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

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

Kinetics and toxic effects of repeated intravenous dosage of formic acid in rabbits.

PubMed Central

Liesivuori, J.; Kosma, V. M.; Naukkarinen, A.; Savolainen, H.

1987-01-01

Adult male rabbits were injected i.v. with 100 mg buffered formic acid per kg body weight daily for 5 days with 24 h between the doses. The fifth dose was labelled with 14C-formic acid. Rabbits were killed 1, 2 and 20 h after the last injection. The highest formic acid concentrations were found one hour after the fifth dose. Total formic acid concentrations were always higher than radiometrically measured. The maximum concentrations of formic acid in brain, heart, kidney and liver were roughly similar to the concentration which inhibits half of the cytochrome oxidase activity in vitro. Histological studies clearly demonstrated the histotoxic changes at cellular level. Calcium deposits were detected in all organs of the injected rabbits. They were absent in control animals. It seems that the formic acid metabolism is slow and that it may cause sufficient hypoxic acidosis to allow the calcium influx and cellular damage. Images Fig. 1 Fig. 2 Fig. 3 Fig. 4 PMID:3426949

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

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

Bennett, Chris J.; Kim, Yong Seol; Kaiser, Ralf I.

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 labeledmore » 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.« less

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

Formic acid dimers in a nitrogen matrix

NASA Astrophysics Data System (ADS)

Lopes, Susy; Fausto, Rui; Khriachtchev, Leonid

2018-01-01

Formic acid (HCOOH) dimers are studied by infrared spectroscopy in a nitrogen matrix and by ab initio calculations. We benefit from the use of a nitrogen matrix where the lifetime of the higher-energy (cis) conformer is very long (˜11 h vs. 7 min in an argon matrix). As a result, in a nitrogen matrix, a large proportion of the cis conformer can be produced by vibrational excitation of the lower-energy (trans) conformer. Three trans-trans, four trans-cis, and three cis-cis dimers are found in the experiments. The spectroscopic information on most of these dimers is enriched compared to the previous studies in an argon matrix. The cis-cis dimers of ordinary formic acid (without deuteration) are reported here for the first time. Several conformational processes are obtained using selective excitation by infrared light, some of them also for the first time. In particular, we report on the formation of cis-cis dimers upon vibrational excitation of trans-cis dimers. Tunneling decays of several dimers have been detected in the dark. The tunneling decay of cis-cis dimers of formic acid as well as the stabilization of cis units in cis-cis dimers is also observed for the first time.

Formic acid dimers in a nitrogen matrix.

PubMed

Lopes, Susy; Fausto, Rui; Khriachtchev, Leonid

2018-01-21

Formic acid (HCOOH) dimers are studied by infrared spectroscopy in a nitrogen matrix and by ab initio calculations. We benefit from the use of a nitrogen matrix where the lifetime of the higher-energy (cis) conformer is very long (∼11 h vs. 7 min in an argon matrix). As a result, in a nitrogen matrix, a large proportion of the cis conformer can be produced by vibrational excitation of the lower-energy (trans) conformer. Three trans-trans, four trans-cis, and three cis-cis dimers are found in the experiments. The spectroscopic information on most of these dimers is enriched compared to the previous studies in an argon matrix. The cis-cis dimers of ordinary formic acid (without deuteration) are reported here for the first time. Several conformational processes are obtained using selective excitation by infrared light, some of them also for the first time. In particular, we report on the formation of cis-cis dimers upon vibrational excitation of trans-cis dimers. Tunneling decays of several dimers have been detected in the dark. The tunneling decay of cis-cis dimers of formic acid as well as the stabilization of cis units in cis-cis dimers is also observed for the first time.

Toxicity of formic acid to red imported fire ants, Solenopsis invicta Buren.

PubMed

Chen, Jian; Rashid, Tahir; Feng, Guolei

2012-10-01

Ants often compete with other ants for resources. Although formic acid is a common defensive chemical of formicine ants, it does not occur in any other subfamilies in Formicidae. No information on toxicity of formic acid to red imported fire ants, Solenopsis invicta, is available. This study examined its contact and fumigation toxicity to S. invicta in the laboratory. In a contact toxicity bioassay, 24 h LD50 values of formic acid for workers ranged from 124.54 to 197.71 µg ant(-1) . Female alates and queens were much less sensitive to formic acid than workers. At a concentration of 271.72 µg ant(-1) , which killed 81.09 ± 16.04% of workers, the 24 h mortality was up to 39.64% for female alates and 38.89% for queens. In fumigation bioassays, 24 h LC50 values ranged from 0.26 to 0.50 µg mL(-1) for workers, 0.32 µg mL(-1) for male alates and 0.70 µg mL(-1) for female alates. Complete mortality (100%) in queens occurred 24 h after they had been exposed to 1.57 µg mL(-1) of formic acid. At a concentration of 2.09 µg mL(-1) , KT50 values ranged from 23.03 to 43.85 min for workers, from 37.84 to 58.37 min for male alates, from 86.06 to 121.05 min for female alates and from 68.00 to 85.92 min for queens. When applied topically, formic acid was significantly less toxic than bifenthrin to red imported fire ants. Although its fumigation toxicity was lower than that of dichlorvos, formic acid had about an order of magnitude higher toxicity to S. invicta than to other insects studied so far. It may be worth investigating the use of formic acid for managing imported fire ants. This article is a US Government work and is in the public domain in the USA.

Towards a practical setup for hydrogen production from formic acid.

PubMed

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

2013-07-01

Formic acid cracker: A mini plant that allows for continuous formic acid decomposition to hydrogen and carbon dioxide under ambient conditions is presented. By using an in situ-formed ruthenium catalyst, unprecedented turnover numbers over 1,000,000 are achieved. The active catalyst is formed in situ from commercially available [RuCl2 (benzene)]2 and 1,2-bisdiphenylphosphinoethane. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An Alternative Mechanism for the Dimerization of Formic Acid

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

Brinkman, Nicole R.; Tschumper, Gregory; Yan, Ge

Gas-phase formic acid exists primarily as a cyclic dimer. The mechanism of dimerization has been traditionally considered to be a synchronous process; however, recent experimental findings suggest a possible alternative mechanism by which two formic acid monomers proceed through an acyclic dimer to the cyclic dimer in a stepwise process. To investigate this newly proposed process of dimerization in formic acid, density functional theory and second-order Moeller-Plesset perturbation theory (MP2) have been used to optimize cis and trans monomers of formic acid, the acyclic and cyclic dimers, and the acyclic and cyclic transition states between minima. Single-point energies of themore » trans monomer, dimer minima, and transition states at the MP2/TZ2P+diff optimized geometries were computed at the coupled-cluster level of theory including singles and doubles with perturbatively applied triple excitations [CCSD(T)] with an aug-cc-pVTZ basis set to obtain an accurate determination of energy barriers and dissociation energies. A counterpoise correction was performed to determine an estimate of the basis set superposition error in computing relative energies. The explicitly correlated MP2 method of Kutzelnigg and Klopper (MP2-R12) was used to provide an independent means for obtaining the MP2 one-particle limit. The cyclic minimum is predicted to be 6.3 kcal/mol more stable than the acyclic minimum, and the barrier to double proton transfer is 7.1 kcal/mol.« less

[Discovery of the target genes inhibited by formic acid in Candida shehatae].

PubMed

Cai, Peng; Xiong, Xujie; Xu, Yong; Yong, Qiang; Zhu, Junjun; Shiyuan, Yu

2014-01-04

At transcriptional level, the inhibitory effects of formic acid was investigated on Candida shehatae, a model yeast strain capable of fermenting xylose to ethanol. Thereby, the target genes were regulated by formic acid and the transcript profiles were discovered. On the basis of the transcriptome data of C. shehatae metabolizing glucose and xylose, the genes responsible for ethanol fermentation were chosen as candidates by the combined method of yeast metabolic pathway analysis and manual gene BLAST search. These candidates were then quantitatively detected by RQ-PCR technique to find the regulating genes under gradient doses of formic acid. By quantitative analysis of 42 candidate genes, we finally identified 10 and 5 genes as markedly down-regulated and up-regulated targets by formic acid, respectively. With regard to gene transcripts regulated by formic acid in C. shehatae, the markedly down-regulated genes ranking declines as follows: xylitol dehydrogenase (XYL2), acetyl-CoA synthetase (ACS), ribose-5-phosphate isomerase (RKI), transaldolase (TAL), phosphogluconate dehydrogenase (GND1), transketolase (TKL), glucose-6-phosphate dehydrogenase (ZWF1), xylose reductase (XYL1), pyruvate dehydrogenase (PDH) and pyruvate decarboxylase (PDC); and a declining rank for up-regulated gens as follows: fructose-bisphosphate aldolase (ALD), glucokinase (GLK), malate dehydrogenase (MDH), 6-phosphofructokinase (PFK) and alcohol dehydrogenase (ADH).

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 Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS FOOD ADDITIVES PERMITTED IN FEED AND DRINKING WATER OF ANIMALS Food Additive...

Microwave structure for the propiolic acid-formic acid complex.

PubMed

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

2013-10-03

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.

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.

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

Hydrolysis of Ketene Catalyzed by Formic Acid: Modification of Reaction Mechanism, Energetics, and Kinetics with Organic Acid Catalysis

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

Louie, Matthew K.; Francisco, Joseph S.; Verdicchio, Marco

2015-05-14

The hydrolysis of ketene (H2C=C=O) to form acetic acid involving two water molecules and also separately in the presence of one to two water molecules and formic acid (FA) was investigated. Our results show that, while the currently accepted indirect mechanism, involving addition of water across the carbonyl C=O bond of ketene to form an ene-diol followed by tautomerization of the ene-diol to form acetic acid, is the preferred pathway when water alone is present, with formic acid as catalyst, addition of water across the ketene C=C double bond to directly produce acetic acid becomes the kinetically favored pathway formore » temperatures below 400 K. We find not only that the overall barrier for ketene hydrolysis involving one water molecule and formic acid (H2C2O + H2O + FA) is significantly lower than that involving two water molecules (H2C2O + 2H(2)O) but also that FA is able to reduce the barrier height for the direct path, involving addition of water across the C=C double bond, so that it is essentially identical with (6.4 kcal/mol) that for the indirect ene-diol formation path involving addition of water across the C=O bond. For the case of ketene hydrolysis involving two water molecules and formic acid (H2C2O + 2H(2)O + FA), the barrier for the direct addition of water across the C=C double bond is reduced even further and is 2.5 kcal/mol lower relative to the ene-diol path involving addition of water across the C=O bond. In fact, the hydrolysis barrier for the H2C2O + 2H(2)O + FA reaction through the direct path is sufficiently low (2.5 kcal/mol) for it to be an energetically accessible pathway for acetic acid formation under atmospheric conditions. Given the structural similarity between acetic and formic acid, our results also have potential implications for aqueous-phase chemistry. Thus, in an aqueous environment, even in the absence of formic acid, though the initial mechanism for ketene hydrolysis is expected to involve addition of water across the

DFT study of hydrogen production from formic acid decomposition on Pd-Au alloy nanoclusters

NASA Astrophysics Data System (ADS)

Liu, D.; Gao, Z. Y.; Wang, X. C.; Zeng, J.; Li, Y. M.

2017-12-01

Recently, it has been reported that the hydrogen production rate of formic acid decomposition can be significantly increased using Pd-Au binary alloy nano-catalysts [Wang et al. J. Mater. Chem. A 1 (2013) 12721-12725]. To explain the reaction mechanism of this alloy catalysis method, formic acid decomposition reactions on pure Pd and Pd-Au alloy nanoclusters are studied via density functional theory simulations. The simulation results indicate that the addition of inert element Au would not influence formic acid decomposition on Pd surface sites of Pd-Au alloy nanoclusters. On the other hand, the existence of Au surface sites brings relative weak hydrogen atom adsorption. On Pd-Au alloy nanoclusters, the dissociated hydrogen atoms from formic acid are easier to combine as hydrogen molecules than that on pure Pd clusters. Via the synergetic effect between Pd and Au, both formic acid decomposition and hydrogen production are events with large probability, which eventually results in high hydrogen production rate.

21 CFR 186.1316 - Formic acid.

Code of Federal Regulations, 2014 CFR

2014-04-01

... used for food packaging. (c) The ingredient is used at levels not to exceed good manufacturing practice... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Formic acid. 186.1316 Section 186.1316 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) INDIRECT FOOD...

Topical formic acid puncture technique for the treatment of common warts.

PubMed

Bhat, R M; Vidya, K; Kamath, G

2001-06-01

Warts are a common chronic skin disorder that can be cosmetically disfiguring and, depending on the location, cause inhibition of function. The presence of dozens of topical and systemic treatments for warts is a testament to the lack of a rapid, simple, uniformly effective, inexpensive, nonscarring, and painless treatment. The purpose of this study was to determine the efficacy and safety of 85% formic acid application, an inexpensive therapy, for the treatment of warts. A placebo-controlled, nonrandomized, open trial was performed in 100 patients with common warts attending Father Muller's Medical College Hospital, Mangalore. Fifty patients received 85% formic acid application and 50 patients received placebo (water) using a topical application/needle puncture technique every other day. Ninety-two per cent of patients who received formic acid application showed complete disappearance of warts after a 3-4-week treatment period, compared to 6% in the placebo group. The results show that 85% formic acid application is a safe, economical, and effective alternative in the treatment of common warts with few side-effects and good compliance. A multicenter trial is needed to examine the efficacy and safety of this treatment.

21 CFR 186.1316 - Formic acid.

Code of Federal Regulations, 2011 CFR

2011-04-01

... paper and paperboard used for food packaging. (c) The ingredient is used at levels not to exceed good... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Formic acid. 186.1316 Section 186.1316 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN...

21 CFR 186.1316 - Formic acid.

Code of Federal Regulations, 2010 CFR

2010-04-01

... paper and paperboard used for food packaging. (c) The ingredient is used at levels not to exceed good... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Formic acid. 186.1316 Section 186.1316 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN...

21 CFR 186.1316 - Formic acid.

Code of Federal Regulations, 2012 CFR

2012-04-01

... paper and paperboard used for food packaging. (c) The ingredient is used at levels not to exceed good... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Formic acid. 186.1316 Section 186.1316 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN...

21 CFR 186.1316 - Formic acid.

Code of Federal Regulations, 2013 CFR

2013-04-01

... paper and paperboard used for food packaging. (c) The ingredient is used at levels not to exceed good... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Formic acid. 186.1316 Section 186.1316 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN...

Formic Acid: Development of an Analytical Method and Use as Process Indicator in Anaerobic Systems

DTIC Science & Technology

1992-03-01

distilled to remove compounds such as cinnamic , glycolic and levulinic acids which can be oxidized to formic acid by ceric sulfate, thus interfering...I AD-A250 668 D0 ,I I I 111 Wl’i ill EDT|CS ELECTE MAY 27 1992 I C I FORMIC ACID : DEVELCPMENT OF AN ANALYTICAL METHOD AND USE AS A PROCESS INDICATOR...OF TECHNOLOGY A UNIT OF THE UNIVERSITY SYSTEM OF GEORGIA SCHOOL OF CIVIL ENGINEERING ATLANTA, GEORGIA 30332 iIi ii FORMIC ACID : DEVELOPMENT OF AN

Reaction of atomic hydrogen with formic acid.

PubMed

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

2014-04-07

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.

Formic acid interaction with the uranyl(VI) ion: structural and photochemical characterization.

PubMed

Lucks, Christian; Rossberg, André; Tsushima, Satoru; Foerstendorf, Harald; Fahmy, Karim; Bernhard, Gert

2013-10-07

Complex formation between the uranyl(VI) ion and formic acid was studied by infrared absorption (IR) and X-ray absorption (EXAFS) spectroscopy as well as density functional theory (DFT) calculations. In contrast to the acetate ion which forms exclusively a bidentate complex with uranyl(VI), the formate ion binds to uranyl(VI) in a unidentate fashion. The photochemistry of the uranyl(VI)-formic acid system was explored by DFT calculations and photoreduction of uranyl(VI) in the presence of formic acid was found to occur via an intermolecular process, that is, hydrogen abstraction from hydrogenformate by the photo-excited uranyl(VI). There is no photo-induced decarboxylation of uranyl(VI) formate via an intramolecular process, presumably due to lack of a C=C double bond.

Evaluation of the effect of formic acid and sodium formate on hair reduction in rat

PubMed Central

Banihashemi, Mahnaz; Rad, Abolfazl Khajavi; Yazdi, Seyed Abbas Tabatabaee; Rakhshande, Hasan; Ghoyonlo, Vahid Mashayekhi; Zabihi, Zahra; Yousefzadeh, Hadis

2011-01-01

Hirsutism is a common problem in dermatology that imposes high socioeconomical costs on medical care. Consequently, researchers are actively searching for cheaper and safer methods for therapeutic treatment. The objective of the present study is to evaluate formic oil, enriched from formic acid, for the removal of unwanted hair. In this study, 32 female rats (150–200 g) were randomly divided into four groups and maintained with normal water and food availability. A patch of skin was shaved on each rat for application of test solutions. The control group was treated with local once-daily applications of normal saline. The formic acid, acetic acid, and sodium formate groups were treated with once-daily applications of formic acid (pH 5.5), acetic acid (pH 5.5), or sodium formate, respectively. After 2 weeks, horizontally cut sample biopsies were removed, and the numbers of hair follicles were counted under high field microscopy by a specialist blinded to the treatments. Kolmogorov–Smirnov test results indicated a nonparametric distribution for the rat groups. ANOVA analysis indicated no statistically significant differences between groups (P < 0.05). There weren’t any side effects or evidence for toxicity during the study period. However, hair follicle counts showed a descending order of control, acetic acid, formic acid, and sodium formate. Although the sodium formate group had the lowest hair follicle numbers, the difference was not statistically significant (P > 0.05). Formic acid was not effective in reducing hair follicle numbers in rats. PMID:21760741

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.

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.

Measurement of formic acid, acetic acid and hydroxyacetaldehyde, hydrogen peroxide, and methyl peroxide in air by chemical ionization mass spectrometry: airborne method development

NASA Astrophysics Data System (ADS)

Treadaway, Victoria; Heikes, Brian G.; McNeill, Ashley S.; Silwal, Indira K. C.; O'Sullivan, Daniel W.

2018-04-01

A chemical ionization mass spectrometry (CIMS) method utilizing a reagent gas mixture of O2, CO2, and CH3I in N2 is described and optimized for quantitative gas-phase measurements of hydrogen peroxide (H2O2), methyl peroxide (CH3OOH), formic acid (HCOOH), and the sum of acetic acid (CH3COOH) and hydroxyacetaldehyde (HOCH2CHO; also known as glycolaldehyde). The instrumentation and methodology were designed for airborne in situ field measurements. The CIMS quantification of formic acid, acetic acid, and hydroxyacetaldehyde used I- cluster formation to produce and detect the ion clusters I-(HCOOH), I-(CH3COOH), and I-(HOCH2CHO), respectively. The CIMS also produced and detected I- clusters with hydrogen peroxide and methyl peroxide, I-(H2O2) and I-(CH3OOH), though the sensitivity was lower than with the O2- (CO2) and O2- ion clusters, respectively. For that reason, while the I- peroxide clusters are presented, the focus is on the organic acids. Acetic acid and hydroxyacetaldehyde were found to yield equivalent CIMS responses. They are exact isobaric compounds and indistinguishable in the CIMS used. Consequently, their combined signal is referred to as the acetic acid equivalent sum. Within the resolution of the quadrupole used in the CIMS (1 m/z), ethanol and 1- and 2-propanol were potential isobaric interferences to the measurement of formic acid and the acetic acid equivalent sum, respectively. The CIMS response to ethanol was 3.3 % that of formic acid and the response to either 1- or 2-propanol was 1 % of the acetic acid response; therefore, the alcohols were not considered to be significant interferences to formic acid or the acetic acid equivalent sum. The multi-reagent ion system was successfully deployed during the Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ) in 2014. The combination of FRAPPÉ and laboratory calibrations allowed for the post-mission quantification of formic acid and the acetic acid equivalent sum observed during

Formic acid excretion in rats exposed to trichloroethylene: a possible explanation for renal toxicity in long-term studies.

PubMed

Green, T; Dow, J; Foster, J R; Hext, P M

1998-05-15

Rats exposed to trichloroethylene, either by gavage or by inhalation, excreted large amounts of formic acid in urine which was accompanied by a change in urinary pH, increased excretion of ammonia, and slight increases in the excretion of calcium. Following a single 6-h exposure to 500 ppm trichloroethylene, the excretion of formic acid was comparable to that seen after a 500 mg/kg dose of formic acid itself, yet the half-life was markedly different. Formate excretion in trichloroethylene treated rats reached a maximum on day 2 and had a half-life of 4-5 days, whereas urinary excretion was complete within 24 h following a single dose of formic acid itself. Formic acid was shown not to be a metabolite of trichloroethylene. When rats were exposed to 250 or 500 ppm trichloroethylene, 6 h/day, for 28 days, the only significant effects were increased formic acid and ammonia excretion, and a change in urinary pH. There was no evidence of morphological liver or kidney damage. Long-term exposure to formic acid is known to cause kidney damage suggesting that excretion of this acid may contribute to the kidney damage seen in the long-term studies with trichloroethylene.

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.

Simple and rapid hydrogenation of p-nitrophenol with aqueous formic acid in catalytic flow reactors

PubMed Central

Kawasaki, Shin-ichiro; Suzuki, Akira

2013-01-01

Summary The inner surface of a metallic tube (i.d. 0.5 mm) was coated with a palladium (Pd)-based thin metallic layer by flow electroless plating. Simultaneous plating of Pd and silver (Ag) from their electroless-plating solution produced a mixed distributed bimetallic layer. Preferential acid leaching of Ag from the Pd–Ag layer produced a porous Pd surface. Hydrogenation of p-nitrophenol was examined in the presence of formic acid simply by passing the reaction solution through the catalytic tubular reactors. p-Aminophenol was the sole product of hydrogenation. No side reaction occurred. Reaction conversion with respect to p-nitrophenol was dependent on the catalyst layer type, the temperature, pH, amount of formic acid, and the residence time. A porous and oxidized Pd (PdO) surface gave the best reaction conversion among the catalytic reactors examined. p-Nitrophenol was converted quantitatively to p-aminophenol within 15 s of residence time in the porous PdO reactor at 40 °C. Evolution of carbon dioxide (CO2) was observed during the reaction, although hydrogen (H2) was not found in the gas phase. Dehydrogenation of formic acid did not occur to any practical degree in the absence of p-nitrophenol. Consequently, the nitro group was reduced via hydrogen transfer from formic acid to p-nitrophenol and not by hydrogen generated by dehydrogenation of formic acid. PMID:23843908

Determination of formic acid tissue and fluid concentrations in three fatalities due to methanol poisoning.

PubMed

Hantson, P; Haufroid, V; Mahieu, P

2000-12-01

Three fatalities caused by methanol ingestion are reported. Admission blood methanol concentrations ranged from 0.28 to 4.6 g/L. Two patients had been admitted after a significant delay (>20 hours), and one patient was observed within 90 minutes following ingestion. Formic acid levels were determined in blood samples at admission and ranged from 302 to 680 mg/L. The patients died 44, 55, and 82 hours after poisoning. Formic acid determinations in postmortem tissues were performed by a gas chromatograph method. The authors found great variability in formic acid distribution among the patients and among organs.

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

PubMed Central

Lock, Edward A; Reed, Celia J; McMillan, JoEllyn M; Oatis, John R; Schnellmann, Rick G

2007-01-01

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 metabolised 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 3-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 et al., 2006) supporting the view that glutathione derived metabolites are likely to be responsible for nephrotoxicity. PMID:17161896

Copper-catalyzed formic acid synthesis from CO2 with hydrosilanes and H2O.

PubMed

Motokura, Ken; Kashiwame, Daiki; Miyaji, Akimitsu; Baba, Toshihide

2012-05-18

A copper-catalyzed formic acid synthesis from CO2 with hydrosilanes has been accomplished. The Cu(OAc)2·H2O-1,2-bis(diphenylphosphino)benzene system is highly effective for the formic acid synthesis under 1 atm of CO2. The TON value approached 8100 in 6 h. The reaction pathway was revealed by in situ NMR analysis and isotopic experiments.

Formic acid-assisted synthesis of palladium nanocrystals and their electrocatalytic properties.

PubMed

Wang, Qinchao; Wang, Yiqian; Guo, Peizhi; Li, Qun; Ding, Ruixue; Wang, Baoyan; Li, Hongliang; Liu, Jingquan; Zhao, X S

2014-01-14

Palladium (Pd) nanocrystals have been synthesized by using formic acid as the reducing agent at room temperature. When the concentration of formic acid was increased continuously, the size of Pd nanocrystals first decreased to a minimum and then increased slightly again. The products have been investigated by a series of techniques, including X-ray diffraction, high-resolution transmission electron microscopy (HRTEM), UV-vis absorption, and electrochemical measurements. The formation of Pd nanocrystals is proposed to be closely related to the dynamical imbalance of the growth and dissolution rate of Pd nanocrystals associated with the adsorption of formate ions onto the surface of the intermediates. It is found that small Pd nanocrystals showed blue-shifted adsorption peaks compared with large ones. Pd nanocrystals with the smallest size display the highest electrocatalytic activity for the electrooxidation of formic acid and ethanol on the basis of cyclic voltammetry and chronoamperometric data. It is suggested that both the electrochemical active surface area and the small size effect are the key roles in determining the electrocatalytic performances of Pd nanocrystals. A "dissolution-deposition-aggregation" process is proposed to explain the variation of the electrocatalytic activity during the electrocatalysis according to the HRTEM characterization.

Formic acid production using a microbial electrolysis desalination and chemical-production cell.

PubMed

Lu, Yaobin; Luo, Haiping; Yang, Kunpeng; Liu, Guangli; Zhang, Renduo; Li, Xiao; Ye, Bo

2017-11-01

The aim of this study was to investigate the feasibility and optimization of formic acid production in the microbial electrolysis desalination and chemical-production cell (MEDCC). The maximum current density in the MEDCC with 72cm of the anode fiber length (72-MEDCC) reached 24.0±2.0A/m 2 , which was much higher than previously reported. The maximum average formic acid production rate in the 72-MEDCC was 5.28 times higher than that in the MEDCC with 24cm of the anode fiber length (37.00±1.15vs. 7.00±0.25mg/h). High performance in the 72-MEDCC was attributed to small membrane spacing (1mm), high flow rate (1500μL/min) on the membrane surface and high anode biomass. The minimum electricity consumption of 0.34±0.04kWh/kg in the 72-MEDCC was only 3.1-18.8% of those in the EDBMs. The MEDCC should be a promising technology for the formic acid production. Copyright © 2017 Elsevier Ltd. All rights reserved.

Tunneling dynamics of double proton transfer in formic acid and benzoic acid dimers

NASA Astrophysics Data System (ADS)

Smedarchina, Zorka; Fernández-Ramos, Antonio; Siebrand, Willem

2005-04-01

Direct dynamics calculations based on instanton techniques are reported of tunneling splittings due to double proton transfer in formic and benzoic acid dimers. The results are used to assign the observed splittings to levels for which the authors of the high-resolution spectra could not provide a definitive assignment. In both cases the splitting is shown to be due mainly to the zero-point level rather than to the vibrationally or electronically excited level whose spectrum was investigated. This leads to zero-point splittings of 375MHz for (DCOOH)2 and 1107MHz for the benzoic acid dimer. Thus, contrary to earlier calculations, it is found that the splitting is considerably larger in the benzoic than in the formic acid dimer. The calculations are extended to solid benzoic acid where the asymmetry of the proton-transfer potential induced by the crystal can be overcome by suitable doping. This has allowed direct measurement of the interactions responsible for double proton transfer, which were found to be much larger than those in the isolated dimer. To account for this observation both static and dynamic effects of the crystal forces on the intradimer hydrogen bonds are included in the calculations. The same methodology, extended to higher temperatures, is used to calculate rate constants for HH, HD, and DD transfers in neat benzoic acid crystals. The results are in good agreement with reported experimental rate constants measured by NMR relaxometry and, if allowance is made for small structural changes induced by doping, with the transfer matrix elements observed in doped crystals. Hence the method used allows a unified description of tunneling splittings in the gas phase and in doped crystals as well as of transfer rates in neat crystals.

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).

Fractionation of lignocellulosic biopolymers from sugarcane bagasse using formic acid-catalyzed organosolv process.

PubMed

Suriyachai, Nopparat; Champreda, Verawat; Kraikul, Natthakorn; Techanan, Wikanda; Laosiripojana, Navadol

2018-05-01

A one-step formic acid-catalyzed organosolv process using a low-boiling point acid-solvent system was studied for fractionation of sugarcane bagasse. Compared to H 2 SO 4 , the use of formic acid as a promoter resulted in higher efficiency and selectivity on removals of hemicellulose and lignin with increased enzymatic digestibility of the cellulose-enriched solid fraction. The optimal condition from central composite design analysis was determined as 40 min residence time at 159 °C using water/ethanol/ethyl acetate/formic acid in the respective ratios of 43:20:16:21%v/v. Under this condition, a 94.6% recovery of cellulose was obtained in the solid with 80.2% cellulose content while 91.4 and 80.4% of hemicellulose and lignin were removed to the aqueous-alcohol-acid and ethyl acetate phases, respectively. Enzymatic hydrolysis of the solid yielded 84.5% glucose recovery compared to available glucan in the raw material. Physicochemical analysis revealed intact cellulose fibers with decreased crystallinity while the hemicellulose was partially recovered as mono- and oligomeric sugars. High-purity organosolv lignin with < 1% sugar cross-contamination was obtained with no major structural modification according to Fourier-transform infrared spectroscopy. The work represents an alternative process for efficient fractionation of lignocellulosic biomass in biorefineries.

Structural characteristics and properties of the regenerated silk fibroin prepared from formic acid.

PubMed

Um, I C; Kweon, H Y; Park, Y H; Hudson, S

2001-08-20

Structural characteristics and thermal and solution properties of the regenerated silk fibroin (SF) prepared from formic acid (FU) were compared with those of SF from water (AU). According to the turbidity and shear viscosity measurement, SF formic acid solution was stable and transparent, no molecular aggregations occurred. The sample FU exhibited the beta-sheet structure, while AU random coil conformation using Fourier transform infrared (FTIR), X-ray diffraction (XRD), and differential scanning calorimetry. The effects of methanol treatment on samples were also examined. According to the measurement of crystallinity (XRD) and crystallinity index (FTIR), the concept of long/short-range ordered structure formation was proposed. Long-range ordered crystallites are predominantly formed for methanol treated SF film while SF film cast from formic acid favors the formation of short-range ordered structure. The relaxation temperatures of SF films measured by dynamic thermomechanical analysis supported the above mechanism due to the sensitivity of relaxation temperature on the short-range order.

Depolymerization and hydrodeoxygenation of switchgrass lignin with formic acid.

PubMed

Xu, Weiyin; Miller, Stephen J; Agrawal, Pradeep K; Jones, Christopher W

2012-04-01

Organosolv switchgrass lignin is depolymerized and hydrodeoxygenated with a formic acid hydrogen source, 20 wt % Pt/C catalyst, and ethanol solvent. The combination of formic acid and Pt/C is found to promote production of higher fractions of lower molecular weight compounds in the liquid products. After 4 h of reaction, all of the switchgrass lignin is solubilized and 21 wt % of the biomass is shown to be converted into seven prominent molecular species that are identified and quantified. Reaction time is shown to be an important variable in affecting changes in product distributions and bulk liquid product properties. At 20 h of reaction, the lignin is significantly depolymerized to form liquid products with a 76 % reduction in the weighted average molecular weight. Elemental analysis also shows that the resultant liquid products have a 50 % reduction in O/C and 10 % increase in H/C molar ratios compared to the switchgrass lignin after 20 h. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Glycerol-plasticised silk membranes made using formic acid are ductile, transparent and degradation-resistant.

PubMed

Allardyce, Benjamin J; Rajkhowa, Rangam; Dilley, Rodney J; Redmond, Sharon L; Atlas, Marcus D; Wang, Xungai

2017-11-01

Regenerated silk fibroin membranes tend to be brittle when dry. The use of plasticisers such as glycerol improve membrane ductility, but, when combined with aqueous processing, can lead to a higher degradation rate than solvent-annealed membranes. This study investigated the use of formic acid as the solvent with glycerol to make deformable yet degradation-resistant silk membranes. Here we show that membranes cast using formic acid had low light scattering, with a diffuse transmittance of less than 5% over the visible wavelengths, significantly lower than the 20% transmittance of aqueous derived silk/glycerol membranes. They had 64% β-sheet content and lost just 30% of the initial silk weight over 6h when tested with an accelerated enzymatic degradation assay, in comparison the aqueous membranes completely degraded within this timeframe. The addition of glycerol also improved the maximum elongation of formic acid derived membranes from under 3% to over 100%. They also showed good cytocompatibility and supported the adhesion and migration of human tympanic membrane keratinocytes. Formic acid based, silk/glycerol membranes may be of great use in medical applications such as repair of tympanic membrane perforation or ocular applications where transparency and resistance to enzymatic degradation are important. Copyright © 2017 Elsevier B.V. All rights reserved.

Pd and polyaniline nanocomposite on carbon fiber paper as an efficient direct formic acid fuel cell anode

NASA Astrophysics Data System (ADS)

Pandey, Rakesh K.

2018-03-01

Direct formic acid fuel cells are advantageous as portable power generating devices. In the present work, an anode catalyst for direct formic acid fuel cell (DFAFC) is presented which has good catalytic activity for formic acid oxidation. The catalyst is composed of Pd and conducting polymer polyaniline (Pd-PANI) nanocomposite. The catalyst was prepared by using a single step galvanostatic electrochemical deposition method. The Pd-PANI catalyst was electrodeposited at different time durations and a comparison of the catalytic activity at each deposition time was carried out and optimized.

CaCO3 supplementation alleviates the inhibition of formic acid on acetone/butanol/ethanol fermentation by Clostridium acetobutylicum.

PubMed

Qi, Gaoxiang; Xiong, Lian; Lin, Xiaoqing; Huang, Chao; Li, Hailong; Chen, Xuefang; Chen, Xinde

2017-01-01

To investigate the inhibiting effect of formic acid on acetone/butanol/ethanol (ABE) fermentation and explain the mechanism of the alleviation in the inhibiting effect under CaCO 3 supplementation condition. From the medium containing 50 g sugars l -1 and 0.5 g formic acid l -1 , only 0.75 g ABE l -1 was produced when pH was adjusted by KOH and fermentation ended prematurely before the transformation from acidogenesis to solventogenesis. In contrast, 11.4 g ABE l -1 was produced when pH was adjusted by 4 g CaCO 3 l -1 . The beneficial effect can be ascribed to the buffering capacity of CaCO 3 . Comparative analysis results showed that the undissociated formic acid concentration and acid production coupled with ATP and NADH was affected by the pH buffering capacity of CaCO 3 . Four millimole undissociated formic acid was the threshold at which the transformation to solventogenesis occurred. The inhibiting effect of formic acid on ABE fermentation can be alleviated by CaCO 3 supplementation due to its buffering capacity.

Optimal Electrocatalytic Pd/MWNTs Nanocatalysts toward Formic Acid Oxidation

PubMed Central

Wang, Yiran; He, Qingliang; Wei, Huige; Guo, Jiang; Ding, Keqiang; Wang, Qiang; Wang, Zhe; Wei, Suying; Guo, Zhanhu

2017-01-01

The operating conditions such as composition of electrolyte and temperature can greatly influence the formic acid (HCOOH) oxidation reaction (FAOR). Palladium decorated multi-walled carbon nanotubes (Pd/MWNTs) were successfully synthesized and employed as nanocatalysts to explore the effects of formic acid, sulfuric acid (H2SO4) concentration and temperature on FAOR. Both the hydrogen adsorption in low potential range and the oxidation of poisoning species during the high potential range in cyclic voltammetry were demonstrated to contribute to the enhanced electroactivity of Pd/MWNTs. The as-synthesized Pd/MWNTs gave the best performance under a condition with balanced adsorptions of HCOOH and H2SO4 molecules. The dominant dehydrogenation pathway on Pd/MWNTs can be largely depressed by the increased dehydration pathway, leading to an increased charge transfer resistance (Rct). Increasing HCOOH concentration could directly increase the dehydration process proportion and cause the production of COads species. H2SO4 as donor of H+ greatly facilitated the onset oxidation of HCOOH in the beginning process but it largely depressed the HCOOH oxidation with excess amount of H+. Enhanced ion mobility with increasing the temperature was mainly responsible for the increased current densities, improved tolerance stabilities and reduced Rct values, while dehydration process was also increased simultaneously. PMID:29622817

Theoretical study on the mechanism of aqueous synthesis of formic acid catalyzed by [Ru3+]-EDTA complex.

PubMed

Chen, Zhe-Ning; Chan, Kwong-Yu; Pulleri, Jayasree K; Kong, Jing; Hu, Hao

2015-02-16

Because formic acid can be effectively decomposed by catalysis into very pure hydrogen gas, the synthesis of formic acid, especially using CO and H2O as an intermediate of the water gas shift reaction (WGSR), bears important application significance in industrial hydrogen gas production. Here we report a theoretical study on the mechanism of efficient preparation of formic acid using CO and H2O catalyzed by a water-soluble [Ru(3+)]-EDTA complex. To determine the feasibility of using the [Ru(3+)]-EDTA catalyst to produce CO-free hydrogen gas in WGSR, two probable reaction paths have been examined: one synthesizes formic acid, while the other converts the reactants directly into CO2 and H2, the final products of WGSR. Our calculation results provide a detailed mechanistic rationalization for the experimentally observed selective synthesis of HCOOH by the [Ru(3+)]-EDTA catalyst. The results support the applicability of using the [Ru(3+)]-EDTA catalyst to efficiently synthesize formic acid for hydrogen production. Careful analyses of the electronic structure and interactions of different reaction complexes suggest that the selectivity of the reaction processes is achieved through the proper charge/valence state of the metal center of the [Ru(3+)]-EDTA complex. With the catalytic roles of the ruthenium center and the EDTA ligand being carefully understood, the detailed mechanistic information obtained in this study will help to design more efficient catalysts for the preparation of formic acid and further to produce CO-free H2 at ambient temperature.

Dehydrogenation, disproportionation and transfer hydrogenation reactions of formic acid catalyzed by molybdenum hydride compounds.

PubMed

Neary, Michelle C; Parkin, Gerard

2015-03-01

The cyclopentadienyl molybdenum hydride compounds, Cp R Mo(PMe 3 ) 3- x (CO) x H (Cp R = Cp, Cp*; x = 0, 1, 2 or 3), are catalysts for the dehydrogenation of formic acid, with the most active catalysts having the composition Cp R Mo(PMe 3 ) 2 (CO)H. The mechanism of the catalytic cycle is proposed to involve (i) protonation of the molybdenum hydride complex, (ii) elimination of H 2 and coordination of formate, and (iii) decarboxylation of the formate ligand to regenerate the hydride species. NMR spectroscopy indicates that the nature of the resting state depends on the composition of the catalyst. For example, (i) the resting states for the CpMo(CO) 3 H and CpMo(PMe 3 )(CO) 2 H systems are the hydride complexes themselves, (ii) the resting state for the CpMo(PMe 3 ) 3 H system is the protonated species [CpMo(PMe 3 ) 3 H 2 ] + , and (iii) the resting state for the CpMo(PMe 3 ) 2 (CO)H system is the formate complex, CpMo(PMe 3 ) 2 (CO)(κ 1 -O 2 CH), in the presence of a high concentration of formic acid, but CpMo(PMe 3 ) 2 (CO)H when the concentration of acid is low. While CO 2 and H 2 are the principal products of the catalytic reaction induced by Cp R Mo(PMe 3 ) 3- x (CO) x H, methanol and methyl formate are also observed. The generation of methanol is a consequence of disproportionation of formic acid, while methyl formate is a product of subsequent esterification. The disproportionation of formic acid is a manifestation of a transfer hydrogenation reaction, which may also be applied to the reduction of aldehydes and ketones. Thus, CpMo(CO) 3 H also catalyzes the reduction of a variety of ketones and aldehydes to alcohols by formic acid, via a mechanism that involves ionic hydrogenation.

Optimal design and experimental validation of a simulated moving bed chromatography for continuous recovery of formic acid in a model mixture of three organic acids from Actinobacillus bacteria fermentation.

PubMed

Park, Chanhun; Nam, Hee-Geun; Lee, Ki Bong; Mun, Sungyong

2014-10-24

The economically-efficient separation of formic acid from acetic acid and succinic acid has been a key issue in the production of formic acid with the Actinobacillus bacteria fermentation. To address this issue, an optimal three-zone simulated moving bed (SMB) chromatography for continuous separation of formic acid from acetic acid and succinic acid was developed in this study. As a first step for this task, the adsorption isotherm and mass-transfer parameters of each organic acid on the qualified adsorbent (Amberchrom-CG300C) were determined through a series of multiple frontal experiments. The determined parameters were then used in optimizing the SMB process for the considered separation. During such optimization, the additional investigation for selecting a proper SMB port configuration, which could be more advantageous for attaining better process performances, was carried out between two possible configurations. It was found that if the properly selected port configuration was adopted in the SMB of interest, the throughout and the formic-acid product concentration could be increased by 82% and 181% respectively. Finally, the optimized SMB process based on the properly selected port configuration was tested experimentally using a self-assembled SMB unit with three zones. The SMB experimental results and the relevant computer simulation verified that the developed process in this study was successful in continuous recovery of formic acid from a ternary organic-acid mixture of interest with high throughput, high purity, high yield, and high product concentration. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Synthesizing Pt nanoparticles in the presence of methylamine: Impact of acetic acid treatment in the electrocatalytic activity of formic acid oxidation

NASA Astrophysics Data System (ADS)

Ooi, M. D. Johan; Aziz, A. Abdul

2017-05-01

Surfactant removal from the surface of platinum nanoparticles prepared by solution based method is a prerequisite process to accomplish a high catalytic activity for electrochemical reactions. Here, we report a possible approach of combining acid acetic with thermal treatment for improving catalytic performance of formic acid oxidation. This strategy involves conversion of amine to amide in acetic acid followed by surfactant removal via subsequent thermal treatment at 85 °C. This combined activation technique produced monodisperse nanoparticle with the size of 3 to 5 nm with enhanced formic acid oxidation activity, particularly in perchloric acid solution. Pt treated in 1 h of acetic acid and heat treatment of 9 h shows high electrochemical surface area value (27.6 m2/g) compares to Pt without activation (16.6 m2/g). The treated samples also exhibit high current stability of 0.3 mA/cm2 compares to the as-prepared mA/cm2). Shorter duration of acid wash and longer duration of heating process result in high electrocatalytic activity. This work demonstrates a possible technique in improving catalytic activity of platinum nanoparticles synthesized using methylamine as surfactant.

Formic Acid Dissociative Adsorption on NiO(111): Energetics and Structure of Adsorbed Formate

DOE PAGES

Zhao, Wei; Doyle, Andrew D.; Morgan, Sawyer E.; ...

2017-11-21

Here, the dissociative adsorption of carboxylic acids on oxide surfaces is important for understanding adsorbed carboxylates, which are important as intermediates in catalytic reactions, for the organo-functionalization of oxide surfaces, and in many other aspects of oxide surface chemistry. We present here the first direct experimental measurement of the heat of dissociative adsorption of any carboxylic acid on any single-crystal oxide surface. The enthalpy of the dissociative adsorption of formic acid, the simplest carboxylic acid, to produce adsorbed formate and hydrogen (as a surface hydroxyl) on a (2 × 2)-NiO(111) surface is measured by single crystal adsorption calorimetry. The differentialmore » heat of adsorption decreases with formic acid coverage from 202 to 99 kJ/mol at saturation (0.25 ML). The structure of the adsorbed products is clarified by density functional theory (DFT) calculations, which provide energies in reasonable agreement with the calorimetry. These calculations show that formic acid readily dissociates on both the oxygen and Ni terminations of the octapolar NiO(111) surfaces, donating its acid H to a surface lattice oxygen, while HCOO adsorbs preferentially with bridging-type geometry near the M-O 3/O-M 3 sites. The calculated energetics at low coverages agrees well with experimental data, while larger differences are observed at high coverage (0.25 ML). The large decrease in experimental heat of adsorption with coverage can be brought into agreement with the DFT energies if we assume that both types of octapolar surface terminations (O- and Ni-) are present on the starting surface.« less

Formic Acid Dissociative Adsorption on NiO(111): Energetics and Structure of Adsorbed Formate

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

Zhao, Wei; Doyle, Andrew D.; Morgan, Sawyer E.

Here, the dissociative adsorption of carboxylic acids on oxide surfaces is important for understanding adsorbed carboxylates, which are important as intermediates in catalytic reactions, for the organo-functionalization of oxide surfaces, and in many other aspects of oxide surface chemistry. We present here the first direct experimental measurement of the heat of dissociative adsorption of any carboxylic acid on any single-crystal oxide surface. The enthalpy of the dissociative adsorption of formic acid, the simplest carboxylic acid, to produce adsorbed formate and hydrogen (as a surface hydroxyl) on a (2 × 2)-NiO(111) surface is measured by single crystal adsorption calorimetry. The differentialmore » heat of adsorption decreases with formic acid coverage from 202 to 99 kJ/mol at saturation (0.25 ML). The structure of the adsorbed products is clarified by density functional theory (DFT) calculations, which provide energies in reasonable agreement with the calorimetry. These calculations show that formic acid readily dissociates on both the oxygen and Ni terminations of the octapolar NiO(111) surfaces, donating its acid H to a surface lattice oxygen, while HCOO adsorbs preferentially with bridging-type geometry near the M-O 3/O-M 3 sites. The calculated energetics at low coverages agrees well with experimental data, while larger differences are observed at high coverage (0.25 ML). The large decrease in experimental heat of adsorption with coverage can be brought into agreement with the DFT energies if we assume that both types of octapolar surface terminations (O- and Ni-) are present on the starting surface.« less

Unraveling the Role of Formic Acid and the Type of Solvent in the Catalytic Conversion of Lignin: A Holistic Approach.

PubMed

Oregui-Bengoechea, Mikel; Gandarias, Inaki; Arias, Pedro L; Barth, Tanja

2017-02-22

The role of formic acid together with the effect of the solvent type and their synergic interactions with a NiMo catalyst were studied for the conversion of lignin into bio-oil in an alcohol/formic acid media. The replacement of formic acid with H 2 or isopropanol decreased the oil yield to a considerable degree, increased the solid yield, and altered the nature of the bio-oil. The differences induced by the presence of H 2 were comparable to those observed in the isopropanol system, which suggests similar lignin conversion mechanisms for both systems. Additional semi-batch experiments confirmed that formic acid does not act merely as an in situ hydrogen source or hydrogen donor molecule. Actually, is seems to react with lignin through a formylation-elimination-hydrogenolysis mechanism that leads to the depolymerization of the biopolymer. This reaction competes with formic acid decomposition, which gives mainly H 2 and CO 2 , and forms a complex reaction system. To the best of our knowledge, this is the first time that the distinctive role/mechanism of formic acid has been observed in the conversion of real lignin feedstock. In addition, the solvent, especially ethanol, seems also to play a vital role in the stabilization of the depolymerized monomers and in the elimination/deformylation step. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Base-free production of H2 by dehydrogenation of formic acid using an iridium-bisMETAMORPhos complex.

PubMed

Oldenhof, Sander; de Bruin, Bas; Lutz, Martin; Siegler, Maxime A; Patureau, Frederic W; van der Vlugt, Jarl Ivar; Reek, Joost N H

2013-08-26

Erase the base: An iridium complex based on a cooperative ligand that functions as an internal base is reported. This complex can rapidly and cleanly dehydrogenate formic acid in absence of external base, a reaction that is required if formic acid is to be exploited as an energy carrier (see scheme). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic Reduction of Hexavalent Uranium by Formic Acid; RIDUZIONE CATALITICA DELL'URANIO ESAVALENTE MEDIANTE ACIDO FORMICO

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

Cogliati, G.; Lanz, R.; Lepscky, C.

1963-10-01

S>The catalytic reduction of U(VI) to U(IV) by means of formic acid has been studied, considering particularly the uranyl nltrate solutions, This process will be applied in the urania--thoria mixed fuel reprocessing plant, (PCUT). Various catalysts have been tested and the influence of formic acid concentration, temperature and catalyst concentration on the reaction rate have been determined. A possible reduction mechanism coherent with Ihe experimental data is discussed. (auth)

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.

Hydrolysis of glyoxal in water-restricted environments: formation of organic aerosol precursors through formic acid catalysis.

PubMed

Hazra, Montu K; Francisco, Joseph S; Sinha, Amitabha

2014-06-12

The hydrolysis of glyoxal involving one to three water molecules and also in the presence of a water molecule and formic acid has been investigated. Our results show that glyoxal-diol is the major product of the hydrolysis and that formic acid, through its ability to facilitate intermolecular hydrogen atom transfer, is considerably more efficient than water as a catalyst in the hydrolysis process. Additionally, once the glyoxal-diol is formed, the barrier for further hydrolysis to form the glyoxal-tetrol is effectively reduced to zero in the presence of a single water and formic acid molecule. There are two important implications arising from these findings. First, the results suggest that under the catalytic influence of formic acid, glyoxal hydrolysis can impact the growth of atmospheric aerosols. As a result of enhanced hydrogen bonding, mediated through their polar OH functional groups, the diol and tetrol products are expected to have significantly lower vapor pressure than the parent glyoxal molecule; hence they can more readily partition into the particle phase and contribute to the growth of secondary organic aerosols. In addition, our findings provide insight into how glyoxal-diol and glyoxal-tetrol might be formed under atmospheric conditions associated with water-restricted environments and strongly suggest that the formation of these precursors for secondary organic aerosol growth is not likely restricted solely to the bulk aqueous phase as is currently assumed.

Intake, digestibility, and composition of orchardgrass and alfalfa silages treated with cellulase, inoculant, and formic acid fed to lambs.

PubMed

Nadeau, E M; Russell, J R; Buxton, D R

2000-11-01

The objectives of this study were to determine the effect of a cellulase (from Trichoderma longibrachiatum) alone or combined with a bacterial inoculant (Lactobacillus plantarum and Pediococcus cerevisiae) or formic acid on composition, intake, and digestibility of orchardgrass (Dactylis glomerata L.) and alfalfa (Medicago sativa L.) silages. Orchardgrass and alfalfa were harvested at the early heading stage and at the early bloom stage of maturity and wilted to approximately 22 and 32% DM, respectively. Forages were then ensiled in 100-L sealed barrels for at least 60 d before they were fed to lambs. Silage treated with cellulase had lower (P < .001) pH and lower (P < .001) acetic acid and NH3 N concentrations than untreated silage of both plant species and a higher (P = .004) lactic acid concentration than the control treatment of alfalfa silage. Fermentation characteristics of cellulase-treated silages, especially of alfalfa, were further enhanced by use of inoculant. Formic acid addition increased (P < .001), reducing sugar concentration of cellulase-treated orchardgrass and alfalfa silage by 90 and 154%, respectively, and decreased (P < .001) NH3 N concentration of cellulase-treated alfalfa silage by 19%. Averaged across plant species, cellulase, combined with inoculant or formic acid, resulted in 8 and 13% greater (P = .03) DMI, respectively, than the control silage. Extensive enzymatic cell-wall degradation during ensiling decreased (P = .003) NDF intake of cellulase-treated orchardgrass silage by 25% and decreased (P = .001) cellulose intake by 23%, when averaged across plant species. Addition of formic acid increased (P = .003) NDF intake of cellulase-treated orchardgrass silage by 19%. Averaged across species, cellulase application decreased (P < .05) silage NDF digestibility by 18%. Greater sugar and lower acetic acid, NH3 N, and NDF concentrations resulted in greater DMI of cellulase-treated silage than of control silage, when cellulase was combined

An investigation about the structures, thermodynamics and kinetics of the formic acid involved molecular clusters

NASA Astrophysics Data System (ADS)

Zhang, Rui; Jiang, Shuai; Liu, Yi-Rong; Wen, Hui; Feng, Ya-Juan; Huang, Teng; Huang, Wei

2018-05-01

Despite the very important role of atmospheric aerosol nucleation in climate change and air quality, the detailed aerosol nucleation mechanism is still unclear. Here we investigated the formic acid (FA) involved multicomponent nucleation molecular clusters including sulfuric acid (SA), dimethylamine (DMA) and water (W) through a quantum chemical method. The thermodynamics and kinetics analysis was based on the global minima given by Basin-Hopping (BH) algorithm coupled with Density Functional Theory (DFT) and subsequent benchmarked calculations. Then the interaction analysis based on ElectroStatic Potential (ESP), Topological and Atomic Charges analysis was made to characterize the binding features of the clusters. The results show that FA binds weakly with the other molecules in the cluster while W binds more weakly. Further kinetic analysis about the time evolution of the clusters show that even though the formic acid's weak interaction with other nucleation precursors, its effect on sulfuric acid dimer steady state concentration cannot be neglected due to its high concentration in the atmosphere.

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

Code of Federal Regulations, 2013 CFR

2013-07-01

... 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 with...

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

Code of Federal Regulations, 2012 CFR

2012-07-01

... 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 with...

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

Code of Federal Regulations, 2011 CFR

2011-07-01

... 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 with...

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

Code of Federal Regulations, 2010 CFR

2010-07-01

... 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 with...

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

Code of Federal Regulations, 2014 CFR

2014-07-01

... 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 with...

Hydrogen storage and delivery: the carbon dioxide - formic acid couple.

PubMed

Laurenczy, Gábor

2011-01-01

Carbon dioxide and the carbonates, the available natural C1 sources, can be easily hydrogenated into formic acid and formates in water; the rate of this reduction strongly depends on the pH of the solution. This reaction is catalysed by ruthenium(II) pre-catalyst complexes with a large variety of water-soluble phosphine ligands; high conversions and turnover numbers have been realised. Although ruthenium(II) is predominant in these reactions, the iron(II) - tris[(2-diphenylphosphino)-ethyl]phosphine (PP3) complex is also active, showing a new perspective to use abundant and inexpensive iron-based compounds in the CO2 reduction. In the catalytic hydrogenation cycles the in situ formed metal hydride complexes play a key role, their structures with several other intermediates have been proven by multinuclear NMR spectroscopy. In the other hand safe and convenient hydrogen storage and supply is the fundamental question for the further development of the hydrogen economy; and carbon dioxide has been recognised to be a viable H2 vector. Formic acid--containing 4.4 weight % of H2, that is 53 g hydrogen per litre--is suitable for H2 storage; we have shown that in aqueous solutions it can be selectively decomposed into CO-free (CO < 10 ppm) CO2 and H2. The reaction takes place under mild experimental conditions and it is able to generate high pressure H2 (up to 600 bar). The cleavage of HCOOH is catalysed by several hydrophilic Ru(II) phosphine complexes (meta-trisulfonated triphenylphosphine, mTPPTS, being the most efficient one), either in homogeneous systems or as immobilised catalysts. We have also shown that the iron(II)--hydrido tris[(2-diphenylphosphino)ethyl]phosphine complex catalyses with an exceptionally high rate and efficiency (turnover frequency, TOF = 9425 h(-1)mol(-1); turnover number, TON = 92400) the formic acid cleavage, in environmentally friendly propylene carbonate solution, opening the way to use cheap, non-noble metal based catalysts for this

Gas phase hydrolysis of formaldehyde to form methanediol: impact of formic acid catalysis.

PubMed

Hazra, Montu K; Francisco, Joseph S; Sinha, Amitabha

2013-11-21

We find that formic acid (FA) is very effective at facilitating diol formation through its ability to reduce the barrier for the formaldehyde (HCHO) hydrolysis reaction. The rate limiting step in the mechanism involves the isomerization of a prereactive collision complex formed through either the HCHO···H2O + FA and/or HCHO + FA···H2O pathways. The present study finds that the effective barrier height, defined as the difference between the zero-point vibrational energy (ZPE) corrected energy of the transition state (TS) and the HCHO···H2O + FA and HCHO + FA···H2O starting reagents, are respectively only ∼1 and ∼4 kcal/mol. These barriers are substantially lower than the ∼17 kcal/mol barrier associated with the corresponding step in the hydrolysis of HCHO catalyzed by a single water molecule (HCHO + H2O + H2O). The significantly lower barrier heights for the formic acid catalyzed pathway reveal a new important role that organic acids play in the gas phase hydrolysis of atmospheric carbonyl compounds.

Inactivation of the transcription factor mig1 (YGL035C) in Saccharomyces cerevisiae improves tolerance towards monocarboxylic weak acids: acetic, formic and levulinic acid.

PubMed

Balderas-Hernández, Victor E; Correia, Kevin; Mahadevan, Radhakrishnan

2018-06-06

Toxic concentrations of monocarboxylic weak acids present in lignocellulosic hydrolyzates affect cell integrity and fermentative performance of Saccharomyces cerevisiae. In this work, we report the deletion of the general catabolite repressor Mig1p as a strategy to improve the tolerance of S. cerevisiae towards inhibitory concentrations of acetic, formic or levulinic acid. In contrast with the wt yeast, where the growth and ethanol production were ceased in presence of acetic acid 5 g/L or formic acid 1.75 g/L (initial pH not adjusted), the m9 strain (Δmig1::kan) produced 4.06 ± 0.14 and 3.87 ± 0.06 g/L of ethanol, respectively. Also, m9 strain tolerated a higher concentration of 12.5 g/L acetic acid (initial pH adjusted to 4.5) without affecting its fermentative performance. Moreover, m9 strain produced 33% less acetic acid and 50-70% less glycerol in presence of weak acids, and consumed acetate and formate as carbon sources under aerobic conditions. Our results show that the deletion of Mig1p provides a single gene deletion target for improving the acid tolerance of yeast strains significantly.

Local vibrational modes of the formic acid dimer - the strength of the double hydrogen bond

NASA Astrophysics Data System (ADS)

Kalescky, R.; Kraka, E.; Cremer, D.

2013-07-01

The 24 normal and 24 local vibrational modes of the formic acid dimer formed by two trans formic acid monomers to a ring (TT1) are analysed utilising preferentially experimental frequencies, but also CCSD(T)/CBS and ωB97X-D harmonic vibrational frequencies. The local hydrogen bond (HB) stretching frequencies are at 676 cm-1 and by this 482 and 412 cm-1 higher compared to the measured symmetric and asymmetric HB stretching frequencies at 264 and 194 cm-1. The adiabatic connection scheme between local and normal vibrational modes reveals that the lowering is due to the topology of dimer TT1, mass coupling, and avoided crossings involving the HṡṡṡOC bending modes. The HB local mode stretching force constant is related to the strength of the HB whereas the normal mode stretching force constant and frequency lead to an erroneous underestimation of the HB strength. The HB in TT1 is stabilised by electron delocalisation in the O=C-O units fostered by forming a ring via double HBs. This implies that the CO apart from the OH local stretching frequencies reflect the strength of the HB via their red or blue shifts relative to their corresponding values in trans formic acid.

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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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. Copyright © 2016 Elsevier Ltd. All rights reserved.

Photocatalytic CO2 reduction with high turnover frequency and selectivity of formic acid formation using Ru(II) multinuclear complexes.

PubMed

Tamaki, Yusuke; Morimoto, Tatsuki; Koike, Kazuhide; Ishitani, Osamu

2012-09-25

Previously undescribed supramolecules constructed with various ratios of two kinds of Ru(II) complexes-a photosensitizer and a catalyst-were synthesized. These complexes can photocatalyze the reduction of CO(2) to formic acid with high selectivity and durability using a wide range of wavelengths of visible light and NADH model compounds as electron donors in a mixed solution of dimethylformamide-triethanolamine. Using a higher ratio of the photosensitizer unit to the catalyst unit led to a higher yield of formic acid. In particular, of the reported photocatalysts, a trinuclear complex with two photosensitizer units and one catalyst unit photocatalyzed CO(2) reduction (Φ(HCOOH) = 0.061, TON(HCOOH) = 671) with the fastest reaction rate (TOF(HCOOH) = 11.6 min(-1)). On the other hand, photocatalyses of a mixed system containing two kinds of model mononuclear Ru(II) complexes, and supramolecules with a higher ratio of the catalyst unit were much less efficient, and black oligomers and polymers were produced from the Ru complexes during photocatalytic reactions, which reduced the yield of formic acid. The photocatalytic formation of formic acid using the supramolecules described herein proceeds via two sequential processes: the photochemical reduction of the photosensitizer unit by NADH model compounds and intramolecular electron transfer to the catalyst unit.

Photocatalytic CO2 reduction with high turnover frequency and selectivity of formic acid formation using Ru(II) multinuclear complexes

PubMed Central

Tamaki, Yusuke; Morimoto, Tatsuki; Koike, Kazuhide; Ishitani, Osamu

2012-01-01

Previously undescribed supramolecules constructed with various ratios of two kinds of Ru(II) complexes—a photosensitizer and a catalyst—were synthesized. These complexes can photocatalyze the reduction of CO2 to formic acid with high selectivity and durability using a wide range of wavelengths of visible light and NADH model compounds as electron donors in a mixed solution of dimethylformamide–triethanolamine. Using a higher ratio of the photosensitizer unit to the catalyst unit led to a higher yield of formic acid. In particular, of the reported photocatalysts, a trinuclear complex with two photosensitizer units and one catalyst unit photocatalyzed CO2 reduction (ΦHCOOH = 0.061, TONHCOOH = 671) with the fastest reaction rate (TOFHCOOH = 11.6 min-1). On the other hand, photocatalyses of a mixed system containing two kinds of model mononuclear Ru(II) complexes, and supramolecules with a higher ratio of the catalyst unit were much less efficient, and black oligomers and polymers were produced from the Ru complexes during photocatalytic reactions, which reduced the yield of formic acid. The photocatalytic formation of formic acid using the supramolecules described herein proceeds via two sequential processes: the photochemical reduction of the photosensitizer unit by NADH model compounds and intramolecular electron transfer to the catalyst unit. PMID:22908243

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

2016-05-06

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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The chemisorption and reactions of formic acid on Cu films on ZnO (000 overline1)-O

NASA Astrophysics Data System (ADS)

Ludviksson, A.; Zhang, R.; Campbell, Charles T.; Griffiths, K.

1994-06-01

The adsorption and reactions of formic acid (HCOOD : HCOOH = 3:1) on the oxygen-terminated ZnO(0001¯)-O surface and on thin Cu films deposited on the ZnO(0001¯)-O surface have been studied with temperature programmed desorption (TPD) and XPS. Small amounts of formic acid dissociate at defect sites on clean ZnO(0001¯)-O to yield surface formate (HCOO). The acid D(H) from this dissociation does not reappear in TPD, and is lost to the ZnO bulk, as confirmed by nuclear reaction analysis. The surface HCOO decomposes to yield nearly simultaneous CO 2 (37%), CO (63%) and H 2 TPD peaks at 560 K. Substantial amounts of D (˜ 20%) are incorporated in this hydrogen TPD peak resulting from formate decomposition at ZnO defects, indicating that bulk D is readily accessible. Submonolayer and multilayer Cu films that are deposited at 130 K and partially cover the ZnO surface as 2D and 3D islands adsorb formic acid and decompose it into formate and hydrogen much like the Cu(110) surface. The surface formate from the Cu film decomposes at 470-500 K to give primarily CO 2 and H 2, also much like Cu(110), although atom-thin Cu islands also give ˜ 40% CO. Annealed Cu films give formate decomposition peaks at 25-50 K lower in temperature, attributed to thickening and ordering of the Cu islands to form Cu(111)-like sites. The acid D(H) atom from the formic acid is partially lost by hydrogen spillover from the Cu islands into the ZnO substrate, especially for thin Cu films. This effect partially desorbs and is enhanced upon preannealing the Cu layers, due to increased H diffusion rates across the annealed Cu islands, and/or the decrease in island size. Bulk D(H) is slowly removed as D 2, HD and H 2 above 400 K in diffusion-limited desorption, catalyzed by Cu.

Electrochemical synthesis of formic acid from CO2 catalyzed by Shewanella oneidensis MR-1 whole-cell biocatalyst.

PubMed

Le, Quang Anh Tuan; Kim, Hee Gon; Kim, Yong Hwan

2018-09-01

The electro-biocatalytic conversion of CO 2 into formic acid using whole-cell and isolated biocatalysts is useful as an alternative route for CO 2 sequestration. In this study, Shewanella oneidensis MR-1 (S. oneidensis MR-1), a facultative aerobic bacterium that has been extensively studied for its utility as biofuel cells as well as for the detoxification of heavy metal oxides (i.e., MnO 2 , uranium), has been applied for the first time as a whole-cell biocatalyst for formic acid synthesis from gaseous CO 2 and electrons supplied from an electrode. S. oneidensis MR-1, when aerobically grown in Luria-Bertani (LB) medium, exhibited its ability as a whole-cell biocatalyst for the conversion of CO 2 into formic acid with moderate productivity of 0.59 mM h -1 for 24 h. In addition, an optimization of growth conditions of S. oneidensis MR-1 resulted in a remarkable increase in productivity. The CO 2 reduction reaction catalyzed by S. oneidensis MR-1, when anaerobically grown in newly optimized LB medium supplemented with fumarate and nitrate, exhibited 3.2-fold higher productivity (1.9 mM h -1 for 72 h) compared to that grown aerobically in only LB medium. Furthermore, the average conversion rate of formic acid synthesis catalyzed by S. oneidensis MR-1 when grown in the optimal medium over a period of 72 h was 3.8 mM h -1  g -1 wet-cell, which is 9.6-fold higher than that catalyzed by Methylobacterium extorquens AM1 whole-cells in our previous study. Copyright © 2018 Elsevier Inc. All rights reserved.

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

Structural studies of Proteus mirabilis catalase in its ground state, oxidized state and in complex with formic acid.

PubMed

Andreoletti, Pierre; Pernoud, Anaïs; Sainz, Germaine; Gouet, Patrice; Jouve, Hélène Marie

2003-12-01

The structure of Proteus mirabilis catalase in complex with an inhibitor, formic acid, has been solved at 2.3 A resolution. Formic acid is a key ligand of catalase because of its ability to react with the ferric enzyme, giving a high-spin iron complex. Alternatively, it can react with two transient oxidized intermediates of the enzymatic mechanism, compounds I and II. In this work, the structures of native P. mirabilis catalase (PMC) and compound I have also been determined at high resolution (2.0 and 2.5 A, respectively) from frozen crystals. Comparisons between these three PMC structures show that a water molecule present at a distance of 3.5 A from the haem iron in the resting state is absent in the formic acid complex, but reappears in compound I. In addition, movements of solvent molecules are observed during formation of compound I in a cavity located away from the active site, in which a glycerol molecule is replaced by a sulfate. These results give structural insights into the movement of solvent molecules, which may be important in the enzymatic reaction.

Different catalytic effects of a single water molecule: the gas-phase reaction of formic acid with hydroxyl radical in water vapor.

PubMed

Anglada, Josep M; Gonzalez, Javier

2009-12-07

The effect of a single water molecule on the reaction mechanism of the gas-phase reaction between formic acid and the hydroxyl radical was investigated with high-level quantum mechanical calculations using DFT-B3LYP, MP2 and CCSD(T) theoretical approaches in concert with the 6-311+G(2df,2p) and aug-cc-pVTZ basis sets. The reaction between HCOOH and HO has a very complex mechanism involving a proton-coupled electron transfer process (pcet), two hydrogen-atom transfer reactions (hat) and a double proton transfer process (dpt). The hydroxyl radical predominantly abstracts the acidic hydrogen of formic acid through a pcet mechanism. A single water molecule affects each one of these reaction mechanisms in different ways, depending on the way the water interacts. Very interesting is also the fact that our calculations predict that the participation of a single water molecule results in the abstraction of the formyl hydrogen of formic acid through a hydrogen atom transfer process (hat).

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.

One-Pot Synthesis of Graphene-Supported Monodisperse Pd Nanoparticles as Catalyst for Formic Acid Electro-oxidation

PubMed Central

Yang, Sudong; Dong, Jing; Yao, Zhaohui; Shen, Chengmin; Shi, Xuezhao; Tian, Yuan; Lin, Shaoxiong; Zhang, Xiaogang

2014-01-01

To synthesize monodisperse palladium nanoparticles dispersed on reduced graphene oxide (RGO) sheets, we have developed an easy and scalable solvothermal reduction method from an organic solution system. The RGO-supported palladium nanoparticles with a diameter of 3.8 nm are synthesized in N-methyl-2-pyrrolidone (NMP) and in the presence of oleylamine and trioctylphosphine, which facilitates simultaneous reduction of graphene oxide and formation of Pd nanocrystals. So-produced Pd/RGO was tested for potential use as electrocatalyst for the electro-oxidation of formic acid. Pd/RGO catalyzes formic acid oxidation very well compared to Pd/Vulcan XC-72 catalyst. This synthesis method is a new way to prepare excellent electrocatalysts, which is of great significance in energy-related catalysis. PMID:24675779

A [NiFe]hydrogenase model that catalyses the release of hydrogen from formic acid.

PubMed

Nguyen, Nga T; Mori, Yuki; Matsumoto, Takahiro; Yatabe, Takeshi; Kabe, Ryota; Nakai, Hidetaka; Yoon, Ki-Seok; Ogo, Seiji

2014-11-11

We report the decomposition of formic acid to hydrogen and carbon dioxide, catalysed by a NiRu complex originally developed as a [NiFe]hydrogenase model. This is the first example of H2 evolution, catalysed by a [NiFe]hydrogenase model, which does not require additional energy.

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. Copyright © 2014 Elsevier B.V. All rights reserved.

Energetics of formic acid conversion to adsorbed formates on Pt(111) by transient calorimetry.

PubMed

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

2014-03-12

Carboxylates adsorbed on solid surfaces are important in many technological applications, ranging from heterogeneous catalysis and surface organo-functionalization to medical implants. We report here the first experimentally determined enthalpy of formation of any surface bound carboxylate on any surface, formate on Pt(111). This was accomplished by studying the dissociative adsorption of formic acid on oxygen-presaturated (O-sat) Pt(111) to make adsorbed monodentate and bidentate formates using single-crystal adsorption calorimetry. The integral heat of molecular adsorption of formic acid on clean Pt(111) at 100 K is 62.5 kJ/mol at 0.25 monolayer (ML). On O-sat Pt(111), the integral heat of the dissociative adsorption of formic acid to make monodentate formate (HCOOmon,ad) plus the water-hydroxyl complex ((H2O-OH)ad) was found to be 76 kJ/mol at 3/8 ML and 100-150 K. Similarly, its integral heat of dissociative adsorption to make bidentate formate (HCOObi,ad) plus (H2O-OH)ad was 106 kJ/mol at 3/8 ML and 150 K. These heats give the standard enthalpies of formation of adsorbed monodentate and bidentate formate on Pt(111) to be -354 ± 5 and -384 ± 5 kJ/mol, respectively, and their net bond enthalpies to the Pt(111) surface to be 224 ± 13 and 254 ± 13 kJ/mol, respectively. Coverage-dependent enthalpies of formation were used to estimate the enthalpy of the elementary reaction HCOOHad → HCOObi,ad + Had to be -4 kJ/mol at zero coverage and +24 kJ/mol at 3/8 ML.

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

PubMed

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

2012-07-01

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

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.

Effects of Formic or Acetic Acid on the Storage Quality
 of Mixed Air-Dried Corn Stover and Cabbage Waste,
and Microbial Community Analysis.

PubMed

Ren, Haiwei; Wang, Cong; Fan, Wenguang; Zhang, Bingyun; Li, Zhizhong; Li, Dong

2018-03-01

A mixture of air-dried corn stover and cabbage waste was ensiled to preserve lignocellulosic biomass for use as biofuel. Furthermore, the effects of different fresh mass fractions (0.3 and 0.6%) of formic or acetic acid on the mixed silage quality were evaluated to guarantee its quality. The application of formic or acetic acid prior to mixing the silage led to higher water-soluble carbohydrate fractions than the negative control, indicating that both acids contributed to preservation of water-soluble carbohydrates during storage for 170 days. The dry matter content was also increased after storage from 90 to 170 days. It was found that the content of neutral and acid detergent fibre, cellulose and holocellulose (the sum of cellulose and hemicellulose) in mixed silage treated with formic or acetic acid was significantly lower than that obtained in the negative control. The pH and the ratio of ammoniacal nitrogen to total nitrogen in mixed silage treated with acetic acid also significantly decreased. Furthermore, the addition of formic or acetic acid significantly weakened the fermentation intensity of lactic acid, depending on the ratio of lactic to acetic acid, as well as the ratio of lactic acid to total organic acids. The number of bacterial species and their relative abundance shifted during silage mixing, wherein microbial communities at phylum level mainly consisted of Proteobacteria and Firmicutes. The dominant bacteria were also observed to shift from Lactobacillus and Enterobacter in presilage biomass to Lactobacillus and Paralactobacillus . Specifically, Enterobacter disappeared after 130 days of storage. In conclusion, the addition of a low dose of acetic acid to fresh mass (0.3%) could effectively improve the fermentation quality and is conducive to the preservation of the organic components.

Direction to practical production of hydrogen by formic acid dehydrogenation with Cp*Ir complexes bearing imidazoline ligands

DOE PAGES

Onishi, Naoya; Ertem, Mehmed Z.; Xu, Shaoan; ...

2016-11-10

In a Cp*Ir complex with a bidentate pyridyl-imidazoline ligand achieved the evolution of 1.02 m 3 of H 2/CO 2 gases by formic acid dehydrogenation without any additives or adjustments in the solution system. Furthermore, the pyridyl-imidazoline moieties provided the optimum pH to be 1.7, resulting in high activity and stability even at very acidic conditions.

Direction to practical production of hydrogen by formic acid dehydrogenation with Cp*Ir complexes bearing imidazoline ligands

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

Onishi, Naoya; Ertem, Mehmed Z.; Xu, Shaoan

In a Cp*Ir complex with a bidentate pyridyl-imidazoline ligand achieved the evolution of 1.02 m 3 of H 2/CO 2 gases by formic acid dehydrogenation without any additives or adjustments in the solution system. Furthermore, the pyridyl-imidazoline moieties provided the optimum pH to be 1.7, resulting in high activity and stability even at very acidic conditions.

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.

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.

Formic Acid Formation by Clostridium ljungdahlii at Elevated Pressures of Carbon Dioxide and Hydrogen

PubMed Central

Oswald, Florian; Stoll, I. Katharina; Zwick, Michaela; Herbig, Sophia; Sauer, Jörg; Boukis, Nikolaos; Neumann, Anke

2018-01-01

Low productivities of bioprocesses using gaseous carbon and energy sources are usually caused by the low solubility of those gases (e.g., H2 and CO). It has been suggested that increasing the partial pressure of those gases will result in higher dissolved concentrations and should, therefore, be helpful to overcome this obstacle. Investigations of the late 1980s with mixtures of hydrogen and carbon monoxide showed inhibitory effects of carbon monoxide partial pressures above 0.8 bar. Avoiding any effects of carbon monoxide, we investigate growth and product formation of Clostridium ljungdahlii at absolute process pressures of 1, 4, and 7 bar in batch stirred tank reactor cultivations with carbon dioxide and hydrogen as sole gaseous carbon and energy source. With increasing process pressure, the product spectrum shifts from mainly acetic acid and ethanol to almost only formic acid at a total system pressure of 7 bar. On the other hand, no significant changes in overall product yield can be observed. By keeping the amount of substance flow rate constant instead of the volumetric gas feed rate when increasing the process pressure, we increased the overall product yield of 7.5 times of what has been previously reported in the literature. After 90 h of cultivation at a total pressure of 7 bar a total of 4 g L−1 of products is produced consisting of 82.7 % formic acid, 15.6 % acetic acid, and 1.7 % ethanol. PMID:29484294

Porous AgPt@Pt Nanooctahedra as an Efficient Catalyst toward Formic Acid Oxidation with Predominant Dehydrogenation Pathway.

PubMed

Jiang, Xian; Yan, Xiaoxiao; Ren, Wangyu; Jia, Yufeng; Chen, Jianian; Sun, Dongmei; Xu, Lin; Tang, Yawen

2016-11-16

For direct formic acid fuel cells (DFAFCs), the dehydrogenation pathway is a desired reaction pathway, to boost the overall cell efficiency. Elaborate composition tuning and nanostructure engineering provide two promising strategies to design efficient electrocatalysts for DFAFCs. Herein, we present a facile synthesis of porous AgPt bimetallic nanooctahedra with enriched Pt surface (denoted as AgPt@Pt nanooctahedra) by a selective etching strategy. The smart integration of geometric and electronic effect confers a substantial enhancement of desired dehydrogenation pathway as well as electro-oxidation activity for the formic acid oxidation reaction (FAOR). We anticipate that the obtained nanocatalyst may hold great promises in fuel cell devices, and furthermore, the facile synthetic strategy demonstrated here can be extendable for the fabrication of other multicomponent nanoalloys with desirable morphologies and enhanced electrocatalytic performances.

Fe2P as a novel efficient catalyst promoter in Pd/C system for formic acid electro-oxidation in fuel cells reaction

NASA Astrophysics Data System (ADS)

Wang, Fulong; Xue, Huaiguo; Tian, Zhiqun; Xing, Wei; Feng, Ligang

2018-01-01

Developing catalyst promoter for Pd/C catalyst is significant for the catalytic ability improvement in energy transfer related electrochemical reactions. Herein, we demonstrate Fe2P as an efficient catalyst promoter in Pd/C catalyst system for formic acid electro-oxidation in fuel cells reactions. Adding Fe2P in the Pd/C catalyst system greatly increases the performances for formic acid oxidation by 3-4 times; the CO stripping technique displays two kinds of active sites formation in the Pd-Fe2P/C catalyst system coming from the interaction of Pd, Fe2P and Pd oxide species and both are more efficient for formic acid and CO-species electrooxidation. The smaller charge transfer resistance and Tafel slope for formic acid oxidation indicate the improvements in kinetics by Fe2P in the Pd-Fe2P/C system. The nanostructured hybrid units of Pd, Fe2P and carbon are evidently visible in the high resolution microscopy images and XPS technique confirmes the electronic effect in the catalyst system. The promotion effect of Fe2P in the catalyst system arising from the structure, composition and electronic effect changes is discussed with the help from multiple physical and electrochemical techniques. It is concluded that Fe2P as a significant catalyst promoter will have potential application in energy transfer related electrochemical reactions.

76 FR 7106 - Food Additives Permitted in Feed and Drinking Water of Animals; Formic Acid

Federal Register 2010, 2011, 2012, 2013, 2014

2011-02-09

.... FDA-2009-F-0525] Food Additives Permitted in Feed and Drinking Water of Animals; Formic Acid AGENCY...) is amending the regulations for food additives permitted in feed and drinking water of animals to... to a food additive petition filed by Kemira Oyj of Finland. DATES: This rule is effective February 9...

Size effects in electronic and catalytic properties of unsupported palladium nanoparticles in electrooxidation of formic acid.

PubMed

Zhou, Wei Ping; Lewera, Adam; Larsen, Robert; Masel, Rich I; Bagus, Paul S; Wieckowski, Andrzej

2006-07-13

We report a combined X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and chronoamperometry (CA) study of formic acid electrooxidation on unsupported palladium nanoparticle catalysts in the particle size range from 9 to 40 nm. The CV and CA measurements show that the most active catalyst is made of the smallest (9 and 11 nm) Pd nanoparticles. Besides the high reactivity, XPS data show that such nanoparticles display the highest core-level binding energy (BE) shift and the highest valence band (VB) center downshift with respect to the Fermi level. We believe therefore that we found a correlation between formic acid oxidation current and BE and VB center shifts, which, in turn, can directly be related to the electronic structure of palladium nanoparticles of different particle sizes. Clearly, such a trend using unsupported catalysts has never been reported. According to the density functional theory of heterogeneous catalysis, and mechanistic considerations, the observed shifts are caused by a weakening of the bond strength of the COOH intermediate adsorption on the catalyst surface. This, in turn, results in the increase in the formic acid oxidation rate to CO2 (and in the associated oxidation current). Overall, our measurements demonstrate the particle size effect on the electronic properties of palladium that yields different catalytic activity in the HCOOH oxidation reaction. Our work highlights the significance of the core-level binding energy and center of the d-band shifts in electrocatalysis and underlines the value of the theory that connects the center of the d-band shifts to catalytic reactivity.

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

PubMed

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

2010-11-07

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.

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. Copyright © 2012 Elsevier B.V. All rights reserved.

Double proton transfer behavior and one-electron oxidation effect in double H-bonded glycinamide-formic acid complex.

PubMed

Li, Ping; Bu, Yuxiang

2004-11-22

The behavior of double proton transfer occurring in a representative glycinamide-formic acid complex has been investigated at the B3LYP/6-311 + + G( * *) level of theory. Thermodynamic and, especially, kinetic parameters, such as tautomeric energy, equilibrium constant, and barrier heights have been discussed, respectively. The relevant quantities involved in the double proton transfer process, such as geometrical changes, interaction energies, and intrinsic reaction coordinate calculations have also been studied. Computational results show that the participation of a formic acid molecule favors the proceeding of the proton transfer for glycinamide compared with that without mediate-assisted case. The double proton transfer process proceeds with a concerted mechanism rather than a stepwise one since no ion-pair complexes have been located during the proton transfer process. The calculated barrier heights are 11.48 and 0.85 kcal/mol for the forward and reverse directions, respectively. However, both of them have been reduced by 2.95 and 2.61 kcal/mol to 8.53 and -1.76 kcal/mol if further inclusion of zero-point vibrational energy corrections, where the negative barrier height implies that the reverse reaction should proceed with barrierless spontaneously, analogous to that occurring between glycinamide and formamide. Furthermore, solvent effects on the thermodynamic and kinetic processes have also been predicted qualitatively employing the isodensity surface polarized continuum model within the framework of the self-consistent reaction field theory. Additionally, the oxidation process for the double H-bonded glycinamide-formic acid complex has also been investigated. Contrary to that neutral form possessing a pair of two parallel intermolecular H bonds, only a single H bond with a comparable strength has been found in its ionized form. The vertical and adiabatic ionization potentials for the neutral complex have been determined to be about 9.40 and 8.69 e

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. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

2006-12-05

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.

Dehydrogenation of formic acid catalyzed by magnesium hydride anions, HMgL2- (L = Cl and HCO2)

NASA Astrophysics Data System (ADS)

Khairallah, George N.; O'Hair, Richard A. J.

2006-08-01

A two step gas-phase catalytic cycle for the dehydrogenation of formic acid was established using a combination of experiments carried out on a quadrupole ion trap mass spectrometer and DFT calculations. The catalysts are the magnesium hydride anions HMgL2- (L = Cl and HCO2), which are formed from the formate complexes, HCO2MgL2-, via elimination of carbon dioxide under conditions of collision induced dissociation. This is followed by an ion-molecule reaction between HMgL2- and formic acid, which yields hydrogen and also reforms the formate complex, HCO2MgL2-. A kinetic isotope effect in the range 2.3-2.9 was estimated for the rate determining decarboxylation step by carrying out CID on the (HCO2)(DCO2)MgCl2- and subjecting the resultant mixture of (H)(DCO2)MgCl2- and (HCO2)(D)MgCl2- ions at m/z 106 to ion-molecule reactions. DFT calculations (at the B3LYP/6-31 + G* level of theory) were carried out on the HMgCl2- system and revealed that: (i) the decarboxylation of HCO2MgCl2- is endothermic by 47.8 kcal mol-1, consistent with the need to carry out CID to form the HMgCl2-; (ii) HMgCl2- can react with formic acid via either a four centred transition state or a six centred transition state. The former reaction is favoured by 7.8 kcal mol-1.

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.

Homogeneous Catalysis for Sustainable Hydrogen Storage in Formic Acid and Alcohols.

PubMed

Sordakis, Katerina; Tang, Conghui; Vogt, Lydia K; Junge, Henrik; Dyson, Paul J; Beller, Matthias; Laurenczy, Gábor

2018-01-24

Hydrogen gas is a storable form of chemical energy that could complement intermittent renewable energy conversion. One of the main disadvantages of hydrogen gas arises from its low density, and therefore, efficient handling and storage methods are key factors that need to be addressed to realize a hydrogen-based economy. Storage systems based on liquids, in particular, formic acid and alcohols, are highly attractive hydrogen carriers as they can be made from CO 2 or other renewable materials, they can be used in stationary power storage units such as hydrogen filling stations, and they can be used directly as transportation fuels. However, to bring about a paradigm change in our energy infrastructure, efficient catalytic processes that release the hydrogen from these molecules, as well as catalysts that regenerate these molecules from CO 2 and hydrogen, are required. In this review, we describe the considerable progress that has been made in homogeneous catalysis for these critical reactions, namely, the hydrogenation of CO 2 to formic acid and methanol and the reverse dehydrogenation reactions. The dehydrogenation of higher alcohols available from renewable feedstocks is also described. Key structural features of the catalysts are analyzed, as is the role of additives, which are required in many systems. Particular attention is paid to advances in sustainable catalytic processes, especially to additive-free processes and catalysts based on Earth-abundant metal ions. Mechanistic information is also presented, and it is hoped that this review not only provides an account of the state of the art in the field but also offers insights into how superior catalytic systems can be obtained in the future.

Formic acid catalyzed hydrolysis of SO3 in the gas phase: a barrierless mechanism for sulfuric acid production of potential atmospheric importance.

PubMed

Hazra, Montu K; Sinha, Amitabha

2011-11-02

Computational studies at the B3LYP/6-311++G(3df,3pd) and MP2/6-311++G(3df,3pd) levels are performed to explore the changes in reaction barrier height for the gas phase hydrolysis of SO(3) to form H(2)SO(4) in the presence of a single formic acid (FA) molecule. For comparison, we have also performed calculations for the reference reaction involving water assisted hydrolysis of SO(3) at the same level. Our results show that the FA assisted hydrolysis of SO(3) to form H(2)SO(4) is effectively a barrierless process. The barrier heights for the isomerization of the SO(3)···H(2)O···FA prereactive collision complex, which is the rate limiting step in the FA assisted hydrolysis, are found to be respectively 0.59 and 0.08 kcal/mol at the B3LYP/6-311++G(3df,3pd) and MP2/6-311++G(3df,3pd) levels. This is substantially lower than the ~7 kcal/mol barrier for the corresponding step in the hydrolysis of SO(3) by two water molecules--which is currently the accepted mechanism for atmospheric sulfuric acid production. Simple kinetic analysis of the relative rates suggests that the reduction in barrier height facilitated by FA, combined with the greater stability of the prereactive SO(3)···H(2)O···FA collision complex compared to SO(3)···H(2)O···H(2)O and the rather plentiful atmospheric abundance of FA, makes the formic acid mediated hydrolysis reaction a potentially important pathway for atmospheric sulfuric acid production.

Boron Nitride-supported Sub-nanometer Pd 6 Clusters for Formic Acid Decomposition: A DFT Study

DOE PAGES

Schimmenti, Roberto; Cortese, Remedios; Duca, Dario; ...

2017-04-25

A periodic, self-consistent planewave DFT study was carried out to explore the potential use of Pd 6 clusters supported on a boron nitride sheet as a catalyst for the selective decomposition of formic acid (HCOOH) to CO 2 and H 2. The competition between formate (HCOO) and carboxyl (COOH) paths on catalytic sites, with different proximities to the support, was studied. Based on energetics alone, the reaction may mainly follow the HCOO route. Slightly lower activation energies were found at the lateral sites of the cluster as compared to top face sites. This is particularly true for the bidentate tomore » monodentate HCOO conversion. Through comparison of results with similar studies on HCOOH decomposition on extended Pd surfaces, it was demonstrated that the existence of undercoordinated sites in the sub-nanometer cluster could play a key role in preferentially stabilizing HCOO over COOH, which is a common CO precursor in this reaction. A hydrogen spillover mechanism was also investigated; migration toward the boron nitride support is not favorable, at least in the early stages of the reaction. However, hydrogen diffusion on the cluster has low barriers compared to those involved in formic acid decomposition.« less

Boron Nitride-supported Sub-nanometer Pd 6 Clusters for Formic Acid Decomposition: A DFT Study

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

Schimmenti, Roberto; Cortese, Remedios; Duca, Dario

A periodic, self-consistent planewave DFT study was carried out to explore the potential use of Pd 6 clusters supported on a boron nitride sheet as a catalyst for the selective decomposition of formic acid (HCOOH) to CO 2 and H 2. The competition between formate (HCOO) and carboxyl (COOH) paths on catalytic sites, with different proximities to the support, was studied. Based on energetics alone, the reaction may mainly follow the HCOO route. Slightly lower activation energies were found at the lateral sites of the cluster as compared to top face sites. This is particularly true for the bidentate tomore » monodentate HCOO conversion. Through comparison of results with similar studies on HCOOH decomposition on extended Pd surfaces, it was demonstrated that the existence of undercoordinated sites in the sub-nanometer cluster could play a key role in preferentially stabilizing HCOO over COOH, which is a common CO precursor in this reaction. A hydrogen spillover mechanism was also investigated; migration toward the boron nitride support is not favorable, at least in the early stages of the reaction. However, hydrogen diffusion on the cluster has low barriers compared to those involved in formic acid decomposition.« less

Decomposition mechanism of formic acid on Cu (111) surface: A theoretical study

NASA Astrophysics Data System (ADS)

Jiang, Zhao; Qin, Pei; Fang, Tao

2017-02-01

The study of formic acid decomposition on transition metal surfaces is important to obtain useful information for vapor phase catalysis involving HCOOH and for the development of direct formic acid fuel cells. In this study, periodic density functional theory calculations have been employed to investigate the dissociation pathways of HCOOH on Cu (111) surface. About adsorption, it is found that the adsorption of HCOO, COOH, HCO, CO, OH and H on Cu (111) are considered chemisorption, whereas HCOOH, CO2, H2O and H2 have the weak interaction with Cu (111) surface. Furthermore, the minimum energy pathways are analyzed for the decomposition of HCOOH to CO2 and CO through the scission of Hsbnd O, Csbnd H and Csbnd O bonds. It is found that HCOOH, HCOO and COOH prefer to dissociate in the related reactions rather than desorb. For the decomposition, it is indicated that HCO and COOH are the main dissociated intermediates of trans-HCOOH, CO2 is the main dissociated intermediates of bidentate-HCOO, and CO is the main dissociated product of cis-COOH. The co-adsorbed H atom is beneficial for the formation of CO2 from cis-COOH. Besides, it is found that the most favorable path for HCOOH decomposition on Cu (111) surface is HCOOH-HCO-CO (Path 5), where the step of CO formation from HCO dehydrogenation is considered to be the rate-determining step. The results also show that CO is preferentially formed as the dominant product of HCOOH on Cu (111) surface.

Weak hydrogen bonds in complexes pairing monohalomethanes with neutral formic acid

NASA Astrophysics Data System (ADS)

Solimannejad, Mohammad; Scheiner, Steve

2006-06-01

Ab initio calculations are used to analyze the interaction between formic acid and CH 3X, for X equal to each of F, Cl, and Br. All minima are cyclic in that they contain more than one H-bond. The most strongly bound contain a OH⋯X bond, along with CH⋯O, and the others contain CH⋯X and CH⋯O interactions. Alterations of the covalent bond lengths within each subunit, and vibrational frequency shifts, coupled with electronic charge shifts, reveal fundamental features of these complexes, and the nature of the interactions. The OH⋯X bond is the strongest of those examined here, followed by CH⋯X and CH⋯O.

FEL-FTIR spectroscopy of matrix-isolated formic acid

NASA Astrophysics Data System (ADS)

Henderson, Don O.; Mu, Richard; Silberman, Enrique; Berryman, Kenneth W.; Rella, Chris W.

1994-07-01

Infrared spectral hole burning studies have provided a wealth of information concerning site reorientation of defects in solids and vibrational relaxation dynamics. The most investigated systems appear to be impurities trapped in alkali halides. Limited studies on molecules trapped in noble gas matrices have demonstrated that these systems are good candidates for investigating persistent spectral holes. However, most infrared spectral hole burning studies have been limited by the tunability of commercially available infrared lasers which in turn restricts the spectral feature which can be burned. On the other hand, the tunability of Infrared Free Electron Lasers (IR-FELs) allows for targeting radiation into vibrational of the molecular system under study. We have used the Free Electron Laser-Fourier Transform Infrared Spectroscopy to investigate infrared hole burning of formic acid (HCOOD) isolated in an Ar matrix at a matrix/sample ratio of 4000/1. The results of the FEL radiation tuned to v2 mode of HCOOD are discussed together with matrix induced frequency shifts and matrix induced band splittings.

Microwave measurements of proton tunneling and structural parameters for the propiolic acid-formic acid dimer.

PubMed

Daly, Adam M; Douglass, Kevin O; Sarkozy, Laszlo C; Neill, Justin L; Muckle, Matt T; Zaleski, Daniel P; Pate, Brooks H; Kukolich, Stephen G

2011-10-21

Microwave spectra of the propiolic acid-formic acid doubly hydrogen bonded complex were measured in the 1 GHz to 21 GHz range using four different Fourier transform spectrometers. Rotational spectra for seven isotopologues were obtained. For the parent isotopologue, a total of 138 a-dipole transitions and 28 b-dipole transitions were measured for which the a-dipole transitions exhibited splittings of a few MHz into pairs of lines and the b-type dipole transitions were split by ~580 MHz. The transitions assigned to this complex were fit to obtain rotational and distortion constants for both tunneling levels: A(0+) = 6005.289(8), B(0+) = 930.553(8), C(0+) = 803.9948(6) MHz, Δ(0+)(J) = 0.075(1), Δ(0+)(JK) = 0.71(1), and δ(0+)(j) = -0.010(1) kHz and A(0-) = 6005.275(8), B(0-) = 930.546(8), C(0-) = 803.9907(5) MHz, Δ(0-)(J) = 0.076(1), Δ(0-)(JK) = 0.70(2), and δ(0-)(j) = -0.008(1) kHz. Double resonance experiments were used on some transitions to verify assignments and to obtain splittings for cases when the b-dipole transitions were difficult to measure. The experimental difference in energy between the two tunneling states is 291.428(5) MHz for proton-proton exchange and 3.35(2) MHz for the deuterium-deuterium exchange. The vibration-rotation coupling constant between the two levels, F(ab), is 120.7(2) MHz for the proton-proton exchange. With one deuterium atom substituted in either of the hydrogen-bonding protons, the tunneling splittings were not observed for a-dipole transitions, supporting the assignment of the splitting to the concerted proton tunneling motion. The spectra were obtained using three Flygare-Balle type spectrometers and one chirped-pulse machine at the University of Virginia. Rotational constants and centrifugal distortion constants were obtained for HCOOH···HOOCCCH, H(13)COOH···HOOCCCH, HCOOD···HOOCCCH, HCOOH···DOOCCCH, HCOOD···DOOCCCH, DCOOH···HOOCCCH, and DCOOD···HOOCCCH. High-level ab initio calculations provided

Effective depolymerization of concentrated acid hydrolysis lignin using a carbon-supported ruthenium catalyst in ethanol/formic acid media.

PubMed

Kristianto, Ivan; Limarta, Susan Olivia; Lee, Hyunjoo; Ha, Jeong-Myeong; Suh, Dong Jin; Jae, Jungho

2017-06-01

Lignin isolated by two-step concentrated acid hydrolysis of empty fruit bunch (EFB) was effectively depolymerized into a high-quality bio-oil using formic acid (FA) as an in-situ hydrogen source and Ru/C as a catalyst in supercritical ethanol. A bio-oil yield of 66.3wt% with an average molecular weight of 822g/mol and an aromatic monomer content of 6.1wt% was achieved at 350°C and a FA-to-lignin mass ratio of 3 after a reaction time of 60min. The combination of Ru/C and FA also resulted in a significant reduction in the oxygen content of the bio-oil by ∼60% and a corresponding increase in the higher heating value (HHV) to 32.7MJ/kg due to the enhanced hydrodeoxygenation activity. An examination of the FA decomposition characteristics revealed that Ru/C provides a greater increase in the rate of hydrogen production from FA, explaining the efficient depolymerization of lignin in a combined system. Copyright © 2017 Elsevier Ltd. All rights reserved.

Facile regio- and stereoselective hydrometalation of alkynes with a combination of carboxylic acids and group 10 transition metal complexes: selective hydrogenation of alkynes with formic acid.

PubMed

Shen, Ruwei; Chen, Tieqiao; Zhao, Yalei; Qiu, Renhua; Zhou, Yongbo; Yin, Shuangfeng; Wang, Xiangbo; Goto, Midori; Han, Li-Biao

2011-10-26

A facile, highly stereo- and regioselective hydrometalation of alkynes generating alkenylmetal complex is disclosed for the first time from a reaction of alkyne, carboxylic acid, and a zerovalent group 10 transition metal complex M(PEt(3))(4) (M = Ni, Pd, Pt). A mechanistic study showed that the hydrometalation does not proceed via the reaction of alkyne with a hydridometal generated by the protonation of a carboxylic acid with Pt(PEt(3))(4), but proceeds via a reaction of an alkyne coordinate metal complex with the acid. This finding clarifies the long proposed reaction mechanism that operates via the generation of an alkenylpalladium intermediate and subsequent transformation of this complex in a variety of reactions catalyzed by a combination of Brϕnsted acid and Pd(0) complex. This finding also leads to the disclosure of an unprecedented reduction of alkynes with formic acid that can selectively produce cis-, trans-alkenes and alkanes by slightly tuning the conditions.

Photocatalytic dehydrogenation of formic acid on CdS nanorods through Ni and Co redox mediation under mild conditions.

PubMed

Khan, Muhammad Abdullah; Rehman, Zia-Ur-; Nasir, Jamal Abdul; Hafeez, Muhammad; Arshad, Muhammad; Ali, Naveed Zafar; Teixieira, Ivo F; McPherson, Ian

2018-05-30

Selective release of hydrogen from formic acid (FA) is deemed feasible to solve issues associated with the release and storage of hydrogen. Here, we present a new efficient photocatalytic system consisting of CdS nanorods (NR), Ni, and Co to liberate hydrogen from formic acid. The optimised noble metal free catalytic system employs Ni/Co as a redox mediator to relay electrons and holes from CdS-NR to the Ni and Co respectively, which also deters the oxidation of CdS-NR. As a result, a high hydrogen production activity of 32.6 mmolh-1g-1 from the decomposition of FA was noted. Furthermore, the photocatalytic system exhibit sustained H2 production rate for 12 hours with sequential turnover numbers surpassing 4×103, 3×103 and 2×103 for Co-Ni/CdS-NR, Ni-CdS-NR and CoCl2/CdS-NR respectively. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The anionic (9-methyladenine)-(1-methylthymine) base pair solvated by formic acid. A computational and photoelectron spectroscopy study.

PubMed

Storoniak, Piotr; Mazurkiewicz, Kamil; Haranczyk, Maciej; Gutowski, Maciej; Rak, Janusz; Eustis, Soren N; Ko, Yeon Jae; Wang, Haopeng; Bowen, Kit H

2010-09-02

The photoelectron spectrum for (1-methylthymine)-(9-methyladenine)...(formic acid) (1MT-9MA...FA) anions with the maximum at ca. 1.87 eV was recorded with 2.54 eV photons and interpreted through the quantum-chemical modeling carried out at the B3LYP/6-31+G(d,p) level. The relative free energies of the anions and their calculated vertical detachment energies suggest that only seven anionic structures contribute to the observed PES signal. We demonstrate that electron binding to the (1MT-9MA...FA) complex can trigger intermolecular proton transfer from formic acid, leading to the strong stabilization of the resulting radical anion. The SOMO distribution indicates that an excess electron may localize not only on the pyrimidine but also on the purine moiety. The biological context of DNA-environment interactions concerning the formation of single-strand breaks induced by excess electrons has been briefly discussed.

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

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

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

Theel, Elitza S; Schmitt, Bryan H; Hall, Leslie; Cunningham, Scott A; Walchak, Robert C; Patel, Robin; Wengenack, Nancy L

2012-09-01

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.

Life cycle, techno-economic and dynamic simulation assessment of bioelectrochemical systems: A case of formic acid synthesis.

PubMed

Shemfe, Mobolaji; Gadkari, Siddharth; Yu, Eileen; Rasul, Shahid; Scott, Keith; Head, Ian M; Gu, Sai; Sadhukhan, Jhuma

2018-05-01

A novel framework, integrating dynamic simulation (DS), life cycle assessment (LCA) and techno-economic assessment (TEA) of a bioelectrochemical system (BES), has been developed to study for the first time wastewater treatment by removal of chemical oxygen demand (COD) by oxidation in anode and thereby harvesting electron and proton for carbon dioxide reduction reaction or reuse to produce products in cathode. Increases in initial COD and applied potential increase COD removal and production (in this case formic acid) rates. DS correlations are used in LCA and TEA for holistic performance analyses. The cost of production of HCOOH is €0.015-0.005 g -1 for its production rate of 0.094-0.26 kg yr -1 and a COD removal rate of 0.038-0.106 kg yr -1 . The life cycle (LC) benefits by avoiding fossil-based formic acid production (93%) and electricity for wastewater treatment (12%) outweigh LC costs of operation and assemblage of BES (-5%), giving a net 61MJkg -1 HCOOH saving. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

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

PubMed

Metin, Önder; Sun, Xiaolian; Sun, Shouheng

2013-02-07

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.

A Large Underestimate of Formic Acid from Tropical Fires: Constraints from Space-Borne Measurements.

PubMed

Chaliyakunnel, S; Millet, D B; Wells, K C; Cady-Pereira, K E; Shephard, M W

2016-06-07

Formic acid (HCOOH) is one of the most abundant carboxylic acids and a dominant source of atmospheric acidity. Recent work indicates a major gap in the HCOOH budget, with atmospheric concentrations much larger than expected from known sources. Here, we employ recent space-based observations from the Tropospheric Emission Spectrometer with the GEOS-Chem atmospheric model to better quantify the HCOOH source from biomass burning, and assess whether fire emissions can help close the large budget gap for this species. The space-based data reveal a severe model HCOOH underestimate most prominent over tropical burning regions, suggesting a major missing source of organic acids from fires. We develop an approach for inferring the fractional fire contribution to ambient HCOOH and find, based on measurements over Africa, that pyrogenic HCOOH:CO enhancement ratios are much higher than expected from direct emissions alone, revealing substantial secondary organic acid production in fire plumes. Current models strongly underestimate (by 10 ± 5 times) the total primary and secondary HCOOH source from African fires. If a 10-fold bias were to extend to fires in other regions, biomass burning could produce 14 Tg/a of HCOOH in the tropics or 16 Tg/a worldwide. However, even such an increase would only represent 15-20% of the total required HCOOH source, implying the existence of other larger missing sources.

Co-adsorption of oxygen and formic acid on rutile TiO2 (110) studied by infrared reflection-absorption spectroscopy

NASA Astrophysics Data System (ADS)

Mattsson, Andreas; Österlund, Lars

2017-09-01

Adsorption of formic acid and co-adsorption with oxygen have been investigated on the rutile TiO2(110) surface using p- and s-polarized infrared reflection-absorption spectroscopy (IRRAS) at O2 exposures between 45 L to 8100 L and at temperatures between 273 K and 343 K. On the clean surface formic acid dissociates into a formate ion (formate) and a proton. Formate binds to two five-fold coordinated Ti atoms in the troughs along the [001] direction, and the proton binds to neighboring bridging O atoms. Exposure of adsorbed formate to O2 leads to a decrease in the asymmetric νas(OCO) band at 1532 cm-1 and to the concomitant formation of a new vibration band at 1516 cm-1. From the s-and p-polarized IRRAS measurements performed at different O2 exposures, surface pre-treatments and substrate temperatures, and by comparisons with previous reports, we conclude that the new species is a bidentate surface hydrogen carbonate, which is formed by reaction between formate and oxygen adatoms on the surface. The σv reflection plane of the surface hydrogen carbonate molecule is oriented along the [001] direction, i.e. the same direction as the adsorbed formate molecule. On the clean TiO2(110) surface exposed to O2 prior to formic acid adsorption, similar results are obtained. The reaction rate to form surface hydrogen carbonate from formate is found to follow first-order kinetics, with an apparent activation energy of Er=0.25 eV.

Effect of the ortho-Hydroxyl Groups on a Bipyridine Ligand of Iridium Complexes for the High-Pressure Gas Generation from the Catalytic Decomposition of Formic Acid.

PubMed

Iguchi, Masayuki; Zhong, Heng; Himeda, Yuichiro; Kawanami, Hajime

2017-12-14

The hydroxyl groups of a 2,2'-bipyridine (bpy) ligand near the metal center activated the catalytic performance of the Ir complex for the dehydrogenation of formic acid at high pressure. The position of the hydroxyl groups on the ligand affected the catalytic durability for the high-pressure H 2 generation through the decomposition of formic acid. The Ir complex with a bipyridine ligand functionalized with para-hydroxyl groups shows a good durability with a constant catalytic activity during the reaction even under high-pressure conditions, whereas deactivation was observed for an Ir complex with a bipyridine ligand with ortho-hydroxyl groups (2). In the presence of high-pressure H 2 , complex 2 decomposed into the ligand and an Ir trihydride complex through the isomerization of the bpy ligand. This work provides the development of a durable catalyst for the high-pressure H 2 production from formic acid. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Iodide-Photocatalyzed Reduction of Carbon Dioxide to Formic Acid with Thiols and Hydrogen Sulfide.

PubMed

Berton, Mateo; Mello, Rossella; González-Núñez, María Elena

2016-12-20

The photolysis of iodide anions promotes the reaction of carbon dioxide with hydrogen sulfide or thiols to quantitatively yield formic acid and sulfur or disulfides. The reaction proceeds in acetonitrile and aqueous solutions, at atmospheric pressure and room temperature by irradiation using a low-pressure mercury lamp. This transition-metal-free photocatalytic process for CO 2 capture coupled with H 2 S removal may have been relevant as a prebiotic carbon dioxide fixation. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solar to Liquid Fuels Production: Light-Driven Reduction of Carbon Dioxide to Formic Acid

DTIC Science & Technology

2014-03-29

molecular wire. The X-ray crystal structure for the E . coli FDH enzyme shows that a [4Fe-4S] cluster is located near the surface of the protein. The...CO2 to formic acid. E . coli FDH, encoded by fdhF, was chosen for this work because it is a single-subunit enzyme that has been studied in detail, and...mutagenesis was employed to change surface-located Cys11 to Gly to open a coordination site. The proteins were overproduced in E . coli and purified

Propitious Dendritic Cu2O-Pt Nanostructured Anodes for Direct Formic Acid Fuel Cells.

PubMed

El-Nagar, Gumaa A; Mohammad, Ahmad M; El-Deab, Mohamed S; El-Anadouli, Bahgat E

2017-06-14

This study introduces a novel competent dendritic copper oxide-platinum nanocatalyst (nano-Cu 2 O-Pt) immobilized onto a glassy carbon (GC) substrate for formic acid (FA) electro-oxidation (FAO); the prime reaction in the anodic compartment of direct formic acid fuel cells (DFAFCs). Interestingly, the proposed catalyst exhibited an outstanding improvement for FAO compared to the traditional platinum nanoparticles (nano-Pt) modified GC (nano-Pt/GC) catalyst. This was evaluated from steering the reaction mechanism toward the desired direct route producing carbon dioxide (CO 2 ); consistently with mitigating the other undesired indirect pathway producing carbon monoxide (CO); the potential poison deteriorating the catalytic activity of typical Pt-based catalysts. Moreover, the developed catalyst showed a reasonable long-term catalytic stability along with a significant lowering in onset potential of direct FAO that ultimately reduces the polarization and amplifies the fuel cell's voltage. The observed catalytic enhancement was believed to originate bifunctionally; while nano-Pt represented the base for the FA adsorption, nanostructured copper oxide (nano-Cu 2 O) behaved as a catalytic mediator facilitating the charge transfer during FAO and providing the oxygen atmosphere inspiring the poison's (CO) oxidation at relatively lower potential. Surprisingly, moreover, nano-Cu 2 O induced a surface retrieval of nano-Pt active sites by capturing the poisoning CO via "a spillover mechanism" to renovate the Pt surface for the direct FAO. Finally, the catalytic tolerance of the developed catalyst toward halides' poisoning was discussed.

Metabolic pathway engineering based on metabolomics confers acetic and formic acid tolerance to a recombinant xylose-fermenting strain of Saccharomyces cerevisiae

PubMed Central

2011-01-01

Background The development of novel yeast strains with increased tolerance toward inhibitors in lignocellulosic hydrolysates is highly desirable for the production of bio-ethanol. Weak organic acids such as acetic and formic acids are necessarily released during the pretreatment (i.e. solubilization and hydrolysis) of lignocelluloses, which negatively affect microbial growth and ethanol production. However, since the mode of toxicity is complicated, genetic engineering strategies addressing yeast tolerance to weak organic acids have been rare. Thus, enhanced basic research is expected to identify target genes for improved weak acid tolerance. Results In this study, the effect of acetic acid on xylose fermentation was analyzed by examining metabolite profiles in a recombinant xylose-fermenting strain of Saccharomyces cerevisiae. Metabolome analysis revealed that metabolites involved in the non-oxidative pentose phosphate pathway (PPP) [e.g. sedoheptulose-7-phosphate, ribulose-5-phosphate, ribose-5-phosphate and erythrose-4-phosphate] were significantly accumulated by the addition of acetate, indicating the possibility that acetic acid slows down the flux of the pathway. Accordingly, a gene encoding a PPP-related enzyme, transaldolase or transketolase, was overexpressed in the xylose-fermenting yeast, which successfully conferred increased ethanol productivity in the presence of acetic and formic acid. Conclusions Our metabolomic approach revealed one of the molecular events underlying the response to acetic acid and focuses attention on the non-oxidative PPP as a target for metabolic engineering. An important challenge for metabolic engineering is identification of gene targets that have material importance. This study has demonstrated that metabolomics is a powerful tool to develop rational strategies to confer tolerance to stress through genetic engineering. PMID:21219616

Evaluation of Pd Nanoparticle-Decorated CeO2-MWCNT Nanocomposite as an Electrocatalyst for Formic Acid Fuel Cells

NASA Astrophysics Data System (ADS)

Saleem, Junaid; Safdar Hossain, SK.; Al-Ahmed, Amir; Rahman, Ateequr; McKay, Gordon; Hossain, Mohammed M.

2018-04-01

In this work, CeO2-modified Pd/CeO2-carbon nanotube (CNT) electrocatalyst for the electro-oxidation of formic acid has been investigated. The support CNT was first modified with different amounts (5-30 wt.%) of CeO2 using a precipitation-deposition method. The electrocatalysts were developed by dispersing Pd on the CeO2-CNT supports using the borohydride reduction method. The synthesized electrocatalysts were analyzed for composition, morphology and electronic structure using x-ray diffraction (XRD), scanning electron microscopy with energy-dispersive x-ray spectroscopy (SEM/EDX), transmission electron microscopy (TEM), x-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA) techniques. The formation of Pd nanoparticles on the CeO2-CNT support was confirmed using TEM. The activity of Pd/CeO2-CNT and of Pd-CNT samples upon oxidation of formic acid was evaluated by using carbon monoxide stripping voltammetry, cyclic voltammetry, and chronoamperometry. The addition of moderate amounts of cerium oxide (up to 10 wt.%) significantly improved the activity of Pd/CeO2-CNT compared to the unmodified Pd-CNT. Pd/10 wt.% CeO2-CNT showed a current density of 2 A mg-1, which is ten times higher than that of the unmodified Pd-CNT (0.2 A mg-1). Similarly, the power density obtained for Pd/10 wt.% CeO2-CNT in an air-breathing formic acid fuel cell was 6.8 mW/cm2 which is two times higher than Pd-CNT (3.2 mW/cm2), thus exhibiting the promotional effects of CeO2 to Pd/CeO2-CNT. A plausible justification for the improved catalytic performance and stability is provided in the light of the physical characterization results.

PdCo supported on multiwalled carbon nanotubes as an anode catalyst in a microfluidic formic acid fuel cell

NASA Astrophysics Data System (ADS)

Morales-Acosta, D.; Morales-Acosta, M. D.; Godinez, L. A.; Álvarez-Contreras, L.; Duron-Torres, S. M.; Ledesma-García, J.; Arriaga, L. G.

This work reports the synthesis of Pd-based alloys of Co and their evaluation as anode materials in a microfluidic formic acid fuel cell (μFAFC). The catalysts were prepared using the impregnation method followed by thermal treatment. The synthesized catalysts contain 22 wt.% Pd on multiwalled carbon nanotubes (Pd/MWCNT) and its alloys with two Co atomic percent in the sample with 4 at.% Co (PdCo1/MWCNT) and 10 at.% Co (PdCo2/MWCNT). The role of the alloying element was determined by XRD and XPS techniques. Both catalysts were evaluated as anode materials in a μFAFC operating with different concentrations of HCOOH (0.1 and 0.5 M), and the results were compared to those obtained with Pd/MWCNT. A better performance was obtained for the cell using PdCo1/MWCNT (1.75 mW cm -2) compared to Pd/MWCNT (0.85 mW cm -2) in the presence of 0.5 M HCOOH. By means of external electrode measurements, it was also possible to observe shifts in the formic acid oxidation potential due to a fuel concentration increment (ca. 0.05 V for both PdCo1/MWCNT and PdCo2/MWCNT catalysts and 0.23 V for Pd/MWCNT) that was attributed to deactivation of the catalyst material. The maximum current densities obtained were 8 mA cm -2 and 5.2 mA cm -2 for PdCo2/MWCNT and Pd/MWCNT, respectively. In this way, the addition of Co to the Pd catalyst was shown to improve the tolerance of intermediates produced during formic acid oxidation that tend to poison Pd, thus improving the catalytic activity and stability of the cell.

Pd/WO3/C nanocomposite with APTMS-functionalized tungsten oxide nanosheet for formic acid electrooxidation enhancement

NASA Astrophysics Data System (ADS)

Yang, Yang; Li, Yun-Hua; Zhao, Ya-Fei; Li, Peng-Wei; Li, Qiao-Xia

2018-01-01

A Pd/WO3/C nanocomposite with 3-aminopropyltrimethoxysilane (APTMS)-functionalized tungsten oxide nanosheets (Pd/WO3/C-APTMS) was synthesized and applied as the efficient anode catalyst for direct formic acid fuel cells (DFAFCs). The mechanism for synthesizing the nanocomposite is as follows: initially, [PdCl4]2- was assembled onto the tungsten oxide nanosheets modified with APTMS. Following this, Pd nanoparticles were reduced via traditional impregnation reduction of [PdCl4]2- with NaBH4. The transmission electron microscope (TEM) images revealed that the Pd nanoparticles were uniformly dispersed on WO3 nanosheets and were approximately 2.7 nm in size. The electrochemical test results showed that enhanced electrocatalytic activity for the formic acid oxidation reaction (FAOR) was obtained on the Pd/WO3/C catalyst compared with Pd/C. The higher electrocatalytic activity might be attributed to the uniform distribution of Pd with smaller particles. Furthermore, it is likely that the improvement in catalytic stability for the Pd/WO3/C catalyst is due to the hydrogen spillover effect of WO3 particles. These results indicate that this novel Pd/WO3/C-APTMS nanocomposite exhibits promising potential for use as an anode electrocatalyst in DFAFCs.

Formic acid decomposition on Pt1/Cu (111) single platinum atom catalyst: Insights from DFT calculations and energetic span model analysis

NASA Astrophysics Data System (ADS)

Wang, Ying-Fan; Li, Kun; Wang, Gui-Chang

2018-04-01

Inspired by the recent surface experimental results that the monatomic Pt catalysts has more excellent hydrogen production that Cu(111) surface, the mechanism of decomposition of formic acid on Cu(111) and single atom Pt1/Cu(111) surface was studied by periodic density functional theory calculations in the present work. The results show that the formic acid tends to undergo dehydrogenation on both surfaces to obtain the hydrogen product of the target product, and the selectivity and catalytic activity of Pt1/Cu (111) surface for formic acid dehydrogenation are better. The reason is that the single atom Pt1/Cu(111) catalyst reduces the reaction energy barrier (i.e., HCOO → CO2 + H) of the critical step of the dehydrogenation reaction due to the fact that the single atom Pt1/Cu(111) catalyst binds formate weakly compared to that of Cu (111) one. Moreover, it was found that the Pt1/Cu (111) binds CO more strongly than that of Cu (111) one and thus leading to the difficult for the formation of CO. These two factors would make the single Pt atom catalyst had the high selectivity for the H2 production. It is hoped that the present work may help people to design the efficient H2 production from HCOOH decomposition by reduce the surface binding strength of HCOO species, for example, using the low coordination number active site like single atom or other related catalytic system.

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.

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. Copyright © 2014 Elsevier Ltd. All rights reserved.

Computational Design of Cobalt Catalysts for Hydrogenation of Carbon Dioxide and Dehydrogenation of Formic Acid.

PubMed

Ge, Hongyu; Jing, Yuanyuan; Yang, Xinzheng

2016-12-05

A series of cobalt complexes with acylmethylpyridinol and aliphatic PNP pincer ligands are proposed based on the active site structure of [Fe]-hydrogenase. Density functional theory calculations indicate that the total free energy barriers of the hydrogenation of CO 2 and dehydrogenation of formic acid catalyzed by these Co complexes are as low as 23.1 kcal/mol in water. The acylmethylpyridinol ligand plays a significant role in the cleavage of H 2 by forming a strong Co-H δ- ···H δ+ -O dihydrogen bond in a fashion of frustrated Lewis pairs.

Photochemically engineering the metal-semiconductor interface for room-temperature transfer hydrogenation of nitroarenes with formic acid.

PubMed

Li, Xin-Hao; Cai, Yi-Yu; Gong, Ling-Hong; Fu, Wei; Wang, Kai-Xue; Bao, Hong-Liang; Wei, Xiao; Chen, Jie-Sheng

2014-12-08

A mild photochemical approach was applied to construct highly coupled metal-semiconductor dyads, which were found to efficiently facilitate the hydrogenation of nitrobenzene. Aniline was produced in excellent yield (>99 %, TOF: 1183) using formic acid as hydrogen source and water as solvent at room temperature. This general and green catalytic process is applicable to a wide range of nitroarenes without the involvement of high-pressure gases or sacrificial additives. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Field measurement evidence for an atmospheric chemical source of formic and acetic acids in the tropic

NASA Astrophysics Data System (ADS)

Sanhueza, Eugenio; Santana, Magaly; Trapp, Dorothea; de Serves, Claes; Figueroa, Luis; Romero, Rodrigo; Rondón, Alberto; Donoso, Loreto

The simultaneous measurements of atmospheric HCOOH, CH3COOH H2O2, organic peroxides, HCHO, CH3CHO and isoprene made in the Venezuelan savannah region, in the wet season (September, 1993) and during the period of high solar irradiation is reported. The average concentrations (in ppbv) between 10:00 and 16:00 were: HCOOH 0.75±0.32, CH3COOH 0.56±0.28, H2O2 1.37±0.48, the total peroxides 1.83±0.60, HCHO 1.38± .43, CH3CHO 0.35±0.15, and isoprene 2.18±0.78. A good correlation was observed between the concentrations (15 min averages) of both acids. The acids also correlate with isoprene (the most abundant olefin in the savannah atmosphere), H2O2 and the total peroxides. HCOOH also correlates well with HCHO and CH3CHO. These results support the hypothesis that significant amount of formic and acetic acids are produced in the tropical atmosphere as a result of the oxidation of reactive hydrocarbons.

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. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

High Upward Fluxes of Formic Acid from a Boreal Forest Canopy

NASA Technical Reports Server (NTRS)

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

High upward fluxes of formic acid from a boreal forest canopy

DOE PAGES

Schobesberger, Siegfried; Lopez-Hilfiker, Felipe D.; Taipale, Ditte; ...

2016-08-14

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. Here,more » 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.« less

Glycolic acid physical properties and impurities assessment

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

Lambert, D. P.; Pickenheim, B. R.; Bibler, N. E.

This document has been revised due to recent information that the glycolic acid used in Savannah River National Laboratory (SRNL) experiments contains both formaldehyde and methoxyacetic acid. These impurities were in the glycolic acid used in the testing included in this report and in subsequent testing using DuPont (now called Chemours) supplied Technical Grade 70 wt% glycolic acid. However, these impurities were not reported in earlier revisions. Additional data concerning the properties of glycolic acid have also been added to this report. The Defense Waste Processing Facility (DWPF) is planning to implement a nitric-glycolic acid flowsheets to increase attainment tomore » meet closure commitment dates during Sludge Batch 9. In fiscal year 2009, SRNL was requested to determine the physical properties of formic and glycolic acid blends. Blends of formic acid in glycolic acid were prepared and their physical properties tested. Increasing amounts of glycolic acid led to increases in blend density, viscosity and surface tension as compared to the 90 wt% formic acid that is currently used at DWPF. These increases are small, however, and are not expected to present any difficulties in terms of processing. The effect of sulfur impurities in Technical Grade glycolic acid was studied for its impact on DWPF glass quality. While the glycolic acid specification allows for more sulfate than the current formic acid specification, the ultimate impact is expected to be on the order of 0.033 wt% sulfur in glass. Note that lower sulfur content glycolic acid could likely be procured at some increased cost if deemed necessary. A paper study on the effects of radiation on glycolic acid was performed. The analysis indicates that substitution of glycolic acid for formic acid would not increase the radiolytic production rate of H2 and cause an adverse effect in the Slurry Receipt and Adjustment Tank (SRAT) or Slurry Mix Evaporator (SME) process. It has been cited that glycolic acid

Mechanistic insights into iron catalyzed dehydrogenation of formic acid: β-hydride elimination vs. direct hydride transfer.

PubMed

Yang, Xinzheng

2013-09-07

Density functional theory calculations reveal a complete reaction mechanism with detailed energy profiles and transition state structures for the dehydrogenation of formic acid catalyzed by an iron complex, [P(CH2CH2PPh2)3FeH](+). In the cationic reaction pathway, a β-hydride elimination process is confirmed to be the rate-determining step in this catalytic reaction. A potential reaction pathway starting with a direct hydride transfer from HCOO(-) to Fe is found to be possible, but slightly less favorable than the catalytic cycle with a β-hydride elimination step.

Impact of scaling on the nitric-glycolic acid flowsheet

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

Lambert, D.

Savannah River Remediation (SRR) is considering using glycolic acid as a replacement for formic acid in Sludge Receipt and Adjustment Tank (SRAT) processing in the Defense Waste Processing Facility (DWPF). Catalytic decomposition of formic acid is responsible for the generation of hydrogen, a potentially flammable gas, during processing. To prevent the formation of a flammable mixture in the offgas, an air purge is used to dilute the hydrogen concentration below the 60% of the Composite Lower Flammability Limit (CLFL). The offgas is continuously monitored for hydrogen using Gas Chromatographs (GCs). Since formic acid is much more volatile and toxic thanmore » glycolic acid, a formic acid spill would lead to the release of much larger quantities to the environment. Switching from formic acid to glycolic acid is expected to eliminate the hydrogen flammability hazard leading to lower air purges, thus downgrading of Safety Significant GCs to Process Support GCs, and minimizing the consequence of a glycolic acid tank leak in DWPF. Overall this leads to a reduction in process operation costs and an increase in safety margin. Experiments were completed at three different scales to demonstrate that the nitric-glycolic acid flowsheet scales from the 4-L lab scale to the 22-L bench scale and 220-L engineering scale. Ten process demonstrations of the sludge-only flowsheet for SRAT and Slurry Mix Evaporator (SME) cycles were performed using Sludge Batch 8 (SB8)-Tank 40 simulant. No Actinide Removal Process (ARP) product or strip effluent was added during the runs. Six experiments were completed at the 4-L scale, two experiments were completed at the 22-L scale, and two experiments were completed at the 220-L scale. Experiments completed at the 4-L scale (100 and 110% acid stoichiometry) were repeated at the 22-L and 220-L scale for scale comparisons.« less

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.

Hydrogen Production and Storage on a Formic Acid/Bicarbonate Platform using Water-Soluble N-Heterocyclic Carbene Complexes of Late Transition Metals.

PubMed

Jantke, Dominik; Pardatscher, Lorenz; Drees, Markus; Cokoja, Mirza; Herrmann, Wolfgang A; Kühn, Fritz E

2016-10-06

The synthesis and characterization of two water-soluble bis-N-heterocyclic carbene (NHC) complexes of rhodium and iridium is presented. Both compounds are active in H 2 generation from formic acid and in hydrogenation of bicarbonate to formate. The rhodium derivative is most active in both reactions, reaching a TOF of 39 000 h -1 and a TON of 449 000 for H 2 production. The catalytic hydrogenation reactions were carried out in an autoclave system and analyzed using the integrated peak areas in the 1 H NMR spectra. Decomposition of formic acid was investigated using a Fisher-Porter bottle equipped with a pressure transducer. Long-term stability for hydrogen evolution was tested by surveillance of the gas flow rate. The procedure does not require any additives like amines or inert gas conditions. Density functional theory calculations in agreement with experimental results suggest a bicarbonate reduction mechanism involving a second catalyst molecule, which provides an external hydride acting as reducing agent. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

X-ray and neutron scattering studies of liquid formic acid DCOOD at various temperatures and under pressure

NASA Astrophysics Data System (ADS)

Nasr, Salah; Bellissent-Funel, Marie-Claire; Cortès, Robert

1999-06-01

A structural investigation of fully deuterated liquid formic acid was performed by neutron scattering at pressure up to 3 kbar. The molecular pair correlation function was also deduced from x-ray study of DCOOD at ambient pressure and at 294 K. The results could be explained in terms of an open-chain structure with only two H bonds per molecule. The mean O⋯O distance is about 2.72 Å. The effect of both temperature and pressure on the hydrogen bond network is examined.

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...

The Jet-Cooled High-Resolution IR Spectrum of Formic Acid Cyclic Dimer

NASA Astrophysics Data System (ADS)

Goubet, Manuel; Bteich, Sabath; Huet, Therese R.; Pirali, Olivier; Asselin, Pierre; Soulard, Pascale; Jabri, Atef; Roy, P.; Georges, Robert

2017-06-01

As the simplest carboxylic acid, formic acid (FA) is an excellent model molecule to investigate the general properties of carboxylic acids. FA is also an atmospherically and astrophysically relevant molecule. It is well known that its dimeric form is predominant in the gas phase at temperatures below 423 K. The cyclic conformation of the dimer (FACD) is an elementary system to be understood for the concerted hydrogen transfer through equivalent hydrogen bonds, an essential process within biomolecules. The IR range is a crucial spectral region, particularly the far-IR, as it gives a direct access to the intermolecular vibrational modes involved in this process. Moreover, due to its centrosymmetric conformation, the FACD exhibits no pure rotation spectrum and, due to spectral line congestion and Doppler broadening, IR bands cannot be rotationally resolved at room temperature. So far, only parts of the ν_{5}-GS band (C-O stretch) have been observed under jet-cooled conditions using laser techniques. We present here six rotationally resolved IR bands of FACD recorded under jet-cooled conditions using the Jet-AILES apparatus and the QCL spectrometer at MONARIS, including the far-IR ν_{24}-GS band (intermolecular in-plane bending). Splitting due to vibration-rotation-tunneling motions are clearly observed. A full spectral analysis is in progress starting from the GS constants obtained by Goroya et al. and with the support of electronic structure calculations. T. Miyazawa and K. S. Pitzer, J. Am. Chem. Soc. 81, 74, 1959 R. Georges, M. Freytes, D. Hurtmans, I. Kleiner, J. Vander Auwera, M. Herman, Chem. Phys. 305, 187, 2004 M. Ortlieb and M. Havenith, J. Phys. Chem. A 111, 7355, 2007; K. G. Goroya, Y. Zhu, P. Sun and C. Duan, J. Chem. Phys. 140, 164311, 2014 This work is supported by the CaPPA project (Chemical and Physical Properties of the Atmosphere) ANR-11-LABX-0005-01

Efficient dehydrogenation of formic acid using Al12N12 nanocage: A DFT study

NASA Astrophysics Data System (ADS)

Esrafili, Mehdi D.; Nurazar, Roghaye

2014-11-01

We have studied the adsorption and decomposition of formic acid (HCOOH) on the surface of Al12N12 fullerene-like nanocage using density functional theory. Different adsorption modes were found for HCOOH on the Al12N12, i.e. molecular and dissociative monodentate or bidentate adsorption. Three reaction pathways were proposed to understand gas-phase HCOOH decomposition on the Al12N12 nanocage. Our results reveal that for the decomposition of HCOOH into CO2 and H2, the most favorable pathway should be the Csbnd H bond activation reaction. The reaction energies and the activation barriers obtained here suggest that for the dissociative adsorption configuration on the Al12N12 surface, the rate-determining step is the Csbnd H bond breaking.

Microwave measurements of the tropolone–formic acid doubly hydrogen bonded dimer

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

Pejlovas, Aaron M.; Kukolich, Stephen G.; Serrato, Agapito

2016-01-28

The microwave spectrum was measured for the doubly hydrogen bonded dimer formed between tropolone and formic acid. The predicted symmetry of this dimer was C{sub 2v}(M), and it was expected that the concerted proton tunneling motion would be observed. After measuring 25 a- and b-type rotational transitions, no splittings which could be associated with a concerted double proton tunneling motion were observed. The calculated barrier to the proton tunneling motion is near 15 000 cm{sup −1}, which would likely make the tunneling frequencies too small to observe in the microwave spectra. The rotational and centrifugal distortion constants determined from the measuredmore » transitions were A = 2180.7186(98) MHz, B = 470.873 90(25) MHz, C = 387.689 84(22) MHz, D{sub J} = 0.0100(14) kHz, D{sub JK} = 0.102(28) kHz, and D{sub K} = 13.2(81) kHz. The B3LYP/aug-cc-pVTZ calculated rotational constants were within 1% of the experimentally determined values.« less

Homogeneous Palladium-Catalyzed Transfer Hydrogenolysis of Benzylic Alcohols Using Formic Acid as Reductant.

PubMed

Ciszek, Benjamin; Fleischer, Ivana

2018-04-12

Herein we report the first homogeneous palladium-based transfer hydrogenolysis of benzylic alcohols using an in situ formed palladium-phosphine complex and formic acid as reducing agent. The reaction requires a catalyst loading as low as only 1 mol% of palladium and just a slight excess of reductant to obtain the deoxygenated alkylarenes in good to excellent yields. Besides demonstrating the broad applicability for primary, secondary and tertiary benzylic alcohols, a reaction intermediate could be identified. Additionally, it could be shown that partial oxidation of the applied phosphine ligand was beneficial for the course of the reaction, presumably by stabilizing the active catalyst. Reaction profiles and catalyst poisoning experiments were used to characterize the catalyst, the results indicate a homogeneous metal complex as active species. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Picolinamide-Based Iridium Catalysts for Dehydrogenation of Formic Acid in Water: Effect of Amide N Substituent on Activity and Stability

DOE PAGES

Kanega, Ryoichi; Onishi, Naoya; Wang, Lin; ...

2018-03-01

To develop highly efficient catalysts for dehydrogenation of formic acid in water, we investigated in this paper several Cp*Ir catalysts with various amide ligands. The catalyst with an N-phenylpicolinamide ligand exhibited a TOF of 118 000 h -1 at 60 °C. A constant rate (TOF>35 000 h -1) was maintained for six hours, and a TON of 1 000 000 was achieved at 50 °C.

Electronic effects on the catalytic disproportionation of formic acid to methanol by [Cp*Ir(III)(R-bpy)Cl]Cl complexes.

PubMed

Sasayama, A F; Moore, C E; Kubiak, C P

2016-02-14

A series of [Cp*Ir(III)(R-bpy)Cl]Cl (R-bpy = 4,4'-di-R-2,2'-bipyridine; R = CF3, H, Me, tBu, OMe) complexes was prepared and studied for catalytic formic acid disproportionation. The relationship between the electron donating strength of the bipyridine substituents and methanol production of the corresponding complexes was analyzed; the unsubstituted (R = H) complex was the most selective for methanol formation.

Picolinamide-Based Iridium Catalysts for Dehydrogenation of Formic Acid in Water: Effect of Amide N Substituent on Activity and Stability

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

Kanega, Ryoichi; Onishi, Naoya; Wang, Lin

To develop highly efficient catalysts for dehydrogenation of formic acid in water, we investigated in this paper several Cp*Ir catalysts with various amide ligands. The catalyst with an N-phenylpicolinamide ligand exhibited a TOF of 118 000 h -1 at 60 °C. A constant rate (TOF>35 000 h -1) was maintained for six hours, and a TON of 1 000 000 was achieved at 50 °C.

A reassessment of the budget of formic and acetic acids in the boundary layer at Dumont d'Urville (coastal Antarctica): The role of penguin emissions on the budget of several oxygenated volatile organic compounds

NASA Astrophysics Data System (ADS)

Legrand, Michel; Gros, ValéRie; Preunkert, Susanne; Sarda-EstèVe, Roland; Thierry, Anne-Mathilde; PéPy, Guillaume; Jourdain, B.

2012-03-01

Initiated in 1997, the year-round study of formic and acetic acids was maintained until 2011 at the coastal Antarctic site of Dumont d'Urville. The records show that formic and acetic acids are rather abundant in summer with typical mixing ratios of 200 pptv and 700 pptv, respectively. With the aim to constrain their budget, investigations of their potential marine precursors like short-chain alkenes and acetaldehyde were initiated in 2011. Acetic acid levels in December 2010 were four times higher than those observed over summers back to 1997. These unusually high levels were accompanied by unusually high levels of ammonia, and by an enrichment of oxalate in aerosols. These observations suggest that the guano decomposition in the large penguin colonies present at the site was particularly strong under weather conditions encountered in spring 2010 (important snow storms followed by sunny days with mild temperatures). Although being dependent on environmental conditions, this process greatly impacts the local atmospheric budget of acetic acid, acetaldehyde, and acetone during the entire summer season. Present at levels as high as 500 pptv, acetaldehyde may represent the major precursor of acetic acid, alkene-ozone reactions remaining insignificant sources. Far less influenced by penguin emissions, the budget of formic acid remains not fully understood even if alkene-ozone reactions contribute significantly.

Postmortem computed tomography and magnetic resonance imaging facilitates forensic autopsy in a fatal case of poisoning with formic acid, diphenhydramine, and ethanol.

PubMed

Berger, Florian; Steuer, Andrea E; Rentsch, Katharina; Gascho, Dominic; Stamou, Stamatios; Schärli, Sarah; Thali, Michael J; Krämer, Thomas; Flach, Patricia M

2016-09-01

A case of fatal poisoning by ingesting formic acid, diphenhydramine, and ethanol by a 25-year-old woman who committed suicide is presented. Prior to autopsy, postmortem computed tomography and postmortem magnetic resonance tomography were performed and revealed severe damage to the stomach, the left thoracic wall, and parts of the liver. Imaging detected acid-induced fluid-fluid level within the thoracic cavity (fat-equivalent fluid and necrotic pleural effusion). This case report illustrates that postmortem cross-sectional imaging may facilitate dissection of severely damaged or complex regions, and may provide additional information compared to autopsy and toxicological examinations alone.

Acid-catalysed xylose dehydration into furfural in the presence of kraft lignin.

PubMed

Lamminpää, Kaisa; Ahola, Juha; Tanskanen, Juha

2015-02-01

In this study, the effects of kraft lignin (Indulin AT) on acid-catalysed xylose dehydration into furfural were studied in formic and sulphuric acids. The study was done using D-optimal design. Three variables in both acids were included in the design: time (20-80 min), temperature (160-180°C) and initial lignin concentration (0-20 g/l). The dependent variables were xylose conversion, furfural yield, furfural selectivity and pH change. The results showed that the xylose conversion and furfural yield decreased in sulphuric acid, while in formic acid the changes were minor. Additionally, it was showed that lignin has an acid-neutralising capacity, and the added lignin increased the pH of reactant solutions in both acids. The pH rise was considerably lower in formic acid than in sulphuric acid. However, the higher pH did not explain all the changes in conversion and yield, and thus lignin evidently inhibits the formation of furfural. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

2012-08-07

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.

Continuous-flow hydrogenation of carbon dioxide to pure formic acid using an integrated scCO2 process with immobilized catalyst and base.

PubMed

Wesselbaum, Sebastian; Hintermair, Ulrich; Leitner, Walter

2012-08-20

Dual role for CO(2): Pure formic acid can be obtained continuously by hydrogenation of CO(2) in a single processing unit. An immobilized ruthenium organometallic catalyst and a nonvolatile base in an ionic liquid (IL) are combined with supercritical CO(2) as both reactant and extractive phase. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rheological Properties and Electrospinnability of High-Amylose Starch in Formic Acid.

PubMed

Lancuški, Anica; Vasilyev, Gleb; Putaux, Jean-Luc; Zussman, Eyal

2015-08-10

Starch derivatives, such as starch-esters, are commonly used as alternatives to pure starch due to their enhanced mechanical properties. However, simple and efficient processing routes are still being sought out. In the present article, we report on a straightforward method for electrospinning high-amylose starch-formate nanofibers from 17 wt % aqueous formic acid (FA) dispersions. The diameter of the electrospun starch-formate fibers ranged from 80 to 300 nm. The electrospinnability window between starch gelatinization and phase separation was determined using optical microscopy and rheological studies. This window was shown to strongly depend on the water content in the FA dispersions. While pure FA rapidly gelatinized starch, yielding solutions suitable for electrospinning within a few hours at room temperature, the presence of water (80 and 90 vol % FA) significantly delayed gelatinization and dissolution, which deteriorated fiber quality. A complete destabilization of the electrospinning process was observed in 70 vol % FA dispersions. Optical micrographs showed that FA induced a disruption of starch granule with a loss of crystallinity confirmed by X-ray diffraction. As a result, starch fiber mats exhibited a higher elongation at break when compared to brittle starch films.

High-Yield Production of Levulinic Acid from Pretreated Cow Dung in Dilute Acid Aqueous Solution.

PubMed

Su, Jialei; Shen, Feng; Qiu, Mo; Qi, Xinhua

2017-02-14

Agricultural waste cow dung was used as feedstock for the production of a high value-added chemical levulinic acid (LA) in dilute acid aqueous solutions. A high LA yield of 338.9 g/kg was obtained from the pretreated cow dung, which was much higher than that obtained from the crude cow dung (135 g/kg), mainly attributed to the breakage of the lignin fraction in the lignocellulose structure of the cow dung by potassium hydroxide (KOH) pretreatment, and thus enhanced the accessibility of cow dung to the acid sites in the catalytic reaction. Meanwhile, another value-added chemical formic acid could be obtained with a yield of ca. 160 g/kg in the process, implying a total production of ca. 500 g/kg yield for LA and formic acid from the pretreated cow dung with the proposed process. The developed process was shown to be tolerant to high initial substrate loading with a satisfied LA yield. This work provides a promising strategy for the value-increment utilization of liglocellulosic agricultural residues.

Electrocatalytic behavior of a nanocomposite of Ni/Pd supported by carbonized PVA nanofibers towards formic acid, ethanol and urea oxidation: A physicochemical and electro-analysis study

NASA Astrophysics Data System (ADS)

Mohamed, Ibrahim M. A.; Yasin, Ahmed S.; Barakat, Nasser A. M.; Song, Seung A.; Lee, Ha Eun; Kim, Seong Su

2018-03-01

A nanocomposite of Ni/Pd supported by carbonized poly-vinyl alcohol (PVA) nanofibers (NFs) was synthesized via electrospinning followed by calcination under an argon atmosphere. The as-synthesized NFs were studied using physicochemical analyses, such as field-emission scanning electron microscopy (FESEM), Transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTsbnd IR) and X-ray photoelectron spectroscopy (XPS), to investigate the morphology, crystallinity, effect of carbonization and surface chemistry of the NFs, respectively. Cyclic voltammetry (CV) and chronoamperometry (CA) were utilized to study the performance of the NFs towards electrooxidation reactions. The designed NFs present superior electrocatalytic behavior in an acid medium towards formic acid oxidation, as well as urea and ethanol oxidation in an alkaline medium. The electrocatalytic performance of the bimetallic NFs appears to arise from the assembly of bimetallic Ni/Pd@NFs based on PVA, which has hydroxyl groups. These hydroxyl groups can decrease the negative processes that occur as a result of metal-metal interactions, such as the aggregation process. This study introduces a novel non-precious electrocatalyst to facilitate the commercialization of fuel cells based on formic acid, urea and ethanol.

Sequential lignin depolymerization by combination of biocatalytic and formic acid/formate treatment steps.

PubMed

Gasser, Christoph A; Čvančarová, Monika; Ammann, Erik M; Schäffer, Andreas; Shahgaldian, Patrick; Corvini, Philippe F-X

2017-03-01

Lignin, a complex three-dimensional amorphous polymer, is considered to be a potential natural renewable resource for the production of low-molecular-weight aromatic compounds. In the present study, a novel sequential lignin treatment method consisting of a biocatalytic oxidation step followed by a formic acid-induced lignin depolymerization step was developed and optimized using response surface methodology. The biocatalytic step employed a laccase mediator system using the redox mediator 1-hydroxybenzotriazole. Laccases were immobilized on superparamagnetic nanoparticles using a sorption-assisted surface conjugation method allowing easy separation and reuse of the biocatalysts after treatment. Under optimized conditions, as much as 45 wt% of lignin could be solubilized either in aqueous solution after the first treatment or in ethyl acetate after the second (chemical) treatment. The solubilized products were found to be mainly low-molecular-weight aromatic monomers and oligomers. The process might be used for the production of low-molecular-weight soluble aromatic products that can be purified and/or upgraded applying further downstream processes.

THE PRODUCTION OF VOLATILE FATTY ACIDS BY BACTERIA OF THE DYSENTERY GROUP

PubMed Central

Zoller, Harper F.; Clark, W. Mansfield

1921-01-01

These studies show: 1. A close agreement exists among all the organisms studied in the total quantity of volatile fatty acids produced and in the ratio of formic to acetic, under aerobic conditions, and in the presence of 1 per cent of glucose. 2. When grown upon peptone alone, with free access of air to the cultures, volatile fatty acids are produced in appreciable quantities, although the reaction of the solution has gone more alkaline as shown by colorimetric pH tests. Formic acid is not found, but in its place we obtain propionic acid. 3. Upon exhaustion of air from the non-sugar medium the bacteria again produce formic acid, and in addition some butyric. This is true for both Shiga and non-Shiga cultures. The reaction is distinctly more acid. 4. The presence of glucose in the medium from which the air has been pumped furnishes a condition which provokes about the same type and degree of fermentation that operates in the glucose medium bathed in air at atmospheric pressure. 5. The enormous quantity of formic acid produced by these bacteria may play a significant part in the digestive disturbances and toxic symptoms accompanying their infection of the human intestinal tract. PMID:19871867

Highly biocompatible yogurt-derived carbon dots as multipurpose sensors for detection of formic acid vapor and metal ions

NASA Astrophysics Data System (ADS)

Moonrinta, Sasaluck; Kwon, Binhee; In, Insik; Kladsomboon, Sumana; Sajomsang, Warayuth; Paoprasert, Peerasak

2018-07-01

Carbon dots are fascinating nanomaterials given their straightforward synthesis, unique optical properties, sensing capabilities, and biocompatibility. In this work, biocompatible carbon dots were prepared from yogurt using a two-step pyrolysis/hydrothermal method. The dots were spherical in shape with an average size of 4.7 nm. They showed blue emission under UV illumination with a quantum yield of 1.5%. Their photoluminescence was stable over three months and in both strong buffer solutions and highly concentrated salt solutions. The optical absorption and photoluminescence properties of the dots were employed for vapor and metal ion sensing, respectively. For the first time, the carbon dots were integrated into an optical electronic nose, and used for the detection of formic acid vapor at room temperature. Sensing was based on monitoring the optical transmission through a carbon dot film upon exposure to vapor, and the results were confirmed by UV-visible spectroscopy. The carbon dot-integrated electronic nose was able to distinguish vapor from formic acid/water solutions at different concentrations, with a detection limit of 7.3% v/v. The sensitivity of the dots to metal ions was tested by measuring the photoluminescence emission intensity at different excitation wavelengths. Principal component analysis was used to differentiate between the ions. The results suggested that interactions between carbon dots and metals ions occurred at a range of binding sites. The biocompability of the dots was demonstrated to be excellent. The study identified carbon dots produced from yogurt as multipurpose fluorescent nanomaterials with potential sensing and biomedical applications.

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

DOE PAGES

Choi, Sang-Il; Herron, Jeffrey A.; Scaranto, Jessica; ...

2015-04-13

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 {100} facets have higher specific activities than those enclosed by {111} facets, in agreement with prior observations for Pd single-crystal substrates. If comparing nanocrystalsmore » predominantly enclosed by a specific type of facet, {100} or {111}, 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(211) sites, compared to the activity of both Pd(100) and Pd(111) surfaces, could be attributed to an increased flux through the HCOO-mediated pathway rather than the COOH-mediated pathway on Pd(211). 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.« less

Surface reaction modification: The effect of structured overlayers of sulfur on the kinetics and mechanism of the decomposition of formic acid on Pt(111)

NASA Astrophysics Data System (ADS)

Abbas, N.; Madix, R. J.

The reaction of formic acid (DCOOH) on Pt(111), Pt(111)-(2×2)S and Pt(111)-(√3×√3)R30°S surfaces was examined by temperature programmed reaction spectroscopy. On the clean surface formic acid decomposed to yield primarily carbon dioxide and the hydrogenic species (H 2, HD and D 2) at low coverages. Although the formation of water and carbon monoxide via a dehydration reaction was observed at these coverages, the yield of these products was small when compared to the other products of reaction. The evolution of CO 2 at low temperature was ascribed to the decomposition of the formate intermediate. In the presence of sulfur the amount of molecularly adsorbed formic acid decreased up to a factor of three on the (√3×√3)R30°S surface, and a decline in the reactivity of over an order of magnitude was also observed. The only products formed were the hydrogenic species and carbon dioxide. The absence of carbon monoxide indicated that the dehydration pathway was blocked by sulfur. In addition to the low temperature CO 2 peak a high temperature CO 2-producing path was also evident. It was inferred from both the stoichiometry and the coincident evolution of D 2 and CO 2 in the high temperature states that these products also evolved due to the decomposition of the formate intermediate. On increasing the sulfur coverage to one-third monolayer this intermediate was further stabilized, and a predominance of the decomposition via the high temperature path was observed. Stability of the formate intermediate was attributed to inhibition of the decomposition reaction by sulfur atoms. The activation energy for formate decomposition increased from 15 kcal/gmole on the clean surface to 24.3 kcal/gmol on the (√3×√3)R30°S overlayer.

Kinetics of Maleic Acid and Aluminum Chloride Catalyzed Dehydration and Degradation of Glucose

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

Zhang, Ximing; Hewetson, Barron B.; Mosier, Nathan S.

We report the positive effect of maleic acid, a dicarboxylic acid, on the selectivity of hexose dehydration to 5-hydroxymethyfurfural (HMF) and subsequent hydrolysis to levulinic and formic acids. We also describe the kinetic analysis of a Lewis acid (AlCl3) alone and in combination with HCl or maleic acid to catalyze the isomerization of glucose to fructose, dehydration of fructose to HMF, hydration of HMF to levulinic and formic acids, and degradation of these compounds to humins. The results show that AlCl3 significantly enhances the rate of glucose conversion to HMF and levulinic acid in the presence of both maleic acidmore » and HCl. In addition, the degradation of HMF to humins, rather than levulinic and formic acids, is reduced by 50% in the presence of maleic acid and AlCl3 compared to HCl combined with AlCl3. The results suggest different reaction mechanisms for the dehydration of glucose and rehydration of HMF between maleic acid and HCl.« less

Formic acid acting as an efficient oxygen scavenger in four-electron reduction of oxygen catalyzed by a heterodinuclear iridium-ruthenium complex in water.

PubMed

Fukuzumi, Shunichi; Kobayashi, Takeshi; Suenobu, Tomoyoshi

2010-09-01

A heterodinuclear iridium-ruthenium complex [Ir(III)(Cp*)(H(2)O)(bpm)Ru(II)(bpy)(2)](SO(4))(2) (Cp* = eta(5)-pentamethyl-cyclopentadienyl, bpm = 2,2'-bipyrimidine, bpy = 2,2'-bipyridine) acts as an effective catalyst for removal of dissolved O(2) by the four-electron reduction of O(2) with formic acid in water at an ambient temperature.

Effect of strategic administration of an encapsulated blend of formic acid, citric acid, and essential oils on Salmonella carriage, seroprevalence, and growth of finishing pigs.

PubMed

Walia, Kavita; Argüello, Hector; Lynch, Helen; Leonard, Finola C; Grant, Jim; Yearsley, Dermot; Kelly, Sinead; Duffy, Geraldine; Gardiner, Gillian E; Lawlor, Peadar G

2017-02-01

Controlling Salmonella at farm level can act as the first line of defence in reducing salmonellosis from pork. This study investigated the efficacy of an encapsulated blend of formic acid, citric acid, and essential oils (FormaXOL™) administered to finisher pigs for 28days prior to slaughter in controlling Salmonella shedding on a commercial farm with a history of high Salmonella seroprevalence. Fourteen pens of 8-10 pigs/pen were randomly assigned to a control (finisher diet without additive) or a treatment group (the same diet with 4kg/t of FormaXOL™) for 28 days. Faeces were collected from each pig on days 0, 14, and 28, while on day 29 blood, caecal digesta and ileocaecal-mesenteric lymph nodes were collected at slaughter. Pigs were weighed at the start and end of the trial, feed intake was recorded, and carcass quality parameters were recorded at slaughter. On day 14, Salmonella shedding was reduced in the treatment compared to the control group (27.9% versus 51.7% probability of detecting Salmonella in faeces, respectively; p=0.001). However, on day 28, no reduction was observed (20.6% versus 35.9% probability of detecting Salmonella in faeces, respectively; p=0.07). Interestingly, Salmonella shedding rates in the treated pigs remained stable throughout the trial compared to the control group. This suggests that the feed additive prevented additional pigs from acquiring the Salmonella infection. A lower Salmonella seroprevalence was detected at slaughter in the treatment compared to the control group using the 40% optical density cut-off (64.5% versus 88.5%, respectively; p=0.01). However, no significant differences in Salmonella recovery rates were observed in the caecal digesta or lymph nodes between treated and control groups. Treated pigs had a lower feed intake than pigs fed the control diet (p=0.001); however, average daily gain and feed conversion efficiency were not affected by treatment (p=0.45 and 0.55, respectively). Consequently, supplementing

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.

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.

Trichloroethylene-induced formic aciduria in the male C57 Bl/6 mouse.

PubMed

Lock, Edward A; Keane, Paul; Rowe, Philip H; Foster, John R; Antoine, Daniel; Morris, Christopher M

2017-03-01

1, 1, 2-Trichloroethylene (TCE) is of environmental concern, due to evaporation while handling, chemical processing and leakage from chemical waste sites, leading to its contamination of ground water and air. For several decades there has been issues about possible long term health effects of TCE but recently the International Agency for Research on Cancer (IARC) and the US Environmental Protection Agency classified TCE as a human carcinogen. Links having been established between occupational exposures and kidney cancer and possible links to non-Hodgkin lymphoma and liver cancer, but there is more still more to learn. In male rats, TCE produces a small increase in the incidence of renal tubule tumours but not in female rats or mice of either sex. However, chronic renal injury was seen in these bioassays in both sexes of rats and mice. The mechanism of kidney injury from TCE is thought to be due to reductive metabolism forming a cysteine conjugate that is converted to a reactive metabolite via the enzyme cysteine conjugate β-lyase. However, TCE also produces a marked and sustained formic aciduria in male rats and it has been suggested that long term exposure to formic acid could lead to renal tubule injury and regeneration. In this study we have determined if TCE produces formic aciduria in male mice following a single and repeat dosing. Male C 57 Bl/6OlaHsd mice were dosed with 1000mg/kg by ip injection and urine collected overnight 24, 48, 72 and 96h after dosing. Formic acid was present in urine 24h after dosing, peaked around 48h at 8mg formic acid excreted/mouse, and remained constant over the next 24h and was not back to normal 96h after dosing. This was associated with a marked acidification of the urine. Plasma creatinine and renal pathology was normal. Plasma kinetics of formic acid showed it was readily cleared with an initial half-life of 2.42h followed by a slower rate with a half-life of 239h. Male mice were then dosed twice/week at 1000mg/kg TCE for

Excessive S-Adenosyl-L-Methionine-Dependent Methylation Increases Levels of Methanol, Formaldehyde and Formic Acid in Rat Brain Striatal Homogenates: Possible role in S-adenosyl-L-methionine-induced Parkinson’s disease-like disorders

PubMed Central

Lee, Eun-Sook; Chen, Hongtao; Hardman, Chadwick; Simm, Anthony; Charlton, Clivel

2009-01-01

Aims Excessive methylation may be a precipitating factor for Parkinson’s disease (PD) since S-adenosylmethionine (SAM), the endogenous methyl donor, induces PD-like changes when injected into the rat brain. The hydrolysis of the methyl ester bond of the methylated proteins produces methanol. Since methanol is oxidized into formaldehyde, and formaldehyde into formic acid in the body, we investigated the effects of SAM on the production of methanol, formaldehyde and formic acid in rat brain striatal homogenates and the toxicity of these products in PC12 cells. Main methods radio-enzymatic and colorimetric assays, cell viability, Western blot. Key findings SAM increased the formation of methanol, formaldehyde and formic acid in a concentration and time-dependent manner. Concentrations of [3H-methyl]-SAM at 0.17, 0.33, 0.67 and 1.34 nM produced 3.8, 8.0, 18.3 and 34.4 fmol/mg protein/h of [3H] methanol in rat striatal homogenates, respectively. SAM also significantly generated formaldehyde and formic acid in striatal homogenates. Formaldehyde was the most toxic metabolite to differentiated PC12 pheochromocytoma cells in cell culture studies, indicating that formaldehyde formed endogenously may contribute to neuronal damage in excessive methylation conditions. Subtoxic concentration of formaldehyde decreased the expression of tyrosine hydroxylase, the limiting factor in dopamine synthesis. Formaldehyde was more toxic to catecholaminergic PC12 cells than C6 glioma cells, indicating that neurons are more vulnerable to formaldehyde than glia cells. Significance We suggest that excessive carboxylmethylation of proteins might be involved in the SAM-induced PD-like changes and in the aging process via the toxic effects of formaldehyde. PMID:18930743

Picolinamide-Based Iridium Catalysts for Dehydrogenation of Formic Acid in Water: Effect of Amide N Substituent on Activity and Stability.

PubMed

Kanega, Ryoichi; Onishi, Naoya; Wang, Lin; Murata, Kazuhisa; Muckerman, James T; Fujita, Etsuko; Himeda, Yuichiro

2018-03-01

To develop highly efficient catalysts for dehydrogenation of formic acid in water, we investigated several Cp*Ir catalysts with various amide ligands. The catalyst with an N-phenylpicolinamide ligand exhibited a TOF of 118 000 h -1 at 60 °C. A constant rate (TOF>35 000 h -1 ) was maintained for six hours, and a TON of 1 000 000 was achieved at 50 °C. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly active carbon supported Pd cathode catalysts for direct formic acid fuel cells

NASA Astrophysics Data System (ADS)

Mikolajczuk-Zychora, A.; Borodzinski, A.; Kedzierzawski, P.; Mierzwa, B.; Mazurkiewicz-Pawlicka, M.; Stobinski, L.; Ciecierska, E.; Zimoch, A.; Opałło, M.

2016-12-01

One of the drawbacks of low-temperature fuel cells is high price of platinum-based catalysts used for the electroreduction of oxygen at the cathode of the fuel cell. The aim of this work is to develop the palladium catalyst that will replace commonly used platinum cathode catalysts. A series of palladium catalysts for oxygen reduction reaction (ORR) were prepared and tested on the cathode of Direct Formic Acid Fuel Cell (DFAFC). Palladium nanoparticles were deposited on the carbon black (Vulcan) and on multiwall carbon nanotubes (MWCNTs) surface by reduction of palladium(II) acetate dissolved in ethanol. Hydrazine was used as a reducing agent. The effect of functionalization of the carbon supports on the catalysts physicochemical properties and the ORR catalytic activity on the cathode of DFAFC was studied. The supports were functionalized by treatment in nitric acid for 4 h at 80 °C. The structure of the prepared catalysts has been characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscope (TEM) and cyclic voltammetry (CV). Hydrophilicity of the catalytic layers was determined by measuring contact angles of water droplets. The performance of the prepared catalysts has been compared with that of the commercial 20 wt.% Pt/C (Premetek) catalyst. The maximum power density obtained for the best palladium catalyst, deposited on the surface of functionalized carbon black, is the same as that for the commercial Pt/C (Premetek). Palladium is cheaper than platinum, therefore the developed cathode catalyst is promising for future applications.

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. Copyright © 2014. Published by Elsevier Ltd.

Simple interface of high-performance liquid chromatography-atomic fluorescence spectrometry hyphenated system for speciation of mercury based on photo-induced chemical vapour generation with formic acid in mobile phase as reaction reagent.

PubMed

Yin, Yongguang; Liu, Jingfu; He, Bin; Shi, Jianbo; Jiang, Guibin

2008-02-15

Photo-induced chemical vapour generation (CVG) with formic acid in mobile phase as reaction reagent was developed as interface to on-line couple HPLC with atomic fluorescence spectrometry for the separation and determination of inorganic mercury, methylmercury (MeHg), ethylmercury (EtHg) and phenylmercury (PhHg). In the developed procedure, formic acid in mobile phase was used to decompose organomercuries and reduce Hg(2+) to mercury cold vapour under UV irradiation. Therefore, no post-column reagent was used and the flow injection system in traditional procedure is omitted. A number of operating parameters including pH of mobile phase, concentration of formate, flow rate of mobile phase, length of PTFE reaction coil, flow rate of carrier gas and Na(2)S(2)O(3) in sample matrix were optimized. The limits of detection at the optimized conditions were 0.085, 0.033, 0.029 and 0.038 microg L(-1) for inorganic mercury, MeHg, EtHg and PhHg, respectively. The developed method was validated by determination of certified reference material DORM-2 and was further applied in analyses of seafood samples from Yantai port, China. The UV-CVG with formic acid simplifies the instrumentation and reduces the analytical cost significantly.

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

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

Choi, Sang; Herron, Jeffrey A.; Scaranto, Jessica

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-crystalmore » 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.« less

The High-Resolution Infrared Spectrum of the ν 5Band of Deuterated Formic Acid (DCOOH)

NASA Astrophysics Data System (ADS)

Goh, K. L.; Ong, P. P.; Tan, T. L.; Wang, W. F.; Teo, H. H.

1998-07-01

The Fourier transform infrared spectrum of the ν5band of deuterated formic acid (DCOOH) has been measured with a resolution of 0.004 cm-1in the frequency range of 1090-1180 cm-1. Using a Watson'sA-reduced Hamiltonian in theIrrepresentation, a total of 1731 assigned unperturbed transitions have been analyzed to provide rovibrational constants for the upper state (v5= 1) with a standard deviation of 0.000363 cm-1. The band isAtype with an unperturbed band center at 1142.31075 ± 0.00002 cm-1. The band is expected to be perturbed by a nearby ν4band through a Fermi resonance term and possibly a Coriolis term. The resonance is particularly noticeable forKa= 10, and 11, at highJvalues. About 215 perturbed lines were identified but they were not included in the final fit.

Interaction of formic acid with nitrogen: stabilization of the higher-energy conformer.

PubMed

Marushkevich, Kseniya; Räsänen, Markku; Khriachtchev, Leonid

2010-10-07

Conformational change is an important concept in chemistry and physics. In the present work, we study conformations of formic acid (HCOOH, FA) and report the preparation and identification of the complex of the higher-energy conformer cis-FA with N(2) in an argon matrix. The cis-FA···N(2) complex was synthesized by combining annealing and vibrational excitation of the ground-state trans-FA in a FA/N(2)/Ar matrix. The assignment is based on IR spectroscopic measurements and ab initio calculations. The cis-FA···N(2) complex decay in an argon matrix is much slower compared with the cis-FA monomer. In agreement with the experimental observations, the calculations predict a substantial increase in the stabilization barrier for the cis-FA···N(2) complex compared with the uncomplexed cis-FA monomer. A number of solvation effects in an argon matrix are computationally estimated and discussed. The present results on the cis-FA···N(2) complex show that intermolecular interaction can stabilize intrinsically unstable conformers, as previously found for some other cis-FA complexes.

Identification of oxalic acid and tartaric acid as major persistent pain-inducing toxins in the stinging hairs of the nettle, Urtica thunbergiana.

PubMed

Fu, Han Yi; Chen, Shiang Jiuun; Chen, Ruei Feng; Ding, Wang Hsien; Kuo-Huang, Ling Long; Huang, Rong Nan

2006-07-01

Once human skin contacts stinging hairs of Urtica spp. (stinging nettles), the irritant is released and produces pain, wheals or a stinging sensation which may last for >12 h. However, the existence of pain-inducing toxins in the stinging hairs of Urtica thunbergiana has never been systematically demonstrated. Experiments were therefore conducted to identify the persistent pain-inducing agents in the stinging hairs of U. thunbergiana. The stinging hairs of U. thunbergiana were removed and immersed in deionized water. After centrifugation, the clear supernatants were then subjected to high-performance liquid chromatography (HPLC), enzymatic analysis and/or behavioural bioassays. The HPLC results showed that the major constituents in the stinging hairs of U. thunbergiana were histamine, oxalic acid and tartaric acid. However, the well-recognized pain-inducing agents, serotonin and formic acid, existed at a low concentration as estimated by HPLC and/or enzymatic analyses. The behavioural tests showed that 2% oxalic acid and 10% tartaric acid dramatically elicited persistent pain sensations in rats. In contrast, 10% formic acid and 2% serotonin only elicited moderate pain sensation in the first 10 min. Moreover, no significant pain-related behavioural response was observed after injecting 10% acetylcholine and histamine in rats. Oxalic acid and tartaric acid were identified, for the first time, as major long-lasting pain-inducing toxins in the stinging hairs of U. thunbergiana. The general view that formic acid, histamine and serotonin are the pain-inducing agents in the stinging hairs of U. dioica may require updating, since their concentrations in U. thunbergiana were too low to induce significant pain sensation in behavioural bioassays.

Organic acids in cloud water and rainwater at a mountain site in acid rain areas of South China.

PubMed

Sun, Xiao; Wang, Yan; Li, Haiyan; Yang, Xueqiao; Sun, Lei; Wang, Xinfeng; Wang, Tao; Wang, Wenxing

2016-05-01

To investigate the chemical characteristics of organic acids and to identify their source, cloud water and rainwater samples were collected at Mount Lu, a mountain site located in the acid rain-affected area of south China, from August to September of 2011 and March to May of 2012. The volume-weighted mean (VWM) concentration of organic acids in cloud water was 38.42 μeq/L, ranging from 7.45 to 111.46 μeq/L, contributing to 2.50 % of acidity. In rainwater samples, organic acid concentrations varied from 12.39 to 68.97 μeq/L (VWM of 33.39 μeq/L). Organic acids contributed significant acidity to rainwater, with a value of 17.66 %. Formic acid, acetic acid, and oxalic acid were the most common organic acids in both cloud water and rainwater. Organic acids had an obviously higher concentration in summer than in spring in cloud water, whereas there was much less discrimination in rainwater between the two seasons. The contribution of organic acids to acidity was lower during summer than during spring in both cloud water (2.20 % in summer vs 2.83 % in spring) and rainwater (12.24 % in summer vs 19.89 % in spring). The formic-to-acetic acid ratio (F/A) showed that organic acids were dominated by primary emissions in 71.31 % of the cloud water samples and whole rainwater samples. Positive matrix factorization (PMF) analysis determined four factors as the sources of organic acids in cloud water, including biogenic emissions (61.8 %), anthropogenic emissions (15.28 %), marine emissions (15.07 %) and soil emissions (7.85 %). The findings from this study imply an indispensable role of organic acids in wet deposition, but organic acids may have a limited capacity to increase ecological risks in local environments.

Pd Nanoparticles Coupled to WO 2.72 Nanorods for Enhanced Electrochemical Oxidation of Formic Acid

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

Xi, Zheng; Erdosy, Daniel P.; Mendoza-Garcia, Adriana

We synthesize a new type of hybrid Pd/WO2.72 structure with 5 nm Pd nanoparticles (NPs) anchored on 50 × 5 nm WO2.72 nanorods. The strong Pd/WO2.72 coupling results in the lattice expansion of Pd from 0.23 to 0.27 nm and the decrease of Pd surface electron density. As a result, the Pd/WO2.72 shows much enhanced catalysis toward electrochemical oxidation of formic acid in 0.1 M HClO4; it has a mass activity of ~1600 mA/mgPd in a broad potential range of 0.4–0.85 V (vs RHE) and shows no obvious activity loss after a 12 h chronoamperometry test at 0.4 V. Ourmore » work demonstrates an important strategy to enhance Pd NP catalyst efficiency for energy conversion reactions.« less

Deprotonation of formic acid in collisions with a liquid water surface studied by molecular dynamics and metadynamics simulations.

PubMed

Murdachaew, Garold; Nathanson, Gilbert M; Benny Gerber, R; Halonen, Lauri

2016-11-21

Deprotonation of organic acids at aqueous surfaces has important implications in atmospheric chemistry and other disciplines, yet it is not well-characterized or understood. This article explores the interactions of formic acid (FA), including ionization, in collisions at the air-water interface. Ab initio molecular dynamics simulations with dispersion-corrected density functional theory were used. The 8-50 picosecond duration trajectories all resulted in the adsorption of FA within the interfacial region, with no scattering, absorption into the bulk or desorption into the vapor. Despite the known weak acidity of FA, spontaneous deprotonation of the acid was observed at the interface on a broad picosecond timescale, ranging from a few picoseconds typical for stronger acids to tens of picoseconds. Deprotonation occurred in 4% of the trajectories, and was followed by Grotthuss proton transfer through adjacent water molecules. Both sequential and ultrafast concerted proton transfer were observed. The formation of contact ion pairs and solvent-separated ion pairs, and finally the reformation of neutral FA, both trans and cis conformers, occurred in different stages of the dynamics. To better understand the deprotonation mechanisms at the interface compared with the process in bulk water, we used well-tempered metadynamics to obtain deprotonation free energy profiles. While in bulk water FA deprotonation has a free energy barrier of 14.8 kJ mol -1 , in fair agreement with the earlier work, the barrier at the interface is only 7.5 kJ mol -1 . Thus, at the air-water interface, FA may dissociate more rapidly than in the bulk. This finding can be rationalized with reference to the dissimilar aqueous solvation and hydrogen-bonding environments in the interface compared to those in bulk liquid water.

Nonequimolar Mixture of Organic Acids and Bases: An Exception to the Rule of Thumb for Salt or Cocrystal.

PubMed

Pratik, Saied Md; Datta, Ayan

2016-08-04

Formation of salt and/or cocrystal from organic acid-base mixtures has significant consequences in the pharmaceutical industry and its related intellectual property rights (IPR). On the basis of calculations using periodic dispersion corrected DFT (DFT-D2) on formic acid-pyridine adduct, we have demonstrated that an equimolar stoichiometric ratio (1:1) exists as a neutral cocrystal. On the other hand, the nonequimolar stoichiometry (4:1) readily forms an ionic salt. While the former result is in agreement with the ΔpKa rule between the base and the acid, the latter is not. Calculations reveal that, within the equimolar manifold (n:n; n = 1-4), the mixture exists as a hydrogen bonded complex in a cocrystal-like environment. However, the nonequimolar mixture in a ratio of 5:1 and above readily forms salt-like structures. Because of the cooperative nature of hydrogen bonding, the strength of the O-H···N hydrogen bond increases and eventually transforms into O(-)···H-N(+) (complete proton transfer) as the ratio of formic acid increases and forms salt as experimentally observed. Clearly, an enhanced polarization of formic acid on aggregation increases its acidity and, hence, facilitates its transfer to pyridine. Motion of the proton from formic acid to pyridine is shown to follow a relay mechanism wherein the proton that is far away from pyridine is ionized and is subsequently transferred to pyridine via hopping across the neutral formic acid molecules (Grotthuss type pathway). The dynamic nature of protons in the condensed phase is also evident for cocrystals as the barrier of intramolecular proton migration in formic acid (leading to tautomerism), ΔH(⧧)tautomer = 17.1 kcal/mol in the presence of pyridine is half of that in free formic acid (cf. ΔH(⧧)tautomer = 34.2 kcal/mol). We show that an acid-base reaction can be altered in the solid state to selectively form a cocrystal or salt depending on the strength and nature of aggregation.

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; ...

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

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).

On the origin of red and blue shifts of X-H and C-H stretching vibrations in formic acid (formate ion) and proton donor complexes.

PubMed

Tâme Parreira, Renato Luis; Galembeck, Sérgio Emanuel; Hobza, Pavel

2007-01-08

Complexes between formic acid or formate anion and various proton donors (HF, H(2)O, NH(3), and CH(4)) are studied by the MP2 and B3LYP methods with the 6-311++G(3df,3pd) basis set. Formation of a complex is characterized by electron-density transfer from electron donor to ligands. This transfer is much larger with the formate anion, for which it exceeds 0.1 e. Electron-density transfer from electron lone pairs of the electron donor is directed into sigma* antibonding orbitals of X--H bonds of the electron acceptor and leads to elongation of the bond and a red shift of the X--H stretching frequency (standard H-bonding). However, pronounced electron-density transfer from electron lone pairs of the electron donor also leads to reorganization of the electron density in the electron donor, which results in changes in geometry and vibrational frequency. These changes are largest for the C--H bonds of formic acid and formate anion, which do not participate in H-bonding. The resulting blue shift of this stretching frequency is substantial and amounts to almost 35 and 170 cm(-1), respectively.

A study on lithium/air secondary batteries-Stability of NASICON-type glass ceramics in acid solutions

NASA Astrophysics Data System (ADS)

Shimonishi, Y.; Zhang, T.; Johnson, P.; Imanishi, N.; Hirano, A.; Takeda, Y.; Yamamoto, O.; Sammes, N.

The stability of a NASICON-type lithium ion conducting solid electrolyte, Li 1+ x+ yTi 2- xAl xP 3- ySi yO 12 (LTAP), in acetic acid and formic acid solutions was examined. XRD patterns of the LTAP powders immersed in 100% acetic acid and formic acid at 50 °C for 4 months showed no change as compared to the pristine LTAP. However, the electrical conductivity of LTAP drastically decreased. On the other hand, no significant electrical conductivity change of LTAP immersed in lithium formate saturated formic acid-water solution was observed, and the electrical conductivity of LTAP immersed in lithium acetate saturated acetic acid-water increased. Cyclic voltammogram tests suggested that acetic acid was stable up to a high potential, but formic acid decomposed under the decomposition potential of water. The acetic acid solution was considered to be a candidate for the active material in the air electrode of lithium-air rechargeable batteries. The cell reaction was considered as 2Li + 2 CH 3COOH + 1/2O 2 = 2CH 3COOLi + H 2O. The energy density of this lithium-air system is calculated to be 1477 Wh kg -1 from the weights of Li and CH 3COOH, and an observed open-circuit voltage of 3.69 V.

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

DOE PAGES

Zhu, Jing; Zheng, Xin; Wang, Jie; ...

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 Pt 3Zn and PtZn have been successfully synthesized via an impregnation reduction method, followed by post heat-treatment. The Pt 3Zn 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 relativemore » 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.« less

Reversible Hydrogenation of Carbon Dioxide to Formic Acid and Methanol: Lewis Acid Enhancement of Base Metal Catalysts.

PubMed

Bernskoetter, Wesley H; Hazari, Nilay

2017-04-18

New and sustainable energy vectors are required as a consequence of the environmental issues associated with the continued use of fossil fuels. H 2 is a potential clean energy source, but as a result of problems associated with its storage and transport as a gas, chemical H 2 storage (CHS), which involves the dehydrogenation of small molecules, is an attractive alternative. In principle, formic acid (FA, 4.4 wt % H 2 ) and methanol (MeOH, 12.6 wt % H 2 ) can be obtained renewably and are excellent prospective liquid CHS materials. In addition, MeOH has considerable potential both as a direct replacement for gasoline and as a fuel cell input. The current commercial syntheses of FA and MeOH, however, use nonrenewable feedstocks and will not facilitate the use of these molecules for CHS. An appealing option for the sustainable synthesis of both FA and MeOH, which could be implemented on a large scale, is the direct metal catalyzed hydrogenation of CO 2 . Furthermore, given that CO 2 is a readily available, nontoxic and inexpensive source of carbon, it is expected that there will be economic and environmental benefits from using CO 2 as a feedstock. One strategy to facilitate both the dehydrogenation of FA and MeOH and the hydrogenation of CO 2 and H 2 to FA and MeOH is to utilize a homogeneous transition metal catalyst. In particular, the development of catalysts based on first row transition metals, which are cheaper, and more abundant than their precious metal counterparts, is desirable. In this Account, we describe recent advances in the development of iron and cobalt systems for the hydrogenation of CO 2 to FA and MeOH and the dehydrogenation of FA and MeOH and provide a brief comparison between precious metal and base metal systems. We highlight the different ligands that have been used to stabilize first row transition metal catalysts and discuss the use of additives to promote catalytic activity. In particular, the Account focuses on the crucial role that

Catalytic production of levulinic acid and ethyl levulinate from uniconazole-induced duckweed (Lemna minor).

PubMed

Liu, Chunguang; Feng, Qingna; Yang, Jirui; Qi, Xinhua

2018-05-01

Duckweed (Lemna minor) with a high starch content of 50.4% was cultivated by uniconazole-induction method. The cultivated duckweed was used to produce value-added chemicals such as glucose, levulinic acid and formic acid in diluted HCl aqueous solution. A high glucose yield of 93.4% (471 g/kg based on loading duckweed mass) could be achieved at 180 °C in short reaction time, and the generated glucose was converted into levulinic acid and formic acid with yields of 52.0% and 34.1%, respectively, for 150 min, corresponding to 262 g/kg levulinic acid yield and 171 g/kg formic acid yield based on the mass of loading duckweed, respectively. Moreover, the duckweed was efficiently converted to ethyl levulinate with 55.2% yield (400.6 g/kg) at 200 °C in ethanol. This work provides a promising strategy for the production of value-added chemicals from phytoplankton that is able to purify the wastewater containing high content of P and N. Copyright © 2018 Elsevier Ltd. All rights reserved.

Electron collisions with the HCOOH···(H2O)n complexes (n = 1, 2) in liquid phase: the influence of microsolvation on the π* resonance of formic acid.

PubMed

Freitas, T C; Coutinho, K; Varella, M T do N; Lima, M A P; Canuto, S; Bettega, M H F

2013-05-07

We report momentum transfer cross sections for elastic collisions of low-energy electrons with the HCOOH···(H2O)n complexes, with n = 1, 2, in liquid phase. The scattering cross sections were computed using the Schwinger multichannel method with pseudopotentials in the static-exchange and static-exchange plus polarization approximations, for energies ranging from 0.5 eV to 6 eV. We considered ten different structures of HCOOH···H2O and six structures of HCOOH···(H2O)2 which were generated using classical Monte Carlo simulations of formic acid in aqueous solution at normal conditions of temperature and pressure. The aim of this work is to investigate the influence of microsolvation on the π* shape resonance of formic acid. Previous theoretical and experimental studies reported a π* shape resonance for HCOOH at around 1.9 eV. This resonance can be either more stable or less stable in comparison to the isolated molecule depending on the complex structure and the water role played in the hydrogen bond interaction. This behavior is explained in terms of (i) the polarization of the formic acid molecule due to the water molecules and (ii) the net charge of the solute. The proton donor or acceptor character of the water molecules in the hydrogen bond is important for understanding the stabilization versus destabilization of the π* resonances in the complexes. Our results indicate that the surrounding water molecules may affect the lifetime of the π* resonance and hence the processes driven by this anion state, such as the dissociative electron attachment.

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.

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

Simultaneous assay of multiple antibiotics in human plasma by LC-MS/MS: importance of optimizing formic acid concentration.

PubMed

Chen, Feng; Hu, Zhe-Yi; Laizure, S Casey; Hudson, Joanna Q

2017-03-01

Optimal dosing of antibiotics in critically ill patients is complicated by the development of resistant organisms requiring treatment with multiple antibiotics and alterations in systemic exposure due to diseases and extracorporeal drug removal. Developing guidelines for optimal antibiotic dosing is an important therapeutic goal requiring robust analytical methods to simultaneously measure multiple antibiotics. An LC-MS/MS assay using protein precipitation for cleanup followed by a 6-min gradient separation was developed to simultaneously determine five antibiotics in human plasma. The precision and accuracy were within the 15% acceptance range. The formic acid concentration was an important determinant of signal intensity, peak shape and matrix effects. The method was designed to be simple and successfully applied to a clinical pharmacokinetic study.

Evaluation of the addition of organic acids in the feed and/or water for broilers and the subsequent recovery of Salmonella Typhimurium from litter and ceca.

PubMed

Bourassa, D V; Wilson, K M; Ritz, C R; Kiepper, B K; Buhr, R J

2018-01-01

Three separate broiler Salmonella Typhimurium challenge experiments were conducted evaluating efficacy of formic and propionic acid feed supplements to suppress environmental and cecal Salmonella Typhimurium prevalence. In experiment 1, broilers were provided feed with 1 kg/ton formic acid or 5 kg/ton propionic acid feed additives or a basal control diet. At the day of placement, half of the pens were inoculated with seeder chicks orally challenged with a marker strain of Salmonella Typhimurium and to yield challenged and adjacent nonchallenged pens. No differences in weekly litter samples or cecal Salmonella prevalence at 3 or 6 wk among feeding treatments were detected. In experiment 2, treatments were: 2 kg/ton propionic acid in feed, 1.0 mL/L formic acid in water, both propionic acid in feed and formic acid in water, and a basal control. Every pen was challenged with seeder chicks inoculated with Salmonella Typhimurium. By 6 wk all pens maintained detectable litter Salmonella, and broilers provided both propionic acid in feed and formic acid in water had the lowest cecal recovery (35%), compared to the control (60%). In experiment 3, treatments were: formic acid at 4 or 6 kg/ton from wk 0 to 6 or for only the last wk, propionic acid at 5 or 10 kg/ton for only the last wk, and a basal control. Each pen was challenged with Salmonella Typhimurium inoculated seeder chicks. By 6 wk, broilers fed formic acid (4 kg/ton) for the entire growout had no Salmonella-positive ceca (0/30). All treatments that provided acid supplemented feed for only the last wk had 3-13% Salmonella-positive ceca. These experiments indicate that adding formic acid to broiler feed appears to prevent Salmonella colonization from challenge pens entering into the adjacent nonchallenge pens. Feeding formic acid (4 kg/ton) for 6 wk resulted in no recovery of Salmonella from ceca compared to the control prevalence of 17%. Published by Oxford University Press on behalf of Poultry Science

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

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.

Tandem Nitrogen Functionalization of Porous Carbon: Toward Immobilizing Highly Active Palladium Nanoclusters for Dehydrogenation of Formic Acid

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

Li, Zhangpeng; Yang, Xinchun; Tsumori, Nobuko

2017-03-10

Highly dispersed palladium nanoclusters (Pd NCs) immobilized by a nitrogen (N)-functionalized porous carbon support (N-MSC-30) are synthesized by a wet chemical reduction method, wherein the N-MSC-30 prepared by a tandem low temperature heat-treatment approach proved to be a distinct support for stabilizing the Pd NCs. The prepared Pd/N-MSC-30 shows extremely high catalytic activity and recyclability for the dehydrogenation of formic acid (FA), affording the highest turnover frequency (TOF = 8414 h -1) at 333 K, which is much higher than that of the Pd catalyst supported on the N-MSC-30 prepared via a one-step process. This tandem heat treatment strategy providesmore » a facile and effective synthetic methodology to immobilize ultrafine metal NPs on N-functionalized carbon materials, which have tremendous application prospects in various catalytic fields.« less

Growth and survival kinetics of Yersinia enterocolitica IP 383 0:9 as affected by equimolar concentrations of undissociated short-chain organic acids.

PubMed

el-Ziney, M G; De Meyer, H; Debevere, J M

1997-03-03

The influence of different organic acids (lactic, acetic, formic and propionic acids) at equimolar concentrations of undissociated acid with pH range of 3.9, 5.8, on the aerobic and anaerobic growth and survival kinetics of the virulent strain of Y. enterocolitica IP 383 0:9, was determined in tryptone soy broth at 4 degrees C. Growth and survival data were analyzed and fitted by a modification of the Whiting and Cygnarowicz-Provost model, using the Minpack software library. Initial generation times, initial specific growth rates, lag time and dead rate were subsequently calculated from the model parameters. The results demonstrate that the inhibitory effects of the acids were divided into two categories dependent upon pH. At high pH (5.8) the order of inhibition was formic acid > acetic acid > propionic acid > lactic acid, whereas at lower pH it became formic acid > lactic acid > acetic acid > propionic acid. The inhibitory effect of lactic acid is enhanced under anaerobic condition. Nevertheless, when the organism was cultured anaerobically, it was shown to be more tolerant to formic and acetic acids. Moreover, these variables (type of organic acid, pH and atmosphere) did not lead to the loss of the virulence plasmid in growing and surviving cells. The mechanism of inhibitory effect for each of the acids are also discussed.

Evaluation of the addition of organic acids in the feed and/or water for broilers and the subsequent recovery of salmonella typhimurium from litter and ceca

USDA-ARS?s Scientific Manuscript database

Broiler Salmonella challenge experiments were conducted evaluating efficacy of formic and propionic acid feed supplements to suppress environmental and cecal Salmonella prevalence. In experiment 1, treatments were: formic acid, propionic acid, or basal control with no added acids. Seeder chicks we...

Formation of formic acid and organic peroxides in the ozonolysis of ethene with added water vapour

NASA Astrophysics Data System (ADS)

Horie, Osamu; Neeb, Peter; Limbach, Stefan; Moortgat, Geert K.

1994-07-01

Ozonolysis of C2H4 was carried out in a 580 l glass reaction vessel at 1-5 ppm reactant concentrations, with added water vapour. Under dry conditions ([H2O]0 = 0.5 ppm), HCHO, CO, CO2, (CHO)2O (formic acid anhydride), H2O2, and CH3OOH were identified as the reaction products. Under wet conditions ([H2O]0 = 2 × 104 ppm), HCOOH yields approaching ca. 20% of the converted C2H4, were observed, while no (CHO)2O was formed. Hydroxymethyl hydroperoxide, HOCH2OOH, was observed as the major peroxide, and found to be formed only in the presence of water vapour. Direct reactions of H2O vapour with the excited CH2OO* radicals and with stabilized CH2OO radicals are postulated to explain the formation of HCOOH and HOCH2OOH in the presence of water vapour, respectively.

Seasonal measurements of organic acid fluxes over a ponderosa pine forest

NASA Astrophysics Data System (ADS)

Fulgham, S. R.; Brophy, P.; Link, M.; Ortega, J. V.; Farmer, D.

2016-12-01

The biosphere acts as both a source and a sink of oxidized organic compounds. Ignoring dry deposition leads to overestimation of secondary organic aerosols by aerosol models, while ignoring emission sources underestimates the budget of organic acids. Developing parameterizations for oxidized organic dry deposition and emission requires observational constraints. Although biosphere parameters are impacted by seasonal variability, most reactive, trace-gas exchange measurements are made for only short periods of time in the main growing season. Here we make fast (5 - 10 Hz) and sensitive (e.g. 0.73 ppt mean limit of detection for formic acid with 10 s averaging) eddy covariance measurements of gas-phase organic acids and other oxidized organic species with a high resolution Time-of-Flight Chemical Ionization Mass Spectrometer with acetate and iodide reagent ions. Measurements were made in 4 - 6 week campaigns over five seasons from summer 2015 to fall 2016 as part of the Seasonal Particles in Forests Flux studY (SPIFFY) at the Manitou Experimental Forest Observatory near Woodland Park, Colorado. Permeation tubes were used for online calibration of carboxylic acids including formic (C1), propionic (C3), butyric (C4), methacrylic (CH2C(CH3)COOH), valeric (C5), and heptanoic (C7) acids. Average daytime mixing ratios for formic acid were 100 ± 100 ppt in winter and 1500 ± 1000 ppt in summer 2016. Upward fluxes of formic acid were observed throughout the experiment, daytime averages and standard deviations ranging from 1900 ± 1000 ppt cm s-1 in winter to 170 ± 130 ppt cm s-1 in spring. Propionic (22 ± 22 ppt cm s-1), butyric (17 ± 16 ppt cm s-1), and methacrylic (3.5 ± 6.1 ppt cm s-1) acids exhibit a mix of upward, near-zero, and downward fluxes. Fluxes were exponentially correlated to temperature, suggesting an ecosystem-scale source of these acids. We also measure exchange velocities of a broad suite of other oxidized organic compounds (31.99 m/z to 311.523 m/z in

Biosorption of formic and acetic acids from aqueous solution using activated carbon from shea butter seed shells

NASA Astrophysics Data System (ADS)

Adekola, Folahan A.; Oba, Ismaila A.

2017-10-01

The efficiency of prepared activated carbon from shea butter seed shells (SB-AC) for the adsorption of formic acid (FA) and acetic acid (AA) from aqueous solution was investigated. The effect of optimization parameters including initial concentration, agitation time, adsorbent dosage and temperature of adsorbate solution on the sorption capacity were studied. The SB-AC was characterized for the following parameters: bulk density, moisture content, ash content, pH, Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The optimal conditions for the adsorption were established and the adsorption data for AA fitted Dubinin-Radushkevich (D-R) isotherm well, whereas FA followed Langmuir isotherm. The kinetic data were examined. It was found that pseudo-second-order kinetic model was found to adequately explain the sorption kinetic of AA and FA from aqueous solution. It was again found that intraparticle diffusion was found to explain the adsorption mechanism. Adsorption thermodynamic parameters were estimated and the negative values of Δ G showed that the adsorption process was feasible and spontaneous in nature, while the negative values of Δ H indicate that the adsorption process was exothermic. It is therefore established that SB-AC has good potential for the removal of AA and FA from aqueous solution. Hence, it should find application in the regular treatment of polluted water in aquaculture and fish breeding system.

Characterization nano crystalline cellulose from sugarcane baggase for reinforcement in polymer composites: Effect of formic acid concentrations

NASA Astrophysics Data System (ADS)

Aprilia, N. A. S.; Mulyati, S.; Alam, P. N.; Karmila; Ambarita, A. C.

2018-04-01

Nanocellulose from sugarcane bagasse for reinforcement in polymer composites has isolated from formic acid (FA) with different concentration. This research was conducted with three level concentration of FA ei. 15, 30 and 50%. The nanocellulose were successfully prepared with variations of total yields of 66.66, 67.33 and 69.33% respectively with increase of FA concentrations at 6 hours of hidrolysis time. The obtained nanocellulose were characterized by fourier transform infrared (FT-IR) spectroscopy confirmed the introduction of carboxyl goups on the surface of cellulose. The X-ray diffraction (XRD) spectra proved the existence of cellulose, with a highly crystalline of 62.466, 71.033, and 76.296% with increase of FA concentrations. The size of crystallinity of nanocellulose were decreased with increased of FA concentration. The result investigated that size of crystallinity of nano cellulose reduced from 4.37, 4.15 and 3.94 nm.

Evaluation of Adsorption Characteristics of a Fibrous Adsorbent Containing Zwitter-Ionic Functional Group, Targeting Organic Acids.

PubMed

Nakazawa, Akira; Tang, Ning; Inoue, Yoshinori; Kamichatani, Waka; Katoh, Toshifumi; Saito, Mitsuru; Obara, Kenji; Toriba, Akira; Hayakawa, Kazuichi

2017-01-01

Diallylamine-maleic acid copolymer (DAM)-nonwoven fabric (DAM-f), a fibrous adsorbent, contains DAM with zwitter-ionic functional groups and forms a hydration layer on the surface. The aim of this report was to evaluate the adsorption selectivity of DAM-f to semi-volatile organic acid (C1-C5). In the aqueous phase, formic acid dissolved in the hydration layer bound to the imino group of DAM-f due to anion exchange interaction. In the gas phase, the adsorption amounts of organic acids increased with the exposure time. Moreover, the adsorption rate constants correlated with the air/water partition coefficients (log K aw ) for formic acid, propionic acid, butyric acid, valeric acid and isovaleric acid, except for acetic acid. These results indicate that DAM-f is highly selective to hydrophilic compounds which easily move from the air to the hydration layer of DAM-f.

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 ...

Challenges in the Greener Production of Formates/Formic Acid, Methanol, and DME by Heterogeneously Catalyzed CO2 Hydrogenation Processes

PubMed Central

2017-01-01

The recent advances in the development of heterogeneous catalysts and processes for the direct hydrogenation of CO2 to formate/formic acid, methanol, and dimethyl ether are thoroughly reviewed, with special emphasis on thermodynamics and catalyst design considerations. After introducing the main motivation for the development of such processes, we first summarize the most important aspects of CO2 capture and green routes to produce H2. Once the scene in terms of feedstocks is introduced, we carefully summarize the state of the art in the development of heterogeneous catalysts for these important hydrogenation reactions. Finally, in an attempt to give an order of magnitude regarding CO2 valorization, we critically assess economical aspects of the production of methanol and DME and outline future research and development directions. PMID:28656757

HCOOH-induced Controlled-release Hydrolysis of Microalgae (Scenedesmus) to Lactic Acid over Sn-Beta Catalyst.

PubMed

Zan, Yifan; Sun, Yuanyuan; Kong, Lingzhao; Miao, Gai; Bao, Liwei; Wang, Hao; Li, Shenggang; Sun, Yuhan

2018-06-12

Formic acid induced controlled-release hydrolysis of sugar-rich microalgae (Scenedesmus) over the Sn-Beta catalyst was found to be a highly efficient process for producing lactic acid as a platform chemical. One-pot reaction with a very high lactic acid yield of 83.0% was realized in a batch reactor using water as the solvent. Under the attack of formic acid, the cell wall of Scenedesmus was disintegrated, and hydrolysis of the starch inside the cell was strengthened in a controlled-release mode, resulting in a stable and relatively low glucose concentration. Subsequently, the Sn-Beta catalyst was employed for the efficient conversion of glucose into lactic acid with stable catalytic performance through isomerization, retro-aldol and de-/rehydration reactions. Thus, the hydrolysis of polysaccharides and the catalytic conversion of the monosaccharide into lactic acid was realized by the synergy between an organic Brønsted acid and a heterogeneous Lewis acid catalyst. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method for the isolation of citric acid and malic acid in Japanese apricot liqueur for carbon stable isotope analysis.

PubMed

Akamatsu, Fumikazu; Hashiguchi, Tomokazu; Hisatsune, Yuri; Oe, Takaaki; Kawao, Takafumi; Fujii, Tsutomu

2017-02-15

A method for detecting the undeclared addition of acidic ingredients is required to control the authenticity of Japanese apricot liqueur. We developed an analytical procedure that minimizes carbon isotope discrimination for measurement of the δ(13)C values of citric and malic acid isolated from Japanese apricot liqueur. Our results demonstrated that freeze-drying is preferable to nitrogen spray-drying, because it does not significantly affect the δ(13)C values of citric acid and results in smaller isotope discrimination for malic acid. Both 0.1% formic acid and 0.2% phosphoric acid are acceptable HPLC mobile phases for the isolation of citric and malic acid, although the δ(13)C values of malic acid exhibited relatively large variation compared with citric acid following isolation using either mobile phase. The developed procedure allows precise δ(13)C measurements of citric and malic acid isolated from Japanese apricot liqueur. Copyright © 2016 Elsevier Ltd. All rights reserved.

Highly efficient hydrogen release from formic acid using a graphitic carbon nitride-supported AgPd nanoparticle catalyst

NASA Astrophysics Data System (ADS)

Yao, Fang; Li, Xiao; Wan, Chao; Xu, Lixin; An, Yue; Ye, Mingfu; Lei, Zhao

2017-12-01

Bimetallic AgPd nanoparticles with various molar ratios immobilized on graphitic carbon nitride (g-C3N4) were successfully synthesized via a facile co-reduction approach. The powder XRD, XPS, TEM, EDX, ICP-AES and BET were employed to characterize the structure, size, composition and loading metal electronic states of the AgPd/g-C3N4 catalysts. The catalytic property of as-prepared catalysts for the dehydrogenation of formic acid (FA) with sodium formate (SF) as the additive was investigated. The performance of these catalysts, as indicated by the turnover frequency (TOF), depended on the composition of the prepared catalysts. Among all the AgPd/g-C3N4 catalysts tested, Ag9Pd91/g-C3N4 was found to be an exceedingly high activity for decomposing FA into H2 with TOF up to 480 h-1 at 323 K. The prepared catalyst is thus a potential candidate for triggering the widespread use of FA for H2 storage.

Material compatibility evaluation for DWPF nitric-glycolic acid-literature review

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

Mickalonis, J.; Skidmore, E.

2013-06-01

Glycolic acid is being evaluated as an alternative for formic and nitric acid in the DWPF flowsheet. Demonstration testing and modeling for this new flowsheet has shown that glycolic acid and glycolate has a potential to remain in certain streams generated during the production of the nuclear waste glass. A literature review was conducted to assess the impact of glycolic acid on the corrosion of the materials of construction for the DWPF facility as well as facilities downstream which may have residual glycolic acid and glycolates present. The literature data was limited to solutions containing principally glycolic acid.

Highly efficient and autocatalytic H2₂ dissociation for CO₂ reduction into formic acid with zinc.

PubMed

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

2014-03-28

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.

Organic acids and thymol: unsuitable alternative control of Aethina tumida Murray (Coleoptera: Nitidulidae)

USDA-ARS?s Scientific Manuscript database

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...

Hierarchical concave layered triangular PtCu alloy nanostructures: rational integration of dendritic nanostructures for efficient formic acid electrooxidation.

PubMed

Wu, Fengxia; Lai, Jianping; Zhang, Ling; Niu, Wenxin; Lou, Baohua; Luque, Rafael; Xu, Guobao

2018-05-08

The rational construction of multi-dimensional layered noble metal nanostructures is a great challenge since noble metals are not layer-structured materials. Herein, we report a one-pot hydrothermal synthetic method for PtCu hierarchical concave layered triangular (HCLT) nanostructures using dl-carnitine, KI, poly(vinylpyrrolidone), CuCl2, and H2PtCl6. The PtCu HCLT nanostructure is comprised of multilayered triangular dendrites. Its layer number is tunable by changing dl-carnitine concentrations, and the concavity/convexity of the PtCu triangle nanostructures is tunable by changing the H2PtCl6/CuCl2 ratio or KI concentrations. Hierarchical trigonal bipyramid nanoframes are also obtained under certain conditions. Because of its advantageous nanostructure and bimetallic synergetic effect, the obtained PtCu HCLT nanostructure exhibits enhanced electrocatalytic activity and prolonged stability to formic acid oxidation compared to commercial Pt black, Pd/C and some other nanostructures.

Behaviors of glucose decomposition during acid-catalyzed hydrothermal hydrolysis of pretreated Gelidium amansii.

PubMed

Jeong, Tae Su; Choi, Chang Ho; Lee, Ji Ye; Oh, Kyeong Keun

2012-07-01

Acid-catalyzed hydrothermal hydrolysis is one path to cellulosic glucose and subsequently to its dehydration end products such as hydroxymethyl furfural (HMF), formic acid and levulinic acid. The effect of sugar decomposition not only lowers the yield of fermentable sugars but also forms decomposition products that inhibit subsequent fermentation. The present experiments were conducted with four different acid catalysts (H(2)SO(4), HNO(3), HCl, and H(3)PO(4)) at various acid normalities (0.5-2.1N) in batch reactors at 180-210 °C. From the results, H(2)SO(4) was the most suitable catalyst for glucose production, but glucose decomposition occurred during the hydrolysis. The glucose production was maximized at 160.7 °C, 2.0% (w/v) H(2)SO(4), and 40 min, but resulted in a low glucan yield of 33.05% due to the decomposition reactions, which generated formic acid and levulinic acid. The highest concentration of levulinic acid, 7.82 g/L, was obtained at 181.2 °C, 2.0% (w/v) H(2)SO(4), and 40 min. Copyright © 2012 Elsevier Ltd. All rights reserved.

Protic NNN and NCN Pincer-Type Ruthenium Complexes Featuring (Trifluoromethyl)pyrazole Arms: Synthesis and Application to Catalytic Hydrogen Evolution from Formic Acid.

PubMed

Nakahara, Yoshiko; Toda, Tatsuro; Matsunami, Asuka; Kayaki, Yoshihito; Kuwata, Shigeki

2018-01-04

NNN and NCN pincer-type ruthenium(II) complexes featuring two protic pyrazol-3-yl arms with a trifluoromethyl (CF 3 ) group at the 5-position were synthesized and structurally characterized to evaluate the impact of the substitution on the properties and catalysis. The increased Brønsted acidity by the highly electron-withdrawing CF 3 pendants was demonstrated by protonation-deprotonation experiments. By contrast, the IR spectra of the carbonyl derivatives as well as the cyclic voltammogram indicated that the electron density of the ruthenium atom is negligibly influenced by the CF 3 group. Catalysis of these complexes in the decomposition of formic acid to dihydrogen and carbon dioxide was also examined. The NNN pincer-type complex 1 a with the CF 3 group exhibited a higher catalytic activity than the tBu-substituted analogue 1 b. In addition, the bis(CF 3 -pyrazolato) ammine derivative 4 catalyzed the reaction even in the absence of base additives. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly efficient organosolv fractionation of cornstalk into cellulose and lignin in organic acids.

PubMed

Shui, Tao; Feng, Shanghuan; Yuan, Zhongshun; Kuboki, Takashi; Xu, Chunbao Charles

2016-10-01

In this study, effects of fractionation solvents, catalysts, temperatures and residence time on yields, purity and chemical composition of the products were investigated at the solid/solvent ratio of 1:5 (g/g). It was revealed that mixture of acetic acid/formic acid/water at the ratio of 3:6:1 (v/v/v) resulted in crude cellulose and lignin products of relatively high purity. The use of HCl catalyst contributed to a high crude cellulose yield, while H2SO4 showed an adverse effect on cellulose yield. However, both of these acidic catalysts contributed to much lower hemicellulose contents in the resulted crude cellulose products compared with those obtained without a catalyst. Fractionation at 90°C for 180min in mixed solvents of acetic acid/formic acid/water (3:6:1, v/v/v) with or without catalyst produced crude cellulose with very low residual lignin contents (<4%). Copyright © 2016. Published by Elsevier Ltd.

Generation of organic acids and monosaccharides by hydrolytic and oxidative transformation of food processing residues.

PubMed

Fischer, Klaus; Bipp, Hans-Peter

2005-05-01

Carbohydrate-rich biomass residues, i.e. sugar beet molasses, whey powder, wine yeast, potato peel sludge, spent hops, malt dust and apple marc, were tested as starting materials for the generation of marketable chemicals, e.g. aliphatic acids, sugar acids and mono-/disaccharides. Residues were oxidized or hydrolyzed under acidic or alkaline conditions applying conventional laboratory digestion methods and microwave assisted techniques. Yields and compositions of the oxidation products differed according to the oxidizing agent used. Main products of oxidation by 30% HNO(3) were acetic, glucaric, oxalic and glycolic acids. Applying H(2)O(2)/CuO in alkaline solution, the organic acid yields were remarkably lower with formic, acetic and threonic acids as main products. Gluconic acid was formed instead of glucaric acid throughout. Reaction of a 10% H(2)O(2) solution with sugar beet molasses generated formic and lactic acids mainly. Na(2)S(2)O(8) solutions were very inefficient at oxidizing the residues. Glucose, arabinose and galactose were formed during acidic hydrolysis of malt dust and apple marc. The glucose content reached 0.35 g per gram of residue. Important advantages of the microwave application were lower reaction times and reduced reagent demands.

Glycolic acid physical properties and impurities assessment

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

Lambert, D. P.; Pickenheim, B. R.; Hay, M. S.

This document has been revised to add analytical data for fresh, 1 year old, and 4 year old glycolic acid as recommended in Revision 2 of this document. This was needed to understand the concentration of formaldehyde and methoxyacetic acid, impurities present in the glycolic acid used in Savannah River National Laboratory (SRNL) experiments. Based on this information, the concentration of these impurities did not change during storage. These impurities were in the glycolic acid used in the testing included in this report and in subsequent testing using DuPont (now called Chemours) supplied Technical Grade 70 wt% glycolic acid. However,more » these impurities were not reported in the first two versions of this report. The Defense Waste Processing Facility (DWPF) is planning to implement a nitric-glycolic acid flowsheets to increase attainment to meet closure commitment dates during Sludge Batch 9. In fiscal year 2009, SRNL was requested to determine the physical properties of formic and glycolic acid blends.« less

Effects of dissolved low molecular weight organic acids on oxidation of ferrous iron by Acidithiobacillus ferrooxidans.

PubMed

Ren, Wan-Xia; Li, Pei-Jun; Zheng, Le; Fan, Shu-Xiu; Verhozina, V A

2009-02-15

A few researchers have reported on work concerning bioleaching of heavy-metal-contaminated soil using Acidithiobacillus ferrooxidans, since this acidophile is sensitive to dissolved low molecular weight (LMW) organic acids. Iron oxidation by A. ferrooxidans R2 as well as growth on ferrous iron was inhibited by a variety of dissolved LMW organic acids. Growth experiments with ferrous iron as an oxidant showed that the inhibition capability sequence was formic acid>acetic acid>propionic acid>oxalic acid>malic acid>citric acid. The concentrations that R2 might tolerate were formic acid 0.1mmolL(-1) (2mmolkg(-1)soil), acetic and propionic acids 0.4mmolL(-1) (8mmolkg(-1)soil), oxalic acid 2.0mmolL(-1) (40mmolkg(-1)soil), malic acid 20mmolL(-1) (400mmolkg(-1)soil), citric acid 40mmolL(-1) (800mmolkg(-1)soil), respectively. Although R2 was sensitive to organic acids, the concentrations of LMW organic acids in the contaminated soils were rather lower than the tolerable levels. Hence, it is feasible that R2 might be used for bioleaching of soils contaminated with metals or metals coupled with organic compounds because of the higher concentrations of LMW organic acids to which R2 is tolerant.

Enhanced Hydrogen Production from Formic Acid by Formate Hydrogen Lyase-Overexpressing Escherichia coli Strains

PubMed Central

Yoshida, Akihito; Nishimura, Taku; Kawaguchi, Hideo; Inui, Masayuki; Yukawa, Hideaki

2005-01-01

Genetic recombination of Escherichia coli in conjunction with process manipulation was employed to elevate the efficiency of hydrogen production in the resultant strain SR13 2 orders of magnitude above that of conventional methods. The formate hydrogen lyase (FHL)-overexpressing strain SR13 was constructed by combining FHL repressor (hycA) inactivation with FHL activator (fhlA) overexpression. Transcription of large-subunit formate dehydrogenase, fdhF, and large-subunit hydrogenase, hycE, in strain SR13 increased 6.5- and 7.0-fold, respectively, compared to the wild-type strain. On its own, this genetic modification effectively resulted in a 2.8-fold increase in hydrogen productivity of SR13 compared to the wild-type strain. Further enhancement of productivity was attained by using a novel method involving the induction of the FHL complex with high-cell-density filling of a reactor under anaerobic conditions. Continuous hydrogen production was achieved by maintaining the reactor concentration of the substrate (free formic acid) under 25 mM. An initial productivity of 23.6 g hydrogen h−1 liter−1 (300 liters h−1 liter−1 at 37°C) was achieved using strain SR13 at a cell density of 93 g (dry weight) cells/liter. The hydrogen productivity reported in this work has great potential for practical application. PMID:16269707

Enhanced hydrogen production from formic acid by formate hydrogen lyase-overexpressing Escherichia coli strains.

PubMed

Yoshida, Akihito; Nishimura, Taku; Kawaguchi, Hideo; Inui, Masayuki; Yukawa, Hideaki

2005-11-01

Genetic recombination of Escherichia coli in conjunction with process manipulation was employed to elevate the efficiency of hydrogen production in the resultant strain SR13 2 orders of magnitude above that of conventional methods. The formate hydrogen lyase (FHL)-overexpressing strain SR13 was constructed by combining FHL repressor (hycA) inactivation with FHL activator (fhlA) overexpression. Transcription of large-subunit formate dehydrogenase, fdhF, and large-subunit hydrogenase, hycE, in strain SR13 increased 6.5- and 7.0-fold, respectively, compared to the wild-type strain. On its own, this genetic modification effectively resulted in a 2.8-fold increase in hydrogen productivity of SR13 compared to the wild-type strain. Further enhancement of productivity was attained by using a novel method involving the induction of the FHL complex with high-cell-density filling of a reactor under anaerobic conditions. Continuous hydrogen production was achieved by maintaining the reactor concentration of the substrate (free formic acid) under 25 mM. An initial productivity of 23.6 g hydrogen h(-1) liter(-1) (300 liters h(-1) liter(-1) at 37 degrees C) was achieved using strain SR13 at a cell density of 93 g (dry weight) cells/liter. The hydrogen productivity reported in this work has great potential for practical application.

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

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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Native lignin structure of Miscanthus x giganteus and its changes during acetic and formic acid fractionation.

PubMed

Villaverde, Juan José; Li, Jiebing; Ek, Monica; Ligero, Pablo; de Vega, Alberto

2009-07-22

Milled wood lignin (MWL) and acetic and formic acid lignin (AL and FL) from Miscanthus x giganteus bark were produced, respectively, before and after organosolv fractionations under optimal conditions, in terms of organic and hydrochloric acid concentrations, liquid/wood ratio, and reaction time. In order to study the M. x giganteus native lignin structure and its modifications during the fractionation process, the lignins were studied by two-dimensional heteronuclear single quantum coherence (2D-(HSQC)), (13)C- and (31)P nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared (FTIR), size-exclusion chromatography (SEC) both before and after thioacidolysis, and elemental analysis. In addition, chemical composition analysis was performed on ash, Klason lignin, and carbohydrate content. The analyses demonstrated that M. x giganteus native lignin (MWL) is highly acylated at the C(gamma) of the lignin side chain (46%), possibly with p-coumarate and/or acetate groups. This is newsworthy since several earlier studies showed that acylation at the gamma-carbon commonly occurs in C(3) and CAM grasses, whereas M. x giganteus is a C(4) grass. Furthermore, M. x giganteus showed a low S/G ratio (0.7) and a predominance of beta-O-4' linkages (up to 93% of all linkages). AL and FL lose part of these linkages during organosolv fractionation (up to 21 and 32%, respectively). The p-coumarate groups resist fractionation processes and are still present in high quantities in AL and FL. During the fractionation process, lignin is acetylated (acetic acid process) and condensed, with the G units condensing more than S units. M. x giganteus MWL contains a high content of carbohydrates (22.8%), suggesting that it is a lignin-carbohydrate complex (LCC). AL and FL showed low carbohydrate contents because of the breaking down of the LCC structures. AL and FL have high molecular weights and low polydispersities, and are high in phenolic content, qualities that make these

Material Compatibility Evaluation for DWPF Nitric-Glycolic Acid - Literature Review

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

Mickalonis, J. I.; Skidmore, T. E.

Glycolic acid is being evaluated as an alternative for formic and nitric acid in the DWPF flowsheet. Demonstration testing and modeling for this new flowsheet has shown that glycolic acid and glycolate has a potential to remain in certain streams generated during the production of the nuclear waste glass. A literature review was conducted to assess the impact of glycolic acid on the corrosion of the materials of construction for the DWPF facility as well as facilities downstream which may have residual glycolic acid and glycolates present. The literature data was limited to solutions containing principally glycolic acid. The reportedmore » corrosion rates and degradation characteristics have shown the following for the materials of construction.« less

Isotopomer enrichment assay for very short chain fatty acids and its metabolic applications.

PubMed

Tomcik, Kristyen; Ibarra, Rafael A; Sadhukhan, Sushabhan; Han, Yong; Tochtrop, Gregory P; Zhang, Guo-Fang

2011-03-01

The present work illustrated an accurate GC/MS measurement for the low isotopomer enrichment assay of formic acid, acetic acid, propionic aicd, butyric acid, and pentanoic acid. The pentafluorobenzyl bromide derivatives of these very short chain fatty acids have high sensitivity of isotopoic enrichment due to their low natural isotopomer distribution in negative chemical ionization mass spectrometric mode. Pentafluorobenzyl bromide derivatization reaction was optimized in terms of pH, temperature, reaction time, and the amount of pentafluorobenzyl bromide versus sample. The precision, stability, and accuracy of this method for the isotopomer analysis were validated. This method was applied to measure the enrichments of formic acid, acetic acid, and propionic acid in the perfusate from rat liver exposed to Krebs-Ringer bicarbonate buffer only, 0-1mM [3,4-(13)C(2)]-4-hydroxynonanoate, and 0-2mM [5,6,7-(13)C(3)]heptanoate. The enrichments of acetic acid and propionic acid in the perfusate are comparable to the labeling pattern of acetyl-CoA and propionyl-CoA in the rat liver tissues. The enrichment of the acetic acid assay is much more sensitive and precise than the enrichment of acetyl-CoA by LC-MS/MS. The reversibility of propionyl-CoA from succinyl-CoA was confirmed by the low labeling of M1 and M2 of propionic acid from [5,6,7-(13)C(3)]heptanoate perfusates. 2010 Elsevier Inc. All rights reserved.

Anchoring and Upgrading Ultrafine NiPd on Room-Temperature-Synthesized Bifunctional NH2 -N-rGO toward Low-Cost and Highly Efficient Catalysts for Selective Formic Acid Dehydrogenation.

PubMed

Yan, Jun-Min; Li, Si-Jia; Yi, Sha-Sha; Wulan, Ba-Ri; Zheng, Wei-Tao; Jiang, Qing

2018-03-01

Hydrogen is widely considered to be a sustainable and clean energy alternative to the use of fossil fuels in the future. Its high hydrogen content, nontoxicity, and liquid state at room temperature make formic acid a promising hydrogen carrier. Designing highly efficient and low-cost heterogeneous catalysts is a major challenge for realizing the practical application of formic acid in the fuel-cell-based hydrogen economy. Herein, a simple but effective and rapid strategy is proposed, which demonstrates the synthesis of NiPd bimetallic ultrafine particles (UPs) supported on NH 2 -functionalized and N-doped reduced graphene oxide (NH 2 -N-rGO) at room temperature. The introduction of the NH 2 N group to rGO is the key reason for the formation of the ultrafine and well-dispersed Ni 0.4 Pd 0.6 UPs (1.8 nm) with relatively large surface area and more active sites. Surprisingly, the as-prepared low-cost NiPd/NH 2 -N-rGO dsiplays excellent hydrophilicity, 100% H 2 selectivity, 100% conversion, and remarkable catalytic activity (up to 954.3 mol H 2 (mol catalyst) -1 h -1 ) for FA decomposition at room temperature even with no additive, which is much higher than that of the best catalysts so far reported. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of ferromagnetic nanoparticles, formic acid oxidation catalyst nanocomposites, and late-transition metal-boride intermetallics by unique synthetic methods and single-source precursors

NASA Astrophysics Data System (ADS)

Wellons, Matthew S.

The design, synthesis, and characterization of magnetic alloy nanoparticles, supported formic acid oxidation catalysts, and superhard intermetallic composites are presented. Ferromagnetic equatomic alloy nanoparticles of FePt, FePd, and CoPt were synthesized utilizing single-source heteronuclear organometallic precursors supported on an inert water-soluble matrix. Direct conversion of the precursor-support composite to supported ferromagnetic nanoparticles occurs under elevated temperatures and reducing conditions with metal-ion reduction and minimal nanoparticle coalescence. Nanoparticles were easily extracted from the support by addition of water and characterized in structure and magnetic properties. Palladium and platinum based nanoparticles were synthesized with microwave-based and chemical metal-ion reduction strategies, respectively, and tested for catalytic performance in a direct formic acid fuel cell (DFAFC). A study of palladium carbide nanocomposites with various carbonaceous supports was conducted and demonstrated strong activity comparable to commercially available palladium black, but poor catalytic longevity. Platinum-lead alloy nanocomposites synthesized with chemical reduction and supported on Vulcan carbon demonstrated strong activity, excellent catalytic longevity, and were subsequently incorporated into a prototype DFAFC. A new method for the synthesis of superhard ceramics on polymer substrates called Confined Plasma Chemical Deposition (CPCD) was developed. The CPCD method utilizes a tuned Free Electron Laser to selectively decompose the single-source precursor, Re(CO)4(B3H8), in a plasma-like state resulting in the superhard intermetallic ReB2 deposited on polymer substrates. Extension of this method to the synthesis of other hard of superhard ceramics; WB4, RuB2, and B4C was demonstrated. These three areas of research show new synthetic methods and novel materials of technological importance, resulting in a substantial advance in their

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

PubMed

Ohta, Kazutoku; Ohashi, Masayoshi; Jin, Ji-Ye; Takeuchi, Toyohide; Fujimoto, Chuzo; Choi, Seong-Ho; Ryoo, Jae-Jeong; Lee, Kwang-Pill

2003-05-16

The application of various hydrophilic cation-exchange resins for high-performance liquid chromatography (sulfonated silica gel: TSKgel SP-2SW, carboxylated silica gel: TSKgel CM-2SW, sulfonated polymethacrylate resin: TSKgel SP-5PW, carboxylated polymethacrylate resins: TSKgel CM-5PW and TSKgel OA-Pak A) as stationary phases in ion-exclusion chromatography for C1-C7 aliphatic carboxylic acids (formic, acetic, propionic, butyric, isovaleric, valeric, isocaproic, caproic, 2-methylhexanoic and heptanoic acids) and benzenecarboxylic acids (pyromellitic, trimellitic, hemimellitic, o-phthalic, m-phthalic, p-phthalic, benzoic, salicylic acids and phenol) was carried out using diluted sulfuric acid as the eluent. Silica-based cation-exchange resins (TSKgel SP-2SW and TSKgel CM-2SW) were very suitable for the ion-exclusion chromatographic separation of these benzenecarboxylic acids. Excellent simultaneous separation of these benzenecarboxylic acids was achieved on a TSKgel SP-2SW column (150 x 6 mm I.D.) in 17 min using a 2.5 mM sulfuric acid at pH 2.4 as the eluent. Polymethacrylate-based cation-exchange resins (TSKgel SP-5PW, TSKgel CM-5PW and TSKgel OA-Pak A) acted as advanced stationary phases for the ion-exclusion chromatographic separation of these C1-C7 aliphatic carboxylic acids. Excellent simultaneous separation of these C1-C7 acids was achieved on a TSKgel CM-5PW column (150 x 6 mm I.D.) in 32 min using a 0.05 mM sulfuric acid at pH 4.0 as the eluent.

Multiple Hydrogen Bond Tethers for Grazing Formic Acid in Its Complexes with Phenylacetylene.

PubMed

Karir, Ginny; Kumar, Gaurav; Kar, Bishnu Prasad; Viswanathan, K S

2018-03-01

Complexes of phenylacetylene (PhAc) and formic acid (FA) present an interesting picture, where the two submolecules are tethered, sometimes multiply, by hydrogen bonds. The multiple tentacles adopted by PhAc-FA complexes stem from the fact that both submolecules can, in the same complex, serve as proton acceptors and/or proton donors. The acetylenic and phenyl π systems of PhAc can serve as proton acceptors, while the ≡C-H or -C-H of the phenyl ring can act as a proton donor. Likewise, FA also is amphiprotic. Hence, more than 10 hydrogen-bonded structures, involving O-H···π, C-H···π, and C-H···O contacts, were indicated by our computations, some with multiple tentacles. Interestingly, despite the multiple contacts in the complexes, the barrier between some of the structures is small, and hence, FA grazes around PhAc, even while being tethered to it, with hydrogen bonds. We used matrix isolation infrared spectroscopy to experimentally study the PhAc-FA complexes, with which we located global and a few local minima, involving primarily an O-H···π interaction. Experiments were corroborated by ab initio computations, which were performed using MP2 and M06-2X methods, with 6-311++G (d,p) and aug-cc-pVDZ basis sets. Single-point energy calculations were also done at MP2/CBS and CCSD(T)/CBS levels. The nature, strength, and origin of these noncovalent interactions were studied using AIM, NBO, and LMO-EDA analysis.

Cirrus cloud mimic surfaces in the laboratory: organic acids, bases and NOx heterogeneous reactions

NASA Astrophysics Data System (ADS)

Sodeau, J.; Oriordan, B.

2003-04-01

CIRRUS CLOUD MIMIC SURFACES IN THE LABORATORY:ORGANIC ACIDS, BASES AND NOX HETEROGENEOUS REACTIONS. B. ORiordan, J. Sodeau Department of Chemistry and Environment Research Institute, University College Cork, Ireland j.sodeau@ucc.ie /Fax: +353-21-4902680 There are a variety of biogenic and anthropogenic sources for the simple carboxylic acids to be found in the troposphere giving rise to levels as high as 45 ppb in certain urban areas. In this regard it is of note that ants of genus Formica produce some 10Tg of formic acid each year; some ten times that produced by industry. The expected sinks are those generally associated with tropospheric chemistry: the major routes studied, to date, being wet and dry deposition. No studies have been carried out hitherto on the role of water-ice surfaces in the atmospheric chemistry of carboxylic acids and the purpose of this paper is to indicate their potential function in the heterogeneous release of atmospheric species such as HONO. The deposition of formic acid on a water-ice surface was studied using FT-RAIR spectroscopy over a range of temperatures between 100 and 165K. In all cases ionization to the formate (and oxonium) ions was observed. The results were confirmed by TPD (Temperature Programmed Desorption) measurements, which indicated that two distinct surface species adsorb to the ice. Potential reactions between the formic acid/formate ion surface and nitrogen dioxide were subsequently investigated by FT-RAIRS. Co-deposition experiments showed that N2O3 and the NO+ ion (associated with water) were formed as products. A mechanism is proposed to explain these results, which involves direct reaction between the organic acid and nitrogen dioxide. Similar experiments involving acetic acid also indicate ionization on a water-ice surface. The results are put into the context of atmospheric chemistry potentially occuring on cirrus cloud surfaces.

Enhanced levels of atmospheric low-molecular weight monocarboxylic acids in gas and particulates over Mt. Tai, North China, during field burning of agricultural wastes

NASA Astrophysics Data System (ADS)

Mochizuki, Tomoki; Kawamura, Kimitaka; Nakamura, Shinnosuke; Kanaya, Yugo; Wang, Zifa

2017-12-01

To understand the source and atmospheric behaviour of low molecular weight monocarboxylic acids (monoacids), gaseous (G) and particulate (P) organic acids were collected at the summit of Mt. Tai in the North China Plain (NCP) during field burning of agricultural waste (wheat straw). Particulate organic acids were collected with neutral quartz filter whereas gaseous organic acids were collected with KOH-impregnated quartz filter. Normal (C1-C10), branched (iC4-iC6), hydroxy (lactic and glycolic), and aromatic (benzoic) monoacids were determined with a capillary gas chromatography employing p-bromophenacyl esters. We found acetic acid as the most abundant gas-phase species whereas formic acid is the dominant particle-phase species. Concentrations of formic (G/P 1 570/1 410 ng m-3) and acetic (3 960/1 120 ng m-3) acids significantly increased during the enhanced field burning of agricultural wastes. Concentrations of formic and acetic acids in daytime were found to increase in both G and P phases with those of K+, a field-burning tracer (r = 0.32-0.64). Primary emission and secondary formation of acetic acid is linked with field burning of agricultural wastes. In addition, we found that particle-phase fractions (Fp = P/(G + P)) of formic (0.50) and acetic (0.31) acids are significantly high, indicating that semi-volatile organic acids largely exist as particles. Field burning of agricultural wastes may play an important role in the formation of particulate monoacids in the NCP. High levels (917 ng m-3) of particle-phase lactic acid, which is characteristic of microorganisms, suggest that microbial activity associated with terrestrial ecosystem significantly contributes to the formation of organic aerosols.

Reductive de-polymerization of kraft lignin for chemicals and fuels using formic acid as an in-situ hydrogen source.

PubMed

Huang, Shanhua; Mahmood, Nubla; Tymchyshyn, Matthew; Yuan, Zhongshun; Xu, Chunbao Charles

2014-11-01

In this study, formic acid (FA) was employed as an in-situ hydrogen donor for the reductive de-polymerization of kraft lignin (KL). Under the optimum operating conditions, i.e., 300 °C, 1 h, 18.6 wt.% substrate concentration, 50/50 (v/v) water-ethanol medium with FA at a FA-to-lignin mass ratio of 0.7, KL (Mw∼10,000 g/mol) was effectively de-polymerized, producing de-polymerized lignin (DL, Mw 1270 g/mol) at a yield of ∼90 wt.% and <1 wt.% yield of solid residue (SR). The MW of the DL products decreased with increasing reaction temperature, time and FA-to-lignin mass ratio. The sulfur contents of all DL products were remarkably lower than that in the original KL. It was also demonstrated that FA is a more reactive hydrogen source than external hydrogen for reductive de-polymerization of KL. Copyright © 2014 Elsevier Ltd. All rights reserved.

[Catalytic stability in wet air oxidation of carboxylic acids over ZnFe0.25Al1.75 O4 catalyst].

PubMed

Xu, Ai-hua; Yang, Min; Du, Hong-zhang; Peng, Fu-yong; Sun, Cheng-lin

2007-07-01

Oxalic, formic and acetic acid are main intermediate products in catalytic wet air oxidation process (CWAO). The catalytic activity and stability in CWAO of the three short-chain organic acids over ZnFe0.25Al1.75O4 catalyst were studied. Oxalic acid is the only oxidizable intermediate and the largest amount of Fe leaching is 9.5 mg L(-1) at 160 degrees C during CWAO process. Formic and acetic acid have little influence on Fe leaching. Due to the strong reducible ability of oxalic acid, the amount of Fe leaching is larger in nitrogen atmosphere than that in oxygen atmosphere. Salicylic acid can be also degraded by ZnFe0.25Al1.75O4 catalyst with a high catalytic activity and stability.

On the Structure Sensitivity of Formic Acid Decomposition on Cu Catalysts

DOE PAGES

Li, Sha; Scaranto, Jessica; Mavrikakis, Manos

2016-08-03

Catalytic decomposition of formic acid (HCOOH) has attracted substantial attention since HCOOH is a major by-product in biomass reforming, a promising hydrogen carrier, and also a potential low temperature fuel cell feed. Despite the abundance of experimental studies for vapor-phase HCOOH decomposition on Cu catalysts, the reaction mechanism and its structure sensitivity is still under debate. In this work, self-consistent, periodic density functional theory calculations were performed on three model surfaces of copper—Cu(111), Cu(100) and Cu(211), and both the HCOO (formate)-mediated and COOH (carboxyl)-mediated pathways were investigated for HCOOH decomposition. The energetics of both pathways suggest that the HCOO-mediated routemore » is more favorable than the COOH-mediated route on all three surfaces, and that HCOOH decomposition proceeds through two consecutive dehydrogenation steps via the HCOO intermediate followed by the recombinative desorption of H 2. On all three surfaces, HCOO dehydrogenation is the likely rate determining step since it has the highest transition state energy and also the highest activation energy among the three catalytic steps in the HCOO pathway. The reaction is structure sensitive on Cu catalysts since the examined three Cu facets have dramatically different binding strengths for the key intermediate HCOO and varied barriers for the likely rate determining step—HCOO dehydrogenation. Cu(100) and Cu(211) bind HCOO much more strongly than Cu(111), and they are also characterized by potential energy surfaces that are lower in energy than that for the Cu(111) facet. Coadsorbed HCOO and H represents the most stable state along the reaction coordinate, indicating that, under reaction conditions, there might be a substantial surface coverage of the HCOO intermediate, especially at under-coordinated step, corner or defect sites. Therefore, under reaction conditions, HCOOH decomposition is predicted to occur most readily on the terrace

Stabilizing CuPd Nanoparticles via CuPd Coupling to WO 2.72 Nanorods in Electrochemical Oxidation of Formic Acid

DOE PAGES

Xi, Zheng; Li, Junrui; Su, Dong; ...

2017-10-05

Stabilizing a 3d-transition metal component M from an MPd alloy structure in an acidic environment is key to the enhancement of MPd catalysis for various reactions. Here we show a strategy to stabilize Cu in 5 nm CuPd nanoparticles (NPs) by coupling the CuPd NPs with perovskite-type WO 2.72 nanorods (NRs). The CuPd NPs are prepared by controlled diffusion of Cu into Pd NPs and the coupled CuPd/WO 2.72 are synthesized by growing WO 2.72 NRs in the presence of CuPd NPs. The CuPd/WO 2.72 can stabilize Cu in 0.1 M HClO4 solution and, as a result, they show Cu,more » Pd composition dependent activity for the electrochemical oxidation of formic acid in 0.1 M HClO 4 + 0.1 M HCOOH. Among three different CuPd/WO 2.72 studied, the Cu 48Pd 52/WO 2.72 is the most efficient catalyst with its mass activity reaching 2086 mA/mgPd in a broad potential range of 0.40 to 0.80 V (vs. RHE) and staying at this value after the 12 h chronoamperometry test at 0.40 V. The synthesis can be extended to obtain other MPd/WO 2.72 (M = Fe, Co, Ni), making it possible to study MPd-WO 2.72 interactions and MPd stabilization on enhancing MPd catalysis for various chemical reactions.« less

Reactivity of formic acid (HCOOD and DCOOH) at uranium and UO 2.0 surfaces

NASA Astrophysics Data System (ADS)

Manner, William L.; Lloyd, Jane A.; Paffett, Mark T.

1999-10-01

Interactions of DCOOH and HCOOD with uranium and UO 2.0 surfaces have been examined using surface-specific techniques of thermal desorption mass spectroscopy (TDMS), X-ray photoelectron spectroscopy (XPS), and static secondary ion mass spectroscopy (SSIMS). On the clean uranium surface, formate is the predominant product following formic acid adsorption at 100 K. A wide range of products is observed after annealing to 200 K, including formate, hydroxyl, O ads, and H ads (D ads) groups. Adsorbed formate decomposes by 300 K increasing the concentration of the remaining surface products. Surface-adsorbed carbon following TDMS measurements remains as the carbide, as indicated from XPS and SSIMS measurements. The only gaseous species created in high yields from the clean surface upon annealing are H 2, HD, and D 2. On the oxide surface (UO 2.0), adsorbed formate groups are more stable toward dissociation in comparison with the clean uranium surface. Between 100 and 300 K the predominant species on the UO 2.0 surface are surface formate and hydroxyl groups. Hydroxyl groups react between 300 and 350 K to release water from the surface. Adsorbed formate groups decompose between 400 and 500 K to release CO and H 2CO (D 2CO) groups from the oxide surface. Carbon was not detected on the oxide surface by XPS or SSIMS after annealing to 500 K, indicating that all carbon-containing species either desorb in the form of CO-containing products or migrate into the surface.

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.

Fabrication of Nitrogen-Doped Mesoporous-Carbon-Coated Palladium Nanoparticles: An Intriguing Electrocatalyst for Methanol and Formic Acid Oxidation.

PubMed

Ray, Chaiti; Dutta, Soumen; Sahoo, Ramkrishna; Roy, Anindita; Negishi, Yuichi; Pal, Tarasankar

2016-05-20

Inspired by the attractive catalytic properties of palladium and the inert nature of carbon supports in catalysis, a concise and simple methodology for in situ nitrogen-doped mesoporous-carbon-supported palladium nanoparticles (Pd/N-C) has been developed by carbonizing a palladium dimethylglyoximate complex. The as-synthesized Pd/N-C has been exfoliated as a fuel cell catalyst by studying the electro-oxidation of methanol and formic acid. The material synthesized at 400 °C,namely, Pd/N-C-400,exhibitssuperior mass activity and stability among catalysts synthesized under different carbonization temperaturesbetween300 and 500 °C. The unique 1D porous structure in Pd/N-C-400 helps better electron transport at the electrode surface, which eventually leads to about five times better catalytic activity and about two times higher stability than that of commercial Pd/C. Thus, our designed sacrificial metal-organic templatedirected pathway becomes a promising technique for Pd/N-C synthesis with superior catalytic performances. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel Hybrid Catalyst for the Oxidation of Organic Acids: Pd Nanoparticles Supported on Mn-N-3D-Graphene Nanosheets

DOE PAGES

Perry, Albert; Kabir, Sadia; Matanovic, Ivana; ...

2017-06-16

This paper reports the fabrication and electrochemical performance of a hybrid catalyst composed of Pd nanoparticles and atomically dispersed Mn active centers integrated into the nitrogen-doped three-dimensional graphene nanosheets (Pd/Mn-N-3D-GNS). Our results show that the synergistic integration of both Pd nanoparticles and atomically dispersed Mn can be used to enhance the activity toward the electrochemical oxidation of organic acids at biologically relevant pH values. The hybrid catalyst (Pd/Mn-N-3D-GNS) showed increased maximum currents toward the oxidation of oxalic acid when compared to its individual catalysts, namely, Pd/3D-GNS and Mn N-3D-GNS catalysts. The hybrid also showed a decreased onset potential for oxidationmore » of mesoxalic acid as compared to Mn-N-3D-GNS and decreased onset potentials for the oxidation of glyoxalic acid when compared to both of its constituent catalysts. Oxidation of formic acid was also tested and the hybrid was shown to catalyze both dehydration and dehydrogenation mechanisms of formic acid electro-oxidation. Using density functional theory calculations, it was elucidated that a two-site catalysis most likely promotes dehydrogenation reaction for formic acid oxidation, which can explain the selectivity of Pd nanoparticles and atomically dispersed Mn towards the dehydrogenation/ dehydration pathway.« less

Novel Hybrid Catalyst for the Oxidation of Organic Acids: Pd Nanoparticles Supported on Mn-N-3D-Graphene Nanosheets

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

Perry, Albert; Kabir, Sadia; Matanovic, Ivana

This paper reports the fabrication and electrochemical performance of a hybrid catalyst composed of Pd nanoparticles and atomically dispersed Mn active centers integrated into the nitrogen-doped three-dimensional graphene nanosheets (Pd/Mn-N-3D-GNS). Our results show that the synergistic integration of both Pd nanoparticles and atomically dispersed Mn can be used to enhance the activity toward the electrochemical oxidation of organic acids at biologically relevant pH values. The hybrid catalyst (Pd/Mn-N-3D-GNS) showed increased maximum currents toward the oxidation of oxalic acid when compared to its individual catalysts, namely, Pd/3D-GNS and Mn N-3D-GNS catalysts. The hybrid also showed a decreased onset potential for oxidationmore » of mesoxalic acid as compared to Mn-N-3D-GNS and decreased onset potentials for the oxidation of glyoxalic acid when compared to both of its constituent catalysts. Oxidation of formic acid was also tested and the hybrid was shown to catalyze both dehydration and dehydrogenation mechanisms of formic acid electro-oxidation. Using density functional theory calculations, it was elucidated that a two-site catalysis most likely promotes dehydrogenation reaction for formic acid oxidation, which can explain the selectivity of Pd nanoparticles and atomically dispersed Mn towards the dehydrogenation/ dehydration pathway.« less

FY13 GLYCOLIC-NITRIC ACID FLOWSHEET DEMONSTRATIONS OF THE DWPF CHEMICAL PROCESS CELL WITH SIMULANTS

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

Lambert, D.; Zamecnik, J.; Best, D.

Savannah River Remediation is evaluating changes to its current Defense Waste Processing Facility flowsheet to replace formic acid with glycolic acid in order to improve processing cycle times and decrease by approximately 100x the production of hydrogen, a potentially flammable gas. Higher throughput is needed in the Chemical Processing Cell since the installation of the bubblers into the melter has increased melt rate. Due to the significant maintenance required for the safety significant gas chromatographs and the potential for production of flammable quantities of hydrogen, eliminating the use of formic acid is highly desirable. Previous testing at the Savannah Rivermore » National Laboratory has shown that replacing formic acid with glycolic acid allows the reduction and removal of mercury without significant catalytic hydrogen generation. Five back-to-back Sludge Receipt and Adjustment Tank (SRAT) cycles and four back-to-back Slurry Mix Evaporator (SME) cycles were successful in demonstrating the viability of the nitric/glycolic acid flowsheet. The testing was completed in FY13 to determine the impact of process heels (approximately 25% of the material is left behind after transfers). In addition, back-to-back experiments might identify longer-term processing problems. The testing was designed to be prototypic by including sludge simulant, Actinide Removal Product simulant, nitric acid, glycolic acid, and Strip Effluent simulant containing Next Generation Solvent in the SRAT processing and SRAT product simulant, decontamination frit slurry, and process frit slurry in the SME processing. A heel was produced in the first cycle and each subsequent cycle utilized the remaining heel from the previous cycle. Lower SRAT purges were utilized due to the low hydrogen generation. Design basis addition rates and boilup rates were used so the processing time was shorter than current processing rates.« less

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.

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

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

Sweeting, J. Nicole; Siu, Michelle; McCallum, Gordon P.

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)more » 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.« less

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

PubMed

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

2006-01-01

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

A search for formic acid in the upper troposphere - A tentative identification of the 1105-per cm nu-6 band Q branch in high-resolution balloon-borne solar absorption spectra

NASA Technical Reports Server (NTRS)

Goldman, A.; Murcray, F. H.; Murcray, D. G.; Rinsland, C. P.

1984-01-01

Infrared solar absorption spectra recorded at 0.02-per cm resolution during a balloon flight from Alamogordo, NM (33 deg N), on March 23, 1981, have been analyzed for the possible presence of absorption by formic acid (HCOOH). An absorption feature at 1105 per cm has been tentatively identified in upper tropospheric spectra as due to the nu-6 band Q branch. A preliminary analysis indicates a concentration of about 0.6 ppbv and 0.4 ppbv near 8 and 10 km, respectively.

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.

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.

Identification of anaerobic bacteria by Bruker Biotyper matrix-assisted laser desorption ionization-time of flight mass spectrometry with on-plate formic acid preparation.

PubMed

Schmitt, Bryan H; Cunningham, Scott A; Dailey, Aaron L; Gustafson, Daniel R; Patel, Robin

2013-03-01

Identification of anaerobic bacteria using phenotypic methods is often time-consuming; methods such as 16S rRNA gene sequencing are costly and may not be readily available. We evaluated 253 clinical isolates of anaerobic bacteria using the Bruker MALDI Biotyper (Bruker Daltonics, Billerica, MA) matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) system with a user-supplemented database and an on-plate formic acid-based preparation method and compared results to those of conventional identification using biochemical testing or 16S rRNA gene sequencing. A total of 179 (70.8%) and 232 (91.7%) isolates were correctly identified to the species and genus levels, respectively, using manufacturer-recommended score cutoffs. MALDI-TOF MS offers a rapid, inexpensive method for identification of anaerobic bacteria.

Pharmacokinetics of Caffeic Acid, Ferulic Acid, Formononetin, Cryptotanshinone, and Tanshinone IIA after Oral Administration of Naoxintong Capsule in Rat by HPLC-MS/MS.

PubMed

Li, Jin; Bai, Yang; Bai, Yun; Zhu, Ruichao; Liu, Wei; Cao, Jun; An, Mingrui; Tan, Zhijing; Chang, Yan-Xu

2017-01-01

Naoxintong capsule (NXTC) was a famous patent medicine of Traditional Chinese Medicine (TCM) to treat cerebrovascular diseases in China. An LC-MS/MS method was developed for simultaneous determination of 11 major ingredients (paeoniflorin, ecdysterone, amygdalin, mulberroside A, caffeic acid, ferulic acid, salvianolic acid B, astragaloside IV, formononetin, cryptotanshinone, and tanshinone IIA) in NXTC in rat plasma. All analytes were separated on an Eclipse plus C 18 column using a gradient mobile phase system of acetonitrile-0.1% formic acid aqueous solution. The lower limits of quantification of 11 ingredients were between 0.075 and 10 ng mL -1 . The precision was less than 15% and the accuracies were between 85% and 115%. The results showed that caffeic acid, ferulic acid, formononetin, cryptotanshinone, and tanshinone IIA could be detected after oral administration of NXTC. The validated method was successfully applied to pharmacokinetic study of the caffeic acid, ferulic acid, formononetin, cryptotanshinone, and tanshinone IIA in rats after oral administration of NXTC at single and triple dose.

Dual hydrogen-bonding motifs in complexes formed between tropolone and formic acid

NASA Astrophysics Data System (ADS)

Nemchick, Deacon J.; Cohen, Michael K.; Vaccaro, Patrick H.

2016-11-01

The near-ultraviolet π*←π absorption system of weakly bound complexes formed between tropolone (TrOH) and formic acid (FA) under cryogenic free-jet expansion conditions has been interrogated by exploiting a variety of fluorescence-based laser-spectroscopic probes, with synergistic quantum-chemical calculations built upon diverse model chemistries being enlisted to unravel the structural and dynamical properties of the pertinent ground [X˜ 1A'] and excited [A˜ 1A'(" separators="π*π )] electronic states. For binary TrOH ṡ FA adducts, the presence of dual hydrogen-bond linkages gives rise to three low-lying isomers designated (in relative energy order) as INT, EXT1, and EXT2 depending on whether docking of the FA ligand to the TrOH substrate takes place internal or external to the five-membered reaction cleft of tropolone. While the symmetric double-minimum topography predicted for the INT potential surface mediates an intermolecular double proton-transfer event, the EXT1 and EXT2 structures are interconverted by an asymmetric single proton-transfer process that is TrOH-centric in nature. The A ˜ -X ˜ origin of TrOH ṡ FA at ν˜ 00=27 484 .45 cm-1 is displaced by δ ν˜ 00=+466 .76 cm-1 with respect to the analogous feature for bare tropolone and displays a hybrid type - a/b rotational contour that reflects the configuration of binding. A comprehensive analysis of vibrational landscapes supported by the optically connected X˜ 1A' and A˜ 1A'(" separators="π*π ) manifolds, including the characteristic isotopic shifts incurred by partial deuteration of the labile TrOH and FA protons, has been performed leading to the uniform assignment of numerous intermolecular (viz., modulating hydrogen-bond linkages) and intramolecular (viz., localized on monomer subunits) degrees of freedom. The holistic interpretation of all experimental and computational findings affords compelling evidence that an external-binding motif (attributed to EXT1), rather than the

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.

Selection of anion exchangers for detoxification of dilute-acid hydrolysates from spruce.

PubMed

Horváth, Ilona Sárvári; Sjöde, Anders; Nilvebrant, Nils-Olof; Zagorodni, Andrei; Jönsson, Leif J

2004-01-01

Six anion-exchange resins with different properties were compared with respect to detoxification of a dilute-acid hydrolysate of spruce prior to ethanolic fermentation with Saccharomyces cerevisiae. The six resins encompassed strong and weak functional groups as well as styrene-, phenol-, and acrylic-based matrices. In an analytical experimental series, fractions from columns packed with the different resins were analyzed regarding pH, glucose, furfural, hydroxymethylfurfural, phenolic compounds, levulinic acid, acetic acid, formic acid, and sulfate. An initial adsorption of glucose occurred in the strong alkaline environment and led to glucose accumulation at a later stage. Acetic and levulinic acid passed through the column before formic acid, whereas sulfate had the strongest affinity. In a preparative experimental series, one fraction from each of six columns packed with the different resins was collected for assay of the fermentability and analysis of glucose, mannose, and fermentation inhibitors. The fractions collected from strong anion-exchange resins with styrene-based matrices displayed the best fermentability: a sevenfold enhancement of ethanol productivity compared with untreated hydrolysate. Fractions from a strong anion exchanger with acrylic-based matrix and a weak exchanger with phenol-based resin displayed an intermediate improvement in fermentability, a four- to fivefold increase in ethanol productivity. The fractions from two weak exchangers with styrene- and acrylic-based matrices displayed a twofold increase in ethanol productivity. Phenolic compounds were more efficiently removed by resins with styrene- and phenol-based matrices than by resins with acrylic-based matrices.

Solvent Dependence of Double Proton Transfer in the Formic Acid-Formamidine Complex: Path Integral Molecular Dynamics Investigation.

PubMed

Kungwan, Nawee; Ngaojampa, Chanisorn; Ogata, Yudai; Kawatsu, Tsutomu; Oba, Yuki; Kawashima, Yukio; Tachikawa, Masanori

2017-10-05

Solvent dependence of double proton transfer in the formic acid-formamidine (FA-FN) complex at room temperature was investigated by means of ab initio path integral molecular dynamics (AIPIMD) simulation with taking nuclear quantum and thermal effects into account. The conductor-like screening model (COSMO) was applied for solvent effect. In comparison with gas phase, double proton delocalization between two heavy atoms (O and N) in FA-FN were observed with reduced proton transfer barrier height in low dielectric constant medium (<4.8). For dielectric constant medium at 4.8, the chance of finding these two protons are more pronounced due to the solvent effect which completely washes out the proton transfer barrier. In the case of higher dielectric constant medium (>4.8), the ionic species becomes more stable than the neutral ones and the formate anion and formamidium cation are thermodynamically stable. For ab initio molecular dynamics simulation, in low dielectric constant medium (<4.8) a reduction of proton transfer barrier with solvent effect is found to be less pronounced than the AIPIMD due to the absence of nuclear quantum effect. Moreover, the motions of FA-FN complex are significantly different with increasing dielectric constant medium. Such a difference is revealed in detail by the principal component analysis.

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. (c) 2006 Wiley Periodicals, Inc. J Comput Chem, 2006.

Quantitative analysis of desorption and decomposition kinetics of formic acid on Cu(111): The importance of hydrogen bonding between adsorbed species

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

Shiozawa, Yuichiro; Koitaya, Takanori; Mukai, Kozo

2015-12-21

Quantitative analysis of desorption and decomposition kinetics of formic acid (HCOOH) on Cu(111) was performed by temperature programmed desorption (TPD), X-ray photoelectron spectroscopy, and time-resolved infrared reflection absorption spectroscopy. The activation energy for desorption is estimated to be 53–75 kJ/mol by the threshold TPD method as a function of coverage. Vibrational spectra of the first layer HCOOH at 155.3 K show that adsorbed molecules form a polymeric structure via the hydrogen bonding network. Adsorbed HCOOH molecules are dissociated gradually into monodentate formate species. The activation energy for the dissociation into monodentate formate species is estimated to be 65.0 kJ/mol atmore » a submonolayer coverage (0.26 molecules/surface Cu atom). The hydrogen bonding between adsorbed HCOOH species plays an important role in the stabilization of HCOOH on Cu(111). The monodentate formate species are stabilized at higher coverages, because of the lack of vacant sites for the bidentate formation.« less

Effect of dietary formic acid and astaxanthin on the survival and growth of Pacific white shrimp (Litopenaeus vannamei) and their resistance to Vibrio parahaemolyticus.

PubMed

Chuchird, Niti; Rorkwiree, Phitsanu; Rairat, Tirawat

2015-01-01

A 90-day feeding trial was conducted to evaluate the effects of formic acid (FA) and astaxanthin (AX) on growth, survival, immune parameters, and tolerance to Vibrio infection in Pacific white shrimp. The study was divided into two experiments. In experiment 1, postlarvae-12 were randomly distributed into six groups and then fed four times daily with six experimental diets contained 0.3 % FA, 0.6 % FA, 50 ppm AX, 0.3 % FA + 50 ppm AX, 0.6 % FA + 50 ppm AX, or none of these supplements (control diet). After 60 days of the feeding trials, the body weight of all treatment groups was not significantly different from the control group, although shrimp fed formic acid had significantly lower body weight than shrimp fed 50 ppm AX. However, the 0.6 % FA + 50 ppm AX group had a significantly higher survival rate (82.33 ± 8.32 %) than the control group (64.33 ± 10.12 %). In experiment 2, Vibrio parahaemolyticus was added to each tank to obtain a final concentration of 10(4) colony-forming units/mL. Each treatment group received the aforementioned diets for another 30 days. At the end of this experiment, there was no difference in the weight gain among all experimental groups. However, the survival rate of shrimps whose diet included FA, AX, and their combination (in the range of 45.83-67.50 %) was significantly higher than the control group (20.00 ± 17.32 %). FA-fed shrimps also had significantly lower total intestinal bacteria and Vibrio spp. counts, while immune parameters [total hemocyte count (THC), phagocytosis activity, phenoloxidase (PO) activity, and superoxide dismutase (SOD) activity] of AX-fed groups were significantly improved compared with the other groups. In conclusion, FA, AX, and their combination are useful in shrimp aquaculture.

Oxidation Chemistry and Kinetics of Model Compounds in Supercritical Water: Glucose, Acetic Acid, and Methylene Chloride

DTIC Science & Technology

1993-06-01

adsorption may be needed. I The underground SCWO process is not discussed in detail here. For a more in- i depth discussion see Gloyna (1989). One noteworthy... furfural were also detected. Xylose hydrolysis produced furfural . Other products identified included formic acid, lactic acid, U levulinic acid...noted, and the liquid products consisted namely of furans and furfurals (Amin et al., I 1975; Modell, 1985b). Woerner (1976) corroborates the results

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

Survival and reproduction of some nematodes as affected by muck and organic acids.

PubMed

Elmiligy, I A; Norton, D C

1973-01-01

Fulvic, humic, acetic, N-bulyric, formic, lactic, and propionic acids were inhibitory to the survival or reproduction of Aphelenchus avenae, Aphelenchoides goodeyi, Helicotylenchus pseudorobustus, Meloidogyne hapla or Xiphinema americanum. Reproduction of H. pseudorobustus and M. hapla significantly increased with increasing amounts of muck added to sand, and with the initial amount of nematode inoculum. All acids except humic and fulvic were lethal, in vitro, to all nematode species tested. When A. goodeyi was treated with fulvic acid, reproduction was reduced significantly when compared with sodium humate or water treatments. Treatment of H. pseudorobustus with fulvic acid (pH 3.5) resulted in a greater reduction in reproduction in soil than did treatment with humic acid (pH 3.5).

Iridium and Ruthenium Complexes of N-Heterocyclic Carbene- and Pyridinol-Derived Chelates as Catalysts for Aqueous Carbon Dioxide Hydrogenation and Formic Acid Dehydrogenation: The Role of the Alkali Metal

PubMed Central

2017-01-01

Hydrogenation reactions can be used to store energy in chemical bonds, and if these reactions are reversible, that energy can be released on demand. Some of the most effective transition metal catalysts for CO2 hydrogenation have featured pyridin-2-ol-based ligands (e.g., 6,6′-dihydroxybipyridine (6,6′-dhbp)) for both their proton-responsive features and for metal–ligand bifunctional catalysis. We aimed to compare bidentate pyridin-2-ol based ligands with a new scaffold featuring an N-heterocyclic carbene (NHC) bound to pyridin-2-ol. Toward this aim, we have synthesized a series of [Cp*Ir(NHC-pyOR)Cl]OTf complexes where R = tBu (1), H (2), or Me (3). For comparison, we tested analogous bipy-derived iridium complexes as catalysts, specifically [Cp*Ir(6,6′-dxbp)Cl]OTf, where x = hydroxy (4Ir) or methoxy (5Ir); 4Ir was reported previously, but 5Ir is new. The analogous ruthenium complexes were also tested using [(η6-cymene)Ru(6,6′-dxbp)Cl]OTf, where x = hydroxy (4Ru) or methoxy (5Ru); 4Ru and 5Ru were both reported previously. All new complexes were fully characterized by spectroscopic and analytical methods and by single-crystal X-ray diffraction for 1, 2, 3, 5Ir, and for two [Ag(NHC-pyOR)2]OTf complexes 6 (R = tBu) and 7 (R = Me). The aqueous catalytic studies of both CO2 hydrogenation and formic acid dehydrogenation were performed with catalysts 1–5. In general, NHC-pyOR complexes 1–3 were modest precatalysts for both reactions. NHC complexes 1–3 all underwent transformations under basic CO2 hydrogenation conditions, and for 3, we trapped a product of its transformation, 3SP, which we characterized crystallographically. For CO2 hydrogenation with base and dxbp-based catalysts, we observed that x = hydroxy (4Ir) is 5–8 times more active than x = methoxy (5Ir). Notably, ruthenium complex 4Ru showed 95% of the activity of 4Ir. For formic acid dehydrogenation, the trends were quite different with catalytic activity showing 4Ir ≫ 4Ru and 4Ir ≈ 5Ir

Iridium and Ruthenium Complexes of N-Heterocyclic Carbene- and Pyridinol-Derived Chelates as Catalysts for Aqueous Carbon Dioxide Hydrogenation and Formic Acid Dehydrogenation: The Role of the Alkali Metal.

PubMed

Siek, Sopheavy; Burks, Dalton B; Gerlach, Deidra L; Liang, Guangchao; Tesh, Jamie M; Thompson, Courtney R; Qu, Fengrui; Shankwitz, Jennifer E; Vasquez, Robert M; Chambers, Nicole; Szulczewski, Gregory J; Grotjahn, Douglas B; Webster, Charles Edwin; Papish, Elizabeth T

2017-03-27

Hydrogenation reactions can be used to store energy in chemical bonds, and if these reactions are reversible, that energy can be released on demand. Some of the most effective transition metal catalysts for CO 2 hydrogenation have featured pyridin-2-ol-based ligands (e.g., 6,6'-dihydroxybipyridine (6,6'-dhbp)) for both their proton-responsive features and for metal-ligand bifunctional catalysis. We aimed to compare bidentate pyridin-2-ol based ligands with a new scaffold featuring an N -heterocyclic carbene (NHC) bound to pyridin-2-ol. Toward this aim, we have synthesized a series of [Cp*Ir(NHC-py OR )Cl]OTf complexes where R = t Bu ( 1 ), H ( 2 ), or Me ( 3 ). For comparison, we tested analogous bipy-derived iridium complexes as catalysts, specifically [Cp*Ir(6,6'-dxbp)Cl]OTf, where x = hydroxy ( 4 Ir ) or methoxy ( 5 Ir ); 4 Ir was reported previously, but 5 Ir is new. The analogous ruthenium complexes were also tested using [(η 6 -cymene)Ru(6,6'-dxbp)Cl]OTf, where x = hydroxy ( 4 Ru ) or methoxy ( 5 Ru ); 4 Ru and 5 Ru were both reported previously. All new complexes were fully characterized by spectroscopic and analytical methods and by single-crystal X-ray diffraction for 1 , 2 , 3 , 5 Ir , and for two [Ag(NHC-py OR ) 2 ]OTf complexes 6 (R = t Bu) and 7 (R = Me). The aqueous catalytic studies of both CO 2 hydrogenation and formic acid dehydrogenation were performed with catalysts 1 - 5 . In general, NHC-py OR complexes 1 - 3 were modest precatalysts for both reactions. NHC complexes 1 - 3 all underwent transformations under basic CO 2 hydrogenation conditions, and for 3 , we trapped a product of its transformation, 3 SP , which we characterized crystallographically. For CO 2 hydrogenation with base and dxbp-based catalysts, we observed that x = hydroxy ( 4 Ir ) is 5-8 times more active than x = methoxy ( 5 Ir ). Notably, ruthenium complex 4 Ru showed 95% of the activity of 4 Ir . For formic acid dehydrogenation, the trends were quite different with catalytic

Degradation of clofibric acid in acidic aqueous medium by electro-Fenton and photoelectro-Fenton.

PubMed

Sirés, Ignasi; Arias, Conchita; Cabot, Pere Lluís; Centellas, Francesc; Garrido, José Antonio; Rodríguez, Rosa María; Brillas, Enric

2007-01-01

Acidic aqueous solutions of clofibric acid (2-(4-chlorophenoxy)-2-methylpropionic acid), the bioactive metabolite of various lipid-regulating drugs, have been degraded by indirect electrooxidation methods such as electro-Fenton and photoelectro-Fenton with Fe(2+) as catalyst using an undivided electrolytic cell with a Pt anode and an O(2)-diffusion cathode able to electrogenerate H(2)O(2). At pH 3.0 about 80% of mineralization is achieved with the electro-Fenton method due to the efficient production of oxidant hydroxyl radical from Fenton's reaction between Fe(2+) and H(2)O(2), but stable Fe(3+) complexes are formed. The photoelectro-Fenton method favors the photodecomposition of these species under UVA irradiation, reaching more than 96% of decontamination. The mineralization current efficiency increases with rising metabolite concentration up to saturation and with decreasing current density. The photoelectro-Fenton method is then viable for treating acidic wastewaters containing this pollutant. Comparative degradation by anodic oxidation (without Fe(2+)) yields poor decontamination. Chloride ion is released during all degradation processes. The decay kinetics of clofibric acid always follows a pseudo-first-order reaction, with a similar rate constant in electro-Fenton and photoelectro-Fenton that increases with rising current density, but decreases at greater metabolite concentration. 4-Chlorophenol, 4-chlorocatechol, 4-chlororesorcinol, hydroquinone, p-benzoquinone and 1,2,4-benzenetriol, along with carboxylic acids such as 2-hydroxyisobutyric, tartronic, maleic, fumaric, formic and oxalic, are detected as intermediates. The ultimate product is oxalic acid, which forms very stable Fe(3+)-oxalato complexes under electro-Fenton conditions. These complexes are efficiently photodecarboxylated in photoelectro-Fenton under the action of UVA light.

[Determination of aristolochic acid A in Guanxinsuhe preparations by RP-HPLC].

PubMed

Li, Lin; Gao, Hui-Min; Wang, Zhi-Min; Wang, Wei-Hao

2006-01-01

To establish a determination method of aristolochic acid A in Guanxisuhe preparations by RP-HPLC. The instrument used was Hewlett-Packard 1100 HPLC with a Alltech C18 column (4.6 mm x 250 mm, 5 microm). The mobile phase was methanol-water-acetic acid (68: 32:1) and the flow rate was 1.0 mL x min(-1). The UV detection wavelength was 390 nm and the column temperature was at 35 degrees C. The extracted solvent for the preparations was methanol solution contained 10% formic acid. The calibration curve was linear (r = 0.999 9) within the range of 0.119-1.89 microg for aristolochic acid A. The average recovery 99.0%, RSD 0.63%. The method with good linear relationship was convenient, quick, accurate, and suitable for the quality control of the aristolochic acid A in Guanxinsuhe and other traditional Chinese medicines containing aristolochic acid A.

Synergism between hydrogen peroxide and seventeen acids against five agri-food-borne fungi and one yeast strain.

PubMed

Martin, H; Maris, P

2012-12-01

The objective of this study was to evaluate fungicidal efficacy of hydrogen peroxide administered in combination with 17 mineral and organic acids authorized for use in the food industry. The assays were performed on a 96-well microplate using a microdilution technique based on the checkerboard titration method. The six selected strains (one yeast and five fungi) were reference strains and strains representative of contaminating fungi found in the food industry. Each synergistic hydrogen peroxide/acid combination found after fifteen minutes contact time at 20 °C in distilled water was then tested in conditions simulating four different use conditions. Twelve combinations were synergistic in distilled water, eleven of these remained synergistic with one or more of the four mineral and organic interfering substances selected. Hydrogen peroxide/formic acid combination remained effective against four strains and was never antagonistic against the other two fungi. Combinations with propionic acid and acetic acid stayed synergistic against two strains. Those with oxalic acid and lactic acid kept their synergism only against Candida albicans. No synergism was detected against Penicillium cyclopium. Synergistic combinations of disinfectants were revealed, among them the promising hydrogen peroxide/formic acid combination. A rapid screening method developed in our laboratory for bacteria was adapted to fungi and used to reveal the synergistic potential of disinfectants and/or sanitizers combinations. © 2012 The Society for Applied Microbiology.

Acidic organic compounds in beverage, food, and feed production.

PubMed

Quitmann, Hendrich; Fan, Rong; Czermak, Peter

2014-01-01

Organic acids and their derivatives are frequently used in beverage, food, and feed production. Acidic additives may act as buffers to regulate acidity, antioxidants, preservatives, flavor enhancers, and sequestrants. Beneficial effects on animal health and growth performance have been observed when using acidic substances as feed additives. Organic acids could be classified in groups according to their chemical structure. Each group of organic acids has its own specific properties and is used for different applications. Organic acids with low molecular weight (e.g. acetic acid, lactic acid, and citric acid), which are part of the primary metabolism, are often produced by fermentation. Others are produced more economically by chemical synthesis based on petrochemical raw materials on an industrial scale (e.g. formic acid, propionic and benzoic acid). Biotechnology-based production is of interest due to legislation, consumer demand for natural ingredients, and increasing environmental awareness. In the United States, for example, biocatalytically produced esters for food applications can be labeled as "natural," whereas identical conventional acid catalyst-based molecules cannot. Natural esters command a price several times that of non-natural esters. Biotechnological routes need to be optimized regarding raw materials and yield, microorganisms, and recovery methods. New bioprocesses are being developed for organic acids, which are at this time commercially produced by chemical synthesis. Moreover, new organic acids that could be produced with biotechnological methods are under investigation for food applications.

A nanoporous PdCo alloy as a highly active electrocatalyst for the oxygen-reduction reaction and formic acid electrooxidation.

PubMed

Xu, Caixia; Liu, Yunqing; Zhang, Huan; Geng, Haoran

2013-11-01

A nanoporous (NP) PdCo alloy with uniform structure size and controllable bimetallic ratio was fabricated simply by one-step mild dealloying of a PdCoAl precursor alloy. The as-made alloy consists of a nanoscaled bicontinuous network skeleton with interconnected hollow channels that extend in all three dimensions. With a narrow ligament size distribution around 5 nm, the NP PdCo alloy exhibits much higher electrocatalytic activity towards the oxygen-reduction reaction (ORR) with enhanced specific and mass activities relative to NP Pd and commercial Pt/C catalysts. A long-term stability test demonstrated that NP PdCo has comparable catalytic durability with less loss of ORR activity and electrochemical surface area than Pt/C. The NP PdCo alloy also shows dramatically enhanced catalytic activity towards formic acid electrooxidation relative to NP Pd and Pd/C catalysts. The as-made NP PdCo holds great application potential as a promising cathode as well as an anode electrocatalyst in fuel cells with the advantages of superior catalytic performance and easy preparation. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantitative determination of oxygen defects, surface lewis acidity, and catalytic properties of mesoporous MoO3/SBA-15 catalysts

NASA Astrophysics Data System (ADS)

González, Julio; Wang, Jin An; Chen, Lifang; Manríquez, Maria; Salmones, José; Limas, Roberto; Arellano, Ulises

2018-07-01

A set of MoO3/SBA-15 mesoporous catalysts were characterized with a variety of spectroscopic techniques and their crystalline structures were refined with Rietveld method. Oxygen defect concentration, crystallite size, phase composition, surface acidity, mesoporous regularity, and textural properties were reported. Both α-MoO3 and β-MoO3 phases coexisted but α-MoO3 was predominated. Oxygen defects were created in the orthorhombic structure and its concentration decreased from 3.08% for the 20 wt%MoO3/SBA-15 to 0.55% for the 25 wt%MoO3/SBA-15. All the MoO3/SBA-15 catalysts chiefly contained a big number of Lewis acid sites originating from oxygen defects in MoO3 crystals. In the absence of formic acid, the oxidation of 4,6-dibenzothiophene (4,6-DMDBT) in a model diesel was almost proportional to the number of Lewis acid sites. In the presence of formic acid, 4,6-DMDBT oxidation was significantly affected by the formation of surface peroxometallic complex and Lewis acidity. Formic acid addition could improve the ODS efficiency by promoting peroxometallic complex formation and enhancing oxidant stability. Under the optimal reaction condition using the best 15 and 20 wt%MoO3/SBA-15 catalysts, more than 99% 4,6-DMDBT could be removed at 70 °C within 30 min. This work confirmed that 4,6-DMDBT oxidation is a texture and particle size sensitive and Lewis acidity dependent reaction. This work also shows that crystalline structure refinement combination with experiments can gain new insights in the design of heterogeneous nanocatalysts and help to better understand the catalytic behavior in the oxidative desulfurization reactions.

Epoxidation of cottonseed oil by aqueous hydrogen peroxide catalysed by liquid inorganic acids.

PubMed

Dinda, Srikanta; Patwardhan, Anand V; Goud, Vaibhav V; Pradhan, Narayan C

2008-06-01

The kinetics of epoxidation of cottonseed oil by peroxyacetic acid generated in situ from hydrogen peroxide and glacial acetic acid in the presence of liquid inorganic acid catalysts were studied. It was possible to obtain up to 78% relative conversion to oxirane with very less oxirane cleavage by in situ technique. The rate constants for sulphuric acid catalysed epoxidation of cottonseed oil were in the range 0.39-5.4 x 10(-6)L mol(-1)s(-1) and the activation energy was found to be 11.7 kcal mol(-1). Some thermodynamic parameters such as enthalpy, entropy, and free energy of activation were determined to be of 11.0 kcal mol(-1), -51.4 cal mol(-1)K(-1) and 28.1 kcal mol(-1), respectively. The order of effectiveness of catalysts was found to be sulphuric acid>phosphoric acid>nitric acid>hydrochloric acid. Acetic acid was found to be superior to formic acid for the in situ cottonseed oil epoxidation.

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.

Simultaneous determination of C1-C4 carboxylic acids and aldehydes using 2,4-dinitrophenylhydrazine-impregnated silica gel and high-performance liquid chromatography.

PubMed

Uchiyama, Shigehisa; Matsushima, Erika; Aoyagi, Shohei; Ando, Masanori

2004-10-01

A new method for the simultaneous determination of aliphatic carboxylic acids and aldehydes in air is described. In this work, carboxylic acids were allowed to react with 2,4-dinitrophenylhydrazine (DNPH) to form the corresponding carboxylic 2,4-dinitrophenylhydrazides. These derivatives have excellent thermal stability, with melting points higher than those of the corresponding hydrazones by 32-50 degrees C. C1-C4 carboxylic acid 2,4-dinitrophenylhydrazides exhibited maximum absorption wavelengths of 331-334 nm and molar absorption coefficients of 1.4 x 10(4) L/mol/cm. They were completely separated by high-performance liquid chromatography (HPLC) with an RP-Amide C16 column. Cartridges packed with DNPH-coated silica particles (DNPH cartridge) were used for sampling formic acid and aldehydes. Formic acid was physically adsorbed on the silica particles as the first step of the sampling mechanism. Gradual reaction with DNPH followed. Formic acid reacted very slowly with DNPH at room temperature (20 degrees C), but reacted completely at 80 degrees C over 4 h. In field measurements, the sample air was drawn through a DNPH cartridge. After sampling, the cartridges were heated at 80 degrees C for 5 h and extracted with acetonitrile for HPLC analysis. Under these optimized conditions, the LOD is 0.4 ug/m(3) for an air sample collected for 24 h at 100 mL/min (144 L).

Simultaneous determination of gallic acid and gentisic acid in organic anion transporter expressing cells by liquid chromatography-tandem mass spectrometry.

PubMed

Wang, Li; Halquist, Matthew S; Sweet, Douglas H

2013-10-15

In order to elucidate the role of organic anion transporters (OATs) in the renal elimination of gallic acid and gentisic acid, a new, rapid, and sensitive liquid chromatography-tandem mass spectrometry (LC-MS/MS) method has been developed and validated for the simultaneous determination of gallic acid and gentisic acid in cell lysate, using Danshensu as the internal standard (IS). After a simple liquid-liquid extraction, the analytes were detected in negative ESI mode using selected reaction monitoring. The precursor-to-product ion transitions (m/z) were 169.0→125.0, 153.1→108.0, and 196.8→135.2 for gallic acid, gentisic acid, and the IS, respectively. Chromatographic separation was achieved on a C18 column using mobile phases consisting of water with 0.1% acetic acid (A) and acetonitrile with 0.05% formic acid. (B) The total run time was 3min and calibration curves were linear over the concentrations of 0.33-2400ng/mL for both compounds (r(2)>0.995). Good precision (between 3.11% and 14.1% RSD) and accuracy (between -12.7% and 11% bias) was observed for quality controls at concentrations of 0.33 (lower limit of quantification), 1, 50, and 2000ng/mL. The mean extraction recovery of gallic acid and gentisic acid was 80.7% and 83.5%, respectively. Results from post-column infusion and post-extraction methods indicated that the analytical method exhibited negligible matrix effects. Finally, this validated assay was successfully applied in a cellular uptake study to determine the intracellular concentrations of gallic acid and gentisic acid in OAT expressing cells. Copyright © 2013 Elsevier B.V. All rights reserved.

Succinic Acid Production from Cheese Whey using Actinobacillus succinogenes 130 Z

NASA Astrophysics Data System (ADS)

Wan, Caixia; Li, Yebo; Shahbazi, Abolghasem; Xiu, Shuangning

Actinobacillus succinogenes 130 Z was used to produce succinic acid from cheese whey in this study. At the presence of external CO2 supply, the effects of initial cheese whey concentration, pH, and inoculum size on the succinic acid production were studied. The by-product formation during the fermentation process was also analyzed. The highest succinic acid yield of 0.57 was obtained at initial cheese whey concentration of 50 g/L, while the highest succinic acid productivity of 0.58 g h-1 L-1 was obtained at initial cheese whey concentration of 100 g/L. Increase in pH and inoculum size caused higher succinic acid yield and productivity. At the preferred fermentation condition of pH 6.8, inoculum size of 5% and initial cheese whey concentration of 50 g/L, succinic acid yield of 0.57, and productivity of 0.44 g h-1 L-1 were obtained. Acetic acid and formic acid were the main by-products throughout the fermentation run of 48 h. It is feasible to produce succinic acid using lactose from cheese whey as carbon resource by A. succinogenes 130 Z.

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

NASA Astrophysics Data System (ADS)

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

2003-04-01

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

A Facile Synthesis of MPd (M=Co, Cu) Nanoparticles and Their Catalysis for Formic Acid Oxidation

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

Mazumder, Vismadeb; Chi, Miaofang; Mankin, Max

2012-01-01

Monodisperse CoPd nanoparticles (NPs) were synthesized and studied for catalytic formic acid (HCOOH) oxidation (FAO). The NPs were prepared by coreduction of Co(acac)2 (acac = acetylacetonate) and PdBr2 at 260 C in oleylamine and trioctylphosphine, and their sizes (5-12 nm) and compositions (Co10Pd90 to Co60Pd40) were controlled by heating ramp rate, metal salt concentration, or metal molar ratios. The 8 nm CoPd NPs were activated for HCOOH oxidation by a simple ethanol wash. In 0.1 M HClO4 and 2 M HCOOH solution, their catalytic activities followed the trend of Co50Pd50 > Co60Pd40 > Co10Pd90 > Pd. The Co50Pd50 NPs hadmore » an oxidation peak at 0.4 V with a peak current density of 774 A/gPd. As a comparison, commercial Pd catalysts showed an oxidation peak at 0.75 V with peak current density of only 254 A/gPd. The synthesis procedure could also be extended to prepare CuPd NPs when Co(acac)2 was replaced by Cu(ac)2 (ac = acetate) in an otherwise identical condition. The CuPd NPs were less active catalysts than CoPd or even Pd for FAO in HClO4 solution. The synthesis provides a general approach to Pd-based bimetallic NPs and will enable further investigation of Pd-based alloy NPs for electro-oxidation and other catalytic reactions.« less

Fuel blends: Enhanced electro-oxidation of formic acid in its blend with methanol at platinum nanoparticles modified glassy carbon electrodes

NASA Astrophysics Data System (ADS)

El-Deab, Mohamed S.; El-Nagar, Gumaa A.; Mohammad, Ahmad M.; El-Anadouli, Bahgat E.

2015-07-01

The current study addresses, for the first time, the enhanced direct electro-oxidation of formic acid (FA) at platinum-nanoparticles modified glassy carbon (nano-Pt/GC) electrode in the presence of methanol (MeOH) as a blending fuel. This enhancement is probed by: (i) the increase of the direct oxidation current of FA to CO2 (Ipd, dehydrogenation pathway), (ii) suppressing the dehydration pathway (Ipind, producing the poisoning intermediate CO) and (iii) a favorable negative shift of the onset potential of Ipd with increasing the mole fraction of MeOH in the blend. Furthermore, the charge of the direct FA oxidation in 0.3 M FA + 0.3 M MeOH blend is by 14 and 21times higher than that observed for 0.3 M FA and 0.3 M MeOH, respectively. MeOH is believed to adsorb at the Pt surface sites and thus disfavor the "non-faradaic" dissociation of FA (which produces the poisoning CO intermediate), i.e., MeOH induces a high CO tolerance of the Pt catalyst. The enhanced oxidation activity indicates that FA/MeOH blend is a promising fuel system.

Quantum studies of deprotonated forms of malonic acid

NASA Astrophysics Data System (ADS)

Asciutto, Eliana; Lee, Jung Goo; Pedersen, Lee G.; Sagui, Celeste

2004-03-01

There have been numerous computational studies on carboxylic acids, specially in the simplest ones (formic and acetic acids). A considerable amount of these computations has been dedicated towards developing an understanding of proton transfer. In this work we study malonate as a model for γ-carboxyglutamic acid (Gla). Gla is a metal-binding amino acid whose synthesis is dependent upon vitamin K. Of the classes of proteins that contain Gla, the vitamin K-dependent blood coagulation and regulatory proteins have have been most thoroughly studied. The Gla domain in these proteins (generally consisting of 10-12 Gla residues) induces an structure that facilitates calcium-mediated interactions of the protein with membrane surfaces. In order to get a better understanding of this fundamental role of Gla at a quantum level, we study the role of intramolecular proton transfer in malonate in its divalent anionic form. The di-anion is particularly challenging. A correct description of the potential energy hypersurface is obtained only by application of large basis sets in conjunction with methods including high-level treatment of electron correlation effects.

Measurement of Organic and Inorganic Acids in the Uintah Basin, Utah during UBWOS 2012 and 2013

NASA Astrophysics Data System (ADS)

Yuan, B.; Roberts, J. M.; Warneke, C.; Gilman, J.; Li, S.; Edwards, P. M.; Wild, R.; Min, K.; Brown, S. S.; Johnson, J. E.; Bates, T. S.; Quinn, P.; Koss, A.; Veres, P. R.; De Gouw, J. A.

2013-12-01

Recently, high concentrations of ozone in winter have occurred in the winter in the Uintah Basin in Utah, a region with intensive oil and gas extraction activities. Two field campaigns (Uintah Basin Winter Ozone Study, UBWOS 2012 and 2013) aiming to understand the formation mechanisms of winter ozone were conducted in Jan.-Feb. in the two years. Snow cover and temperature were the main difference between the two campaigns: the winter in 2013 had a snow cover and several cold-pool conditions, whereas the winter of 2012 did not. As a result, only the winter of 2013 saw extensive ozone build-up during several episodes. A chemical ionization mass spectrometer (CIMS) using acetate as reagent ion was deployed to measure organic and inorganic acids. Concentrations of formic acid in 2013 were much higher (a factor of 4.0) than those in 2012, consistent with higher concentrations of other VOCs species and ozone in 2013. Enhancement ratios of formic acid to acetone in Uintah Basin are comparable to those measured in Los Angeles (LA), even though Uintah Basin has much higher alkanes and lower alkenes mixing ratios compared to those in LA. The results are in contrast with the dominant role of alkenes in secondary formation of formic acid in state-of-art chemical mechanisms. The comparisons of these datasets can provide insight into missing secondary sources of formic acid. HONO concentrations measured with the CIMS were also significantly elevated in 2013, especially during daytime. The high daytime HONO measured by CIMS could be caused by three reasons: (1) photolysis of nitrate in snow and aerosol that generates HONO photochemically; (2) evolution of HONO from snow due to acidification and warming during the daytime; (3) potential interferences of other reactive nitrogen species to form NO2- (m/z 46), the ion for quantification of HONO in CIMS. The potential interferences will be explored through laboratory experiments and from the results of box model calculations. The HONO

Influence of carbon source and inoculum type on anaerobic biomass adhesion on polyurethane foam in reactors fed with acid mine drainage.

PubMed

Rodriguez, Renata P; Zaiat, Marcelo

2011-04-01

This paper analyzes the influence of carbon source and inoculum origin on the dynamics of biomass adhesion to an inert support in anaerobic reactors fed with acid mine drainage. Formic acid, lactic acid and ethanol were used as carbon sources. Two different inocula were evaluated: one taken from an UASB reactor and other from the sediment of a uranium mine. The values of average colonization rates and the maximum biomass concentration (C(max)) were inversely proportional to the number of carbon atoms in each substrate. The highest C(max) value (0.35 g TVS g(-1) foam) was observed with formic acid and anaerobic sludge as inoculum. Maximum colonization rates (v(max)) were strongly influenced by the type of inoculum when ethanol and lactic acid were used. For both carbon sources, the use of mine sediment as inoculum resulted in a v(max) of 0.013 g TVS g(-1) foam day(-1), whereas 0.024 g TVS g(-1) foam day(-1) was achieved with anaerobic sludge. Copyright © 2011 Elsevier Ltd. All rights reserved.

Method for the routine quantitative gas chromatographic analysis of major free fatty acids in butter and cream.

PubMed

Woo, A H; Lindsay, R C

1980-07-01

A rapid quantiative method was developed for routine analysis of the major, even carbon-numbered free fatty acids in butter and cream. Free fatty acids were isolated directly from intact samples by a modified silicic acid-potassium hydroxide arrestant column and were separated by gas chromatography with a 1.8 m x 2 mm inner diameter glass column packed with 10% neopentyl glycol adipate on 80/100 Chromosorb W. Purified, formic acid-saturated carrier gas was required for minimal peak tailing and extended column life. The accuracy and reproducibility of the mmethod was established through quantitative recovery studies of free fatty acid mixtures, free fatty acids added to butter, and replicate analysis of butter and cream samples.

Sustainable Synthesis of Oxalic and Succinic Acid through Aerobic Oxidation of C6 Polyols Under Mild Conditions.

PubMed

Ventura, Maria; Williamson, David; Lobefaro, Francesco; Jones, Matthew D; Mattia, Davide; Nocito, Francesco; Aresta, Michele; Dibenedetto, Angela

2018-03-22

The sustainable chemical industry encompasses a shift from the use of fossil carbon to renewable carbon. The synthesis of chemicals from nonedible biomass (cellulosic or oil) represents one of the key steps for "greening" the chemical industry. In this paper, we report the aerobic oxidative cleavage of C6 polyols (5-HMF, glucose, fructose and sucrose) to oxalic acid (OA) and succinic acid (SA) in water under mild conditions using M@CNT and M@NCNT (M=Fe, V; CNT=carbon nanotubes; NCNT=N-doped CNT), which, under suitable conditions, were recoverable and reusable without any loss of efficiency. The influence of the temperature, O 2 pressure (PO2 ), reaction time and stirring rate are discussed and the best reaction conditions are determined for an almost complete conversion of the starting material and a good OA yield of 48 %. SA and formic acid were the only co-products. The former could be further converted into OA by oxidation in the presence of formic acid, resulting in an overall OA yield of >62 %. This process was clean and did not produce organic waste nor gas emissions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Matrix-elimination with steam distillation for determination of short-chain fatty acids in hypersaline waters from pre-salt layer by ion-exclusion chromatography.

PubMed

Ferreira, Fernanda N; Carneiro, Manuel C; Vaitsman, Delmo S; Pontes, Fernanda V M; Monteiro, Maria Inês C; Silva, Lílian Irene D da; Neto, Arnaldo Alcover

2012-02-03

A method for determination of formic, acetic, propionic and butyric acids in hypersaline waters by ion-exclusion chromatography (IEC), using steam distillation to eliminate matrix-interference, was developed. The steam distillation variables such as type of solution to collect the distillate, distillation time and volume of the 50% v/v H₂SO₄ solution were optimized. The effect of the addition of NaCl different concentrations to the calibration standards on the carboxylic acid recovery was also investigated. Detection limits of 0.2, 0.5, 0.3 and 1.5 mg L⁻¹ were obtained for formic, acetic, propionic and butyric acids, respectively. Produced waters from petroleum reservoirs in the Brazilian pre-salt layer containing about 19% m/v of NaCl were analyzed. Good recoveries (99-108%) were obtained for all acids in spiked produced water samples. Copyright © 2011 Elsevier B.V. All rights reserved.

Electrochemical Reduction of CO2 to Organic Acids by a Pd-MWNTs Gas-Diffusion Electrode in Aqueous Medium

PubMed Central

Lu, Guang; Bian, Zhaoyong; Liu, Xin

2013-01-01

Pd-multiwalled carbon nanotubes (Pd-MWNTs) catalysts for the conversion of CO2 to organic acids were prepared by the ethylene glycol reduction and fully characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) technologies. The amorphous Pd particles with an average size of 5.7 nm were highly dispersed on the surface of carbon nanotubes. Functional groups of the MWNTs played a key role in the palladium deposition. The results indicated that Pd-MWNTs could transform CO2 into organic acid with high catalytic activity and CO2 could take part in the reduction reaction directly. Additionally, the electrochemical reduction of CO2 was investigated by a diaphragm electrolysis device, using a Pd-MWNTs gas-diffusion electrode as a cathode and a Ti/RuO2 net as an anode. The main products in present system were formic acid and acetic acid identified by ion chromatograph. The selectivity of the products could be achieved by reaction conditions changing. The optimum faraday efficiencies of formic and acetic acids formed on the Pd-MWNTs gas-diffusion electrode at 4 V electrode voltages under 1 atm CO2 were 34.5% and 52.3%, respectively. PMID:24453849

Structural and electrochemical characterization of carbon supported Pt-Pr catalysts for direct ethanol fuel cells prepared using a modified formic acid method in a CO atmosphere.

PubMed

Corradini, Patricia Gon; Antolini, Ermete; Perez, Joelma

2013-07-28

Pt-Pr/C electrocatalysts were prepared using a modified formic acid method, and their activity for carbon monoxide and ethanol oxidation was compared to Pt/C. No appreciable alloy formation was detected by XRD analysis. By TEM measurements it was found that Pt particle size increases with an increasing Pr content in the catalysts and with decreasing metal precursor addition time. XPS measurements indicated Pt segregation on the catalyst surface and the presence of Pr2O3 and PrO2 oxides. The addition of Pr increased the electro-catalytic activity of Pt for both CO and CH3CH2OH oxidation. The enhanced activity of Pt-Pr/C catalysts was ascribed to both an electronic effect, caused by the presence of Pr2O3, and the bi-functional mechanism, caused by the presence of PrO2.

Low to middle tropospheric profiles and biosphere/troposphere fluxes of acidic gases in the summertime Canadian taiga

NASA Technical Reports Server (NTRS)

Klemm, O.; Talbot, R. W.; Fitzgerald, D. R.; Klemm, K. I.; Lefer, B. L.

1994-01-01

We report features of acidic gases in the troposphere from 9 to 5000 m altitude above ground over the Canadian taiga in the summer of 1990. The measurements were conducted at a 30-m meteorological tower and from the NASA Wallops Electra aircraft as part of the joint U.S.-Canadian Arctic Boundary Layer Expedition (ABLE) 3B Northern Wetland Studies (NOWES). We sampled air for acidic gases using the mist chamber collector coupled with subsequent analysis using ion chromatography. At the tower we collected samples at two heights during a 13-day period, including diurnal studies. Using eddy flux and profile data, we estimated the biosphere/troposphere fluxes of nitric, formic, and acetic acids and sulfur dioxide. For the organic acids, emissions from the taiga in the afternoon hours and deposition during the predawn morning hours were observed. The flux intensities alone were however not high enough to explain the observed changes in mixing ratios. The measured deposition fluxes of nitric acid were high enough to have a significant influence on its mixing ratio in the boundary layer. On three days we measured vertical profiles of nitric, formic, and acetic acids through the lower to midtroposphere. We found that the chemical composition of the troposphere was extremely heterogenous. Pronounced layers of polluted air were readily apparent from our measurements. Local photochemical production and episodic long-range transport of trace components, originating from biomass burning and possibly industrial emissions, appear to have a strong influence on the composition of the troposphere and biosphere/troposphere fluxes of acidic gases at this site.

Quantum free energy landscapes from ab initio path integral metadynamics: Double proton transfer in the formic acid dimer is concerted but not correlated.

PubMed

Ivanov, Sergei D; Grant, Ian M; Marx, Dominik

2015-09-28

With the goal of computing quantum free energy landscapes of reactive (bio)chemical systems in multi-dimensional space, we combine the metadynamics technique for sampling potential energy surfaces with the ab initio path integral approach to treating nuclear quantum motion. This unified method is applied to the double proton transfer process in the formic acid dimer (FAD), in order to study the nuclear quantum effects at finite temperatures without imposing a one-dimensional reaction coordinate or reducing the dimensionality. Importantly, the ab initio path integral metadynamics technique allows one to treat the hydrogen bonds and concomitant proton transfers in FAD strictly independently and thus provides direct access to the much discussed issue of whether the double proton transfer proceeds via a stepwise or concerted mechanism. The quantum free energy landscape we compute for this H-bonded molecular complex reveals that the two protons move in a concerted fashion from initial to product state, yet world-line analysis of the quantum correlations demonstrates that the protons are as quantum-uncorrelated at the transition state as they are when close to the equilibrium structure.

Preparation of sulfonic acid-containing rubbers from natural rubber vulcanizates

NASA Astrophysics Data System (ADS)

Poonsawat, Worapong; Poompradub, Sirilux; Ngamcharussrivichai, Chawalit

2014-06-01

In this work, a series of sulfonic acid-containing rubbers were prepared by aqueous phase oxidation of natural rubber vulcanizates in the presence of hydrogen peroxide (H2O2) and formic acid (HCOOH). The starting vulcanizates were neatly prepared via an efficient vulcanization (EV) system by varying mass ratio of N-cyclohexyl-2-benzothiazole sulfonamide (CBS), as an accelerator, to sulfur. The oxidation conditions were controlled at the molar ratio of H2O2: HCOOH = 1:1, the concentration of H2O2 = 15 wt.%, the temperature = 50 °C, and the reaction time = 3 h. The rubber materials before and after the oxidation were characterized for their physicochemical properties by using Fourier transform infrared spectroscopy, bomb calorimetry, acid-base titration and swelling measurements. The results indicated the presence of sulfonic acid group in the oxidized rubbers, generated by the oxidative cleaves of sulfide crosslinks in the rubber vulcanizates. The oxidation decreased the sulfur content of the rubber in which the level of sulfur loss was determined by the CBS/sulfur ratio. Moreover, the acidity of the oxidized products was correlated with the amount of sulfur remaining.

[Inhibition of Low Molecular Organic Acids on the Activity of Acidithiobacillus Species and Its Effect on the Removal of Heavy Metals from Contaminated Soil].

PubMed

Song, Yong-wei; Wang, He-rul; Cao, Yan-xiao; Li, Fei; Cui, Chun-hong; Zhou, Li

2016-05-15

Application of organic fertilizer can reduce the solubility and bioavailability of heavy metals in contaminated soil, but in the flooded anaerobic environment, organic fertilizer will be decomposed to produce a large number of low molecular organic acids, which can inhibit the biological activity of Acidithiobacillus species. Batch cultures studies showed that the monocarboxylic organic acids including formic acid, acetic acid, propionic acid, and butyric acid exhibited a marked toxicity to Acidithiobacillus species, as indicated by that 90% of inhibitory rate for Fe2 and So oxidation in 72 h were achieved at extremely low concentrations of 41.2 mg · L⁻¹, 78.3 mg · L⁻¹, 43.2 mg · L⁻¹, 123.4 mg · L⁻¹ and 81.9 mg 230. 4 mg · L⁻¹, 170.1 mg · L⁻¹, 123.4 mg · L⁻¹ respectively. Of these organic acids, formic acid was the most toxic one as indicated by that Fe2 and So oxidation was almost entirely inhibited at a low concentration. In addition, it was found that Acidithiobacillus ferrooxidans was more sensitive to low molecular organic acids than Acidithiobacillus thiooxidans. What's more, there was little effect on biological acidification process of heavy metal contaminated soil when organic acids were added at initial stage (Oh), but it was completely inhibited when these acids were added after 12 h of conventional biological acidification, thus decreasing the efficiency of heavy metals dissolution from soil.

High-density defects on PdAg nanowire networks as catalytic hot spots for efficient dehydrogenation of formic acid and reduction of nitrate.

PubMed

Liu, Hu; Yu, Yongsheng; Yang, Weiwei; Lei, Wenjuan; Gao, Manyi; Guo, Shaojun

2017-07-13

Controlling the surface defects of nanocrystals is a new way of tuning/boosting their catalytic properties. Herein, we report networked PdAg nanowires (NWs) with high-density defects as catalytic hot spots for efficient catalytic dehydrogenation of formic acid (FA) and catalytic reduction of nitrates. The networked PdAg NWs exhibit composition-dependent catalytic activity for the dehydrogenation reaction of FA without any additive, with Pd 5 Ag 5 NWs exhibiting the highest activity. They also show good durability, reflected by the retention of their initial activity during the dehydrogenation reaction of FA even after five cycles. Their initial TOF is 419 h -1 at 60 °C in water solution, much higher than those of the most Pd-based catalysts with a support. Moreover, they can efficiently reduce nitrates to alleviate nitrate pollution in water (conversion yield >99%). This strategy opens up a new green synthetic technique to design support-free heterogeneous catalysts with high-density defects as catalytic hot spots for efficient dehydrogenation catalysis of FA to meet the requirement of fuel cell applications and catalytic reduction of nitrates in water polluted with nitrates.

Adaptation and Transcriptome Analysis of Aureobasidium pullulans in Corncob Hydrolysate for Increased Inhibitor Tolerance to Malic Acid Production

PubMed Central

Zou, Xiang; Wang, Yongkang; Tu, Guangwei; Zan, Zhanquan; Wu, Xiaoyan

2015-01-01

Malic acid is a dicarboxylic acid widely used in the food industry, and is also a potential C4 platform chemical. Corncob is a low-cost renewable feedstock from agricultural industry. However, side-reaction products (furfural, 5-hydroxymethylfurfural (HMF), formic acid, and acetic acid) that severely hinder fermentation are formed during corncob pretreatment. The process for producing malic acid from a hydrolysate of corncob was investigated with a polymalic acid (PMA)-producing Aureobasidium pullulans strain. Under the optimal hydrolysate sugar concentration 110 g/L, A. pullulans was further adapted in an aerobic fibrous bed bioreactor (AFBB) by gradually increasing the sugar concentration of hydrolysate. After nine batches of fermentation, the production and productivity of malic acid reached 38.6 g/L and 0.4 g/L h, respectively, which was higher than that in the first batch (27.6 g/L and 0.29 g/L h, respectively). The adapted strain could grow under the stress of 0.5 g/L furfural, 3 g/L HMF, 2g/L acetic acid, and 0.5 g/L formic acid, whereas the wild type did not. Transcriptome analysis revealed that the differentially expressed genes were related to carbohydrate transport and metabolism, lipid transport and metabolism, signal transduction mechanism, redox metabolism, and energy production and conversion under 0.5 g/L furfural and 3 g/L HMF stress conditions. In total, 42 genes in the adapted strain were upregulated by 15-fold or more, and qRT-PCR also confirmed that the expression levels of key genes (i.e. SIR, GSS, CYS, and GSR) involved in sulfur assimilation pathway were upregulated by over 10-fold in adapted strain for cellular protection against oxidative stress. PMID:25793624

Observation of the side chain O-methylation of glutamic acid or aspartic acid containing model peptides by electrospray ionization-mass spectrometry.

PubMed

Atik, A Emin; Guray, Melda Z; Yalcin, Talat

2017-03-15

O-methylation of the side chains of glutamic acid (E) and aspartic acid (D) residues is generally observed modification when an acidified methanol/water (MeOH/dH 2 O) mixture is used as a solvent system during sample preparation for proteomic research. This chemical modification may result misidentification with endogenous protein methylation; therefore, a special care should be taken during sample handling prior to mass spectrometric analysis. In the current study, we systematically examined the extent of E/D methylation and C-terminus carboxyl group of synthetic model peptides in terms of different incubation temperatures, storage times, and added acid types as well as its percentages. To monitor these effects, C-terminus amidated and free acid forms of synthetic model peptides comprised of E or D residue(s) have been analyzed by electrospray ionization-mass spectrometry (ESI-MS). Additionally, LC-MS/MS experiments were performed to confirm the formation of methylated peptide product. The results showed that the rate of methylation was increased as the temperature increases along with prolong incubation times. Moreover, the extent of methylation was remarkably high when formic acid (FA) used as a protonation agent instead of acetic acid (AA). In addition, it was found that the degree of methylation was significantly decreased by lowering acid percentages in ESI solution. More than one acidic residue containing model peptides have been also used to explore the extent of multiple methylation reaction. Lastly, the ethanol (EtOH) and isopropanol (iPrOH) have been substituted separately with MeOH in sample preparation step to investigate the extent of esterification reaction under the same experimental conditions. However, in the positive perspective of view, this method can be used as a simple, rapid and cheap method for methylation of acidic residues under normal laboratory conditions. Copyright © 2017 Elsevier B.V. All rights reserved.

An in Situ NMR Study of the Mechanism for the Catalytic Conversion of Fructose to 5-Hydroxymethylfurfural and then to Levulinic Acid Using 13 C Labeled d -Fructose

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

Zhang, Jing; Weitz, Eric

The pathways for the formation of 5-hydroxymethylfurfural (HMF) by dehydration of d-fructose and for the formation of levulinic acid and formic acid from HMF by rehydration were investigated by in situ13C and 1H NMR using both unlabeled and 13C-labeled fructose. Water or DMSO was used as the solvent with Amberlyst 70, PO43–/niobic acid, or sulfuric acid as catalysts. Only HMF is observed using NMR for fructose dehydration in DMSO with any of the three catalysts or without a catalyst. For each system, results with 13C-labeled fructose indicate that the first carbon (C-1) or sixth carbon (C-6) of fructose maps ontomore » the corresponding carbons of HMF. For fructose dehydration in H2O with a PO43–/niobic acid catalyst, in addition to HMF, furfural was observed as a product. However, we show that furfural is not a reaction product deriving from HMF under our conditions. Rather our data indicate that there is a parallel reaction pathway open to fructose when the reaction takes place in H2O with a PO43–/niobic acid catalyst. The corresponding 13C-labeled results show that the first carbon in fructose maps onto the first carbon (aldehyde carbon) in furfural. Using 13C-enriched HMF formed from dehydration of 13C-labeled fructose in DMSO or H2O, we investigated the pathway for HMF rehydration to levulinic and formic acid. The data in different solvents and with different catalysts are consistent with a common mechanism for HMF rehydration, which results in the C-1 and C-6 carbon of HMF being transformed to the carbon of formic acid and methyl carbon (C-5) of levulinic acid, respectively.« less

Contamination of commercial cane sugars by some organic acids and some inorganic anions.

PubMed

Wojtczak, Maciej; Antczak, Aneta; Lisik, Krystyna

2013-01-01

The aim of the paper was the identification and the quantitative evaluation of the following inorganic anions: chloride, phosphate, nitrate, nitrite, sulphate and the following organic acids: lactic, acetic, formic, malic and citric in commercial "unrefined" brown cane sugars and in cane raw sugars. The determination was carried out by high performance anion exchange chromatography with conductivity detector HPAEC-CD. The conducted analyses have shown that the content of some inorganic anions and organic acids in cane sugars may be an important criterion of the quality of commercial "unrefined" brown cane sugars. Copyright © 2012 Elsevier Ltd. All rights reserved.

Direct injection analysis of fatty and resin acids in papermaking process waters by HPLC/MS.

PubMed

Valto, Piia; Knuutinen, Juha; Alén, Raimo

2011-04-01

A novel HPLC-atmospheric pressure chemical ionization/MS (HPLC-APCI/MS) method was developed for the rapid analysis of selected fatty and resin acids typically present in papermaking process waters. A mixture of palmitic, stearic, oleic, linolenic, and dehydroabietic acids was separated by a commercial HPLC column (a modified stationary C(18) phase) using gradient elution with methanol/0.15% formic acid (pH 2.5) as a mobile phase. The internal standard (myristic acid) method was used to calculate the correlation coefficients and in the quantitation of the results. In the thorough quality parameters measurement, a mixture of these model acids in aqueous media as well as in six different paper machine process waters was quantitatively determined. The measured quality parameters, such as selectivity, linearity, precision, and accuracy, clearly indicated that, compared with traditional gas chromatographic techniques, the simple method developed provided a faster chromatographic analysis with almost real-time monitoring of these acids. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Efficient catalytic decomposition of formic acid for the selective generation of H2 and H/D exchange with a water-soluble rhodium complex in aqueous solution.

PubMed

Fukuzumi, Shunichi; Kobayashi, Takeshi; Suenobu, Tomoyoshi

2008-01-01

Formic acid (HCOOH) decomposes efficiently to afford H2 and CO2 selectively in the presence of a catalytic amount of a water-soluble rhodium aqua complex, [Rh(III)(Cp*)(bpy)(H2O)]2+ (Cp*=pentamethylcyclopentadienyl, bpy=2,2'-bipyridine) in aqueous solution at 298 K. No CO was produced in this catalytic decomposition of HCOOH. The decomposition rate reached a maximum value at pH 3.8. No deterioration of the catalyst was observed during the catalytic decomposition of HCOOH, and the catalytic activity remained the same for the repeated addition of HCOOH. The rhodium-hydride complex was detected as the catalytic active species that undergoes efficient H/D exchange with water. When the catalytic decomposition of HCOOH was performed in D2O, D2 was produced selectively. Such an efficient H/D exchange and the observation of a deuterium kinetic isotope effect in the catalytic decomposition of DCOOH in H2O provide valuable mechanistic insight into this efficient and selective decomposition process.

Wind tunnel investigations on the retention of carboxylic acids during riming

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

Removal of lead by apatite and its stability in the presence of organic acids.

PubMed

Katoh, Masahiko; Makimura, Akihiko; Sato, Takeshi

2016-12-01

In this study, lead sorption and desorption tests were conducted with apatite and organic acids (i.e. citric, malic, and formic acids) to understand lead removal by apatite in the presence of an organic acid and lead dissolution from the lead- and organic-acid-sorbed apatite by such organic acid exposure. The lead sorption test showed that the amount of lead removed by apatite in the presence of organic acid varied depending on the type of acid used. The molar amounts of calcium dissolved from apatite in the presence and absence of organic acid were exactly the same as those of lead removed even under different pH conditions as well as different organic acid concentrations, indicating that the varying amount of lead removal in the presence of different organic acids resulted from the magnitude of the dissolution of apatite and the precipitation of lead phosphate minerals. The percentages of lead dissolved from the organic-acid-sorbed and non-organic-acid-sorbed apatite by all the organic acid extractions were equal and higher than those by water extraction. In particular, the highest extractions were observed in the non-organic-acid-sorbed apatite by citric and malic acids. These results suggest that to immobilize lead by the use of apatite in the presence of organic acids, much more apatite must be added than in the absence of organic acid, and that measures must be taken to ensure that the immobilized lead is not dissolved.

[Determination of aristolochic acid A in Radix Aristolociae and Herba Asari by RP-HPLC].

PubMed

Jiang, Xu; Wang, Zhi-min; You, Li-shuan; Dai, Li-ping; Ding, Guang-zhi

2004-05-01

To develop a HPLC method to determine the contents of aristolochic A in aristolochia debilis and Asarun spp.. Methanol-water-formic acid extracts were separated on an Alltech C18 column with methanol-water-acetic acid (68:32:1) as mobile phase. The flow rate was 1.0 mL x min(-1). UV detection wavelength was 390 nm. Column temperature was 35 degrees C. Aristolochic acid A was separated well. The relationship of injection amounts and peak areas was linear (r = 0.9999) the range of 0.12-1.89 microg x g(-1) and the recovery rate was 101.8% (n = 5). 11 samples of aristolochia debilis which bought from different areas in China were determined, and the contents of aristolochic acid A varied from 0.9 to 2 mg x g(-1). The difference of the contents in Asarum spp. was obvious. The highest is 0.35, and aristolochic acid A couldn't be detected in one sample.

Sustainable Soil Washing: Shredded Card Filtration of Potentially Toxic Elements after Leaching from Soil Using Organic Acid Solutions

PubMed Central

Ash, Christopher; Drábek, Ondřej; Tejnecký, Václav; Jehlička, Jan; Michon, Ninon; Borůvka, Luboš

2016-01-01

Shredded card (SC) was assessed for use as a sorbent of potentially toxic elements (PTE) carried from contaminated soil in various leachates (oxalic acid, formic acid, CaCl2, water). We further assessed SC for retention of PTE, using acidified water (pH 3.4). Vertical columns and a peristaltic pump were used to leach PTE from soils (O and A/B horizons) before passing through SC. Sorption onto SC was studied by comparing leachates, and by monitoring total PTE contents on SC before and after leaching. SC buffers against acidic soil conditions that promote metals solubility; considerable increases in solution pH (+4.49) were observed. Greatest differences in solution PTE content after leaching with/without SC occurred for Pb. In oxalic acid, As, Cd, Pb showed a high level of sorption (25, 15, and 58x more of the respective PTE in leachates without SC). In formic acid, Pb sorption was highly efficient (219x more Pb in leachate without SC). In water, only Pb showed high sorption (191x more Pb in leachate without SC). In desorption experiments, release of PTE from SC varied according to the source of PTE (organic/mineral soil), and type of solvent used. Arsenic was the PTE most readily leached in desorption experiments. Low As sorption from water was followed by fast release (70% As released from SC). A high rate of Cd sorption from organic acid solutions was followed by strong retention (~12% Cd desorption). SC also retained Pb after sorption from water, with subsequent losses of ≤8.5% of total bound Pb. The proposed use of this material is for the filtration of PTE from extract solution following soil washing. Low-molecular-mass organic acids offer a less destructive, biodegradable alternative to strong inorganic acids for soil washing. PMID:26900684

Evaluation of modeled cloud chemistry mechanism against laboratory irradiation experiments: The HxOy/iron/carboxylic acid chemical system

NASA Astrophysics Data System (ADS)

Long, Yoann; Charbouillot, Tiffany; Brigante, Marcello; Mailhot, Gilles; Delort, Anne-Marie; Chaumerliac, Nadine; Deguillaume, Laurent

2013-10-01

Currently, cloud chemistry models are including more detailed and explicit multiphase mechanisms based on laboratory experiments that determine such values as kinetic constants, stability constants of complexes and hydration constants. However, these models are still subject to many uncertainties related to the aqueous chemical mechanism they used. Particularly, the role of oxidants such as iron and hydrogen peroxide in the oxidative capacity of the cloud aqueous phase has typically never been validated against laboratory experimental data. To fill this gap, we adapted the M2C2 model (Model of Multiphase Cloud Chemistry) to simulate irradiation experiments on synthetic aqueous solutions under controlled conditions (e.g., pH, temperature, light intensity) and for actual cloud water samples. Various chemical compounds that purportedly contribute to the oxidative budget in cloud water (i.e., iron, oxidants, such as hydrogen peroxide: H2O2) were considered. Organic compounds (oxalic, formic and acetic acids) were taken into account as target species because they have the potential to form iron complexes and are good indicators of the oxidative capacity of the cloud aqueous phase via their oxidation in this medium. The range of concentrations for all of the chemical compounds evaluated was representative of in situ measurements. Numerical outputs were compared with experimental data that consisted of a time evolution of the concentrations of the target species. The chemical mechanism in the model describing the “oxidative engine” of the HxOy/iron (HxOy = H2O2, HO2rad /O2rad - and HOrad ) chemical system was consistent with laboratory measurements. Thus, the degradation of the carboxylic acids evaluated was closely reproduced by the model. However, photolysis of the Fe(C2O4)+ complex needs to be considered in cloud chemistry models for polluted conditions (i.e., acidic pH) to correctly reproduce oxalic acid degradation. We also show that iron and formic acid lead to

Physiological responses to acid stress by Saccharomyces cerevisiae when applying high initial cell density

PubMed Central

2016-01-01

High initial cell density is used to increase volumetric productivity and shorten production time in lignocellulosic hydrolysate fermentation. Comparison of physiological parameters in high initial cell density cultivation of Saccharomyces cerevisiae in the presence of acetic, formic, levulinic and cinnamic acids demonstrated general and acid-specific responses of cells. All the acids studied impaired growth and inhibited glycolytic flux, and caused oxidative stress and accumulation of trehalose. However, trehalose may play a role other than protecting yeast cells from acid-induced oxidative stress. Unlike the other acids, cinnamic acid did not cause depletion of cellular ATP, but abolished the growth of yeast on ethanol. Compared with low initial cell density, increasing initial cell density reduced the lag phase and improved the bioconversion yield of cinnamic acid during acid adaptation. In addition, yeast cells were able to grow at elevated concentrations of acid, probable due to the increase in phenotypic cell-to-cell heterogeneity in large inoculum size. Furthermore, the specific growth rate and the specific rates of glucose consumption and metabolite production were significantly lower than at low initial cell density, which was a result of the accumulation of a large fraction of cells that persisted in a viable but non-proliferating state. PMID:27620460

Simultaneous determination of acetylsalicylic acid and salicylic acid in human plasma by isocratic high-pressure liquid chromatography with post-column hydrolysis and fluorescence detection.

PubMed

Hobl, Eva-Luise; Jilma, Bernd; Ebner, Josef; Schmid, Rainer W

2013-06-01

A selective, sensitive and rapid high-performance liquid chromatography method with post-column hydrolysis and fluorescence detection was developed for the simultaneous quantification of acetylsalicylic acid and its metabolite salicylic acid in human plasma. Following the addition of 2-hydroxy-3-methoxybenzoic acid as internal standard and simple protein precipitation with acetonitrile, the analytes were separated on a ProntoSIL 120 C18 ace-EPS column (150 × 2 mm, 3 µm) protected by a C8 guard column (5 µm). The mobile phase, 10 mm formic acid in water (pH 2.9) and acetonitrile (70:30, v/v), was used at a flow rate of 0.35 mL/min. After on-line post-column hydrolysis of acetylsalicylic acid (ASA) to salicylic acid (SA) by addition of alkaline solution, the analytes were measured at 290 nm (λex ) and 400 nm (λem ). The method was linear in the concentration ranges between 0.05 and 20 ng/μL for both ASA and SA with a lower limit of quantification of 25 pg/μL for SA and 50 pg/μL for ASA. The limit of detection was 15 pg/μL for SA and 32.5 pg/μL for ASA. The analysis of ASA and SA can be carried out within 8 min; therefore this method is suitable for measuring plasma concentrations of salicylates in clinical routine. Copyright © 2012 John Wiley & Sons, Ltd.

Reactivity of Silanes with ( tBuPONOP)Ruthenium Dichloride: Facile Synthesis of Chloro-Silyl Ruthenium Compounds and Formic Acid Decomposition

DOE PAGES

Anderson, Nickolas H.; Boncella, James M.; Tondreau, Aaron M.

2017-08-15

The coordination of tBuPONOP ( tBuPONOP=2,6-bis(ditert-butylphosphinito)pyridine) to different ruthenium starting materials, to generate ( tBuPONOP)RuCl 2, was investigated in this paper. The resultant ( tBuPONOP)RuCl 2 reactivity with three different silanes was then investigated and contrasted dramatically with the reactivity of ( iPrPONOP)RuCl 2(DMSO) ( iPrPONOP=2,6-bis(diisopropylphosphinito)pyridine) with the same silanes. The 16-electron species ( tBuPONOP)Ru(H)Cl was produced from the reaction of triethylsilane with ( tBuPONOP)RuCl 2. Reactions of ( tBuPONOP)RuCl 2 with both phenylsilane or diphenylsilane afforded the 16-electron hydrido-silyl species ( tBuPONOP)Ru(H)(PhSiCl 2) and ( tBuPONOP)Ru(H)(Ph 2SiCl), respectively. Reactions of all three of these complexes with silver triflate affordedmore » the simple salt metathesis products of ( tBuPONOP)Ru(H)(OTf), ( tBuPONOP)Ru(H)(PhSiCl(OTf)), and ( tBuPONOP)Ru(H)(Ph 2Si(OTf)). Formic acid dehydrogenation was performed in the presence of triethylamine (TEA), and each species proved competent for gas-pressure generation of CO 2 and H 2. Finally, the hydride species ( tBuPONOP)Ru(H)Cl, ( tBuPONOP)Ru(H)(OTf), and ( tBuPONOP)Ru(H)(PhSiCl 2) exhibited faster catalytic activity than the other compounds tested.« less

pH shift protein recovery with organic acids on texture and color of cooked gels.

PubMed

Paker, Ilgin; Beamer, Sarah; Jaczynski, Jacek; Matak, Kristen E

2015-01-01

Isoelectric solubilization and precipitation (ISP) processing uses pH shifts to separate protein from fish frames, which may increase commercial interest for silver carp. Texture and color properties of gels made from silver carp protein recovered at different pH strategies and organic acid types were compared. ISP was applied to headed gutted silver carp using 10 mol L(-1) sodium hydroxide (NaOH) and either glacial acetic acid (AA) or a (1:1) formic and lactic acid combination (F&L). Protein gels were made with recovered protein and standard functional additives. Texture profile analysis and the Kramer shear test showed that protein gels made from protein solubilized at basic pH values were firmer, harder, more cohesive, gummier and chewier (P < 0.05) than proteins solubilized under acidic conditions. Acidic solubilization led to whiter (P < 0.05) gels, and using F&L during ISP yielded whiter gels under all treatments (P < 0.05). Gels made from ISP-recovered silver carp protein using organic acids show potential for use as a functional ingredient in restructured foods. © 2014 Society of Chemical Industry.

A TRPA1-dependent mechanism for the pungent sensation of weak acids

PubMed Central

Wang, Yuanyuan Y.; Chang, Rui B.; Allgood, Sallie D.; Silver, Wayne L.

2011-01-01

Acetic acid produces an irritating sensation that can be attributed to activation of nociceptors within the trigeminal ganglion that innervate the nasal or oral cavities. These sensory neurons sense a diverse array of noxious agents in the environment, allowing animals to actively avoid tissue damage. Although receptor mechanisms have been identified for many noxious chemicals, the mechanisms by which animals detect weak acids, such as acetic acid, are less well understood. Weak acids are only partially dissociated at neutral pH and, as such, some can cross the cell membrane, acidifying the cell cytosol. The nociceptor ion channel TRPA1 is activated by CO2, through gating of the channel by intracellular protons, making it a candidate to more generally mediate sensory responses to weak acids. To test this possibility, we measured responses to weak acids from heterologously expressed TRPA1 channels and trigeminal neurons with patch clamp recording and Ca2+ microfluorometry. Our results show that heterologously expressed TRPA1 currents can be induced by a series of weak organic acids, including acetic, propionic, formic, and lactic acid, but not by strong acids. Notably, the degree of channel activation was predicted by the degree of intracellular acidification produced by each acid, suggesting that intracellular protons are the proximate stimulus that gates the channel. Responses to weak acids produced a Ca2+-independent inactivation that precluded further activation by weak acids or reactive chemicals, whereas preactivation by reactive electrophiles sensitized TRPA1 channels to weak acids. Importantly, responses of trigeminal neurons to weak acids were highly overrepresented in the subpopulation of TRPA1-expressing neurons and were severely reduced in neurons from TRPA1 knockout mice. We conclude that TRPA1 is a general sensor for weak acids that produce intracellular acidification and suggest that it functions within the pain pathway to mediate sensitivity to

Recent Selected Ion Flow Tube (SIFT) Studies Concerning the Formation of Amino Acids in the Gas Phase

NASA Technical Reports Server (NTRS)

Jackson, Douglas M.; Adams, Nigel G.; Babcock, Lucia M.

2006-01-01

Recently the simplest amino acid, glycine, has been detected in interstellar clouds, ISC, although this has since been contested. In order to substantiate either of these claims, plausible routes to amino acids need to be investigated. For gas phase synthesis, the SIFT technique has been employed to study simple amino acids via ion-molecule reactions of several ions of interstellar interest with methylamine, ethylamine, formic acid, acetic acid, and methyl formate. Carboxylic acid type ions were considered in the reactions involving the amines. In reactions where the carboxylic acid and methyl formate neutrals were studied, the reactant ions were primarily amine ion fragments. It was observed that the amines and acids preferentially fragment or accept a proton whenever energetically possible. NH3(+), however, uniquely reacted with the neutrals via atom abstraction to form NH4(+). These studies yielded a body of data relevant to astrochemistry, supplementing the available literature. However, the search for gas phase routes to amino acids using conventional molecules has been frustrated. Our most recent research investigates the fragmentation patterns of several amino acids and several possible routes have been suggested for future study.

Production of lactic acid from hemicellulose extracts by Bacillus coagulans MXL-9.

PubMed

Walton, Sara L; Bischoff, Kenneth M; van Heiningen, Adriaan R P; van Walsum, G Peter

2010-08-01

Bacillus coagulans MXL-9 was found capable of growing on pre-pulping hemicellulose extracts, utilizing all of the principle monosugars found in woody biomass. This organism is a moderate thermophile isolated from compost for its pentose-utilizing capabilities. It was found to have high tolerance for inhibitors such as acetic acid and sodium, which are present in pre-pulping hemicellulose extracts. Fermentation of 20 g/l xylose in the presence of 30 g/l acetic acid required a longer lag phase but overall lactic acid yield was not diminished. Similarly, fermentation of xylose in the presence of 20 g/l sodium increased the lag time but did not affect overall product yield, though 30 g/l sodium proved completely inhibitory. Fermentation of hot water-extracted Siberian larch containing 45 g/l total monosaccharides, mainly galactose and arabinose, produced 33 g/l lactic acid in 60 h and completely consumed all sugars. Small amounts of co-products were formed, including acetic acid, formic acid, and ethanol. Hemicellulose extract formed during autohydrolysis of mixed hardwoods contained mainly xylose and was converted into lactic acid with a 94% yield. Green liquor-extracted hardwood hemicellulose containing 10 g/l acetic acid and 6 g/l sodium was also completely converted into lactic acid at a 72% yield. The Bacillus coagulans MXL-9 strain was found to be well suited to production of lactic acid from lignocellulosic biomass due to its compatibility with conditions favorable to industrial enzymes and its ability to withstand inhibitors while rapidly consuming all pentose and hexose sugars of interest at high product yields.

Trace analysis of acids and bases by conductometric titration with multiparametric non-linear regression.

PubMed

Coelho, Lúcia H G; Gutz, Ivano G R

2006-03-15

A chemometric method for analysis of conductometric titration data was introduced to extend its applicability to lower concentrations and more complex acid-base systems. Auxiliary pH measurements were made during the titration to assist the calculation of the distribution of protonable species on base of known or guessed equilibrium constants. Conductivity values of each ionized or ionizable species possibly present in the sample were introduced in a general equation where the only unknown parameters were the total concentrations of (conjugated) bases and of strong electrolytes not involved in acid-base equilibria. All these concentrations were adjusted by a multiparametric nonlinear regression (NLR) method, based on the Levenberg-Marquardt algorithm. This first conductometric titration method with NLR analysis (CT-NLR) was successfully applied to simulated conductometric titration data and to synthetic samples with multiple components at concentrations as low as those found in rainwater (approximately 10 micromol L(-1)). It was possible to resolve and quantify mixtures containing a strong acid, formic acid, acetic acid, ammonium ion, bicarbonate and inert electrolyte with accuracy of 5% or better.

Recovery of succinic acid produced by fermentation of a metabolically engineered Mannheimia succiniciproducens strain.

PubMed

Song, Hyohak; Huh, Yun Suk; Lee, Sang Yup; Hong, Won Hi; Hong, Yeon Ki

2007-12-01

There have recently been much advances in the production of succinic acid, an important four-carbon dicarboxylic acid for many industrial applications, by fermentation of several natural and engineered bacterial strains. Mannheimia succiniciproducens MBEL55E isolated from bovine rumen is able to produce succinic acid with high efficiency, but also produces acetic, formic and lactic acids just like other anaerobic succinic acid producers. We recently reported the development of an engineered M. succiniciproducens LPK7 strain which produces succinic acid as a major fermentation product while producing much reduced by-products. Having an improved succinic acid producer developed, it is equally important to develop a cost-effective downstream process for the recovery of succinic acid. In this paper, we report the development of a simpler and more efficient method for the recovery of succinic acid. For the recovery of succinic acid from the fermentation broth of LPK7 strain, a simple process composed of a single reactive extraction, vacuum distillation, and crystallization yielded highly purified succinic acid (greater than 99.5% purity, wt%) with a high yield of 67.05wt%. When the same recovery process or even multiple reactive extraction steps were applied to the fermentation broth of MBEL55E, lower purity and yield of succinic acid were obtained. These results suggest that succinic acid can be purified in a cost-effective manner by using the fermentation broth of engineered LPK7 strain, showing the importance of integrating the strain development, fermentation and downstream process for optimizing the whole processes for succinic acid production.

Highly robust hydrogen generation by bio-inspired Ir complexes for dehydrogenation of formic acid in water: Experimental and theoretical mechanistic investigations at different pH

DOE PAGES

Wang, Wan -Hui; Fujita, Etsuko; Ertem, Mehmed Z.; ...

2015-07-30

Hydrogen generation from formic acid (FA), one of the most promising hydrogen storage materials, has attracted much attention due to the demand for the development of renewable energy carriers. Catalytic dehydrogenation of FA in an efficient and green manner remains challenging. Here, we report a series of bio-inspired Ir complexes for highly robust and selective hydrogen production from FA in aqueous solutions without organic solvents or additives. One of these complexes bearing an imidazoline moiety (complex 6) achieved a turnover frequency (TOF) of 322,000 h⁻¹ at 100 °C, which is higher than ever reported. The novel catalysts are very stablemore » and applicable in highly concentrated FA. For instance, complex 3 (1 μmol) affords an unprecedented turnover number (TON) of 2,050,000 at 60 °C. Deuterium kinetic isotope effect experiments and density functional theory (DFT) calculations employing a “speciation” approach demonstrated a change in the rate-determining step with increasing solution pH. This study provides not only more insight into the mechanism of dehydrogenation of FA but also offers a new principle for the design of effective homogeneous organometallic catalysts for H₂ generation from FA.« less

Efficient non-sterilized fermentation of biomass-derived xylose to lactic acid by a thermotolerant Bacillus coagulans NL01.

PubMed

Ouyang, Jia; Cai, Cong; Chen, Hai; Jiang, Ting; Zheng, Zhaojuan

2012-12-01

Xylose is the major pentose and the second most abundant sugar in lignocellulosic feedstock. Its efficient utilization is regarded as a technical barrier to the commercial production of bulk chemicals from lignocellulosic biomass. This work aimed at evaluating the lactic acid production from the biomass-derived xylose using non-sterilized fermentation by Bacillus coagulans NL01. A maximum lactic acid concentration of about 75 g/L was achieved from xylose of 100 g/L after 72 h batch fermentation. Acetic acid and levulinic acid were identified as important inhibitors in xylose fermentation, which markedly reduced lactic acid productivity at 15 and 1.0 g/L, respectively. But low concentrations of formic acid (<2 g/L) exerted a stimulating effect on the lactic acid production. When prehydrolysate containing total 25.45 g/L monosaccharide was fermented with B. coagulans NL01, the same preference for glucose, xylose, and arabinose was observed and18.2 g/L lactic acid was obtained after 48 h fermentation. These results proved that B. coagulans NL01 was potentially well-suited for producing lactic acid from underutilized xylose-rich prehydrolysates.

Ultra-pressure liquid chromatography/tandem mass spectrometry targeted profiling of arachidonic acid and eicosanoids in human colorectal cancer.

PubMed

Mal, Mainak; Koh, Poh Koon; Cheah, Peh Yean; Chan, Eric Chun Yong

2011-03-30

Cumulative evidence shows that eicosanoids such as prostaglandins, leukotrienes, thromboxanes and hydroxy eicosatetraenoic acids play an important role in associating inflammation with human colorectal cancer (CRC). In this study an ultra-pressure liquid chromatography/tandem mass spectrometry (UPLC/MS/MS) method was developed and validated for the targeted profiling of eight relevant eicosanoids and the major metabolic precursor, arachidonic acid (AA), in human colon. Multiple reaction monitoring (MRM) experiments were performed in negative electrospray ionization mode. The metabolites were separated using a C(18) column consisting of 1.7 µm ethylene-bridged hybrid particles (100 × 2.1 mm i.d.) and gradient elution (50 to 95% of solvent B) with a mobile phase comprising water (0.1% formic acid) [solvent A] and acetonitrile (0.1% formic acid) [solvent B] at a flow rate of 0.4 mL/min. The analysis time for each sample was 5.5 min. Our UPLC/MS/MS method demonstrated satisfactory validation results in terms of selectivity, sensitivity, matrix effect, linearity, extraction efficiency, intra- and inter-day precision, accuracy and autosampler stability. The method was applied for the clinical profiling of matched pairs of cancerous and normal colon mucosae obtained from eight colorectal cancer patients. Endogenous levels of AA and selected eicosanoids such as prostaglandin E(2) (PGE(2)), prostacyclin (PGI(2)) [assayed as its stable hydrolytic product 6-keto-prostaglandin(1α) (6-k PGF(1α))] and 12-hydroxy-5Z,8Z,10E,14Z-eicosatetraenoic acid (12-HETE) were found to be significantly different (p <0.05; paired t-test) between cancerous and normal mucosae. Copyright © 2011 John Wiley & Sons, Ltd.

Chemically Activated Formation of Organic Acids in Reactions of the Criegee Intermediate with Aldehydes and Ketones

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

Jalan, Amrit; Allen, Joshua W.; Green, William H.

Reactions of the Criegee intermediate (CI, .CH2OO.) are important in atmospheric ozonolysis models. In this work, we compute the rates for reactions between .CH2OO. and HCHO, CH3CHO and CH3COCH3 leading to the formation of secondary ozonides (SOZ) and organic acids. Relative to infinitely separated reactants, the SOZ in all three cases is found to be 48–51 kcal mol-1 lower in energy, formed via 1,3- cycloaddition of .CH2OO. across the CQO bond. The lowest energy pathway found for SOZ decomposition is intramolecular disproportionation of the singlet biradical intermediate formed from cleavage of the O–O bond to form hydroxyalkyl esters. These hydroxyalkylmore » esters undergo concerted decomposition providing a low energy pathway from SOZ to acids. Geometries and frequencies of all stationary points were obtained using the B3LYP/MG3S DFT model chemistry, and energies were refined using RCCSD(T)-F12a/cc-pVTZ-F12 single-point calculations. RRKM calculations were used to obtain microcanonical rate coefficients (k(E)) and the reservoir state method was used to obtain temperature and pressure dependent rate coefficients (k(T, P)) and product branching ratios. At atmospheric pressure, the yield of collisionally stabilized SOZ was found to increase in the order HCHO o CH3CHO o CH3COCH3 (the highest yield being 10-4 times lower than the initial .CH2OO. concentration). At low pressures, chemically activated formation of organic acids (formic acid in the case of HCHO and CH3COCH3, formic and acetic acid in the case of CH3CHO) was found to be the major product channel in agreement with recent direct measurements. Collisional energy transfer parameters and the barrier heights for SOZ reactions were found to be the most sensitive parameters determining SOZ and organic acid yield.« less

Quantitative Determination of Δ9-THC, CBG, CBD, Their Acid Precursors and Five Other Neutral Cannabinoids by UHPLC-UV-MS.

PubMed

Wang, Yan-Hong; Avula, Bharathi; ElSohly, Mahmoud A; Radwan, Mohamed M; Wang, Mei; Wanas, Amira S; Mehmedic, Zlatko; Khan, Ikhlas A

2018-03-01

Cannabinoids are a group of terpenophenolic compounds in the medicinal plant Cannabis sativa (Cannabaceae family). Cannabigerolic acid, Δ 9 -tetrahydrocannabinolic acid A, cannabidiolic acid, Δ 9 -tetrahydrocannabinol, cannabigerol, cannabidiol, cannabichromene, and tetrahydrocannabivarin are major metabolites in the classification of different strains of C. sativa . Degradation or artifact cannabinoids cannabinol, cannabicyclol, and Δ 8 -tetrahydrocannabinol are formed under the influence of heat and light during processing and storage of the plant sample. An ultrahigh-performance liquid chromatographic method coupled with photodiode array and single quadruple mass spectrometry detectors was developed and validated for quantitative determination of 11 cannabinoids in different C. sativa samples. Compounds 1:  - 11: were baseline separated with an acetonitrile (with 0.05% formic acid) and water (with 0.05% formic acid) gradient at a flow rate of 0.25 mL/min on a Waters Cortec UPLC C18 column (100 mm × 2.1 mm I. D., 1.6 µm). The limits of detection and limits of quantitation of the 11 cannabinoids were below 0.2 and 0.5 µg/mL, respectively. The relative standard deviation for the precision test was below 2.4%. A mixture of acetonitrile and methanol (80 : 20, v / v ) was proven to be the best solvent system for the sample preparation. The recovery of all analytes was in the range of 97 - 105%. A total of 32 Cannabis samples including hashish, leaves, and flower buds were analyzed. Georg Thieme Verlag KG Stuttgart · New York.

[[Chiral separation of five arylpropionic acid drugs and determination of their enantiomers in pharmaceutical preparations by reversed-phase high performance liquid chromatography with cellulose-tris-(4-methylbenzoate) stationary phase

PubMed

Luo, An; Wan, Qiang; Fan, Huajun; Chen, Zhi; Wu, Xuehao; Huang, Xiaowen; Zang, Linquan

2014-09-01

Chromatographic behaviors for enantiomeric separation of arylpropionic acid drugs were systematically developed by reversed phase-high performance liquid chromatography (RP-HPLC) using cellulose-tris-(4-methylbenzoate) (CTMB) as chiral stationary phase (CSP). The effects of the composition of the mobile phase, additives and temperature on chiral separation of flurbiprofen, pranoprofen, naproxen, ibuprofen and loxoprofen were further investigated. The enantiomers had been successfully separated on CSP of CTMB by the mobile phase of methanol-0.1% (v/v) formic acid except naproxen by acetonitrile-0.1% (v/v) formic acid at 25 °C. The mechanisms of the racemic resolution for the above mentioned five drugs are discussed thermodynamically and structurally. The resolutions between respective enantiomers for arylpropionic acid drugs on CTMB had significant differences due to their chromatographic behaviors. The order of resolutions ranked pranoprofen, loxoprofen, flurbiprofen, ibuprofen and naproxen. The method established has been successfully applied to the determination of the enantiomers of the five drugs in commercial preparations under the optimized conditions. It proved that the method is simple, reliable and accurate.

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. Copyright © 2016 Elsevier Ltd. All rights reserved.

A validated UHPLC method for the determination of caffeoylquinic and di-caffeoylquinic acids in green coffee extracts using an RP-Amide fused-core column.

PubMed

Fibigr, Jakub; Majorová, Michaela; Kočová Vlčková, Hana; Solich, Petr; Šatínský, Dalibor

2018-03-20

The presented work describes the development and validation of a rapid UHPLC-UV method using a fused core particle column with an RP-Amide stationary phase for the separation and quantitative analysis of caffeoylquinic and di-caffeoylquinic acids in green coffee extracts. Three caffeoylquinic acids (3-caffeoylquinic acid, 4-caffeoylquinic acid, and 5-caffeoylquinic acid) and two di-caffeoylquinic acids (1,3-di-caffeoylquinic acid, and 3,5-di-caffeoylquinic acid) were separated and analyzed in 8 min. That was possible due to the unique selectivity of the RP-Amide stationary phase for the analyzed acids. The retention behavior of all analytes under different compositions of the mobile phase on different columns was evaluated in this study. The optimal chromatographic separation was performed using an Ascentis Express RP-Amide (100 × 2.1 mm) fused-core column with a particle size of 2.7 μm at a temperature of 30 °C. For validation of the newly developed method, acetonitrile was used as mobile phase B and 5% formic acid, filtrated through a 0.22 μm filter, was used as mobile phase A. They were delivered at a flow rate of 0.9 mL min -1 according to the elution gradient program. The detection wavelength was set at 325 nm. A solid-liquid extraction with a solution of methanol and a 5% water solution of formic acid (25 + 75 v/v) using an ultrasonic bath was chosen for the preparation of the available commercial samples of food supplements containing a green coffee extract. Recoveries for all analyzed acids were 98.2-101.0% and the relative standard deviation ranged from 0.3% to 1.4% for intra-day and from 0.3% to 3.0% for inter-day repeatability. The limits of detection were in the range of 0.30-0.53 μg mL -1 . Copyright © 2018. Published by Elsevier B.V.

Microwave-assisted organic acid extraction of lignin from bamboo: structure and antioxidant activity investigation.

PubMed

Li, Ming-Fei; Sun, Shao-Ni; Xu, Feng; Sun, Run-Cang

2012-10-01

Microwave-assisted extraction in organic acid aqueous solution (formic acid/acetic acid/water, 3/5/2, v/v/v) was applied to isolate lignin from bamboo. Additionally, the structural features of the extracted lignins were thoroughly investigated in terms of C₉ formula, molecular weight distribution, FT-IR, (1)H NMR and HSQC spectroscopy. It was found that with an increase in the severity of microwave-assisted extraction, there was an increase of phenolic hydroxyl content in the lignin. In addition, an increase of the severity resulted in a decrease of the bound carbohydrate content as well as molecular weight of the lignin. Antioxidant activity investigation indicated that the radical scavenging index of the extracted lignins (0.35-1.15) was higher than that of BHT (0.29) but lower than that of BHA (3.85). The results suggested that microwave-assisted organic acid extraction provides a promising way to prepare lignin from bamboo with good antioxidant activity for potential application in the food industry. Copyright © 2012 Elsevier Ltd. All rights reserved.

Hydrophilic interaction liquid chromatography-mass spectrometry of (lyso)phosphatidic acids, (lyso)phosphatidylserines and other lipid classes.

PubMed

Cífková, Eva; Hájek, Roman; Lísa, Miroslav; HolĿapek, Michal

2016-03-25

The goal of this work is a systematic optimization of hydrophilic interaction liquid chromatography (HILIC) separation of acidic lipid classes (namely phosphatidic acids-PA, lysophosphatidic acids-LPA, phosphatidylserines-PS and lysophosphatidylserines-LPS) and other lipid classes under mass spectrometry (MS) compatible conditions. The main parameters included in this optimization are the type of stationary phases used in HILIC, pH of the mobile phase, the type and concentration of mobile phase additives. Nine HILIC columns with different chemistries (unmodified silica, modified silica using diol, 2-picolylamine, diethylamine and 1-aminoanthracene and hydride silica) are compared with the emphasis on peak shapes of acidic lipid classes. The optimization of pH is correlated with the theoretical calculation of acidobasic equilibria of studied lipid classes. The final method using the hydride column, pH 4 adjusted by formic acid and the gradient of acetonitrile and 40 mmol/L of aqueous ammonium formate provides good peak shapes for all analyzed lipid classes including acidic lipids. This method is applied for the identification of lipids in real samples of porcine brain and kidney extracts. Copyright © 2016 Elsevier B.V. All rights reserved.

N-doped carbon dots derived from bovine serum albumin and formic acid with one- and two-photon fluorescence for live cell nuclear imaging.

PubMed

Tan, Mingqian; Li, Xintong; Wu, Hao; Wang, Beibei; Wu, Jing

2015-12-01

Carbon dots with both one- and two-photon fluorescence have drawn great attention for biomedical imaging. Herein, nitrogen-doped carbon dots were facilely developed by one-pot hydrothermal method using bovine serum albumin and formic acid as carbon sources. They are highly water-soluble with strong fluorescence when excited with ultraviolet or near infrared light. The carbon dots have a diameter of ~8.32 nm and can emit strong two-photon induced fluorescence upon excitation at 750 nm with a femtosecond laser. X-ray photoelectron spectrometer analysis revealed that the carbon dots contained three components, C, N and O, corresponding to the peak at 285, 398 and 532 eV, respectively. The Fourier-transform infrared spectroscopy analysis revealed that there are carboxyl and carboxylic groups on the surface, which allowed further linking of functional molecules. pH stability study demonstrated that the carbon dots are able to be used in a wide range of pH values. The fluorescence mechanism is also discussed in this study. Importantly, these carbon dots are biocompatible and highly photostable, which can be directly applied for both one- and two-photon living cell imaging. After proper surface functionalization with TAT peptide, they can be used as fluorescent probes for live cell nuclear-targeted imaging. Copyright © 2015 Elsevier B.V. All rights reserved.

A study of organic acid production in contrasts between two phosphate solubilizing fungi: Penicillium oxalicum and Aspergillus niger

NASA Astrophysics Data System (ADS)

Li, Zhen; Bai, Tongshuo; Dai, Letian; Wang, Fuwei; Tao, Jinjin; Meng, Shiting; Hu, Yunxiao; Wang, Shimei; Hu, Shuijin

2016-04-01

Phosphate solubilizing fungi (PSF) have huge potentials in enhancing release of phosphorus from fertilizer. Two PSF (NJDL-03 and NJDL-12) were isolated and identified as Penicillium oxalicum and Aspergillus niger respectively in this study. The quantification and identification of organic acids were performed by HPLC. Total concentrations of organic acids secreted by NJDL-03 and NJDL-12 are ~4000 and ~10,000 mg/L with pH values of 3.6 and 2.4 respectively after five-days culture. Oxalic acid dominates acidity in the medium due to its high concentration and high acidity constant. The two fungi were also cultured for five days with the initial pH values of the medium varied from 6.5 to 1.5. The biomass reached the maximum when the initial pH values are 4.5 for NJDL-03 and 2.5 for NJDL-12. The organic acids for NJDL-12 reach the maximum at the initial pH = 5.5. However, the acids by NJDL-03 continue to decrease and proliferation of the fungus terminates at pH = 2.5. The citric acid production increases significantly for NJDL-12 at acidic environment, whereas formic and oxalic acids decrease sharply for both two fungi. This study shows that NJDL-12 has higher ability in acid production and has stronger adaptability to acidic environment than NJDL-03.

A study of organic acid production in contrasts between two phosphate solubilizing fungi: Penicillium oxalicum and Aspergillus niger

PubMed Central

Li, Zhen; Bai, Tongshuo; Dai, Letian; Wang, Fuwei; Tao, Jinjin; Meng, Shiting; Hu, Yunxiao; Wang, Shimei; Hu, Shuijin

2016-01-01

Phosphate solubilizing fungi (PSF) have huge potentials in enhancing release of phosphorus from fertilizer. Two PSF (NJDL-03 and NJDL-12) were isolated and identified as Penicillium oxalicum and Aspergillus niger respectively in this study. The quantification and identification of organic acids were performed by HPLC. Total concentrations of organic acids secreted by NJDL-03 and NJDL-12 are ~4000 and ~10,000 mg/L with pH values of 3.6 and 2.4 respectively after five-days culture. Oxalic acid dominates acidity in the medium due to its high concentration and high acidity constant. The two fungi were also cultured for five days with the initial pH values of the medium varied from 6.5 to 1.5. The biomass reached the maximum when the initial pH values are 4.5 for NJDL-03 and 2.5 for NJDL-12. The organic acids for NJDL-12 reach the maximum at the initial pH = 5.5. However, the acids by NJDL-03 continue to decrease and proliferation of the fungus terminates at pH = 2.5. The citric acid production increases significantly for NJDL-12 at acidic environment, whereas formic and oxalic acids decrease sharply for both two fungi. This study shows that NJDL-12 has higher ability in acid production and has stronger adaptability to acidic environment than NJDL-03. PMID:27126606

Simple and Rapid Determination of Ferulic Acid Levels in Food and Cosmetic Samples Using Paper-Based Platforms

PubMed Central

Tee-ngam, Prinjaporn; Nunant, Namthip; Rattanarat, Poomrat; Siangproh, Weena; Chailapakul, Orawon

2013-01-01

Ferulic acid is an important phenolic antioxidant found in or added to diet supplements, beverages, and cosmetic creams. Two designs of paper-based platforms for the fast, simple and inexpensive evaluation of ferulic acid contents in food and pharmaceutical cosmetics were evaluated. The first, a paper-based electrochemical device, was developed for ferulic acid detection in uncomplicated matrix samples and was created by the photolithographic method. The second, a paper-based colorimetric device was preceded by thin layer chromatography (TLC) for the separation and detection of ferulic acid in complex samples using a silica plate stationary phase and an 85:15:1 (v/v/v) chloroform: methanol: formic acid mobile phase. After separation, ferulic acid containing section of the TLC plate was attached onto the patterned paper containing the colorimetric reagent and eluted with ethanol. The resulting color change was photographed and quantitatively converted to intensity. Under the optimal conditions, the limit of detection of ferulic acid was found to be 1 ppm and 7 ppm (S/N = 3) for first and second designs, respectively, with good agreement with the standard HPLC-UV detection method. Therefore, these methods can be used for the simple, rapid, inexpensive and sensitive quantification of ferulic acid in a variety of samples. PMID:24077320

Organic acids for control of Salmonella in different feed materials

PubMed Central

2013-01-01

Background Salmonella control in animal feed is important in order to protect animal and public health. Organic acids is one of the control measures used for treatment of Salmonella contaminated feed or feed ingredients. In the present study, the efficacy of formic acid (FA) and different blends of FA, propionic acid (PA) and sodium formate (SF) was investigated. Four Salmonella strains isolated from feed were assayed for their acid tolerance. Also, the effect of lower temperatures (5°C and 15°C) compared to room temperature was investigated in rape seed and soybean meal. Results The efficacy of acid treatments varied significantly between different feed materials. The strongest reduction was seen in pelleted and compound mash feed (2.5 log10 reduction) followed by rapeseed meal (1 log10 reduction) after 5 days exposure. However, in soybean meal the acid effects were limited (less than 0.5 log10 reduction) even after several weeks’ exposure. In all experiments the survival curves showed a concave shape, with a fast initial death phase followed by reduction at a slower rate during the remaining time of the experiment. No difference in Salmonella reduction was observed between FA and a blend of FA and PA, whereas a commercial blend of FA and SF (Amasil) was slightly more efficacious (0.5-1 log10 reduction) than a blend of FA and PA (Luprocid) in compound mash feed. The Salmonella Infantis strain was found to be the most acid tolerant strain followed by, S. Putten, S. Senftenberg and S. Typhimurium. The tolerance of the S. Infantis strain compared with the S. Typhimurium strain was statistically significant (p<0.05). The lethal effect of FA on the S. Typhimurium strain and the S. Infantis strain was lower at 5°C and 15°C compared to room temperatures. Conclusions Acid treatment of Salmonella in feed is a matter of reducing the number of viable bacterial cells rather than eliminating the organism. Recommendations on the use of acids for controlling Salmonella in

Organic acids for control of Salmonella in different feed materials.

PubMed

Koyuncu, Sevinc; Andersson, Mats Gunnar; Löfström, Charlotta; Skandamis, Panagiotis N; Gounadaki, Antonia; Zentek, Jürgen; Häggblom, Per

2013-04-18

Salmonella control in animal feed is important in order to protect animal and public health. Organic acids is one of the control measures used for treatment of Salmonella contaminated feed or feed ingredients. In the present study, the efficacy of formic acid (FA) and different blends of FA, propionic acid (PA) and sodium formate (SF) was investigated. Four Salmonella strains isolated from feed were assayed for their acid tolerance. Also, the effect of lower temperatures (5°C and 15°C) compared to room temperature was investigated in rape seed and soybean meal. The efficacy of acid treatments varied significantly between different feed materials. The strongest reduction was seen in pelleted and compound mash feed (2.5 log10 reduction) followed by rapeseed meal (1 log10 reduction) after 5 days exposure. However, in soybean meal the acid effects were limited (less than 0.5 log10 reduction) even after several weeks' exposure. In all experiments the survival curves showed a concave shape, with a fast initial death phase followed by reduction at a slower rate during the remaining time of the experiment.No difference in Salmonella reduction was observed between FA and a blend of FA and PA, whereas a commercial blend of FA and SF (Amasil) was slightly more efficacious (0.5-1 log10 reduction) than a blend of FA and PA (Luprocid) in compound mash feed. The Salmonella Infantis strain was found to be the most acid tolerant strain followed by, S. Putten, S. Senftenberg and S. Typhimurium. The tolerance of the S. Infantis strain compared with the S. Typhimurium strain was statistically significant (p<0.05). The lethal effect of FA on the S. Typhimurium strain and the S. Infantis strain was lower at 5°C and 15°C compared to room temperatures. Acid treatment of Salmonella in feed is a matter of reducing the number of viable bacterial cells rather than eliminating the organism. Recommendations on the use of acids for controlling Salmonella in feed should take into account the

Detection of high concentrations of organic acids in fish emulsion and their role in pathogen or disease suppression.

PubMed

Abbasi, Pervaiz A; Lazarovits, George; Jabaji-Hare, Suha

2009-03-01

Fish emulsion (FE) added to a sandy-loam soil at 1 and 2% rates reduced the viability of Verticillium dahliae microsclerotia by 39 and 74% in 1 day, 87 and 98% in 3 days, and 95 and 99% in 6 days, respectively. The immediate kill of microsclerotia indicated that FE contains toxic substances. We found in FE high concentrations (400 mmol/liter) of organic acids, including some known toxicants. Glycolic, acetic, formic, n-butyric, and propionic acids were the major organic acids detected in FE at the proportions of 52.5, 26.9, 7.9, 7.2, and 4.7%, respectively. In solution assays, the viability of V. dahliae microsclerotia treated for 24 h in 1, 2, 5, and 10% FE (pH 3.6 to 3.0) or a mixture of organic acids (pH 4.1 to 3.9) equivalent to the proportions in FE was reduced by 74, 94, 97, and 99% or 81, 91, 98, and 99%, respectively. The viability of microsclerotia was increased when the treatment solutions were buffered to pH 6.0. The organic acids mixtures and formic (0.025%) and acetic (0.1%) acids were toxic to Pythium ultimum. A mixture of organic acids (1, 2, and 4%) provided immediate protection of cucumber seedlings from damping-off in P. ultimum-infested muck and sandy-loam soils but not in peat-based mix. FE (1 and 2%) provided immediate protection of cucumber seedlings from damping-off in an infested muck soil, and disease protection was consistent when planting was delayed for 7, 14, and 28 days after adding FE. FE (1, 2, and 4%) did not provide immediate protection of cucumber seedlings from damping-off in a P. ultimum-infested peat-based mix; however, disease suppression was evident when planting was delayed for 7, 14, and 21 days after adding FE. Real-time polymerase chain reaction analyses of the peat-based mix indicated that the P. ultimum populations in the FE-amended mix declined over time. This study suggests that these organic acids in FE played a major role in pathogen or disease suppression, depending on the soil and substrate.

Usefulness of organic acid produced by Exiguobacterium sp. 12/1 on neutralization of alkaline wastewater.

PubMed

Kulshreshtha, Niha Mohan; Kumar, Anil; Bisht, Gopal; Pasha, Santosh; Kumar, Rita

2012-01-01

The aim of this study was to investigate the role of organic acids produced by Exiguobacterium sp. strain 12/1 (DSM 21148) in neutralization of alkaline wastewater emanated from beverage industry. This bacterium is known to be able to grow in medium of pH as high as pH 12.0 and to neutralize alkaline industrial wastewater from pH 12.0 to pH 7.5. The initial investigation on the type of functional groups present in medium, carried out using FT-IR spectroscopy, revealed the presence of peaks corresponding to carbonyl group and hydroxyl group, suggesting the release of carboxylic acid or related metabolic product(s). The identification of specific carboxylic group, carried out using RP-HPLC, revealed the presence of a single peak in the culture supernatant with retention time most similar to formic acid. The concentration of acid produced on different carbon sources was studied as a function of time. Although acid was present in same final concentration, the rate of acid production was highest in case of medium supplemented with sucrose followed by fructose and glucose. The knowledge of metabolic products of the bacterium can be considered as a first step towards realization of its potential for large-scale bioremediation of alkaline wastewater from beverage industry.

Usefulness of Organic Acid Produced by Exiguobacterium sp. 12/1 on Neutralization of Alkaline Wastewater

PubMed Central

Kulshreshtha, Niha Mohan; Kumar, Anil; Bisht, Gopal; Pasha, Santosh; Kumar, Rita

2012-01-01

The aim of this study was to investigate the role of organic acids produced by Exiguobacterium sp. strain 12/1 (DSM 21148) in neutralization of alkaline wastewater emanated from beverage industry. This bacterium is known to be able to grow in medium of pH as high as pH 12.0 and to neutralize alkaline industrial wastewater from pH 12.0 to pH 7.5. The initial investigation on the type of functional groups present in medium, carried out using FT-IR spectroscopy, revealed the presence of peaks corresponding to carbonyl group and hydroxyl group, suggesting the release of carboxylic acid or related metabolic product(s). The identification of specific carboxylic group, carried out using RP-HPLC, revealed the presence of a single peak in the culture supernatant with retention time most similar to formic acid. The concentration of acid produced on different carbon sources was studied as a function of time. Although acid was present in same final concentration, the rate of acid production was highest in case of medium supplemented with sucrose followed by fructose and glucose. The knowledge of metabolic products of the bacterium can be considered as a first step towards realization of its potential for large-scale bioremediation of alkaline wastewater from beverage industry. PMID:22666107

[Studies on interaction of acid-treated nanotube titanic acid and amino acids].

PubMed

Zhang, Huqin; Chen, Xuemei; Jin, Zhensheng; Liao, Guangxi; Wu, Xiaoming; Du, Jianqiang; Cao, Xiang

2010-06-01

Nanotube titanic acid (NTA) has distinct optical and electrical character, and has photocatalysis character. In accordance with these qualities, NTA was treated with acid so as to enhance its surface activity. Surface structures and surface groups of acid-treated NTA were characterized and analyzed by Transmission Electron Microscope (TEM) and Fourier Transform Infrared Spectrometry (FT-IR). The interaction between acid-treated NTA and amino acids was investigated. Analysis results showed that the lengths of acid-treated NTA became obviously shorter. The diameters of nanotube bundles did not change obviously with acid-treating. Meanwhile, the surface of acid-treated NTA was cross-linked with carboxyl or esterfunction. In addition, acid-treated NTA can catch amino acid residues easily, and then form close combination.

Microgravity Compatible Reagentless Instrumentation for Detection of Dissolved Organic Acids and Alcohols in Potable Water

NASA Technical Reports Server (NTRS)

Akse, James R.; Jan, Darrell L. (Technical Monitor)

2002-01-01

The Organic Acid and Alcohol Monitor (OAAM) program has resulted in the successful development of a computer controlled prototype analyzer capable of accurately determining aqueous organic acids and primary alcohol concentrations over a large dynamic range with high sensitivity. Formic, acetic, and propionic acid were accurately determined at concentrations as low as 5 to 10 micrograms/L in under 20 minutes, or as high as 10 to 20 mg/L in under 30 minutes. Methanol, ethanol, and propanol were determined at concentrations as low as 20 to 100 micrograms/L, or as high as 10 mg/L in under 30 minutes. Importantly for space based application, the OAAM requires no reagents or hazardous chemicals to perform these analyses needing only power, water, and CO2 free purge gas. The OAAM utilized two membrane processes to segregate organic acids from interfering ions. The organic acid concentration was then determined based upon the conductiometric signal. Separation of individual organic acids was accomplished using a chromatographic column. Alcohols are determined in a similar manner after conversion to organic acids by sequential biocatalytic and catalytic oxidation steps. The OAAM was designed to allow the early diagnosis of under performing or failing sub-systems within the Water Recovery System (WRS) baselined for the International Space Station (ISS). To achieve this goal, several new technologies were developed over the course of the OAAM program.

Characteristic chromatographic fingerprint study of short-chain fatty acids in human milk, infant formula, pure milk and fermented milk by gas chromatography-mass spectrometry.

PubMed

Jiang, Zhenzuo; Liu, Yanan; Zhu, Yan; Yang, Jing; Sun, Lili; Chai, Xin; Wang, Yuefei

2016-09-01

Human milk, infant formula, pure milk and fermented milk as food products or dietary supplements provide a range of nutrients required to both infants and adults. Recently, a growing body of evidence has revealed the beneficial roles of short-chain fatty acids (SCFAs), a subset of fatty acids produced from the fermentation of dietary fibers by gut microbiota. The objective of this study was to establish a chromatographic fingerprint technique to investigate SCFAs in human milk and dairy products by gas chromatography coupled with mass spectrometry. The multivariate method for principal component analysis assessed differences between milk types. Human milk, infant formula, pure milk and fermented milk were grouped independently, mainly because of differences in formic acid, acetic acid, propionic acid and hexanoic acid levels. This method will be important for the assessment of SCFAs in human milk and various dairy products.

Surface Engineering of a Supported PdAg Catalyst for Hydrogenation of CO2 to Formic Acid: Elucidating the Active Pd Atoms in Alloy Nanoparticles.

PubMed

Mori, Kohsuke; Sano, Taiki; Kobayashi, Hisayoshi; Yamashita, Hiromi

2018-06-22

The hydrogenation of carbon dioxide (CO 2 ) to formic acid (FA; HCOOH), a renewable hydrogen storage material, is a promising means of realizing an economical CO 2 -mediated hydrogen energy cycle. The development of reliable heter-ogeneous catalysts is an urgent yet challenging task associated with such systems, although precise catalytic site design protocols are still lacking. In the present study, we demonstrate that PdAg alloy nanoparticles (NPs) supported on TiO 2 promote the efficient selective hydrogenation of CO 2 to give FA even under mild reaction conditions (2.0 MPa, 100 °C). Specimens made using surface engineering with atomic precision reveal a strong correlation between increased cata-lytic activity and decreased electron density of active Pd atoms resulting from a synergistic effect of alloying with Ag atoms. The isolated and electronically promoted surface-exposed Pd atoms in Pd@Ag alloy NPs exhibit a maximum turnover number of 14,839 based on the quantity of surface Pd atoms, which represents a more than ten-fold increase compared to the activity of monometallic Pd/TiO 2 . Kinetic and density functional theory (DFT) calculations show that the attack on the C atom in HCO 3 - by a dissociated H atom over an active Pd site is the rate-determining step during this reaction, and this step is boosted by PdAg alloy NPs having a low Pd/Ag ratio.

A rapid method for the simultaneous determination of L-ascorbic acid and acetylsalicylic acid in aspirin C effervescent tablet by ultra performance liquid chromatography-tandem mass spectrometry

NASA Astrophysics Data System (ADS)

Wabaidur, Saikh Mohammad; Alothman, Zeid Abdullah; Khan, Mohammad Rizwan

2013-05-01

In present study, a rapid and sensitive method using ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was developed for the simultaneous determination of L-ascorbic acid and acetylsalicylic acid in aspirin C effervescent tablet. The optimum chromatographic separation was carried out on a reversed phase Waters® Acquity UPLC BEH C18 column (1.7 μm particle size, 100 mm × 2.1 mm ID) with an isocratic elution profile and mobile phase consisting of 0.1% formic acid in water and acetonitrile (75:25, v/v, pH 3.5) at flow rate of 0.5 mL min-1. The influences of mobile phase composition, flow rate and pH on chromatographic resolution were investigated. The total chromatographic analysis time was as short as 2 min with excellent resolution. Detection and quantification of the target compounds were carried out with a triple quadrupole mass spectrometer using negative electrospray ionization (ESI) and multiple reaction monitoring (MRM) modes. The performance of the method was evaluated and very low limits of detection less than 0.09 μg g-1, excellent coefficient correlation (r2 > 0.999) with liner range over a concentration range of 0.1-1.0 μg g-1 for both L-ascorbic acid and acetylsalicylic acid, and good intraday and interday precisions (relative standard deviations (R.S.D.) <3%), were obtained. Comparison of system performance with traditional liquid chromatography-photo diode array detector (HPLC-PDA) was made with respect to analysis time, sensitivity, linearity and precisions. The proposed UPLC-MS/MS method was found to be reproducible and appropriate for quantitative analysis of L-ascorbic acid and acetylsalicylic acid in aspirin C effervescent tablet.

Determination of Acid Herbicides Using Modified QuEChERS with Fast Switching ESI(+)/ESI(-) LC-MS/MS.

PubMed

Sack, Chris; Vonderbrink, John; Smoker, Michael; Smith, Robert E

2015-11-04

A method for the determination of 35 acid herbicides in food matrices was developed, validated, and implemented. It utilizes a modified QuEChERS extraction procedure coupled with quantitation by liquid chromatography tandem mass spectrometry (LC-MS/MS). The acid herbicides analyzed are all organic carboxylic acids, including the older chlorophenoxy acid herbicides such as 2,4-dichlorophenoxyacetic acid (2,4-D), dicamba, 4-chlorophenoxyacetic acid (4-CPA), quinclorac, and many of the newer imidazolinone herbicides such as imazethapyr and imazaquin. In the procedure, 10 mL of water is added to 5 g of sample and then extracted with 1% formic acid in acetonitrile for 1 min. The acetonitrile phase is salted out of the extract by adding sodium chloride and magnesium sulfate, followed by centrifugation. The acetonitrile is diluted 1:1 with water to enable quantitation by LC-MS/MS using fast switching between positive and negative electrospray ionization modes. The average recoveries for all the compounds except aminocyclopyrachlor were 95% with a precision of 8%. The method detection limits for all residues were less than 10 ng/g, and the correlation coefficients for the calibration curves was greater than 0.99 for all but two compounds tested. The method was used successfully for the quantitation of acid herbicides in the FDA's total diet study. The procedure proved to be accurate, precise, linear, sensitive, and rugged.

Lactobacilli Inactivate Chlamydia trachomatis through Lactic Acid but Not H2O2

PubMed Central

Gong, Zheng; Luna, Yesmin; Yu, Ping; Fan, Huizhou

2014-01-01

Lactobacillus species dominate the microbiome in the lower genital tract of most reproductive-age women. Producing lactic acid and H2O2, lactobacilli are believed to play an important role in prevention of colonization by and growth of pathogens. However, to date, there have been no reported studies characterizing how lactobacilli interact with Chlamydia trachomatis, a leading sexually transmitted bacterium. In this report, we demonstrate inactivation of C. trachomatis infectivity by culture media conditioned by Lactobacillus crispatus, L. gasseri and L. jensenii, known to be dominating organisms in the human vaginal microbiome. Lactobacillus still cultures produced lactic acid, leading to time- and concentration-dependent killing of C. trachomatis. Neutralization of the acidic media completely reversed chlamydia killing. Addition of lactic acid into Lactobacillus-unconditioned growth medium recapitulated the chlamydiacidal activity of conditioned media. The H2O2 concentrations in the still cultures were found to be comparable to those reported for the cervicovaginal fluid, but insufficient to inactivate chlamydiae. Aeration of Lactobacillus cultures by shaking markedly induced H2O2 production, but strongly inhibited Lactobacillus growth and lactic acid production, and thus severely affected acidification, leading to significantly reduced chlamydiacidal efficiency. These observations indicate lactobacilli inactivate chlamydiae primarily through maintaining acidity in a relatively hypoxic environment in the vaginal lumen with limited H2O2, which is consistent with the notion that women with higher vaginal pH are more prone to sexually transmitted C. trachomatis infection. In addition to lactic acid, formic acid and acetic acid also exhibited potent chlamydiacidal activities. Taken together, our findings imply that lowering the vaginal pH through engineering of the vaginal microbiome and other means will make women less susceptible to C. trachomatis infection. PMID

Microbial degradation of poly(amino acid)s.

PubMed

Obst, Martin; Steinbüchel, Alexander

2004-01-01

Natural poly(amino acid)s are a group of poly(ionic) molecules (ionomers) with various biological functions and putative technical applications and play, therefore, an important role both in nature and in human life. Because of their biocompatibility and their synthesis from renewable resources, poly(amino acid)s may be employed for many different purposes covering a broad spectrum of medical, pharmaceutical, and personal care applications as well as the domains of agriculture and of environmental applications. Biodegradability is one important advantage of naturally occurring poly(amino acid)s over many synthetic polymers. The intention of this review is to give an overview about the enzyme systems catalyzing the initial steps in poly(amino acid) degradation. The focus is on the naturally occurring poly(amino acid)s cyanophycin, poly(epsilon-L-lysine) and poly(gamma-glutamic acid); but biodegradation of structurally related synthetic polyamides such as poly(aspartic acid) and nylons, which are known from various technical applications, is also included.

Urea free and more efficient sample preparation method for mass spectrometry based protein identification via combining the formic acid-assisted chemical cleavage and trypsin digestion.

PubMed

Wu, Shuaibin; Yang, Kaiguang; Liang, Zhen; Zhang, Lihua; Zhang, Yukui

2011-10-30

A formic acid (FA)-assisted sample preparation method was presented for protein identification via mass spectrometry (MS). Detailedly, an aqueous solution containing 2% FA and dithiothreitol was selected to perform protein denaturation, aspartic acid (D) sites cleavage and disulfide linkages reduction simultaneously at 108°C for 2h. Subsequently, FA wiped off via vacuum concentration. Finally, iodoacetamide (IAA) alkylation and trypsin digestion could be performed ordinally. A series of model proteins (BSA, β-lactoglobulin and apo-Transferrin) were treated respectively using such method, followed by matrix-assisted laser desorption ionization-time-of-flight mass spectrometry (MALDI-TOF MS) analysis. The identified peptide number was increased by ∼ 80% in comparison with the conventional urea-assisted sample preparation method. Moreover, BSA identification was achieved efficiently down to femtomole (25 ± 0 sequence coverage and 16 ± 1 peptides) via such method. In contrast, there were not peptides identified confidently via the urea-assisted method before desalination via the C18 zip tip. The absence of urea in this sample preparation method was an advantage for the more favorable digestion and MALDI-TOF MS analysis. The performances of two methods for the real sample (rat liver proteome) were also compared, followed by a nanoflow reversed-phase liquid chromatography with electrospray ionization tandem mass spectrometry system analysis. As a result, 1335 ± 43 peptides were identified confidently (false discovery rate <1%) via FA-assisted method, corresponding to 295 ± 12 proteins (of top match=1 and requiring 2 unique peptides at least). In contrast, there were only 1107 ± 16 peptides (corresponding to 231 ± 10 proteins) obtained from the conventional urea-assisted method. It was serving as a more efficient protein sample preparation method for researching specific proteomes better, and providing assistance to develop other proteomics analysis methods

Ketonization of levulinic acid and γ-valerolactone to hydrocarbon fuel precursors

DOE PAGES

Lilga, Michael A.; Padmaperuma, Asanga B.; Auberry, Deanna L.; ...

2017-06-21

We studied a new process for direct conversion of either levulinic acid (LA) or γ-valerolactone (GVL) to hydrocarbon fuel precursors. The process involves passing an aqueous solution of LA or GVL containing a reducing agent, such as ethylene glycol or formic acid, over a ketonization catalyst at 380–400 °C and atmospheric pressure to form a biphasic liquid product. The organic phase is significantly oligomerized and deoxygenated and comprises a complex mixture of open-chain alkanes and olefins, aromatics, and low concentrations of ketones, alcohols, ethers, and carboxylates or lactones. Carbon content in the aqueous phase decreases with decreasing feed rate; themore » aqueous phase can be reprocessed through the same catalyst to form additional organic oils to improve carbon yield. Catalysts are readily regenerated to restore initial activity. Furthermore, the process might be valuable in converting cellulosics to biorenewable gasoline, jet, and diesel fuels as a means to decrease petroleum use and decrease greenhouse gas emissions.« less

The Acid-Base Titration of a Very Weak Acid: Boric Acid

ERIC Educational Resources Information Center

Celeste, M.; Azevedo, C.; Cavaleiro, Ana M. V.

2012-01-01

A laboratory experiment based on the titration of boric acid with strong base in the presence of d-mannitol is described. Boric acid is a very weak acid and direct titration with NaOH is not possible. An auxiliary reagent that contributes to the release of protons in a known stoichiometry facilitates the acid-base titration. Students obtain the…

Omega-3 fatty acids: new insights into the pharmacology and biology of docosahexaenoic acid, docosapentaenoic acid, and eicosapentaenoic acid.

PubMed

Davidson, Michael H

2013-12-01

Fish oil contains a complex mixture of omega-3 fatty acids, which are predominantly eicosapentaenoic acid (EPA), docosapentaenoic acid, and docosahexaenoic acid (DHA). Each of these omega-3 fatty acids has distinct biological effects that may have variable clinical effects. In addition, plasma levels of omega-3 fatty acids are affected not only by dietary intake, but also by the polymorphisms of coding genes fatty acid desaturase 1-3 for the desaturase enzymes that convert short-chain polyunsaturated fatty acids to long-chain polyunsaturated fatty acids. The clinical significance of this new understanding regarding the complexity of omega-3 fatty acid biology is the purpose of this review. FADS polymorphisms that result in either lower levels of long-chain omega-3 fatty acids or higher levels of long-chain omega-6 polyunsaturated fatty acids, such as arachidonic acid, are associated with dyslipidemia and other cardiovascular risk factors. EPA and DHA have differences in their effects on lipoprotein metabolism, in which EPA, with a more potent peroxisome proliferator-activated receptor-alpha effect, decreases hepatic lipogenesis, whereas DHA not only enhances VLDL lipolysis, resulting in greater conversion to LDL, but also increases HDL cholesterol and larger, more buoyant LDL particles. Overall, these results emphasize that blood concentrations of individual long-chain polyunsaturated fatty acids, which reflect both dietary intake and metabolic influences, may have independent, but also complementary- biological effects and reinforce the need to potentially provide a complex mixture of omega-3 fatty acids to maximize cardiovascular risk reduction.

Organics Characterization Of DWPF Alternative Reductant Simulants, Glycolic Acid, And Antifoam 747

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

White, T. L.; Wiedenman, B. J.; Lambert, D. P.

amounts of impurities such as formic and diglycolic acid that were then carried over in the SME products. Oxalic acid present in the simulated tank farm waste was also detected. Finally, numerous other compounds, at low concentrations, were observed present in etheric extracts of aqueous supernate solutions of the SME samples and are thought to be breakdown products of antifoam 747. The data collectively suggest that although addition of glycolic acid and antifoam 747 will introduce a number of impurities and breakdown products into the melter feed, the concentrations of these organics is expected to remain low and may not significantly impact REDOX or off-gas flammability predictions. In the SME products examined presently, which contained variant amounts of glycolic acid and antifoam 747, no unexpected organic degradation product was found at concentrations above 500 mg/kg, a reasonable threshold concentration for an organic compound to be taken into account in the REDOX modeling. This statement does not include oxalic or formic acid that were sometimes observed above 500 mg/kg and acetic acid that has an analytical detection limit of 1250 mg/kg due to high glycolate concentration in the SME products tested. Once a finalized REDOX equation has been developed and implemented, REDOX properties of known organic species will be determined and their impact assessed. Although no immediate concerns arose during the study in terms of a negative impact of organics present in SME products of the glycolic flowsheet, evidence of antifoam degradation suggest that an alternative antifoam to antifoam 747 is worth considering. The determination and implementation of an antifoam that is more hydrolysis resistant would have benefits such as increasing its effectiveness over time and reducing the generation of degradation products.« less

Lipid production by Cryptococcus curvatus on hydrolysates derived from corn fiber and sweet sorghum bagasse following dilute acid pretreatment.

PubMed

Liang, Yanna; Jarosz, Kimberly; Wardlow, Ashley T; Zhang, Ji; Cui, Yi

2014-08-01

Corn fiber and sweet sorghum bagasse (SSB) are both pre-processed lignocellulosic materials that can be used to produce liquid biofuels. Pretreatment using dilute sulfuric acid at a severity factor of 1.06 and 1.02 released 83.2 and 86.5 % of theoretically available sugars out of corn fiber and SSB, respectively. The resulting hydrolysates derived from pretreatment of SSB at SF of 1.02 supported growth of Cryptococcus curvatus well. In 6 days, the dry cell density reached 10.8 g/l with a lipid content of 40 % (w/w). Hydrolysates from corn fiber, however, did not lead to any significant cell growth even with addition of nutrients. In addition to consuming glucose, xylose, and arabinose, C. curvatus also utilized formic acid, acetic acid, 4-hydroxymethylfurfural, and levulinic acid for growth. Thus, C. curvatus appeared to be an excellent yeast strain for producing lipids from hydrolysates developed from lignocellulosic feedstocks.

APPLICATION OF FORMOHYDROXAMIC ACID IN NUCLEAR PROCESSING: SYNTHESIS AND COMPLEXATION WITH TECHNETIUM-99

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

Amber Wright; Edward Mausolf; Keri Campbell

2010-05-01

Acetohydroxamic acid (AHA) is an organic ligand planned for use in the Uranium Extraction (UREX) process. It reduces neptunium and plutonium, and the resultant hydrophilic complexes are separated from uranium by extraction with tributyl phosphate (TBP) in a hydrocarbon diluent. AHA undergoes hydrolysis to acetic acid which will impede the recycling of nitric acid. During recent discussions of the UREX process, it has been proposed to replace AHA by formohydroxamic acid (FHA). FHA will undergo hydrolysis to formic acid which is volatile, thus allowing the recycling of nitric acid. The reported reduction potentials of AHA and pertechnetate (TcO{sub 4}{sup -})more » indicated that it may be possible for AHA to reduce technetium, altering its fate in the fuel cycle. At UNLV, it has been demonstrated that TcO{sub 4}{sup -} undergoes reductive nitrosylation by AHA under a variety of conditions. The resulting divalent technetium is complexed by AHA to form the pseudo-octahedral trans-aquonitrosyl (diacetohydroxamic)-technetium(II) complex ([Tc{sup II}(NO)(AHA){sub 2}H{sub 2}O]{sup +}). In this paper, we are reporting the synthesis of FHA and its complex formation with technetium along with the characterization of FHA crystals achieved by NMR and IR spectroscopy. Two experiments were conducted to investigate the complexation of FHA with Tc and the results were compared with previous data on AHA. The first experiment involved the elution of Tc from a Reillex HP anion exchange resin, and the second one monitored the complexation of technetium with FHA by UV-visible spectrophotometry.« less

Tropospheric Emission Spectrometer (TES) satellite validations of ammonia, methanol, formic acid, and carbon monoxide over the Canadian oil sands

NASA Astrophysics Data System (ADS)

Shephard, M. W.; McLinden, C. A.; Cady-Pereira, K. E.; Luo, M.; Moussa, S. G.; Leithead, A.; Liggio, J.; Staebler, R. M.; Akingunola, A.; Makar, P.; Lehr, P.; Zhang, J.; Henze, D. K.; Millet, D. B.; Bash, J. O.; Zhu, L.; Wells, K. C.; Capps, S. L.; Chaliyakunnel, S.; Gordon, M.; Hayden, K.; Brook, J. R.; Wolde, M.; Li, S.-M.

2015-09-01

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 number of applications, especially at regional or global scales. These applications include air quality monitoring, trend analysis, emissions, and model evaluation. This study provides one of the first direct validations of Tropospheric Emission Spectrometer (TES) satellite retrieved profiles of NH3, CH3OH, and HCOOH through comparisons with coincident aircraft profiles. The comparisons are performed over the Canadian oil sands region during the intensive field campaign (August-September~2013) in support of the Joint Canada-Alberta Implementation Plan for the Oil Sands Monitoring (JOSM). The satellite/aircraft comparisons over this region during this period produced errors of: (i) + 0.08 ± 0.25 ppbv for NH3, (ii) + 7.5 ± 23 ppbv for CO, (iii) + 0.19 ± 0.46 ppbv for HCOOH, and (iv) -1.1 ± 0.39 ppbv for CH3OH. These values mostly agree with previously estimated retrieval errors; however, the relatively large negative bias in CH3OH and the significantly greater positive bias for larger HCOOH and CO values observed during this study warrant further investigation. Satellite and aircraft ammonia observations during the field campaign are also used in an initial effort to perform preliminary evaluations of Environment Canada's Global Environmental Multi-scale - Modelling Air quality and CHemistry (GEM-MACH) air quality modelling system at high-resolution (2.5 km × 2.5 km). These initial results indicate model under-prediction of ~ 0.6 ppbv (~ 60 %) for NH3, during the field campaign period. The TES-model CO comparison differences are ~ +20 ppbv (~ +20 %), but given that under these conditions the TES/aircraft comparisons also show a small positive TES CO bias indicates that the overall model under-prediction of CO is closer to ~ 10 % at 681 hPa (~ 3 km) during this

Simultaneous determination and pharmacokinetics of danshensu, protocatechuic aldehyde, 4-hydroxy-3-methyloxyphenyl lactic acid and protocatechuic acid in human plasma by LC-MS/MS after oral administration of Compound Danshen Dripping Pills.

PubMed

Li, Wei; Zhou, Hongjie; Chu, Yang; Wang, Xiangyang; Luo, Ruizhi; Yang, Liu; Polachi, Navaneethakrishnan; Li, Xiao; Chen, Min; Huang, Luqi; Yan, Xueying; Guo, Zhixin; Sun, He

2017-10-25

Compound Danshen Dripping Pills (CDDP), a herbal patent medicine, is widely used in China for the prevention and treatment of cardiovascular diseases. A simple, sensitive and reliable method for simultaneous determination of danshensu (DSS), protocatechuic aldehyde (PCA), and their related metabolites, 4-hydroxy-3-methyloxyphenyl lactic acid (HMLA) and protocatechuic acid (PAA) in human plasma was developed and validated based on liquid chromatography tandem mass spectrometry (LC-MS/MS). The analytes and internal standard (IS), vanillic acid (VAA), were extracted from plasma with ethyl acetate and separated on a C 18 column by using the mobile phase consisted of methanol-0.1% formic acid via gradient elution. The electrospray ionization (ESI) source was applied and operated under the multiple reaction monitoring (MRM) mode. The linear calibration curves were obtained at the concentration ranges of 0.46-1000ng/mL for DSS and PAA, and 1.38-1000ng/mL for PCA and HMLA, respectively. The inter- and intra-day precisions (RSD%) were less than 13.5%, and the accuracy (±RE%) was within 13.4%. The described method was successfully applied for the clinical pharmacokinetics of CDDP in Chinese healthy volunteers. Copyright © 2017. Published by Elsevier B.V.

Sludge batch 9 simulant runs using the nitric-glycolic acid flowsheet

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

Lambert, D. P.; Williams, M. S.; Brandenburg, C. H.

Testing was completed to develop a Sludge Batch 9 (SB9) nitric-glycolic acid chemical process flowsheet for the Defense Waste Processing Facility’s (DWPF) Chemical Process Cell (CPC). CPC simulations were completed using SB9 sludge simulant, Strip Effluent Feed Tank (SEFT) simulant and Precipitate Reactor Feed Tank (PRFT) simulant. Ten sludge-only Sludge Receipt and Adjustment Tank (SRAT) cycles and four SRAT/Slurry Mix Evaporator (SME) cycles, and one actual SB9 sludge (SRAT/SME cycle) were completed. As has been demonstrated in over 100 simulations, the replacement of formic acid with glycolic acid virtually eliminates the CPC’s largest flammability hazards, hydrogen and ammonia. Recommended processingmore » conditions are summarized in section 3.5.1. Testing demonstrated that the interim chemistry and Reduction/Oxidation (REDOX) equations are sufficient to predict the composition of DWPF SRAT product and SME product. Additional reports will finalize the chemistry and REDOX equations. Additional testing developed an antifoam strategy to minimize the hexamethyldisiloxane (HMDSO) peak at boiling, while controlling foam based on testing with simulant and actual waste. Implementation of the nitric-glycolic acid flowsheet in DWPF is recommended. This flowsheet not only eliminates the hydrogen and ammonia hazards but will lead to shorter processing times, higher elemental mercury recovery, and more concentrated SRAT and SME products. The steady pH profile is expected to provide flexibility in processing the high volume of strip effluent expected once the Salt Waste Processing Facility starts up.« less

Boric acid and boronic acids inhibition of pigeonpea urease.

PubMed

Reddy, K Ravi Charan; Kayastha, Arvind M

2006-08-01

Urease from the seeds of pigeonpea was competitively inhibited by boric acid, butylboronic acid, phenylboronic acid, and 4-bromophenylboronic acid; 4-bromophenylboronic acid being the strongest inhibitor, followed by boric acid > butylboronic acid > phenylboronic acid, respectively. Urease inhibition by boric acid is maximal at acidic pH (5.0) and minimal at alkaline pH (10.0), i.e., the trigonal planar B(OH)3 form is a more effective inhibitor than the tetrahedral B(OH)4 -anionic form. Similarly, the anionic form of phenylboronic acid was least inhibiting in nature.

Utilization of acetic acid-rich pyrolytic bio-oil by microalga Chlamydomonas reinhardtii: reducing bio-oil toxicity and enhancing algal toxicity tolerance.

PubMed

Liang, Yi; Zhao, Xuefei; Chi, Zhanyou; Rover, Marjorie; Johnston, Patrick; Brown, Robert; Jarboe, Laura; Wen, Zhiyou

2013-04-01

This work was to utilize acetic acid contained in bio-oil for growth and lipid production of the microalga Chlamydomonas reinhardtii. The acetic acid-rich bio-oil fraction derived from fast pyrolysis of softwood contained 26% (w/w) acetic acid, formic acid, methanol, furfural, acetol, and phenolics as identified compounds, and 13% (w/w) unidentified compounds. Among those identified compounds, phenolics were most inhibitory to algal growth, followed by furfural and acetol. To enhance the fermentability of the bio-oil fraction, activated carbon was used to reduce the toxicity of the bio-oil, while metabolic evolution was used to enhance the toxicity tolerance of the microalgae. Combining activated carbon treatment and using evolved algal strain resulted in significant algal growth improvement. The results collectively showed that fast pyrolysis-fermentation process was a viable approach for converting biomass into fuels and chemicals. Copyright © 2013 Elsevier Ltd. All rights reserved.

Biosuccinic Acid from Lignocellulosic-Based Hexoses and Pentoses by Actinobacillus succinogenes: Characterization of the Conversion Process.

PubMed

Ferone, Mariateresa; Raganati, Francesca; Olivieri, Giuseppe; Salatino, Piero; Marzocchella, Antonio

2017-12-01

Succinic acid (SA) is a well-established chemical building block. Actinobacillus succinogenes fermentation is by far the most investigated route due to very promising high SA yield and titer on several sugars. This study contributes to include the SA production within the concept of biorefinery of lignocellulose biomass. The study was focused on the SA production by A. succinogenes DSM 22257 using sugars representative from lignocellulose hydrolysis-glucose, mannose, arabinose, and xylose-as carbon source. Single sugar batch fermentation tests and mixture sugar fermentation tests were carried out. All the sugars investigated were converted in succinic acid by A. succinogenes. The best fermentation performances were measured in tests with glucose as carbon source. The bacterial growth kinetics was characterized by glucose inhibition. No inhibition phenomena were observed with the other sugar investigated. The sugar mixture fermentation tests highlighted the synergic effects of the co-presence of the four sugars. Under the operating conditions tested, the final concentration of succinic acid in the sugar mixture test was larger (27 g/L) than that expected (25.5 g/L) by combining the fermentation of the single sugar. Moreover, the concentration of acetic and formic acid was lower, consequently obtaining an increment in the succinic acid specificity.

Acid Rain

USGS Publications Warehouse

Bricker, Owen P.; Rice, Karen C.

1995-01-01

Although acid rain is fading as a political issue in the United States and funds for research in this area have largely disappeared, the acidity of rain in the Eastern United States has not changed significantly over the last decade, and it continues to be a serious environmental problem. Acid deposition (commonly called acid rain) is a term applied to all forms of atmospheric deposition of acidic substances - rain, snow, fog, acidic dry particulates, aerosols, and acid-forming gases. Water in the atmosphere reacts with certain atmospheric gases to become acidic. For example, water reacts with carbon dioxide in the atmosphere to produce a solution with a pH of about 5.6. Gases that produce acids in the presence of water in the atmosphere include carbon dioxide (which converts to carbonic acid), oxides of sulfur and nitrogen (which convert to sulfuric and nitric acids}, and hydrogen chloride (which converts to hydrochloric acid). These acid-producing gases are released to the atmosphere through natural processes, such as volcanic emissions, lightning, forest fires, and decay of organic matter. Accordingly, precipitation is slightly acidic, with a pH of 5.0 to 5.7 even in undeveloped areas. In industrialized areas, most of the acid-producing gases are released to the atmosphere from burning fossil fuels. Major emitters of acid-producing gases include power plants, industrial operations, and motor vehicles. Acid-producing gases can be transported through the atmosphere for hundreds of miles before being converted to acids and deposited as acid rain. Because acids tend to build up in the atmosphere between storms, the most acidic rain falls at the beginning of a storm, and as the rain continues, the acids "wash out" of the atmosphere.

Production of d-lactic acid from hardwood pulp by mechanical milling followed by simultaneous saccharification and fermentation using metabolically engineered Lactobacillus plantarum.

PubMed

Hama, Shinji; Mizuno, Shino; Kihara, Maki; Tanaka, Tsutomu; Ogino, Chiaki; Noda, Hideo; Kondo, Akihiko

2015-01-01

This study focused on the process development for the d-lactic acid production from cellulosic feedstocks using the Lactobacillus plantarum mutant, genetically modified to produce optically pure d-lactic acid from both glucose and xylose. The simultaneous saccharification and fermentation (SSF) using delignified hardwood pulp (5-15% loads) resulted in the lactic acid titers of 55.2-84.6g/L after 72h and increased productivities of 1.77-2.61g/L/h. To facilitate the enzymatic saccharification of high-load pulp at a fermentation temperature, short-term (⩽10min) pulverization of pulp was conducted, leading to a significantly improved saccharification with the suppressed formation of formic acid by-product. The short-term milling followed by SSF resulted in a lactic acid titer of 102.3g/L, an optical purity of 99.2%, and a yield of 0.879g/g-sugars without fed-batch process control. Therefore, the process presented here shows promise for the production of high-titer d-lactic acid using the L. plantarum mutant. Copyright © 2015 Elsevier Ltd. All rights reserved.

Effect of organic acids production and bacterial community on the possible mechanism of phosphorus solubilization during composting with enriched phosphate-solubilizing bacteria inoculation.

PubMed

Wei, Yuquan; Zhao, Yue; Shi, Mingzi; Cao, Zhenyu; Lu, Qian; Yang, Tianxue; Fan, Yuying; Wei, Zimin

2018-01-01

Enriched phosphate-solubilizing bacteria (PSB) agent were acquired by domesticated cultivation, and inoculated into kitchen waste composting in different stages. The effect of different treatments on organic acids production, tricalcium phosphate (TCP) solubilization and their relationship with bacterial community were investigated during composting. Our results pointed out that inoculation affected pH, total acidity and the production of oxalic, lactic, citric, succinic, acetic and formic acids. We also found a strong advantage in the solubilization of TCP and phosphorus (P) availability for PSB inoculation especially in the cooling stage. Redundancy analysis and structural equation models demonstrated inoculation by different methods changed the correlation of the bacterial community composition with P fractions as well as organic acids, and strengthened the cooperative function related to P transformation among species during composting. Finally, we proposed a possible mechanism of P solubilization with enriched PSB inoculation, which was induced by bacterial community and organic acids production. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

PubMed

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

2002-12-06

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

Fuel cells and fuel cell catalysts

DOEpatents

Masel, Richard I.; Rice, Cynthia A.; Waszczuk, Piotr; Wieckowski, Andrzej

2006-11-07

A direct organic fuel cell includes a formic acid fuel solution having between about 10% and about 95% formic acid. The formic acid is oxidized at an anode. The anode may include a Pt/Pd catalyst that promotes the direct oxidation of the formic acid via a direct reaction path that does not include formation of a CO intermediate.

Organic acids and selected nitrogen species for ABLE-3

NASA Technical Reports Server (NTRS)

Talbot, Robert W.

1991-01-01

The NASA Global Tropospheric Experiment (GTE) executed airborne science missions aboard the NASA Wallops Electra (NA429) in the North American high latitude (greater than 45 deg North) atmosphere during Jul. to Aug. 1988 and Jul. to Aug. 1990. These missions were part of GTE's Atmospheric Boundary Layer Experiment (ABLE). The 1988 mission , ABLE-3A, examined the ecosystems of Alaska as a source and/or sink for important tropospheric gases and particles, and gained new information on the chemical composition of the Arctic atmosphere during the summertime. During 1990 the second high latitude mission, ABLE-3B, focused on the Hudson Bay Lowland and Labrador regions of Canada. Both of these missions provided benchmark data sets on atmosphere biosphere exchange and atmospheric chemistry over largely uninhabited regions of North America. In support of the GTE/ABLE-3A and -3B field missions, the University of New Hampshire flew instrumentation aboard the Wallops Electra research aircraft to provide measurements of the trace gases nitric (HNO3), formic (HCOOH), and acetic (CH3COOH) acid. In addition, measurements were conducted to determine the major water soluble ionic composition of the atmospheric aerosol. For ABLE-3B, groundbased measurements of the acidic trace gases were also performed from the NASA micrometerological tower situated at Schefferville, Laborador. These measurements were aimed at assessing dry deposition of acidic gases to the taiga ecosystem in the Laborador region of Canada.

Pt/Ni(OH)2–NiOOH/Pd multi-walled hollow nanorod arrays as superior electrocatalysts for formic acid electrooxidation† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5sc02544c Click here for additional data file.

PubMed Central

Xu, Han; Ding, Liang-Xin; Feng, Jin-Xian

2015-01-01

The catalytic activity and durability are crucial for the development of high-performance electrocatalysts. To design electrocatalysts with excellent electroactivity and durability, the structure and composition are two important guiding principles. In this work, novel Pt/Ni(OH)2–NiOOH/Pd multi-walled hollow nanorod arrays (MHNRAs) are successfully synthesized. The unique MHNRAs provide fast transport and short diffusion paths for electroactive species and high utilization rate of catalysts. Because of the special surface and synergistic effects, the Pt/Ni(OH)2–NiOOH/Pd MHNRA electrocatalysts exhibit high catalytic activity, high durability and superior CO poisoning tolerance for the electrooxidation of formic acid in comparison with Pt@Pd MHNRAs, commercial Pt/C, Pd/C and PtRu/C catalysts. PMID:28757980

Enantioselective oxidation of racemic lactic acid to D-lactic acid and pyruvic acid by Pseudomonas stutzeri SDM.

PubMed

Gao, Chao; Qiu, Jianhua; Li, Jingchen; Ma, Cuiqing; Tang, Hongzhi; Xu, Ping

2009-03-01

D-lactic acid and pyruvic acid are two important building block intermediates. Production of D-lactic acid and pyruvic acid from racemic lactic acid by biotransformation is economically interesting. Biocatalyst prepared from 9 g dry cell wt l(-1) of Pseudomonas stutzeri SDM could catalyze 45.00 g l(-1)DL-lactic acid into 25.23 g l(-1)D-lactic acid and 19.70 g l(-1) pyruvic acid in 10h. Using a simple ion exchange process, D-lactic acid and pyruvic acid were effectively separated from the biotransformation system. Co-production of d-lactic acid and pyruvic acid by enantioselective oxidation of racemic lactic acid is technically feasible.

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

PubMed

Xu, Jian; Bao, Jia-Wei; Su, Xian-Feng; Zhang, Hong-Jian; Zeng, Xin; Tang, Lei; Wang, Ke; Zhang, Jian-Hua; Chen, Xu-Sheng; Mao, Zhong-Gui

2016-03-01

In this study, an integrated citric acid-methane fermentation process was established to solve the problem of wastewater treatment in citric acid production. Citric acid wastewater was treated through anaerobic digestion and then the anaerobic digestion effluent (ADE) was further treated and recycled for the next batch citric acid fermentation. This process could eliminate wastewater discharge and reduce water resource consumption. Propionic acid was found in the ADE and its concentration continually increased in recycling. Effect of propionic acid on citric acid fermentation was investigated, and results indicated that influence of propionic acid on citric acid fermentation was contributed to the undissociated form. Citric acid fermentation was inhibited when the concentration of propionic acid was above 2, 4, and 6 mM in initial pH 4.0, 4.5 and, 5.0, respectively. However, low concentration of propionic acid could promote isomaltase activity which converted more isomaltose to available sugar, thereby increasing citric acid production. High concentration of propionic acid could influence the vitality of cell and prolong the lag phase, causing large amount of glucose still remaining in medium at the end of fermentation and decreasing citric acid production.

Effect of baseline plasma fatty acids on eicosapentaenoic acid levels in individuals supplemented with alpha-linolenic acid.

PubMed

DeFilippis, Andrew P; Harper, Charles R; Cotsonis, George A; Jacobson, Terry A

2009-01-01

We previously reported a >50% increase in mean plasma eicosapentaenoic acid levels in a general medicine clinic population after supplementation with alpha-linolenic acid. In the current analysis, we evaluate the variability of changes in eicosapentaenoic acid levels among individuals supplemented with alpha-linolenic acid and evaluated the impact of baseline plasma fatty acids levels on changes in eicosapentaenoic acid levels in these individuals. Changes in eicosapentaenoic acid levels among individuals supplemented with alpha-linolenic acid ranged from a 55% decrease to a 967% increase. Baseline plasma fatty acids had no statistically significant effect on changes in eicosapentaenoic levels acid after alpha-linolenic acid supplementation. Changes in eicosapentaenoic acid levels varied considerably in a general internal medicine clinic population supplemented with alpha-linolenic acid. Factors that may impact changes in plasma eicosapentaenoic acid levels after alpha-linolenic acid supplementation warrant further study.

Specific bile acids inhibit hepatic fatty acid uptake

PubMed Central

Nie, Biao; Park, Hyo Min; Kazantzis, Melissa; Lin, Min; Henkin, Amy; Ng, Stephanie; Song, Sujin; Chen, Yuli; Tran, Heather; Lai, Robin; Her, Chris; Maher, Jacquelyn J.; Forman, Barry M.; Stahl, Andreas

2012-01-01

Bile acids are known to play important roles as detergents in the absorption of hydrophobic nutrients and as signaling molecules in the regulation of metabolism. Here we tested the novel hypothesis that naturally occurring bile acids interfere with protein-mediated hepatic long chain free fatty acid (LCFA) uptake. To this end stable cell lines expressing fatty acid transporters as well as primary hepatocytes from mouse and human livers were incubated with primary and secondary bile acids to determine their effects on LCFA uptake rates. We identified ursodeoxycholic acid (UDCA) and deoxycholic acid (DCA) as the two most potent inhibitors of the liver-specific fatty acid transport protein 5 (FATP5). Both UDCA and DCA were able to inhibit LCFA uptake by primary hepatocytes in a FATP5-dependent manner. Subsequently, mice were treated with these secondary bile acids in vivo to assess their ability to inhibit diet-induced hepatic triglyceride accumulation. Administration of DCA in vivo via injection or as part of a high-fat diet significantly inhibited hepatic fatty acid uptake and reduced liver triglycerides by more than 50%. In summary, the data demonstrate a novel role for specific bile acids, and the secondary bile acid DCA in particular, in the regulation of hepatic LCFA uptake. The results illuminate a previously unappreciated means by which specific bile acids, such as UDCA and DCA, can impact hepatic triglyceride metabolism and may lead to novel approaches to combat obesity-associated fatty liver disease. PMID:22531947

[Lipid synthesis by an acidic acid tolerant Rhodotorula glutinis].

PubMed

Lin, Zhangnan; Liu, Hongjuan; Zhang, Jian'an; Wang, Gehua

2016-03-01

Acetic acid, as a main by-product generated in the pretreatment process of lignocellulose hydrolysis, significantly affects cell growth and lipid synthesis of oleaginous microorganisms. Therefore, we studied the tolerance of Rhodotorula glutinis to acetic acid and its lipid synthesis from substrate containing acetic acid. In the mixed sugar medium containing 6 g/L glucose and 44 g/L xylose, and supplemented with acetic acid, the cell growth was not:inhibited when the acetic acid concentration was below 10 g/L. Compared with the control, the biomass, lipid concentration and lipid content of R. glutinis increased 21.5%, 171% and 122% respectively when acetic acid concentration was 10 g/L. Furthermore, R. glutinis could accumulate lipid with acetate as the sole carbon source. Lipid concentration and lipid yield reached 3.20 g/L and 13% respectively with the initial acetic acid concentration of 25 g/L. The lipid composition was analyzed by gas chromatograph. The main composition of lipid produced with acetic acid was palmitic acid, stearic acid, oleic acid, linoleic acid and linolenic acid, including 40.9% saturated fatty acids and 59.1% unsaturated fatty acids. The lipid composition was similar to that of plant oil, indicating that lipid from oleaginous yeast R. glutinis had potential as the feedstock of biodiesel production. These results demonstrated that a certain concentration of acetic acid need not to be removed in the detoxification process when using lignocelluloses hydrolysate to produce microbial lipid by R. glutinis.

Favorable Effects of Weak Acids on Negative-Ion Electrospray Ionization Mass Spectrometry

PubMed Central

Wu, Zengru; Gao, Wenqing; Phelps, Mitch A.; Wu, Di; Miller, Duane D.; Dalton, James T.

2007-01-01

Despite widespread use in pharmacokinetic, drug metabolism, and pesticide residue studies, little is known about the factors governing response during reversed-phase liquid chromatography coupled with negative-ion electrospray ionization (ESI−) mass spectrometry. We examined the effects of various mobile-phase modifiers on the ESI− response of four selective androgen receptor modulators using a postcolumn infusion system. Acetic, propionic, and butyric acid improved the ESI− responses of analytes to varying extents at low concentrations. Formic acid suppressed ionization, as did neutral salts (ammonium formate, ammonium acetate) and bases (ammonium hydroxide, triethylamine) under most conditions. Two modifiers (2,2,2-trifluoroethanol, formaldehyde) that produce anions with high gas-phase proton affinity increased ESI− responses. However, the concentrations of these modifiers required to enhance ESI− response were higher than that of acidic modifiers, which is a phenomenon likely related to their low pKa values. 2,2,2-Trifluoroethanol increased response of more hydrophobic compounds but decreased response of a more hydrophilic compound. Formaldehyde improved response of all the compounds, especially the hydrophilic compound with lower surface activity. In summary, these results suggest that an ideal ESI− modifier should provide cations that can be easily electrochemically reduced and produce anions with small molecular volume and high gas-phase proton affinity. PMID:14750883

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

PubMed

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

2012-11-01

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

Quantification of γ-Aminobutyric Acid in Cerebrospinal Fluid Using Liquid Chromatography-Electrospray Tandem Mass Spectrometry.

PubMed

Arning, Erland; Bottiglieri, Teodoro

2016-01-01

We describe a simple stable isotope dilution method for accurate and precise measurement of γ-aminobutyric acid (GABA), a major inhibitory neurotransmitter in human cerebrospinal fluid (CSF) as a clinical diagnostic test. Determination of GABA in CSF (50 μL) was performed utilizing high performance liquid chromatography coupled with electrospray positive ionization tandem mass spectrometry (HPLC-ESI-MS/MS). Analysis of free and total GABA requires two individual sample preparations and mass spectrometry analyses. Free GABA in CSF is determined by a 1:2 dilution with internal standard (GABA-D2) and injected directly onto the HPLC-ESI-MS/MS system. Determination of total GABA in CSF requires additional sample preparation in order to hydrolyze all the bound GABA in the sample to the free form. This requires hydrolyzing the sample by boiling in acidic conditions (hydrochloric acid) for 4 h. The sample is then further diluted 1:10 with a 90 % acetonitrile/0.1 % formic acid solution and injected into the HPLC-ESI-MS/MS system. Each assay is quantified using a five-point standard curve and is linear from 6 nM to 1000 nM and 0.63 μM to 80 μM for free and total GABA, respectively.

[Analysis of sialic acid in infant formulas using ultra performance liquid chromatography-triple quadrupole mass spectrometry].

PubMed

Xie, Honglei; Li, Chun; Liu, Ning

2013-08-01

The method for analysing sialic acid in infant formulas by ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) has been established. Sialic acid in milk was released via acid hydrolysis, and purified by an HLB solid phase extraction cartridge. The UPLC separation was performed on an ACQUITY UPLC BEH HILIC column (50 mm x 2.1 mm, 1.7 microm) utilizing a gradient elution program of acetonitrile and water (containing 0.1% formic acid) as the mobile phases at a flow rate of 0.25 mL/min. Injection volume and column temperature were set at 5 microL and 30 degrees C, respectively. The identification and quantification were achieved by using electrospray ionisation (ESI)-MS/MS in positive ion mode and multiple reaction monitoring (MRM) mode. The linear range was from 0.05 to 5.0 mg/L for sialic acid and the correlation coefficient (R(2)) was greater than 0.99. The average recoveries spiked at the four concentration levels of 0.1, 0.5, 2.5 and 5.0 mg/L ranged between 84.3% and 98.9% with the relative standard deviations from 4.9% to 8.2%. The limit of detection was 0.01 mg/L. Therefore, this method has the characteristics of simple operation, high reproducibility and sensitivity. It can be widely applied to determine the total contents of sialic acid in infant formula, cow milk and human milk.

Production of Succinic Acid from Citric Acid and Related Acids by Lactobacillus Strains

PubMed Central

Kaneuchi, Choji; Seki, Masako; Komagata, Kazuo

1988-01-01

A number of Lactobacillus strains produced succinic acid in de Man-Rogosa-Sharpe broth to various extents. Among 86 fresh isolates from fermented cane molasses in Thailand, 30 strains (35%) produced succinic acid; namely, 23 of 39 Lactobacillus reuteri strains, 6 of 18 L. cellobiosus strains, and 1 of 6 unidentified strains. All of 10 L. casei subsp. casei strains, 5 L. casei subsp. rhamnosus strains, 6 L. mali strains, and 2 L. buchneri strains did not produce succinic acid. Among 58 known strains including 48 type strains of different Lactobacillus species, the strains of L. acidophilus, L. crispatus, L. jensenii, and L. parvus produced succinic acid to the same extent as the most active fresh isolates, and those of L. alimentarius, L. collinoides, L. farciminis, L. fructivorans (1 of 2 strains tested), L. malefermentans, and L. reuteri were also positive, to lesser extents. Diammonium citrate in de Man-Rogosa-Sharpe broth was determined as a precursor of the succinic acid produced. Production rates were about 70% on a molar basis with two fresh strains tested. Succinic acid was also produced from fumaric and malic acids but not from dl-isocitric, α-ketoglutaric, and pyruvic acids. The present study is considered to provide the first evidence on the production of succinic acid, an important flavoring substance in dairy products and fermented beverages, from citrate by lactobacilli. PMID:16347795

Production of succinic Acid from citric Acid and related acids by lactobacillus strains.

PubMed

Kaneuchi, C; Seki, M; Komagata, K

1988-12-01

A number of Lactobacillus strains produced succinic acid in de Man-Rogosa-Sharpe broth to various extents. Among 86 fresh isolates from fermented cane molasses in Thailand, 30 strains (35%) produced succinic acid; namely, 23 of 39 Lactobacillus reuteri strains, 6 of 18 L. cellobiosus strains, and 1 of 6 unidentified strains. All of 10 L. casei subsp. casei strains, 5 L. casei subsp. rhamnosus strains, 6 L. mali strains, and 2 L. buchneri strains did not produce succinic acid. Among 58 known strains including 48 type strains of different Lactobacillus species, the strains of L. acidophilus, L. crispatus, L. jensenii, and L. parvus produced succinic acid to the same extent as the most active fresh isolates, and those of L. alimentarius, L. collinoides, L. farciminis, L. fructivorans (1 of 2 strains tested), L. malefermentans, and L. reuteri were also positive, to lesser extents. Diammonium citrate in de Man-Rogosa-Sharpe broth was determined as a precursor of the succinic acid produced. Production rates were about 70% on a molar basis with two fresh strains tested. Succinic acid was also produced from fumaric and malic acids but not from dl-isocitric, alpha-ketoglutaric, and pyruvic acids. The present study is considered to provide the first evidence on the production of succinic acid, an important flavoring substance in dairy products and fermented beverages, from citrate by lactobacilli.

Preparation and characterization Al3+-bentonite Turen Malang for esterification fatty acid (palmitic acid, oleic acid and linoleic acid)

NASA Astrophysics Data System (ADS)

Abdulloh, Abdulloh; Aminah, Nanik Siti; Triyono, Mudasir, Trisunaryanti, Wega

2016-03-01

Catalyst preparation and characterization of Al3+-bentonite for esterification of palmitic acid, oleic acid and linoleic acid has been done. Al3+-bentonite catalyst was prepared from natural bentonite of Turen Malang through cation exchange reaction using AlCl3 solution. The catalysts obtained were characterized by XRD, XRF, pyridine-FTIR and surface area analyser using the BET method. Catalyst activity test of Al3+-bentonite for esterification reaction was done at 65°C using molar ratio of metanol-fatty acid of 30:1 and 0.25 g of Al3+-bentonite catalyst for the period of ½, 1, 2, 3, 4 and 5 hours. Based on the characterization results, the Al3+-bentonite Turen Malang catalyst has a d-spacing of 15.63 Ǻ, acid sites of Brönsted and Lewis respectively of 230.79 µmol/g and 99.39 µmol/g, surface area of 507.3 m2/g and the average of radius pore of 20.09 Å. GC-MS analysis results of the oil phase after esterification reaction showed the formation of biodiesel (FAME: Fatty acid methyl ester), namely methyl palmitate, methyl oleate and methyl linoleate. The number of conversions resulted in esterification reaction using Al3+-bentonite Turen Malang catalyst was 74.61%, 37.75%, and 20, 93% for the esterification of palmitic acid, oleic acid and linoleic acid respectively.

An ab initio potential energy surface for the formic acid dimer: zero-point energy, selected anharmonic fundamental energies, and ground-state tunneling splitting calculated in relaxed 1-4-mode subspaces.

PubMed

Qu, Chen; Bowman, Joel M

2016-09-14

We report a full-dimensional, permutationally invariant potential energy surface (PES) for the cyclic formic acid dimer. This PES is a least-squares fit to 13475 CCSD(T)-F12a/haTZ (VTZ for H and aVTZ for C and O) energies. The energy-weighted, root-mean-square fitting error is 11 cm -1 and the barrier for the double-proton transfer on the PES is 2848 cm -1 , in good agreement with the directly-calculated ab initio value of 2853 cm -1 . The zero-point vibrational energy of 15 337 ± 7 cm -1 is obtained from diffusion Monte Carlo calculations. Energies of fundamentals of fifteen modes are calculated using the vibrational self-consistent field and virtual-state configuration interaction method. The ground-state tunneling splitting is computed using a reduced-dimensional Hamiltonian with relaxed potentials. The highest-level, four-mode coupled calculation gives a tunneling splitting of 0.037 cm -1 , which is roughly twice the experimental value. The tunneling splittings of (DCOOH) 2 and (DCOOD) 2 from one to three mode calculations are, as expected, smaller than that for (HCOOH) 2 and consistent with experiment.

Efficacy of Lactic Acid, Lactic Acid-Acetic Acid Blends, and Peracetic Acid To Reduce Salmonella on Chicken Parts under Simulated Commercial Processing Conditions.

PubMed

Ramirez-Hernandez, Alejandra; Brashears, Mindy M; Sanchez-Plata, Marcos X

2018-01-01

The poultry processing industry has been undergoing a series of changes as it modifies processing practices to comply with new performance standards for chicken parts and comminuted poultry products. The regulatory approach encourages the use of intervention strategies to prevent and control foodborne pathogens in poultry products and thus improve food safety and protect human health. The present studies were conducted to evaluate the efficacy of antimicrobial interventions for reducing Salmonella on inoculated chicken parts under simulated commercial processing conditions. Chicken pieces were inoculated by immersion in a five-strain Salmonella cocktail at 6 log CFU/mL and then treated with organic acids and oxidizing agents on a commercial rinsing conveyor belt. The efficacy of spraying with six different treatments (sterile water, lactic acid, acetic acid, buffered lactic acid, acetic acid in combination with lactic acid, and peracetic acid) at two concentrations was evaluated on skin-on and skin-off chicken thighs at three application temperatures. Skinless chicken breasts were used to evaluate the antimicrobial efficacy of lactic acid and peracetic acid. The color stability of treated and untreated chicken parts was assessed after the acid interventions. The lactic acid and buffered lactic acid treatments produced the greatest reductions in Salmonella counts. Significant differences between the control and water treatments were identified for 5.11% lactic acid and 5.85% buffered lactic acid in both skin-on and skin-off chicken thighs. No significant effect of treatment temperature for skin-on chicken thighs was found. Lactic acid and peracetic acid were effective agents for eluting Salmonella cells attached to chicken breasts.

Preparation of the 3-monosulphates of cholic acid, chenodeoxycholic acid and deoxycholic acid.

PubMed Central

Haslewood, E S; Haslewood, G A

1976-01-01

1. The 3-sulphates of cholic, chenodeoxycholic and deoxycholic acids were prepared as crystalline disodium salts. 2. The method described shows that it is possible to prepare specific sulphate esters of polyhydroxy bile acids and to remove protecting acyl groups without removing the sulphate. 3. A study of bile acid sulphate solvolysis showed that none of the usual methods give the original bile acid in major yield in a single step. 4. An understanding of the preparation, properties and methods of solvolysis of bile acid sulphates is basic for investigations of cholestasis and liver disease. PMID:938488

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.

Acid Rain, pH & Acidity: A Common Misinterpretation.

ERIC Educational Resources Information Center

Clark, David B.; Thompson, Ronald E.

1989-01-01

Illustrates the basis for misleading statements about the relationship between pH and acid content in acid rain. Explains why pH cannot be used as a measure of acidity for rain or any other solution. Suggests that teachers present acidity and pH as two separate and distinct concepts. (RT)

High-dimensional fitting of sparse datasets of CCSD(T) electronic energies and MP2 dipole moments, illustrated for the formic acid dimer and its complex IR spectrum

NASA Astrophysics Data System (ADS)

Qu, Chen; Bowman, Joel M.

2018-06-01

We present high-level, coupled-mode calculations of the infrared spectrum of the cyclic formic acid dimer. The calculations make use of full-dimensional, ab initio potential energy and dipole moment surfaces. The potential is a linear least-squares fit to 13 475 CCSD(T)-F12a/haTZ (haTZ means aug-cc-pVTZ basis set for O and C, and cc-pVTZ for H) energies, and the dipole moment surface is a fit to the dipole components, calculated at the MP2/haTZ level of theory. The variables of both fits are all (45) internuclear distances (actually Morse variables). The potential, which is fully permutationally invariant, is the one published recently and the dipole moment surface is newly reported here. Details of the fits, especially the dipole moment, and the database of configurations are given. The infrared spectrum of the dimer is calculated by solving the nuclear Schrödinger equation using a vibrational self-consistent field and virtual-state configuration interaction method, with subsets of the 24 normal modes, up to 15 modes. The calculations indicate strong mode-coupling in the C—H and O—H stretching region of the spectrum. Comparisons are made with experiments and the complexity of the experimental spectrum in the C—H and O—H stretching region is successfully reproduced.

Production of polymalic acid and malic acid by Aureobasidium pullulans fermentation and acid hydrolysis.

PubMed

Zou, Xiang; Zhou, Yipin; Yang, Shang-Tian

2013-08-01

Malic acid is a dicarboxylic acid widely used in the food industry and also a potential C4 platform chemical that can be produced from biomass. However, microbial fermentation for direct malic acid production is limited by low product yield, titer, and productivity due to end-product inhibition. In this work, a novel process for malic acid production from polymalic acid (PMA) fermentation followed by acid hydrolysis was developed. First, a PMA-producing Aureobasidium pullulans strain ZX-10 was screened and isolated. This microbe produced PMA as the major fermentation product at a high-titer equivalent to 87.6 g/L of malic acid and high-productivity of 0.61 g/L h in free-cell fermentation in a stirred-tank bioreactor. Fed-batch fermentations with cells immobilized in a fibrous-bed bioreactor (FBB) achieved the highest product titer of 144.2 g/L and productivity of 0.74 g/L h. The fermentation produced PMA was purified by adsorption with IRA-900 anion-exchange resins, achieving a ∼100% purity and a high recovery rate of 84%. Pure malic acid was then produced from PMA by hydrolysis with 2 M sulfuric acid at 85°C, which followed the first-order reaction kinetics. This process provides an efficient and economical way for PMA and malic acid production, and is promising for industrial application. Copyright © 2013 Wiley Periodicals, Inc.

Effect of basic and acidic additives on the separation of some basic drug enantiomers on polysaccharide-based chiral columns with acetonitrile as mobile phase.

PubMed

Gogaladze, Khatuna; Chankvetadze, Lali; Tsintsadze, Maia; Farkas, Tivadar; Chankvetadze, Bezhan

2015-03-01

The separation of enantiomers of 16 basic drugs was studied using polysaccharide-based chiral selectors and acetonitrile as mobile phase with emphasis on the role of basic and acidic additives on the separation and elution order of enantiomers. Out of the studied chiral selectors, amylose phenylcarbamate-based ones more often showed a chiral recognition ability compared to cellulose phenylcarbamate derivatives. An interesting effect was observed with formic acid as additive on enantiomer resolution and enantiomer elution order for some basic drugs. Thus, for instance, the enantioseparation of several β-blockers (atenolol, sotalol, toliprolol) improved not only by the addition of a more conventional basic additive to the mobile phase, but also by the addition of an acidic additive. Moreover, an opposite elution order of enantiomers was observed depending on the nature of the additive (basic or acidic) in the mobile phase. © 2015 Wiley Periodicals, Inc.

Spatiotemporal distribution and source apportionment of low molecular weight organic acids in wet precipitation at a coastal city, China.

PubMed

Du, Wenjiao; Hong, Zhenyu; Chen, Yanting; Deng, Junjun; Chen, Jinsheng; Xu, Lingling; Hong, Youwei; Xiao, Hang

2017-03-01

To investigate the characteristics and sources of low molecular weight (LMW) organic acids in wet precipitation at a coastal city, Xiamen, a total of 313 rainwater samples were collected at seven different functional areas from September 2012 to August 2013. Spatiotemporal characteristics of LMW organic acids as well as pH and electrical conductivity were analyzed. Meanwhile, air mass clusters in different seasons and the positive matrix factorization (PMF) source apportion model were comprehensively used to identify the sources of organic acids. In conclusion, the volume-weighted mean (VWM) concentration of formic (3.20 μmol/L), acetic (1.84 μmol/L), lactic (0.44 μmol/L), and oxalic acid (0.53 μmol/L) were obtained, which jointly contributed to 4.33% of the total free acidity (TFA). At the same time, the highest wet deposition flux of LMW organic acids and contribution of that to TFA were achieved at the forest protection area during growing season in Xiamen. In addition, biogenic emissions (77.12%), sea salts (13.77%), regional agriculture activities (3.92%), soil emissions (2.56%), biomass burning (1.47%), and secondary aerosols (1.15%) were determined as the source of LMW organic acids. Besides, the dominancy of biomass burning via long-range transport in non-growing season (NGS) and the contribution of biogenic emission in growing season (GS) were recognized. Finally, the considerable influence of sea salts on the LMW organic acids (13.77%) in Xiamen was quantified, especially for oxalic acid.

Molecular and isotopic analyses of the hydroxy acids, dicarboxylic acids, and hydroxydicarboxylic acids of the Murchison meteorite

NASA Astrophysics Data System (ADS)

Cronin, J. R.; Pizzarello, S.; Epstein, S.; Krishnamurthy, R. V.

1993-10-01

The hydroxymonocarboxylic acids, dicarboxylic acids, and hydroxydicarboxylic acids of the Murchison meteorite were analyzed as their tert-butyldimethylsilyl derivatives using combined gas chromatography-mass spectrometry. The hydroxydicarboxylic acids have not been found previously in meteorites. Each class of compounds is numerous with carbon chains up to C8 or C9 and many, if not all, chain and substitution position isomers represented at each carbon number. The alpha-hydroxycarboxylic acids and alpha-hydroxydicarboxylic acids correspond structurally to many of the known meteoritic alpha-aminocarboxylic acids and alpha-aminodicarboxylic acids, a fact that supports the proposal that a Strecker synthesis was involved in the formation of both classes of compounds. Isotopic analyses show these acids to be D-rich relative to terrestrial organic compounds, as expected; however, the hydroxy acids appear to be isotopically lighter than the amino acids with respect to both carbon and hydrogen.

Simultaneous determination of flavonoids, isochlorogenic acids and triterpenoids in Ilex hainanensis Using high performance liquid chromatography coupled with diode array and evaporative light scattering detection.

PubMed

Peng, Bo; Qiao, Chun-Feng; Zhao, Jing; Huang, Wei-Hua; Hu, De-Jun; Liu, Hua-Gang; Li, Shao-Ping

2013-03-04

A high performance liquid chromatography coupled with diode array and evaporative light scattering detection (HPLC-DAD-ELSD) method for simultaneous determination of eight major bioactive compounds including two flavonoids (rutin and eriodictyol-7-O-β-D-glucopyranoside), two isochlorogenic acids (isochlorogenic acid A and isochlorogenic acid C) and four triterpenoids (ilexhainanoside D, ilexsaponin A1, ilexgenin A and ursolic acid) in Ilex hainanensis has been developed for the first time. The 283 nm wavelength was chosen for determination of two flavonoids and two isochlorogenic acids. ELSD was applied to determine four triterpenoids. The analysis was performed on an Agilent Zorbax SB-C18 column (250 × 4.6 mm i.d., 5 µm) with gradient elution of 0.2% formic acid in water and acetonitrile. The method was validated for linearity, limit of detection, limit of quantification, precision, repeatability and accuracy. The proposed method has been successfully applied for simultaneous quantification of the analytes in four samples of Ilex hainanensis, which is helpful for quality control of this plant.

The cyst wall of Colpoda steinii. A substance rich in glutamic acid residues

PubMed Central

Tibbs, J.

1966-01-01

1. The cyst wall of Colpoda steinii has been isolated and its chemical nature examined. It had a nitrogen content 13·9±0·2% (s.d.) and an ash 8·6±1·6% (s.d.). After lipid and hot-acid extraction there was a variable residual phosphorus of 0·19–0·64%. The protein nature, indicated by infrared and ultraviolet absorption, was confirmed when 100μg. of hydrolysed wall gave a ninhydrin colour equivalent to that given by 0·88–1·01μmoles of glycine. Hexosamine, hexose, pentose, lipid and dipicolinic acid were absent. 2. Paper chromatography of hydrolysates, besides showing the presence of the usual protein amino acids and three unidentified ninhydrin-reacting spots, indicated the presence of large amounts of glutamic acid. Estimated by chromatography, the amount present was 52·9±0·6 (s.d.) g./100g. of ash-free wall; manometric estimation of l-glutamic acid with l-glutamate 1-carboxy-lyase gave 46·5±0·9 (s.d.) g./100g. 3. Free carboxyl groups were estimated by titration as 0·159±0·011 (s.d.) mole/100g. and those present as amide as 0·154±0·004 (s.d.) mole/100g., and the total was compared with the dicarboxylic acid content 0·360±0·010 (s.d.) mole/100g. 4. After treatment with 98% formic acid 25–30% of the wall material could be extracted by 0·05m-sodium carbonate solution (extract 1); after treatment of the residue with performic acid a further 62–63% based on the original weight could be extracted by 0·05m-sodium carbonate (extract 2). 5. The average values found for the glutamic acid contents were 21·7g./100g. for extract 1 and 58·0g./100g. for extract 2. The cysteic acid content of whole oxidized wall was about 5·8g./100g. and of extract 2 also about 5·8g./100g. The glutamic acid and cysteic acid contents of the final residue were also investigated. 6. The significance of these extraction experiments in relation to the wall structure is discussed. ImagesPlate 1. PMID:4957913

Aspartic acid

MedlinePlus

... we eat. Aspartic acid is also called asparaginic acid. Aspartic acid helps every cell in the body work. It ... release Normal nervous system function Plant sources of aspartic acid include: avocado, asparagus, and molasses. Animal sources of ...

Synthesis of acid addition salt of delta-aminolevulinic acid from 5-bromo levulinic acid esters

DOEpatents

Moens, Luc

2003-06-24

A process of preparing an acid addition salt of delta-aminolevulinc acid comprising: a) dissolving a lower alkyl 5-bromolevulinate and hexamethylenetetramine in a solvent selected from the group consisting of water, ethyl acetate, chloroform, acetone, ethanol, tetrahydrofuran and acetonitrile, to form a quaternary ammonium salt of the lower alkyl 5-bromolevulinate; and b) hydrolyzing the quaternary ammonium salt with an inorganic acid to form an acid addition salt of delta-aminolevulinic acid.

5-(Tetradecyloxy)-2-furancarboxylic acid and related hypolipidemic fatty acid-like alkyloxyarylcarboxylic acids.

PubMed

Parker, R A; Kariya, T; Grisar, J M; Petrow, V

1977-06-01

5-(Tetradecyloxy)-2-furancarboxylic acid (91, RMI 14514) was found to lower blood lipids and to inhibit fatty acid synthesis with minimal effects on liver weight and liver fat content. This fatty acid-like compound represents a new class of hypolipidemic agent; it is effective in rats and monkeys. The compound resulted from discovery of hypolipidemic activity in certain beta-keto esters, postulation and confirmation of the corresponding benzoic acids as active metabolites, and systematic exploration of the structure--activity relationships.