Fate and Transport of CL-20 and RDX in Unsaturated Laboratory Columns

NASA Astrophysics Data System (ADS)

Lemond, L. A.; Gamerdinger, A. P.; Szecsody, J. E.

2005-05-01

This research examines the fate and transport of two explosive compounds, Hexanitrohexaazaisowurtzitane (CL-20) and Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in unsaturated laboratory columns. The transport and fate of these compounds were studied under saturated and unsaturated conditions in three natural soils: coarse sand, sandy loam, and a silt loam. Unsaturated column experiments were conducted using an ultra-centrifugation method. Sorption and degradation parameters were determined by moment analysis and hydrodynamic parameters were assessed with a two-region flow model. Differences in these parameters were evaluated as a function of water content. The fate and transport of CL-20 is highly dependent on 1) the soil type and 2) the compound's residence time in the soil and 3) water content of the media. Sorption of CL-20 was rate-limited. CL-20 degradation in saturated columns produced a half-life of as much as 22hr, but in unsaturated columns the degradation rate increased considerably, producing a half life of as little as 2hr. The fate and transport of RDX are also affected by the soil type, but sorption appeared to be instantaneous. Degradation of RDX was negligible. Our results suggest that at very low water content immobile water regions may become (at least in effect) isolated water regions and significantly alter the retardation of the tracer. In the sandy loam, there was as much as a 20-fold over-prediction of the retardation factor in the unsaturated saturated columns when predicted by Kd values derived from saturated columns. In the coarse sand, Kd values derived from saturated columns over-predicted retardation in the unsaturated columns by as much as 30%. In the silt loam, retardation factors were over-predicted by as much as 80%. At very low water contents, predictions of tracer behavior become very difficult because of changes in the flow regime that cannot be directly accounted for.

Highly stereoselective three-component reactions of phenylselenomagnesium bromide, acetylenic sulfones, and saturated aldehydes/ketones or alpha,beta-unsaturated enals or enones.

PubMed

Huang, Xian; Xie, Meihua

2002-12-13

beta-Phenylseleno-alpha-tolylsulfonyl-substituted alkenes were synthesized via the three-component conjugate-nucleophilic addition of acetylenic sulfones, phenylselenomagnesium bromide, and carbonyl compounds, such as aldehydes, aliphatic ketones, or alpha,beta-unsaturated enals or enones. The reaction is highly regio- and stereoselective with moderate to good yields. Functionalized allylic alcohols were obtained in the case of aldehydes and aliphatic ketones. In the case of alpha,beta-unsaturated enones, functionalized allylic alcohols or functionalized gamma,delta-unsaturated ketones were obtained, depending on the structures of the ketones.

Fe(OTf)3-catalysed Friedel–Crafts reaction of benzenoid arenes with α,β-unsaturated carbonyl compounds: easy access to 1,1-diarylalkanes

PubMed Central

Bhattacharya, Aditya; Shukla, Pushpendra Mani

2017-01-01

A simple and efficient method for the synthesis of 1,1-diarylalkanes via the Friedel–Crafts-type alkylation reaction of electron-rich arenes with cinnamic acid ester derivatives or chalcones is reported. Iron triflate has been found to be the best catalyst for the Friedel–Crafts-type alkylation reaction with α,β-unsaturated carbonyl compounds. This reaction afforded β,β-diaryl carbonyl compounds in good yields (65–93%) and with excellent regioselectivities. Remarkably, this method is also compatible with a variety of indoles to provide 3-indolyl-aryl carbonyl compounds in excellent yields. Great efforts have been made to deduce a plausible reaction mechanism based on isotopic labelling experiments. PMID:29134078

Gold-catalyzed heterogeneous aerobic dehydrogenative amination of α,β-unsaturated aldehydes to enaminals.

PubMed

Jin, Xiongjie; Yamaguchi, Kazuya; Mizuno, Noritaka

2014-01-07

Although enaminals (β-enaminals) are very important compounds and have been utilized as useful synthons for various important compounds, they have been synthesized through non-green and/or limited procedures until now. Herein, we have successfully developed a green synthetic procedure using a heterogeneous catalyst. In the presence of gold nanoparticles supported on manganese-oxide-based octahedral molecular sieves OMS-2 (Au/OMS-2), dehydrogenative amination of α,β-unsaturated aldehydes with amines proceeded efficiently, with the corresponding enaminals isolated in moderate to high yields (50-97 %). The catalysis was truly heterogeneous, and Au/OMS-2 could be reused. Furthermore, the formal Wacker-type oxidation of α,β-unsaturated aldehydes to enaminones has been realized. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Consideration of reactivity to acute fish toxicity of α,β-unsaturated carbonyl ketones and aldehydes.

PubMed

Furuhama, A; Aoki, Y; Shiraishi, H

2012-01-01

To understand the key factor for fish toxicity of 11 α,β-unsaturated carbonyl aldehydes and ketones, we used quantum chemical calculations to investigate their Michael reactions with methanethiol or glutathione. We used two reaction schemes, with and without an explicit water molecule (Scheme-1wat and Scheme-0wat, respectively), to account for the effects of a catalytic water molecule on the reaction pathway. We determined the energies of the reactants, transition states (TS), and products, as well as the activation energies of the reactions. The acute fish toxicities of nine of the carbonyl compounds were evaluated to correlate with their hydrophobicities; no correlation was observed for acrolein and crotonaldehyde. The most toxic compound, acrolein, had the lowest activation energy. The activation energy of the reaction could be estimated with Scheme-1wat but not with Scheme-0wat. The complexity of the reaction pathways of the compounds was reflected in the difficulty of the TS structure searches when Scheme-1wat was used with the polarizable continuum model. The theoretical estimations of activation energies of α,β-unsaturated carbonyl compounds with catalytic molecules or groups including hydrogen-bond networks may complement traditional tools for predicting the acute aquatic toxicities of compounds that cannot be easily obtained experimentally.

Fatty Acid Structure and Degradation Analysis in Fingerprint Residues

NASA Astrophysics Data System (ADS)

Pleik, Stefanie; Spengler, Bernhard; Schäfer, Thomas; Urbach, Dieter; Luhn, Steven; Kirsch, Dieter

2016-09-01

GC-MS investigations were carried out to elucidate the aging behavior of unsaturated fatty acids in fingerprint residues and to identify their degradation products in aged samples. For this purpose, a new sample preparation technique for fingerprint residues was developed that allows producing N-methyl- N-trimethylsilyl-trifluoroacetamide (MSTFA) derivatives of the analyzed unsaturated fatty acids and their degradation products. MSTFA derivatization catalyzed by iodotrimethylsilane enables the reliable identification of aldehydes and oxoacids as characteristic MSTFA derivatives in GCMS. The obtained results elucidate the degradation pathway of unsaturated fatty acids. Our study of aged fingerprint residues reveals that decanal is the main degradation product of the observed unsaturated fatty acids. Furthermore, oxoacids with different chain lengths are detected as specific degradation products of the unsaturated fatty acids. The detection of the degradation products and their chain length is a simple and effective method to determine the double bond position in unsaturated compounds. We can show that the hexadecenoic and octadecenoic acids found in fingerprint residues are not the pervasive fatty acids Δ9-hexadecenoic (palmitoleic acid) and Δ9-octadecenoic (oleic acid) acid but Δ6-hexadecenoic acid (sapienic acid) and Δ8-octadecenoic acid. The present study focuses on the structure identification of human sebum-specific unsaturated fatty acids in fingerprint residues based on the identification of their degradation products. These results are discussed for further investigations and method developments for age determination of fingerprints, which is still a tremendous challenge because of several factors affecting the aging behavior of individual compounds in fingerprints.

Fatty Acid Structure and Degradation Analysis in Fingerprint Residues.

PubMed

Pleik, Stefanie; Spengler, Bernhard; Schäfer, Thomas; Urbach, Dieter; Luhn, Steven; Kirsch, Dieter

2016-09-01

GC-MS investigations were carried out to elucidate the aging behavior of unsaturated fatty acids in fingerprint residues and to identify their degradation products in aged samples. For this purpose, a new sample preparation technique for fingerprint residues was developed that allows producing N-methyl-N-trimethylsilyl-trifluoroacetamide (MSTFA) derivatives of the analyzed unsaturated fatty acids and their degradation products. MSTFA derivatization catalyzed by iodotrimethylsilane enables the reliable identification of aldehydes and oxoacids as characteristic MSTFA derivatives in GCMS. The obtained results elucidate the degradation pathway of unsaturated fatty acids. Our study of aged fingerprint residues reveals that decanal is the main degradation product of the observed unsaturated fatty acids. Furthermore, oxoacids with different chain lengths are detected as specific degradation products of the unsaturated fatty acids. The detection of the degradation products and their chain length is a simple and effective method to determine the double bond position in unsaturated compounds. We can show that the hexadecenoic and octadecenoic acids found in fingerprint residues are not the pervasive fatty acids Δ9-hexadecenoic (palmitoleic acid) and Δ9-octadecenoic (oleic acid) acid but Δ6-hexadecenoic acid (sapienic acid) and Δ8-octadecenoic acid. The present study focuses on the structure identification of human sebum-specific unsaturated fatty acids in fingerprint residues based on the identification of their degradation products. These results are discussed for further investigations and method developments for age determination of fingerprints, which is still a tremendous challenge because of several factors affecting the aging behavior of individual compounds in fingerprints. Graphical Abstract ᅟ.

Biodegradation of vapor-phase toluene in unsaturated porous media: Column experiments.

PubMed

Khan, Ali M; Wick, Lukas Y; Harms, Hauke; Thullner, Martin

2016-04-01

Biodegradation of organic chemicals in the vapor phase of soils and vertical flow filters has gained attention as promising approach to clean up volatile organic compounds (VOC). The drivers of VOC biodegradation in unsaturated systems however still remain poorly understood. Here, we analyzed the processes controlling aerobic VOC biodegradation in a laboratory setup mimicking the unsaturated zone above a shallow aquifer. The setup allowed for diffusive vapor-phase transport and biodegradation of three VOC: non-deuterated and deuterated toluene as two compounds of highly differing biodegradability but (nearly) identical physical and chemical properties, and MTBE as (at the applied experimental conditions) non-biodegradable tracer and internal control. Our results showed for toluene an effective microbial degradation within centimeter VOC transport distances despite high gas-phase diffusivity. Degradation rates were controlled by the reactivity of the compounds while oxic conditions were found everywhere in the system. This confirms hypotheses that vadose zone biodegradation rates can be extremely high and are able to prevent the outgassing of VOC to the atmosphere within a centimeter range if compound properties and site conditions allow for sufficiently high degradation rates. Copyright © 2016 Elsevier Ltd. All rights reserved.

Vapor port and groundwater sampling well

DOEpatents

Hubbell, Joel M.; Wylie, Allan H.

1996-01-01

A method and apparatus has been developed for combining groundwater monitoring wells with unsaturated-zone vapor sampling ports. The apparatus allows concurrent monitoring of both the unsaturated and the saturated zone from the same well at contaminated areas. The innovative well design allows for concurrent sampling of groundwater and volatile organic compounds (VOCs) in the vadose (unsaturated) zone from a single well, saving considerable time and money. The sample tubes are banded to the outer well casing during installation of the well casing.

Vapor port and groundwater sampling well

DOEpatents

Hubbell, J.M.; Wylie, A.H.

1996-01-09

A method and apparatus have been developed for combining groundwater monitoring wells with unsaturated-zone vapor sampling ports. The apparatus allows concurrent monitoring of both the unsaturated and the saturated zone from the same well at contaminated areas. The innovative well design allows for concurrent sampling of groundwater and volatile organic compounds (VOCs) in the vadose (unsaturated) zone from a single well, saving considerable time and money. The sample tubes are banded to the outer well casing during installation of the well casing. 10 figs.

Base-catalyzed efficient tandem [3 + 3] and [3 + 2 + 1] annulation-aerobic oxidative benzannulations.

PubMed

Diallo, Aboubacar; Zhao, Yu-Long; Wang, He; Li, Sha-Sha; Ren, Chuan-Qing; Liu, Qun

2012-11-16

An efficient synthesis of substituted benzenes via a base-catalyzed [3 + 3] aerobic oxidative aromatization of α,β-unsaturated carbonyl compounds with dimethyl glutaconate was reported. All the reactions were carried out under mild, metal-free conditions to afford the products in high to excellent yields with molecular oxygen as the sole oxidant and water as the sole byproduct. Furthermore, a more convenient tandem [3 + 2 + 1] aerobic oxidative aromatization reaction was developed through the in situ generation of the α,β-unsaturated carbonyl compounds from aldehydes and ketones.

42 CFR 1000.20 - Definitions specific to Medicare.

Code of Federal Regulations, 2010 CFR

2010-10-01

... A of Title XVIII of the Act. Intermediary means an entity that has a contract with CMS to determine... XVIII of the Act. Medicare Part B means the supplementary medical insurance program authorized under Part B of Title XVIII of the Act. Provider means a hospital, a skilled nursing facility, a...

42 CFR 1000.20 - Definitions specific to Medicare.

Code of Federal Regulations, 2011 CFR

2011-10-01

... A of Title XVIII of the Act. Intermediary means an entity that has a contract with CMS to determine... XVIII of the Act. Medicare Part B means the supplementary medical insurance program authorized under Part B of Title XVIII of the Act. Provider means a hospital, a skilled nursing facility, a...

76 FR 73612 - Lock Hydro Friends Fund XVIII; Upper Hydroelectric LLC; FFP Project 95 LLC; Riverbank Hydro No...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-11-29

... DEPARTMENT OF ENERGY Federal Energy Regulatory Commission [Project Nos. 14261-000; 14268-000; 14277-000; 14281-000] Lock Hydro Friends Fund XVIII; Upper Hydroelectric LLC; FFP Project 95 LLC... Friends Fund XVIII (Lock Hydro), Upper Hydroelectric LLC (Upper Hydro), Riverbank Hydro No. 25 LLC...

42 CFR 476.86 - Correlation of Title XI functions with Title XVIII functions.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 42 Public Health 4 2011-10-01 2011-10-01 false Correlation of Title XI functions with Title XVIII functions. 476.86 Section 476.86 Public Health CENTERS FOR MEDICARE & MEDICAID SERVICES, DEPARTMENT OF...) Qio Review Functions § 476.86 Correlation of Title XI functions with Title XVIII functions. (a...

40 CFR Appendix Xviii to Part 86 - Statistical Outlier Identification Procedure for Light-Duty Vehicles and Light Light-Duty Trucks...

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 19 2011-07-01 2011-07-01 false Statistical Outlier Identification... (CONTINUED) Pt. 86, App. XVIII Appendix XVIII to Part 86—Statistical Outlier Identification Procedure for..., but suffer theoretical deficiencies if statistical significance tests are required. Consequently, the...

40 CFR Appendix Xviii to Part 86 - Statistical Outlier Identification Procedure for Light-Duty Vehicles and Light Light-Duty Trucks...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 19 2010-07-01 2010-07-01 false Statistical Outlier Identification... (CONTINUED) Pt. 86, App. XVIII Appendix XVIII to Part 86—Statistical Outlier Identification Procedure for..., but suffer theoretical deficiencies if statistical significance tests are required. Consequently, the...

Intermetallic nickel silicide nanocatalyst—A non-noble metal–based general hydrogenation catalyst

PubMed Central

Pohl, Marga-Martina; Agapova, Anastasiya

2018-01-01

Hydrogenation reactions are essential processes in the chemical industry, giving access to a variety of valuable compounds including fine chemicals, agrochemicals, and pharmachemicals. On an industrial scale, hydrogenations are typically performed with precious metal catalysts or with base metal catalysts, such as Raney nickel, which requires special handling due to its pyrophoric nature. We report a stable and highly active intermetallic nickel silicide catalyst that can be used for hydrogenations of a wide range of unsaturated compounds. The catalyst is prepared via a straightforward procedure using SiO2 as the silicon atom source. The process involves thermal reduction of Si–O bonds in the presence of Ni nanoparticles at temperatures below 1000°C. The presence of silicon as a secondary component in the nickel metal lattice plays the key role in its properties and is of crucial importance for improved catalytic activity. This novel catalyst allows for efficient reduction of nitroarenes, carbonyls, nitriles, N-containing heterocycles, and unsaturated carbon–carbon bonds. Moreover, the reported catalyst can be used for oxidation reactions in the presence of molecular oxygen and is capable of promoting acceptorless dehydrogenation of unsaturated N-containing heterocycles, opening avenues for H2 storage in organic compounds. The generality of the nickel silicide catalyst is demonstrated in the hydrogenation of over a hundred of structurally diverse unsaturated compounds. The wide application scope and high catalytic activity of this novel catalyst make it a nice alternative to known general hydrogenation catalysts, such as Raney nickel and noble metal–based catalysts. PMID:29888329

Intermetallic nickel silicide nanocatalyst-A non-noble metal-based general hydrogenation catalyst.

PubMed

Ryabchuk, Pavel; Agostini, Giovanni; Pohl, Marga-Martina; Lund, Henrik; Agapova, Anastasiya; Junge, Henrik; Junge, Kathrin; Beller, Matthias

2018-06-01

Hydrogenation reactions are essential processes in the chemical industry, giving access to a variety of valuable compounds including fine chemicals, agrochemicals, and pharmachemicals. On an industrial scale, hydrogenations are typically performed with precious metal catalysts or with base metal catalysts, such as Raney nickel, which requires special handling due to its pyrophoric nature. We report a stable and highly active intermetallic nickel silicide catalyst that can be used for hydrogenations of a wide range of unsaturated compounds. The catalyst is prepared via a straightforward procedure using SiO 2 as the silicon atom source. The process involves thermal reduction of Si-O bonds in the presence of Ni nanoparticles at temperatures below 1000°C. The presence of silicon as a secondary component in the nickel metal lattice plays the key role in its properties and is of crucial importance for improved catalytic activity. This novel catalyst allows for efficient reduction of nitroarenes, carbonyls, nitriles, N-containing heterocycles, and unsaturated carbon-carbon bonds. Moreover, the reported catalyst can be used for oxidation reactions in the presence of molecular oxygen and is capable of promoting acceptorless dehydrogenation of unsaturated N-containing heterocycles, opening avenues for H 2 storage in organic compounds. The generality of the nickel silicide catalyst is demonstrated in the hydrogenation of over a hundred of structurally diverse unsaturated compounds. The wide application scope and high catalytic activity of this novel catalyst make it a nice alternative to known general hydrogenation catalysts, such as Raney nickel and noble metal-based catalysts.

2,3-Dideoxyglucosides of selected terpene phenols and alcohols as potent antifungal compounds.

PubMed

James Bound, D; Murthy, Pushpa S; Srinivas, P

2016-11-01

The antifungal activities of novel 2,3-unsaturated and 2,3-dideoxy 1-O-glucosides of carvacrol, thymol, and perillyl alcohol were tested against Aspergillus flavus, Aspergillus ochraceus, Fusarium oxysporum, Saccharomyces cerevisiae and Candida albicans. In the agar well diffusion tests, zones of inhibition for the derivatives of carvacrol, thymol and perillyl alcohol were higher (15-30mm) in the case of filamentous fungi than those for the parent compounds. Their MIC and MFC values indicated that the 2,3-unsaturated and 2,3-dideoxy 1-O-glucosides of carvacrol and thymol exhibited more fungicidal activity than the other compounds. Further, the 2,3-dideoxyglucosides of carvacrol and thymol, exhibited antitoxigenic effects against A. ochraceus and A. flavus and inhibited the production of ochratoxin and aflatoxin-B2. Propidium iodide influx assay demonstrated the lysis of C. albicans cells by carvacrol and its 2,3-unsaturated 1-O-glucoside and the loss of the membrane integrity. These new 2,3-dideoxyglucosides can be useful as antifungal agents and condiments in foods. Copyright © 2016 Elsevier Ltd. All rights reserved.

Macromolecular metal carboxylates

NASA Astrophysics Data System (ADS)

Dzhardimalieva, G. I.; Pomogailo, A. D.

2008-03-01

Data on the synthesis and physicochemical studies of salts of mono- or dibasic unsaturated carboxylic acids and unsaturated metal oxo-carboxylates are generalised and described systematically. The structures and properties of the COO group in various compounds and characteristic features of the structures of carboxylate complexes are analysed. The main routes and kinetics of polymerisation transformations of unsaturated metal carboxylates are considered. The attention is focused on the effect of the metal ion on the monomer reactivity and the polymer morphology and structure. The possibility of stereochemical control of radical polymerisation of unsaturated metal carboxylates is demonstrated. The electronic, magnetic, optical, absorption and thermal properties of metal (co)polymers and nanocomposites and their main applications are considered.

77 FR 13317 - Lock+ Hydro Friends Fund XVIII, Upper Hydroelectric, LLC, FFP Project 95, LLC, Riverbank Hydro No...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-03-06

... DEPARTMENT OF ENERGY Federal Energy Regulatory Commission [Project Nos. 14261-000, 14268-000, 14277-000, 14281-000] Lock+ Hydro Friends Fund XVIII, Upper Hydroelectric, LLC, FFP Project 95, LLC.... Lock+ Hydro Friends Fund XVIII: Project No. 14261-000. 2. Riverbank Hydro No. 25, LLC: Project No...

Novel amine-based presursor compounds and composite membranes thereof

DOEpatents

Lee, Eric K. L.; Tuttle, Mark E.

1989-01-01

Novel amine-based precursor compounds comprising the condensation products of dialkylenetriamine and alpha, beta-unsaturated acid halides are disclosed, as well as composite membranes containing such compounds, the membranes being useful in RO-type processes for desalination and the removal of low molecular weight organic compounds such as phenols and carboxylic acids.

Biological activity and molecular docking studies of curcumin-related α,β-unsaturated carbonyl-based synthetic compounds as anticancer agents and mushroom tyrosinase inhibitors.

PubMed

Bukhari, Syed Nasir Abbas; Jantan, Ibrahim; Unsal Tan, Oya; Sher, Muhammad; Naeem-Ul-Hassan, M; Qin, Hua-Li

2014-06-18

Hyperpigmentation in human skin and enzymatic browning in fruits, which are caused by tyrosinase enzyme, are not desirable. Investigations in the discovery of tyrosinase enzyme inhibitors and search for improved cytotoxic agents continue to be an important line in drug discovery and development. In present work, a new series of 30 compounds bearing α,β-unsaturated carbonyl moiety was designed and synthesized following curcumin as model. All compounds were evaluated for their effects on human cancer cell lines and mushroom tyrosinase enzyme. Moreover, the structure-activity relationships of these compounds are also explained. Molecular modeling studies of these new compounds were carried out to explore interactions with tyrosinase enzyme. Synthetic curcumin-like compounds (2a-b) were identified as potent anticancer agents with 81-82% cytotoxicity. Five of these newly synthesized compounds (1a, 8a-b, 10a-b) emerged to be the potent inhibitors of mushroom tyrosinase, providing further insight into designing compounds useful in fields of food, health, and agriculture.

Three new fatty acids from the roots of Boehmeria nivea (L.) Gaudich and their antifungal activities.

PubMed

Xu, Qiong-Ming; Liu, Yan-Li; Li, Xiao-Ran; Li, Xia; Yang, Shi-Lin

2011-03-01

Three new unsaturated fatty acids, (Z)-9,10,11-trihydroxy-12-octadecenoic acid (1), (Z)-7,8,9-trihydroxy-10-hexadecenoic acid (2) and (Z)-12-keto-7,8,9-trihydroxy-10-hexadecenoic acid (3) were isolated from the roots of Boehmeria nivea (L.) Gaudich, along with a known unsaturated fatty acid, (E)-8,11,12-trihydroxy-9-octadecenoic acid (4). The structures of the new compounds were established by HR ESI-MS, (1)H, (13)C, 2D ((1)H-(1)H COSY, HSQC, HMBC) NMR experiments. The known compound was identified by a comparison of its spectral data with published references. The three new compounds showed some antifungal activities by agar assay.

Rhodium-catalyzed 1,4-addition of arylboronic acids to alpha,beta-unsaturated carbonyl compounds: large accelerating effects of bases and ligands.

PubMed

Itooka, Ryoh; Iguchi, Yuki; Miyaura, Norio

2003-07-25

The effects of ligands and bases in the rhodium(I)-catalyzed 1,4-addition of arylboronic acids to alpha,beta-unsaturated carbonyl compounds were reinvestigated to carry out the reaction under mild conditions. Rhodium(I) complexes possessing a 1,5-cyclooctadiene (cod) and a hydroxo ligand such as [RhOH(cod)](2) exhibited excellent catalyst activities compared to those of the corresponding rhodium-acac or -chloro complexes and their phosphine derivatives. The reaction was further accelerated in the presence of KOH, thus allowing the 1,4-addition even at 0 degrees C. A cationic rhodium(I)-(R)-binap complex, [Rh(R-binap)(nbd)]BF(4), catalyzed the reaction at 25-50 degrees C in the presence of Et(3)N with high enantioselectivities of up to 99% ee for alpha,beta-unsaturated ketones, 92% for aldehydes, 94% for esters, and 92% for amides.

The acyl desaturase CER17 is involved in producing wax unsaturated primary alcohols and cutin monomers

USDA-ARS?s Scientific Manuscript database

We report here n-6 mono-unsaturated primary alcohols (the C26:1, C28:1, and C30:1 homologues) in the cuticular waxes of Arabidopsis inflorescence stem, a class of wax compound not previously reported in Arabidopsis. Further, we used mutation and transgenic complementation analyses to demonstrate tha...

RHODIUM CATALYZED CONJUGATED ADDITION OF UNSATURATED CARBONYL COMPOUNDS BY TRIPHENYLBISMUTH IN AQUEOUS MEDIA AND UNDER AN AIR ATMOSPHERE. (R822668)

EPA Science Inventory

Abstract

In the presence of a rhodium catalyst, ,-unsaturated est...

Asymmetric conjugate addition of Grignard reagents to 3-silyl unsaturated esters for the facile preparation of enantioenriched β-silylcarbonyl compounds and allylic silanes.

PubMed

Zhao, Kai; Loh, Teck-Peng

2014-12-08

A highly enantioselective conjugate addition of Grignard reagents to 3-silyl unsaturated esters to deliver synthetically useful chiral β-silylcarbonyl compounds was developed. The synthetic value of this methodology was further illustrated by the synthesis of enantioenriched β-hydroxyl esters and the facile access granted to various α-chiral allylic silanes. A plethora of diastereoselective transformations of β-silylenolates were also investigated and afforded manifold organosilanes that contained contiguous stereogenic centers with excellent enantioselectivity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Borylation of α,β-Unsaturated Acceptors by Chitosan Composite Film Supported Copper Nanoparticles

PubMed Central

Wen, Wu; Han, Biao; Yan, Feng; Ding, Liang; Li, Bojie; Wang, Liansheng

2018-01-01

We describe here the preparation of copper nanoparticles stabilized on a chitosan/poly (vinyl alcohol) composite film. This material could catalyze the borylation of α,β-unsaturated acceptors in aqueous media under mild conditions. The corresponding organoboron compounds as well as their converted β-hydroxyl products were all obtained in good to excellent yields. It is noteworthy that this catalyst of copper nanoparticles can be easily recycled eight times and remained catalytically reactive. This newly developed methodology provides an efficient and sustainable pathway for the synthesis of organoboron compounds and application of copper nanoparticles. PMID:29757981

Origin and diagenetic transformations of C 25 and C 30 highly branched isoprenoid sulphur compounds: Further evidence for the formation of organically bound sulphur during early diagenesis

NASA Astrophysics Data System (ADS)

Kohnen, M. E. L.; Damsté, J. S. Slnninghe; Kock-van Dalen, A. C.; Haven, H. L. Ten; Rullkötter, J.; De Leeuw, J. W.

1990-11-01

A number of C 25 and C 30 highly branched isoprenoid (HBI) sulphur compounds (E.G., thiolanes, 1-oxo-thiolanes, thiophenes, and benzo[ b]thiophenes) with 2,6,10,14-tetramethyl-7-(3-methylpentyl)pentadecane and 2,6,10,14,18-pentamethyl-7-(3-methylpentyl)nonadecane carbon skeletons were identified in sediments, ranging from Holocene to Upper Cretaceous. These identifications are based on mass spectral characterisation, desulphurisation, and, in some cases, by comparison of mass spectral and relative retention time data with those of authentic standards. The presence of unsaturated C 25 and C 30 HBI thiolanes in a Recent sediment from the Black Sea (age 3-6 × 10 3 a) strongly supports their formation during early diagenesis. The co-occurrence of HBI polyenes (C 25 and C 30) and unsaturated HBI thiolanes (C 25 and C 30) possessing two double bonds less than the corresponding HBI polyenes, in this Recent sediment, testifies to the formation of unsaturated HBI thiolanes by a reaction of inorganic sulphur species with double bonds of the HBI polyenes. Furthermore, a diagenetic scheme for HBI sulphur compounds is proposed based on the identification of HBI sulphur compounds in sediment samples with different maturity levels.

Photochemical dimerization of organic compounds

DOEpatents

Crabtree, Robert H.; Brown, Stephen H.; Muedas, Cesar A.; Ferguson, Richard R.

1992-01-01

At least one of selectivity and reaction rate of photosensitized vapor phase dimerizations, including dehydrodimerizations, hydrodimerizations and cross-dimerizations of saturated and unsaturated organic compounds is improved by conducting the dimerization in the presence of hydrogen or nitrous oxide.

Optimization of conditions for thermal treatment of rice bran using an accelerator including an organo-iron compound.

PubMed

Kanno, Hikari; Tachibana, Naoya; Fukushima, Masami

2011-02-01

A method for thermal conversion of raw organic waste (ROW) to a compost-like material (CLM) with higher levels of unsaturated carbohydrates, nitrogen- and oxygen-containing compounds was developed, in which rice bran and an organo-iron compound were employed as a model ROW and the accelerator, respectively. To evaluate the qualities of CLMs, organic substances of an acid insoluble fraction of alkaline extracts (AIAEs) from a CLM were structurally characterized by elemental analysis, pyrolysis-gas chromatography/mass spectrometry and FT-IR. The levels of unsaturated carbohydrates, and nitrogen- and oxygen-containing compounds in the CLM samples were increased by long-term treatment (60°C for 5 days, 170°C for 3 days). In particular, the high lipid content of the AIAEs, which was indicative of inadequate digestion of CLM components, was dramatically reduced in the presence of the accelerator. Copyright © 2010 Elsevier Ltd. All rights reserved.

Characterization of polar organosulfates in secondary organic aerosol from the unsaturated aldehydes 2-E-pentenal, 2-E-hexenal, and 3-Z-hexenal

EPA Science Inventory

We show in the present study that the unsaturated aldehydes 2-E-pentenal, 2-E-hexenal, and 3-Z-hexenal are biogenic volatile organic compound (BVOC) precursors for polar organosulfates with molecular weights (MWs) 230 and 214, which are also present in ambient fine aerosol from a...

Sorption Equilibria of Vapor Phase Organic Pollutants on Unsaturated Soils and Soil Minerals

DTIC Science & Technology

1990-04-01

Sorbent Characterization .. ........ .......... 6 a. Description of Inorganic Solids and Soils. .... ........ 6 b. Moisture Content...compounds (TCE and toluene) is compared for a cored depth profile obtained from an unsaturated soil and for simulated profiles using inorganic solids. The...Sorbent Characterization a. Description of Inorganic Solids and Soils Inorganic solids were used for initial sorption studies to develop experimental

Linking ground-water age and chemistry data along flow paths: Implications for trends and transformations of nitrate and pesticides

USGS Publications Warehouse

Tesoriero, A.J.; Saad, D.A.; Burow, K.R.; Frick, E.A.; Puckett, L.J.; Barbash, J.E.

2007-01-01

Tracer-based ground-water ages, along with the concentrations of pesticides, nitrogen species, and other redox-active constituents, were used to evaluate the trends and transformations of agricultural chemicals along flow paths in diverse hydrogeologic settings. A range of conditions affecting the transformation of nitrate and pesticides (e.g., thickness of unsaturated zone, redox conditions) was examined at study sites in Georgia, North Carolina, Wisconsin, and California. Deethylatrazine (DEA), a transformation product of atrazine, was typically present at concentrations higher than those of atrazine at study sites with thick unsaturated zones but not at sites with thin unsaturated zones. Furthermore, the fraction of atrazine plus DEA that was present as DEA did not increase as a function of ground-water age. These findings suggest that atrazine degradation occurs primarily in the unsaturated zone with little or no degradation in the saturated zone. Similar observations were also made for metolachlor and alachlor. The fraction of the initial nitrate concentration found as excess N2 (N2 derived from denitrification) increased with ground-water age only at the North Carolina site, where oxic conditions were generally limited to the top 5??m of saturated thickness. Historical trends in fluxes to ground water were evaluated by relating the times of recharge of ground-water samples, estimated using chlorofluorocarbon concentrations, with concentrations of the parent compound at the time of recharge, estimated by summing the molar concentrations of the parent compound and its transformation products in the age-dated sample. Using this approach, nitrate concentrations were estimated to have increased markedly from 1960 to the present at all study sites. Trends in concentrations of atrazine, metolachlor, alachlor, and their degradates were related to the timing of introduction and use of these compounds. Degradates, and to a lesser extent parent compounds, were detected in ground water dating back to the time these compounds were introduced.

Unsaturated Mn complex decorated hybrid thioarsenates: Syntheses, crystal structures and physical properties

NASA Astrophysics Data System (ADS)

Yue, Cheng-Yang; Lei, Xiao-Wu; Tian, Ya-Wei; Xu, Jing; Bai, Yi-Qun; Wang, Fei; Zhou, Peng-Fei; Liu, Xiao-Fan; Yi, Fei-Yan

2016-03-01

The incorporation of unsaturated [Mn(1,2-dap)]2+, [Mn(1,2-dap)2]2+, [Mn(2,2-bipy)]2+ (1,2-dap=1,2-diaminopropane) complex cations with thioarsenate anions of [AsIIIS3]3- and [AsVS4]3- led to three new hybrid manganese thioarsenates, namely, [Mn(1,2-dap)]2MnAs2S6 (1), [Mn(1,2-dap)2]{[Mn(1,2-dap)]2As2S8} (2) and (NH4)[Mn(2,2-bipy)2]AsS4 (3). In compound 1, the unsaturated [Mn(1,2-dap)]2+ complexes, [MnS4]6- tetrahedra and [AsIIIS3]3- trigonal-pyramids are condensed to form the 1D [Mn(1,2-dap)]2MnAs2S6 chain, whereas compound 2 features 2D layer composed of [Mn(1,2-dap)]2+ and [Mn(1,2-dap)2]2+ complexes as well as [AsVS4]3- tetrahedral units. For compound 3, two [AsVS4]3- anions bridge two [Mn(2,2-bipy)]2+ complex cations into a butterfly like {[Mn(2,2-bipy)]2As2S8}2- anionic unit. Magnetic measurements indicate the ferrimagnetic behavior for compound 1 and antiferromagnetic (AF) behaviors for compounds 2-3. The UV-vis diffuse-reflectance measurements and electronic structural calculations based on density functional theory (DFT) revealed the title compounds belong to semiconductors with band gaps of 2.63, 2.21, and 1.97 eV, respectively. The narrow band-gap of compound 3 led to the efficient and stable photocatalytic degradation activity over organic pollutant than N-doped P25 under visible light irradiation.

Data from a thick unsaturated zone in Joshua Tree, San Bernardino County, California, 2007--09

USGS Publications Warehouse

Burgess, Matthew; Izbicki, John; Teague, Nicholas; O'Leary, David R.; Clark, Dennis; Land, Michael

2012-01-01

Data were collected on the physical properties of unsaturated alluvial deposits, the chemical composition of leachate extracted from unsaturated alluvial deposits, the chemical and isotopic composition of groundwater and unsaturated-zone water, and the chemical composition of unsaturated-zone gas at four monitoring sites in the southwestern part of the Mojave Desert in the town of Joshua Tree, San Bernardino County, California. The presence of denitrifying and nitrate-reducing bacteria from unsaturated alluvial deposits was evaluated for two of these monitoring sites that underlie unsewered residential development. Four unsaturated-zone monitoring sites were installed in the Joshua Tree area—two in an unsewered residential development and two adjacent to a proposed artificial-recharge site in an undeveloped area. The two boreholes in residential development areas were installed by using the ODEX air-hammer method. One borehole was drilled through the unsaturated zone to a depth of 541 ft (feet) below land surface; a well screened across the water table was installed. Groundwater was sampled from this well. The second borehole was drilled to a depth of 81 ft below land surface. Drilling procedures, lithologic and geophysical data, construction details, and instrumentation placed in these boreholes are described. Core material was analyzed for water content, bulk density, matric potential, particle size, and water retention. The leachate from over 500 subsamples of cores and cuttings was analyzed for soluble anions, including fluoride, sulfate, bromide, chloride, nitrate, nitrite, and orthophosphate. Groundwater was analyzed for major ions, inorganic compounds, select trace elements, and isotopic composition. Unsaturated-zone water from suction-cup lysimeters was analyzed for major ions, inorganic compounds, select trace elements, and isotopic composition. Unsaturated-zone gas samples were analyzed for argon, oxygen, nitrogen, methane, carbon dioxide, ethane, nitrous oxide, and carbon monoxide. Drill cuttings were analyzed for denitrifying and nitrate-reducing bacteria. One of the boreholes installed adjacent to the Joshua Basin Water District proposed groundwater-recharge facility was installed by using the ODEX air-hammer method and the other was installed by using a 7.875-inch hollow-stem auger. Drilling procedures, lithologic and geophysical data, construction details, and instrumentation placed in these boreholes are described; however, geochemical data were not available at the time of publication.

Simultaneous counter-flow of chlorinated volatile organic compounds across the saturated-unsaturated interface region of an aquifer.

PubMed

Ronen, Daniel; Lev-Wiener, Hagit; Graber, Ellen R; Dahan, Ofer; Weisbrod, Noam

2010-04-01

Concentrations of chlorinated volatile organic compounds (Cl-VOCs) at the saturated-unsaturated interface region (SUIR; depth of approximately 18m) of a sandy phreatic aquifer were measured in two monitoring wells located 25m apart. The concentrations of the Cl-VOCs obtained above and below the water table along a 413-day period are interpreted to depict variable, simultaneous and independent movement of trichlorothene, tetrachloroethene, 1,1-dichloroethene, cis-1,2-dichloroethene, 1,1,1-trichloroethane, chloroform and 1,1-dichloroethane vapors in opposite directions across the SUIR. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

C–H Functionalization of Cyclic Amines: Redox-Annulations with α,β-Unsaturated Carbonyl Compounds

PubMed Central

Kang, YoungKu; Richers, Matthew T.; Sawicki, Conrad H.; Seidel, Daniel

2015-01-01

Cyclic amines such as pyrrolidine and 1,2,3,4-tetrahydroisoquinoline undergo redox-annulations with α,β-unsaturated aldehydes and ketones. Carboxylic acid promoted generation of a conjugated azomethine ylide is followed by 6π-electrocylization, and, in some cases, tautomerization. The resulting ring-fused pyrrolines are readily oxidized to the corresponding pyrroles or reduced to pyrrolidines. PMID:26051897

Kinetic study of the degradation of C5 and C6 unsaturated aldehydes and alcohols by ozone

NASA Astrophysics Data System (ADS)

Kalalian, Carmen; Roth, Estelle; Chakir, Abdelkhaleq

2017-04-01

Emissions of biogenic volatile organic compounds (VOCs) are higher than those from anthropogenic sources. They are therefore likely to have a great influence on atmospheric chemistry both locally and regionally, through their impact on the HOx balance (HOx = HO + HO2), ozone production and ability to form secondary organic aerosols (SOA). Among the volatile organic compounds of biogenic origin are the family of C5 and C6 unsaturated aldehydes and alcohols. Few information exist regarding the fate of these compounds in the atmosphere especially there reaction with ozone. In this work, we studied the kinetics of the reaction of three unsaturated aldehydes (trans-2-pentenal, trans-2-hexenal and 2-methyl-2-pentenal) and three unsaturated alcohols (1-penten-3-ol, cis-2-penten-1-ol and trans-3-hexen-1-ol) with ozone O3 in a rigid atmospheric simulation chamber coupled to an FTIR spectrometer at four different temperatures (273, 298, 333 and 353 K) and at atmospheric pressure. The rate constants of the ozonolysis reaction of the unsaturated aldehydes and the unsaturated alcohols studied were determined and the following Arrhenius expression was obtained (cm3 molecule -1 s -1): k (Trans -2-pentenal)= (3.83 ± 3.71) x 10-16 exp (- (1706 ± 295) / T) k (Trans-2-hexenal)= (1.43 ± 0.67) x 10-16 exp (- (1369 ± 141) / T) k(2-Methyl-2-pentenal)= (3.62± 0.22) x 10-18 exp (- (121 ± 20) / T) k(1-penten-3-ol) = (1.42 ± 1.24) x 10-16 exp (- (642 ± 250) / T) k(Cis-2-penten-1-ol)= (3.14 ± 0.45) x 10-15 exp (- (1045 ± 40) / T) k(Trans-3-hexen-1-ol)= (6.38 ± 1.75) x 10-16 exp (- (686 ± 89) / T) The obtained data will be discussed in terms of structure-reactivity relationship and compared with the reported reactivity with OH radicals. The atmospheric implications derived from this study are discussed as well.

Air-water partition coefficients for a suite of polycyclic aromatic and other C10 through C20 unsaturated hydrocarbons.

PubMed

Rayne, Sierra; Forest, Kaya

2016-09-18

The air-water partition coefficients (Kaw) for 86 large polycyclic aromatic hydrocarbons and their unsaturated relatives were estimated using high-level G4(MP2) gas and aqueous phase calculations with the SMD, IEFPCM-UFF, and CPCM solvation models. An extensive method validation effort was undertaken which involved confirming that, via comparisons to experimental enthalpies of formation, gas-phase energies at the G4(MP2) level for the compounds of interest were at or near thermochemical accuracy. Investigations of the three solvation models using a range of neutral and ionic compounds suggested that while no clear preferential solvation model could be chosen in advance for accurate Kaw estimates of the target compounds, the employment of increasingly higher levels of theory would result in lower Kaw errors. Subsequent calculations on the polycyclic aromatic and unsaturated hydrocarbons at the G4(MP2) level revealed excellent agreement for the IEFPCM-UFF and CPCM models against limited available experimental data. The IEFPCM-UFF-G4(MP2) and CPCM-G4(MP2) solvation energy calculation approaches are anticipated to give Kaw estimates within typical experimental ranges, each having general Kaw errors of less than 0.5 log10 units. When applied to other large organic compounds, the method should allow development of a broad and reliable Kaw database for multimedia environmental modeling efforts on various contaminants.

Reactions of aromatic diazonium salts with unsaturated compounds in the presence of nucleophiles

NASA Astrophysics Data System (ADS)

Grishchuk, B. D.; Gorbovoi, P. M.; Ganushchak, N. I.; Dombrovskii, A. V.

1994-03-01

The review surveys the reactions of aromatic diazonium salts with diene and monounsaturated compounds in the presence of nucleophiles. Certain further reactions of the reaction products and their application are considered. The bibliography includes 63 references.

Identification of the toxic compounds produced by Sargassum thunbergii to red tide microalgae

NASA Astrophysics Data System (ADS)

Wang, Renjun; Wang, You; Tang, Xuexi

2012-09-01

The inhibitory effects of methanol extracts from the tissues of three macroalgal species on the growths of three marine red tide microalgae were assessed under laboratory conditions. Extracts of Sargassum thunbergii (Mertens ex Roth) Kuntz tissue had stronger inhibitory effects than those of either Sargassum pallidum (Turner) C. Agardh or Sargassum kjellmanianum Yendo on the growths of Heterosigma akashiwo (Hada) Hada, Skeletonema costatum (Grev.) Grev, and Prorocentrum micans Ehrenberg. Methanol extracts of S. thunbergii were further divided into petroleum ether, ethyl acetate, butanol, and distilled water phases by liquid-liquid fractionation. The petroleum ether and ethyl acetate fractions had strong algicidal effects on the microalgae. Gas chromatography-mass spectrometry analyses of these two phases identified nine fatty acids, most of which were unsaturated fatty acids. In addition, pure compounds of four of the nine unsaturated fatty acids had effective concentrations below 5 mg/L. Therefore, unsaturated fatty acids are a component of the allelochemicals in S. thunbergii tissue.

Titan aerosol analogues: analysis of the nonvolatile tholins.

PubMed

Sarker, Niladri; Somogyi, Arpad; Lunine, Jonathan I; Smith, Mark A

2003-01-01

Laboratory experiments that produced tholins in a simulated Titan atmosphere were conducted. We report the first systematic analyses of these compounds using Fourier-transform ion cyclotron resonance mass spectrometry. The findings suggest surprising simplicity and nonrandomness in the mass distribution and regularity in species clusters. The degree of unsaturation generally increased with increasing molecular weight in a predictable fashion, and nitrogen is proposed as the dominant carrier of unsaturation. In detected compounds with a general formula of C(x)H(y)N(z), the carbon to nitrogen ratio (x/z) varied only slightly within a narrow limit, and decreased with increasing molecular weights. These compounds are of potential prebiotic interest since they sediment to the surface of Titan, and would dissolve readily in transient aqueous pools that might be generated from time to time by impacts and volcanic

Synthesis, characterization and biological evaluation of novel α, β unsaturated amides.

PubMed

Esmailzadeh, K; Housaindokht, M R; Moradi, A; Esmaeili, A A; Sharifi, Z

2016-05-15

Three derivatives of α,β unsaturated amides have been successfully synthesized via Ugi-four component (U-4CR) reaction. The interactions of the amides with calf thymus deoxyribonucleic acid (ct-DNA) have been investigated in the Tris-HCl buffer (pH=7.4) using viscometric, spectroscopic, thermal denaturation studies, and also molecular docking. By UV-Vis absorption spectroscopy studies, adding CT-DNA to the compound solution caused the hypochromism indicates that there are interactions between the compounds and DNA base pairs. In competitive fluorescence with methylene blue as an intercalator probe, adding compounds to DNA-MB solution caused an increase in emission spectra of the complex. This could be because of compound replacing, with similar binding mode of MB, between the DNA base pairs due to release of bonded MB molecules from DNA-MB complex. Thermal denaturation studies and viscometric experiments also indicated that all three investigated compounds bind to CT-DNA by non-classical intercalation mode. Additionally, molecular docking technique predicted partial intercalation binding mode for the compounds. Also, the highest binding energy was obtained for compound 5a. These results are in agreement with results obtained by empirical methods. Copyright © 2016 Elsevier B.V. All rights reserved.

Compounds and methods for the production of long chain hydrocarbons from biological sources

DOEpatents

Gordon, John Cameron; Silks, Louis A; Sutton, Andrew D; Wu, Ruilian; Schlaf, Marcel; Waldie, Fraser; West, Ryan; Collias, Dimitris Ioannis

2016-08-23

The present invention is directed to the preparation of oxygenated, unsaturated hydrocarbon compounds, such as derivatives of furfural or hydroxymethyl furfural produced by aldol condensation with a ketone or a ketoester, as well as methods of deoxidatively reducing those compounds with hydrogen under acidic conditions to provide saturated hydrocarbons useful as fuels.

ONR Far East Scientific Bulletin. Volume 13, Number 2, April - June 1988

DTIC Science & Technology

1988-06-01

Low Temperature Physics and the Yamada Conference XVIII on Superconductivity in H ighly Correlated Ferm ion Systems...Br I ,--. UBIC Ag Cd In Sri Sb TellI CRYSTfl Au H I ,. -L ------- I. AMONl Z INCBI-ENDE CJIA LCOPYR I TI IU--LU Ill U, I 1--U! I I IU-U 2 , I- IlI-UI...2-0 3.0 4.0 ENERGY GAPEg (eV) Figure 5. Lattice constant - Bandgap diagram for the Il-VI compounds and their derivatives (courtesy of H . Kukimoto

Induction of quinone reductase (QR) by withanolides isolated from Physalis pubescens L. (Solanaceae).

PubMed

Ji, Long; Yuan, Yonglei; Ma, Zhongjun; Chen, Zhe; Gan, Lishe; Ma, Xiaoqiong; Huang, Dongsheng

2013-09-01

In the present study, it was demonstrated that the dichloromethane extract of Physalis pubescens L. (DEPP) had weak potential quinone reductase (QR) inducing activity, but an UPLC-ESI-MS method with glutathione (GSH) as the substrate revealed that the DEPP had electrophiles (with an α,β-unsaturated ketone moiety). These electrophiles could induce quinone reductase (QR) activity, which might be attributed to the modification of the highly reactive cysteine residues in Keap1. Herein, four withanolides, including three new compounds physapubescin B (2), physapubescin C (3), physapubescin D (4), together with one known steroidal compound physapubescin (1) were isolated. Structures of these compounds were determined by spectroscopic analysis and that of physapubescin C (3) was confirmed by a combination of molecular modeling and quantum chemical DFT-GIAO calculations. Evaluation of the QR inducing activities of all withanolides indicated potent activities of compounds 1 and 2, which had a common α,β-unsaturated ketone moiety. Copyright © 2013 Elsevier Ltd. All rights reserved.

Molecular-Scale Investigation with ESI-FT-ICR-MS on Fractionation of Dissolved Organic Matter Induced by Adsorption on Iron Oxyhydroxides.

PubMed

Lv, Jitao; Zhang, Shuzhen; Wang, Songshan; Luo, Lei; Cao, Dong; Christie, Peter

2016-03-01

Adsorption by minerals is a common geochemical process of dissolved organic matter (DOM) which may induce fractionation of DOM at the mineral-water interface. Here, we examine the molecular fractionation of DOM induced by adsorption onto three common iron oxyhydroxides using electrospray ionization coupled with Fourier-transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS). Ferrihydrite exhibited higher affinity to DOM and induced more pronounced molecular fractionation of DOM than did goethite or lepidocrocite. High molecular weight (>500 Da) compounds and compounds high in unsaturation or rich in oxygen including polycyclic aromatics, polyphenols and carboxylic compounds had higher affinity to iron oxyhydroxides and especially to ferrihydrite. Low molecular weight compounds and compounds low in unsaturation or containing few oxygenated groups (mainly alcohols and ethers) were preferentially maintained in solution. This study confirms that the double bond equivalence and the number of oxygen atoms are valuable parameters indicating the selective fractionation of DOM at mineral and water interfaces. The results of this study provide important information for further understanding the behavior of DOM in the natural environment.

Design and laboratory testing of a chamber device to measure total flux of volatile organic compounds from the unsaturated zone under natural conditions.

PubMed

Tillman, Fred D; Smith, James A

2004-11-01

To determine if an aquifer contaminated with volatile organic compounds (VOCs) has potential for natural remediation, all natural processes affecting the fate and transport of VOCs in the subsurface must be identified and quantified. This research addresses the quantification of air-phase volatile organic compounds (VOCs) leaving the unsaturated zone soil gas and entering the atmosphere-including the additional flux provided by advective soil-gas movement induced by barometric pumping. A simple and easy-to-use device for measuring VOC flux under natural conditions is presented. The vertical flux chamber (VFC) was designed using numerical simulations and evaluated in the laboratory. Mass-balance numerical simulations based on continuously stirred tank reactor equations (CSTR) provided information on flux measurement performance of several sampling configurations with the final chamber configuration measuring greater than 96% of model-simulated fluxes. A laboratory device was constructed to evaluate the flux chamber under both diffusion-only and advection-plus-diffusion transport conditions. The flux chamber measured an average of 82% of 15 diffusion-only fluxes and an average of 95% of 15 additional advection-plus-diffusion flux experiments. The vertical flux chamber has the capability of providing reliable measurement of VOC flux from the unsaturated zone under both diffusion and advection transport conditions.

Variation in the chemical composition of cone volatiles within the African cycad genus Encephalartos.

PubMed

Suinyuy, Terence N; Donaldson, John S; Johnson, Steven D

2013-01-01

Volatiles play a key role in attraction of pollinators to cycad cones, but the extent to which volatile chemistry varies among cycad species is still poorly documented. Volatile composition of male and female cones of nineteen African cycad species (Encephalartos; Zamiaceae) was analysed using headspace technique and gas chromatography-mass spectrometry (GC-MS). A total of 152 compounds were identified among the species included in this study, the most common of which were monoterpenes, nitrogen-containing compounds and unsaturated hydrocarbons. Male and female cones emitted similar volatile compounds which varied in relative amounts with two unsaturated hydrocarbons (3E)-1,3-octadiene and (3E,5Z)-1,3,5-octatriene present in the volatile profile of most species. In a multivariate analysis of volatile profiles using non-metric multidimensional scaling (NMDS), a number of species clusters were identified according to shared emission of unsaturated hydrocarbons, pyrazines, benzenoids, aldehydes, alkanes and terpenoids. In comparison, terpenoids are common in Zamia and dominant in Macrozamia species (both in the family Zamiaceae) while benzenoids, esters, and alcohols are dominant in Cycas (Cycadaceae) and in Stangeria (Stangeriaceae). It is likely that volatile variation among Encephalartos species reflects both phylogeny and adaptations to specific beetle pollinators. Copyright © 2012 Elsevier Ltd. All rights reserved.

DEMONSTRATION BULLETIN: IN-SITU VACUUM EXRACTION: TERRA VAC, INC.

EPA Science Inventory

This in-situ vacuum extraction technology is a process for the removal and venting of volatile organic compounds (VOCs) from the vadose or unsaturated zone of soils. Often, these compounds can be removed from the vadose zone before they have a chance to contaminate groundwater. ...

Polymerizable 2(2-hydroxynaphthyl)2H-benzotriazole compounds

DOEpatents

Gomez, P.M.; Neidlinger, H.H.

1991-07-16

Benzotriazole compounds having the formula: ##STR1## wherein R.sub.1 is H, Cl, or OCH.sub.3 ; R.sub.2 is a hydroxynaphthyl group; and R.sub.3 is a vinyl unsaturated polymerizable group. Homopolymers or copolymers thereof are effective as UV light stabilizers and absorbers.

Polymerizable 2(2-hydroxynaphthyl)2H-benzotriazole compounds

DOEpatents

Gomez, Peter M.; Neidlinger, Hermann H.

1991-01-01

Benzotriazole compounds having the formula: ##STR1## wherein R.sub.1 is H, Cl, or OCH.sub.3 ; R.sub.2 is a hydroxynaphthyl group; and R.sub.3 is a vinyl unsaturated polymerizable group. Homopolymers or copolymers thereof are effective as UV light stabilizers and absorbers.

Scent gland constituents of the Middle American burrowing python, Loxocemus bicolor (Serpentes: Loxocemidae).

PubMed

Schulze, Thies; Weldon, Paul J; Schulz, Stefan

2017-07-14

Analysis by gas chromatography/mass spectrometry of the scent gland secretions of male and female Middle American burrowing pythons (Loxocemus bicolor) revealed the presence of over 300 components including cholesterol, fatty acids, glyceryl monoalkyl ethers, and alcohols. The fatty acids, over 100 of which were identified, constitute most of the compounds in the secretions and show the greatest structural diversity. They include saturated and unsaturated, unbranched and mono-, di-, and trimethyl-branched compounds ranging in carbon-chain length from 13 to 24. The glyceryl monoethers possess saturated or unsaturated, straight or methyl-branched alkyl chains ranging in carbon-chain length from 13 to 24. Alcohols, which have not previously been reported from the scent glands, possess straight, chiefly saturated carbon chains ranging in length from 13 to 24. Sex or individual differences in secretion composition were not observed. Compounds in the scent gland secretions of L. bicolor may deter offending arthropods, such as ants.

Diastereoselective synthesis of chiral 1,3-cyclohexadienals

PubMed Central

de la Granja, Ángela P.; Capitán, M. Carmen; Moro, R. F.; Marcos, Isidro S.; Garrido, Narciso M.; Sanz, Francisca; Calle, Emilio

2018-01-01

A novel approach to the production of chiral 1,3-cyclohexadienals has been developed. The organocatalysed asymmetric reaction of different β-disubstituted-α,β-unsaturated aldehydes with a chiral α,β-unsaturated aldehyde in the presence of a Jørgensen-Hayashi organocatalyst provides easy and stereocontrolled access to the cyclohexadienal backbone. This method allows for the synthesis of potential photoprotective chiral 1,3-cyclohexadienals and extra extended conjugation compounds in a simple manner. PMID:29438416

Diastereoselective synthesis of chiral 1,3-cyclohexadienals.

PubMed

Urosa, Aitor; Tobal, Ignacio E; de la Granja, Ángela P; Capitán, M Carmen; Moro, R F; Marcos, Isidro S; Garrido, Narciso M; Sanz, Francisca; Calle, Emilio; Díez, David

2018-01-01

A novel approach to the production of chiral 1,3-cyclohexadienals has been developed. The organocatalysed asymmetric reaction of different β-disubstituted-α,β-unsaturated aldehydes with a chiral α,β-unsaturated aldehyde in the presence of a Jørgensen-Hayashi organocatalyst provides easy and stereocontrolled access to the cyclohexadienal backbone. This method allows for the synthesis of potential photoprotective chiral 1,3-cyclohexadienals and extra extended conjugation compounds in a simple manner.

Patent application for a process for production of effective catalysts for polymerization of unsaturated compounds (in German)

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

Ibing, G.

Organic compounds which contain one or more double carbon bonds per molecule frequently display the ability of polymerizing with each other and with other compounds. It is mainly compounds containing peroxide that serve as catalysts for such operations. Examples of recommended substances are hydrogen peroxide, ozone, perbenzoic acid, benzoin peroxide, peroxide-containing ethers, persulfates, etc. It was found that a catalyst of much greater effectiveness in the polymerization of unsaturated compounds can be obtained from one of the previously-known catalysts if the hydrocarbons are processed with lateral-chain substances (e.g., toluene, xylene, ethyl benzene, propyl benzene, diethyl benzene, etc.) in boiling heatmore » with damp air. In this process there develops a small measure of peroxide of previously unknown make-up, which possess outstanding catalytic effectiveness. For production of the catalyst, the aromatics are heated by return-flow cooler and conducted for several hours through an air stream which has been saturated with steam. Oxidation can be undertaken with other substances also; for example, oxygen, ozone, or compounds which give off oxygen. Activation with air, however, is the simplest way and yields the most effective catalyst. Examples of the process are provided.« less

42 CFR 1004.20 - Sanctions.

Code of Federal Regulations, 2010 CFR

2010-10-01

... from participating in programs under titles V, XVIII, XIX, and XX of the Social Security Act for a... in titles V, XVIII, XIX, and XX of the Act, if the violation involved the provision or ordering of...

FATE OF PAH COMPOUNDS IN TWO SOIL TYPES: INFLUENCE OF VOLATILIZATION, ABIOTIC LOSS, AND BIOLOGICAL ACTIVITY

EPA Science Inventory

The fate of 14 polycyclic aromatic hydrocarbon (PAH) compounds was evaluated with regard to interphase transfer potential and mechanisms of treatment in soil under unsaturated conditions. Volatilization and abiotic and biotic fate of the PAHs were determined using two soils not p...

Unsaturated fatty acids lactose esters: cytotoxicity, permeability enhancement and antimicrobial activity.

PubMed

Lucarini, Simone; Fagioli, Laura; Campana, Raffaella; Cole, Hannah; Duranti, Andrea; Baffone, Wally; Vllasaliu, Driton; Casettari, Luca

2016-10-01

Sugar based surfactants conjugated with fatty acid chains are an emerging broad group of highly biocompatible and biodegradable compounds with established and potential future applications in the pharmaceutical, cosmetic and food industries. In this work, we investigated absorption enhancing and antimicrobial properties of disaccharide lactose, monoesterified with unsaturated fatty acids through an enzymatic synthetic approach. After chemical and cytotoxicity characterizations, their permeability enhancing activity was demonstrated using intestinal Caco-2 monolayers through transepithelial electrical resistance (TEER) and permeability studies. The synthesized compounds, namely lactose palmitoleate (URB1076) and lactose nervonate (URB1077), were shown to exhibit antimicrobial activity versus eight pathogenic species belonging to Gram-positive, Gram-negative microorganisms and fungi. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis, antimycobacterial and cytotoxic activity of α,β-unsaturated amides and 2,4-disubstituted oxazoline derivatives.

PubMed

Avalos-Alanís, Francisco G; Hernández-Fernández, Eugenio; Carranza-Rosales, Pilar; López-Cortina, Susana; Hernández-Fernández, Jorge; Ordóñez, Mario; Guzmán-Delgado, Nancy E; Morales-Vargas, Alejandro; Velázquez-Moreno, Víctor M; Santiago-Mauricio, María G

2017-02-15

The synthesis of six α,β,-unsaturated amides and six 2,4-disubstituted oxazolines derivatives and their evaluation against two Mycobacterium tuberculosis strains (sensitive H37Rv and a resistant clinical isolate) is reported. 2,4-Disubstituted oxazolines (S)-3b,d,e were the most active in the sensitive strain with a MIC of 14.2, 13.6 and 10.8μM, respectively, and the compounds (S)-3d,f were the most active against resistant strain with a MIC of 6.8 and 7.4μM. The ex-vivo evaluation of hepatotoxicity on precision-cut rat liver slices was also tested for the α,β-unsaturated amides (S)-2b and (S)-2d,f and for the oxazolines (S)-3b and (S)-3d,f at different concentrations (5, 15 and 30μg/mL). The results indicate that these compounds possess promising antimycobacterial activity and at the same time are not hepatotoxic. These findings open the possibility for development of new drugs against tuberculosis. Copyright © 2017 Elsevier Ltd. All rights reserved.

New hits as phase II enzymes inducers from a focused library with heteroatom-heteroatom and Michael-acceptor motives.

PubMed

Cabrera, Mauricio; de Ovalle, Stefani; Bollati-Fogolín, Mariela; Nascimento, Fabiana; Corbelini, Patrícia; Janarelli, Fernanda; Kawano, Daniel; Eifler-Lima, Vera Lucia; González, Mercedes; Cerecetto, Hugo

2015-11-01

The increased activity of phase-II-detoxification enzymes, such as quinone reductase (QR) and glutation S -transferase (GST), correlates with protection against chemically induced carcinogenesis. Herein we studied 11 different chemotypes, pyrazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiazole, 1,3,4-oxathiazole, thienyl hydrazone, α,β-unsaturated-oxime, α,β-unsaturated- N -oxide, coumarin and α,β-unsaturated-carbonyl, as phase-II enzymes inducers in order to identify new pharmacophores with chemopreventive activity. Fifty-four compounds were analyzed on wild-type mouse-hepatoma Hepa-1c1c7 and on the aryl-hydrocarbon-nuclear-translocator (Arnt)-defective mutant BpRc1 cells. New monofunctional inducers of QR and GST were identified, the 1,2,5-oxadiazol-2-oxide (3) , the 1,2,4-triazine-4-oxides (23) and (32) and the tetrahydropyrimidinones (28) and (49) . It was confirmed that Nrf2 nuclear translocation is the operative molecular mechanism that allows compound (3) to exert protective effects via expression of downstream phase-II enzymes.

New hits as phase II enzymes inducers from a focused library with heteroatom–heteroatom and Michael-acceptor motives

PubMed Central

Cabrera, Mauricio; de Ovalle, Stefani; Bollati-Fogolín, Mariela; Nascimento, Fabiana; Corbelini, Patrícia; Janarelli, Fernanda; Kawano, Daniel; Eifler-Lima, Vera Lucia; González, Mercedes; Cerecetto, Hugo

2015-01-01

The increased activity of phase-II-detoxification enzymes, such as quinone reductase (QR) and glutation S-transferase (GST), correlates with protection against chemically induced carcinogenesis. Herein we studied 11 different chemotypes, pyrazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiazole, 1,3,4-oxathiazole, thienyl hydrazone, α,β-unsaturated-oxime, α,β-unsaturated-N-oxide, coumarin and α,β-unsaturated-carbonyl, as phase-II enzymes inducers in order to identify new pharmacophores with chemopreventive activity. Fifty-four compounds were analyzed on wild-type mouse-hepatoma Hepa-1c1c7 and on the aryl-hydrocarbon-nuclear-translocator (Arnt)-defective mutant BpRc1 cells. New monofunctional inducers of QR and GST were identified, the 1,2,5-oxadiazol-2-oxide (3), the 1,2,4-triazine-4-oxides (23) and (32) and the tetrahydropyrimidinones (28) and (49). It was confirmed that Nrf2 nuclear translocation is the operative molecular mechanism that allows compound (3) to exert protective effects via expression of downstream phase-II enzymes. PMID:28031894

Comparison of the skin sensitizing potential of unsaturated compounds as assessed by the murine local lymph node assay (LLNA) and the guinea pig maximization test (GPMT).

PubMed

Kreiling, R; Hollnagel, H M; Hareng, L; Eigler, D; Lee, M S; Griem, P; Dreessen, B; Kleber, M; Albrecht, A; Garcia, C; Wendel, A

2008-06-01

The skin sensitization potential of eight unsaturated and one saturated lipid (bio)chemicals was tested in both the LLNA and the GPMT to address the hypothesis that chemicals with unsaturated carbon-carbon double bonds may result in a higher number of unspecific (false positive) results in the LLNA compared to the GPMT. Seven substances (oleic acid, linoleic acid, linolenic acid, undecylenic acid, maleic acid, squalene and octinol) gave clear positive results in the LLNA (stimulation index (SI)> or = 3) and thus would require labelling as skin sensitizer. Fumaric acid and succinic acid gave clearly negative results. In the GPMT, besides some sporadic skin reactions, reproducible skin reactions indicating an allergic response were found in a few animals for four test substances. Based on the GPMT results, only undecylenic acid would have to be classified and labelled as a skin sensitizer according to the European Dangerous Substance Directive (67/548/EEC) (results for linoleic acid were inconclusive), while the other seven test substances would not require labelling. Possible mechanisms for unspecific skin cell stimulation and lymph node responses are discussed. In conclusion, the suitability of the LLNA for unsaturated compounds bearing structural similarity to the tested substances should be carefully considered and the GPMT should remain available as an accepted test method for skin sensitization hazard identification.

UNSATURATED AMINO ACIDS V.

PubMed Central

Shapira, Jacob; Dittmer, Karl

1961-01-01

Shapira, Jacob (Department of Chemistry, Florida State University, Tallahassee) and Karl Dittmer. Unsaturated amino acids. V. Microbiological properties of some halogenated olefinic amino acids. J. Bacteriol. 82:640–647. 1961.—It has been shown previously that several amino acid analogues containing unsaturated linkages were inhibitors of the growth of Escherichia coli and Saccharomyces cerevisiae. This paper reports the results obtained when a series of unsaturated halogen-containing amino acids was examined. The cis isomer of ω-chloroallylglycine showed the greatest toxicity yet found in this series of unsaturated amino acids toward E. coli, whereas the trans-isomer was usually far less toxic. The major effect of cis-ω-chloroallylglycine in E. coli appeared to be to extend the lag phase before the normal rate of growth began. A wide variety of amino acids was capable of partially or completely preventing the toxicity of low levels of these compounds. At higher levels, relatively few amino acids (primarily valine, leucine, and glutamic acid) were effective. In E. coli, cis-ω-chloroallylglycine showed an unusual [Formula: see text] relationship with both glutamic acid and valine over a wide range in concentration. PMID:13911278

Old yellow enzymes protect against acrolein toxicity in the yeast Saccharomyces cerevisiae.

PubMed

Trotter, Eleanor W; Collinson, Emma J; Dawes, Ian W; Grant, Chris M

2006-07-01

Acrolein is a ubiquitous reactive aldehyde which is formed as a product of lipid peroxidation in biological systems. In this present study, we screened the complete set of viable deletion strains in Saccharomyces cerevisiae for sensitivity to acrolein to identify cell functions involved in resistance to reactive aldehydes. We identified 128 mutants whose gene products are localized throughout the cell. Acrolein-sensitive mutants were distributed among most major biological processes but particularly affected gene expression, metabolism, and cellular signaling. Surprisingly, the screen did not identify any antioxidants or similar stress-protective molecules, indicating that acrolein toxicity may not be mediated via reactive oxygen species. Most strikingly, a mutant lacking an old yellow enzyme (OYE2) was identified as being acrolein sensitive. Old yellow enzymes are known to reduce alpha,beta-unsaturated carbonyl compounds in vitro, but their physiological roles have remained uncertain. We show that mutants lacking OYE2, but not OYE3, are sensitive to acrolein, and overexpression of both isoenzymes increases acrolein tolerance. Our data indicate that OYE2 is required for basal levels of tolerance, whereas OYE3 expression is particularly induced following acrolein stress. Despite the range of alpha,beta-unsaturated carbonyl compounds that have been identified as substrates of old yellow enzymes in vitro, we show that old yellow enzymes specifically mediate resistance to small alpha,beta-unsaturated carbonyl compounds, such as acrolein, in vivo.

A NONSTEADY-STATE ANALYTICAL MODEL TO PREDICT GASEOUS EMISSIONS OF VOLATILE ORGANIC COMPOUNDS FROM LANDFILLS. (R825689C072)

EPA Science Inventory

Abstract

A general mathematical model is developed to predict emissions of volatile organic compounds (VOCs) from hazardous or sanitary landfills. The model is analytical in nature and includes important mechanisms occurring in unsaturated subsurface landfill environme...

Adsorptive desulfurization with metal-organic frameworks: A density functional theory investigation

NASA Astrophysics Data System (ADS)

Chen, Zhiping; Ling, Lixia; Wang, Baojun; Fan, Huiling; Shangguan, Ju; Mi, Jie

2016-11-01

The contribution of each fragment of metal-organic frameworks (MOFs) to the adsorption of sulfur compounds were investigated using density functional theory (DFT). The involved sulfur compounds are dimethyl sulfide (CH3SCH3), ethyl mercaptan (CH3CH2SH) and hydrogen sulfide (H2S). MOFs with different organic ligands (NH2-BDC, BDC and NDC), metal centers structures (M, M-M and M3O) and metal ions (Zn, Cu and Fe) were used to study their effects on sulfur species adsorption. The results revealed that, MOFs with coordinatively unsaturated sites (CUS) have the strongest binding strength with sulfur compounds, MOFs with NH2-BDC substituent group ligand comes second, followed by that with saturated metal center, and the organic ligands without substituent group has the weakest adsorption strength. Moreover, it was also found that, among different metal ions (Fe, Zn and Cu), MOFs with unsaturated Fe has the strongest adsorption strength for sulfur compounds. These results are consistent with our previous experimental observations, and therefore provide insights on the better design of MOFs for desulfurization application.

Photosensitized oxidation of unsaturated polymers

NASA Technical Reports Server (NTRS)

Golub, M. A.

1979-01-01

The photosensitized oxidation or singlet oxygenation of unsaturated hydrocarbon polymers and of their model compounds was reviewed. Emphasis was on cis and trans forms of 1,4-polyisoprene, 1,4-polybutadiene and 1,2-poly(1,4-hexadiene), and on 1,4-poly(2,3-dimethyl-1,3-butadiene). The microstructural changes which occur in these polymers on reaction with O2-1 in solution were investigated by infrared H-1 and C-13 NMR spectroscopy. The polymers were shown to yield allylic hydroperoxides with shifted double bonds according to the ene mechanism established for simple olefins. The photosensitized oxidation of the above unsaturated polymer exhibited zero order kinetics, the relative rates paralleling the reactivities of the corresponding simple olefins towards O2-1.

Organic Compounds Complexify Transport in the Amargosa Desert—The Case for Phytotritiation

NASA Astrophysics Data System (ADS)

Stonestrom, D. A.; Luo, W.; Andraski, B. J.; Baker, R. J.; Maples, S.; Mayers, C. J.; Young, M. B.

2014-12-01

Civilian low-level radioactive waste containing organic compounds was disposed in 2- to 15-m deep unlined trenches in a 110-m deep unsaturated zone at the present-day USGS Amargosa Desert Research Site. Tritium represents the plurality of disposed activity. A plume of gas-phase contaminants surrounds the disposal area, with 60 distinct volatile organic compounds (VOCs) identified to date. The distribution of tritiated water in the unsaturated zone surrounding the disposal area is highly enigmatic, with orders of magnitude separating observed levels from those predicted by multiphase models of mass and energy transport. Peaks of tritium and VOCs are coincidently located in sediments tens of meters below the root zone, suggesting abiotic stratigraphic control on lateral transport at depth. Surprisingly, the highest observed levels of tritium occur at a depth of about 1.5 m, the base of the creosote-bush plant-community root zone, where levels of waste-derived VOCs are low (approaching atmospheric levels). Bulk water-vapor samples from shallow and deep unsaturated-zone profile hot spots were trapped as water ice in cold fingers immersed in dry ice-isopropyl alcohol filled Dewar flasks, then melted and sequentially extracted by purge-and-trap VOC degassing followed by elution through activated carbon solid-phase extraction (SPE) cartridges. Analysis of tritium activities and mass spectrometer results indicate that over 98% of tritium activity at depth is present as water, whereas about 15% of basal root zone tritium activity is present as organic compounds trapped with the water. Of these, the less-volatile compound group removed by SPE accounted for about 85% of the organic tritium activity, with mass spectrometry identifying 2-ethyl-1-hexanol as the principal compound removed. This plant-produced fatty alcohol is ubiquitous in the root zone of creosote-bush communities and represents a family of hydroxyl-containing plant produced compounds that give the plants their pungency. These findings suggest that tritiated hydroxyl groups on plant-produced organic compounds provide an important reservoir and pathway for tritium transport.

THE NATURE OF SERUM ANTITRYPSIN

PubMed Central

Jobling, James W.; Petersen, William

1914-01-01

1. The ferment-inhibiting action of the serum is due to the presence of compounds of the unsaturated fatty acids. 2. These fatty acid compounds may be removed from the serum by means of chloroform or ether. 3. Soaps prepared by saponifying the chloroform or ether extracts inhibit the action of trypsin. 4. The anti-enzyme action of the serum can be removed by filtering acid serum through kaolin, and can in part be restored by extracting the kaolin. 5. The decrease in strength of anti-enzyme in old sera is probably due to the action of the serum lipase. 6. Iodin, potassium iodide, or hydrogen peroxide remove the inhibiting action of the serum. 7. Soaps of the unsaturated fatty acids lose their ferment-inhibiting action when heated with serum at 70° C. PMID:19867786

Organocatalysed asymmetric beta-amination and multicomponent syn-selective diamination of alpha,beta-unsaturated aldehydes.

PubMed

Jiang, Hao; Nielsen, Johanne B; Nielsen, Martin; Jørgensen, Karl Anker

2007-01-01

An easy and affordable route for obtaining chiral beta-aminated- and alpha,beta-diaminated aldehydes, 1,3-aminoalcohols, and related compounds by using organocatalysis is presented. The chiral secondary amine (S)-2-[bis(3,5-bistrifluoromethylphenyl)trimethylsilanyloxymethyl]pyrrolidine is used as the catalyst to activate alpha,beta-unsaturated aldehydes, which allows succinimide to add in a 1,4-regio- and stereoselective fashion thereby forming N-protected 1,3-aminoaldehydes in good yields and enantioselectivities. This is followed by two easy transformations giving rise to optically active 1,3-aminoalcohols, a common motif in many biologically active compounds, for example, fibrinogen receptor antagonists. Furthermore, optically active alpha,beta-syn-diaminated aldehydes were obtained by the addition of diethyl azodicarboxylate in a one-pot reaction.

The high-throughput synthesis and phase characterisation of amphiphiles: a sweet case study.

PubMed

Feast, George C; Hutt, Oliver E; Mulet, Xavier; Conn, Charlotte E; Drummond, Calum J; Savage, G Paul

2014-03-03

A new method for the discovery of amphiphiles by using high-throughput (HT) methods to synthesise and characterise a library of galactose- and glucose-containing amphiphilic compounds is presented. The copper-catalysed azide–alkyne cycloaddition (CuAAC) “click” reaction between azide-tethered simple sugars and alkyne-substituted hydrophobic tails was employed to synthesise a library of compounds with systematic variations in chain length and unsaturation in a 24-vial array format. The liquid–crystalline phase behaviour was characterised in a HT manner by using synchrotron small-angle X-ray scattering (SSAXS). The observed structural variation with respect to chain parameters, including chain length and degree of unsaturation, is discussed, as well as hydration effects and degree of hydrogen bonding between head groups. The validity of our HT screening approach was verified by resynthesising a short-chain glucose amphiphile. A separate phase analysis of this compound confirmed the presence of numerous lyotropic liquid–crystalline phases.

Thiol reactivity and its impact on the ciliate toxicity of α,β-unsaturated aldehydes, ketones, and esters.

PubMed

Böhme, Alexander; Thaens, Diana; Schramm, Franziska; Paschke, Albrecht; Schüürmann, Gerrit

2010-12-20

A recently introduced chemoassay has been used to determine second-order rate constants of the electrophile-nucleophile reaction of 15 α,β-unsaturated aldehydes with glutathione. The respective kGSH values vary for more than 3 orders of magnitude, and are within the range determined previously for 31 α,β-unsaturated ketones and esters. Structure-reactivity analyses yield distinct relationships between kGSH and structural features of the compounds. Moreover, increasing kGSH increases the aldehyde toxicity toward ciliates in terms of 48 h-EC50 values (effective concentration yielding 50% growth inhibition of Tetrahymena pyriformis within 48 h). A respective log-log regression equation including both kGSH and the octanol/water partition coefficient, Kow, yields a squared correlation coefficient of 0.96. Comparative analysis with corresponding data for 15 ketones and 16 esters reveals systematic differences between the three compound classes with regard to the individual contributions of hydrophobicity and electrophilic reactivity to aquatic toxicity. The former is particularly pronounced for aldehydes, while the ester toxicity is largely governed by reactivity, with ketones showing an intermediate pattern that is more similar to the one of esters than of aldehydes. It follows that within the Michael acceptor domain of α,β-unsaturated carbonyls, a distinction between aldehydes and nonaldehydic derivatives appears necessary when employing electrophilic reactivity as a component for the quantitative prediction of their reactive toxicity toward aquatic organisms.

Lipid biomarkers of thermal stress in scleractinian corals

NASA Astrophysics Data System (ADS)

Kneeland, J. M.; Hughen, K.; Cervino, J.; Eglinton, T. I.; Bartels, E.

2007-12-01

Lipid content and fatty acid profiles of corals and their symbiotic dinoflagellates are known to vary in response to heat stress and bleaching. To develop lipid biomarkers of heat stress and bleaching response in scleractinian corals, clones of Symbiodinium algae of clade subtypes C1 and D1 were cultured under a range of temperatures. The predominant lipids produced are palmitic (C16) and stearic (C18) saturated fatty acids and their unsaturated analogs. Other important compounds included a C22 penta-unsaturated fatty acid, which is thought to be a specific dinoflagellate marker, and a variety of sterols. Analysis of lipids extracted from coral skeleton indicated that palmitic and stearic acids were the most abundant compounds. The amount of unsaturated C16 and C18 fatty acids in coral skeleton relative to the saturated versions of those acids was much lower in coral skeleton than in the zooxanthellae tissue. This could indicate the incorporation of lipids from outside the coral host-symbiont system into the coral aragonite, or it could reflect diagenesis. A comparison between the lipids found in cloned zooxanthellae, coral tissue, and aragonitic skeleton will be presented to assess the usefulness of lipid biomarkers as indicators of temperature stress on corals.

Green Remediation Best Management Practices: Soil Vapor Extraction & Air Sparging

EPA Pesticide Factsheets

Historically, approximately one-quarter of Superfund source control projects have involved soil vapor extraction (SVE) to remove volatile organic compounds (VOCs) sorbed to soil in the unsaturated (vadose) zone.

5 CFR 890.1303 - Eligibility.

Code of Federal Regulations, 2012 CFR

2012-01-01

... EMPLOYEES HEALTH BENEFITS PROGRAM Department of Defense Federal Employees Health Benefits Program... insurance benefits under part A of title XVIII of the Social Security Act (42 U.S.C. 1395c et seq.); (2) An..., United States Code, who is entitled to hospital insurance benefits under part A of title XVIII of the...

5 CFR 890.1303 - Eligibility.

Code of Federal Regulations, 2011 CFR

2011-01-01

... EMPLOYEES HEALTH BENEFITS PROGRAM Department of Defense Federal Employees Health Benefits Program... insurance benefits under part A of title XVIII of the Social Security Act (42 U.S.C. 1395c et seq.); (2) An..., United States Code, who is entitled to hospital insurance benefits under part A of title XVIII of the...

42 CFR 405.352 - Adjustment of title XVIII incorrect payments.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 42 Public Health 2 2011-10-01 2011-10-01 false Adjustment of title XVIII incorrect payments. 405.352 Section 405.352 Public Health CENTERS FOR MEDICARE & MEDICAID SERVICES, DEPARTMENT OF HEALTH AND HUMAN SERVICES MEDICARE PROGRAM FEDERAL HEALTH INSURANCE FOR THE AGED AND DISABLED Suspension of Payment...

42 CFR 405.352 - Adjustment of title XVIII incorrect payments.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 42 Public Health 2 2010-10-01 2010-10-01 false Adjustment of title XVIII incorrect payments. 405.352 Section 405.352 Public Health CENTERS FOR MEDICARE & MEDICAID SERVICES, DEPARTMENT OF HEALTH AND HUMAN SERVICES MEDICARE PROGRAM FEDERAL HEALTH INSURANCE FOR THE AGED AND DISABLED Suspension of Payment...

Unsaturated Mn complex decorated hybrid thioarsenates: Syntheses, crystal structures and physical properties

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

Yue, Cheng-Yang; State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002; Lei, Xiao-Wu, E-mail: xwlei_jnu@163.com

2016-03-15

The incorporation of unsaturated [Mn(1,2-dap)]{sup 2+}, [Mn(1,2-dap){sub 2}]{sup 2+}, [Mn(2,2-bipy)]{sup 2+} (1,2-dap=1,2-diaminopropane) complex cations with thioarsenate anions of [As{sup III}S{sub 3}]{sup 3−} and [As{sup V}S{sub 4}]{sup 3−} led to three new hybrid manganese thioarsenates, namely, [Mn(1,2-dap)]{sub 2}MnAs{sub 2}S{sub 6} (1), [Mn(1,2-dap){sub 2}]{[Mn(1,2-dap)]_2As_2S_8} (2) and (NH{sub 4})[Mn(2,2-bipy){sub 2}]AsS{sub 4} (3). In compound 1, the unsaturated [Mn(1,2-dap)]{sup 2+} complexes, [MnS{sub 4}]{sup 6−} tetrahedra and [As{sup III}S{sub 3}]{sup 3−} trigonal-pyramids are condensed to form the 1D [Mn(1,2-dap)]{sub 2}MnAs{sub 2}S{sub 6} chain, whereas compound 2 features 2D layer composed of [Mn(1,2-dap)]{sup 2+} and [Mn(1,2-dap){sub 2}]{sup 2+} complexes as well as [As{sup V}S{sub 4}]{sup 3−}more » tetrahedral units. For compound 3, two [As{sup V}S{sub 4}]{sup 3−} anions bridge two [Mn(2,2-bipy)]{sup 2+} complex cations into a butterfly like {[Mn(2,2-bipy)]_2As_2S_8}{sup 2−} anionic unit. Magnetic measurements indicate the ferrimagnetic behavior for compound 1 and antiferromagnetic (AF) behaviors for compounds 2–3. The UV–vis diffuse-reflectance measurements and electronic structural calculations based on density functional theory (DFT) revealed the title compounds belong to semiconductors with band gaps of 2.63, 2.21, and 1.97 eV, respectively. The narrow band-gap of compound 3 led to the efficient and stable photocatalytic degradation activity over organic pollutant than N-doped P25 under visible light irradiation. - Highlights: Three new hybrid manganese thioarsenates have been prepared and structurally characterized. These hybrid phases feature interesting magnetic and visible light responding photocatalytic properties.« less

Atmospheric degradation of 2-chloroethyl vinyl ether, allyl ether and allyl ethyl ether: Kinetics with OH radicals and UV photochemistry.

PubMed

Antiñolo, M; Ocaña, A J; Aranguren, J P; Lane, S I; Albaladejo, J; Jiménez, E

2017-08-01

Unsaturated ethers are oxygenated volatile organic compounds (OVOCs) emitted by anthropogenic sources. Potential removal processes in the troposphere are initiated by hydroxyl (OH) radicals and photochemistry. In this work, we report for the first time the rate coefficients of the gas-phase reaction with OH radicals (k OH ) of 2-chloroethyl vinyl ether (2ClEVE), allyl ether (AE), and allyl ethyl ether (AEE) as a function of temperature in the 263-358 K range, measured by the pulsed laser photolysis-laser induced fluorescence technique. No pressure dependence of k OH was observed in the 50-500 Torr range in He as bath gas, while a slightly negative T-dependence was observed. The temperature dependent expressions for the rate coefficients determined in this work are: The estimated atmospheric lifetimes (τ OH ) assuming k OH at 288 K were 3, 2, and 4 h for 2ClEVE, AE and AEE, respectively. The kinetic results are discussed in terms of the chemical structure of the unsaturated ethers by comparison with similar compounds. We also report ultraviolet (UV) and infrared (IR) absorption cross sections (σ λ and σ(ν˜), respectively). We estimate the photolysis rate coefficients in the solar UV actinic region to be less than 10 -7 s -1 , implying that these compounds are not removed from the atmosphere by this process. In addition, from σ(ν˜) and τ OH , the global warming potential of each unsaturated ether was calculated to be almost zero. A discussion on the atmospheric implications of the titled compounds is presented. Copyright © 2017 Elsevier Ltd. All rights reserved.

Valuable natural products from marine and freshwater macroalgae obtained from supercritical fluid extracts.

PubMed

Messyasz, Beata; Michalak, Izabela; Łęska, Bogusława; Schroeder, Grzegorz; Górka, Bogusława; Korzeniowska, Karolina; Lipok, Jacek; Wieczorek, Piotr; Rój, Edward; Wilk, Radosław; Dobrzyńska-Inger, Agnieszka; Górecki, Henryk; Chojnacka, Katarzyna

2018-01-01

The biologically active compounds (fatty acids, pigments, phenolics, and flavonoid content) were studied in supercritical fluid extracts from the biomass of marine ( Ulva clathrata , Cladophora glomerata , Polysiphonia fucoides , and their multi-species mixture) and freshwater ( C. glomerata ) macroalgae. Different extraction techniques were used in order to compare differences in the biologically active compound composition of the macroalgal extracts. The results indicated that the saturated and unsaturated fatty acids ranged from C9:0 to C22:0. The analysis of differences in the composition of unsaturated to saturated fatty acids in extracts showed that palmitic acid (C16:0) and oleic acid (C18:1, n-9) reached the highest value not only in marine monospecies and multi-species biomass but also in the freshwater macroalga C. glomerata . When comparing the similarity between the concentration of fatty acids and the ratio of the concentration of unsaturated fatty acids to saturated in macroalgal extracts, we found small but not statistically significant variations in values between years (up to 10%). This is acceptable for applications as a stable raw material for industrial purposes. Significantly higher values of fatty acids, carotenoids, and chlorophylls were obtained in the case of SC-CO 2 extraction. The active ingredients of polyphenols, possessing antioxidant activity ranged from approximately 2-4%. Moreover, flavonoids represented less than 10% of the total content of polyphenolic compounds. The extraction efficiency of polyphenols was higher from a mixture of marine algae for the ultrasound-assisted extraction compared to freshwater. All these findings show that marine and freshwater macroalgae, as a raw material, have the optimal biologically active compounds composition for cosmetics.

High-speed vibrational imaging and spectral analysis of lipid bodies by compound Raman microscopy.

PubMed

Slipchenko, Mikhail N; Le, Thuc T; Chen, Hongtao; Cheng, Ji-Xin

2009-05-28

Cells store excess energy in the form of cytoplasmic lipid droplets. At present, it is unclear how different types of fatty acids contribute to the formation of lipid droplets. We describe a compound Raman microscope capable of both high-speed chemical imaging and quantitative spectral analysis on the same platform. We used a picosecond laser source to perform coherent Raman scattering imaging of a biological sample and confocal Raman spectral analysis at points of interest. The potential of the compound Raman microscope was evaluated on lipid bodies of cultured cells and live animals. Our data indicate that the in vivo fat contains much more unsaturated fatty acids (FAs) than the fat formed via de novo synthesis in 3T3-L1 cells. Furthermore, in vivo analysis of subcutaneous adipocytes and glands revealed a dramatic difference not only in the unsaturation level but also in the thermodynamic state of FAs inside their lipid bodies. Additionally, the compound Raman microscope allows tracking of the cellular uptake of a specific fatty acid and its abundance in nascent cytoplasmic lipid droplets. The high-speed vibrational imaging and spectral analysis capability renders compound Raman microscopy an indispensible analytical tool for the study of lipid-droplet biology.

Screening of Chlorinated Paraffins and Unsaturated Analogues in Commercial Mixtures: Confirmation of Their Occurrences in the Atmosphere.

PubMed

Li, Tong; Gao, Shixiong; Ben, Yujie; Zhang, Hong; Kang, Qiyue; Wan, Yi

2018-02-20

Characterizing the detailed compositions of chlorinated paraffins (CPs) commercial mixtures is crucial to understand their environmental sources, fates, and potential risks. In this study, dichloromethane (DCM)-enhanced UPLC-ESI-QTOFMS analysis combined with characteristic isotope chlorine peaks is applied to screen all CPs and their structural analogues in the three most commonly produced CP commercial mixtures (CP-42, CP-52, and CP-70). Mass fractions of total short-chain CPs (SCCPs), medium-chain CPs (MCCPs) and long-chain CPs (LCCPs) ranged from 0.64 to 31.9%, 0.64 to 21.8%, and 0.04 to 43.9%, respectively, in the three commercial mixtures. 113 unsaturated SCCPs, MCCPs, and LCCPs were identified in the commercial mixtures. The detailed mass percentages of saturated and unsaturated CPs with carbon numbers of 10-30, chlorine numbers of 5-28, and unsaturated degrees of 0-7 were characterized in all commercial mixtures. Occurrences of the predominant saturated and unsaturated CPs were further confirmed in air samples collected in Guangdong Province, one of the major CP production areas in China, over one year. The profiles of the detected compounds indicated that LCCPs in air samples might come mainly from the production and usage of CP-52, and unsaturated C 24-29 -LCCPs were specifically originated from CP-70 used in the area.

Aqueous phase oligomerization of α,β-unsaturated carbonyls and acids investigated using ion mobility spectrometry coupled to mass spectrometry (IMS-MS)

NASA Astrophysics Data System (ADS)

Renard, Pascal; Tlili, Sabrine; Ravier, Sylvain; Quivet, Etienne; Monod, Anne

2016-04-01

One of the current essential issues to unravel our ability to forecast future climate change and air quality, implies a better understanding of natural processes leading to secondary organic aerosol (SOA) formation, and in particular the formation and fate of oligomers. The difficulty in characterizing macromolecules is to discern between large oxygenated molecules from series of oligomers containing repeated small monomers of diverse structures. In the present study, taking advantage from previously established radical vinyl oligomerization of methyl vinylketone (MVK) in the aqueous phase, where relatively simple oligomers containing up to 14 monomers were observed, we have investigated the same reactivity on several other unsaturated water soluble organic compounds (UWSOCs) and on a few mixtures of these precursor compounds. The technique used to characterize the formed oligomers was a traveling wave ion mobility spectrometry coupled to a hybrid quadrupole - time of flight mass spectrometer (IMS-MS) fitted with an electrospray source and ultra-high performance liquid chromatography (UPLC). The technique allows for an additional separation, especially for large ions, containing long carbon chains. We have shown the efficiency of the IMS-mass spectrometry technique to detect oligomers derived from MVK photooxidation in the aqueous phase. The results were then compared to other oligomers, derived from ten other individual biogenic UWSOCs. The technique allowed distinguishing between different oligomers arising from different precursors. It also clearly showed that compounds bearing a non-conjugated unsaturation did not provide oligomerization. Finally, it was shown that the IMS-mass spectrometry technique, applied to mixtures of unsaturated conjugated precursors, exhibited the ability of these precursors to co-oligomerize, i.e. forming only one complex oligomer system bearing monomers of different structures. The results are discussed in terms of atmospheric implications for the detection of oligomers in complex chamber and/or field samples.

77 FR 10740 - Lock+ Hydro Friends Fund XVIII, Upper Hydroelectric, LLC, FFP Project 95, LLC, Riverbank Hydro No...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-02-23

... DEPARTMENT OF ENERGY Federal Energy Regulatory Commission [Project Nos. 14261-000, 14268-000, 14277-000, 14281-000] Lock+ Hydro Friends Fund XVIII, Upper Hydroelectric, LLC, FFP Project 95, LLC...-Tombigbee Waterway in Lowndes County, Mississippi. The applications were filed by Lock+ Hydro Friends Fund...

Regulation for "saving" the drowned in Italy (XVIII-XIXth century), with particular reference to the Republic of Venice.

PubMed

D'Este, B R

1990-01-01

The author gives a brief chronological syntesis, starting from the XVIII century, of the various provisions issued in Italy, with particular reference to the Republic of Venice, relating to the saving of the drowned, as an introduction to the discipline of "Life-Saving" oriented swimming.

25 CFR 36.51 - Standard XVIII-Office of Indian Education Programs and Agency monitoring and evaluation...

Code of Federal Regulations, 2010 CFR

2010-04-01

... 25 Indians 1 2010-04-01 2010-04-01 false Standard XVIII-Office of Indian Education Programs and..., DEPARTMENT OF THE INTERIOR EDUCATION MINIMUM ACADEMIC STANDARDS FOR THE BASIC EDUCATION OF INDIAN CHILDREN... XVIII—Office of Indian Education Programs and Agency monitoring and evaluation responsibilities. (a) The...

International Conference on Metalorganic Vapor Chase Epitaxy (ICMOVPE) XVIII

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

Dupuis, Russell D.

The ICMOVPE-XVIII conference created meaningful opportunities for intellectual challenge, networking opportunities, and intellectual stimulation for graduate students, Post-Doctoral Fellows and all attendees. This technical and social program further provided many opportunities for communication, brainstorming, and transfer of information as well as the development of collaborations across many institutions and companies. We had a significant number of members of underrepresented groups in STEM attending this conference. We also are publishing the proceedings of this conference with the Journal of Crystal Growth, a journal which receives wide electronic distribution in many academic institutions world-wide, making the technical information presented at ICMOVPE-XVIII havemore » a much broader impact than would otherwise be possible. ICMOVPE XVIII had a total of 216 presentations and of these; there were 70 Student oral or poster presentations. The funds we obtained for student support from the Department of Energy were distributed among the registered students and Post Docs to supplement the full cost of registration of $1,100 each for regular registration to the reduced rate of at $850 each for graduate students and Post Docs.« less

Fluoralkenyl nortropanes

DOEpatents

Goodman, Mark M.; Chen, Ping

2002-02-05

Provided are compounds of the following formula: ##STR1## wherein R is C2-C6 mono- or multi-unsaturated hydrocarbon having one or more ethylene, acetylene or allene groups, A is 18 or 19, and X is H or halogen. The compounds of the invention bind to dopamine transporter with high affinity and selectivity and are thus useful as diagnostic and therapeutic agents for diseases associated with dopamine transporter dysfunction. The radiolabeled compounds are useful as imaging agents for visualizing the location and density of dopamine transporter by PET imaging.

n-Nonacosadienes from the marine haptophytes Emiliania huxleyi and Gephyrocapsa oceanica.

PubMed

Nakamura, Hideto; Sawada, Ken; Araie, Hiroya; Suzuki, Iwane; Shiraiwa, Yoshihiro

2015-03-01

The hydrocarbons in cultures of marine haptophytes Emiliania huxleyi NIES837 and Gephyrocapsa oceanica NIES1315 were analyzed, and nonacosadienes and hentriacontadienes were detected as the major compounds in both strains. C29 and C31 monoenes and di-, tri- and tetra-unsaturated C33 alkenes were also detected as minor compounds but not C37 and C38 alkenes. The positions of the double bonds in the C29 and C31 alkenes were determined by mass spectrometry of their dimethyl disulfide (DMDS) adducts. Among the four C29 alkenes identified, the most abundant isomer was 2,20-nonacosadiene, and the other three compounds were 1,20-nonacosadiene, 3,20-nonacosadiene and 9-nonacosene, respectively. Hitherto, 2,20-nonacosadiene and 3,20-nonacosadiene were unknown to be natural products. The double bond at the n-9 (ω9) position in these C29 alkenes is hypothesized to be derived from precursors of unsaturated fatty acids possessing an n-9 double bond, such as (9Z)-9-octadecenoic acid. Nonacosadienes have the potential for being used as distinct haptophyte biomarkers. Copyright © 2015 Elsevier Ltd. All rights reserved.

42 CFR 423.772 - Definitions.

Code of Federal Regulations, 2011 CFR

2011-10-01

... month— (1) Has coverage for the month under a prescription drug plan under Part D of title XVIII, or under an MA-PD plan under Part C of title XVIII; and (2) Is determined eligible by the State for medical...)(1) of the Act without use of any more liberal disregards under section 1902(r)(2) of the Act (that...

42 CFR 423.772 - Definitions.

Code of Federal Regulations, 2013 CFR

2013-10-01

... month— (1) Has coverage for the month under a prescription drug plan under Part D of title XVIII, or under an MA-PD plan under Part C of title XVIII; and (2) Is determined eligible by the State for medical...)(1) of the Act without use of any more liberal disregards under section 1902(r)(2) of the Act (that...

42 CFR 423.772 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-10-01

... month— (1) Has coverage for the month under a prescription drug plan under Part D of title XVIII, or under an MA-PD plan under Part C of title XVIII; and (2) Is determined eligible by the State for medical...)(1) of the Act without use of any more liberal disregards under section 1902(r)(2) of the Act (that...

42 CFR 423.772 - Definitions.

Code of Federal Regulations, 2012 CFR

2012-10-01

... month— (1) Has coverage for the month under a prescription drug plan under Part D of title XVIII, or under an MA-PD plan under Part C of title XVIII; and (2) Is determined eligible by the State for medical...)(1) of the Act without use of any more liberal disregards under section 1902(r)(2) of the Act (that...

25 CFR 36.51 - Standard XVIII-Office of Indian Education Programs and Agency monitoring and evaluation...

Code of Federal Regulations, 2014 CFR

2014-04-01

... 25 Indians 1 2014-04-01 2014-04-01 false Standard XVIII-Office of Indian Education Programs and Agency monitoring and evaluation responsibilities. 36.51 Section 36.51 Indians BUREAU OF INDIAN AFFAIRS, DEPARTMENT OF THE INTERIOR EDUCATION MINIMUM ACADEMIC STANDARDS FOR THE BASIC EDUCATION OF INDIAN CHILDREN...

Investigations of novel unsaturated bile salts of male sea lamprey as potential chemical cues

USGS Publications Warehouse

Johnson, Nicholas S.; Yun, Sang-Seon; Li, Weiming

2014-01-01

Sulfated bile salts function as chemical cues that coordinate reproduction in sea lamprey, Petromyzon marinus. 7α, 12α, 24-trihydroxy-5α-cholan-3-one 24-sulfate (3kPZS) is the most abundant known bile salt released by sexually mature male sea lampreys and attracts ovulated females. However, previous studies showed that the male-produced pheromone consists of unidentified components in addition to 3kPZS. Here, analysis of water conditioned with mature male sea lampreys indicated the presence of 4 oxidized, unsaturated compounds with molecular weights of 466 Da, 468 Da, and 2 of 470 Da. These compounds were not detectable in water conditioned with immature male sea lampreys. By using mass spectrometry, 4 A-ring unsaturated sulfated bile salts were tentatively identified from male washings as 2 4-ene, a 1-ene, and a 1,4-diene analogs. These were synthesized to determine if they attracted ovulated female sea lampreys to spawning nests in natural streams. One of the novel synthetic bile salts, 3 keto-1-ene PZS, attracted ovulated females to the point of application at a concentration of 10-12 M. This study reveals the structural diversity of bile salts in sea lamprey, some of which have been demonstrated to be pheromonal cues.

QSAR models to predict mutagenicity of acrylates, methacrylates and alpha,beta-unsaturated carbonyl compounds.

PubMed

Pérez-Garrido, Alfonso; Helguera, Aliuska Morales; Rodríguez, Francisco Girón; Cordeiro, M Natália D S

2010-05-01

The purpose of this study is to develop a quantitative structure-activity relationship (QSAR) model that can distinguish mutagenic from non-mutagenic species with alpha,beta-unsaturated carbonyl moiety using two endpoints for this activity - Ames test and mammalian cell gene mutation test - and also to gather information about the molecular features that most contribute to eliminate the mutagenic effects of these chemicals. Two data sets were used for modeling the two mutagenicity endpoints: (1) Ames test and (2) mammalian cells mutagenesis. The first one comprised 220 molecules, while the second one 48 substances, ranging from acrylates, methacrylates to alpha,beta-unsaturated carbonyl compounds. The QSAR models were developed by applying linear discriminant analysis (LDA) along with different sets of descriptors computed using the DRAGON software. For both endpoints, there was a concordance of 89% in the prediction and 97% confidentiality by combining the three models for the Ames test mutagenicity. We have also identified several structural alerts to assist the design of new monomers. These individual models and especially their combination are attractive from the point of view of molecular modeling and could be used for the prediction and design of new monomers that do not pose a human health risk. 2010 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Conversion of Cn-Unsaturated into Cn-2-Saturated LCFA Can Occur Uncoupled from Methanogenesis in Anaerobic Bioreactors.

PubMed

Cavaleiro, Ana J; Pereira, Maria Alcina; Guedes, Ana P; Stams, Alfons J M; Alves, M Madalena; Sousa, Diana Z

2016-03-15

Fat, oils, and grease present in complex wastewater can be readily converted to methane, but the energy potential of these compounds is not always recyclable, due to incomplete degradation of long chain fatty acids (LCFA) released during lipids hydrolysis. Oleate (C18:1) is generally the dominant LCFA in lipid-containing wastewater, and its conversion in anaerobic bioreactors results in palmitate (C16:0) accumulation. The reason why oleate is continuously converted to palmitate without further degradation via β-oxidation is still unknown. In this work, the influence of methanogenic activity in the initial conversion steps of unsaturated LCFA was studied in 10 bioreactors continuously operated with saturated or unsaturated C16- and C18-LCFA, in the presence or absence of the methanogenic inhibitor bromoethanesulfonate (BrES). Saturated Cn-2-LCFA accumulated both in the presence and absence of BrES during the degradation of unsaturated Cn-LCFA, and represented more than 50% of total LCFA. In the presence of BrES further conversion of saturated intermediates did not proceed, not even when prolonged batch incubation was applied. As the initial steps of unsaturated LCFA degradation proceed uncoupled from methanogenesis, accumulation of saturated LCFA can be expected. Analysis of the active microbial communities suggests a role for facultative anaerobic bacteria in the initial steps of unsaturated LCFA biodegradation. Understanding this role is now imperative to optimize methane production from LCFA.

[Inhibition of Linseed Oil Autooxidation by Essential Oils and Extracts from Spice Plants].

PubMed

Misharina, T A; Alinkina, E S; Terenina, M B; Krikunova, N I; Kiseleva, V I; Medvedeva, I B; Semenova, M G

2015-01-01

Clove bud essential oil, extracts from ginger, pimento and black pepper, or ascorbyl palmytate were studied as natural antioxidants for the inhibition of autooxidation of polyunsaturated fatty acids in linseed oil. Different methods were used to estimate antioxidant efficiency. These methods are based on the following parameters: peroxide values; peroxide concentration; content of degradation products of unsaturated fatty acid peroxides, which acted with thiobarbituric acid; diene conjugate content; the content of volatile compounds that formed as products of unsaturated fatty acid peroxide degradation; and the composition of methyl esters of fatty acids in samples of oxidized linseed oil.

Enantioselective Synthesis of Medium-Sized Lactams via Chiral α,β-Unsaturated Acylammonium Salts.

PubMed

Kang, Guowei; Yamagami, Masaki; Vellalath, Sreekumar; Romo, Daniel

2018-04-06

Medium-sized lactams are important structural motifs found in a variety of bioactive compounds and natural products but are challenging to prepare, especially in optically active form. A Michael addition/proton transfer/lactamization organocascade process is described that delivers medium-sized lactams, including azepanones, benzazepinones, azocanones, and benzazocinones, in high enantiopurity through the intermediacy of chiral α,β-unsaturated acylammonium salts. An unexpected indoline synthesis was also uncovered, and the benzazocinone skeleton was transformed into other complex heterocyclic derivatives, including spiroglutarimides, isoquinolinones, and δ-lactones. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Review of unsaturated-zone transport and attenuation of volatile organic compound (VOC) plumes leached from shallow source zones

NASA Astrophysics Data System (ADS)

Rivett, Michael O.; Wealthall, Gary P.; Dearden, Rachel A.; McAlary, Todd A.

2011-04-01

Reliable prediction of the unsaturated zone transport and attenuation of dissolved-phase VOC (volatile organic compound) plumes leached from shallow source zones is a complex, multi-process, environmental problem. It is an important problem as sources, which include solid-waste landfills, aqueous-phase liquid discharge lagoons and NAPL releases partially penetrating the unsaturated zone, may persist for decades. Natural attenuation processes operating in the unsaturated zone that, uniquely for VOCs includes volatilisation, may, however, serve to protect underlying groundwater and potentially reduce the need for expensive remedial actions. Review of the literature indicates that only a few studies have focused upon the overall leached VOC source and plume scenario as a whole. These are mostly modelling studies that often involve high strength, non-aqueous phase liquid (NAPL) sources for which density-induced and diffusive vapour transport is significant. Occasional dissolved-phase aromatic hydrocarbon controlled infiltration field studies also exist. Despite this lack of focus on the overall problem, a wide range of process-based unsaturated zone — VOC research has been conducted that may be collated to build good conceptual model understanding of the scenario, particularly for the much studied aromatic hydrocarbons and chlorinated aliphatic hydrocarbons (CAHs). In general, the former group is likely to be attenuated in the unsaturated zone due to their ready aerobic biodegradation, albeit with rate variability across the literature, whereas the fate of the latter is far less likely to be dominated by a single mechanism and dependent upon the relative importance of the various attenuation processes within individual site — VOC scenarios. Analytical and numerical modelling tools permit effective process representation of the whole scenario, albeit with potential for inclusion of additional processes — e.g., multi-mechanistic sorption phase partitioning, and provide good opportunity for further sensitivity analysis and development to practitioner use. There remains a significant need to obtain intermediate laboratory-scale and particularly field-scale (actual site and controlled release) datasets that address the scenario as a whole and permit validation of the available models. Integrated assessment of the range of simultaneous processes that combine to influence leached plume generation, transport and attenuation in the unsaturated zone is required. Component process research needs are required across the problem scenario and include: the simultaneous volatilisation and dissolution of source zones; development of appropriate field-scale dispersion estimates for the unsaturated zone; assessment of transient VOC exchanges between aqueous, vapour and sorbed phases and their influence upon plume attenuation; development of improved field methods to recognise and quantify biodegradation of CAHs; establishment of the influence of co-contaminants; and, finally, translation of research findings into more robust practitioner practice.

Homolytic substitution at phosphorus for C–P bond formation in organic synthesis

PubMed Central

2013-01-01

Summary Organophosphorus compounds are important in organic chemistry. This review article covers emerging, powerful synthetic approaches to organophosphorus compounds by homolytic substitution at phosphorus with a carbon-centered radical. Phosphination reagents include diphosphines, chalcogenophosphines and stannylphosphines, which bear a weak P–heteroatom bond for homolysis. This article deals with two transformations, radical phosphination by addition across unsaturated C–C bonds and substitution of organic halides. PMID:23843922

IN SITU SOIL VAPOR EXTRACTION TREATMENT

EPA Science Inventory

Soil vapor extraction (SVE) is designed to physically remove volatile compounds, generally from the vadose or unsaturated zone. t is an in situ process employing vapor extraction wells alone or in combination with air injection wells. acuum blowers supply the motive force, induci...

Photochemical Degradation of Petroleum-Derived Water-Soluble Organics into the Background Dissolved Organic Carbon Pool

NASA Astrophysics Data System (ADS)

Podgorski, D. C.; Ray, P. Z.; Roland, N. V.; Corilo, Y. E.; Tarr, M. A.; Guillemette, F.; Spencer, R. G.

2016-02-01

Water-soluble organic (WSO) photoproducts produced from Macondo crude oil (MC252) and a heavy fuel oil (HFO), a surrogate for that which was spilled into the San Francisco Bay by the M/V Cosco Busan, were isolated and irradiated with simulated sunlight to examine the photochemical fate of the products in aquatic ecosystems. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) reveals marked transformations in the elemental composition of WSOs at specific irradiation periods across a time series that correspond with shifts in bulk properties determined with optical measurements. Blue shifts in EEMs spectra correlate with an increase in formulas classified as unsaturated, high oxygen while the polyphenols and unsaturated, low oxygen compounds decrease. The characteristic A and C humic- and fulvic-like FDOM signatures begin to appear in the EEM spectra of WSOs that were irradiated for as little as 8 to 12 hours, the equivalent of 2 to 3 days of natural sunlight. The presence of the A and C signatures correlate to elemental compositions that exhibit a further decrease in the unsaturated, low oxygen and subsequent increase of unsaturated, high oxygen and highly oxygenated aliphatic compounds. Furthermore, van Krevelen plots reveal a shift toward the compositional space associated with carboxyl-rich aromatic moieties (CRAM) as a function of irradiation period and the appearance of the humic- and fulvic-like FDOM signatures in the EEM spectra. Although the photodegraded WSO products show similarities in FDOM and elemental composition to representative natural dissolved organic matter from their respective pools, persistent petroleum signatures that are not photoactive are still detected. Future studies are required to examine the bioavailability of these photodegraded WSO products to determine if they degrade or persist in the environment.

Cyclic 3-alkyl pyridinium alkaloid monomers from a New Zealand Haliclona sp. marine sponge.

PubMed

Damodaran, Vidhiya; Ryan, Jason L; Keyzers, Robert A

2013-10-25

Bioassay and NMR approaches have been used to guide the isolation of one known and two new cyclic 3-alkyl pyridinium alkaloid (3-APA) monomers from the New Zealand marine sponge Haliclona sp. The new compounds, dehydrohaliclocyclins C (3) and F (4), are the first reported examples of cyclic 3-APA monomers with unsaturation in the alkyl chain. The known compound haliclocyclin C (2) was also isolated from a mixture with 4. The structures of compounds 2-4 were elucidated using NMR spectroscopy, mass spectrometry, and chemical degradation.

Monitoring radionuclide contamination in the unsaturated zone - Lessons learned at the Amargosa Desert Research Site, Nye County, Nevada

USGS Publications Warehouse

Stonestrom, David A.; Abraham, Jared D.; Andraski, Brian J.; Baker, Ronald J.; Mayers, C. Justin; Michel, Robert L.; Prudic, David E.; Striegl, Robert G.; Walvoord, Michelle Ann

2004-01-01

Contaminant-transport processes are being investigated at the U.S. Geological Survey’s Amargosa Desert Research Site (A DRS), adjacent to the Nation’s first commercial disposal facility for low-level radioactive waste. Gases containing tritium and radiocarbon are migrating through a 110-m thick unsaturated zone from unlined trenches that received waste from 1962 to 1992. Results relevant to long- term monitoring of radionuclides are summarized as follows. Contaminant plumes have unexpected histories and spatial configurations due to uncertainties in the: (1) geologic framework, (2) biochemical reactions involving waste components, (3) interactions between plume components and unsaturated-zone materials, (4) disposal practices, and (5) physical transport processes. Information on plume dynamics depends on ex-situ wet-chemical techniques because in-situ sensors for the radionuclides of interest do not exist. As at other radioactive-waste disposal facilities, radionuclides at the ADRS are mixed with varying amounts of volatile organic compounds (VOCs). Carbon-dioxide and VOC anomalies provide proxies for radioactive contamination. Contaminants in the unsaturated zone migrate along preferential pathways. Effective monitoring thus requires accurate geologic characterization. Direct- current electrical-resistivity imaging successfully mapped geologic units controlling preferential transport at the ADRS. Direct sampling of water from the unsaturated zone is complex and time consuming. Sampling plant water is an efficient alternative for mapping shallow tritium contamination.

Around the world with professor Vening Meinesz onboard the submarine K-XVIII

NASA Astrophysics Data System (ADS)

Root, Bart; Hanssen, Ramon; Vermeersen, Bert; Munnik, Michiel; Vlijm, Rozemarijn

2015-04-01

In November 1934, Den Helder, The Netherlands, the start of a remarkable voyage commenced. The Hr. Ms. K-XVIII, a Dutch submarine, was about to set sail to Soerabaya, Indonesia. Onboard was a Dutch professor, Felix Andries Vening Meinesz. He was able to measure the Earth's gravity field with similar precision as on land for the first time in history using his innovative pendulum apparatus. His ground breaking data and systematic way of working changed the way of performing scientific expeditions. With the Library of the TUDelft and "Stichting Academisch Erfgoed" (Academic Heritage Foundation), we revisit this particular expedition and use it as a stepping stone to web-based geodetic and geophysical education for students and the public. The K-XVIII sailed over spreading ridges, transform faults, hotspot volcanos, subduction zones and many more interesting geological structures, which are discussed in this application. The importance of geodetic research is heavily present along the complete voyage in the form of global geoid determination. Moreover, the precision of the observations onboard the K-XVIII are compared with current satellite gravimetry and prove to be remarkable accurate. The goal of the project is to make the several datasets of Vening Meinesz, his measurements, articles, media, old foto's and other objects of the K-XVIII voyage, accessible for the public. The user can follow the famous voyage from Den Helder to Soerabaya in an interactive web application, stopping at interesting geophysical or historical places in space and time. The user can learn about plate tectonics and its historical findings, study the equipment that Vening Meinesz used to observe the gravity field with extreme precision, and learn about the important collaboration between science and the Navy. Dive into the adventure of the geo-scientific research of professor Vening Meinesz.

Pesticide fate and transport throughout unsaturated zones in five agricultural settings, USA

USGS Publications Warehouse

Hancock, T.C.; Sandstrom, M.W.; Vogel, J.R.; Webb, R.M.T.; Bayless, E.R.; Barbash, J.E.

2008-01-01

Pesticide transport through the unsaturated zone is a function of chemical and soil characteristics, application, and water recharge rate. The fate and transport of 82 pesticides and degradates were investigated at five different agricultural sites. Atrazine and metolachlor, as well as several of the degradates of atrazine, metolachlor, acetochlor, and alachlor, were frequently detected in soil water during the 2004 growing season, and degradates were generally more abundant than parent compounds. Metolachlor and atrazine were applied at a Nebraska site the same year as sampling, and focused recharge coupled with the short time since application resulted in their movement in the unsaturated zone 9 m below the surface. At other sites where the herbicides were applied 1 to 2 yr before sampling, only degradates were found in soil water. Transformations of herbicides were evident with depth and during the 4-mo sampling time and reflected the faster degradation of metolachlor oxanilic acid and persistence of metolachor ethanesulfonic acid. The fraction of metolachlor ethanesulfonic acid relative to metolachlor and metolachlor oxanilic acid increased from 0.3 to > 0.9 at a site in Maryland where the unsaturated zone was 5 m deep and from 0.3 to 0.5 at the shallowest depth. The flux of pesticide degradates from the deepest sites to the shallow ground water was greatest (3.0–4.9 μmol m−2 yr−1) where upland recharge or focused flow moved the most water through the unsaturated zone. Flux estimates based on estimated recharge rates and measured concentrations were in agreement with fluxes estimated using an unsaturated-zone computer model (LEACHM).

Reduction of unsaturated compounds under interstellar conditions: chemoselective reduction of C≡C and C=C bonds over C=O functional group

NASA Astrophysics Data System (ADS)

Jonusas, Mindaugas; Guillemin, Jean-Claude; Krim, Lahouari

2017-07-01

The knowledge of the H-addition reactions on unsaturated organic molecules bearing a triple or a double carbon-carbon bond such as propargyl or allyl alcohols and a CO functional group such as propynal, propenal or propanal may play an important role in the understanding of the chemical complexity of the interstellar medium. Why different aldehydes like methanal, ethanal, propynal and propanal are present in dense molecular clouds while the only alcohol detected in those cold regions is methanol? In addition, ethanol has only been detected in hot molecular cores. Are those saturated and unsaturated aldehyde and alcohol species chemically linked in molecular clouds through solid phase H-addition surface reactions or are they formed through different chemical routes? To answer such questions, we have investigated a hydrogenation study of saturated and unsaturated aldehydes and alcohols at 10 K. We prove through this experimental study that while pure unsaturated alcohol ices bombarded by H atoms lead to the formation of the corresponding fully or partially saturated alcohols, surface H-addition reactions on unsaturated aldehyde ices exclusively lead to the formation of fully saturated aldehyde. Such results show that in addition to a chemoselective reduction of C≡C and C=C bonds over the C=O group, there is no link between aldehydes and their corresponding alcohols in reactions involving H atoms in dense molecular clouds. Consequently, this could be one of the reasons why some aldehydes such as propanal are abundant in dense molecular clouds in contrast to the non-detection of alcohol species larger than methanol.

A Series of Lanthanide Selenidogermanates: The First Coexistence of Three Types of Selenidogermanate Units in the Same Architecture.

PubMed

Tang, Shimei; Zhou, Jian; Zou, Hua-Hong; Liu, Xing; Zhang, Li

2018-02-05

A series of lanthanide selenidogermanates, (H 2 peha)[Ln 2 (μ-OH) 2 (tepa) 2 Cl 2 ]{[Ln 2 (μ-OH) 2 (tepa) 2 Cl] 2 (μ-Ge 2 Se 6 )}[Ge 2 Se 6 ]Cl 2 [Ln = Y (1a) and Er (1b); peha = pentaethylenexamine, tepa = tetraethylenepentamine], [Sm 2 (μ-OH) 2 (tepa) 2 (μ-Ge 2 Se 6 )] n (2), [Ho 2 (μ-OH) 2 (tepa) 2 (μ-Ge 2 Se 6 )] n (3), and [Ce 4 (tepa) 4 (μ-GeSe 4 )(μ-GeSe 5 )(μ-Ge 2 Se 6 )] n (4), were made under solvothermal conditions. Compounds 1a and 1b contain a protonated H 2 peha 2+ ion, the complex cation [Ln 2 (μ-OH) 2 (tepa) 2 Cl 2 ] 2+ , a [Ge 2 Se 6 ] 4- anion, free Cl - ions, and a {[Ln 2 (μ-OH) 2 (tepa) 2 Cl] 2 (μ-Ge 2 Se 6 )} 2+ cation constructed by two unsaturated [Ln 2 (μ-OH) 2 (tepa) 2 Cl] 3+ groups connecting via the trans terminal Se atoms of the [Ge 2 Se 6 ] 4- anion, which provides the first example of an organic decorated lanthanide selenidogermanate cation. Both compounds 2 and 3 contain one-dimensional chains [Ln 2 (μ-OH) 2 (tepa) 2 (μ-Ge 2 Se 6 )] n constructed by a combination of unsaturated complex cations [Ln 2 (μ-OH) 2 (tepa) 2 ] 4+ and [Ge 2 Se 6 ] 4- anions, but their stacking patterns of neutral chains are different. Compound 4 contains one-dimensional chain [Ce 4 (tepa) 4 (μ-GeSe 4 )(μ-GeSe 5 )(μ-Ge 2 Se 6 )] n , where three different selenidogermanate units acting as bridging ligands connect unsaturated [Ce(tepa)] 3+ ions. Compound 4 represents the first example of the coexistence of three different selenidogermanate anions in the same architecture. Their optical properties are studied, and the magnetic properties of compounds 1b and 2-4 are also investigated.

Experimental investigation of the auto-ignition characteristics of oxygenated reference fuel compounds

NASA Astrophysics Data System (ADS)

Walton, Stephen Michael

The increased use of biofuels presents an opportunity to improve combustion performance while simultaneously reducing greenhouse gases and pollutant emissions. This work focused on improving the fundamental understanding of the auto-ignition chemistry of oxygenated reference fuel compounds. A systematic study of the effects of ester structure on ignition chemistry was performed using the University of Michigan Rapid Compression Facility. The ignition properties of the ester compounds were investigated over a broad range of pressures (P=5-20 atm) and temperatures (T=850-1150 K) which are directly relevant to advanced combustion engine strategies. Ignition delay times for five esters were determined using the RCF. The esters were selected to systematically consider the chemical structure of the compounds. Three esters were saturated: methyl butanoate, butyl methanoate, and ethyl propanoate; and two were unsaturated: methyl crotonate and methyl trans-3-hexenoate. The unsaturated esters were more reactive than their saturated counterparts, with the largest unsaturated ester, methyl trans-3-hexenoate having the highest reactivity. Two isomers of the saturated esters, butyl methanoate and ethyl propanoate, were more reactive than the isomer methyl butanoate. The results are explained if we assume that butyl methanoate and ethyl propanoate form intermediate ring structures which decompose more rapidly than esters such as methyl butanoate, which do not form ring structures. Modeling studies of the reaction chemistry were conducted for methyl butanoate and ethyl propanoate, for which detailed mechanisms were available in the literature. The new experimental data indicated that literature rate coefficients for some of the methyl butanoate/HO2 reactions were too fast. Modifying these within the theoretical uncertainties for the reaction rates, led to excellent agreement between the model predictions and the experimental data. Comparison of the modeling results with the intermediates measured during methyl butanoate ignition indicated that pathways leading to the formation of small hydrocarbons are relatively well represented in the reaction mechanism. The results of this work provide archival benchmark data for improved understanding of the dominant reaction pathways and species controlling the auto-ignition of oxygenated reference fuel compounds. These data also provide a path for continued development of chemical kinetic models to optimize practical combustion systems.

Hydrogenation of Organic Matter as a Terminal Electron Sink Sustains High CO 2 :CH 4 Production Ratios During Anaerobic Decomposition

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

Wilson, Rachel M.; Tfaily, Malak M.; Rich, Virginia I.

Once inorganic electron acceptors are depleted, organic matter in anoxic environments decomposes by hydrolysis, fermentation, and methanogenesis, requiring syntrophic interactions between microorganisms to achieve energetic favorability. In this classic anaerobic food chain, methanogenesis represents the terminal electron accepting (TEA) process, ultimately producing equimolar CO 2 and CH 4 for each molecule of organic matter degraded. However, CO 2:CH 4 production in Sphagnum-derived, mineral-poor, cellulosic peat often substantially exceeds this 1:1 ratio, even in the absence of measureable inorganic TEAs. Since the oxidation state of C in both cellulose-derived organic matter and acetate is 0, and CO 2 has an oxidationmore » state of +4, if CH 4 (oxidation state -4) is not produced in equal ratio, then some other compound(s) must balance CO 2 production by receiving 4 electrons. Here we present evidence for ubiquitous hydrogenation of diverse unsaturated compounds that appear to serve as organic TEAs in peat, thereby providing the necessary electron balance to sustain CO 2:CH 4 >1. While organic electron acceptors have previously been proposed to drive microbial respiration of organic matter through the reversible reduction of quinone moieties, the hydrogenation mechanism that we propose, by contrast, reduces C-C double bonds in organic matter thereby serving as 1) a terminal electron sink, 2) a mechanism for degrading complex unsaturated organic molecules, 3) a potential mechanism to regenerate electron-accepting quinones, and, in some cases, 4) a means to alleviate the toxicity of unsaturated aromatic acids. In conclusion, this mechanism for CO 2 generation without concomitant CH 4 production has the potential to regulate the global warming potential of peatlands by elevating CO 2:CH 4 production ratios.« less

Hydrogenation of Organic Matter as a Terminal Electron Sink Sustains High CO 2 :CH 4 Production Ratios During Anaerobic Decomposition

DOE PAGES

Wilson, Rachel M.; Tfaily, Malak M.; Rich, Virginia I.; ...

2017-07-03

Once inorganic electron acceptors are depleted, organic matter in anoxic environments decomposes by hydrolysis, fermentation, and methanogenesis, requiring syntrophic interactions between microorganisms to achieve energetic favorability. In this classic anaerobic food chain, methanogenesis represents the terminal electron accepting (TEA) process, ultimately producing equimolar CO 2 and CH 4 for each molecule of organic matter degraded. However, CO 2:CH 4 production in Sphagnum-derived, mineral-poor, cellulosic peat often substantially exceeds this 1:1 ratio, even in the absence of measureable inorganic TEAs. Since the oxidation state of C in both cellulose-derived organic matter and acetate is 0, and CO 2 has an oxidationmore » state of +4, if CH 4 (oxidation state -4) is not produced in equal ratio, then some other compound(s) must balance CO 2 production by receiving 4 electrons. Here we present evidence for ubiquitous hydrogenation of diverse unsaturated compounds that appear to serve as organic TEAs in peat, thereby providing the necessary electron balance to sustain CO 2:CH 4 >1. While organic electron acceptors have previously been proposed to drive microbial respiration of organic matter through the reversible reduction of quinone moieties, the hydrogenation mechanism that we propose, by contrast, reduces C-C double bonds in organic matter thereby serving as 1) a terminal electron sink, 2) a mechanism for degrading complex unsaturated organic molecules, 3) a potential mechanism to regenerate electron-accepting quinones, and, in some cases, 4) a means to alleviate the toxicity of unsaturated aromatic acids. In conclusion, this mechanism for CO 2 generation without concomitant CH 4 production has the potential to regulate the global warming potential of peatlands by elevating CO 2:CH 4 production ratios.« less

Sterol Alkyl Ethers in Immature Callovian (Middle Jurassic) Sediments of Pas de Calais and Normandy (France): Environmental Constraints on their Potential Origins.

NASA Astrophysics Data System (ADS)

Kenig, F. P. H.

2017-12-01

Steryl alkyl ethers (SAEs), steroids with C8-C12 alkyl ether substituent at C3have only been reported in a limited number of studies since their first identification in modern diatomaceous ooze (Boon and de Leeuw, 1979 Mar. Chem. 7, 117-132). These compounds were identified in Holocene to Eocene sediments, but only once in the Cretaceous, in the Valanginian sediments of Shasky Rise (Brassell, 2009; Palaeo Palaeo Palaeo 282, 45-57). The origin of these compounds remains unclear, though they have been proposed to be associated with diatoms and biologically productive environments and cold water. Here we report the occurrence of SAEs in Callovian (Middle Jurassic), thermally immature sediments of the Marnes d'Argences near Caen (Normandy, France) and near Le Wast (Pas de Calais, France), extanding their geological occurrence by 28 million years. These marls contain C36 to C41 SAEs with C9 or C10 alkyl moieties. The steroid moieties (C27 to C31) are saturated, unsaturated (at C5 or C22), or di-unsaturated (at C5 and C22). Some of the samples collected near Le Wast contain only 4-methyl substituted C27, C28 and C29 steroid moieties as well as steroid moieties typical of dinoflagellates such 4,23,24-trimethylsteroids saturated and unsaturated at C22, and diatoms such as 4-desmethyl-23,24-dimethyl-steroid. The origin of SAEs will be discussed in view of their novel identification in Jurassic sediments and considering the environment of deposition of the Marnes d'Argences and comparison with their stratigraphic equivalent in England (Oxford Clay) and Eastern France where none of these compounds were observed.

Hydrogenation of organic matter as a terminal electron sink sustains high CO 2 :CH 4 production ratios during anaerobic decomposition

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

Wilson, Rachel M.; Tfaily, Malak M.; Rich, Virginia I.

Once inorganic electron acceptors are depleted, organic matter in anoxic environments decomposes by hydrolysis, fermentation, and methanogenesis, requiring syntrophic interactions between microorganisms to achieve energetic favorability. In this classic anaerobic food chain, methanogenesis represents the terminal electron accepting (TEA) process, ultimately producing equimolar CO2 and CH4 for each molecule of organic matter degraded. However, CO2:CH4 production in Sphagnum-derived, mineral-poor, cellulosic peat often substantially exceeds this 1:1 ratio, even in the absence of measureable inorganic TEAs. Since the oxidation state of C in both cellulose-derived organic matter and acetate is 0, and CO2 has an oxidation state of +4, if CH4more » (oxidation state -4) is not produced in equal ratio, then some other compound(s) must balance CO2 production by receiving 4 electrons. Here we present evidence for ubiquitous hydrogenation of diverse unsaturated compounds that appear to serve as organic TEAs in peat, thereby providing the necessary electron balance to sustain CO2:CH4 >1. While organic electron acceptors have previously been proposed to drive microbial respiration of organic matter through the reversible reduction of quinone moieties, the hydrogenation mechanism that we propose, by contrast, reduces C-C double bonds in organic matter thereby serving as 1) a terminal electron sink, 2) a mechanism for degrading complex unsaturated organic molecules, 3) a potential mechanism to regenerate electron-accepting quinones, and, in some cases, 4) a means to alleviate the toxicity of unsaturated aromatic acids. This mechanism for CO2 generation without concomitant CH4 production has the potential to regulate the global warming potential of peatlands by elevating CO2:CH4 production ratios.« less

Variations in pesticide leaching related to land use, pesticide properties, and unsaturated zone thickness

USGS Publications Warehouse

Webb, R.M.T.; Wieczorek, M.E.; Nolan, B.T.; Hancock, T.C.; Sandstrom, M.W.; Barbash, J.E.; Bayless, E.R.; Healy, R.W.; Linard, J.

2008-01-01

Pesticide leaching through variably thick soils beneath agricultural fields in Morgan Creek, Maryland was simulated for water years 1995 to 2004 using LEACHM (Leaching Estimation and Chemistry Model). Fifteen individual models were constructed to simulate five depths and three crop rotations with associated pesticide applications. Unsaturated zone thickness averaged 4.7 m but reached a maximum of 18.7 m. Average annual recharge to ground water decreased from 15.9 to 11.1 cm as the unsaturated zone increased in thickness from 1 to 10 m. These point estimates of recharge are at the lower end of previously published values, which used methods that integrate over larger areas capturing focused recharge in the numerous detention ponds in the watershed. The total amount of applied and leached masses for five parent pesticide compounds and seven metabolites were estimated for the 32-km2 Morgan Creek watershed by associating each hectare to the closest one-dimensional model analog of model depth and crop rotation scenario as determined from land-use surveys. LEACHM parameters were set such that branched, serial, first-order decay of pesticides and metabolites was realistically simulated. Leaching is predicted to be greatest for shallow soils and for persistent compounds with low sorptivity. Based on simulation results, percent parent compounds leached within the watershed can be described by a regression model of the form e−depth (a ln t½−b ln KOC) where t 1/2 is the degradation half-life in aerobic soils, K OC is the organic carbon normalized sorption coefficient, and a and b are fitted coefficients (R 2 = 0.86, p value = 7 × 10−9).

Biodegradation, sorption, and transport of 2,4-dichlorophenoxyacetic acid in saturated and unsaturated soils.

PubMed Central

Estrella, M R; Brusseau, M L; Maier, R S; Pepper, I L; Wierenga, P J; Miller, R M

1993-01-01

The fate of an organic contaminant in soil depends on many factors, including sorption, biodegradation, and transport. The herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) was used as a model compound to illustrate the impact of these interacting factors on the fate of an organic contaminant. Batch and column experiments performed with a sandy loam soil mixture under saturated and unsaturated conditions were used to determine the effects of sorption and biodegradation on the fate and transport of 2,4-D. Sorption of 2,4-D was found to have a slight but significant effect on transport of 2,4-D under saturated conditions (retardation factor, 1.8) and unsaturated conditions (retardation factor, 3.4). Biodegradation of 2,4-D was extensive under both batch and column conditions and was found to have a significant impact on 2,4-D transport in column experiments. In batch experiments, complete mineralization of 2,4-D (100 mg kg-1) occurred over a 4-day period following a 3-day lag phase under both saturated and unsaturated conditions. The biodegradation rate parameters calculated for batch experiments were found to be significantly different from those estimated for column experiments. PMID:8285717

The effects of diet and breed on the volatile compounds of cooked lamb.

PubMed

Elmore, J S; Mottram, D S; Enser, M; Wood, J D

2000-06-01

The effect of varying the n-3 polyunsaturated fatty acid (PUFA) composition of lamb muscle on the formation of aroma volatiles during cooking has been examined. The meat was obtained from four groups of Suffolk and Soay lambs fed different supplementary fats: a palm-oil based control; bruised whole linseed, which increased muscle levels of α-linolenic acid (C18:3 n-3); fish oil, which increased eicosapentaenoic acid (EPA, C20:5 n-3) and docosahexaenoic acid (DHA, C22:6 n-3); and equal quantities of linseed and fish oil (fat basis). Higher quantities of lipid oxidation products were found in the aroma volatiles of lamb muscle from animals fed fish oil, compared to the control. In particular, unsaturated aldehydes, unsaturated hydrocarbons and alkylfurans increased up to fourfold. These compounds derived from the autoxidation of PUFAs during cooking. Although some of these volatiles were increased in meat from animals fed the linseed supplement, the effect was not as great as with the fish oil fed lambs. Levels of volatiles derived from the Maillard reaction, such as pyrazines and sulfur compounds, were up to four times higher in Soays than Suffolks.

Novel aminobenzyl and imidobenzyl benzenes

NASA Technical Reports Server (NTRS)

Bell, V. L.; Pratt, J. R.; Stump, B. L.

1976-01-01

Compounds are useful as intermediates for several classes of polymers. Amines can function as cross-linking agents for epoxide and urethane polymers, as well as intermediates for synthesis of thermally-stable addition-type polyimides. Imide derivatives can be obtained by reacting amines with certain monoanhydrides containing olefinic unsaturation.

Novel α,β-unsaturated amide derivatives bearing α-amino phosphonate moiety as potential antiviral agents.

PubMed

Lan, Xianmin; Xie, Dandan; Yin, Limin; Wang, Zhenzhen; Chen, Jin; Zhang, Awei; Song, Baoan; Hu, Deyu

2017-09-15

Based on flexible construction and broad bioactivity of ferulic acid, a series of novel α,β-unsaturated amide derivatives bearing α-aminophosphonate moiety were designed, synthesized and systematically evaluated for their antiviral activity. Bioassay results indicated that some compounds exhibited good antiviral activities against cucumber mosaic virus (CMV) and tobacco mosaic virus (TMV) in vivo. Especially, compound g18 showed excellent curative and protective activities against CMV, with half-maximal effective concentration (EC 50 ) values of 284.67μg/mL and 216.30μg/mL, which were obviously superior to that of Ningnanmycin (352.08μg/mL and 262.53μg/mL). Preliminary structure-activity relationships (SARs) analysis revealed that the introduction of electron-withdrawing group at the 2-position or 4-position of the aromatic ring is favorable for antiviral activity. Present work provides a promising template for development of potential inhibitor of plant virus. Copyright © 2017 Elsevier Ltd. All rights reserved.

Brown Algae Padina sanctae-crucis Børgesen: A Potential Nutraceutical

PubMed Central

Nogueira, Raquel B. S. S.; Tomaz, Anna Cláudia A.; Pessoa, Déborah R.; Xavier, Aline L.; Pita, João Carlos L. R.; Sobral, Marianna V.; Pontes, Marcela L. C.; Pessôa, Hilzeth L. F.; Diniz, Margareth F. F. M.; Miranda, George Emmanuel C.; Vieira, Maria Aparecida R.; Marques, Marcia O. M.; Souza, Maria de Fátima V.; Cunha, Emídio V. L.

2017-01-01

Padina sanctae-crucis Børgesen is distributed worldwide in tropical and subtropical seas; belongs to the Dictyotaceae family, and has proven to be an exceptional source of biologically active compounds. Four compounds were isolated and identified, namely: dolastane diterpene new for the genus Padina; phaeophytin and hidroxy-phaeophytin new for the family Dictyotaceae, and; mannitol first described in this species. Saturated fatty acids as compared to the percentages of unsaturated fatty acids were shown to be present in greater abundance. Palmitic and linolenic acid were the main saturated and unsaturated acids, respectively. Cytotoxic and antioxidant activities were evaluated using human erythrocytes. In vivo evaluations of acute toxicity and genotoxicity were performed in mice. Methanolic extract of P. sanctae-crucis presented antioxidant activity and did not induce cytotoxicity, genotoxicity or acute toxicity. Since Padina sanctae-crucis is already used as food, has essential fatty acids for the nutrition of mammals, does not present toxicity and has antioxidant activity, it can be considered as a potential nutraceutical. PMID:28954390

Electrocatalytic hydrogenation and hydrodeoxygenation of oxygenated and unsaturated organic compounds

DOEpatents

Jackson, James E.; Lam, Chun Ho; Saffron, Christopher M.; Miller, Dennis J.

2018-04-24

A process and related electrode composition are disclosed for the electrocatalytic hydrogenation and/or hydrodeoxygenation of organic substrates such as biomass-derived bio-oil components by the production of hydrogen atoms on a catalyst surface followed by the reaction of the hydrogen atoms with the organic reactants. Biomass fast pyrolysis-derived bio-oil is a liquid mixture containing hundreds of organic compounds with chemical functionalities that are corrosive to container materials and are prone to polymerization. A high surface area skeletal metal catalyst material such as Raney Nickel can be used as the cathode. Electrocatalytic hydrogenation and/or hydrodeoxygenation convert the organic substrates under mild conditions to reduce coke formation and catalyst deactivation. The process converts oxygen-containing functionalities and unsaturated bonds into chemically reduced forms with an increased hydrogen content. The process is operated at mild conditions, which enables it to be a good means for stabilizing bio-oil to a form that can be stored and transported using metal containers and pipes.

Long-Chain Alkyl Cyanides: Unprecedented Volatile Compounds Released by Pseudomonas and Micromonospora Bacteria.

PubMed

Montes Vidal, Diogo; von Rymon-Lipinski, Anna-Lena; Ravella, Srinivasa; Groenhagen, Ulrike; Herrmann, Jennifer; Zaburannyi, Nestor; Zarbin, Paulo H G; Varadarajan, Adithi R; Ahrens, Christian H; Weisskopf, Laure; Müller, Rolf; Schulz, Stefan

2017-04-03

The analysis of volatiles from bacterial cultures revealed long-chain aliphatic nitriles, a new class of natural products. Such nitriles are produced by both Gram-positive Micromonospora echinospora and Gram-negative Pseudomonas veronii bacteria, although the structures differ. A variable sequence of chain elongation and dehydration in the fatty acid biosynthesis leads to either unbranched saturated or unsaturated nitriles with an ω-7 double bond, such as (Z)-11-octadecenenitrile, or methyl-branched unsaturated nitriles with the double bond located at C-3, such as (Z)-13-methyltetradec-3-enenitrile. The nitrile biosynthesis starts from fatty acids, which are converted into their amides and finally dehydrated. The structures and biosyntheses of the 19 naturally occurring compounds were elucidated by mass spectrometry, synthesis, and feeding experiments with deuterium-labeled precursors. Some of the nitriles showed antimicrobial activity, for example, against multiresistant Staphylococcus aureus strains. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Compounds formed by treatment of corn (Zea mays) with nitrous acid.

PubMed

Archer, M C; Hansen, T J; Tannenbaum, S R

1980-01-01

Nitrohexane has been identified as a major product formed following treatment of corn (Zea mays) with nitrous acid. Preliminary evidence suggests that another compound isolated from the nitrosated corn is an unsaturated nitrolic acid. As an aid to the analysis of N-nitro compounds, we have characterized the response of a chemiluminescence detector (Thermal Energy Analyzer) as a function of pyrolysis chamber temperature for several nitrosamines and for an aliphatic C-nitroso compound, an aromatic C-nitro compound, a nitramine and an alkyl nitrite. The response-temperature profiles are valuable in distinguishing among the various compounds and in optimizing the sensitivity of the detector for use in chromatography. Other tests, including photolysis and stability toward nitrite-scavenging reagents, further aid in distinguishing among the various compounds.

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

PubMed Central

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

2017-01-01

Increasing prevalence of allergic diseases with an inadequate variety of treatment drives forward search for new alternative drugs. Fatty acids, abundant in nature, are regarded as important bioactive compounds and powerful nutrients playing an important role in lipid homeostasis and inflammation. Phytochemical study on Typhonium blumei Nicolson and Sivadasan (Araceae), a folk anti-cancer and anti-inflammatory medicine, yielded four oxygenated fatty acids, 12R-hydroxyoctadec-9Z,13E-dienoic acid methyl ester (1) and 10R-hydroxyoctadec-8E,12Z-dienoic acid methyl ester (2), 9R-hydroxy-10E-octadecenoic acid methyl ester (3), and 12R*-hydroxy-10E-octadecenoic acid methyl ester (4). Isolated compounds were identified by spectroscopic methods along with GC-MS analysis. Isolated fatty acids together with a series of saturated, unsaturated and oxygenated fatty acids were evaluated for their anti-inflammatory and anti-allergic activities in vitro. Unsaturated (including docosahexaenoic and eicosapentaenoic acids) as well as hydroxylated unsaturated fatty acids exerted strong anti-inflammatory activity in superoxide anion generation (IC50 2.14–3.73 μM) and elastase release (IC50 1.26–4.57 μM) assays. On the other hand, in the anti-allergic assays, the unsaturated fatty acids were inactive, while hydroxylated fatty acids showed promising inhibitory activity in A23187- and antigen-induced degranulation assays (e.g., 9S-hydroxy-10E,12Z-octadecadienoic acid, IC50 92.4 and 49.7 μM, respectively). According to our results, the presence of a hydroxy group in the long chain did not influence the potent anti-inflammatory activity of free unsaturated acids. Nevertheless, hydroxylation of fatty acids (or their methyl esters) seems to be a key factor for the anti-allergic activity observed in the current study. Moreover, ChemGPS-NP was explored to predict the structure-activity relationship of fatty acids. The anti-allergic fatty acids formed different cluster distant from clinically used drugs. The bioactivity of T. blumei, which is historically utilized in folk medicine, might be related to the content of fatty acids and their metabolites. PMID:28674495

20 CFR 655.1111 - Element I-What hospitals are eligible to participate in the H-1C program?

Code of Federal Regulations, 2010 CFR

2010-04-01

...) hospital,” as defined in Section 1886(d)(1)(B) of the Social Security Act, 42 U.S.C. 1395ww(d)(1)(B), which... settled cost report, filed under Title XVIII of the Social Security Act, (42 U.S.C. 1395 et seq.), for its... settled cost report, filed under Title XVIII of the Social Security Act, for its fiscal year 1994 cost...

20 CFR 655.1111 - Element I-What hospitals are eligible to participate in the H-1C program?

Code of Federal Regulations, 2011 CFR

2011-04-01

...) hospital,” as defined in Section 1886(d)(1)(B) of the Social Security Act, 42 U.S.C. 1395ww(d)(1)(B), which... settled cost report, filed under Title XVIII of the Social Security Act, (42 U.S.C. 1395 et seq.), for its... settled cost report, filed under Title XVIII of the Social Security Act, for its fiscal year 1994 cost...

Monitoring Production of Methane from Spills of Gasoline at UST Release Sites (Boston, MA)

EPA Science Inventory

Anaerobic biodegradation of the BTEX compounds can produce substantial concentrations of methane in ground water at gasoline spill sites. This methane can escape the ground water, move through the unsaturated zone and potentially produce explosive concentrations of methane in c...

Dehydrogenative [2 + 2 + 2] Cycloaddition of Cyano-yne-allene Substrates: Convenient Access to 2,6-Naphthyridine Scaffolds.

PubMed

Haraburda, Ewelina; Lledó, Agustí; Roglans, Anna; Pla-Quintana, Anna

2015-06-19

A rhodium-catalyzed [2 + 2 + 2] cycloaddition of cyano-yne-allene scaffolds followed by a dehydrogenative process enabling the direct synthesis of unsaturated pyridine-containing compounds that can be conveniently converted to 2,6-naphthyridine derivatives is reported.

Whole eggs enhance antioxidant activity when combined with energy dense, cooked breakfast foods

USDA-ARS?s Scientific Manuscript database

Acute metabolic changes following the consumption of energy dense foods high in saturated fat (SFA) and glycemic load (GL) may contribute to the pathogenesis of several chronic diseases. Eggs provide highly digestible protein, unsaturated fatty acids, carotenoids, and other antioxidant compounds tha...

Delivery of Polyunsaturated Fatty Acids from a Glycerol Polyester Matrix with Anti-oxidant Properties

USDA-ARS?s Scientific Manuscript database

Awareness of the health benefits associated with the polyunsaturated acids such as alpha linolenic (ALA), eicosapentaenoic acid (EPA), and docosahexaenoic acid (DHA), has generated interest in formulating foods and dietary supplements with these compounds. However, the highly unsaturated structure o...

Effects of double and triple bonds on the spatial representations of odorants in the rat olfactory bulb.

PubMed

Johnson, Brett A; Ong, Joan; Lee, Kaman; Ho, Sabrina L; Arguello, Spart; Leon, Michael

2007-02-01

Many naturally occurring volatile chemicals that are detected through the sense of smell contain unsaturated (double or triple) carbon-carbon bonds. These bonds can affect odors perceived by humans, yet in a prior study of unsaturated hydrocarbons we found only very minor effects of unsaturated bonds. In the present study, we tested the possibility that unsaturated bonds affect the recognition of oxygen-containing functional groups, because humans perceive odor differences between such molecules. We therefore compared spatial activity patterns across the entire glomerular layer of the rat olfactory bulb evoked by oxygen-containing odorants differing systematically in the presence, position, number, and stereochemistry of unsaturated bonds. We quantified activity patterns by mapping [(14)C]2-deoxyglucose uptake into anatomically standardized data matrices, which we compared statistically. We found that the presence and number of unsaturated bonds consistently affected activity patterns, with the largest effect related to the presence of a triple bond. Effects of bond saturation included a loss of activity in glomeruli strongly activated by the corresponding saturated odorants and/or the presence of activity in areas not stimulated by the corresponding saturated compounds. The position of double bonds also affected patterns of activity, but cis vs. trans configuration had no measurable impact in all five sets of stereoisomers that we studied. These results simultaneously indicate the importance of interactions between carbon-carbon bond types and functional groups in the neural coding of odorant chemical information and highlight the emerging concept that the rat olfactory system is more sensitive to certain types of chemical differences than others. (c) 2006 Wiley-Liss, Inc.

Effects of substrate fatty acids on products of lecithin hydrolysis and acyl-CoA-independent transacylation with cholesterol by aortic enzyme preparations.

PubMed

Patelski, J; Pioruńska-Stolzmann, M

1985-01-01

The acyl composition of substrates and products of enzymatic hydrolysis and transacylation of lecithin with cholesterol in the arterial wall was investigated. Saturated acyl residues predominated in lysolecithin and unsaturated ones in acids released by hydrolysis of egg lecithin. In the reaction system with cholesterol, saturated acyls predominated in both lysolecithin and acids released whereas unsaturated ones were more abundant in newly formed acylcholesterols. Mainly unsaturated acyls were present in the hydrolysis products from soybean lecithin in the reaction systems with and without cholesterol. For acylcholesterols formed in the presence of either lecithin, the percent values are in the numerical order of C18:2 greater than C18:1 greater than C16:0 greater than or equal to C18:0. It It is concluded that acyl preferences and interactions in the enzyme-catalyzed reactions studied may contribute to the different accumulation and removal of the compounds involved from the artery.

Maleate/vinyl ether UV-cured coatings: Effects of composition on curing and properties

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

Noren, G.K.

1996-10-01

The effect of the composition of the maleate polyester and the vinyl ether terminated compound on their UV-curing and properties has been investigated. Linear unsaturated polyester resins based on maleic anhydride and 1,5-pentane diol were synthesized. The molecular weight of the unsaturated polyesters was varied by changing the ratio of maleic anhydride to 1,5-pentane diol and the double bond equivalent weight was varied by replacing maleic anhydride with succinic anhydride. Coating formulations containing these unsaturated polyesters, triethylene glycol divinyl ether and a free radical photoinitiator were crosslinked in the presence of UV light. The coatings were very brittle, exhibiting tensilemore » strengths in the range of 1.5-4.0 MPa and elongations of only 3-7%. Diethyl maleate and isobutyl vinyl ether were effective diluents for reducing viscosity but reduced the cure speed. A vinyl ether urethane oligomer was synthesized and enhanced the flexibility and toughness of the coatings when substituted for triethylene glycol divinyl ether.« less

Lewis super-acid catalyzed cyclizations: a new route to fragrance compounds.

PubMed

Coulombel, Lydie; Grau, Fanny; Weïwer, Michel; Favier, Isabelle; Chaminade, Xavier; Heumann, Andreas; Bayón, J Carles; Aguirre, Pedro A; Duñach, Elisabet

2008-06-01

This review deals with the application of Lewis super acids such as Al(III), In(III), and Sn(IV) triflates and triflimidates as catalysts in the synthesis of fragrance materials. Novel catalytic reactions involving C-C and C-heteroatom bond-forming reactions, as well as cycloisomerization processes are presented. In particular, Sn(IV) and Al(III) triflates were employed as catalysts in the selective cyclization of unsaturated alcohols to cyclic ethers, as well as in the cyclization of unsaturated carboxylic acids to lactones. The addition of thiols and thioacids to non-activated olefins, both in intra- and intermolecular versions, was efficiently catalyzed by In(III) derivatives. Sn(IV) Triflimidates catalyzed the cycloisomerization of highly substituted 1,6-dienes to gem-dimethyl-substituted cyclohexanes bearing an isopropylidene substituent. The hydroformylation of these unsaturated substrates, catalyzed by a Rh(I) complex with a bulky phosphite ligand, selectively afforded the corresponding linear aldehydes. The olfactory evaluation of selected heterocycles, carbocycles, and aldehydes synthesized is also discussed.

Unsaturated fatty acids promote bioaccessibility and basolateral secretion of carotenoids and α-tocopherol by Caco-2 cells.

PubMed

Failla, Mark L; Chitchumronchokchai, Chureeporn; Ferruzzi, Mario G; Goltz, Shellen R; Campbell, Wayne W

2014-06-01

Bioavailability of carotenoids and tocopherols from foods is determined by the efficiency of transfer from food/meal to mixed micelles during digestion, incorporation into chylomicrons for trans-epithelial transport to lymphatic/blood system, and distribution to target tissues. Fats and oils are important factors for facilitating the absorption of lipophilic compounds. However, dietary fats and oils are composed of various types of saturated and unsaturated fatty acids which may differentially impact the bioavailability of carotenoids and tocopherols from foods. We have investigated the effects of several common commercial lipids on bioavailability using an in vitro digestion model and Caco-2 human intestinal cells. Meals consisted of mixed salad vegetables containing a single test lipid. Micellarization and cellular uptake of β-carotene (βC) and lycopene (LYC) during small intestinal digestion was increased by lipids rich in unsaturated fatty acids: soybean oil > olive > canola > butter. In contrast, type of lipid minimally affected the bioaccessibility of lutein (LUT) and zeaxanthin (ZEA). To examine the influence of type of dietary triglyceride on uptake and basolateral secretion of carotenoids, Caco-2 cells grown on Transwell membranes were incubated with micellar mixtures of fatty acids (1.0 mM) mimicking the types and ratio of saturated to unsaturated (mono- + poly-unsaturated) fatty acids (FA) present in butter (70 : 30), olive oil (7 : 93) and soybean oil (11 : 89). Cells were exposed to micelles containing βC, LUT, α-tocopherol (α-TC) and a mixture of test fatty acids. Uptake and basolateral secretion of βC, LUT and α-TC were greater in cells pre-treated with mixtures enriched in unsaturated compared to saturated FA and these effects were mediated by increased assembly and secretion of chylomicrons. These results suggest that dietary fats/oils rich in unsaturated fatty acids promote carotenoid and α-TC bioavailability by enhancing their micellarization during digestion and intestinal transport.

Introducing the Wittig Reaction.

ERIC Educational Resources Information Center

Armstead, D. E. F.

1979-01-01

An experiment is described which provides a simple example of the application of the Wittig reaction to the synthesis of unsaturated compounds. The experiment was designed with British HNC chemistry students in mind, but it is also suitable as a project-type exercise for final year GCE A-level students. (Author/BB)

Monitoring Production of Methane from Spills of Gasoline at UST Release Sites.

EPA Science Inventory

ORD-362 (Rev 06/10/05) (Webforms v2.4) Abstract: Anaerobic biodegradation of the BTEX compounds can produce substantial concentrations of methane in ground water at gasoline spill sites. This methane can escape the ground water, move through the unsaturated zone and potentiall...

Ozonolysis and Oxyphotolysis of Municipal and Industrial Effluents.

DTIC Science & Technology

1981-07-14

which it reacts. Reaction rates of such materials as bacteria, nitrites, hydrojen sulphide , unsaturated compounds, etc., are limited only by mass transfer...rate. The runs were conducted only A{ter allowing several minutes for the U.V. lamp to attain the ried power levels. 1 Two types of mercury lamp (low

Omega-functionalized fatty acids, alcohols, and ethers via olefin metathesis

USDA-ARS?s Scientific Manuscript database

Methyl 17-hydroxy stearate was converted to methyl octadec-16-enoate using copper sulfate adsorbed on silica gel. This compound, possessing unsaturation at the opposite end of the chain from the carboxylate, served as a useful substrate for the olefin metathesis reaction. As a result, several fatt...

Solid-state radioluminescent compositions

DOEpatents

Clough, Roger L.; Gill, John T.; Hawkins, Daniel B.; Renschler, Clifford L.; Shepodd, Timothy J.; Smith, Henry M.

1991-01-01

A solid state radioluminescent composition for light source comprises an optically clear polymer organic matrix containing tritiated organic materials and dyes capable of "red" shifting primary scintillation emissions from the polymer matrix. The tritiated organic materials are made by reducing, with tritium, an unsaturated organic compound that prior to reduction contains olefinic or alkynylic bonds.

Utilization of oxygen difluoride for syntheses of fluoropolymers

NASA Technical Reports Server (NTRS)

Toy, M. S. (Inventor)

1976-01-01

The reaction oxygen difluoride, OF2, with ethylenically unsaturated fluorocarbon compounds is examined. Depending upon the fluorocarbon material and reaction conditions, OF2 can chain extend fluoropolyenes, convert functional perfluorovinyl groups to acyl fluoride and/or epoxide groups, and act as a monomer for an addition type copolymerization with diolefins.

Aromaticity and Antiaromaticity in Zintl Clusters

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

Sun, Zhong -Ming; Liu, Chao; Popov, Ivan Aleksandrovich

Originally, the concepts of aromaticity and antiaromaticity were introduced to explain the stability and reactivity of unsaturated organic compounds. Since then, they have been extended to other species with delocalized electrons including various saturated systems, organometallic compounds, and even inorganic clusters and molecules. In this study, we focus on the most recent progress of using these concepts to guide experimental synthesis and rationalize geometrical and electronic structures of a particular family of polyanions composed of Group 14 and 15 elements, namely Zintl clusters.

Algae as promising organisms for environment and health

PubMed Central

2011-01-01

Algae, like other plants, produce a variety of remarkable compounds collectively referred to as secondary metabolites. They are synthesized by these organisms at the end of the growth phase and/or due to metabolic alterations induced by environmental stress conditions. Carotenoids, phenolic compounds, phycobiliprotein pigments, polysaccharides and unsaturated fatty acids are same of the algal natural products, which were reported to have variable biological activities, including antioxidant activity, anticancer activity, antimicroabial activity against bacteria-virus-algae-fungi, organic fertilizer and bioremediation potentials. PMID:21862867

Aromaticity and Antiaromaticity in Zintl Clusters

DOE PAGES

Sun, Zhong -Ming; Liu, Chao; Popov, Ivan Aleksandrovich; ...

2018-05-18

Originally, the concepts of aromaticity and antiaromaticity were introduced to explain the stability and reactivity of unsaturated organic compounds. Since then, they have been extended to other species with delocalized electrons including various saturated systems, organometallic compounds, and even inorganic clusters and molecules. In this study, we focus on the most recent progress of using these concepts to guide experimental synthesis and rationalize geometrical and electronic structures of a particular family of polyanions composed of Group 14 and 15 elements, namely Zintl clusters.

Infrared and reflectron time-of-flight mass spectroscopic analysis of methane (CH4)-carbon monoxide (CO) ices exposed to ionization radiation--toward the formation of carbonyl-bearing molecules in extraterrestrial ices.

PubMed

Kaiser, Ralf I; Maity, Surajit; Jones, Brant M

2014-02-28

Ice mixtures of methane and carbon monoxide were exposed to ionizing radiation in the form of energetic electrons at 5.5 K to investigate the formation of carbonyl bearing molecules in extraterrestrial ices. The radiation induced chemical processing of the mixed ices along with their isotopically labeled counterparts was probed online and in situ via infrared spectroscopy (solid state) aided with reflectron time-of-flight mass spectrometry (ReTOFMS) coupled to single photon photoionization (PI) at 10.49 eV (gas phase). Deconvolution of the carbonyl absorption feature centered at 1727 cm(-1) in the processed ices and subsequent kinetic fitting to the temporal growth of the newly formed species suggests the formation of acetaldehyde (CH3CHO) together with four key classes of carbonyl-bearing molecules: (i) alkyl aldehydes, (ii) alkyl ketones, (iii) α,β-unsaturated ketones/aldehydes and (iv) α,β,γ,δ-unsaturated ketones/α,β-dicarbonyl compounds in keto-enol form. The mechanistical studies indicate that acetaldehyde acts as the key building block of higher aldehydes (i) and ketones (ii) with unsaturated ketones/aldehydes (iii) and/or α,β-dicarbonyl compounds (iv) formed from the latter. Upon sublimation of the newly synthesized molecules, ReTOFMS together with isotopic shifts of the mass-to-charge ratios was exploited to identify eleven product classes containing molecules with up to six carbon atoms, which can be formally derived from C1-C5 hydrocarbons incorporating up to three carbon monoxide building blocks. The classes are (i) saturated aldehydes/ketones, (ii) unsaturated aldehydes/ketones, (iii) doubly unsaturated aldehydes/ketones, (iv) saturated dicarbonyls (aldehydes/ketones), (v) unsaturated dicarbonyls (aldehydes/ketones), (vi) saturated tricarbonyls (aldehydes/ketones), molecules containing (vii) one carbonyl - one alcohol (viii), two carbonyls - one alcohol, (ix) one carbonyl - two alcohol groups along with (x) alcohols and (xi) diols. Reaction pathways to synthesize these classes were derived as well. The present experiments provide clear evidence for the formation of key organic molecules--acetaldehyde, acetone, and potentially vinylalcohol--which are among the 15 carbonyl containing organic molecules detected in the interstellar medium. Despite numerous previous experimental investigations probing the effect of ionizing radiation on simple astrophysical ice representatives, our results suggest that more complex organic molecules can be formed in extraterrestrial ices than previously suggested. An outlook on further identification of individual isomers is also presented.

Transport of volatile organic compounds across the capillary fringe

USGS Publications Warehouse

McCarthy, Kathleen A.; Johnson, Richard L.

1993-01-01

Physical experiments were conducted to investigate the transport of a dissolved volatile organic compound (trichloroethylene, TCE) from shallow groundwater to the unsaturated zone under a variety of conditions including changes in the soil moisture profile and water table position. Experimental data indicated that at moderate groundwater velocities (0.1 m/d), vertical mechanical dispersion was negligible and molecular diffusion was the dominant vertical transport mechanism. Under these conditions, TCE concentrations decreased nearly 3 orders of magnitude across the capillary fringe and soil gas concentrations remained low relative to those of underlying groundwater. Data collected during a water table drop showed a short-term increase in concentrations throughout most of the unsaturated zone, but these concentrations quickly declined and approached initial values after the water table was returned to its original level. In the deep part of the unsaturated zone, the water table drop resulted in a long-term decrease in concentrations, illustrating the effects of hysteresis in the soil moisture profile. A two-dimensional random walk advection-diffusion model was developed to simulate the experimental conditions, and numerical simulations agreed well with experimental data. A simpler, one-dimensional finite-difference diffusion-dispersion model was also developed. One-dimensional simulations based on molecular diffusion also agreed well with experimental data. Simulations which incorporated mechanical dispersion tended to overestimate flux across the capillary fringe. Good agreement between the one- and two-dimensional models suggested that a simple, one-dimensional approximation of vertical transport across the capillary fringe can be useful when conditions are appropriate.

Unsaturated Fatty Acids Supplementation Reduces Blood Lead Level in Rats

PubMed Central

Skoczyńska, Anna; Wojakowska, Anna; Nowacki, Dorian; Bobak, Łukasz; Turczyn, Barbara; Smyk, Beata; Szuba, Andrzej; Trziszka, Tadeusz

2015-01-01

Some dietary factors could inhibit lead toxicity. The aim of this study was to evaluate the effect of dietary compounds rich in unsaturated fatty acids (FA) on blood lead level, lipid metabolism, and vascular reactivity in rats. Serum metallothionein and organs' lead level were evaluated with the aim of assessing the possible mechanism of unsaturated FA impact on blood lead level. For three months, male Wistar rats that were receiving drinking water with (100 ppm Pb) or without lead acetate were supplemented per os daily with virgin olive oil or linseed oil (0.2 mL/kg b.w.) or egg derived lecithin fraction: “super lecithin” (50 g/kg b.w.). Mesenteric artery was stimulated ex vivo by norepinephrine (NE) administered at six different doses. Lecithin supplementation slightly reduced pressor responses of artery to NE. Lead administered to rats attenuated the beneficial effect of unsaturated FA on lipid metabolism and vascular reactivity to adrenergic stimulation. On the other hand, the super lecithin and linseed oil that were characterized by low omega-6 to omega-3 ratio (about 1) reduced the blood lead concentration. This effect was observed in lead poisoned rats (p < 0.0001) and also in rats nonpoisoned with lead (p < 0.05). PMID:26075218

Unsaturated fatty acids supplementation reduces blood lead level in rats.

PubMed

Skoczyńska, Anna; Wojakowska, Anna; Nowacki, Dorian; Bobak, Łukasz; Turczyn, Barbara; Smyk, Beata; Szuba, Andrzej; Trziszka, Tadeusz

2015-01-01

Some dietary factors could inhibit lead toxicity. The aim of this study was to evaluate the effect of dietary compounds rich in unsaturated fatty acids (FA) on blood lead level, lipid metabolism, and vascular reactivity in rats. Serum metallothionein and organs' lead level were evaluated with the aim of assessing the possible mechanism of unsaturated FA impact on blood lead level. For three months, male Wistar rats that were receiving drinking water with (100 ppm Pb) or without lead acetate were supplemented per os daily with virgin olive oil or linseed oil (0.2 mL/kg b.w.) or egg derived lecithin fraction: "super lecithin" (50 g/kg b.w.). Mesenteric artery was stimulated ex vivo by norepinephrine (NE) administered at six different doses. Lecithin supplementation slightly reduced pressor responses of artery to NE. Lead administered to rats attenuated the beneficial effect of unsaturated FA on lipid metabolism and vascular reactivity to adrenergic stimulation. On the other hand, the super lecithin and linseed oil that were characterized by low omega-6 to omega-3 ratio (about 1) reduced the blood lead concentration. This effect was observed in lead poisoned rats (p < 0.0001) and also in rats nonpoisoned with lead (p < 0.05).

Marigold flower-powder exhibits significant potential to inhibit lipid oxidation in rice bran tea.

PubMed

Wanyo, Pitchaporn; Kaewseejan, Niwat; Meeso, Naret; Siriamornpun, Sirithon

2015-06-01

We supplemented marigold flower-powder (MFP) in rice bran tea at different proportions as a source of natural antioxidant compounds. Changes of phenolic compounds, antioxidant activity, fatty acid composition and lipid oxidation in the rice bran tea with MFP after 30 days of storage were investigated, comparing results with the initial data. Adding MFP in rice bran tea resulted in an increased content and composition of phenolics and flavonoids along with enhanced antioxidant activities, which were increased in a dose-dependent manner. As a result, MFP supplementation of rice bran tea was able to retard the lipid oxidation as determined by the peroxide value (PV), due to the protection of essential fatty acids during 30 days of storage. The PVs were strongly negatively correlated (p < 0.01) with phenolic compounds, total phenolic content (TPC) and total flavonoid content (TFC), but were positively correlated with tocopherols and γ-oryzanol contents. We also found that the PV was positively correlated with the PUFA (poly unsaturated fatty acid) content but adverse results were found for SFA (saturated fatty acid) and MUFA (mono unsaturated fatty acid) contents. These findings suggest that MFP could be used as a natural antioxidant in foods for preventing lipid oxidation as well as extending the shelf-life of food products.

Multiple QSAR models, pharmacophore pattern and molecular docking analysis for anticancer activity of α, β-unsaturated carbonyl-based compounds, oxime and oxime ether analogues

NASA Astrophysics Data System (ADS)

Masand, Vijay H.; El-Sayed, Nahed N. E.; Bambole, Mukesh U.; Quazi, Syed A.

2018-04-01

Multiple discrete quantitative structure-activity relationships (QSARs) models were constructed for the anticancer activity of α, β-unsaturated carbonyl-based compounds, oxime and oxime ether analogues with a variety of substituents like sbnd Br, sbnd OH, -OMe, etc. at different positions. A big pool of descriptors was considered for QSAR model building. Genetic algorithm (GA), available in QSARINS-Chem, was executed to choose optimum number and set of descriptors to create the multi-linear regression equations for a dataset of sixty-nine compounds. The newly developed five parametric models were subjected to exhaustive internal and external validation along with Y-scrambling using QSARINS-Chem, according to the OECD principles for QSAR model validation. The models were built using easily interpretable descriptors and accepted after confirming statistically robustness with high external predictive ability. The five parametric models were found to have R2 = 0.80 to 0.86, R2ex = 0.75 to 0.84, and CCCex = 0.85 to 0.90. The models indicate that frequency of nitrogen and oxygen atoms separated by five bonds from each other and internal electronic environment of the molecule have correlation with the anticancer activity.

Potential for ground-water contamination from movement of wastewater through the unsaturated zone, upper Mojave River Basin, California

USGS Publications Warehouse

Umari, A.M.; Martin, P.M.; Schroeder, R.A.; Duell, L.F.; Fay, R.G.

1993-01-01

Septic-tank wastewater disposed in 30-foot-deep seepage pits (dry wells) at 46,000 residences is estimated to equal 18 percent of the natural recharge to the sole-source aquifer in the rapidly developing upper Mojave River Basin (Victor Valley) in the high desert northeast of Los Angeles. Vertical rates of movement of the wastewater wetting front through the unsaturated zone at three newly occupied residences ranged from 0.07 to 1.0 foot per day. These rates translate to traveltimes of several months to several years for the wastewater wetting front to reach the water table and imply that wastewater from many disposal systems already has reached the water table, which averages about 150 feet below land surface in the Victor Valley. As wastewater percolates from seepage pits into the adjacent unsaturated zone, the nitrogen present in reduced form is rapidly converted to nitrate. Analyses on soil-core extracts and soil moisturefrom suction lysimeters installed beneath the seepage pits at eight residences showed that nitrate concentrations and nitrate/ chloride ratios generally become lower with increasing depth. The intervals of greatest decline seemed to coincide with finer soil texture or were near the water table. Nitrate-reducing bacteria were tested for and found to be present in soil cores from two residences. Sparse nitrogen-15 data from suction lysimeters at one of these residences, where thenitrate concentration decreased by about one-half at a depth of 200 feet, indicate that the nitrate decline was accompanied by nitrogen-15 enrichment in the residual nitrate with an isotope-separation factor of about -10 permil. Despite the potential input of abundant nitrogen with the domestic wastewater recharge, nitrate concentrations in the area's ground water are generally low. The absence of high nitrate concentrations in the ground water is consistent with the existence of denitrification, a microbial nitrogen-removal mechanism, as wastewater moves through the thick unsaturated zone and mixes with the ground water. The observed low nitrate concentrations also could be explained by a dilution by vertical mixing in the saturated zone and retention of the wastewater in the unsaturated zone. Results of a single-cell mixing model that allows nitrate from wastewater to be mixedinstantaneously with the underlying ground water suggest that measurable increases in nitrate concentration should be expected within 5 to 10 years after wastewater reaches the water table if the mixing depth is less than 100 feet. Although high fecal-coliform densities were measured in wastewater from septic tanks and seepage pits, removal of these enteric bacteria in the unsaturated zone is very effective, as was indicated by their absence in soil only a few feet from the seepage pits. In testing for organic priority pollutants in wastewater, 17 of 85 compounds were detected. Most compounds detected were present in low concentrations, except at one residence where the concentration of three compounds exceeded 100 micrograms per liter. These high concentrations may be a consequence of disposal practices unique to this residence. Extractable organic priority pollutants were not found in any soil cores taken adjacent to seepage pits and, therefore, are not of concern.

Oligomerization-Dependent Regulation of Motility and Morphogenesis by the Collagen Xviii Nc1/Endostatin Domain

PubMed Central

Kuo, Calvin J.; LaMontagne, Kenneth R.; Garcia-Cardeña, Guillermo; Ackley, Brian D.; Kalman, Daniel; Park, Susan; Christofferson, Rolf; Kamihara, Junne; Ding, Yuan-Hua; Lo, Kin-Ming; Gillies, Stephen; Folkman, Judah; Mulligan, Richard C.; Javaherian, Kashi

2001-01-01

Collagen XVIII (c18) is a triple helical endothelial/epithelial basement membrane protein whose noncollagenous (NC)1 region trimerizes a COOH-terminal endostatin (ES) domain conserved in vertebrates, Caenorhabditis elegans and Drosophila. Here, the c18 NC1 domain functioned as a motility-inducing factor regulating the extracellular matrix (ECM)-dependent morphogenesis of endothelial and other cell types. This motogenic activity required ES domain oligomerization, was dependent on rac, cdc42, and mitogen-activated protein kinase, and exhibited functional distinction from the archetypal motogenic scatter factors hepatocyte growth factor and macrophage stimulatory protein. The motility-inducing and mitogen-activated protein kinase–stimulating activities of c18 NC1 were blocked by its physiologic cleavage product ES monomer, consistent with a proteolysis-dependent negative feedback mechanism. These data indicate that the collagen XVIII NC1 region encodes a motogen strictly requiring ES domain oligomerization and suggest a previously unsuspected mechanism for ECM regulation of motility and morphogenesis. PMID:11257123

Synthesis and biological evaluation of chalcone derivatives (mini review).

PubMed

Bukhari, Syed Nasir Abbas; Jasamai, Malina; Jantan, Ibrahim

2012-11-01

Chalcones are the principal precursors for the biosynthesis of flavonoids and isoflavonoids. A three carbon α, β-unsaturated carbonyl system constitutes chalcones. Chalcones are the condensation products of aromatic aldehyde with acetophenones in attendance of catalyst. They go through an assortment of chemical reactions and are found advantageous in synthesis of pyrazoline, isoxazole and a variety of heterocyclic compounds. In synthesizing a range of therapeutic compounds, chalcones impart key role. They have showed worth mentioning therapeutic efficacy for the treatment of various diseases. Chalcone based derivatives have gained heed since they own simple structures, and diverse pharmacological actions. A lot of methods and schemes have been reported for the synthesis of these compounds. Amongst all, Aldol condensation and Claisen-Schmidt condensation still grasp high up position. Other distinguished techniques include Suzuki reaction, Witting reaction, Friedel-Crafts acylation with cinnamoyl chloride, Photo-Fries rearrangement of phenyl cinnamates etc. These inventive techniques utilize various catalysts and reagents including SOCl(2) natural phosphate, lithium nitrate, amino grafted zeolites, zinc oxide, water, Na(2)CO(3), PEG400, silicasulfuric acid, ZrCl(4) and ionic liquid etc. The development of better techniques for the synthesis of α, β- unsaturated carbonyl compounds is still in high demand. In brief, we have explained the methods and catalysts used in the synthesis of chalcones along with their biological activities in a review form to provide information for the development of new-fangled processes targeting better yield, less reaction time and least side effects with utmost pharmacological properties.

Phosphorus-containing nucleophiles in reactions with polyfluorinated organic compounds

NASA Astrophysics Data System (ADS)

Furin, Georgii G.

1993-03-01

The review presents a compilation of new expelimental data on the reactions of phosphorus-containing nucleophiles [triphenylphosphine, trialkylphosphines, trialkyl phosphites, phosphorus tris(diethylamide), etc.] with perfluorinated olefins and aromatic and heterocyclic compounds, leading to substances both with and without a phosphorus atom. It is shown that the interaction of phosphorus tris(diethylamide) and trialkylphosphines with organic polyfluoro-compounds and perfluoroolefins leads to the formation of phosphoranes, the decomposition of which is accompanied by the generation of aryl and alkenyl anions. The reactions of these anions with C-electrophiles and compounds containing mobile halogen atoms are examined. In addition, the pathways in the Arbuzov reaction involving a series of unsaturated perfluorinated compounds are analysed. Possible applications of these reactions in organic synthesis are demonstrated. The bibliography includes 120 references.

Long Chain Saturated and Unsaturated Carboxylic Acids: Filling a Large Gap of Knowledge in Their Enthalpies of Formation.

PubMed

Rogers, Donald W; Zavitsas, Andreas A

2017-01-06

Despite their abundance in nature and their importance in biology, medicine, nutrition, and in industry, gas phase enthalpies of formation of many long chain saturated and unsaturated fatty acids and of dicarboxylic acids are either unavailable or have been estimated with large uncertainties. Available experimental values for stearic acid show a spread of 68 kJ mol -1 . This work fills the knowledge gap by obtaining reliable values by quantum theoretical calculations using G4 model chemistry. Compounds with up to 20 carbon atoms are treated. The theoretical results are in excellent agreement with well established experimental values when such values exist, and they provide a large number of previously unavailable values.

Atmospheric photochemistry at a fatty acid coated air/water interface

NASA Astrophysics Data System (ADS)

George, Christian; Rossignol, Stéphanie; Passananti, Monica; Tinel, Liselotte; Perrier, Sebastien; Kong, Lingdong; Brigante, Marcello; Bianco, Angelica; Chen, Jianmin; Donaldson, James

2017-04-01

Over the past 20 years, interfacial processes have become increasingly of interest in the field of atmospheric chemistry, with many studies showing that environmental surfaces display specific chemistry and photochemistry, enhancing certain reactions and acting as reactive sinks or sources for various atmospherically relevant species. Many molecules display a free energy minimum at the air-water interface, making it a favored venue for compound accumulation and reaction. Indeed, surface active molecules have been shown to undergo specific photochemistry at the air-water interface. This presentation will address some recent surprises. Indeed, while fatty acids are believed to be photochemically inert in the actinic region, complex volatile organic compounds (VOCs) are produced during illumination of an air-water interface coated solely with a monolayer of carboxylic acid. When aqueous solutions containing nonanoic acid (NA) at bulk concentrations that give rise to just over monolayer NA coverage are illuminated with actinic radiation, saturated and unsaturated aldehydes are seen in the gas phase and more highly oxygenated products appear in the aqueous phase. This chemistry is probably initiated by triplet state NA molecules excited by direct absorption of actinic light at the water surface. As fatty acids covered interfaces are ubiquitous in the environment, such photochemical processing will have a significant impact on local ozone and particle formation. In addition, it was shown recently that a heterogeneous reaction between SO2 and oleic acid (OA; an unsaturated fatty acid) takes place and leads efficiently to the formation of organosulfur products. Here, we demonstrate that this reaction proceeds photochemically on various unsaturated fatty acids compounds, and may therefore have a general environmental impact. This is probably due to the chromophoric nature of the SO2 adduct with C=C bonds, and means that the contribution of this direct addition of SO2 could be in excess of 5%.

Feeding deterrent compounds to the boll weevil,Anthonomus grandis Boheman in Rose-of-Sharon,Hibiscus syriacus L.

PubMed

Bird, T G; Hedin, P A; Burks, M L

1987-05-01

The Rose-of-Sharon,Hibiscus syriacus (L.), can be a significant alternate host plant for the boll weevil,Anthonomus gradis (Boh.). Boll weevils are known to be deterred from feeding and ovipositing in the buds unless the calyx is removed. This investigation was initiated to identify calyx allelochemicals that deter feeding with the eventual strategy of breeding for cotton lines high in these allelochemicals in the appropriate tissues. The feeding deterrency of calyx tissue from the buds of Rose-of-Sharon for the boll weevil was confirmed. The most active deterrent fraction was found to contain mostly fatty acids and their methyl esters. Saturated fatty acids and their methyl esters were generally found to be stimulatory, while the unsaturated species were found to be deterrent. Higher quantities of the fatty acids, particularly the unsaturated species, were found in Rose-of-Sharon calyx tissue than in the buds without calyx. This supports the hypothesis developed through the isolational work and testing of standards that the unsaturated fatty acids are significant deterrents of boll weevil feeding.

Waste isolation and contaminant migration - Tools and techniques for monitoring the saturated zone-unsaturated zone-plant-atmosphere continuum

USGS Publications Warehouse

Andraski, Brian J.; Stonestrom, David A.; Nicholson, T.J.; Arlt, H.D.

2011-01-01

In 1976 the U.S. Geological Survey (USGS) began studies of unsaturated zone hydrology next to the Nation’s first commercial disposal facility for low-level radioactive waste (LLRW) near Beatty, NV. Recognizing the need for long-term data collection, the USGS in 1983 established research management areas in the vicinity of the waste-burial facility through agreements with the Bureau of Land Management and the State of Nevada. Within this framework, the Amargosa Desert Research Site (ADRS; http://nevada.usgs.gov/adrs/) is serving as a field laboratory for the sustained study of water-, gas-, and contaminant-transport processes, and the development of models and methods to characterize flow and transport. The research is built on multiple lines of data that include: micrometeorology; evapotranspiration; plant metrics; soil and sediment properties; unsaturated-zone moisture, temperature, and gas composition; geology and geophysics; and groundwater. Contaminant data include tritium, radiocarbon, volatile-organic compounds (VOCs), and elemental mercury. Presented here is a summary of monitoring tools and techniques that are being applied in studies of waste isolation and contaminant migration.

Alkoxide-based magnesium electrolyte compositions for magnesium batteries

DOEpatents

Dai, Sheng; Sun, Xiao-Guang; Liao, Chen; Guo, Bingkun

2018-01-30

Alkoxide magnesium halide compounds having the formula: RO--Mg--X (1) wherein R is a saturated or unsaturated hydrocarbon group that is unsubstituted, or alternatively, substituted with one or more heteroatom linkers and/or one or more heteroatom-containing groups comprising at least one heteroatom selected from fluorine, nitrogen, oxygen, sulfur, and silicon; and X is a halide atom. Also described are electrolyte compositions containing a compound of Formula (1) in a suitable polar aprotic or ionic solvent, as well as magnesium batteries in which such electrolytes are incorporated.

Synthesis of monomeric and dimeric steroids containing [1,2,4]triazolo[1,5-a]pyrimidines.

PubMed

Arenas-González, Ailed; Mendez-Delgado, Luis Antonio; Merino-Montiel, Penélope; Padrón, José M; Montiel-Smith, Sara; Vega-Báez, José Luis; Meza-Reyes, Socorro

2016-12-01

The synthesis of several monomeric and dimeric steroidal [1,2,4]triazolo[1,5-a]pyrimidines (TPs) derived from steroids are described. These derivatives were prepared from α,β-unsaturated carbonyl compounds through a Claisen Schmidt condensation and rearrangement of the spiro moiety followed by a cycloaddition with 3-amino-1,2,4-triazole. The antiproliferative activity of compounds 7, 13-15 was tested against human cancer cells; several IG 50 values were below 10μM. Copyright © 2016 Elsevier Inc. All rights reserved.

Delineation of ground-water contamination using soil-gas analyses near Jackson, Tennessee

USGS Publications Warehouse

Lee, R.W.

1991-01-01

An investigation of the ground-water resources near Jackson, West Tennessee, was conducted during 1988-89. The study included determination of the occurrence of contaminants in the shallow aquifer using soil-gas analyses in the unsaturated zone. Between 1980 and 1988, an underground fuel-storage tank leaked about 3,000 gallons of unleaded fuel to the water table about 4 feet below land surface. A survey of soil gas using a gas chromatograph equipped with a photoionization detector showed concentrations of volatile organic compounds greater than IO, 000 parts per million near the leak These compounds were detected in an area about 240 feet long and 110 feet wide extending west from the point source. The chromatograms provided two distinct 'fingerprints' of volatile organic compounds. The first revealed the presence of benzene, toluene, andxylenes, which are constituents of unleaded fuel, in addition to other volatile compounds, in soil gas in the area near the leak The second did not reveal any detectable benzene, toluene, or xylenes in the soil-gas samples, but showed the presence of other unidentified volatile organic compounds in soil gas north of the storage tank. The distribution of total concentrations of volatile organic compounds in the unsaturated zone indicated that a second plume about 200 feet long and 90 feet wide was present about 100 feet north of the storage tank The second plume could have been the result of previous activities at this site during the 1950's or earlier. Activities at the site are believed to have included storage of solvents used at the nearby railyard and flushing of tanks containing tar onto a gravel-covered parking area. The delineation of these plumes has shown that soil-gas analyses can be a useful technique for identifying areas of contamination with volatile organic compounds in shallow water-table aquifers and may have broad applications in similar situations where the water table is relatively close to the surface.

Occurrence of active and inactive herbicide ingredients at selected sites in Iowa

USGS Publications Warehouse

Wang, W.; Liszewski, M.; Buchmiller, R.; Cherryholmes, K.

1995-01-01

Herbicides were detected in 50% of water samples, ranging from 78% of water samples from the Ames site to 25% from the Walnut Creek site. Among herbicides detected, listed in decreasing order of frequency, were atrazine > alachlor > cyanazine > metolachlor > metribuzin. Volatile organic compounds were detected in 11% of water samples. Among the compounds detected, listed in decreasing order of frequency, were xylene > toluene > acetone. One sample contained a detectable amount of aliphatic compound(s), with the empirical formula of C8H18. Results from the Deer Creek site showed that herbicides were detected primarily in the top layer (1.2 m), whereas xylene and other alkylbenzenes were detected at 2.1 m or deeper. Apparently, physico-chemical and other factors are separating herbicides and volatile organic compounds in the shallow unsaturated zone.

Acarbose, a Pseudooligosaccharide, Is Transported but Not Metabolized by the Maltose-Maltodextrin System of Escherichia coli

PubMed Central

Brunkhorst, Claudia; Andersen, Christian; Schneider, Erwin

1999-01-01

The pseudooligosaccharide acarbose is a potent inhibitor of amylases, glucosidases, and cyclodextrin glycosyltransferase and is clinically used for the treatment of so-called type II or insulin-independent diabetes. The compound consists of an unsaturated aminocyclitol, a deoxyhexose, and a maltose. The unsaturated aminocyclitol moiety (also called valienamine) is primarily responsible for the inhibition of glucosidases. Due to its structural similarity to maltotetraose, we have investigated whether acarbose is recognized as a substrate by the maltose/maltodextrin system of Escherichia coli. Acarbose at millimolar concentrations specifically affected the growth of E. coli K-12 on maltose as the sole source of carbon and energy. Uptake of radiolabeled maltose was competitively inhibited by acarbose, with a Ki of 1.1 μM. Maltose-grown cells transported radiolabeled acarbose, indicating that the compound is recognized as a substrate. Studying the interaction of acarbose with purified maltoporin in black lipid membranes revealed that the kinetics of acarbose binding to LamB is asymmetric. The on-rate of acarbose is approximately 30 times lower when the molecule enters the pore from the extracellular side than when it enters from the periplasmic side. Acarbose could not be utilized as a carbon source since the compound alone was not a substrate of amylomaltase (MalQ) and was only poorly attacked by maltodextrin glucosidase (MalZ). PMID:10198028

Probing and Comparing the Photobromination and Photoiodination of Dissolved Organic Matter by Using Ultra-High-Resolution Mass Spectrometry.

PubMed

Hao, Zhineng; Yin, Yongguang; Cao, Dong; Liu, Jingfu

2017-05-16

Photochemical halogenation of dissolved organic matter (DOM) may represent an important abiotic process for the formation of natural organobromine compounds (OBCs) and natural organoiodine compounds (OICs) within surface waters. Here we report the enhanced formation of OBCs and OICs by photohalogenating DOM in freshwater and seawater, as well as the noticeable difference in the distribution and composition pattern of newly formed OBCs and OICs. By using negative ion electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry, various OBCs and OICs were identified during the photohalogenation processes in sunlit waters. The respective number of OBCs and OICs formed in artificial seawater (ASW) under light radiation was higher than that in artificial freshwater (AFW), suggesting a possible role of the mixed reactive halogen species. OBCs were formed mainly via substitution reactions and addition reactions accompanied by other reactions and distributed into three classes: unsaturated hydrocarbons with relatively low oxygen content, unsaturated aliphatic compounds, and saturated fatty acids and carbohydrates with relatively high hydrogen content. Unlike the OBCs, OICs were located primarily in the region of carboxylic-rich alicyclic molecules composed of esterified phenolic, carboxylated, and fused alicyclic structures and were generated mainly through electrophilic substitution of the aromatic proton. Our findings call for further investigation on the exact structure and toxicity of the OBCs and OICs generated in the natural environment.

Biochemical characterization of blood orange, sweet orange, lemon, bergamot and bitter orange.

PubMed

Moufida, Saïdani; Marzouk, Brahim

2003-04-01

This paper reports on the composition of aroma compounds and fatty acids and some physico-chemical parameters (juice percentage, acidity and total sugars) in five varieties of citrus: blood orange, sweet orange, lemon, bergamot and bitter orange. Volatile compounds and methyl esters have been analyzed by gas chromatography. Limonene is the most abundant compound of monoterpene hydrocarbons for all of the examined juices. Eighteen fatty acids have been identified in the studied citrus juices, their quantification points out that unsaturated acids predominate over the saturated ones. Mean concentration of fatty acids varies from 311.8 mg/l in blood orange juice to 678 mg/l in bitter orange juice. Copyright 2003 Elsevier Science Ltd.

Nonsaponifiable lipid components of the pollen of elder (Sambucus nigra L.).

PubMed

Stránsky, K; Valterová, I; Fiedler, P

2001-11-30

Pollen of the elder (Sambucus nigra L.) was extracted with chloroform-methanol. The extract was separated by column chromatography into the following groups of compounds: hydrocarbons (8.7%). polycyclic aromatic hydrocarbons (0.2%), complex esters (5.2%), triglycerides (18.7%), hydroxy esters (27.9%), free fatty acids and alcohols (16.8%), free sterols (6.8%), and triterpenic alcohols (4.0%). The nonsaponifiable components (hydrocarbons, fatty acids, alcohols, and sterols) were examined in detail using spectroscopic and chromatographic methods (IR spectroscopy, GC, and GC-MS). The identified compounds were characterized by their mass spectra and Kováts retention indices. The double bond positions and their configurations in unsaturated compounds are also reported.

The mycotoxin patulin reacts with DNA bases with and without previous conjugation to GSH: implication for related α,β-unsaturated carbonyl compounds?

PubMed

Pfenning, Carolin; Esch, Harald L; Fliege, Ralph; Lehmann, Leane

2016-02-01

The α,β-unsaturated carbonyl group is recognized as alert for mutagenicity, attributed to (1) its direct reaction with DNA, counteractable by glutathione (GSH), and (2) oxidative stress caused indirectly by GSH depletion. Accordingly, the α,β,γ,δ-unsaturated lactone patulin (PAT), a mycotoxin detected in fruits and products derived thereof, is known to induce gene, chromosome, and genome mutations in vitro, its mutagenicity correlating inversely with intracellular GSH levels. Thus, the reactivity of PAT against DNA bases and nucleosides in the absence and presence of GSH and glutathione S-transferases (GSTs) was investigated under cell-free conditions using HPLC mass spectrometry techniques for identification of reaction products. Adduct formation with all four nucleobases as well as with purine base nucleosides occurred even in the presence of GSH, revealing several adducts of PAT, mono- and disubstituted with nucleobases/nucleosides as well as novel GSH-PAT adducts. In addition, novel mixed GSH-PAT-nucleobase adducts were observed. These adducts exhibited a ketohexanoic acid-type structure of the PAT molecule, C6 substituted with GSH and linking C1 of PAT with nitrogens of nucleobases/nucleosides via an amide bond. Formation of GSH-PAT-adenine adducts was not prevented by GSTs, and excess of GSH needed to reduce their formation was higher than for PAT-adenine adducts. The formation of mixed GSH-DNA base adducts has not been described for PAT or any other α,β-unsaturated carbonyl before, although the reaction mechanism seems to be applicable to a variety of α,β-unsaturated carbonyls occurring in food and in the environment.

An Approach Using Gas Monitoring to Find the Residual TCE Location in the Unsaturated Zone of Woosan Industrial Complex (WIC), Korea

NASA Astrophysics Data System (ADS)

Koh, Y.; Lee, S.; Yang, J.; Lee, K.

2012-12-01

An area accommodating various industrial facilities has fairly high probability of groundwater contamination with multiple chlorinated solvents such as trichloroethene (TCE), carbon tetrachloride (CT), and chloroform (CF). Source tracing of chlorinated solvents in the unsaturated zone is an essential procedure for the management and remediation of contaminated area. From the previous study on seasonal variations in hydrological stresses and spatial variations in geologic conditions on a TCE plume, the existence of residual DNAPLs at or above the water table has proved. Since TCE is one of the frequently detected VOCs (Volatile Organic Compounds) in groundwater, residual TCE can be detected by gas monitoring. Therefore, monitoring of temporal and spatial variations in the gas phase TCE contaminant at an industrial complex in Wonju, Korea, were used to find the residual TCE locations. As pilot tests, TCE gas samples collected in the unsaturated zone at 4 different wells were analyzed using SPME (Solid Phase MicroExtraction) fiber and Gas Chromatography (GC). The results indicated that detecting TCE in gas phase was successful from these wells and TCE analysis on gas samples, collected from the unsaturated zone, will be useful for source area characterization. However, some values were too high to doubt the accuracy of the current method, which needs a preliminary lab test with known concentrations. The modified experiment setups using packer at different depths are in process to find residual TCE locations in the unsaturated zone. Meanwhile, several PVD (polyethylene-membrane Passive Vapor Diffusion) samplers were placed under water table to detect VOCs by equilibrium between air in the vial and VOCs in pore water.

Occurrence of Agricultural Chemicals in Shallow Ground Water and the Unsaturated Zone, Northeast Nebraska Glacial Till, 2002-04

USGS Publications Warehouse

Stanton, Jennifer S.; Steele, Gregory V.; Vogel, Jason R.

2007-01-01

Agricultural chemicals applied at the land surface in northeast Nebraska can move downward, past the crop root zone, to ground water. Because agricultural chemicals applied at the land surface are more likely to be observed in the shallowest part of an aquifer, an assessment of shallow ground-water and unsaturated zone quality in the northeast Nebraska glacial till was completed between 2002 and 2004. Ground-water samples were collected at the first occurrence of ground water or just below the water table at 32 sites located in areas likely affected by agriculture. Four of the 32 sites were situated along a ground-water flow path with its downgradient end next to Maple Creek. Twenty-eight sites were installed immediately adjacent to agricultural fields throughout the glacial-till area. In addition to those 32 sites, two sites were installed in pastures to represent ground-water conditions in a non-cropland setting. Ground-water samples were analyzed for physical properties and concentrations of nitrogen and phosphorus compounds, selected pesticides and pesticide degradates, dissolved solids, major ions, trace elements, and dissolved organic carbon. Chlorofluorocarbons (CFCs) or sulfur hexafluoride (SF6) concentrations were analyzed at about 70 percent of the monitoring wells to estimate the residence time of ground water. Borehole-core samples were collected from 28 of the well boreholes. Sediment in the unsaturated zone was analyzed for nitrate, chloride, and ammonia concentrations. Analytical results indicated that the agricultural chemicals most often detected during this study were nitrates and herbicides. Nitrate as nitrogen (nitrate-N) concentrations (2003 median 9.53 milligrams per liter) indicated that human activity has affected the water quality of recently recharged ground water in approximately two-thirds of the wells near corn and soybean fields. The principal pesticide compounds that were detected reflect the most-used pesticides in the area and included parent or degradate compounds of acetochlor, alachlor, atrazine, and metolachlor. Overall, pesticide concentrations in ground-water samples collected in 2003 and 2004 were small and did not exceed public drinking-water standards where established. On average, more pesticides were detected in the flow-path wells than in the glacial-till network wells. The presence of a perennial stream within 1,640 feet of a well was correlated to smaller nitrate-N concentrations in the well water, and the presence of a road ditch within 164 feet of the well was correlated to the presence of detectable pesticides in the well water. All other variables tested showed no significant correlations to nitrate-N concentrations or pesticide detections. Unsaturated zone soil cores collected in 2002 from well boreholes indicated that nitrogen in the forms of nitrate-N and ammonia as nitrogen (ammonia-N) was available in the unsaturated zone for transport to ground water. Concentrations of nitrate-N and ammonia-N in these soil cores were inversely correlated to depth, and nitrate-N concentrations were correlated to chloride concentrations.

Synthesis of silyl iron hydride via Si-H activation and its dual catalytic application in the hydrosilylation of carbonyl compounds and dehydration of benzamides.

PubMed

Ren, Shishuai; Xie, Shangqing; Zheng, Tingting; Wang, Yangyang; Xu, Shilu; Xue, Benjing; Li, Xiaoyan; Sun, Hongjian; Fuhr, Olaf; Fenske, Dieter

2018-03-28

The hydrido silyl iron complex (o-Ph 2 PC 6 H 4 SiMe 2 )Fe(PMe 3 ) 3 H (2) was obtained via the activation of the Si-H bond of the bidentate silyl ligand o-Ph 2 P(C 6 H 4 )SiMe 2 H (1) by Fe(PMe 3 ) 4 . 2 showed good to excellent catalytic activity in both the reduction of aldehydes/ketones and the dehydration of benzamide. In addition, with complex 2 as a catalyst, α,β-unsaturated carbonyls could be selectively reduced to the corresponding α,β-unsaturated alcohols. The mechanisms of the formation of 2 and the catalytic dehydration process are proposed and partly experimentally verified.

Solvent Extraction and GC-MS Analysis of Sesame Seeds for Determination of Bioactive Antioxidant Fatty Acid/Fatty Oil Components.

PubMed

Qadir, Abdul; Ali, Athar; Arif, Muhammad; Al-Rohaimi, Abdulmohsen H; Singh, Satya Prakash; Ahmad, Usama; Khalid, Mohd; Kumar, Arun

2018-06-01

The seed kernels of Sesamum indicum L. (family: Pedaliaceae) were extracted with ethanol and yield of components determined by Gas Chromatography/Mass Spectrometry (GC/MS). The free radical scavenging activities of ethanolic extract against1, 1-Diphenyl-2-picrylhydrazyl (DPPH) were determined by UV spectrophotometer at 517 nm. Phytochemical screening revealed the presence of numerous bioactive compounds including steroids, phenolic, terpenoids, fatty acids and different types of ester compounds. The ethanolic extract was purified and analyzed by GC MS.The prevailing compounds found in ethanolic extract were Carvacrol (0.04%),Sesamol (0.11%), 4-Allyl-2-methoxy-phenol(0.04%),Palmitic acid (1.08%), cis-9-Hexadecenal (85.40%), Lineoleoyl chloride (0.52%), Palmitic acid β-monoglyceride (0.40%), Dihydro-aplotaxene (0.61%), Oleoyl chloride (1.11%), (+)-Sesamin (4.73%), 1,3-Benzodioxole, 5-[4-(1,3-benzodioxol-5-yloxy)tetrahydro-1 H,3 H-furo [3,4-c]furan-1-yl], [1 S-(1,3,4,6α.), (2.01%)], 6-Nitrocholest-5-en-3-yl acetate (0.22%), Ergost-5-en-3β-ol (2.35%) and 24-Propylidenecholesterol (0.16%). The presence ofsaturated and unsaturated fatty acids in ethanolicextract justifies the use of this plant to treat many ailments in folk and traditional medicine. Ethanolic extract have shown significant antioxidant activity(IC 50 120.38±2.8 µg/ml). The presence of phenolic (Sesamol), lignin (Sesamin) compounds and unsaturated fatty acids are reported as possible contributor for antioxidantactivity of seed extract. © Georg Thieme Verlag KG Stuttgart · New York.

Kinetics and product identification of the reactions of (E)-2-hexenyl acetate and 4-methyl-3-penten-2-one with OH radicals and Cl atoms at 298 K and atmospheric pressure

NASA Astrophysics Data System (ADS)

Gaona-Colmán, Elizabeth; Blanco, María B.; Teruel, Mariano A.

2017-07-01

Rate coefficients for the reactions of hydroxyl radicals and chlorine atoms with two biogenic volatile organic compounds as (E)-2-hexenyl acetate and 4-methyl-3-penten-2-one have been determined at 298 K and atmospheric pressure. The decay of the organics was followed using a chromatograph with a flame ionization detector (GC-FID) and the rate constants were determined using a relative rate method. Rate coefficients are found to be (in cm3 molecule-1 s-1): k1(OH + (E)-2-hexenyl acetate) = (6.88 ± 1.41) × 10-11, k2(Cl + (E)-2-hexenyl acetate) = (3.10 ± 1.13) × 10-10, k3(OH + 4-methyl-3-penten-2-one) = (1.02 ± 0.20) × 10-10 and k4(Cl + 4-methyl-3-penten-2-one) = (2.66 ± 0.90) × 10-10 at 298 K. This is the first kinetic experimental study for these reactions studied under atmospheric pressure. The rate coefficients are compared with previous determinations for other unsaturated and oxygenated compounds and reactivity trends are presented. Products identification studies were performed using solid-phase microextraction (SPME) method employing on-fiber products derivatization with o-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine hydrochloride using gas chromatograph with a mass spectrometer detector (GC-MS) for the reactions studied. In addition, atmospheric lifetimes of the unsaturated compounds studied are estimated and compared with other tropospheric sinks for these compounds.

Stellar and laboratory XUV/EUV line ratios in Fe XVIII and Fe XIX

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

Traebert, E.; Beiersdorfer, P.; Clementson, J.

2012-05-25

A so-called XUV excess has been suspected with the relative fluxes of Fe XVIII and Fe XIX lines observed in the XUV and EUV ranges of the spectrum of the star Capella as observed by the Chandra spacecraft, even after correction for interstellar absorption. This excess becomes apparent in the comparison of the observations with simulations of stellar spectra obtained using collisional-radiative models that employ, for example, the Atomic Plasma Emission Code (APEC) or the Flexible Atomic Code (FAC). We have addressed this problem by laboratory studies using the Livermore electron beam ion trap (EBIT).

Hydrogenation of biomass-derived substrates

DOEpatents

Gordon, John C.; Waidmann, Christopher R.

2016-06-07

The .alpha.,.beta.-unsaturated ketone moiety of a substrate representative of non-food based biomass was hydrogenated to the corresponding saturated alcohol moiety using a composition including (1) a copper salt; (2) a phosphine; (3) a polar aprotic solvent such as acetonitrile, and (4) a compound suitable for providing hydrogen for the hydrogenation, such as a suitable silane material or a suitable siloxane material.

Effect of cuprous oxide with different sizes on thermal and combustion behaviors of unsaturated polyester resin.

PubMed

Hou, Yanbei; Hu, Weizhao; Gui, Zhou; Hu, Yuan

2017-07-15

Cuprous oxide (Cu 2 O) as an effective catalyst has been applied to enhance the fire safety of unsaturated polyester resin (UPR), but the particle size influence on combustion behaviors has not been previously reported. Herein, the UPR/Cu 2 O composites (metal oxide particles with average particle-size of 10, 100, and 200nm) were successfully synthesized by thermosetting process. The effects of Cu 2 O with different sizes on thermostability and combustion behaviors of UPR were characterized by TGA, MCC, TG-IR, FTIR, and SSTF. The results revel that the addition of Cu 2 O contributes to sufficient decomposition of oxygen-containing compounds, which is beneficial to the release of nontoxic compounds. The smallest-sized Cu 2 O performs the excellent catalytic decomposition effect and promotes the complete combustion of UPR, which benefits the enhancement of fire safety. While the other additives retard pyrolysis process and yield more char residue, and thus the flame retardancy of UPR composites was improved. Therefore, catalysis plays a major role for smaller-sized particles during thermal decomposition of matrix, while flame retarded effect became gradual distinctly for the larger-sized additives. Copyright © 2017 Elsevier B.V. All rights reserved.

Assessing the role of Pseudomonas aeruginosa surface-active gene expression in hexadecane biodegradation in sand.

PubMed

Holden, P A; LaMontagne, M G; Bruce, A K; Miller, W G; Lindow, S E

2002-05-01

Low pollutant substrate bioavailability limits hydrocarbon biodegradation in soils. Bacterially produced surface-active compounds, such as rhamnolipid biosurfactant and the PA bioemulsifying protein produced by Pseudomonas aeruginosa, can improve bioavailability and biodegradation in liquid culture, but their production and roles in soils are unknown. In this study, we asked if the genes for surface-active compounds are expressed in unsaturated porous media contaminated with hexadecane. Furthermore, if expression does occur, is biodegradation enhanced? To detect expression of genes for surface-active compounds, we fused the gfp reporter gene either to the promoter region of pra, which encodes for the emulsifying PA protein, or to the promoter of the transcriptional activator rhlR. We assessed green fluorescent protein (GFP) production conferred by these gene fusions in P. aeruginosa PG201. GFP was produced in sand culture, indicating that the rhlR and pra genes are both transcribed in unsaturated porous media. Confocal laser scanning microscopy of liquid drops revealed that gfp expression was localized at the hexadecane-water interface. Wild-type PG201 and its mutants that are deficient in either PA protein, rhamnolipid synthesis, or both were studied to determine if the genetic potential to make surface-active compounds confers an advantage to P. aeruginosa biodegrading hexadecane in sand. Hexadecane depletion rates and carbon utilization efficiency in sand culture were the same for wild-type and mutant strains, i.e., whether PG201 was proficient or deficient in surfactant or emulsifier production. Environmental scanning electron microscopy revealed that colonization of sand grains was sparse, with cells in small monolayer clusters instead of multilayered biofilms. Our findings suggest that P. aeruginosa likely produces surface-active compounds in sand culture. However, the ability to produce surface-active compounds did not enhance biodegradation in sand culture because well-distributed cells and well-distributed hexadecane favored direct contact to hexadecane for most cells. In contrast, surface-active compounds enable bacteria in liquid culture to adhere to the hexadecane-water interface when they otherwise would not, and thus production of surface-active compounds is an advantage for hexadecane biodegradation in well-dispersed liquid systems.

Comparison and characterization of volatile compounds as markers of oils stability during frying by HS-SPME-GC/MS and Chemometric analysis.

PubMed

Ben Hammouda, Ibtissem; Freitas, Flavia; Ammar, Sonda; Da Silva, M D R Gomes; Bouaziz, Mohamed

2017-11-15

The formation and emission of volatile compounds, including the aldehydes and some toxic compounds of oil samples, ROPO pure (100%) and the blended ROPO/RCO (80-20%), were carried out during deep frying at 180°C. The volatile profile of both oil samples was evaluated by an optimized HS-SPME-GC/MS method, before and after 20, 40 and 60 successive sessions of deep-frying. Actually, from 100 detected compounds, aldehydes were found to be the main group formed. In addition, the oil degradation under thermal treatment regarding the volatile compounds were evaluated and compared. Consequently, the blended ROPO/RCO revealed fewer formations of unsaturated aldehydes, including toxic ones, such as acrolein, and showed a greater stability against oxidative thermal degradation compared to ROPO pure. Copyright © 2017 Elsevier B.V. All rights reserved.

Thermal Decomposition of Methyl Esters in Biodiesel Fuel: Kinetics, Mechanisms and Products

NASA Astrophysics Data System (ADS)

Chai, Ming

Biodiesel continues to enjoy increasing popularity. However, recent studies on carbonyl compounds emissions from biodiesel fuel are inconclusive. Emissions of carbonyl compounds from petroleum diesel fuels were compared to emissions from pure biodiesel fuels and petroleum-biodiesel blends used in a non-road diesel generator. The concentration of total carbonyl compounds was the highest when the engine was idling. The carbonyl emissions, as well as ozone formation potential, from biodiesel fuel blends were higher than those emitted from petroleum diesel fuel. The sulfur content of diesel fuel and the source of biodiesel fuel were not found to have a significant impact on emissions of carbonyl compounds. Mechanism parameters of the thermal decomposition of biodiesel-range methyl esters were obtained from the results of thermal gravimetric analysis (TGA). The overall reaction orders are between 0.49 and 0.71 and the energies of activation are between 59.9 and 101.3 kJ/mole. Methyl esters in air have lower activation energies than those in nitrogen. Methyl linoleate has the lowest activation energy, followed by methyl oleate, and methyl stearate. The pyrolysis and oxidation of the three methyl esters were investigated using a semi-isothermal tubular flow reactor. The profiles of major products versus reaction temperature are presented. In the pyrolysis of methyl stearate, the primary reaction pathway is the decarboxylic reaction at the methyl ester functional group. Methyl oleate's products indicate more reactions on its carbon-carbon double bond. Methyl linoleate shows highest reactivity among the three methyl esters, and 87 products were detected. The oxidation of three methyl esters resulted in more products in all compound classes, and 55, 114, and 127 products were detected, respectively. The oxidation of methyl esters includes decarboxylation on ester group. The methyl ester's carbon chain could be oxidized as a hydrocarbon compound and form oxidized esters and unsaturated esters, which have been observed in methyl ester's oxidation products. The oxidation of methyl stearate, methyl oleate and methyl linoleate produces 16, 28 and 34 types of carbonyl compounds, respectively. The unsaturated methyl ester forms more carbonyl compounds compared to the saturated methyl ester, which indicates the formation of carbonyl compounds might be more related to the unsaturated carbon bond rather than the methyl ester group. Good agreement between results for total carbon (TC) generally has been found, but the organic and elemental carbon (OC and EC) fractions determined by different methods often disagree. Lack of reference materials has impeded progress on method standardization and understanding method biases. As part of this dissertation, uniform carbon distribution for the filter sets is prepared by using a simply aerosol generation and collection method. The relative standard deviations for the mean TC, OC, and EC results reported by the seven laboratories were below 10%, 11% and 12% (respectively). The method of filter generation is generally applicable and reproducible. Depending on the application, different filter loadings and types of OC materials can be employed. Matched filter sets prepared by this approach can be used for determining the accuracy of various OC-EC methods and thereby contribute to method standardization.

B-535a, b and c, new sphingosine kinase inhibitors, produced by a marine bacterium; taxonomy, fermentation, isolation, physico-chemical properties and structure determination.

PubMed

Kono, K; Tanaka, M; Mizuno, T; Kodama, K; Ogita, T; Kohama, T

2000-08-01

In the course of our screening for inhibitors of sphingosine kinase, we found a series of active compounds in a culture broth of a novel marine bacterium, SANK 71896. The structures of the compounds, named B-5354a, b and c, were elucidated by a combination of spectroscopic analyses to be new esters of 4-amino-3-hydroxybenzoic acid with long-chain unsaturated alcohols. B-5354a, b and c inhibit sphingosine kinase activity with IC50 values of 21, 58 and 38 microm, respectively.

A review on chemistry of a powerful organic electron acceptor 7, 7, 8, 8, tetracynoquinodimethane (TCNQ)

NASA Astrophysics Data System (ADS)

Singh, Yadunath

2018-05-01

Organic semiconductors have so far found extensive practical applications similar to inorganic semiconductors. Interest in these compounds has been stimulated by the synthesis of several powerful electron acceptors, such as tetracynoethylene (TCNE), 7, 7, 8, 8, tetracynoquinodimethane (TCNQ) and cyno-p-benzoquinone. In this connection TCNQ is of particular interest, due to presence of four powerful electron accepting groups in its molecule. Nucleophillic addition reactions, which are rarely encountered among unsaturated compounds, as well as addition reactions proceeding via a one electron transfer stage are characteristic of this substance.

Para-hydrogen induced polarization of Si-29 NMR resonances as a potentially useful tool for analytical applications.

PubMed

Ellena, Silvano; Viale, Alessandra; Gobetto, Roberto; Aime, Silvio

2012-08-01

Para-hydrogen-induced polarization effects have been observed in the (29)Si NMR spectra of trimethylsilyl para-hydrogenated molecules. The high signal enhancements and the long T(1) values observed for the (29)Si hyperpolarized resonances point toward the possibility of using (29)Si for hyperpolarization applications. A method for the discrimination of multiple compounds and/or complex mixtures of hydroxylic compounds (such as steroids), consisting of the silylization of alcoholic functionalities with an unsaturated silylalkyl moiety and subsequent reaction with para-H(2), is proposed. Copyright © 2012 John Wiley & Sons, Ltd.

Asymmetric bioreduction of activated alkenes to industrially relevant optically active compounds

PubMed Central

Winkler, Christoph K.; Tasnádi, Gábor; Clay, Dorina; Hall, Mélanie; Faber, Kurt

2012-01-01

Ene-reductases from the ‘Old Yellow Enzyme’ family of flavoproteins catalyze the asymmetric reduction of various α,β-unsaturated compounds at the expense of a nicotinamide cofactor. They have been applied to the synthesis of valuable enantiopure products, including chiral building blocks with broad industrial applications, terpenoids, amino acid derivatives and fragrances. The combination of these highly stereoselective biocatalysts with a cofactor recycling system has allowed the development of cost-effective methods for the generation of optically active molecules, which is strengthened by the availability of stereo-complementary enzyme homologues. PMID:22498437

Investigation and simulation on fate and transport of leachate from a livestock mortality burial site

NASA Astrophysics Data System (ADS)

Lim, J.-W.; Lee, S.; Kaown, D.; Lee, K.-K.

2012-04-01

Leachate released from livestock mortality burial during decomposition of carcasses can be a threat to groundwater quality. Monitoring study of groundwater quality in the vicinity of livestock burial reported that a caution is needed to prevent contamination of both groundwater and soil, especially in case of mortality burial (Glanville, 2000; Ritter and Chirnside, 1995). The average concentration of ammonium-N and chloride is reported to be 12,600 mg/l and 2,600 mg/l respectively, which is 2-4 times higher than leachate from earthen manure storages and landfills (Pratt, 2009). To assess the potential threat of burial leachate to groundwater quality, simulation of leachate transport is performed based on a hydrogeologic model of an actual mortality burial site. At the burial site of this study located at a hill slope, two mortality pits have been constructed along the slope to bury swine during the outbreak of nationwide foot and mouth disease(FMD) in 2011. Though the pits were partially lined with impermeable material, potential threat of leachate leakage is still in concern. Electrical resistivity survey has been performed several times at the burial site and abnormal resistivity zones have been detected which are supposed as leachate leakage from the burial. Subsurface model including unsaturated zone is built since the leakage is supposed to occur mainly in lateral of the burial pits which is in unsaturated zone. When examining leachate transport, main focus is given to a nitrogenous compound and colloidal character of FMD virus. Nitrifying of denitrifying characters of nitrogenous compound and transport of colloidal particles are affected mainly by soil water content in unsaturated zone. Thus, the fate and transport of burial leachate affected by seasonal variation in recharge pattern is investigated.

Synthesis, evaluation, and metabolism of novel [6]-shogaol derivatives as potent Nrf2 activators.

PubMed

Zhu, Yingdong; Wang, Pei; Zhao, Yantao; Yang, Chun; Clark, Anderson; Leung, TinChung; Chen, Xiaoxin; Sang, Shengmin

2016-06-01

Oxidative stress is a central component of many chronic diseases. The Kelch-like ECH-associated protein 1 (Keap1)-nuclear factor erythroid 2 p45-related factor 2 (Nrf2) system is a major regulatory pathway of cytoprotective genes against oxidative and electrophilic stress. Activation of the Nrf2 pathway plays crucial roles in the chemopreventive effects of various inducers. In this study, we developed a novel class of potent Nrf2 activators derived from ginger compound, [6]-shogaol (6S), using the Tg[glutathione S-transferase pi 1 (gstp1):green fluorescent protein (GFP)] transgenic zebrafish model. Investigation of structure-activity relationships of 6S derivatives indicates that the combination of an α,β-unsaturated carbonyl entity and a catechol moiety in one compound enhances the Tg(gstp1:GFP) fluorescence signal in zebrafish embryos. Chemical reaction and in vivo metabolism studies of the four most potent 6S derivatives showed that both α,β-unsaturated carbonyl entity and catechol moiety act as major active groups for conjugation with the sulfhydryl groups of the cysteine residues. In addition, we further demonstrated that 6S derivatives increased the expression of Nrf2 downstream target, heme oxygenase-1, in both a dose- and time-dependent manner. These results suggest that α,β-unsaturated carbonyl entity and catechol moiety of 6S derivatives may react with the cysteine residues of Keap1, disrupting the Keap1-Nrf2 complex, thereby liberating and activating Nrf2. Our findings of natural product-derived Nrf2 activators lead to design options of potent Nrf2 activators for further optimization. Copyright © 2016 Elsevier Inc. All rights reserved.

Anacardic Acid Constituents from Cashew Nut Shell Liquid: NMR Characterization and the Effect of Unsaturation on Its Biological Activities

PubMed Central

Morais, Selene M.; Silva, Katherine A.; Araujo, Halisson; Vieira, Icaro G.P.; Alves, Daniela R.; Fontenelle, Raquel O.S.; Silva, Artur M.S.

2017-01-01

Anacardic acids are the main constituents of natural cashew nut shell liquid (CNSL), obtained via the extraction of cashew shells with hexane at room temperature. This raw material presents high technological potential due to its various biological properties. The main components of CNSL are the anacardic acids, salicylic acid derivatives presenting a side chain of fifteen carbon atoms with different degrees of unsaturation (monoene–15:1, diene–15:2, and triene–15:3). Each constituent was isolated by column chromatography using silica gel impregnated with silver nitrate. The structures of the compounds were characterized by nuclear magnetic resonance through complete and unequivocal proton and carbon assignments. The effect of the side chain unsaturation was also evaluated in relation to antioxidant, antifungal and anticholinesterase activities, and toxicity against Artemia salina. The triene anacardic acid provided better results in antioxidant activity assessed by the inhibition of the free radical 1,1-diphenyl-2-picrylhydrazyl (DPPH), higher cytotoxicity against A. salina, and acetylcholinesterase (AChE) inhibition. Thus, increasing the unsaturation of the side chain of anacardic acid increases its action against free radicals, AChE enzyme, and A. salina nauplii. In relation to antifungal activity, an inverse result was obtained, and the linearity of the molecule plays an important role, with monoene being the most active. In conclusion, the changes in structure of anacardic acids, which cause differences in polarity, contribute to the increase or decrease in the biological activity assessed. PMID:28300791

Microwave-assisted cationic polymerization of palm olein and their urea inclusion products

NASA Astrophysics Data System (ADS)

Soegijono, Bambang; Farid, Muhamad; Alim Mas'ud, Zainal

2018-01-01

Cationic polymerization is affected by the relative amount of unsaturated bond (C=C) in the compound. The enrichment of an unsaturated triglyceride fraction from oils may be performed using urea inclusion techniques. In this study, palm olein was enriched-unsaturated fraction using urea-methanol system. The palm olein and its urea-inclusion products were cationic polymerized with ethereal boron trifluoride catalyst and followed by irradiation using a commercial microwave (microwave-assisted). The microwave irradiated products were cured at 110 °C for 24 hours. Fatty acid composition of the palm olein and its urea-inclusion products were analyzed by gas chromatography. Iodine numbers, functional groups, and ultraviolet absorption spectra of all palm olein origin, urea inclusion products and polymerization products were analyzed using titrimetric, ultraviolet spectrophotometric, and Fourier Transform infrared spectrophotometric methods. Differential scanning calorimetric (DSC) was used to observe the thermal characteristics of the polymer. Urea-inclusion process increased the unsaturated fatty acid components as indicated by the increased iodine number, intensity of alkene band absorptions in the infrared spectra, and the absorbance of the ultraviolet spectra. The polymer formation is converting the C=C group to C-C, which is indicated by the opposite of the urea inclusion process. The curing process results in reformation of new C=C bonds that were similar to that of the urea inclusion process. The DSC thermogram curve shows that the enrichment process improves the thermal stability of the polymer formed.

Molecular species composition of plant cardiolipin determined by liquid chromatography mass spectrometry

PubMed Central

Zhou, Yonghong; Peisker, Helga

2016-01-01

Cardiolipin (CL), an anionic phospholipid of the inner mitochondrial membrane, provides essential functions for stabilizing respiratory complexes and is involved in mitochondrial morphogenesis and programmed cell death in animals. The role of CL and its metabolism in plants are less well understood. The measurement of CL in plants, including its molecular species composition, is hampered by the fact that CL is of extremely low abundance, and that plants contain large amounts of interfering compounds including galactolipids, neutral lipids, and pigments. We used solid phase extraction by anion exchange chromatography to purify CL from crude plant lipid extracts. LC/MS was used to determine the content and molecular species composition of CL. Thus, up to 23 different molecular species of CL were detected in different plant species, including Arabidopsis, mung bean, spinach, barley, and tobacco. Similar to animals, plant CL is dominated by highly unsaturated species, mostly containing linoleic and linolenic acid. During phosphate deprivation or exposure to an extended dark period, the amount of CL decreased in Arabidopsis, accompanied with an increased degree in unsaturation. The mechanism of CL remodeling during stress, and the function of highly unsaturated CL molecular species, remains to be defined. PMID:27179363

Partial Hydrothermal Oxidation of High Molecular Weight Unsaturated Carboxylic Acids for Upgrading of Biodiesel Fuel

NASA Astrophysics Data System (ADS)

Kawasaki, K.; Jin, F.; Kishita, A.; Tohji, K.; Enomoto, H.

2007-03-01

With increasing environmental awareness and crude oil price, biodiesel fuel (BDF) is gaining recognition as a renewable fuel which may be used as an alternative diesel fuel without any modification to the engine. The cold flow and viscosity of BDF, however, is a major drawback that limited its use in cold area. In this study, therefore, we investigated that partial oxidation of high molecular weight unsaturated carboxylic acids in subcritical water, which major compositions in BDF, to upgrade biodiesel fuel. Oleic acid, (HOOC(CH2)7CH=CH(CH2)7CH3), was selected as a model compound of high molecular weight unsaturated carboxylic acids. All experiments were performed with a batch reactor made of SUS 316 with an internal volume of 5.7 cm3. Oleic acid was oxidized at 300 °C with oxygen supply varying from 1-10 %. Results showed that a large amount of carboxylic acids and aldehydes having 8-9 carbon atoms were formed. These experimental results suggest that the hydrothermal oxidative cleavage may mainly occur at double bonds and the cleavage of double bonds could improve the cold flow and viscosity of BDF.

Raman microspectroscopy of noncancerous and cancerous human breast tissues. Identification and phase transitions of linoleic and oleic acids by Raman low-temperature studies.

PubMed

Brozek-Pluska, Beata; Kopec, Monika; Surmacki, Jakub; Abramczyk, Halina

2015-04-07

We present the results of Raman studies in the temperature range of 293-77 K on vibrational properties of linoleic and oleic acids and Raman microspectroscopy of human breast tissues at room temperature. Our results confirmed the significant role of unsaturated fatty acids in differentiation of noncancerous and cancerous breast tissues and the role of vibrational spectroscopy in phase transition identification. We have found that vibrational properties are very sensitive indicators to specify phases and phase transitions typical of unsaturated fatty acids at the molecular level. Using Raman spectroscopy we have identified high-temperature, middle-temperature and low-temperature phases of linoleic acid. Results obtained for linoleic acid were compared with parameters characteristic of α and γ phases of oleic acid - the parent compound of polyunsaturated fatty acids.

Design new P-glycoprotein modulators based on molecular docking and CoMFA study of α, β-unsaturated carbonyl-based compounds and oxime analogs as anticancer agents

NASA Astrophysics Data System (ADS)

Sepehri, Bakhtyar; Ghavami, Raouf

2017-02-01

In this research, molecular docking and CoMFA were used to determine interactions of α, β-unsaturated carbonyl-based compounds and oxime analogs with P-glycoprotein and prediction of their activity. Molecular docking study shown these molecules establish strong Van der Waals interactions with side chain of PHE-332, PHE-728 and PHE-974. Based on the effect of component numbers on squared correlation coefficient for cross validation tests (including leave-one-out and leave-many-out), CoMFA models with five components were built to predict pIC50 of molecules in seven cancer cell lines (including Panc-1 (pancreas cancer cell line), PaCa-2 (pancreatic carcinoma cell line), MCF-7 (breast cancer cell line), A-549 (epithelial), HT-29 (colon cancer cell line), H-460 (lung cancer cell line), PC-3 (prostate cancer cell line)). R2 values for training and test sets were in the range of 0.94-0.97 and 0.84 to 0.92, respectively, and for LOO and LMO cross validation test, q2 values were in the range of 0.75-0.82 and 0.65 to 0.73, respectively. Based on molecular docking results and extracted steric and electrostatic contour maps for CoMFA models, four new molecules with higher activity with respect to the most active compound in data set were designed.

Mulliken-Hush analysis of a bis(triarylamine) mixed-valence system with a N...N distance of 28.7 A.

PubMed

Heckmann, Alexander; Amthor, Stephan; Lambert, Christoph

2006-07-28

An organic mixed valence compound with a spacer length of 25 unsaturated bonds separating two amine redox centres was synthesised and the electron transfer behaviour was investigated in the context of a Mulliken-Hush analysis in order to estimate the longest redox centre separation for which an intervalence charge transfer band can be observed.

Plastic Media Blasting Data Gathering Study

DTIC Science & Technology

1986-12-01

products of organic compounds containing the amino group (-NH 2 ) and an aldehyde. The better known members of this group are urea formaldehyde (a...suspected carcinogen) and melamine formaldehyde . The actual composition and toxicity of the dust from the various operations must be collected and...blasting is a paint removal technique in which small, granular amino thermoset or unsaturated polyester resins (plastic beads) are forced at high

Circulating Vascular Basement Membrane Fragments are Associated with the Diameter of the Abdominal Aorta and Their Expression Pattern is Altered in AAA Tissue.

PubMed

Holsti, Mari; Wanhainen, Anders; Lundin, Christina; Björck, Martin; Tegler, Gustaf; Svensson, Johan; Sund, Malin

2018-04-12

Abdominal aortic aneurysm (AAA) is characterised by enhanced proteolytic activity, and extracellular matrix (ECM) remodelling in the vascular wall. Type IV and XVIII collagen/endostatin are structural proteins in vascular basement membrane (VBM), a specialised ECM structure. Here the association between plasma levels of these collagens with the aortic diameter and expansion rate is studied, and their expression in aortic tissue characterised. This was a retrospective population based cohort study. Type IV and XVIII collagen/endostatin were analysed in plasma by ELISA assay in 615 men, divided into three groups based on the aortic diameter: 1) normal aorta ≤ 25 mm, 2) sub-aneurysmal aorta (SAA) 26-29 mm, and 3) AAA ≥ 30 mm. Follow up data were available for 159 men. The association between collagen levels and aortic diameter at baseline, and with the expansion rate at follow up were analysed in ordinal logistic regression and linear regression models, controlling for common confounding factors. Tissue expression of the collagens was analysed in normal aorta (n = 6) and AAA (n = 6) by immunofluorescence. Plasma levels of type XVIII collagen/endostatin (136 ng/mL [SD 29] in individuals with a normal aorta diameter, 154 ng/ml [SD 45] in SAA, and 162 ng/ml [SD 46] in AAA; p = .001) and type IV collagen (105 ng/mL [SD 42] normal aorta, 124 ng/ml [SD 46] SAA, and 127 ng/ml [SD 47] AAA; p = .037) were associated with a larger aortic diameter. A significant association was found between the baseline levels of type XVIII/endostatin and the aortic expansion rate (p = .035), but in the multivariable model, only the initial aortic diameter remained significantly associated with expansion (p = .005). Altered expression patterns of both collagens were observed in AAA tissue. Plasma levels of circulating type IV and XVIII collagen/endostatin increase with AAA diameter. The expression pattern of VBM proteins is altered in the aneurysm wall. Copyright © 2018 European Society for Vascular Surgery. Published by Elsevier B.V. All rights reserved.

The Molecular Composition of Dissolved Organic Matter in Forest Soils as a Function of pH and Temperature

PubMed Central

Roth, Vanessa-Nina; Dittmar, Thorsten; Gaupp, Reinhard; Gleixner, Gerd

2015-01-01

We examined the molecular composition of forest soil water during three different seasons at three different sites, using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS). We examined oxic soils and tested the hypothesis that pH and season correlate with the molecular composition of dissolved organic matter (DOM). We used molecular formulae and their relative intensity from ESI-FT-ICR-MS for statistical analysis. Applying unconstrained and constrained ordination methods, we observed that pH, dissolved organic carbon (DOC) concentration and season were the main factors correlating with DOM molecular composition. This result is consistent with a previous study where pH was a main driver of the molecular differences between DOM from oxic rivers and anoxic bog systems in the Yenisei River catchment. At a higher pH, the molecular formulae had a lower degree of unsaturation and oxygenation, lower molecular size and a higher abundance of nitrogen-containing compounds. These characteristics suggest a higher abundance of tannin connected to lower pH that possibly inhibited biological decomposition. Higher biological activity at a higher pH might also be related to the higher abundance of nitrogen-containing compounds. Comparing the seasons, we observed a decrease in unsaturation, molecular diversity and the number of nitrogen-containing compounds in the course of the year from March to November. Temperature possibly inhibited biological degradation during winter, which could cause the accumulation of a more diverse compound spectrum until the temperature increased again. Our findings suggest that the molecular composition of DOM in soil pore waters is dynamic and a function of ecosystem activity, pH and temperature. PMID:25793306

Contamination of shallow ground water in the area of building 95, Picatinny Arsenal, New Jersey, 1985-90

USGS Publications Warehouse

Sargent, B.P.; Storck, D.A.

1994-01-01

A zone of contaminated ground water at Picatinny Arsenal has resulted from the operation of a metal- plating facility in building 95 during 1960-81, and the wastewater-treatment system that is in and adjacent to the building. Thirty-two monitoring wells were installed in 1989 to supplement 12 previously installed wells. All wells were sampled in 1989 and 1990 for analysis of ground water for inorganic constituents, trace elements, volatile organic compounds, and nutrients. Four wells also were sampled for analysis for base/neutral- and acid-extractable compounds and pesticides, and soil gas from the unsaturated zone at eight sites was analyzed for volatile organic compounds. Concentrations of dissolved solids and sulfate in the study area were consistently above the U.S. Environmental Protection Agency's secondary drinking-water regulations. The areal distribution of sulfate differed from that of the volatile organic compounds. Concentrations of trace elements were not elevated downgradient from the source. The estimated average velocity of contaminant movement is 0.1 to 1.1 feet per day. The major organic contaminants identified in the study area are trichloroethylene, tetrachloroethylene, and 1,1,1-trichloroethane. Trichloroethylene was detected in wells upgradient from the wastewater- treatment site. Tetrachloroethylene and 1,1,1-trichloroethane might originate at tanks in the basement of building 95 rather than at the adjacent wastewater-treatment system. The pre- dominant gas-phase contaminant, 1,1,1- trichloroethane, was detected at a maximum con- centration of 15.7 micrograms per liter. Both trichoroethylene and tetrachloroethylene were detected in concentrations greater than 0.10 micrograms per liter in five of the eight soil- gas samples, indicating that volatilization and diffusion through the unsaturated zone could be a significant mechanism of contaminant loss from the aquifer.

Fate of effluent-borne contaminants beneath septic tank drainfields overlying a Karst aquifer.

PubMed

Katz, Brian G; Griffin, Dale W; McMahon, Peter B; Harden, Harmon S; Wade, Edgar; Hicks, Richard W; Chanton, Jeffrey P

2010-01-01

Groundwater quality effects from septic tanks were investigated in the Woodville Karst Plain, an area that contains numerous sinkholes and a thin veneer of sands and clays overlying the Upper Floridan aquifer (UFA). Concerns have emerged about elevated nitrate concentrations in the UFA, which is the source of water supply in this area of northern Florida. At three sites during dry and wet periods in 2007-2008, water samples were collected from the septic tank, shallow and deep lysimeters, and drainfield and background wells in the UFA and analyzed for multiple chemical indicators including nutrients, nitrate isotopes, organic wastewater compounds (OWCs), pharmaceutical compounds, and microbiological indicators (bacteria and viruses). Median NO3-N concentration in groundwater beneath the septic tank drainfields was 20 mg L(-1) (8.0-26 mg L(-1)). After adjusting for dilution, about 25 to 40% N loss (from denitrification, ammonium sorption, and ammonia volatilization) occurs as septic tank effluent moves through the unsaturated zone to the water table. Nitrogen loading rates to groundwater were highly variable at each site (3.9-12 kg N yr(-1)), as were N and chloride depth profiles in the unsaturated zone. Most OWCs and pharmaceutical compounds were highly attenuated beneath the drainfields; however, five Cs (caffeine, 1,7-dimethylxanthine, phenol, galaxolide, and tris(dichloroisotopropyl)phosphate) and two pharmaceutical compounds (acetaminophen and sulfamethoxazole) were detected in groundwater samples. Indicator bacteria and human enteric viruses were detected in septic tank effluent samples but only intermittently in soil water and groundwater. Contaminant movement to groundwater beneath each septic tank system also was related to water use and differences in lithology at each site.

Sources, compositions, and optical properties of humic-like substances in Beijing during the 2014 APEC summit: Results from dual carbon isotope and Fourier-transform ion cyclotron resonance mass spectrometry analyses.

PubMed

Mo, Yangzhi; Li, Jun; Jiang, Bin; Su, Tao; Geng, Xiaofei; Liu, Junwen; Jiang, Haoyu; Shen, Chengde; Ding, Ping; Zhong, Guangcai; Cheng, Zhineng; Liao, Yuhong; Tian, Chongguo; Chen, Yingjun; Zhang, Gan

2018-08-01

Humic-like substances (HULIS) are a class of high molecular weight, light-absorbing compounds that are highly related to brown carbon (BrC). In this study, the sources and compositions of HULIS isolated from fine particles collected in Beijing, China during the 2014 Asia-Pacific Economic Cooperation (APEC) summit were characterized based on carbon isotope ( 13 C and 14 C) and Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) analyses, respectively. HULIS were the main light-absorbing components of water-soluble organic carbon (WSOC), accounting for 80.2 ± 6.1% of the WSOC absorption capacity at 365 nm. The carbon isotope data showed that HULIS had a lower non-fossil contribution (53 ± 4%) and were less enriched with 13 C (-24.2 ± 0.6‰) relative to non-HULIS (62 ± 8% and -20.8 ± 0.3‰, respectively). The higher relative intensity fraction of sulfur-containing compounds in HULIS before and after APEC was attributed to higher sulfur dioxide levels emitted from fossil fuel combustion, whereas the higher fraction of nitrogen-containing compounds during APEC may have been due to the relatively greater contribution of non-fossil compounds or the influence of nitrate radical chemistry. The results of investigating the relationships among the sources, elemental compositions, and optical properties of HULIS demonstrated that the light absorption of HULIS appeared to increase with increasing unsaturation degree, but decrease with increasing oxidation level. The unsaturation of HULIS was affected by both sources and aging level. Copyright © 2018 Elsevier Ltd. All rights reserved.

Rapid Reconnaissance Mapping of Volatile Organic Compounds by Photoionization Detection at the USGS Amargosa Desert Research Site

NASA Astrophysics Data System (ADS)

Thordsen, J. J.; Stonestrom, D. A.; Conaway, C. H.; Luo, W.; Baker, R. J.; Andraski, B. J.

2015-12-01

Two types of handheld photoionization detectors were evaluated in April 2015 for reconnaissance mapping of volatile organic compounds (VOCs) in the unsaturated zone surrounding legacy disposal trenches for commercial low-level radioactive waste near Beatty, Nevada (USA). This method is rapid and cost effective when compared to the more conventional procedure used ate the site, where VOCs are collected on sorbent cartridges in the field followed by thermal desorption, gas chromatographic separation, and quantitation by mass spectroscopy in the laboratory (TD-GC-MS analysis). Using the conventional method, more than sixty distinct compounds have been identified in the 110-m deep unsaturated zone vapor phase, and the changing nature of the VOC mix over a 15-yr timeframe has been recorded. Analyses to date have identified chlorofluorocarbons (CFCs), chlorinated ethenes, chlorinated ethanes, gasoline-range hydrocarbons, chloroform, and carbon tetrachloride as the main classes of VOCs present. The VOC plumes emanating from the various subgroups of trenches are characterized by different relative abundances of the compound classes, and total VOC concentrations that cover several orders of magnitude. One of the photoionization detectors, designed for industrial compliance testing, lacked sufficient dynamic range and sensitivity to be useful. The other, a wide range (1 ppb-20,000 ppm) research-grade instrument with a 10.6 eV photoionization detector (PID) lamp, produced promising results, detecting roughly half of the non-CFC VOCs present. The rapid and inexpensive photoionization method is envisioned as a screening tool to supplement, expedite, and direct the collection of additional samples for TD-GC-MS analyses at this and other VOC-contaminated sites.

Characterization of polar organics in airborne particulate matter

NASA Astrophysics Data System (ADS)

Yokouchi, Y.; Ambe, Y.

The methanol-extractable highly polar organics in atmospheric aerosol were characterized using GC-MS. Dicarboxylic acids having 2-16 carbon numbers were detected with a total concentration of 172 ng m -3. Azelaic acid ( C9) was the most abundant diacid and it possibly originated from the ozonolysis of unsaturated carboxylic acids such as oleic acid and linoleic acid, which mainly originate from terrestrial plants. A compound, which was tentatively identified as tetrahydrofuroic acid, contributed to about 10% of the highly polar organics. Other polyfunctional compounds found in the samples included some ketocarboxylic acids and aromatic acids such as phthalic acids, anisic acid and vanillic acid.

Relationship between chemical structure and rat repellency

USGS Publications Warehouse

Bellack, E.; DeWitt, J.B.; Treichler, R.

1953-01-01

Repellent activity is defined as the activity of a compound in preventing consumption of, or gnawing attacks upon, foodstuffs or articles containing or treated with the candidate substance. Data are presented on repellency indices of 2700 compounds, and it is shown that repellency is associated with specific functional groups attached to alkyl, aryl, or heterocyclic nuclei. Functional groups containing nitrogen, sulfur or halogens are most active, with amines, imides, thiocyanates and thiocarbamates forming some of the most active classes. Activity of any functional group may be affected by molecular weight, unsaturation, or spatial configuration of the nucleus, or by the presence of additional substituent groups.

[Branched alkanes and other apolar compounds produced by the cyanobacterium Microcoleus vaginatus from the Negev desert].

PubMed

Dembitskiĭ, V M; Dor, I; Shkrob, I; Aki, M

2001-01-01

Gas chromatography-mass spectrometry on serially coupled capillary columns with different polarity of stationary phases showed that the soil cyanobacterium Microcoleus vaginatus from the Negev desert produces an unusual mixture of 4 normal and more than 60 branched alkanes, as well as a number of fatty acids, cyclic and unsaturated hydrocarbons, aldehydes, alcohols, and ketones. The dominant compounds were heptadecane (12%), 7-methylheptadecane (7.8%), hexadecanoic acid (6.5%), (Z)-9-hexadecenoic acid (5.6%), 4-ethyl-2,2,6,6-tetramethylheptane (2.8%), (Z)-9-octadecenoic acid (2.8%), and 4-methyl-5-propylnonane (2.7%).

Synthesis, reactivity and application studies for different biolubricants

PubMed Central

2014-01-01

Vegetable oils have different unique properties owing to their unique chemical structure. Vegetable oils have a greater ability to lubricate and have higher viscosity indices. Therefore, they are being more closely examined as base oil for biolubricants and functional fluids. In spite of their many advantages, vegetable oils suffer from two major drawbacks of inadequate oxidative stability and poor low-temperature properties, which hinder their utilization as biolubricant base oils. Transforming alkene groups in fatty acids to other stable functional groups could improve the oxidative stability, whereas reducing structural uniformity of the oil by attaching alkyl side chains could improve the low-temperature performance. In that light, the epoxidation of unsaturated fatty acids is very interesting as it can provide diverse side chains arising from the mono- or di-epoxidation of the unsaturated fatty acid. Oxirane ring opening by an acid-catalyzed reaction with a suitable reagent provides interesting polyfunctional compounds. PMID:24612780

Kinetic analysis of competition between aerosol particle removal and generation by ionization air purifiers.

PubMed

Alshawa, Ahmad; Russell, Ashley R; Nizkorodov, Sergey A

2007-04-01

Ionization air purifiers are increasingly used to remove aerosol particles from indoor air. However, certain ionization air purifiers also emit ozone. Reactions between the emitted ozone and unsaturated volatile organic compounds (VOC) commonly found in indoor air produce additional respirable aerosol particles in the ultrafine (<0.1 microm) and fine (<2.5 microm) size domains. A simple kinetic model is used to analyze the competition between the removal and generation of particulate matter by ionization air purifiers under conditions of a typical residential building. This model predicts that certain widely used ionization air purifiers may actually increase the mass concentration of fine and ultrafine particulates in the presence of common unsaturated VOC, such as limonene contained in many household cleaning products. This prediction is supported by an explicit observation of ultrafine particle nucleation events caused by the addition of D-limonene to a ventilated office room equipped with a common ionization air purifier.

Protective effect of vanilloids against tert-butyl hydroperoxide-induced oxidative stress in vero cells culture.

PubMed

Rosa, Antonella; Atzeri, Angela; Deiana, Monica; Melis, M Paola; Incani, Alessandra; Corona, Giulia; Loru, Debora; Appendino, Giovanni; Dessì, M Assunta

2008-05-28

This study investigated the effect of synthetic capsiate, a simplified analogue of capsiate, and vanillyl alcohol on the oxidative stress induced by tert-butyl hydroperoxide (TBH) in a line of fibroblasts derived from monkey kidney (Vero cells). In response to the TBH-mediated oxidative stress, a reduction of the levels of total unsaturated fatty acids and cholesterol was observed, and a rise in the concentrations of conjugated dienes fatty acids hydroperoxides and 7-ketocholesterol. Pretreatment with both synthetic capsiate and vanillyl alcohol preserved Vero cells from oxidative damage and showed a remarkable protective effect on the reduction of the levels of total unsaturated fatty acids and cholesterol, inhibiting the increase of MDA, conjugated dienes fatty acids hydroperoxides, and 7-ketocholesterol. Both compounds were effective against peroxidation of cell membrane lipids induced by TBH, with synthetic capsiate essentially acting as a pro-drug of vanillyl alcohol, its hydrophilic hydrolytic derivative.

Covalent Modifiers: A Chemical Perspective on the Reactivity of α,β-Unsaturated Carbonyls with Thiols via Hetero-Michael Addition Reactions.

PubMed

Jackson, Paul A; Widen, John C; Harki, Daniel A; Brummond, Kay M

2017-02-09

Although Michael acceptors display a potent and broad spectrum of bioactivity, they have largely been ignored in drug discovery because of their presumed indiscriminate reactivity. As such, a dearth of information exists relevant to the thiol reactivity of natural products and their analogues possessing this moiety. In the midst of recently approved acrylamide-containing drugs, it is clear that a good understanding of the hetero-Michael addition reaction and the relative reactivities of biological thiols with Michael acceptors under physiological conditions is needed for the design and use of these compounds as biological tools and potential therapeutics. This Perspective provides information that will contribute to this understanding, such as kinetics of thiol addition reactions, bioactivities, as well as steric and electronic factors that influence the electrophilicity and reversibility of Michael acceptors. This Perspective is focused on α,β-unsaturated carbonyls given their preponderance in bioactive natural products.

An Approach that Uses the Concentrations of Hydrocarbon Compounds in Soil Gas at the Source of Contamination to Evaluate the Potential for Intrusion of Petroleum Vapors into Buildings (PVI)

EPA Science Inventory

If motor fuels are spilled from underground storage tanks, petroleum hydrocarbons can vaporize from the spill and move as a vapor through the unsaturated zone. If a building is sited above or near the spill, the hydrocarbons may intrude into the air space of the building. This ...

Does Aging or Endothelial Dysfunction Pose a Threat to Military Crewmembers

DTIC Science & Technology

1999-10-01

that have proven its vulnerable to oxidation. Eicosapentaenoic and primary medical effect to ameliorate or even docosahexaenoic acids in marine lipids...and a family of 21-amino acid peptide prostanoids like thromboxane A2, prostaglandin BIOLOGY OF ENDOTHELIUM H2 and components of renin-angiotensin...oxidizable compounds like LDL-cholesterol and Moreover, the whole process is influenced unsaturated fatty acids . There is a battery of negatively by

Mass Spectrometric Approaches to the Identification of Potential Ingredients in Cigarette Smoke Causing Cytotoxicity.

PubMed

Horiyama, Shizuyo; Kunitomo, Masaru; Yoshikawa, Noriko; Nakamura, Kazuki

2016-01-01

Cigarette smoke contains many harmful chemicals that contribute to the pathogenesis of smoking-related diseases such as chronic obstructive pulmonary disease, cancer, and cardiovascular disease. Many studies have been done to identify cytotoxic chemicals in cigarette smoke and elucidate the onset of the above-mentioned diseases caused by smoking. However, definitive mechanisms for cigarette smoke toxicity remain unknown. As candidates for cytotoxic chemicals, we have recently found methyl vinyl ketone (MVK) and acetic anhydride in nicotine/tar-free cigarette smoke extract (CSE) using L-tyrosine (Tyr), an amino acid with highly reactive hydroxyl group. The presence of MVK and acetic anhydride in CSE was confirmed by gas chromatography-mass spectrometry (GC/MS). We also found new reaction products formed in B16-BL6 mouse melanoma (B16-BL6) cells treated with CSE using LC/MS. These were identified as glutathione (GSH) conjugates of α,β-unsaturated carbonyl compounds, MVK, crotonaldehyde (CA), and acrolein (ACR), by the mass value and product ion spectra of these new products. ACR and MVK are type-2 alkenes, which are well known as electron acceptors and form Michael-type adducts to nucleophilic side chain of amino acids on peptides. These α,β-unsaturated carbonyl compounds may have a key role in CSE-induced cell death.

Formation of doubly and triply bonded unsaturated compounds HCN, HNC, and CH2NH via N + CH4 low-temperature solid state reaction: from molecular clouds to solar system objects

NASA Astrophysics Data System (ADS)

Mencos, Alejandro; Krim, Lahouari

2018-06-01

We show in the current study carried out in solid phase at cryogenic temperatures that methane (CH4) ice exposed to nitrogen atoms is a source of two acids HCN, HNC, and their corresponding hydrogenated unsaturated species CH2NH, in addition to CH3, C2H6, CN-, and three nitrogen hydrides NH, NH2, and NH3. The solid state N + CH4 reaction taken in the ground state seems to be strongly temperature dependent. While at temperatures lower than 10 K only CH3, NH, NH2, and NH3 species formation is promoted due to CH bond dissociation and NH bond formation, stable compounds with CN bonds are formed at temperatures ranged between 10 and 40 K. Many of these reaction products, resulting from CH4 + N reaction, have already been observed in N2-rich regions such as the atmospheres of Titan, Kuiper belt objects, and molecular clouds of the interstellar medium. Our results show the power of the solid state N-atom chemistry in the transformation of simple astrochemical relevant species, such as CH4 molecules and N atoms into complex organic molecules which are also potentially prebiotic species.

Ferric hydroxide supported gold subnano clusters or quantum dots: enhanced catalytic performance in chemoselective hydrogenation.

PubMed

Liu, Lequan; Qiao, Botao; Ma, Yubo; Zhang, Juan; Deng, Youquan

2008-05-21

An attempt to prepare ferric hydroxide supported Au subnano clusters via modified co-precipitation without any calcination was made. High resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) have been employed to study the structure and chemical states of these catalysts. No Au species could be observed in the HRTEM image nor from the XRD pattern, suggesting that the sizes of the Au species in and on the ferric hydroxide support were less than or around 1 nm. Chemoselective hydrogenation of aromatic nitro compounds and alpha,beta-unsaturated aldehydes was selected as a probe reaction to examine the catalytic properties of this catalyst. Under the same reaction conditions, such as 100 degrees C and 1 MPa H2 in the hydrogenation of aromatic nitro compounds, a 96-99% conversion (except for 4-nitrobenzonitrile) with 99% selectivity was obtained over the ferric hydroxide supported Au catalyst, and the TOF values were 2-6 times higher than that of the corresponding ferric oxide supported catalyst with 3-5 nm size Au particles. For further evaluation of this Au catalyst in the hydrogenation of citral and cinnamaldehyde, selectivity towards unsaturated alcohols was 2-20 times higher than that of the corresponding ferric oxide Au catalyst.

Measurement of wavelengths and lamb shifts for inner-shell transitions in Fe XVIII-XXIV. [from solar flare X-ray spectra

NASA Technical Reports Server (NTRS)

Seely, J. F.; Feldman, U.; Safronova, U. I.

1986-01-01

The wavelengths of inner-shell 1s-2p transitions in the ions Fe XVIII-XXIV have been measured in solar flare spectra recorded by the Naval Research Laboratory crystal spectrometer (SOLFLEX) on the Air Force P78-1 spacecraft. The measurements are compared with previous measurements and with recently calculated wavelengths. It is found that the measured wavelengths are systematically larger than the wavelengths calculated using the Z-expansion method by up to 0.65 mA. For the more highly charged ions, these differences can be attributed to the QED contributions to the transition energies that are not included in the Z-expansion calculations.

Identification of a Novel Class of Covalent Modifiers of Hemoglobin as Potential Antisickling Agents

PubMed Central

Omar, A. M.; Mahran, M. A.; Ghatge, M. S.; Chowdhury, N.; Bamane, F. H. A.; El-Araby, M. E.; Abdulmalik, O.; Safo, M. K.

2015-01-01

Aromatic aldehydes and ethacrynic acid (ECA) exhibit antipolymerization properties that are beneficial for sickle cell disease therapy. Based on ECA pharmacophore and its atomic interaction with hemoglobin, we designed and synthesized several compounds--designated as KAUS (imidazolylacryloyl derivatives)--that we hypothesized would bind covalently to βCys93 of hemoglobin and inhibit sickling. The compounds surprisingly showed weak allosteric and antisickling properties. X-ray studies of hemoglobin in complex with representative KAUS compounds revealed an unanticipated mode of Michael addition reaction between the β-unsaturated carbon and the N-terminal αVal1 nitrogen at the α-cleft of hemoglobin, with no observable interaction with βCys93. Interestingly, the compounds exhibited almost no reactivity with the free amino acids, L-Val, L-His and L-Lys, however showed some reactivity with both glutathione and L-Cys. Our findings provide a molecular level explanation to the compounds biological activities and an important framework for targeted modifications that would yield novel potent antisickling agents. PMID:25974708

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

Ford, JP; Thapaliya, N; Kelly, MJ

Fatty acids (FAs) derived via thermal hydrolysis of food-grade lard and canola oil were deoxygenated in the liquid phase using a commercially available 5 wt % Pd/C catalyst. Online quadrupole mass spectrometry and gas chromatography were used to monitor the effluent gases from the semi-batch stirred autoclave reactors. Stearic, oleic, and palmitic acids were employed as model compounds. A catalyst lifetime exceeding 2200 turnovers for oleic acid deoxygenation was demonstrated at 300 degrees C and 15 atm under 10% H-2. The initial decarboxylation rate of palmitic acid under 5% H-2 decreases sharply with increasing initial concentration; in contrast, the initialmore » decarbonylation rate increases linearly, indicative of first-order kinetics. Scale-up of diesel-range hydrocarbon production was investigated by increasing the reactor vessel size, initial FA concentration, and FA/catalyst mass ratio. Lower CO2 selectivity and batch productivity were observed at the larger scales (600 and 5000 mL), primarily because of the higher initial FA concentration (67 wt %) employed. Because unsaturated FAs must be hydrogenated before deoxygenation can proceed at an appreciable rate, the additional batch time required for FA hydrogenation reduces the batch productivity for unsaturated feedstocks. Low-temperature hydrogenation of unsaturated feedstocks (using Pd/C or another less-expensive catalyst) prior to deoxygenation is recommended.« less

Endostatin expression in a pancreatic cell line is modulated by a TNFα-dependent elastase

PubMed Central

Brammer, R D; Bramhall, S R; Eggo, M C

2005-01-01

Endostatin, an inhibitor of angiogenesis, is a 20 kDa fragment of the basement membrane protein, collagen XVIII. The formation of endostatin relies upon the action of proteases on collagen XVIII. TNFα, produced by activated macrophages, is a multifunctional proinflammatory cytokine with known effects on endothelial function. We postulated that TNFα may modulate the activities of proteases and thus regulate endostatin formation in pancreatic cells. Collagen XVIII/endostatin mRNA was expressed in one pancreatic cell line, SUIT-2, but not in BxPc-3. The 20 kDa endostatin was found in the cell-conditioned medium of SUIT-2 cells. Precursor forms only were found in the cells. Exogenous endostatin was degraded by cellular lysates of SUIT-2 cells. Elastase activity was found in cell extracts but not the cell-conditioned media of SUIT-2 cells. Incubation of SUIT-2 cells with TNFα increased intracellular elastase activity and also increased secretion of endostatin into the medium. We conclude that endostatin is released by SUIT-2 cells and that increases in intracellular elastase, induced by TNFα, are correlated with increased secretion. Endostatin is however susceptible to degradation by intracellular proteases and if tissue injury accompanies inflammation, endostatin may be degraded, allowing angiogenesis to occur. PMID:16234817

Characterization of the Chemical Constitution and Profile of Pharmacological Activity of PGB(x).

DTIC Science & Technology

1982-02-26

ischemia. Fed. Proc. 40 , 692 (1980). 3. Burkman, A. M. and Phornchirasilp, S., Prostaglandin Bx enhances the inotropic efficacy (Emax) of...nitroketone 10 was then converted to the sodium salt of the corresponding nitronic acid on treatment with an equimolar amount of sodium metabolite in...bromide in chloroform-ethyl acetate to give unsaturated aldehyde 12 in 40 ’ yield. The reaction of compound 9 with dimethyl (2-oxoheptvl) phosphonate in

α-Pyrone derivatives with cytotoxic activities, from the endophytic fungus Phoma sp. YN02-P-3.

PubMed

Sang, Xia-Nan; Chen, Shao-Fei; Tang, Ming-Xu; Wang, Hai-Feng; An, Xiao; Lu, Xiao-Jie; Zhao, Dan; Wang, Yu-Bo; Bai, Jiao; Hua, Hui-Ming; Chen, Gang; Pei, Yue-Hu

2017-08-15

Four new α-pyrone derivatives phomones C-F (1-4) together with four known compounds (5-8) were isolated from the endophytic fungus Phoma sp. YN02-P-3. Compound 1 is the first example of 6-α,β-unsaturated ester-2-pyrone dimers via intermolecular symmetrical [2+2] cycloaddition. The chemical structures of these compounds were determined from spectroscopic data (1D/2D NMR, MS and IR). The acetylated product (9) of 1 along with compounds 1-8 were then tested for their cytotoxicity against HL-60, PC-3 and HCT-116 cell lines. Compounds 2, 3, 5 and 9 with acetyl groups showed significant inhibitory activities against the three cell lines with IC 50 values in the range 0.52-9.85μM. while compounds 1, 4 and 6-8 that possess no acetyl group showed no inhibitory activity (IC 50 >50μM), indicating that the acetyl group at 10- or 12- are essential for their cytotoxic activities. The structure-activity relationships of these phomones were also reported. Copyright © 2017 Elsevier Ltd. All rights reserved.

Low-valent group 14 element hydride chemistry: towards catalysis.

PubMed

Hadlington, Terrance J; Driess, Matthias; Jones, Cameron

2018-06-05

The chemistry of group 14 element(ii) hydride complexes has rapidly expanded since the first stable example of such a compound was reported in 2000. Since that time it has become apparent that these systems display remarkable reactivity patterns, in some cases mimicking those of late transition-metal (TM) hydride compounds. This is especially so for the hydroelementation of unsaturated organic substrates. Recently, this aspect of their reactivity has been extended to the use of group 14 element(ii) hydrides as efficient, "TM-like" catalysts in organic synthesis. This review will detail how the chemistry of these hydride compounds has advanced since their early development. Throughout, there is a focus on the importance of ligand effects in these systems, and how ligand design can greatly modify a coordinated complex's electronic structure, reactivity, and catalytic efficiency.

[The becoming of public medicine (second half of XVIII-first half of xix centuries). Report I: The origin of concept of medical police, governing bodies of medical sanitary business, physician sanitary legislation].

PubMed

Stotchik, A M; Zatravkin, S N; Stotchik, A A

2013-01-01

The present report covers the history of origination of concept of medical police in the second half of XVIII century. This body became one of the most important tool of state governance in Austria. France, Prussia and Russia. The relationship between origin of this concept and the results of scientific studies in area of investigation of epidemic constitutions is demonstrated. Two directions of activity of bodies of state governance are considered concerning the implementation of medical police--imposition of public administration of activities of physicians and development by joint efforts of physicians and lawyers of special physician sanitary legislation.

Evaluation of unsaturated-zone solute-transport models for studies of agricultural chemicals

USGS Publications Warehouse

Nolan, Bernard T.; Bayless, E. Randall; Green, Christopher T.; Garg, Sheena; Voss, Frank D.; Lampe, David C.; Barbash, Jack E.; Capel, Paul D.; Bekins, Barbara A.

2005-01-01

Of the models tested, RZWQM, HYDRUS2D, VS2DT, GLEAMS and PRZM had graphical user interfaces. Extensive documentation was available for RZWQM, HYDRUS2D, and VS2DT. RZWQM can explicitly simulate water and solute flux in macropores, and both HYDRUS2D and VS2DT can simulate water and solute flux in two dimensions. The version of RZWQM tested had a maximum simulation depth of 3 meters. The complex models simulate the formation, transport, and fate of degradates of up to three to five compounds including the parent, with the exception of VS2DT, which simulates the transport and fate of a single compound.

Sea buckthorn as a source of important bioactive compounds in cardiovascular diseases.

PubMed

Olas, Beata

2016-11-01

Hippophae rhamnoides (sea buckthorn) offers many health benefits. It has significant cardioprotective activity and exerts many positive healing effects on the cardiovascular system, including inhibiting blood platelet activation (especially platelet aggregation), lowering cholesterol concentration and blood pressure, and providing antioxidant activity. In addition, sea buckthorn has antibacterial and antiviral properties. The leaves and fruits of the plant, and its oils, are sources of many bioactive substances including vitamins (A, C and E), unsaturated fatty acids, phenolic compounds, especially flavonoids, and phytosterols, which bestow positive effects on the cardiovascular system. This review article summarizes the current knowledge of the biological roles of sea buckthorn in cardiovascular diseases. Copyright © 2016 Elsevier Ltd. All rights reserved.

2-Hydroxy-succinaldehyde, a lipid peroxidation product proving that polyunsaturated fatty acids are able to react with three molecules of oxygen.

PubMed

Mlakar, A; Spiteller, G

1997-01-01

2-Hydroxy-succinaldehyde was detected by a GC/MS analysis of trapped aldehydic compounds obtained after Fe2+/ascorbate lipid peroxidation of arachidonic acid. Precursor molecules of aldehydes are hydroperoxy compounds. Thus the generation of the two aldehydic groups in 2-hydroxysuccinaldehyde requires a precursor molecule with two hydroperoxy groups. The hydroxy group in 2-position is generated by a third hydroperoxidation reaction. The detection of 2-hydroxysuccinaldehyde--although found only in traces--is the first example for triple dioxigenation of unsaturated fatty acid. Linolenic acid produces 2-hydroxysuccinaldehyde in much lower amounts than arachidonic acid. A similar oxidation of linoleic acid was not observed.

A series of new manganese thioarsenates(v) based on different unsaturated [Mn(amine)x](2+) complexes.

PubMed

Zhou, Jian; Tan, Xiao-Feng; Liu, Xing; Qing, Miao; Zhao, Rong-Qing; Tang, Qiuling

2015-10-07

A series of new manganese thioarsenates(V) [Mn(en)2Cu(AsVS4)]n (1, en = ethylenediamine), [Mn(dien)2][Mn(dien)(AsVS4)]2 (2, dien = diethylenetriamine), [Mn(teta)(AsVS4)]n (3, teta = triethylenetetramine), and {[Mn(dap)2][Mn(dap)(AsVS4)]2}n (4, dap = 1,2-diaminopropane) have been solvothermally synthesized and structurally characterized. 1 displays a neutral heterometallic [Mn(en)2Cu(AsVS4)]n chain built up from the linkages of [Mn(en)2]2+ complexes and infinite heterometallic [Cu(AsVS4)2−]n chains, and represents the only example of incorporation of an unsaturated [Mn(en)2]2+ complex into the 1-D [Cu(AsVS4)2−]n framework. 2 consists of a discrete {[Mn(dien)]2(AsVS4)2}2− cluster and a charge compensating complex cation [Mn(dien)2]2+. 3 shows a 1-D neutral [Mn(teta)(AsVS4)]n chain constructed by the combination of both complex [Mn(teta)]2+ ions and tetrahedral [AsVS4]3− anions. 4 exhibits a rare 2-D {[Mn(dap)2][Mn(dap)(AsVS4)]2}n layer based on the linkages of [AsVS4]3− anions and [Mn(dap)x]2+ (x = 1, 2) groups. These results show that different unsaturated [Mn(amine)x]2+ complexes are directly bonded to [AsVS4]3− anions to give different manganese thioarsenates(V), which have a significant structure directing effect on the structures of manganese thioarsenates(V) under similar solvothermal conditions. The present compounds exhibit wide-band-gap semiconducting properties with absorption band edges between 2.00 and 2.58 eV, and density functional theory calculations for compounds 1, 3 and 4 have also been performed.

Herbicide Transport and Transformations in the Unsaturated Zone of Three Small Agricultural Basins with Corn and Soybean Row Crops

NASA Astrophysics Data System (ADS)

Hancock, T. C.; Vogel, J. R.; Sandstrom, M. W.; Capel, P. D.; Bayless, R. E.; Webb, R. M.

2006-05-01

In the United States, herbicides are among the most significant nonpoint-source pollutants and were applied to 95% of all fields in corn production and 97% of all fields in soybean production in 2003 and 2004. The United States Geological Survey (USGS) has conducted a study on select herbicides in the unsaturated zone under corn and soybean fields in three predominantly agricultural basins: Morgan Creek (Maryland), Leary Weber Ditch within Sugar Creek (Indiana), and Maple Creek (Nebraska). In 2004, the Morgan Creek and Leary Weber Ditch fields were in soybeans and the Maple Creek fields were in corn. The Maple Creek fields were irrigated, whereas those in Morgan Creek and Leary Weber Ditch were not. Similarities and differences in agricultural management practices, climatic conditions, and natural features, such as soil types and geology, were evaluated as part of the study. In general, the amounts of herbicides entering the unsaturated zone from rain in these basins were minor (1%) compared to amounts commonly applied to the land surface during agricultural practices. Few herbicides were detected on solid core samples from the unsaturated zones of these basins. An exception was found at a Morgan Creek site in an upland recharge area with sandier soils. Here, atrazine concentrations were highest in the near surface solids and decreased with depth. In the unsaturated-zone porewater of the Morgan Creek Basin, parent triazine and acetanilide herbicides were detected and only at the site in the upland recharge area at relatively low concentrations at depths greater than 4 meters, probably because these compounds had not been applied for several years. At the Morgan Creek and Leary Weber Ditch sites, acetanilide metabolites were frequently detected in the unsaturated-zone porewater. In general, the fraction of metolachlor ethane sulfonic acid (ESA) relative to the total mass of parent and metabolites increased with depth overall and at several individual sampling locations this fraction increased over time. At the Maple Creek sites, atrazine, metalochlor, acetochlor, and alachlor were detected, typically at concentrations higher than their metabolites. The Maple Creek site is influenced by focused recharge, macropore flow, and variable soil-moisture retention properties in soils that transition from loess to sand.

Electromagnetic induction of foam-based nanoscale zerovalent iron (NZVI) particles to thermally enhance non-aqueous phase liquid (NAPL) volatilization in unsaturated porous media: Proof of concept.

PubMed

Srirattana, Supawan; Piaowan, Kitsanateen; Lowry, Gregory V; Phenrat, Tanapon

2017-09-01

Nanoscale zerovalent iron (NZVI) is a promising remediation agent for volatile organic compound (VOC) contamination in saturated sub-surfaces, but is rarely applied to the vadose zone as there are not enough water molecules in the unsaturated zone to participate in reductive dechlorination. In this study, we evaluated the possibility of using foam as a carrying vehicle to emplace NZVI in unsaturated porous media followed by the application of low frequency-electromagnetic field (LF-EMF) to enhance VOC volatilization in laboratory batch reactors. We found that the optimal condition for generating foam-based NZVI (F-NZVI) was using sodium lauryl ether sulfate (SLES) at a concentration of 3% (w/w) and a N 2 flow rate of 500 mL/min. Also, F-NZVI could carry as much as 41.31 g/L of NZVI in the liquid phase of the foam and generate heat to raise ΔT to 77 °C in 15 min under an applied LF-EMF (150 kHz and 13 A). Under these conditions, F-NZVI together with LF-EMF enhanced trichloroethylene (TCE) volatilization from TCE-dense non-aqueous phase liquid (DNAPL) in unsaturated sand by 39.51 ± 6.59-fold compared to reactors without LF-EMF application. This suggested that using F-NZVI together with LF-EMF could theoretically be an alternative to radio frequency heating (RFH) as it requires a much lower irradiation frequency (336-fold lower), which should result in significantly lower capital and operational costs compared to RFH. Copyright © 2017 Elsevier Ltd. All rights reserved.

Controls on atrazine leaching through a soil-unsaturated fractured limestone sequence at Brévilles, France.

PubMed

Roulier, Stéphanie; Baran, Nicole; Mouvet, Christophe; Stenemo, Fredrik; Morvan, Xavier; Albrechtsen, Hans-Jørgen; Clausen, Liselotte; Jarvis, Nicholas

2006-03-01

The objective of this study was to identify the main controls on atrazine leaching through luvisols and calcisols overlying fissured limestone using the dual-permeability model MACRO. The model parameterisation was based on a combination of direct measurements (e.g. hydraulic properties, adsorption and degradation), literature data and calibration against bromide leaching experiments in field plots. A Monte Carlo sensitivity analysis was carried out for a typical application pattern, considering two different depths of unsaturated limestone (15 and 30 m). MACRO calibrations to the field experiments demonstrated the occurrence of strong macropore flow in the luvisol, while transport in the calcisol could be described by the advection-dispersion equation. MACRO simulations of tritium and atrazine leaching qualitatively matched tritium concentration profiles measured in the limestone and atrazine concentrations measured in piezometers and in aquifer discharge via a spring. The sensitivity analysis suggested that the thickness of the limestone, as well as the transport properties and processes occurring in the unsaturated rock (e.g. matrix vs. fissure flow) will have little significant long-term effect on atrazine leaching, mainly because degradation is very slow in the limestone. No mineralization of atrazine was detected in one-year incubations and a mean half-life of 10 years was assumed in the simulations. Instead, processes occurring in the soil exerted the main control on predicted atrazine leaching, especially variations in the degradation rate and the strength of sorption and macropore flow. However, fissure flow in unsaturated rock is expected to exert a much more significant control on groundwater contamination for compounds that degrade more readily in the deep vadose zone.

Crystal structure of 4,5-dinitro-1 H-imidazole

DOE PAGES

Windler, G. Kenneth; Scott, Brian L.; Tomson, Neil C.; ...

2015-01-01

Here, the title compound, C 3H 2N 4O 4, forms crystals with two molecules in the asymmetric unit which are conformationally similar. With the exception of the O atoms of the nitro groups, the molecules are essentially planar. In the crystal, adjacent molecules are associated by N—H...N hydrogen bonds involving the imidazole N—H donors and N-atom acceptors of the unsaturated nitrogen of neighboring rings, forming layers parallel to (010).

[The remove characteristics of dissolved organic matter in landfill leachate during the treatment process].

PubMed

He, Xiao-Song; Yu, Jing; Xi, Bei-Dou; Jiang, Yong-Hai; Zhang, Jin-Bao; Li, Dan; Pan, Hong-Wei; Liu, Hong-Liang

2012-09-01

In order to investigate remove characteristics of dissolved organic matter in landfill leachate, leachates were sampled during the process (i. e. , adjusting tank, anaerobic zone, oxidation ditch and MBR processing). Dissolved organic matter was extracted and its content and structure were characterized by fluorescence excitation-emission matrix spectra, UV-Vis specrtra and FTIR spectra. The results showed that an amount of 377.6 mg x L(-1) dissolved organic carbon (DOC) was removed during the whole treatment process, and the total removal rate was up to 78.34%. The 25.56% of DOC in the adjusting tank was removed during the anaerobic zone, 41.58% of DOC in anaerobic effluent was removed during the oxidation ditch, while 50.19% of DOC in the oxidation ditch effluent decreased in the MBR process. The anaerobic process increased the content of unsaturated compound and polysaccharides in leachate DOM, which improved the leachate biochemical characteristics. The unsaturated compound and polysaccharides were removed effectively during being in oxidation ditch. Protein-like and humic-like fluorescence peaks were observed in the adjusting tank and anaerobic zone, while humic-like fluorescence peaks were just presented in the oxidation ditch and MBR processing. Protein-like and fulvic-like substances were biodegraded in the adjusting tank and anaerobic zone, while humic-like materials were removed in the MBR process.

Using Metal Complex Ion-Molecule Reactions in a Miniature Rectilinear Ion Trap Mass Spectrometer to Detect Chemical Warfare Agents

NASA Astrophysics Data System (ADS)

Graichen, Adam M.; Vachet, Richard W.

2013-06-01

The gas-phase reactions of a series of coordinatively unsaturated [Ni(L)n]y+ complexes, where L is a nitrogen-containing ligand, with chemical warfare agent (CWA) simulants in a miniature rectilinear ion trap mass spectrometer were investigated as part of a new approach to detect CWAs. Results show that upon entering the vacuum system via a poly(dimethylsiloxane) (PDMS) membrane introduction, low concentrations of several CWA simulants, including dipropyl sulfide (simulant for mustard gas), acetonitrile (simulant for the nerve agent tabun), and diethyl phosphite (simulant for nerve agents sarin, soman, tabun, and VX), can react with metal complex ions generated by electrospray ionization (ESI), thereby providing a sensitive means of detecting these compounds. The [Ni(L)n]2+ complexes are found to be particularly reactive with the simulants of mustard gas and tabun, allowing their detection at low parts-per-billion (ppb) levels. These detection limits are well below reported exposure limits for these CWAs, which indicates the applicability of this new approach, and are about two orders of magnitude lower than electron ionization detection limits on the same mass spectrometer. The use of coordinatively unsaturated metal complexes as reagent ions offers the possibility of further tuning the ion-molecule chemistry so that desired compounds can be detected selectively or at even lower concentrations.

A review of characterization of tocotrienols from plant oils and foods.

PubMed

Ahsan, Haseeb; Ahad, Amjid; Siddiqui, Waseem A

2015-04-01

Tocotrienols, members of the vitamin E family, are natural compounds found in a number of vegetable oils, wheat germ, barley and certain types of nuts and grains. Vegetable oils provide the best sources of these vitamin E forms, particularly palm oil and rice bran oil contain higher amounts of tocotrienols. Other sources of tocotrienols include grape fruit seed oil, oats, hazelnuts, maize, olive oil, buckthorn berry, rye, flax seed oil, poppy seed oil and sunflower oil. Tocotrienols are of four types, viz. alpha (α), beta (β), gamma (γ) and delta (δ). Unlike tocopherols, tocotrienols are unsaturated and possess an isoprenoid side chain. A number of researchers have developed methods for the extraction, analysis, identification and quantification of different types of vitamin E compounds. This article constitutes an in-depth review of the chemistry and extraction of the unsaturated vitamin E derivatives, tocotrienols, from various sources using different methods. This review article lists the different techniques that are used in the characterization and purification of tocotrienols such as soxhlet and solid-liquid extractions, saponification method, chromatography (thin layer, column chromatography, gas chromatography, supercritical fluid, high performance), capillary electrochromatography and mass spectrometry. Some of the methods described were able to identify one form or type while others could analyse all the analogues of tocotrienol molecules. Hence, this article will be helpful in understanding the various methods used in the characterization of this lesser known vitamin E variant.

Coronal Current Sheet Evolution in the Aftermath of a CME

NASA Technical Reports Server (NTRS)

Bemporad, A.; Poletto, G.; Suess, S. T.; Ko, Y.-K.; Schwadron, N. A.; Elliott, H. A.; Raymond, J. C.

2005-01-01

We report on SOHO-UVCS observations of coronal restructuring following a Coronal Mass Ejection (CME) on November 26, 2002, at the time of a SOHO-Ulysses quadrature campaign. Starting about 3 hours after the CME, which was directed towards Ulysses, UVCS began taking spectra at 1.7 solar radii, covering emission from both cool and hot plasma. Observations continued, with occasional gaps, for more than 2 days. Emission in the 974.8 Angstrom line of [Fe XVIII], indicating temperatures above 6x10(6) K, was observed throughout the campaign in a spatially limited location. Comparison with EIT images shows the [Fe XVIII] emission to overlie a growing post-flare loop system formed in the aftermath of the CME. The emission most likely originates in a current sheet overlying the arcade. Analysis of the [Fe XVIII] emission allows us to infer the evolution of physical parameters in the current sheet over the entire span of our observations: in particular, we give the temperature vs. time in the current sheet and estimate the density. Ulysses was directly above the location of the CME and intercepted the ejecta. High ionization state Fe was detected by SWICS throughout the magnetic cloud associated with the CME, although the rapid temporal variation suggests bursty, rather than smooth, reconnection in the coronal current sheet. Both the remote and in situ observations are compared with predictions of theoretical CME models.

Current Sheet Evolution in the Aftermath of a CME Event

NASA Technical Reports Server (NTRS)

Bemporad, A.; Poletto, G.; Suess, S. T.; Ko, Y.-K.; Schwadron, N. A.; Elliott, H. A.; Raymond, J. C.

2005-01-01

We report on SOHO-UVCS observations of the coronal restructuring following a Coronal Mass Ejection (CME) on November 26,2002, at the time of a SOHO-Ulysses quadrature campaign. Starting about 3 hours after a CME in the NW quadrant, UVCS began taking spectra at 1.7 solar radius, covering emission from both cool and hot plasma. Observations continued, with occasional gaps, for more than 2 days. Emission in the 974.8 Angstrom line of [Fe XVIII], indicating temperatures above 6 x 10(exp 6) K, was observed throughout the campaign in a spatially limited location. Comparison with EIT images shows the Fe XVIII emission to overlie a growing post-flare loop system formed in the aftermath of the CME. The emission most likely originates in a current sheet overlying the arcade. Analysis of the [Fe XVIII] emission allows us to infer the evolution of physical parameters in the current sheet over the entire span of our observations: in particular, we give the temperature vs. time in the current sheet and estimate the density. At the time of the quadrature, Ulysses was directly above the location of the CME and intercepted the ejecta. High ionization state Fe was detected by Ulysses-SWICS throughout the magnetic cloud associated with the CME. Both the remote and in situ observations are compared with predictions of theoretical CME models.

Identification of fused 16β,17β-oxazinone-estradiol derivatives as a new family of non-estrogenic 17β-hydroxysteroid dehydrogenase type 1 inhibitors.

PubMed

Maltais, René; Trottier, Alexandre; Delhomme, Audrey; Barbeau, Xavier; Lagüe, Patrick; Poirier, Donald

2015-03-26

A new family of cyclic carbamate-estradiol derivatives has been designed to remove the intrinsic estrogenic activity of a parent acyclic compound reported as a potent inhibitor of 17β-hydroxysteroid dehydrogenase type 1 (17β-HSD1). The synthesis of two series of fused 16β,17β-oxazinone-estradiol derivatives, saturated compounds 7a-d and unsaturated compounds 10a-d, led to the identification of 10b, a 17β-HSD1 inhibitor (IC50 = 1.4 μM) without estrogenic activity in estrogen-sensitive T-47D cells. Interestingly, this compound was found selective over 17β-HSD2 and 17β-HSD12. A computational analysis of inhibitors into 17β-HSD1 by molecular docking also revealed interesting structure-activity relationships that could be helpful in the design of new generation of 16β,17β-oxazinone-estradiol analogs. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

PHT3D-UZF: A reactive transport model for variably-saturated porous media

USGS Publications Warehouse

Wu, Ming Zhi; Post, Vincent E. A.; Salmon, S. Ursula; Morway, Eric D.; Prommer, H.

2016-01-01

A modified version of the MODFLOW/MT3DMS-based reactive transport model PHT3D was developed to extend current reactive transport capabilities to the variably-saturated component of the subsurface system and incorporate diffusive reactive transport of gaseous species. Referred to as PHT3D-UZF, this code incorporates flux terms calculated by MODFLOW's unsaturated-zone flow (UZF1) package. A volume-averaged approach similar to the method used in UZF-MT3DMS was adopted. The PHREEQC-based computation of chemical processes within PHT3D-UZF in combination with the analytical solution method of UZF1 allows for comprehensive reactive transport investigations (i.e., biogeochemical transformations) that jointly involve saturated and unsaturated zone processes. Intended for regional-scale applications, UZF1 simulates downward-only flux within the unsaturated zone. The model was tested by comparing simulation results with those of existing numerical models. The comparison was performed for several benchmark problems that cover a range of important hydrological and reactive transport processes. A 2D simulation scenario was defined to illustrate the geochemical evolution following dewatering in a sandy acid sulfate soil environment. Other potential applications include the simulation of biogeochemical processes in variably-saturated systems that track the transport and fate of agricultural pollutants, nutrients, natural and xenobiotic organic compounds and micropollutants such as pharmaceuticals, as well as the evolution of isotope patterns.

Free and glycosidically bound volatile compounds in sun-dried raisins made from different fragrance intensities grape varieties using a validated HS-SPME with GC-MS method.

PubMed

Wang, Dong; Duan, Chang-Qing; Shi, Ying; Zhu, Bao-Qing; Javed, Hafiz Umer; Wang, Jun

2017-08-01

The conditions of sample pretreatments and HS-SPME for extracting volatile compounds from raisins were optimized, and the method was validated in the study. Free and glycosidically bound volatile compounds in three different fragrance intensities raisins were analysed using this method. There were 91 compounds identified, and 72, 26 and 8 of these compounds came from fresh grapes, the auto-oxidation of unsaturated fatty acids (UFAO) and the Maillard reaction, respectively. The aroma profiles of Thompson Seedless raisins (TSRs) and Centennial Seedless raisins (CSRs) were similar, while the floral, fruity, green and roasted aromas of CSRs were higher than those of TSRs due to the contributions of benzeneacetaldehyde, 2-pentylfuran, (E)-2-nonenal and 3-ethyl-2,5-dimethyl pyrazine. Decanal, rose oxide, geraniol, linalool and β-damascenone made the floral and fruity aromas of Zixiang Seedless raisins (ZSRs) greater than those in TSRs and CSRs, but the green and roasted aroma intensities of ZSRs were lower. Copyright © 2017 Elsevier Ltd. All rights reserved.

Synthesis and mechanistic studies of curcumin analog-based oximes as potential anticancer agents.

PubMed

Qin, Hua-Li; Leng, Jing; Youssif, Bahaa G M; Amjad, Muhammad Wahab; Raja, Maria Abdul Ghafoor; Hussain, Muhammad Ajaz; Hussain, Zahid; Kazmi, Syeda Naveed; Bukhari, Syed Nasir Abbas

2017-09-01

The incidence of cancer can be decreased by chemoprevention using either natural or synthetic agents. Apart from synthetic compounds, numerous natural products have exhibited promising potential to inhibit carcinogenesis in vivo. In this study, α, β-unsaturated carbonyl-based anticancer compounds were used as starting materials to synthesize new oxime analogs. The findings from the antiproliferative assay using seven different human cancer cell lines provided a clear picture of structure-activity relationship. The oxime analogs namely 7a and 8a showed strong antiproliferative activity against the cell lines. The mechanistic effects of compounds on EGFR-TK kinases and tubulin polymerization and BRAF V 600E were investigated. In addition, the efficacy of compounds in reversing the efflux-mediated resistance developed by cancer cells was also studied. The compounds 5a and 6a displayed potent activity on various targets such as BRAF V 600E and EGFR-TK kinases and also exhibited strong antiproliferative activity against different cell lines hence showing potential of multifunctional anticancer agents. © 2017 John Wiley & Sons A/S.

Pattern of dental development in Hominid XVIII from the Middle Pleistocene Atapuerca-Sima de los Huesos site (Spain).

PubMed

Bermudez De Castro, J M; Rosas, A

2001-04-01

. We describe the pattern of dental development of Hominid XVIII from the Middle Pleistocene Sima de los Huesos (SH) site of the Sierra de Atapuerca (Burgos, Spain). As expected, this pattern is similar to that of modern humans. A delay of development of the lower and upper canines was observed. In contrast, the relative advanced development of the lower second molars and, especially, the upper and lower third molars is noteworthy. This latter feature seems to be common in Pleistocene hominids, and suggests that the pattern of dental development evolved in the genus Homo during the Pleistocene. In European Middle Pleistocene hominids, this pattern probably was facilitated by the extra space available in the mandible and maxilla for developing teeth. Copyright 2001 Wiley-Liss, Inc.

[The becoming of public medicine in the second half of XVIII-first half of XIX centuries. Report II. The development of public systems of training of medical manpower and charity provision to socially unprotected groups of population].

PubMed

Stochik, A M; Zatravkin, S N; Stochik, A A

2013-01-01

The present report considers the history of becoming of concept of medical police in second half of XVIII century. This concept became one of the most important instruments of public management in Austria, France, Prussia and Russia. Two directions of activity of public authorities in the area of implementation of medical police are discussed i.e. control of frauds and development of public systems of training of medical manpower and charity provision to socially unprotected groups of population. The historiographical data is presented concerning the development of public systems of training of medical manpower, reform of university medical education, implementation of hospital reform.

Derivation of ionization balance for calcium XVIII/XIX using XRP solar X-ray data

NASA Astrophysics Data System (ADS)

Antonucci, E.; Gabriel, A. H.; Doyle, J. G.; Dubau, J.; Faucher, P.; Jordan, C.; Veck, N.

1984-04-01

Spectra of calcium from solar flares are used in an attempt to derive an ionization balance for Ca XVIII/Ca XIX. The isothermal assumption inherent in this derivation is shown not to introduce errors, by modelling a number of hypothetical nonisothermal plasmas. The unresolved blend of calcium and argon lines prevents a definitive determination of the results, owing to uncertainties in the ratio of abundances of these elements. The resulting ionization balance curves are presented as a function of the solar argon/calcium abundance ratio. The theoretical ionization balance of Doyle and Raymond is consistent with the data. To within the expected accuracy of the atomic theories, there is no reason to assume that the flare plasma is other than close to steady-state ionization balance.

Isosorbide as the structural component of bio-based unsaturated polyesters for use as thermosetting resins.

PubMed

Sadler, Joshua M; Toulan, Faye R; Nguyen, Anh-Phuong T; Kayea, Ronald V; Ziaee, Saeed; Palmese, Giuseppe R; La Scala, John J

2014-01-16

In recent years, the development of renewable bio-based resins has gained interest as potential replacements for petroleum based resins. Modified carbohydrate-based derivatives have favorable structural features such as fused bicyclic rings that offer promising candidates for the development of novel renewable polymers with improved thermomechanical properties when compared to early bio-based resins. Isosorbide is one such compound and has been utilized as the stiffness component for the synthesis of novel unsaturated polyesters (UPE) resins. Resin blends of BioUPE systems with styrene were shown to possess viscosities (120-2200 cP) amenable to a variety of liquid molding techniques, and after cure had Tgs (53-107 °C) and storage moduli (430-1650 MPa) that are in the desired range for composite materials. These investigations show that BioUPEs containing isosorbide can be tailored during synthesis of the prepolymer to meet the needs of different property profiles. Copyright © 2013 Elsevier Ltd. All rights reserved.

Enantioselective chromatography in analysis of triacylglycerols common in edible fats and oils.

PubMed

Kalpio, Marika; Nylund, Matts; Linderborg, Kaisa M; Yang, Baoru; Kristinsson, Björn; Haraldsson, Gudmundur G; Kallio, Heikki

2015-04-01

Enantiomers of racemic triacylglycerol (TAG) mixtures were separated using two chiral HPLC columns with a sample recycling system and a UV detector. A closed system without sample derivatisation enabled separation and identification by using enantiopure reference compounds of eleven racemic TAGs with C12-C22 fatty acids with 0-2 double bonds. The prolonged separation time was compensated for by fewer pretreatment steps. Presence of one saturated and one unsaturated fatty acid in the asymmetric TAG favoured the separation. Enantiomeric resolution, at the same time with stronger retention of TAGs, increased with increasing fatty acid chain length in the sn-1(3) position. Triunsaturated TAGs containing oleic, linoleic or palmitoleic acids did not separate. The elution order of enantiomers was determined by chemoenzymatically synthesised enantiopure TAGs with a co-injection method. The method is applicable to many natural fats and oils of low unsaturation level assisting advanced investigation of lipid synthesis and metabolism. Copyright © 2014 Elsevier Ltd. All rights reserved.

Oxygen and the evolution of metabolic pathways

NASA Technical Reports Server (NTRS)

Jahnke, L. L.

1986-01-01

While a considerable amount of evidence has been accumulated about the history of oxygen on this planet, little is known about the relative amounts to which primitive cells might have been exposed. One clue may be found in the metabolic pathways of extant microorganisms. While eucaryotes are principally aerobic organisms, a number are capable of anaerobic growth by fermentation. One such eucaryotic microorganism, Saccharomyces cerevisiae, will grow in the complete absence of oxygen when supplemented with unsaturated fatty acid and sterol. Oxygen-requiring enzymes are involved in the synthesis of both of these compounds. Studies have demonstrated that the oxidative desaturation of palmitic acid and the conversion of squalene to sterols occur in the range of 10-(3) to 10(-2) PAL. Thus, if the oxygen requirements of these enzymatic processes are an indication, eucaryotes might be more primitive than anticipated from the microfossil record. Results of studies on the oxygen requirements for sterol and unsaturated fatty acid synthesis in a more primitive procaryotic system are also discussed.

Covalent Modifiers: A Chemical Perspective on the Reactivity of α,β-Unsaturated Carbonyls with Thiols via Hetero-Michael Addition Reactions

PubMed Central

Jackson, Paul A.; Widen, John C.; Harki, Daniel A.; Brummond, Kay M.

2017-01-01

Although Michael acceptors display a potent and broad spectrum of bioactivity, they have largely been ignored in drug discovery because of their presumed indiscriminate reactivity. As such, a dearth of information exists relevant to the thiol reactivity of natural products and their analogs possessing this moiety. In the midst of recently approved acrylamide-containing drugs, it is clear that a good understanding of the hetero-Michael addition reaction and the relative reactivities of biological thiols with Michael acceptors under physiological conditions is needed for the design and use of these compounds as biological tools and potential therapeutics. This perspective provides information that will contribute to this understanding, such as kinetics of thiol addition reactions, bioactivities, as well as steric and electronic factors that influence the electrophilicity and reversibility of Michael acceptors. This perspective is focused on α,β-unsaturated carbonyls given their preponderance in bioactive natural products. PMID:27996267

Catchment scale molecular composition of hydrologically mobilized dissolved organic matter

NASA Astrophysics Data System (ADS)

Raeke, Julia; Lechtenfeld, Oliver J.; Oosterwoud, Marieke R.; Bornmann, Katrin; Tittel, Jörg; Reemtsma, Thorsten

2016-04-01

Increasing concentrations of dissolved organic matter (DOM) in rivers of temperate catchments in Europe and North Amerika impose new technical challenges for drinking water production. The driving factors for this decadal increase in DOM concentration are not conclusive and changes in annual temperatures, precipitation and atmospheric deposition are intensely discussed. It is known that the majority of DOM is released by few but large hydrologic events, mobilizing DOM from riparian wetlands for export by rivers and streams. The mechanisms of this mobilization and the resulting molecular composition of the released DOM may be used to infer long-term changes in the biogeochemistry of the respective catchment. Event-based samples collected over two years from streams in three temperate catchments in the German mid-range mountains were analyzed after solid-phase extraction of DOM for their molecular composition by ultra-high resolution mass spectrometry (FT-ICR MS). Hydrologic conditions, land use and water chemistry parameters were used to complement the molecular analysis. The molecular composition of the riverine DOM was strongly dependent on the magnitude of the hydrologic events, with unsaturated, oxygen-enriched compounds being preferentially mobilized by large events. This pattern is consistent with an increase in dissolved iron and aluminum concentrations. In contrast, the relative proportions of nitrogen and sulfur bearing compounds increased with an increased agricultural land use but were less affected by the mobilization events. Co-precipitation experiments with colloidal aluminum showed that unsaturated and oxygen-rich compounds are preferentially removed from the dissolved phase. The precipitated compounds thus had similar chemical characteristics as compared to the mobilized DOM from heavy rain events. Radiocarbon analyses also indicated that this precipitated fraction of DOM was of comparably young radiocarbon age. DOM radiocarbon from field samples showed that also the event-mobilized DOM had higher radiocarbon content. Overall, hydrology not only controls the quantity of exported carbon from temperate catchments but also strongly influences the molecular composition by mobilizing distinct compound classes in conjunction with dissolved iron and aluminum. From these results future compositional changes in temperate river DOM can be assessed, given an expected increase in the magnitude of hydrologic events, and technical advice for drinking water production may be inferred.

Reversible Dehydration Behavior Reveals Coordinatively Unsaturated Metal Sites in Microporous Aluminum Phosphonates

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

Kinnibrugh, Tiffany L.; Bakhmutov, Vladimir I.; Clearfield, Abraham

2014-10-01

Incorporation of the same ligand into three different aluminum phenylenediphosphonates (Al(H 2O)(O 3PC 6H 4PO 3H) (1), Al-4(H 2O)(2)(O 3PC 6H 4PO 3)(3) (2), and Al-4(H 2O)(4)(O 3PC 6H 4PO 3)(2.84)(OH)(0.64) (3)) was accomplished by varying the synthetic conditions. The compounds have different sorption properties; however, all exhibit reversible dehydration behavior. The structures of the hydrated and dehydrated phases were determined from powder X-ray diffraction data. Compounds 2 and 3 were found to be microporous, while compound 1 was found to be nonporous. The stability of the dehydrated phase and the resulting porosity was found to be influenced by themore » change in the structure upon loss of water.« less

Halogenated fatty amides - A brand new class of disinfection by-products.

PubMed

Kosyakov, Dmitry S; Ul'yanovskii, Nikolay V; Popov, Mark S; Latkin, Tomas B; Lebedev, Albert T

2017-12-15

An array of similar halogenated nitrogen-containing compounds with elemental composition C n H 2n NO 2 X, C n H 2n-2 NO 2 X and C n H 2n-1 NOX 2 (X = Cl, Br; n = 16, 18, 22) was detected in drinking water with high performance liquid chromatography - high resolution mass spectrometry (HPLC-HRMS) method. Compounds of this type were never mentioned among disinfection by-products. Tandem mass spectrometry allowed referring them to halohydrines or dihalogenated fatty amides, the products of conjugated electrophilic addition of halogens to the double bonds of unsaturated fatty amides. The proposed structures were confirmed by conducting aqueous chlorination with standard solution of oleamide. These compounds may be considered as a brand new class of disinfection by products, while their toxicities require special study. Copyright © 2017 Elsevier Ltd. All rights reserved.

Platinum(II) acetate complexes in hydrogenation of unsaturated compounds

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

Berenblyum, A.S.; Goranskaya, T.P.; Mund, S.L.

1979-12-20

In order to further elucidate the effect of the ligand environment in the complexes of group VIII metals on the activity of H/sub 2/, the catalytic properties of Pt(II) compounds with oxygen-containing acido ligands was studied. The platinum(II) acetate complexes with aniline and triphenylphosphine were synthesized. IR spectral studies indicated that platinum(II) acetate formed complexes with either of the other compounds singly or together. Dimethylformamide(DMF) solutions of platinum acetate and its complexes with aniline and/or triphenylphosphine all absorb H/sub 2/ in the temperature range of 20 to 90/sup 0/C and at a H/sub 2/ pressure of 1 atm. After themore » absorption of H/sub 2/, the DMF solutions of (aniline)(triphenylphosphine)platinum(II)diacetate complex were found to catalyze the hydrogenaton of O/sub 2/ and 1,3-pentadiene.« less

Antifouling potential of the marine microalga Dunaliella salina.

PubMed

Gao, Min; Li, Fengchao; Su, Rongguo; Wang, Ke; Li, Xuzhao; Lu, Wei

2014-11-01

Marine organisms have usually been viewed as sources of environmentally friendly compounds with antifouling activity. We performed a series of operations to investigate the antifouling potential of the marine microalga Dunaliella salina. For the ethyl acetate crude extract, the antialgal activity was significant, and the EC50 value against Skeletonema costatum was 58.9 μg ml(-1). The isolated purified extract was tested for antifouling activity, the EC 50 value against S. costatum was 21.2 μg ml(-1), and the LC50 against Balanus amphitrite larvae was 18.8 μg ml(-1). Subsequently, both UHR-TOF-MS and GC-MS were used for the structural elucidation of the compounds, and a series of unsaturated and saturated 16- and 18-carbon fatty acids were detected. The data suggested that the fatty acid extracts from D. salina possess high antifouling activity, and could be used as substitutes for potent, toxic antifouling compounds.

42 CFR 423.505 - Contract provisions.

Code of Federal Regulations, 2010 CFR

2010-10-01

...) Conducting evaluations of the overall Medicare program, including the interaction between prescription drug coverage under Part D of Title XVIII of the Social Security Act and the services and utilization under...

Synthetic routes to 3(5)-phosphonylated pyrazoles

NASA Astrophysics Data System (ADS)

Goulioukina, N. S.; Makukhin, N. N.; Beletskaya, I. P.

2016-07-01

This review comprehensively covers the currently available synthetic routes to 3(5)-phosphonylated pyrazoles. There are demonstrated significant advances in this field over the last 10-15 years caused by the use of the Bestmann-Ohira reagent [as well as (diazomethyl)phosphonates and phosphonylated hydrazonoyl halides] in reactions with diverse dipolarophiles. 1,3-Dipolar cycloaddition of diazo compounds to α,β-unsaturated phosphonates as well as intramolecular heterocyclization of (1-diazoallyl)phosphonates and (3--diazo-1-propenyl)phosphonates are discussed. Synthetic potential of cyclocondensation of organophosphorus 1,3-dielectrophilic compounds with hydrazines is shown. Ways to introduce a phosphonate group into the pyrazole ring are considered. Examples of chemical transformations of 3(5)-phosphonylated pyrazoles are reported. The bibliography includes 88 references.

Innovative applications of food-related emulsions.

PubMed

Kiokias, S; Varzakas, T

2017-10-13

Research on oxidative stability of multiple emulsions is very scarce. Given that this is a relevant topic that must be ascertained before the successful application of multiple emulsions in foods (especially when a combination of highly unsaturated oils is used as a lipid phase), this review mainly focuses on various aspects of the multiple emulsions. Fat replacement in meat products using emulsions is critically discussed along with innovative applications of natural antioxidants in food-based emulsions and multiple emulsions based on bioactive compounds/encapsulation as well as confectionery products.

Chemistry of rubber processing and disposal.

PubMed Central

Bebb, R L

1976-01-01

The major chemical changes during the processing of rubber occur with the breakdown in mastication and during vulcanization of the molded tire. There is little chemical change during the compounding, calendering, extrusion, and molding steps. Reclaiming is the process of converting scrap rubber into an unsaturated, processible product that can be vulcanized with sulfur. Pyrolysis of scrap rubber yields a complex mixture of liquids, gas, and residue in varying ratios dependent on the nature of the scrap and the conditions of pyrolysis. PMID:799964

Lipid oxidation in baked products: impact of formula and process on the generation of volatile compounds.

PubMed

Maire, Murielle; Rega, Barbara; Cuvelier, Marie-Elisabeth; Soto, Paola; Giampaoli, Pierre

2013-12-15

This paper investigates the effect of ingredients on the reactions occurring during the making of sponge cake and leading to the generation of volatile compounds related to flavour quality. To obtain systems sensitive to lipid oxidation (LO), a formulation design was applied varying the composition of fatty matter and eggs. Oxidation of polyunsaturated fatty acids (PUFA) and formation of related volatile compounds were followed at the different steps of cake-making. Optimised dynamic Solid Phase Micro Extraction was applied to selectively extract either volatile or semi-volatile compounds directly from the baking vapours. We show for the first time that in the case of alveolar baked products, lipid oxidation occurs very early during the step of dough preparation and to a minor extent during the baking process. The generation of lipid oxidation compounds depends on PUFA content and on the presence of endogenous antioxidants in the raw matter. Egg yolk seemed to play a double role on reactivity: protecting unsaturated lipids from oxidation and being necessary to generate a broad class of compounds of the Maillard reaction during baking and linked to the typical flavour of sponge cake. Copyright © 2013 Elsevier Ltd. All rights reserved.

Isolation of cholinesterase and β-secretase 1 inhibiting compounds from Lycopodiella cernua.

PubMed

Nguyen, Van Thu; To, Dao Cuong; Tran, Manh Hung; Oh, Sang Ho; Kim, Jeong Ah; Ali, Md Yousof; Woo, Mi-Hee; Choi, Jae Sue; Min, Byung Sun

2015-07-01

Three new serratene-type triterpenoids (1-3) and a new hydroxy unsaturated fatty acid (13) together with nine known compounds (4-12) were isolated from Lycopodiella cernua. The chemical structures were established using NMR, MS, and Mosher's method. Compound 13 showed the most potent inhibitory activity against acetylcholinesterase (AChE) with an IC50 value of 0.22μM. For butyrylcholinesterase (BChE) inhibitory activity, 5 showed the most potent activity with an IC50 value of 0.42μM. Compound 2 showed the most potent activity with an IC50 of 0.23μM for BACE-1 inhibitory activity. The kinetic activities were investigated to determine the type of enzyme inhibition involved. The types of AChE inhibition shown by compounds 4, 5, and 13 were mixed; BChE inhibition by 5 was competitive, while 2 and 6 showed mixed-types. In addition, molecular docking studies were performed to investigate the interaction of these compounds with the pocket sites of AChE. The docking results revealed that the tested inhibitors 3, 4, and 13 were stably present in several pocket domains of the AChE residue. Copyright © 2015 Elsevier Ltd. All rights reserved.

42 CFR 413.171 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-10-01

... individuals for the treatment of ESRD; (3) Other drugs and biologicals that are furnished to individuals for... XVIII of the Act (including drugs and biologicals with only an oral form), (4) Diagnostic laboratory...

42 CFR 413.171 - Definitions.

Code of Federal Regulations, 2011 CFR

2011-10-01

... individuals for the treatment of ESRD; (3) Other drugs and biologicals that are furnished to individuals for... XVIII of the Act (including drugs and biologicals with only an oral form), (4) Diagnostic laboratory...

Ultrasound-assisted synthesis of santalbic acid and a study of triacylglycerol species in Santalum album (Linn.) seed oil.

PubMed

Lie Ken Jie, M S; Pasha, M K; Ahmad, F

1996-10-01

Methyl ricinoleate (1) was treated with bromine and the dibromo derivative (2) was reacted with ethanolic KOH under ultrasonic irradiation to give 12-hydroxy-octadec-9-ynoic acid upon acidification with dil. HCI. The latter compound was methylated with BF3/methanol to give methyl 12-hydroxy-octadec-9-ynoate (3). Compound 3 was treated with methanesulfonyl chloride in the presence of triethylamine in CH2Cl2 to give methyl 12-mesyloxy-octadec-9-ynoate (4). Reaction of methyl 12-mesyloxy-octadec-9-ynoate with aqueous KOH under ultrasonic irradiation (20 kHz) gave (11E)-octadecen-9-ynoic acid (5, santalbic acid, 40%) and (11Z)-octadecen-9-ynoic acid (6, 60%) on acidification with dil. HCI. These isomers were separated by urea fractionation. The 13C nuclear magnetic resonance (NMR) spectroscopic properties of the methyl ester and the triacylglycerol (TAG) esters of these enynoic fatty acid isomers were studied. The carbon shifts of the unsaturated carbon nuclei of the methyl ester of the E-isomer were unambiguously assigned as 88.547 (C-9), 79.287 (C-10), 109.760 (C-11), and 143.450 (C-12) ppm, while the unsaturated carbon shifts of the (Z)-enynoate isomer appeared at 94.277 (C-9), 77.561 (C-10), 109.297 (C-11), and 142.668 (C-12) ppm. In the 13C NMR spectral analysis of the TAG molecules of type AAA containing either the (Z)- or (E)-enyne fatty acid, the C-1 to C-6 carbon atoms on the alpha- and beta-acyl positions were differentiated. The unsaturated carbon atoms in the alpha- and beta-acyl chains were also resolved into two signals except that of the C-11 olefinic carbon. Sandal (Santalum album) wood seed oil (a source of santalbic acid) was separated by silica chromatography into three fractions. The least polar fraction (7.2 wt%) contained TAG which had a random distribution of saturated and unsaturated fatty acids, of which oleic acid (69%) was the predominant component. The second fraction (3.8 wt%) contained santalbic acid (58%) and oleic acid (28%) together with some other normal fatty acids. Santalbic acid in this fraction was found in both the alpha- and beta-acyl positions of the glycerol "backbone." The most polar fraction (89 wt%) consisted of TAG containing santalbic acid only. The distribution of the various fatty acids on the glycerol "backbone" was supported by the results from the 13C NMR spectroscopic analysis.

42 CFR 486.303 - Requirements for certification.

Code of Federal Regulations, 2010 CFR

2010-10-01

..., including procedures to obtain payment for kidneys and non-renal organs provided to transplant hospitals. (d... XVIII for the procurement of kidneys. (e) Have been re-certified as an OPO under the Medicare program...

42 CFR 455.101 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-10-01

..., XVIII, or XX of the Act. This includes: (a) Any hospital, skilled nursing facility, home health agency... established under title V or title XX of the Act. Fiscal agent means a contractor that processes or pays...

19 CFR 122.183 - Denial of access.

Code of Federal Regulations, 2014 CFR

2014-04-01

...) Destruction of an aircraft or aircraft facility (18 U.S.C. 32); (xiii) Murder; (xiv) Assault with intent to murder; (xv) Espionage; (xvi) Sedition; (xvii) Kidnapping or hostage taking; (xviii) Treason; (xix) Rape...

19 CFR 122.183 - Denial of access.

Code of Federal Regulations, 2013 CFR

2013-04-01

...) Destruction of an aircraft or aircraft facility (18 U.S.C. 32); (xiii) Murder; (xiv) Assault with intent to murder; (xv) Espionage; (xvi) Sedition; (xvii) Kidnapping or hostage taking; (xviii) Treason; (xix) Rape...

Type XVIII collagen degradation products in acute lung injury

PubMed Central

Perkins, Gavin D; Nathani, Nazim; Richter, Alex G; Park, Daniel; Shyamsundar, Murali; Heljasvaara, Ritva; Pihlajaniemi, Taina; Manji, Mav; Tunnicliffe, W; McAuley, Danny; Gao, Fang; Thickett, David R

2009-01-01

Introduction In acute lung injury, repair of the damaged alveolar-capillary barrier is an essential part of recovery. Endostatin is a 20 to 28 kDa proteolytic fragment of the basement membrane collagen XVIII, which has been shown to inhibit angiogenesis via action on endothelial cells. We hypothesised that endostatin may have a role in inhibiting lung repair in patients with lung injury. The aims of the study were to determine if endostatin is elevated in the plasma/bronchoalveolar lavage fluid of patients with acute lung injury and ascertain whether the levels reflect the severity of injury and alveolar inflammation, and to assess if endostatin changes occur early after the injurious lung stimuli of one lung ventilation and lipopolysaccharide (LPS) challenge. Methods Endostatin was measured by ELISA and western blotting. Results Endostatin is elevated within the plasma and bronchoalveolar lavage fluid of patients with acute lung injury. Lavage endostatin reflected the degree of alveolar neutrophilia and the extent of the loss of protein selectivity of the alveolar-capillary barrier. Plasma levels of endostatin correlated with the severity of physiological derangement. Western blotting confirmed elevated type XVIII collagen precursor levels in the plasma and lavage and multiple endostatin-like fragments in the lavage of patients. One lung ventilation and LPS challenge rapidly induce increases in lung endostatin levels. Conclusions Endostatin may adversely affect both alveolar barrier endothelial and epithelial cells, so its presence within both the circulation and the lung may have a pathophysiological role in acute lung injury that warrants further evaluation. PMID:19358707

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

Tao, Shikang; Lu, Xiaohui; Levac, Nicole

Aerosol samples collected in the urban areas of Shanghai and Los Angeles were analyzed by nanospray-desorption electrospray ionization mass spectrometry (nano-DESI MS) with high mass resolution (m/Δm=100,000). Solvent mixtures of acetonitrile/water and acetonitrile/toluene were used to extract and ionize polar and non-polar compounds, respectively. A diverse mixture of oxygenated hydrocarbons, organosulfates, organonitrates, and organics with reduced nitrogen were detected in the Los Angeles sample. Majority of the organics in the Shanghai sample were detected as organosulfates. The dominant organosulfates in the two samples have distinctly different molecular characteristics. Specifically, organosulfates in the Los Angeles sample were dominated by isoprene- ormore » monoterpene-derived products, while organosulfates of yet unknown origin in the Shanghai sample had distinctive characteristics of long aliphatic carbon chains and low degree of oxidation and unsaturation. The use of acetonitrile/toluene solvent facilitated identification of this type of organosulfates, suggesting they could be missed in previous studies relying on sample extraction using common polar solvents. The high molecular weight and low degree of unsaturation and oxidization of the organosulfates detected in the Shanghai sample suggest that they may act as surfactants, and plausibly affect the surface tension and hygroscopicity of the atmospheric particulate matter. We propose that direct esterification of carbonyl or hydroxyl compounds by sulfates or sulfuric acid in liquid phase could be the formation pathway of these special organosulfates. Finally, long-chain alkanes from vehicle emissions might be their precursors.« less

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.

Degradation rates of CFC-11, CFC-12 and CFC-113 in anoxic shallow aquifers of Araihazar, Bangladesh.

PubMed

Horneman, A; Stute, M; Schlosser, P; Smethie, W; Santella, N; Ho, D T; Mailloux, B; Gorman, E; Zheng, Y; van Geen, A

2008-04-04

Chlorofluorocarbons CFC-11 (CCl(3)F), CFC-12 (CCl(2)F(2)), and CFC-113 (CCl(2)F-CClF(2)) are used in hydrology as transient tracers under the assumption of conservative behavior in the unsaturated and saturated soil zones. However, laboratory and field studies have shown that these compounds are not stable under anaerobic conditions. To determine the degradation rates of CFCs in a tropical environment, atmospheric air, unsaturated zone soil gas, and anoxic groundwater samples were collected in Araihazar upazila, Bangladesh. Observed CFC concentrations in both soil gas and groundwater were significantly below those expected from atmospheric levels. The CFC deficits in the unsaturated zone can be explained by gas exchange with groundwater undersaturated in CFCs. The CFC deficits observed in (3)H/(3)He dated groundwater were used to estimate degradation rates in the saturated zone. The results show that CFCs are degraded to the point where practically no (<5%) CFC-11, CFC-12, or CFC-113 remains in groundwater with (3)H/(3)He ages above 10 yr. In groundwater sampled at our site CFC-11 and CFC-12 appear to degrade at similar rates with estimated degradation rates ranging from approximately 0.25 yr(-1) to approximately 6 yr(-1). Degradation rates increased as a function of reducing conditions. This indicates that CFC dating of groundwater in regions of humid tropical climate has to be carried out with great caution.

Tri- and tetraterpenoid hydrocarbons in the Messel oil shale

NASA Technical Reports Server (NTRS)

Kimble, B. J.; Maxwell, J. R.; Philp, R. P.; Eglinton, G.; Albrecht, P.; Ensminger, A.; Arpino, P.; Ourisson, G.

1974-01-01

The high-molecular-weight constituents of the branched and cyclic hydrocarbon fraction of the Messel oil shale (Eocene) have been examined by high-resolution gas chromatography and combined gas chromatography/mass spectrometry. The following compounds are present: perhydrolycopene, together with one or more unsaturated analogs with the same skeleton; a series of 4-methylsteranes in higher abundance than their 4-desmethyl analogs; two series of pentacyclic triterpanes, one series based on the hopane structure, and the other based on the 17 alpha-H hopane structure; and an intact triterpene hop-17(21)-ene. Only two additional triterpanes were detected in minor concentrations - namely, 30-normoretane and a C31 triterpane based on the hopane/lupane-type skeleton. The presence of these compounds suggests a significant microbial contribution to the forming sediment.

[The composition of volatile components of cepe (Boletus edulis) and oyster mushrooms (Pleurotus ostreatus)].

PubMed

Misharina, T A; Mukhutdinova, S M; Zharikova, G G; Terenina, M B; Krikunova, N I

2009-01-01

The composition of aroma compounds in cooked and canned cepe (Boletus edulis) and in cooked oyster mushrooms (Pleurotus ostreatus) is studied using capillary gas chromatography and chromatography-mass spectrometry. It is found that unsaturated alcohols and ketones containing eight atoms of carbon determine the aroma of raw mushrooms and take part in the formation of the aroma of cooked mushrooms as well. The content of these compounds was the highest in canned cepes. In oyster mushrooms, the concentration of these alcohols and ketones was lower in comparison with cepes. The content of aliphatic and aromatic aldehydes was much higher in oyster mushrooms. Volatile aliphatic and heterocyclic Maillard reaction products and isomeric octenols and octenones formed the aroma of cooked and canned mushrooms.

Amonia gas: an improved reagent for chemical ionization mass spectrometry of bile acid methyl ester acetates

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

DeMark, B.R.; Klein, P.D.

1981-01-01

The ammonia chemical ionization mass spectra of 28 methyl ester acetate derivatives of bile acids and related compounds have been determined by gas-liquid chromatography-mass spectrometry. Advantages of ammonia ionization over the previously studied isobutane ionization include a 130 to 270% enhancement in the sensitivity of base peak monitoring, and direct determination of molecular weight from the base peak (M + NH/sub 4//sup +/) in the mass spectrum of any of the derivatives. Minor ions in the ammonia spectra also allow selective detection of 3-keto compounds and can indicate unsaturation or double bond conjugation in the molecule. The significance of thesemore » studies for the detection and quantitation of bile acids is discussed. 2 tables.« less

Electrophilic activation and cycloisomerization of enynes: a new route to functional cyclopropanes.

PubMed

Bruneau, Christian

2005-04-15

Transformations of enynes in the presence of transition-metal catalysts have played an important role in the preparation of a variety of cyclic compounds. Recent developments in the activation of triple carbon-carbon bonds by electrophilic metal centers have provided a new entry to the selective synthesis of cyclopropane derivatives from enynes. The mechanisms of these reactions involve catalytic species with both ionic and cyclopropylcarbenoid character. This type of activation will undoubtedly be further developed for application to other unsaturated hydrocarbons and inspire new catalytic cascade reaction sequences. This Minireview discusses the recent developments in electrophilic activation of enynes and shows that simple catalysts such as [Ru(3)(CO)(12)], PtCl(2), and cationic gold complexes are efficient precursors to promote the formation of functional polyclic compounds.

Synthesis and chemical reactions of the steroidal hormone 17α-methyltestosterone.

PubMed

El-Desoky, El-Sayed Ibrahim; Reyad, Mahmoud; Afsah, Elsayed Mohammed; Dawidar, Abdel-Aziz Mahmoud

2016-01-01

Structural modifications of natural products with complex structures like steroids require great synthetic effort. A review of literature is presented on the chemistry of the steroidal hormone 17α-methyltestosterone that is approved by Food and Drug Administration (FDA) in the United States as an androgen for estrogen-androgen hormone replacement therapy treatment. The analog also offers special possibilities for the prevention/treatment of hormone-sensitive cancers. The testosterone skeleton has important functionalities in the molecule that can act as a carbonyl component, an active methylene compound, α,β-unsaturated enone and tertiary hydroxyl group in various chemical reactions to access stereoisomeric steroidal compounds with potent activity. In addition, microbiological methods of synthesis and transformation of this hormone are presented. Copyright © 2015 Elsevier Inc. All rights reserved.

Recent progress in the synthesis of thiazolo[3,2-a]pyrimidine compounds

NASA Astrophysics Data System (ADS)

Wu, F. Y.; Luo, Y.; Hu, C. B.

2018-01-01

In this paper, the progress in the synthesis of thiazole[3,2-a]pyrimidine compounds in the field of medicine and pesticide were reviewed. The main synthetic routes include: (i) synthesis of thiazolo[3,2-a]pyrimidines, spiro thiazolo[3,2-a]pyrimidines and pyrazolo[3,4-d]thiazolo[3,2-a]pyrimidines by multicomponent reactions (MCRs). (ii) synthesis of thiazolo[3,2-a]pyrimidines by condensation of pyrimidine-2-thiones, which were obtained by Biginelli reaction between aromatic aldehydes and thiourea, with substituted 2-bromo-1-phenylethanone or chloroacetic acid. (iii) synthesis of pyridothieno-fused thiazolo[3,2-a]pyrimidinones via Pictet-Spengler reaction. (iv) synthesis of pyrido[4,3-d]thiazolo[3,2-a]pyrimidine by reacting 2-aminothiazole with the α, β-unsaturated ketones.

Further evaluation of long-chain alkenones as indicators of paleoceanographic conditions

NASA Astrophysics Data System (ADS)

Prahl, Fredrick G.; Muehlhausen, Laurel A.; Zahnle, Debra L.

1988-09-01

Cultures of the marine coccolithophorid, Emiliania huxleyi, were grown in the laboratory at five temperatures (8°, 10°, 15°, 20°, 25°C) and monitored by capillary gas chromatography for their long-chain, unsaturated lipid compositions. The long-chain lipids of this plant comprise a series of C 37, C 38 and C 39 di-, tri- and, in cells grown below 15°C, tetra-unsaturated methyl and ethyl ketones and a methyl and ethyl ester of a di-unsaturated C 36 fatty acid. Systematic changes in the degree of unsaturation and in the overall carbon chain length distribution of the alkenones and in the proportion of fatty acid esters relative to alkenones are noted as a function of growth temperature. We present temperature calibrations for these changes in the lipid composition of laboratory cultures and compare these results with the compositions of this biomarker series measured in a variety of sediments accumulating beneath warm (⩾25°C) and cold (⩽12°C) surface waters in the tropical and temperate North Pacific Ocean, respectively. The comparisons demonstrate 1) this series of biomarkers is deposited in these oceanic sediments with minimal evidence of alteration to its original composition and 2) the strain of E. huxleyi used in this laboratory calibration is representative of the "average" marine phytoplankton supplying this novel series of biomarkers to contemporary sediments in these two environments and a wide variety of other oceanic environments. The long-chain alkenones constitute a major component (8.0 ± 2.9%) of the total organic carbon content of living cells of E. huxleyi. The high cellular abundance of these compounds appears to be relatively constant and independent of the growth temperature of the plant. These biomarkers provide a well-designed and useful geochemical tool for assessing variations not only in surface water temperatures but potentially also in the productivity of an important group of marine phytoplankton in oceans of the recent and distant past.

Vinasse application to sugar cane fields. Effect on the unsaturated zone and groundwater at Valle del Cauca (Colombia).

PubMed

Ortegón, Gloria Páez; Arboleda, Fernando Muñoz; Candela, Lucila; Tamoh, Karim; Valdes-Abellan, Javier

2016-01-01

Extensive application of vinasse, a subproduct from sugar cane plantations for bioethanol production, is currently taking place as a source of nutrients that forms part of agricultural management in different agroclimatic regions. Liquid vinasse composition is characterised by high variability of organic compounds and major ions, acid pH (4.7), high TDS concentration (117,416-599,400mgL(-1)) and elevated EC (14,350-64,099μScm(-1)). A large-scale sugar cane field application is taking place in Valle del Cauca (Colombia), where monitoring of soil, unsaturated zone and the aquifer underneath has been made since 2006 to evaluate possible impacts on three experimental plots. For this assessment, monitoring wells and piezometers were installed to determine groundwater flow and water samples were collected for chemical analysis. In the unsaturated zone, tensiometers were installed at different depths to determine flow patterns, while suction lysimeters were used for water sample chemical determinations. The findings show that in the sandy loam plot (Hacienda Real), the unsaturated zone is characterised by low water retention, showing a high transport capacity, while the other two plots of silty composition presented temporal saturation due to La Niña event (2010-2011). The strong La Niña effect on aquifer recharge which would dilute the infiltrated water during the monitoring period and, on the other hand dissolution of possible precipitated salts bringing them back into solution may occur. A slight increase in the concentration of major ions was observed in groundwater (~5% of TDS), which can be attributed to a combination of factors: vinasse dilution produced by water input and hydrochemical processes along with nutrient removal produced by sugar cane uptake. This fact may make the aquifer vulnerable to contamination. Copyright © 2015 Elsevier B.V. All rights reserved.

Is fatty acid composition of human bone marrow significant to bone health?

PubMed

Pino, Ana María; Rodríguez, J Pablo

2017-12-16

The bone marrow adipose tissue (BMAT) is a conserved component of the marrow microenvironment, providing storage and release of energy and stabilizing the marrow extent. Also, it is recognized both the amount and quality of BMAT are relevant to preserve the functional relationships between BMAT, bone, and blood cell production. In this article we ponder the information supporting the tenet that the quality of BMAT is relevant to bone health. In the human adult the distribution of BMAT is heterogeneous over the entire skeleton, and both BMAT accumulation and bone loss come about with aging in healthy populations. But some pathological conditions which increase BMAT formation lead to bone impairment and fragility. Analysis in vivo of the relative content of saturated and unsaturated fatty acids (FA) in BMAT indicates site-related bone marrow fat composition and an association between increased unsaturation index (UI) and bone health. With aging some impairment ensues in the regulation of bone marrow cells and systemic signals leading to local chronic inflammation. Most of the bone loss diseases which evolve altered BMAT composition have as common factors aging and/or chronic inflammation. Both saturated and unsaturated FAs originate lipid species which are active mediators in the inflammation process. Increased free saturated FAs may lead to lipotoxicity of bone marrow cells. The pro-inflammatory, anti-inflammatory or resolving actions of compounds derived from long chain poly unsaturated FAs (PUFA) on bone cells is varied, and depending on the metabolism of the parent n:3 or n:6 PUFAs series. Taking together the evidence substantiate that marrow adipocyte function is fundamental for an efficient link between systemic and marrow fatty acids to accomplish specific energy or regulatory needs of skeletal and marrow cells. Further, they reveal marrow requirements of PUFAs. Copyright © 2017 Elsevier Inc. All rights reserved.

Molecular Mechanisms of Aldehyde Toxicity: A Chemical Perspective

PubMed Central

2015-01-01

Aldehydes are electrophilic compounds to which humans are pervasively exposed. Despite a significant health risk due to exposure, the mechanisms of aldehyde toxicity are poorly understood. This ambiguity is likely due to the structural diversity of aldehyde derivatives and corresponding differences in chemical reactions and biological targets. To gain mechanistic insight, we have used parameters based on the hard and soft, acids and bases (HSAB) theory to profile the different aldehyde subclasses with respect to electronic character (softness, hardness), electrophilic reactivity (electrophilic index), and biological nucleophilic targets. Our analyses indicate that short chain aldehydes and longer chain saturated alkanals are hard electrophiles that cause toxicity by forming adducts with hard biological nucleophiles, e.g., primary nitrogen groups on lysine residues. In contrast, α,β-unsaturated carbonyl derivatives, alkenals, and the α-oxoaldehydes are soft electrophiles that preferentially react with soft nucleophilic thiolate groups on cysteine residues. The aldehydes can therefore be grouped into subclasses according to common electronic characteristics (softness/hardness) and molecular mechanisms of toxicity. As we will discuss, the toxic potencies of these subgroups are generally related to corresponding electrophilicities. For some aldehydes, however, predictions of toxicity based on electrophilicity are less accurate due to inherent physicochemical variables that limit target accessibility, e.g., steric hindrance and solubility. The unsaturated aldehydes are also members of the conjugated type-2 alkene chemical class that includes α,β-unsaturated amide, ketone, and ester derivatives. Type-2 alkenes are electrophiles of varying softness and electrophilicity that share a common mechanism of toxicity. Therefore, exposure to an environmental mixture of unsaturated carbonyl derivatives could cause “type-2 alkene toxicity” through additive interactions. Finally, we propose that environmentally derived aldehydes can accelerate diseases by interacting with endogenous aldehydes generated during oxidative stress. This review provides a basis for understanding aldehyde mechanisms and environmental toxicity through the context of electronic structure, electrophilicity, and nucleophile target selectivity. PMID:24911545

Sesquiterpenes from Neurolaena lobata and their antiproliferative and anti-inflammatory activities.

PubMed

Lajter, Ildikó; Vasas, Andrea; Béni, Zoltán; Forgo, Peter; Binder, Markus; Bochkov, Valery; Zupkó, István; Krupitza, Georg; Frisch, Richard; Kopp, Brigitte; Hohmann, Judit

2014-03-28

Five new sesquiterpenes, neurolobatin A (1), neurolobatin B (2), 5β-hydroxy-8β-isovaleroyloxy-9α-hydroxycalyculatolide (3), 3-epi-desacetylisovaleroylheliangine (4), and 3β-acetoxy-8β-isovaleroyloxyreynosin (5), were isolated from the aerial parts of Neurolaena lobata. The structures were established by means of a combined spectroscopic data analysis, including ESIMS, APCI-MS, and 1D- and 2D-NMR techniques. Neurolobatin A (1) and B (2) are unusual isomeric seco-germacranolide sesquiterpenes with a bicyclic acetal moiety, compounds 3 and 4 are unsaturated epoxy-germacranolide esters, and compound 5 is the first eudesmanolide isolated from the genus Neurolaena. The isolated compounds (1-5) were shown to have noteworthy antiproliferative activities against human tumor cell lines (A2780, A431, HeLa, and MCF7). The anti-inflammatory effects of 1-5, evaluated in vitro using LPS- and TNF-α-induced IL-8 expression inhibitory assays, revealed that all these compounds strongly down-regulated the LPS-induced production of IL-8 protein, with neurolobatin B (2) and 3-epi-desacetylisovaleroylheliangine (4) being the most effective.

Sesquiterpenes from Neurolaena lobata and Their Antiproliferative and Anti-inflammatory Activities

PubMed Central

2014-01-01

Five new sesquiterpenes, neurolobatin A (1), neurolobatin B (2), 5β-hydroxy-8β-isovaleroyloxy-9α-hydroxycalyculatolide (3), 3-epi-desacetylisovaleroylheliangine (4), and 3β-acetoxy-8β-isovaleroyloxyreynosin (5), were isolated from the aerial parts of Neurolaena lobata. The structures were established by means of a combined spectroscopic data analysis, including ESIMS, APCI-MS, and 1D- and 2D-NMR techniques. Neurolobatin A (1) and B (2) are unusual isomeric seco-germacranolide sesquiterpenes with a bicyclic acetal moiety, compounds 3 and 4 are unsaturated epoxy-germacranolide esters, and compound 5 is the first eudesmanolide isolated from the genus Neurolaena. The isolated compounds (1–5) were shown to have noteworthy antiproliferative activities against human tumor cell lines (A2780, A431, HeLa, and MCF7). The anti-inflammatory effects of 1–5, evaluated in vitro using LPS- and TNF-α-induced IL-8 expression inhibitory assays, revealed that all these compounds strongly down-regulated the LPS-induced production of IL-8 protein, with neurolobatin B (2) and 3-epi-desacetylisovaleroylheliangine (4) being the most effective. PMID:24476550

Gum formation tendencies of olefinic structures in gasoline and synergistic effect of sulphur compounds

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

Nagpal, J.M.; Joshi, G.C.; Aswal, D.S.

1995-04-01

The high octane gasoline pool contains varying amounts of cracked naphthas as an important ingredient in formulating high octane lead free gasoline. The cracked naphthas are largely from Fluidized Catalytic Cracking (FCC) units and to lesser extend from thermal cracking units. While the role of olefinic unsaturation in gum formation during storage of gasoline has been extensively studied, there is little published work on contribution of individual olefin types in storage stability and gum formation tendency of gasoline containing these compound types. In the present work we report our results on storage stability and gum formation tendency of different olefinmore » types present in cracked naphthas through model compound matrix. It is found that cyclic olefins and cyclic diolefins are the most prolific gum formers. We have also studied the role of sulfur compounds present in the gasolines on gum formation tendency of olefins. While thiols enhance gum formation from all olefinic types, sulfides and disulfides interact depending on the structure of olefins. These can have either an accelerating, or inhibiting effect on gum formation.« less

Submerged Cultivation of Pleurotus sapidus with Molasses: Aroma Dilution Analyses by Means of Solid Phase Microextraction and Stir Bar Sorptive Extraction.

PubMed

Trapp, Tobias; Zajul, Martina; Ahlborn, Jenny; Stephan, Alexander; Zorn, Holger; Fraatz, Marco Alexander

2018-03-14

The basidiomycete Pleurotus sapidus (PSA) was grown in submerged cultures with molasses as substrate for the production of mycelium as a protein source for food applications. The volatilomes of the substrate, the submerged culture, and the mycelia were analyzed by gas chromatography-tandem mass spectrometry-olfactometry. For compound identification, aroma dilution analyses by means of headspace solid phase microextraction and stir bar sorptive extraction were performed via variation of the split vent flow rate. Among the most potent odorants formed by PSA were arylic compounds (e.g., p-anisaldehyde), unsaturated carbonyls (e.g., 1-octen-3-one, ( E)-2-octenal, ( E, E)-2,4-decadienal), and cyclic monoterpenoids (e.g., 3,9-epoxy- p-menth-1-ene, 3,6-dimethyl-3a,4,5,7a-tetrahydro-1-benzofuran-2(3 H)-one). Several compounds from the latter group were described for the first time in Pleurotus spp. After separation of the mycelia from the medium, the aroma compounds were mainly enriched in the culture supernatant. The sensory analysis of the mycelium correlated well with the instrumental results.

Unique distributions of hydrocarbons and sulphur compounds released by flash pyrolysis from the fossilised alga Gloeocapsomorpha prisca , a major constituent in one of four Ordovician kerogens

NASA Astrophysics Data System (ADS)

Douglas, A. G.; Damsté, J. S. Sinninghe; Fowler, M. G.; Eglinton, T. I.; de Leeuw, J. W.

1991-01-01

Kerogens isolated from four rocks of Ordovician age from North America have been analysed by combined pyrolysis-gas chromatography-mass spectrometry to compare and contrast the type and distribution of sulphur-containing compounds and aromatic and aliphatic hydrocarbons present in the pyrolysates. When pyrolysed, all of the kerogens released several series of heterocyclic sulphur compounds including alkylthiophenes, alkylthiolanes, alkylthianes and alkylbenzothiophenes together with n-alkanes, n-alklenes and alkylcyclohexanes as well as alkyl-substituted benzenes and naphthalenes. One of the kerogens, isolated from the Guttenberg oil rock, consisted predominantly of the alga Gloeocapsomorpha prisca, which produced sulphur compounds and hydrocarbons with fingerprint pyrograms that were different from those of the other three kerogens. The data provide prima facie evidence that these distributions may act as pseudo "biological markers" for this species of alga, namely that unsaturated kerogen moieties available for the uptake of sulphur, or which can cyclise to form hydrocarbons, distinguish Gloeocapsomorpha prisca from the contributing organisms of the other kerogens analysed.

Comprehension of direct extraction of hydrophilic antioxidants using vegetable oils by polar paradox theory and small angle X-ray scattering analysis.

PubMed

Li, Ying; Fabiano-Tixier, Anne Sylvie; Ruiz, Karine; Rossignol Castera, Anne; Bauduin, Pierre; Diat, Olivier; Chemat, Farid

2015-04-15

Since the polar paradox theory rationalised the fact that polar antioxidants are more effective in nonpolar media, extractions of phenolic compounds in vegetable oils were inspired and achieved in this study for obtaining oils enriched in phenolic compounds. Moreover, the influence of surfactants on the extractability of phenolic compounds was experimentally studied first, followed by the small angle X-ray scattering analysis for the oil structural observation before and after extraction so as to better understand the dissolving mechanism underpinning the extraction. The results showed a significant difference on the extraction yield of phenolic compounds among oils, which was mainly dependent on their composition instead of the unsaturation of fatty acids. Appropriate surfactant additions could significantly improve extraction yield for refined sunflower oils, which 1% w/w addition of glyceryl oleate was determined as the optimal. Besides, 5% w/w addition of lecithin performed the best in oil enrichments compared with mono- and di-glycerides. Copyright © 2014 Elsevier Ltd. All rights reserved.

Novel function of N,N-bis(2-chloroethyl)docos-13-enamide for reversal of multidrug resistance in tongue cancer.

PubMed

Qin, Qing; Ma, Peng-Fei; Kuang, Xiao-Cong; Gao, Ming-Xing; Mo, De-Huan; Xia, Shuang; Jin, Ning; Xia, Jun-Jie; Qi, Zhong-Quan; Lin, Cui-Wu

2013-12-05

Multidrug resistance (MDR) is a key element in the failure of chemotherapies, and development of agents to overcome MDR is crucial to improving cancer treatments. The overexpression of glutathione-S-transferases (GSTs) is one of the major mechanisms of MDR. Because some agents used in traditional Chinese medicine have strong antitumor effects coupled with low toxicity; we investigated the ability of N,N-bis(2-chloroethyl)docos-13-enamide (compound J), the synthesized analog of a highly unsaturated fatty acid from Isatis tinctoria L., to reverse the MDR induced by adriamycin (ADM) in TCA8113/ADM cells. We found that compound J significantly increased the cytotoxicity of ADM in TCA8113/ADM cells, with a reversal fold of 2.461. Analysis of the mechanisms through which compound J reversed MDR indicated that compound J significantly decreased the activity of GSTs and enhanced the depletion of GSH in TCA8113/ADM cells, but did not affect the P-glycoprotein (P-gp) efflux. Taken together, our data suggested that compound J was an excellent candidate for reversing MDR in cancer therapy. © 2013 Published by Elsevier B.V.

Reduction of chemical formulas from the isotopic peak distributions of high-resolution mass spectra.

PubMed

Roussis, Stilianos G; Proulx, Richard

2003-03-15

A method has been developed for the reduction of the chemical formulas of compounds in complex mixtures from the isotopic peak distributions of high-resolution mass spectra. The method is based on the principle that the observed isotopic peak distribution of a mixture of compounds is a linear combination of the isotopic peak distributions of the individual compounds in the mixture. All possible chemical formulas that meet specific criteria (e.g., type and number of atoms in structure, limits of unsaturation, etc.) are enumerated, and theoretical isotopic peak distributions are generated for each formula. The relative amount of each formula is obtained from the accurately measured isotopic peak distribution and the calculated isotopic peak distributions of all candidate formulas. The formulas of compounds in simple spectra, where peak components are fully resolved, are rapidly determined by direct comparison of the calculated and experimental isotopic peak distributions. The singular value decomposition linear algebra method is used to determine the contributions of compounds in complex spectra containing unresolved peak components. The principles of the approach and typical application examples are presented. The method is most useful for the characterization of complex spectra containing partially resolved peaks and structures with multiisotopic elements.

Tanshinones and diethyl blechnics with anti-inflammatory and anti-cancer activities from Salvia miltiorrhiza Bunge (Danshen)

NASA Astrophysics Data System (ADS)

Gao, Hongwei; Sun, Wen; Zhao, Jianping; Wu, Xiaxia; Lu, Jin-Jian; Chen, Xiuping; Xu, Qiong-Ming; Khan, Ikhlas A.; Yang, Shilin

2016-09-01

Four novel compounds (1-4) as well as fourteen reported compounds (5-18) were isolated and purified from Salvia miltiorrhiza Bunge (Danshen). The structures of novel compounds were determined by 1D and 2D NMR, HRESIMS data, etc. The anti-inflammatory properties of all the compounds on RAW264.7 macrophages and their cytotoxicity on H1299 and Bel-7402 cell lines coupled with a structure-activity relationship (SAR) were investigated. Compound 4 demonstrated the best anti-inflammatory activity and was chosen for further research. Compound 4 greatly suppressed secretion of nitric oxide (NO), tumor necrosis factor (TNF)-α and interleukin-6 (IL-6) in the RAW264.7 macrophages stimulated by LPS. Additionally, the protein expression of inducible nitric oxide synthase (iNOS) and cyclooxygenase-2 (COX-2) was decreased and the nuclear translocation of NF-κB was attenuated after treatment with compound 4 in vitro. Compound 4 was able to dramatically inhibit LPS-induced activation of JNK1/2 and ERK1/2 and remarkably disrupted the TLR4 dimerization in LPS-induced RAW264.7 macrophages. Thus, the new compound 4 suppressed LPS-induced inflammation partially is due to the blocking TLR4 dimerization. In addition, the anti-cancer activity investigation indicated that most of isolated compounds exhibited cytotoxicity and the SAR analysis showed that the intact D ring was indispensable and unsaturated D ring played vital role.

45 CFR 79.3 - Basis for civil penalties and assessments.

Code of Federal Regulations, 2013 CFR

2013-10-01

... shall be in lieu of damages sustained by the Government because of such claim. (b) Statements. (1... title XVIII of the Social Security Act; (iv) Aid to families with dependent children under a State plan...

45 CFR 79.3 - Basis for civil penalties and assessments.

Code of Federal Regulations, 2012 CFR

2012-10-01

... shall be in lieu of damages sustained by the Government because of such claim. (b) Statements. (1... title XVIII of the Social Security Act; (iv) Aid to families with dependent children under a State plan...

45 CFR 79.3 - Basis for civil penalties and assessments.

Code of Federal Regulations, 2011 CFR

2011-10-01

... shall be in lieu of damages sustained by the Government because of such claim. (b) Statements. (1... title XVIII of the Social Security Act; (iv) Aid to families with dependent children under a State plan...

[Organization of clinical care of North Fleet hospitals in XVIII century].

PubMed

Kostiuk, A V

2013-02-01

Clinical care of national navy hospitals was normed from reception of patients till hospital discharge. After admission to the hospital, patient got competent medical care and corresponding attendance. But the situation changed in XVIII century, period of wars. In conditions of war time hospitals were overcrowded with patients and wounded. The number of patients went beyond the bedspace. Deficit of vacant beds was supplied with the help of additional beds; deficit of medical staff was supplied with the help of participation of another medial staff. Huge number of patients with different diseases, including contagious diseases, conduced communication of contagious diseases inside the hospital. Diagnostics and methods of treatment of these diseases were not enough researched. Taking into account results of statistical analysis of data about the number of fatality cases (peace time--4-10%, war time--20%), we can make a conclusion that clinical care of national navy hospitals was satisfying.

Hg diffusion in books of XVIII and XIX centuries by synchrotron microprobe

NASA Astrophysics Data System (ADS)

Pessanha, S.; Carvalho, M. L.; Manso, M.; Guilherme, A.; Marques, A. F.; Perez, C. A.

2009-08-01

The pigment vermilion (HgS) was used to color the fore edge, tail and head of books. Dissemination and quantification of Hg present in the ink used to color books from XVIII and XIX centuries are reported. Mercury is a very toxic element for the human body, therefore it is extremely important to know whether Hg tends to disseminate throughout the paper or stays confined to the borders of the books with less danger for readers. Synchrotron X-ray microprobe was used to evaluate Hg dissemination from the border to the centre of the paper sheet. The diffusion pattern of Hg was compared with the results obtained by a portable X-ray fluorescence spectrometer and mean quantitative calculations were obtained by a stationary X-ray fluorescence system with triaxial geometry. The results showed high concentrations of Hg in the external regions, but no diffusion was observed for the inner parts of the paper.

[The crisis of medicine or the antimedicine crisis].

PubMed

Foucault, M

1976-01-01

In this lecture, Professor Michel Foucault makes an in-depth study of the problems currently afflicting medical institutions and the medical practice. He deals with the thesis set forth by Ivan Illich in his book Medical Nemesis--The expropriation of Health, as well as the 1942 Beveridge Plan, but goes even further back in history to discover the origin of the medical crisis common throughout the world--back to the XVIII century roots of the social practice of medicine. He also describes the phases through which medical activity has passed from then until now and deals with what he calls the political economy of medicine. Finally, he reaches the conclusion that what matters is not so much the present crisis of medicine, which he considers to be a false concept, but the discipline's historical model dating from the XVIII century and serving to determine to what extent it can be modified.

Effect of e-beam irradiation and microwave heating on the fatty acid composition and volatile compound profile of grass carp surimi

NASA Astrophysics Data System (ADS)

Zhang, Hongfei; Wang, Wei; Wang, Haiyan; Ye, Qingfu

2017-01-01

In this study, we evaluated the effects of e-beam irradiation（1-7 kGy） and irradiation coupled to microwave heating (e-I-MC, 70 °C internal temperature) on the fatty acid composition and volatile compound profile of grass carp surimi. Compared to control samples, e-beam irradiation generated three novel volatile compounds (heptane, 2,6-dimethyl-nonane, and dimethyl disulfide) and increased the relative proportions of alcohols, aldehydes, and ketones. Meanwhile, e-I-MC significantly increased aldehyde levels and generated five heterocyclic compounds along with these three novel compounds. No significant difference in volatile compounds were detected in e-I-MC samples with increasing irradiation dose (p>0.05), comparing to the control group. E-beam irradiation at 5 and 7 kGy increased the levels of saturated fatty acids (SFAs) and decreased the levels of unsaturated fatty acids (p≤0.05), but did not affect the content of trans fatty acid levels (p>0.05). Irradiation, which had no significant effects on (Eicosapentaenoic acid) EPA, decreased (Docose Hexaenoie Acid) DHA levels. In the e-I-MC group, SFA levels increased and PUFA levels decreased. Additionally, MUFA levels were unaffected and trans fatty acid levels increased slightly following e-I-MC.

Characterization of the components of meleumycin by liquid chromatography with photo-diode array detection and electrospray ionization tandem mass spectrometry.

PubMed

Wang, Ming-Juan; Li, Ya-Ping; Wang, Yan; Li, Jin; Hu, Chang-Qin; Hoogmartens, Jos; Van Schepdael, Ann; Adams, Erwin

2013-10-01

Reversed-phase liquid chromatography coupled with photo-diode array (PDA) detection and electrospray ionization tandem mass spectrometry (ESI-MS/MS) was used to characterize the components of meleumycin, a 16-membered macrolide antibiotic produced by fermentation. In total 31 components were characterized in commercial samples, including 12 impurities that had never been reported before and 12 others that were partially characterized. The structures of these unknown compounds were deduced by comparison of their fragmentation patterns with those of known components. Their ultraviolet spectra and chromatographic behavior were used to confirm the proposed structures: e.g. λmax shift from 232 nm to 282 nm would indicate the presence of an α-, β-, γ-, δ-unsaturated ketone instead of a normal α-, β-, γ-, δ-unsaturated alcohol in the 16-membered ring of the examined components. Compared to other methods, this LC/MS(n) method is particularly advantageous to characterize minor components at trace levels in multi-components antibiotics, in terms of sensitivity and efficiency. Copyright © 2013 Elsevier B.V. All rights reserved.

Verification and benchmark testing of the NUFT computer code

NASA Astrophysics Data System (ADS)

Lee, K. H.; Nitao, J. J.; Kulshrestha, A.

1993-10-01

This interim report presents results of work completed in the ongoing verification and benchmark testing of the NUFT (Nonisothermal Unsaturated-saturated Flow and Transport) computer code. NUFT is a suite of multiphase, multicomponent models for numerical solution of thermal and isothermal flow and transport in porous media, with application to subsurface contaminant transport problems. The code simulates the coupled transport of heat, fluids, and chemical components, including volatile organic compounds. Grid systems may be cartesian or cylindrical, with one-, two-, or fully three-dimensional configurations possible. In this initial phase of testing, the NUFT code was used to solve seven one-dimensional unsaturated flow and heat transfer problems. Three verification and four benchmarking problems were solved. In the verification testing, excellent agreement was observed between NUFT results and the analytical or quasianalytical solutions. In the benchmark testing, results of code intercomparison were very satisfactory. From these testing results, it is concluded that the NUFT code is ready for application to field and laboratory problems similar to those addressed here. Multidimensional problems, including those dealing with chemical transport, will be addressed in a subsequent report.

Occurrence, biological activity and metabolism of 6-shogaol.

PubMed

Kou, Xingran; Wang, Xiaoqi; Ji, Ruya; Liu, Lang; Qiao, Yening; Lou, Zaixiang; Ma, Chaoyang; Li, Shiming; Wang, Hongxin; Ho, Chi-Tang

2018-03-01

As one of the main bioactive compounds of dried ginger, 6-shogaol has been widely used to alleviate many ailments. It is also a major pungent flavor component, and its precursor prior to dehydration is 6-gingerol, which is reported to be responsible for the pungent flavor and biological activity of fresh ginger. Structurally, gingerols including 6-gingerol have a β-hydroxyl ketone moiety and is liable to dehydrate to generate an α,β-unsaturated ketone under heat and/or acidic conditions. The conjugation of the α,β-unsaturated ketone skeleton in the chemical structure of 6-shogaol explicates its higher potency and efficacy than 6-gingerol in terms of antioxidant, anti-inflammatory, anticancer, antiemetic and other bioactivities. Research on the health benefits of 6-shogaol has been conducted and results have been reported recently; however, scientific data are scattered due to a lack of systematic collection. In addition, action mechanisms of the preventive and/or therapeutic actions of 6-shogaol remain obscurely non-collective. Herein, we review the preparations, biological activity and mechanisms, and metabolism of 6-shogaol as well as the properties of 6-shogaol metabolites.

Fatty acid constituents of Peganum harmala plant using Gas Chromatography-Mass Spectroscopy.

PubMed

Moussa, Tarek A A; Almaghrabi, Omar A

2016-05-01

Fatty acid contents of the Peganum harmala plant as a result of hexane extraction were analyzed using GC-MS. The saturated fatty acid composition of the harmal plant was tetradecanoic, pentadecanoic, tridecanoic, hexadecanoic, heptadecanoic and octadecanoic acids, while the saturated fatty acid derivatives were 12-methyl tetradecanoic, 5,9,13-trimethyl tetradecanoic and 2-methyl octadecanoic acids. The most abundant fatty acid was hexadecanoic with concentration 48.13% followed by octadecanoic with concentration 13.80%. There are four unsaturated fatty acids called (E)-9-dodecenoic, (Z)-9-hexadecenoic, (Z,Z)-9,12-octadecadienoic and (Z,Z,Z)-9,12,15-octadecatrienoic. The most abundant unsaturated fatty acid was (Z,Z,Z)-9,12,15-octadecatrienoic with concentration 14.79% followed by (Z,Z)-9,12-octadecadienoic with concentration 10.61%. Also, there are eight non-fatty acid compounds 1-octadecene, 6,10,14-trimethyl-2-pentadecanone, (E)-15-heptadecenal, oxacyclohexadecan-2 one, 1,2,2,6,8-pentamethyl-7-oxabicyclo[4.3.1]dec-8-en-10-one, hexadecane-1,2-diol, n-heneicosane and eicosan-3-ol.

Fatty acid constituents of Peganum harmala plant using Gas Chromatography–Mass Spectroscopy

PubMed Central

Moussa, Tarek A.A.; Almaghrabi, Omar A.

2015-01-01

Fatty acid contents of the Peganum harmala plant as a result of hexane extraction were analyzed using GC–MS. The saturated fatty acid composition of the harmal plant was tetradecanoic, pentadecanoic, tridecanoic, hexadecanoic, heptadecanoic and octadecanoic acids, while the saturated fatty acid derivatives were 12-methyl tetradecanoic, 5,9,13-trimethyl tetradecanoic and 2-methyl octadecanoic acids. The most abundant fatty acid was hexadecanoic with concentration 48.13% followed by octadecanoic with concentration 13.80%. There are four unsaturated fatty acids called (E)-9-dodecenoic, (Z)-9-hexadecenoic, (Z,Z)-9,12-octadecadienoic and (Z,Z,Z)-9,12,15-octadecatrienoic. The most abundant unsaturated fatty acid was (Z,Z,Z)-9,12,15-octadecatrienoic with concentration 14.79% followed by (Z,Z)-9,12-octadecadienoic with concentration 10.61%. Also, there are eight non-fatty acid compounds 1-octadecene, 6,10,14-trimethyl-2-pentadecanone, (E)-15-heptadecenal, oxacyclohexadecan-2 one, 1,2,2,6,8-pentamethyl-7-oxabicyclo[4.3.1]dec-8-en-10-one, hexadecane-1,2-diol, n-heneicosane and eicosan-3-ol. PMID:27081366

Preparation of optically active bicyclodihydrosiloles by a radical cascade reaction

PubMed Central

Miyazaki, Koichiro; Yamane, Yu; Yo, Ryuichiro; Uno, Hidemitsu

2013-01-01

Summary Bicyclodihydrosiloles were readily prepared from optically active enyne compounds by a radical cascade reaction triggered by tris(trimethylsilyl)silane ((Me3Si)3SiH). The reaction was initiated by the addition of a silyl radical to an α,β-unsaturated ester, forming an α-carbonyl radical that underwent radical cyclization to a terminal alkyne unit. The resulting vinyl radical attacked the silicon atom in an SHi manner to give dihydrosilole. The reaction preferentially formed trans isomers of bicyclosiloles with an approximately 7:3 to 9:1 selectivity. PMID:23946827

Mixtures of Quaternary Ammonium Compounds and Long-chain Fatty Acids as Antifungal Agents

PubMed Central

Kull, F. C.; Eisman, P. C.; Sylwestrowicz, H. D.; Mayer, R. L.

1961-01-01

The influence of undecylenic acid on the fungistatic effect of phenoxyethyldimethyldodecylammonium bromide (Domiphen bromide) against Trichophyton mentagrophytes was investigated. The unsaturated fatty acid was found to enhance the fungistatic activity of Domiphen bromide against this organism. The ratio of concentrations of these agents has a marked influence on the results of in vitro tests for antifungal action resulting in a completely different effect than heretofore noted in combination experiments against bacteria. The enhancing phenomenon is not particular to T. mentagrophytes, it was observed also with Candida albicans. PMID:14460466

Chemiluminescent reaction of oxygen atoms with some nitrile compounds

NASA Astrophysics Data System (ADS)

Upadhyaya, Hari P.; Pavanaja, Ubaradka B.; Sapre, Avinash V.; Rama Rao, Kuchimanchi V. S.; Mittal, Jai P.

1994-09-01

In a discharge-flow experiment, chemiluminescent reactions of oxygen atoms (O( 3P)) with organic nitriles (RCN) are studied. For unsaturated nitriles RCN (R: CH 2=CH; CH 2=C(CH 3); CH 2=CH(CH 2)) the observed emission is attributed to CN * (B→X) and NO * (γ:A→X and β: B→X, bands). For saturated and phenyl nitriles (R: CH 3; C 2H 5; C 6H 5) emission is only observed from CN * (B 2Σ +). A suitable reaction mechanism for the observed emission is proposed.

Titanium isopropoxide as efficient catalyst for the aza-Baylis-Hillman reaction. Selective formation of alpha-methylene-beta-amino acid derivatives.

PubMed

Balan, Daniela; Adolfsson, Hans

2002-04-05

The direct formation of alpha-methylene-beta-amino acid derivatives is achieved using the aza version of the Baylis-Hillman protocol. The products are readily formed in a three-component one-pot reaction between arylaldehydes, sulfonamides, and alpha,beta-unsaturated carbonyl compounds. The reaction is efficiently catalyzed by titanium isopropoxide and 2-hydroxyquinuclidine in the presence of molecular sieves. The protocol allows for structural variation of the substrates, tolerating electron-poor and electron-rich arylaldehydes and various Michael acceptors.

Iterative Coupling of Two Different Enones by Nitromethane Using Bifunctional Thiourea Organocatalysts. Stereocontrolled Assembly of Cyclic and Acyclic Structures.

PubMed

Varga, Szilárd; Jakab, Gergely; Csámpai, Antal; Soós, Tibor

2015-09-18

An organocatalytic iterative assembly line has been developed in which nitromethane was sequentially coupled with two different enones using a combination of pseudoenantiomeric cinchona-based thiourea catalysts. Application of unsaturated aldehydes and ketones in the second step of the iterative sequence allows the construction of cyclic syn-ketols and acyclic compounds with multiple contiguous stereocenters. The combination of the multifunctional substrates and ambident electrophiles rendered some organocatalytic transformations possible that have not yet been realized in bifunctional noncovalent organocatalysis.

Design and synthesis of aryl ether and sulfone hydroxamic acids as potent histone deacetylase (HDAC) inhibitors.

PubMed

Pabba, Chittari; Gregg, Brian T; Kitchen, Douglas B; Chen, Zhen Jia; Judkins, Angela

2011-01-01

A series of novel hydroxamic acid based histone deacetylases (HDAC) inhibitors with aryl ether and aryl sulfone residues at the terminus of a substituted, unsaturated 5-carbon spacer moiety have been synthesized for the first time and evaluated. Compounds with meta- and para-substitution on the aryl ring of ether hydroxamic acids 19c, 20c, 19e, 19f and 19g are potent HDAC inhibitors with activities at low nanomolar levels. Copyright © 2010 Elsevier Ltd. All rights reserved.

Enantioselective Copper-Catalyzed Carboetherification of Unactivated Alkenes**

PubMed Central

Bovino, Michael T.; Liwosz, Timothy W.; Kendel, Nicole E.; Miller, Yan; Tyminska, Nina

2014-01-01

Chiral saturated oxygen heterocycles are important components of bioactive compounds. Cyclization of alcohols onto pendant alkenes is a direct route to their synthesis, but few catalytic enantioselective methods enabling cyclization onto unactivated alkenes exist. Herein is reported a highly efficient copper-catalyzed cyclization of γ-unsaturated pentenols that terminates in C-C bond formation, a net alkene carboetherification. Both intra- and intermolecular C-C bond formations are demonstrated, yielding functionalized chiral tetrahydrofurans as well as fused-ring and bridged-ring oxabicyclic products. Transition state calculations support a cis-oxycupration stereochemistry-determining step. PMID:24798697

User’s guide to the collection and analysis of tree cores to assess the distribution of subsurface volatile organic compounds

USGS Publications Warehouse

Vroblesky, Don A.

2008-01-01

Analysis of the volatile organic compound content of tree cores is an inexpensive, rapid, simple approach to examining the distribution of subsurface volatile organic compound contaminants. The method has been shown to detect several volatile petroleum hydrocarbons and chlorinated aliphatic compounds associated with vapor intrusion and ground-water contamination. Tree cores, which are approximately 3 inches long, are obtained by using an increment borer. The cores are placed in vials and sealed. After a period of equilibration, the cores can be analyzed by headspace analysis gas chromatography. Because the roots are exposed to volatile organic compound contamination in the unsaturated zone or shallow ground water, the volatile organic compound concentrations in the tree cores are an indication of the presence of subsurface volatile organic compound contamination. Thus, tree coring can be used to detect and map subsurface volatile organic compound contamination. For comparison of tree-core data at a particular site, it is important to maintain consistent methods for all aspects of tree-core collection, handling, and analysis. Factors affecting the volatile organic compound concentrations in tree cores include the type of volatile organic compound, the tree species, the rooting depth, ground-water chemistry, the depth to the contaminated horizon, concentration differences around the trunk related to variations in the distribution of subsurface volatile organic compounds, concentration differences with depth of coring related to volatilization loss through the bark and possibly other unknown factors, dilution by rain, seasonal influences, sorption, vapor-exchange rates, and within-tree volatile organic compound degradation.

Volatiles formation in gelled emulsions enriched in polyunsaturated fatty acids during storage: type of oil and antioxidant.

PubMed

Gayoso, Lucía; Poyato, Candelaria; Calvo, María Isabel; Cavero, Rita Yolanda; Ansorena, Diana; Astiasarán, Iciar

2017-08-01

Gelled emulsions with carrageenan are a novel type of emulsion that could be used as a carrier of unsaturated fatty acids in functional foods formulations. Lipid degradation through volatile compounds was studied in gelled emulsions which were high in polyunsaturated oils (sunflower or algae oil) after 49 days of storage. Aqueous Lavandula latifolia extract was tested as a natural antioxidant. Analysis of the complete volatile profile of the samples resulted in a total of 40 compounds, classified in alkanes, alkenes, aldehydes, ketones, acids, alcohols, furans, terpenes and aromatic hydrocarbons. During storage, the formation of the volatile compounds was mostly related to the oxidation of the main fatty acids of the sunflower oil (linolenic acid) and the algae oil (docosahexaenoic acid). Despite the antioxidant capacity shown by the L. latifolia extract, its influence in the oxidative stability in terms of total volatiles was only noticed in sunflower oil gels ( p  < 0.05), where a significant decrease in the aldehydes fraction was found.

Photocatalytic degradation of paracetamol: intermediates and total reaction mechanism.

PubMed

Moctezuma, Edgar; Leyva, Elisa; Aguilar, Claudia A; Luna, Raúl A; Montalvo, Carlos

2012-12-01

The advanced oxidation of paracetamol (PAM) promoted by TiO(2)/UV system in aqueous medium was investigated. Monitoring this reaction by HPLC and TOC, it was demonstrated that while oxidation of paracetamol is quite efficient under these conditions, its mineralization is not complete. HPLC indicated the formation of hydroquinone, benzoquinone, p-aminophenol and p-nitrophenol in the reaction mixtures. Further evidence of p-nitrophenol formation was obtained following the reaction by UV-vis spectroscopy. Continuous monitoring by IR spectroscopy demonstrated the breaking of the aromatic amide present in PAM and subsequent formation of several aromatic intermediate compounds such as p-aminophenol and p-nitrophenol. These aromatic compounds were eventually converted into trans-unsaturated carboxylic acids. Based on these experimental results, an alternative deacylation mechanism for the photocatalytic oxidation of paracetamol is proposed. Our studies also demonstrated IR spectroscopy to be a useful technique to investigate oxidative mechanisms of pharmaceutical compounds. Copyright © 2012 Elsevier B.V. All rights reserved.

The search for new amphiphiles: synthesis of a modular, high-throughput library

PubMed Central

Feast, George C; Lepitre, Thomas; Mulet, Xavier; Conn, Charlotte E; Hutt, Oliver E

2014-01-01

Summary Amphiphilic compounds are used in a variety of applications due to their lyotropic liquid-crystalline phase formation, however only a limited number of compounds, in a potentially limitless field, are currently in use. A library of organic amphiphilic compounds was synthesised consisting of glucose, galactose, lactose, xylose and mannose head groups and double and triple-chain hydrophobic tails. A modular, high-throughput approach was developed, whereby head and tail components were conjugated using the copper-catalysed azide–alkyne cycloaddition (CuAAC) reaction. The tails were synthesised from two core alkyne-tethered intermediates, which were subsequently functionalised with hydrocarbon chains varying in length and degree of unsaturation and branching, while the five sugar head groups were selected with ranging substitution patterns and anomeric linkages. A library of 80 amphiphiles was subsequently produced, using a 24-vial array, with the majority formed in very good to excellent yields. A preliminary assessment of the liquid-crystalline phase behaviour is also presented. PMID:25161714

The search for new amphiphiles: synthesis of a modular, high-throughput library.

PubMed

Feast, George C; Lepitre, Thomas; Mulet, Xavier; Conn, Charlotte E; Hutt, Oliver E; Savage, G Paul; Drummond, Calum J

2014-01-01

Amphiphilic compounds are used in a variety of applications due to their lyotropic liquid-crystalline phase formation, however only a limited number of compounds, in a potentially limitless field, are currently in use. A library of organic amphiphilic compounds was synthesised consisting of glucose, galactose, lactose, xylose and mannose head groups and double and triple-chain hydrophobic tails. A modular, high-throughput approach was developed, whereby head and tail components were conjugated using the copper-catalysed azide-alkyne cycloaddition (CuAAC) reaction. The tails were synthesised from two core alkyne-tethered intermediates, which were subsequently functionalised with hydrocarbon chains varying in length and degree of unsaturation and branching, while the five sugar head groups were selected with ranging substitution patterns and anomeric linkages. A library of 80 amphiphiles was subsequently produced, using a 24-vial array, with the majority formed in very good to excellent yields. A preliminary assessment of the liquid-crystalline phase behaviour is also presented.

Ripening-dependent metabolic changes in the volatiles of pineapple (Ananas comosus (L.) Merr.) fruit: I. Characterization of pineapple aroma compounds by comprehensive two-dimensional gas chromatography-mass spectrometry.

PubMed

Steingass, Christof Björn; Carle, Reinhold; Schmarr, Hans-Georg

2015-03-01

Qualitative ripening-dependent changes of pineapple volatiles were studied via headspace solid-phase microextraction and analyzed by comprehensive two-dimensional gas chromatography quadrupole mass spectrometry (HS-SPME-GC×GC-qMS). Early green-ripe stage, post-harvest ripened, and green-ripe fruits at the end of their commercial shelf-life were compared to air-freighted pineapples harvested at full maturity. In total, more than 290 volatiles could be identified by mass spectrometry and their linear retention indices. The majority of compounds comprise esters (methyl and ethyl esters of saturated and unsaturated fatty acids, acetates), terpenes, alcohols, aldehydes, 2-ketones, free fatty acids, and miscellaneous γ- and δ-lactones. The structured separation space obtained by GC×GC allowed revealing various homologous series of compound classes as well as clustering of sesquiterpenes. Post-harvest ripening increased the diversity of the volatile profile compared to both early green-ripe maturity stages and on-plant ripened fruits.

Double-stabilized neurotensin analogues as potential radiopharmaceuticals for NTR-positive tumors.

PubMed

García-Garayoa, Elisa; Maes, Veronique; Bläuenstein, Peter; Blanc, Alain; Hohn, Alexander; Tourwé, Dirk; Schubiger, P August

2006-05-01

Overexpression of neurotensin (NT) receptors in exocrine pancreatic cancer and other neuroendocrine cancers make them interesting targets for tumor imaging and therapy. Modifications at the cleavage bonds 8-9 and 11-12 led to the synthesis of NT-XII, NT-XIII and NT-XVIII, three new stabilized analogues. (NalphaHis)Ac was coupled to the N-terminus for labeling with [(99m)Tc]-tricarbonyl. Stability was tested in vitro in human plasma and HT-29 cells. Binding to NT1 receptors and internalization/efflux were analyzed in intact HT-29 cells. Biodistribution studies were performed in nude mice bearing HT-29 xenografts. All analogues were very stable in human plasma, with half-lives of 20-21 days. Degradation in HT-29 cells was more rapid (t(1/2) of 6.5, 5 and 2.5 h for NT-XII, NT-XIII and NT-XVIII, respectively). They also showed high affinity and specificity for NT1 receptors. Bound activity was rapidly internalized at 37 degrees C. The pattern of externalization was different. NT-XII was released more slowly than NT-XIII and NT-XVIII (half of the activity still inside the cells after 24 h). Bigger differences were found in the biodistribution studies. NT-XII showed the highest tumor uptake as well as the best tumor to nontumor ratios. The modifications introduced in NT(8-13) increased plasma stability, maintaining unaffected the in vitro binding properties. The best biodistribution corresponded to NT-XII, which shows to be a good candidate for NT1 receptors overexpressing tumors. First clinical trials are ongoing.

Molecular and isotopic analyses of Tagish Lake alkyl dicarboxylic acids

NASA Astrophysics Data System (ADS)

Pizzarello, Sandra; Huang, Yongsong

2002-05-01

The Tagish Lake meteorite soluble organic suite has a general composition that differs from those of both CI- and CM chondrites. These differences suggest that distinct processes may have been involved in the formation of different groups of organics in meteorites. Tagish Lake alkyl dicarboxylic acids have a varied, abundant distribution and are, with carboxylated pyridines, the only compounds to have an occurrence comparable to that of the Murchison meteorite. This study has undertaken their molecular and isotopic characterization, with the aim to understand their origin and to gain insights into the evolutionary history of the meteorite parent body. Tagish Lake alkyl dicarboxylic acids are present as a homologous series of saturated and unsaturated species with three through ten-carbon atom chain length. Linear saturated acids are predominant and show decreasing amounts with increasing chain length. A total of forty-four of these compounds were detected with the most abundant, succinic acid, present at ~40 nmoles/g. met. Overall the molecular distribution of Tagish Lake dicarboxylic acids shows a remarkable compound to compound correspondence with those observed in the Murchison and Murray meteorites. In both Tagish Lake and Murchison, the imides of the more abundant dicarboxylic acids were also observed. The hydrogen and carbon isotopic compositions of individual Tagish Lake dicarboxylic acids were determined and compared to those of the corresponding acids in the Murchison meteorite. All delta D and delta 13C values for Tagish Lake acids are positive and show a substantial isotopic enrichment. Delta D values vary from, approximately, + 1120 deg for succinic acid to + 1530 deg for methyl glutaric acid. Delta 13C values ranged from + 12.6 deg for methyl glutaric acid to + 22.9 deg for glutaric acid, with adipic acid having a significantly lower value (+ 5.5 deg). Murchison dicarboxylic acid showed similar isotopic values: their delta 13C values were generally higher by an average 17% and delta D values were lower for succinic and glutaric acids, possibly due to contamination. The molecular and isotopic data collected for these compounds restrict their possible origin to processes, either interstellar or of very cold nebular regions, that produced significant isotopic enrichments. Saturated or partially unsaturated nitriles and dinitriles appear to be good precursor candidates as their hydrolysis, upon water exposure, would produce dicarboxylic acids and other carboxylated species found in Tagish Lake. This evolutionary course could possibly include pre-accretionary processes.

Particulate sulfur-containing lipids: Production and cycling from the epipelagic to the abyssopelagic zone

NASA Astrophysics Data System (ADS)

Gašparović, Blaženka; Penezić, Abra; Frka, Sanja; Kazazić, Saša; Lampitt, Richard S.; Holguin, F. Omar; Sudasinghe, Nilusha; Schaub, Tanner

2018-04-01

There are major gaps in our understanding of the distribution and role of lipids in the open ocean especially with regard to sulfur-containing lipids (S-lipids). Here, we employ a powerful analytical approach based on high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to elucidate depth-related S-lipid production and molecular transformations in suspended particulate matter from the Northeast Atlantic Ocean in this depth range. We show that within the open-ocean environment S-lipids contribute up to 4.2% of the particulate organic carbon, and that up to 95% of these compounds have elemental compositions that do not match those found in the Nature Lipidomics Gateway database (termed "novel"). Among the remaining 5% of lipids that match the database, we find that sulphoquinovosyldiacylglycerol (SQDG) are efficiently removed while sinking through the mesopelagic zone. The relative abundance of other assigned lipids (sulphoquinovosylmonoacylglycerol (SQMG), sulfite and sulfate lipids, Vitamin D2 and D3 derivatives, and sphingolipids) did not change substantially with depth. The novel S-lipids, represented by hundreds of distinct elemental compositions (160-300 molecules at any one depth), contribute increasingly to the lipid and particulate organic matter pools with increased depth. Depth-related transformations cause (i) incomplete degradation/transformation of unsaturated S-lipids which leads to the depth-related accumulation of the refractory saturated compounds with reduced molecular weight (average 455 Da) and (ii) formation of highly unsaturated S-lipids (average abyssopelagic molecular double bond equivalents, DBE=7.8) with lower molecular weight (average 567 Da) than surface S-lipids (average 592 Da). A depth-related increase in molecular oxygen content is observed for all novel S-lipids and indicates that oxidation has a significant role in their transformation while (bio)hydrogenation possibly impacts the formation of saturated compounds. The instrumentation approach applied here represents a step change in our comprehension of marine S-lipid diversity and the potential role of these compounds in the oceanic carbon cycle. We describe a very much higher number of compounds than previously reported, albeit at the level of elemental composition and fold-change quantitation with depth, rather than isomeric confirmation and absolute quantitation of individual lipids. We emphasize that saturated S-lipids have the potential to transfer carbon from the upper ocean to depth and hence are significant vectors for carbon sequestration.

The use of natural products to minimize and or counter act the risk of exposure to environmental pollutants

NASA Astrophysics Data System (ADS)

Anthony, Kevin P.

Essential oils have been studied for their unique ability to act as antioxidants. There is a large pool of publications describing the antioxidant activity of essential oils, however they all present results of research that was performed on a small number of oils and at most an individual botanical family or related species Antioxidant activities of 423 essential oils of 48 different botanical families were evaluated for their antioxidant activities as free radical scavenging agents using the 1,1-diphenyl-2-picryihydrazyl method. The EC50 of the 84 most active oils ranged from 4 to 2000 microg/mL. Oils having an EC50 of less than 300 mug/mL, (20 selected samples) were subjected to beta-carotene bleaching antioxidant activity test. Milk thistle dietary supplements that contain silymarin are widely marketed and used in the U.S.A and other countries for liver enhancement and recovery. More recently, silymarin has also been identified as a possible antiviral for the treatment of hepatitis C virus (HCV) infection. To assess different brands of commercially sold milk thistle, 45 products were collected from local stores and analyzed for their silymarin content, antioxidant activities and anti-HCV activity. Rumex dentatus L. and Rumex vesicarius L. of the family Polygonaceae, are edible herbs growing wild in Egypt. There are few phytochemical studies found in the literature describing the chemical constituents of the two described species. Their lipoid constituents were examined to determine their essential oil and fatty acid composition. Both extracts were also tested for their radical scavenging activity. We investigated three groups of natural herbal antioxidants . One group related to essential oils showed the active antioxidant is mostly related to monoterpenes (or phenolic compounds) and ciscoterpenes. With silymarin , the active antioxidant chemicals are polyphenolic compounds. With the Rumnex , they showed the possibility of significant antioxidant activity and the chemical groups of most importance were the phenolic compounds and omega-3 poly unsaturated fatty acids. We investigated three groups of natural herbal antioxidants. One group related to essential oils showed the active antioxidant is mostly related to monoterpenes (or phenolic compounds) and ciscoterpenes. With silymarin, the active antioxidant chemicals are polyphenolic compounds. With rumnex, the chemical group of most interest were the omega-3 poly unsaturated fatty acids.

4. AERIAL VIEW OF DAM SITE SHOWING OUTLET WORKS AND ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

4. AERIAL VIEW OF DAM SITE SHOWING OUTLET WORKS AND DIVERSION CHANNEL IN FOREGROUND.... Volume XVIII, No. 9, March 5, 1940. - Prado Dam, Santa Ana River near junction of State Highways 71 & 91, Corona, Riverside County, CA

42 CFR 480.101 - Scope and definitions.

Code of Federal Regulations, 2010 CFR

2010-10-01

... ORGANIZATION REVIEW INFORMATION Utilization and Quality Control Quality Improvement Organizations (QIOs... Quality Control Quality Improvement Organization (QIO) (or the review component of a QIO subcontractor) in... sought under Title XVIII of the Act. Aggregate statistical data means any utilization, admission...

50 CFR 216.174 - Mitigation.

Code of Federal Regulations, 2012 CFR

2012-10-01

... operation (including aircraft, surface ships, or submarines) shall monitor for marine mammal vocalizations... mammals. (xvii) Navy aircraft participating in exercises at sea shall conduct and maintain, when... constraints or interfere with the accomplishment of primary operational duties. (xviii) Aircraft with deployed...

50 CFR 216.174 - Mitigation.

Code of Federal Regulations, 2011 CFR

2011-10-01

... operation (including aircraft, surface ships, or submarines) shall monitor for marine mammal vocalizations... mammals. (xvii) Navy aircraft participating in exercises at sea shall conduct and maintain, when... constraints or interfere with the accomplishment of primary operational duties. (xviii) Aircraft with deployed...

50 CFR 216.174 - Mitigation.

Code of Federal Regulations, 2013 CFR

2013-10-01

... operation (including aircraft, surface ships, or submarines) shall monitor for marine mammal vocalizations... mammals. (xvii) Navy aircraft participating in exercises at sea shall conduct and maintain, when... constraints or interfere with the accomplishment of primary operational duties. (xviii) Aircraft with deployed...

Structural changes in plastids of developing Splachnum ampullaceum sporophytes and relationship to odour production

PubMed Central

McCuaig, B.; Dufour, S. C.; Raguso, R. A.; Bhatt, A. P.; Marino, P.

2014-01-01

Many mosses of the family Splachnaceae are entomophilous and rely on flies for spore dispersal. Splachnum ampullaceum produces a yellow- or pink-coloured hypophysis that releases volatile compounds, attracting flies to the mature moss. The biosynthetic sources of the visual and aromatic cues within the hypophysis have not been identified, and may be either symbiotic cyanobacteria or chromoplasts that break down lipids into volatile compounds. Here, we used transmission electron microscopy and gas chromatography-mass spectrometry (GC-MS) to investigate the sources of these attractants, focusing on different tissues and stages of maturation. Microscopy revealed an abundance of plastids within the hypophysis, while no symbiotic bacteria were observed. During plant maturation, plastids differentiated from amyloplasts with large starch granules to photosynthetic chloroplasts and finally to chromoplasts with lipid accumulations. We used GC-MS to identify over 50 volatile organic compounds from mature sporophytes including short-chain oxygenated compounds, unsaturated irregular terpenoids, fatty acid-derived 6- and 8-carbon alcohols and ketones, and the aromatic compounds acetophenone and p-cresol. The hypophysis showed localised production of pungent volatiles, mainly short-chain fermentation compounds and p-cresol. Some of these volatiles have been shown to be produced from lipid oxidase degradation of linolenic acid within chromoplasts. However, other compounds (such as cyclohexanecarboxylic acid esters) may have a microbial origin. Further investigation is necessary to identify the origin of fly attractants in these mosses. PMID:25213550

Catalytic enantioselective 1,6-conjugate additions of propargyl and allyl groups

NASA Astrophysics Data System (ADS)

Meng, Fanke; Li, Xiben; Torker, Sebastian; Shi, Ying; Shen, Xiao; Hoveyda, Amir H.

2016-09-01

Conjugate (or 1,4-) additions of carbanionic species to α,β-unsaturated carbonyl compounds are vital to research in organic and medicinal chemistry, and there are several chiral catalysts that facilitate the catalytic enantioselective additions of nucleophiles to enoates. Nonetheless, catalytic enantioselective 1,6-conjugate additions are uncommon, and ones that incorporate readily functionalizable moieties, such as propargyl or allyl groups, into acyclic α,β,γ,δ-doubly unsaturated acceptors are unknown. Chemical transformations that could generate a new bond at the C6 position of a dienoate are particularly desirable because the resulting products could then be subjected to further modifications. However, such reactions, especially when dienoates contain two equally substituted olefins, are scarce and are confined to reactions promoted by a phosphine-copper catalyst (with an alkyl Grignard reagent, dialkylzinc or trialkylaluminium compounds), a diene-iridium catalyst (with arylboroxines), or a bisphosphine-cobalt catalyst (with monosilyl-acetylenes). 1,6-Conjugate additions are otherwise limited to substrates where there is full substitution at the C4 position. It is unclear why certain catalysts favour bond formation at C6, and—although there are a small number of catalytic enantioselective conjugate allyl additions—related 1,6-additions and processes involving a propargyl unit are non-existent. Here we show that an easily accessible organocopper catalyst can promote 1,6-conjugate additions of propargyl and 2-boryl-substituted allyl groups to acyclic dienoates with high selectivity. A commercially available allenyl-boron compound or a monosubstituted allene may be used. Products can be obtained in up to 83 per cent yield, >98:2 diastereomeric ratio (for allyl additions) and 99:1 enantiomeric ratio. We elucidate the mechanistic details, including the origins of high site selectivity (1,6- versus 1,4-) and enantioselectivity as a function of the catalyst structure and reaction type, by means of density functional theory calculations. The utility of the approach is highlighted by an application towards enantioselective synthesis of the anti-HIV agent (-)-equisetin.

New Photosensitized Processes at Aerosol and Ocean Surfaces

NASA Astrophysics Data System (ADS)

Rossignol, S.; Aregahegn, K. Z.; Ciuraru, R.; Bernard, F.; Tinel, L.; Fine, L.; George, C.

2014-12-01

From a few years now, there is a growing body of evidence that photoinduced processes could be of great importance for the tropospheric chemistry. Here, we would like to present two additional outcomes of this new area of research, firstly the photosensitized direct VOC uptake by aerosols and, secondly, the photoinduced chemical formation of unsaturated VOC from marine microlayer proxy. It was recently shown that the chemistry of glyoxal toward ammonium ions into droplets and wet aerosols leads to the formation of light-absorbing compounds. Among them, we found that imidazole-2-carboxaldehyde (IC) acts as a photosensitizer and is able to initiate the growth of organic aerosols via the uptake of VOC, such as limonene. Given its potential importance, the mechanism of this photoinduced uptake was investigated thanks to aerosol flow tube experiments and UPLC-ESI-HRMS analysis. Results reveal hydrogen abstraction on the VOC molecule by the triplet state of IC leading to the VOC oxidation without any traditional oxidant. As well as aerosol, the sea-surface microlayer, known to be enriched in light-absorbing organics, is largely impacted by photochemical processes. Recent studies have pointed out for example the role of photosentitized processes in the loss of NO2 and ozone at water surfaces containing photoactive compounds such as chlorophyll. In order to go further, we worked from sea-surface microlayer proxy containing humic acids as photoactive material and organic acids as surfactants. Beside oxidation processes, we monitored by high resolution PTR-MS the release in the gas phase of unsaturated compounds, including C5 dienes (isoprene ?). A strong correlation between the measured surface tension and the C5 diene concentration in the gas phase was evidenced, clearly pointing toward an interfacial process. This contribution will highlight the similarities between both systems and will attempt to present a general chemical scheme for photosensitized chemistry at interfaces.

Di-Peptide-Modified Gemini Surfactants as Gene Delivery Vectors: Exploring the Role of the Alkyl Tail in Their Physicochemical Behavior and Biological Activity.

PubMed

Al-Dulaymi, Mays A; Chitanda, Jackson M; Mohammed-Saeid, Waleed; Araghi, Hessamaddin Younesi; Verrall, Ronald E; Grochulski, Pawel; Badea, Ildiko

2016-09-01

The aim of this work was to elucidate the structure-activity relationship of new peptide-modified gemini surfactant-based carriers. Glycyl-lysine modified gemini surfactants that differ in the length and degree of unsaturation of their alkyl tail were used to engineer DNA nano-assemblies. To probe the optimal nitrogen to phosphate (N/P) ratio in the presence of helper lipid, in vitro gene expression and cell toxicity measurements were carried out. Characterization of the nano-assemblies was accomplished by measuring the particle size and surface charge. Morphological characteristics and lipid organization were studied by small angle X-ray scattering technique. Lipid monolayers were studied using a Langmuir-Blodgett trough. The highest activity of glycyl-lysine modified gemini surfactants was observed with the 16-carbon tail compound at 2.5 N/P ratio, showing a 5- to 10-fold increase in the level of reporter protein compared to the 12 and 18:1 carbon tail compounds. This ratio is significantly lower compared to the previously studied gemini surfactants with alkyl or amino- spacers. In addition, the 16-carbon tail compound exhibited the highest cell viability (85%). This high efficiency is attributed to the lowest critical micelle concentration of the 16-tail gemini surfactant and a balanced packing of the nanoparticles by mixing a saturated and unsaturated lipid together. At the optimal N/P ratio, all nanoparticles exhibited an inverted hexagonal lipid assembly. The results show that the length and nature of the tail of the gemini surfactants play an important role in determining the transgene efficiency of the delivery system. We demonstrated here that the interplay between the headgroup and the nature of tail is specific to each series, thus in the process of rational design, the contribution of the latter should be assessed in the appropriate context.

Assembly of Four Diverse Heterocyclic Libraries Enabled by Prins Cyclization, Au-Catalyzed Enyne Cycloisomerization, and Automated Amide Synthesis

PubMed Central

Cui, Jiayue; Chai, David I.; Miller, Christopher; Hao, Jason; Thomas, Christopher; Wang, JingQi; Scheidt, Karl A.; Kozmin, Sergey A.

2013-01-01

We describe a unified synthetic strategy for efficient assembly of four new heterocyclic libraries. The synthesis began by creating a range of structurally diverse pyrrolidinones or piperidinones. Such compounds were obtained in a simple one-flask operation starting with readily available amines, ketoesters, and unsaturated anhydrides. The use of tetrahydropyran-containing ketoesters, which were rapidly assembled by our Prins cyclization protocol, enabled efficient fusion of pyran and piperidinone cores. A newly developed Au(I)-catalyzed cycloisomerization of alkyne-containing enamides further expanded heterocyclic diversity by providing rapid entry into a wide range of bicyclic and tricyclic dienamides. The final stage of the process entailed diversification of each of the initially produced carboxylic acids using a fully automated platform for amide synthesis, which delivered 1872 compounds in high diastereomeric and chemical purity. PMID:22860634

[Optimization for supercritical CO2 extraction with response surface methodology of Prunus armeniaca oil].

PubMed

Chen, Fei-Fei; Wu, Yan; Ge, Fa-Huan

2012-03-01

To optimize the extraction conditions of Prunus armeniaca oil by Supercritical CO2 extraction and identify its components by GC-MS. Optimized of SFE-CO extraction by response surface methodology and used GC-MS to analysis Prunus armeniaca oil compounds. Established the model of an equation for the extraction rate of Prunus armeniaca oil by supercritical CO2 extraction, and the optimal parameters for the supercritical CO2 extraction determined by the equation were: the extraction pressure was 27 MPa, temperature was 39 degrees C, the extraction rate of Prunus armeniaca oil was 44.5%. 16 main compounds of Prunus armeniaca oil extracted by supercritical CO2 were identified by GC-MS, unsaturated fatty acids were 92.6%. This process is simple, and can be used for the extraction of Prunus armeniaca oil.

16. VIEW EASTERLY ALONG THE UPSTREAM SIDE OF THE OGEE ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

16. VIEW EASTERLY ALONG THE UPSTREAM SIDE OF THE OGEE SECTION OF THE SPILLWAY.... Volume XVIII, No. 13, January 29, 1940. - Prado Dam, Spillway, Santa Ana River near junction of State Highways 71 & 91, Corona, Riverside County, CA

20 CFR 655.1110 - What requirements are imposed in the filing of an attestation?

Code of Federal Regulations, 2011 CFR

2011-04-01

... 2552 filed with the Department of Health and Human Services (pursuant to title XVIII of the Social... intended or designed to influence an election for a bargaining representative for RNs at the facility, and...

Experimental and modeling study of the thermal decomposition of methyl decanoate

PubMed Central

Herbinet, Olivier; Glaude, Pierre-Alexandre; Warth, Valérie; Battin-Leclerc, Frédérique

2013-01-01

The experimental study of the thermal decomposition of methyl decanoate was performed in a jet-stirred reactor at temperatures ranging from 773 to 1123 K, at residence times between 1 and 4 s, at a pressure of 800 Torr (106.6 kPa) and at high dilution in helium (fuel inlet mole fraction of 0.0218). Species leaving the reactor were analyzed by gas chromatography. Main reaction products were hydrogen, carbon oxides, small hydrocarbons from C1 to C3, large 1-olefins from 1-butene to 1-nonene, and unsaturated esters with one double bond at the end of the alkyl chain from methyl-2-propenoate to methyl-8-nonenoate. At the highest temperatures, the formation of polyunsaturated species was observed: 1,3-butadiene, 1,3-cyclopentadiene, benzene, toluene, indene, and naphthalene. These results were compared with previous ones about the pyrolysis of n-dodecane, an n-alkane of similar size. The reactivity of both molecules was found to be very close. The alkane produces more olefins while the ester yields unsaturated oxygenated compounds. A detailed kinetic model for the thermal decomposition of methyl decanoate has been generated using the version of software EXGAS which was updated to take into account the specific chemistry involved in the oxidation of methyl esters. This model contains 324 species and 3231 reactions. It provided a very good prediction of the experimental data obtained in jet-stirred reactor. The formation of the major products was analyzed. The kinetic analysis showed that the retro-ene reactions of intermediate unsaturated methyl esters are of importance in low reactivity systems. PMID:23710078

Quantum Chemical Investigation on Photochemical Reactions of Nonanoic Acids at Air-Water Interface.

PubMed

Xiao, Pin; Wang, Qian; Fang, Wei-Hai; Cui, Ganglong

2017-06-08

Photoinduced chemical reactions of organic compounds at the marine boundary layer have recently attracted significant experimental attention because this kind of photoreactions has been proposed to have substantial impact on local new particle formation and their photoproducts could be a source of secondary organic aerosols. In this work, we have employed first-principles density functional theory method combined with cluster models to systematically explore photochemical reaction pathways of nonanoic acids (NAs) to form volatile saturated and unsaturated C 9 and C 8 aldehydes at air-water interfaces. On the basis of the results, we have found that the formation of C 9 aldehydes is not initiated by intermolecular Norrish type II reaction between two NAs but by intramolecular T 1 C-O bond fission of NA generating acyl and hydroxyl radicals. Subsequently, saturated C 9 aldehydes are formed through hydrogenation reaction of acyl radical by another intact NA. Following two dehydrogenation reactions, unsaturated C 9 aldehydes are generated. In parallel, the pathway to C 8 aldehydes is initiated by T 1 C-C bond fission of NA, which generates octyl and carboxyl radicals; then, an octanol is formed through recombination reaction of octyl with hydroxyl radical. In the following, two dehydrogenation reactions result into an enol intermediate from which saturated C 8 aldehydes are produced via NA-assisted intermolecular hydrogen transfer. Finally, two dehydrogenation reactions generate unsaturated C 8 aldehydes. In these reactions, water and NA molecules are found to play important roles. They significantly reduce relevant reaction barriers. Our work has also explored oxygenation reactions of NA with molecular oxygen and radical-radical dimerization reactions.

Identification and geochemical significance of sulphurized fatty acids in sedimentary organic matter from the Lorca Basin, SE Spain

NASA Astrophysics Data System (ADS)

Russell, Marie; Hartgers, Walter A.; Grimalt, Joan O.

2000-11-01

The presence of free sulphurized fatty acids in various sediment types (carbonates, marls, organic-rich shales) of the Messinian of the Lorca Basin, SE Spain, is reported. These compounds are found in the majority, but not all, of the samples from this basin which also contain sulphur-bound hydrocarbons. They constitute mixtures of C 16-C 26 linear fatty acids predominated by the C 18 homologues with thiophene, thiolane, and thiane rings attached at various chain positions, with the most abundant isomers being those with ring substitution at position C-9. The dominance of these isomers points to an early sulphurization process involving octadec-9,12-dienoic acid and/or octadeca-9-enoic acid, major lipid constituents of algae. In general, the alkylthiophene fatty acids are more abundant than the alkylthiolane or alkylthiane fatty acids. The presence of the sulphur moiety and structural identification was confirmed by GC-HRMS and by desulphurization of the fatty acid fraction. Desulphurization also showed that a portion of the sulphur containing fatty acids is intermolecularly bound to the polymeric organic matter. The samples exhibiting higher proportions of macromolecularly bound fatty acids were also those showing higher abundances of alkylthiolane or alkylthiane fatty acids. The identification of these compounds shows that the original algal lipids, including the fatty acid pool, can be effectively preserved in sedimentary samples by sulphurization. However, sulphur-bonding only occurs by addition to the unsaturated carbons. Thus, only unsaturated fatty acids are preserved, constituting a major bias in terms of the original sedimentary distributions.

The molecular distribution of fine particulate organic matter emitted from Western-style fast food cooking

NASA Astrophysics Data System (ADS)

Zhao, Yunliang; Hu, Min; Slanina, Sjaak; Zhang, Yuanhang

The emissions from food cooking could be a significant contributor to atmospheric particulate organic matter (POM) and its chemical composition would vary with different cooking styles. In this study, the chemical composition of POM emitted from Western-style fast food cooking was investigated. A total of six PM 2.5 samples was collected from a commercial restaurant and determined by gas chromatography-mass spectrometry (GC-MS). It is found that the total amount of quantified compounds of per mg POM in Western-style fast food cooking is much higher than that in Chinese cooking. The predominant homologue is fatty acids, accounting for 78% of total quantified POM, with the predominant one being palmitic acid. Dicarboxylic acids display the second highest concentration in the quantified homologues with hexanedioic acid being predominant, followed by nonanedioic acid. Cmax of n-alkanes occurs at C25, but they still appear relative higher concentrations at C29 and C31. In addition, both levoglucosan and cholesterol are quantified. The relationship of concentrations of unsaturated fatty acids (C16 and C18) with a double bond at C9 position and C9 acids indicates the reduction of the unsaturated fatty acids in the emissions could form the C9 acids. Moreover, the nonlinear fit indicates that other C9 species or other compounds are also produced, except for the C9 acids. The potential candidates of tracers for the emissions from Western-fast food cooking could be: tetradecanoic acid, hexadecanoic acid, octadecanoic acid, 9-octadecenoic acid, nonanal, lactones, levoglucosan, hexanedioic acid and nonanedioic acid.

Reconnaissance investigation of petroleum products in soil and ground water at Longmire, Mount Rainier National Park, Washington, 1990

USGS Publications Warehouse

Sumioka, S.S.

1995-01-01

The removal of an underground waste-oil storage tank in Mount Rainier National Park, at Longmire, Washington, led to the discovery that soil surrounding the tank was saturated with unidentified petroleum hydrocarbons. Subsequent investigations by the National Park Service indicated that a petroleum product smelling like diesel oil was present in the unsaturated zone as far as 120 feet from the tank site. A study was conducted by the U.S. Geological Survey in cooperation with the National Park Service to determine the extent to which the petroleum hydrocarbons have affected the unsaturated zone and ground water in the Longmire area. Measurements of water levels in wells and of water-surface elevations of the Nisqually River and a wetland west of Longmire indicate that ground water does not flow from the maintenance area to the river or to the wetland. Waste oil and diesel oil were detected in soil samples from the site closest to the waste-oil storage-tank site. Diesel oil was also detected in samples from a site about 200 feet northwest of the storage-tank site. Organic compounds of undetermined origin were detected in soil samples from all of the other sites. Waste oil was not conclusively detected in any of the ground-water samples. Diesel oil was detected in water samples from the well closest to the storage tank and from a well about 200 feet west of the storage-tank site. Ground-water samples from all of the other wells contained organic compounds of undetermined origin.

The Path of Carbon in Photosynthesis XVIII. The Identification of Nucleotide Coenzymes

DOE R&D Accomplishments Database

Buchanan, J. G.; Lynch, V. H.; Benson, A. A.; Calvin, M.; Bradley, D. F.

1953-01-19

The radioactive compounds to be observed when algae or green leaves are allowed to photosynthesize in C{sup 14}O{sub 2} for short periods are almost all phosphorylated derivatives of sugars. Of these, phosphate esters of trioses, sedoheptulose and fructose are the first to incorporate C{sup 14} followed closely by ribulose diphosphate, glucose-6-phosphate and a phosphate of mannose. It has been noted, in earlier papers of this series, that on radiograms of the products of photosynthesis, a dark area appeared in a position occupied by no known sugar phosphate and which gave glucose on acid hydrolysis or on treatment with a phosphatase preparation. This has hitherto been referred to as an 'unknown glucose phosphate'. It was found that this substance was more labile to acid than glucose-l-phosphate, itself a readily hydrolysable phosphate, and furthermore that other labile glucose derivatives were formed as intermediates during the acid hydrolysis. Accumulation of labeled glucose in this area precedes that in sucrose and suggests its synthetic relationship to sucrose phosphate synthesis.

Characterization of a xylose containing oligosaccharide, an inhibitor of multidrug resistance in Staphylococcus aureus, from Ipomoea pes-caprae.

PubMed

Escobedo-Martínez, Carolina; Cruz-Morales, Sara; Fragoso-Serrano, Mabel; Rahman, M Mukhlesur; Gibbons, Simon; Pereda-Miranda, Rogelio

2010-10-01

Pescaprein XVIII (1), a type of bacterial efflux pump inhibitor, was obtained from the CHCl(3)-soluble resin glycosides of beach morning glory (Ipomoea pes-caprae). The glycosidation sequence for pescaproside C, the glycosidic acid core of the lipophilic macrolactone 1 containing D-xylose and L-rhamnose, was characterized by means of several NMR techniques and FAB mass spectrometry. Recycling HPLC also yielded eight non-cytotoxic bacterial resistance modifiers, the two pescapreins XIX (2) and XX (3) as well as the known murucoidin VI (4), pecapreins II (6) and III (7), and stoloniferins III (5), IX (8) and X (9), all of which contain simonic acid B as their oligosaccharide core. Compounds 1-9 were tested for in vitro antibacterial and resistance-modifying activity against strains of Staphylococcus aureus possessing multidrug resistance efflux mechanisms. All of the pescapreins potentiated the action of norfloxacin against the NorA over-expressing strain by 4-fold (8 microg/mL from 32 microg/mL) at a concentration of 25 microg/mL. Copyright © 2010 Elsevier Ltd. All rights reserved.

Improved forward and inverse analyses of saturated-unsaturated flow toward a well in a compressible unconfined aquifer

NASA Astrophysics Data System (ADS)

Mishra, Phoolendra Kumar; Neuman, Shlomo P.

2010-07-01

We present an analytical solution for flow to a partially penetrating well in a compressible unconfined aquifer that allows inferring its saturated and unsaturated hydraulic properties from drawdowns recorded in the saturated and/or unsaturated zone. We improve upon a previous such solution due to Tartakovsky and Neuman (2007) by (1) adopting a more flexible representation of unsaturated zone constitutive properties and (2) allowing the unsaturated zone to have finite thickness. Both solutions account for horizontal as well as vertical flows throughout the system. We investigate the effects of unsaturated zone constitutive parameters and thickness on drawdowns in the saturated and unsaturated zones as functions of position and time; demonstrate the development of significant horizontal hydraulic gradients in the unsaturated zone in response to pumping; validate our solution against numerical simulations of drawdown in a synthetic aquifer having unsaturated properties described by the van Genuchten-Mualem constitutive model; use our solution to analyze drawdown data from a pumping test conducted by the U.S. Geological Survey at Cape Cod, Massachusetts; and compare our estimates of van Genuchten-Mualem parameters with laboratory values obtained for similar materials in the area.

42 CFR 489.53 - Termination by CMS.

Code of Federal Regulations, 2010 CFR

2010-10-01

... Health CENTERS FOR MEDICARE & MEDICAID SERVICES, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) STANDARDS AND CERTIFICATION PROVIDER AGREEMENTS AND SUPPLIER APPROVAL Termination of Agreement and... is attributable to that provider: (1) It is not complying with the provisions of title XVIII and the...

22. UPSTREAM VIEW OF THE OUTLET CONTROL STRUCTURE AND THE ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

22. UPSTREAM VIEW OF THE OUTLET CONTROL STRUCTURE AND THE PIER FOR THE SERVICE BRIDGE.... Volume XVIII, No. 12, January 29, 1940. - Prado Dam, Outlet Works, Santa Ana River near junction of State Highways 71 & 91, Corona, Riverside County, CA

15. AERIAL PHOTOGRAPH OF DAM SITE SHOWING SPILLWAY OGEE SECTION ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

15. AERIAL PHOTOGRAPH OF DAM SITE SHOWING SPILLWAY OGEE SECTION AND SPILLWAY APRON EXCAVATION IN FOREGROUND.... Volume XVIII, No. 10, January 18, 1940. - Prado Dam, Spillway, Santa Ana River near junction of State Highways 71 & 91, Corona, Riverside County, CA

40 CFR 80.70 - Covered areas.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 17 2013-07-01 2013-07-01 false Covered areas. 80.70 Section 80.70 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) REGULATION OF...) Hopewell; (xvii) Richmond; (xviii) Chesapeake; (xix) Hampton; (xx) James City County; (xxi) Newport News...

40 CFR 80.70 - Covered areas.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 17 2014-07-01 2014-07-01 false Covered areas. 80.70 Section 80.70 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) REGULATION OF...) Hopewell; (xvii) Richmond; (xviii) Chesapeake; (xix) Hampton; (xx) James City County; (xxi) Newport News...

40 CFR 80.70 - Covered areas.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 17 2012-07-01 2012-07-01 false Covered areas. 80.70 Section 80.70 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) REGULATION OF...) Hopewell; (xvii) Richmond; (xviii) Chesapeake; (xix) Hampton; (xx) James City County; (xxi) Newport News...

75 FR 417 - National Protection and Programs Directorate; Statewide Communication Interoperability Plan...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-01-05

... Communication Interoperability Plan Implementation Report AGENCY: National Protection and Programs Directorate... Directorate/Cybersecurity and Communications/Office of Emergency Communications, has submitted the following... INFORMATION: The Office of Emergency Communications (OEC), formed under Title XVIII of the Homeland Security...

Diversity of compounds in femoral secretions of Galápagos iguanas (genera: Amblyrhynchus and Conolophus), and their potential role in sexual communication in lek-mating marine iguanas (Amblyrhynchus cristatus).

PubMed

Ibáñez, Alejandro; Menke, Markus; Quezada, Galo; Jiménez-Uzcátegui, Gustavo; Schulz, Stefan; Steinfartz, Sebastian

2017-01-01

Chemical signals are widely used in the animal kingdom, enabling communication in various social contexts, including mate selection and the establishment of dominance. Femoral glands, which produce and release waxy secretions into the environment, are organs of central importance in lizard chemical communication. The Galápagos marine iguana ( Amblyrhynchus cristatus ) is a squamate reptile with a lek-mating system. Although the lekking behaviour of marine iguanas has been well-studied, their potential for sexual communication via chemical cues has not yet been investigated. Here we describe the diversity of the lipophilic fraction of males' femoral gland secretions among 11 island populations of marine iguanas, and compare it with the composition of its sister species, the Galápagos land iguana ( Conolophus subcristatus ). We also conducted behavioural observations in marine iguana territorial males in order to explore the possible function of these substances in the context of male dominance in leks. Femoral secretions were analysed by gas chromatography coupled to mass spectrometry (GC-MS), and chromatography with a flame ionisation detector (GC-FID) in order to characterise the lipophilic composition. To understand the potential role of femoral secretions in marine iguana intraspecific communication, territorial males were sampled for their femoral glands and monitored to record their head bob rate-a territorial display behaviour in males-as well as the number of females present in their leks. We found that the gland secretions were composed of ten saturated and unsaturated carboxylic acids ranging in chain length between C 16 and C 24 , as well as three sterols. Cholesterol was the main compound found. Intriguingly, land iguanas have a higher diversity of lipophilic compounds, with structural group of lipids (i.e. aldehydes) entirely absent in marine iguanas; overall the chemical signals of both species were strongly differentiated. Lipid profiles also differed among populations of marine iguanas from different islands, with some islands demonstrating a high diversity of lipophilic compounds (i.e. full spectra of compounds), and others lacking one or more compounds. Among the compounds most frequently found missing were 11- and 13-eicosenoic acids. Gland secretions of males with a better body condition and with a higher dominance status (i.e. those accompanied by females and with higher head bob display) were proportionately richer in C 20 -unsaturated fatty acids (11-eicosenoic acid). Land and marine iguanas strongly diverged in their chemical composition of the femoral glands likely due to ecological differences between both species. Despite that marine iguana populations varied in their femoral gland composition that was not related to their genetic structure. Our results indicated that 11-eicosenoic acid may play an important role in intraspecific chemical communication in marine iguanas.

Modeling Coronal Response in Decaying Active Regions with Magnetic Flux Transport and Steady Heating

NASA Astrophysics Data System (ADS)

Ugarte-Urra, Ignacio; Warren, Harry P.; Upton, Lisa A.; Young, Peter R.

2017-09-01

We present new measurements of the dependence of the extreme ultraviolet (EUV) radiance on the total magnetic flux in active regions as obtained from the Atmospheric Imaging Assembly (AIA) and the Helioseismic and Magnetic Imager on board the Solar Dynamics Observatory. Using observations of nine active regions tracked along different stages of evolution, we extend the known radiance—magnetic flux power-law relationship (I\\propto {{{Φ }}}α ) to the AIA 335 Å passband, and the Fe xviii 93.93 Å spectral line in the 94 Å passband. We find that the total unsigned magnetic flux divided by the polarity separation ({{Φ }}/D) is a better indicator of radiance for the Fe xviii line with a slope of α =3.22+/- 0.03. We then use these results to test our current understanding of magnetic flux evolution and coronal heating. We use magnetograms from the simulated decay of these active regions produced by the Advective Flux Transport model as boundary conditions for potential extrapolations of the magnetic field in the corona. We then model the hydrodynamics of each individual field line with the Enthalpy-based Thermal Evolution of Loops model with steady heating scaled as the ratio of the average field strength and the length (\\bar{B}/L) and render the Fe xviii and 335 Å emission. We find that steady heating is able to partially reproduce the magnitudes and slopes of the EUV radiance—magnetic flux relationships and discuss how impulsive heating can help reconcile the discrepancies. This study demonstrates that combined models of magnetic flux transport, magnetic topology, and heating can yield realistic estimates for the decay of active region radiances with time.

Current Sheet Evolution In The Aftermath Of A CME Event

NASA Technical Reports Server (NTRS)

Bemporad, A.; Poletto, G.; Seuss, S. T.; Schwardron, N. A.; Elliott, H. A.; Raymond, J. C.

2006-01-01

We report on SOHO UVCS observations of the coronal restructuring following a coronal mass ejection (CME) on 2002 November 26, at the time of a SOHO-Ulysses quadrature campaign. Starting about 1.5 hr after a CME in the northwest quadrant, UVCS began taking spectra at 1.7 R, covering emission from both cool and hot plasma. Observations continued, with occasional gaps, for more than 2 days. Emission in the 974.8 A line of [Fe XVIII], indicating temperatures above 6 x 10(exp 6) K, was observed throughout the campaign in a spatially limited location. Comparison with EIT images shows the [Fe XVIII] emission to overlie a growing post-flare loop system formed in the aftermath of the CME. The emission most likely originates in a current sheet overlying the arcade. Analysis of the [Fe XVIII] emission allows us to infer the evolution of physical parameters in the current sheet over the entire span of our observations: in particular, we give the temperature versus time in the current sheet and estimate its density. At the time of the quadrature, Ulysses was directly above the location of the CME and intercepted the ejecta. High ionization state Fe was detected by the Ulysses SWICS throughout the magnetic cloud associated with the CME, although its rapid temporal variation suggests bursty, rather than smooth, reconnection in the coronal current sheet. The SOHO-Ulysses data set provided us with the unique opportunity of analyzing a current sheet structure from its lowest coronal levels out to its in situ properties. Both the remote and in situ observations are compared with predictions of theoretical CME models.

Evaluating the Role of Drone-Produced Chemical Signals in Mediating Social Interactions in Honey Bees (Apis mellifera).

PubMed

Villar, Gabriel; Wolfson, Megan D; Hefetz, Abraham; Grozinger, Christina M

2018-01-01

Pheromones play a critical role in shaping societies of social insects, including honey bees, Apis mellifera. While diverse functions have been ascribed to queen- and worker-produced compounds, few studies have explored the identity and function of male-produced (drone) compounds. However, several lines of evidence suggest that drones engage in a variety of social interactions inside and outside of the colony. Here we elucidate the chemical composition of extracts of the drone mandibular gland, and test the hypothesis that compounds produced in these glands, or a synthetic blend consisting of the six main compounds, mediate drone social interactions in and out of the colony. Drone mandibular glands primarily produce a blend of saturated, unsaturated and methyl branched fatty acids ranging in chain length from nonanoic to docosanoic acids, and both gland extracts and synthetic blends of these chemicals serve to attract drones outside of the hive, but do not attract workers inside the hive. These studies shed light on the role drones and drone-produced chemicals have on mediating social interactions with other drones and highlight their potential importance in communicating with other castes.

Cuticular hydrocarbons as sex pheromone of the bee Colletes cunicularius and the key to its mimicry by the sexually deceptive orchid, Ophrys exaltata.

PubMed

Mant, Jim; Brändli, Christoph; Vereecken, Nicolas J; Schulz, Claudia M; Francke, Wittko; Schiestl, Florian P

2005-08-01

Male Colletes cunicularius bees pollinate the orchid, Ophrys exaltata, after being sexually deceived by the orchid's odor-mimicry of the female bee's sex pheromone. We detected biologically active volatiles of C. cunicularius by using gas chromatographic-electroantennographic detection (GC-EAD) with simultaneous flame ionization detection. After identification of the target compounds by coupled gas chromatography mass spectrometry (GC-MS), we performed behavioral tests using synthetic blends of the active components. We detected 22 EAD active compounds in cuticular extracts of C. cunicularius females. Blends of straight chain, odd-numbered alkanes and (Z)-7-alkenes with 21-29 carbon atoms constituted the major biologically active compounds. Alkenes were the key compounds releasing mating behavior, especially those with (Z)-7 unsaturation. Comparison of patterns of bee volatiles with those of O. exaltata subsp. archipelagi revealed that all EAD-active compounds were also found in extracts of orchid labella. Previous studies of the mating behavior in C. cunicularius showed linalool to be an important attractant for patrolling males. We confirmed this with synthetic linalool but found that it rarely elicited copulatory behavior, in accordance with previous studies. A blend of active cuticular compounds with linalool elicited both attraction and copulation behavior in patrolling males. Thus, linalool appears to function as a long-range attractant, whereas cuticular hydrocarbons are necessary for inducing short-range mating behavior.

Biotechnological production of aromatic compounds of the extended shikimate pathway from renewable biomass.

PubMed

Lee, Jin-Ho; Wendisch, Volker F

2017-09-10

Aromatic chemicals that contain an unsaturated ring with alternating double and single bonds find numerous applications in a wide range of industries, e.g. paper and dye manufacture, as fuel additives, electrical insulation, resins, pharmaceuticals, agrochemicals, in food, feed and cosmetics. Their chemical production is based on petroleum (BTX; benzene, toluene, and xylene), but they can also be obtained from plants by extraction. Due to petroleum depletion, health compliance, or environmental issues such as global warming, the biotechnological production of aromatics from renewable biomass came more and more into focus. Lignin, a complex polymeric aromatic molecule itself, is a natural source of aromatic compounds. Many microorganisms are able to catabolize a plethora of aromatic compounds and interception of these pathways may lead to the biotechnological production of value-added aromatic compounds which will be discussed for Corynebacterium glutamicum. Biosynthesis of aromatic amino acids not only gives rise to l-tryptophan, L-tyrosine and l-phenylalanine, but also to aromatic intermediates such as dehydroshikimate or chorismate from which value-added aromatic compounds can be derived. In this review, we will summarize recent strategies for the biotechnological production of aromatic and related compounds from renewable biomass by Escherichia coli, Pseudomonas putida, C. glutamicum and Saccharomyces cerevisiae. In particular, we will focus on metabolic engineering of the extended shikimate pathway. Copyright © 2016 Elsevier B.V. All rights reserved.

Milk fatty acid unsaturation: genetic parameters and effects of stearoyl-CoA desaturase (SCD1) and acyl CoA: diacylglycerol acyltransferase 1 (DGAT1).

PubMed

Schennink, A; Heck, J M L; Bovenhuis, H; Visker, M H P W; van Valenberg, H J F; van Arendonk, J A M

2008-05-01

With regard to human health aspects of milk fat, increasing the amount of unsaturated fatty acids in milk is an important selection objective. The cow's diet has an influence on the degree of unsaturation, but literature suggests that genetics also plays a role. To estimate genetic variation in milk fatty acid unsaturation indices, milk fatty acid composition of 1,933 Dutch Holstein Friesian heifers was measured and unsaturation indices were calculated. An unsaturation index represents the concentration of the unsaturated product proportional to the sum of the unsaturated product and the saturated substrate. Intraherd heritabilities were moderate, ranging from 0.23 +/- 0.07 for conjugated linoleic acid (CLA) index to 0.46 +/- 0.09 for C16 index. We genotyped the cows for the SCD1 A293V and DGAT1 K232A polymorphisms, which are known to alter milk fatty acid composition. Both genes explain part of the genetic variation in unsaturation indices. The SCD1 V allele is associated with lower C10, C12, and C14 indices, and with higher C16, C18, and CLA indices in comparison to the SCD1 A allele, with no differences in total unsaturation index. In comparison to the DGAT1 K allele, the DGAT1 A allele is associated with lower C10, C12, C14, and C16 indices and with higher C18, CLA, and total indices. We conclude that selective breeding can contribute to higher unsaturation indices, and that selective breeding can capitalize on genotypic information of both the SCD1 A293V and the DGAT1 K232A polymorphism.

Short communication: Estimates of heritabilities and genetic correlations among milk fatty acid unsaturation indices in Canadian Holsteins.

PubMed

Bilal, G; Cue, R I; Mustafa, A F; Hayes, J F

2012-12-01

The objectives of the present study were to estimate genetic parameters of milk fatty acid unsaturation indices in Canadian Holsteins. Data were available on milk fatty acid composition of 2,573 Canadian Holstein cows from 46 commercial herds enrolled in the Québec Dairy Production Centre of Expertise, Valacta (Sainte-Anne-de-Bellevue, Quebec, Canada). Individual fatty acid percentages (g/100 g of total fatty acids) were determined for each milk sample by gas chromatography. The unsaturation indices were calculated as the ratio of an unsaturated fatty acid to the sum of that unsaturated fatty acid and its corresponding substrate fatty acid, multiplied by 100. A mixed linear model was fitted under REML for the statistical analysis of milk fatty acid unsaturation indices. The statistical model included the fixed effects of parity, age at calving, and stage of lactation, each nested within parity, and the random effects of herd-year-season of calving, animal, and residual. Estimates of heritabilities for the C14, C16, C18, conjugated linoleic acid, and total unsaturation indices were 0.48, 0.25, 0.29, 0.14, and 0.19, respectively. Phenotypic and genetic correlation estimates among unsaturation indices were all positive and ranged from 0.20 to 0.65 and 0.23 to 0.81, respectively. The estimates of heritabilities and genetic correlations for milk fatty acid unsaturation indices suggest that genetic variation exists among cows in milk fatty acid unsaturation, and the proportions of desirable unsaturated fatty acids from a human health point of view may be increased in bovine milk through genetic selection. Copyright © 2012 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Enantioselective copper-catalyzed carboetherification of unactivated alkenes.

PubMed

Bovino, Michael T; Liwosz, Timothy W; Kendel, Nicole E; Miller, Yan; Tyminska, Nina; Zurek, Eva; Chemler, Sherry R

2014-06-16

Chiral saturated oxygen heterocycles are important components of bioactive compounds. Cyclization of alcohols onto pendant alkenes is a direct route to their synthesis, but few catalytic enantioselective methods enabling cyclization onto unactivated alkenes exist. Herein reported is a highly efficient copper-catalyzed cyclization of γ-unsaturated pentenols which terminates in C-C bond formation, a net alkene carboetherification. Both intra- and intermolecular C-C bond formations are demonstrated, thus yielding functionalized chiral tetrahydrofurans as well as fused-ring and bridged-ring oxabicyclic products. Transition-state calculations support a cis-oxycupration stereochemistry-determining step. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Radiation cured polyester compositions containing metal-properties

NASA Astrophysics Data System (ADS)

Szalińska, H.; Pietrzak, M.; Gonerski, A.

The subject of the studies was unsaturated polyester resin, Polimal-109 and its compositions containing acrylates of: sodium, potassium, calcium, magnesium, barium, manganese, iron, cobalt, copper and acrylic acid. Polyester resin modified with acrylic acid salts was cured with 60Co gamma radiation. Measurements of Vicat softening temperature, water absorption, creep current resistance, volume and surface resistivity, the tangent of dielectric loss angle and permittivity of radiation cured compositions were carried out. The results of the studies presented testify to the fact that the properties of cross-linked polymers alter after ionogenic compounds have been introduced into them.

Synthesis, biological evaluation, and metabolic stability of chlorogenic acid derivatives possessing thiazole as potent inhibitors of α-MSH-stimulated melanogenesis.

PubMed

Jo, Hyeju; Zhou, Yuanyuan; Viji, Mayavan; Choi, Minho; Lim, Jae Young; Sim, Jaeuk; Rhee, Jeongtae; Kim, Youngsoo; Seo, Seung-Yong; Kim, Wun-Jae; Hong, Jin Tae; Lee, Heesoon; Lee, Kiho; Jung, Jae-Kyung

2017-11-01

A series of catechol and dioxolane analogs containing thiazole CGA derivatives have been synthesized and evaluated for their inhibitory activity against α-MSH. The inhibitory activity was improved by replacing an α,β-unsaturated carbonyl of previously reported caffeamides with thiazole motif. Surprisingly, compound 7d, one of the derivatives of dioxolane analogs, displayed the most potent inhibitory activity with an IC 50 of 0.90μM. Further studies on metabolic stability and bioactivation potential were also accomplished. Copyright © 2017 Elsevier Ltd. All rights reserved.

[Component and content changes of volatiles from Chinese cabbage damaged by Plutella xylostella].

PubMed

Yang, Guang; You, Minsheng; Wei, Hui

2004-11-01

The study showed that Chinese cabbage, Brassica campestris could release a variety of volatiles, especially when infested by Plutella xylostella larvae. Among these volatiles, saturated hydrocarbon was dominant, aromatic hydrocarbon was the second, and unsaturated hydrocarbon, aldehyde, alcohol, ketone, acid and heteroaromatic compounds were existed with a small amount. Chinese cabbage damaged by Plutella xylostella larvae produced 3 times of volatiles in amount with more species than the control. The volatiles from control plants were mostly of small molecular weight, and those from Chinese cabbage damaged by Plutella xylostella were mostly of high molecular weight.

[4 + 3] Cycloaddition of aromatic α,β-unsaturated aldehydes and ketones with epoxides: one-step approach to synthesize seven-membered oxacycles catalyzed by Lewis acid.

PubMed

Zhou, Yu-Qiang; Wang, Nai-Xing; Zhou, Shu-Bao; Huang, Zhong; Cao, Linghua

2011-01-21

A novel intermolecular [4 + 3] cycloaddition method to construct 1,4-dioxide seven-membered oxacycles was developed. This one-step method was carried out in the presence of catalytic amount of (C(2)H(5))(2)OBF(3) under mild conditions. Seven-membered oxacycles and some natural compounds could be easily synthesized via this protocol. Control experiments were carried out and possible mechanism for the reaction was proposed. Asymmetric reactions were proceeded and 3e was obtained with moderate ee value.

Documentation of the Streamflow-Routing (SFR2) Package to Include Unsaturated Flow Beneath Streams - A Modification to SFR1

USGS Publications Warehouse

Niswonger, Richard G.; Prudic, David E.

2005-01-01

Many streams in the United States, especially those in semiarid regions, have reaches that are hydraulically disconnected from underlying aquifers. Ground-water withdrawals have decreased water levels in valley aquifers beneath streams, increasing the occurrence of disconnected streams and aquifers. The U.S. Geological Survey modular ground-water model (MODFLOW-2000) can be used to model these interactions using the Streamflow-Routing (SFR1) Package. However, the approach does not consider unsaturated flow between streams and aquifers and may not give realistic results in areas with significantly deep unsaturated zones. This documentation describes a method for extending the capabilities of MODFLOW-2000 by incorporating the ability to simulate unsaturated flow beneath streams. A kinematic-wave approximation to Richards' equation was solved by the method of characteristics to simulate unsaturated flow beneath streams in SFR1. This new package, called SFR2, includes all the capabilities of SFR1 and is designed to be used with MODFLOW-2000. Unlike SFR1, seepage loss from the stream may be restricted by the hydraulic conductivity of the unsaturated zone. Unsaturated flow is simulated independently of saturated flow within each model cell corresponding to a stream reach whenever the water table (head in MODFLOW) is below the elevation of the streambed. The relation between unsaturated hydraulic conductivity and water content is defined by the Brooks-Corey function. Unsaturated flow variables specified in SFR2 include saturated and initial water contents; saturated vertical hydraulic conductivity; and the Brooks-Corey exponent. These variables are defined independently for each stream reach. Unsaturated flow in SFR2 was compared to the U.S. Geological Survey's Variably Saturated Two-Dimensional Flow and Transport (VS2DT) Model for two test simulations. For both test simulations, results of the two models were in good agreement with respect to the magnitude and downward progression of a wetting front through an unsaturated column. A third hypothetical simulation is presented that includes interaction between a stream and aquifer separated by an unsaturated zone. This simulation is included to demonstrate the utility of unsaturated flow in SFR2 with MODFLOW-2000. This report includes a description of the data input requirements for simulating unsaturated flow in SFR2.

Quantifying Preferential Flow and Seasonal Storage in an Unsaturated Fracture-Facial Domain

NASA Astrophysics Data System (ADS)

Nimmo, J. R.; Malek-Mohammadi, S.

2012-12-01

Preferential flow through deep unsaturated zones of fractured rock is hydrologically important to a variety of contaminant transport and water-resource issues. The unsaturated zone of the English Chalk Aquifer provides an important opportunity for a case study of unsaturated preferential flow in isolation from other flow modes. The chalk matrix has low hydraulic conductivity and stays saturated, owing to its fine uniform pores and the wet climate of the region. Therefore the substantial fluxes observed in the unsaturated chalk must be within fractures and interact minimally with matrix material. Price et al. [2000] showed that irregularities on fracture surfaces provide a significant storage capacity in the chalk unsaturated zone, likely accounting for volumes of water required to explain unexpected dry-season water-table stability during substantial continuing streamflow observed by Lewis et al. [1993] In this presentation we discuss and quantify the dynamics of replenishment and drainage of this unsaturated zone fracture-face storage domain using a modification of the source-responsive model of Nimmo [2010]. This model explains the processes in terms of two interacting flow regimes: a film or rivulet preferential flow regime on rough fracture faces, active on an individual-storm timescale, and a regime of adsorptive and surface-tension influences, resembling traditional diffuse formulations of unsaturated flow, effective mainly on a seasonal timescale. The modified model identifies hydraulic parameters for an unsaturated fracture-facial domain lining the fractures. Besides helping to quantify the unsaturated zone storage described by Price et al., these results highlight the importance of research on the topic of unsaturated-flow relations within a near-fracture-surface domain. This model can also facilitate understanding of mechanisms for reinitiation of preferential flow after temporary cessation, which is important in multi-year preferential flow through deep unsaturated zones [Pruess, 1999]. Lewis, M.A., H.K. Jones, D.M.J. Macdonald, M. Price, J.A. Barker, T.R. Shearer, A.J. Wesselink, and D.J. Evans (1993), Groundwater storage in British aquifers--Chalk, National Rivers Authority R&D Note, 169, Bristol, UK. Nimmo, J.R. (2010), Theory for Source-Responsive and Free-Surface Film Modeling of Unsaturated Flow, Vadose Zone Journal, 9(2), 295-306, doi:10.2136/vzj2009.0085. Price, M., R.G. Low, and C. McCann (2000), Mechanisms of water storage and flow in the unsaturated zone of the Chalk aquifer, Journal of Hydrology, 233(1-4), 54-71. Pruess, K. (1999), A mechanistic model for water seepage through thick unsaturated zones in fractured rocks of low matrix permeability, Water Resources Research, 35(4), 1039-1051.

20 CFR 410.561c - Defeat the purpose of title IV.

Code of Federal Regulations, 2010 CFR

2010-04-01

... Section 410.561c Employees' Benefits SOCIAL SECURITY ADMINISTRATION FEDERAL COAL MINE HEALTH AND SAFETY..., accident, and health insurance including premiums for supplementary medical insurance benefits under title XVIII of the Social Security Act), taxes, installment payments, etc.; (2) Medical, hospitalization, and...

20 CFR 401.25 - Terms defined.

Code of Federal Regulations, 2013 CFR

2013-04-01

... information about an individual, and includes, but is not limited to, vital statistics; race, sex, or other... psychological or psychiatric information or lay information used in a medical determination; and information..., XVI, and XVIII of the Act; and (2) units of State governments which make determinations under...

[Concept and history of public health in Mexico (XVIII to XX century)].

PubMed

Fierros Hernández, Arturo

2014-01-01

This paper is a brief history of public health. I review the concept of public health and its origins in the West, and also analyze the input of politics in the Mexican health system through the government of Porfirio Diaz.

42 CFR 476.86 - Correlation of Title XI functions with Title XVIII functions.

Code of Federal Regulations, 2010 CFR

2010-10-01

... functions. 476.86 Section 476.86 Public Health CENTERS FOR MEDICARE & MEDICAID SERVICES, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) QUALITY IMPROVEMENT ORGANIZATIONS UTILIZATION AND QUALITY CONTROL REVIEW Review Responsibilities of Utilization and Quality Control Quality Improvement Organizations (QIOs...

Evidence of a louse-borne outbreak involving typhus in Douai, 1710-1712 during the war of Spanish succession.

PubMed

Nguyen-Hieu, Tung; Aboudharam, Gérard; Signoli, Michel; Rigeade, Catherine; Drancourt, Michel; Raoult, Didier

2010-10-27

The new field of paleomicrobiology allows past outbreaks to be identified by testing dental pulp of human remains with PCR. We identified a mass grave in Douai, France dating from the early XVIII(th) century. This city was besieged during the European war of Spanish succession. We tested dental pulp from 1192 teeth (including 40 from Douai) by quantitative PCR (qPCR) for R. prowazekii and B. quintana. We also used ultra-sensitive suicide PCR to detect R. prowazekii and genotyped positive samples. In the Douai remains, we identified one case of B. quintana infection (by qPCR) and R. prowazekii (by suicide PCR) in 6/21 individuals (29%). The R. prowazekii was genotype B, a genotype previously found in a Spanish isolate obtained in the first part of the XX(th) century. Louse-borne outbreaks were raging during the XVIII(th) century; our results support the hypothesis that typhus was imported into Europe by Spanish soldiers from America.

Long-term trend of dicarboxylic acids, ketoacids and dicarbonyls in the marine aerosols over the western North Pacific in 2001-2006

NASA Astrophysics Data System (ADS)

Kawamura, K.; Tachibana, E.; Mochida, M.

2006-12-01

To understand a long-range atmospheric transport of water-soluble organics in the western North Pacific, remote marine aerosols were collected on weekly basis at a subtropical island (Chichijima, 142E; 27N) from 2001 to 2006 using a high volume air sampler and pre-combusted quartz filter. The island is located in the boundary of westerly and trade wind regimes. The aerosols were analyzed for dicarboxylic acids, ketoacids and dicarbonyls employing butyl ester derivatization followed by GC determination. Homologous saturated diacids (C2-C11) were detected with a predominance of oxalic (C2) acid followed by malonic (C3) and succinic (C4) acids as well as unsaturated diacids, including maleic (M), fumaric (F), phthalic acids. Ketoacids and dicarbonyls were also detected. Concentrations of total diacids fluctuated significantly in a range of 10-600 ngm-3 with winter/spring maximum and summer minimum. The winter/spring maximum can be explained by a combinattion of enhanced emissions of polluted aerosols and their precursors in Asia and the intensified westerlies over the North Pacific in the season. Seasonal trends of the molecular compositions were also found. For example, concentration ratios of C3 to C4 acid showed a maximum in summer, indicating more oxidation of longer-chain diacids to shorter ones. M/F ratios increased from summer to winter as a result of photochemically-induced isomerization of cis and trans configuration of unsaturated diacids. On the other hand, azelaic acid (C9) relative to other diacids showed a sharp increase in summer. Because C9 is a specific photo-oxidation product of unsaturated fatty acid such as oleic acid, this demonstrates an enhanced sea-to- air emission of unsaturated fatty acids in summer followed by photochemical oxidation. Long-term trends of diacids and related compounds in the aerosols will be discussed for 2001 to 2006. The results will also be compared with those obtained at the same site for 1990 to 1993 to detect long-term changes in the organic aerosol compositions that might be happened over the western North Pacific due to the enhanced human activity in East Asia.

Isatis tinctoria L. combined with co-stimulatory molecules blockade prolongs survival of cardiac allografts in alloantigen-primed mice.

PubMed

Kang, Xiangpeng; Chen, Jibing; Qin, Qing; Wang, Feng; Wang, Yongzhi; Lan, Tianshu; Xu, Shuo; Wang, Feiyu; Xia, Junjie; Ekberg, Henrik; Qi, Zhongquan; Liu, Zhongchen

2010-05-01

Memory T cells present a unique challenge in transplantation. Although memory T cells express robust immune responses to invading pathogens, they may be resistant to the effects of immunosuppressive therapies used to prolong graft survival. In previous studies, we found that compound K, the synthesized analogue of highly unsaturated fatty acids from Isatis tinctoria L., reduced acute cardiac allograft rejection in mice (Wang et al., 2009 [1]). Here, we further investigated the effect of compound K on cardiac allograft rejection in alloantigen-primed mice. We found that compound K significantly inhibited CD4(+) and CD8(+) memory T cells proliferation in a mixed lymphocyte reaction (MLR). In vivo, compound K combined with anti-CD154 and anti-LFA-1 monoclonal antibodies (mAbs) significantly extended the survival time of heart grafts in alloantigen-primed mice with no obvious toxic side effects. Furthermore, our data suggests that compound K works by reducing the expression of both IL-2 and IFN-gamma within the graft rather than enhancing expression of regulatory T cells (Tregs). Compound K can also inhibit the alloresponses of memory T cells, while increasing the proportion of CD4(+) memory T cells in the spleen of the recipients and significantly reducing the level of alloantibodies in the serum. Our study highlights the unique immune effects of compound K that may be further explored for clinical use in extending the survival of transplant grafts. Copyright (c) 2010 Elsevier B.V. All rights reserved.

PTP1B inhibitors from Selaginella tamariscina (Beauv.) Spring and their kinetic properties and molecular docking simulation.

PubMed

Le, Duc Dat; Nguyen, Duc Hung; Zhao, Bing Tian; Seong, Su Hui; Choi, Jae Sue; Kim, Seok Kyu; Kim, Jeong Ah; Min, Byung Sun; Woo, Mi Hee

2017-06-01

Diabetes is one of the most popular worldwide diseases, regulated by the defects in insulin secretion, insulin action, or both. The overexpression of protein tyrosine phosphatase 1B (PTP1B) was found to down-regulate the insulin-receptor activation. PTP1B has been known as a strategy for the treatment of diabetes via the regulation of insulin signal transduction pathway. Herein, we investigated the PTP1B inhibitors isolated from natural sources. The chemical investigation of Selaginella tamariscina (Beauv.) Spring revealed seven unsaturated alkynyl phenols 1-7, four new selaginellins T-W 1-4 together with three known compounds 5-7 isolated from the aerial parts. The structures of the isolates were determined by spectroscopic techniques (1D/2D-NMR, MS, and CD). The inhibitory effects of these isolates on the PTP1B enzyme activity were investigated. Among them, compounds 2-7 significantly exhibited the inhibitory effects with the IC 50 values ranging from 4.8 to 15.9μM. Compound 1 moderately displayed the inhibitory activity with an IC 50 of 57.9μM. Furthermore, active compounds were discovered from their kinetic and molecular docking analysis. The results revealed that compounds 2 and 4-7 were mixed-competitive inhibitors, whereas compound 3 was a non-competitive inhibitor. This data confirm that these compounds exhibited potential inhibitory effect on the PTP1B enzyme activity. Copyright © 2017 Elsevier Inc. All rights reserved.

Application of response surface methodology to optimise supercritical carbon dioxide extraction of volatile compounds from Crocus sativus.

PubMed

Shao, Qingsong; Huang, Yuqiu; Zhou, Aicun; Guo, Haipeng; Zhang, Ailian; Wang, Yong

2014-05-01

Crocus sativus has been used as a traditional Chinese medicine for a long time. The volatile compounds of C. sativus appear biologically active and may act as antioxidants as well as anticonvulsants, antidepressants and antitumour agents. In order to obtain the highest possible yield of essential oils from C. sativus, response surface methodology was employed to optimise the conditions of supercritical fluid carbon dioxide extraction of the volatile compounds from C. sativus. Four factorswere investigated: temperature, pressure, extraction time and carbon dioxide flow rate. Furthermore, the chemical compositions of the volatile compounds extracted by supercritical fluid extraction were compared with those obtained by hydro-distillation and Soxhlet extraction. The optimum extraction conditions were found to be: optimised temperature 44.9°C, pressure 34.9 MPa, extraction time 150.2 min and CO₂ flow rate 10.1 L h⁻¹. Under these conditions, the mean extraction yield was 10.94 g kg⁻¹. The volatile compounds extracted by supercritical fluid extraction and Soxhlet extraction contained a large amount of unsaturated fatty acids. Response surface methodology was successfully applied for supercritical fluid CO₂ extraction optimisation of the volatile compounds from C. sativus. The study showed that pressure and CO₂ flow rate had significant effect on volatile compounds yield produced by supercritical fluid extraction. This study is beneficial for the further research operating on a large scale. © 2013 Society of Chemical Industry.

Structural changes in plastids of developing Splachnum ampullaceum sporophytes and relationship to odour production.

PubMed

McCuaig, B; Dufour, S C; Raguso, R A; Bhatt, A P; Marino, P

2015-03-01

Many mosses of the family Splachnaceae are entomophilous and rely on flies for spore dispersal. Splachnum ampullaceum produces a yellow- or pink-coloured hypophysis that releases volatile compounds, attracting flies to the mature moss. The biosynthetic sources of the visual and aromatic cues within the hypophysis have not been identified, and may be either symbiotic cyanobacteria or chromoplasts that break down lipids into volatile compounds. Here, we used transmission electron microscopy and gas chromatography-mass spectrometry (GC-MS) to investigate the sources of these attractants, focusing on different tissues and stages of maturation. Microscopy revealed an abundance of plastids within the hypophysis, while no symbiotic bacteria were observed. During plant maturation, plastids differentiated from amyloplasts with large starch granules to photosynthetic chloroplasts and finally to chromoplasts with lipid accumulations. We used GC-MS to identify over 50 volatile organic compounds from mature sporophytes including short-chain oxygenated compounds, unsaturated irregular terpenoids, fatty acid-derived 6- and 8-carbon alcohols and ketones, and the aromatic compounds acetophenone and p-cresol. The hypophysis showed localised production of pungent volatiles, mainly short-chain fermentation compounds and p-cresol. Some of these volatiles have been shown to be produced from lipid oxidase degradation of linolenic acid within chromoplasts. However, other compounds (such as cyclohexanecarboxylic acid esters) may have a microbial origin. Further investigation is necessary to identify the origin of fly attractants in these mosses. © 2014 German Botanical Society and The Royal Botanical Society of the Netherlands.

The chemistry of gamete attraction: chemical structures, biosynthesis, and (a)biotic degradation of algal pheromones.

PubMed Central

Boland, W

1995-01-01

Female gametes of marine brown algae release and/or attract their conspecific males by chemical signals. The majority of these compounds are unsaturated, nonfunctionalized acyclic, and/or alicyclic C11 hydrocarbons. Threshold concentrations for release and attraction are generally observed in the range of 1-1000 pmol. The blends may contain various configurational isomers of the genuine pheromones as well as mixtures of enantiomers. Higher plants produce the C11 hydrocarbons from dodeca-3,6,9-trienoic acid; brown algae exploit the family of icosanoids for biosynthesis of the same compounds. The biosynthetic routes comprise several spontaneously occurring pericyclic reactions such as [3.3]-sigmatropic rearrangements, [1.7]-hydrogen shifts, and electrocyclic ring closures. All pheromones are (a)biotically degraded by ubiquitous oxidative pathways involving singlet oxygen or hydroxyl radicals, which may be produced through the agency of heavy metals, huminic acids, or light. PMID:7816845

Chemical Constitution of the Host-Specific Toxin of Helminthosporium carbonum1

PubMed Central

Pringle, Ross B.

1970-01-01

The host-specific toxin of Helminthosporium carbonum Ullstrup has a molecular formula approximating C32H50N6O10. The compound has been crystallized and a crystalline hydrochloride derivative has been produced. The molecular weight, as determined by chromatography on Sephadex G-10, is slightly less than 700. The toxin appears to be a cyclic peptide, since, although it does not react with ninhydrin or dinitrofluorobenzene, it yields, on hydrolysis, compounds which react to these reagents. It is unstable in dilute acids, yielding ninhydrin-reacting products. Complete acid hydrolysis yields alanine, proline, and three other ninhydrin-reacting components. The infrared spectrum of the toxin reveals an ester band in addition to amide absorption. Its ultraviolet spectrum reveals the presence of unsaturation in the molecule. The toxin is relatively unstable and loses its specific toxicity. This loss of activity appears to be associated with loss of nitrogen and with decreased solubility in water. PMID:5481091

Chemical constitution of the host-specific toxin of Helminthosporium carbonum.

PubMed

Pringle, R B

1970-07-01

The host-specific toxin of Helminthosporium carbonum Ullstrup has a molecular formula approximating C(32)H(50)N(6)O(10). The compound has been crystallized and a crystalline hydrochloride derivative has been produced. The molecular weight, as determined by chromatography on Sephadex G-10, is slightly less than 700. The toxin appears to be a cyclic peptide, since, although it does not react with ninhydrin or dinitrofluorobenzene, it yields, on hydrolysis, compounds which react to these reagents. It is unstable in dilute acids, yielding ninhydrin-reacting products. Complete acid hydrolysis yields alanine, proline, and three other ninhydrin-reacting components. The infrared spectrum of the toxin reveals an ester band in addition to amide absorption. Its ultraviolet spectrum reveals the presence of unsaturation in the molecule. The toxin is relatively unstable and loses its specific toxicity. This loss of activity appears to be associated with loss of nitrogen and with decreased solubility in water.

Sustainable Materials for Sustainable Energy Storage: Organic Na Electrodes

PubMed Central

Oltean, Viorica-Alina; Renault, Stéven; Valvo, Mario; Brandell, Daniel

2016-01-01

In this review, we summarize research efforts to realize Na-based organic materials for novel battery chemistries. Na is a more abundant element than Li, thereby contributing to less costly materials with limited to no geopolitical constraints while organic electrode materials harvested from biomass resources provide the possibility of achieving renewable battery components with low environmental impact during processing and recycling. Together, this can form the basis for truly sustainable electrochemical energy storage. We explore the efforts made on electrode materials of organic salts, primarily carbonyl compounds but also Schiff bases, unsaturated compounds, nitroxides and polymers. Moreover, sodiated carbonaceous materials derived from biomasses and waste products are surveyed. As a conclusion to the review, some shortcomings of the currently investigated materials are highlighted together with the major limitations for future development in this field. Finally, routes to move forward in this direction are suggested. PMID:28773272

Mannich Bases: An Important Pharmacophore in Present Scenario

PubMed Central

Sharma, Neha; Kajal, Anu; Saini, Vipin

2014-01-01

Mannich bases are the end products of Mannich reaction and are known as beta-amino ketone carrying compounds. Mannich reaction is a carbon-carbon bond forming nucleophilic addition reaction and is a key step in synthesis of a wide variety of natural products, pharmaceuticals, and so forth. Mannich reaction is important for the construction of nitrogen containing compounds. There is a number of aminoalkyl chain bearing Mannich bases like fluoxetine, atropine, ethacrynic acid, trihexyphenidyl, and so forth with high curative value. The literature studies enlighten the fact that Mannich bases are very reactive and recognized to possess potent diverse activities like anti-inflammatory, anticancer, antifilarial, antibacterial, antifungal, anticonvulsant, anthelmintic, antitubercular, analgesic, anti-HIV, antimalarial, antipsychotic, antiviral activities and so forth. The biological activity of Mannich bases is mainly attributed to α, β-unsaturated ketone which can be generated by deamination of hydrogen atom of the amine group. PMID:25478226

Chinese Herbal Medicines as Potential Agents for Alleviation of Heat Stress in Poultry

PubMed Central

MD Saadand, Salwani; Idrus, Zulkifli; Diao, Xiao Ping

2017-01-01

Heat stress negatively affects the productivity of chickens in commercial poultry farms in humid tropics. In this study, the concentrations and types of the antioxidant compounds of eight Chinese herbal medicines, which have previously demonstrated promising effects on suppressing heat stress as a mixture, were investigated using reversed-phase High Performance Liquid Chromatography, spectrophotometry, Liquid Chromatography Mass Spectrometry, and Gas-Liquid Chromatography. Our results provided the levels of phenolic compounds, total amounts of sugars, and total unsaturated fatty acids in the herbal extracts. Apart from the detection and quantification of the active ingredients of herbs that have the potential to mitigate heat stress in poultry, results of this study also provide useful data for developing an efficient and accurate formulation of the herbs' mixtures in order to induce positive effects against heat stress in in vivo studies. PMID:29209556

Sustainable Materials for Sustainable Energy Storage: Organic Na Electrodes.

PubMed

Oltean, Viorica-Alina; Renault, Stéven; Valvo, Mario; Brandell, Daniel

2016-03-01

In this review, we summarize research efforts to realize Na-based organic materials for novel battery chemistries. Na is a more abundant element than Li, thereby contributing to less costly materials with limited to no geopolitical constraints while organic electrode materials harvested from biomass resources provide the possibility of achieving renewable battery components with low environmental impact during processing and recycling. Together, this can form the basis for truly sustainable electrochemical energy storage. We explore the efforts made on electrode materials of organic salts, primarily carbonyl compounds but also Schiff bases, unsaturated compounds, nitroxides and polymers. Moreover, sodiated carbonaceous materials derived from biomasses and waste products are surveyed. As a conclusion to the review, some shortcomings of the currently investigated materials are highlighted together with the major limitations for future development in this field. Finally, routes to move forward in this direction are suggested.

Treponemycin, a nitrile antibiotic active against Treponema hyodysenteriae.

PubMed

Singh, S K; Gurusiddaiah, S; Whalen, J W

1985-02-01

Two strains of Streptomyces sp. (isolates 275 and 124) were isolated from soil samples collected from the fields around Lewiston, Idaho. Based on their cellular morphology and physiology, the two isolates were identified as Streptomyces albovinaceous. Both isolates produced an antibiotic when grown in liquid culture medium containing homogenized oats. The antibiotic (treponemycin) was isolated from the culture broth by solvent extraction and purified by silica gel column and preparative thin-layer chromatographies. Treponemycin is a crystalline light-yellow compound with an mp of 93 to 95 degrees C, levorotatory, and soluble in most organic solvents. It is sparingly soluble in water but insoluble in petroleum ether. On the basis of elemental analysis and mass spectral data, the molecular formula of the antibiotic was deduced to be C28H43O6N. The infrared spectrum of the antibiotic indicated the presence of unsaturation, nitrile, lactone, or ester or all three functions, and carbonyl functions in the molecule. A sharp infrared absorption band for nitrile at 2,220 cm-1 and the presence of an unsaturated group indicated that the nitrile function may be attached to an unsaturated carbon atom. The presence of dienenitrile functions was further supported by the UV absorption spectrum of the antibiotic, which gave a UVmax at 257 nm. The proton magnetic resonance spectrum of the antibiotic did not give any peak which could be exchanged with deuterated water, which is an indication of the absence of carboxylic and hydroxyl functions in the molecule. All of the functional groupings indicated by the infrared and UV spectra of the molecule were further confirmed by the 13C-magnetic resonance spectrum of the compound. A brief hydrogenation of the antibiotic yielded a biologically active tetrahydro derivative, whereas extended hydrogenation produced an inactive primary amine. Mild alkaline hydrolysis and subsequent esterification of the antibiotic with diazomethane produced an inactive dimethyl ester. Apparently both the nitrile and the lactone functions are essential for the treponomycin molecule to show antimicrobial activity. The antibiotic showed inhibitory activity against several species of bacteria, especially Treponema hyodysenteriae, the causative agent of swine dysentery. In view of the oral 50% lethal dose of 400 mg/g and its low MIC against four stains of T.hyodysenteriae, the antibiotic may have value as a swine dysentery therapeutic.

Treponemycin, a nitrile antibiotic active against Treponema hyodysenteriae.

PubMed Central

Singh, S K; Gurusiddaiah, S; Whalen, J W

1985-01-01

Two strains of Streptomyces sp. (isolates 275 and 124) were isolated from soil samples collected from the fields around Lewiston, Idaho. Based on their cellular morphology and physiology, the two isolates were identified as Streptomyces albovinaceous. Both isolates produced an antibiotic when grown in liquid culture medium containing homogenized oats. The antibiotic (treponemycin) was isolated from the culture broth by solvent extraction and purified by silica gel column and preparative thin-layer chromatographies. Treponemycin is a crystalline light-yellow compound with an mp of 93 to 95 degrees C, levorotatory, and soluble in most organic solvents. It is sparingly soluble in water but insoluble in petroleum ether. On the basis of elemental analysis and mass spectral data, the molecular formula of the antibiotic was deduced to be C28H43O6N. The infrared spectrum of the antibiotic indicated the presence of unsaturation, nitrile, lactone, or ester or all three functions, and carbonyl functions in the molecule. A sharp infrared absorption band for nitrile at 2,220 cm-1 and the presence of an unsaturated group indicated that the nitrile function may be attached to an unsaturated carbon atom. The presence of dienenitrile functions was further supported by the UV absorption spectrum of the antibiotic, which gave a UVmax at 257 nm. The proton magnetic resonance spectrum of the antibiotic did not give any peak which could be exchanged with deuterated water, which is an indication of the absence of carboxylic and hydroxyl functions in the molecule. All of the functional groupings indicated by the infrared and UV spectra of the molecule were further confirmed by the 13C-magnetic resonance spectrum of the compound. A brief hydrogenation of the antibiotic yielded a biologically active tetrahydro derivative, whereas extended hydrogenation produced an inactive primary amine. Mild alkaline hydrolysis and subsequent esterification of the antibiotic with diazomethane produced an inactive dimethyl ester. Apparently both the nitrile and the lactone functions are essential for the treponomycin molecule to show antimicrobial activity. The antibiotic showed inhibitory activity against several species of bacteria, especially Treponema hyodysenteriae, the causative agent of swine dysentery. In view of the oral 50% lethal dose of 400 mg/g and its low MIC against four stains of T.hyodysenteriae, the antibiotic may have value as a swine dysentery therapeutic. Images PMID:3838636

Korean Red Ginseng water extract inhibits COX-2 expression by suppressing p38 in acrolein-treated human endothelial cells

PubMed Central

Lee, Seung Eun; Park, Yong Seek

2013-01-01

Cigarette smoke is considered a major risk factor for vascular diseases. There are many toxic compounds in cigarette smoke, including acrolein and other α,β-unsaturated aldehydes, which are regarded as mediators of inflammation and vascular dysfunction. Furthermore, recent studies have revealed that acrolein, an α,β-unsaturated aldehyde in cigarette smoke, induces inflammatory mediator expression, which is known to be related to vascular diseases. In this study, we investigated whether Korean Red Ginseng (KRG) water extract suppressed acrolein-induced cyclooxygenase (COX)-2 expression in human umbilical vein endothelial cells (HUVECs). Acrolein-induced COX-2 expression was accompanied by increased levels of phosphorylated p38 in HUVECs and KRG inhibited COX-2 expression in HUVECs. These results suggest that KRG suppresses acrolein-induced COX-2 expression via inhibition of the p38 mitogen-activated protein kinase signaling pathway. In addition, KRG exhibited an inhibitory effect on acrolein-induced apoptosis, as demonstrated by annexin V–propidium iodide staining and terminal deoxynucleotidyl transferase-mediated dUTP nick end-labeling assay. Consistent with these results, KRG may exert a vasculoprotective effect through inhibition of COX-2 expression in acrolein-stimulated human endothelial cells. PMID:24558308

NMR-Based Metabolomic Study on Isatis tinctoria: Comparison of Different Accessions, Harvesting Dates, and the Effect of Repeated Harvesting.

PubMed

Guldbrandsen, Niels; Kostidis, Sarantos; Schäfer, Hartmut; De Mieri, Maria; Spraul, Manfred; Skaltsounis, Alexios-Leandros; Mikros, Emmanuel; Hamburger, Matthias

2015-05-22

Isatis tinctoria is an ancient dye and medicinal plant with potent anti-inflammatory and antiallergic properties. Metabolic differences were investigated by NMR spectroscopy of accessions from different origins that were grown under identical conditions on experimental plots. For these accessions, metabolite profiles at different harvesting dates were analyzed, and single and repeatedly harvested plants were compared. Leaf samples were shock-frozen in liquid N2 immediately after being harvested, freeze-dried, and cryomilled prior to extraction. Extracts were prepared by pressurized liquid extraction with ethyl acetate and 70% aqueous methanol. NMR spectra were analyzed using a combination of different methods of multivariate data analysis such as principal component analysis (PCA), canonical analysis (CA), and k-nearest neighbor concept (k-NN). Accessions and harvesting dates were well separated in the PCA/CA/k-NN analysis in both extracts. Pairwise statistical total correlation spectroscopy (STOCSY) revealed unsaturated fatty acids, porphyrins, carbohydrates, indole derivatives, isoprenoids, phenylpropanoids, and minor aromatic compounds as the cause of these differences. In addition, the metabolite profile was affected by the repeated harvest regime, causing a decrease of 1,5-anhydroglucitol, sucrose, unsaturated fatty acids, porphyrins, isoprenoids, and a flavonoid.

Mechanism of falcipain-2 inhibition by α,β-unsaturated benzo[1,4]diazepin-2-one methyl ester

NASA Astrophysics Data System (ADS)

Grazioso, Giovanni; Legnani, Laura; Toma, Lucio; Ettari, Roberta; Micale, Nicola; De Micheli, Carlo

2012-09-01

Falcipain-2 (FP-2) is a papain-family cysteine protease of Plasmodium falciparum whose primary function is to degrade the host red cell hemoglobin, within the food vacuole, in order to provide free amino acids for parasite protein synthesis. Additionally it promotes host cell rupture by cleaving the skeletal proteins of the erythrocyte membrane. Therefore, the inhibition of FP-2 represents a promising target in the search of novel anti-malarial drugs. A potent FP-2 inhibitor, characterized by the presence in its structure of the 1,4-benzodiazepine scaffold and an α,β-unsaturated methyl ester moiety capable to react with the Cys42 thiol group located in the active site of FP-2, has been recently reported in literature. In order to study in depth the inhibition mechanism triggered by this interesting compound, we carried out, through ONIOM hybrid calculations, a computational investigation of the processes occurring when the inhibitor targets the enzyme and eventually leads to an irreversible covalent Michael adduct. Each step of the reaction mechanism has been accurately characterized and a detailed description of each possible intermediate and transition state along the pathway has been reported.

Characterization and quantification of odor-active compounds in unsaturated fatty acid/conjugated linoleic acid (UFA/CLA)-enriched butter and in conventional butter during storage and induced oxidation.

PubMed

Mallia, Silvia; Escher, Felix; Dubois, Sébastien; Schieberle, Peter; Schlichtherle-Cerny, Hedwig

2009-08-26

Dairy products enriched in unsaturated fatty acids (UFA) and conjugated linoleic acids (CLA) have a higher nutritional value and are suggested to have beneficial health effects. However, such acids are susceptible to oxidation, and off-flavors may be formed during storage. This study was aimed to compare the most important odorants in UFA/CLA-enriched butter to that of conventional butter during storage and induced oxidation. Volatiles were isolated by solvent-assisted flavor evaporation and identified by gas chromatography-olfactometry and mass spectrometry. Aroma extract dilution analysis revealed 18 odorants that were quantified by stable isotope dilution analysis. Another important odorant, 3-methyl-1H-indole (mothball-like odor), was quantified by high-performance liquid chromatography. After storage, UFA/CLA-enriched butter showed higher concentrations of pentanal (fatty), heptanal (green), butanoic acid (cheesy), and delta-decalactone (peach-like). Photo-oxidation of butter samples induced increases in heptanal, (E)-2-octenal, and trans-4,5-epoxy-(E)-2-decenal, especially in conventional butter. The higher vitamin content in UFA/CLA samples may protect this butter from oxidation.

New insights into hydrosilylation of unsaturated carbon-heteroatom (C═O, C═N) bonds by rhenium(V)-dioxo complexes.

PubMed

Huang, Liangfang; Wang, Wenmin; Wei, Xiaoqin; Wei, Haiyan

2015-04-23

The hydrosilylation of unsaturated carbon-heteroatom (C═O, C═N) bonds catalyzed by high-valent rhenium(V)-dioxo complex ReO2I(PPh3)2 (1) were studied computationally to determine the underlying mechanism. Our calculations revealed that the ionic outer-sphere pathway in which the organic substrate attacks the Si center in an η(1)-silane rhenium adduct to prompt the heterolytic cleavage of the Si-H bond is the most energetically favorable process for rhenium(V)-dioxo complex 1 catalyzed hydrosilylation of imines. The activation energy of the turnover-limiting step was calculated to be 22.8 kcal/mol with phenylmethanimine. This value is energetically more favorable than the [2 + 2] addition pathway by as much as 10.0 kcal/mol. Moreover, the ionic outer-sphere pathway competes with the [2 + 2] addition mechanism for rhenium(V)-dioxo complex 1 catalyzing the hydrosilylation of carbonyl compounds. Furthermore, the electron-donating group on the organic substrates would induce a better activity favoring the ionic outer-sphere mechanistic pathway. These findings highlight the unique features of high-valent transition-metal complexes as Lewis acids in activating the Si-H bond and catalyzing the reduction reactions.

Storage and mobilization of natural and septic nitrate in thick unsaturated zones, California

USGS Publications Warehouse

Izbicki, John A.; Flint, Alan L.; O'Leary, David R.; Nishikawa, Tracy; Martin, Peter; Johnson, Russell D.; Clark, Dennis A.

2015-01-01

Mobilization of natural and septic nitrate from the unsaturated zone as a result of managed aquifer recharge has degraded water quality from public-supply wells near Yucca Valley in the western Mojave Desert, California. The effect of nitrate storage and potential for denitrification in the unsaturated zone to mitigate increasing nitrate concentrations were investigated. Storage of water extractable nitrate in unsaturated alluvium up to 160 meters (m) thick, ranged from 420 to 6600 kilograms per hectare (kg/ha) as nitrogen (N) beneath undeveloped sites, from 6100 to 9200 kg/ha as N beneath unsewered sites. Nitrate reducing and denitrifying bacteria were less abundant under undeveloped sites and more abundant under unsewered sites; however, δ15N–NO3, and δ18O–NO3 data show only about 5–10% denitrification of septic nitrate in most samples—although as much as 40% denitrification occurred in some parts the unsaturated zone and near the top of the water table. Storage of nitrate in thick unsaturated zones and dilution with low-nitrate groundwater are the primary attenuation mechanisms for nitrate from septic discharges in the study area. Numerical simulations of unsaturated flow, using the computer program TOUGH2, showed septic effluent movement through the unsaturated zone increased as the number and density of the septic tanks increased, and decreased with increased layering, and increased slope of layers, within the unsaturated zone. Managing housing density can delay arrival of septic discharges at the water table, especially in layered unsaturated alluvium, allowing time for development of strategies to address future water-quality issues.

Storage and mobilization of natural and septic nitrate in thick unsaturated zones, California

NASA Astrophysics Data System (ADS)

Izbicki, John A.; Flint, Alan L.; O'Leary, David R.; Nishikawa, Tracy; Martin, Peter; Johnson, Russell D.; Clark, Dennis A.

2015-05-01

Mobilization of natural and septic nitrate from the unsaturated zone as a result of managed aquifer recharge has degraded water quality from public-supply wells near Yucca Valley in the western Mojave Desert, California. The effect of nitrate storage and potential for denitrification in the unsaturated zone to mitigate increasing nitrate concentrations were investigated. Storage of water extractable nitrate in unsaturated alluvium up to 160 meters (m) thick, ranged from 420 to 6600 kilograms per hectare (kg/ha) as nitrogen (N) beneath undeveloped sites, from 6100 to 9200 kg/ha as N beneath unsewered sites. Nitrate reducing and denitrifying bacteria were less abundant under undeveloped sites and more abundant under unsewered sites; however, δ15N-NO3, and δ18O-NO3 data show only about 5-10% denitrification of septic nitrate in most samples-although as much as 40% denitrification occurred in some parts the unsaturated zone and near the top of the water table. Storage of nitrate in thick unsaturated zones and dilution with low-nitrate groundwater are the primary attenuation mechanisms for nitrate from septic discharges in the study area. Numerical simulations of unsaturated flow, using the computer program TOUGH2, showed septic effluent movement through the unsaturated zone increased as the number and density of the septic tanks increased, and decreased with increased layering, and increased slope of layers, within the unsaturated zone. Managing housing density can delay arrival of septic discharges at the water table, especially in layered unsaturated alluvium, allowing time for development of strategies to address future water-quality issues.

49 CFR 229.135 - Event recorders.

Code of Federal Regulations, 2012 CFR

2012-10-01

...) Locomotive position in consist (lead or trail); (xxiii) Tractive effort; (xxiv) Cruise control on/off, if so...; (xviii) Brakes apply summary train line; (xix) Brakes released summary train line; (xx) Cruise control on... determining, that a brake application or release resulted from manipulation of brake controls at the position...

49 CFR 229.135 - Event recorders.

Code of Federal Regulations, 2014 CFR

2014-10-01

...) Locomotive position in consist (lead or trail); (xxiii) Tractive effort; (xxiv) Cruise control on/off, if so...; (xviii) Brakes apply summary train line; (xix) Brakes released summary train line; (xx) Cruise control on... determining, that a brake application or release resulted from manipulation of brake controls at the position...

49 CFR 229.135 - Event recorders.

Code of Federal Regulations, 2013 CFR

2013-10-01

...) Locomotive position in consist (lead or trail); (xxiii) Tractive effort; (xxiv) Cruise control on/off, if so...; (xviii) Brakes apply summary train line; (xix) Brakes released summary train line; (xx) Cruise control on... determining, that a brake application or release resulted from manipulation of brake controls at the position...

49 CFR 229.135 - Event recorders.

Code of Federal Regulations, 2011 CFR

2011-10-01

...) Locomotive position in consist (lead or trail); (xxiii) Tractive effort; (xxiv) Cruise control on/off, if so...; (xviii) Brakes apply summary train line; (xix) Brakes released summary train line; (xx) Cruise control on... determining, that a brake application or release resulted from manipulation of brake controls at the position...

42 CFR 124.513 - Public facility compliance alternative.

Code of Federal Regulations, 2010 CFR

2010-10-01

... if not received, claimed, as reimbursement under titles XVIII and XIX of the Social Security Act... certified audit, conducted in accordance with procedures specified by the Secretary, of the facility's records maintained pursuant to § 124.510. If the audit establishes to the Secretary's satisfaction that no...

42 CFR 124.513 - Public facility compliance alternative.

Code of Federal Regulations, 2011 CFR

2011-10-01

... if not received, claimed, as reimbursement under titles XVIII and XIX of the Social Security Act... certified audit, conducted in accordance with procedures specified by the Secretary, of the facility's records maintained pursuant to § 124.510. If the audit establishes to the Secretary's satisfaction that no...

Experimental Study on Shear Strength of Unsaturated Loess Based on Different Water Content in Xining Area

NASA Astrophysics Data System (ADS)

guibo, Bao; hui, Li; yu, Zhang; wuyu, Zhang; ningshan, Jiang

2018-05-01

Today, the study of shear strength of unsaturated soils has become a hot topic in unsaturated soil mechanics research. There are any number of factors affecting the strength of unsaturated soils. Among these factors, the moisture content has the most significant effect on the shear strength. In this paper, unsaturated loess in Xining is taken as the research object, the triaxial test without consolidation and undrain is used to determine the shear strength and its parameters under the condition of different water content, then the relationship between unsaturated loess’ water content and shear strength parameters is explored, and curve fitting is performed. The relevantily approximate mathematics formulas are obtained. The study can provide strength parameter for slope stability and foundation pit support in Xining.

Pyrolysis kinetic and product analysis of different microalgal biomass by distributed activation energy model and pyrolysis-gas chromatography-mass spectrometry.

PubMed

Yang, Xuewei; Zhang, Rui; Fu, Juan; Geng, Shu; Cheng, Jay Jiayang; Sun, Yuan

2014-07-01

To assess the energy potential of different microalgae, Chlorella sorokiniana and Monoraphidium were selected for studying the pyrolytic behavior at different heating rates with the analytical method of thermogravimetric analysis (TG), distributed activation energy model (DAEM) and pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS). Results presented that Monoraphidium 3s35 showed superiority for pyrolysis at low heating rate. Calculated by DAEM, during the conversion rate range from 0.1 to 0.7, the activation energies of C. sorokiniana 21 were much lower than that of Monoraphidium 3s35. Both C. sorokiniana 21 and Monoraphidium 3s35 can produce certain amount (up to 20.50%) of alkane compounds, with 9-Octadecyne (C18H34) as the primary compound. Short-chain alkanes (C7-C13) with unsaturated carbon can be released in the pyrolysis at 500°C for both microalgal biomass. It was also observed that the pyrolysis of C. sorokiniana 21 released more alcohol compounds, while Monoraphidium 3s35 produced more saccharides. Copyright © 2014 Elsevier Ltd. All rights reserved.

Bioactive compounds in cashew nut (Anacardium occidentale L.) kernels: effect of different shelling methods.

PubMed

Trox, Jennifer; Vadivel, Vellingiri; Vetter, Walter; Stuetz, Wolfgang; Scherbaum, Veronika; Gola, Ute; Nohr, Donatus; Biesalski, Hans Konrad

2010-05-12

In the present study, the effects of various conventional shelling methods (oil-bath roasting, direct steam roasting, drying, and open pan roasting) as well as a novel "Flores" hand-cracking method on the levels of bioactive compounds of cashew nut kernels were investigated. The raw cashew nut kernels were found to possess appreciable levels of certain bioactive compounds such as beta-carotene (9.57 microg/100 g of DM), lutein (30.29 microg/100 g of DM), zeaxanthin (0.56 microg/100 g of DM), alpha-tocopherol (0.29 mg/100 g of DM), gamma-tocopherol (1.10 mg/100 g of DM), thiamin (1.08 mg/100 g of DM), stearic acid (4.96 g/100 g of DM), oleic acid (21.87 g/100 g of DM), and linoleic acid (5.55 g/100 g of DM). All of the conventional shelling methods including oil-bath roasting, steam roasting, drying, and open pan roasting revealed a significant reduction, whereas the Flores hand-cracking method exhibited similar levels of carotenoids, thiamin, and unsaturated fatty acids in cashew nuts when compared to raw unprocessed samples.

Quantification and sensory studies of character impact odorants of different soybean lecithins.

PubMed

Stephan, A; Steinhart, H

1999-10-01

Fifty-four potent odorants in standardized, hydrolyzed, and deoiled and hydrolyzed soybean lecithins were quantified by high-resolution gas chromatography/mass spectrometry (HRGC/MS). The characterization of their aroma impact was performed by calculation of nasal (n) and retronasal (r) odor activity values (OAVs). For this, the nasal and retronasal recognition thresholds of 18 odor-active compounds were determined in vegetable oil. The following compounds showed the highest nOAVs: 2,3-diethyl-5-methylpyrazine, methylpropanal, acetic acid, pentanoic acid, 2-ethyl-3,5-dimethylpyrazine, pentylpyridine, (Z)-1,5-octadien-3-one, 2-methylbutanal, and beta-damascenone. In addition to the compounds above, 1-octen-3-one, 1-nonen-3-one, and 3-methyl-2,4-nonandione showed potent rOAVs. The results of quantification and OAV calculation were confirmed by a model mixture of 25 impact odorants, which yielded a highly similar sensory profile to that of the original soybean lecithin. The sensory importance of pyrazines and free acids increased through enzymatic hydrolysis and decreased by the process of deoiling. The impact of unsaturated ketones on the lecithin aroma was not changed by either process.

Integrative taxonomy of the fly orchid group: insights from chemical ecology

NASA Astrophysics Data System (ADS)

Joffard, Nina; Buatois, Bruno; Schatz, Bertrand

2016-10-01

Several authors have recently stressed the need to develop an integrative approach in taxonomy, but studies applying such an approach to Mediterranean orchids are scarce. In sexually deceptive orchids from the taxonomically difficult genus Ophrys, pollination is specific and performed by male insects attracted to the flowers by sex pheromone-mimicking floral scents. Floral compounds are therefore of primary importance for reproductive isolation and species delimitations in this genus. In the fly orchid group, molecular, morphological, and ecological characters have been extensively studied, but a comprehensive survey of floral scents is still lacking. In the present study, the blends of floral compounds of its three members, Ophrys insectifera, Ophrys aymoninii, and Ophrys subinsectifera, were extracted and analyzed by gas chromatography-mass spectrometry. A total of 107 compounds were found, with a majority of saturated and unsaturated hydrocarbons. Significant differentiation, both qualitative and quantitative, was found among the three taxa. This result, pooled with those from the literature, forms a comprehensive and congruent dataset that allows us to elucidate the taxonomic rank of the three members of the fly orchid group.

A Review of Nanoliposomal Delivery System for Stabilization of Bioactive Omega-3 Fatty Acids

PubMed Central

Hadian, Zahra

2016-01-01

Currently, bioactive compounds are required in the design and production of functional foods, with the aim of improving the health status of consumers all around the world. Various epidemiological and clinical studies have demonstrated the salutary role of eicosapentaenoic acid (EPA, 22:6 n−3) and docosahexaenoic acid (DHA, 22:5 n−3) in preventing diseases and reducing mortality from cardiovascular diseases. The unsaturated nature of bioactive lipids leads to susceptibility to oxidation under environmental conditions. Oxidative deterioration of omega-3 fatty acids can cause the reduction in their nutritional quality and sensory properties. Encapsulation of these fatty acids could create a barrier against reaction with harmful environmental factors. Currently, fortification of foods containing bioactive omega-3 fatty acids has found great application in the food industries of different countries. Previous studies have suggested that nano-encapsulation has significant effects on the stability of physical and chemical properties of bioactive compounds. Considering the functional role of omega-3 fatty acids, this study has provided a literature review on applications of nanoliposomal delivery systems for encapsulation of these bioactive compounds. PMID:26955449

Renewable unsaturated polyesters from muconic acid

DOE PAGES

Rorrer, Nicholas A.; Dorgan, John R.; Vardon, Derek R.; ...

2016-09-27

cis,cis-Muconic acid is an unsaturated dicarboxylic acid that can be produced in high yields via biological conversion of sugars and lignin-derived aromatic compounds. Muconic acid is often targeted as an intermediate to direct replacement monomers such as adipic or terephthalic acid. However, the alkene groups in muconic acid provide incentive for its direct use in polymers, for example, in the synthesis of unsaturated polyester resins. Here, biologically derived muconic acid is incorporated into polyesters via condensation polymerization using the homologous series of poly(ethylene succinate), poly(propylene succinate), poly(butylene succinate), and poly(hexylene succinate). Additionally, dimethyl cis,cis-muconate is synthesized and subsequently incorporated intomore » poly(butylene succinate). NMR measurements demonstrate that alkene bonds are present in the polymer backbones. In all cases, the glass transition temperatures are increased whereas the melting and degradation temperatures are decreased. In the case of poly(butylene succinate), utilization of neat muconic acid yields substoichiometric incorporation consistent with a tapered copolymer structure, whereas the muconate diester exhibits stoichiometric incorporation and a random copolymer structure based on thermal and mechanical properties. Prototypical fiberglass panels were produced by infusing a mixture of low molecular weight poly(butylene succinate-co-muconate) and styrene into a woven glass mat and thermally initiating polymerization resulting in thermoset composites with shear moduli in excess of 30 GPa, a value typical of commercial composites. The increased glass transition temperatures with increasing mucconic incorporation leads to improved composites properties. We find that the molecular tunability of poly(butylene succinate-co-muconate) as a tapered or random copolymer enables the tunability of composite properties. Altogether, this study demonstrates the utility of muconic acid as a monomer suitable for direct use in commercial composites.« less

Renewable unsaturated polyesters from muconic acid

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

Rorrer, Nicholas A.; Dorgan, John R.; Vardon, Derek R.

cis,cis-Muconic acid is an unsaturated dicarboxylic acid that can be produced in high yields via biological conversion of sugars and lignin-derived aromatic compounds. Muconic acid is often targeted as an intermediate to direct replacement monomers such as adipic or terephthalic acid. However, the alkene groups in muconic acid provide incentive for its direct use in polymers, for example, in the synthesis of unsaturated polyester resins. Here, biologically derived muconic acid is incorporated into polyesters via condensation polymerization using the homologous series of poly(ethylene succinate), poly(propylene succinate), poly(butylene succinate), and poly(hexylene succinate). Additionally, dimethyl cis,cis-muconate is synthesized and subsequently incorporated intomore » poly(butylene succinate). NMR measurements demonstrate that alkene bonds are present in the polymer backbones. In all cases, the glass transition temperatures are increased whereas the melting and degradation temperatures are decreased. In the case of poly(butylene succinate), utilization of neat muconic acid yields substoichiometric incorporation consistent with a tapered copolymer structure, whereas the muconate diester exhibits stoichiometric incorporation and a random copolymer structure based on thermal and mechanical properties. Prototypical fiberglass panels were produced by infusing a mixture of low molecular weight poly(butylene succinate-co-muconate) and styrene into a woven glass mat and thermally initiating polymerization resulting in thermoset composites with shear moduli in excess of 30 GPa, a value typical of commercial composites. The increased glass transition temperatures with increasing mucconic incorporation leads to improved composites properties. We find that the molecular tunability of poly(butylene succinate-co-muconate) as a tapered or random copolymer enables the tunability of composite properties. Altogether, this study demonstrates the utility of muconic acid as a monomer suitable for direct use in commercial composites.« less

Mobilization of phenol and dichlorophenol in unsaturated soils by non-uniform electrokinetics.

PubMed

Luo, Qishi; Zhang, Xihui; Wang, Hui; Qian, Yi

2005-06-01

The poor mobility of organic pollutants in contaminated sites frequently results in slow remediation processes. Organics, especially hydrophobic compounds, are generally retained strongly in soil matrix as a result of sorption, sequestration, or even formation into non-aqueous-phase liquids and their mobility is thus greatly reduced. The objective of this study was to evaluate the feasibility of using non-uniform electrokinetic transport processes to enhance the mobility of organic pollutants in unsaturated soils with no injection reagents. Phenol and 2,4-dichlorophenol (2,4-DCP), and kaolin and a natural sandy loam soil were selected as model organics and soils, respectively. The results showed that non-uniform electrokinetics can accelerate the desorption and movement of phenol and 2,4-DCP in unsaturated soils. Electromigration and electroosmotic flow were the main driving forces, and their role in the mobilization of phenol and 2,4-DCP varied with soil pH. The movement of 2,4-DCP in the sandy loam towards the anode (about 1.0 cmd(-1)V(-1)) was 1.0-1.5 cmd(-1)V(-1) slower than that in the kaolin soil, but about 0.5 cmd(-1)V(-1) greater than that of phenol in the sandy loam. When the sandy loam was adjusted to pH 9.3, the movement of phenol and 2,4-DCP towards the anode was about twice and five times faster than that at pH 7.7, respectively. The results also demonstrated that the movement of phenol and 2,4-DCP in soils can be easily controlled by regulating the operational mode of electric field. It is believed that non-uniform electrokinetics has the potential for practical application to in situ remediation of organics-contaminated sites.

Physio-Biochemical Composition and Untargeted Metabolomics of Cumin (Cuminum cyminum L.) Make It Promising Functional Food and Help in Mitigating Salinity Stress

PubMed Central

Pandey, Sonika; Patel, Manish Kumar; Mishra, Avinash; Jha, Bhavanath

2015-01-01

Cumin is an annual, aromatic, herbaceous, medicinal, spice plant, most widely used as a food additive and flavoring agent in different cuisines. The study is intended to comprehensively analyse physiological parameters, biochemical composition and metabolites under salinity stress. Seed germination index, rate of seed emergence, rate of seed germination, mean germination time, plant biomass, total chlorophyll and carotenoid contents decreased concomitantly with salinity. In contrast, total antioxidant activity, H2O2, proline and MDA contents increased concurrently with stress treatments. Total phenolic and flavonoid contents were decreased initially about 1.4-fold at 50 mM, and thereafter increased about 1.2-fold at 100 mM NaCl stress. Relative water content remained unchanged up to 50 mM NaCl stress, and thereafter decreased significantly. About 2.8-fold electrolyte leakage was found in 50 mM, which increases further 4-fold at 100 mM NaCl stress. Saturated fatty acids (FAs) increased gradually with salinity, whereas unsaturation index and degree of unsaturation change arbitrarily along with the percent quantity of unsaturated FAs. Total lipid and fatty acid composition were significantly influenced by salinity stress. A total of 45 differentially expressed metabolites were identified, including luteolin, salvianolic acid, kaempferol and quercetin, which are phenolic, flavonoid or alkaloids in nature and contain antioxidant activities. Additionally, metabolites with bioactivity such as anticancerous (docetaxel) and antimicrobial (megalomicin) properties were also identified. The study evidenced that plant shoots are a rich source of metabolites, essential amino acids, phenolic compounds and fatty acids, which unveil the medicinal potential of this plant, and also provide useful insight about metabolic responses under salinity stress. PMID:26641494

Physio-Biochemical Composition and Untargeted Metabolomics of Cumin (Cuminum cyminum L.) Make It Promising Functional Food and Help in Mitigating Salinity Stress.

PubMed

Pandey, Sonika; Patel, Manish Kumar; Mishra, Avinash; Jha, Bhavanath

2015-01-01

Cumin is an annual, aromatic, herbaceous, medicinal, spice plant, most widely used as a food additive and flavoring agent in different cuisines. The study is intended to comprehensively analyse physiological parameters, biochemical composition and metabolites under salinity stress. Seed germination index, rate of seed emergence, rate of seed germination, mean germination time, plant biomass, total chlorophyll and carotenoid contents decreased concomitantly with salinity. In contrast, total antioxidant activity, H2O2, proline and MDA contents increased concurrently with stress treatments. Total phenolic and flavonoid contents were decreased initially about 1.4-fold at 50 mM, and thereafter increased about 1.2-fold at 100 mM NaCl stress. Relative water content remained unchanged up to 50 mM NaCl stress, and thereafter decreased significantly. About 2.8-fold electrolyte leakage was found in 50 mM, which increases further 4-fold at 100 mM NaCl stress. Saturated fatty acids (FAs) increased gradually with salinity, whereas unsaturation index and degree of unsaturation change arbitrarily along with the percent quantity of unsaturated FAs. Total lipid and fatty acid composition were significantly influenced by salinity stress. A total of 45 differentially expressed metabolites were identified, including luteolin, salvianolic acid, kaempferol and quercetin, which are phenolic, flavonoid or alkaloids in nature and contain antioxidant activities. Additionally, metabolites with bioactivity such as anticancerous (docetaxel) and antimicrobial (megalomicin) properties were also identified. The study evidenced that plant shoots are a rich source of metabolites, essential amino acids, phenolic compounds and fatty acids, which unveil the medicinal potential of this plant, and also provide useful insight about metabolic responses under salinity stress.

Geraniol attenuates hydrogen peroxide-induced liver fatty acid alterations in male rats.

PubMed

Ozkaya, Ahmet; Sahin, Zafer; Gorgulu, Ahmet Orhan; Yuce, Abdurrauf; Celik, Sait

2017-01-01

Hydrogen peroxide (H 2 O 2 ) is an oxidant agent and this molecule naturally occurs in the body as a product of aerobic metabolism. Geraniol is a plant-derived natural antioxidant. The aim of this study was to determine the role of geraniol on hepatic fatty acids alterations following H 2 O 2 -induced oxidative stress in male rats. After randomization, male Wistar rats were divided into four groups ( n = 7 each group). Geraniol (50 mg/kg, dissolved in corn oil) and H 2 O 2 (16 mg/kg, dissolved in distilled water) were administered by an intraperitoneal injection. Administrations were performed during 30 days with 1-day interval. Administration of H 2 O 2 resulted with a significant increase in malondialdehyde (MDA) and a significant decrease in glutathione (GSH) peroxidase glutathione level; geraniol restored its effects on liver. However, hepatic catalase (CAT) activities were significantly higher in H 2 O 2 , geraniol, and geraniol+H 2 O 2 groups than control group. The ratio of hepatic total saturated fatty acids increased in H 2 O 2 -treated animals compared with control. In addition, hepatic total unsaturated fatty acids reduced in H 2 O 2 group compared with control. The percentages of both hepatic total saturated and unsaturated fatty acids were not different between geraniol+H 2 O 2 and control groups. H 2 O 2 -induced oxidative stress may affect fatty acid composition in liver and body. Geraniol can partly restore oxidative hepatic damage because it cannot completely reverse the H 2 O 2 -induced increase in hepatic CAT activities. Moreover, this natural compound can regulate hepatic total saturated and unsaturated fatty acids percentages against H 2 O 2 -induced alterations.

Friction and wear performance of some thermoplastic polymers and polymer composites against unsaturated polyester

NASA Astrophysics Data System (ADS)

Unal, H.; Mimaroglu, A.; Arda, T.

2006-09-01

Wear experiments have been carried out with a range of unfilled and filled engineering thermoplastic polymers sliding against a 15% glass fibre reinforced unsaturated polyester polymer under 20, 40 and 60 N loads and 0.5 m/s sliding speed. Pin materials used in this experimental investigation are polyamide 66 (PA 66), poly-ether-ether-ketone (PEEK) and aliphatic polyketone (APK), glass fibre reinforced polyamide 46 (PA 46 + 30% GFR), glass fibre reinforced polytetrafluoroethylene (PTFE + 17% GFR), glass fibre reinforced poly-ether-ether-ketone (PEEK + 20% GFR), glass fibre reinforced poly-phylene-sulfide (PPS + 30% GFR), polytetrafluoroethylene filled polyamide 66 (PA 66 + 10% PTFE) and bronze filled pofytetrafluoroethylene (PTFE + 25% bronze) engineering polymers. The disc material is a 15% glass fibre reinforced unsaturated polyester thermoset polymer produced by Bulk Moulding Compound (BMC). Sliding wear tests were carried out on a pin-on-disc apparatus under 0.5 m/s sliding speed and load values of 20, 40 and 60 N. The results showed that the highest specific wear rate is for PPS + 30% GFR with a value of 1 × 10 -11 m 2/N and the lowest wear rate is for PTFE + 17% GFR with a value of 9.41 × 10 -15 m 2/N. For the materials and test conditions of this investigation, apart from polyamide 66 and PA 46 + 30% GFR polymers, the coefficient of friction and specific wear rates are not significantly affected by the change in load value. For polyamide 66 and PA 46 + 30% GFR polymers the coefficient of friction and specific wear rates vary linearly with the variation in load values.

Paracellular transport of avidin saturated or not with biotinylated cobalamin through Caco-2 cell epithelium monolayer.

PubMed

Guy, M; Pons, L; Namour, F; de Nonancourt, M; Michalski, J C; Hatier, R; Guéant, J L

2001-01-01

The cationic charge of molecules may promote their uptake across epithelia, which are rich in brush border anionic sites. The transport of unsaturated avidin and avidin saturated with a biotinylated compound was investigated across Caco-2 adenocarcinoma cell with fetal enterocyte phenotype. The unsaturated avidin and avidin saturated with either biotin or a biotinyl-cobalamin conjugate (biotinyl-Cbl) were iodinated to follow their transport through the cell monolayer. Their apparent permeability coefficient (Papp) and transepithelial pathway were determined and compared to those for control radiolabeled markers [3H]-mannitol, [125I]-beta-lactoglobulin and [57Co]-cobalamin/intrinsic factor (Cbl/IF). The Papp of [125I]-avidin estimated at 2.8 x 10(-7) +/- 0.08 cm/s was close to that for mannitol that uses paracellular pathway. The binding of biotin or biotin conjugate to avidin enhanced its tetrameric conformation. The Papp for [125I]-avidin/biotin and [125I]- avidin/biotinyl-Cbl were respectively increased by 2-fold, compared to that for [125I]-avidin and 4-fold, compared to that for [125I]-beta-lactoglobulin and [54Co]-Cbl/IF. The protein was not accumulated in the cell and was found in intact form in the basolateral side, after its transport across the monolayer. Chloroquine (0.66 micromol/ml) did not significantly decrease the Papp for [125I]-avidin/biotinyl-Cbl. Conversely it decreased by 80% the Papp for Cbl/IF, that uses transepithelial pathway. Avidin (either saturated or not with biotin and biotinyl-Cbl) was able to cross the monolayer of Caco-2 cell line through a paracellular pathway. This study pointed out the interest for using this protein as a shuttle for increasing the transport rate of biotinylated compounds through fetal epithelial barriers. Copyright 2001 S. Karger AG, Basel

Coordinatively Unsaturated Metal-Organic Frameworks M3(btc)2 (M = Cr, Fe, Co, Ni, Cu, and Zn) Catalyzing the Oxidation of CO by N2O: Insight from DFT Calculations.

PubMed

Ketrat, Sombat; Maihom, Thana; Wannakao, Sippakorn; Probst, Michael; Nokbin, Somkiat; Limtrakul, Jumras

2017-11-20

The oxidation of CO by N 2 O over metal-organic framework (MOF) M 3 (btc) 2 (M = Fe, Cr, Co, Ni, Cu, and Zn) catalysts that contain coordinatively unsaturated sites has been investigated by means of density functional theory calculations. The reaction proceeds in two steps. First, the N-O bond of N 2 O is broken to form a metal oxo intermediate. Second, a CO molecule reacts with the oxygen atom of the metal oxo site, forming one C-O bond of CO 2 . The first step is a rate-determining step for both Cu 3 (btc) 2 and Fe 3 (btc) 2 , where it requires the highest activation energy (67.3 and 19.6 kcal/mol, respectively). The lower value for the iron compound compared to the copper one can be explained by the larger amount of electron density transferred from the catalytic site to the antibonding of N 2 O molecules. This, in turn, is due to the smaller gap between the highest occupied molecular orbital (HOMO) of the MOF and the lowest unoccupied molecular orbital (LUMO)  of N 2 O for Fe 3 (btc) 2 compared to Cu 3 (btc) 2 . The results indicate the important role of charge transfer for the N-O bond breaking in N 2 O. We computationally screened other MOF M 3 (btc) 2 (M = Cr, Fe, Co, Ni, Cu, and Zn) compounds in this respect and show some relationships between the activation energy and orbital properties like HOMO energies and the spin densities of the metals at the active sites of the MOFs.

Molecular characterization of organosulfates in organic aerosols from Shanghai and Los Angeles urban areas by nanospray-desorption electrospray ionization high-resolution mass spectrometry.

PubMed

Tao, Shikang; Lu, Xiaohui; Levac, Nicole; Bateman, Adam P; Nguyen, Tran B; Bones, David L; Nizkorodov, Sergey A; Laskin, Julia; Laskin, Alexander; Yang, Xin

2014-09-16

Fine aerosol particles in the urban areas of Shanghai and Los Angeles were collected on days that were characterized by their stagnant air and high organic aerosol concentrations. They were analyzed by nanospray-desorption electrospray ionization mass spectrometry with high mass resolution (m/Δm = 100,000). Solvent mixtures of acetonitrile and water and acetonitrile and toluene were used to extract and ionize polar and nonpolar compounds, respectively. A diverse mixture of oxygenated hydrocarbons, organosulfates, organonitrates, and organics with reduced nitrogen were detected in the Los Angeles sample. A majority of the organics in the Shanghai sample were detected as organosulfates. The dominant organosulfates that were detected at two locations have distinctly different molecular characteristics. Specifically, the organosulfates in the Los Angeles sample were dominated by biogenic products, while the organosulfates of a yet unknown origin found in the Shanghai sample had distinctive characteristics of long aliphatic carbon chains and low degrees of oxidation and unsaturation. The use of the acetonitrile and toluene solvent facilitated the observation of this type of organosulfates, which suggests that they could have been missed in previous studies that relied on sample extraction using common polar solvents. The high molecular weight and low degree of unsaturation and oxidization of the uncommon organosulfates suggest that they may act as surfactants and plausibly affect the surface tension and hygroscopicity of atmospheric particles. We propose that direct esterification of carbonyl or hydroxyl compounds by sulfates or sulfuric acid in the liquid phase could be the formation pathway of these special organosulfates. Long-chain alkanes from vehicle emissions might be their precursors.

Mechanistic Insights on the Hydrogenation of α,β-Unsaturated Ketones and Aldehydes to Unsaturated Alcohols over Metal Catalysts

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

Ide, Matthew S.; Hao, Bing; Neurock, Matthew

The selective hydrogenation of unsaturated ketones (methyl vinyl ketone and benzalacetone) and unsaturated aldehydes (crotonaldehyde and cinnamaldehyde) was carried out with H₂ at 2 bar absolute over Pd/C, Pt/C, Ru/C, Au/C, Au/TiO₂, or Au/Fe₂O₃ catalysts in ethanol or water solvent at 333 K. Comparison of the turnover frequencies revealed Pd/C to be the most active hydrogenation catalyst, but the catalyst failed to produce unsaturated alcohols, indicating hydrogenation of the C=C bond was highly preferred over the C=O bond on Pd. The Pt and Ru catalysts were able to produce unsaturated alcohols from unsaturated aldehydes, but not from unsaturated ketones. Althoughmore » Au/ Fe₂O₃ was able to partially hydrogenate unsaturated ketones to unsaturated alcohols, the overall hydrogenation rate over gold was the lowest of all of the metals examined. First-principles density functional theory calculations were therefore used to explore the reactivity trends of methyl vinyl ketone (MVK) and benzalacetone (BA) hydrogenation over model Pt(111) and Ru(0001) surfaces. The observed selectivity over these metals is likely controlled by the significantly higher activation barriers to hydrogenate the C=O bond compared with those required to hydrogenate the C=C bond. Both the unsaturated alcohol and the saturated ketone, which are the primary reaction products, are strongly bound to Ru and can react further to the saturated alcohol. The lower calculated barriers for the hydrogenation steps over Pt compared with Ru account for the higher observed turnover frequencies for the hydrogenation of MVK and BA over Pt. The presence of a phenyl substituent α to the C=C bond in BA increased the barrier for C=C hydrogenation over those associated with the C=C bond in MVK; however, the increase in barriers with phenyl substitution was not adequate to reverse the selectivity trend.« less

78 FR 54178 - Virginia: Final Authorization of State Hazardous Waste Management Program Revisions

Federal Register 2010, 2011, 2012, 2013, 2014

2013-09-03

...] Perform inspections, and require monitoring, tests, analyses or reports; [cir] Enforce RCRA requirements... (revision Federal Register Analogous Virginia checklists \\1\\) authority RCRA Cluster XVII Hazardous Waste... Cluster XVIII Regulation of Oil-Bearing 73 FR 57, January 9 VAC Sec. Sec. 20- Hazardous Secondary...

29 CFR 1926.57 - Ventilation.

Code of Federal Regulations, 2011 CFR

2011-07-01

... into a duct or hood. It is usually expressed in inches of water gauge. (vii) Exhaust system. A system... velocity. It is usually expressed in inches of water gauge. (xviii) Vertical spindle disc grinder. A... operate the booth without the filters in place. (iv) (A) For wet or water-wash spray booths, the water...

29 CFR 1926.57 - Ventilation.

Code of Federal Regulations, 2010 CFR

2010-07-01

... into a duct or hood. It is usually expressed in inches of water gauge. (vii) Exhaust system. A system... velocity. It is usually expressed in inches of water gauge. (xviii) Vertical spindle disc grinder. A... operate the booth without the filters in place. (iv) (A) For wet or water-wash spray booths, the water...

42 CFR 56.603 - Project elements.

Code of Federal Regulations, 2010 CFR

2010-10-01

... of the Social Security Act, obtain or make every reasonable effort to obtain a written agreement with... entitled to insurance benefits under title XVIII of the Social Security Act, to medical assistance under a State plan approved under title XIX of such Act, to social services and family planning under title XX...

20 CFR 404.515 - Collection and compromise of claims for overpayment.

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2010-04-01

..., SURVIVORS AND DISABILITY INSURANCE (1950- ) Overpayments, Underpayments, Waiver of Adjustment or Recovery of... against an individual for recovery of overpayments under title II or title XVIII (not including title... services) of the Act, not exceeding the sum of $20,000, exclusive of interest, may be compromised, or...

42 CFR 405.2401 - Scope and definitions.

Code of Federal Regulations, 2014 CFR

2014-10-01

... for the Aged and Disabled (part of title XVIII of the Act). Certified nurse midwife (CNM) means an... chapter. Nurse practitioner (NP) means individuals who meet the applicable education, training, and other requirements of § 410.75(b) of this chapter. Physician assistant (PA) means an individual who meet the...

3. DOWNSTREAM AERIAL VIEW OF THE DIVERSION CHANNEL AND CONTROL ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

3. DOWNSTREAM AERIAL VIEW OF THE DIVERSION CHANNEL AND CONTROL WORKS. THE OUTLET CONTROL TOWER AND THE PIER FOR THE SERVICE BRIDGE ARE SHOWN COMPLETED.... Volume XVIII, No. 11, January 18, 1940. - Prado Dam, Santa Ana River near junction of State Highways 71 & 91, Corona, Riverside County, CA

High Power Microwave (HPM) and Ionizing Radiation Effects on CMOS Devices

DTIC Science & Technology

2010-03-01

24 xviii Symbol Page VIH minimum input voltage for proper high voltage output...38 VOH output voltage corresponding to VIH ...design. The high level at the input, VIH , along with VDD, define the maximum permitted “Logic 1” region, which allows for proper state change for a

75 FR 43709 - Privacy Act of 1974; New and Revised Systems of Records

Federal Register 2010, 2011, 2012, 2013, 2014

2010-07-26

... Title XVIII of the Social Security Act for qualified railroad retirement beneficiaries. ROUTINE USES OF... representative or his/her survivors, the Social Security Administration, the Centers for Medicare & Medicaid... for information regarding an individual's record should be in writing, including the full name, Social...

32 CFR 199.9 - Administrative remedies for fraud, abuse, and conflict of interest.

Code of Federal Regulations, 2012 CFR

2012-07-01

... actually furnished by a licensed social worker, psychiatric nurse, or marriage and family counselor); or (v... titles XVIII and XIX of the Social Security Act, Federal Workmen's Compensation, and the Federal... media. (A) Adequate evidence is any information sufficient to support the reasonable belief that a...

32 CFR 199.9 - Administrative remedies for fraud, abuse, and conflict of interest.

Code of Federal Regulations, 2014 CFR

2014-07-01

... actually furnished by a licensed social worker, psychiatric nurse, or marriage and family counselor); or (v... titles XVIII and XIX of the Social Security Act, Federal Workmen's Compensation, and the Federal... media. (A) Adequate evidence is any information sufficient to support the reasonable belief that a...

32 CFR 199.9 - Administrative remedies for fraud, abuse, and conflict of interest.

Code of Federal Regulations, 2011 CFR

2011-07-01

... actually furnished by a licensed social worker, psychiatric nurse, or marriage and family counselor); or (v... titles XVIII and XIX of the Social Security Act, Federal Workmen's Compensation, and the Federal... media. (A) Adequate evidence is any information sufficient to support the reasonable belief that a...

32 CFR 199.9 - Administrative remedies for fraud, abuse, and conflict of interest.

Code of Federal Regulations, 2010 CFR

2010-07-01

... actually furnished by a licensed social worker, psychiatric nurse, or marriage and family counselor); or (v... titles XVIII and XIX of the Social Security Act, Federal Workmen's Compensation, and the Federal... media. (A) Adequate evidence is any information sufficient to support the reasonable belief that a...

32 CFR 199.9 - Administrative remedies for fraud, abuse, and conflict of interest.

Code of Federal Regulations, 2013 CFR

2013-07-01

... actually furnished by a licensed social worker, psychiatric nurse, or marriage and family counselor); or (v... titles XVIII and XIX of the Social Security Act, Federal Workmen's Compensation, and the Federal... media. (A) Adequate evidence is any information sufficient to support the reasonable belief that a...

42 CFR 56.603 - Project elements.

Code of Federal Regulations, 2011 CFR

2011-10-01

..., including the provision for an audit conducted in accordance with the DHHS Audit Agency Guide for Audits of... of the Social Security Act, obtain or make every reasonable effort to obtain a written agreement with... entitled to insurance benefits under title XVIII of the Social Security Act, to medical assistance under a...

40 CFR 721.3025 - Fatty acids C12-18, C18 unsaturated, C12-18 alkyl esters (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Fatty acids C12-18, C18 unsaturated... Significant New Uses for Specific Chemical Substances § 721.3025 Fatty acids C12-18, C18 unsaturated, C12-18... chemical substance identified generically as fatty acids C12-18, C18 unsaturated, C12-18 alkyl esters (PMNs...

Fourier transform infrared imaging showing reduced unsaturated lipid content in the hippocampus of a mouse model of Alzheimer's disease.

PubMed

Leskovjan, Andreana C; Kretlow, Ariane; Miller, Lisa M

2010-04-01

Polyunsaturated fatty acids are essential to brain functions such as membrane fluidity, signal transduction, and cell survival. It is also thought that low levels of unsaturated lipid in the brain may contribute to Alzheimer's disease (AD) risk or severity. However, it is not known how accumulation of unsaturated lipids is affected in different regions of the hippocampus, which is a central target of AD plaque pathology, during aging. In this study, we used Fourier transform infrared imaging (FTIRI) to visualize the unsaturated lipid content in specific regions of the hippocampus in the PSAPP mouse model of AD as a function of plaque formation. Specifically, the unsaturated lipid content was imaged using the olefinic =CH stretching mode at 3012 cm(-1). The axonal, dendritic, and somatic layers of the hippocampus were examined in the mice at 13, 24, 40, and 56 weeks old. Results showed that lipid unsaturation in the axonal layer was significantly increased with normal aging in control (CNT) mice (p < 0.01) but remained low and relatively constant in PSAPP mice. Thus, these findings indicate that unsaturated lipid content is reduced in hippocampal white matter during amyloid pathogenesis and that maintaining unsaturated lipid content early in the disease may be critical in avoiding progression of the disease.

Antialgal and antilarval activities of bioactive compounds extracted from the marine dinoflagellate Amphidinium carterae

NASA Astrophysics Data System (ADS)

Kong, Xianyu; Han, Xiurong; Gao, Min; Su, Rongguo; Wang, Ke; Li, Xuzhao; Lu, Wei

2016-12-01

With the global ban on the application of organotin-based marine coatings by the International Maritime Organization, the development of environmentally friendly, low-toxic and nontoxic antifouling compounds for marine industries has become an urgent need. Marine microorganisms have been considered as a potential source of natural antifoulants. In this study, the antifouling potential of marine dinoflagellate Amphidinium carterae, the toxic and red-tide microalgae, was investigated. We performed a series of operations to extract the bioactive substances from Amphidinium carterae and tested their antialgal and antilarval activities. The crude extract of Amphidinium carterae showed significant antialgal activity and the EC50 value against Skeletonema costatum was 55.4 μg mL-1. After purification, the isolated bioactive substances (the organic extract C) exhibited much higher antialgal and antilarval activities with EC50 of 12.9 μg mL-1 against Skeletonema costatum and LC50 of 15.1 μg mL-1 against Amphibalanus amphitrite larvae. Subsequently, IR, Q-TOFMS, and GC-MS were utilized for the structural elucidation of the bioactive compounds, and a series of unsaturated and saturated 16- to 22-carbon fatty acids were detected. The data suggested the bioactive compounds isolated from Amphidinium carterae exhibited a significant inhibiting effect against the diatom Skeletonema costatum and Amphibalanus amphitrite larvae, and could be substitutes for persistent, toxic antifouling compounds.

Nuclear medicine technology progress report for quarter ending June 30, 1978. ABELLED COMPOUNDS; PATIENTS; POSITRON SOURCES; CARBON 11; ISOMERIC NUCLEI; LABELLED COMPOUNDS; BIOLOGICAL LOCALIZATION; CHEMICAL PREPARATION; ISOMERIC NUCLEI; LABELLED COMPOUNDS; RATS; CHEMICAL PREPARATION; LABELLED COMPOUNDS; RATS; TISSUE DISTRIBUTION

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

Knapp, Jr., F. F.

Progress is reported for the applications of /sup 11/C, /sup 195m/Pt, /sup 75/Se, and /sup 123m/Te. Additional human clinical trials with /sup 11/C-DL-tryptophan and /sup 11/C-l-aminocyclobutane carboxylic acid have been completed. The modified Buecherer-Strecker amino acid synthesis has been used to prepare /sup 11/C-DL-phenylglycine and /sup 11/C-DL-phenylalanine. These two new /sup 11/C-labeled amino acids will be studied as potential tumor localizing agents. Preliminary studies concerning the comparative organ and subcellular distribution of /sup 195m/Pt-labeled cis- and trans- dichlorodiamineplatinum(II) have been completed. The results of in vivo studies have shown the cis isomer to bind to nuclear DNA to a significantlymore » greater extent than the trans isomer. A series of /sup 123m/Te-labeled long-chain fatty acid analogs have been prepared as isosteres of unsaturated fatty acids. Several of these compounds show pronounced heart uptake in rats and may represent a new class of potential myocardial imaging agents. Studies on the preparation and tissue distribution of /sup 75/Se-..beta..-aminoethyl selenosulfate continue.« less

Fatty acid composition of intramuscular fat and odour-active compounds of lamb commercialized in northern Spain.

PubMed

Bravo-Lamas, Leire; Barron, Luis J R; Farmer, Linda; Aldai, Noelia

2018-05-01

Muscle fatty acid composition and odour-active compounds released during cooking were characterized in lamb chops (Longissimus thoracis et lumborum, n = 48) collected at retail level in northern Spain. Lamb samples were classified in two groups according to their 10 t/11 t-18:1 ratio: ≤1 (10 t-non-shifted, n = 21) and >1 (10 t-shifted, n = 27). Higher n-3 polyunsaturated fatty acid, vaccenic (11 t-18:1) and rumenic acid (9c,11 t-18:2), and iso-branched chain fatty acid contents were found in non-shifted lamb samples while n-6 polyunsaturated fatty acid, internal methyl-branched chain fatty acid, and 10 t-18:1 contents were greater in shifted samples. Regardless the fatty acid profile differences between lamb sample groups, odour-active compound profile was very similar and mostly affected by the cooking conditions. Overall, the main odour-active compounds of cooked lamb were described as "green", "meaty", "roasted", and "fatty" being methyl pyrazine, methional, dimethyl pyrazine, and dimethyl trisulphide the main odour-active compounds. Aldehydes and alcohols were the most abundant volatiles in all samples, and they were mostly originated from the oxidation of unsaturated fatty acids during cooking. Copyright © 2018 Elsevier Ltd. All rights reserved.

Mainstream Smoke Levels of Volatile Organic Compounds in 50 US Domestic Cigarette Brands Smoked with the ISO and Canadian Intense Protocols

PubMed Central

Pazo, Daniel Y.; Moliere, Fallon; Sampson, Maureen M.; Reese, Christopher M.; Agnew-Heard, Kimberly A.; Walters, Matthew J.; Holman, Matthew R.; Blount, Benjamin C.; Watson, Clifford; Chambers, David M.

2017-01-01

Introduction A significant portion of the increased risk of cancer and respiratory disease from exposure to cigarette smoke is attributed to volatile organic compounds (VOCs). In this study, 21 VOCs were quantified in mainstream cigarette smoke from 50 U.S. domestic brand varieties that included high market share brands and two Kentucky research cigarettes (3R4F and 1R5F). Methods Mainstream smoke was generated under ISO 3308 and Canadian Intense (CI) smoking protocols with linear smoking machines with a gas sampling bag collection followed by SPME/GC/MS analysis. Results For both protocols, mainstream smoke VOC amounts among the different brand varieties were strongly correlated between the majority of the analytes. Overall, Pearson correlation (r) ranged from 0.68 to 0.99 for ISO and 0.36 to 0.95 for CI. However, monoaromatic compounds were found to increase disproportionately compared to unsaturated, nitro, and carbonyl compounds under the CI smoking protocol where filter ventilation is blocked. Conclusions Overall, machine generated “vapor phase” amounts (μg/cigarette) are primarily attributed to smoking protocol (e.g., blocking of vent holes, puff volume, and puff duration) and filter ventilation. A possible cause for the disproportionate increase in monoaromatic compounds could be increased pyrolysis under low oxygen conditions associated with the CI protocol. PMID:27113015

Different stabilities of liposomes containing saturated and unsaturated lipids toward the addition of cyclodextrins.

PubMed

Ikeda, Atsushi; Funada, Rikushi; Sugikawa, Kouta

2016-06-14

Liposomes composed of unsaturated lipids were more stable than those containing saturated lipids toward DMe-β-CDx, DMe-α-CDx and DMe-β-CDx. The Hill coefficient values (n) indicated that the saturated lipid·DMe-CDx complexes had stoichiometric ratios in the range of 1 : 3-1 : 4, while the unsaturated lipid·DMe-CDx complexes had ratios in the range of 1 : 1.5-1 : 3. That is, a cis alkene group in the unsaturated lipids prevented complexation with a second DMe-CDx in the direction toward each acyl chain. Furthermore, the liposomes composed of the unsaturated lipids were much slower to form precipitates upon the addition of α-CDx than those of the saturated lipids. To the best of our knowledge, this is the first example showing that CDxs interact with unsaturated lipids.

Total fatty acid content of the plasma membrane of Saccharomyces cerevisiae is more responsible for ethanol tolerance than the degree of unsaturation.

PubMed

Kim, Hyun-Soo; Kim, Na-Rae; Choi, Wonja

2011-03-01

The effect of change in unsaturated fatty acid composition on ethanol tolerance in Saccharomyces cerevisiae overexpressing ScOLE1 (∆9 fatty acid desaturase gene of S. cerevisiae), CaFAD2 (∆12 fatty acid desaturase gene of Candida albicans), or CaFAD3 (ω3 fatty acid desaturase gene of C. albicans) was examined. ScOLE1 over-expression increased the total unsaturated fatty acid content and enhanced ethanol tolerance, compared with a control strain. In contrast, overexpression of CaFAD2 and CaFAD3, which led to production of linoleic acid (18:2) and α-linolenic acid (18:3), respectively, neither changed total unsaturated fatty acids nor enhanced ethanol tolerance. The total unsaturated fatty acid content rather than the degree of unsaturation is thus an important factor for ethanol tolerance.

Molecular characterization of low molecular weight dissolved organic matter in water reclamation processes using Orbitrap mass spectrometry.

PubMed

Phungsai, Phanwatt; Kurisu, Futoshi; Kasuga, Ikuro; Furumai, Hiroaki

2016-09-01

Reclaimed water has recently become an important water source for urban use, but the composition of dissolved organic matter (DOM) in reclaimed water has rarely been characterized at the compound level because of its complexity. In this study, the transformation and changes in composition of low molecular weight DOM in water reclamation processes, where secondary effluent of the municipal wastewater treatment plant was further treated by biofiltration, ozonation and chlorination, were investigated by "unknown" screening analysis using Orbitrap mass spectrometry (Orbitrap MS). The intense ions were detected over an m/z range from 100 to 450. In total, 2412 formulae with various heteroatoms were assigned, and formulae with carbon (C), hydrogen (H) and oxygen (O) only and C, H, O and sulfur (S) were the most abundant species. During biofiltration, CHO-only compounds with relatively high hydrogen to carbon (H/C) ratio or with saturated structure were preferentially removed, while CHOS compounds were mostly removed. Ozonation induced the greatest changes in DOM composition. CHOS compounds were mostly decreased after ozonation while ozone selectively removed CHO compounds with relatively unsaturated structure and produced compounds that were more saturated and with a higher degree of oxidation. After chlorination, 168 chlorine-containing formulae, chlorinated disinfection by-products (DBPs), were additionally detected. Candidate DBP precursors were determined by tracking chlorinated DBPs formed via electrophilic substitution, half of which were generated during the ozonation. Copyright © 2016 Elsevier Ltd. All rights reserved.

Diversity of compounds in femoral secretions of Galápagos iguanas (genera: Amblyrhynchus and Conolophus), and their potential role in sexual communication in lek-mating marine iguanas (Amblyrhynchus cristatus)

PubMed Central

Menke, Markus; Quezada, Galo; Jiménez-Uzcátegui, Gustavo; Steinfartz, Sebastian

2017-01-01

Background Chemical signals are widely used in the animal kingdom, enabling communication in various social contexts, including mate selection and the establishment of dominance. Femoral glands, which produce and release waxy secretions into the environment, are organs of central importance in lizard chemical communication. The Galápagos marine iguana (Amblyrhynchus cristatus) is a squamate reptile with a lek-mating system. Although the lekking behaviour of marine iguanas has been well-studied, their potential for sexual communication via chemical cues has not yet been investigated. Here we describe the diversity of the lipophilic fraction of males’ femoral gland secretions among 11 island populations of marine iguanas, and compare it with the composition of its sister species, the Galápagos land iguana (Conolophus subcristatus). We also conducted behavioural observations in marine iguana territorial males in order to explore the possible function of these substances in the context of male dominance in leks. Methods Femoral secretions were analysed by gas chromatography coupled to mass spectrometry (GC–MS), and chromatography with a flame ionisation detector (GC-FID) in order to characterise the lipophilic composition. To understand the potential role of femoral secretions in marine iguana intraspecific communication, territorial males were sampled for their femoral glands and monitored to record their head bob rate—a territorial display behaviour in males—as well as the number of females present in their leks. Results We found that the gland secretions were composed of ten saturated and unsaturated carboxylic acids ranging in chain length between C16 and C24, as well as three sterols. Cholesterol was the main compound found. Intriguingly, land iguanas have a higher diversity of lipophilic compounds, with structural group of lipids (i.e. aldehydes) entirely absent in marine iguanas; overall the chemical signals of both species were strongly differentiated. Lipid profiles also differed among populations of marine iguanas from different islands, with some islands demonstrating a high diversity of lipophilic compounds (i.e. full spectra of compounds), and others lacking one or more compounds. Among the compounds most frequently found missing were 11- and 13-eicosenoic acids. Gland secretions of males with a better body condition and with a higher dominance status (i.e. those accompanied by females and with higher head bob display) were proportionately richer in C20-unsaturated fatty acids (11-eicosenoic acid). Discussion Land and marine iguanas strongly diverged in their chemical composition of the femoral glands likely due to ecological differences between both species. Despite that marine iguana populations varied in their femoral gland composition that was not related to their genetic structure. Our results indicated that 11-eicosenoic acid may play an important role in intraspecific chemical communication in marine iguanas. PMID:28828277

Practical synthesis of Shi's diester fructose derivative for catalytic asymmetric epoxidation of alkenes.

PubMed

Nieto, N; Molas, P; Benet-Buchholz, J; Vidal-Ferran, A

2005-11-25

[reaction: see text] A practical synthesis of Shi's diester 3 for catalytic asymmetric epoxidations has been developed. The catalyst has been prepared in multigram quantities from D-fructose in four steps with a 66% overall yield. Efficiency, cost, and selectivity aspects of the reagents involved for its preparation have been taken care of during its preparation. The workup procedures have been simplified to the bare minimum, rendering a very practical preparation method. The well-known high efficiency of this catalyst 3 in the epoxidation of alpha,beta-unsaturated carbonyl compounds has also proved to be high in unfunctionalized alkenes.

Fungal strains as catalysts for the biotransformation of halolactones by hydrolytic dehalogenation with the dimethylcyclohexane system.

PubMed

Grabarczyk, Małgorzata

2012-08-14

Bicyclic chloro-, bromo- and iodo-γ-lactones with dimethylcyclohexane rings were used as substrates for bioconversion by several fungal strains (Fusarium, Botrytis and Beauveria). Most of the selected microorganisms transformed these lactones by hydrolytic dehalogenation into the new compound cis-2-hydroxy-4,6-dimethyl-9-oxabicyclo[4.3.0]- nonan-8-one, mainly the (-)-isomer. When iodo-γ-lactone was used as the substrate, two products were observed: a hydroxy-γ-lactone and an unsaturated lactone. The structures of all substrates and products were established on the basis of their spectral data. The mechanism of dehalogenation of three halolactones was also studied.

Effect of various alanine analogues on the L-alanine-adding enzyme from Escherichia coli.

PubMed

Liger, D; Blanot, D; van Heijenoort, J

1991-05-01

An extract from Escherichia coli containing the L-alanine-adding enzyme with a high specific activity was prepared. Several compounds structurally related to L-alanine were tested as inhibitors of this activity. Intact amino and carboxyl groups were necessary for an interaction with the enzyme. Certain halogenated (haloalanines) or unsaturated (L-vinylglycine, L-propargylglycine, 3-cyano-L-alanine) amino acids were good inhibitors. Radioactive glycine, serine and 1-aminoethylphosphonic acid were tested as substrates. Whereas glycine or L-serine gave rise to the formation of the corresponding nucleotide product, no synthesis of UDP-N-acetylmuramyl-L-1-aminoethylphosphonic acid could be detected.

Organic matter in meteorites and comets - Possible origins

NASA Technical Reports Server (NTRS)

Anders, Edward

1991-01-01

At least six extraterrestrial environments may have contributed organic compounds to meteorites and comets: solar nebula, giant-planet subnebulae, asteroid interiors containing liquid water, carbon star atmospheres, and diffuse or dark interstellar clouds. The record in meteorites is partly obscured by pervasive reheating that transformed much of the organic matter to kerogen; nonetheless, it seems that all six formation sites contributed. For comets, the large abundance of HCHO, HCN, and unsaturated hydrocarbons suggests an interstellar component of 50 percent or more, but the contributions of various interstellar processes, and of a solar-nebula component, are hard to quantify. A research program is outlined that may help reduce these uncertainties.

Formation of organic compounds from simulated Titan atmosphere: perspectives of the Cassini mission.

PubMed

Koike, Toshiyuki; Kaneko, Takeo; Kobayashi, Kensei; Miyakawa, Shin; Takano, Yoshinori

2003-10-01

Gas mixtures of methane and nitrogen were subjected to proton irradiation (PI), gamma irradiation (GI), UV irradiation (UV) or spark discharges (SD), and the products were analyzed to compare possible energy sources for synthesis of organics in Titan. SD mainly gave unsaturated hydrocarbons, while PI gave saturated hydrocarbons. N-containing organics were detected in PI, GI and SD, but not in UV. The formers yielded amino acids after acid-hydrolysis of solid phase products (tholin). Comparison of the present results with those by Cassini-Huygens [correction of Heygens] mission will make it possible to prove major energy sources for organic synthesis in Titan atmosphere.

Acrolein Microspheres Are Bonded To Large-Area Substrates

NASA Technical Reports Server (NTRS)

Rembaum, Alan; Yen, Richard C. K.

1988-01-01

Reactive cross-linked microspheres produced under influence of ionizing radiation in aqueous solutions of unsaturated aldehydes, such as acrolein, with sodium dodecyl sulfate. Diameters of spheres depend on concentrations of ingredients. If polystyrene, polymethylmethacrylate, or polypropylene object immersed in solution during irradiation, microspheres become attached to surface. Resulting modified surface has grainy coating with reactivity similar to free microspheres. Aldehyde-substituted-functional microspheres react under mild conditions with number of organic reagents and with most proteins. Microsphere-coated macrospheres or films used to immobilize high concentrations of proteins, enzymes, hormones, viruses, cells, and large number of organic compounds. Applications include separation techniques, clinical diagnostic tests, catalytic processes, and battery separators.

Unsaturated soil moisture drying and wetting diffusion coefficient measurements in the laboratory.

DOT National Transportation Integrated Search

2009-09-01

ABSTRACTTransient moisture flow in an unsaturated soil in response to suction changes is controlled by the unsaturated moisture diffusion coefficient. The moisture diffusion coefficient can be determined by measuring suction profiles over time. The l...

A UV resonance Raman (UVRR) spectroscopic study on the extractable compounds of Scots pine ( Pinus sylvestris) wood . Part I: Lipophilic compounds

NASA Astrophysics Data System (ADS)

Nuopponen, M.; Willför, S.; Jääskeläinen, A.-S.; Sundberg, A.; Vuorinen, T.

2004-11-01

The wood resin in Scots pine ( Pinus sylvestris) stemwood and branch wood were studied using UV resonance Raman (UVRR) spectroscopy. UVRR spectra of the sapwood and heartwood hexane extracts, solid wood samples and model compounds (six resin acids, three fatty acids, a fatty acid ester, sitosterol and sitosterol acetate) were collected using excitation wavelengths of 229, 244 and 257 nm. In addition, visible Raman spectra of the fatty and resin acids were recorded. Resin compositions of heartwood and sapwood hexane extracts were determined using gas chromatography. Raman signals of both conjugated and isolated double bonds of all the model compounds were resonance enhanced by UV excitation. The oleophilic structures showed strong bands in the region of 1660-1630 cm -1. Distinct structures were enhanced depending on the excitation wavelength. The UVRR spectra of the hexane extracts showed characteristic bands for resin and fatty acids. It was possible to identify certain resin acids from the spectra. UV Raman spectra collected from the solid wood samples containing wood resin showed a band at ˜1650 cm -1 due to unsaturated resin components. The Raman signals from extractives in the resin rich branch wood sample gave even more strongly enhanced signals than the aromatic lignin.

A UV resonance Raman (UVRR) spectroscopic study on the extractable compounds of Scots pine (Pinus sylvestris) wood. Part I: lipophilic compounds.

PubMed

Nuopponen, M; Willför, S; Jääskeläinen, A-S; Sundberg, A; Vuorinen, T

2004-11-01

The wood resin in Scots pine (Pinus sylvestris) stemwood and branch wood were studied using UV resonance Raman (UVRR) spectroscopy. UVRR spectra of the sapwood and heartwood hexane extracts, solid wood samples and model compounds (six resin acids, three fatty acids, a fatty acid ester, sitosterol and sitosterol acetate) were collected using excitation wavelengths of 229, 244 and 257 nm. In addition, visible Raman spectra of the fatty and resin acids were recorded. Resin compositions of heartwood and sapwood hexane extracts were determined using gas chromatography. Raman signals of both conjugated and isolated double bonds of all the model compounds were resonance enhanced by UV excitation. The oleophilic structures showed strong bands in the region of 1660-1630 cm(-1). Distinct structures were enhanced depending on the excitation wavelength. The UVRR spectra of the hexane extracts showed characteristic bands for resin and fatty acids. It was possible to identify certain resin acids from the spectra. UV Raman spectra collected from the solid wood samples containing wood resin showed a band at approximately 1650 cm(-1) due to unsaturated resin components. The Raman signals from extractives in the resin rich branch wood sample gave even more strongly enhanced signals than the aromatic lignin.

Quinazolinones-Phenylquinoxaline hybrids with unsaturation/saturation linkers as novel anti-proliferative agents.

PubMed

Palem, Jyothsna Devi; Alugubelli, Gopi Reddy; Bantu, Rajashaker; Nagarapu, Lingaiah; Polepalli, Sowjanya; Jain, S Nishanth; Bathini, Raju; Manga, Vijjulatha

2016-07-01

A new series of novel quinazolinones with allylphenyl quinoxaline hybrids 9a-n were efficiently synthesized in good yields by the reaction of 3-allyl-2-methylquinazolin-4(3H)-one (5a-n) with bromophenyl)quinoxaline (8) utilizing Pd catalyzed Heck-cross coupling and evaluated for anti-proliferative activity against four cancer cell lines such as HeLa (cervical), MIAPACA (pancreatic), MDA-MB-231 (breast) and IMR32 (neuroblastoma). Compounds 9a, 9e, 9g and 9h exhibited promising anti-proliferative activity with GI50 values ranging from 0.06 to 0.2μM against four cell lines, while compounds 9e and 9k showed significant activity against HeLa and MIAPACA cell lines and compounds 9b, 9d, 9h and 9j showed selective potency against IMR32 and MDA-MB-231 cell lines. This is the first report on the synthesis and in vitro anti-proliferative evaluation of E-2-(4-substituted)-3-(3-(4-(quinoxalin-2-yl)phenyl)allyl)quinazolin-4(3H)-ones (9a-n). Docking results indicate a sign of good correlation between experimental activity and calculated binding affinity (dock score), suggesting that these compounds could act as promising DNA intercalates. Copyright © 2016 Elsevier Ltd. All rights reserved.

Organic compounds in indoor air—their relevance for perceived indoor air quality?

NASA Astrophysics Data System (ADS)

Wolkoff, Peder; Nielsen, Gunnar D.

It is generally believed that indoor air pollution, one way or another may cause indoor air complaints. However, any association between volatile organic compounds (VOCs) concentrations and increase of indoor climate complaints, like the sick-building syndrome symptoms, is not straightforward. The reported symptom rates of, in particular, eye and upper airway irritation cannot generally be explained by our present knowledge of common chemically non-reactive VOCs measured indoors. Recently, experimental evidence has shown those chemical reactions between ozone (either with or without nitrogen dioxide) and unsaturated organic compounds (e.g. from citrus and pine oils) produce strong eye and airway irritating species. These have not yet been well characterised by conventional sampling and analytical techniques. The chemical reactions can occur indoors, and there is indirect evidence that they are associated with eye and airway irritation. However, many other volatile and non-volatile organic compounds have not generally been measured which could equally well have potent biological effects and cause an increase of complaint rates, and posses a health/comfort risk. As a consequence, it is recommended to use a broader analytical window of organic compounds than the classic VOC window as defined by the World Health Organisation. It may include hitherto not yet sampled or identified intermediary species (e.g., radicals, hydroperoxides and ionic compounds like detergents) as well as species deposited onto particles. Additionally, sampling strategies including emission testing of building products should carefully be linked to the measurement of organic compounds that are expected, based on the best available toxicological knowledge, to have biological effects at indoor concentrations.

STRUCTURE TOXICITY IN RELATIONSHIPS FOR A,B-UNSATURATED ALCOHOLS IN FISH

EPA Science Inventory

Previous toxicity testing with fathead minnows (Pimephales promelas) indicated that some unsaturated acetylenic and allylic alcohols can be metabolically activated, via alcohol dehydrogenase, to highly toxic a,B-unsaturated aldehydes and ketones or allene derivatives. lthough sev...

42 CFR 56.303 - Project elements.

Code of Federal Regulations, 2010 CFR

2010-10-01

... furnished by or through the center is to be reimbursed under title XIX or title XX of the Social Security... insurance benefits under title XVIII of the Social Security Act, to medical assistance under a State plan approved under title XIX of such Act, to social services and family planning under title XX of such Act, or...

42 CFR 124.502 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-10-01

... Social Security Act (42 U.S.C. 1395, et seq.) and the implementing regulations (42 CFR part 413) bears to... Works Capital Development and Investment Act of 1976 (Pub. L. 94-369). In the case of a loan guaranteed... XVIII and XIX of the Social Security Act. (j) Persons unable to pay means persons who meet the...

Speckle Interferometry at the U.S. Naval Observatory. XVIII

DTIC Science & Technology

2012-05-01

1 1.9 −0.03 Novakovic & Todorovic (2006) a Notes. a These are smallΔm system. The orbit indicates a quadrant flip is needed; however, based on...109, 332 Novakovic , B., & Todorovic, N. 2006, Serb. Astron. J., 172, 21 Popovic, G. M., & Pavlovic, R. 1996, Bull. Obs. Astron. Belgr., 153, 57 Scardia

Follow-Up Study of 1988 Nursing Graduates. Volume XVIII, No. 8.

ERIC Educational Resources Information Center

Dincher, J.; Meltesen, Cal

In 1989, a follow-up study of nursing program graduates was conducted at William Rainey Harper College (WRHC) to examine their employment patterns, further education plans, and evaluate particular aspects of their WRHC experience. Questionnaires were mailed to 105 nursing students who graduated in 1988. Results were compared with previous surveys…

26 CFR 54.9801-4 - Rules relating to creditable coverage.

Code of Federal Regulations, 2014 CFR

2014-04-01

... Subtitle K, and without regard to whether the coverage is offered in the group market, the individual market, or otherwise). (iii) Part A or B of title XVIII of the Social Security Act (Medicare). (iv) Title... complete application for a health insurance policy in the individual market. E's application is accepted...

[Medical bioclimatology: aspects of the historical evolution, with special reference to the contribution of Piedmontese scientists].

PubMed

Cremona, G F

1982-01-01

A short historical review on medical-meteorological and environmental research is presented. It is particularly stressed the contribution by piedmontese scientists of the XVIII century to investigations about the atmospheric electricity (Beccaria and Gardini) and the relations between diseases and atmospheric factors (Somis, Vassalli Eandi, Mullatera).

42 CFR 403.902 - Definitions.

Code of Federal Regulations, 2013 CFR

2013-10-01

..., repackagers, relabelers, and kit assemblers) that do not hold title to any covered drug, device, biological or... sister corporations. Covered device means any device for which payment is available under Title XVIII of the Act or under a State plan under Title XIX or XXI of the Act (or a waiver of such plan), either...

42 CFR 403.902 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-10-01

..., repackagers, relabelers, and kit assemblers) that do not hold title to any covered drug, device, biological or... sister corporations. Covered device means any device for which payment is available under Title XVIII of the Act or under a State plan under Title XIX or XXI of the Act (or a waiver of such plan), either...

78 FR 9457 - Medicare, Medicaid, Children's Health Insurance Programs; Transparency Reports and Reporting of...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-02-08

... applicable manufacturers of drugs, devices, biologicals, or medical supplies covered under title XVIII of the Act (Medicare) or a State plan under title XIX (Medicaid) or XXI of the Act (the Children's Health..., ``Conflict of Interest in Medical Research, Education and Practice.'' Given these recommendations and other...

42 CFR 422.6 - Cost-sharing in enrollment-related costs.

Code of Federal Regulations, 2014 CFR

2014-10-01

... counseling and assistance program) and section 1860D-1(c) of the Act (relating to dissemination of enrollment...—(1) Timing of collection. CMS collects the fees over 9 consecutive months beginning with January of... under title XVIII. (f) Assessment methodology. (1) The amount of the applicable portion of the user fee...

42 CFR 422.6 - Cost-sharing in enrollment-related costs.

Code of Federal Regulations, 2011 CFR

2011-10-01

... assistance program) and section 1860D-1(c) of the Act (relating to dissemination of enrollment information... which enrollment is effected or coordinated under section 1851 of the Act. (d) Collection of fees—(1... under title XVIII. (f) Assessment methodology. (1) The amount of the applicable portion of the user fee...

42 CFR 422.6 - Cost-sharing in enrollment-related costs.

Code of Federal Regulations, 2012 CFR

2012-10-01

... counseling and assistance program) and section 1860D-1(c) of the Act (relating to dissemination of enrollment...—(1) Timing of collection. CMS collects the fees over 9 consecutive months beginning with January of... under title XVIII. (f) Assessment methodology. (1) The amount of the applicable portion of the user fee...

42 CFR 422.6 - Cost-sharing in enrollment-related costs.

Code of Federal Regulations, 2013 CFR

2013-10-01

... counseling and assistance program) and section 1860D-1(c) of the Act (relating to dissemination of enrollment...—(1) Timing of collection. CMS collects the fees over 9 consecutive months beginning with January of... under title XVIII. (f) Assessment methodology. (1) The amount of the applicable portion of the user fee...

Advanced Pattern Recognition Techniques (Techniques avancees de reconnaissance de forme)

DTIC Science & Technology

1998-09-01

alarmes dans la d6tection des mines terrestres et des munitions explosives non explos6es. Les m~thodes classiques de reconnaissance de forme...the XVIII. Congress of the International Society for [19] DIN EN 60825-1(IEC 825-1) VDE 0837, Photogrammetry and Remote Sensing Sicherheit von Laser

2 CFR 376.370 - What are the obligations of Medicare carriers and intermediaries?

Code of Federal Regulations, 2010 CFR

2010-01-01

... responsibilities on behalf of the Medicare program (Title XVIII of the Social Security Act), these entities assume the same obligations and responsibilities as the HHS Medicare officials responsible for the Medicare... Responsibilities of Participants Regarding Transactions § 376.370 What are the obligations of Medicare carriers and...

Journal of College Reading and Learning, Volume XVIII, 1985.

ERIC Educational Resources Information Center

O'Hear, Michael F., Ed.; Knowles, Ramona, Ed.

1985-01-01

Drawn from the proceedings of the 1985 Western College Reading and Learning Association, as well as articles submitted for juried selection, the papers in this journal issue focus on reading, learning assistance, developmental education, and tutorial services at the college level. Titles and authors of the papers include (1) "Reaching New Heights:…

37 CFR 202.20 - Deposit of copies and phonorecords for copyright registration.

Code of Federal Regulations, 2010 CFR

2010-07-01

... motion pictures made from pre-existing black and white motion pictures, in addition to the deposit of one... work consists of a repeated pictorial or graphic design, the complete design and at least part of one.... (xviii) Architectural works. (A) For designs of unconstructed buildings, the deposit must consist of one...

[Growth of the neurocranium].

PubMed

Hodacová, Z; Skalská, H

1998-01-01

The present study demonstrates the results of evaluation of growth changes of the neurocranium in a set of 98 human skulls of immature individuals aged 6-18/20/ years from the XIII.-XVIII. century. Craniometric values were matched with the corresponding values measured on the skulls of the same age groups from the IX. century and IX.-XII. centuries.

Improved solution for saturated-unsaturated flow to a partially penetrating well in a compressible unconfined aquifer

NASA Astrophysics Data System (ADS)

Mishra, P. K.; Neuman, S. P.

2009-12-01

Tartakovsky and Neuman [2007] developed an analytical solution for flow to a partially penetrating well pumping at a constant rate from a compressible unconfined aquifer considering an unsaturated zone of infinite thickness. In their solution three-dimensional, axially symmetric unsaturated flow was described by a linearized version of Richards’ equation in which both relative hydraulic conductivity and water content vary exponentially with incremental capillary pressure head relative to its air entry value. Both exponential functions were characterized by a common exponent. We present an improved solution in which relative hydraulic conductivity and water content are characterized by separate parameters and the unsaturated zone has finite thickness. Our four-parameter representation of these functions is more flexible than the three-parameter version of Mathias and Butler [2006], who consider flow in the unsaturated zone to be strictly vertical and the pumping well to be fully penetrating. We investigate the effects of unsaturated zone thickness and constitutive parameters on drawdown in the unsaturated and saturated zones as functions of position and time. We then use our new solution to analyze data from synthetic and real pumping tests.

A Novel Multi-voxel Based Quantitation of Metabolites and Lipids Non-invasively Combined with Diffusion Weighted Imaging in Breast Cancer

DTIC Science & Technology

2011-09-01

SATURATED AND UNSATURATED LIPIDS 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT 18. NUMBER OF PAGES 19a. NAME OF RESPONSIBLE PERSON... saturated fatty acid, mono- unsaturated and poly unsaturated fatty acids. 6 Figure 3. Prior-knowledge COSY spectra for the breast metabolites (top...In addition to water, presence of 2D diagonal and cross peaks from the methyl, methylene, and olefenic protons of unsaturated and saturated 8

On the coupled unsaturated-saturated flow process induced by vertical, horizontal, and slant wells in unconfined aquifers

NASA Astrophysics Data System (ADS)

Liang, Xiuyu; Zhan, Hongbin; Zhang, You-Kuan; Liu, Jin

2017-03-01

Conventional models of pumping tests in unconfined aquifers often neglect the unsaturated flow process. This study concerns the coupled unsaturated-saturated flow process induced by vertical, horizontal, and slant wells positioned in an unconfined aquifer. A mathematical model is established with special consideration of the coupled unsaturated-saturated flow process and the well orientation. Groundwater flow in the saturated zone is described by a three-dimensional governing equation and a linearized three-dimensional Richards' equation in the unsaturated zone. A solution in the Laplace domain is derived by the Laplace-finite-Fourier-transform and the method of separation of variables, and the semi-analytical solutions are obtained using a numerical inverse Laplace method. The solution is verified by a finite-element numerical model. It is found that the effects of the unsaturated zone on the drawdown of a pumping test exist at any angle of inclination of the pumping well, and this impact is more significant in the case of a horizontal well. The effects of the unsaturated zone on the drawdown are independent of the length of the horizontal well screen. The vertical well leads to the largest water volume drained from the unsaturated zone (W) during the early pumping time, and the effects of the well orientation on W values become insignificant at the later time. The screen length of the horizontal well does not affect W for the whole pumping period. The proposed solutions are useful for the parameter identification of pumping tests with a general well orientation (vertical, horizontal, and slant) in unconfined aquifers affected from above by the unsaturated flow process.

Structural requirements for the cytoprotective actions of mono-unsaturated fatty acids in the pancreatic β-cell line, BRIN-BD11

PubMed Central

Dhayal, S; Welters, H J; Morgan, N G

2008-01-01

Background and purpose: Exposure of pancreatic β-cells to long-chain free fatty acids leads to differential responses according to the chain length and degree of unsaturation. In particular, long-chain saturated molecules such as palmitate (C16:0) cause apoptosis, whereas equivalent mono-unsaturated species (for example, palmitoleate (C16:1)) are not overtly toxic. Moreover, mono-unsaturates exert a powerful cytoprotective response against a range of proapoptotic stimuli. However, the structural requirements that determine cytoprotection have not been determined and form the basis of the present study. Experimental approach: BRIN-BD11 and INS-1 β-cells were exposed either to the saturated fatty acid palmitate, or to serum withdrawal, to mediate cytotoxicity. The protective effects of a wide range of mono-unsaturated fatty acid derivatives were tested in cytotoxicity assays. Effector caspase activity was also measured and correlated with viability. Key results: The cytotoxic actions of palmitate were inhibited dose-dependently by long-chain mono-unsaturated fatty acids with a defined potency order C18:1>C16:1≫C14:1. The configuration of the double bond was also important with cis forms being more potent than trans forms. Alkylated mono-unsaturated fatty-acid derivates were also cytoprotective, although their efficacy declined as the alkyl chain length increased. Cytoprotection was achieved rapidly on addition of mono-unsaturates and correlated with a rapid and dramatic inhibition of caspase-3/7 activity in palmitate-treated cells. Conclusions and implications: The data reveal the structural requirements that dictate the cytoprotective actions of mono-unsaturated fatty acids in pancreatic β-cells. Metabolic activation is not required and the data point at the potential involvement of a fatty acid receptor in mediating cytoprotection. PMID:18297101

Studies on unsaturated flow in dual-scale fiber fabrics

NASA Astrophysics Data System (ADS)

Yan, Fei; Yan, Shilin; Li, Yongjing

2018-03-01

Fiber fabrics in liquid composite molding (LCM) can be recognized as a dual-scale structure. As sink theory developed, this unsaturated flow behavior has already been simulated successfully; however, most of simulated results based on a unit cell under ideal status, thus making results were not agreement with experiment. In this study, an experimental method to establish sink function was proposed. After compared the simulation results by this sink function, it shows high accuracy with the experimental data. Subsequently, the key influencing factors for unsaturated flow have been further investigated; results show that the filling time for unsaturated flow was much longer than saturated flow. In addition, the injection pressure and permeability were the key factors lead to unsaturated flow.

Compounds from the Fruits of the Popular European Medicinal Plant Vitex agnus-castus in Chemoprevention via NADP(H):Quinone Oxidoreductase Type 1 Induction.

PubMed

Li, Shenghong; Qiu, Shengxiang; Yao, Ping; Sun, Handong; Fong, Harry H S; Zhang, Hongjie

2013-01-01

As part of our continuing efforts in the search for potential biologically active compounds from medicinal plants, we have isolated 18 compounds including two novel nitrogen containing diterpenes from extracts of the fruits of Vitex agnus-castus. These isolates, along with our previously obtained novel compound vitexlactam A (1), were evaluated for potential biological effects, including cancer chemoprevention. Chemically, the nitrogenous isolates were found to be two labdane diterpene alkaloids, each containing an α , β -unsaturated γ -lactam moiety. Structurally, they were elucidated to be 9 α -hydroxy-13(14)-labden-16,15-amide (2) and 6 β -acetoxy-9 α -hydroxy-13(14)-labden-15,16-amide (3), which were named vitexlactams B and C, respectively. The 15 known isolates were identified as vitexilactone (4), rotundifuran (5), 8-epi-manoyl oxide (6), vitetrifolin D (7), spathulenol (8), cis-dihydro-dehydro-diconiferylalcohol-9-O- β -D-glucoside (9), luteolin-7-O-glucoside (10), 5-hydroxy-3,6,7,4'-tetramethoxyflavone (11), casticin (12), artemetin (13), aucubin (14), agnuside (15), β -sitosterol (16), p-hydroxybenzoic acid (17), and p-hydroxybenzoic acid glucose ester (18). All compound structures were determined/identified on the basis of 1D and/or 2D NMR and mass spectrometry techniques. Compounds 6, 8, 9, and 18 were reported from a Vitex spieces for the first time. The cancer chemopreventive potentials of these isolates were evaluated for NADP(H):quinone oxidoreductase type 1 (QR1) induction activity. Compound 7 demonstrated promising QR1 induction effect, while the new compound vitexlactam (3) was only slightly active.

Compounds from the Fruits of the Popular European Medicinal Plant Vitex agnus-castus in Chemoprevention via NADP(H):Quinone Oxidoreductase Type 1 Induction

PubMed Central

Li, Shenghong; Qiu, Shengxiang; Yao, Ping; Sun, Handong; Fong, Harry H. S.; Zhang, Hongjie

2013-01-01

As part of our continuing efforts in the search for potential biologically active compounds from medicinal plants, we have isolated 18 compounds including two novel nitrogen containing diterpenes from extracts of the fruits of Vitex agnus-castus. These isolates, along with our previously obtained novel compound vitexlactam A (1), were evaluated for potential biological effects, including cancer chemoprevention. Chemically, the nitrogenous isolates were found to be two labdane diterpene alkaloids, each containing an α, β-unsaturated γ-lactam moiety. Structurally, they were elucidated to be 9α-hydroxy-13(14)-labden-16,15-amide (2) and 6β-acetoxy-9α-hydroxy-13(14)-labden-15,16-amide (3), which were named vitexlactams B and C, respectively. The 15 known isolates were identified as vitexilactone (4), rotundifuran (5), 8-epi-manoyl oxide (6), vitetrifolin D (7), spathulenol (8), cis-dihydro-dehydro-diconiferylalcohol-9-O-β-D-glucoside (9), luteolin-7-O-glucoside (10), 5-hydroxy-3,6,7,4′-tetramethoxyflavone (11), casticin (12), artemetin (13), aucubin (14), agnuside (15), β-sitosterol (16), p-hydroxybenzoic acid (17), and p-hydroxybenzoic acid glucose ester (18). All compound structures were determined/identified on the basis of 1D and/or 2D NMR and mass spectrometry techniques. Compounds 6, 8, 9, and 18 were reported from a Vitex spieces for the first time. The cancer chemopreventive potentials of these isolates were evaluated for NADP(H):quinone oxidoreductase type 1 (QR1) induction activity. Compound 7 demonstrated promising QR1 induction effect, while the new compound vitexlactam (3) was only slightly active. PMID:23662135

THE RETC CODE FOR QUANTIFYING THE HYDRAULIC FUNCTIONS OF UNSATURATED SOILS

EPA Science Inventory

This report describes the RETC computer code for analyzing the soil water retention and hydraulic conductivity functions of unsaturated soils. These hydraulic properties are key parameters in any quantitative description of water flow into and through the unsaturated zone of soil...

Novel pathogenic mutations and skin biopsy analysis in Knobloch syndrome

PubMed Central

Suzuki, Oscar; Kague, Erika; Bagatini, Kelly; Tu, Hongmin; Heljasvaara, Ritva; Carvalhaes, Lorenza; Gava, Elisandra; de Oliveira, Gisele; Godoi, Paulo; Oliva, Glaucius; Kitten, Gregory; Pihlajaniemi, Taina; Passos-Bueno, Maria-Rita

2009-01-01

Purpose To facilitate future diagnosis of Knobloch syndrome (KS) and better understand its etiology, we sought to identify not yet described COL18A1 mutations in KS patients. In addition, we tested whether mutations in this gene lead to absence of the COL18A1 gene product and attempted to better characterize the functional effect of a previously reported missense mutation. Methods Direct sequencing of COL18A1 exons was performed in KS patients from four unrelated pedigrees. We used immunofluorescent histochemistry in skin biopsies to evaluate the presence of type XVIII collagen in four KS patients carrying two already described mutations: c.3277C>T, a nonsense mutation, and c.3601G>A, a missense mutation. Furthermore, we determined the binding properties of the mutated endostatin domain p.A1381T (c.3601G>A) to extracellular matrix proteins using ELISA and surface plasmon resonance assays. Results We identified four novel mutations in COL18A1, including a large deletion involving exon 41. Skin biopsies from KS patients revealed lack of type XVIII collagen in epithelial basement membranes and blood vessels. We also found a reduced affinity of p.A1381T endostatin to some extracellular matrix components. Conclusions COL18A1 mutations involved in Knobloch syndrome have a distribution bias toward the coding exons of the C-terminal end. Large deletions must also be considered when point mutations are not identified in patients with characteristic KS phenotype. We report, for the first time, lack of type XVIII collagen in KS patients by immunofluorescent histochemistry in skin biopsy samples. As a final point, we suggest the employment of this technique as a preliminary and complementary test for diagnosis of KS in cases when mutation screening either does not detect mutations or reveals mutations of uncertain effect, such as the p.A1381T change. PMID:19390655

Novel pathogenic mutations and skin biopsy analysis in Knobloch syndrome.

PubMed

Suzuki, Oscar; Kague, Erika; Bagatini, Kelly; Tu, Hongmin; Heljasvaara, Ritva; Carvalhaes, Lorenza; Gava, Elisandra; de Oliveira, Gisele; Godoi, Paulo; Oliva, Glaucius; Kitten, Gregory; Pihlajaniemi, Taina; Passos-Bueno, Maria-Rita

2009-01-01

To facilitate future diagnosis of Knobloch syndrome (KS) and better understand its etiology, we sought to identify not yet described COL18A1 mutations in KS patients. In addition, we tested whether mutations in this gene lead to absence of the COL18A1 gene product and attempted to better characterize the functional effect of a previously reported missense mutation. Direct sequencing of COL18A1 exons was performed in KS patients from four unrelated pedigrees. We used immunofluorescent histochemistry in skin biopsies to evaluate the presence of type XVIII collagen in four KS patients carrying two already described mutations: c.3277C>T, a nonsense mutation, and c.3601G>A, a missense mutation. Furthermore, we determined the binding properties of the mutated endostatin domain p.A1381T (c.3601G>A) to extracellular matrix proteins using ELISA and surface plasmon resonance assays. We identified four novel mutations in COL18A1, including a large deletion involving exon 41. Skin biopsies from KS patients revealed lack of type XVIII collagen in epithelial basement membranes and blood vessels. We also found a reduced affinity of p.A1381T endostatin to some extracellular matrix components. COL18A1 mutations involved in Knobloch syndrome have a distribution bias toward the coding exons of the C-terminal end. Large deletions must also be considered when point mutations are not identified in patients with characteristic KS phenotype. We report, for the first time, lack of type XVIII collagen in KS patients by immunofluorescent histochemistry in skin biopsy samples. As a final point, we suggest the employment of this technique as a preliminary and complementary test for diagnosis of KS in cases when mutation screening either does not detect mutations or reveals mutations of uncertain effect, such as the p.A1381T change.

Chemical composition of the ethanolic propolis extracts and its effect on HeLa cells.

PubMed

Barbarić, Monika; Mišković, Katarina; Bojić, Mirza; Lončar, Mirela Baus; Smolčić-Bubalo, Asja; Debeljak, Zeljko; Medić-Šarić, Marica

2011-06-01

Propolis is a resinous hive product collected by honeybees from various plant sources. It is widely used in traditional medicine and is reported to have a broad spectrum of pharmacological effects (antibacterial, antihepatoxic, antioxidative, anti-inflammatory, etc.). Thus the aim of this study was to assess cytotoxic effect of various ethanol propolis extractions on the cervical tumor cell line (HeLa) and compare it with their phenolic acids and flavonoids composition. Twenty samples of raw propolis were collected from 17 localities of Croatia (I-XVII), 2 of Bosnia and Hercegovina (XVIII, XIX) and 1 of Macedonia (XX). Reverse phase HPLC was used to determine the chemical composition of polyphenols. Biological experiments were carried out in vitro on cervix adenocarcinoma cell line (HeLa). Phenolic acids (ferulic acid, p-coumaric acid, caffeic acid) and flavonoids (tectochrysin, galangin, pinocembrin, pinocembrin-7-methylether, chrysin, apigenin, kaempferol, quercetin) have been determined using HPLC analysis in 20 ethanolic propolis extracts. All samples contain tectochrysin in ranges of 0.1988 mg/g (XVIII) to 1.2004 mg/g (III), while caffeic acid and quercetin have not been found. Flavonoid that is most abundant is galangin in ranges from 0.3706 mg/g (XVII) to 47.4879 mg/g (IX). The samples of propolis numbers I, VI and X applied in the investigated concentration range manifested significant reduction of cell growth. GI(50) value as indicator of cytotoxicity among propolis samples showed that propolis number VII is the most effective (GI(50) =76 μg/ml) followed by propolis nos. XV, XVIII and I. Antiproliferative and cytotoxic effect of propolis on the HeLa cells is not correlating with the concentration of particular components but on establishing the possible synergistic antiproliferative activity of individual phenolic acid and flavonoids. Differences in the chemical composition lead to diversity in biological activity of propolis samples. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

Alkenone Paleotemperature Determinations

NASA Astrophysics Data System (ADS)

Herbert, T. D.

2003-12-01

The organic biomarker proxy for past sea surface temperatures ("U37k") came to paleoceanography from an unexpected direction. Nearly all paleoceanographic tools rely on some aspect of the fossilized hard parts of marine organisms. Thus, assemblages of calcareous microplankton such as foraminifera and coccoliths, or of siliceous plankton such as radiolaria and diatoms, provided the basis for the CLIMAP reconstruction of the Ice Age ocean (CLIMAP, 1976, 1981). Additionally, a host of chemical methods relies on the same hard parts to furnish isotopic and trace element signatures, and generally requires that skeletal material be well preserved. The alkenone method differs in several important ways. Individual molecules, extracted and separated from a matrix of hundreds to thousands of other organic compounds, are the targets. In most cases, the remnant alkenones and alkenoates that are the subject of this review constitute no more, and often considerably less, than a few percent of their initial flux that left the surface layer of the ocean and fell toward the sediments. Good preservation is thus not a major issue for use of the proxy. In addition, while many geochemical techniques assume that skeletal material is a passive recorder of isotopic and trace element composition of seawater, and that incorporation of paleo-environmental signals follows thermodynamic laws that can be modeled using nonbiogenic phases in the laboratory, the alkenone method assumes that the ratios of biomarkers measured were actively regulated by the producing organisms in life according to the temperature of the water in which they grew.Alkenone paleothermometry promises a direct estimate of near-surface ocean temperatures. Alkenones and the related alkenoates come exclusively from a few species of haptophyte algae. These organisms require sunlight, and they generally prefer the upper photic zone. The environmental information contained in their molecular fossils therefore is quite specific, although, as will be discussed at length in a later section, ambiguities still exist on the depth and seasonal variations of alkenone-producing species in the ocean. In contrast, many assemblages of planktonic organisms such as foraminifera and radiolaria contain many species known to live well below the surface mixed layer. The link between microfossil assemblages and sea surface temperature and salinity is therefore indirect and statistical, rather than mechanistic.As originally defined by the Bristol organic geochemistry group (Brassell, 1986a, b), the U37k index reflected the proportions of the di-(C37:2), tri-(C37:3), and tetra-(C37:4) unsaturated ketones. Subsequent work showed that there was no empirical benefit to including the C37:4 ketone in a paleotemperature equation. The currently accepted U37k' index (Prahl and Wakeham, 1987) varies positively with temperature, and is defined as C37:2/(C37:2+C37:3), where C37:2 represents the quantity of the di-unsaturated ketone and C37:3 the quantity of the tri-unsaturated form. The alkenone paleotemperature proxy thus depends only on the relative proportions of the common C37 ketones and not on their absolute amounts. Furthermore, although the alkenones are produced by calcareous algae, they survive in sediments where carbonate has dissolved, as first recognized by Marlowe et al. (1984a, b) and Brassell et al. (1986a). The above expression for the index shows that it can vary between 0 and 1.0; thus, it may saturate at either extremely cold or warm temperatures.Alkenones appear recalcitrant to diagenesis in the water column and within sediments relative to other large macromolecules. Indeed, the first reported occurrence of alkenones came not from recent material, but from Miocene age sediments of the Walvis Ridge (Boon et al., 1978). Shortly thereafter, these compounds were linked to modern haptophyte algae, principally Emiliania huxleyi (de Leeuw et al., 1980; Volkman et al., 1980a, b; Marlowe et al., 1984a, b). Reviews of lipid analyses of Deep Sea Drilling Project sediments revealed that most sediments of Pleistocene through mid-Eocene age appeared to contain measurable quantities of alkenones and alkenoates ( Marlowe et al., 1984a, 1990; Brassell, 1993). Brassell et al. (1986a) provided the seminal study linking alkenone unsaturation to paleotemperature fluctuations in the Late Pleistocene. After noting that modern surface sediments differed in their unsaturation ratios depending on latitude, Brassell et al. (1986a, b) reconstructed alkenone unsaturation in conjunction with benthic and planktonic foraminiferal δ18O over the last 8×105 yr in a core from the subtropical North Atlantic. The unsaturation index declined during glacial periods, suggesting cooler surface ocean temperatures during ice age conditions. The authors further demonstrated that the alkenone index gave a continuous paleoclimatic curve, even in intervals barren of foraminifera due to dissolution. Prahl and Wakeham (1987) and Prahl et al. (1988) proposed the first quantitative calibration of alkenone unsaturation to growth temperature. Unsaturation parameters measured on a strain of E.huxleyi grown in the laboratory at known temperatures were compared to the unsaturation index on particulate material collected from the near-surface ocean in the northeast Pacific. Prahl and Wakeham (1987) showed that the laboratory calibration appeared to apply well to the field observations of unsaturation and the water temperature in which the alkenones apparently were synthesized. The calibration of alkenone unsaturation to temperatures expanded with the first systematic study of core-top sediments by Sikes et al. (1991). That study produced two important results: (i) the unsaturation index in recent sediments followed a relation to overlying sea surface temperatures (SSTs) very similar to the Prahl et al. (1988) calibration, and (ii) there appeared to be no ill effects on the unsaturation index over the time of core storage. Pristine or frozen samples were therefore not needed to produce good estimates of the U37k' index for paleoceanographic studies.As with any paleoceanographic proxy, a number of uncertainties must be evaluated that could affect the accuracy measurement as an estimate of past SSTs. The principal caveats raised can be broadly categorized as ecological, physiological, genetic, and diagenetic. All describe factors, which could cause the U37k' index to deviate from a unique relation to SSTs. Ecological concerns come from observations that alkenone-producing species do not inhabit precisely the same depth throughout the ocean, and that they vary in abundance seasonally. The alkenone unsaturation parameter recorded by sediments could therefore measure past temperatures very precisely, but at which depths, and with what seasonal bias? It is also possible that the proportions of alkenones synthesized by haptophyte algae vary with growth rate, independent of temperature. Our present state of ignorance dictates that we do not know the growth phase of haptophyte material exported out of the photic zone - whether the products represent the initial exponential growth phase observed in culture or stationary growth. Natural populations also differ in their genetic composition. Alkenone-producing species are notable for their wide range of environmental tolerances. The consequences for the U37k' index of genetic variations within strains of the same producing species and between the different alkenone-synthesizing species are still debated. In addition, alkenones measured in sediments represent the surviving molecules of a series of degradational pathways that begin in the water column, proceed to the sediment/water interface, and may continue into the sediment. Should there be a bias in the relative lability of the C37:2 and C37:3 ketones, this would be imparted to paleoceanographic reconstructions of temperature.As should become clear, the U37k' index appears nevertheless to provide a remarkably faithful estimate of paleotemperatures near the sea surface. At the same time, difficulties in matching the space and timescales of modern process studies to the information contained in sediments mean that the caveats raised above remain significant. Field studies provide only snapshots of haptophyte abundance and alkenone unsaturation parameters, sediment traps provide only a few years of data at only a few locations in the global ocean, and it is unclear how well laboratory cultures replicate the natural environment. I have endeavored to treat different lines of evidence systematically, but I have found it difficult to discuss each aspect in a purely serial way. The reader will therefore be asked to digest a review in which very diverse measurements and paradigms are woven together to answer the central question of how to reconstruct past ocean surface temperatures with the U37k' proxy.

Effect of Unsaturated Flow on Delayed Response of Unconfined Aquifiers to Pumping

NASA Astrophysics Data System (ADS)

Tartakovsky, G.; Neuman, S. P.

2005-12-01

A new analytical solution is presented for the delayed response process characterizing flow to a partially penetrating well in an unconfined aquifer. The new solution generalizes that of Neuman [1972, 1974] by accounting for unsaturated flow above the water table. Axially symmetric three-dimensional flow in the unsaturated zone is described by a linearized version of Richards' equation in which hydraulic conductivity and water content vary exponentially with incremental capillary pressure head relative to its air entry value (defining the interface between the saturated and unsaturated zones). Unsaturated soil properties are characterized by an exponent κ having the dimension of inverse length and a dimensionless exponent κD = κb where b is initial saturated thickness. Our treatment of the unsaturated zone is similar to that of Kroszynski and Dagan [1975] who however have ignored internal (artesian) aquifer storage. It has been suggested by Boulton [1954, 1963, 1970] and Neuman [1972, 1974], and is confirmed by our solution, that internal storage is required to reproduce the early increase in drawdown characterizing delayed response to pumping in typical aquifers. According to our new solution such aquifers are characterized by relatively large κ_ D values, typically 10 or larger; in the limit as κD tends to infinity (the soil unsaturated water retention capacity becomes insignificant and/or aquifer thickness become large), unsaturated flow becomes unimportant and our solution reduces to that of Neuman. In typical cases corresponding to κD larger than or equal to 10, unsaturated flow is found to have little impact on early and late dimensionless time behaviors of drawdown measured wholly or in part at some distance below the water table; unsaturated flow causes drawdown to increase slightly at intermediate dimensionless time values that represent transition from an early artesian dominated to a late water-table dominated flow regime. The increase in drawdown during this transition period is caused by delayed drainage from the unsaturated zone, whose relatively small effect is superimposed on the more pronounced phenomenon of delay in water table decline relative to artesian head drops below it. Delayed drainage from the unsaturated zone becomes less and less important as κD increases; as it approaches infinity, this effect dies out completely and drawdown is controlled entirely by delayed decline in the water table. The unsaturated zone has major impact on drawdown at intermediate time, and significant impact at early and late times, in the atypical case of small κD values (1 or less), becoming the dominant factor as κD approaches zero (the soil water retention capacity becomes very large and/or saturated thickness becomes insignificant).

Estimating the Spatial Extent of Unsaturated Zones in Heterogeneous River-Aquifer Systems

NASA Astrophysics Data System (ADS)

Schilling, Oliver S.; Irvine, Dylan J.; Hendricks Franssen, Harrie-Jan; Brunner, Philip

2017-12-01

The presence of unsaturated zones at the river-aquifer interface has large implications on numerous hydraulic and chemical processes. However, the hydrological and geological controls that influence the development of unsaturated zones have so far only been analyzed with simplified conceptualizations of flow processes, or homogeneous conceptualizations of the hydraulic conductivity in either the aquifer or the riverbed. We systematically investigated the influence of heterogeneous structures in both the riverbed and the aquifer on the development of unsaturated zones. A stochastic 1-D criterion that takes both riverbed and aquifer heterogeneity into account was developed using a Monte Carlo sampling technique. The approach allows the reliable estimation of the upper bound of the spatial extent of unsaturated areas underneath a riverbed. Through systematic numerical modeling experiments, we furthermore show that horizontal capillary forces can reduce the spatial extent of unsaturated zones under clogged areas. This analysis shows how the spatial structure of clogging layers and aquifers influence the propensity for unsaturated zones to develop: In riverbeds where clogged areas are made up of many small, spatially disconnected patches with a diameter in the order of 1 m, unsaturated areas are less likely to develop compared to riverbeds where large clogged areas exist adjacent to unclogged areas. A combination of the stochastic 1-D criterion with an analysis of the spatial structure of the clogging layers and the potential for resaturation can help develop an appropriate conceptual model and inform the choice of a suitable numerical simulator for river-aquifer systems.

Investigations of the unsaturated zone at two radioactive waste disposal sites in Lithuania.

PubMed

Skuratovič, Žana; Mažeika, Jonas; Petrošius, Rimantas; Martma, Tõnu

2016-01-01

The unsaturated zone is an important part of the water cycle, governed by many hydrological and hydrogeological factors and processes and provide water and nutrients to the terrestrial ecosystem. Besides, the soils of the unsaturated zone are regarded as the first natural barrier to a large extent and are able to limit the spread of contaminants depending on their properties. The unsaturated zone provides a linkage between atmospheric moisture, groundwater, and seepage of groundwater to streams, lakes, or other surface water bodies. The major difference between water flow in saturated and unsaturated soils is that the hydraulic conductivity, which is conventionally assumed to be a constant in saturated soils, is a function of the degree of saturation or matrix suction in the unsaturated soils. In Lithuania, low and intermediate level radioactive wastes generated from medicine, industry and research were accumulated at the Maisiagala radioactive waste repository. Short-lived low and intermediate levels radioactive waste, generated during the operation of the Ignalina Nuclear Power Plant (INPP) and arising after the INPP decommissioning will be disposed of in the near surface repository close to the INPP (Stabatiske site). Extensive data sets of the hydraulic properties and water content attributed to unsaturated zone soil profiles of the two radioactive waste disposal sites have been collected and summarized. Globally widespread radionuclide tritium ((3)H) and stable isotope ratio ((18)O/(16)O and (2)H/(1)H) distribution features were determined in precipitation, unsaturated zone soil moisture profiles and groundwater.

Enhancing Bioremediation of Oil-contaminated Soils by Controlling Nutrient Transport using Dual Characteristics of Soil Pore Structure

NASA Astrophysics Data System (ADS)

Mori, Y.; Suetsugu, A.; Matsumoto, Y.; Fujihara, A.; Suyama, K.; Miyamoto, T.

2012-12-01

Soil structure is heterogeneous with cracks or macropores allowing bypass flow, which may lead to applied chemicals avoiding interaction with soil particles or the contaminated area. We investigated the bioremediation efficiency of oil-contaminated soils by applying suction at the bottom of soil columns during bioremediation. Unsaturated flow conditions were investigated so as to avoid bypass flow and achieve sufficient dispersion of chemicals in the soil column. The boundary conditions at the bottom of the soil columns were 0 kPa and -3 kPa, and were applied to a volcanic ash soil with and without macropores. Unsaturated flow was achieved with -3 kPa and an injection rate of 1/10 of the saturated hydraulic conductivity. The resultant biological activities of the effluent increased dramatically in the unsaturated flow with macropores condition. Unsaturated conditions prevented bypass flow and allowed dispersion of the injected nutrients. Unsaturated flow achieved 60-80% of saturation, which enhanced biological activity in the soil column. Remediation results were better for unsaturated conditions because of higher biological activity. Moreover, unsaturated flow with macropores achieved uniform remediation efficiency from upper through lower positions in the column. Finally, taking the applied solution volume into consideration, unsaturated flow with -3 kPa achieved 10 times higher efficiency when compared with conventional saturated flow application. These results suggest that effective use of nutrients or remediation chemicals is possible by avoiding bypass flow and enhancing biological activity using relatively simple and inexpensive techniques.