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Sample records for acetic acid formic

  1. Atmospheric geochemistry of formic and acetic acids at a mid-latitude temperate site

    NASA Technical Reports Server (NTRS)

    Talbot, R. W.; Beecher, K. M.; Harriss, R. C.; Cofer, R. W., III

    1988-01-01

    Tropospheric concentrations of formic and acetic acids in the gas, the aerosol, and the rainwater phases were determined in samples collected 1-2 m above ground level at an open field site in eastern Virginia. These acids were found to occur principally (98 percent or above) in the gas phase, with a marked annual seasonality, averaging 1890 ppt for formate and 1310 ppt for acetate during the growing season, as compared to 695 ppt and 700 ppt, respectively, over the nongrowing season. The data support the hypothesis that biogenic emissions from vegatation are important sources of atmospheric formic and acetic acid during the local growing season. The same time trends were observed for precipitation, although with less defined seasonality. The relative increase of the acetic acid/formic acid ratio during the nongrowing season points to the dominance of anthropogenic inputs of acetic acid from motor vehicles and biomass combustion in the wintertime.

  2. Formic acid and acetic acid induce a programmed cell death in pathogenic Candida species.

    PubMed

    Lastauskienė, Eglė; Zinkevičienė, Auksė; Girkontaitė, Irutė; Kaunietis, Arnoldas; Kvedarienė, Violeta

    2014-09-01

    Cutaneous fungal infections are common and widespread. Antifungal agents used for the treatment of these infections often have undesirable side effects. Furthermore, increased resistance of the microorganisms to the antifungal drugs becomes the growing problem. Accordingly, the search for natural antifungal compounds continues to receive attention. Apoptosis is highly regulated programmed cell death. During yeast cell apoptosis, amino acids and peptides are released and can stimulate regeneration of human epithelium cells. Thus, detection of chemical compounds inducing apoptosis in yeast and nontoxic for humans is of great medical relevance. The aim of this study was to detect chemical compound inducing apoptosis in pathogenic Candida species with the lowest toxicity to the mammalian cells. Five chemical compounds--acetic acid, sodium bicarbonate, potassium carbonate, lithium acetate, and formic acid--were tested for evaluation of antifungal activity on C. albicans, C. guilliermondii, and C. lusitaniae. The results showed that acetic acid and formic acid at the lowest concentrations induced yeast cells death. Apoptosis analysis revealed that cells death was accompanied by activation of caspase. Minimal inhibitory concentrations of potassium carbonate and sodium bicarbonate induced Candida cells necrosis. Toxicity test with mammalian cell cultures showed that formic acid has the lowest effect on the growth of Jurkat and NIH 3T3 cells. In conclusion, our results show that a low concentration of formic acid induces apoptosis-like programmed cell death in the Candida yeast and has a minimal effect on the survivability of mammalian cells, suggesting potential applications in the treatment of these infections. PMID:24752490

  3. Formic acid and acetic acid measurements during the Southern California Air Quality Study

    NASA Astrophysics Data System (ADS)

    Grosjean, Daniel

    As part of the Southern California Air Quality Study (SCAQS), ambient levels of gas phase formic acid and acetic acid have been measured at four locations: a 'control' site (San Nicholas Island), a source-dominated coastal site (Long Beach) and two inland smog receptor sites (Claremont and Palm Springs). Samples were collected on alkaline traps and were analyzed by size exclusion liquid chromatography with ultraviolet detection. Levels of gas phase formic acid (up to 19 ppb) and acetic acid (up to 17 ppb) exhibited diurnal (frequent night-time maxima), spatial and seasonal variations. During summer smog episodes, concentrations increased from 0.6 ppb at the 'control' site to up to 13-19 ppb at the inland smog receptor sites reflecting primary emissions and in situ formation during transport inland. The acetic acid/formic acid (A/F) ratio decreased from coastal to inland sites. At the coastal site levels of both acids and the A/F ratio were substantially higher during the fall than during the summer.

  4. Measurements of acetone, acetic acid, and formic acid in the northern midlatitude upper troposphere and lower stratosphere

    NASA Astrophysics Data System (ADS)

    Reiner, Thomas; MöHler, Ottmar; Arnold, Frank

    1999-06-01

    We have measured acetone, acetic acid, and formic acid concentrations in the upper troposphere and lower stratosphere over Germany. The measurements were performed by ion molecule reaction mass spectrometry using new kinetic data on ion molecule reactions of formic and acetic acids with negative ions obtained at our laboratory. Mean volume mixing ratios between 384 and 832 parts per trillion (pptv) for acetone, 110 and 357 pptv for acetic acid, and 59 and 215 pptv for formic acid were obtained. The correlation between formic acid and acetic acid was very poor (r2 = 0.14). A better correlation could be observed for acetone and acetic acid, with a correlation coefficient r2 = 0.46 and a slope (acetic acid/acetone) of 0.31. For acetic acid a maximum around 9 km was observed. A significant fraction of the acetic acid observed in the lower stratosphere may be due to in situ photochemical production by reactions of HO2 and CH3O2 with peroxy acetyl radicals produced by the photolysis of acetone. In the upper troposphere, vertical transport is much more efficient, and significant acetic acid production is only possible if HOx concentrations are elevated, making the production of acetic acid fast enough to compete with vertical transport.

  5. Anhydrous formic acid and acetic anhydride as solvent or additive in nonaqueous titrations.

    PubMed

    Buvári-Barcza, A; Tóth, I; Barcza, L

    2005-09-01

    The use and importance of formic acid and acetic anhydride (Ac2O) is increasing in nonaqueous acid-base titrations, but their interaction with the solutes is poorly understood. This paper attempts to clarify the effect of the solvents; NMR and spectrophotometric investigations were done to reveal the interactions between some bases and the mentioned solvents. Anhydrous formic acid is a typical protogenic solvent but both the relative permittivity and acidity are higher than those of acetic acid (mostly used in assays of bases). These differences originate from the different chemical structures: liquid acetic acid contains basically cyclic dimers while formic acid forms linear associates. Ac2O is obviously not an acidic but an aprotic (very slightly protophilic) solvent, which supposedly dissociates slightly into acetyl (CH3CO+) and acetate (AcO-) ions. In fact, some bases react with Ac2O forming an associate: the Ac+ group is bound to the delta- charged atom of the reactant while AcO- is associated with the delta+ group at appropriate distance.

  6. Decadal variations of rainwater formic and acetic acid concentrations in Wilmington, NC, USA

    NASA Astrophysics Data System (ADS)

    Willey, Joan D.; Glinski, Donna A.; Southwell, Melissa; Long, Michael S.; Avery, G. Brooks, Jr.; Kieber, Robert J.

    2011-02-01

    Concentrations of formic and acetic acid from January 2008 through March 2009 were compared to two previous studies at this location (conducted in 1987-1990 and 1996-1998) in order to quantify the extent to which temporal changes in DOC and pH can be explained by changes in these organic acids. The volume weighted 2008 formic and acetic acid concentrations (5.6 and 2.6 μM respectively) have decreased dramatically compared with those observed during the 1996-1998 study (9.9 and 7.3 μM) and are also lower than concentrations observed in the 1987-1990 study (7.4 and 3.6 μM). Changes in formic and acetic acids between 1996-97 and 2008 can account for approximately 50% of the DOC change and 40% of the H + change in rainwater over this same time period. These changes are most pronounced during the growing season, which is also the tourist and high traffic season at this location. Determining causation of these changes is difficult due to multiple biogenic and anthropogenic sources. However, the ratio of formic to acetic acid has also reverted back to a value consistent with reduced vehicular emissions, possibly related to the introduction of improved emission control technology including the use of reformulated gasoline in the late 1990's. Long term monitoring of seasonal, annual, and decadal trends will be of critical importance for evaluating the effects of future changes to atmospheric inputs such as the increased use of ethanol and other alternative fuels.

  7. Inhibition of enterobacteria and Listeria growth by lactic, acetic and formic acids.

    PubMed

    Ostling, C E; Lindgren, S E

    1993-07-01

    Minimum inhibitory concentrations (MIC) of undissociated lactic, acetic and formic acids were evaluated for 23 strains of enterobacteria and two of Listeria monocytogenes. The evaluation was performed aerobically and anaerobically in a liquid test system at pH intervals of between 4.2 and 5.4. Growth of the enterobacteria was inhibited at 2-11 mmol l-1, 0.5-14 mmol l-1 and 0.1-1.5 mmol l-1 of undissociated lactic, acetic and formic acids, respectively. The MIC value was slightly lower with anaerobic conditions compared with aerobic conditions. The influence of protons on the inhibition was observed for acetic acid at the low pH values. Undissociated lactic acid was 2 to 5 times more efficient in inhibiting L. monocytogenes than enterobacteria. Acetic acid had a similar inhibitory action on L. monocytogenes compared with enterobacteria. Inorganic acid (HCl) inhibited most enterobacteria at pH 4.0; some strains, however, were able to initiate growth to pH 3.8. The results indicate that the values of undissociated acid which occur in a silage of pH 4.1-4.5 are about 10-100 times higher than required in order to protect the forage from the growth of enterobacteria and L. monocytogenes.

  8. Formic acid

    Integrated Risk Information System (IRIS)

    Formic acid ; CASRN 64 - 18 - 6 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effect

  9. 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).

  10. Formic and acetic acid over the central Amazon region, Brazil. I - Dry season

    NASA Technical Reports Server (NTRS)

    Andreae, M. O.; Andreae, T. W.; Talbot, R. W.; Harriss, R. C.

    1988-01-01

    The concentrations of formic and acetic acids in the gas phase, atmospheric aerosol, and rainwater samples collected in Amazonia at ground level and in the atmosphere during the Amazon Boundary Layer Experiment in July/August 1985 were analyzed by ion exchange chromatography. The diurnal behavior of both acids at ground level and their vertical distribution in the forest canopy point to the existence of vegetative sources as well as to production by chemical reactions in the atmosphere. The concentrations of formic and acetic acids in the gas phase were about 2 orders of magnitude higher than the corresponding concentrations in the atmospheric aerosol. In rainwater, the total formate and acetate represented about one half of the anion equivalents, in contrast to less than 10 percent of the soluble anionic equivalents contributed by these acids in the atmospheric aerosol. The observed levels of these ions in rainwater are considered to be the result of a combination of chemical reactions in hydrometeors and the scavenging of the gaseous acids by cloud droplets.

  11. 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.

  12. The Partitioning of Acetic, Formic, and Phosphoric Acids Between Liquid Water and Steam

    SciTech Connect

    Gruszkiewicz, M.S.; Marshall, S.L.; Palmer, D.A.; Simonson, J.M.

    1999-06-22

    The chemical carryover of impurities and treatment chemicals from the boiler to the steam phase, and ultimately to the low-pressure turbine and condenser, can be quantified based on laboratory experiments preformed over ranges of temperature, pH, and composition. The two major assumptions are that thermodynamic equilibrium is maintained and no deposition, adsorption or decomposition occurs. The most recent results on acetic, formic and phosphoric acids are presented with consideration of the effects of hydrolysis and dimerization reactions. Complications arising from thermal decomposition of the organic acids are discussed. The partitioning constants for these acids and other solutes measured in this program have been incorporated into a simple thermodynamic computer code that calculates the effect of chemical and mechanical carryover on the composition of the condensate formed to varying extents in the water/steam cycle.

  13. An intercomparison of measurement systems for vapor and particulate phase concentrations of formic and acetic acids

    NASA Technical Reports Server (NTRS)

    Keene, William C.; Talbot, Robert W.; Andreae, Meinrat O.; Beecher, Kristene; Berresheim, Harold

    1989-01-01

    During June 1986, eight systems for measuring vapor phase and four for measuring particulate phase concentrations of formic acid (HCOOH) and acetic acid (CH3COOH) were intercompared in central Virginia. HCOOH and CH3COOH vapors were sampled by condensate, mist, Chromosorb 103 GC resin, NaOH-coated annular denuders, NaOH-impregnated quartz filters, K2CO3 and NaCO3-impregnated cellulose filters, and Nylasorb membranes. Atmospheric aerosol was collected on Teflon and Nuclepore filters using both hi-vol and lo-vol systems to measure particulate phase concentrations. Performances of the mist chamber and K2CO3-impregnated filter techniques were evaluated using zero air and ambient air spiked with HCOOH(g) and CH3COOH(g), and formaldehyde from permeation sources. The advantages and drawbacks of these methods are reported and discussed.

  14. Biorefining of wheat straw using an acetic and formic acid based organosolv fractionation process.

    PubMed

    Snelders, Jeroen; Dornez, Emmie; Benjelloun-Mlayah, Bouchra; Huijgen, Wouter J J; de Wild, Paul J; Gosselink, Richard J A; Gerritsma, Jort; Courtin, Christophe M

    2014-03-01

    To assess the potential of acetic and formic acid organosolv fractionation of wheat straw as basis of an integral biorefinery concept, detailed knowledge on yield, composition and purity of the obtained streams is needed. Therefore, the process was performed, all fractions extensively characterized and the mass balance studied. Cellulose pulp yield was 48% of straw dry matter, while it was 21% and 27% for the lignin and hemicellulose-rich fractions. Composition analysis showed that 67% of wheat straw xylan and 96% of lignin were solubilized during the process, resulting in cellulose pulp of 63% purity, containing 93% of wheat straw cellulose. The isolated lignin fraction contained 84% of initial lignin and had a purity of 78%. A good part of wheat straw xylan (58%) ended up in the hemicellulose-rich fraction, half of it as monomeric xylose, together with proteins (44%), minerals (69%) and noticeable amounts of acids used during processing.

  15. Formic and Acetic Acids in Degradation Products of Plant Volatiles Elicit Olfactory and Behavioral Responses from an Insect Vector.

    PubMed

    George, Justin; Robbins, Paul S; Alessandro, Rocco T; Stelinski, Lukasz L; Lapointe, Stephen L

    2016-05-01

    Volatile phytochemicals play a role in orientation by phytophagous insects. We studied antennal and behavioral responses of the Asian citrus psyllid, Diaphorina citri, vector of the citrus greening disease pathogen. Little or no response to citrus leaf volatiles was detected by electroantennography. Glass cartridges prepared with β-ocimene or citral produced no response initially but became stimulatory after several days. Both compounds degraded completely in air to a number of smaller molecules. Two peaks elicited large antennal responses and were identified as acetic and formic acids. Probing by D. citri of a wax substrate containing odorants was significantly increased by a blend of formic and acetic acids compared with either compound separately or blends containing β-ocimene and/or citral. Response surface modeling based on a 4-component mixture design and a 2-component mixture-amount design predicted an optimal probing response on wax substrate containing a blend of formic and acetic acids. Our study suggests that formic and acetic acids play a role in host selection by D. citri and perhaps by phytophagous insects in general even when parent compounds from which they are derived are not active. These results have implications for the investigation of arthropod olfaction and may lead to elaboration of attract-and-kill formulations to reduce nontarget effects of chemical control in agriculture. PMID:26857741

  16. In situ decarboxylation of acetic and formic acids in aqueous inclusions as a possible way to produce excess CH4

    NASA Astrophysics Data System (ADS)

    Ong, Anthony; Pironon, Jacques; Robert, Pascal; Dubessy, Jean; Caumon, Marie-Camille; Randi, Aurélien; Chailan, Olivier; Girard, Jean-Pierre

    2013-04-01

    Accurate reconstruction of diagenetic P-T conditions in petroleum reservoirs from fluid inclusion data relies on valid measurements of methane concentration in aqueous inclusions. Techniques have been developed (Raman spectrometry) to provide sufficiently accurate data, assuming measured methane concentration has not been modified after aqueous inclusion entrapment. In petroleum reservoirs, acetic (CH3COOH) and formic (HCOOH) acids are the most commonly reported organic acids, and the concentration of the total organic acids can be as high as 10,000 ppm at temperature below 120°C. This study investigates the likelihood that organic acids derived from petroleum fluids and dissolved in formation water might suffer decarboxylation upon post-entrapment heating within the fluid inclusion chamber upon post-entrapment heating, thereby generating excess CH4 in the inclusions. Four different experiments were conducted in Fused Silica Capillary Capsules (FSCCs), mimicking fluid inclusions. The capsules were loaded with acetic (CH3COOH) or formic (HCOOH) acid solution and were heated to 250°C for short durations (< 72hrs) in closed system conditions, with or without applying a fixed PH2. Reaction products were characterized by Raman and FT-IR spectrometry. The beginning of the decarboxylation of acetic acid is reached in 32 h at 250°C, with production of CH4 and CO2. Complete decarboxylation of formic acid is reached in 5 h at 250°C, with production of CO2, CO and H2. The lack of CH4 production in experiments with formic acid may be attributed to the relatively short duration of the experiments and/or the loss of H2 through the FSCC by diffusion during the experiment. Further experiments with a longer heating duration should be performed to assess the possibility of reducing the CO2 into CH4 from the formic acid. 2) The injection of H2 in the FSCC as a way to promote CO2 reduction did not promote decarboxylation in the duration of our experiment. These results suggest

  17. Exchange of atmospheric formic and acetic acids with trees and crop plants under controlled chamber and purified air conditions

    NASA Astrophysics Data System (ADS)

    Kesselmeier, J.; Bode, K.; Gerlach, C.; Jork, E.-M.

    We investigated the exchange of formic and acetic acids between the atmosphere and various tree species such as beech ( Fagus sylvatica L.), ash ( Fraxinus excelsior L.), spruce ( Picea abies L.) Karst, holm oak ( Quercus ilex L.), and birch ( Betula pendula L.). and some crop-plant species such as corn ( Zea mays, var. Banjo), pea ( Pisum sativum, var. Solara), barley ( Hordeum vulgare, var. Igri) and oat (Avena sativa, var. Wiesel). All experiments were done with dynamic enclosures flushed with purified oxidant-free air, containing only low or controlled amounts of the two acids. Significant and light-triggered emission of both acids from all tree species was observed. For one tree species (ash) a seasonal large increase in fall due to early leaf decomposition was found. The standard emission factors (30°C and PAR=1000 μmol m 2 s -1) given as (nmol m -2 min -1) for acetic and formic acids, respectively, were 8.1 and 29.7 (ash, autumn), 1.0 and 3.3 (ash, summer), 0.9 and 1.4 (beech), 0.7 and 1.45 (spruce), 1.9 and 2.4 (Holm oak) and 1.7 and 6.7 (birch). Rough estimation of global annual emissions range between 20 and 130 Gmol formic acid and 10 and 33 Gmol acetic acid. These numbers reflect a 15-30% contribution by forest emissions to the continental organic acid budget. As compared to the global total NMHC emissions low molecular weight organic acids are of minor importance. In contrast to the trees, none of the crop-plant species investigated showed an emission, but always a clear deposition of both acids. Both emission from trees as well as uptake by the agricultural plants could be related to transpiration rates and leaf conductances.

  18. An atom-economic approach to carboxylic acids via Pd-catalyzed direct addition of formic acid to olefins with acetic anhydride as a co-catalyst.

    PubMed

    Wang, Yang; Ren, Wenlong; Shi, Yian

    2015-08-21

    An effective Pd-catalyzed hydrocarboxylation of olefins using formic acid with acetic anhydride as a co-catalyst is described. A variety of carboxylic acids are obtained in good yields with high regioselectivities under mild reaction conditions without the use of toxic CO gas.

  19. Ecosystem-scale compensation points of formic and acetic acid in the central Amazon

    NASA Astrophysics Data System (ADS)

    Jardine, K.; Yañez Serrano, A.; Arneth, A.; Abrell, L.; Jardine, A.; Artaxo, P.; Alves, E.; Kesselmeier, J.; Taylor, T.; Saleska, S.; Huxman, T.

    2011-09-01

    Organic acids, central to terrestrial carbon metabolism and atmospheric photochemistry, are ubiquitous in the troposphere in the gas, particle, and aqueous phases. As the dominant organic acids in the atmosphere, formic acid (FA, HCOOH) and acetic acid (AA, CH3COOH) control precipitation acidity in remote regions and may represent a critical link between the terrestrial carbon and water cycles by acting as key intermediates in plant carbon and energy metabolism and aerosol-cloud-precipitation interactions. However, our understanding of the exchange of these acids between terrestrial ecosystems and the atmosphere is limited by a lack of field observations, the existence of biogenic and anthropogenic primary and secondary sources whose relative importance is unclear, and the fact that vegetation can act as both a source and a sink. Here, we first present data obtained from the tropical rainforest mesocosm at Biosphere 2 which isolates primary vegetation sources. Strong light and temperature dependent emissions enriched in FA relative to AA were simultaneously observed from individual branches (FA/AA = 2.1 ± 0.6) and mesocosm ambient air (FA/AA = 1.4 ± 0.3). We also present long-term observations of vertical concentration gradients of FA and AA within and above a primary rainforest canopy in the central Amazon during the 2010 dry and 2011 wet seasons. We observed a seasonal switch from net ecosystem-scale deposition during the dry season to net emissions during the wet season. This switch was associated with reduced ambient concentrations in the wet season (FA < 1.3 nmol mol-1, AA < 2.0 nmol mol-1) relative to the dry season (FA up to 3.3 nmol mol-1, AA up to 6.0 nmol mol-1), and a simultaneous increase in the FA/AA ambient concentration ratios from 0.3-0.8 in the dry season to 1.0-2.1 in the wet season. These observations are consistent with a switch between a biomass burning dominated source in the dry season (FA/AA < 1.0) to a vegetation dominated source in the

  20. Ecosystem-scale compensation points of formic and acetic acid in the central Amazon

    NASA Astrophysics Data System (ADS)

    Jardine, K.; Yañez Serrano, A.; Arneth, A.; Abrell, L.; Jardine, A.; Artaxo, P.; Alves, E.; Kesselmeier, J.; Taylor, T.; Saleska, S.; Huxman, T.

    2011-12-01

    Organic acids, central to terrestrial carbon metabolism and atmospheric photochemistry, are ubiquitous in the troposphere in the gas, particle, and aqueous phases. As the dominant organic acids in the atmosphere, formic acid (FA, HCOOH) and acetic acid (AA, CH3COOH) control precipitation acidity in remote regions and may represent a critical link between the terrestrial carbon and water cycles by acting as key intermediates in plant carbon and energy metabolism and aerosol-cloud-precipitation interactions. However, our understanding of the exchange of these acids between terrestrial ecosystems and the atmosphere is limited by a lack of field observations, the existence of biogenic and anthropogenic primary and secondary sources whose relative importance is unclear, and the fact that vegetation can act as both a source and a sink. Here, we first present data obtained from the tropical rainforest mesocosm at Biosphere 2 which isolates primary vegetation sources. Strong light and temperature dependent emissions enriched in FA relative to AA were simultaneously observed from individual branches (FA/AA = 3.0 ± 0.7) and mesocosm ambient air (FA/AA = 1.4 ± 0.3). We also present long-term observations of vertical concentration gradients of FA and AA within and above a primary rainforest canopy in the central Amazon during the 2010 dry and 2011 wet seasons. We observed a seasonal switch from net ecosystem-scale deposition during the dry season to net emissions during the wet season. This switch was associated with reduced ambient concentrations in the wet season (FA < 1.3 nmol mol-1, AA < 2.0 nmol mol-1) relative to the dry season (FA up to 3.3 nmol mol-1, AA up to 6.0 nmol mol-1), and a simultaneous increase in the FA/AA ambient concentration ratios from 0.3-0.8 in the dry season to 1.0-2.1 in the wet season. These observations are consistent with a switch between a biomass burning dominated source in the dry season (FA/AA < 1.0) to a vegetation dominated source in the

  1. Ecosystem-Scale Compensation Point Analysis of Formic and Acetic Acid in the Central Amazon

    NASA Astrophysics Data System (ADS)

    Yanez-Serrano, A. M.; Jardine, K. J.; Arneth, A.; Abrell, L.; Jardine, A. B.; Artaxo, P.; Gomes, E.; Kesselmeier, J.; Saleska, S. R.; Huxman, T. E.

    2011-12-01

    Organic acids, central to terrestrial carbon metabolism and atmospheric photochemistry, are ubiquitous in the troposphere in the gas, particle, and aqueous phases. As the dominant organic acids in the atmosphere, formic acid (FA, HCOOH) and acetic acid (AA, CH3COOH) control precipitation acidity in remote regions and may represent a critical link between the terrestrial carbon and water cycles by acting as key intermediates in plant carbon and energy metabolism and aerosol-cloud-precipitation interactions. However, our understanding of the exchange of these acids between terrestrial ecosystems and the atmosphere is limited by a lack of field observations, the existence of biogenic and anthropogenic primary and secondary sources whose relative importance is unclear, and the fact that vegetation can act as both a source and a sink. Here, we present results from the tropical rainforest mescosom at Biosphere 2 which isolates primary vegetation sources. Strong light and temperature dependent emissions of FA and AA were simultaneously observed from individual branches and mesocosm ambient air with a strong enrichment in FA (FA/AA = 1.4 +/- 0.3, R2 of 0.89 +/- 0.10). We also present long-term observations of vertical concentration gradients of FA and AA within and above a primary rainforest canopy in central Amazonia during the 2010 dry and 2011 wet seasons. We observed a seasonal switch from net ecosystem-scale deposition during the dry season to net emissions during the wet season. This switch was associated with reduced ambient concentrations in the wet season (FA < 1.3 ppbv, AA < 2.0 ppbv) relative to the dry season (FA up to 3.3 ppbv, AA up to 6.0 ppbv), and a simultaneous increase in the FA/AA ambient concentration ratios from 0.3-0.8 in the dry season to 1.0-2.1 in the wet season. These observations are consistent with a switch between a biomass burning dominated source in the dry season (FA/AA < 1.0) to a vegetation dominated source in the wet season and call into

  2. Characteristics and sources of formic, acetic and oxalic acids in PM 2.5 and PM 10 aerosols in Beijing, China

    NASA Astrophysics Data System (ADS)

    Wang, Ying; Zhuang, Guoshun; Chen, Shuang; An, Zhisheng; Zheng, Aihua

    2007-04-01

    Chemistry of formic, acetic and oxalic acids was studied at four sites representing the urban and rural conditions in Beijing from March 2002 to October 2003. The investigation was based on the PM 2.5 and PM 10 aerosols collected with virtual samplers. The total concentrations of these carboxylic acids averaged at 541 ng m - 3 in PM 2.5 and 615 ng m - 3 in PM 10, contributing 0.4% and 0.3% to the total mass of the aerosol, respectively. Oxalic acid was the most abundant carboxylic acids in aerosols. Formic and acetic acids displayed different seasonal variations (formic: spring < summer < autumn < winter; acetic: spring > summer > autumn > winter), and the variations of these acids were consistent among different sites in urban area. Formic and oxalic acids had a diurnal variation of nighttime < daytime. Formic and acetic acids had mass both in the fine and in the coarse modes, while oxalic acid predominated in the fine mode. The coarse mode fraction of these acids was elevated in summer. The traffic/dust/soil/vegetation emissions, coal/waste/biomass burnings, cooking and secondary formation from anthropogenic or natural gas-phase precursors could be the major sources of these acids. Acetic-to-formic acid ratio (A/F) was used to distinguish the primary sources and the secondary sources, and it indicated that the contribution of the primary sources was higher at rural site than at urban sites. A new method was developed to study the contribution of the biomass burning to these acids, which was estimated to be 30-60% for formic and oxalic acids in aerosols.

  3. Formic and Acetic Acid Observations over Colorado by Chemical Ionization Mass Spectrometry and Organic Acids' Role in Air Quality

    NASA Astrophysics Data System (ADS)

    Treadaway, V.; O'Sullivan, D. W.; Heikes, B.; Silwal, I.; McNeill, A.

    2015-12-01

    Formic acid (HFo) and acetic acid (HAc) have both natural and anthropogenic sources and a role in the atmospheric processing of carbon. These organic acids also have an increasing importance in setting the acidity of rain and snow as precipitation nitrate and sulfate concentrations have decreased. Primary emissions for both organic acids include biomass burning, agriculture, and motor vehicle emissions. Secondary production is also a substantial source for both acids especially from biogenic precursors, secondary organic aerosols (SOAs), and photochemical production from volatile organic compounds (VOCs) and oxygenated volatile organic compounds (OVOCs). Chemical transport models underestimate organic acid concentrations and recent research has sought to develop additional production mechanisms. Here we report HFo and HAc measurements during two campaigns over Colorado using the peroxide chemical ionization mass spectrometer (PCIMS). Iodide clusters of both HFo and HAc were recorded at mass-to-charge ratios of 173 and 187, respectively. The PCIMS was flown aboard the NCAR Gulfstream-V platform during the Deep Convective Clouds and Chemistry Experiment (DC3) and aboard the NCAR C-130 during the Front Range Air Pollution and Photochemistry Experiment (FRAPPE). The DC3 observations were made in May and June 2012 extending from the surface to 13 km over the central and eastern United States. FRAPPE observations were made in July and August 2014 from the surface to 7 km over Colorado. DC3 measurements reported here are focused over the Colorado Front Range and complement the FRAPPE observations. DC3 HFo altitude profiles are characterized by a decrease up to 6 km followed by an increase either back to boundary layer mixing ratio values or higher (a "C" shape). Organic acid measurements from both campaigns are interpreted with an emphasis on emission sources (both natural and anthropogenic) over Colorado and in situ photochemical production especially ozone precursors.

  4. Large-Scale Distributions of Tropospheric Nitric, Formic, and Acetic acids Over the Westerm Pacific Basin During Wintertime

    NASA Technical Reports Server (NTRS)

    Talbot, R. W.; Dibb, J. E.; Lefer, B. L.; Scheuer, E. M.; Bradshaw, J. D.; Sandholm, S. T.; Smyth, S.; Blake, D. R.; Blake, N. J.; Sachse, G. W.; Collins, J. E.; Gregory, G. L.

    1997-01-01

    We report here measurements of the acidic gases nitric (HNO3), formic (HCOOH), and acetic (CH3COOH) over the western Pacific basin during the February-March 1994 Pacific Exploratory Mission-West (PEM-West B). These data were obtained aboard the NASA DC-8 research aircraft as it flew missions in the altitude range of 0.3 - 12.5 km over equatorial regions near Guam and then further westward encompassing the entire Pacific Rim arc. Aged marine air over the equatorial Pacific generally exhibited mixing ratios of acidic gases less than 100 parts per trillion by volume (pptv). Near the Asian continent, discrete plumes encountered below 6 km altitude contained up to 8 parts per billion by volume (ppbv) HNO3 and 10 ppbv HCOOH and CH3COOH. Overall there was a general correlation between mixing ratios of acidic gases with those of CO, C2H2, and C2Cl4, indicative of emissions from combustion and industrial sources. The latitudinal distributions of HNO3 and CO showed that the largest mixing ratios were centered around 15 deg N, while HCOOH, CH3COOH, and C2Cl4 peaked at 25 deg N. The mixing ratios of HCOOH and CH3COOH were highly correlated (r(sup 2) = 0.87) below 6 km altitude, with a slope (0.89) characteristic of the nongrowing season at midlatitudes in the northern hemisphere. Above 6 km altitude, HCOOH and CH3COOH were marginally correlated (r(sup 2) = 0.50), and plumes well defined by CO, C2H2, and C2Cl4 were depleted in acidic gases, most likely due to scavenging during vertical transport of air masses through convective cloud systems over the Asian continent. In stratospheric air masses, HNO, mixing ratios were several parts per billion by volume (ppbv), yielding relationships with 03 and N2O consistent with those previously reported for NO(y).

  5. Measuring acetic and formic acid by proton-transfer-reaction mass spectrometry: sensitivity, humidity dependence, and quantifying interferences

    NASA Astrophysics Data System (ADS)

    Baasandorj, M.; Millet, D. B.; Hu, L.; Mitroo, D.; Williams, B. J.

    2015-03-01

    We present a detailed investigation of the factors governing the quantification of formic acid (FA), acetic acid (AA), and their relevant mass analogues by proton-transfer-reaction mass spectrometry (PTR-MS), assess the underlying fragmentation pathways and humidity dependencies, and present a new method for separating FA and AA from their main isobaric interferences. PTR-MS sensitivities towards glycolaldehyde, ethyl acetate, and peroxyacetic acid at m/z 61 are comparable to that for AA; when present, these species will interfere with ambient AA measurements by PTR-MS. Likewise, when it is present, dimethyl ether can interfere with FA measurements. For a reduced electric field (E/N) of 125 Townsend (Td), the PTR-MS sensitivity towards ethanol at m/z 47 is 5-20 times lower than for FA; ethanol will then only be an important interference when present in much higher abundance than FA. Sensitivity towards 2-propanol is <1% of that for AA, so that propanols will not in general represent a significant interference for AA. Hydrated product ions of AA, glycolaldehyde, and propanols occur at m/z 79, which is also commonly used to measure benzene. However, the resulting interference for benzene is only significant when E/N is low (≲100 Td). Addition of water vapor affects the PTR-MS response to a given compound by (i) changing the yield for fragmentation reactions and (ii) increasing the importance of ligand switching reactions. In the case of AA, sensitivity to the molecular ion increases with humidity at low E/N but decreases with humidity at high E/N due to water-driven fragmentation. Sensitivity towards FA decreases with humidity throughout the full range of E/N. For glycolaldehyde and the alcohols, the sensitivity increases with humidity due to ligand switching reactions (at low E/N) and reduced fragmentation in the presence of water (at high E/N). Their role as interferences will typically be greatest at high humidity. For compounds such as AA where the

  6. Barriers to rotation adjacent to double bonds. 3. The C-O barrier in formic acid, methyl formate, acetic acid, and methyl acetate. The origin of ester and amide resonance

    SciTech Connect

    Wiberg, K.B.; Laidig, K.E.

    1987-09-30

    The structures of the rotamers about the C-O bonds of formic acid, methyl formate, acetic acid, and methyl acetate were calculated by using the 6-31G* basis set and complete geometrical relaxation. Large basis sets (6-311+G**) and correction for electron correlation were needed in order to obtain calculated barriers that were in good agreement with the available experimental data. The factors that control the geometry at a carbonyl group are considered, and it is shown that an analysis in terms of bond path angles leads to a direct connection with electronegativity. The nature of the interaction between an amino group and a carbonyl, as in an amide, is examined and shown not to involve charge transfer from the nitrogen to the carbonyl oxygen, but rather it involves charge transfer between carbon and nitrogen. The origin of the rotational barrier in esters and of the difference in energy between the E and Z conformers is discussed.

  7. 21 CFR 573.480 - Formic acid.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Formic acid. 573.480 Section 573.480 Food and... Listing § 573.480 Formic acid. The food additive, formic acid, may be safely used in accordance with the...) The top foot of silage stored should not contain formic acid and (2) Silage should not be fed...

  8. 21 CFR 573.480 - Formic acid.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Formic acid. 573.480 Section 573.480 Food and... Listing § 573.480 Formic acid. The food additive, formic acid, may be safely used in accordance with the...) The top foot of silage stored should not contain formic acid and (2) Silage should not be fed...

  9. 21 CFR 573.480 - Formic acid.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Formic acid. 573.480 Section 573.480 Food and... Listing § 573.480 Formic acid. The food additive, formic acid, may be safely used in accordance with the...) The top foot of silage stored should not contain formic acid and (2) Silage should not be fed...

  10. 21 CFR 573.480 - Formic acid.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Formic acid. 573.480 Section 573.480 Food and... Listing § 573.480 Formic acid. The food additive, formic acid, may be safely used in accordance with the...) The top foot of silage stored should not contain formic acid and (2) Silage should not be fed...

  11. GLYCOLIC - FORMIC ACID FLOWSHEET DEVELOPMENT

    SciTech Connect

    Pickenheim, B.; Stone, M.; Newell, J.

    2010-11-08

    Flowsheet testing was performed to further develop the nitric/glycolic/formic acid flowsheet as an alternative to the nitric/formic flowsheet currently being processed at the DWPF. This new flowsheet has shown that mercury can be removed in the Sludge Receipt and Adjustment Tank (SRAT) with minimal hydrogen generation. All other processing objectives were also met, including greatly reducing the Slurry Mix Evaporator (SME) product yield stress as compared to the baseline nitric/formic flowsheet. Eight runs were performed in total, including the baseline run. The baseline nitric/formic flowsheet run was extremely difficult to process under existing DWPF acceptance criteria with this simulant at the HM levels of noble metals. While nitrite was destroyed and mercury was removed to near the DWPF limit, the rheology of the SRAT and SME products were well above design basis and hydrogen generation far exceeded the DWPF limit. In addition, mixing during the SME cycle was very poor. In this sense, the nitric/glycolic/formic acid flowsheet represents a significant upgrade over the current flowsheet. In the nitric/glycolic/formic flowsheet runs, mercury was successfully removed with almost no hydrogen generation and the SRAT and SME products yield stresses were within process limits or previously processed ranges. It is recommended that DWPF continue to support development of the nitric/glycolic/formic flowsheet. Although experience is limited at this time, this flowsheet meets or outperforms the current flowsheet in many regards, including off-gas generation, mercury removal, product rheology and general ease of processing. Additional flowsheet testing will allow for a more thorough understanding of the chemistry and effectiveness of the flowsheet over a range of sludge compositions and formic/glycolic ratios. This testing will also show whether the REDOX and metal solubility concerns with this change in the flowsheet can be addressed by just adjusting the volumes of

  12. Dehydrogenation of Formic Acid by Heterogeneous Catalysts.

    PubMed

    Li, Jun; Zhu, Qi-Long; Xu, Qiang

    2015-01-01

    Formic acid has recently been considered as one of the most promising hydrogen storage materials. The basic concept is briefly discussed and the research progress is detailledly reviewed on the dehydrogenation of aqueous formic acid by heterogeneous catalysts. PMID:26507481

  13. 21 CFR 573.480 - Formic acid.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Formic acid. 573.480 Section 573.480 Food and... Listing § 573.480 Formic acid. Formic acid may be safely used as a preservative in hay crop silage in an.... The top foot of silage stored should not contain formic acid and silage should not be fed to...

  14. 21 CFR 186.1316 - Formic acid.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Formic acid. 186.1316 Section 186.1316 Food and... Substances Affirmed as GRAS § 186.1316 Formic acid. (a) Formic acid (CH2O2, CAS Reg. No. 64-18-6) is also referred to as methanoic acid or hydrogen carboxylic acid. It occurs naturally in some insects and...

  15. 21 CFR 186.1316 - Formic acid.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Formic acid. 186.1316 Section 186.1316 Food and... Substances Affirmed as GRAS § 186.1316 Formic acid. (a) Formic acid (CH2O2, CAS Reg. No. 64-18-6) is also referred to as methanoic acid or hydrogen carboxylic acid. It occurs naturally in some insects and...

  16. 21 CFR 186.1316 - Formic acid.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Formic acid. 186.1316 Section 186.1316 Food and... Substances Affirmed as GRAS § 186.1316 Formic acid. (a) Formic acid (CH2O2, CAS Reg. No. 64-18-6) is also referred to as methanoic acid or hydrogen carboxylic acid. It occurs naturally in some insects and...

  17. 21 CFR 186.1316 - Formic acid.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Formic acid. 186.1316 Section 186.1316 Food and....1316 Formic acid. (a) Formic acid (CH2O2, CAS Reg. No. 64-18-6) is also referred to as methanoic acid or hydrogen carboxylic acid. It occurs naturally in some insects and is contained in the free...

  18. 21 CFR 186.1316 - Formic acid.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Formic acid. 186.1316 Section 186.1316 Food and... Substances Affirmed as GRAS § 186.1316 Formic acid. (a) Formic acid (CH2O2, CAS Reg. No. 64-18-6) is also referred to as methanoic acid or hydrogen carboxylic acid. It occurs naturally in some insects and...

  19. Aqueous-phase source of formic acid in clouds

    NASA Technical Reports Server (NTRS)

    Chameides, W. L.; Davis, D. D.

    1983-01-01

    The coupled gas- and aqueous-phase cloud chemistry of HCOOH were examined for controlling factors in the acidity of cloud and rainwater. Attention was given to the aqueous OH/HO2 system that yields an OH species that is highly reactive with other species, notably SO2 and the formaldehyde/formic acid complex. A numerical model was developed to simulate the cloud chemistry in the remote troposphere, with considerations given to CH4-CO-NO(x)-O3-H(x)O(y) system. It was determined that aqueous phase OH radicals can produce and destroy formic acid droplets in daylight conditions, as well as control formic acid levels in rainwater. It is sugested that the same types of reactions may be involved in the control of acetic acid and other organic acids.

  20. Inverse metabolic engineering based on transient acclimation of yeast improves acid-containing xylose fermentation and tolerance to formic and acetic acids.

    PubMed

    Hasunuma, Tomohisa; Sakamoto, Takatoshi; Kondo, Akihiko

    2016-01-01

    Improving the production of ethanol from xylose is an important goal in metabolic engineering of Saccharomyces cerevisiae. Furthermore, S. cerevisiae must produce ethanol in the presence of weak acids (formate and acetate) generated during pre-treatment of lignocellulosic biomass. In this study, weak acid-containing xylose fermentation was significantly improved using cells that were acclimated to the weak acids during pre-cultivation. Transcriptome analyses showed that levels of transcripts for transcriptional/translational machinery-related genes (RTC3 and ANB1) were enhanced by formate and acetate acclimation. Recombinant yeast strains overexpressing RTC3 and ANB1 demonstrated improved ethanol production from xylose in the presence of the weak acids, along with improved tolerance to the acids. Novel metabolic engineering strategy based on the combination of short-term acclimation and system-wide analysis was developed, which can develop stress-tolerant strains in a short period of time, although conventional evolutionary engineering approach has required long periods of time to isolate inhibitor-adapted strains.

  1. Low contaminant formic acid fuel for direct liquid fuel cell

    DOEpatents

    Masel, Richard I.; Zhu, Yimin; Kahn, Zakia; Man, Malcolm

    2009-11-17

    A low contaminant formic acid fuel is especially suited toward use in a direct organic liquid fuel cell. A fuel of the invention provides high power output that is maintained for a substantial time and the fuel is substantially non-flammable. Specific contaminants and contaminant levels have been identified as being deleterious to the performance of a formic acid fuel in a fuel cell, and embodiments of the invention provide low contaminant fuels that have improved performance compared to known commercial bulk grade and commercial purified grade formic acid fuels. Preferred embodiment fuels (and fuel cells containing such fuels) including low levels of a combination of key contaminants, including acetic acid, methyl formate, and methanol.

  2. Flexible fibers wet-spun from formic acid modified chitosan.

    PubMed

    Li, Jinlei; Liu, Dagang; Hu, Chengming; Sun, Fengxiang; Gustave, Williamson; Tian, Huafeng; Yang, Shuguang

    2016-01-20

    The rigidity and low strain of chitosan fibers hindered their broader utility for biomedical applications. In present work, formic acid was employed as an efficient modifier for chitosan to prepare flexible fibers wet-spun from the formic acid modified chitosan solution. The formation of amide linkages between chitosan and formic acid was confirmed by FTIR, (13)C NMR, (1)H NMR and XRD measurements. The degree of formylation evaluated by (1)H NMR spectra was varied from 14.1% to 37.2% as a function of the reaction temperature. The results of the mechanical properties showed that the as-spun fibers exhibited an enhanced ductility with a maximum elongation at break of 21.7% compared with that spun from the chitosan dissolved in diluted acetic acid. The novel flexible chitosan fibers were anticipated to be used as comfortable wound dressing and bandages in biomedical fields.

  3. Atmospheric measurements of pyruvic and formic acid

    NASA Technical Reports Server (NTRS)

    Andreae, Meinrat O.; Li, Shao-Meng; Talbot, Robert W.

    1987-01-01

    Pyruvic acid, a product of the atmospheric oxidation of cresols and probably of isoprene, has been determined together with formic acid in atmospheric aerosols and rain as well as in the vapor phase. Both acids are present predominantly as vapor; only about 10-20 percent of the total atmospheric pyruvate and 1-2 percent of the total formate are in the particulate phase. The concentrations of pyruvic and formic acid are highly correlated, with typical formic-to-pyruvic ratios of 10-30 in the gas phase, 20-30 in rain, and 2-10 in aerosols. The gas-phase and rain ratios are comparable to those predicted to result from isoprene oxidation. Pyruvic acid levels were similar in the eastern United States (during summer) and the Amazon Basin, suggesting that natural processes, particularly the photochemical oxidation of isoprene, could account for most of the pyruvic acid present in the atmosphere.

  4. Photolysis of formic acid at 355 nm

    NASA Astrophysics Data System (ADS)

    Martinez, Denhi; Bautista, Teonanacatl; Guerrero, Alfonso; Alvarez, Ignacio; Cisneros, Carmen

    2015-05-01

    Formic acid is well known as a food additive and recently an application on fuel cell technology has emerged. In this work we have studied the dissociative ionization process by multiphoton absorption of formic acid molecules at 355nm wavelength photons, using TOF spectrometry in reflectron mode (R-TOF). Some of the most abundant ionic fragments produced are studied at different settings of the laser harmonic generator. The dependence of the products on these conditions is reported. This work was supported by CONACYT Project 165410 and PAPIIT IN102613 and IN101215.

  5. Formic acid fuel cells and catalysts

    DOEpatents

    Masel, Richard I.; Larsen, Robert; Ha, Su Yun

    2010-06-22

    An exemplary fuel cell of the invention includes a formic acid fuel solution in communication with an anode (12, 134), an oxidizer in communication with a cathode (16, 135) electrically linked to the anode, and an anode catalyst that includes Pd. An exemplary formic acid fuel cell membrane electrode assembly (130) includes a proton-conducting membrane (131) having opposing first (132) and second surfaces (133), a cathode catalyst on the second membrane surface, and an anode catalyst including Pd on the first surface.

  6. Versatile microanalytical system with porous polypropylene capillary membrane for calibration gas generation and trace gaseous pollutants sampling applied to the analysis of formaldehyde, formic acid, acetic acid and ammonia in outdoor air.

    PubMed

    Coelho, Lúcia H G; Melchert, Wanessa R; Rocha, Flavio R; Rocha, Fábio R P; Gutz, Ivano G R

    2010-11-15

    The analytical determination of atmospheric pollutants still presents challenges due to the low-level concentrations (frequently in the μg m(-3) range) and their variations with sampling site and time. In this work, a capillary membrane diffusion scrubber (CMDS) was scaled down to match with capillary electrophoresis (CE), a quick separation technique that requires nothing more than some nanoliters of sample and, when combined with capacitively coupled contactless conductometric detection (C(4)D), is particularly favorable for ionic species that do not absorb in the UV-vis region, like the target analytes formaldehyde, formic acid, acetic acid and ammonium. The CMDS was coaxially assembled inside a PTFE tube and fed with acceptor phase (deionized water for species with a high Henry's constant such as formaldehyde and carboxylic acids, or acidic solution for ammonia sampling with equilibrium displacement to the non-volatile ammonium ion) at a low flow rate (8.3 nL s(-1)), while the sample was aspirated through the annular gap of the concentric tubes at 2.5 mL s(-1). A second unit, in all similar to the CMDS, was operated as a capillary membrane diffusion emitter (CMDE), generating a gas flow with know concentrations of ammonia for the evaluation of the CMDS. The fluids of the system were driven with inexpensive aquarium air pumps, and the collected samples were stored in vials cooled by a Peltier element. Complete protocols were developed for the analysis, in air, of NH(3), CH(3)COOH, HCOOH and, with a derivatization setup, CH(2)O, by associating the CMDS collection with the determination by CE-C(4)D. The ammonia concentrations obtained by electrophoresis were checked against the reference spectrophotometric method based on Berthelot's reaction. Sensitivity enhancements of this reference method were achieved by using a modified Berthelot reaction, solenoid micro-pumps for liquid propulsion and a long optical path cell based on a liquid core waveguide (LCW). All

  7. Reaction of atomic hydrogen with formic acid.

    PubMed

    Cao, Qian; Berski, Slawomir; Latajka, Zdzislaw; Räsänen, Markku; Khriachtchev, Leonid

    2014-04-01

    We study the reaction of atomic hydrogen with formic acid and characterize the radical products using IR spectroscopy in a Kr matrix and quantum chemical calculations. The reaction first leads to the formation of an intermediate radical trans-H2COOH, which converts to the more stable radical trans-cis-HC(OH)2via hydrogen atom tunneling on a timescale of hours at 4.3 K. These open-shell species are observed for the first time as well as a reaction between atomic hydrogen and formic acid. The structural assignment is aided by extensive deuteration experiments and ab initio calculations at the UMP2 and UCCSD(T) levels of theory. The simplest geminal diol radical trans-cis-HC(OH)2 identified in the present work as the final product of the reaction should be very reactive, and further reaction channels are of particular interest. These reactions and species may constitute new channels for the initiation and propagation of more complex organic species in the interstellar clouds.

  8. Technical and economical assessment of formic acid to recycle phosphorus from pig slurry by a combined acidification-precipitation process.

    PubMed

    Daumer, M-L; Picard, S; Saint-Cast, P; Dabert, P

    2010-08-15

    Dissolution by acidification followed by a liquid/solid separation and precipitation of phosphorus from the liquid phase is one possibility to recycle phosphorus from livestock effluents. To avoid increase of effluent salinity by using mineral acids in the recycling process, the efficiency of two organic acids, formic and acetic acid, in dissolving the mineral phosphorus from piggery wastewater was compared. The amount of formic acid needed to dissolve the phosphorus was reduced three fold, compared to acetic acid. The amount of magnesium oxide needed for further precipitation was decreased by two with formic acid. Neither the carbon load nor the effluent salinity was significantly increased by using formic acid. An economical comparison was performed for the chemical recycling process (mineral fertilizer) vs. centrifugation (organic fertilizer) considering the centrifugation and the mineral fertilizers sold in the market. After optimisation of the process, the product could be economically competitive with mineral fertilizer as superphosphate in less than 10 years. PMID:20471746

  9. Suicidal chemistry: combined intoxication with carbon monoxide and formic acid.

    PubMed

    Bakovic, Marija; Nestic, Marina; Mayer, Davor

    2016-05-01

    Herein, we present a rare case of suicidal intoxication with carbon monoxide produced via reaction of formic and sulphuric acid with additional toxic effect of formic acid. The deceased was a 22-year-old men found dead in the bathroom locked from the inside. A bucket filled with liquid was found next to him, together with an almost empty canister labeled "formic acid" and another empty unlabeled canister. The postmortem examination revealed corrosive burns of the face, neck and chest, cherry-pink livor mortis, corrosive injury to the oropharyngeal area and trachea, subpleural petechiae, 100 mL of blood in stomach and superficial erosions of stomach mucosa. Toxicology analysis revealed 30% of carboxyhemoglobin in the femoral blood and the presence of the formic acid in various samples. Quantitative analysis of formic acid was performed by measuring methyl ester derivative of formic acid by using headspace gas chromatography with flame ionization detection. The highest concentration of formic acid was measured in the lungs (0.55 g/kg), gastric content (0.39 g/L), and blood (0.28 g/L). In addition, it was established that content of the unlabeled canister had a pH value of 0.79 and contained sulphuric ions. Morphological and toxicology findings suggested that the main route of exposure to formic acid was inhalation of vapors with a possible ingestion of only small amount of liquid acid. The cause of death was determined to be combined intoxication with carbon monoxide and formic acid. PMID:26041513

  10. Suicidal chemistry: combined intoxication with carbon monoxide and formic acid.

    PubMed

    Bakovic, Marija; Nestic, Marina; Mayer, Davor

    2016-05-01

    Herein, we present a rare case of suicidal intoxication with carbon monoxide produced via reaction of formic and sulphuric acid with additional toxic effect of formic acid. The deceased was a 22-year-old men found dead in the bathroom locked from the inside. A bucket filled with liquid was found next to him, together with an almost empty canister labeled "formic acid" and another empty unlabeled canister. The postmortem examination revealed corrosive burns of the face, neck and chest, cherry-pink livor mortis, corrosive injury to the oropharyngeal area and trachea, subpleural petechiae, 100 mL of blood in stomach and superficial erosions of stomach mucosa. Toxicology analysis revealed 30% of carboxyhemoglobin in the femoral blood and the presence of the formic acid in various samples. Quantitative analysis of formic acid was performed by measuring methyl ester derivative of formic acid by using headspace gas chromatography with flame ionization detection. The highest concentration of formic acid was measured in the lungs (0.55 g/kg), gastric content (0.39 g/L), and blood (0.28 g/L). In addition, it was established that content of the unlabeled canister had a pH value of 0.79 and contained sulphuric ions. Morphological and toxicology findings suggested that the main route of exposure to formic acid was inhalation of vapors with a possible ingestion of only small amount of liquid acid. The cause of death was determined to be combined intoxication with carbon monoxide and formic acid.

  11. A prolific catalyst for dehydrogenation of neat formic acid

    PubMed Central

    Celaje, Jeff Joseph A.; Lu, Zhiyao; Kedzie, Elyse A.; Terrile, Nicholas J.; Lo, Jonathan N.; Williams, Travis J.

    2016-01-01

    Formic acid is a promising energy carrier for on-demand hydrogen generation. Because the reverse reaction is also feasible, formic acid is a form of stored hydrogen. Here we present a robust, reusable iridium catalyst that enables hydrogen gas release from neat formic acid. This catalysis works under mild conditions in the presence of air, is highly selective and affords millions of turnovers. While many catalysts exist for both formic acid dehydrogenation and carbon dioxide reduction, solutions to date on hydrogen gas release rely on volatile components that reduce the weight content of stored hydrogen and/or introduce fuel cell poisons. These are avoided here. The catalyst utilizes an interesting chemical mechanism, which is described on the basis of kinetic and synthetic experiments. PMID:27076111

  12. A prolific catalyst for dehydrogenation of neat formic acid.

    PubMed

    Celaje, Jeff Joseph A; Lu, Zhiyao; Kedzie, Elyse A; Terrile, Nicholas J; Lo, Jonathan N; Williams, Travis J

    2016-01-01

    Formic acid is a promising energy carrier for on-demand hydrogen generation. Because the reverse reaction is also feasible, formic acid is a form of stored hydrogen. Here we present a robust, reusable iridium catalyst that enables hydrogen gas release from neat formic acid. This catalysis works under mild conditions in the presence of air, is highly selective and affords millions of turnovers. While many catalysts exist for both formic acid dehydrogenation and carbon dioxide reduction, solutions to date on hydrogen gas release rely on volatile components that reduce the weight content of stored hydrogen and/or introduce fuel cell poisons. These are avoided here. The catalyst utilizes an interesting chemical mechanism, which is described on the basis of kinetic and synthetic experiments. PMID:27076111

  13. GLYCOLIC-FORMIC ACID FLOWSHEET FINAL REPORT FOR DOWNSELECTION DECISION

    SciTech Connect

    Lambert, D.; Pickenheim, B.; Stone, M.; Newell, J.; Best, D.

    2011-03-10

    Flowsheet testing was performed to develop the nitric-glycolic-formic acid flowsheet (referred to as the glycolic-formic flowsheet throughout the rest of the report) as an alternative to the nitric/formic flowsheet currently being processed at the DWPF. This new flowsheet has shown that mercury can be removed in the Sludge Receipt and Adjustment Tank (SRAT) with minimal hydrogen generation. All processing objectives were also met, including greatly reducing the Slurry Mix Evaporator (SME) product yield stress as compared to the baseline nitric/formic flowsheet. Forty-six runs were performed in total, including the baseline run and the melter feed preparation runs. Significant results are summarized. The baseline nitric/formic flowsheet run, using the SB6 simulant produced by Harrell was extremely difficult to process successfully under existing DWPF acceptance criteria with this simulant at the HM levels of noble metals. While nitrite was destroyed and mercury was removed to near the DWPF limit, the rheology of the SRAT and SME products were well above design basis and hydrogen generation far exceeded the DWPF SRAT limit. In addition, mixing during the SME cycle was very poor. In this sense, the nitric/glycolic/formic acid flowsheet represents a significant upgrade over the current flowsheet. Mercury was successfully removed with almost no hydrogen generation and the SRAT and SME products yield stresses were within process limits or previously processed ranges. The glycolic-formic flowsheet has a very wide processing window. Testing was completed from 100% to 200% of acid stoichiometry and using a glycolic-formic mixture from 40% to 100% glycolic acid. The testing met all processing requirements throughout these processing windows. This should allow processing at an acid stoichiometry of 100% and a glycolic-formic mixture of 80% glycolic acid with minimal hydrogen generation. It should also allow processing endpoints in the SRAT and SME at significantly higher

  14. Hydrogen Storage in the Carbon Dioxide - Formic Acid Cycle.

    PubMed

    Fink, Cornel; Montandon-Clerc, Mickael; Laurenczy, Gabor

    2015-01-01

    This year Mankind will release about 39 Gt carbon dioxide into the earth's atmosphere, where it acts as a greenhouse gas. The chemical transformation of carbon dioxide into useful products becomes increasingly important, as the CO(2) concentration in the atmosphere has reached 400 ppm. One approach to contribute to the decrease of this hazardous emission is to recycle CO(2), for example reducing it to formic acid. The hydrogenation of CO(2) can be achieved with a series of catalysts under basic and acidic conditions, in wide variety of solvents. To realize a hydrogen-based charge-discharge device ('hydrogen battery'), one also needs efficient catalysts for the reverse reaction, the dehydrogenation of formic acid. Despite of the fact that the overwhelming majority of these reactions are carried out using precious metals-based catalysts (mainly Ru), we review here developments for catalytic hydrogen evolution from formic acid with iron-based complexes. PMID:26842324

  15. Microwave structure for the propiolic acid-formic acid complex.

    PubMed

    Kukolich, Stephen G; Mitchell, Erik G; Carey, Spencer J; Sun, Ming; Sargus, Bryan A

    2013-10-01

    New microwave spectra were measured to obtain rotational constants and centrifugal distortion constants for the DCCCOOH···HOOCH and HCCCOOD···DOOCH isotopologues. Rotational transitions were measured in the frequency range of 4.9-15.4 GHz, providing accurate rotational constants, which, combined with previous rotational constants, allowed an improved structural fit for the propiolic acid-formic acid complex. The new structural fit yields reasonably accurate orientations for both the propiolic and formic acid monomers in the complex and more accurate structural parameters describing the hydrogen bonding. The structure is planar, with a positive inertial defect of Δ = 1.33 amu Å(2). The experimental structure exhibits a greater asymmetry for the two hydrogen bond lengths than was obtained from the ab initio mp2 calculations. The best-fit hydrogen bond lengths have an r(O1-H1···O4) of 1.64 Å and an r(O3-H2···O2) of 1.87 Å. The average of the two hydrogen bond lengths is r(av)(exp) = 1.76 Å, in good agreement with r(av)(theory) = 1.72 Å. The center of mass separation of the monomers is R(CM) = 3.864 Å. Other structural parameters from the least-squares fit using the experimental rotational constants are compared with theoretical values. The spectra were obtained using two different pulsed beam Fourier transform microwave spectrometers.

  16. State-selected imaging studies of formic acid photodissociation dynamics

    SciTech Connect

    Huang Cunshun; Yang Xueming; Zhang Cuimei

    2010-04-21

    The photodissociation dynamics of formic acid have been studied using the velocity map ion imaging at the UV region. The measurements were made with resonance enhancement multiphoton ionization (REMPI) spectroscopy and dc slicing ion imaging. The OH REMPI spectrum from the photodissociation of formic acid at 244 nm has been recorded. The spectrum shows low rotational excitation (N{<=}4). By fixing the probe laser at the specific rotational transitions, the resulting OH images from various dissociation wavelengths have been accumulated. The translational energy distributions derived from the OH images imply that about half of the available energies go to the photofragments internal excitation. The dissociation dynamics of formic acid were also discussed in view of the recent theoretical calculations.

  17. Enhanced formic acid oxidation on Cu-Pd nanoparticles

    NASA Astrophysics Data System (ADS)

    Dai, Lin; Zou, Shouzhong

    Developing catalysts with high activity and high resistance to surface poisoning remains a challenge in direct formic acid fuel cell research. In this work, copper-palladium nanoparticles were formed through a galvanic replacement process. After electrochemically selective dissolution of surface Cu, Pd-enriched Cu-Pd nanoparticles were formed. These particles exhibit much higher formic acid oxidation activities than that on pure Pd nanoparticles, and they are much more resistant to the surface poisoning. Possible mechanisms of catalytic activity enhancement are briefly discussed.

  18. CO2 Hydrogenation to Formic Acid on Ni(110)

    SciTech Connect

    Peng, Guowen; Sibener, S. J.; Schatz, George C.; Mavrikakis, Manos

    2012-03-06

    Hydrogen (H) in the subsurface of transition-metal surfaces exhibits unique reactivity for heterogeneously catalyzed hydrogenation reactions. Here, we explore the potential of subsurface H for hydrogenating carbon dioxide (CO2) on Ni(110). The energetics of surface and subsurface H reacting with surface CO2 to form formate, carboxyl, and formic acid on Ni(110) is systematically studied using self-consistent, spin-polarized, periodic density functional theory (DFT-GGA-PW91) calculations. We show that on Ni(110), CO2 can be hydrogenated to formate by surface H. However, further hydrogenation of formate to formic acid by surface H is hindered by a larger activation energy barrier. The relative energetics of hydrogenation barriers is reversed for the carboxyl-mediated route to formic acid.We suggest that the energetics of subsurface H emerging to the surface is suitable for providing the extra energy needed to overcome the barrier to formate hydrogenation. CO2 hydrogenation to formic acid could take place on Ni(110) when subsurface H is available to react with CO2. Additional electronic-structure based dynamic calculations would be needed to elucidate the detailed reaction paths for these transformations.

  19. TES/Aura L2 Formic Acid (FOR) Nadir (TL2FORN)

    Atmospheric Science Data Center

    2015-02-04

    TES/Aura L2 Formic Acid (FOR) Nadir (TL2FORN) News:  TES News Join ... L2 Platform:  TES/Aura L2 Formic Acid Spatial Coverage:  5.3 x 8.5 km nadir Spatial ... Access:  OPeNDAP Parameters:  Formic Acid Volume Mixing Ratio Precision Vertical Resolution Order ...

  20. TES/Aura L2 Formic Acid (FOR) Lite Nadir (TL2FORLN)

    Atmospheric Science Data Center

    2015-06-16

    TES/Aura L2 Formic Acid (FOR) Lite Nadir (TL2FORLN) News:  TES News ... L2 Instrument:  TES/Aura L2 Formic Acid Spatial Coverage:  5.3 km nadir Spatial ... Access:  OPeNDAP Parameters:  Formic Acid Volume Mixing Ratio Vertical Resolution Precision Order ...

  1. TES/Aura L2 Formic Acid (FOR) Nadir (TL2FORNS)

    Atmospheric Science Data Center

    2015-02-04

    TES/Aura L2 Formic Acid (FOR) Nadir (TL2FORNS) News:  TES News Join ... L2 Platform:  TES/Aura L2 Formic Acid Spatial Coverage:  5.3 x 8.5 km nadir Spatial ... Access:  OPeNDAP Parameters:  Formic Acid Volume Mixing Ratio Precision Vertical Resolution Order ...

  2. GLYCOLIC-FORMIC ACID FLOWSHEET SLUDGE MATRIX STUDY

    SciTech Connect

    Lambert, D.; Koopman, D.

    2011-06-30

    Testing was completed to demonstrate the viability of the newly developed glycolic acid/formic acid flowsheet on processing in the Defense Waste Processing Facility's (DWPF) Chemical Process Cell (CPC). The Savannah River National Laboratory (SRNL) initiated a sludge matrix study to evaluate the impact of changing insoluble solid composition on the processing characteristics of slurries in DWPF. Four sludge simulants were prepared to cover two compositional ranges in the waste. The first was high iron/low aluminum versus low iron/high aluminum (referred to as HiFe or LoFe in this report). The second was high calcium-manganese/low nickel, chromium, and magnesium versus low calcium-manganese/high nickel, chromium, and magnesium (referred to as HiMn or LoMn in this report). These two options can be combined to form four distinct sludge compositions. The sludge matrix study called for testing each of these four simulants near the minimum acid required for nitrite destruction (100% acid stoichiometry) and at a second acid level that produced significant hydrogen by noble metal catalyzed decomposition of formic acid (150% acid stoichiometry). Four simulants were prepared based on the four possible combinations of the Al/Fe and Mn-Ca/Mg-Ni-Cr options. Preliminary simulant preparation work has already been documented. The four simulants were used for high and low acid testing. Eight planned experiments (GF26 to GF33) were completed to demonstrate the viability of the glycolic-formic flowsheet. Composition and physical property measurements were made on the SRAT product. Composition measurements were made on the condensate from the Mercury Water Wash Tank (MWWT), Formic Acid Vent Condenser (FAVC), ammonia scrubber and on SRAT samples pulled throughout the SRAT cycle. Updated values for formate loss and nitrite-tonitrate conversion were found that can be used in the acid calculations for future sludge matrix process simulations with the glycolic acid/formic acid flowsheet

  3. Sphingolipids contribute to acetic acid resistance in Zygosaccharomyces bailii.

    PubMed

    Lindahl, Lina; Genheden, Samuel; Eriksson, Leif A; Olsson, Lisbeth; Bettiga, Maurizio

    2016-04-01

    Lignocellulosic raw material plays a crucial role in the development of sustainable processes for the production of fuels and chemicals. Weak acids such as acetic acid and formic acid are troublesome inhibitors restricting efficient microbial conversion of the biomass to desired products. To improve our understanding of weak acid inhibition and to identify engineering strategies to reduce acetic acid toxicity, the highly acetic-acid-tolerant yeast Zygosaccharomyces bailii was studied. The impact of acetic acid membrane permeability on acetic acid tolerance in Z. bailii was investigated with particular focus on how the previously demonstrated high sphingolipid content in the plasma membrane influences acetic acid tolerance and membrane permeability. Through molecular dynamics simulations, we concluded that membranes with a high content of sphingolipids are thicker and more dense, increasing the free energy barrier for the permeation of acetic acid through the membrane. Z. bailii cultured with the drug myriocin, known to decrease cellular sphingo-lipid levels, exhibited significant growth inhibition in the presence of acetic acid, while growth in medium without acetic acid was unaffected by the myriocin addition. Furthermore, following an acetic acid pulse, the intracellular pH decreased more in myriocin-treated cells than in control cells. This indicates a higher inflow rate of acetic acid and confirms that the reduction in growth of cells cultured with myriocin in the medium with acetic acid was due to an increase in membrane permeability, thereby demonstrating the importance of a high fraction of sphingolipids in the membrane of Z. bailii to facilitate acetic acid resistance; a property potentially transferable to desired production organisms suffering from weak acid stress. PMID:26416641

  4. Sphingolipids contribute to acetic acid resistance in Zygosaccharomyces bailii.

    PubMed

    Lindahl, Lina; Genheden, Samuel; Eriksson, Leif A; Olsson, Lisbeth; Bettiga, Maurizio

    2016-04-01

    Lignocellulosic raw material plays a crucial role in the development of sustainable processes for the production of fuels and chemicals. Weak acids such as acetic acid and formic acid are troublesome inhibitors restricting efficient microbial conversion of the biomass to desired products. To improve our understanding of weak acid inhibition and to identify engineering strategies to reduce acetic acid toxicity, the highly acetic-acid-tolerant yeast Zygosaccharomyces bailii was studied. The impact of acetic acid membrane permeability on acetic acid tolerance in Z. bailii was investigated with particular focus on how the previously demonstrated high sphingolipid content in the plasma membrane influences acetic acid tolerance and membrane permeability. Through molecular dynamics simulations, we concluded that membranes with a high content of sphingolipids are thicker and more dense, increasing the free energy barrier for the permeation of acetic acid through the membrane. Z. bailii cultured with the drug myriocin, known to decrease cellular sphingo-lipid levels, exhibited significant growth inhibition in the presence of acetic acid, while growth in medium without acetic acid was unaffected by the myriocin addition. Furthermore, following an acetic acid pulse, the intracellular pH decreased more in myriocin-treated cells than in control cells. This indicates a higher inflow rate of acetic acid and confirms that the reduction in growth of cells cultured with myriocin in the medium with acetic acid was due to an increase in membrane permeability, thereby demonstrating the importance of a high fraction of sphingolipids in the membrane of Z. bailii to facilitate acetic acid resistance; a property potentially transferable to desired production organisms suffering from weak acid stress.

  5. Formic acid production from carbohydrates biomass by hydrothermal reaction

    NASA Astrophysics Data System (ADS)

    Yun, J.; Jin, F.; Kishita, A.; Tohji, K.; Enomoto, H.

    2010-03-01

    The formation of formic acid or formate salts by hydrothermal oxidation of model biomass materials (glucose, starch and cellulose) was investigated. All experiments were conducted in a batch reactor, made of SUS 316 tubing, providing an internal volume of 5.7 cm3. A 30 wt% hydrogen peroxide aqueous solution was used as an oxidant. The experiments were carried out with temperature of 250°C, reaction time varying from 0.5 min to 5 min, H2O2 supply of 240%, and alkaline concentration varying from 0 to 1.25 M. Similar to glucose, in the cases of the oxidation of hydrothermal starch and cellulose, the addition of alkaline can also improve the yield of formic acid. And the yield were glucose>starch> cellulose in cases of with or without of alkaline addition.

  6. Tested Demonstrations: Color Oscillations in the Formic Acid-Nitric Acid-Sulfuric Acid System.

    ERIC Educational Resources Information Center

    Raw, C. J. G.; And Others

    1983-01-01

    Presented are procedures for demonstrating the production of color oscillations when nitric acid is added to a formic acid/concentrated sulfuric acid mixture. Because of safety considerations, "Super-8" home movie of the color changes was found to be satisfactory for demonstration purposes. (JN)

  7. Theoretical study of water cluster catalyzed decomposition of formic acid.

    PubMed

    Inaba, Satoshi

    2014-04-24

    We have performed a number of quantum chemical simulations to examine water cluster catalyzed decomposition of formic acid. The decomposition of formic acid consists of two competing pathways, dehydration, and decarboxylation. We use the Gaussian 4 method of the Gaussian09 software to locate and optimize a transition state of the decomposition reaction and obtain the activation energy. The decomposition starts by transferring a proton of a formic acid to a water molecule. The de Broglie wavelength of a proton is similar to the width of the potential barrier of the decomposition reaction at low temperature. The tunneling, in which a proton penetrates the potential barrier, enhances the decomposition rate. Water molecules serve as the catalyst in the decomposition and reduce the activation energy. The relay of a proton from a water molecule to a neighboring water molecule is accomplished with little change of the geometry of a molecule, resulting in the reduction of the activation energy. Two water molecules are actively involved in the decomposition reaction to reduce the activation energy. We have also examined the effect of water clusters with three, four, and five water molecules on the decomposition reaction. The noncovalent distance between a hydrogen atom of a water molecule and an oxygen atom of a neighboring water molecule decreases in a water cluster due to the cooperative many-body interactions. A water molecule in a water cluster becomes a better proton donor as well as a better proton acceptor. The activation energy of the decomposition is further decreased by the catalytic effect of a water cluster. We calculate the reaction rate using the transition state theory corrected by the tunneling effect of a proton. The calculated reaction rate of the decarboxylation is smaller than that of the dehydration when less than three water molecules are included in the simulation. However, the major product of the decomposition of a formic acid becomes carbon dioxide

  8. Sphingolipids contribute to acetic acid resistance in Zygosaccharomyces bailii

    PubMed Central

    Lindahl, Lina; Genheden, Samuel; Eriksson, Leif A.; Olsson, Lisbeth

    2015-01-01

    ABSTRACT Lignocellulosic raw material plays a crucial role in the development of sustainable processes for the production of fuels and chemicals. Weak acids such as acetic acid and formic acid are troublesome inhibitors restricting efficient microbial conversion of the biomass to desired products. To improve our understanding of weak acid inhibition and to identify engineering strategies to reduce acetic acid toxicity, the highly acetic‐acid‐tolerant yeast Zygosaccharomyces bailii was studied. The impact of acetic acid membrane permeability on acetic acid tolerance in Z. bailii was investigated with particular focus on how the previously demonstrated high sphingolipid content in the plasma membrane influences acetic acid tolerance and membrane permeability. Through molecular dynamics simulations, we concluded that membranes with a high content of sphingolipids are thicker and more dense, increasing the free energy barrier for the permeation of acetic acid through the membrane. Z. bailii cultured with the drug myriocin, known to decrease cellular sphingo­lipid levels, exhibited significant growth inhibition in the presence of acetic acid, while growth in medium without acetic acid was unaffected by the myriocin addition. Furthermore, following an acetic acid pulse, the intracellular pH decreased more in myriocin‐treated cells than in control cells. This indicates a higher inflow rate of acetic acid and confirms that the reduction in growth of cells cultured with myriocin in the medium with acetic acid was due to an increase in membrane permeability, thereby demonstrating the importance of a high fraction of sphingolipids in the membrane of Z. bailii to facilitate acetic acid resistance; a property potentially transferable to desired production organisms suffering from weak acid stress. Biotechnol. Bioeng. 2016;113: 744–753. © 2015 The Authors. Biotechnology and Bioengineering Published by Wiley Periodicals, Inc. PMID:26416641

  9. Structure Study of Formic Acid Clusters by Chirped-Pulse Ftmw Spectroscopy

    NASA Astrophysics Data System (ADS)

    Zaleski, Daniel P.; Neill, Justin L.; Muckle, Matt T.; Steber, Amanda L.; Pate, Brooks H.; Douglass, Kevin O.

    2011-06-01

    The large bandwidths and high sensitivity afforded by chirped-pulse FTMW spectrometers allow for the detection of large molecules (10+ heavy atoms) and their isotopomers in natural abundance. With the isotopic information, an experimental structure can be obtained by using Kraitchman's equations. Clusters of carboxylic acids are of interest because of the different possibilities for hydrogen bonding that lead to the formation of larger clusters. The first study of formic acid clusters by microwave spectroscopy was presented by Bauder and the formic acid dimer with one water molecule complexed was identified. Previously the formic acid trimer cluster was reported where the third formic acid attaches itself to the already formed formic acid dimer. Here we present the full heavy atom and partial deuterium Kraitchman substitution structure of formic acid trimer. In addition we have identified two new nonplanar formic acid clusters - formic acid pentamer and the cluster of formic acid trimer with one water molecule attached. For the latter, two tunneling states with an energy splitting of 178 MHz are observed for the normal species and 13C isotopomers. Candidate structures and the difficulty of modeling these clusters by electronic structure theory will be discussed. Dominque Priem, Tae-Kyu Ha, and Alfred Bauder. J. Chem. Phys. 113, 1, (2000), 169-175. Conformational Studies in Formic Acid Oligimers. Richard D. Suenram, Pam L. Crum, Kevin O. Douglass, and Brooks H. Pate. The Ohio State 59th International Symposium on Molecular Spectroscopy.

  10. Direct synthesis of formic acid from carbon dioxide by hydrogenation in acidic media

    PubMed Central

    Moret, Séverine; Dyson, Paul J.; Laurenczy, Gábor

    2014-01-01

    The chemical transformation of carbon dioxide into useful products becomes increasingly important as CO2 levels in the atmosphere continue to rise as a consequence of human activities. In this article we describe the direct hydrogenation of CO2 into formic acid using a homogeneous ruthenium catalyst, in aqueous solution and in dimethyl sulphoxide (DMSO), without any additives. In water, at 40 °C, 0.2 M formic acid can be obtained under 200 bar, however, in DMSO the same catalyst affords 1.9 M formic acid. In both solvents the catalysts can be reused multiple times without a decrease in activity. Worldwide demand for formic acid continues to grow, especially in the context of a renewable energy hydrogen carrier, and its production from CO2 without base, via the direct catalytic carbon dioxide hydrogenation, is considerably more sustainable than the existing routes. PMID:24886955

  11. Catalytic air oxidation of biomass-derived carbohydrates to formic acid.

    PubMed

    Li, Jiang; Ding, Dao-Jun; Deng, Li; Guo, Qing-Xiang; Fu, Yao

    2012-07-01

    An efficient catalytic system for biomass oxidation to form formic acid was developed. The conversion of glucose to formic acid can reach up to 52% yield within 3 h when catalyzed by 5 mol% of H(5)PV(2)Mo(10)O(40) at only 373 K using air as the oxidant. Furthermore, the heteropolyacid can be used as a bifunctional catalyst in the conversion of cellulose to formic acid (yield=35%) with air as the oxidant. PMID:22499553

  12. Catalytic air oxidation of biomass-derived carbohydrates to formic acid.

    PubMed

    Li, Jiang; Ding, Dao-Jun; Deng, Li; Guo, Qing-Xiang; Fu, Yao

    2012-07-01

    An efficient catalytic system for biomass oxidation to form formic acid was developed. The conversion of glucose to formic acid can reach up to 52% yield within 3 h when catalyzed by 5 mol% of H(5)PV(2)Mo(10)O(40) at only 373 K using air as the oxidant. Furthermore, the heteropolyacid can be used as a bifunctional catalyst in the conversion of cellulose to formic acid (yield=35%) with air as the oxidant.

  13. Direct formic acid microfluidic fuel cell design and performance evolution

    NASA Astrophysics Data System (ADS)

    Moreno-Zuria, A.; Dector, A.; Cuevas-Muñiz, F. M.; Esquivel, J. P.; Sabaté, N.; Ledesma-García, J.; Arriaga, L. G.; Chávez-Ramírez, A. U.

    2014-12-01

    This work reports the evolution of design, fabrication and testing of direct formic acid microfluidic fuel cells (DFAμFFC), the architecture and channel dimensions are miniaturized from a thousand to few cents of micrometers. Three generations of DFAμFFCs are presented, from the initial Y-shape configuration made by a hot pressing technique; evolving into a novel miniaturized fuel cell based on microfabrication technology using SU-8 photoresist as core material; to the last air-breathing μFFC with enhanced performance and built with low cost materials and processes. The three devices were evaluated in acidic media in the presence of formic acid as fuel and oxygen/air as oxidant. Commercial Pt/C (30 wt. % E-TEK) and Pd/C XC-72 (20 wt. %, E-TEK) were used as cathode and anode electrodes respectively. The air-breathing μFFC generation, delivered up to 27.3 mW cm-2 for at least 30 min, which is a competitive power density value at the lowest fuel flow of 200 μL min-1 reported to date.

  14. New Theoretical Insight into the Interactions and Properties of Formic Acid: Development of a Quantum-Based Pair Potential for Formic Acid.

    SciTech Connect

    Roszak, S; Gee, R; Balasubramanian, K; Fried, L

    2005-08-08

    We performed ab initio quantum chemical studies for the development of intra and intermolecular interaction potentials for formic acid for use in molecular dynamics simulations of formic acid molecular crystal. The formic acid structures considered in the ab initio studies include both the cis and trans monomers which are the conformers that have been postulated as part of chains constituting liquid and crystal phases under extreme conditions. Although the cis to trans transformation is not energetically favored, the trans isomer was found as a component of stable gas-phase species. Our decomposition scheme for the interaction energy indicates that the hydrogen bonded complexes are dominated by the Hartree-Fock forces while parallel clusters are stabilized by the electron correlation energy. The calculated three-body and higher interactions are found to be negligible, thus rationalizing the development of an atom-atom pair potential for formic acid based on high-level ab initio calculations of small formic acid clusters. Here we present an atom-atom pair potential that includes both intra- and inter-molecular degrees of freedom for formic acid. The newly developed pair potential is used to examine formic acid in the condensed phase via molecular dynamics simulations. The isothermal compression under hydrostatic pressure obtained from molecular dynamics simulations is in good agreement with experiment. Further, the calculated equilibrium melting temperature is found to be in good agreement with experiment.

  15. New theoretical insight into the interactions and properties of formic acid: development of a quantum-based pair potential for formic acid.

    PubMed

    Roszak, Szczepan; Gee, Richard H; Balasubramanian, Krishnan; Fried, Laurence E

    2005-10-01

    We performed ab initio quantum-chemical studies for the development of intra- and intermolecular interaction potentials for formic acid for use in molecular-dynamics simulations of formic acid molecular crystal. The formic acid structures considered in the ab initio studies include both the cis and trans monomers which are the conformers that have been postulated as part of chains constituting liquid and crystal phases under extreme conditions. Although the cis to trans transformation is not energetically favored, the trans isomer was found as a component of stable gas-phase species. Our decomposition scheme for the interaction energy indicates that the hydrogen-bonded complexes are dominated by the Hartree-Fock forces while parallel clusters are stabilized by the electron correlation energy. The calculated three-body and higher interactions are found to be negligible, thus rationalizing the development of an atom-atom pair potential for formic acid based on high-level ab initio calculations of small formic acid clusters. Here we present an atom-atom pair potential that includes both intra- and inter molecular degrees of freedom for formic acid. The newly developed pair potential is used to examine formic acid in the condensed phase via molecular-dynamics simulations. The isothermal compression under hydrostatic pressure obtained from molecular-dynamics simulations is in good agreement with experiment. Further, the calculated equilibrium melting temperature is found to be in good agreement with experiment. PMID:16238411

  16. Catalytic Conversion of Biomass for the Production of Hydrogen; Decomposition of Formic Acid

    NASA Astrophysics Data System (ADS)

    Azadi Manzour, Faraz

    Highly active bimetallic catalysts were synthesized and used for the decomposition of formic acid for the production of hydrogen. Ruthenium alloys were prepared and resulted in a maximum formic acid conversion of 68% (after one hour at 180 °C) and a turnover frequency of 0.7/s (at 5 wt% formic acid). The most promising catalysts were characterized by the means of X-ray diffraction and scanning electron microscopy. Kinetic studies were also carried out over these catalysts for the determination of reaction rate and turnover frequency. Promotion of Ru/C with tin, barium and cesium increased the formic acid conversion by 55%, 18% and 11% respectively.

  17. Elucidation of noble metal/formic acid chemistry during DWPF feed preparation. Revision 1

    SciTech Connect

    Landon, L.F.

    1991-12-31

    Eleven reports are included: evaluation of noble metal compounds as catalysts for aerobic decomposition of formic acid; reaction of NaNO{sub 3} and NaNO{sub 2} with formic acid under argon; effects of Ru, Rh, Pd chlorides on formic acid decomposition in presence of IDMS (pH=11.0) sludge; effects of additives on catalysts on decomposition of formic acid to hydrogen; Rh-catalyzed decomposition of formic acid; the question of whether this decomposition can be heterogeneous catalysis; inhibition of this reaction by additives; nitrilotriacetic acid inhibitor; uses of gelatin and other water soluble polymers to control flocculation rate; comparison of catalytic activities of Rh, Ru, Pd in Purex and HM sludges; experiments on homogeneous vs heterogeneous nature of Rh catalyst. Figs, refs, tabs.

  18. Elucidation of noble metal/formic acid chemistry during DWPF feed preparation

    SciTech Connect

    Landon, L.F.

    1991-01-01

    Eleven reports are included: evaluation of noble metal compounds as catalysts for aerobic decomposition of formic acid; reaction of NaNO[sub 3] and NaNO[sub 2] with formic acid under argon; effects of Ru, Rh, Pd chlorides on formic acid decomposition in presence of IDMS (pH=11.0) sludge; effects of additives on catalysts on decomposition of formic acid to hydrogen; Rh-catalyzed decomposition of formic acid; the question of whether this decomposition can be heterogeneous catalysis; inhibition of this reaction by additives; nitrilotriacetic acid inhibitor; uses of gelatin and other water soluble polymers to control flocculation rate; comparison of catalytic activities of Rh, Ru, Pd in Purex and HM sludges; experiments on homogeneous vs heterogeneous nature of Rh catalyst. Figs, refs, tabs.

  19. Investigation of secondary formation of formic acid: urban environment vs. oil and gas producing region

    NASA Astrophysics Data System (ADS)

    Yuan, B.; Veres, P. R.; Warneke, C.; Roberts, J. M.; Gilman, J. B.; Koss, A.; Edwards, P. M.; Graus, M.; Kuster, W. C.; Li, S.-M.; Wild, R. J.; Brown, S. S.; Dubé, W. P.; Lerner, B. M.; Williams, E. J.; Johnson, J. E.; Quinn, P. K.; Bates, T. S.; Lefer, B.; Hayes, P. L.; Jimenez, J. L.; Weber, R. J.; Zamora, R.; Ervens, B.; Millet, D. B.; Rappenglück, B.; de Gouw, J. A.

    2015-02-01

    Formic acid (HCOOH) is one of the most abundant carboxylic acids in the atmosphere. However, current photochemical models cannot fully explain observed concentrations and in particular secondary formation of formic acid across various environments. In this work, formic acid measurements made at an urban receptor site (Pasadena) in June-July 2010 during CalNex (California Research at the Nexus of Air Quality and Climate Change) and a site in an oil and gas producing region (Uintah Basin) in January-February 2013 during UBWOS 2013 (Uintah Basin Winter Ozone Studies) will be discussed. Although the VOC (volatile organic compounds) compositions differed dramatically at the two sites, measured formic acid concentrations were comparable: 2.3 ± 1.3 in UBWOS 2013 and 2.0 ± 1.0 ppb in CalNex. We determine that concentrations of formic acid at both sites were dominated by secondary formation (> 99%). A constrained box model using the Master Chemical Mechanism (MCM v3.2) underestimates the measured formic acid concentrations drastically at both sites (by a factor of > 10). Compared to the original MCM model that includes only ozonolysis of unsaturated organic compounds and OH oxidation of acetylene, when we updated yields of ozonolysis of alkenes and included OH oxidation of isoprene, vinyl alcohol chemistry, reaction of formaldehyde with HO2, oxidation of aromatics, and reaction of CH3O2 with OH, the model predictions for formic acid were improved by a factor of 6.4 in UBWOS 2013 and 4.5 in CalNex, respectively. A comparison of measured and modeled HCOOH/acetone ratios is used to evaluate the model performance for formic acid. We conclude that the modified chemical mechanism can explain 19 and 45% of secondary formation of formic acid in UBWOS 2013 and CalNex, respectively. The contributions from aqueous reactions in aerosol and heterogeneous reactions on aerosol surface to formic acid are estimated to be 0-6 and 0-5% in UBWOS 2013 and CalNex, respectively. We observe that

  20. Efficient dehydrogenation of formic acid using an iron catalyst.

    PubMed

    Boddien, Albert; Mellmann, Dörthe; Gärtner, Felix; Jackstell, Ralf; Junge, Henrik; Dyson, Paul J; Laurenczy, Gábor; Ludwig, Ralf; Beller, Matthias

    2011-09-23

    Hydrogen is one of the essential reactants in the chemical industry, though its generation from renewable sources and storage in a safe and reversible manner remain challenging. Formic acid (HCO(2)H or FA) is a promising source and storage material in this respect. Here, we present a highly active iron catalyst system for the liberation of H(2) from FA. Applying 0.005 mole percent of Fe(BF(4))(2)·6H(2)O and tris[(2-diphenylphosphino)ethyl]phosphine [P(CH(2)CH(2)PPh(2))(3), PP(3)] to a solution of FA in environmentally benign propylene carbonate, with no further additives or base, affords turnover frequencies up to 9425 per hour and a turnover number of more than 92,000 at 80°C. We used in situ nuclear magnetic resonance spectroscopy, kinetic studies, and density functional theory calculations to explain possible reaction mechanisms. PMID:21940890

  1. Influence of Sodium Carbonate on Decomposition of Formic Acid by Discharge inside Bubble in Water

    NASA Astrophysics Data System (ADS)

    Iwabuchi, Masashi; Takahashi, Katsuyuki; Takaki, Koichi; Satta, Naoya

    2015-09-01

    An influence of sodium carbonate on decomposition of formic acid by discharge inside bubble in water was investigated. Oxygen or argon gases were injected into the water through a vertically positioned glass tube, in which the high-voltage wire electrode was placed to generate plasmas at low applied voltage. The concentration of formic acid was determined by ion chromatography. In the case of addition of sodium carbonate, the pH value increased with decomposition of the formic acid. In the case of oxygen injection, the increase of pH value contributed to improve an efficiency of the formic acid decomposition because the reaction rate of ozone and formic acid increased with increasing pH value. In the case of argon injection, the decomposition rate was not affected by the pH value owing to the high rate constants for loss of hydroxyl radicals.

  2. Selective Production of Formic Acid by Hydrothermal Alkaline Oxidation of Carbohydrates

    NASA Astrophysics Data System (ADS)

    Yun, J.; Li, G.; Enomoto, H.; Jin, F.

    2007-03-01

    Formic acid is a familiar product in hydrothermal oxidation of carbohydrates and is an important organic compound. In this study, the production of formic acid from the hydrothermal oxidation of glucose with and without the addition of alkali was investigated with temperature varying from 250 to 300°C, reaction time varying from 30 s to 240 s, and oxygen supply varying from 60 % to 140 %. Results showed that the highest yield of formic acid was only about 24 % in hydrothermal oxidation of glucose without the addition of alkali. It is very interest that the oxidation of glucose with the addition of alkali showed a high selective and effective for the production of formic acid. An excellent formic acid yield of about 74 % was achieved, which occurred at 250°C for 60 s with 120 % oxygen supply and the KOH concentration of 1.25 M.

  3. LABORATORY STUDIES ON THE FORMATION OF FORMIC ACID (HCOOH) IN INTERSTELLAR AND COMETARY ICES

    SciTech Connect

    Bennett, Chris J.; Kim, Yong Seol; Kaiser, Ralf I.; Hama, Tetsuya; Kawasaki, Masahiro

    2011-01-20

    Mixtures of water (H{sub 2}O) and carbon monoxide (CO) ices were irradiated at 10 K with energetic electrons to simulate the energy transfer processes that occur in the track of galactic cosmic-ray particles penetrating interstellar ices. We identified formic acid (HCOOH) through new absorption bands in the infrared spectra at 1690 and 1224 cm{sup -1} (5.92 and 8.17 {mu}m, respectively). During the subsequent warm-up of the irradiated samples, formic acid is evident from the mass spectrometer signal at the mass-to-charge ratio, m/z = 46 (HCOOH{sup +}) as the ice sublimates. The detection of formic acid was confirmed using isotopically labeled water-d2 with carbon monoxide, leading to formic acid-d2 (DCOOD). The temporal fits of the reactants, reaction intermediates, and products elucidate two reaction pathways to formic acid in carbon monoxide-water ices. The reaction is induced by unimolecular decomposition of water forming atomic hydrogen (H) and the hydroxyl radical (OH). The dominating pathway to formic acid (HCOOH) was found to involve addition of suprathermal hydrogen atoms to carbon monoxide forming the formyl radical (HCO); the latter recombined with neighboring hydroxyl radicals to yield formic acid (HCOOH). To a lesser extent, hydroxyl radicals react with carbon monoxide to yield the hydroxyformyl radical (HOCO), which recombined with atomic hydrogen to produce formic acid. Similar processes are expected to produce formic acid within interstellar ices, cometary ices, and icy satellites, thus providing alternative processes for the generation of formic acid whose abundance in hot cores such as Sgr-B2 cannot be accounted for solely by gas-phase chemistry.

  4. Analysis of proteins responsive to acetic acid in Acetobacter: molecular mechanisms conferring acetic acid resistance in acetic acid bacteria.

    PubMed

    Nakano, Shigeru; Fukaya, Masahiro

    2008-06-30

    Acetic acid bacteria are used for industrial vinegar production because of their remarkable ability to oxidize ethanol and high resistance to acetic acid. Although several molecular machineries responsible for acetic acid resistance in acetic acid bacteria have been reported, the entire mechanism that confers acetic acid resistance has not been completely understood. One of the promising methods to elucidate the entire mechanism is global analysis of proteins responsive to acetic acid by two-dimensional gel electrophoresis. Recently, two proteins whose production was greatly enhanced by acetic acid in Acetobacter aceti were identified to be aconitase and a putative ABC-transporter, respectively; furthermore, overexpression or disruption of the genes encoding these proteins affected acetic acid resistance in A. aceti, indicating that these proteins are involved in acetic acid resistance. Overexpression of each gene increased acetic acid resistance in Acetobacter, which resulted in an improvement in the productivity of acetic acid fermentation. Taken together, the results of the proteomic analysis and those of previous studies indicate that acetic acid resistance in acetic acid bacteria is conferred by several mechanisms. These findings also provide a clue to breed a strain having high resistance to acetic acid for vinegar fermentation.

  5. Screening of Non- Saccharomyces cerevisiae Strains for Tolerance to Formic Acid in Bioethanol Fermentation.

    PubMed

    Oshoma, Cyprian E; Greetham, Darren; Louis, Edward J; Smart, Katherine A; Phister, Trevor G; Powell, Chris; Du, Chenyu

    2015-01-01

    Formic acid is one of the major inhibitory compounds present in hydrolysates derived from lignocellulosic materials, the presence of which can significantly hamper the efficiency of converting available sugars into bioethanol. This study investigated the potential for screening formic acid tolerance in non-Saccharomyces cerevisiae yeast strains, which could be used for the development of advanced generation bioethanol processes. Spot plate and phenotypic microarray methods were used to screen the formic acid tolerance of 7 non-Saccharomyces cerevisiae yeasts. S. kudriavzeii IFO1802 and S. arboricolus 2.3319 displayed a higher formic acid tolerance when compared to other strains in the study. Strain S. arboricolus 2.3319 was selected for further investigation due to its genetic variability among the Saccharomyces species as related to Saccharomyces cerevisiae and availability of two sibling strains: S. arboricolus 2.3317 and 2.3318 in the lab. The tolerance of S. arboricolus strains (2.3317, 2.3318 and 2.3319) to formic acid was further investigated by lab-scale fermentation analysis, and compared with S. cerevisiae NCYC2592. S. arboricolus 2.3319 demonstrated improved formic acid tolerance and a similar bioethanol synthesis capacity to S. cerevisiae NCYC2592, while S. arboricolus 2.3317 and 2.3318 exhibited an overall inferior performance. Metabolite analysis indicated that S. arboricolus strain 2.3319 accumulated comparatively high concentrations of glycerol and glycogen, which may have contributed to its ability to tolerate high levels of formic acid.

  6. Screening of Non- Saccharomyces cerevisiae Strains for Tolerance to Formic Acid in Bioethanol Fermentation

    PubMed Central

    Oshoma, Cyprian E.; Greetham, Darren; Louis, Edward J.; Smart, Katherine A.; Phister, Trevor G.; Powell, Chris; Du, Chenyu

    2015-01-01

    Formic acid is one of the major inhibitory compounds present in hydrolysates derived from lignocellulosic materials, the presence of which can significantly hamper the efficiency of converting available sugars into bioethanol. This study investigated the potential for screening formic acid tolerance in non-Saccharomyces cerevisiae yeast strains, which could be used for the development of advanced generation bioethanol processes. Spot plate and phenotypic microarray methods were used to screen the formic acid tolerance of 7 non-Saccharomyces cerevisiae yeasts. S. kudriavzeii IFO1802 and S. arboricolus 2.3319 displayed a higher formic acid tolerance when compared to other strains in the study. Strain S. arboricolus 2.3319 was selected for further investigation due to its genetic variability among the Saccharomyces species as related to Saccharomyces cerevisiae and availability of two sibling strains: S. arboricolus 2.3317 and 2.3318 in the lab. The tolerance of S. arboricolus strains (2.3317, 2.3318 and 2.3319) to formic acid was further investigated by lab-scale fermentation analysis, and compared with S. cerevisiae NCYC2592. S. arboricolus 2.3319 demonstrated improved formic acid tolerance and a similar bioethanol synthesis capacity to S. cerevisiae NCYC2592, while S. arboricolus 2.3317 and 2.3318 exhibited an overall inferior performance. Metabolite analysis indicated that S. arboricolus strain 2.3319 accumulated comparatively high concentrations of glycerol and glycogen, which may have contributed to its ability to tolerate high levels of formic acid. PMID:26284784

  7. Repellent Effect of Formic Acid Against the Red Imported Fire Ant (Hymenoptera: Formicidae): A Field Study.

    PubMed

    Wang, Cai; Henderson, Gregg

    2016-04-01

    Previous studies showed that the formic acid secreted by tawny crazy ants not only has fumigation toxicity to the red imported fire ant, Solenopsis invicta Buren (Chen et al. 2013), but also can detoxify fire ant venom (LeBrun et al. 2014). These lead us to a field study to determine if low concentrations of formic acid might be useful in repelling S. invicta. Filter paper discs treated with 1.3% or 5% formic acid (v: v) or distilled water (control) were placed on each of the 46 S. invicta mounds and a disturbance was created. For a minute or less, there were significantly more defending ants on the control discs than that on the paper discs treated with formic acid. After food was added and for the next 40 min, there were significantly more foraging ants on the control discs compared to the treated discs. At 50 min into the test, the number of foraging ants on the control and 1.3% formic acid-treated discs was similar, but both were significantly higher than that on the 5% formic acid-treated discs. In addition, the active foraging (≥10 ants stayed on or around the food) and burying behavior (soil particles were deposited around the food) continued to be inhibited by 5% formic acid. The potential application and ecological significant of this repellent effect is discussed. PMID:26700488

  8. Spectroscopy and dynamics of double proton transfer in formic acid dimer.

    PubMed

    Mackeprang, Kasper; Xu, Zhen-Hao; Maroun, Zeina; Meuwly, Markus; Kjaergaard, Henrik G

    2016-09-21

    We present the isolated gas phase infrared spectra of formic acid dimer, (HCOOH)2, and its deuterated counterpart formic-d acid, (DCOOH)2, at room temperature. The formic acid dimer spectrum was obtained by spectral subtraction of a spectrum of formic acid vapor recorded at low pressure from that recorded at a higher pressure. The spectra of formic acid vapor contain features from both formic acid monomer and formic acid dimer, but at low and high pressures of formic acid, the equilibrium is pushed towards the monomer and dimer, respectively. A similar approach was used for the formic-d acid dimer. Building on the previous development of the Molecular Mechanics with Proton Transfer (MMPT) force field for simulating proton transfer reactions, molecular dynamics (MD) simulations were carried out to interpret the experimental spectra in the OH-stretching region. Within the framework of MMPT, a combination of symmetric single and double minimum potential energy surfaces (PESs) provides a good description of the double proton transfer PES. In a next step, potential morphing together with electronic structure calculations at the B3LYP and MP2 level of theory was used to align the computed and experimentally observed spectral features in the OH-stretching region. From this analysis, a barrier for double proton transfer between 5 and 7 kcal mol(-1) was derived, which compares with a CCSD(T)/aug-cc-pVTZ calculated barrier of 7.9 kcal mol(-1). Such a combination of experimental and computational techniques for estimating barriers for proton transfer in gas phase systems is generic and holds promise for further improved PESs and energetics of these important systems. Additional MD simulations at the semi-empirical DFTB level of theory agree quite well for the center band position but underestimate the width of the OH-stretching band. PMID:27545453

  9. A Direct, Biomass-Based Synthesis of Benzoic Acid: Formic Acid-Mediated Deoxygenation of the Glucose-Derived Materials Quinic Acid and Shikimic Acid

    SciTech Connect

    Arceo, Elena; Ellman, Jonathan; Bergman, Robert

    2010-05-03

    An alternative biomass-based route to benzoic acid from the renewable starting materials quinic acid and shikimic acid is described. Benzoic acid is obtained selectively using a highly efficient, one-step formic acid-mediated deoxygenation method.

  10. Kinetics of gas phase formic acid decomposition on platinum single crystal and polycrystalline surfaces

    NASA Astrophysics Data System (ADS)

    Detwiler, Michael D.; Milligan, Cory A.; Zemlyanov, Dmitry Y.; Delgass, W. Nicholas; Ribeiro, Fabio H.

    2016-06-01

    Formic acid dehydrogenation turnover rates (TORs) were measured on Pt(111), Pt(100), and polycrystalline Pt foil surfaces at a total pressure of 800 Torr between 413 and 513 K in a batch reactor connected to an ultra-high vacuum (UHV) system. The TORs, apparent activation energies, and reaction orders are not sensitive to the structure of the Pt surface, within the precision of the measurements. CO introduced into the batch reactor depressed the formic acid dehydrogenation TOR and increased the reaction's apparent activation energies on Pt(111) and Pt(100), consistent with behavior predicted by the Temkin equation. Two reaction mechanisms were explored which explain the formic acid decomposition mechanism on Pt, both of which include dissociative adsorption of formic acid, rate limiting formate decomposition, and quasi-equilibrated hydrogen recombination and CO adsorption. No evidence was found that catalytic supports used in previous studies altered the reaction kinetics or mechanism.

  11. A large and ubiquitous source of atmospheric formic acid

    NASA Astrophysics Data System (ADS)

    Millet, D. B.; Baasandorj, M.; Farmer, D. K.; Thornton, J. A.; Baumann, K.; Brophy, P.; Chaliyakunnel, S.; de Gouw, J. A.; Graus, M.; Hu, L.; Koss, A.; Lee, B. H.; Lopez-Hilfiker, F. D.; Neuman, J. A.; Paulot, F.; Peischl, J.; Pollack, I. B.; Ryerson, T. B.; Warneke, C.; Williams, B. J.; Xu, J.

    2015-06-01

    Formic acid (HCOOH) is one of the most abundant acids in the atmosphere, with an important influence on precipitation chemistry and acidity. Here we employ a chemical transport model (GEOS-Chem CTM) to interpret recent airborne and ground-based measurements over the US Southeast in terms of the constraints they provide on HCOOH sources and sinks. Summertime boundary layer concentrations average several parts-per-billion, 2-3× larger than can be explained based on known production and loss pathways. This indicates one or more large missing HCOOH sources, and suggests either a key gap in current understanding of hydrocarbon oxidation or a large, unidentified, direct flux of HCOOH. Model-measurement comparisons implicate biogenic sources (e.g., isoprene oxidation) as the predominant HCOOH source. Resolving the unexplained boundary layer concentrations based (i) solely on isoprene oxidation would require a 3× increase in the model HCOOH yield, or (ii) solely on direct HCOOH emissions would require approximately a 25× increase in its biogenic flux. However, neither of these can explain the high HCOOH amounts seen in anthropogenic air masses and in the free troposphere. The overall indication is of a large biogenic source combined with ubiquitous chemical production of HCOOH across a range of precursors. Laboratory work is needed to better quantify the rates and mechanisms of carboxylic acid production from isoprene and other prevalent organics. Stabilized Criegee intermediates (SCIs) provide a large model source of HCOOH, while acetaldehyde tautomerization accounts for ~ 15% of the simulated global burden. Because carboxylic acids also react with SCIs and catalyze the reverse tautomerization reaction, HCOOH buffers against its own production by both of these pathways. Based on recent laboratory results, reaction between CH3O2 and OH could provide a major source of atmospheric HCOOH; however, including this chemistry degrades the model simulation of CH3OOH and NOx

  12. A large and ubiquitous source of atmospheric formic acid

    NASA Astrophysics Data System (ADS)

    Millet, D. B.; Baasandorj, M.; Farmer, D. K.; Thornton, J. A.; Baumann, K.; Brophy, P.; Chaliyakunnel, S.; de Gouw, J. A.; Graus, M.; Hu, L.; Koss, A.; Lee, B. H.; Lopez-Hilfiker, F. D.; Neuman, J. A.; Paulot, F.; Peischl, J.; Pollack, I. B.; Ryerson, T. B.; Warneke, C.; Williams, B. J.; Xu, J.

    2015-02-01

    Formic acid (HCOOH) is one of the most abundant acids in the atmosphere, with an important influence on precipitation chemistry and acidity. Here we employ a chemical transport model (GEOS-Chem) to interpret recent airborne and ground-based measurements over the US Southeast in terms of the constraints they provide on HCOOH sources and sinks. Summertime boundary layer concentrations average several parts-per-billion, 2-3× larger than can be explained based on known production and loss pathways. This indicates one or more large missing HCOOH sources, and suggests either a key gap in current understanding of hydrocarbon oxidation or a large, unidentified, direct flux of HCOOH. Model-measurement comparisons implicate biogenic sources (e.g., isoprene oxidation) as the predominant HCOOH source. Resolving the unexplained boundary layer concentrations based: (i) solely on isoprene oxidation would require a 3× increase in the model HCOOH yield, or (ii) solely on direct HCOOH emissions would require approximately a 25× increase in its biogenic flux. However, neither of these can explain the high HCOOH amounts seen in anthropogenic air masses and in the free troposphere. The overall indication is of a large biogenic source combined with ubiquitous chemical production of HCOOH across a range of precursors. Laboratory work is needed to better quantify the rates and mechanisms of carboxylic acid production from isoprene and other prevalent organics. Stabilized Criegee intermediates (SCIs) provide a large model source of HCOOH, while acetaldehyde tautomerization accounts for ~ 15% of the simulated global burden. Because carboxylic acids also react with SCIs and catalyze the reverse tautomerization reaction, HCOOH buffers against its own production by both of these pathways. Based on recent laboratory results, reaction between CH3O2 and OH could provide a major source of atmospheric HCOOH; however, including this chemistry degrades the model simulation of CH3OOH and NOx:CH3OOH

  13. Structure and NLO properties of halogen (F, Cl) substituted formic acid dimers.

    PubMed

    Umadevi, P; Senthilkumar, L; Gayathri, M; Kolandaivel, P

    2014-11-11

    In this work, using ab initio and density functional theory (DFT) methods halogen substituted formic acid (FA) dimer is studied. The dimer stability is due to the hydrogen bonds, either conventional (OH⋯O, OH⋯F, OH⋯Cl) or non-conventional (CH⋯O, CH⋯F, CH⋯Cl). Among all the dimers, trans-trans form is more stable than the trans-cis, and cis-cis form. Basis set extrapolated counterpoise corrected interaction energy results for the FA dimer are in excellent agreement with BSSE corrected MP2 interaction energy. Symmetry Adopted Perturbation Theory (SAPT) analysis reveals that the electrostatic effect plays a dominant role in stabilization among the dimers with maximum interaction energy. Chlorine substituted FA dimer has high hyperpolarizability, which makes them excellent candidate for nonlinear optical materials (NLO). The halogen substituted formic acid dimers have higher stability and polarizability value than the unsubstituted formic acid dimer. The hyperpolarizability values depend on the geometrical structures of halogenated formic acid dimers than the type of hydrogen bonds. The small excitation energy and HOMO-LUMO gap in the halogenated formic acid dimer has led to the strong nonlinear optical response. The depolarization ratio and Rayleigh scattering increases in formic acid dimer after the halogen atom substitution.

  14. 21 CFR 582.1005 - Acetic acid.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Acetic acid. 582.1005 Section 582.1005 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS....1005 Acetic acid. (a) Product. Acetic acid. (b) Conditions of use. This substance is...

  15. 21 CFR 582.1005 - Acetic acid.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Acetic acid. 582.1005 Section 582.1005 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS....1005 Acetic acid. (a) Product. Acetic acid. (b) Conditions of use. This substance is...

  16. 21 CFR 582.1005 - Acetic acid.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Acetic acid. 582.1005 Section 582.1005 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS....1005 Acetic acid. (a) Product. Acetic acid. (b) Conditions of use. This substance is...

  17. 21 CFR 582.1005 - Acetic acid.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Acetic acid. 582.1005 Section 582.1005 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS....1005 Acetic acid. (a) Product. Acetic acid. (b) Conditions of use. This substance is...

  18. 21 CFR 582.1005 - Acetic acid.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Acetic acid. 582.1005 Section 582.1005 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS....1005 Acetic acid. (a) Product. Acetic acid. (b) Conditions of use. This substance is...

  19. Formic-acid-induced depolymerization of oxidized lignin to aromatics.

    PubMed

    Rahimi, Alireza; Ulbrich, Arne; Coon, Joshua J; Stahl, Shannon S

    2014-11-13

    Lignin is a heterogeneous aromatic biopolymer that accounts for nearly 30% of the organic carbon on Earth and is one of the few renewable sources of aromatic chemicals. As the most recalcitrant of the three components of lignocellulosic biomass (cellulose, hemicellulose and lignin), lignin has been treated as a waste product in the pulp and paper industry, where it is burned to supply energy and recover pulping chemicals in the operation of paper mills. Extraction of higher value from lignin is increasingly recognized as being crucial to the economic viability of integrated biorefineries. Depolymerization is an important starting point for many lignin valorization strategies, because it could generate valuable aromatic chemicals and/or provide a source of low-molecular-mass feedstocks suitable for downstream processing. Commercial precedents show that certain types of lignin (lignosulphonates) may be converted into vanillin and other marketable products, but new technologies are needed to enhance the lignin value chain. The complex, irregular structure of lignin complicates chemical conversion efforts, and known depolymerization methods typically afford ill-defined products in low yields (that is, less than 10-20wt%). Here we describe a method for the depolymerization of oxidized lignin under mild conditions in aqueous formic acid that results in more than 60wt% yield of low-molecular-mass aromatics. We present the discovery of this facile C-O cleavage method, its application to aspen lignin depolymerization, and mechanistic insights into the reaction. The broader implications of these results for lignin conversion and biomass refining are also considered.

  20. Formic-acid-induced depolymerization of oxidized lignin to aromatics

    NASA Astrophysics Data System (ADS)

    Rahimi, Alireza; Ulbrich, Arne; Coon, Joshua J.; Stahl, Shannon S.

    2014-11-01

    Lignin is a heterogeneous aromatic biopolymer that accounts for nearly 30% of the organic carbon on Earth and is one of the few renewable sources of aromatic chemicals. As the most recalcitrant of the three components of lignocellulosic biomass (cellulose, hemicellulose and lignin), lignin has been treated as a waste product in the pulp and paper industry, where it is burned to supply energy and recover pulping chemicals in the operation of paper mills. Extraction of higher value from lignin is increasingly recognized as being crucial to the economic viability of integrated biorefineries. Depolymerization is an important starting point for many lignin valorization strategies, because it could generate valuable aromatic chemicals and/or provide a source of low-molecular-mass feedstocks suitable for downstream processing. Commercial precedents show that certain types of lignin (lignosulphonates) may be converted into vanillin and other marketable products, but new technologies are needed to enhance the lignin value chain. The complex, irregular structure of lignin complicates chemical conversion efforts, and known depolymerization methods typically afford ill-defined products in low yields (that is, less than 10-20wt%). Here we describe a method for the depolymerization of oxidized lignin under mild conditions in aqueous formic acid that results in more than 60wt% yield of low-molecular-mass aromatics. We present the discovery of this facile C-O cleavage method, its application to aspen lignin depolymerization, and mechanistic insights into the reaction. The broader implications of these results for lignin conversion and biomass refining are also considered.

  1. Importance of acid-base equilibrium in electrocatalytic oxidation of formic acid on platinum.

    PubMed

    Joo, Jiyong; Uchida, Taro; Cuesta, Angel; Koper, Marc T M; Osawa, Masatoshi

    2013-07-10

    Electro-oxidation of formic acid on Pt in acid is one of the most fundamental model reactions in electrocatalysis. However, its reaction mechanism is still a matter of strong debate. Two different mechanisms, bridge-bonded adsorbed formate mechanism and direct HCOOH oxidation mechanism, have been proposed by assuming a priori that formic acid is the major reactant. Through systematic examination of the reaction over a wide pH range (0-12) by cyclic voltammetry and surface-enhanced infrared spectroscopy, we show that the formate ion is the major reactant over the whole pH range examined, even in strong acid. The performance of the reaction is maximal at a pH close to the pKa of formic acid. The experimental results are reasonably explained by a new mechanism in which formate ion is directly oxidized via a weakly adsorbed formate precursor. The reaction serves as a generic example illustrating the importance of pH variation in catalytic proton-coupled electron-transfer reactions.

  2. Extractive fermentation of acetic acid

    SciTech Connect

    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 of 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.

  3. Formic Acid Free Flowsheet Development To Eliminate Catalytic Hydrogen Generation In The Defense Waste Processing

    SciTech Connect

    Lambert, Dan P.; Stone, Michael E.; Newell, J. David; Fellinger, Terri L.; Bricker, Jonathan M.

    2012-09-14

    The Defense Waste Processing Facility (DWPF) processes legacy nuclear waste generated at the Savannah River Site (SRS) during production of plutonium and tritium demanded by the Cold War. The nuclear waste is first treated via a complex sequence of controlled chemical reactions and then vitrified into a borosilicate glass form and poured into stainless steel canisters. Converting the nuclear waste into borosilicate glass canisters is a safe, effective way to reduce the volume of the waste and stabilize the radionuclides. Testing was initiated to determine whether the elimination of formic acid from the DWPF's chemical processing flowsheet would eliminate catalytic hydrogen generation. Historically, hydrogen is generated in chemical processing of alkaline High Level Waste sludge in DWPF. In current processing, sludge is combined with nitric and formic acid to neutralize the waste, reduce mercury and manganese, destroy nitrite, and modify (thin) the slurry rheology. The noble metal catalyzed formic acid decomposition produces hydrogen and carbon dioxide. Elimination of formic acid by replacement with glycolic acid has the potential to eliminate the production of catalytic hydrogen. Flowsheet testing was performed to develop the nitric-glycolic acid flowsheet as an alternative to the nitric-formic flowsheet currently being processed at the DWPF. This new flowsheet has shown that mercury can be reduced and removed by steam stripping in DWPF with no catalytic hydrogen generation. All processing objectives were also met, including greatly reducing the Slurry Mix Evaporator (SME) product yield stress as compared to the baseline nitric/formic flowsheet. Ten DWPF tests were performed with nonradioactive simulants designed to cover a broad compositional range. No hydrogen was generated in testing without formic acid.

  4. Solid Molecular Phosphine Catalysts for Formic Acid Decomposition in the Biorefinery.

    PubMed

    Hausoul, Peter J C; Broicher, Cornelia; Vegliante, Roberta; Göb, Christian; Palkovits, Regina

    2016-04-25

    The co-production of formic acid during the conversion of cellulose to levulinic acid offers the possibility for on-site hydrogen production and reductive transformations. Phosphorus-based porous polymers loaded with Ru complexes exhibit high activity and selectivity in the base-free decomposition of formic acid to CO2 and H2 . A polymeric analogue of 1,2-bis(diphenylphosphino)ethane (DPPE) gave the best results in terms of performance and stability. Recycling tests revealed low levels of leaching and only a gradual decrease in the activity over seven runs. An applicability study revealed that these catalysts even facilitate selective removal of formic acid from crude product mixtures arising from the synthesis of levulinic acid.

  5. Rotational Investigation of the Adducts of Formic Acid with Alcohols, Ethers and Esters

    NASA Astrophysics Data System (ADS)

    Evangelisti, Luca; Spada, Lorenzo; Li, Weixing; Caminati, Walther

    2016-06-01

    Mixtures of formic acid with methyl alcohol, with isopropyl alcohol, with tert-butyl alcohol, with dimethylether and with isopropylformiate have been supersonically expanded as pulsed jets. The obtained cool plumes have been analyzed by Fourier transform microwave spectroscopy. It has been possible to assign the rotational spectra of the 1:1 adducts of formic acid with tert-butyl alcohol, with dimethyl ether and with isopropylformiate. The conformational shapes and geometries of these adducts, as well as the topologies of their itermolecular hydrogen bonds will be presented. An explanation is given of the failure of the assignments of the rotational spectra of the adducts of formic acid with methyl alcohol and isopropyl alcohol.

  6. Facile synthesis of PtAu alloy nanoparticles with high activity for formic acid oxidation

    SciTech Connect

    Zhang, Sheng; Shao, Yuyan; Yin, Geping; Lin, Yuehe

    2010-02-15

    We report the facile synthesis of carbon supported PtAu alloy nanoparticles with high electrocatalytic activity as the anode catalyst for direct formic acid fuel cells (DFAFCs). PtAu alloy nanopaticles are synthesized by co-reducing HAuCl4 and H2PtCl6 with NaBH4 in the presence of sodium citrate and then the nanoparticles are deposited on Vulcan XC-72R carbon support (PtAu/C). The obtained catalysts are characterized with X-ray diffraction (XRD) and transmission electron microscope (TEM), which reveal PtAu alloy formation with an average diameter of 4.6 nm. PtAu/C exhibits 8 times higher catalytic activity toward formic acid oxidation than Pt/C. The enhanced activity of PtAu/C catalyst is attributed to noncontinuous Pt sites formed in the presence of the neighbored Au sites, which promotes direct oxidation of formic acid by avoiding poison CO.

  7. 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.

  8. Formic acid as a hydrogen storage material - development of homogeneous catalysts for selective hydrogen release.

    PubMed

    Mellmann, Dörthe; Sponholz, Peter; Junge, Henrik; Beller, Matthias

    2016-07-11

    Formic acid (FA, HCO2H) receives considerable attention as a hydrogen storage material. In this respect, hydrogenation of CO2 to FA and dehydrogenation of FA are crucial reaction steps. In the past decade, for both reactions, several molecularly defined and nanostructured catalysts have been developed and intensively studied. From 2010 onwards, this review covers recent advancements in this area using homogeneous catalysts. In addition to the development of catalysts for H2 generation, reversible H2 storage including continuous H2 production from formic acid is highlighted. Special focus is put on recent progress in non-noble metal catalysts.

  9. A ruthenium-based biomimetic hydrogen cluster for efficient photocatalytic hydrogen generation from formic acid.

    PubMed

    Chang, Chin-Hao; Chen, Mei-Hua; Du, Wan-Shan; Gliniak, Jacek; Lin, Jia-Hoa; Wu, Hsin-Hua; Chan, Hsin-Fang; Yu, Jen-Shiang K; Wu, Tung-Kung

    2015-04-20

    A ruthenium-based biomimetic hydrogen cluster, [Ru2 (CO)6 (μ-SCH2 CH2 CH2 S)] (1), has been synthesized and, in the presence of the P ligand tri(o-tolyl)phosphine, demonstrated efficient photocatalytic hydrogen generation from formic acid decomposition. Turnover frequencies (TOFs) of 5500 h(-1) and turnover numbers (TONs) over 24 700 were obtained with less than 50 ppm of the catalyst, thus representing the highest TOFs for ruthenium complexes as well as the best efficiency for photocatalytic hydrogen production from formic acid. Moreover, 1 showed high stability with no significant degradation of the photocatalyst observed after prolonged photoirradiation at 90 °C.

  10. Oxidation mechanism of formic acid on the bismuth adatom-modified Pt(111) surface.

    PubMed

    Perales-Rondón, Juan Victor; Ferre-Vilaplana, Adolfo; Feliu, Juan M; Herrero, Enrique

    2014-09-24

    In order to improve catalytic processes, elucidation of reaction mechanisms is essential. Here, supported by a combination of experimental and computational results, the oxidation mechanism of formic acid on Pt(111) electrodes modified by the incorporation of bismuth adatoms is revealed. In the proposed model, formic acid is first physisorbed on bismuth and then deprotonated and chemisorbed in formate form, also on bismuth, from which configuration the C-H bond is cleaved, on a neighbor Pt site, yielding CO2. It was found computationally that the activation energy for the C-H bond cleavage step is negligible, which was also verified experimentally. PMID:25188779

  11. Transformation of cellulose and its derived carbohydrates into formic and lactic acids catalyzed by vanadyl cations.

    PubMed

    Tang, Zhenchen; Deng, Weiping; Wang, Yanliang; Zhu, Enze; Wan, Xiaoyue; Zhang, Qinghong; Wang, Ye

    2014-06-01

    The transformation of cellulose or cellulose-derived carbohydrates into platform chemicals is the key to establish biomass-based sustainable chemical processes. The systems able to catalyze the conversion of cellulose into key chemicals in water without the consumption of hydrogen are limited. We report that simple vanadyl (VO(2+)) cations catalyze the conversions of cellulose and its monomer, glucose, into lactic acid and formic acid in water. We have discovered an interesting shift of the major product from formic acid to lactic acid on switching the reaction atmosphere from oxygen to nitrogen. Our studies suggest that VO(2+) catalyzes the isomerization of glucose to fructose, the retro-aldol fragmentation of fructose to two trioses, and the isomerization of trioses, which leads to the formation of lactic acid under anaerobic conditions. The oxidative cleavage of C-C bonds in the intermediates caused by the redox conversion of VO2(+)/VO(2+) under aerobic conditions results in formic acid and CO2. We demonstrate that the addition of an alcohol suppresses the formation of CO2 and enhances the formic acid yield significantly to 70-75 %.

  12. Transformation of cellulose and its derived carbohydrates into formic and lactic acids catalyzed by vanadyl cations.

    PubMed

    Tang, Zhenchen; Deng, Weiping; Wang, Yanliang; Zhu, Enze; Wan, Xiaoyue; Zhang, Qinghong; Wang, Ye

    2014-06-01

    The transformation of cellulose or cellulose-derived carbohydrates into platform chemicals is the key to establish biomass-based sustainable chemical processes. The systems able to catalyze the conversion of cellulose into key chemicals in water without the consumption of hydrogen are limited. We report that simple vanadyl (VO(2+)) cations catalyze the conversions of cellulose and its monomer, glucose, into lactic acid and formic acid in water. We have discovered an interesting shift of the major product from formic acid to lactic acid on switching the reaction atmosphere from oxygen to nitrogen. Our studies suggest that VO(2+) catalyzes the isomerization of glucose to fructose, the retro-aldol fragmentation of fructose to two trioses, and the isomerization of trioses, which leads to the formation of lactic acid under anaerobic conditions. The oxidative cleavage of C-C bonds in the intermediates caused by the redox conversion of VO2(+)/VO(2+) under aerobic conditions results in formic acid and CO2. We demonstrate that the addition of an alcohol suppresses the formation of CO2 and enhances the formic acid yield significantly to 70-75 %. PMID:24798653

  13. Copper corrosion mechanism in the presence of formic acid vapor for short exposure times

    SciTech Connect

    Bastidas, J.M.; Lopez-Delgado, A.; Cano, E.; Polo, J.L.; Lopez, F.A.

    2000-03-01

    The rate of copper corrosion originated by the action of formic acid vapors at 100% relative humidity was studied. Five formic vapor concentration levels (10, 50, 100, 200, and 300 ppm) were used. A copper corrosion rate of up to 1,300 mg/m{sup 2} d was measured for a period of 21 days using a gravimetric method. The patina layers were characterized using cathodic reduction, X-ray powder diffraction. Fourier transform infrared spectrometry, and scanning electron microscopy techniques. Some of the components identified in the corrosion-product layers were cuprite (Cu{sub 2}O), cupric hydroxide hydrate [Cu(OH){sub 2}{sm_bullet}H{sub 2}O], and copper formate hydrate [Cu(HCOO){sub 2}{sm_bullet}4H{sub 2}O]. The latter was formed by both cupric hydroxide and formic acid-cuprous ion complex mechanisms.

  14. Pd nanoparticles supported on functionalized multi-walled carbon nanotubes (MWCNTs) and electrooxidation for formic acid

    NASA Astrophysics Data System (ADS)

    Yang, Sudong; Zhang, Xiaogang; Mi, Hongyu; Ye, Xiangguo

    To improve the utilization and activity of anodic catalysts for formic acid electrooxidation, palladium (Pd) particles were loaded on the MWCNTs, which were functionalized in a mixture of 96% sulfuric acid and 4-aminobenzenesulfonic acid, using sodium nitrite to produce intermediate diazonium salts from substituted anilines. The composition, particle size, and crystallinity of the Pd/f-MWCNTs catalysts were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and energy dispersive spectroscopy (EDS) measurements. The electrocatalytic properties of the Pd/f-MWCNTs catalysts for formic acid oxidation were investigated by cyclic voltammetry (CV) and linear sweep voltammetry (LSV) in 0.5 mol L -1 H 2SO 4 solution. The results demonstrated that the catalytic activity was greatly enhanced due to the improved water-solubility and dispersion of the f-MWCNTs, which were facile to make the small particle size (3.8 nm) and uniform dispersion of Pd particles loading on the surface of the MWCNTs. In addition, the functionalized MWCNTs with benzenesulfonic group can provide benzenesulfonic anions in aqueous solution, which may combine with hydrogen cation and then promote the oxidation of formic acid reactive intermediates. So the Pd/f-MWCNTs composites showed excellent electrocatalytic activity for formic acid oxidation.

  15. Bridge-bonded formate: active intermediate or spectator species in formic acid oxidation on a Pt film electrode?

    PubMed

    Chen, Y-X; Heinen, M; Jusys, Z; Behm, R J

    2006-12-01

    We present and discuss the results of an in situ IR study on the mechanism and kinetics of formic acid oxidation on a Pt film/Si electrode, performed in an attenuated total reflection (ATR) flow cell configuration under controlled mass transport conditions, which specifically aimed at elucidating the role of the adsorbed bridge-bonded formates in this reaction. Potentiodynamic measurements show a complex interplay between formation and desorption/oxidation of COad and formate species and the total Faradaic current. The notably faster increase of the Faradaic current compared to the coverage of bridge-bonded formate in transient measurements at constant potential, but with different formic acid concentrations, reveals that adsorbed formate decomposition is not rate-limiting in the dominant reaction pathway. If being reactive intermediate at all, the contribution of formate adsorption/decomposition to the reaction current decreases with increasing formic acid concentration, accounting for at most 15% for 0.2 M DCOOH at 0.7 VRHE. The rapid build-up/removal of the formate adlayer and its similarity with acetate or (bi-)sulfate adsorption/desorption indicate that the formate adlayer coverage is dominated by a fast dynamic adsorption-desorption equilibrium with the electrolyte, and that formate desorption is much faster than its decomposition. The results corroborate the proposal of a triple pathway reaction mechanism including an indirect pathway, a formate pathway, and a dominant direct pathway, as presented previously (Chen, Y. X.; et al. Angew. Chem. Int. Ed. 2006, 45, 981), in which adsorbed formates act as a site-blocking spectator in the dominant pathway rather than as an active intermediate.

  16. Catalytic effect of water, formic acid, or sulfuric acid on the reaction of formaldehyde with OH radicals.

    PubMed

    Zhang, Weichao; Du, Benni; Qin, Zhenglong

    2014-07-01

    In this paper, for the hydrogen abstraction reaction of HCHO by OH radicals assisted by water, formic acid, or sulfur acid, the possible reaction mechanisms and kinetics have been investigated theoretically using quantum chemistry methods and transition-state theory. The potential energy surfaces calculated at the CCSD(T)/6-311++G(df,pd)//MP2(full)/6-311++G(df,pd) levels of theory reveal that, due to the formation of strong hydrogen bond(s), the relative energies of the transition states involving catalyst are significantly reduced compared to that reaction without catalyst. However, the kinetics calculations show that the rate constants are smaller by about 3, 9, or 10 orders of magnitude for water, formic acid, or sulfur acid assisted reactions than that uncatalyzed reaction, respectively. Consequently, none of the water, formic acid, or sulfur acid can accelerate the title reaction in the atmosphere.

  17. Reaction sequences in simulated neutralized current acid waste slurry during processing with formic acid

    SciTech Connect

    Smith, H.D.; Wiemers, K.D.; Langowski, M.H.; Powell, M.R.; Larson, D.E.

    1993-11-01

    The Hanford Waste Vitrification Plant (HWVP) is being designed for the Department of Energy to immobilize high-level and transuranic wastes as glass for permanent disposal. Pacific Northwest Laboratory is supporting the HWVP design activities by conducting laboratory-scale studies using a HWVP simulated waste slurry. Conditions which affect the slurry processing chemistry were evaluated in terms of offgas composition and peak generation rate and changes in slurry composition. A standard offgas profile defined in terms of three reaction phases, decomposition of H{sub 2}CO{sub 3}, destruction of NO{sub 2}{sup {minus}}, and production of H{sub 2} and NH{sub 3} was used as a baseline against which changes were evaluated. The test variables include nitrite concentration, acid neutralization capacity, temperature, and formic acid addition rate. Results to date indicate that pH is an important parameter influencing the N{sub 2}O/NO{sub x} generation ratio; nitrite can both inhibit and activate rhodium as a catalyst for formic acid decomposition to CO{sub 2} and H{sub 2}; and a separate reduced metal phase forms in the reducing environment. These data are being compiled to provide a basis for predicting the HWVP feed processing chemistry as a function of feed composition and operation variables, recommending criteria for chemical adjustments, and providing guidelines with respect to important control parameters to consider during routine and upset plant operation.

  18. Hanford waste vitrification plant hydrogen generation study: Preliminary evaluation of alternatives to formic acid

    SciTech Connect

    King, R.B.; Bhattacharyya, N.K.; Kumar, V.

    1996-02-01

    Oxalic, glyoxylic, glycolic, malonic, pyruvic, lactic, levulinic, and citric acids as well as glycine have been evaluated as possible substitutes for formic acid in the preparation of feed for the Hanford waste vitrification plant using a non-radioactive feed stimulant UGA-12M1 containing substantial amounts of aluminum and iron oxides as well as nitrate and nitrite at 90C in the presence of hydrated rhodium trichloride. Unlike formic acid none of these carboxylic acids liberate hydrogen under these conditions and only malonic and citric acids form ammonia. Glyoxylic, glycolic, malonic, pyruvic, lactic, levulinic, and citric acids all appear to have significant reducing properties under the reaction conditions of interest as indicated by the observation of appreciable amounts of N{sub 2}O as a reduction product of,nitrite or, less likely, nitrate at 90C. Glyoxylic, pyruvic, and malonic acids all appear to be unstable towards decarboxylation at 90C in the presence of Al(OH){sub 3}. Among the carboxylic acids investigated in this study the {alpha}-hydroxycarboxylic acids glycolic and lactic acids appear to be the most interesting potential substitutes for formic acid in the feed preparation for the vitrification plant because of their failure to produce hydrogen or ammonia or to undergo decarboxylation under the reaction conditions although they exhibit some reducing properties in feed stimulant experiments.

  19. Influence of sodium carbonate on decomposition of formic acid by pulsed discharge plasma inside bubble in water

    NASA Astrophysics Data System (ADS)

    Iwabuchi, Masashi; Takahashi, Katsuyuki; Takaki, Koichi; Satta, Naoya

    2016-07-01

    The influence of sodium carbonate on the decomposition of formic acid by discharge inside bubbles in water was investigated experimentally. Oxygen or argon gases were injected into the water through a vertically positioned glass tube, in which the high-voltage wire electrode was placed to generate plasmas at low applied voltage. The concentration of formic acid was determined by ion chromatography. In the case of sodium carbonate additive, the pH increased owing to the decomposition of the formic acid. In the case of oxygen injection, the percentage of conversion of formic acid increased with increasing pH because the reaction rate of ozone with formic acid increased with increasing pH. In the case of argon injection, the percentage of conversion was not affected by the pH owing to the high rate loss of hydroxyl radicals.

  20. The effect of formic acid concentration on the conductivity and corrosion resistance of chromium carbide coatings electroplated with trivalent chromium

    NASA Astrophysics Data System (ADS)

    Lu, Chen-En; Pu, Nen-Wen; Hou, Kung-Hsu; Tseng, Chun-Chieh; Ger, Ming-Der

    2013-10-01

    Different concentrations of formic acid were added into a trivalent chromium electroplating solution to produce chromium carbide (Crsbnd C) coatings. The influence of the formic acid concentration on chemical composition, microstructure, surface morphology, corrosion resistance, conductivity and carbon content of the resulting Crsbnd C coatings was studied. Formic acid was found to increase the carbon content in the coatings so as to form Crsbnd C films. These coatings had a nearly amorphous structure containing Cr, Cr2O3, and various Crsbnd C compounds with carbon content uniformly distributed throughout the coatings. The carbon content and the conductivity of the Crsbnd C layer were correlated with formic acid concentration. For a formic acid concentration of 2 M, the Crsbnd C layer had the highest carbon content (∼28%), the lowest contact resistance, and the best corrosion resistance along with a corrosion current density of ∼6.4 × 10-7 A/cm2.

  1. 40 CFR 180.1178 - Formic acid; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD... pesticide formic acid is exempted from the requirement of a tolerance in or on honey and honeycomb when used to control tracheal mites and suppress varroa mites in bee colonies, and applied in accordance...

  2. 40 CFR 180.1178 - Formic acid; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD... pesticide formic acid is exempted from the requirement of a tolerance in or on honey and honeycomb when used to control tracheal mites and suppress varroa mites in bee colonies, and applied in accordance...

  3. 40 CFR 180.1178 - Formic acid; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD... pesticide formic acid is exempted from the requirement of a tolerance in or on honey and honeycomb when used to control tracheal mites and suppress varroa mites in bee colonies, and applied in accordance...

  4. 40 CFR 180.1178 - Formic acid; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD... pesticide formic acid is exempted from the requirement of a tolerance in or on honey and honeycomb when used to control tracheal mites and suppress varroa mites in bee colonies, and applied in accordance...

  5. 40 CFR 180.1178 - Formic acid; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD... pesticide formic acid is exempted from the requirement of a tolerance in or on honey and honeycomb when used to control tracheal mites and suppress varroa mites in bee colonies, and applied in accordance...

  6. Formic acid, ethanol in vycor glass, and water in aluminosilicate zeolites

    SciTech Connect

    Loong, C.K.; Trouw, F.; Iton, L.E.

    1993-11-01

    We present results of incoherent inelastic neutron-scattering experiments on formic acid, ethanol in vycor glass, and water in aluminosilicate zeolites performed at Argonne`s spallation neutron source, IPNS. The forming and breaking of hydrogen bonds are discussed in terms of translational and rotational diffusion, and vibrational footprints of various molecular species in these systems.

  7. Localized Pd Overgrowth on Cubic Pt Nanocrystals for Enhanced Electrocatalytic Oxidation of Formic Acid

    SciTech Connect

    Lee, H.; Habas, S.E.; Somorjai, G.A.; Yang, P.

    2008-03-20

    Binary Pt/Pd nanoparticles were synthesized by localized overgrowth of Pd on cubic Pt seeds for the investigation of electrocatalytic formic acid oxidation. The binary particles exhibited much less self-poisoning and a lower activation energy relative to Pt nanocubes, consistent with the single crystal study.

  8. Pd/C Synthesized with Citric Acid: An Efficient Catalyst for Hydrogen Generation from Formic Acid/Sodium Formate

    PubMed Central

    Wang, Zhi-Li; Yan, Jun-Min; Wang, Hong-Li; Ping, Yun; Jiang, Qing

    2012-01-01

    A highly efficient hydrogen generation from formic acid/sodium formate aqueous solution catalyzed by in situ synthesized Pd/C with citric acid has been successfully achieved at room temperature. Interestingly, the presence of citric acid during the formation and growth of the Pd nanoparticles on carbon can drastically enhance the catalytic property of the resulted Pd/C, on which the conversion and turnover frequency for decomposition of formic acid/sodium formate system can reach the highest values ever reported of 85% within 160 min and 64 mol H2 mol−1 catalyst h−1, respectively, at room temperature. The present simple, low cost, but highly efficient CO-free hydrogen generation system at room temperature is believed to greatly promote the practical application of formic acid system on fuel cells. PMID:22953041

  9. Properties of nanocellulose isolated from corncob residue using sulfuric acid, formic acid, oxidative and mechanical methods.

    PubMed

    Liu, Chao; Li, Bin; Du, Haishun; Lv, Dong; Zhang, Yuedong; Yu, Guang; Mu, Xindong; Peng, Hui

    2016-10-20

    In this work, nanocellulose was extracted from bleached corncob residue (CCR), an underutilized lignocellulose waste from furfural industry, using four different methods (i.e. sulfuric acid hydrolysis, formic acid (FA) hydrolysis, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation, and pulp refining, respectively). The self-assembled structure, morphology, dimension, crystallinity, chemical structure and thermal stability of prepared nanocellulose were investigated. FA hydrolysis produced longer cellulose nanocrystals (CNCs) than the one obtained by sulfuric acid hydrolysis, and resulted in high crystallinity and thermal stability due to its preferential degradation of amorphous cellulose and lignin. The cellulose nanofibrils (CNFs) with fine and individualized structure could be isolated by TEMPO-mediated oxidation. In comparison with other nanocellulose products, the intensive pulp refining led to the CNFs with the longest length and the thickest diameter. This comparative study can help to provide an insight into the utilization of CCR as a potential source for nanocellulose production. PMID:27474618

  10. Pd clusters supported on amorphous, low-porosity carbon spheres for hydrogen production from formic acid.

    PubMed

    Bulushev, Dmitri A; Bulusheva, Lyubov G; Beloshapkin, Sergey; O'Connor, Thomas; Okotrub, Alexander V; Ryan, Kevin M

    2015-04-29

    Amorphous, low-porosity carbon spheres on the order of a few micrometers in size were prepared by carbonization of squalane (C30H62) in supercritical CO2 at 823 K. The spheres were characterized and used as catalysts' supports for Pd. Near-edge X-ray absorption fine structure studies of the spheres revealed sp(2) and sp(3) hybridized carbon. To activate carbons for interaction with a metal precursor, often oxidative treatment of a support is needed. We showed that boiling of the obtained spheres in 28 wt % HNO3 did not affect the shape and bulk structure of the spheres, but led to creation of a considerable amount of surface oxygen-containing functional groups and increase of the content of sp(2) hybridized carbon on the surface. This carbon was seen by scanning transmission electron microscopy in the form of waving graphene flakes. The H/C atomic ratio in the spheres was relatively high (0.4) and did not change with the HNO3 treatment. Palladium was deposited by impregnation with Pd acetate followed by reduction in H2. This gave uniform Pd clusters with a size of 2-4 nm. The Pd supported on the original C spheres showed 2-3 times higher catalytic activity in vapor phase formic acid decomposition and higher selectivity for H2 formation (98-99%) than those for the catalyst based on the HNO3 treated spheres. Using of such low-porosity spheres as a catalyst support should prevent mass transfer limitations for fast catalytic reactions.

  11. Putative ABC transporter responsible for acetic acid resistance in Acetobacter aceti.

    PubMed

    Nakano, Shigeru; Fukaya, Masahiro; Horinouchi, Sueharu

    2006-01-01

    Two-dimensional gel electrophoretic analysis of the membrane fraction of Acetobacter aceti revealed the presence of several proteins that were produced in response to acetic acid. A 60-kDa protein, named AatA, which was mostly induced by acetic acid, was prepared; aatA was cloned on the basis of its NH2-terminal amino acid sequence. AatA, consisting of 591 amino acids and containing ATP-binding cassette (ABC) sequences and ABC signature sequences, belonged to the ABC transporter superfamily. The aatA mutation with an insertion of the neomycin resistance gene within the aatA coding region showed reduced resistance to acetic acid, formic acid, propionic acid, and lactic acid, whereas the aatA mutation exerted no effects on resistance to various drugs, growth at low pH (adjusted with HCl), assimilation of acetic acid, or resistance to citric acid. Introduction of plasmid pABC101 containing aatA under the control of the Escherichia coli lac promoter into the aatA mutant restored the defect in acetic acid resistance. In addition, pABC101 conferred acetic acid resistance on E. coli. These findings showed that AatA was a putative ABC transporter conferring acetic acid resistance on the host cell. Southern blot analysis and subsequent nucleotide sequencing predicted the presence of aatA orthologues in a variety of acetic acid bacteria belonging to the genera Acetobacter and Gluconacetobacter. The fermentation with A. aceti containing aatA on a multicopy plasmid resulted in an increase in the final yield of acetic acid.

  12. The vertical transmission of salmonellas and formic acid treatment of chicken feed. A possible strategy for control.

    PubMed Central

    Humphrey, T. J.; Lanning, D. G.

    1988-01-01

    The treatment of feed given to laying hens with 0.5% formic acid reduced significantly the isolation rate of salmonellas and was associated with a reduction in the incidence of infection in newly hatched chicks. These improvements were not sustained until slaughter, however, as growing birds acquired salmonellas, probably from feed which was not acid treated. The data indicate that formic acid treatment of chicken food could have important benefits for the public health. PMID:3338506

  13. Electrons Mediate the Gas-Phase Oxidation of Formic Acid with Ozone.

    PubMed

    van der Linde, Christian; Tang, Wai-Kit; Siu, Chi-Kit; Beyer, Martin K

    2016-08-26

    Gas-phase reactions of CO3 (.-) with formic acid are studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Signal loss indicates the release of a free electron, with the formation of neutral reaction products. This is corroborated by adding traces of SF6 to the reaction gas, which scavenges 38 % of the electrons. Quantum chemical calculations of the reaction potential energy surface provide a reaction path for the formation of neutral carbon dioxide and water as the thermochemically favored products. From the literature, it is known that free electrons in the troposphere attach to O2 , which in turn transfer the electron to O3 . O3 (.-) reacts with CO2 to form CO3 (.-) . The reaction reported here formally closes the catalytic cycle for the oxidation of formic acid with ozone, catalyzed by free electrons.

  14. Efficient disproportionation of formic acid to methanol using molecular ruthenium catalysts.

    PubMed

    Savourey, Solène; Lefèvre, Guillaume; Berthet, Jean-Claude; Thuéry, Pierre; Genre, Caroline; Cantat, Thibault

    2014-09-22

    The disproportionation of formic acid to methanol was unveiled in 2013 using iridium catalysts. Although attractive, this transformation suffers from very low yields; methanol was produced in less than 2% yield, because the competitive dehydrogenation of formic acid (to CO2 and H2) is favored. We report herein the efficient and selective conversion of HCOOH to methanol in 50% yield, utilizing ruthenium(II) phosphine complexes under mild conditions. Experimental and theoretical (DFT) results show that different convergent pathways are involved in the production of methanol, depending on the nature of the catalyst. Reaction intermediates have been isolated and fully characterized and the reaction chemistry of the resulting ruthenium complexes has been studied. PMID:25088282

  15. Computational Study of Formic Acid Dehydrogenation Catalyzed by Al(III)-Bis(imino)pyridine.

    PubMed

    Lu, Qian-Qian; Yu, Hai-Zhu; Fu, Yao

    2016-03-18

    The mechanism of formic acid dehydrogenation catalyzed by the bis(imino)pyridine-ligated aluminum hydride complex (PDI(2-))Al(THF)H (PDI=bis(imino)pyridine) was studied by density functional theory calculations. The overall transformation is composed of two stages: catalyst activation and the catalytic cycle. The catalyst activation begins with O-H bond cleavage of HCOOH promoted by aluminum-ligand cooperation, followed by HCOOH-assisted Al-H bond cleavage, and protonation of the imine carbon atom of the bis(imino)pyridine ligand. The resultant doubly protonated complex ((H,H) PDI)Al(OOCH)3 is the active catalyst for formic acid dehydrogenation. Given this, the catalytic cycle includes β-hydride elimination of ((H,H) PDI)Al(OOCH)3 to produce CO2, and the formed ((H,H) PDI)Al(OOCH)2 H mediates HCOOH to release H2. PMID:26879469

  16. One site is enough: a theoretical investigation of iron-catalyzed dehydrogenation of formic Acid.

    PubMed

    Sánchez-de-Armas, Rocío; Xue, Liqin; Ahlquist, Mårten S G

    2013-09-01

    Dehydrogenation of HCO2H: The reaction mechanism for the dehydrogenation of formic acid catalyzed by a highly active and selective iron complex has been studied by DFT. The most favorable pathway shows the hydride in Fe-H complexes acting as a spectator ligand throughout the catalytic cycle. This result opens up the Fe complex for modification in order to achieve more efficient and selective catalysts. PMID:23907850

  17. 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.

  18. Electrocatalysis of formic acid on palladium and platinum surfaces: from fundamental mechanisms to fuel cell applications.

    PubMed

    Jiang, Kun; Zhang, Han-Xuan; Zou, Shouzhong; Cai, Wen-Bin

    2014-10-14

    Formic acid as a natural biomass and a CO2 reduction product has attracted considerable interest in renewable energy exploitation, serving as both a promising candidate for chemical hydrogen storage material and a direct fuel for low temperature liquid fed fuel cells. In addition to its chemical dehydrogenation, formic acid oxidation (FAO) is a model reaction in the study of electrocatalysis of C1 molecules and the anode reaction in direct formic acid fuel cells (DFAFCs). Thanks to a deeper mechanistic understanding of FAO on Pt and Pd surfaces brought about by recent advances in the fundamental investigations, the "synthesis-by-design" concept has become a mainstream idea to attain high-performance Pt- and Pd-based nanocatalysts. As a result, a large number of efficient nanocatalysts have been obtained through different synthesis strategies by tailoring geometric and electronic structures of the two primary catalytic metals. In this paper, we provide a brief overview of recent progress in the mechanistic studies of FAO, the synthesis of novel Pd- and Pt-based nanocatalysts as well as their practical applications in DFAFCs with a focus on discussing studies significantly contributing to these areas in the past five years.

  19. DISSOCIATIVE RECOMBINATION OF PROTONATED FORMIC ACID: IMPLICATIONS FOR MOLECULAR CLOUD AND COMETARY CHEMISTRY

    SciTech Connect

    Vigren, E.; Hamberg, M.; Zhaunerchyk, V.; Larsson, M.; Thomas, R. D.; Af Ugglas, M.; Kashperka, I.; Geppert, W. D.; Kaminska, M.; Semaniak, J.; Millar, T. J.; Walsh, C.; Roberts, H.

    2010-02-01

    At the heavy ion storage ring CRYRING in Stockholm, Sweden, we have investigated the dissociative recombination of DCOOD{sup +}{sub 2} at low relative kinetic energies, from approx1 meV to 1 eV. The thermal rate coefficient has been found to follow the expression k(T) = 8.43 x 10{sup -7} (T/300){sup -0.78} cm{sup 3} s{sup -1} for electron temperatures, T, ranging from approx10 to approx1000 K. The branching fractions of the reaction have been studied at approx2 meV relative kinetic energy. It has been found that approx87% of the reactions involve breaking a bond between heavy atoms. In only 13% of the reactions do the heavy atoms remain in the same product fragment. This puts limits on the gas-phase production of formic acid, observed in both molecular clouds and cometary comae. Using the experimental results in chemical models of the dark cloud, TMC-1, and using the latest release of the UMIST Database for Astrochemistry improves the agreement with observations for the abundance of formic acid. Our results also strengthen the assumption that formic acid is a component of cometary ices.

  20. Electrocatalysis of formic acid on palladium and platinum surfaces: from fundamental mechanisms to fuel cell applications.

    PubMed

    Jiang, Kun; Zhang, Han-Xuan; Zou, Shouzhong; Cai, Wen-Bin

    2014-10-14

    Formic acid as a natural biomass and a CO2 reduction product has attracted considerable interest in renewable energy exploitation, serving as both a promising candidate for chemical hydrogen storage material and a direct fuel for low temperature liquid fed fuel cells. In addition to its chemical dehydrogenation, formic acid oxidation (FAO) is a model reaction in the study of electrocatalysis of C1 molecules and the anode reaction in direct formic acid fuel cells (DFAFCs). Thanks to a deeper mechanistic understanding of FAO on Pt and Pd surfaces brought about by recent advances in the fundamental investigations, the "synthesis-by-design" concept has become a mainstream idea to attain high-performance Pt- and Pd-based nanocatalysts. As a result, a large number of efficient nanocatalysts have been obtained through different synthesis strategies by tailoring geometric and electronic structures of the two primary catalytic metals. In this paper, we provide a brief overview of recent progress in the mechanistic studies of FAO, the synthesis of novel Pd- and Pt-based nanocatalysts as well as their practical applications in DFAFCs with a focus on discussing studies significantly contributing to these areas in the past five years. PMID:25144896

  1. CO2 Hydrogenation to Formic Acid on Ni(111)

    SciTech Connect

    Peng, Guowen; Sibener, S. J.; Schatz, George C.; Ceyer, Sylvia T.; Mavrikakis, Manos

    2011-12-26

    Periodic, self-consistent, density functional theory (DFT) calculations are employed to study CO2 hydrogenation on Ni(111). CO2 hydrogenation with H adsorbed on the surface and with H absorbed in the subsurface is investigated systematically, and the respective microscopic reaction mechanisms are elucidated. We show that on Ni(111) CO2 hydrogenation to formate intermediate is more favorable than to carboxyl intermediate. The hydrogenation to formate goes through the unidentate structure that rapidly transforms into the bidentate structure. Further hydrogenation from formate to formic acid is energetically more difficult than formate formation. Formation of adsorbed formic acid from adsorbed CO2 and surface hydrogen is an endothermic reaction. Because subsurface H in Ni(111) is substantially less stable compared to surface H, its reaction with adsorbed CO2 to adsorbed formic acid is an exothermic one. Finally, our results may have significant implications for the synthesis of liquid fuels from CO2 and for catalytic hydrogenation reactions in general.

  2. Trends in Formic Acid Decomposition on Model Transition Metal Surfaces: A Density Functional Theory Study

    SciTech Connect

    Herron, Jeffrey A.; Scaranto, Jessica; Ferrin, Peter A.; Li, Sha; Mavrikakis, Manos

    2014-12-05

    We present a first-principles, self-consistent periodic density functional theory (PW91-GGA) study of formic acid (HCOOH) decomposition on model (111) and (100) facets of eight fcc metals (Au, Ag, Cu, Pt, Pd, Ni, Ir, and Rh) and (0001) facets of four hcp (Co, Os, Ru, and Re) metals. The calculated binding energies of key formic acid decomposition intermediates including formate (HCOO), carboxyl (COOH), carbon monoxide (CO), water (H2O), carbon dioxide (CO2), hydroxyl (OH), carbon (C), oxygen (O), and hydrogen (H; H2) are presented. Using these energetics, we develop thermochemical potential energy diagrams for both the carboxyl-mediated and the formate-mediated dehydrogenation mechanisms on each surface. We evaluate the relative stability of COOH, HCOO, and other isomeric intermediates (i.e., CO + OH, CO2 + H, CO + O + H) on these surfaces. These results provide insights into formic acid decomposition selectivity (dehydrogenation versus dehydration), and in conjunction with calculated vibrational frequency modes, the results can assist with the experimental search for the elusive carboxyl (COOH) surface intermediate. Results are compared against experimental reports in the literature.

  3. Hydrogen from formic acid through its selective disproportionation over sodium germanate--a non-transition-metal catalysis system.

    PubMed

    Amos, Ruth I J; Heinroth, Falk; Chan, Bun; Zheng, Sisi; Haynes, Brian S; Easton, Christopher J; Masters, Anthony F; Radom, Leo; Maschmeyer, Thomas

    2014-10-13

    A robust catalyst for the selective dehydrogenation of formic acid to liberate hydrogen gas has been designed computationally, and also successfully demonstrated experimentally. This is the first such catalyst not based on transition metals, and it exhibits very encouraging performance. It represents an important step towards the use of renewable formic acid as a hydrogen-storage and transport vector in fuel and energy applications. PMID:25169798

  4. Dynamic Protonation Equilibrium of Solvated Acetic Acid

    SciTech Connect

    Gu, Wei; Frigato, Tomaso; Straatsma, TP; Helms, Volkhard H.

    2007-04-13

    For the first time, the dynamic protonation equilibrium between an amino acid side chain analogue and bulk water as well as the diffusion properties of the excess proton were successfully reproduced through unbiased computer simulations. During a 50 ns Q-HOP MD simulation, two different regimes of proton transfer were observed. Extended phases of frequent proton swapping between acetic acid and nearby water were separated by phases where the proton freely diffuses in the simulation box until it is captured again by acetic acid. The pKa of acetic acid was calculated around 3.0 based on the relative population of protonated and deprotonated states and the diffusion coefficient of excess proton was computed from the average mean squared displacement in the simulation. Both calculated values agree well with the experimental measurements.

  5. Electrospun homogeneous silk fibroin/poly (ɛ-caprolactone) nanofibrous scaffolds by addition of acetic acid for tissue engineering.

    PubMed

    Zhu, Jiang; Luo, Jingjing; Zhao, Xingyan; Gao, Junjiu; Xiong, Jie

    2016-09-01

    In this study, we investigated the phase separation phenomenon of silk fibroin/poly (ɛ-caprolactone) electrospinning solution to improve the performance of silk fibroin/poly (ɛ-caprolactone) electrospun nanofibers. It showed that phase separation does occur in just a few hours in the silk fibroin/poly (ɛ-caprolactone)/formic acid mixture solution. Acetic acid, small molecule nonsolvent for silk fibroin, was first introduced to silk fibroin/poly (ɛ-caprolactone)/formic acid solution, a homogeneous solution without separation for over several days was achieved after mixing for 5 h. The morphology and composition of the silk fibroin/poly (ɛ-caprolactone) and acetic acid-modified silk fibroin/poly (ɛ-caprolactone) fibrous scaffolds were examined by scanning electron microscopy, Fourier transform infrared spectroscopy and thermal gravimetric analyzer. Attachment and proliferation of mouse osteoblast MC3T3-E1 cells were tested by scanning electron microscopy and cytotoxity assay. The results indicated that the phase separation of silk fibroin/poly (ɛ-caprolactone) solution might led to inhomogeneous morphology and composition of the composite scaffolds, and the inhomogeneity of the silk fibroin/poly (ɛ-caprolactone) scaffolds with formic acid as solvent had a remarkable difference on cell adhesion and proliferation. In contrast, there was no significant difference among the silk fibroin/poly (ɛ-caprolactone) scaffolds with formic acid/acetic acid as solvent because of their good consistency in fiber morphology and composition. These obtained silk fibroin/poly (ɛ-caprolactone) nanofibers had small average diameter of 190 ± 40 nm. The obtained results proved that this study provided a facile and effective approach to achieve compositionally homogeneous silk fibroin/poly (ɛ-caprolactone) scaffolds with formic acid as solvent for effective applications. PMID:27422715

  6. Microwave spectra and structure of the cyclopropanecarboxylic acid-formic acid dimer.

    PubMed

    Pejlovas, Aaron M; Lin, Wei; Kukolich, Stephen G

    2015-09-28

    The rotational spectrum of the cyclopropanecarboxylic acid-formic acid doubly hydrogen bonded dimer has been measured in the 4-11 GHz region using a Flygare-Balle type pulsed-beam Fourier transform microwave spectrometer. Rotational transitions were measured for the parent, four unique singly substituted (13)C isotopologues, and a singly deuterated isotopologue. Splittings due to a possible concerted double proton tunneling motion were not observed. Rotational constants (A, B, and C) and centrifugal distortion constants (DJ and DJK) were determined from the measured transitions for the dimer. The values of the rotational (in MHz) and centrifugal distortion constants (in kHz) for the parent isotopologue are A = 4045.4193(16), B = 740.583 80(14), C = 658.567 60(23), DJ = 0.0499(16), and DJK = 0.108(14). A partial gas phase structure of the dimer was derived from the rotational constants of the measured isotopologues, previous structural work on each monomer units and results of the calculations.

  7. Effect of plant extracts and formic acid on the intestinal equilibrium of early-weaned pigs.

    PubMed

    Manzanilla, E G; Perez, J F; Martin, M; Kamel, C; Baucells, F; Gasa, J

    2004-11-01

    We evaluated the effects of a plant extracts mixture (XT) standardized in 5% (wt/wt) carvacrol, 3% cinnamaldehyde, and 2% capsicum oleoresin (oregano, cinnamon and Mexican pepper), alone or in combination with formic acid (FA), on the productive performance and the intestinal ecosystem of the early-weaned pig. Pigs weaned at 20 +/- 1 d of age (n = 216) were allocated in 24 pens and fed a standard medicated prestarter diet for 12 d. Twelve days after weaning, a stress management system based on social and dietary stress factors was applied to the animals, after which, each group was allocated to one of six dietary treatments, which followed a factorial arrangement, with three levels (as-fed basis) of the XT (0, 150, and 300 mg/kg) and two levels of FA (0 and 0.5%). On d 24 and 25 after the stress episode, eight pigs per treatment were killed to examine variables describing some aspects of the gastrointestinal ecology. Two days after the stress episode, an Escherichia coli K88 diarrhea episode occurred, and five casualties were registered. Four of the five deaths occurred in pens of pigs not fed the XT. The FA resulted in better G:F (P = 0.040) in coincidence with shorter villous height (P = 0.073) and lower rectal total microbial mass (P = 0.078). Both XT and FA addition increased stomach content (P = 0.006 and 0.003, respectively) and percentage of DM (P = 0.089 and 0.010, respectively), suggesting an increased gastric retention time; consequently, pH was also increased (P = 0.005 and 0.060, respectively). The XT decreased ileum total microbial mass (P = 0.025) and increased the lactobacilli:enterobacteria ratio (P = 0.002). The VFA profile in the cecum and colon was modified by XT inclusion, increasing the proportion of acetate (P = 0.018 and 0.025, respectively) and diminishing the proportion of butyrate (P = 0.096 and 0.040, respectively) and valerate (P = 0.001 and 0.039, respectively). Both XT and FA were shown to be effective in modifying the gastrointestinal

  8. Effect of plant extracts and formic acid on the intestinal equilibrium of early-weaned pigs.

    PubMed

    Manzanilla, E G; Perez, J F; Martin, M; Kamel, C; Baucells, F; Gasa, J

    2004-11-01

    We evaluated the effects of a plant extracts mixture (XT) standardized in 5% (wt/wt) carvacrol, 3% cinnamaldehyde, and 2% capsicum oleoresin (oregano, cinnamon and Mexican pepper), alone or in combination with formic acid (FA), on the productive performance and the intestinal ecosystem of the early-weaned pig. Pigs weaned at 20 +/- 1 d of age (n = 216) were allocated in 24 pens and fed a standard medicated prestarter diet for 12 d. Twelve days after weaning, a stress management system based on social and dietary stress factors was applied to the animals, after which, each group was allocated to one of six dietary treatments, which followed a factorial arrangement, with three levels (as-fed basis) of the XT (0, 150, and 300 mg/kg) and two levels of FA (0 and 0.5%). On d 24 and 25 after the stress episode, eight pigs per treatment were killed to examine variables describing some aspects of the gastrointestinal ecology. Two days after the stress episode, an Escherichia coli K88 diarrhea episode occurred, and five casualties were registered. Four of the five deaths occurred in pens of pigs not fed the XT. The FA resulted in better G:F (P = 0.040) in coincidence with shorter villous height (P = 0.073) and lower rectal total microbial mass (P = 0.078). Both XT and FA addition increased stomach content (P = 0.006 and 0.003, respectively) and percentage of DM (P = 0.089 and 0.010, respectively), suggesting an increased gastric retention time; consequently, pH was also increased (P = 0.005 and 0.060, respectively). The XT decreased ileum total microbial mass (P = 0.025) and increased the lactobacilli:enterobacteria ratio (P = 0.002). The VFA profile in the cecum and colon was modified by XT inclusion, increasing the proportion of acetate (P = 0.018 and 0.025, respectively) and diminishing the proportion of butyrate (P = 0.096 and 0.040, respectively) and valerate (P = 0.001 and 0.039, respectively). Both XT and FA were shown to be effective in modifying the gastrointestinal

  9. Acetal phosphatidic acids: novel platelet aggregating agents.

    PubMed

    Brammer, J P; Maguire, M H; Walaszek, E J; Wiley, R A

    1983-05-01

    1 Palmitaldehyde, olealdehyde and linolealdehyde acetal phosphatidic acids induced rapid shape change and dose-dependent biphasic aggregation of human platelets in platelet-rich plasma; aggregation was reversible at low doses and irreversible at high doses of the acetal phosphatidic acids. The palmitaldehyde congener elicited monophasic dose-dependent aggregation of sheep platelets in platelet-rich plasma.2 The threshold concentration for palmitaldehyde acetal phosphatidic acid (PGAP)-induced platelet aggregation was 2.5-5 muM for human platelets and 0.25-0.5 muM for sheep platelets. PGAP was 4-5 times as potent versus human platelets as the olealdehyde and linolealdehyde acetal phosphatidic acids, which were equipotent.3 PGAP-induced irreversible aggregation of [(14)C]-5-hydroxytryptamine ([(14)C]-5-HT)-labelled human platelets in platelet-rich plasma was accompanied by release of 44.0+/-2.4% (s.e.) of the platelet [(14)C]-5-HT; reversible aggregation was not associated with release. In contrast, PGAP-induced release of [(14)C]-5-HT-labelled sheep platelets was dose-dependent.4 The adenosine diphosphate (ADP) antagonist, 2-methylthio-AMP, and the cyclo-oxygenase inhibitor, aspirin, abolished PGAP-induced second phase aggregation and release in human platelets but did not affect the first, reversible, phase of aggregation. Both the first and second phases of PGAP-induced aggregation were abolished by chlorpromazine, by the phospholipase A(2) inhibitor, mepacrine, and by nmolar concentrations of prostaglandin E(1) (PGE(1)); these agents abolished the second, but not the first phase of ADP-induced aggregation.5 The related phospholipids, lecithin, lysolecithin and phosphatidic acid, at <100 muM, neither induced aggregation of human platelets in platelet-rich plasma, nor modified PGAP-induced aggregation; 1-palmityl lysophosphatidic acid elicited aggregation of human platelets at a threshold concentration of 100 muM.6 It is concluded that the acetal phosphatidic acids

  10. Microwave spectra and structure of the cyclopropanecarboxylic acid-formic acid dimer

    SciTech Connect

    Pejlovas, Aaron M.; Kukolich, Stephen G.; Lin, Wei

    2015-09-28

    The rotational spectrum of the cyclopropanecarboxylic acid–formic acid doubly hydrogen bonded dimer has been measured in the 4-11 GHz region using a Flygare-Balle type pulsed-beam Fourier transform microwave spectrometer. Rotational transitions were measured for the parent, four unique singly substituted {sup 13}C isotopologues, and a singly deuterated isotopologue. Splittings due to a possible concerted double proton tunneling motion were not observed. Rotational constants (A, B, and C) and centrifugal distortion constants (D{sub J} and D{sub JK}) were determined from the measured transitions for the dimer. The values of the rotational (in MHz) and centrifugal distortion constants (in kHz) for the parent isotopologue are A = 4045.4193(16), B = 740.583 80(14), C = 658.567 60(23), D{sub J} = 0.0499(16), and D{sub JK} = 0.108(14). A partial gas phase structure of the dimer was derived from the rotational constants of the measured isotopologues, previous structural work on each monomer units and results of the calculations.

  11. Single particle and pair dynamics in water-formic acid mixtures containing ionic and neutral solutes: nonideality in dynamical properties.

    PubMed

    Gupta, Rini; Chandra, Amalendu

    2008-05-14

    A series of molecular dynamics simulations of water-formic acid mixtures containing either an ionic solute or a neutral hydrophobic solute has been performed to study the extent of nonideality in the dynamics of these solutes for varying composition of the mixtures. The diffusion coefficients of the charged solutes, both cationic and anionic, are found to show nonideal behavior with variation of composition, and similar nonideality is also observed for the diffusion and orientational relaxation of solvent molecules in these mixtures. The diffusion coefficient of a neutral hydrophobic solute, however, decreases monotonically with increase in water concentration. We have also investigated some of the pair dynamical properties such as water-water and water-formic acid hydrogen bond relaxation and residence dynamics of water molecules in water and formic acid hydration shells. The lifetimes of water-water hydrogen bonds are found to be longer than those between formic acid carbonyl oxygen-water hydrogen bonds, whereas the lifetimes of formic acid hydroxyl hydrogen-water hydrogen bonds are longer than those of water-water hydrogen bonds. In general, the hydrogen bond lifetimes for both water-water and water-formic acid hydrogen bonds are found to decrease with increase in water concentration. Residence times of water molecules also show the same trend with increase in formic acid concentration. Interestingly, these pair dynamical properties show a monotonic dependence on composition without any maximum or minimum and behave almost ideally with respect to changes in the composition of the mixtures. The present calculations are performed with fixed-charge nonpolarizable models of the solvent and solute molecules without taking into account many-body polarization effects in an explicit manner. PMID:18532825

  12. Hydrogen evolution from formic acid in an ionic liquid solvent: a mechanistic study by ab initio molecular dynamics.

    PubMed

    Bhargava, B L; Yasaka, Yoshiro; Klein, Michael L

    2011-12-01

    The reversible decomposition of formic acid (HCOOH ⇌ CO(2) + H(2)) has been attracting attention for its potential utility in hydrogen storage and production. It is therefore of interest to explore the influence of solvents on the decomposition reaction. To this end, Born-Oppenheimer (BO) molecular dynamics (MD) calculations have been performed to explore the mechanism involved in hydrogen (H(2)) evolution from formic acid decomposition in an ionic liquid solvent. Specifically, for a solvent consisting of 1,3-dimethylimidazolium cations and formate anions, evolution of hydrogen (H(2)) and carbon dioxide (CO(2)) was observed within a few picoseconds when BO-MD trajectories were carried out at an elevated temperature of 3000 K. The observed dehydrogenation involved a reaction between a formic acid solute and a nearby solvent formate anion. The observed mechanism contrasts with the unimolecular mechanism proposed in the gas phase. Specifically, in the ionic liquid, the reaction is initiated from a C-H bond dissociation of a formate anion to produce a short-lived hydride anion, which subsequently captures the acidic proton of a nearby formic acid molecule. The present BO-MD computations suggest that the high reducing ability of formic acid in the ionic liquid is due in part to its acid-dissociated form: the formate anion, which is encouraged to dissociate into a hydride anion and CO(2) by the strong electrostatic field of the ionic liquid solvent. PMID:21774513

  13. Targeted Car-Parrinello molecular dynamics: Elucidating double proton transfer in formic acid dimer

    NASA Astrophysics Data System (ADS)

    Markwick, Phineus R. L.; Doltsinis, Nikos L.; Marx, Dominik

    2005-02-01

    The targeted molecular dynamics method, making possible the study of rare events, has been assessed in the framework of Car-Parrinello ab initio molecular dynamics. As a test case, we have studied the staggered-eclipsed rotation of ethane. The technique has subsequently been applied to investigate the nature of double proton transfer in formic acid dimer. The latter is found to follow a concerted transfer mechanism involving an essentially planar transition state. A "funnel-like region" of the potential energy surface is identified, where floppy intermolecular modes stiffen upon approaching the transition state.

  14. Formic acid dehydrogenation catalysed by ruthenium complexes bearing the tripodal ligands triphos and NP3.

    PubMed

    Mellone, Irene; Peruzzini, Maurizio; Rosi, Luca; Mellmann, Dörthe; Junge, Henrik; Beller, Matthias; Gonsalvi, Luca

    2013-02-21

    The selective formic acid dehydrogenation to a mixture of CO(2) and H(2) was achieved with moderate to good productivities in the presence of homogeneous Ru catalysts bearing the polydentate tripodal ligands 1,1,1-tris-(diphenylphosphinomethyl)ethane (triphos) and tris-[2-(diphenylphosphino)ethyl]amine (NP(3)), either made in situ from suitable Ru(III) precursors or as molecular complexes. Preliminary mechanistic studies highlighting subtle differences due to ligand effects in the corresponding systems under study are also presented. PMID:23212285

  15. Oxidation of formic acid on platinum surfaces decorated with cobalt(III) macrocyclic complexes

    NASA Astrophysics Data System (ADS)

    Stevanović, S.; Babić-Samardžija, K.; Sovilj, S. P.; Tripković, A.; Jovanović, V. M.

    2009-09-01

    Platinum electrode decorated with three different mixed-ligand cobalt(III) complexes of the general formula [Co(Rdtc)cyclam](ClO4)2 [cyclam = 1,4,8,11-tetraazacyclotetradecane, Rdtc- = morpholine-(Morphdtc), piperidine-(Pipdtc), and 4-methylpiperidine-(4-Mepipdtc) dithiocarbamates, respectively] was used to study oxidation of formic acid in acidic solution. The complexes were adsorbed on differently prepared Pt surfaces, at open circuit potential. The preliminary results show increased catalytic activity of Pt for formic acid oxidation with complex ion adsorbed on the polycrystalline surfaces. The increase in catalytic activity depends on the structure of the complex applied and follows the order of metal-coordinated bidentate ligand as Morphdtc > Pipdtc > 4-Mepipdtc. Based on IR and NMR data, the main characteristics of the Rdtc ligands do not vary dramatically, but high symmetry of the corresponding complexes decreases in the same order. Accordingly, the complexes are distinctively more mobile, causing chemical interactions to occur on the surface with appreciable speed and enhanced selectivity. The effect of the complexes on catalytic activity presumably depends on structural changes on Pt surfaces caused by their adsorption.

  16. Mesoporous Silica Supported Pd-MnOx Catalysts with Excellent Catalytic Activity in Room-Temperature Formic Acid Decomposition

    NASA Astrophysics Data System (ADS)

    Jin, Min-Ho; Oh, Duckkyu; Park, Ju-Hyoung; Lee, Chun-Boo; Lee, Sung-Wook; Park, Jong-Soo; Lee, Kwan-Young; Lee, Dong-Wook

    2016-09-01

    For the application of formic acid as a liquid organic hydrogen carrier, development of efficient catalysts for dehydrogenation of formic acid is a challenging topic, and most studies have so far focused on the composition of metals and supports, the size effect of metal nanoparticles, and surface chemistry of supports. Another influential factor is highly desired to overcome the current limitation of heterogeneous catalysis for formic acid decomposition. Here, we first investigated the effect of support pore structure on formic acid decomposition performance at room temperature by using mesoporous silica materials with different pore structures such as KIE-6, MCM-41, and SBA-15, and achieved the excellent catalytic activity (TOF: 593 h‑1) by only controlling the pore structure of mesoporous silica supports. In addition, we demonstrated that 3D interconnected pore structure of mesoporous silica supports is more favorable to the mass transfer than 2D cylindrical mesopore structure, and the better mass transfer provides higher catalytic activity in formic acid decomposition. If the pore morphology of catalytic supports such as 3D wormhole or 2D cylinder is identical, large pore size combined with high pore volume is a crucial factor to achieve high catalytic performance.

  17. Mesoporous Silica Supported Pd-MnOx Catalysts with Excellent Catalytic Activity in Room-Temperature Formic Acid Decomposition

    PubMed Central

    Jin, Min-Ho; Oh, Duckkyu; Park, Ju-Hyoung; Lee, Chun-Boo; Lee, Sung-Wook; Park, Jong-Soo; Lee, Kwan-Young; Lee, Dong-Wook

    2016-01-01

    For the application of formic acid as a liquid organic hydrogen carrier, development of efficient catalysts for dehydrogenation of formic acid is a challenging topic, and most studies have so far focused on the composition of metals and supports, the size effect of metal nanoparticles, and surface chemistry of supports. Another influential factor is highly desired to overcome the current limitation of heterogeneous catalysis for formic acid decomposition. Here, we first investigated the effect of support pore structure on formic acid decomposition performance at room temperature by using mesoporous silica materials with different pore structures such as KIE-6, MCM-41, and SBA-15, and achieved the excellent catalytic activity (TOF: 593 h−1) by only controlling the pore structure of mesoporous silica supports. In addition, we demonstrated that 3D interconnected pore structure of mesoporous silica supports is more favorable to the mass transfer than 2D cylindrical mesopore structure, and the better mass transfer provides higher catalytic activity in formic acid decomposition. If the pore morphology of catalytic supports such as 3D wormhole or 2D cylinder is identical, large pore size combined with high pore volume is a crucial factor to achieve high catalytic performance. PMID:27666280

  18. Novel silk fibroin films prepared by formic acid/hydroxyapatite dissolution method.

    PubMed

    Ming, Jinfa; Liu, Zhi; Bie, Shiyu; Zhang, Feng; Zuo, Baoqi

    2014-04-01

    Bombyx mori silk fibroin from the silkworm was firstly found to be soluble in formic acid/hydroxyapatite system. The rheological behavior of silk fibroin solution was significantly influenced by HAp contents in dissolved solution. At the same time, silk fibroin nanofibers were observed in dissolved solution with 103.6±20.4nm in diameter. Moreover, the structure behavior of SF films prepared by formic acid/hydroxyapatite dissolution method was examined. The secondary structure of silk fibroin films was attributed to silk II structure (β-sheet), indicating that the hydroxyapatite contents in dissolved solution were not significantly affected by the structure of silk fibroin. The X-ray diffraction results exhibited obviously hydroxyapatite crystalline nature existing in silk fibroin films; however, when the hydroxyapatite content was 5.0wt.% in dissolved solution, some hydroxyapatite crystals were converted to calcium hydrogen phosphate dehydrate in silk fibroin dissolution process. This result was also confirmed by Fourier transform infrared analysis and DSC measurement. In addition, silk fibroin films prepared by this dissolution method had higher breaking strength and extension at break. Based on these analyses, an understanding of novel SF dissolution method may provide an additional tool for designing and synthesizing advanced materials with more complex structures, which should be helpful in different fields, including biomaterial applications.

  19. The Intoxication Effects of Methanol and Formic Acid on Rat Retina Function

    PubMed Central

    Liu, Dong-Mei; Zhou, Shu; Peng, Shu-Ya

    2016-01-01

    Objective. To explore the potential effects of methanol and its metabolite, formic acid, on rat retina function. Methods. Sprague-Dawley rats were divided into 3- and 7-day groups and a control. Experimental groups were given methanol and the control group were provided saline by gavage. Retinal function of each group was assessed by electroretinogram. Concentrations of methanol and formic acid were detected by GC/HS and HPLC, respectively. Results. The a and b amplitudes of methanol treated groups decreased and latent periods delayed in scotopic and photopic ERG recordings. The summed amplitudes of oscillatory potentials (OPs) of groups B and C decreased and the elapsed time delayed. The amplitudes of OS1, OS3, OS4, and OS5 of group B and OS3, OS4, and OS5 of group C decreased compared with the control group. The IPI1 of group B and IPI1-4 of group C were broader compared with the control group and the IPI1-4 and ET of group B were broader than group C. Conclusions. Both of scotopic and photopic retinal functions were impaired by methanol poisoning, and impairment was more serious in the 7-day than in the 3-day group. OPs, especially later OPs and IPI2, were more sensitive to methanol intoxication than other eletroretinogram subcomponents. PMID:27688906

  20. Hydrogenation of CO2 to formic acid over a Cu-embedded graphene: A DFT study

    NASA Astrophysics Data System (ADS)

    Sirijaraensre, J.; Limtrakul, J.

    2016-02-01

    DFT calculations were used to investigate the properties of the atomic copper embedded in the surface of graphene (Cu/dG) and the catalytic reaction pathway for the CO2 hydrogenation to formic acid (FA). The Cu/dG was active for the adsorption of the hydrogen molecule (H2), and provided a reaction site for the heterolytic cleavage of H2, leading to the formation of Cu-H deposited on a singly hydrogenated vacancy graphene (Cu-H/H-dG). The protonation of CO2 takes place facilely over the generated metal-hydride species (Cu-H). Under the dilution of H2, the catalytic process would be hampered by the formation of copper-formate deposited on the H-dG due mainly to the very high energy demand for the transformation of the copper-formate to FA through the protonation from the H-dG. It was further found that the presence of H2 in the system plays a significant role in producing the FA on the Cu/dG catalyst. The copper-formate species can be converted into formic acid via the heterolytic cleavage of the second hydrogen molecule, yielding the FA and Cu-H species.

  1. Efficient production of hydrogen from formic acid using a covalent triazine framework supported molecular catalyst.

    PubMed

    Bavykina, A V; Goesten, M G; Kapteijn, F; Makkee, M; Gascon, J

    2015-03-01

    A heterogeneous molecular catalyst based on Ir(III) Cp* (Cp*=pentamethylcyclopentadienyl) attached to a covalent triazine framework (CTF) is reported. It catalyses the production of hydrogen from formic acid with initial turnover frequencies (TOFs) up to 27,000 h(-1) and turnover numbers (TONs) of more than one million in continuous operation. The CTF support, with a Brunauer-Emmett-Teller (BET) surface area of 1800 m(2)  g(-1), was constructed from an optimal 2:1 ratio of biphenyl and pyridine carbonitrile building blocks. Biphenyl building blocks induce mesoporosity and, therefore, facilitate diffusion of reactants and products whereas free pyridinic sites activate formic acid towards β-hydride elimination at the metal, rendering unprecedented rates in hydrogen production. The catalyst is air stable, produces CO-free hydrogen, and is fully recyclable. Hydrogen production rates of more than 60 mol L(-1)  h(-1) were obtained at high catalyst loadings of 16 wt % Ir, making it attractive towards process intensification.

  2. Formic acid microfluidic fuel cell based on well-defined Pd nanocubes

    NASA Astrophysics Data System (ADS)

    Moreno-Zuria, A.; Dector, A.; Arjona, N.; Guerra-Balcázar, M.; Ledesma-García, J.; Esquivel, J. P.; Sabaté, N.; Arrriaga, L. G.; Chávez-Ramírez, A. U.

    2013-12-01

    Microfluidic fuel cells (μFFC) are emerging as a promising solution for small-scale power demands. The T-shaped architecture of the μFFC promotes a laminar flow regimen between the catholyte and anolyte streams excluding the use of a membrane, this property allows a simplest design and the use of several micromachining techniques based on a lab-on-chip technologies. This work presents a combination of new materials and low cost fabrication processes to develop a light, small, flexible and environmental friendly device able to supply the energy demand of some portable devices. Well-defined and homogeneous Pd nanocubes which exhibited the (100) preferential crystallographic plane were supported on Vulcan carbon and used as anodic electrocatalyst in a novel and compact design of a SU-8 μFFC feeded with formic acid as fuel. The SU-8 photoresist properties and the organic microelectronic technology were important factors to reduce the dimensions of the μFFC structure. The results obtained from polarization and power density curves exhibited the highest power density (8.3 mW cm-2) reported in literature for direct formic acid μFFCs.

  3. Formic acid electrooxidation on Bi-modified polyoriented and preferential (111) Pt nanoparticles.

    PubMed

    López-Cudero, Ana; Vidal-Iglesias, Francisco J; Solla-Gullón, José; Herrero, Enrique; Aldaz, Antonio; Feliu, Juan M

    2009-01-14

    Formic acid electrooxidation was studied on Bi modified polyoriented and preferential (111) Pt nanoparticles. For both types of nanoparticles, Bi coverage was progressively increased and its effect on formic acid electrooxidation was evaluated using cyclic voltammetry and chronoamperometric measurements. In both experiments, significant and progressive enhancements on the electrooxidation current densities were obtained in comparison to the bare Pt nanoparticles. In voltammetry, at maximum Bi coverage, higher current densities at peak potential were obtained with the preferential (111) Pt nanoparticles (approximately 42 mA cm(-2)) as compared to the polyoriented Pt nanoparticles (approximately 32 mA cm(-2)) in agreement with previous single crystal studies. Nevertheless, this tendency was not observed in chronoamperometry at 0.4 V where currents obtained at maximum Bi coverage were similar. On the other hand, CO poison formation was also evaluated at open circuit potential. The resulting electrochemical activity has been rationalized using different parameters, such as surface structure, size domains, particle size and Bi coverage. PMID:19088999

  4. The Intoxication Effects of Methanol and Formic Acid on Rat Retina Function

    PubMed Central

    Liu, Dong-Mei; Zhou, Shu; Peng, Shu-Ya

    2016-01-01

    Objective. To explore the potential effects of methanol and its metabolite, formic acid, on rat retina function. Methods. Sprague-Dawley rats were divided into 3- and 7-day groups and a control. Experimental groups were given methanol and the control group were provided saline by gavage. Retinal function of each group was assessed by electroretinogram. Concentrations of methanol and formic acid were detected by GC/HS and HPLC, respectively. Results. The a and b amplitudes of methanol treated groups decreased and latent periods delayed in scotopic and photopic ERG recordings. The summed amplitudes of oscillatory potentials (OPs) of groups B and C decreased and the elapsed time delayed. The amplitudes of OS1, OS3, OS4, and OS5 of group B and OS3, OS4, and OS5 of group C decreased compared with the control group. The IPI1 of group B and IPI1-4 of group C were broader compared with the control group and the IPI1-4 and ET of group B were broader than group C. Conclusions. Both of scotopic and photopic retinal functions were impaired by methanol poisoning, and impairment was more serious in the 7-day than in the 3-day group. OPs, especially later OPs and IPI2, were more sensitive to methanol intoxication than other eletroretinogram subcomponents.

  5. 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.

  6. Interconversion of CO2 and formic acid by bio-inspired Ir complexes with pendent bases.

    PubMed

    Fujita, Etsuko; Muckerman, James T; Himeda, Yuichiro

    2013-01-01

    Recent investigations of the interconversion of CO2 and formic acid using Ru, Ir and Fe complexes are summarized in this review. During the past several years, both the reaction rates and catalyst stabilities have been significantly improved. Remarkably, the interconversion (i.e., reversibility) has also been achieved under mild conditions in environmentally benign water solvent by slightly changing the pH of the aqueous solution. Only a few catalysts seem to reflect a bio-inspired design such as the use of proton responsive ligands, ligands with pendent bases or acids for a second-coordination-sphere interaction, electroresponsive ligands, and/or ligands having a hydrogen bonding function with a solvent molecule or an added reagent. The most successful of these is an iridium dinuclear complex catalyst that at least has the first three of these characteristics associated with its bridging ligand. By utilizing an acid/base equilibrium for proton removal, the ligand becomes a strong electron donor, resulting in Ir(I) character with a vacant coordination site at each metal center in slightly basic solution. Complemented by DFT calculations, kinetic studies of the rates of formate production using a related family of Ir complexes with and without such functions on the ligand reveal that the rate-determining step for the CO2 hydrogenation is likely to be H2 addition through heterolytic cleavage involving a "proton relay" through the pendent base. The dehydrogenation of formic acid, owing to the proton responsive ligands changing character under slightly acidic pH conditions, is likely to occur by a mechanism with a different rate-determining step. This article is part of a Special Issue entitled: Metals in Bioenergetics and Biomimetics Systems. PMID:23174332

  7. Reactions of atomic hydrogen with formic acid and carbon monoxide in solid parahydrogen II: Deuterated reaction studies.

    PubMed

    Wonderly, William R; Anderson, David T

    2014-09-11

    It is difficult to determine whether the measured rate constant for reaction of atomic hydrogen with formic acid reported in Part 1 reflects the H atom quantum diffusion rate or the rate constant for the tunneling reaction step. In Part 2 of this series, we present kinetic studies of the postphotolysis H atom reactions with deuterated formic acid (DCOOD) to address this ambiguity. Short duration 193 nm in situ photolysis of DCOOD trapped in solid parahydrogen results in partial depletion of the DCOOD precursor and photoproduction of primarily CO, CO2, DOCO, HCO and mobile H atoms. At 1.9 K we observe post-irradiation growth in the concentrations of DOCO and HCO that can be explained by H atom tunneling reactions with DCOOD and CO, respectively. Conducting experiments with different deuterium isotopomers of formic acid (DCOOD, DCOOH, HCOOD and HCOOH) provides strong circumstantial evidence the reaction involves H atom abstraction from the alkyl group of formic acid. Further, the anomalous temperature dependence measured for the H + HCOOH reaction in Part 1 is also observed for the analogous reactions with deuterated formic acid. The rate constants extracted for H atom reactions with DCOOD and HCOOH are equivalent to within experimental uncertainty. This lack of a kinetic isotope effect in the measured rate constant is interpreted as evidence the reactions are diffusion limited; the measured rate constant reflects the H atom diffusion rate and not the tunneling reaction rate. Whether or not H atom reactions with chemical species in solid parahydrogen are diffusion limited is one of the outstanding questions in this field, and this work makes significant strides toward showing the reaction kinetics with formic acid are diffusion limited.

  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. Hydrolysis of organosolv wheat pulp in formic acid at high temperature for glucose production.

    PubMed

    Kupiainen, Laura; Ahola, Juha; Tanskanen, Juha

    2012-07-01

    Organosolv methods can be used to delignify lignocellulosic crop residues for pulp production or to pretreat them prior to enzymatic hydrolysis for bioethanol production. In this study, organic solvent was used as an acidic hydrolysis catalyst to produce glucose. Hydrolysis experiments were carried out in 5-20% formic acid at 180-220 °C. Wheat straw pulp delignified with a formicodeli™ method was used as a raw material. It was found that glucose yields from pulp are significantly higher than yields from microcrystalline cellulose, a model component for cellulose hydrolysis. The results indicate that cellulose hydrolysis of real fibers takes place more selectively to glucose than hydrolysis of microcrystalline cellulose particles does. The effect of the particle size on pulp hydrolysis was investigated, the crystallinity of hydrolyzed pulp was measured by XRD analysis, and the product distribution and its influence on the process was discussed. PMID:22609651

  10. Graphene decorated with PtAu alloy nanoparticles: facile synthesis and promising application for formic acid oxidation

    SciTech Connect

    Zhang, Sheng; Shao, Yuyan; Liao, Honggang; Liu, Jun; Aksay, Ilhan A.; Yin, Geping; Lin, Yuehe

    2011-03-01

    PtAu alloy nanoparticles (~ 3.2 nm in diameter) are synthesized in poly(diallyldimethylammonium chloride) (PDDA) aqueous solution and uniformly dispersed on graphene nanosheets. PtAu/graphene exhibits high electrocatalytic activity and stability for formic acid oxidation, which is attributed to the high dispersion of PtAu nanoparticles and the specific interaction between PtAu and graphene, indicating a promising catalyst for direct formic acid fuel cells. The facile method can be readily extended to the synthesis of other alloy nanoparticles.

  11. Hydrogen production from formic acid in pH-stat fed-batch operation for direct supply to fuel cell.

    PubMed

    Shin, Jong-Hwan; Yoon, Jong Hyun; Lee, Seung Hoon; Park, Tai Hyun

    2010-01-01

    Enterobacter asburiae SNU-1 harvested after cultivation was used as a whole cell biocatalyst, for the production of hydrogen. Formic acid was efficiently converted to hydrogen using the harvested cells with an initial hydrogen production rate and total hydrogen production of 491 ml/l/h and 6668 ml/l, respectively, when 1 g/l of whole cell enzyme was used. Moreover, new pH-stat fed-batch operation was conducted, and total hydrogen production was 1.4 times higher than that of batch operation. For practical application, bio-hydrogen produced from formic acid using harvested cells was directly applied to PEMFC for power generation.

  12. Separating acetic acid from furol (furfural) by electrodialysis method

    SciTech Connect

    Guan, S.F.; Li, C.S. Ye, S.T.; Shen, S.Y.; Wang, Y.T.; Yu, S.H.

    1981-01-01

    Furfural production by hydrolysis of fibrous plant materials is accompanied by formation of acetic acid in amounts depending on the material used. The amount of acetic formed in the hydrolysis of the fruit shell of oil-tea camellia (Camellia oleosa) (an oilseed-bearing tree) is equal to the amount of furfural. The acetic acid can be separated from the furfural and concentrated to 10% by electrodialysis. A smaller amount of furfural is separated with acetic acid.

  13. Adaptation and tolerance of bacteria against acetic acid.

    PubMed

    Trček, Janja; Mira, Nuno Pereira; Jarboe, Laura R

    2015-08-01

    Acetic acid is a weak organic acid exerting a toxic effect to most microorganisms at concentrations as low as 0.5 wt%. This toxic effect results mostly from acetic acid dissociation inside microbial cells, causing a decrease of intracellular pH and metabolic disturbance by the anion, among other deleterious effects. These microbial inhibition mechanisms enable acetic acid to be used as a preservative, although its usefulness is limited by the emergence of highly tolerant spoilage strains. Several biotechnological processes are also inhibited by the accumulation of acetic acid in the growth medium including production of bioethanol from lignocellulosics, wine making, and microbe-based production of acetic acid itself. To design better preservation strategies based on acetic acid and to improve the robustness of industrial biotechnological processes limited by this acid's toxicity, it is essential to deepen the understanding of the underlying toxicity mechanisms. In this sense, adaptive responses that improve tolerance to acetic acid have been well studied in Escherichia coli and Saccharomyces cerevisiae. Strains highly tolerant to acetic acid, either isolated from natural environments or specifically engineered for this effect, represent a unique reservoir of information that could increase our understanding of acetic acid tolerance and contribute to the design of additional tolerance mechanisms. In this article, the mechanisms underlying the acetic acid tolerance exhibited by several bacterial strains are reviewed, with emphasis on the knowledge gathered in acetic acid bacteria and E. coli. A comparison of how these bacterial adaptive responses to acetic acid stress fit to those described in the yeast Saccharomyces cerevisiae is also performed. A systematic comparison of the similarities and dissimilarities of the ways by which different microbial systems surpass the deleterious effects of acetic acid toxicity has not been performed so far, although such exchange

  14. Selective Hydrogen Generation from Formic Acid with Well-Defined Complexes of Ruthenium and Phosphorus-Nitrogen PN(3) -Pincer Ligand.

    PubMed

    Pan, Yupeng; Pan, Cheng-Ling; Zhang, Yufan; Li, Huaifeng; Min, Shixiong; Guo, Xunmun; Zheng, Bin; Chen, Hailong; Anders, Addison; Lai, Zhiping; Zheng, Junrong; Huang, Kuo-Wei

    2016-05-01

    An unsymmetrically protonated PN(3) -pincer complex in which ruthenium is coordinated by one nitrogen and two phosphorus atoms was employed for the selective generation of hydrogen from formic acid. Mechanistic studies suggest that the imine arm participates in the formic acid activation/deprotonation step. A long life time of 150 h with a turnover number over 1 million was achieved.

  15. Determination of water-soluble forms of oxalic and formic acids in soils by ion chromatography

    NASA Astrophysics Data System (ADS)

    Karicheva, E.; Guseva, N.; Kambalina, M.

    2016-03-01

    Carboxylic acids (CA) play an important role in the chemical composition origin of soils and migration of elements. The content of these acids and their salts is one of the important characteristics for agrochemical, ecological, ameliorative and hygienic assessment of soils. The aim of the article is to determine water-soluble forms of same carboxylic acids — (oxalic and formic acids) in soils by ion chromatography with gradient elution. For the separation and determination of water-soluble carboxylic acids we used reagent-free gradient elution ion-exchange chromatography ICS-2000 (Dionex, USA), the model solutions of oxalate and formate ions, and leachates from soils of the Kola Peninsula. The optimal gradient program was established for separation and detection of oxalate and formate ions in water solutions by ion chromatography. A stability indicating method was developed for the simultaneous determination of water-soluble organic acids in soils. The method has shown high detection limits such as 0.03 mg/L for oxalate ion and 0.02 mg/L for formate ion. High signal reproducibility was achieved in wide range of intensities which correspond to the following ion concentrations: from 0.04 mg/g to 10 mg/L (formate), from 0.1 mg/g to 25 mg/L (oxalate). The concentration of formate and oxalate ions in soil samples is from 0.04 to 0.9 mg/L and 0.45 to 17 mg/L respectively.

  16. Production of hybrid diesel fuel precursors from carbohydrates and petrochemicals using formic acid as a reactive solvent.

    PubMed

    Zhou, Xiaoyuan; Rauchfuss, Thomas B

    2013-02-01

    We report the one-pot alkylation of mesitylene with carbohydrate-derived 5-(hydroxymethyl)furfural (HMF) as a step toward diesel-range liquids. Using FeCl(3) as a catalyst, HMF is shown to alkylate toluene, xylene, and mesitylene in high yields in CH(2)Cl(2) and MeNO(2) solvents. Efforts to extend this reaction to greener or safer solvents showed that most ether-based solvents are unsatisfactory. Acid catalysts (e.g, p-TsOH) also proved to be ineffective. Using formic acid as a reactive solvent, mesitylene could be alkylated to give mesitylmethylfurfural (MMF) starting from fructose with yields up to approximately 70 %. The reaction of fructose with formic acid in the absence of mesitylene gave rise to low yields of the formate ester of HMF, which indicates the stabilizing effect of replacing the hydroxyl substituent with mesityl. The arene also serves as a second phase into which the product is extracted. Even by using formic acid, the mesitylation of less expensive precursors such as glucose and cellulose proceeded only in modest yields (ca. 20 %). These simpler substrates were found to undergo mesitylation by using hydrogen chloride/formic acid via the intermediate chloromethylfurfural. PMID:23281330

  17. Production of hybrid diesel fuel precursors from carbohydrates and petrochemicals using formic acid as a reactive solvent.

    PubMed

    Zhou, Xiaoyuan; Rauchfuss, Thomas B

    2013-02-01

    We report the one-pot alkylation of mesitylene with carbohydrate-derived 5-(hydroxymethyl)furfural (HMF) as a step toward diesel-range liquids. Using FeCl(3) as a catalyst, HMF is shown to alkylate toluene, xylene, and mesitylene in high yields in CH(2)Cl(2) and MeNO(2) solvents. Efforts to extend this reaction to greener or safer solvents showed that most ether-based solvents are unsatisfactory. Acid catalysts (e.g, p-TsOH) also proved to be ineffective. Using formic acid as a reactive solvent, mesitylene could be alkylated to give mesitylmethylfurfural (MMF) starting from fructose with yields up to approximately 70 %. The reaction of fructose with formic acid in the absence of mesitylene gave rise to low yields of the formate ester of HMF, which indicates the stabilizing effect of replacing the hydroxyl substituent with mesityl. The arene also serves as a second phase into which the product is extracted. Even by using formic acid, the mesitylation of less expensive precursors such as glucose and cellulose proceeded only in modest yields (ca. 20 %). These simpler substrates were found to undergo mesitylation by using hydrogen chloride/formic acid via the intermediate chloromethylfurfural.

  18. [Degradation of oxytetracycline with ozonation in acetic acid solvent].

    PubMed

    Li, Shi-Yin; Li, Xiao-Rong; Zhu, Yi-Ping; Zhu, Jiang-Peng; Wang, Guo-Xiang

    2012-12-01

    Use acetic acid as the media of ozone degradation of oxytetracycline (OTC), and effects of the initial dosing ratio of ozone/OTC, ozone flow, free radical scavenger, metal ions on the removal rate of OTC were investigated respectively. The results showed that acetic acid had a high ozone stability and solubility. OTC had a high removal rate and degradation rate in acetic acid solution. With the increase of OTC dosage, the removal rate of OTC decreased in acetic acid. Removal rate of OTC was increased distinctly when ozone flow increased properly. It was also observed that free radical scavenger had a significantly negative effect on OTC ozonation degradation in acetic acid. Furthermore the main reactions of OTC ozone oxidation were direct oxidation and indirect oxidation in acetic acid. When Fe3+ and Co2+ were existent in acetic acid, the degradation of OTC was inhibited significantly.

  19. Microwave Measurements of Maleimide and its Doubly Hydrogen Bonded Dimer with Formic ACID*

    NASA Astrophysics Data System (ADS)

    Pejlovas, Aaron M.; Kang, Lu; Kukolich, Stephen G.

    2016-06-01

    The microwave spectra were measured for the maleimide monomer and the maleimide-formic acid doubly hydrogen bonded dimer using a pulsed-beam Fourier transform microwave spectrometer. Many previously studied doubly hydrogen bonded dimers are formed between oxygen containing species, so it is important to also characterize and study other dimers containing nitrogen, as hydrogen bonding interactions with nitrogen are found in biological systems such as in DNA. The transition state of the dimer does not exhibit C_2_V symmetry, so the tunneling motion was not expected to be observed based on the symmetry, but it would be very important to also observe the tunneling process for an asymmetric dimer. Single-line b-type transitions were observed, so the tunneling motion was not observed in our microwave spectra. The hydrogen bond lengths were determined using a nonlinear least squares fitting program. *Supported by the NSF CHE-1057796

  20. High upward fluxes of formic acid from a boreal forest canopy

    NASA Astrophysics Data System (ADS)

    Schobesberger, Siegfried; Lopez-Hilfiker, Felipe D.; Taipale, Ditte; Millet, Dylan B.; D'Ambro, Emma L.; Rantala, Pekka; Mammarella, Ivan; Zhou, Putian; Wolfe, Glenn M.; Lee, Ben H.; Boy, Michael; Thornton, Joel A.

    2016-09-01

    Eddy covariance fluxes of formic acid, HCOOH, were measured over a boreal forest canopy in spring/summer 2014. The HCOOH fluxes were bidirectional but mostly upward during daytime, in contrast to studies elsewhere that reported mostly downward fluxes. Downward flux episodes were explained well by modeled dry deposition rates. The sum of net observed flux and modeled dry deposition yields an upward "gross flux" of HCOOH, which could not be quantitatively explained by literature estimates of direct vegetative/soil emissions nor by efficient chemical production from other volatile organic compounds, suggesting missing or greatly underestimated HCOOH sources in the boreal ecosystem. We implemented a vegetative HCOOH source into the GEOS-Chem chemical transport model to match our derived gross flux and evaluated the updated model against airborne and spaceborne observations. Model biases in the boundary layer were substantially reduced based on this revised treatment, but biases in the free troposphere remain unexplained.

  1. Cellulose nanocrystals prepared via formic acid hydrolysis followed by TEMPO-mediated oxidation.

    PubMed

    Li, Bin; Xu, Wenyang; Kronlund, Dennis; Määttänen, Anni; Liu, Jun; Smått, Jan-Henrik; Peltonen, Jouko; Willför, Stefan; Mu, Xindong; Xu, Chunlin

    2015-11-20

    Cellulose nanocrystals (CNCs) as a renewable and biodegradable nanomaterial have wide application value. In this work, CNCs were extracted from bleached chemical pulp using two stages of isolation (i.e. formic acid (FA) hydrolysis and 2,2,6,6-tetramethyl-piperidine-1-oxyl (TEMPO) mediated oxidation) under mild conditions. In the first stage, FA was used to remove hemicellulose, swell cellulose fibers, and release CNCs. The FA could be readily recovered and reused. In the second stage, the CNCs isolated by FA were further modified by TEMPO-mediated oxidation to increase the surface charge of CNCs. It was found that the modified CNCs with more ordered crystal structure and higher surface charge had better redispersibility and higher viscosity in aqueous phase. Therefore, the modified CNCs could be more effective when used as rheology modifier in the fields of water based coating, paint, food etc.

  2. Hydrogen generation during treatment of simulated high-level radioactive waste with formic acid

    SciTech Connect

    Ritter, J.A.; Zamecnik, J.R.; Hsu, C.W.

    1992-01-01

    The Integrated Defense Waste Processing Facility (DWPF) Melter System (IDMS), operated by the Savannah River Laboratory, is a one-fifth scale pilot facility used in support of the start-up and operation of the Department of Energy's DWPF. Five IDMS runs determined the effect of the presence of noble metals in HLW sludge on the H{sub 2} generation rate during the preparation of melter feed with formic acid. Overall, the results clearly showed that H{sub 2} generation in the DWPF SRAT could, at times, exceed the lower flammable limit of H{sub 2} in air (4 vol%), depending on such factors as offgas generation and air inleakage of the DWPF vessels. Therefore, the installation of a forced air purge system and H{sub 2} monitors were recommended to the DWPF to control the generation of H{sub 2} during melter feed preparation by fuel dilution.

  3. Hydrogen generation during treatment of simulated high-level radioactive waste with formic acid

    SciTech Connect

    Ritter, J.A.; Zamecnik, J.R.; Hsu, C.W.

    1992-05-01

    The Integrated Defense Waste Processing Facility (DWPF) Melter System (IDMS), operated by the Savannah River Laboratory, is a one-fifth scale pilot facility used in support of the start-up and operation of the Department of Energy`s DWPF. Five IDMS runs determined the effect of the presence of noble metals in HLW sludge on the H{sub 2} generation rate during the preparation of melter feed with formic acid. Overall, the results clearly showed that H{sub 2} generation in the DWPF SRAT could, at times, exceed the lower flammable limit of H{sub 2} in air (4 vol%), depending on such factors as offgas generation and air inleakage of the DWPF vessels. Therefore, the installation of a forced air purge system and H{sub 2} monitors were recommended to the DWPF to control the generation of H{sub 2} during melter feed preparation by fuel dilution.

  4. Degradation of trichloroethylene by hydrodechlorination using formic acid as hydrogen source over supported Pd catalysts.

    PubMed

    Yu, Xin; Wu, Ting; Yang, Xue-Jing; Xu, Jing; Auzam, Jordan; Semiat, Raphael; Han, Yi-Fan

    2016-03-15

    An advanced method for the degradation of trichloroethylene (TCE) over Pd/MCM-41 catalysts through a hydrogen-transfer was investigated. Formic acid (FA) was used instead of gaseous H2 as the hydrogen resource. As a model H-carrier compound, FA has proven to yield less by-products and second-hand pollution during the reaction. Several factors have been studied, including: the property of catalyst supports, Pd loading and size, temperature, initial concentrations of FA and TCE (potential impact on the reaction rates of TCE degradation), and FA decomposition. The intrinsic kinetics for TCE degradation were measured, while the apparent activation energies and the reaction orders with respect to TCE and FA were calculated through power law models. On the basis of kinetics, we assumed a plausible reaction pathway for TCE degradation in which the catalytic degradation of TCE is most likely the rate-determining step for this reaction. PMID:26685065

  5. Shape-dependent electrocatalysis: methanol and formic acid electrooxidation on preferentially oriented Pt nanoparticles.

    PubMed

    Solla-Gullón, J; Vidal-Iglesias, F J; López-Cudero, A; Garnier, E; Feliu, J M; Aldaz, A

    2008-07-01

    Reactivity towards methanol and formic acid electrooxidation on Pt nanoparticles with well characterised surfaces were studied and compared with the behaviour of single crystal electrodes with basal orientations. Polyoriented and preferential (100), (111) and (100)-(111) Pt nanoparticles were synthesised, cleaned preserving its surface structure, characterised and employed to evaluate the influence of the surface structure/shape of the Pt nanoparticles on these two relevant electrochemical reactions. The results pointed out that, in agreement with fundamental studies with Pt single crystal electrodes, the surface structure of the electrodes plays an important role on the reactivity of both oxidation processes, and thus the electrocatalytic properties strongly depend on the surface structure/shape of the nanoparticles, in particular on the presence of sites with (111) symmetry. These findings open the possibility of designing new and better electrocatalytic materials using decorated shape-controlled Pt nanoparticles as previously described with Pt single crystal electrodes. PMID:18563230

  6. Energetics of methanol and formic acid oxidation on Pt(111): Mechanistic insights from adsorption calorimetry

    NASA Astrophysics Data System (ADS)

    Silbaugh, Trent L.; Karp, Eric M.; Campbell, Charles T.

    2016-08-01

    The catalytic and electrocatalytic oxidation and reforming of methanol and formic acid have received intense interest due to potential use in direct fuel cells and as prototype models for understanding electrocatalysis. Consequently, the reaction energy diagram (energies of all the adsorbed intermediates and activation energies of all the elementary steps) have been estimated for these reactions on Pt(111) by density functional theory (DFT) in several studies. However, no experimental measurement of these energy diagrams have been reported, nor is there a consensus on the mechanisms. Here, we use energies of key intermediates on Pt(111) from single crystal adsorption calorimetry (SCAC) and temperature programmed desorption (TPD) to build a combined energy diagram for these reactions. It suggests a new pathway involving monodentate formate as a key intermediate, with bidentate formate only being a spectator species that slows the rate. This helps reconcile conflicting proposed mechanisms.

  7. Infrared and density functional theory studies of formic acid hydrate clusters in noble gas matrices

    NASA Astrophysics Data System (ADS)

    Ito, Fumiyuki

    2016-08-01

    Infrared absorption spectra of formic acid hydrate clusters (HCOOH)m(H2O)n have been measured in noble gas matrices (Ar and Kr). The concentration dependence of the spectra and the comparison with a previous experimental study on HCOOH(H2O) and HCOOH(H2O)2 [Geoge et al., Spectrochim. Acta, Part A 60 (2004) 3225] led to the identification of large clusters. Density functional theory calculations at the B3LYP-DCP/6-31+G(2d,2p) level were carried out to determine the anharmonic vibrational properties of the clusters, enabling a consistent assignment of the observed vibrational peaks to specific clusters.

  8. Microwave spectrum and structural parameters for the formamide-formic acid dimer.

    PubMed

    Daly, Adam M; Sargus, Bryan A; Kukolich, Stephen G

    2010-11-01

    The rotational spectra for six isotopologues of the complex formed between formamide and formic acid have been measured using a pulsed-beam Fourier transform microwave spectrometer and analyzed to obtain rotational constants and quadrupole coupling parameters. The rotational constants and quadrupole coupling strengths obtained for H  (12)COOH-H(2)  (14)NCOH are A = 5889.465(2), B = 2148.7409(7), 1575.1234(6), eQq(aa) = 1.014(5), eQq(bb) = 1.99(1), and eQq(cc) = -3.00(1) MHz. Using the 15 rotational constants obtained for the H  (13)COOH, HCOOD, DCOOH, and H(2)  (15)NCHO isotopologues, key structural parameters were obtained from a least-squares structure fit. Hydrogen bond distances of 1.78 Å for R(O3⋯H1) and 1.79 Å for R(H4⋯O1) were obtained. The "best fit" value for the angle(C-O-H) of formic acid is significantly larger than the monomer value of 106.9° with an optimum value of 121.7(3)°. The complex is nearly planar with inertial defect Δ = -0.158 amu  Å(2). The formamide proton is moved out of the molecular plane by 15(3)° for the best fit structure. Density functional theory using B3PW91, HCTH407, and TPSS as well as MP2 and CCSD calculations were performed using 6-311++G(d,p) and the results were compared to experimentally determined parameters.

  9. Highly Active Pt(3)Pb and Core-Shell Pt(3)Pb-Pt Electrocatalysts for Formic Acid Oxidation

    SciTech Connect

    Kang Y.; Stach E.; Qi L.; Li M.; Diaz R.E.; Su D.; Adzic R.R.; Li J.; Murray C.B.

    2012-03-27

    Formic acid is a promising chemical fuel for fuel cell applications. However, due to the dominance of the indirect reaction pathway and strong poisoning effects, the development of direct formic acid fuel cells has been impeded by the low activity of existing electrocatalysts at desirable operating voltage. We report the first synthesis of Pt{sub 3}Pb nanocrystals through solution phase synthesis and show they are highly efficient formic acid oxidation electrocatalysts. The activity can be further improved by manipulating the Pt{sub 3}Pb-Pt core-shell structure. Combined experimental and theoretical studies suggest that the high activity from Pt{sub 3}Pb and the Pt-Pb core-shell nanocrystals results from the elimination of CO poisoning and decreased barriers for the dehydrogenation steps. Therefore, the Pt{sub 3}Pb and Pt-Pb core-shell nanocrystals can improve the performance of direct formic acid fuel cells at desired operating voltage to enable their practical application.

  10. Metal-free boron-doped graphene for selective electroreduction of carbon dioxide to formic acid/formate.

    PubMed

    Sreekanth, Narayanaru; Nazrulla, Mohammed Azeezulla; Vineesh, Thazhe Veettil; Sailaja, Krishnamurty; Phani, Kanala Lakshminarasimha

    2015-11-18

    Herein we report the electrocatalytic activity of boron-doped graphene for the reduction of CO2. Electrolysis takes place at low overpotentials leading exclusively to formate as the product (vis-à-vis benchmark Bi catalyst). Computational studies reveal mechanistic details of CO2 adsorption and subsequent conversion to formic acid/formate.

  11. Low activation energy dehydrogenation of aqueous formic acid on platinum-ruthenium-bismuth oxide at near ambient temperature and pressure.

    PubMed

    Ting, Siu-Wa; Cheng, Shaoan; Tsang, Kwok-Ying; van der Laak, Nicole; Chan, Kwong-Yu

    2009-12-21

    Highly selective dehydrogenation of formic acid in water was observed at near ambient temperature on a metal/metal oxide catalyst composed of platinum ruthenium and bismuth with a low activation energy of 37.3 kJ mol(-1). PMID:20024219

  12. Excluding hyperconjugation from the Z conformational preference and investigating its origin: formic acid and beyond.

    PubMed

    Ferro-Costas, David; Mosquera, Ricardo A

    2015-10-28

    Carboxylic acids, esters, secondary amides, and related molecules share a thermodynamic preference for the Z arrangement of their X[double bond, length as m-dash]C-Y-R moiety. This conformational predisposition is known as the Z effect and its most common explanation invokes the hyperconjugation from a Y lone pair to the σCX* orbital. In this work, we present clear topological evidence that hyperconjugation is not responsible for the Z preference. Diverse tools defined within the quantum chemical topology framework (such as, for example, atomic and electron localization function populations or the interacting quantum atoms energy decomposition) were used to analyse the evolution of formic acid from the E conformer towards the Z conformation. The results highlight the important role of the π resonance in the barrier between conformers and they also indicate that the hyperconjugative interaction lacks a leading role. Concretely, in an X[double bond, length as m-dash]C-Y-R structure, the XR interaction seems to be the key to understanding the preference for the Z arrangement of the moiety. Interestingly, our proposed explanation can be extended to a wide range of molecules presenting the same conformational preference, such as proteins or peptide nucleic acids. PMID:26403150

  13. 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)

  14. Differential titration of bases in glacial acetic acid.

    PubMed

    Castellano, T; Medwick, T; Shinkai, J H; Bailey, L

    1981-01-01

    A study of bases in acetic acid and their differential titration was carried out. The overall basicity constants for 20 bases were measured in acetic acid, and the differential titration of five binary mixtures of variable delta pKb values in acetic acid was followed using a glass electrode-modified calomel electrode system. Agreement with literature values was good. A leveling diagram was constructed that indicated that bases stronger than aqueous pKb 10 are leveled to an acetous pKb 5.69, whereas weaker bases are not leveled but instead exhibit their own intrinsic basicity, with the acetous pKb to aqueous pKb values being linearly related (slope 1.18, correlation coefficient 0.962). A minimum acetous delta pKb of four units is required for the satisfactory differential titration of two bases in acetic acid.

  15. 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.

  16. Chemical relaxation of H bonds in formic acid vapor studied by resonant photoacoustic spectroscopy

    NASA Astrophysics Data System (ADS)

    Winkler, A.; Mehl, J. B.; Hess, P.

    1994-02-01

    The chemical relaxation of hydrogen bonds in dimeric formic acid (methanoic acid) was studied in the gas phase by means of precise measurement of the speed of sound and the sound absorption as functions of the pressure and the temperature by exciting standing acoustic waves. The first radial acoustic resonance of a cylindrical cavity was excited by a modulated CO2 laser beam. Resonance profiles were measured and recorded by a computer-controlled system. Due to the high information content of this method, a consistent set of thermodynamic and kinetic parameters can be obtained. The equilibrium constants of the dimer/monomer and the cis-/trans-monomer equilibrium, the dissociation rate constant of (HCOOH)2 and the mean relaxation time of the vibrational states of the monomer-dimer mixture were determined by fitting a detailed theoretical model of the resonator to the measured values for the resonance frequency and the resonance broadening for total pressures in the range from 0.3 to 50 mbar and temperatures from 290 to 325 K. We obtained 159±2 J/(mol K) for the entropy and 61.8±0.5 kJ/mol for the enthalpy of dissociation at 300 K. We inferred a value for the enthalpy of isomerization of 10±5 kJ/mol. For the first time the pressure dependence of the dissociation rate constant was determined. It was found that the unimolecular decay is in the second-order regime at these low pressures as expected. The mean collision efficiency for the dissociation process relative to the dimer was obtained for HCOOH, He, and Ar to be 0.5±0.2, 0.05±0.02, and 0.08±0.02, respectively, independent of the temperature. We measured an average (pτ) value of 10±2 ns bar for the relaxation of the vibrational degrees of freedom. The activation energy of the dissociation of dimeric formic acid was determined to be 33±1 kJ/mol.

  17. The Trimethylamine-Formic Acid Complex: Microwave Characterization of a Prototype for Potential Precursors to Atmospheric Aerosol.

    PubMed

    Mackenzie, Rebecca B; Dewberry, Christopher T; Leopold, Kenneth R

    2016-04-14

    The reactions of amines and carboxylic acids have recently received attention for their possible role in the formation of atmospheric aerosol. Here, we report a microwave study of the trimethylamine-formic acid hydrogen-bonded complex, a simple prototype in which to study amine-carboxylic acid interactions. Spectra of three isotopologues of the system have been observed using a tandem cavity and chirped-pulse Fourier transform microwave spectrometer. The complex has a plane of symmetry, with the acidic proton of the formic acid directed toward the lone pair of the nitrogen. The zero-point-averaged hydrogen bond length is 1.702 Å, and the O-H···N angle is 177°. (14)N nuclear quadrupole hyperfine structure has been used to assess the degree of proton transfer from the formic acid to the trimethylamine. Experimental results are supplemented with density functional theory calculations. M06-2X/6-311++G(3df,3pd) calculations indicate a binding energy of 16.8 kcal/mol with counterpoise correction (17.4 kcal/mol without counterpoise correction).

  18. Evaluation of Hanford high level waste vitrification chemistry for an NCAW simulant -- FY 1994: Potential exothermic reactions in the presence of formic acid, glycolic acid, and oxalic acid

    SciTech Connect

    Sills, J.A.

    1995-07-01

    A potential for an uncontrollable exothermic reaction between nitrate and organic salts during preparation of a high level waste melter feed has been identified. In order to examine this potential more closely, the thermal behavior of simulated neutralized current acid waste (NCAW) treated with various organic reductants was studied. Differential scanning calorimetry (DSC) measurements were collected on simulated waste samples and their supernates treated with organics. Organic reductants used were formic acid, glycolic acid, and oxalic acid. For comparison, samples of untreated simulant and untreated simulant with added noble metals were tested. When heated, untreated simulant samples both with and without noble metals showed no exothermic behavior. All of the treated waste simulant samples showed exothermic behavior. Onset temperatures of exothermic reactions were 120 C to 210 C. Many onset temperatures, particularly those for formic acid treated samples, are well below 181 C, the estimated maximum steam coil temperature (considered to be a worst case maximum temperature for chemical process tank contents). The enthalpies of the reactions were {minus}180 {times} 10{sup {minus}3} J/Kg supernate ({minus}181 J/g) for the oxalic acid treated simulant supernate to {minus}1,150 {times} 10{sup {minus}3} J/Kg supernate ({minus}1,153 J/g) for the formic acid treated simulant supernate.

  19. Catalytic Hydrotreatment of Humins in Mixtures of Formic Acid/2-Propanol with Supported Ruthenium Catalysts.

    PubMed

    Wang, Yuehu; Agarwal, Shilpa; Kloekhorst, Arjan; Heeres, Hero Jan

    2016-05-10

    The catalytic hydrotreatment of humins, which are the solid byproducts from the conversion of C6 sugars (glucose, fructose) into 5-hydroxymethylfurfural (HMF) and levulinic acid (LA), by using supported ruthenium catalysts has been investigated. Reactions were carried out in a batch setup at elevated temperatures (400 °C) by using a hydrogen donor (formic acid (FA) in isopropanol (IPA) or hydrogen gas), with humins obtained from d-glucose. Humin conversions of up to 69 % were achieved with Ru/C and FA, whereas the performance for Ru on alumina was slightly poorer (59 % humin conversion). Humin oils were characterized by using a range of analytical techniques (GC, GC-MS, GCxGC, gel permeation chromatography) and were shown to consist of monomers, mainly alkyl phenolics (>45 % based on compounds detectable by GC) and higher oligomers. A reaction network for the reaction is proposed based on structural proposals for humins and the main reaction products. PMID:26836970

  20. Retention of ionisable compounds on high-performance liquid chromatography XIX. pH variation in mobile phases containing formic acid, piperazine and tris as buffering systems and methanol as organic modifier.

    PubMed

    Subirats, Xavier; Bosch, Elisabeth; Rosés, Martí

    2009-07-10

    In previous works a model to estimate the pH of methanol-aqueous buffer mobile phases from the aqueous pH and concentration of the buffer and the fraction of organic modifier was developed. This model was successfully applied and validated for buffers prepared from ammonia, acetic, phosphoric and citric acids. In the present communication this model has been extended to formic acid, piperazine and tris(hydroxymethyl)aminomethane buffers. Prior to the modelling work, the pK(a) values of the studied buffers at several methanol-water compositions were determined.

  1. Simultaneous Determination of Methanol, Ethanol and Formic Acid in Serum and Urine by Headspace GC-FID.

    PubMed

    Bursová, Miroslava; Hložek, Tomáš; Čabala, Radomír

    2015-01-01

    A simple, cost-effective headspace gas chromatography (GC) method coupled with GC with flame ionization detection for simultaneous determination of methanol, ethanol and formic acid was developed and validated for clinical and toxicological purposes. Formic acid was derivatized with an excess of isopropanol under acidic conditions to its volatile isopropyl ester while methanol and ethanol remained unchanged. The entire sample preparation procedure is complete within 6 min. The design of the experiment (the face-centered central composite design) was used for finding the optimal conditions for derivatization, headspace sampling and chromatographic separation. The calibration dependences of the method were quadratic in the range from 50 to 5,000 mg/L, with adequate accuracy (89.0-114.4%) and precision (<12%) in the serum. The new method was successfully used for determination of selected analytes in serum samples of intoxicated patients from among those affected by massive methanol poisonings in the Czech Republic in 2012.

  2. Suppression of Growth Rate of Colony-Associated Fungi by High Fructose Corn Syrup Feeding Supplement, Formic Acid, and Oxalic Acid

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Select colony-associated fungi (bee isolates). Absidia sp., Ascosphaera apis, Aspergillus flavus, Fusarium sp., Penicillium glabrum, Mucor sp., showed a 40% reduction in radial growth rate with formic acid, a 28% reduction with oxalic acid, and a 15% reduction with fructose and high fructose corn sy...

  3. 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.

  4. Formic acid electrooxidation on thallium-decorated shape-controlled platinum nanoparticles: an improvement in electrocatalytic activity.

    PubMed

    Busó-Rogero, Carlos; Perales-Rondón, Juan V; Farias, Manuel J S; Vidal-Iglesias, Francisco J; Solla-Gullon, Jose; Herrero, Enrique; Feliu, Juan M

    2014-07-21

    Thallium modified shape-controlled Pt nanoparticles were prepared and their electrocatalytic activity towards formic acid electrooxidation was evaluated in 0.5 M sulfuric acid. The electrochemical and in situ FTIR spectroscopic results show a remarkable improvement in the electrocatalytic activity, especially in the low potential region (around 0.1-0.2 V vs. RHE). Cubic Pt nanoparticles modified with Tl were found to be more active than the octahedral Pt ones in the entire range of Tl coverages and potential windows. In situ FTIR spectra indicate that the promotional effect produced by Tl results in the inhibition of the poisoning step leading to COads, thus improving the onset potential for the complete formic acid oxidation to CO2. Chronoamperometric experiments were also performed at 0.2 V to evaluate the stability of the electrocatalysts at constant potential. Finally, experiments with different concentrations of formic acid (0.05-1 M) were also carried out. In all cases, Tl-modified cubic Pt nanoparticles result to be the most active. All these facts reinforce the importance of controlling the surface structure of the electrocatalysts to optimize their electrocatalytic properties. PMID:24638124

  5. Optimization of a permeation-based microfluidic direct formic acid fuel cell (DFAFC).

    PubMed

    Erickson, Evan M; Mitrovski, Svetlana M; Gewirth, Andrew A; Nuzzo, Ralph G

    2011-04-01

    A design for a passive, air-breathing microfluidic fuel cell utilizing formic acid (FA) as a fuel is described and its performance characterized. The fuel cell integrates high surface area platinum (cathode) and palladium-platinum (anode) alloy electrodes within a PDMS microfluidic network that keeps them fully immersed in a liquid electrolyte. The polymer network that comprises the device also serves as a self-supporting membrane through which FA and oxygen are supplied to the alloy anode and cathode, respectively, by passive permeation from external sources. The cell is based on a planar form-factor and in its operation exploits FA concentration gradients that form across the PDMS membrane. These latter gradients allow the device to operate stably, producing a nearly constant limiting power density of ~0.2 mW/cm², without driven laminar flow of fluids or the incorporation of an in-channel separator between the anodic and the cathodic compartments. The power output of this elementary device in air is subject to electrolyte mass transport impacts, which can be reduced for a given design rule by decreasing the internal ohmic resistance of the cell. The results suggest that operational stability can be improved by decreasing the kinetic losses imposed on the cathode side of the cell due to FA crossover and modalities for doing so, such as by increasing the efficiency of fuel capture at the anode.

  6. Accurate determination of the binding energy of the formic acid dimer: the importance of geometry relaxation.

    PubMed

    Kalescky, Robert; Kraka, Elfi; Cremer, Dieter

    2014-02-28

    The formic acid dimer in its C2h-symmetrical cyclic form is stabilized by two equivalent H-bonds. The currently accepted interaction energy is 18.75 kcal/mol whereas the experimental binding energy D0 value is only 14.22 ±0.12 kcal/mol [F. Kollipost, R. W. Larsen, A. V. Domanskaya, M. Nörenberg, and M. A. Suhm, J. Chem. Phys. 136, 151101 (2012)]. Calculation of the binding energies De and D0 at the CCSD(T) (Coupled Cluster with Single and Double excitations and perturbative Triple excitations)/CBS (Complete Basis Set) level of theory, utilizing CCSD(T)/CBS geometries and the frequencies of the dimer and monomer, reveals that there is a 3.2 kcal/mol difference between interaction energy and binding energy De, which results from (i) not relaxing the geometry of the monomers upon dissociation of the dimer and (ii) approximating CCSD(T) correlation effects with MP2. The most accurate CCSD(T)/CBS values obtained in this work are De = 15.55 and D0 = 14.32 kcal/mol where the latter binding energy differs from the experimental value by 0.1 kcal/mol. The necessity of employing augmented VQZ and VPZ calculations and relaxing monomer geometries of H-bonded complexes upon dissociation to obtain reliable binding energies is emphasized.

  7. Accurate determination of the binding energy of the formic acid dimer: The importance of geometry relaxation

    NASA Astrophysics Data System (ADS)

    Kalescky, Robert; Kraka, Elfi; Cremer, Dieter

    2014-02-01

    The formic acid dimer in its C2h-symmetrical cyclic form is stabilized by two equivalent H-bonds. The currently accepted interaction energy is 18.75 kcal/mol whereas the experimental binding energy D0 value is only 14.22 ±0.12 kcal/mol [F. Kollipost, R. W. Larsen, A. V. Domanskaya, M. Nörenberg, and M. A. Suhm, J. Chem. Phys. 136, 151101 (2012)]. Calculation of the binding energies De and D0 at the CCSD(T) (Coupled Cluster with Single and Double excitations and perturbative Triple excitations)/CBS (Complete Basis Set) level of theory, utilizing CCSD(T)/CBS geometries and the frequencies of the dimer and monomer, reveals that there is a 3.2 kcal/mol difference between interaction energy and binding energy De, which results from (i) not relaxing the geometry of the monomers upon dissociation of the dimer and (ii) approximating CCSD(T) correlation effects with MP2. The most accurate CCSD(T)/CBS values obtained in this work are De = 15.55 and D0 = 14.32 kcal/mol where the latter binding energy differs from the experimental value by 0.1 kcal/mol. The necessity of employing augmented VQZ and VPZ calculations and relaxing monomer geometries of H-bonded complexes upon dissociation to obtain reliable binding energies is emphasized.

  8. Formic Acid Dehydrogenation on Au-Based Catalysts at Near-Ambient Temperatures

    SciTech Connect

    Ojeda, Manuel; Iglesia, Enrique

    2008-11-24

    Formic acid (HCOOH) is a convenient hydrogen carrier in fuel cells designed for portable use. Recent studies have shown that HCOOH decomposition is catalyzed with Ru-based complexes in the aqueous phase at near-ambient temperatures. HCOOH decomposition reactions are used frequently to probe the effects of alloying and cluster size and of geometric and electronic factors in catalysis. These studies have concluded that Pt is the most active metal for HCOOH decomposition, at least as large crystallites and extended surfaces. The identity and oxidation state of surface metal atoms influence the relative rates of dehydrogenation (HCOOH {yields} H{sub 2} + CO{sub 2}) and dehydration (HCOOH {yields} H{sub 2}O + CO) routes, a selectivity requirement for the synthesis of CO-free H{sub 2} streams for low-temperature fuel cells. Group Ib and Group VIII noble metals catalyze dehydrogenation selectively, while base metals and metal oxides catalyze both routes, either directly or indirectly via subsequent water-gas shift (WGS) reactions.

  9. Revisiting formic acid decomposition on metallic powder catalysts: Exploding the HCOOH decomposition volcano curve

    NASA Astrophysics Data System (ADS)

    Tang, Yadan; Roberts, Charles A.; Perkins, Ryan T.; Wachs, Israel E.

    2016-08-01

    This study revisits the classic volcano curve for HCOOH decomposition by metal catalysts by taking a modern catalysis approach. The metal catalysts (Au, Ag, Cu, Pt, Pd, Ni, Rh, Co and Fe) were prepared by H2 reduction of the corresponding metal oxides. The number of surface active sites (Ns) was determined by formic acid chemisorption. In situ IR indicated that both monodentate and bidentate/bridged surface HCOO* were present on the metals. Heats of adsorption (ΔHads) for surface HCOO* values on metals were taken from recently reported DFT calculations. Kinetics for surface HCOO* decomposition (krds) were determined with TPD spectroscopy. Steady-state specific activity (TOF = activity/Ns) for HCOOH decomposition over the metals was calculated from steady-state activity (μmol/g-s) and Ns (μmol/g). Steady-state TOFs for HCOOH decomposition weakly correlated with surface HCOO* decomposition kinetics (krds) and ΔHads of surface HCOO* intermediates. The plot of TOF vs. ΔHads for HCOOH decomposition on metal catalysts does not reproduce the classic volcano curve, but shows that TOF depends on both ΔHads and decomposition kinetics (krds) of surface HCOO* intermediates. This is the first time that the classic catalysis study of HCOOH decomposition on metallic powder catalysts has been repeated since its original publication.

  10. Formic Acid Decomposition on Au catalysts: DFT, Microkinetic Modeling, and Reaction Kinetics Experiments

    SciTech Connect

    Singh, Suyash; Li, Sha; Carrasquillo-Flores, Ronald; Alba-Rubio, Ana C.; Dumesic, James A.; Mavrikakis, Manos

    2014-04-01

    A combined theoretical and experimental approach is presented that uses a comprehensive mean-field microkinetic model, reaction kinetics experiments, and scanning transmission electron microscopy imaging to unravel the reaction mechanism and provide insights into the nature of active sites for formic acid (HCOOH) decomposition on Au/SiC catalysts. All input parameters for the microkinetic model are derived from periodic, self-consistent, generalized gradient approximation (GGA-PW91) density functional theory calculations on the Au(111), Au(100), and Au(211) surfaces and are subsequently adjusted to describe the experimental HCOOH decomposition rate and selectivity data. It is shown that the HCOOH decomposition follows the formate (HCOO) mediated path, with 100% selectivity toward the dehydrogenation products (CO21H2) under all reaction conditions. An analysis of the kinetic parameters suggests that an Au surface in which the coordination number of surface Au atoms is 4 may provide a better model for the active site of HCOOH decomposition on these specific supported Au catalysts.

  11. Selective hydrogen production from formic acid decomposition on Pd-Au bimetallic surfaces.

    PubMed

    Yu, Wen-Yueh; Mullen, Gregory M; Flaherty, David W; Mullins, C Buddie

    2014-08-01

    Pd-Au catalysts have shown exceptional performance for selective hydrogen production via HCOOH decomposition, a promising alternative to solve issues associated with hydrogen storage and distribution. In this study, we utilized temperature-programmed desorption (TPD) and reactive molecular beam scattering (RMBS) in an attempt to unravel the factors governing the catalytic properties of Pd-Au bimetallic surfaces for HCOOH decomposition. Our results show that Pd atoms at the Pd-Au surface are responsible for activating HCOOH molecules; however, the selectivity of the reaction is dictated by the identity of the surface metal atoms adjacent to the Pd atoms. Pd atoms that reside at Pd-Au interface sites tend to favor dehydrogenation of HCOOH, whereas Pd atoms in Pd(111)-like sites, which lack neighboring Au atoms, favor dehydration of HCOOH. These observations suggest that the reactivity and selectivity of HCOOH decomposition on Pd-Au catalysts can be tailored by controlling the arrangement of surface Pd and Au atoms. The findings in this study may prove informative for rational design of Pd-Au catalysts for associated reactions including selective HCOOH decomposition for hydrogen production and electro-oxidation of HCOOH in the direct formic acid fuel cell.

  12. Fundamental mechanistic studies in formic acid decomposition on transition metal surfaces

    NASA Astrophysics Data System (ADS)

    Mavrikakis, Manos

    2014-03-01

    Formic acid (HCOOH) is a simple molecule that is an abundant product of biomass processing and can serve as an internal source of hydrogen for oxygen removal and upgrading of biomass to chemicals and fuels. In addition, HCOOH can be used as a fuel for low temperature direct fuel cells. We present a systematic study of the HCOOH decomposition reaction mechanism starting from first-principles and including reactivity experiments and microkinetic modeling. In particular, periodic self-consistent Density Functional Theory (DFT) calculations are performed to determine the stability of reactive intermediates and activation energy barriers of elementary steps. Pre-exponential factors are determined from vibrational frequency calculations. Mean-field microkinetic models are developed and calculated reaction rates and reaction orders are then compared with experimentally measured ones. These comparisons provide useful insights on the nature of the active site, most-abundant surface intermediates as a function of reaction conditions and feed composition. Trends across metals on the fundamental atomic-scale level up to selectivity trends will be discussed. Finally, we identify from first-principles alloy surfaces, which may possess better catalytic properties for selective dehydrogenation of HCOOH than monometallic surfaces, thereby guiding synthesis towards promising novel catalytic materials. Work supported as part of the Institute of Atom-efficient Chemical Transformation (IACT), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.

  13. Tunneling splittings in formic acid dimer: An adiabatic approximation to the Herring formula

    NASA Astrophysics Data System (ADS)

    Jain, Amber; Sibert, Edwin L.

    2015-02-01

    Small symmetric molecules and low-dimensional model Hamiltonians are excellent systems for benchmarking theories to compute tunneling splittings. In this work, we investigate a three dimensional model Hamiltonian coupled to a harmonic bath that describes concerted proton transfer in the formic acid dimer. The three modes include the symmetric proton stretch, the symmetric dimer rock, and the dimer stretch. These modes provide a paradigm for the symmetric and anti-symmetric coupled tunneling pathways, these being recognized in the literature as two of the more important classes of coupling. The effects of selective vibrational excitation and coupling to a bath on the tunneling splittings are presented. The splittings for highly excited states are computed using a novel method that makes an adiabatic approximation to the Herring estimate. Results, which are in excellent agreement with the exact splittings, are compared with those obtained using the Makri-Miller approach. This latter method has been shown to provide quality results for tunneling splittings including highly excited vibrational states.

  14. Tunneling splittings in formic acid dimer: An adiabatic approximation to the Herring formula

    SciTech Connect

    Jain, Amber; Sibert, Edwin L.

    2015-02-28

    Small symmetric molecules and low-dimensional model Hamiltonians are excellent systems for benchmarking theories to compute tunneling splittings. In this work, we investigate a three dimensional model Hamiltonian coupled to a harmonic bath that describes concerted proton transfer in the formic acid dimer. The three modes include the symmetric proton stretch, the symmetric dimer rock, and the dimer stretch. These modes provide a paradigm for the symmetric and anti-symmetric coupled tunneling pathways, these being recognized in the literature as two of the more important classes of coupling. The effects of selective vibrational excitation and coupling to a bath on the tunneling splittings are presented. The splittings for highly excited states are computed using a novel method that makes an adiabatic approximation to the Herring estimate. Results, which are in excellent agreement with the exact splittings, are compared with those obtained using the Makri-Miller approach. This latter method has been shown to provide quality results for tunneling splittings including highly excited vibrational states.

  15. Shape-dependent electrocatalysis: formic acid electrooxidation on cubic Pd nanoparticles.

    PubMed

    Vidal-Iglesias, Francisco J; Arán-Ais, Rosa M; Solla-Gullón, José; Garnier, Emmanuel; Herrero, Enrique; Aldaz, Antonio; Feliu, Juan M

    2012-08-01

    The electrocatalytic properties of palladium nanocubes towards the electrochemical oxidation of formic acid were studied in H(2)SO(4) and HClO(4) solutions and compared with those of spherical Pd nanoparticles. The spherical and cubic Pd nanoparticles were characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The intrinsic electrocatalytic properties of both nanoparticles were shown to be strongly dependent on the amount of metal deposited on the gold substrate. Thus, to properly compare the activity of both systems (spheres and nanocubes), the amount of sample has to be optimized to avoid problems due to a lower diffusion flux of reactants in the internal parts of the catalyst layer resulting in a lower apparent activity. Under the optimized conditions, the activity of the spheres and nanocubes was very similar between 0.1 and 0.35 V. From this potential value, the activity of the Pd nanocubes was remarkably higher. This enhanced electrocatalytic activity was attributed to the prevalence of Pd(100) facets in agreement with previous studies with Pd single crystal electrodes. The effect of HSO(4)(-)/SO(4)(2-) desorption-adsorption was also evaluated. The activity found in HClO(4) was significantly higher than that obtained in H(2)SO(4) in the whole potential range. PMID:22722609

  16. Formic acid dehydrogenation with bioinspired iridium complexes: a kinetic isotope effect study and mechanistic insight.

    PubMed

    Wang, Wan-Hui; Xu, Shaoan; Manaka, Yuichi; Suna, Yuki; Kambayashi, Hide; Muckerman, James T; Fujita, Etsuko; Himeda, Yuichiro

    2014-07-01

    Highly efficient hydrogen generation from dehydrogenation of formic acid is achieved by using bioinspired iridium complexes that have hydroxyl groups at the ortho positions of the bipyridine or bipyrimidine ligand (i.e., OH in the second coordination sphere of the metal center). In particular, [Ir(Cp*)(TH4BPM)(H2 O)]SO4 (TH4BPM: 2,2',6,6'-tetrahydroxyl-4,4'-bipyrimidine; Cp*: pentamethylcyclopentadienyl) has a high turnover frequency of 39 500 h(-1) at 80 °C in a 1 M aqueous solution of HCO2 H/HCO2 Na and produces hydrogen and carbon dioxide without carbon monoxide contamination. The deuterium kinetic isotope effect study clearly indicates a different rate-determining step for complexes with hydroxyl groups at different positions of the ligands. The rate-limiting step is β-hydrogen elimination from the iridium-formate intermediate for complexes with hydroxyl groups at ortho positions, owing to a proton relay (i.e., pendent-base effect), which lowers the energy barrier of hydrogen generation. In contrast, the reaction of iridium hydride with a proton to liberate hydrogen is demonstrated to be the rate-determining step for complexes that do not have hydroxyl groups at the ortho positions.

  17. Air-breathing direct formic acid microfluidic fuel cell with an array of cylinder anodes

    NASA Astrophysics Data System (ADS)

    Zhu, Xun; Zhang, Biao; Ye, Ding-Ding; Li, Jun; Liao, Qiang

    2014-02-01

    An air-breathing direct formic acid membraneless microfluidic fuel cell using graphite cylinder arrays as the anode is proposed. The three dimensional anode volumetrically extends the reactive surface area and improves fuel utilization. The effects of spacer configuration, fuel and electrolyte concentration as well as reactant flow rate on the species transport and cell performance are investigated. The dynamic behavior of generated CO2 bubbles is visualized and its effect on current generation is discussed. The results show that the absence of two spacers adjacent to the cathode surface improves the cell performance by reducing the proton transfer resistance. The CO2 gas bubbles are constrained within the anode array and expelled by the fluid flow periodically. Proper reactant concentration and flow rate are crucial for cell operation. At optimum conditions, a maximum current density of 118.3 mA cm-3 and a peak power density of 21.5 mW cm-3 are obtained. In addition, benefit from the volumetrically stacked anodes and enhanced fuel transfer, the maximum single pass fuel utilization rate reaches up to 87.6% at the flow rate of 1 mL h-1.

  18. Enhancement of biomass conversion in catalytic fast pyrolysis by microwave-assisted formic acid pretreatment.

    PubMed

    Feng, Yu; Li, Guangyu; Li, Xiangyu; Zhu, Ning; Xiao, Bo; Li, Jian; Wang, Yujue

    2016-08-01

    This study investigated microwave-assisted formic acid (MW-FA) pretreatment as a possible way to improve aromatic production from catalytic fast pyrolysis (CFP) of lignocellulosic biomass. Results showed that short duration of MW-FA pretreatment (5-10min) could effectively disrupt the recalcitrant structure of beech wood and selectively remove its hemicellulose and lignin components. This increased the accessibility of cellulose component of biomass to subsequent thermal conversion in CFP. Consequently, the MW-FA pretreated beech wood produced 14.0-28.3% higher yields (26.4-29.8C%) for valuable aromatic products in CFP than the untreated control (23.2C%). In addition, the yields of undesired solid residue (char/coke) decreased from 33.1C% for the untreated control to 28.6-29.8C% for the MW-FA pretreated samples. These results demonstrate that MW-FA pretreatment can provide an effective way to improve the product distribution from CFP of lignocellulose. PMID:27176672

  19. Palladium-atom catalyzed formic acid decomposition and the switch of reaction mechanism with temperature.

    PubMed

    He, Nan; Li, Zhen Hua

    2016-04-21

    Formic acid decomposition (FAD) reaction has been an innovative way for hydrogen energy. Noble metal catalysts, especially palladium-containing nanoparticles, supported or unsupported, perform well in this reaction. Herein, we considered the simplest model, wherein one Pd atom is used as the FAD catalyst. With high-level theoretical calculations of CCSD(T)/CBS quality, we investigated all possible FAD pathways. The results show that FAD catalyzed by one Pd atom follows a different mechanism compared with that catalyzed by surfaces or larger clusters. At the initial stage of the reaction, FAD follows a dehydration route and is quickly poisoned by CO due to the formation of very stable PdCO. PdCO then becomes the actual catalyst for FAD at temperatures approximately below 1050 K. Beyond 1050 K, there is a switch of catalyst from PdCO to Pd atom. The results also show that dehydration is always favoured over dehydrogenation on either the Pd-atom or PdCO catalyst. On the Pd-atom catalyst, neither dehydrogenation nor dehydration follows the formate mechanism. In contrast, on the PdCO catalyst, dehydrogenation follows the formate mechanism, whereas dehydration does not. We also systematically investigated the performance of 24 density functional theory methods. We found that the performance of the double hybrid mPW2PLYP functional is the best, followed by the B3LYP, B3PW91, N12SX, M11, and B2PLYP functionals.

  20. Enhanced formic acid electro-oxidation reaction on ternary Pd-Ir-Cu/C catalyst

    NASA Astrophysics Data System (ADS)

    Chen, Jinwei; Zhang, Jie; Jiang, Yiwu; Yang, Liu; Zhong, Jing; Wang, Gang; Wang, Ruilin

    2015-12-01

    Aim to further reduce the cost of Pd-Ir for formic acid electro-oxidation (FAEO), the Cu was used to construct a ternary metallic alloy catalyst. The prepared catalysts are characterized using XRD, TGA, EDX, TEM, XPS, CO-stripping, cyclic voltammetry and chronoamperometry. It is found that the Pd18Ir1Cu6 nanoparticles with a mean size of 3.3 nm are highly dispersed on carbon support. Componential distributions on catalyst are consistent with initial contents. Electrochemical measurements show that the PdIrCu/C catalyst exhibits the highest activity for FAEO. The mass activity of Pd in Pd18Ir1Cu6/C at 0.16 V (vs. SCE) is about 1.47, 1.62 and 2.08 times as high as that of Pd18Cu6/C, Pd18Ir1/C and Pd/C, respectively. The activity enhancement of PdIrCu/C should be attributed to the weakened CO adsorption strength and the removal of adsorbed intermediates at lower potential with the addition of Cu and Ir.

  1. Structurally ordered Pt–Zn/C series nanoparticles as efficient anode catalysts for formic acid electrooxidation

    SciTech Connect

    Zhu, Jing; Zheng, Xin; Wang, Jie; Wu, Zexing; Han, Lili; Lin, Ruoqian; Xin, Huolin L.; Wang, Deli

    2015-09-15

    Controlling the size, composition, and structure of bimetallic nanoparticles is of particular interest in the field of electrocatalysts for fuel cells. In the present work, structurally ordered nanoparticles with intermetallic phases of Pt3Zn and PtZn have been successfully synthesized via an impregnation reduction method, followed by post heat-treatment. The Pt3Zn and PtZn ordered intermetallic nanoparticles are well dispersed on a carbon support with ultrasmall mean particle sizes of ~5 nm and ~3 nm in diameter, respectively, which are credited to the evaporation of the zinc element at high temperature. These catalysts are less susceptible to CO poisoning relative to Pt/C and exhibited enhanced catalytic activity and stability toward formic acid electrooxidation. The mass activities of the as-prepared catalysts were approximately 2 to 3 times that of commercial Pt at 0.5 V (vs. RHE). As a result, this facile synthetic strategy is scalable for mass production of catalytic materials.

  2. Structurally ordered Pt–Zn/C series nanoparticles as efficient anode catalysts for formic acid electrooxidation

    DOE PAGES

    Zhu, Jing; Zheng, Xin; Wang, Jie; Wu, Zexing; Han, Lili; Lin, Ruoqian; Xin, Huolin L.; Wang, Deli

    2015-09-15

    Controlling the size, composition, and structure of bimetallic nanoparticles is of particular interest in the field of electrocatalysts for fuel cells. In the present work, structurally ordered nanoparticles with intermetallic phases of Pt3Zn and PtZn have been successfully synthesized via an impregnation reduction method, followed by post heat-treatment. The Pt3Zn and PtZn ordered intermetallic nanoparticles are well dispersed on a carbon support with ultrasmall mean particle sizes of ~5 nm and ~3 nm in diameter, respectively, which are credited to the evaporation of the zinc element at high temperature. These catalysts are less susceptible to CO poisoning relative to Pt/Cmore » and exhibited enhanced catalytic activity and stability toward formic acid electrooxidation. The mass activities of the as-prepared catalysts were approximately 2 to 3 times that of commercial Pt at 0.5 V (vs. RHE). As a result, this facile synthetic strategy is scalable for mass production of catalytic materials.« less

  3. Palladium-atom catalyzed formic acid decomposition and the switch of reaction mechanism with temperature.

    PubMed

    He, Nan; Li, Zhen Hua

    2016-04-21

    Formic acid decomposition (FAD) reaction has been an innovative way for hydrogen energy. Noble metal catalysts, especially palladium-containing nanoparticles, supported or unsupported, perform well in this reaction. Herein, we considered the simplest model, wherein one Pd atom is used as the FAD catalyst. With high-level theoretical calculations of CCSD(T)/CBS quality, we investigated all possible FAD pathways. The results show that FAD catalyzed by one Pd atom follows a different mechanism compared with that catalyzed by surfaces or larger clusters. At the initial stage of the reaction, FAD follows a dehydration route and is quickly poisoned by CO due to the formation of very stable PdCO. PdCO then becomes the actual catalyst for FAD at temperatures approximately below 1050 K. Beyond 1050 K, there is a switch of catalyst from PdCO to Pd atom. The results also show that dehydration is always favoured over dehydrogenation on either the Pd-atom or PdCO catalyst. On the Pd-atom catalyst, neither dehydrogenation nor dehydration follows the formate mechanism. In contrast, on the PdCO catalyst, dehydrogenation follows the formate mechanism, whereas dehydration does not. We also systematically investigated the performance of 24 density functional theory methods. We found that the performance of the double hybrid mPW2PLYP functional is the best, followed by the B3LYP, B3PW91, N12SX, M11, and B2PLYP functionals. PMID:27005983

  4. Reducing Pt use in the catalysts for formic acid electrooxidation via nanoengineered surface structure

    NASA Astrophysics Data System (ADS)

    Liao, Mengyin; Wang, Yulu; Chen, Guoqin; Zhou, Hua; Li, Yunhua; Zhong, Chuan-Jian; Chen, Bing H.

    2014-07-01

    The design of active and durable catalysts for formic acid (FA) electrooxidation requires controlling the amount of three neighboring platinum atoms in the surface of Pt-based catalysts. Such requirement is studied by preparing Pt decorated Pd/C (donated as Pt-Pd/C) with various Pt:Pd molar ratios via galvanic displacement making the amount of three neighboring Pt atoms in the surface of Pt-Pd/C tunable. The decorated nanostructures are confirmed by XPS, HS-LEIS, cyclic voltammetry and chronoamperometric measurements, demonstrating that Pt-Pd/C (the optimal molar ratio, Pt:Pd = 1:250) exhibits superior activity and durability than Pd/C and commercial Pt/C (J-M, 20%) catalysts for FA electrooxidation. The mass activity of Pt-Pd/C (Pt:Pd = 1:250) (3.91 A mg-1) is about 98 and 6 times higher than that of commercial Pt/C (0.04 A mg-1) and Pd/C (0.63 A mg-1) at a given potential of 0.1 V vs SCE, respectively. The controlled synthesis of Pt-Pd/C lead to the formation of largely discontinuous Pd and Pt sites and inhibition of CO formation, exhibiting unprecedented electrocatalytic performance toward FA electrooxidation while the cost of the catalyst almost the same as Pd/C. These findings have profound implications to the design and nanoengineering of decorated surfaces of catalysts for FA electrooxidation.

  5. Viscometric study of chitosan solutions in acetic acid/sodium acetate and acetic acid/sodium chloride.

    PubMed

    Costa, Cristiane N; Teixeira, Viviane G; Delpech, Marcia C; Souza, Josefa Virginia S; Costa, Marcos A S

    2015-11-20

    A viscometric study was carried out at 25°C to assess the physical-chemical behavior in solution and the mean viscometric molar mass (M¯v) of chitosan solutions with different deacetylation degrees, in two solvent mixtures: medium 1-acetic acid 0.3mol/L and sodium acetate 0.2mol/L; and medium 2-acetic acid 0.1mol/L and sodium chloride 0.2mol/L. Different equations were employed, by graphical extrapolation, to calculate the intrinsic viscosities [η] and the viscometric constants, to reveal the solvent's quality: Huggins (H), Kraemer (K) and Schulz-Blaschke (SB). For single-point determination, the equations used were SB, Solomon-Ciuta (SC) and Deb-Chanterjee (DC), resulting in a faster form of analysis. The values of ̄M¯v were calculated by applying the equation of Mark-Houwink-Sakurada. The SB and SC equations were most suitable for single-point determination of [η] and ̄M¯v and the Schulz-Blachke constant (kSB), equal to 0.28, already utilized for various systems, can also be employed to analyze chitosan solutions under the conditions studied.

  6. Optimization of furfural production from D-xylose with formic acid as catalyst in a reactive extraction system.

    PubMed

    Yang, Wandian; Li, Pingli; Bo, Dechen; Chang, Heying; Wang, Xiaowei; Zhu, Tao

    2013-04-01

    Furfural is one of the most promising platform chemicals derived from biomass. In this study, response surface methodology (RSM) was utilized to determine four important parameters including reaction temperature (170-210°C), formic acid concentration (5-25 g/L), o-nitrotoluene volume percentage (20-80 vt.%), and residence time (40-200 min). The maximum furfural yield of 74% and selectivity of 86% were achieved at 190°C for 20 g/L formic acid concentration and 75 vt.% o-nitrotoluene by 75 min. The high boiling solvent, o-nitrotoluene, was recommended as extraction solvent in a reactive extraction system to obtain high furfural yield and reduce furfural-solvent separation costs. Although the addition of halides to the xylose solutions enhanced the furfural yield and selectivity, the concentration of halides was not an important factor on the furfural yield and selectivity.

  7. Development of Pd and Pd-Co catalysts supported on multi-walled carbon nanotubes for formic acid oxidation

    NASA Astrophysics Data System (ADS)

    Morales-Acosta, D.; Ledesma-Garcia, J.; Godinez, Luis A.; Rodríguez, H. G.; Álvarez-Contreras, L.; Arriaga, L. G.

    Pd-Co and Pd catalysts were prepared by the impregnation synthesis method at low temperature on multi-walled carbon nanotubes (MWCNTs). The nanotubes were synthesized by spray pyrolysis technique. Both catalysts were obtained with high homogeneous distribution and particle size around 4 nm. The morphology, composition and electrocatalytic properties were investigated by transmission electron microscopy, scanning electron microscopy-energy dispersive X-ray analysis, X-ray diffraction and electrochemical measurements, respectively. The electrocatalytic activity of Pd and PdCo/MWCNTs catalysts was investigated in terms of formic acid electrooxidation at low concentration in H 2SO 4 aqueous solution. The results obtained from voltamperometric studies showed that the current density achieved with the PdCo/MWCNTs catalyst is 3 times higher than that reached with the Pd/MWCNTs catalyst. The onset potential for formic acid electrooxidation on PdCo/MWCNTs electrocatalyst showed a negative shift ca. 50 mV compared with Pd/MWCNTs.

  8. Hydrogenation of biofuels with formic acid over a palladium-based ternary catalyst with two types of active sites.

    PubMed

    Wang, Liang; Zhang, Bingsen; Meng, Xiangju; Su, Dang Sheng; Xiao, Feng-Shou

    2014-06-01

    A composite catalyst including palladium nanoparticles on titania (TiO2) and on nitrogen-modified porous carbon (Pd/TiO2@N-C) is synthesized from palladium salts, tetrabutyl titanate, and chitosan. N2 sorption isotherms show that the catalyst has a high BET surface area (229 m(2)  g(-1)) and large porosity. XPS and TEM characterization of the catalyst shows that palladium species with different chemical states are well dispersed across the TiO2 and nitrogen-modified porous carbon, respectively. The Pd/TiO2@N-C catalyst is very active and shows excellent stability towards hydrogenation of vanillin to 2-methoxy-4-methylphenol using formic acid as hydrogen source. This activity can be attributed to a synergistic effect between the Pd/TiO2 (a catalyst for dehydrogenation of formic acid) and Pd/N-C (a catalyst for hydrogenation of vanillin) sites.

  9. Monodisperse gold-palladium alloy nanoparticles and their composition-controlled catalysis in formic acid dehydrogenation under mild conditions.

    PubMed

    Metin, Önder; Sun, Xiaolian; Sun, Shouheng

    2013-02-01

    Monodisperse 4 nm AuPd alloy nanoparticles with controlled composition were synthesized by co-reduction of hydrogen tetrachloroaurate(III) hydrate and palladium(II) acetylacetonate with a borane-morpholine complex in oleylamine. These NPs showed high activity (TOF = 230 h(-1)) and stability in catalyzing formic acid dehydrogenation and hydrogen production in water at 50 °C without any additives. PMID:23254519

  10. Biological Function of Acetic Acid-Improvement in Obesity and Glucose Tolerance by Acetic Acid in Type 2 Diabetic Rats.

    PubMed

    Yamashita, Hiromi

    2016-07-29

    Fatty acids derived from adipose tissue are oxidized by β-oxidation to form ketone bodies as final products under the starving condition. Previously, we found that free acetic acid was formed concomitantly with the production of ketone bodies in isolated rat liver perfusion, and mitochondrial acetyl CoA hydrolase was appeared to be involved with the acetic acid production. It was revealed that acetic acid was formed as a final product of enhanced β-oxidation of fatty acids and utilized as a fuel in extrahepatic tissues under the starving condition. Under the fed condition, β-oxidation is suppressed and acetic acid production is decreased. When acetic acid was taken daily by obesity-linked type 2 diabetic Otsuka Long-Evans Tokushima Fatty (OLETF) rats under the fed condition, it protected OLETF rats against obesity. Furthermore, acetic acid contributed to protect from the accumulation of lipid in the liver as well as abdominal fat in OLETF rats. Transcripts of lipogenic genes in the liver were decreased, while transcripts of myoglobin and Glut4 genes in abdominal muscles were increased in the acetic acid-administered OLETF rats. It is indicated that exogenously administered acetic acid would have effects on lipid metabolism in both the liver and the skeletal muscles, and have function that works against obesity and obesity-linked type 2 diabetes.

  11. 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.

  12. Photocatalytic Formic Acid Conversion on CdS Nanocrystals with Controllable Selectivity for H2 or CO**

    PubMed Central

    Kuehnel, Moritz F; Wakerley, David W; Orchard, Katherine L; Reisner, Erwin

    2015-01-01

    Formic acid is considered a promising energy carrier and hydrogen storage material for a carbon-neutral economy. We present an inexpensive system for the selective room-temperature photocatalytic conversion of formic acid into either hydrogen or carbon monoxide. Under visible-light irradiation (λ>420 nm, 1 sun), suspensions of ligand-capped cadmium sulfide nanocrystals in formic acid/sodium formate release up to 116±14 mmol H2 gcat−1 h−1 with >99 % selectivity when combined with a cobalt co-catalyst; the quantum yield at λ=460 nm was 21.2±2.7 %. In the absence of capping ligands, suspensions of the same photocatalyst in aqueous sodium formate generate up to 102±13 mmol CO gcat−1 h−1 with >95 % selectivity and 19.7±2.7 % quantum yield. H2 and CO production was sustained for more than one week with turnover numbers greater than 6×105 and 3×106, respectively. PMID:26201752

  13. Understanding the enhanced catalytic activity of Cu1@Pd3(111) in formic acid dissociation, a theoretical perspective

    NASA Astrophysics Data System (ADS)

    He, Feng; Li, Kai; Xie, Guangyou; Wang, Ying; Jiao, Menggai; Tang, Hao; Wu, Zhijian

    2016-06-01

    The bimetallic Cu1@Pd3(111) catalyst has been synthesized recently and exhibits better catalytic activity and durability compared with pure Pd(111) as anode catalyst in direct formic acid fuel cells (DFAFCs). In this work, we studied the reaction mechanism of formic acid dissociation on both Pd(111) and Cu1@Pd3(111) by using the density functional method. Our calculations showed that the surface adsorption of the poisoning species CO on Cu1@Pd3(111) is weakened mainly by the strain effect rather than the Cusbnd Pd ligand effect. The Cu1@Pd3(111) can effectively promote the catalytic activity for formic acid dissociation by decreasing the barrier of CO2 formation from the preferential trans-COOH intermediate and increasing the barrier of CO formation from the reduction of CO2. We found that the H atom accumulation, electron accumulation and low electrode potential could accelerate the catalyst deactivation due to the contamination of the poisoning species CO. Furthermore, under low anode potential, the Cu1@Pd3(111) has better durability than pure Pd(111), which can be attributed to the unfavorable CO formation and the favorable CO desorption.

  14. Repellent efficacy of formic acid and the abdominal secretion of carpenter ants (Hymenoptera: Formicidae) against Amblyomma ticks (Acari: Ixodidae).

    PubMed

    Falótico, Tiago; Labruna, Marcelo B; Verderane, Michele P; De Resende, Briseida D; Izar, Patrícia; Ottoni, Eduardo B

    2007-07-01

    Formic acid is a substance produced by some ants for defense, trail marking, and recruitment. Some animals are known to rub ants or other arthropods on parts of their plumage or fur to anoint themselves with released substances. A recent study with a semifree-ranging group of capuchin monkeys, Cebus apella L., in the Tietê Ecological Park, Sao Paulo, Brazil, an area of occurrence of the tick species Amblyomma cajennense (F.), revealed that "anting" with carpenter ants, Camponotus rufipes F. (Hymenoptera: Formicidae), occurs frequently, especially during the A. cajennense subadult season. Based on these observations, we tested the repellent effect of the formic acid and the ants themselves against A. cajennense and Amblyomma incisum Neumann nymphs, and Amblyomma parcum Aragdo adult ticks in the laboratory. The results revealed a significant repellent effect of formic acid and ant secretion, and a significant duration of the repellent effect. The results suggest that the anting behavior of capuchin monkeys, and other vertebrates, may be related with repellence of ticks and other ectoparasites.

  15. Ligand-induced substrate steering and reshaping of [Ag2(H)](+) scaffold for selective CO2 extrusion from formic acid.

    PubMed

    Zavras, Athanasios; Khairallah, George N; Krstić, Marjan; Girod, Marion; Daly, Steven; Antoine, Rodolphe; Maitre, Philippe; Mulder, Roger J; Alexander, Stefanie-Ann; Bonačić-Koutecký, Vlasta; Dugourd, Philippe; O'Hair, Richard A J

    2016-01-01

    Metalloenzymes preorganize the reaction environment to steer substrate(s) along the required reaction coordinate. Here, we show that phosphine ligands selectively facilitate protonation of binuclear silver hydride cations, [LAg2(H)](+) by optimizing the geometry of the active site. This is a key step in the selective, catalysed extrusion of carbon dioxide from formic acid, HO2CH, with important applications (for example, hydrogen storage). Gas-phase ion-molecule reactions, collision-induced dissociation (CID), infrared and ultraviolet action spectroscopy and computational chemistry link structure to reactivity and mechanism. [Ag2(H)](+) and [Ph3PAg2(H)](+) react with formic acid yielding Lewis adducts, while [(Ph3P)2Ag2(H)](+) is unreactive. Using bis(diphenylphosphino)methane (dppm) reshapes the geometry of the binuclear Ag2(H)(+) scaffold, triggering reactivity towards formic acid, to produce [dppmAg2(O2CH)](+) and H2. Decarboxylation of [dppmAg2(O2CH)](+) via CID regenerates [dppmAg2(H)](+). These gas-phase insights inspired variable temperature NMR studies that show CO2 and H2 production at 70 °C from solutions containing dppm, AgBF4, NaO2CH and HO2CH. PMID:27265868

  16. Repellent efficacy of formic acid and the abdominal secretion of carpenter ants (Hymenoptera: Formicidae) against Amblyomma ticks (Acari: Ixodidae).

    PubMed

    Falótico, Tiago; Labruna, Marcelo B; Verderane, Michele P; De Resende, Briseida D; Izar, Patrícia; Ottoni, Eduardo B

    2007-07-01

    Formic acid is a substance produced by some ants for defense, trail marking, and recruitment. Some animals are known to rub ants or other arthropods on parts of their plumage or fur to anoint themselves with released substances. A recent study with a semifree-ranging group of capuchin monkeys, Cebus apella L., in the Tietê Ecological Park, Sao Paulo, Brazil, an area of occurrence of the tick species Amblyomma cajennense (F.), revealed that "anting" with carpenter ants, Camponotus rufipes F. (Hymenoptera: Formicidae), occurs frequently, especially during the A. cajennense subadult season. Based on these observations, we tested the repellent effect of the formic acid and the ants themselves against A. cajennense and Amblyomma incisum Neumann nymphs, and Amblyomma parcum Aragdo adult ticks in the laboratory. The results revealed a significant repellent effect of formic acid and ant secretion, and a significant duration of the repellent effect. The results suggest that the anting behavior of capuchin monkeys, and other vertebrates, may be related with repellence of ticks and other ectoparasites. PMID:17695031

  17. Ligand-induced substrate steering and reshaping of [Ag2(H)]+ scaffold for selective CO2 extrusion from formic acid

    PubMed Central

    Zavras, Athanasios; Khairallah, George N.; Krstić, Marjan; Girod, Marion; Daly, Steven; Antoine, Rodolphe; Maitre, Philippe; Mulder, Roger J.; Alexander, Stefanie-Ann; Bonačić-Koutecký, Vlasta; Dugourd, Philippe; O'Hair, Richard A. J.

    2016-01-01

    Metalloenzymes preorganize the reaction environment to steer substrate(s) along the required reaction coordinate. Here, we show that phosphine ligands selectively facilitate protonation of binuclear silver hydride cations, [LAg2(H)]+ by optimizing the geometry of the active site. This is a key step in the selective, catalysed extrusion of carbon dioxide from formic acid, HO2CH, with important applications (for example, hydrogen storage). Gas-phase ion-molecule reactions, collision-induced dissociation (CID), infrared and ultraviolet action spectroscopy and computational chemistry link structure to reactivity and mechanism. [Ag2(H)]+ and [Ph3PAg2(H)]+ react with formic acid yielding Lewis adducts, while [(Ph3P)2Ag2(H)]+ is unreactive. Using bis(diphenylphosphino)methane (dppm) reshapes the geometry of the binuclear Ag2(H)+ scaffold, triggering reactivity towards formic acid, to produce [dppmAg2(O2CH)]+ and H2. Decarboxylation of [dppmAg2(O2CH)]+ via CID regenerates [dppmAg2(H)]+. These gas-phase insights inspired variable temperature NMR studies that show CO2 and H2 production at 70 °C from solutions containing dppm, AgBF4, NaO2CH and HO2CH. PMID:27265868

  18. Ambient formic acid in southern California air: A comparison of two methods, Fourier transform infrared spectroscopy and alkaline trap-liquid chromatography with UV detection

    SciTech Connect

    Grosjean, D. ); Tuazon, E.C. ); Fujita, E. )

    1990-01-01

    Formic acid is an ubiquitous component of urban smog. Sources of formic acid in urban air include direct emissions from vehicles and in situ reaction of ozone with olefins. Ambient levels of formic acid in southern California air were first measured some 15 years ago by Hanst et al. using long-path Fourier transform infrared spectroscopy (FTIR). All subsequent studies of formic acid in the Los Angeles area have involved the use of two methods, either FTIR or collection on alkaline traps followed by gas chromatography, ion chromatography, or liquid chromatography analysis with UV detection, ATLC-UV. The Carbon Species Methods Comparison Study (CSMCS), a multilaboratory air quality study carried out in August 1986 at a southern California smog receptor site, provided an opportunity for direct field comparison of the FTIR and alkaline trap methods. The results of the comparison are presented in this brief report.

  19. 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.

  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. PMID:26992903

  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. Quantification and Evidence for Mechanically Metered Release of Pygidial Secretions in Formic Acid-Producing Carabid Beetles

    PubMed Central

    Will, Kipling W.; Gill, Aman S.; Lee, Hyeunjoo; Attygalle, Athula B.

    2010-01-01

    This study is the first to measure the quantity of pygidial gland secretions released defensively by carabid beetles (Coleoptera: Carabidae) and to accurately measure the relative quantity of formic acid contained in their pygidial gland reservoirs and spray emissions. Individuals of three typical formic acid producing species were induced to repeatedly spray, ultimately exhausting their chemical compound reserves. Beetles were subjected to faux attacks using forceps and weighed before and after each ejection of chemicals. Platynus brunneomarginatus (Mannerheim) (Platynini), P. ovipennis (Mannerheim) (Platynini) and Calathus ruficollis Dejean (Sphodrini), sprayed average quantities with standard error of 0.313 ± 0.172 mg, 0.337 ± 0.230 mg, and 0.197 ± 0.117 mg per spray event, respectively. The quantity an individual beetle released when induced to spray tended to decrease with each subsequent spray event. The quantity emitted in a single spray was correlated to the quantity held in the reservoirs at the time of spraying for beetles whose reserves are greater than the average amount emitted in a spray event. For beetles with a quantity less than the average amount sprayed in reserve there was no significant correlation. For beetles comparable in terms of size, physiological condition and gland reservoir fullness, the shape of the gland reservoirs and musculature determined that a similar effort at each spray event would mechanically meter out the release so that a greater amount was emitted when more was available in the reservoir. The average percentage of formic acid was established for these species as 34.2%, 73.5% and 34.1% for for P. brunneomarginatus, P. ovipennis and C. ruficollis, respectively. The average quantities of formic acid released by individuals of these species was less than two-thirds the amount shown to be lethal to ants in previously published experiments. However, the total quantity from multiple spray events from a single individual could

  3. Quantification and evidence for mechanically metered release of pygidial secretions in formic acid-producing carabid beetles.

    PubMed

    Will, Kipling W; Gill, Aman S; Lee, Hyeunjoo; Attygalle, Athula B

    2010-01-01

    This study is the first to measure the quantity of pygidial gland secretions released defensively by carabid beetles (Coleoptera: Carabidae) and to accurately measure the relative quantity of formic acid contained in their pygidial gland reservoirs and spray emissions. Individuals of three typical formic acid producing species were induced to repeatedly spray, ultimately exhausting their chemical compound reserves. Beetles were subjected to faux attacks using forceps and weighed before and after each ejection of chemicals. Platynus brunneomarginatus (Mannerheim) (Platynini), P. ovipennis (Mannerheim) (Platynini) and Calathus ruficollis Dejean (Sphodrini), sprayed average quantities with standard error of 0.313 +/- 0.172 mg, 0.337 +/- 0.230 mg, and 0.197 +/- 0.117 mg per spray event, respectively. The quantity an individual beetle released when induced to spray tended to decrease with each subsequent spray event. The quantity emitted in a single spray was correlated to the quantity held in the reservoirs at the time of spraying for beetles whose reserves are greater than the average amount emitted in a spray event. For beetles with a quantity less than the average amount sprayed in reserve there was no significant correlation. For beetles comparable in terms of size, physiological condition and gland reservoir fullness, the shape of the gland reservoirs and musculature determined that a similar effort at each spray event would mechanically meter out the release so that a greater amount was emitted when more was available in the reservoir. The average percentage of formic acid was established for these species as 34.2%, 73.5% and 34.1% for for P. brunneomarginatus, P. ovipennis and C. ruficollis, respectively. The average quantities of formic acid released by individuals of these species was less than two-thirds the amount shown to be lethal to ants in previously published experiments. However, the total quantity from multiple spray events from a single individual

  4. Enrichment of amino acid-oxidizing, acetate-reducing bacteria.

    PubMed

    Ato, Makoto; Ishii, Masaharu; Igarashi, Yasuo

    2014-08-01

    In anaerobic condition, amino acids are oxidatively deaminated, and decarboxylated, resulting in the production of volatile fatty acids. In this process, excess electrons are produced and their consumption is necessary for the accomplishment of amino acid degradation. In this study, we anaerobically constructed leucine-degrading enrichment cultures from three different environmental samples (compost, excess sludge, and rice field soil) in order to investigate the diversity of electron-consuming reaction coupled to amino acid oxidation. Constructed enrichment cultures oxidized leucine to isovalerate and their activities were strongly dependent on acetate. Analysis of volatile fatty acids (VFAs) profiles and community structure analysis during batch culture of each enrichment indicated that Clostridium cluster I coupled leucine oxidation to acetate reduction in the enrichment from the compost and the rice field soil. In these cases, acetate was reduced to butyrate. On the other hand, Clostridium cluster XIVb coupled leucine oxidation to acetate reduction in the enrichment from the excess sludge. In this case, acetate was reduced to propionate. To our surprise, the enrichment from rice field soil oxidized leucine even in the absence of acetate and produced butyrate. The enrichment would couple leucine oxidation to reductive butyrate synthesis from CO2. The coupling reaction would be achieved based on trophic link between hydrogenotrophic acetogenic bacteria and acetate-reducing bacteria by sequential reduction of CO2 and acetate. Our study suggests anaerobic degradation of amino acids is achieved yet-to-be described reactions. PMID:24630616

  5. 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.

  6. Species differences in methanol and formic acid pharmacokinetics in mice, rabbits and primates

    SciTech Connect

    Sweeting, J. Nicole; Siu, Michelle; McCallum, Gordon P.; Miller, Lutfiya; Wells, Peter G.

    2010-08-15

    Methanol (MeOH) is metabolized primarily by alcohol dehydrogenase in humans, but by catalase in rodents, with species variations in the pharmacokinetics of its formic acid (FA) metabolite. The teratogenic potential of MeOH in humans is unknown, and its teratogenicity in rodents may not accurately reflect human developmental risk due to differential species metabolism, as for some other teratogens. To determine if human MeOH metabolism might be better reflected in rabbits than rodents, the plasma pharmacokinetics of MeOH and FA were compared in male CD-1 mice, New Zealand white rabbits and cynomolgus monkeys over time (24, 48 and 6 h, respectively) following a single intraperitoneal injection of 0.5 or 2 g/kg MeOH or its saline vehicle. Following the high dose, MeOH exhibited saturated elimination kinetics in all 3 species, with similar peak concentrations and a 2.5-fold higher clearance in mice than rabbits. FA accumulation within 6 h in primates was 5-fold and 43-fold higher than in rabbits and mice respectively, with accumulation being 10-fold higher in rabbits than mice. Over 48 h, FA accumulation was nearly 5-fold higher in rabbits than mice. Low-dose MeOH in mice and rabbits resulted in similarly saturated MeOH elimination in both species, but with approximately 2-fold higher clearance rates in mice. FA accumulation was 3.8-fold higher in rabbits than mice. Rabbits more closely than mice reflected primates for in vivo MeOH metabolism, and particularly FA accumulation, suggesting that developmental studies in rabbits may be useful for assessing potential human teratological risk.

  7. 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.

  8. Biosynthesis of the halogenated auxin, 4-chloroindole-3-acetic acid.

    PubMed

    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

    2012-07-01

    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

  9. One-pot transformation of cellobiose to formic acid and levulinic acid over ionic-liquid-based polyoxometalate hybrids.

    PubMed

    Li, Kaixin; Bai, Linlu; Amaniampong, Prince Nana; Jia, Xinli; Lee, Jong-Min; Yang, Yanhui

    2014-09-01

    Currently, levulinic acid (LA) and formic acid (FA) are considered as important carbohydrates for the production of value-added chemicals. Their direct production from biomass will open up a new opportunity for the transformation of biomass resource to valuable chemicals. In this study, one-pot transformation of cellobiose into LA and FA was demonstrated, using a series of multiple-functional ionic liquid-based polyoxometalate (IL-POM) hybrids as catalytic materials. These IL-POMs not only markedly promoted the production of valuable chemicals including LA, FA and monosaccharides with high selectivities, but also provided great convenience of the recovery and the reuse of the catalytic materials in an environmentally friendly manner. Cellobiose conversion of 100%, LA selectivity of 46.3%, and FA selectivity of 26.1% were obtained at 423 K and 3 MPa for 3 h in presence of oxygen. A detailed catalytic mechanism for the one-pot transformation of cellobiose was also presented. PMID:25110998

  10. The effects of temperature and dose of formic acid on treatment efficacy against Varroa destructor (Acari: Varroidae), a parasite of Apis mellifera (Hymenoptera: Apidae).

    PubMed

    Underwood, Robyn M; Currie, Robert W

    2003-01-01

    In order to decrease the variability of formic acid treatments against the honey bee parasite the varroa mite, Varroa destructor (Anderson and Trueman 2000), it is necessary to determine the dose-time combination that best controls mites without harming bees. The concentration x time (CT) product is a valuable tool for studying fumigants and how they might perform under various environmental conditions. This laboratory study is an assessment of the efficacy of formic acid against the varroa mite under a range of formic acid concentrations and temperatures. The objectives are 1) to determine the effect of temperature and dose of formic acid on worker honey bee and varroa mite survival, 2) to determine the CT50 products for both honey bees and varroa mites and 3) to determine the best temperature and dose to optimize selectivity of formic acid treatment for control of varroa mites. Worker honey bees and varroa mites were fumigated at 0, 0.01, 0.02, 0.04, 0.08, and 0.16 mg/L at 5, 15, 25, and 35 degrees C for 12 d. Mite and bee mortality were assessed at regular intervals. Both mite and bee survival were affected by formic acid dose. Doses of 0.08 and 0.16 mg/L were effective at killing mites at all temperatures tested above 5 degrees C. There was a significant interaction between temperature, dose, and species for the CT50 product. The difference between the CT50 product of bees and mites was significant at only a few temperature-dose combinations. CT product values showed that at most temperatures the greatest fumigation efficiency occurred at lower doses of formic acid. However, the best fumigation efficiency and selectivity combination for treatments occurred at a dose of 0.16 mg/L when the temperature was 35 degrees C. PMID:14635816

  11. Red- and blue-shifted hydrogen bonds in the cis-trans noncyclic formic acid dimer.

    PubMed

    Zhou, Pan-Pan; Qiu, Wen-Yuan

    2009-08-01

    The cis-trans noncyclic formic acid dimer was studied by means of MP2 method with 6-31G(d,p), 6-31+G(d,p) and 6-311+G(d,p) basis sets. It exhibits simultaneously red-shifted O-H...O and blue-shifted C-H...O hydrogen bonds. AIM and NBO analyses are performed at the MP2/6-31+G(d,p) level to explore their properties and origins. AIM analysis provides the evidence that the O-H bond becomes weaker and the C-H bond becomes stronger upon the hydrogen bond formations. Intermolecular and intramolecular hyperconjugations have important influence on the electron densities in the X-H (X = O, C) sigma bonding orbital and its sigma* antibonding orbital. The electron densities in the two orbitals are closely connected with the X-H (X = O, C) bond length, and they are used to quantitatively estimate the bond length variation. The larger amount of charge transfer in the red-shifted O-H...O hydrogen bond is due to its favorable H...O electron channel, whereas the H...O electron channel in the blue-shifted C-H...O hydrogen bond is weaker. Structural reorganization effects shorten the C-H bond by approximately 30% when compared to the C-H bond contraction upon the dimerization. Strikingly, it leads to a small elongation and a slight red shift of the O-H bond. Both rehybridization and repolarization result in the X-H (X = O, C) bond contraction, but their effects on the O-H bond do not hold a dominant position. The hydrogen-bonding processes go through the electrostatic attractions, van der Waals interactions, charge-transfer interactions, hydrogen-bonding interactions and electrostatic repulsions. Electrostatic attractions are of great importance on the origin of the red-shifted O-H...O hydrogen bond, especially the strong H(delta+)...O(delta-) attraction. For the blue-shifted C-H...O hydrogen bond, the considerable nucleus-nucleus repulsion between H and O atoms caused by the strong electrostatic attraction between C and O atoms is a possible reason for the C-H bond contraction and

  12. Elevated formic acid concentrations in putrefied post-mortem blood and urine samples.

    PubMed

    Viinamäki, Jenni; Rasanen, Ilpo; Vuori, Erkki; Ojanperä, Ilkka

    2011-05-20

    Formic acid (FA) concentration was measured in post-mortem blood and urine samples as methyl formate using a headspace in-tube extraction gas-chromatography-mass-spectrometry method. A total of 113 cases were analyzed, each including a blood and urine sample fortified with 1% sodium fluoride. The cases were divided into three groups: regular (n=59), putrefied (n=30), and methanol-positive (n=22) cases. There was no evidence of ante-mortem methanol consumption in the regular and putrefied cases. In regular cases, the mean (and median) FA concentrations were 0.04 g/l (0.04 g/l) and 0.06 g/l (0.04 g/l) in blood and urine, respectively. In putrefied cases, the mean (and median) FA concentrations were substantially higher, 0.24 g/l (0.22 g/l) and 0.25 g/l (0.15 g/l) in blood and urine, respectively. In three putrefied cases, FA concentration in blood exceeded 0.5 g/l, a level associated with fatal methanol poisoning. Ten putrefied cases were reanalyzed after 3-4 months storage, and no significant changes in FA concentrations were seen. These observations suggest that FA was formed by putrefaction during the post-mortem period, not during sample storage when sodium fluoride was added as a preservative. In methanol-positive cases, the mean (and median) FA concentrations were 0.80 g/l (0.88 g/l) and 3.4 g/l (3.3 g/l) in blood and urine, respectively, and the concentrations ranged from 0.19 to 1.0 g/l in blood and from 1.7 to 5.6 g/l in urine. The mean (and median) methanol concentrations in methanol-positive cases were 3.0 g/l (3.0 g/l) and 4.4 g/l (4.7 g/l) in blood and in urine, respectively. The highest methanol concentrations were 6.0 g/l and 8.7 g/l in blood and urine, respectively. No ethyl alcohol was found in the methanol-positive blood samples. Poor correlation was shown between blood and urine concentrations of FA. Poor correlations were also shown, in both blood and urine, between methanol and FA concentrations. PMID:21112705

  13. Au-supported Pt-Au mixed atomic monolayer electrocatalyst with ultrahigh specific activity for oxidation of formic acid in acidic solution.

    PubMed

    Huang, Zhao; Liu, Yan; Xie, Fangyun; Fu, Yingchun; He, Yong; Ma, Ming; Xie, Qingji; Yao, Shouzhuo

    2012-12-25

    Au-supported Pt-Au mixed atomic monolayer electrocatalyst was prepared by underpotential deposition of Cu on Au and then redox replacement with noble metal atoms, which shows an ultrahigh Pt-mass (or Pt-area) normalized specific electrocatalytic activity of 102 mA μg(Pt)(-1) (124 mA cm(Pt)(-2)) for oxidation of formic acid in acidic aqueous solution.

  14. 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

    2002-12-01

    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.

  15. Adsorption and thermal chemistry of formic acid on clean and oxygen-predosed Cu(110) single-crystal surfaces revisited

    NASA Astrophysics Data System (ADS)

    Yao, Yunxi; Zaera, Francisco

    2016-04-01

    The thermal chemistry of formic acid on clean and oxygen-predosed Cu(110) single-crystal surfaces was studied under ultrahigh-vacuum (UHV) conditions by temperature programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS). Key results reported in the past were confirmed, including the partial switchover from H2 to H2O desorption upon oxygen addition on the surface and the development of a second decomposition regime at 420 K, in addition to the one observed at 460 K on the clean substrate. In addition, new observations were added, including the previously missed desorption of H2 at 420 K and the existence of a normal kinetic isotope effect in both TPD peaks. Peak fitting of the XPS data afforded the identification of an asymmetric geometry for the formate intermediate, which was established to form by 200 K, and the presence of coadsorbed molecular formic acid up to the temperatures of decomposition, probably in a second layer and held by hydrogen bonding. Quantitative analysis of the TPD data indicated a one-to-one correspondence between the increase in oxygen coverage beyond θO = 0.5 ML and a decrease in formic acid uptake that mainly manifests itself in a decrease in the decomposition seen in the 460 K TPD peak. All these observations were interpreted in terms of a simple decomposition mechanism involving hydrogen abstraction from adsorbed formate species, possibly aided by coadsorbed oxygen, and a change in reaction activation energy as a function of the structure of the oxygen overlayer, which reverts from a O-c(6 × 2) structure at high oxygen coverages to the O-(2 × 1) order seen at θO = 0.5 ML.

  16. Genetic organization of Acetobacter for acetic acid fermentation.

    PubMed

    Beppu, T

    Plasmid vectors for the acetic acid-producing strains of Acetobacter and Gluconobacter were constructed from their cryptic plasmids and the efficient transformation conditions were established. The systems allowed to reveal the genetic background of the strains used in the acetic acid fermentation. Genes encoding indispensable components in the acetic acid fermentation, such as alcohol dehydrogenase, aldehyde dehydrogenase and terminal oxidase, were cloned and characterized. Spontaneous mutations at high frequencies in the acetic acid bacteria to cause the deficiency in ethanol oxidation were analyzed. A new insertion sequence element, IS1380, was identified as a major factor of the genetic instability, which causes insertional inactivation of the gene encoding cytochrome c, an essential component of the functional alcohol dehydrogenase complex. Several genes including the citrate synthase gene of A. aceti were identified to confer acetic acid resistance, and the histidinolphosphate aminotransferase gene was cloned as a multicopy suppressor of an ethanol sensitive mutant. Improvement of the acetic acid productivity of an A. aceti strain was achieved through amplification of the aldehyde dehydrogenase gene with a multicopy vector. In addition, spheroplast fusion of the Acetobacter strains was developed and applied to improve their properties.

  17. 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. PMID:27430512

  18. Regeneration of high-quality silk fibroin fiber by wet spinning from CaCl2-formic acid solvent.

    PubMed

    Zhang, Feng; Lu, Qiang; Yue, Xiaoxiao; Zuo, Baoqi; Qin, Mingde; Li, Fang; Kaplan, David L; Zhang, Xueguang

    2015-01-01

    Silks spun by silkworms and spiders feature outstanding mechanical properties despite being spun under benign conditions. The superior physical properties of silk are closely related to its complicated hierarchical structures constructed from nanoscale building blocks, such as nanocrystals and nanofibrils. Here, we report a novel silk dissolution behavior, which preserved nanofibrils in CaCl2-formic acid solution, that enables spinning of high-quality fibers with a hierarchical structure. This process is characterized by simplicity, high efficiency, low cost, environmental compatibility and large-scale industrialization potential, as well as having utility and potential for the recycling of silk waste and the production of silk-based functional materials.

  19. One-step and rapid synthesis of porous Pd nanoparticles with superior catalytic activity toward ethanol/formic acid electrooxidation

    NASA Astrophysics Data System (ADS)

    Hong, Wei; Fang, Youxing; Wang, Jin; Wang, Erkang

    2014-02-01

    Porous Pd nanoparticles are successfully prepared by a rapid, one-step, and efficient route with high yield in aqueous solution. The developed method is very simple, just by mixing sodium tetrachloropalladate, polyvinylpyrrolidone and hydroquinone and heated at 70 °C for 15 min. The structure and composition are analyzed by transmission electron microscope, selected-area electron diffraction, inductively coupled plasma optical emission spectrometer, X-ray diffraction, energy dispersive X-ray spectrum and X-ray photoelectron spectroscopy. Electrochemical catalytic measurement results prove that the as synthesized porous Pd nanoparticles exhibit superior catalytic activity towards ethanol and formic acid electrooxidation.

  20. Reexamination of CO formation during formic acid decomposition on the Pt(1 1 1) surface in the gas phase

    NASA Astrophysics Data System (ADS)

    Wang, Yingying; Zhang, Dongju; Liu, Peng; Liu, Chengbu

    2016-08-01

    Existing theoretical results for formic acid (HCOOH) decomposition on Pt(1 1 1) cannot rationalize the easy CO poisoning of the catalysts in the gas phase. The present work reexamined HCOOH decomposition on Pt(1 1 1) by considering the effect of the initial adsorption structure of the reactant on the reactivity. Our calculations present a new adsorption configuration of HCOOH on Pt(1 1 1), from which the formation of CO is found to be competing with the formation of CO2. The newly proposed mechanism improves our understanding for the mechanism of HCOOH decomposition catalyzed by Pt-based catalysts.

  1. Lack of formic acid production in rat hepatocytes and human renal proximal tubule cells exposed to chloral hydrate or trichloroacetic acid.

    PubMed

    Lock, Edward A; Reed, Celia J; McMillan, Joellyn M; Oatis, John E; Schnellmann, Rick G

    2007-02-12

    The industrial solvent trichloroethylene (TCE) and its major metabolites have been shown to cause formic aciduria in male rats. We have examined whether chloral hydrate (CH) and trichloroacetic acid (TCA), known metabolites of TCE, produce an increase in formic acid in vitro in cultures of rat hepatocytes or human renal proximal tubule cells (HRPTC). The metabolism and cytotoxicity of CH was also examined to establish that the cells were metabolically active and not compromised by toxicity. Rat hepatocytes and HRPTC were cultured in serum-free medium and then treated with 0.3-3mM CH for 3 days or 0.03-3mM CH for 10 days, respectively and formic acid production, metabolism to trichloroethanol (TCE-OH) and TCA and cytotoxicity determined. No increase in formic acid production in rat hepatocytes or HRPTC exposed to CH was observed over and above that due to chemical degradation, neither was formic acid production observed in rat hepatocytes exposed to TCA. HRPTC metabolized CH to TCE-OH and TCA with a 12-fold greater capacity to form TCE-OH versus TCA. Rat hepatocytes exhibited a 1.6-fold and three-fold greater capacity than HRPTC to form TCE-OH and TCA, respectively. CH and TCA were not cytotoxic to rat hepatocytes at concentrations up to 3mM/day for 3 days. With HRPTC, one sample showed no cytotoxicity to CH at concentrations up to 3mM/day for 10 days, while in another cytotoxicity was seen at 1mM/day for 3 days. In summary, increased formic acid production was not observed in rat hepatocytes or HRPTC exposed to TCE metabolites, suggesting that the in vivo response cannot be modelled in vitro. CH was toxic to HRPTC at millimolar concentrations/day over 10 days, while glutathione derived metabolites of TCE were toxic at micromolar concentrations/day over 10 days [Lock, E.A., Reed, C.J., 2006. Trichloroethylene: mechanisms of renal toxicity and renal cancer and relevance to risk assessment. Toxicol. Sci. 19, 313-331] supporting the view that glutathione derived

  2. Formation of Amino Acids from Reactor Irradiated Ammonium Acetate

    NASA Astrophysics Data System (ADS)

    Akaboshi, M.; Kawai, K.; Maki, H.; Kawamoto, K.; Honda, Y.

    1982-12-01

    Ammonium acetate in various conditions was irradiated in a reactor to examine the contributions of both the reactor radiations and recoiled14C nucleis to form the biologically interesting molecules. Present investigations demonstrated that several amino acids, glycine, alanine, β-alanine and GABA, and may-be aspartic acid, serine and valine by prolonged irradiation, were formed in the aqueous solutions of ammonium acetate.14C-radioactivities were also found distributed in these amino acids. However, no special relationship between14C-radioactivity and these amino acids formed was observed.

  3. Tetrazole acetic acid: tautomers, conformers, and isomerization.

    PubMed

    Araujo-Andrade, C; Reva, I; Fausto, R

    2014-02-14

    Monomers of (tetrazol-5-yl)-acetic acid (TAA) were obtained by sublimation of the crystalline compound and the resulting vapors were isolated in cryogenic nitrogen matrices at 13 K. The conformational and tautomeric composition of TAA in the matrix was characterized by infrared spectroscopy and vibrational calculations carried out at the B3LYP/6-311++G(d,p) level. TAA may adopt two tautomeric modifications, 1H- and 2H-, depending on the position of the annular hydrogen atom. Two-dimensional potential energy surfaces (PESs) of TAA were theoretically calculated at the MP2/6-311++G(d,p) level, for each tautomer. Four and six symmetry-unique minima were located on these PESs, for 1H- and 2H-TAA, respectively. The energetics of the detected minima was subsequently refined by calculations at the QCISD level. Two 1H- and three 2H-conformers fall within the 0-8 kJ mol(-1) energy range and should be appreciably populated at the sublimation temperature (∼330 K). Observation of only one conformer for each tautomer (1ccc and 2pcc) is explained in terms of calculated barriers to conformational rearrangements. All conformers with the cis O=COH moiety are separated by low barriers (less than 10 kJ mol(-1)) and collapse to the most stable 1ccc (1H-) and 2pcc (2H-) forms during deposition of the matrix. On the trans O=COH surfaces, the relative energies are very high (between 12 and 27 kJ mol(-1)). The trans forms are not thermally populated at the sublimation conditions and were not detected in matrices. One high-energy form in each tautomer, 1cct (1H-) and 2pct (2H-), was found to differ from the most stable form only by rotation of the OH group and separated from other forms by high barriers. This opened a perspective for their stabilization in a matrix. 1cct and 2pct were generated in the matrices selectively by means of narrow-band near-infrared (NIR) irradiations of the samples at 6920 and 6937 cm(-1), where the first OH stretching overtone vibrations of 1ccc and 2pcc occur

  4. Tetrazole acetic acid: Tautomers, conformers, and isomerization

    SciTech Connect

    Araujo-Andrade, C.; Reva, I. Fausto, R.

    2014-02-14

    Monomers of (tetrazol-5-yl)-acetic acid (TAA) were obtained by sublimation of the crystalline compound and the resulting vapors were isolated in cryogenic nitrogen matrices at 13 K. The conformational and tautomeric composition of TAA in the matrix was characterized by infrared spectroscopy and vibrational calculations carried out at the B3LYP/6-311++G(d,p) level. TAA may adopt two tautomeric modifications, 1H- and 2H-, depending on the position of the annular hydrogen atom. Two-dimensional potential energy surfaces (PESs) of TAA were theoretically calculated at the MP2/6-311++G(d,p) level, for each tautomer. Four and six symmetry-unique minima were located on these PESs, for 1H- and 2H-TAA, respectively. The energetics of the detected minima was subsequently refined by calculations at the QCISD level. Two 1H- and three 2H-conformers fall within the 0–8 kJ mol{sup −1} energy range and should be appreciably populated at the sublimation temperature (∼330 K). Observation of only one conformer for each tautomer (1ccc and 2pcc) is explained in terms of calculated barriers to conformational rearrangements. All conformers with the cis O=COH moiety are separated by low barriers (less than 10 kJ mol{sup −1}) and collapse to the most stable 1ccc (1H-) and 2pcc (2H-) forms during deposition of the matrix. On the trans O=COH surfaces, the relative energies are very high (between 12 and 27 kJ mol{sup −1}). The trans forms are not thermally populated at the sublimation conditions and were not detected in matrices. One high-energy form in each tautomer, 1cct (1H-) and 2pct (2H-), was found to differ from the most stable form only by rotation of the OH group and separated from other forms by high barriers. This opened a perspective for their stabilization in a matrix. 1cct and 2pct were generated in the matrices selectively by means of narrow-band near-infrared (NIR) irradiations of the samples at 6920 and 6937 cm{sup −1}, where the first OH stretching overtone

  5. The formic acid-nitric acid complex: microwave spectrum, structure, and proton transfer.

    PubMed

    Mackenzie, Rebecca B; Dewberry, Christopher T; Leopold, Kenneth R

    2014-09-11

    Rotational spectra are reported for seven isotopologues of the complex HCOOH-HNO3 in a supersonic jet. The system is planar and bound by a pair of hydrogen bonds, much like the more widely studied carboxylic acid dimers. Double proton exchange interconverts the system between a pair of equivalent structures, as revealed by a splitting of the a-type spectrum that disappears when one of the hydrogen bonding protons is replaced by deuterium. The observation of relative intensities that are consistent with nuclear spin statistics in a symmetric and antisymmetric pair of tunneling states provides additional evidence for such a motion. The observed splittings in the pure rotational spectrum are 1-2 orders of magnitude smaller than those recently reported in the pure rotational spectra of several related carboxylic acid dimers. This is a curious difference, although we note that because the observed spectra do not cross the tunneling doublet, the splittings are a measure of the difference in effective rotational constants for the two states, not the tunneling frequency itself. The observed rotational constants have been used to determine an accurate vibrationally averaged structure for the complex. The two hydrogen bond lengths, 1.686(17) Å and 1.813(10) Å for the hydrogen bonds involving the HNO3 and HCOOH protons, respectively, differ by 0.127(27) Å. Likewise, the associated oxygen-oxygen distances determined for the parent species, 2.631 and 2.794 Å, differ by 0.163 Å. These results suggest that the double proton transfer is necessarily accompanied by substantial motion of the heavy atom frame, and thus this system, in principle, provides an excellent prototype for multidimensional tunneling processes. Ab initio calculations of the binding energy and the barrier height are presented. Excellent agreement between the calculated equilibrium structure and the experimental, vibrationally averaged structure suggests that the vibrational wave function is not highly

  6. Base-free non-noble-metal-catalyzed hydrogen generation from formic acid: scope and mechanistic insights.

    PubMed

    Mellmann, Dörthe; Barsch, Enrico; Bauer, Matthias; Grabow, Kathleen; Boddien, Albert; Kammer, Anja; Sponholz, Peter; Bentrup, Ursula; Jackstell, Ralf; Junge, Henrik; Laurenczy, Gábor; Ludwig, Ralf; Beller, Matthias

    2014-10-13

    The iron-catalyzed dehydrogenation of formic acid has been studied both experimentally and mechanistically. The most active catalysts were generated in situ from cationic Fe(II) /Fe(III) precursors and tris[2-(diphenylphosphino)ethyl]phosphine (1, PP3 ). In contrast to most known noble-metal catalysts used for this transformation, no additional base was necessary. The activity of the iron catalyst depended highly on the solvent used, the presence of halide ions, the water content, and the ligand-to-metal ratio. The optimal catalytic performance was achieved by using [FeH(PP3 )]BF4 /PP3 in propylene carbonate in the presence of traces of water. With the exception of fluoride, the presence of halide ions in solution inhibited the catalytic activity. IR, Raman, UV/Vis, and EXAFS/XANES analyses gave detailed insights into the mechanism of hydrogen generation from formic acid at low temperature, supported by DFT calculations. In situ transmission FTIR measurements revealed the formation of an active iron formate species by the band observed at 1543 cm(-1) , which could be correlated with the evolution of gas. This active species was deactivated in the presence of chloride ions due to the formation of a chloro species (UV/Vis, Raman, IR, and XAS). In addition, XAS measurements demonstrated the importance of the solvent for the coordination of the PP3 ligand. PMID:25196789

  7. Base-free non-noble-metal-catalyzed hydrogen generation from formic acid: scope and mechanistic insights.

    PubMed

    Mellmann, Dörthe; Barsch, Enrico; Bauer, Matthias; Grabow, Kathleen; Boddien, Albert; Kammer, Anja; Sponholz, Peter; Bentrup, Ursula; Jackstell, Ralf; Junge, Henrik; Laurenczy, Gábor; Ludwig, Ralf; Beller, Matthias

    2014-10-13

    The iron-catalyzed dehydrogenation of formic acid has been studied both experimentally and mechanistically. The most active catalysts were generated in situ from cationic Fe(II) /Fe(III) precursors and tris[2-(diphenylphosphino)ethyl]phosphine (1, PP3 ). In contrast to most known noble-metal catalysts used for this transformation, no additional base was necessary. The activity of the iron catalyst depended highly on the solvent used, the presence of halide ions, the water content, and the ligand-to-metal ratio. The optimal catalytic performance was achieved by using [FeH(PP3 )]BF4 /PP3 in propylene carbonate in the presence of traces of water. With the exception of fluoride, the presence of halide ions in solution inhibited the catalytic activity. IR, Raman, UV/Vis, and EXAFS/XANES analyses gave detailed insights into the mechanism of hydrogen generation from formic acid at low temperature, supported by DFT calculations. In situ transmission FTIR measurements revealed the formation of an active iron formate species by the band observed at 1543 cm(-1) , which could be correlated with the evolution of gas. This active species was deactivated in the presence of chloride ions due to the formation of a chloro species (UV/Vis, Raman, IR, and XAS). In addition, XAS measurements demonstrated the importance of the solvent for the coordination of the PP3 ligand.

  8. 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 ...

  9. Conversion of hemicellulose sugars catalyzed by formic acid: kinetics of the dehydration of D-xylose, L-arabinose, and D-glucose.

    PubMed

    Dussan, Karla; Girisuta, Buana; Lopes, Marystela; Leahy, James J; Hayes, Michael H B

    2015-04-24

    The pre-treatment of lignocellulosic biomass produces a liquid stream of hemicellulose-based sugars, which can be further converted to high-value chemicals. Formosolv pulping and the Milox process use formic acid as the fractionating agent, which can be used as the catalyst for the valorisation of hemicellulose sugars to platform chemicals. The objective of this study was to investigate the reaction kinetics of major components in the hemicelluloses fraction of biomass, that is, D-xylose, L-arabinose and D-glucose. The kinetics experiments for each sugar were performed at temperatures between 130 and 170 °C in various formic acid concentrations (10-64 wt %). The implications of these kinetic models on the selectivity of each sugar to the desired products are discussed. The models were used to predict the reaction kinetics of solutions that resemble the liquid stream obtained from the fractionation process of biomass using formic acid. PMID:25821128

  10. CONDENSED MATTER: STRUCTURE, MECHANICAL AND THERMAL PROPERTIES: Electro-oxidation of Formic Acid on Carbon Supported Edge-Truncated Cubic Platinum Nanoparticles Catalysts

    NASA Astrophysics Data System (ADS)

    Li, She-Qiang; Fu, Xing-Qiu; Hu, Bing; Deng, Jia-Jun; Chen, Lei

    2009-11-01

    The oxidation of formic acid on edge-truncated cubic platinum nanoparticles/C catalysts is investigated. X-ray photoelectron spectroscopy analysis indicates that the surface of edge-truncated cubic platinum nanoparticles is composed of two types of coordination sites. The oxidation behavior of formic acid on edge-truncated cubic platinum nanoparticles/C is investigated using cyclic voltammetry. The apparent activation energies are found to be 54.2, 55.0, 61.8, 69.5, 71.9, 69.26, 65.28kJ/mol at 0.15, 0.3, 0.4, 0.5, 0.6, 0.65, 0.7V, respectively. A specific surface area activity of 1.76 mA·cm-2 at 0.4 V indicates that the edge-truncated cubic Platinum nanoparticles are a promising anode catalyst for direct formic acid fuel cells.

  11. Conversion of hemicellulose sugars catalyzed by formic acid: kinetics of the dehydration of D-xylose, L-arabinose, and D-glucose.

    PubMed

    Dussan, Karla; Girisuta, Buana; Lopes, Marystela; Leahy, James J; Hayes, Michael H B

    2015-04-24

    The pre-treatment of lignocellulosic biomass produces a liquid stream of hemicellulose-based sugars, which can be further converted to high-value chemicals. Formosolv pulping and the Milox process use formic acid as the fractionating agent, which can be used as the catalyst for the valorisation of hemicellulose sugars to platform chemicals. The objective of this study was to investigate the reaction kinetics of major components in the hemicelluloses fraction of biomass, that is, D-xylose, L-arabinose and D-glucose. The kinetics experiments for each sugar were performed at temperatures between 130 and 170 °C in various formic acid concentrations (10-64 wt %). The implications of these kinetic models on the selectivity of each sugar to the desired products are discussed. The models were used to predict the reaction kinetics of solutions that resemble the liquid stream obtained from the fractionation process of biomass using formic acid.

  12. 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

    2016-07-01

    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.

  13. 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

    2016-07-01

    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. PMID:27090191

  14. Controls on the microbial utilization of carbon monoxide and formic acid in Acidic Hydrothermal Springs in Yellowstone National Park

    NASA Astrophysics Data System (ADS)

    Urschel, M.; Kubo, M. W.; Hoehler, T. M.; Boyd, E. S.; Peters, J.

    2012-12-01

    In hydrothermal systems, dissolved carbon dioxide (CO2) in the presence of reduced iron-bearing minerals, such as those found in basalt, can be reduced to form formic acid (HCOOH). HCOOH can then be dehydrated in a side reaction, resulting in the generation of carbon monoxide (CO), which forms an equilibrium with HCOOH. HCOOH can also be further reduced to methane, and longer chain hydrocarbons. Geochemical measurements have demonstrated the presence of elevated concentrations of HCOOH, dissolved CO, and dissolved inorganic carbon (CO2, H2CO3), in high temperature, low pH springs in Yellowstone National Park (YNP). Likewise, a number of compounds that could potentially serve as electron acceptors (e.g. S0, SO42-, NO3-, Fe3+) in the oxidation of CO or formic acid have been detected in many of these systems. We hypothesized that the utilization of CO and HCOOH as carbon and/or energy sources is a broadly-distributed metabolic strategy in high temperature, low pH springs in YNP. To test this hypothesis, radiolabeled CO (14CO) and HCOOH (H14COOH) were used to determine rates of CO and formate oxidation activity in three hot springs in YNP ranging in temperature from 53 °C to 89 °C and pH from 2.5 to 5.3. In parallel, 16S rRNA gene sequencing and enrichment isolation techniques were employed to identify the microorganisms responsible for these activities. Our results indicate that CO and HCOOH are important sources of carbon and/or energy in high temperature, low pH hydrothermal springs in Yellowstone National Park. Rates of CO oxidation appear to be orders of magnitude lower than those of HCOOH oxidation. One possible explanation for this result is that HCOOH is preferentially utilized, consistent with thermodynamic calculations indicating that HCOOH liberates approximately 215 kJ/mol more Gibbs energy (under standard conditions) than CO when oxidized with oxygen (O2) as the electron acceptor. Redox couples of HCOOH oxidation with other electron acceptors (e.g. SO4

  15. Simultaneous acetic acid separation and monosaccharide concentration by reverse osmosis.

    PubMed

    Zhou, Fanglei; Wang, Cunwen; Wei, Jiang

    2013-03-01

    This study aimed to investigate the feasibility and efficiency of simultaneous acetic acid separation and sugar concentration in model lignocellulosic hydrolyzates by reverse osmosis. The effects of operation parameters such as pH, temperature, pressure and feed concentration on the solute retentions were examined with a synthetic xylose–glucose–acetic acid model solution. Results showed that the monosaccharides were almost completely rejected at above 20 bar, while the acetic acid retention increased with the increase in pH and pressure, and decreased with the temperature increase. The maximum separation factors of acetic acid over xylose and glucose reached as high as 211.5 and 228.4 at pH 2.93 (the initial pH of model lignocellulosic hydrolyzates), 40 °C and 20 bar. Furthermore, the concentration and diafiltration process were employed at optimal operation conditions. Consequently, a high sugar concentration and a beneficially lower acetic acid concentration were simultaneously achieved by reverse osmosis.

  16. Photodissociation spectroscopy of the Mg{sup +}-acetic acid complex

    SciTech Connect

    Abate, Yohannes; Kleiber, P. D.

    2006-11-14

    We have studied the structure and photodissociation of Mg{sup +}-acetic acid clusters. Ab initio calculations suggest four relatively strongly bound ground state isomers for the [MgC{sub 2}H{sub 4}O{sub 2}]{sup +} complex. These isomers include the cis and trans forms of the Mg{sup +}-acetic acid association complex with Mg{sup +} bonded to the carbonyl O atom of acetic acid, the Mg{sup +}-acetic acid association complex with Mg{sup +} bonded to the hydroxyl O atom of acetic acid, or to a Mg{sup +}-ethenediol association complex. Photodissociation through the Mg{sup +}-based 3p<-3s absorption bands in the near UV leads to direct (nonreactive) and reactive dissociation products: Mg{sup +}, MgOH{sup +}, Mg(H{sub 2}O){sup +}, CH{sub 3}CO{sup +}, and MgCH{sub 3}{sup +}. At low energies the dominant reactive quenching pathway is through dehydration to Mg(H{sub 2}O){sup +}, but additional reaction channels involving C-H and C-C bond activation are also open at higher energies.

  17. Acetic Acid Increases Stability of Silage under Aerobic Conditions

    PubMed Central

    Danner, H.; Holzer, M.; Mayrhuber, E.; Braun, R.

    2003-01-01

    The effects of various compounds on the aerobic stability of silages were evaluated. It has been observed that inoculation of whole-crop maize with homofermentative lactic acid bacteria leads to silages which have low stability against aerobic deterioration, while inoculation with heterofermentative lactic acid bacteria, such as Lactobacillus brevis or Lactobacillus buchneri, increases stability. Acetic acid has been proven to be the sole substance responsible for the increased aerobic stability, and this acid acts as an inhibitor of spoilage organisms. Therefore, stability increases exponentially with acetic acid concentration. Only butyric acid has a similar effect. Other compounds, like lactic acid, 1,2-propanediol, and 1-propanol, have been shown to have no effect, while fructose and mannitol reduce stability. PMID:12514042

  18. Carbon nanotube/raspberry hollow Pd nanosphere hybrids for methanol, ethanol, and formic acid electro-oxidation in alkaline media.

    PubMed

    Liu, Zhelin; Zhao, Bo; Guo, Cunlan; Sun, Yujing; Shi, Yan; Yang, Haibin; Li, Zhuang

    2010-11-01

    In this paper, raspberry hollow Pd nanospheres (HPNs)-decorated carbon nanotube (CNT) was developed for electro-oxidation of methanol, ethanol, and formic acid in alkaline media. The electrocatalyst was fabricated simply by attaching HPNs onto the surface of CNT which had been functionalized by polymer wrapping. The as-prepared HPN-CNTs (CHPNs) were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS). The increasing interest and intensive research on fuel cell inspire us to investigate the electrocatalytic properties of the prepared nanostructures. Besides that, previous reports about alkaline other than acidic media could supply a more active environment guide us to examine the electrocatalytic properties in alkaline electrolyte. It is found that this novel hybrid electrocatalyst exhibits excellent electrocatalytic properties and can be further applied in fuel cells, catalysts, and sensors.

  19. Bimetallic catalysts for CO.sub.2 hydrogenation and H.sub.2 generation from formic acid and/or salts thereof

    DOEpatents

    Hull, Jonathan F.; Himeda, Yuichiro; Fujita, Etsuko; Muckeman, James T.

    2015-08-04

    The invention relates to a ligand that may be used to create a catalyst including a coordination complex is formed by the addition of two metals; Cp, Cp* or an unsubstituted or substituted .pi.-arene; and two coordinating solvent species or solvent molecules. The bimetallic catalyst may be used in the hydrogenation of CO.sub.2 to form formic acid and/or salts thereof, and in the dehydrogenation of formic acid and/or salts thereof to form H.sub.2 and CO.sub.2.

  20. 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)

  1. Effects of plant species, stage of maturity, and level of formic acid addition on lipolysis, lipid content, and fatty acid composition during ensiling.

    PubMed

    Koivunen, E; Jaakkola, S; Heikkilä, T; Lampi, A-M; Halmemies-Beauchet-Filleau, A; Lee, M R F; Winters, A L; Shingfield, K J; Vanhatalo, A

    2015-09-01

    Forage type and management influences the nutritional quality and fatty acid composition of ruminant milk. Replacing grass silage with red clover (RC; L.) silage increases milk fat 18:3-3 concentration. Red clover has a higher polyphenol oxidase (PPO) activity compared with grasses, which has been suggested to decrease lipolysis and . The present study characterized the abundance and fatty acid composition of esterified lipid and NEFA before and after ensiling of grass and RC to investigate the influence of forage species, growth stage, and extent of fermentation on lipolysis. A randomized block design with a 2 × 3 × 4 factorial arrangement of treatments was used. Treatments comprised RC or a mixture of timothy ( L.) and meadow fescue ( Huds.) harvested at 3 growth stages and treated with 4 levels of formic acid (0, 2, 4, and 6 L/t). Lipid in silages treated with 0 or 6 L/t formic acid were extracted and separated into 4 fractions by TLC. Total PPO activity in fresh herbage and the content of soluble bound phenols in all silages were determined. Concentrations of 18:3-3 and total fatty acids (TFA) were higher ( < 0.001) for RC than for grass. For both forage species, 18:3-3 and TFA content decreased linearly ( < 0.001) with advancing growth stage, with the highest abundance at the vegetative stage. Most of lipid in fresh RC and grass herbage (97%) was esterified, whereas NEFA accounted for 71% of TFA in both silages. Ensiling resulted in marginal increases in TFA content and the amounts of individual fatty acids compared with fresh herbages. Herbage total PPO activity was higher ( < 0.001) for RC than grass (11 vs. 0.11 μkatal/g leaf fresh weight). Net lipolysis during ensiling was extensive for both forage species (660 to 759 g/kg fatty acid for grass and 563 to 737 g/kg fatty acid for RC). Formic acid application (0 vs. 6 L/t) resulted in a marked decrease ( = 0.026) in net lipolysis during the ensiling of RC, whereas the opposite was true ( = 0.026) for grass

  2. 21 CFR 184.1005 - Acetic acid.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... as ethanoic acid. It occurs naturally in plant and animal tissues. It is produced by fermentation of...). Current good manufacturing practice results in a maximum level as served, of 0.25 percent for baked...

  3. 21 CFR 184.1005 - Acetic acid.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... as ethanoic acid. It occurs naturally in plant and animal tissues. It is produced by fermentation of...). Current good manufacturing practice results in a maximum level as served, of 0.25 percent for baked...

  4. 21 CFR 184.1005 - Acetic acid.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... as ethanoic acid. It occurs naturally in plant and animal tissues. It is produced by fermentation of...). Current good manufacturing practice results in a maximum level as served, of 0.25 percent for baked...

  5. 21 CFR 184.1005 - Acetic acid.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... as ethanoic acid. It occurs naturally in plant and animal tissues. It is produced by fermentation of...). Current good manufacturing practice results in a maximum level as served, of 0.25 percent for baked...

  6. 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...

  7. 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...

  8. 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...

  9. 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...

  10. Different Protonation Equilibria of 4-Methylimidazole and Acetic Acid

    SciTech Connect

    Gu, Wei; Helms, Volkhard H.

    2007-12-03

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Dynamic protonation equilibria in water of one 4-methylimidazole molecule as well as for pairs and groups consisting of 4- methylimidazole, acetic acid and bridging water molecules are studied using Q-HOP molecular dynamics simulation. We find a qualitatively different protonation behavior of 4-methylimidazole compared to that of acetic acid. On one hand, deprotonated, neutral 4-methylimidazole cannot as easily attract a freely diffusing extra proton from solution. Once the proton is bound, however, it remains tightly bound on a time scale of tens of nanoseconds. In a linear chain composed of acetic acid, a separating water molecule and 4-methylimidazole, an excess proton is equally shared between 4-methylimidazole and water. When a water molecule is linearly placed between two acetic acid molecules, the excess proton is always found on the central water. On the other hand, an excess proton in a 4-methylimidazole-water- 4-methylimidazole chain is always localized on one of the two 4- methylimidazoles. These findings are of interest to the discussion of proton transfer along chains of amino acids and water molecules in biomolecules.

  11. Dehydrogenation of Formic Acid at Room Temperature: Boosting Palladium Nanoparticle Efficiency by Coupling with Pyridinic-Nitrogen-Doped Carbon.

    PubMed

    Bi, Qing-Yuan; Lin, Jian-Dong; Liu, Yong-Mei; He, He-Yong; Huang, Fu-Qiang; Cao, Yong

    2016-09-19

    The use of formic acid (FA) to produce molecular H2 is a promising means of efficient energy storage in a fuel-cell-based hydrogen economy. To date, there has been a lack of heterogeneous catalyst systems that are sufficiently active, selective, and stable for clean H2 production by FA decomposition at room temperature. For the first time, we report that flexible pyridinic-N-doped carbon hybrids as support materials can significantly boost the efficiency of palladium nanoparticle for H2 generation; this is due to prominent surface electronic modulation. Under mild conditions, the optimized engineered Pd/CN0.25 catalyst exhibited high performance in both FA dehydrogenation (achieving almost full conversion, and a turnover frequency of 5530 h(-1) at 25 °C) and the reversible process of CO2 hydrogenation into FA. This system can lead to a full carbon-neutral energy cycle. PMID:27552650

  12. Complementary cavity-enhanced spectrometers to investigate the OH + CH combination band in trans-formic acid.

    PubMed

    Golebiowski, D; Földes, T; Vanfleteren, T; Herman, M; Perrin, A

    2015-07-01

    We have used continuous-wave cavity ring-down and femto-Fourier transform-cavity-enhanced absorption spectrometers to record the spectrum of the OH-stretching + CH-stretching (ν1 + ν2) combination band in trans-formic acid, with origin close to 6507 cm(-1). They, respectively, allowed resolving and simplifying the rotational structure of the band near its origin under jet-cooled conditions (Trot = 10 K) and highlighting the overview of the band under room temperature conditions. The stronger B-type and weaker A-type subbands close to the band origin could be assigned, as well as the main B-type Q branches. The high-resolution analysis was hindered by numerous, severe perturbations. Rotational constants are reported with, however, limited physical meaning. The ν1 + ν2 transition moment is estimated from relative intensities to be 24° away from the principal b-axis of inertia.

  13. Vibration-Rotation Spectrum of Formic Acid Dimer in the 7.3μm Region

    NASA Astrophysics Data System (ADS)

    Duan, Chuanxi

    2016-06-01

    The vibration-rotation-tunneling spectrum of formic acid dimer, (HCOOH)2, in the spectral region 1369-1375 wn has been measured by a multi-step rapid-can method in a slit jet expansion using a distributed-feedback quantum cascade laser. The observed spectrum is assigned to the O-C-H bending fundamental band. The tunneling splitting in the vibrational excited state is determined to be about 0.005 wn, which is much smaller than that in the ground state, 0.0165 wn (Goroya et al.,J. Chem. Phys. 140, 164311 (2014)). Strong local perturbations involving transitions with J > 9, K = 0 and 1 are identified in the observed spectrum. The deperturbation analysis will be presented.

  14. Polyhedral Palladium–Silver Alloy Nanocrystals as Highly Active and Stable Electrocatalysts for the Formic Acid Oxidation Reaction

    PubMed Central

    Fu, Geng-Tao; Liu, Chang; Zhang, Qi; Chen, Yu; Tang, Ya-Wen

    2015-01-01

    Polyhedral noble–metal nanocrystals have received much attention and wide applications as electrical and optical devices as well as catalysts. In this work, a straightforward and effective hydrothermal route for the controllable synthesis of the high-quality Pd–Ag alloy polyhedrons with uniform size is presented. The morphology, composition and structure of the Pd–Ag alloy polyhedrons are fully characterized by the various physical techniques, demonstrating the Pd–Ag alloy polyhedrons are highly alloying. The formation/growth mechanisms of the Pd–Ag alloy polyhedrons are explored and discussed based on the experimental observations and discussions. As a preliminary electrochemical application, the Pd–Ag alloy polyhedrons are applied in the formic acid oxidation reaction, which shows higher electrocatalytic activity and stability than commercially available Pd black due to the “synergistic effects” between Pd and Ag atoms. PMID:26329555

  15. Synchronized Current Oscillations of Formic Acid Electro-oxidation in a Microchip-based Dual-Electrode Flow Cell

    PubMed Central

    Kiss, István Z.; Munjal, Neil; Martin, R. Scott

    2009-01-01

    We investigate the oscillatory electro-oxidation of formic acid on platinum in a microchip-based dual-electrode cell with microfluidic flow control. The main dynamical features of current oscillations on single Pt electrode that had been observed in macro-cells are reproduced in the microfabricated electrochemical cell. In dual-electrode configuration nearly in-phase synchronized current oscillations occur when the reference/counter electrodes are placed far away from the microelectrodes. The synchronization disappears with close reference/counter electrode placements. We show that the cause for synchronization is weak albeit important, bidirectional electrical coupling between the electrodes; therefore the unidirectional mass transfer interactions are negligible. The experimental design enables the investigation of the dynamical behavior in micro-electrode arrays with well-defined control of flow of the electrolyte in a manner where the size and spacing of the electrodes can be easily varied. PMID:20160883

  16. Synchronized Current Oscillations of Formic Acid Electro-oxidation in a Microchip-based Dual-Electrode Flow Cell.

    PubMed

    Kiss, István Z; Munjal, Neil; Martin, R Scott

    2009-12-30

    We investigate the oscillatory electro-oxidation of formic acid on platinum in a microchip-based dual-electrode cell with microfluidic flow control. The main dynamical features of current oscillations on single Pt electrode that had been observed in macro-cells are reproduced in the microfabricated electrochemical cell. In dual-electrode configuration nearly in-phase synchronized current oscillations occur when the reference/counter electrodes are placed far away from the microelectrodes. The synchronization disappears with close reference/counter electrode placements. We show that the cause for synchronization is weak albeit important, bidirectional electrical coupling between the electrodes; therefore the unidirectional mass transfer interactions are negligible. The experimental design enables the investigation of the dynamical behavior in micro-electrode arrays with well-defined control of flow of the electrolyte in a manner where the size and spacing of the electrodes can be easily varied.

  17. Morphological features of electrodeposited Pt nanoparticles and its application as anode catalysts in polymer electrolyte formic acid fuel cells

    NASA Astrophysics Data System (ADS)

    Jeon, Hongrae; Joo, Jiyong; Kwon, Youngkook; Uhm, Sunghyun; Lee, Jaeyoung

    Electrodeposited Pt nanoparticles on carbon substrate show various morphologies depending on the applied potentials. Dendritic, pyramidal, cauliflower-like, and hemi-spherical morphologies of Pt are formed at potential ranges between -0.2 and 0.3 V (vs. Ag/AgCl) and its particle sizes are distributed from 8 to 26 nm. Dendritic bulky particles over 20 nm are formed at an applied potential of -0.2 V, while low deposition potential of 0.2 V causes dense hemi-spherical structure of Pt less than 10 nm. The influence of different Pt shapes on an electrocatalytic oxidation of formic acid is represented. Consequently, homogeneous distribution of Pt nanoparticles with average particle of ca. 14 nm on carbon paper results in a high surface to volume ratio and the better power performance in a fuel cell application.

  18. Graphene nanosheets-polypyrrole hybrid material as a highly active catalyst support for formic acid electro-oxidation.

    PubMed

    Yang, Sudong; Shen, Chengmin; Liang, Yanyu; Tong, Hao; He, Wei; Shi, Xuezhao; Zhang, Xiaogang; Gao, Hong-jun

    2011-08-01

    A novel electrode material based on graphene oxide (GO)-polypyrrole (PPy) composites was synthesized by in situ chemical oxidation polymerization. Palladium nanoparticles (NPs) with a diameter of 4.0 nm were loaded on the reduced graphene oxide(RGO)-PPy composites by a microwave-assisted polyol process. Microstructure analysis showed that a layer of coated PPy film with monodisperse Pd NPs is present on the RGO surface. The Pd/RGO-PPy catalysts exhibit excellent catalytic activity and stability for formic acid electro-oxidation when the weight feed ratio of GO to pyrrole monomer is 2:1. The superior performance of Pd/RGO-PPy catalysts may arise from utilization of heterogeneous nucleation sites for NPs and the greatly increased electronic conductivity of the supports.

  19. Preparation of Nanoporous Pd by Dealloying Al-Pd Slice and Its Electrocatalysts for Formic Acid Oxidation

    NASA Astrophysics Data System (ADS)

    Yu, Nana; Wang, Tianning; Nie, Chen; Sun, Lanju; Li, Jie; Geng, Haoran

    2016-01-01

    AlPd alloy slices with a thickness of 0.5 mm were taken as precursors during the fabrication of nanoporous palladium (np-Pd) using chemical dealloying in NaOH solution or electrochemical dealloying in NaCl solution. Scanning electron microscope photos and x-ray diffraction patterns demonstrate a full dealloying of Al out of the precursors and the formation of nP-Pd which is characterized by a three-dimensional, bicontinuous, ligament-channel structure with nanoscale length scales. Electrochemical measurements were performed to evaluate the electrocatalytic activity and structure stability of np-Pd towards formic acid oxidation and it showed a good structure stability.

  20. Chemistry of OH in remote clouds and its role in the production of formic acid and peroxymonosulfate

    NASA Technical Reports Server (NTRS)

    Jacob, D. J.

    1986-01-01

    The chemistry of OH in nonprecipitating tropospheric clouds was studied using a coupled gas phase/aqueous phase chemical model. The simulation takes into account the radial dependence of the concentrations of short lived aqueous phase species, in particular, O3(aq) OH(aq). Formic acid is shown to be rapidly produced by the aqueous phase reaction between H2C(OH)2 and OH, but HCOO(-) and OH, but HCOO(-) is in turn rapidly oxidized by OH(aq). The HCOOH concentration in cloud is shown to be strongly dependent on the pH of the cloud water; clouds with pH greater than 5 are not efficient HCOOH sources. A novel mechanism is proposed for the oxidation of S(IV) by OH(aq), with the main product predicted to be peroxymonosulfate, HSO5(-). The latter could contribute significantly to total cloud water sulfur.

  1. FORMATION OF CARBON DIOXIDE, METHANOL, ETHANOL, AND FORMIC ACID ON AN ICY GRAIN ANALOG USING FAST OXYGEN ATOMS

    SciTech Connect

    Madzunkov, S. M.; MacAskill, J. A.; Chutjian, A.

    2010-03-20

    Carbon dioxide (CO{sub 2}), methanol (CH{sub 3}OH), ethanol (CH{sub 3}CH{sub 2}OH), and formic acid (HCOOH) have been formed in collisions of a superthermal, 9 eV beam of O({sup 3} P) atoms with CH{sub 4} molecules, with an over coat of CO molecules, adsorbed on a gold surface at 4.8 K. The products are detected using temperature programmed-desorption and quadrupole mass spectrometry. Identification of the species is carried out through use of the Metropolis random walk algorithm as constrained by the fractionation patterns of the detected species. Relative formation yields are reported and reaction sequences are given to account for possible formation routes.

  2. Polyhedral Palladium-Silver Alloy Nanocrystals as Highly Active and Stable Electrocatalysts for the Formic Acid Oxidation Reaction

    NASA Astrophysics Data System (ADS)

    Fu, Geng-Tao; Liu, Chang; Zhang, Qi; Chen, Yu; Tang, Ya-Wen

    2015-09-01

    Polyhedral noble-metal nanocrystals have received much attention and wide applications as electrical and optical devices as well as catalysts. In this work, a straightforward and effective hydrothermal route for the controllable synthesis of the high-quality Pd-Ag alloy polyhedrons with uniform size is presented. The morphology, composition and structure of the Pd-Ag alloy polyhedrons are fully characterized by the various physical techniques, demonstrating the Pd-Ag alloy polyhedrons are highly alloying. The formation/growth mechanisms of the Pd-Ag alloy polyhedrons are explored and discussed based on the experimental observations and discussions. As a preliminary electrochemical application, the Pd-Ag alloy polyhedrons are applied in the formic acid oxidation reaction, which shows higher electrocatalytic activity and stability than commercially available Pd black due to the “synergistic effects” between Pd and Ag atoms.

  3. A photocatalyst-enzyme coupled artificial photosynthesis system for solar energy in production of formic acid from CO2.

    PubMed

    Yadav, Rajesh K; Baeg, Jin-Ook; Oh, Gyu Hwan; Park, No-Joong; Kong, Ki-jeong; Kim, Jinheung; Hwang, Dong Won; Biswas, Soumya K

    2012-07-18

    The photocatalyst-enzyme coupled system for artificial photosynthesis process is one of the most promising methods of solar energy conversion for the synthesis of organic chemicals or fuel. Here we report the synthesis of a novel graphene-based visible light active photocatalyst which covalently bonded the chromophore, such as multianthraquinone substituted porphyrin with the chemically converted graphene as a photocatalyst of the artificial photosynthesis system for an efficient photosynthetic production of formic acid from CO(2). The results not only show a benchmark example of the graphene-based material used as a photocatalyst in general artificial photosynthesis but also the benchmark example of the selective production system of solar chemicals/solar fuel directly from CO(2).

  4. Graphene nanosheets-polypyrrole hybrid material as a highly active catalyst support for formic acid electro-oxidation.

    PubMed

    Yang, Sudong; Shen, Chengmin; Liang, Yanyu; Tong, Hao; He, Wei; Shi, Xuezhao; Zhang, Xiaogang; Gao, Hong-jun

    2011-08-01

    A novel electrode material based on graphene oxide (GO)-polypyrrole (PPy) composites was synthesized by in situ chemical oxidation polymerization. Palladium nanoparticles (NPs) with a diameter of 4.0 nm were loaded on the reduced graphene oxide(RGO)-PPy composites by a microwave-assisted polyol process. Microstructure analysis showed that a layer of coated PPy film with monodisperse Pd NPs is present on the RGO surface. The Pd/RGO-PPy catalysts exhibit excellent catalytic activity and stability for formic acid electro-oxidation when the weight feed ratio of GO to pyrrole monomer is 2:1. The superior performance of Pd/RGO-PPy catalysts may arise from utilization of heterogeneous nucleation sites for NPs and the greatly increased electronic conductivity of the supports. PMID:21713273

  5. The Melting Curve and High-Pressure Chemistry of Formic Acid to 8 GPa and 600 K

    SciTech Connect

    Montgomery, W; Zaug, J M; Howard, W M; Goncharov, A F; Crowhurst, J C; Jeanloz, R

    2005-04-13

    We have determined the melting temperature of formic acid (HCOOH) to 8.5 GPa using infrared absorption spectroscopy, Raman spectroscopy and visual observation of samples in a resistively heated diamond-anvil cell. The experimentally determined melting curve compares favorably with a two-phase thermodynamic model. Decomposition reactions were observed above the melting temperature up to a pressure of 6.5 GPa, where principal products were CO{sub 2}, H{sub 2}O and CO. At pressures above 6.5 GPa, decomposition led to solid-like reaction products. Infrared and Raman spectra of these recovered products indicate that pressure affects the nature of carbon-carbon bonding.

  6. Nanobranched porous palladium-tin intermetallics: One-step synthesis and their superior electrocatalysis towards formic acid oxidation

    NASA Astrophysics Data System (ADS)

    Sun, Dandan; Si, Ling; Fu, Gengtao; Liu, Chang; Sun, Dongmei; Chen, Yu; Tang, Yawen; Lu, Tianhong

    2015-04-01

    Nanocrystalline intermetallics in bulk with high surface area hold enormous promise as an efficient catalyst for real fuel cell applications due to their unique electrocatalytic properties. In this work, a novel three-dimensional (3D) porous Pd-Sn intermetallics in network nanostructures (Pd-Sn-INNs) has been fabricated at relatively low temperature for the first time by one-step ethylene glycol-assisted hydrothermal reduction method. The structure characteristics of the Pd-Sn-INNs are confirmed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray (EDX), selected-area electron diffraction (SAED), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The as-prepared 3D Pd-Sn-INNs exhibit remarkably improved electrocatalytic activity and stability towards formic acid oxidation reaction (FAOR) over commercially available Pd black.

  7. A Comprehensive Study of Formic Acid Oxidation on Palladium Nanocrystals with Different Types of Facets and Twin Defects

    SciTech Connect

    Choi, Sang; Herron, Jeffrey A.; Scaranto, Jessica; Huang, Hongwen; Wang, Yi; Xia, Xiaohu; Lv, Tian; Park, Jinho; Peng, Hsin-Chieh; Mavrikakis, Manos; Xia, Younan

    2015-07-13

    Palladium has been recognized as the best anodic, monometallic electrocatalyst for the formic acid oxidation (FAO) reaction in a direct formic acid fuel cell. Here we report a systematic study of FAO on a variety of Pd nanocrystals, including cubes, right bipyramids, octahedra, tetrahedra, decahedra, and icosahedra. These nanocrystals were synthesized with approximately the same size, but different types of facets and twin defects on their surfaces. Our measurements indicate that the Pd nanocrystals enclosed by {1 0 0} facets have higher specific activities than those enclosed by {1 1 1} facets, in agreement with prior observations for Pd single-crystal substrates. If comparing nanocrystals predominantly enclosed by a specific type of facet, {1 0 0} or {1 1 1}, those with twin defects displayed greatly enhanced FAO activities compared to their single-crystal counterparts. To rationalize these experimental results, we performed periodic, self-consistent DFT calculations on model single-crystal substrates of Pd, representing the active sites present in the nanocrystals used in the experiments. The calculation results suggest that the enhancement of FAO activity on defect regions, represented by Pd(2 1 1) sites, compared to the activity of both Pd(1 0 0) and Pd(1 1 1) surfaces, could be attributed to an increased flux through the HCOO-mediated pathway rather than the COOH-mediated pathway on Pd(2 1 1). Since COOH has been identified as a precursor to CO, a site-poisoning species, a lower coverage of CO at the defect regions will lead to a higher activity for the corresponding nanocrystal catalysts, containing those defect regions.

  8. Tropospheric Emission Spectrometer (TES) satellite observations of ammonia, methanol, formic acid, and carbon monoxide over the Canadian oil sands: validation and model evaluation

    EPA Science Inventory

    The wealth of air quality information provided by satellite infrared observations of ammonia (NH3), carbon monoxide (CO), formic acid (HCOOH), and methanol (CH3OH) is currently being explored and used for a number of applications, especially at regional or global scales. These ap...

  9. Ultrafast synthesis of flower-like ordered Pd3Pb nanocrystals with superior electrocatalytic activities towards oxidation of formic acid and ethanol

    NASA Astrophysics Data System (ADS)

    Jana, Rajkumar; Subbarao, Udumula; Peter, Sebastian C.

    2016-01-01

    Ordered intermetallic nanocrystals with high surface area are highly promising as efficient catalysts for fuel cell applications because of their unique electrocatalytic properties. The present work discusses about the controlled synthesis of ordered intermetallic Pd3Pb nanocrystals in different morphologies at relatively low temperature for the first time by polyol and hydrothermal methods both in presence and absence of surfactant. Here for the first time we report surfactant free synthesis of ordered flower-like intermetallic Pd3Pb nanocrystals in 10 s. The structural characteristics of the nanocrystals are confirmed by powder X-ray diffraction, transmission electron microscopy, field emission scanning electron microscopy, X-ray photoelectron spectroscopy and energy-dispersive X-ray spectroscopy. The as synthesized ordered Pd3Pb nanocrystals exhibit far superior electrocatalytic activity and durability towards formic acid and ethanol oxidation over commercially available Pd black (Pd/C). The morphological variation of nanocrystals plays a crucial role in the electrocatalytic oxidation of formic acid and ethanol. Among the catalysts, the flower-like Pd3Pb shows enhanced activity and stability in electrocatalytic formic acid and ethanol oxidation. The current density and mass activity of flower-like Pd3Pb catalyst are higher by 2.5 and 2.4 times than that of Pd/C for the formic acid oxidation and 1.5 times each for ethanol oxidation.

  10. Structure-dependent photocatalytic decomposition of formic acid on the anatase TiO2(101) surface and strategies to increase its reaction rate

    NASA Astrophysics Data System (ADS)

    Ji, Yongfei; Luo, Yi

    2016-02-01

    Formic acid is a typical molecule that is involved in a lot important solar energy conversion processes. We perform first-principles calculations on the molecular mechanism of its photocatalytic decomposition reaction (PCD) on the anatase TiO2(101) surface. We find that the reaction barrier is sensitively dependent on the adsorption structure of the molecule. The one-step PCD of the monodentate formic acid has a lower barrier than that of bidentate formate. Coadsorbed water molecules can transform the formate from a bidentate to a monodentate configuration which greatly lower its decomposition barrier. Water molecule can also induce the spontaneous dissociation of the formic acid molecule. The monodentate dissociated formic acid is stabilized by the hydrogen bonds which will slightly enhance the barrier for its photodecomposition. However, the reaction rate can be further enhanced if the hydrogens are removed (for example, by oxygen molecules). Therefore, using coadsorbate and deliberately introducing and removing hydrogen bonds can be two strategies to tailor the photoreaction rate of the molecules.

  11. A Convenient Palladium-Catalyzed Carbonylative Synthesis of Benzofuran-2(3 H)-ones with Formic Acid as the CO Source.

    PubMed

    Qi, Xinxin; Li, Hao-Peng; Wu, Xiao-Feng

    2016-09-01

    A general and convenient palladium-catalyzed carbonylation procedure for the synthesis of benzofuran-2(3 H)-ones from phenols and aldehydes has been developed. With formic acid as the CO source, a variety of benzofuran-2(3 H)-ones were obtained in moderate to good yields. PMID:27539230

  12. Condensation of acetol and acetic acid vapor with sprayed liquid

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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 ...

  13. Thermodynamic analysis of acetic acid steam reforming for hydrogen production

    NASA Astrophysics Data System (ADS)

    Goicoechea, Saioa; Ehrich, Heike; Arias, Pedro L.; Kockmann, Norbert

    2015-04-01

    A thermodynamic analysis of hydrogen generation by acetic acid steam reforming has been carried out with respect to applications in solid oxide fuel cells. The effect of operating parameters on equilibrium composition has been examined focusing especially on hydrogen and carbon monoxide production, which are the fuels in this type of fuel cell. The temperature, steam to acetic acid ratio, and to a lesser extent pressure affect significantly the equilibrium product distribution due to their influence on steam reforming, thermal decomposition and water-gas shift reaction. The study shows that steam reforming of acetic acid with a steam to acetic acid ratio of 2 to 1 is thermodynamically feasible with hydrogen, carbon monoxide and water as the main products at the equilibrium at temperatures higher than 700 °C, and achieving CO/CO2 ratios higher than 1. Thus, it can be concluded that within the operation temperature range of solid oxide fuel cells - between 700 °C and 1000 °C - the production of a gas rich in hydrogen and carbon monoxide is promoted.

  14. Intramolecular carbon isotope distribution of acetic acid in vinegar.

    PubMed

    Hattori, Ryota; Yamada, Keita; Kikuchi, Makiko; Hirano, Satoshi; Yoshida, Naohiro

    2011-09-14

    Compound-specific carbon isotope analysis of acetic acid is useful for origin discrimination and quality control of vinegar. Intramolecular carbon isotope distributions, which are each carbon isotope ratios of the methyl and carboxyl carbons in the acetic acid molecule, may be required to obtain more detailed information to discriminate such origin. In this study, improved gas chromatography-pyrolysis-gas chromatography-combustion-isotope ratio mass spectrometry (GC-Py-GC-C-IRMS) combined with headspace solid-phase microextraction (HS-SPME) was used to measure the intramolecular carbon isotope distributions of acetic acid in 14 Japanese vinegars. The results demonstrated that the methyl carbons of acetic acid molecules in vinegars produced from plants were mostly isotopically depleted in (13)C relative to the carboxyl carbon. Moreover, isotopic differences (δ(13)C(carboxyl) - δ(13)C(methyl)) had a wide range from -0.3 to 18.2‰, and these values differed among botanical origins, C3, C4, and CAM plants.

  15. Release of acetic acid and furfural from cork products.

    PubMed

    Salthammer, T; Fuhrmann, F

    2000-06-01

    Cork samples were exposed to different temperatures and volatile ingredients were analyzed using gas chromatography/mass spectrometry (GC/MS). Thermal treatment at 180 degrees C yielded considerable amounts of furfural and acetic acid. In accordance with previous investigations it was concluded that both compounds are produced under thermal stress from degradation of polyoses.

  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. Effects of acetic acid on light scattering from cells

    NASA Astrophysics Data System (ADS)

    Marina, Oana C.; Sanders, Claire K.; Mourant, Judith R.

    2012-08-01

    Acetic acid has been used for decades as an aid for the detection of precancerous cervical lesions, and the use of acetic acid is being investigated in several other tissues. Nonetheless, the mechanism of acetowhitening is unclear. This work tests some of the hypotheses in the literature and measures changes in light scattering specific to the nucleus and the cytoplasm. Wide angle side scattering from both the nucleus and the cytoplasm increases with acetic application to tumorigenic cells, with the increase in nuclear scattering being greater. In one cell line, the changes in nuclear scattering are likely due to an increase in number or scattering efficiency of scattering centers smaller than the wavelength of excitation light. There are likely several cellular changes that cause acetowhitening and the cellular changes may differ with cell type. These results should lead to a better understanding of acetowhitening and potentially the development of adjunct techniques to improve the utility of acetic acid application. For the well-studied case of cervical tissue, acetowhitening has been shown to be sensitive, but not specific for oncogenic changes needing treatment.

  18. Calculations and measurements of the deuterium tunneling frequency in the propiolic acid-formic acid dimer and description of a newly constructed Fourier transform microwave spectrometer.

    PubMed

    Sun, Ming; Wang, Yimin; Carey, Spencer J; Mitchell, Erik G; Bowman, Joel; Kukolich, Stephen G

    2013-08-28

    The concerted proton tunneling frequency for the propiolic acid-formic acid dimer was calculated using a relaxed ab initio double-well potential in the imaginary-frequency mode of the saddle point, and new measurements were made for the deuterated propiolic acid-formic acid (ProOD-FAOD) isotopologue. It is important to have consistent calculated tunneling frequency values between normal and deuterated isotopologues since parameters can be readily adjusted to get good agreement with one isotopologue. High-resolution rotational spectra of deuterated (ProOD-FAOD) dimer were measured using a newly constructed Fourier Transform microwave spectrometer. The new spectrometer has mirror size: 30 cm in diameter with a radius of curvature of 59 cm and is equipped with multiple-FID data collection (5-10 FID's for each gas pulse). For the deuterated (ProOD-FAOD) isotopologue, 45 rotational lines (a type: 34; b type: 11) were measured in the lowest tunneling states range between 6.5 GHz and 15.5 GHz. With the new high-resolution measurements of the tunneling doublets (b-dipole transitions), the double potential well responsible for the deuterium tunneling was depicted much more precisely. The two tunneling states are separated by 3.48 MHz. The rotational constants obtained in this work are quite helpful for further structure analysis as well.

  19. 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. PMID:26253254

  20. 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.

  1. [Conversion of acetic acid to methane by thermophiles

    SciTech Connect

    Zinder, S.H.

    1993-01-01

    The primary goal of this project is to obtain a better understanding of thermophilic microorganisms which convert acetic acid to CH[sub 4]. The previous funding period represents a departure from earlier research in this laboratory, which was more physiological and ecological. The present work is centered on the biochemistry of the thermophile Methanothrix sp. strain CALS-1. this organism presents a unique opportunity, with its purity and relatively rapid growth, to do comparative biochemical studies with the other major acetotrophic genus Methanosarcina. We previously found that Methanothrix is capable of using acetate at concentrations 100 fold lower than Methanosarcina. This finding suggests that there are significant differences in the pathways of methanogenesis from acetate in the two genera.

  2. (Conversion of acetic acid to methane by thermophiles: Progress report)

    SciTech Connect

    Zinder, S.

    1991-01-01

    The objective of this project is to provide an understanding of thermophilic anaerobic microorganisms capable of breaking down acetic acid, the precursor of two-thirds of the methane produced by anaerobic bioreactors. Recent results include: (1) the isolation of Methanothrix strain CALLS-1, which grows much more rapidly than mesophilic strains; (2) the demonstration that thermophilic cultures of Methanosarcina and Methanothrix show minimum thresholds for acetate utilization of 1--2.5 mM and 10--20{mu}m respectively, in agreement with ecological data indicating that Methanothrix is favored by low acetate concentration; (3) the demonstration of high levels of thermostable acetyl-coA synthetase and carbon monoxide dehydrogenase in cell-free extracts of Methanothrix strains CALS-1; (4) the demonstration of methanogenesis from acetate and ATP in cell free extracts of strain CALS-1. (5) the demonstration that methanogenesis from acetate required 2 ATP/methane, and, in contrast to Methanosarcina, was independent of hydrogen and other electron donors; (6) the finding that entropy effects must be considered when predicting the level of hydrogen in thermophilic syntrophic cultures. (7) the isolation and characterization of the Desulfotomaculum thermoacetoxidans. Current research is centered on factors which allow thermophilic Methanothrix to compete with Methanosarcina.

  3. [Conversion of acetic acid to methane by thermophiles: Progress report

    SciTech Connect

    Zinder, S.

    1991-12-31

    The objective of this project is to provide an understanding of thermophilic anaerobic microorganisms capable of breaking down acetic acid, the precursor of two-thirds of the methane produced by anaerobic bioreactors. Recent results include: (1) the isolation of Methanothrix strain CALLS-1, which grows much more rapidly than mesophilic strains; (2) the demonstration that thermophilic cultures of Methanosarcina and Methanothrix show minimum thresholds for acetate utilization of 1--2.5 mM and 10--20{mu}m respectively, in agreement with ecological data indicating that Methanothrix is favored by low acetate concentration; (3) the demonstration of high levels of thermostable acetyl-coA synthetase and carbon monoxide dehydrogenase in cell-free extracts of Methanothrix strains CALS-1; (4) the demonstration of methanogenesis from acetate and ATP in cell free extracts of strain CALS-1. (5) the demonstration that methanogenesis from acetate required 2 ATP/methane, and, in contrast to Methanosarcina, was independent of hydrogen and other electron donors; (6) the finding that entropy effects must be considered when predicting the level of hydrogen in thermophilic syntrophic cultures. (7) the isolation and characterization of the Desulfotomaculum thermoacetoxidans. Current research is centered on factors which allow thermophilic Methanothrix to compete with Methanosarcina.

  4. Comparative genotoxicity of halogenated acetic acids found in drinking water.

    PubMed

    Giller, S; Le Curieux, F; Erb, F; Marzin, D

    1997-09-01

    Three short-term assays (SOS chromotest, Ames fluctuation test and newt micronucleus test) were performed to detect the genotoxic activity of organohalides, compounds likely to be found in chlorinated and/or ozonated drinking water: monochloro-, dichloro- and trichloroacetic acids and monobromo-, dibromo- and tribromoacetic acids. With the SOS chromotest, only three of the chemicals studied (dichloroacetic acid, dibromo- and tribromoacetic acids) were found to induce primary DNA damage in Escherichia coli PQ 37. In the Ames fluctuation test, all the compounds except monochloroacetic acid showed mutagenic activity in Salmonella typhimurium strain TA100. In these two in vitro tests, a good correlation between increasing number of substituents and decreasing mutagenicity was observed. Namely, the toxicity of brominated and chlorinated acetic acids decreased when the number of substituents increased. The newt micronucleus test detected a weak clastogenic effect on the peripheral blood erythrocytes of Pleurodeles waltl larvae for trichloroacetic acid only.

  5. Analytical continuation in coupling constant method; application to the calculation of resonance energies and widths for organic molecules: Glycine, alanine and valine and dimer of formic acid

    NASA Astrophysics Data System (ADS)

    Papp, P.; Matejčík, Š.; Mach, P.; Urban, J.; Paidarová, I.; Horáček, J.

    2013-06-01

    The method of analytic continuation in the coupling constant (ACCC) in combination with use of the statistical Padé approximation is applied to the determination of resonance energy and width of some amino acids and formic acid dimer. Standard quantum chemistry codes provide accurate data which can be used for analytic continuation in the coupling constant to obtain the resonance energy and width of organic molecules with a good accuracy. The obtained results are compared with the existing experimental ones.

  6. Evaporation kinetics of acetic acid-water solutions

    NASA Astrophysics Data System (ADS)

    Duffey, K.; Wong, N.; Saykally, R.; Cohen, R. C.

    2012-12-01

    The transport of water molecules across vapor-liquid interfaces in the atmosphere is a crucial step in the formation and evolution of cloud droplets. Despite decades of study, the effects of solutes on the mechanism and rate of evaporation and condensation remain poorly characterized. The present work aims to determine the effect of atmospherically-relevant solutes on the evaporation rate of water. In our experiments, we create a train of micron-sized droplets and measure their temperature via Raman thermometry as they undergo evaporation without condensation. Analysis of the cooling rate yields the evaporation coefficient (γ). Previous work has shown that inorganic salts have little effect on γ, with surface-adsorbing anions causing a slight reduction in the coefficient from that measured for pure water. Organic acids are ubiquitous in aqueous aerosol and have been shown to disrupt the surface structure of water. Here we describe measurements of the evaporation rate of acetic acid solutions, showing that acetic acid reduces γ to a larger extent than inorganic ions, and that γ decreases with increasing acetic acid concentration.

  7. 40 CFR 721.10448 - Acetic acid, hydroxy- methoxy-, methyl ester, reaction products with substituted alkylamine...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... ester, reaction products with substituted alkylamine (generic). 721.10448 Section 721.10448 Protection... Acetic acid, hydroxy- methoxy-, methyl ester, reaction products with substituted alkylamine (generic). (a... generically as acetic acid, hydroxymethoxy-, methyl ester, reaction products with substituted alkylamine...

  8. 40 CFR 721.10448 - Acetic acid, hydroxy- methoxy-, methylester, reaction products with substituted alkylamine...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...-, methylester, reaction products with substituted alkylamine (generic). 721.10448 Section 721.10448 Protection... Acetic acid, hydroxy- methoxy-, methylester, reaction products with substituted alkylamine (generic). (a... generically as acetic acid, hydroxymethoxy-, methyl ester, reaction products with substituted alkylamine...

  9. 3D-nanoarchitectured Pd/Ni catalysts prepared by atomic layer deposition for the electrooxidation of formic acid.

    PubMed

    Assaud, Loïc; Monyoncho, Evans; Pitzschel, Kristina; Allagui, Anis; Petit, Matthieu; Hanbücken, Margrit; Baranova, Elena A; Santinacci, Lionel

    2014-01-01

    Three-dimensionally (3D) nanoarchitectured palladium/nickel (Pd/Ni) catalysts, which were prepared by atomic layer deposition (ALD) on high-aspect-ratio nanoporous alumina templates are investigated with regard to the electrooxidation of formic acid in an acidic medium (0.5 M H2SO4). Both deposition processes, Ni and Pd, with various mass content ratios have been continuously monitored by using a quartz crystal microbalance. The morphology of the Pd/Ni systems has been studied by electron microscopy and shows a homogeneous deposition of granularly structured Pd onto the Ni substrate. X-ray diffraction analysis performed on Ni and NiO substrates revealed an amorphous structure, while the Pd coating crystallized into a fcc lattice with a preferential orientation along the [220]-direction. Surface chemistry analysis by X-ray photoelectron spectroscopy showed both metallic and oxide contributions for the Ni and Pd deposits. Cyclic voltammetry of the Pd/Ni nanocatalysts revealed that the electrooxidation of HCOOH proceeds through the direct dehydrogenation mechanism with the formation of active intermediates. High catalytic activities are measured for low masses of Pd coatings that were generated by a low number of ALD cycles, probably because of the cluster size effect, electronic interactions between Pd and Ni, or diffusion effects.

  10. 3D-nanoarchitectured Pd/Ni catalysts prepared by atomic layer deposition for the electrooxidation of formic acid

    PubMed Central

    Assaud, Loïc; Monyoncho, Evans; Pitzschel, Kristina; Allagui, Anis; Petit, Matthieu; Hanbücken, Margrit

    2014-01-01

    Summary Three-dimensionally (3D) nanoarchitectured palladium/nickel (Pd/Ni) catalysts, which were prepared by atomic layer deposition (ALD) on high-aspect-ratio nanoporous alumina templates are investigated with regard to the electrooxidation of formic acid in an acidic medium (0.5 M H2SO4). Both deposition processes, Ni and Pd, with various mass content ratios have been continuously monitored by using a quartz crystal microbalance. The morphology of the Pd/Ni systems has been studied by electron microscopy and shows a homogeneous deposition of granularly structured Pd onto the Ni substrate. X-ray diffraction analysis performed on Ni and NiO substrates revealed an amorphous structure, while the Pd coating crystallized into a fcc lattice with a preferential orientation along the [220]-direction. Surface chemistry analysis by X-ray photoelectron spectroscopy showed both metallic and oxide contributions for the Ni and Pd deposits. Cyclic voltammetry of the Pd/Ni nanocatalysts revealed that the electrooxidation of HCOOH proceeds through the direct dehydrogenation mechanism with the formation of active intermediates. High catalytic activities are measured for low masses of Pd coatings that were generated by a low number of ALD cycles, probably because of the cluster size effect, electronic interactions between Pd and Ni, or diffusion effects. PMID:24605281

  11. Theoretical Modeling of Formic Acid (HCOOH), Formate (HCOO(-)), and Ammonia (NH(4)) Vibrational Spectra in Astrophysical Ices

    NASA Technical Reports Server (NTRS)

    Park, Jin-Young; Woon, David E.

    2006-01-01

    Ions embedded in icy grain mantles are thought to account for various observed infrared spectroscopic features, particularly in certain young stellar objects. The dissociation of formic acid (HCOOH) in astrophysical ices to form the formate ion (HCOO(-)) was modeled with density functional theory cluster calculations. Like isocyanic acid (HOCN), HCOOH was found to spontaneously deprotonate when sufficient water is present to stabilize charge transfer complexes. Both ammonia and water can serve as proton acceptors, yielding ammonium (NH4(+)) and hydronium (H3O(+)) counterions. Computed frequencies of weak infrared features produced by stretching and bending modes in both HCOO(-) and HCOOH were compared with experimental and astronomical data. Our results confirm laboratory assignments that a band at 1381 cm(exp -1) can be attributed to the CH bend in either HCOO(-) or HCOOH, but a band at 1349 cm(exp -1) corresponds to CO stretching in HCOO(-). Another feature at 1710 cm(exp -1) (5.85 m) can possibly be assigned to a CO stretching mode in HCOOH, as suggested by experiment, but the agreement is less satisfactory. In addition, we examine and analyze spectroscopic features associated with NH+4, both as a counterion to HCOO(-) or OCN(-) and in isolation, in order to compare with experimental and astronomical data in the 7 m region.

  12. 3D-nanoarchitectured Pd/Ni catalysts prepared by atomic layer deposition for the electrooxidation of formic acid.

    PubMed

    Assaud, Loïc; Monyoncho, Evans; Pitzschel, Kristina; Allagui, Anis; Petit, Matthieu; Hanbücken, Margrit; Baranova, Elena A; Santinacci, Lionel

    2014-01-01

    Three-dimensionally (3D) nanoarchitectured palladium/nickel (Pd/Ni) catalysts, which were prepared by atomic layer deposition (ALD) on high-aspect-ratio nanoporous alumina templates are investigated with regard to the electrooxidation of formic acid in an acidic medium (0.5 M H2SO4). Both deposition processes, Ni and Pd, with various mass content ratios have been continuously monitored by using a quartz crystal microbalance. The morphology of the Pd/Ni systems has been studied by electron microscopy and shows a homogeneous deposition of granularly structured Pd onto the Ni substrate. X-ray diffraction analysis performed on Ni and NiO substrates revealed an amorphous structure, while the Pd coating crystallized into a fcc lattice with a preferential orientation along the [220]-direction. Surface chemistry analysis by X-ray photoelectron spectroscopy showed both metallic and oxide contributions for the Ni and Pd deposits. Cyclic voltammetry of the Pd/Ni nanocatalysts revealed that the electrooxidation of HCOOH proceeds through the direct dehydrogenation mechanism with the formation of active intermediates. High catalytic activities are measured for low masses of Pd coatings that were generated by a low number of ALD cycles, probably because of the cluster size effect, electronic interactions between Pd and Ni, or diffusion effects. PMID:24605281

  13. Acetic acid enhances endurance capacity of exercise-trained mice by increasing skeletal muscle oxidative properties.

    PubMed

    Pan, Jeong Hoon; Kim, Jun Ho; Kim, Hyung Min; Lee, Eui Seop; Shin, Dong-Hoon; Kim, Seongpil; Shin, Minkyeong; Kim, Sang Ho; Lee, Jin Hyup; Kim, Young Jun

    2015-01-01

    Acetic acid has been shown to promote glycogen replenishment in skeletal muscle during exercise training. In this study, we investigated the effects of acetic acid on endurance capacity and muscle oxidative metabolism in the exercise training using in vivo mice model. In exercised mice, acetic acid induced a significant increase in endurance capacity accompanying a reduction in visceral adipose depots. Serum levels of non-esterified fatty acid and urea nitrogen were significantly lower in acetic acid-fed mice in the exercised mice. Importantly, in the mice, acetic acid significantly increased the muscle expression of key enzymes involved in fatty acid oxidation and glycolytic-to-oxidative fiber-type transformation. Taken together, these findings suggest that acetic acid improves endurance exercise capacity by promoting muscle oxidative properties, in part through the AMPK-mediated fatty acid oxidation and provide an important basis for the application of acetic acid as a major component of novel ergogenic aids.

  14. 40 CFR 180.1258 - Acetic acid; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 24 2014-07-01 2014-07-01 false Acetic acid; exemption from the... Exemptions From Tolerances § 180.1258 Acetic acid; exemption from the requirement of a tolerance. (a) An... acetic acid when used as a preservative on post-harvest agricultural commodities intended for animal...

  15. Acetic Acid bacteria: physiology and carbon sources oxidation.

    PubMed

    Mamlouk, Dhouha; Gullo, Maria

    2013-12-01

    Acetic acid bacteria (AAB) are obligately aerobic bacteria within the family Acetobacteraceae, widespread in sugary, acidic and alcoholic niches. They are known for their ability to partially oxidise a variety of carbohydrates and to release the corresponding metabolites (aldehydes, ketones and organic acids) into the media. Since a long time they are used to perform specific oxidation reactions through processes called "oxidative fermentations", especially in vinegar production. In the last decades physiology of AAB have been widely studied because of their role in food production, where they act as beneficial or spoiling organisms, and in biotechnological industry, where their oxidation machinery is exploited to produce a number of compounds such as l-ascorbic acid, dihydroxyacetone, gluconic acid and cellulose. The present review aims to provide an overview of AAB physiology focusing carbon sources oxidation and main products of their metabolism.

  16. Morphological diversity of Blastocystis hominis in sodium acetate-acetic acid-formalin-preserved stool samples stained with iron hematoxylin.

    PubMed

    MacPherson, D W; MacQueen, W M

    1994-01-01

    The objective of this investigation was to study the morphological characteristics of Blastocystis hominis in sodium acetate-acetic acid-Formalin-preserved stool samples. Routinely processed samples were examined for morphological detail, including size, shape, nuclear detail, and central body characteristics. Morphological findings revealing the importance of recognizing B. hominis in the diagnostic laboratory are described. PMID:7510311

  17. 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.

  18. 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. PMID:25575969

  19. A first-principles study on the effect of phosphorus-doped palladium catalyst for formic acid dissociation

    NASA Astrophysics Data System (ADS)

    He, Feng; Li, Kai; Yin, Cong; Wang, Ying; Jiao, Menggai; Tang, Hao; Wu, Zhijian

    2016-11-01

    The effect of phosphorus-doped Pd(111) catalyst for the formic acid (HCOOH) dissociation has been investigated by using the density functional theory. The adsorption configurations and active sites of the intermediates involved in the HCOOH dissociation on the Pd/P(111) surface are studied. Our results showed that the doping of P on Pd catalyst could strengthen the adsorption of the intermediates. The Pd/P(111) catalyst exhibits higher catalytic activity by the easy formation of CO2 and H2 compared with the Pd(111) catalyst. The dominant HCOOH dissociation product on Pd/P(111) surface is CO2 rather than CO. Based on the computational hydrogen electrode (CHE) model, we found that CO formation is unfavorable on Pd/P(111) under the anode potential condition compared with the Pd(111) catalyst. Furthermore, the microkinetic analysis based on the DFT calculations showed that at high temperatures, the HCOOH dissociation is disfavored on the Pd/P(111) surface.

  20. Highly efficient and autocatalytic H2O dissociation for CO2 reduction into formic acid with zinc

    NASA Astrophysics Data System (ADS)

    Jin, Fangming; Zeng, Xu; Liu, Jianke; Jin, Yujia; Wang, Lunying; Zhong, Heng; Yao, Guodong; Huo, Zhibao

    2014-03-01

    Artificial photosynthesis, specifically H2O dissociation for CO2 reduction with solar energy, is regarded as one of the most promising methods for sustainable energy and utilisation of environmental resources. However, a highly efficient conversion still remains extremely challenging. The hydrogenation of CO2 is regarded as the most commercially feasible method, but this method requires either exotic catalysts or high-purity hydrogen and hydrogen storage, which are regarded as an energy-intensive process. Here we report a highly efficient method of H2O dissociation for reducing CO2 into chemicals with Zn powder that produces formic acid with a high yield of approximately 80%, and this reaction is revealed for the first time as an autocatalytic process in which an active intermediate, ZnH- complex, serves as the active hydrogen. The proposed process can assist in developing a new concept for improving artificial photosynthetic efficiency by coupling geochemistry, specifically the metal-based reduction of H2O and CO2, with solar-driven thermochemistry for reducing metal oxide into metal.

  1. Preparation of Pd-Co-based nanocatalysts and their superior applications in formic acid decomposition and methanol oxidation.

    PubMed

    Qin, Yu-ling; Liu, Ya-cheng; Liang, Fei; Wang, Li-min

    2015-01-01

    Formic acid (FA) and methanol, as convenient hydrogen-containing materials, are most widely used for fuel cells. However, using suitable and low-cost catalysts to further improve their energy performance still is a matter of great significance. Herein, PdCo and PdCo@Pd nanocatalysts (NCs) are successfully prepared by the facile method. Pd 3d binding energy decreases due to the presence of Co. Consequently, PdCo@Pd NCs exhibit high catalytic activity and selectivity toward FA dehydrogenation at room temperature. The gas-generation rate at 30 min is 65.4 L h(-1)  g(-1) . PdCo/C has the worst catalytic performance in this reaction, despite the fact that it has a high gas-generation rate in the initial 30 min. Furthermore, both PdCo and PdCo@Pd NCs have enhanced electrocatalytic performance toward methanol oxidation. Their maximum currents are 966 and 1205 mA mg(-1) , respectively, which is much higher than monometallic Pd/C. PMID:25504901

  2. Deciphering visible light photoreductive conversion of CO2 to formic acid and methanol using waste prepared material.

    PubMed

    Zhang, Qian; Lin, Cheng-Fang; Chen, Bor-Yann; Ouyang, Tong; Chang, Chang-Tang

    2015-02-17

    As gradual increases in atmospheric CO2 and depletion of fossil fuels have raised considerable public concern in recent decades, utilizing the unlimited solar energy to convert CO2 to fuels (e.g., formic acid and methanol) apparently could simultaneously resolve these issues for sustainable development. However, due to the complicated characteristics of CO2 reduction, the mechanism has yet to be disclosed. To clarify the postulated pathway as mentioned in the literature, the technique of electron paramagnetic resonance (ESR) was implemented herein to confirm the mechanism and related pathways of CO2 reduction under visible light using graphene-TiO2 as catalyst. The findings indicated that CO(-•) radicals, as the main intermediates, were first detected herein to react with several hydrogen ions and electrons for the formation of CH3OH. For example, the generation of CO(-•) radicals is possibly the vital rate-controlling step for conversion of CO2 to methanol as hypothesized elsewhere. The kinetics behind the proposed mechanism was also determined in this study. The mechanism and kinetics could provide the in-depth understanding to the pathway of CO2 reduction and disclose system optimization of maximal conversion for further application.

  3. Au/Pd core-shell nanoparticles with varied hollow Au cores for enhanced formic acid oxidation

    NASA Astrophysics Data System (ADS)

    Hsu, Chiajen; Huang, Chienwen; Hao, Yaowu; Liu, Fuqiang

    2013-03-01

    A facile method has been developed to synthesize Au/Pd core-shell nanoparticles via galvanic replacement of Cu by Pd on hollow Au nanospheres. The unique nanoparticles were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, ultraviolet-visible spectroscopy, and electrochemical measurements. When the concentration of the Au solution was decreased, grain size of the polycrystalline hollow Au nanospheres was reduced, and the structures became highly porous. After the Pd shell formed on these Au nanospheres, the morphology and structure of the Au/Pd nanoparticles varied and hence significantly affected the catalytic properties. The Au/Pd nanoparticles synthesized with reduced Au concentrations showed higher formic acid oxidation activity (0.93 mA cm-2 at 0.3 V) than the commercial Pd black (0.85 mA cm-2 at 0.3 V), suggesting a promising candidate as fuel cell catalysts. In addition, the Au/Pd nanoparticles displayed lower CO-stripping potential, improved stability, and higher durability compared to the Pd black due to their unique core-shell structures tuned by Au core morphologies.

  4. Adsorption behaviors of monomer and dimer of formic acid on Pt(111) in the absence and presence of water.

    PubMed

    Qi, Yuanyuan; Zhu, Rongxiu; Zhang, Dongju

    2014-06-01

    By performing density functional theory (DFT) theory calculations, we studied the adsorption behaviors of the monomer and dimer of formic acid (HCOOH, FA) on the Pt(111) surface with and without the presence of water molecules. The monomer prefers to stand on the surface of Pt(111), and in the most stable adsorption configuration the carbonyl O of HCOOH binds to the atop site of a Pt atom and the hydroxyl H points asymmetrically to two neighboring Pt atoms. The dimer of HCOOH not only exists in the gas-phase but also on Pt(111) surface, and the eight-membered ring dimer is identified as the energetically most favorable dimeric structure of HCOOH both in gas-phase and on Pt(111) surface. With the presence of water molecules, both the monomer and dimer of HCOOH prefer to lie parallel to the surface so as to maximize the number of H-bonds to adjacent water molecules. These results indicate that water molecules significantly influence the initial adsorption manner of HCOOH and further its decomposition reactivity on Pt(111) surface. The present work shows the adsorption behavior of HCOOH dimer on Pt(111) for the first time and also gives several new adsorption configurations of the monomer that are not reported in literature. The theoretical results are expected to provide a valuable input to understand the reactivity of HCOOH on Pt(111). PMID:24827612

  5. Synergic Catalysis of PdCu Alloy Nanoparticles within a Macroreticular Basic Resin for Hydrogen Production from Formic Acid.

    PubMed

    Mori, Kohsuke; Tanaka, Hiromasa; Dojo, Masahiro; Yoshizawa, Kazunari; Yamashita, Hiromi

    2015-08-17

    Highly dispersed PdCu alloy nanoparticles have been successfully prepared within a macroreticular basic resin bearing N(CH3 )2 functional groups. This previously unappreciated combination of alloy is first proven to be responsible for the efficient production of high-purity H2 from formic acid (HCOOH) dehydrogenation for chemical hydrogen storage. By the addition of Cu, the electronically promoted Pd sites show significantly higher catalytic activity as well as a better tolerance towards CO poisoning as compared to their monometallic Pd counterparts. Experimental and DFT calculation studies revealed not only the synergic alloying effect but also cooperative action by the N(CH3 )2 groups within the resin play crucial roles in achieving exceptional catalytic performances. In addition to the advantages such as, facile preparation method, free of additives, recyclable without leaching of active component, and suppression of unfavorable CO formation less than 3 ppm, the present catalytic system is cost-effective because of the superior catalytic activity compared with that of well-established precious PdAg or PdAu catalysts. The present catalytic system is particularly desirable for an ideal hydrogen vector in terms of potential industrial application for fuel cells. PMID:26178687

  6. Gold supported on zirconia polymorphs for hydrogen generation from formic acid in base-free aqueous medium

    NASA Astrophysics Data System (ADS)

    Bi, Qing-Yuan; Lin, Jian-Dong; Liu, Yong-Mei; He, He-Yong; Huang, Fu-Qiang; Cao, Yong

    2016-10-01

    Formic acid (FA) has attracted considerable attention as a safe and convenient hydrogen storage material for renewable energy transformation. However, development of an efficient heterogeneous catalyst for selective FA decomposition for ultraclean H2 gas in the absence of any alkalis or additives under mild conditions remains a major challenge. Based on our previous work on Au/ZrO2 as a robust and efficient catalyst for FA dehydrogenation in amine system, we report here ZrO2 with different nanocrystal polymorphs supported Au nanoparticles can achieve near completion of FA dehydrogenation in base-free aqueous medium. Of significant importance is that an excellent rate of up to 81.8 L H2 gAu-1 h-1 in open system and highly pressurized gas of 5.9 MPa in closed one can be readily attained at 80 °C for Au/m-ZrO2. In situ diffuse reflectance infrared Fourier transform (DRIFT) and CO2-temperature programmed desorption (TPD) techniques revealed that Au/m-ZrO2 exhibits a higher density of surface basic sites than Au/t-ZrO2 and Au/a-ZrO2. Basic sites in surface can substantially facilitate crucial FA deprotonation process which appears to be a key factor for achieving high dehydrogenation activity. The H/D exchange between solvent of H2O and substrate of FA was observed by the kinetic isotope effect experiments.

  7. The effect of hydrogen peroxide concentration and solid loading on the fractionation of biomass in formic acid.

    PubMed

    Dussan, K; Girisuta, B; Haverty, D; Leahy, J J; Hayes, M H B

    2014-10-13

    This study investigated the fractionation of biomass using a decomposing mixture of hydrogen peroxide-formic acid as a pretreatment for the biorefining of Miscanthus × giganteus and of sugarcane bagasse. The main parameters investigated were the hydrogen peroxide concentration (2.5, 5.0 and 7.5 wt%) and biomass loading (5.0 and 10.0 wt%). At the highest hydrogen peroxide concentration used (7.5 wt%), the energy released by the decomposition of the H2O2 could heat the reaction mixture up to 180 °C in a short time (6-16 min). As a result, highly delignified pulps, with lignin removal as high as 92 wt%, were obtained. This delignification process also solubilised a significant amount of pentosan (82-98 wt%) from the initial biomass feedstock, and the resulting pulp had a high cellulosic content (92 wt%). The biomass loading only affected the reaction rate of hydrogen peroxide decomposition. Various analytical methods, including Fourier transform infrared spectroscopy, and thermogravimetric and elemental analyses, characterized the lignin obtained.

  8. Computational study of the process of hydrogen bond breaking: the case of the formamide-formic acid complex.

    PubMed

    Pacios, Luis F

    2006-11-15

    MP2/6-311++G(d,p) and B3LYP/6-311++G(d,p) quantum calculations are used to study the formamide-formic acid complex (FFAC), a system bound by two hydrogen bonds, N--H...O and O--H...O, that forms a bond ring at equilibrium. When the intermolecular separation between monomers R increases, this ring opens at a distance for which the weaker N--H...O bond breaks remaining the stronger O--H...O bond. The computational study characterizes that process addressing changes of interaction energy DeltaE, structure and properties of the electron density rho(r) as well as spatial distributions of rho(r), the electrostatic potential U(r), and the electron localization function eta(r). It is shown that the spatial derivatives of DeltaE, the topology of rho(r), and qualitative changes noticed in U(r) = 0 isocontours allow to identify a precise distance R for which one can say the N--H...O hydrogen bond has broken. Both levels of theory predict essentially the same changes of structure and electron properties associated to the process of breaking and virtually identical distances at which it takes place.

  9. Au/Pd core-shell nanoparticles with varied hollow Au cores for enhanced formic acid oxidation.

    PubMed

    Hsu, Chiajen; Huang, Chienwen; Hao, Yaowu; Liu, Fuqiang

    2013-03-01

    A facile method has been developed to synthesize Au/Pd core-shell nanoparticles via galvanic replacement of Cu by Pd on hollow Au nanospheres. The unique nanoparticles were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, ultraviolet-visible spectroscopy, and electrochemical measurements. When the concentration of the Au solution was decreased, grain size of the polycrystalline hollow Au nanospheres was reduced, and the structures became highly porous. After the Pd shell formed on these Au nanospheres, the morphology and structure of the Au/Pd nanoparticles varied and hence significantly affected the catalytic properties. The Au/Pd nanoparticles synthesized with reduced Au concentrations showed higher formic acid oxidation activity (0.93 mA cm-2 at 0.3 V) than the commercial Pd black (0.85 mA cm-2 at 0.3 V), suggesting a promising candidate as fuel cell catalysts. In addition, the Au/Pd nanoparticles displayed lower CO-stripping potential, improved stability, and higher durability compared to the Pd black due to their unique core-shell structures tuned by Au core morphologies.

  10. Au/Pd core-shell nanoparticles with varied hollow Au cores for enhanced formic acid oxidation

    PubMed Central

    2013-01-01

    A facile method has been developed to synthesize Au/Pd core-shell nanoparticles via galvanic replacement of Cu by Pd on hollow Au nanospheres. The unique nanoparticles were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, ultraviolet–visible spectroscopy, and electrochemical measurements. When the concentration of the Au solution was decreased, grain size of the polycrystalline hollow Au nanospheres was reduced, and the structures became highly porous. After the Pd shell formed on these Au nanospheres, the morphology and structure of the Au/Pd nanoparticles varied and hence significantly affected the catalytic properties. The Au/Pd nanoparticles synthesized with reduced Au concentrations showed higher formic acid oxidation activity (0.93 mA cm-2 at 0.3 V) than the commercial Pd black (0.85 mA cm-2 at 0.3 V), suggesting a promising candidate as fuel cell catalysts. In addition, the Au/Pd nanoparticles displayed lower CO-stripping potential, improved stability, and higher durability compared to the Pd black due to their unique core-shell structures tuned by Au core morphologies. PMID:23452438

  11. One-step electrochemical synthesis of preferentially oriented (111) Pd nanocrystals supported on graphene nanoplatelets for formic acid electrooxidation

    NASA Astrophysics Data System (ADS)

    Chen, Qing-Song; Xu, Zhong-Ning; Peng, Si-Yan; Chen, Yu-Min; Lv, Dong-Mei; Wang, Zhi-Qiao; Sun, Jing; Guo, Guo-Cong

    2015-05-01

    Pd nanocrystals supported on graphene nanoplatelets (Pd/GNP) have been successfully synthesized by simultaneously electrochemical milling of Pd wire and graphite rod. It should be stressed that without the assistance of graphite rod, the Pd nanocrystals are unable to be obtained individually from Pd wire under the same conditions. Investigations of SEM and TEM demonstrate that Pd/GNP are preferentially decorated with (111) faceted nanocrystals. XPS studies confirm the strong metal-support interaction in Pd/GNP and reveal the surface is almost composed of Pd(0) species. Electrochemical measurements show that the prepared Pd based catalyst exhibits superior electrocatalytic activity towards formic acid oxidation, which may be attributed to the combined effects involving the preferentially oriented (111) surface structure, specific electronic structure and high dispersion of Pd nanocrystals as well as the support effects of graphene nanoplatelets. The synthesis method is simple and effective to prepare excellent new carbon-supported electrocatalysts, which is of great significance for direct organic molecule fuel cell.

  12. Deciphering visible light photoreductive conversion of CO2 to formic acid and methanol using waste prepared material.

    PubMed

    Zhang, Qian; Lin, Cheng-Fang; Chen, Bor-Yann; Ouyang, Tong; Chang, Chang-Tang

    2015-02-17

    As gradual increases in atmospheric CO2 and depletion of fossil fuels have raised considerable public concern in recent decades, utilizing the unlimited solar energy to convert CO2 to fuels (e.g., formic acid and methanol) apparently could simultaneously resolve these issues for sustainable development. However, due to the complicated characteristics of CO2 reduction, the mechanism has yet to be disclosed. To clarify the postulated pathway as mentioned in the literature, the technique of electron paramagnetic resonance (ESR) was implemented herein to confirm the mechanism and related pathways of CO2 reduction under visible light using graphene-TiO2 as catalyst. The findings indicated that CO(-•) radicals, as the main intermediates, were first detected herein to react with several hydrogen ions and electrons for the formation of CH3OH. For example, the generation of CO(-•) radicals is possibly the vital rate-controlling step for conversion of CO2 to methanol as hypothesized elsewhere. The kinetics behind the proposed mechanism was also determined in this study. The mechanism and kinetics could provide the in-depth understanding to the pathway of CO2 reduction and disclose system optimization of maximal conversion for further application. PMID:25612092

  13. Highly efficient and autocatalytic H2O dissociation for CO2 reduction into formic acid with zinc

    PubMed Central

    Jin, Fangming; Zeng, Xu; Liu, Jianke; Jin, Yujia; Wang, Lunying; Zhong, Heng; Yao, Guodong; Huo, Zhibao

    2014-01-01

    Artificial photosynthesis, specifically H2O dissociation for CO2 reduction with solar energy, is regarded as one of the most promising methods for sustainable energy and utilisation of environmental resources. However, a highly efficient conversion still remains extremely challenging. The hydrogenation of CO2 is regarded as the most commercially feasible method, but this method requires either exotic catalysts or high-purity hydrogen and hydrogen storage, which are regarded as an energy-intensive process. Here we report a highly efficient method of H2O dissociation for reducing CO2 into chemicals with Zn powder that produces formic acid with a high yield of approximately 80%, and this reaction is revealed for the first time as an autocatalytic process in which an active intermediate, ZnH− complex, serves as the active hydrogen. The proposed process can assist in developing a new concept for improving artificial photosynthetic efficiency by coupling geochemistry, specifically the metal-based reduction of H2O and CO2, with solar-driven thermochemistry for reducing metal oxide into metal. PMID:24675820

  14. Distinct Effects of Sorbic Acid and Acetic Acid on the Electrophysiology and Metabolism of Bacillus subtilis

    PubMed Central

    van Beilen, J. W. A.; Teixeira de Mattos, M. J.; Hellingwerf, K. J.

    2014-01-01

    Sorbic acid and acetic acid are among the weak organic acid preservatives most commonly used to improve the microbiological stability of foods. They have similar pKa values, but sorbic acid is a far more potent preservative. Weak organic acids are most effective at low pH. Under these circumstances, they are assumed to diffuse across the membrane as neutral undissociated acids. We show here that the level of initial intracellular acidification depends on the concentration of undissociated acid and less on the nature of the acid. Recovery of the internal pH depends on the presence of an energy source, but acidification of the cytosol causes a decrease in glucose flux. Furthermore, sorbic acid is a more potent uncoupler of the membrane potential than acetic acid. Together these effects may also slow the rate of ATP synthesis significantly and may thus (partially) explain sorbic acid's effectiveness. PMID:25038097

  15. Gas-Phase Structures of Ketene and Acetic Acid from Acetic Anhydride Using Very-High-Temperature Gas Electron Diffraction.

    PubMed

    Atkinson, Sandra J; Noble-Eddy, Robert; Masters, Sarah L

    2016-03-31

    The gas-phase molecular structure of ketene has been determined using samples generated by the pyrolysis of acetic anhydride (giving acetic acid and ketene), using one permutation of the very-high-temperature (VHT) inlet nozzle system designed and constructed for the gas electron diffraction (GED) apparatus based at the University of Canterbury. The gas-phase structures of acetic anhydride, acetic acid, and ketene are presented and compared to previous electron diffraction and microwave spectroscopy data to show improvements in data extraction and manipulation with current methods. Acetic anhydride was modeled with two conformers, rather than a complex dynamic model as in the previous study, to allow for inclusion of multiple pyrolysis products. The redetermined gas-phase structure of acetic anhydride (obtained using the structure analysis restrained by ab initio calculations for electron diffraction method) was compared to that from the original study, providing an improvement on the description of the low vibrational torsions compared to the dynamic model. Parameters for ketene and acetic acid (both generated by the pyrolysis of acetic anhydride) were also refined with higher accuracy than previously reported in GED studies, with structural parameter comparisons being made to prior experimental and theoretical studies. PMID:26916368

  16. Gas-Phase Structures of Ketene and Acetic Acid from Acetic Anhydride Using Very-High-Temperature Gas Electron Diffraction.

    PubMed

    Atkinson, Sandra J; Noble-Eddy, Robert; Masters, Sarah L

    2016-03-31

    The gas-phase molecular structure of ketene has been determined using samples generated by the pyrolysis of acetic anhydride (giving acetic acid and ketene), using one permutation of the very-high-temperature (VHT) inlet nozzle system designed and constructed for the gas electron diffraction (GED) apparatus based at the University of Canterbury. The gas-phase structures of acetic anhydride, acetic acid, and ketene are presented and compared to previous electron diffraction and microwave spectroscopy data to show improvements in data extraction and manipulation with current methods. Acetic anhydride was modeled with two conformers, rather than a complex dynamic model as in the previous study, to allow for inclusion of multiple pyrolysis products. The redetermined gas-phase structure of acetic anhydride (obtained using the structure analysis restrained by ab initio calculations for electron diffraction method) was compared to that from the original study, providing an improvement on the description of the low vibrational torsions compared to the dynamic model. Parameters for ketene and acetic acid (both generated by the pyrolysis of acetic anhydride) were also refined with higher accuracy than previously reported in GED studies, with structural parameter comparisons being made to prior experimental and theoretical studies.

  17. MERCURY-NITRITE-RHODIUM-RUTHENIUM INTERACTIONS IN NOBLE METAL CATALYZED HYDROGEN GENERATION FROM FORMIC ACID DURING NUCLEAR WASTE PROCESSING AT THE SAVANNAH RIVER SITE - 136C

    SciTech Connect

    Koopman, D.; Pickenheim, B.; Lambert, D.; Newell, J; Stone, M.

    2009-09-02

    Chemical pre-treatment of radioactive waste at the Savannah River Site is performed to prepare the waste for vitrification into a stable waste glass form. During pre-treatment, compounds in the waste become catalytically active. Mercury, rhodium, and palladium become active for nitrite destruction by formic acid, while rhodium and ruthenium become active for catalytic conversion of formic acid into hydrogen and carbon dioxide. Nitrite ion is present during the maximum activity of rhodium, but is consumed prior to the activation of ruthenium. Catalytic hydrogen generation during pre-treatment can exceed radiolytic hydrogen generation by several orders of magnitude. Palladium and mercury impact the maximum catalytic hydrogen generation rates of rhodium and ruthenium by altering the kinetics of nitrite ion decomposition. New data are presented that illustrate the interactions of these various species.

  18. Effects of Soluble Lignin on the Formic Acid-Catalyzed Formation of Furfural: A Case Study for the Upgrading of Hemicellulose.

    PubMed

    Dussan, Karla; Girisuta, Buana; Lopes, Marystela; Leahy, James J; Hayes, Michael H B

    2016-03-01

    A comprehensive study is presented on the conversion of hemicellulose sugars in liquors obtained from the fractionation of Miscanthus, spruce bark, sawdust, and hemp by using formic acid. Experimental tests with varying temperature (130-170 °C), formic acid concentration (10-80 wt%), carbohydrate concentrations, and lignin separation were carried out, and experimental data were compared with predictions obtained by reaction kinetics developed in a previous study. The conversions of xylose and arabinose into furfural were inherently affected by the presence of polymeric soluble lignin, decreasing the maximum furfural yields observed experimentally by up to 24%. These results were also confirmed in synthetic mixtures of pentoses with Miscanthus and commercial alkali lignin. This observation was attributed to side reactions involving intermediate stable sugar species reacting with solubilized lignin during the conversion of xylose into furfural.

  19. Communication: Protonation process of formic acid from the ionization and fragmentation of dimers induced by synchrotron radiation in the valence region

    NASA Astrophysics Data System (ADS)

    Arruda, Manuela S.; Medina, Aline; Sousa, Josenilton N.; Mendes, Luiz A. V.; Marinho, Ricardo R. T.; Prudente, Frederico V.

    2016-04-01

    The ionization and fragmentation of monomers of organic molecules have been extensively studied in the gas phase using mass spectroscopy. In the spectra of these molecules it is possible to identify the presence of protonated cations, which have a mass-to-charge ratio one unit larger than the parent ion. In this work, we investigate this protonation process as a result of dimers photofragmentation. Experimental photoionization and photofragmentation results of doubly deuterated formic acid (DCOOD) in the gas phase by photons in the vacuum ultraviolet region are presented. The experiment was performed by using a time-of-flight mass spectrometer installed at the Brazilian Synchrotron Light Laboratory and spectra for different pressure values in the experimental chamber were obtained. The coupled cluster approach with single and double substitutions was employed to assist the experimental analysis. Results indicate that protonated formic acid ions are originated from dimer dissociation, and the threshold photoionization of (DCOOD)ṡD+ is also determined.

  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. 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.

  2. 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. PMID:25673654

  3. Indoor winter fumigation of Apis mellifera (Hymenoptera: Apidae) colonies infested with Varroa destructor (Acari: Varroidae) with formic acid is a potential control alternative in northern climates.

    PubMed

    Underwood, Robyn M; Currie, Robert W

    2004-04-01

    Formic acid treatment for the control of the ectoparasitic varroa mite, Varroa destructor Anderson & Trueman, infesting honey bee, Apis mellifera L., colonies is usually carried out as an in-hive outdoor treatment. This study examined the use of formic acid on wintered colonies kept indoors at 5 degrees C from 24 November 1999 to 24 March 2000. Colonies were placed in small treatment rooms that were not treated (control) or fumigated at three different concentrations of formic acid: low (mean 11.9 +/- 1.2 ppm), medium (mean 25.8 +/- 1.4 ppm), or high (mean 41.2 +/- 3.3 ppm), for 48 h on 22-24 January 2000. Queen bee, worker bee, and varroa mite mortality were monitored throughout the winter, and tracheal mite, Acarapis woodi (Rennie), prevalence and mean abundance of nosema, Nosema apis Zander, spores were assessed. This study revealed that formic acid fumigation of indoor-wintered honey bees is feasible and effective. The highest concentration significantly reduced the mean abundance of varroa mites and nosema spores without increasing bee mortality. Tracheal mite prevalence did not change significantly at any concentration, although we did not measure mortality directly. The highest concentration treatment killed 33.3% of queens compared with 4.8% loss in the control. Repeated fumigation periods at high concentrations or extended fumigation at low concentrations may increase the efficacy of this treatment method and should be tested in future studies. An understanding of the cause of queen loss and methods to prevent it must be developed for this method to be generally accepted.

  4. 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.

  5. Use of Activated Carbon in Packaging to Attenuate Formaldehyde-Induced and Formic Acid-Induced Degradation and Reduce Gelatin Cross-Linking in Solid Dosage Forms.

    PubMed

    Colgan, Stephen T; Zelesky, Todd C; Chen, Raymond; Likar, Michael D; MacDonald, Bruce C; Hawkins, Joel M; Carroll, Sophia C; Johnson, Gail M; Space, J Sean; Jensen, James F; DeMatteo, Vincent A

    2016-07-01

    Formaldehyde and formic acid are reactive impurities found in commonly used excipients and can be responsible for limiting drug product shelf-life. Described here is the use of activated carbon in drug product packaging to attenuate formaldehyde-induced and formic acid-induced drug degradation in tablets and cross-linking in hard gelatin capsules. Several pharmaceutical products with known or potential vulnerabilities to formaldehyde-induced or formic acid-induced degradation or gelatin cross-linking were subjected to accelerated stability challenges in the presence and absence of activated carbon. The effects of time and storage conditions were determined. For all of the products studied, activated carbon attenuated drug degradation or gelatin cross-linking. This novel use of activated carbon in pharmaceutical packaging may be useful for enhancing the chemical stability of drug products or the dissolution stability of gelatin-containing dosage forms and may allow for the 1) extension of a drug product's shelf-life when the limiting attribute is a degradation product induced by a reactive impurity, 2) marketing of a drug product in hotter and more humid climatic zones than currently supported without the use of activated carbon, and 3) enhanced dissolution stability of products that are vulnerable to gelatin cross-linking.

  6. Pd and PdCo alloy nanoparticles supported on polypropylenimine dendrimer-grafted graphene: A highly efficient anodic catalyst for direct formic acid fuel cells

    NASA Astrophysics Data System (ADS)

    Hosseini, Hadi; Mahyari, Mojtaba; Bagheri, Akbar; Shaabani, Ahmad

    2014-02-01

    For the first time, Pd and PdCo alloy nanoparticles supported on polypropylenimine dendrimer-grafted graphene (Pd and PdCo/PPI-g-G) are prepared and characterized with Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The electrocatalytic activity of Pd and PdCo/PPI-g-G are investigated in terms of formic acid electrooxidation in H2SO4 aqueous solution. The PdCo/PPI-g-G shows much higher formic acid oxidation activities in comparison with Pd/PPI-g-G, and it is more resistant to the surface poisoning. This improved electrocatalytic performance may be due to the fine dispersion of PdCo alloy nanoparticles and bi-functional effect. The kinetic parameters such as charge transfer coefficient and the diffusion coefficient of formic acid are estimated under the quasi steady-state conditions.

  7. 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.

  8. Temperature dependence of hydrogen-bond dynamics in acetic acid-water solutions.

    PubMed

    D'Amico, Francesco; Bencivenga, Filippo; Gessini, Alessandro; Masciovecchio, Claudio

    2010-08-19

    An inelastic UV scattering experiment has been carried out on acetic acid-water solutions as a function of temperature and concentration. The analysis of experimental data indicates the presence of a crossover temperature (T(c) approximately 325 +/- 10 K). Above T(c), the energy of hydrogen bonds responsible for water-acetic acid and acetic acid-acetic acid interactions is strongly reduced. This leads to a reduction in the average number of water molecule interacting with acetic acid, as well as to a lower number of acetic acid clusters. The latter behavior can be mainly ascribed to a temperature change in the activation energy of carboxylic groups of acetic acid. These results may be also relevant to better understand the folding mechanism in protein-water solutions. PMID:20701390

  9. Oxidation of formic acid by oxyanions of chlorine and its implications to the Viking Labeled Release experiment

    NASA Astrophysics Data System (ADS)

    Martinez, P.; Navarro-gonzalez, R.

    2013-05-01

    The Viking Landers that arrived on Mars in 1976 carried out three biological experiments designed to investigate if there was microbial life. These were the Gas-Exchange, Pyrolitic Release and Labeled Release experiments. The three experiments yielded positive responses but the Labeled Release experiment had a kinetic response indicative of microbial activity. The experiment consisted of adding a broth of nutrients (formic acid, glycolic acid, glycine, D- and L-alanine and D- and L-lactic acid uniformly marked with 14C) to martian soil samples. The results were surprising; the nutrients were consumed releasing radioactive gases in a manner that is compatible by terrestrial microorganisms. The existence of Martian life was contradicted by soil chemical analysis that indicated the absence of organic compounds above the detection limits of parts per billion (ppb). Instead the positive response of the Labeled Release Experiment was attributed to the existence of peroxides and/or superoxides in the Martian soils that destroyed the nutrients upon contact. Recently, the Phoenix mission that landed in the Martian Arctic in 2008 revealed the presence of a highly oxidized form of the element chlorine in the soil: perchlorate. Perchlorate is thought to have formed in the Martian atmosphere by the oxidation of chloride from volcanic sources with ozone. Therefore perchlorate is formed by the stepwise oxidation of hypochlorite, chlorite and chlorate. These oxyanions of chlorine are powerful oxidizers that may exist in the Martian soil and may have reacted with the nutrients of the Labeled Release Experiment. This paper aims to better understand these results by designing experiments to determine the kinetics of decomposition of formic acid to carbon dioxide with different oxidized forms of chlorine by headspace technique in gas chromatography coupled to mass spectrometry (GC / MS). Previous studies done in the laboratory showed that only hypochlorite quantitatively reacted with

  10. FIRST ACETIC ACID SURVEY WITH CARMA IN HOT MOLECULAR CORES

    SciTech Connect

    Shiao, Y.-S. Jerry; Looney, Leslie W.; Snyder, Lewis E.; Friedel, Douglas N.; Remijan, Anthony J. E-mail: aremijan@nrao.ed

    2010-06-10

    Acetic acid (CH{sub 3}COOH) has been detected mainly in hot molecular cores where the distribution between oxygen (O) and nitrogen (N) containing molecular species is cospatial within the telescope beam. Previous work has presumed that similar cores with cospatial O and N species may be an indicator for detecting acetic acid. However, does this presumption hold as higher spatial resolution observations of large O- and N-containing molecules become available? As the number of detected acetic acid sources is still low, more observations are needed to support this postulate. In this paper, we report the first acetic acid survey conducted with the Combined Array for Research in Millimeter-wave Astronomy at 3 mm wavelengths toward G19.61-0.23, G29.96-0.02, and IRAS 16293-2422. We have successfully detected CH{sub 3}COOH via two transitions toward G19.61-0.23 and tentatively confirmed the detection toward IRAS 16293-2422 A. The determined column density of CH{sub 3}COOH is 2.0(1.0) x 10{sup 16} cm{sup -2} and the abundance ratio of CH{sub 3}COOH to methyl formate (HCOOCH{sub 3}) is 2.2(0.1) x 10{sup -1} toward G19.61-0.23. Toward IRAS 16293 A, the determined column density of CH{sub 3}COOH is {approx}1.6 x 10{sup 15} cm{sup -2} and the abundance ratio of CH{sub 3}COOH to methyl formate (HCOOCH{sub 3}) is {approx}1.0 x 10{sup -1}, both of which are consistent with abundance ratios determined toward other hot cores. Finally, we model all known line emission in our passband to determine physical conditions in the regions and introduce a new metric to better reveal weak spectral features that are blended with stronger lines or that may be near the 1{sigma}-2{sigma} detection limit.

  11. Kinetic Modeling of Esterification of Ethylene Glycol with Acetic Acid

    NASA Astrophysics Data System (ADS)

    Yadav, Vishnu P.; Mukherjee, Rudra Palash; Bantraj, Kandi; Maity, Sunil K.

    2010-10-01

    The reaction kinetics of the esterification of ethylene glycol with acetic acid in the presence of cation exchange resin has been studied and kinetic models based on empirical and Langmuir approach has been developed. The Langmuir based model involving eight kinetic parameters fits experimental data much better compared to empirical model involving four kinetic parameters. The effect of temperature and catalyst loading on the reaction system has been analyzed. Further, the activation energy and frequency factor of the rate constants for Langmuir based model has been estimated.

  12. Kinetic Modeling of Esterification of Ethylene Glycol with Acetic Acid

    SciTech Connect

    Yadav, Vishnu P.; Maity, Sunil K.; Mukherjee, Rudra Palash; Bantraj, Kandi

    2010-10-26

    The reaction kinetics of the esterification of ethylene glycol with acetic acid in the presence of cation exchange resin has been studied and kinetic models based on empirical and Langmuir approach has been developed. The Langmuir based model involving eight kinetic parameters fits experimental data much better compared to empirical model involving four kinetic parameters. The effect of temperature and catalyst loading on the reaction system has been analyzed. Further, the activation energy and frequency factor of the rate constants for Langmuir based model has been estimated.

  13. Radioiron utilization and gossypol acetic acid in male rats

    SciTech Connect

    Tone, J.N.; Jensen, D.R.

    1985-01-01

    The 24-h incorporation of VZFe into circulating red blood cells, bone marrow, urine, liver, spleen, and skeletal muscle was measured in splenectomized and sham-splenectomized rats which had received a daily, oral dose of gossypol acetic acid (20 mg GAA/kg body wt) for 91 days. A significant decrease in total body weight gain was observed in all GAA treated animals. Splenectomized rats dosed with GAA exhibited a significant decrease in hemoglobin concentration, hematocrit and erythrocyte count. A significant increase in VZFe incorporation by red blood cells and a decrease in hepatic incorporation of VZFe indicate a preferential utilization of iron in erythropoiesis among GAA treated animals.

  14. NTP technical report on the toxicity studies of Formic Acid (CAS No. 64-18-6) Administered by Inhalation to F344/N Rats and B6C3F1 Mice.

    PubMed

    Thompson, Morrow

    1992-07-01

    Formic acid occurs in a variety of plants and fruits, mammalian tissues, and insect venoms. It is used industrially in preparing a variety of drugs, dyes, and chemicals; as a decalcifier; and in leather tanning. Formic acid also is an environmental contaminant of air and water and has been identified as the toxic intermediate (formate) in methanol poisoning. Two- and 13-week toxicity studies of formic acid were conducted in male and female F344/N rats and B6C3F1 mice by whole body inhalation exposure to formic acid vapors. In addition, in vitro genetic toxicity studies were performed with Salmonella typhimurium, with or without metabolic activation. Formic acid was not mutagenic in this assay. In 2-week studies, groups of 5 F344/N rats and 5 B6C3F1 mice of each sex were exposed to formic acid for 6 hours a day, 5 days a week, at concentrations of 0, 31, 62.5, 125, 250, or 500 ppm. Deaths occurred in animals exposed to 500 ppm (rats and mice) and 250 ppm (1 female mouse). Microscopic lesions in the respiratory and olfactory epithelia occurred in rats and mice exposed to 62.5 ppm and higher concentrations, with the severity related to the exposure concentration. The lesions consisted of squamous metaplasia, necrosis, and inflammation. Exposures had minimal or no effects on coagulation times, blood pH and electrolytes, or on concentrations and activities of urine analytes in rats during the 2-week studies. In 13-week studies, groups of 10 animals of each species and sex were exposed to formic acid at concentrations of 0, 8, 16, 32, 64, and 128 ppm for 6 hours a day, 5 days a week. Two mice, 1 male and 1 female, died in the 128 ppm groups. Body weight gains were significantly decreased in mice exposed to 64 and 128 ppm formic acid. Microscopic changes in rats and mice ranged from minimal to mild in severity and generally were limited to animals in the 128 ppm groups. Lesions related to exposure to formic acid consisted of squamous metaplasia and degeneration of the

  15. Quantitative Structure of an Acetate Dye Molecule Analogue at the TiO2–Acetic Acid Interface

    PubMed Central

    2016-01-01

    The positions of atoms in and around acetate molecules at the rutile TiO2(110) interface with 0.1 M acetic acid have been determined with a precision of ±0.05 Å. Acetate is used as a surrogate for the carboxylate groups typically employed to anchor monocarboxylate dye molecules to TiO2 in dye-sensitized solar cells (DSSC). Structural analysis reveals small domains of ordered (2 × 1) acetate molecules, with substrate atoms closer to their bulk terminated positions compared to the clean UHV surface. Acetate is found in a bidentate bridge position, binding through both oxygen atoms to two 5-fold titanium atoms such that the molecular plane is along the [001] azimuth. Density functional theory calculations provide adsorption geometries in excellent agreement with experiment. The availability of these structural data will improve the accuracy of charge transport models for DSSC. PMID:27110318

  16. 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.

  17. 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. PMID:25698512

  18. On the primary emission of formic acid from light duty gasoline vehicles and ocean-going vessels

    NASA Astrophysics Data System (ADS)

    Crisp, Timia A.; Brady, James M.; Cappa, Christopher D.; Collier, Sonya; Forestieri, Sara D.; Kleeman, Michael J.; Kuwayama, Toshihiro; Lerner, Brian M.; Williams, Eric J.; Zhang, Qi; Bertram, Timothy H.

    2014-12-01

    We present determinations of fuel-based emission factors for formic acid (EFHCOOH) from light duty gasoline vehicles (LDGVs) and in-use ocean-going vessels. Emission ratios, from which the emission factors were derived, were determined from LDGVs through measurement of HCOOH and carbon dioxide (CO2) in the exhaust of a fleet of eight LDGVs driven under the California Unified Cycle at the California Air Resources Board's Haagen-Smit Laboratory. Emission ratios from in-use ocean-going vessels were determined through direct measurement of HCOOH and CO2 in ship plumes intercepted by the R/V Atlantis during the 2010 California Research at the Nexus of Air Quality and Climate Change (CalNex) campaign within 24 nautical miles of the California coast. The eight car fleet average EFHCOOH was 0.94 ± 0.32 (1σ) and 0.57 ± 0.18 mg (kg fuel)-1 for the cold start and hot running phases of the drive cycle, respectively. This difference suggests that catalytic converter performance and the air/fuel equivalence ratio are important metrics contributing to EFHCOOH. EFHCOOH was determined to be 1.94 ± 1.06 mg (kg fuel)-1 for a single diesel vehicle driven under highway driving conditions, higher on average than any individual LDGV tested. In comparison, HCOOH primary emissions from in-use ocean-going vessels were substantially larger, averaging 20.89 ± 8.50 mg (kg fuel)-1. On a global scale, HCOOH primary emissions from fossil fuel combustion are likely to be insignificant relative to secondary production mechanisms, however primary emissions may contribute more significantly on a finer, regional scale in urban locations.

  19. Acetobacter aceti possesses a proton motive force-dependent efflux system for acetic acid.

    PubMed

    Matsushita, Kazunobu; Inoue, Taketo; Adachi, Osao; Toyama, Hirohide

    2005-07-01

    Acetic acid bacteria are obligate aerobes able to oxidize ethanol, sugar alcohols, and sugars into their corresponding acids. Among them, Acetobacter and Gluconacetobacter species have very high ethanol oxidation capacity, leading to accumulation of vast amounts of acetic acid outside the cell. Since these bacteria are able to grow in media with high concentrations of acetic acid, they must possess a specific mechanism such as an efflux pump by which they can resist the toxic effects of acetic acid. In this study, the efflux pump of Acetobacter aceti IFO 3283 was examined using intact cells and membrane vesicles. The accumulation of acetic acid/acetate in intact cells was increased by the addition of a proton uncoupler and/or cyanide, suggesting the presence of an energy-dependent efflux system. To confirm this, right-side-out and inside-out membrane vesicles were prepared from A. aceti IFO 3283, and the accumulation of acetic acid/acetate in the vesicles was examined. Upon the addition of a respiratory substrate, the accumulation of acetic acid/acetate in the right-side-out vesicles was largely decreased, while its accumulation was very much increased in the inside-out vesicles. These respiration-dependent phenomena observed in both types of membrane vesicles were all sensitive to a proton uncoupler. Acetic acid/acetate uptake in the inside-out membrane vesicles was dependent not on ATP but on the proton motive force. Furthermore, uptake was shown to be rather specific for acetic acid and to be pH dependent, because higher uptake was observed at lower pH. Thus, A. aceti IFO 3283 possesses a proton motive force-dependent efflux pump for acetic acid.

  20. Oxidation of indole-3-acetic acid to oxindole-3-acetic acid by etiolated and green corn tissues

    SciTech Connect

    Reinecke, D. )

    1989-04-01

    Etiolated corn tissues oxidase indole-3-acetic acid (IAA) to oxindole-3-acetic acid (OxIAA). This oxidation results in loss of auxin activity and may plant a role in regulating IAA-stimulated growth. The enzyme has been partially purified and characterized and shown to require O{sub 2}, and a heat-stable lipid-soluble corn factor which can be replaced by linolenic or linoleic acids in the oxidation of IAA. Corn oil was tested as a cofactor in the IAA oxidation reaction. Corn oil stimulated enzyme activity by 30% while trilinolein was inactive. The capacity of green tissue to oxidize IAA was examined by incubating leaf sections from 2 week old light-grown corn seedlings with {sup 14}C-IAA. OxIAA and IAA were separated from other IAA metabolites on a 3 ml anion exchange column. Of the IAA taken up by the sections, 13% was oxidized to OxIAA. This is the first evidence that green tissue of corn may also regulate IAA levels by oxidizing IAA to OxIAA.

  1. Unusal pattern of product inhibition: batch acetic acid fermentation

    SciTech Connect

    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 behavior 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.

  2. Lactobionic and cellobionic acid production profiles of the resting cells of acetic acid bacteria.

    PubMed

    Kiryu, Takaaki; Kiso, Taro; Nakano, Hirofumi; Murakami, Hiromi

    2015-01-01

    Lactobionic acid was produced by acetic acid bacteria to oxidize lactose. Gluconobacter spp. and Gluconacetobacter spp. showed higher lactose-oxidizing activities than Acetobacter spp. Gluconobacter frateurii NBRC3285 produced the highest amount of lactobionic acid per cell, among the strains tested. This bacterium assimilated neither lactose nor lactobionic acid. At high lactose concentration (30%), resting cells of the bacterium showed sufficient oxidizing activity for efficient production of lactobionic acid. These properties may contribute to industrial production of lactobionic acid by the bacterium. The bacterium showed higher oxidizing activity on cellobiose than that on lactose and produced cellobionic acid. PMID:25965080

  3. Heterogeneous Reactions of Acetic Acid with Oxide Surfaces: Effects of Mineralogy and Relative Humidity.

    PubMed

    Tang, Mingjin; Larish, Whitney A; Fang, Yuan; Gankanda, Aruni; Grassian, Vicki H

    2016-07-21

    We have investigated the heterogeneous uptake of gaseous acetic acid on different oxides including γ-Al2O3, SiO2, and CaO under a range of relative humidity conditions. Under dry conditions, the uptake of acetic acid leads to the formation of both acetate and molecularly adsorbed acetic acid on γ-Al2O3 and CaO and only molecularly adsorbed acetic acid on SiO2. More importantly, under the conditions of this study, dimers are the major form for molecularly adsorbed acetic acid on all three particle surfaces investigated, even at low acetic acid pressures under which monomers are the dominant species in the gas phase. We have also determined saturation surface coverages for acetic acid adsorption on these three oxides under dry conditions as well as Langmuir adsorption constants in some cases. Kinetic analysis shows that the reaction rate of acetic acid increases by a factor of 3-5 for γ-Al2O3 when relative humidity increases from 0% to 15%, whereas for SiO2 particles, acetic acid and water are found to compete for surface adsorption sites. PMID:27322707

  4. Heterogeneous Reactions of Acetic Acid with Oxide Surfaces: Effects of Mineralogy and Relative Humidity.

    PubMed

    Tang, Mingjin; Larish, Whitney A; Fang, Yuan; Gankanda, Aruni; Grassian, Vicki H

    2016-07-21

    We have investigated the heterogeneous uptake of gaseous acetic acid on different oxides including γ-Al2O3, SiO2, and CaO under a range of relative humidity conditions. Under dry conditions, the uptake of acetic acid leads to the formation of both acetate and molecularly adsorbed acetic acid on γ-Al2O3 and CaO and only molecularly adsorbed acetic acid on SiO2. More importantly, under the conditions of this study, dimers are the major form for molecularly adsorbed acetic acid on all three particle surfaces investigated, even at low acetic acid pressures under which monomers are the dominant species in the gas phase. We have also determined saturation surface coverages for acetic acid adsorption on these three oxides under dry conditions as well as Langmuir adsorption constants in some cases. Kinetic analysis shows that the reaction rate of acetic acid increases by a factor of 3-5 for γ-Al2O3 when relative humidity increases from 0% to 15%, whereas for SiO2 particles, acetic acid and water are found to compete for surface adsorption sites.

  5. Benzylidene Acetal Protecting Group as Carboxylic Acid Surrogate: Synthesis of Functionalized Uronic Acids and Sugar Amino Acids.

    PubMed

    Banerjee, Amit; Senthilkumar, Soundararasu; Baskaran, Sundarababu

    2016-01-18

    Direct oxidation of the 4,6-O-benzylidene acetal protecting group to C-6 carboxylic acid has been developed that provides an easy access to a wide range of biologically important and synthetically challenging uronic acid and sugar amino acid derivatives in good yields. The RuCl3 -NaIO4 -mediated oxidative cleavage method eliminates protection and deprotection steps and the reaction takes place under mild conditions. The dual role of the benzylidene acetal, as a protecting group and source of carboxylic acid, was exploited in the efficient synthesis of six-carbon sialic acid analogues and disaccharides bearing uronic acids, including glycosaminoglycan analogues.

  6. Recent advances in nitrogen-fixing acetic acid bacteria.

    PubMed

    Pedraza, Raúl O

    2008-06-30

    Nitrogen is an essential plant nutrient, widely applied as N-fertilizer to improve yield of agriculturally important crops. An interesting alternative to avoid or reduce the use of N-fertilizers could be the exploitation of plant growth-promoting bacteria (PGPB), capable of enhancing growth and yield of many plant species, several of agronomic and ecological significance. PGPB belong to diverse genera, including Azospirillum, Azotobacter, Herbaspirillum, Bacillus, Burkholderia, Pseudomonas, Rhizobium, and Gluconacetobacter, among others. They are capable of promoting plant growth through different mechanisms including (in some cases), the biological nitrogen fixation (BNF), the enzymatic reduction of the atmospheric dinitrogen (N(2)) to ammonia, catalyzed by nitrogenase. Aerobic bacteria able to oxidize ethanol to acetic acid in neutral or acid media are candidates of belonging to the family Acetobacteraceae. At present, this family has been divided into ten genera: Acetobacter, Gluconacetobacter, Gluconobacter, Acidomonas, Asaia, Kozakia, Saccharibacter, Swaminathania, Neoasaia, and Granulibacter. Among them, only three genera include N(2)-fixing species: Gluconacetobacter, Swaminathania and Acetobacter. The first N(2)-fixing acetic acid bacterium (AAB) was described in Brazil. It was found inside tissues of the sugarcane plant, and first named as Acetobacter diazotrophicus, but then renamed as Gluconacetobacter diazotrophicus. Later, two new species within the genus Gluconacetobacter, associated to coffee plants, were described in Mexico: G. johannae and G. azotocaptans. A salt-tolerant bacterium named Swaminathania salitolerans was found associated to wild rice plants. Recently, N(2)-fixing Acetobacter peroxydans and Acetobacter nitrogenifigens, associated with rice plants and Kombucha tea, respectively, were described in India. In this paper, recent advances involving nitrogen-fixing AAB are presented. Their natural habitats, physiological and genetic aspects

  7. 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.

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

    SciTech Connect

    Mondala, Andro; Hernandez, Rafael; French, Todd; McFarland, Linda; Sparks, Darrell; Holmes, William; Haque, Monica

    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% 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.

  9. Transcript and metabolite alterations increase ganoderic acid content in Ganoderma lucidum using acetic acid as an inducer.

    PubMed

    Ren, Ang; Li, Xiong-Biao; Miao, Zhi-Gang; Shi, Liang; Jaing, Ai-Liang; Zhao, Ming-Wen

    2014-12-01

    Acetic acid at 5-8 mM increased ganoderic acid (GA) accumulation in Ganoderma lucidum. After optimization by the response surface methodology, the GA content reached 5.5/100 mg dry weight, an increase of 105% compared with the control. The intermediate metabolites of GA biosynthesis, lanosterol and squalene also increased to 47 and 15.8 μg/g dry weight, respectively, in response to acetic acid. Acetic acid significantly induced transcription levels of sqs, lano, hmgs and cyp51 in the GA biosynthesis pathway. An acetic acid-unregulated acetyl coenzyme A synthase (acs) gene was selected from ten candidate homologous acs genes. The results indicate that acetic acid alters the expression of genes related to acetic acid assimilation and increases GA biosynthesis and the metabolic levels of lanosterol, squalene and GA-a, thereby resulting in GA accumulation.

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

    SciTech Connect

    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 the 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.

  11. Leaching of spent lead acid battery paste components by sodium citrate and acetic acid.

    PubMed

    Zhu, Xinfeng; He, Xiong; Yang, Jiakuan; Gao, Linxia; Liu, Jianwen; Yang, Danni; Sun, Xiaojuan; Zhang, Wei; Wang, Qin; Kumar, R Vasant

    2013-04-15

    A sustainable method, with minimal pollution and low energy cost in comparison with the conventional smelting methods, is proposed for treating components of spent lead-acid battery pastes in aqueous organic acid(s). In this study, PbO, PbO2, and PbSO4, the three major components in a spent lead paste, were individually reacted with a mixture of aqueous sodium citrate and acetic acid solution. Pure lead citrate precursor of Pb3(C6H5O7)2 · 3H2O is the only product crystallized in each leaching experiment. Conditions were optimized for individual lead compounds which were then used as the basis for leaching real industrial spent paste. In this work, efficient leaching process is achieved and raw material cost is reduced by using aqueous sodium citrate and acetic acid, instead of aqueous sodium citrate and citric acid as reported in a pioneering hydrometallurgical method earlier. Acetic acid is not only cheaper than citric acid but is also more effective in aiding dissolution of the lead compounds thus speeding up the leaching process in comparison with citric acid. Lead citrate is readily crystallized from the aqueous solution due to its low solubility and can be combusted to directly produce leady oxide as a precursor for making new battery pastes.

  12. [Removal of tattoos by CO2 laser and acetic acid].

    PubMed

    Di Quirico, R; Pallini, G; Di Domenicantonio, G; Astolfi, A; Bindi, F; Gianfelice, F

    1992-10-31

    The Authors pay attention to small tattoo removal by means of the utilization of the CO2 laser. Moreover, the Authors emphasize the drawback of double treatment which, usually, the patient suffers in tattoo removal by CO2 laser. Then, the pressure of the Authors is small sized tattoo removal in only one sitting achieving so an excellent esthetic result. Besides, the Authors, in this medical study, explains two methods for tattoo removal. In the study's results, the Authors describes the manner and the time of the two lesion recovery by the different manners of treatment. Finally, the Authors affirms the great consequence of the surgical CO2 laser, they don't fail, however, to affirm that the laser and acetic acid combination is an excellent procedure for small tattoo removal. PMID:1480288

  13. Transcriptome analysis of acetic-acid-treated yeast cells identifies a large set of genes whose overexpression or deletion enhances acetic acid tolerance.

    PubMed

    Lee, Yeji; Nasution, Olviyani; Choi, Eunyong; Choi, In-Geol; Kim, Wankee; Choi, Wonja

    2015-08-01

    Acetic acid inhibits the metabolic activities of Saccharomyces cerevisiae. Therefore, a better understanding of how S. cerevisiae cells acquire the tolerance to acetic acid is of importance to develop robust yeast strains to be used in industry. To do this, we examined the transcriptional changes that occur at 12 h post-exposure to acetic acid, revealing that 56 and 58 genes were upregulated and downregulated, respectively. Functional categorization of them revealed that 22 protein synthesis genes and 14 stress response genes constituted the largest portion of the upregulated and downregulated genes, respectively. To evaluate the association of the regulated genes with acetic acid tolerance, 3 upregulated genes (DBP2, ASC1, and GND1) were selected among 34 non-protein synthesis genes, and 54 viable mutants individually deleted for the downregulated genes were retrieved from the non-essential haploid deletion library. Strains overexpressing ASC1 and GND1 displayed enhanced tolerance to acetic acid, whereas a strain overexpressing DBP2 was sensitive. Fifty of 54 deletion mutants displayed enhanced acetic acid tolerance. Three chosen deletion mutants (hsps82Δ, ato2Δ, and ssa3Δ) were also tolerant to benzoic acid but not propionic and sorbic acids. Moreover, all those five (two overexpressing and three deleted) strains were more efficient in proton efflux and lower in membrane permeability and internal hydrogen peroxide content than controls. Individually or in combination, those physiological changes are likely to contribute at least in part to enhanced acetic acid tolerance. Overall, information of our transcriptional profile was very useful to identify molecular factors associated with acetic acid tolerance.

  14. Formic acid enhanced effective degradation of methyl orange dye in aqueous solutions under UV-Vis irradiation.

    PubMed

    Wang, Jingjing; Bai, Renbi

    2016-09-15

    Developing efficient technologies to treat recalcitrant organic dye wastewater has long been of great research and practical interest. In this study, a small molecule, formic acid (FA), was applied as a process enhancer for the degradation of methyl orange (MO) dye as a model recalcitrant organic pollutant in aqueous solutions under the condition of UV-Vis light irradiation and air aeration at the ambient temperature of 25 °C. It was found that the decolouration of the dye solutions can be rapidly achieved, reducing the time, for example, from around 17.6 h without FA to mostly about less than 2 h with the presence of FA. The mineralization rate of MO dye reached as high as 81.8% in 1.5 h in the case of initial MO dye concentration at 25 mg L(-1), which is in contrast to nearly no mineralization of the MO dye for a similar system without the FA added. The study revealed that the generation of the H2O2 species in the system was enhanced and the produced OH radicals effectively contributed to the degradation of the MO dye. Process parameters such as the initial concentration of MO dye, FA dosage and solution pH were all found to have some effect on the degradation efficiency under the same condition of UV-Vis light irradiation and air aeration. The MO dye degradation performance was found to follow a first-order reaction rate to the MO dye concentration in most cases and there existed a positive correlation between the reaction rate constant and the initial FA concentration. Compared to the traditional H2O2/UV-Vis oxidation system, the use of FA as a process-enhancing agent can have the advantages of low cost, easy availability, and safe to use. The study hence demonstrates a promising approach to use a readily available small molecule of FA to enhance the degradation of recalcitrant organic pollutants, such as MO dye, especially for their pre-treatment. PMID:27258621

  15. 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.

  16. Temperature evolution of structure and bonding of formic acid and formate on fully oxidized and highly reduced CeO2(111)

    SciTech Connect

    Gordon, Wesley O; Xu, Ye; Mullins, David R; Overbury, Steven {Steve} H

    2009-01-01

    Adsorption of formate on oxide surfaces plays a role in water-gas shift (WGS) and other reactions related to H2 production and CO2 utilization. CeO2 is of particular interest because its reducibility affects the redox of organic molecules. In this work, the adsorption and thermal evolution of formic acid and formate on highly ordered films of fully oxidized CeO2(111) and highly reduced CeOx(111) surfaces have been studied using reflection absorption infrared spectroscopy (RAIRS) under ultra-high vacuum conditions, and the experimental results are combined with density functional theory (DFT) calculations to probe the identity, symmetry, and bonding of the surface intermediates. Disordered ice, ordered a-polymorph and molecular formic acid bonded through the carbonyl are observed at low temperatures. By 250 K, desorption and deprotonation lead to formate coexisting with hydroxyl on CeO2(111), identified to be a bridging bidentate formate species that is coordinated to Ce cations in nearly C2v symmetry and interacting strongly with neighboring H. Changes in the spectra at higher temperatures are consistent with additional tilting of the formate, resulting in Cs(2) or lower symmetry. This change in bonding is caused primarily by interaction with oxygen vacancies introduced by water desorption at 300 K. On reduced CeOx, multiple low-symmetry formate states exist likewise due to interactions with oxygen vacancies. Isotopic studies demonstrate that the formyl hydrogen does not contribute to H incorporated in hydroxyl on the surface, and that both formate oxygen atoms may exchange with lattice oxygen at 400 K. The combined experimental and theoretical results thus provide important insights on the surface reaction pathways of formic acid on ceria.

  17. Natural DNA-modified graphene/Pd nanoparticles as highly active catalyst for formic acid electro-oxidation and for the Suzuki reaction.

    PubMed

    Qu, Konggang; Wu, Li; Ren, Jinsong; Qu, Xiaogang

    2012-09-26

    Natural DNA has been considered as a building block for developing novel functional materials. It is abundant, renewable, and biodegradable and has a well-defined structure and conformation with many unique features, which are difficult to find in other polymers. Herein, calf thymus DNA modified graphene/Pd nanoparticle (DNA-G-Pd) hybrid materials are constructed for the first time using DNA as a mediator, and the prepared DNA-G-Pd hybrid shows high catalytic activity for fuel cell formic acid electro-oxidation and for organic Suzuki reaction. The main advantages of using DNA are not only because the aromatic nucleobases in DNA can interact through π-π stacking with graphene basal surface but also because they can chelate Pd via dative bonding in such defined sites along the DNA lattice. Our results indicate that isolated, homogeneous, and ultrafine spherical Pd nanoparticles are densely in situ decorated on DNA-modified graphene surfaces with high stability and dispersibility. The prepared DNA-G-Pd hybrid has much greater activity and durability for formic acid electro-oxidation than the commercial Pd/C catalyst and polyvinylpyrrolidone-mediated graphene/Pd nanoparticle (PVP-G-Pd) hybrid used for direct formic acid fuel cells (DFAFCs). Besides, the DNA-G-Pd hybrid can also be an efficient and recyclable catalyst for the organic Suzuki reaction in aqueous solution under aerobic conditions without any preactivation. Since DNA can chelate various transition metal cations, this proof-of-concept protocol provides the possibility for the tailored design of other novel catalytic materials based on graphene with full exploitation of their properties.

  18. Natural DNA-modified graphene/Pd nanoparticles as highly active catalyst for formic acid electro-oxidation and for the Suzuki reaction.

    PubMed

    Qu, Konggang; Wu, Li; Ren, Jinsong; Qu, Xiaogang

    2012-09-26

    Natural DNA has been considered as a building block for developing novel functional materials. It is abundant, renewable, and biodegradable and has a well-defined structure and conformation with many unique features, which are difficult to find in other polymers. Herein, calf thymus DNA modified graphene/Pd nanoparticle (DNA-G-Pd) hybrid materials are constructed for the first time using DNA as a mediator, and the prepared DNA-G-Pd hybrid shows high catalytic activity for fuel cell formic acid electro-oxidation and for organic Suzuki reaction. The main advantages of using DNA are not only because the aromatic nucleobases in DNA can interact through π-π stacking with graphene basal surface but also because they can chelate Pd via dative bonding in such defined sites along the DNA lattice. Our results indicate that isolated, homogeneous, and ultrafine spherical Pd nanoparticles are densely in situ decorated on DNA-modified graphene surfaces with high stability and dispersibility. The prepared DNA-G-Pd hybrid has much greater activity and durability for formic acid electro-oxidation than the commercial Pd/C catalyst and polyvinylpyrrolidone-mediated graphene/Pd nanoparticle (PVP-G-Pd) hybrid used for direct formic acid fuel cells (DFAFCs). Besides, the DNA-G-Pd hybrid can also be an efficient and recyclable catalyst for the organic Suzuki reaction in aqueous solution under aerobic conditions without any preactivation. Since DNA can chelate various transition metal cations, this proof-of-concept protocol provides the possibility for the tailored design of other novel catalytic materials based on graphene with full exploitation of their properties. PMID:22973944

  19. Synergistic catalysis of metal-organic framework-immobilized Au-Pd nanoparticles in dehydrogenation of formic acid for chemical hydrogen storage.

    PubMed

    Gu, Xiaojun; Lu, Zhang-Hui; Jiang, Hai-Long; Akita, Tomoki; Xu, Qiang

    2011-08-10

    Bimetallic Au-Pd nanoparticles (NPs) were successfully immobilized in the metal-organic frameworks (MOFs) MIL-101 and ethylenediamine (ED)-grafted MIL-101 (ED-MIL-101) using a simple liquid impregnation method. The resulting composites, Au-Pd/MIL-101 and Au-Pd/ED-MIL-101, represent the first highly active MOF-immobilized metal catalysts for the complete conversion of formic acid to high-quality hydrogen at a convenient temperature for chemical hydrogen storage. Au-Pd NPs with strong bimetallic synergistic effects have a much higher catalytic activity and a higher tolerance with respect to CO poisoning than monometallic Au and Pd counterparts. PMID:21761819

  20. Germanium(II) hydride mediated reduction of carbon dioxide to formic acid and methanol with ammonia borane as the hydrogen source.

    PubMed

    Jana, Anukul; Tavčar, Gašper; Roesky, Herbert W; John, Michael

    2010-10-28

    LGeOC(O)H (3) (L = CH{(CMe)(2,6-iPr(2)C(6)H(3)N)}(2)), from the straightforward conversion of LGeH (2) with CO(2), reacts with LiH(2)NBH(3) giving 2 and LiOC(O)H (4), while the corresponding reaction of 3 with H(3)NBH(3) after aqueous workup releases 2 and CH(3)OH (5). This opens the possibility to use hydride 2 as a mediator in the reduction of carbon dioxide to formic acid and methanol. PMID:20830405

  1. Germanium(II) hydride mediated reduction of carbon dioxide to formic acid and methanol with ammonia borane as the hydrogen source.

    PubMed

    Jana, Anukul; Tavčar, Gašper; Roesky, Herbert W; John, Michael

    2010-10-28

    LGeOC(O)H (3) (L = CH{(CMe)(2,6-iPr(2)C(6)H(3)N)}(2)), from the straightforward conversion of LGeH (2) with CO(2), reacts with LiH(2)NBH(3) giving 2 and LiOC(O)H (4), while the corresponding reaction of 3 with H(3)NBH(3) after aqueous workup releases 2 and CH(3)OH (5). This opens the possibility to use hydride 2 as a mediator in the reduction of carbon dioxide to formic acid and methanol.

  2. Enhanced expression of aconitase raises acetic acid resistance in Acetobacter aceti.

    PubMed

    Nakano, Shigeru; Fukaya, Masahiro; Horinouchi, Sueharu

    2004-06-15

    Acetobacter spp. are used for industrial vinegar production because of their high ability to oxidize ethanol to acetic acid and high resistance to acetic acid. Two-dimensional gel electrophoretic analysis of a soluble fraction of Acetobacter aceti revealed the presence of several proteins whose production was enhanced, to various extents, in response to acetic acid in the medium. A protein with an apparent molecular mass of 100 kDa was significantly enhanced in amount by acetic acid and identified to be aconitase by NH2-terminal amino acid sequencing and subsequent gene cloning. Amplification of the aconitase gene by use of a multicopy plasmid in A. aceti enhanced the enzymatic activity and acetic acid resistance. These results showed that aconitase is concerned with acetic acid resistance. Enhancement of the aconitase activity turned out to be practically useful for acetic acid fermentation, because the A. aceti transformant harboring multiple copies of the aconitase gene produced a higher concentration of acetic acid with a reduced growth lag-time.

  3. [Advances in functional genomics studies underlying acetic acid tolerance of Saccharomyces cerevisiae].

    PubMed

    Zhao, Xinqing; Zhang, Mingming; Xu, Guihong; Xu, Jianren; Bai, Fengwu

    2014-03-01

    Industrial microorganisms are subject to various stress conditions, including products and substrates inhibitions. Therefore, improvement of stress tolerance is of great importance for industrial microbial production. Acetic acid is one of the major inhibitors in the cellulosic hydrolysates, which affects seriously on cell growth and metabolism of Saccharomyces cerevisiae. Studies on the molecular mechanisms underlying adaptive response and tolerance of acetic acid of S. cerevisiae benefit breeding of robust strains of industrial yeast for more efficient production. In recent years, more insights into the molecular mechanisms underlying acetic acid tolerance have been revealed through analysis of global gene expression and metabolomics analysis, as well as phenomics analysis by single gene deletion libraries. Novel genes related to response to acetic acid and improvement of acetic acid tolerance have been identified, and novel strains with improved acetic acid tolerance were constructed by modifying key genes. Metal ions including potassium and zinc play important roles in acetic acid tolerance in S. cerevisiae, and the effect of zinc was first discovered in our previous studies on flocculating yeast. Genes involved in cell wall remodeling, membrane transport, energy metabolism, amino acid biosynthesis and transport, as well as global transcription regulation were discussed. Exploration and modification of the molecular mechanisms of yeast acetic acid tolerance will be done further on levels such as post-translational modifications and synthetic biology and engineering; and the knowledge obtained will pave the way for breeding robust strains for more efficient bioconversion of cellulosic materials to produce biofuels and bio-based chemicals.

  4. 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.

  5. Phenyl Acetate Preparation from Phenol and Acetic Acid: Reassessment of a Common Textbook Misconception.

    ERIC Educational Resources Information Center

    Hocking, M. B.

    1980-01-01

    Reassesses a common textbook misconception that "...phenols cannot be esterified directly." Results of experiments are discussed and data tables provided of an effective method for the direct preparation of phenyl acetate. (CS)

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

    PubMed Central

    2010-01-01

    Background 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. Results 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. Conclusions 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

  7. Electromembrane extraction and HPLC analysis of haloacetic acids and aromatic acetic acids in wastewater.

    PubMed

    Alhooshani, Khalid; Basheer, Chanbasha; Kaur, Jagjit; Gjelstad, Astrid; Rasmussen, Knut E; Pedersen-Bjergaard, Stig; Lee, Hian Kee

    2011-10-30

    For the first time, haloacetic acids and aromatic acetic acids were extracted from wastewater samples using electromembrane extraction (EME). A thin layer of toluene immobilized on the walls of a polypropylene membrane envelope served as an artificial supported liquid membrane (SLM). The haloacetic acids (HAAs) (chloroacetic acid, dichloroacetic acid, and trifluoroacetic acid) and aromatic acetic acids (phenylacetic acid and p-hydroxyphenylacetic acid) were extracted through the SLM and into an alkalized aqueous buffer solution. The buffer solution was located inside the membrane envelope. The electrical potential difference sustained over the membrane acted as the driving force for the transport of haloacetic acids into the membrane by electrokinetic migration. After extraction, the extracts were analyzed by high-performance liquid chromatography-ultraviolet detection. The detection limits were between 0.072 and 40.3 ng L(-1). The calibration plot linearity was in the range of 5 and 200 μg L(-1) while the correlation coefficients for the analytes ranged from 0.9932 to 0.9967. Relative recoveries were in the range of 87-106%. The extraction efficiency was found to be comparable to that of solid-phase extraction.

  8. A Binary Host Plant Volatile Lure Combined With Acetic Acid to Monitor Codling Moth (Lepidoptera: Tortricidae).

    PubMed

    Knight, A L; Basoalto, E; Katalin, J; El-Sayed, A M

    2015-10-01

    Field studies were conducted in the United States, Hungary, and New Zealand to evaluate the effectiveness of septa lures loaded with ethyl (E,Z)-2,4-decadienoate (pear ester) and (E)-4,8-dimethyl-1,3,7-nonatriene (nonatriene) alone and in combination with an acetic acid co-lure for both sexes of codling moth, Cydia pomonella (L.). Additional studies were conducted to evaluate these host plant volatiles and acetic acid in combination with the sex pheromone, (E,E)-8,10-dodecadien-1-ol (codlemone). Traps baited with pear ester/nonatriene + acetic acid placed within orchards treated either with codlemone dispensers or left untreated caught significantly more males, females, and total moths than similar traps baited with pear ester + acetic acid in some assays. Similarly, traps baited with codlemone/pear ester/nonatriene + acetic acid caught significantly greater numbers of moths than traps with codlemone/pear ester + acetic acid lures in some assays in orchards treated with combinational dispensers (dispensers loaded with codlemone/pear ester). These data suggest that monitoring of codling moth can be marginally improved in orchards under variable management plans using a binary host plant volatile lure in combination with codlemone and acetic acid. These results are likely to be most significant in orchards treated with combinational dispensers. Significant increases in the catch of female codling moths in traps with the binary host plant volatile blend plus acetic acid should be useful in developing more effective mass trapping strategies.

  9. A Binary Host Plant Volatile Lure Combined With Acetic Acid to Monitor Codling Moth (Lepidoptera: Tortricidae).

    PubMed

    Knight, A L; Basoalto, E; Katalin, J; El-Sayed, A M

    2015-10-01

    Field studies were conducted in the United States, Hungary, and New Zealand to evaluate the effectiveness of septa lures loaded with ethyl (E,Z)-2,4-decadienoate (pear ester) and (E)-4,8-dimethyl-1,3,7-nonatriene (nonatriene) alone and in combination with an acetic acid co-lure for both sexes of codling moth, Cydia pomonella (L.). Additional studies were conducted to evaluate these host plant volatiles and acetic acid in combination with the sex pheromone, (E,E)-8,10-dodecadien-1-ol (codlemone). Traps baited with pear ester/nonatriene + acetic acid placed within orchards treated either with codlemone dispensers or left untreated caught significantly more males, females, and total moths than similar traps baited with pear ester + acetic acid in some assays. Similarly, traps baited with codlemone/pear ester/nonatriene + acetic acid caught significantly greater numbers of moths than traps with codlemone/pear ester + acetic acid lures in some assays in orchards treated with combinational dispensers (dispensers loaded with codlemone/pear ester). These data suggest that monitoring of codling moth can be marginally improved in orchards under variable management plans using a binary host plant volatile lure in combination with codlemone and acetic acid. These results are likely to be most significant in orchards treated with combinational dispensers. Significant increases in the catch of female codling moths in traps with the binary host plant volatile blend plus acetic acid should be useful in developing more effective mass trapping strategies. PMID:26314018

  10. Evidence for a Complex Between Thf and Acetic Acid from Broadband Rotational Spectroscopy

    NASA Astrophysics Data System (ADS)

    Zaleski, Daniel P.; Bittner, Dror M.; Mullaney, John Connor; Stephens, Susanna L.; King, Adrian; Habgood, Matthew; Walker, Nick

    2015-06-01

    Evidence for a complex between tetrahydrofuran (THF) and acetic acid from broadband rotational spectroscopy will be presented. Transitions believed to belong to the complex were first identified in a gas mixture containing small amounts of THF, triethyl borane, and acetic acid balanced in argon. Ab initio calculations suggest a complex between THF and acetic acid is more likely to form compared to the analogous acetic acid complex with triethyl borane, the initial target. The observed rotational constants are also more similar to those predicted for a complex formed between THF and acetic acid, than for those of a complex formed between triethyl borane and acetic acid. Subsequently, multiple isotopologues of acetic acid have been measured, confirming its presence in the structure. No information has yet been obtained through isotopic substitution within the THF sub-unit. Ab initio calculations predict the most likely structure is one where the acetic acid subunit coordinates over the ring creating a "bridge" between the THF oxygen, the carboxylic O-H, and the carbonyl oxygen to a hydrogen atom on the back of the ring.

  11. Microbiological preservation of cucumbers for bulk storage by the use of acetic acid and food preservatives

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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 assure preservation were low en...

  12. 40 CFR 180.1258 - Acetic acid; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD... acetic acid when used as a preservative on post-harvest agricultural commodities intended for animal feed... of acetic acid in or on all food crops resulting from unintentional spray and drift to...

  13. 40 CFR 180.1258 - Acetic acid; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD... acetic acid when used as a preservative on post-harvest agricultural commodities intended for animal feed... of acetic acid in or on all food crops resulting from unintentional spray and drift to...

  14. Development of xylose-fermenting yeasts for ethanol production at high acetic acid concentrations

    SciTech Connect

    Mohandas, D.V.; Whelan, D.R.; Panchal, C.J.

    1995-12-31

    Mutants resistant to comparatively high levels of acetic acid were isolated from the xylose-fermenting yeasts Candida shehatae and Pichia Stipitis by adapting these cultures to increasing concentrations of acetic acid grown in shake-flask cultures. These mutants were tested for their ability to ferment xylose in presence of high acetic acid concentrations, in acid hydrolysates of wood, and in hardwood spent sulfite liquor, and compared with their wild-type counterparts and between themselves. The P. stipitis mutant exhibited faster fermentation times, better tolerance to acid hydrolysates, and tolerance to lower pH.

  15. No catalyst addition and highly efficient dissociation of H2O for the reduction of CO2 to formic acid with Mn.

    PubMed

    Lyu, Lingyun; Zeng, Xu; Yun, Jun; Wei, Feng; Jin, Fangming

    2014-05-20

    The "greenhouse effect" caused by the increasing atmospheric CO2 level is becoming extremely serious, and thus, the reduction of CO2 emissions has become an extensive, urgent, and long-term task. The dissociation of water for CO2 reduction with solar energy is regarded as one of the most promising methods for the sustainable development of the environment and energy. However, a high solar-to-fuel efficiency keeps a great challenge. In this work, the first observation of a highly effective, highly selective, and robust system of dissociating water for the reduction of carbon dioxide (CO2) into formic acid with metallic manganese (Mn) is reported. A considerably high formic acid yield of more than 75% on a carbon basis from NaHCO3 was achieved with 98% selectivity in the presence of simple commercially available Mn powder without the addition of any catalyst, and the proposed process is exothermic. Thus, this study may provide a promising method for the highly efficient dissociation of water for CO2 reduction by combining solar-driven thermochemistry with the reduction of MnO into Mn.

  16. Waste-Glycerol-Directed Synthesis of Mesoporous Silica and Carbon with Superior Performance in Room-Temperature Hydrogen Production from Formic Acid

    PubMed Central

    Lee, Dong-Wook; Jin, Min-Ho; Park, Ji Chan; Lee, Chun-Boo; Oh, Duckkyu; Lee, Sung-Wook; Park, Jin-Woo; Park, Jong-Soo

    2015-01-01

    The development of easier, cheaper, and more ecofriendly synthetic methods for mesoporous materials remains a challenging topic to commercialize them, and the transformation of waste glycerol, as a biodiesel byproduct, into something useful and salable is one of the pending issues to be resolved. Here we first report that mesoporous silica (KIE-6) and carbon (KIE-7) can be simultaneously synthesized by using cheap and ecofriendly crude-waste-glycerol of biodiesel with or without glycerol purification, and we demonstrated the excellent performance of the mesoporous material as a catalyst support for formic acid decomposition. As a result, Pd-MnOx catalysts supported on NH2-functionalized KIE-6 showed the highest catalytic activity (TOF: 540.6 h−1) ever reported for room-temperature formic acid decomposition without additives. Moreover, we conducted life-cycle assessment (LCA) from biomass cultivation through biodiesel production to KIE-6 and KIE-7 preparation, and it was confirmed that CO2 emission during synthesis of KIE-6 and KIE-7 could be reduced by 87.1% and 85.7%, respectively. We believe that our study suggested more ecofriendly and industry-friendly approaches for preparation of mesoporous materials, and utilization of waste glycerol. PMID:26515193

  17. Catalytic performance comparison of shape-dependent nanocrystals and oriented ultra thin films of Pt4Cu alloy in the formic acid oxidation process

    NASA Astrophysics Data System (ADS)

    Bromberg, Lori Ana

    Research efforts continue to focus on the development of viable and cost effective fuel cell catalysts with minimized Pt content. This work presents a comparison study between Pt4Cu nanocubes and nano-octahedra as well as Pt4Cu (100) and (111) thin films used as catalysts for formic acid oxidation. The paper introduces a novel synthetic method for Pt 4Cu nano-octahedra and it also demonstrates for the first time the use of surface limited redox replacement of Pb underpotentially deposited layer for epitaxial growth of thin alloy films. Overall, the nanoparticle catalysts exhibit superior performance in terms of durability when compared to their thin film counterparts, but feature nearly five-fold lower activity. As a result it was determined that both types of catalysts accumulate nearly equal charge density in their lifespan. In terms of crystallographic orientation, the results indicate that the nanocubes and Pt4Cu (100) thin films outperform the nano-octahedra and Pt4Cu (111) thin films in terms of durability but feature equal to slightly lower activity. This significant difference in durability of catalysts with different crystallographic orientation is attributed to interplay of passivation (from CO poisoning and Pt oxidation) and dissolution of Pt. When compared to pure Pt catalysts (nanoparticles and thin films), all of the Pt4Cu catalysts in this work exhibit superior performance towards formic acid oxidation in terms of activity and durability.

  18. Waste-Glycerol-Directed Synthesis of Mesoporous Silica and Carbon with Superior Performance in Room-Temperature Hydrogen Production from Formic Acid

    NASA Astrophysics Data System (ADS)

    Lee, Dong-Wook; Jin, Min-Ho; Park, Ji Chan; Lee, Chun-Boo; Oh, Duckkyu; Lee, Sung-Wook; Park, Jin-Woo; Park, Jong-Soo

    2015-10-01

    The development of easier, cheaper, and more ecofriendly synthetic methods for mesoporous materials remains a challenging topic to commercialize them, and the transformation of waste glycerol, as a biodiesel byproduct, into something useful and salable is one of the pending issues to be resolved. Here we first report that mesoporous silica (KIE-6) and carbon (KIE-7) can be simultaneously synthesized by using cheap and ecofriendly crude-waste-glycerol of biodiesel with or without glycerol purification, and we demonstrated the excellent performance of the mesoporous material as a catalyst support for formic acid decomposition. As a result, Pd-MnOx catalysts supported on NH2-functionalized KIE-6 showed the highest catalytic activity (TOF: 540.6 h-1) ever reported for room-temperature formic acid decomposition without additives. Moreover, we conducted life-cycle assessment (LCA) from biomass cultivation through biodiesel production to KIE-6 and KIE-7 preparation, and it was confirmed that CO2 emission during synthesis of KIE-6 and KIE-7 could be reduced by 87.1% and 85.7%, respectively. We believe that our study suggested more ecofriendly and industry-friendly approaches for preparation of mesoporous materials, and utilization of waste glycerol.

  19. Tailoring the composition of ultrathin, ternary alloy PtRuFe nanowires for the methanol oxidation reaction and formic acid oxidation reaction

    DOE PAGES

    Scofield, Megan E.; Koenigsmann, Christopher; Wang, Lei; Liu, Haiqing; Wong, Stanislaus S.

    2014-11-25

    In the search for alternatives to conventional Pt electrocatalysts, we have synthesized ultrathin, ternary PtRuFe nanowires (NW), possessing different chemical compositions in order to probe their CO tolerance as well as electrochemical activity as a function of composition for both (i) the methanol oxidation reaction (MOR) and (ii) the formic acid oxidation reaction (FAOR). As-prepared ‘multifunctional’ ternary NW catalysts exhibited both higher MOR and FAOR activity as compared with binary Pt₇Ru₃ NW, monometallic Pt NW, and commercial catalyst control samples. In terms of synthetic novelty, we utilized a sustainably mild, ambient wet-synthesis method never previously applied to the fabrication ofmore » crystalline, pure ternary systems in order to fabricate ultrathin, homogeneous alloy PtRuFe NWs with a range of controlled compositions. Thus, these NWs were subsequently characterized using a suite of techniques including XRD, TEM, SAED, and EDAX in order to verify not only the incorporation of Ru and Fe into the Pt lattice but also their chemical homogeneity, morphology, as well as physical structure and integrity. Lastly, these NWs were electrochemically tested in order to deduce the appropriateness of conventional explanations such as (i) the bi-functional mechanism as well as (ii) the ligand effect to account for our MOR and FAOR reaction data. Specifically, methanol oxidation appears to be predominantly influenced by the Ru content, whereas formic acid oxidation is primarily impacted by the corresponding Fe content within the ternary metal alloy catalyst itself.« less

  20. Waste-Glycerol-Directed Synthesis of Mesoporous Silica and Carbon with Superior Performance in Room-Temperature Hydrogen Production from Formic Acid.

    PubMed

    Lee, Dong-Wook; Jin, Min-Ho; Park, Ji Chan; Lee, Chun-Boo; Oh, Duckkyu; Lee, Sung-Wook; Park, Jin-Woo; Park, Jong-Soo

    2015-01-01

    The development of easier, cheaper, and more ecofriendly synthetic methods for mesoporous materials remains a challenging topic to commercialize them, and the transformation of waste glycerol, as a biodiesel byproduct, into something useful and salable is one of the pending issues to be resolved. Here we first report that mesoporous silica (KIE-6) and carbon (KIE-7) can be simultaneously synthesized by using cheap and ecofriendly crude-waste-glycerol of biodiesel with or without glycerol purification, and we demonstrated the excellent performance of the mesoporous material as a catalyst support for formic acid decomposition. As a result, Pd-MnOx catalysts supported on NH2-functionalized KIE-6 showed the highest catalytic activity (TOF: 540.6 h(-1)) ever reported for room-temperature formic acid decomposition without additives. Moreover, we conducted life-cycle assessment (LCA) from biomass cultivation through biodiesel production to KIE-6 and KIE-7 preparation, and it was confirmed that CO2 emission during synthesis of KIE-6 and KIE-7 could be reduced by 87.1% and 85.7%, respectively. We believe that our study suggested more ecofriendly and industry-friendly approaches for preparation of mesoporous materials, and utilization of waste glycerol. PMID:26515193

  1. No catalyst addition and highly efficient dissociation of H2O for the reduction of CO2 to formic acid with Mn.

    PubMed

    Lyu, Lingyun; Zeng, Xu; Yun, Jun; Wei, Feng; Jin, Fangming

    2014-05-20

    The "greenhouse effect" caused by the increasing atmospheric CO2 level is becoming extremely serious, and thus, the reduction of CO2 emissions has become an extensive, urgent, and long-term task. The dissociation of water for CO2 reduction with solar energy is regarded as one of the most promising methods for the sustainable development of the environment and energy. However, a high solar-to-fuel efficiency keeps a great challenge. In this work, the first observation of a highly effective, highly selective, and robust system of dissociating water for the reduction of carbon dioxide (CO2) into formic acid with metallic manganese (Mn) is reported. A considerably high formic acid yield of more than 75% on a carbon basis from NaHCO3 was achieved with 98% selectivity in the presence of simple commercially available Mn powder without the addition of any catalyst, and the proposed process is exothermic. Thus, this study may provide a promising method for the highly efficient dissociation of water for CO2 reduction by combining solar-driven thermochemistry with the reduction of MnO into Mn. PMID:24787746

  2. Effect of the Pd/MWCNTs anode catalysts preparation methods on their morphology and activity in a direct formic acid fuel cell

    NASA Astrophysics Data System (ADS)

    Lesiak, B.; Mazurkiewicz, M.; Malolepszy, A.; Stobinski, L.; Mierzwa, B.; Mikolajczuk-Zychora, A.; Juchniewicz, K.; Borodzinski, A.; Zemek, J.; Jiricek, P.

    2016-11-01

    Impact of Pd/MWCNTs catalysts preparation method on the catalysts morphology and activity in a formic acid electrooxidation reaction was investigated. Three reduction methods of Pd precursor involving reduction in a high pressure microwave reactor (Pd1), reduction with NaBH4 (Pd2) and microwave-assisted polyol method (Pd3) were used in this paper. Crystallites size and morphology were studied using the scanning transmission electron microscopy (STEM), X-ray diffraction (XRD), whereas elemental composition, Pd chemical state and functional groups content by the X-ray photoelectron spectroscopy (XPS). The prepared catalysts were tested in a direct formic acid fuel cell (DFAFC) as an anode material. The catalytic activity was correlated with a mean fraction of the total Pd atoms exposed at the surface (FE). The value of FE was calculated from the crystallites size distribution determined by the STEM measurements. Non-linear dependence of a current density versus FE, approaching the maximum at FE≈0.25 suggests that the catalytic process proceeded at Pd nanocrystallites faces, with inactive edges and corners. Pd2 catalyst exhibited highest activity due to its smallest Pd crystallites (3.2 nm), however the absence of Pd crystallites aggregation and low content of carbon in PdCx phase, i.e. x = 4 at.% may also affect the observed.

  3. Highly catalytic hollow palladium nanoparticles derived from silver@silver-palladium core-shell nanostructures for the oxidation of formic acid

    NASA Astrophysics Data System (ADS)

    Chen, Dong; Cui, Penglei; He, Hongyan; Liu, Hui; Yang, Jun

    2014-12-01

    Hollow Palladium (hPd) nanoparticles (NPs) are prepared via a simple and mild successive method. Firstly, core-shell NPs with silver (Ag) cores and silver-palladium (Ag-Pd) alloy shells are synthesized in aqueous phase by galvanic replacement reaction (GRR) between Ag NPs and Pd2+ ion precursors. Saturated aqueous sodium chloride (NaCl) solution was then employed to remove the Ag component from the core and shell regions of core-shell Ag@Ag-Pd NPs, resulting in the formation of hPd NPs with shrunk sizes in comparison with their core-shell parents. Specifically, the hPd NPs exhibit superior catalytic activity and durability for catalyzing the oxidation of formic acid, compared with the Pd NPs reduced by NaBH4 in aqueous solution and commercial Pd/C catalyst from Johnson Matthey, mainly due to the large electrochemically active surface areas of the hollow particles. In addition, The Ag component in core-shell Ag@Ag-Pd NPs has an unfavorable influence on catalytic activity of NPs for formic acid oxidation. However, the durability could be improved due to the electron donating effect from Ag to Pd atoms in the core-shell NPs.

  4. Tailoring the composition of ultrathin, ternary alloy PtRuFe nanowires for the methanol oxidation reaction and formic acid oxidation reaction

    SciTech Connect

    Scofield, Megan E.; Koenigsmann, Christopher; Wang, Lei; Liu, Haiqing; Wong, Stanislaus S.

    2014-11-25

    In the search for alternatives to conventional Pt electrocatalysts, we have synthesized ultrathin, ternary PtRuFe nanowires (NW), possessing different chemical compositions in order to probe their CO tolerance as well as electrochemical activity as a function of composition for both (i) the methanol oxidation reaction (MOR) and (ii) the formic acid oxidation reaction (FAOR). As-prepared ‘multifunctional’ ternary NW catalysts exhibited both higher MOR and FAOR activity as compared with binary Pt₇Ru₃ NW, monometallic Pt NW, and commercial catalyst control samples. In terms of synthetic novelty, we utilized a sustainably mild, ambient wet-synthesis method never previously applied to the fabrication of crystalline, pure ternary systems in order to fabricate ultrathin, homogeneous alloy PtRuFe NWs with a range of controlled compositions. Thus, these NWs were subsequently characterized using a suite of techniques including XRD, TEM, SAED, and EDAX in order to verify not only the incorporation of Ru and Fe into the Pt lattice but also their chemical homogeneity, morphology, as well as physical structure and integrity. Lastly, these NWs were electrochemically tested in order to deduce the appropriateness of conventional explanations such as (i) the bi-functional mechanism as well as (ii) the ligand effect to account for our MOR and FAOR reaction data. Specifically, methanol oxidation appears to be predominantly influenced by the Ru content, whereas formic acid oxidation is primarily impacted by the corresponding Fe content within the ternary metal alloy catalyst itself.

  5. Acetate/acetyl-CoA metabolism associated with cancer fatty acid synthesis: overview and application.

    PubMed

    Yoshii, Yukie; Furukawa, Takako; Saga, Tsuneo; Fujibayashi, Yasuhisa

    2015-01-28

    Understanding cancer-specific metabolism is important for identifying novel targets for cancer diagnosis and therapy. Induced acetate/acetyl CoA metabolism is a notable feature that is related to fatty acid synthesis supporting tumor growth. In this review, we focused on the recent findings related to cancer acetate/acetyl CoA metabolism. We also introduce [1-¹¹C]acetate positron emission tomography (PET), which is a useful tool to visualize up-regulation of acetate/acetyl CoA metabolism in cancer, and discuss the utility of [1-¹¹C]acetate PET in cancer diagnosis and its application to personalized medicine.

  6. 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

  7. Glacial Acetic Acid Adverse Events: Case Reports and Review of the Literature

    PubMed Central

    Doles, William; Wilkerson, Garrett; Morrison, Samantha

    2015-01-01

    Glacial acetic acid is a dangerous chemical that has been associated with several adverse drug events involving patients over recent years. When diluted to the proper concentration, acetic acid solutions have a variety of medicinal uses. Unfortunately, despite warnings, the improper dilution of concentrated glacial acetic acid has resulted in severe burns and other related morbidities. We report on 2 additional case reports of adverse drug events involving glacial acetic acid as well as a review of the literature. A summary of published case reports is provided, including the intended and actual concentration of glacial acetic acid involved, the indication for use, degree of exposure, and resultant outcome. Strategies that have been recommended to improve patient safety are summarized within the context of the key elements of the medication use process. PMID:26448660

  8. 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

  9. Acetic acid induces pH-independent cellular energy depletion in Salmonella enterica.

    PubMed

    Tan, Sin Mei; Lee, Sui Mae; Dykes, Gary A

    2015-03-01

    Weak organic acids are widely used as preservatives and disinfectants in the food industry. Despite their widespread use, the antimicrobial mode of action of organic acids is still not fully understood. This study investigated the effect of acetic acid on the cell membranes and cellular energy generation of four Salmonella strains. Using a nucleic acid/protein assay, it was established that acetic acid did not cause leakage of intracellular components from the strains. A scanning electron microscopy study further confirmed that membrane disruption was not the antimicrobial mode of action of acetic acid. Some elongated Salmonella cells observed in the micrographs indicated a possibility that acetic acid may inhibit DNA synthesis in the bacterial cells. Using an ATP assay, it was found that at a neutral pH, acetic acid caused cellular energy depletion with an ADP/ATP ratio in the range between 0.48 and 2.63 (p<0.05) that was apparent for the four Salmonella strains. We suggest that this effect was probably due solely to the action of undissociated acid molecules. The antimicrobial effect of acetic acid was better under acidic conditions (ADP/ATP ratio of 5.56 ± 1.27; p<0.05), where the role of both pH and undissociated acid molecules can act together. We concluded that the inhibitory effect of acetic acid is not solely attributable to acidic pH but also to undissociated acid molecules. This finding has implication for the use of acetic acid as an antimicrobial against Salmonella on food products, such as chicken meat, which can buffer its pH.

  10. Formic and acetic acids in degradation products of plant volatiles elicit olfactory and behavorial responses from an insect vector

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The Asian citrus psyllid, Diaphorina citri Kuwayama (Hemiptera: Liviidae) vectors the bacterial pathogen presumed to be the etiological agent of citrus greening disease, Huanglongbing (HLB), a major threat to citrus industry worldwide. We studied antennal and behavioral responses of Diaphorina citri...

  11. Metabolic regulation of the plant hormone indole-3-acetic acid

    SciTech Connect

    Jerry D. Cohen

    2009-11-01

    The phytohormone indole-3-acetic acid (IAA, auxin) is important for many aspects of plant growth, development and responses to the environment yet the routes to is biosynthesis and mechanisms for regulation of IAA levels remain important research questions. A critical issue concerning the biosynthesis if IAA in plants is that redundant pathways for IAA biosynthesis exist in plants. We showed that these redundant pathways and their relative contribution to net IAA production are under both developmental and environmental control. We worked on three fundamental problems related to how plants get their IAA: 1) An in vitro biochemical approach was used to define the tryptophan dependent pathway to IAA using maize endosperm, where relatively large amounts of IAA are produced over a short developmental period. Both a stable isotope dilution and a protein MS approach were used to identify intermediates and enzymes in the reactions. 2) We developed an in vitro system for analysis of tryptophan-independent IAA biosynthesis in maize seedlings and we used a metabolite profiling approach to isolate intermediates in this reaction. 3) Arabidopsis contains a small family of genes that encode potential indolepyruvate decarboxylase enzymes. We cloned these genes and studied plants that are mutant in these genes and that over-express each member in the family in terms of the level and route of IAA biosynthesis. Together, these allowed further development of a comprehensive picture of the pathways and regulatory components that are involved in IAA homeostasis in higher plants.

  12. Acetic acid chromoendoscopy: Improving neoplasia detection in Barrett's esophagus

    PubMed Central

    Chedgy, Fergus J Q; Subramaniam, Sharmila; Kandiah, Kesavan; Thayalasekaran, Sreedhari; Bhandari, Pradeep

    2016-01-01

    Barrett’s esophagus (BE) is an important condition given its significant premalignant potential and dismal five-year survival outcomes of advanced esophageal adenocarcinoma. It is therefore suggested that patients with a diagnosis of BE undergo regular surveillance in order to pick up dysplasia at an earlier stage to improve survival. Current “gold-standard” surveillance protocols suggest targeted biopsy of visible lesions followed by four quadrant random biopsies every 2 cm. However, this method of Barrett’s surveillance is fraught with poor endoscopist compliance as the procedures are time consuming and poorly tolerated by patients. There are also significant miss-rates with this technique for the detection of neoplasia as only 13% of early neoplastic lesions appear as visible nodules. Despite improvements in endoscope resolution these problems persist. Chromoendoscopy is an extremely useful adjunct to enhance mucosal visualization and characterization of Barrett’s mucosa. Acetic acid chromoendoscopy (AAC) is a simple, non-proprietary technique that can significantly improve neoplasia detection rates. This topic highlight summarizes the current evidence base behind AAC for the detection of neoplasia in BE and provides an insight into the direction of travel for further research in this area. PMID:27433088

  13. Acetic acid chromoendoscopy: Improving neoplasia detection in Barrett's esophagus.

    PubMed

    Chedgy, Fergus J Q; Subramaniam, Sharmila; Kandiah, Kesavan; Thayalasekaran, Sreedhari; Bhandari, Pradeep

    2016-07-01

    Barrett's esophagus (BE) is an important condition given its significant premalignant potential and dismal five-year survival outcomes of advanced esophageal adenocarcinoma. It is therefore suggested that patients with a diagnosis of BE undergo regular surveillance in order to pick up dysplasia at an earlier stage to improve survival. Current "gold-standard" surveillance protocols suggest targeted biopsy of visible lesions followed by four quadrant random biopsies every 2 cm. However, this method of Barrett's surveillance is fraught with poor endoscopist compliance as the procedures are time consuming and poorly tolerated by patients. There are also significant miss-rates with this technique for the detection of neoplasia as only 13% of early neoplastic lesions appear as visible nodules. Despite improvements in endoscope resolution these problems persist. Chromoendoscopy is an extremely useful adjunct to enhance mucosal visualization and characterization of Barrett's mucosa. Acetic acid chromoendoscopy (AAC) is a simple, non-proprietary technique that can significantly improve neoplasia detection rates. This topic highlight summarizes the current evidence base behind AAC for the detection of neoplasia in BE and provides an insight into the direction of travel for further research in this area. PMID:27433088

  14. Acetic acid bacteria isolated from grapes of South Australian vineyards.

    PubMed

    Mateo, E; Torija, M J; Mas, A; Bartowsky, E J

    2014-05-16

    Acetic acid bacteria (AAB) diversity from healthy, mould-infected and rot-affected grapes collected from three vineyards of Adelaide Hills (South Australia) was analyzed by molecular typing and identification methods. Nine different AAB species were identified from the 624 isolates recovered: Four species from Gluconobacter genus, two from Asaia and one from Acetobacter were identified by the analysis of 16S rRNA gene and 16S-23S rRNA gene internal transcribed spacer. However, the identification of other isolates that were assigned as Asaia sp. and Ameyamaea chiangmaiensis required more analysis for a correct species classification. The species of Gluconobacter cerinus was the main one identified; while one genotype of Asaia siamensis presented the highest number of isolates. The number of colonies recovered and genotypes identified was strongly affected by the infection status of the grapes; the rot-affected with the highest number. However, the species diversity was similar in all the cases. High AAB diversity was detected with a specific genotype distribution for each vineyard.

  15. Evaluation of the morphological changes of gastric mucosa induced by a low concentration of acetic acid using a rat model.

    PubMed

    Nakao, Ken-ichiro; Ro, Ayako; Kibayashi, Kazuhiko

    2014-02-01

    Oral ingestion of concentrated acetic acid causes corrosive injury of the gastrointestinal tract. To assess the effects of a low concentration of acetic acid on gastric mucosa, we examined the gastric mucosal changes in rats at 1 and 3 days after the injection of 5% or 25% acetic acid into the gastric lumen. The area of the gastric ulcerative lesions in the 25% acetic acid group was significantly larger than that in the 5% acetic acid group. The lesion area was reduced significantly at 3 days after injection in the 5% acetic acid group, whereas no significant difference in lesion area was observed at 1 and 3 days in the 25% acetic acid group. Histologically, corrosive necrosis was limited to the mucosal layer in the 5% acetic acid group, whereas necrosis extended throughout the gastric wall in the 25% acetic acid group. At 3 days post-injection, the 25% acetic acid group showed widespread persistent inflammation, whereas the 5% acetic acid group showed widespread appearance of fibroblasts indicative of a healing process. These results indicate that a low concentration of acetic acid damages the gastric mucosa and that the degree of mucosal damage depends on the concentration of acetic acid.

  16. Absorption cross section for the 5νOH stretch of acetic acid and peracetic acid

    NASA Astrophysics Data System (ADS)

    Begashaw, I. G.; Collingwood, M.; Bililign, S.

    2009-12-01

    We report measurements of the absorption cross sections for the vibrational O-H stretch (5νOH) overtone transitions in glacial acetic acid and peracetic acid. The photochemistry that results from overtone excitation has been shown to lead to OH radical production in molecules containing O-H (HNO3, H2O2). In addition the overtone excitation has been observed to result in light initiated chemical reaction. A Cavity ring-down spectroscopy (CRDS) instrument comprising of an Nd:YAG pumped dye laser and 620nm high reflectivity mirrors (R=99.995%) was used to measure the cross sections. The dye laser wavelength was calibrated using water vapor spectrum and the HITRAN 2008 database. The instrument’s minimum detectable absorption is αmin =4.5 *10-9cm-1 Hz-1/2 at 2σ noise level near the peak of the absorption feature. This measurement is the first for acetic acid at this excitation level. Preliminary results for acetic acid show the peak occurs near 615nm. Procedures for separating the monomer and dimer contribution will be presented. We would like to acknowledge support from NSF award #0803016 and NOAA-EPP award #NA06OAR4810187.

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

    SciTech Connect

    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 with 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 (4

  18. Transcriptome shifts in response to furfural and acetic acid in Saccharomyces cerevisiae.

    PubMed

    Li, Bing-Zhi; Yuan, Ying-Jin

    2010-05-01

    Furfural and acetic acid are two prevalent inhibitors to microorganisms during cellulosic ethanol production, but molecular mechanisms of tolerance to these inhibitors are still unclear. In this study, genome-wide transcriptional responses to furfural and acetic acid were investigated in Saccharomyces cerevisiae using microarray analysis. We found that 103 and 227 genes were differentially expressed in the response to furfural and acetic acid, respectively. Furfural downregulated genes related to transcriptional control and translational control, while it upregulated stress-responsive genes. Furthermore, furfural also interrupted the transcription of genes involved in metabolism of essential chemicals, such as etrahydrofolate, spermidine, spermine, and riboflavin monophosphate. Acetic acid downregulated genes encoding mitochondrial ribosomal proteins and genes involved in carbohydrate metabolism and regulation and upregulated genes related to amino acid metabolism. The results revealed that furfural and acetic acid had effects on multiple aspects of cellular metabolism on the transcriptional level and that mitochondria might play important roles in response to both furfural and acetic acid. This research has provided insights into molecular response to furfural and acetic acid in S. cerevisiae, and it will be helpful to construct more resistant strains for cellulosic ethanol production.

  19. Beneficial Effect of Acetic Acid on the Xylose Utilization and Bacterial Cellulose Production by Gluconacetobacter xylinus.

    PubMed

    Yang, Xiao-Yan; Huang, Chao; Guo, Hai-Jun; Xiong, Lian; Luo, Jun; Wang, Bo; Chen, Xue-Fang; Lin, Xiao-Qing; Chen, Xin-De

    2014-09-01

    In this work, acetic acid was found as one promising substrate to improve xylose utilization by Gluconacetobacter xylinus CH001. Also, with the help of adding acetic acid into medium, the bacterial cellulose (BC) production by G. xylinus was increased significantly. In the medium containing 3 g l(-1) acetic acid, the optimal xylose concentration for BC production was 20 g l(-1). In the medium containing 20 g l(-1) xylose, the xylose utilization and BC production by G. xylinus were stimulated by acetic acid within certain concentration. The highest BC yield (1.35 ± 0.06 g l(-1)) was obtained in the medium containing 20 g l(-1) xylose and 3 g l(-1) acetic acid after 14 days. This value was 6.17-fold higher than the yield (0.21 ± 0.01 g l(-1)) in the medium only containing 20 g l(-1) xylose. The results analyzed by FE-SEM, FTIR, and XRD showed that acetic acid affected little on the microscopic morphology and physicochemical characteristics of BC. Base on the phenomenon observed, lignocellulosic acid hydrolysates (xylose and acetic acid are main carbon sources present in it) could be considered as one potential substrate for BC production.

  20. Formic Acid-Based Direct, On-Plate Testing of Yeast and Corynebacterium Species by Bruker Biotyper Matrix-Assisted Laser Desorption Ionization–Time of Flight Mass Spectrometry

    PubMed Central

    Theel, Elitza S.; Schmitt, Bryan H.; Hall, Leslie; Cunningham, Scott A.; Walchak, Robert C.; Patel, Robin

    2012-01-01

    An on-plate testing method using formic acid was evaluated on the Bruker Biotyper matrix-assisted laser desorption ionization–time of flight (MALDI-TOF) mass spectrometry system using 90 yeast and 78 Corynebacterium species isolates, and 95.6 and 81.1% of yeast and 96.1 and 92.3% of Corynebacterium isolates were correctly identified to the genus and species levels, respectively. The on-plate method using formic acid yielded identification percentages similar to those for the conventional but more laborious tube-based extraction. PMID:22760034

  1. Selection of a Bifidobacterium animalis subsp. lactis Strain with a Decreased Ability To Produce Acetic Acid

    PubMed Central

    Margolles, Abelardo

    2012-01-01

    We have characterized a new strain, Bifidobacterium animalis subsp. lactis CECT 7953, obtained by random UV mutagenesis, which produces less acetic acid than the wild type (CECT 7954) in three different experimental settings: De Man-Rogosa-Sharpe broth without sodium acetate, resting cells, and skim milk. Genome sequencing revealed a single Phe-Ser substitution in the acetate kinase gene product that seems to be responsible for the strain's reduced acid production. Accordingly, acetate kinase specific activity was lower in the low acetate producer. Strain CECT 7953 produced less acetate, less ethanol, and more yoghourt-related volatile compounds in skim milk than the wild type did. Thus, CECT 7953 shows promising potential for the development of dairy products fermented exclusively by a bifidobacterial strain. PMID:22389372

  2. Organic acids and thymol: unsuitable alternative control of Aethina tumida Murray (Coleoptera: Nitidulidae)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    To explore alternative small hive beetle control strategies, established Varroa destructor and Galleria mellonella treatments with organic acids (formic, lactic, oxalic and acetic) and thymol were investigated in the laboratory against eggs, larvae and adult small hive beetle (SHB). As formic and ox...

  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.

    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.

  4. 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.

  5. 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.

  6. Acetic acid-water complex: The first observation of structures containing the higher-energy acetic acid conformer

    NASA Astrophysics Data System (ADS)

    Lopes, Susy; Fausto, Rui; Khriachtchev, Leonid

    2016-02-01

    Non-covalent interaction of acetic acid (AA) and water is studied experimentally by IR spectroscopy in a nitrogen matrix and theoretically at the MP2 and coupled-cluster with single and double and perturbative triple excitations [CCSD(T)]/6-311++G(2d,2p) levels of theory. This work is focused on the first preparation and characterization of complexes of higher-energy (cis) conformer of AA with water. The calculations show three 1:1 structures for the trans-AA⋯H2O complexes and three 1:1 structures for the cis-AA⋯H2O complexes. Two trans-AA⋯H2O and two cis-AA⋯H2O complexes are found and structurally assigned in the experiments. The two cis-AA⋯ ṡ H2O complexes are obtained by annealing of a matrix containing water and cis-AA molecules prepared by selective vibrational excitation of the ground-state trans form. The less stable trans-AA⋯H2O complex is obtained by vibrational excitation of the less stable cis-AA⋯H2O complex. In addition, the 1:2 complexes of trans-AA and cis-AA with water molecules are studied computationally and the most stable forms of the 1:2 complexes are experimentally identified.

  7. 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

  8. 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.

  9. 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.

  10. 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. PMID:18177968

  11. Infrared spectroscopy study of adsorption and photodecomposition of formic acid on reduced and defective rutile TiO{sub 2} (110) surfaces

    SciTech Connect

    Mattsson, Andreas Österlund, Lars; Hu, Shuanglin; Hermansson, Kersti

    2014-11-01

    Adsorption and photodecomposition of formic acid on rutile TiO{sub 2} (110) have been investigated with infrared reflection–absorption spectroscopy (IRRAS) employing p- and s-polarized light along the [001] and [11{sup ¯}0] crystal directions. The single crystal surfaces were prepared either by sputtering and annealing in ultrahigh vacuum (UHV) to obtain a reduced surface (r-TiO{sub 2}), or by sputtering without annealing to create a rough, highly defective surface (sp-TiO{sub 2}). Results are compared with corresponding measurements on rutile nanocrystals performed in synthetic air. IRRAS spectra obtained on r-TiO{sub 2} and rutile nanocrystals are very similar, and show that in both cases formic acid dissociates and is predominately adsorbed as a bridging bidentate formate species, and that the formate adsorption structure on the nanocrystals is dominated by interactions with majority (110) surfaces. In contrast, the IRRAS spectra on sp-TiO{sub 2} are different, with only minor spectral features associated with (110) surfaces and lost azimuthal symmetry, both of which imply changed adsorption geometry due to bonding to low-coordinated Ti atoms with lower valences. The UV-induced rate of formate photodecomposition is about 30 times higher on rutile nanocrystals in synthetic air compared with sp-TiO{sub 2} under UHV conditions, and even larger than on r-TiO{sub 2}. These differences are explained by the lack of oxygen and limited hydroxyl coverage under UHV conditions. The difference in reactivity between the r-TiO{sub 2} and sp-TiO{sub 2} surfaces is attributed to a high concentration of strongly bonded bridging bidentate formate species on the (110) surface, which lowers its reactivity. The results point to a pressure gap where the availability of molecular oxygen and the hydroxyl concentration limit the photoreactivity in UHV leading to an almost 20-fold decrease of the formate degradation rate in UHV. In contrast, the structure represented by the single

  12. Theophylline-7-acetic acid derivatives with amino acids as anti-tuberculosis agents.

    PubMed

    Voynikov, Yulian; Valcheva, Violeta; Momekov, Georgi; Peikov, Plamen; Stavrakov, Georgi

    2014-07-15

    A series of amides were synthesized by condensation of theophylline-7-acetic acid and eight commercially available amino acid methyl ester hydrochlorides. Consecutive hydrolysis of six of the amido-esters resulted in the formation of corresponding amido-acids. The newly synthesized compounds were evaluated for their in vitro activity against Mycobacterium tuberculosis H37Rv. The activity varied depending on the amino acid fragments and in seven cases exerted excellent values with MICs 0.46-0.26 μM. Assessment of the cytotoxicity revealed that the compounds were not cytotoxic against the human embryonal kidney cell line HEK-293T. The theophylline-7-acetamides containing amino acid moieties appear to be promising lead compounds for the development of antimycobacterial agents.

  13. 40 CFR 721.304 - Acetic acid, [(5-chloro-8-quinolinyl)oxy-], 1-methyl hexyl ester.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Acetic acid, , 1-methyl hexyl ester... Substances § 721.304 Acetic acid, , 1-methyl hexyl ester. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as acetic acid, -, 1-methylhexyl ester (PMN...

  14. 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.

  15. 40 CFR 721.304 - Acetic acid, [(5-chloro-8-quinolinyl)oxy-], 1-methyl hexyl ester.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Acetic acid, , 1-methyl hexyl ester... Substances § 721.304 Acetic acid, , 1-methyl hexyl ester. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as acetic acid, -, 1-methylhexyl ester (PMN...

  16. 40 CFR 721.304 - Acetic acid, [(5-chloro-8-quinolinyl)oxy-], 1-methyl hexyl ester.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Acetic acid, , 1-methyl hexyl ester... Substances § 721.304 Acetic acid, , 1-methyl hexyl ester. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as acetic acid, -, 1-methylhexyl ester (PMN...

  17. 40 CFR 721.304 - Acetic acid, [(5-chloro-8-quinolinyl)oxy-], 1-methyl hexyl ester.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Acetic acid, , 1-methyl hexyl ester... Substances § 721.304 Acetic acid, , 1-methyl hexyl ester. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as acetic acid, -, 1-methylhexyl ester (PMN...

  18. 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

  19. Acetic Acid Acts as a Volatile Signal To Stimulate Bacterial Biofilm Formation

    PubMed Central

    Chen, Yun; Gozzi, Kevin; Yan, Fang

    2015-01-01

    ABSTRACT Volatiles are small air-transmittable chemicals with diverse biological activities. In this study, we showed that volatiles produced by the bacterium Bacillus subtilis had a profound effect on biofilm formation of neighboring B. subtilis cells that grew in proximity but were physically separated. We further demonstrated that one such volatile, acetic acid, is particularly potent in stimulating biofilm formation. Multiple lines of genetic evidence based on B. subtilis mutants that are defective in either acetic acid production or transportation suggest that B. subtilis uses acetic acid as a metabolic signal to coordinate the timing of biofilm formation. Lastly, we investigated how B. subtilis cells sense and respond to acetic acid in regulating biofilm formation. We showed the possible involvement of three sets of genes (ywbHG, ysbAB, and yxaKC), all encoding putative holin-antiholin-like proteins, in cells responding to acetic acid and stimulating biofilm formation. All three sets of genes were induced by acetate. A mutant with a triple mutation of those genes showed a severe delay in biofilm formation, whereas a strain overexpressing ywbHG showed early and robust biofilm formation. Results of our studies suggest that B. subtilis and possibly other bacteria use acetic acid as a metabolic signal to regulate biofilm formation as well as a quorum-sensing-like airborne signal to coordinate the timing of biofilm formation by physically separated cells in the community. PMID:26060272

  20. Isolation of cellulose from rice straw and its conversion into cellulose acetate catalyzed by phosphotungstic acid.

    PubMed

    Fan, Guozhi; Wang, Min; Liao, Chongjing; Fang, Tao; Li, Jianfen; Zhou, Ronghui

    2013-04-15

    Cellulose was isolated from rice straw by pretreatment with dilute alkaline and acid solutions successively, and it was further transferred into cellulose acetate in the presence of acetic anhydride and phosphotungstic acid (H3PW12O40·6H2O). The removal of hemicellulose and lignin was affected by the concentration of KOH and the immersion time in acetic acid solution, and 83wt.% content of cellulose in the treated rice straw was obtained after pretreatment with 4% KOH and immersion in acetic acid for 5h. Phosphotungstic acid was found to be an effective catalyst for the acetylation of the cellulose derived from rice straw. The degree of substitution (DS) values revealed a significant effect for the solubility of cellulose acetate, and the acetone-soluble cellulose acetate with DS values around 2.2 can be obtained by changing the amount of phosphotungstic acid and the time of acetylation. Both the structure of cellulose separated from rice straw and cellulose acetate were confirmed by FTIR and XRD.

  1. Anaerobic conversion of lactic acid to acetic acid and 1, 2-propanediol by Lactobacillus buchneri.

    PubMed

    Oude Elferink, S J; Krooneman, J; Gottschal, J C; Spoelstra, S F; Faber, F; Driehuis, F

    2001-01-01

    The degradation of lactic acid under anoxic conditions was studied in several strains of Lactobacillus buchneri and in close relatives such as Lactobacillus parabuchneri, Lactobacillus kefir, and Lactobacillus hilgardii. Of these lactobacilli, L. buchneri and L. parabuchneri were able to degrade lactic acid under anoxic conditions, without requiring an external electron acceptor. Each mole of lactic acid was converted into approximately 0.5 mol of acetic acid, 0.5 mol of 1,2-propanediol, and traces of ethanol. Based on stoichiometry studies and the high levels of NAD-linked 1, 2-propanediol-dependent oxidoreductase (530 to 790 nmol min(-1) mg of protein(-1)), a novel pathway for anaerobic lactic acid degradation is proposed. The anaerobic degradation of lactic acid by L. buchneri does not support cell growth and is pH dependent. Acidic conditions are needed to induce the lactic-acid-degrading capacity of the cells and to maintain the lactic-acid-degrading activity. At a pH above 5.8 hardly any lactic acid degradation was observed. The exact function of anaerobic lactic acid degradation by L. buchneri is not certain, but some results indicate that it plays a role in maintaining cell viability.

  2. Molten salt medium synthesis of wormlike platinum silver nanotubes without any organic surfactant or solvent for methanol and formic acid oxidation.

    PubMed

    Zhao, Haidong; Liu, Rui; Guo, Yong; Yang, Shengchun

    2015-12-14

    In the current research, the PtxAgy (x/y = 86/14, 79/21, 52/48, 21/79, 11/89) nanoparticles (NPs) are synthesized in the KNO3-LiNO3 molten salts without using any organic surfactant or solvent. The SEM results suggest that when the content of Ag is higher than 48%, the wormlike PtxAgy nanotubes (NTs) can be synthesized. The diameter of the PtxAgyNTs shows a slow decrease with the increase of Ag content. The TEM and HRTEM results indicate that the growth of hollow PtxAgy NTs undergoes an oriented attachment process and a Kirkendall effect approach. The results of cyclic voltammetry (CV) measurement indicate that the Pt52Ag48 catalyst presents a remarkable enhancement for methanol electrooxidation, while the Pt86Ag14 catalyst prefers electrochemically oxidizing formic acid compared with that of the commercially available Pt black.

  3. Auxin Biosynthesis: Are the Indole-3-Acetic Acid and Phenylacetic Acid Biosynthesis Pathways Mirror Images?

    PubMed

    Cook, Sam D; Nichols, David S; Smith, Jason; Chourey, Prem S; McAdam, Erin L; Quittenden, Laura; Ross, John J

    2016-06-01

    The biosynthesis of the main auxin in plants (indole-3-acetic acid [IAA]) has been elucidated recently and is thought to involve the sequential conversion of Trp to indole-3-pyruvic acid to IAA However, the pathway leading to a less well studied auxin, phenylacetic acid (PAA), remains unclear. Here, we present evidence from metabolism experiments that PAA is synthesized from the amino acid Phe, via phenylpyruvate. In pea (Pisum sativum), the reverse reaction, phenylpyruvate to Phe, is also demonstrated. However, despite similarities between the pathways leading to IAA and PAA, evidence from mutants in pea and maize (Zea mays) indicate that IAA biosynthetic enzymes are not the main enzymes for PAA biosynthesis. Instead, we identified a putative aromatic aminotransferase (PsArAT) from pea that may function in the PAA synthesis pathway. PMID:27208245

  4. 40 CFR 180.1258 - Acetic acid; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... AGENCY (CONTINUED) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD... acetic acid when used as a preservative on post-harvest agricultural commodities intended for animal...

  5. Effect of metal ions on decomposition of chlorinated organic substances by ozonation in acetic acid.

    PubMed

    Okawa, Kiyokazu; Tsai, Tsung-Yueh; Nakano, Yoichi; Nishijima, Wataru; Okada, Mitsumasa

    2005-01-01

    The objective of this study is to find metal ions that enhance the ozone decomposition of chlorinated organic substances in acetic acid. Although the pseudo-first order degradation rate constant for 2,4-DCP by ozone in acetic acid in addition of Ca2+, Mg2+, Al3+ and Fe2+ were almost the same as that with no metal ion, the degradation rate in addition of Mn2+ and Fe3+ were 2.4 and 4.5 times as high as that with no metal ion, respectively. The presence of Fe3+ enhanced the degradation of 2,4-DCP by ozone in acetic acid because Fe3+-phenolate complex which have high reactivity with ozone was produced by the reaction between 2,4-DCP and Fe3+ in acetic acid. PMID:15620744

  6. Percutaneous Sclerotherapy Using Acetic Acid After Failure of Alcohol Ablation in an Intra-abdominal Lymphangioma

    SciTech Connect

    Park, Sang Woo Cha, In Ho; Kim, Kyeong Ah; Hong, Suk Joo; Park, Cheol Min; Chung, Hwan Hoon

    2004-09-15

    We report a case of percutaneous sclerotherapy using acetic acid in a 22-year-old woman with an intra-abdominal cystic lymphangioma who was not successfully treated with ethanol despite multiple trials.

  7. Kinetic model for methanogenesis of acetic acid in a multireactor system

    SciTech Connect

    Bhadra, A.; Mukhopadhyay, S.N.; Ghose, T.K.

    1984-01-01

    Bioconversion of acetic acid to methane by a crude culture of methanogens in a continuous multireactor system was investigateed. Culture of methanogens was drawn from an active cow-dung digester (12 days) and was grown in a semisynthetic medium (pH 6.3, 37/sup 0/C) with acetic acid as the sole carbon source. The solubilities of CO/sub 2/, HCO/sub 3//sup -/ and CO/sub 3//sup 2 -/ increased with the rise in pH and exercised considerable influence on the gas composition. Various mechanisms for methanogenesis of acetic acid based on the available pathways were considered. Experimental data were compared with these mechansims, the best fit was determined, and the corresponding rate expression was identified. This mechanism predicted that, of the total methane produced, 72% comes from acetic acid directly and 28% via the CO/sub 2/ reduction route.

  8. 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. PMID:23290939

  9. The antimicrobial effect of acetic acid--an alternative to common local antiseptics?

    PubMed

    Ryssel, H; Kloeters, O; Germann, G; Schäfer, Th; Wiedemann, G; Oehlbauer, M

    2009-08-01

    Acetic acid has been commonly used in medicine for more than 6000 years for the disinfection of wounds and especially as an antiseptic agent in the treatment and prophylaxis of the plague. The main goal of this study was to prove the suitability of acetic acid, in low concentration of 3%, as a local antiseptic agent, especially for use in salvage procedures in problematic infections caused by organisms such as Proteus vulgaris, Acinetobacter baumannii or Pseudomonas aeruginosa. This study was designed to compare the in vitro antimicrobial effect of acetic acid with those of common local antiseptics such as povidone-iodine 11% (Betaisodona), polyhexanide 0.04% (Lavasept), mafenide 5% and chlohexidine gluconate 1.5% cetrimide 15% (Hibicet). Former studies suggest the bactericidal effect of acetic acid, but these data are very heterogeneous; therefore, a standardised in vitro study was conducted. To cover the typical bacterial spectrum of a burn unit, the following Gram-negative and Gram-positive bacterial strains were tested: Escherichia coli, P. vulgaris, P. aeruginosa, A. baumannii, Enterococcus faecalis, Staphylococcus epidermidis, methicillin-resistant Staphylococcus aureus (MRSA) and beta-haemolytic Streptococcus group A and B. The tests showed excellent bactericidal effect of acetic acid, particularly with problematic Gram-negative bacteria such as P. vulgaris, P. aeruginosa and A. baumannii. The microbiological spectrum of acetic acid is wide, even when tested at a low concentration of 3%. In comparison to our currently used antiseptic solutions, it showed similar - in some bacteria, even better - bactericidal properties. An evaluation of the clinical value of topical application of acetic acid is currently underway. It can be concluded that acetic acid in a concentration of 3% has excellent bactericidal effect and, therefore, seems to be suitable as a local antiseptic agent, but further clinical studies are necessary.

  10. Responses of Pisum sativum L. to exogenous indole acetic acid application under manganese toxicity.

    PubMed

    Gangwar, Savita; Singh, Vijay Pratap; Maurya, Jagat Narayan

    2011-06-01

    Responses of pea (Pisum sativum L.) seedlings to manganese (50, 100 and 250 μM) and indole acetic acid (10 and 100 μM) treatments were investigated. Single and combined exposure of pea to manganese and 100 μM indole acetic acid decreased root and shoot fresh mass, chlorophyll, carotenoids, protein and nitrogen while ammonium content increased compared to the control. Combined treatment of pea with 250 μM manganese and 100 μM indole acetic acid decreased root and shoot fresh mass by 54% and 51%, chlorophyll and carotenoids by 31% and 26%, root and shoot protein by 47% and 44%, and root and shoot nitrogen by 44% and 40%, respectively. Activities of glutamine synthetase and glutamate synthase were decreased by the exposure of manganese and 100 μM indole acetic acid while glutamate dehydrogenase activity increased. Combined application of 250 μM manganese and 100 μM indole acetic acid decreased root and shoot glutamine synthetase activity by 44% and 39%, and glutamate synthase activity by 39% and 37% while root and shoot glutamate dehydrogenase activity increased by 47% and 42%, respectively compared to the control. In contrast, application of 10 μM indole acetic acid together with manganese decreased the negative impacts of manganese, and promoted seedling growth compared to the manganese treatments alone. This study has shown that 10 μM indole acetic acid protected pea seedlings appreciably from manganese toxicity by regulating ammonium content and the activities of enzymes of ammonium assimilation, while 100 μM of indole acetic acid exhibited opposite response under manganese toxicity. PMID:21516457

  11. Iontophoretic enhancement of leuprolide acetate by fatty acids, limonene, and depilatory lotions through porcine epidermis.

    PubMed

    Rastogi, Sumeet K; Singh, Jagdish

    2004-11-01

    The effect of chemical enhancers (e.g., fatty acids, limonene, depilatory lotions) and iontophoresis was investigated on the in vitro permeability of leuprolide acetate through porcine epidermis. Franz diffusion cells and Scepter iontophoretic power source were used for the percutaneous absorption studies. Anodal iontophoresis was performed at 0.2 mA/cm2 current density. Fatty acids used were palmitic (C16:0), palmitoleic (C16:1), stearic (C18:0), oleic (C18:1), linoleic (C18:2), and linolenic (C18:3) acids. The passive and iontophoretic flux were significantly (p < 0.05) greater through fatty acids-treated porcine epidermis in comparison to the control (untreated epidermis) for leuprolide acetate. The passive and iontophoretic permeability of leuprolide acetate increased with increasing number of cis double bonds. Among the fatty acids tested, linolenic acid (C18:3) exhibited the maximum permeability of leuprolide acetate during passive (51.42 x 10(-4) cm/hr) and iontophoretic (318.98 x 10(-4) cm/hr) transport. The passive and iontophoretic flux of leuprolide acetate were significantly (p < 0.05) greater through the limonene and depilatory lotion treated epidermis in comparison to their respective control. In conclusion, iontophoresis in combination with chemical enhancers synergistically increased (p < 0.05) the in vitro permeability of leuprolide acetate through porcine epidermis.

  12. Origin and yields of acetic acid in pentose-based Maillard reaction systems.

    PubMed

    Davidek, Tomas; Gouézec, Elisabeth; Devaud, Stéphanie; Blank, Imre

    2008-04-01

    The formation of acetic acid from pentoses was studied in aqueous buffered systems (90-120 degrees C, pH 6.0-8.0) containing equimolar concentrations of 13C-labeled xylose and glycine. Acetic acid was quantified by gas chromatography-mass spectroscopy using an isotope dilution assay. Acetic acid was mainly formed from the C-1/C-2 carbon atoms of xylose (77-87%), while small amounts were also formed from the C-4/C-5 atoms of the pentose sugar (9-15%). Temperature and pH had only a small effect on the relative contribution of the sugar carbon atoms to acetic acid. These results support beta-dicarbonyl cleavage of 1-deoxypento-2,4-diulose as a major pathway leading to acetic acid in pentose-based Maillard reaction systems under food processing conditions. Acetic acid was confirmed as a major degradation product of pentoses at the early stage of the Maillard reaction, yielding 16 mol% and 28 mol% at pH 6.0 and pH 8.0, respectively. PMID:18448822

  13. Effects of acetic acid and lactic acid on physicochemical characteristics of native and cross-linked wheat starches.

    PubMed

    Majzoobi, Mahsa; Beparva, Paniz

    2014-03-15

    The effects of two common organic acids; lactic and acetic acids (150 mg/kg) on physicochemical properties of native and cross-linked wheat starches were investigated prior and after gelatinization. These acids caused formation of some cracks and spots on the granules. The intrinsic viscosity of both starches decreased in the presence of the acids particularly after gelatinization. Water solubility increased while water absorption reduced after addition of the acids. The acids caused reduction in gelatinization temperature and enthalpy of gelatinization of both starches. The starch gels became softer, less cohesive, elastic and gummy when acids were added. These changes may indicate the degradation of the starch molecules by the acids. Cross-linked wheat starch was more resistant to the acids. However, both starches became more susceptible to the acids after gelatinization. The effect of lactic acid on physicochemical properties of both starches before and after gelatinization was greater than acetic acid.

  14. Comparison of D-gluconic acid production in selected strains of acetic acid bacteria.

    PubMed

    Sainz, F; Navarro, D; Mateo, E; Torija, M J; Mas, A

    2016-04-01

    The oxidative metabolism of acetic acid bacteria (AAB) can be exploited for the production of several compounds, including D-gluconic acid. The production of D-gluconic acid in fermented beverages could be useful for the development of new products without glucose. In the present study, we analyzed nineteen strains belonging to eight different species of AAB to select those that could produce D-gluconic acid from D-glucose without consuming D-fructose. We tested their performance in three different media and analyzed the changes in the levels of D-glucose, D-fructose, D-gluconic acid and the derived gluconates. D-Glucose and D-fructose consumption and D-gluconic acid production were heavily dependent on the strain and the media. The most suitable strains for our purpose were Gluconobacter japonicus CECT 8443 and Gluconobacter oxydans Po5. The strawberry isolate Acetobacter malorum (CECT 7749) also produced D-gluconic acid; however, it further oxidized D-gluconic acid to keto-D-gluconates.

  15. [Advances in the progress of anti-bacterial biofilms properties of acetic acid].

    PubMed

    Gao, Xinxin; Jin, Zhenghua; Chen, Xinxin; Yu, Jia'ao

    2016-06-01

    Bacterial biofilms are considered to be the hindrance in the treatment of chronic wound, because of their tolerance toward antibiotics and other antimicrobial agents. They also have strong ability to escape from the host immune attack. Acetic acid, as a kind of organic weak acid, can disturb the biofilms by freely diffusing through the bacterial biofilms and bacterial cell membrane structure. Then the acid dissociates to release the hydrogen ions, leading to the disorder of the acid-base imbalance, change of protein conformation, and the degradation of the DNA within the membranes. This paper reviews the literature on the characteristics and treatment strategies of the bacterial biofilms and the acetic acid intervention on them, so as to demonstrate the roles acetic acid may play in the treatment of chronic wound, and thus provide a convincing treatment strategy for this kind of disease. PMID:27321493

  16. [Advances in the progress of anti-bacterial biofilms properties of acetic acid].

    PubMed

    Gao, Xinxin; Jin, Zhenghua; Chen, Xinxin; Yu, Jia'ao

    2016-06-01

    Bacterial biofilms are considered to be the hindrance in the treatment of chronic wound, because of their tolerance toward antibiotics and other antimicrobial agents. They also have strong ability to escape from the host immune attack. Acetic acid, as a kind of organic weak acid, can disturb the biofilms by freely diffusing through the bacterial biofilms and bacterial cell membrane structure. Then the acid dissociates to release the hydrogen ions, leading to the disorder of the acid-base imbalance, change of protein conformation, and the degradation of the DNA within the membranes. This paper reviews the literature on the characteristics and treatment strategies of the bacterial biofilms and the acetic acid intervention on them, so as to demonstrate the roles acetic acid may play in the treatment of chronic wound, and thus provide a convincing treatment strategy for this kind of disease.

  17. The fraction of cells that resume growth after acetic acid addition is a strain-dependent parameter of acetic acid tolerance in Saccharomyces cerevisiae.

    PubMed

    Swinnen, Steve; Fernández-Niño, Miguel; González-Ramos, Daniel; van Maris, Antonius J A; Nevoigt, Elke

    2014-06-01

    High acetic acid tolerance of Saccharomyces cerevisiae is a relevant phenotype in industrial biotechnology when using lignocellulosic hydrolysates as feedstock. A screening of 38 S. cerevisiae strains for tolerance to acetic acid revealed considerable differences, particularly with regard to the duration of the latency phase. To understand how this phenotype is quantitatively manifested, four strains exhibiting significant differences were studied in more detail. Our data show that the duration of the latency phase is primarily determined by the fraction of cells within the population that resume growth. Only this fraction contributed to the exponential growth observed after the latency phase, while all other cells persisted in a viable but non-proliferating state. A remarkable variation in the size of the fraction was observed among the tested strains differing by several orders of magnitude. In fact, only 11 out of 10(7)  cells of the industrial bioethanol production strain Ethanol Red resumed growth after exposure to 157 mM acetic acid at pH 4.5, while this fraction was 3.6 × 10(6) (out of 10(7)  cells) in the highly acetic acid tolerant isolate ATCC 96581. These strain-specific differences are genetically determined and represent a valuable starting point to identify genetic targets for future strain improvement.

  18. Conformational equilibria and large-amplitude motions in dimers of carboxylic acids: rotational spectrum of acetic acid-difluoroacetic acid.

    PubMed

    Gou, Qian; Feng, Gang; Evangelisti, Luca; Caminati, Walther

    2014-10-01

    We report the rotational spectra of two conformers of the acetic acid-difluoroacetic acid adduct (CH3COOH-CHF2COOH) and supply information on its internal dynamics. The two conformers differ from each other, depending on the trans or gauche orientation of the terminal -CHF2 group. Both conformers display splittings of the rotational transitions, due to the internal rotation of the methyl group of acetic acid. The corresponding barriers are determined to be V3(trans)=99.8(3) and V3(gauche)=90.5(9) cm(-1) (where V3 is the methyl rotation barrier height). The gauche form displays a further doubling of the rotational transitions, due to the tunneling motion of the -CHF2 group between its two equivalent conformations. The corresponding B2 barrier is estimated to be 108(2) cm(-1). The increase in the distance between the two monomers upon OH→OD deuteration (the Ubbelohde effect) is determined.

  19. 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.

  20. 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.

  1. Brønsted Acid/Lewis Acid Cooperatively Catalyzed Addition of Diazoester to 2H-chromene Acetals

    PubMed Central

    Luan, Yi; Qi, Yue; Gao, Hongyi; Ma, Qianqian; Schaus, Scott E.

    2014-01-01

    A novel Brønsted acid/Lewis acid dual catalyst system has been developed to promote an efficient C–C bond formation between a range of oxocarbenium precursors derived from chromene acetals and ethyl diazoacetate. The reaction proceeds under mild conditions and is tolerant of common functionalized 2H-chromene and isochromene acetals. In addition, an asymmetric variant of diazoacetate addition towards 2H-chromene acetal is described. Continued investigations include the further optimization of asymmetric induction towards the formation of diazo ester substituted 2H-chromene. PMID:25411552

  2. Adsorptive Membranes vs. Resins for Acetic Acid Removal from Biomass Hydrolysates

    SciTech Connect

    Han, B.; Carvalho, W.; Canilha, L.; da Silva, S. S.; e Silva, J. B. A.; McMillan, J. D.; Wickramasinghe, S. R.

    2006-01-01

    Acetic acid is a compound commonly found in hemicellulosic hydrolysates. This weak acid strongly influences the bioconversion of sugar containing hydrolysates. Previous investigators have used anion exchange resins for acetic acid removal from different hemicellulosic hydrolysates. In this study, the efficiency of an anion exchange membrane was compared to that of an anion exchange resin, for acetic acid removal from a DI water solution and an acidic hemicellulose hydrolysate pretreated using two different methods. Ion exchange membranes and resins have very different geometries. Here the performance of membranes and resins is compared using two dimensionless parameters, the relative mass throughput and chromatographic bed number. The relative mass throughput arises naturally from the Thomas solution for ion exchange. The results show that the membrane exhibit better performance in terms of capacity, and loss of the desired sugars. In addition acetic acid may be eluted at a higher concentration from the membrane thus leading to the possibility of recovery and re-use of the acetic acid.

  3. 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.

  4. Growth and survival of various strains of enterohemorrhagic Escherichia coli in hydrochloric and acetic acid.

    PubMed

    McKellar, R C; Knight, K P

    1999-12-01

    Nineteen strains of enterohemorrhagic Escherichia coli isolated from humans and foods were examined for their ability to grow and survive at low pH in organic (acetic) and mineral (HCl) acids. Strains were subcultured in tryptic soy broth adjusted to various pH values (3.75 to 4.75 for HCl and 4.75 to 5.75 for acetic acid) and incubated for 72 h at 37 degrees C to determine the minimum growth pH value. Minimum pH values for growth of 4.25 and 5.5 were found for HCl and acetic acid, respectively. Strains were also exposed to pH 2.0 (HCl) and pH 4.0 (acetic acid) for up to 24 h at 37 degrees C to assess their ability to survive. HCl was a more effective inhibitor after 6 h of exposure, whereas acetic acid was more effective after 24 h. Outbreak strains survived acid treatment significantly (P < or = 0.05) better than strains isolated from fermented or high-pH foods or animal or human isolates. Significant (P < or = 0.05) differences among serotypes and between O157:H7 and other serotypes were apparent after 3 or 6 h of exposure to acids. PMID:10606153

  5. 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.

  6. Conductometric simultaneous determination of acetic acid, monochloroacetic acid and trichloroacetic acid using orthogonal signal correction-partial least squares.

    PubMed

    Ghorbani, R; Ghasemi, J; Abdollahi, B

    2006-04-17

    A simultaneous conductometric titration method for determination of mixtures of acetic acid, monochloroacetic acid and trichloroacetic acid based on the multivariate calibration partial least squares is proposed. It is possible to obtain an adjustable model to relate squared concentration values of the mixtures used in the calibration range by conductance. The effect of orthogonal signal correction (OSC) as a preprocessing technique used to remove the information unrelated to the target variables is studied. The calibration model was build using conductometric titrations data of 16 mixtures of three acids. The concentration matrix was designed by a orthogonal design. The root mean squares error of prediction (RMSEP) for acetic acid, monochloroacetic acid and trichloroacetic acid with and without OSC were 0.08, 0.30 and 0.08, and 0.15, 0.40 and 0.18, respectively. The results obtained by OSC-PLS are better than the PLS and this indicate the successful application of the OSC filter as a good preprocessing method in multivariate calibration methods. The proposed procedure allows the simultaneous determination of these acids, in the synthetic mixtures.

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

    SciTech Connect

    Lubienski, Andreas Duex, Markus; Lubienski, Katrin; Grenacher, Lars; Kauffmann, Guenter

    2005-12-15

    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, 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.

  8. 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.

  9. 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. PMID:25485864

  10. Laboratory Studies of the Tropospheric Loss Processes for Acetic and Peracetic Acid

    NASA Astrophysics Data System (ADS)

    Orlando, J. J.; Tyndall, G. S.

    2002-12-01

    Organic acids are ubiquitous components of tropospheric air and contribute to acid precipitation, particularly in remote regions. These species are present in the troposphere as the result of direct emissions from anthropogenic and biogenic sources, and as the result of photochemical processing of hydrocarbons. Production of organic acids can occur following ozonolysis of unsaturated hydrocarbons, while both organic acids and peroxyacids are formed from the reactions of HO2 with acylperoxy radicals. For example, both acetic and peracetic acid are known products of the reaction of HO2 with acetylperoxy radicals. In this paper, data relevant to the gas-phase tropospheric destruction of both acetic and peracetic acid are reported, including studies of their UV absorption spectra and of their rate coefficients for reaction with OH radicals. The data, the first of their kind for peracetic acid, show that the gas-phase lifetime of this species will be on the order of 10 days, with OH reaction occurring more rapidly than photolysis. Data on the rate coefficient for reaction of OH with acetic acid appear to resolve some conflicting data in the previous literature, and show 1) that reaction of OH with the acetic acid dimer is slow compared to the monomer and 2) that the rate coefficient possesses a negative temperature dependence near room temperature.

  11. Retention of ionisable compounds on high-performance liquid chromatography XVIII: pH variation in mobile phases containing formic acid, piperazine, tris, boric acid or carbonate as buffering systems and acetonitrile as organic modifier.

    PubMed

    Subirats, Xavier; Bosch, Elisabeth; Rosés, Martí

    2009-03-20

    In the present work dissociation constants of commonly used buffering species, formic acid, piperazine, tris(hydroxymethyl)-aminomethane, boric acid and carbonate, have been determined for several acetonitrile-water mixtures. From these pK(a) values a previous model has been successfully evaluated to estimate pH values in acetonitrile-aqueous buffer mobile phases from the aqueous pH and concentration of the above mentioned buffers up to 60% of acetonitrile, and aqueous buffer concentrations between 0.005 (0.001 mol L(-1) for formic acid-formate) and 0.1 mol L(-1). The relationships derived for the presently studied buffers, together with those established for previously considered buffering systems, allow a general prediction of the pH variation of the most commonly used HPLC buffers when the composition of the acetonitrile-water mobile phase changes during the chromatographic process, such as in gradient elution. Thus, they are an interesting tool that can be easily implemented in general retention models to predict retention of acid-base analytes and optimize chromatographic separations.

  12. Reactivity and reaction intermediates for acetic acid adsorbed on CeO2(111)

    SciTech Connect

    Calaza, Florencia C.; Chen, Tsung -Liang; Mullins, David R.; Xu, Ye; Steven H. Overbury

    2015-05-02

    Adsorption and reaction of acetic acid on a CeO2(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 CeO2 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 and 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.

  13. A laboratory study of the effect of acetic acid vapor on atmospheric copper corrosion

    SciTech Connect

    Lopez-Delgado, A.; Cano, E.; Bastidas, J.M.; Lopez, F.A.

    1998-12-01

    A study was made of the copper corrosion rate and corrosion products originated by the action of acetic acid vapor at 100% relative humidity. Copper plates were exposed to an acetic acid contaminated atmosphere for a period of 21 days. Five acetic vapor concentration levels were used. The copper corrosion rate was in the range of 1 to 23 mg/dm{sup 2} day. The corrosion-product layers were characterized using electrochemical, X-ray powder diffraction, Fourier transform infrared spectrometry, and scanning electron microscopy techniques. Thermal and calorimetric studies were also performed. Some of the compounds identified were cuprite (Cu{sub 2}O), copper acetate hydrate [Cu(CH{sub 3}COO){sub 2}{center_dot}2H{sub 2}O], and copper hydroxide acetate [Cu{sub 4}(OH)(CH{sub 3}COO){sub 7}{center_dot}2H{sub 2}O]. This last compound was also characterized. The thickness of the patina layers was 4 to 8 nm for amorphous cuprite, 11 to 48 nm for cuprite, and 225 nm for copper acetate. The patina, in which the cementation process of different corrosion-product layers plays an important role, is formed by the reaction of acetic vapor with copper through porous cuprite paths.

  14. Feulgen staining of mammalian tissues fixed in picro-formol-acetic acid.

    PubMed

    Dutt, M K

    1975-01-01

    The paper describes a highly satisfactory method for in situ localization of DNA in tissues fixed in picro-formol-acetic acid or picro-formol-acetic-chromic acid mixtures following a technique in the Feulgen procedure as devised by the author. Mammalian tissues fixed in these fixatives can be hydrolysed in 6N HCl at 35 degrees C for 10 min, rinsed in water, stained with Schiff reagent after exposing the sections under UV light for 10 min, washed in water, dehydrated through a graduated series of ethanol, cleared in xylol and mounted in DPX. Sections of tissues fixed in picro-formol-acetic-chromic acid mixtures after acid hydrolysis when stained with an aqueous solution of basic fuchsin are also found to be very satisfactory for in situ localization of DNA. PMID:55054

  15. Modeling of yeast Brettanomyces bruxellensis growth at different acetic acid concentrations under aerobic and anaerobic conditions.

    PubMed

    Yahara, Garcia Alvarado; Javier, Mendez Ancona; Tulio, Mata Jimenez Marco; Javier, Gómez Rodriguez; Guadalupe, Aguilar Uscanga Maria

    2007-11-01

    Glucose utilization by Brettanomyces bruxellensis at different acetic acid concentrations under aerobic and anaerobic conditions was investigated. The presence of the organic acid disturbs the growth and fermentative activity of the yeast when its concentration exceeds 2 g l(-1). A mathematical model is proposed for the kinetic behavior analysis of yeast growing in batch culture. A Matlab algorithm was used for estimation of model parameters, whose confidence intervals were also calculated at a 0.95 probability level using a t-Student distribution for f degrees of freedom. The model successfully simulated the batch kinetics observed at different concentrations of acetic acid under both oxygen conditions.

  16. Conversion of Acetic Acid from the Catalytic Pyrolysis of Xylan Over CeO2.

    PubMed

    Lee, Heejin; Ko, Jeong Huy; Kwon, Woo Hyun; Park, Young-Kwon

    2016-05-01

    CeO2 was synthesized hydrothermally in supercritical water and applied to the catalytic pyrolysis of xylan. Acetic acid, which is the main component in bio-oil produced from the non-catalytic pyrolysis of xylan, deteriorates the fuel quality of the oil. Catalysis over CeO2 effectively converted the acetic acid to ketone species, such as acetone, thereby reducing the acidity of the oil considerably. The content of aromatics in bio-oil was also increased substantially by catalysis. PMID:27483777

  17. The Fate of Acetic Acid during Glucose Co-Metabolism by the Spoilage Yeast Zygosaccharomyces bailii

    PubMed Central

    Rodrigues, Fernando; Sousa, Maria João; Ludovico, Paula; Santos, Helena; Côrte-Real, Manuela; Leão, Cecília

    2012-01-01

    Zygosaccharomyces bailii is one of the most widely represented spoilage yeast species, being able to metabolise acetic acid in the presence of glucose. To clarify whether simultaneous utilisation of the two substrates affects growth efficiency, we examined growth in single- and mixed-substrate cultures with glucose and acetic acid. Our findings indicate that the biomass yield in the first phase of growth is the result of the weighted sum of the respective biomass yields on single-substrate medium, supporting the conclusion that biomass yield on each substrate is not affected by the presence of the other at pH 3.0 and 5.0, at least for the substrate concentrations examined. In vivo 13C-NMR spectroscopy studies showed that the gluconeogenic pathway is not operational and that [2−13C]acetate is metabolised via the Krebs cycle leading to the production of glutamate labelled on C2, C3 and C4. The incorporation of [U-14C]acetate in the cellular constituents resulted mainly in the labelling of the protein and lipid pools 51.5% and 31.5%, respectively. Overall, our data establish that glucose is metabolised primarily through the glycolytic pathway, and acetic acid is used as an additional source of acetyl-CoA both for lipid synthesis and the Krebs cycle. This study provides useful clues for the design of new strategies aimed at overcoming yeast spoilage in acidic, sugar-containing food environments. Moreover, the elucidation of the molecular basis underlying the resistance phenotype of Z. bailii to acetic acid will have a potential impact on the improvement of the performance of S. cerevisiae industrial strains often exposed to acetic acid stress conditions, such as in wine and bioethanol production. PMID:23285028

  18. Use of multi-parameter flow cytometry as tool to monitor the impact of formic acid on Saccharomyces carlsbergensis batch ethanol fermentations.

    PubMed

    Freitas, Cláudia; Neves, Elisabete; Reis, Alberto; Passarinho, Paula C; da Silva, Teresa Lopes

    2013-04-01

    The use of lignocellulosic materials as substrate for bioethanol production is considered a cost-effective approach to make the biofuel production process economically sustainable. However, lignocellulosic hydrolysis releases toxic compounds such as weak acids which inhibit microorganism growth and ethanol production. In order to understand the physiological response of Saccharomyces carlsbergensis when fermenting glucose in the presence of formic acid (HF), the yeast growth was monitored by multi-parameter flow cytometry. Cytoplasmic membrane potential decreased as the HF concentration increased and as the yeast culture reached the stationary phase. However, the proportion of cells with permeabilized membrane did not increase with the HF concentration increase. The accumulation of reactive oxygen species was also monitored. Control and fermentations at low HF concentrations (<1 g/L) resulted in a high proportion of highly oxidized cells at the stationary phase. The multi-parameter flow cytometry approach proved to be a useful tool to monitor the physiological stress response of S. carlsbergensis growth and ethanol production in the presence of HF, an inhibitor present in lignocellulosic hydrolysates. The information here obtained at near real time can be used to enhance second-generation bioethanol production process efficiency.

  19. The electrooxidation mechanism of formic acid on platinum and on lead ad-atoms modified platinum studied with the kinetic isotope effect

    NASA Astrophysics Data System (ADS)

    Bełtowska-Brzezinska, M.; Łuczak, T.; Stelmach, J.; Holze, R.

    2014-04-01

    Kinetics and mechanism of formic acid (FA) oxidation on platinum and upd-lead ad-atoms modified platinum electrodes have been studied using unlabelled and deuterated compounds. Poisoning of the electrode surface by CO-like species was prevented by suppression of dissociative chemisorption of FA due to a fast competitive underpotential deposition of lead ad-atoms on the Pt surface from an acidic solution containing Pb2+ cations. Modification of the Pt electrode with upd lead induced a catalytic effect in the direct electrooxidation of physisorbed FA to CO2. With increasing degree of H/D substitution, the rate of this reaction decreased in the order: HCOOH > DCOOH ≥ HCOOD > DCOOD. HCOOH was oxidized 8.5-times faster on a Pt/Pb electrode than DCOOD. This primary kinetic isotope effect proves that the C-H- and O-H-bonds are simultaneously cleaved in the rate determining step. A secondary kinetic isotope effect was found in the dissociative chemisorption of FA in the hydrogen adsorption-desorption range on a bare Pt electrode after H/D exchange in the C-H bond, wherein the influence of deuterium substitution in the O-H group was negligibly small. Thus the C-H bond cleavage is accompanied by the C-OH and not the O-H bond split in the FA decomposition, producing CO-like species on the Pt surface sites.

  20. Structural characterization of electron-induced proton transfer in the formic acid dimer anion, (HCOOH)2-, with vibrational and photoelectron spectroscopies.

    PubMed

    Gerardi, Helen K; DeBlase, Andrew F; Leavitt, Christopher M; Su, Xiaoge; Jordan, Kenneth D; McCoy, Anne B; Johnson, Mark A

    2012-04-01

    The (HCOOH)(2) anion, formed by electron attachment to the formic acid dimer (FA(2)), is an archetypal system for exploring the mechanics of the electron-induced proton transfer motif that is purported to occur when neutral nucleic acid base-pairs accommodate an excess electron [K. Aflatooni, G. A. Gallup, and P. D. Burrow, J. Phys. Chem. A 102, 6205 (1998); J. H. Hendricks, S. A. Lyapustina, H. L. de Clercq, J. T. Snodgrass, and K. H. Bowen, J. Chem Phys. 104, 7788 (1996); C. Desfrancois, H. Abdoul-Carime, and J. P. Schermann, ibid. 104, 7792 (1996)]. The FA(2) anion and several of its H∕D isotopologues were isolated in the gas phase and characterized using Ar-tagged vibrational predissociation and electron autodetachment spectroscopies. The photoelectron spectrum of the FA(2) anion was also recorded using velocity-map imaging. The resulting spectroscopic information verifies the equilibrium FA(2)(-) geometry predicted by theory which features a symmetrical, double H-bonded bridge effectively linking together constituents that most closely resemble the formate ion and a dihydroxymethyl radical. The spectroscopic signatures of this ion were analyzed with the aid of calculated anharmonic vibrational band patterns. PMID:22482563