Sample records for acetals carboxylic acids

  1. Catalysis of the Carbonylation of Alcohols to Carboxylic Acids Including Acetic Acid Synthesis from Methanol.

    ERIC Educational Resources Information Center

    Forster, Denis; DeKleva, Thomas W.

    1986-01-01

    Monsanto's highly successful synthesis of acetic acid from methanol and carbon monoxide illustrates use of new starting materials to replace pretroleum-derived ethylene. Outlines the fundamental aspects of the acetic acid process and suggests ways of extending the synthesis to higher carboxylic acids. (JN)

  2. Formation of biologically relevant carboxylic acids during the gamma irradiation of acetic acid

    NASA Technical Reports Server (NTRS)

    Negron-Mendoza, A.; Ponnamperuma, C.

    1976-01-01

    Irradiation of aqueous solutions of acetic acid with gamma rays produced several carboxylic acids in small yield. Their identification was based on the technique of gas chromatography combined with mass spectrometry. Some of these acids are Krebs Cycle intermediates. Their simultaneous formation in experiments simulating the primitive conditions on the earth suggests that metabolic pathways may have had their origin in prebiotic chemical processes.

  3. Year-round records of gas and particulate carboxylic acids (formate and acetate) in the boundary layer at Dumont d'Urville (coastal Antarctica): Production of carboxylic acids from biogenic NMHC emissions from the Antarctic ocean

    NASA Astrophysics Data System (ADS)

    Legrand, M.; Preunkert, S.; Jourdain, B.

    2003-04-01

    Multiple year-round concentrations of acetic and formic acids were measured both in gas and aerosol phases at Dumont d'Urville (DDU, a coastal Antarctic site: 66^o40'S, 140^o01'E) by using mist chamber and aerosol filter sampling. Aerosol levels of the 2 carboxylates range from less than one ng m-3 in winter to 5--10 ng m-3 in summer. Comparison with gas phase concentrations shows that almost 99% of the 2 carboxylic acids are present in the gas phase. Concentrations of formic acid in the gas phase are minima in June--July (70 ng m-3) and increase regularly towards summer months when levels reach ˜400 ng m-3. Concentrations of acetic acid in the gas phase exhibit a more well-marked seasonal cycle with values remaining close to 50 ng m-3 from April to October and strongly increase during summer months (mean value of 800 ng m-3). Such a strong seasonal cycle of carboxylic acids in the high southern latitude marine boundary layer displays with observations made at numerous continental sites where a more weak seasonality is generally observed. It is suggested that carboxylic acids present at DDU mainly originate from biogenic emissions from the Antarctic ocean which are expected to closely follow annual cycle of the sea ice extent and solar radiation, affecting in particular photochemical production of alkenes from dissolved organic carbon released from phytoplancton. Summer levels of carboxylic acids are discussed in terms of air-sea fluxes of NMHCs and photochemical production of carboxylic acids from ozone-alkene reactions and HO_2 reaction with peroxyacetal radical in these poor NOx environments.

  4. Emission characteristics of carboxylates in PM2.5 from incense burning with the effect of light on acetate

    NASA Astrophysics Data System (ADS)

    Kuo, Su-Ching; Tsai, Ying I.; Sopajaree, Khajornsak

    2016-08-01

    Incense burning produces potentially harmful particulate matter. In this study we investigated the emissions of PM2.5 and gaseous acetic acid from four brands of traditional incense; Liao and Shang Lao Shan (SLS), sold in Taiwan, and Thai Yellow (Thai Y) and Thai Black (Thai B), sold in Thailand. Additionally, photochemical reactions of PM2.5 carboxylates emitted from incense burning were studied via a simulated light experiment. The average PM2.5 mass emission factor of each incense type was inversely correlated with the ash production of that incense. The Thailand incense carboxylate emissions were markedly higher than the Taiwan incense. Acetate accounted for 87.46% of total carboxylate emissions, with acetate emitted from the Thailand incense 1.26 times higher than from the Taiwan incense. Phthalate was detected in the PM2.5, indicating the presence of plasticizer. Concentrations of PM2.5 acetate, formate, pyruvate, glutarate, succinate, fumarate and tartarate were reduced in simulated light (51.5%-97.1% of those under dark), indicating that these seven types of carboxylate are easily photodegradable. In contrast, malonate, maleate, oxalate and phthalate concentrations in light were 1.17-1.84 times higher than in darkness, indicating photochemical reactions contribute to the formation of these species. The formation of the low-molecular weight dicarboxylates oxalate and malonate was most noticeable. Acetic acid, highly irritating to the respiratory system and skin, was present at high levels for all four incense types, as shown by the gaseous acetic acid/PM2.5 acetate ratios of 1.03-3.61. Burning incense indoors can generate high concentrations of PM2.5 acetate that increases the risks of respiratory and contact irritation, particularly when burning the Thailand incense. Moreover, burning incense in poorly ventilated, dimly lit indoor areas (e.g., temples and homes) can markedly increase the risk of irritation because the gaseous acetic acid is not degraded as

  5. Carboxylic Acids Plasma Membrane Transporters in Saccharomyces cerevisiae.

    PubMed

    Casal, Margarida; Queirós, Odília; Talaia, Gabriel; Ribas, David; Paiva, Sandra

    2016-01-01

    This chapter covers the functionally characterized plasma membrane carboxylic acids transporters Jen1, Ady2, Fps1 and Pdr12 in the yeast Saccharomyces cerevisiae, addressing also their homologues in other microorganisms, as filamentous fungi and bacteria. Carboxylic acids can either be transported into the cells, to be used as nutrients, or extruded in response to acid stress conditions. The secondary active transporters Jen1 and Ady2 can mediate the uptake of the anionic form of these substrates by a H(+)-symport mechanism. The undissociated form of carboxylic acids is lipid-soluble, crossing the plasma membrane by simple diffusion. Furthermore, acetic acid can also be transported by facilitated diffusion via Fps1 channel. At the cytoplasmic physiological pH, the anionic form of the acid prevails and it can be exported by the Pdr12 pump. This review will highlight the mechanisms involving carboxylic acids transporters, and the way they operate according to the yeast cell response to environmental changes, as carbon source availability, extracellular pH and acid stress conditions.

  6. Ethylene-enhanced catabolism of ( sup 14 C)indole-3-acetic acid to indole-3-carboxylic acid in citrus leaf tissues. [Citrus sinensis

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

    Sagee, O.; Riov, J.; Goren, J.

    Exogenous ({sup 14}C)indole-3-acetic acid (IAA) is conjugated in citrus (Citrus sinensis) leaf tissues to one major substance which has been identified as indole-3-acetylaspartic acid (IAAsp). Ethylene pretreatment enhanced the catabolism of ({sup 14}C)IAA to indole-3-carboxylic acid (ICA), which accumulated as glucose esters (ICGlu). Increased formation of ICGlu by ethylene was accompanied by a concomitant decrease in IAAsp formation. IAAsp and ICGlu were identified by combined gas chromatography-mass spectrometry. Formation of ICGlu was dependent on the concentration of ethylene and the duration of the ethylene pretreatment. It is suggested that the catabolism of IAA to ICA may be one of themore » mechanisms by which ethylene endogenous IAA levels.« less

  7. Atmospheric chemistry of carboxylic acids: microbial implication versus photochemistry

    NASA Astrophysics Data System (ADS)

    Vaïtilingom, M.; Charbouillot, T.; Deguillaume, L.; Maisonobe, R.; Parazols, M.; Amato, P.; Sancelme, M.; Delort, A.-M.

    2011-02-01

    Clouds are multiphasic atmospheric systems in which the dissolved organic compounds, dominated by carboxylic acids, are subject to multiple chemical transformations in the aqueous phase. Among them, solar radiation, by generating hydroxyl radicals (•OH), is considered as the main catalyzer of the reactivity of organic species in clouds. We investigated to which extent the active biomass existing in cloud water represents an alternative route to the chemical reactivity of carboxylic acids. Pure cultures of seventeen bacterial strains (Arthrobacter, Bacillus, Clavibacter, Frigoribacterium, Pseudomonas, Sphingomonas and Rhodococcus), previously isolated from cloud water and representative of the viable community of clouds were first individually incubated in two artificial bulk cloud water solutions at 17 °C and 5 °C. These solutions mimicked the chemical composition of cloud water from "marine" and "continental" air masses, and contained the major carboxylic acids existing in the cloud water (i.e. acetate, formate, succinate and oxalate). The concentrations of these carboxylic compounds were monitored over time and biodegradation rates were determined. In average, they ranged from 2 ×10-19 for succinate to 1 × 10-18 mol cell-1 s-1 for formate at 17 °C and from 4 × 10-20 for succinate to 6 × 10-19 mol cell-1 s-1 for formate at 5 °C, with no significant difference between "marine" and "continental" media. In parallel, irradiation experiments were also conducted in these two artificial media to compare biodegradation and photodegradation of carboxylic compounds. To complete this comparison, the photodegradation rates of carboxylic acids by •OH radicals were calculated from literature data. Inferred estimations suggested a significant participation of microbes to the transformation of carboxylic acids in cloud water, particularly for acetate and succinate (up to 90%). Furthermore, a natural cloud water sample was incubated (including its indigenous microflora

  8. Prevention of acetic acid-induced colitis by desferrithiocin analogs in a rat model.

    PubMed

    Bergeron, Raymond J; Wiegand, Jan; Weimar, William R; Nguyen, John Nhut; Sninsky, Charles A

    2003-02-01

    Iron contributes significantly to the formation of reactive oxygen species via the Fenton reaction. Therefore, we assessed whether a series of desferrithiocin analogs, both carboxylic acids and hydroxamates, could (1) either promote or diminish the iron-mediated oxidation of ascorbate, (2) quench a model radical species, 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS+), and (3) when applied topically, prevent acetic acid-induced colitis in rats. Surprisingly, most of the desferrithiocin analogs inhibited the Fenton reaction to an approximately equivalent degree; however, substantial differences were observed in the capacity of the analogs to scavenge the model radical cation. Four carboxylic acid desferrithiocin analogs and their respective N-methylhydroxamates were tested along with desferrioxamine and Rowasa, a currently accepted topical therapeutic agent for inflammatory bowel disease (IBD), in a rodent model of acetic acid-induced colitis. The colonic damage was quantitated by two independent measurements. Although neither radical scavenging nor prevention of Fenton chemistry was a definitive predictor of in vivo efficacy, the overall trend is that desferrithiocin analogs substituted with an N-methylhydroxamate in the place of the carboxylic acid are both better free radical scavengers and more active against acetic acid-induced colitis. These results represent an intriguing alternative avenue to the development of improved IBD therapeutic agents.

  9. Odor detection of mixtures of homologous carboxylic acids and coffee aroma compounds by humans.

    PubMed

    Miyazawa, Toshio; Gallagher, Michele; Preti, George; Wise, Paul M

    2009-11-11

    Mixture summation among homologous carboxylic acids, that is, the relationship between detection probabilities for mixtures and detection probabilities for their unmixed components, varies with similarity in carbon-chain length. The current study examined detection of acetic, butyric, hexanoic, and octanoic acids mixed with three other model odorants that differ greatly from the acids in both structure and odor character, namely, 2-hydroxy-3-methylcyclopent-2-en-1-one, furan-2-ylmethanethiol, and (3-methyl-3-sulfanylbutyl) acetate. Psychometric functions were measured for both single compounds and binary mixtures (2 of 5, forced-choice method). An air dilution olfactometer delivered stimuli, with vapor-phase calibration using gas chromatography-mass spectrometry. Across the three odorants that differed from the acids, acetic and butyric acid showed approximately additive (or perhaps even supra-additive) summation at low perithreshold concentrations, but subadditive interactions at high perithreshold concentrations. In contrast, the medium-chain acids showed subadditive interactions across a wide range of concentrations. Thus, carbon-chain length appears to influence not only summation with other carboxylic acids but also summation with at least some unrelated compounds.

  10. Beyond ketonization: selective conversion of carboxylic acids to olefins over balanced Lewis acid–base pairs

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

    Baylon, Rebecca A. L.; Sun, Junming; Martin, Kevin J.

    Dwindling petroleum reserves combined with increased energy demand and political factors encouraging an increase in energy independence have led to a large amount of research on sustainable alternatives. To this end, biomass conversion has been recognized as themost readily viable technology to produce biofuel concerning our reliance on liquid fuels for transportation and has the advantage of being easily integrated into our heavy use of combustion engines. The interest in biomass conversion has also resulted in reduced costs and a greater abundance of bio-oil, a mixture of hundreds of oxygenates including alcohols, aldehydes, carboxylic acids, and ketones. However, the presencemore » of carboxylic acids in bio-oil derived from lignocellulose pyrolysis leads to low pH, instability, and corrosiveness. In addition, carboxylic acids (i.e. acetic acid) can also be produced via fermentation of sugars. This can be accomplished by a variety of homoacetogenic microorganisms that can produce acetic acid with 100% carbon yield.« less

  11. Formation and High-order Carboxylic Acids (RCOOH) in Interstellar Analogous Ices of Carbon Dioxide (CO2) and Methane(CH4)

    NASA Astrophysics Data System (ADS)

    Zhu, Cheng; Turner, Andrew M.; Abplanalp, Matthew J.; Kaiser, Ralf I.

    2018-01-01

    This laboratory study simulated the abiotic formation of carboxylic acids (RCOOH) in interstellar analogous ices of carbon dioxide (CO2) and methane (CH4) at 10 K upon exposure to energetic electrons. The chemical processing of the ices and the subsequent warm-up phase were monitored online and in situ, exploiting Fourier Transform Infrared Spectrometry and quadrupole mass spectrometry. Characteristic absorptions of functional groups of carboxylic acids (RCOOH) were observed in the infrared spectra of the irradiated ice. Two proposed reaction mechanisms replicated the kinetic profiles of the carboxylic acids along with the decay profile of the precursors during the irradiation via hydrocarbon formation, followed by carboxylation and/or through acetic acid along with mass growth processes of the alkyl chain. Mass spectra recorded during the warm-up phase demonstrated that these acids are distributed from acetic acid (CH3COOH) up to decanoic acid (C9H19COOH). High-dose irradiation studies (91 ± 14 eV) converted low-molecular-weight acids such as acetic acid (CH3COOH) and propionic acid (C2H5COOH) to higher-molecular-weight carboxylic acids, compared to low-dose irradiation studies (18 ± 3 eV). The traces of the {{{H}}}2{{C}}= {{C}}({OH}{)}2+ (m/z = 60) fragment—a link to linear carboxylic acids—implied that higher-order acids (C n H2n+1COOH, n ≥ 5) are likely branched, which correlates with the recent analysis of the structures of the monocarboxylic acids in the Murchison meteorite.

  12. Anaerobic Fermentation for Production of Carboxylic Acids as Bulk Chemicals from Renewable Biomass.

    PubMed

    Wang, Jufang; Lin, Meng; Xu, Mengmeng; Yang, Shang-Tian

    Biomass represents an abundant carbon-neutral renewable resource which can be converted to bulk chemicals to replace petrochemicals. Carboxylic acids have wide applications in the chemical, food, and pharmaceutical industries. This chapter provides an overview of recent advances and challenges in the industrial production of various types of carboxylic acids, including short-chain fatty acids (acetic, propionic, butyric), hydroxy acids (lactic, 3-hydroxypropionic), dicarboxylic acids (succinic, malic, fumaric, itaconic, adipic, muconic, glucaric), and others (acrylic, citric, gluconic, pyruvic) by anaerobic fermentation. For economic production of these carboxylic acids as bulk chemicals, the fermentation process must have a sufficiently high product titer, productivity and yield, and low impurity acid byproducts to compete with their petrochemical counterparts. System metabolic engineering offers the tools needed to develop novel strains that can meet these process requirements for converting biomass feedstock to the desirable product.

  13. Organotin(IV) carboxylates based on 2-(1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)acetic acid: Syntheses, crystal structures, luminescent properties and antitumor activities

    NASA Astrophysics Data System (ADS)

    Xiao, Xiao; Liang, Jingwen; Xie, Jingyi; Liu, Xin; Zhu, Dongsheng; Dong, Yuan

    2017-10-01

    Organotin carboxylates based on an amide carboxylic acid 2-(1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)acetic acid (HL): [(Bn2Sn)2O2L]2·2C6H6 (1) (Bn = benzyl group) and (Ph2Sn)(L)2 (2) were synthesized and characterized by elemental analysis, IR, 1H, 13C, 119Sn NMR spectroscopy and X-ray crystallography diffraction analysis. Complex 1 is dimeric carboxylate tetraorganodistannoxane and show a "ladder-like" molecular structure. Complex 2 is a dialkyltin carboxylate monomer possessing crystallographically imposed two-fold symmetry. Ligand in 1 and 2 adopts unidentate and bidentate coordination respectively. Both 1 and 2 form 1D, 2D and 3D supramolecular organizations in the solid state mediated through Csbnd H⋯O and π⋯π interactions which are discussed in detail. The luminescent properties and preliminary antitumor activities about this series of complexes were also studied.

  14. Speciation of aqueous Ni(II)-carboxylate and Ni(II)-fulvic acid solutions: Combined ATR-FTIR and XAFS analysis

    NASA Astrophysics Data System (ADS)

    Strathmann, Timothy J.; Myneni, Satish C. B.

    2004-09-01

    Aqueous solutions containing Ni(II) and a series of structurally related carboxylic acids were analyzed using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and Ni K-edge X-ray absorption fine structure spectroscopy (XAFS). XAFS spectra were also collected for solutions containing Ni 2+ and chelating ligands (ethylenediaminetetraacetic acid, nitrilotriacetic acid (NTA)) as well as soil fulvic acid. Limited spectral changes are observed for aqueous Ni(II) complexes with monocarboxylates (formate, acetate) and long-chain polycarboxylates (succinate, tricarballylate), where individual donor groups are separated by multiple bridging methylene groups. These spectral changes indicate weak interactions between Ni(II) and carboxylates, and the trends are similar to some earlier reports for crystalline Ni(II)-acetate solids, for which X-ray crystallography studies have indicated monodentate Ni(II)-carboxylate coordination. Nonetheless, electrostatic or outer-sphere coordination cannot be ruled out for these complexes. However, spectral changes observed for short-chain dicarboxylates (oxalate, malonate) and carboxylates that contain an alcohol donor group adjacent to one of the carboxylate groups (lactate, malate, citrate) demonstrate inner-sphere metal coordination by multiple donor groups. XAFS spectral fits of Ni(II) solutions containing soil fulvic acid are consistent with inner-sphere Ni(II) coordination by one or more carboxylate groups, but spectra are noisy and outer-sphere modes of coordination cannot be ruled out. These molecular studies refine our understanding of the interactions between carboxylates and weakly complexing divalent transition metals, such as Ni(II).

  15. Carboxylic acid sorption regeneration process

    DOEpatents

    King, C. Judson; Poole, Loree J.

    1995-01-01

    Carboxylic acids are sorbed from aqueous feedstocks into an organic liquid phase or onto a solid adsorbent. The acids are freed from the sorbent phase by treating it with aqueous alkylamine thus forming an alkylammonium carboxylate which is dewatered and decomposed to the desired carboxylic acid and the alkylamine.

  16. An enantioselective route to alpha-methyl carboxylic acids via metal and enzyme catalysis.

    PubMed

    Norinder, Jakob; Bogár, Krisztián; Kanupp, Lisa; Bäckvall, Jan-E

    2007-11-22

    Dynamic kinetic resolution of allylic alcohols to allylic acetates followed by copper-catalyzed allylic substitution gave alkenes in high yields and high optical purity. Subsequent oxidative C-C double bond cleavage afforded pharmaceutically important alpha-methyl substituted carboxylic acids in high ee.

  17. Carboxylic acid sorption regeneration process

    DOEpatents

    King, C.J.; Poole, L.J.

    1995-05-02

    Carboxylic acids are sorbed from aqueous feedstocks into an organic liquid phase or onto a solid adsorbent. The acids are freed from the sorbent phase by treating it with aqueous alkylamine thus forming an alkylammonium carboxylate which is dewatered and decomposed to the desired carboxylic acid and the alkylamine. 10 figs.

  18. Mechanistic Insights into the Catalytic Oxidation of Carboxylic Acids on Au/TiO 2: Partial Oxidation of Propionic and Butyric Acid to Gold Ketenylidene through Unsaturated Acids

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

    McEntee, Monica; Tang, Wenjie; Neurock, Matthew

    Here, the partial oxidation of model C 2–C 4 (acetic, propionic, and butyric) carboxylic acids on Au/TiO 2 catalysts consisting of Au particles ~3 nm in size was investigated using transmission infrared spectroscopy and density functional theory. All three acids readily undergo oxidative dehydrogenation on Au/TiO 2. Propionic and butyric acid dehydrogenate at the C2–C3 positions, whereas acetic acid dehydrogenates at the C1–C2 position. The resulting acrylate and crotonate intermediates are subsequently oxidized to form β-keto acids that decarboxylate. All three acids form a gold ketenylidene intermediate, Au 2C=C=O, along the way to their full oxidation to form CO 2.more » Infrared measurements of Au 2C=C=O formation as a function of time provides a surface spectroscopic probe of the kinetics for the activation and oxidative dehydrogenation of the alkyl groups in the carboxylate intermediates that form.« less

  19. Mechanistic Insights into the Catalytic Oxidation of Carboxylic Acids on Au/TiO 2: Partial Oxidation of Propionic and Butyric Acid to Gold Ketenylidene through Unsaturated Acids

    DOE PAGES

    McEntee, Monica; Tang, Wenjie; Neurock, Matthew; ...

    2014-12-12

    Here, the partial oxidation of model C 2–C 4 (acetic, propionic, and butyric) carboxylic acids on Au/TiO 2 catalysts consisting of Au particles ~3 nm in size was investigated using transmission infrared spectroscopy and density functional theory. All three acids readily undergo oxidative dehydrogenation on Au/TiO 2. Propionic and butyric acid dehydrogenate at the C2–C3 positions, whereas acetic acid dehydrogenates at the C1–C2 position. The resulting acrylate and crotonate intermediates are subsequently oxidized to form β-keto acids that decarboxylate. All three acids form a gold ketenylidene intermediate, Au 2C=C=O, along the way to their full oxidation to form CO 2.more » Infrared measurements of Au 2C=C=O formation as a function of time provides a surface spectroscopic probe of the kinetics for the activation and oxidative dehydrogenation of the alkyl groups in the carboxylate intermediates that form.« less

  20. Conversion of municipal solid wastes to carboxylic acids by thermophilic fermentation.

    PubMed

    Chan, Wen Ning; Holtzapple, Mark T

    2003-11-01

    The purpose of this research is to generate carboxylic acids from the biodegradable fraction of municipal solid wastes (MSW) and municipal sewage sludge (MSS) by using a thermophilic (55 degrees C), anaerobic, high-solid fermentation. With terrestrial inocula, the highest total carboxylic acid concentration achieved was 20.5 g/L, the highest conversion obtained was 69%, and the highest acetic acid selectivity was 86.4%. Marine inocula were also used to compare against terrestrial sources. Continuum particle distribution modeling (CPDM) was used to predict the final acid product concentrations and substrate conversions at a wide range of liquid residence times (LRT) and volatile solid loading rates (VSLR). "Maps" showing the product concentration and conversion for various LRT and VSLR were generated from CPDM. The predictions were compared to the experimental results. On average, the difference between the predicted and experimental values were 13% for acid concentration and 10% for conversion. CPDM "maps" show that marine inocula produce higher concentrations than terrestrial inocula.

  1. Deletion of acetate transporter gene ADY2 improved tolerance of Saccharomyces cerevisiae against multiple stresses and enhanced ethanol production in the presence of acetic acid.

    PubMed

    Zhang, Mingming; Zhang, Keyu; Mehmood, Muhammad Aamer; Zhao, Zongbao Kent; Bai, Fengwu; Zhao, Xinqing

    2017-12-01

    The aim of this work was to study the effects of deleting acetate transporter gene ADY2 on growth and fermentation of Saccharomyces cerevisiae in the presence of inhibitors. Comparative transcriptome analysis revealed that three genes encoding plasma membrane carboxylic acid transporters, especially ADY2, were significantly downregulated under the zinc sulfate addition condition in the presence of acetic acid stress, and the deletion of ADY2 improved growth of S. cerevisiae under acetic acid, ethanol and hydrogen peroxide stresses. Consistently, a concomitant increase in ethanol production by 14.7% in the presence of 3.6g/L acetic acid was observed in the ADY2 deletion mutant of S. cerevisiae BY4741. Decreased intracellular acetic acid, ROS accumulation, and plasma membrane permeability were observed in the ADY2 deletion mutant. These findings would be useful for developing robust yeast strains for efficient ethanol production. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. STABILITY OF MFI ZEOLITE-FILLED PDMS MEMBRANES DURING PERVAPORATIVE ETHANOL RECOVERY FROM AQUEOUS MIXTURES CONTAINING ACETIC ACID

    EPA Science Inventory

    Pervaporation is a potential process for recovering bioethanol produced from biomass fermentation. Fermentation broths contain ethanol, water, and a variety of other compounds, often including carboxylic acids. The effects of acetic acid on long-term pervaporation of aqueous et...

  3. Separation of aromatic carboxylic acids using quaternary ammonium salts on reversed-phase HPLC. 1. Separation behavior of aromatic carboxylic acids

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

    Kawamura, K.; Okuwaki, A.; Verheyen, T.

    In order to develop separation processes and analytical methods for aromatic carboxylic acids for the coal oxidation products, the separation behavior of aromatic carboxylic acids on a reversed-phase HPLC using eluent containing quaternary ammonium salt has been investigated. The retention mechanism of aromatic carboxylic acids was discussed on the basis of both ion-pair partition model and ion-exchange model. The retention behavior of aromatic carboxylic acids possessing one (or two) carboxylic acid group(s) followed the ion-pair partition model, where linear free energy relationship was observed between the capacity factor and the extraction equilibrium constants of benzoic acid and naphthalene carboxylic acid.more » Besides, the retention behavior followed ion-exchange model with increasing the number of carboxylic acids, where the capacity factor of benzene polycarboxylic acids is proportional to the association constants between aromatic acids and quaternary ammonium ions calculated on the basis of an electrostatic interaction model.« less

  4. Comparative Indole-3-Acetic Acid Levels in the Slender Pea and Other Pea Phenotypes 1

    PubMed Central

    Law, David M.; Davies, Peter J.

    1990-01-01

    Free indole-3-acetic acid levels were measured by gas chromatography-mass spectrometry in three ultra-tall `slender' Pisum sativum L. lines differing in gibberellin content. Measurements were made for apices and stem elongation zones of light-grown plants and values were compared with wild-type, dwarf, and nana phenotypes in which internode length is genetically regulated, purportedly via the gibberellin level. Indole-3-acetic acid levels of growing stems paralleled growth rates in all lines, and were high in all three slender genotypes. Growth was inhibited by p-chlorophenoxyisobutyric acid, demonstrating the requirement of auxin activity for stem elongation, and also by the ethylene precursor 1-aminocyclopropane-1-carboxylic acid. It is concluded that the slender phenotype may arise from constant activation of a gibberellin receptor or transduction chain event leading directly or indirectly to elevated levels of indole-3-acetic acid, and that increased indole-3-acetic acid levels are a significant factor in the promotion of stem elongation. PMID:16667653

  5. Influence of ultrasound on the heterogeneous Fenton-like oxidation of acetic acid.

    PubMed

    Cihanoğlu, Aydın; Gündüz, Gönül; Dükkancı, Meral

    2017-11-01

    The main objective of this study is to investigate the effect of ultrasound on the heterogeneous Fenton-like oxidation of acetic acid, which is one of the most resistant carboxylic acids to oxidation. For this purpose, firstly, the degradation of acetic acid was examined by using ultrasound alone and the effects of different parameters such as: type of sonication system, ultrasonic power, and addition of H 2 O 2 were investigated on the degradation of acetic acid. There was no chemical oxygen demand (COD) reduction in the presence of sonication alone. In the presence of the heterogeneous Fenton-like oxidation process alone, at 303 K, COD reduction reached only 7.1% after 2 h of reaction. However, the combination of the heterogeneous Fenton-like oxidation process with ultrasound increased the COD reduction from 7.1% to 25.5% after 2 h of reaction in an ultrasonic bath operated at 40 kHz, while the COD reduction only increased from 7.1% to 8.9% in the ultrasonic reactor operated at 850 kHz. This result indicates that the hybrid process of ultrasound and heterogeneous Fenton-like oxidation is a promising process to degrade acetic acid.

  6. Atmospheric chemistry of carboxylic acids: microbial implication versus photochemistry

    NASA Astrophysics Data System (ADS)

    Vaïtilingom, M.; Charbouillot, T.; Deguillaume, L.; Maisonobe, R.; Parazols, M.; Amato, P.; Sancelme, M.; Delort, A.-M.

    2011-08-01

    The objective of this work was to compare experimentally the contribution of photochemistry vs. microbial activity to the degradation of carboxylic acids present in cloud water. For this, we selected 17 strains representative of the microflora existing in real clouds and worked on two distinct artificial cloud media that reproduce marine and continental cloud chemical composition. Photodegradation experiments with hydrogen peroxide (H2O2) as a source of hydroxyl radicals were performed under the same microcosm conditions using two irradiation systems. Biodegradation and photodegradation rates of acetate, formate, oxalate and succinate were measured on both media at 5 °C and 17 °C and were shown to be on the same order of magnitude (around 10-10-10-11 M s-1). The chemical composition (marine or continental origin) had little influence on photodegradation and biodegradation rates while the temperature shift from 17 °C to 5 °C decreased biodegradation rates of a factor 2 to 5. In order to test other photochemical scenarios, theoretical photodegradation rates were calculated considering hydroxyl (OH) radical concentration values in cloud water estimated by cloud chemistry modelling studies and available reaction rate constants of carboxylic compounds with both hydroxyl and nitrate radicals. Considering high OH concentration ([OH] = 1 × 10-12 M) led to no significant contribution of microbial activity in the destruction of carboxylic acids. On the contrary, for lower OH concentration (at noon, [OH] = 1 × 10-14 M), microorganisms could efficiently compete with photochemistry and in similar contributions than the ones estimated by our experimental approach. Combining these two approaches (experimental and theoretical), our results led to the following conclusions: oxalate was only photodegraded; the photodegradation of formate was usually more efficient than its biodegradation; the biodegradation of acetate and succinate seemed to exceed their photodegradation.

  7. Use of RSM for the multivariate, simultaneous multiobjective optimization of the operating conditions of aliphatic carboxylic acids ion-exclusion chromatography column: Quantitative study of hydrodynamic, isotherm, and thermodynamic behavior.

    PubMed

    Shojaeimehr, Tahereh; Rahimpour, Farshad; Schwarze, Michael; Repke, Jens-Uwe; Godini, Hamid Reza; Wozny, Günter

    2018-04-15

    The present study evaluates the capability of ion exclusion chromatography (IEC) of short chain aliphatic carboxylic acids using a cation exchange column (8% sulfonated cross-linked styrene-divinylbenzene copolymer) in different experimental conditions. Since one of the prerequisites to the development of an efficient carboxylic acid separation process is to obtain the optimum operational conditions, response surface methodology (RSM) was used to develop an approach to evaluate carboxylic acids separation process in IEC columns. The effect of the operating conditions such as column temperature, sulfuric acid concentration as the mobile phase, and the flow rate was studied using Central Composite Face (CCF) design. The optimum operating conditions for the separate injection of lactic acid and acetic acid is temperature of 75 °C, sulfuric acid concentration of 0.003 N for both acids and flow rate of 0.916 (0.886) mL/min for acetic acid (lactic acid). Likewise, the optimum conditions for the simultaneous injection of acetic and lactic acid mixture are the column temperature of 68 °C, sulfuric acid concentration of 0.0003 N, and flow rate of 0.777 mL/min. In the next step, the adsorption equilibria of acetic acid and lactic acid on the stationary phase were investigated through a series of Frontal Analysis (FA), Frontal Analysis by Characteristic Points (FACP), and using Langmuir isotherm model. The results showed an excellent agreement between the model and experimental data. Finally, the results of thermodynamic studies proved that the IEC process for separation of acetic and lactic acid is a spontaneous, feasible, exothermic, and random process with a physical adsorption mechanism. The results of the current paper can be a valuable information in the stages of designing IEC columns for separation of aliphatic carboxylic acids. Copyright © 2018 Elsevier B.V. All rights reserved.

  8. Structure Property Relationships of Carboxylic Acid Isosteres.

    PubMed

    Lassalas, Pierrik; Gay, Bryant; Lasfargeas, Caroline; James, Michael J; Tran, Van; Vijayendran, Krishna G; Brunden, Kurt R; Kozlowski, Marisa C; Thomas, Craig J; Smith, Amos B; Huryn, Donna M; Ballatore, Carlo

    2016-04-14

    The replacement of a carboxylic acid with a surrogate structure, or (bio)-isostere, is a classical strategy in medicinal chemistry. The general underlying principle is that by maintaining the features of the carboxylic acid critical for biological activity, but appropriately modifying the physicochemical properties, improved analogs may result. In this context, a systematic assessment of the physicochemical properties of carboxylic acid isosteres would be desirable to enable more informed decisions of potential replacements to be used for analog design. Herein we report the structure-property relationships (SPR) of 35 phenylpropionic acid derivatives, in which the carboxylic acid moiety is replaced with a series of known isosteres. The data set generated provides an assessment of the relative impact on the physicochemical properties that these replacements may have compared to the carboxylic acid analog. As such, this study presents a framework for how to rationally apply isosteric replacements of the carboxylic acid functional group.

  9. Separation of aliphatic carboxylic acids and benzenecarboxylic acids by ion-exclusion chromatography with various cation-exchange resin columns and sulfuric acid as eluent.

    PubMed

    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.

  10. Overview on mechanisms of acetic acid resistance in acetic acid bacteria.

    PubMed

    Wang, Bin; Shao, Yanchun; Chen, Fusheng

    2015-02-01

    Acetic acid bacteria (AAB) are a group of gram-negative or gram-variable bacteria which possess an obligate aerobic property with oxygen as the terminal electron acceptor, meanwhile transform ethanol and sugar to corresponding aldehydes, ketones and organic acids. Since the first genus Acetobacter of AAB was established in 1898, 16 AAB genera have been recorded so far. As the main producer of a world-wide condiment, vinegar, AAB have evolved an elegant adaptive system that enables them to survive and produce a high concentration of acetic acid. Some researches and reviews focused on mechanisms of acid resistance in enteric bacteria and made the mechanisms thoroughly understood, while a few investigations did in AAB. As the related technologies with proteome, transcriptome and genome were rapidly developed and applied to AAB research, some plausible mechanisms conferring acetic acid resistance in some AAB strains have been published. In this review, the related mechanisms of AAB against acetic acid with acetic acid assimilation, transportation systems, cell morphology and membrane compositions, adaptation response, and fermentation conditions will be described. Finally, a framework for future research for anti-acid AAB will be provided.

  11. Wind tunnel investigations on the retention of carboxylic acids during riming

    NASA Astrophysics Data System (ADS)

    Jost, Alexander; Szakáll, Miklós; Diehl, Karoline; Mitra, Subir K.; Borrmann, Stephan

    2015-04-01

    In mid-latitudes, precipitation is mainly initiated via the ice phase in mixed phase clouds. In such clouds the ice particles grow to precipitation sizes at the expense of liquid drops through riming which means that supercooled droplets collide with ice particles and subsequently freeze. Water-soluble trace substances present in the liquid phase might remain only fractionally in the ice phase after freezing. This fractionation is called retention and is an important ratio which quantifies the partitioning of atmospheric trace substances between the phases. Laboratory experiments were carried out at the Mainz vertical wind tunnel to determine the retention of lower mono- and di-carboxylic acids during riming. Due to their low molecular weight and their polarity these acids are water-soluble. In the atmosphere formic acid and acetic acid are the most abundant mono-carboxylic acids in the gas and aqueous phase, thus, they represent the major fraction of carboxylic acids in cloud water. Oxalic and malonic acid are common coatings on aerosol particles because of their relatively low saturation vapor pressure. These di-carboxylic acids might therefore promote the aerosol particles to act as cloud condensation nuclei and additionally contribute to the aqueous phase chemistry in cloud droplets. The conditions during the riming experiments in the wind tunnel were similar to those in atmospheric mixed phase clouds, i.e. temperatures from -18°C to -6 °C, liquid water contents between 0.5 and 1.5 g/m3, and liquid drop radii between 10 and 20 μm. The liquid phase concentrations ranged from 3 to 5 mg/l (4.1 < pH < 4.5). As rime collectors captively floating ice particles and quasi-floating snowflakes with diameters between 0.6 and 1.5 cm were used. The wind speed in the vertical wind tunnel was very close to the terminal velocities of the rime collectors, thus, the ventilation during riming was in the same order of magnitude as under atmospheric riming conditions. After

  12. Sources and sinks of formic, acetic, and pyruvic acids over central Amazonia. II - Wet season

    NASA Technical Reports Server (NTRS)

    Talbot, R. W.; Andreae, M. O.; Berresheim, H.; Jacob, D. J.; Beecher, K. M.

    1990-01-01

    Potential sources and sinks of formic, acetic, and pyruvic acids over the Amazon forest were investigated using a photochemical model and data collected on gas phase concentrations of these acids in the forest canopy, boundary layer, and free troposphere over the central Amazon Basin during the 1987 wet season. It was found that the atmospheric reactions previously suggested in the literature as sources of carboxylic acids (i.e., the gas phase decomposition of isoprene, the reaction between CH3CO3 and a peroxide, and aqueous phase oxidation of CH2O) appear to be too slow to explain the observed concentrations, suggesting that other atmospheric reactions, so far unidentified, could make a major contribution to the carboxylic acid budgets.

  13. Acetic acid production from food wastes using yeast and acetic acid bacteria micro-aerobic fermentation.

    PubMed

    Li, Yang; He, Dongwei; Niu, Dongjie; Zhao, Youcai

    2015-05-01

    In this study, yeast and acetic acid bacteria strains were adopted to enhance the ethanol-type fermentation resulting to a volatile fatty acids yield of 30.22 g/L, and improve acetic acid production to 25.88 g/L, with food wastes as substrate. In contrast, only 12.81 g/L acetic acid can be obtained in the absence of strains. The parameters such as pH, oxidation reduction potential and volatile fatty acids were tested and the microbial diversity of different strains and activity of hydrolytic ferment were investigated to reveal the mechanism. The optimum pH and oxidation reduction potential for the acetic acid production were determined to be at 3.0-3.5 and -500 mV, respectively. Yeast can convert organic matters into ethanol, which is used by acetic acid bacteria to convert the organic wastes into acetic acid. The acetic acid thus obtained from food wastes micro-aerobic fermentation liquid could be extracted by distillation to get high-pure acetic acid.

  14. Gas chromatographic determination of carboxylic acid chlorides and residual carboxylic acid precursors used in the production of some penicillins.

    PubMed

    Lauback, R G; Balitz, D F; Mays, D L

    1976-05-01

    An improved gas chromatographic method is described for the simultaneous determination of carboxylic acid chlorides and related carboxylic acids used in the production of some commercial semisynthetic penicillins. The acid chloride reacts with diethylamine to form the corresponding diethylamide. Carboxylic acid impurities are converted to trimethylsilyl esters. The two derivatives are separated and quantitated in the same chromatographic run. This method, an extension of the earlier procedure of Hishta and Bomstein (1), has been applied to the acid chlorides used to make oxacillin, cloxacillin, dicloxacillin, and methicillin (Figure 1); it shows promise of application to other acid chlorides. The determination is more selective than the usual titration methods, which do not differentiate among acids with similar pK's. Relative standard deviations of the acid chloride determination are 1.0-2.5%. Residual carboxylic acid can be repetitively determined within a range of 0.6% absolute.

  15. 40 CFR 721.2950 - Carboxylic acid glycidyl esters.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Carboxylic acid glycidyl esters. 721... Substances § 721.2950 Carboxylic acid glycidyl esters. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as carboxylic acid glycidyl ester...

  16. Production of carboxylic acid and salt co-products

    DOEpatents

    Hanchar, Robert J.; Kleff, Susanne; Guettler, Michael V.

    2014-09-09

    This invention provide processes for producing carboxylic acid product, along with useful salts. The carboxylic acid product that is produced according to this invention is preferably a C.sub.2-C.sub.12 carboxylic acid. Among the salts produced in the process of the invention are ammonium salts.

  17. Aqueous infrared carboxylate absorbances: Aliphatic di-acids

    USGS Publications Warehouse

    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.

  18. Physicochemical properties of betaine monohydrate-carboxylic acid mixtures

    NASA Astrophysics Data System (ADS)

    Zahrina, I.; Nasikin, M.; Mulia, K.

    2018-05-01

    Green solvents are widely used to minimize environmental problems associated with the use of volatile organic solvents in many industries. DES are new green solvents in recent. The physicochemical properties of DES can be varied by properly combining of salts with different hydrogen bond donors. The objective of this work is to investigate the effect of varying molar ratios on the physicochemical properties of betaine monohydrate-carboxylic acid (i.e,. propionic or acetic acid) mixtures. Properties of mixtures were measured at 40°C. The viscosity, polarity scale (ENR), density, pH, and water content tend to decrease with the decrease in a molar ratio of betaine monohydrate to acid. Conversely, the ionic conductivity was increased. The physicochemical properties of these mixtures depend on the hydrogen bonding interactions between betaine, water and acid molecules. Betaine monohydratecarboxylic acid mixtures have wide range of polarity, low viscosity, high ionic conductivity, and density higher than 1 g·cm-3 that make them fit for numerous various applications. Additionally, due to these mixtures have acidic pH, it should be properly selected of metal type to minimize corrosion problems in industrial application.

  19. Acetobacter pasteurianus metabolic change induced by initial acetic acid to adapt to acetic acid fermentation conditions.

    PubMed

    Zheng, Yu; Zhang, Renkuan; Yin, Haisong; Bai, Xiaolei; Chang, Yangang; Xia, Menglei; Wang, Min

    2017-09-01

    Initial acetic acid can improve the ethanol oxidation rate of acetic acid bacteria for acetic acid fermentation. In this work, Acetobacter pasteurianus was cultured in ethanol-free medium, and energy production was found to increase by 150% through glucose consumption induced by initial acetic acid. However, oxidation of ethanol, instead of glucose, became the main energy production pathway when upon culturing ethanol containing medium. Proteome assay was used to analyze the metabolism change induced by initial acetic acid, which provided insight into carbon metabolic and energy regulation of A. pasteurianus to adapt to acetic acid fermentation conditions. Results were further confirmed by quantitative real-time PCR. In summary, decreased intracellular ATP as a result of initial acetic acid inhibition improved the energy metabolism to produce more energy and thus adapt to the acetic acid fermentation conditions. A. pasteurianus upregulated the expression of enzymes related to TCA and ethanol oxidation to improve the energy metabolism pathway upon the addition of initial acetic acid. However, enzymes involved in the pentose phosphate pathway, the main pathway of glucose metabolism, were downregulated to induce a change in carbon metabolism. Additionally, the enhancement of alcohol dehydrogenase expression promoted ethanol oxidation and strengthened the acetification rate, thereby producing a strong proton motive force that was necessary for energy production and cell tolerance to acetic acid.

  20. Carboxylic acid accelerated formation of diesters

    DOEpatents

    Tustin, G.C.; Dickson, T.J.

    1998-04-28

    This invention pertains to accelerating the rate of formation of 1,1-dicarboxylic esters from the reaction of an aldehyde with a carboxylic acid anhydride or a ketene in the presence of a non-iodide containing a strong Bronsted acid catalyst by the addition of a carboxylic acid at about one bar pressure and between about 0 and 80 C in the substantial absence of a hydrogenation or carbonylation catalyst.

  1. Acetic acid fermentation of acetobacter pasteurianus: relationship between acetic acid resistance and pellicle polysaccharide formation.

    PubMed

    Kanchanarach, Watchara; Theeragool, Gunjana; Inoue, Taketo; Yakushi, Toshiharu; Adachi, Osao; Matsushita, Kazunobu

    2010-01-01

    Acetobacter pasteurianus strains IFO3283, SKU1108, and MSU10 were grown under acetic acid fermentation conditions, and their growth behavior was examined together with their capacity for acetic acid resistance and pellicle formation. In the fermentation process, the cells became aggregated and covered by amorphous materials in the late-log and stationary phases, but dispersed again in the second growth phase (due to overoxidation). The morphological change in the cells was accompanied by changes in sugar contents, which might be related to pellicle polysaccharide formation. To determine the relationship between pellicle formation and acetic acid resistance, a pellicle-forming R strain and a non-forming S strain were isolated, and their fermentation ability and acetic acid diffusion activity were compared. The results suggest that pellicle formation is directly related to acetic acid resistance ability, and thus is important to acetic acid fermentation in these A. pasteurianus strains.

  2. Carboxylic acid accelerated formation of diesters

    DOEpatents

    Tustin, Gerald Charles; Dickson, Todd Jay

    1998-01-01

    This invention pertains to accelerating the rate of formation of 1,1-dicarboxylic esters from the reaction of an aldehyde with a carboxylic acid anhydride or a ketene in the presence of a non-iodide containing a strong Bronsted acid catalyst by the addition of a carboxylic acid at about one bar pressure and between about 0.degree. and 80.degree. C. in the substantial absence of a hydrogenation or carbonylation catalyst.

  3. Approaches to α-amino acids via rearrangement to electron-deficient nitrogen: Beckmann and Hofmann rearrangements of appropriate carboxyl-protected substrates

    PubMed Central

    Rao, V Mohana

    2012-01-01

    Summary The titled approaches were effected with various 2-substituted benzoylacetic acid oximes 3 (Beckmann) and 2-substituted malonamic acids 9 (Hofmann), their carboxyl groups being masked as a 2,4,10-trioxaadamantane unit (an orthoacetate). The oxime mesylates have been rearranged with basic Al2O3 in refluxing CHCl3, and the malonamic acids with phenyliodoso acetate and KOH/MeOH. Both routes are characterized by excellent overall yields. Structure confirmation of final products was conducted with X-ray diffraction in selected cases. The final N-benzoyl and N-(methoxycarbonyl) products are α-amino acids with both carboxyl and amino protection; hence, they are of great interest in peptide synthesis. PMID:23019476

  4. Cationic mononuclear ruthenium carboxylates as catalyst prototypes for self-induced hydrogenation of carboxylic acids.

    PubMed

    Naruto, Masayuki; Saito, Susumu

    2015-08-28

    Carboxylic acids are ubiquitous in bio-renewable and petrochemical sources of carbon. Hydrogenation of carboxylic acids to yield alcohols produces water as the only byproduct, and thus represents a possible next generation, sustainable method for the production of these alternative energy carriers/platform chemicals on a large scale. Reported herein are molecular insights into cationic mononuclear ruthenium carboxylates ([Ru(OCOR)](+)) as prototypical catalysts for the hydrogenation of carboxylic acids. The substrate-derived coordinated carboxylate was found to function initially as a proton acceptor for the heterolytic cleavage of dihydrogen, and subsequently also as an acceptor for the hydride from [Ru-H](+), which was generated in the first step (self-induced catalysis). The hydrogenation proceeded selectively and at high levels of functional group tolerance, a feature that is challenging to achieve with existing heterogeneous/homogeneous catalyst systems. These fundamental insights are expected to significantly benefit the future development of metal carboxylate-catalysed hydrogenation processes of bio-renewable resources.

  5. Cationic mononuclear ruthenium carboxylates as catalyst prototypes for self-induced hydrogenation of carboxylic acids

    PubMed Central

    Naruto, Masayuki; Saito, Susumu

    2015-01-01

    Carboxylic acids are ubiquitous in bio-renewable and petrochemical sources of carbon. Hydrogenation of carboxylic acids to yield alcohols produces water as the only byproduct, and thus represents a possible next generation, sustainable method for the production of these alternative energy carriers/platform chemicals on a large scale. Reported herein are molecular insights into cationic mononuclear ruthenium carboxylates ([Ru(OCOR)]+) as prototypical catalysts for the hydrogenation of carboxylic acids. The substrate-derived coordinated carboxylate was found to function initially as a proton acceptor for the heterolytic cleavage of dihydrogen, and subsequently also as an acceptor for the hydride from [Ru–H]+, which was generated in the first step (self-induced catalysis). The hydrogenation proceeded selectively and at high levels of functional group tolerance, a feature that is challenging to achieve with existing heterogeneous/homogeneous catalyst systems. These fundamental insights are expected to significantly benefit the future development of metal carboxylate-catalysed hydrogenation processes of bio-renewable resources. PMID:26314266

  6. Applications of Carboxylic Acid Reductases in Oleaginous Microbes

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

    Resch, Michael G.; Linger, Jeffrey; McGeehan, John

    2016-05-26

    Carboxylic acid reductases (CARs) are recently emerging reductive enzymes for the direct production of aldehydes from biologically-produced carboxylic acids. Recent work has demonstrated that these powerful enzymes are able to reduce a very broad range of volatile- to long-chain fatty acids as well as aromatic acids. Here, we express four CAR enzymes from different fungal origins to test their activity against fatty acids commonly produced in oleaginous microbes. These in vitro results will inform metabolic engineering strategies to conduct mild biological reduction of carboxylic acids in situ, which is conventionally done via hydrotreating catalysis at high temperatures and hydrogen pressures.

  7. Isotopic composition of Murchison organic compounds: Intramolecular carbon isotope fractionation of acetic acid. Simulation studies of cosmochemical organic syntheses

    NASA Technical Reports Server (NTRS)

    Yuen, G. U.; Cronin, J. R.; Blair, N. E.; Desmarais, D. J.; Chang, S.

    1991-01-01

    Recently, in our laboratories, samples of Murchison acetic acid were decarboxylated successfully and the carbon isotopic composition was measured for the methane released by this procedure. These analyses showed significant differences in C-13/C-12 ratios for the methyl and carboxyl carbons of the acetic acid molecule, strongly suggesting that more than one carbon source may be involved in the synthesis of the Murchison organic compounds. On the basis of this finding, laboratory model systems simulating cosmochemical synthesis are being studied, especially those processes capable of involving two or more starting carbon sources.

  8. In vitro assessment of potential intestinal absorption of some phenolic families and carboxylic acids from commercial instant coffee samples.

    PubMed

    López-Froilán, R; Ramírez-Moreno, E; Podio, N S; Pérez-Rodríguez, M L; Cámara, M; Baroni, M V; Wunderlin, D A; Sánchez-Mata, M C

    2016-06-15

    Coffee is one of the most consumed beverages in the world, being a source of bioactive compounds as well as flavors. Hydroxycinnamic acids, flavonols, and carboxylic acids have been studied in the samples of instant coffee commercialized in Spain. The studies about contents of food components should be complemented with either in vitro or in vivo bioaccessibility studies to know the amount of food components effectively available for functions in the human body. In this sense, a widely used in vitro model has been applied to assess the potential intestinal absorption of phenolic compounds and organic acids. The contents of hydroxycinnamic acids and flavonols were higher in instant regular coffee samples than in the decaffeinated ones. Bioaccessible phenolic compounds in most analyzed samples account for 20-25% of hydroxycinnamic acids and 17-26% of flavonols. This could mean that a great part of them can remain in the gut, acting as potential in situ antioxidants. Quinic, acetic, pyroglutamic, citric and fumaric acids were identified in commercial instant coffee samples. Succinic acid was found in the coffee blend containing chicory. All carboxylic acids showed a very high bioaccessibility. Particularly, acetic acid and quinic acid were found in higher contents in the samples treated with the in vitro simulation of gastrointestinal processes, compared to the original ones, which can be explained by their cleavage from chlorogenic acid during digestion. This is considered as a positive effect, since quinic acid is considered as an antioxidant inducer.

  9. Ultrasonic-assisted preparation of graphene oxide carboxylic acid polyvinyl alcohol polymer film and studies of thermal stability and surface resistivity.

    PubMed

    Li, Yongshen; Li, Jihui; Li, Yuehai; Li, Yali; Song, Yunan; Niu, Shuai; Li, Ning

    2018-01-01

    In this paper, flake graphite, nitric acid and acetic anhydride are used to prepare graphene oxide carboxylic acid (GO-COOH) via an ultrasonic-assisted method, and GO-COOH and polyvinyl alcohol polymer (PVA) are used to synthesize graphene oxide carboxylic acid polyvinyl alcohol polymer (GO-COOPVA) via the ultrasonic-assisted method, and GO-COOPVA is used to manufacture graphene oxide carboxylic acid polyvinyl alcohol polymer film (GO-COOPVA film) via a solidification method, and the structure and morphology of GO-COOH, GO-COOPVA and GO-COOPVA film are characterized, and the thermal stability and surface resistivity are measured in the case of the different amount of GO-COOH. Based on the characterization and measurement, it has been successively confirmed and attested that carboxyl groups implant on 2D lattice of GO to form GO-COOH, and GO-COOH and PVA have the esterification reaction to produce GO-COOPVA, and GO-COOPVA consists of 2D lattice of GO-COOH and the chain of PVA connected in the form of carboxylic ester, and GO-COOPVA film is composed of GO-COOPVA, and the thermal stability of GO-COOPVA film obviously improves in comparison with PVA film, and the surface resistivity of GO-COOPVA film clearly decreases. Copyright © 2017 Elsevier B.V. All rights reserved.

  10. Oxidation of indole-3-acetic acid and oxindole-3-acetic acid to 2,3-dihydro-7-hydroxy-2-oxo-1H indole-3-acetic acid-7'-O-beta-D-glucopyranoside in Zea mays seedlings

    NASA Technical Reports Server (NTRS)

    Nonhebel, H. M.; Bandurski, R. S.

    1984-01-01

    Radiolabeled oxindole-3-acetic acid was metabolized by roots, shoots, and caryopses of dark grown Zea mays seedlings to 2,3-dihydro-7-hydroxy-2-oxo-1H indole-3-acetic acid-7'-O-beta-D-glycopyranoside with the simpler name of 7-hydroxyoxindole-3-acetic acid-glucoside. This compound was also formed from labeled indole-3-acetic acid supplied to intact seedlings and root segments. The glucoside of 7-hydroxyoxindole-3-acetic acid was also isolated as an endogenous compound in the caryopses and shoots of 4-day-old seedlings. It accumulates to a level of 4.8 nanomoles per plant in the kernel, more than 10 times the amount of oxindole-3-acetic acid. In the shoot it is present at levels comparable to that of oxindole-3-acetic acid and indole-3-acetic acid (62 picomoles per shoot). We conclude that 7-hydroxyoxindole-3-acetic acid-glucoside is a natural metabolite of indole-3-acetic acid in Z. mays seedlings. From the data presented in this paper and in previous work, we propose the following route as the principal catabolic pathway for indole-3-acetic acid in Zea seedlings: Indole-3-acetic acid --> Oxindole-3-acetic acid --> 7-Hydroxyoxindole-3-acetic acid --> 7-Hydroxyoxindole-3-acetic acid-glucoside.

  11. Decarboxylative Trifluoromethylation of Aliphatic Carboxylic Acids.

    PubMed

    Kautzky, Jacob A; Wang, Tao; Evans, Ryan W; MacMillan, David W C

    2018-05-14

    Herein we disclose an efficient method for the conversion of carboxylic acids to trifluoromethyl groups via the combination of photoredox and copper catalysis. This transformation tolerates a wide range of functionality including heterocycles, olefins, alcohols, and strained ring systems. To demonstrate the broad potential of this new methodology for late-stage functionalization, we successfully converted a diverse array of carboxylic acid-bearing natural products and medicinal agents to the corresponding trifluoromethyl analogues.

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

    USGS Publications Warehouse

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

    2003-01-01

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

  13. Recovery of carboxylic acids produced during dark fermentation of food waste by adsorption on Amberlite IRA-67 and activated carbon.

    PubMed

    Yousuf, Ahasa; Bonk, Fabian; Bastidas-Oyanedel, Juan-Rodrigo; Schmidt, Jens Ejbye

    2016-10-01

    Amberlite IRA-67 and activated carbon were tested as promising candidates for carboxylic acid recovery by adsorption. Dark fermentation was performed without pH control and without addition of external inoculum at 37°C in batch mode. Lactic, acetic and butyric acids, were obtained, after 7days of fermentation. The maximum acid removal, 74%, from the Amberlite IRA-67 and 63% from activated carbon was obtained from clarified fermentation broth using 200gadsorbent/Lbroth at pH 3.3. The pH has significant effect and pH below the carboxylic acids pKa showed to be beneficial for both the adsorbents. The un-controlled pH fermentation creates acidic environment, aiding in adsorption by eliminating use of chemicals for efficient removal. This study proposes simple and easy valorization of waste to valuable chemicals. Copyright © 2016 Elsevier Ltd. All rights reserved.

  14. Removal of dicyclohexyl acetic acid from aqueous solution using ultrasound, ozone and their combination.

    PubMed

    Kumar, Pardeep; Headley, John; Peru, Kerry; Bailey, Jon; Dalai, Ajay

    2014-01-01

    Naphthenic acids are a complex mixture of organic components, some of which include saturated alkyl-substituted cycloaliphatic carboxylic acids and acyclic aliphatic acids. They are naturally found in hydrocarbon deposits like oil sand, petroleum, bitumen and crude oil. In this study, the oxidation of a relatively high molecular weight naphthenic acid (Dicyclohexyl acetic acid) was investigated using ozonation, ultrasonication and hydrogen peroxide alone and their combinations. Effects on oxidation of dicyclohexyl acetic acid (DAA) were measured for different concentrations of ozone ranging between 0.7 to 3.3 mg L(-1) and pH in the range 6 to 10. Ultrasonication and hydrogen peroxide alone were not effective to oxidize dicyclohexyl acetic acid, but combining ultrasonication with H2O2 had a significant effect on oxidation of dicyclohexyl acetic acid with maximum removal reaching to 84 ± 2.2% with 81 ± 2.1% reduction in chemical oxygen demand (COD). Synergistic effects were observed for combining ultrasonication with ozonation and resulted in 100% DAA removal with 98 ± 0.8% reduction in COD within 15 min at 3.3 mg L(-1) ozone concentration and 130 Watts ultrasonication power. The reaction conditions obtained for the maximum oxidation of DAA and COD removal were used for the degradation of naphthenic acids mixture extracted from oil sands process water (OSPW). The percentage oxidation of NAs mixture extracted from OSPW was 89.3 ± 1.1% in ozonation and combined ozonation and ultrasonication, but COD removal observed was 65 ± 1.2% and 78 ± 1.4% for ozonation and combined ozonation and ultrasonication treatments, respectively.

  15. Short Carboxylic Acid-Carboxylate Hydrogen Bonds Can Have Fully Localized Protons.

    PubMed

    Lin, Jiusheng; Pozharski, Edwin; Wilson, Mark A

    2017-01-17

    Short hydrogen bonds (H-bonds) have been proposed to play key functional roles in several proteins. The location of the proton in short H-bonds is of central importance, as proton delocalization is a defining feature of low-barrier hydrogen bonds (LBHBs). Experimentally determining proton location in H-bonds is challenging. Here, bond length analysis of atomic (1.15-0.98 Å) resolution X-ray crystal structures of the human protein DJ-1 and its bacterial homologue, YajL, was used to determine the protonation states of H-bonded carboxylic acids. DJ-1 contains a buried, dimer-spanning 2.49 Å H-bond between Glu15 and Asp24 that satisfies standard donor-acceptor distance criteria for a LBHB. Bond length analysis indicates that the proton is localized on Asp24, excluding a LBHB at this location. However, similar analysis of the Escherichia coli homologue YajL shows both residues may be protonated at the H-bonded oxygen atoms, potentially consistent with a LBHB. A Protein Data Bank-wide screen identifies candidate carboxylic acid H-bonds in approximately 14% of proteins, which are typically short [⟨d O-O ⟩ = 2.542(2) Å]. Chemically similar H-bonds between hydroxylated residues (Ser/Thr/Tyr) and carboxylates show a trend of lengthening O-O distance with increasing H-bond donor pK a . This trend suggests that conventional electronic effects provide an adequate explanation for short, charge-assisted carboxylic acid-carboxylate H-bonds in proteins, without the need to invoke LBHBs in general. This study demonstrates that bond length analysis of atomic resolution X-ray crystal structures provides a useful experimental test of certain candidate LBHBs.

  16. Synthesis of carboxylic acids, esters, alcohols and ethers containing a tetrahydropyran ring derived from 6-methyl-5-hepten-2-one.

    PubMed

    Hanzawa, Yohko; Hashimoto, Kahoko; Kasashima, Yoshio; Takahashi, Yoshiko; Mino, Takashi; Sakamoto, Masami; Fujita, Tsutomu

    2012-01-01

    3-hydroxy acids, 3-hydroxy-3,7-dimethyloct-6-enoic acid (1) and 3-hydroxy-2,2,3,7-tetramethyloct-6-enoic acid (2), were prepared from 6-methyl-5-hepten-2-one, and they were subsequently used to prepare (2,6,6-trimethyltetrahydropyran-2-yl)acetic acid (3) and 2-methyl-2-(2,6,6-trimethyltetrahydropyran-2-yl)propanoic acid (4), respectively, via cyclization with an acidic catalyst such as boron trifluoride diethyl etherate or iodine. The reaction of carboxylic acids 3 and 4 with alcohols, including methanol, ethanol, and 1-propanol, produced the corresponding methyl, ethyl, and propyl esters, which all contained a tetrahydropyran ring. Reduction of carboxylic acids 3 and 4 afforded the corresponding alcohols. Subsequent reactions of these alcohols with several acyl chlorides produced novel esters. The alcohols also reacted with methyl iodide and sodium hydride to provide novel ethers. A one-pot cyclization-esterification of 1 to produce esters containing a tetrahydropyran ring, using iodine as a catalyst, was also investigated.

  17. Antibiofilm Properties of Acetic Acid

    PubMed Central

    Bjarnsholt, Thomas; Alhede, Morten; Jensen, Peter Østrup; Nielsen, Anne K.; Johansen, Helle Krogh; Homøe, Preben; Høiby, Niels; Givskov, Michael; Kirketerp-Møller, Klaus

    2015-01-01

    Bacterial biofilms are known to be extremely tolerant toward antibiotics and other antimicrobial agents. These biofilms cause the persistence of chronic infections. Since antibiotics rarely resolve these infections, the only effective treatment of chronic infections is surgical removal of the infected implant, tissue, or organ and thereby the biofilm. Acetic acid is known for its antimicrobial effect on bacteria in general, but has never been thoroughly tested for its efficacy against bacterial biofilms. In this article, we describe complete eradication of both Gram-positive and Gram-negative biofilms using acetic acid both as a liquid and as a dry salt. In addition, we present our clinical experience of acetic acid treatment of chronic wounds. In conclusion, we here present the first comprehensive in vitro and in vivo testing of acetic acid against bacterial biofilms. PMID:26155378

  18. Supramolecular architectures in two 1:1 cocrystals of 5-fluorouracil with 5-bromothiophene-2-carboxylic acid and thiophene-2-carboxylic acid.

    PubMed

    Mohana, Marimuthu; Thomas Muthiah, Packianathan; McMillen, Colin D

    2017-06-01

    In solid-state engineering, cocrystallization is a strategy actively pursued for pharmaceuticals. Two 1:1 cocrystals of 5-fluorouracil (5FU; systematic name: 5-fluoro-1,3-dihydropyrimidine-2,4-dione), namely 5-fluorouracil-5-bromothiophene-2-carboxylic acid (1/1), C 5 H 3 BrO 2 S·C 4 H 3 FN 2 O 2 , (I), and 5-fluorouracil-thiophene-2-carboxylic acid (1/1), C 4 H 3 FN 2 O 2 ·C 5 H 4 O 2 S, (II), have been synthesized and characterized by single-crystal X-ray diffraction studies. In both cocrystals, carboxylic acid molecules are linked through an acid-acid R 2 2 (8) homosynthon (O-H...O) to form a carboxylic acid dimer and 5FU molecules are connected through two types of base pairs [homosynthon, R 2 2 (8) motif] via a pair of N-H...O hydrogen bonds. The crystal structures are further stabilized by C-H...O interactions in (II) and C-Br...O interactions in (I). In both crystal structures, π-π stacking and C-F...π interactions are also observed.

  19. Decarboxylative Fluorination of Aliphatic Carboxylic Acids via Photoredox Catalysis

    PubMed Central

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

    2016-01-01

    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. PMID:25881929

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

    PubMed

    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.

  1. Measurement of the rates of oxindole-3-acetic acid turnover, and indole-3-acetic acid oxidation in Zea mays seedlings

    NASA Technical Reports Server (NTRS)

    Nonhebel, H. M.; Bandurski, R. S. (Principal Investigator)

    1986-01-01

    Oxindole-3-acetic acid is the principal catabolite of indole-3-acetic acid in Zea mays seedlings. In this paper measurements of the turnover of oxindole-3-acetic acid are presented and used to calculate the rate of indole-3-acetic acid oxidation. [3H]Oxindole-3-acetic acid was applied to the endosperm of Zea mays seedlings and allowed to equilibrate for 24 h before the start of the experiment. The subsequent decrease in its specific activity was used to calculate the turnover rate. The average half-life of oxindole-3-acetic acid in the shoots was found to be 30 h while that in the kernels had an average half-life of 35h. Using previously published values of the pool sizes of oxindole-3-acetic acid in shoots and kernels from seedlings of the same age and variety, and grown under the same conditions, the rate of indole-3-acetic acid oxidation was calculated to be 1.1 pmol plant-1 h-1 in the shoots and 7.1 pmol plant-1 h-1 in the kernels.

  2. Mechanism of Indole-3-acetic Acid Conjugation

    PubMed Central

    Goren, Raphael; Bukovac, Martin J.; Flore, James A.

    1974-01-01

    Formation of indole-3-acetic acid-aspartate in detached primary leaves of cowpea (Vigna sinensis Endl.) floating on 14C-indole-3-acetic acid (3 μc; 3.15 μm, phosphate-citrate buffer, pH 4.75), almost doubled when leaves were pretreated with 31.5 μm12C-indole-3-acetic acid for 17 hr and then transferred to 14C-indole-3-acetic acid for 4 hours as compared with leaves preincubated in buffer only. When leaves were preincubated with ethylene (11.0 and 104 μl/l) instead of 12C-indole-3-acetic acid, no induction of indole-3-acetylaspartic acid formation was observed, and the rate of indole-3-acetylaspartic acid formation decreased as compared with control leaves. Rhizobitoxine (1.87 μm) inhibited indole-3-acetic acid-induced ethylene production but did not prevent the formation of indole-3-acetylaspartic acid. In view of the similarity of these results and those previously obtained with α-naphthaleneacetic acid, it is concluded that ethylene has no role in the auxin-induced indole-3-acetylaspartic acid formation in cowpea leaves. PMID:16658669

  3. A method for measuring low-weight carboxylic acids from biosolid compost.

    PubMed

    Himanen, Marina; Latva-Kala, Kyösti; Itävaara, Merja; Hänninen, Kari

    2006-01-01

    Concentration of low-weight carboxylic acids (LWCA) is one of the important parameters that should be taken into consideration when compost is applied as soil improver for plant cultivation, because high amounts of LWCA can be toxic to plants. The present work describes a method for analysis of LWCA in compost as a useful tool for monitoring compost quality and safety. The method was tested on compost samples of two different ages: 3 (immature) and 6 (mature) months old. Acids from compost samples were extracted at high pH, filtered, and freeze-dried. The dried sodium salts were derivatized with a sulfuric acid-methanol mixture and concentrations of 11 low-weight fatty acids (C1-C10) were analyzed using headspace gas chromatography. The material was analyzed with two analytical techniques: the external calibration method (tested on 11 LWCA) and the standard addition method (tested only on formic, acetic, propionic, butyric, and iso-butyric acids). The two techniques were compared for efficiency of acids quantification. The method allowed good separation and quantification of a wide range of individual acids with high sensitivity at low concentrations. Detection limit for propionic, butyric, caproic, caprylic, and capric acids was 1 mg kg(-1) compost; for formic, acetic, valeric, enanthoic and pelargonic acids it was 5 mg kg(-1) compost; and for iso-butyric acid it was 10 mg kg(-1) compost. Recovery rates of LWCA were higher in 3-mo-old compost (57-99%) than in 6-mo-old compost (29-45%). In comparison with the external calibration technique the standard addition technique proved to be three to four times more precise for older compost and two times for younger compost. Disadvantages of the standard addition technique are that it is more time demanding and laborious.

  4. Alkali-catalyzed low temperature wet crosslinking of plant proteins using carboxylic acids.

    PubMed

    Reddy, Narendra; Li, Ying; Yang, Yiqi

    2009-01-01

    We report the development of a new method of alkali-catalyzed low temperature wet crosslinking of plant proteins to improve their breaking tenacity without using high temperatures or phosphorus-containing catalysts used in conventional poly(carboxylic acid) crosslinking of cellulose and proteins. Carboxylic acids are preferred over aldehyde-containing crosslinkers for crosslinking proteins and cellulose because of their low toxicity and cost and ability to improve the desired properties of the materials. However, current knowledge in carboxylic acid crosslinking of proteins and cellulose requires the use of carboxylic acids with at least three carboxylic groups, toxic phosphorous-containing catalysts and curing at high temperatures (150-185 degrees C). The use of high temperatures and low pH in conventional carboxylic acid crosslinking has been reported to cause substantial strength loss and/or undesired changes in the properties of the crosslinked materials. In this research, gliadin, soy protein, and zein fibers have been crosslinked with malic acid, citric acid, and butanetetracarboxylic acid to improve the tenacity of the fibers without using high temperatures and phosphorus-containing catalysts. The new method of wet crosslinking using carboxylic acids containing two or more carboxylic groups will be useful to crosslink proteins for various industrial applications.

  5. Polythermal investigation of viscosity of solution of metal carboxylates in VIK-grade mixed carboxylic acids: Yttrium and gadolinium carboxylates

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

    Mezhov, E.A.; Samatov, A.V.; Troyanovskii, L.V.

    Kinematic viscosities have been measured for solutions of yttrium and gadolinium carboxylates in grade VIK mixed carboxylic acids (MCA). It has been established that the optimal fluidity of these metal carboxylate solutions for application to articles is reached at 333 K. A regression model has been developed to describe the concentration and temperature dependences of the viscosity of yttrium- and gadolinium-containing MCA solutions. 2 refs., 3 tabs.

  6. Preparation of .alpha.,.beta.-unsaturated carboxylic acids and esters

    DOEpatents

    Gogate, Makarand Ratnakar; Spivey, James Jerry; Zoeller, Joseph Robert

    1998-01-01

    Disclosed is a process for the preparation of .alpha.,.beta.-unsaturated carboxylic acids and esters thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic acid, ester or anhydride in the presence of a catalyst comprising an oxide of niobium.

  7. Preparation of {alpha},{beta}-unsaturated carboxylic acids and esters

    DOEpatents

    Gogate, M.R.; Spivey, J.J.; Zoeller, J.R.

    1998-09-15

    Disclosed is a process for the preparation of {alpha},{beta}-unsaturated carboxylic acids and esters thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic acid, ester or anhydride in the presence of a catalyst comprising an oxide of niobium.

  8. Oxidation of indole-3-acetic acid to oxindole-3-acetic acid by an enzyme preparation from Zea mays

    NASA Technical Reports Server (NTRS)

    Reinecke, D. M.; Bandurski, R. S.

    1988-01-01

    Indole-3-acetic acid is oxidized to oxindole-3-acetic acid by Zea mays tissue extracts. Shoot, root, and endosperm tissues have enzyme activities of 1 to 10 picomoles per hour per milligram protein. The enzyme is heat labile, is soluble, and requires oxygen for activity. Cofactors of mixed function oxygenase, peroxidase, and intermolecular dioxygenase are not stimulatory to enzymic activity. A heat-stable, detergent-extractable component from corn enhances enzyme activity 6- to 10-fold. This is the first demonstration of the in vitro enzymic oxidation of indole-3-acetic acid to oxindole-3-acetic acid in higher plants.

  9. Separation of certain carboxylic acids utilizing cation exchange membranes

    DOEpatents

    Chum, H.L.; Sopher, D.W.

    1983-05-09

    A method of substantially separating monofunctional lower carboxylic acids from a liquid mixture containing the acids wherein the pH of the mixture is adjusted to a value in the range of from about 1 to about 5 to form protonated acids. The mixture is heated to an elevated temperature not greater than about 100/sup 0/C and brought in contact with one side of a perfluorinated cation exchange membrane having sulfonate or carboxylate groups or mixtures thereof with the mixture containing the protonated acids. A pressure gradient can be established across the membrane with the mixture being under higher pressure, so that protonated monofunctional lower carboxylic acids pass through the membrane at a substantially faster rate than the remainder of the mixture thereby substantially separating the acids from the mixture.

  10. Separation of certain carboxylic acids utilizing cation exchange membranes

    DOEpatents

    Chum, Helena L.; Sopher, David W.

    1984-01-01

    A method of substantially separating monofunctional lower carboxylic acids from a liquid mixture containing the acids wherein the pH of the mixture is adjusted to a value in the range of from about 1 to about 5 to form protonated acids. The mixture is heated to an elevated temperature not greater than about 100.degree. C. and brought in contact with one side of a perfluorinated cation exchange membrane having sulfonate or carboxylate groups or mixtures thereof with the mixture containing the protonated acids. A pressure gradient can be established across the membrane with the mixture being under higher pressure, so that protonated monofunctional lower carboxylic acids pass through the membrane at a substantially faster rate than the remainder of the mixture thereby substantially separating the acids from the mixture.

  11. Rapid Screening of Carboxylic Acids from Waste and Surface Waters by ESI-MS/MS Using Barium Ion Chemistry and On-Line Membrane Sampling.

    PubMed

    Duncan, Kyle D; Volmer, Dietrich A; Gill, Chris G; Krogh, Erik T

    2016-03-01

    Negative ion tandem mass spectrometric analysis of aliphatic carboxylic acids often yields only non-diagnostic ([M - H](-)) ions with limited selective fragmentation. However, carboxylates cationized with Ba(2+) have demonstrated efficient dissociation in positive ion mode, providing structurally diagnostic product ions. We report the application of barium adducts followed by collision induced dissociation (CID), to improve selectivity for rapid screening of carboxylic acids in complex aqueous samples. The quantitative MS/MS method presented utilizes common product ions of [M - H + Ba](+) precursor ions. The mechanism of product ion formation is investigated using isotopically labeled standards and a series of structurally related carboxylic acids. The results suggest that hydrogen atoms in the β and γ positions yield common product ions ([BaH](+) and [BaOH](+)). Furthermore, the diagnostic product ion at m/z 196 serves as a qualifying ion for carboxylate species. This methodology has been successfully used in conjunction with condensed phase membrane introduction mass spectrometry (CP-MIMS), with barium acetate added directly to the methanol acceptor phase. The combination enables rapid screening of carboxylic acids directly from acidified water samples (wastewater effluent, spiked natural waters) using a capillary hollow fiber PDMS membrane immersion probe. We have applied this technique for the direct analysis of complex naphthenic acid mixtures spiked into natural surface waters using CP-MIMS. Selectivity at the ionization and tandem mass spectrometry level eliminate isobaric interferences from hydroxylated species present within the samples, which have been observed in negative electrospray ionization.

  12. Complexation of carboxylate on smectite surfaces.

    PubMed

    Liu, Xiandong; Lu, Xiancai; Zhang, Yingchun; Zhang, Chi; Wang, Rucheng

    2017-07-19

    We report a first principles molecular dynamics (FPMD) study of carboxylate complexation on clay surfaces. By taking acetate as a model carboxylate, we investigate its inner-sphere complexes adsorbed on clay edges (including (010) and (110) surfaces) and in interlayer space. Simulations show that acetate forms stable monodentate complexes on edge surfaces and a bidentate complex with Ca 2+ in the interlayer region. The free energy calculations indicate that the complexation on edge surfaces is slightly more stable than in interlayer space. By integrating pK a s and desorption free energies of Al coordinated water calculated previously (X. Liu, X. Lu, E. J. Meijer, R. Wang and H. Zhou, Geochim. Cosmochim. Acta, 2012, 81, 56-68; X. Liu, J. Cheng, M. Sprik, X. Lu and R. Wang, Geochim. Cosmochim. Acta, 2014, 140, 410-417), the pH dependence of acetate complexation has been revealed. It shows that acetate forms inner-sphere complexes on (110) in a very limited mildly acidic pH range while it can complex on (010) in the whole common pH range. The results presented in this study form a physical basis for understanding the geochemical processes involving clay-organics interactions.

  13. Piperidine carboxylic acid derivatives of 10H-pyrazino[2,3-b][1,4]benzothiazine as orally-active adhesion molecule inhibitors.

    PubMed

    Kaneko, Toshihiko; Clark, Richard S J; Ohi, Norihito; Ozaki, Fumihiro; Kawahara, Tetsuya; Kamada, Atsushi; Okano, Kazuo; Yokohama, Hiromitsu; Ohkuro, Masayoshi; Muramoto, Kenzo; Takenaka, Osamu; Kobayashi, Seiichi

    2004-06-01

    Novel piperidine carboxylic acid derivatives of 10H-pyrazino[2,3-b][1,4]benzothiazine were prepared and evaluated for their inhibitory activity on the upregulation of adhesion molecules such as intercellular adhesion molecule-1 (ICAM-1). Replacement of the methanesulfonyl group on the piperidine ring of previously prepared derivatives with a carboxylic acid-containing moiety resulted in a number of potent adhesion molecule inhibitors. Of these, (anti) [3-(10H-pyrazino[2,3-b][1,4]benzothiazin-8-yl)methyl-3-azabicyclo[3.3.1]non-9-yl]acetic acid 2q (ER-49890), showed the most potent oral inhibitory activities against neutrophil migration in an interleukin-1 (IL-1) induced paw inflammation model using mice, and leukocyte accumulation in a carrageenan pleurisy model in the rat, and therapeutic effect on collagen-induced arthritis in rats.

  14. Hydrogenation of carboxylic acids with a homogeneous cobalt catalyst.

    PubMed

    Korstanje, Ties J; van der Vlugt, Jarl Ivar; Elsevier, Cornelis J; de Bruin, Bas

    2015-10-16

    The reduction of esters and carboxylic acids to alcohols is a highly relevant conversion for the pharmaceutical and fine-chemical industries and for biomass conversion. It is commonly performed using stoichiometric reagents, and the catalytic hydrogenation of the acids previously required precious metals. Here we report the homogeneously catalyzed hydrogenation of carboxylic acids to alcohols using earth-abundant cobalt. This system, which pairs Co(BF4)2·6H2O with a tridentate phosphine ligand, can reduce a wide range of esters and carboxylic acids under relatively mild conditions (100°C, 80 bar H2) and reaches turnover numbers of up to 8000. Copyright © 2015, American Association for the Advancement of Science.

  15. Microbial Transformation of Esters of Chlorinated Carboxylic Acids

    PubMed Central

    Paris, D. F.; Wolfe, N. L.; Steen, W. C.

    1984-01-01

    Two groups of compounds were selected for microbial transformation studies. In the first group were carboxylic acid esters having a fixed aromatic moiety and an increasing length of the alkyl component. Ethyl esters of chlorine-substituted carboxylic acids were in the second group. Microorganisms from environmental waters and a pure culture of Pseudomonas putida U were used. The bacterial populations were monitored by plate counts, and disappearance of the parent compound was followed by gas-liquid chromatography as a function of time. The products of microbial hydrolysis were the respective carboxylic acids. Octanol-water partition coefficients (Kow) for the compounds were measured. These values spanned three orders of magnitude, whereas microbial transformation rate constants (kb) varied only 50-fold. The microbial rate constants of the carboxylic acid esters with a fixed aromatic moiety increased with an increasing length of alkyl substituents. The regression coefficient for the linear relationships between log kb and log Kow was high for group 1 compounds, indicating that these parameters correlated well. The regression coefficient for the linear relationships for group 2 compounds, however, was low, indicating that these parameters correlated poorly. PMID:16346459

  16. Measurement and correlation of the solubility of gossypol acetic acid and gossypol acetic acid of optical activity in different solvents

    NASA Astrophysics Data System (ADS)

    Zhang, B.; Tang, H.; Liu, X. Y.; Zhai, X.; Yao, X. C.

    2018-01-01

    The equilibrium method was used to measure the solubility of gossypol acetic acid and gossypol acetic acid of optical activity in isopropyl alcohol, ethanol, acetic acid and ethyl acetate at temperature from 288.15 to 315.15. The Empirical equation and the Apelblat equation model were adopted to correlate the experimental data. For gossypol acetic acid, the root-mean-square deviations (RMSD) were observed in the range of 0.023-4.979 and 0.0112-0.614 for the Empirical equation and the Apelblat equation, respectively. For gossypol acetic acid of optical activity, the RMSD were observed in the range of 0.021-2.211 and 0.021-2.243 for the Empirical equation and the Apelblat equation, individually. And the maximum relative average deviation was 7.5%. Both equations offered an accurate mathematical expression of the experimental results. The calculated solubility showed a good relationship with the experimental solubility for most of solvents. This study provided valuable datas not only for optimizing the process of purification of gossypol acetic acid of optical activity in industry but also for further theoretical studies.

  17. Alcohols enhance the rate of acetic acid diffusion in S. cerevisiae: biophysical mechanisms and implications for acetic acid tolerance.

    PubMed

    Lindahl, Lina; Genheden, Samuel; Faria-Oliveira, Fábio; Allard, Stefan; Eriksson, Leif A; Olsson, Lisbeth; Bettiga, Maurizio

    2017-12-01

    Microbial cell factories with the ability to maintain high productivity in the presence of weak organic acids, such as acetic acid, are required in many industrial processes. For example, fermentation media derived from lignocellulosic biomass are rich in acetic acid and other weak acids. The rate of diffusional entry of acetic acid is one parameter determining the ability of microorganisms to tolerance the acid. The present study demonstrates that the rate of acetic acid diffusion in S. cerevisiae is strongly affected by the alcohols ethanol and n-butanol. Ethanol of 40 g/L and n-butanol of 8 g/L both caused a 65% increase in the rate of acetic acid diffusion, and higher alcohol concentrations caused even greater increases. Molecular dynamics simulations of membrane dynamics in the presence of alcohols demonstrated that the partitioning of alcohols to the head group region of the lipid bilayer causes a considerable increase in the membrane area, together with reduced membrane thickness and lipid order. These changes in physiochemical membrane properties lead to an increased number of water molecules in the membrane interior, providing biophysical mechanisms for the alcohol-induced increase in acetic acid diffusion rate. n-butanol affected S. cerevisiae and the cell membrane properties at lower concentrations than ethanol, due to greater and deeper partitioning in the membrane. This study demonstrates that the rate of acetic acid diffusion can be strongly affected by compounds that partition into the cell membrane, and highlights the need for considering interaction effects between compounds in the design of microbial processes.

  18. Alcohols enhance the rate of acetic acid diffusion in S. cerevisiae: biophysical mechanisms and implications for acetic acid tolerance

    PubMed Central

    Lindahl, Lina; Genheden, Samuel; Faria-Oliveira, Fábio; Allard, Stefan; Eriksson, Leif A.; Olsson, Lisbeth; Bettiga, Maurizio

    2017-01-01

    Microbial cell factories with the ability to maintain high productivity in the presence of weak organic acids, such as acetic acid, are required in many industrial processes. For example, fermentation media derived from lignocellulosic biomass are rich in acetic acid and other weak acids. The rate of diffusional entry of acetic acid is one parameter determining the ability of microorganisms to tolerance the acid. The present study demonstrates that the rate of acetic acid diffusion in S. cerevisiae is strongly affected by the alcohols ethanol and n-butanol. Ethanol of 40 g/L and n-butanol of 8 g/L both caused a 65% increase in the rate of acetic acid diffusion, and higher alcohol concentrations caused even greater increases. Molecular dynamics simulations of membrane dynamics in the presence of alcohols demonstrated that the partitioning of alcohols to the head group region of the lipid bilayer causes a considerable increase in the membrane area, together with reduced membrane thickness and lipid order. These changes in physiochemical membrane properties lead to an increased number of water molecules in the membrane interior, providing biophysical mechanisms for the alcohol-induced increase in acetic acid diffusion rate. n-butanol affected S. cerevisiae and the cell membrane properties at lower concentrations than ethanol, due to greater and deeper partitioning in the membrane. This study demonstrates that the rate of acetic acid diffusion can be strongly affected by compounds that partition into the cell membrane, and highlights the need for considering interaction effects between compounds in the design of microbial processes. PMID:29354649

  19. Acetic Acid Can Catalyze Succinimide Formation from Aspartic Acid Residues by a Concerted Bond Reorganization Mechanism: A Computational Study

    PubMed Central

    Takahashi, Ohgi; Kirikoshi, Ryota; Manabe, Noriyoshi

    2015-01-01

    Succinimide formation from aspartic acid (Asp) residues is a concern in the formulation of protein drugs. Based on density functional theory calculations using Ace-Asp-Nme (Ace = acetyl, Nme = NHMe) as a model compound, we propose the possibility that acetic acid (AA), which is often used in protein drug formulation for mildly acidic buffer solutions, catalyzes the succinimide formation from Asp residues by acting as a proton-transfer mediator. The proposed mechanism comprises two steps: cyclization (intramolecular addition) to form a gem-diol tetrahedral intermediate and dehydration of the intermediate. Both steps are catalyzed by an AA molecule, and the first step was predicted to be rate-determining. The cyclization results from a bond formation between the amide nitrogen on the C-terminal side and the side-chain carboxyl carbon, which is part of an extensive bond reorganization (formation and breaking of single bonds and the interchange of single and double bonds) occurring concertedly in a cyclic structure formed by the amide NH bond, the AA molecule and the side-chain C=O group and involving a double proton transfer. The second step also involves an AA-mediated bond reorganization. Carboxylic acids other than AA are also expected to catalyze the succinimide formation by a similar mechanism. PMID:25588215

  20. Acetic acid can catalyze succinimide formation from aspartic acid residues by a concerted bond reorganization mechanism: a computational study.

    PubMed

    Takahashi, Ohgi; Kirikoshi, Ryota; Manabe, Noriyoshi

    2015-01-12

    Succinimide formation from aspartic acid (Asp) residues is a concern in the formulation of protein drugs. Based on density functional theory calculations using Ace-Asp-Nme (Ace = acetyl, Nme = NHMe) as a model compound, we propose the possibility that acetic acid (AA), which is often used in protein drug formulation for mildly acidic buffer solutions, catalyzes the succinimide formation from Asp residues by acting as a proton-transfer mediator. The proposed mechanism comprises two steps: cyclization (intramolecular addition) to form a gem-diol tetrahedral intermediate and dehydration of the intermediate. Both steps are catalyzed by an AA molecule, and the first step was predicted to be rate-determining. The cyclization results from a bond formation between the amide nitrogen on the C-terminal side and the side-chain carboxyl carbon, which is part of an extensive bond reorganization (formation and breaking of single bonds and the interchange of single and double bonds) occurring concertedly in a cyclic structure formed by the amide NH bond, the AA molecule and the side-chain C=O group and involving a double proton transfer. The second step also involves an AA-mediated bond reorganization. Carboxylic acids other than AA are also expected to catalyze the succinimide formation by a similar mechanism.

  1. Boron-containing amino carboxylic acid compounds and uses thereof

    DOEpatents

    Kabalka, George W.; Srivastava, Rajiv R.

    2000-03-14

    Novel compounds which are useful for boron neutron capture therapy (BNCT) are disclosed. The compounds comprise a stable boron-containing group and an aminocycloalkane carboxylic acid group or a boronated acyclic hydrocarbon-linked amino carboxylic acid. Methods for synthesis of the compounds and for use of the compounds in BNCT are disclosed.

  2. Spectral and in vitro antimicrobial properties of 2-oxo-4-phenyl-6-styryl-1,2,3,4-tetrahydro-pyrimidine-5-carboxylic acid transition metal complexes

    NASA Astrophysics Data System (ADS)

    Dhankar, Raksha P.; Rahatgaonkar, Anjali M.; Chorghade, Mukund S.; Tiwari, Ashutosh

    2-oxo-4-phenyl-6-styryl-1,2,3,4-tetrahydro-pyrimidine-5-carboxylic acid (ADP) was complexed with acetates of Mn(II), Ni(II), Cu(II) and Zn(II). The structures of the ligand and its metal complexes were characterized by microanalysis, IR, NMR, UV-vis spectroscopy, magnetic susceptibility and TGA-DTA analyses. Octahedral and square planar geometries were suggested for the complexes in which the central metal ion coordinated with sbnd O donors of ligand and acetate ions. Each ligand binds the metal using carboxylate oxygens. The ligand and complexes were evaluated for their antimicrobial activities against different species of pathogenic bacteria and fungi. The present novel pyrimidine containing complexes could constitute a new group of antibacterial and antifungal agents.

  3. Omics analysis of acetic acid tolerance in Saccharomyces cerevisiae.

    PubMed

    Geng, Peng; Zhang, Liang; Shi, Gui Yang

    2017-05-01

    Acetic acid is an inhibitor in industrial processes such as wine making and bioethanol production from cellulosic hydrolysate. It causes energy depletion, inhibition of metabolic enzyme activity, growth arrest and ethanol productivity losses in Saccharomyces cerevisiae. Therefore, understanding the mechanisms of the yeast responses to acetic acid stress is essential for improving acetic acid tolerance and ethanol production. Although 329 genes associated with acetic acid tolerance have been identified in the Saccharomyces genome and included in the database ( http://www.yeastgenome.org/observable/resistance_to_acetic_acid/overview ), the cellular mechanistic responses to acetic acid remain unclear in this organism. Post-genomic approaches such as transcriptomics, proteomics, metabolomics and chemogenomics are being applied to yeast and are providing insight into the mechanisms and interactions of genes, proteins and other components that together determine complex quantitative phenotypic traits such as acetic acid tolerance. This review focuses on these omics approaches in the response to acetic acid in S. cerevisiae. Additionally, several novel strains with improved acetic acid tolerance have been engineered by modifying key genes, and the application of these strains and recently acquired knowledge to industrial processes is also discussed.

  4. The Conversion of Carboxylic Acids to Ketones: A Repeated Discovery

    ERIC Educational Resources Information Center

    Nicholson, John W.; Wilson, Alan D.

    2004-01-01

    The conversion of carboxylic acids to ketones is a useful chemical transformation with a long history. Several chemists have claimed that they discovered the conversion of carboxylic acids to ketones yet in fact the reaction is actually known for centuries.

  5. 40 CFR 721.10550 - Rare earth salt of a carboxylic acid (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Rare earth salt of a carboxylic acid... Specific Chemical Substances § 721.10550 Rare earth salt of a carboxylic acid (generic). (a) Chemical... as rare earth salt of a carboxylic acid (PMN P-05-324) is subject to reporting under this section for...

  6. 40 CFR 721.10550 - Rare earth salt of a carboxylic acid (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Rare earth salt of a carboxylic acid... Specific Chemical Substances § 721.10550 Rare earth salt of a carboxylic acid (generic). (a) Chemical... as rare earth salt of a carboxylic acid (PMN P-05-324) is subject to reporting under this section for...

  7. Modification of wheat starch with succinic acid/acetic anhydride and azelaic acid/acetic anhydride mixtures I. Thermophysical and pasting properties.

    PubMed

    Subarić, Drago; Ačkar, Durđica; Babić, Jurislav; Sakač, Nikola; Jozinović, Antun

    2014-10-01

    The aim of this research was to investigate the influence of modification with succinic acid/acetic anhydride and azelaic acid/acetic anhydride mixtures on thermophysical and pasting properties of wheat starch. Starch was isolated from two wheat varieties and modified with mixtures of succinic acid and acetic anhydride, and azelaic acid and acetic anhydride in 4, 6 and 8 % (w/w). Thermophysical, pasting properties, swelling power, solubility and amylose content of modified starches were determined. The results showed that modifications with mixtures of afore mentioned dicarboxylic acids with acetic anhydride decreased gelatinisation and pasting temperatures. Gelatinisation enthalpy of Golubica starch increased, while of Srpanjka starch decreased by modifications. Retrogradation after 7 and 14 day-storage at 4 °C decreased after modifications of both starches. Maximum, hot and cold paste viscosity of both starches increased, while stability during shearing at high temperatures decreased. % setback of starches modified with azelaic acid/acetic anhydride mixture decreased. Swelling power and solubility of both starches increased by both modifications.

  8. Performance, kinetics, and equilibrium of methylene blue adsorption on biochar derived from eucalyptus saw dust modified with citric, tartaric, and acetic acids.

    PubMed

    Sun, Lei; Chen, Dongmei; Wan, Shungang; Yu, Zebin

    2015-12-01

    Biochar derived from eucalyptus saw dust modified with citric, tartaric, and acetic acids at low temperatures was utilized as adsorbent to remove methylene blue (MB) from aqueous solutions. Fourier transform infrared spectroscopy analysis showed that the carboxyl group was introduced on the biochar surface. Adsorption experiment data indicated that eucalyptus saw dust modified with citric acid showed higher MB adsorption efficiency than that modified with tartaric and acetic acids. Pseudo-second-order kinetics was the most suitable model for describing MB adsorption on biochar compared with pseudo-first-order, Elovich, and intraparticle diffusion models. The calculated values of ΔG(0) and ΔH(0) indicated the spontaneous and endothermic nature of the adsorption process. MB adsorption on biochar followed the Langmuir isotherm. The maximum adsorption capacities for eucalyptus saw dust modified with citric, tartaric, and acetic acids were 178.57, 99.01, and 29.94 mg g(-1), respectively, at 35°C. Copyright © 2015 Elsevier Ltd. All rights reserved.

  9. 40 CFR 721.4663 - Fluorinated carboxylic acid alkali metal salts.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... metal salts. 721.4663 Section 721.4663 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4663 Fluorinated carboxylic acid alkali metal salts. (a) Chemical... fluorinated carboxylic acid alkali metal salts (PMNs P-95-979/980/981) are subject to reporting under this...

  10. Effect of surface oxygen vacancy sites on ethanol synthesis from acetic acid hydrogenation on a defective In2O3(110) surface.

    PubMed

    Lyu, Huisheng; Liu, Jiatao; Chen, Yifei; Li, Guiming; Jiang, Haoxi; Zhang, Minhua

    2018-03-07

    Developing a new type of low-cost and high-efficiency non-noble metal catalyst is beneficial for industrially massive synthesis of alcohols from carboxylic acids which can be obtained from renewable biomass. In this work, the effect of active oxygen vacancies on ethanol synthesis from acetic acid hydrogenation over defective In 2 O 3 (110) surfaces has been studied using periodic density functional theory (DFT) calculations. The relative stabilities of six surface oxygen vacancies from O v1 to O v6 on the In 2 O 3 (110) surface were compared. D1 and D4 surfaces with respective O v1 and O v4 oxygen vacancies were chosen to map out the reaction paths from acetic acid to ethanol. A reaction cycle mechanism between the perfect and defective states of the In 2 O 3 surface was found to catalyze the formation of ethanol from acetic acid hydrogenation. By H 2 reduction the oxygen vacancies on the In 2 O 3 surface play key roles in promoting CH 3 COO* hydrogenation and C-O bond breaking in acetic acid hydrogenation. The acetic acid, in turn, benefits the creation of oxygen vacancies, while the C-O bond breaking of acetic acid refills the oxygen vacancy and, thereby, sustains the catalytic cycle. The In 2 O 3 based catalysts were shown to be advantageous over traditional noble metal catalysts in this paper by theoretical analysis.

  11. Development of an automated modular system for the synthesis of [11C]acetate.

    PubMed

    Felicini, Chiara; Någren, Kjell; Berton, Andrea; Pascali, Giancarlo; Salvadori, Piero Alberto

    2010-12-01

    Carboxylation reactions offer a straightforward method for the synthesis of carbon-11 labelled carboxylic acids. Among these, the preparation of carbon-11 (C)-acetate is receiving increasing attention because of diagnostic applications in oncology in addition to its well-established use as a probe for myocardial oxidative metabolism. Although a number of dedicated modules are commercially available, the development of the synthesis on flexible platforms would be beneficial to widen the number of tracers, in particular for preclinical assessment and testing. In this study, the carboxylation reaction was implemented for the synthesis of sodium 1-[C]acetate after the classic route of carboxylation of methylmagnesium chloride by [C]carbon dioxide, followed by the acidic hydrolysis, purification and sterile filtration. This was performed using a commercially available kit of preassembled hardware units and fully compatible components of radiochemistry automation (VarioSystem). The system proved be to highly versatile and inexpensive and allowed a quick translation of the radiochemistry project into a working system even by less experienced personnel, because of predefined interfaces between electronic parts and operating software (preloaded on a laptop and included in the kit). The automatic module proved to be a simple and reliable system for the production of 1-[C]acetate that was prepared in 24 min (total synthesis time) with stable radiochemical yields (20% nondecay corrected) and high radiochemical purity (>97%). The module is used routinely to produce 1-[C]acetate for preclinical studies and is being implemented for the production of the labelled fatty acids.

  12. Chemical rescue of the post-translationally carboxylated lysine mutant of allantoinase and dihydroorotase by metal ions and short-chain carboxylic acids.

    PubMed

    Ho, Ya-Yeh; Huang, Yen-Hua; Huang, Cheng-Yang

    2013-04-01

    Bacterial allantoinase (ALLase) and dihydroorotase (DHOase) are members of the cyclic amidohydrolase family. ALLase and DHOase possess similar binuclear metal centers in the active site in which two metals are bridged by a post-translationally carboxylated lysine. In this study, we determined the effects of carboxylated lysine and metal binding on the activities of ALLase and DHOase. Although DHOase is a metalloenzyme, purified DHOase showed high activity without additional metal supplementation in a reaction mixture or bacterial culture. However, unlike DHOase, ALLase had no activity unless some specific metal ions were added to the reaction mixture or culture. Substituting the metal binding sites H59, H61, K146, H186, H242, or D315 with alanine completely abolished the activity of ALLase. However, the K146C, K146D and K146E mutants of ALLase were still active with about 1-6% activity of the wild-type enzyme. These ALLase K146 mutants were found to have 1.4-1.7 mol metal per mole enzyme subunit, which may indicate that they still contained the binuclear metal center in the active site. The activity of the K146A mutant of the ALLase and the K103A mutant of DHOase can be chemically rescued by short-chain carboxylic acids, such as acetic, propionic, and butyric acids, but not by ethanol, propan-1-ol, and imidazole, in the presence of Co2+ or Mn2+ ions. However, the activity was still ~10-fold less than that of wild-type ALLase. Overall, these results indicated that the 20 natural basic amino acid residues were not sufficiently able to play the role of lysine. Accordingly, we proposed that during evolution, the post-translational modification of carboxylated lysine in the cyclic amidohydrolase family was selected for promoting binuclear metal center self-assembly and increasing the nucleophilicity of the hydroxide at the active site for enzyme catalysis. This kind of chemical rescue combined with site-directed mutagenesis may also be used to identify a binuclear metal

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

    USGS Publications Warehouse

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

    1995-01-01

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

  14. Novel Three-Component Phenazine-1-Carboxylic Acid 1,2-Dioxygenase in Sphingomonas wittichii DP58

    PubMed Central

    Zhao, Qiang; Wang, Wei; Huang, Xian-Qing; Zhang, Xue-Hong

    2017-01-01

    ABSTRACT Phenazine-1-carboxylic acid, the main component of shenqinmycin, is widely used in southern China for the prevention of rice sheath blight. However, the fate of phenazine-1-carboxylic acid in soil remains uncertain. Sphingomonas wittichii DP58 can use phenazine-1-carboxylic acid as its sole carbon and nitrogen sources for growth. In this study, dioxygenase-encoding genes, pcaA1A2, were found using transcriptome analysis to be highly upregulated upon phenazine-1-carboxylic acid biodegradation. PcaA1 shares 68% amino acid sequence identity with the large oxygenase subunit of anthranilate 1,2-dioxygenase from Rhodococcus maanshanensis DSM 44675. The dioxygenase was coexpressed in Escherichia coli with its adjacent reductase-encoding gene, pcaA3, and ferredoxin-encoding gene, pcaA4, and showed phenazine-1-carboxylic acid consumption. The dioxygenase-, ferredoxin-, and reductase-encoding genes were expressed in Pseudomonas putida KT2440 or E. coli BL21, and the three recombinant proteins were purified. A phenazine-1-carboxylic acid conversion capability occurred in vitro only when all three components were present. However, P. putida KT2440 transformed with pcaA1A2 obtained phenazine-1-carboxylic acid degradation ability, suggesting that phenazine-1-carboxylic acid 1,2-dioxygenase has low specificities for its ferredoxin and reductase. This was verified by replacing PcaA3 with RedA2 in the in vitro enzyme assay. High-performance liquid chromatography–mass spectrometry (HPLC-MS) and nuclear magnetic resonance (NMR) analysis showed that phenazine-1-carboxylic acid was converted to 1,2-dihydroxyphenazine through decarboxylation and hydroxylation, indicating that PcaA1A2A3A4 constitutes the initial phenazine-1-carboxylic acid 1,2-dioxygenase. This study fills a gap in our understanding of the biodegradation of phenazine-1-carboxylic acid and illustrates a new dioxygenase for decarboxylation. IMPORTANCE Phenazine-1-carboxylic acid is widely used in southern China

  15. Amavadin and other vanadium complexes as remarkably efficient catalysts for one-pot conversion of ethane to propionic and acetic acids.

    PubMed

    Kirillova, Marina V; Kuznetsov, Maxim L; da Silva, José A L; Guedes da Silva, Maria Fátima C; Fraústo da Silva, João J R; Pombeiro, Armando J L

    2008-01-01

    Synthetic amavadin Ca[V{ON[CH(CH(3))COO](2)}(2)] and its models Ca[V{ON(CH(2)COO)(2)}(2)] and [VO{N(CH(2)CH(2)O)(3)}], in the presence of K(2)S(2)O(8) in trifluoroacetic acid (TFA), exhibit remarkable catalytic activity for the one-pot carboxylation of ethane to propionic and acetic acids with the former as the main product (overall yields up to 93 %, catalyst turnover numbers (TONs) up to 2.0 x 10(4)). The simpler V complexes [VO(CF(3)SO(3))(2)], [VO(acac)(2)] and VOSO(4) are less active. The effects of various factors, namely, C(2)H(6) and CO pressures, time, temperature, and amounts of catalyst, TFA and K(2)S(2)O(8), have been investigated, and this allowed optimisation of the process and control of selectivity. (13)C-labelling experiments indicated that the formation of acetic acid follows two pathways, the dominant one via oxidation of ethane with preservation of the C--C bond, and the other via rupture of this bond and carbonylation of the methyl group by CO; the C--C bond is retained in the formation of propionic acid upon carbonylation of ethane. The reactions proceed via both C- and O-centred radicals, as shown by experiments with radical traps. On the basis of detailed DFT calculations, plausible reaction mechanisms are discussed. The carboxylation of ethane in the presence of CO follows the sequential formation of C(2)H(5) (*), C(2)H(5)CO(*), C(2)H(5)COO(*) and C(2)H(5)COOH. The C(2)H(5)COO(*) radical is easily formed on reaction of C(2)H(5)CO(*) with a peroxo V catalyst via a V{eta(1)-OOC(O)C(2)H(5)} intermediate. In the absence of CO, carboxylation proceeds by reaction of C(2)H(5) (*) with TFA. For the oxidation of ethane to acetic acid, either with preservation or cleavage of the C-C bond, metal-assisted and purely organic pathways are also proposed and discussed.

  16. Biotechnological applications of acetic acid bacteria.

    PubMed

    Raspor, Peter; Goranovic, Dusan

    2008-01-01

    The acetic acid bacteria (AAB) have important roles in food and beverage production, as well as in the bioproduction of industrial chemicals. In recent years, there have been major advances in understanding their taxonomy, molecular biology, and physiology, and in methods for their isolation and identification. AAB are obligate aerobes that oxidize sugars, sugar alcohols, and ethanol with the production of acetic acid as the major end product. This special type of metabolism differentiates them from all other bacteria. Recently, the AAB taxonomy has been strongly rearranged as new techniques using 16S rRNA sequence analysis have been introduced. Currently, the AAB are classified in ten genera in the family Acetobacteriaceae. AAB can not only play a positive role in the production of selected foods and beverages, but they can also spoil other foods and beverages. AAB occur in sugar- and alcohol-enriched environments. The difficulty of cultivation of AAB on semisolid media in the past resulted in poor knowledge of the species present in industrial processes. The first step of acetic acid production is the conversion of ethanol from a carbohydrate carried out by yeasts, and the second step is the oxidation of ethanol to acetic acid carried out by AAB. Vinegar is traditionally the product of acetous fermentation of natural alcoholic substrates. Depending on the substrate, vinegars can be classified as fruit, starch, or spirit substrate vinegars. Although a variety of bacteria can produce acetic acid, mostly members of Acetobacter, Gluconacetobacter, and Gluconobacter are used commercially. Industrial vinegar manufacturing processes fall into three main categories: slow processes, quick processes, and submerged processes. AAB also play an important role in cocoa production, which represents a significant means of income for some countries. Microbial cellulose, produced by AAB, possesses some excellent physical properties and has potential for many applications. Other

  17. Sequential injection redox or acid-base titration for determination of ascorbic acid or acetic acid.

    PubMed

    Lenghor, Narong; Jakmunee, Jaroon; Vilen, Michael; Sara, Rolf; Christian, Gary D; Grudpan, Kate

    2002-12-06

    Two sequential injection titration systems with spectrophotometric detection have been developed. The first system for determination of ascorbic acid was based on redox reaction between ascorbic acid and permanganate in an acidic medium and lead to a decrease in color intensity of permanganate, monitored at 525 nm. A linear dependence of peak area obtained with ascorbic acid concentration up to 1200 mg l(-1) was achieved. The relative standard deviation for 11 replicate determinations of 400 mg l(-1) ascorbic acid was 2.9%. The second system, for acetic acid determination, was based on acid-base titration of acetic acid with sodium hydroxide using phenolphthalein as an indicator. The decrease in color intensity of the indicator was proportional to the acid content. A linear calibration graph in the range of 2-8% w v(-1) of acetic acid with a relative standard deviation of 4.8% (5.0% w v(-1) acetic acid, n=11) was obtained. Sample throughputs of 60 h(-1) were achieved for both systems. The systems were successfully applied for the assays of ascorbic acid in vitamin C tablets and acetic acid content in vinegars, respectively.

  18. Histochemical Demonstration of Protein-Bound Alpha-Acylamido Carboxyl Groups

    PubMed Central

    Barrnett, Russell J.; Seligman, Arnold M.

    1958-01-01

    A method has been developed to demonstrate the alpha-acylamido carboxyl groups of protein, taking advantage of the fact that acylamido carboxyl groups are converted to ketonic carbonyls by the action of acetic anhydride and absolute pyridine. The method utilizes deparaffinized sections of tissues fixed in a variety of fixatives. Following the conversion of carboxyls to the methyl ketones, the latter are stained with 2-hydroxy-3-naphthoic acid hydrazide. Control experiments have indicated that methylation of carboxyls prevented staining, as did carbonyl reagents after the carboxyls were transformed to methyl ketones. Leucofuchsin did not stain the ketonic carbonyls, and only elastic tissue stained with 2-hydroxy-3-naphthoic acid hydrazide without the previous use of the catalyzed reaction with anhydride. A brief survey of the reaction on various tissues of the albino rat was made, and the effects of various fixatives were assayed. Of particular interest were certain sites, such as acidophiles of the anterior pituitary gland, where an intense reaction occurred. The possibility exists that certain specific proteins rich in terminal acylamido carboxyl groups, by virtue of their protein side chains or low molecular weight, may be demonstrated by this method. PMID:13525430

  19. Mechanistic Insights on C-O and C-C Bond Activation and Hydrogen Insertion during Acetic Acid Hydrogenation Catalyzed by Ruthenium Clusters in Aqueous Medium

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

    Shangguan, Junnan; Olarte, Mariefel V.; Chin, Ya-Huei

    Catalytic pathways for acetic acid (CH3COOH) and hydrogen (H2) reactions on dispersed Ru clusters in the aqueous medium and the associated kinetic requirements for C-O and C-C bond cleavages and hydrogen insertion are established from rate and isotopic assessments. CH3COOH reacts with H2 in steps that either retain its carbon backbone and lead to ethanol, ethyl acetate, and ethane (47-95 %, 1-23 %, and 2-17 % carbon selectivities, respectively) or break its C-C bond and form methane (1-43 % carbon selectivities) at moderate temperatures (413-523 K) and H2 pressures (10-60 bar, 298 K). Initial CH3COOH activation is the kinetically relevantmore » step, during which CH3C(O)-OH bond cleaves on a metal site pair at Ru cluster surfaces nearly saturated with adsorbed hydroxyl (OH*) and acetate (CH3COO*) intermediates, forming an adsorbed acetyl (CH3CO*) and hydroxyl (OH*) species. Acetic acid turnover rates increase proportionally with both H2 (10-60 bar) and CH3COOH concentrations at low CH3COOH concentrations (<0.83 M), but decrease from first to zero order as the CH3COOH concentration and the CH3COO* coverages increase and the vacant Ru sites concomitantly decrease. Beyond the initial CH3C(O)-OH bond activation, sequential H-insertions on the surface acetyl species (CH3CO*) lead to C2 products and their derivative (ethanol, ethane, and ethyl acetate) and the competitive C-C bond cleavage of CH3CO* causes the eventual methane formation. The instantaneous carbon selectivities towards C2 species (ethanol, ethane, and ethyl acetate) increase linearly with the concentration of proton-type Hδ+ (derived from carboxylic acid dissociation) and chemisorbed H*. The selectivities towards C2 products decrease with increasing temperature, because of higher observed barriers for C-C bond cleavage than H-insertion. This study offers an interpretation of mechanism and energetics and provides kinetic evidence of carboxylic acid assisted proton-type hydrogen (Hδ+) shuffling during H

  20. Computerized image analysis for acetic acid induced intraepithelial lesions

    NASA Astrophysics Data System (ADS)

    Li, Wenjing; Ferris, Daron G.; Lieberman, Rich W.

    2008-03-01

    Cervical Intraepithelial Neoplasia (CIN) exhibits certain morphologic features that can be identified during a visual inspection exam. Immature and dysphasic cervical squamous epithelium turns white after application of acetic acid during the exam. The whitening process occurs visually over several minutes and subjectively discriminates between dysphasic and normal tissue. Digital imaging technologies allow us to assist the physician analyzing the acetic acid induced lesions (acetowhite region) in a fully automatic way. This paper reports a study designed to measure multiple parameters of the acetowhitening process from two images captured with a digital colposcope. One image is captured before the acetic acid application, and the other is captured after the acetic acid application. The spatial change of the acetowhitening is extracted using color and texture information in the post acetic acid image; the temporal change is extracted from the intensity and color changes between the post acetic acid and pre acetic acid images with an automatic alignment. The imaging and data analysis system has been evaluated with a total of 99 human subjects and demonstrate its potential to screening underserved women where access to skilled colposcopists is limited.

  1. Effect of acetic acid on citric acid fermentation in an integrated citric acid-methane fermentation process.

    PubMed

    Xu, Jian; Chen, Yang-Qiu; Zhang, Hong-Jian; Tang, Lei; Wang, Ke; Zhang, Jian-Hua; Chen, Xu-Sheng; Mao, Zhong-Gui

    2014-09-01

    An integrated citric acid-methane fermentation process was proposed to solve the problem of extraction wastewater in citric acid fermentation process. Extraction wastewater was treated by anaerobic digestion and then recycled for the next batch of citric acid fermentation to eliminate wastewater discharge and reduce water resource consumption. Acetic acid as an intermediate product of methane fermentation was present in anaerobic digestion effluent. In this study, the effect of acetic acid on citric acid fermentation was investigated and results showed that lower concentration of acetic acid could promote Aspergillus niger growth and citric acid production. 5-Cyano-2,3-ditolyl tetrazolium chloride (CTC) staining was used to quantify the activity of A. niger cells, and the results suggested that when acetic acid concentration was above 8 mM at initial pH 4.5, the morphology of A. niger became uneven and the part of the cells' activity was significantly reduced, thereby resulting in deceasing of citric acid production. Effects of acetic acid on citric acid fermentation, as influenced by initial pH and cell number in inocula, were also examined. The result indicated that inhibition by acetic acid increased as initial pH declined and was rarely influenced by cell number in inocula.

  2. Acetic acid removal from corn stover hydrolysate using ethyl acetate and the impact on Saccharomyces cerevisiae bioethanol fermentation.

    PubMed

    Aghazadeh, Mahdieh; Ladisch, Michael R; Engelberth, Abigail S

    2016-07-08

    Acetic acid is introduced into cellulose conversion processes as a consequence of composition of lignocellulose feedstocks, causing significant inhibition of adapted, genetically modified and wild-type S. cerevisiae in bioethanol fermentation. While adaptation or modification of yeast may reduce inhibition, the most effective approach is to remove the acetic acid prior to fermentation. This work addresses liquid-liquid extraction of acetic acid from biomass hydrolysate through a pathway that mitigates acetic acid inhibition while avoiding the negative effects of the extractant, which itself may exhibit inhibition. Candidate solvents were selected using simulation results from Aspen Plus™, based on their ability to extract acetic acid which was confirmed by experimentation. All solvents showed varying degrees of toxicity toward yeast, but the relative volatility of ethyl acetate enabled its use as simple vacuum evaporation could reduce small concentrations of aqueous ethyl acetate to minimally inhibitory levels. The toxicity threshold of ethyl acetate, in the presence of acetic acid, was found to be 10 g L(-1) . The fermentation was enhanced by extracting 90% of the acetic acid using ethyl acetate, followed by vacuum evaporation to remove 88% removal of residual ethyl acetate along with 10% of the broth. NRRL Y-1546 yeast was used to demonstrate a 13% increase in concentration, 14% in ethanol specific production rate, and 11% ethanol yield. This study demonstrated that extraction of acetic acid with ethyl acetate followed by evaporative removal of ethyl acetate from the raffinate phase has potential to significantly enhance ethanol fermentation in a corn stover bioethanol facility. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:929-937, 2016. © 2016 American Institute of Chemical Engineers.

  3. Genetic dissection of acetic acid tolerance in Saccharomyces cerevisiae.

    PubMed

    Geng, Peng; Xiao, Yin; Hu, Yun; Sun, Haiye; Xue, Wei; Zhang, Liang; Shi, Gui-Yang

    2016-09-01

    Dissection of the hereditary architecture underlying Saccharomyces cerevisiae tolerance to acetic acid is essential for ethanol fermentation. In this work, a genomics approach was used to dissect hereditary variations in acetic acid tolerance between two phenotypically different strains. A total of 160 segregants derived from these two strains were obtained. Phenotypic analysis indicated that the acetic acid tolerance displayed a normal distribution in these segregants, and suggested that the acetic acid tolerant traits were controlled by multiple quantitative trait loci (QTLs). Thus, 220 SSR markers covering the whole genome were used to detect QTLs of acetic acid tolerant traits. As a result, three QTLs were located on chromosomes 9, 12, and 16, respectively, which explained 38.8-65.9 % of the range of phenotypic variation. Furthermore, twelve genes of the candidates fell into the three QTL regions by integrating the QTL analysis with candidates of acetic acid tolerant genes. These results provided a novel avenue to obtain more robust strains.

  4. Origin of the 900 cm{sup −1} broad double-hump OH vibrational feature of strongly hydrogen-bonded carboxylic acids

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

    Van Hoozen, Brian L.; Petersen, Poul B.

    2015-03-14

    Medium and strong hydrogen bonds are common in biological systems. Here, they provide structural support and can act as proton transfer relays to drive electron and/or energy transfer. Infrared spectroscopy is a sensitive probe of molecular structure and hydrogen bond strength but strongly hydrogen-bonded structures often exhibit very broad and complex vibrational bands. As an example, strong hydrogen bonds between carboxylic acids and nitrogen-containing aromatic bases commonly display a 900 cm{sup −1} broad feature with a remarkable double-hump structure. Although previous studies have assigned this feature to the OH, the exact origin of the shape and width of this unusualmore » feature is not well understood. In this study, we present ab initio calculations of the contributions of the OH stretch and bend vibrational modes to the vibrational spectrum of strongly hydrogen-bonded heterodimers of carboxylic acids and nitrogen-containing aromatic bases, taking the 7-azaindole—acetic acid and pyridine—acetic acid dimers as examples. Our calculations take into account coupling between the OH stretch and bend modes as well as how both of these modes are affected by lower frequency dimer stretch modes, which modulate the distance between the monomers. Our calculations reproduce the broadness and the double-hump structure of the OH vibrational feature. Where the spectral broadness is primarily caused by the dimer stretch modes strongly modulating the frequency of the OH stretch mode, the double-hump structure results from a Fermi resonance between the out of the plane OH bend and the OH stretch modes.« less

  5. Charge-transfer excited state in pyrene-1-carboxylic acids adsorbed on titanium dioxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Krawczyk, S.; Nawrocka, A.; Zdyb, A.

    2018-06-01

    The electronic structure of excited photosensitizer adsorbed at the surface of a solid is the key factor in the electron transfer processes that underlie the efficiency of dye-sensitized solar cells and photocatalysts. In this work, Stark effect (electroabsorption) spectroscopy has been used to measure the polarizability and dipole moment changes in electronic transitions of pyrene-1-carboxylic (PCA), -acetic (PAA) and -butyric (PBA) acids in ethanol, both free and adsorbed on colloidal TiO2, in glassy ethanol at low temperature. The lack of appreciable increase of dipole moment in the excited state of free and adsorbed PAA and PBA points that two or more single bonds completely prevent the expansion of π-electrons from the aromatic ring towards the carboxylic group, thus excluding the possibility of direct electron injection into TiO2. In free PCA, the pyrene's forbidden S0 → S1 transition has increased intensity, exhibits a long progression in 1400 cm-1 Ag mode and is associated with |Δμ| of 2 D. Adsorption of PCA on TiO2 causes a broadening and red shift of the S0 → S1 absorption band and an increase in dipole moment change on electronic excitation to |Δμ| = 6.5 D. This value increased further to about 15 D when the content of acetic acid in the colloid was changed from 0.2% to 2%, and this effect is ascribed to the surface electric field. The large increase of |Δμ| points that the electric field effect can not only change the energetics of electron transfer from the excited sensitizer into the solid, but can also shift the molecular electronic density, thus directly influencing the electronic coupling factor relevant for electron transfer at the molecule-solid interface.

  6. Methane Upgrading of Acetic Acid as a Model Compound for a Biomass-Derived Liquid over a Modified Zeolite Catalyst

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

    Wang, Aiguo; Austin, Danielle; Karmakar, Abhoy

    The technical feasibility of coaromatization of acetic acid derived from biomass and methane was investigated under mild reaction conditions (400 °C and 30 bar) over silver-, zinc-, and/or gallium-modified zeolite catalysts. On the basis of GC-MS, Micro-GC, and TGA analysis, more light aromatic hydrocarbons, less phenol formation, lower coke production, and higher methane conversion are observed over 5%Zn-1%Ga/ZSM-5 catalyst in comparison with catalytic performance over the other catalysts. Direct evidence of methane incorporation into aromatics over 5%Zn-1%Ga/ZSM-5 catalyst is witnessed in 1H, 2H, and 13C NMR spectra, revealing that the carbon from methane prefers to occupy the phenyl carbon sitesmore » and the benzylic carbon sites, and the hydrogen of methane favors the aromatic and benzylic substitutions of product molecules. In combination with the 13C NMR results for isotopically labeled acetic acid ( 13CH 3COOH and CH 3 13COOH), it can be seen that the methyl and carbonyl carbons of acetic acid are equally involved in the formation of ortho, meta and para carbons of the aromatics, whereas the phenyl carbons directly bonded with alkyl substituent groups and benzylic carbons are derived mainly from the carboxyl carbon of acetic acid. After various catalyst characterizations by using TEM, XRD, DRIFT, NH 3-TPD, and XPS, the excellent catalytic performance might be closely related to the highly dispersed zinc and gallium species on the zeolite support, moderate surface acidity, and an appropriate ratio of weak acidic sites to strong acidic sites as well as the fairly stable oxidation state during acetic acid conversion under a methane environment. Two mechanisms of the coaromatization of acetic acid and methane have also been proposed after consulting all the collected data in this study. In conclusion, the results reported in this paper could potentially lead to more cost-effective utilization of abundant natural gas and biomass.« less

  7. Methane Upgrading of Acetic Acid as a Model Compound for a Biomass-Derived Liquid over a Modified Zeolite Catalyst

    DOE PAGES

    Wang, Aiguo; Austin, Danielle; Karmakar, Abhoy; ...

    2017-04-19

    The technical feasibility of coaromatization of acetic acid derived from biomass and methane was investigated under mild reaction conditions (400 °C and 30 bar) over silver-, zinc-, and/or gallium-modified zeolite catalysts. On the basis of GC-MS, Micro-GC, and TGA analysis, more light aromatic hydrocarbons, less phenol formation, lower coke production, and higher methane conversion are observed over 5%Zn-1%Ga/ZSM-5 catalyst in comparison with catalytic performance over the other catalysts. Direct evidence of methane incorporation into aromatics over 5%Zn-1%Ga/ZSM-5 catalyst is witnessed in 1H, 2H, and 13C NMR spectra, revealing that the carbon from methane prefers to occupy the phenyl carbon sitesmore » and the benzylic carbon sites, and the hydrogen of methane favors the aromatic and benzylic substitutions of product molecules. In combination with the 13C NMR results for isotopically labeled acetic acid ( 13CH 3COOH and CH 3 13COOH), it can be seen that the methyl and carbonyl carbons of acetic acid are equally involved in the formation of ortho, meta and para carbons of the aromatics, whereas the phenyl carbons directly bonded with alkyl substituent groups and benzylic carbons are derived mainly from the carboxyl carbon of acetic acid. After various catalyst characterizations by using TEM, XRD, DRIFT, NH 3-TPD, and XPS, the excellent catalytic performance might be closely related to the highly dispersed zinc and gallium species on the zeolite support, moderate surface acidity, and an appropriate ratio of weak acidic sites to strong acidic sites as well as the fairly stable oxidation state during acetic acid conversion under a methane environment. Two mechanisms of the coaromatization of acetic acid and methane have also been proposed after consulting all the collected data in this study. In conclusion, the results reported in this paper could potentially lead to more cost-effective utilization of abundant natural gas and biomass.« less

  8. Kinetics of Ethyl Acetate Synthesis Catalyzed by Acidic Resins

    ERIC Educational Resources Information Center

    Antunes, Bruno M.; Cardoso, Simao P.; Silva, Carlos M.; Portugal, Ines

    2011-01-01

    A low-cost experiment to carry out the second-order reversible reaction of acetic acid esterification with ethanol to produce ethyl acetate is presented to illustrate concepts of kinetics and reactor modeling. The reaction is performed in a batch reactor, and the acetic acid concentration is measured by acid-base titration versus time. The…

  9. Carboxylic acids in crystallization of macromolecules: learning from successful crystallization experiments.

    PubMed

    Offermann, Lesa R; He, John Z; Mank, Nicholas J; Booth, William T; Chruszcz, Maksymilian

    2014-03-01

    The production of macromolecular crystals suitable for structural analysis is one of the most important and limiting steps in the structure determination process. Often, preliminary crystallization trials are performed using hundreds of empirically selected conditions. Carboxylic acids and/or their salts are one of the most popular components of these empirically derived crystallization conditions. Our findings indicate that almost 40 % of entries deposited to the Protein Data Bank (PDB) reporting crystallization conditions contain at least one carboxylic acid. In order to analyze the role of carboxylic acids in macromolecular crystallization, a large-scale analysis of the successful crystallization experiments reported to the PDB was performed. The PDB is currently the largest source of crystallization data, however it is not easily searchable. These complications are due to a combination of a free text format, which is used to capture information on the crystallization experiments, and the inconsistent naming of chemicals used in crystallization experiments. Despite these difficulties, our approach allows for the extraction of over 47,000 crystallization conditions from the PDB. Initially, the selected conditions were investigated to determine which carboxylic acids or their salts are most often present in crystallization solutions. From this group, selected sets of crystallization conditions were analyzed in detail, assessing parameters such as concentration, pH, and precipitant used. Our findings will lead to the design of new crystallization screens focused around carboxylic acids.

  10. Carboxylic acid reductase enzymes (CARs).

    PubMed

    Winkler, Margit

    2018-04-01

    Carboxylate reductases (CARs) are emerging as valuable catalysts for the selective one-step reduction of carboxylic acids to their corresponding aldehydes. The substrate scope of CARs is exceptionally broad and offers potential for their application in diverse synthetic processes. Two major fields of application are the preparation of aldehydes as end products for the flavor and fragrance sector and the integration of CARs in cascade reactions with aldehydes as the key intermediates. The latest applications of CARs are dominated by in vivo cascades and chemo-enzymatic reaction sequences. The challenge to fully exploit product selectivity is discussed. Recent developments in the characterization of CARs are summarized, with a focus on aspects related to the domain architecture and protein sequences of CAR enzymes. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Simultaneous production of acetic and gluconic acids by a thermotolerant Acetobacter strain during acetous fermentation in a bioreactor.

    PubMed

    Mounir, Majid; Shafiei, Rasoul; Zarmehrkhorshid, Raziyeh; Hamouda, Allal; Ismaili Alaoui, Mustapha; Thonart, Philippe

    2016-02-01

    The activity of bacterial strains significantly influences the quality and the taste of vinegar. Previous studies of acetic acid bacteria have primarily focused on the ability of bacterial strains to produce high amounts of acetic acid. However, few studies have examined the production of gluconic acid during acetous fermentation at high temperatures. The production of vinegar at high temperatures by two strains of acetic acid bacteria isolated from apple and cactus fruits, namely AF01 and CV01, respectively, was evaluated in this study. The simultaneous production of gluconic and acetic acids was also examined in this study. Biochemical and molecular identification based on a 16s rDNA sequence analysis confirmed that these strains can be classified as Acetobacter pasteurianus. To assess the ability of the isolated strains to grow and produce acetic acid and gluconic acid at high temperatures, a semi-continuous fermentation was performed in a 20-L bioreactor. The two strains abundantly grew at a high temperature (41°C). At the end of the fermentation, the AF01 and CV01 strains yielded acetic acid concentrations of 7.64% (w/v) and 10.08% (w/v), respectively. Interestingly, CV01 was able to simultaneously produce acetic and gluconic acids during acetic fermentation, whereas AF01 mainly produced acetic acid. In addition, CV01 was less sensitive to ethanol depletion during semi-continuous fermentation. Finally, the enzymatic study showed that the two strains exhibited high ADH and ALDH enzyme activity at 38°C compared with the mesophilic reference strain LMG 1632, which was significantly susceptible to thermal inactivation. Copyright © 2015 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

  12. Synthesis of Highly Polymerized Water-soluble Cellulose Acetate by the Side Reaction in Carboxylate Ionic Liquid 1-ethyl-3-methylimidazolium Acetate

    NASA Astrophysics Data System (ADS)

    Pang, Jinhui; Liu, Xin; Yang, Jun; Lu, Fachuang; Wang, Bo; Xu, Feng; Ma, Mingguo; Zhang, Xueming

    2016-09-01

    In the present study, we describe a novel one-step method to prepare water-soluble cellulose acetate (WSCA) with higher degree of polymerization values (DP = 650-680) by in situ activation of carboxyl group in ionic liquid. First of all, cellulose was dissolved in 1-ethyl-3-methylimidazolium acetate (EmimAc) and reacted with dichloroacetyl chloride (Cl2AcCl) in order to make cellulose dichloroacetate. Under various conditions, a series of water soluble products were produced. Elemental analysis and NMR results confirmed that they were cellulose acetate with DS (degree of substitution) values in the range from 0.30 to 0.63. NMR studies demonstrated that Cl2AcCl reacted with acetate anion of EmimAc producing a mixed anhydride that acetylated cellulose. Other acylating reagents such as benzoyl chloride, chloroacetyl chloride can also work similarly. 2D NMR characterization suggested that 6-mono-O-acetyl moiety, 3,6-di-O-acetylcellulose and 2,6-di-O-acetyl cellulose were all synthesized and the reactivity of hydroxyl groups in anhydro-glucose units was in the order C-6>C-3>C-2. This work provides an alternative way to make WSCA, meanwhile, also services as a reminder that the activity of EmimAc toward carbohydrate as acylating reagents could be a problem, because the expected acylated products may not be resulted and recycling of this ionic liquid could also be difficult.

  13. Preparation of .alpha., .beta.-unsaturated carboxylic acids and anhydrides

    DOEpatents

    Spivey, James Jerry; Gogate, Makarand Ratnakav; Zoeller, Joseph Robert; Tustin, Gerald Charles

    1998-01-01

    Disclosed is a process for the preparation of .alpha.,.beta.-unsaturated carboxylic acids and anhydrides thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic anhydride in the presence of a catalyst comprising mixed oxides of vanadium, phosphorus and, optionally, a third component selected from titanium, aluminum or, preferably silicon.

  14. Preparation of {alpha}, {beta}-unsaturated carboxylic acids and anhydrides

    DOEpatents

    Spivey, J.J.; Gogate, M.R.; Zoeller, J.R.; Tustin, G.C.

    1998-01-20

    Disclosed is a process for the preparation of {alpha},{beta}-unsaturated carboxylic acids and anhydrides thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic anhydride in the presence of a catalyst comprising mixed oxides of vanadium, phosphorus and, optionally, a third component selected from titanium, aluminum or, preferably silicon.

  15. Characterization of Lactobacillus salivarius alanine racemase: short-chain carboxylate-activation and the role of A131.

    PubMed

    Kobayashi, Jyumpei; Yukimoto, Jotaro; Shimizu, Yasuhiro; Ohmori, Taketo; Suzuki, Hirokazu; Doi, Katsumi; Ohshima, Toshihisa

    2015-01-01

    Many strains of lactic acid bacteria produce high concentrations of d-amino acids. Among them, Lactobacillus salivarius UCC 118 produces d-alanine at a relative concentration much greater than 50 % of the total d, l-alanine (100d/d, l-alanine). We characterized the L. salivarius alanine racemase (ALR) likely responsible for this d-alanine production and found that the enzyme was activated by carboxylates, which is an unique characteristic among ALRs. In addition, alignment of the amino acid sequences of several ALRs revealed that A131 of L. salivarius ALR is likely involved in the activation. To confirm that finding, an L. salivarius ALR variant with an A131K (ALR(A131K)) substitution was prepared, and its properties were compared with those of ALR. The activity of ALR(A131K) was about three times greater than that of ALR. In addition, whereas L. salivarius ALR was strongly activated by low concentrations (e.g., 1 mM) of short chain carboxylates, and was inhibited at higher concentrations (e.g., 10 mM), ALR(A131K) was clearly inhibited at all carboxylate concentrations tested (1-40 mM). Acetate also increased the stability of ALR such that maximum activity was observed at 35 °C and pH 8.0 without acetate, but at 50 °C in the presence of 1 mM acetate. On the other hand, maximum ALR(A131K) activity was observed at 45 °C and around pH 9.0 with or without acetate. It thus appears that A131 mediates the activation and stabilization of L. salivarius ALR by short chain carboxylates.

  16. 21 CFR 862.1390 - 5-Hydroxyindole acetic acid/serotonin test system.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false 5-Hydroxyindole acetic acid/serotonin test system... Test Systems § 862.1390 5-Hydroxyindole acetic acid/serotonin test system. (a) Identification. A 5-hydroxyindole acetic acid/serotonin test system is a device intended to measure 5-hydroxyindole acetic acid...

  17. 21 CFR 862.1390 - 5-Hydroxyindole acetic acid/serotonin test system.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false 5-Hydroxyindole acetic acid/serotonin test system... Test Systems § 862.1390 5-Hydroxyindole acetic acid/serotonin test system. (a) Identification. A 5-hydroxyindole acetic acid/serotonin test system is a device intended to measure 5-hydroxyindole acetic acid...

  18. 21 CFR 862.1390 - 5-Hydroxyindole acetic acid/serotonin test system.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 8 2012-04-01 2012-04-01 false 5-Hydroxyindole acetic acid/serotonin test system... Test Systems § 862.1390 5-Hydroxyindole acetic acid/serotonin test system. (a) Identification. A 5-hydroxyindole acetic acid/serotonin test system is a device intended to measure 5-hydroxyindole acetic acid...

  19. 21 CFR 862.1390 - 5-Hydroxyindole acetic acid/serotonin test system.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false 5-Hydroxyindole acetic acid/serotonin test system... Test Systems § 862.1390 5-Hydroxyindole acetic acid/serotonin test system. (a) Identification. A 5-hydroxyindole acetic acid/serotonin test system is a device intended to measure 5-hydroxyindole acetic acid...

  20. Fermentation of lignocellulosic sugars to acetic acid by Moorella thermoacetica.

    PubMed

    Ehsanipour, Mandana; Suko, Azra Vajzovic; Bura, Renata

    2016-06-01

    A systematic study of bioconversion of lignocellulosic sugars to acetic acid by Moorella thermoacetica (strain ATCC 39073) was conducted. Four different water-soluble fractions (hydrolysates) obtained after steam pretreatment of lignocellulosic biomass were selected and fermented to acetic acid in batch fermentations. M. thermoacetica can effectively ferment xylose and glucose in hydrolysates from wheat straw, forest residues, switchgrass, and sugarcane straw to acetic acid. Xylose and glucose were completely utilized, with xylose being consumed first. M. thermoacetica consumed up to 62 % of arabinose, 49 % galactose and 66 % of mannose within 72 h of fermentation in the mixture of lignocellulosic sugars. The highest acetic acid yield was obtained from sugarcane straw hydrolysate, with 71 % of theoretical yield based on total sugars (17 g/L acetic acid from 24 g/L total sugars). The lowest acetic acid yield was observed in forest residues hydrolysate, with 39 % of theoretical yield based on total sugars (18 g/L acetic acid from 49 g/L total sugars). Process derived compounds from steam explosion pretreatment, including 5-hydroxymethylfurfural (0.4 g/L), furfural (0.1 g/L) and total phenolics (3 g/L), did not inhibit microbial growth and acetic acid production yield. This research identified two major factors that adversely affected acetic acid yield in all hydrolysates, especially in forest residues: (i) glucose to xylose ratio and (ii) incomplete consumption of arabinose, galactose and mannose. For efficient bioconversion of lignocellulosic sugars to acetic acid, it is imperative to have an appropriate balance of sugars in a hydrolysate. Hence, the choice of lignocellulosic biomass and steam pretreatment design are fundamental steps for the industrial application of this process.

  1. Olfactory Sensitivity and Odor Structure-Activity Relationships for Aliphatic Carboxylic Acids in CD-1 Mice

    PubMed Central

    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 (C2 to C4) aliphatic n-carboxylic acids than other mammalian species, but not for longer-chained ones (C5 to C8). Further comparisons suggest that odor structure-activity relationships are both substance class- and species-specific. PMID:22479594

  2. Improvement of acetic acid tolerance of Saccharomyces cerevisiae using a zinc-finger-based artificial transcription factor and identification of novel genes involved in acetic acid tolerance.

    PubMed

    Ma, Cui; Wei, Xiaowen; Sun, Cuihuan; Zhang, Fei; Xu, Jianren; Zhao, Xinqing; Bai, Fengwu

    2015-03-01

    Acetic acid is present in cellulosic hydrolysate as a potent inhibitor, and the superior acetic acid tolerance of Saccharomyces cerevisiae ensures good cell viability and efficient ethanol production when cellulosic raw materials are used as substrates. In this study, a mutant strain of S. cerevisiae ATCC4126 (Sc4126-M01) with improved acetic acid tolerance was obtained through screening strains transformed with an artificial zinc finger protein transcription factor (ZFP-TF) library. Further analysis indicated that improved acetic acid tolerance was associated with improved catalase (CAT) activity. The ZFP coding sequence associated with the improved phenotype was identified, and real-time RT-PCR analysis revealed that three of the possible genes involved in the enhanced acetic acid tolerance regulated by this ZFP-TF, namely YFL040W, QDR3, and IKS1, showed decreased transcription levels in Sc4126-M01 in the presence of acetic acid, compared to those in the control strain. Sc4126-M01 mutants having QDR3 and IKS1 deletion (ΔQDR3 and ΔIKS1) exhibited higher acetic acid tolerance than the wild-type strain under acetic acid treatment. Glucose consumption rate and ethanol productivity in the presence of 5 g/L acetic acid were improved in the ΔQDR3 mutant compared to the wild-type strain. Our studies demonstrated that the synthetic ZFP-TF library can be used to improve acetic acid tolerance of S. cerevisiae and that the employment of an artificial transcription factor can facilitate the exploration of novel functional genes involved in stress tolerance of S. cerevisiae.

  3. Development of Acetic Acid Removal Technology for the UREX+Process

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

    Robert M. Counce; Jack S. Watson

    2009-06-30

    It is imperative that acetic acid is removed from a waste stream in the UREX+process so that nitric acid can be recycled and possible interference with downstreatm steps can be avoidec. Acetic acid arises from acetohydrozamic acid (AHA), and is used to suppress plutonium in the first step of the UREX+process. Later, it is hydrolyzed into hydroxyl amine nitrate and acetic acid. Many common separation technologies were examined, and solvent extraction was determined to be the best choice under process conditions. Solvents already used in the UREX+ process were then tested to determine if they would be sufficient for themore » removal of acetic acid. The tributyl phosphage (TBP)-dodecane diluent, used in both UREX and NPEX, was determined to be a solvent system that gave sufficient distribution coefficients for acetic acid in addition to a high separation factor from nitric acid.« less

  4. Novel Lactate Transporters from Carboxylic Acid-Producing Rhizopus

    USDA-ARS?s Scientific Manuscript database

    The fungus Rhizopus is frequently used for fermentative production of lactic acid, but little is known about the mechanisms or proteins for transporting this carboxylic acid. Since transport of the lactate anion across the plasma membrane is critical to prevent acidification of the cytoplasm, we ev...

  5. Tested Demonstrations: Buffer Capacity of Various Acetic Acid-Sodium Acetate Systems: A Lecture Experiment.

    ERIC Educational Resources Information Center

    Donahue, Craig J.; Panek, Mary G.

    1985-01-01

    Background information and procedures are provided for a lecture experiment which uses indicators to illustrate the concept of differing buffer capacities by titrating acetic acid/sodium acetate buffers with 1.0 molar hydrochloric acid and 1.0 molar sodium hydroxide. A table with data used to plot the titration curve is included. (JN)

  6. Regeneration of carboxylic acid-laden basic sorbents by leaching with a volatile base in an organic solvent

    DOEpatents

    King, C. Judson; Husson, Scott M.

    1999-01-01

    Carboxylic acids are sorbed from aqueous feedstocks onto a solid adsorbent. The acids are freed from the sorbent phase by treating it with an organic solution of alkylamine thus forming an alkylamine/carboxylic acid complex which is decomposed with improved efficiency to the desired carboxylic acid and the alkylamine. Carbon dioxide addition can be used to improve the adsorption or the carboxylic acids by the solid phase sorbent.

  7. Needle trap extraction for GC analysis of formic and acetic acids in aqueous solution.

    PubMed

    Lee, Xinqing; Huang, Daikuan; Lou, Dawei; Pawliszyn, Janusz

    2012-07-01

    Formic and acetic acids are ubiquitous in the environment, food, and most of the natural products. Extraction of the acids from aqueous solution is required for their isotope analysis by the gas chromatography-isotope ratio mass spectrometry. To this objective, we have previously developed a purge-and-trap technique using the dynamic solid-phase microextraction technology, the NeedlEX. The extraction efficiency, however, remains unexamined. Here, we address this question using the flame ionization detector and isotope ratio mass spectrometer while comparing it with that of the CAR/PDMS fiber. The results show that the NeedlEX is applicable at a wide range of concentration through coordination of purge volume given the minimum amount 3.7 ng and 1.8 ng of formic and acetic, respectively, is extracted. The efficiency of NeedlEX was 6-7 times lower than the fiber at 1000 μg/mL depending on the analyte. It is, however, superior to the latter at 10 μg/mL or less owing to its lower detection limit. The extraction efficiency of both acids is equivalent in molar amount. This is, however, disguised by the different response of the flame ionization detector. The isotope ratio mass spectrometor overcomes this problem but is compromised by relatively large errors. These results are particularly useful for isotopic analysis of carboxylic acids. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Accumulation of n-alkanes and carboxylic acids in peat mounds

    NASA Astrophysics Data System (ADS)

    Gabov, D. N.; Beznosikov, V. A.; Gruzdev, I. V.; Yakovleva, E. V.

    2017-10-01

    The quantitative and qualitative compositions of n-alkanes and carboxylic acids have been identified, and the features of their vertical stratification in peat mound profiles of the forest-tundra zone of Komi Republic have been revealed. The composition of n-alkanes (structures with C23, C25, C27, C29, and C31) and carboxylic acids (C24, C26, and C28) and their proportions make it possible to determine changes in plant communities of peat mounds with time and can be used as markers for the degree of decomposition of organic matter. In cryogenic horizons, the contents of n-alkanes (mainly C23, C25, and C27) and carboxylic acids (C24, C26, and C28) significantly decrease because of the different botanic composition of cryogenic horizons (grass-woody residues) and seasonally thawing horizons (moss-subshrub residues) and the almost complete stopping of the equilibrium accumulation and transformation of organic compounds in permafrost.

  9. Production of itaconic acid from acetate by engineering acid-tolerant Escherichia coli W.

    PubMed

    Noh, Myung Hyun; Lim, Hyun Gyu; Woo, Sung Hwa; Song, Jinyi; Jung, Gyoo Yeol

    2018-03-01

    Utilization of abundant and cheap carbon sources can effectively reduce the production cost and enhance the economic feasibility. Acetate is a promising carbon source to achieve cost-effective microbial processes. In this study, we engineered an Escherichia coli strain to produce itaconic acid from acetate. As acetate is known to inhibit cell growth, we initially screened for a strain with a high tolerance to 10 g/L of acetate in the medium, and the W strain was selected as the host. Subsequently, the WC strain was obtained by overexpression of cad (encoding cis-aconitate decarboxylase) using a synthetic promoter and 5' UTR. However, the WC strain produced only 0.13 g/L itaconic acid because of low acetate uptake. To improve the production, the acetate assimilating pathway and glyoxylate shunt pathway were amplified by overexpression of pathway genes as well as its deregulation. The resulting strain, WCIAG4 produced 3.57 g/L itaconic acid (16.1% of theoretical maximum yield) after 88 hr of fermentation with rapid acetate assimilation. These efforts support that acetate can be a potential feedstock for biochemical production with engineered E. coli. © 2017 Wiley Periodicals, Inc.

  10. Acetic acid in aged vinegar affects molecular targets for thrombus disease management.

    PubMed

    Jing, Li; Yanyan, Zhang; Junfeng, Fan

    2015-08-01

    To elucidate the mechanism underlying the action of dietary vinegar on antithrombotic activity, acetic acid, the main acidic component of dietary vinegar, was used to determine antiplatelet and fibrinolytic activity. The results revealed that acetic acid significantly inhibits adenosine diphosphate (ADP)-, collagen-, thrombin-, and arachidonic acid (AA)-induced platelet aggregation. Acetic acid (2.00 mM) reduced AA-induced platelet aggregation to approximately 36.82 ± 1.31%, and vinegar (0.12 mL L(-1)) reduced the platelet aggregation induced by AA to 30.25 ± 1.34%. Further studies revealed that acetic acid exerts its effects by inhibiting cyclooxygenase-1 and the formation of thromboxane-A2. Organic acids including acetic acid, formic acid, lactic acid, citric acid, and malic acid also showed fibrinolytic activity; specifically, the fibrinolytic activity of acetic acid amounted to 1.866 IU urokinase per mL. Acetic acid exerted its fibrinolytic activity by activating plasminogen during fibrin crossing, thus leading to crosslinked fibrin degradation by the activated plasmin. These results suggest that organic acids in dietary vinegar play important roles in the prevention and cure of cardiovascular diseases.

  11. The Conversion of Carboxylic Acids to Ketones: A Repeated Discovery

    NASA Astrophysics Data System (ADS)

    Nicholson, John W.; Wilson, Alan

    2004-09-01

    This article describes the history of the reaction converting carboxylic acids to ketones. The reaction has been rediscovered several times, yet has actually been known for centuries. The best known version of the process is the Dakin West reaction (1928), which applies to α-amino acids and also involves the simultaneous conversion of the amine group to amido functionality. Unlike other examples, this particular reaction has attracted a reasonable amount of attention and it appears to be better known than the conversion of simple carboxylic acids to ketones. However, this reaction was described as long ago as 1612, when Beguin published an account of it in his book, Tyrocinium Chymicum . Since then, many chemists have rediscovered the reaction, apparently independently. One of the earliest modern accounts was by W. H. Perkin, Sr., in 1886, who made various simple ketones by refluxing the appropriate carboxylic acids with base. However, this work has been largely ignored, including by his son, W. H. Perkin, Jr., who used a more complicated base-catalyzed ketonization to prepare small ring compounds in the early years of the 20th century. Other articles detailing the application of ketonization to organic acids are discussed, including our own work, which employed the process to crosslink carboxylated polymers for possible technical application in coatings. Despite its relative obscurity, the reaction was used by Woodward et al. in the total synthesis of strychnine, reported in 1963, and this is discussed in detail at the end of the article. See Featured Molecules .

  12. Low molecular weight carboxylic acids in oxidizing porphyry copper tailings.

    PubMed

    Dold, Bernhard; Blowes, David W; Dickhout, Ralph; Spangenberg, Jorge E; Pfeifer, Hans-Rudolf

    2005-04-15

    The distribution of low molecular weight carboxylic acids (LMWCA) was investigated in pore water profiles from two porphyry copper tailings impoundments in Chile (Piuquenes at La Andina and Cauquenes at El Teniente mine). The objectives of this study were (1) to determine the distribution of LMWCA, which are interpreted to be the metabolic byproducts of the autotroph microbial community in this low organic carbon system, and (2) to infer the potential role of these acids in cycling of Fe and other elements in the tailings impoundments. The speciation and mobility of iron, and potential for the release of H+ via hydrolysis of the ferric iron, are key factors in the formation of acid mine drainage in sulfidic mine wastes. In the low-pH oxidation zone of the Piuquenes tailings, Fe(III) is the dominant iron species and shows high mobility. LMWCA, which occur mainly between the oxidation front down to 300 cm below the tailings surface at both locations (e.g., max concentrations of 0.12 mmol/L formate, 0.17 mmol/L acetate, and 0.01 mmol/L pyruvate at Piuquenes and 0.14 mmol/L formate, 0.14 mmol/L acetate, and 0.006 mmol/L pyruvate at Cauquenes), are observed at the same location as high Fe concentrations (up to 71.2 mmol/L Fe(II) and 16.1 mmol/L Fe(III), respectively). In this zone, secondary Fe(III) hydroxides are depleted. Our data suggest that LMWCA may influence the mobility of iron in two ways. First, complexation of Fe(III), through formation of bidentate Fe(III)-LMWCA complexes (e.g., pyruvate, oxalate), may enhance the dissolution of Fe(III) (oxy)hydroxides or may prevent precipitation of Fe(III) (oxy)hydroxides. Soluble Fe(III) chelate complexes which may be mobilized downward and convert to Fe(II) by Fe(III) reducing bacteria. Second, monodentate LMWCA (e.g., acetate and formate) can be used by iron-reducing bacteria as electron donors (e.g., Acidophilum spp.), with ferric iron as the electron acceptor. These processes may, in part, explain the low abundances

  13. L-Lactic acid production from glycerol coupled with acetic acid metabolism by Enterococcus faecalis without carbon loss.

    PubMed

    Murakami, Nao; Oba, Mana; Iwamoto, Mariko; Tashiro, Yukihiro; Noguchi, Takuya; Bonkohara, Kaori; Abdel-Rahman, Mohamed Ali; Zendo, Takeshi; Shimoda, Mitsuya; Sakai, Kenji; Sonomoto, Kenji

    2016-01-01

    Glycerol is a by-product in the biodiesel production process and considered as one of the prospective carbon sources for microbial fermentation including lactic acid fermentation, which has received considerable interest due to its potential application. Enterococcus faecalis isolated in our laboratory produced optically pure L-lactic acid from glycerol in the presence of acetic acid. Gas chromatography-mass spectrometry analysis using [1, 2-(13)C2] acetic acid proved that the E. faecalis strain QU 11 was capable of converting acetic acid to ethanol during lactic acid fermentation of glycerol. This indicated that strain QU 11 restored the redox balance by oxidizing excess NADH though acetic acid metabolism, during ethanol production, which resulted in lactic acid production from glycerol. The effects of pH control and substrate concentration on lactic acid fermentation were also investigated. Glycerol and acetic acid concentrations of 30 g/L and 10 g/L, respectively, were expected to be appropriate for lactic acid fermentation of glycerol by strain QU 11 at a pH of 6.5. Furthermore, fed-batch fermentation with 30 g/L glycerol and 10 g/L acetic acid wholly exhibited the best performance including lactic acid production (55.3 g/L), lactic acid yield (0.991 mol-lactic acid/mol-glycerol), total yield [1.08 mol-(lactic acid and ethanol)]/mol-(glycerol and acetic acid)], and total carbon yield [1.06 C-mol-(lactic acid and ethanol)/C-mol-(glycerol and acetic acid)] of lactic acid and ethanol. In summary, the strain QU 11 successfully produced lactic acid from glycerol with acetic acid metabolism, and an efficient fermentation system was established without carbon loss. Copyright © 2015 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

  14. Free acetate production by rat hepatocytes during peroxisomal fatty acid and dicarboxylic acid oxidation.

    PubMed

    Leighton, F; Bergseth, S; Rørtveit, T; Christiansen, E N; Bremer, J

    1989-06-25

    The fate of the acetyl-CoA units released during peroxisomal fatty acid oxidation was studied in isolated hepatocytes from normal and peroxisome-proliferated rats. Ketogenesis and hydrogen peroxide generation were employed as indicators of mitochondrial and peroxisomal fatty acid oxidation, respectively. Butyric and hexanoic acids were employed as mitochondrial substrates, 1, omega-dicarboxylic acids as predominantly peroxisomal substrates, and lauric acid as a substrate for both mitochondria and peroxisomes. Ketogenesis from dicarboxylic acids was either absent or very low in normal and peroxisome-proliferated hepatocytes, but free acetate release was detected at rates that could account for all the acetyl-CoA produced in peroxisomes by dicarboxylic and also by monocarboxylic acids. Mitochondrial fatty acid oxidation also led to free acetate generation but at low rates relative to ketogenesis. The origin of the acetate released was confirmed employing [1-14C]dodecanedioic acid. Thus, the activity of peroxisomes might contribute significantly to the free acetate generation known to occur during fatty acid oxidation in rats and possibly also in humans.

  15. Proteome analysis of Acetobacter pasteurianus during acetic acid fermentation.

    PubMed

    Andrés-Barrao, Cristina; Saad, Maged M; Chappuis, Marie-Louise; Boffa, Mauro; Perret, Xavier; Ortega Pérez, Ruben; Barja, François

    2012-03-16

    Acetic acid bacteria (AAB) are Gram-negative, strictly aerobic microorganisms that show a unique resistance to ethanol (EtOH) and acetic acid (AcH). Members of the Acetobacter and Gluconacetobacter genera are capable of transforming EtOH into AcH via the alcohol dehydrogenase (ADH) and aldehyde dehydrogenase (ALDH) enzymes and are used for the industrial production of vinegar. Several mechanisms have been proposed to explain how AAB resist high concentrations of AcH, such as the assimilation of acetate through the tricarboxylic acid (TCA) cycle, the export of acetate by various transporters and modifications of the outer membrane. However, except for a few acetate-specific proteins, little is known about the global proteome responses to AcH. In this study, we used 2D-DIGE to compare the proteome of Acetobacter pasteurianus LMG 1262(T) when growing in glucose or ethanol and in the presence of acetic acid. Interesting protein spots were selected using the ANOVA p-value of 0.05 as threshold and 1.5-fold as the minimal level of differential expression, and a total of 53 proteins were successfully identified. Additionally, the size of AAB was reduced by approximately 30% in length as a consequence of the acidity. A modification in the membrane polysaccharides was also revealed by PATAg specific staining. Copyright © 2011 Elsevier B.V. All rights reserved.

  16. Amino Acids, Aromatic Compounds, and Carboxylic Acids: How Did They Get Their Common Names?

    ERIC Educational Resources Information Center

    Leung, Sam H.

    2000-01-01

    Surveys the roots of the common names of organic compounds most likely to be encountered by undergraduate organic chemistry students. Includes information for 19 amino acids, 17 aromatic compounds, and 21 carboxylic acids. (WRM)

  17. Electron mobility enhancement in ZnO thin films via surface modification by carboxylic acids

    NASA Astrophysics Data System (ADS)

    Spalenka, Josef W.; Gopalan, Padma; Katz, Howard E.; Evans, Paul G.

    2013-01-01

    Modifying the surface of polycrystalline ZnO films using a monolayer of organic molecules with carboxylic acid attachment groups increases the field-effect electron mobility and zero-bias conductivity, resulting in improved transistors and transparent conductors. The improvement is consistent with the passivation of defects via covalent bonding of the carboxylic acid and is reversible by exposure to a UV-ozone lamp. The properties of the solvent used for the attachment are crucial because solvents with high acid dissociation constants (Ka) for carboxylic acids lead to high proton activities and etching of the nanometers-thick ZnO films, masking the electronic effect.

  18. Protonation of Excited State Pyrene-1-Carboxylate by Phosphate and Organic Acids in Aqueous Solution Studied by Fluorescence Spectroscopy

    PubMed Central

    Zelent, Bogumil; Vanderkooi, Jane M.; Coleman, Ryan G.; Gryczynski, Ignacy; Gryczynski, Zygmunt

    2006-01-01

    Pyrene-1-carboxylic acid has a pK of 4.0 in the ground state and 8.1 in the singlet electronic excited state. In the pH range of physiological interest (pH ∼5–8), the ground state compound is largely ionized as pyrene-1-carboxylate, but protonation of the excited state molecule occurs when a proton donor reacts with the carboxylate during the excited state lifetime of the fluorophore. Both forms of the pyrene derivatives are fluorescent, and in this work the protonation reaction was measured by monitoring steady-state and time-resolved fluorescence. The rate of protonation of pyrene-COO− by acetic, chloroacetic, lactic, and cacodylic acids is a function of ΔpK, as predicted by Marcus theory. The rate of proton transfer from these acids saturates at high concentration, as expected for the existence of an encounter complex. Trihydrogen-phosphate is a much better proton donor than dihydrogen- and monohydrogen-phosphate, as can be seen by the pH dependence. The proton-donating ability of phosphate does not saturate at high concentrations, but increases with increasing phosphate concentration. We suggest that enhanced rate of proton transfer at high phosphate concentrations may be due to the dual proton donating and accepting nature of phosphate, in analogy to the Grotthuss mechanism for proton transfer in water. It is suggested that in molecular structures containing multiple phosphates, such as membrane surfaces and DNA, proton transfer rates will be enhanced by this mechanism. PMID:16920831

  19. Analysis of Chiral Carboxylic Acids in Meteorites

    NASA Technical Reports Server (NTRS)

    Burton, A. S.; Elsila, J. E.; Hein, J. E.; Aponte, J. C.; Parker, E. T.; Glavin, D. P.; Dworkin, J. P.

    2015-01-01

    Homochirality of amino acids in proteins and sugars in DNA and RNA is a critical feature of life on Earth. In the absence of a chiral driving force, however, reactions leading to the synthesis of amino acids and sugars result in racemic mixtures. It is currently unknown whether homochirality was necessary for the origins of life or if it was a product of early life. The observation of enantiomeric excesses of certain amino acids of extraterrestrial origins in meteorites provides evidence to support the hypothesis that there was a mechanism for the preferential synthesis or destruction of a particular amino acid enantiomer [e.g., 1-3]. The cause of the observed chiral excesses is un-clear, although at least in the case of the amino acid isovaline, the degree of aqueous alteration that occurred on the meteorite parent body is correlated to the isovaline L-enantiomeric excess [3, 4]. This suggests that chiral symmetry is broken and/or amplified within the meteorite parent bodies. Besides amino acids, there have been only a few reports of other meteoritic compounds found in enantiomeric excess: sugars and sugar acids [5, 6] and the hydroxy acid lactic acid [7]. Determining whether or not additional types of molecules in meteorites are also present in enantiomeric excesses of extraterrestrial information will provide insights into mechanisms for breaking chiral symmetry. Though the previous measurements (e.g., enantiomeric composition of lactic acid [7], and chiral carboxylic acids [8]) were made by gas chromatography-mass spectrometry, the potential for increased sensitivity of liquid chromatography-mass spectrometry (LC-MS) analyses is important because for many meteorite samples, only small sample masses are available for study. Furthermore, at least in the case of amino acids, many of the largest amino acid enantiomeric excesses were observed in samples that contained lower abundances (tens of ppb) of a given amino acid enantiomer. In the present work, we describe

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

    USGS Publications Warehouse

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

    1995-01-01

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

  1. Measuring the concentration of carboxylic acid groups in torrefied spruce wood.

    PubMed

    Khazraie Shoulaifar, Tooran; Demartini, Nikolai; Ivaska, Ari; Fardim, Pedro; Hupa, Mikko

    2012-11-01

    Torrefaction is moderate thermal treatment (∼200-300°C) to improve the energy density, handling and storage properties of biomass fuels. In biomass, carboxylic sites are partially responsible for its hygroscopic. These sites are degraded to varying extents during torrefaction. In this paper, we apply methylene blue sorption and potentiometric titration to measure the concentration of carboxylic acid groups in spruce wood torrefied for 30min at temperatures between 180 and 300°C. The results from both methods were applicable and the values agreed well. A decrease in the equilibrium moisture content at different humidity was also measured for the torrefied wood samples, which is in good agreement with the decrease in carboxylic acid sites. Thus both methods offer a means of directly measuring the decomposition of carboxylic groups in biomass during torrefaction as a valuable parameter in evaluating the extent of torrefaction which provides new information to the chemical changes occurring during torrefaction. Copyright © 2012 Elsevier Ltd. All rights reserved.

  2. Transcriptomic Analysis of Carboxylic Acid Challenge in Escherichia coli: Beyond Membrane Damage

    PubMed Central

    Royce, Liam A.; Boggess, Erin; Fu, Yao; Liu, Ping; Shanks, Jacqueline V.; Dickerson, Julie; Jarboe, Laura R.

    2014-01-01

    Carboxylic acids are an attractive biorenewable chemical. Enormous progress has been made in engineering microbes for production of these compounds though titers remain lower than desired. Here we used transcriptome analysis of Escherichia coli during exogenous challenge with octanoic acid (C8) at pH 7.0 to probe mechanisms of toxicity. This analysis highlights the intracellular acidification and membrane damage caused by C8 challenge. Network component analysis identified transcription factors with altered activity including GadE, the activator of the glutamate-dependent acid resistance system (AR2) and Lrp, the amino acid biosynthesis regulator. The intracellular acidification was quantified during exogenous challenge, but was not observed in a carboxylic acid producing strain, though this may be due to lower titers than those used in our exogenous challenge studies. We developed a framework for predicting the proton motive force during adaptation to strong inorganic acids and carboxylic acids. This model predicts that inorganic acid challenge is mitigated by cation accumulation, but that carboxylic acid challenge inverts the proton motive force and requires anion accumulation. Utilization of native acid resistance systems was not useful in terms of supporting growth or alleviating intracellular acidification. AR2 was found to be non-functional, possibly due to membrane damage. We proposed that interaction of Lrp and C8 resulted in repression of amino acid biosynthesis. However, this hypothesis was not supported by perturbation of lrp expression or amino acid supplementation. E. coli strains were also engineered for altered cyclopropane fatty acid content in the membrane, which had a dramatic effect on membrane properties, though C8 tolerance was not increased. We conclude that achieving higher production titers requires circumventing the membrane damage. As higher titers are achieved, acidification may become problematic. PMID:24586888

  3. Direct esterification of ammonium salts of carboxylic acids

    DOEpatents

    Halpern, Yuval [Skokie, IL

    2003-06-24

    A non-catalytic process for producing esters, the process comprising reacting an ammonium salt of a carboxylic acid with an alcohol and removing ammonia from the reaction mixture. Selectivities for the desired ester product can exceed 95 percent.

  4. Sorption of carboxylic acid from carboxylic salt solutions at pHs close to or above the pK[sub a] of the acid, with regeneration with an aqueous solution of ammonia or low-molecular-weight alkylamine

    DOEpatents

    King, C.J.; Tung, L.A.

    1992-07-21

    Carboxylic acids are sorbed from aqueous feedstocks at pHs close to or above the acids' pH[sub a] into a strongly basic organic liquid phase or onto a basic solid adsorbent or moderately basic ion exchange resin. The acids are freed from the sorbent phase by treating it with aqueous alkylamine or ammonia thus forming an alkylammonium or ammonium carboxylate which dewatered and decomposed to the desired carboxylic acid and the alkylamine or ammonia. 8 figs.

  5. Rh(III)-Catalyzed Decarboxylative Coupling of Acrylic Acids with Unsaturated Oxime Esters: Carboxylic Acids Serve as Traceless Activators

    PubMed Central

    2015-01-01

    α,β-Unsaturated carboxylic acids undergo Rh(III)-catalyzed decarboxylative coupling with α,β-unsaturated O-pivaloyl oximes to provide substituted pyridines in good yield. The carboxylic acid, which is removed by decarboxylation, serves as a traceless activating group, giving 5-substituted pyridines with very high levels of regioselectivity. Mechanistic studies rule out a picolinic acid intermediate, and an isolable rhodium complex sheds further light on the reaction mechanism. PMID:24512241

  6. Carboxylic Acids as Indicators of Parent Body Conditions

    NASA Technical Reports Server (NTRS)

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

    1995-01-01

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

  7. ESTIMATION OF CARBOXYLIC ACID ESTER HYDROLYSIS RATE CONSTANTS

    EPA Science Inventory

    SPARC chemical reactivity models were extended to calculate hydrolysis rate constants for carboxylic acid esters from molecular structure. The energy differences between the initial state and the transition state for a molecule of interest are factored into internal and external...

  8. Selective reduction of carboxylic acids to aldehydes with hydrosilane via photoredox catalysis.

    PubMed

    Zhang, Muliang; Li, Nan; Tao, Xingyu; Ruzi, Rehanguli; Yu, Shouyun; Zhu, Chengjian

    2017-09-12

    The direct reduction of carboxylic acids to aldehydes with hydrosilane was achieved through visible light photoredox catalysis. The combination of both single electron transfer and hydrogen atom transfer steps offers a novel and convenient approach to selective reduction of carboxylic acids to aldehydes. The method also features mild conditions, high yields, broad substrate scope, and good functional group tolerance, such as alkyne, ester, ketone, amide and amine groups.

  9. The effect of carboxylic acids on the oxidation of coated iron oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Lengyel, Attila; Tolnai, Gyula; Klencsár, Zoltán; Garg, Vijayendra Kumar; de Oliveira, Aderbal Carlos; Herojit Singh, L.; Homonnay, Zoltán; Szalay, Roland; Németh, Péter; Szabolcs, Bálint; Ristic, Mira; Music, Svetozar; Kuzmann, Ernő

    2018-05-01

    57Fe Mössbauer spectroscopy, XRD, and TEM were used to investigate the effect of mandelic- and salicylic acid coatings on the iron oxide nanoparticles. These two carboxylic acids have similar molecules size and stoichiometry, but different structure and acidity. Significant differences were observed between the Mössbauer spectra of samples coated with mandelic acid and salicylic acid. These results indicate that the occurrence of iron microenvironments in the mandelic- and salicylic acid-coated iron oxide nanoparticles is different. The results can be interpreted in terms of the influence of the acidity of carboxylic acids on the formation, core/shell structure, and oxidation of coated iron oxide nanocomposites.

  10. [Physiological response to acetic acid stress of Acetobacter pasteuranus during vinegar fermentation].

    PubMed

    Qi, Zhengliang; Yang, Hailin; Xia, Xiaole; Wang, Wu; Leng, Yunwei; Yu, Xiaobin; Quan, Wu

    2014-03-04

    The aim of the study is to propose a dynamic acetic acid resistance mechanism through analysis on response of cellular morphology, physiology and metabolism of A. pasteurianus CICIM B7003 during vinegar fermentation. Vinegar fermentation was carried out in a Frings 9 L acetator by strain B7003 and cultures were sampled at different cellular growth phases. Simultaneously, percentage of capsular polysaccharide versus dry cells weight, ratio of unsaturated fatty acids to saturated fatty acids, transcription of acetic acid resistance genes, activity of alcohol respiratory chain enzymes and ATPase were detected for these samples to assay the responses of bacterial morphology, physiology and metabolism. When acetic acid was existed, no obvious capsular polysaccharide was secreted by cells. As vinegar fermentation proceeding, percentage of capsular polysaccharide versus dry cells weight was reduced from 2.5% to 0.89%. Ratio of unsaturated fatty acids to saturated fatty acids was increased obviously which can improve membrane fluidity. Also transcription level of acetic acid resistance genes was promoted. Interestingly, activity of alcohol respiratory chain and ATPase was not inhibited but promoted obviously with acetic acid accumulation which could provide enough energy for acetic acid resistance mechanism. On the basis of the results obtained from the experiment, A. pasteurianus CICIM B7003 relies mainly on the cooperation of changes of extracellular capsular polysaccharide and membrane fatty acids, activation of acid resistance genes transcription, enhancement of activity of alcohol respiratory chain and rapid energy production to tolerate acidic environment.

  11. Effect of acetic acid on lipid accumulation by glucose-fed activated sludge cultures

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

    Mondala, Andro; Hernandez, Rafael; French, Todd

    2012-01-01

    The effect of acetic acid, a lignocellulose hydrolysis by-product, on lipid accumulation by activated sludge cultures grown on glucose was investigated. This was done to assess the possible application of lignocellulose as low-cost and renewable fermentation substrates for biofuel feedstock production. Results: Biomass yield was reduced by around 54% at a 2 g L -1 acetic acid dosage but was increased by around 18% at 10 g L -1 acetic acid dosage relative to the control run. The final gravimetric lipid contents at 2 and 10 g L -1 acetic acid levels were 12.5 + 0.7% and 8.8 + 3.2%more » w/w, respectively, which were lower than the control (17.8 + 2.8% w/w). However, biodiesel yields from activated sludge grown with acetic acid (5.6 + 0.6% w/w for 2 g L -1 acetic acid and 4.2 + 3.0% w/w for 10 g L -1 acetic acid) were higher than in raw activated sludge (1-2% w/w). The fatty acid profiles of the accumulated lipids were similar with conventional plant oil biodiesel feedstocks. Conclusions: Acetic acid enhanced biomass production by activated sludge at high levels but reduced lipid production. Further studies are needed to enhance acetic acid utilization by activated sludge microorganisms for lipid biosynthesis.« less

  12. Genome-wide identification of Saccharomyces cerevisiae genes required for tolerance to acetic acid.

    PubMed

    Mira, Nuno P; Palma, Margarida; Guerreiro, Joana F; Sá-Correia, Isabel

    2010-10-25

    Acetic acid is a byproduct of Saccharomyces cerevisiae alcoholic fermentation. Together with high concentrations of ethanol and other toxic metabolites, acetic acid may contribute to fermentation arrest and reduced ethanol productivity. This weak acid is also a present in lignocellulosic hydrolysates, a highly interesting non-feedstock substrate in industrial biotechnology. Therefore, the better understanding of the molecular mechanisms underlying S. cerevisiae tolerance to acetic acid is essential for the rational selection of optimal fermentation conditions and the engineering of more robust industrial strains to be used in processes in which yeast is explored as cell factory. The yeast genes conferring protection against acetic acid were identified in this study at a genome-wide scale, based on the screening of the EUROSCARF haploid mutant collection for susceptibility phenotypes to this weak acid (concentrations in the range 70-110 mM, at pH 4.5). Approximately 650 determinants of tolerance to acetic acid were identified. Clustering of these acetic acid-resistance genes based on their biological function indicated an enrichment of genes involved in transcription, internal pH homeostasis, carbohydrate metabolism, cell wall assembly, biogenesis of mitochondria, ribosome and vacuole, and in the sensing, signalling and uptake of various nutrients in particular iron, potassium, glucose and amino acids. A correlation between increased resistance to acetic acid and the level of potassium in the growth medium was found. The activation of the Snf1p signalling pathway, involved in yeast response to glucose starvation, is demonstrated to occur in response to acetic acid stress but no evidence was obtained supporting the acetic acid-induced inhibition of glucose uptake. Approximately 490 of the 650 determinants of tolerance to acetic acid identified in this work are implicated, for the first time, in tolerance to this weak acid. These are novel candidate genes for genetic

  13. Effects of acetic acid on the viability of Ascaris lumbricoides eggs

    PubMed Central

    Beyhan, Yunus E.; Yilmaz, Hasan; Hokelek, Murat

    2016-01-01

    Objectives: To investigate the effects of acetic acid on durable Ascaris lumbricoides (A. lumbricoides) eggs to determine the effective concentration of vinegar and the implementation period to render the consumption of raw vegetables more reliable. Methods: This experimental study was performed in May 2015 in the Parasitology Laboratory, Faculty of Medicine, Yuzuncu Yil University, Van, Turkey. The A. lumbricoides eggs were divided into 2 groups. Eggs in the study group were treated with 1, 3, 5, and 10% acetic acid concentrations, and eggs in the control group were treated with Eosin. The eggs’ viability was observed at the following points in time during the experiment: 0, 10, 15, 20, 30, 45, and 60 minutes. Results: The 1% acetic acid was determined insufficient on the viability of Ascaris eggs. At the 30th minute, 3% acetic acid demonstrated 95% effectiveness, and at 5% concentration, all eggs lost their viability. Treatment of acetic acid at the ratio of 4.8% in 30 minutes, or a ratio of 4.3% in 60 minutes is required for full success of tretment. Conclusion: Since Ascaris eggs have 3 layers and are very resistant, the acetic acid concentration, which can be effective on these eggs are thought to be effective also on many other parasitic agents. In order to attain an active protection, after washing the vegetables, direct treatment with a vinegar containing 5% acetic acid for 30 minutes is essential. PMID:26905351

  14. Aerobic Oxidation of 5-(Hydroxymethyl)furfural Cyclic Acetal Enables Selective Furan-2,5-dicarboxylic Acid Formation with CeO2 -Supported Gold Catalyst.

    PubMed

    Kim, Minjune; Su, Yaqiong; Fukuoka, Atsushi; Hensen, Emiel J M; Nakajima, Kiyotaka

    2018-05-14

    The utilization of 5-(hydroxymethyl)furfural (HMF) for the large-scale production of essential chemicals has been largely limited by the formation of solid humin as a byproduct, which prevents the operation of stepwise batch-type and continuous flow-type processes. The reaction of HMF with 1,3-propanediol produces an HMF acetal derivative that exhibits excellent thermal stability. Aerobic oxidation of the HMF acetal with a CeO 2 -supported Au catalyst and Na 2 CO 3 in water gives a 90-95 % yield of furan 2,5-dicarboxylic acid, an increasingly important commodity chemical for the biorenewables industry, from concentrated solutions (10-20 wt %) without humin formation. The six-membered acetal ring suppresses thermal decomposition and self-polymerization of HMF in concentrated solutions. Kinetic studies supported by DFT calculations identify two crucial steps in the reaction mechanism, that is, the partial hydrolysis of the acetal into 5-formyl-2-furan carboxylic acid involving OH - and Lewis acid sites on CeO 2 , and subsequent oxidative dehydrogenation of the in situ generated hemiacetal involving Au nanoparticles. These results represent a significant advance over the current state of the art, overcoming an inherent limitation of the oxidation of HMF to an important monomer for biopolymer production. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Scaleable production and separation of fermentation-derived acetic acid. Final CRADA report.

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

    Snyder, S. W.; Energy Systems

    2010-02-08

    Half of U.S. acetic acid production is used in manufacturing vinyl acetate monomer (VAM) and is economical only in very large production plants. Nearly 80% of the VAM is produced by methanol carbonylation, which requires high temperatures and exotic construction materials and is energy intensive. Fermentation-derived acetic acid production allows for small-scale production at low temperatures, significantly reducing the energy requirement of the process. The goal of the project is to develop a scaleable production and separation process for fermentation-derived acetic acid. Synthesis gas (syngas) will be fermented to acetic acid, and the fermentation broth will be continuously neutralized withmore » ammonia. The acetic acid product will be recovered from the ammonium acid broth using vapor-based membrane separation technology. The process is summarized in Figure 1. The two technical challenges to success are selecting and developing (1) microbial strains that efficiently ferment syngas to acetic acid in high salt environments and (2) membranes that efficiently separate ammonia from the acetic acid/water mixture and are stable at high enough temperature to facilitate high thermal cracking of the ammonium acetate salt. Fermentation - Microbial strains were procured from a variety of public culture collections (Table 1). Strains were incubated and grown in the presence of the ammonium acetate product and the fastest growing cultures were selected and incubated at higher product concentrations. An example of the performance of a selected culture is shown in Figure 2. Separations - Several membranes were considered. Testing was performed on a new product line produced by Sulzer Chemtech (Germany). These are tubular ceramic membranes with weak acid functionality (see Figure 3). The following results were observed: (1) The membranes were relatively fragile in a laboratory setting; (2) Thermally stable {at} 130 C in hot organic acids; (3) Acetic acid rejection > 99%; and

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

    NASA Technical Reports Server (NTRS)

    Lewer, P.; Bandurski, R. S.

    1987-01-01

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

  17. Aqueous-Phase Acetic Acid Ketonization over Monoclinic Zirconia

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

    Cai, Qiuxia; Lopez-Ruiz, Juan A.; Cooper, Alan R.

    The effect of aqueous phase on the acetic acid ketonization over monoclinic zirconia has been investigated using first-principles based density functional theory (DFT) calculations. To capture the aqueous phase chemistry over the solid zirconia catalyst surface, the aqueous phase is represented by 111 explicit water molecules with a liquid water density of 0.93 g/cm3 and the monoclinic zirconia is modeled by the most stable surface structure . The dynamic nature of aqueous phase/ interface was studied using ab initio molecular dynamics simulation, indicating that nearly half of the surface Zr sites are occupied by either adsorbed water molecules or hydroxylmore » groups at 550 K. DFT calculations show that the adsorption process of acetic acid from the liquid water phase to the surface is nearly thermodynamically neutral with a Gibbs free energy of -2.3 kJ/mol although the adsorption strength of acetic acid on the surface in aqueous phase is much stronger than in vapor phase. Therefore it is expected that the adsorption of acetic acid will dramatically affects aqueous phase ketonization reactivity over the monoclinic zirconia catalyst. Using the same ketonization mechanism via the β-keto acid intermediate, we have compared acetic acid ketonization to acetone in both vapor and aqueous phases. Our DFT calculation results show although the rate-determining step of the β-keto acid formation via the C-C coupling is not pronouncedly affected, the presence of liquid water molecules will dramatically affect dehydrogenation and hydrogenation steps via proton transfer mechanism. This work was financially supported by the United States Department of Energy (DOE)’s Bioenergy Technologies Office (BETO) and performed at the Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated for DOE by Battelle Memorial Institute. Computing time and advanced catalyst characterization use was granted by a user proposal at the William R. Wiley

  18. Detection of CIN by naked eye visualization after application of acetic acid.

    PubMed

    Londhe, M; George, S S; Seshadri, L

    1997-06-01

    A prospective study was undertaken to determine the sensitivity and specificity of acetic application to the cervix followed by naked eye visualization as a screening test for detection of cervical intraepithelial neoplasia. Three hundred and seventy two sexually active woman in the reproductive age group were studied. All the women underwent Papanicolaou test, acetic acid test and colposcopy. One hundred and seventy five woman were acetic acid test negative, 197 women were acetic acid test positive. The sensitivity of acetic acid test was 72.4%, specificity 54% and false negative rate 15.2%, as compared to papanicolaou test which had a sensitivity of 13.2%, specificity of 96.3% and false negative rate of 24.4%. The advantage of the acetic acid test lies in its easy technique, low cost and high sensitivity which are important factors for determining the efficacy of any screening programme in developing countries.

  19. Acetic acid bacteria: A group of bacteria with versatile biotechnological applications.

    PubMed

    Saichana, Natsaran; Matsushita, Kazunobu; Adachi, Osao; Frébort, Ivo; Frebortova, Jitka

    2015-11-01

    Acetic acid bacteria are gram-negative obligate aerobic bacteria assigned to the family Acetobacteraceae of Alphaproteobacteria. They are members of the genera Acetobacter, Gluconobacter, Gluconacetobacter, Acidomonas, Asaia, Kozakia, Swaminathania, Saccharibacter, Neoasaia, Granulibacter, Tanticharoenia, Ameyamaea, Neokomagataea, and Komagataeibacter. Many strains of Acetobacter and Komagataeibacter have been known to possess high acetic acid fermentation ability as well as the acetic acid and ethanol resistance, which are considered to be useful features for industrial production of acetic acid and vinegar, the commercial product. On the other hand, Gluconobacter strains have the ability to perform oxidative fermentation of various sugars, sugar alcohols, and sugar acids leading to the formation of several valuable products. Thermotolerant strains of acetic acid bacteria were isolated in order to serve as the new strains of choice for industrial fermentations, in which the cooling costs for maintaining optimum growth and production temperature in the fermentation vessels could be significantly reduced. Genetic modifications by adaptation and genetic engineering were also applied to improve their properties, such as productivity and heat resistance. Copyright © 2014 Elsevier Inc. All rights reserved.

  20. Overexpression of acetyl-CoA synthetase in Saccharomyces cerevisiae increases acetic acid tolerance

    PubMed Central

    Ding, Jun; Holzwarth, Garrett; Penner, Michael H.; Patton-Vogt, Jana; Bakalinsky, Alan T.

    2015-01-01

    Acetic acid-mediated inhibition of the fermentation of lignocellulose-derived sugars impedes development of plant biomass as a source of renewable ethanol. In order to overcome this inhibition, the capacity of Saccharomyces cerevisiae to synthesize acetyl-CoA from acetic acid was increased by overexpressing ACS2 encoding acetyl-coenzyme A synthetase. Overexpression of ACS2 resulted in higher resistance to acetic acid as measured by an increased growth rate and shorter lag phase relative to a wild-type control strain, suggesting that Acs2-mediated consumption of acetic acid during fermentation contributes to acetic acid detoxification. PMID:25673654

  1. Extractive fermentation of acetic acid

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

    Busche, R.M.

    1991-12-31

    In this technoeconomic evaluation of the manufacture of acetic acid by fermentation, the use of the bacterium: Acetobacter suboxydans from the old vinegar process was compared with expected performance of the newer Clostridium thermoaceticum bacterium. Both systems were projected to operate as immobilized cells in a continuous, fluidized bed bioreactor, using solvent extraction to recover the product. Acetobacter metabolizes ethanol aerobically to produce acid at 100 g/L in a low pH medium. This ensures that the product is in the form of a concentrated extractable free acid, rather than as an unextractable salt. Unfortunately, yields from glucose by way ofmore » the ethanol fermentation are poor, but near the biological limits of the organisms involved. Conversely, C. thermoaceticum is a thermophilic anaerobe that operates at high fermentation rates on glucose at neutral pH to produce acetate salts directly in substantially quantitative yields. However, it is severely inhibited by product, which restricts concentration to a dilute 20 g/L. An improved Acetobacter system operating with recycled cells at 50 g/L appears capable of producing acid at $0.38/lb, as compared with a $0.29/lb price for synthetic acid. However, this system has only a limited margin for process improvement. The present Clostridium system cannot compete, since the required selling price would be $0.42/lb. However, if the organism could be adapted to tolerate higher product concentrations at acid pH, selling price could be reduced to $0.22/lb, or about 80% of the price of synthetic acid.« less

  2. Gas chromatography/isotope ratio mass spectrometry: analysis of methanol, ethanol and acetic acid by direct injection of aqueous alcoholic and acetic acid samples.

    PubMed

    Ai, Guomin; Sun, Tong; Dong, Xiuzhu

    2014-08-15

    Methanol, ethanol, and acetic acid are not easily extracted from aqueous samples and are susceptible to isotope fractionation in gas chromatography/isotope ratio mass spectrometry (GC/IRMS) analysis. Developing a direct dilution GC/IRMS method for aqueous samples, by adjusting the sample concentrations in common solvents to be similar to each other and using a fixed GC split ratio, is very convenient and important because any linearity effects caused by amount-dependent isotope fractionation can be avoided. The suitability of acetonitrile and acetone solvents for the GC/IRMS analysis of pure methanol, ethanol and acetic acid, and commercial liquor and vinegar samples was evaluated using n-hexane and water as control solvents. All the solvents including water were separated from the analyte on a HP-INNOWAX column and were diverted away from the combustion interface. The influence of liquor matrix on the ethanol GC/IRMS analyses was evaluated by adding pure ethanol to liquor samples. Acetonitrile and acetone gave similar δ(13) C values for pure ethanol and pure acetic acid to those obtained in water and n-hexane, and also gave similar δ(13) C values of ethanol in liquor and acetic acid in white vinegar to that obtained in water. For methanol analysis, acetonitrile and refined acetone gave similar δ(13) C values to that obtained in water, but n-hexane was not a suitable solvent. In addition, isotopic fractionation caused by solvent and solute interactions was observed. We recommend using acetonitrile for the GC/IRMS analysis of aqueous alcoholic samples, and acetone for the analysis of aqueous acetic acid samples. This direct dilution method can provide high accurate and precise GC/IRMS analysis of the relative changes in δ(13) C values of methanol, ethanol, and acetic acid. Copyright © 2014 John Wiley & Sons, Ltd.

  3. Improvement of ruthenium based decarboxylation of carboxylic acids

    USDA-ARS?s Scientific Manuscript database

    The removal of oxygen atoms from biobased carboxylic acids is an attractive route to provide the drop in replacement feedstocks that industry needs to continue to provide high performance products. Through the use of ruthenium catalysis, an efficient method where this process can be accomplished on ...

  4. Zwitterionic metal carboxylate complexes: In solid state

    NASA Astrophysics Data System (ADS)

    Nath, Bhaskar; Kalita, Dipjyoti; Baruah, Jubaraj B.

    2012-07-01

    A flexible dicarboxylic acid having composition [(CH(o-C5H4N)(p-C6H4OCH2CO2H)2] derived from corresponding bis-phenol reacts with various metal(II) acetates such as manganese(II), cobalt(II) and nickel(II) acetate leads to zwtterionic complexes with compositions [CH(o-C5H4N)(p-C6H4OCH2CO2){p-C6H4OCH2CO2M(H2O)5}].6H2O (where M = Mn, Co, Ni). The complexes are characterised by X-ray crystallography. These complexes have chiral center due to unsymmetric structure conferred to the ligand through coordination at only one carboxylate group of the ligand. In solid state these complexes are racemic.

  5. Effect of salt addition on acid resistance response of Escherichia coli O157:H7 against acetic acid.

    PubMed

    Bae, Young-Min; Lee, Sun-Young

    2017-08-01

    A combination of salt and acid is commonly used in the production of many foods, such as pickles and fermented foods. However, in our previous studies, addition of salt significantly reduced the inhibitory effect of acetic acid against E. coli O157:H7 in laboratory media and pickled cucumbers. Therefore, this study was conducted to determine the effect of salt addition on the acid resistance (AR) response of E. coli O157:H7 after treatment with acetic acid. The combined effect of acetic acid and salt showed different results depending on media tested. Organic compounds such as yeast extract and tryptone were required to observe the antagonistic effect of salt and acetic acid in combination. However, use of an rpoS mutant or addition of chloramphenicol resulted in no changes in the antagonistic effect of acetic acid and salt. The addition of glutamate to phosphate buffer significantly increased the survival levels of E. coli O157:H7 after the acetic acid treatment; however, the survival levels were lower than those after the treatment with acetic acid alone. Thus, the addition of salt may increase the AR response of E. coli O157:H7; however, these survival mechanisms were not proven clearly. Therefore, further studies need to be performed to better understand the antagonism of acetic acid salt against E. coli O157:H7. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. Ion-exclusion chromatography with conductimetric detection of aliphatic carboxylic acids on a weakly acidic cation-exchange resin by elution with benzoic acid-beta-cyclodextrin.

    PubMed

    Tanaka, Kazuhiko; Mori, Masanobu; Xu, Qun; Helaleh, Murad I H; Ikedo, Mikaru; Taoda, Hiroshi; Hu, Wenzhi; Hasebe, Kiyoshi; Fritz, James S; Haddad, Paul R

    2003-05-16

    In this study, an aqueous solution consisting of benzoic acid with low background conductivity and beta-cyclodextrin (beta-CD) of hydrophilic nature and the inclusion effect to benzoic acid were used as eluent for the ion-exclusion chromatographic separation of aliphatic carboxylic acids with different pKa values and hydrophobicity on a polymethacrylate-based weakly acidic cation-exchange resin in the H+ form. With increasing concentration of beta-cyclodextrin in the eluent, the retention times of the carboxylic acids decreased due to the increased hydrophilicity of the polymethacrylate-based cation-exchange resin surface from the adsorption of OH groups of beta-cyclodextrin. Moreover, the eluent background conductivity decreased with increasing concentration of beta-cyclodextrin in 1 mM benzoic acid, which could result in higher sensitivity for conductimetric detection. The ion-exclusion chromatographic separation of carboxylic acids with high resolution and sensitivity was accomplished successfully by elution with a 1 mM benzoic acid-10 mM cyclodextrin solution without chemical suppression.

  7. Electrocarboxylation: towards sustainable and efficient synthesis of valuable carboxylic acids

    PubMed Central

    Matthessen, Roman; Fransaer, Jan; Binnemans, Koen

    2014-01-01

    Summary The near-unlimited availability of CO2 has stimulated a growing research effort in creating value-added products from this greenhouse gas. This paper presents the trends on the most important methods used in the electrochemical synthesis of carboxylic acids from carbon dioxide. An overview is given of different substrate groups which form carboxylic acids upon CO2 fixation, including mechanistic considerations. While most work focuses on the electrocarboxylation of substrates with sacrificial anodes, this review considers the possibilities and challenges of implementing other synthetic methodologies. In view of potential industrial application, the choice of reactor setup, electrode type and reaction pathway has a large influence on the sustainability and efficiency of the process. PMID:25383120

  8. Effects of Ethanol and Other Alkanols on Transport of Acetic Acid in Saccharomyces cerevisiae

    PubMed Central

    Casal, Margarida; Cardoso, Helena; Leão, Cecília

    1998-01-01

    In glucose-grown cells of Saccharomyces cerevisiae IGC 4072, acetic acid enters only by simple diffusion of the undissociated acid. In these cells, ethanol and other alkanols enhanced the passive influx of labelled acetic acid. The influx of the acid followed first-order kinetics with a rate constant that increased exponentially with the alcohol concentration, and an exponential enhancement constant for each alkanol was estimated. The intracellular concentration of labelled acetic acid was also enhanced by alkanols, and the effect increased exponentially with alcohol concentration. Acetic acid is transported across the plasma membrane of acetic acid-, lactic acid-, and ethanol-grown cells by acetate-proton symports. We found that in these cells ethanol and butanol inhibited the transport of labelled acetic acid in a noncompetitive way; the maximum transport velocity decreased with alcohol concentration, while the affinity of the system for acetate was not significantly affected by the alcohol. Semilog plots of Vmax versus alcohol concentration yielded straight lines with negative slopes from which estimates of the inhibition constant for each alkanol could be obtained. The intracellular concentration of labelled acid was significantly reduced in the presence of ethanol or butanol, and the effect increased with the alcohol concentration. We postulate that the absence of an operational carrier for acetate in glucose-grown cells of S. cerevisiae, combined with the relatively high permeability of the plasma membrane for the undissociated acid and the inability of the organism to metabolize acetic acid, could be one of the reasons why this species exhibits low tolerance to acidic environments containing ethanol. PMID:9464405

  9. Two Dimensional Polyamides Prepared From Unsaturated Carboxylic Acids And Amines.

    DOEpatents

    McDonald, William F.; Huang, Zhi Heng; Wright, Stacy C.; Danzig, Morris; Taylor, Andrew C.

    2002-07-17

    A polyamide and a process for preparing the polyamide are disclosed. The process comprises reacting in a reaction mixture a monomer selected from unsaturated carboxylic acids, esters of unsaturated carboxylic acids, anhydrides of unsaturated carboxylic acids, and mixtures thereof, and a first amine to form an intermediate reaction product in the reaction mixture, wherein the first amine is selected from RR.sub.1 NH, RNH.sub.2, RR.sub.1 NH.sub.2.sup.+, RNH.sub.3.sup.+ and mixtures thereof, wherein R and R.sub.1 can be the same or different and each contain between about 1 and 50 carbon atoms and are optionally substituted with heteroatoms oxygen, nitrogen, sulfur, and phosphorus and combinations thereof, and reacting the intermediate reaction product and a second amine to form a polyamide, wherein the second amine is selected from R.sub.2 R.sub.3 NH, R.sub.2 NH.sub.2, R.sub.2 R.sub.3 NH.sub.2.sup.+, R.sub.2 NH.sub.3.sup.+ and mixtures thereof wherein R.sub.2 and R.sub.3 can be the same or different and each contain between about 1 and 50 carbon atoms and are optionally substituted with heteroatoms oxygen, nitrogen, sulfur, and phosphorus and combinations thereof, wherein multiple of the R, R.sub.1, R.sub.2, and R.sub.3 are in vertically aligned spaced relationship along a backbone formed by the polyamide. In one version of the invention, the monomer is selected from maleic anhydride, maleic acid esters, and mixtures thereof. In another version of the invention, the first amine is an alkylamine, such as tetradecylamine, and the second amine is a polyalkylene polyamine, such as pentaethylenehexamine. In yet another version of the invention, the first amine and the second amine are olefinic or acetylenic amines, such as the reaction products of an alkyldiamine and an acetylenic carboxylic acid. The first amine and the second amine may be the same or different depending on the desired polyamide polymer structure.

  10. Interaction effects of lactic acid and acetic acid at different temperatures on ethanol production by Saccharomyces cerevisiae in corn mash.

    PubMed

    Graves, Tara; Narendranath, Neelakantam V; Dawson, Karl; Power, Ronan

    2007-01-01

    The combined effects of lactic acid and acetic acid on ethanol production by S. cerevisiae in corn mash, as influenced by temperature, were examined. Duplicate full factorial experiments (three lactic acid concentrations x three acetic acid concentrations) were performed to evaluate the interaction between lactic and acetic acids on the ethanol production of yeast at each of the three temperatures, 30, 34, and 37 degrees C. Corn mash at 30% dry solids adjusted to pH 4 after lactic and acetic acid addition was used as the substrate. Ethanol production rates and final ethanol concentrations decreased (P<0.001) progressively as the concentration of combined lactic and acetic acids in the corn mash increased and the temperature was raised from 30 to 37 degrees C. At 30 degrees C, essentially no ethanol was produced after 96 h when 0.5% w/v acetic acid was present in the mash (with 0.5, 2, and 4% w/v lactic acid). At 34 and 37 degrees C, the final concentrations of ethanol produced by the yeast were noticeably reduced by the presence of 0.3% w/v acetic acid and >or=2% w/v lactic acid. It can be concluded that, as in previous studies with defined media, lactic acid and acetic acid act synergistically to reduce ethanol production by yeast in corn mash. In addition, the inhibitory effects of combined lactic and acetic acid in corn mash were more apparent at elevated temperatures.

  11. Overexpression of acetyl-CoA synthetase in Saccharomyces cerevisiae increases acetic acid tolerance.

    PubMed

    Ding, Jun; Holzwarth, Garrett; Penner, Michael H; Patton-Vogt, Jana; Bakalinsky, Alan T

    2015-01-01

    Acetic acid-mediated inhibition of the fermentation of lignocellulose-derived sugars impedes development of plant biomass as a source of renewable ethanol. In order to overcome this inhibition, the capacity of Saccharomyces cerevisiae to synthesize acetyl-CoA from acetic acid was increased by overexpressing ACS2 encoding acetyl-coenzyme A synthetase. Overexpression of ACS2 resulted in higher resistance to acetic acid as measured by an increased growth rate and shorter lag phase relative to a wild-type control strain, suggesting that Acs2-mediated consumption of acetic acid during fermentation contributes to acetic acid detoxification. © FEMS 2014. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  12. Analysis of carbonaceous biomarkers with the Mars Organic Analyzer microchip capillary electrophoresis system: carboxylic acids.

    PubMed

    Stockton, Amanda M; Tjin, Caroline Chandra; Chiesl, Thomas N; Mathies, Richard A

    2011-01-01

    The oxidizing surface chemistry on Mars argues that any comprehensive search for organic compounds indicative of life requires methods to analyze higher oxidation states of carbon with very low limits of detection. To address this goal, microchip capillary electrophoresis (μCE) methods were developed for analysis of carboxylic acids with the Mars Organic Analyzer (MOA). Fluorescent derivatization was achieved by activation with the water soluble 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) followed by reaction with Cascade Blue hydrazide in 30 mM borate, pH 3. A standard containing 12 carboxylic acids found in terrestrial life was successfully labeled and separated in 30 mM borate at pH 9.5, 20 °C by using the MOA CE system. Limits of detection were 5-10 nM for aliphatic monoacids, 20 nM for malic acid (diacid), and 230 nM for citric acid (triacid). Polyacid benzene derivatives containing 2, 3, 4, and 6 carboxyl groups were also analyzed. In particular, mellitic acid was successfully labeled and analyzed with a limit of detection of 300 nM (5 ppb). Analyses of carboxylic acids sampled from a lava tube cave and a hydrothermal area demonstrated the versatility and robustness of our method. This work establishes that the MOA can be used for sensitive analyses of a wide range of carboxylic acids in the search for extraterrestrial organic molecules. © Mary Ann Liebert, Inc.

  13. Dissolving Carboxylic Acids and Primary Amines on the Overhead Projector

    ERIC Educational Resources Information Center

    Solomon, Sally D.; Rutkowsky, Susan A.

    2010-01-01

    Liquid carboxylic acids (or primary amines) with limited solubility in water are dissolved by addition of aqueous sodium hydroxide (or hydrochloric acid) on the stage of an overhead projector using simple glassware and very small quantities of chemicals. This effective and colorful demonstration can be used to accompany discussions of the…

  14. Performance of dairy cows fed high levels of acetic acid or ethanol.

    PubMed

    Daniel, J L P; Amaral, R C; Sá Neto, A; Cabezas-Garcia, E H; Bispo, A W; Zopollatto, M; Cardoso, T L; Spoto, M H F; Santos, F A P; Nussio, L G

    2013-01-01

    Ethanol and acetic acid are common end products from silages. The main objective of this study was to determine whether high concentrations of ethanol or acetic acid in total mixed ration would affect performance in dairy cows. Thirty mid-lactation Holstein cows were grouped in 10 blocks and fed one of the following diets for 7 wk: (1) control (33% Bermuda hay + 67% concentrates), (2) ethanol [control diet + 5% ethanol, dry matter (DM) basis], or (3) acetic acid (control diet + 5% acetic acid, DM basis). Ethanol and acetic acid were diluted in water (1:2) and sprayed onto total mixed rations twice daily before feeding. An equal amount of water was mixed with the control ration. To adapt animals to these treatments, cows were fed only half of the treatment dose during the first week of study. Cows fed ethanol yielded more milk (37.9 kg/d) than those fed the control (35.8 kg/d) or acetic acid (35.3 kg/d) diets, mainly due to the higher DM intake (DMI; 23.7, 22.2, and 21.6 kg/d, respectively). The significant diet × week interaction for DMI, mainly during wk 2 and 3 (when acetic acid reached the full dose), was related to the decrease in DMI observed for the acetic acid treatment. There was a diet × week interaction in excretion of milk energy per DMI during wk 2 and 3, due to cows fed acetic acid sustained milk yield despite lower DMI. Energy efficiency was similar across diets. Blood metabolites (glucose, insulin, nonesterified fatty acids, ethanol, and γ-glutamyl transferase activity) and sensory characteristics of milk were not affected by these treatments. Animal performance suggested similar energy value for the diet containing ethanol compared with other diets. Rumen conversion of ethanol to acetate and a concomitant increase in methane production might be a plausible explanation for the deviation of the predicted energy value based on the heat of combustion. Therefore, the loss of volatile compounds during the drying process in the laboratory should be

  15. Photoelectron spectra of some antibiotic building blocks: 2-azetidinone and thiazolidine-carboxylic acid.

    PubMed

    Ahmed, Marawan; Ganesan, Aravindhan; Wang, Feng; Feyer, Vitaliy; Plekan, Oksana; Prince, Kevin C

    2012-08-23

    X-ray photoelectron spectra of the core and valence levels of the fundamental building blocks of β-lactam antibiotics have been investigated and compared with theoretical calculations. The spectra of the compounds 2-azetidinone and the 2- and 4-isomers of thiazolidine-carboxylic acid are interpreted in the light of theoretical calculations. The spectra of the two isomers of thiazolidine-carboxylic acid are rather similar, as expected, but show clear effects due to isomerization. Both isomers are analogues of proline, which is well-known to populate several low energy conformers in the gas phase. We have investigated the low energy conformers of thiazolidine-4-carboxylic acid theoretically in more detail and find some spectroscopic evidence that multiple conformers may be present. The measured valence levels are assigned for all three compounds, and the character of the frontier orbitals is identified and analyzed.

  16. Acetic Acid Causes Endoplasmic Reticulum Stress and Induces the Unfolded Protein Response in Saccharomyces cerevisiae

    PubMed Central

    Kawazoe, Nozomi; Kimata, Yukio; Izawa, Shingo

    2017-01-01

    Since acetic acid inhibits the growth and fermentation ability of Saccharomyces cerevisiae, it is one of the practical hindrances to the efficient production of bioethanol from a lignocellulosic biomass. Although extensive information is available on yeast response to acetic acid stress, the involvement of endoplasmic reticulum (ER) and unfolded protein response (UPR) has not been addressed. We herein demonstrated that acetic acid causes ER stress and induces the UPR. The accumulation of misfolded proteins in the ER and activation of Ire1p and Hac1p, an ER-stress sensor and ER stress-responsive transcription factor, respectively, were induced by a treatment with acetic acid stress (>0.2% v/v). Other monocarboxylic acids such as propionic acid and sorbic acid, but not lactic acid, also induced the UPR. Additionally, ire1Δ and hac1Δ cells were more sensitive to acetic acid than wild-type cells, indicating that activation of the Ire1p-Hac1p pathway is required for maximum tolerance to acetic acid. Furthermore, the combination of mild acetic acid stress (0.1% acetic acid) and mild ethanol stress (5% ethanol) induced the UPR, whereas neither mild ethanol stress nor mild acetic acid stress individually activated Ire1p, suggesting that ER stress is easily induced in yeast cells during the fermentation process of lignocellulosic hydrolysates. It was possible to avoid the induction of ER stress caused by acetic acid and the combined stress by adjusting extracellular pH. PMID:28702017

  17. Megasphaera hexanoica sp. nov., a medium-chain carboxylic acid-producing bacterium isolated from a cow rumen.

    PubMed

    Jeon, Byoung Seung; Kim, Seil; Sang, Byoung-In

    2017-07-01

    Strain MHT, a strictly anaerobic, Gram-stain-negative, non-spore-forming, spherical coccus or coccoid-shaped microorganism, was isolated from a cow rumen during a screen for hexanoic acid-producing bacteria. The microorganism grew at 30-40 °C and pH 5.5-7.5 and exhibited production of various short- and medium-chain carboxylic acids (acetic acid, butyric acid, pentanoic acid, isobutyric acid, isovaleric acid, hexanoic acid, heptanoic acid and octanoic acid), as well as H2 and CO2 as biogas. Phylogenetic analysis based on 16S rRNA gene sequencing demonstrated that MHT represents a member of the genus Megasphaera, with the closest relatives being Megapsphaera indica NMBHI-10T (94.1 % 16S rRNA sequence similarity), Megasphaera elsdenii DSM 20460T (93.8 %) and Megasphaera paucivorans DSM 16981T (93.8 %). The major cellular fatty acids produced by MHT included C12 : 0, C16 : 0, C18 : 1cis 9, and C18 : 0, and the DNA G+C content of the MHT genome is 51.8 mol%. Together, the distinctive phenotypic and phylogenetic characteristics of MHT indicate that this microorganism represents a novel species of the genus Megasphaera, for which the name Megasphaera hexanoica sp. nov. is herein proposed. The type strain of this species is MHT (=KCCM 43214T=JCM 31403T).

  18. Using parahydrogen to hyperpolarize amines, amides, carboxylic acids, alcohols, phosphates, and carbonates

    PubMed Central

    Iali, Wissam; Rayner, Peter J.; Duckett, Simon B.

    2018-01-01

    Hyperpolarization turns weak nuclear magnetic resonance (NMR) and magnetic resonance imaging (MRI) responses into strong signals, so normally impractical measurements are possible. We use parahydrogen to rapidly hyperpolarize appropriate 1H, 13C, 15N, and 31P responses of analytes (such as NH3) and important amines (such as phenylethylamine), amides (such as acetamide, urea, and methacrylamide), alcohols spanning methanol through octanol and glucose, the sodium salts of carboxylic acids (such as acetic acid and pyruvic acid), sodium phosphate, disodium adenosine 5′-triphosphate, and sodium hydrogen carbonate. The associated signal gains are used to demonstrate that it is possible to collect informative single-shot NMR spectra of these analytes in seconds at the micromole level in a 9.4-T observation field. To achieve these wide-ranging signal gains, we first use the signal amplification by reversible exchange (SABRE) process to hyperpolarize an amine or ammonia and then use their exchangeable NH protons to relay polarization into the analyte without changing its identity. We found that the 1H signal gains reach as high as 650-fold per proton, whereas for 13C, the corresponding signal gains achieved in a 1H-13C refocused insensitive nuclei enhanced by polarization transfer (INEPT) experiment exceed 570-fold and those in a direct-detected 13C measurement exceed 400-fold. Thirty-one examples are described to demonstrate the applicability of this technique. PMID:29326984

  19. Crystal structures and hydrogen bonding in the anhydrous tryptaminium salts of the isomeric (2,4-di­chloro­phen­oxy)acetic and (3,5-di­chloro­phen­oxy)acetic acids

    PubMed Central

    Smith, Graham; Lynch, Daniel E.

    2015-01-01

    The anhydrous salts of 2-(1H-indol-3-yl)ethanamine (tryptamine) with isomeric (2,4-di­chloro­phen­oxy)acetic acid (2,4-D) and (3,5-di­chloro­phen­oxy)acetic (3,5-D), both C10H13N2 +·C8H5Cl2O3 − [(I) and (II), respectively], have been determined and their one-dimensional hydrogen-bonded polymeric structures are described. In the crystal of (I), the aminium H atoms are involved in three separate inter-species N—H⋯O hydrogen-bonding inter­actions, two with carboxyl­ate O-atom acceptors and the third in an asymmetric three-centre bidentate carboxyl­ate O,O′ chelate [graph set R 1 2(4)]. The indole H atom forms an N—H⋯Ocarboxyl­ate hydrogen bond, extending the chain structure along the b-axis direction. In (II), two of the three aminium H atoms are also involved in N—H⋯Ocarboxyl­ate hydrogen bonds similar to (I) but with the third, a three-centre asymmetric inter­action with carboxyl­ate and phen­oxy O atoms is found [graph set R 1 2(5)]. The chain polymeric extension is also along b. There are no π–π ring inter­actions in either of the structures. The aminium side-chain conformations differ significantly between the two structures, reflecting the conformational ambivalence of the tryptaminium cation, as found also in the benzoate salts. PMID:26090147

  20. Interconversion of biologically important carboxylic acids by radiation

    NASA Technical Reports Server (NTRS)

    Negron-Mendoza, A.; Ponnamperuma, C.

    1978-01-01

    The interconversion of a group of biologically important polycarboxylic acids (acetic, fumaric, malic, malonic, succinic, citric, isocitric, tricarballylic) under gamma-ray or ultraviolet radiation was investigated. The formation of high molecular weight compounds was observed in all cases. Succinic acid was formed in almost all radiolysis experiments. Citric, malonic, and succinic acids appeared to be relatively insensitive to radiation. Interconversion of the polycarboxylic acids studied may have occurred under the effect of radiation in the prebiotic earth.

  1. ON THE FORMATION OF BENZOIC ACID AND HIGHER-ORDER BENZENE CARBOXYLIC ACIDS IN INTERSTELLAR MODEL ICE GRAINS

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

    McMurtry, Brandon M.; Saito, Sean E. J.; Turner, A

    With a binary ice mixture of benzene (C{sub 6}H{sub 6}) and carbon dioxide (CO{sub 2}) at 10 K under contamination-free ultrahigh vacuum conditions, the formation of benzene carboxylic acids in interstellar ice grains was studied. Fourier transform infrared spectroscopy was used to probe for the formation of new species during the chemical processing of the ice mixture and during the following temperature-programmed desorption. Newly formed benzene carboxylic acid species, i.e., benzoic acid, as well as meta - and para -benzene dicarboxylic acid, were assigned using newly emerging bands in the infrared spectrum; a reaction mechanism, along with rate constants, wasmore » proposed utilizing the kinetic fitting of the coupled differential equations.« less

  2. Acetate accumulation enhances mixed culture fermentation of biomass to lactic acid.

    PubMed

    Khor, Way Cern; Roume, Hugo; Coma, Marta; Vervaeren, Han; Rabaey, Korneel

    2016-10-01

    Lactic acid is a high-in-demand chemical, which can be produced through fermentation of lignocellulosic feedstock. However, fermentation of complex substrate produces a mixture of products at efficiencies too low to justify a production process. We hypothesized that the background acetic acid concentration plays a critical role in lactic acid yield; therefore, its retention via selective extraction of lactic acid or its addition would improve overall lactic acid production and eliminate net production of acetic acid. To test this hypothesis, we added 10 g/L of acetate to fermentation broth to investigate its effect on products composition and concentration and bacterial community evolution using several substrate-inoculum combinations. With rumen fluid inoculum, lactate concentrations increased by 80 ± 12 % (cornstarch, p < 0.05) and 16.7 ± 0.4 % (extruded grass, p < 0.05) while with pure culture inoculum (Lactobacillus delbrueckii and genetically modified (GM) Escherichia coli), a 4 to 23 % increase was observed. Using rumen fluid inoculum, the bacterial community was enriched within 8 days to >69 % lactic acid bacteria (LAB), predominantly Lactobacillaceae. Higher acetate concentration promoted a more diverse LAB population, especially on non-inoculated bottles. In subsequent tests, acetate was added in a semi-continuous percolation system with grass as substrate. These tests confirmed our findings producing lactate at concentrations 26 ± 5 % (p < 0.05) higher than the control reactor over 20 days operation. Overall, our work shows that recirculating acetate has the potential to boost lactic acid production from waste biomass to levels more attractive for application.

  3. High-level production of C-11-carboxyl-labeled amino acids. [For use in tumor and pancreatic imaging

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

    Washburn, L. C.; Sun, T. T.; Byrd, B. L.

    Carbon-11-labeled amino acids have significant potential as agents for positron tomographic functional imaging. We have developed a rapid, high-temperature, high-pressure modification of the Buecherer--Strecker amino acid synthesis and found it to be quite general for the production of C-11-carboxyl-labeled neutral amino acids. Production of C-11-carboxyl-labeled DL-tryptophan requires certain modifications in the procedure. Twelve different amino acids have been produced to date by this technique. Synthesis and chromatographic purification require approximately 40 min, and C-11-carboxyl-labeled amino acids have been produced in yields of up to 425 mCi. Two C-11-carboxyl-labeled amino acids are being investigated clinically for tumor scanning and two othersmore » for pancreatic imaging. Over 120 batches of the various agents have been produced for clinical use over a three-year period.« less

  4. Functionalised carboxylic acids in atmospheric particles: An annual cycle revealing seasonal trends and possible sources

    NASA Astrophysics Data System (ADS)

    Teich, Monique; van Pinxteren, Dominik; Herrmann, Hartmut

    2013-04-01

    Carboxylic acids represent a major fraction of the water soluble organic carbon (WSOC) in atmospheric particles. Among the particle phase carboxylic acids, straight-chain monocarboxylic acids (MCA) and dicarboxylic acids (DCA) with 2-10 carbon atoms have extensively been studied in the past. However, only a few studies exist dealing with functionalised carboxylic acids, i.e. having additional hydroxyl-, oxo- or nitro-groups. Regarding atmospheric chemistry, these functionalised carboxylic acids are of particular interest as they are supposed to be formed during atmospheric oxidation processes, e.g. through radical reactions. Therefore they can provide insights into the tropospheric multiphase chemistry. During this work 28 carboxylic acids (4 functionalised aliphatic MCAs, 5 aromatic MCAs, 3 nitroaromatic MCAs, 6 aliphatic DCAs, 6 functionalised aliphatic DCAs, 4 aromatic DCAs) were quantitatively determined in 256 filter samples taken at the rural research station Melpitz (Saxony, Germany) with a PM10 Digitel DHA-80 filter sampler. All samples were taken in 2010 covering a whole annual cycle. The resulting dataset was examined for a possible seasonal dependency of the acid concentrations. Furthermore the influence of the air mass origin on the acid concentrations was studied based on a simple two-sector classification (western or eastern sector) using a back trajectory analysis. Regarding the annual average, adipic acid was found to be the most abundant compound with a mean concentration of 7.8 ng m-3 followed by 4-oxopimelic acid with 6.1 ng m-3. The sum of all acid concentrations showed two maxima during the seasonal cycle; one in summer and one in winter, whereas the highest overall acid concentrations were found in summer. In general the target acids could be divided into two different groups, where one group has its maximum concentration in summer and the other group during winter. The first group contains all investigated aliphatic mono- and dicarboxylic

  5. Sorption of carboxylic acid from carboxylic salt solutions at PHS close to or above the pK.sub.a of the acid, with regeneration with an aqueous solution of ammonia or low-molecular-weight alkylamine

    DOEpatents

    King, C. Judson; Tung, Lisa A.

    1992-01-01

    Carboxylic acids are sorbed from aqueous feedstocks at pHs close to or above the acids' pH.sub.a into a strongly basic organic liquid phase or onto a basic solid adsorbent or moderately basic ion exchange resin. the acids are freed from the sorbent phase by treating it with aqueous alkylamine or ammonia thus forming an alkylammonium or ammonium carobxylate which dewatered and decomposed to the desired carboxylic acid and the alkylamine or ammonia.

  6. Efficacy of Acetic Acid against Listeria monocytogenes Attached to Poultry Skin during Refrigerated Storage

    PubMed Central

    Gonzalez-Fandos, Elena; Herrera, Barbara

    2014-01-01

    This work evaluates the effect of acetic acid dipping on the growth of L. monocytogenes on poultry legs stored at 4 °C for eight days. Fresh inoculated chicken legs were dipped into either a 1% or 2% acetic acid solution (v/v) or distilled water (control). Changes in mesophiles, psychrotrophs, Enterobacteriaceae counts and sensorial characteristics (odor, color, texture and overall appearance) were also evaluated. The shelf life of the samples washed with acetic acid was extended by at least two days over the control samples washed with distilled water. L. monocytogenes counts before decontamination were 5.57 log UFC/g, and after treatment with 2% acetic acid (Day 0), L. monocytogenes counts were 4.47 log UFC/g. Legs washed with 2% acetic acid showed a significant (p < 0.05) inhibitory effect on L. monocytogenes compared to control legs, with a decrease of about 1.31 log units after eight days of storage. Sensory quality was not adversely affected by acetic acid. This study demonstrates that while acetic acid did reduce populations of L. monocytogenes on meat, it did not completely inactivate the pathogen. The application of acetic acid may be used as an additional hurdle contributing to extend the shelf life of raw poultry and reducing populations of L. monocytogenes. PMID:28234335

  7. Development of PEGylated carboxylic acid-modified polyamidoamine dendrimers as bone-targeting carriers for the treatment of bone diseases.

    PubMed

    Yamashita, Shugo; Katsumi, Hidemasa; Hibino, Nozomi; Isobe, Yugo; Yagi, Yumiko; Kusamori, Kosuke; Sakane, Toshiyasu; Yamamoto, Akira

    2017-09-28

    In this study, we aimed to develop a polyethylene glycol (PEG)-conjugated third generation polyamidoamine (PAMAM) dendrimer with multiple carboxylic acids as a bone-targeting carrier for the treatment of bone diseases. We conjugated PAMAM backbones to various carboxylic acids [aspartic acid (Asp), glutamic acid (Glu), succinic acid (Suc), or aconitic acid (Aco)] to obtain four different types of carboxylic acid-modified PAMAMs. PEG was covalently bound to carboxylic acid-modified PAMAMs to obtain PEGylated carboxylic acid-modified PAMAMs. In a tissue distribution study, the amount of 111 In-labeled unmodified PAMAM taken up by the bone after intravenous injection in mice was 11.3%. In contrast, the dose of 111 In-labeled PEG(5)-Asp-PAMAM, PEG(5)-Glu-PAMAM, PEG(5)-Suc-PAMAM, or PEG(5)-Aco-PAMAM that accumulated in the bone after injection was approximately 46.0, 15.6, 22.6, and 24.5%, respectively. The bone clearance rates of 111 In-labeled PEGylated carboxylic acid-modified PAMAMs were proportional to their affinities to hydroxyapatite and Ca 2+ . An intra-bone distribution study showed that fluorescein isothiocyanate-labeled PEG(5)-Asp-PAMAM predominantly accumulated on eroded and quiescent surfaces, a pattern associated with the pathogenesis of bone diseases, such as rheumatoid arthritis and osteoporosis. Our findings indicate that PEG(5)-Asp-PAMAM is a promising drug carrier for efficient drug targeting to the bones. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Change in the plasmid copy number in acetic acid bacteria in response to growth phase and acetic acid concentration.

    PubMed

    Akasaka, Naoki; Astuti, Wiwik; Ishii, Yuri; Hidese, Ryota; Sakoda, Hisao; Fujiwara, Shinsuke

    2015-06-01

    Plasmids pGE1 (2.5 kb), pGE2 (7.2 kb), and pGE3 (5.5 kb) were isolated from Gluconacetobacter europaeus KGMA0119, and sequence analyses revealed they harbored 3, 8, and 4 genes, respectively. Plasmid copy numbers (PCNs) were determined by real-time quantitative PCR at different stages of bacterial growth. When KGMA0119 was cultured in medium containing 0.4% ethanol and 0.5% acetic acid, PCN of pGE1 increased from 7 copies/genome in the logarithmic phase to a maximum of 12 copies/genome at the beginning of the stationary phase, before decreasing to 4 copies/genome in the late stationary phase. PCNs for pGE2 and pGE3 were maintained at 1-3 copies/genome during all phases of growth. Under a higher concentration of ethanol (3.2%) the PCN for pGE1 was slightly lower in all the growth stages, and those of pGE2 and pGE3 were unchanged. In the presence of 1.0% acetic acid, PCNs were higher for pGE1 (10 copies/genome) and pGE3 (6 copies/genome) during the logarithmic phase. Numbers for pGE2 did not change, indicating that pGE1 and pGE3 increase their PCNs in response to acetic acid. Plasmids pBE2 and pBE3 were constructed by ligating linearized pGE2 and pGE3 into pBR322. Both plasmids were replicable in Escherichia coli, Acetobacter pasteurianus and G. europaeus, highlighting their suitability as vectors for acetic acid bacteria. Copyright © 2014 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

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

    PubMed

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

    2017-09-01

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

  10. Endogenous lycopene improves ethanol production under acetic acid stress in Saccharomyces cerevisiae.

    PubMed

    Pan, Shuo; Jia, Bin; Liu, Hong; Wang, Zhen; Chai, Meng-Zhe; Ding, Ming-Zhu; Zhou, Xiao; Li, Xia; Li, Chun; Li, Bing-Zhi; Yuan, Ying-Jin

    2018-01-01

    Acetic acid, generated from the pretreatment of lignocellulosic biomass, is a significant obstacle for lignocellulosic ethanol production. Reactive oxidative species (ROS)-mediated cell damage is one of important issues caused by acetic acid. It has been reported that decreasing ROS level can improve the acetic acid tolerance of Saccharomyces cerevisiae . Lycopene is known as an antioxidant. In the study, we investigated effects of endogenous lycopene on cell growth and ethanol production of S. cerevisiae in acetic acid media. By accumulating endogenous lycopene during the aerobic fermentation of the seed stage, the intracellular ROS level of strain decreased to 1.4% of that of the control strain during ethanol fermentation. In the ethanol fermentation system containing 100 g/L glucose and 5.5 g/L acetic acid, the lag phase of strain was 24 h shorter than that of control strain. Glucose consumption rate and ethanol titer of yPS002 got to 2.08 g/L/h and 44.25 g/L, respectively, which were 2.6- and 1.3-fold of the control strain. Transcriptional changes of INO1 gene and CTT1 gene confirmed that endogenous lycopene can decrease oxidative stress and improve intracellular environment. Biosynthesis of endogenous lycopene is first associated with enhancing tolerance to acetic acid in S. cerevisiae . We demonstrate that endogenous lycopene can decrease intracellular ROS level caused by acetic acid, thus increasing cell growth and ethanol production. This work innovatively   puts forward a new strategy for second generation bioethanol production during lignocellulosic fermentation.

  11. Improvement in HPLC separation of acetic acid and levulinic acid in the profiling of biomass hydrolysate.

    PubMed

    Xie, Rui; Tu, Maobing; Wu, Yonnie; Adhikari, Sushil

    2011-04-01

    5-Hydroxymethylfurfural (HMF) and furfural could be separated by the Aminex HPX-87H column chromatography, however, the separation and quantification of acetic acid and levulinic acid in biomass hydrolysate have been difficult with this method. In present study, the HPLC separation of acetic acid and levulinic acid on Aminex HPX-87H column has been investigated by varying column temperature, flow rate, and sulfuric acid content in the mobile phase. The column temperature was found critical in resolving acetic acid and levulinic acid. The resolution for two acids increased dramatically from 0.42 to 1.86 when the column temperature was lowered from 60 to 30 °C. So did the capacity factors for levulinic acid that was increased from 1.20 to 1.44 as the column temperature dropped. The optimum column temperature for the separation was found at 45 °C. Variation in flow rate and sulfuric acid concentration improved not as much as the column temperature did. Published by Elsevier Ltd.

  12. Improving the acetic acid tolerance and fermentation of Acetobacter pasteurianus by nucleotide excision repair protein UvrA.

    PubMed

    Zheng, Yu; Wang, Jing; Bai, Xiaolei; Chang, Yangang; Mou, Jun; Song, Jia; Wang, Min

    2018-05-21

    Acetic acid bacteria (AAB) are widely used in acetic acid fermentation due to their remarkable ability to oxidize ethanol and high tolerance against acetic acid. In Acetobacter pasteurianus, nucleotide excision repair protein UvrA was up-regulated 2.1 times by acetic acid when compared with that without acetic acid. To study the effects of UvrA on A. pasteurianus acetic acid tolerance, uvrA knockout strain AC2005-ΔuvrA, uvrA overexpression strain AC2005 (pMV24-uvrA), and the control strain AC2005 (pMV24), were constructed. One percent initial acetic acid was almost lethal to AC2005-ΔuvrA. However, the biomass of the UvrA overexpression strain was higher than that of the control under acetic acid concentrations. After 6% acetic acid shock for 20 and 40 min, the survival ratios of AC2005 (pMV24-uvrA) were 2 and 0.12%, respectively; however, they were 1.5 and 0.06% for the control strain AC2005 (pMV24). UvrA overexpression enhanced the acetification rate by 21.7% when compared with the control. The enzymes involved in ethanol oxidation and acetic acid tolerance were up-regulated during acetic acid fermentation due to the overexpression of UvrA. Therefore, in A. pasteurianus, UvrA could be induced by acetic acid and is related with the acetic acid tolerance by protecting the genome against acetic acid to ensure the protein expression and metabolism.

  13. Metabolic engineering of Clostridium tyrobutyricum for enhanced butyric acid production with high butyrate/acetate ratio.

    PubMed

    Suo, Yukai; Ren, Mengmeng; Yang, Xitong; Liao, Zhengping; Fu, Hongxin; Wang, Jufang

    2018-05-01

    Butyric acid fermentation by Clostridium couples with the synthesis of acetic acid. But the presence of acetic acid reduces butyric acid yield and increases separation and purification costs of butyric acid. Hence, enhancing the butyrate/acetate ratio is important for economical butyric acid production. This study indicated that enhancing the acetyl-CoA to butyrate flux by overexpression of both the butyryl-CoA/acetate CoA transferase (cat1) and crotonase (crt) genes in C. tyrobutyricum could significantly reduce acetic acid concentration. Fed-batch fermentation of ATCC 25755/cat1 + crt resulted in increased butyrate/acetate ratio of 15.76 g/g, which was 2.24-fold higher than that of the wild-type strain. Furthermore, in order to simultaneously increase the butyrate/acetate ratio, butyric acid concentration and productivity, the recombinant strain ATCC 25755/ppcc (co-expression of 6-phosphofructokinase (pfkA) gene, pyruvate kinase (pykA) gene, cat1, and crt) was constructed. Consequently, ATCC 25755/ppcc produced more butyric acid (46.8 vs. 35.0 g/L) with a higher productivity (0.83 vs. 0.49 g/L·h) and butyrate/acetate ratio (13.22 vs. 7.22 g/g) as compared with the wild-type strain in batch fermentation using high glucose concentration (120 g/L). This study demonstrates that enhancing the acetyl-CoA to butyrate flux is an effective way to reduce acetic acid production and increase butyrate/acetate ratio.

  14. Carboxylator: incorporating solvent-accessible surface area for identifying protein carboxylation sites

    NASA Astrophysics Data System (ADS)

    Lu, Cheng-Tsung; Chen, Shu-An; Bretaña, Neil Arvin; Cheng, Tzu-Hsiu; Lee, Tzong-Yi

    2011-10-01

    In proteins, glutamate (Glu) residues are transformed into γ-carboxyglutamate (Gla) residues in a process called carboxylation. The process of protein carboxylation catalyzed by γ-glutamyl carboxylase is deemed to be important due to its involvement in biological processes such as blood clotting cascade and bone growth. There is an increasing interest within the scientific community to identify protein carboxylation sites. However, experimental identification of carboxylation sites via mass spectrometry-based methods is observed to be expensive, time-consuming, and labor-intensive. Thus, we were motivated to design a computational method for identifying protein carboxylation sites. This work aims to investigate the protein carboxylation by considering the composition of amino acids that surround modification sites. With the implication of a modified residue prefers to be accessible on the surface of a protein, the solvent-accessible surface area (ASA) around carboxylation sites is also investigated. Radial basis function network is then employed to build a predictive model using various features for identifying carboxylation sites. Based on a five-fold cross-validation evaluation, a predictive model trained using the combined features of amino acid sequence (AA20D), amino acid composition, and ASA, yields the highest accuracy at 0.874. Furthermore, an independent test done involving data not included in the cross-validation process indicates that in silico identification is a feasible means of preliminary analysis. Additionally, the predictive method presented in this work is implemented as Carboxylator (http://csb.cse.yzu.edu.tw/Carboxylator/), a web-based tool for identifying carboxylated proteins with modification sites in order to help users in investigating γ-glutamyl carboxylation.

  15. Thermal decarboxylation of acetic acid: Implications for origin of natural gas

    USGS Publications Warehouse

    Kharaka, Y.K.; Carothers, W.W.; Rosenbauer, R.J.

    1983-01-01

    Laboratory experiments on the thermal decarboxylation of solutions of acetic acid at 200??C and 300??C were carried out in hydrothermal equipment allowing for on-line sampling of both the gas and liquid phases for chemical and stable-carbon-isotope analyses. The solutions had ambient pH values between 2.5 and 7.1; pH values and the concentrations of the various acetate species at the conditions of the experiments were computed using a chemical model. Results show that the concentrations of acetic acid, and not total acetate in solution, control the reaction rates which follow a first order equation based on decreasing concentrations of acetic acid with time. The decarboxylation rates at 200??C (1.81 ?? 10-8 per second) and 300??C (8.17 ?? 10-8 per second) and the extrapolated rates at lower temperatures are relatively high. The activation energy of decarboxylation is only 8.1 kcal/mole. These high decarboxylation rates, together with the distribution of short-chained aliphatic acid anions in formation waters, support the hypothesis that acid anions are precursors for an important portion of natural gas. Results of the ??13C values of CO2, CH4, and total acetate show a reasonably constant fractionation factor of about 20 permil between CO2 and CH4 at 300??C. The ??13C values of CO2 and CH4 are initially low and become higher as decarboxylation increases. ?? 1983.

  16. Molecular complexes of alprazolam with carboxylic acids, boric acid, boronic acids, and phenols. Evaluation of supramolecular heterosynthons mediated by a triazole ring.

    PubMed

    Varughese, Sunil; Azim, Yasser; Desiraju, Gautam R

    2010-09-01

    A series of molecular complexes, both co-crystals and salts, of a triazole drug-alprazolam-with carboxylic acids, boric acid, boronic acids, and phenols have been analyzed with respect to heterosynthons present in the crystal structures. In all cases, the triazole ring behaves as an efficient hydrogen bond acceptor with the acidic coformers. The hydrogen bond patterns exhibited with aromatic carboxylic acids were found to depend on the nature and position of the substituents. Being a strong acid, 2,6-dihydroxybenzoic acid forms a salt with alprazolam. With aliphatic dicarboxylic acids alprazolam forms hydrates and the water molecules play a central role in synthon formation and crystal packing. The triazole ring makes two distinct heterosynthons in the molecular complex with boric acid. Boronic acids and phenols form consistent hydrogen bond patterns, and these are seemingly independent of the substitutional effects. Boronic acids form noncentrosymmetric cyclic synthons, while phenols form O--H...N hydrogen bonds with the triazole ring.

  17. Inactivation by Phenylglyoxal of the Specific Binding of 1-Naphthyl Acetic Acid with Membrane-Bound Auxin Binding Sites from Maize Coleoptiles

    PubMed Central

    Navé, Jean-François; Benveniste, Pierre

    1984-01-01

    The specific binding of 1-[3H]naphthyl acetic acid (NAA) to membrane-bound binding sites from maize (Zea mays cv INRA 258) coleoptiles is inactivated by phenylglyoxal. The inactivation obeys pseudo first-order kinetics. The rate of inactivation is proportional to phenylglyoxal concentration. Under conditions at which significant binding occurs, NAA, R and S-1-naphthyl 2-propionic acids protect the auxin binding site against inactivation by phenylglyoxal. Scatchard analysis shows that the inhibition of binding corresponds to a decrease in the concentration of sites but not in the affinity. The results of the present chemical modification study indicate that at least one arginyl residue is involved in the positively charged recognition site of the carboxylate anion of NAA. PMID:16663499

  18. Unravelling the contribution of lactic acid bacteria and acetic acid bacteria to cocoa fermentation using inoculated organisms.

    PubMed

    Ho, Van Thi Thuy; Fleet, Graham H; Zhao, Jian

    2018-08-20

    Cocoa beans (Theobroma cacao L.) are the raw material for chocolate production. Fermentation of the bean pulp by microorganisms is essential for developing the precursors of chocolate flavour. Currently, the cocoa fermentation is still conducted by an uncontrolled traditional process via a consortium of indigenous species of yeasts, lactic acid bacteria and acetic acid bacteria. Although the essential contribution of yeasts to the production of good quality beans and, typical chocolate character is generally agreed, the roles of lactic acid bacteria and acetic acid bacteria are less certain. The objective of this study was to investigate the contribution of LAB and AAB in cocoa bean fermentation by conducting small scale laboratory fermentations under aseptic conditions, inoculated with different groups of microorganisms previously isolated from spontaneous cocoa fermentations. The inoculation protocols were: (1) four yeasts Hanseniaspora guilliermondii, Pichia kudriavzevii, Kluyveromyces marxianus and Saccharomyces cerevisiae; (2) four yeasts plus the lactic acid bacteria Lactobacillus plantarum and Lactobacillus fermentum; (3) four yeasts plus the acetic acid bacteria Acetobacter pasteurianus and Gluconobacter frateuri and (4) four yeasts plus two lactic acid bacteria and two acetic acid bacteria. Only the inoculated species were detected in the microbiota of their respective fermentations. Beans from the inoculated fermentations showed no significant differences in colour, shell weights and concentrations of residual sugars, alcohols and esters (p>0.05), but they were slightly different in contents of lactic acid and acetic acid (p<0.05). All beans were fully brown and free of mould. Residual sugar levels were less than 2.6 mg/g while the shell contents and ethanol were in the range of 11-13.4% and 4.8-7 mg/g, respectively. Beans fermented in the presence of LAB contained higher levels of lactic acid (0.6-1.2 mg/g) whereas higher concentrations of acetic acid

  19. Effects of Oxygen Availability on Acetic Acid Tolerance and Intracellular pH in Dekkera bruxellensis.

    PubMed

    Capusoni, Claudia; Arioli, Stefania; Zambelli, Paolo; Moktaduzzaman, M; Mora, Diego; Compagno, Concetta

    2016-08-01

    The yeast Dekkera bruxellensis, associated with wine and beer production, has recently received attention, because its high ethanol and acid tolerance enables it to compete with Saccharomyces cerevisiae in distilleries that produce fuel ethanol. We investigated how different cultivation conditions affect the acetic acid tolerance of D. bruxellensis We analyzed the ability of two strains (CBS 98 and CBS 4482) exhibiting different degrees of tolerance to grow in the presence of acetic acid under aerobic and oxygen-limited conditions. We found that the concomitant presence of acetic acid and oxygen had a negative effect on D. bruxellensis growth. In contrast, incubation under oxygen-limited conditions resulted in reproducible growth kinetics that exhibited a shorter adaptive phase and higher growth rates than those with cultivation under aerobic conditions. This positive effect was more pronounced in CBS 98, the more-sensitive strain. Cultivation of CBS 98 cells under oxygen-limited conditions improved their ability to restore their intracellular pH upon acetic acid exposure and to reduce the oxidative damage to intracellular macromolecules caused by the presence of acetic acid. This study reveals an important role of oxidative stress in acetic acid tolerance in D. bruxellensis, indicating that reduced oxygen availability can protect against the damage caused by the presence of acetic acid. This aspect is important for optimizing industrial processes performed in the presence of acetic acid. This study reveals an important role of oxidative stress in acetic acid tolerance in D. bruxellensis, indicating that reduced oxygen availability can have a protective role against the damage caused by the presence of acetic acid. This aspect is important for the optimization of industrial processes performed in the presence of acetic acid. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

  20. Effects of Oxygen Availability on Acetic Acid Tolerance and Intracellular pH in Dekkera bruxellensis

    PubMed Central

    Capusoni, Claudia; Arioli, Stefania; Zambelli, Paolo; Moktaduzzaman, M.; Mora, Diego

    2016-01-01

    ABSTRACT The yeast Dekkera bruxellensis, associated with wine and beer production, has recently received attention, because its high ethanol and acid tolerance enables it to compete with Saccharomyces cerevisiae in distilleries that produce fuel ethanol. We investigated how different cultivation conditions affect the acetic acid tolerance of D. bruxellensis. We analyzed the ability of two strains (CBS 98 and CBS 4482) exhibiting different degrees of tolerance to grow in the presence of acetic acid under aerobic and oxygen-limited conditions. We found that the concomitant presence of acetic acid and oxygen had a negative effect on D. bruxellensis growth. In contrast, incubation under oxygen-limited conditions resulted in reproducible growth kinetics that exhibited a shorter adaptive phase and higher growth rates than those with cultivation under aerobic conditions. This positive effect was more pronounced in CBS 98, the more-sensitive strain. Cultivation of CBS 98 cells under oxygen-limited conditions improved their ability to restore their intracellular pH upon acetic acid exposure and to reduce the oxidative damage to intracellular macromolecules caused by the presence of acetic acid. This study reveals an important role of oxidative stress in acetic acid tolerance in D. bruxellensis, indicating that reduced oxygen availability can protect against the damage caused by the presence of acetic acid. This aspect is important for optimizing industrial processes performed in the presence of acetic acid. IMPORTANCE This study reveals an important role of oxidative stress in acetic acid tolerance in D. bruxellensis, indicating that reduced oxygen availability can have a protective role against the damage caused by the presence of acetic acid. This aspect is important for the optimization of industrial processes performed in the presence of acetic acid. PMID:27235432

  1. Drug resistance marker-aided genome shuffling to improve acetic acid tolerance in Saccharomyces cerevisiae.

    PubMed

    Zheng, Dao-Qiong; Wu, Xue-Chang; Wang, Pin-Mei; Chi, Xiao-Qin; Tao, Xiang-Lin; Li, Ping; Jiang, Xin-Hang; Zhao, Yu-Hua

    2011-03-01

    Acetic acid existing in a culture medium is one of the most limiting constraints in yeast growth and viability during ethanol fermentation. To improve acetic acid tolerance in Saccharomyces cerevisiae strains, a drug resistance marker-aided genome shuffling approach with higher screen efficiency of shuffled mutants was developed in this work. Through two rounds of genome shuffling of ultraviolet mutants derived from the original strain 308, we obtained a shuffled strain YZ2, which shows significantly faster growth and higher cell viability under acetic acid stress. Ethanol production of YZ2 (within 60 h) was 21.6% higher than that of 308 when 0.5% (v/v) acetic acid was added to fermentation medium. Membrane integrity, higher in vivo activity of the H+-ATPase, and lower oxidative damage after acetic acid treatment are the possible reasons for the acetic acid-tolerance phenotype of YZ2. These results indicated that this novel genome shuffling approach is powerful to rapidly improve the complex traits of industrial yeast strains.

  2. Synthesis of acetic acid via methanol hydrocarboxylation with CO2 and H2

    PubMed Central

    Qian, Qingli; Zhang, Jingjing; Cui, Meng; Han, Buxing

    2016-01-01

    Acetic acid is an important bulk chemical that is currently produced via methanol carbonylation using fossil based CO. Synthesis of acetic acid from the renewable and cheap CO2 is of great importance, but state of the art routes encounter difficulties, especially in reaction selectivity and activity. Here we report a route to produce acetic acid from CO2, methanol and H2. The reaction can be efficiently catalysed by Ru–Rh bimetallic catalyst using imidazole as the ligand and LiI as the promoter in 1,3-dimethyl-2-imidazolidinone (DMI) solvent. It is confirmed that methanol is hydrocarboxylated into acetic acid by CO2 and H2, which accounts for the outstanding reaction results. The reaction mechanism is proposed based on the control experiments. The strategy opens a new way for acetic acid production and CO2 transformation, and represents a significant progress in synthetic chemistry. PMID:27165850

  3. Synthesis of acetic acid via methanol hydrocarboxylation with CO2 and H2.

    PubMed

    Qian, Qingli; Zhang, Jingjing; Cui, Meng; Han, Buxing

    2016-05-11

    Acetic acid is an important bulk chemical that is currently produced via methanol carbonylation using fossil based CO. Synthesis of acetic acid from the renewable and cheap CO2 is of great importance, but state of the art routes encounter difficulties, especially in reaction selectivity and activity. Here we report a route to produce acetic acid from CO2, methanol and H2. The reaction can be efficiently catalysed by Ru-Rh bimetallic catalyst using imidazole as the ligand and LiI as the promoter in 1,3-dimethyl-2-imidazolidinone (DMI) solvent. It is confirmed that methanol is hydrocarboxylated into acetic acid by CO2 and H2, which accounts for the outstanding reaction results. The reaction mechanism is proposed based on the control experiments. The strategy opens a new way for acetic acid production and CO2 transformation, and represents a significant progress in synthetic chemistry.

  4. A novel fermentation pathway in an Escherichia coli mutant producing succinic acid, acetic acid, and ethanol.

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

    Donnelly, M. I.; Millard, C. S.; Clark, D. P.

    1998-04-01

    Escherichia coli strain NZN111, which is unable to grow fermentatively because of insertional inactivation of the genes encoding pyruvate: formate lyase and the fermentative lactate dehydrogenase, gave rise spontaneously to a chromosomal mutation that restored its ability to ferment glucose. The mutant strain, named AFP111, fermented glucose more slowly than did its wild-type ancestor, strain W1485, and generated a very different spectrum of products. AFP111 produced succinic acid, acetic acid, and ethanol in proportions of approx 2:1:1. Calculations of carbon and electron balances accounted fully for the observed products; 1 mol of glucose was converted to 1 mol of succinicmore » acid and 0.5 mol each of acetic acid and ethanol. The data support the emergence in E.coli of a novel succinic acid:acetic acid:ethanol fermentation pathway.« less

  5. Direct enantioselective conjugate addition of carboxylic acids with chiral lithium amides as traceless auxiliaries.

    PubMed

    Lu, Ping; Jackson, Jeffrey J; Eickhoff, John A; Zakarian, Armen

    2015-01-21

    Michael addition is a premier synthetic method for carbon-carbon and carbon-heteroatom bond formation. Using chiral dilithium amides as traceless auxiliaries, we report the direct enantioselective Michael addition of carboxylic acids. A free carboxyl group in the product provides versatility for further functionalization, and the chiral reagent can be readily recovered by extraction with aqueous acid. The method has been applied in the enantioselective total synthesis of the purported structure of pulveraven B.

  6. Trehalose accumulation enhances tolerance of Saccharomyces cerevisiae to acetic acid.

    PubMed

    Yoshiyama, Yoko; Tanaka, Koichi; Yoshiyama, Kohei; Hibi, Makoto; Ogawa, Jun; Shima, Jun

    2015-02-01

    Trehalose confers protection against various environmental stresses on yeast cells. In this study, trehalase gene deletion mutants that accumulate trehalose at high levels showed significant stress tolerance to acetic acid. The enhancement of trehalose accumulation can thus be considered a target in the breeding of acetic acid-tolerant yeast strains. Copyright © 2014 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

  7. Biosynthesis of the Halogenated Auxin, 4-Chloroindole-3-Acetic Acid1[W][OA

    PubMed Central

    Tivendale, Nathan D.; Davidson, Sandra E.; Davies, Noel W.; Smith, Jason A.; Dalmais, Marion; Bendahmane, Abdelhafid I.; Quittenden, Laura J.; Sutton, Lily; Bala, Raj K.; Le Signor, Christine; Thompson, Richard; Horne, James; Reid, James B.; Ross, John J.

    2012-01-01

    Seeds of several agriculturally important legumes are rich sources of the only halogenated plant hormone, 4-chloroindole-3-acetic acid. However, the biosynthesis of this auxin is poorly understood. Here, we show that in pea (Pisum sativum) seeds, 4-chloroindole-3-acetic acid is synthesized via the novel intermediate 4-chloroindole-3-pyruvic acid, which is produced from 4-chlorotryptophan by two aminotransferases, TRYPTOPHAN AMINOTRANSFERASE RELATED1 and TRYPTOPHAN AMINOTRANSFERASE RELATED2. We characterize a tar2 mutant, obtained by Targeting Induced Local Lesions in Genomes, the seeds of which contain dramatically reduced 4-chloroindole-3-acetic acid levels as they mature. We also show that the widespread auxin, indole-3-acetic acid, is synthesized by a parallel pathway in pea. PMID:22573801

  8. Pretreatment of corn stover with diluted acetic acid for enhancement of acidogenic fermentation.

    PubMed

    Zhao, Xu; Wang, Lijuan; Lu, Xuebin; Zhang, Shuting

    2014-04-01

    A Box-Behnken design of response surface method was used to optimize acetic acid-catalyzed hydrothermal pretreatment of corn stover, in respect to acid concentration (0.05-0.25%), treatment time (5-15 min) and reaction temperature (180-210°C). Acidogenic fermentations with different initial pH and hydrolyzates were also measured to evaluate the optimal pretreatment conditions for maximizing acid production. The results showed that pretreatment with 0.25% acetic acid at 191°C for 7.74 min was found to be the most optimal condition for pretreatment of corn stover under which the production of acids can reach the highest level. Acidogenic fermentation with the hydrolyzate of pretreatment at the optimal condition at the initial pH=5 was shown to be butyric acid type fermentation, producing 21.84 g acetic acid, 7.246 g propionic acid, 9.170 butyric acid and 1.035 g isovaleric acid from 100g of corn stover in 900 g of water containing 2.25 g acetic acid. Copyright © 2014 Elsevier Ltd. All rights reserved.

  9. Physiological responses of insects to microbial fermentation products: Insights from the interactions between Drosophila and acetic acid.

    PubMed

    Kim, Geonho; Huang, Jia Hsin; McMullen, John G; Newell, Peter D; Douglas, Angela E

    2018-04-01

    Acetic acid is a fermentation product of many microorganisms, including some that inhabit the food and guts of Drosophila. Here, we investigated the effect of dietary acetic acid on oviposition and larval performance of Drosophila. At all concentrations tested (0.34-3.4%), acetic acid promoted egg deposition by mated females in no-choice assays; and females preferred to oviposit on diet with acetic acid relative to acetic acid-free diet. However, acetic acid depressed larval performance, particularly extending the development time of both larvae colonized with the bacterium Acetobacter pomorum and axenic (microbe-free) larvae. The larvae may incur an energetic cost associated with dissipating the high acid load on acetic acid-supplemented diets. This effect was compounded by suppressed population growth of A. pomorum on the 3.4% acetic acid diet, such that the gnotobiotic Drosophila on this diet displayed traits characteristic of axenic Drosophila, specifically reduced developmental rate and elevated lipid content. It is concluded that acetic acid is deleterious to larval Drosophila, and hypothesized that acetic acid may function as a reliable cue for females to oviposit in substrates bearing microbial communities that promote larval nutrition. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Radiofrequency Thermal Ablation: Increase in Lesion Diameter with Continuous Acetic Acid Infusion

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

    Lubienski, Andreas; Duex, Markus; Lubienski, Katrin

    Purpose. To evaluate the influence of continuous infusion of acetic acid 50% during radiofrequency ablation (RFA) on the size of the thermal lesion produced. Methods. Radiofrequency (RF) was applied to excised bovine liver by using an expandable needle electrode with 10 retractable tines (LeVeen Needle Electrode, RadioTherapeutics, Sunnyvale, CA) connected to a commercially available RF generator (RF 2000, RadioTherapeutics, Sunnyvale, CA). Experiments were performed using three different treatment modalities: RF only (n = 15), RF with continuous saline 0.9% infusion (n = 15), and RF with continuous acetic acid 50% infusion (n = 15). RF duration, power output, tissue impedance,more » and time to a rapid rise in impedance were recorded. The ablated lesions were evaluated both macroscopically and histologically. Results. The ablated lesions appeared as spherical or ellipsoid, well-demarcated pale areas with a surrounding brown rim with both RF only and RF plus saline 0.9% infusion. In contrast, thermolesions generated with RF in combination with acetic acid 50% infusion were irregular in shape and the central portion was jelly-like. Mean diameter of the coagulation necrosis was 22.3 {+-} 2.1 mm (RF only), 29.2 {+-} 4.8 mm (RF + saline 0.9%) and 30.7 {+-} 5.7 mm (RF + acetic acid 50%), with a significant increase in the RF plus saline 0.9% and RF plus acetic acid 50% groups compared with RF alone. Time to a rapid rise in impedance was significantly prolonged in the RF plus saline 0.9% and RF plus acetic acid 50% groups compared with RF alone. Conclusions. A combination of RF plus acetic acid 50% infusion is able to generate larger thermolesions than RF only or RF combined with saline 0.9% infusion.« less

  11. Acetic acid bacteria in traditional balsamic vinegar: phenotypic traits relevant for starter cultures selection.

    PubMed

    Gullo, Maria; Giudici, Paolo

    2008-06-30

    This review focuses on acetic acid bacteria in traditional balsamic vinegar process. Although several studies are available on acetic acid bacteria ecology, metabolism and nutritional requirements, their activity as well as their technological traits in homemade vinegars as traditional balsamic vinegar is not well known. The basic technology to oxidise cooked grape must to produce traditional balsamic vinegar is performed by the so called "seed-vinegar" that is a microbiologically undefined starter culture obtained from spontaneous acetification of previous raw material. Selected starter cultures are the main technological improvement in order to innovate traditional balsamic vinegar production but until now they are rarely applied. To develop acetic acid bacteria starter cultures, selection criteria have to take in account composition of raw material, acetic acid bacteria metabolic activities, applied technology and desired characteristics of the final product. For traditional balsamic vinegar, significative phenotypical traits of acetic acid bacteria have been highlighted. Basic traits are: ethanol preferred and efficient oxidation, fast rate of acetic acid production, tolerance to high concentration of acetic acid, no overoxidation and low pH resistance. Specific traits are tolerance to high sugar concentration and to a wide temperature range. Gluconacetobacter europaeus and Acetobacter malorum strains can be evaluated to develop selected starter cultures since they show one or more suitable characters.

  12. Gas-Phase Amidation of Carboxylic Acids with Woodward’s Reagent K Ions

    PubMed Central

    Peng, Zhou; Pilo, Alice L.; Luongo, Carl A.; McLuckey, Scott A.

    2015-01-01

    Gas-phase amidation of carboxylic acids in multiply-charged peptides is demonstrated via ion/ion reactions with Woodward’s reagent K (wrk) in both positive and negative mode. Woodward’s reagent K, N-ethyl-3-phenylisoxazolium-3′-sulfonate, is a commonly used reagent that activates carboxylates to form amide bonds with amines in solution. Here, we demonstrate that the analogous gas-phase chemistry occurs upon reaction of the wrk ions and doubly protonated (or doubly deprotonated) peptide ions containing the carboxylic acid functionality. The reaction involves the formation of the enol ester intermediate in the electrostatic complex. Upon collisional activation, the ethyl amine on the reagent is transferred to the activated carbonyl carbon on the peptide, resulting in the formation of an ethyl amide (addition of 27 Da to the peptide) with loss of a neutral ketene derivative. Further collision-induced dissociation (CID) of the products and comparison with solution-phase amidation product confirms the structure of the ethyl amide. PMID:26122523

  13. Point mutation of H3/H4 histones affects acetic acid tolerance in Saccharomyces cerevisiae.

    PubMed

    Liu, Xiangyong; Zhang, Xiaohua; Zhang, Zhaojie

    2014-10-10

    The molecular mechanism of acetic acid tolerance in yeast remains unclear despite of its importance for efficient cellulosic ethanol production. In this study, we examined the effects of histone H3/H4 point mutations on yeast acetic acid tolerance by comprehensively screening a histone H3/H4 mutant library. A total of 24 histone H3/H4 mutants (six acetic acid resistant and 18 sensitive) were identified. Compared to the wild-type strain, the histone acetic acid-resistant mutants exhibited improved ethanol fermentation performance under acetic acid stress. Genome-wide transcriptome analysis revealed that changes in the gene expression in the acetic acid-resistant mutants H3 K37A and H4 K16Q were mainly related to energy production, antioxidative stress. Our results provide novel insights into yeast acetic acid tolerance on the basis of histone, and suggest a novel approach to improve ethanol production by altering the histone H3/H4 sequences. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Isolation of acetic, propionic and butyric acid-forming bacteria from biogas plants.

    PubMed

    Cibis, Katharina Gabriela; Gneipel, Armin; König, Helmut

    2016-02-20

    In this study, acetic, propionic and butyric acid-forming bacteria were isolated from thermophilic and mesophilic biogas plants (BGP) located in Germany. The fermenters were fed with maize silage and cattle or swine manure. Furthermore, pressurized laboratory fermenters digesting maize silage were sampled. Enrichment cultures for the isolation of acid-forming bacteria were grown in minimal medium supplemented with one of the following carbon sources: Na(+)-dl-lactate, succinate, ethanol, glycerol, glucose or a mixture of amino acids. These substrates could be converted by the isolates to acetic, propionic or butyric acid. In total, 49 isolates were obtained, which belonged to the phyla Firmicutes, Tenericutes or Thermotogae. According to 16S rRNA gene sequences, most isolates were related to Clostridium sporosphaeroides, Defluviitoga tunisiensis and Dendrosporobacter quercicolus. Acetic, propionic or butyric acid were produced in cultures of isolates affiliated to Bacillus thermoamylovorans, Clostridium aminovalericum, Clostridium cochlearium/Clostridium tetani, C. sporosphaeroides, D. quercicolus, Proteiniborus ethanoligenes, Selenomonas bovis and Tepidanaerobacter sp. Isolates related to Thermoanaerobacterium thermosaccharolyticum produced acetic, butyric and lactic acid, and isolates related to D. tunisiensis formed acetic acid. Specific primer sets targeting 16S rRNA gene sequences were designed and used for real-time quantitative PCR (qPCR). The isolates were physiologically characterized and their role in BGP discussed. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. Direct Enantioselective Conjugate Addition of Carboxylic Acids with Chiral Lithium Amides as Traceless Auxiliaries

    PubMed Central

    2016-01-01

    Michael addition is a premier synthetic method for carbon–carbon and carbon–heteroatom bond formation. Using chiral dilithium amides as traceless auxiliaries, we report the direct enantioselective Michael addition of carboxylic acids. A free carboxyl group in the product provides versatility for further functionalization, and the chiral reagent can be readily recovered by extraction with aqueous acid. The method has been applied in the enantioselective total synthesis of the purported structure of pulveraven B. PMID:25562717

  16. Simple quantification of surface carboxylic acids on chemically oxidized multi-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Gong, Hyejin; Kim, Seong-Taek; Lee, Jong Doo; Yim, Sanggyu

    2013-02-01

    The surface of multi-walled carbon nanotube (MWCNT) was chemically oxidized using nitric acid and sulfuric-nitric acid mixtures. Thermogravimetric analysis, transmission electron microscopy and infrared spectroscopy revealed that the use of acid mixtures led to higher degree of oxidation. More quantitative identification of surface carboxylic acids was carried out using X-ray photoelectron spectroscopy (XPS) and acid-base titration. However, these techniques are costly and require very long analysis times to promptly respond to the extent of the reaction. We propose a much simpler method using pH measurements and pre-determined pKa value in order to estimate the concentration of carboxylic acids on the oxidized MWCNT surfaces. The results from this technique were consistent with those obtained from XPS and titration, and it is expected that this simple quantification method can provide a cheap and fast way to monitor and control the oxidation reaction of MWCNT.

  17. Enhanced detection of amino acids in hydrophilic interaction chromatography electrospray tandem mass spectrometry with carboxylic acids as mobile phase additives.

    PubMed

    Yin, Dengyang; Hu, Xunxiu; Liu, Dantong; Du, Wencheng; Wang, Haibo; Guo, Mengzhe; Tang, Daoquan

    2017-06-01

    Liquid chromatography coupled with mass spectrometry technique has been widely used in the analysis of biological targets such as amino acids, peptides, and proteins. In this work, eight common single carboxylic acids or diacids, which contain different pKa have been investigated as the additives to the analysis of amino acids. As the results, carboxylic acid additive can improve the signal intensity of acidity amino acids such as Asp and Glu and the chromatographic separation of basic amino acids such as Arg, His, and Lys. In particular, the diacids have better performance than single acids. The proposed mechanism is that the diacid has hydrogen bond interaction with amino acids to reduce their polarity/amphiprotic characteristics. Besides, oxalic acid has been found having better enhancement than phthalic acid by overall consideration. Therefore, we successfully quantified the 15 amino acids in Sepia bulk pharmaceutical chemical by using oxalic acid as the additive.

  18. Additive postprandial blood glucose-attenuating and satiety-enhancing effect of cinnamon and acetic acid.

    PubMed

    Mettler, Samuel; Schwarz, Isaline; Colombani, Paolo C

    2009-10-01

    Cinnamon and vinegar or acetic acid were reported to reduce the postprandial blood glucose response. We hypothesized that the combination of these substances might result in an additive effect. Therefore, we determined the 2-hour postprandial blood glucose and satiety response to a milk rice meal supplemented with either cinnamon or acetic acid on their own or in combination. Subjects (n = 27) consumed the meal on 4 occasions as either pure (control trial), with 4 g cinnamon, 28 mmol acetic acid, or the combination of cinnamon + acetic acid. Blood glucose and satiety were assessed before eating and 15, 30, 45, 60, 90, and 120 minutes postprandially. At 15 minutes, the combination of cinnamon + acetic acid resulted in a significantly reduced blood glucose concentration compared with the control meal (P = .021). The incremental area under the blood glucose response curve over 120 minutes did, however, not differ between the trials (P = .539). The satiety score of the cinnamon + acetic acid trial was significantly higher than that in the control trial at 15 (P = .024) and 30 minutes (P = .024), but the incremental area under the curve of the satiety response did not differ (P = .116) between the trials. In conclusion, the significant effect of the combination of cinnamon and acetic acid on blood glucose and satiety immediately after meal intake indicated an additive effect of the 2 substances. Whether larger doses of cinnamon and acetic acid may result in a more substantial additive effect on blood glucose or satiety remains to be investigated.

  19. The Genealogical Tree of Ethanol: Gas-phase Formation of Glycolaldehyde, Acetic Acid, and Formic Acid

    NASA Astrophysics Data System (ADS)

    Skouteris, Dimitrios; Balucani, Nadia; Ceccarelli, Cecilia; Vazart, Fanny; Puzzarini, Cristina; Barone, Vincenzo; Codella, Claudio; Lefloch, Bertrand

    2018-02-01

    Despite the harsh conditions of the interstellar medium, chemistry thrives in it, especially in star-forming regions where several interstellar complex organic molecules (iCOMs) have been detected. Yet, how these species are synthesized is a mystery. The majority of current models claim that this happens on interstellar grain surfaces. Nevertheless, evidence is mounting that neutral gas-phase chemistry plays an important role. In this paper, we propose a new scheme for the gas-phase synthesis of glycolaldehyde, a species with a prebiotic potential and for which no gas-phase formation route was previously known. In the proposed scheme, the ancestor is ethanol and the glycolaldehyde sister species are acetic acid (another iCOM with unknown gas-phase formation routes) and formic acid. For the reactions of the new scheme with no available data, we have performed electronic structure and kinetics calculations deriving rate coefficients and branching ratios. Furthermore, after a careful review of the chemistry literature, we revised the available chemical networks, adding and correcting several reactions related to glycolaldehyde, acetic acid, and formic acid. The new chemical network has been used in an astrochemical model to predict the abundance of glycolaldehyde, acetic acid, and formic acid. The predicted abundance of glycolaldehyde depends on the ethanol abundance in the gas phase and is in excellent agreement with the measured one in hot corinos and shock sites. Our new model overpredicts the abundance of acetic acid and formic acid by about a factor of 10, which might imply a yet incomplete reaction network.

  20. Revising Estimates of the Methane Production Pathway in Peatland Porewater Using Intramolecular Isotopic Analyses of Acetate

    NASA Astrophysics Data System (ADS)

    Thomas, B.; Arthur, M. A.; Freeman, K. H.

    2007-12-01

    fraction of methane derived from carbon dioxide, with deeper peat dominated by hydrogenotrophic methanogenesis, but shallow peat dominated by aceticlastic methanogens. Significant aceticlastic methane production from autotrophically produced acetate challenges the ability of hydrogen isotopic measurements of methane to represent the pathway of methanogenesis. Supplementing our field observations, intramolecular acetate measurements of incubation experiments confirm that an aceticlastic methanogen can facilitate significant acetate-carboxyl exchange with DIC. This novel technique confirms two caveats associated with whole acetate carbon isotopic data: 1, the carboxyl carbon isotopic composition may not accurately reflect the composition of the parent molecule, and 2, the acetate methyl may be derived from inorganic carbon or the fractionation effect of fermentation in acidic porewaters may be significant.

  1. Tolerance to acetic acid is improved by mutations of the TATA-binding protein gene.

    PubMed

    An, Jieun; Kwon, Hyeji; Kim, Eunjung; Lee, Young Mi; Ko, Hyeok Jin; Park, Hongjae; Choi, In-Geol; Kim, Sooah; Kim, Kyoung Heon; Kim, Wankee; Choi, Wonja

    2015-03-01

    Screening a library of overexpressing mutant alleles of the TATA-binding gene SPT15 yielded two Saccharomyces cerevisiae strains (MRRC 3252 and 3253) with enhanced tolerance to acetic acid. They were also tolerant to propionic acid and hydrogen peroxide. Transcriptome profile analysis identified 58 upregulated genes and 106 downregulated genes in MRRC 3252. Stress- and protein synthesis-related transcription factors were predominantly enriched in the upregulated and downregulated genes respectively. Eight deletion mutants for some of the highly downregulated genes were acetic acid-tolerant. The level of intracellular reactive oxygen species was considerably lessened in MRRC 3252 and 3253 upon exposure to acetic acid. Metabolome profile analysis revealed that intracellular concentrations of 5 and 102 metabolites were increased and decreased, respectively, in MRRC 3252, featuring a large increase of urea and a significant decrease of amino acids. The dur1/2Δmutant, in which the urea degradation gene DUR1/2 is deleted, displayed enhanced tolerance to acetic acid. Enhanced tolerance to acetic acid was also observed on the medium containing a low concentration of amino acids. Taken together, this study identified two SPT15 alleles, nine gene deletions and low concentration of amino acids in the medium that confer enhanced tolerance to acetic acid. © 2014 Society for Applied Microbiology and John Wiley & Sons Ltd.

  2. Production of alpha-hydroxy carboxylic acids and esters from higher sugars using tandem catalyst systems

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

    Orazov, Marat; Davis, Mark E.

    The present disclosure is directed to methods and composition used in the preparation of alpha-hydroxy carboxylic acids and esters from higher sugars using a tandem catalyst system comprising retro-aldol catalysts and Lewis acid catalysts. In some embodiments, these alpha-hydroxy carboxylic acids may be prepared from pentoses and hexoses. The retro-aldol and Lewis catalysts may be characterized by their respective ability to catalyze a 1,2-carbon shift reaction and a 1,2-hydride shift reaction on an aldose or ketose substrate.

  3. Occurrence of carboxylic acids in different steps of two drinking-water treatment plants using different disinfectants.

    PubMed

    Jurado-Sánchez, Beatriz; Ballesteros, Evaristo; Gallego, Mercedes

    2014-03-15

    The occurrence of 35 aliphatic and aromatic carboxylic acids within two full scale drinking-water treatment plants was evaluated for the first time in this research. At the intake of each plant (raw water), the occurrence of carboxylic acids varied according to the quality of the water source although in both cases 13 acids were detected at average concentrations of 6.9 and 4.7 μg/L (in winter). In the following steps in each treatment plant, the concentration patterns of these compounds differed depending on the type of disinfectant applied. Thus, after disinfection by chloramination, the levels of the acids remained almost constant (average concentration, 6.3 μg/L) and four new acids were formed (butyric, 2-methylbutyric, 3-hydroxybenzoic and 2-nitrobenzoic) at low levels (1.1-5 μg/L). When ozonation/chlorination was used, the total concentration of the carboxylic acids in the raw water sample (4.7 μg/L) increased up to 6 times (average concentration, 26.3 μg/L) after disinfection and 6 new acids (mainly aromatic) were produced at high levels (3.5-100 μg/L). Seasonal variations of the carboxylic acids under study showed that in both plants, maximum levels of all the analytes were reached in the coldest months (autumn and winter), aromatic acids only being found in those seasons. Copyright © 2013 Elsevier Ltd. All rights reserved.

  4. ANALYSIS OF PERFLUORINATED CARBOXYLIC ACIDS IN SOILS II: OPTIMIZATION OF CHROMATOGRAPHY AND EXTRACTION

    EPA Science Inventory

    With the objective of detecting and quantitating low concentrations of perfluorinated carboxylic acids (PFCAs), including perfluorinated octanoic acid (PFOA), in soils, we compared the analytical suitability of liquid chromatography columns containing three different stationary p...

  5. Enantiomer analysis of chiral carboxylic acids by AIE molecules bearing optically pure aminol groups.

    PubMed

    Zheng, Yan-Song; Hu, Yu-Jian; Li, Dong-Mi; Chen, Yi-Chang

    2010-01-15

    Pure enantiomers of carboxylic acids are a class of important biomolecules, chiral drugs, chiral reagents, etc. Analysis of the enantiomers usually needs expensive instrument or complex chiral receptors. However, to develop simple and reliable methods for the enantiomer analysis of acids is difficult. In this paper, chiral recognition of 2,3-dibenzoyltartaric acid and mandelic acid was first carried out by aggregation-induced emission molecules bearing optically pure aminol group, which was easily synthesized. The chiral recognition is not only seen by naked eyes but also measured by fluorophotometer. The difference of fluorescence intensity between the two enantiomers of the acids aroused by the aggregation-induced emission molecules was up to 598. The chiral recognition could be applied to quantitative analysis of enantiomer content of chiral acids. More chiral AIE amines need to be developed for enantiomer analysis of more carboxylic acids.

  6. Carboxylic acid functional group analysis using constant neutral loss scanning-mass spectrometry.

    PubMed

    Dron, Julien; Eyglunent, Gregory; Temime-Roussel, Brice; Marchand, Nicolas; Wortham, Henri

    2007-12-12

    The present study describes the development of a new analytical technique for the functional group determination of the carboxylic moiety using atmospheric pressure chemical ionization-mass spectrometry (APCI-MS/MS) operated in the constant neutral loss scanning (CNLS) mode. Carboxylic groups were first derivatized into their corresponding methyl esters by reacting with BF3/methanol mix and the reaction mixture was then directly injected into the APCI chamber. The loss of methanol (m/z = 32 amu) resulting from the fragmentation of the protonated methyl esters was then monitored. Applying this method together with a statistical approach to reference mixtures containing 31 different carboxylic acids at randomly calculated concentrations demonstrated its suitability for quantitative functional group measurements with relative standard deviations below 15% and a detection limit of 0.005 mmol L(-1). Its applicability to environmental matrices was also shown through the determination of carboxylic acid concentrations inside atmospheric aerosol samples. To the best of our knowledge, it is the first time that the tandem mass spectrometry was successfully applied to functional group analysis, offering great perspectives in the characterization of complex mixtures which are prevailing in the field of environmental analysis as well as in the understanding of the chemical processes occurring in these matrices.

  7. Culture medium optimization for acetic acid production by a persimmon vinegar-derived bacterium.

    PubMed

    Kim, Jin-Nam; Choo, Jong-Sok; Wee, Young-Jung; Yun, Jong-Sun; Ryu, Hwa-Won

    2005-01-01

    A new acetic acid-producing microorganism, Acetobacter sp. RKY4, was isolated from Korean traditional persimmon vinegar, and we optimized the culture medium for acetic acid production from ethanol using the newly isolated Acetobacter sp. RKY4. The optimized culture medium for acetic acid production using this microorganism was found to be 40 g/L ethanol, 10 g/L glycerol, 10 g/L corn steep liquor, 0.5 g/L MgSO4.7H2O, and 1.0 g/L (NH4)H2PO4. Acetobacter sp. RKY4 produced 47.1 g/L of acetic acid after 48 h of fermentation in a 250 mL Erlenmeyer flask containing 50 mL of the optimized medium.

  8. Producing Acetic Acid of Acetobacter pasteurianus by Fermentation Characteristics and Metabolic Flux Analysis.

    PubMed

    Wu, Xuefeng; Yao, Hongli; Liu, Qing; Zheng, Zhi; Cao, Lili; Mu, Dongdong; Wang, Hualin; Jiang, Shaotong; Li, Xingjiang

    2018-03-19

    The acetic acid bacterium Acetobacter pasteurianus plays an important role in acetic acid fermentation, which involves oxidation of ethanol to acetic acid through the ethanol respiratory chain under specific conditions. In order to obtain more suitable bacteria for the acetic acid industry, A. pasteurianus JST-S screened in this laboratory was compared with A. pasteurianus CICC 20001, a current industrial strain in China, to determine optimal fermentation parameters under different environmental stresses. The maximum total acid content of A. pasteurianus JST-S was 57.14 ± 1.09 g/L, whereas that of A. pasteurianus CICC 20001 reached 48.24 ± 1.15 g/L in a 15-L stir stank. Metabolic flux analysis was also performed to compare the reaction byproducts. Our findings revealed the potential value of the strain in improvement of industrial vinegar fermentation.

  9. Predicting the crystallization propensity of carboxylic acid buffers in frozen systems--relevance to freeze-drying.

    PubMed

    Sundaramurthi, Prakash; Suryanarayanan, Raj

    2011-04-01

    Selective crystallization of buffer components in frozen solutions is known to cause pronounced pH shifts. Our objective was to study the crystallization behavior and the consequent pH shift in frozen aqueous carboxylic acid buffers. Aqueous carboxylic acid buffers were cooled to -25°C and the pH of the solution was measured as a function of temperature. The thermal behavior of solutions during freezing and thawing was investigated by differential scanning calorimetry. The crystallized phases in frozen solution were identified by X-ray diffractometry. The malate buffer system was robust with no evidence of buffer component crystallization and hence negligible pH shift. In the citrate and tartarate systems, at initial pH acidic buffer component (neutral form) crystallized on cooling, causing an increase in the freeze-concentrate pH. Carboxylic acid buffers were rank ordered based on their propensity to crystallize in frozen solutions. From the aqueous solubility values of these carboxylic acids, which have been reported over a range of temperatures, it was also possible to estimate the degree of supersaturation at the subambient temperature of interest. This enabled us to predict their crystallization propensity in frozen systems. The experimental and the predicted rank orderings were in excellent agreement. Copyright © 2010 Wiley-Liss, Inc.

  10. Vaporization of protic ionic liquids derived from organic superbases and short carboxylic acids.

    PubMed

    Ribeiro, Filipe M S; Lima, Carlos F R A C; Vaz, Inês C M; Rodrigues, Ana S M C; Sapei, Erlin; Melo, André; Silva, Artur M S; Santos, Luís M N B F

    2017-06-28

    This work presents a comprehensive evaluation of the phase behaviour and cohesive enthalpy of protic ionic liquids (PILs) composed of 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) organic superbases with short-chain length (acetic, propionic and butyric) carboxylic acids. Glass transition temperatures, T g , and enthalpies of vaporization, ΔH vap , were measured for six [BH][A] (1 : 1) PILs (B = DBN, DBU; A = MeCOO, EtCOO, nPrCOO), revealing more significant changes upon increasing the number of -CH 2 - groups in the base than in the acid. The magnitude of ΔH vap evidences that liquid PILs have a high proportion of ions, although the results also indicate that in DBN PILs the concentration of neutral species is not negligible. In the gas phase, these PILs exist as a distribution of ion pairs and isolated neutral species, with speciation being dependent on the temperature and pressure conditions - at high temperatures and low pressures the separated neutral species dominate. The higher T g and ΔH vap of the DBU PILs are explained by the stronger basicity of DBU (as supported by NMR and computational calculations), which increases the extent of proton exchange and the ionic character of the corresponding PILs, resulting in stronger intermolecular interactions in condensed phases.

  11. Sclerotherapy of renal cysts using acetic acid: a comparison with ethanol sclerotherapy.

    PubMed

    Cho, D S; Ahn, H S; Kim, S I; Kim, Y S; Kim, S J; Jeon, G S; Won, J H

    2008-12-01

    This study compared percutaneous sclerotherapy using 50% acetic acid with that using 99% ethanol for patients with simple renal cysts. The study included 72 simple renal cysts in 64 patients (male/female ratio = 31/33; age range, 31-75 years). Under fluoroscopic guidance, the cyst fluid was aspirated completely. Sclerotherapy was then performed using 50% acetic acid for 32 cysts and 99% ethanol for 40 cysts. The volumes of each renal cyst before and after sclerotherapy were compared using ultrasonography or CT. Medical records were reviewed to analyse any complications. The mean follow-up period was 21.5 months (range, 3-75 months). The mean remnant volume of the cyst after sclerotherapy was 2.6% of the initial volume in the acetic acid group and 14.0% in the ethanol group. The rates of complete remission, partial remission and treatment failure were 90.6%, 9.4% and 0%, respectively, in the acetic acid group, and 60.0%, 30.0% and 10.0%, respectively, in the ethanol group. There were no complications related to sclerotherapy in either group. In conclusion, acetic acid is a safe and effective sclerosing agent, with clinical results superior to those of ethanol, and is an alternative to ethanol for sclerotherapy of renal cysts.

  12. Determination of tertiary amines and salts of organic acids in acetic acid by catalytic thermometric titration.

    PubMed

    Vajgand, V J; Gaál, F F

    1967-03-01

    A new method of determination of tertiary amines and salts of organic adds in acetic acid solution, to which about 2 % of water and 8% acetic anhydride are added, is described. After the equivalence point, the excess of perchloric acid catalyses the exothermic reaction of water with acetic anhydride. The end-point is determined from the graph of temperature against volume of added titrant. If a slightly soluble compound is produced during the titration, the precision of the new method is superior to that of the potentiometric method.

  13. Prebiotic synthesis of carboxylic acids, amino acids and nucleic acid bases from formamide under photochemical conditions⋆

    NASA Astrophysics Data System (ADS)

    Botta, Lorenzo; Mattia Bizzarri, Bruno; Piccinino, Davide; Fornaro, Teresa; Robert Brucato, John; Saladino, Raffaele

    2017-07-01

    The photochemical transformation of formamide in the presence of a mixture of TiO2 and ZnO metal oxides as catalysts afforded a large panel of molecules of biological relevance, including carboxylic acids, amino acids and nucleic acid bases. The reaction was less effective when performed in the presence of only one mineral, highlighting the role of synergic effects between the photoactive catalysts. Taken together, these results suggest that the synthesis of chemical precursors for both the genetic and the metabolic apparatuses might have occurred in a simple environment, consisting of formamide, photoactive metal oxides and UV-radiation.

  14. Spectroscopic studies of transition-metal ions in molten alkali-metal carboxylates

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

    Maroni, V.A.; Maciejewski, M.L.

    This paper presents the results of electronic absorption and /sup 13/C-NMR measurements on molten alkali metal formates and acetates and on solutions of selected 3d transition metal ions therein. These studies provide a unique opportunity to explore (1) the highly ordered nature of alkali carboxylates, (2) the ligand field properties of acetate and formate ions, and (3) the coordination chemistry of the 3d transition metals in molten carboxylates. 1 figure, 2 tables.

  15. 21 CFR 184.1005 - Acetic acid.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... other food categories. The ingredient may also be used in boiler water additives at levels not to exceed... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Acetic acid. 184.1005 Section 184.1005 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN...

  16. Extraction of ethanol with higher carboxylic acid solvents and their toxicity to yeast

    USDA-ARS?s Scientific Manuscript database

    In a screening exercise for ethanol-selective extraction solvents, partitioning of ethanol and water from a 5 wt% aqueous solution into several C8 – C18 carboxylic acids was studied. Results for the acids are compared with those from alcohols of similar structure. In all cases studied, the acids exh...

  17. Determination of polyfluoroalkyl phosphoric acid diesters, perfluoroalkyl phosphonic acids, perfluoroalkyl phosphinic acids, perfluoroalkyl carboxylic acids, and perfluoroalkane sulfonic acids in lake trout from the Great Lakes region.

    PubMed

    Guo, Rui; Reiner, Eric J; Bhavsar, Satyendra P; Helm, Paul A; Mabury, Scott A; Braekevelt, Eric; Tittlemier, Sheryl A

    2012-11-01

    A comprehensive method to extract perfluoroalkyl carboxylic acids, perfluoroalkane sulfonic acids, perfluoroalkyl phosphonic acids, perfluoroalkyl phosphinic acids, and polyfluoroalkyl phosphoric acid diesters simultaneously from fish samples has been developed. The recoveries of target compounds ranged from 78 % to 121 %. The new method was used to analyze lake trout (Salvelinus namaycush) from the Great Lakes region. The results showed that the total perfluoroalkane sulfonate concentrations ranged from 0.1 to 145 ng/g (wet weight) with perfluorooctane sulfonate (PFOS) as the dominant contaminant. Concentrations in fish between lakes were in the order of Lakes Ontario ≈ Erie > Huron > Superior ≈ Nipigon. The total perfluoroalkyl carboxylic acid concentrations ranged from 0.2 to 18.2 ng/g wet weight. The aggregate mean perfluorooctanoic acid (PFOA) concentration in fish across all lakes was 0.045 ± 0.023 ng/g. Mean concentrations of PFOA were not significantly different (p > 0.1) among the five lakes. Perfluoroalkyl phosphinic acids were detected in lake trout from Lake Ontario, Lake Erie, and Lake Huron with concentration ranging from non-detect (ND) to 0.032 ng/g. Polyfluoroalkyl phosphoric acid diesters were detected only in lake trout from Lake Huron, at levels similar to perfluorooctanoic acid.

  18. DETERMINATION OF CARBOXYLIC ACIDS BY ION-EXCLUSION CHROMATOGRAPHY WITH NON-SUPPRESSED CONDUCTIVITY AND OPTICAL DETECTORS

    EPA Science Inventory

    Determination of carboxylic acids using non-suppressed conductivity and UV detections is described. The background conductance of 1-octanesulfonic acid, hexane sulfonic acid and sulfuric acid at varying concentrations was determined. Using 0.2 mM 1-octanesulfonic acid as a mobile...

  19. Properties of Acetate Kinase Isozymes and a Branched-Chain Fatty Acid Kinase from a Spirochete

    PubMed Central

    Harwood, Caroline S.; Canale-Parola, Ercole

    1982-01-01

    Spirochete MA-2, which is anaerobic, ferments glucose, forming acetate as a major product. The spirochete also ferments (but does not utilize as growth substrates) small amounts of l-leucine, l-isoleucine, and l-valine, forming the branched-chain fatty acids isovalerate, 2-methylbutyrate, and isobutyrate, respectively, as end products. Energy generated through the fermentation of these amino acids is utilized to prolong cell survival under conditions of growth substrate starvation. A branched-chain fatty acid kinase and two acetate kinase isozymes were resolved from spirochete MA-2 cell extracts. Kinase activity was followed by measuring the formation of acyl phosphate from fatty acid and ATP. The branched-chain fatty acid kinase was active with isobutyrate, 2-methylbutyrate, isovalerate, butyrate, valerate, or propionate as a substrate but not with acetate as a substrate. The acetate kinase isozymes were active with acetate and propionate as substrates but not with longer-chain fatty acids as substrates. The acetate kinase isozymes and the branched-chain fatty acid kinase differed in nucleoside triphosphate and cation specificities. Each acetate kinase isozyme had an apparent molecular weight of approximately 125,000, whereas the branched-chain fatty acid kinase had a molecular weight of approximately 76,000. These results show that spirochete MA-2 synthesizes a branched-chain fatty acid kinase specific for leucine, isoleucine, and valine fermentation. It is likely that a phosphate branched-chain amino acids is also synthesized by spirochete MA-2. Thus, in spirochete MA-2, physiological mechanisms have evolved which serve specifically to generate maintenance energy from branched-chain amino acids. PMID:6288660

  20. The Key to Acetate: Metabolic Fluxes of Acetic Acid Bacteria under Cocoa Pulp Fermentation-Simulating Conditions

    PubMed Central

    Adler, Philipp; Frey, Lasse Jannis; Berger, Antje; Bolten, Christoph Josef; Hansen, Carl Erik

    2014-01-01

    Acetic acid bacteria (AAB) play an important role during cocoa fermentation, as their main product, acetate, is a major driver for the development of the desired cocoa flavors. Here, we investigated the specialized metabolism of these bacteria under cocoa pulp fermentation-simulating conditions. A carefully designed combination of parallel 13C isotope labeling experiments allowed the elucidation of intracellular fluxes in the complex environment of cocoa pulp, when lactate and ethanol were included as primary substrates among undefined ingredients. We demonstrate that AAB exhibit a functionally separated metabolism during coconsumption of two-carbon and three-carbon substrates. Acetate is almost exclusively derived from ethanol, while lactate serves for the formation of acetoin and biomass building blocks. Although this is suboptimal for cellular energetics, this allows maximized growth and conversion rates. The functional separation results from a lack of phosphoenolpyruvate carboxykinase and malic enzymes, typically present in bacteria to interconnect metabolism. In fact, gluconeogenesis is driven by pyruvate phosphate dikinase. Consequently, a balanced ratio of lactate and ethanol is important for the optimum performance of AAB. As lactate and ethanol are individually supplied by lactic acid bacteria and yeasts during the initial phase of cocoa fermentation, respectively, this underlines the importance of a well-balanced microbial consortium for a successful fermentation process. Indeed, AAB performed the best and produced the largest amounts of acetate in mixed culture experiments when lactic acid bacteria and yeasts were both present. PMID:24837393

  1. The key to acetate: metabolic fluxes of acetic acid bacteria under cocoa pulp fermentation-simulating conditions.

    PubMed

    Adler, Philipp; Frey, Lasse Jannis; Berger, Antje; Bolten, Christoph Josef; Hansen, Carl Erik; Wittmann, Christoph

    2014-08-01

    Acetic acid bacteria (AAB) play an important role during cocoa fermentation, as their main product, acetate, is a major driver for the development of the desired cocoa flavors. Here, we investigated the specialized metabolism of these bacteria under cocoa pulp fermentation-simulating conditions. A carefully designed combination of parallel 13C isotope labeling experiments allowed the elucidation of intracellular fluxes in the complex environment of cocoa pulp, when lactate and ethanol were included as primary substrates among undefined ingredients. We demonstrate that AAB exhibit a functionally separated metabolism during coconsumption of two-carbon and three-carbon substrates. Acetate is almost exclusively derived from ethanol, while lactate serves for the formation of acetoin and biomass building blocks. Although this is suboptimal for cellular energetics, this allows maximized growth and conversion rates. The functional separation results from a lack of phosphoenolpyruvate carboxykinase and malic enzymes, typically present in bacteria to interconnect metabolism. In fact, gluconeogenesis is driven by pyruvate phosphate dikinase. Consequently, a balanced ratio of lactate and ethanol is important for the optimum performance of AAB. As lactate and ethanol are individually supplied by lactic acid bacteria and yeasts during the initial phase of cocoa fermentation, respectively, this underlines the importance of a well-balanced microbial consortium for a successful fermentation process. Indeed, AAB performed the best and produced the largest amounts of acetate in mixed culture experiments when lactic acid bacteria and yeasts were both present.

  2. 40 CFR 721.4663 - Fluorinated carboxylic acid alkali metal salts.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fluorinated carboxylic acid alkali metal salts. 721.4663 Section 721.4663 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.4663...

  3. The effect of methanogenesis inhibition, inoculum and substrate concentration on hydrogen and carboxylic acids production from cassava wastewater.

    PubMed

    Amorim, Norma C S; Amorim, Eduardo L C; Kato, Mario T; Florencio, Lourdinha; Gavazza, Savia

    2018-02-01

    Manipueira is a carbohydrate-rich agro-industrial waste from cassava processing. It is considered well suitable for biotechnological processes, such as hydrogen and carboxylic acids production, due to the high content of easily degradable organic matter. However, the proper methanogenesis inhibition method, inoculum type, and organic loads are factors still limiting the processes. The objective in this work was to evaluate the effects of such factors on byproducts production in anaerobic reactors. Batch experiments were conducted with 2.3-L flasks during two operational phases. In the first phase (P1), inhibition of methanogens in the sludge was evaluated using acetylene (1% v/v of headspace) and heat treatment (120 °C, 1 atm for 30 min). In the second phase (P2), three inoculum types obtained from common anaerobic sludges (bovine rumen and sludges from municipal and textile industrial wastewater treatment plants) were individually assayed. P2 aimed to identify the best inoculum, based on hydrogen production ability, which was tested for three initial concentrations of manipueira in terms of chemical oxygen demand (COD) (10, 20 and 40 g O 2 /L). Results of P1 indicated that either acetylene or heat treatment efficiently inhibited methanogenesis, with no methane production. However, the maximum H 2 production potential by applying heat treatment (~ 563 mL) was more than twice compared with that by acetylene treatment (~ 257 mL); and butyrate was the main carboxylic acid by-product (~ 3 g/L). In P2 experiments after sludge heat treatment, the highest hydrogen yield (1.66 ± 0.07 mol H 2 /mol glucose) and caproic acid production (~ 2 g/L) were observed at 20 g O 2 /L of manipueira COD, when bovine rumen was the inoculum. The primary metabolic degradation products in all P2 experiments were ethanol, acetic, butyric, propionic and caproic acids. The finding of caproic acid detection indicated that the applied conditions in manipueira anaerobic

  4. Iron-catalyzed olefin epoxidation in the presence of acetic acid: insights into the nature of the metal-based oxidant.

    PubMed

    Mas-Ballesté, Rubén; Que, Lawrence

    2007-12-26

    The iron complexes [(BPMEN)Fe(OTf)2] (1) and [(TPA)Fe(OTf)2] (2) [BPMEN = N,N'-bis-(2-pyridylmethyl)-N,N'-dimethyl-1,2-ethylenediamine; TPA = tris-(2-pyridylmethyl)amine] catalyze the oxidation of olefins by H2O2 to yield epoxides and cis-diols. The addition of acetic acid inhibits olefin cis-dihydroxylation and enhances epoxidation for both 1 and 2. Reactions carried out at 0 degrees C with 0.5 mol % catalyst and a 1:1.5 olefin/H2O2 ratio in a 1:2 CH3CN/CH3COOH solvent mixture result in nearly quantitative conversions of cyclooctene to epoxide within 1 min. The nature of the active species formed in the presence of acetic acid has been probed at low temperature. For 2, in the absence of substrate, [(TPA)FeIII(OOH)(CH3COOH)]2+ and [(TPA)FeIVO(NCCH3)]2+ intermediates can be observed. However, neither is the active epoxidizing species. In fact, [(TPA)FeIVO(NCCH3)]2+ is shown to form in competition with substrate oxidation. Consequently, it is proposed that epoxidation is mediated by [(TPA)FeV(O)(OOCCH3)]2+, generated from O-O bond heterolysis of the [(TPA)FeIII(OOH)(CH3COOH)]2+ intermediate, which is promoted by the protonation of the terminal oxygen atom of the hydroperoxide by the coordinated carboxylic acid.

  5. Butyric acid production from softwood hydrolysate by acetate-consuming Clostridium sp. S1 with high butyric acid yield and selectivity.

    PubMed

    Kim, Minsun; Kim, Ki-Yeon; Lee, Kyung Min; Youn, Sung Hun; Lee, Sun-Mi; Woo, Han Min; Oh, Min-Kyu; Um, Youngsoon

    2016-10-01

    The aim of this work was to study the butyric acid production from softwood hydrolysate by acetate-consuming Clostridium sp. S1. Results showed that Clostridium sp. S1 produced butyric acid by simultaneously utilizing glucose and mannose in softwood hydrolysate and, more remarkably, it consumed acetic acid in hydrolysate. Clostridium sp. S1 utilized each of glucose, mannose, and xylose as well as mixed sugars simultaneously with partially repressed xylose utilization. When softwood (Japanese larch) hydrolysate containing glucose and mannose as the main sugars was used, Clostridium sp. S1 produced 21.17g/L butyric acid with the yield of 0.47g/g sugar and the selectivity of 1 (g butyric acid/g total acids) owing to the consumption of acetic acid in hydrolysate. The results demonstrate potential of Clostridium sp. S1 to produce butyric acid selectively and effectively from hydrolysate not only by utilizing mixed sugars simultaneously but also by converting acetic acid to butyric acid. Copyright © 2016 Elsevier Ltd. All rights reserved.

  6. Granisetron ameliorates acetic acid-induced colitis in rats.

    PubMed

    Fakhfouri, Gohar; Rahimian, Reza; Daneshmand, Ali; Bahremand, Arash; Rasouli, Mohammad Reza; Dehpour, Ahmad Reza; Mehr, Shahram Ejtemaei; Mousavizadeh, Kazem

    2010-04-01

    Inflammatory bowel disease (IBD) is a chronically relapsing inflammation of the gastrointestinal tract, of which the definite etiology remains ambiguous. Considering the adverse effects and incomplete efficacy of currently administered drugs, it is indispensable to explore new candidates with more desirable therapeutic profiles. 5-HT( 3) receptor antagonists have shown analgesic and anti-inflammatory properties in vitro and in vivo. This study aims to investigate granisetron, a 5-HT( 3) receptor antagonist, in acetic acid-induced rat colitis and probable involvement of 5-HT(3) receptors. Colitis was rendered by instillation of 1 mL of 4% acetic acid (vol/vol) and after 1 hour, granisetron (2 mg/kg), dexamethasone (1 mg/kg), meta-chlorophenylbiguanide (mCPBG, 5 mg/kg), a 5-HT( 3) receptor agonist, or granisetron + mCPBG was given intraperitoneally. Twenty-four hours following colitis induction, animals were sacrificed and distal colons were assessed macroscopically, histologically and biochemically (malondialdehyde, myeloperoxidase, tumor necrosis factor-alpha, interleukin-1 beta and interleukin-6). Granisetron or dexamethasone significantly (p < .05) improved macroscopic and histologic scores, curtailed myeloperoxidase activity and diminished colonic levels of inflammatory cytokines and malondialdehyde. The protective effects of granisetron were reversed by concurrent administration of mCPBG. Our data suggests that the salutary effects of granisetron in acetic acid colitis could be mediated by 5-HT(3) receptors.

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

    NASA Astrophysics Data System (ADS)

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

    2007-03-01

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

  8. [Comparative genomics and evolutionary analysis of CRISPR loci in acetic acid bacteria].

    PubMed

    Xia, Kai; Liang, Xin-le; Li, Yu-dong

    2015-12-01

    The clustered regularly interspaced short palindromic repeat (CRISPR) is a widespread adaptive immunity system that exists in most archaea and many bacteria against foreign DNA, such as phages, viruses and plasmids. In general, CRISPR system consists of direct repeat, leader, spacer and CRISPR-associated sequences. Acetic acid bacteria (AAB) play an important role in industrial fermentation of vinegar and bioelectrochemistry. To investigate the polymorphism and evolution pattern of CRISPR loci in acetic acid bacteria, bioinformatic analyses were performed on 48 species from three main genera (Acetobacter, Gluconacetobacter and Gluconobacter) with whole genome sequences available from the NCBI database. The results showed that the CRISPR system existed in 32 species of the 48 strains studied. Most of the CRISPR-Cas system in AAB belonged to type I CRISPR-Cas system (subtype E and C), but type II CRISPR-Cas system which contain cas9 gene was only found in the genus Acetobacter and Gluconacetobacter. The repeat sequences of some CRISPR were highly conserved among species from different genera, and the leader sequences of some CRISPR possessed conservative motif, which was associated with regulated promoters. Moreover, phylogenetic analysis of cas1 demonstrated that they were suitable for classification of species. The conservation of cas1 genes was associated with that of repeat sequences among different strains, suggesting they were subjected to similar functional constraints. Moreover, the number of spacer was positively correlated with the number of prophages and insertion sequences, indicating the acetic acid bacteria were continually invaded by new foreign DNA. The comparative analysis of CRISR loci in acetic acid bacteria provided the basis for investigating the molecular mechanism of different acetic acid tolerance and genome stability in acetic acid bacteria.

  9. Effect of manganese ions on ethanol fermentation by xylose isomerase expressing Saccharomyces cerevisiae under acetic acid stress.

    PubMed

    Ko, Ja Kyong; Um, Youngsoon; Lee, Sun-Mi

    2016-12-01

    The efficient fermentation of lignocellulosic hydrolysates in the presence of inhibitors is highly desirable for bioethanol production. Among the inhibitors, acetic acid released during the pretreatment of lignocellulose negatively affects the fermentation performance of biofuel producing organisms. In this study, we evaluated the inhibitory effects of acetic acid on glucose and xylose fermentation by a high performance engineered strain of xylose utilizing Saccharomyces cerevisiae, SXA-R2P-E, harboring a xylose isomerase based pathway. The presence of acetic acid severely decreased the xylose fermentation performance of this strain. However, the acetic acid stress was alleviated by metal ion supplementation resulting in a 52% increased ethanol production rate under 2g/L of acetic acid stress. This study shows the inhibitory effect of acetic acid on an engineered isomerase-based xylose utilizing strain and suggests a simple but effective method to improve the co-fermentation performance under acetic acid stress for efficient bioethanol production. Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. Properties of MgB 2 superconductor chemically treated by acetic acid

    NASA Astrophysics Data System (ADS)

    Hušeková, K.; Hušek, I.; Kováč, P.; Kulich, M.; Dobročka, E.; Štrbík, V.

    2010-03-01

    Commercial Alfa Aesar MgB 2 powder was chemically treated by acetic acid with the aim of MgO removing. Single-core MgB 2/Fe ex situ wires have been made by powder-in-tube (PIT) process using the powders treated with different acid concentration. All samples were annealed in argon at 950 °C/0.5 h. Differences in transition temperatures and critical currents of acetic acid treated MgB 2 are related to the normal state resistivity, effective carbon substitution from the organic solvent and the active area fraction (grain-connectivity).

  11. Discovery of a Novel Series of CRTH2 (DP2) Receptor Antagonists Devoid of Carboxylic Acids

    PubMed Central

    2011-01-01

    Antagonism of the CRTH2 receptor represents a very attractive target for a variety of allergic diseases. Most CRTH2 antagonists known to date possess a carboxylic acid moiety, which is essential for binding. However, potential acid metabolites O-acyl glucuronides might be linked to idiosynchratic toxicity in humans. In this communication, we describe a new series of compounds that lack the carboxylic acid moiety. Compounds with high affinity (Ki < 10 nM) for the receptor have been identified. Subsequent optimization succeeded in reducing the high metabolic clearance of the first compounds in human and rat liver microsomes. At the same time, inhibition of the CYP isoforms was optimized, giving rise to stable compounds with an acceptable CYP inhibition profile (IC50 CYP2C9 and 2C19 > 1 μM). Taken together, these data show that compounds devoid of carboxylic acid groups could represent an interesting alternative to current CRTH2 antagonists in development. PMID:24900284

  12. Effect of acetic acid on ethanol production by Zymomonas mobilis mutant strains through continuous adaptation.

    PubMed

    Liu, Yu-Fan; Hsieh, Chia-Wen; Chang, Yao-Sheng; Wung, Being-Sun

    2017-08-01

    Acetic acid is a predominant by-product of lignocellulosic biofuel process, which inhibits microbial biocatalysts. Development of bacterial strains that are tolerant to acetic acid is challenging due to poor understanding of the underlying molecular mechanisms. In this study, we generated and characterized two acetic acid-tolerant strains of Zymomonas mobilis using N-methyl-N'-nitro-N-nitrosoguanidine (NTG)-acetate adaptive breeding. Two mutants, ZMA-142 and ZMA-167, were obtained, showing a significant growth rate at a concentration of 244 mM sodium acetate, while the growth of Z. mobilis ATCC 31823 were completely inhibited in presence of 195 mM sodium acetate. Our data showed that acetate-tolerance of ZMA-167 was attributed to a co-transcription of nhaA from ZMO0117, whereas the co-transcription was absent in ATCC 31823 and ZMA-142. Moreover, ZMA-142 and ZMA-167 exhibited a converstion rate (practical ethanol yield to theorical ethanol yield) of 90.16% and 86% at 195 mM acetate-pH 5 stress condition, respectively. We showed that acid adaptation of ZMA-142 and ZMA-167 to 146 mM acetate increased ZMA-142 and ZMA-167 resulted in an increase in ethanol yield by 32.21% and 21.16% under 195 mM acetate-pH 5 stress condition, respectively. The results indicate the acetate-adaptive seed culture of acetate-tolerant strains, ZMA-142 and ZMA-167, could enhance the ethanol production during fermentation.

  13. On the formation of niacin (vitamin B3) and pyridine carboxylic acids in interstellar model ices

    NASA Astrophysics Data System (ADS)

    McMurtry, Brandon M.; Turner, Andrew M.; Saito, Sean E. J.; Kaiser, Ralf I.

    2016-06-01

    The formation of pyridine carboxylic acids in interstellar ice grains was simulated by electron exposures of binary pyridine (C5H5N)-carbon dioxide (CO2) ice mixtures at 10 K under contamination-free ultrahigh vacuum conditions. Chemical processing of the pristine ice and subsequent warm-up phase was monitored on line and in situ via Fourier transform infrared spectroscopy to probe for the formation of new radiation induced species. In the infrared spectra of the irradiated ice, bands assigned to nicotinic acid (niacin; vitamin B3; m-C5H4NCOOH) along with 2,3-, 2,5-, 3,4-, and 3,5-pyridine dicarboxylic acid (C5H3N(COOH)2) were unambiguously identified along with the hydroxycarbonyl (HOCO) radical. Our study suggests that the reactive pathway responsible for pyridine carboxylic acids formation involves a HOCO intermediate, which forms through the reaction of suprathermal hydrogen ejected from pyridine with carbon dioxide. The newly formed pyridinyl radical may then undergo radical-radical recombination with a hydroxycarbonyl radical to form a pyridine carboxylic acid.

  14. Additional Nucleophile-Free FeCl3-Catalyzed Green Deprotection of 2,4-Dimethoxyphenylmethyl-Protected Alcohols and Carboxylic Acids.

    PubMed

    Sawama, Yoshinari; Masuda, Masahiro; Honda, Akie; Yokoyama, Hiroki; Park, Kwihwan; Yasukawa, Naoki; Monguchi, Yasunari; Sajiki, Hironao

    2016-01-01

    The deprotection of the methoxyphenylmethyl (MPM) ether and ester derivatives can be generally achieved by the combinatorial use of a catalytic Lewis acid and stoichiometric nucleophile. The deprotections of 2,4-dimethoxyphenylmethyl (DMPM)-protected alcohols and carboxylic acids were found to be effectively catalyzed by iron(III) chloride without any additional nucleophile to form the deprotected mother alcohols and carboxylic acids in excellent yields. Since the present deprotection proceeds via the self-assembling mechanism of the 2,4-DMPM protective group itself to give the hardly-soluble resorcinarene derivative as a precipitate, the rigorous purification process by silica-gel column chromatography was unnecessary and the sufficiently-pure alcohols and carboxylic acids were easily obtained in satisfactory yields after simple filtration.

  15. Structural characterization of 1,3-propanedithiols that feature carboxylic acids: Homologues of mercury chelating agents ✩

    PubMed Central

    Sattler, Wesley; Palmer, Joshua H.; Bridges, Christy C.; Joshee, Lucy; Zalups, Rudolfs K.; Parkin, Gerard

    2013-01-01

    The molecular structures of a series of 1,3-propanedithiols that contain carboxylic acid groups, namely rac- and meso-2,4-dimercaptoglutaric acid (H4DMGA) and 2-carboxy-1,3-propanedithiol (H3DMCP), have been determined by X-ray diffraction. Each compound exhibits two centrosymmetric intermolecular hydrogen bonding interactions between pairs of carboxylic acid groups, which result in a dimeric structure for H3DMCP and a polymeric tape-like structure for rac- and meso-H4DMGA. Significantly, the hydrogen bonding motifs observed for rac- and meso-H4DMGA are very different to those observed for the 1,2-dithiol, rac-2,3-dimercaptosuccinic acid (rac-H4DMSA), in which the two oxygen atoms of each carboxylic acid group hydrogen bond to two different carboxylic acid groups, thereby resulting in a hydrogen bonded sheet-like structure rather than a tape. Density functional theory calculations indicate that 1,3-dithiolate coordination to mercury results in larger S–Hg–S bond angles than does 1,2-dithiolate coordination, but these angles are far from linear. As such, κ2-S2 coordination of these dithiolate ligands is expected to be associated with mercury coordination numbers of greater than two. In vivo studies demonstrate that both rac-H4DMGA and H3DMCP reduce the renal burden of mercury in rats, although the compounds are not as effective as either 2,3-dimercaptopropane-1-sulfonic acid (H3DMPS) or meso-H4DMSA. PMID:24187425

  16. Novel lead(II) carboxylate-arsonate hybrids

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

    Yi Feiyan; Song Junling; Zhao Na

    2008-06-15

    Hydrothermal reactions of lead(II) acetate with phenylarsonic acid (H{sub 2}L{sup 1}) (or 4-hydroxy-3-nitrophenylarsonic acid, H{sub 3}L{sup 2}) and 5-sulfoisophthalic acid monosodium salt (NaH{sub 2}SIP) (or 1,3,5-benzenetricarboxylic acid (H{sub 3}BTC)) as the second metal linkers afforded three novel mixed-ligand lead(II) carboxylate-arsonates, namely, Pb{sub 5}(SIP){sub 2}(L{sup 1}){sub 2}(H{sub 2}O) 1, Pb{sub 3}(SIP)(L{sup 2})(H{sub 2}O) 2 and Pb(H{sub 2}L{sup 2})(H{sub 2}BTC) 3. The structure of 1 features a complicated 3D network composed of 2D double layers of lead(II) sulfoisophthalate bridged by 1D chains of lead(II) arsonates along b-axis, forming large tunnels along b-axis which are occupied by phenyl rings of the arsonate ligands.more » In 2, the Pb(II) ions are bridged by {l_brace}L{sup 2}{r_brace}{sup 3-} anions into a 2D double layer whereas the interconnection of the Pb(II) ions via bridging and chelating SIP anions gave a 2D double layer. The cross-linkage of the above two building units leads to a complicated 3D network. In 3, the interconnection of the Pb(II) ions via bridging {l_brace}H{sub 2}L{sup 2}{r_brace}{sup -} and {l_brace}H{sub 2}BTC{r_brace}{sup -} anions leads to a 1D double chain down a-axis. These 1D chains are further interconnected via hydrogen bonds among non-coordination carboxylate groups and arsonate oxygens into a 3D supramolecular architecture. - Graphical abstract: Three novel mixed-ligand lead(II) carboxylate-arsonates, namely, Pb{sub 5}(SIP){sub 2}(L{sup 1}){sub 2}(H{sub 2}O) 1, Pb{sub 3}(SIP)(L{sup 2})(H{sub 2}O) 2 and Pb(H{sub 2}L{sup 2})(H{sub 2}BTC) 3 have been synthesized and structurally characterized. Compounds 1 and 2 feature complicated 3D network structures whereas compound 3 features 1D lead(II) carboxylate-arsonate chains that are further interlinked by strong hydrogen bonds into a 3D supramolecular assembly.« less

  17. Impact of acetic acid concentration, application volume, and adjuvants on weed control efficacy

    USDA-ARS?s Scientific Manuscript database

    Vinegar has been identified as a potential organic herbicide, yet additional information is needed to determine the influence of acetic acid concentration, application volume, and adjuvants on weed control. Acetic acid is a contact herbicide, injuring and killing plants by first destroying the cell ...

  18. Solvent-Free Esterification of Carboxylic Acids Using Supported Iron Oxide Nanoparticles as an Efficient and Recoverable Catalyst

    PubMed Central

    Rajabi, Fatemeh; Abdollahi, Mohammad; Luque, Rafael

    2016-01-01

    Supported iron oxide nanoparticles on mesoporous materials (FeNP@SBA-15) have been successfully utilized in the esterification of a variety carboxylic acids including aromatic, aliphatic, and long-chain carboxylic acids under convenient reaction conditions. The supported catalyst could be easily recovered after reaction completion and reused several times without any loss in activity after up to 10 runs. PMID:28773685

  19. Synthesis of aminocarbonyl N-acylhydrazones by a three-component reaction of isocyanides, hydrazonoyl chlorides, and carboxylic acids.

    PubMed

    Giustiniano, Mariateresa; Meneghetti, Fiorella; Mercalli, Valentina; Varese, Monica; Giustiniano, Francesco; Novellino, Ettore; Tron, Gian Cesare

    2014-10-17

    A novel one-pot multicomponent synthesis of α-aminocarbonyl N-acylhydrazones starting from readily available hydrazonoyl chlorides, isocyanides, and carboxylic acids is reported. The strategy exploits the ability of the carboxylic acid as a third component to suppress all competing reactions between nitrile imines and isocyanides, channeling the course of the reaction toward the formation of this novel class of compounds.

  20. Surface Patterning of Benzene Carboxylic Acids on Graphite: Influence of structure, solvent, and concentration on molecular self-assembly

    NASA Astrophysics Data System (ADS)

    Florio, Gina; Stiso, Kimberly; Campanelli, Joseph; Dessources, Kimberly; Folkes, Trudi

    2012-02-01

    Scanning tunneling microscopy (STM) was used to investigate the molecular self-assembly of four different benzene carboxylic acid derivatives at the liquid/graphite interface: pyromellitic acid (1,2,4,5-benzenetetracarboxylic acid), trimellitic acid (1,2,4-benzenetricarboxylic acid), trimesic acid (1,3,5-benzenetricarboxylic acid), and 1,3,5-benzenetriacetic acid. A range of two dimensional networks are observed that depend sensitively on the number of carboxylic acids present, the nature of the solvent, and the solution concentration. We will describe our recent efforts to determine (a) the preferential two-dimensional structure(s) for each benzene carboxylic acid at the liquid/graphite interface, (b) the thermodynamic and kinetic factors influencing self-assembly (or lack thereof), (c) the role solvent plays in the assembly, (e) the effect of in situ versus ex situ dilution on surface packing density, and (f) the temporal evolution of the self-assembled monolayer. Results of computational analysis of analog molecules and model monolayer films will also be presented to aid assignment of network structures and to provide a qualitative picture of surface adsorption and network formation.

  1. Improved Acetic Acid Resistance in Saccharomyces cerevisiae by Overexpression of the WHI2 Gene Identified through Inverse Metabolic Engineering

    PubMed Central

    Chen, Yingying; Stabryla, Lisa

    2016-01-01

    Development of acetic acid-resistant Saccharomyces cerevisiae is important for economically viable production of biofuels from lignocellulosic biomass, but the goal remains a critical challenge due to limited information on effective genetic perturbation targets for improving acetic acid resistance in the yeast. This study employed a genomic-library-based inverse metabolic engineering approach to successfully identify a novel gene target, WHI2 (encoding a cytoplasmatic globular scaffold protein), which elicited improved acetic acid resistance in S. cerevisiae. Overexpression of WHI2 significantly improved glucose and/or xylose fermentation under acetic acid stress in engineered yeast. The WHI2-overexpressing strain had 5-times-higher specific ethanol productivity than the control in glucose fermentation with acetic acid. Analysis of the expression of WHI2 gene products (including protein and transcript) determined that acetic acid induced endogenous expression of Whi2 in S. cerevisiae. Meanwhile, the whi2Δ mutant strain had substantially higher susceptibility to acetic acid than the wild type, suggesting the important role of Whi2 in the acetic acid response in S. cerevisiae. Additionally, overexpression of WHI2 and of a cognate phosphatase gene, PSR1, had a synergistic effect in improving acetic acid resistance, suggesting that Whi2 might function in combination with Psr1 to elicit the acetic acid resistance mechanism. These results improve our understanding of the yeast response to acetic acid stress and provide a new strategy to breed acetic acid-resistant yeast strains for renewable biofuel production. PMID:26826231

  2. The effects of borate minerals on the synthesis of nucleic acid bases, amino acids and biogenic carboxylic acids from formamide.

    PubMed

    Saladino, Raffaele; Barontini, Maurizio; Cossetti, Cristina; Di Mauro, Ernesto; Crestini, Claudia

    2011-08-01

    The thermal condensation of formamide in the presence of mineral borates is reported. The products afforded are precursors of nucleic acids, amino acids derivatives and carboxylic acids. The efficiency and the selectivity of the reaction was studied in relation to the elemental composition of the 18 minerals analyzed. The possibility of synthesizing at the same time building blocks of both genetic and metabolic apparatuses, along with the production of amino acids, highlights the interest of the formamide/borate system in prebiotic chemistry.

  3. Fermentative utilization of glycerol residue for the production of acetic acid

    NASA Astrophysics Data System (ADS)

    Irvan; Trisakti, B.; Hasibuan, R.; Joli, M.

    2018-02-01

    Glycerol residue, frequently known as pitch, is a waste produced from the downstream product of crude glycerine distillation. With the increasing need of pure glycerine in the world, the glycerol residue produced is also increasing. Glycerol residue is a solid waste at room temperature, highly alkaline (pH > 13), corrosive, and categorized as hazardous and poisonous waste. In this research, acetic acid was produced from glycerol residue through the anaerobic fermentation process by using purple non-sulphur photosynthetic bacteria. The purpose of this study was to find out the influence of concentration change of glycerol residue on time and to find out the possibility of glycerol residue to be utilized as acetic acid. In this research, at first 400 g of glycerol residue was diluted with 200 ml of distilled water to change the glycerine phase, from solid to liquid at room temperature, acidified by using hydrochloric acid until pH 2. The top layer formed was fatty acid and triglycerides that should be removed. Meanwhile, the bottom layer was diluted glycerol residue which was then neutralized with caustic soda. To produce acetic acid, glycerol residue with various concentrations, salt, and purple non-sulphur photosynthetic bacteria were put together into a 100 ml bottle which had been previously sterilized, then incubated for four weeks under the light of 40-watt bulb. The result showed that on the 28th day of fermentation, the produced acetic acid were 0.28, 1.85, and 0.2% (w/w) by using glycerine with the concentration of 0.5, 1.0, and 1.5% (w/w), respectively.

  4. Sphingolipid biosynthesis upregulation by TOR Complex 2-Ypk1 signaling during yeast adaptive response to acetic acid stress

    PubMed Central

    Guerreiro, Joana F.; Muir, Alexander; Ramachandran, Subramaniam; Thorner, Jeremy; Sá-Correia, Isabel

    2016-01-01

    Acetic acid-induced inhibition of yeast growth and metabolism limits the productivity of industrial fermentation processes, especially when lignocellulosic hydrolysates are used as feedstock in industrial biotechnology. Tolerance to acetic acid of food spoilage yeasts is also a problem in the preservation of acidic foods and beverages. Thus, understanding the molecular mechanisms underlying adaptation and tolerance to acetic acid stress is increasingly important in industrial biotechnology and the food industry. Prior genetic screens for S. cerevisiae mutants with increased sensitivity to acetic acid identified loss-of-function mutations in the YPK1 gene, which encodes a protein kinase activated by the Target of Rapamycin (TOR) Complex 2 (TORC2). We show here by several independent criteria that TORC2-Ypk1 signaling is stimulated in response to acetic acid stress. Moreover, we demonstrate that TORC2-mediated Ypk1 phosphorylation and activation is necessary for acetic acid tolerance, and occurs independently of Hrk1, a protein kinase previously implicated in the cellular response to acetic acid. In addition, we show that TORC2-Ypk1-mediated activation of L-serine: palmitoyl-CoA acyltransferase, the enzyme complex that catalyzes the first committed step of sphingolipid biosynthesis, is required for acetic acid tolerance. Furthermore, analysis of the sphingolipid pathway using inhibitors and mutants indicates that it is production of certain complex sphingolipids that contributes to conferring acetic acid tolerance. Consistent with that conclusion, promoting sphingolipid synthesis by adding exogenous long-chain base precursor phytosphingosine to the growth medium enhanced acetic acid tolerance. Thus, appropriate modulation of the TORC2-Ypk1-sphingolipid axis in industrial yeast strains may have utility in improving fermentations of acetic acid-containing feedstocks. PMID:27671892

  5. Effects of acetic acid, ethanol, and SO(2) on the removal of volatile acidity from acidic wines by two Saccharomyces cerevisiae commercial strains.

    PubMed

    Vilela-Moura, Alice; Schuller, Dorit; Mendes-Faia, Arlete; Côrte-Real, Manuela

    2010-07-01

    Herein, we report the influence of different combinations of initial concentration of acetic acid and ethanol on the removal of acetic acid from acidic wines by two commercial Saccharomyces cerevisiae strains S26 and S29. Both strains reduced the volatile acidity of an acidic wine (1.0 gl(-1) acetic acid and 11% (v/v) ethanol) by 78% and 48%, respectively. Acetic acid removal by strains S26 and S29 was associated with a decrease in ethanol concentration of 0.7 and 1.2% (v/v), respectively. Strain S26 revealed better removal efficiency due to its higher tolerance to stress factors imposed by acidic wines. Sulfur dioxide (SO(2)) in the concentration range 95-170 mg l(-1)inhibits the ability of both strains to reduce the volatile acidity of the acidic wine used under our experimental conditions. Therefore, deacidification should be carried out either in wines stabilized by filtration or in wines with SO(2)concentrations up to 70 mg l(-1). Deacidification of wines with the better performing strain S26 was associated with changes in the concentration of volatile compounds. The most pronounced increase was observed for isoamyl acetate (banana) and ethyl hexanoate (apple, pineapple), with an 18- and 25-fold increment, respectively, to values above the detection threshold. The acetaldehyde concentration of the deacidified wine was 2.3 times higher, and may have a detrimental effect on the wine aroma. Moreover, deacidification led to increased fatty acids concentration, but still within the range of values described for spontaneous fermentations, and with apparently no negative impact on the organoleptical properties.

  6. Tuning the properties of polyhydroxybutyrate films using acetic acid via solvent casting

    NASA Astrophysics Data System (ADS)

    Anbukarasu, Preetam; Sauvageau, Dominic; Elias, Anastasia

    2015-12-01

    Biodegradable polyhydroxybutyrate (PHB) films were fabricated using acetic acid as an alternative to common solvents such as chloroform. The PHB films were prepared using a solvent casting process at temperatures ranging from 80 °C to 160 °C. The crystallinity, mechanical properties and surface morphology of the films cast at different temperatures were characterized and compared to PHB films cast using chloroform as a solvent. Results revealed that the properties of the PHB film varied considerably with solvent casting temperature. In general, samples processed with acetic acid at low temperatures had comparable mechanical properties to PHB cast using chloroform. This acetic acid based method is environmentally friendly, cost efficient and allows more flexible processing conditions and broader ranges of polymer properties than traditional methods.

  7. Theoretical prediction of pKa in methanol: testing SM8 and SMD models for carboxylic acids, phenols, and amines.

    PubMed

    Miguel, Elizabeth L M; Silva, Poliana L; Pliego, Josefredo R

    2014-05-29

    Methanol is a widely used solvent for chemical reactions and has solvation properties similar to those of water. However, the performance of continuum solvation models in this solvent has not been tested yet. In this report, we have investigated the performance of the SM8 and SMD models for pKa prediction of 26 carboxylic acids, 24 phenols, and 23 amines in methanol. The gas phase contribution was included at the X3LYP/TZVPP+diff//X3LYP/DZV+P(d) level. Using the proton exchange reaction with acetic acid, phenol, and ammonia as reference species leads to RMS error in the range of 1.4 to 3.6 pKa units. This finding suggests that the performance of the continuum models for methanol is similar to that found for aqueous solvent. Application of simple empirical correction through a linear equation leads to accurate pKa prediction, with uncertainty less than 0.8 units with the SM8 method. Testing with the less expensive PBE1PBE/6-311+G** method results in a slight improvement in the results.

  8. Investigating the photostability of carboxylic acids exposed to Mars surface ultraviolet radiation conditions.

    PubMed

    Stalport, F; Coll, P; Szopa, C; Cottin, H; Raulin, F

    2009-01-01

    The detection and identification of organic molecules on Mars are of primary importance to establish the existence of a possible ancient prebiotic chemistry or even biological activity. The harsh environmental conditions at the surface of Mars could explain why the Viking probes-the only efforts, to date, to search for organics on Mars-detected no organic matter. To investigate the nature, abundance, and stability of organic molecules that could survive such environmental conditions, we developed a series of experiments that simulate martian surface environmental conditions. Here, we present results with regard to the impact of solar UV radiation on various carboxylic acids, such as mellitic acid, which are of astrobiological interest to the study of Mars. Our results show that at least one carboxylic acid, mellitic acid, could produce a resistant compound-benzenehexacarboxylic acid-trianhydride (C(12)O(9))-when exposed to martian surface radiation conditions. The formation of such products could contribute to the presence of organic matter in the martian regolith, which should be considered a primary target for in situ molecular analyses during future surface missions.

  9. Characterization of Carboxylic Acid Reductases as Enzymes in the Toolbox for Synthetic Chemistry.

    PubMed

    Finnigan, William; Thomas, Adam; Cromar, Holly; Gough, Ben; Snajdrova, Radka; Adams, Joseph P; Littlechild, Jennifer A; Harmer, Nicholas J

    2017-03-20

    Carboxylic acid reductase enzymes (CARs) meet the demand in synthetic chemistry for a green and regiospecific route to aldehydes from their respective carboxylic acids. However, relatively few of these enzymes have been characterized. A sequence alignment with members of the ANL (Acyl-CoA synthetase/ NRPS adenylation domain/Luciferase) superfamily of enzymes shed light on CAR functional dynamics. Four unstudied enzymes were selected by using a phylogenetic analysis of known and hypothetical CARs, and for the first time, a thorough biochemical characterization was performed. Kinetic analysis of these enzymes with various substrates shows that they have a broad but similar substrate specificity. Electron-rich acids are favored, which suggests that the first step in the proposed reaction mechanism, attack by the carboxylate on the α-phosphate of adenosine triphosphate (ATP), is the step that determines the substrate specificity and reaction kinetics. The effects of pH and temperature provide a clear operational window for the use of these CARs, whereas an investigation of product inhibition by NADP + , adenosine monophosphate, and pyrophosphate indicates that the binding of substrates at the adenylation domain is ordered with ATP binding first. This study consolidates CARs as important and exciting enzymes in the toolbox for sustainable chemistry and provides specifications for their use as a biocatalyst.

  10. Factors influencing the rate of non-enzymatic activation of carboxylic and amino acids by ATP

    NASA Technical Reports Server (NTRS)

    Mullins, D. W., Jr.; Lacey, J. C., Jr.

    1981-01-01

    The nonenzymatic formation of adenylate anhydrides of carboxylic and amino acids is discussed as a necessary step in the origin of the genetic code and protein biosynthesis. Results of studies are presented which have shown the rate of activation to depend on the pKa of the carboxyl group, the pH of the medium, temperature, the divalent metal ion catalyst, salt concentration, and the nature of the amino acid. In particular, it was found that of the various amino acids investigated, phenylalanine had the greatest affinity for the adenine derivatives adenosine and ATP. Results thus indicate that selective affinities between amino acids and nucleotides were important during prebiotic chemical evolution, and may have played a major role in the origin of protein synthesis and genetic coding.

  11. Application of 1-aminocyclohexane carboxylic acid to protein nanostructure computer design

    PubMed Central

    Rodríguez-Ropero, Francisco; Zanuy, David; Casanovas, Jordi; Nussinov, Ruth; Alemán, Carlos

    2009-01-01

    Conformationally restricted amino acids are promising candidates to serve as basic pieces in redesigned protein motifs which constitute the basic modules in synthetic nanoconstructs. Here we study the ability of constrained cyclic amino acid 1-aminocyclohexane-1-carboxylic acid (Ac6c) to stabilize highly regular β-helical motifs excised from naturally occurring proteins. Calculations indicate that the conformational flexibility observed in both the ring and the main chain is significantly higher than that detected for other 1-aminocycloalkane-1-carboxylic acid (Acnc, where n refers to the size of the ring) with smaller cycles. Incorporation of Ac6c into the flexible loops of β-helical motifs indicates that the stability of such excised building blocks as well as the nano-assemblies derived from them is significantly enhanced. Thus, the intrinsic Ac6c tendency to adopt folded conformations combined with the low structural strain of the cyclohexane ring confers the ability to both self-adapt to the β-helix motif and to stabilize the overall structure by absorbing part of its conformational fluctuations. Comparison with other Acnc residues indicates that the ability to adapt to the targeted position improves considerably with the ring size, i.e. when the rigidity introduced by the strain of the ring decreases. PMID:18201062

  12. Improved Acetic Acid Resistance in Saccharomyces cerevisiae by Overexpression of the WHI2 Gene Identified through Inverse Metabolic Engineering.

    PubMed

    Chen, Yingying; Stabryla, Lisa; Wei, Na

    2016-01-29

    Development of acetic acid-resistant Saccharomyces cerevisiae is important for economically viable production of biofuels from lignocellulosic biomass, but the goal remains a critical challenge due to limited information on effective genetic perturbation targets for improving acetic acid resistance in the yeast. This study employed a genomic-library-based inverse metabolic engineering approach to successfully identify a novel gene target, WHI2 (encoding a cytoplasmatic globular scaffold protein), which elicited improved acetic acid resistance in S. cerevisiae. Overexpression of WHI2 significantly improved glucose and/or xylose fermentation under acetic acid stress in engineered yeast. The WHI2-overexpressing strain had 5-times-higher specific ethanol productivity than the control in glucose fermentation with acetic acid. Analysis of the expression of WHI2 gene products (including protein and transcript) determined that acetic acid induced endogenous expression of Whi2 in S. cerevisiae. Meanwhile, the whi2Δ mutant strain had substantially higher susceptibility to acetic acid than the wild type, suggesting the important role of Whi2 in the acetic acid response in S. cerevisiae. Additionally, overexpression of WHI2 and of a cognate phosphatase gene, PSR1, had a synergistic effect in improving acetic acid resistance, suggesting that Whi2 might function in combination with Psr1 to elicit the acetic acid resistance mechanism. These results improve our understanding of the yeast response to acetic acid stress and provide a new strategy to breed acetic acid-resistant yeast strains for renewable biofuel production. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

  13. Mentha longifolia protects against acetic-acid induced colitis in rats.

    PubMed

    Murad, Hussam A S; Abdallah, Hossam M; Ali, Soad S

    2016-08-22

    Mentha longifolia L (Wild Mint or Habak) (ML) is used in traditional medicine in treatment of many gastrointestinal disorders. This study aimed to evaluate potential protecting effect of ML and its major constituent, eucalyptol, against acetic acid-induced colitis in rats, a model of human inflammatory bowel disease (IBD). Rats were divided into ten groups (n=8) given orally for three days (mg/kg/day) the following: normal control, acetic acid-induced colitis (un-treated, positive control), vehicle (DMSO), sulfasalazine (500), ML extract (100, 500, 1000), and eucalyptol (100, 200, 400). After 24h-fasting, two ML of acetic acid (3%) was administered intrarectally. On the fifth day, serum and colonic biochemical markers, and histopathological changes were evaluated. Colitis significantly increased colonic myeloperoxidase activity and malonaldehyde level, and serum tumor necrosis factor-α, interleukin-6, and malonaldehyde levels while significantly decreased colonic and serum glutathione levels. All treatments (except ML 100, ML 1000, and eucalyptol 100) significantly reversed these changes where eucalyptol (400) showed the highest activity in a dose-dependent manner. The colitis-induced histopathological changes were mild in sulfasalazine and eucalyptol 400 groups, moderate in ML 500 and eucalyptol 200 groups, and severe in ML 100, ML 1000, and eucalyptol 100 groups nearly similar to colitis-untreated rats. ML (in moderate doses) and eucalyptol (dose-dependently) exerted protective effects against acetic acid-induced colitis in rats possibly through antioxidant and antiinflammatory properties suggesting a potential benefit in treatments of IBD. To our knowledge this is the first report addressing this point. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  14. Use of a polystyrene-divinylbenzene-based weakly acidic cation-exchange resin column and propionic acid as an eluent in ion-exclusion/adsorption chromatography of aliphatic carboxylic acids and ethanol in food samples.

    PubMed

    Mori, Masanobu; Hironaga, Takahiro; Kajiwara, Hiroe; Nakatani, Nobutake; Kozaki, Daisuke; Itabashi, Hideyuki; Tanaka, Kazuhiko

    2011-01-01

    We developed an ion-exclusion/adsorption chromatography (IEAC) method employing a polystyrene-divinylbenzene-based weakly acidic cation-exchange resin (PS-WCX) column with propionic acid as the eluent for the simultaneous determination of multivalent aliphatic carboxylic acids and ethanol in food samples. The PS-WCX column well resolved mono-, di-, and trivalent carboxylic acids in the acidic eluent. Propionic acid as the eluent gave a higher signal-to-noise ratio, and enabled sensitive conductimetric detection of analyte acids. We found the optimal separation condition to be the combination of a PS-WCX column and 20-mM propionic acid. Practical applicability of the developed method was confirmed by using a short precolumn with a strongly acidic cation-exchange resin in the H(+)-form connected before the separation column; this was to remove cations from food samples by converting them to hydrogen ions. Consequently, common carboxylic acids and ethanol in beer, wine, and soy sauce were successfully separated by the developed method.

  15. Deletion of JJJ1 improves acetic acid tolerance and bioethanol fermentation performance of Saccharomyces cerevisiae strains.

    PubMed

    Wu, Xuechang; Zhang, Lijie; Jin, Xinna; Fang, Yahong; Zhang, Ke; Qi, Lei; Zheng, Daoqiong

    2016-07-01

    To improve tolerance to acetic acid that is present in lignocellulosic hydrolysates and affects bioethanol production by Saccharomyces cerevisiae. Saccharomyces cerevisiae strains with improved tolerance to acetic acid were obtained through deletion of the JJJ1 gene. The lag phase of the JJJ1 deletion mutant BYΔJJJ1 was ~16 h shorter than that of the parent strain, BY4741, when the fermentation medium contained 4.5 g acetic acid/l. Additionally, the specific ethanol production rate of BYΔJJJ1 was increased (0.057 g/g h) compared to that of the parent strain (0.051 g/g h). Comparative transcription and physiological analyses revealed higher long chain fatty acid, trehalose, and catalase contents might be critical factors responsible for the acetic acid resistance of JJJ1 knockout strains. JJJ1 deletion improves acetic acid tolerance and ethanol fermentation performance of S. cerevisiae.

  16. Steam Reforming of Acetic Acid over Co-Supported Catalysts: Coupling Ketonization for Greater Stability

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

    Davidson, Stephen D.; Spies, Kurt A.; Mei, Donghai

    We report on the markedly improved stability of a novel 2-bed catalytic system, as compared to a conventional 1-bed steam reforming catalyst, for the production of H2 from acetic acid. The 2-bed catalytic system comprises of i) a basic oxide ketonization catalyst for the conversion of acetic acid to acetone, and a ii) Co-based steam reforming catalyst, both catalytic beds placed in sequence within the same unit operation. Steam reforming catalysts are particularly prone to catalytic deactivation when steam reforming acetic acid, used here as a model compound for the aqueous fraction of bio-oil. Catalysts comprising MgAl2O4, ZnO, CeO2, andmore » activated carbon (AC) both with and without Co-addition were evaluated for conversion of acetic acid and acetone, its ketonization product, in the presence of steam. It was found that over the bare oxide support only ketonization activity was observed and coke deposition was minimal. With addition of Co to the oxide support steam reforming activity was facilitated and coke deposition was significantly increased. Acetone steam reforming over the same Co-supported catalysts demonstrated more stable performance and with less coke deposition than with acetic acid feedstock. DFT analysis suggests that over Co surface CHxCOO species are more favorably formed from acetic acid versus acetone. These CHxCOO species are strongly bound to the Co catalyst surface and could explain the higher propensity for coke formation from acetic acid. Based on these findings, in order to enhance stability of the steam reforming catalyst a dual-bed (2-bed) catalyst system was implemented. Comparing the 2-bed and 1-bed (Co-supported catalyst only) systems under otherwise identical reaction conditions the 2-bed demonstrated significantly improved stability and coke deposition was decreased by a factor of 4.« less

  17. Employing natural reagents from turmeric and lime for acetic acid determination in vinegar sample.

    PubMed

    Supharoek, Sam-Ang; Ponhong, Kraingkrai; Siriangkhawut, Watsaka; Grudpan, Kate

    2018-04-01

    A simple, rapid and environmentally friendly sequential injection analysis system employing natural extract reagents was developed for the determination of acetic acid following an acid-base reaction in the presence of an indicator. Powdered lime and turmeric were utilized as the natural base and indicator, respectively. Mixing lime and turmeric produced an orange to reddish-brown color solution which absorbed the maximum wavelength at 455 nm, with absorbance decreasing with increasing acetic acid concentration. Influential parameters including lime and turmeric concentrations, reagent and sample aspirated volumes, mixing coil length and dispensing flow rate were investigated and optimized. A standard calibration graph was plotted for 0-5.0 mmol/L acetic acid with r 2  = 0.9925. Relative standard deviations (RSD) at 2.0 and 4.0 mmol/L acetic acid were less than 3% (n = 7), with limit of detection (LOD) and limit of quantification (LOQ) at 0.12 and 0.24 mmol/L, respectively. The method was successfully applied to assay acetic acid concentration in cooking vinegar samples. Results achieved were not significantly different from those obtained following a batchwise standard AOAC titration method. Copyright © 2017. Published by Elsevier B.V.

  18. Signal enhancement of carboxylic acids by inclusion with β-cyclodextrin in negative high-voltage-assisted laser desorption ionization mass spectrometry.

    PubMed

    Ren, Xinxin; Liu, Jia; Zhang, Chengsen; Sun, Jiamu; Luo, Hai

    2014-01-15

    It is difficult to directly analyze carboxylic acids in complex mixtures by ambient high-voltage-assisted laser desorption ionization mass spectrometry (HALDI-MS) in negative ion mode due to the low ionization efficiency of carboxylic acids. A method for the rapid detection of carboxylic acids in negative HALDI-MS has been developed based on their inclusion with β-cyclodextrin (β-CD). The negative HALDI-MS signal-to-noise ratios (S/Ns) of aliphatic, aromatic and hetero atom-containing carboxylic acids can all be significantly improved by forming 1:1 complexes with β-CD. These complexes are mainly formed by specific inclusion interactions which are verified by their collision-induced dissociation behaviors in comparison with that of their corresponding maltoheptaose complexes. A HALDI-MS/MS method has been successfully developed for the detection of α-lipoic acid in complex cosmetics and ibuprofen in a viscous drug suspension. The negative HALDI-MS S/Ns of carboxylic acids can be improved up to 30 times via forming non-covalent complexes with β-CD. The developed method shows the advantages of being rapid and simple, and is promising for rapid detection of active ingredients in complex samples or fast screening of drugs and cosmetics. Copyright © 2013 John Wiley & Sons, Ltd.

  19. ReaxFF molecular dynamics simulation of intermolecular structure formation in acetic acid-water mixtures at elevated temperatures and pressures

    NASA Astrophysics Data System (ADS)

    Sengul, Mert Y.; Randall, Clive A.; van Duin, Adri C. T.

    2018-04-01

    The intermolecular structure formation in liquid and supercritical acetic acid-water mixtures was investigated using ReaxFF-based molecular dynamics simulations. The microscopic structures of acetic acid-water mixtures with different acetic acid mole fractions (1.0 ≥ xHAc ≥ 0.2) at ambient and critical conditions were examined. The potential energy surface associated with the dissociation of acetic acid molecules was calculated using a metadynamics procedure to optimize the dissociation energy of ReaxFF potential. At ambient conditions, depending on the acetic acid concentration, either acetic acid clusters or water clusters are dominant in the liquid mixture. When acetic acid is dominant (0.4 ≤ xHAc), cyclic dimers and chain structures between acetic acid molecules are present in the mixture. Both structures disappear at increased water content of the mixture. It was found by simulations that the acetic acid molecules released from these dimer and chain structures tend to stay in a dipole-dipole interaction. These structural changes are in agreement with the experimental results. When switched to critical conditions, the long-range interactions (e.g., second or fourth neighbor) disappear and the water-water and acetic acid-acetic acid structural formations become disordered. The simulated radial distribution function for water-water interactions is in agreement with experimental and computational studies. The first neighbor interactions between acetic acid and water molecules are preserved at relatively lower temperatures of the critical region. As higher temperatures are reached in the critical region, these interactions were observed to weaken. These simulations indicate that ReaxFF molecular dynamics simulations are an appropriate tool for studying supercritical water/organic acid mixtures.

  20. Carboxylic acid isosteres improve the activity of ring-fused 2-pyridones that inhibit pilus biogenesis in E. coli

    PubMed Central

    Åberg, Veronica; Das, Pralay; Chorell, Erik; Hedenström, Mattias; Pinkner, Jerome S.; Hultgren, Scott J.; Almqvist, Fredrik

    2009-01-01

    Ring-fused 2-pyridones, termed pilicides, are small synthetic compounds that inhibit pilus assembly in uropathogenic E. coli. Their biological activity is clearly dependent upon a carboxylic acid functionality. Here we present the synthesis and biological evaluation of carboxylic acid isosteres, including e.g. tetrazoles, acyl sulfonamides and hydroxamic acids, of two lead 2-pyridones. Two independent biological evaluations show that acyl sulfonamides and tetrazoles significantly improve pilicide activity against uropathogenic E. coli. PMID:18499455

  1. Microbiological preservation of cucumbers for bulk storage using acetic acid and food preservatives.

    PubMed

    Pérez-Díaz, I M; McFeeters, R F

    2008-08-01

    Microbial growth did not occur when cucumbers were preserved without a thermal process by storage in solutions containing acetic acid, sodium benzoate, and calcium chloride to maintain tissue firmness. The concentrations of acetic acid and sodium benzoate required to ensure preservation were low enough so that stored cucumbers could be converted to the finished product without the need to wash out and discard excess acid or preservative. Since no thermal process was required, this method of preservation would be applicable for storing cucumbers in bulk containers. Acid tolerant pathogens died off in less than 24 h with the pH, acetic acid, and sodium benzoate concentrations required to assure the microbial stability of cucumbers stored at 30 degrees C. Potassium sorbate as a preservative in this application was not effective. Yeast growth was observed when sulfite was used as a preservative.

  2. Microbial process for the preparation of acetic acid, as well as solvent for its extraction from the fermentation broth

    DOEpatents

    Gaddy, James L.; Clausen, Edgar C.; Ko, Ching-Whan; Wade, Leslie E.; Wikstrom, Carl V.

    2007-03-27

    A modified water-immiscible solvent useful in the extraction of acetic acid from aqueous streams is a substantially pure mixture of isomers of highly branched di-alkyl amines. Solvent mixtures formed of such a modified solvent with a desired co-solvent, preferably a low boiling hydrocarbon, are useful in the extraction of acetic acid from aqueous gaseous streams. An anaerobic microbial fermentation process for the production of acetic acid employs such solvents, under conditions which limit amide formation by the solvent and thus increase the efficiency of acetic acid recovery. Methods for the direct extraction of acetic acid and the extractive fermentation of acetic acid also employ the modified solvents and increase efficiency of acetic acid production. Such increases in efficiency are also obtained where the energy source for the microbial fermentation contains carbon dioxide and the method includes a carbon dioxide stripping step prior to extraction of acetic acid in solvent.

  3. Microbial process for the preparation of acetic acid, as well as solvent for its extraction from the fermentation broth

    DOEpatents

    Gaddy, James L.; Clausen, Edgar C.; Ko, Ching-Whan; Wade, Leslie E.; Wikstrom, Carl V.

    2004-06-22

    A modified water-immiscible solvent useful in the extraction of acetic acid from aqueous streams is a substantially pure mixture of isomers of highly branched di-alkyl amines. Solvent mixtures formed of such a modified solvent with a desired co-solvent, preferably a low boiling hydrocarbon, are useful in the extraction of acetic acid from aqueous gaseous streams. An anaerobic microbial fermentation process for the production of acetic acid employs such solvents, under conditions which limit amide formation by the solvent and thus increase the efficiency of acetic acid recovery. Methods for the direct extraction of acetic acid and the extractive fermentation of acetic acid also employ the modified solvents and increase efficiency of acetic acid production. Such increases in efficiency are also obtained where the energy source for the microbial fermentation contains carbon dioxide and the method includes a carbon dioxide stripping step prior to extraction of acetic acid in solvent.

  4. A comparative study on the concentrations of 11-nor-Δ9-tetrahydrocannabinol-9-carboxylic acid (THCCOOH) in head and pubic hair.

    PubMed

    Han, Eunyoung; Choi, Hwakyung; Lee, Sangki; Chung, Heesun; Song, Joon Myong

    2011-10-10

    In this study, the concentrations of 11-nor-Δ(9)-tetrahydrocannabinol-9-carboxylic acid (THCCOOH) in pubic, axillary and beard hair were measured and the correlation between the concentrations of THCCOOH in head and pubic hair from same cannabis users were evaluated. The papers on body hair analysis for THCCOOH were rarely found although police officers submit body hair as a complimentary specimen to forensic laboratories in case cannabis users had no hair. Head, pubic, axillary, and beard hair were collected. All hair samples were cut into 0.5mm segments and decontaminated with methanol, digested with 1 mL of 1M NaOH at 85 °C for 30 min and extracted in 2 mL of n-hexane:ethyl acetate (9:1) two times after adding 1 mL of 0.1N sodium acetate buffer (pH = 4.5) and 200 μL of acetic acid followed by derivatization with 50 μL of PFPA and 25 μL of PFPOH for 30 min at 70 °C. The extracts were analyzed using gas chromatography tandem mass spectrometry operating in negative chemical ionization mode (GC/MS/MS-NCI). We determined the concentrations of THCCOOH in both pubic and head hair. The concentrations of THCCOOH in pubic hair were higher than those in head hair. We also evaluated the concentrations of THCCOOH in body hair (pubic, axillary and beard hair) and head hair according to the positive/negative urine test results. There was no statistically significant difference in the concentrations of THCCOOH in head and body hair according to urine results. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

  5. Structural studies of crystalline forms of triamterene with carboxylic acid, GRAS and API molecules

    PubMed Central

    Rehman, Abida

    2018-01-01

    Pharmaceutical salt solvates (dimethyl sulfoxide, DMSO) of the drug triamterene with the coformers acetic, succinic, adipic, pimelic, azelaic and nicotinic acid and ibuprofen are prepared by liquid-assisted grinding and solvent-evaporative crystallization. The modified ΔpK a rule as proposed by Cruz-Cabeza [(2012 ▸). CrystEngComm, 14, 6362–6365] is in close agreement with the results of this study. All adducts were characterized by X-ray diffraction and thermal analytical techniques, including single-crystal X-ray diffraction, powder X-ray diffraction, differential scanning calorimetry and thermal gravimetric analysis. Hydrogen-bonded motifs combined to form a variety of extended tapes and sheets. Analysis of the crystal structures showed that all adducts existed as salt solvates and contained the amino­pyridinium–carboxyl­ate heterodimer, except for the solvate containing triamterene, ibuprofen and DMSO, as a result of the presence of a strong and stable hemitriamterenium duplex. A search of the Cambridge Structural Database (CSD 5.36, Version 1.18) to determine the frequency of occurrence of the putative supramolecular synthons found in this study showed good agreement with previous work. PMID:29755747

  6. Bacterial conversion of phenylalanine and aromatic carboxylic acids into dihydrodiols.

    PubMed Central

    Wegst, W; Tittmann, U; Eberspächer, J; Lingens, F

    1981-01-01

    Strain E of chloridazon-degrading bacteria, when grown on L-phenylalanine accumulates cis-2,3-dihydro-2,3-dihydroxyphenylalanine. In experiments with resting cells and during growth the bacterium converts the aromatic carboxylic acids phenylacetate, phenylpropionate, phenylbutyrate and phenyl-lactate into the corresponding cis-2,3-dihydrodiol compounds. The amino acids L-phenylalanine, N-acetyl-L-phenylalanine and t-butyloxycarbonyl-L-phenylalanine were also transformed into dihydrodiols. All seven dihydrodiols, thus obtained, were characterized both by conventional analytical techniques and by the ability to serve as substrates for a cis-dihydrodiol dehydrogenase. PMID:7306016

  7. Tuning the properties of polyhydroxybutyrate films using acetic acid via solvent casting

    PubMed Central

    Anbukarasu, Preetam; Sauvageau, Dominic; Elias, Anastasia

    2015-01-01

    Biodegradable polyhydroxybutyrate (PHB) films were fabricated using acetic acid as an alternative to common solvents such as chloroform. The PHB films were prepared using a solvent casting process at temperatures ranging from 80 °C to 160 °C. The crystallinity, mechanical properties and surface morphology of the films cast at different temperatures were characterized and compared to PHB films cast using chloroform as a solvent. Results revealed that the properties of the PHB film varied considerably with solvent casting temperature. In general, samples processed with acetic acid at low temperatures had comparable mechanical properties to PHB cast using chloroform. This acetic acid based method is environmentally friendly, cost efficient and allows more flexible processing conditions and broader ranges of polymer properties than traditional methods. PMID:26640089

  8. Comparison of acetic acid and ethanol sclerotherapy for simple renal cysts: clinical experience with 86 patients.

    PubMed

    Cho, Young Jun; Shin, Ji Hoon

    2016-01-01

    To compare the efficacy and treatment session numbers of acetic acid to that of ethanol sclerotherapy for the treatment of simple renal cysts. Between February 2004 and June 2013, 86 patients with simple renal cysts underwent percutaneous aspiration and injection of 50 %-acetic-acid (42 cysts) and 95 %-ethanol (44 cysts). The patient demographics, volume reduction rate, number of treatment sessions, and complications were then analyzed. The volume reduction rate was 94.1 ± 7.6 % in the 50 %-acetic acid group and 94.7 ± 11.7 % in the 95 %-ethanol group, and without a statistical difference. The rates of complete remission, partial remission, and no response were 57.1, 42.9 and 0 %, respectively, for the acetic acid group, and 70.5, 25.0, and 4.5 %, respectively, for the ethanol group. No statistical difference was observed between the two groups. Compared to the acetic acid group, the ethanol group had a higher number of treatment sessions, i.e. 1.10 ± 0.30 in the acetic acid group and 1.80 ± 0.79 in the ethanol group. Mild flank pain was a minor complication that occurred in both groups. Acetic acid seems to have equivalent sclerosing effects on simple renal cysts compared with those of ethanol despites of fewer treatment sessions.

  9. Effect of acetic acid in recycling water on ethanol production for cassava in an integrated ethanol-methane fermentation process.

    PubMed

    Yang, Xinchao; Wang, Ke; Zhang, Jianhua; Tang, Lei; Mao, Zhonggui

    2016-11-01

    Recently, the integrated ethanol-methane fermentation process has been studied to prevent wastewater pollution. However, when the anaerobic digestion reaction runs poorly, acetic acid will accumulate in the recycling water. In this paper, we studied the effect of low concentration of acetic acid (≤25 mM) on ethanol fermentation at different initial pH values (4.2, 5.2 or 6.2). At an initial pH of 4.2, ethanol yields increased by 3.0% and glycerol yields decreased by 33.6% as the acetic acid concentration was increased from 0 to 25 mM. Raising the concentration of acetic acid to 25 mM increased the buffering capacity of the medium without obvious effects on biomass production in the cassava medium. Acetic acid was metabolized by Saccharomyces cerevisiae for the reason that the final concentration of acetic acid was 38.17% lower than initial concentration at pH 5.2 when 25 mM acetic acid was added. These results confirmed that a low concentration of acetic acid in the process stimulated ethanol fermentation. Thus, reducing the acetic acid concentration to a controlled low level is more advantageous than completely removing it.

  10. Cu-catalyzed formal methylative and hydrogenative carboxylation of alkynes with carbon dioxide: efficient synthesis of α,β-unsaturated carboxylic acids.

    PubMed

    Takimoto, Masanori; Hou, Zhaomin

    2013-08-19

    The sequential hydroalumination or methylalumination of various alkynes catalyzed by different catalyst systems, such those based on Sc, Zr, and Ni complexes, and the subsequent carboxylation of the resulting alkenylaluminum species with CO2 catalyzed by an N-heterocyclic carbene (NHC)-copper catalyst have been examined in detail. The regio- and stereoselectivity of the overall reaction relied largely on the hydroalumination or methylalumination reactions, which significantly depended on the catalyst and alkyne substrates. The subsequent Cu-catalyzed carboxylation proceeded with retention of the stereoconfiguration of the alkenylaluminum species. All the reactions could be carried out in one-pot to afford efficiently a variety of α,β-unsaturated carboxylic acids with well-controlled configurations, which are difficult to construct by previously reported methods. This protocol could be practically useful and attractive because of its high regio- and stereoselectivity, simple one-pot reaction operation, and the use of CO2 as a starting material. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Organogel polymers from 10-undecenoic acid and poly(vinyl acetate)

    USDA-ARS?s Scientific Manuscript database

    Organogels are used in a variety of high value applications including the removal of toxic solvents from aqueous environments and the time-controlled release of compounds. One of the most promising gelators is a polyvinyl polymer containing medium chain length carboxylic acids. The existing producti...

  12. Guiding principle for crystalline Si photovoltaic modules with high tolerance to acetic acid

    NASA Astrophysics Data System (ADS)

    Masuda, Atsushi; Hara, Yukiko

    2018-04-01

    A guiding principle for highly reliable crystalline Si photovoltaic modules, especially those with high tolerance to acetic acid generated by hydrolysis reaction between water vapor and an ethylene-vinyl acetate (EVA) encapsulant, is proposed. Degradation behavior evaluated by the damp heat test strongly depends on Ag finger electrodes and also EVA encapsulants. The acetic acid concentration in EVA on the glass side directly determines the degradation behavior. The most important factor for high tolerance is the type of Ag finger electrode materials when using an EVA encapsulant. Photovoltaic modules using newly developed crystalline Si cells with improved Ag finger electrode materials keep their maximum power of 80% of the initial value even after the damp heat test at 85 °C and 85% relative humidity for 10000 h. The pattern of dark regions in electroluminescence images is also discussed on the basis of the dynamics of acetic acid in the modules.

  13. Macromolecular metal carboxylates

    NASA Astrophysics Data System (ADS)

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

    2008-03-01

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

  14. Free fatty acid (FFA) and hydroxy carboxylic acid (HCA) receptors.

    PubMed

    Offermanns, Stefan

    2014-01-01

    Saturated and unsaturated free fatty acids (FFAs), as well as hydroxy carboxylic acids (HCAs) such as lactate and ketone bodies, are carriers of metabolic energy, precursors of biological mediators, and components of biological structures. However, they are also able to exert cellular effects through G protein-coupled receptors named FFA1-FFA4 and HCA1-HCA3. Work during the past decade has shown that these receptors are widely expressed in the human body and regulate the metabolic, endocrine, immune and other systems to maintain homeostasis under changing dietary conditions. The development of genetic mouse models and the generation of synthetic ligands of individual FFA and HCA receptors have been instrumental in identifying cellular and biological functions of these receptors. These studies have produced strong evidence that several FFA and HCA receptors can be targets for the prevention and treatment of various diseases, including type 2 diabetes mellitus, obesity, and inflammation.

  15. Microbial process for the preparation of acetic acid as well as solvent for its extraction from the fermentation broth

    DOEpatents

    Gaddy, James L.; Clausen, Edgar C.; Ko, Ching-Whan; Wade, Leslie E.; Wikstrom, Carl V.

    2006-07-11

    A modified water-immiscible solvent useful in the extraction of acetic acid from aqueous streams is a substantially pure mixture of isomers of highly branched di-alkyl amines. This solvent is substantially devoid of mono-alkyl amines and alcohols. Solvent mixtures formed of such a modified solvent with a desired cosolvent, preferably a low boiling hydrocarbon which forms an azeotrope with water are useful in the extraction of acetic acid from aqueous gaseous streams. An anaerobic microbial fermentation process for the production of acetic acid employs such solvents, under conditions which limit amide formation by the solvent and thus increase the efficiency of acetic acid recovery. Methods for the direct extraction of acetic acid and the extractive fermentation of acetic acid also employ the modified solvents and increase efficiency of acetic acid production. Such increases in efficiency are also obtained where the energy source for the microbial fermentation contains carbon dioxide and the method includes a carbon dioxide stripping step prior to extraction of acetic acid in solvent.

  16. Microbial process for the preparation of acetic acid as well as solvent for its extraction from the fermentation broth

    DOEpatents

    Gaddy, James L.; Clausen, Edgar C.; Ko, Ching-Whan; Wade, Leslie E.; Wikstrom, Carl V.

    2002-01-01

    A modified water-immiscible solvent useful in the extraction of acetic acid from aqueous streams is a substantially pure mixture of isomers of highly branched di-alkyl amines. This solvent is substantially devoid of mono-alkyl amines and alcohols. Solvent mixtures formed of such a modified solvent with a desired cosolvent, preferably a low boiling hydrocarbon which forms an azeotrope with water are useful in the extraction of acetic acid from aqueous gaseous streams. An anaerobic microbial fermentation process for the production of acetic acid employs such solvents, under conditions which limit amide formation by the solvent and thus increase the efficiency of acetic acid recovery. Methods for the direct extraction of acetic acid and the extractive fermentation of acetic acid also employ the modified solvents and increase efficiency of acetic acid production. Such increases in efficiency are also obtained where the energy source for the microbial fermentation contains carbon dioxide and the method includes a carbon dioxide stripping step prior to extraction of acetic acid in solvent.

  17. Mutants of the pentose-fermenting yeast Pachysolen tannophilus tolerant to hardwood spent sulfite liquor and acetic acid.

    PubMed

    Harner, Nicole K; Bajwa, Paramjit K; Habash, Marc B; Trevors, Jack T; Austin, Glen D; Lee, Hung

    2014-01-01

    A strain development program was initiated to improve the tolerance of the pentose-fermenting yeast Pachysolen tannophilus to inhibitors in lignocellulosic hydrolysates. Several rounds of UV mutagenesis followed by screening were used to select for mutants of P. tannophilus NRRL Y2460 with improved tolerance to hardwood spent sulfite liquor (HW SSL) and acetic acid in separate selection lines. The wild type (WT) strain grew in 50 % (v/v) HW SSL while third round HW SSL mutants (designated UHW301, UHW302 and UHW303) grew in 60 % (v/v) HW SSL, with two of these isolates (UHW302 and UHW303) being viable and growing, respectively, in 70 % (v/v) HW SSL. In defined liquid media containing acetic acid, the WT strain grew in 0.70 % (w/v) acetic acid, while third round acetic acid mutants (designated UAA301, UAA302 and UAA303) grew in 0.80 % (w/v) acetic acid, with one isolate (UAA302) growing in 0.90 % (w/v) acetic acid. Cross-tolerance of HW SSL-tolerant mutants to acetic acid and vice versa was observed with UHW303 able to grow in 0.90 % (w/v) acetic acid and UAA302 growing in 60 % (v/v) HW SSL. The UV-induced mutants retained the ability to ferment glucose and xylose to ethanol in defined media. These mutants of P. tannophilus are of considerable interest for bioconversion of the sugars in lignocellulosic hydrolysates to ethanol.

  18. Syntrophic acetate oxidation in two-phase (acid-methane) anaerobic digesters.

    PubMed

    Shimada, T; Morgenroth, E; Tandukar, M; Pavlostathis, S G; Smith, A; Raskin, L; Kilian, R E

    2011-01-01

    The microbial processes involved in two-phase anaerobic digestion were investigated by operating a laboratory-scale acid-phase (AP) reactor and analyzing two full-scale, two-phase anaerobic digesters operated under mesophilic (35 °C) conditions. The digesters received a blend of primary sludge and waste activated sludge (WAS). Methane levels of 20% in the laboratory-scale reactor indicated the presence of methanogenic activity in the AP. A phylogenetic analysis of an archaeal 16S rRNA gene clone library of one of the full-scale AP digesters showed that 82% and 5% of the clones were affiliated with the orders Methanobacteriales and Methanosarcinales, respectively. These results indicate that substantial levels of aceticlastic methanogens (order Methanosarcinales) were not maintained at the low solids retention times and acidic conditions (pH 5.2-5.5) of the AP, and that methanogenesis was carried out by hydrogen-utilizing methanogens of the order Methanobacteriales. Approximately 43, 31, and 9% of the archaeal clones from the methanogenic phase (MP) digester were affiliated with the orders Methanosarcinales, Methanomicrobiales, and Methanobacteriales, respectively. A phylogenetic analysis of a bacterial 16S rRNA gene clone library suggested the presence of acetate-oxidizing bacteria (close relatives of Thermacetogenium phaeum, 'Syntrophaceticus schinkii,' and Clostridium ultunense). The high abundance of hydrogen consuming methanogens and the presence of known acetate-oxidizing bacteria suggest that acetate utilization by acetate oxidizing bacteria in syntrophic interaction with hydrogen-utilizing methanogens was an important pathway in the second-stage of the two-phase digestion, which was operated at high ammonium-N concentrations (1.0 and 1.4 g/L). A modified version of the IWA Anaerobic Digestion Model No. 1 (ADM1) with extensions for syntrophic acetate oxidation and weak-acid inhibition adequately described the dynamic profiles of volatile acid production

  19. Improvement in wettability of porous Si by carboxylate termination

    NASA Astrophysics Data System (ADS)

    Sakakibara, Masanori; Matsumoto, Kimihisa; Kamiya, Kazuhide; Kawabata, Shigeki; Inada, Mitsuru; Suzuki, Shinya

    2018-02-01

    The effects of the surface terminations of carboxylic acid and carboxylate on the hydrophilicity of porous Si were studied to observe the changes in the photoluminescence (PL) intensity of water-dispersed porous Si powder over time. Porous Si terminated by carboxylate was produced from carboxylic acid-terminated porous Si by a neutralization reaction with an alkali metal. After the neutralization of porous Si terminated by carboxylic acid, the formation of carboxylate-terminated porous Si was confirmed by observing the absorption peaks corresponding to Si-C and COO- from Fourier transform infrared (FT-IR) spectra. On the basis of changes in the PL intensity of porous Si over time, the hydrophilicity of porous Si terminated by carboxylate was determined to be higher than that of porous Si terminated by carboxylic acid. On the other hand, nonradiative recombination centers on the surface of carboxylate-terminated porous Si were formed during the neutralization process, which reduced the PL intensity. The PL from porous Si terminated by carboxylic acid and carboxylate was caused by the quantum size effect regardless of the termination molecules, which was confirmed by the wavelength dependence of the PL lifetime. Porous Si terminated by undecylenate is an effective material for applications such as bio-labels owing to its hydrophilicity and high PL stability.

  20. [Chloroquine analogues from benzofuro- and benzothieno[3,2-b]-4-pyridone-2-carboxylic acid esters].

    PubMed

    Gölitzer, K; Meyer, H; Jomaa, H; Wiesner, J

    2004-08-01

    The amides 7 were synthesized from the annulated methyl 4-pyridone-2-carboxylates 4 via the carboxylic acids 5 and their acid chlorides by reacting with the novaldiamine base 6. The alcohol 8b, obtained from DIBAH reduction of the ester 4b, was transformed to the chloromethyl derivative 9 which reacted with 6 and 18-crown-6 leading to the 2-novaldiaminomethyl-4-pyridone 10. Compound 10 was obtained with higher yield from DIBAH reduction of the amide 7b. The substances 7 and 10 were inactive when tested against the chloroquine resistant Plasmodium falciparum strain Dd2.

  1. Organocatalyzed, Visible-Light Photoredox-Mediated, One-Pot Minisci Reaction Using Carboxylic Acids via N-(Acyloxy)phthalimides.

    PubMed

    Sherwood, Trevor C; Li, Ning; Yazdani, Aliza N; Dhar, T G Murali

    2018-03-02

    An improved, one-pot Minisci reaction has been developed using visible light, an organic photocatalyst, and carboxylic acids as radical precursors via the intermediacy of in situ-generated N-(acyloxy)phthalimides. The conditions employed are mild, demonstrate a high degree of functional group tolerance, and do not require a large excess of the carboxylic acid reactant. As a result, this reaction can be applied to drug-like scaffolds and molecules with sensitive functional groups, enabling late-stage functionalization, which is of high interest to medicinal chemistry.

  2. Intramolecular Tsuji-Trost-type Allylation of Carboxylic Acids: Asymmetric Synthesis of Highly π-Allyl Donative Lactones.

    PubMed

    Suzuki, Yusuke; Seki, Tomoaki; Tanaka, Shinji; Kitamura, Masato

    2015-08-05

    Tsuji-Trost-type asymmetric allylation of carboxylic acids has been realized by using a cationic CpRu complex with an axially chiral picolinic acid-type ligand (Cl-Naph-PyCOOH: naph = naphthyl, py = pyridine). The carboxylic acid and allylic alcohol intramolecularly condense by the liberation of water without stoichiometric activation of either nucleophile or electrophile part, thereby attaining high atom- and step-economy, and low E factor. This success can be ascribed to the higher reactivity of allylic alcohols as compared with the allyl ester products in soft Ru/hard Brønstead acid combined catalysis, which can function under slightly acidic conditions unlike the traditional Pd-catalyzed system. Detailed analysis of the stereochemical outcome of the reaction using an enantiomerically enriched D-labeled substrate provides an intriguing view of enantioselection.

  3. Acetic Acid Detection Threshold in Synthetic Wine Samples of a Portable Electronic Nose

    PubMed Central

    Macías, Miguel Macías; Manso, Antonio García; Orellana, Carlos Javier García; Velasco, Horacio Manuel González; Caballero, Ramón Gallardo; Chamizo, Juan Carlos Peguero

    2013-01-01

    Wine quality is related to its intrinsic visual, taste, or aroma characteristics and is reflected in the price paid for that wine. One of the most important wine faults is the excessive concentration of acetic acid which can cause a wine to take on vinegar aromas and reduce its varietal character. Thereby it is very important for the wine industry to have methods, like electronic noses, for real-time monitoring the excessive concentration of acetic acid in wines. However, aroma characterization of alcoholic beverages with sensor array electronic noses is a difficult challenge due to the masking effect of ethanol. In this work, in order to detect the presence of acetic acid in synthetic wine samples (aqueous ethanol solution at 10% v/v) we use a detection unit which consists of a commercial electronic nose and a HSS32 auto sampler, in combination with a neural network classifier (MLP). To find the characteristic vector representative of the sample that we want to classify, first we select the sensors, and the section of the sensors response curves, where the probability of detecting the presence of acetic acid will be higher, and then we apply Principal Component Analysis (PCA) such that each sensor response curve is represented by the coefficients of its first principal components. Results show that the PEN3 electronic nose is able to detect and discriminate wine samples doped with acetic acid in concentrations equal or greater than 2 g/L. PMID:23262483

  4. 40 CFR 180.426 - 2-[4,5-Dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-3-quinoline carboxylic acid...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...-methylethyl)-5-oxo-1H-imidazol-2-yl]-3-quinoline carboxylic acid; tolerance for residues. 180.426 Section 180...-Dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-3-quinoline carboxylic acid; tolerance for...)-5-oxo-1H-imidazol-2-yl]-3-quinoline carboxylic acid, in or on the raw agricultural commodity soybean...

  5. Recovery of acetic acid from dilute aqueous solutions using catalytic dehydrative esterification with ethanol.

    PubMed

    Yagyu, Daisuke; Ohishi, Tetsuo; Igarashi, Takeshi; Okumura, Yoshikuni; Nakajo, Tetsuo; Mori, Yuichiro; Kobayashi, Shū

    2013-03-01

    We have developed a direct esterification of aqueous acetic acid with ethanol (molar ratio=1:1) catalyzed by polystyrene-supported or homogeneous sulfonic acids toward the recovery of acetic acid from wastewater in chemical plants. The equilibrium yield was significantly increased by the addition of toluene, which had a high ability to extract ethyl acetate from the aqueous phase. It was shown that low-loading and alkylated polystyrene-supported sulfonic acid efficiently accelerated the reaction. These results suggest that the construction of hydrophobic reaction environments in water was critical in improving the chemical yield. Addition of inorganic salts was also effective for the reaction under not only biphasic conditions (toluene-water) but also toluene-free conditions, because the mutual solubility of ethyl acetate and water was suppressed by the salting-out effect. Among the tested salts, CaCl(2) was found to be the most suitable for this reaction system. Copyright © 2012 Elsevier Ltd. All rights reserved.

  6. Anhydrosugar and sugar alcohol organic markers associated with carboxylic acids in particulate matter from incense burning

    NASA Astrophysics Data System (ADS)

    Tsai, Ying I.; Wu, Pei-Ling; Hsu, Yu-Ting; Yang, Chi-Ru

    2010-09-01

    Aerosol from the burning two types of sandalwood-based incense, Hsing Shan and Lao Shan, was analyzed to characterize the chemical profile of total particulate matter emitted. The total particulate matter (PM) mass emission factors were 46.3 ± 2.68 mg g -1 of Hsing Shan incense and 43.7 ± 1.08 mg g -1 of Lao Shan incense. Chemical analysis of emissions from the two types of incense revealed that of the 25 components in four groups characterized, anhydrosugars formed the major group, at 46.7-52.2% w/w of the identified particulate and 1078.3-1169.8 μg g -1 of incense, followed by inorganic salts at 30.4-31.8% w/w of identified particulate and 681.6-734.0 μg g -1 of incense, carboxylic acids at 12.0-17.1% w/w of the identified particulate and 268.6-392.8 μg g -1 of incense, and sugar alcohols at 4.44-5.38% w/w of the identified particulate and 102.3-120.6 μg g -1 of incense. More anhydrosugars and sugar alcohols were emitted from Lao Shan incense than from Hsing Shan incense whereas more carboxylic acids and organic salts were emitted from Hsing Shan than from Lao Shan. These differences were due to structural and functional differences in the young sandalwood used to make Hsing Shan and the aged sandalwood used to make Lao Shan. The anhydrosugar levoglucosan, used as a marker of biomass burning, was always the most abundant species in emitted PM for both incenses ( Lao Shan 21.7 mg g -1 of PM and Hsing Shan 18.7 mg g -1). K + and Cl - were the second most abundant components (K + and Cl - were summed), accounting for 10.6 mg g -1 of Hsing Shan PM and 9.85 mg g -1 of Lao Shan PM. The most abundant carboxylic acids in the emissions were formic, acetic, succinic, glutaric and phthalic acid. The latter is a fragrance ingredient and a potential health hazard and was twice as prevalent in Lao Shan emissions. Xylitol was the most prevalent of the sugar alcohols at 35.7-36.6% w/w of total identified sugar alcohols. These abundant species are potential markers for

  7. From molecular salt to pseudo CAB cocrystal: Expanding solid-state landscape of carboxylic acids based on charge-assisted COOH⋯COO- hydrogen bonds

    NASA Astrophysics Data System (ADS)

    Lou, Benyong; Perumalla, Sathyanarayana Reddy; Sun, Changquan Calvin

    2015-11-01

    Using three carboxylic acids, we show that the COOH⋯COO- synthon is robust for directing the cocrystallization between a carboxylic acid and a carboxylate of either the same or a chemically different molecule to form a CAB or pseudo CAB cocrystal, respectively. For a given carboxylic acid and a counterion, only one salt could be prepared. However, additional one CAB cocrystals and two pseudo CAB cocrystals could be prepared based on the COOH⋯COO- synthon. The same synthon has the potential to enable the preparation of additional molecular pseudo CAB cocrystals using other chemically distinct carboxylic acids. This significantly increased number of solid forms highlights the values of charge-assisted synthons, such as COOH⋯COO-, in crystal engineering for expanding the range of material properties of a given molecule for optimum performance in product design.

  8. Computer simulations of alkali-acetate solutions: Accuracy of the forcefields in difference concentrations

    NASA Astrophysics Data System (ADS)

    Ahlstrand, Emma; Zukerman Schpector, Julio; Friedman, Ran

    2017-11-01

    When proteins are solvated in electrolyte solutions that contain alkali ions, the ions interact mostly with carboxylates on the protein surface. Correctly accounting for alkali-carboxylate interactions is thus important for realistic simulations of proteins. Acetates are the simplest carboxylates that are amphipathic, and experimental data for alkali acetate solutions are available and can be compared with observables obtained from simulations. We carried out molecular dynamics simulations of alkali acetate solutions using polarizable and non-polarizable forcefields and examined the ion-acetate interactions. In particular, activity coefficients and association constants were studied in a range of concentrations (0.03, 0.1, and 1M). In addition, quantum-mechanics (QM) based energy decomposition analysis was performed in order to estimate the contribution of polarization, electrostatics, dispersion, and QM (non-classical) effects on the cation-acetate and cation-water interactions. Simulations of Li-acetate solutions in general overestimated the binding of Li+ and acetates. In lower concentrations, the activity coefficients of alkali-acetate solutions were too high, which is suggested to be due to the simulation protocol and not the forcefields. Energy decomposition analysis suggested that improvement of the forcefield parameters to enable accurate simulations of Li-acetate solutions can be achieved but may require the use of a polarizable forcefield. Importantly, simulations with some ion parameters could not reproduce the correct ion-oxygen distances, which calls for caution in the choice of ion parameters when protein simulations are performed in electrolyte solutions.

  9. Measurement of formic acid, acetic acid and hydroxyacetaldehyde, hydrogen peroxide, and methyl peroxide in air by chemical ionization mass spectrometry: airborne method development

    NASA Astrophysics Data System (ADS)

    Treadaway, Victoria; Heikes, Brian G.; McNeill, Ashley S.; Silwal, Indira K. C.; O'Sullivan, Daniel W.

    2018-04-01

    A chemical ionization mass spectrometry (CIMS) method utilizing a reagent gas mixture of O2, CO2, and CH3I in N2 is described and optimized for quantitative gas-phase measurements of hydrogen peroxide (H2O2), methyl peroxide (CH3OOH), formic acid (HCOOH), and the sum of acetic acid (CH3COOH) and hydroxyacetaldehyde (HOCH2CHO; also known as glycolaldehyde). The instrumentation and methodology were designed for airborne in situ field measurements. The CIMS quantification of formic acid, acetic acid, and hydroxyacetaldehyde used I- cluster formation to produce and detect the ion clusters I-(HCOOH), I-(CH3COOH), and I-(HOCH2CHO), respectively. The CIMS also produced and detected I- clusters with hydrogen peroxide and methyl peroxide, I-(H2O2) and I-(CH3OOH), though the sensitivity was lower than with the O2- (CO2) and O2- ion clusters, respectively. For that reason, while the I- peroxide clusters are presented, the focus is on the organic acids. Acetic acid and hydroxyacetaldehyde were found to yield equivalent CIMS responses. They are exact isobaric compounds and indistinguishable in the CIMS used. Consequently, their combined signal is referred to as the acetic acid equivalent sum. Within the resolution of the quadrupole used in the CIMS (1 m/z), ethanol and 1- and 2-propanol were potential isobaric interferences to the measurement of formic acid and the acetic acid equivalent sum, respectively. The CIMS response to ethanol was 3.3 % that of formic acid and the response to either 1- or 2-propanol was 1 % of the acetic acid response; therefore, the alcohols were not considered to be significant interferences to formic acid or the acetic acid equivalent sum. The multi-reagent ion system was successfully deployed during the Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ) in 2014. The combination of FRAPPÉ and laboratory calibrations allowed for the post-mission quantification of formic acid and the acetic acid equivalent sum observed during

  10. 75 FR 40736 - Acetic Acid; Exemption from the Requirement of a Tolerance

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-07-14

    ... known as the citric acid (Ref. 1.) or krebs cycle (Ref. 2.), which is the chemical activity in all cells... as antibiotics, antibacterials and antimicrobials. Acetic acid is also the main acid in vinegars, and...

  11. Protective effect of natural honey against acetic acid-induced colitis in rats.

    PubMed

    Mahgoub, A A; el-Medany, A H; Hagar, H H; Sabah, D M

    2002-01-01

    The protective effects of natural honey against acetic acid-induced colitis were investigated in rats. Honey and glucose, fructose, sucrose, maltose mixture were administered, orally and rectally, daily for a period of 4 days. Induction of colitis was done on the third day using 3% acetic acid. Animals were killed on day 4 two hours after administration of the dose and colonic biopsies were taken for macroscopic scoring, histopathological and biochemical studies. Honey dose-dependently afforded protection against acetic acid-induced colonic damage. There was almost 100% protection with the highest dose (5 g/kg) used while glucose, fructose, sucrose, maltose mixture produced no significant protective effect. Also, honey prevented the depletion of the antioxidant enzymes reduced glutathione and catalase and restored the lipid peroxide malondialdehyde towards normal levels. Further studies are required to explore the active ingredients responsible for the antioxidant effect of honey and its therapeutic potential in humans.

  12. Theoretical Study of the Thermal Decomposition of Carboxylic Acids at Pyrolysis Temperature

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

    Clark, J. M.; Robichaud, D. J.; Nimlos, M. R.

    2013-01-01

    Carboxylic acids are important in the processing of biomass into renewable fuels and chemicals. They are formed from the pretreatment and pyrolysis of hemicellulose biopolymers and are released from the decomposition of sugars. They result from the deconstruction of polyhydroxyalkanoates (bacterial carbon storage polymers) from fatty acids derived from algae, bacteria, and oil crops. The thermal deoxygenation of carboxylic acids is an important step in the conversion of biomass into aliphatic hydrocarbons suitable for use in renewable biofuels and as petrochemical replacements. Decarboxylation, a primary decomposition pathway under pyrolysis conditions, represents an ideal conversion process, because it eliminates two atomsmore » of oxygen for every carbon atom removed. Problematically, additional deoxygenation processes exist (e.g. dehydration) that are in direct competition with decarboxylation and result in the formation of reactive and more fragmented end products. To better understand the competition between decarboxylation and other deoxygenation processes and to gain insight into possible catalysts that would favor decarboxylation, we have investigated the mechanisms and thermochemistry of the various unimolecular and bimolecular deoxygenation pathways for a family of C1-C4 organic acids using electronic structure calculations at the M06-2X/6-311++G(2df,p) level of theory.« less

  13. Process for the generation of .alpha., .beta.-unsaturated carboxylic acids and esters using niobium catalyst

    DOEpatents

    Gogate, Makarand Ratnakav; Spivey, James Jerome; Zoeller, Joseph Robert

    1999-01-01

    A process using a niobium catalyst includes the step of reacting an ester or carboxylic acid with oxygen and an alcohol in the presence a niobium catalyst to respectively produce an .alpha.,.beta.-unsaturated ester or carboxylic acid. Methanol may be used as the alcohol, and the ester or carboxylic acid may be passed over the niobium catalyst in a vapor stream containing oxygen and methanol. Alternatively, the process using a niobium catalyst may involve the step of reacting an ester and oxygen in the presence the niobium catalyst to produce an .alpha.,.beta.-unsaturated carboxylic acid. In this case the ester may be a methyl ester. In either case, niobium oxide may be used as the niobium catalyst with the niobium oxide being present on a support. The support may be an oxide selected from the group consisting of silicon oxide, aluminum oxide, titanium oxide and mixtures thereof. The catalyst may be formed by reacting niobium fluoride with the oxide serving as the support. The niobium catalyst may contain elemental niobium within the range of 1 wt % to 70 wt %, and more preferably within the range of 10 wt % to 30 wt %. The process may be operated at a temperature from 150 to 450.degree. C. and preferably from 250 to 350.degree. C. The process may be operated at a pressure from 0.1 to 15 atm. absolute and preferably from 0.5-5 atm. absolute. The flow rate of reactants may be from 10 to 10,000 L/kg.sub.(cat) /h, and preferably from 100 to 1,000 L/kg.sub.(cat) /h.

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

    PubMed

    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.

  15. Cellulose acetate layer effect toward aluminium corrosion rate in hydrochloric acid media

    NASA Astrophysics Data System (ADS)

    Andarany, K. S.; Sagir, A.; Ahmad, A.; Deni, S. K.; Gunawan, W.

    2017-09-01

    Corrosion occurs due to the oxidation and reduction reactions between the material and its environment. The oxidation reaction defined as reactions that produce electrons and reduction is between two elements that bind the electrons. Corrosion cannot be inevitable in life both within the industry and household. Corrosion cannot eliminate but can be control. According to the voltaic table, Aluminum is a metal that easily corroded. This study attempts to characterize the type of corrosion by using a strong acid media (HCl). Experiment using a strong acid (HCl), at a low concentration that occurs is pitting corrosion, whereas at high concentrations that occurs is corrosion erosion. One of prevention method is by using a coating method. An efforts are made to slow the rate of corrosion is by coating the metal with “cellulose acetate” (CA). cellulose acetate consisted of cellulose powder dissolved in 99% acetic acid, and then applied to the aluminum metal. Soaking experiments using hydrochloric acid, cellulose acetate is able to slow down the corrosion rate of 47 479%.

  16. Candida zemplinina can reduce acetic acid produced by Saccharomyces cerevisiae in sweet wine fermentations.

    PubMed

    Rantsiou, Kalliopi; Dolci, Paola; Giacosa, Simone; Torchio, Fabrizio; Tofalo, Rosanna; Torriani, Sandra; Suzzi, Giovanna; Rolle, Luca; Cocolin, Luca

    2012-03-01

    In this study we investigated the possibility of using Candida zemplinina, as a partner of Saccharomyces cerevisiae, in mixed fermentations of must with a high sugar content, in order to reduce its acetic acid production. Thirty-five C. zemplinina strains, which were isolated from different geographic regions, were molecularly characterized, and their fermentation performances were determined. Five genetically different strains were selected for mixed fermentations with S. cerevisiae. Two types of inoculation were carried out: coinoculation and sequential inoculation. A balance between the two species was generally observed for the first 6 days, after which the levels of C. zemplinina started to decrease. Relevant differences were observed concerning the consumption of sugars, the ethanol and glycerol content, and acetic acid production, depending on which strain was used and which type of inoculation was performed. Sequential inoculation led to the reduction of about half of the acetic acid content compared to the pure S. cerevisiae fermentation, but the ethanol and glycerol amounts were also low. A coinoculation with selected combinations of S. cerevisiae and C. zemplinina resulted in a decrease of ~0.3 g of acetic acid/liter, while maintaining high ethanol and glycerol levels. This study demonstrates that mixed S. cerevisiae and C. zemplinina fermentation could be applied in sweet wine fermentation to reduce the production of acetic acid, connected to the S. cerevisiae osmotic stress response.

  17. Evaluation of fermentation kinetics of acid-treated corn cob hydrolysate for xylose fermentation in the presence of acetic acid by Pichia stipitis.

    PubMed

    Kashid, Mohan; Ghosalkar, Anand

    2017-08-01

    The efficient utilization of lignocellulosic biomass for ethanol production depends on the fermentability of the biomass hydrolysate obtained after pretreatment. In this work we evaluated the kinetics of ethanol production from xylose using Pichia stipitis in acid-treated corn cob hydrolysate. Acetic acid is one of the main inhibitors in corn cob hydrolysate that negatively impacts kinetics of xylose fermentation by P. stipitis. Unstructured kinetic model has been formulated that describes cell mass growth and ethanol production as a function of xylose, oxygen, ethanol, and acetic acid concentration. Kinetic parameters were estimated under different operating conditions affecting xylose fermentation. This is the first report on kinetics of xylose fermentation by P. stipitis which includes inhibition of acetic acid on growth and product formation. In the presence of acetic acid in the hydrolysate, the model accurately predicted reduction in maximum specific growth rate (from 0.23 to 0.15 h -1 ) and increase in ethanol yield per unit biomass (from 3 to 6.2 gg -1 ), which was also observed during experimental trials. Presence of acetic acid in the fermentation led to significant reduction in the cell growth rate, reduction in xylose consumption and ethanol production rate. The developed model accurately described physiological state of P. stipitis during corn cob hydrolysate fermentation. Proposed model can be used to predict the influence of xylose, ethanol, oxygen, and acetic acid concentration on cell growth and ethanol productivity in industrial fermentation.

  18. REACTIONS OF MERCAPTANS. I. FORMATION OF 2-METHYL-2-THIAZOLINE-4- CARBOXYLIC ACID FROM N-ACETYLCYSTEINE. II. A SPECTROPHOTOMETRIC METHOD FOR STUDY OF THE REACTION OF RADIATION-PROTECTIVE MERCAPTANS WITH ARYL DISULFIDES

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

    Smith, H.A. Jr.

    1962-08-01

    I. Methyl 2-methyl-2-thiazoline-4-carboxylate was synthesized and converted to the corresponding acid. The behavior of the carboxythiazoline in various concentrations of mineral acids was studied spectrophotometrically. The cyclization of N-acetylcysteine to form a thiazoline-ring compound in concentrated mineral acids was also studied by this means. N-Acetylcysteine in concentrated mineral acid solutions yielded 2-methyl-2-thiazoline-4-carboxylic acid, which also was obtained by controlied hydrolysis of the corresponding methyl ester. Hydrolysis of methyl 2-methyl2-thiazoline-4-carboxylate, pK 3.05, in 0.1M sodium hydroxide yielded the corresponding carboxythiazoline in solution, pK 2.20 and 4.95. The carboxythiazoline was hydrolyzed very slowly in 7M hydrochloric acid, but the velocity of reactionmore » increased with decreasing acid concentration to a maximum at about pH 1.7; the products were N- and Sacetylcysteine, as well as cysteine and acetic acid. At acid concentrations below 0.2M, the last two products were formed slowly, and a pseudo-equilibrium could be established between thiazolinium ion, N-, and S-acetylcysteine. Equilibrium constants were determined. II. 4,4'-Dithiobis (benzenesulfonic acid) (I) and 4,4'-dithiobis(1-naphthalenesulfonic acid) (II) were synthesized from sulfanilic and naphthionic acids, respectively. The absorption spectra of I and II and of the corresponding mercaptans were determined. The thiol-disuifide interchange reactions were studied by spectrophotometric means for the reactions of cysteine with I and with II, and the equilibrium constants were determined. The systems had spectra very similar to those of the respective mixed disuifides with cysteine, and it was not possible to determine the concentrations from absorbancy measurements. On the other hand, the mercaptide ions had spectra different from the other species, with maxima at 285 and 348 m mu , respectively, and the concentrations of the corresponding mercaptans could

  19. Osmoadaptation of wine yeast (Saccharomyces cerevisiae) during Icewine fermentation leads to high levels of acetic acid.

    PubMed

    Heit, C; Martin, S J; Yang, F; Inglis, D L

    2018-06-01

    Volatile acidity (VA) production along with gene expression patterns, encoding enzymes involved in both acetic acid production and utilization, were investigated to relate gene expression patterns to the production of undesired VA during Icewine fermentation. Icewine juice and diluted Icewine juice were fermented using the Saccharomyces cerevisiae wine yeast K1-V1116. Acetic acid production increased sixfold during the Icewine fermentation vs the diluted juice condition, while ethyl acetate production increased 2·4-fold in the diluted fermentation relative to the Icewine. Microarray analysis profiled the transcriptional response of K1-V1116 under both conditions. ACS1 and ACS2 were downregulated 19·0-fold and 11·2-fold, respectively, in cells fermenting Icewine juice compared to diluted juice. ALD3 expression was upregulated 14·6-fold, and gene expressions involved in lipid and ergosterol synthesis decreased during Icewine fermentation. Decreased expression of ACS1 and ACS2 together with increased ALD3 expression contributes to the higher acetic acid and lower ethyl acetate levels generated by K1-V1116 fermenting under hyperosmotic stress. This work represents a more comprehensive understanding of how and why commercial wine yeast respond at the transcriptional and metabolic level during fermentation of Icewine juice, and how these responses contribute to increased acetic acid and decreased ethyl acetate production. © 2018 The Society for Applied Microbiology.

  20. Merging photoredox and nickel catalysis: decarboxylative cross-coupling of carboxylic acids with vinyl halides.

    PubMed

    Noble, Adam; McCarver, Stefan J; MacMillan, David W C

    2015-01-21

    Decarboxylative cross-coupling of alkyl carboxylic acids with vinyl halides has been accomplished through the synergistic merger of photoredox and nickel catalysis. This new methodology has been successfully applied to a variety of α-oxy and α-amino acids, as well as simple hydrocarbon-substituted acids. Diverse vinyl iodides and bromides give rise to vinylation products in high efficiency under mild, operationally simple reaction conditions.

  1. Merging Photoredox and Nickel Catalysis: Decarboxylative Cross-Coupling of Carboxylic Acids with Vinyl Halides

    PubMed Central

    2015-01-01

    Decarboxylative cross-coupling of alkyl carboxylic acids with vinyl halides has been accomplished through the synergistic merger of photoredox and nickel catalysis. This new methodology has been successfully applied to a variety of α-oxy and α-amino acids, as well as simple hydrocarbon-substituted acids. Diverse vinyl iodides and bromides give rise to vinylation products in high efficiency under mild, operationally simple reaction conditions. PMID:25521443

  2. Peptide and protein quantitation by acid-catalyzed 18O-labeling of carboxyl groups.

    PubMed

    Haaf, Erik; Schlosser, Andreas

    2012-01-03

    We have developed a new method that applies acidic catalysis with hydrochloric acid for (18)O-labeling of peptides at their carboxyl groups. With this method, peptides get labeled at their C-terminus, at Asp and Glu residues, and at carboxymethylated cysteine residues. Oxygen atoms at phosphate groups of phosphopeptide are not exchanged. Our elaborated labeling protocol is easy to perform, fast (5 h and 30 min), and results in 95-97 atom % incorporation of (18)O at carboxyl groups. Undesired side reactions, such as deamidation or peptide hydrolysis, occur only at a very low level under the conditions applied. In addition, data analysis can be performed automatically using common software tools, such as Mascot Distiller. We have demonstrated the capability of this method for the quantitation of peptides as well as for phosphopeptides. © 2011 American Chemical Society

  3. Mechanisms leading to oligomers and SOA through aqueous photooxidation: insights from OH radical oxidation of acetic acid and methylglyoxal

    NASA Astrophysics Data System (ADS)

    Tan, Y.; Lim, Y. B.; Altieri, K. E.; Seitzinger, S. P.; Turpin, B. J.

    2012-01-01

    Previous experiments have demonstrated that the aqueous OH radical oxidation of methylglyoxal produces low volatility products including pyruvate, oxalate and oligomers. These products are found predominantly in the particle phase in the atmosphere, suggesting that methylglyoxal is a precursor of secondary organic aerosol (SOA). Acetic acid plays a central role in the aqueous oxidation of methylglyoxal and it is a ubiquitous product of gas phase photochemistry, making it a potential "aqueous" SOA precursor in its own right. However, the fate of acetic acid upon aqueous-phase oxidation is not well understood. In this research, acetic acid (20 μM-10 mM) was oxidized by OH radicals, and pyruvic acid and methylglyoxal experimental samples were analyzed using new analytical methods, in order to better understand the formation of SOA from acetic acid and methylglyoxal. Glyoxylic, glycolic, and oxalic acids formed from acetic acid and OH radicals. In contrast to the aqueous OH radical oxidation of methylglyoxal, the aqueous OH radical oxidation of acetic acid did not produce succinic acid and oligomers. This suggests that the methylgloxal-derived oligomers do not form through the acid catalyzed esterification pathway proposed previously. Using results from these experiments, radical mechanisms responsible for oligomer formation from methylglyoxal oxidation in clouds and wet aerosols are proposed. The importance of acetic acid/acetate as an SOA precursor is also discussed. We hypothesize that this and similar chemistry is central to the daytime formation of oligomers in wet aerosols.

  4. [Effect of acetic acid, furfural and 5-hydroxymethylfurfural on production of 2,3-butanediol by Klebsiella oxytoca].

    PubMed

    Wu, Jing; Cheng, Keke; Li, Wenying; Feng, Jie; Zhang, Jian'an

    2013-03-01

    To get the tolerability and consumption of Klebsiella oxytoca on major inhibitors in lignocelluloses hydrolysate, we studied the effect of acetic acid, furfural and 5-hydroxymethylfurfural on production of 2,3-butanediol by Klebsiella oxytoca. The metabolites of furfural and 5-hydroxymethylfurfural were measured. The results show that when acetic acid, furfural and 5-hydroxymethylfurfural was individually added, tolerance threshold for Klebsiella oxytoca was 30 g/L, 4 g/L and 5 g/L, respectively. Acetic acid was likely used as substrate to produce 2,3-butanediol. The yield of 2,3-butanediol increased when acetic acid concentration was lower than 30 g/L. In the fermentation, more than 70% 5-hydroxymethylfurfural was converted to 2,5-furandimethanol. All furfural and the rest of 5-hydroxymethylfurfural were metabolized by Klebsiella oxytoca. It showed that in the detoxification process of 2,3-butanediol production using lignocelluloses hydrolysate, furfural should be given priority to remove and a certain concentration of acetic acid is not need to removal.

  5. Fermentation of sugarcane bagasse and chicken manure to calcium carboxylates under thermophilic conditions.

    PubMed

    Fu, Zhihong; Holtzapple, Mark T

    2010-09-01

    Sugarcane bagasse and chicken manure were anaerobically fermented to carboxylic acids using a mixed culture of marine microorganisms at 55 degrees C. Using the MixAlco process--an example of consolidated bioprocessing--the resulting carboxylate salts can be converted to mixed alcohol fuels or gasoline. To enhance digestibility, sugarcane bagasse was lime pretreated with 0.1 g Ca(OH)(2)/g dry biomass at 100 degrees C for 2 h. Four-stage countercurrent fermentation of 80% sugarcane bagasse/20% chicken manure was performed at various volatile solids (VS) loading rates and liquid residence times. Calcium carbonate was used as a buffer during fermentation. The highest acid productivity of 0.79 g/(L day) occurred at a total acid concentration of 21.5 g/L. The highest conversion (0.59 g VS digested/g VS fed) and yield (0.18 g total acids/g VS fed) occurred at a total acid concentration of 15.5 g/L. The continuum particle distribution model (CPDM) predicted the experimental total acid concentrations and conversions at an average error of 10.14% and 12.68%, respectively. CPDM optimizations show that high conversion (>80%) and total acid concentration of 21.3 g/L are possible with 300 g substrate/(L liquid), 30 days liquid residence time, and 3 g/(L day) solid loading rate. Thermophilic fermentation has a higher acetate content (approximately 63 wt%) than mesophilic fermentation (approximately 39 wt%).

  6. Norfloxacin salts of carboxylic acids curtail planktonic and biofilm mode of growth in ESKAPE pathogens.

    PubMed

    Lowrence, R C; Ramakrishnan, A; Sundaramoorthy, N S; Shyam, A; Mohan, V; Subbarao, H M V; Ulaganathan, V; Raman, T; Solomon, A; Nagarajan, S

    2018-02-01

    To enhance the antimicrobial and antibiofilm activity of norfloxacin against the planktonic and biofilm mode of growth in ESKAPE pathogens using chemically modified norfloxacin salts. Antimicrobial testing, synergy testing and time-kill curve analysis were performed to evaluate antibacterial effect of norfloxacin carboxylic acid salts against ESKAPE pathogens. In vivo efficacy to reduce bacterial bioburden was evaluated in zebrafish infection model. Crystal violet assay and live-dead staining were performed to discern antibiofilm effect. Membrane permeability, integrity and molecular docking studies were carried out to ascertain the mechanism of action. The carboxylic acid salts, relative to parent molecule norfloxacin, displayed two- to fourfold reduction in minimum inhibitory concentration against Staphylococcus aureus and Pseudomonas aeruginosa, in addition to displaying potent bacteriostatic effect against certain members of ESKAPE pathogens. In vivo treatments revealed that norfloxacin tartrate (SRIN2) reduced MRSA bioburden by greater than 1 log fold relative to parent molecule in the muscle tissue. In silico docking with gyrA of S. aureus showed increased affinity of SRIN2 towards DNA gyrase. The enhanced antibacterial effect of norfloxacin salts could be partially accounted by altered membrane permeability in S. aureus and perturbed membrane integrity in P. aeruginosa. Antibiofilm studies revealed that SRIN2 (norfloxacin tartrate) and SRIN3 (norfloxacin benzoate) exerted potent antibiofilm effect particularly against Gram-negative ESKAPE pathogens. The impaired colonization of both S. aureus and P. aeruginosa due to improved norfloxacin salts was further supported by live-dead imaging. Norfloxacin carboxylic acid salts can act as potential alternatives in terms of drug resensitization and reuse. Our study shows that carboxylic acid salts of norfloxacin could be effectively employed to treat both planktonic- and biofilm-based infections caused by select

  7. Loxoprofen inhibits facilitated micturition reflex induced by acetic acid urinary bladder infusion of the rats.

    PubMed

    Shinozaki, Sachiyo; Saito, Motoaki; Kawatani, Masahito

    2005-02-01

    Prostaglandins (PGs) are well known as one of the chemical mediators of inflammation. Nonsteroidal anti-inflammatory drugs (NSAIDs), PG synthesis inhibitors, are used for anti-nociception and/or anti-inflammation. We examine the effect of loxoprofen, an NSAID, on micturiton in acetic acid-induced bladder inflammation of the rats. In cystometrogram study with saline infusion into the urinary bladder, loxoprofen did not alter the interval of bladder contraction (IC, 107% of the control). IC was shortened by acetic acid infusion (65% of the control) and loxoprofen prolonged the IC (162% of acetic acid infused period). This prolonged IC was approximately same as the control. Loxoprofen did not alter the threshold pressure and the maximal voiding pressure. These data suggest that PGE2 might not play a part of normal micturition and may play a part of the micturition reflex during acetic acid infusion. That is, loxoprofen might be useful for pathological hyperreflex of the micturition.

  8. Mechanisms leading to oligomers and SOA through aqueous photooxidation: insights from OH radical oxidation of acetic acid

    NASA Astrophysics Data System (ADS)

    Tan, Y.; Lim, Y. B.; Altieri, K. E.; Seitzinger, S. P.; Turpin, B. J.

    2011-06-01

    Previous experiments have demonstrated that the aqueous OH radical oxidation of methylglyoxal produces low volatility products including oxalate and oligomers. These products are found predominantly in the particle phase in the atmosphere, suggesting that methylglyoxal is a precursor of secondary organic aerosol (SOA). Acetic acid is an important intermediate in aqueous methylglyoxal oxidation and a ubiquitous product of gas phase photochemistry, making it a potential "aqueous" SOA precursor in its own right. Altieri et al. (2008) proposed that acetic acid was the precursor of oligoesters observed in methylglyoxal oxidation. However, the fate of acetic acid upon aqueous-phase oxidation is not well understood. In this research, acetic acid at concentrations relevant to atmospheric waters (20 μM-10 mM) was oxidized by OH radical. Products were analyzed by ion chromatography (IC), electrospray ionization mass spectrometry (ESI-MS), and IC-ESI-MS. The formation of glyoxylic, glycolic, and oxalic acids were observed. In contrast to methylglyoxal oxidation, succinic acid and oligomers were not detected. Using results from these and methylglyoxal + OH radical experiments, radical mechanisms responsible for oligomer formation from methylglyoxal oxidation in clouds and wet aerosols are proposed. The importance of acetic acid/acetate as an SOA precursor is also discussed. We hypothesize that this and similar chemistry is central to the daytime formation of oligomers in wet aerosols.

  9. Acetic Acid Bacteria and the Production and Quality of Wine Vinegar

    PubMed Central

    Torija, María Jesús; García-Parrilla, María del Carmen; Troncoso, Ana María

    2014-01-01

    The production of vinegar depends on an oxidation process that is mainly performed by acetic acid bacteria. Despite the different methods of vinegar production (more or less designated as either “fast” or “traditional”), the use of pure starter cultures remains far from being a reality. Uncontrolled mixed cultures are normally used, but this review proposes the use of controlled mixed cultures. The acetic acid bacteria species determine the quality of vinegar, although the final quality is a combined result of technological process, wood contact, and aging. This discussion centers on wine vinegar and evaluates the effects of these different processes on its chemical and sensory properties. PMID:24574887

  10. Facile Formation of Acetic Sulfuric Anhydride in a Supersonic Jet: Characterization by Microwave Spectroscopy and Computational Chemistry

    NASA Astrophysics Data System (ADS)

    Huff, Anna; Smith, CJ; Mackenzie, Becca; Leopold, Ken

    2017-06-01

    Sulfur trioxide and acetic acid are shown to react under supersonic jet conditions to form acetic sulfuric anhydride, CH_{3}COOSO_{2}OH. Rotational spectra of the parent, ^{34}S, methyl ^{13}C, and fully deuterated isotopologues have been observed by chirped-pulse and conventional cavity microwave spectroscopy. A and E internal rotation states have been observed for each isotopologue studied and the methyl group internal rotation barriers have been determined (241.043(65) \\wn for the parent species). The reaction is analogous to that of our previous report on the reaction of sulfur trioxide and formic acid. DFT and CCSD calculations are also presented which indicate that the reaction proceeds via a π_{2} + π_{2} + σ_{2} cycloaddition reaction. These results support our previous conjecture that the reaction of SO_{3} with carboxylic acids is both facile and general. Possible implications for atmospheric aerosol formation are discussed.

  11. Discovery of novel BTK inhibitors with carboxylic acids.

    PubMed

    Gao, Xiaolei; Wang, James; Liu, Jian; Guiadeen, Deodial; Krikorian, Arto; Boga, Sobhana Babu; Alhassan, Abdul-Basit; Selyutin, Oleg; Yu, Wensheng; Yu, Younong; Anand, Rajan; Liu, Shilan; Yang, Chundao; Wu, Hao; Cai, Jiaqiang; Cooper, Alan; Zhu, Hugh; Maloney, Kevin; Gao, Ying-Duo; Fischmann, Thierry O; Presland, Jeremy; Mansueto, My; Xu, Zangwei; Leccese, Erica; Zhang-Hoover, Jie; Knemeyer, Ian; Garlisi, Charles G; Bays, Nathan; Stivers, Peter; Brandish, Philip E; Hicks, Alexandra; Kim, Ronald; Kozlowski, Joeseph A

    2017-03-15

    We report the design and synthesis of a series of novel Bruton's Tyrosine Kinase (BTK) inhibitors with a carboxylic acid moiety in the ribose pocket. This series of compounds has demonstrated much improved off-target selectivities including adenosine uptake (AdU) inhibition compared to the piperidine amide series. Optimization of the initial lead compound 4 based on BTK enzyme inhibition, and human peripheral blood mononuclear cell (hPBMC) and human whole blood (hWB) activity led to the discovery of compound 40, with potent BTK inhibition, reduced off target activities, as well as favorable pharmacokinetic profile in both rat and dog. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. Neuron-astrocyte interactions, pyruvate carboxylation and the pentose phosphate pathway in the neonatal rat brain.

    PubMed

    Morken, Tora Sund; Brekke, Eva; Håberg, Asta; Widerøe, Marius; Brubakk, Ann-Mari; Sonnewald, Ursula

    2014-01-01

    Glucose and acetate metabolism and the synthesis of amino acid neurotransmitters, anaplerosis, glutamate-glutamine cycling and the pentose phosphate pathway (PPP) have been extensively investigated in the adult, but not the neonatal rat brain. To do this, 7 day postnatal (P7) rats were injected with [1-(13)C]glucose and [1,2-(13)C]acetate and sacrificed 5, 10, 15, 30 and 45 min later. Adult rats were injected and sacrificed after 15 min. To analyse pyruvate carboxylation and PPP activity during development, P7 rats received [1,2-(13)C]glucose and were sacrificed 30 min later. Brain extracts were analysed using (1)H- and (13)C-NMR spectroscopy. Numerous differences in metabolism were found between the neonatal and adult brain. The neonatal brain contained lower levels of glutamate, aspartate and N-acetylaspartate but similar levels of GABA and glutamine per mg tissue. Metabolism of [1-(13)C]glucose at the acetyl CoA stage was reduced much more than that of [1,2-(13)C]acetate. The transfer of glutamate from neurons to astrocytes was much lower while transfer of glutamine from astrocytes to glutamatergic neurons was relatively higher. However, transport of glutamine from astrocytes to GABAergic neurons was lower. Using [1,2-(13)C]glucose it could be shown that despite much lower pyruvate carboxylation, relatively more pyruvate from glycolysis was directed towards anaplerosis than pyruvate dehydrogenation in astrocytes. Moreover, the ratio of PPP/glucose-metabolism was higher. These findings indicate that only the part of the glutamate-glutamine cycle that transfers glutamine from astrocytes to neurons is operating in the neonatal brain and that compared to adults, relatively more glucose is prioritised to PPP and pyruvate carboxylation. Our results may have implications for the capacity to protect the neonatal brain against excitotoxicity and oxidative stress.

  13. 40 CFR 721.304 - Acetic acid, [(5-chloro-8-quinolinyl)oxy-], 1-methyl hexyl ester.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Acetic acid, [(5-chloro-8-quinolinyl)oxy-], 1-methyl hexyl ester. 721.304 Section 721.304 Protection of Environment ENVIRONMENTAL... Significant New Uses for Specific Chemical Substances § 721.304 Acetic acid, [(5-chloro-8-quinolinyl)oxy-], 1...

  14. Influence of levan-producing acetic acid bacteria on buckwheat-sourdough breads.

    PubMed

    Ua-Arak, Tharalinee; Jakob, Frank; Vogel, Rudi F

    2017-08-01

    Buckwheat sourdoughs supplemented with molasses as natural sucrose source were fermented with levan-producing Gluconobacter (G.) albidus TMW 2.1191 and Kozakia (K.) baliensis NBRC 16680. Cell growth, concomitant levan and low-molecular-weight metabolite production were monitored. Sourdough breads were prepared with different sourdoughs from both strains (24, 30 and 48 h fermentation, respectively) and analyzed with respect to bread volume, crumb hardness and sensory characteristics. During fermentation, levan, acetic and gluconic acids were increasingly produced, while spontaneously co-growing lactic acid bacteria additionally formed acetic and lactic acids. Sourdoughs from both strains obtained upon 24 h of fermentation significantly improved the bread sensory and quality, including higher specific volume as well as lower crumb hardness. Buckwheat doughs containing isolated levan, with similar molecular size and mass compared to in situ produced levan in the sourdough at 48 h, verified the positive effect of levan on bread quality. However, the positive effects of levan were masked to a certain extent by the impact from the natural acidification during fermentations. While levan-producing acetic acid bacteria are a promising alternative for the development of clean-label gluten-free breads without the need of additives, an appropriate balance between acidification and levan production (amount and structure) must be reached. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Translocation of radiolabeled indole-3-acetic acid and indole-3-acetyl-myo-inositol from kernel to shoot of Zea mays L

    NASA Technical Reports Server (NTRS)

    Chisnell, J. R.; Bandurski, R. S.

    1988-01-01

    Either 5-[3H]indole-3-acetic acid (IAA) or 5-[3H]indole-3-acetyl-myo-inositol was applied to the endosperm of kernels of dark-grown Zea mays seedlings. The distribution of total radioactivity, radiolabeled indole-3-acetic acid, and radiolabeled ester conjugated indole-3-acetic acid, in the shoots was then determined. Differences were found in the distribution and chemical form of the radiolabeled indole-3-acetic acid in the shoot depending upon whether 5-[3H]indole-3-acetic acid or 5-[3H]indole-3-acetyl-myo-inositol was applied to the endosperm. We demonstrated that indole-3-acetyl-myo-inositol applied to the endosperm provides both free and ester conjugated indole-3-acetic acid to the mesocotyl and coleoptile. Free indole-3-acetic acid applied to the endosperm supplies some of the indole-3-acetic acid in the mesocotyl but essentially no indole-3-acetic acid to the coleoptile or primary leaves. It is concluded that free IAA from the endosperm is not a source of IAA for the coleoptile. Neither radioactive indole-3-acetyl-myo-inositol nor IAA accumulates in the tip of the coleoptile or the mesocotyl node and thus these studies do not explain how the coleoptile tip controls the amount of IAA in the shoot.

  16. Single and combined effects of acetic acid, furfural, and sugars on the growth of the pentose-fermenting yeast Meyerozyma guilliermondii.

    PubMed

    Perna, Michelle Dos Santos Cordeiro; Bastos, Reinaldo Gaspar; Ceccato-Antonini, Sandra Regina

    2018-02-01

    The tolerance of the pentose-fermenting yeast Meyerozyma guilliermondii to the inhibitors released after the biomass hydrolysis, such as acetic acid and furfural, was surveyed. We first verified the effects of acetic acid and cell concentrations and initial pH on the growth of a M. guilliermondii strain in a semi-synthetic medium containing acetic acid as the sole carbon source. Second, the single and combined effects of furfural, acetic acid, and sugars (xylose, arabinose, and glucose) on the sugar uptake, cell growth, and ethanol production were also analysed. Growth inhibition occurred in concentrations higher than 10.5 g l -1 acetic acid and initial pH 3.5. The maximum specific growth rate (µ) was 0.023 h -1 and the saturation constant (ks) was 0.75 g l -1 acetic acid. Initial cell concentration also influenced µ. Acetic acid (initial concentration 5 g l -1 ) was co-consumed with sugars even in the presence of 20 mg l -1 furfural without inhibition to the yeast growth. The yeast grew and fermented sugars in a sugar-based medium with acetic acid and furfural in concentrations much higher than those usually found in hemicellulosic hydrolysates.

  17. Reactivity and reaction intermediates for acetic acid adsorbed on CeO 2(111)

    DOE PAGES

    Calaza, Florencia C.; Chen, Tsung -Liang; Mullins, David R.; ...

    2015-05-02

    Adsorption and reaction of acetic acid on a CeO 2(1 1 1) surface was studied by a combination of ultra-highvacuum based methods including temperature desorption spectroscopy (TPD), soft X-ray photoelectronspectroscopy (sXPS), near edge X-ray absorption spectroscopy (NEXAFS) and reflection absorption IRspectroscopy (RAIRS), together with density functional theory (DFT) calculations. TPD shows that thedesorption products are strongly dependent upon the initial oxidation state of the CeO 2 surface, includingselectivity between acetone and acetaldehyde products. The combination of sXPS and NEXAFS demon-strate that acetate forms upon adsorption at low temperature and is stable to above 500 K, above whichpoint ketene, acetone andmore » acetic acid desorb. Furthermore, DFT and RAIRS show that below 500 K, bridge bondedacetate coexists with a moiety formed by adsorption of an acetate at an oxygen vacancy, formed bywater desorption.« less

  18. Inactivation of the transcription factor mig1 (YGL035C) in Saccharomyces cerevisiae improves tolerance towards monocarboxylic weak acids: acetic, formic and levulinic acid.

    PubMed

    Balderas-Hernández, Victor E; Correia, Kevin; Mahadevan, Radhakrishnan

    2018-06-06

    Toxic concentrations of monocarboxylic weak acids present in lignocellulosic hydrolyzates affect cell integrity and fermentative performance of Saccharomyces cerevisiae. In this work, we report the deletion of the general catabolite repressor Mig1p as a strategy to improve the tolerance of S. cerevisiae towards inhibitory concentrations of acetic, formic or levulinic acid. In contrast with the wt yeast, where the growth and ethanol production were ceased in presence of acetic acid 5 g/L or formic acid 1.75 g/L (initial pH not adjusted), the m9 strain (Δmig1::kan) produced 4.06 ± 0.14 and 3.87 ± 0.06 g/L of ethanol, respectively. Also, m9 strain tolerated a higher concentration of 12.5 g/L acetic acid (initial pH adjusted to 4.5) without affecting its fermentative performance. Moreover, m9 strain produced 33% less acetic acid and 50-70% less glycerol in presence of weak acids, and consumed acetate and formate as carbon sources under aerobic conditions. Our results show that the deletion of Mig1p provides a single gene deletion target for improving the acid tolerance of yeast strains significantly.

  19. Ethylene Production and 1-Aminocyclopropane-1-Carboxylic Acid Conjugation in Thermoinhibited Cicer arietinum L. Seeds 1

    PubMed Central

    Gallardo, Mercedes; Delgado, María del Mar; Sánchez-Calle, Isabel María; Matilla, Angel Jesús

    1991-01-01

    The effect of supraoptimal temperatures (30°C, 35°C) on germination and ethylene production of Cicer arietinum (chick-pea) seeds was measured. Compared with a 25°C control, these temperatures inhibited both germination and ethylene production. The effect of supraoptimal temperatures could be alleviated by treating the seeds with ethylene. It was concluded that one effect of high temperature on germination was due to its negative effect on ethylene production. This inhibitory effect of high temperature was due to increased conjugation of 1-aminocyclopropane-1-carboxylic acid to 1-(malonylamino)cyclopropane-1-carboxylic acid and to an inhibition of ethylene-forming enzyme activity. PMID:16668358

  20. Determination of the asphaltene and carboxylic acid content of a heavy oil using a microfluidic device.

    PubMed

    Bowden, Stephen A; Wilson, Rab; Parnell, John; Cooper, Jonathan M

    2009-03-21

    Heavy oil utilisation is set to increase over the coming decades as reserves of conventional oil decline. Heavy oil differs from conventional oil in containing relatively large quantities of asphaltene and carboxylic acids. The proportions of these compounds greatly influence how oil behaves during production and its utilisation as a fuel or feedstock. We report the development of a microfluidic technique, based on a H-cell, that can extract the carboxylic acid components of an oil and assess its asphaltene content. Ultimately this technology could yield a field-deployable device capable of performing measurements that facilitate improved resource management at the point of resource-extraction.

  1. Determination of carboxyl groups in wood fibers by headspace gas chromatography

    Treesearch

    X.-S. Chai; Q.X. Hou; J.Y. Zhu; S.-L. Chen; S.F. Wang; L. Lucia

    2003-01-01

    The phase reaction conversion (PRC) headspace gas chromatographic (HSGC) technique was employed to develop a method for the determination of the content of carboxyl groups in wood fibers. Acid treatment of the wood fibers using hydrochloric was applied to convert carboxyl groups to carboxyl acids. Bicarbonate solution is then used to react with carboxyl acids on the...

  2. Adaptive Response and Tolerance to Acetic Acid in Saccharomyces cerevisiae and Zygosaccharomyces bailii: A Physiological Genomics Perspective.

    PubMed

    Palma, Margarida; Guerreiro, Joana F; Sá-Correia, Isabel

    2018-01-01

    Acetic acid is an important microbial growth inhibitor in the food industry; it is used as a preservative in foods and beverages and is produced during normal yeast metabolism in biotechnological processes. Acetic acid is also a major inhibitory compound present in lignocellulosic hydrolysates affecting the use of this promising carbon source for sustainable bioprocesses. Although the molecular mechanisms underlying Saccharomyces cerevisiae response and adaptation to acetic acid have been studied for years, only recently they have been examined in more detail in Zygosaccharomyces bailii . However, due to its remarkable tolerance to acetic acid and other weak acids this yeast species is a major threat in the spoilage of acidic foods and beverages and considered as an interesting alternative cell factory in Biotechnology. This review paper emphasizes genome-wide strategies that are providing global insights into the molecular targets, signaling pathways and mechanisms behind S. cerevisiae and Z. bailii tolerance to acetic acid, and extends this information to other weak acids whenever relevant. Such comprehensive perspective and the knowledge gathered in these two yeast species allowed the identification of candidate molecular targets, either for the design of effective strategies to overcome yeast spoilage in acidic foods and beverages, or for the rational genome engineering to construct more robust industrial strains. Examples of successful applications are provided.

  3. Adaptive Response and Tolerance to Acetic Acid in Saccharomyces cerevisiae and Zygosaccharomyces bailii: A Physiological Genomics Perspective

    PubMed Central

    Palma, Margarida; Guerreiro, Joana F.; Sá-Correia, Isabel

    2018-01-01

    Acetic acid is an important microbial growth inhibitor in the food industry; it is used as a preservative in foods and beverages and is produced during normal yeast metabolism in biotechnological processes. Acetic acid is also a major inhibitory compound present in lignocellulosic hydrolysates affecting the use of this promising carbon source for sustainable bioprocesses. Although the molecular mechanisms underlying Saccharomyces cerevisiae response and adaptation to acetic acid have been studied for years, only recently they have been examined in more detail in Zygosaccharomyces bailii. However, due to its remarkable tolerance to acetic acid and other weak acids this yeast species is a major threat in the spoilage of acidic foods and beverages and considered as an interesting alternative cell factory in Biotechnology. This review paper emphasizes genome-wide strategies that are providing global insights into the molecular targets, signaling pathways and mechanisms behind S. cerevisiae and Z. bailii tolerance to acetic acid, and extends this information to other weak acids whenever relevant. Such comprehensive perspective and the knowledge gathered in these two yeast species allowed the identification of candidate molecular targets, either for the design of effective strategies to overcome yeast spoilage in acidic foods and beverages, or for the rational genome engineering to construct more robust industrial strains. Examples of successful applications are provided. PMID:29515554

  4. Ethylene biosynthesis by 1-aminocyclopropane-1-carboxylic acid oxidase: a DFT study.

    PubMed

    Bassan, Arianna; Borowski, Tomasz; Schofield, Christopher J; Siegbahn, Per E M

    2006-11-24

    The reaction catalyzed by the plant enzyme 1-aminocyclopropane-1-carboxylic acid oxidase (ACCO) was investigated by using hybrid density functional theory. ACCO belongs to the non-heme iron(II) enzyme superfamily and carries out the bicarbonate-dependent two-electron oxidation of its substrate ACC (1-aminocyclopropane-1-carboxylic acid) concomitant with the reduction of dioxygen and oxidation of a reducing agent probably ascorbate. The reaction gives ethylene, CO(2), cyanide and two water molecules. A model including the mononuclear iron complex with ACC in the first coordination sphere was used to study the details of O-O bond cleavage and cyclopropane ring opening. Calculations imply that this unusual and complex reaction is triggered by a hydrogen atom abstraction step generating a radical on the amino nitrogen of ACC. Subsequently, cyclopropane ring opening followed by O-O bond heterolysis leads to a very reactive iron(IV)-oxo intermediate, which decomposes to ethylene and cyanoformate with very low energy barriers. The reaction is assisted by bicarbonate located in the second coordination sphere of the metal.

  5. Comparison of Three Solid Phase Materials for the Extraction of Carboxylic Acids from River Water Followed by 2D GC × GC-TOFMS Determination

    PubMed Central

    Bosire, G. O.; Ngila, J. C.; Parshotam, H.

    2016-01-01

    The extraction and determination of aliphatic and aromatic carboxylic acids as well as their influence on the aromaticity and molecularity relationship of natural organic matter (NOM) in water are reported in this study. Three solid phase extraction (SPE) sorbents were used and their extraction efficiencies evaluated after chromatographic determinations (using gas chromatography with a time of flight mass spectrometer (GC × GC-TOFMS) and liquid chromatography with organic carbon detector (LC-OCD)). More than 42 carboxylic acids were identified in raw water from the Vaal River, which feeds the Lethabo Power Generation Station, South Africa, with cooling water. The aromatic carboxylic acid efficiency (28%) was achieved by using Strata™ X SPE while the highest aliphatic carboxylic acid efficiency (92.08%) was achieved by silica SPE. The hydrophobic nature of NOM in water depends on the nature of organic compounds in water, whether aromatic or aliphatic. The LC-OCD was used to assess the hydrophobicity levels of NOM as a function of these carboxylic acids in cooling water. The LC-OCD results showed that the aromatic nature of NOM in SPE filtered water followed the order Silica>Strata X>C-18. From the results, the hydrophobicity degree of the samples depended on the type and number of carboxylic acids that were removed by the SPE cartridges. PMID:27274730

  6. Global insights into acetic acid resistance mechanisms and genetic stability of Acetobacter pasteurianus strains by comparative genomics

    NASA Astrophysics Data System (ADS)

    Wang, Bin; Shao, Yanchun; Chen, Tao; Chen, Wanping; Chen, Fusheng

    2015-12-01

    Acetobacter pasteurianus (Ap) CICC 20001 and CGMCC 1.41 are two acetic acid bacteria strains that, because of their strong abilities to produce and tolerate high concentrations of acetic acid, have been widely used to brew vinegar in China. To globally understand the fermentation characteristics, acid-tolerant mechanisms and genetic stabilities, their genomes were sequenced. Genomic comparisons with 9 other sequenced Ap strains revealed that their chromosomes were evolutionarily conserved, whereas the plasmids were unique compared with other Ap strains. Analysis of the acid-tolerant metabolic pathway at the genomic level indicated that the metabolism of some amino acids and the known mechanisms of acetic acid tolerance, might collaboratively contribute to acetic acid resistance in Ap strains. The balance of instability factors and stability factors in the genomes of Ap CICC 20001 and CGMCC 1.41 strains might be the basis for their genetic stability, consistent with their stable industrial performances. These observations provide important insights into the acid resistance mechanism and the genetic stability of Ap strains and lay a foundation for future genetic manipulation and engineering of these two strains.

  7. Global insights into acetic acid resistance mechanisms and genetic stability of Acetobacter pasteurianus strains by comparative genomics.

    PubMed

    Wang, Bin; Shao, Yanchun; Chen, Tao; Chen, Wanping; Chen, Fusheng

    2015-12-22

    Acetobacter pasteurianus (Ap) CICC 20001 and CGMCC 1.41 are two acetic acid bacteria strains that, because of their strong abilities to produce and tolerate high concentrations of acetic acid, have been widely used to brew vinegar in China. To globally understand the fermentation characteristics, acid-tolerant mechanisms and genetic stabilities, their genomes were sequenced. Genomic comparisons with 9 other sequenced Ap strains revealed that their chromosomes were evolutionarily conserved, whereas the plasmids were unique compared with other Ap strains. Analysis of the acid-tolerant metabolic pathway at the genomic level indicated that the metabolism of some amino acids and the known mechanisms of acetic acid tolerance, might collaboratively contribute to acetic acid resistance in Ap strains. The balance of instability factors and stability factors in the genomes of Ap CICC 20001 and CGMCC 1.41 strains might be the basis for their genetic stability, consistent with their stable industrial performances. These observations provide important insights into the acid resistance mechanism and the genetic stability of Ap strains and lay a foundation for future genetic manipulation and engineering of these two strains.

  8. Metal-Organic Frameworks for Cultural Heritage Preservation: The Case of Acetic Acid Removal.

    PubMed

    Dedecker, Kevin; Pillai, Renjith S; Nouar, Farid; Pires, João; Steunou, Nathalie; Dumas, Eddy; Maurin, Guillaume; Serre, Christian; Pinto, Moisés L

    2018-04-25

    The removal of low concentrations of acetic acid from indoor air at museums poses serious preservation problems that the current adsorbents cannot easily address owing to their poor affinity for acetic acid and/or their low adsorption selectivity versus water. In this context, a series of topical water-stable metal-organic frameworks (MOFs) with different pore sizes, topologies, hydrophobic characters, and functional groups was explored through a joint experimental-computational exploration. We demonstrate how a subtle combination of sufficient hydrophobicity and optimized host-guest interactions allows one to overcome the challenge of capturing traces of this very polar volatile organic compound in the presence of humidity. The optimal capture of acetic acid was accomplished with MOFs that do not show polar groups in the inorganic node or have lipophilic but polar (e.g., perfluoro) groups functionalized to the organic linkers, that is, the best candidates from the list of explored MOFs are MIL-140B and UiO-66-2CF 3 . These two MOFs present the appropriate pore size to favor a high degree of confinement, together with organic spacers that allow an enhancement of the van der Waals interactions with the acetic acid. We establish in this work that MOFs can be a viable solution to this highly challenging problem in cultural heritage protection, which is a new field of application for this type of hybrid materials.

  9. New trends and applications in carboxylation for isotope chemistry.

    PubMed

    Bragg, Ryan A; Sardana, Malvika; Artelsmair, Markus; Elmore, Charles S

    2018-05-08

    Carboxylations are an important method for the incorporation of isotopically labeled 14 CO 2 into molecules. This manuscript will review labeled carboxylations since 2010 and will present a perspective on the potential of recent unlabeled methodology for labeled carboxylations. The perspective portion of the manuscript is broken into 3 major sections based on product type, arylcarboxylic acids, benzylcarboxylic acids, and alkyl carboxylic acids, and each of those sections is further subdivided by substrate. © 2018 AstraZeneca. Journal of Labelled Compounds and Radiopharmaceuticals Published by John Wiley & Sons, Ltd.

  10. Lipidomic Profiling of Saccharomyces cerevisiae and Zygosaccharomyces bailii Reveals Critical Changes in Lipid Composition in Response to Acetic Acid Stress

    PubMed Central

    Riezman, Howard; Olsson, Lisbeth; Bettiga, Maurizio

    2013-01-01

    When using microorganisms as cell factories in the production of bio-based fuels or chemicals from lignocellulosic hydrolysate, inhibitory concentrations of acetic acid, released from the biomass, reduce the production rate. The undissociated form of acetic acid enters the cell by passive diffusion across the lipid bilayer, mediating toxic effects inside the cell. In order to elucidate a possible link between lipid composition and acetic acid stress, the present study presents detailed lipidomic profiling of the major lipid species found in the plasma membrane, including glycerophospholipids, sphingolipids and sterols, in Saccharomyces cerevisiae (CEN.PK 113_7D) and Zygosaccharomyces bailii (CBS7555) cultured with acetic acid. Detailed physiological characterization of the response of the two yeasts to acetic acid has also been performed in aerobic batch cultivations using bioreactors. Physiological characterization revealed, as expected, that Z. bailii is more tolerant to acetic acid than S. cerevisiae. Z. bailii grew at acetic acid concentrations above 24 g L−1, while limited growth of S. cerevisiae was observed after 11 h when cultured with only 12 g L−1 acetic acid. Detailed lipidomic profiling using electrospray ionization, multiple-reaction-monitoring mass spectrometry (ESI-MRM-MS) showed remarkable changes in the glycerophospholipid composition of Z. bailii, including an increase in saturated glycerophospholipids and considerable increases in complex sphingolipids in both S. cerevisiae (IPC 6.2×, MIPC 9.1×, M(IP)2C 2.2×) and Z. bailii (IPC 4.9×, MIPC 2.7×, M(IP)2C 2.7×), when cultured with acetic acid. In addition, the basal level of complex sphingolipids was significantly higher in Z. bailii than in S. cerevisiae, further emphasizing the proposed link between lipid saturation, high sphingolipid levels and acetic acid tolerance. The results also suggest that acetic acid tolerance is associated with the ability of a given strain to generate large

  11. Expeditious Synthesis of Dianionic-Headed 4-Sulfoalkanoic Acid Surfactants.

    PubMed

    Jiang, Jianghui; Xu, Jiaxi

    2017-04-16

    4-Sulfoalkanoic acids are a class of important dianionic-headed surfactants. Various 4-sulfoalkanoic acids with straight C8, C10, C12, C14, C16, and C18 chains were synthesized expeditiously through the radical addition of methyl 2-((ethoxycarbonothioyl)thio)acetate to linear terminal olefins and subsequent oxidation with peroxyformic acid. This is a useful and convenient strategy for the synthesis of dianionic-headed surfactants with a carboxylic acid and sulfonic acid functionalities in the head group region.

  12. Effects of urea and acetic acid on the heme axial ligation structure of ferric myoglobin at very acidic pH.

    PubMed

    Droghetti, Enrica; Sumithran, Suganya; Sono, Masanori; Antalík, Marián; Fedurco, Milan; Dawson, John H; Smulevich, Giulietta

    2009-09-01

    The heme iron coordination of ferric myoglobin (Mb) in the presence of 9.0M urea and 8.0M acetic acid at acidic pH values has been probed by electronic absorption, magnetic circular dichroism and resonance Raman spectroscopic techniques. Unlike Mb at pH 2.0, where heme is not released from the protein despite the acid denaturation and the loss of the axial ligand, upon increasing the concentration of either urea or acetic acid, a spin state change is observed, and a novel, non-native six-coordinated high-spin species prevails, where heme is released from the protein.

  13. Design of co-crystals/salts of some Nitrogenous bases and some derivatives of thiophene carboxylic acids through a combination of hydrogen and halogen bonds.

    PubMed

    Jennifer, Samson Jegan; Muthiah, Packianathan Thomas

    2014-01-01

    The utility of N-heterocyclic bases to obtain molecular complexes with carboxylic acids is well studied. Depending on the solid state interaction between the N-heterocyclic base and a carboxylic acid a variety of neutral or ionic synthons are observed. Meanwhile, pyridines and pyrimidines have been frequently chosen in the area of crystal engineering for their multipurpose functionality. HT (hetero trimers) and LHT (linear heterotetramers) are the well known synthons that are formed in the presence of pyrimidines and carboxylic acids. Fourteen crystals involving various substituted thiophene carboxylic acid derivatives and nitrogenous bases were prepared and characterized by using single crystal X-ray diffraction. The 14 crystals can further be divided into two groups [1a-7a], [8b-14b] based on the nature of the nitrogenous base. Carboxylic acid to pyridine proton transfer has occurred in 3 compounds of each group. In addition to the commonly occurring hydrogen bond based pyridine/carboxylic acid and pyrimidine/carboxylic acid synthons which is the reason for assembly of primary motifs, various other interactions like Cl…Cl, Cl…O, C-H…Cl, C-H…S add additional support in organizing these supermolecules into extended architectures. It is also interesting to note that in all the compounds π-π stacking occurs between the pyrimidine-pyrimidine or pyridine-pyridine or acid-acid moieties rather than acid-pyrimidine/pyridine. In all the compounds (1a-14b) either neutral O-H…Npyridyl/pyrimidine or charge-assisted Npyridinium-H…Ocarboxylate hydrogen bonds are present. The HT (hetero trimers) and LHT (linear heterotetramers) are dominant in the crystal structures of the adducts containing N-heterocyclic bases with two proton acceptors (1a-7a). Similar type supramolecular ladders are observed in 5TPC44BIPY (8b), TPC44BIPY (9b), TPC44TMBP (11b). Among the seven compounds [8b-14b] the extended ligands are linear in all except for the TMBP (10b, 11b, 12b). The

  14. Measurement of the isotope ratio of acetic acid in vinegar by HS-SPME-GC-TC/C-IRMS.

    PubMed

    Hattori, Ryota; Yamada, Keita; Shibata, Hiroki; Hirano, Satoshi; Tajima, Osamu; Yoshida, Naohiro

    2010-06-23

    Acetic acid is the main ingredient of vinegar, and the worth of vinegar often depends on the fermentation of raw materials. In this study, we have developed a simple and rapid method for discriminating the fermentation of the raw materials of vinegar by measuring the hydrogen and carbon isotope ratio of acetic acid using head space solid-phase microextraction (HS-SPME) combined with gas chromatography-high temperature conversion or combustion-isotope ratio mass spectrometry (GC-TC/C-IRMS). The measurement of acetic acid in vinegar by this method was possible with repeatabilities (1sigma) of +/-5.0 per thousand for hydrogen and +/-0.4 per thousand for carbon, which are sufficient to discriminate the origin of acetic acid. The fermentation of raw materials of several vinegars was evaluated by this method.

  15. Profile of preoperative fecal organic acids closely predicts the incidence of postoperative infectious complications after major hepatectomy with extrahepatic bile duct resection: Importance of fecal acetic acid plus butyric acid minus lactic acid gap.

    PubMed

    Yokoyama, Yukihiro; Mizuno, Takashi; Sugawara, Gen; Asahara, Takashi; Nomoto, Koji; Igami, Tsuyoshi; Ebata, Tomoki; Nagino, Masato

    2017-10-01

    To investigate the association between preoperative fecal organic acid concentrations and the incidence of postoperative infectious complications in patients undergoing major hepatectomy with extrahepatic bile duct resection for biliary malignancies. The fecal samples of 44 patients were collected before undergoing hepatectomy with bile duct resection for biliary malignancies. The concentrations of fecal organic acids, including acetic acid, butyric acid, and lactic acid, and representative fecal bacteria were measured. The perioperative clinical characteristics and the concentrations of fecal organic acids were compared between patients with and without postoperative infectious complications. Among 44 patients, 13 (30%) developed postoperative infectious complications. Patient age and intraoperative bleeding were significantly greater in patients with postoperative infectious complications compared with those without postoperative infectious complications. The concentrations of fecal acetic acid and butyric acid were significantly less, whereas the concentration of fecal lactic acid tended to be greater in the patients with postoperative infectious complications. The calculated gap between the concentrations of fecal acetic acid plus butyric acid minus lactic acid gap was less in the patients with postoperative infectious complications (median 43.5 vs 76.1 μmol/g of feces, P = .011). Multivariate analysis revealed that an acetic acid plus butyric acid minus lactic acid gap <60 μmol/g was an independent risk factor for postoperative infectious complications with an odds ratio of 15.6; 95% confidence interval 1.8-384.1. The preoperative fecal organic acid profile (especially low acetic acid, low butyric acid, and high lactic acid) had a clinically important impact on the incidence of postoperative infectious complications in patients undergoing major hepatectomy with extrahepatic bile duct resection. Copyright © 2017. Published by Elsevier Inc.

  16. Japan Flavour and Fragrance Materials Association's (JFFMA) safety assessment of food-flavouring substances uniquely used in Japan that belong to the class of aliphatic primary alcohols, aldehydes, carboxylic acids, acetals and esters containing additional oxygenated functional groups.

    PubMed

    Saito, Kenji; Hasegawa-Baba, Yasuko; Sekiya, Fumiko; Hayashi, Shim-Mo; Mirokuji, Yoshiharu; Okamura, Hiroyuki; Maruyama, Shinpei; Ono, Atsushi; Nakajima, Madoka; Degawa, Masakuni; Ozawa, Shogo; Shibutani, Makoto; Maitani, Tamio

    2017-09-01

    We performed a safety evaluation using the procedure devised by the Joint FAO/WHO Expert Committee on Food Additives (JECFA) of the following four flavouring substances that belong to the class of 'aliphatic primary alcohols, aldehydes, carboxylic acids, acetals, and esters containing additional oxygenated functional groups' and are uniquely used in Japan: butyl butyrylacetate, ethyl 2-hydroxy-4-methylpentanoate, 3-hydroxyhexanoic acid and methyl hydroxyacetate. Although no genotoxicity study data were found in the published literature, none of the four substances had chemical structural alerts predicting genotoxicity. All four substances were categorised as class I by using Cramer's classification. The estimated daily intake of each of the four substances was determined to be 0.007-2.9 μg/person/day by using the maximised survey-derived intake method and based on the annual production data in Japan in 2001, 2005 and 2010, and was determined to be 0.250-600.0 μg/person/day by using the single-portion exposure technique and based on average-use levels in standard portion sizes of flavoured foods. Both of these estimated daily intake ranges were below the threshold of toxicological concern for class I substances, which is 1800 μg/person/day. Although no information from in vitro and in vivo toxicity studies for the four substances was available, these substances were judged to raise no safety concerns at the current levels of intake.

  17. Coproduction of acetic acid and electricity by application of microbial fuel cell technology to vinegar fermentation.

    PubMed

    Tanino, Takanori; Nara, Youhei; Tsujiguchi, Takuya; Ohshima, Takayuki

    2013-08-01

    The coproduction of a useful material and electricity via a novel application of microbial fuel cell (MFC) technology to oxidative fermentation was investigated. We focused on vinegar production, i.e., acetic acid fermentation, as an initial and model useful material that can be produced by oxidative fermentation in combination with MFC technology. The coproduction of acetic acid and electricity by applying MFC technology was successfully demonstrated by the simultaneous progress of acetic acid fermentation and electricity generation through a series of repeated batch fermentations. Although the production rate of acetic acid was very small, it increased with the number of repeated batch fermentations that were conducted. We obtained nearly identical (73.1%) or larger (89.9%) acetic acid yields than that typically achieved by aerated fermentation (75.8%). The open-cycle voltages measured before and after fermentation increased with the total fermentation time and reached a maximum value of 0.521 V prior to the third batch fermentation. The maximum current and power densities measured in this study (19.1 μA/cm² and 2.47 μW/cm², respectively) were obtained after the second batch fermentation. Copyright © 2013 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

  18. Process design of SSCF for ethanol production from steam-pretreated, acetic-acid-impregnated wheat straw.

    PubMed

    Bondesson, Pia-Maria; Galbe, Mats

    2016-01-01

    Pretreatment is an important step in the production of ethanol from lignocellulosic material. Using acetic acid together with steam pretreatment allows the positive effects of an acid catalyst to be retained, while avoiding the negative environmental effects associated with sulphuric acid. Acetic acid is also formed during the pretreatment and hydrolysis of hemicellulose, and is a known inhibitor that may impair fermentation at high concentrations. The purpose of this study was to improve ethanol production from glucose and xylose in steam-pretreated, acetic-acid-impregnated wheat straw by process design of simultaneous saccharification and co-fermentation (SSCF), using a genetically modified pentose fermenting yeast strain Saccharomyces cerevisiae . Ethanol was produced from glucose and xylose using both the liquid fraction and the whole slurry from pretreated materials. The highest ethanol concentration achieved was 37.5 g/L, corresponding to an overall ethanol yield of 0.32 g/g based on the glucose and xylose available in the pretreated material. To obtain this concentration, a slurry with a water-insoluble solids (WIS) content of 11.7 % was used, using a fed-batch SSCF strategy. A higher overall ethanol yield (0.36 g/g) was obtained at 10 % WIS. Ethanol production from steam-pretreated, acetic-acid-impregnated wheat straw through SSCF with a pentose fermenting S. cerevisiae strain was successfully demonstrated. However, the ethanol concentration was too low and the residence time too long to be suitable for large-scale applications. It is hoped that further process design focusing on the enzymatic conversion of cellulose to glucose will allow the combination of acetic acid pretreatment and co-fermentation of glucose and xylose.

  19. Calibration and intercomparison of acetic acid measurements using proton transfer reaction mass spectrometry (PTR-MS)

    USGS Publications Warehouse

    Haase, K.B.; Keene, W.C.; Pszenny, A.A.P.; Mayne, H.R.; Talbot, R.W.; Sive, B.C.

    2012-01-01

    Acetic acid is one of the most abundant organic acids in the ambient atmosphere, with maximum mixing ratios reaching into the tens of parts per billion by volume (ppbv) range. The identities and associated magnitudes of the major sources and sinks for acetic acid are poorly characterized, due in part to the limitation in available measurement techniques. This paper demonstrates that Proton Transfer Reaction Mass Spectrometry (PTR-MS) can reliably quantify acetic acid vapor in ambient air. Three different PTR-MS configurations were calibrated at low ppbv mixing ratios using permeation tubes, which yielded calibration factors between 7.0 and 10.9 normalized counts per second per ppbv (ncps ppbv−1) at a drift tube field strength of 132 townsend (Td). Detection limits ranged from 0.06 to 0.32 ppbv with dwell times of 5 s. These calibration factors showed negligible humidity dependence. Using the experimentally determined calibration factors, PTR-MS measurements of acetic acid during the International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) campaign were validated against results obtained using Mist Chambers coupled with Ion Chromatography (MC/IC). An orthogonal least squares linear regression of paired data yielded a slope of 1.14 ± 0.06 (2σ), an intercept of 0.049 ± 20 (2σ) ppbv, and an R2 of 0.78. The median mixing ratio of acetic acid on Appledore Island, ME during the ICARTT campaign was 0.530 ± 0.025 ppbv with a minimum of 0.075 ± 0.004 ppbv, and a maximum of 3.555 ± 0.171 ppbv.

  20. 21 CFR 175.350 - Vinyl acetate/crotonic acid copolymer.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Vinyl acetate/crotonic acid copolymer. 175.350 Section 175.350 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: ADHESIVES AND COMPONENTS OF...

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

    PubMed

    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. Copyright © 2016. Published by Elsevier B.V.

  2. Dynamics of three organic acids (malic, acetic and succinic acid) in sunflower exposed to cadmium and lead.

    PubMed

    Niu, Zhixin; Li, Xiaodong; Sun, Lina; Sun, Tieheng

    2013-01-01

    Sunflower (Helianthus annuus L.) has been considered as a good candidate for bioaccumulation of heavy metals. In the present study, sunflower was used to enrich the cadmium and lead in sand culture during 90 days. Biomass, Cd and Pb uptake, three organic acids and pH in cultures were investigated. Results showed that the existence of Cd and Pb showed different interactions on the organic acids exudation. In single Cd treatments, malic and acetic acids in Cd10 showed an incremental tendency with time. In the mixed treatments of Cd and Pb, malic acids increased when 10 and 40 mg x L(-1) Cd were added into Pb50, but acetic acids in Pb50 were inhibited by Cd addition. The Cd10 supplied in Pb10 stimulated the secretion of malic and succinic acids. Moreover, the Cd or Pb uptake in sunflower showed various correlations with pH and some organic acids, which might be due to the fact that the Cd and Pb interfere with the organic acids secretion in rhizosphere of sunflower, and the changes of organic acids altered the form and bioavailability of Cd and Pb in cultures conversely.

  3. Survival mechanism of Escherichia coli O157:H7 against combined treatment with acetic acid and sodium chloride.

    PubMed

    Lee, Sun-Young; Kang, Dong-Hyun

    2016-05-01

    The combination of salt and acid is commonly used in the production of many foods, including pickles and fermented foods. However, in our previous studies, the addition of salt significantly reduced the inhibitory effect of acetic acid on Escherichia coli O157:H7 in laboratory media and pickled cucumbers. Therefore, this study was conducted to determine the mechanism by which salt confers resistance against acetic acid in E. coli O157:H7. The addition of high concentrations (up to 9% or 15% [w/v]) of salt increased the resistance of E. coli O157:H7 to acetic acid treatment. Combined treatment with acetic acid and salt showed varying results among different bacterial strains (an antagonistic effect for E. coli O157:H7 and Shigella and a synergistic effect for Listeria monocytogenes and Staphylococcus aureus). The addition of salt increased the cytoplasmic pH of E. coli O157:H7, but decreased the cytoplasmic pH of L. monocytogenes and S. aureus on treatment with acetic acid. Therefore, the addition of salt increases the acid resistance of E. coli O157:H7 possibly by increasing its acid resistance response and consequently preventing the acidification of its cytoplasm by organic acids. Copyright © 2015 Elsevier Ltd. All rights reserved.

  4. Comparative Genomics of Acetobacterpasteurianus Ab3, an Acetic Acid Producing Strain Isolated from Chinese Traditional Rice Vinegar Meiguichu.

    PubMed

    Xia, Kai; Li, Yudong; Sun, Jing; Liang, Xinle

    2016-01-01

    Acetobacter pasteurianus, an acetic acid resistant bacterium belonging to alpha-proteobacteria, has been widely used to produce vinegar in the food industry. To understand the mechanism of its high tolerance to acetic acid and robust ability of oxidizing ethanol to acetic acid (> 12%, w/v), we described the 3.1 Mb complete genome sequence (including 0.28 M plasmid sequence) with a G+C content of 52.4% of A. pasteurianus Ab3, which was isolated from the traditional Chinese rice vinegar (Meiguichu) fermentation process. Automatic annotation of the complete genome revealed 2,786 protein-coding genes and 73 RNA genes. The comparative genome analysis among A. pasteurianus strains revealed that A. pasteurianus Ab3 possesses many unique genes potentially involved in acetic acid resistance mechanisms. In particular, two-component systems or toxin-antitoxin systems may be the signal pathway and modulatory network in A. pasteurianus to cope with acid stress. In addition, the large numbers of unique transport systems may also be related to its acid resistance capacity and cell fitness. Our results provide new clues to understanding the underlying mechanisms of acetic acid resistance in Acetobacter species and guiding industrial strain breeding for vinegar fermentation processes.

  5. The CgHaa1-Regulon Mediates Response and Tolerance to Acetic Acid Stress in the Human Pathogen Candida glabrata

    PubMed Central

    Bernardo, Ruben T.; Cunha, Diana V.; Wang, Can; Pereira, Leonel; Silva, Sónia; Salazar, Sara B.; Schröder, Markus S.; Okamoto, Michiyo; Takahashi-Nakaguchi, Azusa; Chibana, Hiroji; Aoyama, Toshihiro; Sá-Correia, Isabel; Azeredo, Joana; Butler, Geraldine; Mira, Nuno Pereira

    2016-01-01

    To thrive in the acidic vaginal tract, Candida glabrata has to cope with high concentrations of acetic acid. The mechanisms underlying C. glabrata tolerance to acetic acid at low pH remain largely uncharacterized. In this work, the essential role of the CgHaa1 transcription factor (encoded by ORF CAGL0L09339g) in the response and tolerance of C. glabrata to acetic acid is demonstrated. Transcriptomic analysis showed that CgHaa1 regulates, directly or indirectly, the expression of about 75% of the genes activated under acetic acid stress. CgHaa1-activated targets are involved in multiple physiological functions including membrane transport, metabolism of carbohydrates and amino acids, regulation of the activity of the plasma membrane H+-ATPase, and adhesion. Under acetic acid stress, CgHaa1 increased the activity and the expression of the CgPma1 proton pump and contributed to increased colonization of vaginal epithelial cells by C. glabrata. CgHAA1, and two identified CgHaa1-activated targets, CgTPO3 and CgHSP30, are herein demonstrated to be determinants of C. glabrata tolerance to acetic acid. The protective effect of CgTpo3 and of CgHaa1 was linked to a role of these proteins in reducing the accumulation of acetic acid inside C. glabrata cells. In response to acetic acid stress, marked differences were found in the regulons controlled by CgHaa1 and by its S. cerevisiae ScHaa1 ortholog, demonstrating a clear divergent evolution of the two regulatory networks. The results gathered in this study significantly advance the understanding of the molecular mechanisms underlying the success of C. glabrata as a vaginal colonizer. PMID:27815348

  6. Carboxylate-containing chelating agent interactions with amorphous chromium hydroxide: Adsorption and dissolution

    NASA Astrophysics Data System (ADS)

    Carbonaro, Richard F.; Gray, Benjamin N.; Whitehead, Charles F.; Stone, Alan T.

    2008-07-01

    Anthropogenic chelating agents and biological chelating agents produced by indigenous organisms may dissolve Cr III (hydr)oxides in soils and sediments. The resulting dissolved Cr III-chelating agent complexes are more readily transported through porous media, thereby spreading contamination. With this work, we examine chelating agent-assisted dissolution of amorphous chromium hydroxide (ACH) by the (amino)carboxylate chelating agents iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), tricarballylic acid (TCA), citric acid (CIT), ethylenediaminetetraacetic acid (EDTA), trans-1,2-cyclohexanediaminetetraacetic acid (CDTA), and trimethylenediaminetetraacetic acid (TMDTA). The extent of chelating agent adsorption onto ACH increased quickly over the first few hours, and then increased more gradually until a constant extent was attained. The extent of chelating agent adsorption versus pH followed "ligand-like" behavior. All chelating agents with the exception of TCA and IDA effectively dissolved significant amounts of ACH within 10 days from pH 4.0 to 9.4. IDA dissolved ACH below pH 6.5 and above pH 7.5. Rates of ACH dissolution normalized to the extent of chelating agent adsorption were pH dependent. IDA, NTA, CIT, and CDTA exhibited an increase in normalized dissolution rate with decreasing pH. EDTA and TMDTA exhibited a maximum in normalized dissolution rate near pH 8.5. Use of acetic acid as a pH buffer in experiments decreased the extent of chelating agent adsorption for IDA, NTA, and CIT but increased normalized rates of chelating agent-assisted dissolution for all chelating agents except EDTA. The results from this study provide the necessary information to calculate the extents and time scales of ACH dissolution in the presence of (amino)carboxylate chelating agents.

  7. Preferential deprotonation and conformational stability of dicarboxylic acids: A packing effect

    NASA Astrophysics Data System (ADS)

    Barooah, Nilotpal; Singh, W. Marjit; Baruah, Jubaraj B.

    2008-03-01

    Crystal structures of a series of salts of (6-carboxymethyl-1,3,5,7-tetraoxo-3,5,6,7-tetrahydro-1 H-pyrrolo[3,4- f]isoindol-2-yl)-acetic acid ( 1) and 2-carboxymethyl-1,3-dioxo-2,3-dihydro-1 H-isoinodole-5-carboxylic acid ( 2) with different polynuclear nitrogen containing heterocyclic compounds, namely, quinoline, 1,10-phenanthroline and 8-hydroxyquinoline are determined. In the case of salt of 1 with quinolinium and 1,10-phenanthrolinium cations syn disposition between the carboxylate anion and carboxylic acid groups is observed; whereas in the case of the 8-hydroxyquinolinium salt of 1, it is the anti disposition. It is also found that the solid state structure of 1,10-phenanthrolinium salt of 2 has deprotonation at the aromatic end, whereas in 8-hydroxy-quinolinium salt of 2 is formed by deprotonation of carboxylic acid group on the aliphatic side. The dicarboxylic acid 2 forms 1:2 co-crystals with quinoline. From crystallographic study it is shown that the weak interactions become prominent in stabilising the observed conformers and also in stabilising specific deprotonated species.

  8. Direct hydrogenation of biomass-derived butyric acid to n-butanol over a ruthenium-tin bimetallic catalyst.

    PubMed

    Lee, Jong-Min; Upare, Pravin P; Chang, Jong-San; Hwang, Young Kyu; Lee, Jeong Ho; Hwang, Dong Won; Hong, Do-Young; Lee, Seung Hwan; Jeong, Myung-Geun; Kim, Young Dok; Kwon, Young-Uk

    2014-11-01

    Catalytic hydrogenation of organic carboxylic acids and their esters, for example, cellulosic ethanol from fermentation of acetic acid and hydrogenation of ethyl acetate is a promising possibility for future biorefinery concepts. A hybrid conversion process based on selective hydrogenation of butyric acid combined with fermentation of glucose has been developed for producing biobutanol. ZnO-supported Ru-Sn bimetallic catalysts exhibits unprecedentedly superior performance in the vapor-phase hydrogenation of biomass-derived butyric acid to n-butanol (>98% yield) for 3500 h without deactivation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Global insights into acetic acid resistance mechanisms and genetic stability of Acetobacter pasteurianus strains by comparative genomics

    PubMed Central

    Wang, Bin; Shao, Yanchun; Chen, Tao; Chen, Wanping; Chen, Fusheng

    2015-01-01

    Acetobacter pasteurianus (Ap) CICC 20001 and CGMCC 1.41 are two acetic acid bacteria strains that, because of their strong abilities to produce and tolerate high concentrations of acetic acid, have been widely used to brew vinegar in China. To globally understand the fermentation characteristics, acid-tolerant mechanisms and genetic stabilities, their genomes were sequenced. Genomic comparisons with 9 other sequenced Ap strains revealed that their chromosomes were evolutionarily conserved, whereas the plasmids were unique compared with other Ap strains. Analysis of the acid-tolerant metabolic pathway at the genomic level indicated that the metabolism of some amino acids and the known mechanisms of acetic acid tolerance, might collaboratively contribute to acetic acid resistance in Ap strains. The balance of instability factors and stability factors in the genomes of Ap CICC 20001 and CGMCC 1.41 strains might be the basis for their genetic stability, consistent with their stable industrial performances. These observations provide important insights into the acid resistance mechanism and the genetic stability of Ap strains and lay a foundation for future genetic manipulation and engineering of these two strains. PMID:26691589

  10. Co-production of functional xylooligosaccharides and fermentable sugars from corncob with effective acetic acid prehydrolysis.

    PubMed

    Zhang, Hongyu; Xu, Yong; Yu, Shiyuan

    2017-06-01

    A novel and green approach for the coproduction of xylooligosaccharides (XOS), in terms of a series of oligosaccharide components from xylobiose to xylohexose, and fermentable sugars was developed using the prehydrolysis of acetic acid that was fully recyclable and environmentally friendly, followed by enzymatic hydrolysis. Compared to hydrochloric acid and sulfuric acid, acetic acid hydrolysis provided the highest XOS yield of 45.91% and the highest enzymatic hydrolysis yield. More than 91% conversion of cellulose was achieved in a batch-hydrolysis using only a cellulase loading of 20FPU/g cellulose and even a high solid loading of 20% without any special strategies. The acetic acid pretreated corncob should be washed adequately before saccharification to achieve complete hydrolysis. Consequently, a mass balance analysis showed that 139.8g XOS, 328.1g glucose, 25.1g cellobiose, and 147.8g xylose were produced from 1000g oven dried raw corncob. Copyright © 2017. Published by Elsevier Ltd.

  11. New insights into the mechanisms of acetic acid resistance in Acetobacter pasteurianus using iTRAQ-dependent quantitative proteomic analysis.

    PubMed

    Xia, Kai; Zang, Ning; Zhang, Junmei; Zhang, Hong; Li, Yudong; Liu, Ye; Feng, Wei; Liang, Xinle

    2016-12-05

    Acetobacter pasteurianus is the main starter in rice vinegar manufacturing due to its remarkable abilities to resist and produce acetic acid. Although several mechanisms of acetic acid resistance have been proposed and only a few effector proteins have been identified, a comprehensive depiction of the biological processes involved in acetic acid resistance is needed. In this study, iTRAQ-based quantitative proteomic analysis was adopted to investigate the whole proteome of different acidic titers (3.6, 7.1 and 9.3%, w/v) of Acetobacter pasteurianus Ab3 during the vinegar fermentation process. Consequently, 1386 proteins, including 318 differentially expressed proteins (p<0.05), were identified. Compared to that in the low titer circumstance, cells conducted distinct biological processes under high acetic acid stress, where >150 proteins were differentially expressed. Specifically, proteins involved in amino acid metabolic processes and fatty acid biosynthesis were differentially expressed, which may contribute to the acetic acid resistance of Acetobacter. Transcription factors, two component systems and toxin-antitoxin systems were implicated in the modulatory network at multiple levels. In addition, the identification of proteins involved in redox homeostasis, protein metabolism, and the cell envelope suggested that the whole cellular system is mobilized in response to acid stress. These findings provide a differential proteomic profile of acetic acid resistance in Acetobacter pasteurianus and have potential application to highly acidic rice vinegar manufacturing. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Plasma membrane proteins Yro2 and Mrh1 are required for acetic acid tolerance in Saccharomyces cerevisiae.

    PubMed

    Takabatake, Akiko; Kawazoe, Nozomi; Izawa, Shingo

    2015-03-01

    Yro2 and its paralogous protein Mrh1 of Saccharomyces cerevisiae have seven predicted transmembrane domains and predominantly localize to the plasma membrane. Their physiological functions and regulation of gene expression have not yet been elucidated in detail. We herein demonstrated that MRH1 was constitutively expressed, whereas the expression of YRO2 was induced by acetic acid stress and entering the stationary phase. Fluorescence microscopic analysis revealed that Mrh1 and Yro2 were distributed as small foci in the plasma membrane under acetic acid stress conditions. The null mutants of these genes (mrh1∆, yro2∆, and mrh1∆yro2∆) showed delayed growth and a decrease in the productivity of ethanol in the presence of acetic acid, indicating that Yro2 and Mrh1 are involved in tolerance to acetic acid stress.

  13. Biodiversity of yeasts, lactic acid bacteria and acetic acid bacteria in the fermentation of "Shanxi aged vinegar", a traditional Chinese vinegar.

    PubMed

    Wu, Jia Jia; Ma, Ying Kun; Zhang, Fen Fen; Chen, Fu Sheng

    2012-05-01

    Shanxi aged vinegar is a famous traditional Chinese vinegar made from several kinds of cereal by spontaneous solid-state fermentation techniques. In order to get a comprehensive understanding of culturable microorganism's diversity present in its fermentation, the indigenous microorganisms including 47 yeast isolates, 28 lactic acid bacteria isolates and 58 acetic acid bacteria isolates were recovered in different fermenting time and characterized based on a combination of phenotypic and genotypic approaches including inter-delta/PCR, PCR-RFLP, ERIC/PCR analysis, as well as 16S rRNA and 26S rRNA partial gene sequencing. In the alcoholic fermentation, the dominant yeast species Saccharomyces (S.) cerevisiae (96%) exhibited low phenotypic and genotypic diversity among the isolates, while Lactobacillus (Lb.) fermentum together with Lb. plantarum, Lb. buchneri, Lb. casei, Pediococcus (P.) acidilactici, P. pentosaceus and Weissella confusa were predominated in the bacterial population at the same stage. Acetobacter (A.) pasteurianus showing great variety both in genotypic and phenotypic tests was the dominant species (76%) in the acetic acid fermentation stage, while the other acetic acid bacteria species including A. senegalensis, A. indonesiensis, A. malorum and A. orientalis, as well as Gluconobacter (G.) oxydans were detected at initial point of alcoholic and acetic acid fermentation stage respectively. Copyright © 2011 Elsevier Ltd. All rights reserved.

  14. Are carboxyl groups the most acidic sites in amino acids? Gas-phase acidities, photoelectron spectra, and computations on tyrosine, p-hydroxybenzoic acid, and their conjugate bases.

    PubMed

    Tian, Zhixin; Wang, Xue-Bin; Wang, Lai-Sheng; Kass, Steven R

    2009-01-28

    Deprotonation of tyrosine in the gas phase was found to occur preferentially at the phenolic site, and the conjugate base consists of a 70:30 mixture of phenoxide and carboxylate anions at equilibrium. This result was established by developing a chemical probe for differentiating these two isomers, and the presence of both ions was confirmed by photoelectron spectroscopy. Equilibrium acidity measurements on tyrosine indicated that deltaG(acid)(o) = 332.5 +/- 1.5 kcal mol(-1) and deltaH(acid)(o) = 340.7 +/- 1.5 kcal mol(-1). Photoelectron spectra yielded adiabatic electron detachment energies of 2.70 +/- 0.05 and 3.55 +/- 0.10 eV for the phenoxide and carboxylate anions, respectively. The H/D exchange behavior of deprotonated tyrosine was examined using three different alcohols (CF3CH2OD, C6H5CH2OD, and CH3CH2OD), and incorporation of up to three deuterium atoms was observed. Two pathways are proposed to account for these results, and all of the experimental findings are supplemented with B3LYP/aug-cc-pVDZ and G3B3 calculations. In addition, it was found that electrospray ionization of tyrosine from a 3:1 (v/v) CH3OH/H2O solution using a commercial source produces a deprotonated [M-H]- anion with the gas-phase equilibrium composition rather than the structure of the ion that exists in aqueous media. Electrospray ionization from acetonitrile, however, leads largely to the liquid-phase (carboxylate) structure. A control molecule, p-hydroxybenzoic acid, was found to behave in a similar manner. Thus, the electrospray conditions that are employed for the analysis of a compound can alter the isomeric composition of the resulting anion.

  15. A Quick and Simple Conversion of Carboxylic Acids into Their Anilides of Heating with Phenyl Isothiocyanate.

    ERIC Educational Resources Information Center

    Ram, Ram N.; And Others

    1983-01-01

    Converting carboxylic acids into their anilides, which usually involves preparation of acid chloride or mixed anhydride followed by treatment with aniline, is tedious and/or time-consuming. A quick and easier procedure, using phenyl isothiocyanate, is provided. Reactions involved and a summary table of results are included. (JN)

  16. Application of L-proline derivatives as chiral shift reagents for enantiomeric recognition of carboxylic acids.

    PubMed

    Naziroglu, Hayriye Nevin; Durmaz, Mustafa; Bozkurt, Selahattin; Sirit, Abdulkadir

    2011-07-01

    Four proline-derived chiral receptors 5-8 were readily synthesized starting from L-proline. The enantiomeric recognition ability of chiral receptors was examined with a series of carboxylic acids by (1) H NMR spectroscopy. The molar ratio and the association constants of the chiral compounds with each of the enantiomers of guest molecules were determined by using Job plots and a nonlinear least-squares fitting method, respectively. The Job plots indicate that the hosts form 1:1 instantaneous complexes with all guests. The receptors exhibited different chiral recognition abilities toward the enantiomers of racemic guests. Among the chiral receptors used in this study, prolinamide 6 was found to be the best chiral shift reagent and is effective for the determination of the enantiomeric excess of chiral carboxylic acids. Copyright © 2011 Wiley-Liss, Inc.

  17. Gamma-irradiation of malic acid in aqueous solutions. [prebiotic significance

    NASA Technical Reports Server (NTRS)

    Negron-Mendoza, A.; Graff, R. L.; Ponnamperuma, C.

    1980-01-01

    The gamma-irradiation of malic acid in aqueous solutions was studied under initially oxygenated and oxygen-free conditions in an attempt to determine the possible interconversion of malic acid into other carboxylic acids, specifically those associated with Krebs cycle. The effect of dose on product formation of the system was investigated. Gas-liquid chromatography combined with mass spectrometry was used as the principal means of identification of the nonvolatile products. Thin layer chromatography and direct probe mass spectroscopy were also employed. The findings show that a variety of carboxylic acids are formed, with malonic and succinic acids in greatest abundance. These products have all been identified as being formed in the gamma-irradiation of acetic acid, suggesting a common intermediary. Since these molecules fit into a metabolic cycle, it is strongly suggestive that prebiotic pathways provided the basis for biological systems.

  18. Vinegar Production from Jabuticaba (Myrciaria jaboticaba) Fruit Using Immobilized Acetic Acid Bacteria

    PubMed Central

    Silva, Monique Suela; Cristina de Souza, Angélica; Magalhăes-Guedes, Karina Teixeira; Ribeiro, Fernanda Severo de Rezende; Schwan, Rosane Freitas

    2016-01-01

    Summary Cell immobilization comprises the retention of metabolically active cells inside a polymeric matrix. In this study, the production of jabuticaba (Myrciaria jaboticaba) vinegar using immobilized Acetobacter aceti and Gluconobacter oxydans cells is proposed as a new method to prevent losses of jabuticaba fruit surplus. The pulp of jabuticaba was processed and Saccharomyces cerevisiae CCMA 0200 was used to ferment the must for jabuticaba wine production. Sugars, alcohols (ethanol and glycerol) and organic acids were assayed by high-performance liquid chromatography. Volatile compounds were determined by gas chromatography-flame ionization detector. The ethanol content of the produced jabuticaba wine was approx. 74.8 g/L (9.5% by volume) after 168 h of fermentation. Acetic acid fermentation for vinegar production was performed using a mixed culture of immobilized A. aceti CCT 0190 and G. oxydans CCMA 0350 cells. The acetic acid yield was 74.4% and productivity was 0.29 g/(L·h). The vinegar had particularly high concentrations of citric (6.67 g/L), malic (7.02 g/L) and succinic (5.60 g/L) acids. These organic acids give a suitable taste and flavour to the vinegar. Seventeen compounds (aldehydes, higher alcohols, terpene, acetate, diether, furans, acids, ketones and ethyl esters) were identified in the jabuticaba vinegar. In conclusion, vinegar was successfully produced from jabuticaba fruits using yeast and immobilized mixed cultures of A. aceti and G. oxydans. To the best of our knowledge, this is the first study to use mixed culture of immobilized cells for the production of jabuticaba vinegar. PMID:27956867

  19. Vinegar Production from Jabuticaba (Myrciaria jaboticaba) Fruit Using Immobilized Acetic Acid Bacteria.

    PubMed

    Dias, Disney Ribeiro; Silva, Monique Suela; Cristina de Souza, Angélica; Magalhăes-Guedes, Karina Teixeira; Ribeiro, Fernanda Severo de Rezende; Schwan, Rosane Freitas

    2016-09-01

    Cell immobilization comprises the retention of metabolically active cells inside a polymeric matrix. In this study, the production of jabuticaba ( Myrciaria jaboticaba ) vinegar using immobilized Acetobacter aceti and Gluconobacter oxydans cells is proposed as a new method to prevent losses of jabuticaba fruit surplus. The pulp of jabuticaba was processed and Saccharomyces cerevisiae CCMA 0200 was used to ferment the must for jabuticaba wine production. Sugars, alcohols (ethanol and glycerol) and organic acids were assayed by high-performance liquid chromatography. Volatile compounds were determined by gas chromatography-flame ionization detector. The ethanol content of the produced jabuticaba wine was approx. 74.8 g/L (9.5% by volume) after 168 h of fermentation. Acetic acid fermentation for vinegar production was performed using a mixed culture of immobilized A. aceti CCT 0190 and G. oxydans CCMA 0350 cells. The acetic acid yield was 74.4% and productivity was 0.29 g/(L·h). The vinegar had particularly high concentrations of citric (6.67 g/L), malic (7.02 g/L) and succinic (5.60 g/L) acids. These organic acids give a suitable taste and flavour to the vinegar. Seventeen compounds (aldehydes, higher alcohols, terpene, acetate, diether, furans, acids, ketones and ethyl esters) were identified in the jabuticaba vinegar. In conclusion, vinegar was successfully produced from jabuticaba fruits using yeast and immobilized mixed cultures of A. aceti and G. oxydans . To the best of our knowledge, this is the first study to use mixed culture of immobilized cells for the production of jabuticaba vinegar.

  20. Effective Trapping of Fruit Flies with Cultures of Metabolically Modified Acetic Acid Bacteria

    PubMed Central

    Ishii, Yuri; Akasaka, Naoki; Goda, Itsuko; Sakoda, Hisao

    2015-01-01

    Acetoin in vinegar is an attractant to fruit flies when combined with acetic acid. To make vinegar more effective in attracting fruit flies with increased acetoin production, Komagataeibacter europaeus KGMA0119 was modified by specific gene disruption of the acetohydroxyacid isomeroreductase gene (ilvC). A previously constructed mutant lacking the putative ligand-sensing region in the leucine-responsive regulatory protein (KeLrp, encoded by Kelrp) was also used. The ilvC and Kelrp disruptants (KGMA5511 and KGMA7203, respectively) produced greater amounts of acetoin (KGMA5511, 0.11%; KGMA7203, 0.13%) than the wild-type strain KGMA0119 (0.069%). KGMA7203 produced a trace amount of isobutyric acid (0.007%), but the other strains did not. These strains produced approximately equal amounts of acetic acid (0.7%). The efficiency of fruit fly attraction was investigated with cultured Drosophila melanogaster. D. melanogaster flies (approximately 1,500) were released inside a cage (2.5 m by 2.5 m by 1.5 m) and were trapped with a device containing vinegar and a sticky sheet. The flies trapped on the sticky sheet were counted. The cell-free supernatant from KGMA7203 culture captured significantly more flies (19.36 to 36.96% of released flies) than did KGMA0119 (3.25 to 11.40%) and KGMA5511 (6.87 to 21.50%) cultures. Contrastingly, a 0.7% acetic acid solution containing acetoin (0.13%) and isobutyric acid (0.007%), which mimicked the KGMA7203 supernatant, captured significantly fewer flies (0.88 to 4.57%). Furthermore, the KGMA0119 supernatant with additional acetoin (0.13%) and isobutyric acid (0.007%) captured slightly more flies than the original KGMA0119 supernatant but fewer than the KGMA7203 supernatant, suggesting that the synergistic effects of acetic acid, acetoin, isobutyric acid, and unidentified metabolites achieved the efficient fly trapping of the KGMA7203 supernatant. PMID:25595769

  1. The Effect of Acid Pre-Treatment using Acetic Acid and Nitric Acid in The Production of Biogas from Rice Husk during Solid State Anaerobic Digestion (SS-AD)

    NASA Astrophysics Data System (ADS)

    Nugraha, Winardi Dwi; Syafrudin; Keumala, Cut Fadhila; Matin, Hasfi Hawali Abdul; Budiyono

    2018-02-01

    Pretreatment during biogas production aims to assist in degradation of lignin contained in the rice husk. In this study, pretreatment which is used are acid and biological pretreatment. Acid pretreatment was performed using acetic acid and nitric acid with a variety levels of 3% and 5%. While biological pretreatment as a control variable. Acid pretreatment was conducted by soaking the rice straw for 24 hours with acid variation. The study was conducted using Solid State Anaerobic Digestion (SS-AD) with 21% TS. Biogas production was measured using water displacement method every two days for 60 days at room temperature conditions. The results showed that acid pretreatment gave an effect on the production of biogas yield. The yield of the biogas produced by pretreatment of acetic acid of 5% and 3% was 43.28 and 45.86 ml/gr.TS. While the results without pretreatment biogas yield was 29.51 ml/gr.TS. The results yield biogas produced by pretreatment using nitric acid of 5% and 3% was 12.14 ml/gr.TS and 21.85 ml/gr.TS. Results biogas yield with acetic acid pretreatment was better than the biogas yield results with nitric acid pretreatment.

  2. 1-11C-acetate as a PET radiopharmaceutical for imaging fatty acid synthase expression in prostate cancer.

    PubMed

    Vāvere, Amy L; Kridel, Steven J; Wheeler, Frances B; Lewis, Jason S

    2008-02-01

    Although it is accepted that the metabolic fate of 1-(11)C-acetate is different in tumors than in myocardial tissue because of different clearance patterns, the exact pathway has not been fully elucidated. For decades, fatty acid synthesis has been quantified in vitro by the incubation of cells with (14)C-acetate. Fatty acid synthase (FAS) has been found to be overexpressed in prostate carcinomas, as well as other cancers, and it is possible that imaging with 1-(11)C-acetate could be a marker for its expression. In vitro and in vivo uptake experiments in prostate tumor models with 1-(11)C-acetate were performed both with and without blocking of fatty acid synthesis with either C75, an inhibitor of FAS, or 5-(tetradecyloxy)-2-furoic acid (TOFA), an inhibitor of acetyl-CoA carboxylase (ACC). FAS levels were measured by Western blot and immunohistochemical techniques for comparison. In vitro studies in 3 different prostate tumor models (PC-3, LNCaP, and 22Rv1) demonstrated blocking of 1-(11)C-acetate accumulation after treatment with both C75 and TOFA. This was further shown in vivo in PC-3 and LNCaP tumor-bearing mice after a single treatment with C75. A positive correlation between 1-(11)C-acetate uptake into the solid tumors and FAS expression levels was found. Extensive involvement of the fatty acid synthesis pathway in 1-(11)C-acetate uptake in prostate tumors was confirmed, leading to a possible marker for FAS expression in vivo by noninvasive PET.

  3. Radiolysis of aqueous solutions of acetic acid in the presence of Na-montmorillonite

    NASA Technical Reports Server (NTRS)

    Navarro-Gonzalez, R.; Negron-Mendoza, A.; Ramos, S.; Ponnamperuma, C.

    1990-01-01

    The gamma-irradiation of 0.8 mol dm-3 aqueous, oxygen-free acetic acid solutions was investigated in the presence or absence of Na-montmorillonite. H2, CH4, CO, CO2, and several polycarboxylic acids were formed in all systems. The primary characteristics observed in the latter system were: (1) Higher yield of the decomposition of acetic acid; (2) Lower yield of the formation of polycarboxylic acids; (3) No effect on the formation of methane; (4) Higher yield of the formation of carbon dioxide; and (5) The reduction of Fe3+ in the octahedral sites of Na-montmorillonite. A possible reaction scheme was proposed to account for the observed changes. The results are important in understanding heterogeneous processes in radiation catalysis and might be significant to prebiotic chemistry.

  4. Peptide Conjugates of Benzene Carboxylic Acids as Agonists and Antagonists of Amylin Aggregation.

    PubMed

    Profit, Adam A; Vedad, Jayson; Desamero, Ruel Z B

    2017-02-15

    Human islet amyloid polypeptide (hIAPP), also known as amylin, is a 37 residue peptide hormone that is stored and co-secreted with insulin. hIAPP plays a pivotal role in type 2 diabetes and is the major component of amyloid deposits found in the pancreas of patients afflicted with the disease. The self-assembly of hIAPP and the formation of amyloid is linked to the death of insulin producing β-cells. Recent findings suggest that soluble hIAPP oligomers are the cytotoxic species responsible for β-cell loss whereas amyloid fibrils themselves may indeed be innocuous. Potential avenues of therapeutic intervention include the development of compounds that prevent hIAPP self-assembly as well as those that reduce or eliminate lag time and rapidly accelerate the formation of amyloid fibrils. Both of these approaches minimize temporal exposure to soluble cytotoxic hIAPP oligomers. Toward this end our laboratory has pursued an electrostatic repulsion approach to the development of potential inhibitors and modulators of hIAPP self-assembly. Peptide conjugates were constructed in which benzene carboxylic acids of varying charge were employed as electrostatic disrupting elements and appended to the N-terminal of the hIAPP 22-29 (NFGAILSS) self-recognition sequence. The self-assembly kinetics of conjugates were characterized by turbidity measurements and the structure of aggregates probed by Raman and CD spectroscopy while the morphology was assessed using transmission electron microscopy. Several benzene carboxylic acid peptide conjugates failed to self-assemble and some were found to inhibit the aggregation of full-length amylin while others served to enhance the rate of amyloid formation and/or increase the yield of amyloid produced. Studies reveal that the geometric display of free carboxylates on the benzene ring of the conjugates plays an important role in the activity of conjugates. In addition, a number of free benzene carboxylic acids were found to modulate amylin

  5. Robust Extracellular pH Modulation by Candida albicans during Growth in Carboxylic Acids

    PubMed Central

    Danhof, Heather A.; Vylkova, Slavena; Vesely, Elisa M.; Ford, Amy E.; Gonzalez-Garay, Manuel

    2016-01-01

    ABSTRACT The opportunistic fungal pathogen Candida albicans thrives within diverse niches in the mammalian host. Among the adaptations that underlie this fitness is an ability to utilize a wide array of nutrients, especially sources of carbon that are disfavored by many other fungi; this contributes to its ability to survive interactions with the phagocytes that serve as key barriers against disseminated infections. We have reported that C. albicans generates ammonia as a byproduct of amino acid catabolism to neutralize the acidic phagolysosome and promote hyphal morphogenesis in a manner dependent on the Stp2 transcription factor. Here, we report that this species rapidly neutralizes acidic environments when utilizing carboxylic acids like pyruvate, α-ketoglutarate (αKG), or lactate as the primary carbon source. Unlike in cells growing in amino acid-rich medium, this does not result in ammonia release, does not induce hyphal differentiation, and is genetically distinct. While transcript profiling revealed significant similarities in gene expression in cells grown on either carboxylic or amino acids, genetic screens for mutants that fail to neutralize αKG medium identified a nonoverlapping set of genes, including CWT1, encoding a transcription factor responsive to cell wall and nitrosative stresses. Strains lacking CWT1 exhibit retarded αKG-mediated neutralization in vitro, exist in a more acidic phagolysosome, and are more susceptible to macrophage killing, while double cwt1Δ stp2Δ mutants are more impaired than either single mutant. Together, our observations indicate that C. albicans has evolved multiple ways to modulate the pH of host-relevant environments to promote its fitness as a pathogen. PMID:27935835

  6. Acetic acid induces Sch9p-dependent translocation of Isc1p from the endoplasmic reticulum into mitochondria.

    PubMed

    Rego, António; Cooper, Katrina F; Snider, Justin; Hannun, Yusuf A; Costa, Vítor; Côrte-Real, Manuela; Chaves, Susana R

    2018-06-01

    Changes in sphingolipid metabolism have been linked to modulation of cell fate in both yeast and mammalian cells. We previously assessed the role of sphingolipids in cell death regulation using a well characterized yeast model of acetic acid-induced regulated cell death, finding that Isc1p, inositol phosphosphingolipid phospholipase C, plays a pro-death role in this process. Indeed, isc1∆ mutants exhibited a higher resistance to acetic acid associated with reduced mitochondrial alterations. Here, we show that Isc1p is regulated by Sch9p under acetic acid stress, since both single and double mutants lacking Isc1p or/and Sch9p have the same resistant phenotype, and SCH9 deletion leads to a higher retention of Isc1p in the endoplasmic reticulum upon acetic acid exposure. We also found that the higher resistance of all mutants correlates with higher levels of endogenous mitochondrial phosphorylated long chain bases (LCBPs), suggesting that changing the sphingolipid balance in favour of LCBPs in mitochondria results in increased survival to acetic acid. In conclusion, our results suggest that Sch9p pathways modulate acetic acid-induced cell death, through the regulation of Isc1p cellular distribution, thus affecting the sphingolipid balance that regulates cell fate. Copyright © 2018 Elsevier B.V. All rights reserved.

  7. Synthesizing Pt nanoparticles in the presence of methylamine: Impact of acetic acid treatment in the electrocatalytic activity of formic acid oxidation

    NASA Astrophysics Data System (ADS)

    Ooi, M. D. Johan; Aziz, A. Abdul

    2017-05-01

    Surfactant removal from the surface of platinum nanoparticles prepared by solution based method is a prerequisite process to accomplish a high catalytic activity for electrochemical reactions. Here, we report a possible approach of combining acid acetic with thermal treatment for improving catalytic performance of formic acid oxidation. This strategy involves conversion of amine to amide in acetic acid followed by surfactant removal via subsequent thermal treatment at 85 °C. This combined activation technique produced monodisperse nanoparticle with the size of 3 to 5 nm with enhanced formic acid oxidation activity, particularly in perchloric acid solution. Pt treated in 1 h of acetic acid and heat treatment of 9 h shows high electrochemical surface area value (27.6 m2/g) compares to Pt without activation (16.6 m2/g). The treated samples also exhibit high current stability of 0.3 mA/cm2 compares to the as-prepared mA/cm2). Shorter duration of acid wash and longer duration of heating process result in high electrocatalytic activity. This work demonstrates a possible technique in improving catalytic activity of platinum nanoparticles synthesized using methylamine as surfactant.

  8. Iron dissolution of dust source materials during simulated acidic processing: the effect of sulfuric, acetic, and oxalic acids.

    PubMed

    Chen, Haihan; Grassian, Vicki H

    2013-09-17

    Atmospheric organic acids potentially display different capacities in iron (Fe) mobilization from atmospheric dust compared with inorganic acids, but few measurements have been made on this comparison. We report here a laboratory investigation of Fe mobilization of coal fly ash, a representative Fe-containing anthropogenic aerosol, and Arizona test dust, a reference source material for mineral dust, in pH 2 sulfuric acid, acetic acid, and oxalic acid, respectively. The effects of pH and solar radiation on Fe dissolution have also been explored. The relative capacities of these three acids in Fe dissolution are in the order of oxalic acid > sulfuric acid > acetic acid. Oxalate forms mononuclear bidentate ligand with surface Fe and promotes Fe dissolution to the greatest extent. Photolysis of Fe-oxalate complexes further enhances Fe dissolution with the concomitant degradation of oxalate. These results suggest that ligand-promoted dissolution of Fe may play a more significant role in mobilizing Fe from atmospheric dust compared with proton-assisted processing. The role of atmospheric organic acids should be taken into account in global-biogeochemical modeling to better access dissolved atmospheric Fe deposition flux at the ocean surface.

  9. Comparative Genomics of Acetobacterpasteurianus Ab3, an Acetic Acid Producing Strain Isolated from Chinese Traditional Rice Vinegar Meiguichu

    PubMed Central

    Xia, Kai; Li, Yudong; Sun, Jing; Liang, Xinle

    2016-01-01

    Acetobacter pasteurianus, an acetic acid resistant bacterium belonging to alpha-proteobacteria, has been widely used to produce vinegar in the food industry. To understand the mechanism of its high tolerance to acetic acid and robust ability of oxidizing ethanol to acetic acid (> 12%, w/v), we described the 3.1 Mb complete genome sequence (including 0.28 M plasmid sequence) with a G+C content of 52.4% of A. pasteurianus Ab3, which was isolated from the traditional Chinese rice vinegar (Meiguichu) fermentation process. Automatic annotation of the complete genome revealed 2,786 protein-coding genes and 73 RNA genes. The comparative genome analysis among A. pasteurianus strains revealed that A. pasteurianus Ab3 possesses many unique genes potentially involved in acetic acid resistance mechanisms. In particular, two-component systems or toxin-antitoxin systems may be the signal pathway and modulatory network in A. pasteurianus to cope with acid stress. In addition, the large numbers of unique transport systems may also be related to its acid resistance capacity and cell fitness. Our results provide new clues to understanding the underlying mechanisms of acetic acid resistance in Acetobacter species and guiding industrial strain breeding for vinegar fermentation processes. PMID:27611790

  10. Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts

    NASA Astrophysics Data System (ADS)

    Shan, Junjun; Li, Mengwei; Allard, Lawrence F.; Lee, Sungsik; Flytzani-Stephanopoulos, Maria

    2017-11-01

    An efficient and direct method of catalytic conversion of methane to liquid methanol and other oxygenates would be of considerable practical value. However, it remains an unsolved problem in catalysis, as typically it involves expensive or corrosive oxidants or reaction media that are not amenable to commercialization. Although methane can be directly converted to methanol using molecular oxygen under mild conditions in the gas phase, the process is either stoichiometric (and therefore requires a water extraction step) or is too slow and low-yielding to be practical. Methane could, in principle, also be transformed through direct oxidative carbonylation to acetic acid, which is commercially obtained through methane steam reforming, methanol synthesis, and subsequent methanol carbonylation on homogeneous catalysts. However, an effective catalyst for the direct carbonylation of methane to acetic acid, which might enable the economical small-scale utilization of natural gas that is currently flared or stranded, has not yet been reported. Here we show that mononuclear rhodium species, anchored on a zeolite or titanium dioxide support suspended in aqueous solution, catalyse the direct conversion of methane to methanol and acetic acid, using oxygen and carbon monoxide under mild conditions. We find that the two products form through independent pathways, which allows us to tune the conversion: three-hour-long batch-reactor tests conducted at 150 degrees Celsius, using either the zeolite-supported or the titanium-dioxide-supported catalyst, yield around 22,000 micromoles of acetic acid per gram of catalyst, or around 230 micromoles of methanol per gram of catalyst, respectively, with selectivities of 60-100 per cent. We anticipate that these unusually high activities, despite still being too low for commercial application, may guide the development of optimized catalysts and practical processes for the direct conversion of methane to methanol, acetic acid and other useful

  11. Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts

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

    Shan, Junjun; Li, Mengwei; Allard, Lawrence F.

    An efficient and direct method of catalytic conversion of methane to liquid methanol and other oxygenates would be of considerable practical value. However, it remains an unsolved problem in catalysis, as typically it involves expensive or corrosive oxidants or reaction media(5-8) that are not amenable to commercialization. Although methane can be directly converted to methanol using molecular oxygen under mild conditions in the gas phase, the process is either stoichiometric (and therefore requires a water extraction step) or is too slow and low-yielding to be practical. Methane could, in principle, also be transformed through direct oxidative carbonylation to acetic acid,more » which is commercially obtained through methane steam reforming, methanol synthesis, and subsequent methanol carbonylation on homogeneous catalysts. However, an effective catalyst for the direct carbonylation of methane to acetic acid, which might enable the economical small-scale utilization of natural gas that is currently flared or stranded, has not yet been reported. Here we show that mononuclear rhodium species, anchored on a zeolite or titanium dioxide support suspended in aqueous solution, catalyse the direct conversion of methane to methanol and acetic acid, using oxygen and carbon monoxide under mild conditions. Here, we find that the two products form through independent pathways, which allows us to tune the conversion: three-hour-long batch-reactor tests conducted at 150 degrees Celsius, using either the zeolitesupported or the titanium-dioxide-supported catalyst, yield around 22,000 micromoles of acetic acid per gram of catalyst, or around 230 micromoles of methanol per gram of catalyst, respectively, with selectivities of 60-100 per cent. Finally, we anticipate that these unusually high activities, despite still being too low for commercial application, may guide the development of optimized catalysts and practical processes for the direct conversion of methane to methanol

  12. Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts

    DOE PAGES

    Shan, Junjun; Li, Mengwei; Allard, Lawrence F.; ...

    2017-11-30

    An efficient and direct method of catalytic conversion of methane to liquid methanol and other oxygenates would be of considerable practical value. However, it remains an unsolved problem in catalysis, as typically it involves expensive or corrosive oxidants or reaction media(5-8) that are not amenable to commercialization. Although methane can be directly converted to methanol using molecular oxygen under mild conditions in the gas phase, the process is either stoichiometric (and therefore requires a water extraction step) or is too slow and low-yielding to be practical. Methane could, in principle, also be transformed through direct oxidative carbonylation to acetic acid,more » which is commercially obtained through methane steam reforming, methanol synthesis, and subsequent methanol carbonylation on homogeneous catalysts. However, an effective catalyst for the direct carbonylation of methane to acetic acid, which might enable the economical small-scale utilization of natural gas that is currently flared or stranded, has not yet been reported. Here we show that mononuclear rhodium species, anchored on a zeolite or titanium dioxide support suspended in aqueous solution, catalyse the direct conversion of methane to methanol and acetic acid, using oxygen and carbon monoxide under mild conditions. Here, we find that the two products form through independent pathways, which allows us to tune the conversion: three-hour-long batch-reactor tests conducted at 150 degrees Celsius, using either the zeolitesupported or the titanium-dioxide-supported catalyst, yield around 22,000 micromoles of acetic acid per gram of catalyst, or around 230 micromoles of methanol per gram of catalyst, respectively, with selectivities of 60-100 per cent. Finally, we anticipate that these unusually high activities, despite still being too low for commercial application, may guide the development of optimized catalysts and practical processes for the direct conversion of methane to methanol

  13. Experimental investigation of thermodynamic properties of binary mixture of acetic acid + n-butanol and acetic acid + water at temperature from 293.15 K to 343.15 K

    NASA Astrophysics Data System (ADS)

    Paul, M. Danish John; Shruthi, N.; Anantharaj, R.

    2018-04-01

    The derived thermodynamic properties like excess molar volume, partial molar volume, excess partial molar volume and apparent volume of binary mixture of acetic acid + n-butanolandacetic acid + water has been investigated using measured density of mixtures at temperatures from 293.15 K to 343.15.

  14. Alkenyl Carboxylic Acid: Engineering the Nanomorphology in Polymer-Polymer Solar Cells as Solvent Additive.

    PubMed

    Zhang, Yannan; Yuan, Jianyu; Sun, Jianxia; Ding, Guanqun; Han, Lu; Ling, Xufeng; Ma, Wanli

    2017-04-19

    We have investigated a series of commercially available alkenyl carboxylic acids with different alkenyl chain lengths (trans-2-hexenoic acid (CA-6), trans-2-decenoic acid (CA-10), 9-tetradecenoic acid (CA-14)) for use as solvent additives in polymer-polymer non-fullerene solar cells. We systematically investigated their effect on the film absorption, morphology, carrier generation, transport, and recombination in all-polymer solar cells. We revealed that these additives have a significant impact on the aggregation of polymer acceptor, leading to improved phase segregation in the blend film. This in-depth understanding of the additives effect on the nanomorphology in all-polymer solar cell can help further boost the device performance. By using CA-10 with the optimal alkenyl chain length, we achieved fine phase separation, balanced charge transport, and suppressed recombination in all-polymer solar cells. As a result, an optimal power conversion efficiency (PCE) of 5.71% was demonstrated which is over 50% higher than that of the as-cast device (PCE = 3.71%) and slightly higher than that of devices with DIO treatment (PCE = 5.68%). Compared with widely used DIO, these halogen-free alkenyl carboxylic acids have a more sustainable processing as well as better performance, which may make them more promising candidates for use as processing additives in organic non-fullerene solar cells.

  15. Determining aromatic and aliphatic carboxylic acids in biomass-derived oil samples using 2,4-dinitrophenylhydrazine and liquid chromatography-electrospray injection-mass spectrometry/mass spectrometry

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

    Lewis, Sr., Samuel A.; Connatser, Raynella M.; Olarte, Mariefel V.

    Here, converting biomass to a useful fuel commonly incorporates the pyrolysis of the biomass feed stock. The base liquid fraction usually contains high concentrations of ketones, aldehydes and carboxylic acids, of which each can cause detrimental issues related to the storage and upgrading process. Knowing the carbonyl species and the concentration of each will provide value information to the pyrolysis researchers, specifically as that community branches into more targeted end-products such as jet fuel or biogenic-derived oxygenate-containing fuel products. The analysis of aldehydes, ketones and small alkyl carboxylic acids using 2,4-dinitrophenylhydrazine (DNPH) derivation method has been well documented and themore » method is commonly used the analytical community. By using liquid chromatograph coupled to tandem mass spectrometry, biomass sample analysis can be complete with identification of most carbonyl species. The issue of identifying isobaric ketone and aldehyde compounds can be resolved by utilizing differences in retention time or characteristic fragment ions of ketones and aldehydes. One issue which could not resolved using published methods was identifying aromatic or large non-aromatic carboxylic acids from their corresponding hydroxyl aldehyde or ketone analogs. By modifying the current method for determining carbonyls in biomass samples, carboxylic and hydroxyl-carbonyl can be determined. A careful adjustment of the pH during the extraction procedure and extended heating time of the DNPH solution allowed for the successful derivation of aromatic carboxylic acids. Like other dinitrophenylhydrazones, carboxylic acid derivatives also produce a unique secondary ion pattern, which was useful to distinguish these species from the non-acid analogs.« less

  16. Determining aromatic and aliphatic carboxylic acids in biomass-derived oil samples using 2,4-dinitrophenylhydrazine and liquid chromatography-electrospray injection-mass spectrometry/mass spectrometry

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

    Lewis, Samuel A.; Connatser, Raynella M.; Olarte, Mariefel V.

    Converting biomass to a useful fuel commonly incorporates the pyrolysis of the biomass feed stock. The base liquid fraction usually contains high concentrations of ketones, aldehydes and carboxylic acids, of which each can cause detrimental issues related to the storage and upgrading process. Knowing the carbonyl species and the concentration of each will provide value information to the pyrolysis researchers, specifically as that community branches into more targeted end-products such as jet fuel or biogenic-derived oxygenate-containing fuel products. The analysis of aldehydes, ketones and small alkyl carboxylic acids using 2,4-dinitrophenylhydrazine (DNPH) derivation method has been well documented and the methodmore » is commonly used the analytical community. By using liquid chromatograph coupled to tandem mass spectrometry, biomass sample analysis can be complete with identification of most carbonyl species. The issue of identifying isobaric ketone and aldehyde compounds can be resolved by utilizing differences in retention time or characteristic fragment ions of ketones and aldehydes. One issue which could not resolved using published methods was identifying aromatic or large non-aromatic carboxylic acids from their corresponding hydroxyl aldehyde or ketone analogs. By modifying the current method for determining carbonyls in biomass samples, carboxylic and hydroxyl-carbonyl can be determined. A careful adjustment of the pH during the extraction procedure and extended heating time of the DNPH solution allowed for the successful derivation of aromatic carboxylic acids. Like other dinitrophenylhydrazones, carboxylic acid derivatives also produce a unique secondary ion pattern, which was useful to distinguish these species from the non-acid analogs.« less

  17. Determining aromatic and aliphatic carboxylic acids in biomass-derived oil samples using 2,4-dinitrophenylhydrazine and liquid chromatography-electrospray injection-mass spectrometry/mass spectrometry

    DOE PAGES

    Lewis, Sr., Samuel A.; Connatser, Raynella M.; Olarte, Mariefel V.; ...

    2017-11-22

    Here, converting biomass to a useful fuel commonly incorporates the pyrolysis of the biomass feed stock. The base liquid fraction usually contains high concentrations of ketones, aldehydes and carboxylic acids, of which each can cause detrimental issues related to the storage and upgrading process. Knowing the carbonyl species and the concentration of each will provide value information to the pyrolysis researchers, specifically as that community branches into more targeted end-products such as jet fuel or biogenic-derived oxygenate-containing fuel products. The analysis of aldehydes, ketones and small alkyl carboxylic acids using 2,4-dinitrophenylhydrazine (DNPH) derivation method has been well documented and themore » method is commonly used the analytical community. By using liquid chromatograph coupled to tandem mass spectrometry, biomass sample analysis can be complete with identification of most carbonyl species. The issue of identifying isobaric ketone and aldehyde compounds can be resolved by utilizing differences in retention time or characteristic fragment ions of ketones and aldehydes. One issue which could not resolved using published methods was identifying aromatic or large non-aromatic carboxylic acids from their corresponding hydroxyl aldehyde or ketone analogs. By modifying the current method for determining carbonyls in biomass samples, carboxylic and hydroxyl-carbonyl can be determined. A careful adjustment of the pH during the extraction procedure and extended heating time of the DNPH solution allowed for the successful derivation of aromatic carboxylic acids. Like other dinitrophenylhydrazones, carboxylic acid derivatives also produce a unique secondary ion pattern, which was useful to distinguish these species from the non-acid analogs.« less

  18. Structure and thermotropic phase behavior of sodium and potassium carboxylate ionomers

    NASA Astrophysics Data System (ADS)

    Mantsch, H. H.; Weng, S. F.; Yang, P. W.; Eysel, H. H.

    1994-07-01

    A molecular complex is formed between long-chain carboxylic acids and their alkali salts in a 1 : 1 mixture. These so-called "acid soaps" or carboxylate ionomers have multilamellar bilayer-type structures in solid state, which are retained in the presence of excess water, resembling the dispersions (gels) formed by typical two-chain amphiphiles, e.g. lipids. The special arrangement of hydrogen-bonded pairs of carboxylic acid and carboxylate groups into a unique "head-group" is supported by frequency shifts and partial or total disappearance of the characteristic vibrations of carboxylic acid dimers and of carboxylate groups. The existence of well-ordered hydrocarbon chains is demonstrated by the existence and polarization properties of the methylene rocking and wagging propagation modes. The gel to liquid-crystal phase transition of the hydrated acid soaps shows practically no cation dependence, unlike the corresponding phase transition in neutral soaps which varies considerably with the nature of the counterion. There is spectroscopic evidence to suggest a cooperative process that involves "melting" of the alkyl chains and disintegration of the hydrogen-bonded carboxylate—carboxylic acid complex, followed by a cation-dependent equilibrium that favors the formation of acid dimers at elevated temperatures and some form of hydrogen-bonded ion pair aggregates at intermediate temperatures.

  19. N-(6-Methylpyridin-2-yl)mesitylenesulfonamide and acetic acid--a salt, a cocrystal or both?

    PubMed

    Pan, Fangfang; Kalf, Irmgard; Englert, Ulli

    2015-08-01

    In the solid obtained from N-(6-methylpyridin-2-yl)mesitylenesulfonamide and acetic acid, the constituents interact via two N-H···O hydrogen bonds. The H atom situated in one of these short contacts is disordered over two positions: one of these positions is formally associated with an adduct of the neutral sulfonamide molecule and the neutral acetic acid molecule, and corresponds to a cocrystal, while the alternative site is associated with salt formation between a protonated sulfonamide molecule and deprotonated acetic acid molecule. Site-occupancy refinements and electron densities from difference Fourier maps suggest a trend with temperature, albeit of limited significance; the cocrystal is more relevant at 100 K, whereas the intensity data collected at room temperature match the description as cocrystal and salt equally well.

  20. Isolation and characterization of esters of indole-3-acetic acid from the liquid endosperm of the horse chestnut (Aesculus species)

    NASA Technical Reports Server (NTRS)

    Domagalski, W.; Schulze, A.; Bandurski, R. S.

    1987-01-01

    Esters of indole-3-acetic acid were extracted and purified from the liquid endosperm of immature fruits of various species of the horse chestnut (Aesculus parviflora, A. baumanni, A. pavia rubra, and A. pavia humulis). The liquid endosperm contained, at least 12 chromatographically distinct esters. One of these compounds was purified and characterized as an ester of indole-3-acetic acid and myo-inositol. A second compound was found to be an ester of indole-3-acetic acid and the disaccharide rutinose (glucosyl-rhamnose). A third compound was partially characterized as an ester of indole-3-acetic acid and a desoxyaminohexose.

  1. Degradation of chitosan hydrogel dispersed in dilute carboxylic acids by solution plasma and evaluation of anticancer activity of degraded products

    NASA Astrophysics Data System (ADS)

    Chokradjaroen, Chayanaphat; Rujiravanit, Ratana; Theeramunkong, Sewan; Saito, Nagahiro

    2018-01-01

    Chitosan is a polysaccharide that has been extensively studied in the field of biomedicine, especially its water-soluble degraded products called chitooligosaccharides (COS). In this study, COS were produced by the degradation of chitosan hydrogel dispersed in a dilute solution (i.e., 1.55 mM) of various kinds of carboxylic acids using a non-thermal plasma technology called solution plasma (SP). The degradation rates of chitosan were influenced by the type of carboxylic acids, depending on the interaction between chitosan and each carboxylic acid. After SP treatment, the water-soluble degraded products containing COS could be easily separated from the water-insoluble residue of chitosan hydrogel by centrifugation. The production yields of the COS were mostly higher than 55%. Furthermore, the obtained COS products were evaluated for their inhibitory effect as well as their selectivity against human lung cancer cells (H460) and human lung normal cells (MRC-5).

  2. The sensitivity of the yeast, Saccharomyces cerevisiae, to acetic acid is influenced by DOM34 and RPL36A.

    PubMed

    Samanfar, Bahram; Shostak, Kristina; Moteshareie, Houman; Hajikarimlou, Maryam; Shaikho, Sarah; Omidi, Katayoun; Hooshyar, Mohsen; Burnside, Daniel; Márquez, Imelda Galván; Kazmirchuk, Tom; Naing, Thet; Ludovico, Paula; York-Lyon, Anna; Szereszewski, Kama; Leung, Cindy; Jin, Jennifer Yixin; Megarbane, Rami; Smith, Myron L; Babu, Mohan; Holcik, Martin; Golshani, Ashkan

    2017-01-01

    The presence of acetic acid during industrial alcohol fermentation reduces the yield of fermentation by imposing additional stress on the yeast cells. The biology of cellular responses to stress has been a subject of vigorous investigations. Although much has been learned, details of some of these responses remain poorly understood. Members of heat shock chaperone HSP proteins have been linked to acetic acid and heat shock stress responses in yeast. Both acetic acid and heat shock have been identified to trigger different cellular responses including reduction of global protein synthesis and induction of programmed cell death. Yeast HSC82 and HSP82 code for two important heat shock proteins that together account for 1-2% of total cellular proteins. Both proteins have been linked to responses to acetic acid and heat shock. In contrast to the overall rate of protein synthesis which is reduced, the expression of HSC82 and HSP82 is induced in response to acetic acid stress. In the current study we identified two yeast genes DOM34 and RPL36A that are linked to acetic acid and heat shock sensitivity. We investigated the influence of these genes on the expression of HSP proteins. Our observations suggest that Dom34 and RPL36A influence translation in a CAP-independent manner.

  3. Short-Chain Fatty Acid Acetate Stimulates Adipogenesis and Mitochondrial Biogenesis via GPR43 in Brown Adipocytes.

    PubMed

    Hu, Jiamiao; Kyrou, Ioannis; Tan, Bee K; Dimitriadis, Georgios K; Ramanjaneya, Manjunath; Tripathi, Gyanendra; Patel, Vanlata; James, Sean; Kawan, Mohamed; Chen, Jing; Randeva, Harpal S

    2016-05-01

    Short-chain fatty acids play crucial roles in a range of physiological functions. However, the effects of short-chain fatty acids on brown adipose tissue have not been fully investigated. We examined the role of acetate, a short-chain fatty acid formed by fermentation in the gut, in the regulation of brown adipocyte metabolism. Our results show that acetate up-regulates adipocyte protein 2, peroxisomal proliferator-activated receptor-γ coactivator-1α, and uncoupling protein-1 expression and affects the morphological changes of brown adipocytes during adipogenesis. Moreover, an increase in mitochondrial biogenesis was observed after acetate treatment. Acetate also elicited the activation of ERK and cAMP response element-binding protein, and these responses were sensitive to G(i/o)-type G protein inactivator, Gβγ-subunit inhibitor, phospholipase C inhibitor, and MAPK kinase inhibitor, indicating a role for the G(i/o)βγ/phospholipase C/protein kinase C/MAPK kinase signaling pathway in these responses. These effects of acetate were mimicked by treatment with 4-chloro-α-(1-methylethyl)-N-2-thiazolylbenzeneacetamide, a synthetic G protein-coupled receptor 43 (GPR43) agonist and were impaired in GPR43 knockdown cells. Taken together, our results indicate that acetate may have important physiological roles in brown adipocytes through the activation of GPR43.

  4. Metabolism of indole-3-acetic acid by orange (Citrus sinensis) flavedo tissue during fruit development.

    PubMed

    Chamarro, J; Ostin, A; Sandberg, G

    2001-05-01

    [5-3H, 1'-14C, 13C6, 12C] Indole-3-acetic acid (IAA), was applied to the flavedo (epicarp) of intact orange fruits at different stages of development. After incubation in the dark, at 25 degrees C, the tissue was extracted with MeOH and the partially purified extracts were analyzed by reversed phase HPLC-RC. Six major metabolite peaks were detected and subsequently analyzed by combined HPLC-frit-FAB MS. The metabolite peak 6 contained oxindole-3-acetic acid (OxIAA), indole-3-acetyl-N-aspartic acid (IAAsp) and also indole-3-acetyl-N-glutamic acid (IAGlu). The nature of metabolite 5 remains unknown. Metabolites 3 and 4 were diastereomers of oxindole-3-acetyl-N-aspartic acid (OxIAAsp). Metabolite 2 was identified as dioxindole-3-acetic acid and metabolite 1 as a DiOx-IAA linked in position three to a hexose, which is suggested to be 3-(-O-beta-glucosyl) dioxindole-3-acetic acid (DiOxIAGlc). Identification work as well as feeding experiments with the [5-3H]IAA labeled metabolites suggest that IAA is metabolized in flavedo tissue mainly through two pathways, namely IAA-OxIAA-DiOxIAA-DiOxIAGlc and IAA-IAAsp-OxIAAsp. The flavedo of citrus fruit has a high capacity for IAA catabolism until the beginning of fruit senescence, with the major route having DiOxIAGlc as end product. This capacity is operative even at high IAA concentrations and is accelerated by pretreatment with the synthetic auxins 2,4-D, NAA and the gibberellin GA3.

  5. Use of acetic and citric acids to inhibit Escherichia coli O157:H7, Salmonella Typhimurium and Staphylococcus aureus in tabbouleh salad.

    PubMed

    Al-Rousan, Walid M; Olaimat, Amin N; Osaili, Tareq M; Al-Nabulsi, Anas A; Ajo, Radwan Y; Holley, Richard A

    2018-08-01

    The objective of the current study was to evaluate the antimicrobial action of different concentrations of acetic (0.3% and 0.4%) or citric (1% and 1.4%) acids and their combinations (1% citric acid plus 0.4% acetic acid and 1.4% citric acid plus 0.3% acetic acid) against Salmonella Typhimurium, Escherichia coli O157:H7 and Staphylococcus aureus in tabbouleh salad stored at 21, 10 and 4 °C. Acetic acid was more inhibitory toward S. Typhimurium and E. coli O157:H7 than citric acid at 21 °C; S. Typhimurium and E. coli O157:H7 cells were not detected in tabbouleh treated with 0.4% acetic acid after 5 and 7 days, respectively. The combined effect of acetic and citric acid was synergistic against S. Typhimurium, and E. coli O157:H7, but not against S. aureus. The combinations of acetic and citric acids reduced S. Typhimurium, and E. coli O157:H7 to below the detection levels after 2 and 3 days at 21 °C, respectively. However, these treatments significantly reduced S. aureus numbers compared to the control at tested temperatures by the end of storage. Acetic and citric acids have the potential to be used in tabbouleh salad to reduce the risk from S. Typhimurium, E. coli O157:H7 and S. aureus. Copyright © 2018. Published by Elsevier Ltd.

  6. Quantifying Effect of Lactic, Acetic, and Propionic Acids on Growth of Molds Isolated from Spoiled Bakery Products.

    PubMed

    Dagnas, Stéphane; Gauvry, Emilie; Onno, Bernard; Membré, Jeanne-Marie

    2015-09-01

    The combined effect of undissociated lactic acid (0 to 180 mmol/liter), acetic acid (0 to 60 mmol/liter), and propionic acid (0 to 12 mmol/liter) on growth of the molds Aspergillus niger, Penicillium corylophilum, and Eurotium repens was quantified at pH 3.8 and 25°C on malt extract agar acid medium. The impact of these acids on lag time for growth (λ) was quantified through a gamma model based on the MIC. The impact of these acids on radial growth rate (μ) was analyzed statistically through polynomial regression. Concerning λ, propionic acid exhibited a stronger inhibitory effect (MIC of 8 to 20 mmol/liter depending on the mold species) than did acetic acid (MIC of 23 to 72 mmol/liter). The lactic acid effect was null on E. repens and inhibitory on A. niger and P. corylophilum. These results were validated using independent sets of data for the three acids at pH 3.8 but for only acetic and propionic acids at pH 4.5. Concerning μ, the effect of acetic and propionic acids was slightly inhibitory for A. niger and P. corylophilum but was not significant for E. repens. In contrast, lactic acid promoted radial growth of all three molds. The gamma terms developed here for these acids will be incorporated in a predictive model for temperature, water activity, and acid. More generally, results for μ and λ will be used to identify and evaluate solutions for controlling bakery product spoilage.

  7. Different response to acetic acid stress in Saccharomyces cerevisiae wild-type and l-ascorbic acid-producing strains.

    PubMed

    Martani, Francesca; Fossati, Tiziana; Posteri, Riccardo; Signori, Lorenzo; Porro, Danilo; Branduardi, Paola

    2013-09-01

    Biotechnological processes are of increasing significance for industrial production of fine and bulk chemicals, including biofuels. Unfortunately, under operative conditions microorganisms meet multiple stresses, such as non-optimal pH, temperature, oxygenation and osmotic stress. Moreover, they have to face inhibitory compounds released during the pretreatment of lignocellulosic biomasses, which constitute the preferential substrate for second-generation processes. Inhibitors include furan derivatives, phenolic compounds and weak organic acids, among which acetic acid is one of the most abundant and detrimental for cells. They impair cellular metabolism and growth, reducing the productivity of the process: therefore, the development of robust cell factories with improved production rates and resistance is of crucial importance. Here we show that a yeast strain engineered to endogenously produce vitamin C exhibits an increased tolerance compared to the parental strain when exposed to acetic acid at moderately toxic concentrations, measured as viability on plates. Starting from this evidence, we investigated more deeply: (a) the nature and levels of reactive oxygen species (ROS); (b) the activation of enzymes that act directly as detoxifiers of reactive oxygen species, such as superoxide dismutase (SOD) and catalase, in parental and engineered strains during acetic acid stress. The data indicate that the engineered strain can better recover from stress by limiting ROS accumulation, independently from SOD activation. The engineered yeast can be proposed as a model for further investigating direct and indirect mechanism(s) by which an antioxidant can rescue cells from organic acid damage; moreover, these studies will possibly provide additional targets for further strain improvements. Copyright © 2013 John Wiley & Sons, Ltd.

  8. 6-Substituted 3,4-dihydro-naphthalene-2-carboxylic acids: synthesis and structure-activity studies in a novel class of human 5alpha reductase inhibitors.

    PubMed

    Baston, Eckhard; Salem, Ola I A; Hartmann, Rolf W

    2002-10-01

    Novel 3,4-dihydro-naphthalene-2-carboxylic acids were synthesized and evaluated for 5alpha reductase inhibitory activity. This enzyme exists in two isoforms and is a pharmacological target for the treatment of benign prostatic hyperplasia, male pattern baldness and acne. In the present study non-steroidal compounds capable of mimicking the transition state of the steroidal substrates were prepared. The synthetic strategy for the preparation of compounds 1-6 consisted of triflation followed by subsequent Heck-type carboxylation or methoxy carbonylation for 6-phenyl-3,4-dihydronaphthalen-2(1H)-one 1c. A Negishi-type coupling reaction between 6-(trifluoro-methanesulfonyloxy)-3,4-dihydro-naphthalene-2-carboxylic acid methyl ester 7b and various aryl bromides led, after further transformations, to 6-substituted 3,4-dihydro-naphthalene-2-carboxylic acids 7-15. In a similar way the corresponding naphthalene-2-carboxylic acids 16 and 17 were obtained. The DU 145 cell line and prostate homogenates served as enzyme sources for the human type 1 and type 2 isozymes, whereas ventral prostate was employed to evaluate rat isozyme inhibitory potency. The most active inhibitors identified in this study were 6-[4-(N,N-dicyclohexylaminocarbonyl)phenyl]-3,4-dihydro-naphthalene-2-carboxylic acid (3) (IC50 = 0.09 microM, rat type 1), 6-[3-(N,N-dicyclohexylaminocarbonyl)phenyl]-3,4-dihydro-naphthalene-2-carboxylic acid (13) (IC50 = 0.75 microM, human type 2; IC50 = 0.81 microM, human type 1) and 6-[4-(N,N-diisopropylamino-carbonyl)phenyl]naphthalene-2-carboxylic acid (16) (IC50 = 0.2 microM, human type 2). The latter compound was shown to deactivate the enzyme in an uncompetitive manner (Ki = 90 nM; Km, Testosterone = 0.8-1.0 microM) similar to the steroidal inhibitor Epristeride. Select inhibitors (13 and 16) were tested in vivo using testosterone propionate-treated, juvenile, orchiectomized SD-rats. None of the compounds was active at a dose of 25 mg/kg. This result might in part be

  9. Effect of acetic acid on physical properties of pregelatinized wheat and corn starch gels.

    PubMed

    Majzoobi, Mahsa; Kaveh, Zahra; Farahnaky, Asgar

    2016-04-01

    Pregelatinized starches are physically modified starches with ability to absorb water and increase viscosity at ambient temperature. The main purpose of this study was to determine how different concentrations of acetic acid (0, 500, 1000, 10,000 mg/kg) can affect functional properties of pregelatinized wheat and corn starches (PGWS and PGCS, respectively) produced by a twin drum drier. With increasing acetic acid following changes occurred for both samples; cold water solubility (at 25 °C) increased, water absorption and apparent cold water viscosity (at 25 °C) reduced, the smooth surface of the starch particles converted to an uneven surface as confirmed by scanning electron microscopy, cohesiveness, consistency and turbidity of the starch gels reduced while their syneresis increased. It was found that in presence of acetic acid, PGWS resulted in higher water absorption and apparent cold water viscosity and produced more cohesive and turbid gels with less syneresis compared to PGCS. Copyright © 2015 Elsevier Ltd. All rights reserved.

  10. Efficacy of Lactic Acid, Lactic Acid-Acetic Acid Blends, and Peracetic Acid To Reduce Salmonella on Chicken Parts under Simulated Commercial Processing Conditions.

    PubMed

    Ramirez-Hernandez, Alejandra; Brashears, Mindy M; Sanchez-Plata, Marcos X

    2018-01-01

    The poultry processing industry has been undergoing a series of changes as it modifies processing practices to comply with new performance standards for chicken parts and comminuted poultry products. The regulatory approach encourages the use of intervention strategies to prevent and control foodborne pathogens in poultry products and thus improve food safety and protect human health. The present studies were conducted to evaluate the efficacy of antimicrobial interventions for reducing Salmonella on inoculated chicken parts under simulated commercial processing conditions. Chicken pieces were inoculated by immersion in a five-strain Salmonella cocktail at 6 log CFU/mL and then treated with organic acids and oxidizing agents on a commercial rinsing conveyor belt. The efficacy of spraying with six different treatments (sterile water, lactic acid, acetic acid, buffered lactic acid, acetic acid in combination with lactic acid, and peracetic acid) at two concentrations was evaluated on skin-on and skin-off chicken thighs at three application temperatures. Skinless chicken breasts were used to evaluate the antimicrobial efficacy of lactic acid and peracetic acid. The color stability of treated and untreated chicken parts was assessed after the acid interventions. The lactic acid and buffered lactic acid treatments produced the greatest reductions in Salmonella counts. Significant differences between the control and water treatments were identified for 5.11% lactic acid and 5.85% buffered lactic acid in both skin-on and skin-off chicken thighs. No significant effect of treatment temperature for skin-on chicken thighs was found. Lactic acid and peracetic acid were effective agents for eluting Salmonella cells attached to chicken breasts.

  11. The kinetics of photocatalytic degradation of aliphatic carboxylic acids in an UV/TiO2 suspension system.

    PubMed

    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.

  12. ION-EXCLUSION CHROMATOGRAPHIC DETERMINATION OF CARBOXYLIC ACIDS USED TO SUPPORT THE MICROBIALLY MEDIATED REDUCTIVE DECHLORINATION OF TETRACHLOROETHENE

    EPA Science Inventory

    An analytical method was developed for the determination of lactic acid, formic acid, acetic acid, propionic acid, and butyric acid in environmental microcosm samples using ion-exclusion chromatography. The chromatographic behavior of various eluents was studied to determine the ...

  13. Structures of aspartic acid-96 in the L and N intermediates of bacteriorhodopsin: analysis by Fourier transform infrared spectroscopy

    NASA Technical Reports Server (NTRS)

    Maeda, A.; Sasaki, J.; Shichida, Y.; Yoshizawa, T.; Chang, M.; Ni, B.; Needleman, R.; Lanyi, J. K.

    1992-01-01

    The light-induced difference Fourier transform infrared spectrum between the L or N intermediate minus light-adapted bacteriorhodopsin (BR) was measured in order to examine the protonated states and the changes in the interactions of carboxylic acids of Asp-96 and Asp-115 in these intermediates. Vibrational bands due to the protonated and unprotonated carboxylic acid were identified by isotope shift and band depletion upon substitution of Asp-96 or -115 by asparagine. While the signal due to the deprotonation of Asp-96 was clearly observed in the N intermediate, this residue remained protonated in L. Asp-115 was partially deprotonated in L. The C = O stretching vibration of protonated Asp-96 of L showed almost no shift upon 2H2O substitution, in contrast to the corresponding band of Asp-96 or Asp-115 of BR, which shifted by 9-12 cm-1 under the same conditions. In the model system of acetic acid in organic solvents, such an absence of the shift of the C = O stretching vibration of the protonated carboxylic acid upon 2H2O substitution was seen only when the O-H of acetic acid is hydrogen-bonded. The non-hydrogen-bonded monomer showed the 2H2O-dependent shift. Thus, the O-H bond of Asp-96 enters into hydrogen bonding upon conversion of BR to L. Its increased hydrogen bonding in L is consistent with the observed downshift of the O-H stretching vibration of the carboxylic acid of Asp-96.

  14. Crystal and molecular structures of sixteen charge-assisted hydrogen bond-mediated diisopropylammonium salts from different carboxylic acids

    NASA Astrophysics Data System (ADS)

    Lin, Zhihao; Hu, Kaikai; Jin, Shouwen; Ding, Aihua; Wang, Yining; Dong, Lingfeng; Gao, Xingjun; Wang, Daqi

    2017-10-01

    Cocrystallization of the commonly available organic amine, diisopropylamine, with a series of carboxylic acids gave a total of sixteen molecular salts with the compositions: diisopropylaminium 2-methyl-2-phenoxypropanate [(Hdpa)+ · (mpa-), mpa- = 2-methyl-2-phenoxypropanoate] (1), diisopropylaminium 2-methyl-2-(naphthalen-2-yloxy)-propionate [(Hdpa)+ · (npa-), npa- = 2-methyl-2-(naphthalen-2-yloxy)-propionate] (2), diisopropylaminium indole-3-acetate [(Hdpa)+ · (iaa-), iaa- = indole-3-acetate] (3), diisopropylaminium 4-chlorophenoxyacetate [(Hdpa)+ · (cpa-), cpa- = 4-chlorophenoxyacetate] (4), diisopropylaminium 2,4-dichlorophenoxyacetate [(Hdpa)+ · (dcpa-), dcpa- = 2,4-dichlorophenoxyacetate] (5), diisopropylaminium 4-hydroxybenzoate [(Hdpa)+ · (hba-), hba- = 4-hydroxybenzoate] (6), diisopropylaminium 4-aminobenzoate [(Hdpa)+ · (aba-), aba- = 4-aminobenzoate] (7), tetra(diisopropylaminium) tetra(1-hydroxy-2-naphthoate) trihydrate [(Hdpa)44+ · (2-hnpa)44- · 3H2O, 2-hnpa = 1-hydroxy-2-naphthoate] (8), diisopropylaminium 2-hydroxy-3-naphthoate [(Hdpa)+ · (3-hnpa-), 3-hnpa- = 2-hydroxy-3-naphthoate] (9), diisopropylaminium 5-bromosalicylate [(Hdpa)+ · (bsa-), bsa- = 5-bromosalicylate] (10), diisopropylaminium 3,5-dinitrobenzoate [(Hdpa)+ · (dna-), dna- = 3,5-dinitrobenzoate] (11), diisopropylaminium 3,5-dinitrosalicylate [(Hdpa)+ · (3,5-dns-), 3,5-dns- = 3,5-dinitrosalicylate] (12), tetra(diisopropylaminium) bis(m-phthalate) monohydrate [(Hdpa+)4 · (mpta2-)2 · H2O, mpta2- = m-phthalate] (13), bis(diisopropylaminium) dihydrogen 1,2,3,4-butane tetracarboxylate [(Hdpa+)2 · (H2Bta2-), H2Bta2- = dihydrogen 1,2,3,4-butane tetracarboxylate] (14), bis(diisopropylaminium) mucate [(Hdpa+)2 · (muc2-), muc2- = mucate] (15), and diisopropylaminium hydrogen 1,2-phenylenediacetate [(Hdpa) · (Hpda-), Hpda- = hydrogen 1,2-phenylenediacetate] (16). The sixteen salts have been characterised by XRD technique, IR, and elemental analysis, and the melting points of all the

  15. Metabolizable energy values and amino acid availability of vetch (Vicia sativa) and ervil (Vicia ervilia) seeds soaked in water and acetic acid.

    PubMed

    Farran, M T; Barbour, G W; Uwayjan, M G; Ashkarian, V M

    2001-07-01

    In two experiments we evaluated the effect of water and acetic acid soaking on ME, apparent amino acid (AA) availability, and true AA availability of vetch (V) and ervil (E) seeds. In Experiment 1, the feedstuffs were untreated (U) V or coarsely ground V soaked in water (1:10, wt/vol) at 40 C for 72 h with a water change every 12 h (40WV), vetch soaked in 1% acetic acid for 24 h at 40 C (40AAV) or at room temperature (RTAAV), or dehulled soybean meal (SBM). In Experiment 2, E seeds were subjected to the same soaking methods, and the ingredients were UE, 40WE, 40AAE, RTAAE, and SBM. Each feedstuff was precision-fed to five individually caged mature ISA Brown roosters. A group of five roosters was used to correct for metabolic and endogenous energy and amino acid losses. The AME, AMEn, TME, and TMEn of UV and UE (in parentheses) were 2,558 (2,663), 2,840 (3,098), 3,026 (3,154), and 2,934 (3,176) kcal/kg DM, respectively, and were, in general, higher than those of SBM. The TMEn of V increased as a result of soaking in water or acetic acid, whereas that of E decreased in 40WE and RTAAE by 492 and 920 kcal/kg DM, respectively (P < 0.05). The apparent availability of most essential amino acids in UV and UE was lower (P < 0.05) than that of SBM. Acetic acid soaking of V, irrespective of temperature, and E at 40 C resulted in apparent AA availability similar to that of SBM except for Met. The true AA availability of V treated or not, and that of E soaked at 40 C, were similar to that of SBM. Results indicated that UV and UE are energy rich ingredients but detrimental to amino acid availability. Soaking the seeds in acetic acid at room temperature and at 40 C improved the nutritional value of V and E, respectively.

  16. Lewis base activation of Lewis acids: catalytic, enantioselective addition of silyl ketene acetals to aldehydes.

    PubMed

    Denmark, Scott E; Beutner, Gregory L; Wynn, Thomas; Eastgate, Martin D

    2005-03-23

    The concept of Lewis base activation of Lewis acids has been reduced to practice for catalysis of the aldol reaction of silyl ketene acetals and silyl dienol ethers with aldehydes. The weakly acidic species, silicon tetrachloride (SiCl4), can be activated by binding of a strongly Lewis basic chiral phosphoramide, leading to in situ formation of a chiral Lewis acid. This species has proven to be a competent catalyst for the aldol addition of acetate-, propanoate-, and isobutyrate-derived silyl ketene acetals to conjugated and nonconjugated aldehydes. Furthermore, vinylogous aldol reactions of silyl dienol ethers are also demonstrated. The high levels of regio-, anti diastereo-, and enantioselectivity observed in these reactions can be rationalized through consideration of an open transition structure where steric interactions between the silyl cation complex and the approaching nucleophile are dominant.

  17. Co-administration of α-lipoic acid and cyclosporine aggravates colon ulceration of acetic acid-induced ulcerative colitis via facilitation of NO/COX-2/miR-210 cascade.

    PubMed

    El-Gowelli, Hanan M; Saad, Evan I; Abdel-Galil, Abdel-Galil A; Ibrahim, Einas R

    2015-11-01

    In this work, α-lipoic acid and cyclosporine demonstrated significant protection against acetic acid-induced ulcerative colitis in rats. We proposed that α-lipoic acid and cyclosporine co-administration might modulate their individual effects. Induction of ulcerative colitis in rats was performed by intra-rectal acetic acid (5% v/v) administration for 3 consecutive days. Effects of individual or combined used of α-lipoic acid (35 mg/kg ip) or cyclosporine (5mg/kg sc) for 6 days starting 2 days prior to acetic acid were assessed. Acetic acid caused colon ulceration, bloody diarrhea and weight loss. Histologically, there was mucosal atrophy and inflammatory cells infiltration in submucosa, associated with depletion of colon reduced glutathione, superoxide dismutase and catalase activities and elevated colon malondialdehyde, serum C-reactive protein (C-RP) and tumor necrosis factor-α (TNF-α). Colon gene expression of cyclooxygenase-2 and miR-210 was also elevated. These devastating effects of acetic acid were abolished upon concurrent administration of α-lipoic acid. Alternatively, cyclosporine caused partial protection against acetic acid-induced ulcerative colitis. Cyclosporine did not restore colon reduced glutathione, catalase activity, serum C-RP or TNF-α. Unexpectedly, co-administration of α-lipoic acid and cyclosporine aggravated colon ulceration. Concomitant use of α-lipoic acid and cyclosporine significantly increased nitric oxide production, cyclooxygenase-2 and miR-210 gene expression compared to all other studied groups. The current findings suggest that facilitation of nitric oxide/cyclooxygenase-2/miR-210 cascade constitutes, at least partially, the cellular mechanism by which concurrent use of α-lipoic acid and cyclosporine aggravates colon damage. Collectively, the present work highlights the probable risk of using α-lipoic acid/cyclosporine combination in ulcerative colitis patients. Copyright © 2015 Elsevier Inc. All rights reserved.

  18. Effect of Amine Modification on the Properties of Zirconium-Carboxylic Acid Based Materials and Their Applications as NO2 Adsorbents at Ambient Conditions

    DTIC Science & Technology

    2014-01-06

    as a source of –SH [23]. Nitrogen dioxide (NO2) is an acidic , corrosive , and toxic gas present in the atmosphere. The main sources of NO2 pollution is...occurring are the Lewis acid –base reactions. These reactions are facilitated by the formation of nitric Schematic reaction between the urea incorporated in...of zirconium– carboxylic acid based materials and their applications as NO2 adsorbents at ambient conditions Zirconium–carboxylic ligand-based porous

  19. Ab initio Hartree-Fock investigation of 1- H-pyrrolo[3,2- b]pyridine-3-yl acetic acid

    NASA Astrophysics Data System (ADS)

    Ramek, Michael; Tomić, Sanja

    2001-09-01

    The potential energy surface of 1- H-pyrrolo[3,2- b]pyridine-3-yl acetic acid has been investigated via RIIF/6-31G* calculations. The stationary points and reaction paths for syn orientation of the COOH group were determined and are compared with those of the derivatives of 3-indole acetic acid, which act as plant growth hormones. 1- H-pyrrolo[3,2- b]pyridine-3-yl acetic acid forms a kinetically stable conformer with a strong intramolecular hydrogen bond, in which the COOH group is in anti orientation. The influence of this hydrogen bond on bond lengths and vibration frequencies is described.

  20. A Precise Method for Processing Data to Determine the Dissociation Constants of Polyhydroxy Carboxylic Acids via Potentiometric Titration.

    PubMed

    Huang, Kaixuan; Xu, Yong; Lu, Wen; Yu, Shiyuan

    2017-12-01

    The thermodynamic dissociation constants of xylonic acid and gluconic acid were studied via potentiometric methods, and the results were verified using lactic acid, which has a known pKa value, as a model compound. Solutions of xylonic acid and gluconic acid were titrated with a standard solution of sodium hydroxide. The determined pKa data were processed via the method of derivative plots using computer software, and the accuracy was validated using the Gran method. The dissociation constants associated with the carboxylic acid group of xylonic and gluconic acids were determined to be pKa 1  = 3.56 ± 0.07 and pKa 1  = 3.74 ± 0.06, respectively. Further, the experimental data showed that the second deprotonation constants associated with a hydroxyl group of each of the two acids were pKa 2  = 8.58 ± 0.12 and pKa 2  = 7.06 ± 0.08, respectively. The deprotonation behavior of polyhydroxy carboxylic acids was altered using various ratios with Cu(II) to form complexes in solution, and this led to proposing a hypothesis for further study.

  1. Influence of Acidic pH on Hydrogen and Acetate Production by an Electrosynthetic Microbiome

    PubMed Central

    LaBelle, Edward V.; Marshall, Christopher W.; Gilbert, Jack A.; May, Harold D.

    2014-01-01

    Production of hydrogen and organic compounds by an electrosynthetic microbiome using electrodes and carbon dioxide as sole electron donor and carbon source, respectively, was examined after exposure to acidic pH (∼5). Hydrogen production by biocathodes poised at −600 mV vs. SHE increased>100-fold and acetate production ceased at acidic pH, but ∼5–15 mM (catholyte volume)/day acetate and>1,000 mM/day hydrogen were attained at pH ∼6.5 following repeated exposure to acidic pH. Cyclic voltammetry revealed a 250 mV decrease in hydrogen overpotential and a maximum current density of 12.2 mA/cm2 at −765 mV (0.065 mA/cm2 sterile control at −800 mV) by the Acetobacterium-dominated community. Supplying −800 mV to the microbiome after repeated exposure to acidic pH resulted in up to 2.6 kg/m3/day hydrogen (≈2.6 gallons gasoline equivalent), 0.7 kg/m3/day formate, and 3.1 kg/m3/day acetate ( = 4.7 kg CO2 captured). PMID:25333313

  2. Influence of acidic pH on hydrogen and acetate production by an electrosynthetic microbiome

    DOE PAGES

    LaBelle, Edward V.; Marshall, Christopher W.; Gilbert, Jack A.; ...

    2014-10-15

    Production of hydrogen and organic compounds by an electrosynthetic microbiome using electrodes and carbon dioxide as sole electron donor and carbon source, respectively, was examined after exposure to acidic pH (~5). Hydrogen production by biocathodes poised at -600 mV vs. SHE increased>100-fold and acetate production ceased at acidic pH, but ~5–15 mM (catholyte volume)/day acetate and>1,000 mM/day hydrogen were attained at pH ~6.5 following repeated exposure to acidic pH. Cyclic voltammetry revealed a 250 mV decrease in hydrogen overpotential and a maximum current density of 12.2 mA/cm 2 at -765 mV (0.065 mA/cm 2 sterile control at -800 mV) bymore » the Acetobacterium-dominated community. Supplying -800 mV to the microbiome after repeated exposure to acidic pH resulted in up to 2.6 kg/m 3/day hydrogen (≈2.6 gallons gasoline equivalent), 0.7 kg/m 3/day formate, and 3.1 kg/m 3/day acetate ( = 4.7 kg CO 2 captured).« less

  3. On the inhibition of muscle membrane chloride conductance by aromatic carboxylic acids

    PubMed Central

    Palade, PT; Barchi, RL

    1977-01-01

    25 aromatic carboxylic acids which are analogs of benzoic acid were tested in the rat diaphragm preparation for effects on chloride conductance (G(Cl)). Of the 25, 19 were shown to reduce membrane G(Cl) with little effect on other membrane parameters, although their apparent K(i) varied widely. This inhibition was reversible if exposure times were not prolonged. The most effective analog studied was anthracene-9-COOH (9-AC; K(i) = 1.1 x 10(-5) M). Active analogs produced concentration-dependent inhibition of a type consistent with interaction at a single site or group of sites having similar binding affinities, although a correlation could also be shown between lipophilicity and K(i). Structure-activity analysis indicated that hydrophobic ring substitution usually increased inhibitory activity while para polar substitutions reduced effectiveness. These compounds do not appear to inhibit G(Cl) by altering membrane surface charge and the inhibition produced is not voltage dependent. Qualitative characteristics of the I-V relationship for Cl(-) current are not altered. Conductance to all anions is not uniformly altered by these acids as would be expected from steric occlusion of a common channel. Concentrations of 9-AC reducing G(Cl) by more than 90 percent resulted in slight augmentation of G(I). The complete conductance sequence obtained at high levels of 9-AC was the reverse of that obtained under control conditions. Permeability sequences underwent progressive changes with increasing 9-AC concentration and ultimately inverted at high levels of the analog. Aromatic carboxylic acids appear to inhibit G(Cl) by binding to a specific intramembrane site and altering the selectivity sequence of the membrane anion channel. PMID:894246

  4. Co-administration of α-lipoic acid and cyclosporine aggravates colon ulceration of acetic acid-induced ulcerative colitis via facilitation of NO/COX-2/miR-210 cascade

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

    El-Gowelli, Hanan M., E-mail: dr_Hanan_el_gowali@hotmail.com; Saad, Evan I.; Abdel-Galil, Abdel-Galil A.

    In this work, α-lipoic acid and cyclosporine demonstrated significant protection against acetic acid-induced ulcerative colitis in rats. We proposed that α-lipoic acid and cyclosporine co-administration might modulate their individual effects. Induction of ulcerative colitis in rats was performed by intra-rectal acetic acid (5% v/v) administration for 3 consecutive days. Effects of individual or combined used of α-lipoic acid (35 mg/kg ip) or cyclosporine (5 mg/kg sc) for 6 days starting 2 days prior to acetic acid were assessed. Acetic acid caused colon ulceration, bloody diarrhea and weight loss. Histologically, there was mucosal atrophy and inflammatory cells infiltration in submucosa, associatedmore » with depletion of colon reduced glutathione, superoxide dismutase and catalase activities and elevated colon malondialdehyde, serum C-reactive protein (C-RP) and tumor necrosis factor-α (TNF-α). Colon gene expression of cyclooxygenase-2 and miR-210 was also elevated. These devastating effects of acetic acid were abolished upon concurrent administration of α-lipoic acid. Alternatively, cyclosporine caused partial protection against acetic acid-induced ulcerative colitis. Cyclosporine did not restore colon reduced glutathione, catalase activity, serum C-RP or TNF-α. Unexpectedly, co-administration of α-lipoic acid and cyclosporine aggravated colon ulceration. Concomitant use of α-lipoic acid and cyclosporine significantly increased nitric oxide production, cyclooxygenase-2 and miR-210 gene expression compared to all other studied groups. The current findings suggest that facilitation of nitric oxide/cyclooxygenase-2/miR-210 cascade constitutes, at least partially, the cellular mechanism by which concurrent use of α-lipoic acid and cyclosporine aggravates colon damage. Collectively, the present work highlights the probable risk of using α-lipoic acid/cyclosporine combination in ulcerative colitis patients. - Highlights: • Lipoic acid is more effective

  5. Structure-Activity Relationship Study of Ionotropic Glutamate Receptor Antagonist (2S,3R)-3-(3-Carboxyphenyl)pyrrolidine-2-carboxylic Acid.

    PubMed

    Krogsgaard-Larsen, Niels; Storgaard, Morten; Møller, Charlotte; Demmer, Charles S; Hansen, Jeanette; Han, Liwei; Monrad, Rune N; Nielsen, Birgitte; Tapken, Daniel; Pickering, Darryl S; Kastrup, Jette S; Frydenvang, Karla; Bunch, Lennart

    2015-08-13

    Herein we describe the first structure-activity relationship study of the broad-range iGluR antagonist (2S,3R)-3-(3-carboxyphenyl)pyrrolidine-2-carboxylic acid (1) by exploring the pharmacological effect of substituents in the 4, 4', or 5' positions and the bioisosteric substitution of the distal carboxylic acid for a phosphonic acid moiety. Of particular interest is a hydroxyl group in the 4' position 2a which induced a preference in binding affinity for homomeric GluK3 over GluK1 (Ki = 0.87 and 4.8 μM, respectively). Two X-ray structures of ligand binding domains were obtained: 2e in GluA2-LBD and 2f in GluK1-LBD, both at 1.9 Å resolution. Compound 2e induces a D1-D2 domain opening in GluA2-LBD of 17.3-18.8° and 2f a domain opening in GluK1-LBD of 17.0-17.5° relative to the structures with glutamate. The pyrrolidine-2-carboxylate moiety of 2e and 2f shows a similar binding mode as kainate. The 3-carboxyphenyl ring of 2e and 2f forms contacts comparable to those of the distal carboxylate in kainate.

  6. Isolation and Characterization of Esters of Indole-3-Acetic Acid from the Liquid Endosperm of the Horse Chestnut (Aesculus species) 1

    PubMed Central

    Domagalski, Wojciech; Schulze, Aga; Bandurski, Robert S.

    1987-01-01

    Esters of indole-3-acetic acid were extracted and purified from the liquid endosperm of immature fruits of various species of the horse chestnut (Aesculus parviflora, A. baumanni, A.pavia rubra, and A. pavia humulis). The liquid endosperm contained, at least 12 chromatographically distinct esters. One of these compounds was purified and characterized as an ester of indole-3-acetic acid and myo-inositol. A second compound was found to be an ester of indole-3-acetic acid and the disaccharide rutinose (glucosyl-rhamnose). A third compound was partially characterized as an ester of indole-3-acetic acid and a desoxyaminohexose. PMID:11539676

  7. Solubility of small-chain carboxylic acids in supercritical carbon dioxide

    DOE PAGES

    Sparks, Darrell L.; Estevez, L. Antonio; Hernandez, Rafael; ...

    2010-07-08

    The solubility of heptanoic acid and octanoic acid in supercritical carbon dioxide has been determined at temperatures of (313.15, 323.15, and 333.15) K over a pressure range of (8.5 to 30.0) MPa, depending upon the solute. The solubility of heptanoic acid ranged from a solute concentration of (0.08 ± 0.03) kg • m -3 (T = 323.15 K, p = 8.5 MPa) to (147 ± 0.2) kg • m -3 (T = 323.15 K, p = 20.0 MPa). The lowest octanoic acid solubility obtained was a solute concentration of (0.40 ± 0.1) kg • m -3 (T = 333.15 K,more » p = 10.0 MPa), while the highest solute concentration was (151 ± 2) kg • m -3 (T = 333.15 K, p = 26.7 MPa). In addition, solubility experiments were performed for nonanoic acid in supercritical carbon dioxide at 323.15 K and pressures of (10.0 to 30.0) MPa to add to the solubility data previously published by the authors. In general, carboxylic acid solubility increased with increasing solvent density. The results also showed that the solubility of the solutes decreased with increasing molar mass at constant supercritical-fluid density. Additionally, the efficacy of Chrastil's equation and other density-based models was evaluated for each fatty acid.« less

  8. Condensation of acetol and acetic acid vapor with sprayed liquid

    USDA-ARS?s Scientific Manuscript database

    A cellulose-derived fraction of biomass pyrolysis vapor was simulated by evaporating acetol and acetic acid (AA) from flasks on a hot plate. The liquid in the flasks was infused with heated nitrogen. The vapor/nitrogen stream was superheated in a tube oven and condensed by contact with a cloud of ...

  9. Evaluation of sanitizing efficacy of acetic acid on Piper betle leaves and its effect on antioxidant properties.

    PubMed

    Singla, Richu; Ganguli, Abhijit; Ghosh, Moushumi; Sohal, Sapna

    2009-01-01

    The sanitizing efficacy of acetic acid and its effect on health beneficial properties of Piper betle leaves were determined. Betel leaves artificially inoculated with Aeromonas, Salmonella and Yersinia were subjected to organic acid (citric acid, acetic acid and lactic acid) treatment. Pathogen populations reduced by 4 log upon individual inoculation and up to 2 log in a mixed cocktail following treatment with 2% acetic acid during storage up to 20 h at 28 degrees C, indicating a residual antimicrobial effect on pathogen during storage. Antioxidant potential ethanolic extracts of both raw and treated P. betle leaves were assayed for free radical scavenging activities against 2,2-diphenyl-1-picryhydrazyl. Polyphenols, flavonoids and the reducing power of treated and untreated P. betle were also compared. No significant (P>0.05) changes were observed in antioxidant status; flavonoids, polyphenols and reducing power of treated betel leaves. Results indicate the feasibility of a simple intervention strategy for inactivating pathogens in edible leaves of P. betle.

  10. Elemental sulfur and acetate can support life of a novel strictly anaerobic haloarchaeon

    PubMed Central

    Sorokin, Dimitry Y; Kublanov, Ilya V; Gavrilov, Sergei N; Rojo, David; Roman, Pawel; Golyshin, Peter N; Slepak, Vladlen Z; Smedile, Francesco; Ferrer, Manuel; Messina, Enzo; La Cono, Violetta; Yakimov, Michail M

    2016-01-01

    Archaea domain is comprised of many versatile taxa that often colonize extreme habitats. Here, we report the discovery of strictly anaerobic extremely halophilic euryarchaeon, capable of obtaining energy by dissimilatory reduction of elemental sulfur using acetate as the only electron donor and forming sulfide and CO2 as the only products. This type of respiration has never been observed in hypersaline anoxic habitats and is the first example of such metabolic capability in the entire Archaea domain. We isolated and cultivated these unusual organisms, selecting one representative strain, HSR2, for detailed characterization. Our studies including physiological tests, genome sequencing, gene expression, metabolomics and [14C]-bicarbonate assimilation assays revealed that HSR2 oxidized acetate completely via the tricarboxylic acid cycle. Anabolic assimilation of acetate occurred via activated glyoxylate bypass and anaplerotic carboxylation. HSR2 possessed sulfurtransferase and an array of membrane-bound polysulfide reductase genes, all of which were expressed during the growth. Our findings suggest the biogeochemical contribution of haloarchaea in hypersaline anoxic environments must be reconsidered. PMID:25978546

  11. Lead acetate trihydrate precursor route to synthesize novel ultrafine lead oxide from spent lead acid battery pastes

    NASA Astrophysics Data System (ADS)

    Sun, Xiaojuan; Yang, Jiakuan; Zhang, Wei; Zhu, Xinfeng; Hu, Yuchen; Yang, Danni; Yuan, Xiqing; Yu, Wenhao; Dong, Jinxin; Wang, Haifeng; Li, Lei; Vasant Kumar, R.; Liang, Sha

    2014-12-01

    A novel green recycling process is investigated to prepare lead acetate trihydrate precursors and novel ultrafine lead oxide from spent lead acid battery pastes. The route contains the following four processes. (1) The spent lead pastes are desulphurized by (NH4)2CO3. (2) The desulphurized pastes are converted into lead acetate solution by leaching with acetic acid solution and H2O2; (3) The Pb(CH3COO)2·3H2O precursor is crystallized and purified from the lead acetate solution with the addition of glacial acetic acid; (4) The novel ultrafine lead oxide is prepared by the calcination of lead acetate trihydrate precursor in N2 or air at 320-400 °C. Both the lead acetate trihydrate and lead oxide products are characterized by TG-DTA, XRD, and SEM techniques. The calcination products are mainly α-PbO, β-PbO, and a small amount of metallic Pb. The particle size of the calcination products in air is significantly larger than that in N2. Cyclic voltammetry measurements of the novel ultrafine lead oxide products show good reversibility and cycle stability. The assembled batteries using the lead oxide products as cathode active materials show a good cyclic stability in 80 charge/discharge cycles with the depth of discharge (DOD) of 100%.

  12. Short Carboxylic Acid–Carboxylate Hydrogen Bonds Can Have Fully Localized Protons

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

    Lin, Jiusheng; Pozharski, Edwin; Wilson, Mark A.

    Short hydrogen bonds (H-bonds) have been proposed to play key functional roles in several proteins. The location of the proton in short H-bonds is of central importance, as proton delocalization is a defining feature of low-barrier hydrogen bonds (LBHBs). Experimentally determining proton location in H-bonds is challenging. Here, bond length analysis of atomic (1.15–0.98 Å) resolution X-ray crystal structures of the human protein DJ-1 and its bacterial homologue, YajL, was used to determine the protonation states of H-bonded carboxylic acids. DJ-1 contains a buried, dimer-spanning 2.49 Å H-bond between Glu15 and Asp24 that satisfies standard donor–acceptor distance criteria for amore » LBHB. Bond length analysis indicates that the proton is localized on Asp24, excluding a LBHB at this location. However, similar analysis of the Escherichia coli homologue YajL shows both residues may be protonated at the H-bonded oxygen atoms, potentially consistent with a LBHB. A Protein Data Bank-wide screen identifies candidate carboxylic acid H-bonds in approximately 14% of proteins, which are typically short [O–O> = 2.542(2) Å]. Chemically similar H-bonds between hydroxylated residues (Ser/Thr/Tyr) and carboxylates show a trend of lengthening O–O distance with increasing H-bond donor pK a. This trend suggests that conventional electronic effects provide an adequate explanation for short, charge-assisted carboxylic acid–carboxylate H-bonds in proteins, without the need to invoke LBHBs in general. This study demonstrates that bond length analysis of atomic resolution X-ray crystal structures provides a useful experimental test of certain candidate LBHBs.« less

  13. Validation of a multi-analyte HPLC-DAD method for determination of uric acid, creatinine, homovanillic acid, niacinamide, hippuric acid, indole-3-acetic acid and 2-methylhippuric acid in human urine.

    PubMed

    Remane, Daniela; Grunwald, Soeren; Hoeke, Henrike; Mueller, Andrea; Roeder, Stefan; von Bergen, Martin; Wissenbach, Dirk K

    2015-08-15

    During the last decades exposure sciences and epidemiological studies attracts more attention to unravel the mechanisms for the development of chronic diseases. According to this an existing HPLC-DAD method for determination of creatinine in urine samples was expended for seven analytes and validated. Creatinine, uric acid, homovanillic acid, niacinamide, hippuric acid, indole-3-acetic acid, and 2-methylhippuric acid were separated by gradient elution (formate buffer/methanol) using an Eclipse Plus C18 Rapid Resolution column (4.6mm×100mm). No interfering signals were detected in mobile phase. After injection of blank urine samples signals for the endogenous compounds but no interferences were detected. All analytes were linear in the selected calibration range and a non weighted calibration model was chosen. Bias, intra-day and inter-day precision for all analytes were below 20% for quality control (QC) low and below 10% for QC medium and high. The limits of quantification in mobile phase were in line with reported reference values but had to be adjusted in urine for homovanillic acid (45mg/L), niacinamide 58.5(mg/L), and indole-3-acetic acid (63mg/L). Comparison of creatinine data obtained by the existing method with those of the developed method showing differences from -120mg/L to +110mg/L with a mean of differences of 29.0mg/L for 50 authentic urine samples. Analyzing 50 authentic urine samples, uric acid, creatinine, hippuric acid, and 2-methylhippuric acid were detected in (nearly) all samples. However, homovanillic acid was detected in 40%, niacinamide in 4% and indole-3-acetic acid was never detected within the selected samples. Copyright © 2015 Elsevier B.V. All rights reserved.

  14. Identification and characterization of thermotolerant acetic acid bacteria strains isolated from coconut water vinegar in Sri Lanka.

    PubMed

    Perumpuli, P A B N; Watanabe, Taisuke; Toyama, Hirohide

    2014-01-01

    From the pellicle formed on top of brewing coconut water vinegar in Sri Lanka, three Acetobacter strains (SL13E-2, SL13E-3, and SL13E-4) that grow at 42 °C and four Gluconobacter strains (SL13-5, SL13-6, SL13-7, and SL13-8) grow at 37 °C were identified as Acetobacter pasteurianus and Gluconobacter frateurii, respectively. Acetic acid production by the isolated Acetobacter strains was examined. All three strains gave 4% acetic acid from 6% initial ethanol at 37 °C, and 2.5% acetic acid from 4% initial ethanol at 40 °C. Compared with the two other strains, SL13E-4 showed both slower growth and slower acetic acid production. As well as the thermotolerant SKU1108 strain, the activities of the alcohol dehydrogenase and the aldehyde dehydrogenase of SL13E-2 and SL13E-4 were more stable than those of the mesophilic strain. The isolated strains were used to produce coconut water vinegar at higher temperatures than typically used for vinegar production.

  15. Tailored and integrated production of carboxylated cellulose nanocrystals (CNC) with nanofibrils (CNF) through maleic acid hydrolysis

    Treesearch

    Ruibin Wang; Liheng Chen; J.Y. Zhu; Rendang Yang

    2017-01-01

    This study demonstrates the feasibility of tailored and integrated production of carboxylated cellulose nanocrystals (CNC) with nanofibrils (CNF) from bleached pulp fibers through hydrolysis using a recyclable dicarboxylic acid. Hydrolysis experiments were conducted using ranges of 15–75 wt% maleic acid concentrations, 60–120°C temperatures, and 5–300 min reaction...

  16. Investigation of Pyridine Carboxylic Acids in CM2 Carbonaceous Chondrites: Potential Precursor Molecules for Ancient Coenzymes

    NASA Technical Reports Server (NTRS)

    Smith, Karen E.; Callahan, Michael P.; Gerakines, Perry A.; Dworkin, Jason P.; House, Christopher H.

    2014-01-01

    The distribution and abundances of pyridine carboxylic acids (including nicotinic acid) in eight CM2 carbonaceous chondrites (ALH 85013, DOM 03183, DOM 08003, EET 96016, LAP 02333, LAP 02336, LEW 85311, and WIS 91600) were investigated by liquid chromatography coupled to UV detection and high resolution Orbitrap mass spectrometry. We find that pyridine monocarboxylic acids are prevalent in CM2-type chondrites and their abundance negatively correlates with the degree of pre-terrestrial aqueous alteration that the meteorite parent body experienced. We lso report the first detection of pyridine dicarboxylic acids in carbonaceous chondrites. Additionally, we carried out laboratory studies of proton-irradiated pyridine in carbon dioxide-rich ices (a 1:1 mixture) to serve as a model of the interstellar ice chemistry that may have led to the synthesis of pyridine carboxylic acids. Analysis of the irradiated ice residue shows that a comparable suite of pyridine mono- and dicarboxylic acids was produced, although aqueous alteration may still play a role in the synthesis (and ultimate yield) of these compounds in carbonaceous meteorites. Nicotinic acid is a precursor to nicotinamide adenine dinucleotide, a likely ancient molecule used in cellular metabolism in all of life, and its common occurrence in CM2 chondrites may indicate that meteorites may have been a source of molecules for the emergence of more complex coenzymes on the early Earth.

  17. Investigation of Pyridine Carboxylic Acids in CM2 Carbonaceous Chondrites: Potential Precursor Molecules for Ancient Coenzymes

    NASA Technical Reports Server (NTRS)

    Smith, Karen E.; Callahan, Michael P.; Gerakines, Perry A.; Dworkin, Jason P.; House, Christopher H.

    2014-01-01

    The distribution and abundances of pyridine carboxylic acids (including nicotinic acid) in eight CM2 carbonaceous chondrites (ALH 85013, DOM 03183, DOM 08003, EET 96016, LAP 02333, LAP 02336, LEW 85311, and WIS 91600) were investigated by liquid chromatography coupled to UV detection and high resolution Orbitrap mass spectrometry. We find that pyridine monocarboxylic acids are prevalent in CM2-type chondrites and their abundance negatively correlates with the degree of pre-terrestrial aqueous alteration that the meteorite parent body experienced. We also report the first detection of pyridine dicarboxylic acids in carbonaceous chondrites. Additionally, we carried out laboratory studies of proton-irradiated pyridine in carbon dioxide-rich ices (a 1:1 mixture) to serve as a model of the interstellar ice chemistry that may have led to the synthesis of pyridine carboxylic acids. Analysis of the irradiated ice residue shows that a comparable suite of pyridine mono- and dicarboxylic acids was produced, although aqueous alteration may still play a role in the synthesis (and ultimate yield) of these compounds in carbonaceous meteorites. Nicotinic acid is a precursor to nicotinamide adenine dinucleotide, a likely ancient molecule used in cellular metabolism in all of life, and its common occurrence in CM2 chondrites may indicate that meteorites may have been a source of molecules for the emergence of more complex coenzymes on the early Earth.

  18. 40 CFR 721.2076 - D-Glucuronic acid, polymer with 6-deoxy-L-mannose and D-glucose, acetate, calcium magnesium...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false D-Glucuronic acid, polymer with 6...-Glucuronic acid, polymer with 6-deoxy-L-mannose and D-glucose, acetate, calcium magnesium potassium sodium... identified as D-Glucuronic acid, polymer with 6-deoxy-L-mannose and D-glucose, acetate, calcium magnesium...

  19. Direct amidation of carboxylic acids catalyzed by ortho-iodo arylboronic acids: catalyst optimization, scope, and preliminary mechanistic study supporting a peculiar halogen acceleration effect.

    PubMed

    Gernigon, Nicolas; Al-Zoubi, Raed M; Hall, Dennis G

    2012-10-05

    The importance of amides as a component of biomolecules and synthetic products motivates the development of catalytic, direct amidation methods employing free carboxylic acids and amines that circumvent the need for stoichiometric activation or coupling reagents. ortho-Iodophenylboronic acid 4a has recently been shown to catalyze direct amidation reactions at room temperature in the presence of 4A molecular sieves as dehydrating agent. Herein, the arene core of ortho-iodoarylboronic acid catalysts has been optimized with regards to the electronic effects of ring substitution. Contrary to the expectation, it was found that electron-donating substituents are preferable, in particular, an alkoxy substituent positioned para to the iodide. The optimal new catalyst, 5-methoxy-2-iodophenylboronic acid (MIBA, 4f), was demonstrated to be kinetically more active than the parent des-methoxy catalyst 4a, providing higher yields of amide products in shorter reaction times under mild conditions at ambient temperature. Catalyst 4f is recyclable and promotes the formation of amides from aliphatic carboxylic acids and amines, and from heteroaromatic carboxylic acids and other functionalized substrates containing moieties like a free phenol, indole and pyridine. Mechanistic studies demonstrated the essential role of molecular sieves in this complex amidation process. The effect of substrate stoichiometry, concentration, and measurement of the catalyst order led to a possible catalytic cycle based on the presumed formation of an acylborate intermediate. The need for an electronically enriched ortho-iodo substituent in catalyst 4f supports a recent theoretical study (Marcelli, T. Angew. Chem. Int. Ed.2010, 49, 6840-6843) with a purported role for the iodide as a hydrogen-bond acceptor in the orthoaminal transition state.

  20. Commandant’s International Technical Series. Volume 9. International Regulations on the Prevention of Pollution from Ships Carrying Hazardous Chemicals in Bulk.

    DTIC Science & Technology

    1985-12-01

    Styrene monomer 2055 B Sulphuric acid 1830 C " Sulphuric acid, spent 1832 C - Sulphurous acid 1633 (C) Sunflover oil D...anhydrides (e.g. formic, acetic); .3 halogenated carboxylic acids (e.g. chloracetic); .4 sulpnonic acids (e.g. benzene sulphonic); .5 caustic alkalis...acetic); (iii) halogenated carboxylic acids (e.g. cbloracetic); (iv) sulphonic acids (e.g. benzene sulphonic);II (v) caustic alkalis (e.g. sodium

  1. Integrated production of lignin containing cellulose nanocrystals (LCNC) and nanofibrils (LCNF) using an easily recyclable di-carboxylic acid

    Treesearch

    Huiyang Bian; Liheng Chen; Hongqi Dai; J.Y. Zhu

    2017-01-01

    Here we demonstrate di-carboxylic acid hydrolysis for the integrated production of lignin containing cellulose nanocrystals (LCNC) and nanofibrils (LCNF) using two unbleached hardwood chemical pulps of lignin contents of 3.9 and 17.2%. Acid hydrolysis experiments used maleic acid solution of 60 wt% concentration at 120°C for 120 min under ambient pressure. Yields of...

  2. Simultaneous determination of C1-C4 carboxylic acids and aldehydes using 2,4-dinitrophenylhydrazine-impregnated silica gel and high-performance liquid chromatography.

    PubMed

    Uchiyama, Shigehisa; Matsushima, Erika; Aoyagi, Shohei; Ando, Masanori

    2004-10-01

    A new method for the simultaneous determination of aliphatic carboxylic acids and aldehydes in air is described. In this work, carboxylic acids were allowed to react with 2,4-dinitrophenylhydrazine (DNPH) to form the corresponding carboxylic 2,4-dinitrophenylhydrazides. These derivatives have excellent thermal stability, with melting points higher than those of the corresponding hydrazones by 32-50 degrees C. C1-C4 carboxylic acid 2,4-dinitrophenylhydrazides exhibited maximum absorption wavelengths of 331-334 nm and molar absorption coefficients of 1.4 x 10(4) L/mol/cm. They were completely separated by high-performance liquid chromatography (HPLC) with an RP-Amide C16 column. Cartridges packed with DNPH-coated silica particles (DNPH cartridge) were used for sampling formic acid and aldehydes. Formic acid was physically adsorbed on the silica particles as the first step of the sampling mechanism. Gradual reaction with DNPH followed. Formic acid reacted very slowly with DNPH at room temperature (20 degrees C), but reacted completely at 80 degrees C over 4 h. In field measurements, the sample air was drawn through a DNPH cartridge. After sampling, the cartridges were heated at 80 degrees C for 5 h and extracted with acetonitrile for HPLC analysis. Under these optimized conditions, the LOD is 0.4 ug/m(3) for an air sample collected for 24 h at 100 mL/min (144 L).

  3. Microwave Spectroscopy and Proton Transfer Dynamics in the Formic Acid-Acetic Acid Dimer

    NASA Astrophysics Data System (ADS)

    Howard, B. J.; Steer, E.; Page, F.; Tayler, M.; Ouyang, B.; Leung, H. O.; Marshall, M. D.; Muenter, J. S.

    2012-06-01

    The rotational spectrum of the doubly hydrogen-bonded {hetero} dimer formed between formic acid and acetic acid has been recorded between 4 and 18 GHz using a pulsed-nozzle Fourier transform microwave spectrometer. Each rigid-molecule rotational transition is split into four as a result of two concurrent tunnelling motions, one being proton transfer between the two acid molecules, and the other the torsion/rotation of the methyl group within the acetic acid. We present a full assignment of the spectrum for {J} = 1 to {J} = 7 for these four torsion/tunnelling states. Spectra have been observed for the main isotopic species, with deuterium substitution at the C of the formic acid and all 13C species in natural abundance, The observed transitions are fitted to within a few kilohertz using a molecule-fixed effective rotational Hamiltonian for the separate {A} and {E} vibrational species of the G12 permutation-inversion group which is applicable to this complex. To reduce the effects of internal angular momentum, a non-principal axis system is used throughout. Interpretation of the internal motion uses an internal-vibration and overall rotation scheme, and full sets of rotational and centrifugal distortion constants are determined. The proton tunnelling rates and the internal angular momentum of the methyl group in the {E} states is interpreted in terms of a dynamical model which involves coupled proton transfer and internal rotation. The resulting potential energy surface not only describes these internal motions, but can also explain the observed shifts in rotational constants between {A} and {E} species, and the deviations of the tunnelling frequencies from the expected 2:1 ratio. It also permits the determination of spectral constants free from the contamination effects of the internal dynamics. M.C.D. Tayler, B. Ouyang and B.J. Howard, J. Chem. Phys., {134}, 054316 (2011).

  4. ANALYSIS OF AIRBORNE CARBOXYLIC ACIDS AND PHENOLS AS THEIR PENTAFLUOROBENZYL DERIVATIVES: GAS CHROMATOGRAPHY/ION TRAP MASS SPECTROMETRY WITH A NOVEL CHEMICAL IONIZATION REAGENT, PFBOH. (R826247)

    EPA Science Inventory

    The complex photochemical transformations of biogenic
    hydrocarbons such as isoprene and of anthropogenic
    hydrocarbons such as aromatics are an important source
    of carboxylic acids in the troposphere. The
    identification
    of unknown carboxylic acids can be difficul...

  5. Effect of carboxylic acids as compatibilizer agent on mechanical properties of thermoplastic starch and polypropylene blends.

    PubMed

    Martins, Andréa Bercini; Santana, Ruth Marlene Campomanes

    2016-01-01

    In this work, polypropylene/thermoplastic starch (PP/TPS) blends were prepared as an alternative material to use in disposable packaging, reducing the negative polymeric environmental impact. Unfortunately, this material displays morphological characteristics typical of immiscible polymer blends and a compatibilizer agent is needed. Three different carboxyl acids: myristic (C14), palmitic (C16) and stearic acids (C18) were used as natural compatibilizer agent (NCA). The effects of NCA on the mechanical, physical, thermal and morphological properties of PP/TPS blends were investigated and compared against PP/TPS with and without PP-grafted maleic anhydride (PPgMA). When compared to PP/TPS, blends with C18, PPgMA and C14 presented an improvement of 25, 22 and 17% in tensile strength at break and of 180, 194 and 259% in elongation at break, respectively. The highest increase, 54%, in the impact strength was achieved with C14 incorporation. Improvements could be seen, through scanning electron microscopy (SEM) images, in the compatibility between the immiscible components by acids incorporation. These results showed that carboxylic acids, specifically C14, could be used as compatibilizer agent and could substitute PPgMA. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. Conformational characterization of the 1-aminocyclobutane-1-carboxylic acid residue in model peptides.

    PubMed

    Gatos, M; Formaggio, F; Crisma, M; Toniolo, C; Bonora, G M; Benedetti, Z; Di Blasio, B; Iacovino, R; Santini, A; Saviano, M; Kamphuis, J

    1997-01-01

    A series of N- and C-protected, monodispersed homo-oligopeptides (to the dodecamer level) from the small-ring alicyclic C alpha, alpha-dialkylated glycine 1-aminocyclobutane-1-carboxylic acid (Ac4c) and two Ala/Ac4c tripeptides were synthesized by solution methods and fully characterized. The conformational preferences of all the model peptides were determined in deuterochloroform solution by FT-IR absorption and 1H-NMR. The molecular structures of the amino acid derivatives Z-Ac4c-OH and Z2-Ac4c-OH, the tripeptides Z-(Ac4c)3-OtBu, Z-Ac4c-(L-Ala)2-OMe and Z-L-Ala-Ac4c-L-Ala-OMe, and the tetrapeptide Z-(Ac4c)4-OtBu were determined in the crystal state by X-ray diffraction. The average geometry of the cyclobutyl moiety of the Ac4c residue was assessed and the tau(N-C alpha-C') bond angle was found to be significantly expanded from the regular tetrahedral value. The conformational data are strongly in favour of the conclusion that the Ac4c residue is an effective beta-turn and helix former. A comparison with the structural propensities of alpha-aminoisobutyric acid, the prototype of C alpha, alpha-dialkylated glycines, and the other extensively investigated members of the family of 1-aminocycloalkane-1-carboxylic acids (Acnc, with n = 3, 5-8) is made and the implications for the use of the Ac4c residue in conformationally constrained peptide analogues are briefly examined.

  7. Stereospecific synthesis of syn-α-oximinoamides by a three-component reaction of isocyanides, syn-chlorooximes, and carboxylic acids.

    PubMed

    Pirali, Tracey; Mossetti, Riccardo; Galli, Simona; Tron, Gian Cesare

    2011-07-15

    A stereospecific multicomponent reaction among isocyanides, syn-chlorooximes, and carboxylic acids provides an efficient synthesis of biologically relevant syn-α-oximinoamides. © 2011 American Chemical Society

  8. Copper coordination polymers constructed from thiazole-5-carboxylic acid: Synthesis, crystal structures, and structural transformation

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

    Meundaeng, Natthaya; Rujiwatra, Apinpus; Prior, Timothy J., E-mail: t.prior@hull.ac.uk

    2017-01-15

    We have successfully prepared crystals of thiazole-5-carboxylic acid (5-Htza) (L) and three new thiazole-5-carboxylate-based Cu{sup 2+} coordination polymers with different dimensionality, namely, 1D [Cu{sub 2}(5-tza){sub 2}(1,10-phenanthroline){sub 2}(NO{sub 3}){sub 2}] (1), 2D [Cu(5-tza){sub 2}(MeOH){sub 2}] (2), and 3D [Cu(5-tza){sub 2}]·H{sub 2}O (3). These have been characterized by single crystal X-ray diffraction and thermogravimetry. Interestingly, the 2D network structure of 2 can directly transform into the 3D framework of 3 upon removal of methanol molecules at room temperature. 2 can also undergo structural transformation to produce the same 2D network present in the known [Cu(5-tza){sub 2}]·1.5H{sub 2}O upon heat treatment for 2more » h. This 2D network can adsorb water and convert to 3 upon exposure to air. - Highlights: • Rare examples of coordination polymers of thiazole-5-carboxylic acid were prepared. • Non-covalent interactions play a key role on the assembly of the complexes in solid state. • Structural transformation of a 2D framework to a 3D upon removal of methanol is observed.« less

  9. Amino- and carboxyl-terminal amino acid sequences of proteins coded by gag gene of murine leukemia virus

    PubMed Central

    Oroszlan, Stephen; Henderson, Louis E.; Stephenson, John R.; Copeland, Terry D.; Long, Cedric W.; Ihle, James N.; Gilden, Raymond V.

    1978-01-01

    The amino- and carboxyl-terminal amino acid sequences of proteins (p10, p12, p15, and p30) coded by the gag gene of Rauscher and AKR murine leukemia viruses were determined. Among these proteins, p15 from both viruses appears to have a blocked amino end. Proline was found to be the common NH2 terminus of both p30s and both p12s, and alanine of both p10s. The amino-terminal sequences of p30s are identical, as are those of p10s, while the p12 sequences are clearly distinctive but also show substantial homology. The carboxyl-terminal amino acids of both viral p30s and p12s are leucine and phenylalanine, respectively. Rauscher leukemia virus p15 has tyrosine as the carboxyl terminus while AKR virus p15 has phenylalanine in this position. The compositional and sequence data provide definite chemical criteria for the identification of analogous gag gene products and for the comparison of viral proteins isolated in different laboratories. On the basis of amino acid sequences and the previously proposed H-p15-p12-p30-p10-COOH peptide sequence in the precursor polyprotein, a model for cleavage sites involved in the post-translational processing of the precursor coded for by the gag gene is proposed. PMID:206897

  10. The Effects of Benzofuran-2-Carboxylic Acid Derivatives as Countermeasures in Immune Modulation and Cancer Cell Inhibition

    NASA Astrophysics Data System (ADS)

    Sundaresan, A.; Marriott, K.; Mao, J.; Bhuiyan, S.; Denkins, P.

    2015-06-01

    Microgravity and radiation exposure experienced during space flights result in immune system suppression. In long-term spaceflight, the crew is exposed to space radiation, microgravity, infectious agents from other crew members, and microbial contamination, all of which have a significant impact on the body's immune system and may contribute to the development of autoimmune diseases, allergic reactions, and/or cancer initiation. Many studies have revealed strong effects of microgravity on immune cell function, and microgravity is now considered as one of the major causes of immune dysfunction during space flight (Sundaresan, Int. J. Transp. Phenom. 12(1-2), 93-100, 2011; Martinelli et al., IEEE Eng. Biol. Med. 28(4), 85-90, 2009). We screened two newly synthetized derivatives of benzofuran 2-carboxylic acid, KMEG and KM12. The former KMEG was assessed for lymphoproliferative activities while the latter, KM12, was used in an array of cancer cell lines for testing its cancer inhibiting effects. For ground-based studies, synthetic benzofuran-2-carboxylic acid derivatives were assessed for biological effects in several scenarios, which involved exposure to modeled microgravity and radiation, as well as their immune enhancement and anti-cancer effects. Initial findings indicate that the benzofuran-2-carboxylic acid derivatives possibly have immune enhancing and anti-tumor properties in human lymphocytes and cancer cells exposed to analog spaceflight conditions modeled microgravity and γ-radiation).

  11. Facile regio- and stereoselective hydrometalation of alkynes with a combination of carboxylic acids and group 10 transition metal complexes: selective hydrogenation of alkynes with formic acid.

    PubMed

    Shen, Ruwei; Chen, Tieqiao; Zhao, Yalei; Qiu, Renhua; Zhou, Yongbo; Yin, Shuangfeng; Wang, Xiangbo; Goto, Midori; Han, Li-Biao

    2011-10-26

    A facile, highly stereo- and regioselective hydrometalation of alkynes generating alkenylmetal complex is disclosed for the first time from a reaction of alkyne, carboxylic acid, and a zerovalent group 10 transition metal complex M(PEt(3))(4) (M = Ni, Pd, Pt). A mechanistic study showed that the hydrometalation does not proceed via the reaction of alkyne with a hydridometal generated by the protonation of a carboxylic acid with Pt(PEt(3))(4), but proceeds via a reaction of an alkyne coordinate metal complex with the acid. This finding clarifies the long proposed reaction mechanism that operates via the generation of an alkenylpalladium intermediate and subsequent transformation of this complex in a variety of reactions catalyzed by a combination of Brϕnsted acid and Pd(0) complex. This finding also leads to the disclosure of an unprecedented reduction of alkynes with formic acid that can selectively produce cis-, trans-alkenes and alkanes by slightly tuning the conditions.

  12. Temperature-programmed deoxygenation of acetic acid on molybdenum carbide catalysts

    DOE PAGES

    Nash, Connor P.; Farberow, Carrie A.; Hensley, Jesse E.

    2017-02-07

    Temperature programmed reaction (TPRxn) is a simple yet powerful tool for screening solid catalyst performance at a variety of conditions. A TPRxn system includes a reactor, furnace, gas and vapor sources, flow control, instrumentation to quantify reaction products (e.g., gas chromatograph), and instrumentation to monitor the reaction in real time (e.g., mass spectrometer). Here, we apply the TPRxn methodology to study molybdenum carbide catalysts for the deoxygenation of acetic acid, an important reaction among many in the upgrading/stabilization of biomass pyrolysis vapors. TPRxn is used to evaluate catalyst activity and selectivity and to test hypothetical reaction pathways (e.g., decarbonylation, ketonization,more » and hydrogenation). Furthermore, the results of the TPRxn study of acetic acid deoxygenation show that molybdenum carbide is an active catalyst for this reaction at temperatures above ca. 300 °C and that the reaction favors deoxygenation (i.e., C-O bond-breaking) products at temperatures below ca. 400 °C and decarbonylation (i.e., C-C bond-breaking) products at temperatures above ca. 400 °C.« less

  13. Acetic acid as a decontamination method for sink drains in a nosocomial outbreak of metallo-β-lactamase-producing Pseudomonas aeruginosa.

    PubMed

    Stjärne Aspelund, A; Sjöström, K; Olsson Liljequist, B; Mörgelin, M; Melander, E; Påhlman, L I

    2016-09-01

    Pseudomonas aeruginosa may colonize water systems via biofilm formation. In hospital environments, contaminated sinks have been associated with nosocomial transmission. Here we describe a prolonged outbreak of a metallo-β-lactamase-producing P. aeruginosa (Pae-MBL) associated with sink drains, and propose a previously unreported decontamination method with acetic acid. To describe a nosocomial outbreak of Pae-MBL associated with hospital sink drains and to evaluate acetic acid as a decontamination method. The outbreak was investigated by searching the microbiology database, microbiological sampling and strain typing. Antibacterial and antibiofilm properties of acetic acid were evaluated in vitro. Pae-MBL-positive sinks were treated with 24% acetic acid once weekly and monitored with repeated cultures. Fourteen patients with positive cultures for Pae-MBL were identified from 2008 to 2014. The patients had been admitted to three wards, where screening discovered Pae-MBL in 12 sink drains located in the patient bathrooms. Typing of clinical and sink drain isolates revealed identical or closely related strains. Pae-MBL biofilm was highly sensitive to acetic acid with a minimum biofilm eradication concentration of 0.75% (range: 0.19-1.5). Weekly treatment of colonized sink drains with acetic acid resulted in negative cultures and terminated transmission. Acetic acid is highly effective against Pae-MBL biofilms, and may be used as a simple method to decontaminate sink drains and to prevent nosocomial transmission. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

  14. The integration of acetic acid iontophoresis, orthotic therapy and physical rehabilitation for chronic plantar fasciitis: a case study

    PubMed Central

    Costa, Ivano A; Dyson, Anita

    2007-01-01

    A 15-year-old female soccer player presented with chronic plantar fasciitis. She was treated with acetic acid iontophoresis and a combination of rehabilitation protocols, ultrasound, athletic taping, custom orthotics and soft tissue therapies with symptom resolution and return to full activities within a period of 6 weeks. She reported no significant return of symptoms post follow-up at 2 months. Acetic acid iontophoresis has shown promising results and further studies should be considered to determine clinical effectiveness. The combination of acetic acid iontophoresis with conservative treatments may promote recovery within a shorter duration compared to the use of one-method treatment approaches. PMID:17885679

  15. 1-Azaniumylcyclobutane-1-carboxylate monohydrate

    NASA Technical Reports Server (NTRS)

    Butcher, Ray J.; Brewer, Greg; Burton, Aaron S.; Dworkin, Jason

    2014-01-01

    In the title compound, C5H9NO2H2O, the amino acid is in the usual zwitterionic form involving the carboxylate group. The cyclobutane backbone of the amino acid is disordered over two conformations, with occupancies of 0.882 (7) and0.118 (7). In the crystal, NH O and OH O hydrogen bonds link the zwitterions [with the water molecule involved as both acceptor (with the NH3+) and donor (through a single carboxylate O from two different aminocyclobutane carboxylatemoities)], resulting in a two-dimensional layered structure lying parallel to (100).

  16. Mechanism of heterogeneous catalytic oxidation of organic compounds to carboxylic acids

    NASA Astrophysics Data System (ADS)

    Andrushkevich, T. V.; Chesalov, Yu A.

    2018-06-01

    The results of studies on the mechanism of heterogeneous catalytic oxidation of organic compounds of different chemical structure to carboxylic acids are analyzed and generalized. The concept developed by Academician G.K.Boreskov, according to which the direction of the reaction is governed by the structure and bond energy of surface intermediates, was confirmed taking the title processes as examples. Quantitative criteria of the bond energies of surface compounds of oxidizable reactants, reaction products and oxygen that determine the selective course of the reaction are presented. The bibliography includes 195 references.

  17. Aerosol volatility and enthalpy of sublimation of carboxylic acids.

    PubMed

    Salo, Kent; Jonsson, Asa M; Andersson, Patrik U; Hallquist, Mattias

    2010-04-08

    The enthalpy of sublimation has been determined for nine carboxylic acids, two cyclic (pinonic and pinic acid) and seven straight-chain dicarboxylic acids (C(4) to C(10)). The enthalpy of sublimation was determined from volatility measurements of nano aerosol particles using a volatility tandem differential mobility analyzer (VTDMA) set-up. Compared to the previous use of a VTDMA, this novel method gives enthalpy of sublimation determined over an extended temperature range (DeltaT approximately 40 K). The determined enthalpy of sublimation for the straight-chain dicarboxylic acids ranged from 96 to 161 kJ mol(-1), and the calculated vapor pressures at 298 K are in the range of 10(-6)-10(-3) Pa. These values indicate that dicarboxylic acids can take part in gas-to-particle partitioning at ambient conditions and may contribute to atmospheric nucleation, even though homogeneous nucleation is unlikely. To obtain consistent results, some experimental complications in producing nanosized crystalline aerosol particles were addressed. It was demonstrated that pinonic acid "used as received" needed a further purification step before being suspended as a nanoparticle aerosol. Furthermore, it was noted from distinct differences in thermal properties that aerosols generated from pimelic acid solutions gave two types of particles. These two types were attributed to crystalline and amorphous configurations, and based on measured thermal properties, the enthalpy of vaporization was 127 kJ mol(-1) and that of sublimation was 161 kJ mol(-1). This paper describes a new method that is complementary to other similar methods and provides an extension of existing experimental data on physical properties of atmospherically relevant compounds.

  18. Oxoiron(IV) Tetramethylcyclam Complexes with Axial Carboxylate Ligands: Effect of Tethering the Carboxylate on Reactivity.

    PubMed

    Bigelow, Jennifer O; England, Jason; Klein, Johannes E M N; Farquhar, Erik R; Frisch, Jonathan R; Martinho, Marlène; Mandal, Debasish; Münck, Eckard; Shaik, Sason; Que, Lawrence

    2017-03-20

    Oxoiron(IV) species are implicated as reactive intermediates in nonheme monoiron oxygenases, often acting as the agent for hydrogen-atom transfer from substrate. A histidine is the most likely ligand trans to the oxo unit in most enzymes characterized thus far but is replaced by a carboxylate in the case of isopenicillin N synthase. As the effect of a trans carboxylate ligand on the properties of the oxoiron(IV) unit has not been systematically studied, we have synthesized and characterized four oxoiron(IV) complexes supported by the tetramethylcyclam (TMC) macrocycle and having a carboxylate ligand trans to the oxo unit. Two complexes have acetate or propionate axial ligands, while the other two have the carboxylate functionality tethered to the macrocyclic ligand framework by one or two methylene units. Interestingly, these four complexes exhibit substrate oxidation rates that differ by more than 100-fold, despite having E p,c values for the reduction of the Fe═O unit that span a range of only 130 mV. Eyring parameters for 1,4-cyclohexadiene oxidation show that reactivity differences originate from differences in activation enthalpy between complexes with tethered carboxylates and those with untethered carboxylates, in agreement with computational results. As noted previously for the initial subset of four complexes, the logarithms of the oxygen atom transfer rates of 11 complexes of the Fe IV (O)TMC(X) series increase linearly with the observed E p,c values, reflecting the electrophilicity of the Fe═O unit. In contrast, no correlation with E p,c values is observed for the corresponding hydrogen atom transfer (HAT) reaction rates; instead, the HAT rates increase as the computed triplet-quintet spin state gap narrows, consistent with Shaik's two-state-reactivity model. In fact, the two complexes with untethered carboxylates are among the most reactive HAT agents in this series, demonstrating that the axial ligand can play a key role in tuning the HAT

  19. Sulfonated reduced graphene oxide as a highly efficient catalyst for direct amidation of carboxylic acids with amines using ultrasonic irradiation.

    PubMed

    Mirza-Aghayan, Maryam; Tavana, Mahdieh Molaee; Boukherroub, Rabah

    2016-03-01

    Sulfonated reduced graphene oxide nanosheets (rGO-SO3H) were prepared by grafting sulfonic acid-containing aryl radicals onto chemically reduced graphene oxide (rGO) under sonochemical conditions. rGO-SO3H catalyst was characterized by Fourier-transform infrared (FT-IR) spectroscopy, Raman spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and X-ray photoelectron spectroscopy (XPS). rGO-SO3H catalyst was successfully applied as a reusable solid acid catalyst for the direct amidation of carboxylic acids with amines into the corresponding amides under ultrasonic irradiation. The direct sonochemical amidation of carboxylic acid takes place under mild conditions affording in good to high yields (56-95%) the corresponding amides in short reaction times. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. Molecular dynamics simulations of the auxin-binding protein 1 in complex with indole-3-acetic acid and naphthalen-1-acetic acid.

    PubMed

    Grandits, Melanie; Oostenbrink, Chris

    2014-10-01

    Auxin-binding protein 1 (ABP1) is suggested to be an auxin receptor which plays an important role in several processes in green plants. Maize ABP1 was simulated with the natural auxin indole-3-acetic acid (IAA) and the synthetic analog naphthalen-1-acetic acid (NAA), to elucidate the role of the KDEL sequence and the helix at the C-terminus. The KDEL sequence weakens the intermolecular interactions between the monomers but stabilizes the C-terminal helix. Conformational changes at the C-terminus occur within the KDEL sequence and are influenced by the binding of the simulated ligands. This observation helps to explain experimental findings on ABP1 interactions with antibodies that are modulated by the presence of auxin, and supports the hypothesis that ABP1 acts as an auxin receptor. Stable hydrogen bonds between the monomers are formed between Glu40 and Glu62, Arg10 and Thr97, Lys39, and Glu62 in all simulations. The amino acids Ile22, Leu25, Trp44, Pro55, Ile130, and Phe149 are located in the binding pocket and are involved in hydrophobic interactions with the ring system of the ligand. Trp151 is stably involved in a face to end interaction with the ligand. The calculated free energy of binding using the linear interaction energy approach showed a higher binding affinity for NAA as compared to IAA. Our simulations confirm the asymmetric behavior of the two monomers, the stronger interaction of NAA than IAA and offers insight into the possible mechanism of ABP1 as an auxin receptor. © 2014 Wiley Periodicals, Inc.

  1. The profile of volatile compounds in the outer and inner parts of broiled pork neck is strongly influenced by the acetic-acid marination conditions.

    PubMed

    Biller, Elżbieta; Boselli, Emanuele; Obiedziński, Mieczysław; Karpiński, Piotr; Waszkiewicz-Robak, Bożena

    2016-11-01

    Raw pork neck cutlets were marinated in an aqueous solution of acetic acid (pH4, 24h, 4°C) without (M) or with 1% (w/w) of glucose. The control (K) was formed by non-treated raw pork neck. The cutlets were then broiled (185°C, 30min). In all K cutlets, significant higher amounts of volatile compounds (VCs) were developed after broiling than the other samples. Significant more aldehydes and alcohols were present in the inner parts than in the surface. The correlation between surface and internal layers was high only for aldehydes. Marinating decreased the differences among VCs and led to the standardization of the processed meat. The addition of glucose to the marinade led to more volatile aldehydes, carboxylic acids, esters, furan, pyran, pyrazine, pyrrol and pyridine derivatives than in M samples. Several (53) specific VCs explained the differences among the surface samples related to the marinating process. However, only 16 VCs explained the variance among the inner parts. Copyright © 2016 Elsevier Ltd. All rights reserved.

  2. Effect of acetic acid and pH on the cofermentation of glucose and xylose to ethanol by a genetically engineered strain of Saccharomyces cerevisiae.

    PubMed

    Casey, Elizabeth; Sedlak, Miroslav; Ho, Nancy W Y; Mosier, Nathan S

    2010-06-01

    A current challenge of the cellulosic ethanol industry is the effect of inhibitors present in biomass hydrolysates. Acetic acid is an example of one such inhibitor that is released during the pretreatment of hemicellulose. This study examined the effect of acetic acid on the cofermentation of glucose and xylose under controlled pH conditions by Saccharomyces cerevisiae 424A(LNH-ST), a genetically engineered industrial yeast strain. Acetic acid concentrations of 7.5 and 15 g L(-1), representing the range of concentrations expected in actual biomass hydrolysates, were tested under controlled pH conditions of 5, 5.5, and 6. The presence of acetic acid in the fermentation media led to a significant decrease in the observed maximum cell biomass concentration. Glucose- and xylose-specific consumption rates decreased as the acetic acid concentration increased, with the inhibitory effect being more severe for xylose consumption. The ethanol production rates also decreased when acetic acid was present, but ethanol metabolic yields increased under the same conditions. The results also revealed that the inhibitory effect of acetic acid could be reduced by increasing media pH, thus confirming that the undissociated form of acetic acid is the inhibitory form of the molecule.

  3. Polyacetal Carboxylic Acids: a New Group of Antiviral Polyanions

    PubMed Central

    Claes, P.; Billiau, A.; De Clercq, E.; Desmyter, J.; Schonne, E.; Vanderhaeghe, H.; De Somer, P.

    1970-01-01

    Chlorite-oxidized oxypolysaccharides are polyacetal carboxylic acids. They inhibited the cytopathic effect of vesicular stomatitis virus in mouse embryo cell cultures challenged at low input multiplicity. After intraperitoneal injection of these compounds in mice, interferon appeared in the circulation. The compounds also protected mice against lethal mengovirus infection and against the development of experimental pox lesions on the tail. Chlorite-oxidized oxyamylose was antiviral only when at least 64% of the glucopyranose units were oxidized, an observation which suggested a correlation between charge density and antiviral effect. The antiviral activity was also influenced by the molecular weight, as demonstrated by the fact that chlorite-oxidized dextrans which had a high intrinsic viscosity were more active than those with low intrinsic viscosity. PMID:4314553

  4. Simultaneous determination of trace concentrations of aldehydes and carboxylic acids in particulate matter.

    PubMed

    Rousová, Jana; Chintapalli, Manikyala R; Lindahl, Anastasia; Casey, Jana; Kubátová, Alena

    2018-04-06

    Carboxylic acids and aldehydes are present in ambient air particulate matter (PM) originating from both primary emission and secondary production in air and may, due to their polarity have, an impact on formation of cloud condensation nuclei. Their simultaneous determination may provide improved understanding of atmospheric processes. We developed a new analytical method allowing for a single step determination of majority of carboxylic acids and aldehydes (+95 compounds). This sample preparation employed O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA·HCl) in methanol to yield oximes (for aldehydes) and methyl esters (for majority of acids); with the limits of detection of 0.02-1 ng per injection, corresponding to approximately 0.4-20 μg/g PM . Subsequent trimethylsilylation with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) was employed only for aromatic acids, which were not completely esterified, and for hydroxyl groups. Our method, in contrast to previous primarily qualitative studies, based on derivatization with an aqueous PFBHA followed by BSTFA derivatization, is less labor-intesive and reduces sample losses caused by an evaporation. The method was tested with a broad range of functionalized compounds (95), including monocarboxylic, dicarboxylic and aromatic acids, ketoacids, hydroxyacids and aldehydes. The developed protocol was applied to wood smoke (WS) and urban air standard reference material 1648b (UA) PM. The observed concentrations of aldehydes were 10-3000 μg/g PM in WS PM and 10-900 μg/g PM in UA PM, while those of acids were 20-1800 μg/g PM in WS PM and 15-1200 μg/g PM in UA PM. The most prominent aldehydes were syringaldehyde and vanillin in WS PM and glyoxal in UA PM. The most abundant acids in both PM samples were short-chain dicarboxylic acids (≤C 10 ). WS PM had a high abundance of hydroxyacids (vanillic and malic acids) as well as ketoacids (glutaric and oxalacetic) while UA PM also featured a high abundance of

  5. Ulcer healing activity of Mumijo aqueous extract against acetic acid induced gastric ulcer in rats

    PubMed Central

    Shahrokhi, Nader; Keshavarzi, Zakieh; Khaksari, Mohammad

    2015-01-01

    Objective: Gastric ulcer is an important clinical problem, chiefly due to extensive use of some drugs. The aim was to assess the activity of Mumijo extract (which is used in traditional medicine) against acetic acid induced gastric ulcer in rats. Materials and Methods: The aqueous extract of Mumijo was prepared. Animals were randomly (n = 10) divided into four groups: Control, sham-operated group (received 0.2 ml of acetic acid to induce gastric ulcer), Mumijo (100 mg/kg/daily) were given for 4 days postacetic acid administration, and ranitidine group (20 mg/kg). The assessed parameters were pH and pepsin levels (by Anson method) of gastric contents and gastric histopathology. Ranitidine was used as reference anti-ulcer drug. Results: The extract (100 mg/kg/daily, p.o.) inhibited acid acetic-induced gastric ulceration by elevating its pH versus sham group (P < 0.01) and decreasing the pepsin levels compared to standard drug, ranitidine (P < 0.05). The histopathology data showed that the treatment with Mumijo extract had a significant protection against all mucosal damages. Conclusion: Mumijo extract has potent antiulcer activity. Its anti-ulcer property probably acts via a reduction in gastric acid secretion and pepsin levels. The obtained results support the use of this herbal material in folk medicine. PMID:25709338

  6. Contribution to the analysis of the essential oil of Helichrysum italicum (Roth) G. Don. Determination of ester bonded acids and phenols.

    PubMed

    Mastelić, Josip; Politeo, Olivera; Jerković, Igor

    2008-04-07

    The essential oil of Helichrysum italicum (Roth) G. Don (everlasting or Immortelle essential oil) was isolated by hydrodistillation and analysed by GC and GCMS. Forty four compounds were identified. The main components were alpha-pinene(12.8%), 2-methyl-cyclohexyl pentanoate (11.1 %), neryl acetate (10.4%), 1,7-di-epi-alpha-cedrene (6.8%) and other compounds. The oil was fractionated and ester-containing fraction was hydrolysed with KOH/H(2)SO(4). The liberated volatiles were analysed by GC and GC-MS: three phenols and twenty seven volatile carboxylic acids were identified[70% low fatty acids (C(2)-C(5)), 15% C(10)-C(12) acids and 15% other acids]. The main acids were acetic acid (24.3%) propanoic acid (17.2%), 2-methylpropanoic acid (11.4%),dodecanoic acid (8.7%), 2-methylbutanoic acid (8.3%), (Z)-2-methylbutenoic acid(5.1%) and decanoic acid (4.6%). With respect to the identified bonded carboxylic acids,the minimal number of esters in the oil was twenty seven, but their overall quantity was probably larger due to different possible combinations of alcohols with acids to form esters. On the other hand, only six main esters were identified in the oil before fractionation and hydrolysis.

  7. Validation of a method for quantitation of the clopidogrel active metabolite, clopidogrel, clopidogrel carboxylic acid, and 2-oxo-clopidogrel in feline plasma.

    PubMed

    Lyngby, Janne G; Court, Michael H; Lee, Pamela M

    2017-08-01

    The clopidogrel active metabolite (CAM) is unstable and challenging to quantitate. The objective was to validate a new method for stabilization and quantitation of CAM, clopidogrel, and the inactive metabolites clopidogrel carboxylic acid and 2-oxo-clopiodgrel in feline plasma. Two healthy cats administered clopidogrel to demonstrate assay in vivo utility. Stabilization of CAM was achieved by adding 2-bromo-3'methoxyacetophenone to blood tubes to form a derivatized CAM (CAM-D). Method validation included evaluation of calibration curve linearity, accuracy, and precision; within and between assay precision and accuracy; and compound stability using spiked blank feline plasma. Analytes were measured by high performance liquid chromatography with tandem mass spectrometry. In vivo utility was demonstrated by a pharmacokinetic study of cats given a single oral dose of 18.75mg clopidogrel. The 2-oxo-clopidogrel metabolite was unstable. Clopidogrel, CAM-D, and clopidogrel carboxylic acid appear stable for 1 week at room temperature and 9 months at -80°C. Standard curves showed linearity for CAM-D, clopidogrel, and clopidogrel carboxylic acid (r > 0.99). Between assay accuracy and precision was ≤2.6% and ≤7.1% for CAM-D and ≤17.9% and ≤11.3% for clopidogrel and clopidogrel carboxylic acid. Within assay precision for all three compounds was ≤7%. All three compounds were detected in plasma from healthy cats receiving clopidogrel. This methodology is accurate and precise for simultaneous quantitation of CAM-D, clopidogrel, and clopidogrel carboxylic acid in feline plasma but not 2-oxo-clopidogrel. Validation of this assay is the first step to more fully understanding the use of clopidogrel in cats. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Screening and characterization of ethanol-tolerant and thermotolerant acetic acid bacteria from Chinese vinegar Pei.

    PubMed

    Chen, Yang; Bai, Ye; Li, Dongsheng; Wang, Chao; Xu, Ning; Hu, Yong

    2016-01-01

    Acetic acid bacteria (AAB) are important microorganisms in the vinegar industry. However, AAB have to tolerate the presence of ethanol and high temperatures, especially in submerged fermentation (SF), which inhibits AAB growth and acid yield. In this study, seven AAB that are tolerant to temperatures above 40 °C and ethanol concentrations above 10% (v/v) were isolated from Chinese vinegar Pei. All the isolated AAB belong to Acetobacter pasteurianus according to 16S rDNA analysis. Among all AAB, AAB4 produced the highest acid yield under high temperature and ethanol test conditions. At 4% ethanol and 30-40 °C temperatures, AAB4 maintained an alcohol-acid transform ratio of more than 90.5 %. High alcohol-acid transform ratio was still maintained even at higher temperatures, namely, 87.2, 77.1, 14.5 and 2.9% at 41, 42, 43 and 44 °C, respectively. At 30 °C and different initial ethanol concentrations (4-10%), the acid yield by AAB4 increased gradually, although the alcohol-acid transform ratio decreased to some extent. However, 46.5, 8.7 and 0.9% ratios were retained at ethanol concentrations of 11, 12 and 13%, respectively. When compared with AS1.41 (an AAB widely used in China) using a 10 L fermentor, AAB4 produced 42.0 g/L acetic acid at 37 °C with 10% ethanol, whereas AS1.41 almost stopped producing acetic acid. In conclusion, these traits suggest that AAB4 is a valuable strain for vinegar production in SF.

  9. Coordination and structure of Ca(II)-acetate complexes in aqueous solution studied by a combination of Raman and XAFS spectroscopies

    NASA Astrophysics Data System (ADS)

    Muñoz Noval, Álvaro; Nishio, Daisuke; Kuruma, Takuya; Hayakawa, Shinjiro

    2018-06-01

    The determination of the structure of Ca(II)-acetate in aqueous solution has been addressed by combining Raman and X-ray absorption fine structure spectroscopies. The pH-dependent speciation of the acetate/Ca(II) system has been studied observing modifications in specific Raman bands of the carboxyl group. The current results evidence the Ca(II)-acetate above acetate pKa forms a bidentate complex and presents a coordination 6, in which the Ca-O shell radius decrease of about 0.1 Å with respect the hydrated Ca2+ with coordination 8. The experimental results show the OCO angle of the carboxyl in the complex is close to 124°, being the OCaO angle about 60°.

  10. Unusal pattern of product inhibition: batch acetic acid fermentation

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

    Bar, R.; Gainer, J.L.; Kirwan, D.J.

    1987-04-20

    The limited tolerance of microorganisms to their metabolic products results in inhibited growth and product formation. The relationship between the specific growth rate, micro, and the concentration of an inhibitory product has been described by a number of mathematical models. In most cases, micro was found to be inversely proportional to the product concentration and invariably the rate of substrate utilization followed the same pattern. In this communication, the authors report a rather unusual case in which the formation rate of a product, acetic acid, increased with a decreasing growth rate of the microorganism, Acetobacter aceti. Apparently, a similar behaviormore » was mentioned in a review report with respect to Clostridium thermocellum in a batch culture but was not published in the freely circulating literature. The fermentation of ethanol to acetic acid, C/sub 2/H/sub 5/OH + O/sub 2/ = CH/sub 3/COOH + H/sub 2/O is clearly one of the oldest known fermentations. Because of its association with the commercial production of vinegar it has been a subject of extensive but rather technically oriented studies. Suprisingly, the uncommon uncoupling between the inhibited microbial growth and the product formation appears to have been unnoticed. 13 references.« less

  11. Free acetic acid as the key factor for the inhibition of hydrogenotrophic methanogenesis in mesophilic mixed culture fermentation.

    PubMed

    Zhang, Wei; Dai, Kun; Xia, Xiu-Yang; Wang, Hua-Jie; Chen, Yun; Lu, Yong-Ze; Zhang, Fang; Zeng, Raymond Jianxiong

    2018-05-18

    The inhibition of acetate under acidic pH is an ideal way to reduce methanogenesis in mesophilic mixed culture fermentation (MCF). However, the effects of acetate concentration and acidic pH on methanogenesis remain unclear. Besides, although hydrogenotrophic methanogens can be suitable targets in MCF, they are generally ignored. Therefore, we intentionally enriched hydrogenotrophic methanogens and found that free acetic acid (FAA, x) concentration and specific methanogenic activity (SMA, y) were correlated according to the equation: y = 0.86 × 0.31/(0.31 + x) (R 2  = 0.909). The SMA was decreased by 50% and 90% at the FAA concentrations of 0.31 and 2.36 g/L, respectively. The coenzyme M concentration and relative electron transport activity agreed well with the FAA concentration. Moreover, the methanogenic activity could not be recovered when the FAA concentration exceeded 0.81 g/L. These findings indicated that neither acetate nor acidic pH, but FAA was the key factor to inhibit methanogenesis in MCF. Copyright © 2018 Elsevier Ltd. All rights reserved.

  12. Comparison of Cultivable Acetic Acid Bacterial Microbiota in Organic and Conventional Apple Cider Vinegar.

    PubMed

    Štornik, Aleksandra; Skok, Barbara; Trček, Janja

    2016-03-01

    Organic apple cider vinegar is produced from apples that go through very restricted treatment in orchard. During the first stage of the process, the sugars from apples are fermented by yeasts to cider. The produced ethanol is used as a substrate by acetic acid bacteria in a second separated bioprocess. In both, the organic and conventional apple cider vinegars the ethanol oxidation to acetic acid is initiated by native microbiota that survived alcohol fermentation. We compared the cultivable acetic acid bacterial microbiota in the production of organic and conventional apple cider vinegars from a smoothly running oxidation cycle of a submerged industrial process. In this way we isolated and characterized 96 bacteria from organic and 72 bacteria from conventional apple cider vinegar. Using the restriction analysis of the PCR-amplified 16S-23S rRNA gene ITS regions, we identified four different Hae III and five different Hpa II restriction profiles for bacterial isolates from organic apple cider vinegar. Each type of restriction profile was further analyzed by sequence analysis of the 16S-23S rRNA gene ITS regions, resulting in identification of the following species: Acetobacter pasteurianus (71.90%), Acetobacter ghanensis (12.50%), Komagataeibacter oboediens (9.35%) and Komagataeibacter saccharivorans (6.25%). Using the same analytical approach in conventional apple cider vinegar, we identified only two different Hae III and two different Hpa II restriction profiles of the 16S‒23S rRNA gene ITS regions, which belong to the species Acetobacter pasteurianus (66.70%) and Komagataeibacter oboediens (33.30%). Yeasts that are able to resist 30 g/L of acetic acid were isolated from the acetic acid production phase and further identified by sequence analysis of the ITS1-5.8S rDNA‒ITS2 region as Candida ethanolica , Pichia membranifaciens and Saccharomycodes ludwigii . This study has shown for the first time that the bacterial microbiota for the industrial production of

  13. Comparison of Cultivable Acetic Acid Bacterial Microbiota in Organic and Conventional Apple Cider Vinegar

    PubMed Central

    Štornik, Aleksandra; Skok, Barbara

    2016-01-01

    Summary Organic apple cider vinegar is produced from apples that go through very restricted treatment in orchard. During the first stage of the process, the sugars from apples are fermented by yeasts to cider. The produced ethanol is used as a substrate by acetic acid bacteria in a second separated bioprocess. In both, the organic and conventional apple cider vinegars the ethanol oxidation to acetic acid is initiated by native microbiota that survived alcohol fermentation. We compared the cultivable acetic acid bacterial microbiota in the production of organic and conventional apple cider vinegars from a smoothly running oxidation cycle of a submerged industrial process. In this way we isolated and characterized 96 bacteria from organic and 72 bacteria from conventional apple cider vinegar. Using the restriction analysis of the PCR-amplified 16S−23S rRNA gene ITS regions, we identified four different HaeIII and five different HpaII restriction profiles for bacterial isolates from organic apple cider vinegar. Each type of restriction profile was further analyzed by sequence analysis of the 16S−23S rRNA gene ITS regions, resulting in identification of the following species: Acetobacter pasteurianus (71.90%), Acetobacter ghanensis (12.50%), Komagataeibacter oboediens (9.35%) and Komagataeibacter saccharivorans (6.25%). Using the same analytical approach in conventional apple cider vinegar, we identified only two different HaeIII and two different HpaII restriction profiles of the 16S‒23S rRNA gene ITS regions, which belong to the species Acetobacter pasteurianus (66.70%) and Komagataeibacter oboediens (33.30%). Yeasts that are able to resist 30 g/L of acetic acid were isolated from the acetic acid production phase and further identified by sequence analysis of the ITS1−5.8S rDNA‒ITS2 region as Candida ethanolica, Pichia membranifaciens and Saccharomycodes ludwigii. This study has shown for the first time that the bacterial microbiota for the industrial

  14. Effect of Concentrated Apple Extract on Experimental Colitis Induced by Acetic Acid.

    PubMed

    Pastrelo, Maurício Mercaldi; Dias Ribeiro, Carla Caroline; Duarte, Joselmo Willamys; Bioago Gollücke, Andréa Pitelli; Artigiani-Neto, Ricardo; Ribeiro, Daniel Araki; Miszputen, Sender Jankiel; Fujiyama Oshima, Celina Tizuko; Ribeiro Paiotti, Ana Paula

    2017-01-01

    Reactive oxygen and nitrogen species (ROS/RNS) play a crucial role in inflammatory bowel disease (IBD) exacerbating the chronic inflammatory process. Endogenous and diet antioxidants can neutralize these compounds. The apple is widely consumed, with several antioxidant activity compounds. The present study evaluated the effects of concentrated apple extract (CAE) in acetic acid induced colitis. 29 Wistar male rats were randomized into 5 groups. G1-Sham/saline solution, G2-CAE/control, G3-acetic acid/control, G4-curative- CAE treatment and G5-preventive-CAE treatment. Eight days later, the animals were euthanized and the colonic segment resected for macroscopic and histological analysis. Gene expression was evaluated for inducible nitric oxide synthase (iNOS), cyclooxygenase-2 (COX-2), catalase and copper and zinc superoxide dismutase (CuZnSOD) by quantitative real time PCR, while protein expression was assessed for iNOS, COX-2 and 8-hydroxy-20-deoxyguanosine (8-OHdG) via immunohistochemistry. The groups G3, G4 and G5 had weight loss, while G5 had weight increase at the end of the experiment. The treatment with CAE reduced the macroscopic and microscopic injury, decreased iNOS mRNA expression and increased CuZnSOD mRNA expression in animals with induced acetic acid-colitis. The findings of the present study suggest that CAE treatment exerts an antioxidant role by downregulating iNOS and upregulating CuZnSOD.

  15. Regulation of Auxin Homeostasis and Gradients in Arabidopsis Roots through the Formation of the Indole-3-Acetic Acid Catabolite 2-Oxindole-3-Acetic Acid[C][W][OPEN

    PubMed Central

    Pěnčík, Aleš; Simonovik, Biljana; Petersson, Sara V.; Henyková, Eva; Simon, Sibu; Greenham, Kathleen; Zhang, Yi; Kowalczyk, Mariusz; Estelle, Mark; Zažímalová, Eva; Novák, Ondřej; Sandberg, Göran; Ljung, Karin

    2013-01-01

    The native auxin, indole-3-acetic acid (IAA), is a major regulator of plant growth and development. Its nonuniform distribution between cells and tissues underlies the spatiotemporal coordination of many developmental events and responses to environmental stimuli. The regulation of auxin gradients and the formation of auxin maxima/minima most likely involve the regulation of both metabolic and transport processes. In this article, we have demonstrated that 2-oxindole-3-acetic acid (oxIAA) is a major primary IAA catabolite formed in Arabidopsis thaliana root tissues. OxIAA had little biological activity and was formed rapidly and irreversibly in response to increases in auxin levels. We further showed that there is cell type–specific regulation of oxIAA levels in the Arabidopsis root apex. We propose that oxIAA is an important element in the regulation of output from auxin gradients and, therefore, in the regulation of auxin homeostasis and response mechanisms. PMID:24163311

  16. (GTG)5-PCR reference framework for acetic acid bacteria.

    PubMed

    Papalexandratou, Zoi; Cleenwerck, Ilse; De Vos, Paul; De Vuyst, Luc

    2009-11-01

    One hundred and fifty-eight strains of acetic acid bacteria (AAB) were subjected to (GTG)(5)-PCR fingerprinting to construct a reference framework for their rapid classification and identification. Most of them clustered according to their respective taxonomic designation; others had to be reclassified based on polyphasic data. This study shows the usefulness of the method to determine the taxonomic and phylogenetic relationships among AAB and to study the AAB diversity of complex ecosystems.

  17. 21 CFR 862.1390 - 5-Hydroxyindole acetic acid/serotonin test system.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 8 2014-04-01 2014-04-01 false 5-Hydroxyindole acetic acid/serotonin test system. 862.1390 Section 862.1390 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES CLINICAL CHEMISTRY AND CLINICAL TOXICOLOGY DEVICES Clinical Chemistry...

  18. Construction of a recombinant strain of Pseudomonas fluorescens producing both phenazine-1-carboxylic acid and cyclic lipopeptide for the biocontrol of take-all disease of wheat.

    USDA-ARS?s Scientific Manuscript database

    The primary mechanism of biocontrol by Pseudomonas fluorescens strains HC1-07 and HC9-07 is production of a cyclic lipopeptide (CLP) and phenazine-1-carboxylic acid, respectively. We introduced the seven-gene operon for the synthesis of phenazine-1-carboxylic acid (PCA) from P. synxantha 2-79 into P...

  19. Separation of the isomers of benzene poly(carboxylic acid)s by quaternary ammonium salt via formation of deep eutectic solvents.

    PubMed

    Hou, Yucui; Li, Jian; Ren, Shuhang; Niu, Muge; Wu, Weize

    2014-11-26

    Because of similar properties and very low volatility, isomers of benzene poly(carboxylic acid)s (BPCAs) are very difficult to separate. In this work, we found that isomers of BPCAs could be separated efficiently by quaternary ammonium salts (QASs) via formation of deep eutectic solvents (DESs). Three kinds of QASs were used to separate the isomers of BPCAs, including the isomers of benzene tricarboxylic acids (trimellitic acid, trimesic acid, and hemimellitic acid) and the isomers of benzene dicarboxylic acids (phthalic acid and isophthalic acid). Among the QASs, tetraethylammonium chloride was found to have the best performance, which could completely separate BPCA isomers in methyl ethyl ketone solutions. It was found that the hydrogen bond forming between QAS and BPCA results in the selective separation of BPCA isomers. QAS in DES was regenerated effectively by the antisolvent method, and the regenerated QAS was reused four times with the same high efficiency.

  20. Luminescent hybrid lanthanide sulfates and lanthanide sulfonate-carboxylates with 1,10-phenanthroline involving in-situ oxidation of 2-mercaptonbenzoic acid

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

    Zhong, Jie-Cen; Wan, Fang; State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002

    A series of lanthanide sulfates and lanthanide sulfonate-carboxylates, [Ln{sub 2}(phen){sub 2}(SO{sub 4}){sub 3}(H{sub 2}O){sub 2}]{sub n} (I:Ln=Nd(1a), Sm(1b), Eu(1c), phen=1,10-phenanthroline) and [Ln(phen)(2-SBA)(BZA)]{sub n} (II: Ln=Sm(2a), Eu(2b), Dy(2c), 2-SBA=2-sulfobenzoate, BZA=benzoate) have been hydrothermally synthesized from lanthanide oxide, 2-mercaptonbenzoic acid with phen as auxiliary ligand and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, TG analyses and luminescence spectroscopy. Interestingly, SO{sub 4}{sup 2−} anions in I came from the in situ deep oxidation of thiol groups of 2-mercaptonbenzoic acid while 2-sulfobenzoate and benzoate ligands in II from the middle oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. Compounds I are organic–inorganic hybridmore » lanthanide sulfates, which have rare one-dimensional column-like structures. Complexes II are binuclear lanthanide sulfonate-carboxylates with 2-sulfobenzoate and benzoate as bridges and 1,10-phenanthroline as terminal. Photoluminescence studies reveal that complexes I and II exhibit strong lanthanide characteristic emission bands in the solid state at room temperature. - Graphical abstract: Lanthanide sulfates and lanthanide sulfonate-carboxylates have been hydrothermally synthesized. Interestingly, sulfate anions, 2-sulfobenzoate and benzoate ligands came from the in situ oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. - Highlights: • In situ oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. • The organic–inorganic hybrid lanthanide sulfates with one-dimensional column-like structure. • The dinuclear lanthanide sulfonate-carboxylates. • The emission spectra exhibit the characteristic transition of {sup 5}D{sub 0}→{sup 7}F{sub J} (J=0–4) of the Eu(III)« less

  1. Acidogenic fermentation of food waste for volatile fatty acid production with co-generation of biohydrogen.

    PubMed

    Dahiya, Shikha; Sarkar, Omprakash; Swamy, Y V; Venkata Mohan, S

    2015-04-01

    Fermentation experiments were designed to elucidate the functional role of the redox microenvironment on volatile fatty acid (VFA, short chain carboxylic acid) production and co-generation of biohydrogen (H2). Higher VFA productivity was observed at pH 10 operation (6.3g/l) followed by pH 9, pH 6, pH 5, pH 7, pH 8 and pH 11 (3.5 g/l). High degree of acidification, good system buffering capacity along with co-generation of higher H2 production from food waste was also noticed at alkaline condition. Experiments illustrated the role of initial pH on carboxylic acids synthesis. Alkaline redox conditions assist solubilization of carbohydrates, protein and fats and also suppress the growth of methanogens. Among the carboxylic acids, acetate fraction was higher at alkaline condition than corresponding neutral or acidic operations. Integrated process of VFA production from waste with co-generation of H2 can be considered as a green and sustainable platform for value-addition. Copyright © 2015 Elsevier Ltd. All rights reserved.

  2. Rapid degradation of 2,4-dichlorophenoxyacetic acid facilitated by acetate under methanogenic condition.

    PubMed

    Yang, Zhiman; Xu, Xiaohui; Dai, Meng; Wang, Lin; Shi, Xiaoshuang; Guo, Rongbo

    2017-05-01

    Acetate can be used as an electron donor to stimulate 2,4-dichlorophenoxyacetic acid (2,4-D), which has not been determined under methanogenic condition. This study applied high-throughput sequencing and methanogenic inhibition approaches to investigate the 2,4-D degradation process using the enrichments obtained from paddy soil. Acetate addition significantly promoted 2,4-D degradation, which was 5-fold higher than in the acetate-unsupplemented enrichments in terms of the 2,4-D degradation rate constant. Dechloromonas and Pseudomonas were the dominant 2,4-D degraders. Methanogenic inhibition experiments indicated that the 2,4-D degradation was independent of methanogenesis. It was proposed that the accelerated 2,4-D degradation in the acetate-supplemented enrichment involved an unusual interaction, where members of the acetate oxidizers primarily oxidized acetate and produced H 2 . H 2 was utilized by the 2,4-D degraders to degrade 2,4-D, but also partially consumed by the hydrogenotrophic methanogens to produce methane. The findings presented here provide a new strategy for the remediation of 2,4-D-polluted soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Direct carbon-carbon coupling of furanics with acetic acid over Bronsted zeolites

    DOE PAGES

    Gumidyala, Abhishek; Wang, Bin; Crossley, Steven

    2016-09-16

    Effective carbon-carbon coupling of acetic acid to form larger products while minimizing CO 2 emissions is critical to achieving a step change in efficiency for the production of transportation fuels from sustainable biomass. Here, we report the direct acylation of methylfuran with acetic acid in the presence ofwater, all ofwhich can be readily produced from biomass. This direct coupling limits unwanted polymerization of furanics while producing acetyl methylfuran. Reaction kinetics and density functional theory calculations illustrate that the calculated apparent barrier for the dehydration of the acid to form surface acyl species is similar to the experimentally measured barrier, implyingmore » that this step plays a significant role in determining the net reaction rate. Water inhibits the overall rate, but selectivity to acylated products is not affected.We show that furanic species effectively stabilize the charge of the transition state, therefore lowering the overall activation barrier. These results demonstrate a promising new route to C–C bond–forming reactions for the production of higher-value products from biomass.« less

  4. Calcium Supplementation Abates the Inhibition Effects of Acetic Acid on Saccharomyces cerevisiae.

    PubMed

    Zhao, Hongwei; Li, Jingyuan; Wang, Jiming; Xu, Xin; Xian, Mo; Liu, Huizhou; Zhang, Haibo

    2017-04-01

    The toxic level of acetic acid could be released during the pretreatment of lignocellulosic biomass, and an economical method was reported to minimize the acidic stress on the fermentation of Saccharomyces cerevisiae by cation supplementation. A dose-dependent protection of Ca 2+ was monitored, and the optimal concentration of Ca 2+ was 8 mM under 4.5 g/L acetic acid stress. The activities of catalase and superoxide dismutase of yeast cells supplemented with optimal Ca 2+ increased by 18.6 and 27.3 %, respectively, coupling with an obvious decrease of reactive oxygen species content. Cell viability also performed a significant increase from 52.4 % (without Ca 2+ addition) to 73.56 % (with 8 mM Ca 2+ addition). No significant improvements were found in the bioethanol yields by Ca 2+ supplementation; however, the fermentation time was shortened by about 8 h obviously. Our results illustrated that the Ca 2+ supplementation could be an economical method to make the bioethanol production more efficient and cost-effective.

  5. Modeling of acetate-type fermentation of sugar-containing wastewater under acidic pH conditions.

    PubMed

    Huang, Liang; Pan, Xin-Rong; Wang, Ya-Zhou; Li, Chen-Xuan; Chen, Chang-Bin; Zhao, Quan-Bao; Mu, Yang; Yu, Han-Qing; Li, Wen-Wei

    2018-01-01

    In this study, a kinetic model was developed based on Anaerobic Digestion Model No. 1 to provide insights into the directed production of acetate and methane from sugar-containing wastewater under low pH conditions. The model sufficiently described the dynamics of liquid-phase and gaseous products in an anaerobic membrane bioreactor by comprehensively considering the syntrophic bioconversion steps of sucrose hydrolysis, acidogenesis, acetogenesis and methanogenesis under acidic pH conditions. The modeling results revealed a significant pH-dependency of hydrogenotrophic methanogenesis and ethanol-producing processes that govern the sucrose fermentative pathway through changing the hydrogen yield. The reaction thermodynamics of such acetate-type fermentation were evaluated, and the implications for process optimization by adjusting the hydraulic retention time were discussed. This work sheds light on the acid-stimulated acetate-type fermentation process and may lay a foundation for optimization of resource-oriented processes for treatment of food wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. Co-production of furfural and acetic acid from corncob using ZnCl2 through fast pyrolysis in a fluidized bed reactor.

    PubMed

    Oh, Seung-Jin; Jung, Su-Hwa; Kim, Joo-Sik

    2013-09-01

    Corncob was pyrolyzed using ZnCl2 in a pyrolysis plant equipped with a fluidized bed reactor to co-produce furfural and acetic acid. The effects of reaction conditions, the ZnCl2 content and contacting method of ZnCl2 with corncob on the yields of furfural and acetic acid were investigated. The pyrolysis was performed within the temperature range between 310 and 410°C, and the bio-oil yield were 30-60 wt% of the product. The furfural yield increased up to 8.2 wt%. The acetic acid yield was maximized with a value of 13.1 wt%. A lower feed rate in the presence of ZnCl2 was advantageous for the production of acetic acid. The fast pyrolysis of a smaller corncob sample mechanically mixed with 20 wt% of ZnCl2 gave rise to a distinct increase in furfural. A high selectivity for furfural and acetic acid in bio-oil would make the pyrolysis of corncob with ZnCl2 very economically attractive. Copyright © 2013 Elsevier Ltd. All rights reserved.

  7. Sulfur-containing constituents and one 1H-pyrrole-2-carboxylic acid derivative from pineapple [Ananas comosus (L.) Merr.] fruit.

    PubMed

    Zheng, Zong-Ping; Ma, Jinyu; Cheng, Ka-Wing; Chao, Jianfei; Zhu, Qin; Chang, Raymond Chuen-Chung; Zhao, Ming; Lin, Zhi-Xiu; Wang, Mingfu

    2010-12-01

    Two sulfur-containing compounds, (S)-2-amino-5-((R)-1-carboxy-2-((E)-3-(4-hydroxy-3-methoxyphenyl)allylthio)ethyl-amino)-5-oxopentanoic acid (1) and (S)-2-amino-5-((R)-1-(carboxymethylamino)-3-((E)-3-(4-hydroxyphenyl)allylthio)-1-oxopropan-2-ylamino)-5-oxopentanoic acid (2), and one 1H-pyrrole-2-carboxylic acid derivative, 6-(3-(1H-pyrrole-2-carbonyloxy)-2-hydroxypropoxy)-3,4,5-trihydroxy-tetrahydro-2H-pyran-2-carboxylic acid (3), together with eighteen known phenolic compounds, were isolated from the fruits of pineapple. Their structures were elucidated by a combination of spectroscopic analyses. Some of these compounds showed inhibitory activities against tyrosinase. The half maximal inhibitory concentration values of compounds 1, 4, 5, 6, 7 are lower than 1 mM. These compounds may contribute to the well-known anti-browning effect of pineapple juice and be potential skin whitening agents in cosmetic applications. Copyright © 2010 Elsevier Ltd. All rights reserved.

  8. High-level expression of recombinant thermostable β-glucosidase in Escherichia coli by regulating acetic acid.

    PubMed

    Shi, Xuejia; Xie, Jingcong; Liao, Shiyong; Wu, Tao; Zhao, Lin-Guo; Ding, Gang; Wang, Zhenzhong; Xiao, Wei

    2017-10-01

    In the fermentation progress, fermentation parameters including the feed rate, induction temperature, and induction pH evidently regulate the accumulation of acetic acid generated by recombinant E. coli in the medium. The production of thermostable β-glucosidase (Tpebgl3) was increased by optimizing the parameters mentioned step by step. The optimal conditions were obtained with the highest enzyme expression (560.4U/mL) and the maximum DCW (65g/L) at the pre-induction specific growth rate of 0.2h -1 followed by a post-induction specific growth rate (0.18h -1 ); induction temperature is 39°C; the pH is 7.2; the concentration of acetic acid was maintained all along below 0.9g/L. Results show it is necessary for the synthesis of Tpebgl3 to regulate the accumulation of acetic acid at the premise of feeding to meet the normal growth of E. coli. The production of Tpebgl3 by recombinant E. coli is the highest reported to date. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Role of the glyoxylate pathway in acetic acid production by Acetobacter aceti.

    PubMed

    Sakurai, Kenta; Yamazaki, Shoko; Ishii, Masaharu; Igarashi, Yasuo; Arai, Hiroyuki

    2013-01-01

    Wild-type Acetobacter aceti NBRC 14818 possesses genes encoding isocitrate lyase (aceA) and malate synthase (glcB), which constitute the glyoxylate pathway. In contrast, several acetic acid bacteria that are utilized for vinegar production lack these genes. Here, an aceA-glcB knockout mutant of NBRC 14818 was constructed and used for investigating the role of the glyoxylate pathway in acetate productivity. In medium containing ethanol as a carbon source, the mutant grew normally during ethanol oxidation to acetate, but exhibited slower growth than that of the wild-type strain as the accumulated acetate was oxidized. The mutant grew similarly to that of the wild-type strain in medium containing glucose as a carbon source, indicating that the glyoxylate pathway was not necessary for glucose utilization. However, in medium containing both ethanol and glucose, the mutant exhibited significantly poorer growth and lower glucose consumption compared to the wild-type strain. Notably, the mutant oxidized ethanol nearly stoichiometrically to acetate, which was retained in the medium for a longer period of time than the acetate produced by wild-type strain. The features of the aceA-glcB knockout mutant revealed here indicate that the lack of the glyoxylate pathway is advantageous for industrial vinegar production by A. aceti. Copyright © 2012 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

  10. Efficacy of Trichloro-Acetic Acid Peel Alone Versus Combined Topical Magnesium Ascorbyl Phosphate for Epidermal Melasma.

    PubMed

    Murtaza, Fatima; Bangash, Abdur Rahim; Khushdil, Arshad; Noor, Sahibzada Mahmood

    2016-07-01

    To compare the efficacy in terms of reduction in melasma area and severity index (MASI) score by more than 10 of a combination of 20% trichloro-acetic acid peel plus 5% topical magnesium ascorbyl phosphate versus 20% trichloroacetic acid peel alone in the treatment of epidermal melasma. Randomized controlled trial. Department of Dermatology, Lady Reading Hospital (LRH), Peshawar, from May 2012 to May 2013. Patients aged 18 - 65 years, with Fitzpatrick skin type III-V were divided into two equal groups having 74 patients each. Detailed history was taken and Wood's lamp examination done to rule out mixed and dermal melasma. Melasma area and severity index (MASI) score was calculated for every patient. Priming was done for all patients with tretinoin cream applied once daily at night for 2 weeks, and to use a broad spectrum sun block cream before sun exposure. Patients in group Awere subjected to combined treatment, i.e. trichloro-acetic acid peel 20% (weekly) plus magnesium ascorbyl phosphate cream (applied once daily), while patients in group B were subjected to trichloro-acetic acid peel 20% (weekly) alone. Treatment was continued for 6 weeks. After completion of treatment, MASI score was recalculated. Proportion of patients with significant MASI score reduction was compared using chi-square test with significance at p < 0.05. Male and female patients were 11 (14.9%) and 63 (85.1%), respectively in group A, whereas 13 (17.6%) and 61 (82.4%) in group B. The mean age in group Awas 30.28 ±8.08 years, and 29.36 ±6.84 years in group B. Significant MASI score reduction in group Awas seen in 60 (81.1%) patients and in group B 49 (66.2%, p= 0.040). Combination of trichloro-acetic acid peel and topical magnesium ascorbyl phosphate cream was significantly more effective than trichloro-acetic acid peel alone in treatment of melasma.

  11. Lipase catalyzed epoxidation of fatty acid methyl esters derived from unsaturated vegetable oils in absence of carboxylic acid.

    PubMed

    Sustaita-Rodríguez, Alejandro; Ramos-Sánchez, Víctor H; Camacho-Dávila, Alejandro A; Zaragoza-Galán, Gerardo; Espinoza-Hicks, José C; Chávez-Flores, David

    2018-04-11

    Nowadays the industrial chemistry reactions rely on green technologies. Enzymes as lipases are increasing its use in diverse chemical processes. Epoxidized fatty acid methyl esters obtained from transesterification of vegetable oils have recently found applications as polymer plasticizer, agrochemical, cosmetics, pharmaceuticals and food additives. In this research article, grapeseed, avocado and olive oils naturally containing high percents of mono and poly unsaturations were used as starting materials for the production of unsaturated fatty acid methyl esters. The effect of lauric acid as an active oxygen carrier was studied on epoxidation reactions where unsaturated fatty acid methyl esters were converted to epoxy fatty acid methyl esters using immobilized Candida antarctica Lipase type B as catalyst and hydrogen peroxide as oxygen donor at mild temperature and pressure conditions. After this study it was confirmed by 1 H NMR, 13 C NMR and GC-MS that the addition of lauric acid to the enzymatic reaction is unnecessary to transform the alkenes in to epoxides. It was found that quantitative conversions were possible in despite of a carboxylic acid absence.

  12. Synthesis, Properties, and Two-Dimensional Adsorption Characteristics of [6]Hexahelicene-7-carboxylic acid.

    PubMed

    van der Meijden, Maarten W; Balandina, Tatyana; Ivasenko, Oleksandr; De Feyter, Steven; Wurst, Klaus; Kellogg, Richard M

    2016-10-04

    A convergent synthesis of racemic [6]hexahelicene-7-carboxylic acid by cross-coupling of a bicyclic and a tricyclic component is described. A metal-catalyzed ring-closure is also a fundamental component of the synthetic approach. Scanning tunneling microscopy (STM) measurements of the racemate self-assembled on Au(111) at liquid-solid interface revealed the formation of ordered racemic 2D crystals. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Synthesis and biological evaluation of pyrazolylthiazole carboxylic acids as potent anti-inflammatory-antimicrobial agents.

    PubMed

    Khloya, Poonam; Kumar, Satish; Kaushik, Pawan; Surain, Parveen; Kaushik, Dhirender; Sharma, Pawan K

    2015-03-15

    Current Letter presents design, synthesis and biological evaluation of a novel series of pyrazolylthiazole carboxylates 1a-1p and corresponding acid derivatives 2a-2p. All 32 novel compounds were tested for their in vivo anti-inflammatory activity by carrageenan-induced rat paw edema method as well as for in vitro antimicrobial activity. All the tested compounds exhibited excellent AI activity profile. Three compounds 1p (R=Cl, R(1)=Cl), 2c (R=H, R(1)=F) and 2n (R=Cl, R(1)=OCH3) were identified as potent anti-inflammatory agents exhibiting edema inhibition of 93.06-89.59% which is comparable to the reference drug indomethacin (91.32%) after 3h of carrageenan injection while most of the other compounds displayed inhibition ⩾80%. In addition, pyrazolylthiazole carboxylic acids (2a-2p) also showed good antimicrobial profile. Compound 2h (R=OCH3, R(1)=Cl) showed excellent antimicrobial activity (MIC 6.25μg/mL) against both Gram positive bacteria comparable with the reference drug ciprofloxacin (MIC 6.25μg/mL). Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Waterborne carboxyl-terminated hyperbranched oligomer polyester ligand: Synthesis, characterization and chelation with chromium(III)

    NASA Astrophysics Data System (ADS)

    Yao, Qi; Li, Chenying; Huang, Henghui; Chen, Hualin; Liu, Bailing

    2017-09-01

    A series of carboxyl-terminated hyperbranched oligomer polyester (HBP) with different degree of branching (DB) and number average molar mass (Mbarn) have been prepared. The molecular structure, degree of branching, molecular mass and its distribution of HBP were investigated by FTIR, 1H NMR, and GPC, respectively. And the coordination number, stability constant and degree of dissociation (α) between HBP and chromium(Ⅲ) were measured via continuous variation method (Job's plot). Experimental results show that the coordination capability between HBP and chromium(Ⅲ) affected by both DB and molecular mass, and the latter plays a decisive role. Moreover HBP outperforms low molecular weight of organic acids (citric acid, acetic acid) and linear polyacrylic acid with similar molecular mass. The coordination number and stability constants of HBP-3 (Mbarn = 1713 Da, Mbarw /Mbarn (PDI) = 1.11 and DB = 0.72) can reach 4 and 6.55e+008, which demonstrated it can be selected as a good ligand to coordination with chromium(Ⅲ). Therefore HBP can be used as chrome auxiliary in chrome tanning to improve the absorption of chromium.

  15. Regioselective Ni-Catalyzed Carboxylation of Allylic and Propargylic Alcohols with Carbon Dioxide.

    PubMed

    Chen, Yue-Gang; Shuai, Bin; Ma, Cong; Zhang, Xiu-Jie; Fang, Ping; Mei, Tian-Sheng

    2017-06-02

    An efficient Ni-catalyzed reductive carboxylation of allylic alcohols with CO 2 has been successfully developed, providing linear β,γ-unsaturated carboxylic acids as the sole regioisomer with generally high E/Z stereoselectivity. In addition, the carboxylic acids can be generated from propargylic alcohols via hydrogenation to give allylic alcohol intermediates, followed by carboxylation. A preliminary mechanistic investigation suggests that the hydrogenation step is made possible by a Ni hydride intermediate produced by a hydrogen atom transfer from water.

  16. Enhanced acetic acid production from manalagi apple (Malus sylvestris mill) by mixed cultures of Saccharomyces cerevisiae and Acetobacter aceti in submerged fermentation

    NASA Astrophysics Data System (ADS)

    Rosada, K. K.

    2018-05-01

    The production of acetic acid from Manalagi apple was studied using a mixed culture of S. cerevisiae and A. aceti by submerged fermentation technique. Determination of the best conditions for producing acetic acid was performed by stratified optimization with variations that were made on the concentration of the initial sugar addition to the medium (0%, 10%, 20% w/v), the ratio of the number of inocula S. cerevisiae and A. aceti (7:3, 1:1, 3:7), and agitation rate (80 and 160 rpm). All experiments were done by using the initial pH medium of 4.5 and incubated at room temperature (28±2oC) for 14 days. The concentration of reducing sugar, alcohol, acetic acid, and the pH were measured every 48 hours. The efficiency of sugar conversion to acetic acid with the addition of initial sugar 0%, 10%, and20%were 233%, 46.6%, and 6.4% respectively after ten days of incubation. Overall, the result showed that the highest acetic acid was produced from Manalagi apple juice when no sugar was added, using seven parts of S. cerevisiae to three parts of A. aceti and agitation rate of 160 rpm on the tenth day of fermentation. Under these conditions, glucose conversion efficiency to acetic acid increased to 362%.

  17. Benzene carboxylic acid derivatized graphene oxide nanosheets on natural zeolites as effective adsorbents for cationic dye removal.

    PubMed

    Yu, Yang; Murthy, Bandaru N; Shapter, Joseph G; Constantopoulos, Kristina T; Voelcker, Nicolas H; Ellis, Amanda V

    2013-09-15

    Graphene oxide (GO) nanosheets were grafted to acid-treated natural clinoptilolite-rich zeolite powders followed by a coupling reaction with a diazonium salt (4-carboxybenzenediazoniumtetrafluoroborate) to the GO surface. Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and thermogravimetric analysis (TGA) revealed successful grafting of GO nanosheets onto the zeolite surface. The application of the adsorbents for the adsorption of rhodamine B from aqueous solutions was then demonstrated. After reaching adsorption equilibrium the maximum adsorption capacities were shown to be 50.25, 55.56 and 67.56 mg g(-1) for pristine natural zeolite, GO grafted zeolite (GO-zeolite) and benzene carboxylic acid derivatized GO-zeolite powders, respectively. The adsorption behavior was fitted to a Langmuir isotherm and shown to follow a pseudo-second-order reaction model. Further, a relationship between surface functional groups, pH and adsorption efficiency was established. Results indicate that benzene carboxylic acid derivatized GO-zeolite powders are environmentally favorable adsorbents for the removal of cationic dyes from aqueous solutions. Copyright © 2013 Elsevier B.V. All rights reserved.

  18. [Comparison of the diagnostic utility from visual inspection with acetic acid and cervical cytology].

    PubMed

    Velázquez-Hernández, Nadia; Sánchez-Anguiano, Luis Francisco; Lares-Bayona, Edgar Felipe; Cisneros-Pérez, Vicente; Milla-Villeda, Reinaldo Humberto; Arreola-Herrera, Francisco de Asís; Navarrete-Flores, José Antonio; Aguilar-Durán, Maricela; Núñez-Márquez, Teresita; Rueda-Cisneros, Dora Alicia

    2010-05-01

    In Mexico, cervical cancer is the second leading cause of death in women after breast cancer. The human papillomavirus is associated with intraepithelial lesions, detected up to 99.7% of cervical carcinomas. Despite being easy to detect is a condition that many women suffer. To determine the diagnostic utility of the visual inspection with acetic acid of the uterine cervix compared with the cervical cytology. Study of diagnostic tests. The study was realized in the Centro de Atención Materno Infantil y Planificación Familiar of the Instituto de Investigación Científica, Durango, Mexico, research of the Juárez University of the State of Durango, from August 23, 2005 to November 13, 2006. 1,521 participants were examined who went consecutively to opportune detection of cervical cancer. One doctor practiced the test of acetic acid and cervical cytology to them, and one digital photograph, which was evaluated by three inter-observers triple blind. Those that was positive to anyone of these tests, were remitted to colposcopy and/or biopsy; also to 10% of selected negative population randomly was realized this procedure. Sensitivity, specificity, positive and negative predictive values and exactitude were determined. For the agreement inter-observer index of Kappa was used. Sensitivity, specificity, values predictive positive, negative and exactitude for the visual inspection with acetic acid were 20, 97, 5 and 99%, respectively. For the cervical cytology were of 80, 99, 57 and 99%, respectively. The force of agreement between the interobservant was poor. In this study cervical cytology was more useful than visual inspection with acetic acid to detect dysplasias or cervical cancer opportunely, due to detect all the positive true cases confirmed by biopsy.

  19. Study on the extraction, purification and quantification of jasmonic acid, abscisic acid and indole-3-acetic acid in plants.

    PubMed

    Zhang, Feng Juan; Jin, You Ju; Xu, Xing You; Lu, Rong Chun; Chen, Hua Jun

    2008-01-01

    Jasmonic acid (JA), abscisic acid (ABA) and indole-3-acetic acid (IAA) are important plant hormones. Plant hormones are difficult to analyse because they occur in small concentrations and other substances in the plant interfere with their detection. To develop a new, inexpensive procedure for the rapid extraction and purification of IAA, ABA and JA from various plant species. Samples were prepared by extraction of plant tissues with methanol and ethyl acetate. Then the extracts were further purified and enriched with C(18) cartridges. The final extracts were derivatised with diazomethane and then measured by GC-MS. The results of the new methodology were compared with those of the Creelman and Mullet procedure. Sequential elution of the assimilates from the C(18 )cartridges revealed that IAA and ABA eluted in 40% methanol, while JA subsequently eluted in 60% methanol. The new plant hormone extraction and purification procedure produced results that were comparable to those obtained with the Creelman and Mullet's procedure. This new procedure requires only 0.5 g leaf samples to quantify these compounds with high reliability and can simultaneously determine the concentrations of the three plant hormones. A simple, inexpensive method was developed for determining endogenous IAA, ABA and JA concentrations in plant tissue.

  20. High temperature stimulates acetic acid accumulation and enhances the growth inhibition and ethanol production by Saccharomyces cerevisiae under fermenting conditions.

    PubMed

    Woo, Ji-Min; Yang, Kyung-Mi; Kim, Sae-Um; Blank, Lars M; Park, Jin-Byung

    2014-07-01

    Cellular responses of Saccharomyces cerevisiae to high temperatures of up to 42 °C during ethanol fermentation at a high glucose concentration (i.e., 100 g/L) were investigated. Increased temperature correlated with stimulated glucose uptake to produce not only the thermal protectant glycerol but also ethanol and acetic acid. Carbon flux into the tricarboxylic acid (TCA) cycle correlated positively with cultivation temperature. These results indicate that the increased demand for energy (in the form of ATP), most likely caused by multiple stressors, including heat, acetic acid, and ethanol, was matched by both the fermentation and respiration pathways. Notably, acetic acid production was substantially stimulated compared to that of other metabolites during growth at increased temperature. The acetic acid produced in addition to ethanol seemed to subsequently result in adverse effects, leading to increased production of reactive oxygen species. This, in turn, appeared to cause the specific growth rate, and glucose uptake rate reduced leading to a decrease of the specific ethanol production rate far before glucose depletion. These results suggest that adverse effects from heat, acetic acid, ethanol, and oxidative stressors are synergistic, resulting in a decrease of the specific growth rate and ethanol production rate and, hence, are major determinants of cell stability and ethanol fermentation performance of S. cerevisiae at high temperatures. The results are discussed in the context of possible applications.