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Aliphatic
Terms modified by Aliphatic Selected AbstractsThe molecular composition of soil organic matter as determined by 13C NMR and elemental analyses and correlation with pesticide sorptionEUROPEAN JOURNAL OF SOIL SCIENCE, Issue 6 2006R. Ahmad Summary Although the chemical composition of soil organic matter (SOM) is known to significantly influence sorption of pesticides and other pollutants, it has been difficult to determine the molecular nature of SOM in situ. Here, using 13C nuclear magnetic resonance (NMR) data and elemental composition in a molecular mixing model, we estimated the molecular components of SOM in 24 soils from various agro-ecological regions. Substantial variations were revealed in the molecular nature of SOM. As a proportion of soil carbon the proportion of the carbonyl component ranged from 0.006 to 0.05, charcoal from 0 to 0.15, protein from 0.09 to 0.29, aliphatic from 0.14 to 0.30, carbohydrate from 0.21 to 0.31, and lignin from 0.05 to 0.42. The relationships between Koc (sorption per unit mass of organic carbon) of carbaryl (1-naphthyl methylcarbamate) and phosalone (S- 6-chloro-2,3-dihydro-2-oxobenzoxazol-3-ylmethyl O,O -diethyl phosphorodithioate) and the molecular nature of organic matter in the soils were significant. Of the molecular components estimated, lignin and charcoal contents correlated best with sorption of carbaryl and phosalone. Aliphatic, carbohydrate and protein contents were found to be negatively correlated with the Koc of both pesticides. The study highlights the importance of the molecular nature of SOM in determining sorption affinities of non-ionic pesticides and presents an indirect method for sorption estimation of pesticides. [source] Enantioselective Aza-Morita,Baylis,Hillman Reaction Using Aliphatic ,-Amidosulfones as Imine SurrogatesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 4 2010Nacim Abermil Abstract The bifunctional catalyst 6,-deoxy-6,-acylamino-,-isocupreidine (1) served both as a base to trigger the in situ generation of N -sulfonylimine from readily available ,-amidosulfones and as a chiral nucleophile to initiate the enantioselective aza-Morita,Baylis,Hillman (aza-MBH) reaction. ,-Methylene-,-amino-,-alkyl carbonyl compounds, difficultly accessible previously, can now be synthesized in excellent yields and enantioselectivities. [source] Synthesis of Aliphatic (S)-,-Hydroxycarboxylic Amides using a One-Pot Bienzymatic Cascade of Immobilised Oxynitrilase and Nitrile HydrataseADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 3 2009Sander van Pelt Abstract A one-pot bienzymatic cascade combining a hydroxynitrile lyase (Manihot esculenta, E.C. 4.1.2.10) and a nitrile hydratase (Nitriliruptor alkaliphilus, E.C. 4.2.1.84) for the synthesis of enantiopure aliphatic ,-hydroxycarboxylic amides from aldehydes is described. Both enzymes were immobilised as cross-linked enzyme aggregates (CLEAs). Stability tests show that the nitrile hydratase CLEAs are sensitive to water-immiscible organic solvents as well as to aldehydes and hydrogen cyanide (HCN), but are remarkably stable and show useful activity in acidic aqueous environments of pH,4,5. The cascade reactions are consequently carried out by using a portionwise feed of HCN and moderate concentrations of aldehyde in acidic aqueous buffer to suppress the uncatalysed hydrocyanation background reaction. After optimisation, this method was used to synthesise five different kinds of aliphatic ,-hydroxycarboxylic amides from the corresponding aldehydes with good yields and with enantiomeric purities comparable to those obtained for the ,-hydroxynitriles in the microaqueous hydrocyanation using hydroxynitrile lyase and an excess of HCN. [source] Aliphatic and enantioselective amidases: from hydrolysis to acyl transfer activityJOURNAL OF APPLIED MICROBIOLOGY, Issue 3 2001D. Fournand [source] Linear polyurethanes made from naturally occurring tartaric acidJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 9 2009Romina Marín Abstract Naturally occurring tartaric acid was used as raw material for the synthesis of novel linear polyurethanes (PURs) bearing two carboxylate side-groups in the repeating unit. Aliphatic and aromatic PURs were obtained by reaction in solution of alkyl and benzyl tartrates with hexamethylene diisocyanate and 4,4,-methylene-bis(phenyl isocyanate), respectively. All the novel PURs were thermally stable and optically active. The aliphatic carboxylate-containing PURs had Mw in the 40,70 kDa range, with PD between 2.1 and 2.5; all were semicrystalline polymers with melting temperatures between 100 and 150 °C and Tg in the 50,80 °C range. The aromatic PURs were amorphous materials with molecular weights between 18 kDa and 25 kDa and Tg above 130 °C. Hydrogenolysis of the PUR made from hexamethylene diisocyanate and benzyl tartrate yielded PURs containing up to 40% of free carboxylic side-groups. The tartrate-derived PURs displayed enhanced sensitivity to hydrolysis compared with their unsubstituted 2,6-PUR homologs. The PURs bearing free carboxylic groups were unique in being degraded by water upon incubation under physiological conditions. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2391,2407, 2009 [source] ChemInform Abstract: Reductions of Aliphatic and Aromatic Nitriles to Primary Amines with Diisopropylaminoborane.CHEMINFORM, Issue 29 2009Dustin Haddenham Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] ChemInform Abstract: Asymmetric Hydrogenation of Aromatic, Aliphatic, and ,,,-Unsaturated Acyl Silanes Catalyzed by Tol-binap/Pica Ruthenium(II) Complexes: Practical Synthesis of Optically Active ,-Hydroxysilanes.CHEMINFORM, Issue 26 2008Noriyoshi Arai Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] A Convenient Samarium-Promoted Synthesis of Aliphatic (E)-Nitroalkenes under Mild Conditions.CHEMINFORM, Issue 48 2007Jose M. Concellon Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Chiral Macrocycle-Catalyzed Highly Enantioselective Phenylacetylene Addition to Aliphatic and Vinyl Aldehydes.CHEMINFORM, Issue 42 2007Zi-Bo Li Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] A Convenient Preparation of Aliphatic and Aromatic N-Sulfonylimines Mediated by Sulfamic Acid in Aqueous Media.CHEMINFORM, Issue 39 2006Zhenjiang Li Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Synthesis of S-(3-Chloroquinoxalin-2-yl) Esters of Aliphatic and Aromatic Thiosulfonic Acids.CHEMINFORM, Issue 32 2006V. I. Lubenets Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] ChemInform Abstract: Structurally Dependent Behavior of the Nitromethyl Group of Aliphatic ,-Nitrothioamides under Nitrile Oxide Generation Reaction Conditions.CHEMINFORM, Issue 21 2002Jacek G. Sosnicki Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Contact allergy to epoxy (meth)acrylatesCONTACT DERMATITIS, Issue 1 2009Kristiina Aalto-Korte Background: Contact allergy to epoxy (meth)acrylates, 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy) phenyl]propane (bis-GMA), 2,2-bis[4-(2-hydroxy-3-acryloxypropoxy)phenyl]-propane (bis-GA), 2,2-bis[4-(methacryl-oxyethoxy)phenyl] propane (bis-EMA), 2,2-bis[4-(methacryloxy)phenyl]-propane (bis-MA), and glycidyl methacrylate (GMA) is often manifested together with contact allergy to diglycidyl ether of bisphenol A (DGEBA) epoxy resin. Objective: To analyse patterns of concomitant allergic reactions to the five epoxy (meth)acrylates in relation to exposure. Methods: We reviewed the 1994,2008 patch test files at the Finnish Institute of Occupational Health (FIOH) for reactions to the five epoxy (meth)acrylates, and examined the patients' medical records for exposure. Results: Twenty-four patients had an allergic reaction to at least one of the studied epoxy (meth)acrylates, but specific exposure was found only in five patients: two bis-GMA allergies from dental products, two bis-GA allergies from UV-curable printing inks, and one bis-GA allergy from an anaerobic glue. Only 25% of the patients were negative to DGEBA epoxy resin. Conclusions: The great majority of allergic patch test reactions to bis-GMA, bis-GA, GMA and bis-EMA were not associated with specific exposure, and cross-allergy to DGEBA epoxy resin remained a probable explanation. However, independent reactions to bis-GA indicated specific exposure. Anaerobic sealants may induce sensitization not only to aliphatic (meth)acrylates but also to aromatic bis-GA. [source] DNA damage assessment by comet assay of human lymphocytes exposed to jet propulsion fuelsENVIRONMENTAL AND MOLECULAR MUTAGENESIS, Issue 1 2002Shawna M. Jackman Abstract Exposure to jet fuel damages DNA and results in a number of physiological changes in liver, lung, immune, and neurological tissue. In this study the single-cell gel electrophoresis assay or comet assay was used to compare the DNA damage in human peripheral lymphocytes produced by three jet propulsion fuels: JP-8, JP-5, and JP-8+100. These fuels consist of complex mixtures of aliphatic, aromatic, and substituted naphthalene hydrocarbons. Two exposure times were investigated which correspond to estimated occupational exposure times and concentrations of fuels were used that were based on previous fuel toxicity studies. Analysis of samples for the extent of DNA damage as determined by tail moment and percent tail DNA was performed on exposed cells following a brief recovery time. All fuels produced significant increases in DNA damage; however, only JP-8+100 was genotoxic at the lowest exposure concentration (1:500). At the highest exposure concentration (1:75), the mean tail moments for JP-8 and JP-8+100 (32.041 ± 2.599 and 45.774 ± 4.743, respectively) were significantly greater than for JP-5 (1.314 ± 0.474). These results indicate that JP-8+100 is the most potent inducer of DNA damage in human peripheral lymphocytes and that both JP-8+100 and JP-8 are capable of damaging lymphocyte DNA to a greater extent than JP-5. Environ. Mol. Mutagen. 40:18,23, 2002. © 2002 Wiley-Liss, Inc. [source] The effects of chronic nitrogen fertilization on alpine tundra soil microbial communities: implications for carbon and nitrogen cyclingENVIRONMENTAL MICROBIOLOGY, Issue 11 2008Diana R. Nemergut Summary Many studies have shown that changes in nitrogen (N) availability affect primary productivity in a variety of terrestrial systems, but less is known about the effects of the changing N cycle on soil organic matter (SOM) decomposition. We used a variety of techniques to examine the effects of chronic N amendments on SOM chemistry and microbial community structure and function in an alpine tundra soil. We collected surface soil (0,5 cm) samples from five control and five long-term N-amended plots established and maintained at the Niwot Ridge Long-term Ecological Research (LTER) site. Samples were bulked by treatment and all analyses were conducted on composite samples. The fungal community shifted in response to N amendments, with a decrease in the relative abundance of basidiomycetes. Bacterial community composition also shifted in the fertilized soil, with increases in the relative abundance of sequences related to the Bacteroidetes and Gemmatimonadetes, and decreases in the relative abundance of the Verrucomicrobia. We did not uncover any bacterial sequences that were closely related to known nitrifiers in either soil, but sequences related to archaeal nitrifiers were found in control soils. The ratio of fungi to bacteria did not change in the N-amended soils, but the ratio of archaea to bacteria dropped from 20% to less than 1% in the N-amended plots. Comparisons of aliphatic and aromatic carbon compounds, two broad categories of soil carbon compounds, revealed no between treatment differences. However, G-lignins were found in higher relative abundance in the fertilized soils, while proteins were detected in lower relative abundance. Finally, the activities of two soil enzymes involved in N cycling changed in response to chronic N amendments. These results suggest that chronic N fertilization induces significant shifts in soil carbon dynamics that correspond to shifts in microbial community structure and function. [source] Genetically engineered Pseudomonas: a factory of new bioplastics with broad applicationsENVIRONMENTAL MICROBIOLOGY, Issue 10 2001Elías R. Olivera Summary New bioplastics containing aromatic or mixtures of aliphatic and aromatic monomers have been obtained using genetically engineered strains of Pseudomonas putida. The mutation (,) or deletion (,) of some of the genes involved in the ,-oxidation pathway (fadA,, fadB,,fadA or ,fad,BA mutants) elicits a strong intracellular accumulation of unusual homo- or co-polymers that dramatically alter the morphology of these bacteria, as more than 90% of the cytoplasm is occupied by these macromolecules. The introduction of a blockade in the ,-oxidation pathway, or in other related catabolic routes, has allowed the synthesis of polymers other than those accumulated in the wild type (with regard to both monomer size and relative percentage), the accumulation of certain intermediates that are rapidly catabolized in the wild type and the accumulation in the culture broths of end catabolites that, as in the case of phenylacetic acid, phenylbutyric acid, trans -cinnamic acid or their derivatives, have important medical or pharmaceutical applications (antitumoral, analgesic, radiopotentiators, chemopreventive or antihelmintic). Furthermore, using one of these polyesters (poly 3-hydroxy-6-phenylhexanoate), we obtained polymeric microspheres that could be used as drug vehicles. [source] Synthesis of ,-Amino Nitriles from Carbonyl Compounds, Amines, and Trimethylsilyl Cyanide: Comparison between Catalyst-Free Conditions and the Presence of Tin Ion-Exchanged MontmorilloniteEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 9 2010Jiacheng Wang Abstract In the absence of catalysts, the three-component, one-pot synthesis of ,-amino nitriles proceeded using various aldehydes and ketones together with amines and trimethylsilyl cyanide (TMSCN) in high yields under neat conditions at room temperature. The addition order of the reagents had a significant influence on the yields of the desired ,-amino nitriles. In contrast, when tin ion-exchanged montmorillonite (Sn-Mont), prepared by the ion-exchange of sodium montmorillonite (Na-Mont) with a tin tetrachloride solution, was used as a catalyst, the reaction rates significantly increased compared with those without catalysts, and the range of the applicable carbonyl compounds was also extended: structurally diverse aromatic, aliphatic and heteroatom-containing carbonyl compounds, including sterically hindered ketones as well as aliphatic and aromatic amines, were converted into the desired ,-amino nitriles in good to excellent yields with short reaction times under mild conditions. Sn-Mont showed a better catalytic activity than proton or other metal ion-exchanged montmorillonites, supported SnO2 catalysts and the previously reported homogeneous or heterogeneous catalysts. The recovered catalyst was reused several times without loss of catalytic performance. Along with the expansion of the interlayer space of Sn-Mont, the strong Brønsted acid and Lewis acid nature of Sn-Mont derived from protons and SnO2 nanoparticles present in the interlayers of Sn-Mont likely played important and cooperative roles in the high catalytic activity. [source] A Novel Direct Conversion of Primary Amides to Their Corresponding Methyl EstersEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 6 2007Liang-Chun Li Abstract A novel method was used to directly convert aliphatic and aromatic primary amides into their corresponding methyl esters in high yields (up to 99,%) under mild reaction conditions. Possible mechanisms were studied at the B3LYP/6-31++G(d,p) level of theory. Formation of the ester proceeded through a rearrangement of the ,OMe and ,NH2 groups in the RC(O)NHS(O)OMe intermediate in a H+ -catalyzed six-membered ring transition state structure. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] 3,5-Bis(trifluoromethyl)phenyl Sulfones in the Julia,Kocienski Olefination , Application to the Synthesis of Tri- and Tetrasubstituted OlefinsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 20 2006Diego A. Alonso Abstract 3,5-Bis(trifluoromethyl)phenyl (BTFP) sulfones 8a,d are successfully employed in the modified Julia olefination reaction with carbonyl compounds employing phosphazene base P4- tBu at room temp. in THF, affording tri- and tetrasubstituted olefins in good yields. The Julia,Kocienski olefination between primary alkyl BTFP sulfones 8a,b and aromatic and aliphatic ketones affords the corresponding trisubstituted alkenes in good yields and low stereoselectivities. On the other hand, higher yields and stereoselectivities are obtained in the synthesis of trisubstituted olefins through the other approach, the coupling of secondary alkyl BTFP sulfones 8c,d with aliphatic, aromatic and ,,,-unsaturated aldehydes. For the first time, tetrasubstituted olefins are synthesized by means of the Julia,Kocienski protocol when the isopropyl BTFP sulfone 8c reacts with aliphatic and aromatic ketones, employing P4- tBu as base at THF reflux. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] One-Pot Synthesis of 3-Substituted Isoquinolin-1-(2H)-ones and Fused Isoquinolin-1-(2H)-ones by SRN1 Reactions in DMSOEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 17 2006Javier F. Guastavino Abstract 3-Substituted isoquinolin-1-(2H)-ones and fused isoquinolin-1-(2H)-ones have been obtained by the photostimulated SRN1 reactions of 2-iodobenzamide with the enolates of aromatic (acetophenone, 1-(benzo[d][1,3]dioxol-5-yl)ethanone, 1- and 2-naphthyl methyl ketones, and 2-, 3-, and 4-acetylpyridine), aliphatic (1-adamantyl methyl ketone), and cyclic ketones (1- and 2-indanone, ,- and ,-tetralone, and 1-benzosuberone) in DMSO. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Aliphatic Thiocarbonyl Ylides and Thiobenzophenone: Experimental Study of Regiochemistry and Methylene Transfer in CycloadditionsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 8 2005Rolf Huisgen Abstract 1,3-Dipolar cycloadditions of aliphatic or alicyclic thiocarbonyl ylides 3A-D , sterically hindered at least at one terminus , with thiobenzophenone produce both regioisomeric 1,3-dithiolanes 4 and 5. According to quantum-chemical calculations (preceding paper), a concerted cycloaddition furnishing 2,4-substituted dithiolanes 4 competes with the formation of an intermediate C,C -biradical 9 which cyclizes to the more crowded 4,5-substituted dithiolanes 5. When steric hindrance of 3 increases, the cycloaddition is superseded by ,methylene transfer', i.e., the transfer of the less hindered terminus of 3E-J to the S-atom of thiobenzophenone. The thiobenzophenone S -alkylide 11, thus formed, rapidly reacts with a second molecule ofthiobenzophenone to generate the 4,4,5,5-tetraphenyl-1,3-dithiolane 12 via the highly stabilized C,C -biradical 10. Methylene transfer occurs when the cyclization of the mixed C,C -biradical 9 requires a higher activation barrier than its dissociation to aliphatic thioketone + 11; the threshold is surprisingly well reproduced by calculations. The structural assignment of sixteen 1,3-dithiolanes is based on their formation from corresponding reactant pairs as well as on 1H and 13C chemical shifts. X-ray diffraction analyses of three spiro-1,3-dithiolanes reveal the van der Waals strain in non-bonded interactions, folding angles, shearing forces, and bond lengths. Comparison of the mass spectra of many 1,3-dithiolanes allows the reconstruction of major fragmentation pathways. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Reinvestigation of the Mechanism of gem -Diacylation: Chemoselective Conversion of Aldehydes to Various gem -Diacylates and Their Cleavage under Acidic and Basic ConditionsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 2 2005Veerababurao Kavala Abstract The mechanism of gem -diacylate formation has been studied extensively using tetrabutylammonium tribromide (TBATB) as the catalyst. The reaction proceeds by a nucleophilic attack of an anhydride on an aldehydic carbonyl group, nucleophilic attack of the hemiacylate intermediate on a second molecule of the anhydride, followed by an intermolecular attack of a second acetate group to regenerate the anhydride. gem -Diacylates of various aliphatic and aromatic aldehydes were obtained directly from the reaction of a variety of aliphatic and aromatic acid anhydrides in the presence of a catalytic quantity of tetrabutylammonium tribromide (TBATB) under solvent-free conditions. A significant electronic effect was observed during its formation as well as deprotection to the corresponding aldehyde. Chemoselective gem -diacylation of the aromatic aldehyde containing an electron-donating group has been achieved in the presence of an aldehyde containing an electron-withdrawing group. Deprotection of the gem -diacylate to the parent carbonyl compound can be accomplished in methanol in presence of the same catalyst. Here again, chemoselective deprotection of the gem -diacylate of a substrate containing an electrondonating group has been achieved in the presence of a substrate containing an electron-withdrawing group. Both the acid and base stability order of the various gem -diacylates examined follow a similar order. The stability order determined from the present study is: gem -dibenzoate > gemdipivalate > gem -diisobutyrate > gem -diacetate > gem -dipropionate. All the gem -diacylals are more stable under basic conditions than acidic condition. No correlation was found between the stability order and the pKa's of the corresponding acids; rather, the stability order is directly related to the steric crowding around the carbonyl carbon. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Synthesis of Polyfluorinated Nitrogen-Containing Heterocycles from Hemifluorinated Enones or Organofluorosilicon Building Blocks as Synthetic EquivalentsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 7 2004Frédéric Chanteau Abstract A series of polyfluorinated heterocycles has been prepared by heterocyclisation of hemifluorinated enones or organofluorosilicon synthetic equivalents with different bis(nucleophiles). These polyfluorinated building blocks were obtained by treatment of acylsilanes with perfluoro organometallic reagents. The method is general and has been applied to aliphatic, aromatic and carbohydrate derivatives, to give oxazolidines, imidazolidines, benzodia- and -thiazepines, quinolines and pyrimidines bearing both a fluorine atom and a perfluoroalkyl group in vicinal positions. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Effect of organic matter applications on 13C-NMR spectra of humic acids of soilEUROPEAN JOURNAL OF SOIL SCIENCE, Issue 3 2008S. Dou Summary Much attention has been paid to improving soil fertility with organic matter (OM) application, which not only deals with organic wastes and protects the environment, but also maintains soil fertility and increases crop yields. Much research has also been on the effects of OM applications on the soil's physical, chemical and biological properties, but relatively less attention has been spent on humic substance (HS). In order to clarify the mechanism of improving soil fertility by applying OM, we analysed the changes of structural characteristics of humic acid (HA) from OM applications to soils by 13C-NMR, chemical analysis, thermal analysis, optical properties, IR and fluorescence spectroscopy. Samples of a brown soil (Paleudalf) and a paddy soil (an anthropogenic soil originating from Udifluvents) were collected from the plough layer of the long-term field experiment at Shenyang Agricultural University and Liaoning Provincial Alkali-Saline Soil Institute, respectively. Both field experiments included three treatments each: (i) brown soil, zero-treatment (CKbr) and two pig manure (PM) applications (O1 and O2) at annual rates of 0.9 t ha,1 and 1.8 t ha,1 of organic carbon, respectively; and (ii) paddy soil, zero-treatment (CKpad), pig manure (Op) and rice straw (Or) at annual rates of 2.62 t ha,1 and 1.43 t ha,1 of organic carbon, respectively. An incubation experiment was also carried out to test the field experiment on the brown soil, namely four treatments: zero-treatment (CKc), and three pig manure applications at rates of 30 g kg,1 (C1), 50 g kg,1 (C2) and 70 g kg,1 (C3), respectively. The total incubation was 180 days. The results indicated that number-average molecular weights (Mn), total acidity, aromaticity, excitation maximum wavelength (,Exmax), and the heat ratio of the high to moderate temperature exothermic regions (H3/H2) of the HA all decreased after OM application. The degree of activation (AD), the absorption intensity ratio of 2920 cm,1 to 1720 cm,1 in infrared spectra (IR2920/1720), alkyl C and O-alkyl C of the HA increased. The HA structure tended to become simpler and more aliphatic. [source] The molecular composition of soil organic matter as determined by 13C NMR and elemental analyses and correlation with pesticide sorptionEUROPEAN JOURNAL OF SOIL SCIENCE, Issue 6 2006R. Ahmad Summary Although the chemical composition of soil organic matter (SOM) is known to significantly influence sorption of pesticides and other pollutants, it has been difficult to determine the molecular nature of SOM in situ. Here, using 13C nuclear magnetic resonance (NMR) data and elemental composition in a molecular mixing model, we estimated the molecular components of SOM in 24 soils from various agro-ecological regions. Substantial variations were revealed in the molecular nature of SOM. As a proportion of soil carbon the proportion of the carbonyl component ranged from 0.006 to 0.05, charcoal from 0 to 0.15, protein from 0.09 to 0.29, aliphatic from 0.14 to 0.30, carbohydrate from 0.21 to 0.31, and lignin from 0.05 to 0.42. The relationships between Koc (sorption per unit mass of organic carbon) of carbaryl (1-naphthyl methylcarbamate) and phosalone (S- 6-chloro-2,3-dihydro-2-oxobenzoxazol-3-ylmethyl O,O -diethyl phosphorodithioate) and the molecular nature of organic matter in the soils were significant. Of the molecular components estimated, lignin and charcoal contents correlated best with sorption of carbaryl and phosalone. Aliphatic, carbohydrate and protein contents were found to be negatively correlated with the Koc of both pesticides. The study highlights the importance of the molecular nature of SOM in determining sorption affinities of non-ionic pesticides and presents an indirect method for sorption estimation of pesticides. [source] Riding the sulfur cycle , metabolism of sulfonates and sulfate esters in Gram-negative bacteriaFEMS MICROBIOLOGY REVIEWS, Issue 2 2000Michael A. Kertesz Abstract Sulfonates and sulfate esters are widespread in nature, and make up over 95% of the sulfur content of most aerobic soils. Many microorganisms can use sulfonates and sulfate esters as a source of sulfur for growth, even when they are unable to metabolize the carbon skeleton of the compounds. In these organisms, expression of sulfatases and sulfonatases is repressed in the presence of sulfate, in a process mediated by the LysR-type regulator protein CysB, and the corresponding genes therefore constitute an extension of the cys regulon. Additional regulator proteins required for sulfonate desulfonation have been identified in Escherichia coli (the Cbl protein) and Pseudomonas putida (the AsfR protein). Desulfonation of aromatic and aliphatic sulfonates as sulfur sources by aerobic bacteria is oxygen-dependent, carried out by the ,-ketoglutarate-dependent taurine dioxygenase, or by one of several FMNH2 -dependent monooxygenases. Desulfurization of condensed thiophenes is also FMNH2 -dependent, both in the rhodococci and in two Gram-negative species. Bacterial utilization of aromatic sulfate esters is catalyzed by arylsulfatases, most of which are related to human lysosomal sulfatases and contain an active-site formylglycine group that is generated post-translationally. Sulfate-regulated alkylsulfatases, by contrast, are less well characterized. Our increasing knowledge of the sulfur-regulated metabolism of organosulfur compounds suggests applications in practical fields such as biodesulfurization, bioremediation, and optimization of crop sulfur nutrition. [source] Organic geochemistry indicates Gebel El Zeit, Gulf of Suez, is a source of bitumen used in some Egyptian mummiesGEOARCHAEOLOGY: AN INTERNATIONAL JOURNAL, Issue 3 2005A.O. Barakat Molecular geochemical properties of crude oils and surface petroleum seeps from the southern part of the Gulf of Suez were evaluated. The characterizations of individual aliphatic, aromatic, and biomarker compounds were based on gas chromatography (GC) and gas chromatography/mass spectrometry (GC/MS) analyses. The results provided strong evidence for a close genetic association of these samples. The geochemical characteristics suggest an origin from Tertiary source rocks deposited in a normal marine environment that received continental runoff. The molecular signatures of the investigated samples were very similar to those of the Lower Miocene Rudeis Formation source rock in the southern Gulf of Suez. Further, biomarker fingerprints of the investigated oil seeps were compared with those of the Dead Sea asphalt, as well as the bitumen from some Egyptian mummies reported in the literature. The results demonstrate that oil seeps from the southern end of Gebel El Zeit were used by ancient Egyptians for embalming. © 2005 Wiley Periodicals, Inc. [source] Reactions of Allyl Alcohols of the Pinane Series and of Their Epoxides in the Presence of Montmorillonite ClayHELVETICA CHIMICA ACTA, Issue 2 2007Irina Abstract The reactivity of allyl alcohols of the pinane series and of their epoxides in the presence of montmorillonite clay in intra- and intermolecular reactions was studied. Mutual transformations of (+)- trans -pinocarveol ((+)- 2) and (,)-myrtenol ((,)- 3a) were major reactions of these compounds on askanite,bentonite clay (Schemes,1 and 2). However, the two reactions gave different isomerization products, indicating that the reactivity of the starting alcohol (+)- 2 or (,)- 3a was different from that of the same compound (+)- 2 or (,)- 3 formed in the course of the reactions. (,)- cis - and (+)- trans -Verbenol ((,)- 16 and (+)- 12, resp.), as well as (,)- cis -verbenol epoxide ((,)- 20) reacted with both aliphatic and aromatic aldehydes on askanite,bentonite clay giving various heterocyclic compounds (Schemes,4, 5 and 7); the reaction path depended on the structure of both the terpenoid and the aldehyde. [source] Radical Polymers for Organic Electronic Devices: A Radical Departure from Conjugated Polymers?ADVANCED MATERIALS, Issue 22 2009Kenichi Oyaizu Abstract Radical polymers are aliphatic or nonconjugated polymers bearing organic robust radicals as pendant groups per repeating unit. A large population of the radical redox sites allows the efficient redox gradient-driven electron transport through the polymer layer by outer-sphere self-exchange reactions in electrolyte solutions. The radical polymers are emerging as a new class of electroactive materials useful for various kinds of wet-type energy storage, transport, and conversion devices. Electric-field-driven charge transport by hopping between the densely populated radical sites is also a remarkable aspect of the radical polymers in the solid state, which leads to many dry-type devices such as organic memories, diodes, and switches. [source] Efficient Catalytic Corey,Chaykovsky Reactions Involving Ketone SubstratesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 11-12 2010Sarah Abstract It has been demonstrated for the first time that a sulfide catalyst, utilised at 20,mol% loading, can promote methylene transfer to ketones in the presence of methyl triflate and an organic base. This metal-free methodology is of broad scope , both aliphatic and aromatic ketones (including trifluoromethyl ketones) can be converted to synthetically useful terminal epoxides in excellent yields at room temperature. [source] | ||||||||||||||||||||||||||||||||||||||||