WorldWideScience

Sample records for approach aliphatic monoesters

  1. Non-hazardous organic solvents in the paraffin-embedding technique: a rational approach. Aliphatic monoesters for clearing and dewaxing: butyldecanoate

    DEFF Research Database (Denmark)

    Lyon, H; Holm, I; Prentø, P

    1995-01-01

    and aliphatic hydrocarbons (e.g. alkanes, isoparaffins, petroleum distillates, etc.) were rejected, primarily due to their high vapour pressure. Based on a theoretical study of compounds used for clearing, a number of non-hazardous potential substitutes were chosen. The following experimental study narrowed....... Butyldecanoate has only a slight odour, insignificant vapour pressure (biodegradable....

  2. A biocatalytic approach towards sustainable furanic-aliphatic polyesters

    NARCIS (Netherlands)

    Jiang, Yi; Woortman, Albert J. J.; van Ekenstein, Gert O. R. Alberda; Loos, Katja

    2015-01-01

    An eco-friendly approach towards furanic-aliphatic polyesters as sustainable alternatives to aromatic-aliphatic polyesters is presented. In this approach, biobased dimethyl 2,5-furandicarboxylate (DMFDCA) is polymerized with various (potentially) renewable aliphatic diols via Candida antarctica

  3. A bio-catalytic approach to aliphatic ketones.

    Science.gov (United States)

    Xiong, Mingyong; Deng, Jin; Woodruff, Adam P; Zhu, Minshan; Zhou, Jun; Park, Sun Wook; Li, Hui; Fu, Yao; Zhang, Kechun

    2012-01-01

    Depleting oil reserves and growing environmental concerns have necessitated the development of sustainable processes to fuels and chemicals. Here we have developed a general metabolic platform in E. coli to biosynthesize carboxylic acids. By engineering selectivity of 2-ketoacid decarboxylases and screening for promiscuous aldehyde dehydrogenases, synthetic pathways were constructed to produce both C5 and C6 acids. In particular, the production of isovaleric acid reached 32 g/L (0.22 g/g glucose yield), which is 58% of the theoretical yield. Furthermore, we have developed solid base catalysts to efficiently ketonize the bio-derived carboxylic acids such as isovaleric acid and isocaproic acid into high volume industrial ketones: methyl isobutyl ketone (MIBK, yield 84%), diisobutyl ketone (DIBK, yield 66%) and methyl isoamyl ketone (MIAK, yield 81%). This hybrid "Bio-Catalytic conversion" approach provides a general strategy to manufacture aliphatic ketones, and represents an alternate route to expanding the repertoire of renewable chemicals.

  4. Vapor liquid equilibrium constants through a non-equation of state approach: methane-free aliphatic binary systems

    Energy Technology Data Exchange (ETDEWEB)

    Hsiung, T.H.; Thodos, G.

    1975-06-01

    Northwestern University developed an alternate method to help predict vapor-liquid equilibrium constants without an equation of state by using the fundamental properties associated with the pure-state components and the critical pressure of the mixture. The method consists of developing correlations to help predict K-constants for other aliphatic binary mixtures not containing methane from vapor-liquid equilibrium measurements available in the literature for the 3 binaries of the system ethane-butane-heptane. This approach was tested for 7 other binaries (ethane/n-hexane, propane/i-butane, propane/i-butane, propane/n-pentane, propane/i-pentane, poprane/n-decane, and propylene/i-butane). The K-values obtained displayed good agreement with experimental measurements, especially in the vicinity of the critical point.

  5. Lubricating and Waxy Esters. VI. Effect of Symmetry about Ester on Crystallization of Linear Monoester Isomers

    Directory of Open Access Journals (Sweden)

    Laziz Bouzidi

    2014-08-01

    Full Text Available The crystal structure development of jojoba-like esters incorporating either 1-decenoic acid and/or 1-decenol, namely octadec-9-enyl dec-9-enoate (JLE-281, and its isomer dec-9-enyl oleate (JLE-282 was investigated to reveal the effect of symmetry about the ester group on crystallization of aliphatic fatty monoesters. The phase transformation path was investigated with temperature-time resolved X-ray diffraction during stepped isothermal crystallization, and while cooling from the melt at a fixed rate. Startling differences in phase behavior were uncovered between the isomers. When stepped isothermals were used, selective extinctions occurred at a transition temperature for JLE-281 but not for JLE-282. The extinctions, which are due to dramatic changes in the electronic density of certain families of planes, indicate a phase transition attributed to a brusque rearrangement of the oxygen atoms in the crystal subcell. The phase transition did not occur when the JLEs were cooled continuously. The crucial role played by the position of the alkyl chain and its orientation relative to the easy rotation site of the C–O bond in the phase trajectories of the JLEs was particularly highlighted.

  6. A systems biology approach identifies a R2R3 MYB gene subfamily with distinct and overlapping functions in regulation of aliphatic glucosinolates.

    Directory of Open Access Journals (Sweden)

    Ida Elken Sønderby

    Full Text Available BACKGROUND: Glucosinolates are natural metabolites in the order Brassicales that defend plants against both herbivores and pathogens and can attract specialized insects. Knowledge about the genes controlling glucosinolate regulation is limited. Here, we identify three R2R3 MYB transcription factors regulating aliphatic glucosinolate biosynthesis in Arabidopsis by combining several systems biology tools. METHODOLOGY/PRINCIPAL FINDINGS: MYB28 was identified as a candidate regulator of aliphatic glucosinolates based on its co-localization within a genomic region controlling variation both in aliphatic glucosinolate content (metabolite QTL and in transcript level for genes involved in the biosynthesis of aliphatic glucosinolates (expression QTL, as well as its co-expression with genes in aliphatic glucosinolate biosynthesis. A phylogenetic analysis with the R2R3 motif of MYB28 showed that it and two homologues, MYB29 and MYB76, were members of an Arabidopsis-specific clade that included three characterized regulators of indole glucosinolates. Over-expression of the individual MYB genes showed that they all had the capacity to increase the production of aliphatic glucosinolates in leaves and seeds and induce gene expression of aliphatic biosynthetic genes within leaves. Analysis of leaves and seeds of single knockout mutants showed that mutants of MYB29 and MYB76 have reductions in only short-chained aliphatic glucosinolates whereas a mutant in MYB28 has reductions in both short- and long-chained aliphatic glucosinolates. Furthermore, analysis of a double knockout in MYB28 and MYB29 identified an emergent property of the system since the absence of aliphatic glucosinolates in these plants could not be predicted by the chemotype of the single knockouts. CONCLUSIONS/SIGNIFICANCE: It seems that these cruciferous-specific MYB regulatory genes have evolved both overlapping and specific regulatory capacities. This provides a unique system within which to

  7. A Novel Approach in Cinnamic Acid Synthesis: Direct Synthesis of Cinnamic Acids from Aromatic Aldehydes and Aliphatic Carboxylic Acids in the Presence of Boron Tribromide

    OpenAIRE

    Onciu, M.; Tanasa, F.; C. Chiriac

    2005-01-01

    Cinnamic acids have been prepared in moderate to high yields by a new direct synthesis using aromatic aldehydes and aliphatic carboxylic acids, in the presence of boron tribromide as reagent, 4-dimethylaminopyridine (4-DMAP) and pyridine (Py) as bases and N-methyl-2-pyrolidinone (NMP) as solvent, at reflux (180-190°C) for 8-12 hours.

  8. MALEIC AND SULFOSUCCINIC SATURATED ALIPHATIC (C18) MONOESTERS WITH HETEROGENEOUS POLYOXYETHYLENE (n=8) CHAINS - POTENTIAL AGROALIMENTARY PELLICULAR PROTECTION SYSTEMS

    OpenAIRE

    Mihaela Cazacu; Teodor Trasca; Adrian Rivis; Ileana Cocan; Calin Jianu; Corina Costescu

    2014-01-01

    Natural vegetable waxes in general and the epicuticular in particular, present on the surface of many horticultural products (fruits, vegetables), confer upon them two distinct competences: controlled permeability for water transfer, and respectively for gas transfer in the respiratory process, which significantly affects their window-shop quality. The knowledge and recognition of these qualities has stimulated the study of food product–environment interphase mass transfer mechanisms, along w...

  9. A Novel Approach in Cinnamic Acid Synthesis: Direct Synthesis of Cinnamic Acids from Aromatic Aldehydes and Aliphatic Carboxylic Acids in the Presence of Boron Tribromide

    Directory of Open Access Journals (Sweden)

    M. Onciu

    2005-02-01

    Full Text Available Cinnamic acids have been prepared in moderate to high yields by a new direct synthesis using aromatic aldehydes and aliphatic carboxylic acids, in the presence of boron tribromide as reagent, 4-dimethylaminopyridine (4-DMAP and pyridine (Py as bases and N-methyl-2-pyrolidinone (NMP as solvent, at reflux (180-190°C for 8-12 hours.

  10. Convenient synthesis of β-allenic α-difluoromethylenephosphonic acid monoesters: Potential synthons for cyclic phosphate mimics

    Institute of Scientific and Technical Information of China (English)

    Yun Lin; Jin Tao Liu

    2007-01-01

    β-Allenic α-difluoromethylenephosphonic acid monoesters were prepared under mild conditions for the first time by hydrolyzing the corresponding diethyl phosphonates in aqueous sodium hydroxide solution.

  11. Synthesis and pharmacological activity evaluation of arctigenin monoester derivatives.

    Science.gov (United States)

    Chen, Qiulian; Yang, Limin; Han, Mei; Cai, Enbo; Zhao, Yan

    2016-12-01

    Arctigenin (ARG), a nature medicine with many pharmacological activities, was poorly soluble in water and placed restriction on practical usage. Six novel arctigenin monoester derivatives were obtained from the reflux reaction with arctigenin, carboxylic acids (crotonic acid, furoic acid, 2-naphthalene acid and indol-3-acetic acid), EDCI and DMAP in dichloromethane at 60°C for 4-6h and their properties on nitrite scavenging assay were investigated in vitro. Based on the results, the one of the most effective derivatives, arctigenin β-indolylacetate (ARG6), was selected to study anti-tumor activity in vivo at doses of 20 and 40mg/kg. The results showed that comparison with ARG group, ARG6 exhibited more anti-tumor activity in H22 tumor-bearing mice. Furthermore, ARG6 exhibited less damage to the liver, kidney, spleen and thymus when compared with those in positive group. Biochemical parameters of ALT, AST, BUN and Cre showed ARG6 had little toxicity to mice as well. ARG6 significantly improved serum cytokine levels of IL-2, IL-6, IFN-γ and TNF-α, and decreased VEGF compared with ARG. Moreover, H & E staining, TUNEL assay and immunohistochemical of tumor issues also indicated that ARG6 exhibited anti-tumor activity in vivo. In brief, the present study provide a method to improve ARG anti-tumor activity and provide a reference for new anti-tumor agent.

  12. Urinary phthalate monoesters and endometriosis in infertile Japanese women

    Energy Technology Data Exchange (ETDEWEB)

    Itoh, Hiroaki [Epidemiology and Prevention Division, Research Center for Cancer Prevention and Screening, National Cancer Center, 5-1-1 Tsukiji, Chuo-ku, Tokyo 104-0045 (Japan); Iwasaki, Motoki, E-mail: moiwasak@ncc.go.jp [Epidemiology and Prevention Division, Research Center for Cancer Prevention and Screening, National Cancer Center, 5-1-1 Tsukiji, Chuo-ku, Tokyo 104-0045 (Japan); Hanaoka, Tomoyuki [Epidemiology and Prevention Division, Research Center for Cancer Prevention and Screening, National Cancer Center, 5-1-1 Tsukiji, Chuo-ku, Tokyo 104-0045 (Japan); Sasaki, Hiroshi; Tanaka, Tadao [Department of Obstetrics and Gynecology, Jikei University School of Medicine, 3-25-8, Nishi-Shimbashi, Minato-ku, Tokyo 105-8461 (Japan); Tsugane, Shoichiro [Epidemiology and Prevention Division, Research Center for Cancer Prevention and Screening, National Cancer Center, 5-1-1 Tsukiji, Chuo-ku, Tokyo 104-0045 (Japan)

    2009-12-15

    Phthalates may act as an estrogen and are a potential risk factor for estrogen-related diseases such as endometriosis. We assessed the association between phthalate exposure and endometriosis in 166 consecutive women who presented at a university hospital for consultation regarding infertility. The subjects were interviewed and provided a urine specimen prior to a laparoscopic diagnosis of endometriosis. They were then categorized by the severity of endometriosis as controls (stages 0-I) and cases (stages II-IV). Urinary concentrations of the phthalate metabolites monoethyl phthalate, mono-n-butyl phthalate, monobenzyl phthalate, mono(2-ethylhexyl) phthalate (MEHP), mono(2-ethyl-5-oxohexyl) phthalate, and mono(2-ethyl-5-hydroxyhexyl) phthalate were measured in 57 cases and 80 controls using high-performance liquid chromatography isotope-dilution tandem mass spectrometry. Adjusted odds ratios for endometriosis in relation to dichotomized individual phthalate metabolites (standardized for creatinine) were calculated. No significant association between endometriosis and any urinary creatinine-adjusted phthalate monoester was seen. Adjusted odds ratio (95% confidence interval) for higher dichotomized MEHP by endometriosis was 1.57 (0.74-3.30). No monotonic trend was seen in urinary creatinine-adjusted concentration of phthalate metabolites by endometriosis stage (p = 0.23-0.90). Our results do not support the hypothesis that higher urinary concentrations of phthalate metabolites are associated with the risk of endometriosis in infertile Japanese women.

  13. On the inclusion of alkanes into the monolayer of aliphatic alcohols at the water/alkane vapor interface: a quantum chemical approach.

    Science.gov (United States)

    Vysotsky, Yuri B; Fomina, Elena S; Belyaeva, Elena A; Fainerman, Valentin B; Vollhardt, Dieter

    2013-02-14

    In the framework of the quantum chemical semiempirical PM3 method thermodynamic and structural parameters of the formation and clusterization of aliphatic alcohols C(n)H(2n+1)OH (n(OH) = 8-16) at 298 K at the water/alkane vapor C(n)H(2n+2), (n(CH(3)) = 6-16) interface were calculated. The dependencies of enthalpy, entropy and Gibbs' energy of clusterization per one monomer molecule of 2D films on the alkyl chain length of corresponding alcohols and alkanes, the molar fraction of alkanes in the monolayers and the immersion degree of alcohol molecules into the water phase were shown to be linear or stepwise. The threshold of spontaneous clusterization of aliphatic alcohols at the water/alkane vapor interface was 10-11 carbon atoms at 298 K which is in line with experimental data at the air/water interface. It is shown that the presence of alkane vapor does not influence the process of alcohol monolayer formation. The structure of these monolayers is analogous to those obtained at the air/water interface in agreement with experimental data. The inclusion of alkane molecules into the amphiphilic monolayer at the water/alkane vapor interface is possible for amphiphiles with the spontaneous clusterization threshold at the air/water interface (n(s)(0)) of at least 16 methylene units in the alkyl chain, and it does not depend on the molar fraction of alkanes in the corresponding monolayer. The inclusion of alkanes from the vapor phase into the amphiphilic monolayer also requires that the difference between the alkyl chain lengths of alcohols and alkanes is not larger than n(s)(0) - 15 and n(s)(0) - 14 for the 2D film 1 and 2D film 2, respectively.

  14. Highly selective methodology for the direct conversion of aromatic aldehydes to glycol monoesters.

    Science.gov (United States)

    Sharghi, Hashem; Sarvari, Mona Hosseini

    2003-05-16

    Al(2)O(3)/MeSO(3)H (AMA) was found to be an extremely efficient reagent for the conversion of aromatic aldehydes and diols to glycol monoesters. The remarkable selectivity achieved with this reagent is an attractive feature of the present method.

  15. Synthesis of Versatile Building Blocks through Asymmetric Hydrogenation of Functionalized Itaconic Acid Mono-Esters

    NARCIS (Netherlands)

    Hekking, Koen F.W.; Lefort, Laurent; Vries, André H.M. de; Delft, Floris L. van; Schoemaker, Hans E.; Vries, Johannes G. de; Rutjes, Floris P.J.T.

    2008-01-01

    The rhodium-catalyzed asymmetric hydrogenation of several β-substituted itaconic acid mono-esters, using a library of monodentate phosphoramidite and phosphite ligands is described. Two β-alkyl-substituted substrates were readily hydrogenated by the rhodium complex Rh(COD)2BF4 in combination with (S

  16. Study on biodegradable aromatic/aliphatic copolyesters

    Energy Technology Data Exchange (ETDEWEB)

    Yiwang Chen; Licheng Tan; Lie Chen; Yan, Yang; Xiaofeng Wang [Nanchang University, Nanchang (China). School of Materials Science and Engineering. Inst. of Polymer Materials]. E-mail: ywchen@ncu.edu.cn

    2008-04-15

    Progress on biodegradable aromatic/aliphatic copolyesters based on aliphatic and aromatic diacids, diols and ester monomers was reviewed. The aromatic/aliphatic copolyesters combined excellent mechanical properties with biodegradability. Physical properties and biodegradability of copolyesters varied with chain length of the aliphatic polyester segment and atacticity of copolyesters. The process ability of copolyesters could be improved significantly after incorporating a stiff chain segment through copolymerization of aliphatic polyesters with an aromatic liquid crystal element. The aromatic/aliphatic copolyesters as a new type of biodegradable materials could replace some general plastics in certain applications, namely biomedical and environmental friendly fields. (author)

  17. Study on biodegradable aromatic/aliphatic copolyesters

    Directory of Open Access Journals (Sweden)

    Yiwang Chen

    2008-06-01

    Full Text Available Progress on biodegradable aromatic/aliphatic copolyesters based on aliphatic and aromatic diacids, diols and ester monomers was reviewed. The aromatic/aliphatic copolyesters combined excellent mechanical properties with biodegradability. Physical properties and biodegradability of copolyesters varied with chain length of the aliphatic polyester segment and atacticity of copolyesters. The processability of copolyesters could be improved significantly after incorporating a stiff chain segment through copolymerization of aliphatic polyesters with an aromatic liquid crystal element. The aromatic/aliphatic copolyesters as a new type of biodegradable materials could replace some general plastics in certain applications, namely biomedical and environmental friendly fields.

  18. Cobalt‐Porphyrin‐Catalysed Intramolecular Ring‐Closing C−H Amination of Aliphatic Azides: A Nitrene‐Radical Approach to Saturated Heterocycles

    Science.gov (United States)

    Kuijpers, Petrus F.; Tiekink, Martijn J.; Breukelaar, Willem B.; Broere, Daniël L. J.; van Leest, Nicolaas P.; van der Vlugt, Jarl Ivar; Reek, Joost N. H.

    2017-01-01

    Abstract Cobalt‐porphyrin‐catalysed intramolecular ring‐closing C−H bond amination enables direct synthesis of various N‐heterocycles from aliphatic azides. Pyrrolidines, oxazolidines, imidazolidines, isoindolines and tetrahydroisoquinoline can be obtained in good to excellent yields in a single reaction step with an air‐ and moisture‐stable catalyst. Kinetic studies of the reaction in combination with DFT calculations reveal a metallo‐radical‐type mechanism involving rate‐limiting azide activation to form the key cobalt(III)‐nitrene radical intermediate. A subsequent low barrier intramolecular hydrogen‐atom transfer from a benzylic C−H bond to the nitrene‐radical intermediate followed by a radical rebound step leads to formation of the desired N‐heterocyclic ring products. Kinetic isotope competition experiments are in agreement with a radical‐type C−H bond‐activation step (intramolecular KIE=7), which occurs after the rate‐limiting azide activation step. The use of di‐tert‐butyldicarbonate (Boc2O) significantly enhances the reaction rate by preventing competitive binding of the formed amine product. Under these conditions, the reaction shows clean first‐order kinetics in both the [catalyst] and the [azide substrate], and is zero‐order in [Boc2O]. Modest enantioselectivities (29–46 % ee in the temperature range of 100–80 °C) could be achieved in the ring closure of (4‐azidobutyl)benzene using a new chiral cobalt‐porphyrin catalyst equipped with four (1S)‐(−)‐camphanic‐ester groups. PMID:28332743

  19. Phthalate monoesters in perfusate from a dual placenta perfusion system, the placenta tissue and umbilical cord blood

    DEFF Research Database (Denmark)

    Mose, Tina; Mortensen, Gerda K; Hedegaard, Morten;

    2006-01-01

    Fetal exposure to phthalates may be associated with adverse reproductive effects, including cryptorchidism and decreased semen quality. Information about human placental transfer is needed to qualify the hypotheses. A dual recirculating placenta perfusion system to monitor concentrations of eight...... phthalate monoesters in fetal and maternal perfusates was established. In addition to perfusate background measures of phthalate monoesters, the concentrations in umbilical cord plasma and placenta tissue were measured. Monomethyl phthalate (mMP), monoethyl phthalate (mEP), monobutyl phthalate (m...

  20. Comparisons of phosphorothioate with phosphate transfer reactions for a monoester, diester, and triester: isotope effect studies.

    Science.gov (United States)

    Catrina, Irina E; Hengge, Alvan C

    2003-06-25

    Phosphorothioate esters are sometimes used as surrogates for phosphate ester substrates in studies of enzymatic phosphoryl transfer reactions. To gain better understanding of the comparative inherent chemistry of the two types of esters, we have measured equilibrium and kinetic isotope effects for several phosphorothioate esters of p-nitrophenol (pNPPT) and compared the results with data from phosphate esters. The primary (18)O isotope effect at the phenolic group ((18)k(bridge)), the secondary nitrogen-15 isotope effect ((15)k) in the nitro group, and (for the monoester and diester) the secondary oxygen-18 isotope effect ((18)k(nonbridge)) in the phosphoryl oxygens were measured. The equilibrium isotope effect (EIE) (18)k(nonbridge) for the deprotonation of the monoanion of pNPPT is 1.015 +/- 0.002, very similar to values previously reported for phosphate monoesters. The EIEs for complexation of Zn(2+) and Cd(2+) with the dianion pNPPT(2-) were both unity. The mechanism of the aqueous hydrolysis of the monoanion and dianion of pNPPT, the diester ethyl pNPPT, and the triester dimethyl pNPPT was probed using heavy atom kinetic isotope effects. The results were compared with the data reported for analogous phosphate monoester, diester, and triester reactions. The results suggest that leaving group bond fission in the transition state of reactions of the monoester pNPPT is more advanced than for its phosphate counterpart pNPP, while alkaline hydrolysis of the phosphorothioate diester and triester exhibits somewhat less advanced bond fission than that of their phosphate ester counterparts.

  1. Guided desaturation of unactivated aliphatics

    Science.gov (United States)

    Voica, Ana-Florina; Mendoza, Abraham; Gutekunst, Will R.; Fraga, Jorge Otero; Baran, Phil S.

    2012-08-01

    The excision of hydrogen from an aliphatic carbon chain to produce an isolated olefin (desaturation) without overoxidation is one of the most impressive and powerful biosynthetic transformations for which there are no simple and mild laboratory substitutes. The versatility of olefins and the range of reactions they undergo are unsurpassed in functional group space. Thus, the conversion of a relatively inert aliphatic system into its unsaturated counterpart could open new possibilities in retrosynthesis. In this article, the invention of a directing group to achieve such a transformation under mild, operationally simple, metal-free conditions is outlined. This ‘portable desaturase’ (TzoCl) is a bench-stable, commercial entity (Aldrich, catalogue number L510092) that is facile to install on alcohol and amine functionalities to ultimately effect remote desaturation, while leaving behind a synthetically useful tosyl group.

  2. Aliphatic hydrocarbons of the fungi.

    Science.gov (United States)

    Weete, J. D.

    1972-01-01

    Review of studies of aliphatic hydrocarbons which have been recently detected in the spores of phytopathogenic fungi, and are found to be structurally very similar to the alkanes of higher plants. It appears that the hydrocarbon components of the few mycelial and yeast forms reported resemble the distribution found in bacteria. The occurence and distribution of these compounds in the fungi is discussed. Suggested functional roles of fungal spore alkanes are presented.

  3. Combinatorics of aliphatic amino acids.

    Science.gov (United States)

    Grützmann, Konrad; Böcker, Sebastian; Schuster, Stefan

    2011-01-01

    This study combines biology and mathematics, showing that a relatively simple question from molecular biology can lead to complicated mathematics. The question is how to calculate the number of theoretically possible aliphatic amino acids as a function of the number of carbon atoms in the side chain. The presented calculation is based on earlier results from theoretical chemistry concerning alkyl compounds. Mathematical properties of this number series are highlighted. We discuss which of the theoretically possible structures really occur in living organisms, such as leucine and isoleucine with a chain length of four. This is done both for a strict definition of aliphatic amino acids only involving carbon and hydrogen atoms in their side chain and for a less strict definition allowing sulphur, nitrogen and oxygen atoms. While the main focus is on proteinogenic amino acids, we also give several examples of non-proteinogenic aliphatic amino acids, playing a role, for instance, in signalling. The results are in agreement with a general phenomenon found in biology: Usually, only a small number of molecules are chosen as building blocks to assemble an inconceivable number of different macromolecules as proteins. Thus, natural biological complexity arises from the multifarious combination of building blocks.

  4. A nucleophilic catalysis step is involved in the hydrolysis of aryl phosphate monoesters by human CT acylphosphatase.

    Science.gov (United States)

    Paoli, Paolo; Pazzagli, Luigia; Giannoni, Elisa; Caselli, Anna; Manao, Giampaolo; Camici, Guido; Ramponi, Giampietro

    2003-01-03

    Acylphosphatase, one of the smallest enzymes, is expressed in all organisms. It displays hydrolytic activity on acyl phosphates, nucleoside di- and triphosphates, aryl phosphate monoesters, and polynucleotides, with acyl phosphates being the most specific substrates in vitro. The mechanism of catalysis for human acylphosphatase (the organ-common type isoenzyme) was investigated using both aryl phosphate monoesters and acyl phosphates as substrates. The enzyme is able to catalyze phosphotransfer from p-nitrophenyl phosphate to glycerol (but not from benzoyl phosphate to glycerol), as well as the inorganic phosphate-H(2)18O oxygen exchange reaction in the absence of carboxylic acids or phenols. In short, our findings point to two different catalytic pathways for aryl phosphate monoesters and acyl phosphates. In particular, in the aryl phosphate monoester hydrolysis pathway, an enzyme-phosphate covalent intermediate is formed, whereas the hydrolysis of acyl phosphates seems a more simple process in which the Michaelis complex is attacked directly by a water molecule generating the reaction products. The formation of an enzyme-phosphate covalent complex is consistent with the experiments of isotope exchange and transphosphorylation from substrates to glycerol, as well as with the measurements of the Brønsted free energy relationships using a panel of aryl phosphates with different structures. His-25 involvement in the formation of the enzyme-phosphate covalent complex during the hydrolysis of aryl phosphate monoesters finds significant confirmation in experiments performed with the H25Q mutated enzyme.

  5. Electrochemical study of astaxanthin and astaxanthin n-octanoic monoester and diester: tendency to form radicals.

    Science.gov (United States)

    Focsan, A Ligia; Pan, Shanlin; Kispert, Lowell D

    2014-03-06

    The carotenoid astaxanthin known for its powerful antioxidant activity was electrochemically investigated along with the synthesized astaxanthin n-octanoic monoester and astaxanthin n-octanoic diester. Cyclic voltammograms (CVs) revealed a two-electron transfer oxidation for all three carotenoids with a difference in the two oxidation potentials (ΔE = E2(0) - E1(0)) slightly increasing from astaxanthin to the monoester to diester. Minimal or no exposure to water prevented the formation of carotenoid neutral radicals from dications and radical cations, causing near absence of the fifth peak in the CVs. This makes the CVs almost reversible and enables a more precise simulation of the redox potentials and the equilibrium constants for the formation of radical cations. The first oxidation potential (E1(0)) of 0.767₈, 0.773₈, and 0.775₃ V versus SCE and the second oxidation potential (E2(0)) of 0.982₈, 0.993₁, and 0.996₆ V versus SCE for astaxanthin, monoester, and diester, respectively, have been standardized to the potential of ferrocene of 0.528 V vs SCE given in a previous study. Reduction potentials (E3(0)) for formation of carotenoid neutral radicals from dications after proton loss from the three studied carotenoids are presented and compared to those of other carotenoids. According to our DFT calculations, the most favorable sites for deprotonation of radical cations and dications are found on the cyclohexene rings. These measurements provide insight into important properties of these carotenoids like radical scavenging of (•)OH, (•)CH3, and (•)OOH by proton abstraction from the carotenoid or the formation of carotenoid neutral radicals from radical cations which can quench photoexcited states. There is no essential difference in first oxidation potentials for the three carotenoids, which suggests a similar scavenging rate of the esters of astaxanthin toward (•)OH, (•)CH3, and (•)OOH radicals when compared to astaxanthin itself. The

  6. Bacterial isolates degrading aliphatic polycarbonates.

    Science.gov (United States)

    Suyama, T; Hosoya, H; Tokiwa, Y

    1998-04-15

    Bacteria that degrade an aliphatic polycarbonate, poly(hexamethylene carbonate), were isolated from river water in Ibaraki. Prefecture, Japan, after enrichment in liquid medium containing poly(hexamethylene carbonate) suspensions as carbon source, and dilution to single cells. Four of the strains, 35L, WFF52, 61A and 61B2, degraded poly(hexamethylene carbonate) on agar plate containing suspended poly(hexamethylene carbonate). Degradation of poly(hexamethylene carbonate) was confirmed by gel permeation chromatography. Besides poly(hexamethylene carbonate), the strains were found to degrade poly(tetramethylene carbonate). The strains were characterized morphologically, physiologically, and by 16S rDNA sequence analysis. Strains 35L and WFF52 were tentatively identified as Pseudomonas sp. and Variovorax sp., respectively, while strains 61A and 61B2 constitute an unidentified branch within the beta subclass of the Proteobacteria.

  7. Rapeseed Oil Monoester of Ethylene Glycol Monomethyl Ether as a New Biodiesel

    Directory of Open Access Journals (Sweden)

    Jiang Dayong

    2011-01-01

    Full Text Available A novel biodiesel named rapeseed oil monoester of ethylene glycol monomethyl ether is developed. This fuel has one more ester group than the traditional biodiesel. The fuel was synthesized and structurally identified through FT-IR and P1PH NMR analyses. Engine test results show that when a tested diesel engine is fueled with this biodiesel in place of 0# diesel fuel, engine-out smoke emissions can be decreased by 25.0%–75.0%, CO emissions can be reduced by 50.0%, and unburned HC emissions are lessened significantly. However, NOx emissions generally do not change noticeably. In the area of combustion performance, both engine in-cylinder pressure and its changing rate with crankshaft angle are increased to some extent. Rapeseed oil monoester of ethylene glycol monomethyl ether has a much higher cetane number and shorter ignition delay, leading to autoignition 1.1°CA earlier than diesel fuel during engine operation. Because of certain amount of oxygen contained in the new biodiesel, the engine thermal efficiency is improved 13.5%–20.4% when fueled with the biodiesel compared with diesel fuel.

  8. Synthesis of medronic acid monoesters and their purification by high-performance countercurrent chromatography or by hydroxyapatite

    OpenAIRE

    Elina Puljula; Jouko Vepsäläinen; Petri A. Turhanen

    2016-01-01

    We achieved the synthesis of important medronic acid monoalkyl esters via the dealkylation of mixed trimethyl monoalkyl esters of medronic acid. Two methods were developed for the purification of medronic acid monoesters: 1) small scale (10–20 mg) purification by using hydroxyapatite and 2) large scale (tested up to 140 mg) purification by high-performance countercurrent chromatography (HPCCC).

  9. Synthesis of medronic acid monoesters and their purification by high-performance countercurrent chromatography or by hydroxyapatite

    Directory of Open Access Journals (Sweden)

    Elina Puljula

    2016-10-01

    Full Text Available We achieved the synthesis of important medronic acid monoalkyl esters via the dealkylation of mixed trimethyl monoalkyl esters of medronic acid. Two methods were developed for the purification of medronic acid monoesters: 1 small scale (10–20 mg purification by using hydroxyapatite and 2 large scale (tested up to 140 mg purification by high-performance countercurrent chromatography (HPCCC.

  10. Preliminary safety assessment of C-8 xylitol monoester and xylitol phosphate esters.

    Science.gov (United States)

    Silveira, J E P S; Pereda, M C V; Nogueira, C; Dieamant, G; Cesar, C K M; Assanome, K M; Silva, M S; Torello, C O; Queiroz, M L S; Eberlin, S

    2016-02-01

    Most of the cosmetic compounds with preservative properties available in the market pose some risks concerning safety, such as the possibility of causing sensitization. Due to the fact that there are few options, the proper development of new molecules with this purpose is needed. Xylitol is a natural sugar, and the antimicrobial properties of xylitol-derived compounds have already been described in the literature. C-8 xylitol monoester and xylitol phosphate esters may be useful for the development of skincare products. As an initial screen for safety of chemicals, the combination of in silico methods and in vitro testing can aid in prioritizing resources in toxicological investigations while reducing the ethical and monetary costs that are related to animal and human testing. This study was designed to evaluate the safety of C-8 xylitol monoester and xylitol phosphate esters regarding carcinogenicity, mutagenicity, skin and eye irritation/corrosion and sensitization through alternative methods. For the initial safety assessment, quantitative structure-activity relationship methodology was used. The prediction of the parameters carcinogenicity/mutagenicity, skin and eye irritation/corrosion and sensitization was generated from the chemical structure. The analysis also comprised physical-chemical properties, Cramer rules, threshold of toxicological concern and Michael reaction. In silico results of candidate molecules were compared to 19 compounds with preservative properties that are available in the market. Additionally, in vitro tests (Ames test for mutagenicity, cytotoxicity and phototoxicity tests and hen's egg test--chorioallantoic membrane for irritation) were performed to complement the evaluation. In silico evaluation of both molecules presented no structural alerts related to eye and skin irritation, corrosion and sensitization, but some alerts for micronucleus and carcinogenicity were detected. However, by comparison, C-8 xylitol monoester, xylitol

  11. The base-free chemoselective ring opening of epoxides with carboxylic acids using [bmim]Br: a rapid entry into 1,2-diol mono-esters synthesis.

    Science.gov (United States)

    Rad, Mohammad Navid Soltani; Behrouz, Somayeh

    2013-02-01

    A facile and highly convenient base-free protocol for the chemoselective preparation of 1,2-diol mono-esters is described. In this method, the regioselective ring opening of epoxides with carboxylic acids in the presence of [bmim]Br furnishes the corresponding 1,2-diol mono-esters in excellent yields. This method is efficient for various structurally diverse epoxides and carboxylic acids and it can be efficiently applied for the scale up synthesis of 1,2-diol mono-esters in reasonable to good yields. [bmim]Br remarkably influences the reaction progress and acts as both solvent and catalyst in this protocol.

  12. Synthesis and in vitro antitumor activities of lupeol dicarboxylic acid monoester derivatives.

    Science.gov (United States)

    Li, Weijie; Hao, Jing; Xiao, Yeyu

    2013-12-01

    Ten lupeol dicarboxylic acid monoester derivatives as new potent antitumor agents were synthesized and evaluated for in vitro antitumor activities against A549, LAC, HepG2 and HeLa cell lines. Among them, compounds 1-5 showed excellent antitumor activities against all tested tumor cell lines and compounds 6-10 exhibited high activities against A549, HepG2 and HeLa cells, exceeded lupeol, lupanol and doxorubicin. Compound 2 displayed the highest potent antitumor activities with IC50 values of 5.78 μM against A549 cell, 2.38 μM against LAC cell, 6.14 μM against HepG2 cell and 0.00842 μM against HeLa cell.

  13. Structure-dependent activity of phthalate esters and phthalate monoesters binding to human constitutive androstane receptor.

    Science.gov (United States)

    Zhang, Hong; Zhang, Zhaobin; Nakanishi, Tsuyoshi; Wan, Yi; Hiromori, Youhei; Nagase, Hisamistu; Hu, Jianying

    2015-06-15

    The present study investigated the human constitutive androstane receptor (CAR) binding activities of 23 phthalate esters and 10 phthalate monoesters using a fast and sensitive human CAR yeast two-hybrid assay. Of 23 phthalate esters, 16 were evaluated as positive, and the 10% relative effective concentrations (REC10) ranged from 0.28 (BBP) to 29.51 μM (DEHP), whereas no obvious binding activities were found for the phthalate esters having alkyl chains more than six carbons in length. Of 10 phthalate monoesters, only monoethyl phthalate (MEP), monoisobutyl phthalate (MIBP), and mono-(2-ethyhexyl) tetrabromophthalate (TBMEHP) elicited human CAR binding activities. The REC10 values of MEP and MIBP were 4.27 and 14.13 μM, respectively, higher than those of their corresponding phthalate esters (1.45 μM for DEP and 0.83 μM for DIBP), whereas TBMEHP (0.66 μM) was much lower than TBHP (>10(2) μM). A molecular docking method was performed to simulate the interaction modes between phthalates and human CAR, and active phthalates were found to lie at almost the same site in the human CAR pocket. The docking results suggest that the strong binding of phthalates to human CAR arises primarily from hydrophobic interactions, π-π interactions, and steric effects and that weak hydrogen bonds and weak halogen bonds greatly contribute to the high binding activity of TBMEHP. In conclusion, the current study clarified that an extensive array of phthalates are activators of human CAR.

  14. Approach to the study of C-glycosyl flavones acylated with aliphatic and aromatic acids from Spergularia rubra by high-performance liquid chromatography-photodiode array detection/electrospray ionization multi-stage mass spectrometry.

    Science.gov (United States)

    Ferreres, Federico; Gil-Izquierdo, Angel; Vinholes, Juliana; Grosso, Clara; Valentão, Patrícia; Andrade, Paula B

    2011-03-30

    The use of mass spectrometry (MS) coupled to liquid chromatography (LC) as working tool for the study of the C-glycosyl flavones acylated with aliphatic and aromatic acids has allowed the tentative characterization of these compounds in Spergularia rubra and the establishment of the position of the acylation on the sugar moiety of the C-glycosylation by use of MS data. The combination of retention time (Rt), ultraviolet (UV) and MS(n) data of the compounds revealed their C-glycosyl flavone nature, being luteolin, apigenin and chrysoeriol derivatives. Ten non-acylated flavones were identified, from which six are described for the first time (one 7-O-glycosyl-6,8-diC-glycosyl flavone, four 6,8-diC-glycosyl flavones and one 2"-O-glycosyl-6-C-glycosyl flavone). Twenty-six acylated derivatives were also found for the first time. These compounds are grouped in three classes, namely, C-glycosyl flavones acylated with aliphatic acids, with aromatic acids or with a mixed acylation. The first group is characterized by the presence of one 6,8-diC-(acetyl)glycosyl flavone, four 6,8-diC-(malonyl)glycosyl flavones and two 7-O-glycosyl-6,8-diC-(malonyl)glycosyl flavones, while in the second one twelve 6,8-diC-(acyl)glycosyl flavones and two 7-O-glycosyl-6,8-diC-(acyl)glycosyl flavones are described. The last class contained five 6,8-diC-(malonyl,acyl)glycosyl flavones. No previous work has described the presence of C-glycosyl flavones acylated with aliphatic acids in this genus.

  15. Click Chemistry in Functional Aliphatic Polycarbonates.

    Science.gov (United States)

    Dai, Yu; Zhang, Xiaojin; Xia, Fan

    2017-10-01

    Click chemistry, one of the most important methods in conjugation, plays an extremely significant role in the synthesis of functional aliphatic polycarbonates, which are a group of biodegradable polymers containing carbonate bonds in their main chains. To date, more than 75 articles have been reported on the topic of click chemistry in functional aliphatic polycarbonates. However, these efforts have not yet been highlighted. Six categories of click reactions (alkyne-azide reaction, thiol-ene reaction, Michael addition, epoxy-amine/thiol reaction, Diels-Alder reaction, and imine formation) that have been afforded for further post-polymerization modification of polycarbonates are reviewed. Through this review, a comprehensive understanding of functional aliphatic polycarbonates aims to afford insight on the design of polycarbonates for further post-polymerization modification via click chemistry and the expectation of the practical application. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Microbial degradation of aliphatic and aliphatic-aromatic co-polyesters.

    Science.gov (United States)

    Shah, Aamer Ali; Kato, Satoshi; Shintani, Noboru; Kamini, Numbi Ramudu; Nakajima-Kambe, Toshiaki

    2014-04-01

    Biodegradable plastics (BPs) have attracted much attention since more than a decade because they can easily be degraded by microorganisms in the environment. The development of aliphatic-aromatic co-polyesters has combined excellent mechanical properties with biodegradability and an ideal replacement for the conventional nondegradable thermoplastics. The microorganisms degrading these polyesters are widely distributed in various environments. Although various aliphatic, aromatic, and aliphatic-aromatic co-polyester-degrading microorganisms and their enzymes have been studied and characterized, there are still many groups of microorganisms and enzymes with varying properties awaiting various applications. In this review, we have reported some new microorganisms and their enzymes which could degrade various aliphatic, aromatic, as well as aliphatic-aromatic co-polyesters like poly(butylene succinate) (PBS), poly(butylene succinate)-co-(butylene adipate) (PBSA), poly(ε-caprolactone) (PCL), poly(ethylene succinate) (PES), poly(L-lactic acid) (PLA), poly(3-hydroxybutyrate) and poly(3-hydoxybutyrate-co-3-hydroxyvalterate) (PHB/PHBV), poly(ethylene terephthalate) (PET), poly(butylene terephthalate) (PBT), poly(butylene adipate-co-terephthalate (PBAT), poly(butylene succinate-co-terephthalate) (PBST), and poly(butylene succinate/terephthalate/isophthalate)-co-(lactate) (PBSTIL). The mechanism of degradation of aliphatic as well as aliphatic-aromatic co-polyesters has also been discussed. The degradation ability of microorganisms against various polyesters might be useful for the treatment and recycling of biodegradable wastes or bioremediation of the polyester-contaminated environments.

  17. Rigid particle toughening of aliphatic polyketone

    NARCIS (Netherlands)

    Zuiderduin, W.C.J.; Huetink, Han; Gaymans, R.J.

    2006-01-01

    The influence of precipitated calcium carbonate particles on the toughening behaviour of aliphatic polyketone has been studied. The calcium carbonate particles had a particle size of 0.7 mm and a stearic acid coating (1%). Composites of 0e31.5 vol% CaCO3 content have been compounded and injection

  18. Notch sensitivity of aliphatic polyketone terpolymers

    NARCIS (Netherlands)

    Zuiderduin, W.C.J.; Huetink, J.; Gaymans, R.J.

    2004-01-01

    The notch sensitivity of aliphatic polyketone (PK) terpolymers was investigated in this article. The notch-tip radius was varied between the size of an actual propagating crack tip of 1-2 m and the largest notch tip of 1000 m radius. The larger notch-tip radii (1000-15 m) were milled into the polyme

  19. CCN activity of aliphatic amine secondary aerosol

    Directory of Open Access Journals (Sweden)

    X. Tang

    2014-01-01

    Full Text Available Aliphatic amines can form secondary aerosol via oxidation with atmospheric radicals (e.g. hydroxyl radical and nitrate radical. The particle composition can contain both secondary organic aerosol (SOA and inorganic salts. The fraction of organic to inorganic materials in the particulate phase influences aerosol hygroscopicity and cloud condensation nuclei (CCN activity. SOA formed from trimethylamine (TMA and butylamine (BA reactions with hydroxyl radical (OH is composed of organic material of low hygroscopicity (single hygroscopicity parameter, κ ≤ 0.25. Secondary aerosol formed from the tertiary aliphatic amine (TMA with N2O5 (source of nitrate radical, NO3, contains less volatile compounds than the primary aliphatic amine (BA aerosol. TMA + N2O5 form semi-volatile organics in low RH conditions that have κ ~ 0.20, indicative of slightly soluble organic material. As RH increases, several inorganic amine salts are formed as a result of acid-base reactions. The CCN activity of the humid TMA-N2O5 aerosol obeys Zdanovskii, Stokes, and Robinson (ZSR ideal mixing rules. Higher CCN activity (κ > 0.3 was also observed for humid BA+N2O5 aerosols compared with dry aerosol (κ ~ 0.2, as a result of the formation of inorganic salts such as NH4NO3 and butylamine nitrate (C4H11N · HNO3. Compared with TMA, BA+N2O5 reactions produce more volatile aerosols. The BA+N2O5 aerosol products under humid experiments were found to be very sensitive to the temperature within the stream-wise continuous flow thermal gradient CCN counter. The CCN counter, when set above a 21 °C temperature difference, evaporates BA+N2O5 aerosol formed at RH ≥ 30%; κ ranges from 0.4 to 0.7 and is dependent on the instrument supersaturation (ss settings. The aerosol behaves non-ideally, hence simple ZSR rules cannot be applied to the CCN results from the primary aliphatic amine system. Overall, aliphatic amine aerosol systems κ ranges from 0.2 < κ < 0.7. This work indicates that

  20. 40 CFR 721.6140 - Dialkyldithiophosphoric acid, aliphatic amine salt.

    Science.gov (United States)

    2010-07-01

    ..., aliphatic amine salt. 721.6140 Section 721.6140 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.6140 Dialkyldithiophosphoric acid, aliphatic amine salt. (a) Chemical... as a dialkyldithiophosphoric acid, aliphatic amine salt (P-90-1839) is subject to reporting under...

  1. The Feasibility of Enzyme Targeted Activation for Amino Acid/Dipeptide Monoester Prodrugs of Floxuridine; Cathepsin D as a Potential Targeted Enzyme

    Directory of Open Access Journals (Sweden)

    Gordon L. Amidon

    2012-03-01

    Full Text Available The improvement of therapeutic efficacy for cancer agents has been a big challenge which includes the increase of tumor selectivity and the reduction of adverse effects at non-tumor sites. In order to achieve those goals, prodrug approaches have been extensively investigated. In this report, the potential activation enzymes for 5¢-amino acid/dipeptide monoester floxuridine prodrugs in pancreatic cancer cells were selected and the feasibility of enzyme specific activation of prodrugs was evaluated. All prodrugs exhibited the range of 3.0–105.7 min of half life in Capan-2 cell homogenate with the presence and the absence of selective enzyme inhibitors. 5¢-O-L-Phenylalanyl-L-tyrosyl-floxuridine exhibited longer half life only with the presence of pepstatin A. Human cathepsin B and D selectively hydrolized 5¢-O-L-phenylalanyl-L-tyrosylfloxuridine and 5¢-O-L-phenylalanyl-L-glycylfloxuridine compared to the other tested prodrugs. The wide range of growth inhibitory effect by floxuridine prodrugs in Capan-2 cells was observed due to the different affinities of prodrug promoieties to enyzmes. In conclusion, it is feasible to design prodrugs which are activated by specific enzymes. Cathepsin D might be a good candidate as a target enzyme for prodrug activation and 5¢-O-L-phenylalanyl-L-tyrosylfloxuridine may be the best candidate among the tested floxuridine prodrugs.

  2. Attachment of inorganic moieties onto aliphatic polyurethanes

    OpenAIRE

    Eliane Ayres; Wander Luiz Vasconcelos; Rodrigo Lambert Oréfice

    2007-01-01

    Polyurethanes have been used in a series of applications due basically to their versatility in terms of controlling the behavior by altering basically the type of reagents used. However, for more specific and advanced applications, such as in membranes, biomaterials and sensors, well-organized and defined chemical functionalities are necessary. In this work, inorganic functionalities were incorporated into aliphatic polyurethanes (PU) having different macromolecular architectures. Polyurethan...

  3. EPR study of the astaxanthin n-octanoic acid monoester and diester radicals on silica-alumina.

    Science.gov (United States)

    Focsan, A Ligia; Bowman, Michael K; Shamshina, Julia; Krzyaniak, Matthew D; Magyar, Adam; Polyakov, Nikolay E; Kispert, Lowell D

    2012-11-08

    The radical intermediates of the n-octanoic monoester and n-octanoic diester of astaxanthin were detected by pulsed EPR measurements carried out on the UV-produced radicals on silica-alumina artificial matrix and characterized by density functional theory (DFT) calculations. Previous Mims ENDOR for astaxanthin detected the radical cation and neutral radicals formed by proton loss from the C3 (or C3') position and from the methyl groups. Deprotonation of the astaxanthin neutral radical formed at the C3 (or C3') position resulted in a radical anion. DFT calculations for astaxanthin showed that the lowest energy neutral radical forms by proton loss at the C3 (or C3') position of the terminal ring followed by proton loss at the methyl groups of the polyene chain. Contrary to astaxanthin where proton loss can occur at either end of the symmetrical radical, for the diester of astaxanthin, this loss is prevented at the cyclohexene ends and is favored for its methyl groups. The monoester of astaxanthin, however, allows formation of the neutral radical at C3' and prevents its formation at the opposite end where the ester group is attached. At the terminal ring without the ester group attached, migration of proton from hydroxyl group to carbonyl group facilitates resonance stabilization, similarly to already published results for astaxanthin. However, cw EPR shows no evidence of a monoester radical anion formed. This study suggests the different radicals of astaxanthin and its esters that would form in a preferred environment, either hydrophobic or hydrophilic, depending on their structure.

  4. Synthesis of fatty monoester lubricant base oil catalyzed by Fe-Zn double-metal cyanide complex

    Indian Academy of Sciences (India)

    Ravindra K Raut; Mehejabeen Shaikh; Srinivas Darbha

    2014-07-01

    Fatty monoester lubricant base oils as high as 96.7 mol% were prepared by reacting methyl oleate with long-chain alcohols viz., 2-ethyl-1-hexanol (C8−OH), 1-decanol (C10OH) and 1-dodecanol (C12OH) in the presence of a solid Fe-Zn double-metal cyanide (DMC) complex catalyst. Unlike many other acid catalysts, DMC doesn't produce undesired ether side products. The catalyst was reusable in four recycling experiments with little loss in catalytic activity and ester yield. The long-chain esters prepared in the study have the desired physical properties for their application as lubricant base oils.

  5. CCN activity of aliphatic amine secondary aerosol

    Science.gov (United States)

    Tang, X.; Price, D.; Praske, E.; Vu, D.; Purvis-Roberts, K.; Silva, P. J.; Cocker, D. R., III; Asa-Awuku, A.

    2014-01-01

    Aliphatic amines can form secondary aerosol via oxidation with atmospheric radicals (e.g. hydroxyl radical and nitrate radical). The particle composition can contain both secondary organic aerosol (SOA) and inorganic salts. The fraction of organic to inorganic materials in the particulate phase influences aerosol hygroscopicity and cloud condensation nuclei (CCN) activity. SOA formed from trimethylamine (TMA) and butylamine (BA) reactions with hydroxyl radical (OH) is composed of organic material of low hygroscopicity (single hygroscopicity parameter, κ ≤ 0.25). Secondary aerosol formed from the tertiary aliphatic amine (TMA) with N2O5 (source of nitrate radical, NO3), contains less volatile compounds than the primary aliphatic amine (BA) aerosol. TMA + N2O5 form semi-volatile organics in low RH conditions that have κ ~ 0.20, indicative of slightly soluble organic material. As RH increases, several inorganic amine salts are formed as a result of acid-base reactions. The CCN activity of the humid TMA-N2O5 aerosol obeys Zdanovskii, Stokes, and Robinson (ZSR) ideal mixing rules. Higher CCN activity (κ > 0.3) was also observed for humid BA+N2O5 aerosols compared with dry aerosol (κ ~ 0.2), as a result of the formation of inorganic salts such as NH4NO3 and butylamine nitrate (C4H11N · HNO3). Compared with TMA, BA+N2O5 reactions produce more volatile aerosols. The BA+N2O5 aerosol products under humid experiments were found to be very sensitive to the temperature within the stream-wise continuous flow thermal gradient CCN counter. The CCN counter, when set above a 21 °C temperature difference, evaporates BA+N2O5 aerosol formed at RH ≥ 30%; κ ranges from 0.4 to 0.7 and is dependent on the instrument supersaturation (ss) settings. The aerosol behaves non-ideally, hence simple ZSR rules cannot be applied to the CCN results from the primary aliphatic amine system. Overall, aliphatic amine aerosol systems κ ranges from 0.2 systems.

  6. In vitro and in vivo evaluations of the activities of lauric acid monoester formulations against Staphylococcus aureus.

    Science.gov (United States)

    Rouse, Mark S; Rotger, Margalida; Piper, Kerryl E; Steckelberg, James M; Scholz, Matthew; Andrews, Jeffrey; Patel, Robin

    2005-08-01

    Due to increasing mupirocin resistance, alternatives for Staphylococcus aureus nasal decolonization are needed. Lauric acid monoesters combined with lactic, mandelic, malic, or benzoic acid are being evaluated as possible alternatives. We determined the in vitro activity of 13 lauric acid monoester (LAM) formulations and mupirocin against 30 methicillin-susceptible S. aureus (MSSA) isolates and 30 methicillin-resistant S. aureus (MRSA) isolates. We then used a murine model of MRSA nasopharyngeal colonization to compare the in vivo activity of mupirocin with three LAM formulations. MSSA and MRSA MIC(90) values were 0.25 microg/ml for mupirocin and

  7. Enhanced Absorption and Growth Inhibition with Amino Acid Monoester Prodrugs of Floxuridine by Targeting hPEPT1 Transporters

    Directory of Open Access Journals (Sweden)

    Gordon L. Amidon

    2008-06-01

    Full Text Available A series of amino acid monoester prodrugs of floxuridine was synthesized and evaluated for the improvement of oral bioavailability and the feasibility of target drug delivery via oligopeptide transporters. All floxuridine 5′-amino acid monoester prodrugs exhibited PEPT1 affinity, with inhibition coefficients of Gly-Sar uptake (IC50 ranging from 0.7 – 2.3 mM in Caco-2 and 2.0 – 4.8 mM in AsPC-1 cells, while that of floxuridine was 7.3 mM and 6.3 mM, respectively. Caco-2 membrane permeabilities of floxuridine prodrugs (1.01 – 5.31 x 10-6 cm/sec and floxuridine (0.48 x 10-6 cm/sec were much higher than that of 5-FU (0.038 x 10-6 cm/sec. MDCK cells stably transfected with the human oligopeptide transporter PEPT1 (MDCK/hPEPT1 exhibited enhanced cell growth inhibition in the presence of the prodrugs. This prodrug strategy offers great potential, not only for increased drug absorption but also for improved tumor selectivity and drug efficacy.

  8. Preparation and surface active properties of oxypropylated diol monoesters of fatty acids with an amide oxime terminal group

    Directory of Open Access Journals (Sweden)

    Eissa, A. M.F.

    1994-10-01

    Full Text Available Locally produced non-edible oil, namely, rice bran oil (R.B.O. was utilized as starting materials for preparing new nonionic surfactant. Oxypropylated diol monoesters of linoleic and rice bran oil fatty acids were prepared. Also amide oxime derivatives were obtained. Surface active properties of these compounds were measured. Under neutral condition amide eximes served as nonionic surfactants and their properties were similar to other oxypropylated monoesters.

    Se ha utilizado un aceite no comestible de producción local, denominado, aceite de salvado de arroz (R.B.O. como materia prima para la preparación de nuevos tensioactivos no iónicos. Se prepararon diol monoésteres oxipropilados de ácido linoleico y ácidos grasos de aceite de salvado de arroz. También se obtuvieron los derivados de amido oxima. Se midieron las propiedades de tensión superficial de estos compuestos. Bajo condiciones neutras las amido eximas sirvieron como tensioactivos no iónicos y sus propiedades fueron similares a los de otros monoésteres oxipropilados.

  9. Interaction between hypocrellin and aliphatic amines

    Institute of Scientific and Technical Information of China (English)

    张曼华; 陈申; 夏万林; 蒋丽金; 陈德文

    1996-01-01

    The interaction of hypocrellin, including hypocrellin A (HA) and hypocrellin B (HB), with aliphatic amines in deaerated solutions has been studied by ESR and nanosecond transient absorption spectra. In polar solvents, the acid-base interaction between hypocrellin and amines was observed without irradiation. The signals of semiquinone radical anions of hypocrellm and the spin-trapping adduct of α-phenyl-N-tertbutyl-ratrone (PNB) with the aminoalkyl radicals have been detected in photoinduced ESR studies. The transient absorption of excited triplet state of HA and semiquinone radical anion of HA have been observed in laser flash photolysis studies.

  10. The effect of diesters and lauric acid on rheological properties of air/water interfaces stabilized by oligofructose lauric acid monoesters

    NARCIS (Netherlands)

    Kempen, van S.E.H.J.; Schols, H.A.; Linden, van der E.; Sagis, L.M.C.

    2013-01-01

    In this study, the rheological properties of interfaces stabilized by oligofructose fatty acid esters were elucidated. First, the properties of interfaces stabilized by monoesters (ME), diesters (DE), lauric acid (LA), oligofructose (OF), and mixtures of ME with DE, LA, or OF were studied. Second, t

  11. 40 CFR 180.1250 - C8, C10, and C12 fatty acid monoesters of glycerol and propylene glycol; exemption from the...

    Science.gov (United States)

    2010-07-01

    ... of glycerol and propylene glycol; exemption from the requirement of a tolerance. 180.1250 Section 180..., C10, and C12 fatty acid monoesters of glycerol and propylene glycol; exemption from the requirement of... monocaprylate, glycerol monocaprate, and glycerol monolaurate) and propylene glycol (propylene...

  12. Biofiltration of gasoline and diesel aliphatic hydrocarbons.

    Science.gov (United States)

    Halecky, Martin; Rousova, Jana; Paca, Jan; Kozliak, Evguenii; Seames, Wayne; Jones, Kim

    2015-02-01

    The ability of a biofilm to switch between the mixtures of mostly aromatic and aliphatic hydrocarbons was investigated to assess biofiltration efficiency and potential substrate interactions. A switch from gasoline, which consisted of both aliphatic and aromatic hydrocarbons, to a mixture of volatile diesel n-alkanes resulted in a significant increase in biofiltration efficiency, despite the lack of readily biodegradable aromatic hydrocarbons in the diesel mixture. This improved biofilter performance was shown to be the result of the presence of larger size (C₉-C(12)) linear alkanes in diesel, which turned out to be more degradable than their shorter-chain (C₆-C₈) homologues in gasoline. The evidence obtained from both biofiltration-based and independent microbiological tests indicated that the rate was limited by biochemical reactions, with the inhibition of shorter chain alkane biodegradation by their larger size homologues as corroborated by a significant substrate specialization along the biofilter bed. These observations were explained by the lack of specific enzymes designed for the oxidation of short-chain alkanes as opposed to their longer carbon chain homologues.

  13. Gaseous aliphatic aldehydes in Chinese incense smoke

    Energy Technology Data Exchange (ETDEWEB)

    Lin, J.M.; Wang, L.H. (National Taiwan Univ., Taipei (China))

    1994-09-01

    Aliphatic aldehydes were found during the combustion of materials. Tobacco smoke contains aldehydes. Fire fighters were exposed to aldehydes when they conducted firefighting. Aldehydes in ambient air come mainly from the incomplete combustion of hydrocarbons and from photochemical reaction. Most aldehydes in ambient air are formaldehyde and acetaldehyde. Formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, and benzaldehyde were found in the atmosphere in Los Angeles. Burning Chinese incense for worshipping deities is a Chinese daily routine. It was suspected to be a factor causing nasopharynegeal cancer. Epidemiological studies correlated it with the high risk of childhood brain tumor and the high risk of childhood leukemia. Ames test identified the mutagenic effect of the smoke from burning Chinese incense. The smoke had bee proved to contain polycyclic aromatic hydrocarbons and aromatic aldehydes. Suspicion about formaldehyde and other alphatic aldehydes was evoked, when a survey of indoor air pollution was conducted in Taipei city. This study determined the presence of aliphatic aldehydes in the smoke from burning Chinese incense under a controlled atmosphere. 12 refs., 5 figs., 2 tabs.

  14. Biodegradation of aliphatic and aromatic polycarbonates.

    Science.gov (United States)

    Artham, Trishul; Doble, Mukesh

    2008-01-01

    Polycarbonate is one of the most widely used engineering plastics because of its superior physical, chemical, and mechanical properties. Understanding the biodegradation of this polymer is of great importance to answer the increasing problems in waste management of this polymer. Aliphatic polycarbonates are known to biodegrade either through the action of pure enzymes or by bacterial whole cells. Very little information is available that deals with the biodegradation of aromatic polycarbonates. Biodegradation is governed by different factors that include polymer characteristics, type of organism, and nature of pretreatment. The polymer characteristics such as its mobility, tacticity, crystallinity, molecular weight, the type of functional groups and substituents present in its structure, and plasticizers or additives added to the polymer all play an important role in its degradation. The carbonate bond in aliphatic polycarbonates is facile and hence this polymer is easily biodegradable. On the other hand, bisphenol A polycarbonate contains benzene rings and quaternary carbon atoms which form bulky and stiff chains that enhance rigidity. Even though this polycarbonate is amorphous in nature because of considerable free volume, it is non-biodegradable since the carbonate bond is inaccessible to enzymes because of the presence of bulky phenyl groups on either side. In order to facilitate the biodegradation of polymers few pretreatment techniques which include photo-oxidation, gamma-irradiation, or use of chemicals have been tested. Addition of biosurfactants to improve the interaction between the polymer and the microorganisms, and blending with natural or synthetic polymers that degrade easily, can also enhance the biodegradation.

  15. Effects of alkyl side chains on properties of aliphatic amino acids probed using quantum chemical calculations.

    Science.gov (United States)

    Ganesan, Aravindhan; Wang, Feng; Brunger, Michael; Prince, Kevin

    2011-09-01

    Effects of alkyl side chains (R-) on the electronic structural properties of aliphatic amino acids are investigated using quantum mechanical approaches. The carbon (C 1s) binding energy spectra of the aliphatic amino acids are derived from the C 1s spectrum of glycine (the parent spectrum) by the addition of spectral peaks, depending on the alkyl side chains, appearing in the lower energy region IP aliphatic amino acids owing to perturbations depending on the size and structure of the alkyl chains. The pattern of the N 1s and O 1s spectra in glycine is retained in the spectra of the other amino acids with small shifts to lower energy, again depending on the alkyl side chain. The Hirshfeld charge analyses confirm the observations. The alkyl effects on the valence binding energy spectra of the amino acids are concentrated in the middle valence energy region of 12-16 eV, and hence this energy region of 12-16 eV is considered as the `fingerprint' of the alkyl side chains. Selected valence orbitals, either inside or outside of the alkyl fingerprint region, are presented using both density distributions and orbital momentum distributions, in order to understand the chemical bonding of the amino acids. It is also observed that the HOMO-LUMO energy gaps of the aliphatic amino acids are reduced with the growth of the alkyl side chain.

  16. Implications of protonation and substituent effects for C-O and O-P bond cleavage in phosphate monoesters.

    Science.gov (United States)

    Loncke, Paul G; Berti, Paul J

    2006-05-10

    A recent study of phosphate monoesters that broke down exclusively through C-O bond cleavage and whose reactivity was unaffected by protonation of the nonbridging oxygens (Byczynski et al. J. Am. Chem. Soc. 2003, 125, 12541) raised several questions about the reactivity of phosphate monoesters, R-O-P(i). Potential catalytic strategies, particularly with regard to selectively promoting C-O or O-P bond cleavage, were investigated computationally through simple alkyl and aryl phosphate monoesters. Both C-O and O-P bonds lengthened upon protonating the bridging oxygen, R-O(H(+))-P(i), and heterolytic bond dissociation energies, DeltaH(C)(-)(O) and DeltaH(O)(-)(P), decreased. Which bond will break depends on the protonation state of the phosphoryl moiety, P(i), and the identity of the organosubstituent, R. Protonating the bridging oxygen when the nonbridging oxygens were already protonated favored C-O cleavage, while protonating the bridging oxygen of the dianion form, R-O-PO(3)(2)(-), favored O-P cleavage. Alkyl R groups capable of forming stable cations were more prone to C-O bond cleavage, with tBu > iPr > F(2)iPr > Me. The lack of effect on the C-O cleavage rate from protonating nonbridging oxygens could arise from two precisely offsetting effects: Protonating nonbridging oxygens lengthens the C-O bond, making it more reactive, but also decreases the bridging oxygen proton affinity, making it less likely to be protonated and, therefore, less reactive. The lack of effect could also arise without bridging oxygen protonation if the ratio of rate constants with different protonation states precisely matched the ratio of acidity constants, K(a). Calculations used hybrid density functional theory (B3PW91/6-31++G) methods with a conductor-like polarizable continuum model (CPCM) of solvation. Calculations on Me-phosphate using MP2/aug-cc-pVDZ and PBE0/aug-cc-pVDZ levels of theory, and variations on the solvation model, confirmed the reproducibility with different

  17. 40 CFR 721.4568 - Methylpolychloro aliphatic ketone.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Methylpolychloro aliphatic ketone. 721... Substances § 721.4568 Methylpolychloro aliphatic ketone. (a) Chemical substance and significant new uses... ketone (PMN No. P-91-1321) is subject to reporting under this section for the significant new uses...

  18. 40 CFR 721.2270 - Aliphatic dicarboxylic acid salt.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Aliphatic dicarboxylic acid salt. 721... Substances § 721.2270 Aliphatic dicarboxylic acid salt. (a) Chemical substance and significant new uses... salt (PMN P-92-1352) is subject to reporting under this section for the significant new uses described...

  19. Determination of phthalate monoesters in human milk, consumer milk, and infant formula by tandem mass spectrometry (LC-MS-MS)

    DEFF Research Database (Denmark)

    Mortensen, Gerda Krog; Main, Katharina M; Andersson, Anna-Maria

    2005-01-01

    phthalate (mBzP), mono-(2-ethylhexyl) phthalate (mEHP), and monoisononyl phthalate (mNP). The method is based on liquid extraction with a mixture of ethyl acetate and cyclohexane (95:5) followed by two-step solid-phase extraction (SPE). Detection and quantification of the phthalate monoesters were...... these phthalates were present, albeit at different concentrations. Median values (microg L(-1)) obtained were 0.11 (mMP), 0.95 (mEP), 3.5 (mBP), 0.8 (mBzP), 9.5 (mEHP), and 101 (mNP). We also analysed seven samples of consumer milk and ten samples of infant formula. Only mBP and mEHP were detected in these samples...

  20. Thermal stability of aliphatic hyperbranched polyesters

    Directory of Open Access Journals (Sweden)

    Vuković Jasna

    2002-01-01

    Full Text Available The influence of the molar mass (generation, number and type of end groups on the thermal stability of aliphatic hyperbranched polyesters are presented in this study. Different end groups were obtained by modification of the samples with chlorides of propionic acid and stearic acid. The thermal stability of the hyperbranched polyesters was determined by thermogravimetry using a NET-ZSCH TG 209 instrument in nitrogen atmosphere at a heating rate of 10°C/min. A comparison of the temperatures obtained for mass losses of 5 20 and 40 wt% for unmodified samples showed that the thermal stability increased up to the fourth generation and then remained practically constant. An increase in the thermal stability of modified samples of the second, third and fourth generation was observed.

  1. Development of aliphatic biodegradable photoluminescent polymers

    Science.gov (United States)

    Yang, Jian; Zhang, Yi; Gautam, Santosh; Liu, Li; Dey, Jagannath; Chen, Wei; Mason, Ralph P.; Serrano, Carlos A.; Schug, Kevin A.; Tang, Liping

    2009-01-01

    None of the current biodegradable polymers can function as both implant materials and fluorescent imaging probes. The objective of this study was to develop aliphatic biodegradable photoluminescent polymers (BPLPs) and their associated cross-linked variants (CBPLPs) for biomedical applications. BPLPs are degradable oligomers synthesized from biocompatible monomers including citric acid, aliphatic diols, and various amino acids via a convenient and cost-effective polycondensation reaction. BPLPs can be further cross-linked into elastomeric cross-linked polymers, CBPLPs. We have shown representatively that BPLP-cysteine (BPLP-Cys) and BPLP-serine (BPLP-Ser) offer advantages over the traditional fluorescent organic dyes and quantum dots because of their preliminarily demonstrated cytocompatibility in vitro, minimal chronic inflammatory responses in vivo, controlled degradability and high quantum yields (up to 62.33%), tunable fluorescence emission (up to 725 nm), and photostability. The tensile strength of CBPLP-Cys film ranged from 3.25 ± 0.13 MPa to 6.5 ± 0.8 MPa and the initial Modulus was in a range of 3.34 ± 0.15 MPa to 7.02 ± 1.40 MPa. Elastic CBPLP-Cys could be elongated up to 240 ± 36%. The compressive modulus of BPLP-Cys (0.6) (1:1:0.6 OD:CA:Cys) porous scaffold was 39.60 ± 5.90 KPa confirming the soft nature of the scaffolds. BPLPs also possess great processability for micro/nano-fabrication. We demonstrate the feasibility of using BPLP-Ser nanoparticles (“biodegradable quantum dots”) for in vitro cellular labeling and noninvasive in vivo imaging of tissue engineering scaffolds. The development of BPLPs and CBPLPs represents a new direction in developing fluorescent biomaterials and could impact tissue engineering, drug delivery, bioimaging. PMID:19506254

  2. Formulações monoestágio para o problema de programação da produção de bebidas dois estágios com sincronia Mono-stage formulations for the soft drink production process with two synchronized stages

    Directory of Open Access Journals (Sweden)

    Deisemara Ferreira

    2013-03-01

    Full Text Available Neste trabalho, apresentamos formulações monoestágio para o problema integrado de dimensionamento e sequenciamento de lotes de produção de bebidas dois estágios com sincronia. O problema envolve múltiplos produtos, múltiplas máquinas e tempos e custos de troca dependentes da sequência de produção. As formulações monoestágio apresentadas não têm perda de generalidade para representar o problema e, em geral, reduzem as dimensões da formulação dois estágios com sincronia apresentadas em Ferreira, Morabito e Rangel (2009 em termos dos números de variáveis e restrições. Experimentos computacionais preliminares realizados com exemplares baseados em dados reais de uma fábrica de bebidas mostram que os modelos monoestágio propostos são competitivos, quando comparados com o modelo anterior dois estágios com sincronia.In this work we present single-stage formulations for the integrated soft drink lot-sizing and scheduling problem with two-stage synchronization. It is a multi-product, multi-machine problem, with sequence-dependent setup times and costs. Without loss of generality, these single-stage reformulations address the problem correctly and, in general, reduce the size of the synchronized two-stage model of Ferreira, Morabito e Rangel (2009, regarding the number of variables and constraints. The preliminary computational experiments on real-world instances from a soft-drink company show the competitiveness of the single-stage models against other formulations and solution approaches reported in the literature.

  3. Adsorption of halogenated aliphatic contaminants by graphene nanomaterials.

    Science.gov (United States)

    Zhou, Yang; Apul, Onur Guven; Karanfil, Tanju

    2015-08-01

    In this study, adsorption of ten environmentally halogenated aliphatic synthetic organic compounds (SOCs) by a pristine graphene nanosheet (GNS) and a reduced graphene oxide (rGO) was examined, and their adsorption behaviors were compared with those of a single-walled carbon nanotube (SWCNT) and a granular activated carbon (GAC). In addition, the impacts of background water components (i.e., natural organic matter (NOM), ionic strength (IS) and pH) on the SOC adsorption behavior were investigated. The results indicated HD3000 and SWCNT with higher microporous volumes exhibited higher adsorption capacities for the selected aliphatic SOCs than graphenes, demonstrating microporosity of carbonaceous adsorbents played an important role in the adsorption. Analysis of adsorption isotherms demonstrated that hydrophobic interactions were the dominant contributor to the adsorption of aliphatic SOCs by graphenes. However, π-π electron donor-acceptor and van der Waals interactions are likely the additional mechanisms contributing to the adsorption of aliphatic SOCs on graphenes. Among the three background solution components examined, NOM showed the most influential effect on adsorption of the selected aliphatic SOCs, while pH and ionic strength had a negligible effects. The NOM competition on aliphatic adsorption was less pronounced on graphenes than SWCNT. Overall, in terms of adsorption capacities, graphenes tested in this study did not exhibit a major advantage over SWCNT and GAC for the adsorption of aliphatic SOCs. Copyright © 2015 Elsevier Ltd. All rights reserved.

  4. Ecotoxicologically based environmental risk limits for several volatile aliphatic hydrocarbons

    NARCIS (Netherlands)

    Jong FMW de; Posthuma-Doodeman CJAM; Verbruggen EMJ; SEC

    2007-01-01

    This report describes ecotoxicological environmental risk limits derived for a number of volatile aliphatic hydrocarbons. On the basis of evaluated literature, the National Institute for Public Health and the Environment (RIVM) proposes ecotoxicological environmental risk limits for these compounds

  5. Aliphatic nitro alcohols. Synthesis, chemical transformations and applications

    Energy Technology Data Exchange (ETDEWEB)

    Shvekhgeimer, Mai-Genrikh A [A.N. Kosygin Moscow State Textile Academy, Moscow (Russian Federation)

    1998-01-31

    The data on the synthesis, chemical transformations and practical use of aliphatic nitro alcohols published over the last 25 years are described systematically and analysed. The bibliography includes 316 references.

  6. Nano-biocomposites based on synthetic aliphatic polyesters and nanoclay

    CSIR Research Space (South Africa)

    Ojijo, Vincent O

    2014-05-01

    Full Text Available This article gives an overview of the recent developments in the preparation, characterisation, properties, crystallisation behaviour, and melt rheology of clay-containing composites of biodegradable synthetic aliphatic polyesters such as poly...

  7. Gold-Catalyzed Regioselective Dimerization of Aliphatic Terminal Alkynes.

    Science.gov (United States)

    Sun, Sheng; Kroll, Julien; Luo, Yingdong; Zhang, Liming

    2012-01-01

    A gold-catalyzed regioselective homodimerization of aliphatic terminal alkynes is described. Bulky and less Lewis acidic tBuXPhosAuNTf(2) is the preferred catalyst, and the additive, anhydrous NaOAc, substantially facilitates the reaction.

  8. Renewable Aliphatic Polyester Block Polymer Thermoplastic Elastomers

    Science.gov (United States)

    Martello, Mark Thomas

    The performance of thermoplastic elastomers is predicated on their ability to form mechanically tough physically crosslinked elastomeric networks at low temperatures and be able to flow at elevated temperatures. This dissertation focuses on renewable aliphatic polyester block polymers with amorphous polylactide (PLA) and their performance as TPEs. The goal of this work was to enhance the mechanical toughness of PLA containing TPEs; fundamental properties ranging from chemical composition and phase behavior, molecular architecture and melt processability, to melt polymerization strategies were investigated. ABA triblock polymers with PLA end-blocks and rubbery mid-blocks from substituted lactones comprised of poly(6-methyl-epsilon-caprolactone)(PMCL), poly(delta-decalactone), and poly(epsilon-decalactone)(PDL) were produced by sequential ring-opening polymerizations in the bulk. The bulk microstructure of symmetric PLA-PMCL-PLA and PLA-PDL-PLA triblock polymers formed long-range ordered morphologies and the interaction parameter of the repeat units was determined. High molar mass triblocks exhibited elastomeric behavior with good tensile strengths and high elongations. Small triblocks were coupled to produced (PLA-PDL-PLA)n multiblock polymers with high molar mass and accessible order-disorder transitions allowing for melt processing via injection molding. The mechanical toughness of the multiblocks was comparable to the high molar mass triblocks. The controlled polymerization of renewable delta-decalactone was accomplished with an organocatalyst at low temperatures in the bulk to maximize the equilibrium conversion of the monomer.

  9. Attachment of inorganic moieties onto aliphatic polyurethanes

    Directory of Open Access Journals (Sweden)

    Eliane Ayres

    2007-06-01

    Full Text Available Polyurethanes have been used in a series of applications due basically to their versatility in terms of controlling the behavior by altering basically the type of reagents used. However, for more specific and advanced applications, such as in membranes, biomaterials and sensors, well-organized and defined chemical functionalities are necessary. In this work, inorganic functionalities were incorporated into aliphatic polyurethanes (PU having different macromolecular architectures. Polyurethanes were synthesized using a polyether diol and dicyclohexylmethane 4,4' diisocyanate (H12-MDI. Polyurethanes having carboxylic acid groups were also produced by introducing 2,2- bis (hydroxymethyl propionic acid in the polymerization process. Inorganic functionalities were inserted into polyurethanes by reacting isocyanate end capped chains with aminopropyltriethoxysilane followed by tetraethoxysilane. PU having carboxylic acid groups yielded transparent samples after the incorporation of inorganic entities, as an evidence of smaller and better dispersed inorganic entities in the polymer network. FTIR and swelling measurements showed that polyurethanes having carboxylic acid groups had inorganic domains less packed, condensed and cross-linked when compared to polyurethanes with no carboxylic acid groups. Results also suggested that the progressive incorporation of inorganic moieties in both types of polyurethanes occurred in regions previously activated with inorganic functionalities, instead of by the creation of new domains. The temperatures of thermal decomposition and glass transition were also shifted to higher temperatures when inorganic functionalities were incorporated into polyurethanes.

  10. Silver-mediated decarboxylative C-S cross-coupling of aliphatic carboxylic acids under mild conditions.

    Science.gov (United States)

    Wang, Peng-Fei; Wang, Xiao-Qing; Dai, Jian-Jun; Feng, Yi-Si; Xu, Hua-Jian

    2014-09-05

    A silver-mediated decarboxylative C-S cross-coupling reaction of aliphatic carboxylic acid is described. This reaction occurs smoothly under mild conditions and shows good tolerance of functional groups. It provides an alternative approach for the synthesis of alkyl aryl sulfides.

  11. Quantum chemical approach in the description of the amphiphile clusterization at the air/liquid and liquid/liquid interfaces with phase nature accounting. I. Aliphatic normal alcohols at the air/water interface.

    Science.gov (United States)

    Vysotsky, Yuri B; Belyaeva, Elena A; Kartashynska, Elena S; Fainerman, Valentine B; Smirnova, Natalia A

    2015-02-19

    A new model based on the quantum chemical approach is proposed to describe structural and thermodynamic parameters of clusterization for substituted alkanes at the air/liquid and liquid/liquid interfaces. The new model by the authors, unlike the previous one, proposes an explicit account of the liquid phase (phases) influence on the parameters of monomers, clusters and monolayers of substituted alkanes at the regarded interface. The calculations were carried out in the frameworks of the quantum chemical semiempirical PM3 method (Mopac 2012), using the COSMO procedure. The new model was tested in the calculations of the clusterization parameters of fatty alcohols under the standard conditions at the air/water interface. The enthalpy, Gibbs' energy and absolute entropy of formation for alcohol monomers alongside with clusterization parameters for the cluster series including the monolayer at air/water interface were calculated. In our calculations the sinkage of monomers, molecules in clusters and monolayers was varied from 1 up to 5 methylene groups. Thermodynamic parameters calculated using the proposed model for the alcohol monolayers are in a good agreement with the corresponding experimental data. However, the proposed model cannot define the most energetically preferable immersion of the monolayer molecules in the water phase.

  12. Formation of 3-MCPD Fatty Acid Esters from Monostearoyl Glycerol and the Thermal Stability of 3-MCPD Monoesters.

    Science.gov (United States)

    Zhao, Yue; Zhang, Yaqiong; Zhang, Zhongfei; Liu, Jie; Wang, Yi-Lin; Gao, Boyan; Niu, Yuge; Sun, Xiangjun; Yu, Liangli

    2016-11-23

    Formation of 3-monochloropropanediol (3-MCPD) esters from monostearoyl glycerol (MSG) was investigated under high temperature and low moisture conditions. Different organic and inorganic chlorides, including lindane, KCl, CaCl2, NaCl, MgCl2, AlCl3, CuCl2, MnCl2, SnCl2, ZnCl2, and FeCl3, were evaluated for their potential to react with MSG to form 3-MCPD and glycidyl esters at 120 and 240 °C using a UPLC-Q-TOF MS analysis. The results indicated that different chlorine compounds differed in their capacity to react with MSG and formed different products including 3-MCPD mono- and diesters, distearoylglycerol, and glycidyl esters. According to electron spin resonance (ESR) and Fourier transform infrared (FT-IR) spectroscopies, free radical mediated formation mechanisms involving either five-membered or six-membered cyclic acyloxonium free radicals (CAFR) from monoacylglycerol (MAG) were proposed. Tandem quadrupole-time-of-flight (Q-TOF) MS and MS/MS analyses confirmed the free radical mechanisms. In addition, the results from the present study showed that 3-MCPD monoester could be degraded upon thermal treatment and suggested a possible catalytic role of Fe(3+) under the experimental conditions.

  13. Cloud condensation nuclei (CCN) activity of aliphatic amine secondary aerosol

    Science.gov (United States)

    Tang, X.; Price, D.; Praske, E.; Vu, D. N.; Purvis-Roberts, K.; Silva, P. J.; Cocker, D. R., III; Asa-Awuku, A.

    2014-06-01

    Aliphatic amines can form secondary aerosol via oxidation with atmospheric radicals (e.g., hydroxyl radical and nitrate radical). The particle can contain both secondary organic aerosol (SOA) and inorganic salts. The ratio of organic to inorganic materials in the particulate phase influences aerosol hygroscopicity and cloud condensation nuclei (CCN) activity. SOA formed from trimethylamine (TMA) and butylamine (BA) reactions with hydroxyl radical (OH) is composed of organic material of low hygroscopicity (single hygroscopicity parameter, κ, ≤ 0.25). Secondary aerosol formed from the tertiary aliphatic amine (TMA) with N2O5 (source of nitrate radical, NO3) contains less volatile compounds than the primary aliphatic amine (BA) aerosol. As relative humidity (RH) increases, inorganic amine salts are formed as a result of acid-base reactions. The CCN activity of the humid TMA-N2O5 aerosol obeys Zdanovskii, Stokes, and Robinson (ZSR) ideal mixing rules. The humid BA + N2O5 aerosol products were found to be very sensitive to the temperature at which the measurements were made within the streamwise continuous-flow thermal gradient CCN counter; κ ranges from 0.4 to 0.7 dependent on the instrument supersaturation (ss) settings. The variance of the measured aerosol κ values indicates that simple ZSR rules cannot be applied to the CCN results from the primary aliphatic amine system. Overall, aliphatic amine aerosol systems' κ ranges within 0.2 systems.

  14. Iodine - catalyzed prins cyclization of aliphatic and aromatic ketones

    Energy Technology Data Exchange (ETDEWEB)

    Kishore, K.R.; Reddy, K.; Silva Junior, Luiz F., E-mail: luizfsjr@iq.usp.br [Universidade de Sao Paulo (IQ/USP), SP (Brazil). Inst. de Quimica. Dept. de Quimica Fundamental

    2013-09-15

    Iodine-catalyzed Prins cyclization of homoallylic alcohols and ketones was investigated. Anhydrous conditions and inert atmosphere are not required in this metal-free protocol. The reaction of 2-(3,4-dihydronaphthalene-1-yl)propan-1-ol with six aliphatic symmetric ketones gave the desired products in 67-77% yield. Cyclization was performed with four aliphatic unsymmetric ketones, leading to corresponding pyrans in 66-76% yield. Prins cyclization was also accomplished with four aromatic ketones in 37-66% yield. Finally, Prins cyclization of the monoterpene isopulegol and acetone was successfully achieved. (author)

  15. Silver-Catalyzed Decarboxylative Azidation of Aliphatic Carboxylic Acids.

    Science.gov (United States)

    Zhu, Yuchao; Li, Xinyao; Wang, Xiaoyang; Huang, Xiaoqiang; Shen, Tao; Zhang, Yiqun; Sun, Xiang; Zou, Miancheng; Song, Song; Jiao, Ning

    2015-10-02

    The catalytic decarboxylative nitrogenation of aliphatic carboxylic acids for the synthesis of alkyl azides is reported. A series of tertiary, secondary, and primary organoazides were prepared from easily available aliphatic carboxylic acids by using K2S2O8 as the oxidant and PhSO2N3 as the nitrogen source. The EPR experiment sufficiently proved that an alkyl radical process was generated in the process, and DFT calculations further supported the SET process followed by a stepwise SH2 reaction to afford azide product.

  16. 多聚磷酸法合成醇醚磷酸单酯%Synthesis of alcohol ether phosphate monoester phosphate by polyphosphoric acid method

    Institute of Scientific and Technical Information of China (English)

    徐进云; 宁庆然; 郑帼; 孙玉; 彭浩凯

    2015-01-01

    采用直接酯化法,以多聚磷酸和脂肪醇醚为原料合成了高含量单醇醚磷酸酯,并设计正交实验考察了合成工艺条件对单酯含量和醇醚转化率的影响;研究了不同单酯含量、pH值和含油率对芳砜纶纤维的抗静电性影响,并利用环境扫描电子显微镜和扫描隧道显微镜对醚磷酸酯钾盐浸丝处理后的芳砜纶纤维表面形貌特征进行了表征.结果表明:醇醚和多聚磷酸酯化反应的最优化条件为投料比3∶1,反应温度80℃,反应时间4 h,此时磷酸酯产品中单酯质量分数为91.8%,醇醚转化率为95%;磷酸酯钾盐的单酯含量和纤维表面的含油率比磷酸酯钾盐的pH值对芳砜纶纤维的抗静电性能影响大,综合考虑,纤维最佳含油率为0.3%,磷酸酯钾盐单酯含量越高,纤维的抗静电性能越好.%The high monoester content of alcohol ether phosphate was synthesized by direct esterification,using polyphosphoric acid and fatty alcohol ether as starting materials. The conditions on content of monoester and conversion rate of alcohol ether were investigated by orthogonal experimental analyses. In addition,the influences on the antistatic property of polysulfonamide fiber (PSF) by monoester content,pH value and oil content were explored. Simultaneously, environmental scanning electron microscope (ESEM) and scanning tunneling microscope (STM) were used to characterize the surface topography of PSF after dipping treatment by alcohol ether phosphate. The results showed that the optimum of esterification was the ratio of alcohol ether to polyphosphoric acid is 3∶1,the reaction temperature is 80 ℃ and the reaction time is 4 h,with the monoester content of optimal product and the percent conversion of alcohol ether being 91.8%! and 95%! respectively. Furthermore,the monoester content and oil content had greater impact on antistatic property PSF of than the pH value,and the best oil content was 0.3%!and

  17. Synthesis and Biological Evaluation of 5′-O-Dicarboxylic Fatty Acyl Monoester Derivatives of Anti-HIV Nucleoside Reverse Transcriptase Inhibitors

    OpenAIRE

    Pemmaraju, Bhanu; Agarwal, Hitesh K; Oh, Donghoon; Buckheit, Karen W.; Buckheit, Robert W.; Tiwari, Rakesh; Parang, Keykavous

    2014-01-01

    A number of 5′-O-dicarboxylic fatty acyl monoester derivatives of 3′-azido-3′-deoxythymidine (zidovudine, AZT), 2′,3′-didehydro-2′,3′-dideoxythymidine (stavudine, d4T), and 3′-fluoro-3′-deoxythymidine (alovudine, FLT) were synthesized to improve the lipophilicity and potentially the cellular delivery of parent polar 2′, 3′-dideoxynucleoside (ddN) analogues. The compounds were evaluated for their anti-HIV activity. Three different fatty acids with varying chain length of suberic acid (octanedi...

  18. Ultrasound-assisted synthesis of aliphatic acid esters at room temperature.

    Science.gov (United States)

    Hobuss, Cristiane B; Venzke, Dalila; Pacheco, Bruna S; Souza, Alexander O; Santos, Marco A Z; Moura, Sidnei; Quina, Frank H; Fiametti, Karina G; Vladimir Oliveira, J; Pereira, Claudio M P

    2012-05-01

    This work describes the ultrasound-assisted synthesis of saturated aliphatic esters from synthetic aliphatic acids and either methanol or ethanol. The products were isolated in good yields after short reaction times under mild conditions.

  19. Aliphatic polyester block polymers: renewable, degradable, and sustainable.

    Science.gov (United States)

    Hillmyer, Marc A; Tolman, William B

    2014-08-19

    Nearly all polymers are derived from nonrenewable fossil resources, and their disposal at their end of use presents significant environmental problems. Nonetheless, polymers are ubiquitous, key components in myriad technologies and are simply indispensible for modern society. An important overarching goal in contemporary polymer research is to develop sustainable alternatives to "petro-polymers" that have competitive performance properties and price, are derived from renewable resources, and may be easily and safely recycled or degraded. Aliphatic polyesters are particularly attractive targets that may be prepared in highly controlled fashion by ring-opening polymerization of bioderived lactones. However, property profiles of polyesters derived from single monomers (homopolymers) can limit their applications, thus demanding alternative strategies. One such strategy is to link distinct polymeric segments in an A-B-A fashion, with A and B chosen to be thermodynamically incompatible so that they can self-organize on a nanometer-length scale and adopt morphologies that endow them with tunable properties. For example, such triblock copolymers can be useful as thermoplastic elastomers, in pressure sensitive adhesive formulations, and as toughening modifiers. Inspired by the tremendous utility of petroleum-derived styrenic triblock copolymers, we aimed to develop syntheses and understand the structure-property profiles of sustainable alternatives, focusing on all renewable and all readily degradable aliphatic polyester triblocks as targets. Building upon oxidation chemistry reported more than a century ago, a constituent of the peppermint plant, (-)-menthol, was converted to the ε-caprolactone derivative menthide. Using a diol initiator and controlled catalysis, menthide was polymerized to yield a low glass transition temperature telechelic polymer (PM) that was then further functionalized using the biomass-derived monomer lactide (LA) to yield fully renewable PLA

  20. Sulfonyl fluorides as alternative to sulfonyl chlorides in parallel synthesis of aliphatic sulfonamides.

    Science.gov (United States)

    Bogolubsky, Andrey V; Moroz, Yurii S; Mykhailiuk, Pavel K; Pipko, Sergey E; Konovets, Anzhelika I; Sadkova, Irina V; Tolmachev, Andrey

    2014-04-14

    Two types of aliphatic sulfonyl halides (Cl versus F) were compared in parallel synthesis of sulfonamides derived from aliphatic amines. Aliphatic sulfonyl fluorides showed good results with amines bearing an additional functionality, while the corresponding chlorides failed. Both sulfonyl halides were effective in the reactions with amines having an easily accessible amino group. Aliphatic sulfonyl chlorides reacted efficiently with amines bearing sterically hindered amino group while the corresponding fluorides showed low activity.

  1. Polymeric Amines by chemical modifications of alternating aliphatic polyketones

    NARCIS (Netherlands)

    Zhang, Youchun; Broekhuis, A. A.; Stuart, Marc C. A.; Picchioni, F.

    2008-01-01

    Alternating, aliphatic polyketones were chemically modified by using di-amines to obtain polymeric products having pendant amino groups. The used reaction, Paal-Knorr, involves the formation of pyrrole rings along the polyketone backbone. The corresponding kinetics and final conversions are clearly

  2. Chemical modifications and applications of alternating aliphatic polyketones

    NARCIS (Netherlands)

    Zhang, Youchun

    2008-01-01

    Alternating aliphatic polyketones, produced by co- and terpolymerization of carbon monoxide and olefins (mixtures of ethylene and propylene) using palladium-based homogeneous catalysis represent a very promising class of polymers for a wide range of applications. Besides many interesting chemical

  3. Cloud condensation nuclei activity of aliphatic amine secondary aerosol

    Science.gov (United States)

    Aliphatic amines can form secondary aerosol via oxidation with atmospheric radicals (e.g. hydroxyl radical and nitrate radical). The resulting particle composition can contain both secondary organic aerosol (SOA) and inorganic salts. The fraction of organic to inorganic materials in the particulate ...

  4. 40 CFR 721.7250 - Polyaziridinyl ester of an aliphatic alcohol (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Polyaziridinyl ester of an aliphatic... Specific Chemical Substances § 721.7250 Polyaziridinyl ester of an aliphatic alcohol (generic). (a... generically as a polyaziridinyl ester of an aliphatic alcohol (PMN P-01-97) is subject to reporting under...

  5. 40 CFR 721.2098 - Aliphatic polycarboxylic acid metal salt (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Aliphatic polycarboxylic acid metal... Specific Chemical Substances § 721.2098 Aliphatic polycarboxylic acid metal salt (generic). (a) Chemical... as an aliphatic polycarboxylic acid metal salt (PMN P-01-7) is subject to reporting under...

  6. Efficient catalytic promiscuity in an enzyme superfamily: an arylsulfatase shows a rate acceleration of 10(13) for phosphate monoester hydrolysis.

    Science.gov (United States)

    Olguin, Luis F; Askew, Sarah E; O'Donoghue, Annmarie C; Hollfelder, Florian

    2008-12-10

    We report a second catalytic activity of Pseudomonas aeruginosa arylsulfatase (PAS). Besides hydrolyzing sulfate monoesters, this enzyme catalyzes the hydrolysis of phosphate monoesters with multiple turnovers (>90), a k(cat) value of 0.023 s(-1), a K(M) value of 29 microM, and a kcat/K(M) ratio of 790 M(-1) s(-1) at pH 8.0. This corresponds to a remarkably high rate acceleration of 10(13) relative to the nonenzymatic hydrolysis [(k(cat)/K(M))/k(w)] and a transition-state binding constant (K(tx)) of 3.4 pM. Promiscuous phosphatase and original sulfatase activities only differ by a factor of 620 (measured by k(cat)), so the enzyme provides high accelerations for both reactions. The magnitudes and relative similarity of the kinetic parameters suggest that a functional switch from sulfatase to phosphatase activities is feasible, either by gene duplication or by direct evolution via an intermediate enzyme with dual specificity.

  7. Monoester-Diterpene Aconitum Alkaloid Metabolism in Human Liver Microsomes: Predominant Role of CYP3A4 and CYP3A5

    Science.gov (United States)

    Ye, Ling; Yang, Xiao-Shan; Lu, Lin-lin; Chen, Wei-Ying; Zeng, Shan; Yan, Tong-Meng; Dong, Ling-Na; Peng, Xiao-Juan; Shi, Jian; Liu, Zhong-Qiu

    2013-01-01

    Aconitum, widely used to treat rheumatoid arthritis for thousands of years, is a toxic herb that can frequently cause fatal cardiac poisoning. Aconitum toxicity could be decreased by properly hydrolyzing diester-diterpene alkaloids into monoester-diterpene alkaloids. Monoester-diterpene alkaloids, including benzoylaconine (BAC), benzoylmesaconine (BMA), and benzoylhypaconine (BHA), are the primary active and toxic constituents of processed Aconitum. Cytochrome P450 (CYP) enzymes protect the human body by functioning as the defense line that limits the invasion of toxicants. Our purposes were to identify the CYP metabolites of BAC, BMA, and BHA in human liver microsomes and to distinguish which isozymes are responsible for their metabolism through the use of chemical inhibitors, monoclonal antibodies, and cDNA-expressed CYP enzyme. High-resolution mass spectrometry was used to characterize the metabolites. A total of 7, 8, and 9 metabolites were detected for BAC, BMA, and BHA, respectively. The main metabolic pathways were demethylation, dehydrogenation, demethylation-dehydrogenation, hydroxylation and didemethylation, which produced less toxic metabolites by decomposing the group responsible for the toxicity of the parent compound. Taken together, the results of the chemical inhibitors, monoclonal antibodies, and cDNA-expressed CYP enzymes experiments demonstrated that CYP3A4 and CYP3A5 have essential functions in the metabolism of BAC, BMA, and BHA. PMID:23864901

  8. Monoester-Diterpene Aconitum Alkaloid Metabolism in Human Liver Microsomes: Predominant Role of CYP3A4 and CYP3A5

    Directory of Open Access Journals (Sweden)

    Ling Ye

    2013-01-01

    Full Text Available Aconitum, widely used to treat rheumatoid arthritis for thousands of years, is a toxic herb that can frequently cause fatal cardiac poisoning. Aconitum toxicity could be decreased by properly hydrolyzing diester-diterpene alkaloids into monoester-diterpene alkaloids. Monoester-diterpene alkaloids, including benzoylaconine (BAC, benzoylmesaconine (BMA, and benzoylhypaconine (BHA, are the primary active and toxic constituents of processed Aconitum. Cytochrome P450 (CYP enzymes protect the human body by functioning as the defense line that limits the invasion of toxicants. Our purposes were to identify the CYP metabolites of BAC, BMA, and BHA in human liver microsomes and to distinguish which isozymes are responsible for their metabolism through the use of chemical inhibitors, monoclonal antibodies, and cDNA-expressed CYP enzyme. High-resolution mass spectrometry was used to characterize the metabolites. A total of 7, 8, and 9 metabolites were detected for BAC, BMA, and BHA, respectively. The main metabolic pathways were demethylation, dehydrogenation, demethylation-dehydrogenation, hydroxylation and didemethylation, which produced less toxic metabolites by decomposing the group responsible for the toxicity of the parent compound. Taken together, the results of the chemical inhibitors, monoclonal antibodies, and cDNA-expressed CYP enzymes experiments demonstrated that CYP3A4 and CYP3A5 have essential functions in the metabolism of BAC, BMA, and BHA.

  9. Biodegradation of Trihalomethanes and Other Halogenated Aliphatic Compounds

    Science.gov (United States)

    Smith, G. B.

    1996-01-01

    The biological dehalogenation of common water pollutants such as trichloromethane (chloroform) and other halogenated aliphatic compounds was the subject of this project. Samples from diverse water environments such as from groundwater contaminated with halogenated compounds and wastewaters from regional treatment plants were studied to identify conditions that favor certain dehalogenation reactions over others. Gene probe analyses of DNA extracted from the dichlormethane-degrading wastewater indicated the presence of the gene coding for dichloromethane dehalogenase, indicating the genetic basis for the dechlorination activity observed. These studies indicate that methanogenic bacteria are the organisms responsible for the chloroform dechlorination. Dechlorination of a common chlorofluorocarbon (CFC-11) was identified in samples taken from a regional aquifer contaminated with halogenated aliphatic compounds.

  10. Lipstick dermatitis due to C18 aliphatic compounds.

    Science.gov (United States)

    Hayakawa, R; Matsunaga, K; Suzuki, M; Arima, Y; Ohkido, Y

    1987-04-01

    An 18-year-old girl developed cheilitis. She had a past history of lip cream dermatitis, but the cause was not found. Patch tests with 2 lipsticks were strongly positive. Tests with the ingredients were positive to 2 aliphatic compounds, glyceryl diisostearate and diisostearyl malate. Impurities in the materials were suspected as the cause. Analysis by gas chromatography detected 3 chemicals in glyceryl diisostearate and 1 in diisostearyl malate as impurities. Patch testing with the impurities and glyceryl monoisostearate 0.01% pet in glyceryl diisostearate and isostearyl alcohol 0.25% pet in diisostearyl malate were strongly positive. The characteristics common to the 2 chemicals were liquidity at room temperature, branched C18 aliphatic compound and primary alcohol. Chemicals lacking any of the above 3 features did not react.

  11. Determination of aliphatic hydrocarbons in the alga Himanthalia elongata.

    Science.gov (United States)

    Punín Crespo, M O; Lage Yusty, M A

    2004-02-01

    The algae considered new foods according to Regulation CE 258/97 need a guarantee of their healthfulness before being in the European market. In this work ten samples of the brown alga Himanthalia elongata have been analyzed with the aim of verifying the absence of aliphatic hydrocarbons, due to the ability of the macroalgae to capture lipophilic organic compounds of the marine water coming from accidental or continuous leaks of raw oil and refined products, which happen each year with the growth of the industrialization and the demand of energy. The fat of the samples were Soxhlet extracted using hexane:dichloromethane (1:1) for 7h. The organic fractions were purified using silica microcolumns. The identification and quantification of the aliphatic hydrocarbons have been carried out using gas chromatography (GC) with flame ionization detector (FID). The total hydrocarbon content was between 14.8 and 40.2 microg g(-1) dry weight.

  12. Silver-catalyzed decarboxylative chlorination of aliphatic carboxylic acids.

    Science.gov (United States)

    Wang, Zhentao; Zhu, Lin; Yin, Feng; Su, Zhongquan; Li, Zhaodong; Li, Chaozhong

    2012-03-07

    Decarboxylative halogenation of carboxylic acids, the Hunsdiecker reaction, is one of the fundamental functional group transformations in organic chemistry. As the initial method requires the preparations of strictly anhydrous silver carboxylates, several modifications have been developed to simplify the procedures. However, these methods suffer from the use of highly toxic reagents, harsh reaction conditions, or limited scope of application. In addition, none is catalytic for aliphatic carboxylic acids. In this Article, we report the first catalytic Hunsdiecker reaction of aliphatic carboxylic acids. Thus, with the catalysis of Ag(Phen)(2)OTf, the reactions of carboxylic acids with t-butyl hypochlorite afforded the corresponding chlorodecarboxylation products in high yields under mild conditions. This method is not only efficient and general, but also chemoselective. Moreover, it exhibits remarkable functional group compatibility, making it of more practical value in organic synthesis. The mechanism of single electron transfer followed by chlorine atom transfer is proposed for the catalytic chlorodecarboxylation.

  13. Aliphatics hydrocarbon content in surface sediment from Jakarta Bay, Indonesia

    Science.gov (United States)

    YAzis, M.; Asia, L.; Piram, A.; Doumenq, P.; Syakti, A. D.

    2016-02-01

    Sedimentary aliphatic hydrocarbons content have been studied quantitatively and qualitatively using GC/MS method in eight coastal stations located in the Jakarta Bay, North of Jakarta, Indonesia. The total concentrations n-alkanes have ranged from 480 μg.kg-1to 1,935 μg.kg-1sediment dry weight. Several ratios (e.g. CPI24-32, NAR, TAR, Pr/Phy, n-C17/Pr, n- C18/Phyt,n-C29/n-C17, Ʃn-alkanes/n-C16LMW/HMW, Paq and TMD) were used to evaluate the possible sources of terrestrial-marine inputs of these hydrocarbons in the sediments. The various origins of aliphatic hydrocarbons were generally biogenic, including both terrigenous and marine, with an anthropogenic pyrolytic contribution (petrogenic and biogenic combustion). Two stations (G,H) were thehighest concentration and had potential risk to environment

  14. Japodic Acid, A Novel Aliphatic Acid from Jatropha podagrica Hook

    OpenAIRE

    Aiyelaagbe, Olapeju O.; Gloer, James B.

    2008-01-01

    A new aliphatic acid named japodic acid (1) with a gem-dimethyl cyclopropane ring has been isolated from the roots of Jatropha podagrica. Its structure was established by 1D and 2D NMR and mass spectrometric data. Two other known compounds, erythrinasinate (2) and fraxidin (3) were also isolated from this plant for the first time. Japodic acid showed mild insect growth inhibition activity against Helicoverpa zea (37% growth reduction at 100 ppm). Fraxidin and erythrinasinate exhibited antibac...

  15. Biodegradation of aliphatic vs. aromatic hydrocarbons in fertilized arctic soils

    Science.gov (United States)

    Braddock, J.F.

    1999-01-01

    A study was carried out to test a simple bioremediation treatment strategy in the Arctic and analyze the influence of fertilization the degradation of aliphatic and aromatic hydrocarbons, e.g., pristine, n-tetradecane, n-pentadecane, 2-methylnaphthalene, naphthalene, and acenaphthalene. The site was a coarse sand pad that once supported fuel storage tanks. Diesel-range organics concentrations were 250-860 mg/kg soil at the beginning of the study. Replicate field plots treated with fertilizer yielded final concentrations of 0, 50, 100, or 200 mg N/kg soil. Soil pH and soil-water potentials decreased due to fertilizer application. The addition of fertilizer considerably increased soil respiration potentials, but not the populations of microorganisms measured. Fertilizer addition also led to ??? 50% loss of measured aliphatic and aromatic hydrocarbons in surface and subsurface soils. For fertilized plots, hydrocarbon loss was not associated with the quantity of fertilizer added. Losses of aliphatic hydrocarbons were ascribed to biotic processes, while losses of aromatic hydrocarbons were due to biotic and abiotic processes.

  16. 酶法制备丙二醇单酯的研究%Study on propylene glycol monoester by lipase method

    Institute of Scientific and Technical Information of China (English)

    钟遇安; 姜土; 吴炜亮; 杨修斌

    2012-01-01

    为制备丙二醇单酯,以叔丁醇为溶剂,对脂肪酶催化橄榄油与1,2-丙二醇进行酯交换反应合成丙二醇单酯进行研究.考察脂肪酶种类和酶反应条件对酯交换反应的影响.结果表明,在叔丁醇体系中来自Rhizomucor miehei的固定化脂肪酶Lipozyme RM IM适用于催化橄榄油与丙二醇的醇解反应合成1,2-丙二醇单酯.最佳的反应条件:橄榄油和1,2-丙二醇的摩尔比为1∶4,叔丁醇体系中底物混合物的浓度为30%,反应温度为50℃,脂肪酶的添加量为底物质量的3%,酯交换反应12h.该条件下,产物中1,2-丙二醇单酯的含量达到72.4%.%Investigated the synthesis of propylen, glycol monoester u-sing lipase catalyzed transesterification between olive oil and 1, 2-propanediol in tert-butanol, and the effects of different lipases and processing parameters on transesterification were studied. The results showed that immobilized lipase Lipozyme RM IM from Rhizo-mucor miehei was suitable for catalyzed the alcoholysis between olive oil and 1, 2-propanediol for synthesis of propylcne glycol monoester. The optimal parameters were mole ratio of olive oil to 1, 2-propanediol 1 : 4, the concentration of substrates in tert-butanol 30% , reaction temperature 50 ? , enzyme load was 3% (m/m) of substrates, duration of reaction 12 h. 72. 4% of 1 , 2-propylene glycol monoester was obtained after the reaction conducted with optimum conditions.

  17. Screening of lipases for the synthesis of xylitol monoesters by chemoenzymatic esterification and the potential of microwave and ultrasound irradiations to enhance the reaction rate.

    Science.gov (United States)

    Rufino, Alessandra R; Biaggio, Francisco C; Santos, Julio C; de Castro, Heizir F

    2010-07-01

    Lipases from different sources, Pseudomonas fluorescens (AK lipase), Burkholderia cepacia (PS lipase), Penicillium camembertii (lipase G) and Porcine pancreas lipase (PPL), previously immobilized on epoxy SiO(2)-PVA, were screened for the synthesis of xylitol monoesters by esterification of the protected xylitol using oleic acid as acyl donor group. Among all immobilized derivatives, the highest esterification yield was achieved by P. camembertii lipase, showing to be attractive alternative to bulk chemical routes to satisfy increasing commercial demands. Further experiments were performed to determine the influence of fatty acids chain size on the reaction yield and the feasibility of using non-conventional heating systems (microwave and ultrasound irradiations) to enhance the reaction rate.

  18. Site-selective C-H arylation of primary aliphatic amines enabled by a catalytic transient directing group

    Science.gov (United States)

    Liu, Yongbing; Ge, Haibo

    2017-01-01

    Transition-metal-catalysed direct C-H bond functionalization of aliphatic amines is of great importance in organic and medicinal chemistry research. Several methods have been developed for the direct sp3 C-H functionalization of secondary and tertiary aliphatic amines, but site-selective functionalization of primary aliphatic amines in remote positions remains a challenge. Here, we report the direct, highly site-selective γ-arylation of primary alkylamines via a palladium-catalysed C-H bond functionalization process on unactivated sp3 carbons. Using glyoxylic acid as an inexpensive, catalytic and transient directing group, a wide array of γ-arylated primary alkylamines were prepared without any protection or deprotection steps. This approach provides straightforward access to important structural motifs in organic and medicinal chemistry without the need for pre-functionalized substrates or stoichiometric directing groups and is demonstrated here in the synthesis of analogues of the immunomodulatory drug fingolimod directly from commercially available 2-amino-2-propylpropane-1,3-diol.

  19. Synthesis of aliphatic amidediol and used as a novel mixed plasticizer for thermoplastic starch

    Institute of Scientific and Technical Information of China (English)

    Jian She Zhang; Jiu Gao Yu; Ying Wu; Xiao Fei Ma

    2008-01-01

    In this paper,aliphatic amidediol was synthesized and mixed with glycerol used as a plasticizer for preparing thermoplastic starch (AGPTPS).The yield of aliphatic amidediol was 91%.FT-IR expressed that the mixture of aliphatic amidediol and glycerol formed stronger and stable hydrogen bond with starch molecules compared to the native cornstarch.By scanning electron microscope (SEM) native cornstarch granules were proved to transfer to a homogeneous continuous system.After being stored for a period time at room temperature,the mechanical properties of AGPTPS were also studied.As a mixed plasticizer,aliphatic amidediol and glycerol would be practical to extend TPS application scopes.

  20. Synthesis and Characterization of Aliphatic-Aromatic Hyperbranched Polyesters

    Institute of Scientific and Technical Information of China (English)

    唐黎明; 张晓龙; 邱藤; 刘德山

    2002-01-01

    Hyperbranched polymers possess special architectures and have potential applications in various areas. In this study, two AB2 monomers, dipropyl 5-(hydroxyethoxy) isophthalate (I) and 5-hydroxyethoxyisophthaic acid (II), were prepared. By bulk polycondensation of each monomer, two aliphatic-aromatic hyperbranched polyesters were prepared and characterized by 1H-nuclear magnetic resonance (1H-NMR), differential scanning calorimetry (DSC), thermogravimetry analysis (TGA), and scanning electron microscopy (SEM). Compared with all-aromatic hyperbranched polyesters, the prepared polymers showed lower glass transition temperatures in connection with the moderate decrease in their decomposition temperatures.

  1. A Comprehensive Review of Aliphatic Hydrocarbon Biodegradation by Bacteria.

    Science.gov (United States)

    Abbasian, Firouz; Lockington, Robin; Mallavarapu, Megharaj; Naidu, Ravi

    2015-06-01

    Hydrocarbons are relatively recalcitrant compounds and are classified as high-priority pollutants. However, these compounds are slowly degraded by a large variety of microorganisms. Bacteria are able to degrade aliphatic saturated and unsaturated hydrocarbons via both aerobic and anaerobic pathways. Branched hydrocarbons and cyclic hydrocarbons are also degraded by bacteria. The aerobic bacteria use different types of oxygenases, including monooxygenase, cytochrome-dependent oxygenase and dioxygenase, to insert one or two atoms of oxygen into their targets. Anaerobic bacteria, on the other hand, employ a variety of simple organic and inorganic molecules, including sulphate, nitrate, carbonate and metals, for hydrocarbon oxidation.

  2. Decarboxylative Fluorination of Aliphatic Carboxylic Acids via Photoredox Catalysis.

    Science.gov (United States)

    Ventre, Sandrine; Petronijevic, Filip R; MacMillan, David W C

    2015-05-06

    The direct conversion of aliphatic carboxylic acids to the corresponding alkyl fluorides has been achieved via visible light-promoted photoredox catalysis. This operationally simple, redox-neutral fluorination method is amenable to a wide variety of carboxylic acids. Photon-induced oxidation of carboxylates leads to the formation of carboxyl radicals, which upon rapid CO2-extrusion and F(•) transfer from a fluorinating reagent yield the desired fluoroalkanes with high efficiency. Experimental evidence indicates that an oxidative quenching pathway is operable in this broadly applicable fluorination protocol.

  3. 醇醚糖苷柠檬酸单酯盐的制备与性能研究%Preparation and performance of citrate monoesters salt of ethoxylated fatty alcohols glucoside

    Institute of Scientific and Technical Information of China (English)

    牛少勇; 杨秀全; 白亮; 周媛; 张军

    2012-01-01

    Through indirect eaterification,citric acid anhydride was synthesized with citric acid and acetic anhydride as raw materials,the citrate monoesters were prepared with synthetic citric acid anhydride and ethoxylated fatty alcohols glucoside (containing excess ethoxylated fatty alcohols) ,and then neutralization with NaOH,Ca (OH)2 and Mg (OH)2 obtained the citrate monoesters disodium salt of ethoxylated fatty alcohols glucoside (MAEG-EC-Na) , citrate monoesters calcium salt of ethoxylated fatty alcohols glucoside (MAEC-EC-Ca) and citrate monoesters magnesium salt of ethoxylated fatty alcohols glucoside (MAEG- EC-Mg). The physicochemical properties of the products were measured. Results showed that the γcmc range of the three products are very small, and the one of citric acid monoester disodium salt of ethoxylated fatty alcohols glucoside is minimum. The order of foaming ability and foam stability of citric acid monoester salt is MAEG-EC-Mg > MAEG-EC-Ca > MAEG-EC-Na.%采用间接酯化法,以柠檬酸和乙酸酐为原料,先合成柠檬酸酐,后与醇醚糖苷(含有未反应的脂肪醇醚)反应,合成了醇醚糖苷柠檬酸单酯,再用NaOH溶液、饱和Ca(OH)2水溶液和Mg(OH)2乳浊液中和制得醇醚糖苷柠檬酸单酯二钠盐(MAEG-EC-Na)、醇醚糖苷柠檬酸单酯钙盐(MAEG-EC-Ca)和醇醚糖苷柠檬酸单酯镁盐(MAEGEC-Mg),对产物的物化性能进行了测定.结果表明,上述3种产品的γcmc变化范围均很小,而柠檬酸单酯二钠盐的cmc最小,柠檬酸单酯盐起泡性能、泡沫稳定性的顺序为MAEG-EC-Mg> MAEG-EC-Ca> MAEG-EC-Na.

  4. Short-chain aliphatic ester synthesis using Thermobifida fusca cutinase.

    Science.gov (United States)

    Su, Lingqia; Hong, Ruoyu; Guo, Xiaojie; Wu, Jing; Xia, Yongmei

    2016-09-01

    Short-chain aliphatic esters are commonly used as fruit flavorings in the food industry. In this study, Thermobifida fusca (T. fusca) cutinase was used for the synthesis of aliphatic esters, and the maximum yield of ethyl caproate reached 99.2% at a cutinase concentration of 50U/ml, 40°C, and water content of 0.5%, representing the highest ester yield to date. The cutinase-catalyzed esterification displayed strong tolerance for water content (up to 8%) and acid concentration (up to 0.8M). At substrate concentrations ⩽0.8M, the ester yield remained above 80%. Moreover, ester yields of more than 98% and 95% were achieved for acids of C3-C8 and alcohols of C1-C6, respectively, indicating extensive chain length selectivity of the cutinase. These results demonstrate the superior ability of T. fusca cutinase to catalyze the synthesis of short-chain esters. This study provides the basis for industrial production of short-chain esters using T. fusca cutinase.

  5. Study on the Synthesis and Biodegradation of Aliphatic Polyester

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    An aliphatic polyester, poly(hexalene adipate) (PHA) and an aliphatic copolyester, poly (hexalene adipate succinate) (PHAS) were synthesized by direct condensation of corresponding binary acid and binary alcohol in the presence of a catalyst, p-toluene sulfonic acid. The biodegradation of these polyesters were studied in the laboratory by enzyme attack and outdoor soil burial. The results show that these polyesters have good biodegradability and the copolyester PHAS, even displayed a better biodegradability than the polyester PHA. In the presence of Penicillium chrysogenum the weight loss reached 18.3% for the PHAS (film thickness 1.0 mm)and 9.1% for the PHA (film thickness 1.0 mm) after 28 days. Outdoor soil burial tests indicate that these polyesters also have good biodegradability in natural conditions. The weight loss reached 14.2% for PHAS (film thickness 0.1 mm) and 6.7% for PHA (film thickness 0.1mm) after burying in soil for 36 days.

  6. Contact allergy to reactive diluents and related aliphatic epoxy resins.

    Science.gov (United States)

    Aalto-Korte, Kristiina; Kuuliala, Outi; Henriks-Eckerman, Maj-Len; Suuronen, Katri

    2015-06-01

    Diglycidyl ether of bisphenol A resin (DGEBA-R) is the most common sensitizer in epoxy systems, but a minority of patients also develop contact allergy to reactive diluents. To analyse the frequency and clinical relevance of allergic reactions to different epoxy reactive diluents and related aliphatic epoxy resins. Test files (January 1991 to June 2014) were screened, and the clinical records of patients with allergic reactions were analysed for occupation, concomitant allergic reactions, and exposure. A total of 67 patients reacted to at least one of the compounds. The largest numbers of allergic reactions were to phenyl glycidyl ether (PGE; n = 41), 1,4-butanediol diglycidyl ether (BDDGE; n = 34), and p-tert-butylphenyl glycidyl ether (PTBPGE; n = 19). Ten of the patients did not have contact allergy to DGEBA-R. The reactions of 5 of these were related to the use of BDDGE-containing products. We found no significant exposure to PGE or PTBPGE in patients sensitized to them, but some of the patients had used cresyl glycidyl ether-containing products. Allergic reactions to reactive diluents and related aliphatic epoxy resins usually occurred together with reactions to DGEBA-R. BDDGE was the clinically most significant compound, and was the sole cause of occupational allergic contact dermatitis in 3 patients. © 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  7. Facile synthesis of aliphatic isothiocyanates and thioureas on solid phase using peptide coupling reagents

    DEFF Research Database (Denmark)

    Boas, Ulrik; Andersen, Heidi Gertz; Christensen, Jørn B.;

    2004-01-01

    Peptide coupling reagents can be used as versatile reagents for the formation of aliphatic isothiocyanates and thioureas on solid phase from the corresponding solid-phase anchored aliphatic primary amines. The formation of the thioureas is fast and highly chemoselective, and proceeds via formation...

  8. Estimates of Gibbs free energies of formation of chlorinated aliphatic compounds

    NARCIS (Netherlands)

    Dolfing, Jan; Janssen, Dick B.

    1994-01-01

    The Gibbs free energy of formation of chlorinated aliphatic compounds was estimated with Mavrovouniotis' group contribution method. The group contribution of chlorine was estimated from the scarce data available on chlorinated aliphatics in the literature, and found to vary somewhat according to the

  9. Chemiluminescence of the peroxomonosulphate-cobalt(II)-aliphatic monocarboxylic acids system.

    Science.gov (United States)

    Wang, Min; Zhao, Lixia; Lin, Jin-Ming

    2007-01-01

    A weak chemiluminescence (CL) emission was observed due to the production of singlet oxygen ((1)O(2)) during the decomposition of peroxomonosulphate (HSO(5)(-)) catalysed by cobalt(II). Low molecular mass aliphatic monocarboxylic acids, such as formic, acetic, propionic, butyric and valeric acids, influenced the CL emission, and the reaction of aliphatic monocarboxylic acids with HSO(5)(-)/Co(2+) solution was further investigated using a flow injection analysis (FIA) CL method. The results indicated that the CL intensities of aliphatic monocarboxylic acids were improved with increase in the carbon chain length in the potassium peroxomonosulphate-cobalt(II) sulphate system. Generation of singlet oxygen was confirmed by the fact that the CL emission of aliphatic monocarboxylic acids with the HSO(5)(-)/Co(2+) solution was quenched by NaN(3), and from the CL spectrum of the reaction system. Additionally, a possible mechanism of aliphatic monocarboxylic acids CL emission enhancement was proposed.

  10. A Theoretical Study on the Vibrational Spectra of PAH Molecules with Aliphatic Sidegroups

    CERN Document Server

    Sadjadi, SeyedAbdolreza; Kwok, Sun

    2015-01-01

    The role of aliphatic side groups on the formation of astronomical unidentified infrared emission (UIE) features is investigated by applying the density functional theory (DFT) to a series of molecules with mixed aliphatic-aromatic structures. The effects of introducing various aliphatic groups to a fixed polycyclic aromatic hydrocarbon (PAH) core (ovalene) are studied. Simulated spectra for each molecule are produced by applying a Drude profile at $T$=500 K while the molecule is kept at its electronic ground state. The vibrational normal modes are classified using a semi-quantitative method. This allows us to separate the aromatic and aliphatic vibrations and therefore provide clues to what types of vibrations are responsible for the emissions bands at different wavelengths. We find that many of the UIE bands are not pure aromatic vibrational bands but may represent coupled vibrational modes. The effects of aliphatic groups on the formation of the 8 $\\mu$m plateau are qua ntitatively determined. The vibratio...

  11. Low—Molecular—Weight Aliphatic Acids in Soils Inculbated with Plant Residues Under Different Moisture Conditions

    Institute of Scientific and Technical Information of China (English)

    SHENALIN; LIXUEYUAN; 等

    1997-01-01

    Iucubation experiments were conducted to investigate the dynamics of low-molecular-weight aliphatic acids i two andosols with and without plant materials.Results showed that amount of low-molecular-weight aliphatic acids in soils alone varied considerably with water regime under which the soil was incubated,duration of incubation and soil organic matter content,ranging from 257-860μmol kg-1 soil,of which 19%-33% was in free state.Incorporation of plant matrials increased greatly both the amount and unmber of members of low-molecular-weight aliphatic acids,and also the proportion of low-molecular-weght aliphatic acids occurred in free state ,Generally,among these ,aliphatic acids detected,acetic,propionic,glyoxalic and formic acids were predominant.

  12. Environmentally benign synthesis of saturated and unsaturated aliphatic polyesters via enzymatic polymerization of biobased monomers derived from renewable resources

    NARCIS (Netherlands)

    Jiang, Yi; Woortman, Albert J. J.; van Ekenstein, Gert O. R. Alberda; Loos, Katja

    2015-01-01

    Aliphatic polyesters are of great interest due to their broad potential applications and sustainability. Itaconate-based aliphatic polyesters are even more appealing in biomedical and pharmaceutical fields, as they are renewable functional polymers that can be biodegradable, biocompatible, and

  13. 酶法制备椰子油基丙二醇单酯的研究%Enzymatic synthesis of propylene glycol monoester by alcoholysis of coconut oil

    Institute of Scientific and Technical Information of China (English)

    汪运明; 覃小丽; 王卫飞; 杨博; 王永华

    2012-01-01

    The synthesis of propylene glycol monoester, using coconut oil and 1,2- propanediol as raw materials via alcoholysis in solvent - free system was studied, and the reaction products were analyzed by HPLC - RID. Compared with other eleven kinds of common commercial lipases, the immobilized Jipase Novozyme 435 from Candida antarctic had the best effect. The effects of enzyme dosage, substrate molar ratio, reaction temperature and water dosage on the alcoholysis reaction were investigated. The reaction conditions were optimized as follows; molar ratio of 1 ,2 -propanediol to coconut oil 8 : 1, reaction temperature 50 ℃ , enzyme dosage 300 U/g(based on the mass of substrate) , water dosage 1. 0% (based on the mass of 1,2 - propanediol). After reaction for 6 h under the optimal conditions, the content of propylene glycol monoester was 53.48% .%在无溶剂体系中,对脂肪酶催化椰子油与1,2-丙二醇醇解反应合成椰子油基丙二醇单酯进行了研究,采用HPLC-RID对目标产物进行分析.比较了12种常用商品化脂肪酶,结果表明固定化脂肪酶Novozyme 435合成椰子油基丙二醇单酯的效果最好.以Novozyme 435为催化剂,进一步研究了酶加量、底物摩尔比、反应温度和水加量对醇解反应的影响.确定最优的反应条件为:1,2-丙二醇与椰子油摩尔比8∶1,反应温度50℃,水加量1.0%(以1,2-丙二醇质量计),酶加量300U/g(以底物质量计).在最优反应条件下,醇解反应6h,椰子油基丙二醇单酯生成量达到53.48%.

  14. The impact of the absence of aliphatic glucosinolates on insect herbivory in Arabidopsis.

    Directory of Open Access Journals (Sweden)

    Jules Beekwilder

    Full Text Available Aliphatic glucosinolates are compounds which occur in high concentrations in Arabidopsis thaliana and other Brassicaceae species. They are important for the resistance of the plant to pest insects. Previously, the biosynthesis of these compounds was shown to be regulated by transcription factors MYB28 and MYB29. We now show that MYB28 and MYB29 are partially redundant, but in the absence of both, the synthesis of all aliphatic glucosinolates is blocked. Untargeted and targeted biochemical analyses of leaf metabolites showed that differences between single and double knock-out mutants and wild type plants were restricted to glucosinolates. Biosynthesis of long-chain aliphatic glucosinolates was blocked by the myb28 mutation, while short-chain aliphatic glucosinolates were reduced by about 50% in both the myb28 and the myb29 single mutants. Most remarkably, all aliphatic glucosinolates were completely absent in the double mutant. Expression of glucosinolate biosynthetic genes was slightly but significantly reduced by the single myb mutations, while the double mutation resulted in a drastic decrease in expression of these genes. Since the myb28myb29 double mutant is the first Arabidopsis genotype without any aliphatic glucosinolates, we used it to establish the relevance of aliphatic glucosinolate biosynthesis to herbivory by larvae of the lepidopteran insect Mamestra brassicae. Plant damage correlated inversely to the levels of aliphatic glucosinolates observed in those plants: Larval weight gain was 2.6 fold higher on the double myb28myb29 mutant completely lacking aliphatic glucosinolates and 1.8 higher on the single mutants with intermediate levels of aliphatic glucosinolates compared to wild type plants.

  15. The impact of the absence of aliphatic glucosinolates on insect herbivory in Arabidopsis.

    Science.gov (United States)

    Beekwilder, Jules; van Leeuwen, Wessel; van Dam, Nicole M; Bertossi, Monica; Grandi, Valentina; Mizzi, Luca; Soloviev, Mikhail; Szabados, Laszlo; Molthoff, Jos W; Schipper, Bert; Verbocht, Hans; de Vos, Ric C H; Morandini, Piero; Aarts, Mark G M; Bovy, Arnaud

    2008-04-30

    Aliphatic glucosinolates are compounds which occur in high concentrations in Arabidopsis thaliana and other Brassicaceae species. They are important for the resistance of the plant to pest insects. Previously, the biosynthesis of these compounds was shown to be regulated by transcription factors MYB28 and MYB29. We now show that MYB28 and MYB29 are partially redundant, but in the absence of both, the synthesis of all aliphatic glucosinolates is blocked. Untargeted and targeted biochemical analyses of leaf metabolites showed that differences between single and double knock-out mutants and wild type plants were restricted to glucosinolates. Biosynthesis of long-chain aliphatic glucosinolates was blocked by the myb28 mutation, while short-chain aliphatic glucosinolates were reduced by about 50% in both the myb28 and the myb29 single mutants. Most remarkably, all aliphatic glucosinolates were completely absent in the double mutant. Expression of glucosinolate biosynthetic genes was slightly but significantly reduced by the single myb mutations, while the double mutation resulted in a drastic decrease in expression of these genes. Since the myb28myb29 double mutant is the first Arabidopsis genotype without any aliphatic glucosinolates, we used it to establish the relevance of aliphatic glucosinolate biosynthesis to herbivory by larvae of the lepidopteran insect Mamestra brassicae. Plant damage correlated inversely to the levels of aliphatic glucosinolates observed in those plants: Larval weight gain was 2.6 fold higher on the double myb28myb29 mutant completely lacking aliphatic glucosinolates and 1.8 higher on the single mutants with intermediate levels of aliphatic glucosinolates compared to wild type plants.

  16. Vapour pressure and enthalpy of vaporization of aliphatic dialkyl carbonates

    Energy Technology Data Exchange (ETDEWEB)

    Kozlova, Svetlana A.; Emel' yanenko, Vladimir N.; Georgieva, Miglena [Department of Physical Chemistry, University of Rostock, Hermannstrasse 14, D-18051 Rostock (Germany); Verevkin, Sergey P. [Department of Physical Chemistry, University of Rostock, Hermannstrasse 14, D-18051 Rostock (Germany)], E-mail: sergey.verevkin@uni-rostock.de; Chernyak, Yury [Huntsman Corporation, Advanced Technology Center, 8600 Gosling Road, The Woodlands, TX 77381 (United States); Schaeffner, Benjamin; Boerner, Armin [Leibniz Institut fuer Katalyse an der Universitaet Rostock e.V., Albert-Einstein Strasse 29a, 18059 Rostock (Germany)

    2008-07-15

    Molar enthalpies of vaporization of aliphatic alkyl carbonates: dimethyl carbonate [616-38-6], diethyl carbonate [105-58-8], di-n-propyl carbonate [623-96-1], di-n-butyl carbonate [542-52-9], and dibenzyl carbonate [3459-92-5] were obtained from the temperature dependence of the vapour pressure measured by the transpiration method. A large number of the primary experimental results on temperature dependences of vapour pressures have been collected from the literature and have been treated uniformly in order to derive vaporization enthalpies of dialkyl carbonates at the reference temperature 298.15 K. An internal consistency check was performed on enthalpy of vaporization values for dialkyl carbonates studied in this work.

  17. Aliphatic Polyethers: Classical Polymers for the 21st Century.

    Science.gov (United States)

    Klein, Rebecca; Wurm, Frederik R

    2015-06-01

    Polyethers-polymers with the structural element (R'-O-R)n in their backbone--are an old class of polymers which were already used at the time of the ancient Egyptians. However, still today these materials are highly important with applications in all areas of our life, reaching from the automotive and paper industry to cosmetics and biomedical applications. In this Review, different aliphatic polyethers like poly(epoxide)s, poly(oxetane)s, and poly(tetrahydrofuran) are discussed. Special emphasis is placed on the history, the polymerization techniques (industrially and in academia), the properties, the applications as well as recent developments of these materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Aqueous infrared carboxylate absorbances: Aliphatic di-acids

    Science.gov (United States)

    Cabaniss, S.E.; Leenheer, J.A.; McVey, I.F.

    1998-01-01

    Aqueous attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectra of 18 aliphatic di-carboxylic acids are reported as a function of pH. The spectra show isosbestic points and intensity changes which indicate that Beer's law is obeyed, and peak frequencies lie within previously reported ranges for aqueous carboxylates and pure carboxylic acids. Intensity sharing from the symmetric carboxylate stretch is evident in many cases, so that bands which are nominally due to alkyl groups show increased intensity at higher pH. The asymmetric stretch of the HA- species is linearly related to the microscopic acidity constant of the H2A species, with ??pK 2 intervening atoms). The results suggest that aqueous ATR-FTIR may be able to estimate 'intrinsic' pKa values of carboxylic acids, in addition to providing quantitative estimates of ionization. ?? 1998 Elsevier Science B.V. All rights reserved.

  19. Localized aliphatic organic material on the surface of Ceres

    Science.gov (United States)

    De Sanctis, M. C.; Ammannito, E.; McSween, H. Y.; Raponi, A.; Marchi, S.; Capaccioni, F.; Capria, M. T.; Carrozzo, F. G.; Ciarniello, M.; Fonte, S.; Formisano, M.; Frigeri, A.; Giardino, M.; Longobardo, A.; Magni, G.; McFadden, L. A.; Palomba, E.; Pieters, C. M.; Tosi, F.; Zambon, F.; Raymond, C. A.; Russell, C. T.

    2017-02-01

    Organic compounds occur in some chondritic meteorites, and their signatures on solar system bodies have been sought for decades. Spectral signatures of organics have not been unambiguously identified on the surfaces of asteroids, whereas they have been detected on cometary nuclei. Data returned by the Visible and InfraRed Mapping Spectrometer on board the Dawn spacecraft show a clear detection of an organic absorption feature at 3.4 micrometers on dwarf planet Ceres. This signature is characteristic of aliphatic organic matter and is mainly localized on a broad region of ~1000 square kilometers close to the ~50-kilometer Ernutet crater. The combined presence on Ceres of ammonia-bearing hydrated minerals, water ice, carbonates, salts, and organic material indicates a very complex chemical environment, suggesting favorable environments to prebiotic chemistry.

  20. Hydrolytic And Enzymatic Degradation Characteristics Of Biodegradable Aliphatic Polysters

    Institute of Scientific and Technical Information of China (English)

    LI Suming

    2004-01-01

    Aliphatic polyesters, especially those derived from lactide (PLA), glycolide (PGA) and ε-caprolactone (PCL), are being investigated worldwide for applications in the field of surgery (suture material, devices for internal bone fracture fixation), pharmacology (sustained drug delivery systems), and tissue engineering (scaffold for tissue regeneration) [1,2]. This is mainly due to their good biocompatibility and variable degradability. These polymers present also a growing interest for environmental applications in agriculture (mulch films) and in our everyday life (packaging material)as the development of biodegradable materials is now considered as one of the potential solutions to the problem of plastic waste management.For both biomedical and environmental applications, it is of major importance to understand the degradation characteristics of the polymers. The hydrolytic degradation of aliphatic polyesters has been investigated by many research groups. Our group has shown that degradation of PLAGA large size devices is faster inside than at the surface. This heterogeneous degradation is due to the autocatalytic effect of carboxylic endgroups formed by ester bond cleavage. Moreover,degradation-induced morphological and compositional changes were also elucidated. In the case of PCL, the hydrolytic degradation is very slow due to its hydrophobicity and crystallinity.The enzymatic degradation of these polymers has been investigated by a number of authors. A specific enzyme, proteinase K, has been shown to have significant effects on PLA degradation. This enzyme preferentially degrade L-lactate units as opposed to D-lactate ones, amorphous zones as opposed to crystalline ones [3]. The enzymatic degradation of PCL polymers has also been investigated. A number of lipase-type enzymes were found to significantly accelerate the degradation of PCL despite its high crystallinity. In the case of PLA/PCL blends, the two components exhibited well separated crystalline domains

  1. 40 CFR 721.3830 - Formaldehyde, reaction products with an alkylated phenol and an aliphatic amine (generic).

    Science.gov (United States)

    2010-07-01

    ... an alkylated phenol and an aliphatic amine (generic). 721.3830 Section 721.3830 Protection of... products with an alkylated phenol and an aliphatic amine (generic). (a) Chemical substance and significant..., reaction products with an alkylated phenol and an aliphatic amine (PMN P-99-0531) is subject to...

  2. 不同比例制川乌配伍甘草对单酯型生物碱煎出量的影响%Effect of Aconiti Radix Preparata combined with Glycyrrhizae Radix in different ratios on monoester alkaloids

    Institute of Scientific and Technical Information of China (English)

    王峰峰; 宋兆辉; 张兰兰; 周水平; 冯锋

    2012-01-01

    目的 研究制川乌配伍甘草对制川乌中多种单酯型生物碱煎出量的影响,探索其变化规律,以指导制川乌与甘草的合理配伍.方法 HPLC法测定制川乌与甘草不同比例配伍时煎出液中单酯型生物碱的总量,并通过对比,分析不同配比对煎出量的影响.结果 随着甘草配伍量的增加,煎煮液中单酯型生物碱总量逐渐降低,每种单酯型生物碱煎出量趋于单煎液煎出量的40%.结论 甘草配伍制川乌时,甘草的使用量应是制川乌的一半以上,既可以保证煎出液中单酯型生物碱总量稳定可控,又可以防止制川乌毒性过大造成使用危险.%Objective To study the effect of Aconiti Radix Preparata (RAP) combined with Glycyrrhizae Radix (RG) in different ratios on the decocted yield of monoester-type alkaloid from RAP and to investigate the disciplines of various compatibilities. Methods HPLC was adopted to determine the monoester-type alkaloid in decoction with different ratios of RAP and RG The influence of the various compatibilities or alkaloid was analyzed. Results The total decocted yields of monoester-type alkaloid in the decoction decreased with the increasing of RG in the decoction. The monoester-type alkaloid in compatibility tended to be 20% of RAP single decoction. Conclusion The usage of RG should be more than half of that of RAP when using together, which could make the yields of monoester-type alkaloid stable and controllable and avoid the danger for use from the excessive toxicity of RAP.

  3. The effect of diesters and lauric acid on rheological properties of air/water interfaces stabilized by oligofructose lauric acid monoesters.

    Science.gov (United States)

    van Kempen, Silvia E H J; Schols, Henk A; van der Linden, Erik; Sagis, Leonard M C

    2013-08-14

    In this study, the rheological properties of interfaces stabilized by oligofructose fatty acid esters were elucidated. First, the properties of interfaces stabilized by monoesters (ME), diesters (DE), lauric acid (LA), oligofructose (OF), and mixtures of ME with DE, LA, or OF were studied. Second, the properties of interfaces stabilized by the crude product (CP) containing ME, DE, LA, and OF were studied. The dependency of the dilatational modulus on frequency and deformation amplitude indicated the possible formation of a soft glass phase for ME, and a viscous interface for DE. When ME and DE were mixed at a ratio of 0.8/0.2, the experimental results suggest that the interfacial structure consists of islands of a glass phase formed by ME, dispersed in a 2D viscous phase of DE. CP stabilized interfaces, where the ratio ME/DE was higher, lead to a different rheological response. The ratio ME/DE plays an important role in the surface properties of the CP. This may have significant consequences for applications in macroscopic systems such as foams.

  4. Synthesis and Biological Evaluation of 5′-O-Dicarboxylic Fatty Acyl Monoester Derivatives of Anti-HIV Nucleoside Reverse Transcriptase Inhibitors

    Science.gov (United States)

    Pemmaraju, Bhanu; Agarwal, Hitesh K; Oh, Donghoon; Buckheit, Karen W.; Buckheit, Robert W.; Tiwari, Rakesh; Parang, Keykavous

    2014-01-01

    A number of 5′-O-dicarboxylic fatty acyl monoester derivatives of 3′-azido-3′-deoxythymidine (zidovudine, AZT), 2′,3′-didehydro-2′,3′-dideoxythymidine (stavudine, d4T), and 3′-fluoro-3′-deoxythymidine (alovudine, FLT) were synthesized to improve the lipophilicity and potentially the cellular delivery of parent polar 2′, 3′-dideoxynucleoside (ddN) analogues. The compounds were evaluated for their anti-HIV activity. Three different fatty acids with varying chain length of suberic acid (octanedioic acid), sebacic acid (decanedioic acid), and dodecanedioic acid were used for the conjugation with the nucleosides. The compounds were evaluated for anti-HIV activity and cytotoxicity. All dicarboxylic ester conjugates of nucleosides exhibited significantly higher anti-HIV activity than that of the corresponding parent nucleoside analogs. Among all the tested conjugates, 5′-O-suberate derivative of AZT (EC50 = 0.10 nM) was found to be the most potent compound and showed 80-fold higher anti-HIV activity than AZT without any significant toxicity (TC50 > 500 nM). PMID:24791029

  5. Synthesis and Biological Evaluation of 5'-O-Dicarboxylic Fatty Acyl Monoester Derivatives of Anti-HIV Nucleoside Reverse Transcriptase Inhibitors.

    Science.gov (United States)

    Pemmaraju, Bhanu; Agarwal, Hitesh K; Oh, Donghoon; Buckheit, Karen W; Buckheit, Robert W; Tiwari, Rakesh; Parang, Keykavous

    2014-03-19

    A number of 5'-O-dicarboxylic fatty acyl monoester derivatives of 3'-azido-3'-deoxythymidine (zidovudine, AZT), 2',3'-didehydro-2',3'-dideoxythymidine (stavudine, d4T), and 3'-fluoro-3'-deoxythymidine (alovudine, FLT) were synthesized to improve the lipophilicity and potentially the cellular delivery of parent polar 2', 3'-dideoxynucleoside (ddN) analogues. The compounds were evaluated for their anti-HIV activity. Three different fatty acids with varying chain length of suberic acid (octanedioic acid), sebacic acid (decanedioic acid), and dodecanedioic acid were used for the conjugation with the nucleosides. The compounds were evaluated for anti-HIV activity and cytotoxicity. All dicarboxylic ester conjugates of nucleosides exhibited significantly higher anti-HIV activity than that of the corresponding parent nucleoside analogs. Among all the tested conjugates, 5'-O-suberate derivative of AZT (EC50 = 0.10 nM) was found to be the most potent compound and showed 80-fold higher anti-HIV activity than AZT without any significant toxicity (TC50 > 500 nM).

  6. Characterization, Distribution, Sources and Origins of Aliphatic Hydrocarbons from Surface Sediment of Prai Strait, Penang, Malaysia: A Widespread Anthropogenic Input

    Directory of Open Access Journals (Sweden)

    Mahyar Sakari

    2008-07-01

    Full Text Available Persistent organic pollutants such as petroleum hydrocarbons are one of the most serious and important class of pollutants that face to many countries including Malaysia. Aliphatic hydrocarbons contain straight chain alkane; derive from anthropogenic and natural sources to the marine environment. The multi-purpose strait of Prai is located in the Northwest of Peninsular Malaysia plays an important economic role in the Southeast Asia. Twenty surface sediment samples were collected using Eckman dredge to measure the concentration and determine the characterization, sources and origins of the aliphatic hydrocarbons in December 2006. Samples (top 4 cm were extracted with Soxhlet, treated with activated copper and subjected to 2 steps column chromatography for purification and fractionation. Alkane fraction injected into Gas Chromatography–Flame Ionization Detector (GC-FID for instrumental analysis. The results showed that total n-alkane concentrations are ranging from 512 to 10770 ng/mg d. w. Carbon Preferences Index (CPI revealed an extreme widespread anthropogenic input and naturally derived (CPI= 0 to 4.88 hydrocarbons in the study area. The ratio of C31/C19 indicated that natural hydrocarbons are generating from terrestrial vascular plants and transferring by rivers. The characteristics of Major Hydrocarbons provided evidences that oil and its derivatives either fresh or degraded are the major contributors of the pollution in the study area. Statistical approaches also confirmed that 85% of study area affected by oil sources of pollution. It is seen that aliphatic hydrocarbons mostly transfer by lateral input to the marine environment than atmospheric movements.

  7. The molecular assembly of the ionic liquid/aliphatic carboxylic acid/aliphatic amine as effective and safety transdermal permeation enhancers.

    Science.gov (United States)

    Kubota, Koji; Shibata, Akira; Yamaguchi, Toshikazu

    2016-04-30

    In spite of numerous advantages, transdermal drug delivery systems are unfeasible for most drugs because of the barrier effect of the stratum corneum. Ionic liquids were recently used to enhance transdermal drug delivery by improving drug solubility. In the present study, safe and effective ionic liquids for transdermal absorption were obtained as salts generated by a neutralization reaction between highly biocompatible aliphatic carboxylic acids (octanoic acid or isostearic acid) and aliphatic amines (diisopropanolamine or triisopropanolamine) (Medrx Co., Ltd., 2009). The mechanism of skin permeability enhancement by ionic liquids was investigated by hydrophilic phenol red and hydrophobic tulobuterol. Further, the skin permeation enhancing effect was remarkably superior in the acid excess state rather than the neutralization state. Infrared absorption spectrum analysis confirmed that ionic liquids/aliphatic carboxylic acid/aliphatic amine are coexisting at all mixing states. In the acid excess state, ionic liquids interact with aliphatic carboxylic acids via hydrogen bonds. Thus, the skin permeation enhancing effect is not caused by the ionic liquid alone. The "liquid salt mixture," referred to as a complex of ingredients coexisting with ionic liquids, forms a molecular assembly incorporating hydrophilic drug. This molecular assembly was considered an effective and safety enhancer of transdermal drug permeation.

  8. Seasonal distribution of aliphatic hydrocarbons in the Vaza Barris Estuarine System, Sergipe, Brazil.

    Science.gov (United States)

    Barbosa, José Carlos S; Santos, Lukas G G V; Sant'Anna, Mércia V S; Souza, Michel R R; Damasceno, Flaviana C; Alexandre, Marcelo R

    2016-03-15

    The seasonal assessment of anthropogenic activities in the Vaza Barris estuarine river system, located in the Sergipe state, northeastern Brazil, was performed using the aliphatic hydrocarbon distribution. The aliphatic hydrocarbon and isoprenoid (Pristane and Phytane) concentrations ranged between 0.19 μg g(-1) and 8.5 μg g(-1) of dry weight. Data were analyzed using Kruskal-Wallis test, with significance level set at p n-alkanes/n-C16, Low Molecular Weight/High Molecular Weight ratio (LMW/HMW) and Terrigenous to Aquatic Ratio (TAR) suggested biogenic input of aliphatic hydrocarbons for most samples, with significant contribution of higher plants.

  9. Sum frequency generation image reconstruction: Aliphatic membrane under spherical cap geometry

    Energy Technology Data Exchange (ETDEWEB)

    Volkov, Victor [Bereozovaya 2A, Konstantinovo, Moscow Region 140207 (Russian Federation)

    2014-10-07

    The article explores an opportunity to approach structural properties of phospholipid membranes using Sum Frequency Generation microscopy. To establish the principles of sum frequency generation image reconstruction in such systems, at first approach, we may adopt an idealistic spherical cap uniform assembly of hydrocarbon molecules. Quantum mechanical studies for decanoic acid (used here as a representative molecular system) provide necessary information on transition dipole moments and Raman tensors of the normal modes specific to methyl terminal – a typical moiety in aliphatic (and phospholipid) membranes. Relative degree of localization and frequencies of the normal modes of methyl terminals make nonlinearities of this moiety to be promising in structural analysis using Sum Frequency Generation imaging. Accordingly, the article describes derivations of relevant macroscopic nonlinearities and suggests a mapping procedure to translate amplitudes of the nonlinearities onto microscopy image plane according to geometry of spherical assembly, local molecular orientation, and optical geometry. Reconstructed images indicate a possibility to extract local curvature of bilayer envelopes of spherical character. This may have practical implications for structural extractions in membrane systems of practical relevance.

  10. Thermally reversible thermoset materials based on the chemical modification of alternating aliphatic polyketones

    NARCIS (Netherlands)

    Araya Hermosilla, Rodrigo Andrés

    2016-01-01

    This thesis focused on the synthesis and characterization of different kinds of reversible thermosets and thermoset nanocomposite materials by using alternating aliphatic polyketone (PK) as raw material. Fundamental knowledge was generated regarding the molecular design of new polymers via chemical

  11. Calamistrin E, the First Annonaceous Acetogenin with Double Bond in Aliphatic Chain from Genus Uvaria

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Calamistrin E, the first Annonaceous acetogenin with C=C bond in the aliphatic chain from the genus Uvaria was isolated from U. calamistrata. Its structure including relative and absolute configurations was determined by chemical derivation and spectral analysis.

  12. Fully Biobased Unsaturated Aliphatic Polyesters from Renewable Resources : Enzymatic Synthesis, Characterization, and Properties

    NARCIS (Netherlands)

    Jiang, Yi; Alberda van Ekenstein, Gerhard; Woortman, Albert J. J.; Loos, Katja

    2014-01-01

    Fully biobased saturated and unsaturated aliphatic polyesters and oligoesters are successfully prepared by Candida antarctica lipase B (CALB)-catalyzed polycondensations of succinate, itaconate, and 1,4-butanediol. The effects of monomer substrates and polymerization methods on enzymatic polycondens

  13. Insights into support wettability in tuning catalytic performance in the oxidation of aliphatic alcohols to acids.

    Science.gov (United States)

    Wang, Min; Wang, Feng; Ma, Jiping; Chen, Chen; Shi, Song; Xu, Jie

    2013-07-28

    A superhydrophobic catalyst was prepared by immobilizing Pt nanoparticles on superhydrophobic organic-inorganic hybrid silicas, which showed high activity and selectivity in the oxidation of aliphatic alcohols to carboxylic acids.

  14. Catalytic water dissociation using hyperbranched aliphatic polyester (Boltorn series) as the interface of a bipolar membrane.

    Science.gov (United States)

    Xue, Yanhong; Xu, Tongwen; Fu, Rongqiang; Cheng, Yiyun; Yang, Weihua

    2007-12-15

    The effect of hyperbranched aliphatic polyester (Boltorn series) on the water dissociation in bipolar membranes was firstly investigated in this paper. The bipolar membranes were prepared by immersing the anion exchange layer in a hyperbranched aliphatic polyester solution and then coating on the layer a polyphenylene oxide (SPPO) solution. The SEM observations proved the existence of hyperbranched aliphatic polyester at the membrane intermediate layer. The adsorption amount was evaluated by the oxygen content via XPS. The junction thickness of the prepared bipolar membrane was determined by electrochemical impedance spectroscopy (EIS), and the membrane performances were evaluated by current-voltage curves. The results showed that the amount and generation of Boltorn series, and temperature all affected I-V behaviors of the fabricated bipolar membranes, and the former two played the critical role. These effects were explained on the basis of the water dissociation theory and the characteristics of hyperbranched aliphatic polyester.

  15. Fully Biobased Unsaturated Aliphatic Polyesters from Renewable Resources : Enzymatic Synthesis, Characterization, and Properties

    NARCIS (Netherlands)

    Jiang, Yi; Alberda van Ekenstein, Gerhard; Woortman, Albert J. J.; Loos, Katja

    2014-01-01

    Fully biobased saturated and unsaturated aliphatic polyesters and oligoesters are successfully prepared by Candida antarctica lipase B (CALB)-catalyzed polycondensations of succinate, itaconate, and 1,4-butanediol. The effects of monomer substrates and polymerization methods on enzymatic

  16. Liquid-crystalline aromatic-aliphatic copolyester bioresorbable polymers.

    Science.gov (United States)

    de Oca, Horacio Montes; Wilson, Joanne E; Penrose, Andrew; Langton, David M; Dagger, Anthony C; Anderson, Melissa; Farrar, David F; Lovell, Christopher S; Ries, Michael E; Ward, Ian M; Wilson, Andrew D; Cowling, Stephen J; Saez, Isabel M; Goodby, John W

    2010-10-01

    The synthesis and characterisation of a series of liquid-crystalline aromatic-aliphatic copolyesters are presented. Differential scanning calorimetry showed these polymers have a glass transition temperature in the range 72 degrees C-116 degrees C. Polarised optical microscopy showed each polymer exhibits a nematic mesophase on heating to the molten state at temperatures below 165 degrees C. Melt processing is demonstrated by the production of injection moulded and compression moulded specimens with Young's modulus of 5.7 +/- 0.3 GPa and 2.3 +/- 0.3 GPa, respectively. Wide-angle X-ray scattering data showed molecular orientation is responsible for the increase of mechanical properties along the injection direction. Degradation studies in the temperature range 37 degrees C-80 degrees C are presented for one polymer of this series and a kinetic constant of 0.002 days(-1) is obtained at 37 degrees C assuming a first order reaction. The activation energy (83.4 kJ mol(-1)) is obtained following the Arrhenius analysis of degradation, showing degradation of this material is less temperature sensitive compared with other commercially available biodegradable polyesters. In vitro and in vivo biocompatibility data are presented and it is shown the unique combination of degradative, mechanical and biological properties of these polymers may represent in the future an alternative for medical device manufacturers.

  17. Aliphatic polyesters for medical imaging and theranostic applications.

    Science.gov (United States)

    Nottelet, Benjamin; Darcos, Vincent; Coudane, Jean

    2015-11-01

    Medical imaging is a cornerstone of modern medicine. In that context the development of innovative imaging systems combining biomaterials and contrast agents (CAs)/imaging probes (IPs) for improved diagnostic and theranostic applications focuses intense research efforts. In particular, the classical aliphatic (co)polyesters poly(lactide) (PLA), poly(lactide-co-glycolide) (PLGA) and poly(ɛ-caprolactone) (PCL), attract much attention due to their long track record in the medical field. This review aims therefore at providing a state-of-the-art of polyester-based imaging systems. In a first section a rapid description of the various imaging modalities, including magnetic resonance imaging (MRI), optical imaging, computed tomography (CT), ultrasound (US) and radionuclide imaging (SPECT, PET) will be given. Then, the two main strategies used to combine the CAs/IPs and the polyesters will be discussed. In more detail we will first present the strategies relying on CAs/IPs encapsulation in nanoparticles, micelles, dendrimers or capsules. We will then present chemical modifications of polyesters backbones and/or polyester surfaces to yield macromolecular imaging agents. Finally, opportunities offered by these innovative systems will be illustrated with some recent examples in the fields of cell labeling, diagnostic or theranostic applications and medical devices. Copyright © 2015 Elsevier B.V. All rights reserved.

  18. Shape memory polymers based on uniform aliphatic urethane networks

    Energy Technology Data Exchange (ETDEWEB)

    Wilson, T S; Bearinger, J P; Herberg, J L; Marion III, J E; Wright, W J; Evans, C L; Maitland, D J

    2007-01-19

    Aliphatic urethane polymers have been synthesized and characterized, using monomers with high molecular symmetry, in order to form amorphous networks with very uniform supermolecular structures which can be used as photo-thermally actuable shape memory polymers (SMPs). The monomers used include hexamethylene diisocyanate (HDI), trimethylhexamethylenediamine (TMHDI), N,N,N{prime},N{prime}-tetrakis(hydroxypropyl)ethylenediamine (HPED), triethanolamine (TEA), and 1,3-butanediol (BD). The new polymers were characterized by solvent extraction, NMR, XPS, UV/VIS, DSC, DMTA, and tensile testing. The resulting polymers were found to be single phase amorphous networks with very high gel fraction, excellent optical clarity, and extremely sharp single glass transitions in the range of 34 to 153 C. Thermomechanical testing of these materials confirms their excellent shape memory behavior, high recovery force, and low mechanical hysteresis (especially on multiple cycles), effectively behaving as ideal elastomers above T{sub g}. We believe these materials represent a new and potentially important class of SMPs, and should be especially useful in applications such as biomedical microdevices.

  19. Aliphatic and aromatic hydrocarbons in the mediterranean aerosol.

    Science.gov (United States)

    Sicre, M A; Marty, J C; Saliot, A; Aparicio, X; Grimalt, J; Albaiges, J

    1987-01-01

    The atmospheric transport of organic pollutants over long distances and their effect on the biological cycles of the sea are two major questions of concern in environmental chemistry. These processes are of particular importance in the Mediterranean Sea because of its semi-enclosed characteristics, which determine the accumulation of the pollutants entering into the system. In order to get some insight into these processes a project (PHYCEMED), was developed for the evaluation of the atmospheric budget of organic and inorganic substances in the Western Mediterranean and for the investigation of the exchange mechanisms of these materials across the air/sea interface. A high volume air sampling system including a cascade impactor was placed on board of the R/V le Suroit for collecting the aerosols along several transects parallel to the French, Spanish and North-African coasts, facing areas of different population densities and industrial activities. The cruise was realised on October 1983 and the particulate material was fractionated into the following sizes: 7.2, 3.0, 1.5, 0.96, and 0.03 micron. Quantitative and qualitative analyses of the aliphatic and the aromatic hydrocarbons present in these fractions were performed by high resolution gas chromatography and gas chromatography-mass spectrometry.

  20. Enhanced crystallization of poly (lactic acid) through reactive aliphatic bisamide

    Science.gov (United States)

    Nanthananon, P.; Seadan, M.; Pivsa-Art, S.; Suttiruengwong, S.

    2015-07-01

    The poor crystallization rate of poly (lactic acid) (PLA) is a major drawback in terms of controlling the properties of final products. To overcome this, a nucleating agent is normally applied. In this work, the aliphatic bisamide, N, N'-(1,3-propylene) bis(10-undecenamide) (PBU), having reactive functional groups is used as a crystallization promoter for PLA by adding PBU in various concentration (0.1-0.7 wt%) into PLA together with peroxide via reactive melt blending. The conventional ethylene bis-stearamide(EBS) is used for a comparison. The extruded samples are characterized for gel content and FT-IR spectroscopy. The crystallization behaviour and rate, and spherulites morphology are investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM), respectively. It is found that the addition of PBU into PLA results in the dramatic increase in crystallinity and crystallization rate of PLA compared with neat PLA and PLA added EBS. The crystallinity increases to 24.9-28.3% higher than neat PLA under even cooling rate of 7°C/min. The addition of 0.7 wt% PBU shows the fastest crystallization rate with t1/2 value isothermally crystallized at 130°C of only 6 min. POM images indicate the increase in the nucleation density and very fine spherulitesof PLA added PBU, promoting the fast crystallization.

  1. Electrospun aliphatic polycarbonates as tailored tissue scaffold materials.

    Science.gov (United States)

    Welle, Alexander; Kröger, Mario; Döring, Manfred; Niederer, Kerstin; Pindel, Elvira; Chronakis, Ioannis S

    2007-04-01

    Two different aliphatic polycarbonates were synthesised from CO(2) and the respective epoxides. Poly(propyl carbonate) (PPC) was prepared by heterogeneous catalysis with zinc glutarate. Poly(cyclohexyl carbonate) (PCHC) was prepared via living copolymerisation homogeneously catalysed by a 3-amino-2-cyanoimidoacrylate zinc acetate complex and subjected to electrospinning. The obtained nanofibres had a well-defined morphology free of beads along the fibres and with slightly porous structures on their surface. Subsequently, low-power deep UV irradiations, previously applied for photochemical surface modifications of two-dimensional and three-dimensional scaffolds from biostable polymers, were performed. Here, an effect on surface and bulk properties of PPC nanofibres was observed. Surface modifications of both polymers affected plasma protein adsorption. Photochemical bulk modifications observed for the first time on PPC nanofibres are indicating the possibility of spatial control of biodegradation rates, hence allow for control of the progression of host/implant interactions in vivo. In particular PPC was used for cell culture of L929 fibroblasts and primary rat hepatocytes. Even delicate primary cells showed good adhesion to the scaffolds and high viability.

  2. Thermally reversible thermoset materials based on the chemical modification of alternating aliphatic polyketones

    OpenAIRE

    Araya Hermosilla, Rodrigo Andrés

    2016-01-01

    This thesis focused on the synthesis and characterization of different kinds of reversible thermosets and thermoset nanocomposite materials by using alternating aliphatic polyketone (PK) as raw material. Fundamental knowledge was generated regarding the molecular design of new polymers via chemical modification of PK with aliphatic and aromatic amine compounds. The resulting thermally reversible thermoset systems were investigated to outline the benefits for the synergistic cooperation betwee...

  3. Silver-Catalyzed Decarboxylative Allylation of Aliphatic Carboxylic Acids in Aqueous Solution.

    Science.gov (United States)

    Cui, Lei; Chen, He; Liu, Chao; Li, Chaozhong

    2016-05-06

    Direct decarboxylative radical allylation of aliphatic carboxylic acids is described. With K2S2O8 as the oxidant and AgNO3 as the catalyst, the reactions of aliphatic carboxylic acids with allyl sulfones in aqueous CH3CN solution gave the corresponding alkenes in satisfactory yields under mild conditions. This site-specific allylation method is applicable to all primary, secondary, and tertiary alkyl acids and exhibits wide functional group compatibility.

  4. Aliphatic acetogenin constituents of avocado fruits inhibit human oral cancer cell proliferation by targeting the EGFR/RAS/RAF/MEK/ERK1/2 pathway

    Energy Technology Data Exchange (ETDEWEB)

    D' Ambrosio, Steven M. [Department of Radiology, College of Medicine, The Ohio State University, Columbus, OH 43210 (United States); Comprehensive Cancer Center, The Ohio State University, Columbus, OH 43210 (United States); Han, Chunhua [Department of Radiology, College of Medicine, The Ohio State University, Columbus, OH 43210 (United States); Pan, Li; Douglas Kinghorn, A. [Division of Medicinal Chemistry and Pharmacognosy, College of Pharmacy, The Ohio State University, Columbus, OH 43210 (United States); Ding, Haiming, E-mail: ding.29@osu.edu [Department of Radiology, College of Medicine, The Ohio State University, Columbus, OH 43210 (United States)

    2011-06-10

    Highlights: {yields} The aliphatic acetogenins [(2S,4S)-2,4-dihydroxyheptadec-16-enyl acetate] (1) and [(2S,4S)-2,4-dihydroxyheptadec-16-ynyl acetate] (2) isolated from avocado fruit inhibit phosphorylation of c-RAF (Ser338) and ERK1/2 (Thr202/Tyr204). {yields} Aliphatic acetogenin 2, but not 1, prevents EGF-induced activation of EGFR (Tyr1173). {yields} Combination of both aliphatic acetogenins synergistically inhibits c-RAF (Ser338) and ERK1/2 (Thr202/Tyr204) phosphorylation and human oral cancer cell proliferation. {yields} The potential anticancer activity of avocado fruits is due to a combination of specific aliphatic acetogenins targeting two key components of the EGFR/RAS/RAF/MEK/ERK1/2 cancer pathway. {yields} Providing a double hit on a critical cancer pathway such as EGFR/RAS/RAF/MEK/ERK1/2 by phytochemicals like those found in avocado fruit could lead to more effective approach toward cancer prevention. -- Abstract: Avocado (Persea americana) fruits are consumed as part of the human diet and extracts have shown growth inhibitory effects in various types of human cancer cells, although the effectiveness of individual components and their underlying mechanism are poorly understood. Using activity-guided fractionation of the flesh of avocado fruits, a chloroform-soluble extract (D003) was identified that exhibited high efficacy towards premalignant and malignant human oral cancer cell lines. From this extract, two aliphatic acetogenins of previously known structure were isolated, compounds 1 [(2S,4S)-2,4-dihydroxyheptadec-16-enyl acetate] and 2 [(2S,4S)-2,4-dihydroxyheptadec-16-ynyl acetate]. In this study, we show for the first time that the growth inhibitory efficacy of this chloroform extract is due to blocking the phosphorylation of EGFR (Tyr1173), c-RAF (Ser338), and ERK1/2 (Thr202/Tyr204) in the EGFR/RAS/RAF/MEK/ERK1/2 cancer pathway. Compounds 1 and 2 both inhibited phosphorylation of c-RAF (Ser338) and ERK1/2 (Thr202/Tyr204). Compound 2, but not

  5. 氮川四胺的合成进展%Progress on synthesis of aliphatic tripodal tetramines

    Institute of Scientific and Technical Information of China (English)

    赵蓓; 张兆丽; 秦红艳; 张晓云; 吴伟

    2012-01-01

    The aliphatic tripodal tetramines are usually used as ligands, curing reagents for resins and intermediates for organic synthesis. The synthetic approaches for four aliphatic tripodal tetramines includingtris(2-aminoethyl) amin( tren) , N, N-bis (2 -aminoethyl) propylenediamine ( baep ) , N- ( 2 -ami-noethyl) -N, N-bis ( 3 -aminopropyl) amine ( abap ) andtris ( 3 -aminopropyl) amine ( trpn ) have been reviewed. Among them, tren and trpn are symmetrical tetraamines, whereas baep and abap are asymmetrical tetraaminea.%脂肪族氮氚四胺常用作配体、树脂固化剂、有机合成中间体等.综述了三(2-氨基乙基)胺(Tren)、N,N-二(2-氨基乙基)丙二胺(Baep)、N-2-氨基乙基-N,N-二(3-氨基丙基)胺(Abap)和三(3-氨基丙基)胺(Trpn)脂肪族氮氚四胺的合成方法.其中Tren和Trpn的结构具有对称性,Baep和Abap属于结构不对称氮氚四胺.

  6. Microbe-aliphatic hydrocarbon interactions in soil: implications for biodegradation and bioremediation.

    Science.gov (United States)

    Stroud, J L; Paton, G I; Semple, K T

    2007-05-01

    Aliphatic hydrocarbons make up a substantial portion of organic contamination in the terrestrial environment. However, most studies have focussed on the fate and behaviour of aromatic contaminants in soil. Despite structural differences between aromatic and aliphatic hydrocarbons, both classes of contaminants are subject to physicochemical processes, which can affect the degree of loss, sequestration and interaction with soil microflora. Given the nature of hydrocarbon contamination of soils and the importance of bioremediation strategies, understanding the fate and behaviour of aliphatic hydrocarbons is imperative, particularly microbe-contaminant interactions. Biodegradation by microbes is the key removal process of hydrocarbons in soils, which is controlled by hydrocarbon physicochemistry, environmental conditions, bioavailability and the presence of catabolically active microbes. Therefore, the aims of this review are (i) to consider the physicochemical properties of aliphatic hydrocarbons and highlight mechanisms controlling their fate and behaviour in soil; (ii) to discuss the bioavailability and bioaccessibility of aliphatic hydrocarbons in soil, with particular attention being paid to biodegradation, and (iii) to briefly consider bioremediation techniques that may be applied to remove aliphatic hydrocarbons from soil.

  7. Biodegradation and metabolic pathway of β-chlorinated aliphatic acid in Bacillus sp. CGMCC no. 4196.

    Science.gov (United States)

    Lin, Chunjiao; Yang, Lirong; Xu, Gang; Wu, Jianping

    2011-04-01

    In this study, a bacterial Bacillus sp. CGMCC no. 4196 was isolated from mud. This strain exhibited the ability to degrade high concentration of 3-chloropropionate (3-CPA, 120 mM) or 3-chlorobutyrate (30 mM), but not chloroacetate or 2-chloropropionate (2-CPA). The growing cells, resting cells, and cell-free extracts from this bacterium had the capability of 3-CPA degradation. The results indicated that the optimum biocatalyst for 3-CPA biodegradation was the resting cells. The 3-CPA biodegradation pathway was further studied through the metabolites and critical enzymes analysis by HPLC, LC-MS, and colorimetric method. The results demonstrated that the metabolites of 3-CPA were 3-hydroxypropionic acid (3-HP) and malonic acid semialdehyde, and the critical enzymes were 3-CPA dehalogenase and 3-HP dehydroxygenase. Thus, the mechanism of the dehalogenase-catalyzed reaction was inferred as hydrolytic dehalogenation which was coenzyme A-independent and oxygen-independent. Finally, the pathway of β-chlorinated aliphatic acid biodegradation could be concluded as follows: the β-chlorinated acid is first hydrolytically dehalogenated to the β-hydroxyl aliphatic acid, and the hydroxyl aliphatic acid is oxidized to β-carbonyl aliphatic acid by β-hydroxy aliphatic acid dehydroxygenase. It is the first report that 3-HP was produced from 3-CPA by β-chlorinated aliphatic acid dehalogenase.

  8. On the Aliphatic versus Aromatic Content of the Carriers of the "Unidentified" Infrared Emission Features

    CERN Document Server

    Yang, Xuejuan; Li, Aigen; Zhong, Jianxin

    2016-01-01

    Although it is generally accepted that the so-called "unidentified" infrared emission (UIE) features at 3.3, 6.2, 7.7, 8.6, and 11.3 micrometer are characteristic of the stretching and bending vibrations of aromatic hydrocarbon materials, the exact nature of their carriers remains unknown: whether they are free-flying, predominantly aromatic gas-phase molecules, or amorphous solids with a mixed aromatic/aliphatic composition are being debated. Recently, the 3.3 and 3.4 micrometer features which are commonly respectively attributed to aromatic and aliphatic C-H stretches have been used to place an upper limit of ~2\\% on the aliphatic fraction of the UIE carriers (i.e. the number of C atoms in aliphatic chains to that in aromatic rings). Here we further explore the aliphatic versus aromatic content of the UIE carriers by examining the ratio of the observed intensity of the 6.2 micrometer aromatic C-C feature (I6.2) to that of the 6.85 micrometer aliphatic C-H deformation feature (I6.85). To derive the intrinsic...

  9. Sources and distribution of aliphatic and polyaromatic hydrocarbons in sediments from the Neuquen River, Argentine Patagonia.

    Science.gov (United States)

    Monza, Liliana B; Loewy, Ruth M; Savini, Mónica C; Pechen de d'Angelo, Ana M

    2013-01-01

    Spatial distribution and probable sources of aliphatic and polyaromatic hydrocarbons (AHs, PAHs) were investigated in surface sediments collected along the bank of the Neuquen River, Argentina. Total concentrations of aliphatic hydrocarbons ranged between 0.41 and 125 μg/g dw. Six stations presented low values of resolved aliphatic hydrocarbons and the n-alkane distribution indexes applied suggested a clear biogenic source. These values can be considered the baseline levels of aliphatic hydrocarbons for the river sediments. This constitutes important information for the assessment of future impacts since a strong impulse in the exploitation of shale gas and shale oil in these zones is nowadays undergoing. For the other 11 stations, a mixture of aliphatic hydrocarbons of petrogenic and biogenic origin was observed. The spatial distribution reflects local inputs of these pollutants with a significant increase in concentrations in the lower course, where two major cities are located. The highest values of total aliphatic hydrocarbons were found in this sector which, in turn, was the only one where individual PAHs were detected.

  10. Pharmacological activities of cilantro's aliphatic aldehydes against Leishmania donovani.

    Science.gov (United States)

    Donega, Mateus A; Mello, Simone C; Moraes, Rita M; Jain, Surendra K; Tekwani, Babu L; Cantrell, Charles L

    2014-12-01

    Leishmaniasis is a chronic infectious disease caused by different Leishmania species. Global occurrences of this disease are primarily limited to tropical and subtropical regions. Treatments are available; however, patients complain of side effects. Different species of plants have been screened as a potential source of new drugs against leishmaniasis. In this study, we investigated the antileishmanial activity of cilantro (Coriandrum sativum) essential oil and its main components: (E)-2-undecenal, (E)-2-decenal, (E)-2-dodecenal, decanal, dodecanal, and tetradecanal. The essential oil of C. sativum leaves inhibits growth of Leishmani donovani promastigotes in culture with an IC50 of 26.58 ± 6.11 µg/mL. The aliphatic aldehydes (E)-2-decenal (7.85 ± 0.28 µg/mL), (E)-2-undecenal (2.81 ± 0.21 µg/mL), and (E)-2-dodecenal (4.35 ± 0.15 µg/mL), all isolated from C. sativum essential oil, are effective inhibitors of in vitro cultures of L. donovani promastigotes. Aldehydes (E)-2-decenal, (E)-2-undecenal, and (E)-2-dodecenal were also evaluated against axenic amastigotes and IC50 values were determined to be 2.47 ± 0.25 µg/mL, 1.25 ± 0.11 µg/mL, and 4.78 ± 1.12 µg/mL, respectively. (E)-2-Undecenal and (E)-2-dodecenal demonstrated IC50 values of 5.65 ± 0.19 µg/mL and 9.60 ± 0.89 µg/mL, respectively, against macrophage amastigotes. These cilantro compounds showed no cytotoxicity against THP-1 macrophages.

  11. Secondary aerosol formation from atmospheric reactions of aliphatic amines

    Directory of Open Access Journals (Sweden)

    S. M. Murphy

    2007-01-01

    Full Text Available Although aliphatic amines have been detected in both urban and rural atmospheric aerosols, little is known about the chemistry leading to particle formation or the potential aerosol yields from reactions of gas-phase amines. We present here the first systematic study of aerosol formation from the atmospheric reactions of amines. Based on laboratory chamber experiments and theoretical calculations, we evaluate aerosol formation from reaction of OH, ozone, and nitric acid with trimethylamine, methylamine, triethylamine, diethylamine, ethylamine, and ethanolamine. Entropies of formation for alkylammonium nitrate salts are estimated by molecular dynamics calculations enabling us to estimate equilibrium constants for the reactions of amines with nitric acid. Though subject to significant uncertainty, the calculated dissociation equilibrium constant for diethylammonium nitrate is found to be sufficiently small to allow for its atmospheric formation, even in the presence of ammonia which competes for available nitric acid. Experimental chamber studies indicate that the dissociation equilibrium constant for triethylammonium nitrate is of the same order of magnitude as that for ammonium nitrate. All amines studied form aerosol when photooxidized in the presence of NOx with the majority of the aerosol mass present at the peak of aerosol growth consisting of aminium (R3NH+ nitrate salts, which repartition back to the gas phase as the parent amine is consumed. Only the two tertiary amines studied, trimethylamine and triethylamine, are found to form significant non-salt organic aerosol when oxidized by OH or ozone; calculated organic mass yields for the experiments conducted are similar for ozonolysis (15% and 5% respectively and photooxidation (23% and 8% respectively. The non-salt organic aerosol formed appears to be more stable than the nitrate salts and does not quickly repartition back to the gas phase.

  12. Secondary aerosol formation from atmospheric reactions of aliphatic amines

    Directory of Open Access Journals (Sweden)

    S. M. Murphy

    2007-01-01

    Full Text Available Although aliphatic amines have been detected in both urban and rural atmospheric aerosols, little is known about the chemistry leading to particle formation or the potential aerosol yields from reactions of gas-phase amines. We present here the first systematic study of aerosol formation from the atmospheric reactions of amines. Based on laboratory chamber experiments and theoretical calculations, we evaluate aerosol formation from reaction of OH, ozone, and nitric acid with trimethylamine, methylamine, triethylamine, diethylamine, ethylamine, and ethanolamine. Entropies of formation for alkylammonium nitrate salts are estimated by molecular dynamics calculations enabling us to estimate equilibrium constants for the reactions of amines with nitric acid. Though subject to significant uncertainty, the calculated dissociation equilibrium constant for diethylammonium nitrate is found to be sufficiently small to allow for its atmospheric formation, even in the presence of ammonia which competes for available nitric acid. Experimental chamber studies indicate that the dissociation equilibrium constant for triethylammonium nitrate is of the same order of magnitude as that for ammonium nitrate. All amines studied form aerosol when photooxidized in the presence of NOx with the majority of the aerosol mass present at the peak of aerosol growth consisting of aminium (R3NH+ nitrate salts, which repartition back to the gas phase as the parent amine is consumed. Only the two tertiary amines studied, trimethylamine and triethylamine, are found to form significant non-salt organic aerosol when oxidized by OH or ozone; calculated organic mass yields for the experiments conducted are similar for ozonolysis (15% and 5% respectively and photooxidation (23% and 8% respectively. The non-salt organic aerosol formed appears to be more stable than the nitrate salts and does not quickly repartition back to the gas phase.

  13. Interaction of gaseous aromatic and aliphatic compounds in thermophilic biofilters.

    Science.gov (United States)

    Hu, Qing-yuan; Wang, Can

    2015-12-30

    Two thermophilic biofilters were applied in treating a mixture of gaseous aromatic (benzene) and aliphatic compounds (hexane) to evaluate the interaction of the compounds. The performance of the biofilters was investigated in terms of removal efficiencies, elimination capacity, kinetic analysis, interaction indices, and microbial metabolic characteristics. Results showed that the removal performance of benzene was unaffected by the addition of hexane. The removal efficiencies of benzene were maintained at approximately 80% and the biodegradation rate constant was maintained at 120 h(-1). However, the removal efficiencies of hexane decreased significantly from 60% to 20% and the biodegradation rate constant exhibited a distinct decrease from 93.59 h(-1) to 56.32 h(-1). The interaction index of benzene with the addition of hexane was -0.029, which indicated that hexane had little effect on the degradation of benzene. By contrast, the interaction index of hexane by benzene was -0.557, which showed that benzene inhibited the degradation of hexane significantly. Similar conclusions were obtained about the substrate utilization. Moreover, the utilization degree of carbon sources and the microbial metabolic activities in the biofilter treating hexane were significantly improved with the addition of benzene, whereas the addition of hexane had a slight effect on the microbial communities in the biofilter treating benzene. Conclusions could be obtained that when mixtures of benzene and hexane were treated using biofilters, the degradation of benzene, which was more easily degradable, was dominant and unaffected; whereas the degradation of hexane, which was less easily degradable, was inhibited because of the changing of microbes.

  14. Acid-base thermochemistry of gaseous aliphatic α-aminoacids.

    Science.gov (United States)

    Bouchoux, Guy; Huang, Sihua; Inda, Bhawani Singh

    2011-01-14

    Acid-base thermochemistry of isolated aliphatic amino acids (denoted AAA): glycine, alanine, valine, leucine, isoleucine and proline has been examined theoretically by quantum chemical computations at the G3MP2B3 level. Conformational analysis on neutral, protonated and deprotonated species has been used to identify the lowest energy conformers and to estimate the population of conformers expected to be present at thermal equilibrium at 298 K. Comparison of the G3MP2B3 theoretical proton affinities, PA, and ΔH(acid) with experimental results is shown to be correct if experimental thermochemistry is re-evaluated and adapted to the most recent acidity-basicity scales. From this point of view, a set of evaluated proton affinities of 887, 902, 915, 916, 919 and 941 kJ mol(-1), and a set of evaluated ΔH(acid) of 1433, 1430, 1423, 1423, 1422 and 1426 kJ mol(-1), is proposed for glycine, alanine, valine, leucine, isoleucine and proline, respectively. Correlations with structural parameters (Taft's σ(α) polarizability parameter and molecular size) suggest that polarizability of the side chain is the major origin of the increase in PA and decrease in ΔH(acid) along the homologous series glycine, alanine, valine and leucine/isoleucine. Heats of formation of gaseous species AAA, AAAH(+) and [AAA-H](-) were computed at the G3MP2B3 level. The present study provides previously unavailable Δ(f)H°(298) for the ionized species AAAH(+) and [AAA-H](-). Comparison with Benson's estimate, and correlation with molecular size, show that several experimental Δ(f)H°(298) values of neutral or gaseous AAA might be erroneous.

  15. Vibrational and photoionization spectroscopy of biomolecules: aliphatic amino acid structures.

    Science.gov (United States)

    Hu, Yongjun; Bernstein, Elliot R

    2008-04-28

    The aliphatic amino acids glycine, valine, leucine, and isoleucine are thermally placed into the gas phase and expanded into a vacuum system for access by time of flight mass spectroscopy and infrared (IR) spectroscopy in the energy range of 2500-4000 cm(-1) (CH, NH, OH, and stretching vibrations). The isolated neutral amino acids are ionized by a single photon of 10.5 eV energy (118 nm), which exceeds by less than 2 eV their reported ionization thresholds. As has been reported for many hydrogen bonded acid-base systems (e.g., water, ammonia, alcohol, acid clusters, and acid molecules), the amino acids undergo a structural rearrangement in the ion state (e.g., in simplest form, a proton transfer) that imparts sufficient excess vibrational energy to the ion to completely fragment it. No parent ions are observed. If the neutral ground state amino acids are exposed to IR radiation prior to ionization, an IR spectrum of the individual isomers for each amino acid can be determined by observation of the ion intensity of the different fragment mass channels. Both the IR spectrum and fragmentation patterns for individual isomers can be qualitatively identified and related to a particular isomer in each instance. Thus, each fragment ion detected presents an IR spectrum of its particular parent amino acid isomer. In some instances, the absorption of IR radiation by the neutral amino acid parent isomer increases a particular fragmentation mass channel intensity, while other fragmentation mass channel intensities decrease. This phenomenon can be rationalized by considering that with added energy in the molecule, the fragmentation channel populations can be modulated by the added vibrational energy in the rearranged ions. This observation also suggests that the IR absorption does not induce isomerization in the ground electronic state of these amino acids. These data are consistent with theoretical predictions for isolated amino acid secondary structures and can be related to

  16. Glucose-responsive insulin activity by covalent modification with aliphatic phenylboronic acid conjugates.

    Science.gov (United States)

    Chou, Danny Hung-Chieh; Webber, Matthew J; Tang, Benjamin C; Lin, Amy B; Thapa, Lavanya S; Deng, David; Truong, Jonathan V; Cortinas, Abel B; Langer, Robert; Anderson, Daniel G

    2015-02-24

    Since its discovery and isolation, exogenous insulin has dramatically changed the outlook for patients with diabetes. However, even when patients strictly follow an insulin regimen, serious complications can result as patients experience both hyperglycemic and hypoglycemic states. Several chemically or genetically modified insulins have been developed that tune the pharmacokinetics of insulin activity for personalized therapy. Here, we demonstrate a strategy for the chemical modification of insulin intended to promote both long-lasting and glucose-responsive activity through the incorporation of an aliphatic domain to facilitate hydrophobic interactions, as well as a phenylboronic acid for glucose sensing. These synthetic insulin derivatives enable rapid reversal of blood glucose in a diabetic mouse model following glucose challenge, with some derivatives responding to repeated glucose challenges over a 13-h period. The best-performing insulin derivative provides glucose control that is superior to native insulin, with responsiveness to glucose challenge improved over a clinically used long-acting insulin derivative. Moreover, continuous glucose monitoring reveals responsiveness matching that of a healthy pancreas. This synthetic approach to insulin modification could afford both long-term and glucose-mediated insulin activity, thereby reducing the number of administrations and improving the fidelity of glycemic control for insulin therapy. The described work is to our knowledge the first demonstration of a glucose-binding modified insulin molecule with glucose-responsive activity verified in vivo.

  17. "Green" functionalization of pristine multi-walled carbon nanotubes with long-chain aliphatic amines.

    Science.gov (United States)

    Basiuk, Elena V; Ochoa-Olmos, Omar; Contreras-Torres, Flavio F; Meza-Laguna, Víctor; Alvarez-Zauco, Edgar; Puente-Lee, Iván; Basiuk, Vladimir A

    2011-06-01

    Short pristine multi-walled carbon nanotubes (MWNTs) were functionalized with a series of long-chain (including polymeric) aliphatic amines, namely octadecylamine (ODA), 1,8-diaminooctane (DO), polyethylene glycol diamine (PEGDA) and polyethylenimine (PEI), via two "green" approaches: (1) gas-phase functionalization (for volatile ODA and DO) and (2) direct heating in the melt (for polymeric PEGDA and PEI). Both of them consist in one-step reaction between MWNTs and amine without the use of organic solvents. The nanostructures obtained were characterized by using infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, atomic force microscopy, and transmission electron microscopy. It was observed that both solvent-free methods were efficient in the nanotube functionalization, and the nanostructures of variable solubility and morphology were obtained depending on the amines attached. ODA, PEGDA and PEI-functionalized MWNTs were found to be soluble in propanol, meanwhile the MWNTs-PEGDA and MWNTs-PEI were soluble in water as well. The attachment of 1,8-diaminooctane onto MWNTs resulted in cross-linked stable nanostructure.

  18. Tuning Oleophobicity of Silicon Oxide Surfaces with Mixed Monolayers of Aliphatic and Fluorinated Alcohols.

    Science.gov (United States)

    Lee, Austin W H; Gates, Byron D

    2016-12-13

    We demonstrate the formation of mixed monolayers derived from a microwave-assisted reaction of alcohols with silicon oxide surfaces in order to tune their surface oleophobicity. This simple, rapid method provides an opportunity to precisely tune the constituents of the monolayers. As a demonstration, we sought fluorinated alcohols and aliphatic alcohols as reagents to form monolayers from two distinct constituents for tuning the surface oleophobicity. The first aspect of this study sought to identify a fluorinated alcohol that formed monolayers with a relatively high surface coverage. It was determined that 1H,1H,2H,2H-perfluoro-1-octanol yielded high quality monolayers with a water contact angle (WCA) value of ∼110° and contact angle values of ∼80° with toluene and hexadecane exhibiting both an excellent hydrophobicity and oleophobicity. Tuning of the oleophobicity of the modified silicon oxide surfaces was achieved by controlling the molar ratio of 1H,1H,2H,2H-perfluoro-1-octanol within the reaction mixtures. Surface oleophobicity progressively decreased with a decrease in the fluorinated alcohol content while the monolayers maintained their hydrophobicity with WCA values of ∼110°. The simple and reliable approach to preparing monolayers of a tuned composition that is described in this article can be utilized to control the fluorocarbon content of the hydrophobic monolayers on silicon oxide surfaces.

  19. Separation and conductimetric detection of C1-C7 aliphatic monocarboxylic acids and C1-C7 aliphatic monoamines on unfunctionized polymethacrylate resin columns.

    Science.gov (United States)

    Ohta, Kazutoku; Towata, Atsuya; Ohashi, Masayoshi; Takeuchi, Toyohide

    2004-06-11

    The application of unfunctionized polymethacrylate resin (TSKgel G3000PWXL) as a stationary phase in liquid chromatography with conductimetric detection for C1-C7 aliphatic monocarboxylic acids (formic acid, acetic acid, propionic acid, butyric acid, isovaleric acid, valeric acid, 3,3-dimethylbutyric acid, 4-methylvaleric acid, hexanoic acid, 2-methylhexanoic acid, 5-methylhexanoic acid and heptanoic acid) and C1-C7 aliphatic monoamines (methylamine, ethylamine, propylamine, isobutylamine, butylamine, isoamylamine, amylamine, 1,3-dimethylbutylamine, hexylamine, 2-heptylamine and heptylamine) was attempted with C8 aliphatic monocarboxylic acids (2-propylvaleric acid, 2-ethylhexanoic acid, 2-methylheptanoic acid and octanoic acid) and C8 aliphatic monoamines (1,5-dimethylhexylamine, 2-ethylhexylamine, 1-methylheptylamine and octylamine) as eluents, respectively. Using 1 mM 2-methylheptanoic acid at pH 4.0 as the eluent, excellent separation and relatively high sensitive detection for these C1-C7 carboxylic acids were achieved on a TSKgel G3000PWXL column (150 mm x 6 mm i.d.) in 60 min. Using 2 mM octylamine at pH 11.0 as the eluent, excellent separation and relatively high sensitive detection for these C1-C7 amines were also achieved on the TSKgel G3000PWXL column in 60 min.

  20. Simultaneous and sensitive analysis of aliphatic carboxylic acids by ion-chromatography using on-line complexation with copper(II) ion.

    Science.gov (United States)

    Kemmei, Tomoko; Kodama, Shuji; Yamamoto, Atsushi; Inoue, Yoshinori; Hayakawa, Kazuichi

    2015-01-02

    A new approach to ion chromatography is proposed to improve the UV detection of aliphatic carboxylic acids separated by anion-exchange chromatography. When copper(II) ion added to the mobile phase, it forms complexes with carboxylic acids that can be detected at 240 nm. The absorbance was found to increase with increasing copper(II) ion concentration. The retention times of α-hydroxy acids were also found to depend on the copper(II) ion concentration. Addition of acetonitrile to the mobile phase improved the separation of aliphatic carboxylic acids. The detection limits of the examined carboxylic acids (formate, glycolate, acetate, lactate, propionate, 3-hydroxypropionate, n-butyrate, isobutyrate, n-valerate, isovalerate, n-caproate) calculated at S/N=3 ranged from 0.06 to 3 μM. The detector signal was linear over three orders of magnitude of carboxylic acid concentration. The proposed method was successfully applied to analyze aliphatic carboxylic acids in rainwater and bread.

  1. CZE study on adsorption processes of aliphatic and aromatic amines on PMMA chip.

    Science.gov (United States)

    Masár, Marián; Kruk, Pavol; Luc, Milan; Bodor, Róbert; Danč, Ladislav; Troška, Peter

    2013-02-01

    Adsorption processes on a PMMA chip linked with CZE separations of a group of 13 aliphatic and aromatic mono- and di-amines were studied. Due to the lack of chromophores within aliphatic amines, contact conductivity detection implemented directly onto the chip was used for monitoring of cationic CZE separations. To prevent an adsorption of studied amines to the chip channels, the surface of PMMA chip was modified by dynamic coating. Different surface modifiers, such as aliphatic oligoamines (diethylenetriamine and triethylenetetramine), were added to the BGE solutions filling the chip channels. The effect of various concentrations of surface modifiers on peak profiles and separation parameters of amines was monitored. Of these, mainly, aliphatic di-amines and aromatic mono-amines adversely affected the CZE resolution of a whole group of analytes by their strong adsorption to the chip channels. A propionate BGE with pH 3.2 containing 100 μM triethylenetetramine and 25 mM 18-crown-6-ether was found suitable for CZE resolution of 12 from a total of 13 amines studied. Simple dynamic modification of the surface of PMMA chip enabled fast (analysis time lasted 9 min), sensitive (sub-μM LODs reached) and reproducible (1-3% RSD of the peak areas) CZE analysis of the aliphatic and aromatic amines.

  2. Screening and Quantification of Aliphatic Primary Alkyl Corrosion Inhibitor Amines in Water Samples by Paper Spray Mass Spectrometry.

    Science.gov (United States)

    Jjunju, Fred P M; Maher, Simon; Damon, Deidre E; Barrett, Richard M; Syed, S U; Heeren, Ron M A; Taylor, Stephen; Badu-Tawiah, Abraham K

    2016-01-19

    Direct analysis and identification of long chain aliphatic primary diamine Duomeen O (n-oleyl-1,3-diaminopropane), corrosion inhibitor in raw water samples taken from a large medium pressure water tube boiler plant water samples at low LODs (corrosion inhibitors in an industrial water boiler plant and other related samples in the water treatment industry. This approach was applied for the analysis of three complex water samples including feedwater, condensate water, and boiler water, all collected from large medium pressure (MP) water tube boiler plants, known to be dosed with varying amounts of polyamine and amine corrosion inhibitor components. Polyamine chemistry is widely used for example in large high pressure (HP) boilers operating in municipal waste and recycling facilities to prevent corrosion of metals. The samples used in this study are from such a facility in Coventry waste treatment facility, U.K., which has 3 × 40 tonne/hour boilers operating at 17.5 bar.

  3. Aliphatic amine responsive organogel system based on a simple naphthalimide derivative.

    Science.gov (United States)

    Cao, Xinhua; Zhang, Tingting; Gao, Aiping; Li, Keli; Cheng, Qiuli; Song, Lijuan; Zhang, Min

    2014-09-07

    A new gelator 1 based on a simple naphthalimide derivative was synthesized and fully characterized. It was found that the organogel 1 was formed only in a mixed solvent of methanol and H2O (1/1, v/v). The organogel was thoroughly characterized by using various microscopic techniques including field-emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), and UV-vis, fluorescence and Fourier transform infrared (FTIR) spectroscopy. Hydrogen bonds were the main driving force for the organogel formation. Interestingly, the organogel 1 exhibited the ability to distinguish aliphatic amines from aromatic amines. The gel state and fluorescence emission intensity were both changed after two minutes after the addition of aliphatic amines. This organogel system could be applied in the detection of aliphatic amine pollutants.

  4. On the aliphatic versus aromatic content of the carriers of the `unidentified' infrared emission features

    Science.gov (United States)

    Yang, X. J.; Glaser, R.; Li, Aigen; Zhong, J. X.

    2016-10-01

    Although it is generally accepted that the unidentified infrared emission (UIE) features at 3.3, 6.2, 7.7, 8.6, and 11.3 μm are characteristic of the stretching and bending vibrations of aromatic hydrocarbon materials, the exact nature of their carriers remains unknown: whether they are free-flying, predominantly aromatic gas-phase molecules, or amorphous solids with a mixed aromatic/aliphatic composition are being debated. Recently, the 3.3 and 3.4 μm features which are commonly respectively attributed to aromatic and aliphatic C-H stretches have been used to place an upper limit of ˜2 per cent on the aliphatic fraction of the UIE carriers (i.e. the number of C atoms in aliphatic chains to that in aromatic rings). Here we further explore the aliphatic versus aromatic content of the UIE carriers by examining the ratio of the observed intensity of the 6.2 μm aromatic C-C feature (I6.2) to that of the 6.85 μm aliphatic C-H deformation feature (I6.85). To derive the intrinsic oscillator strengths of the 6.2 μm stretch (A6.2) and the 6.85 μm deformation (A6.85), we employ density functional theory to compute the vibrational spectra of seven methylated polycyclic aromatic hydrocarbon molecules and their cations. By comparing I6.85/I6.2 with A6.85/A6.2, we derive the fraction of C atoms in methyl(ene) aliphatic form to be at most ˜10 per cent, confirming the earlier finding that the UIE emitters are predominantly aromatic. We have also computed the intrinsic strength of the 7.25 μm feature (A7.25), another aliphatic C-H deformation band. We find that A6.85 appreciably exceeds A7.25. This explains why the 6.85 μm feature is more frequently detected in space than the 7.25 μm feature.

  5. ORGANIC CHEMISTRY. Catalytic asymmetric hydroamination of unactivated internal olefins to aliphatic amines.

    Science.gov (United States)

    Yang, Yang; Shi, Shi-Liang; Niu, Dawen; Liu, Peng; Buchwald, Stephen L

    2015-07-01

    Catalytic assembly of enantiopure aliphatic amines from abundant and readily available precursors has long been recognized as a paramount challenge in synthetic chemistry. Here, we describe a mild and general copper-catalyzed hydroamination that effectively converts unactivated internal olefins—an important yet unexploited class of abundant feedstock chemicals—into highly enantioenriched α-branched amines (≥96% enantiomeric excess) featuring two minimally differentiated aliphatic substituents. This method provides a powerful means to access a broad range of advanced, highly functionalized enantioenriched amines of interest in pharmaceutical research and other areas.

  6. Silver-Catalyzed Decarboxylative Radical Azidation of Aliphatic Carboxylic Acids in Aqueous Solution.

    Science.gov (United States)

    Liu, Chao; Wang, Xiaoqing; Li, Zhaodong; Cui, Lei; Li, Chaozhong

    2015-08-12

    We report herein an efficient and general method for the decarboxylative azidation of aliphatic carboxylic acids. Thus, with AgNO3 as the catalyst and K2S2O8 as the oxidant, the reactions of various aliphatic carboxylic acids with tosyl azide or pyridine-3-sulfonyl azide in aqueous CH3CN solution afforded the corresponding alkyl azides under mild conditions. A broad substrate scope and wide functional group compatibility were observed. A radical mechanism is proposed for this site-specific azidation.

  7. 40 CFR 721.10188 - Fatty acids, tall-oil, reaction products with 4-methyl-2-pentanone and aliphatic polyamine...

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fatty acids, tall-oil, reaction... Fatty acids, tall-oil, reaction products with 4-methyl-2-pentanone and aliphatic polyamine (generic). (a... generically as fatty acids, tall-oil, reaction products with 4-methyl-2-pentanone and aliphatic polyamine...

  8. 40 CFR 721.10190 - Formaldehyde, polymer with aliphatic diamine and phenol, reaction products with 4-methyl-2...

    Science.gov (United States)

    2010-07-01

    ... diamine and phenol, reaction products with 4-methyl-2-pentanone (generic). 721.10190 Section 721.10190... Formaldehyde, polymer with aliphatic diamine and phenol, reaction products with 4-methyl-2-pentanone (generic... identified generically as formaldehyde, polymer with aliphatic diamine and phenol, reaction products with...

  9. Environmentally benign synthesis of saturated and unsaturated aliphatic polyesters via enzymatic polymerization of biobased monomers derived from renewable resources

    NARCIS (Netherlands)

    Jiang, Yi; Woortman, Albert J. J.; van Ekenstein, Gert O. R. Alberda; Loos, Katja

    2015-01-01

    Aliphatic polyesters are of great interest due to their broad potential applications and sustainability. Itaconate-based aliphatic polyesters are even more appealing in biomedical and pharmaceutical fields, as they are renewable functional polymers that can be biodegradable, biocompatible, and photo

  10. Palladium-catalyzed addition of potassium aryltrifluoroborates to aliphatic nitriles: synthesis of alkyl aryl ketones, diketone compounds, and 2-arylbenzo[b]furans.

    Science.gov (United States)

    Wang, Xingyong; Liu, Miaochang; Xu, Long; Wang, Qingzong; Chen, Jiuxi; Ding, Jinchang; Wu, Huayue

    2013-06-07

    A palladium-catalyzed addition of potassium aryltrifluoroborates to aliphatic nitriles has been developed, leading to a wide range of alkyl aryl ketones with moderate to excellent yields. Moreover, several dinitriles (e.g., malononitrile, glutaronitrile, and adiponitrile) were applicable to this process for the construction of 1,3-, 1,5-, or 1,6-dicarbonyl compounds. The scope of the developed approach is successfully explored toward the one-step synthesis of 2-arylbenzo[b]furans via sequential addition and intramolecular annulation reactions. The methodology accepted a wide range of substrates and is applicable to library synthesis.

  11. Aliphatic carboxylic acids as new modifiers for separation of 2,4-dinitrophenyl amino acids by micellar liquid chromatography.

    Science.gov (United States)

    Boichenko, Alexander P; Kulikov, Artem U; Loginova, Lidia P; Iwashchenko, Anna L

    2007-07-20

    The possibilities of isocratic separation of 2,4-dinitrophenyl derivatives of 12 amino acids that considerably differ in hydrophobicity by micellar mobile phases with different organic modifiers have been discussed. For the first time aliphatic carboxylic acids have been used as modifiers of micellar eluent in micellar liquid chromatography with C18 columns. Elution strength of hybrid micellar phases on the basis of sodium dodecylsulfate and aliphatic carboxylic acids increases in sequence: aceticacid. The effect of sodium dodecylsulfate micelles on aliphatic carboxylic acids has been characterized by their micellar-induced shifts of ionization constants. The use of aliphatic carboxylic acids as modifiers of SDS micellar eluents provides better overall resolution of 2,4-dinitrophenyl-amino acids in comparison with aliphatic alcohols.

  12. A case study on the myth of emission from aliphatic amides

    Science.gov (United States)

    Singh, Avinash Kumar; Das, Sreyashi; Datta, Anindya

    2016-12-01

    For several decades, aliphatic amidic compounds have been believed to be emissive. We report that this contention is incorrect and that the anomalous emission from amides originates in fluorescent impurities generated during their synthesis. In order to make this point, we have synthesized fluorescent compounds and have compared the absorption spectra with excitation spectra.

  13. The Impact of the Absence of Aliphatic Glucosinolates on Insect Herbivory in Arabidopsis

    NARCIS (Netherlands)

    Beekwilder, J.; van Leeuwen, W.; Van Dam, N.M.; Bertossi, M.; Grandi, V.; Mizzi, L.; Soloviev, M.; Szabados, L.; Molthoff, J.W.; Schipper, B.; Verbocht, H.; de Vos, R.C.H.; Morandini, P.; Aarts, M.G.M.; Bovy, A.

    2008-01-01

    Aliphatic glucosinolates are compounds which occur in high concentrations in Arabidopsis thaliana and other Brassicaceae species. They are important for the resistance of the plant to pest insects. Previously, the biosynthesis of these compounds was shown to be regulated by transcription factors MYB

  14. Fingerprinting aliphatic hydrocarbon pollutants over agricultural lands surrounding Tehran oil refinery.

    Science.gov (United States)

    Bayat, Javad; Hashemi, Seyed Hossein; Khoshbakht, Korros; Deihimfard, Reza

    2016-11-01

    The analysis of aliphatic hydrocarbons, which are composed of n-alkanes as well as branched and cyclic alkanes, can be used to distinguish between the sources of hydrocarbon contamination. In this study, the concentration of aliphatic hydrocarbons, soil pH, and organic matter in agricultural soils located south of Tehran were monitored. Eighty-three soil samples were taken from two depth ranges of 0-30 and 30-60 cm. The results showed that aliphatic compounds ranged from 0.22-68.11 mg kg(-1) at the top to 0.33-53.18 mg kg(-1) at subsoil. The amount of hydrocarbons increases from the northern parts toward the south, and hydrocarbon pollutants originated from both petroleum and non-petroleum sources. Higher concentrations of aliphatic compounds in the southern parts indicated that, aside from the practice of irrigating with untreated wastewater, leakage from oil refinery storage tanks possibly contributed to soil pollution. The results also showed that several sources have polluted the agricultural soils. It is necessary to develop a new local pollution criterion as a diagnostic index that includes not only hydrocarbons but also other parameters such as heavy metal content in both soil and untreated wastewater, surface runoff, and other irrigation water resources to determine the exact origin of pollution.

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

    Science.gov (United States)

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

    2017-03-01

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

  16. Recovery of Aliphatic Hydrocarbons from Oil Field Sludge using Bacillus sp

    Directory of Open Access Journals (Sweden)

    Rizwan Ahmed Bhutto

    2015-04-01

    Full Text Available Bioremediation of aliphatic HC (Hydrocarbons in the oily sludge of Kunnar oil and gas field, Pakistan was attempted by means of previously isolated and developed Bacillus sp. Both autoclaved and non-autoclaved sludge samples were analyzed for a reaction time of 30 days with pH 7 and temperature of 380C in 50 ml MSM growth media for the sludge concentration of 5, 10 and 50% with 2, 4 and 6ml of Bacillus sp. relatively, in air atmosphere. Stabilization of the samples by microbial activity resulted in the decrease in TPH (Total Petroleum Hydrocarbon concentration by 60, 69 and 87% in autoclaved samples in contrast to the decrease of 70, 84 and 94% observed in non-autoclaved samples, relatively. Hydrocarbon degradation in oily sludge was investigated via GC which transpired that 97 and 99% concentration of aliphatic hydrocarbons in autoclaved and non-autoclaved samples was removed at 5% of TPH concentration, relatively. However, with 10% TPH concentration aliphatic hydrocarbons reduction was 68% in autoclaved samples to that of 87% in non-autoclaved samples. Further increase in the hydrocarbons concentration by 50% yielded in the removal of aliphatic hydrocarbons by 65% in autoclaved samples as compared to 98% decrease in non-autoclaved samples.

  17. Ruthenium/Imidazolylphosphine catalysis: hydrogenation of aliphatic and aromatic nitriles to form amines.

    Science.gov (United States)

    Werkmeister, Svenja; Junge, Kathrin; Wendt, Bianca; Spannenberg, Anke; Jiao, Haijun; Bornschein, Christoph; Beller, Matthias

    2014-04-07

    A convenient and efficient catalyst system for the hydrogenation of aliphatic nitriles towards the corresponding primary amines in high to excellent yields is presented. In addition, aromatic nitriles are reduced smoothly, too. The use of low catalyst loadings and molecular hydrogen make this protocol an attractive methodology. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. STUDY ON THE PHASE TRANSITION KINETICS OF THERMOTROPIC LIQUID CRYSTALLINE AROMATIC-ALIPHATIC COPOLYESTER

    Institute of Scientific and Technical Information of China (English)

    LI Minhui; WANG Xiaogong; LIU Deshan; ZHOU Qixiang

    1991-01-01

    The phase transition kinetics of thermotropic liquid crystalline aromatic-aliphatic regular copolyester:(X) were studied by DSC. By means of Kissinger's method the kinetic equation and parameters including activation energy, rate order and preexponential factor for phase transition from nematic to isotropic were obtained. The activation energy from crystal to nematic was also presented.

  19. Lipase-catalyzed synthesis of oligoesters of 2,5-furandicarboxylic acid with aliphatic diols

    NARCIS (Netherlands)

    Cruz-Izquierdo, Álvaro; Broek, van den Lambertus A.M.; Serra, Juan L.; Llama, María J.; Boeriu, Carmen G.

    2015-01-01

    2,5-Furandicarboxylic acid is a platform chemical for the production of biobased polymers and materials. This study reports the synthesis of furan oligoesters via polytransesterification of dimethyl furan-2,5-dicarboxylate and linear α, ω-aliphatic diols with chain length ranging from C2 to C12,

  20. Modification of eucalyptus pulp fiber using silane coupling agents with aliphatic side chains of different length

    Science.gov (United States)

    The objective of this work was to evaluate the effect of three silane coupling agents with different aliphatic chain lengths on the hydrophobicity of eucalyptus pulp fiber. The three silanes coupling agents used (isobutyltrimethoxysilane, methyltrimethoxysilane, and n-octyltriethoxysilane [OTES]) we...

  1. Lipase-catalyzed synthesis of oligoesters of 2,5-furandicarboxylic acid with aliphatic diols

    NARCIS (Netherlands)

    Cruz-Izquierdo, Álvaro; Broek, van den Lambertus A.M.; Serra, Juan L.; Llama, María J.; Boeriu, Carmen G.

    2015-01-01

    2,5-Furandicarboxylic acid is a platform chemical for the production of biobased polymers and materials. This study reports the synthesis of furan oligoesters via polytransesterification of dimethyl furan-2,5-dicarboxylate and linear α, ω-aliphatic diols with chain length ranging from C2 to C12,

  2. Phenolic and short-chained aliphatic organic acid constituents of wild oat (Avena fatua L.) seeds.

    Science.gov (United States)

    Gallagher, R S; Ananth, R; Granger, K; Bradley, B; Anderson, J V; Fuerst, E P

    2010-01-13

    The objective of this research was to identify and quantify the phenolic and short-chained aliphatic organic acids present in the seeds of three wild-type populations of wild oat and compare these results to the chemical composition of seeds from two commonly utilized wild oat isolines (M73 and SH430). Phenolic acids have been shown to serve as germination inhibitors, as well as protection for seeds from biotic and abiotic stress factors in other species, whereas aliphatic organic acids have been linked to germination traits and protection against pathogens. Wild oat populations were grown under a "common garden" environment to remove maternal variation, and the resulting seeds were extracted to remove the readily soluble and chemically bound phenolic and aliphatic organic acid components. Compounds were identified and quantified using gas chromatography-mass spectrometry. Ferulic and p-coumaric acid comprised 99% of the total phenolic acids present in the seeds, of which 91% were contained in the hulls and 98% were in the chemically bound forms. Smaller quantities of OH benzoic and vanillic acid were also detected. Soluble organic acids concentrations were higher in the M73 isoline compared to SH430, suggesting that these chemical constituents could be related to seed dormancy. Malic, succinic, fumaric and azelaic acid were the dominant aliphatic organic acids detected in all seed and chemical fractions.

  3. Palladium-catalyzed regioselective decarboxylative alkylation of arenes and heteroarenes with aliphatic carboxylic acids.

    Science.gov (United States)

    Premi, Chanchal; Dixit, Ankit; Jain, Nidhi

    2015-06-05

    An unprecedented Pd(OAc)2-catalyzed decarboxylative alkylation of unactivated arenes, with aliphatic carboxylic acids as inexpensive alkyl sources, is reported. The alkylation, controlled by the directing group, is regioselective, shows high functional group tolerance, and provides mild access to alkylated indolines, 2-phenylpyridines, and azobenzenes under solvent-free conditions in moderate to high yields.

  4. Mass spectral analysis of C3 and C4 aliphatic amino acid derivatives.

    Science.gov (United States)

    Lawless, J. G.; Chadha, M. S.

    1971-01-01

    Diagnostic criteria are obtained for the distinction of alpha, beta, gamma, and N-methyl isomers of the C3 and C4 aliphatic amino acids, using mass spectral analysis of the derivatives of these acids. The use of deuterium labeling has helped in the understanding of certain fragmentation pathways.

  5. PcMtr, an aromatic and neutral aliphatic amino acid permease of Penicillium chrysogenum

    NARCIS (Netherlands)

    Trip, H; Evers, ME; Driessen, AJM

    2004-01-01

    The gene encoding an aromatic and neutral aliphatic amino acid permease of Penicillium chrysogenum was cloned, functionally expressed and characterized in Saccharomyces cerevisiae M4276. The permease, designated PcMtr, is structurally and functionally homologous to Mtr of Neurospora crassa, and unre

  6. Selection of ionic liquids for the extraction of aromatic hydrocarbons from aromatic/aliphatic mixtures

    NARCIS (Netherlands)

    Meindersma, G. Wytze; Podt, Anita (J.G.); Haan, de André B.

    2005-01-01

    The separation of aromatic hydrocarbons (benzene, toluene, ethyl benzene and xylenes) from C4 to C10 aliphatic hydrocarbon mixtures is challenging since these hydrocarbons have boiling points in a close range and several combinations form azeotropes. In this work, we investigated the separation of t

  7. Development and application of bacterial cultures for the removal of chlorinated aliphatics

    NARCIS (Netherlands)

    Janssen, Dick B.; de Koning, Wim

    1995-01-01

    The possibility of obtaining microbial cultures for the degradation of halogenated aliphatic hydrocarbons is mainly determined by the diversity and activity of catabolic enzymes that exist in nature. If a suitable organism is available, applications for the treatment of different waste streams can

  8. Biological evaluation of porous aliphatic polyurethane/hydroxyapatite composite scaffolds for bone tissue engineering.

    NARCIS (Netherlands)

    Yang, W; Both, S.K.; Zuo, Y.; Birgani, Z.T.; Habibovic, P.; Li, Y.; Jansen, J.A.; Yang, F.

    2015-01-01

    Biomaterial scaffolds meant to function as supporting structures to osteogenic cells play a pivotal role in bone tissue engineering. Recently, we synthesized an aliphatic polyurethane (PU) scaffold via a foaming method using non-toxic components. Through this procedure a uniform interconnected porou

  9. Pseudomonas sax genes overcome aliphatic isothiocyanate-mediated non-host resistance in Arabidopsis

    Science.gov (United States)

    Jun Fan; Casey Crooks; Gary Creissen; Lionel Hill; Shirley Fairhurst; Peter Doerner; Chris Lamb

    2011-01-01

    Most plant-microbe interactions do not result in disease; natural products restrict non-host pathogens. We found that sulforaphane (4-methylsulfinylbutyl isothiocyanate), a natural product derived from aliphatic glucosinolates, inhibits growth in Arabidopsis of non-host Pseudomonas bacteria in planta. Multiple sax genes (saxCAB/F/D/G) were identified in Pseudomonas...

  10. Swift heavy ion induced modification of aliphatic polymers

    Energy Technology Data Exchange (ETDEWEB)

    Hossain, Umme Habiba

    2015-01-15

    In this thesis, the high energy heavy ion induced modification of aliphatic polymers is studied. Two polymer groups, namely polyvinyl polymers (PVF, PVAc, PVA and PMMA) and fluoropolymers (PVDF, ETFE, PFA and FEP) were used in this work. Polyvinyl polymers were investigated since they will be used as insulating materials in the superconducting magnets of the new ion accelerators of the planned International Facility for Antiproton and Ion Research (FAIR) at the GSI Helmholtz-Centre of Heavy Ion Research (GSI) in Darmstadt. In order to study ion-beam induced degradation, all polymer foils were irradiated at the GSI linear accelerator UNILAC using several projectiles (U, Au, Sm, Xe) and experimentation sites (beam lines X0 and M3) over a large fluence regime (1 x 10{sup 10} - 5 x 10{sup 12} ions/cm{sup 2}). Five independent techniques, namely infrared (FT-IR) and ultraviolet-visible (UV-Vis) spectroscopy, residual gas analysis (RGA), thermal gravimetric analysis (TGA), and mass loss analysis (ML), were used to analyze the irradiated samples. FT-IR spectroscopy revealed that ion irradiation led to the decrease of characteristic band intensities showing the general degradation of the polymers, with scission of side groups and the main backbone. As a consequence of the structural modification, new bands appeared. UV-Vis transmission analysis showed an absorption edge shift from the ultraviolet region towards the visible region indicating double bond and conjugated double bond formation. On-line massspectrometric residual gas analysis showed the release of small gaseous fragment molecules. TGA analysis gave evidence of a changed thermal stability. With ML analysis, the considerable mass loss was quantified. The results of the five complementary analytical methods show how heavy ion irradiation changes the molecular structure of the polymers. Molecular degradation mechanisms are postulated. The amount of radiation damage is found to be sensitive to the used type of ionic

  11. Scientific Opinion on Flavouring Group Evaluation 94, Revision 2 (FGE.94Rev2: Consideration of aliphatic amines and amides evaluated in an addendum to the group of aliphatic and aromatic amines and amides evaluated by the JECFA (68th meeting

    Directory of Open Access Journals (Sweden)

    EFSA Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids (CEF

    2014-04-01

    Full Text Available The Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids of the European Food Safety Authority was requested to consider evaluations of flavouring substances assessed since 2000 by the Joint FAO/WHO Expert Committee on Food Additives (the JECFA, and to decide whether further evaluation is necessary, as laid down in Commission Regulation (EC No 1565/2000. The present consideration concerns a group of 12 aliphatic amines and amides evaluated by the JECFA at the 68th meeting in 2007. This revision is required owing to additional toxicity data on 3-(3,4-dimethoxyphenyl-N-[2-(3,4-dimethoxyphenyl-ethyl]-acrylamide [FL-no: 16.090]. The substances were evaluated through a stepwise approach that integrates information on structure-activity relationships, intake from current uses, toxicological threshold of concern and available data on metabolism and toxicity. The Panel agrees with JECFA conclusion “No safety concern at estimated levels of intake as flavouring substances” based on the MSDI approach for all substances considered in this FGE. Besides the safety assessment of these flavouring substances, the specifications for the materials of commerce have been considered and for all 12 substances, the information is adequate.

  12. Estimating the octanol/water partition coefficient for aliphatic organic compounds using semi-empirical electrotopological index.

    Science.gov (United States)

    Souza, Erica Silva; Zaramello, Laize; Kuhnen, Carlos Alberto; Junkes, Berenice da Silva; Yunes, Rosendo Augusto; Heinzen, Vilma Edite Fonseca

    2011-01-01

    A new possibility for estimating the octanol/water coefficient (log P) was investigated using only one descriptor, the semi-empirical electrotopological index (I(SET)). The predictability of four octanol/water partition coefficient (log P) calculation models was compared using a set of 131 aliphatic organic compounds from five different classes. Log P values were calculated employing atomic-contribution methods, as in the Ghose/Crippen approach and its later refinement, AlogP; using fragmental methods through the ClogP method; and employing an approach considering the whole molecule using topological indices with the MlogP method. The efficiency and the applicability of the I(SET) in terms of calculating log P were demonstrated through good statistical quality (r > 0.99; s < 0.18), high internal stability and good predictive ability for an external group of compounds in the same order as the widely used models based on the fragmental method, ClogP, and the atomic contribution method, AlogP, which are among the most used methods of predicting log P.

  13. Self-assembly of short peptides composed of only aliphatic amino acids and a combination of aromatic and aliphatic amino acids.

    Science.gov (United States)

    Subbalakshmi, Chilukuri; Manorama, Sunkara V; Nagaraj, Ramakrishnan

    2012-05-01

    The morphology of structures formed by the self-assembly of short N-terminal t-butyloxycarbonyl (Boc) and C-terminal methyl ester (OMe) protected and Boc-deprotected hydrophobic peptide esters was investigated. We have observed that Boc-protected peptide esters composed of either only aliphatic hydrophobic amino acids or aliphatic hydrophobic amino acids in combination with aromatic amino acids, formed highly organized structures, when dried from methanol solutions. Transmission and scanning electron microscopic images of the peptides Boc-Ile-Ile-OMe, Boc-Phe-Phe-Phe-Ile-Ile-OMe and Boc-Trp-Ile-Ile-OMe showed nanotubular structures. Removal of the Boc group resulted in disruption of the ability to form tubular structures though spherical aggregates were formed. Both Boc-Leu-Ile-Ile-OMe and H-Leu-Ile-Ile-OMe formed only spherical nanostructures. Dynamic light scattering studies showed that aggregates of varying dimensions were present in solution suggesting that self-assembly into ordered structures is facilitated by aggregation in solution. Fourier transform infrared spectroscopy and circular dichroism spectroscopy data show that although all four of the protected peptides adopt well-defined tertiary structures, upon removal of the Boc group, only H-Phe-Phe-Phe-Ile-Ile-OMe had the ability to adopt β-structure. Our results indicate that hydrophobic interaction is a very important determinant for self-assembly and presence of charged and aromatic amino acids in a peptide is not necessary for self-assembly.

  14. Aliphatic C-H---Anion Hydrogen Bonds: Weak Contacts or Strong Interactions?

    Energy Technology Data Exchange (ETDEWEB)

    Hay, Benjamin [ORNL; Pedzisa, Lee [ORNL

    2009-01-01

    Electronic structure calculations, MP2/aug-cc-pVDZ, are used to determine C H---Cl hydrogen bond energies for a series of XCH3 donor groups in which the electron-withdrawing ability of X is varied over a wide range of values. When attached to polarizing substituents, aliphatic CH groups are moderate to strong hydrogen bond donors, exhibiting interaction energies comparable to those obtained with O H and N H groups. The results explain why aliphatic C H donors are observed to function as competitive binding sites in solution and suggest that such C H---anion contacts should be considered as possible contributors when evaluating the denticity of an anion receptor.

  15. Study on Aromatization of C6 Aliphatic Hydrocarbons on ZRP Zeolite Catalyst

    Institute of Scientific and Technical Information of China (English)

    Wang Yongjun; Xie Chaogang

    2004-01-01

    The performance of ZRP zeolite catalysts for aromatization of C6 aliphatic hydrocarbons was investigated in a pulsed microreactor. The influence of metal modified ZRP zeolites on aromatization reaction was also studied, coupled with comparison of aromatization tendencies of olefins, paraffins and paraffins with different degrees of chain branching. Test results had shown that the lower the silicon/aluminum ratio in the ZRP zeolite, the higher the aromatization reactivity of aliphatic hydrocarbons. Modification of ZRP zeolite by zinc and its zinc content had apparent impact on the yield and distribution of aromatics. The aromatization tendency of olefins was apparently better than paraffins, while the aromatization tendency of monomethyl paraffins was better than that of straight-chain paraffins with the exception of dimethyl paraffins, which had worse aromatization tendency because of their steric hindrance.

  16. Biodegradation of aliphatic hydrocarbons in the presence of hydroxy cucurbit[6]uril.

    Science.gov (United States)

    Pasumarthi, Rajesh; Kumar, Vikash; Chandrasekharan, Sivaraman; Ganguly, Anasuya; Banerjee, Mainak; Mutnuri, Srikanth

    2014-11-15

    Aliphatic hydrocarbons are one of the major environmental pollutants with reduced bioavailability. The present study focuses on the effect of hydroxy cucurbit[6]uril on the bioavailability of hydrocarbons. A bacterial consortium was used for biodegradation studies under saline and non-saline conditions. Based on denaturing gradient gel electrophoresis results it was found that the consortium under saline conditions had two different strains. The experiment was conducted in microcosms with tetradecane, hexadecane, octadecane and mixture of the mentioned hydrocarbons as the sole carbon source. The residual hydrocarbon was quantified using gas chromatography every 24h. It was found that biodegradation of tetradecane and hexadecane, as individual carbon source increased in the presence of hydroxy CB[6], probably due to the increase in their bioavailability. In case of octadecane this did not happen. Bioavailability of all three aliphatic hydrocarbons was increased when provided as a mixture to the consortium under saline conditions.

  17. A study of aliphatic amino acids using simulated vibrational circular dichroism and Raman optical activity spectra

    CERN Document Server

    Ganesan, Aravindhan; Wang, Feng

    2013-01-01

    Vibrational optical activity (VOA) spectra, such as vibrational circular dichroism (VCD) and Raman optical activity (ROA) spectra, of aliphatic amino acids are simulated using density functional theory (DFT) methods in both gas phase (neutral form) and solution (zwitterionic form), together with their respective infrared (IR) and Raman spectra of the amino acids. The DFT models, which are validated by excellent agreements with the available experimental Raman and ROA spectra of alanine in solution, are employed to study other aliphatic amino acids. The inferred (IR) intensive region (below 2000 cm-1) reveals the signature of alkyl side chains, whereas the Raman intensive region (above 3000 cm-1) contains the information of the functional groups in the amino acids. Furthermore, the chiral carbons of the amino acids (except for glycine) dominate the VCD and ROA spectra in the gas phase, but the methyl group vibrations produce stronger VCD and ROA signals in solution. The C-H related asymmetric vibrations domina...

  18. Synthetic resveratrol aliphatic acid inhibits TLR2-mediated apoptosis and an involvement of Akt/GSK3beta pathway.

    Science.gov (United States)

    Chen, Lin; Zhang, Yi; Sun, Xiuli; Li, Hui; LeSage, Gene; Javer, Avani; Zhang, Xiumei; Wei, Xinbing; Jiang, Yulin; Yin, Deling

    2009-07-01

    As resveratrol derivatives, resveratrol aliphatic acids were synthesized in our laboratory. Previously, we reported the improved pharmaceutical properties of the compounds compared to resveratrol, including better solubility in water and much tighter binding with human serum albumin. Here, we investigate the role of resveratrol aliphatic acids in Toll-like receptor 2 (TLR2)-mediated apoptosis. We showed that resveratrol aliphatic acid (R6A) significantly inhibits the expression of TLR2. In addition, overexpression of TLR2 in HEK293 cells caused a significant decrease in apoptosis after R6A treatment. Moreover, inhibition of TLR2 by R6A decreases serum deprivation-reduced the levels of phosphorylated Akt and phosphorylated glycogen synthase kinase 3beta (GSK3beta). Our study thus demonstrates that the resveratrol aliphatic acid inhibits cell apoptosis through TLR2 by the involvement of Akt/GSK3beta pathway.

  19. Anomalous Energy Effects in some Aliphatic and Alicyclic Aza Systems and their Nitro Derivatives

    Science.gov (United States)

    1990-03-01

    AUJTHOR(a) 8. CONTRACT OR GRANT NUMBER(-) Jane S. Murray, Paul C. Redfern, Jorge M. Seminario and Peter Politzer N00014-85-K-0217 It) .PERFORMING...Anomalous Energy Effects in Some Aliphatic and Alicyclic Aza Systems and Their Nitro Derivatives Jane S. Murray, Paul C. Redfern, Jorge M. Seminario , and...3801. (25) Politzer. P.: Jayasuriya, K.; Zilles, B. A. J. Am. Chem. Soc. 1985, (20) Murray, J. S.; Seminario . J. M.; Politzer, P. Unpublished work

  20. Coefficients of caffeine distribution in aliphatic alcohol-ammonium sulfate-water systems

    Science.gov (United States)

    Korenman, Ya. I.; Krivosheeva, O. A.; Mokshina, N. Ya.

    2012-11-01

    The extraction of caffeine with aliphatic alcohols C3-C9 from aqueous solutions in the presence of a salting-out agent (ammonium sulfate) is studied. Quantitative characteristics of extraction are calculated: the distribution coefficients ( D) and the degree of recovery ( R, %). Relations are found between log D of caffeine and the length of the hydrocarbon radical in the alcohol molecule, along with certain physicochemical properties of the extragents.

  1. Synthesis and antiproliferative activity of aromatic and aliphatic bis[aminomethylidene(bisphosphonic)] acids.

    Science.gov (United States)

    Goldeman, Waldemar; Nasulewicz-Goldeman, Anna

    2014-08-01

    A series of aromatic and aliphatic bis[aminomethylidene(bisphosphonic)] acids was synthesized in the reaction of triethylphosphite with isonitriles followed by hydrolysis or dealkylation. The in vitro anti-proliferative effect of all synthesized tetraphosphonic acids against MCF-7 breast cancer cells, J774E macrophages and HL-60 promyelocytic leukemia cells was determined. Three aromatic derivatives (5a, 5f and 5j) showed a similar or higher anti-proliferative activity than zoledronic acid.

  2. PcMtr, an aromatic and neutral aliphatic amino acid permease of Penicillium chrysogenum

    OpenAIRE

    Trip, H; EVERS, ME; Driessen, AJM

    2004-01-01

    The gene encoding an aromatic and neutral aliphatic amino acid permease of Penicillium chrysogenum was cloned, functionally expressed and characterized in Saccharomyces cerevisiae M4276. The permease, designated PcMtr, is structurally and functionally homologous to Mtr of Neurospora crassa, and unrelated to the Amino Acid Permease (AAP) family which includes most amino acid permeases in fungi. Database searches of completed fungal genome sequences reveal that Mtr type permeases are not widely...

  3. Modification of nano-sized layered double hydroxides by long-chain organic aliphatic surfactants

    OpenAIRE

    RAMASAMY ANBARASAN; SEUNG SOON IM; WANDUC LEE

    2008-01-01

    The inter-layer anion of layered double hydroxides (LDH) with a hydrotalcite (HT)-like structure was ion-exchanged with various organic surfactants, particularly with long chain aliphatic surfactants. After the ion-exchange process, the basal spacing of the LDH was increased and the increase of the basal spacing depended on various factors, such as the intercalation capacity functionality and orientation capability of the surfactant. Of the employed surfactants, stearic acid intercalated LDH ...

  4. Aliphatic, cyclic, and aromatic organic acids, vitamins, and carbohydrates in soil: a review.

    Science.gov (United States)

    Vranova, Valerie; Rejsek, Klement; Formanek, Pavel

    2013-11-10

    Organic acids, vitamins, and carbohydrates represent important organic compounds in soil. Aliphatic, cyclic, and aromatic organic acids play important roles in rhizosphere ecology, pedogenesis, food-web interactions, and decontamination of sites polluted by heavy metals and organic pollutants. Carbohydrates in soils can be used to estimate changes of soil organic matter due to management practices, whereas vitamins may play an important role in soil biological and biochemical processes. The aim of this work is to review current knowledge on aliphatic, cyclic, and aromatic organic acids, vitamins, and carbohydrates in soil and to identify directions for future research. Assessments of organic acids (aliphatic, cyclic, and aromatic) and carbohydrates, including their behaviour, have been reported in many works. However, knowledge on the occurrence and behaviour of D-enantiomers of organic acids, which may be abundant in soil, is currently lacking. Also, identification of the impact and mechanisms of environmental factors, such as soil water content, on carbohydrate status within soil organic matter remains to be determined. Finally, the occurrence of vitamins in soil and their role in biological and biochemical soil processes represent an important direction for future research.

  5. Tapetum Degeneration Retardation is Critical for Aliphatic Metabolism and Gene Regulation during Rice Pollen Development

    Institute of Scientific and Technical Information of China (English)

    Da-Sheng Zhang; Wan-Qi Liang; Zheng Yuan; Na Li; Jing Shi; Jue Wang; Yu-Min Liu; Wen-Juan Yu; Da-Bing Zhang

    2008-01-01

    As a complex wall system in flowering plants,the pollen outer wall mainly contains aliphatic sporopollenin;however,the mechanism for synthesizing these lipidic precursors during pollen development remains less well under-stood.Here,we report on the function of the rice tapetum-expressing TDR(Tapetum Degeneration Retardation)gene in aliphatic metabolism and its regulatory role during rice pollen development.The observations of transmission electron microscopy (TEM) and scanning electron microscopy(SEM)analyses suggested that pollen wall formation was significantly altered in the tdr mutant.The contents of aliphatic compositions of anther were greatly changed in the tdr mutant revealed by GC-MS(gas chromatography-mass spectrometry)testing,particularly less accumulated in fatty acids, primary alcohols,alkanes and alkenes,and an abnormal increase in secondary alcohols with carbon Iengths from C29 to C35 in tdr.Microarray data revealed that a group of genes putatively involved in lipid transport and metabolism were significantly altered in the tdr mutant,indicating the critical role of TDR in the formation of the pollen wall.Also,a wide range of genes tween wild-type and tdr.In addition to its function in promoting tapetum PCD,TDR possibly plays crucial regulatory roles in several basic biological processes during rice pollen development.

  6. The influence of chemical composition of aliphatic-aromatic copolyesters on their properties

    Energy Technology Data Exchange (ETDEWEB)

    Wojtczak, Malgorzata; Galeski, Andrzej; Piorkowska, Ewa [Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Lodz (Poland); Dutkiewicz, Slawomir [Institute of Biopolymers and Chemical Fibres, Marii Sklodowskiej-Curie 19/27, 90-570 Lodz (Poland)

    2014-05-15

    The chain microstructure and properties of a series of aliphatic-aromatic copolyesters in a range of compositions from 10 to 100% of aromatic components were studied by examining melting and crystallization behaviors, dynamic mechanical response, morphology, wide- (WAXS) and small-angle X-ray scattering (SAXS), and tensile deformation. Chain microstructure was analyzed by {sup 1}H NMR. The results indicate that most of copolyesters used in this study have essentially random distribution of comonomers. Copolyesters with more than 30 mol% of aromatic part crystallize with a crystal structure characteristic for homopolymer poly(butylene terephthalate) (PBT). However, some of the reflections from crystal planes are shifted towards lower diffraction angles as compared to butylene terephthalate homoplymer. The phase transition temperatures decrease with increasing aliphatic content. By means of polarized light microscopy (PLM), small-angle light scattering (SALS) and SAXS, crystallization behavior of a selected aliphatic-aromatic copolyester was further explored. Selected copolyester crystallizes in the form of thin fibrous crystals, few nanometers thick, which is the main factor influencing the depression of its melting temperature.

  7. A comprehensive evaluation of the toxicology of cigarette ingredients: aliphatic carbonyl compounds.

    Science.gov (United States)

    Coggins, Christopher R E; Jerome, Ann M; Edmiston, Jeffery S; Oldham, Michael J

    2011-06-01

    Aliphatic carbonyl compounds are used as ingredients in cigarette tobacco or cigarette filters. A battery of tests was used to compare toxicity of mainstream smoke from experimental cigarettes containing 15 aliphatic carbonyl compounds that were added individually to experimental cigarettes at three different levels. Smoke from experimental and control cigarettes were evaluated using analytical chemistry, in vitro cytotoxicity (neutral red uptake), and mutagenicity (five bacterial strains) studies. For one compound, glycerol triacetate (GTA), two 90-day inhalation studies were also performed, using different inclusion levels into either tobacco or cigarette filter. Several smoke constituent concentrations were reduced with the highest inclusion level of GTA in tobacco; incorporation of GTA into the filter, and the other compounds into tobacco, produced effectively no changes. Cytotoxicity was reduced by the highest inclusion of GTA into tobacco for both gas-vapor and particulate phases of smoke; incorporation of GTA into the filter, and the other compounds into tobacco, showed no changes. Mutagenicity was reduced by the middle and high inclusion levels of GTA into tobacco (TA1537 strain with S9); incorporation of GTA into the filter, and the other compounds into tobacco, showed no changes. Inclusion of GTA in tobacco at 100,000 ppm reduced the biological effects of the smoke in the various test systems reported in this study, although inclusion into the filter did not appear to have any major effect on the endpoints studied. The other 14 aliphatic carbonyl compounds that were tested lacked a toxicological response.

  8. A comprehensive evaluation of the toxicology of cigarette ingredients: aromatic and aliphatic alcohol compounds.

    Science.gov (United States)

    Coggins, Christopher R E; Frost-Pineda, Kimberly; Smith, Donna C; Oldham, Michael J

    2011-06-01

    Various aromatic and aliphatic alcohol compounds are found in tobacco and tobacco smoke. A battery of tests was used to compare the toxicity of mainstream smoke from experimental cigarettes containing eight aromatic and aliphatic alcohol compounds that were added individually to experimental cigarettes at three different levels. The lowest target inclusion level was 100 ppm and the highest level was 24,400 ppm. Mainstream smoke from each of the cigarette types was evaluated using analytical chemistry and assays to measure in vitro cytotoxicity (neutral red uptake) and Salmonella (five strains) mutagenicity. For three of the compounds (benzyl alcohol, propyl paraben, and rum flavor), 90-day smoke inhalation studies with 6-week recovery periods were also performed using rats. Inclusion of eugenol produced several dose-related reductions in concentrations of selected smoke constituents. Cytotoxicity and mutagenicity were unaffected by any of the test ingredients, except for dose-related reductions in cytotoxicity of the gas vapor phase produced by the inclusion of eugenol. The three smoke inhalation studies showed a few sporadic differences between the groups and there were no differences in the patterns of recovery for any of the ingredients. Despite using exaggerated inclusion levels of the eight aliphatic and aromatic alcohol compounds in experimental cigarettes, there was minimal toxicological response, which is consistent with published reports of studies using mixtures of compounds added to tobacco.

  9. Enzymatic degradation of aliphatic nitriles by Rhodococcus rhodochrous BX2, a versatile nitrile-degrading bacterium.

    Science.gov (United States)

    Fang, Shumei; An, Xuejiao; Liu, Hongyuan; Cheng, Yi; Hou, Ning; Feng, Lu; Huang, Xinning; Li, Chunyan

    2015-06-01

    Nitriles are common environmental pollutants, and their removal has attracted increasing attention. Microbial degradation is considered to be the most acceptable method for removal. In this work, we investigated the biodegradation of three aliphatic nitriles (acetonitrile, acrylonitrile and crotononitrile) by Rhodococcus rhodochrous BX2 and the expression of their corresponding metabolic enzymes. This organism can utilize all three aliphatic nitriles as sole carbon and nitrogen sources, resulting in the complete degradation of these compounds. The degradation kinetics were described using a first-order model. The degradation efficiency was ranked according to t1/2 as follows: acetonitrile>trans-crotononitrile>acrylonitrile>cis-crotononitrile. Only ammonia accumulated following the three nitriles degradation, while amides and carboxylic acids were transient and disappeared by the end of the assay. mRNA expression and enzyme activity indicated that the tested aliphatic nitriles were degraded via both the inducible NHase/amidase and the constitutive nitrilase pathways, with the former most likely preferred. Copyright © 2015 Elsevier Ltd. All rights reserved.

  10. Mechanisms and modeling of halogenated aliphatic contaminant adsorption by carbon nanotubes.

    Science.gov (United States)

    Apul, Onur Guven; Zhou, Yang; Karanfil, Tanju

    2015-09-15

    This paper examines the adsorption of environmentally relevant halogenated aliphatic compounds using single-walled (SWCNT) and multi-walled carbon nanotubes (MWCNT), and the development of linear solvation-energy relationships (LSER) to examine those adsorption mechanisms. The poly-parameter LSER model was also compared to those previously generated for the adsorption of aromatic compounds by CNTs. The adsorption affinity of aliphatic compounds was greater on the SWCNT than MWCNT with similar oxygen contents. This was attributed to the pore-filling mechanism that was enhanced by higher micropore volume of the SWCNT bundles over the MWCNT bundles. LSER models showed that, at higher concentrations, B (the hydrogen bond accepting ability) was the most influential descriptor for both SWCNT and MWCNT. Other important descriptors were V followed by P, both of which exhibited a positive correlation with adsorption, indicating that their size and polarizability favors adsorption. The contribution of these descriptors to overall adsorption was 2-3 times less than the B. In comparison, V was the most important descriptor in the aromatic compound LSER models. This difference indicates that adsorbate hydrophobicity greatly affects the adsorption of aromatic compounds by CNTs, whereas, aliphatic compounds are affected by both the hydrophobic driving force and other interactions. Copyright © 2015 Elsevier B.V. All rights reserved.

  11. Bioluminescence inhibition of bacterial luciferase by aliphatic alcohol, amine and carboxylic acid: inhibition potency and mechanism.

    Science.gov (United States)

    Yamasaki, Shinya; Yamada, Shuto; Takehara, Kô

    2013-01-01

    The inhibitory effects of hydrophobic molecules on the bacterial luciferase, BL, luminescence reaction were analyzed using an electrochemically-controlled BL luminescence system. The inhibition potency of alkyl amines, C(n)NH(2), and fatty acids, C(m)COOH (m = n - 1), on the BL reaction increased with an increase in the alkyl chain-length of these aliphatic compounds. C(m)COOH showed lower inhibition potency than C(n)NH(2) and alkyl alcohols, C(n)OH, data for which have been previously reported. To make clear the inhibition mechanisms of the aliphatic compounds on the BL reaction, the initial rate of the BL reaction was measured and analyzed using the Dixon plot and Cornish-Bowden plot. The C(12)OH inhibited the BL reaction in competition with the substrate C(11)CHO, while C(12)NH(2) and C(11)COOH inhibited in an uncompetitive manner with the C(11)CHO. These results suggest that the alkyl chain-length and the terminal unit of the aliphatic compound determine the inhibition potency and the inhibition mechanism, respectively.

  12. Kinetics of aerobic cometabolic biodegradation of chlorinated and brominated aliphatic hydrocarbons: A review.

    Science.gov (United States)

    Jesus, João; Frascari, Dario; Pozdniakova, Tatiana; Danko, Anthony S

    2016-05-15

    This review analyses kinetic studies of aerobic cometabolism (AC) of halogenated aliphatic hydrocarbons (HAHs) from 2001-2015 in order to (i) compare the different kinetic models proposed, (ii) analyse the estimated model parameters with a focus on novel HAHs and the identification of general trends, and (iii) identify further research needs. The results of this analysis show that aerobic cometabolism can degrade a wide range of HAHs, including HAHs that were not previously tested such as chlorinated propanes, highly chlorinated ethanes and brominated methanes and ethanes. The degree of chlorine mineralization was very high for the chlorinated HAHs. Bromine mineralization was not determined for studies with brominated aliphatics. The examined research period led to the identification of novel growth substrates of potentially high interest. Decreasing performance of aerobic cometabolism were found with increasing chlorination, indicating the high potential of aerobic cometabolism in the presence of medium- and low-halogenated HAHs. Further research is needed for the AC of brominated aliphatic hydrocarbons, the potential for biofilm aerobic cometabolism processes, HAH-HAH mutual inhibition and the identification of the enzymes responsible for each aerobic cometabolism process. Lastly, some indications for a possible standardization of future kinetic studies of HAH aerobic cometabolism are provided.

  13. Exploring mild enzymatic sustainable routes for the synthesis of bio-degradable aromatic-aliphatic oligoesters.

    Science.gov (United States)

    Pellis, Alessandro; Guarneri, Alice; Brandauer, Martin; Acero, Enrique Herrero; Peerlings, Henricus; Gardossi, Lucia; Guebitz, Georg M

    2016-05-01

    The application of Candida antarctica lipase B in enzyme-catalyzed synthesis of aromatic-aliphatic oligoesters is here reported. The aim of the present study is to systematically investigate the most favorable conditions for the enzyme catalyzed synthesis of aromatic-aliphatic oligomers using commercially available monomers. Reaction conditions and enzyme selectivity for polymerization of various commercially available monomers were considered using different inactivated/activated aromatic monomers combined with linear polyols ranging from C2 to C12 . The effect of various reaction solvents in enzymatic polymerization was assessed and toluene allowed to achieve the highest conversions for the reaction of dimethyl isophthalate with 1,4-butanediol and with 1,10-decanediol (88 and 87% monomer conversion respectively). Mw as high as 1512 Da was obtained from the reaction of dimethyl isophthalate with 1,10-decanediol. The obtained oligomers have potential applications as raw materials in personal and home care formulations, for the production of aliphatic-aromatic block co-polymers or can be further functionalized with various moieties for a subsequent photo- or radical polymerization.

  14. Triacylglycerols and aliphatic alcohols from fruits of three Tunisian Pistacia lentiscus populations.

    Science.gov (United States)

    Trabelsi, Hajer; Renaud, Justin; Herchi, Wahid; Boukhchina, Sadok; Mayer, Paul

    2015-08-15

    The search for other sources of vegetable oils by the exploitation and the enhancement of other oil plants will be needed to meet the demands of the international market. This study aims to determine the triacylglycerol (TAG) molecular species and aliphatic alcohol compositions of unexploited fruits of three Tunisian Pistacia lentiscus (lentisc) populations from the Korbous, Tebaba and Rimel areas of Tunisia. Results show that the content of total TAG varies from 738.32 mg g(-1) of total lipid in the Tebaba population to 981.15 mg g(-1) of total lipid in the Korbous population. Furthermore, 14 species of TAG were detected in the three studied populations. In addition, 13 aliphatic compounds were identified and classified into two groups: (1) aliphatic alcohols with fewer than 20 carbon atoms (hexadecanol, heptadecanol, (Z)-octadec-9-en-1-ol, octadecanol and nonadécanol); and (2) the policosanol group (eicosenol, docosenol, docosanol tetracosanol, hexacosanol octacosanol and triacontanol). The Tebaba population showed a distinct composition compared to Korbous and Rimel where heptadecanol is the major compound. Quantitatively, the most abundant TAG species are those constituted by palmitic, oleic and/or linoleic acid. Furthermore, the significant difference observed at the oil composition is associated with a remarkable station effect. © 2014 Society of Chemical Industry.

  15. Haloacetic acid and trihalomethane formation from the chlorination and bromination of aliphatic beta-dicarbonyl acid model compounds.

    Science.gov (United States)

    Dickenson, Eric R V; Summers, R Scott; Croué, Jean-Philippe; Gallard, Hervé

    2008-05-01

    While it is known that resorcinol- and phenol-type aromatic structures within natural organic matter (NOM) react during drinking water chlorination to form trihalomethanes (THMs), limited studies have examined aliphatic-type structures as THM and haloacetic acid (HAA) precursors. A suite of aliphatic acid model compounds were chlorinated and brominated separately in controlled laboratory-scale batch experiments. Four and two beta-dicarbonyl acid compounds were found to be important precursors for the formation of THMs (chloroform and bromoform (71-91% mol/mol)), and dihaloacetic acids (DXAAs) (dichloroacetic acid and dibromoacetic acid (5-68% mol/mol)), respectively, after 24 h at pH 8. Based upon adsorbable organic halide formation, THMs and DXAAs, and to a lesser extent mono and trihaloacetic acids, were the majority (> 80%) of the byproducts produced for most of the aliphatic beta-dicarbonyl acid compounds. Aliphatic beta-diketone-acid-type and beta-keto-acid-type structures could be possible fast- and slow-reacting THM precursors, respectively, and aliphatic beta-keto-acid-type structures are possible slow-reacting DXAA precursors. Aliphatic beta-dicarbonyl acid moieties in natural organic matter, particularly in the hydrophilic fraction, could contribute to the significant formation of THMs and DXAAs observed after chlorination of natural waters.

  16. Comprehensive database of Manufactured Gas Plant tars. Part B. Aliphatic and aromatic compounds.

    Science.gov (United States)

    Gallacher, Christopher; Thomas, Russell; Lord, Richard; Kalin, Robert M; Taylor, Chris

    2017-08-15

    Coal tars are a mixture of organic and inorganic compounds that were produced as a by-product from the manufactured gas and coke making industries. The composition of the tar produced varies depending on many factors; these include the temperature of production and the type of retort used. As different production processes produce different tars, a comprehensive database of the compounds present within coal tars from different production processes is a valuable resource. Such a database would help to understand how their chemical properties differ and what hazards the compounds present within these tars might pose. This study focuses on the aliphatic and aromatic compounds present in a database of 16 different tars from five different production processes. Samples of coal tar were extracted using accelerated solvent extraction (ASE) and derivatised post-extraction using N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) with 1% trimethylchlorosilane (TMCS). The derivatised samples were analysed using two-dimensional gas chromatography combined with time-of-flight mass spectrometry (GCxGC/TOFMS). A total of 198 individual aliphatic and 951 individual aromatic compounds were detected within 16 tar samples produced by five different production processes. The polycyclic aromatic hydrocarbon (PAH) content of coal tars varies greatly depending on the production process used to obtain the tars and this is clearly demonstrated within the results. The aliphatic composition of the tars provided an important piece of analytical information that would have otherwise been missed with the detection of petrogenic compounds such as alkyl cyclohexanes. The aromatic compositions of the tar samples varied greatly between the different production processes investigated and useful analytical information was obtained about the individual production process groups. Alkyl cyclohexanes were detected in all samples from sites known to operate Carbureted Water Gas plants and not detected in

  17. Molecular Characterization of MYB28 Involved in Aliphatic Glucosinolate Biosynthesis in Chinese Kale (Brassica oleracea var. alboglabra Bailey

    Directory of Open Access Journals (Sweden)

    Ling Yin

    2017-06-01

    Full Text Available Glucosinolates are Brassicaceae-specific secondary metabolites that act as crop protectants, flavor precursors, and cancer-prevention agents, which shows strong evidences of anticarcinogentic, antioxidant, and antimicrobial activities. MYB28, the R2R3-MYB28 transcription factor, directly activates genes involved in aliphatic glucosinolate biosynthesis. In this study, the MYB28 homology (BoaMYB28 was identified in Chinese kale (Brassica oleracea var. alboglabra Bailey. Analysis of the nucleotide sequence indicated that the cDNA of BoaMYB28 was 1257 bp with an ORF of 1020 bp. The deduced BoaMYB28 protein was a polypeptide of 339 amino acid with a putative molecular mass of 38 kDa and a pI of 6.87. Sequence homology and phylogenetic analysis showed that BoaMYB28 was most closely related to MYB28 homologs from the Brassicaceae family. The expression levels of BoaMYB28 varies across the tissues and developmental stages. BoaMYB28 transcript levels were higher in leaves and stems compared with those in cotyledons, flowers, and siliques. BoaMYB28 was expressed across all developmental leaf stages, with higher transcript accumulation in mature and inflorescence leaves. Over-expression and RNAi studies showed that BoaMYB28 retains the basic MYB28 gene function as a major transcriptional regulator of aliphatic glucosinolate pathway. The results indicated that over-expression and RNAi lines showed no visible difference on plant morphology. The contents of aliphatic glucosinolates and transcript levels of aliphatic glucosinolate biosynthesis genes increased in over-expression lines and decreased in RNAi lines. In over-expression lines, aliphatic glucosinolate contents were 1.5- to 3-fold higher than those in the wild-type, while expression levels of aliphatic glucosinolate biosynthesis genes were 1.5- to 4-fold higher than those in the wild-type. In contrast, the contents of aliphatic glucosinolates and transcript levels of aliphatic glucosinolate

  18. Strong Room-Temperature Photoluminescence from the Novel Adduct of C60 with Aliphatic Amines

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Strong room-temperature photoluminescence from the adducts of C60 reacting with five different aliphatic amines, namely propylethylamine (PPA), n-butyl amine (BTA), n-heptylamine (HPA) and dodecylamine (DDA) and diethylamine (DEA), was firstly found from their toluene solution at relatively shorter wavelength around 519 nm.The fluorescence intensity has a good correlation with the length of n-alkyl group chain, the steric position and concentration of different amines and setting of solution as well as the UV-radiation. Their fluorescence quenching by concentration and by aromatic electron-donor N,N-dimethylaniline (DMA) were first investigated and determined.

  19. Bifunctional Catalysis: Direct Reductive Amination of Aliphatic Ketones with an Iridium-Phosphate Catalyst

    Directory of Open Access Journals (Sweden)

    Barbara Villa-Marcos

    2010-04-01

    Full Text Available Chiral amines are one of the ubiquitous functional groups in fine chemical, pharmaceutical and agrochemical products, and the most convenient, economical, and eco-benign synthetic pathway to these amines is direct asymmetric reductive amination (DARA of prochiral ketones. This paper shows that a wide range of aliphatic ketones can be directly aminated under hydrogenation conditions, affording chiral amines with good to excellent yields and with enantioselectivities up to 96% ee. The catalysis is effected by the cooperative action of a cationic Cp*Ir(III complex and its phosphate counteranion.

  20. Solid state and sub-cooled liquid vapour pressures of cyclic aliphatic dicarboxylic acids

    Directory of Open Access Journals (Sweden)

    A. M. Booth

    2010-10-01

    Full Text Available Knudsen Effusion Mass Spectrometry (KEMS has been used to measure for the first time the solid state vapour pressures of a series of aliphatic cyclic dicarboxylic acids with increasing ring size. Additionally the atmospherically important compounds; cis-pinonic acid and levoglucosan were also measured. Differential Scanning Calorimetry (DSC was used to measure melting points, enthalpies and entropies of fusion, which were used to determine sub-cooled liquid vapour pressures for the compounds. The sub-cooled liquid vapour pressure of straight chain, branched and cyclic dicarboxylic acids was compared to a selection of estimation methods.

  1. "Clip" and "click" chemistries combination: toward easy PEGylation of degradable aliphatic polyesters.

    Science.gov (United States)

    Freichels, Hélène; Pourcelle, Vincent; Le Duff, Cécile S; Marchand-Brynaert, Jacqueline; Jérôme, Christine

    2011-04-04

    α-Methoxy-ω-alkyne poly(ethylene glycol) (PEG) was tagged with pendent N-hydroxy-succinimidyl activated esters by photografting of a molecular clip. This easily synthesized heterofunctional PEG was found to be a versatile building block for (i) conjugation with an amino derivative and (ii) grafting to azido functional aliphatic polyesters backbone by Huisgen's 1,3-dipolar cycloaddition. This original combination of "clip" and "click" reactions provides a versatile and straightforward pathway for the synthesis of functional amphiphilic and degradable copolymers valuable for biomedical applications such as in drug-delivery.

  2. Metal complexes of Schiff bases derived from dicinnamoylmethane and aliphatic diamines

    Directory of Open Access Journals (Sweden)

    K. KRISHNANKUTTY

    2008-04-01

    Full Text Available (Received 26 July, revised 10 December 2007Two new Schiff bases containing olefinic linkages have been synthesized by condensing aliphatic diamines with dicinnamoylmethane under specified conditions. The existence of these compounds predominantly in the intramolecularly hydrogen bonded keto-enamine form was well demonstrated by their IR, 1H-NMR and mass spectral data. Dibasic tetradentate N2O2 coordination of the compounds in their [ML] complexes (M = Ni(II, Cu(II and Zn(II was established on the basis of analytical and spectral data.

  3. A Study of Substituted Aliphatic Sulphides on the Corrosion Behaviour of Zinc in Ammonium Chloride Solution

    Directory of Open Access Journals (Sweden)

    R. Venckatesh

    2007-01-01

    Full Text Available Sulphur containing organic compounds decreases the corrosion rate by increasing the hydrogen over potential on zinc metal due to their electron donating groups. Their inhibiting effect was found to be associated with their adsorption on the active centers of the metal. The inhibition efficiencies of some aliphatic sulphides in ammonium chloride solution have been studied by weight loss studies, polarization and impedance measurements. The effect of substituent groups is correlated with their inhibition performance. These studies due to their relevance in Zn-Manganese dry batteries assume their importance.

  4. A QSPR STUDY OF NORMAL BOILING POINT OF ORGANIC COMPOUNDS (ALIPHATIC ALKANES USING MOLECULAR DESCRIPTORS

    Directory of Open Access Journals (Sweden)

    B. Souyei

    2013-12-01

    Full Text Available A quantitative structure–property relationship (QSPR study is carried out to develop correlations that relate the molecular structures of organic compounds (Aliphatic Alkanes to their normal boiling point (NBP and two correlations were proposed for constitutionals and connectivity indices Models. The correlations are simple in application with good accuracy, which provide an easy, direct and relatively accurate way to calculate NBP. Such calculation gives us a model that gives results in remarkable correlations with the descriptors of blokes constitutionals (CON, and connectivity indices (CI (R2 = 0.950, δ = 0.766 (R2 = 0.969, δ = 0.782 respectively.

  5. Abilities of some higher plants to hydrolyze the acetates of phenols and aromatic-aliphatic alcohols

    Directory of Open Access Journals (Sweden)

    Agnieszka Mironowicz

    2014-01-01

    Full Text Available In the biotransformations carried out under the same conditions, the whole intact plants of Spirodela punctata, Nephrolepis exaltata, Cyrtomium falcatum, Nephrolepis cordifolia and the suspension cultures of Helianthus tuberosus, Daucus carota and Petunia hybrida hydrolyze (partially or totally the ester bonds of the acetates of phenols and aromatic-aliphatic alcohols and also the menthyl acetate. Nevertheless, the methyl esters of aromatic acids, structurally similar to the former substrates, do not undergo hydrolysis. At the same time, the viability of first four plants was observed for different levels of acetate concentration. The method of continuous preparative hydrolysis of the same acetates was worked out in Cyrtomium falcatum culture.

  6. Silver-catalyzed decarboxylative alkynylation of aliphatic carboxylic acids in aqueous solution.

    Science.gov (United States)

    Liu, Xuesong; Wang, Zhentao; Cheng, Xiaomin; Li, Chaozhong

    2012-09-05

    C(sp(3))-C(sp) bond formations are of immense interest in chemistry and material sciences. We report herein a convenient, radical-mediated and catalytic method for C(sp(3))-C(sp) cross-coupling. Thus, with AgNO(3) as the catalyst and K(2)S(2)O(8) as the oxidant, various aliphatic carboxylic acids underwent decarboxylative alkynylation with commercially available ethynylbenziodoxolones in aqueous solution under mild conditions. This site-specific alkynylation is not only general and efficient but also functional group compatible. In addition, it exhibits remarkable chemo- and stereoselectivity.

  7. Simultaneous determination of aliphatic hydrocarbons, PCBs and PCTs in pork liver by gas chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez-Barros, C. [Dept. de Quimica Analitica, Nutricion y Bromatologia, Area Nutricion y Bromatologia, Facultad de Farmacia, Santiago de Compostela (Spain); Alvarez Pineiro, M.E. [Inst. de Investigacion y Analisis Alimentarios, Lab. de Bromatologia, Facultad de Farmacia, Santiago de Compostela (Spain); Simal Lozano, J. [Dept. de Quimica Analitica, Nutricion y Bromatologia, Area Nutricion y Bromatologia, Facultad de Farmacia, Santiago de Compostela (Spain); Lage Yusty, M.A. [Inst. de Investigacion y Analisis Alimentarios, Lab. de Bromatologia, Facultad de Farmacia, Santiago de Compostela (Spain)

    1996-10-01

    A multicomponent extraction/concentration procedure has been developed for the enrichment of PCBs, PCTs and aliphatic hydrocarbons (pristane, C{sub 18}, C{sub 19}, C{sub 20}, C{sub 22}, C{sub 24}, C{sub 28}, C{sub 32} and C{sub 36}) in pork liver. These components of the enriched extract were then simultaneously determined by gas chromatography. Mean recoveries ranged from 81.5% for pristane to 93% for PCBs; CV % (0.9-6.7) indicated the method to be both precise and reproducible. (orig.)

  8. The C--H Stretching Features at 3.2--3.5 Micrometer of Polycyclic Aromatic Hydrocarbons with Aliphatic Sidegroups

    CERN Document Server

    Yang, Xuejuan; Glaser, Rainer; Zhong, Jianxin

    2016-01-01

    The so-called unidentified infrared emission (UIE) features at 3.3, 6.2, 7.7, 8.6, and 11.3 micrometer are ubiquitously seen in a wide variety of astrophysical regions. The UIE features are characteristic of the stretching and bending vibrations of aromatic hydrocarbon materials, e.g., polycyclic aromatic hydrocarbon (PAH) molecules. The 3.3 micrometer aromatic C--H stretching feature is often accompanied by a weaker feature at 3.4 micrometer. The latter is often thought to result from the C--H stretch of aliphatic groups attached to the aromatic systems. The ratio of the observed intensity of the 3.3 micrometer aromatic C--H feature to that of the 3.4 micrometer aliphatic C--H feature allows one to estimate the aliphatic fraction of the UIE carriers, provided that the intrinsic oscillator strengths of the 3.3 micrometer aromatic C--H stretch (A3.3) and the 3.4 micrometer aliphatic C--H stretch (A3.4) are known. While previous studies on the aliphatic fraction of the UIE carriers were mostly based on the A3.4...

  9. Effect of electron beam irradiation on the biodegradability of aromatic aliphatic copolyester film and their blend with corn starch

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Leonardo G. Andrade e; Poveda, Patricia N.S., E-mail: lgasilva@ipen.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Rezende, Maira L.; Rosa, Derval S. [Universidade Sao Francisco, Itatiba, SP (Brazil)

    2009-07-01

    Biodegradable and green plastics have been studied in the last years. The aim of this paper is to study the effect of electron beam irradiation on the biodegradability of aromatic aliphatic copolyester film and their blend with corn starch. The samples were irradiated at different doses 10 and 40 kGy in a linear accelerator. The biodegradability of the materials was evaluated by two methods: soil simulated and enzymatic. In the method enzymatic when it was used alpha-amylase, the irradiated samples presented faster biodegradation than the references non irradiated. The blend of aromatic aliphatic copolyester with corn starch (Ecobras{sup R}) irradiated presented a bigger biodegradability than the aromatic aliphatic copolyester (Ecoflex{sup R}) film in both methods studied. (author)

  10. The FEMA GRAS assessment of aliphatic and aromatic terpene hydrocarbons used as flavor ingredients.

    Science.gov (United States)

    Adams, T B; Gavin, C Lucas; McGowen, M M; Waddell, W J; Cohen, S M; Feron, V J; Marnett, L J; Munro, I C; Portoghese, P S; Rietjens, I M C M; Smith, R L

    2011-10-01

    This publication is the thirteenth in a series of safety evaluations performed by the Expert Panel of the Flavor and Extract Manufacturers Association (FEMA). In 1993, the Panel initiated a comprehensive program to re-evaluate the safety of more than 1700 GRAS flavoring substances under conditions of intended use. Since then, the number of flavoring substances has grown to more than 2600 substances. Elements that are fundamental to the safety evaluation of flavor ingredients include exposure, structural analogy, metabolism, pharmacokinetics and toxicology. Flavor ingredients are evaluated individually and in the context of the available scientific information on the group of structurally related substances. Scientific data relevant to the safety evaluation of the use of aliphatic and aromatic terpene hydrocarbons as flavoring ingredients are evaluated. The group of aliphatic and aromatic terpene hydrocarbons was reaffirmed as GRAS (GRASr) based, in part, on their self-limiting properties as flavoring substances in food; their rapid absorption, metabolic detoxication, and excretion in humans and other animals; their low level of flavor use; the wide margins of safety between the conservative estimates of intake and the no-observed-adverse effect levels determined from subchronic and chronic studies and the lack of significant genotoxic potential. Copyright © 2011 Elsevier Ltd. All rights reserved.

  11. Drude polarizable force field for aliphatic ketones and aldehydes, and their associated acyclic carbohydrates

    Science.gov (United States)

    Small, Meagan C.; Aytenfisu, Asaminew H.; Lin, Fang-Yu; He, Xibing; MacKerell, Alexander D.

    2017-02-01

    The majority of computer simulations exploring biomolecular function employ Class I additive force fields (FF), which do not treat polarization explicitly. Accordingly, much effort has been made into developing models that go beyond the additive approximation. Development and optimization of the Drude polarizable FF has yielded parameters for selected lipids, proteins, DNA and a limited number of carbohydrates. The work presented here details parametrization of aliphatic aldehydes and ketones (viz. acetaldehyde, propionaldehyde, butaryaldehyde, isobutaryaldehyde, acetone, and butanone) as well as their associated acyclic sugars (uc(d)-allose and uc(d)-psicose). LJ parameters are optimized targeting experimental heats of vaporization and molecular volumes, while the electrostatic parameters are optimized targeting QM water interactions, dipole moments, and molecular polarizabilities. Bonded parameters are targeted to both QM and crystal survey values, with the models for ketones and aldehydes shown to be in good agreement with QM and experimental target data. The reported heats of vaporization and molecular volumes represent a compromise between the studied model compounds. Simulations of the model compounds show an increase in the magnitude and the fluctuations of the dipole moments in moving from gas phase to condensed phases, which is a phenomenon that the additive FF is intrinsically unable to reproduce. The result is a polarizable model for aliphatic ketones and aldehydes including the acyclic sugars uc(d)-allose and uc(d)-psicose, thereby extending the available biomolecules in the Drude polarizable FF.

  12. New aliphatic glycerophosphoryl-containing polyurethanes: synthesis, platelet adhesion and elution cytotoxicity studies.

    Science.gov (United States)

    Acetti, Daniela; D'Arrigo, Paola; Giordano, Carmen; Macchi, Piero; Servi, Stefano; Tessaro, Davide

    2009-04-01

    in this study new poly(ether)urethanes (PeUs) based on aliphatic diisocyanates were synthesized with phospholipid-like residues as chain extenders. The primary objective was to prepare new polyurethanes from diisocyanates that are less toxic than the aromatic ones widely used in medical-grade polyurethanes, in order to investigate the effect of the different aromatic or aliphatic hard segment content on the final properties of the materials. Some glycerophospho residues were simultaneously introduced to enhance the hemocompatibility of these materials. Polymers were prepared by a conventional two-step solution polymerization procedure using hexamethylene diisocyanate (HDi) and dodecametilendiisocyanate (DDi) and poly(1,4-butanediol) with molecular weight 1000 to form prepolymers, which were subsequently polymerized with 1-glycerophosphorylcholine (1-GPC) or glycerophosphorylserine (GPS) to act as chain extenders. The reference polymers bearing 1,4-butandiol (BD) were also synthesized. The polymers obtained were characterized by fourier transform infrared spectroscopy (fT-iR), nuclear magnetic resonance (1H nmR), and differential scanning calorimetry (DSC). The hemocompatibility of synthesized segmented polyurethanes was preliminarily investigated by platelet-rich plasma contact studies and related scanning electron microscopy (Sem) photographs as well as by cell viability assay after cell exposure to material elutions to assess the effect of any toxic leachables coming out from the samples. Two of the polymers gave interesting results, suggesting the desirability of further investigation into their possible use in biomedical devices.

  13. Drude polarizable force field for aliphatic ketones and aldehydes, and their associated acyclic carbohydrates

    Science.gov (United States)

    Small, Meagan C.; Aytenfisu, Asaminew H.; Lin, Fang-Yu; He, Xibing; MacKerell, Alexander D.

    2017-04-01

    The majority of computer simulations exploring biomolecular function employ Class I additive force fields (FF), which do not treat polarization explicitly. Accordingly, much effort has been made into developing models that go beyond the additive approximation. Development and optimization of the Drude polarizable FF has yielded parameters for selected lipids, proteins, DNA and a limited number of carbohydrates. The work presented here details parametrization of aliphatic aldehydes and ketones (viz. acetaldehyde, propionaldehyde, butaryaldehyde, isobutaryaldehyde, acetone, and butanone) as well as their associated acyclic sugars ( d-allose and d-psicose). LJ parameters are optimized targeting experimental heats of vaporization and molecular volumes, while the electrostatic parameters are optimized targeting QM water interactions, dipole moments, and molecular polarizabilities. Bonded parameters are targeted to both QM and crystal survey values, with the models for ketones and aldehydes shown to be in good agreement with QM and experimental target data. The reported heats of vaporization and molecular volumes represent a compromise between the studied model compounds. Simulations of the model compounds show an increase in the magnitude and the fluctuations of the dipole moments in moving from gas phase to condensed phases, which is a phenomenon that the additive FF is intrinsically unable to reproduce. The result is a polarizable model for aliphatic ketones and aldehydes including the acyclic sugars d-allose and d-psicose, thereby extending the available biomolecules in the Drude polarizable FF.

  14. Phase diagrams in blends of poly(3-hydroxybutyric acid with various aliphatic polyesters

    Directory of Open Access Journals (Sweden)

    2011-07-01

    Full Text Available Phase behavior with immiscibility, miscibility, crystalline morphology, and kinetic analysis in blends of poly(3-hydroxybutyric acid (PHB with aliphatic polyesters such as poly(butylene adipate (PBA, poly(ethylene adipate (PEA, poly(trimethylene adipate (PTA, or poly(ethylene succinate (PESu, respectively, were explored mainly using differential scanning calorimeter (DSC and polarized-light optical microscopy (POM. Immiscibility phase behavior with reversible upper-critical-solution-temperature (UCST is common in the PHB/polyester blends. The polyester/polyester blend of PHB/PTA is partially miscible with no UCST in melt and amorphous glassy states within a composition range of PTA less than 50 wt%. The miscible crystalline/crystalline blend exhibits ring-banded spherulites at Tc = 50~100°C, with inter-ring spacing dependent on Tc. All immiscible or partially miscible PHB/polyester blends, by contrast, exhibit disrupted ringbanded spherulites or discrete spherical phase domains upon cooling from UCST to crystallization. The blends of PHB with all other aliphatic polyesters, such as PESu, PEA, PBA, etc. are only partially miscible or immiscible with an upper critical solution temperature (UCST at 180~221°C depending on blend composition. UCST with reversibility was verified.

  15. A comprehensive evaluation of the toxicology of cigarette ingredients: aliphatic and aromatic carboxylic acids.

    Science.gov (United States)

    Coggins, Christopher R E; Liu, Jianmin; Merski, Jerome A; Werley, Michael S; Oldham, Michael J

    2011-06-01

    Aromatic and aliphatic carboxylic acids are present in tobacco and tobacco smoke. A battery of tests was used to compare the toxicity of mainstream smoke from experimental cigarettes containing eight aromatic and aliphatic carboxylic acids and the salt of one acid that were added individually at three different levels (lowest and highest target inclusions were 100 and 90,000 ppm, respectively). Mainstream smoke from cigarettes containing each of the test ingredients was evaluated using analytical chemistry and assays to measure in vitro cytotoxicity (neutral red uptake) and Salmonella (five strains) mutagenicity. For four of the compounds (citric, lactic, benzoic acids, and sodium benzoate), 90-day rodent inhalation studies were also performed. Although sporadic statistically significant differences in some experimental cigarette smoke constituents occurred, none resulted in significant changes in mutagenicity or cytotoxicity responses, nor in responses measured in the inhalation studies, except for lactic acid (LA). Inclusion of LA resulted in dose-dependent increase in water and caused a dose-dependent decrease in cytotoxicity. Incorporation of LA into cigarettes resulted in several dose-related reductions in histopathology, which were largely restricted to the nasal passages. Incorporation of LA also ameliorated some of the typical decrease in body weight gain seen in cigarette smoke-exposed rats. Inclusion of these ingredients at exaggerated use levels resulted in sporadic dose-related and treatment effects for some smoke constituents, but no toxicological response was noted in the in vitro and in vivo tests performed.

  16. Effect of Functional Group and Carbon Chain Length on the Odor Detection Threshold of Aliphatic Compounds

    Directory of Open Access Journals (Sweden)

    Manuel Zarzo

    2012-03-01

    Full Text Available Odor detection thresholds (ODTs are used for assessing outdoor and indoor air quality. They are obtained experimentally by olfactometry and psychophysical methods, and large compilations are available in the literature. A non-linear regression equation was fitted to describe the ODT variability of 114 aliphatic compounds based on the alkyl chain length for different homologous series (carboxylic acids, aldehydes, 2-ketones, esters, 1-alcohols, amines, thiols, thioethers and hydrocarbons. The resulting equation reveals an effect of the functional group, molecular size and also an interaction between both factors. Although the mechanistic interpretation of results is uncertain, the relatively high goodness-of-fit (R2 = 0.90 suggests that ODT values of aliphatic compounds can be predicted rather accurately, which is not the case for rigid molecules. This equation may serve as a basis for the development of more complex ODT models taking into account diverse structural features of odorants. The variability of power-law exponents was also investigated for the homologous series.

  17. Effect of testosterone and its aliphatic and aromatic dimers on DNA morphology.

    Science.gov (United States)

    Chanphai, P; Agudelo, D; Vesper, A R; Bérubé, G; Tajmir-Riahi, H A

    2017-02-01

    Conjugation of DNA with testosterone and it aliphatic dimer (alip) and aromatic dimer (arom) was investigated in aqueous solution at pH 7.4. Multiple spectroscopic methods, transmission electron microscopy (TEM) and molecular modeling were used to characterize steroid-DNA binding and DNA morphology. Spectroscopic analysis showed that testosterone binds DNA via A7, A16, A17, T8, T15 and T18 nucleobases with overall binding constants Ktest-DNA=1.8 (±0.4)×10(4)M(-1), Ktest-dimeralip-DNA=5.7 (±0.7)×10(4)M(-1) and Ktest-dimer-arom-DNA=7.3 (±0.9)×10(4)M(-1). The binding affinity increases in this order: testosterone dimer-aromatic>testosterone dimer-aliphatic>testosterone. The steroid loading efficacy was 40-50%. Transmission electron microscopy showed major changes in DNA morphology as testosterone-DNA interaction occurred with increase in the diameter of the DNA aggregate, indicating encapsulation of testosterone by DNA. Modeling showed the presence of several nucleobases attached to testosterone with the free binding energy of -4.93Kcal/mol.

  18. Aliphatic and aromatic hydrocarbons in particulate fallout of Alexandria, Egypt: Sources and implications

    Energy Technology Data Exchange (ETDEWEB)

    Aboul-Kassim, T.A.T.; Simoneit, B.R.T. [Oregon State Univ., Corvallis, OR (United States)

    1995-10-01

    Particulate fallout samples (PFS) were collected in Alexandria, and their aliphatic and aromatic hydrocarbon compositions were determined both quantitatively and qualitatively to characterize the homologous and biomarker compounds in terms of their original sources. The results show that all samples contain aliphatic hydrocarbons, including n-alkanes, UCM, isoprenoids, tri- and tetracyclic terpanes, hopanes, and steranes/diasteranes. The main source of these compounds is from petrochemical contamination with trace input of terrestrial higher plant wax. In addition, polycyclic aromatic hydrocarbons, which are considered to be combustion products from fossil fuels such as petroleum, are also widely distributed in all samples. Multivariate statistical analysis, including extended Q-mode factor analysis and linear programming technique, was performed in order to reduce the hydrocarbon data set into a meaningful number of end members (sources). This analysis indicates that there are two significant end members explaining 90% of the total variation among the samples and confirming petrochemical (79.6%), and thermogenic/pyrolytic (10.4%) sources in the PFS model. 65 refs., 7 figs., 4 tabs.

  19. Decomposition mechanisms of trinitroalkyl compounds: a theoretical study from aliphatic to aromatic nitro compounds.

    Science.gov (United States)

    Fayet, Guillaume; Rotureau, Patricia; Minisini, Benoit

    2014-04-14

    The chemical mechanisms involved in the decomposition of trinitroethyl compounds were studied for both aliphatic and aromatic derivatives using density functional theory calculations. At first, in the case of 1,1,1-trinitrobutane, used as a reference molecule, two primary channels were highlighted among the five investigated ones: the breaking of the C-N bond and the HONO elimination. Then, the influence of various structural parameters was studied for these two reactions by changing the length of the carbon chain, adding substituents or double bonds along the carbon chain. If some slight changes in activation energies were observed for most of these features, no modification of the competition between the two investigated reactions was highlighted and the breaking of the C-N bond remained the favoured mechanism. At last, the reactions involving the trinitroalkyl fragments were highlighted to be more competitive than reactions involving nitro groups linked to aromatic cycles in two aromatic systems (4-(1,1,1-trinitrobutyl)-nitrobenzene and 2-(1,1,1-trinitrobutyl)-nitrobenzene). This showed that aromatic nitro compounds with trinitroalkyl derivatives decompose from their alkyl part and may be considered more likely as aliphatic than as aromatic regarding the initiation of their decomposition process.

  20. Amount of aliphatic double carbon-carbon bonds in the kerogen of the Baltic shale kuckersite

    Energy Technology Data Exchange (ETDEWEB)

    Cheshko, I.D.; Kutuev, R.Kh.; Yakovlev, V.I.; Sendyurev, M.V.; Proskuryakov, V.A.

    1980-01-01

    In conclusion, among the questions of the chemical structure of the kerogen of combustible shales, one of the most important is that of the presence of multiple carbon-carbon bonds in the organic matter of these combustible minerals. In spite of a series of studies that have been performed this question has long remained open because of the contradictory opinions expressed. In the present paper, in order to evaluate the quantitative content of aliphatic bonds C-C in kerogen the authors analyze the results obtained by previous researchers in the study of the ozonization and chlorination of kuckersite, figures from balance experiments on chlorination, and the results of the use of ESR spectroscopy for these purposes and certain literature information on the halogenation of kuckersite kerogen. The presence in the kerogen of the Baltic combustible shale kuckersite of from 6 to 8 aliphatic double carbon-carbon bonds per 100 C atoms has been shown by the methods of chlorination, ozonization, and ESR spectroscopy, and this agrees with the figures calculated from certain results on the bromination of kuckersite. 18 refs.

  1. [Cloning and analysis of a new aliphatic amidase gene from Rhodococcus erythropolis TA37].

    Science.gov (United States)

    Lavrov, K V; Karpova, I Yu; Epremyan, A S; Yanenko, A S

    2014-10-01

    A new aliphatic amidase gene (ami), having a level of similarity with the nearest homologs of no more than 77%, was identified in the Rhodococcus erythropolis TA37 strain, which is able to hydrolyze a wide range of amides. The amidase gene was cloned within a 3.7 kb chromosomal locus, which also contains putative acetyl-CoA ligase and ABC-type transportergenes. The structure of this locus in the R. erythropolis TA37 strain differs from the structure of loci in other Rhodococcus strains. The amidase gene is expressed in Escherichia coli cells. It was demonstrated that amidase (generated in the recombinant strain) efficiently hydrolyzes acetamide (aliphatic anmide) and does not use 4'-nitroacetanilide (N-substituted amide) as a substrate. Insertional inactivation of the amidase gene in the R. erythropolis TA37 strain results in a considerable decrease (by at least 6-7 times) in basal amidase activity, indicating functional amidase activity in the R. erythropolis TA37 strain.

  2. Trapping by amylose of the aliphatic chain grafted onto chlorogenic acid: importance of the graft position.

    Science.gov (United States)

    Le-Bail, P; Lorentz, C; Pencreac'h, G; Soultani-Vigneron, S; Pontoire, B; López Giraldo, L J; Villeneuve, P; Hendrickx, J; Tran, V

    2015-03-06

    5-Caffeoylquinic acid (chlorogenic acid), is classified in acid-phenols family and as polyphenolic compounds it possesses antioxidant activity. The oxydative modification of chlorogenic acid in foods may lead to alteration of their qualities; to counteract these degradation effects, molecular encapsulation was used to protect chlorogenic acid. Amylose can interact strongly with a number of small molecules, including lipids. In order to enable chlorogenic acid complexation by amylose, a C16 aliphatic chain was previously grafted onto the cycle of quinic acid. This work showed that for the two lipophilic derivatives of chlorogenic acid: hexadecyl chlorogenate obtained by alkylation and 3-O-palmitoyl chlorogenic acid obtained by acylation; only the 3-O-palmitoyl chlorogenic acid complexed amylose. The chlorogenic acid derivatives were studied by X-ray diffraction, differential scanning calorimetry and NMR to elucidate the interaction. By comparing the results with previous work on the complexation of amylose by 4-O-palmitoyl chlorogenic acid, the importance of the aliphatic chain position on the cycle of the quinic acid is clearly highlighted. A study in molecular modeling helped to understand the difference in behavior relative to amylose of these three derivatives of chlorogenic acid.

  3. Application of flow-injection potentiometric system for determination of total concentration of aliphatic carboxylic acids.

    Science.gov (United States)

    Mroczkiewicz, Monika; Górski, Łukasz; Zamojska-Jaroszewicz, Anna; Szewczyk, Krzysztof W; Malinowska, Elżbieta

    2011-09-30

    In this work, flow-injection system with potentiometric detection was tested for determination of total carboxylic acid concentration. Detection part of the examined system consists of ion-selective electrodes (ISEs) with polymer membranes of different compositions. First electrode is based on Zr(IV)-tetraphenylporphyrin as ionophore selective towards carboxylic acid anions, the membrane of second one contains only liphophilic anion exchanger - tridodecylmethylammonium chloride. Final response of the system is a result of combination of EMF signals from both electrodes. Combination of two detectors enables significant decrease of differences between potentiometric signals induced by mixtures of studied anions of various concentrations as compared to results obtained only with metalloporphyrin-based ISE. The use of anion-exchanger based detector allows for elimination of the influence of aliphatic carboxylic acids lipophilicity. Proposed potentiometric flow-injection system was employed for determination of short-chain aliphatic carboxylic acids (so-called VFA - volatile fatty acids) in samples originating from an anaerobic digester. Results obtained for these relatively complicated samples are in good agreement with results obtained with the use of reference colorimetric method. Linear response towards carboxylic acids was observed in the concentration range of 10(-4) to 10(-2)mold m(-3), with the slopes in the range of -110 to -150 mV dec(-1) (for acetate(-) and butyrate(-), respectively). System enables for determination of about 6 samples per hour. Life time of ISEs average about 2 months.

  4. Aliphatic amidase of Rhodococcus rhodochrous PA-34: Purification, characterization and application in synthesis of acrylic acid.

    Science.gov (United States)

    Thakur, Neerja; Kumar, Vijay; Sharma, Nirmal Kant; Thakur, Shikha; Bhalla, Tek Chand

    2016-01-01

    An intracellular aliphatic amide degrading inducible amidase produced by Rhodococcus rhodochrous PA-34 was characterized and acrylic acid synthesis from acrylamide was carried out using whole cell amidase. A bioprocess was developed at 50 ml fed batch reaction using 400 mM acrylamide feeding at an interval of 30 min resulted in the production of 4 g acrylic acid with volumetric and catalytic productivity of 80 g/l and 19 g/g/h respectively. The amidase of this organism had molecular weight of 40 kDa and was purified to 8.5 fold with 8% yield. This enzyme was active within the temperature range of 30 to 60 °C, with optimum temperature 45 °C and pH 7.5. The Vmax, Km, and kcat of purified amidase were calculated as 250 U/mg protein, 4.5 mM, and 166 sec-1 for acrylamide. The enzyme showed tolerance to metal chelating agent (EDTA) and was strongly inhibited by heavy metal ions Hg2+, Ag2+, Cu2+ and Co2+. R. rhodochrous PA-34 amidase preferentially hydrolyzed small aliphatic toxic amide such as acrylamide. Thus, the amidase of R. rhodochrous PA-34 is promising biocatalyst for the synthesis of industrially important acids and biodegradation of toxic amides.

  5. [Analysis of aliphatic carboxylic acids in anaerobic digestion process waters by ion-exclusion chromatography].

    Science.gov (United States)

    Ito, Kazuaki; Sakamoto, Jun; Nagaoka, Kazuya; Takayama, Yohichi; Kanahori, Takashi; Sunahara, Hiroshi; Hayashi, Tsuneo; Sato, Shinji; Hirokawa, Takeshi; Tanaka, Kazuhiko

    2012-04-01

    The analysis of seven aliphatic carboxylic acids (formic, acetic, propionic, iso-butyric, n-butyric, iso-valeric and n-valeric acid) in anaerobic digestion process waters for biogas production was examined by ion-exclusion chromatography with dilute acidic eluents (benzoic acid, perfluorobutyric acid (PFBA) and sulfuric acid) and non-suppressed conductivity/ultraviolet (UV) detection. The columns used were a styrene/divinylbenzene-based strongly acidic cation-exchange resin column (TSKgel SCX) and a polymethacrylate-based weakly acidic cation-exchange resin column (TSKgel Super IC-A/C). Good separation was performed on the TSKgel SCX in shorter retention times. For the TSKgel Super IC-A/C, peak shape of the acids was sharp and symmetrical in spite of longer retention times. In addition, the mutual separation of the acids was good except for iso- and n-butyric acids. The better separation and good detection was achieved by using the two columns (TSKgel SCX and TSKgel Super IC-A/C connected in series), lower concentrations of PFBA and sulfuric acid as eluents, non-suppressed conductivity detection and UV detection at 210 nm. This analysis was applied to anaerobic digestion process waters. The chromatograms with conductivity detection were relatively simpler compared with those of UV detection. The use of two columns with different selectivities for the aliphatic carboxylic acids and the two detection modes was effective for the determination and identification of the analytes in anaerobic digestion process waters containing complex matrices.

  6. Olfactory sensitivity and odor structure-activity relationships for aliphatic carboxylic acids in CD-1 mice.

    Science.gov (United States)

    Can Güven, Selçuk; Laska, Matthias

    2012-01-01

    Using a conditioning paradigm, the olfactory sensitivity of CD-1 mice for a homologous series of aliphatic n-carboxylic acids (ethanoic acid to n-octanoic acid) and several of their isomeric forms was investigated. With all 14 odorants, the animals significantly discriminated concentrations as low as 0.03 ppm (parts per million) from the solvent, and with four odorants the best-scoring animals even detected concentrations as low as 3 ppt (parts per trillion). Analysis of odor structure-activity relationships showed that the correlation between olfactory detection thresholds of the mice for the unbranched carboxylic acids and carbon chain length can best be described as a U-shaped function with the lowest threshold values at n-butanoic acid. A significant positive correlation between olfactory detection thresholds and carbon chain length of the carboxylic acids with their branching next to the functional carboxyl group was found. In contrast, no such correlation was found for carboxylic acids with their branching at the distal end of the carbon chain relative to the functional carboxyl group. Finally, a significant correlation was found between olfactory detection thresholds and the position of the branching of the carboxylic acids. Across-species comparisons suggest that mice are more sensitive for short-chained (C(2) to C(4)) aliphatic n-carboxylic acids than other mammalian species, but not for longer-chained ones (C(5) to C(8)). Further comparisons suggest that odor structure-activity relationships are both substance class- and species-specific.

  7. Chiroptical study of α-aliphatic amino acid films in the vacuum ultraviolet region.

    Science.gov (United States)

    Tanaka, Masahito; Yagi-Watanabe, Kazutoshi; Kaneko, Fusae; Nakagawa, Kazumichi

    2010-11-11

    A series of natural circular dichroism (CD) and absorption spectra for films of α-aliphatic amino acids--such as alanine, aminobutyric acid, norvaline, norleucine, valine, leucine, and isoleucine--in the vacuum ultraviolet (VUV) region were observed with the absolute values of optical constants at the undulator-based CD beamline TERAS BL5. Preliminary predictions of some CD spectra were also performed, based on quantum-chemical calculations using the crystal structure. Although the absorption spectra show similar features to each other, significant differences between the CD spectra were found, especially in the 7-8 eV region. The CD spectra of aliphatic amino acids with branched alkyl groups in the side-chain--such as valine, leucine, and isoleucine--exhibit strong negative CD peaks in this energy region. In contrast, the corresponding CD peaks were weak or absent in the spectra of amino acids with straight alkyl groups. Our simple calculation, and the absorption spectra of alkanes, suggest that this difference partly originates from the contribution of the alkyl group. Clear discrepancies between the CD spectra of these amino acids in solutions and those in the solid state were also observed; this is probably caused by the different molecular structures in each state. Our results clearly indicated that CD spectra in the VUV region were very sensitive to the conformations of chiral molecules.

  8. Aliphatic carboxylic acids and alcohols as efficiency and elution strength enhancers in micellar liquid chromatography.

    Science.gov (United States)

    Boichenko, Alexander P; Berthod, Alain

    2010-09-03

    Micellar liquid chromatography (MLC) uses surfactant solutions as mobile phases with added organic additives to enhance both the elution strength and the chromatographic efficiency. Two aliphatic carboxylic acids (1-butanoic and 1-pentanoic) were used as MLC additives and compared with the two corresponding alcohols (1-butanol, 1-pentanol) in terms of elution strength, efficiency and selectivity. A set of 11 phenol derivatives was used as probe compounds. All micellar mobile phases were prepared with sodium dodecylsulfate (SDS) with concentration ranging from 0.05 to 0.15M and the modifier content within 1.0 and 5.0% (v/v). The elution strength of different mobile phases containing a constant amount of SDS and different amounts of modifiers; and mobile phases containing a constant amount of modifier and different SDS concentration were determined and discussed. The effect of the acid modifiers on efficiency was studied constructing van Deemter plots that showed no minimum within the 0.01-0.7mL/min flow rate range studied. Temperature effects were also studied constructing the classical van't Hoff plots. The slight curvature of the plots in the 25-70 degrees C range may indicate some modification of the surfactant-bonded moiety layer on the stationary phase surface. Since no definitive advantage of the use of aliphatic acids were established compared to their alcohol counterpart, their terrible smell will probably preclude their use as MLC organic modifiers.

  9. Correlation between NQR parameters and residue size of aliphatic amino acids and their dimers.

    Science.gov (United States)

    Ghaderi, Ali Reza; Sabzyan, Hassan; Hadipour, Nasser L

    2006-03-01

    Nuclear quadrupole coupling constants (NQCC), chi, and asymmetry parameters, eta, of 2D, 14N and 17O nuclei have been calculated for aliphatic amino acids and their dimers using MP2/6-311++G** method to shed some light on the differences between the structural parameters in the aliphatic amino acids and their dimers. For this purpose, electric field gradient (EFG) at the sites of quadrupolar nuclei have been calculated and evaluated for each compound. A correlation is observed between the calculated NQCC parameters and the conformational structures of the compounds, showing that extraction of structural data from the NQR spectra might be promising. Our results showed that 17O NQCC of terminal carboxylic acid and 14N NQCC of the terminal amino groups are, respectively, the least and the most sensitive parameters to the variation of the size of the residue. It is found also that conformation of R (i.e. values of the dihedral angles) plays a very effective role in the determination of the values of the calculated NQCC parameters. Sensitivity of the NQR parameters to the changes in the conformational structure is significantly greater (nearly 20-fold) than that to the changes in the other structural parameters such as bond lengths.

  10. Drude polarizable force field for aliphatic ketones and aldehydes, and their associated acyclic carbohydrates.

    Science.gov (United States)

    Small, Meagan C; Aytenfisu, Asaminew H; Lin, Fang-Yu; He, Xibing; MacKerell, Alexander D

    2017-02-11

    The majority of computer simulations exploring biomolecular function employ Class I additive force fields (FF), which do not treat polarization explicitly. Accordingly, much effort has been made into developing models that go beyond the additive approximation. Development and optimization of the Drude polarizable FF has yielded parameters for selected lipids, proteins, DNA and a limited number of carbohydrates. The work presented here details parametrization of aliphatic aldehydes and ketones (viz. acetaldehyde, propionaldehyde, butaryaldehyde, isobutaryaldehyde, acetone, and butanone) as well as their associated acyclic sugars (D-allose and D-psicose). LJ parameters are optimized targeting experimental heats of vaporization and molecular volumes, while the electrostatic parameters are optimized targeting QM water interactions, dipole moments, and molecular polarizabilities. Bonded parameters are targeted to both QM and crystal survey values, with the models for ketones and aldehydes shown to be in good agreement with QM and experimental target data. The reported heats of vaporization and molecular volumes represent a compromise between the studied model compounds. Simulations of the model compounds show an increase in the magnitude and the fluctuations of the dipole moments in moving from gas phase to condensed phases, which is a phenomenon that the additive FF is intrinsically unable to reproduce. The result is a polarizable model for aliphatic ketones and aldehydes including the acyclic sugars D-allose and D-psicose, thereby extending the available biomolecules in the Drude polarizable FF.

  11. Branched aliphatic alkanes of shell bar section in Qarhan Lake, Qaidam Basin and their paleoclimate significance

    Institute of Scientific and Technical Information of China (English)

    ZHANG HuCai; CHANG FengQin; LI Bin; LEI GuoLiang; CHEN Yue; ZHANG WenXiang; NIU Jie; FAN HongFang; YANG MingSheng

    2007-01-01

    Biomarkers of paleolake deposits from Qarhan Salt Lake in Qaidam Basin, northwest China were systematically analyzed and the A-C series compounds of branched aliphatic alkanes with quaternary substituted carbon atom (BAQCs) were identified. The homologous distinguished three series, A-C,were identified as 5,5-diethylalkanes, 6,6-diethylalkanes and 5-butyl, 5-ethylalkanes series, and their relative abundance was A > B > C. Series A and C were characterized by odd carbon numbers, whereas series B was characterized by even carbon numbers. The high values of series A corresponded with the high values of series B and C. Therefore, it can be concluded that series A, B and C possess a similar biological origin. The abundance of series A was relatively Iow in the lower part of the section compared with that in the upper part, implying that these series originated from bacteria and/or algae more prevalent in fresh-mesohaline water, and such kinds of bacteria and/or algae are most likely to be thermophilous species. The A25/nC25 ratio differences in the section show that such branched aliphatic alkanes can be treated as one kind of environmental change proxy for paleolake evolution and may provide important information for the climate reconstruction of the Late Pleistocene.

  12. Transition-metal-free visible-light photoredox catalysis at room-temperature for decarboxylative fluorination of aliphatic carboxylic acids by organic dyes.

    Science.gov (United States)

    Wu, Xinxin; Meng, Chunna; Yuan, Xiaoqian; Jia, Xiaotong; Qian, Xuhong; Ye, Jinxing

    2015-07-28

    We report herein an efficient, general and green method for decarboxylative fluorination of aliphatic carboxylic acids. By using a transition-metal-free, organocatalytic photoredox system, the reaction of various aliphatic carboxylic acids with the Selectfluor reagent afforded the corresponding alkyl fluorides in satisfactory yields under visible light irradiation at room temperature.

  13. Ascorbyl palmitate/d-α-tocopheryl polyethylene glycol 1000 succinate monoester mixed micelles for prolonged circulation and targeted delivery of compound K for antilung cancer therapy in vitro and in vivo

    Directory of Open Access Journals (Sweden)

    Zhang Y

    2017-01-01

    Full Text Available Youwen Zhang, Deyin Tong, Daobiao Che, Bing Pei, Xiaodong Xia, Gaofeng Yuan, Xin Jin Department of Hospital Pharmacy, The First Hospital of Suqian, Suqian, People’s Republic of China Abstract: The roles of ginsenoside compound K (CK in inhibiting tumor have been widely recognized in recent years. However, low water solubility and significant P-gp efflux have restricted its application. In this study, CK ascorbyl palmitate (AP/d-α-tocopheryl polyethylene glycol 1000 succinate monoester (TPGS mixed micelles were prepared as a delivery system to increase the absorption and targeted antitumor effect of CK. Consequently, the solubility of CK increased from 35.2±4.3 to 1,463.2±153.3 µg/mL. Furthermore, in an in vitro A549 cell model, CK AP/TPGS mixed micelles significantly inhibited cell growth, induced G0/G1 phase cell cycle arrest, induced cell apoptosis, and inhibited cell migration compared to free CK, all indicating that the developed micellar delivery system could increase the antitumor effect of CK in vitro. Both in vitro cellular fluorescence uptake and in vivo near-infrared imaging studies indicated that AP/TPGS mixed micelles can promote cellular uptake and enhance tumor targeting. Moreover, studies in the A549 lung cancer xenograft mouse model showed that CK AP/TPGS mixed micelles are an efficient tumor-targeted drug delivery system with an effective antitumor effect. Western blot analysis further confirmed that the marked antitumor effect in vivo could likely be due to apoptosis promotion and P-gp efflux inhibition. Therefore, these findings suggest that the AP/TPGS mixed micellar delivery system could be an efficient delivery strategy for enhanced tumor targeting and antitumor effects. Keywords: ginsenoside CK, ascorbyl palmitate, TPGS, mixed micelles, anti-tumor therapy

  14. SPE-UPLC-MS/MS for the determination of phthalate monoesters in rats urine and its application to study the effects of food emulsifier on the bioavailability of priority controlling PAEs.

    Science.gov (United States)

    Xu, R; Gao, H T; Zhu, F; Cao, W X; Yan, Y H M; Zhou, X; Xu, Q; Ji, W L

    2016-02-15

    This research was mainly focused on the effects of food emulsifier on the bioavailability of six priority controlling phthalate acid esters (PAEs) for the further accurate assessment of their toxic effects, using the corresponding phthalate acid monoesters (PAMEs) in rats urine as biomarkers. Glycerin monostearate was chosen as typical food emulsifier. A method was established to determine PAMEs in urine from rats either in experimental group (integrated gavaged with glycerin monostearate and PAEs) or in control group (gavaged with PAEs only), by using solid-phase extraction (SPE) coupled with ultra performance liquid chromatography tandem mass spectrometry (SPE-UPLC-MS/MS). Extraction recoveries were more than 75% for all the PAMEs; the calibration curve was linear in the range of 1.0-1000.0ng/mL with R(2)>0.995; the limits of detection (LOD) were 0.30ng/mL-0.50ng/mL. In addition, by analysing quality control (QC) urine samples in 3 days, it showed that the method was precise and accurate, for the intra-day and inter-day RSD within 16%, and the accuracy more than 82%. Internal exposure amount of all PAEs in experimental group was significantly higher than that in control group with p values of less than 0.05 except for butyl benzyl phthalates (BBP) (P=0.07). The bioavailability of all PAEs ranged from 5.03% to 109.35% with the presence of food emulsifiers glycerin monostearate, observably higher than that without glycerin monostearate (1.12% to 54.39%). It indicated that food emulsifiers increased the bioavailability of PAEs and may lead to potential food safety risk, which should bring awareness and be further studied.

  15. Influence of starch phosphate monoester on shrimp dumpling skin transparency%淀粉磷酸单酯对虾饺皮透明度的影响研究

    Institute of Scientific and Technical Information of China (English)

    焦云鹏

    2012-01-01

    广式面点虾饺是以外观晶莹透明,馅心鲜嫩可口而闻名中外的面点食品,在皮料制作中加入不同比例同一取代度的淀粉磷酸单酯和加入同一比例不同取代度的淀粉磷酸单酯分别制成糊状液和成品虾饺,通过单因素实验检测糊状液的透光率,排序检验法鉴定成品间透明度的显著差异,从而得出淀粉糊状液的透明度与虾饺成品的透明度有正相关关系,同时也说明淀粉磷酸单酯显著提高了虾饺皮的透明度,且随着取代度的增加,其效果越显著。%Cantonese pastry shrimp dumplings are very popular foods in Chinese and foreign with transparent crystal appearance, fresh delicious filling. The same substitution degrees and the different proportion starch phosphate monoester (SPM) or the different substitution degrees and the same proportion SPM were added to the dumpling skin. the positive correlation relationship of SPM and shrimp dumplings transparency were obtained in the dumpling wrapper making. SPM changed the gelatinization degree and transparency of dumpling wrapper through the single factor experiment detection and sorting test method. The substitution degree of SPM was higher, and improvement effect was better.

  16. Reductions of aliphatic and aromatic nitriles to primary amines with diisopropylaminoborane.

    Science.gov (United States)

    Haddenham, Dustin; Pasumansky, Lubov; DeSoto, Jamie; Eagon, Scott; Singaram, Bakthan

    2009-03-06

    Diisopropylaminoborane [BH(2)N(iPr)(2)] in the presence of a catalytic amount of lithium borohydride (LiBH(4)) reduces a large variety of aliphatic and aromatic nitriles in excellent yields. BH(2)N(iPr)(2) can be prepared by two methods: first by reacting diisopropylamineborane [(iPr)(2)N:BH(3)] with 1.1 equiv of n-butyllithium (n-BuLi) followed by methyl iodide (MeI), or reacting iPrN:BH(3) with 1 equiv of n-BuLi followed by trimethylsilyl chloride (TMSCl). BH(2)N(iPr)(2) prepared with MeI was found to reduce benzonitriles to the corresponding benzylamines at ambient temperatures, whereas diisopropylaminoborane prepared with TMSCl does not reduce nitriles unless a catalytic amount of a lithium ion source, such as LiBH(4) or lithium tetraphenylborate (LiBPh(4)), is added to the reaction. The reductions of benzonitriles with one or more electron-withdrawing groups on the aromatic ring generally occur much faster with higher yields. For example, 2,4-dichlorobenzonitrile was successfully reduced to 2,4-dichlorobenzylamine in 99% yield after 5 h at 25 degrees C. On the other hand, benzonitriles containing electron-donating groups on the aromatic ring require refluxing in tetrahydrofuran (THF) for complete reduction. For instance, 4-methoxybenzonitrile was successfully reduced to 4-methoxybenzylamine in 80% yield. Aliphatic nitriles can also be reduced by the BH(2)N(iPr)(2)/cat. LiBH(4) reducing system. Benzyl cyanide was reduced to phenethylamine in 83% yield. BH(2)N(iPr)(2) can also reduce nitriles in the presence of unconjugated alkenes and alkynes such as the reduction of 2-hexynenitrile to hex-5-yn-1-amine in 80% yield. Unfortunately, selective reduction of a nitrile in the presence of an aldehyde is not possible as aldehydes are reduced along with the nitrile. However, selective reduction of the nitrile group at 25 degrees C in the presence of an ester is possible as long as the nitrile group is activated by an electron-withdrawing substituent. It should be

  17. Mortality of Bemisia tabaci biotype B (sternorrhyncha: aleyrodidae adults by aliphatic and aromatic synthetic sucrose esters

    Directory of Open Access Journals (Sweden)

    Mariangela Alves

    2008-12-01

    Full Text Available The B-strain of Bemisia tabaci Gennadius is a key pest of several crops and chemical control is the main control method used by growers, although reduction in efficacy due to insecticide resistance has already been reported. The aim of this work was to investigate the insecticidal effect of an array of synthetic sucrose esters with the aliphatic and aromatic groups on whitefly adults. Sucrose butyrate, caprate, octanoate, palmitate, oleate, octaacetate, phthalate, benzoate, and sucrose diacetate hexaisobutyrate were tested. The solutions were prepared and applied on the adults caught on yellow sticky traps using the Potter spray tower. Long-chains sucrose aliphatic esters were more effective against the silverleaf whiteflies and the highest mortality was obtained with sucrose oleate and sucrose octanoate. Since these compounds were tensoactive, sodium dodecylsulphate was also tested for the comparison but no effect was observed. Sucrose butyrate and other aliphatic and aromatic sucrose polyesters showed negligible effect on the silverleaf whiteflies.O biótipo B de B. tabaci Gennadius tem se destacado como uma praga-chave de diversas culturas. O controle químico tem sido a principal tática de controle utilizada, embora já se tenha observado redução na eficiência dos produtos devido ao desenvolvimento de resistência. Assim, o objetivo do presente trabalho foi avaliar o efeito de diversos ésteres de sacarose com grupos alifáticos ou aromáticos sobre adultos de mosca-branca. Butirato de sacarose, caprato, octanoato, palmitato, oleato, actaacetato, ftlato, benzoato e diacetato hexaisobutirato de sacarose foram testados. Soluções de éster de sacarose foram preparadas e aplicadas sobre adultos capturados em armadilhas adesivas utilizando Torre de Potter. Ésteres alifáticos de sacarose com longas cadeias foram mais efetivos contra mosca-branca e as maiores taxas de mortalidade foram obtidas com oleato e octanoato de sacarose. Uma vez que

  18. The impact of the absence of aliphatic glucosinolates on water transport under salt stress in Arabidopsis thaliana

    Directory of Open Access Journals (Sweden)

    Mcarmen eMartinez-Ballesta

    2015-07-01

    Full Text Available Members of the Brassicaceae are known for their contents of nutrients and health-promoting phytochemicals, including glucosinolatesExposure to salinity increases the levels of several of these compounds, but their role in abiotic stress response is unclear. The effect of aliphatic glucosinolates on plant water balance and growth under salt stress, involving aquaporins, was investigated by means of Arabidopsis thaliana mutants impaired in aliphatic glucosinolate biosynthesis, which is controlled by two transcription factors: Myb28 and Myb29. The double mutant myb28myb29, completely lacking aliphatic glucosinolates, was compared to wild type Col-0 (WT and the single mutant myb28. A greater reduction in the hydraulic conductivity of myb28myb29 was observed under salt stress, when compared to the WT and myb28; this correlated with the abundance of both PIP1 and PIP2 aquaporin subfamilies. Also, changes in root architecture in response to salinity were genotype dependent. Treatment with NaCl altered glucosinolates biosynthesis in a similar way in WT and the single mutant and differently in the double mutant. The results indicate that short-chain aliphatic glucosinolates may contribute to water saving under salt stress

  19. Preparation and characterization of protein loaded microspheres based on a hydroxylated aliphatic polyester, poly (lactic-co-hydroxymethyl glycolic acid)

    NARCIS (Netherlands)

    Ghassemi, A.H.; van Steenbergen, M.J.; Talsma, H.; van Nostrum, C.F.; Jiskoot, W.; Crommelin, D.J.A.; Hennink, W.E.

    2009-01-01

    The purpose of this study was to investigate the suitability of a novel hydroxylated aliphatic polyester, poly (lactic-co-hydroxymethyl glycolic acid) (PLHMGA), as controlled release system for pharmaceutical proteins. Dextran Blue (as a macromolecular model compound) and lysozyme-loaded PLHMGA and

  20. Amperometric detection and electrochemical oxidation of aliphatic amines and ammonia on silver-lead oxide thin-film electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Ge, Jisheng [Iowa State Univ., Ames, IA (United States)

    1996-01-08

    This thesis comprises three parts: Electrocatalysis of anodic oxygen-transfer reactions: aliphatic amines at mixed Ag-Pb oxide thin-film electrodes; oxidation of ammonia at anodized Ag-Pb eutectic alloy electrodes; and temperature effects on oxidation of ethylamine, alanine, and aquated ammonia.

  1. Biocompatibility and degradation of aliphatic segmented poly(ester amide)s : in vitro and in vivo evaluation

    NARCIS (Netherlands)

    Lips, PAM; van Luyn, MJA; Chiellini, F; Brouwer, LA; Velthoen, IW; Dijkstra, PJ; Feijen, J

    2006-01-01

    Aliphatic segmented poly(ester amide)s, comprising a crystallizable amide phase and a flexible amorphous ester phase, were investigated for potential use in biomedical applications. By varying the amide content and the type of crystallizable amide segments, the polymer's thermal and mechanical prope

  2. Changes in the molecular composition of ester-bound aliphatics with depth in an acid andic forest soil

    NARCIS (Netherlands)

    Naafs, Derck Ferdinand Werner; Nierop, K.G.J.; Bergen, P.F. van; Leeuw, J.W. de

    2005-01-01

    Changes in the molecular composition of ester-linked aliphatic compounds with depth in an acid andic forest soil are studied. Thermally assisted hydrolysis and methylation (THM) using tetramethylammonium hydroxide in combination with gas chromatography/mass spectrometry revealed a dominance of cutin

  3. Ru/Me-BIPAM-Catalyzed Asymmetric Addition of Arylboronic Acids to Aliphatic Aldehydes and α-Ketoesters

    Directory of Open Access Journals (Sweden)

    Momoko Watanabe

    2011-06-01

    Full Text Available A ruthenium-catalyzed asymmetric arylation of aliphatic aldehydes and α-ketoesters with arylboronic acids has been developed, giving chiral alkyl(arylmethanols and α-hydroxy esters in good yields. The use of a chiral bidentate phosphoramidite ligand (Me-BIPAM achieved excellent enantioselectivities.

  4. Biocompatibility and degradation of aliphatic segmented poly(ester amide)s : in vitro and in vivo evaluation

    NARCIS (Netherlands)

    Lips, PAM; van Luyn, MJA; Chiellini, F; Brouwer, LA; Velthoen, IW; Dijkstra, PJ; Feijen, J

    2006-01-01

    Aliphatic segmented poly(ester amide)s, comprising a crystallizable amide phase and a flexible amorphous ester phase, were investigated for potential use in biomedical applications. By varying the amide content and the type of crystallizable amide segments, the polymer's thermal and mechanical prope

  5. Structural characterisation of aliphatic, non-hydrolyzable biopolymers in freshwater algae and a leaf cuticle by ruthenium tetroxide degradation

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Schouten, S.; Moerkerken, P.; Gelin, F.; Baas, M.; Leeuw, J.W. de

    1998-01-01

    Aliphatic, non-hydrolyzable biopolymers were subjected to RuO4-oxidation in order to examine the potential of this method in revealing details on their structures. The method was tested on model compounds first and found to cleave alkyl chains of aromatic moieties, double bonds and ether bonds. Oxid

  6. Liquid-phase synthesis of bridged peptides using olefin metathesis of a protected peptide with a long aliphatic chain anchor.

    Science.gov (United States)

    Aihara, Keisuke; Komiya, Chiaki; Shigenaga, Akira; Inokuma, Tsubasa; Takahashi, Daisuke; Otaka, Akira

    2015-02-01

    Bridged peptides including stapled peptides are attractive tools for regulating protein-protein interactions (PPIs). An effective synthetic methodology in a heterogeneous system for the preparation of these peptides using olefin metathesis and hydrogenation of protected peptides with a long aliphatic chain anchor is reported.

  7. Preparation and characterization of protein loaded microspheres based on a hydroxylated aliphatic polyester, poly (lactic-co-hydroxymethyl glycolic acid)

    NARCIS (Netherlands)

    Ghassemi, A.H.|info:eu-repo/dai/nl/314132945; van Steenbergen, M.J.|info:eu-repo/dai/nl/304839302; Talsma, H.|info:eu-repo/dai/nl/08138212X; van Nostrum, C.F.|info:eu-repo/dai/nl/134498690; Jiskoot, W.|info:eu-repo/dai/nl/084557397; Crommelin, D.J.A.|info:eu-repo/dai/nl/074578804; Hennink, W.E.|info:eu-repo/dai/nl/070880409

    2009-01-01

    The purpose of this study was to investigate the suitability of a novel hydroxylated aliphatic polyester, poly (lactic-co-hydroxymethyl glycolic acid) (PLHMGA), as controlled release system for pharmaceutical proteins. Dextran Blue (as a macromolecular model compound) and lysozyme-loaded PLHMGA and

  8. Ru/Me-BIPAM-catalyzed asymmetric addition of arylboronic acids to aliphatic aldehydes and α-ketoesters.

    Science.gov (United States)

    Yamamoto, Yasunori; Shirai, Tomohiko; Watanabe, Momoko; Kurihara, Kazunori; Miyaura, Norio

    2011-06-17

    A ruthenium-catalyzed asymmetric arylation of aliphatic aldehydes and α-ketoesters with arylboronic acids has been developed, giving chiral alkyl(aryl)methanols and α-hydroxy esters in good yields. The use of a chiral bidentate phosphoramidite ligand (Me-BIPAM) achieved excellent enantioselectivities.

  9. Enzymatic Polymerization of Furan-2,5-Dicarboxylic Acid-Based Furanic-Aliphatic Polyamides as Sustainable Alternatives to Polyphthalamides

    NARCIS (Netherlands)

    Jiang, Yi; Maniar, Dina; Woortman, Albert J. J.; van Ekenstein, Gert O. R. Alberda; Loos, Katja

    2015-01-01

    Furan-2,5-dicarboxylic acid (FDCA)-based furanic-aliphatic polyamides can be used as promising sustainable alternatives to polyphthalamides (semiaromatic polyamides) and be applied as high performance materials with great commercial interest. In this study, poly(octamethylene furanamide) (PA8F), an

  10. Selective preparation of terminal alkenes from aliphatic carboxylic acids by a palladium-catalysed decarbonylation-eliminiation reaction

    NARCIS (Netherlands)

    Notre, le J.E.L.; Scott, E.L.; Franssen, M.C.R.; Sanders, J.P.M.

    2010-01-01

    Trialkylamines were used as additives in the decarbonylation–elimination reaction catalysed by the combination of palladium(II) chloride and DPE-Phos. Aliphatic carboxylic acids were transformed at relatively low temperature into terminal alkenes in high yield and high selectivity, without the need

  11. STUDIES ON MISCIBILITY OF POLY (ε-CAPROLACTONE) AND ALIPHATIC POLYCARBONATE BLENDS AND DETERMINATION OF THEIR INTERACTION PARAMETER

    Institute of Scientific and Technical Information of China (English)

    CHEN Li; HUANG Yuhui; SONG Mo; CONG Guangmin

    1992-01-01

    In this paper the miscibility of poly (ε-caprolactone) (PCL) and aliphatic polycarbonate (AP C) is studied by using DSC. The results show that PCL and APC are miscible in all ranges of composition. The interaction parameter between the polymers is calculated from the melting point depression data. Using optical microscope, the shapes of the PCL spherulites in the blends are observed.

  12. A New Form of Triple-Stranded Helicate Found in Uranyl Complexes of Aliphatic α,ω-Dicarboxylates.

    Science.gov (United States)

    Thuéry, Pierre; Harrowfield, Jack

    2015-11-16

    The reaction of uranyl ions with azelaic or dodecanedioic acids under solvohydrothermal conditions leads to crystallization of anionic dinuclear cage compounds with [M(bipy/phen)3](2+) counterions (M = 3d-block cation), while the smaller suberic acid yields heterometallic metallacycles. Complexes with the longer aliphatic chains are the first triple-stranded helicates reported in actinide chemistry.

  13. Sources and distribution of aliphatic and polyaromatic hydrocarbons in coastal sediments from the Ushuaia Bay (Tierra del Fuego, Patagonia, Argentina).

    Science.gov (United States)

    Commendatore, Marta G; Nievas, Marina L; Amin, Oscar; Esteves, José L

    2012-03-01

    The environmental quality of Ushuaia Bay, located at the southernmost tip of South America, is affected by the anthropogenic pressure of Ushuaia city. In this study, levels and sources of hydrocarbons in coastal sediments were assessed. Aliphatic hydrocarbon fractions ranged between 5.5 and 1185.3 μg/g dry weight and PAHs from not detected to 360 ng/g. Aliphatic diagnostic indices, the nalkanes homologous series occurrence, Aliphatic Unresolved Complex Mixtures (AliUCMs), and pristane and phytane isoprenoids indicated a petrogenic input. Some sites showed biogenic features masked by the anthropogenic signature. Particularly in port areas biodegradation processes were evident. PAH ratios showed a mixture of petrogenic and pyrogenic sources. Aliphatic and aromatic UCMs were strongly correlated, reflecting chronic pollution. Three areas were distinguished inside the bay: (1) east, with low hydrocarbons impact; (2) central, where hydrocarbons accumulation was related to source proximity and sediment characteristics; (3) south-west, where sediment characteristics and current circulation favour hydrocarbons accumulation. Copyright © 2011 Elsevier Ltd. All rights reserved.

  14. Kinetics and mechanism of oxidation of aliphatic alcohols by tetrabutylammonium tribromide

    Indian Academy of Sciences (India)

    Manju Baghmar; Pradeep K Sharma

    2001-04-01

    Oxidation of nine primary aliphatic alcohols by tetrabutylammonium tribromide (TBATB) in aqueous acetic acid leads to the formation of the corresponding aldehydes. The reaction is first order with respect to TBATB. Michaelis-Menten type kinetics is observed with respect to alcohols. The reaction failed to induce the polymerization of acrylonitrile. Tetrabutylammonium chloride has no effect on the reaction rate. The proposed reactive oxidizing species is the tribromide ion. The oxidation of [1,1-2H2]ethanol exhibits a substantial kinetic isotope effect. The effect of solvent composition indicates that the rate increases with increase in the polarity of the solvent. The reaction is susceptible to both polar and steric effects of substituents. A mechanism involving transfer of a hydride ion in the ratedetermining step has been proposed.

  15. Aliphatic hydrocarbons in sediment cores from the southern basin of Lake Michigan

    Energy Technology Data Exchange (ETDEWEB)

    Doskey, P.V. [Argonne National Lab., IL (United States). Environmental Research Division; Andren, A.W. [Univ. of Wisconsin, Madison, WI (United States). Water Chemistry Program

    1991-10-01

    Aliphatic hydrocarbons in sediments of the southern basin of Lake Michigan have planktonic, terrigenous, and petroleum residue origins. Surficial sediments collected near the eastern shore in 60-80 m of water contained more petroleum residue and planktonic hydrocarbons and exhibited less terrigenous character than sediments collected from the deepest location in the basin. Petroleum residue inputs have increased since 1900 as evidenced by a change in the flux of an unresolved complex mixture (UCM) of hydrocarbons from 6 ng/cm{sup 2}{center_dot}yr to a flux of approximately 100 ng/cm{sup 2}{center_dot}yr in 1980. Sediment profiles of the UCM exhibited subsurface concentration maxima that may be due to reduced inputs of combustion products or feeding by oligochaetes. Profiles of n-C{sub l7} and pristane indicated that planktonic n-alkanes undergo degradation in the aerobic, mixed zone of the sediments.

  16. Vapour pressure and enthalpy of vaporization of aliphatic poly-amines

    Energy Technology Data Exchange (ETDEWEB)

    Efimova, Anastasia A.; Emel' yanenko, Vladimir N. [Department of Physical Chemistry, University of Rostock, Dr-Lorenz-Weg 1, D-18059 Rostock (Germany); Verevkin, Sergey P., E-mail: sergey.verevkin@uni-rostock.d [Department of Physical Chemistry, University of Rostock, Dr-Lorenz-Weg 1, D-18059 Rostock (Germany); Chernyak, Yury [Huntsman Corporation, Advanced Technology Center, 8600 Gosling Road, The Woodlands, 77381 TX (United States)

    2010-03-15

    Molar enthalpies of vaporization of aliphatic poly-amines: 1,4-dimethylpiperazine [106-58-1], 1-(2-aminoethyl)-piperazine, [140-31-8], 1-(2-aminoethyl)-4-methyl-piperazine [934-98-5], and triethylenetetramine [112-24-3] were obtained from the temperature dependence of the vapour pressure measured by the transpiration method. A large number of the primary experimental results on temperature dependences of vapour pressures of the parent compounds have been collected from the literature and have been treated uniformly in order to derive vaporization enthalpies of poly-amines at the reference temperature 298.15 K. An internal consistency check was performed on enthalpy of vaporization values for poly-amines studied in this work.

  17. Preparation and characterization of aliphatic diphenyl esters intended as precursors for polyesters

    DEFF Research Database (Denmark)

    Hvilsted, S.; Andruzzi, F.; Cerrai, P.

    1991-01-01

    An extensive number of aliphatic diphenyl esters, C6H5OOC(CH2)nCOOC6H5 (n = O,...,8,10,11,12,14), have been prepared in pure form. The crystalline melting points these esters exhibit an odd-even temperature behaviour, with the higher-melting even series (n even) displaying a minimum for n = 8 while...... based on similar data from phenyl esters, interpreted as the results of an apparent macrocyclic conformation of the larger diphenyl esters. High-performance size exclusion chromatography (s.e.c.) of diphenyl esters, phenyl esters, aromatic and linear hydrocarbons in tetrahydrofuran, toluene...... and chloroform points to specific phenyl ester-solvent interactions, which obscure a potential s.e.c. conformational analysis of the diphenyl esters....

  18. Oxidative aliphatic C-H fluorination with manganese catalysts and fluoride ion.

    Science.gov (United States)

    Liu, Wei; Huang, Xiongyi; Groves, John T

    2013-12-01

    Fluorination is a reaction that is useful in improving the chemical stability and changing the binding affinity of biologically active compounds. The protocol described here can be used to replace aliphatic, C(sp(3))-H hydrogen in small molecules with fluorine. Notably, isolated methylene groups and unactivated benzylic sites are accessible. The method uses readily available manganese porphyrin and manganese salen catalysts and various fluoride ion reagents, including silver fluoride (AgF), tetrabutylammonium fluoride and triethylamine trihydrofluoride (TREAT·HF), as the source of fluorine. Typically, the reactions afford 50-70% yield of mono-fluorinated products in one step. Two representative examples, the fragrance component celestolide and the nonsteroidal anti-inflammatory drug ibuprofen, are described; they produced useful isolated quantities (250-300 mg, ~50% yield) of fluorinated material over periods of 1-8 h. The procedures are performed in a typical fume hood using ordinary laboratory glassware. No special precautions to rigorously exclude water are required.

  19. Chemically responsive nanoporous pigments: colorimetric sensor arrays and the identification of aliphatic amines.

    Science.gov (United States)

    Bang, Jin Ho; Lim, Sung H; Park, Erwin; Suslick, Kenneth S

    2008-11-18

    A general method has been developed for the preparation of microspheres of nanoporous pigments, their formulation into chemically responsive pigment inks, and the printing of these inks as colorimetric sensor arrays. Using an ultrasonic-spray aerosol-gel synthesis from chemically responsive dyes and common silica precursors, 16 different nanoporous pigment microspheres have been prepared and characterized. New colorimetric sensor arrays have been created by printing inks of these chemically responsive pigments as primary sensor elements; these arrays have been successfully tested for the detection, identification, and quantitation of toxic aliphatic amines. Among 11 structurally similar amines, complete identification of each analyte without confusion was achieved using hierarchical cluster analysis (HCA). Furthermore, visual identification of ammonia gas was easily made at the IDLH (immediately dangerous to life or health), PEL (permissible exposure limits), and 0.1 PEL concentrations with high reproducibility.

  20. Catalytic activity of carbon nanotubes in the conversion of aliphatic alcohols

    Science.gov (United States)

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

    2016-06-01

    Carbon nanotubes (CNTs) obtained via the catalytic pyrolysis of hexane at 750°C were studied as the catalysts in conversion of C2-C4 alcohols. The efficiency of CNTs as catalysts in dehydration and dehydrogenation of ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and tert-butanol was studied by means of pulse microcatalysis. The surface and structural characteristics of CNTs are investigated via SEM, TEM, DTA, BET, and XPS. CNTs are shown to be effective catalysts in the conversion of alcohols and do not require additional oxidative treatment. The regularities of the conversion of aliphatic alcohols, related to the properties of the CNTs surface and the structure of the alcohols are identified.

  1. Electrochemical oxidation of aliphatic amines and their attachment to carbon and metal surfaces.

    Science.gov (United States)

    Adenier, Alain; Chehimi, Mohamed M; Gallardo, Iluminada; Pinson, Jean; Vilà, Neus

    2004-09-14

    The electrochemical oxidation of aliphatic amines (primary, secondary, and tertiary) has been investigated by cyclic voltammetry and preparative electrolysis. The oxidation mechanisms have been established, and the lifetimes of the radical cations have been measured for secondary and tertiary amines. These results have been put in parallel with the attachment of amines to glassy carbon, Au, and Pt electrodes by cyclic voltammetry, X-ray photoelectron spectroscopy (XPS), and infrared reflection-absorption spectroscopy (IRRAS). It is then possible to show that it is not the radical cation but the radical obtained after the deprotonation which reacts with the electrode surface. XPS results also point to the existence of a covalent bond between Au or Pt and the organic moiety.

  2. Development and Characterization of Novel Interpenetrating Network (IPN Foams from Epoxy Ester and Aliphatic Epoxy Resin

    Directory of Open Access Journals (Sweden)

    Kanuprasad Patel

    2009-01-01

    Full Text Available Diglycidyl ether of bisphenol-A (DGEBA was reacted with acrylate monomer at variable molar ratios. The reaction between glycerine and epichlorohydrine form glycidyl ether of polyol aliphatic epoxy resin. The resultant resins were characterized duly. Both the resins were mixed at different ratios with constant high shear stirring. The obtained mixture and suitable additives were heated at 150oC for one and half hour. The so called Interpenetrating Network (IPN transformed into foams. The performance of foams was evaluated by testing for compression in both parallel and perpendicular to rise direction. The tests were carried out at room temperature and at the elevated temperature. The compression properties showed a decreasing trend for increasing amounts of glycerine resin. The density and thermal properties of epoxy foams were also evaluated. The relation between the composition, density and properties of the foam was analyzed.

  3. Modification of nano-sized layered double hydroxides by long-chain organic aliphatic surfactants

    Directory of Open Access Journals (Sweden)

    RAMASAMY ANBARASAN

    2008-03-01

    Full Text Available The inter-layer anion of layered double hydroxides (LDH with a hydrotalcite (HT-like structure was ion-exchanged with various organic surfactants, particularly with long chain aliphatic surfactants. After the ion-exchange process, the basal spacing of the LDH was increased and the increase of the basal spacing depended on various factors, such as the intercalation capacity functionality and orientation capability of the surfactant. Of the employed surfactants, stearic acid intercalated LDH showed the highest increase of the basal spacing, which was confirmed by XRD analysis. FTIR results supported the interaction of the surfactants with the LDH. In addition, an increase in the thermal stability of the dodecanedioic acid intercalated HT was evidenced by the TGA method.

  4. In vitro antibacterial activity of some aliphatic aldehydes from Olea europaea L.

    Science.gov (United States)

    Bisignano, G; Laganà, M G; Trombetta, D; Arena, S; Nostro, A; Uccella, N; Mazzanti, G; Saija, A

    2001-04-20

    In the present paper we report the 'in vitro' activity of eight aliphatic long-chain aldehydes from olive flavor (hexanal, nonanal, (E)-2-hexenal, (E)-2-eptenal, (E)-2-octenal, (E)-2-nonenal, (E)-2-decenal and (E,E)-2,4-decadienal) against a number of standard and freshly isolated bacterial strains that may be causal agents of human intestinal and respiratory tract infections. The saturated aldehydes characterized in the present study do not exhibit significant antibacterial activity, while the alpha,beta-unsaturated aldehydes have a broad antimicrobial spectrum and show similar activity against Gram-positive and Gram-negative microorganisms. The effectiveness of the aldehydes under investigation seems to depend not only on the presence of the alpha,beta-double bond, but also on the chain length from the enal group and on the microorganism tested.

  5. Kinetics and mechanism of oxidation of aliphatic primary alcohols by quinolinium bromochromate

    Indian Academy of Sciences (India)

    Sonu Saraswat; Vinita Sharma; K K Banerji

    2003-02-01

    Oxidation of nine aliphatic primary alcohols by quinolinium bromochromate (QBC) in dimethylsulphoxide leads to the formation of the corresponding aldehydes. The reaction is first order with respect to both QBC and the alcohol. The reaction is catalysed by hydrogen ions. The hydrogen-ion dependence has the form: obs = + [H+]. The oxidation of [1,1-2H2]ethanol (MeCD2OH) exhibits a substantial primary kinetic isotope effect. The reaction has been studied in nineteen different organic solvents. The solvent effect was analysed using Taft’s and Swain's multiparametric equations. The rate of oxidation is susceptible to both polar and steric effects of the substituents. A suitable mechanism has been proposed.

  6. Recommended Correlations for the Surface Tension of Aliphatic, Carboxylic, and Polyfunctional Organic Acids

    Science.gov (United States)

    Mulero, A.; Cachadiña, I.; Sanjuán, E. L.

    2016-09-01

    In previous papers, we have proposed specific correlations to reproduce the surface tension values for several sets of fluids and for wide ranges of temperatures. In this paper, we focus our attention on organic fatty (aliphatic, carboxylic, and polyfunctional) acids. We have taken into account the available data and values in the DIPPR and DETHERM databases and also Wohlfarth and Wohlfarth's (1997) book. In some cases we have also considered new data published elsewhere. All the data and values have been carefully filtered and subsequently fitted with the use of the model currently implemented in NIST's REFPROP program, calculating two or four adjustable coefficients for each fluid. As a result, we propose recommended correlations for 99 acids, providing mean absolute percentage deviations below 1.6% in all cases.

  7. Propargyl-functional aliphatic polycarbonate obtained from carbon dioxide and glycidyl propargyl ether.

    Science.gov (United States)

    Hilf, Jeannette; Frey, Holger

    2013-09-01

    The synthesis of propargyl-functional poly(carbonate)s with different content of glycidyl propargyl ether (GPE) units is achieved via the copolymerization of propargyl glycidyl ether and carbon dioxide. A new type of functional poly(carbonate) synthesized directly from CO(2) and the glycidyl ether is obtained. The resulting polymers show moderate polydispersities in the range of 1.6-2.5 and molecular weights in the range of 7000-10 500 g mol(-1). The synthesized copolymers with varying number of alkyne functionalities and benzyl azide are used for the copper-catalyzed Huisgen-1,3-dipolar addition. Moreover, the presence of vicinal alkyne groups opens a general pathway to produce functional aliphatic poly(carbonate)s from a single polymer scaffold.

  8. Reaction Engineering of Biocatalytic Enantioselective Reduction: A Case Study for Aliphatic Ketones

    DEFF Research Database (Denmark)

    Leuchs, Susanne; Lima-Ramos, Joana; Greiner, Lasse

    2013-01-01

    Previously, it could be demonstrated, that the monophasic, enzymatic reduction of aliphatic 2-ketones into the corresponding (R)-2-alcohols is an adequate and viable method as carried out in a cascade of two enzyme–membrane reactors (Leuchs, S.; Na’amnieh, S. N.; Greiner, L. Green Chemistry 2013......, 15, 167–176.). In the present work, the process metrics of the ketone reduction were calculated. A cost analysis revealed that the enzyme costs are negligible, but the cost for nicotinamide cofactor NADP+ is dominating the overall cost of the chemical raw material followed by the ionic liquid (TEGO...... IL K5) used as solubiliser and the buffer. The overall cost of chemicals was €148/kgproduct. To assess the environmental impact of the process, the E-factor (kgwaste/kgproduct) 132 and the process mass intensity 133 (PMI, kgsubstrate/kgproduct) were calculated. A process model based on initial rate...

  9. Direct optical observation of the formation of some aliphatic alcohol radicals. A pulse radiolysis study

    Indian Academy of Sciences (India)

    E Janata

    2002-12-01

    The kinetics of the reactions of hydroxyl radicals and hydrogen atoms with some aliphatic alcohols in aqueous solutions were studied using pulse radiolysis. Based on the increase in optical absorption in the UV region, the rate constants for the reaction of hydroxyl radicals and hydrogen atoms with methanol, ethanol, 2-propanol or -butyl alcohol were determined to be 9.0 × 108, 2.2 × 109, 2.0 × 109, 6.2 × 108 and 1.1 × 106, 1.8 × 107, 5.3 × 107, 2.3 × 105 dm3 mol-1 s-1 respectively. The bimolecular decay rate constants for the alcohol radicals produced in methanol and ethanol were evaluated to be 2 .4 × 109 and 1.5 × 109 dm3 mol-1 s-1. The values observed are in fairly good agreement with those reported earlier.

  10. Supercritical fluid extraction of triterpenes and aliphatic hydrocarbons from olive tree derivatives

    Directory of Open Access Journals (Sweden)

    Aimen Issaoui

    2017-05-01

    Full Text Available Olive leaves and tree bark were extracted through supercritical fluid extraction (SFE and the chemical composition of the extracted mixture was determined by Gas Chromatography–Mass Spectrometry (GC–MS. Both samples contain a great number of triterpenes as squalene, which were used since 1997 as a main constituent of the flu vaccine (FLUAD, and the alpha-tocopherol the most biologically active form of vitamin E. We also underline the presence of many aliphatic compounds such nonacosane and heptacosane in low concentrations. The extractions were carried out at 313 and 333 K, at a pressure varying from 90 to 250 bars and using pure carbon dioxide in its supercritical phase. Therefore, their solubilities at equilibrium were numerically optimized via two assumptions and compared with the experimental values. Indeed, a good agreement between several results was shown.

  11. [Aliphatic characteristics of the fractions isolated from the soil fulvic acid using XAD-8 column].

    Science.gov (United States)

    Liu, Ben-ding; Li, Xia; Dai, Jing-yu

    2007-10-01

    In order to truly understand the character and structure of fulvic acid, which contains many substances, the authors isolated fulvic acid detailedly according to its definite character and its characteristic of similar structure. Fulvic acid with H+ can be adsorbed by the XAD-8 column balanced by the usual buffer(pH 2). The hydrophilic fraction in fulvic acid can be divided into three groups using the buffer with various pH (4.8, 7.0 and 11.0), while the hydrophobic fraction can be classified into two groups by the distilled water and alcohol separately. For FTIR (Fourier transform infrared) and NMR (nuclear magnetic resonance) spectroscopy analysis, three paddy soils were used. It may be concluded that the content of oxygen and carboxyl group dissolved at low pH is more than that dissolved in the water and alcohol, but the content of aliphatic fraction is less and has short side chain.

  12. Synthesis, characterization and antimicrobial studies of new bispyrazolines linked via 3-aryl ring with aliphatic chains

    Science.gov (United States)

    Yusuf, Mohamad; Jain, Payal

    2012-10-01

    The bispyrazolines 4a(a'-f') and 4b(a'-f') built around the aliphatic chains of varying lengths have been prepared by refluxing bischalcones 3a(a'-f') and 3b(a'-f') with phenyl hydrazine in alcoholic medium. The reactions of chalcones 2a and 2b with suitable 1,ω-dibromoalkanes in the presence of anhydrous K2CO3/dry acetone and Bu4N+I- (PTC) provided 3a(a'-f') and 3b(a'-f'), respectively. The antibacterial and antifungal activities of the synthesized compounds were evaluated against five bacterial and four fungal strains. The compounds 3ba', 3bc', 3bd', 3be', 3af', 4aa' and 4ba' showed better MIC (μg/mL) against the tested microorganisms.

  13. Aliphatic and aromatic plant biopolymer dynamics in soil particles isolated from sequential density fractionation

    Science.gov (United States)

    Caldwell, B.; Filley, T.; Sollins, P.; Lajtha, K.; Swanston, C.; Kleber, M.; Kramer, M.

    2007-12-01

    A recent multi-layer-based soil organic matter-mineral interaction mechanistic model to describe the nature of soil organic matter-mineral surface mechanism for soil organic matter stabilization predicts that proteinaceous and aliphatic materials establish the core of strong binding-interactions upon which other organic matter is layered. A key methodology providing data underpinning this hypothesis is sequential density fractionation where soil is partitioned into particles of increasing density with the assumption that a partial control on organic matter distribution through density series is the thickness of its layering. Four soils of varying mineralogy and texture were investigated for their biopolymer, isotopic, and mineralogical properties. Light fractions (cutin and suberin while heavier fractions, 1.8-2.6 g/cm3, exhibited a progressive decrease in concentration in plant derived biopolymers with density. Extractable lignin phenols exhibited a progressive oxidation state with density. The concentration of biopolymers roughly mirrored the C:N ratio of soil particles which dropped consistently with increasing particle density. Although, in all soils, both lignin phenols and SFA concentration generally decreased with increasing density the ratio SFA/lignin varied with density and depending upon the soil. All soils, except the oxisol, exhibited an increase in SFA with respect to lignin suggesting a selective stabilization of those material with respect to lignin. In the oxisol, which showed little variation in its hematite dominated mineralogy across density, SFA/lignin remained constant, potentially indicating a greater capacity to stabilize lignin in that system. Interestingly, the lignin oxidation state increased with density in the oxisol. Given the variation in soil character, the consistency in these trends it suggests a general phenomenon of progressive decay in plant derived material with thinness of mineral coating but an overall relative increase in

  14. Occurrence of selected aliphatic amines in source water of major cities in China

    Institute of Scientific and Technical Information of China (English)

    Haifeng Zhang; Shuoyi Ren; Jianwei Yu; Min Yang

    2012-01-01

    The formation of toxic nitrogenous disinfection byproducts (N-DBPs),such as nitrosamines,halonitromethanes and haloacetonitriles,from reactions between chlorine/chloramine and dissolved organic nitrogen in drinking water has caused great concern with regarding public health.This study revealed the occurrence of 17 aliphatic amines,some of which have been confirmed to be the precursors of N-DBPs,in source water across China.A sensitive method based on benzenesulfonyl chloride derivatization and liquid-liquid extraction followed by GC-MS analysis was established for the simultaneous analysis of the selected amines in aqueous samples.In total,37 source water samples from the capital cities of 20 provinces were collected for the survey.Among the 17 amines,14 were detected with an average frequency of detection of 36%.The most relevant amines in terms of frequency and maximum concentrations detected were dimethylamine (100%,24.82 μg/L),methylamine (78%,0.92 μg/L),N-methylethylamine (70%,8.84 μg/L),propylamine (59%,10.69 μg/L),diethylamine (54%,3.76 μg/L),N-methylbutylamine (35%,3.07 μg/L),N-ethylpropylamine (35%,0.52 μg/L),and piperidine (32%,2.35 μg/L).This is the first large scale survey of the aliphatic amines occurrence in source water in the world.The wide presence of nitrosamine precursors like dimethylamine,N-methylethylamine and diethylamine,and the precursors of haloacetonitriles and halonitromethanes like methylamine and propylamine suggests that better source water management is required to ensure the safety of drinking water.

  15. Seasonal variation of aliphatic amines in marine sub-micrometer particles at the Cape Verde islands

    Directory of Open Access Journals (Sweden)

    C. Müller

    2009-07-01

    Full Text Available Monomethylamine (MA, dimethylamine (DMA and diethylamine (DEA were detected at non-negligible concentrations in sub-micrometer particles at the Cap Verde Atmospheric Observatory (CVAO located on the island of São Vicente in Cape Verde during algal blooms in 2007. The concentrations of these amines in five stage impactor samples ranged from 0 to 30 pg m−3 for MA, 130 to 360 pg m−3 for DMA and 5 to 110 pg m−3 for DEA during the spring bloom in May 2007 and 2 to 520 pg m−3 for MA, 100 to 1400 pg m−3 for DMA, 90 to 760 pg m−3 for DEA during an unexpected winter algal bloom in December 2007. Anomalously high Saharan dust deposition and intensive ocean layer deepening were found at the Atmospheric Observatory and the associated Ocean Observatory during algal bloom periods. The highest amine concentrations in fine particles (impactor stage 2, 0.14–0.42 μm indicates that amines are likely taken up from the gas phase into the acidic sub-micrometer particles. The contribution of amines to the organic carbon (OC content ranged from 0.2 to 2.5%C in the winter months, indicating the importance of this class of compounds to the carbon cycle in the marine environment. Furthermore, aliphatic amines originating from marine biological sources likely contribute significantly to the organic nitrogen in the marine atmosphere. The average contribution of the amines to the total detected nitrogen content in submicron particles can be non-negligible, especially in the winter months (0.1% N to 1.5% N in the sum of nitrate, ammonium and amines. This indicates that these smaller aliphatic amines can be important for the carbon and the nitrogen cycles in the remote marine environment.

  16. Analysis of aliphatic carboxylic acids in anaerobic digestion process waters by ion-exclusion chromatography

    Institute of Scientific and Technical Information of China (English)

    Kazuaki ITO; Kazuhiko TANAKA; Jun SAKAMOTO; Kazuya NAGAOKA; Yohichi TAKAYAMA; Takashi KANAHORI; Hiroshi SUNAHARA; Tsuneo HAYASHI; Shinji SATO; Takeshi HIROKAWA

    2012-01-01

    The analysis of seven aliphatic carboxylic acids ( formic,acetic,propionic,iso-butyric,n-butyric,iso-valeric and n-valeric acid) in anaerobic digestion process waters for biogas production was examined by ion-exclusion chromatography with dilute acidic eluents (benzoic acid,perfluorobutyric acid (PFBA) and sulfuric acid) and non-suppressed conductivity/ultraviolet (UV) detection.The columns used were a styrene/divinylbenzene-based strongly acidic cation-exchange resin column ( TSKgel SCX) and a polymethacrylate-based weakly acidic cation-exchange resin column ( TSKgel Super IC-A/C ).Good separation was performed on the TSKgel SCX in shorter retention times.For the TSKgel Super IC-A/C,peak shape of the acids was sharp and symmetrical in spite of longer retention times.In addition,the mutual separation of the acids was good except for iso- and n-butyric acids.The better separation and good detection was achieved by using the two columns (TSKgel SCX and TSKgel Super IC-A/C connected in series),lower concentrations of PFBA and sulfuric acid as eluents,non-suppressed conductivity detection and UV detection at 210 nm.This analysis was applied to anaerobic digestion process waters.The chromatograms with conductivity detection were relatively simpler compared with those of UV detection.The use of two columns with different selectivities for the aliphatic carboxylic acids and the two detection modes was effective for the determination and identification of the analytes in anaerobic digestion process waters containing complex matrices.

  17. Seasonal variation of aliphatic amines in marine sub-micrometer particles at the Cape Verde islands

    Science.gov (United States)

    Müller, C.; Iinuma, Y.; Karstensen, J.; van Pinxteren, D.; Lehmann, S.; Gnauk, T.; Herrmann, H.

    2009-12-01

    Monomethylamine (MA), dimethylamine (DMA) and diethylamine (DEA) were detected at non-negligible concentrations in sub-micrometer particles at the Cap Verde Atmospheric Observatory (CVAO) located on the island of São Vicente in Cape Verde during algal blooms in 2007. The concentrations of these amines in five stage impactor samples ranged from 0-30 pg m-3 for MA, 130-360 pg m-3 for DMA and 5-110 pg m-3 for DEA during the spring bloom in May 2007 and 2-520 pg m-3 for MA, 100-1400 pg m-3 for DMA and 90-760 pg m-3 for DEA during an unexpected winter algal bloom in December 2007. Anomalously high Saharan dust deposition and intensive ocean layer deepening were found at the Atmospheric Observatory and the associated Ocean Observatory during algal bloom periods. The highest amine concentrations in fine particles (impactor stage 2, 0.14-0.42 μm) indicate that amines are likely taken up from the gas phase into the acidic sub-micrometer particles. The contribution of amines to the organic carbon (OC) content ranged from 0.2-2.5% C in the winter months, indicating the importance of this class of compounds to the carbon cycle in the marine environment. Furthermore, aliphatic amines originating from marine biological sources likely contribute significantly to the nitrogen content in the marine atmosphere. The average contribution of the amines to the detected nitrogen species in sub-micrometer particles can be non-negligible, especially in the winter months (0.1% N-1.5% N in the sum of nitrate, ammonium and amines). This indicates that these smaller aliphatic amines can be important for the carbon and the nitrogen cycles in the remote marine environment.

  18. Analysis of aliphatic waxes associated with root periderm or exodermis from eleven plant species.

    Science.gov (United States)

    Kosma, Dylan K; Rice, Adam; Pollard, Mike

    2015-09-01

    Aliphatic waxes can be found in association with suberized tissues, including roots. Non-polar lipids were isolated by rapid solvent extraction of mature regions of intact roots from eleven angiosperms, including both monocots and dicots. The majority of roots analyzed were taproots or tuberous taproots that had undergone secondary growth and thus were covered by a suberized periderm. The exceptions therein were maize (Zea mays L.) and rice (Oryza sativa L.), which present a suberized exodermis. The analysis herein focused on aliphatic waxes, with particular emphasis on alkyl hydroxycinnamates (AHCs). AHCs were widely distributed, absent from only one species, were found in both aerial and subterranean portions of tuberous taproots, and were associated with the fibrous roots of both maize and rice. Most species also contained monoacylglycerols, fatty alcohols and/or free fatty acids. Carrot (Daucus carrota L.) was the outlier, containing only free fatty acids, sterols, and polyacetylenes as identified components. Sterols were the only ubiquitous component across all roots analyzed. Monoacylglycerols of ω-hydroxy fatty acids were present in maize and rice root waxes. For species within the Brassiceae, wax compositions varied between subspecies or varieties and between aerial and subterranean portions of taproots. In addition, reduced forms of photo-oxidation products of ω-hydroxy oleate and its corresponding dicarboxylic acid (10,18-dihydroxy-octadec-8-enoate, 9,18-dihydroxy-octadec-10-enoate and 9-hydroxyoctadec-10-ene-1,18-dioate) were identified as naturally occurring suberin monomers in rutabaga (Brassica napus subsp. rapifera Metzg.) periderm tissues.

  19. Effects of aliphatic aldehydes on the growth and patulin production of Penicillium expansum in apple juice.

    Science.gov (United States)

    Taguchi, Tomoyasu; Kozutsumi, Daisuke; Nakamura, Ruka; Sato, Yoshio; Ishihara, Atsushi; Nakajima, Hiromitsu

    2013-01-01

    The effects of 16 aliphatic aldehydes with 3-10 carbons on the growth and patulin production of Penicillium expansum were examined. When P. expansum spores were inoculated into apple juice broth, some alkenals, including 2-propenal, (E)-2-butenal, (E)-2-pentenal, and (E)-2-hexenal, inhibited fungal growth and patulin production. Their minimal inhibitory concentrations were 5, 50, 80, and 80 µg/mL respectively. Vital staining indicated that these alkenals killed mycelia within 4 h. Treatment of the spores with these aldehydes also resulted in rapid loss of germination ability, within 0.5-2 d. On the other hand, aliphatic aldehydes with 8-10 carbons significantly enhanced patulin production without affecting fungal growth: 300 µg/mL of octanal and 100 µg/mL of (E)-2-octenal increased the patulin concentrations in the culture broth by as much as 8.6- and 7.8-fold as compared to that of the control culture respectively. The expression of the genes involved in patulin biosynthesis in P. expansum was investigated in mycelia cultured in apple juice broth containing 300 µg/mL of octanal for 3.5, 5, and 7 d. Transcription of the msas gene, encoding 6-methylsalicylic acid synthase, which catalyzed the first step in the patulin biosynthetic pathway was remarkably high in the 3.5-d and 5-d-old cultures as compared with the control. However, octanal did not any increase the transcription of the msas in the 7-d-old culture or that of the other two genes, IDH and the peab1, in culture. Thus the enhanced patulin accumulation with supplementation with these aldehydes is attributable to the increased amount of the msas transcript.

  20. Synthesis and physicochemical properties of propylene glycol methyl ether palm oil monoester%棕榈油丙二醇甲醚酯生物柴油合成及理化性能试验研究

    Institute of Scientific and Technical Information of China (English)

    王文国; 王煊军; 郭和军; 张剑

    2011-01-01

    以丙二醇甲醚和精制棕榈油为原料,以金属钠为催化剂合成了一种新型生物柴油.即棕榈油丙二醇甲醚酯.通过正交试验设计获得了目标产物的最佳合成条件:醇(丙二醇甲醚)油摩尔比10:1,催化剂用量(占棕榈油质量)1.2%,反应温度90℃,反应时间2 h.在最佳合成条件下所得目标产物产率高达91.3%.利用红外光谱及氢核磁共振分析仪对产物进行了结构表征与化学结构分析,表明目标产物的化学结构与预测结果一致.理化性能试验表明,生物柴油的主要性能指标和我国0柴油较为接近,完全可以满足柴油发动机的使用要求.%A new biodiesel of propylene glycol methyl ether palm oil monoester(PGMEPOM) was synthesized with propylene glycol methyl ether and palm oil as reagents and sodium as a catalyst. The optimum conditions were determined by orthogonal as follows: molar ratio of propylene glycol methyl ether to palm oil 10:1, sodium dose 1.2%, reaction temperature 90℃ and reaction time 2 h. The productive rate of ester reached 91.3% under these conditions. In addition,the FT- IR and 1H NMR analysis showed that the chemical structure of PGMEPOM was consistent with the forecasting result. The main properties of PGMEPOM closed to that of 0# diesel, which proved that the PGMEPOM could meet the demands of diesel engine.

  1. Polycyclic Aromatic Hydrocarbons with Aliphatic Sidegroups: Intensity Scaling for the C–H Stretching Modes and Astrophysical Implications

    Science.gov (United States)

    Yang, X. J.; Li, Aigen; Glaser, R.; Zhong, J. X.

    2017-03-01

    The so-called unidentified infrared emission (UIE) features at 3.3, 6.2, 7.7, 8.6, and 11.3 μ {{m}} ubiquitously seen in a wide variety of astrophysical regions are generally attributed to polycyclic aromatic hydrocarbon (PAH) molecules. Astronomical PAHs may have an aliphatic component, as revealed by the detection in many UIE sources of the aliphatic C–H stretching feature at 3.4 μ {{m}}. The ratio of the observed intensity of the 3.4 μ {{m}} feature to that of the 3.3 μ {{m}} aromatic C–H feature allows one to estimate the aliphatic fraction of the UIE carriers. This requires knowledge of the intrinsic oscillator strengths of the 3.3 μ {{m}} aromatic C–H stretch ({A}3.3) and the 3.4 μ {{m}} aliphatic C–H stretch ({A}3.4). Lacking experimental data on {A}3.3 and {A}3.4 for the UIE candidate materials, one often has to rely on quantum-chemical computations. Although the second-order Møller–Plesset (MP2) perturbation theory with a large basis set is more accurate than the B3LYP density functional theory, MP2 is computationally very demanding and impractical for large molecules. Based on methylated PAHs, we show here that, by scaling the band strengths computed at an inexpensive level (e.g., B3LYP/6-31G*), we are able to obtain band strengths as accurate as those computed at far more expensive levels (e.g., MP2/6-311+G(3df,3pd)). We calculate the model spectra of methylated PAHs and their cations excited by starlight of different spectral shapes and intensities. We find that {({I}3.4/{I}3.3)}{mod}, the ratio of the model intensity of the 3.4 μ {{m}} feature to that of the 3.3 μ {{m}} feature, is insensitive to the spectral shape and intensity of the exciting starlight. We derive a straightforward relation for determining the aliphatic fraction of the UIE carriers (i.e., the ratio of the number of C atoms in aliphatic units {N}{{C},{ali}} to that in aromatic rings {N}{{C},{aro}}) from the observed band ratios {({I}3.4/{I}3.3)}{obs}: {N

  2. Application of Topology Index in Aliphatic Aldehydes,Fatty Amines and Aliphatic Hydrocarbons Boiling Point%拓扑指数在脂肪醛、脂肪胺及脂肪烃沸点中的应用

    Institute of Scientific and Technical Information of China (English)

    周长会; 吴启勋; 侯庆高; 高宴梓; 李洪囡; 张瑞

    2013-01-01

    Two matrices and a topological index W were defined,then,topological index W was put into nonlinear regression with the boiling point of aliphatic aldehydes, fatty amines and aliphatic hydrocarbons, respectively, and with good results,the correlation coefficient reaches a good level. The established topological index and two kinds of matrix are easy and convenient to use, which can quickly predict the boiling point of the molecule.%定义了两种矩阵和一种拓扑指数W,将拓扑指数W分别与脂肪醛、脂肪胺及脂肪烃的沸点进行非线性回归,取得了较好的结果,相关性系数达到了良好级别.建立的拓扑指数和两种矩阵简洁方便,可以快速预测分子的沸点.

  3. Green Aza-Michael Reaction of Aliphatic Amines to á,(a)-Unsaturated Compounds in Water

    Institute of Scientific and Technical Information of China (English)

    XU Li-Wen; XIA Chun-Gu

    2004-01-01

    The hydroamination of olefins is a long-standing goal for transition metal catalysis. And the metal-catalyzed addition of amines to carbon-carbon double bonds is an unsolved, synthetically important problem. Although recent advances have made using lanthanide and precious metal complexes, there are few excellent catalyst that display broad functional group tolerance and useful rates for an intermolecular aza-Michael addition. As such, the development of efficient synthetic methods leading to a-amino carbonyl compounds and derivatives has attracted much attention in organic synthesis. Although recent advances have made this route more attractive, development of cheaper, simpler, and more efficient metal catalyst is highly desirable. We also have been interested in developing a reaction that uses catalytic quantities of minimally toxic, readily available, economic reagent should greatly contribute to the creation of environmental benign processes.The recent interest in aqueous medium metal-mediated carbon-carbon and carbon-heteroatom and formations led to the contributors for such reactions. Furthermore, development of organic reactions in water will contribute to the progress of green and quasi-nature catalysis chemistry. Surprisingly however, there is few report on conjugate additions of amines to a,a-unsaturated carbonyl compounds in water.Herein, we report a new protocol that employs air stable copper salts as efficient catalyst in the aza-Michael reaction under mild reaction conditions. Advantages of the protocol include high-yielding reactions that can be conducted at ambient temperature; the use of readily available and stable copper salts as the catalyst, and the reaction was successfully performed in environmental benign solvent, water.Finally, we have utilized a variety of aliphatic amines successfully with different á,(a)-unsaturated compounds catalyzed by simple hydrophilic ionic liquid, bmimBF4 in water. Interestingly, all the aliphatic amines gave

  4. Seasonal variation of aliphatic amines in marine sub-micrometer particles at the Cape Verde islands

    Directory of Open Access Journals (Sweden)

    H. Herrmann

    2009-12-01

    Full Text Available Monomethylamine (MA, dimethylamine (DMA and diethylamine (DEA were detected at non-negligible concentrations in sub-micrometer particles at the Cap Verde Atmospheric Observatory (CVAO located on the island of São Vicente in Cape Verde during algal blooms in 2007. The concentrations of these amines in five stage impactor samples ranged from 0–30 pg m−3 for MA, 130–360 pg m−3 for DMA and 5–110 pg m−3 for DEA during the spring bloom in May 2007 and 2–520 pg m−3 for MA, 100–1400 pg m−3 for DMA and 90–760 pg m−3 for DEA during an unexpected winter algal bloom in December 2007. Anomalously high Saharan dust deposition and intensive ocean layer deepening were found at the Atmospheric Observatory and the associated Ocean Observatory during algal bloom periods. The highest amine concentrations in fine particles (impactor stage 2, 0.14–0.42 μm indicate that amines are likely taken up from the gas phase into the acidic sub-micrometer particles. The contribution of amines to the organic carbon (OC content ranged from 0.2–2.5% C in the winter months, indicating the importance of this class of compounds to the carbon cycle in the marine environment. Furthermore, aliphatic amines originating from marine biological sources likely contribute significantly to the nitrogen content in the marine atmosphere. The average contribution of the amines to the detected nitrogen species in sub-micrometer particles can be non-negligible, especially in the winter months (0.1% N–1.5% N in the sum of nitrate, ammonium and amines. This indicates that these smaller aliphatic amines can be important for the carbon and the nitrogen cycles in the remote marine environment.

  5. Source apportionment of sediment-associated aliphatic hydrocarbon in a eutrophicated shallow lake, China.

    Science.gov (United States)

    Wang, Ji-Zhong; Yang, Ze-Yu; Chen, Tian-Hu

    2012-11-01

    Chaohu Lake, one of the most eutrophicated lakes in China, has been suffering from long-term outside pollution, urban sewage, river outflows, and agricultural runoff which expectedly have been the main contributors of hydrocarbons. However, the contributions from these various sources have not been specified. The present study is aimed at identifying the potential sources of hydrocarbons in surface sediment around the whole lake and assessing the relative contributions using principal components analysis-multiple linear regression (PCA-MLR). Sixty-one surface sediments covering the whole Chaohu Lake and three main estuaries of inflowing rivers were collected, dried, extracted, and analyzed for 27 normal alkanes (n-alkanes, from C(12) to C(38), defined Σ(27)AH) and unresolved complex mixture (UCM) by GC/MS. Diagnostic ratios and PCA-MLR were utilized to apportion their sources. The concentrations of Σ(27)AH and UCM ranged from 434 to 3,870 ng/g and 11.9 to 325 μg/g dry weight, respectively, for all samples. The concentrations of Σ(27)AH in western region and estuary of Nanfei River were slightly higher but without statistical significance than those from eastern region and estuaries of Yuxi River and Hangbu River. The concentration of UCM from western region was significantly higher than that obtained from eastern region. These results reflect the importance of input of urban runoff by Nanfei River and serious eutrophication in western region. Aliphatic hydrocarbons in Chaohu Lake were mainly derived from high plant wax with mixed sources of phytoplankton and petroleum. Weak microbial decomposition of n-alkanes would be expected to occur from the low ratios of isoprenoid hydrocarbons pristine (pri) and phytane (phy) to n-C(17) and n-C(18), respectively. Higher plant, fossil combustion, petroleum residue, and phytoplankton were proposed as the main origines of aliphatic hydrocarbons by PCA while the contributions of individual n-alkane homologues, pri and phy

  6. Scientific Opinion on Flavouring Group Evaluation 86, Revision 2 (FGE.86Rev2: Consideration of aliphatic and arylalkyl amines and amides evaluated by JECFA (65th meeting

    Directory of Open Access Journals (Sweden)

    EFSA Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids (CEF

    2015-01-01

    Full Text Available The Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids of the European Food Safety Authority was requested to consider evaluations of flavouring substances assessed since 2000 by the Joint FAO/WHO Expert Committee on Food Additives (JECFA, and to decide whether further evaluation is necessary, as laid down in Commission Regulation (EC No 1565/2000. The present consideration concerns a group of 30 aliphatic and arylalkyl amines and amides evaluated by JECFA at the 65th meeting in 2005. This revision is required owing to additional available toxicity data on piperine [FL-no: 14.003] and deca-(2E,4E-dienoic acid isobutyl-amide [FL-no: 16.091]. The substances were evaluated through a stepwise approach that integrates information on structure-activity relationships, intake from current uses, toxicological thresholds of concern and available data on metabolism and toxicity. The Panel agrees with JECFA’s conclusion “No safety concern at estimated levels of intake as flavouring substances” based on the Maximised Survey-derived Daily Intake (MSDI approach for all substances considered in this FGE. Besides the safety assessment of these flavouring substances, the specifications for the materials of commerce have also been considered and for all 30 substances, the information is adequate.

  7. Thermotropic liquid crystalline polyesters derived from bis-(4-hydroxybenzoyloxy)-2-methyl-1,4-benzene and aliphatic dicarboxylic acid chlorides

    Indian Academy of Sciences (India)

    Khudbudin Mulani; Mohasin Momin; Nitin Ganjave; Nayaku Chavan

    2015-09-01

    A series of thermotropic liquid crystalline polyesters derived from bis-(4-hydroxybenzoyloxy)-2-methyl-1,4-benzene (BHBOMB) and aliphatic dicarboxylic acid chlorides were investigated. All these polyesters were synthesized by interfacial polycondensation method and characterized by differential scanning calorimetry and wide-angle X-ray diffractometer. These polyesters consist of BHBOMB as a mesogenic diol and aliphatic diacid chlorides were used as flexible spacers. The length of oligomethylene units in polymer was varied from the trimethylene to the dodecamethylene groups. The transition temperatures and thermodynamic properties were studied for all these polymers. All these polyesters were soluble in chlorinated solvents such as chloroform, dichloromethane, dichloroethane, etc. More importantly, all these polyesters exhibited very large mesophase stability.

  8. Aliphatic and polycyclic aromatic hydrocarbons in the surface sediments of the Mediterranean: assessment and source recognition of petroleum hydrocarbons.

    Science.gov (United States)

    El Nemr, Ahmed; El-Sadaawy, Manal M; Khaled, Azza; Draz, Suzanne O

    2013-06-01

    Coastal marine sediment samples were collected from ten sampling stations along the Egyptian Mediterranean coast in April 2010. All sediment samples were analyzed for aliphatic (C7 to C34) and polycyclic aromatic hydrocarbons (PAHs) as well as total organic carbon (TOC) contents and grain size analysis. Total aliphatic hydrocarbons ranged from 1621.82 to 9069.99 ng/g (dry weight), while aromatic hydrocarbons (16 PAHs) varied between 208.69 and 1020.02 ng/g with an average of 530.68 ± 225.86 ng/g dwt. Good correlations observed between certain PAH concentrations allowed to identify its origin. The average TOC percent was varied from 0.13 to 1.46 %. Principal component analysis was used to determine the sources of hydrocarbon pollutants in sediments of Mediterranean. Additionally, special PAHs compound ratios suggest the petrogenic origins.

  9. Oxidation of aliphatic alcohols by triethylammonium chlorochromate in non-aqueous medium – A kinetic and mechanistic study

    Directory of Open Access Journals (Sweden)

    S. Sheik Mansoor

    2014-07-01

    Full Text Available The oxidation of some aliphatic alcohols by triethylammonium chlorochromate (TriEACC in dimethyl sulfoxide leads to the formation of the corresponding carbonyl compounds. The reaction is first order with respect to TriEACC. The reaction exhibited Michaelis–Menten type kinetics with respect to alcohol. The reaction is catalyzed by hydrogen ions. The hydrogen-ion dependence has the form: kobs = a + b[H+]. The oxidation of [1,1-2H2] ethanol (MeCD2OH exhibits a substantial primary kinetic isotope effect. Oxidation of aliphatic alcohol was studied in 19 different organic solvents. The solvent effect has been analysed using Kamlet’s and Swain’s multi-parametric equation. A suitable mechanism has been proposed.

  10. Syntheses of Enantiopure Aliphatic Secondary Alcohols and Acetates by Bioresolution with Lipase B from Candida antarctica

    Directory of Open Access Journals (Sweden)

    Richele P. Severino

    2012-07-01

    Full Text Available The lipase B from Candida antarctica (Novozym 435®, CALB efficiently catalyzed the kinetic resolution of some aliphatic secondary alcohols: (±-4-methylpentan-2-ol (1, (±-5-methylhexan-2-ol (3, (±-octan-2-ol (4, (±-heptan-3-ol (5 and (±-oct-1-en-3-ol (6. The lipase showed excellent enantioselectivities in the transesterifications of racemic aliphatic secondary alcohols producing the enantiopure alcohols (>99% ee and acetates (>99% ee with good yields. Kinetic resolution of rac-alcohols was successfully achieved with CALB lipase using simple conditions, vinyl acetate as acylating agent, and hexane as non-polar solvent.

  11. Aliphatic acid-conjugated antimicrobial peptides--potential agents with anti-tumor, multidrug resistance-reversing activity and enhanced stability.

    Science.gov (United States)

    Deng, Xin; Qiu, Qianqian; Ma, Ke; Wang, Xuekun; Huang, Wenlong; Qian, Hai

    2015-07-28

    Compared with traditional therapeutics, antimicrobial peptides as novel anti-tumor agents have prominent advantages of higher specificity and circumvention of multi-drug resistance. In a previous study, we found that B1, an antimicrobial peptide derived from Cathelicidin-BF15, presented specific anti-tumor activity against several tumor cells. Since aliphatic chain-conjugated peptides have shown ameliorative activity and stability, we conjugated aliphatic acids with different lengths to the amino terminal of B1. All the conjugated peptides exhibited improved anti-tumor activity over B1. Further investigations revealed that the peptides were capable of disrupting the cell membrane, stimulating cytochrome c release into the cytosol, which results in apoptosis. The peptides also acted against multidrug resistant cells and had multidrug resistance-reversing effects. Additionally, conjugation of aliphatic acid enhanced the peptide stability in plasma. In summary, aliphatic acid-modified peptides might be promising anti-tumor agents in the future.

  12. Distribution and sources of aliphatic hydrocarbons and fatty acids in surface sediments of a tropical estuary south west coast of India (Cochin estuary)

    Digital Repository Service at National Institute of Oceanography (India)

    Gireeshkumar, T.R.; Deepulal, P.M.; Chandramohanakumar, N.

    Surface sediments samples from the Cochin estuary were measured for elemental, stable isotopic and molecular biomarkers (aliphatic hydrocarbons and fatty acids) to study the sources and distribution of sedimentary organic matter. Concentrations...

  13. Aliphatic C-H bond oxidation of toluene using copper peroxo complexes that are stable at room temperature.

    Science.gov (United States)

    Würtele, Christian; Sander, Ole; Lutz, Volker; Waitz, Thomas; Tuczek, Felix; Schindler, Siegfried

    2009-06-10

    Dinuclear copper peroxo complexes obtained from mononuclear copper(I) complexes showed extremely high stabilities under ambient conditions in the solid state and could be heated above 100 degrees C without decomposition. The increased stability could be explained with regard to their molecular structures. Furthermore, the four complexes investigated showed a high potential for aliphatic C-H bond oxidations: for example, technical-grade toluene was oxidized to benzaldehyde in yields of up to 20%.

  14. Composition and sources of aliphatic lipids and sterols in sediments of a tropical island, southern South China Sea: preliminary assessment.

    Science.gov (United States)

    Mohd Tahir, N; Pang, S Y; Abdullah, N A; Suratman, S

    2013-12-01

    Near-shore surface sediment was collected from five stations off Redang Island located on the eastern coast of Peninsular Malaysia. Freeze-dried sediments were Soxhlet extracted and then fractionated using column chromatography into aliphatic and polar fractions. Determination of these fractions was carried out using gas chromatography mass spectrometry. The concentration of total resolved aliphatic hydrocarbons in sediments ranged from 157 to 308 ng/g. The distribution of aliphatic fraction showed the presence of n-alkanes ranging from nC15 to nC33 with a minor odd-to-even predominance exhibiting carbon maximum, depending on station, at nC17, nC26, nC29 or nC31. Calculation of Carbon Preference Index (CPI) for CPI(15-33) gave values ranging from 1.09 to 1.46. n-Alkanol in all sediment exhibits even-to-odd carbon predominance ranging from nC16 to nC28 and maximising at nC22. n-Fatty acids distribution ranged from nC14 to nC24 with a dominant maximum at nC16 and exhibiting high values of short chain fatty acids (≤nC20) to long chain fatty acids (>nC20) ratios. Unsaturated fatty acids, particularly nC16:1 and nC18:1 is also ubiquitous in all samples. Cholesterol is the most abundant compound amongst the sterol group ranging from 42.8 to 62.6% of the total sterols. β-Sitosterol, brassicasterol and stigmasterol, are also present but of relatively lower amount. These observations suggest that the aliphatic lipids and sterols in the study area originate, mainly, from biogenic sources of marine microbial with minor contribution from epiticular waxes of terrestrial plants.

  15. Continuous-flow synthesis of primary amines: Metal-free reduction of aliphatic and aromatic nitro derivatives with trichlorosilane

    Directory of Open Access Journals (Sweden)

    Riccardo Porta

    2016-12-01

    Full Text Available The metal-free reduction of nitro compounds to amines mediated by trichlorosilane was successfully performed for the first time under continuous-flow conditions. Aromatic as well as aliphatic nitro derivatives were converted to the corresponding primary amines in high yields and very short reaction times with no need for purification. The methodology was also extended to the synthesis of two synthetically relevant intermediates (precursors of baclofen and boscalid.

  16. Synthesis and properties of novel aliphatic polycarbonate from carbon dioxide with 1,2-butylene oxide and ε-caprolactone

    Institute of Scientific and Technical Information of China (English)

    Yan Fei Liu; Ke Long Huang; Dong Ming Peng; Su Qin Liu; Hong Wu

    2007-01-01

    A new degradable aliphatic poly(butylene-co-ε-caprolactone carbonate) (PBCL) was synthesized through the terpolymerization of carbon dioxide, 1,2-butylene oxide (BO) and ε-caprolactone (CL), a polymer supported bimetallic complex (PBM) was used as a catalyst. The terpolymers prepared were characterized by FT-IR, 1H NMR, 13C NMR, WXRD and DSC. The hydrolysis tests were carried out to appraise the degradability of the copolymers.

  17. A Novel Guided Bone Regeneration Membrane Composed of Nano-hydroxyapatite and Aliphatic Polyester-amide

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    Hydrothermally synthesized nano-hydroxyapatite ( n-HA ) varing in weight from 10% to 30%was used as filler to make guided bone regeneration (GBR) composite membranes with novel aliphatic polyesteramide (PEA). The structure and properties of PEA and its n- HA composites were investigated through TEM, IR,XRD , SEM and EDX. The shape and size of the n-HA crystals are similar to the apatite crystals in natural bone.Molecule interactions are present between the n- HA and PEA in the composite, which allows the uniform dispersion of n- HA in PEA matrix. This contributes enhanced mechanical property and bioactivity to the composite. The cytocompatibility of the composites has been investigated by culturing osteoblasts on the membranes. Good cell attachment and proliferation manner were observed on the membranes after 1 week. These results suggest that the PEA/n- HA composite membrane prepared in this study may serve as barrier membranes for guided bone regeneration and potential candidate scaffold for tissue engineering.

  18. Relations between aliphatics and silicate components in 12 stratospheric particles deduced from vibrational spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Merouane, S.; Djouadi, Z.; Le Sergeant d' Hendecourt, L., E-mail: sihane.merouane@ias.u-psud.fr [Institut d' Astrophysique Spatiale, CNRS, UMR-8617, Université Paris Sud, Bâtiment 121, F-91405 Orsay Cedex (France)

    2014-01-10

    Interplanetary dust particles (IDPs) are among the most pristine extraterrestrial samples available in the laboratory for analyses with moderate to high spatial- and spectral-resolution spectroscopic techniques. Their composition can provide precious information on the early stages of the solar nebula as well as on the processes on the surfaces of different small bodies in the solar system from which IDPs originate. In this work, we have analyzed six anhydrous IDPs and six stratospheric particles possibly of cosmic origin through infrared (IR) and Raman micro-spectroscopy to study and investigate their silicate and organic components. We find that the length/ramification of the aliphatic organics given by the CH{sub 2}/CH{sub 3} ratios in the IDPs is closely linked to the silicate family (pyroxene or olivine) present in the samples. Both IR and Raman data suggest that this relation is not correlated with either aqueous (as evidenced by the absence of aqueous related minerals) or thermal processes (as deduced from Raman measurements). Therefore, this observation might be related to the initial path of formation of the organics on the silicate surfaces, thus tracing a possible catalytic role that silicates would play in the formation and/or ramification of organic matter in the primitive nebula.

  19. The use of DNA technologies in determining the biotreatability of chlorinated aliphatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Douglas, A. [HydroQual, Calgary, AB (Canada)

    2008-07-01

    HydroQual Laboratories is a wholly-owned subsidiary of Golder Associates and uses biological testing for measuring the effect of toxins and their impact on various links in the food chain in order to evaluate and improve environmental health. It has expertise in various fields of the natural sciences and is ISO certified. This presentation discussed the use of DNA technologies in determining the biotreatability of chlorinated aliphatic hydrocarbons. The paper presented biotreatability studies run by the company which included bench scale testing on various types of contaminants. The testing involved multiple treatments, determination of dosage, and additional amendments. The strategy may vary based on bench test results and legislation. Trichloroethylene/perchloroethylene remediation strategies were also presented for chemical oxidation; aerobic bioremediation; abiotic remediation; and anaerobic biostimulation and augmentation. Biostimulation was defined as the addition of nutrients to influence the redox potential. The presentation also reviewed anaerobic dehalorespiration; detection methods; DNA isolation; polymerase chain reaction (PCR); and biotreatability case studies. The presentation concluded with some future directions and other uses of PCR. tabs., figs.

  20. Secondary organic aerosol formation from primary aliphatic amines with NO3 radical

    Directory of Open Access Journals (Sweden)

    M. E. Erupe

    2008-07-01

    Full Text Available Primary aliphatic amines are an important class of nitrogen containing compounds found to be emitted from automobiles, waste treatment facilities and agricultural animal operations. A series of experiments conducted at the UC-Riverside/CE-CERT Environmental Chamber is presented in which oxidation of methylamine, ethylamine, propylamine, and butylamine with NO3 has been investigated. Very little aerosol formation is observed in the presence of O3 only. However, after addition of NO, and by extension NO3, large yields of aerosol mass loadings (~44% for butylamine are seen. Aerosol generated was determined to be organic in nature due to the small fraction of NO and NO2 in the total signal (<17% for all amines tested as detected by an aerosol mass spectrometer (AMS. We propose a reaction mechanism between carbonyl containing species and the parent amine leading to formation of particulate imine products. These findings can have significant impacts on rural communities and lead to elevated nighttime PM loadings, when significant levels on NO3 exist.

  1. Solid, double-metal cyanide catalysts for synthesis of hyperbranched polyesters and aliphatic polycarbonates

    Indian Academy of Sciences (India)

    Joby Sebastian; Srinivas Darbha

    2014-03-01

    Fe-Zn and Co-Zn double-metal cyanide (DMC) complexes exhibit highly efficient and selective catalytic activity for synthesis of hyperbranched polyesters (glycerol-succinic acid (G-SA) and glycerol-adipic acid (G-AA)) and aliphatic polycarbonates (via., alternative co-polymerization of cyclohexene oxide and CO2), respectively. The influence of method of preparation of DMC, in particular the mode of addition of reagents, on its physicochemical and catalytic properties was investigated. Co-Zn DMC was found highly selective for polycarbonate (than polyethers) formation. Catalysts prepared using tert-butanol and PEG-4000 as complexing and co-complexing agents, respectively, were found superior to those prepared without these agents. Apart from its role as a coordinating ligand, tert-butanol activated the Lewis acidic Zn2+ sites for reactions in polyester and polycarbonate formation. Hydrophobicity, micro-mesoporosity, acid strength and the amount of coordinated complexing agent are some of the crucial factors influenced the catalytic activity of DMC complexes.

  2. Characterization of aliphatic hydrocarbons in deep subsurface soils near the outskirts of Beijing, China

    Institute of Scientific and Technical Information of China (English)

    ZHU You-feng; LIU Hui; XI Zhi-qun; CHENG Hang-xin; XU Xiao-bai

    2005-01-01

    Thirty-nine deep subsurface soils( 150-180 Gm depth) near the outskirts of Beijing were investagated. The concentrations including n-alkanes from C13 to C36, pristane and phytane were in the range of 0.60 to 170.10 μg/g, with a median value of 4.26. Carbon preference index values for n-alkanes ranged from 1.08 to 2.98, with a median value of 1.48. The percentage contribution of "wax" nalkanes was in the range of 6.03%-46.22%. A predominance of odd/even carbon n-alkanes and unresolved complex mixtures with different shapes and ranges were frequently observed. Factor analysis reduced the data set into three principal components and confirming contributions from Iow ( 19.58%), medium (20.49%) molecular weight species and long-chain n-alkanes (43.41%), respectively.Molecular biomarkers such as pristane, phytane, hopanes and steranes were detected. Based on the principal component analysis, the concentration profiles and molecular markers, it was found that the aliphatic hydrocarbons were from both biogenic and anthropogenic sources.

  3. Secondary organic aerosol formation from primary aliphatic amines with NO3 radical

    Directory of Open Access Journals (Sweden)

    P. J. Silva

    2009-03-01

    Full Text Available Primary aliphatic amines are an important class of nitrogen containing compounds emitted from automobiles, waste treatment facilities and agricultural animal operations. A series of experiments conducted at the UC-Riverside/CE-CERT Environmental Chamber is presented in which oxidation of methylamine, ethylamine, propylamine, and butylamine with O3 and NO3 have been investigated. Very little aerosol formation is observed in the presence of O3 only. However, after addition of NO, and by extension NO3, large aerosol mass yields (~44% for butylamine are seen. Aerosol generated was determined to be organic in nature due to the small fraction of NO and NO2 in the total signal (<1% for all amines tested as detected by an aerosol mass spectrometer (AMS. We propose a reaction mechanism between carbonyl containing species and the parent amine leading to formation of particulate imine products. These findings can have significant impacts on rural communities with elevated nighttime PM loadings, when significant levels of NO3 exist.

  4. Synthesis of Carbon Nanotubes of Few Walls Using Aliphatic Alcohols as a Carbon Source

    Directory of Open Access Journals (Sweden)

    Francisco Espinosa-Magaña

    2013-06-01

    Full Text Available Carbon nanotubes with single and few walls are highly appreciated for their technological applications, regardless of the limited availability due to their high production cost. In this paper we present an alternative process that can lead to lowering the manufacturing cost of CNTs of only few walls by means of the use of the spray pyrolysis technique. For this purpose, ferrocene is utilized as a catalyst and aliphatic alcohols (methanol, ethanol, propanol or butanol as the carbon source. The characterization of CNTs was performed by scanning electron microscopy (SEM and transmission electron microscopy (TEM. The study of the synthesized carbon nanotubes (CNTs show important differences in the number of layers that constitute the nanotubes, the diameter length, the quantity and the quality as a function of the number of carbons employed in the alcohol. The main interest of this study is to give the basis of an efficient synthesis process to produce CNTs of few walls for applications where small diameter is required.

  5. Structure and morphology of thin films of linear aliphatic polyesters prepared by spin-coating.

    Science.gov (United States)

    Hernández, J J; Rueda, D R; García-Gutiérrez, M C; Nogales, A; Ezquerra, T A; Soccio, M; Lotti, N; Munari, A

    2010-07-06

    Thin films, with thicknesses from 10 to 400 nm of linear aliphatic polyesters (X, Y), based on propylenediol (X = 3) and on dicarboxylic acid of different chain length (Y = 2, 3, and 4 CH(2) units) were prepared by spin coating of CHCl(3) polymer solutions with different polymer concentrations. Morphology and structure of the spin coated thin films were investigated by atomic force microscopy (AFM) and by grazing incidence X-ray scattering techniques at small, (GISAXS) and wide angles (GIWAXS). AFM revealed a strong dewetting for all three polymers for coatings thinner than 100 nm. The polymer films are clearly semicrystalline for thicknesses higher than 50 nm. GIWAXS of the thicker films revealed their oriented crystalline nature. An edge-on-lamellae morphology is clearly shown by the AFM-phase images even for relatively thin films. SAXS with the beam parallel to the sample plane also support the presence of lamellae perpendicular to the substrate. The use of a mu-beam helped to interpret the GIWAXS patterns and allowed to obtain oriented WAXS patterns from melt solidified filaments. Thus, a crystal chain packing is proposed for the three polymers and consequently the indexing of the observed reflections. Accordingly, the polymer chains lie parallel to the substrate being the bc plane of the monoclinic crystal unit cell parallel to the substrate.

  6. Aliphatic ketones from Ruta chalepensis (Rutaceae) induce paralysis on root knot nematodes.

    Science.gov (United States)

    Ntalli, Nikoletta G; Manconi, Francesca; Leonti, Marco; Maxia, Andrea; Caboni, Pierluigi

    2011-07-13

    This paper reports on the use of Ruta chalepensis L. extracts as a potential nematicide against root knot nematodes Meloidogyne incognita and Meloidogyne javanica . The essential oil (REO) and methanol extract (RME) of R. chalepensis were tested against second-stage juveniles, with REO inducing paralysis in both species (EC(50/1d) = 77.5 and 107.3 mg/L) and RME being selective for M. incognita (EC(50/1d) = 1001 mg/L). Chemical characterization of extracts was done by means of GC-MS and LC-MS, revealing mainly aliphatic ketones and coumarins, respectively. The first-ranking volatile nematicidal component in terms of individual activity against both species was 2-undecanone (EC(50) = 20.6 and 22.5 mg/L for M. incognita and M. javanica, respectively). This fact together with its high concentration in the most active extract found in this study, namely, REO (2926 mg/kg), categorizes 2-undecanone among the nematicidal principles of R. chalepensis. On the contrary, coumarins rutin and 8-methoxypsoralen were not found to be nematicidal at concentrations of ≤500 mg/L. Interestingly, M. incognita was found more sensitive than M. javanica.

  7. The aliphatic amidase AmiE is involved in regulation of Pseudomonas aeruginosa virulence

    Science.gov (United States)

    Clamens, Thomas; Rosay, Thibaut; Crépin, Alexandre; Grandjean, Teddy; Kentache, Takfarinas; Hardouin, Julie; Bortolotti, Perrine; Neidig, Anke; Mooij, Marlies; Hillion, Mélanie; Vieillard, Julien; Cosette, Pascal; Overhage, Joerg; O’Gara, Fergal; Bouffartigues, Emeline; Dufour, Alain; Chevalier, Sylvie; Guery, Benoit; Cornelis, Pierre; Feuilloley, Marc G. J.; Lesouhaitier, Olivier

    2017-01-01

    We have previously shown that the eukaryotic C-type natriuretic peptide hormone (CNP) regulates Pseudomonas aeruginosa virulence and biofilm formation after binding on the AmiC sensor, triggering the amiE transcription. Herein, the involvement of the aliphatic amidase AmiE in P. aeruginosa virulence regulation has been investigated. The proteome analysis of an AmiE over-producing strain (AmiE+) revealed an expression change for 138 proteins, including some that are involved in motility, synthesis of quorum sensing compounds and virulence regulation. We observed that the AmiE+ strain produced less biofilm compared to the wild type, and over-produced rhamnolipids. In the same line, AmiE is involved in P. aeruginosa motilities (swarming and twitching) and production of the quorum sensing molecules N-acyl homoserine lactones and Pseudomonas Quinolone Signal (PQS). We observed that AmiE overproduction reduced levels of HCN and pyocyanin causing a decreased virulence in different hosts (i.e. Dictyostelium discoideum and Caenorhabditis elegans). This phenotype was further confirmed in a mouse model of acute lung infection, in which AmiE overproduction resulted in an almost fully virulence decrease. Taken together, our data suggest that, in addition to its role in bacterial secondary metabolism, AmiE is involved in P. aeruginosa virulence regulation by modulating pilus synthesis and cell-to-cell communication. PMID:28117457

  8. Synthesis, Catalysis of Rare Earth Complexes with Aliphatic Noncyclic Polyether-Amino Acid Schiff Base

    Institute of Scientific and Technical Information of China (English)

    Li Ning; Yao Kemin; Shen Lianfang

    2005-01-01

    Eleven new rare earth complexes with aliphatic Schiff base, condensed from diglycol aldehyde and bis-arginine, were synthesized and characterized. They are confirmed as Ln(H2DAAR)(NO3)3·7H2O (Ln=La, Pr, Nd, Gd), Ln3(H2DAAR)2(NO3)9·5H2O (Ln=Dy, Y) and Ln2(H2DAAR)(NO3)6·3H2O (Ln=La, Nd, Sm, Gd), Ln3(DAAR)(NO3)7·4H2O (Ln=Dy, Yb, Y) respectively under different molar ratios of metal to ligand (DAAR=diglycol aldehyde bis-arginine). The present paper deals with a synthetic method and catalytic properties of obtained complexes. The result shows that proper pH value is important for synthesis of the complexes and compositions of the lighter and the heavier rare earth complexes are different under the same reaction condition. Some new complexes obtained have proved their catalytic activity and 80% conversion with the viscosity-average molecular weight 230,000 for the polymerization of methyl methacrylate (MMA) without addition of any cocatalyst.

  9. Separation of Aliphatic and Aromatic Carboxylic Acids by Conventional and Ultra High Performance Ion Exclusion Chromatography.

    Science.gov (United States)

    Mansour, Fotouh R; Kirkpatrick, Christine L; Danielson, Neil D

    2013-06-01

    An ion exclusion chromatography (IELC) comparison between a conventional ion exchange column and an ultra-high performance liquid chromatography (UHPLC) dynamically surfactant modified C18 column for the separation of an aliphatic carboxylic acid and two aromatic carboxylic acids is presented. Professional software is used to optimize the conventional IELC separation conditions for acetylsalicylic acid and the hydrolysis products: salicylic acid and acetic acid. Four different variables are simultaneously optimized including H2SO4 concentration, pH, flow rate, and sample injection volume. Thirty different runs are suggested by the software. The resolutions and the time of each run are calculated and feed back to the software to predict the optimum conditions. Derringer's desirability functions are used to evaluate the test conditions and those with the highest desirability value are utilized to separate acetylsalicylic acid, salicylic acid, and acetic acid. These conditions include using a 0.35 mM H2SO4 (pH 3.93) eluent at a flow rate of 1 mL min(-1) and an injection volume of 72 μL. To decrease the run time and improve the performance, a UHPLC C18 column is used after dynamic modification with sodium dodecyl sulfate. Using pure water as a mobile phase, a shorter analysis time and better resolution are achieved. In addition, the elution order is different from the IELC method which indicates the contribution of the reversed-phase mode to the separation mechanism.

  10. Syntheses, structures, and properties of multidimensional lithium coordination polymers based on aliphatic carboxylic acids.

    Science.gov (United States)

    Cheng, Pei-Chi; Lin, Wei-Cheng; Tseng, Feng-Shuen; Kao, Ching-Che; Chang, Ting-Guang; Senthil Raja, Duraisamy; Liu, Wei-Ren; Lin, Chia-Her

    2013-02-28

    Three lithium coordination polymers, [Li4(H2O)2(EDTA)] (1), [Li4(H2O)4(BTCA)] (2), and (H2NMe2)2[Li2(H2O)2(BTCA)] (3) (H4EDTA = ethylenediaminetetraacetic acid, H4BTCA = 1,2,3,4-butane tetracarboxylic acid, H2NMe2 = dimethyl amine), have been synthesized by reacting lithium salts with aliphatic carboxylic acids using a solvothermal method. The structures of all the three complexes have been determined by single crystal X-ray diffraction studies. The single crystal structure analysis revealed that complex 1 has a three-dimensional framework, whereas complex 2 has 2D sheets and complex 3 has 1D chains. In addition, these lithium complexes contain various inorganic motifs with a tetramer in 1 and 2, and discrete tetrahedra in 3 and have further been connected through organic ligands to construct multidimensional structures. Further, the electrochemical properties of complexes 1–3 have been studied to evaluate these compounds as electrode materials for lithium ion batteries with discharge capacities of around 100 mA h g(-1) in the first thirty cycles.

  11. Aliphatic Hyperbranched Poly(amido amine)s(PAMAMs): Preparation and Modification

    Institute of Scientific and Technical Information of China (English)

    LIU Cui-hua; GAO Chao; YAN De-yue

    2005-01-01

    A series of water soluble aliphatic hyperbranched poly(amido amine)s(PAMAMs) with the same or similar chemical structure of poly(amido amine) dendrimer was successfully synthesized from commercially available AB and Cn types of monomers by one-pot polymerization via the couple-monomer methodology(CMM). The AB type monomer used in this paper was methyl acrylate, and Cn monomers were multi-amino compounds such as ethylenediamine(EDA), diethylenetriamine(DETA), triethylenetetraamine(TETA), tetraethylenepentaamine(TEPA) and pentaethylenehexamine(PEHA). The reaction mechanism was investigated by means of the mass spectra of the reaction intermediates. Adjusting the feed ratio of AB to Cn, hyperbranched polymers with different terminal groups and properties were obtained. FTIR, NMR, DSC, and TGA were used to characterize the polymers. It was found that the polymers' properties such as solubility, thermal behaviour and encapsulation capability varied with changing the feed ratio of AB to Cn. Benzoyl and palmitoyl groups were introduced into these macromolecules by acidylation to form amphiphilic hyperbranched polymers which have a high capability to encapsulate water soluble dyes such as Congo red. It is expected that the hyperbranched PAMAMs can play an important role in the industrial applications, such as coatings, cross-linking and phase-transferring agents because of their versatility and availability.

  12. The aliphatic counterpart of PET, PPT and PBT aromatic polyesters: effect of the molecular structure on thermo-mechanical properties

    Directory of Open Access Journals (Sweden)

    Morgane Albanese

    2016-02-01

    Full Text Available The aliphatic counterparts of the most used aromatic polyesters (PET, PPT, and PBT have been synthesized by a two-stage polycondensation process, starting from dimethyl 1,4-cyclohexane dicarboxylate and different diols. The fully aliphatic polyesters are characterized by two cis/trans isomeric ratios (50 and 90 mol% of the 1,4-cycloaliphatic rings. According to the cis/trans content, the properties of the materials notably change. Indeed, polymers rich in trans isomer are semicrystalline, whereas polymers with low trans content are fully amorphous, due to the presence of kinks along the chain. Trans isomer is characterized by higher rigidity than the cis one and the corresponding polymers have high glass transition temperatures. Moreover, the length of the methylene sequences in the diol has a notable influence on the final thermal and mechanical properties. Therefore, tunable properties can be easily obtained. This characteristic, in association with good mechanical performances, potential sustainability of the monomers and biodegradability, makes these aliphatic polyesters an interesting class of polyesters for some specific applications.

  13. Biosynthetic pathway of aliphatic formates via a Baeyer–Villiger oxidation in mechanism present in astigmatid mites

    Science.gov (United States)

    Shimizu, Nobuhiro; Sakata, Daisuke; Schmelz, Eric A.; Mori, Naoki; Kuwahara, Yasumasa

    2017-01-01

    Astigmatid mites depend on bioactive glandular secretions, pheromones, and defensive agents to mediate intra- and interspecies interactions. Aliphatic formates, such as (Z,Z)-8,11-heptadecadienyl formate (8,11-F17) and (Z)-8-heptadecenyl formate (8-F17), are rarely encountered natural products that are abundant in Sancassania sp. Sasagawa (Acari: Acaridae) mite secretions. Linoleic acid and oleic acid are predicted as key intermediates in the synthesis of the closely related aliphatic formates. To gain insight in this biosynthetic pathway, acarid mite feeding experiments were conducted using 13C-labeled precursors to precisely track incorporation. Analyses using 13C NMR spectroscopy demonstrated that the 13C-labeling pattern of the precursors was detectable on formates in exocrine secretions and likewise on fatty acids in total lipid pools. Curiously, the results demonstrated that the formates were biosynthesized without the dehomologation of corresponding fatty acids. Careful examination of the mass spectra from labeling experiments revealed that the carbonyl carbon of the formates is originally derived from the C-1 position of the fatty acids. Consistent with a Baeyer–Villiger oxidation reaction, labeling studies support the insertion of an oxygen atom between the carbonyl group and carbon chain. Empirical data support the existence of a Baeyer–Villiger monooxygenase responsible for the catalyzation of the Baeyer–Villiger oxidation. The predicted existence of a Baeyer–Villiger monooxygenase capable of converting aliphatic aldehydes to formates represents an exciting opportunity to expand the enzymatic toolbox available for controlled biochemical synthesis. PMID:28223501

  14. Purification and characterization of a novel nitrilase of Rhodococcus rhodochrous K22 that acts on aliphatic nitriles.

    Science.gov (United States)

    Kobayashi, M; Yanaka, N; Nagasawa, T; Yamada, H

    1990-01-01

    A novel nitrilase that preferentially catalyzes the hydrolysis of aliphatic nitriles to the corresponding carboxylic acids and ammonia was found in the cells of a facultative crotononitrile-utilizing actinomycete isolated from soil. The strain was taxonomically studied and identified as Rhodococcus rhodochrous. The nitrilase was purified, with 9.08% overall recovery, through five steps from a cell extract of the stain. After the last step, the purified enzyme appeared to be homogeneous, as judged by polyacrylamide gel electrophoresis, analytical centrifugation, and double immunodiffusion in agarose. The relative molecular weight values for the native enzyme, estimated from the ultracentrifugal equilibrium and by high-performance liquid chromatography, were approximately 604,000 +/- 30,000 and 650,000, respectively, and the enzyme consisted of 15 to 16 subunits identical in molecular weight (41,000). The enzyme acted on aliphatic olefinic nitriles such as crotononitrile and acrylonitrile as the most suitable substrates. The apparent Km values for crotononitrile and acrylonitrile were 18.9 and 1.14 mM, respectively. The nitrilase also catalyzed the direct hydrolysis of saturated aliphatic nitriles, such as valeronitrile, 4-chlorobutyronitrile, and glutaronitrile, to the corresponding acids without the formation of amide intermediates. Hence, the R. rhodochrous K22 nitrilase is a new type distinct from all other nitrilases that act on aromatic and related nitriles. Images PMID:2394676

  15. Surface complex formation between aliphatic nitrile molecules and transition metal atoms for thermally stable lithium-ion batteries.

    Science.gov (United States)

    Kim, Young-Soo; Lee, Hochun; Song, Hyun-Kon

    2014-06-11

    Non-flammability of electrolyte and tolerance of cells against thermal abuse should be guaranteed for widespread applications of lithium-ion batteries (LIBs). As a strategy to improve thermal stability of LIBs, here, we report on nitrile-based molecular coverage on surface of cathode active materials to block or suppress thermally accelerated side reactions between electrode and electrolyte. Two different series of aliphatic nitriles were introduced as an additive into a carbonate-based electrolyte: di-nitriles (CN-[CH2]n-CN with n = 2, 5, and 10) and mono-nitriles (CH3-[CH2]m-CN with m = 2, 5, and 10). On the basis of the strong interaction between the electronegativity of nitrile functional groups and the electropositivity of cobalt in LiCoO2 cathode, aliphatic mono- and di-nitrile molecules improved the thermal stability of lithium ion cells by efficiently protecting the surface of LiCoO2. Three factors, the surface coverage θ, the steric hindrance of aliphatic moiety within nitrile molecule, and the chain polarity, mainly affect thermal tolerance as well as cell performances at elevated temperature.

  16. Segregation and Alteration of Phenolic and Aliphatic Components of Root and Leaf Litter by Detritivores and Microbes

    Science.gov (United States)

    Filley, T. R.; Altmann, J.; Szlavecz, K. A.; Kalbitz, K.; Gamblin, D.; Nierop, K.

    2012-12-01

    The physical and microbial transformation of plant detritus in the litter layer and soil is accompanied by chemical separation of progressively soluble fractions and their movement into the rhizosphere driving subsequent soil processes. We investigated the combined action of specific detritivores, microbial decay, and leaching on the chemical separation of plant aromatic and aliphatic components from root, wood, and leaf tissue using 13C-TMAH thermochemolysis. This method enabled the simultaneous analysis of hydrolyzable tannin and lignin fragments, substituted fatty acids, and condensed tannin composition and revealed process-specific chemical transformations to plant secondary compounds. Long-term incubation and field sampling demonstrated how plant residues are progressively leached of the water soluble, oxidized fragments generated through decay. The residues appeared only slightly altered, in the case of brown rot wood, or enriched in aliphatic fragments, in the case of leaf and root tissue. Water extractable fractions were always selectively dominated by polyphenolics, either as demethylated lignin or tannins, and nearly devoid of aliphatic materials, despite high concentrations in the starting materials. Additionally, for plant materials with high tannin contents, such as pine needles, consumption and passage through some arthropod guts revealed what appeared to be microbially-mediated methylation of phenols, and a loss of tannins in leachates. These findings are indications for an in-situ phenol detoxification mechanism. This research provides important information regarding the links between biochemical decay and the chemical nature of organic matter removed and remaining in the soil profile.

  17. 红外光谱法测定顺丁烯二酸硬脂酸聚氧乙烯酯单酯二乙醇酰胺含量%The maleic acid poloyxyethylene fatty acide ester monoester diethanolamine assay in infrared spectroscopy

    Institute of Scientific and Technical Information of China (English)

    沈芳; 赵志明

    2013-01-01

      以顺丁烯二酸酐,硬脂酸聚氧乙烯酯为原料制备顺丁烯二酸硬脂酸聚氧乙烯酯单酯,提纯后再与二乙醇胺反应,制备顺丁烯二酸硬脂酸聚氧乙烯酯单酯二乙醇酰胺,提纯后制备酰胺标准物.选择硫氰酸钾为内标物,采用红外光谱法对顺丁烯二酸硬脂酸聚氧乙烯酯单酯二乙醇酰胺与内标物的混合样品进行测试.以酰胺与硫氰酸钾的质量比为横坐标,所对应的峰高比为纵坐标绘制标准曲线.得到的线性回归方程为y=0.3203x-0.0034,相关系数为R2=0.9991,方法的相对标准偏差为0.48%,回收率为91.67%~103.85%.%On this paper the maleic acid polyoxyethylene fatty acid ester monoester diethanolamide was quantitative analysisd by Infrared spectra. First, prepare maleic aicd poloyxyethylene fatty c monoester with maleic anhydride and stearic ester polyoxye , purification and reactact with diethanolamine, than prepare maleic aicd poloyxyethylene fatty ester monoester diethanolamine amide purified preparation of standard. Choose potassium thiocyanate as internal stangard, grinding with amide simples together ,and test with infrared compression method. Make the mass ration amide and potassium thiocyanate of x-coodinate, conresponding to the peak hight ration of the vertical coodinate to map stsndard curve. Linear ression equation is y=0.3203x-0.0034, the correlation cofficient R2=0.9991, and determinade the precision and recovery of the infrared spectroscopy,is to say,the relative standard deviation equal 0.48%, recovery equal 91.67%~101.0%.

  18. Amino Acid Insertion Frequencies Arising from Photoproducts Generated Using Aliphatic Diazirines

    Science.gov (United States)

    Ziemianowicz, Daniel S.; Bomgarden, Ryan; Etienne, Chris; Schriemer, David C.

    2017-10-01

    Mapping proteins with chemical reagents and mass spectrometry can generate a measure of accessible surface area, which in turn can be used to support the modeling and refinement of protein structures. Photolytically generated carbenes are a promising class of reagent for this purpose. Substituent effects appear to influence surface mapping properties, allowing for a useful measure of design control. However, to use carbene labeling data in a quantitative manner for modeling activities, we require a better understanding of their inherent amino acid reactivity, so that incorporation data can be normalized. The current study presents an analysis of the amino acid insertion frequency of aliphatic carbenes generated by the photolysis of three different diazirines: 3,3'-azibutyl-1-ammonium, 3,3'-azibutan-1-ol, and 4,4'-azipentan-1-oate. Leveraging an improved photolysis system for single-shot labeling of sub-microliter frozen samples, we used EThCD to localize insertion products in a large population of labeled peptides. Counting statistics were drawn from data-dependent LC-MS2 experiments and used to estimate the frequencies of insertion as a function of amino acid. We observed labeling of all 20 amino acids over a remarkably narrow range of insertion frequencies. However, the nature of the substituent could influence relative insertion frequencies, within a general preference for larger polar amino acids. We confirm a large (6-fold) increase in labeling yield when carbenes were photogenerated in the solid phase (77 K) relative to the liquid phase (293 K), and we suggest that carbene labeling should always be conducted in the frozen state to avoid information loss in surface mapping experiments. [Figure not available: see fulltext.

  19. Biodegradable aliphatic-aromatic copolyester/corn starch blend composite reinforced with coffee parchment husk

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Valquiria A.; Teixeira, Jaciele G.; Gomes, Michelle G.; Ortiz, Angel V.; Oliveira, Rene R.; Scapin, Marcos A.; Moura, Esperidiana A.B. [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Colombo, Maria A., E-mail: valquiriaalves36@yahoo.com.br [Faculdade de Tecnologia da Zona Leste (FATEC), Sao Paulo, SP (Brazil)

    2013-07-01

    In recent years, studies have shown that the addition of natural fiber or proper filler is an effective strategy for achieving improved properties in biodegradable polymer materials. Moreover, is especially important if such fibers are residues of agro-industrial processes. In this work, a promising technique to develop biodegradable polymer matrix composite based on aliphatic-aromatic copolyester/corn starch blend (Evela®) and coffee parchment husk, which is residue from coffee processing is described. The biodegradable polymeric blend (Evela®) with 5 % (w/w) of ball-milled coffee parchment husk fiber powder, with size ≤250 μm, without any modification was prepared by melt-mixing processing, using a twin screw extruder machine and then pelletized. In a second step, the pelletized Evela®)/coffee parchment (Composite) was then dried at 70 ± 2 deg C for 24 h in a circulating air oven, fed into injection molding machine and test specimens were obtained. The Composite specimen samples were irradiated using an electron beam accelerator, at radiation dose of 20 and 40 kGy, at room temperature in presence of air. The irradiated and non-irradiated samples were characterized by means of scanning electron microscopy (SEM), X-Ray diffraction (XRD), tensile tests and sol-gel analysis and the correlation between their properties was discussed. In addition, coffee parchment husk fiber characterization by SEM, EDS, XRD and WDXRF have also been carried out with a view to evaluate its importance in determining the end-use properties of the composite. (author)

  20. Effect of aliphatic, monocarboxylic, dicarboxylic, heterocyclic and sulphur-containing amino acids on Leishmania spp. chemotaxis.

    Science.gov (United States)

    Diaz, E; Zacarias, A K; Pérez, S; Vanegas, O; Köhidai, L; Padrón-Nieves, M; Ponte-Sucre, A

    2015-11-01

    In the sand-fly mid gut, Leishmania promastigotes are exposed to acute changes in nutrients, e.g. amino acids (AAs). These metabolites are the main energy sources for the parasite, crucial for its differentiation and motility. We analysed the migratory behaviour and morphological changes produced by aliphatic, monocarboxylic, dicarboxylic, heterocyclic and sulphur-containing AAs in Leishmania amazonensis and Leishmania braziliensis and demonstrated that L-methionine (10-12 m), L-tryptophan (10-11 m), L-glutamine and L-glutamic acid (10-6 m), induced positive chemotactic responses, while L-alanine (10-7 m), L-methionine (10-11 and 10-7 m), L-tryptophan (10-11 m), L-glutamine (10-12 m) and L-glutamic acid (10-9 m) induced negative chemotactic responses. L-proline and L-cysteine did not change the migratory potential of Leishmania. The flagellum length of L. braziliensis, but not of L. amazonensis, decreased when incubated in hyperosmotic conditions. However, chemo-repellent concentrations of L-alanine (Hypo-/hyper-osmotic conditions) and L-glutamic acid (hypo-osmotic conditions) decreased L. braziliensis flagellum length and L-methionine (10-11 m, hypo-/hyper-osmotic conditions) decreased L. amazonensis flagellum length. This chemotactic responsiveness suggests that Leishmania discriminate between slight concentration differences of small and structurally closely related molecules and indicates that besides their metabolic effects, AAs play key roles linked to sensory mechanisms that might determine the parasite's behaviour.

  1. Forward targeting of Toxoplasma gondii proproteins to the micronemes involves conserved aliphatic amino acids.

    Science.gov (United States)

    Gaji, Rajshekhar Y; Flammer, Halley P; Carruthers, Vern B

    2011-07-01

    Like other apicomplexan parasites, Toxoplasma gondii actively invades host cells using a combination of secretory proteins and an acto-myosin motor system. Micronemes are the first set of proteins secreted during invasion that play an essential role in host cell entry. Many microneme proteins (MICs) function in protein complexes, and each complex contains at least one protein that displays a cleavable propeptide. Although MIC propeptides have been implicated in forward targeting to micronemes, the specific amino acids involved have not been identified. It was also not known if the propeptide has a general function in MICs trafficking in T. gondii and other apicomplexans. Here we show that propeptide domains are extensively interchangeable between T. gondii MICs and also with that of Eimeria tenella MIC5 (EtMIC5), suggesting a common mechanism of function. We also performed N-terminal deletion and mutational analysis of M2AP and MIC5 propeptides to show that a valine at position +3 (relative to signal peptidase cleavage) of proM2AP and a leucine at position +1 of proMIC5 are crucial for targeting to micronemes. Valine and leucine are closely related amino acids with similar side chains, implying a similar mode of function, a notion that was confirmed by correct trafficking of TgM2AP-V/L and TgMIC5-L/V substitution mutants. Propeptides of AMA1, MIC3 and EtMIC5 have valine or leucine at or near the N-termini and mutagenesis of these conserved residues validated their role in microneme trafficking. Collectively, our findings suggest that discrete, aliphatic residues at the extreme N-termini of proMICs facilitate trafficking to the micronemes.

  2. Degradation kinetics of chlorinated aliphatic hydrocarbons by methane oxidizers naturally-associated with wetland plant roots

    Science.gov (United States)

    Powell, C. L.; Goltz, M. N.; Agrawal, A.

    2014-12-01

    Chlorinated aliphatic hydrocarbons (CAHs) are common groundwater contaminants that can be removed from the environment by natural attenuation processes. CAH biodegradation can occur in wetland environments by reductive dechlorination as well as oxidation pathways. In particular, CAH oxidation may occur in vegetated wetlands, by microorganisms that are naturally associated with the roots of wetland plants. The main objective of this study was to evaluate the cometabolic degradation kinetics of the CAHs, cis-1,2-dichloroethene (cisDCE), trichloroethene (TCE), and 1,1,1-trichloroethane (1,1,1TCA), by methane-oxidizing bacteria associated with the roots of a typical wetland plant in soil-free system. Laboratory microcosms with washed live roots investigated aerobic, cometabolic degradation of CAHs by the root-associated methane-oxidizing bacteria at initial aqueous [CH4] ~ 1.9 mg L- 1, and initial aqueous [CAH] ~ 150 μg L- 1; cisDCE and TCE (in the presence of 1,1,1TCA) degraded significantly, with a removal efficiency of approximately 90% and 46%, respectively. 1,1,1TCA degradation was not observed in the presence of active methane oxidizers. The pseudo first-order degradation rate-constants of TCE and cisDCE were 0.12 ± 0.01 and 0.59 ± 0.07 d- 1, respectively, which are comparable to published values. However, their biomass-normalized degradation rate constants obtained in this study were significantly smaller than pure-culture studies, yet they were comparable to values reported for biofilm systems. The study suggests that CAH removal in wetland plant roots may be comparable to processes within biofilms. This has led us to speculate that the active biomass may be on the root surface as a biofilm. The cisDCE and TCE mass losses due to methane oxidizers in this study offer insight into the role of shallow, vegetated wetlands as an environmental sink for such xenobiotic compounds.

  3. Differential Effects of Falcarinol and Related Aliphatic C17-Polyacetylenes on Intestinal Cell Proliferation

    Science.gov (United States)

    2009-01-01

    Quantitative major polyacetylenes of carrots (falcarinol and falcarindiol) and American ginseng roots (falcarinol and panaxydol) were isolated and tested in human intestinal epithelial cells of normal (FHs 74 Int.) and cancer (Caco-2) origin. A hormesis effect was seen for all isolated polyacetylenes when added to Caco-2 cells in concentrations ranging from 1 ng/mL to 20 μg/mL. The relative inhibitory potency was falcarinol > panaxydol > falcarindiol. No hormesis effect was observed when adding the polyacetylenes to FHs 74 Int. cells. Instead, an inhibitory growth response was observed above 1 μg/mL. The relative inhibitory potency was panaxydol > falcarinol > falcarindiol. Maximal inhibition at 20 μg/mL corresponded to approximately 95% and 80% inhibition of cell proliferation in normal and cancer cells, respectively. Combinations of falcarinol and falcarindiol added to normal and cancer cells showed a synergistic response for the inhibition of cell growth. Furthermore, the oxidized form of falcarinol, falcarinon, showed a significantly less growth inhibitory effect in intestinal cells of both normal and cancer origin; hence, a hydroxyl group at C-3 may be important for activity of falcarinol-type polyacetylenes. Extracts of carrots, containing different amounts of falcarinol, falcarindiol, and falcarindiol 3-acetate had significant inhibitory effects on both normal and cancer cell proliferation. In cancer cells, the extract containing the highest concentration of falcarinol tended to have the highest growth inhibitory effect, in accordance with a higher potency of falcarinol than falcarindiol. The present study demonstrates that aliphatic C17-polyacetylenes are potential anticancer principles of carrots and related vegetables and that synergistic interaction between bioactive polyacetylenes may be important for their bioactivity. PMID:19694436

  4. Differential effects of falcarinol and related aliphatic C(17)-polyacetylenes on intestinal cell proliferation.

    Science.gov (United States)

    Purup, Stig; Larsen, Eric; Christensen, Lars P

    2009-09-23

    Quantitative major polyacetylenes of carrots (falcarinol and falcarindiol) and American ginseng roots (falcarinol and panaxydol) were isolated and tested in human intestinal epithelial cells of normal (FHs 74 Int.) and cancer (Caco-2) origin. A hormesis effect was seen for all isolated polyacetylenes when added to Caco-2 cells in concentrations ranging from 1 ng/mL to 20 microg/mL. The relative inhibitory potency was falcarinol > panaxydol > falcarindiol. No hormesis effect was observed when adding the polyacetylenes to FHs 74 Int. cells. Instead, an inhibitory growth response was observed above 1 microg/mL. The relative inhibitory potency was panaxydol > falcarinol > falcarindiol. Maximal inhibition at 20 microg/mL corresponded to approximately 95% and 80% inhibition of cell proliferation in normal and cancer cells, respectively. Combinations of falcarinol and falcarindiol added to normal and cancer cells showed a synergistic response for the inhibition of cell growth. Furthermore, the oxidized form of falcarinol, falcarinon, showed a significantly less growth inhibitory effect in intestinal cells of both normal and cancer origin; hence, a hydroxyl group at C-3 may be important for activity of falcarinol-type polyacetylenes. Extracts of carrots, containing different amounts of falcarinol, falcarindiol, and falcarindiol 3-acetate had significant inhibitory effects on both normal and cancer cell proliferation. In cancer cells, the extract containing the highest concentration of falcarinol tended to have the highest growth inhibitory effect, in accordance with a higher potency of falcarinol than falcarindiol. The present study demonstrates that aliphatic C(17)-polyacetylenes are potential anticancer principles of carrots and related vegetables and that synergistic interaction between bioactive polyacetylenes may be important for their bioactivity.

  5. Two Novel Flavin-Containing Monooxygenases Involved in Biosynthesis of Aliphatic Glucosinolates

    Directory of Open Access Journals (Sweden)

    Wenwen Kong

    2016-08-01

    Full Text Available Glucosinolates (GSLs, a class of secondary metabolites from cruciferous plants, are derived from amino acids and have diverse biological activities, such as in biotic defense, depending on their side chain modification. The first structural modification step in the synthesis of aliphatic (methionine-derived GSLs—S-oxygenation of methylthioalkyl GSLs to methylsulfinylalkyl GSLs—was found to be catalyzed by five flavin-containing monooxygenases (FMOs, FMOGS-OX1-5. Here, we report two additional FMOGS-OX enzymes, FMOGS-OX6 and FMOGS-OX7, encoded by At1g12130 and At1g12160, respectively. The overexpression of both FMOGS-OX6 and FMOGS-OX7 decreased the ratio of MT GSL to the sum of MT and MS GSL, suggesting that the introduction of the two genes converted MT GSL into MS GSL. Analysis of expression pattern revealed that the spatial expression of the two genes is quite similar and partially overlapped with the other FMOGS-OX genes, which are primarily expressed in vascular tissue. We further analyzed the responsive expression pattern of all the seven FMOGS-OX genes to exogenous treatment with abscisic acid (ABA, 1-aminocyclopropane-1-carboxylic acid (ACC, jasmonic acid (JA, salicylic acid (SA, indole-3-acetic acid (IAA, and low and high temperatures. Although these genes showed same tendency toward the changing stimulus, the sensitivity of each gene was quite different. The variety in spatial expression among the FMOGS-OX genes while responding to environmental stimulus indicated a complex and finely tuned regulation of GSL modifications. Identification of these two novel FMOGS-OX enzymes will enhance the understanding of GSL modifications and the importance of evolution of these duplicated genes.

  6. Impacts of crystal metal on secondary aliphatic amine aerosol formation during dust storm episodes in Beijing

    Science.gov (United States)

    Liu, Qingyang; Bei, Yiling

    2016-03-01

    Trimethylamine (TMA) enters the atmosphere from a variety of sources and is a ubiquitous atmospheric organic base. The atmospheric reaction mechanism of TMA with key atmospheric oxidants is important to predict its distribution and environmental behavior in the particle phase. While previous studies have extensively focused on the production of particle amine salts (i.e. trimethylamine-N-oxide (TMAO)) using chamber experiments, the atmospheric behavior of TMAO in the environment is still poorly understood. Ambient fine particulate matter (PM2.5) was collected at two sampling sites in Beijing from March 10 to May 10, 2012. We analyzed the samples for water-soluble ions, crystal metals, TMA, and TMAO. Water-soluble ions (e.g. SO42-, NO3-, NH4+), TMA, and TMAO were measured using ion chromatography, while crystal metal (e.g. Al, Fe, Mn) in PM2.5 was quantified by inductively coupled plasma mass spectrometry (ICP-MS). Two dust storms (DS) occurred during the sampling period on March 28 and April 28. Mineral dust impacted PM2.5 mass and composition greatly during dust storm days, as it contributed approximately 1.2-4.0 times greater on dust storm days versus non-dust storm days. We found TMAO concentrations were highly associated with aluminum in PM2.5. Further, we applied the density functional theory (DFT) method to confirm that aluminum plays a catalytic effect in the reaction of TMA with ozone (O3). Our work improves understanding of the effect of crystal metals on secondary aliphatic amine aerosol formation in the atmosphere.

  7. Degradation kinetics of chlorinated aliphatic hydrocarbons by methane oxidizers naturally-associated with wetland plant roots.

    Science.gov (United States)

    Powell, C L; Goltz, M N; Agrawal, A

    2014-12-01

    Chlorinated aliphatic hydrocarbons (CAHs) are common groundwater contaminants that can be removed from the environment by natural attenuation processes. CAH biodegradation can occur in wetland environments by reductive dechlorination as well as oxidation pathways. In particular, CAH oxidation may occur in vegetated wetlands, by microorganisms that are naturally associated with the roots of wetland plants. The main objective of this study was to evaluate the cometabolic degradation kinetics of the CAHs, cis-1,2-dichloroethene (cisDCE), trichloroethene (TCE), and 1,1,1-trichloroethane (1,1,1TCA), by methane-oxidizing bacteria associated with the roots of a typical wetland plant in soil-free system. Laboratory microcosms with washed live roots investigated aerobic, cometabolic degradation of CAHs by the root-associated methane-oxidizing bacteria at initial aqueous [CH4] ~1.9mgL(-1), and initial aqueous [CAH] ~150μgL(-1); cisDCE and TCE (in the presence of 1,1,1TCA) degraded significantly, with a removal efficiency of approximately 90% and 46%, respectively. 1,1,1TCA degradation was not observed in the presence of active methane oxidizers. The pseudo first-order degradation rate-constants of TCE and cisDCE were 0.12±0.01 and 0.59±0.07d(-1), respectively, which are comparable to published values. However, their biomass-normalized degradation rate constants obtained in this study were significantly smaller than pure-culture studies, yet they were comparable to values reported for biofilm systems. The study suggests that CAH removal in wetland plant roots may be comparable to processes within biofilms. This has led us to speculate that the active biomass may be on the root surface as a biofilm. The cisDCE and TCE mass losses due to methane oxidizers in this study offer insight into the role of shallow, vegetated wetlands as an environmental sink for such xenobiotic compounds.

  8. Enzymatic synthesis of 3-(tert-butyldimethylsilyloxy)glutaric methyl monoester by immobilized lipase%固定化脂肪酶合成3-TBDMSO戊二酸甲酯

    Institute of Scientific and Technical Information of China (English)

    王霞; 董文癑; 陈雄飞; 付雁

    2014-01-01

    Lipase-catalysed reactions were considered as an effective method to prepare pure enantiomers,based on the esterification of alcohol,acid,or lactone in non-aqueous phase under mild reaction conditions.An enzymatic alcoholysis of 3-(tert-butyldimethylsilyloxy ) glutaric anhydride (3-TBDMSO-GA ) with methanol for preparing 3-(tert-butyldimethylsilyloxy)glutaric methyl monoester (3-TBDMSO-GMM)was studied using immobilized Lipase Novozym 435 .The different solvents including tetrahydrofuran,ethyl acetate,diethyl ether,methyl tert-butyl ether and toluene were investigated under mild conditions.It shows that methyl tert-butyl ether is the most effective solvent in the alcoholysis reaction.The effects of reaction time and temperature,enzyme amount,water activity, substrate concentration,molar ratio of alcohol to substrate on the substrate conversion and the selectivity were studied using the analysis of high performance liquid chromatography with C18 column.The optimal reaction conditions were as follows:temperature 25 ℃,enzyme mass concentration 30 mg/mL,the molar ratio of alcohol to 3-TBDMSO-GA 1.0,anhydride concentration 100 mmol/L,pH 6.5,water activity 0.66 and reaction time 6 h. The product of colorless crystal was obtained through extraction method followed by crystallization purification.By using 1 H-NMR,the product was confirmed as 3-TBDMSO-GMM.CD spectroscopy demonstrates that the product has an enantiomeric excess.%脂肪酶主要催化醇、酸、内酯的酯化反应,脂肪酶催化反应可在非水溶剂中进行,并且反应条件温和,被认为是制备单一对映异构体的有效方法。文中利用固定化脂肪酶Novozym 435催化3-TBDMSO戊二酸酐不对称醇解制备3-TBDMSO戊二酸甲酯,通过高效液相色谱考察了不同反应条件对底物转化率、产物选择性的影响规律。实验研究了四氢呋喃、乙酸乙酯、乙醚、甲基叔丁基醚和甲苯5种溶剂对酶催化反应的影响,结果表明:在甲

  9. An improved reagent for determination of aliphatic amines with fluorescence and online atmospheric chemical ionization-mass spectrometry identification.

    Science.gov (United States)

    You, Jinmao; Song, Cuihua; Yan, Tao; Sun, Zhiwei; Li, Yulin; Suo, Yourui

    2010-01-18

    An improved reagent named 2-[2-(dibenzocarbazole)-ethoxy] ethyl chloroformate (DBCEC-Cl) for the determination of aliphatic amines by high-performance liquid chromatography (HPLC) with fluorescence detection and post-column online atmospheric chemical ionization-mass spectrometry (APCI-MS) identification has been developed. DBCEC-Cl could easily and quickly label aliphatic amines. Derivatives were stable enough to be efficiently analyzed by HPLC and showed an intense protonated molecular ion corresponding m/z [M+H](+) under APCI-MS in positive-ion mode. The ratios for fluorescence responses were I(DBCEC-amine)/I(BCEC-amine)=1.02-1.60; I(DBCEC-amine)/I(BCEOC-amine)=1.30-2.57; and I(DBCEC-amine)/I(FMOC-amine)=2.20-4.12 (here, I was relative fluorescence intensity). The ratios for MS responses were IC(DBCEC-amine)/IC(BCEC-amine)=4.16-29.31 and IC(DBCEC-amine)/IC(BCEOC-amine)=1.23-2.47 (Here, IC: APCI-MS ion current intensity). Detection limits calculated from 0.0244 pmol injection, at a signal-to-noise ratio of 3, were 0.3-3.0 fmol. The relative standard deviations for within-day determination (n=6) were 0.045-0.081% for retention time and 0.86-1.03% for peak area for the tested aliphatic amines. The mean intra- and inter-assay precision for all amine levels were 0.9991. Copyright 2009 Elsevier B.V. All rights reserved.

  10. An improved reagent for determination of aliphatic amines with fluorescence and online atmospheric chemical ionization-mass spectrometry identification

    Energy Technology Data Exchange (ETDEWEB)

    You Jinmao, E-mail: Jmyou6304@163.com [Northwest Plateau Institute of Biology, Chinese Academy of Sciences, Xining, 810001 (China) and Key Laboratory of Life-Organic Analysis, College of Chemistry Science, Qufu Normal University, Qufu Shandong, 273165 (China); Song Cuihua; Yan Tao [Key Laboratory of Life-Organic Analysis, College of Chemistry Science, Qufu Normal University, Qufu Shandong, 273165 (China); Sun Zhiwei [Northwest Plateau Institute of Biology, Chinese Academy of Sciences, Xining, 810001 (China); Graduate University of Chinese Academy of Sciences, Beijing, 100049 (China); Li Yulin; Suo Yourui [Northwest Plateau Institute of Biology, Chinese Academy of Sciences, Xining, 810001 (China)

    2010-01-18

    An improved reagent named 2-[2-(dibenzocarbazole)-ethoxy] ethyl chloroformate (DBCEC-Cl) for the determination of aliphatic amines by high-performance liquid chromatography (HPLC) with fluorescence detection and post-column online atmospheric chemical ionization-mass spectrometry (APCI-MS) identification has been developed. DBCEC-Cl could easily and quickly label aliphatic amines. Derivatives were stable enough to be efficiently analyzed by HPLC and showed an intense protonated molecular ion corresponding m/z [M+H]{sup +} under APCI-MS in positive-ion mode. The ratios for fluorescence responses were I{sub DBCEC-amine}/I{sub BCEC-amine} = 1.02-1.60; I{sub DBCEC-amine}/I{sub BCEOC-amine} = 1.30-2.57; and I{sub DBCEC-amine}/I{sub FMOC-amine} = 2.20-4.12 (here, I was relative fluorescence intensity). The ratios for MS responses were IC{sub DBCEC-amine}/IC{sub BCEC-amine} = 4.16-29.31 and IC{sub DBCEC-amine}/IC{sub BCEOC-amine} = 1.23-2.47 (Here, IC: APCI-MS ion current intensity). Detection limits calculated from 0.0244 pmol injection, at a signal-to-noise ratio of 3, were 0.3-3.0 fmol. The relative standard deviations for within-day determination (n = 6) were 0.045-0.081% for retention time and 0.86-1.03% for peak area for the tested aliphatic amines. The mean intra- and inter-assay precision for all amine levels were <3.64% and 4.67%, respectively. The mean recoveries ranged from 96.9% to 104.7% with their standard deviations in the range of 1.80-2.70 (RSDs%). Excellent linear responses were observed with coefficients of >0.9991.

  11. BSA adsorption on aliphatic and aromatic acid SAMs: investigating the effect of residual surface charge and sublayer nature.

    Science.gov (United States)

    Vallée, Anne; Humblot, Vincent; Al Housseiny, Rana; Boujday, Souhir; Pradier, Claire-Marie

    2013-09-01

    In this work, the influence of surface charge and layer rigidity on Bovin Serum Albumin (BSA) adsorption has been investigated. To this aim, Self Assembled Monolayers (SAMs) bearing terminal COOH or COO(-) groups were built on gold surfaces. The rigidity of the acid terminated SAMs was modified using either an aliphatic, mercaptoundecanoic acid (MUA), or an aromatic, mercaptobenzoic acid (MBA) thiol. X-Ray Photoelectron Spectroscopy (XPS), Polarization Modulation Reflection Absorption Infrared Spectroscopy (PM-RAIRS) and contact angle measurements, were used to deeply characterize the so-built layers. The surface charge was successfully modified by varying the pH of the rinsing solution. Indeed, COOH were the dominating species upon rinsing at pH 2 and COO(-) species dominated upon rinsing at pH 11. Rinsing at an intermediate pH, 5.5, led to the coexistence of both carboxylic and carboxylate moieties. The hydrophilic character of the surface was also found to depend on the rinsing pH, with a minimum after rinsing at intermediate pH. Using aromatic or aliphatic thiols did not affect the speciation but led to considerable differences in the hydrophilic character of these surfaces. Eventually, the adsorption of BSA on the acidic layers was investigated using PM-RAIRS. The results showed interesting differences between the charged layers. Thus, for both MUA and MBA -based SAMs, the amount of adsorbed proteins decreased when the amount of COO(-) on the surface increased. Interestingly, these effects were totally annihilated when the adsorption was carried out in PBS buffer. Moreover, for similar surface charges, the aromatic layers were able to bind higher amounts of proteins than the aliphatic ones. This work points out the key role of both surface charge and rigidity on protein adsorption. The influence of additional parameters, such as hydrophilicity and SAMs' rigidity is also established.

  12. Direct enantioseparation of underivatized aliphatic 3-hydroxyalkanoic acids with a quinine-based zwitterionic chiral stationary phase.

    Science.gov (United States)

    Ianni, Federica; Pataj, Zoltán; Gross, Harald; Sardella, Roccaldo; Natalini, Benedetto; Lindner, Wolfgang; Lämmerhofer, Michael

    2014-10-10

    While aliphatic 2-hydroxyalkanoic acids have been more or less successfully enantioseparated with various chiral stationary phases by HPLC and GC, analogous applications on underivatized aliphatic 3-hydroxyalkanoic acids are completely absent in the scientific literature. With the aim of closing this gap, the enantioseparation of 3-hydroxybutyric acid, 3-hydroxydecanoic acid and 3-hydroxymyristic acid has been performed with two ion-exchange type chiral stationary phases (CSPs): one containing the anion-exchange type tert-butyl carbamoyl quinine chiral selector motif (Chiralpak QN-AX), and the other carrying the new zwitterionic variant based on trans-(S,S)-2-aminocyclohexanesulfonic acid-derivatized quinine carbamate (Chiralpak ZWIX(+)) as the chiral selector and enantiodiscriminating element, respectively. The zwitterionic enantiorecognition material provided better results in terms of enantioselectivity and resolution compared to the anion-exchanger CSP at reduced retention times due to the intramolecular counterion effect imposed by the sulfonic acid moiety and its competition with the 3-hydroxyalkanoic acid analyte for ionic interaction at the quininium-anion exchanger site. It is thus recommended as the CSP of first choice for enantioseparations of the class of aliphatic 3-hydroxyalkanoic acids. With use of polar organic eluent composed of ACN/MeOH/AcOH - 95/5/0.05 (v/v/v), a good compromise in terms of analysis time and enantioresolution quality was accomplished. The major experimental variables have been investigated for optimization of the resolution and allowed to derive information on the enantiorecognition mechanism. Corresponding Chiralpak ZWIX(-), based on pseudo-enantiomeric selector derived from quinidine and trans-(R,R)-2-aminocyclohexanesulfonic acid with opposite configurations provided reversed enantiomer elution orders. It has further to be stressed that these separations can be obtained with mass spectrometry compatible mobile phases.

  13. Determination of Aliphatic Acid and Ester in Ganoderma lucidum by Gas Chromatography-Time of Flight Mass Spectrometry%气相色谱-飞行时间质谱测定灵芝中脂肪酸(酯)

    Institute of Scientific and Technical Information of China (English)

    李前荣; 潘振; 尹浩

    2004-01-01

    The extracts of Ganoderma lucidum capsule powder (A) and natural ganoaerma lucidum (B) have been and analyzed by gas chromatography-time of flight mass spectrometry (GC-TOFMS). A great quantity of aliphatic acid (ester)Was observed at tR= 18min and tR = 20min, including the unsaturated aliphatic acid which is valuable. The relative content of aliphatic acid in sample A was 49.6%, of which 19.4% was linoleic acid, and those in sample B was 32.6%, of which 7.0% was linoleic acid. The relative content of aliphatic acids in sample A was higher than that in sample B.

  14. LLE data for the ionic liquid 3-methyl-N-butyl pyridinium dicyanamide with several aromatic and aliphatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Hansmeier, Antje R., E-mail: a.hansmeier@tue.n [Chair of Process Systems Engineering (SPS), Technical University of Eindhoven, P.O. Box 513, 5600 MB Eindhoven (Netherlands); Jongmans, Mark; Wytze Meindersma, G.; Haan, Andre B. de [Chair of Process Systems Engineering (SPS), Technical University of Eindhoven, P.O. Box 513, 5600 MB Eindhoven (Netherlands)

    2010-04-15

    (Liquid + liquid) equilibrium data for ternary systems of several aromatic and aliphatic hydrocarbons with the ionic liquid 3-methyl-N-butylpyridinium dicyanamide were determined at T = 303.15 K and 328.15 K and atmospheric pressure. As aromatics benzene, cumene and p-xylene have been chosen, as paraffins n-hexane and n-nonane were used. The experimental data were regressed and could be adequately correlated with the NRTL model. A logical order in the extraction capacity of 3-methyl-N-butylpyridinium dicyanamide for the different aromatics is obtained: benzene > p-xylene > cumene.

  15. Application of variable anti-connectivity index to active sites. Modelling pK(a) values of aliphatic monocarboxylic acids.

    Science.gov (United States)

    Sčavničar, A; Balaban, A T; Pompe, M

    2013-01-01

    A partial distance-weighted variable anti-connectivity topological index was introduced for modelling pK(a) values of 31 aliphatic carboxylic acids and haloalkyl-carboxylic acids. The partial distance-weighted variable anti-connectivity index showed superior modelling capabilities compared with the index calculated from the complete graph, because it is capable of accounting correctly for the intramolecular interactions of unconnected vertices to specific bond strengths (active site), thereby improving the RMS(CV) error by about 30% (0.221 pK(a) units).

  16. 脂肪族水性聚氨酯涂料的研制%Development of Waterborne Aliphatic Polyurethane Coatings

    Institute of Scientific and Technical Information of China (English)

    许戈文; 熊潜生; 等

    2001-01-01

    A waterborne aliphatic polyurethane coatings was prepared by epoxy resin modified polyurethane and IPDI instead of TDI. The in fluences ofreaction temperature, catalyst, NCO content and chain extender etc. on the paint property were discussed.%采用环氧树脂改性聚氨酯,异佛尔酮二异氰酸酯代替甲苯二异氰酸酯合成出耐候性好的水性聚氨酯树脂。讨论了反应温度、催化剂、NCO含量及扩链剂等对涂料性能的影响。

  17. Catalysis by amino acid-derived tetracoordinate complexes: enantioselective addition of dialkylzincs to aliphatic and aromatic aldehydes.

    Science.gov (United States)

    Dangel, B D; Polt, R

    2000-09-21

    Me(2)Zn and Et(2)Zn added to aromatic and aliphatic aldehydes in the presence of 3 mol % of 2. (S)-1-Phenylethanol (91% ee) and (S)-1-phenylpropanol (86% ee) were synthesized from benzaldehyde and (S)-1-furan-2-yl-1-propanol (86% ee) from 2-furaldehyde. Nonanal and 3-phenylpropanal provided (S)-3-undecanol (96% ee) and (S)-1-phenyl-3-pentanol (94% ee). A solid-phase variant was effective with reduced ee's (e.g., 86% ee --> 79% ee) for (S)-1-phenylpropanol.

  18. Marsh plant response to metals: Exudation of aliphatic low molecular weight organic acids (ALMWOAs)

    Science.gov (United States)

    Rocha, A. Cristina S.; Almeida, C. Marisa R.; Basto, M. Clara P.; Vasconcelos, M. Teresa S. D.

    2016-03-01

    Metal exposure is known to induce the production and secretion of substances, such as aliphatic low molecular weight organic acids (ALMWOAs), into the rhizosphere by plant roots. Knowledge on this matter is extensive for soil plants but still considerably scarce regarding marsh plants roots adapted to high salinity media. Phragmites australis and Halimione portulacoides, two marsh plants commonly distributed in European estuarine salt marshes, were used to assess the response of roots of both species, in terms of ALMWOAs exudation, to Cu, Ni and Cd exposure (isolated and in mixture since in natural environment, they are exposed to mixture of metals). As previous studies were carried out in unrealistic and synthetic media, here a more natural medium was selected. Therefore, in vitro experiments were carried out, with specimens of both marsh plants, and in freshwater contaminated with two different Cu, Ni and Cd concentrations (individual metal and in mixture). Both marsh plants were capable of liberating ALMWOAs into the surrounding medium. Oxalic, citric and maleic acids were found in P. australis root exudate solutions and oxalic and maleic acids in H. portulacoides root exudate solutions. ALMWOA liberation by both plants was plant species and metal-dependent. For instance, Cu affected the exudation of oxalic acid by H. portulacoides and of oxalic and citric acids by P. australis roots. In contrast, Ni and Cd did not stimulate any specific response. Regarding the combination of all metals, H. portulacoides showed a similar response to that observed for Cu individually. However, in the P. australis case, at high metal concentration mixture, a synergetic effect led to the increase of oxalic acid levels in root exudate solution and to a decrease of citric acid liberation. A correlation between ALMWOAs exudation and metal accumulation could not be established. P. australis and H. portulacoides are considered suitable metal phytoremediators of estuarine impacted areas

  19. Suberin-derived aliphatic monomers as biomarkers for SOM affected by root litter contribution

    Science.gov (United States)

    Kogel-Knabner, I.; Spielvogel, S.-; Prietzel, J.-

    2012-12-01

    The patchy distribution of trees and ground vegetation may have major impact on SOC variability and stability at the small scale. Knowledge about correlations between the pattern of tree and ground vegetation, SOC stocks in different soil depths and the contribution of root- vs. shoot-derived carbon to different SOC fractions is scarce. We have tested analysis of hydrolysable aliphatic monomers derived from the biopolyesters cutin- and suberin to investigate whether their composition can be traced back after decay and transformation into soil organic matter (SOM) to study SOM source, degradation, and stand history. The main objective of this study was to elucidate the relative abundance of cutin and suberin in different particle size and density fractions of a Norway spruce and a European beech site with increasing distance to stems. Soil samples, root, bark and needle/leave samples were analyzed for their cutin and/or suberin signature. Previous to isolation of bound lipids, sequential solvent extraction was used to remove free lipids and other solvent extractable compounds. Cutin- and suberin-derived monomers were extracted from the samples using base hydrolysis. Before analysis by Gas Chromatography/Mass Spectrometry (GC/MS), extracts were derivatized to convert compounds to trimethylsilyl derivatives. Statistical analysis identified four variables which as combined factors discriminated significantly between cutin and suberin based on their structural units. We found a relative enrichment of cutin and suberin contents in the occluded fraction at both sites that decreased with increasing distance to the trees. We conclude from our results that (i) patchy above- and belowground carbon input caused by heterogeneous distribution of trees and ground vegetation has major impact on SOC variability and stability at the small scale, (ii) tree species is an important factor influencing SOC heterogeneity at the stand scale due to pronounced differences in above- and

  20. Lipase-catalyzed synthesis of aliphatic polyesters via copolymerization of lactone, dialkyl diester, and diol.

    Science.gov (United States)

    Jiang, Zhaozhong

    2008-11-01

    Candida antarctica lipase (CALB) has been successfully used as catalyst for copolymerization of dialkyl diester with diol and lactone to form aliphatic polyesters. The polymerization reactions were performed using a two stage process: first stage oligomerization under low vacuum followed by second stage polymerization under high vacuum. Use of the two-stage process is required to obtain products with high molecular weights at high yields for the following reasons: (i) the first stage reaction ensures that the monomer loss via evaporation is minimized to maintain 1:1 diester to diol stoichiometric ratio, and the monomers are converted to nonvolatile oligomers; (ii) use of high vacuum during the second stage accelerates equilibrium transesterification reactions to transform the oligomers to high molecular weight polymers. Thus, terpolymers of omega-pentadecalactone (PDL), diethyl succinate (DES), and 1,4-butanediol (BD) with a M w of whole product (nonfractionated) up to 77000 and M w/ M n between 1.7 and 4.0 were synthesized in high yields (e.g., 95% isolated yield). A desirable reaction temperature for the copolymerizations was found to be around 95 degrees C. At 1:1:1 PDL/DES/BD monomer molar ratio, the resultant terpolymers contained equal moles of PDL, succinate, and butylene repeat units in the polymer chains. (1)H and (13)C NMR analyses were used to determine the polyester microstructures. The synthesized PDL-DES-BD terpolymers possessed near random structures with all possible combinations of PDL, succinate, and butylene units via ester linkages in the polymer backbone. Furthermore, thermal stability and crystallinity of a pure PDL-DES-BD terpolymer with 1:1:1 PDL to succinate to butylene unit ratio and M w of 85400 were studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The copolyester was found to be a semicrystalline material with a T g of -34 degrees C and a T m of 64 degrees C, which degrades in a single weight loss

  1. Aliphatic amines in Antarctic CR2, CM2, and CM1/2 carbonaceous chondrites

    Science.gov (United States)

    Aponte, José C.; McLain, Hannah L.; Dworkin, Jason P.; Elsila, Jamie E.

    2016-09-01

    Meteoritic water-soluble organic compounds provide a unique record of the processes that occurred during the formation of the solar system and the chemistry preceding the origins of life on Earth. We have investigated the molecular distribution, compound-specific δ13C isotopic ratios and enantiomeric compositions of aliphatic monoamines present in the hot acid-water extracts of the carbonaceous chondrites LAP 02342 (CR2), GRA 95229 (CR2), LON 94101 (CM2), LEW 90500 (CM2), and ALH 83100 (CM1/2). Analyses of the concentration of monoamines in these meteorites revealed: (a) the CR2 chondrites studied here contain higher concentrations of monoamines relative to the analyzed CM2 chondrites; (b) the concentration of monoamines decreases with increasing carbon number; and (c) isopropylamine is the most abundant monoamine in these CR2 chondrites, while methylamine is the most abundant amine species in these CM2 and CM1/2 chondrites. The δ13C values of monoamines in CR2 chondrite do not correlate with the number of carbon atoms; however, in CM2 and CM1/2 chondrites, the 13C enrichment decreases with increasing monoamine carbon number. The δ13C values of methylamine in CR2 chondrites ranged from -1 to +10‰, while in CM2 and CM1/2 chondrites the δ13C values of methylamine ranged from +41 to +59‰. We also observed racemic compositions of sec-butylamine, 3-methyl-2-butylamine, and sec-pentylamine in the studied carbonaceous chondrites. Additionally, we compared the abundance and δ13C isotopic composition of monoamines to those of their structurally related amino acids. We found that monoamines are less abundant than amino acids in CR2 chondrites, with the opposite being true in CM2 and CM1/2 chondrites. We used these collective data to evaluate different primordial synthetic pathways for monoamines in carbonaceous chondrites and to understand the potential common origins these molecules may share with meteoritic amino acids.

  2. Mechanism and Thermodynamics of Reductive Cleavage of Carbon-Halogen Bonds in the Polybrominated Aliphatic Electrophiles.

    Science.gov (United States)

    Rosokha, Sergiy V; Lukacs, Emoke; Ritzert, Jeremy T; Wasilewski, Adam

    2016-03-17

    Quantum-mechanical computations revealed that, despite the presence of electron-withdrawing and/or π-acceptor substituents, the lowest unoccupied molecular orbitals (LUMO) of the polybromosubstituted aliphatic molecules R-Br (R-Br = C3Br2F6, CBr3NO2, CBr3CN, CBr3CONH2, CBr3CO2H, CHBr3, CFBr3, CBr4, CBr3COCBr3) are delocalized mostly over their bromine-containing fragments. The singly occupied molecular orbitals in the corresponding vertically excited anion radicals (R-Br(•-))* are characterized by essentially the same shapes and show nodes in the middle of the C-Br bonds. An injection of an electron into the antibonding LUMO results in the barrierless dissociation of the anion-radical species and the concerted reductive cleavages of C-Br bonds leading to the formation of the loosely bonded {R(•)···Br(-)} associates. The interaction energies between the fragments of these ion-radical pairs vary from ∼10 to 20 kcal mol(-1) in the gas phase and from 1 to 3 kcal mol(-1) in acetonitrile. In accord with the concerted mechanism of reductive cleavage, all R-Br molecules showed completely irreversible reduction waves in the voltammograms in the whole range of the scan rates employed (from 0.05 to 5 V s(-1)). Also, the transfer coefficients α, established from the width of these waves and dependence of reduction peak potentials Ep on the scan rates, were significantly lower than 0.5. The standard reduction potentials of the R-Br electrophiles, E(o)R-Br/R·+X(-), and the corresponding R(•) radicals, E(o)R(•)/R(-), were calculated in acetonitrile using the appropriate thermodynamic cycles. In agreement with these calculations, which indicated that the R(•) radicals resulting from the reductive cleavage of the R-Br molecules are stronger oxidants than their parents, the reduction peaks' currents in cyclic voltammograms were consistent with the two-electron transfer processes.

  3. Multilinear relations between {sup 13} C NMR chemical shifts of aliphatic halides; Relacoes lineares multiplas entre deslocamentos quimicos em RMN {sup 13} C de haletos alifaticos

    Energy Technology Data Exchange (ETDEWEB)

    Doyama, Julio Toshimi [UNESP, Botucatu, SP (Brazil). Inst. de Biociencias. Dept. de Quimica e Bioquimica; Tornero, Maria Teresinha Trovarelli [UNESP, Botucatu, SP (Brazil). Inst. de Biociencias. Dept. de Bioestatistica; Yoshida, Massayoshi [UNESP, Araraquara, SP (Brazil). Inst. de Quimica. Dept. de Quimica Organica

    1999-07-01

    The {sup 13} C NMR chemical shifts of the {alpha}, {beta}, {gamma} and {delta} carbons of 17 sets of aliphatic halides (F, Cl, Br and I), including mono, bi and tricyclic compounds, can be reproduced by a linear equation composed with two constants and two variables: {delta}{sub RX} = A{sup *} {delta}{sub R-X2}, where A and B are constants derived from multilinear regression of {sup 13} C chemical shifts observed; {delta}{sub R-X}, the chemical shifts of aliphatic halide (R-X); and {delta}{sub R-X1}, {delta}{sub R-X2} the chemical shifts of other halides. It was observed a better correlation for aliphatic bromides (R-X) by using data of aliphatic fluorides (R-X 1) and aliphatic iodides (R-X 2), resulting R{sup 2} of 0.9989 and average absolute deviation (AVG) of 0.39 ppm. For the chlorides (R-X), the better correlation was observed by using data of bromides (R-X 1) was observed better correlation with data of bromides (R-X 1) and iodides (R-X 2), R{sup 2} of 0.997 and AVG of 1.10 ppm. For the iodides (R-X) was observed better correlation with data of fluorides (R-X 1) and bromides (R-X 2), R{sup 2} of 0.9972 and AVG of 0.60 ppm. (author)

  4. Aliphatic C-C Bond Cleavage in α-Hydroxy Ketones by a Dioxygen-Derived Nucleophilic Iron-Oxygen Oxidant.

    Science.gov (United States)

    Bhattacharya, Shrabanti; Rahaman, Rubina; Chatterjee, Sayanti; Paine, Tapan K

    2017-03-17

    A nucleophilic iron-oxygen oxidant, formed in situ in the reaction between an iron(II)-benzilate complex and O2 , oxidatively cleaves the aliphatic C-C bonds of α-hydroxy ketones. In the cleavage reaction, α-hydroxy ketones without any α-C-H bond afford a 1:1 mixture of carboxylic acid and ketone. Isotope labeling studies established that one of the oxygen atoms from dioxygen is incorporated into the carboxylic acid product. Furthermore, the iron(II) complex cleaves an aliphatic C-C bond of 17-α-hydroxyprogesterone affording androstenedione and acetic acid. The O2 -dependent aliphatic C-C bond cleavage of α-hydroxy ketones containing no α-C-H bond bears similarity to the lyase activity of the heme enzyme, cytochrome P450 17A1 (CYP17A1). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. An amino acid at position 142 in nitrilase from Rhodococcus rhodochrous ATCC 33278 determines the substrate specificity for aliphatic and aromatic nitriles

    Science.gov (United States)

    Yeom, Soo-Jin; Kim, Hye-Jung; Lee, Jung-Kul; Kim, Dong-Eun; Oh, Deok-Kun

    2008-01-01

    Nitrilase from Rhodococcus rhodochrous ATCC 33278 hydrolyses both aliphatic and aromatic nitriles. Replacing Tyr-142 in the wild-type enzyme with the aromatic amino acid phenylalanine did not alter specificity for either substrate. However, the mutants containing non-polar aliphatic amino acids (alanine, valine and leucine) at position 142 were specific only for aromatic substrates such as benzonitrile, m-tolunitrile and 2-cyanopyridine, and not for aliphatic substrates. These results suggest that the hydrolysis of substrates probably involves the conjugated π-electron system of the aromatic ring of substrate or Tyr-142 as an electron acceptor. Moreover, the mutants containing charged amino acids such as aspartate, glutamate, arginine and asparagine at position 142 displayed no activity towards any nitrile, possibly owing to the disruption of hydrophobic interactions with substrates. Thus aromaticity of substrate or amino acid at position 142 in R. rhodochrous nitrilase is required for enzyme activity. PMID:18412544

  6. An amino acid at position 142 in nitrilase from Rhodococcus rhodochrous ATCC 33278 determines the substrate specificity for aliphatic and aromatic nitriles.

    Science.gov (United States)

    Yeom, Soo-Jin; Kim, Hye-Jung; Lee, Jung-Kul; Kim, Dong-Eun; Oh, Deok-Kun

    2008-11-01

    Nitrilase from Rhodococcus rhodochrous ATCC 33278 hydrolyses both aliphatic and aromatic nitriles. Replacing Tyr-142 in the wild-type enzyme with the aromatic amino acid phenylalanine did not alter specificity for either substrate. However, the mutants containing non-polar aliphatic amino acids (alanine, valine and leucine) at position 142 were specific only for aromatic substrates such as benzonitrile, m-tolunitrile and 2-cyanopyridine, and not for aliphatic substrates. These results suggest that the hydrolysis of substrates probably involves the conjugated pi-electron system of the aromatic ring of substrate or Tyr-142 as an electron acceptor. Moreover, the mutants containing charged amino acids such as aspartate, glutamate, arginine and asparagine at position 142 displayed no activity towards any nitrile, possibly owing to the disruption of hydrophobic interactions with substrates. Thus aromaticity of substrate or amino acid at position 142 in R. rhodochrous nitrilase is required for enzyme activity.

  7. Adsorption of 1,13-tetradecadiene on Si(111)7×7 studied by STM: possible electrostatic interactions between the aliphatic chain and the surface

    Science.gov (United States)

    Shachal, D.; Manassen, Y.

    Non-covalent intermolecular forces play an important role in the reactions of complicated chemical systems. In this paper we show how such forces affect the reaction between 1,13-tetradecadiene and Si(111)7×7. Previous work has shown that one double bond reacts with the faulted half of the Si(111)7×7 and the other with the unfaulted half. However, since each half contains six adatoms, there is an additional degree of freedom in which the aliphatic chain can reside mostly above either half. We found a preference of the aliphatic chain to reside above the unfaulted half. This can be explained only as a result of different non-covalent intermolecular forces between the chain and each of the two halves. According to our calculations the difference in energy between the two halves on which an aliphatic chain is physi-sorbed is 30 kcal/molecule.

  8. Camphor-10-sulfonic acid catalyzed condensation of 2-naphthol with aromatic/aliphatic aldehydes to 14-aryl/alkyl-14H-dibenzo[a,j]xanthenes

    Directory of Open Access Journals (Sweden)

    Kundu Kshama

    2014-01-01

    Full Text Available (±-Camphor-10-sulfonic acid (CSA catalyzed condensation of 2-naphthol with both aliphatic/aromatic aldehydes at 80°C yielded 14-alkyl/aryl-dibenzoxanthenes as the sole product in high yields. However, the same condensation with benzaldehyde at 25°C afforded a mixture of intermediate 1,1-bis-(2-hydroxynaphthylphenylmethane and 14-phenyl-dibenzoxanthene while the condensation with aliphatic aldehydes at 25°C furnished the corresponding 14-alkyl-dibenzoxanthenes as the sole product. Moreover, condensation of 2-naphthol with aromatic/aliphatic aldehydes with low catalyst loading (2 mol% was greatly accelerated under microwave irradiation to afford the corresponding 14-aryl/alkyl-dibenzoxanthenes as the sole product in high yields.

  9. A novel high-performance thin layer chromatography method for quantification of long chain aliphatic hydrocarbons from Cissus quadrangularis

    Directory of Open Access Journals (Sweden)

    Vandana Jain

    2016-08-01

    Full Text Available Context: A high-performance thin layer chromatography (HPTLC is an analytical technique, which can be used for the determination of constituents or marker components in various parts of the plants. Earlier studies have estimated phytoconstituents from the stem and other aerial plant parts of Cissus quadrangularis Linn. Estimation of hydrocarbons can also be successfully done using HPTLC technique using suitable derivatization. Aims: To develop and validate a simple and rapid method for the estimation of long chain aliphatic hydrocarbons from the leaves of C. quadrangularis using HPTLC technique. Methods: Precoated silica gel 60 F254 plates were used as stationary phase. The mobile phase used was hexane (100 %. The detection of spots was carried out using berberine sulphate as detecting reagent. Results: The method was validated in terms of linearity, sensitivity, accuracy, and precision. Linearity range was found to be 2-10 µg/mL, limit of detection 0.127 µg/mL, and limit of quantification 0.384 µg/mL. Conclusions: A novel, simple, accurate, precise and sensitive HPTLC method has been developed and validated for the estimation of long chain aliphatic hydrocarbons obtained from the leaves of C. quadrangularis Linn.

  10. Forensic investigation of aliphatic hydrocarbons in the sediments from selected mangrove ecosystems in the west coast of Peninsular Malaysia.

    Science.gov (United States)

    Vaezzadeh, Vahab; Zakaria, Mohamad Pauzi; Shau-Hwai, Aileen Tan; Ibrahim, Zelina Zaiton; Mustafa, Shuhaimi; Abootalebi-Jahromi, Fatemeh; Masood, Najat; Magam, Sami Mohsen; Alkhadher, Sadeq Abdullah Abdo

    2015-11-15

    Peninsular Malaysia has gone through fast development during recent decades resulting in the release of large amounts of petroleum and its products into the environment. Aliphatic hydrocarbons are one of the major components of petroleum. Surface sediment samples were collected from five rivers along the west coast of Peninsular Malaysia and analyzed for aliphatic hydrocarbons. The total concentrations of C10 to C36 n-alkanes ranged from 27,945 to 254,463ng·g(-1)dry weight (dw). Evaluation of various n-alkane indices such as carbon preference index (CPI; 0.35 to 3.10) and average chain length (ACL; 26.74 to 29.23) of C25 to C33 n-alkanes indicated a predominance of petrogenic source n-alkanes in the lower parts of the Rivers, while biogenic origin n-alkanes from vascular plants are more predominant in the upper parts, especially in less polluted areas. Petrogenic sources of n-alkanes are predominantly heavy and degraded oil versus fresh oil inputs.

  11. In-Situ Heating Decrease Kinetics of Aliphatic Hydrocarbons in Tagish Lake Meteorite by Micro-FTIR

    Science.gov (United States)

    Kebukawa, Y.; Nakashima, S.; Zolensky, M. E.

    2005-01-01

    Carbonaceous chondrites are known to contain up to 3wt.% C, the major part of which corresponds to a macromolecular organic fraction. Chondritic organic matter is based on small aromatic units, cross-linked by short aliphatic chains rather than large clusters of polyaromatic structures. Two main characteristic features of those organics measured by FTIR are: (1) an equivalent intensity of the asymmetric stretching mode absorptions for CH3 (2960/cm) and CH2 (2920/cm) and (2) a lack of aromatic CH-stretching mode (3040/cm). Tagish Lake is a new type of water- and carbon-rich type 2 carbonaceous chondrite. Its total carbon content is approx. 5 wt%, of which the organic carbon content reaches approx. 1.3 wt%. Tagish Lake may have never experienced temperatures higher than 120 C after formation of organics based on the disappearance of infrared (IR) organic peaks in step heating experiments. Here we report in-situ kinetic heating experiments of organics in Tagish Lake by micro-FTIR to characterize the nature of aliphatic hydrocarbons and their thermal stabilities.

  12. Content of carotenoids, tocopherols, sterols, triterpenic and aliphatic alcohols, and volatile compounds in six walnuts (Juglans regia L.) varieties.

    Science.gov (United States)

    Abdallah, Ikram Bou; Tlili, Nizar; Martinez-Force, Enrique; Rubio, Ana Gracia Pérez; Perez-Camino, Maria Carmen; Albouchi, Ali; Boukhchina, Sadok

    2015-04-15

    The aim of this work was to study the content of tocopherols, sterols, triterpenic and aliphatic alcohols, carotenoids, and volatile compounds in the kernel oils from six walnut (Juglans regia L.) varieties. The levels of β-carotene ranged between 0.22 and 0.62 mg/kg, followed by lutein (0.01-0.06 mg/kg). The total content of tocopherol ranged from 186.5 to 436.2 mg/kg of the extracted oil and the major isoform in all samples was γ-tocopherol. The most abundant phytosterol was β-sitosterol (974-1494 mg/kg) followed by campesterol then Δ-5-avenasterol. The major triterpenic alcohol was cycloartenol (226.4-532.1 mg/kg). Hexacosanol (9.71-28.15 mg/kg) was the major aliphatic alcohol. The detected volatile compounds were pentanal, hexanal, nonanal, 2-decenal and hexanol. The statistical analysis showed significant differences between varieties, which are probably due to genetic factors.

  13. Ion-Exclusion High-Performance Liquid Chromatography of Aliphatic Organic Acids Using a Surfactant-Modified C18 Column.

    Science.gov (United States)

    Fasciano, Jennifer M; Mansour, Fotouh R; Danielson, Neil D

    2016-07-01

    Ion exclusion chromatography (IELC) of short chain aliphatic carboxylic acids is normally done using a cation exchange column under standard HPLC conditions but not in the ultra-HPLC (UHPLC) mode. A novel IELC method for the separation of this class of carboxylic acids by either HPLC or UHPLC utilizing a C18 column dynamically modified with sodium dodecyl sulfate has been developed. The sample capacity is estimated to be near 10 mM for a 20 µL injection or 0.2 µmol using a 150 × 4.6 mm column. The optimum mobile phase determined for three standard mixtures of organic acids is 1.84 mM sulfuric acid at pH 2.43 and a flow rate of 0.6 mL/min. Under optimized conditions, a HPLC separation of four aliphatic carboxylic acids such as tartaric, malonic, lactic and acetic can be achieved in under 4 min and in column as measured by the retention order of maleic and fumaric acid is estimated to be ∼4,000 column volumes using HPLC and 600 by UHPLC. Reproducible chromatograms are achieved over at least a 2-month period. This study shows that the utility of a C18 column can be easily extended when needed to IELC under either standard or UHPLC conditions.

  14. Vortex-assisted liquid-liquid microextraction coupled with derivatization for the fluorometric determination of aliphatic amines.

    Science.gov (United States)

    Chang, Wei-Yao; Wang, Chin-Yi; Jan, Jeng-Lyan; Lo, Yu-Shiu; Wu, Chien-Hou

    2012-07-27

    A new one-step derivatization and microextraction technique was developed for the fluorometric determination of C(1)-C(8) linear aliphatic primary amines in complex sample solutions containing high levels of amino acids. In this method, amines were derivatized with o-phthalaldehyde (OPA) and 2-mercaptoethanol (2-ME) in aqueous solution and extracted simultaneously by vortex-assisted liquid-liquid microextraction (VALLME). Parameters affecting the extraction efficiency were investigated in detail. The optimum conditions were as follows: 50 μL of isooctane as the extractant phase; 2.0 mL aqueous donor samples with 12 mM OPA, 24 mM 2-ME, and 0.1 M borate buffer at pH 10; 1 min vortex extraction time; centrifugation for 4 min at 6000 rpm. After centrifugation, the enriched analytes in the floated extractant phase were determined by HPLC-FL in less than 14 min. Under the optimum conditions, the limits of detection were of the order of 0.09-0.31 nM. The calibration curves showed good linearity over the investigated concentration range between 0.4 and 40 nM. The proposed method has been applied to the determination of aliphatic amines in acidophilus milk, beer, and Cu(II)/amino acid solution.

  15. The kinetics of photocatalytic degradation of aliphatic carboxylic acids in an UV/TiO2 suspension system.

    Science.gov (United States)

    Chen, Q; Song, J M; Pan, F; Xia, F L; Yuan, J Y

    2009-10-01

    Kinetic studies on the photocatalytic degradation of aliphatic carboxylic acids were carried out in a slurry photoreactor with in-situ monitoring, employing artificial UV light as the source of energy and nano-TiO2 powder as the catalyst. The influences on the photocatalytic degradation such as the initial concentration of reactant (C0), catalyst dosage (CTiO2), UV intensity (Ia) and pH value have been investigated. Good agreement has been obtained between the value calculated by Langmuir-Freundlich-Hinshelwood (L-F-H) model and experimental data, with coefficient of multiple determination (R2) varying from 0.880 to 0.999. The L-F-H model has been proven to be feasible in describing the kinetic characteristic of the photocatalytic degradation of aliphatic carboxylic acids. Moreover, the apparent reaction rate constant (k) of the photocatalytic degradation of dicarboxylic acids is higher than that of monocarboxylic acids with the same carbon atoms. This shows that the photocatalytic degradation rate is favoured by different chemical structure.

  16. Regioselective oxygenation of fatty acids, fatty alcohols and other aliphatic compounds by a basidiomycete heme-thiolate peroxidase.

    Science.gov (United States)

    Gutiérrez, Ana; Babot, Esteban D; Ullrich, René; Hofrichter, Martin; Martínez, Angel T; del Río, José C

    2011-10-01

    Reaction of fatty acids, fatty alcohols, alkanes, sterols, sterol esters and triglycerides with the so-called aromatic peroxygenase from Agrocybe aegerita was investigated using GC-MS. Regioselective hydroxylation of C(12)-C(20) saturated/unsaturated fatty acids was observed at the ω-1 and ω-2 positions (except myristoleic acid only forming the ω-2 derivative). Minor hydroxylation at ω and ω-3 to ω-5 positions was also observed. Further oxidized products were detected, including keto, dihydroxylated, keto-hydroxy and dicarboxylic fatty acids. Fatty alcohols also yielded hydroxy or keto derivatives of the corresponding fatty acid. Finally, alkanes gave, in addition to alcohols at positions 2 or 3, dihydroxylated derivatives at both sides of the molecule; and sterols showed side-chain hydroxylation. No derivatives were found for fatty acids esterified with sterols or forming triglycerides, but methyl esters were ω-1 or ω-2 hydroxylated. Reactions using H(2)(18)O(2) established that peroxide is the source of the oxygen introduced in aliphatic hydroxylations. These studies also indicated that oxidation of alcohols to carbonyl and carboxyl groups is produced by successive hydroxylations combined with one dehydration step. We conclude that the A. aegerita peroxygenase not only oxidizes aromatic compounds but also catalyzes the stepwise oxidation of aliphatic compounds by hydrogen peroxide, with different hydroxylated intermediates.

  17. Surface activity of new invertible amphiphilic polyesters based on poly(ethylene glycol) and aliphatic dicarboxylic acids.

    Science.gov (United States)

    Voronov, A; Vasylyev, S; Kohut, A; Peukert, W

    2008-07-15

    The surface active properties of aqueous solutions of invertible amphiphilic alternated polyesters differing by hydrophilic-lipophilic balance (HLB) and molecular weight have been determined over the wide concentration range. The polyesters are based on poly(ethylene glycol) (PEG) of two molecular weights and aliphatic dicarboxylic acids (decanedioic and dodecanedioic). The surface activity of the polyesters and their ability to form micellar assemblies (which was recently shown for organic solvents) has been confirmed in water. The central role of the balance of hydrophilic to hydrophobic groups ratio in the formation of polymeric arrangements having hydrophobic pockets and external hydrophilic shell has been shown. The effect of molecular weight has been found considerable as well. Two changes in slope have been observed for the more hydrophobic polyesters in the surface tension vs log concentration curve. The change at low concentration is believed to originate from the formation of polyester assemblies with a hydrophobic interior and hydrophilic exterior due to the interaction of hydrophobic fragments and macromolecular flexibility. The higher concentration region exhibits behavior consistent with a cmc, which was confirmed by additional dye solubilization experiments. Molecular structure of the polyester micelles is determined by the solubilization of a solvatochromic dye. The experiment confirmed that micellization of polyesters is accompanied by the association of more hydrophobic (aliphatic) constituents forming the micelle interior. The hydrophilic fragments (ethylene oxide groups) are involved in the formation of micelle exterior.

  18. Fine Control over Site and Substrate Selectivity in Hydrogen Atom Transfer-Based Functionalization of Aliphatic C-H Bonds.

    Science.gov (United States)

    Salamone, Michela; Carboni, Giulia; Bietti, Massimo

    2016-10-07

    The selective functionalization of unactivated aliphatic C-H bonds over intrinsically more reactive ones represents an ongoing challenge of synthetic chemistry. Here we show that in hydrogen atom transfer (HAT) from the aliphatic C-H bonds of alkane, ether, alcohol, amide, and amine substrates to the cumyloxyl radical (CumO(•)) fine control over site and substrate selectivity is achieved by means of acid-base interactions. Protonation of the amines and metal ion binding to amines and amides strongly deactivates the C-H bonds of these substrates toward HAT to CumO(•), providing a powerful method for selective functionalization of unactivated or intrinsically less reactive C-H bonds. With 5-amino-1-pentanol, site-selectivity has been drastically changed through protonation of the strongly activating NH2 group, with HAT that shifts to the C-H bonds that are adjacent to the OH group. In the intermolecular selectivity studies, trifluoroacetic acid, Mg(ClO4)2, and LiClO4 have been employed in a orthogonal fashion for selective functionalization of alkane, ether, alcohol, and amide (or amine) substrates in the presence of an amine (or amide) one. Ca(ClO4)2, that promotes deactivation of amines and amides by Ca(2+) binding, offers, moreover, the opportunity to selectively functionalize the C-H bonds of alkane, ether, and alcohol substrates in the presence of both amines and amides.

  19. A Comparative Study of Two Quantum Chemical Descriptors in Predicting Toxicity of Aliphatic Compounds towards Tetrahymena pyriformis

    Directory of Open Access Journals (Sweden)

    Altaf Hussain Pandith

    2010-01-01

    Full Text Available Quantum chemical parameters such as LUMO energy, HOMO energy, ionization energy (I, electron affinity (A, chemical potential (μ, hardness (η electronegativity (χ, philicity (ωα, and electrophilicity (ω of a series of aliphatic compounds are calculated at the B3LYP/6-31G(d level of theory. Quantitative structure-activity relationship (QSAR models are developed for predicting the toxicity (pIGC50 of 13 classes of aliphatic compounds, including 171 electron acceptors and 81 electron donors, towards Tetrahymena pyriformis. The multiple linear regression modeling of toxicity of these compounds is performed by using the molecular descriptor log P (1-octanol/water partition coefficient in conjunction with two other quantum chemical descriptors, electrophilicity (ω and energy of the lowest unoccupied molecular orbital (ELUMO. A comparison is made towards the toxicity predicting the ability of electrophilicity (ω versus ELUMO as a global chemical reactivity descriptor in addition to log P. The former works marginally better in most cases. There is a slight improvement in the quality of regression by changing the unit of IGC50 from mg/L to molarity and by removing the racemates and the diastereoisomers from the data set.

  20. In Situ and Laboratory Studies on the Fate of Specific Organic Compounds in an Anerobic Landfill Leachate Plume, 2. Fate of Aromatic and Chlorinated Aliphatic Compounds

    DEFF Research Database (Denmark)

    Nielsen, Per Henning; Bjarnadóttir, Helga; Winter, Pia L.

    1995-01-01

    and laboratory batch microcosm experiments performed focusing on redox conditions, microbiology and the fate of 7 phenolic compounds. In this paper we present the results on the fate of 8 aromatic compounds and 4 chlorinated aliphatic compounds. Nitrobenzene was transformed at all distances from the landfill...... the landfill in Fe(IIl)-reducing conditions but not in NO3-reducing conditions at 350 m from the landfill. Abiotic processes apparently contributed to the transformation of tetrachloromethane. A local variation in the transformation of the chlorinated aliphatic hydrocarbons was observed at 2 m from...

  1. The Cer-cqu gene cluster determines three key players in a β-diketone synthase polyketide pathway synthesizing aliphatics in epicuticular waxes

    DEFF Research Database (Denmark)

    Schneider, Lizette Marais; Adamski, Nikolai M.; Christensen, Caspar Elo

    2016-01-01

    Aliphatic compounds on plant surfaces, called epicuticular waxes, are the first line of defense against pathogens and pests, contribute to reducing water loss and determine other important phenotypes. Aliphatics can form crystals affecting light refraction, resulting in a color change and allowing...... and Cer-u is a P450 enzyme. All were highly expressed in pertinent leaf sheath tissue of wild type. A physical map revealed the order Cer-c, Cer-u, Cer-q with the flanking genes 101kb apart, confirming they are a gene cluster, Cer-cqu. Homology-based modeling suggests that many of the mutant alleles...

  2. EFSA CEF Panel (EFSA Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids), 2014. Scientific Opinion on Flavouring Group Evaluation 91, Re vision 2 (FGE.91Rev2): Consid eration of simple aliphatic and aromatic sulphides and thiols evaluated by the JECFA (53rd and 68th meetings

    DEFF Research Database (Denmark)

    Beltoft, Vibe Meister; Binderup, Mona-Lise; Frandsen, Henrik Lauritz

    The Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids of the European Food Safety Authority was requested to consider evaluations of flavouring substances assessed since 2000 by the Joint FAO/WHO Expert Committee on Food Additives (the JECFA), and to decide whether further...... evaluation is necessary, as laid down in Commission Regulation (EC) No 1565/2000. The present consideration concerns a group of 44 simple aliphatic and aromatic sulphides and thiols evaluated by the JECFA at the 53rd and the 68th meeting. The substances were evaluated through a stepwise approach...

  3. Advances in longer-chain aliphatic olefins metathesis%长碳链烯烃歧化研究进展

    Institute of Scientific and Technical Information of China (English)

    郑敏; 陈胜利; 袁桂梅; 王雪莲; 桑磊; 尤菊; 张军辉

    2012-01-01

    The research of C4-olefin to produce propylene was the emphasis of aliphatic olefin metathesis technology,but attentions were also paid to longer-chain aliphatic olefins metathesis reaction.The progress of the metathesis reaction of longer-chain aliphatic olefins over rhenium based catalysis,molybdenum based catalysis and tungsten based catalysis were introduced.The study of longer-chain olefin metathesis over tungsten based catalyst,including the optimal operating condition of 1-hexene self-metathesis,1-heptene self-metathesis and 1-octene self-metathesis.The effect of pretreatment on metathesis performance of tungsten based catalyst is primarily introduced.Moreover,the studies of deactivation of metathesis catalyst by oxygenate poisoning and deactivation of tungsten based catalyst by coke formation are also introduced.%目前,虽然直链烯烃歧化研究的重点仍是碳四烯烃歧化制丙烯技术,但是长碳链烯烃歧化研究已开始引起人们的重视。本文介绍了铼基催化剂、钼基催化剂和钨基催化剂催化长碳链烯烃歧化反应的研究进展。重点介绍了钨基催化剂上长碳链歧化研究状况,分别介绍了钨基催化剂上1-己烯自歧化、1-庚烯自歧化、1-辛烯自歧化的最优工艺条件研究以及预处理条件对钨基催化剂歧化性能的影响。同时分别介绍了含氧化合物对歧化催化剂中毒失活的研究以及钨基催化剂上结焦失活的研究状况。

  4. The effect of aliphatic carboxylic acids on olfaction-based host-seeking of the malaria mosquito Anopheles gambiae sensu stricto

    NARCIS (Netherlands)

    Smallegange, R.C.; Qiu, Y.T.; Bukovinszkine-Kiss, G.; Loon, van J.J.A.; Takken, W.

    2009-01-01

    The role of aliphatic carboxylic acids in host-seeking response of the malaria mosquito Anopheles gambiae sensu stricto was examined both in a dual-choice olfactometer and with indoor traps. A basic attractive blend of ammonia + lactic acid served as internal standard odor. Single carboxylic acids w

  5. Escherichia coli as a potential hydrocarbon conversion microorganism. Oxidation of aliphatic and aromatic compounds by recombinant E. coli in two-liquid phase (aqueous-organic) systems

    NARCIS (Netherlands)

    Favre-Bulle, Olivier

    1992-01-01

    The increased interest in the study of hydrocarbon utilizing microorganisms in recent years has been stimulated by the possibility of using their monooxygenases in the selective oxidation of aliphatic and aromatic compounds. As an example, long chain (>C16) n-alkanes are converted to dicarboxylic

  6. Synthesis and characterization of soluble, blue-fluorescent polyamides and polyimides containing substituted p-terphenyl as well as long aliphatic segments in the main chain

    NARCIS (Netherlands)

    Mikroyannidis, JA; Tsivgoulis, GM

    1999-01-01

    A novel class of semiflexible polyamides and polyimides bearing substituted p-terphenyl as well as long aliphatic segments in the main chain were synthesized through pyrylium salts. Characterization of polymers was accomplished by inherent viscosity, elemental analysis, FT-IR, NMR, UV-vis luminescen

  7. A novel chiral aliphatic-aromatic diamine promoted direct, highly enantio- and diastereoselective Michael addition of cyclohexanone to nitroolefins under solvent-free conditions.

    Science.gov (United States)

    Miao, Shifeng; Bai, Jinjin; Yang, Jin; Zhang, Yawen

    2010-10-01

    A series of new highly efficient chiral aliphatic-aromatic diamine catalysts have been designed and successfully applied to the asymmetric Michael addition of cyclohexanone with nitroolefins under solvent-free conditions without any acidic additives. The desired adducts were obtained in high yields with excellent enantio- and diastereoselectivities of syn products (up to >99% ee, >99:1 dr).

  8. Aliphatic Imines in Titanium-Mediated Reductive Cross-Coupling: Unique Reactivity of Ti(Oi-Pr)4/n-BuLi

    Science.gov (United States)

    Tarselli, Michael A.; Micalizio, Glenn C.

    2009-01-01

    A procedure for the coupling of aliphatic imines with allylic and allenic alkoxides is described. The success of these studies was enabled by a unique reactivity profile of Ti(IV) isopropoxide/n-BuLi compared to well-known Ti(IV) isopropoxide/R-MgX systems. PMID:19810765

  9. A Quantitative Structure-Property Relationship (QSPR Study of Aliphatic Alcohols by the Method of Dividing the Molecular Structure into Substructure

    Directory of Open Access Journals (Sweden)

    Bin Cheng

    2011-04-01

    Full Text Available A quantitative structure–property relationship (QSPR analysis of aliphatic alcohols is presented. Four physicochemical properties were studied: boiling point (BP, n-octanol–water partition coefficient (lg POW, water solubility (lg W and the chromatographic retention indices (RI on different polar stationary phases. In order to investigate the quantitative structure–property relationship of aliphatic alcohols, the molecular structure ROH is divided into two parts, R and OH to generate structural parameter. It was proposed that the property is affected by three main factors for aliphatic alcohols, alkyl group R, substituted group OH, and interaction between R and OH. On the basis of the polarizability effect index (PEI, previously developed by Cao, the novel molecular polarizability effect index (MPEI combined with odd-even index (OEI, the sum eigenvalues of bond-connecting matrix (SX1CH previously developed in our team, were used to predict the property of aliphatic alcohols. The sets of molecular descriptors were derived directly from the structure of the compounds based on graph theory. QSPR models were generated using only calculated descriptors and multiple linear regression techniques. These QSPR models showed high values of multiple correlation coefficient (R > 0.99 and Fisher-ratio statistics. The leave-one-out cross-validation demonstrated the final models to be statistically significant and reliable.

  10. 脂肪族聚碳酸酯及其在医学中的应用%Progress of Aliphatic Polycarbonates and their Applications in the Biomedical Field

    Institute of Scientific and Technical Information of China (English)

    周瑜; 刘芝兰; 陈红祥

    2011-01-01

    During the past decade,aliphatic polycarbonates have been widely studied and used in the biomedical field,because they are biocompatible,biodegradable and able to functionalization.In this article,combining with the authors' work and referring to the research status about biodegradable aliphatic polycarbonates at home and abroad,aliphatic polycarbonates were sorted according to the structure of polymer chains and also introduced briefly.Their synthetic methods and applications in the biomedical field were reviewed.In addition,the future development of aliphatic polycarbonates was also put forward.%脂肪族聚碳酸酯具有优良的生物降解性、生物相容性和可功能化性等特点,近十几年来在生物医学领域得到了迅速发展。结合本实验室对生物可降解脂肪族聚碳酸酯的研究工作以及国内外研究现状,根据高分子链的几何形状对脂肪族聚碳酸酯进行了分类介绍,综述了它们的合成方法及其在生物医学领域中的应用,同时展望了脂肪族聚碳酸酯的未来发展趋势。

  11. Structural criteria for the rational design of selective ligands. Extension of the MM3 force field to aliphatic ether complexes of the alkali and alkaline earth cations

    Energy Technology Data Exchange (ETDEWEB)

    Hay, B.P.; Rustad, J.R. (Pacific Northwest Lab., Richland, WA (United States))

    1994-07-13

    Structural requirements for strain-free metal ion complexation by an aliphatic ether group are investigated through the use of both ab initio molecular orbital and molecular mechanics calculations. Hartree-Fock calculations on simple models, M-O(Me)[sub 2] and M-O(Me)(Et), reveal a preference for trigonal planar geometry when aliphatic ether oxygens are coordinated to alkali and alkaline earth cations. This preference is found to be strongest in small, high-valent cations and weakest in large, low-valent cations. Results from the Hartree-Fock calculations are used to extend the MM3 force field for calculation on aliphatic ether complexes with the alkali (Li to Cs) and alkaline earth (Mg to Ba) cations. The resulting molecular model (i) reproduces the experimental crystal structures of 51 different complexes of multidentate ethers with alkali and alkaline earth cations, (ii) explains experimental trends in the structure of five-membered chelate rings of aliphatic ethers, (iii) reveals a fundamental difference between the metal ion size selectivity of five-membered chelate rings of ethers versus that of amines, and (iv) rationalizes trends in the stability of four potassium complexes with the diasteriomers of dicyclohexyl-18-crown-6. 40 refs., 9 figs., 5 tabs.

  12. Magic-angle spinning NMR studies of cell wall bound aromatic-aliphatic biopolyesters associated with strengthening of intercellular adhesion in potato (Solanum tuberosum L.) tuber parenchyma.

    Science.gov (United States)

    Yu, Bingwu; Vengadesan, G; Wang, Hsin; Jashi, Liana; Yefremov, Tatiana; Tian, Shiying; Gaba, Victor; Shomer, Ilan; Stark, Ruth E

    2006-03-01

    Intercellular adhesion strengthening, a phenomenon that compromises the texture and the edible quality of potatoes (Solanum tuberosum L.), has been induced reproducibly by exposure to low-pH acetic acid solutions under tissue culture conditions. The resulting parenchyma tissues have been examined by solid-state nuclear magnetic resonance (NMR) in order to characterize the biopolymer(s) thought to be associated with this syndrome. Cross polarization-magic angle spinning (CPMAS) (13)C NMR has been used to establish the presence of a polyphenol-suberin-like aromatic-aliphatic polyester within an abundant cell wall polysaccharide matrix in potato tubers that exhibit hardening due to strengthened intercellular adhesion. Dipolar dephasing and CP chemical shift anisotropy experiments suggest that the aromatic domain is composed primarily of guaiacyl and sinapyl groups. Two-dimensional wide-line separation experiments show that the biopolymer associated with parenchyma hardening contains rigid polysaccharide cell walls and mobile aliphatic long-chain fatty acids; (1)H spin diffusion experiments show that these flexible aliphatic chains are proximal to both the phenolics and a subpopulation of the cell wall polysaccharides. Finally, high-resolution MAS NMR of parenchyma samples swelled in DMSO in conjunction with two-dimensional through-bond and through-space NMR spectroscopy provides evidence for covalent linkages among the polysaccharide, phenolic, and aliphatic domains of the intercellular adhesion-strengthening biopolymer in potato parenchyma tissue.

  13. The similarity of chemical structures of soluble aliphatic polyaldehyde and insoluble algaenan in the green microalga Botryococcus braunii race A as revealed by analytical pyrolysis

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Gelin, F.; Leeuw, J.W. de; Derenne, S.; Largeau, C.; Metzger, P.

    1994-01-01

    Curie point pyrolysis-gas chromatographic-mass spectrometric studies of a recently isolated CHCl3-soluble aliphatic polyaldehyde, and of an insoluble biopolymer termed Bb(A) algaenan, of the green microalga Botryococcus braunii (race A) were performed to determine the structural relationships betwee

  14. Thermophysical and Rheological Properties of Imidazolium-Based Ionic Liquids: The Effect of Aliphatic versus Aromatic Functionality

    Science.gov (United States)

    Tao, Ran; Xue, Lianjie; Tamas, George; Quitevis, Edward; Simon, Sindee

    2014-03-01

    As a material class, ionic liquids possess attractive properties and have a wide range of potential uses. In this work, a series of imidazolium-based ionic liquids with the same carbon number varying from aliphatic to aromatic functionalities are investigated. The effects of cation symmetry and larger aromatic polycyclic functionality are studied. The thermal properties, including the glass transition temperature, melting temperature, and decomposition temperature, are characterized, and the density and the ionic conductivity are measured as a function of temperature. Rheological studies are performed using both steady-state and dynamic shear modes. The Cox-Merz relationship between the steady shear viscosity and the dynamic viscosity is examined. The temperature dependence of viscosity is described by the Vogel-Fulcher-Tammann equation and the dynamic fragility is calculated for each ionic liquid and compared to the fragility obtained from calorimetry. Master curves of dynamic shear responses are also constructed and will be discussed.

  15. Oxidation of Aliphatic Alcohols by Using Precious Metals Supported on Hydrotalcite under Solvent- and Base-Free Conditions.

    Science.gov (United States)

    He, Yufei; Feng, Junting; Brett, Gemma L; Liu, Yanan; Miedziak, Peter J; Edwards, Jennifer K; Knight, David W; Li, Dianqing; Hutchings, Graham J

    2015-10-12

    Precious metal nanoparticles supported on magnesium-aluminum hydrotalcite (HT), TiO2 , and MgO were prepared by sol immobilization and assessed for the catalytic oxidation of octanol, which is a relatively unreactive aliphatic alcohol, with molecular oxygen as the oxidant under solvent- and base-free conditions. Compared with the TiO2 - and MgO-supported catalysts, platinum HT gave the highest activity and selectivity towards the aldehyde. The turnover number achieved for the platinum HT catalyst was >3700 after 180 min under mild reaction conditions. Moreover, the results for the oxidation of different substrates indicate that a specific interaction of octanal with the platinum HT catalyst could lead to deactivation of the catalyst.

  16. SYNTHESIS AND AVERAGE SEQUENCE LENGTH DETERMINATION OF AROMATIC-ALIPHATIC COPOLYESTERS CONTAINING POLY(ALKYLENE OXALATE) UNITS

    Institute of Scientific and Technical Information of China (English)

    Yun-hui Zhao; Fen Wang; Xu-bo Yuan; Gen-hui Xu; Jing Sheng

    2008-01-01

    Two series of aromatic-aliphatic random copolyesters (PEBTOXS) with diverse diol ratios have been synthesizedby direct melting polycondensation. Two kinds of diols (glycol (EG) and 1,4-butanediol (BD)) are used in combination inorder to adjust crystallization and tensile properties, and three kinds of diacids (dimethyl terephthalate (DMT), diethyloxalate (DEOX), and sebacic acid (SA)) are involved. IH-NMR spectra quantify both composition and structure, and showthat the final contents in copolyesters appropriate to the feed ratio. Average sequence lengths of six polyester units arecalculated based on the analyses of 1H-NMR spectra and copolyester structure. The results reveal that the average sequencelengths of sebacate related units increase with the increasing content of sebacic acid in copolyesters, while those of oxalaterelated units show a slight rise. Decreases of average sequence length are found for all terephthalate units, which may bebecause of the restriction of rigid aromatic units in reactions.

  17. Characteristics and biotechnology applications of aliphatic amino acid hydroxylases belonging to the Fe(II)/α-ketoglutarate-dependent dioxygenase superfamily.

    Science.gov (United States)

    Hibi, Makoto; Ogawa, Jun

    2014-05-01

    The asymmetric hydroxylation of inactive carbon atoms is still an important reaction in the industrial synthesis of valuable chiral compounds such as pharmaceuticals and fine chemicals. Applications of monooxygenation enzymes, like cytochrome P450 monooxygenases, flavin-containing monooxygenases, and Fe(II)/α-ketoglutarate-dependent dioxygenases (Fe/αKG-DOs), are strongly desired as hydroxylation biocatalysts because they have great advantages in regio- and stereoselectivity of the reactions. Recently, several novel Fe/αKG-DOs have been found to catalyze the asymmetric hydroxylation of aliphatic amino acids. Depending on their amino acid sequences, these Fe/αKG-DOs catalyze different types of regioselective hydroxylations, or C3-, C4-, and C5-hydroxylation. Additionally, most also have stereoselective sulfoxidation activities. Here, we have reviewed the characterization and process development of this novel functioning group of Fe/αKG-DOs.

  18. New soft porous frameworks based on lambda-zirconium phosphate and aliphatic dicarboxylates: Synthesis and structural characterization

    Science.gov (United States)

    Alhendawi, Hussein; Brunet, Ernesto; Juanes, Olga; Hammouda, Huda; Idhair, Salem; Rodríguez Payán, Elena; de Victoria Rodríguez, María

    2015-11-01

    New dicarboxylate-functionalized pillared materials with a general formula of λ-ZrPO4(OH)1-x(OOC(CH2)nCOO)x/2(dmso) (n=6, 8 and 10) have been prepared by post-synthesis modification of the inorganic layers of λ-zirconium phosphate (λ-ZrP), where the superficial Chloride monovalent anionic ligands of λ-layer are partially exchanged with the divalent anionic ligands of a series of long-chain aliphatic dicarboxylic acids, namely octanedioic acid, decanedioic acid and dodecanedioic acid. The synthesized materials are characterized by X-ray diffractometry, FT-IR spectrophotometry, elemental and thermogravimetric analyses. The X-ray diffraction patterns show that the obtained solid phases are pure. Furthermore, the interlayer distance of λ-ZrP systematically increases from 1.02 to 1.59 nm as a result of the incorporation of the mentioned acids inside the interlayer gallery.

  19. Carbon-rich dust past the asymptotic giant branch: Aliphatics, aromatics, and fullerenes in the Magellanic Clouds

    Energy Technology Data Exchange (ETDEWEB)

    Sloan, G. C.; Lagadec, E. [Center for Radiophysics and Space Research, Cornell University, Ithaca, NY 14853-6801 (United States); Zijlstra, A. A. [Jodrell Bank Centre for Astrophysics, University of Manchester, Manchester M13 9PL (United Kingdom); Kraemer, K. E. [Institute for Scientific Research, Boston College, 140 Commonwealth Avenue, Chestnut Hill, MA 02467 (United States); Weis, A. P. [Department of Astronomy and Astrophysics, Columbia University, 550 West 120th Street, New York, NY 10027 (United States); Matsuura, M. [Astrophysics Group, Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT (United Kingdom); Volk, K. [Space Telescope Science Institute, 3700 San Martin Drive, Baltimore, MD 21218 (United States); Peeters, E.; Cami, J. [Department of Physics and Astronomy, University of Western Ontario, London, ON N6A 3K7 (Canada); Duley, W. W. [Department of Physics and Astronomy, University of Waterloo, 200 University Avenue West, Waterloo, ON N2L 3G1 (Canada); Bernard-Salas, J. [Department of Physical Sciences, The Open University, Walton Hall, Milton Keynes, MK7 6AA (United Kingdom); Kemper, F. [Academia Sinica, Institute of Astronomy and Astrophysics, 11F Astronomy-Mathematics Building, NTU/AS, No. 1, Sec. 4, Roosevelt Road, Taipei 10617, Taiwan, R.O.C (China); Sahai, R., E-mail: sloan@isc.astro.cornell.edu [Jet Propulsion Laboratory, MS 183-900, California Institute of Technology, Pasadena, CA 91109 (United States)

    2014-08-10

    Infrared spectra of carbon-rich objects that have evolved off the asymptotic giant branch reveal a range of dust properties, including fullerenes, polycyclic aromatic hydrocarbons (PAHs), aliphatic hydrocarbons, and several unidentified features, including the 21 μm emission feature. To test for the presence of fullerenes, we used the position and width of the feature at 18.7-18.9 μm and examined other features at 17.4 and 6-9 μm. This method adds three new fullerene sources to the known sample, but it also calls into question three previous identifications. We confirm that the strong 11 μm features seen in some sources arise primarily from SiC, which may exist as a coating around carbonaceous cores and result from photo-processing. Spectra showing the 21 μm feature usually show the newly defined Class D PAH profile at 7-9 μm. These spectra exhibit unusual PAH profiles at 11-14 μm, with weak contributions at 12.7 μm, which we define as Class D1, or show features shifted to ∼11.4, 12.4, and 13.2 μm, which we define as Class D2. Alkyne hydrocarbons match the 15.8 μm feature associated with 21 μm emission. Sources showing fullerene emission but no PAHs have blue colors in the optical, suggesting a clear line of sight to the central source. Spectra with 21 μm features and Class D2 PAH emission also show photometric evidence for a relatively clear line of sight to the central source. The multiple associations of the 21 μm feature with aliphatic hydrocarbons suggest that the carrier is related to this material in some way.

  20. Chemical composition of pseudo-phlobaphinite precursors: implications for the presence of aliphatic biopolymers in vitrinite from coal

    Energy Technology Data Exchange (ETDEWEB)

    Etuan Zhang; Hatcher, P.G.; Davis, A. (Pennsylvania State University, University Park, PA (United States). Dept. of Materials Science and Engineering)

    1993-08-01

    Pseudo-phlobaphinite cell inclusions in a buried stem of angiospermous wood of [ital Rhizophora mangle] from Mangrove Lake, Bermuda have been investigated petrographically and chemically. Optical and scanning electron microscopy reveal that the light wood from inner sections of the stem consists predominantly of cell walls with few cell inclusions, whereas the dark wood from outer portion of the stem is composed of both cell walls and cell inclusions which are believed to represent pseudophlobaphinite precursors. [sup 13]C NMR spectroscopy reveals the presence of lignin and tannin structures within the cell walls. The wood also displays resonances suggestive of aliphatic components. The NMR results are further supplemented and confirmed by flash pyrolysis gas chromatography and mass spectrometry analyses. The pyrogram of the cell-wall dominated light wood is characterized by peaks related to both syringyl and guaiacyl units. The major pyrolysis products from the dark wood, however, are a homologous series of long-chain n-alkanes, n-alk-l-enes and [alpha],[omega]-alkadienes extending from chain length C[sub 10] to C[sub 30]. These aliphatic components arise from the material associated with the pseudophlobaphinite cell inclusions. Py-gc/ms analysis of a humic acid extracted from the sediments surrounding the studied wood consists almost exclusively of a homologous series of straight-chain alkanes, alkenes and alkadienes up to C[sub 30]. The striking resemblance between programs of the pseudo-phlobaphinite precursor and humic acid suggests that the possible mechanism for the formation of the pseudo-phlobaphinite is migration and deposition of humic acid into cell lumina. 72 refs., 5 figs., 1 tab.

  1. Retention behavior of a homologous series and positional isomers of aliphatic amino acids in hydrophilic interaction chromatography.

    Science.gov (United States)

    Douša, Michal; Srbek, Jan; Stránský, Zdeněk; Gibala, Petr; Nováková, Lucie

    2014-04-01

    The retention behavior of several series of free α- and ω-amino acids and positional isomers of amino pentanoic acid in the hydrophilic interaction chromatography mode (HILIC) was studied. The study was carried out on three stationary phases followed by post-column derivatization with fluorescence detection in order to describe the retention mechanism of the tested amino acids. The effect of chromatographic conditions including acetonitrile content in the mobile phase, mobile phase pH (ranging from 3.5 to 6.5) and concentration of buffer in the mobile phase was investigated. The effect of the number of carbon atoms (nC) in aliphatic chains of the individual homologue of α- and ω-amino acids and the logarithm of the partition coefficient (logD) on retention was also a part of the presented study. A good correlation (r > 0.98) between the logk and logD values of amino acids or nC, respectively, was observed. The described linear relationships were subsequently applied to predict the retention behavior of individual members of the homologous series of amino acids and to optimize the mobile phase composition in HILIC. The obtained results confirmed that the retention mechanism of α-amino acids, ω-amino acids and positional isomers of amino acids was based on the logD values and the number of carbon atoms in the aliphatic chains of amino acids. The elution order of ω-amino acids and positional isomers of amino pentanoic acid was strongly dependent on the mobile phase pH in the investigated range whereas the retention factors of all α-amino acids remained essentially unchanged on all tested stationary phases.

  2. Progresses in Research of Aliphatic Polycarbonates%脂肪族聚碳酸酯的研究进展

    Institute of Scientific and Technical Information of China (English)

    刘峰; 翟刚; 李建国; 刘绍英; 杨先贵; 王公应

    2013-01-01

    综述了通过环氧化物与CO2共聚法、脂肪族环状碳酸酯开环聚合法及脂肪族二元醇与碳酸二烃基酯聚合法合成脂肪族聚碳酸酯(APCs)的研究进展,特别是对各种反应体系所采用催化剂的突破性研究成果进行了介绍,并对反应机理进行了分析.讨论了APCs的结构与其生物降解性及热分解性等性能的关系;结合APCs的性质介绍了它在医用材料、陶瓷及橡胶工业等领域的应用.比较了合成APCs的不同途径的特点,并对APCs材料的合成方法及其应用的发展趋势进行了展望.%The catalysts for the synthesis of aliphatic polycarbonates(APCs) were summarized according to three reaction systems,namely the copolymerization of carbon dioxide with epoxides,the ring-opening polymerization of cyclic carbonates and the two-step polycondensation of dialkyl carbonates and aliphatic diols.Particularly,the new research achievements for the catalysts and the mechanism of the reactions were introduced.The relationship between the structures and the performances of APCs,such as biodegradability and thermal decomposition,were discussed.The applications of APCs in medical materials,ceramics,rubber industry and so on were introduced.The synthesis of APCs by different methods were analyzed briefly.The development trend of APCs in future was forecasted.

  3. A rapid and sensitive method for the simultaneous analysis of aliphatic and polar molecules containing free carboxyl groups in plant extracts by LC-MS/MS

    Directory of Open Access Journals (Sweden)

    Bonaventure Gustavo

    2009-11-01

    Full Text Available Abstract Background Aliphatic molecules containing free carboxyl groups are important intermediates in many metabolic and signalling reactions, however, they accumulate to low levels in tissues and are not efficiently ionized by electrospray ionization (ESI compared to more polar substances. Quantification of aliphatic molecules becomes therefore difficult when small amounts of tissue are available for analysis. Traditional methods for analysis of these molecules require purification or enrichment steps, which are onerous when multiple samples need to be analyzed. In contrast to aliphatic molecules, more polar substances containing free carboxyl groups such as some phytohormones are efficiently ionized by ESI and suitable for analysis by LC-MS/MS. Thus, the development of a method with which aliphatic and polar molecules -which their unmodified forms differ dramatically in their efficiencies of ionization by ESI- can be simultaneously detected with similar sensitivities would substantially simplify the analysis of complex biological matrices. Results A simple, rapid, specific and sensitive method for the simultaneous detection and quantification of free aliphatic molecules (e.g., free fatty acids (FFA and small polar molecules (e.g., jasmonic acid (JA, salicylic acid (SA containing free carboxyl groups by direct derivatization of leaf extracts with Picolinyl reagent followed by LC-MS/MS analysis is presented. The presence of the N atom in the esterified pyridine moiety allowed the efficient ionization of 25 compounds tested irrespective of their chemical structure. The method was validated by comparing the results obtained after analysis of Nicotiana attenuata leaf material with previously described analytical methods. Conclusion The method presented was used to detect 16 compounds in leaf extracts of N. attenuata plants. Importantly, the method can be adapted based on the specific analytes of interest with the only consideration that the

  4. Two-dimensional inorganic–organic hybrid semiconductors composed of double-layered ZnS and monoamines with aromatic and heterocyclic aliphatic rings: Syntheses, structures, and properties

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Sujing; Li, Jing, E-mail: jingli@rutgers.edu

    2015-04-15

    As an addition to the II–VI based inorganic–organic hybrid semiconductor family, five new two-dimensional (2D) double-layered structures have been synthesized employing monoamines with different aromatic or heterocyclic aliphatic rings. Zn{sub 2}S{sub 2}(bza) (1), Zn{sub 2}S{sub 2}(mbza) (2), Zn{sub 2}S{sub 2}(fbza) (3), Zn{sub 2}S{sub 2}(pca) (4), and Zn{sub 2}S{sub 2}(thfa) (5) (bza=benzylamine, mbza=4-methoxybenzylamine, fbza=4-flurobenzylamine, pca=3-picolylamine, and thfa=tetrahydrofurfurylamine) are prepared by solvothermal reactions and characterized by different analytical methods, including powder X-ray diffraction, optical diffuse reflection, thermogravimetric analysis and photoluminescence spectroscopy. The powder X-ray diffraction patterns show that all five compounds adopt 2D double-layered structures. Optical diffuse reflectance spectra of these compounds suggest that they have notably lower band gaps than those of the similar compounds composed of aliphatic alkyl amines. Their photoluminescence properties and thermal stability are also analyzed. - Graphical abstract: Five new members of two-dimensional double-layered 2D-Zn{sub 2}S{sub 2}(L) (L=Ligand) structures employing monoamines with different aromatic or heterocyclic aliphatic rings have been designed, synthesized, and characterized. - Highlights: • A new sub-family of II-VI based hybrid semiconductors are designed, synthesized, and structurally characterized using amines with aromatic or aliphatic cyclic rings. • These compounds have notably lower band gaps than those made of aliphatic alkyl amines, greatly broadening the range of band gaps of this material family. • They emit strongly with systematically tunable emission intensity and energy.

  5. A Convenient Method for Preparation of Aliphatic Methyl Ketones%带有脂肪链取代基的甲基酮的简便合成方法

    Institute of Scientific and Technical Information of China (English)

    杨小波; 尹健; 陈再新; 张奕华

    2005-01-01

      报道了一种简便有效、经济的合成含有脂肪链取代基的甲基酮的方法,尤其是对于合成带有高级脂肪链取代基的甲基酮。本方法具有工业应用价值。%  A convenient, efficient and economical method for preparation of aliphatic methyl ketones, especially of high aliphatic methyl ketones by using aliphatic acid chlorides and diethyl malonate as starting material was described. It is possible to develop this method for industrial application.

  6. Technical Protocol for Using Soluble Carbohydrates to Enhance Reductive Dechlorination of Chlorinated Aliphatic Hydrocarbons

    Science.gov (United States)

    2002-12-19

    subsurface injection of a soluble electron donor solution (typically comprised of a carbohydrate such as molasses, whey , high fructose corn syrup (HFCS... whey , high fructose corn syrup (HFCS), glucose, lactate, butyrate, benzoate). Other approaches to enhanced anaerobic bioremediation exist, but will...other methods for sample analysis are drawn from standard reference works such as “Standard Methods for the Examination of Water and Wastewater ” (APHA

  7. Silver-Catalyzed Decarboxylative Addition/Cyclization of Activated Alkenes with Aliphatic Carboxylic Acids.

    Science.gov (United States)

    Xia, Xiao-Feng; Zhu, Su-Li; Chen, Chao; Wang, Haijun; Liang, Yong-Min

    2016-02-05

    A silver-catalyzed decarboxylative addition/aryl migration/desulfonylation of N-phenyl-N-(phenylsulfonyl)methacrylamide with primary, secondary, and tertiary carboxylic acids was described. The protocol provides an efficient approach for the synthesis of α-all-carbon quaternary stereocenters amides and isoquinolinediones. It was proposed that the radical generated from the silver-catalyzed decarboxylation was involved in the sequence reaction.

  8. Highly enantioselective synthesis of non-natural aliphatic α-amino acids via asymmetric hydrogenation.

    Science.gov (United States)

    Ji, Jianjian; Chen, Caiyou; Cai, Jiayu; Wang, Xinrui; Zhang, Kai; Shi, Liyang; Lv, Hui; Zhang, Xumu

    2015-07-28

    By employing a rhodium-Duanphos complex as the catalyst, β-alkyl (Z)-N-acetyldehydroamino esters were smoothly hydrogenated in a highly efficient and enantioselective way. Excellent enantioselectivities together with excellent yields were achieved for a series of substrates. An efficient approach for the synthesis of the intermediate of the orally administered anti-diabetic drugs Alogliptin and Linagliptin in the DPP-4 inhibitor class was also developed.

  9. Application of 10-ethyl-acridine-3-sulfonyl chloride for HPLC determination of aliphatic amines in environmental water using fluorescence and APCI-MS.

    Science.gov (United States)

    You, Jinmao; Zhao, Huaixin; Sun, Zhiwei; Xia, Lian; Yan, Tao; Suo, Yourui; Li, Yulin

    2009-05-01

    A simple, sensitive method for the determination of aliphatic amines based on a sulfonylation reaction using 10-ethyl-acridine-3-sulfonyl chloride (EASC) as pre-column labeling reagent with fluorescence detection and APCI-MS identification has been developed. The labeled derivatives exhibited high stability and were enough to be efficiently analyzed by HPLC with an excitation maximum at lambda(ex) 270 nm and an emission maximum at lambda(em) 430 nm. Identification of derivatives was carried out by online post-column MS in positive-ion mode. Comparing with the widely used 5-dimethylaminonaphthalene-1-sulfonylchloride (Dansyl-Cl), EASC-amine derivatives not only exhibited high fluorescence but also exhibited excellent MS ionizable potential. Detection limits obtained from 0.10 pmol injection, at a S/N of 3, were 4.0-12.7 fmol. The mean intra- and inter-assay precision for all aliphatic amine levels were 0.9995.

  10. Effectiveness of a Prudhoe Bay crude oil and its aliphatic, aromatic and heterocyclic fractions in inducing mortality and aryl hydrocarbon hydroxylase in chick embryo in ovo

    Energy Technology Data Exchange (ETDEWEB)

    Walters, P.; Khan, S.; O' Brien, P.J.O.; Rahimtula, A.T.; Payne, J.F.

    1987-08-01

    Prudhoe Bay crude oil (PBCO) and its aliphatic, aromatic and heterocyclic fractions were tested on the developing chick embryo for (i) embryotoxicity (ii) their ability to induce hepatic and renal cytochrome P450 levels as well as hepatic, renal and pulmonary aryl hydrocarbon hydroxylase activities. On the basis of its concentration in PBCO, the aromatic fraction was responsible for most of the embryotoxicity as well as for the enzyme inducing ability. The NOS fraction constituted less than 7% (w/v) of PbCO but, on a weight equivalent basis, was roughly as potent as the aromatic fraction in causing embryotoxicity and in inducing cytochrome P450 levels and aryl hydrocarbon hydroxylase. The aliphatic fraction was found to be essentially inactive. The results are consistent with the concept that elevation of aryl hydrocarbon hydroxylase levels by certain components of PBCO may lead to increased embroyotoxicity.

  11. Molecular polarizability effect index and boiling point of aliphatic aldehydes and alkanones%分子极化效应指数与脂肪族醛酮的沸点

    Institute of Scientific and Technical Information of China (English)

    张秀利; 汪勇先; 林英武; 李俊玲

    2003-01-01

    Based on the molecular polarizabihty effect index,a formula of three parameters was proposed to calculate the boiling point of aliphatic aldehydes and alkanones. ln(820.5 - Tb) = 6.38330- 1.37357 × 10-1 Nc + 5.39350ΔEPI + 8.02603 × 10-2N Where the Nc is the effective length of carbon chain of alkyl group in the aliphatic aldehydes and alkanones. The ΔPEI is the polarizability effect index difference between the corresponding branched and normal alkyl isomer containing the same carbon atom number, which expressed the effcet of carbonyl group on the boiling point of aliphatic aldehydes and alkanones. N is the carbon numbers of aliphatic aldehydes and alkanones.

  12. Assessing the Origins of Aliphatic Amines in the Murchison Meteorite from their Compound-Specific Carbon Isotopic Ratios and Enantiomeric Composition

    Science.gov (United States)

    Aponte, Jose; Dworkin, Jason; Elsila, Jamie E.

    2014-01-01

    The study of meteoritic organic compounds provides a unique window into the chemical inventory of the early Solar System and prebiotic chemistry that may have been important for the origin of life on Earth. Multiple families of organic compounds have been extracted from the Murchison meteorite, which is one of the most thoroughly studied carbonaceous chondrites. The amino acids extracted from Murchison have been extensively analyzed, including measurements of non-terrestrial stable isotopic ratios and discoveries of L-enantiomeric excesses for alpha-dialkyl amino acids, notably isovaline. However, although the isotopic signatures of bulk amine-containing fractions have been measured, the isotopic ratios and enantiomeric composition of individual aliphatic amines, compounds that are chemically related to amino acids, remain unknown. Here, we report a novel method for the extraction, separation, identification and quantitation of aliphatic monoamines extracted from the Murchison meteorite. Our results show a complete suite of structural isomers, with a larger concentration of methylamine and ethylamine and decreasing amine concentrations with increasing carbon number. The carbon isotopic compositions of fourteen meteoritic aliphatic monoamines were measured, with delta C-13 values ranging from +21% to +129%, showing a decrease in C-13 with increasing carbon number, a relationship that may be consistent with the chain elongation mechanism under kinetic control previously proposed for meteoritic amino acids. We also found the enantiomeric composition of sec-butylamine, a structural analog to isovaline, was racemic within error, while the isovaline extracted from the same Murchison piece showed an L-enantiomeric excess of 9.7; this result suggested that processes leading to enantiomeric excess in the amino acid did not affect the amine. We used these collective data to assess the primordial synthetic origins of these meteoritic aliphatic amines and their potential

  13. New tetradentate Schiff bases of 2-amino-3,5-dibromobenzaldehyde with aliphatic diamines and their metal complexes: synthesis, characterization and thermal stability.

    Science.gov (United States)

    Mohammadi, Khosro; Azad, Seyyedeh Sedigheh; Amoozegar, Ameneh

    2015-07-05

    The tetradentate Schiff base ligands (L(1)-L(4)), were synthesized by reaction between 2-amino-3,5-dibromobenzaldehyde and aliphatic diamines. Then, nickel and oxovanadium(IV) complexes of these ligands were synthesized and characterized by (1)H NMR, Mass, IR, UV-Vis spectroscopy and thermogravimetry. The kinetic parameters of oxovanadium(IV) complexes were calculated from thermal studies. According to the results of thermogravimetric data, the thermal stability of oxovanadium(IV) complexes is as follow: [Formula: see text].

  14. Insoluble, nonhydrolyzable highly aliphatic biopolymers from algal cell walls and vascular plant cuticles and barks as sources of N-alkanes in crude oils

    Energy Technology Data Exchange (ETDEWEB)

    Tegelaar, E.W.; De Leeuw, J.E.; Horsfield, B.

    1989-03-01

    Recently discovered insoluble, nonhydrolyzable highly aliphatic biopolymers occurring in cell walls of several extant algae and in cuticles and barks of vascular plants are selectively preserved during diagenesis and represent as such, or in a slightly altered form, a considerable part of kerogens. Thermal simulation experiments performed with these isolated biopolymers of extant organisms yield series of n-alkanes with carbon number distribution patterns very similar to those of n-alkanes in natural crude oils.

  15. Directing Group in Decarboxylative Cross-Coupling: Copper-Catalyzed Site-Selective C-N Bond Formation from Nonactivated Aliphatic Carboxylic Acids.

    Science.gov (United States)

    Liu, Zhao-Jing; Lu, Xi; Wang, Guan; Li, Lei; Jiang, Wei-Tao; Wang, Yu-Dong; Xiao, Bin; Fu, Yao

    2016-08-03

    Copper-catalyzed directed decarboxylative amination of nonactivated aliphatic carboxylic acids is described. This intramolecular C-N bond formation reaction provides efficient access to the synthesis of pyrrolidine and piperidine derivatives as well as the modification of complex natural products. Moreover, this reaction presents excellent site-selectivity in the C-N bond formation step through the use of directing group. Our work can be considered as a big step toward controllable radical decarboxylative carbon-heteroatom cross-coupling.

  16. Use of potassium-form cation-exchange resin as a conductimetric enhancer in ion-exclusion chromatography of aliphatic carboxylic acids.

    Science.gov (United States)

    Iwata, Tomotaka; Mori, Masanobu; Itabashi, Hideyuki; Tanaka, Kazuhiko

    2009-09-15

    In this study, a cation-exchange resin (CEX) of the K(+)-form, i.e., an enhancer resin, is used as a postcolumn conductimetric enhancer in the ion-exclusion chromatography of aliphatic carboxylic acids. The enhancer resin is filled in the switching valve of an ion chromatograph; this valve is usually used as a suppressor valve in ion-exchange chromatography. An aliphatic carboxylic acid (e.g., CH(3)COOH) separated by a weakly acidic CEX column of the H(+)-form converts into that of the K(+)-form (e.g., CH(3)COOK) by passing through the enhancer resin. In contrast, the background conductivity decreases because a strong acid (e.g., HNO(3)) with a higher conductimetric response in an eluent converts into a salt (e.g., KNO(3)) with a lower conductimetric response. Since the pH of the eluent containing the resin enhancer increases from 3.27 to 5.85, the enhancer accelerates the dissociations of analyte acids. Consequently, peak heights and peak areas of aliphatic carboxylic acids (e.g., acetic acid, propionic acid, butyric acid, and valeric acid) with the enhancer resin are 6.3-8.0 times higher and 7.2-9.2 times larger, respectively, than those without the enhancer resin. Calibrations of peak areas for injected analytes are linear in the concentration range of 0.01-1.0mM. The detection limits (signal-to-noise ratio=3) range from 0.10 microM to 0.39 microM in this system, as opposed to those in the range of 0.24-7.1 microM in the separation column alone. The developed system is successfully applied to the determination of aliphatic carboxylic acids in a chicken droppings sample.

  17. Cloning of genes related to aliphatic glucosinolate metabolism and the mechanism of sulforaphane accumulation in broccoli sprouts under jasmonic acid treatment.

    Science.gov (United States)

    Guo, Liping; Yang, Runqiang; Gu, Zhenxin

    2016-10-01

    Cytochrome P450 79F1 (CYP79F1), cytochrome P450 83A1 (CYP83A1), UDP-glucosyltransferase 74B1 (UGT74B1), sulfotransferase 18 (ST5b) and flavin-containing monooxygenase GS-OX1 (FMOGS - OX1 ) are important enzymes in aliphatic glucosinolate biosynthesis. In this study, their full-length cDNA in broccoli was firstly cloned, then the mechanism of sulforaphane accumulation under jasmonic acid (JA) treatment was investigated. The full-length cDNA of CYP79F1, CYP83A1, UGT74B1, ST5b and FMOGS - OX1 comprised 1980, 1652, 1592, 1378 and 1623 bp respectively. The increase in aliphatic glucosinolate accumulation in broccoli sprouts treated with JA was associated with elevated expression of genes in the aliphatic glucosinolate biosynthetic pathway. Application of 100 µmol L(-1) JA increased myrosinase (MYR) activity but did not affect epithiospecifier protein (ESP) activity in broccoli sprouts, which was supported by the expression of MYR and ESP. Sulforaphane formation in 7-day-old sprouts treated with 100 µmol L(-1) JA was 3.36 and 1.30 times that in the control and 300 µmol L(-1) JA treatment respectively. JA enhanced the accumulation of aliphatic glucosinolates in broccoli sprouts via up-regulation of related gene expression. Broccoli sprouts treated with 100 µmol L(-1) JA showed higher sulforphane formation than those treated with 300 µmol L(-1) JA owing to the higher glucoraphanin content and myrosinase activity under 100 µmol L(-1) JA treatment. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

  18. Novel high glass temperature sugar-based epoxy resins: Characterization and comparison to mineral oil-based aliphatic and aromatic resins

    OpenAIRE

    Niedermann, P.; G. Szebenyi; A. Toldy

    2015-01-01

    Curing and rheological behaviour, glass transition temperature, mechanical and thermal properties of two newly synthesized glucopyranoside- (GPTE) and glucofuranoside- (GFTE) based renewable epoxy resin (EP) components were investigated and compared to aromatic and aliphatic EPs. The glucose-based EPs can be successfully cured with amine and anhydride type curing agents, their gel times are suitable for processing and can be well-adopted to the needs of the common composite preparation method...

  19. A fast degrading odd-odd aliphatic polyester-5,7 made by condensation polymerization for biomedical applications.

    Science.gov (United States)

    Chen, Fei; Nölle, Jan Martin; Wietzke, Steffen; Reuter, Marco; Chatterjee, Sangam; Koch, Martin; Agarwal, Seema

    2012-01-01

    A fast enzymatic degradable aliphatic all-odd-polyester-5,7, based on 1,7-heptanedioic acid (pimelic acid) and 1,5-pentanediol, was synthesized by polycondensation. The structural characterization of the polyester was done using 1D- and 2D-NMR spectroscopic techniques. The properties of the resulting polyester-like crystallization behavior, enzymatic degradation, thermal stability, etc., were investigated using differential scanning calorimetry, wide-angle X-ray diffraction, scanning electron microscopy and gel-permeation chromatography. Terahertz time-domain spectroscopy was employed to determine the glass transition temperature, which could not be revealed reliably by conventional thermal analysis. The properties of all-odd-polyester-5,7 were compared with a well-known enzymatic degradable polyester (polycaprolactone). The results indicated that polyester-5,7 has a crystal structure similar to PCL, but a much faster degradation rate. The morphology of polyester-5,7 film during enzymatic degradation showed a fibrillar structure and degradation began by surface erosion.

  20. Lipidic ionic liquid stationary phases for the separation of aliphatic hydrocarbons by comprehensive two-dimensional gas chromatography.

    Science.gov (United States)

    Nan, He; Zhang, Cheng; O'Brien, Richard A; Benchea, Adela; Davis, James H; Anderson, Jared L

    2017-01-20

    Lipidic ionic liquids (ILs) possessing long alkyl chains as well as low melting points have the potential to provide unique selectivity as well as wide operating ranges when used as stationary phases in gas chromatography. In this study, a total of eleven lipidic ILs containing various structural features (i.e., double bonds, linear thioether chains, and cyclopropanyl groups) were examined as stationary phases in comprehensive two dimensional gas chromatography (GC×GC) for the separation of nonpolar analytes in kerosene. N-alkyl-N'-methyl-imidazolium-based ILs containing different alkyl side chains were used as model structures to investigate the effects of alkyl moieties with different structural features on the selectivities and operating temperature ranges of the IL-based stationary phases. Compared to a homologous series of ILs containing saturated side chains, lipidic ILs exhibit improved selectivity toward the aliphatic hydrocarbons in kerosene. The palmitoleyl IL provided the highest selectivity compared to all other lipidic ILs as well as the commercial SUPELCOWAX 10 column. The linoleyl IL containing two double bonds within the alkyl side chain showed the lowest chromatographic selectivity. The lipidic IL possessing a cyclopropanyl group within the alkyl moiety exhibited the highest thermal stability. The Abraham solvation parameter model was used to evaluate the solvation properties of the lipidic ILs. This study provides the first comprehensive examination into the relation between lipidic IL structure and the resulting solvation characteristics. Furthermore, these results establish a basis for applying lipidic ILs as stationary phases for solute specific separations in GC×GC.

  1. Preparation and characterization of biodegradable aliphatic-aromatic copolyesters/nano-SiO_2 hybrids via in situ melt polycondensation

    Institute of Scientific and Technical Information of China (English)

    Yan Zhang; Bing Tao Wang; Zheng Hong Guo; Jie Chen; Zheng Ping Fang

    2009-01-01

    In situ melt polycondensation was proposed to prepare biodegradable aliphatic-aromatic copolyesters/nano-SiO_2 hybrids based on terephthalic acid (TPA), poly(L-lactic acid) oligomer (OLLA), 1,4-butanediol (BDO) and nano-SiO_2. TEM and FT-IR characterizations confirmed that TPA, OLLA and BDO copolymerized to obtain biodegradable copolyesters, poly(butylene terephthalate-co-lactate) (PBTL), and the abundant hydroxyl groups on the surface of nano-SiO_2 provided potential sites for in situ grafting with the simultaneous resulted PBTL. The nano-SiO_2 particles were chemically wrapped with PBTL to form PBTL/nano-SiO2 hybrids. Due to the good dispersion and interfacial adhesion of nano-SiO_2 particles with the copolyester matrix, the tensile strength and the Young's modulus increased from 5.4 and 5.6 Mpa for neat PBTL to 16 and 390 Mpa for PBTL/nano-SiO_2 hybrids with 5 wt.% nano-SiO_2, respectively. The mechanical properties of PBTL/nano-SiO_2 hybrids were substantially improved.

  2. Effect of a long chain aliphatic alkohols on growth. gas exchange and assimilate parlitioning in radish plant

    Directory of Open Access Journals (Sweden)

    Zbyszek K. Blamowski

    2013-12-01

    Full Text Available In pot experiments the influence of long chain aliphatic alcohols (hexacosanol - HEXA, octacosanol - OCTA and triacontanol - TRIA, which were used in concentration O.00l mg·dm3 , on growth, assimilate partitioning and gas exchange of radish plants cv. "Krakowianka" and "Sopel lodu" were studied. The received results showed that triacontanol was characterized by higher physiological activity than remaining alcohols. TRIA significantly increased yield of mass, as well as it changed the pattern of distribution of assimilates in plants. Under its influence the rate of mass of leaves to mass of storage organs decreased as well as the share of mass of leaves in the total mass of both plant cultivars. TRIA stimulated the rate of net photosynthesis (Pn, howewer, it did not influence the other detennined gas exchange parameters: substomatal concentration of CO2 (ci, stomatal conductance for water vapour (gs and rate of transpiration (Tr. Remaining alcohols (HEXA and OCFA did not any influence on growth of plants and their gas exchange but only on distribution of biomass.

  3. Fast Fourier Transform IR Characterization of Epoxy GY Systems Crosslinked with Aliphatic and Cycloaliphatic EH Polyamine Adducts

    Directory of Open Access Journals (Sweden)

    Caslav Lacnjevac

    2010-01-01

    Full Text Available The use of fast FT-IR spectroscopy as a sensitive method to estimate a change of the crosslinking kinetics of epoxy resin with polyamine adducts is described in this study. A new epoxy formulation based on the use of polyamine adducts as the hardeners was analyzed. Crosslinking reactions of the different stoichiometric mixtures of the unmodified GY250 epoxy resin with the aliphatic EH606 and the cycloaliphatic EH637 polyamine adducts were studied using mid FT-IR spectroscopic techniques. As the crosslinking proceeded, the primary amine groups in polyamine adduct are converted to secondary and the tertiary amines. The decrease in the IR band intensity of epoxy groups at about 915 cm-1, as well as at about 3,056 cm-1, was observed due to process. Mid IR spectral analysis was used to calculate the content of the epoxy groups as a function of crosslinking time and the crosslinking degree of resin. The amount of all the epoxy species was estimated from IR spectra to changes during the crosslinking kinetics of epichlorhydrin.

  4. STRUCTURAL PHASE TRANSITION OF ALIPHATIC NYLONS VIEWED FROM THE WAXD/SAXS AND VIBRATIONAL SPECTRAL MEASUREMENTS AND MOLECULAR DYNAMICS CALCULATION

    Institute of Scientific and Technical Information of China (English)

    Kohji Tashiro

    2007-01-01

    The crystalline phase transition of aliphatic nylon 10/10 has been investigated on the basis of the simultaneous measurement of wide-angle and small-angle X-ray scatterings, the infrared spectral measurement and the molecular dynamics calculation. An interpretation of infrared spectra taken for a series of nylon samples and the corresponding model compounds was successfully made, allowing us to assign the infrared bands of the planar-zigzag methylene segments reasonably. As a result the methylene segmental parts of molecular chains were found to experience an order-to-disorder transition in the Brill transition region, where the intermolecular hydrogen bonds are kept alive although the bond strength becomes weaker at higher temperature. The small-angle X-ray scattering data revealed a slight change in lamellar stacking mode in the transition region. The crystal structure has been found to change more remarkably in the temperature region immediately below the melting point, where the conformationally disordered chains experienced drastic rotational and translational motions without any constraints by hydrogen bonds, and the lamellar thickness increased largely along the chain axis. These experimental results were reasonably reproduced by the molecular dynamics calculation performed at the various temperatures.

  5. Aliphatic hydrocarbon levels in turbot and salmon farmed close to the site of the Aegean Sea oil spill

    Energy Technology Data Exchange (ETDEWEB)

    Alvarez Pineiro, M.E. [Institute of Investigation and Food Analysis, La Coruna (Spain); Gonzalez-Barros, S.T.C.; Lozano, J.S. [Area Nutrition and Bromatology, La Coruna (Spain)] [and others

    1996-12-31

    After the Andros Patria oil spill, the most serious oil tanker accident to occur off the coast of Galicia (N.W. Spain) was the running aground and subsequent conflagration of the Aegean Sea supertanker outside the northern Spanish port of La Coruna (December 3rd 1992). Approximately 60,000 tonnes of Brent oil were spilled into the Atlantic Ocean in the cited coastal region. Subsequently, an impropitious combination of a high tide and a change in wind direction caused the resulting slick to rapidly spread into the port. Measures aimed at cleaning up affected areas and evacuating the ca. 11,215 tonnes of oil remaining in the supertanker were immediately implemented. However, within just a few days the resulting contamination had killed some 15000 turbot juveniles and larvae, which are cultivated in fish farms close to the accident site. The environmental impact of major oil spillages has been widely studied. Several scientists have suggested that, in terms of the negative effects on the seawater quality and productive capacity of the affected maritime regions, the magnitudes of the Aegean Sea and Amoco Cadiz accidents are comparable. This paper reports variations over time of aliphatic hydrocarbon levels in turbot and Atlantic salmon sampled from fish farms close to the site of the Aegean Sea oil spill. 6 refs., 2 figs., 1 tab.

  6. Reaction of benzophenone triplet with aliphatic amines. What a potent neurotoxin can tell us about the reaction mechanism.

    Science.gov (United States)

    Grimm, Michelle L; Allen, William J; Finn, Meghan; Castagnoli, Neal; Tanko, James M

    2011-02-15

    A photochemical model study of benzophenone triplet ((3)BP) with the MAO-B substrate 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine [MPTP (1)] and two of it's derivatives, 1-cyclopropyl-4-phenyl-1,2,3,6-tetrahydropyridine (2) and (±)-[trans-2-phenylcyclopropyl-4-phenyl-1,2,3,6-tetrahydropyridine (3) were performed. Literature precedent and calculations reported herein suggest that the barrier to ring opening for aminyl radical cations derived from N-cyclopropyl derivatives of tertiary amines (such as MPTP) will be low. The LFP results reported herein demonstrate that pathways for the reaction of (3)BP with 1, 2, and 3 are very similar. In each instance, disappearance of (3)BP is accompanied solely by appearance of bands corresponding to the diphenylhydroxylmethyl radical and neutral radical derived from MPTP and it's two derivatives 2 and 3. These results suggest that the reaction between benzophenone triplet and tertiary aliphatic amines proceed via a simple hydrogen atom transfer reaction. Additionally these model examinations provide evidence that oxidations of N-cyclopropyl derivatives of MPTP catalyzed by MAO-B may not be consistent with a pure SET pathway.

  7. Aliphatic and polycyclic aromatic hydrocarbons in surface sediments collected from mangroves with different levels of urbanization in southern Brazil.

    Science.gov (United States)

    Assunção, Maíra Algarve; Frena, Morgana; Santos, Ana Paula Stein; Dos Santos Madureira, Luiz Augusto

    2017-06-15

    Three mangroves located in southern Brazil, Carijós (CA), Rio Tavares (RT) and Itacorubi (ITA), with distinct anthropogenic influences, were assessed with regard to the presence of aliphatic and polycyclic aromatic hydrocarbons (PAH). In this study, the n-alkane concentrations ranged from 1.9μg g(-1) (CA) to 55.6μg g(-1) (ITA) (dry weight). The carbon preference index (CPI) ranged from 2.1 to 7.9 and values for the terrestrial/aquatic ratio (TAR) were >1. Thus, both indexes indicated the predominance of sediment of terrestrial origin, mainly comprised of higher plants. Concentrations of total PAH ranged from 6.8ng g(-1) (RT) to 437.3ng g(-1) (ITA). The PAH isomeric ratios indicated that these compounds originated mainly from pyrogenic sources. Nevertheless, levels of n-alkanes in the three mangroves were relatively low and they are considered typical of uncontaminated surface sediments, while the level of contamination with PAH was classified as low to moderate. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Matrix-assisted laser desorption/ionization mass spectrometric analysis of aliphatic biodegradable photoluminescent polymers using new ionic liquid matrices.

    Science.gov (United States)

    Serrano, Carlos A; Zhang, Yi; Yang, Jian; Schug, Kevin A

    2011-05-15

    In this study, two novel ionic liquid matrices (ILMs), N,N-diisopropylethylammonium 3-oxocoumarate and N,N-diisopropylethylammonium dihydroxymonooxoacetophenoate, were tested for the structural elucidation of recently developed aliphatic biodegradable polymers by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). The polymers, formed by a condensation reaction of three components, citric acid, octane diol, and an amino acid, are fluorescent, but the exact mechanism behind their luminescent properties has not been fully elucidated. In the original studies, which introduced the polymer class (J. Yang et al., Proc. Natl. Acad. Sci. USA 2009, 106, 10086-10091), a hyper-conjugated cyclic structure was proposed as the source for the photoluminescent behavior. With the use of the two new ILMs, we present evidence that supports the presence of the proposed cyclization product. In addition, the new ILMs, when compared with a previously established ILM, N,N-diisopropylethylammonium α-cyano-3-hydroxycinnimate, provided similar signal intensities and maintained similar spectral profiles. This research also established that the new ILMs provided good spot-to-spot reproducibility and high ionization efficiency compared with corresponding crystalline matrix preparations. Many polymer features revealed through the use of the ILMs could not be observed with crystalline matrices. Ultimately, the new ILMs highlighted the composition of the synthetic polymers, as well as the loss of water that was expected for the formation of the proposed cyclic structure on the polymer backbone.

  9. Enzymatic Polymerization of Furan-2,5-Dicarboxylic Acid-Based Furanic-Aliphatic Polyamides as Sustainable Alternatives to Polyphthalamides.

    Science.gov (United States)

    Jiang, Yi; Maniar, Dina; Woortman, Albert J J; Alberda van Ekenstein, Gert O R; Loos, Katja

    2015-11-09

    Furan-2,5-dicarboxylic acid (FDCA)-based furanic-aliphatic polyamides can be used as promising sustainable alternatives to polyphthalamides (semiaromatic polyamides) and be applied as high performance materials with great commercial interest. In this study, poly(octamethylene furanamide) (PA8F), an analog to poly(octamethylene terephthalamide) (PA8T), is successfully produced via Novozym 435 (N435)-catalyzed polymerization, using a one-stage method in toluene and a temperature-varied two-stage method in diphenyl ether, respectively. The enzymatic polymerization results in PA8F with high weight-average molecular weight (M̅(w)) up to 54000 g/mol. Studies on the one-stage enzymatic polymerization in toluene indicate that the molecular weights of PA8F increase significantly with the concentration of N435; with an optimal reaction temperature of 90 °C. The temperature-varied, two-stage enzymatic polymerization in diphenyl ether yields PA8F with higher molecular weights, as compared to the one-stage procedure, at higher reaction temperatures. MALDI-ToF MS analysis suggests that eight end groups are present in the obtained PA8F: ester/amine, ester/ester, amine/amine, acid/amine, ester/acid, acid/acid, ester/amide, and no end groups (cyclic). Compared to PA8T, the obtained PA8F possesses a similar Tg and similar crystal structures, a comparable Td, but a lower Tm.

  10. Synthesis of nanomagnetic fluids and their UV spectrophotometric response with aliphatic organic acids and 1st tier dendrimers

    Science.gov (United States)

    Pandya, Shivani R.; Singh, Man

    2016-04-01

    Synthesis of Magnetic nanoparticles were made using coprecipitation method on mixing Fe+3 and Fe+2 in 2:1 ratio with aqueous 8M NaOH which on heating at 90°C for 2 h has yielded 85% magnetic (Fe3O4) nanoparticles (MNPs), characterized by XRD, VSM, SEM, and HR-TEM. The formic acid (FA), oxalic acid (OA) and citric acid (CA), the series of aliphatic organic acids along with Trimesoyl 1, 3, 5 tridimethyl malonate (TTDMM), trimesoyl 1, 3, 5 tridiethyl malonate (TTDEM), trimesoyl 1, 3, 5 tridipropyl malonate (TTDPM), trimesoyl 1, 3, 5 tridibutyl malonate (TTDBM) and trimesoyl 1, 3, 5 tridihexyl malonate (TTDHM) 1st tier dendrimers were used separately for preparing nanomagnetic fluid. From 25 to 150 µM MNPs at an interval of 25 µM were dispersed in 150 µM of acids and dendrimers separately with DMSO. UV-VIS spectrophotometry showed a maximum MNPs dispersion with TTDMM against others and found to be most stable nanomagnetic fluid on account of capping type mechanism of acids.

  11. Enteric polymer based on pH-responsive aliphatic polycarbonate functionalized with vitamin E to facilitate oral delivery of tacrolimus.

    Science.gov (United States)

    Wang, Menglin; Sun, Jin; Zhai, Yinglei; Lian, He; Luo, Cong; Li, Lin; Du, Yuqian; Zhang, Dong; Ding, Wenya; Qiu, Shuhong; Liu, Yuhai; Kou, Longfa; Han, Xiangfei; Xiang, Rongwu; Wang, Yongjun; He, Zhonggui

    2015-04-13

    To improve the bioavailability of orally administered drugs, we synthesized a pH-sensitive polymer (poly(ethylene glycol)-poly(2-methyl-2-carboxyl-propylene carbonate)-vitamin E, mPEG-PCC-VE) attempting to integrate the advantages of enteric coating and P-glycoprotein (P-gp) inhibition. The aliphatic polycarbonate chain was functionalized with carboxyl groups and vitamin E via postpolymerization modification. Optimized by comparison and central composite design, mPEG113-PCC32-VE4 exhibited low critical micelle concentration of 1.7 × 10(-6) mg/mL and high drug loading ability for tacrolimus (21.2% ± 2.7%, w/w). The pH-responsive profile was demonstrated by pH-dependent swelling and in vitro drug release. Less than 4.0% tacrolimus was released under simulated gastric fluid after 2.5 h, whereas an immediate release was observed under simulated intestinal fluid. The mPEG113-PCC32-VE4 micelles significantly increased the absorption of P-gp substrate tacrolimus in the whole intestine. The oral bioavailability of tacrolimus micelles was 6-fold higher than that of tacrolimus solution in rats. This enteric polymer therefore has the potential to become a useful nanoscale carrier for oral delivery of drugs.

  12. Carbon-rich dust past the asymptotic giant branch: aliphatics, aromatics, and fullerenes in the Magellanic Clouds

    CERN Document Server

    Sloan, G C; Zijlstra, A A; Kraemer, K E; Weis, A P; Matsuura, M; Volk, K; Peeters, E; Duley, W W; Cami, J; Bernard-Salas, J; Kemper, F; Sahai, R

    2014-01-01

    Infrared spectra of carbon-rich objects which have evolved off the asymptotic giant branch reveal a range of dust properties, including fullerenes, polycyclic aromatic hydrocarbons (PAHs), aliphatic hydrocarbons, and several unidentified features, including the 21 um emission feature. To test for the presence of fullerenes, we used the position and width of the feature at 18.7-18.9 um and examined other features at 17.4 and 6-9 um. This method adds three new fullerene sources to the known sample, but it also calls into question three previous identifications. We confirm that the strong 11 um features seen in some sources arise primarily from SiC, which may exist as a coating around carbonaceous cores and result from photo-processing. Spectra showing the 21 um feature usually show the newly defined Class D PAH profile at 7-9 um. These spectra exhibit unusual PAH profiles at 11-14 um, with weak contributions at 12.7 um, which we define as Class D1, or show features shifted to ~11.4, 12.4, and 13.2 um, which we ...

  13. Presence of aliphatic and polycyclic aromatic hydrocarbons in near-surface sediments of an oil spill area in Bohai Sea.

    Science.gov (United States)

    Li, Shuanglin; Zhang, Shengyin; Dong, Heping; Zhao, Qingfang; Cao, Chunhui

    2015-11-15

    In order to determine the source of organic matter and the fingerprint of the oil components, 50 samples collected from the near-surface sediments of the oil spill area in Bohai Sea, China, were analyzed for grain size, total organic carbon, aliphatic hydrocarbons (AHs), and polycyclic aromatic hydrocarbons (PAHs). The concentrations of C15-35 n-alkanes and 16 United States Environmental Protection Agency (US EPA) priority pollutant PAHs were found in the ranges of 0.88-3.48μg g(-1) and 9.97-490.13ng/g, respectively. The terrestrial organic matters characterized by C27-C35 n-alkanes and PAHs, resulting from the combustion of higher plants, are dominantly contributed from the transportation of these plants by rivers. Marine organic matters produced from plankton and aquatic plants were represented by C17-C26 n-alkanes in AHs. Crude oil, characterized by C17-C21 n-alkanes, unresolved complex mixture (UCM) with a mean response factor of C19 n-alkanes, low levels of perylene, and a high InP/(InP+BghiP) ratio, seeped into the oceans from deep hydrocarbon reservoirs, as a result of geological faults.

  14. Distribution and sources of aliphatic and polycyclic aromatic hydrocarbons in suspended particulate matter in water from two Brazilian estuarine systems

    Science.gov (United States)

    Maioli, Otávio L. G.; Rodrigues, Kamila C.; Knoppers, Bastiaan A.; Azevedo, Débora A.

    2011-07-01

    The levels of selected organic markers, including 17 polycyclic aromatic hydrocarbons (PAHs), 16 of which are classified as priority pollutants by the US-EPA and perylene, aliphatic hydrocarbons (total and linear alkanes) and petroleum biomarkers (hopanes and steranes), were measured in suspended particulate matter (SPM) of the Mundaú-Manguaba estuarine-lagoon system (MMELS) in northeastern Brazil and the Paraíba do Sul River (PSR) estuary in southeastern Brazil, both of which are affected by sugarcane agriculture and urbanization. A total of 33 surface water samples of SPM were collected (22 from the MMELS and 11 from the PSR). The ∑16PAH ranged from 221 to 1243 ng g -1 in the MMELS and from 228 to 1814 ng g -1 in the PSR. Hopane and sterane concentrations in the PSR were higher than in the MMELS due to the input from petrogenic sources in PSR. The contributions of higher plants were also observed by n-alkane analyses. The PAH isomeric ratios indicated that the SPM from MMELS showed characteristics of combustion from biomass or petroleum and PSR was associated to petrogenic input, either from combustion or from unburned petroleum. Three sampling sites located near to the sugarcane plant and mouth of the rivers showed higher PAH concentrations and may largely be considered as highly contaminated. However, levels of n-alkanes and petroleum biomarkers in both study areas were relatively low.

  15. Controlled oxidation of aliphatic CH bonds in metallo-monooxygenases: mechanistic insights derived from studies on deuterated and fluorinated hydrocarbons.

    Science.gov (United States)

    Chen, Yao-Sheng; Luo, Wen-I; Yang, Chung-Ling; Tu, Yi-Jung; Chang, Chun-Wei; Chiang, Chih-Hsiang; Chang, Chi-Yao; Chan, Sunney I; Yu, Steve S-F

    2014-05-01

    The control over the regio- and/or stereo-selective aliphatic CH oxidation by metalloenzymes is of great interest to scientists. Typically, these enzymes invoke host-guest chemistry to sequester the substrates within the protein pockets, exploiting sizes, shapes and specific interactions such as hydrogen-bonding, electrostatic forces and/or van der Waals interactions to control the substrate specificity, regio-specificity and stereo-selectivity. Over the years, we have developed a series of deuterated and fluorinated variants of these hydrocarbon substrates as probes to gain insights into the controlled CH oxidations of hydrocarbons facilitated by these enzymes. In this review, we illustrate the application of these designed probes in the study of three monooxygenases: (i) the particulate methane monooxygenase (pMMO) from Methylococcus capsulatus (Bath), which oxidizes straight-chain C1-C5 alkanes and alkenes to form their corresponding 2-alcohols and epoxides, respectively; (ii) the recombinant alkane hydroxylase (AlkB) from Pseudomonas putida GPo1, which oxidizes the primary CH bonds of C5-C12 linear alkanes; and (iii) the recombinant cytochrome P450 from Bacillus megaterium, which oxidizes C12-C20 fatty acids at the ω-1, ω-2 or ω-3 CH positions.

  16. FTIR and molecular mechanics studies of H-bonds in aliphatic polyurethane and polyamide-66 model molecules

    Science.gov (United States)

    Wang, Guoqing; Zhang, Chunxia; Guo, Xiaohe; Ren, Zhiyong

    2008-02-01

    Model aliphatic polyurethane (APU) hard segment based on 1,6-hexamethylene diisocyanate (HDI) and 1,4-butanediol (BDO) were prepared. FTIR and molecular mechanics (MM) simulation were used to conduct the systematic studies on APU and polyamide-66 (PA-66) whose sole difference lies in the alkoxyl oxygen. It was found that the introduction of the alkoxyl not only increases the conformations in APU, makes it a possible H-bond acceptor, but also weakens the H-bond between NH and O dbnd C in APU. There are two conformers stably existed in APU with lowest energy, leading to eight H-bond complexes based on NH as donor and (1) O dbnd C as acceptor, and another two complexes based on (2) alkoxyl O and (3) urethane N as acceptors, whereas there is only one stable conformer in PA-66, leading to one H-bond complex. One predominant H-bond complex has been found in APU with probability of about 95%. The simulated results are consistent with the νNH and νC dbnd O band shifting in FTIR.

  17. Aliphatic C(17)-polyacetylenes of the falcarinol type as potential health promoting compounds in food plants of the Apiaceae family.

    Science.gov (United States)

    Christensen, Lars P

    2011-01-01

    Many epidemiological studies have provided evidence that a high intake of fruits and vegetables is associated with a reduced risk for the development of cancer and cardiovascular diseases. Fruits and vegetables are known to contain health promoting components such as vitamins, minerals, antioxidants and dietary fibers, however, it is unclear which of these are responsible for the health promoting properties of fruits and vegetables. Aliphatic C(17)-polyacetylenes of the falcarinol type, which occur in common food plants of the Apiaceae family such as carrot, celeriac, parsnip and parsley, have demonstrated interesting bioactivities including antibacterial, antimycobacterial, and antifungal activity as well as anti-inflammatory, anti-platelet-aggregatory, neuritogenic and serotonergic effects. In addition, the cytotoxicity of falcarinol type polyacetylenes towards human cancer cells, bioavailability, and their potential anticancer effect in vivo indicates that these compounds may contribute to the health effects of certain vegetables and hence could be important nutraceuticals. The bioactivity of falcarinol type polyacetylenes occurring in food plants of the Apiaceae family, their possible mode of action and possible health promoting effects are discussed in this review as well as the effect of storage, processing and other factors that can influence the content of these compounds in particular root vegetables and products. Moreover, recent patents on bioactivity of falcarinol type polyacetylenes and inventions making use of this knowledge are presented and discussed.

  18. Preliminary chemical analysis and biological testing of materials from the HRI catalytic two-stage liquefaction (CTSL) process. [Aliphatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Later, D.W.; Wilson, B.W.

    1985-01-01

    Coal-derived materials from experimental runs of Hydrocarbon Research Incorporated's (HRI) catalytic two-stage liquefaction (CTSL) process were chemically characterized and screened for microbial mutagenicity. This process differs from two-stage coal liquefaction processes in that catalyst is used in both stages. Samples from both the first and second stages were class-fractionated by alumina adsorption chromatography. The fractions were analyzed by capillary column gas chromatography; gas chromatography/mass spectrometry; direct probe, low voltage mass spectrometry; and proton nuclear magnetic resonance spectrometry. Mutagenicity assays were performed with the crude and class fractions in Salmonella typhimurium, TA98. Preliminary results of chemical analyses indicate that >80% CTSL materials from both process stages were aliphatic hydrocarbon and polynuclear aromatic hydrocarbon (PAH) compounds. Furthermore, the gross and specific chemical composition of process materials from the first stage were very similar to those of the second stage. In general, the unfractionated materials were only slightly active in the TA98 mutagenicity assay. Like other coal liquefaction materials investigated in this laboratory, the nitrogen-containing polycyclic aromatic compound (N-PAC) class fractions were responsible for the bulk of the mutagenic activity of the crudes. Finally, it was shown that this activity correlated with the presence of amino-PAH. 20 figures, 9 tables.

  19. Fast Fourier Transform IR Characterization of Epoxy GY Systems Crosslinked with Aliphatic and Cycloaliphatic EH Polyamine Adducts

    Science.gov (United States)

    Nikolic, Goran; Zlatkovic, Sasa; Cakic, Milorad; Cakic, Suzana; Lacnjevac, Caslav; Rajic, Zoran

    2010-01-01

    The use of fast FT-IR spectroscopy as a sensitive method to estimate a change of the crosslinking kinetics of epoxy resin with polyamine adducts is described in this study. A new epoxy formulation based on the use of polyamine adducts as the hardeners was analyzed. Crosslinking reactions of the different stoichiometric mixtures of the unmodified GY250 epoxy resin with the aliphatic EH606 and the cycloaliphatic EH637 polyamine adducts were studied using mid FT-IR spectroscopic techniques. As the crosslinking proceeded, the primary amine groups in polyamine adduct are converted to secondary and the tertiary amines. The decrease in the IR band intensity of epoxy groups at about 915 cm−1, as well as at about 3,056 cm−1, was observed due to process. Mid IR spectral analysis was used to calculate the content of the epoxy groups as a function of crosslinking time and the crosslinking degree of resin. The amount of all the epoxy species was estimated from IR spectra to changes during the crosslinking kinetics of epichlorhydrin. PMID:22315562

  20. Hydrolysis Process of the Anticancer Agents Novel Non-classical trans-Platinum(Ⅱ) with Aliphatic Amines

    Institute of Scientific and Technical Information of China (English)

    YUAN Qing-Hui; ZHOU Li-Xin

    2007-01-01

    The hydrolysis process of the anticancer agents novel non-classical transplatinum( Ⅱ ) with aliphatic amines and the influence of solvent models therein have been studied by using hybrid density functional theory (B3LYP). In this study, the stepwise hydrolysis, trans[PtCl2(Am)(isopropylamine)] + 2H2O → trans-[Pt(Am)(isopropylamine)(OH2)2]2++ 2Cl-, was explored. Implicit solvent effects were incorporated through polarized continuum models. The stationary points on the potential energy surfaces for the first and second hydrolysis steps,proceeding via a general SN2 pathway, were fully optimized and characterized. It was found that the first hydrolysis reaction is easier than the second one and the hydrolysis of trans- [PtCl2-(isopropylamine)2] is the easiest in our studying systems. The result can assist in under- tanding the hydrolysis mechanism of trans-[PtCl2(Am)(isopropylamine)] and designing novel Pt-based anticancer drugs.

  1. TRANSESTERIFICATION OF POLY(BISPHENOL A CARBONATE) WITH AROMATIC AND ALIPHATIC SEGMENTS IN BUTYLENE TEREPHTHALATE-CAPROLACTONE COPOLYESTER

    Institute of Scientific and Technical Information of China (English)

    Song Wang; Yi-ping Huang; Xiao-lie Luo; De-zhu Ma

    2004-01-01

    In this article, the transesterification ofpoly(bisphenol A carbonate) (PC) with butylene terephthalate-caprolactone copolyester at a weight ratio 50/50 (BCL(21)) was thoroughly investigated by proton nuclear magnetic resonance spectroscopy (1H-NMR), in conjunction with a model compound. The 1H-NMR results of the annealed blend PC/BCL(21)show that the formation of bisphenol A-terephthalate ester units is the same as in the annealed blend of PC with PBT, and the transesterification actually occurs between PC and butylene terephthalate (BT) segments in BCL(21). By comparison with the model compound bisphenol A dibutyrate, the new signal appearing at δ = 2.56 in the 1H-NMR spectrum confirms the existence of bisphenol A caprolactone ester units resulting from the exchange reaction of PC with caprolactone (CL)segments. 1H-NMR analysis of the transesterification rates reveals that the reaction of PC with aromatic and aliphatic segments in BCL(21) proceeds in a random manner. The miscibility of the blend PC/BCL(21) copolyester is favorable for the transesterification of PC with BT segments and CL segments.

  2. Close correlation between heat shock response and cytotoxicity in Neurospora crassa treated with aliphatic alcohols and phenols

    Energy Technology Data Exchange (ETDEWEB)

    Meyer, U.; Schweim, P.; Fracella, F.; Rensing, L. [Univ. of Bremen (Germany)

    1995-03-01

    In Neurospora crassa the aliphatic alcohols methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, ethylene glycol, glycerol, and allyl alcohol and the phenolic compounds phenol, hydroquinone, resorcinol, pyrogallol, phloroglucinol, sodium salicylate, and acetylsalicylic acid were analyzed with respect to their capacities to induce heat shock proteins (HSP) and to inhibit protein synthesis. Both the alcohols and phenols showed the greatest levels of HSP induction at concentrations which inhibited the overall protein synthesis by about 50%. The abilities of the different alcohols to induce the heat shock response are proportional to their lipophilicities: the lipophilic alcohol isobutanol is maximally inductive at about 0.6 M, whereas the least lipophilic alcohol, methanol, causes maximal induction at 5.7 M. The phenols, in general, show a higher capability to induce the heat shock response. The concentrations for maximal induction range between 25 mM (sodium salicylate) and 100 mM (resorcinol). Glycerol (4.1 M) shifted the concentration necessary for maximal HSP induction by hydroquinone from 50 to 200 mM. The results reveal that the induction of HSP occurs under conditions which considerably constrain cell metabolism. The heat shock response, therefore, does not represent a sensitive marker for toxicity tests but provides a good estimate for the extent of cell damage.

  3. Fenton process for degradation of selected chlorinated aliphatic hydrocarbons exemplified by trichloroethylene, 1,1-dichloroethylene and chloroform

    Institute of Scientific and Technical Information of China (English)

    Zhimin QIANG; Weiwei BEN; ChinPao HUANG

    2008-01-01

    The degradation of selected chlorinated ali-phatic hydrocarbons (CAHs) exemplified by trichloroethy-lene (TCE), 1,1-dichloroethylene (DCE), and chloroform (CF) was investigated with Fenton oxidation process. The results indicate that the degradation rate was primarily affected by the chemical structures of organic contami-nants. Hydroxyl radicals (·OH) preferred to attack the organic contaminants with an electron-rich structure such as chlorinated alkenes (i.e., TCE and DCE). The dosing mode of Fenton's reagent, particularly of Fe2+, significantly affected the degradation efficiency of studied organic compound. A new "time-squared" kinetic model, C = Coexp(-kobst2), was developed to express the degrada-tion kinetics of selected CAHs. This model was applicable to TCE and DCE, but inapplicable to CF due to their varied reaction rate constants towards ·OH. Chloride release was monitored to examine the degree of dechlorina- tion during the oxidation of selected CAHs. TCE was more easily dechlorinated than DCE and CF. Dichloroacetic acid (DCAA) was identified as the major reaction intermediate in the oxidation of TCE, which could be completely removed as the reaction proceeded. No reaction intermedi- ates or byproducts were identified in the oxidation of DCE and CF. Based on the identified intermediate, the reaction mechanism of TCE with Fenton's reagent was proposed.

  4. Synthesis of novel lanthanide acylpyrazolonato ligands with long aliphatic chains and immobilization of the Tb complex on the surface of silica pre-modified via hydrophobic interactions.

    Science.gov (United States)

    Pettinari, C; Marchetti, F; Pettinari, R; Belousov, Y A; Taydakov, I V; Krasnobrov, V D; Petukhov, D I; Drozdov, A A

    2015-09-01

    Five new complexes Ln(Q(C17))3(H2O)(Solv) (Ln = Y, Solv = H2O, Ln = Tb, Dy, Sm or Eu, Solv = EtOH) were synthesized with the acylpyrazolonato ligand Q(C17) bearing a long aliphatic C17H35 chain in the acyl moiety, and the crystal structure of Y(Q(C17))3(H2O)2 shows the three aliphatic chains from the coordinated ligands positioned in the same direction, affording plane layers built by Y(Q(C17))3(H2O)2 molecules connected through H-bonding interactions. The layers are stitched to each other like in "hook & loop" tapes. Luminescence of complexes was determined and the complex Tb(Q(C17))3(H2O)(EtOH) was immobilized on the surface of silica preprocessed using a C17H35CONH(CH2)3Si(OEt)3 reagent via hydrophobic interactions of long aliphatic chains. Luminescent properties and micromorphology of the obtained hybrid particles and hybrid films were investigated. Intensive green emission of the complex retains after grafting onto the silica surface. Inclusion of the complex on the surface of silica materials occurs as separate molecules, after the disruption of the H-bonding network present in the crystalline phase of the pure terbium sample.

  5. Theoretical structural study on the adsorption properties of aliphatic aldehydes on ZnO nanoclusters and graphene-like nanosheets systems

    Science.gov (United States)

    Tayebee, R.; Zamand, N.; Hosseini-nasr, A.; Kargar Razi, M.

    2014-05-01

    The structure optimizations for some aliphatic aldehydes adsorbed on ZnO nanoclusters, and graphene-like nanosheets were carried out using the B3LYP/LanL2DZ calculations and the adsorption energies were calculated. It was considered that adsorption of the examined aldehydes on the ZnO nanoclusters and graphene-like nanosheets occurred through carbonyl oxygens of aldehyde molecules with the surface Zn2+ ions of the central ring. Aldehydes with the general formula of R-COH (R denotes a branched or linear aliphatic chain with maximum of three carbon atoms) were considered. Also, Effects of chain length were investigated on the orientation of the aldehyde molecules with respect to the nanosheet and nanocluster surfaces. Findings revealed that the adsorption energy was decreased with enhancing chain length. However, the most negative adsorption energy was obtained for iso-butyraldehyde, as a branched aldehyde. Interaction of the aldehyde molecules with the surfaces of nanosheets were analyzed by means of DOS analysis and Bader's method. We hope the obtained results be helpful in identifying the mechanism of cyclotrimerization of aliphatic aldehydes on the surface of zinc oxide nanoparticles.

  6. Effects of halogenated aromatics/aliphatics and nitrogen(N)-heterocyclic aromatics on estimating the persistence of future pharmaceutical compounds using a modified QSAR model.

    Science.gov (United States)

    Lim, Seung Joo; Fox, Peter

    2014-02-01

    The effects of halogenated aromatics/aliphatics and nitrogen(N)-heterocyclic aromatics on estimating the persistence of future pharmaceutical compounds were investigated using a modified half life equation. The potential future pharmaceutical compounds investigated were approximately 2000 pharmaceutical drugs currently undergoing the United States Food and Drug Administration (US FDA) testing. EPI Suite (BIOWIN) model estimates the fates of compounds based on the biodegradability under aerobic conditions. While BIOWIN considered the biodegradability of a compound only, the half life equation used in this study was modified by biodegradability, sorption and cometabolic oxidation. It was possible that the potential future pharmaceutical compounds were more accurately estimated using the modified half life equation. The modified half life equation considered sorption and cometabolic oxidation of halogenated aromatic/aliphatics and nitrogen(N)-heterocyclic aromatics in the sub-surface, while EPI Suite (BIOWIN) did not. Halogenated aliphatics in chemicals were more persistent than halogenated aromatics in the sub-surface. In addition, in the sub-surface environment, the fates of organic chemicals were much more affected by halogenation in chemicals than by nitrogen(N)-heterocyclic aromatics.

  7. Design, Synthesis, EPR-Studies and Conformational Bias of Novel Spin-Labeled DCC-Analogues for the Highly Regioselective Labeling of Aliphatic and Aromatic Carboxylic Acids.

    Science.gov (United States)

    Gölz, Jan Philipp; NejatyJahromy, Yaser; Bauer, Mirko; Muhammad, Ashraf; Schnakenburg, Gregor; Grimme, Stefan; Schiemann, Olav; Menche, Dirk

    2016-07-04

    Novel types of spin-labeled N,N'-dicyclohexylcarbodiimides (DCC) are reported that bear a 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) residue on one side and different aromatic and aliphatic cyclohexyl analogues on the other side of the diimide core. These readily available novel reagents add efficiently to aliphatic and aromatic carboxylic acids, forming two possible spin-labeled amide derivatives with different radical distances of the resulting amide. The addition of aromatic DCC analogues proceeds with excellent selectivity, giving amides where the carboxylic acid is exclusively connected to the aromatic residue, while little or no selectivity was observed for the aliphatic congeners. The usefulness of these adducts in structural studies was demonstrated by EPR (electron paramagnetic resonance) measurements of biradical adducts of biphenyl-4,4'-dicarboxylic acids. These analyses also reveal high degrees of conformational bias for aromatic DCC derivatives, which further underlines the powerfulness of these novel reagents. This observation was further corroborated by quantum chemical calculations, giving a detailed understanding of the structural dynamics, while detailed information on the solid state structure of all novel reagents was obtained by X-ray structure analyses.

  8. VC复合脂肪酸酯的合成及抗氧化性能%SYNTHESIS AND ANTIOXIDANT EFFECTS OF ASCORBYL COMPOSITE ALIPHATIC ESTER

    Institute of Scientific and Technical Information of China (English)

    冯光炷; 谢文磊

    2001-01-01

    猪油与甲醇进行酯交换制备复合脂肪酸甲酯,得率97.2%.再以浓硫酸为溶剂和催化剂,VC和复合脂肪酸甲酯进行酯交换合成VC复合脂肪酸酯.考察了反应时间、反应物配比及浓硫酸用量对酯交换反应的影响,结果表明,最适宜的反应条件为:n(VC)∶n(复合脂肪酸酯)为1∶1.2,反应时间为26h,n(浓H2SO4)∶n(VC+复合脂肪酸酯)为1∶0.15,反应温度为25℃,产率达76%.产品的抗氧化性能测试表明VC复合脂肪酸酯是一种优良的无毒抗氧化剂.%Ascorbyl composite aliphatic ester was synyhesized by transesterificantion of L-ascorbic acid with methyl composite aliphatic ester which is synthesized from lard and methyl alcohol using concentrated sulfuric acid as sol ve nt and catalyst. The yield was up to 76%. The effects of reaction temperature, r atio of reactant, amount of concentrated sulfuric acid on transesterification ha ve been investigated. The optimum synthetic conditions are that the ratio of Vc to composite aliphatic ester is 1∶1.2,reaction time is 26 h, the ratio of conce ntrated H2SO4 to composite aliphatic ester is 1∶0.15,reaction temperatur e is 25 ℃ .The test of antioxidant shows that Ascorbyl composite aliphatic ester is a good oxidant without poison.

  9. Enhancement of the optical properties of a new radiochromic dosimeter based on aliphatic-aromatic biodegradable polymers

    Energy Technology Data Exchange (ETDEWEB)

    Schimitberger, Thiago, E-mail: tschimitberger@ufmg.br [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Escola de Engenharia. Departamento de Engenharia Nuclear; Faria, Luiz O., E-mail: farialo@cdtn.br [Centro de desenvolvimento da Tecnologia Nuclear (CDTN/CNEN-MG), Belo Horizonte, MG (Brazil)

    2015-07-01

    The development of a dosimeter that is of low cost, easy to process without dependence on expensive complex instruments and environment friendly is a challenging in irradiation quality control. Recently, an aliphatic-aromatic biodegradable polymer has been proposed as radiochromic dosimeter. The dosimeter is based on biodegradable poly(butylene adipate-co-terephthalate) copolymers (PBAT). In order to improve the photoluminescence (PL) properties of PBAT, increasing its range of applicability (50 kGy to 1000 kGy), this work investigates the influence of solution concentration in the dose response. Films with thickness of c.a. 80 μm were produce by wirebar coating, a simple deposition method for preparing large areas of organic films at low cost. The irradiation of samples was performed at room temperature using a Co-60 source at dose rate of 20 kGy/h. The films were exposed to doses ranging from 501 kGy to 1000 kGy. A 405 nm LED light source was used to excite the films. The USB2000 spectrometer made by Ocean Optics was used to collect the emission spectra of the luminescent films. The photoluminescent intensity captured by the spectrometer present linear radiation dose dependence. The maximum PL for the film sample made from a 0.05 g.mL{sup -1} solution is 1.5 (a.u.) while it is about 3.5 (a.u.) for a film sample made from a 0.2 mg.mL{sup -1} solution, when irradiated with 1000 kGy. These results indicate that PBAT films have great potential to be used as a high gamma dose radiochromic dosimeter over a wide dose range, expanding its applicability for different radiations process. (author)

  10. PEGylated and Functionalized Aliphatic Polycarbonate Polyplex Nanoparticles for Intravenous Administration of HDAC5 siRNA in Cancer Therapy.

    Science.gov (United States)

    Frère, Antoine; Baroni, Alexandra; Hendrick, Elodie; Delvigne, Anne-Sophie; Orange, François; Peulen, Olivier; Dakwar, George R; Diricq, Jérôme; Dubois, Philippe; Evrard, Brigitte; Remaut, Katrien; Braeckmans, Kevin; De Smedt, Stefaan C; Laloy, Julie; Dogné, Jean-Michel; Feller, Georges; Mespouille, Laetitia; Mottet, Denis; Piel, Géraldine

    2017-01-25

    Guanidine and morpholine functionalized aliphatic polycarbonate polymers are able to deliver efficiently histone deacetylase 5 (HDAC5) siRNA into the cytoplasm of cancer cells in vitro leading to a decrease of cell proliferation were previously developed. To allow these biodegradable and biocompatible polyplex nanoparticles to overcome the extracellular barriers and be effective in vivo after an intravenous injection, polyethylene glycol chains (PEG750 or PEG2000) were grafted on the polymer structure. These nanoparticles showed an average size of about 150 nm and a slightly positive ζ-potential with complete siRNA complexation. Behavior of PEGylated and non-PEGylated polyplexes were investigated in the presence of serum, in terms of siRNA complexation (fluorescence correlation spectroscopy), size (dynamic light scattering and single-particle tracking), interaction with proteins (isothermal titration calorimetry) and cellular uptake. Surprisingly, both PEGylated and non-PEGylated formulations presented relatively good behavior in the presence of fetal bovine serum (FBS). Hemocompatibility tests showed no effect of these polyplexes on hemolysis and coagulation. In vivo biodistribution in mice was performed and showed a better siRNA accumulation at the tumor site for PEGylated polyplexes. However, cellular uptake in protein-rich conditions showed that PEGylated polyplex lost their ability to interact with biological membranes and enter into cells, showing the importance to perform in vitro investigations in physiological conditions closed to in vivo situation. In vitro, the efficiency of PEGylated nanoparticles decreases compared to non-PEGylated particles, leading to the loss of the antiproliferative effect on cancer cells.

  11. Visual Recognition of Aliphatic and Aromatic Amines Using a Fluorescent Gel: Application of a Sonication-Triggered Organogel.

    Science.gov (United States)

    Pang, Xuelei; Yu, Xudong; Lan, Haichuang; Ge, Xiaoting; Li, Yajuan; Zhen, Xiaoli; Yi, Tao

    2015-06-24

    A naphthalimide-based fluorescent gelator (N1) containing an alkenyl group has been designed and characterized. This material is able to gelate alcohols via a precipitate-to-gel transformation when triggered with ultrasound for less than 2 min (S-gel). The gelation process in n-propanol was studied by means of absorption, fluorescence, and IR spectra, scanning electron microscopy (SEM) images, and X-ray diffraction patterns. The fluorescence intensity of N1 decreased during the gelation process in a linear relationship with the sonication time. The S-gel of N1 could be used to sense aliphatic and aromatic amines by measuring the change in the signal output. For example, the addition of propylamine to the S-gel of N1 resulted in a dramatic enhancement of the fluorescence intensity, accompanied by a gel-to-sol transition. On the contrary, when the S-gel of N1 was treated with aromatic amines such as aniline, fluorescence was quenched and there was no gel collapse. The sensing mechanisms were studied by (1)H NMR, small-angle X-ray scattering, SEM and spectroscopic experiments. It is proposed that isomerization of the alkenyl group of N1 from the trans to cis form occurs when the S-gel is treated with propylamine, resulting in a gel-sol transition. However, the aromatic aniline molecules prefer to insert into the gel networks of N1 via hydrogen-bonding and charge-transfer interactions, maintaining the gel state. As potential applications, testing strips of N1 were prepared to detect aniline.

  12. Aliphatic amine cured PDMS–epoxy interpenetrating network system for high performance engineering applications—Development and characterization

    Indian Academy of Sciences (India)

    T V Thanikai Velan; I Mohammed Bilal

    2000-10-01

    A siliconized epoxy interpenetrating network (IPN) was synthesized from commercially available DGEBA epoxy resin GY250 (Ciba-Geigy, epoxy equivalent = 182–192, viscosity = 9000–12000 cP) and hydroxyl terminated polydimethylsiloxane (PDMS). PDMS and GY250 were thoroughly mixed at 30°C to get the prepolymer. Stoichiometric amounts of PDMS–epoxy prepolymer, -aminopropyltriethoxysilane, aliphatic amine curing agent (HY951), and dibutyltindilaurate catalyst, were thoroughly mixed and cast in a mould after evacuating the entrapped air. The cured material was then taken out and post cured at 70°C for 10 h. IPN was characterized by FTIR spectroscopy, SEM, DSC, TGA and viscosity measurements. Incorporation of PDMS in the epoxy matrix increased the viscosity and lowered the exotherm and pot-life. PDMS in IPN increased , heat-distortion temperature and reduced the percentage weight loss with increase in temperature. Incorporation of PDMS drastically reduced the tensile and flexural strengths and hardness. By reducing the tensile and flexural modulus, the siloxane moiety effectively reduced the internal stress of IPN thereby improving its impact strength and percentage elongation. PDMS increased the electric potential gradient of IPN to withstand without breakdown. An increase in the tracking index and arc resistance of IPN were observed, because of the presence of Si–O–Si, which minimized the possibility of forming carbonized path. Volume and surface resistivities of IPN also increased with the incorporation of PDMS. The siliconized epoxy IPN, with better impact and thermal resistance, may be used in automobile and aerospace applications to withstand high temperature, and mechanical stress. The PDMS–epoxy IPN may be used for encapsulation, high temperature and high voltage application due to their low shrinkage and lesser internal stress. With the improved electrical characteristics, IPN may be used for high performance electrical insulation, insulator housings

  13. Coadsorption of low-molecular weight aromatic and aliphatic alcohols and acids with the cationic surfactant, CTAB, on silica surfaces.

    Science.gov (United States)

    Wangchareansak, Thipvaree; Keniry, Max A; Liu, Guangming; Craig, Vincent S J

    2014-06-17

    We have investigated the coadsorption of a range of small molecules with the cationic surfactant CTAB to silica surfaces over a range of concentrations and CTAB to solute ratios and compared the coadsorption with adsorption in the presence of the salicylate ion. We find that molecules with aromatic character and molecules with double bonds are most favorably adsorbed, and we attribute this to cation-π bonding between the surfactant headgroups and the π orbitals of the unsaturated bonds of the solute molecules. The adsorption is complex and depends on chemical interactions between the solute molecules and the surfactant, which are highly specific to the structure of the solute. To improve our understanding of the specifics of these interactions, we have performed one-dimensional rotating frame Overhauser spectroscopy (ROESY) nuclear magnetic resonance experiments. These experiments show the complexity of the intermolecular interactions and can be used to determine the position of the solute molecule with regard to the CTAB molecules in the adsorbed aggregates. The ROESY spectrum for the salicylate anion is distinct from those of the other solute molecules and suggests that the anions are dimerizing. Along with the cation-π bonding between the dimers, this provides a model for the strong influence that salicylate has on adsorption, micellar structure, and viscoelasticity. The ROESY data indicate that the catechol molecule interacts with all parts of the surfactant alkane chains such that they wrap around the molecule, but this has little effect on the interfacial curvature or aggregate shape. More intense isophthalic acid-CTAB intermolecular ROEs compared to those of other aromatic solutes are consistent with an interaction between isophthalic acid and the headgroups of two surfactant molecules that slows the intramicellar motion of isophthalic acid. Differences in interactions between solute molecules and the aliphatic surfactant chains do not result in changes

  14. Resonance-enhanced multiphoton ionization time-of-flight mass spectrometry for detection of nitrogen containing aliphatic and aromatic compounds: resonance-enhanced multiphoton ionization spectroscopic investigation and on-line analytical application.

    Science.gov (United States)

    Streibel, T; Hafner, K; Mühlberger, F; Adam, T; Zimmermann, R

    2006-01-01

    Resonance-enhanced multiphoton ionization (REMPI) combined with time-of-flight mass spectrometry (TOFMS) is an analytical method capable of on-line monitoring of trace compounds in complex matrices. A necessary prerequisite for substance selective detection is spectroscopic investigation of the target molecules. Several organic nitrogen compounds comprising aliphatic and aromatic amines, nitrogen heterocyclic compounds, and aromatic nitriles are spectroscopically investigated with a tunable narrow bandwidth optical parametric oscillator (OPO) laser system providing a scannable wavelength range between 220 and 340 nm. These species are known as possible precursors in fuel-NO formation from combustion of solid fuels such as biomass and waste. A newly conceived double inlet system was used in this study, which allows rapid change between effusive and supersonic molecular beams. The resulting REMPI spectra of the compounds are discussed with respect to electronic transitions that could be utilized for a selective ionization of these compounds in complex mixtures such as combustion and process gases. The practicability of this approach is demonstrated by wavelength selected on-line REMPI-TOFMS detection of aniline and cyanonaphthalene in the burning chamber of a waste incineration plant. REMPI mass spectra recorded at different excitation wavelengths as well as variations in time show the utilization of species-selective REMPI-TOFMS detection for on-line monitoring of crucial substances in pollutant formation.

  15. Synthesis of 4-((1E, 6E)-7-(4-hydroxy-3-methoxyphenyl)-3, 5-dioxohepta-1, 6-dienyl)-2-methoxyphenyl 4-fluorobenzoate, a novel monoester derivative of curcumin, its experimental and theoretical (DFT) studies

    Science.gov (United States)

    Srivastava, Sangeeta; Gupta, Preeti; Amandeep; Singh, Ranvijay Pratap

    2016-04-01

    Curcumin (1), isolated as a major component from the chloroform extract of Curcuma longa was converted to its ester derivative 4-((1E, 6E)-7-(4-hydroxy-3-methoxyphenyl)-3,5-dioxohepta-1,6-dienyl)-2-methoxyphenyl 4-fluorobenzoate (2). The compound has been characterized with the help of 1H, 13C NMR, UV, IR and mass spectrometry. The molecular geometry of synthesized compound was calculated in ground state by Density functional theory (DFT/B3LYP) using 6-31G (d,p) basis set. 1H and 13C NMR chemical shifts were calculated in ground state by using Gauge-Including Atomic Orbital (GIAO) approach and these values were correlated with experimental observations. The electronic properties such as HOMO and LUMO energies were calculated using time dependent Density Functional Theory (TD-DFT). Stability of the molecule as a result of hyper conjugative interactions and electron delocalization were analysed using Natural bond orbital (NBO) analysis. Intramolecular interactions were analysed by AIM (Atom in molecule) approach. Global reactivity descriptors were calculated to study the reactive site within molecule. The vibrational wavenumbers were calculated using DFT method and assigned with the help of potential energy distribution (PED). First hyperpolarizability values have been calculated to describe the nonlinear optical (NLO) property of the synthesized compounds. Molecular electrostatic potential (MEP) analysis has also been carried out.

  16. Mixed aliphatic and aromatic composition of evaporating very small grains in NGC 7023 revealed by the 3.4/3.3 μm ratio

    Science.gov (United States)

    Pilleri, P.; Joblin, C.; Boulanger, F.; Onaka, T.

    2015-01-01

    Context A chemical scenario was proposed for photon-dominated regions (PDRs) according to which UV photons from nearby stars lead to the evaporation of very small grains (VSGs) and the production of gas-phase polycyclic aromatic hydrocarbons (PAHs). Aims Our goal is to achieve better insight into the composition and evolution of evaporating very small grains (eVSGs) and PAHs through analyzing the infrared (IR) aliphatic and aromatic emission bands. Methods We combined spectro-imagery in the near- and mid-IR to study the spatial evolution of the emission bands in the prototypical PDR NGC 7023. We used near-IR spectra obtained with the IRC instrument onboard AKARI to trace the evolution of the 3.3 μm and 3.4 μm bands, which are associated with aromatic and aliphatic C–H bonds on PAHs. The spectral fitting involved an additional broad feature centered at 3.45 μm that is often referred to as the plateau. Mid-IR observations obtained with the IRS instrument onboard the Spitzer Space Telescope were used to distinguish the signatures of eVSGs and neutral and cationic PAHs. We correlated the spatial evolution of all these bands with the intensity of the UV field given in units of the Habing field G0 to explore how their carriers are processed. Results The intensity of the 3.45 μm plateau shows an excellent correlation with that of the 3.3 μm aromatic band (correlation coefficient R = 0.95) and a relatively poor correlation with the aliphatic 3.4 μm band (R=0.77). This indicates that the 3.45 μm feature is dominated by the emission from aromatic bonds. We show that the ratio of the 3.4 μm and 3.3 μm band intensity (I3.4/I3.3) decreases by a factor of 4 at the PDR interface from the more UV-shielded layers (G0 ~ 150, I3.4/I3.3 = 0.13) to the more exposed layers (G0 > 1 × 104, I3.4/I3.3 = 0.03). The intensity of the 3.3 μm band relative to the total neutral PAH intensity shows an overall increase with G0, associated with an increase of both the hardness of the UV

  17. Aliphatic and polycyclic aromatic hydrocarbons (PAHs) in soils of the northwest Qinling Mountains: Patterns, potential risk and an appraisal of the PAH ratios to infer their source.

    Science.gov (United States)

    Liu, Yanhong; Wu, Yingqin; Xia, Yanqing; Lei, Tianzhu; Tian, Chuntao; Hou, Xiaohuan

    2017-03-21

    Surface soils from the tourist areas of the northwest Qinling Mountains were analyzed to determine the concentrations, probable sources and potential risks of hydrocarbons. Concentrations of aliphatic and aromatic hydrocarbons ranged from 4.18 to 3240 ng g(-1) and 0.0462 to 101 ng g(-1) dry weight, respectively. The extent of soil contamination by hydrocarbons was generally typified by unpolluted to slightly polluted levels. The incremental lifetime cancer risks (ILCRs) for exposure to soil-borne PAHs indicated complete safety for tourists. Early diagenesis of natural products, bacteria activities and petroleum were the three main sources of aliphatic hydrocarbons, while the transport of air pollutants from pyrolytic processes was the main origin of PAHs. Because the photochemical reaction of PAHs in the atmosphere would produce lower ratios for Ant/(Ant + Phe), BaA/(BaA + Chr) and IcdP/(IcdP + BghiP), but a higher ratio for Fla/(Fla + Pyr), the source classification highly depended on the diagnostic ratios chosen. The plot of ΣCOM/Σ13PAH vs. ΣLMW/ΣHMWPAH provide additional information to distinguish the origins of PAHs, and it showed a cluster of pyrogenic sources except for sample JFS-8. Four sources were resolved by principal component analysis: (1) a low temperature pyrogenic process related to the use of fossil fuel and biomass, such as charcoal, straw and wood, which contributes 63.1% of the measured PAHs; (2) the potential contribution of diagenetic processes, contributing 18.4%; (3) traffic emissions, contributing 9.27%; and (4) bioconversion/bacterial action, contributing 5.82%. Additionally, there was a good exponential relationship (r(2) = 0.969) between the natural n-alkanes ratio (NAR) and carbon preference index for C23-C35 (CPI23-35) for all samples, which is of great use for the determination of the origins of aliphatic hydrocarbon.

  18. The Cer-cqu gene cluster determines three key players in a β-diketone synthase polyketide pathway synthesizing aliphatics in epicuticular waxes

    Science.gov (United States)

    Schneider, Lizette M; Adamski, Nikolai M; Christensen, Caspar Elo; Stuart, David B; Vautrin, Sonia; Hansson, Mats; Uauy, Cristobal; von Wettstein-Knowles, Penny

    2016-01-01

    Aliphatic compounds on plant surfaces, called epicuticular waxes, are the first line of defense against pathogens and pests, contribute to reducing water loss and determine other important phenotypes. Aliphatics can form crystals affecting light refraction, resulting in a color change and allowing identification of mutants in their synthesis or transport. The present study discloses three such Eceriferum (cer) genes in barley – Cer-c, Cer-q and Cer-u – known to be tightly linked and functioning in a biochemical pathway forming dominating amounts of β-diketone and hydroxy-β-diketones plus some esterified alkan-2-ols. These aliphatics are present in many Triticeae as well as dicotyledons such as Eucalyptus and Dianthus. Recently developed genomic resources and mapping populations in barley defined these genes to a small region on chromosome arm 2HS. Exploiting Cer-c and -u potential functions pinpointed five candidates, of which three were missing in apparent cer-cqu triple mutants. Sequencing more than 50 independent mutants for each gene confirmed their identification. Cer-c is a chalcone synthase-like polyketide synthase, designated diketone synthase (DKS), Cer-q is a lipase/carboxyl transferase and Cer-u is a P450 enzyme. All were highly expressed in pertinent leaf sheath tissue of wild type. A physical map revealed the order Cer-c, Cer-u, Cer-q with the flanking genes 101kb apart, confirming they are a gene cluster, Cer-cqu. Homology-based modeling suggests that many of the mutant alleles affect overall protein structure or specific active site residues. The rich diversity of identified mutations will facilitate future studies of three key enzymes involved in synthesis of plant apoplast waxes. PMID:26962211

  19. The Cer-cqu gene cluster determines three key players in a β-diketone synthase polyketide pathway synthesizing aliphatics in epicuticular waxes.

    Science.gov (United States)

    Schneider, Lizette M; Adamski, Nikolai M; Christensen, Caspar Elo; Stuart, David B; Vautrin, Sonia; Hansson, Mats; Uauy, Cristobal; von Wettstein-Knowles, Penny

    2016-03-09

    Aliphatic compounds on plant surfaces, called epicuticular waxes, are the first line of defense against pathogens and pests, contribute to reducing water loss and determine other important phenotypes. Aliphatics can form crystals affecting light refraction, resulting in a color change and allowing identification of mutants in their synthesis or transport. The present study discloses three such Eceriferum (cer) genes in barley - Cer-c, Cer-q and Cer-u - known to be tightly linked and functioning in a biochemical pathway forming dominating amounts of β-diketone and hydroxy-β-diketones plus some esterified alkan-2-ols. These aliphatics are present in many Triticeae as well as dicotyledons such as Eucalyptus and Dianthus. Recently developed genomic resources and mapping populations in barley defined these genes to a small region on chromosome arm 2HS. Exploiting Cer-c and -u potential functions pinpointed five candidates, of which three were missing in apparent cer-cqu triple mutants. Sequencing more than 50 independent mutants for each gene confirmed their identification. Cer-c is a chalcone synthase-like polyketide synthase, designated diketone synthase (DKS), Cer-q is a lipase/carboxyl transferase and Cer-u is a P450 enzyme. All were highly expressed in pertinent leaf sheath tissue of wild type. A physical map revealed the order Cer-c, Cer-u, Cer-q with the flanking genes 101kb apart, confirming they are a gene cluster, Cer-cqu. Homology-based modeling suggests that many of the mutant alleles affect overall protein structure or specific active site residues. The rich diversity of identified mutations will facilitate future studies of three key enzymes involved in synthesis of plant apoplast waxes.

  20. Enantioselective Alkyne Addition to Aliphatic, Aromatic, and Vinyl Aldehydes Using Zn, (i)PrI, H8BINOL, and Ti(O(i)Pr)4.

    Science.gov (United States)

    Huang, Wen-Cai; Liu, Winnie; Wu, Xue-Dan; Ying, Jun; Pu, Lin

    2015-11-20

    A new catalytic system based on the readily available Zn, (i)PrI, H8BINOL, and Ti(O(i)Pr)4 has been developed which avoids the use of pyrophoric ZnEt2. It can effectively catalyze the reaction of various terminal alkynes with aromatic, aliphatic, and vinyl aldehydes to generate chiral propargylic alcohols at room temperature with up to 98% yield and 98% enantiomeric excess. This new system signifciantly expands the substrate scope of the previously reported system using Zn, EtI, BINOL, and Ti(O(i)Pr)4.

  1. THE EFFECT OF SULPHURIC ACID CONCENTRATION ON SOLVENT EXTRACTION OF ReO4 - BY THE LONG-CHAIN ALIPHATIC TERTIARY AMINES AND ALCOHOLS

    Directory of Open Access Journals (Sweden)

    Aleksander G. Kasikov

    2010-06-01

    Full Text Available The effect of sulphuric acid concentration on solvent extraction of ReO4- by the long-chain aliphatic tertiary amines and alcohols in a wide range of H2SO4 concentrations in initial solutions is discussed. It has been established that the influence of the sulphuric acid concentration on rhenium solvent extraction is largely due to the extraction process mechanism. In the case of the anion-exchange mechanism, ReO4- is best extracted from weakly acidic solutions, whereas when the hydrate-solvate mechanism takes place – from solutions containing 4-7 mole/l H2SO4.

  2. A base-mediated self-propagative Lossen rearrangement of hydroxamic acids for the efficient and facile synthesis of aromatic and aliphatic primary amines.

    Science.gov (United States)

    Ohtsuka, Naoya; Okuno, Moriaki; Hoshino, Yujiro; Honda, Kiyoshi

    2016-10-14

    A variety of aromatic and aliphatic hydroxamic acids were converted to the corresponding primary amines via base-mediated rearrangement. This rearrangement could proceed with less than 1 equiv. of K2CO3 in polar solvents under thermal conditions with no external reagents. This rearrangement has several features including no external activating agents needed for promoting the rearrangement, less than one equivalent of a base is sufficient for the reaction, and a clean reaction in which only carbon dioxide is produced as a by-product. A self-propagating mechanism via an isocyanate intermediate is proposed and elementary reaction steps, namely, chain propagation reactions are supported by experiments.

  3. One-step preparation and pH-tunable self-aggregation of amphoteric aliphatic polycarbonates bearing plenty of amine and carboxyl groups.

    Science.gov (United States)

    Wang, Hua-Fen; Jia, Hui-Zhen; Zhu, Jing-Yi; Chu, Yan-Feng; Feng, Jun; Zhang, Xian-Zheng; Zhuo, Ren-Xi

    2012-12-01

    This paper reports a novel amphoteric aliphatic polycarbonate bearing both amine and carboxyl groups. In the absence of protection-deprotection chemistry, the multi-functionalized copolymer is synthesized by one-step enzymatic copolymerization. The influences of the reaction conditions including monomer feed ratio and polymerization time are explored. The simultaneous incorporation of amine and carboxyl functionalities provides the copolymer with a pH-tunable self-aggregation feature, leading to various aggregation states including precipitated agglomerate, well-dispersed positively or negatively charged nanoparticles in a controlled manner. The copolymer displays minimal cytotoxicity to 293T and HeLa cells.

  4. Novel biodegradable aliphatic poly(butylene succinate-co-cyclic carbonate)s with functional carbonate building blocks. 1. Chemical synthesis and their structural and physical characterization.

    Science.gov (United States)

    Yang, Jing; Hao, Qinghui; Liu, Xiaoyun; Ba, Chaoyi; Cao, Amin

    2004-01-01

    This study presents chemical synthesis, structural, and physical characterization of novel biodegradable aliphatic poly(butylene succinate-co-cyclic carbonate)s P(BS-co-CC) bearing functional carbonate building blocks. First, five kinds of six-membered cyclic carbonate monomers, namely, trimethylene carbonate (TMC), 1-methyl-1,3-trimethylene carbonate (MTMC), 2,2-dimethyl-1,3-trimethylene carbonate (DMTMC), 5-benzyloxytrimethylene carbonate (BTMC), and 5-ethyl-5-benzyloxymethyl trimethylene carbonate (EBTMC), were well prepared from ethyl chloroformate and corresponding diols at 0 degrees C in THF solution with our modified synthetic strategies. Then, a series of new P(BS-co-CC)s were synthesized at 210 degrees C through a simple combination of poly-condensation and ring-opening-polymerization (ROP) of hydroxyl capped PBS macromers and the prepared carbonate monomers, and titanium tetra-isopropoxide Ti(i-OPr)4 was used as a more suitable catalyst of 5 candidate catalysts which could concurrently catalyze poly-condensation and ROP. By means of NMR, GPC, FTIR, and thermal analytical instruments, macromolecular structures and physical properties have been characterized for these aliphatic poly(ester carbonate)s. The experimental results indicated that novel biodegradable P(BS-co-CC)s were successfully synthesized with number average molecular weight Mn ranging from 24.3 to 99.6 KDa and various CC molar contents without any detectable decarboxylation and that the more bulky side group was attached to a cyclic carbonate monomer, the lower reactivity for its copolymerization would be observed. The occurrences of 13C NMR signal splitting of succinyl carbonyl attributed to the BS building blocks could be proposed due to the randomized sequences of BS and CC building blocks. FTIR characterization indicated two distinct absorption bands at 1716 and 1733 approximately 1735 cm(-1), respectively, stemming from carbonyl stretching modes for corresponding BS and CC units. With

  5. Scientific Opinion on Flavouring Group Evaluation 63, Revision 1 (FGE.63Rev1: Consideration of aliphatic secondary alcohols, ketones and related esters evaluated by JECFA (59th and 69th meetings structurally related to saturated and unsaturated aliphatic secondary alcohols, ketones and esters of secondary alcohols and saturated linear or branched-chain carboxylic acids evaluated by EFSA in FGE.07Rev4 (2012

    Directory of Open Access Journals (Sweden)

    EFSA Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids (CEF

    2012-10-01

    Full Text Available

    The Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids of the European Food Safety Authority was requested to consider evaluations of flavouring substances assessed since 2000 by the Joint FAO/WHO Expert Committee on Food Additives (the JECFA, and to decide whether further evaluation is necessary, as laid down in Commission Regulation (EC No 1565/2000. The present consideration concerns a group of 19 aliphatic secondary alcohols, ketones and related esters evaluated by the JECFA at the 59th and 69th meetings in 2002 and 2008. This revision is made due to inclusion of six additional substances, 4,8-dimethyl-3,7-nonadien-2-ol, 6-methylhepta-3,5-dien-2-one, octa-1,5-dien-3-one, (E,E-3,5-octadien-2-one, (3Z-4,8-dimethyl-3,7-nonadiene-2-one and 4,8-dimethyl-3,7-nonadien-2-yl acetate [FL-no: 02.252, 07.099, 07.190, 07.247, 07.256 and 09.936] cleared for genotoxicity concern. The substances were evaluated through a stepwise approach that integrates information on structure-activity relationships, intake from current uses, toxicological threshold of concern, and available data on metabolism and toxicity. The Panel agrees with the application of the Procedure as performed by the JECFA for all 19 substances considered in this FGE and agrees with the JECFA conclusion, “No safety concern at estimated levels of intake as flavouring substances” based on the MSDI approach.

  6. Progress of Aliphatic Polyester Grafted Polysaccharides in Biomimetic Materials%脂肪族聚酯接枝聚多糖仿生材料研究进展!

    Institute of Scientific and Technical Information of China (English)

    周开文; 宋继胜

    2012-01-01

    The tendency of biomedical materials is to design the novel biomaterials by biomimetic or bioinspired methods.Both aliphatic polyester and polysaccharides are biodegradable and biocompatible,and they extensively applied in engineering,gene delivery and drug delivery system.The paper reviewed the new research in aliphatic grafted polysaccharides and commented on the questions and the prospect of the biomimetic materials.%该文针对脂肪族聚酯与多糖都具有可生物降解、生物相容性等优点,以脂肪族聚酯接枝改性聚多糖并成为材料研究的热点,制备完全可生物降解的生物仿生材料,在药物控制释放、组织工程支架材料、基因转染载体材料等方面具有广泛应用。该文综述了脂肪族聚酯与多糖接枝改性的研究进展,同时讨论了各种接枝改性方法的特点并对于这类生物仿生材料目前存在的问题以及前景进行了展望。

  7. Effect of Hydroxyapatite Nanoparticles on the Degradability of Random Poly(butylene terephthalate-co-aliphatic dicarboxylates Having a High Content of Terephthalic Units

    Directory of Open Access Journals (Sweden)

    Nina Heidarzadeh

    2016-07-01

    Full Text Available Copolyesters derived from 1,4-butanediol and constituted also of aliphatic and aromatic dicarboxylate units in a molar ratio of 3:7 were synthesized by a two-step polycondensation procedure. Succinic, adipic, and sebacic acids were specifically selected as the aliphatic component whereas terephthalic acid was chosen as the aromatic moiety. The second synthesis step was a thermal transesterification between the corresponding homopolymers, always attaining a random distribution as verified by NMR spectroscopy. Hybrid polymer composites containing 2.5 wt % of hydroxyapatite (HAp were also prepared by in situ polymerization. Hydroxyl groups on the nanoparticle surface allowed the grafting of polymer chains in such a way that composites were mostly insoluble in the typical solvents of the parent copolyesters. HAp had some influence on crystallization from the melt, thermal stability, and mechanical properties. HAp also improved the biocompatibility of samples due to the presence of Ca2+ cations and the damping effect of phosphate groups. Interestingly, HAp resulted in a significant increase in the hydrophilicity of samples, which considerably affected both enzymatic and hydrolytic degradability. Slight differences were also found in the function of the dicarboxylic component, as the lowest degradation rates was found for the sample constituted of the most hydrophobic sebacic acid units.

  8. Potentiometric studies on ternary complexes involving some divalent transition metal ions, gallic acid and biologically abundant aliphatic dicarboxylic acids in aqueous solutions

    Directory of Open Access Journals (Sweden)

    Abdelatty Mohamed Radalla

    2015-06-01

    Full Text Available Formation of binary and ternary complexes of the divalent transition metal ions, Cu2+, Ni2+, Co2+ and Zn2+ with gallic acid and the biologically important aliphatic dicarboxylic acids (adipic, succinic, malic, malonic, maleic, tartaric and oxalic acids were investigated by means of the potentiometric technique at 25 °C and I = 0.10 mol dm−3 NaNO3. The acid-base properties of the ligands were investigated and discussed. The acidity constants of gallic acid and aliphatic dicarboxylic acids were determined and used for determining the stability constants of the binary and ternary complexes formed in the aqueous medium under the above experimental conditions. The formation of the different 1:1 and 1:2 binary complexes and 1:1:1 ternary complexes are inferred from the corresponding potentiometric pH-metric titration curves. The ternary complex formation was found to occur in a stepwise manner. The stability constants of these binary and ternary systems were calculated. The values of Δ log K, percentage of relative stabilization (%R.S. and log X were evaluated and discussed. The concentration distribution of the various complex species formed in solution was evaluated and discussed. The mode of chelation of ternary complexes formed was ascertained by conductivity measurements.

  9. Click synthesis of neutral, cationic, and zwitterionic poly(propargyl glycolide)-co-poly(ɛ-caprolactone)-based aliphatic polyesters as antifouling biomaterials.

    Science.gov (United States)

    Tu, Qin; Wang, Jian-Chun; Liu, Rui; Chen, Yun; Zhang, Yanrong; Wang, Dong-En; Yuan, Mao-Sen; Xu, Juan; Wang, Jinyi

    2013-08-01

    With the development of polymer-based biomaterials, aliphatic polyesters have attracted considerable interest because of their non-toxicity, non-allergenic property, and good biocompatibility. However, the hydrophobic nature and the lack of side chain functionalities of aliphatic polyesters limit their biomedical applications. In this study, we prepared four new polyesters: poly(sulfobetaine methacrylate)-, poly(2-methacryloyloxyethyl phosphotidylcholine)-, poly(ethylene glycol)-, and quaternized poly[(2-dimethylamino)ethyl methacrylate]-grafted poly(propargyl glycolide)-co-poly(ɛ-caprolactone). Their synthesis was conducted through ring-opening polymerization of acetylene-functionalized lactones and subsequent graft of bioactive units using click chemistry. The chemical structures of the polyesters were characterized through nuclear magnetic resonance and Fourier-transform infrared spectroscopy, and their physical properties (including molecular weight, glass transition temperature, and melting point) were determined using gel permeation chromatography and differential scanning calorimetry. For studies on their hydrophilicity, stability, and anti-bioadhesive property, a series of polymeric surfaces of these polyesters was prepared by coating them onto glass substrates. The hydrophilicity and stability of these polyester surfaces were examined by contact angle measurements and attenuated total reflection Fourier-transform infrared spectroscopy. Their anti-bioadhesive property was investigated through protein adsorption, as well as cellular and bacterial adhesion assays. The prepared polyesters showed good hydrophilicity and long-lasting stability, as well as significant anti-fouling property. The newly prepared polyesters could be developed as promising anti-fouling materials with extensive biomedical applications.

  10. Determination of some aliphatic carboxylic acids in anaerobic digestion process waters by ion-exclusion chromatography with conductimetric detection on a weakly acidic cation-exchange resin column.

    Science.gov (United States)

    Ito, Kazuaki; Takayama, Yohichi; Ikedo, Mikaru; Mori, Masanobu; Taoda, Hiroshi; Xu, Qun; Hu, Wenzhi; Sunahara, Hiroshi; Hayashi, Tsuneo; Sato, Shinji; Hirokawa, Takeshi; Tanaka, Kazuhiko

    2004-06-11

    The determination of seven aliphatic carboxylic acids, formic, acetic, propionic, isobutyric, n-butyric, isovaleric and n-valeric acids in anaerobic digestion process waters was examined using ion-exclusion chromatography with conductimetric detection. The analysis of these biologically important carboxylic acids is necessary as a measure for evaluating and controlling the process. The ion-exclusion chromatography system employed consisted of polymethacrylate-based weakly acidic cation-exchange resin columns (TSKgel OApak-A or TSKgel Super IC-A/C). weakly acidic eluent (benzoic acid), and conductimetric detection. Particle size and cation-exchange capacity were 5 microm and 0.1 meq./ml for TSKgel OApak-A and 3 microm and 0.2 meq./ml for TSKgel Super IC-A/C, respectively. A dilute eluent (1.0-2.0 mM) of benzoic acid was effective for the high resolution and highly conductimetric detection of the carboxylic acids. The good separation of isobutyric and n-butyric acids was performed using the TSKgel Super IC-A/C column (150 mm x 6.0 mm i.d. x 2). The simple and good chromatograms were obtained by the optimized ion-exclusion chromatography conditions for real samples from mesophilic anaerobic digestors, thus the aliphatic carboxylic acids were successfully determined without any interferences.

  11. The mixed aliphatic/aromatic composition of evaporating very small grains in NGC 7023 viewed by the 3.4/3.3 $\\mu$m ratio

    CERN Document Server

    Pilleri, P; Boulanger, F; Onaka, T

    2015-01-01

    In photon-dominated regions (PDRs), UV photons from nearby stars lead to the evaporation of very small grains (VSGs) and the production of gas-phase polycyclic aromatic hydrocarbons (PAHs). Our goal is to get further insights into the composition and evolution of evaporating very small grains (eVSGs) and PAHs through the analysis of the infrared (IR) aliphatic and aromatic emission bands. We combine spectro-imagery in the near- and mid-IR to study the spatial evolution of the emission bands in the prototypical PDR NGC 7023. We use near-IR spectra obtained with AKARI to trace the evolution of the 3.3$\\mu$m and 3.4$\\mu$m bands that are associated with aromatic and aliphatic C-H bonds on PAHs, respectively. The spectral fitting involves an additional broad feature centred at 3.45$\\mu$m. Mid-IR observations obtained with Spitzer are used to discriminate the signatures of eVSGs, neutral and cationic PAHs. We correlate the spatial evolution of all these bands with the intensity of the UV field to explore the proces...

  12. Identification and biotransformation of aliphatic hydrocarbons during co-composting of sewage sludge-Date Palm waste using Pyrolysis-GC/MS technique.

    Science.gov (United States)

    El Fels, Loubna; Lemee, Laurent; Ambles, André; Hafidi, Mohamed

    2016-08-01

    The behavior of aliphatic hydrocarbons during co-composting of sewage sludge activated with palm tree waste was studied for 6 months using Py-GC/MS. The main aliphatic compounds represented as doublet alkenes/alkanes can be classified into three groups. The first group consists of 11 alkenes (undecene, tridecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, uncosene, docosene, tricosene) and 15 alkanes (heptane, octane, nonane, decane, undecane, dodecane, tetradecane, pentadecane, heptadecane, octadecane, nonadecane, eicosane, uncosane, docosane, and tricosane), which remain stable during the co-composting process. The stability of these compounds is related to their recalcitrance behavior. The second group consists of five alkenes (heptene, octene, nonene, decene, dodecene) and tridecane as a single alkane that decreases during co-composting. The decrease in these compounds is the combined result of their metabolism and their conversion into other compounds. The third group is constituted with tetradecene and hexadecane that increase during composting, which could be explained by accumulation of these compounds, which are released by the partial breakdown of the substrate. As a result, these molecules are incorporated or adsorbed in the structure of humic substances.

  13. Distribution of aliphatic hydrocarbons, polycyclic aromatic hydrocarbons and organochlorinated pollutants in deep-sea sediments of the Southern Cretan margin, Eastern Mediterranean Sea: a baseline assessment.

    Science.gov (United States)

    Mandalakis, Manolis; Polymenakou, Paraskevi N; Tselepides, Anastasios; Lampadariou, Nikolaos

    2014-07-01

    Deep sediments from the southern Cretan margin were analyzed to establish baseline levels for various types of organic pollutants before the anticipated intensification of anthropogenic activities. The total concentration of aliphatic hydrocarbons (ΣAH:326-3758ngg(-1), dry weight) was similar to those reported for deep sediments of the western Mediterranean Sea, while considerably lower levels were measured for polycyclic aromatic hydrocarbons (ΣPAH:9-60ngg(-1)). Source-diagnostic ratios suggested that the aliphatic hydrocarbons in sediments were mainly of terrestrial biogenic origin, while polycyclic aromatic hydrocarbons stemmed from the deposition of long-range transported combustion aerosols. Among the organochlorinated compounds analyzed, β-hexachlorocyclohexane (β-HCH:222-7052pgg(-1)), 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane (p,p'-DDT:37-2236pgg(-1)) and polychlorinated biphenyls (ΣPCB:38-1182pgg(-1)) showed the highest abundance in sediments. The presence of HCHs and PCBs was attributed to historical inputs that have undergone extensive weathering, whereas an ongoing fresh input was suggested for p,p'-DDT. Multiple linear regression analysis revealed that the levels of the various pollutants in sediments were controlled by different factors, but with organic carbon content playing a prominent role in most cases.

  14. The difluoromethylene (CF2) group in aliphatic chains: Synthesis and conformational preference of palmitic acids and nonadecane containing CF2 groups.

    Science.gov (United States)

    Wang, Yi; Callejo, Ricardo; Slawin, Alexandra M Z; O'Hagan, David

    2014-01-06

    The syntheses of palmitic acids and a nonadecane are reported with CF2 groups located 1,3 or 1,4 to each other along the aliphatic chain. Specifically 8,8,10,10- and 8,8,11,11-tetrafluorohexadecanoic acids (6b and 6c) are prepared as well as the singly modified analogue 8,8-difluorohexadecanoic acid (6a). Also 8,8,11,11-tetrafluorononadecane (27) is prepared as a pure hydrocarbon containing a 1,4-di-CF2 motif. The modified palmitic acids are characterized by differential scanning calorimetry (DSC) to determine melting points and phase behaviour relative to palmitic acid (62.5 °C). It emerges that 6c, with the CF2 groups placed 1,4- to each other, has a significantly higher melting point (89.9 °C) when compared to the other analogues and palmitic acid itself. It is a crystalline compound and the structure reveals an extended anti-zig-zag chain. Similarly 8,8,11,11-tetrafluorononadecane (27) adopts an extended anti-zig-zag structure. This is rationalized by dipolar relaxation between the two CF2 groups placed 1,4 to each other in the extended anti-zig-zag chain and suggests a design modification for long chain aliphatics which can introduce conformational stability.

  15. Study on New Extraction Technique of Higher Aliphatic Alkanols from Beeswax%蜂蜡中提取高级脂肪醇的新工艺研究

    Institute of Scientific and Technical Information of China (English)

    蔡力创; 罗晓燕; 欧阳克氙; 肖正强; 刘建平

    2011-01-01

    The extraction conditions of higher aliphatie alkanols from beeswax by improved saponification hydrolysis were studied and discussed in this paper. By screening materials and opimizing the influencing factor of saponification hydrolysis, the optimal extraction conditions were researched and obtained. Chinese beeswax from Ganzhou was used as material, aviation kerosene was used as solvent and reaction time was 4.5 hour. As a result, the yield rate of higher aliphatic alkanols could be reached up from 33% to 35%. From the analytic identification and quantification of the higher aliphatic alkanols by C,C,the content of octacosanol and triacontanol was found to be up to 12% and 70% respectively.%研究探讨皂化水解法从蜂蜡中提取高级脂肪醇的工艺条件,通过筛选原料和优化皂化水解反应的影响因素,得出最佳工艺条件:选择赣州的中蜂蜡为原料,航空煤油为溶剂,反应时间为4.5 h,此时的高级脂肪醇的得率为33%~35%。通过GC对高级脂肪醇分析,二十八烷醇的含量达到12%,且三十烷醇含量达到70%。

  16. Unraveling the adsorption mechanism of aromatic and aliphatic diols on the TiO2 surface: a density functional theory analysis.

    Science.gov (United States)

    Giorgi, Giacomo; Fujisawa, Jun-ichi; Segawa, Hiroshi; Yamashita, Koichi

    2013-06-28

    Understanding the adsorption mechanism of organic molecules on inorganic semiconductors is of great importance for generating and control functions in organic-inorganic materials. Here we have comprehensively investigated, by means of the density functional theory, the adsorption structure and energetic stability of aliphatic and aromatic diols on TiO2 using ethylene glycol, 1,2-n-decanediol, and catechol. Our calculations clearly show that the non-dissociative bidentate adsorption is more stable than the dissociative one for the aliphatic diol, both at low and high coverage conditions, result far differently from many other chemical anchor cases for which the dissociative mechanism usually prevails. On the other hand, for catechol the dissociative bidentate is the most stable at low coverage conditions, whereas, surprisingly, increasing the coverage with catechol makes the non-dissociative mechanism the most stable one, revealing possible coexistence of a dissociative and non-dissociative anchoring at high coverage. This work unraveled a variety of adsorption fashions of the diol compounds in conjunction with the impact of the coverage effect, highly dependent on the nature of the lateral chain of the anchor group.

  17. Effect of saline on transitions in poly(ethylene glycol)-grafted succinyl-phosphoethanolamine monolayers bearing C16 aliphatic chains.

    Science.gov (United States)

    Shahid, Muhammad Naeem; Tsoukanova, Valeria

    2011-04-07

    To investigate the effect of saline on miscibility, phase, and conformational transitions in binary mixtures of a succinyl-phosphoethanolamine bearing C(16) aliphatic chains, DPPE-succinyl, and a poly(ethylene glycol) (PEG)-phospholipid conjugate with a PEG molecular weight of 2000, DPPE-PEG2000, we have compared the properties of monolayers spread on water and on phosphate buffered saline (PBS). A comparative analysis of monolayer surface pressure, surface potential, compressibility, and epifluorescence microscopy data has revealed that spreading on PBS induces unfavorable interactions between the two phospholipids, which stabilizes immiscible phases in mixed monolayers. Strikingly, the conformational transition in grafted PEG2000 chains on PBS could not be easily described by the existing interpretive schemes. Plausibly, this transition becomes partially impaired due to interactions with PBS. Thus, saline has a significant effect on miscibility, phase, and conformational transitions in these PEG-grafted monolayers bearing C(16) aliphatic chains, which may have implications for understanding the behavior of PEG-grafted phospholipid surfaces in aqueous media of biological relevance.

  18. Spatially Resolved 3 um Spectroscopy of IRAS 22272+5435 Formation and Evolution of Aliphatic Hydrocarbon Dust in Proto-Planetary Nebula

    CERN Document Server

    Goto, M; Hayano, Y; Iye, M; Kamata, Y; Kanzawa, T; Kobayashi, N; Minowa, Y; Saint-Jacques, D J; Takami, H; Takato, N; Terada, H

    2003-01-01

    We present medium-resolution 3 um spectroscopy of the carbon-rich proto-planetary nebula IRAS 22272+5435. Spectroscopy with the Subaru Telescope adaptive optics system revealed a spatial variation of hydrocarbon molecules and dust surrounding the star. The ro-vibrational bands of acetylene (C2H2) and hydrogen cyanide (HCN) at 3.0 um are evident in the central star spectra. The molecules are concentrated in the compact region near the center. The 3.3 and 3.4 um emission of aromatic and aliphatic hydrocarbons is detected at 600--1300 AU from the central star. The separation of spatial distribution between gas and dust suggests that the small hydrocarbon molecules are indeed the source of solid material, and that the gas leftover from the grain formation is being observed near the central star. The intensity of aliphatic hydrocarbon emission relative to the aromatic hydrocarbon emission decreases with distance from the central star. The spectral variation is well matched to that of a laboratory analog thermally ...

  19. Novel high glass temperature sugar-based epoxy resins: Characterization and comparison to mineral oil-based aliphatic and aromatic resins

    Directory of Open Access Journals (Sweden)

    P. Niedermann

    2015-02-01

    Full Text Available Curing and rheological behaviour, glass transition temperature, mechanical and thermal properties of two newly synthesized glucopyranoside- (GPTE and glucofuranoside- (GFTE based renewable epoxy resin (EP components were investigated and compared to aromatic and aliphatic EPs. The glucose-based EPs can be successfully cured with amine and anhydride type curing agents, their gel times are suitable for processing and can be well-adopted to the needs of the common composite preparation methods. GPTE showed the highest glass transition temperature (Tg among all investigated resins, followed by GFTE and DGEBA. Below the Tg there was no significant difference between the storage modulus values of the EP systems. The glucose-based EPs had lower tensile and bending strength, but their tensile modulus values are not significantly different from the mineral oil based EPs. The thermal stability of the synthesized GPTE and GFTE is between DGEBA and the aliphatic resins. In applications where bending stresses are dominant over the tensile ones, and outstanding Tg is required, these glucose-based resins offer a feasible renewable option.

  20. Aliphatic side chains of proteins as potential geomarkers of NOM liberated from the melting permafrost and discharged to the Arctic Ocean by the Kolyma River run off

    Science.gov (United States)

    Dubinenkov, I. V.; Perminova, I.; Kononikhin, A.; Nikolaev, E.; Hertkorn, N.; Bulygina, E. B.; Holmes, R. M.

    2011-12-01

    The Arctic ecosystem is highly sensitive to climate change. Global warming might have considerable effects on regional carbon cycling due to permafrost melting. Permafrost in the Arctic region represents an extremely large organic carbon reservoir mostly stored in the permafrost. Mobilization of just a small portion of carbon stored in Arctic soils will have considerable impacts on the flux of organic carbon from land to the Arctic Ocean, which can affect the Arctic environment. The Kolyma River watershed is one of the Arctic Ocean's largest. It is dominated by continuous permafrost which is underlain with rich organic soils susceptible to increased fluvial transport. The goal of the work was to analyze the structure of isolated natural organic matter from different fresh water environments of the Kolyma river basin. NOM was isolated from the Kolyma River main stream, its tributaries, a thermokarst lake, a floodplain stream and the permafrost. Solid phase extraction technique was used with Bond Elute PPL cartridges. Nuclear magnetic resonance spectroscopy (NMR) and Fourier Transform Ion Cyclotron Resonance Mass Spectroscopy (FTICRMS) was used for structural studies because of unsurpassed molecular level structural information provided by these high resolution magnetic resonance techniques. The NOM samples from the Kolyma River showed high contents of non-substituted aliphatic structures with a low content of aromatics and carbohydrates. Aliphatic nature may indicate a microbial source of NOM in the form of degraded terpenoids and hopanols. It was shown that almost all NOM samples from the rivers had similar molecular composition enriched with aliphatic units. The samples from permafrost mud streams were significantly different and contained sharp peptide signatures. In general, permafrost NOM contained much less degraded peptide residuest as compared to riverine samples. Identification of these residues showed the presence of branched amino acids (valine, alanine

  1. Sucrose monoester micelles size determined by Fluorescence Correlation Spectroscopy (FCS.

    Directory of Open Access Journals (Sweden)

    Susana A Sanchez

    Full Text Available One of the several uses of sucrose detergents, as well as other micelle forming detergents, is the solubilization of different membrane proteins. Accurate knowledge of the micelle properties, including size and shape, are needed to optimize the surfactant conditions for protein purification and membrane characterization. We synthesized sucrose esters having different numbers of methylene subunits on the substituent to correlate the number of methylene groups with the size of the corresponding micelles. We used Fluorescence Correlation Spectroscopy (FCS and two photon excitation to determine the translational D of the micelles and calculate their corresponding hydrodynamic radius, R(h. As a fluorescent probe we used LAURDAN (6-dodecanoyl-2-dimethylaminonaphthalene, a dye highly fluorescent when integrated in the micelle and non-fluorescent in aqueous media. We found a linear correlation between the size of the tail and the hydrodynamic radius of the micelle for the series of detergents measured.

  2. High-resolution gas chromatographic analysis of polycyclic aromatic hydrocarbons and aliphatic hydrocarbons; Separacion por cromatografia de gases de alta eficiencia de hidrocarburos aromaticos policiclicos, (PAH) y alifaticos (AH) ambientales, empleado como fases estacionarias OV-1 y SE-54

    Energy Technology Data Exchange (ETDEWEB)

    Perez, M.; Gonzalez, D.

    1988-07-01

    A study of the analysis by gas chromatography of aromatic polycyclic hydrocarbons and aliphatic hydrocarbons is presented. The separation has been carried out by glass and fused silica capillary column in two different polar stationary phases OV-1 and SE-54. The limitation and the advantages of the procedure are discussed in terms of separation, sensitivity and precision. (Author) 20 refs.

  3. Palladium-catalyzed Carbonylative Cyclization of 2-Bromocyclohex-1-enecarbalde-hydes with Aliphatic Primary Amines Leading to 3-Aminohydroisoindol-1-ones

    Energy Technology Data Exchange (ETDEWEB)

    Bae, Yeon Kyu; Cho, Chan Sik; Yoon, Nam Sik [Kyungpook National Univ., Daegu (Korea, Republic of)

    2013-09-15

    It has been shown that 2-bromocyclohex-1-enecarbaldehydes, which are readily prepared from α-methylene containing cyclohexanones under the bromination conditions of Vilsmeier-Haak reaction, undergo carbonylative cyclization with aliphatic primary amines in the presence of a palladium catalyst and a bidentate phosphorus ligand to give 3-aminohydroisoindol-1-ones. The present reaction provides a promising route for the synthesis of valuable heterocycles from readily available starting ketones. Further study of synthetic applications to heterocycles using these ketones is currently under investigation. Palladium-catalyzed carbonylation of organic halides (or triflates) followed by intramolecular cyclization (carbonyl-ative cyclization) has been widely explored and used as a promising synthetic tool for the construction of the structural core of many pharmacologically and biologically active lactones and lactams.

  4. Novel platinum(II) complexes of long chain aliphatic diamine ligands with oxalato as the leaving group: Comparative cytotoxic activity relative to chloride precursors

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Heveline; Barra, Carolina V.; Rocha, Fillipe V.; Fontes, Ana Paula S. [Universidade Federal de Juiz de Fora (UFJF), MG (Brazil). Dept. de Quimica; Lopes, Miriam T.P. [Universidade Federal deMinas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Farmacologia; Frezard, Frederic, E-mail: frezard@icb.ufmg.b [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil). Dept. de Fisiologia e Biofisica

    2010-07-01

    Platinum complexes play an important role in the development of anticancer drugs. Their cytotoxicity can be influenced by the nature of the leaving ligands, due to the hydrolysis reaction that occurs prior to the binding of the platinum complex to DNA. Also, non-leaving groups such as lipophilic diamines may affect cellular uptake. In this work, we describe the synthesis of platinum(II) complexes having oxalato and long chain aliphatic N-alkyl ethylenediamines as ligands. The products were characterized by elemental analyses, infrared spectroscopy and {sup 1}H, {sup 13}C and {sup 195}Pt NMR spectroscopy. Biological activity was assessed against tumor cell lines (A{sub 549}, B16-F1, B16-F10, MDA-MB-231) and non-tumor cell lines (BHK-21 and CHO). The length of the carbon chain affects the cytotoxicity and the oxalato complexes were less cytotoxic than the respective chloride-containing analogues. (author)

  5. Electronic Effects of Aluminum Complexes in the Copolymerization of Propylene Oxide with Tricyclic Anhydrides: Access to Well-Defined, Functionalizable Aliphatic Polyesters.

    Science.gov (United States)

    Van Zee, Nathan J; Sanford, Maria J; Coates, Geoffrey W

    2016-03-02

    The synthesis of well-defined and functionalizable aliphatic polyesters remains a key challenge in the advancement of emerging drug delivery and self-assembly technologies. Herein, we investigate the factors that influence the rates of undesirable transesterification and epimerization side reactions at high conversion in the copolymerization of tricyclic anhydrides with excess propylene oxide using aluminum salen catalysts. The structure of the tricyclic anhydride, the molar ratio of the aluminum catalyst to the nucleophilic cocatalyst, and the Lewis acidity of the aluminum catalyst all influence the rates of these side reactions. Optimal catalytic activity and selectivity against these side reactions requires a careful balance of all these factors. Effective suppression of undesirable transesterification and epimerization was achieved even with sterically unhindered monomers using a fluorinated aluminum salph complex with a substoichiometric amount of a nucleophilic cocatalyst. This process can be used to synthesize well-defined block copolymers via a sequential addition strategy.

  6. Peptidyl prolyl isomerase Pin1-inhibitory activity of D-glutamic and D-aspartic acid derivatives bearing a cyclic aliphatic amine moiety.

    Science.gov (United States)

    Nakagawa, Hidehiko; Seike, Suguru; Sugimoto, Masatoshi; Ieda, Naoya; Kawaguchi, Mitsuyasu; Suzuki, Takayoshi; Miyata, Naoki

    2015-12-01

    Pin1 is a peptidyl prolyl isomerase that specifically catalyzes cis-trans isomerization of phosphorylated Thr/Ser-Pro peptide bonds in substrate proteins and peptides. Pin1 is involved in many important cellular processes, including cancer progression, so it is a potential target of cancer therapy. We designed and synthesized a novel series of Pin1 inhibitors based on a glutamic acid or aspartic acid scaffold bearing an aromatic moiety to provide a hydrophobic surface and a cyclic aliphatic amine moiety with affinity for the proline-binding site of Pin1. Glutamic acid derivatives bearing cycloalkylamino and phenylthiazole groups showed potent Pin1-inhibitory activity comparable with that of known inhibitor VER-1. The results indicate that steric interaction of the cyclic alkyl amine moiety with binding site residues plays a key role in enhancing Pin1-inhibitory activity.

  7. Identifying the source of petroleum pollution in sediment cores of southwest of the Caspian Sea using chemical fingerprinting of aliphatic and alicyclic hydrocarbons.

    Science.gov (United States)

    Shirneshan, Golshan; Bakhtiari, Alireza Riyahi; Memariani, Mahmoud

    2017-02-15

    In this study, the concentration and sources of aliphatic and petroleum markers were investigated in 105 samples of Anzali, Rezvanshahr and Astara cores from the southwest of Caspian Sea. Petroleum importation was diagnosed as a main source in most depths of cores by the results of unresolved complex mixture, carbon preference index and hopanes and steranes. From the chemical diagnostic parameters, petroleum inputs in sediment of cores were determined to be different during years and the sources of hydrocarbons in some sections differed than Anzali and Turkmenistan and Azerbaijan oils. Diagenic ratios in most sediments of upper and middle sections in Astara core were determined to be highly similar to those of Azerbaijan oil, while the presence of Turkmenistan and Anzali oils were detected in a few sections of Anzali and Rezvanshahr cores and only five layers of downer section in Anzali core, respectively. Copyright © 2016. Published by Elsevier Ltd.

  8. Tuning reactivity and selectivity in hydrogen atom transfer from aliphatic C-H bonds to alkoxyl radicals: role of structural and medium effects.

    Science.gov (United States)

    Salamone, Michela; Bietti, Massimo

    2015-11-17

    Hydrogen atom transfer (HAT) is a fundamental reaction that takes part in a wide variety of chemical and biological processes, with relevant examples that include the action of antioxidants, damage to biomolecules and polymers, and enzymatic and biomimetic reactions. Moreover, great attention is currently devoted to the selective functionalization of unactivated aliphatic C-H bonds, where HAT based procedures have been shown to play an important role. In this Account, we describe the results of our recent studies on the role of structural and medium effects on HAT from aliphatic C-H bonds to the cumyloxyl radical (CumO(•)). Quantitative information on the reactivity and selectivity patterns observed in these reactions has been obtained by time-resolved kinetic studies, providing a deeper understanding of the factors that govern HAT from carbon and leading to the definition of useful guidelines for the activation or deactivation of aliphatic C-H bonds toward HAT. In keeping with the electrophilic character of alkoxyl radicals, polar effects can play an important role in the reactions of CumO(•). Electron-rich C-H bonds are activated whereas those that are α to electron withdrawing groups are deactivated toward HAT, with these effects being able to override the thermodynamic preference for HAT from the weakest C-H bond. Stereoelectronic effects can also influence the reactivity of the C-H bonds of ethers, amines, and amides. HAT is most rapid when these bonds can be eclipsed with a lone pair on an adjacent heteroatom or with the π-system of an amide functionality, thus allowing for optimal orbital overlap. In HAT from cyclohexane derivatives, tertiary axial C-H bond deactivation and tertiary equatorial C-H bond activation have been observed. These effects have been explained on the basis of an increase in torsional strain or a release in 1,3-diaxial strain in the HAT transition states, with kH(eq)/kH(ax) ratios that have been shown to exceed one order of

  9. Structural Peculiarities of Ion-Conductive Organic-Inorganic Polymer Composites Based on Aliphatic Epoxy Resin and Salt of Lithium Perchlorate

    Science.gov (United States)

    Matkovska, Liubov; Iurzhenko, Maksym; Mamunya, Yevgen; Tkachenko, Igor; Demchenko, Valeriy; Synyuk, Volodymyr; Shadrin, Andriy; Boiteux, Gisele

    2017-06-01

    The article is concerned with hybrid amorphous polymers synthesized basing on epoxy oligomer of diglycide aliphatic ester of polyethylene glycol that was cured by polyethylene polyamine and lithium perchlorate salt. Structural peculiarities of organic-inorganic polymer composites were studied by differential scanning calorimetry, wide-angle X-ray spectra, infrared spectroscopic, scanning electron microscopy, elemental analysis, and transmission and reflective optical microscopy. On the one hand, the results showed that the introduction of LiClO4 salt into epoxy polymer leads to formation of the coordinative metal-polymer complexes of donor-acceptor type between central Li+ ion and ligand. On the other hand, the appearance of amorphous microinclusions, probably of inorganic nature, was also found.

  10. EFSA Scientific Opinion on Flavouring Group Evaluation 78, Revision 1 (FGE.78Rev1): Consideration of aliphatic and alicyclic and aromatic hydrocarbons evaluated by JECFA (63rd meeting) structurally related to aliphatic and aromatic hydrocarbons evaluated by EFSA in FGE.25Rev2

    DEFF Research Database (Denmark)

    Larsen, John Christian; Nørby, Karin Kristiane; Beltoft, Vibe Meister

    The Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids of the European Food Safety Authority was requested to consider evaluations of flavouring substances assessed since 2000 by the Joint FAO/WHO Expert Committee on Food Additives (the JECFA), and to decide whether further...... evaluation is necessary, as laid down in Commission Regulation (EC) No 1565/2000. The present consideration concerns a group of 24 aliphatic, alicyclic and aromatic hydrocarbons evaluated by the JECFA (65th meeting). In the previous version of FGE.78, the Panel concluded that for 13 substances no applicable...

  11. Investigation on modes of toxic action to rats based on aliphatic and aromatic compounds and comparison with fish toxicity based on exposure routes.

    Science.gov (United States)

    He, Jia; Li, Jin J; Wen, Yang; Tai, Hong W; Yu, Yang; Qin, Wei C; Su, Li M; Zhao, Yuan H

    2015-06-01

    The modes of toxic action (MOAs) play an important role in the assessment of the ecotoxicity of organic pollutants. However, few studies have been reported on the MOAs in rat toxicity. In this paper, the toxic contributions of functional groups in 1255 aromatic compounds were calculated from regression and were then compared with the toxic contributions in aliphatic compounds. The results show that some functional groups have same toxic contributions both in aromatic and aliphatic compounds, but some have not. To investigate the MOAs in rat toxicity, the distribution of toxic ratio (TR) was examined for well-known baseline and less inert compounds and thresholds of log TR=0.3 and 0.5 were used to classify baseline, less inert and reactive compounds. The results showed that some compounds identified as baseline compounds in fish toxicity were also classified as baseline compounds in rat toxicity. Except for phenols and anilines which were identified as less inert compounds in fish toxicity, aromatic compounds with functional groups such as ether, nitrile, nitrophenol, isocyanatoe and chloro were identified as less inert chemicals in rat toxicity. Reactive compounds identified in fish toxicity exhibit greater toxicity to rats. These compounds can undergo nucleophilic substitution, acylation and Schiff base formation with biological macromolecules. The critical body residues (CBRs) calculated from absorption and bioconcentration show that log 1/CBRs in rat toxicity are not equal to that in fish for some compounds. It suggests that the exposure route can affect the identification of MOAs between these two species for these compounds.

  12. Separation of aliphatic carboxylic acids and benzenecarboxylic acids by ion-exclusion chromatography with various cation-exchange resin columns and sulfuric acid as eluent.

    Science.gov (United States)

    Ohta, Kazutoku; Ohashi, Masayoshi; Jin, Ji-Ye; Takeuchi, Toyohide; Fujimoto, Chuzo; Choi, Seong-Ho; Ryoo, Jae-Jeong; Lee, Kwang-Pill

    2003-05-16

    The application of various hydrophilic cation-exchange resins for high-performance liquid chromatography (sulfonated silica gel: TSKgel SP-2SW, carboxylated silica gel: TSKgel CM-2SW, sulfonated polymethacrylate resin: TSKgel SP-5PW, carboxylated polymethacrylate resins: TSKgel CM-5PW and TSKgel OA-Pak A) as stationary phases in ion-exclusion chromatography for C1-C7 aliphatic carboxylic acids (formic, acetic, propionic, butyric, isovaleric, valeric, isocaproic, caproic, 2-methylhexanoic and heptanoic acids) and benzenecarboxylic acids (pyromellitic, trimellitic, hemimellitic, o-phthalic, m-phthalic, p-phthalic, benzoic, salicylic acids and phenol) was carried out using diluted sulfuric acid as the eluent. Silica-based cation-exchange resins (TSKgel SP-2SW and TSKgel CM-2SW) were very suitable for the ion-exclusion chromatographic separation of these benzenecarboxylic acids. Excellent simultaneous separation of these benzenecarboxylic acids was achieved on a TSKgel SP-2SW column (150 x 6 mm I.D.) in 17 min using a 2.5 mM sulfuric acid at pH 2.4 as the eluent. Polymethacrylate-based cation-exchange resins (TSKgel SP-5PW, TSKgel CM-5PW and TSKgel OA-Pak A) acted as advanced stationary phases for the ion-exclusion chromatographic separation of these C1-C7 aliphatic carboxylic acids. Excellent simultaneous separation of these C1-C7 acids was achieved on a TSKgel CM-5PW column (150 x 6 mm I.D.) in 32 min using a 0.05 mM sulfuric acid at pH 4.0 as the eluent.

  13. Synthesis of α-MoO{sub 3} nanoplates using organic aliphatic acids and investigation of sunlight enhanced photodegradation of organic dyes

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, V. Vinod; Gayathri, K.; Anthony, Savarimuthu Philip, E-mail: philip@biotech.sastra.edu

    2016-04-15

    Graphical abstract: Thermodynamically stable α-MoO{sub 3} nanoplates and nanorods were synthesized using organic structure controlling agents and demonstrated sun light enhanced photocatalytic degradation of methylene blue (MB) and rhodamine blue (Rh-B) dyes in aqueous solution. - Highlights: • α-MoO{sub 3} hexagonal nanoplates using organic structure controlling agents. • Tunable optical band gap of MoO{sub 3}. • Demonstrated strong sun light mediated enhanced photodegradation of methylene blue and rhodamine blue. • Photodegradation did not use any other external oxidizing agents. - Abstract: Thermodynamically stable α-MoO{sub 3} nanoplates were synthesized using organic aliphatic acids as structure controlling agents and investigated photocatalytic degradation of methylene blue (MB) and rhodamine blue (Rh-B) in presence of sun light. Three different organic aliphatic acids, citric acid (CA), tartaric acid (TA) and ethylene diamine tetra-acetic acid (EDTA), were employed to control morphologies. CA and TA predominantly produced extended hexagonal plates where EDTA gave nanorods as well as nanoplates. PXRD studies confirmed the formation of α-MoO{sub 3} nanoparticles. HR-TEM and FE-SEM reveal the formation of plate morphologies with 20–40 nm thickness, 50–100 nm diameter and 600 nm lengths. The different morphologies of α-MoO{sub 3} nanoparticles lead to the tunable optical band gap between 2.80 and 2.98 eV which was obtained from diffused reflectance spectra (DRS). Interestingly, the synthesized α-MoO{sub 3} nanoplates exhibited strong photocatalytic degradation of MB and Rh-B up to 99% in presence of sun light without using any oxidizing agents.

  14. Aliphatic acetogenin constituents of avocado fruits inhibit human oral cancer cell proliferation by targeting the EGFR/RAS/RAF/MEK/ERK1/2 pathway

    Science.gov (United States)

    D’Ambrosio, Steven M.; Han, Chunhua; Pan, Li; Kinghorn, A. Douglas; Ding, Haiming

    2011-01-01

    Avocado (Persea americana) fruits are consumed as part of the human diet and extracts have shown growth inhibitory effects in various types of human cancer cells, although the effectiveness of individual components and their underlying mechanism are poorly understood. Using activity-guided fractionation of the flesh of avocado fruits, a chloroform-soluble extract (D003), was identified that exhibited high efficacy towards premalignant and malignant human oral cancer cell lines. From this extract, two aliphatic acetogenins of previously known structure were isolated, compounds 1 [(2S,4S)-2,4-dihydroxyheptadec-16-enyl acetate] and 2 [(2S,4S)-2,4-dihydroxyheptadec-16-ynyl acetate]. In this study, we show for the first time that the growth inhibitory efficacy of this chloroform extract is due to blocking the phosphorylation of EGFR (Tyr1173), c-RAF (Ser338), and ERK1/2 (Thr202/Tyr204) in the EGFR/RAS/RAF/MEK/ERK1/2 cancer pathway. Compound 1 and 2 both inhibited phosphorylation of c-RAF (Ser338) and ERK1/2 (Thr202/Tyr204). Compound 2, but not compound 1, prevented EGF-induced activation of EGFR (Tyr1173). When compounds 1 and 2 were combined they synergistically inhibited c-RAF (Ser338) and ERK1/2 (Thr202/Tyr204) phosphorylation, and human oral cancer cell proliferation. The present data suggest that the potential anticancer activity of avocado fruits is due to a combination of specific aliphatic acetogenins that target two key components of the EGFR/RAS/RAF/MEK/ERK1/2 cancer pathway. PMID:21596018

  15. New Synthetic Approaches to Multifunctional Phenazinium Salt Derivatives

    Directory of Open Access Journals (Sweden)

    Vladimir N. Silnikov

    2003-06-01

    Full Text Available Two different approaches are offered for the synthesis under mild conditions of disubstituted phenazinium and benzo[a]phenazinium salts. Direct nucleophilic substitutions by primary and secondary amines in quaternary phenazinium salts containing an additional positive charge in the aliphatic part of the molecule were carried out. The substitution proceeds successively in positions 2 and 7, which allows selective introduction of different substituents into the heterocycle. Direct nucleophilic substitution in quaternary 2-N-alkyl-acetamidophenazinium and 5-alkoxy-benzo[a]phenazinium salts with different amines can also serve as a convenient method for the introduction of two different substituents.

  16. EFSA CEF Panel (EFSA Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids), 2013. Scientific Opinion on Flavouring Group Evaluation 72, Revision 1 (FGE.72Rev1): Consideration of aliphatic, branched-chain saturated and unsaturated alcohols, aldehydes, acids, and related esters, evaluated by the JECFA (61st meeting) structurally related to branched- and straight-chain unsaturated carboxylic acids, esters of these and straight-chain aliphatic saturated alcohols evaluated by EFSA in FGE.05Rev2

    DEFF Research Database (Denmark)

    Beltoft, Vibe Meister; Binderup, Mona-Lise; Frandsen, Henrik Lauritz;

    evaluation is necessary, as laid down in Commission Regulation (EC) No 1565/2000. The present consideration concerns a group of 23 aliphatic branched-chain saturated and unsaturated alcohols, aldehydes, acids and related esters, evaluated by the JECFA at their 61st meeting. This revision is made due...

  17. Review and Analysis of Synthetic Method of Sulfonated Aliphatic Series Water-reducer%脂肪族磺酸盐减水剂合成方法综述和分析

    Institute of Scientific and Technical Information of China (English)

    王宇飞; 严捍东; 全志龙

    2012-01-01

    分析了脂肪族磺酸盐减水剂的合成机理,概述了脂肪族磺酸盐减水剂的合成方法及其性能.提出今后应充分重视引入酸性基团化合物对脂肪族缩合物进行接枝改良处理的研究,加大对微波和无热源法合成脂肪族减水剂工艺和性能的研究,并尝试研究用苯乙酮作为原料生产脂肪族减水剂.并就SAF型脂肪族减水剂的加料顺序、磺化剂种类、溶液pH值对减水剂减水率的影响进行了对比试验.%Synthetic mechanism of sulfonated aliphatic series water reducer is analyzed, and the synthetic method and performance is summarized. It is suggested that we should pay attention to the research of introducing acid groups compound to graft and improving aliphatic series condensation compound in future, microwave method and py-rogen free method to compound aliphatic series should be increased, and try to use acetophenone as the material to produce the aliphatic series water-reducer. Effect of water reducing ratio of SAF sulfonated aliphatic series water reducer by arranging the sequence of adding material, the type of sulfonating agent and the pH value of solution were contrasted.

  18. Biochemistry of Suberization: Incorporation of [1-C]Oleic Acid and [1-C]Acetate into the Aliphatic Components of Suberin in Potato Tuber Disks (Solanum tuberosum).

    Science.gov (United States)

    Dean, B B; Kolattukudy, P E

    1977-01-01

    Biosynthesis of the aliphatic components of suberin was studied in suberizing potato (Solanum tuberosum) slices with [1-(14)C]oleic acid and [1-(14)C]acetate as precursors. In 4-day aged tissue, [1-(14)C]oleic acid was incorporated into an insoluble residue, which, upon hydrogenolysis (LiA1H(4)), released the label into chloroform-soluble products. Radio thin layer and gas chromatographic analyses of these products showed that (14)C was contained exclusively in octadecenol and octadecene-1, 18-diol. OsO(4) treatment and periodate cleavage of the resulting tetraol showed that the labeled diol was octadec-9-ene-1, 18-diol, the product expected from the two major components of suberin, namely 18-hydroxyoleic acid and the corresponding dicarboxylic acid. Aged potato slices also incorporated [1-(14)C]acetate into an insoluble material. Hydrogenolysis followed by radio chromatographic analyses of the products showed that (14)C was contained in alkanols and alkane-alpha,omega-diols. In the former fraction, a substantial proportion of the label was contained in aliphatic chains longer than C(20), which are known to be common constituents of suberin. In the labeled diol fraction, the major component was octadec-9-ene-1,18-diol, with smaller quantities of saturated C(16), C(18), C(20), C(22), and C(24)-alpha,omega-diols. Soluble lipids derived from [1-(14)C]acetate in the aged tissue also contained labeled very long acids from C(20) to C(28), as well as C(22) and C(24) alcohols, but no labeled omega-hydroxy acids or dicarboxylic acids were detected. Label was also found in n-alkanes isolated from the soluble lipids, and the distribution of label among them was consistent with the composition of n-alkanes found in the wound periderm of this tissue; C(21) and C(23) were the major components with lesser amounts of C(19) and C(25). The amount of (14)C incorporated into these bifunctional monomers in 0-, 2-, 4-, 6-, and 8-day aged tissue were 0, 1.5, 2.5, 0.8, and 0.3% of the

  19. Zinc oxide/polypyrrole nanocomposite as a novel solid phase microextraction coating for extraction of aliphatic hydrocarbons from water and soil samples

    Energy Technology Data Exchange (ETDEWEB)

    Amanzadeh, Hatam; Yamini, Yadollah [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175 Tehran (Iran, Islamic Republic of); Moradi, Morteza [Department of Semiconductors, Materials and Energy Research Center, Karaj (Iran, Islamic Republic of)

    2015-07-16

    Highlights: • ZnO/polypyrrole (ZNO/PPY) nanocomposite coating was fabricated on stainless steel. • Nanocomposite coating morphology was evaluated using scanning electron microscopy. • It was applied for HS-SPME of aliphatic hydrocarbons in water and soil samples. • Separation and determination of the hydrocarbons were performed by GC-FID. • The method is suitable for routine analysis of n-alkanes in various environmental samples. - Abstract: In this work, ZnO/PPy nanocomposite coating was fabricated on stainless steel and evaluated as a novel headspace solid phase microextraction (HS-SPME) fiber coating for extraction of ultra-trace amounts of environmental pollutants; namely, aliphatic hydrocarbons in water and soil samples. The ZnO/PPy nanocomposite were prepared by a two-step process including the electrochemical deposition of PPy on the surface of stainless steel in the first step, and the synthesis of ZnO nanorods by hydrothermal process in the pores of PPy matrix in the second step. Porous structure together with ZnO nanorods with the average diameter of 70 nm were observed on the surface by using scanning electron microscopy (SEM). The effective parameters on HS-SPME of hydrocarbons (i.e., extraction temperature, extraction time, desorption temperature, desorption time, salt concentration, and stirring rate) were investigated and optimized by one-variable-at-a-time method. Under optimized conditions (extraction temperature, 65 ± 1 °C; extraction time, 15 min; desorption temperature, 250 °C; desorption time, 3 min; salt concentration, 10% w/v; and stirring rate, 1200 rpm), the limits of detection (LODs) were found in the range of 0.08–0.5 μg L{sup −1}, whereas the repeatability and fiber-to-fiber reproducibility were in the range 5.4–7.6% and 8.6–10.4%, respectively. Also, the accuracies obtained for the spiked n-alkanes were in the range of 85–108%; indicating the absence of matrix effects in the proposed HS-SPME method. The results

  20. Quantum chemical analysis of thermodynamics of 2D cluster formation of alkanes at the water/vapor interface in the presence of aliphatic alcohols.

    Science.gov (United States)

    Vysotsky, Yu B; Kartashynska, E S; Belyaeva, E A; Fainerman, V B; Vollhardt, D; Miller, R

    2015-11-21

    Using the quantum chemical semi-empirical PM3 method it is shown that aliphatic alcohols favor the spontaneous clusterization of vaporous alkanes at the water surface due to the change of adsorption from the barrier to non-barrier mechanism. A theoretical model of the non-barrier mechanism for monolayer formation is developed. In the framework of this model alcohols (or any other surfactants) act as 'floats', which interact with alkane molecules of the vapor phase using their hydrophobic part, whereas the hydrophilic part is immersed into the water phase. This results in a significant increase of contact effectiveness of alkanes with the interface during the adsorption and film formation. The obtained results are in good agreement with the existing experimental data. To test the model the thermodynamic and structural parameters of formation and clusterization are calculated for vaporous alkanes C(n)H(2n+2) (n(CH3) = 6-16) at the water surface in the presence of aliphatic alcohols C(n)H(2n+1)OH (n(OH) = 8-16) at 298 K. It is shown that the values of clusterization enthalpy, entropy and Gibbs' energy per one monomer of the cluster depend on the chain lengths of corresponding alcohols and alkanes, the alcohol molar fraction in the monolayers formed, and the shift of the alkane molecules with respect to the alcohol molecules Δn. Two possible competitive structures of mixed 2D film alkane-alcohol are considered: 2D films 1 with single alcohol molecules enclosed by alkane molecules (the alcohols do not form domains) and 2D films 2 that contain alcohol domains enclosed by alkane molecules. The formation of the alkane films of the first type is nearly independent of the surfactant type present at the interface, but depends on their molar fraction in the monolayer formed and the chain length of the compounds participating in the clusterization, whereas for the formation of the films of the second type the interaction between the hydrophilic parts of the surfactant is