © 2011 Elsevier Inc. All rights reserved.

Synthesis, characterization, swelling and dye adsorption properties of starch incorporated acrylic gels.

PubMed

Mandal, Bidyadhar; Ray, Samit Kumar

2015-11-01

Several hydrogels were prepared by a free radical polymerization of acrylic acid (AA), sodium acrylate (SA) and AA/hydroxy ethyl methacrylate (HEMA) in the presence of starch in water. These starch incorporated acrylic gels were prepared by varying the concentration of the initiator, monomer, crosslinker and the starch. The resulting gels were characterized by FTIR, SEM, XRD, DTA-TGA, pH at point zero charge (PZC), swelling and the diffusion in water. The gels showed high adsorption and removal% of Safranine T (ST) and Brilliant Cresyl Blue (BCB) dyes from water. The swelling and the adsorption data were fitted to different kinetic models and isotherms. Amongst the three kinds of gels, the starch incorporated sodium polyacrylate gel showed the highest adsorption of 9.7-85.3mg/L (97-61% removal) of BCB dye and 9.1-83mg/L (91-60% removal) of ST dye for a feed dye concentration of 10-140mg/L. Copyright © 2015 Elsevier B.V. All rights reserved.

Biotransformations of 2-Methylisoborneol by Camphor-Degrading Bacteria ▿

PubMed Central

Eaton, Richard W.; Sandusky, Peter

2009-01-01

Many camphor-degrading bacteria that are able to transform 2-methylisoborneol (2-MIB) have been identified. Three of these strains have been examined in detail. Rhodococcus ruber T1 metabolizes camphor through 6-hydroxycamphor but converts 2-MIB to 3-hydroxy-2-MIB. Pseudomonas putida G1, which metabolizes camphor through 5-hydroxycamphor, converts MIB primarily to 6-hydroxy-2-MIB. Rhodococcus wratislaviensis DLC-cam converts 2-MIB through 5-hydroxy-2-MIB to 5-keto-2-MIB. Together, these three strains produce metabolites resulting from hydroxylation at all of the three available secondary carbons on the six-member ring of 2-MIB. PMID:19060161

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

PubMed

Longin, Ondřej; Černý, Ivan; Drašar, Pavel

2015-05-01

17β-O-Hemisuccinates of typical representatives of Anabolic-Androgenic Steroids, 17β-hydroxy-17-methylandrostan-4-en-3-one, 17β-hydroxy-17-methyl-2-oxa-5α-androstan-3-one, 17β-hydroxy-17-methyl-5α-androstano-[3,2-c]pyrazole, were prepared. Several methods for the hemisuccinate preparation were tested. The indirect method using 1-ethyl-3-(dimethylaminopropyl)carbodiimide coupling reagent to form an ester bond of steroid with 2-(trimethylsilyl)ethyl hydrogen butanedioate was finally applied. Using the selectively removable protecting group, the desired hemisuccinates of steroids bearing tertiary alcohol group were obtained. Copyright © 2014 Elsevier Ltd. All rights reserved.

Cytotoxic chalcones and flavonoids from the leaves of Muntingia calabura.

PubMed

Chen, Jih-Jung; Lee, Hsinn-Hsing; Duh, Chang-Yih; Chen, Ih-Sheng

2005-10-01

Two new dihydrochalcones, 2',4'-dihydroxy-3'-methoxydihydrochalcone, (-)-3'-methoxy-2',4',beta-trihydroxydihydrochalcone, a new flavanone, (2 S)-(-)-5'-hydroxy-7,3',4'-trimethoxyflavanone, and a new flavonol derivative, muntingone, along with sixteen known compounds, were isolated from the leaves of Muntingia calabura. The structures of these new compounds were determined using spectral analyses including extensive 2D NMR data. Among the isolates, (2 S)-5'-hydroxy-7,3',4'-trimethoxyflavanone, 4'-hydroxy-7-methoxyflavanone, 2',4'-dihydroxychalcone, and 2',4'-dihydroxy-3'-methoxychalcone exhibited cytotoxicity (IC (50) values < 4 microg/mL) against P-388 and/or HT-29 cell lines in vitro.

[Phenanthrene constituents from rhizome of Arundina graminifolia].

PubMed

Liu, Mei-feng; Ding, Yi; Zhang, Dong-ming

2005-03-01

To isolate and elucidate the constituents from rhizome of Arundina graminifolia. Theconstituents were extracted with 95% alcohol and isolated by chromatography on silica gel, Sephedax LH-20. The structures were determined by UV, IR, NMR and MS spectral analysis. Five phenanthrene constituents were identified as 7-hydroxy-2, 4-dimethoxy-9, 10-dihydrophenanthrene( I ), 4, 7-dihydroxy-2-methoxy-9, 10-dihydrophenanthrene ( II ), 2, 7-dihydroxy-4-methoxy-9, 10-dihydrophenanthrene ( III ), 7-hydroxy-2-methoxyphenanthrene-1,4-dione ( IV ), 7-hydroxy-2-methoxy-9, 10-dihydrophenanthrene-1,4-dione (V), respectively. All compounds were isolated from rhizome of A. graminifolia for the first time.

Preparation of 4-amino-2,4-dioxobutanoic acid

DOEpatents

Unkefer, Pat J.; Martinez, Rodolfo A.; Glass, David R.

2016-03-22

A process for synthesizing 4-amino-2,4-dioxobutanoate involves reacting a dialkyl oxalate with an alkoxide in ethanol to form a reaction mixture, and afterward adding an alkyl cyano acetate to the reaction mixture and allowing a reaction to proceed under conditions suitable to form a first reaction product of the formula diethyl 2-cyano-3-hydroxy-butenedioate, and then isolating the diethyl 2-cyano-3-hydroxy-butenedioate, and afterward reacting the diethyl-2-cyano-3-hydroxy-butenedioate with an aqueous hydroxide under conditions suitable to form 4-amino-2,4-dioxobutanoate. The 4-amino-2,4-dioxobutanoate may be acidified into 4-amino-2,4-dioxobutanoic acid.

Exploration of alternate catalytic mechanisms and optimization strategies for retroaldolase design.

PubMed

Bjelic, Sinisa; Kipnis, Yakov; Wang, Ling; Pianowski, Zbigniew; Vorobiev, Sergey; Su, Min; Seetharaman, Jayaraman; Xiao, Rong; Kornhaber, Gregory; Hunt, John F; Tong, Liang; Hilvert, Donald; Baker, David

2014-01-09

Designed retroaldolases have utilized a nucleophilic lysine to promote carbon-carbon bond cleavage of β-hydroxy-ketones via a covalent Schiff base intermediate. Previous computational designs have incorporated a water molecule to facilitate formation and breakdown of the carbinolamine intermediate to give the Schiff base and to function as a general acid/base. Here we investigate an alternative active-site design in which the catalytic water molecule was replaced by the side chain of a glutamic acid. Five out of seven designs expressed solubly and exhibited catalytic efficiencies similar to previously designed retroaldolases for the conversion of 4-hydroxy-4-(6-methoxy-2-naphthyl)-2-butanone to 6-methoxy-2-naphthaldehyde and acetone. After one round of site-directed saturation mutagenesis, improved variants of the two best designs, RA114 and RA117, exhibited among the highest kcat (>10(-3)s(-1)) and kcat/KM (11-25M(-1)s(-1)) values observed for retroaldolase designs prior to comprehensive directed evolution. In both cases, the >10(5)-fold rate accelerations that were achieved are within 1-3 orders of magnitude of the rate enhancements reported for the best catalysts for related reactions, including catalytic antibodies (kcat/kuncat=10(6) to 10(8)) and an extensively evolved computational design (kcat/kuncat>10(7)). The catalytic sites, revealed by X-ray structures of optimized versions of the two active designs, are in close agreement with the design models except for the catalytic lysine in RA114. We further improved the variants by computational remodeling of the loops and yeast display selection for reactivity of the catalytic lysine with a diketone probe, obtaining an additional order of magnitude enhancement in activity with both approaches. © 2013.

A Theoretical Study of 8-Chloro-9-Hydroxy-Aflatoxin B₁, the Conversion Product of Aflatoxin B₁ by Neutral Electrolyzed Water.

PubMed

Escobedo-González, René; Méndez-Albores, Abraham; Villarreal-Barajas, Tania; Aceves-Hernández, Juan Manuel; Miranda-Ruvalcaba, René; Nicolás-Vázquez, Inés

2016-07-21

Theoretical studies of 8-chloro-9-hydroxy-aflatoxin B₁ (2) were carried out by Density Functional Theory (DFT). This molecule is the reaction product of the treatment of aflatoxin B₁ (1) with hypochlorous acid, from neutral electrolyzed water. Determination of the structural, electronic and spectroscopic properties of the reaction product allowed its theoretical characterization. In order to elucidate the formation process of 2, two reaction pathways were evaluated-the first one considering only ionic species (Cl⁺ and OH(-)) and the second one taking into account the entire hypochlorous acid molecule (HOCl). Both pathways were studied theoretically in gas and solution phases. In the first suggested pathway, the reaction involves the addition of chlorenium ion to 1 forming a non-classic carbocation assisted by anchimeric effect of the nearest aromatic system, and then a nucleophilic attack to the intermediate by the hydroxide ion. In the second studied pathway, as a first step, the attack of the double bond from the furanic moiety of 1 to the hypochlorous acid is considered, accomplishing the same non-classical carbocation, and again in the second step, a nucleophilic attack by the hydroxide ion. In order to validate both reaction pathways, the atomic charges, the highest occupied molecular orbital and the lowest unoccupied molecular orbital were obtained for both substrate and product. The corresponding data imply that the C₉ atom is the more suitable site of the substrate to interact with the hydroxide ion. It was demonstrated by theoretical calculations that a vicinal and anti chlorohydrin is produced in the terminal furan ring. Data of the studied compound indicate an important reduction in the cytotoxic and genotoxic potential of the target molecule, as demonstrated previously by our research group using different in vitro assays.

Transformation of alpha-tocopherol (vitamin E) and related chromanol model compounds into their phenoxonium ions by chemical oxidation with the nitrosonium cation.

PubMed

Lee, Stephen B; Lin, Ching Yeh; Gill, Peter M W; Webster, Richard D

2005-12-09

[reaction: see text] Alpha-tocopherol (alpha-TOH), the main oil component making up vitamin E, and its nonnatural solid 6-hydroxy-2,2,5,7,8-pentamethylchroman and 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid structurally related analogues were oxidized quantitatively with 2 mol equiv of NO+ SbF6(-) in CH3CN at 233 K to form phenoxonium cations (alpha-TO+ SbF6(-)) in a chemically reversible two-electron/one-proton process. Solution-phase infrared spectroscopy, 1H and 13C NMR spectroscopy, and corresponding theoretical calculations of the spectroscopic data using density-based and wave-function-based models support the identity of the remarkably stable phenoxonium cations. The presence of an oxygen atom in the para position to the hydroxyl group and the chromanol ring structure appear to be important factors in stabilization of the phenoxonium ions, which raises the interesting possibility that the cations play a crucial role in the mode of action of vitamin E in biological systems. Although the phenoxonium cations are reactive toward nucleophiles such as water, they may be moderately stable in the hydrophobic (lipophilic) environment where vitamin E is known to occur naturally.

Hexagonal ZnO porous plates prepared from microwave synthesized layered zinc hydroxide sulphate via thermal decomposition

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

Machovsky, Michal, E-mail: machovsky@ft.utb.cz; Polymer Centre, Faculty of Technology, Tomas Bata University in Zlin, Nam. T.G. Masaryka 275, 762 72 Zlin; Kuritka, Ivo, E-mail: ivo@kuritka.net

2013-10-15

Graphical abstract: - Highlights: • Zinc hydroxy sulphate was synthesized in 3 min via microwave hydrothermal route. • Zinc hydroxy sulphate was converted into mesh like porous ZnO by calcining at 900°. • The process of transformation is topotactic. - Abstract: Layered zinc hydroxide sulphate (ZHS) was prepared by microwave-assisted hydrothermal precipitation of zinc sulphate monohydrate with hexamethylenetetramine. Under ambient conditions, the structure of ZHS determined by X-ray diffraction (XRD) was found to be a mixture of zinc hydroxide sulphate pentahydrate Zn{sub 4}SO{sub 4}(OH){sub 6}·5H{sub 2}O and tetrahydrate Zn{sub 4}SO{sub 4}(OH){sub 6}·4H{sub 2}O. Fourier transform infrared (FTIR) spectroscopy was usedmore » for characterization of the prepared materials. Based on the interpretation of ZHS's thermal decomposition profile obtained by thermogravimetric analysis, ZnO of high purity was prepared by calcination at 900 °C for 2 h. The structure of the resulting ZnO was confirmed by the XRD. The morphology examination by scanning electron microscopy revealed a porous mesh-like ZnO structure developed from the ZHS precursor at the expense of mass removal due to the release of water and sulphate during the calcination.« less