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Sample records for 4-hydroxy-2-methylbenzoic acid formation

  1. In situ gels improve formation acidizing

    SciTech Connect

    Yeager, V.; Shuchart, C.

    1997-01-20

    Viscosity-controlled acid effectively improves acid placement, provides more uniform damage removal, improves surface etching, and controls acid fluid loss. Viscosity-controlled acid (VCA) contains gels that break back to original viscosity 1 day after being pumped. These acids have been used for: matrix-acidizing long horizontal and vertical well intervals; controlling fluid loss in fracture acidizing to obtain longer fractures and deeper live-acid penetration. Fluid pH controls gel formation and breaking. In one operator`s horizontal wells, viscosity-controlled acid increased production by 2.5--6 fold. In carbonate formation fracture-acidizing, these acids have shown production improvements of 170 to 375%. VCA acid can be used in both cased or open hole, in vertical or deviated/horizontal wells.

  2. Use of Fluorinated Compounds To Detect Aromatic Metabolites from m-Cresol in a Methanogenic Consortium: Evidence for a Demethylation Reaction

    PubMed Central

    Londry, Kathleen L.; Fedorak, Phillip M.

    1993-01-01

    Anaerobic sewage sludge was used to enrich a methanogenic m-cresol-degrading consortium. 6-Fluoro-3-methylphenol was synthesized and added to subcultures of the consortium with m-cresol. This caused the accumulation of 4-hydroxy-2-methylbenzoic acid. In a separate experiment, the addition of 3-fluorobenzoic acid caused the transient accumulation of 4-hydroxybenzoic acid. Inhibition with bromoethanesulfonic acid caused the accumulation of benzoic acid. Thus, the proposed degradation pathway was m-cresol → 4-hydroxy-2-methylbenzoic acid → 4-hydroxybenzoic acid → benzoic acid. The m-cresol-degrading consortium was able to convert exogenous 4-hydroxybenzoic acid and benzoic acid to methane. In addition, for each metabolite of m-cresol identified, the corresponding fluorinated metabolite was detected, giving the following sequence: 6-fluoro-3-methylphenol → 5-fluoro-4-hydroxy-2-methylbenzoic acid → 3-fluoro-4-hydroxybenzoic acid → 3-fluorobenzoic acid. The second step in each of these pathways is a novel demethylation which was rate limiting. This demethylation reaction would likely facilitate the transformation of the methyl group to methane, which is consistent with the results of a previous study that showed that the methyl carbon of m-[methyl-14C]cresol was recovered predominantly as [14C]methane (D. J. Roberts, P. M. Fedorak, and S. E. Hrudey, Can. J. Microbiol. 33:335-338, 1987). The final aromatic compound in the proposed route for m-cresol metabolism was benzoic acid, and its detection in these cultures merges the pathway for the methanogenic degradation of m-cresol with those for the anaerobic metabolism of many phenols. PMID:16348996

  3. Sulfuric acid as autocatalyst in the formation of sulfuric acid.

    PubMed

    Torrent-Sucarrat, Miquel; Francisco, Joseph S; Anglada, Josep M

    2012-12-26

    Sulfuric acid can act as a catalyst of its own formation. We have carried out a computational investigation on the gas-phase formation of H(2)SO(4) by hydrolysis of SO(3) involving one and two water molecules, and also in the presence of sulfuric acid and its complexes with one and two water molecules. The hydrolysis of SO(3) requires the concurrence of two water molecules, one of them acting as a catalyzer, and our results predict an important catalytic effect, ranging between 3 and 11 kcal·mol(-1) when the catalytic water molecule is substituted by a sulfuric acid molecule or one of its hydrates. In these cases, the reaction products are either bare sulfuric acid dimer or sulfuric acid dimer complexed with a water molecule. There are broad implications from these new findings. The results of the present investigation show that the catalytic effect of sulfuric acid in the SO(3) hydrolysis can be important in the Earth's stratosphere, in the heterogeneous formation of sulfuric acid and in the formation of aerosols, in H(2)SO(4) formation by aircraft engines, and also in understanding the formation of sulfuric acid in the atmosphere of Venus.

  4. Carboxylic acid accelerated formation of diesters

    DOEpatents

    Tustin, Gerald Charles; Dickson, Todd Jay

    1998-01-01

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

  5. Some factors affecting cyclopropane acid formation in Escherichia coli

    PubMed Central

    Knivett, V. A.; Cullen, Julia

    1965-01-01

    1. The fatty acid composition of the extractable lipids of Escherichia coli varied with growth conditions. 2. The principal fatty acids were palmitic acid, hexadecenoic acid, octadecenoic acid and the cyclopropane acids, methylenehexadecanoic acid and methyleneoctadecanoic acid. 3. Cyclopropane acid formation from monoenoic acids was increased by acid media, poor oxygen supply, or high growth temperature. 4. Cyclopropane acid formation was decreased by alkaline media, well oxygenated conditions, the presence of citrate, or lack of Mg2+. PMID:5324304

  6. [Significance of hydrocyanic acid formation during fires].

    PubMed

    von Meyer, L; Drasch, G; Kauert, G

    1979-01-01

    Cyanide concentrations of blood samples from fire victims autopsied in the Institute of Legal Medicine, Munich, have been determined. In 25% of 48 analyzed cases cyanide concentrations from 0.52 microgram to 6.24 microgram Cyanide/ml blood have been detected. These results are compared to former studies and the higher mean level in our collective is emphasized. The importance of hydrocyanid acid in the toxicity of fire gases is evidently greater, than assumed. Hydrocyanic acid may be produced from nitrogen continaing polymers during combustion. The quote of these polymers in clothing, furniture, and also in equipment of cars is increasing. Therefore, it is necessary to take more notice of the formation of hydrocyanic acid during combustion, even though carbon monoxide is in general the main toxic agent in fire gases.

  7. Compositions for acid treating subterranean formations

    SciTech Connect

    Clark, E. Jr.; Swanson, B.L.

    1991-03-05

    This patent describes a high viscosity acid composition. It comprises: an aqueous acid solution; one or more acrylamide polymers dissolved in the acid solution in an amount sufficient to increase the viscosity of the acid solution; a liquid hydrocarbon dispersed in the acid solution; and one or more nonionic surface active agents having at least one reactive hydroxyl group per molecule present in the composition in an amount sufficient to interact with the acrylamide polymer or polymers in the presence of the liquid hydrocarbon whereby the viscosity of the acid solution is further increased and stabilized.

  8. Formation of nitric acid hydrates - A chemical equilibrium approach

    NASA Technical Reports Server (NTRS)

    Smith, Roland H.

    1990-01-01

    Published data are used to calculate equilibrium constants for reactions of the formation of nitric acid hydrates over the temperature range 190 to 205 K. Standard enthalpies of formation and standard entropies are calculated for the tri- and mono-hydrates. These are shown to be in reasonable agreement with earlier calorimetric measurements. The formation of nitric acid trihydrate in the polar stratosphere is discussed in terms of these equilibrium constants.

  9. HF acid blends based on formation conditions eliminate precipitation problems

    SciTech Connect

    Gdanski, R.; Shuchart, C.

    1997-03-01

    Formulating HCl-HF acid blends based on the mineralogy and temperature of a formation can increase the success of hydrofluoric acid (HF) treatments. Sodium and potassium in the structures of formation minerals can cause precipitation and matrix plugging problems during acidizing. Slight modifications of the acid blend used in the treatment can help eliminate fluosilicate precipitation. Researchers recently conducted tests to determine how acid blends react in different formations under varying temperatures. The results of the tests indicate that the minimum HCl:HF ratio in an acid blend is 6-to-1, and the optimum ratio is 9-to-1. Regular mud acid (12% HCl-3% HF) has been used successfully for years to enhance production in sandstone formations. By the 1980s, operators began to vary the concentration of HF and HCl acids to solve excessive sanding problems in sandstone. The paper discusses treatment problems, formation characteristics, alumino-silicate scaling, research results, brine compatibility, optimum treatment, and acid volume guidelines.

  10. Amino Acid Formation on Interstellar Dust Particles

    NASA Astrophysics Data System (ADS)

    Meierhenrich, U. J.; Munoz Caro, G. M.; Barbier, B.; Brack, A.; Thiemann, W.; Goesmann, F.; Rosenbauer, H.

    2003-04-01

    In the dense interstellar medium dust particles accrete ice layers of known molecular composition. In the diffuse interstellar medium these ice layers are subjected to energetic UV-irradiation. Here, photoreactions form complex organic molecules. The interstellar processes were recently successfully simulated in two laboratories. At NASA Ames Research Center three amino acids were detected in interstellar ice analogues [1], contemporaneously, our European team reported on the identification of 16 amino acids therein [2]. Amino acids are the molecular building blocks of proteins in living organisms. The identification of amino acids on the simulated icy surface of interstellar dust particles strongly supports the assumption that the precursor molecules of life were delivered from interstellar and interplanetary space via (micro-) meteorites and/or comets to the earyl Earth. The results shall be verified by the COSAC experiment onboard the ESA cometary mission Rosetta [3]. [1] M.P. Bernstein, J.P. Dworkin, S.A. Sandford, G.W. Cooper, L.J. Allamandola: itshape Nature \\upshape 416 (2002), 401-403. [2] G.M. Muñoz Caro, U.J. Meierhenrich, W.A. Schutte, B. Barbier, A. Arcones Sergovia, H. Rosenbauer, W.H.-P. Thiemann, A. Brack, J.M. Greenberg: itshape Nature \\upshape 416 (2002), 403-406. [3] U. Meierhenrich, W.H.-P. Thiemann, H. Rosenbauer: itshape Chirality \\upshape 11 (1999), 575-582.

  11. Stimulation of acid formation in permeable gastric glands by valinomycin

    SciTech Connect

    Hersey, S.J.; Steiner, L. )

    1988-09-01

    Isolated gastric glands made permeable with digitonin treatment were employed to study the ionic requirements of acid formation. Acid formation was monitored by the accumulation of a novel weak base probe, ({sup 14}C)benzylamine. ATP-dependent acid formation was found to require K{sup +} in a concentration-dependent manner, with an apparent K{sub 0.5} = 7 mM. The anion dependence of acid formation gave a selectivity sequence of Cl = I > Br < NO{sub 3} > SO{sub 4} = isethionate, with isethionate being {approximately}50% as effective as Cl. The dependence of acid formation on (Cl) gave an apparent K{sub 0.5} = 6 mM. Addition of the K{sup +} ionophore, valinomycin, to resting glands (cimetidine pretreatment) resulted in a two- to threefold increase in ATP-dependent acid formation. In contrast, stimulated (forskolin pretreated) glands showed a greater accumulation of benzylamine with ATP but significantly less valinomycin stimulation. The valinomycin stimulation required both K{sup +} and Cl{sup {minus}} and was inhibited by omeprazole and Sch 28080. The results and interpreted to indicate that major events in the transition from a resting to a stimulated state include changes in both K{sup +} and anion permeability of the secretory membrane of parietal cells.

  12. Chlorogenic acid increased acrylamide formation through promotion of HMF formation and 3-aminopropionamide deamination.

    PubMed

    Cai, Yun; Zhang, Zhenhua; Jiang, Shanshan; Yu, Miao; Huang, Caihuan; Qiu, Ruixia; Zou, Yueyu; Zhang, Qirui; Ou, Shiyi; Zhou, Hua; Wang, Yong; Bai, Weibing; Li, Yiqun

    2014-03-15

    This research was aimed to investigate why chlorogenic acid, presents at high concentrations in some food raw material, influences acrylamide formation. In the asparagine/glucose Maillard reaction system (pH=6.8), addition of chlorogenic acid significantly increased acrylamide formation and inhibited its elimination. In contrast, the quinone derivative of chlorogenic acid decreased acrylamide formation. Three mechanisms may be involved for increasing acrylamide formation by chlorogenic acid. Firstly, it increased the formation of HMF, which acts as a more efficient precursor than glucose to form acrylamide. Secondly, it decreased activation energy for conversion of 3-aminopropionamide (3-APA) to acrylamide (from 173.2 to 136.6kJ/mol), and enhances deamination from 3-APA. And thirdly, it prevented attack of the produced acrylamide from free radicals by keeping high redox potential during the Maillard reaction.

  13. EFFECT OF ACIDITY ON SECONDARY ORGANIC AEROSOL FORMATION FROM ISOPRENE

    EPA Science Inventory

    The effect of particle-phase acidity on secondary organic aerosol (SOA) formation from isoprene is investigated in a laboratory chamber study, in which the acidity of the inorganic seed aerosol was controlled systematically. The observed enhancement in SOA mass concentration is c...

  14. Nicotinamide metabolism in ferns: formation of nicotinic acid glucoside.

    PubMed

    Ashihara, Hiroshi; Yin, Yuling; Watanabe, Shin

    2011-03-01

    The metabolic fate of [carbonyl-(14)C]nicotinamide was investigated in 9 fern species, Psilotum nudum, Angiopteris evecta, Lygodium japonicum, Acrostichum aureum, Asplenium antiquum, Diplazium subsinuatum, Thelypteris acuminate, Blechnum orientale and Crytomium fortune. All fern species produce a large quantity of nicotinic acid glucoside from [(14)C]nicotinamide, but trigonelline formation is very low. Increases in the release of (14)CO(2) with incubation time was accompanied by decreases in [carboxyl-(14)C]nicotinic acid glucoside. There was slight stimulation of nicotinic acid glucoside formation by 250 mM NaCl in mature leaves of the mangrove fern, Acrostichum aureum, but it is unlikely that this compound acts as a compatible solute. Nicotinamide and nicotinic acid salvage for pyridine nucleotide synthesis was detected in all fern species, although this activity was always less than nicotinic acid glucoside synthesis. Predominant formation of nicotinic acid glucoside is characteristic of nicotinic acid metabolism in ferns. This reaction appears to act as a detoxication mechanism, removing excess nicotinic acid.

  15. An Effective Acid Combination for Enhanced Properties and Corrosion Control of Acidizing Sandstone Formation

    NASA Astrophysics Data System (ADS)

    Umer Shafiq, Mian; Khaled Ben Mahmud, Hisham

    2016-03-01

    To fulfill the demand of the world energy, more technologies to enhance the recovery of oil production are being developed. Sandstone acidizing has been introduced and it acts as one of the important means to increase oil and gas production. Sandstone acidizing operation generally uses acids, which create or enlarge the flow channels of formation around the wellbore. In sandstone matrix acidizing, acids are injected into the formation at a pressure below the formation fracturing pressure, in which the injected acids react with mineral particles that may restrict the flow of hydrocarbons. Most common combination is Hydrofluoric Acid - Hydrochloric with concentration (3% HF - 12% HCl) known as mud acid. But there are some problems associated with the use of mud acid i.e., corrosion, precipitation. In this paper several new combinations of acids were experimentally screened to identify the most effective combination. The combinations used consist of fluoboric, phosphoric, formic and hydrofluoric acids. Cores were allowed to react with these combinations and results are compared with the mud acid. The parameters, which are analyzed, are Improved Permeability Ratio, strength and mineralogy. The analysis showed that the new acid combination has the potential to be used in sandstone acidizing.

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

    NASA Technical Reports Server (NTRS)

    Negron-Mendoza, A.; Ponnamperuma, C.

    1976-01-01

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

  17. Acid-base metabolism: implications for kidney stones formation.

    PubMed

    Hess, Bernhard

    2006-04-01

    The physiology and pathophysiology of renal H+ ion excretion and urinary buffer systems are reviewed. The main focus is on the two major conditions related to acid-base metabolism that cause kidney stone formation, i.e., distal renal tubular acidosis (dRTA) and abnormally low urine pH with subsequent uric acid stone formation. Both the entities can be seen on the background of disturbances of the major urinary buffer system, NH3+ <--> NH4+. On the one hand, reduced distal tubular secretion of H+ ions results in an abnormally high urinary pH and either incomplete or complete dRTA. On the other hand, reduced production/availability of NH4+ is the cause of an abnormally low urinary pH, which predisposes to uric acid stone formation. Most recent research indicates that the latter abnormality may be a renal manifestation of the increasingly prevalent metabolic syndrome. Despite opposite deviations from normal urinary pH values, both the dRTA and uric acid stone formation due to low urinary pH require the same treatment, i.e., alkali. In the dRTA, alkali is needed for improving the body's buffer capacity, whereas the goal of alkali treatment in uric acid stone formers is to increase the urinary pH to 6.2-6.8 in order to minimize uric acid crystallization.

  18. Smectite Formation in Acid Sulfate Environments on Mars

    NASA Technical Reports Server (NTRS)

    Peretyazhko, T. S.; Niles, P. B.; Sutter, B.; Clark, J. V.; Morris, R. V.; Ming, D. W.

    2017-01-01

    Phyllosilicates of the smectite group detected in Noachian and early Hesperian terrains on Mars were hypothesized to form under aqueous conditions that were globally neutral to alkaline. These pH conditions and the presence of a CO2-rich atmosphere should have been favorable for the formation of large carbonate deposits. However, large-scale carbonate deposits have not been detected on Mars. We hypothesized that smectite deposits are consistent with perhaps widespread acidic aqueous conditions that prevented carbonate precipitation. The objective of our work was to investigate smectite formation under acid sulfate conditions in order to provide insight into the possible geochemical conditions required for smectite formation on Mars. Hydrothermal batch incubation experiments were performed with Mars-analogue, glass-rich, basalt simulant in the presence of sulfuric acid of variable concentration.

  19. Prebiotic formation of polyamino acids in molten urea

    NASA Astrophysics Data System (ADS)

    Mita, H.; Nomoto, S.; Terasaki, M.; Shimoyama, A.; Yamamoto, Y.

    2005-04-01

    It is important for research into the origins of life to elucidate polyamino acid formation under prebiotic conditions. Only a limited set of amino acids has been reported to polymerize thermally. In this paper we demonstrate a novel thermal polymerization mechanism in a molten urea of alkylamino acids (i.e. glycine, alanine, β-alanine, α-aminobutyric acid, valine, norvaline, leucine and norleucine), which had been thought to be incapable of undergoing thermal polymerization. Also, aspartic acid was found to polymerize in molten urea at a lower temperature than that at which aspartic acid alone had previously been thermally polymerized. Individual oligomers produced in heating experiments on urea-amino acid mixtures were analysed using a liquid chromatograph mass spectrometer. Major products in the reaction mixture were three different types of polyamino acid derivatives: N-carbamoylpolyamino acids, polyamino acids containing a hydantoin ring at the N-terminal position and unidentified derivatives with molecular weights that were greater by 78 than those of the corresponding peptide forms. The polymerization reaction occurred by taking advantage of the high polarity of molten urea as well as its dehydrating ability. Under the presumed prebiotic conditions employed here, many types of amino acids were thus revealed to undergo thermal polymerization.

  20. Chlorogenic Acid Inhibits Human Platelet Activation and Thrombus Formation

    PubMed Central

    Fuentes, Eduardo; Caballero, Julio; Alarcón, Marcelo; Rojas, Armando; Palomo, Iván

    2014-01-01

    Background Chlorogenic acid is a potent phenolic antioxidant. However, its effect on platelet aggregation, a critical factor in arterial thrombosis, remains unclear. Consequently, chlorogenic acid-action mechanisms in preventing platelet activation and thrombus formation were examined. Methods and Results Chlorogenic acid in a dose-dependent manner (0.1 to 1 mmol/L) inhibited platelet secretion and aggregation induced by ADP, collagen, arachidonic acid and TRAP-6, and diminished platelet firm adhesion/aggregation and platelet-leukocyte interactions under flow conditions. At these concentrations chlorogenic acid significantly decreased platelet inflammatory mediators (sP-selectin, sCD40L, CCL5 and IL-1β) and increased intraplatelet cAMP levels/PKA activation. Interestingly, SQ22536 (an adenylate cyclase inhibitor) and ZM241385 (a potent A2A receptor antagonist) attenuated the antiplatelet effect of chlorogenic acid. Chlorogenic acid is compatible to the active site of the adenosine A2A receptor as revealed through molecular modeling. In addition, chlorogenic acid had a significantly lower effect on mouse bleeding time when compared to the same dose of aspirin. Conclusions Antiplatelet and antithrombotic effects of chlorogenic acid are associated with the A2A receptor/adenylate cyclase/cAMP/PKA signaling pathway. PMID:24598787

  1. Characteristics and formation of amino acids and hydroxy acids of the Murchison meteorite

    NASA Technical Reports Server (NTRS)

    Cronin, J. R.; Cooper, G. W.; Pizzarello, S.

    1995-01-01

    Eight characteristics of the unique suite of amino acids and hydroxy acids found in the Murchison meteorite can be recognized on the basis of detailed molecular and isotopic analyses. The marked structural correspondence between the alpha-amino acids and alpha-hydroxy acids and the high deuterium/hydrogen ratio argue persuasively for their formation by aqueous phase Strecker reactions in the meteorite parent body from presolar, i.e., interstellar, aldehydes, ketones, ammonia, and hydrogen cyanide. The characteristics of the meteoritic suite of amino acids and hydroxy acids are briefly enumerated and discussed with regard to their consonance with this interstellar-parent body formation hypothesis. The hypothesis has interesting implications for the organic composition of both the primitive parent body and the presolar nebula.

  2. Artefact formation during acid hydrolysis of saponins from Medicago spp.

    PubMed

    Tava, Aldo; Biazzi, Elisa; Mella, Mariella; Quadrelli, Paolo; Avato, Pinarosa

    2017-02-28

    Artefact compounds obtained during acid hydrolysis of saponins from Medicago spp. (Fabaceae), have been monitored and evaluated by GC-FID. Their identification has been performed by GC-MS and (1)H and (13)C NMR. Saponins with different substituents on the triterpenic pentacyclic aglycones were considered, and their hydrolysis products were detected and quantified during 10 h of time course reaction. From soyasapogenol B glycoside the well known soyasapogenols B, C, D and F were obtained together with a previously undescribed sapogenol artefact identified as 3β,22β,24-trihydroxyolean-18(19)-en and named soyasapogenol H. From a zanhic acid saponin two major artefact compounds identified as 2β,3β,16α-trihydroxyolean-13(18)-en-23,28-dioic acid and 2β,3β,16α-trihydroxyolean-28,13β-olide-23-oic acid were obtained, together with some zanhic acid. Other compounds, detected in very small amount in the reaction mixture, were also tentatively identified based on their GC-MS and UV spectra. The other most characteristic saponins in Medicago spp., hederagenin, bayogenin and medicagenic acid glycosides, under acidic condition of hydrolysis, released instead the correspondent aglycones and generated a negligible amount of artefacts. Nature of artefacts and mechanism of their formation, involving a stable tertiary carbocation, is here proposed and discussed for the first time.

  3. Amino acids inhibit kynurenic acid formation via suppression of kynurenine uptake or kynurenic acid synthesis in rat brain in vitro.

    PubMed

    Sekine, Airi; Okamoto, Misaki; Kanatani, Yuka; Sano, Mitsue; Shibata, Katsumi; Fukuwatari, Tsutomu

    2015-01-01

    The tryptophan metabolite, kynurenic acid (KYNA), is a preferential antagonist of the α7 nicotinic acetylcholine receptor at endogenous brain concentrations. Recent studies have suggested that increase of brain KYNA levels is involved in psychiatric disorders such as schizophrenia and depression. KYNA-producing enzymes have broad substrate specificity for amino acids, and brain uptake of kynurenine (KYN), the immediate precursor of KYNA, is via large neutral amino acid transporters (LAT). In the present study, to find out amino acids with the potential to suppress KYNA production, we comprehensively investigated the effects of proteinogenic amino acids on KYNA formation and KYN uptake in rat brain in vitro. Cortical slices of rat brain were incubated for 2 h in Krebs-Ringer buffer containing a physiological concentration of KYN with individual amino acids. Ten out of 19 amino acids (specifically, leucine, isoleucine, phenylalanine, methionine, tyrosine, alanine, cysteine, glutamine, glutamate, and aspartate) significantly reduced KYNA formation at 1 mmol/L. These amino acids showed inhibitory effects in a dose-dependent manner, and partially inhibited KYNA production at physiological concentrations. Leucine, isoleucine, methionine, phenylalanine, and tyrosine, all LAT substrates, also reduced tissue KYN concentrations in a dose-dependent manner, with their inhibitory rates for KYN uptake significantly correlated with KYNA formation. These results suggest that five LAT substrates inhibit KYNA formation via blockade of KYN transport, while the other amino acids act via blockade of the KYNA synthesis reaction in brain. Amino acids can be a good tool to modulate brain function by manipulation of KYNA formation in the brain. This approach may be useful in the treatment and prevention of neurological and psychiatric diseases associated with increased KYNA levels.

  4. Dissecting Abscisic Acid Signaling Pathways Involved in Cuticle Formation.

    PubMed

    Cui, Fuqiang; Brosché, Mikael; Lehtonen, Mikko T; Amiryousefi, Ali; Xu, Enjun; Punkkinen, Matleena; Valkonen, Jari P T; Fujii, Hiroaki; Overmyer, Kirk

    2016-06-06

    The cuticle is the outer physical barrier of aerial plant surfaces and an important interaction point between plants and the environment. Many environmental stresses affect cuticle formation, yet the regulatory pathways involved remain undefined. We used a genetics and gene expression analysis in Arabidopsis thaliana to define an abscisic acid (ABA) signaling loop that positively regulates cuticle formation via the core ABA signaling pathway, including the PYR/PYL receptors, PP2C phosphatase, and SNF1-Related Protein Kinase (SnRK) 2.2/SnRK2.3/SnRK2.6. Downstream of the SnRK2 kinases, cuticle formation was not regulated by the ABA-responsive element-binding transcription factors but rather by DEWAX, MYB16, MYB94, and MYB96. Additionally, low air humidity increased cuticle formation independent of the core ABA pathway and cell death/reactive oxygen species signaling attenuated expression of cuticle-biosynthesis genes. In Physcomitrella patens, exogenous ABA suppressed expression of cuticle-related genes, whose Arabidopsis orthologs were ABA-induced. Hence, the mechanisms regulating cuticle formation are conserved but sophisticated in land plants. Signaling specifically related to cuticle deficiency was identified to play a major role in the adaptation of ABA signaling pathway mutants to increased humidity and in modulating their immunity to Botrytis cinerea in Arabidopsis. These results define a cuticle-specific downstream branch in the ABA signaling pathway that regulates responses to the external environment.

  5. Parameters affecting the formation of perfluoroalkyl acids during wastewater treatment.

    PubMed

    Guerra, P; Kim, M; Kinsman, L; Ng, T; Alaee, M; Smyth, S A

    2014-05-15

    This study examined the fate and behaviour of perfluoroalkyl acids (PFAAs) in liquid and solid samples from five different wastewater treatment types: facultative and aerated lagoons, chemically assisted primary treatment, secondary aerobic biological treatment, and advanced biological nutrient removal treatment. To the best of our knowledge, this is the largest data set from a single study available in the literature to date for PFAAs monitoring study in wastewater treatment. Perfluorooctanoic acid (PFOA) was the predominant PFAA in wastewater with levels from 2.2 to 150ng/L (influent) and 1.9 to 140ng/L (effluent). Perfluorooctanesulfonic acid (PFOS) was the predominant compound in primary sludge, waste biological sludge, and treated biosolids with concentrations from 6.4 to 2900ng/g dry weight (dw), 9.7 to 8200ng/gdw, and 2.1 to 17,000ng/gdw, respectively. PFAAs were formed during wastewater treatment and it was dependant on both process temperature and treatment type; with higher rates of formation in biological wastewater treatment plants (WWTPs) operating at longer hydraulic retention times and higher temperatures. PFAA removal by sorption was influenced by different sorption tendencies; median log values of the solid-liquid distribution coefficient estimated from wastewater biological sludge and final effluent were: PFOS (3.73)>PFDA (3.68)>PFNA (3.25)>PFOA (2.49)>PFHxA (1.93). Mass balances confirmed the formation of PFAAs, low PFAA removal by sorption, and high PFAA levels in effluents.

  6. Formation of chloroacetic acids from soil, humic acid and phenolic moieties.

    PubMed

    Fahimi, I J; Keppler, F; Schöler, H F

    2003-07-01

    The mechanism of formation of chloroacetates, which are important toxic environmental substances, has been controversial. Whereas the anthropogenic production has been well established, a natural formation has also been suggested. In this study the natural formation of chloroacetic acids from soil, as well as from humic material which is present in soil and from phenolic model substances has been investigated. It is shown that chloroacetates are formed from humic material with a linear relationship between the amount of humic acid used and chloroacetates found. More dichloroacetate (DCA) than trichloroacetate (TCA) is produced. The addition of Fe(2+), Fe(3+) and H(2)O(2) leads to an increased yield. NaCl was added as a source of chloride. We further examined the relationship between the structure and reactivity of phenolic substances, which can be considered as monomeric units of humic acids. Ethoxyphenol with built-in ethyl groups forms large amounts of DCA and TCA. The experiments with phenoxyacetic acid yielded large amounts of monochloroacetate (MCA). With other phenolic substances a ring cleavage was observed. Our investigations indicate that chloroacetates are formed abiotically from humic material and soils in addition to their known biotic mode of formation.

  7. Biomimetic formation of chicoric-acid-directed luminescent silver nanodendrites.

    PubMed

    Barnaby, Stacey N; Sarker, Nazmul H; Tsiola, Areti; Banerjee, Ipsita A

    2012-07-27

    In this work, we report the formation of well-defined silver nanodendrites via biomineralization under mild conditions in a single step, in the presence of the plant phytohormone chicoric acid (CA), a well-known HIV-I integrase inhibitor. CA played a dual role as reductant as well as directed the growth of the nanodendrites, which were found to grow primarily in the [111] and [200] directions. In addition to the formation of highly ordered hierarchical structures, the formed Ag nanodendrites were found to exhibit luminescence, as observed by confocal microscopy. This study not only demonstrates a new method for the preparation of luminescent silver nanodendrites using a simple, environmentally friendly biological method, but also indicates the ability of CA, a potent HIV-integrase inhibitor, to interact with silver ions which may shed light on its potential for additional biomedical and biosensor applications.

  8. Biomimetic formation of chicoric-acid-directed luminescent silver nanodendrites

    NASA Astrophysics Data System (ADS)

    Barnaby, Stacey N.; Sarker, Nazmul H.; Tsiola, Areti; Banerjee, Ipsita A.

    2012-07-01

    In this work, we report the formation of well-defined silver nanodendrites via biomineralization under mild conditions in a single step, in the presence of the plant phytohormone chicoric acid (CA), a well-known HIV-I integrase inhibitor. CA played a dual role as reductant as well as directed the growth of the nanodendrites, which were found to grow primarily in the [111] and [200] directions. In addition to the formation of highly ordered hierarchical structures, the formed Ag nanodendrites were found to exhibit luminescence, as observed by confocal microscopy. This study not only demonstrates a new method for the preparation of luminescent silver nanodendrites using a simple, environmentally friendly biological method, but also indicates the ability of CA, a potent HIV-integrase inhibitor, to interact with silver ions which may shed light on its potential for additional biomedical and biosensor applications.

  9. Formation and Survival of Amino Acids in Space

    NASA Technical Reports Server (NTRS)

    Bernstein, M. P.; Sandford, S. A.; Allamandola, L. J.

    2003-01-01

    The detection of deuterium enrichments in meteoritic hydroxy and amino acids demonstrates that there is a connection between organic material in the interstellar medium and in primitive meteorites. It has generally been assumed that such molecules formed via reactions of small deuterium enriched insterstellar precursors in liquid water on a large asteroidal or cometary parent body. We have recently show that the W photolysis of interstellar/presolar ices can produce the amino acids alanine, serine, and glycine, as well as hydroxy acids, and glycerol, all of which have been extracted from the Murchison meteorite. Thus, some of the probiologically interesting organic compounds, compounds found in meteorites may have formed in presolar ice and have not solely been a product of parent body liquid water chemistry. We will report on our isotopic labeling studies of the mechanism of formation of these interesting compounds, and on astrophysically relevant kinetic studies UV photodecomposition of amino acid precursors in the solid state. This is our first year of exobiology funding on this project.

  10. Formation and Survival of Amino Acids in Space

    NASA Technical Reports Server (NTRS)

    Bernstein, M. P.; Sandford, S. A.; Allamandola, L. J.

    2003-01-01

    The detection of deuterium enrichments in meteoritic hydroxy and amino acids demonstrates that there is a connection between organic material in the interstellar medium and in piimitive meteorites. It has generally been assumed that such molecules formed via reactions of small deuterium enriched insterstellar precursors in liquid water on a large asteroidal or cometary parent body. We have recently show that the W photolysis of interstellar/presolar ices can produce the amino acids alanine, serine, and glycine, as well as hydroxy acids, and glycerol, all of which have been extracted from the Murchison meteorite. Thus, some of the probiologically interesting organic compounds compounds found in meteorites may have formed in presolar ice and have not solely been a product of parent body liquid water chemistry. We will report on our isotopic labeling studies of the mechanism of formation of these inteiesting compounds, and on astrophysically relevant kinetic studies UV photo-decomposition of amino acid precursors in the solid state. This is our first year of exobiology funding on this project.

  11. Smectite Formation from Basaltic Glass Under Acidic Conditions on Mars

    NASA Technical Reports Server (NTRS)

    Peretyazhko, T. S.; Sutter, B.; Morris, R. V.; Agresti, D. G.; Le, L.; Ming, D. W.

    2015-01-01

    Massive deposits of phyllosilicates of the smectite group, including Mg/Fe-smectite, have been identified in Mars's ancient Noachian terrain. The observed smectite is hypothesized to form through aqueous alteration of basaltic crust under neutral to alkaline pH conditions. These pH conditions and the presence of a CO2-rich atmosphere suggested for ancient Mars were favorable for the formation of large carbonate deposits. However, the detection of large-scale carbonate deposits is limited on Mars. We hypothesized that smectite deposits may have formed under acidic conditions that prevented carbonate precipitation. In this work we investigated formation of saponite at a pH of approximately 4 from Mars-analogue synthetic Adirondack basaltic glass of composition similar to Adirondack class rocks located at Gusev crater. Hydrothermal (200º Centigrade) 14 day experiments were performed with and without 10 millimoles Fe(II) or Mg under anoxic condition [hereafter denoted as anoxic_Fe, anoxic_Mg and anoxic (no addition of Fe(II) or Mg)] and under oxic condition [hereafter denoted as oxic (no addition of Fe(II) or Mg)]. Characterization and formation conditions of the synthesized saponite provided insight into the possible geochemical conditions required for saponite formation on Mars.

  12. Ellagic acid inhibits iron-mediated free radical formation.

    PubMed

    Dalvi, Luana T; Moreira, Daniel C; Andrade, Roberto; Ginani, Janini; Alonso, Antonio; Hermes-Lima, Marcelo

    2017-02-15

    Polyphenols are reported to have some health benefits, which are link to their antioxidant properties. In the case of ellagic acid (EA), there is evidence that it has free radical scavenger properties and that it is able to form complexes with metal ions. However, information on a possible link between the formation of iron-EA complexes and their interference in Haber-Weiss/Fenton reactions was not yet determined. Thus, the present study investigated the in vitro antioxidant mechanism of EA in a system containing ascorbate, Fe(III) and different iron ligands (EDTA, citrate and NTA). Iron-mediated oxidative degradation of 2-deoxyribose was poorly inhibited (by 12%) in the presence of EA (50μM) and EDTA. When citrate or NTA - which form weak iron complexes - were used, the 2-deoxyribose protection increased to 89-97% and 45%, respectively. EA also presented equivalent inhibitory effects on iron-mediated oxygen uptake and ascorbyl radical formation. Spectral analyses of iron-EA complexes show that EA removes Fe(III) from EDTA within hours, and from citrate within 1min. This difference in the rate of iron-EA complex formation may explain the antioxidant effects of EA. Furthermore, the EA antioxidant effectiveness was inversely proportional to the Fe(III) concentration, suggesting a competition with EDTA. In conclusion, the results indicate that EA may prevent in vitro free radical formation when it forms a complex with iron ions.

  13. Ellagic acid inhibits iron-mediated free radical formation

    NASA Astrophysics Data System (ADS)

    Dalvi, Luana T.; Moreira, Daniel C.; Andrade, Roberto; Ginani, Janini; Alonso, Antonio; Hermes-Lima, Marcelo

    2017-02-01

    Polyphenols are reported to have some health benefits, which are link to their antioxidant properties. In the case of ellagic acid (EA), there is evidence that it has free radical scavenger properties and that it is able to form complexes with metal ions. However, information on a possible link between the formation of iron-EA complexes and their interference in Haber-Weiss/Fenton reactions was not yet determined. Thus, the present study investigated the in vitro antioxidant mechanism of EA in a system containing ascorbate, Fe(III) and different iron ligands (EDTA, citrate and NTA). Iron-mediated oxidative degradation of 2-deoxyribose was poorly inhibited (by 12%) in the presence of EA (50 μM) and EDTA. When citrate or NTA - which form weak iron complexes - were used, the 2-deoxyribose protection increased to 89-97% and 45%, respectively. EA also presented equivalent inhibitory effects on iron-mediated oxygen uptake and ascorbyl radical formation. Spectral analyses of iron-EA complexes show that EA removes Fe(III) from EDTA within hours, and from citrate within 1 min. This difference in the rate of iron-EA complex formation may explain the antioxidant effects of EA. Furthermore, the EA antioxidant effectiveness was inversely proportional to the Fe(III) concentration, suggesting a competition with EDTA. In conclusion, the results indicate that EA may prevent in vitro free radical formation when it forms a complex with iron ions.

  14. Sulfuric Acid Monohydrate: Formation and Heterogeneous Chemistry in the Stratosphere

    NASA Technical Reports Server (NTRS)

    Zhang, Renyi; Leu, Ming-Taun; Keyser, Leon F.

    1995-01-01

    We have investigated some thermodynamic properties (i.e., freezing/melting points) and heterogeneous chemistry of sulfuric acid monohydrate (SAM, H2SO4.H2O), using a fast flow reactor coupled to a quadrupole mass spectrometer. The freezing point observations of thin liquid sulfuric acid films show that for acid contents between 75 and 85 wt % the monohydrate crystallizes readily at temperatures between 220 and 240 K on a glass substrate. Once formed, SAM can be thermodynamically stable in the H2O partial pressure range of (1-4) x 10(exp -4) torr and in the temperature range of 220-240 K. For a constant H2O partial pressure, lowering the temperature causes SAM to melt when the temperature and water partial pressure conditions are out of its stability regime. The reaction probability measurements indicate that the hydrolysis of N2O5 is significantly suppressed owing to the formation of crystalline SAM: The reaction probability on water-rich SAM (with higher relative humidity, or RH) is of the order of 10(exp -3) at 210 K and decreases by more than an order of magnitude for the acid-rich form (with lower RH). The hydrolysis rate of ClONO2 on water-rich SAM is even smaller, of the order of 10(exp -4) at 195 K. These reported values on crystalline SAM are much smaller than those on liquid solutions. No enhancement of these reactions is observed in the presence of HCl vapor at the stratospheric concentrations. In addition, Brunauer, Emmett, and Teller analysis of gas adsorption isotherms and photomicrography have been performed to characterize the surface roughness and porosities of the SAM substrate. The results suggest the possible formation of SAM in some regions of the middle- or low-latitude stratosphere and, consequently, much slower heterogeneous reactions on the frozen aerosols.

  15. Method of preparing and using and composition for acidizing subterranean formations

    SciTech Connect

    Dill, W.R.

    1984-08-21

    A composition and method of acidizing or fracturing a subterranean formation comprises contacting the formation with a composition comprising an acid, urea, and a selected gelling agent. The urea is present in an amount sufficient to extend the viscous stability of the gelled acid composition in comparison to the acid and gelling agent alone.

  16. Collapsed state of polyglutamic acid results in amyloid spherulite formation

    PubMed Central

    Stehli, Daniel; Mulaj, Mentor; Miti, Tatiana; Traina, Joshua; Foley, Joseph; Muschol, Martin

    2015-01-01

    Self-assembly of proteins and peptides into amyloid fibrils involves multiple distinct intermediates and late-stage fibrillar polymorphs. Understanding the conditions and mechanisms that promote the formation of one type of intermediate and polymorph over the other represents a fundamental challenge. Answers to this question are also of immediate biomedical relevance since different amyloid aggregate species have been shown to have distinct pathogenic potencies. One amyloid polymorph that has received comparatively little attention are amyloid spherulites. Here we report that self-assembly of the intrinsically disordered polymer poly(L-glutamic) acid (PLE) can generate amyloid spherulites. We characterize spherulite growth kinetics, as well as the morphological, optical and tinctorial features of this amyloid polymorph previously unreported for PLE. We find that PLE spherulites share both tinctorial and structural characteristics with their amyloid fibril counterparts. Differences in PLE's molecular weight, polydispersity or chemistry could not explain the selective propensity toward either fibril or spherulite formation. Instead, we provide evidence that PLE polymers can exist in either a collapsed globule or an extended random coil conformation. The collapsed globule consistently produces spherulites while the extended coil assembles into disordered fibril bundles. This results suggests that these 2 PLE conformers directly affect the morphology of the resulting macroscopic amyloid assembly.

  17. Perfluorocarboxylic acid (PFCA) atmospheric formation and transport to the Arctic.

    NASA Astrophysics Data System (ADS)

    Pike-thackray, C.; Selin, N. E.

    2015-12-01

    Perfluorocarboxylic acids (PFCAs) are highly persistent and toxic environmental contaminants that have been found in remote locations such as the Arctic, far from emission sources. These persistent organic pollutants are emitted directly to the atmosphere as well as being produced by the degradation of precursor compounds in the atmosphere, but recent trends towards increasing precursor emissions and decreasing direct emissions raise the importance of production in the atmosphere. Our work aims to improve understanding of the atmospheric degradation of fluorotelomer precursor compounds to form the long-chain PFCAs PFOA (C8) and PFNA (C9).Using the atmospheric chemical transport model GEOS-Chem, which uses assimilated meteorology to simulate the atmospheric transport of trace gas species, we investigate the interaction of the atmospheric formation of PFCAs and the atmospheric transport of their precursor species. Our simulations are a first application of the GEOS-Chem framework to PFCA chemistry. We highlight the importance of the spatial and temporal variability of background atmospheric chemical conditions experienced during transport. We find that yields and formation times of PFOA and PFNA respond differently and strongly to the photochemical conditions of the atmosphere, such as the abundance of NO, HO2, and other photochemical species.

  18. Biochemical and dietary factors of uric acid stone formation.

    PubMed

    Trinchieri, Alberto; Montanari, Emanuele

    2017-02-28

    The aim of this study was to compare the clinical characteristics of "pure" uric acid renal stone formers (UA-RSFs) with that of mixed uric acid/calcium oxalate stone formers (UC-RSFs) and to identify which urinary and dietary risk factors predispose to their formation. A total of 136 UA-RSFs and 115 UC-RSFs were extracted from our database of renal stone formers. A control group of 60 subjects without history of renal stones was considered for comparison. Data from serum chemistries, 24-h urine collections and 24-h dietary recalls were considered. UA-RSFs had a significantly (p = 0.001) higher body mass index (26.3 ± 3.6 kg/m(2)) than UC-RSFs, whereas body mass index of UA-RSFs was higher but not significantly than in controls (24.6 ± 4.7) (p = 0.108). The mean urinary pH was significantly lower in UA-RSFs (5.57 ± 0.58) and UC-RSFs (5.71 ± 0.56) compared with controls (5.83 ± 0.29) (p = 0.007). No difference of daily urinary uric acid excretion was observed in the three groups (p = 0.902). Daily urinary calcium excretion was significantly (p = 0.018) higher in UC-RSFs (224 ± 149 mg/day) than UA-RSFs (179 ± 115) whereas no significant difference was observed with controls (181 ± 89). UA-RSFs tend to have a lower uric acid fractional excretion (0.083 ± 0.045% vs 0.107+/-0.165; p = 0.120) and had significantly higher serum uric acid (5.33 ± 1.66 vs 4.78 ± 1.44 mg/dl; p = 0.007) than UC-RSFs. The mean energy, carbohydrate and vitamin C intakes were higher in UA-SFs (1987 ± 683 kcal, 272 ± 91 g, 112 ± 72 mg) and UC-SFs (1836 ± 74 kcal, 265 ± 117, 140 ± 118) with respect to controls (1474 ± 601, 188 ± 84, 76 ± 53) (p = 0.000). UA-RSFs should be differentiated from UC-RSFs as they present lower urinary pH, lower uric acid fractional excretion and higher serum uric acid. On the contrary, patients with UC-RSFs show urinary risk factors

  19. Laser photocoagulation stops diabetic retinopathy by controlling lactic acid formation

    NASA Astrophysics Data System (ADS)

    Wolbarsht, Myron L.

    1994-08-01

    Many different types of proliferative retinopathy induced by various types of initial disorders have a common pathology in their mid and terminal stages. Thus, proper therapy is devoted toward elimination of the initial cause as well as alleviation of the proliferative processes. Vasodilatation, which is an initial symptom of diabetes, is itself destructive to the retinal capillary bed and appears to be a constant feature in all stages of diabetic retinopathy. In the mid and late stages, the vasodilatation seems very dependent upon capillary dropout, whereas the initial vasodilatation may derive from quite different causes. The efficacy of photocoagulation as a therapy for all stages seems to derive from decreasing the metabolism in the photoreceptor layer sufficiently to result in vasoconstriction of the retinal vessels. A model is proposed to show how diabetes, by altering the metabolism in the photoreceptor layer to produce excess lactic acid, causes the initial vasodilatation. The lactic acid also induces free radical (superoxide) formation; both act together to destroy the retinal capillary bed followed by vasoproliferation. Photocoagulation, thus, is even more appropriate for this particular syndrome than previously had been thought, as it not only reduces potentially destructive vasodilatation but also removes the metabolic cause of the free radical induced destruction of the capillary endothelium which is the initial step in capillary drop-out. A review of the present data indicates that the best type of pan- retinal photocoagulation is a very light type affecting the photoreceptors only with a minimal amount of damage to other parts of retina and the vessels in the choroid. The possible use of photochemical types of destruction of the photoreceptor as a therapeutic modality is attractive, but it is certainly too speculative to use until more detailed investigations have been completed. However, the basic therapeutic approach of choice may be to prevent the

  20. Granuloma formation by muramyl dipeptide associated with branched fatty acids, a structure probably essential for tubercle formation by Mycobacterium tuberculosis.

    PubMed Central

    Emori, K; Nagao, S; Shigematsu, N; Kotani, S; Tsujimoto, M; Shiba, T; Kusumoto, S; Tanaka, A

    1985-01-01

    Muramyl dipeptide, which does not induce epithelioid granuloma when injected alone dissolved in phosphate-buffered saline, could induce extensive granulomas in guinea pigs when chemically conjugated with branched, but not linear, fatty acids. Peptidoglycan fragments of Staphylococcus epidermidis could evoke epithelioid granulomas when incorporated in a water-in-oil emulsion. These findings suggest the importance of a lipid bound to muramyl dipeptide for granuloma formation. In view of the fact that mycobacteria uniquely contain large amounts of branched fatty acids, it was proposed that the complex of muramyl dipeptide and branched fatty acids, mostly mycolic acids, is a structure in tubercle bacilli responsible for tubercle formation. Images PMID:3924828

  1. Chlorogenic acid increased 5-hydroxymethylfurfural formation when heating fructose alone or with aspartic acid at two pH levels.

    PubMed

    Zhang, Zhenhua; Zou, Yueyu; Wu, Taigang; Huang, Caihuan; Pei, Kehan; Zhang, Guangwen; Lin, Xiaohua; Bai, Weibin; Ou, Shiyi

    2016-01-01

    Chlorogenic acid (CGA) is a phenolic acid that ubiquitously exists in fruits. This work aims to investigate whether and how CGA influences HMF formation during heating fructose alone, or with an amino acid. The results showed that that CGA increased 5-hydroxymethylfurfural (HMF) formation. At pH 5.5 and 7.0, the addition of 5.0 μmol/ml CGA increased HMF formation by 49.4% and 25.2%, respectively when heating fructose alone, and by 9.0% and 16.7%, respectively when heating fructose with aspartic acid. CGA significantly increased HMF formation by promoting 3-deoxosone formation, and its conversion to HMF by inhibiting HMF elimination, especially in the Maillard reaction system. A comparison of the catalytic capacity of CGA with its six analogous compounds showed that both its di-hydroxyphenyl and carboxyl groups function in increasing HMF formation.

  2. On the abiotic formation of amino acids. I - HCN as a precursor of amino acids detected in extracts of lunar samples. II - Formation of HCN and amino acids from simulated mixtures of gases released from lunar samples

    NASA Technical Reports Server (NTRS)

    Yuasa, S.; Flory, D.; Basile, B.; Oro, J.

    1984-01-01

    Two studies on the abiotic formation of amino acids are presented. The first study demonstrates the role of hydrogen cyanide as a precursor of amino acids detected in extracts of lunar samples. The formation of several amino acids, including glycine, alanine, aspartic acid, and glutamic acid, under conditions similar to those used for the analysis of lunar samples is demonstrated. The second study investigates the formation of hydrogen cyanide as well as amino acids from lunar-sample gas mixtures under electrical discharge conditions. These results extend the possibility of synthesis of amino acids to planetary bodies with primordial atmospheres less reducing than a mixture of methane, ammonia, hydrogen and water.

  3. Natural abiotic formation of oxalic acid in soils: results from aromatic model compounds and soil samples.

    PubMed

    Studenroth, Sabine; Huber, Stefan G; Kotte, Karsten; Schöler, Heinz F

    2013-02-05

    Oxalic acid is the smallest dicarboxylic acid and plays an important role in soil processes (e.g., mineral weathering and metal detoxification in plants). We have first proven its abiotic formation in soils and investigated natural abiotic degradation processes based on the oxidation of soil organic matter, enhanced by Fe(3+) and H(2)O(2) as hydroxyl radical suppliers. Experiments with the model compound catechol and further hydroxylated benzenes were performed to examine a common degradation pathway and to presume a general formation mechanism of oxalic acid. Two soil samples were tested for the release of oxalic acid and the potential effects of various soil parameters on oxalic acid formation. Additionally, the soil samples were treated with different soil sterilization methods to prove the oxalic acid formation under abiotic soil conditions. Different series of model experiments were conducted to determine a range of factors including Fe(3+), H(2)O(2), reaction time, pH, and chloride concentration on oxalic acid formation. Under certain conditions, catechol is degraded up to 65.6% to oxalic acid referring to carbon. In serial experiments with two soil samples, oxalic acid was produced, and the obtained results are suggestive of an abiotic degradation process. In conclusion, Fenton-like conditions with low Fe(3+) concentrations and an excess of H(2)O(2) as well as acidic conditions were required for an optimal oxalic acid formation. The presence of chloride reduced oxalic acid formation.

  4. Comparison of the formation of nicotinic acid conjugates in leaves of different plant species.

    PubMed

    Ashihara, Hiroshi; Yin, Yuling; Katahira, Riko; Watanabe, Shin; Mimura, Tetsuro; Sasamoto, Hamako

    2012-11-01

    There are three metabolic fates of nicotinic acid in plants: (1) nicotinic acid mononucleotide formation for NAD synthesis by the so-called salvage pathway of pyridine nucleotide biosynthesis; (2) nicotinic acid N-glucoside formation; and (3) trigonelline (N-methylnicotinic acid) formation. In the present study, the metabolism of [carbonyl-(14)C]nicotinamide was investigated in leaves of 23 wild plant species. All species readily converted nicotinamide to nicotinic acid, and only a fraction of nicotinic acid was utilised for NAD and NADP synthesis. The remaining nicotinic acid is converted to the nicotinic acid conjugates. Only one plant species, Cycas revoluta, produced both nicotinic acid N-glucoside and trigonelline; the other 22 species produced one or other of the conjugates. The nicotinic acid N-glucoside-forming plants are Cyathea lepifera, Arenga trewmula var. englri, Barringtonia racemosa, Ilex paraguariensis, Angelica japonica, Scaevola taccada and Farfugium japonicum. In contrast, trigonelline is formed in C. lepifera, Ginkgo biloba, Pinus luchuensis, Casuarina equisetifolia, Alocasia odora, Pandanus odoratissimus, Hylocereus undatus, Kalanchoe pinnata, Kalanchoe tubiflora, Populus alba, Garcinia subelliptica, Oxalis corymbosa, Leucaena leucocephala, Vigna marina, Hibiscus tiliaceus and Melicope triphylla. The diversity of nicotinic acid conjugate formation in plants is discussed using these results and our previous investigation involving a few model plants, various crops and ferns. Nicotinic acid N-glucoside formation was restricted mostly to ferns and selected orders of angiosperms, whereas other plants produce trigonelline. In most cases the formation of both nicotinic acid conjugates is incompatible, but some exceptions have been found.

  5. Formation of degradation products from the pyrolysis of tall oil fatty acids with kraft lignin

    SciTech Connect

    Traitler, H.; Kratzl, K.

    1980-01-01

    Pyrolysis of tall oil fatty acids containing kraft lignin at 160-280 degrees with or without exclusion of O resulted in formation of alkylbenzenes, carboxylic acids, and hydrocarbons, as determined by gas chomatography. In the pyrolysis, ring cleavage of dehydroabietic acids could not be observed, and no cyclic fatty acids could be detected.

  6. On Monolayer Formation of Pyrenebutyric Acid on Graphene.

    PubMed

    Hinnemo, Malkolm; Zhao, Jie; Ahlberg, Patrik; Hägglund, Carl; Djurberg, Viktor; Scheicher, Ralph H; Zhang, Shi-Li; Zhang, Zhi-Bin

    2017-04-04

    As a two-dimensional material with high charge carrier mobility, graphene may offer ultrahigh sensitivity in biosensing. To realize this, the first step is to functionalize the graphene. This is commonly done by using 1-pyrenebutyric acid (PBA) as a linker for biomolecules. However, the adsorption of PBA on graphene remains poorly understood despite reports of successful biosensors functionalized via this route. Here, the PBA adsorption on graphene is characterized through a combination of Raman spectroscopy, ab initio calculations, and spectroscopic ellipsometry. The PBA molecules are found to form a self-assembled monolayer on graphene, the formation of which is self-limiting and Langmuirian. Intriguingly, in concentrated solutions, the PBA molecules are found to stand up and stack horizontally with their edges contacting the graphene surface. This morphology could facilitate a surface densely populated with carboxylic functional groups. Spectroscopic analyses show that the monolayer saturates at 5.3 PBA molecules per nm(2) and measures ∼0.7 nm in thickness. The morphology study of this PBA monolayer sheds light on the π-π stacking of small-molecule systems on graphene and provides an excellent base for optimizing functionalization procedures.

  7. Formation and transformation of amino acids and amino acid precursors by high-velocity impacts

    NASA Astrophysics Data System (ADS)

    Kaneko, T.; Kobayashi, K.; Yamori, A.

    A wide variety of organic compounds have been found in extraterrestrial bodies such as comets and carbonaceous chondrites. It is plausible that these extraterrestrial bodies carried organic compounds such as amino acids or their precursors to the early Earth. It is claimed, however, that these extraterrestrial organics were destroyed during impacts to the Earth. We therefore examined possible transformation of amino acids and their precursors during high-velocity impacts by using a rail gun "HYPAC" in ISAS. Starting materials used in the impact experiments were (i) aqueous solution of glycine (10 mM or 1.0 M), and (ii) a mixture of ammonia, methanol and water. The target materials were sealed in stainless steel capsules, and shocked by impact with a polycarbonate projectile accelerated with "HYPAC" to the velocities of 2.5 - 7.0 km/s. A part of the products was acid-hydrolyzed. Both hydrolyzed an unhydrolyzed products were analyzed by mass spectrometry, high performance liquid chromatography and capillary electrophoresis and chromatography. When an aqueous solution containing ammonia, methanol and water was shocked by impact at the velocity of 6.4 km/s, a number of amino acids (e.g., serine and glycine) were detected after hydrolysis. The present results suggest that amino acid precursors could be formed during cometary impacts. When glycine solution was used as a starting material, about 40 % of glycine was recovered even after 6 km/s impact. Methylamine and ammonia, which are known as pyrolytic products of glycine, were detected, besides them, diketopiperazine and an unidentified product whose molecular weight was 134, were detected, while no glycine peptides were identified in them. It was shown that the impact processes resulted in the formation of amino acid condensates. Thermal stability of glycine precursor is comparable with glycine. The present results suggest that organic material could survive and/or formed during an impact process. Most of organic

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

    PubMed

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

    2008-05-01

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

  9. Effect of rosmarinic acid and carnosic acid on AGEs formation in vitro.

    PubMed

    Ou, Juanying; Huang, Junqing; Wang, Mingfu; Ou, Shiyi

    2017-04-15

    This work aimed to investigate the effect of the two main components of rosemary extracts, namely rosmarinic acid (RA) and carnosic acid (CA), on the formation of advanced glycation end-products (AGEs) in vitro. In the bovine serum albumin (BSA)/glucose model, addition of RA and CA at 400μg/mL inhibited fluorescent AGEs by more than 90%, and carboxymethyl lysine (CML) and carboxyethyl lysine (CEL) by 82.7% and 75.2%, and 71.4% and 64.2%, respectively. Moreover, the addition of RA and CA at 400μg/mL inhibited fluorescent AGEs by more than 90% both in the BSA/glyoxal (GO) and BSA/methylglyoxal (MGO) models, the formation of CML by 64.9% and 53.9% in BSA/GO model, and CEL by 28.9% and 24.3% in BSA/MGO model, respectively. RA and CA also significantly decreased the concentration of MGO and protein carbonylation.

  10. Formation of diphenylthioarsinic acid from diphenylarsinic acid under anaerobic sulfate-reducing soil conditions.

    PubMed

    Hisatomi, Shihoko; Guan, Ling; Nakajima, Mami; Fujii, Kunihiko; Nonaka, Masanori; Harada, Naoki

    2013-11-15

    Diphenylarsinic acid (DPAA) is a toxic phenylarsenical compound often found around sites contaminated with phenylarsenic chemical warfare agents, diphenylcyanoarsine or diphenylchloroarsine, which were buried in soil after the World Wars. This research concerns the elucidation of the chemical structure of an arsenic metabolite transformed from DPAA under anaerobic sulfate-reducing soil conditions. In LC/ICP-MS analysis, the retention time of the metabolite was identical to that of a major phenylarsenical compound synthesized by chemical reaction of DPAA and hydrogen sulfide. Moreover the mass spectra for the two compounds measured using LC/TOF-MS were similar. Subsequent high resolution mass spectral analysis indicated that two major ions at m/z 261 and 279, observed on both mass spectra, were attributable to C12H10AsS and C12H12AsSO, respectively. These findings strongly suggest that the latter ion is the molecular-related ion ([M+H](+)) of diphenylthioarsinic acid (DPTA; (C6H5)2AsS(OH)) and the former ion is its dehydrated fragment. Thus, our results reveal that DPAA can be transformed to DPTA, as a major metabolite, under sulfate-reducing soil conditions. Moreover, formation of diphenyldithioarsinic acid and subsequent dimerization were predicted by the chemical reaction analysis of DPAA with hydrogen sulfide. This is the first report to elucidate the occurrence of DPAA-thionation in an anaerobic soil.

  11. The Role of Oxalic Acid in New Particle Formation from Methanesulfonic Acid, Methylamine, and Water.

    PubMed

    Arquero, Kristine D; Gerber, R Benny; Finlayson-Pitts, Barbara J

    2017-02-21

    Atmospheric particles are notorious for their effects on human health and visibility and are known to influence climate. Though sulfuric acid and ammonia/amines are recognized as main contributors to new particle formation (NPF), models and observations have indicated that other species may be involved. It has been shown that nucleation from methanesulfonic acid (MSA) and amines, which is enhanced with added water, can also contribute to NPF. While organics are ubiquitous in air and likely to be involved in NPF by stabilizing small clusters for further growth, their effects on the MSA-amine system are not known. This work investigates the effect of oxalic acid (OxA) on NPF from the reaction of MSA and methylamine (MA) at 1 atm and 294 K in the presence and absence of water vapor using an aerosol flow reactor. OxA and MA do not efficiently form particles even in the presence of water, but NPF is enhanced when adding MSA to OxA-MA with and without water. The addition of OxA to MSA-MA mixtures yields a modest NPF enhancement, whereas the addition of OxA to MSA-MA-H2O has no effect. Possible reasons for these effects are discussed.

  12. FORMATION AND ENANTIOSELECTIVE BIODEGRADATION OF THE ENANTIOMERS OF BROMOCHLOROACETIC ACID

    EPA Science Inventory

    Bromochloroacetic acid (BCAA) is formed by chlorination of drinking waters containing naturally occurring bromide. This haloacetic acid is a concern to public health because of suspected carcinogenicity and toxicity, and is a potential target of disinfectant byproduct regulations...

  13. The enthalpies of formation and sublimation of amino acids and peptides

    NASA Astrophysics Data System (ADS)

    Sagadeev, E. V.; Gimadeev, A. A.; Barabanov, V. P.

    2010-02-01

    The experimental enthalpies of formation of L-amino acids and peptides were analyzed using the additive scheme and group contributions. Group contributions to the enthalpies of formation were calculated (increment denotations corresponded to the Benson-Buss symbols). The thermochemical characteristics of a wide range of amino acids and their derivatives were calculated.

  14. Pd/C synthesized with citric acid: an efficient catalyst for hydrogen generation from formic acid/sodium formate.

    PubMed

    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 H(2) 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.

  15. 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

  16. Small molecule-mediated duplex formation of nucleic acids with 'incompatible' backbones.

    PubMed

    Cafferty, Brian J; Musetti, Caterina; Kim, Keunsoo; Horowitz, Eric D; Krishnamurthy, Ramanarayanan; Hud, Nicholas V

    2016-04-07

    Proflavine, a known intercalator of DNA and RNA, promotes duplex formation by nucleic acids with natural and non-natural backbones that otherwise form duplexes with low thermal stability, and even some that show no sign of duplex formation in the absence of proflavine. These findings demonstrate the potential for intercalators to be used as cofactors for the assembly of rationally designed nucleic acid structures, and could provide fundamental insights regarding intercalation of natural nucleic acid duplexes.

  17. Multifunctional acid formation from the gas-phase ozonolysis of beta-pinene.

    PubMed

    Ma, Yan; Marston, George

    2008-10-28

    The gas-phase ozonolysis of beta-pinene was studied in static chamber experiments, using gas chromatography coupled to mass spectrometric and flame ionisation detection to separate and detect products. A range of multifunctional organic acids-including pinic acid, norpinic acid, pinalic-3-acid, pinalic-4-acid, norpinalic acid and OH-pinalic acid-were identified in the condensed phase after derivatisation. Formation yields for these products under systematically varying reaction conditions (by adding different OH radical scavengers and Criegee intermediate scavengers) were investigated and compared with those observed from alpha-pinene ozonolysis, allowing detailed information on product formation mechanisms to be elucidated. In addition, branching ratios for the initial steps of the reaction were inferred from quantitative measurements of primary carbonyl formation. Atmospheric implications of this work are discussed.

  18. Mechanism of carboxylic acid photooxidation in atmospheric aqueous phase: Formation, fate and reactivity

    NASA Astrophysics Data System (ADS)

    Charbouillot, Tiffany; Gorini, Sophie; Voyard, Guillaume; Parazols, Marius; Brigante, Marcello; Deguillaume, Laurent; Delort, Anne-Marie; Mailhot, Gilles

    2012-09-01

    In the first part of the work, we investigated the reactivity toward photogenerated hydroxyl radicals (rad OH) of seven monocarboxylic acids and six dicarboxylic acids found in natural cloud water. This leads to the proposition of a schematic degradation pathway linking glutaric acid (C5) to complete mineralization into CO2. We report a detailed mechanism on the succinic acid reactivity toward rad OH leading to the formation of malonic, glyoxylic and consequently oxalic acids and a comparison with reported pathways proposed by the CAPRAM (Chemical Aqueous Phase RAdical Mechanism) is discussed. We also investigated the photooxidation of formic acid under atmospherically relevant conditions leading to the possible formation of oxalic acid via radical mediated recombination. The second part focuses on the polychromatic irradiation (closed to solar irradiation) of a collected cloud aqueous phase showing that irradiation of cloud water leads to the formation of both formic and acetic acids. Carboxylic acid formation increases in the presence of photogenerated hydroxyl radicals from hydrogen peroxide, showing that photooxidation could play a key role in the formation of carboxylic acids under atmospherically relevant conditions.

  19. Strecker Aldehyde Formation in Wine: New Insights into the Role of Gallic Acid, Glucose, and Metals in Phenylacetaldehyde Formation.

    PubMed

    Monforte, Ana Rita; Martins, Sara I F S; Silva Ferreira, Antonio C

    2017-03-09

    Strecker degradation (SD) leading to the formation of phenylacetaldehyde (PA) was studied in wine systems. New insights were gained by using two full factorial designs focusing on the effects of (1) pH and (2) temperature. In each design of experiments (DoE) three factors, glucose, gallic acid, and metals at two levels (present or absence), were varied while phenylalanine was kept constant. The obtained results gave a clear indication, with statistical significance, that in wine conditions, the SD occurs in the presence of metals preferentially via the phenolic oxidation independent of the temperature (40 or 80 °C). The reaction of the amino acid with the o-quinone formed by the oxidation of the gallic acid seems to be favored when compared with the SD promoted by the reaction with α-dicarbonyls formed by MR between glucose and phenylalanine. In fact, kinetics results showed that the presence of glucose had an inhibitory effect on PA rate of formation. PA formation was 4 times higher in the control wine when compared to the same wine with 10 g/L glucose added. By gallic acid quinone quantitation it is shown that glucose affects directly the concentration of the quinone. decreasing the rate of quinone formation. This highlights the role of sugar in o-quinone concentration and consequently in the impact on Strecker aldehyde formation, a promising new perspective regarding wine shelf-life understanding.

  20. Sugar fatty acid esters inhibit biofilm formation by food-borne pathogenic bacteria.

    PubMed

    Furukawa, Soichi; Akiyoshi, Yuko; O'Toole, George A; Ogihara, Hirokazu; Morinaga, Yasushi

    2010-03-31

    Effects of food additives on biofilm formation by food-borne pathogenic bacteria were investigated. Thirty-three potential food additives and 3 related compounds were added to the culture medium at concentrations from 0.001 to 0.1% (w/w), followed by inoculation and cultivation of five biofilm-forming bacterial strains for the evaluation of biofilm formation. Among the tested food additives, 21 showed inhibitory effects of biofilm formation by Staphylococcus aureus and Escherichia coli, and in particular, sugar fatty acid esters showed significant anti-biofilm activity. Sugar fatty acid esters with long chain fatty acid residues (C14-16) exerted their inhibitory effect at the concentration of 0.001% (w/w), but bacterial growth was not affected at this low concentration. Activities of the sugar fatty acid esters positively correlated with the increase of the chain length of the fatty acid residues. Sugar fatty acid esters inhibited the initial attachment of the S. aureus cells to the abiotic surface. Sugar fatty acid esters with long chain fatty acid residues (C14-16) also inhibited biofilm formation by Streptococcus mutans and Listeria monocytogenes at 0.01% (w/w), while the inhibition of biofilm formation by Pseudomonas aeruginosa required the addition of a far higher concentration (0.1% (w/w)) of the sugar fatty acid esters.

  1. Methane formation by oxidation of ascorbic acid using iron minerals and hydrogen peroxide.

    PubMed

    Althoff, Frederik; Jugold, Alke; Keppler, Frank

    2010-06-01

    The possibility of methane formation in an oxidative environment has been intensely debated, especially since the discovery of methane generation by living plants. However, recent studies with animal tissue suggested that under specific conditions aerobic methane formation is also possible. Here, we investigated the generation of methane in an abiotic model system using bioavailable substances. We show formation of methane in a highly oxidative media, using ascorbic acid, ferrihydrite and hydrogen peroxide as reagents. Methane production was shown to be related to reagent ratio, reaction volume and pH. A 2:1 ratio of hydrogen peroxide to ascorbic acid, catalytic amounts of ferrihydrite and acidic conditions (pH 3) enhanced formation of methane. We further show that gaseous oxygen has a strong influence with higher levels found to inhibit methane formation. This study is a first step towards providing an insight for the reaction mechanism of methane formation that would be applicable to aerobic environments.

  2. Conceptual models of the formation of acid-rock drainage at road cuts in Tennessee

    USGS Publications Warehouse

    Bradley, Michael W.; Worland, Scott; Byl, Tom

    2015-01-01

    Pyrite and other minerals containing sulfur and trace metals occur in several rock formations throughout Middle and East Tennessee. Pyrite (FeS2) weathers in the presence of oxygen and water to form iron hydroxides and sulfuric acid. The weathering and interaction of the acid on the rocks and other minerals at road cuts can result in drainage with low pH (< 4) and high concentrations of trace metals. Acid-rock drainage can cause environmental problems and damage transportation infrastructure. The formation and remediation of acid-drainage from roads cuts has not been researched as thoroughly as acid-mine drainage. The U.S Geological Survey, in cooperation with the Tennessee Department of Transportation, is conducting an investigation to better understand the geologic, hydrologic, and biogeochemical factors that control acid formation at road cuts. Road cuts with the potential for acid-rock drainage were identifed and evaluated in Middle and East Tennessee. The pyrite-bearing formations evaluated were the Chattanooga Shale (Devonian black shale), the Fentress Formation (coal-bearing), and the Precambrian Anakeesta Formation and similar Precambrian rocks. Conceptual models of the formation and transport of acid-rock drainage (ARD) from road cuts were developed based on the results of a literature review, site reconnaissance, and the initial rock and water sampling. The formation of ARD requires a combination of hydrologic, geochemical, and microbial interactions which affect drainage from the site, acidity of the water, and trace metal concentrations. The basic modes of ARD formation from road cuts are; 1 - seeps and springs from pyrite-bearing formations and 2 - runoff over the face of a road cut in a pyrite-bearing formation. Depending on site conditions at road cuts, the basic modes of ARD formation can be altered and the additional modes of ARD formation are; 3 - runoff over and through piles of pyrite-bearing material, either from construction or breakdown

  3. Guanine- Formation During the Thermal Polymerization of Amino Acids

    NASA Technical Reports Server (NTRS)

    Mc Caw, B. K.; Munoz, E. F.; Ponnamperuma, C.; Young, R. S.

    1964-01-01

    The action of heat on a mixture of amino acids was studied as a possible abiological pathway for the synthesis of purines and pyrimidines. Guanine was detected. This result is significant in the context of chemical evolution.

  4. [Investigation on formation mechanism of secologanic acid sulfonates in sulfur-fumigated buds of Lonicera japonica].

    PubMed

    Guo, Ai-Li; Gao, Hui-Min; Chen, Liang-Mian; Zhang, Qi-Wei; Wang, Zhi-Min

    2014-05-01

    To investigate formation mechanism of secologanic acid sulfonates in sulfur-fumigated buds of Lonicera japonica, secologanic acid was enriched and purified from the sun-dried buds of L. japonica by various column chromatography on macroporus resin HPD-100, silica gel and ODS. The stimulation experiments of sulfur-fumigation process were carried out using secologanic acid reacted with SO2 in the aqueous solution. The reaction mechanism could be involved in the esterification or addition reaction. The present investigation provides substantial evidences for interpreting formation pathway of secologanic acid sulfonates in sulfur-fumigated buds of L. japonica.

  5. Ammonia Catalyzed Formation of Sulfuric Acid in Troposphere: The Curious Case of A Base Promoting Acid Rain.

    PubMed

    Bandyopadhyay, Biman; Kumar, Pradeep; Biswas, Partha

    2017-04-03

    Electronic structure calculations have been performed to investigate the role of ammonia in catalyzing the formation of sulfuric acid through hydrolysis of SO3 in Earth's atmosphere. The uncatalyzed process involves a high activation barrier and, till date, is mainly known to occur in Earth's atmosphere only when catalyzed by water and acids. Here we show that hydrolysis of SO3 can be very efficiently catalyzed by ammonia, the most abundant basic component in Earth's atmosphere. It was found, based on magnitude of relative potential energies as well as rate coefficients, that ammonia is the best among all the catalysts studied until now (water and acids) and could be a considerable factor in formation of sulfuric acid in troposphere. The calculated rate coefficient (at 298 K) of ammonia catalyzed reaction has been found to be ~10^5 - 10^7 times greater than that for water catalyzed ones. It was found, based on relative rates of ammonia and water catalyzed processes that in troposphere ammonia, together with water, could be the key factor in determining the rate of formation of sulfuric acid. In fact ammonia could surpass water in catalyzing formation of sulfuric acid via hydrolysis of SO3 at various altitudes in troposphere depending upon their relative concentrations.

  6. Optimized Jasmonic Acid Production by Lasiodiplodia theobromae Reveals Formation of Valuable Plant Secondary Metabolites

    PubMed Central

    Eng, Felipe; Haroth, Sven; Feussner, Kirstin; Meldau, Dorothea; Rekhter, Dmitrij; Ischebeck, Till; Brodhun, Florian

    2016-01-01

    Jasmonic acid is a plant hormone that can be produced by the fungus Lasiodiplodia theobromae via submerged fermentation. From a biotechnological perspective jasmonic acid is a valuable feedstock as its derivatives serve as important ingredients in different cosmetic products and in the future it may be used for pharmaceutical applications. The objective of this work was to improve the production of jasmonic acid by L. theobromae strain 2334. We observed that jasmonic acid formation is dependent on the culture volume. Moreover, cultures grown in medium containing potassium nitrate as nitrogen source produced higher amounts of jasmonic acid than analogous cultures supplemented with ammonium nitrate. When cultivated under optimal conditions for jasmonic acid production, L. theobromae secreted several secondary metabolites known from plants into the medium. Among those we found 3-oxo-2-(pent-2-enyl)-cyclopentane-1-butanoic acid (OPC-4) and hydroxy-jasmonic acid derivatives, respectively, suggesting that fungal jasmonate metabolism may involve similar reaction steps as that of plants. To characterize fungal growth and jasmonic acid-formation, we established a mathematical model describing both processes. This model may form the basis of industrial upscaling attempts. Importantly, it showed that jasmonic acid-formation is not associated to fungal growth. Therefore, this finding suggests that jasmonic acid, despite its enormous amount being produced upon fungal development, serves merely as secondary metabolite. PMID:27907207

  7. Perfluorinated acids in Arctic snow: new evidence for atmospheric formation.

    PubMed

    Young, Cora J; Furdui, Vasile I; Franklin, James; Koerner, Roy M; Muir, Derek C G; Mabury, Scott A

    2007-05-15

    Perfluorinated acids (PFAs) are ubiquitously found in water and biota, including remote regions such as the High Arctic. Under environmental conditions, PFAs exist mainly as anions and are not expected to be subject to long-range atmospheric transport in the gas phase. Fluorinated telomer alcohols (FTOHs) are volatile and can be atmospherically oxidized to form perfluorocarboxylic acids. Analogously, fluorosulfamido alcohols can be oxidized to form perfluorooctane sulfonate (PFOS). High Arctic ice caps experience contamination solely from atmospheric sources. By examining concentrations of PFAs in ice cap samples, it is possible to determine atmospheric fluxes to the Arctic. Ice samples were collected from high Arctic ice caps in the spring of 2005 and 2006. Samples were concentrated using solid-phase extraction and analyzed by LC-MS-MS. PFAs were observed in all samples, dating from 1996 to 2005. Concentrations were in the low-mid pg L(-1) range and exhibited seasonality, with maximum concentrations in the spring-summer. The presence of perfluorodecanoic acid (PFDA) and perfluoroundecanoic acid (PFUnA) on the ice cap was indicative of atmospheric oxidation as a source. Ratios of PFAs to sodium concentrations were highly variable, signifying PFA concentrations on the ice cap were unrelated to marine chemistry. Fluxes of the PFAs were estimated to the area north of 65 degrees N for the 2005 season, which ranged from 114 to 587 kg year(-1) for perfluorooctanoic acid (PFOA), 73 to 860 kg year(-1) for perfluorononanoic acid (PFNA), 16 to 84 kg year(-1) for PFDA, 26 to 62 kg year(-1) for PFUnA, and 18 to 48 kg year(-1) for PFOS. The PFOA and PFNA fluxes agreed with FTOH modeling estimations. A decrease in PFOS concentrations through time was observed, suggesting a fast response to changes in production. These data suggest that atmospheric oxidation of volatile precursors is a primary source of PFAs to the Arctic.

  8. Photoenhanced nitrous acid formation upon NO2 uptake on tannic and gentisic acid films

    NASA Astrophysics Data System (ADS)

    Sosedova, Yulia; Rouvière, Aurélie; Ammann, Markus

    2010-05-01

    The heterogeneous chemistry of nitrogen dioxide (NO2) is a potential source of nitrous acid (HONO). Hydroxy and methoxy substituted phenols may play a significant role in the aqueous-phase chemistry occurring on the ground or within aerosol particles in air masses affected by biomass burning. It is well established that electron transfer between phenols and NO2 in alkaline aqueous solutions is fast and could be a source of nitrite in the aqueous phase and HONO in the gas phase. However its kinetics is very slow under atmospheric conditions. The role of phenolic species as electron donors has also been suspected to be responsible for the photoenhanced transformation of NO2 to HONO over humic acids [1]. In this study we used tannic (TA) and gentisic (GA) as another proxy for atmospheric phenolic compounds. TA was shown to easily decompose under near UV light irradiation [2] resulting in oxidized products that might change the hygroscopic properties of the original material or have some potential photosensitizing effect. It was interesting to check the hypothesis that the presence of such products could lead to photoenhanced HONO formation upon NO2 uptake to aqueous surfaces containing TA. Experiments were performed in a horizontal coated wall flow tube (40 cm × 5.9 cm i.d.) circularly surrounded by 7 fluorescence lamps (UV: 300-420 nm, or visible: 400-750 nm), in an air cooled lamp housing. The inner surface coating was containing ~0.5 mg/cm-2 of either TA or GA, and was operated under RH 20-80%, 21-23 °C and ambient pressure. Concentration of HONO in the gas phase at the flow tube exit was measured with a LOPAP (Long Path Absorption Spectrometer). The uptake coefficient (γ) leading to NO2 to HONO conversion above aqueous films containing GA or TA in the dark was in the range 4×10-7 - 2×10-6. The photochemically enhanced HONO production was demonstrated by UV irradiation of the GA or TA coatings being in contact with gaseous NO2. In this case γ was 3-10 times

  9. The standard enthalpies of formation of crystalline N-(carboxymethyl)aspartic acid and its aqueous solutions

    NASA Astrophysics Data System (ADS)

    Lytkin, A. I.; Chernyavskaya, N. V.; Volkov, A. V.; Nikol'Skii, V. M.

    2007-07-01

    The energy of combustion of N-(carboxymethyl)aspartic acid (CMAA) was determined by bomb calorimetry in oxygen. The standard enthalpies of combustion and formation of crystalline N-(carboxymethyl)aspartic acid were calculated. The heat effects of solution of crystalline CMAA in water and a solution of sodium hydroxide were measured at 298.15 K by direct calorimetry. The standard enthalpies of formation of CMAA and its dissociation products in aqueous solution were determined.

  10. On the Formation of Benzoic Acid and Higher Order Benzene Carboxylic Acids in Interstellar Model Ices grains

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

    With a binary ice mixture of benzene (C6H6) and carbon dioxide (CO2) at 10 K under contamination-free ultrahigh vacuum conditions, the formation of benzene carboxylic acids in interstellar ice grains was studied. Fourier transform infrared spectroscopy was used to probe for the formation of new species during the chemical processing of the ice mixture and during the following temperature-programmed desorption. Newly formed benzene carboxylic acid species, i.e., benzoic acid, as well as meta- and para-benzene dicarboxylic acid, were assigned using newly emerging bands in the infrared spectrum; a reaction mechanism, along with rate constants, was proposed utilizing the kinetic fitting of the coupled differential equations.

  11. Formation of Organic Tracers for Isoprene SOA under Acidic Conditions

    EPA Science Inventory

    The chemical compositions of a series of secondary organic aerosol (SOA) samples, formed by irradiating mixtures of isoprene and NO in a smog chamber in the absence or presence of acidic aerosols, were analyzed using derivatization-based GC-MS methods. In addition to the known is...

  12. The effects of phytic acid on the Maillard reaction and the formation of acrylamide.

    PubMed

    Wang, Huan; Zhou, Yamin; Ma, Jimei; Zhou, Yuanyuan; Jiang, Hong

    2013-11-01

    Phytic acid, myo-inositol hexaphosphoric acid, exists in substantial (1-5%) amounts in edible plant seeds. In this study the effects of phytic acid on the Maillard reaction and the formation of acrylamide were investigated. Both phytic acid and phosphate enhanced browning in glucose/β-alanine system, but phytic acid was less effective than phosphate. Higher pH favoured the catalytic activities for both of them. The influence of the types of sugar and amino acid on the reaction was also examined. Browning was suppressed by the addition of calcium and magnesium ions, but an additive effect was observed for ferrous ions and phytic acid in glucose/β-alanine solution at pH 8.0. Both phytic acid and phosphate promoted the polymerisation of the reaction intermediates. The kinetics of Maillard reaction was first-ordered reaction in the presence of phytic acid. Phytic acid was less effective than phosphate in the formation of acrylamide. When potato slices were treated with sodium phytate and calcium chloride successively, the formation of acrylamide was greatly suppressed.

  13. OH-radical induced degradation of hydroxybenzoic- and hydroxycinnamic acids and formation of aromatic products—A gamma radiolysis study

    NASA Astrophysics Data System (ADS)

    Krimmel, Birgit; Swoboda, Friederike; Solar, Sonja; Reznicek, Gottfried

    2010-12-01

    The OH-radical induced degradation of hydroxybenzoic acids (HBA), hydroxycinnamic acids (HCiA) and methoxylated derivatives, as well as of chlorogenic acid and rosmarinic acid was studied by gamma radiolysis in aerated aqueous solutions. Primary aromatic products resulting from an OH-radical attachment to the ring (hydroxylation), to the position occupied by the methoxyl group (replacement -OCH 3 by -OH) as well as to the propenoic acid side chain of the cinnamic acids (benzaldehyde formations) were analysed by HPLC-UV and LC-ESI-MS. A comparison of the extent of these processes is given for 3,4-dihydroxybenzoic acid, vanillic acid, isovanillic acid, syringic acid, cinnamic acid, 4-hydroxycinnamic acid, caffeic acid, ferulic acid, isoferulic acid, chlorogenic acid, and rosmarinic acid. For all cinnamic acids and derivatives benzaldehydes were significant oxidation products. With the release of caffeic acid from chlorogenic acid the cleavage of a phenolic glycoside could be demonstrated. Reaction mechanisms are discussed.

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

    PubMed Central

    Takahashi, Ohgi; Kirikoshi, Ryota; Manabe, Noriyoshi

    2015-01-01

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

  15. Chiral BINOL-derived phosphoric acids: privileged Brønsted acid organocatalysts for C-C bond formation reactions.

    PubMed

    Zamfir, Alexandru; Schenker, Sebastian; Freund, Matthias; Tsogoeva, Svetlana B

    2010-12-07

    BINOL-derived phosphoric acids have emerged during the last five years as powerful chiral Brønsted acid catalysts in many enantioselective processes. The most successful transformations carried out with chiral BINOL phosphates include C-C bond formation reactions. The recent advances have been reviewed in this article with a focus being placed on hydrocyanations, aldol-type, Mannich, Friedel-Crafts, aza-ene-type, Diels-Alder, as well as cascade and multi-component reactions.

  16. 37 CFR 1.822 - Symbols and format to be used for nucleotide and/or amino acid sequence data.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... for nucleotide and/or amino acid sequence data. 1.822 Section 1.822 Patents, Trademarks, and... Amino Acid Sequences § 1.822 Symbols and format to be used for nucleotide and/or amino acid sequence data. (a) The symbols and format to be used for nucleotide and/or amino acid sequence data...

  17. 37 CFR 1.822 - Symbols and format to be used for nucleotide and/or amino acid sequence data.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... for nucleotide and/or amino acid sequence data. 1.822 Section 1.822 Patents, Trademarks, and... Amino Acid Sequences § 1.822 Symbols and format to be used for nucleotide and/or amino acid sequence data. (a) The symbols and format to be used for nucleotide and/or amino acid sequence data...

  18. 37 CFR 1.822 - Symbols and format to be used for nucleotide and/or amino acid sequence data.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... for nucleotide and/or amino acid sequence data. 1.822 Section 1.822 Patents, Trademarks, and... Amino Acid Sequences § 1.822 Symbols and format to be used for nucleotide and/or amino acid sequence data. (a) The symbols and format to be used for nucleotide and/or amino acid sequence data...

  19. 37 CFR 1.822 - Symbols and format to be used for nucleotide and/or amino acid sequence data.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... for nucleotide and/or amino acid sequence data. 1.822 Section 1.822 Patents, Trademarks, and... Amino Acid Sequences § 1.822 Symbols and format to be used for nucleotide and/or amino acid sequence data. (a) The symbols and format to be used for nucleotide and/or amino acid sequence data...

  20. 37 CFR 1.822 - Symbols and format to be used for nucleotide and/or amino acid sequence data.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... for nucleotide and/or amino acid sequence data. 1.822 Section 1.822 Patents, Trademarks, and... Amino Acid Sequences § 1.822 Symbols and format to be used for nucleotide and/or amino acid sequence data. (a) The symbols and format to be used for nucleotide and/or amino acid sequence data...

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

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

    Formic acid (HCOOH) is one of the most abundant carboxylic acids in the atmosphere. However, current photochemical models cannot fully explain observed concentrations and in particular secondary formation of formic acid across various environments. In this work, formic acid measurements made at an urban receptor site in June-July of 2010 during CalNex and a site in an oil and gas producing region in January-February of 2013 during UBWOS 2013 will be discussed. Although the VOC compositions differed dramatically at the two sites, measured formic acid concentrations were comparable: 2.3 ± 1.3 ppb in UBWOS 2013 and 2.0 ± 1.0 ppb in CalNex. We determine that concentrations of formic acid at both sites were dominated by secondary formation (> 8%). A constrained box model using the Master Chemical Mechanism (MCM v3.2) underestimates the measured formic acid concentrations drastically at both sites (by a factor of > 10). Inclusion of recent findings on additional precursors and formation pathways of formic acid in the box model increases modeled formic acid concentrations for UBWOS 2013 and CalNex by a factor of 6.4 and 4.5, respectively. A comparison of measured and modeled HCOOH/acetone ratios is used to evaluate the model performance for formic acid. We conclude that the modified chemical mechanism can explain 21 and 47% of secondary formation of formic acid in UBWOS 2013 and CalNex, respectively. The contributions from aqueous reactions in aerosol and heterogeneous reactions on aerosol surface to formic acid are estimated to be -7 and 0-6% in UBWOS 2013 and CalNex, respectively. We observe that air-snow exchange processes and morning fog events may also contribute to ambient formic acid concentrations during UBWOS 2013 (∼20% in total). In total, 50-57% in UBWOS 2013 and 48-53% in CalNex of secondary formation of formic acid remains unexplained. More work on formic acid formation pathways is needed to reduce the uncertainties in the sources and budget of formic

  2. Testing the Role of Silicic Acid and Bioorganic Materials in the Formation of Rock Coatings

    SciTech Connect

    Kolb, Vera; Philip, Ajish I.; Perry, Randall S.

    2004-12-01

    Silica, amino acids, and DNA were recently discovered in desert varnish. In this work we experimentally test the proposed role of silicic acid and bio-chemicals in the formation of desert varnish and other rock coatings. We have developed a protocol in which hte rocks were treated with a mixture of silicic acid, sugars, amino acids, metals and clays, under the influence of heat and UV light. This protocol reflects the proposed mechanism of hte polymerization of silicic acid with the bioorganic materials, and the laboratory model for the natural conditions under which the desert varnish is formed. Our experiments produced coatings with a hardness and morphology that resemble the nature ones. These results provide a support for the role of silicic acid in the formation of rock coatings. Since the hard silica-based coatings preserve organic compounds in them, they may serve as a biosignature for life, here or possibly Mars.

  3. Lipid and fatty acid composition of Gluconobacter oxydans before and after intracytoplasmic membrane formation.

    PubMed Central

    Heefner, D L; Claus, G W

    1978-01-01

    Gluconobacter oxydans differentiates by forming quantities of intracytoplasmic membranes at the end of exponential growth, and this formation occurs concurrently with a 60% increase in cellular lipid. The present study was initiated to determine whether this newly synthesized lipid differed from that extracted before intracytoplasmic membrane synthesis. Undifferentiated exponential-phase cells were found to contain 30% phosphatidylcholine, 27.1% caridolipin, 25% phosphatidylethanolamine, 12.5% phosphatidylglycerol, 0.4% phosphatidic acid, 0.2% phosphatidylserine, and four additional unidentified lipids totaling less than 5%. The only change detected after formation of intracytoplasmic membranes was a slight decrease in phosphatidylethanolamine and a corresponding increase in phosphatidylcholine. An examination of lipid hydrolysates revealed 11 different fatty acids in the lipids from each cell type. Hexadecanoic acid and monounsaturated octadecenoic accounted for more than 75% of the total fatty acids for both cell types. Proportional changes were noted in all fatty acids except octadecenoate. Anteiso-pentadecanoate comprised less than 1% of the fatty acids from undifferentiated cells but more than 13% of the total fatty acids from cells containing intracytoplasmic membranes. These results suggest that anteiso-pentadecanoate formation closely parallels the formation of intracytoplasmic membranes. Increased concentrations of this fatty acid may contribute to the fluidity necessary for plasma membrane convolution during intracytoplasmic membrane development. PMID:649571

  4. Studies of the acidic components of the Colorado Green River formation oil shale-Mass spectrometric identification of the methyl esters of extractable acids.

    NASA Technical Reports Server (NTRS)

    Haug, P.; Schnoes, H. K.; Burlingame, A. L.

    1971-01-01

    Study of solvent extractable acidic constituents of oil shale from the Colorado Green River Formation. Identification of individual components is based on gas chromatographic and mass spectrometric data obtained for their respective methyl esters. Normal acids, isoprenoidal acids, alpha, omega-dicarboxylic acids, mono-alpha-methyl dicarboxylic acids and methyl ketoacids were identified. In addition, the presence of monocyclic, benzoic, phenylalkanoic and naphthyl-carboxylic acids, as well as cycloaromatic acids, is demonstrated by partial identification.

  5. Toward the formation of alkylphosphonic acids in phosphine ices

    NASA Astrophysics Data System (ADS)

    Turner, Andrew; Kaiser, Ralf-Ingo

    2016-10-01

    Phosphorus is one of the elemental building blocks of life on Earth and is important for information storage (RNA/DNA), energy transfer (ATP), cell membranes (phospholipids), and structure (bones & teeth). Due to the poor bioavailability of highly oxidized phosphorus (P(V)) found in ubiquitous phosphate (PO43-) minerals, reduced oxidation state (P(III)) compounds have been proposed as a phosphorus source for early life on Earth. Among these, the alkylphosphonic acids, which are the only phosphorus-containing organic compounds discovered in the Murchison meteorite, are a suggested exogenous source of prebiotic phosphorus. Phosphine (PH3) is a known component of the atmospheres of Jupiter and Saturn, and the confirmation of circumstellar phosphine in the carbon-rich envelop of IRC +10216 along with the recent detection of phosphorus in the comet 67P/Churyumov-Gerasimenko provide an additional foundation for studying extraterrestrial phosphorus chemistry and the origins of the alkylphosphonic acids. In the present study, reactions of phosphine ices with water (H2O), carbon dioxide (CO2), and methane (CH4) were investigated using Fourier transform infrared spectroscopy (FTIR), quadrupole mass spectrometry (QMS), and most notably, reflectron time-of-flight mass spectrometry using tunable photoionization (PI-ReTOF-MS). Experiments were conducted at ultra-high vacuum pressures and cryogenic temperatures to better understand reaction pathways and products of phosphorus-containing compounds under icy conditions found in comets or the interstellar medium. The results of this study can provide support to the hypothesis that the alkylphosphonic acids were formed from interstellar phosphine and incorporated into meteorites such as Murchison.

  6. Sulfuric Acid and Soot Particle Formation in Aircraft Exhaust

    NASA Technical Reports Server (NTRS)

    Pueschel, Rudolf F.; Verma, S.; Ferry, G. V.; Howard, S. D.; Vay, S.; Kinne, S. A.; Baumgardner, D.; Dermott, P.; Kreidenweis, S.; Goodman, J.; Gore, Waren J. Y. (Technical Monitor)

    1997-01-01

    A combination of CN counts, Ames wire impactor size analyses and optical particle counter data in aircraft exhaust results in a continuous particle size distribution between 0.01 micrometer and 1 micrometer particle radius sampled in the exhaust of a Boeing 757 research aircraft. The two orders of magnitude size range covered by the measurements correspond to 6-7 orders of magnitude particle concentration. CN counts and small particle wire impactor data determine a nucleation mode, composed of aircraft-emitted sulfuric acid aerosol, that contributes between 62% and 85% to the total aerosol surface area and between 31% and 34% to its volume. Soot aerosol comprises 0.5% of the surface area of the sulfuric acid aerosol. Emission indices are: EIH2SO4 = 0.05 g/kgFUEL and (0.2-0.5) g/kgFUEL (for 75 ppmm and 675 ppmm fuel-S, respectively), 2.5E4

  7. Sulfation mediates activity of zosteric acid against biofilm formation.

    PubMed

    Kurth, Caroline; Cavas, Levent; Pohnert, Georg

    2015-01-01

    Zosteric acid (ZA), a metabolite from the marine sea grass Zostera marina, has attracted much attention due to its attributed antifouling (AF) activity. However, recent results on dynamic transformations of aromatic sulfates in marine phototrophic organisms suggest potential enzymatic desulfation of metabolites like ZA. The activity of ZA was thus re-investigated using biofilm assays and simultaneous analytical monitoring by liquid chromatography/mass spectrometry (LC/MS). Comparison of ZA and its non-sulfated form para-coumaric acid (CA) revealed that the active substance was in all cases the non-sulfated CA while ZA was virtually inactive. CA exhibited a strong biofilm inhibiting activity against Escherichia coli and Vibrio natriegens. The LC/MS data revealed that the apparent biofilm inhibiting effects of ZA on V. natriegens can be entirely attributed to CA released from ZA by sulfatase activity. In the light of various potential applications, the (a)biotic transformation of ZA to CA has thus to be considered in future AF formulations.

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

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

  9. D-Amino acids inhibit biofilm formation in Staphylococcus epidermidis strains from ocular infections.

    PubMed

    Ramón-Peréz, Miriam L; Diaz-Cedillo, Francisco; Ibarra, J Antonio; Torales-Cardeña, Azael; Rodríguez-Martínez, Sandra; Jan-Roblero, Janet; Cancino-Diaz, Mario E; Cancino-Diaz, Juan C

    2014-10-01

    Biofilm formation on medical and surgical devices is a major virulence determinant for Staphylococcus epidermidis. The bacterium S. epidermidis is able to produce biofilms on biotic and abiotic surfaces and is the cause of ocular infection (OI). Recent studies have shown that d-amino acids inhibit and disrupt biofilm formation in the prototype strains Bacillus subtilis NCBI3610 and Staphylococcus aureus SCO1. The effect of d-amino acids on S. epidermidis biofilm formation has yet to be tested for clinical or commensal isolates. S. epidermidis strains isolated from healthy skin (n = 3), conjunctiva (n = 9) and OI (n = 19) were treated with d-Leu, d-Tyr, d-Pro, d-Phe, d-Met or d-Ala and tested for biofilm formation. The presence of d-amino acids during biofilm formation resulted in a variety of patterns. Some strains were sensitive to all amino acids tested, while others were sensitive to one or more, and one strain was resistant to all of them when added individually; in this way d-Met inhibited most of the strains (26/31), followed by d-Phe (21/31). Additionally, the use of d-Met inhibited biofilm formation on a contact lens. The use of l-isomers caused no defect in biofilm formation in all strains tested. In contrast, when biofilms were already formed d-Met, d-Phe and d-Pro were able to disrupt it. In summary, here we demonstrated the inhibitory effect of d-amino acids on biofilm formation in S. epidermidis. Moreover, we showed, for the first time, that S. epidermidis clinical strains have a different sensitivity to these compounds during biofilm formation.

  10. Formation of mutagens following chlorination of humic acid. A model for mutagen formation during drinking water treatment.

    PubMed

    Meier, J R; Lingg, R D; Bull, R J

    1983-07-01

    Aqueous chlorination of humic acids results in the formation of compounds with direct-acting mutagenic activity in the Ames/Salmonella plate assay for tester strains TA98, TA100, TA1535, TA1537 and TA1538. The addition of a rat-liver microsomal fraction (S9) plus cofactors causes a substantial decrease of activity, the extent of which is tester strain dependent. The non-chlorinated humic acids are not mutagenic either in the presence or absence of S9. Formation of mutagenic activity and of total organic halogen (TOX) is linearly related to humic concentration in the range of 0.2-1.6 mg/ml total organic carbon (TOC), and to chlorine concentration in the range of 0.1-1.0 chlorine equivalents per mole of carbon. The mutagenic activity is due predominantly to non-volatile compounds. Mutagenic activity is also detectable, after sample concentration by lyophilization, upon chlorination at a humic acid level of 0.02 mg/ml TOC. The specific mutagenic activities (per mg TOX), and also the degree of chlorine incorporation into humic acid, at 0.02 mg/ml TOC are similar to those present after chlorination at 1 mg/ml TOC. Production of mutagens is greatly dependent on the chlorination pH, with a pattern of decreasing mutagenic activity with increasing pH. This order of activity can be at least partially explained by the alkali liability of the compounds. Chlorination of commercial humic acids is proposed as a model for examination of mutagen formation during water chlorination.

  11. Formation of linear polyenes in poly(vinyl alcohol) films catalyzed by phosphotungstic acid, aluminum chloride, and hydrochloric acid

    NASA Astrophysics Data System (ADS)

    Tretinnikov, O. N.; Sushko, N. I.; Malyi, A. B.

    2016-07-01

    Formation of linear polyenes-(CH=CH)n-via acid-catalyzed thermal dehydration of polyvinyl alcohol in 9- to 40-µm-thick films of this polymer containing hydrochloric acid, aluminum chloride, and phosphotungstic acid as dehydration catalysts was studied by electronic absorption spectroscopy. The concentration of long-chain ( n ≥ 8) polyenes in films containing phosphotungstic acid is found to monotonically increase with the duration of thermal treatment of films, although the kinetics of this process is independent of film thickness. In films containing hydrochloric acid and aluminum chloride, the formation rate of polyenes with n ≥ 8 rapidly drops as film thickness decreases and the annealing time increases. As a result, at a film thickness of less than 10-12 µm, long-chain polyenes are not formed at all in these films no matter how long thermal duration is. The reason for this behavior is that hydrochloric acid catalyzing polymer dehydration in these films evaporates from the films during thermal treatment, the evaporation rate inversely depending on film thickness.

  12. Acid environments affect biofilm formation and gene expression in isolates of Salmonella enterica Typhimurium DT104.

    PubMed

    O'Leary, Denis; McCabe, Evonne M; McCusker, Matthew P; Martins, Marta; Fanning, Séamus; Duffy, Geraldine

    2015-08-03

    The aim of this study was to examine the survival and potential virulence of biofilm-forming Salmonella Typhimurium DT104 under mild acid conditions. Salmonella Typhimurium DT104 employs an acid tolerance response (ATR) allowing it to adapt to acidic environments. The threat that these acid adapted cells pose to food safety could be enhanced if they also produce biofilms in acidic conditions. The cells were acid-adapted by culturing them in 1% glucose and their ability to form biofilms on stainless steel and on the surface of Luria Bertani (LB) broth at pH7 and pH5 was examined. Plate counts were performed to examine cell survival. RNA was isolated from cells to examine changes in the expression of genes associated with virulence, invasion, biofilm formation and global gene regulation in response to acid stress. Of the 4 isolates that were examined only one (1481) that produced a rigid biofilm in LB broth at pH7 also formed this same structure at pH5. This indicated that the lactic acid severely impeded the biofilm producing capabilities of the other isolates examined under these conditions. Isolate 1481 also had higher expression of genes associated with virulence (hilA) and invasion (invA) with a 24.34-fold and 13.68-fold increase in relative gene expression respectively at pH5 compared to pH7. Although genes associated with biofilm formation had increased expression in response to acid stress for all the isolates this only resulted in the formation of a biofilm by isolate 1481. This suggests that in addition to the range of genes associated with biofilm production at neutral pH, there are genes whose protein products specifically aid in biofilm production in acidic environments. Furthermore, it highlights the potential for the use of lactic acid for the inhibition of Salmonella biofilms.

  13. Precipitation pathways for ferrihydrite formation in acidic solutions

    NASA Astrophysics Data System (ADS)

    Zhu, Mengqiang; Frandsen, Cathrine; Wallace, Adam F.; Legg, Benjamin; Khalid, Syed; Zhang, Hengzhong; Mørup, Steen; Banfield, Jillian F.; Waychunas, Glenn A.

    2016-01-01

    Iron oxides and oxyhydroxides form via Fe3+ hydrolysis and polymerization in many aqueous environments, but the pathway from Fe3+ monomers to oligomers and then to solid phase nuclei is unknown. In this work, using combined X-ray, UV-vis, and Mössbauer spectroscopic approaches, we were able to identify and quantify the long-time sought ferric speciation over time during ferric oxyhydroxide formation in partially-neutralized ferric nitrate solutions ([Fe3+] = 0.2 M, 1.8 < pH < 3). Results demonstrate that Fe exists mainly as Fe(H2O)63+, μ-oxo aquo dimers and ferrihydrite, and that with time, the μ-oxo dimer decreases while the other two species increase in their concentrations. No larger Fe oligomers were detected. Given that the structure of the μ-oxo dimer is incompatible with those of all Fe oxides and oxyhydroxides, our results suggest that reconfiguration of the μ-oxo dimer structure occurs prior to further condensation leading up to the nucleation of ferrihydrite. The structural reconfiguration is likely the rate-limiting step involved in the nucleation process.

  14. Precipitation pathways for ferrihydrite formation in acidic solutions

    SciTech Connect

    Zhu, Mengqiang; Khalid, Syed; Frandsen, Cathrine; Wallace, Adam F.; Legg, Benjamin; Zhang, Hengzhong; Morup, Steen; Banfield, Jillian F.; Waychunas, Glenn A.

    2015-10-03

    In this study, iron oxides and oxyhydroxides form via Fe3+ hydrolysis and polymerization in many aqueous environments, but the pathway from Fe3+ monomers to oligomers and then to solid phase nuclei is unknown. In this work, using combined X-ray, UV–vis, and Mössbauer spectroscopic approaches, we were able to identify and quantify the long-time sought ferric speciation over time during ferric oxyhydroxide formation in partially-neutralized ferric nitrate solutions ([Fe3+] = 0.2 M, 1.8 < pH < 3). Results demonstrate that Fe exists mainly as Fe(H2O)63+, μ-oxo aquo dimers and ferrihydrite, and that with time, the μ-oxo dimer decreases while the other two species increase in their concentrations. No larger Fe oligomers were detected. Given that the structure of the μ-oxo dimer is incompatible with those of all Fe oxides and oxyhydroxides, our results suggest that reconfiguration of the μ-oxo dimer structure occurs prior to further condensation leading up to the nucleation of ferrihydrite. The structural reconfiguration is likely the rate-limiting step involved in the nucleation process.

  15. Precipitation pathways for ferrihydrite formation in acidic solutions

    DOE PAGES

    Zhu, Mengqiang; Khalid, Syed; Frandsen, Cathrine; ...

    2015-10-03

    In this study, iron oxides and oxyhydroxides form via Fe3+ hydrolysis and polymerization in many aqueous environments, but the pathway from Fe3+ monomers to oligomers and then to solid phase nuclei is unknown. In this work, using combined X-ray, UV–vis, and Mössbauer spectroscopic approaches, we were able to identify and quantify the long-time sought ferric speciation over time during ferric oxyhydroxide formation in partially-neutralized ferric nitrate solutions ([Fe3+] = 0.2 M, 1.8 < pH < 3). Results demonstrate that Fe exists mainly as Fe(H2O)63+, μ-oxo aquo dimers and ferrihydrite, and that with time, the μ-oxo dimer decreases while the othermore » two species increase in their concentrations. No larger Fe oligomers were detected. Given that the structure of the μ-oxo dimer is incompatible with those of all Fe oxides and oxyhydroxides, our results suggest that reconfiguration of the μ-oxo dimer structure occurs prior to further condensation leading up to the nucleation of ferrihydrite. The structural reconfiguration is likely the rate-limiting step involved in the nucleation process.« less

  16. Reactions Between Water Soluble Organic Acids and Nitrates in Atmospheric Aerosols: Recycling of Nitric Acid and Formation of Organic Salts

    SciTech Connect

    Wang, Bingbing; Laskin, Alexander

    2014-03-25

    Atmospheric particles often include a complex mixture of nitrate and secondary organic materials accumulated within the same individual particles. Nitrate as an important inorganic component can be chemically formed in the atmosphere. For instance, formation of sodium nitrate (NaNO3) and calcium nitrate Ca(NO3)2 when nitrogen oxide and nitric acid (HNO3) species react with sea salt and calcite, respectively. Organic acids contribute a significant fraction of photochemically formed secondary organics that can condense on the preexisting nitrate-containing particles. Here, we present a systematic microanalysis study on chemical composition of laboratory generated particles composed of water soluble organic acids and nitrates (i.e. NaNO3 and Ca(NO3)2) investigated using computer controlled scanning electron microscopy with energy dispersive analysis of X-rays (CCSEM/EDX) and Fourier transform infrared micro-spectroscopy (micro-FTIR). The results show that water-soluble organic acids can react with nitrates releasing gaseous HNO3 during dehydration process. These reactions are attributed to acid displacement of nitrate with weak organic acids driven by the evaporation of HNO3 into gas phase due to its relatively high volatility. The reactions result in significant nitrate depletion and formation of organic salts in mixed organic acids/nitrate particles that in turn may affect their physical and chemical properties relevant to atmospheric environment and climate. Airborne nitrate concentrations are estimated by thermodynamic calculations corresponding to various nitrate depletions in selected organic acids of atmospheric relevance. The results indicate a potential mechanism of HNO3 recycling, which may further affect concentrations of gas- and aerosol-phase species in the atmosphere and the heterogeneous reaction chemistry between them.

  17. Retinoic acid deficiency alters second heart field formation

    PubMed Central

    Ryckebusch, Lucile; Wang, Zengxin; Bertrand, Nicolas; Lin, Song-Chang; Chi, Xuan; Schwartz, Robert; Zaffran, Stéphane; Niederreither, Karen

    2008-01-01

    Retinoic acid (RA), the active derivative of vitamin A, has been implicated in various steps of cardiovascular development. The retinaldehyde dehydrogenase 2 (RALDH2) enzyme catalyzes the second oxidative step in RA biosynthesis and its loss of function creates a severe embryonic RA deficiency. Raldh2−/− knockout embryos fail to undergo heart looping and have impaired atrial and sinus venosus development. To understand the mechanism(s) producing these changes, we examined the contribution of the second heart field (SHF) to pharyngeal mesoderm, atria, and outflow tract in Raldh2−/− embryos. RA deficiency alters SHF gene expression in two ways. First, Raldh2−/− embryos exhibited a posterior expansion of anterior markers of the SHF, including Tbx1, Fgf8, and the Mlc1v-nlacZ-24/Fgf10 reporter transgene as well as of Islet1. This occurred at early somite stages, when cardiac defects became irreversible in an avian vitamin A-deficiency model, indicating that endogenous RA is required to restrict the SHF posteriorly. Explant studies showed that this expanded progenitor population cannot differentiate properly. Second, RA up-regulated cardiac Bmp expression levels at the looping stage. The contribution of the SHF to both inflow and outflow poles was perturbed under RA deficiency, creating a disorganization of the heart tube. We also investigated genetic cross-talk between Nkx2.5 and RA signaling by generating double mutant mice. Strikingly, Nkx2.5 deficiency was able to rescue molecular defects in the posterior region of the Raldh2−/− mutant heart, in a gene dosage-dependent manner. PMID:18287057

  18. Asymptotic Representation of the Temperature Field in Injection Stages During the Cyclic Acidizing of the Formation

    NASA Astrophysics Data System (ADS)

    Filippov, A. I.; Akhmetova, O. V.; Koval‧skii, A. A.; Kabirov, I. F.

    2016-11-01

    The authors have obtained an asymptotic solution to the problem on the temperature fi eld appearing during the injection of a chemically active solvent into a layered inhomogeneous orthotropic formation with account taken of temperature disturbances due to the preceding technological processes. This makes it possible to use the obtained solution for calculations under the conditions of multiple cyclic action. The sources of temperature disturbances are the liberation of heat due to the chemical reaction and the change in the temperature of the acid solution injected into the formation. Therefore, the obtained solution also covers the range of thermal-acidizing processes. The implemented method of construction of the solution is an extension of an asymptotic method accurate in the mean, which has been proposed by the authors as applied to the problems with nonzero initial conditions. The results of calculations of space-time temperature distributions under the conditions of hydrochloric acid treatment of carbonaceous formations have been given.

  19. Formation of catechols via removal of acid side chains from ibuprofen and related aromatic acids.

    PubMed

    Murdoch, Robert W; Hay, Anthony G

    2005-10-01

    Although ibuprofen [2-(4-isobutylphenyl)-propionic acid] is one of the most widely consumed drugs in the world, little is known regarding its degradation by environmental bacteria. Sphingomonas sp. strain Ibu-2 was isolated from a wastewater treatment plant based on its ability to use ibuprofen as a sole carbon and energy source. A slight preference toward the R enantiomer was observed, though both ibuprofen enantiomers were metabolized. A yellow color, indicative of meta-cleavage, accumulated transiently in the culture supernatant when Ibu-2 was grown on ibuprofen. When and only when 3-flurocatechol was used to poison the meta-cleavage system, isobutylcatechol was identified in the culture supernatant via gas chromatography-mass spectrometry analysis. Ibuprofen-induced washed-cell suspensions also metabolized phenylacetic acid and 2-phenylpropionic acid to catechol, while 3- and 4-tolylacetic acids and 2-(4-tolyl)-propionic acid were metabolized to the corresponding methyl catechols before ring cleavage. These data suggest that, in contrast to the widely distributed coenzyme A ligase, homogentisate, or homoprotocatechuate pathway for metabolism of phenylacetic acid and similar compounds, Ibu-2 removes the acidic side chain of ibuprofen and related compounds prior to ring cleavage.

  20. Influence of Oleic Acid on Rumen Fermentation and Fatty Acid Formation In Vitro

    PubMed Central

    Tang, Shaoxun; Guan, Leluo; He, Zhixiong; Guan, Yongjuan; Tan, Zhiliang; Han, Xuefeng; Zhou, Chuanshe; Kang, Jinhe; Wang, Min

    2016-01-01

    A series of batch cultures were conducted to investigate the effects of oleic acid (OA) on in vitro ruminal dry matter degradability (IVDMD), gas production, methane (CH4) and hydrogen (H2) production, and proportion of fatty acids. Rumen fluid was collected from fistulated goats, diluted with incubation buffer, and then incubated with 500 mg Leymus chinensis meal supplemented with different amounts of OA (0, 20, 40, and 60 mg for the CON, OA20, OA40 and OA60 groups, respectively). Incubation was carried out anaerobically at 39°C for 48 h, and the samples were taken at 12, 24 and 48 h and subjected to laboratory analysis. Supplementation of OA decreased IVDMD, the cumulative gas production, theoretical maximum of gas production and CH4 production, but increased H2 production. However, no effect was observed on any parameters of rumen fermentation (pH, ammonia, production of acetate, propionate and butyrate and total volatile fatty acid production). The concentrations of some beneficial fatty acids, such as cis monounsaturated fatty acids and conjugated linoleic acid (CLA) were higher (P < 0.05) from OA groups than those from the control group at 12 h incubation. In summary, these results suggest that the OA supplementation in diet can reduce methane production and increase the amount of some beneficial fatty acids in vitro. PMID:27299526

  1. Fe/Mg smectite formation under acidic conditions on early Mars

    NASA Astrophysics Data System (ADS)

    Peretyazhko, T. S.; Sutter, B.; Morris, R. V.; Agresti, D. G.; Le, L.; Ming, D. W.

    2016-01-01

    Phyllosilicates of the smectite group detected in Noachian and early Hesperian terrains on Mars have been hypothesized to form under neutral to alkaline conditions. These pH conditions would also be favorable for formation of widespread carbonate deposits which have not been detected on Mars. We propose that smectite deposits on Mars formed under moderately acidic conditions inhibiting carbonate formation. We report here the first synthesis of Fe/Mg smectite in an acidic hydrothermal system [200 °C, pHRT ∼ 4 (pH measured at room temperature) buffered with acetic acid] from Mars-analogue, glass-rich, basalt simulant with and without aqueous Mg or Fe(II) addition under N2-purged anoxic and ambient oxic redox conditions. Synthesized Fe/Mg smectite was examined by X-ray-diffraction, Mössbauer spectroscopy, visible and near-infrared reflectance spectroscopy, scanning electron microscopy and electron microprobe to characterize mineralogy, morphology and chemical composition. Alteration of the glass phase of basalt simulant resulted in formation of the Fe/Mg smectite mineral saponite with some mineralogical and chemical properties similar to the properties reported for Fe/Mg smectite on Mars. Our experiments are evidence that neutral to alkaline conditions on early Mars are not necessary for Fe/Mg smectite formation as previously inferred. Phyllosilicate minerals could instead have formed under mildly acidic pH conditions. Volcanic SO2 emanation and sulfuric acid formation is proposed as the major source of acidity for the alteration of basaltic materials and subsequent formation of Fe/Mg smectite.

  2. D‐amino acids do not inhibit Pseudomonas aeruginosa biofilm formation

    PubMed Central

    Frye, Mitchell; Gagnon, Patricia; Vogel, Joseph P.; Chole, Richard

    2016-01-01

    Objective Pseudomonas aeruginosa, a known biofilm‐forming organism, is an opportunistic pathogen that plays an important role in chronic otitis media, tracheitis, cholesteatoma, chronic wounds, and implant infections. Eradication of biofilm infections has been a challenge because the biofilm phenotype provides bacteria with a protective environment from the immune system and antibiotics; thus, there has been great interest in adjunctive molecules that may inhibit biofilm formation or cause biofilm dispersal. There are reports that D‐amino acids may inhibit biofilms. In this study, we test the ability of various D‐amino acids to inhibit P. aeruginosa biofilm formation in vitro. Study Design We evaluated the effect of D‐alanine (10 mM), D‐leucine (10 mM), D‐methionine (10 mM), D‐tryptophan (10 mM), and D‐tyrosine (10 uM and 1 mM) on biofilm formation in two commonly studied laboratory strains of P. aeruginosa: PAO1 and PA14. Methods Biofilms were grown in 24‐well and 96‐well tissue culture plates, documented photographically and stained with 0.1% crystal violet and solubilized in 33% glacial acetic acid for quantification. Results In strains PAO1 and PA14, the addition of D‐amino acids did not result in an inhibitory effect on biofilm growth in 24‐well plates. Repeating the study in 96‐well plates confirmed our findings that D‐amino acids do not inhibit biofilm formation of P. aeruginosa. Conclusion We conclude that D‐amino acids only slow the production of biofilms rather than completely prevent biofilm formation; therefore, D‐amino acids represent a poor option for potential clinically therapeutic interventions. Level of Evidence N/A. PMID:28286870

  3. Insights into the formation mechanism of chloropropanol fatty acid esters under laboratory-scale deodorization conditions.

    PubMed

    Hori, Katsuhito; Hori-Koriyama, Natsuko; Tsumura, Kazunobu; Fukusaki, Eiichiro; Bamba, Takeshi

    2016-08-01

    Chloropropanol fatty acid esters (CPFAEs) are well-known contaminants in refined oils and fats, and several research groups have studied their formation. However, the results obtained in these studies were not satisfactory because the CPFAEs were not analyzed comprehensively. Thus, in the present study, a comprehensive analysis was performed to obtain new details about CPFAE formation. Each lipid (monopalmitin, dipalmitin, tripalmitin, monoolein, diolein, triolein, and crude palm oil) was heated at 250°C for 90 min, and the CPFAEs were analyzed using supercritical fluid chromatography/tandem mass spectrometry. It was found that CP fatty acid monoesters were formed from monoacylglycerols and diacylglycerols after heating in the presence of a chlorine compound. In addition, CP fatty acid diesters were formed from diacylglycerols and triacylglycerols under the same conditions. In the case of crude palm oil, only CP fatty acid diesters were formed. Therefore, these results indicated that CPFAEs in refined palm oil were formed mainly from triacylglycerols.

  4. Nitric acid in polar stratospheric clouds - Similar temperature of nitric acid condensation and cloud formation

    NASA Technical Reports Server (NTRS)

    Pueschel, Rudolf F.; Snetsinger, Kenneth G.; Hamill, Patrick; Goodman, Jindra K.; Mccormick, M. Patrick

    1990-01-01

    As shown independently by two different techniques, nitric acid aerosols and polar stratospheric clouds (PSCs) both form below similar threshold temperatures. This supports the idea that the PSC particles involved in chlorine activation and ozone depletion in the winter polar stratosphere are composed of nitric acid. One technique used to show this is the inertial impaction of nitric acid aerosols using an Er-2 aircraft; the other method is remote sensing of PSCs by the Stratospheric Aerosol Measurement (SAM II) satellite borne optical sensor. Both procedures were in operation during the Arctic Airborne Stratospheric Expedition in 1989, and the Airborne Antarctic Ozone Experiment in 1987. Analysis of Arctic particles gathered in situ indicates the presence of nitric acid below a 'first appearance' temperature Tfa = 202 K. This is the same highest temperature at which PSCs are seen by the SAM II satellite. In comparison, a 'first appearance' temperature Tfa = 198 K as found for the Antarctic samples.

  5. Computational study of the hydration of sulfuric acid dimers: implications for acid dissociation and aerosol formation.

    PubMed

    Temelso, Berhane; Phan, Thuong Ngoc; Shields, George C

    2012-10-04

    We have investigated the thermodynamics of sulfuric acid dimer hydration using ab initio quantum mechanical methods. For (H(2)SO(4))(2)(H(2)O)(n) where n = 0-6, we employed high-level ab initio calculations to locate the most stable minima for each cluster size. The results presented herein yield a detailed understanding of the first deprotonation of sulfuric acid as a function of temperature for a system consisting of two sulfuric acid molecules and up to six waters. At 0 K, a cluster of two sulfuric acid molecules and one water remains undissociated. Addition of a second water begins the deprotonation of the first sulfuric acid leading to the di-ionic species (the bisulfate anion HSO(4)(-), the hydronium cation H(3)O(+), an undissociated sulfuric acid molecule, and a water). Upon the addition of a third water molecule, the second sulfuric acid molecule begins to dissociate. For the (H(2)SO(4))(2)(H(2)O)(3) cluster, the di-ionic cluster is a few kcal mol(-1) more stable than the neutral cluster, which is just slightly more stable than the tetra-ionic cluster (two bisulfate anions, two hydronium cations, and one water). With four water molecules, the tetra-ionic cluster, (HSO(4)(-))(2)(H(3)O(+))(2)(H(2)O)(2), becomes as favorable as the di-ionic cluster H(2)SO(4)(HSO(4)(-))(H(3)O(+))(H(2)O)(3) at 0 K. Increasing the temperature favors the undissociated clusters, and at room temperature we predict that the di-ionic species is slightly more favorable than the neutral cluster once three waters have been added to the cluster. The tetra-ionic species competes with the di-ionic species once five waters have been added to the cluster. The thermodynamics of stepwise hydration of sulfuric acid dimer is similar to that of the monomer; it is favorable up to n = 4-5 at 298 K. A much more thermodynamically favorable pathway forming sulfuric acid dimer hydrates is through the combination of sulfuric acid monomer hydrates, but the low concentration of sulfuric acid relative to

  6. The electrochemical reduction of carbon dioxide to formate/formic acid: engineering and economic feasibility.

    PubMed

    Agarwal, Arun S; Zhai, Yumei; Hill, Davion; Sridhar, Narasi

    2011-09-19

    The engineering and economic feasibility of large-scale electrochemical reduction of carbon dioxide to formate salts and formic acid is the focus of this Full Paper. In our study we investigated the long-term performance of tin and other proprietary catalysts in the reduction of carbon dioxide to formate/formic acid at a gas/solid/liquid interface, using a flow-through reactor. The overall economics and energy consumption of the process are evaluated through a value chain analysis. The sensitivity of the net present value of the process to various process parameters is examined.

  7. Biofilm Formation and Detachment in Gram-Negative Pathogens Is Modulated by Select Bile Acids

    PubMed Central

    Townsley, Loni; Peach, Kelly C.; Navarro, Gabriel; Shikuma, Nicholas J.; Bray, Walter M.; Riener, Romina M.; Yildiz, Fitnat H.; Linington, Roger G.

    2016-01-01

    Biofilms are a ubiquitous feature of microbial community structure in both natural and host environments; they enhance transmission and infectivity of pathogens and provide protection from human defense mechanisms and antibiotics. However, few natural products are known that impact biofilm formation or persistence for either environmental or pathogenic bacteria. Using the combination of a novel natural products library from the fish microbiome and an image-based screen for biofilm inhibition, we describe the identification of taurine-conjugated bile acids as inhibitors of biofilm formation against both Vibrio cholerae and Pseudomonas aeruginosa. Taurocholic acid (1) was isolated from the fermentation broth of the fish microbiome-derived strain of Rhodococcus erythropolis and identified using standard NMR and MS methods. Screening of the twelve predominant human steroidal bile acid components revealed that a subset of these compounds can inhibit biofilm formation, induce detachment of preformed biofilms under static conditions, and that these compounds display distinct structure-activity relationships against V. cholerae and P. aeruginosa. Our findings highlight the significance of distinct bile acid components in the regulation of biofilm formation and dispersion in two different clinically relevant bacterial pathogens, and suggest that the bile acids, which are endogenous mammalian metabolites used to solubilize dietary fats, may also play a role in maintaining host health against bacterial infection. PMID:26992172

  8. Sulfate Formation From Acid-Weathered Phylosilicates: Implications for the Aqueous History of Mars

    NASA Technical Reports Server (NTRS)

    Craig, P. I.; Ming, D. W.; Rampe, E. B.

    2014-01-01

    Most phyllosilicates on Mars are thought to have formed during the planet's earliest Noachian era, then Mars underwent a global change making the planet's surface more acidic [e.g. 1]. Prevailing acidic conditions may have affected the already existing phyllosilicates, resulting in the formation of sulfates. Both sulfates and phyllosilicates have been identified on Mars in a variety of geologic settings [2] but only in a handful of sites are these minerals found in close spatial proximity to each other, including Mawrth Vallis [3,4] and Gale Crater [5]. While sulfate formation from the acidic weathering of basalts is well documented in the literature [6,7], few experimental studies investigate sulfate formation from acid-weathered phyllosilicates [8-10]. The purpose of this study is to characterize the al-teration products of acid-weathered phyllosilicates in laboratory experiments. We focus on three commonly identified phyllosilicates on Mars: nontronite (Fe-smectite), saponite (Mg-smectite), and montmorillonite (Al-smectite) [1, and references therein]. This information will help constrain the formation processes of sulfates observed in close association with phyllosilicates on Mars and provide a better understanding of the aqueous history of such regions as well as the planet as a whole.

  9. Modeling dichloroacetic acid formation from the reaction of monochloramine with natural organic matter.

    PubMed

    Duirk, Stephen E; Valentine, Richard L

    2006-08-01

    A kinetic model was developed to predict dichloroacetic acid (DCAA) formation in chloraminated systems. Equations describing DCAA formation were incorporated into an established comprehensive monochloramine-natural organic matter (NOM) reaction model. DCAA formation was theorized to be proportional to the amount of NOM oxidized by monochloramine and described by a single dimensionless DCAA formation coefficient, theta(DCAA) (M(DCAA)/M(DOC(ox)). The applicability of the model to describe DCAA formation in the presence of six different NOM sources was evaluated. DCAA formation could be described by considering a single NOM source-specific value for theta(DCAA) over a wide range of experimental conditions (i.e., pH, NOM, free ammonia, and monochloramine concentrations). DCAA formation appears to be directly proportional to the amount of active chlorine (monochloramine and free chlorine) that reacted with the NOM under these experimental conditions. Values of theta(DCAA) for all six NOM sources, determined by nonlinear regression analysis, varied from 6.51 x 10(-3) to 1.15 x 10(-2) and were linearly correlated with specific ultraviolet absorbance at 280 nm (SUVA(280)). The ability to model monochloramine loss and DCAA formation in the presence of NOM provides insight into disinfection by-product (DBP) formation pathways under chloramination conditions. The subsequent model and correlations to SUVA has the potential to aid the water treatment industry as a tool in developing strategies that minimize DBP formation while maintaining the microbial integrity of the water distribution system.

  10. Formation of Amino Acid Thioesters for Prebiotic Peptide Synthesis: Catalysis By Amino Acid Products

    NASA Technical Reports Server (NTRS)

    Weber, Arthur L.; DeVincenzi, Donald L. (Technical Monitor)

    1999-01-01

    The origin of life can be described as a series of events in which a prebiotic chemical process came increasingly under the control of its catalytic products. In our search for this prebiotic process that yielded catalytic takeover products (such as polypeptides), we have been investigating a reaction system that generates peptide-forming amino acid thioesters from formaldehyde, glycolaldehyde, and ammonia in the presence of thiols. As shown below, this model process begins by aldol condensation of formaldehyde and glycolaldehyde to give trioses and releases. These sugars then undergo beta-dehydration yielding their respective alpha-ketoaldehydes. Addition of ammonia to the alpha-ketoaldehydes yields imines which can either: (a) rearrange in the presence of thesis to give amino acid thioesters or (be react with another molecule of aldehyde to give imidazoles. This 'one-pot' reaction system operates under mild aqueous conditions, and like modem amino acid biosynthesis, uses sugar intermediates which are converted to products by energy-yielding redox reactions. Recently, we discovered that amino acids, such as the alanine reaction product, catalyze the first and second steps of the process. In the presence of ammonia the process also generates other synthetically useful products, like the important biochemical -- pyruvic acid.

  11. Properties of synthetic ferrihydrite as an amino acid adsorbent and a promoter of peptide bond formation.

    PubMed

    Matrajt, G; Blanot, D

    2004-03-01

    Ferrihydrite, an iron oxide hydroxide, is found in all kinds of environments, from hydrothermal hot springs to extraterrestrial materials. It has been shown that this material is nanoporous, and because of its high surface area, it has outstanding adsorption properties and in some cases catalysis properties. In this work we studied the adsorption properties of ferrihydrite with respect to amino acids. Samples of pure ferrihydrite were synthesised and exposed to solutions of amino acids including both proteinaceous and non-proteinaceous species. These experiments revealed important characteristics of this mineral as both an adsorbent of amino acids and a promoter of peptide bond formation.

  12. Beta-glycerophosphate accelerates RANKL-induced osteoclast formation in the presence of ascorbic acid.

    PubMed

    Noh, A Long Sae Mi; Yim, Mijung

    2011-03-01

    Despite numerous reports of the synergistic effects of beta-glycerophosphate and ascorbic acid in inducing the differentiation of osteoblasts, little is known about their roles in osteoclastic differentiation. Therefore, we investigated the effect of beta-glycerophosphate on osteoclastogenesis in the presence of ascorbic acid using primary mouse bone marrow cultures treated with macrophage colony-stimulating factor (M-CSF) and receptor activator of nuclear factor (NF)-kappaB ligand (RANKL). Beta-Glycerophosphate dose-dependently increased RANKL-induced osteoclast formation in the presence of ascorbic acid. This stimulatory effect was apparent when beta-glycerophosphate and ascorbic acid were only added during the late stages of the culture period, indicating that they influence later events in osteoclastic differentiation. While the combination of beta-glycerophosphate and ascorbic acid inhibited RANKL-stimulated activation of ERK and p38, and degradation of IkappaB, it increased the induction of c-Fos and NFATc1. In addition, beta-glycerophosphate and ascorbic acid together enhanced the induction of COX-2 following RANKL stimulation. Taken together, our data suggest that beta-glycerophosphate and ascorbic acid have synergistic effects on osteoclast formation, increasing RANKL-mediated induction of c-Fos, NFATc1 and COX-2 in osteoclast precursors.

  13. Effect of hyaluronic acid on postoperative intraperitoneal adhesion formation in the rat model

    SciTech Connect

    Urman, B.; Gomel, V.; Jetha, N. )

    1991-09-01

    The aim of this study was to determine the effectiveness of hyaluronic acid solution in preventing intraperitoneal (IP) adhesions. The study design was prospective, randomized and blinded and involved 83 rats. Measured serosal injury was inflicted using a CO2 laser on the right uterine horn of the rat. Animals randomized to groups 1 and 2 received either 0.4% hyaluronic acid or its diluent phosphate-buffered saline (PBS) intraperitoneally before and after the injury. In groups 3 and 4, the same solutions were used only after the injury. Postoperative adhesions were assessed at second-look laparotomy. Histologic assessment of the fresh laser injury was carried out on uteri pretreated with hyaluronic acid, PBS, or nothing. Pretreatment with hyaluronic acid was associated with a significant reduction in postoperative adhesions and a significantly decreased crater depth. Hyaluronic acid appears to reduce postoperative IP adhesion formation by coating the serosal surfaces and decreasing the extent of initial tissue injury.

  14. The Acid Catalyzed Nitration of Methanol: Formation of Methyl Nitrate via Aerosol Chemistry

    NASA Technical Reports Server (NTRS)

    Riffel, Brent G.; Michelsen, Rebecca R.; Iraci, Laura T.

    2004-01-01

    The liquid phase acid catalyzed reaction of methanol with nitric acid to yield methyl nitrate under atmospheric conditions has been investigated using gas phase infrared spectroscopy. This nitration reaction is expected to occur in acidic aerosol particles found in the upper troposphere/lower stratosphere as highly soluble methanol and nitric acid diffuse into these aerosols. Gaseous methyl nitrate is released upon formation, suggesting that some fraction of NO(x) may he liberated from nitric acid (methyl nitrate is later photolyzed to NO(x)) before it is removed from the atmosphere by wet deposition. Thus, this reaction may have important implications for the NO(x) budget. Reactions have been initiated in 45-62 wt% H2SO4 solutions at 10.0 C. Methyl nitrate production rates increased exponentially with acidity within the acidity regime studied. Preliminary calculations suggest that the nitronium ion (NO2(+) is the active nitrating agent under these conditions. The reaction order in methanol appears to depend on the water/methanol ratio and varies from first to zeroth order under conditions investigated. The nitration is first order in nitronium at all acidities investigated. A second order rate constant, kappa(sub 2), has been calculated to be 1 x 10(exp 8)/ M s when the reaction is first order in methanol. Calculations suggest the nitration is first order in methanol under tropospheric conditions. The infinitesimal percentage of nitric acid in the nitronium ion form in this acidity regime probably makes this reaction insignificant for the upper troposphere; however, this nitration may become significant in the mid stratosphere where colder temperatures increase nitric acid solubility and higher sulfuric acid content shifts nitric acid speciation toward the nitronium ion.

  15. Acid-mediated formation of trifluoromethyl sulfonates from sulfonic acids and a hypervalent iodine trifluoromethylating agent.

    PubMed

    Koller, Raffael; Huchet, Quentin; Battaglia, Philip; Welch, Jan M; Togni, Antonio

    2009-10-28

    A variety of sulfonic acids have been trifluoromethylated using 1-trifluoromethyl-1,2-benziodoxol-3(1H)-one under mild conditions in good to excellent yields. Initial mechanistic investigations of this reaction show a clean second-order kinetics and only very weak substrate electronic effects.

  16. Activation of carboxyl group with cyanate: peptide bond formation from dicarboxylic acids.

    PubMed

    Danger, Grégoire; Charlot, Solenne; Boiteau, Laurent; Pascal, Robert

    2012-06-01

    The reaction of cyanate with C-terminal carboxyl groups of peptides in aqueous solution was considered as a potential pathway for the abiotic formation of peptide bonds under the condition of the primitive Earth. The catalytic effect of dicarboxylic acids on cyanate hydrolysis was definitely attributed to intramolecular nucleophilic catalysis by the observation of the 1H-NMR signal of succinic anhydride when reacting succinic acid with KOCN in aqueous solution (pH 2.2-5.5). The formation of amide bonds was noticed when adding amino acids or amino acid derivatives into the solution. The reaction of N-acyl aspartic acid derivatives was observed to proceed similarly and the scope of the cyanate-promoted reaction was analyzed from the standpoint of prebiotic peptide formation. The role of cyanate in activating peptide C-terminus constitutes a proof of principle that intramolecular reactions of adducts of peptides C-terminal carboxyl groups with activating agents represent a pathway for peptide activation in aqueous solution, the relevance of which is discussed in connexion with the issue of the emergence of homochirality.

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  18. Reduced by-product formation and modified oxygen availability improve itaconic acid production in Aspergillus niger.

    PubMed

    Li, An; Pfelzer, Nina; Zuijderwijk, Robbert; Brickwedde, Anja; van Zeijl, Cora; Punt, Peter

    2013-05-01

    Aspergillus niger has an extraordinary potential to produce organic acids as proven by its application in industrial citric acid production. Previously, it was shown that expression of the cis-aconitate decarboxylase gene (cadA) from Aspergillus terreus converted A. niger into an itaconic acid producer (Li et al., Fungal Genet Bio 48: 602-611, 2011). After some initial steps in production optimization in the previous research (Li et al., BMC biotechnol 12: 57, 2012), this research aims at modifying host strains and fermentation conditions to further improve itaconic acid production. Expression of two previously identified A. terreus genes encoding putative organic acid transporters (mttA, mfsA) increased itaconic acid production in an A. niger cis-aconitate decarboxylase expressing strain. Surprisingly, the production did not increase further when both transporters were expressed together. Meanwhile, oxalic acid was accumulated as a by-product in the culture of mfsA transformants. In order to further increase itaconic acid production and eliminate by-product formation, the non-acidifying strain D15#26 and the oxaloacetate acetylhydrolase (oahA) deletion strain AB 1.13 ∆oahA #76 have been analyzed for itaconic acid production. Whereas cadA expression in AB 1.13 ∆oahA #76 resulted in higher itaconic acid production than strain CAD 10.1, this was not the case in strain D15#26. As expected, oxalic acid production was eliminated in both strains. In a further attempt to increase itaconic acid levels, an improved basal citric acid-producing strain, N201, was used for cadA expression. A selected transformant (N201CAD) produced more itaconic acid than strain CAD 10.1, derived from A. niger strain AB1.13. Subsequently, we have focused on the influence of dissolved oxygen (D.O.) on itaconic acid production. Interestingly, reduced D.O. levels (10-25 %) increased itaconic acid production using strain N201 CAD. Similar results were obtained in strain AB 1.13 CAD + HBD2

  19. The chitosan-gelatin (bio)polyelectrolyte complexes formation in an acidic medium.

    PubMed

    Voron'ko, Nicolay G; Derkach, Svetlana R; Kuchina, Yuliya A; Sokolan, Nina I

    2016-03-15

    The interaction of cationic polysaccharide chitosan and gelatin accompanied by the stoichiometric (bio)polyelectrolyte complexes formation has been studied by the methods of capillary viscometry, UV and FTIR spectroscopy and dispersion of light scattering. Complexes were formed in the aqueous phase, with pH being less than the isoelectric point of gelatin (pIgel). The particle size of the disperse phase increases along with the growth of the relative viscosity in comparison with sols of the individual components-polysaccharide and gelatin. Possible models and mechanism of (bio)polyelectrolyte complexes formation have been discussed. It was shown that the complex formation takes place not only due to the hydrogen bonds, but also due to the electrostatic interactions between the positively charged amino-groups of chitosan and negatively charged amino acid residues (glutamic Glu and aspartic Asp acids) of gelatin.

  20. Thermochemistry for silicic acid formation reaction: Prediction of new reaction pathway

    NASA Astrophysics Data System (ADS)

    Mondal, Bhaskar; Ghosh, Deepanwita; Das, Abhijit K.

    2009-08-01

    Reaction between SiO 2 and water has been studied extensively using ab initio methods. The mechanism for formation of metasilicic acid SiO(OH) 2 and orthosilicic acid Si(OH) 4 has been explored and a new pathway for formation of Si(OH) 4 is predicted. Heats of reaction ( ΔrH298∘) and heats of formation ( ΔfH298∘) at 298 K for the related reactions and species calculated at two different theoretical levels G3B3 and G3MP2B3 agree well with the literature values. It is found that when SiO 2 reacts simultaneously with two water molecules, the thermodynamic as well as kinetic feasibility of the process is much greater than that when SiO 2 reacts with one molecule of water.

  1. Processes and fluxes during the initial stage of acid sulfate soil formation

    NASA Astrophysics Data System (ADS)

    Gröger, J.; Hamer, K.; Schulz, H. D.

    2009-04-01

    acid sulfate soils. Furthermore, these experiments can serve as a model for the initial stage of naturally occurring acid sulfate soil formation. Thus, the results will provide a base for the interpretation of element distribution in the solid phase of natural acid sulfate soil profiles. References DENT, D. L. and PONS, L. J. (1995) A world perspective on acid sulphate soils. Geoderma 67, 263-276. PONS, L. J. (1973) Outline of genesis, characteristics, classification and improvement of acid sulphate soils. In Acid Sulphate Soils - Proceedings of the International Symposium on Acid Sulphate Soils - I Introductory Papers and Bibliography (ed. H. Dost). pp. 3-27

  2. Formation of dopamine adducts derived from brain polyunsaturated fatty acids: mechanism for Parkinson disease.

    PubMed

    Liu, Xuebo; Yamada, Naruomi; Maruyama, Wakako; Osawa, Toshihiko

    2008-12-12

    Oxidative stress appears to be directly involved in the pathogenesis of the neurodegeneration of dopaminergic systems in Parkinson disease. In this study, we formed four dopamine modification adducts derived from docosahexaenoic acid (C22:6/omega-3) and arachidonic acid (C18:4/omega-6), which are known as the major polyunsaturated fatty acids in the brain. Upon incubation of dopamine with fatty acid hydroperoxides and an in vivo experiment using rat brain tissue, all four dopamine adducts were detected. Furthermore, hexanoyl dopamine (HED), an arachidonic acid-derived adduct, caused severe cytotoxicity in human dopaminergic neuroblastoma SH-SY5Y cells, whereas the other adducts were only slightly affected. The HED-induced cell death was found to include apoptosis, which also seems to be mediated by reactive oxygen species generation and mitochondrial abnormality. Additionally, the experiments using monoamine transporter inhibitor and mouse embryonic fibroblast NIH-3T3 cells that lack the monoamine transporter indicate that the HED-induced cytotoxicity might specially occur in the neuronal cells. These data suggest that the formation of the docosahexaenoic acid- and arachidonic acid-derived dopamine adducts in vitro and in vivo, and HED, the arachidonic acid-derived dopamine modification adduct, which caused selective cytotoxicity of neuronal cells, may indicate a novel mechanism responsible for the pathogenesis in Parkinson disease.

  3. Formation of β-glucogallin, the precursor of ellagic acid in strawberry and raspberry

    PubMed Central

    Schulenburg, Katja; Feller, Antje; Hoffmann, Thomas; Schecker, Johannes H.; Martens, Stefan; Schwab, Wilfried

    2016-01-01

    Ellagic acid/ellagitannins are plant polyphenolic antioxidants that are synthesized from gallic acid and have been associated with a reduced risk of cancer and cardiovascular diseases. Here, we report the identification and characterization of five glycosyltransferases (GTs) from two genera of the Rosaceae family (Fragaria and Rubus; F.×ananassa FaGT2*, FaGT2, FaGT5, F. vesca FvGT2, and R. idaeus RiGT2) that catalyze the formation of 1-O-galloyl-β-d-glucopyranose (β-glucogallin) the precursor of ellagitannin biosynthesis. The enzymes showed substrate promiscuity as they formed glucose esters of a variety of (hydroxyl)benzoic and (hydroxyl)cinnamic acids. Determination of kinetic values and site-directed mutagenesis revealed amino acids that affected substrate preference and catalytic activity. Green immature strawberry fruits were identified as the main source of gallic acid, β-glucogallin, and ellagic acid in accordance with the highest GT2 gene expression levels. Injection of isotopically labeled gallic acid into green fruits of stable transgenic antisense FaGT2 strawberry plants clearly confirmed the in planta function. Our results indicate that GT2 enzymes might contribute to the production of ellagic acid/ellagitannins in strawberry and raspberry, and are useful to develop strawberry fruit with additional health benefits and for the biotechnological production of bioactive polyphenols. PMID:26884604

  4. Formation of β-glucogallin, the precursor of ellagic acid in strawberry and raspberry.

    PubMed

    Schulenburg, Katja; Feller, Antje; Hoffmann, Thomas; Schecker, Johannes H; Martens, Stefan; Schwab, Wilfried

    2016-04-01

    Ellagic acid/ellagitannins are plant polyphenolic antioxidants that are synthesized from gallic acid and have been associated with a reduced risk of cancer and cardiovascular diseases. Here, we report the identification and characterization of five glycosyltransferases (GTs) from two genera of the Rosaceae family (Fragaria and Rubus; F. × ananassa FaGT2*, FaGT2, FaGT5, F. vesca FvGT2, and R. idaeus RiGT2) that catalyze the formation of 1-O-galloyl-β-D-glucopyranose (β-glucogallin) the precursor of ellagitannin biosynthesis. The enzymes showed substrate promiscuity as they formed glucose esters of a variety of (hydroxyl)benzoic and (hydroxyl)cinnamic acids. Determination of kinetic values and site-directed mutagenesis revealed amino acids that affected substrate preference and catalytic activity. Green immature strawberry fruits were identified as the main source of gallic acid, β-glucogallin, and ellagic acid in accordance with the highest GT2 gene expression levels. Injection of isotopically labeled gallic acid into green fruits of stable transgenic antisense FaGT2 strawberry plants clearly confirmed the in planta function. Our results indicate that GT2 enzymes might contribute to the production of ellagic acid/ellagitannins in strawberry and raspberry, and are useful to develop strawberry fruit with additional health benefits and for the biotechnological production of bioactive polyphenols.

  5. Effect of pH on complex formation between debranched waxy rice starch and fatty acids.

    PubMed

    Yotsawimonwat, Songwut; Sriroth, Klanarong; Kaewvichit, Sayam; Piyachomkwan, Kaukoon; Jane, Jay-Lin; Sirithunyalug, Jakkapan

    2008-08-15

    Complex formations between debranched waxy rice starch (DBS) and fatty acids (FA) of different hydrocarbon chain lengths (8:0, 10:0, 12:0, 14:0, 16:0, and 18:0) were studied in an aqueous solution by measuring the blue colour stained with iodine. The objective of this study was to understand the effects of the solubility and hydrophobicity of guest molecules (FA) on the complex formation with DBS. Lauric acid (12:0) displayed the greatest complex forming ability with DBS by showing the least blue colour developed with iodine. The effect of pH (3-7) on the DBS/FA complex formation was evaluated by measuring the iodine-scanning spectra of the mixture. Short-chain FA (8:0) displayed less complex formation at pH>or=5, above the pK(a) of fatty acid (approximately 4.8), which suggested that the charge formation of the short-chain FA caused a lower partitioning of the FA into the hydrophobic cavity of the DBS single helix. On the contrary, FA of 10:0-18:0 displayed an increased complex formation at pH>5, which could be attributed to increased solubility of these longer-chain FA at a dissociated and ionized form. The hydrocarbon chain length of the FA had an important impact on the extent of the complex formation. A FA that had a shorter hydrocarbon chain was more soluble in an aqueous solution and more readily formed a complex with DBS. At pH 6 and 7 (above the pK(a)), 10:0 formed less inclusion complexes with DBS than did 12:0. Iodine-scanning spectra showed that the absorbances of all iodine-stained DBS/FA solutions at higher wavelength were substantially lower than that of the iodine-stained DBS alone, suggesting that FA preferentially formed inclusion complexes with DBS of longer chains.

  6. Evolution of internal resistance during formation of flooded lead-acid batteries

    NASA Astrophysics Data System (ADS)

    White, Chris; Deveau, Justin; Swan, Lukas G.

    2016-09-01

    This study employs experimental techniques to measure the changing internal resistance of flooded, flat-plate lead-acid batteries during container formation, revealing a novel indicator of formation completeness. In order to measure internal resistance during formation, d.c. current pulses are superimposed over the constant formation current at set intervals, while change in voltage is measured. The resulting "pulsed" internal resistance is divided into ohmic and interfacial components by measuring the ohmic resistance with short d.c. pulses as well as with a.c. injection. Various constant-current container formations are carried out using different current levels, plate thicknesses, and pulsing techniques, yielding an array of resistance trends which are explained using Butler-Volmer kinetic theory. Ohmic and interfacial resistance trends are shown both theoretically and experimentally to eventually decay to a predictable steady-state value as the formation proceeds, suggesting that this internal resistance method can be used to detect the completion of the formation. The same principles are shown to apply to recharge cycles as well, but with potentially limited practical implications in comparison to formation.

  7. Some polyphenols inhibit the formation of pentyl radical and octanoic acid radical in the reaction mixture of linoleic acid hydroperoxide with ferrous ions.

    PubMed Central

    Iwahashi, H

    2000-01-01

    Effects of some polyphenols and their related compounds (chlorogenic acid, caffeic acid, quinic acid, ferulic acid, gallic acid, D-(+)-catechin, D-(-)-catechin, 4-hydroxy-3-methoxybenzoic acid, salicylic acid, L-dopa, dopamine, L-adrenaline, L-noradrenaline, o-dihydroxybenzene, m-dihydroxybenzene, and p-dihydroxybenzene) on the formation of 13-hydroperoxide octadecadienoic (13-HPODE) acid-derived radicals (pentyl radical and octanoic acid radical) were examined. The ESR spin trapping showed that chlorogenic acid, caffeic acid, gallic acid, D-(+)-catechin, D-(-)-catechin, L-dopa, dopamine, L-adrenaline, L-noradrenaline, and o-dihydroxybenzene inhibited the overall formation of 13-HPODE acid-derived radicals in the reaction mixture of 13-HPODE with ferrous ions. The ESR peak heights of alpha-(4-pyridyl-1-oxide)-N-tert-butylnitrone (4-POBN)/13-HPODE-derived radical adducts decreased to 46+/-4% (chlorogenic acid), 54+/-2% (caffeic acid), 49+/-2% (gallic acid), 55+/-1% [D-(+)-catechin], 60+/-3% [D-(-)-catechin], 42+/-1% (L-dopa), 30+/-2% (dopamine), 49+/-2% (L-adrenaline), 24+/-2% (L-noradrenaline), and 54+/-5% (o-dihydroxybenzene) of the control, respectively. The high performance liquid chromatography-electron spin resonance (HPLC-ESR) and high performance liquid chromatography-electron spin resonance-mass spectrometries (HPLC-ESR-MS) showed that caffeic acid inhibited the formation of octanoic acid radical and pentyl radical to 42+/-2% and 52+/-7% of the control, respectively. On the other hand, the polyphenols and their related compounds had few inhibitory effects on the radical formation in the presence of EDTA. Visible absorbance measurement revealed that all the polyphenols exhibiting the inhibitory effect chelate ferrous ions. Above results indicated that the chelation of ferrous ion is essential to the inhibitory effects of the polyphenols. PMID:10677343

  8. Effect of ions on sulfuric acid-water binary particle formation: 1. Theory for kinetic- and nucleation-type particle formation and atmospheric implications

    NASA Astrophysics Data System (ADS)

    Merikanto, Joonas; Duplissy, Jonathan; Määttänen, Anni; Henschel, Henning; Donahue, Neil M.; Brus, David; Schobesberger, Siegfried; Kulmala, Markku; Vehkamäki, Hanna

    2016-02-01

    We derive a version of Classical Nucleation Theory normalized by quantum chemical results on sulfuric acid-water hydration to describe neutral and ion-induced particle formation in the binary sulfuric acid-water system. The theory is extended to treat the kinetic regime where the nucleation free energy barrier vanishes at high sulfuric acid concentrations or low temperatures. In the kinetic regime particle formation rates become proportional to sulfuric acid concentration to second power in the neutral system or first power in the ion-induced system. We derive simple general expressions for the prefactors in kinetic-type and activation-type particle formation calculations applicable also to more complex systems stabilized by other species. The theory predicts that the binary water-sulfuric acid system can produce strong new particle formation in the free troposphere both through barrier crossing and through kinetic pathways. At cold stratospheric and upper free tropospheric temperatures neutral formation dominates the binary particle formation rates. At midtropospheric temperatures the ion-induced pathway becomes the dominant mechanism. However, even the ion-induced binary mechanism does not produce significant particle formation in warm boundary layer conditions, as it requires temperatures below 0°C to take place at atmospheric concentrations. The theory successfully reproduces the characteristics of measured charged and neutral binary particle formation in CERN CLOUD3 and CLOUD5 experiments, as discussed in a companion paper.

  9. The Formation of Fe/Mg Smectite Under Mildly Acidic Conditions on Early Mars

    NASA Astrophysics Data System (ADS)

    Sutter, B.; Golden, D. C.; Ming, D.; Niles, P. B.

    2011-12-01

    The detection of Fe/Mg smectites and carbonate in Noachian and early Hesperian terrain of Mars has been used to suggest that neutral to mildly alkaline conditions prevailed during the early history of Mars. However, if early Mars was neutral to moderately alkaline with a denser CO2 atmosphere than today, then "large" carbonates deposits should be more widely detected in Noachian terrain. The critical question is: Why have so few carbonate deposits been detected compared to Fe/Mg smectites? We suggest that Fe/Mg smectites on early Mars formed under mildly acidic conditions, which would inhibit the extensive formation of carbonate deposits. The goal of this work is to evaluate the formation of Fe/Mg smectites under mildly acidic conditions. The stability of smectites under mildly acidic conditions is attributed to elevated Fe/Mg activities that inhibit smectite dissolution. Beidelite and saponite have been shown to form from hydrothermal alteration of basaltic glass at pH 3.5-4.0 in seawater solutions. Nontronite is also known to be stable in mildly acidic systems associated with mafic and ultramafic rock. Nontronite was shown to form in acid sulfate soils in the Bangkok Plain, Thailand due to oxidation of Fe-sulfides that transformed saponite to nontronite. Smectite is known to transform to kaolinite in naturally acid soils due to selective leaching of Mg. However, if Mg removal is limited, then based on equilibrium relationships, the dissolution of smectite should be minimized. If Fe and Mg solution activities are sufficiently high, such as might be found in a low water/rock ratio system that is poorly drained, smectite could form and remain stable under mildly acidic conditions on Mars. The sources of mild acidity on early Mars includes elevated atmospheric CO2 levels, Fe-hydrolysis reactions, and the presence of volcanic SO2 aerosols. Equilibrium calculations dictate that water equilibrated with an early Mars CO2 atmosphere at 1 to 4 bar yields a pH of 3.6 to 3

  10. The Formation of Fe/Mg Smectite Under Mildly Acidic Conditions on Early Mars

    NASA Technical Reports Server (NTRS)

    Sutter, Brad; Golden, D. C.; Ming, Douglas W.; Niles, P. B.

    2011-01-01

    The detection of Fe/Mg smectites and carbonate in Noachian and early Hesperian terrain of Mars has been used to suggest that neutral to mildly alkaline conditions prevailed during the early history of Mars. However, if early Mars was neutral to moderately alkaline with a denser CO2 atmosphere than today, then large carbonates deposits should be more widely detected in Noachian terrain. The critical question is: Why have so few carbonate deposits been detected compared to Fe/Mg smectites? We suggest that Fe/Mg smectites on early Mars formed under mildly acidic conditions, which would inhibit the extensive formation of carbonate deposits. The goal of this work is to evaluate the formation of Fe/Mg smectites under mildly acidic conditions. The stability of smectites under mildly acidic conditions is attributed to elevated Fe/Mg activities that inhibit smectite dissolution. Beidelite and saponite have been shown to form from hydrothermal alteration of basaltic glass at pH 3.5-4.0 in seawater solutions. Nontronite is also known to be stable in mildly acidic systems associated with mafic and ultramafic rock. Nontronite was shown to form in acid sulfate soils in the Bangkok Plain, Thailand due to oxidation of Fe-sulfides that transformed saponite to nontronite. Smectite is known to transform to kaolinite in naturally acid soils due to selective leaching of Mg. However, if Mg removal is limited, then based on equilibrium relationships, the dissolution of smectite should be minimized. If Fe and Mg solution activities are sufficiently high, such as might be found in a low water/rock ratio system that is poorly drained, smectite could form and remain stable under mildly acidic conditions on Mars. The sources of mild acidity on early Mars includes elevated atmospheric CO2 levels, Fe-hydrolysis reactions, and the presence of volcanic SO2 aerosols. Equilibrium calculations dictate that water equilibrated with an early Mars CO2 atmosphere at 1 to 4 bar yields a pH of 3.6 to 3

  11. Molecular understanding of atmospheric particle formation from sulfuric acid and large oxidized organic molecules

    PubMed Central

    Schobesberger, Siegfried; Junninen, Heikki; Bianchi, Federico; Lönn, Gustaf; Ehn, Mikael; Lehtipalo, Katrianne; Dommen, Josef; Ehrhart, Sebastian; Ortega, Ismael K.; Franchin, Alessandro; Nieminen, Tuomo; Riccobono, Francesco; Hutterli, Manuel; Duplissy, Jonathan; Almeida, João; Amorim, Antonio; Breitenlechner, Martin; Downard, Andrew J.; Dunne, Eimear M.; Flagan, Richard C.; Kajos, Maija; Keskinen, Helmi; Kirkby, Jasper; Kupc, Agnieszka; Kürten, Andreas; Kurtén, Theo; Laaksonen, Ari; Mathot, Serge; Onnela, Antti; Praplan, Arnaud P.; Rondo, Linda; Santos, Filipe D.; Schallhart, Simon; Schnitzhofer, Ralf; Sipilä, Mikko; Tomé, António; Tsagkogeorgas, Georgios; Vehkamäki, Hanna; Wimmer, Daniela; Baltensperger, Urs; Carslaw, Kenneth S.; Curtius, Joachim; Hansel, Armin; Petäjä, Tuukka; Kulmala, Markku; Donahue, Neil M.; Worsnop, Douglas R.

    2013-01-01

    Atmospheric aerosols formed by nucleation of vapors affect radiative forcing and therefore climate. However, the underlying mechanisms of nucleation remain unclear, particularly the involvement of organic compounds. Here, we present high-resolution mass spectra of ion clusters observed during new particle formation experiments performed at the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research. The experiments involved sulfuric acid vapor and different stabilizing species, including ammonia and dimethylamine, as well as oxidation products of pinanediol, a surrogate for organic vapors formed from monoterpenes. A striking resemblance is revealed between the mass spectra from the chamber experiments with oxidized organics and ambient data obtained during new particle formation events at the Hyytiälä boreal forest research station. We observe that large oxidized organic compounds, arising from the oxidation of monoterpenes, cluster directly with single sulfuric acid molecules and then form growing clusters of one to three sulfuric acid molecules plus one to four oxidized organics. Most of these organic compounds retain 10 carbon atoms, and some of them are remarkably highly oxidized (oxygen-to-carbon ratios up to 1.2). The average degree of oxygenation of the organic compounds decreases while the clusters are growing. Our measurements therefore connect oxidized organics directly, and in detail, with the very first steps of new particle formation and their growth between 1 and 2 nm in a controlled environment. Thus, they confirm that oxidized organics are involved in both the formation and growth of particles under ambient conditions. PMID:24101502

  12. Molecular understanding of atmospheric particle formation from sulfuric acid and large oxidized organic molecules.

    PubMed

    Schobesberger, Siegfried; Junninen, Heikki; Bianchi, Federico; Lönn, Gustaf; Ehn, Mikael; Lehtipalo, Katrianne; Dommen, Josef; Ehrhart, Sebastian; Ortega, Ismael K; Franchin, Alessandro; Nieminen, Tuomo; Riccobono, Francesco; Hutterli, Manuel; Duplissy, Jonathan; Almeida, João; Amorim, Antonio; Breitenlechner, Martin; Downard, Andrew J; Dunne, Eimear M; Flagan, Richard C; Kajos, Maija; Keskinen, Helmi; Kirkby, Jasper; Kupc, Agnieszka; Kürten, Andreas; Kurtén, Theo; Laaksonen, Ari; Mathot, Serge; Onnela, Antti; Praplan, Arnaud P; Rondo, Linda; Santos, Filipe D; Schallhart, Simon; Schnitzhofer, Ralf; Sipilä, Mikko; Tomé, António; Tsagkogeorgas, Georgios; Vehkamäki, Hanna; Wimmer, Daniela; Baltensperger, Urs; Carslaw, Kenneth S; Curtius, Joachim; Hansel, Armin; Petäjä, Tuukka; Kulmala, Markku; Donahue, Neil M; Worsnop, Douglas R

    2013-10-22

    Atmospheric aerosols formed by nucleation of vapors affect radiative forcing and therefore climate. However, the underlying mechanisms of nucleation remain unclear, particularly the involvement of organic compounds. Here, we present high-resolution mass spectra of ion clusters observed during new particle formation experiments performed at the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research. The experiments involved sulfuric acid vapor and different stabilizing species, including ammonia and dimethylamine, as well as oxidation products of pinanediol, a surrogate for organic vapors formed from monoterpenes. A striking resemblance is revealed between the mass spectra from the chamber experiments with oxidized organics and ambient data obtained during new particle formation events at the Hyytiälä boreal forest research station. We observe that large oxidized organic compounds, arising from the oxidation of monoterpenes, cluster directly with single sulfuric acid molecules and then form growing clusters of one to three sulfuric acid molecules plus one to four oxidized organics. Most of these organic compounds retain 10 carbon atoms, and some of them are remarkably highly oxidized (oxygen-to-carbon ratios up to 1.2). The average degree of oxygenation of the organic compounds decreases while the clusters are growing. Our measurements therefore connect oxidized organics directly, and in detail, with the very first steps of new particle formation and their growth between 1 and 2 nm in a controlled environment. Thus, they confirm that oxidized organics are involved in both the formation and growth of particles under ambient conditions.

  13. The effects of lactic acid bacteria inoculants and formic acid on the formation of biogenic amines in grass silages.

    PubMed

    Steidlová, S; Kalac, P

    2004-06-01

    Silages were prepared in six laboratory experiments from four direct-cut grassland swards and pure swards of perennial ryegrass and false oat with dry matter contents ranging between 180 and 325 g/kg. Grass was fermented at 22 degrees C and silages were stored at the same temperature for 4 months. Untreated silages (negative control) and silages preserved with 3 g/kg of formic acid (positive control) were compared with silages inoculated with commercial strains of Lactobacillus plantarum, Lactobacillus buchneri and a mixed preparation Microsil. The inoculants were applied at a dose of 5.10(6) CFU/g of grass. Seven biogenic amines were extracted from silages with perchloric acid and determined as N-benzamides by micellar electrokinetic capillary chromatography. Common chemical quality parameters of silages were also determined. Tyramine, cadaverine and putrescine were the amines occurring at the highest concentration. As compared to untreated silages, formic acid was most effective to suppress formation of the main amines. Also the inoculants often decreased amine contents significantly (P < 0.05). The inoculants decreased levels of polyamine spermidine more efficiently than formic acid. Contents of histamine, tryptamine and polyamine spermine were very low, commonly below the detection limits.

  14. Formation and accumulation of alpha-acids, beta-acids, desmethylxanthohumol, and xanthohumol during flowering of hops (Humulus lupulus L.).

    PubMed

    De Keukeleire, Jelle; Ooms, Geert; Heyerick, Arne; Roldan-Ruiz, Isabel; Van Bockstaele, Erik; De Keukeleire, Denis

    2003-07-16

    Important secondary metabolites, present in hops (Humulus lupulus L.), include alpha-acids and beta-acids, which are essential for the brewing of beer, as well as the prenylated chalcones, desmethylxanthohumol, and xanthohumol, which exhibit interesting bioactive properties. Their formation and accumulation in five selected hop varieties, Wye Challenger, Wye Target, Golding, Admiral, and Whitbread Golding Variety, were quantitatively monitored by high-performance liquid chromatography using UV detection. All target compounds were present from the onset of flowering, not only in female hop cones but also in male inflorescences, albeit in low concentrations. During development from female inflorescences to cones, levels of alpha-acids, beta-acids, desmethylxanthohumol, and xanthohumol gradually increased, while each hop variety exhibited individual accumulation rates. Furthermore, these compounds were present in leaves of fully grown hops as well. The study demonstrated that key compounds for flavor and potential beneficial health effects associated with beer not only reside in the glandular lupulin structures but also are distributed over various parts of the hop plant.

  15. Inhibition of acid formation by epidermal growth factor in the isolated rabbit gastric glands.

    PubMed Central

    Dembiński, A; Drozdowicz, D; Gregory, H; Konturek, S J; Warzecha, Z

    1986-01-01

    The effects of epidermal growth factor (EGF) on basal and stimulated (with histamine, dibutyryl cyclic AMP, and high concentrations of K+) acid formation have been studied in isolated glands from the rabbit gastric mucosa. The changes in the accumulation of [14C]aminopyrine [14C]AP have been used as an indirect measurement of acid production in the glands. Unstimulated gastric glands accumulated [14C]AP indicating the existence of basal acid production in these glands, and EGF caused a small but significant reduction in basal [14C]AP uptake. A similar reduction of basal [14C]AP uptake was observed after exposure to omeprazole but not after ranitidine or prostaglandin E2 (PGE2). Histamine, dibutyryl cyclic AMP and K+ caused a strong and dose-dependent stimulation of acid formation by the glands. EGF, like omeprazole, reduced dose-dependently the [14C]AP accumulation stimulated by both histamine and dibutyryl cyclic AMP, while ranitidine and PGE2 reduced histamine- but not dibutyryl-cyclic-AMP-stimulated accumulation of [14C]AP. In the absence of other external stimuli, an increased K+ concentration enhanced [14C]AP accumulation to levels similar to those produced by histamine and this effect was not changed by EGF, ranitidine or PGE2 but was inhibited by omeprazole. We conclude that EGF interferes with the final steps of acid production between cyclic nucleotides and proton pump of the parietal cells. PMID:3025433

  16. Nucleobase and amino acid formation through impacts of meteorites on the early ocean

    NASA Astrophysics Data System (ADS)

    Furukawa, Yoshihiro; Nakazawa, Hiromoto; Sekine, Toshimori; Kobayashi, Takamichi; Kakegawa, Takeshi

    2015-11-01

    The emergence of life's building blocks on the prebiotic Earth was the first crucial step for the origins of life. Extraterrestrial delivery of intact amino acids and nucleobases is the prevailing hypothesis for their availability on prebiotic Earth because of the difficulties associated with the production of these organics from terrestrial carbon and nitrogen sources under plausible prebiotic conditions. However, the variety and amounts of these intact organics delivered by meteorites would have been limited. Previous shock-recovery experiments have demonstrated that meteorite impact reactions could have generated organics on the prebiotic Earth. Here, we report on the simultaneous formation of nucleobases (cytosine and uracil) found in DNA and/or RNA, various proteinogenic amino acids (glycine, alanine, serine, aspartic acid, glutamic acid, valine, leucine, isoleucine, and proline), non-proteinogenic amino acids, and aliphatic amines in experiments simulating reactions induced by extraterrestrial objects impacting on the early oceans. To the best of our knowledge, this is the first report of the formation of nucleobases from inorganic materials by shock conditions. In these experiments, bicarbonate was used as the carbon source. Bicarbonate, which is a common dissolved carbon species in CO2-rich atmospheric conditions, was presumably the most abundant carbon species in the early oceans and in post-impact plumes. Thus, the present results expand the possibility that impact-induced reactions generated various building blocks for life on prebiotic Earth in large quantities through the use of terrestrial carbon reservoirs.

  17. Laboratory photochemical processing of aqueous aerosols: formation and degradation of dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls

    NASA Astrophysics Data System (ADS)

    Pavuluri, C. M.; Kawamura, K.; Mihalopoulos, N.; Swaminathan, T.

    2015-01-01

    To better understand the photochemical processing of dicarboxylic acids and related polar compounds, we conducted batch UV irradiation experiments on two types of aerosol samples collected from India, which represent anthropogenic (AA) and biogenic aerosols (BA), for time periods of 0.5 to 120 h. The irradiated samples were analyzed for molecular compositions of diacids, oxoacids and α-dicarbonyls. The results show that photochemical degradation of oxalic (C2) and malonic (C3) and other C8-C12 diacids overwhelmed their production in aqueous aerosols whereas succinic acid (C4) and C5-C7 diacids showed a significant increase (ca. 10 times) during the course of irradiation experiments. The photochemical formation of oxoacids and α-dicarbonyls overwhelmed their degradation during the early stages of experiment, except for ω-oxooctanoic acid (ωC8) that showed a similar pattern to that of C4. We also found a gradual decrease in the relative abundance of C2 to total diacids and an increase in the relative abundance of C4 during prolonged experiment. Based on the changes in concentrations and mass ratios of selected species with the irradiation time, we hypothesize that iron-catalyzed photolysis of C2 and C3 diacids dominates their concentrations in Fe-rich atmospheric waters, whereas photochemical formation of C4 diacid (via ωC8) is enhanced with photochemical processing of aqueous aerosols in the atmosphere. This study demonstrates that the ambient aerosols contain abundant precursors that produce diacids, oxoacids and α-dicarbonyls, although some species such as oxalic acid decompose extensively during an early stage of photochemical processing.

  18. Laboratory photochemical processing of aqueous aerosols: formation and degradation of dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls

    NASA Astrophysics Data System (ADS)

    Pavuluri, C. M.; Kawamura, K.; Mihalopoulos, N.; Swaminathan, T.

    2015-07-01

    To better understand the photochemical processing of dicarboxylic acids and related polar compounds, we conducted batch UV irradiation experiments on two types of aerosol samples collected from India, which represent anthropogenic (AA) and biogenic (BA) aerosols, for time periods of 0.5 to 120 h. The irradiated samples were analyzed for molecular compositions of diacids, oxoacids and α-dicarbonyls. The results show that photochemical degradation of oxalic (C2), malonic (C3) and other C8-C12 diacids overwhelmed their production in aqueous aerosols, whereas succinic acid (C4) and C5-C7 diacids showed a significant increase (ca. 10 times) during the course of irradiation experiments. The photochemical formation of oxoacids and α-dicarbonyls overwhelmed their degradation during the early stages of experiment except for ω-oxooctanoic acid (ωC8), which showed a similar pattern to that of C4. We also found a gradual decrease in the relative abundance of C2 to total diacids and an increase in the relative abundance of C4 during prolonged experiment. Based on the changes in concentrations and mass ratios of selected species with the irradiation time, we hypothesize that iron-catalyzed photolysis of C2 and C3 diacids controls their concentrations in Fe-rich atmospheric waters, whereas photochemical formation of C4 diacid (via ωC8) is enhanced with photochemical processing of aqueous aerosols in the atmosphere. This study demonstrates that the ambient aerosols contain abundant precursors that produce diacids, oxoacids and α-dicarbonyls, although some species such as oxalic acid decompose extensively during an early stage of photochemical processing.

  19. Five Decades with Polyunsaturated Fatty Acids: Chemical Synthesis, Enzymatic Formation, Lipid Peroxidation and Its Biological Effects

    PubMed Central

    Catalá, Angel

    2013-01-01

    I have been involved in research on polyunsaturated fatty acids since 1964 and this review is intended to cover some of the most important aspects of this work. Polyunsaturated fatty acids have followed me during my whole scientific career and I have published a number of studies concerned with different aspects of them such as chemical synthesis, enzymatic formation, metabolism, transport, physical, chemical, and catalytic properties of a reconstructed desaturase system in liposomes, lipid peroxidation, and their effects. The first project I became involved in was the organic synthesis of [1-14C] eicosa-11,14-dienoic acid, with the aim of demonstrating the participation of that compound as a possible intermediary in the biosynthesis of arachidonic acid “in vivo.” From 1966 to 1982, I was involved in several projects that study the metabolism of polyunsaturated fatty acids. In the eighties, we studied fatty acid binding protein. From 1990 up to now, our laboratory has been interested in the lipid peroxidation of biological membranes from various tissues and different species as well as liposomes prepared with phospholipids rich in PUFAs. We tested the effect of many antioxidants such as alpha tocopherol, vitamin A, melatonin and its structural analogues, and conjugated linoleic acid, among others. PMID:24490074

  20. Sulfate Mineral Formation from Acid-weathered Phyllosilicates: Implications for the Aqueous History of Mars

    NASA Astrophysics Data System (ADS)

    Craig, Patricia; Ming, Douglas; Rampe, Elizabeth

    2014-11-01

    Phyllosilicates on Mars are common in Noachian terrains whereas sulfates are found in the younger Hesperian terrains and suggest alteration under more acidic conditions. Phyllosilicates that formed during the Noachian era would have been exposed to the prevailing acidic conditions during the Hesperian. The purpose of this project is to characterize the effects of acid-weathering on phyllosilicates to better understand the aqueous history of Mars. Nontronite, montmorillonite, and saponite were exposed to H2SO4 solutions at water-rock (WR) ratios of 50 and 25.X-ray diffraction (XRD) patterns of all three acid-treated minerals showed progressive collapse of the phyllosilicate basal spacing with increasing acid concentration. Bassanite formed as an intermediate phase in weathered nontronite and montmorillonite from extracted interlayer Ca. The octahedral cation determined which sulfate formed at high acid concentration: rhomboclase from nontronite, alunogen from montmorillonite, hexahydrite and kieserite from saponite. Gypsum and anhydrite also formed as intermediate phases in nontronite treated at WR=25, showing a change in sulfate hydration state with changing acid concentration (i.e. water activity). Scanning electron microscopy analyses detected phases not identified by XRD. Al-sulfate was found in nontronite weathered at WR=25 and Ca-sulfate in weathered saponite. Near-infrared reflectance spectra of the weathered samples showed decreasing intensity of the hydration/hydroxylation bands and a change or disappearance of metal-OH bands indicating dehydration and dissociation of the interlayers and octahedral layers, respectively, with increased acid weathering.Sulfate mineral formation from acid-weathered phyllosilicates may explain the presence of phyllosilicates and sulfates in close proximity to each other on Mars, such as in Gale Crater. The CheMin XRD instrument on Curiosity may find evidence for acid-weathered phyllosilicates in Mt. Sharp by comparing the 001

  1. Butyric acid released during milk lipolysis triggers biofilm formation of Bacillus species.

    PubMed

    Pasvolsky, Ronit; Zakin, Varda; Ostrova, Ievgeniia; Shemesh, Moshe

    2014-07-02

    Bacillus species form biofilms within milking pipelines and on surfaces of equipment in the dairy industry which represent a continuous hygiene problem and can lead to serious economic losses due to food spoilage and equipment impairment. Although much is known about the mechanism by which the model organism Bacillus subtilis forms biofilms in laboratory mediums in vitro, little is known of how these biofilms are formed in natural environments such as milk. Besides, little is known of the signaling pathways leading to biofilm formation in other Bacillus species, such as Bacillus cereus and Bacillus licheniformis, both of which are known to contaminate milk. In this study, we report that milk triggers the formation of biofilm-related structures, termed bundles. We show this to be a conserved phenomenon among all Bacillus members tested. Moreover, we demonstrate that the tasA gene, which encodes a major portion of the matrix which holds the biofilm together, is vital for this process. Furthermore, we show that the free fatty acid (FFA) - butyric acid (BA), which is released during lipolysis of milk fat and demonstrates antimicrobial activity, is the potent trigger for biofilm bundle formation. We finally show that BA-triggered biofilm bundle formation is mediated by the histidine kinase, KinD. Taken together, these observations indicate that BA, which is a major FFA within milk triggers biofilm formation in a conserved mechanism among members of the Bacillus genus.

  2. Structure-based design of non-natural amino-acid inhibitors of amyloid fibril formation

    SciTech Connect

    Sievers, Stuart A.; Karanicolas, John; Chang, Howard W.; Zhao, Anni; Jiang, Lin; Zirafi, Onofrio; Stevens, Jason T.; Münch, Jan; Baker, David; Eisenberg, David

    2011-09-20

    Many globular and natively disordered proteins can convert into amyloid fibrils. These fibrils are associated with numerous pathologies as well as with normal cellular functions, and frequently form during protein denaturation. Inhibitors of pathological amyloid fibril formation could be useful in the development of therapeutics, provided that the inhibitors were specific enough to avoid interfering with normal processes. Here we show that computer-aided, structure-based design can yield highly specific peptide inhibitors of amyloid formation. Using known atomic structures of segments of amyloid fibrils as templates, we have designed and characterized an all-D-amino-acid inhibitor of the fibril formation of the tau protein associated with Alzheimer's disease, and a non-natural L-amino-acid inhibitor of an amyloid fibril that enhances sexual transmission of human immunodeficiency virus. Our results indicate that peptides from structure-based designs can disrupt the fibril formation of full-length proteins, including those, such as tau protein, that lack fully ordered native structures. Because the inhibiting peptides have been designed on structures of dual-{beta}-sheet 'steric zippers', the successful inhibition of amyloid fibril formation strengthens the hypothesis that amyloid spines contain steric zippers.

  3. Hydroxyl radical formation upon oxidation of reduced humic acids by oxygen in the dark.

    PubMed

    Page, Sarah E; Sander, Michael; Arnold, William A; McNeill, Kristopher

    2012-02-07

    Humic acids (HAs) accept and donate electrons in many biogeochemical redox reactions at oxic/anoxic interfaces. The products of oxidation of reduced HAs by O(2) are unknown but are expected to yield reactive oxygen species, potentially including hydroxyl radical (·OH). To quantify the formation of ·OH upon oxidation of reduced HAs by O(2), three HAs were reduced electrochemically to well-defined redox states and were subsequently oxidized by O(2) in the presence of the ·OH probe terephthalate. The formation of ·OH upon oxidation increased with increasing extent of HA reduction. The yield of ·OH ranged from 42 to 160 mmol per mole of electrons donated by the reduced HA. The intermediacy of hydrogen peroxide (H(2)O(2)) in the formation of ·OH was supported by enhancement of ·OH formation upon addition of exogenous H(2)O(2) sources and by the suppression of ·OH formation upon addition of catalase as a quencher of endogenous H(2)O(2). The formation of ·OH in the dark during oxidation of reduced HA represents a previously unknown source of ·OH formation at oxic/anoxic interfaces and may affect the biogeochemical and pollutant redox dynamics at these interfaces.

  4. Pretreatment of solid carbonaceous material with dicarboxylic aromatic acids to prevent scale formation

    SciTech Connect

    Brunson, R.J.

    1982-06-01

    Scale formation during the liquefaction of lower ranking coals and similar carbonaceous materials is significantly reduced and/or prevented by pretreatment with a pretreating agent selected from the group consisting of phthalic acid, phthalic anhydride, pyromellitic acid and pyromellitic anhydride. The pretreatment is believed to convert the scale-forming components to the corresponding phthalate and/or pyromellitate prior to liquefaction. The pretreatment is accomplished at a total pressure within the range from about 1 to about 2 atmospheres. Temperature during pretreatment will generally be within the range from about 5 to about 80/sup 0/ C.

  5. Pretreatment of solid carbonaceous material with dicarboxylic aromatic acids to prevent scale formation

    SciTech Connect

    Brunson, Roy J.

    1982-01-01

    Scale formation during the liquefaction of lower ranking coals and similar carbonaceous materials is significantly reduced and/or prevented by pretreatment with a pretreating agent selected from the group consisting of phthalic acid, phthalic anhydride, pyromellitic acid and pyromellitic anhydride. The pretreatment is believed to convert the scale-forming components to the corresponding phthalate and/or pyromellitate prior to liquefaction. The pretreatment is accomplished at a total pressure within the range from about 1 to about 2 atmospheres. Temperature during pretreatment will generally be within the range from about 5.degree. to about 80.degree. C.

  6. Radiation- and photo-induced formation of salicylic acid from phenol and CO{sub 2} in aqueous solution

    SciTech Connect

    Krapfenbauer, K.; Getoff, N.

    1996-12-31

    The concentration of CO{sub 2} in the atmosphere is steady increasing because of the combustion of fossil fuels and the industrial pollution. As a result, global warming has occurred. In the present study the formation of the salicylic acid and other products, originating from the carboxylation of phenol is investigated. It has been found that the formation of salicylic acid strongly depend on several experimental conditions: pH of the solution, concentration of phenol and CO{sub 2}, and absorbed dose. The formation of salicylic acid was also studied in the presence of catalysts. Photo-induced carboxylation of phenol to salicylic acid will be also reported. Probable reaction mechanisms for the salicylic acid formation are suggested. Finally, a comparison is made between the well known industrial Kolbe-Schmitt process for salicylic acid production and the aspects of the present new method for CO{sub 2} utilization.

  7. A mammalian fatty acid hydroxylase responsible for the formation of α-hydroxylated galactosylceramide in myelin

    PubMed Central

    Eckhardt, Matthias; Yaghootfam, Afshin; Fewou, Simon N.; Zöller, Inge; Gieselmann, Volkmar

    2005-01-01

    Hydroxylation is an abundant modification of the ceramides in brain, skin, intestinal tract and kidney. Hydroxylation occurs at the sphingosine base at C-4 or within the amide-linked fatty acid. In myelin, hydroxylation of ceramide is exclusively found at the α-C atom of the fatty acid moiety. α-Hydroxylated cerebrosides are the most abundant lipids in the myelin sheath. The functional role of this modification, however, is not known. On the basis of sequence similarity to a yeast C26 fatty acid hydroxylase, we have identified a murine cDNA encoding FA2H (fatty acid 2-hydroxylase). Transfection of FA2H cDNA in CHO cells (Chinese-hamster ovary cells) led to the formation of α-hydroxylated fatty acid containing hexosylceramide. An EGFP (enhanced green fluorescent protein)–FA2H fusion protein co-localized with calnexin, indicating that the enzyme resides in the endoplasmic reticulum. FA2H is expressed in brain, stomach, skin, kidney and testis, i.e. in tissues known to synthesize fatty acid α-hydroxylated sphingolipids. The time course of its expression in brain closely follows the expression of myelin-specific genes, reaching a maximum at 2–3 weeks of age. This is in agreement with the reported time course of fatty acid α-hydroxylase activity in the developing brain. In situ hybridization of brain sections showed expression of FA2H in the white matter. Our results thus strongly suggest that FA2H is the enzyme responsible for the formation of α-hydroxylated ceramide in oligodendrocytes of the mammalian brain. Its further characterization will provide insight into the functional role of α-hydroxylation modification in myelin, skin and other organs. PMID:15658937

  8. Physicochemical consequences of amino acid variations that contribute to fibril formation by immunoglobulin light chains.

    PubMed Central

    Raffen, R.; Dieckman, L. J.; Szpunar, M.; Wunschl, C.; Pokkuluri, P. R.; Dave, P.; Wilkins Stevens, P.; Cai, X.; Schiffer, M.; Stevens, F. J.

    1999-01-01

    The most common form of systemic amyloidosis originates from antibody light chains. The large number of amino acid variations that distinguish amyloidogenic from nonamyloidogenic light chain proteins has impeded our understanding of the structural basis of light-chain fibril formation. Moreover, even among the subset of human light chains that are amyloidogenic, many primary structure differences are found. We compared the thermodynamic stabilities of two recombinant kappa4 light-chain variable domains (V(L)s) derived from amyloidogenic light chains with a V(L) from a benign light chain. The amyloidogenic V(L)s were significantly less stable than the benign V(L). Furthermore, only the amyloidogenic V(L)s formed fibrils under native conditions in an in vitro fibril formation assay. We used site-directed mutagenesis to examine the consequences of individual amino acid substitutions found in the amyloidogenic V(L)s on stability and fibril formation capability. Both stabilizing and destabilizing mutations were found; however, only destabilizing mutations induced fibril formation in vitro. We found that fibril formation by the benign V(L) could be induced by low concentrations of a denaturant. This indicates that there are no structural or sequence-specific features of the benign V(L) that are incompatible with fibril formation, other than its greater stability. These studies demonstrate that the V(L) beta-domain structure is vulnerable to destabilizing mutations at a number of sites, including complementarity determining regions (CDRs), and that loss of variable domain stability is a major driving force in fibril formation. PMID:10091653

  9. UV – INDUCED SYNTHESIS OF AMINO ACIDS FROM AQUEOUS STERILIZED SOLUTION OF AMMONIUM FORMATE AND AMMONIA UNDER HETROGENEOUS CONDITIONS

    PubMed Central

    Bisht, G.; Bisht, L. S.

    1990-01-01

    Irradiation of sterilized aqueous solution of ammonium formate and ammonia with UV light in the presence and or absence of certain inorganic sensitizers for 25 hrs. gave six ninhydrin positive products in appreciable amounts. Out of the six products observed fiver were characterized as lysine, serine, glutemic acid, n-amino butyric acid and leucine. The sensitizing effect of additives on ammonium formate was observed in the order; uranium oxide > ammonium formate > ferric oxide > arsenic oxide. PMID:22556511

  10. Formation mechanism of a new carbamazepine/malonic acid cocrystal polymorph.

    PubMed

    Limwikrant, Waree; Nagai, Aiko; Hagiwara, Yumi; Higashi, Kenjirou; Yamamoto, Keiji; Moribe, Kunikazu

    2012-07-15

    A new 2/1 carbamazepine (CBZ)/malonic acid (MA) cocrystal polymorph form C was formed using a vibrational rod mill, whereas the known cocrystal polymorph form A was prepared using a ball mill. IR measurements showed that the interaction between CBZ and MA in cocrystal form C was formed by amide-carboxylic acid heterosynthons, similar to that in cocrystal form A. However, NMR results showed that the molecular states of CBZ at the dibenzazepine ring appeared to be different, which could be due to variation in either the conjugation of the aromatic rings or the π-π interaction of CBZ. Factors affecting the formation of cocrystal polymorphs, such as heat and force, were investigated to clarify the formation mechanism.

  11. Formation of a seed germination promoter from carbohydrates and amino acids.

    PubMed

    Light, Marnie E; Burger, Barend V; van Staden, Johannes

    2005-07-27

    The ability of plant-derived smoke to act as a germination cue in many species has led to widespread interest in this aspect of seed biology. Recently, 3-methyl-2H-furo[2,3-c]pyran-2-one was identified as the main germination cue from smoke. Here, we report on the formation of this compound from reactions of sugars with amino acids. Heating proteins or amino acids with sugars at 180 degrees C for 30 min produces water soluble extracts that promote germination. High-performance liquid chromatography indicated that the active compound(s) derived from these reactions coeluted with the active fraction from a smoke solution. Gas chromatography-mass spectroscopy showed that the active constituent is identical to the germination cue from plant-derived smoke. The results presented in this paper provide evidence for the formation of the major germination cue found in smoke from ubiquitously occurring organic compounds.

  12. Hydroxyapatite formation on graphene oxide modified with amino acids: arginine versus glutamic acid.

    PubMed

    Tavafoghi, M; Brodusch, N; Gauvin, R; Cerruti, M

    2016-01-01

    Hydroxyapatite (HA, Ca5(PO4)3OH) is the main inorganic component of hard tissues, such as bone and dentine. HA nucleation involves a set of negatively charged phosphorylated proteins known as non-collagenous proteins (NCPs). These proteins attract Ca(2+) and PO4(3-) ions and increase the local supersaturation to a level required for HA precipitation. Polar and charged amino acids (AAs) are highly expressed in NCPs, and seem to be responsible for the mineralizing effect of NCPs; however, the individual effect of these AAs on HA mineralization is still unclear. In this work, we investigate the effect of a negatively charged (Glu) and positively charged (Arg) AA bound to carboxylated graphene oxide (CGO) on HA mineralization in simulated body fluids (SBF). Our results show that Arg induces HA precipitation faster and in larger amounts than Glu. We attribute this to the higher stability of the complexes formed between Arg and Ca(2+) and PO4(3-) ions, and also to the fact that Arg exposes both carboxyl and amino groups on the surface. These can electrostatically attract both Ca(2+) and PO4(3-) ions, thus increasing local supersaturation more than Glu, which exposes carboxyl groups only.

  13. Hydroxyapatite formation on graphene oxide modified with amino acids: arginine versus glutamic acid

    PubMed Central

    Tavafoghi, M.; Brodusch, N.; Gauvin, R.; Cerruti, M.

    2016-01-01

    Hydroxyapatite (HA, Ca5(PO4)3OH) is the main inorganic component of hard tissues, such as bone and dentine. HA nucleation involves a set of negatively charged phosphorylated proteins known as non-collagenous proteins (NCPs). These proteins attract Ca2+ and PO43− ions and increase the local supersaturation to a level required for HA precipitation. Polar and charged amino acids (AAs) are highly expressed in NCPs, and seem to be responsible for the mineralizing effect of NCPs; however, the individual effect of these AAs on HA mineralization is still unclear. In this work, we investigate the effect of a negatively charged (Glu) and positively charged (Arg) AA bound to carboxylated graphene oxide (CGO) on HA mineralization in simulated body fluids (SBF). Our results show that Arg induces HA precipitation faster and in larger amounts than Glu. We attribute this to the higher stability of the complexes formed between Arg and Ca2+ and PO43− ions, and also to the fact that Arg exposes both carboxyl and amino groups on the surface. These can electrostatically attract both Ca2+ and PO43− ions, thus increasing local supersaturation more than Glu, which exposes carboxyl groups only. PMID:26791001

  14. Evidence in the formation of conjugated linoleic acids from thermally induced 9t12t linoleic acid: a study by gas chromatography and infrared spectroscopy.

    PubMed

    Christy, Alfred A

    2009-10-01

    Thermally induced isomerisation leading to the formation of conjugated linoleic acids (CLAs) has been observed for the first time during the thermal treatment of 9t12t fatty acid triacylglycerol, and methyl ester. Fifteen microlitre portions of the triacylglycerol sample containing 9t12t fatty acid (trilinoelaidin) were placed in micro glass ampoules and sealed under nitrogen, then subjected to thermal treatment at 250 degrees C. The glass ampoules were removed at regular time intervals, cut open, and the contents were analysed by infrared spectroscopy using a single reflectance attenuated total internal reflectance crystal accessory. The samples were then subjected to derivatisation into their methyl esters. The methyl esters of the isomerised fatty acids were analysed by gas chromatography. The same procedure was repeated with methyl ester samples containing 9t12t fatty acid (methyl linoelaidate). Each sample was subjected to infrared measurements and gas chromatographic analysis after appropriate dilution in heptane. The results show that the thermally induced isomerisation of 9t12t fatty acids from both triacylglycerol molecules and methyl esters give identical CLA profiles as those found for the thermally induced isomerisation of 9c12c fatty acids. The infrared spectrometry provides additional evidence confirming the formation of CLA acids during thermal treatment. A mechanism for the formation of the CLAs from 9t12t fatty acid molecules is also formulated for the first time. This mechanism complements the pathways of formation of CLAs from 9c12c fatty acids during thermal treatment.

  15. Studying Pellet Formation of a Filamentous Fungus Rhizopus oryzae to Enhance Organic Acid Production

    NASA Astrophysics Data System (ADS)

    Liao, Wei; Liu, Yan; Chen, Shulin

    Using pelletized fungal biomass can effectively improve the fermentation performance for most of fugal strains. This article studied the effects of inoculum and medium compositions such as potato dextrose broth (PDB) as carbon source, soybean peptone, calcium carbonate, and metal ions on pellet formation of Rhizopus oryzae. It has been found that metal ions had significantly negative effects on pellet formation whereas soybean peptone had positive effects. In addition PDB and calcium carbonate were beneficial to R. oryzae for growing small smooth pellets during the culture. The study also demonstrated that an inoculum size of less than 1.5×109 spores/L had no significant influence on pellet formation. Thus, a new approach to form pellets has been developed using only PDB, soybean peptone, and calcium carbonate. Meanwhile, palletized fungal fermentation significantly enhanced organic acid production. Lactic acid concentration reached 65.0 g/L in 30 h using pelletized R. oryzae NRRL 395, and fumeric acid concentration reached 31.0 g/L in 96 h using pelletized R. oryzae ATCC 20344.

  16. Impacts of Sulfate Seed Acidity and Water Content on Isoprene Secondary Organic Aerosol Formation.

    PubMed

    Wong, Jenny P S; Lee, Alex K Y; Abbatt, Jonathan P D

    2015-11-17

    The effects of particle-phase water and the acidity of pre-existing sulfate seed particles on the formation of isoprene secondary organic aerosol (SOA) was investigated. SOA was generated from the photo-oxidation of isoprene in a flow tube reactor at 70% relative humidity (RH) and room temperature in the presence of three different sulfate seeds (effloresced and deliquesced ammonium sulfate and ammonium bisulfate) under low NOx conditions. High OH exposure conditions lead to little isoprene epoxydiol (IEPOX) SOA being generated. The primary result is that particle-phase water had the largest effect on the amount of SOA formed, with 60% more SOA formation occurring with deliquesced ammonium sulfate seeds as compared to that on effloresced ones. The additional organic material was highly oxidized. Although the amount of SOA formed did not exhibit a dependence on the range of seed particle acidity examined, perhaps because of the low amount of IEPOX SOA, the levels of high-molecular-weight material increased with acidity. While the uptake of organics was partially reversible under drying, the results nevertheless indicate that particle-phase water enhanced the amount of organic aerosol material formed and that the RH cycling of sulfate particles may mediate the extent of isoprene SOA formation in the atmosphere.

  17. Microbial mediated formation of Fe-carbonate minerals under extreme acidic conditions

    PubMed Central

    Sánchez-Román, Mónica; Fernández-Remolar, David; Amils, Ricardo; Sánchez-Navas, Antonio; Schmid, Thomas; Martin-Uriz, Patxi San; Rodríguez, Nuria; McKenzie, Judith A.; Vasconcelos, Crisogono

    2014-01-01

    Discovery of Fe-carbonate precipitation in Rio Tinto, a shallow river with very acidic waters, situated in Huelva, South-western Spain, adds a new dimension to our understanding of carbonate formation. Sediment samples from this low-pH system indicate that carbonates are formed in physico-chemical conditions ranging from acid to neutral pH. Evidence for microbial mediation is observed in secondary electron images (Fig. 1), which reveal rod-shaped bacteria embedded in the surface of siderite nanocrystals. The formation of carbonates in Rio Tinto is related to the microbial reduction of ferric iron coupled to the oxidation of organic compounds. Herein, we demonstrate for the first time, that Acidiphilium sp. PM, an iron-reducing bacterium isolated from Rio Tinto, mediates the precipitation of siderite (FeCO3) under acidic conditions and at a low temperature (30°C). We describe nucleation of siderite on nanoglobules in intimate association with the bacteria cell surface. This study has major implications for understanding carbonate formation on the ancient Earth or extraterrestrial planets. PMID:24755961

  18. Microbial mediated formation of Fe-carbonate minerals under extreme acidic conditions.

    PubMed

    Sánchez-Román, Mónica; Fernández-Remolar, David; Amils, Ricardo; Sánchez-Navas, Antonio; Schmid, Thomas; San Martin-Uriz, Patxi; Rodríguez, Nuria; McKenzie, Judith A; Vasconcelos, Crisogono

    2014-04-23

    Discovery of Fe-carbonate precipitation in Rio Tinto, a shallow river with very acidic waters, situated in Huelva, South-western Spain, adds a new dimension to our understanding of carbonate formation. Sediment samples from this low-pH system indicate that carbonates are formed in physico-chemical conditions ranging from acid to neutral pH. Evidence for microbial mediation is observed in secondary electron images (Fig. 1), which reveal rod-shaped bacteria embedded in the surface of siderite nanocrystals. The formation of carbonates in Rio Tinto is related to the microbial reduction of ferric iron coupled to the oxidation of organic compounds. Herein, we demonstrate for the first time, that Acidiphilium sp. PM, an iron-reducing bacterium isolated from Rio Tinto, mediates the precipitation of siderite (FeCO3) under acidic conditions and at a low temperature (30°C). We describe nucleation of siderite on nanoglobules in intimate association with the bacteria cell surface. This study has major implications for understanding carbonate formation on the ancient Earth or extraterrestrial planets.

  19. Potential origin and formation for molecular components of humic acids in soils

    NASA Astrophysics Data System (ADS)

    DiDonato, Nicole; Chen, Hongmei; Waggoner, Derek; Hatcher, Patrick G.

    2016-04-01

    Soil humic acids are the base soluble/acid insoluble organic components of soil organic matter. Most of what we know about humic acids comes from studies of their bulk molecular properties or analysis of individual fractions after extraction from soils. This work attempts to better define humic acids and explain similarities and differences for several soils varying in degrees of humification using advanced molecular level techniques. Our investigation using electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) and nuclear magnetic resonance spectroscopy (NMR) has given new insight into the distinctive molecular characteristics of humic acids which suggest a possible pathway for their formation. Humic acids from various ecosystems, climate regions and soil textural classes are distinguished by the presence of three predominant molecular components: lignin-like molecules, carboxyl-containing aliphatic molecules and condensed aromatic molecules that bear similarity to black carbon. Results show that humification may be linked to the relative abundance of these three types of molecules as well as the relative abundance of carboxyl groups in each molecular type. This work also demonstrates evidence for lignin as the primary source of soil organic matter, particularly condensed aromatic molecules often categorized as black carbon and is the first report of the non-pyrogenic source for these compounds in soils. We also suggest that much of the carboxyl-containing aliphatic molecules are sourced from lignin.

  20. Cluster Formation of Sulfuric Acid with Dimethylamine or Diamines and Detection with Chemical Ionization

    NASA Astrophysics Data System (ADS)

    Jen, C. N.; McMurry, P. H.; Hanson, D. R.

    2015-12-01

    Chemical ionization (CI) mass spectrometers are used to study atmospheric nucleation by detecting clusters produced by reactions of sulfuric acid and various basic gases. These instruments typically use nitrate to chemically ionize clusters for detection. In this study, we compare measured cluster concentrations formed by reacting sulfuric acid vapor with dimethylamine, ethylene diamine, tetramethylethylene diamine, or butanediamine (also known as putrescine) using nitrate and acetate ions. We show from flow reactor measurements that nitrate is unable to chemically ionize clusters with weak acidities. In addition, we vary the ion-molecule reaction time to probe the chemical ionization processes and lifetimes of ions composed of sulfuric acid and base molecules. We then model the neutral and ion cluster formation pathways, including chemical ionization, ion-induced clustering, and ion decomposition, to better identify which cluster types cannot be chemically ionized by nitrate. Our results show that sulfuric acid dimer with two diamines and sulfuric acid trimer with 2 or more base molecules cannot be chemical ionized by nitrate. We conclude that cluster concentrations measured with acetate CI gives a better representation of both cluster abundancies and their base content than nitrate CI.

  1. Formation of complex precursors of amino acids by irradiation of simulated interstellar media with heavy ions

    NASA Astrophysics Data System (ADS)

    Kobayashi, K.; Suzuki, N.; Taniuchi, T.; Kaneko, T.; Yoshida, S.

    A wide variety of organic compounds have been detected in such extraterrestrial bodies as meteorites and comets Amino acids were identified in the extracts from Murchison meteorite and other carbonaceous chondrites It is hypothesized that these compounds are originally formed in ice mantles of interstellar dusts ISDs in molecular clouds by cosmic rays and ultraviolet light UV Formation of amino acid precursors by high energy protons or UV irradiation of simulated ISDs was reported by several groups The amino acid precursors were however not well-characterized We irradiated a frozen mixture of methanol ammonia and water with heavy ions to study possible organic compounds abiotically formed in molecular clouds by cosmic rays A mixture of methanol ammonia and water was irradiated with carbon beams 290 MeV u from a heavy ion accelerator HIMAC of National Institute of Radiological Sciences Japan Irradiation was performed either at room temperature liquid phase or at 77 K solid phase The products were characterized by gel filtration chromatography GFC FT-IR pyrolysis PY -GC MS etc Amino acids were analyzed by HPLC and GC MS after acid hydrolysis or the products Amino acids such as glycine and alanine were identified in the products in both the cases of liquid phase and solid phase irradiation Energy yields G-values of glycine were 0 014 liquid phase and 0 007 solid phase respectively Average molecular weights of the products were estimated as to 2300 in both the case Aromatic hydrocarbons N-containing heterocyclic

  2. Neutral molecular cluster formation of sulfuric acid-dimethylamine observed in real time under atmospheric conditions.

    PubMed

    Kürten, Andreas; Jokinen, Tuija; Simon, Mario; Sipilä, Mikko; Sarnela, Nina; Junninen, Heikki; Adamov, Alexey; Almeida, João; Amorim, Antonio; Bianchi, Federico; Breitenlechner, Martin; Dommen, Josef; Donahue, Neil M; Duplissy, Jonathan; Ehrhart, Sebastian; Flagan, Richard C; Franchin, Alessandro; Hakala, Jani; Hansel, Armin; Heinritzi, Martin; Hutterli, Manuel; Kangasluoma, Juha; Kirkby, Jasper; Laaksonen, Ari; Lehtipalo, Katrianne; Leiminger, Markus; Makhmutov, Vladimir; Mathot, Serge; Onnela, Antti; Petäjä, Tuukka; Praplan, Arnaud P; Riccobono, Francesco; Rissanen, Matti P; Rondo, Linda; Schobesberger, Siegfried; Seinfeld, John H; Steiner, Gerhard; Tomé, António; Tröstl, Jasmin; Winkler, Paul M; Williamson, Christina; Wimmer, Daniela; Ye, Penglin; Baltensperger, Urs; Carslaw, Kenneth S; Kulmala, Markku; Worsnop, Douglas R; Curtius, Joachim

    2014-10-21

    For atmospheric sulfuric acid (SA) concentrations the presence of dimethylamine (DMA) at mixing ratios of several parts per trillion by volume can explain observed boundary layer new particle formation rates. However, the concentration and molecular composition of the neutral (uncharged) clusters have not been reported so far due to the lack of suitable instrumentation. Here we report on experiments from the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research revealing the formation of neutral particles containing up to 14 SA and 16 DMA molecules, corresponding to a mobility diameter of about 2 nm, under atmospherically relevant conditions. These measurements bridge the gap between the molecular and particle perspectives of nucleation, revealing the fundamental processes involved in particle formation and growth. The neutral clusters are found to form at or close to the kinetic limit where particle formation is limited only by the collision rate of SA molecules. Even though the neutral particles are stable against evaporation from the SA dimer onward, the formation rates of particles at 1.7-nm size, which contain about 10 SA molecules, are up to 4 orders of magnitude smaller compared with those of the dimer due to coagulation and wall loss of particles before they reach 1.7 nm in diameter. This demonstrates that neither the atmospheric particle formation rate nor its dependence on SA can simply be interpreted in terms of cluster evaporation or the molecular composition of a critical nucleus.

  3. Light and acid dual-responsive organogel formation based on m-methyl red derivative.

    PubMed

    Cao, Xinhua; Gao, Aiping; Lv, Haiting; Wu, Yan; Wang, Xiuxiu; Fan, Yang

    2013-12-07

    A new gelator 1 that included m-methyl red was synthesized and fully characterized. It was found that the organogel of 1 was stable in DMSO even if the organogel was stimulated by acid or light. The organogel was thoroughly characterized using various microscopic techniques including field-emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), UV-vis and Fourier transform infrared (FTIR) spectra. The organogel exhibited tunable structures and optical properties under different stimulation. The regular nanoring structure was turned into microspheres after the organogel in DMSO was stimulated at 254 nm light or acid. At the same time, the color of molecule 1 in gel state and solution state was all changed after stimulation by light or acid. The hydrogen bonding and π-π stacking were found to be the main driving forces for gel formation. This dual-responsive gel held promise for soft materials application in upscale smart responsive materials.

  4. Highly efficient peptide formation from N-acetylaminoacyl-AMP anhydride and free amino acid

    NASA Technical Reports Server (NTRS)

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

    1983-01-01

    The kinetics of formation of the N-blocked dipeptide, N-acetylglycylglycine, from N-acetylglycyl adenylate anhydride and glycine in aqueous solution at 25 C, and at various PH's are reported. The reaction is of interest in that over a physiologically relevant pH range (6-8), peptide synthesis proceeds more rapidly than hydrolysis, even at those pH's at which this compound becomes increasingly susceptible to base-catalyzed hydrolysis. Under similar conditions, the corresponding unblocked aminoacyl adenylate anhydrides are considerably more unstable, and undergo appreciable hydrlysis in the presence of free amino acid. Because N-blocked aminoacyl adenylate anhydrides serve as model compounds of peptidyl adenylate anhydrides, these results suggest that primitive amino acid polymerization systems may have operated by cyclic reactivation of the peptidyl carboxyl group, rather than that of the incoming amino acid.

  5. The formation of calcium lactate crystals is responsible for concentrated acid whey thickening.

    PubMed

    Mimouni, A; Bouhallab, S; Famelart, M H; Naegele, D; Schuck, P

    2007-01-01

    The use of spray drying for dehydration of acid whey is generally limited by the appearance of uncontrolled thickening and solidifying of the whey mass during the lactose crystallization step. The origin of this physical change is still unknown and probably linked to complex interactions between physical properties and chemical composition of these products. To understand this phenomenon, we simulated the thickening of concentrated acid whey on a laboratory scale by measuring the flow resistance changes as a function of time and whey composition. The thickening process was characterized by an amplitude of torque and a lag time (induction time). Thickening of lactic acid whey concentrate occurred regardless of the presence of whey proteins or lactose crystals. Moreover, this work clearly demonstrated that the thickening process was due to the formation of filamentous structures corresponding to calcium lactate crystals and showed a large dependence on calcium and lactate contents, pH, and phosphate concentration.

  6. Complex formation with nucleic acids and aptamers alters the antigenic properties of platelet factor 4

    PubMed Central

    Jaax, Miriam E.; Krauel, Krystin; Marschall, Thomas; Brandt, Sven; Gansler, Julia; Fürll, Birgitt; Appel, Bettina; Fischer, Silvia; Block, Stephan; Helm, Christiane A.; Müller, Sabine; Preissner, Klaus T.

    2013-01-01

    The tight electrostatic binding of the chemokine platelet factor 4 (PF4) to polyanions induces heparin-induced thrombocytopenia, a prothrombotic adverse drug reaction caused by immunoglobulin G directed against PF4/polyanion complexes. This study demonstrates that nucleic acids, including aptamers, also bind to PF4 and enhance PF4 binding to platelets. Systematic assessment of RNA and DNA constructs, as well as 4 aptamers of different lengths and secondary structures, revealed that increasing length and double-stranded segments of nucleic acids augment complex formation with PF4, while single nucleotides or single-stranded polyA or polyC constructs do not. Aptamers were shown by circular dichroism spectroscopy to induce structural changes in PF4 that resemble those induced by heparin. Moreover, heparin-induced anti-human–PF4/heparin antibodies cross-reacted with human PF4/nucleic acid and PF4/aptamer complexes, as shown by an enzyme immunoassay and a functional platelet activation assay. Finally, administration of PF4/44mer–DNA protein C aptamer complexes in mice induced anti–PF4/aptamer antibodies, which cross-reacted with murine PF4/heparin complexes. These data indicate that the formation of anti-PF4/heparin antibodies in postoperative patients may be augmented by PF4/nucleic acid complexes. Moreover, administration of therapeutic aptamers has the potential to induce anti-PF4/polyanion antibodies and a prothrombotic diathesis. PMID:23673861

  7. Dissociative electron-ion recombination of the interstellar species protonated glycolaldehyde, acetic acid, and methyl formate.

    PubMed

    Lawson, Patrick A; Osborne, David S; Adams, Nigel G

    2012-03-22

    Recently, methyl formate, glycolaldehyde, and acetic acid have been detected in the Interstellar Medium, ISM. The rate constants, α(e), for dissociative electron-ion recombination of protonated gycolaldehyde, (HOCH(2)CHO)H(+), and protonated methyl formate, (HCOOCH(3))H(+), have been determined at 300 K in a variable temperature flowing afterglow using a Langmuir probe to obtain the electron density. The recombination rate constants at 300 K are 3.2 × 10(-7) cm(3) s(-1) for protonated methyl formate and 7.5 × 10(-7) cm(3) s(-1) for protonated glycolaldehyde. The recombination rate constant of protonated acetic acid could not be directly measured, but it appears to have a rate constant, α(e), on the 10(-7) cm(3) s(-1) scale. Several high- and low-temperature measurements for protonated methyl formate were made. In addition, an α(e) measurement at 220 K for protonated glycolaldehyde was performed. The astrochemical implications of the rates of recombination, α(e), and protonation routes are discussed.

  8. Formation of titanium phosphate composites during phosphoric acid decomposition of natural sphene

    NASA Astrophysics Data System (ADS)

    Maslova, Marina V.; Rusanova, Daniela; Naydenov, Valeri; Antzutkin, Oleg N.; Gerasimova, Lidia G.

    2008-12-01

    Decomposition of mineral sphene, CaTiOSiO 4, by H 3PO 4 is investigated in detail. During the dissolution process, simultaneous calcium leaching and formation of titanium phosphate (TiP) take place. The main product of decomposition is a solid titanium phosphate-silica composite. The XRD, solid-sate NMR, IR, TGA, SEM and BET data were used to identify and characterize the composite as a mixture of crystalline Ti(HPO 4) 2·H 2O and silica. When 80% phosphoric acid is used the decomposition degree is higher than 98% and calcium is completely transferred into the liquid phase. Formation of Ti(HPO 4) 2·H 2O proceeds via formation of meta-stable titanium phosphate phases, Ti(H 2PO 4)(PO 4)·2H 2O and Ti(H 2PO 4)(PO 4). The sorption affinities of TiP composites were examined in relation to caesium and strontium ions. A decrease of H 3PO 4 concentration leads to formation of composites with greater sorption properties. The maximum sorption capacity of TiP is observed when 60% H 3PO 4 is used in sphene decomposition. The work demonstrates a valuable option within the Ti(HPO 4) 2·H 2O-SiO 2 composite synthesis scheme, to use phosphoric acid flows for isolation of CaHPO 4·2H 2O fertilizer.

  9. Raman and terahertz spectroscopical investigation of cocrystal formation process of piracetam and 3-hydroxybenzoic acid.

    PubMed

    Du, Yong; Zhang, Huili; Xue, Jiadan; Fang, Hongxia; Zhang, Qi; Xia, Yi; Li, Yafang; Hong, Zhi

    2015-03-15

    Cocrystallization can improve physical and chemical properties of active pharmaceutical ingredient, and this feature has great potential in pharmaceutical development. In this study, the cocrystal of piracetam and 3-hydroxybenzoic acid under grinding condition has been characterized by Raman and terahertz spectroscopical techniques. The major vibrational modes of individual starting components and cocrystal are obtained and assigned. Spectral results show that the vibrational modes of the cocrystal are different from those of the corresponding parent materials. The dynamic process of such pharmaceutical cocrystal formation has also been monitored directly with Raman and THz spectra. The formation rate is pretty fast in first several 20 min grinding time, and then it becomes slow. After ∼35 min, such process has been almost completed. These results offer us the unique means and benchmark for characterizing the cocrystal conformation from molecule-level and also provide us rich information about the reaction dynamic during cocrystal formation process in pharmaceutical fields.

  10. Raman and terahertz spectroscopical investigation of cocrystal formation process of piracetam and 3-hydroxybenzoic acid

    NASA Astrophysics Data System (ADS)

    Du, Yong; Zhang, Huili; Xue, Jiadan; Fang, Hongxia; Zhang, Qi; Xia, Yi; Li, Yafang; Hong, Zhi

    2015-03-01

    Cocrystallization can improve physical and chemical properties of active pharmaceutical ingredient, and this feature has great potential in pharmaceutical development. In this study, the cocrystal of piracetam and 3-hydroxybenzoic acid under grinding condition has been characterized by Raman and terahertz spectroscopical techniques. The major vibrational modes of individual starting components and cocrystal are obtained and assigned. Spectral results show that the vibrational modes of the cocrystal are different from those of the corresponding parent materials. The dynamic process of such pharmaceutical cocrystal formation has also been monitored directly with Raman and THz spectra. The formation rate is pretty fast in first several 20 min grinding time, and then it becomes slow. After ∼35 min, such process has been almost completed. These results offer us the unique means and benchmark for characterizing the cocrystal conformation from molecule-level and also provide us rich information about the reaction dynamic during cocrystal formation process in pharmaceutical fields.

  11. Perfluorooctanoic Acid Degradation Using UV-Persulfate Process: Modeling of the Degradation and Chlorate Formation.

    PubMed

    Qian, Yajie; Guo, Xin; Zhang, Yalei; Peng, Yue; Sun, Peizhe; Huang, Ching-Hua; Niu, Junfeng; Zhou, Xuefei; Crittenden, John C

    2016-01-19

    In this study, we investigated the destruction and by-product formation of perfluorooctanoic acid (PFOA) using ultraviolet light and persulfate (UV-PS). Additionally, we developed a first-principles kinetic model to simulate both PFOA destruction and by-product and chlorate (ClO3(-)) formation in ultrapure water (UW), surface water (SW), and wastewater (WW). PFOA degradation was significantly suppressed in the presence of chloride and carbonate species and did not occur until all the chloride was converted to ClO3(-) in UW and for low DOC concentrations in SW. The model was able to simulate the PS decay, pH changes, radical concentrations, and ClO3(-) formation for UW and SW. However, our model was unable to simulate PFOA degradation well in WW, possibly from PS activation by NOM, which in turn produced sulfate radicals.

  12. Ursodeoxycholic acid protects colon cancer HCT116 cells from deoxycholic acid-induced apoptosis by inhibiting apoptosome formation.

    PubMed

    Saeki, Tohru; Yui, Satoko; Hirai, Tadashi; Fujii, Takami; Okada, Sawami; Kanamoto, Ryuhei

    2012-01-01

    We previously demonstrated that ursodeoxycholic acid (UDC) requires prolonged (≥5 h) preincubation to exhibit effective protection of colon cancer HCT116 cells from deoxycholic acid (DC)-induced apoptosis. Although UDC diminished DC-mediated caspase-9 activation, cytochrome c release from the mitochondria was not inhibited, indicating that UDC acts on the steps of caspase-9 activation. In the present study, therefore, we investigated the effects of UDC on the factors involved in caspase-9 activation. We found that UDC had no significant effect on the expression of antiapoptotic XIAP. Furthermore, UDC did not affect the expression or release of proapoptotic Smac/DIABLO, or the association of XIAP and Smac/DIABLO. In contrast, association of Apaf-1 and caspase-9 stimulated by 500 μM DC was inhibited by UDC pretreatment. Although UDC caused remarkable activation of Akt/PKB, phosphatidylinositol-3-kinase (PI3K) inhibitor did not significantly reduce UDC-mediated cytoprotection. Furthermore, phosphorylation of threonine residues on caspase-9 after UDC pretreatment could not be detected. UDC-mediated cytoprotection was independent of the MAPK pathway, and cyclic AMP (cAMP) analogue did not inhibit DC-induced apoptosis. Our results indicate that UDC protects colon cancer cells from apoptosis induced by hydrophobic bile acids, by inhibiting apoptosome formation independently of the survival signals mediated by the PI3K, MAPK, or cAMP pathways.

  13. Chemically activated formation of organic acids in reactions of the Criegee intermediate with aldehydes and ketones.

    PubMed

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

    2013-10-21

    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 C=O 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 hydroxyalkyl 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 < CH3CHO < 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.

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

    SciTech Connect

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

    2013-08-08

    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 hydroxyalkyl 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.

  15. Effect of pH on conjugated linoleic acid (CLA) formation of linolenic acid biohydrogenation by ruminal microorganisms.

    PubMed

    Lee, Yongjae

    2013-08-01

    Conventional beliefs surrounding the linolenic acid (LNA; cis-9 cis-12 cis-15 C18:3) biohydrogenation (BH) pathway propose that it converts to stearic acid (SA) without the formation of conjugated linoleic acid (CLA) as intermediate isomers. However, an advanced study (Lee and Jenkins, 2011) verified that LNA BH yields multiple CLAs. This study utilized the stable isotope tracer to investigate the BH intermediates of (13)C-LNA with different pH conditions (5.5 and 6.5). The (13)C enrichment was calculated as a (13)C/(12)C ratio of labeled minus unlabeled. After 24 h, eight CLA isomers were significantly enriched on both pH treatment, this result verifies that these CLAs originated from (13)C-LNA BH which supports the results of Lee and Jenkins (2011). The enrichment of cis-cis double bond CLAs (cis-9 cis-11 and cis-10 cis-12 CLA) were significantly higher at low pH conditions. Furthermore, the concentration of cis-10 cis-12 CLA at low pH was four times higher than at high pH conditions after a 3 h incubation. These differences support the LNA BH pathways partial switch under different pH conditions, with a strong influence on the cis-cis CLA at low pH. Several mono-, di-, and tri-enoic fatty acid isomers were enriched during 24 h of incubation, but the enrichment was decreased or restricted at low pH treatment. Based on these results, it is proposed that low pH conditions may cause a changed or limited capacity of the isomerization and reduction steps in BH.

  16. Dietary omega-3 polyunsaturated fatty acids inhibit phosphoinositide formation and chemotaxis in neutrophils.

    PubMed Central

    Sperling, R I; Benincaso, A I; Knoell, C T; Larkin, J K; Austen, K F; Robinson, D R

    1993-01-01

    Earlier studies demonstrated that dietary omega-3 polyunsaturated fatty acid (PUFA) supplementation attenuates the chemotactic response of neutrophils and the generation of leukotriene (LT) B4 by neutrophils stimulated with calcium ionophore; however, the mechanisms and relationship of these effects were not examined. Neutrophils and monocytes from eight healthy individuals were examined before and after 3 and 10 wk of dietary supplementation with 20 g SuperEPA daily, which provides 9.4 g eicosapentaenoic acid (EPA) and 5 g docosahexaenoic acid. The maximal neutrophil chemotactic response to LTB4, assessed in Boyden microchambers, decreased by 69% after 3 wk and by 93% after 10 wk from prediet values. The formation of [3H]inositol tris-phosphate (IP3) by [3H]inositol-labeled neutrophils stimulated by LTB4 decreased by 71% after 3 wk (0.033 +/- 0.013% [3H] release, mean +/- SEM) and by 90% after 10 wk (0.011 +/- 0.011%) from predict values (0.114 +/- 0.030%) as quantitated by beta-scintillation counting after resolution on HPLC. LTB4-stimulated neutrophil chemotaxis and IP3 formation correlated significantly (P < 0.0001); each response correlated closely and negatively with the EPA content of the neutrophil phosphatidylinositol (PI) pool (P = 0.0003 and P = 0.0005, respectively). Neither the affinities and densities of the high and low affinity LTB4 receptors on neutrophils nor LTB4-mediated diglyceride formation changed appreciably during the study. Similar results were observed in neutrophils activated with platelet-activating factor (PAF). The summed formation of LTB4 plus LTB5 was selectively inhibited in calcium ionophore-stimulated neutrophils and was also inhibited in zymosan-stimulated neutrophils. The inhibition of the summed formation of LTB4 plus LTB5 in calcium ionophore-stimulated neutrophils and in zymosan-stimulated neutrophils did not correlate significantly with the EPA content of the PI pool. The data indicate that dietary omega-3 PUFA

  17. Gallstone formation in guinea pigs under different dietary conditions. Effect of vitamin C on bile acid pattern.

    PubMed

    Bergman, F; Curstedt, T; Eriksson, H; van der Linden, W; Sjövall, J

    1981-04-01

    Guinea pigs formed gallstones when fed chow supplemented with cholesterol and cholic acid. Although the stones contained little or no cholesterol the changes in biliary bile acid and lipid composition were similar to those observed in other rodents under conditions of cholesterol gallstone formation. Addition of cholestyramine to chow had a midly lithogenic effect. Hypovitaminosis C in animals given cholesterol and cholic acid resulted in an increase of the cholesterol content of the gallstones. The composition of biliary bile acids was markedly changed. Reductive formation of deoxycholic acid decreased and oxidative formation of ketonic bile acid increased. The results show that vitamin C may influence the redox state of the intestinal microorganisms microorganisms responsible for these conversions.

  18. Formation and growth of molecular clusters containing sulfuric acid, water, ammonia, and dimethylamine.

    PubMed

    DePalma, Joseph W; Doren, Douglas J; Johnston, Murray V

    2014-07-24

    The structures and thermochemistry of molecular clusters containing sulfuric acid, water, ammonia, and/or dimethylamine ((CH3)2NH or DMA) are explored using a combination of Monte Carlo configuration sampling, semiempirical calculations, and density functional theory (DFT) calculations. Clusters are of the general form [(BH(+))n(HSO4(-))n(H2O)y], where B = NH3 or DMA, 2 ≤ n ≤ 8, and 0 ≤ y ≤ 10. Cluster formulas are written based on the computed structures, which uniformly show proton transfer from each sulfuric acid molecule to a base molecule while the water molecules remain un-ionized. Cluster formation is energetically favorable, owing to strong electrostatic attraction among the ions. Water has a minor effect on the energetics of cluster formation, lowering the free energy of formation by ∼ 10% depending on the cluster size and number of water molecules. Cluster growth (addition of one base molecule and one sulfuric acid molecule to a pre-existing cluster) and base substitution (substituting DMA for ammonia) are also energetically favorable processes for both anhydrous and hydrated clusters. However, the effect of water is different for different bases. Hydrated ammonium bisulfate clusters have a more favorable free energy for growth (i.e., incrementing n with fixed y) than anhydrous clusters, while the reverse is observed for dimethylammonium bisulfate clusters, where the free energy for growth is more favorable for anhydrous clusters. The substitution of DMA for ammonia in bisulfate clusters is favorable but exhibits a complex water dependence. Base substitution in smaller bisulfate clusters is enhanced by the presence of water, while base substitution in larger bisulfate clusters is less favorable for hydrated clusters than that for anhydrous clusters. While DMA substitution can stabilize small clusters containing one or a few sulfuric acid molecules, the free energy advantage of forming amine clusters relative to ammonia clusters becomes less

  19. Ketoprofen-induced formation of amino acid photoadducts: possible explanation for photocontact allergy to ketoprofen.

    PubMed

    Karlsson, Isabella; Persson, Elin; Ekebergh, Andreas; Mårtensson, Jerker; Börje, Anna

    2014-07-21

    Photocontact allergy is a well-known side effect of topical preparations of the nonsteroidal anti-inflammatory drug ketoprofen. Photocontact allergy to ketoprofen appears to induce a large number of photocross allergies to both structurally similar and structurally unrelated compounds. Contact and photocontact allergies are explained by structural modification of skin proteins by the allergen. This complex is recognized by the immune system, which initiates an immune response. We have studied ketoprofen's interaction with amino acids to better understand ketoprofen's photoallergenic ability. Irradiation of ketoprofen and amino acid analogues resulted in four different ketoprofen photodecarboxylation products (6-9) together with a fifth photoproduct (5). Dihydroquinazoline 5 was shown to be a reaction product between the indole moiety of 3-methylindole (Trp analogue) and the primary amine benzylamine (Lys analogue). In presence of air, dihydroquinazoline 5 quickly degrades into stable quinazolinone 12. The corresponding quinazolinone (17) was formed upon irradiation of ketoprofen and the amino acids N-acetyl-l-Trp ethyl ester and l-Lys ethyl ester. The formation of these models of an immunogenic complex starts with the ketoprofen-sensitized formation of singlet oxygen, which reacts with the indole moiety of Trp. The formed intermediate subsequently reacts with the primary amino functionality of Lys, or its analogue, to form a Trp-Lys adduct or a mimic thereof. The formation of a specific immunogenic complex that does not contain the allergen but that can still induce photocontact allergy would explain the large number of photocross allergies with ketoprofen. These allergens do not have to be structurally similar as long as they can generate singlet oxygen. To the best of our knowledge, there is no other suggested explanation for ketoprofen's photoallergenic properties that can account for the observed photocross allergies. The formation of a specific immunogenic

  20. New Particle Formation and Growth from Methanesulfonic Acid, Amines, Water, and Organics

    NASA Astrophysics Data System (ADS)

    Arquero, K. D.; Ezell, M. J.; Finlayson-Pitts, B. J.

    2014-12-01

    Particles in the atmosphere can influence visibility, negatively impact human health, and affect climate. The largest uncertainty in determining global radiative forcing is attributed to atmospheric aerosols. While new particle formation in many locations is correlated with sulfuric acid in air, neither the gas-phase binary nucleation of H2SO4-H2O nor the gas-phase ternary nucleation of H2SO4-NH3-H2O alone can fully explain observations. An additional potential particle source, based on previous studies in this laboratory, is methanesulfonic acid (MSA) with amines and water vapor. However, organics are ubiquitous in the atmosphere, with secondary organic aerosol (SOA) being a major component of particles. Organics could be involved in the initial stages of particle formation by enhancing or inhibiting nucleation from sulfuric acid or MSA, in addition to contributing to their growth to form SOA. Experiments to measure the effects of a series of organics of varying structure on particle formation and growth from MSA, amines, and water were performed in a custom-built small volume aerosol flow tube reactor. Analytical instruments and techniques include a scanning mobility particle sizer to measure particle size distributions, sampling onto a weak cation exchange resin with analysis by ion chromatography to measure amine concentrations, and filter collection and analysis by ultra-high performance liquid chromatography tandem mass spectrometry to measure MSA concentrations. Organics were measured by atmospheric pressure chemical ionization tandem mass spectrometry. The impact of these organics on the initial particle formation as well as growth will be reported. The outcome is an improved understanding of fundamental chemistry of nucleation and growth to ultimately be incorporated into climate models to better predict how particles affect the global climate budget.

  1. Deuterium Fractionation during Amino Acid Formation by Photolysis of Interstellar Ice Analogs Containing Deuterated Methanol

    NASA Astrophysics Data System (ADS)

    Oba, Yasuhiro; Takano, Yoshinori; Watanabe, Naoki; Kouchi, Akira

    2016-08-01

    Deuterium (D) atoms in interstellar deuterated methanol might be distributed into complex organic molecules through molecular evolution by photochemical reactions in interstellar grains. In this study, we use a state-of-the-art high-resolution mass spectrometer coupled with a high-performance liquid chromatography system to quantitatively analyze amino acids and their deuterated isotopologues formed by the photolysis of interstellar ice analogs containing singly deuterated methanol CH2DOH at 10 K. Five amino acids (glycine, α-alanine, β-alanine, sarcosine, and serine) and their deuterated isotopologues whose D atoms are bound to carbon atoms are detected in organic residues formed by photolysis followed by warming up to room temperature. The abundances of singly deuterated amino acids are in the range of 0.3-1.1 relative to each nondeuterated counterpart, and the relative abundances of doubly and triply deuterated species decrease with an increasing number of D atoms in a molecule. The abundances of amino acids increase by a factor of more than five upon the hydrolysis of the organic residues, leading to decreases in the relative abundances of deuterated species for α-alanine and β-alanine. On the other hand, the relative abundances of the deuterated isotopologues of the other three amino acids did not decrease upon hydrolysis, indicating different formation mechanisms of these two groups upon hydrolysis. The present study facilitates both qualitative and quantitative evaluations of D fractionation during molecular evolution in the interstellar medium.

  2. Effects of chemical and enzymatic modifications on starch-oleic acid complex formation.

    PubMed

    Arijaje, Emily Oluwaseun; Wang, Ya-Jane

    2015-04-29

    The solubility of starch-inclusion complexes affects the digestibility and bioavailability of the included molecules. Acetylation with two degrees of substitution, 0.041 (low) and 0.091 (high), combined without or with a β-amylase treatment was employed to improve the yield and solubility of the inclusion complex between debranched potato starch and oleic acid. Both soluble and insoluble complexes were recovered and analyzed for their degree of acetylation, complexation yields, molecular size distributions, X-ray diffraction patterns, and thermal properties. Acetylation significantly increased the amount of recovered soluble complexes as well as the complexed oleic acid in both soluble and insoluble complexes. High-acetylated debranched-only starch complexed the highest amount of oleic acid (38.0 mg/g) in the soluble complexes; low-acetylated starch with or without the β-amylase treatment resulted in the highest complexed oleic acid in the insoluble complexes (37.6-42.9 mg/g). All acetylated starches displayed the V-type X-ray pattern, and the melting temperature generally decreased with acetylation. The results indicate that starch acetylation with or without the β-amylase treatment can improve the formation and solubility of the starch-oleic acid complex.

  3. [Spectral Analysis about the Pharmaceutical Cocrystal Formation of Piracetam and 3-Hydroxybenzoic Acid].

    PubMed

    Zhang, Hui-li; Xia, Yi; Hong, Zhi; Du, Yong

    2015-07-01

    Pharmaceutical cocrystal can improve physical and chemical properties of active pharmaceutical ingredient (API), meanwhile this feature has shown great potential in improving the pharmaceutical's properties and characteristics. In this study, cocrystal formation between piracetam and 3-hydroxybenzoic acid (3HBA) using grinding method has been characterized by Fourier transform infrared (FTIR), Raman and terahertz (THz) spectroscopical techniques. The vibrational modes of different motions are obtained by the assignment of the peaks in the spectra of the starting materials and the cocrystal components. FTIR, Raman and THz spectroscopical results show that the vibrational modes of the cocrystal are different from those of the starting materials. In addition, the dynamic process of the above cocrystal formation is investigated in-depth with Raman and THz spec- tra. Piracetam-3HBA cocrystal is formed pretty fast in first several minutes, and then the formation rate becomes slow. After 35 minutes, such formation process has been completed. The results offer the theoretical benchmark and unique means for real-time monitoring pharmaceutical cocrystal formation and also the corresponding quantitative analysis in the pharmaceutical field.

  4. The formate channel FocA exports the products of mixed-acid fermentation.

    PubMed

    Lü, Wei; Du, Juan; Schwarzer, Nikola J; Gerbig-Smentek, Elke; Einsle, Oliver; Andrade, Susana L A

    2012-08-14

    Formate is a major metabolite in the anaerobic fermentation of glucose by many enterobacteria. It is translocated across cellular membranes by the pentameric ion channel/transporter FocA that, together with the nitrite channel NirC, forms the formate/nitrite transporter (FNT) family of membrane transport proteins. Here we have carried out an electrophysiological analysis of FocA from Salmonella typhimurium to characterize the channel properties and assess its specificity toward formate and other possible permeating ions. Single-channel currents for formate, hypophosphite and nitrite revealed two mechanistically distinct modes of gating that reflect different types of structural rearrangements in the transport channel of each FocA protomer. Moreover, FocA did not conduct cations or divalent anions, but the chloride anion was identified as further transported species, along with acetate, lactate and pyruvate. Formate, acetate and lactate are major end products of anaerobic mixed-acid fermentation, the pathway where FocA is predominantly required, so that this channel is ideally adapted to act as a multifunctional export protein to prevent their intracellular accumulation. Because of the high degree of conservation in the residues forming the transport channel among FNT family members, the flexibility in conducting multiple molecules is most likely a general feature of these proteins.

  5. Somite-Derived Retinoic Acid Regulates Zebrafish Hematopoietic Stem Cell Formation

    PubMed Central

    Pillay, Laura M.; Mackowetzky, Kacey J.; Widen, Sonya A.; Waskiewicz, Andrew Jan

    2016-01-01

    Hematopoietic stem cells (HSCs) are multipotent progenitors that generate all vertebrate adult blood lineages. Recent analyses have highlighted the importance of somite-derived signaling factors in regulating HSC specification and emergence from dorsal aorta hemogenic endothelium. However, these factors remain largely uncharacterized. We provide evidence that the vitamin A derivative retinoic acid (RA) functions as an essential regulator of zebrafish HSC formation. Temporal analyses indicate that RA is required for HSC gene expression prior to dorsal aorta formation, at a time when the predominant RA synthesis enzyme, aldh1a2, is strongly expressed within the paraxial mesoderm and somites. Previous research implicated the Cxcl12 chemokine and Notch signaling pathways in HSC formation. Consequently, to understand how RA regulates HSC gene expression, we surveyed the expression of components of these pathways in RA-depleted zebrafish embryos. During somitogenesis, RA-depleted embryos exhibit altered expression of jam1a and jam2a, which potentiate Notch signaling within nascent endothelial cells. RA-depleted embryos also exhibit a severe reduction in the expression of cxcr4a, the predominant Cxcl12b receptor. Furthermore, pharmacological inhibitors of RA synthesis and Cxcr4 signaling act in concert to reduce HSC formation. Our analyses demonstrate that somite-derived RA functions to regulate components of the Notch and Cxcl12 chemokine signaling pathways during HSC formation. PMID:27861498

  6. Slow peptide bond formation by proline and other N-alkylamino acids in translation

    PubMed Central

    Pavlov, Michael Y.; Watts, Richard E.; Tan, Zhongping; Cornish, Virginia W.; Ehrenberg, Måns; Forster, Anthony C.

    2009-01-01

    Proteins are made from 19 aa and, curiously, one N-alkylamino acid (“imino acid”), proline (Pro). Pro is thought to be incorporated by the translation apparatus at the same rate as the 19 aa, even though the alkyl group in Pro resides directly on the nitrogen nucleophile involved in peptide bond formation. Here, by combining quench-flow kinetics and charging of tRNAs with cognate and noncognate amino acids, we find that Pro incorporates in translation significantly more slowly than Phe or Ala and that other N-alkylamino acids incorporate much more slowly. Our results show that the slowest step in incorporation of N-alkylamino acids is accommodation/peptidyl transfer after GTP hydrolysis on EF-Tu. The relative incorporation rates correlate with expectations from organic chemistry, suggesting that amino acid sterics and basicities affect translation rates at the peptidyl transfer step. Cognate isoacceptor tRNAs speed Pro incorporation to rates compatible with in vivo, although still 3–6 times slower than Phe incorporation from Phe-tRNAPhe depending on the Pro codon. Results suggest that Pro is the only N-alkylamino acid in the genetic code because it has a privileged cyclic structure that is more reactive than other N-alkylamino acids. Our data on the variation of the rate of incorporation of Pro from native Pro-tRNAPro isoacceptors at 4 different Pro codons help explain codon bias not accounted for by the “tRNA abundance” hypothesis. PMID:19104062

  7. Insights into the spontaneity of hydrogen bond formation between formic acid and phthalimide derivatives.

    PubMed

    Júnior, Rogério V A; Moura, Gustavo L C; Lima, Nathalia B D

    2016-11-01

    We evaluated a group of phthalimide derivatives, which comprise a convenient test set for the study of the multiple factors involved in the energetics of hydrogen bond formation. Accordingly, we carried out quantum chemical calculations on the hydrogen bonded complexes formed between a sample of phthalimide derivatives with formic acid with the intent of identifying the most important electronic and structural factors related to how their strength and spontaneity vary across the series. The geometries of all species considered were fully optimized at DFT B3LYP/6-31++G(d,p), RM1, RM1-DH2, and RM1-D3H4 level, followed by frequency calculations to determine their Gibbs free energies of hydrogen bond formation using Gaussian 2009 and MOPAC 2012. Our results indicate that the phthalimide derivatives that form hydrogen bond complexes most favorably, have in their structures only one C=O group and at least one NH group. On the other hand, the phthalimide derivatives predicted to form hydrogen bonds least favorably, possess in their structures two carbonyl groups, C=O, and no NH group. The ability to donate electrons and simultaneously receive one acidic hydrogen is the most important property related to the spontaneity of hydrogen bond formation. We further chose two cyclic compounds, phthalimide and isoindolin-1-one, in which to study the main changes in molecular, structural and spectroscopic properties as related to the formation of hydrogen bonds. Thus, the greatest ability of the isoindolin-1-one compound in forming hydrogen bonds is evidenced by the larger effect on the structural, vibrational, and chemical shifts properties associated with the O-H group. In summary, the electron-donating ability of the hydrogen bond acceptor emerged as the most important property differentiating the spontaneity of hydrogen bond formation in this group of complexes.

  8. Effects of sulfhydryl compounds, carbohydrates, organic acids, and sodium sulfite on the formation of lysinoalanine in preserved egg.

    PubMed

    Luo, Xu-Ying; Tu, Yong-Gang; Zhao, Yan; Li, Jian-Ke; Wang, Jun-Jie

    2014-08-01

    To identify inhibitors for lysinoalanine formation in preserved egg, sulfhydryl compounds (glutathione, L-cysteine), carbohydrates (sucrose, D-glucose, maltose), organic acids (L-ascorbic acid, citric acid, DL-malic acid, lactic acid), and sodium sulfite were individually added at different concentrations to a pickling solution to prepare preserved eggs. Lysinoalanine formation as an index of these 10 substances was determined. Results indicate that glutathione, D-glucose, maltose, L-ascorbic acid, citric acid, lactic acid, and sodium sulfite all effectively diminished lysinoalanine formation in preserved egg albumen and yolk. When 40 and 80 mmol/L of sodium sulfite, citric acid, L-ascorbic acid, and D-glucose were individually added into the pickling solution, the inhibition rates of lysinoalanine in the produced preserved egg albumen and yolk were higher. However, the attempt of minimizing lysinoalanine formation was combined with the premise of ensuring preserved eggs quality. Moreover, the addition of 40 and 80 mmol/L of sodium sulfite, 40 and 80 mmol/L of D-glucose, 40 mmol/L of citric acid, and 40 mmol/L of L-ascorbic acid was optimal to produce preserved eggs. The corresponding inhibition rates of lysinoalanine in the albumen were approximately 76.3% to 76.5%, 67.6% to 67.8%, 74.6%, and 74.6%, and the corresponding inhibition rates of lysinoalanine in the yolk were about 68.7% to 69.7%, 50.6% to 51.8%, 70.4%, and 57.8%. It was concluded that sodium sulfite, D-glucose, L-ascorbic, and citric acid at suitable concentrations can be used to control the formation of lysinoalanine during preserved egg processing.

  9. Spectroscopic investigation on cocrystal formation between adenine and fumaric acid based on infrared and Raman techniques.

    PubMed

    Du, Yong; Fang, Hong Xia; Zhang, Qi; Zhang, Hui Li; Hong, Zhi

    2016-01-15

    As an important component of double-stranded DNA, adenine has powerful hydrogen-bond capability, due to rich hydrogen bond donors and acceptors existing within its molecular structure. Therefore, it is easy to form cocrystal between adenine and other small molecules with intermolecular hydrogen-bond effect. In this work, cocrystal of adenine and fumaric acid has been characterized as model system by FT-IR and FT-Raman spectral techniques. The experimental results show that the cocrystal formed between adenine and fumaric acid possesses unique spectroscopical characteristic compared with that of starting materials. Density functional theory (DFT) calculation has been performed to optimize the molecular structures and simulate vibrational modes of adenine, fumaric acid and the corresponding cocrystal. Combining the theoretical and experimental vibrational results, the characteristic bands corresponding to bending and stretching vibrations of amino and carbonyl groups within cocrystal are shifted into lower frequencies upon cocrystal formation, and the corresponding bond lengths show some increase due to the effect of intermolecular hydrogen bonding. Different vibrational modes shown in the experimental spectra have been assigned based on the simulation DFT results. The study could provide experimental and theoretical benchmarks to characterize cocrystal formed between active ingredients and cocrystal formers and also the intermolecular hydrogen-bond effect within cocrystal formation process by vibrational spectroscopic techniques.

  10. Spectroscopic investigation on cocrystal formation between adenine and fumaric acid based on infrared and Raman techniques

    NASA Astrophysics Data System (ADS)

    Du, Yong; Fang, Hong Xia; Zhang, Qi; Zhang, Hui Li; Hong, Zhi

    2016-01-01

    As an important component of double-stranded DNA, adenine has powerful hydrogen-bond capability, due to rich hydrogen bond donors and acceptors existing within its molecular structure. Therefore, it is easy to form cocrystal between adenine and other small molecules with intermolecular hydrogen-bond effect. In this work, cocrystal of adenine and fumaric acid has been characterized as model system by FT-IR and FT-Raman spectral techniques. The experimental results show that the cocrystal formed between adenine and fumaric acid possesses unique spectroscopical characteristic compared with that of starting materials. Density functional theory (DFT) calculation has been performed to optimize the molecular structures and simulate vibrational modes of adenine, fumaric acid and the corresponding cocrystal. Combining the theoretical and experimental vibrational results, the characteristic bands corresponding to bending and stretching vibrations of amino and carbonyl groups within cocrystal are shifted into lower frequencies upon cocrystal formation, and the corresponding bond lengths show some increase due to the effect of intermolecular hydrogen bonding. Different vibrational modes shown in the experimental spectra have been assigned based on the simulation DFT results. The study could provide experimental and theoretical benchmarks to characterize cocrystal formed between active ingredients and cocrystal formers and also the intermolecular hydrogen-bond effect within cocrystal formation process by vibrational spectroscopic techniques.

  11. Arachidonic acid mediates the formation of abundant alpha-helical multimers of alpha-synuclein

    NASA Astrophysics Data System (ADS)

    Iljina, Marija; Tosatto, Laura; Choi, Minee L.; Sang, Jason C.; Ye, Yu; Hughes, Craig D.; Bryant, Clare E.; Gandhi, Sonia; Klenerman, David

    2016-09-01

    The protein alpha-synuclein (αS) self-assembles into toxic beta-sheet aggregates in Parkinson’s disease, while it is proposed that αS forms soluble alpha-helical multimers in healthy neurons. Here, we have made αS multimers in vitro using arachidonic acid (ARA), one of the most abundant fatty acids in the brain, and characterized them by a combination of bulk experiments and single-molecule Fӧrster resonance energy transfer (sm-FRET) measurements. The data suggest that ARA-induced oligomers are alpha-helical, resistant to fibril formation, more prone to disaggregation, enzymatic digestion and degradation by the 26S proteasome, and lead to lower neuronal damage and reduced activation of microglia compared to the oligomers formed in the absence of ARA. These multimers can be formed at physiologically-relevant concentrations, and pathological mutants of αS form less multimers than wild-type αS. Our work provides strong biophysical evidence for the formation of alpha-helical multimers of αS in the presence of a biologically relevant fatty acid, which may have a protective role with respect to the generation of beta-sheet toxic structures during αS fibrillation.

  12. Sulfate Mineral Formation from Acid-Weathered Phyllosilicates: Implications for the Aqueous History of Mars

    NASA Technical Reports Server (NTRS)

    Craig, P. I.; Ming, D. W.; Rampe, E. B.; Morris, R. V.

    2015-01-01

    Phyllosilicates on Mars are thought to have formed under neutral to alkaline conditions during Mars' earliest Noachian geologic era (approx. 4.1-3.7 Gya). Sulfate formation, on the other hand, requires more acidic conditions which are thought to have occurred later during Mars' Hesperian era (approx. 3.7-3.0 Gya). Therefore, regions on Mars where phyllosilicates and sulfates are found in close proximity to each other provide evidence for the geologic and aqueous conditions during this global transition. Both phyllosilicates and sulfates form in the presence of water and thus give clues to the aqueous history of Mars and its potential for habitability. Phyllosilicates that formed during the Noachian era may have been weathered by the prevailing acidic conditions that characterize the Hesperian. Therefore, the purpose of this study is to characterize the alteration products resulting from acid-sulfate weathered phyllosilicates in laboratory experiments. This study focuses on two phyllosilicates commonly identified with sulfates on Mars: nontronite and saponite. We also compare our results to observations of phyllosilicates and sulfates on Mars to better understand the formation process of sulfates in close proximity to phyllosilicates on Mars and constrain the aqueous conditions of these regions on Mars.

  13. Hyaluronic acid membrane for reducing adhesion formation and reformation in the rat uterine horn.

    PubMed

    Yarali, H; Zahradka, B F; Gomel, V

    1994-09-01

    The efficacy of hyaluronic acid (HA) membrane in preventing or reducing intraperitoneal adhesion formation and reformation was evaluated in the rat uterine horn. Forty-seven Wistar rats were employed. Following a measured laser injury on the right uterine horn of each rat, HA membrane was applied to cover the site of injury in 20 (HA membrane group). No membrane was applied in another 20 (control group). The type and extent of adhesions were assessed at relaparotomy. Following microsurgical adhesiolysis at second-look laparotomy, the same animals were randomized to the HA membrane and control groups. The type and extent of adhesion reformation were evaluated at third-look laparotomy. Following a similar injury on the right uterine horn in another seven rats, HA membrane was applied on both uterine horns. A repeat laparotomy was performed three hours later to assess the status of the membrane. The type and extent of adhesion formation and reformation were comparable between the HA membrane and control groups. The HA membrane did not remain on the uterine horn and gelled rapidly. Hyaluronic acid membrane was ineffective in reducing adhesion formation and reformation in the rat uterine horn.

  14. Dissociative Electron-Ion Recombination of the Protonated Interstellar Species Glycolaldehyde, Acetic Acid, and Methyl Formate

    NASA Astrophysics Data System (ADS)

    Lawson, Patrick; Adams, Nigel

    2011-10-01

    Recently, the prebiotic molecule and primitive sugar glycolaldehyde and its structural isomers acetic acid and the abundant methyl formate have been detected in the interstellar medium(ISM). Understanding the processes involving these molecules is vital to understand the ISM, where stars are formed. The rate constants, αe, for dissociative electron-ion recombination of protonated gycolaldehyde, (HOCH2CHO)H^+, and protonated methyl formate, (HCOOCH3)H^+, have been determined at 300K in a variable temperature flowing afterglow using a Langmuir probe to determine the electron density. The αe at 300K are 3.2 x 10-7 cm^3 s-1 for protonated methyl formate and 7.5 x 10-7 cm^3 s-1 for protonated glycolaldehyde. The αe of protonated acetic acid could not be directly measured due to difficulty in producing the ion, but it appears to have a recombination rate constant, αe, on the ˜10-7 cm^3 s-1 scale. Additional temperature dependence information was obtained. The astrochemical implications of the αe measurements and protonation routes are also discussed.

  15. Inhibition of Pseudomonas aeruginosa biofilm formation by 2,2’-bipyridyl, lipoic, kojic and picolinic acids

    PubMed Central

    Çevik, Kübra; Ulusoy, Seyhan

    2015-01-01

    Objective(s): The inhibitory effects of iron chelators, and FeCl3 chelation on biofilm formation and swarming motility were investigated against an opportunistic human pathogen Pseudomonas aeruginosa. Materials and Methods: The inhibitory activity of 2,2’-bipyridyl, lipoic acid, kojic acid and picolinic acid on biofilm formation of P. aeruginosa strain PAO1 and three clinical isolates (P. aeruginosa PAK01, P. aeruginosa PAK02 and P. aeruginosa PAK03) were investigated, based on crystal violet assay, and swarming motility test. Results: The kojic, lipoic and picolinic acid inhibited biofilm formation by 5-33% in all tested P. aeruginosa isolates. When chelated iron was added, biofilm inhibition rates were determined to be 39-57%. Among the tested chelators against P. aeruginosa, lipoic acid (84%) and kojic acid (68%) presented the highest inhibition of swarming motility. This is the first study to report the inhibitory effect of lipoic acid on biofilm formation and swarming motility of P. aeruginosa. Conclusion: It is considered that lipoic and picolinic acids can serve as alternatives for the treatment of the P. aeruginosa infections by inhibiting biofilm formation. PMID:26557964

  16. Formation of Small Gas Phase Carbonyls from Heterogeneous Oxidation of Polyunsaturated Fatty Acids (PUFA)

    NASA Astrophysics Data System (ADS)

    Zhou, S.; Zhao, R.; Lee, A.; Gao, S.; Abbatt, J.

    2011-12-01

    Fatty acids (FAs) are emitted into the atmosphere from gas and diesel powered vehicles, cooking, plants, and marine biota. Field measurements have suggested that FAs, including polyunsaturated fatty acids (PUFA), could make up an important contribution to the organic fraction of atmospheric aerosols. Due to the existence of carbon-carbon double bonds in their molecules, PUFA are believed to be highly reactive towards atmospheric oxidants such as OH and NO3 radicals and ozone, which will contribute to aerosol hygroscopicity and cloud condensation nuclei activity. Previous work from our group has shown that small carbonyls formed from the heterogeneous reaction of linoleic acid (LA) thin films with gas-phase O3. It is known that the formation of small carbonyls in the atmosphere is not only relevant to the atmospheric budget of volatile organic compounds but also to secondary organic aerosol formation. In the present study, using an online proton transfer reaction mass spectrometry (PTR-MS) and off-line gas chromatography-mass spectrometry (GC-MS) we again investigated carbonyl formation from the same reaction system, i.e. the heterogeneous ozonolysis of LA film. In addition to the previously reported carbonyls, malondialdehyde (MDA), a source of reactive oxygen species that is mutagenic, has been identified as a product for the first time. Small dicarbonyls, e.g. glyoxal, are expected to be formed from the further oxidation of MDA. In this presentation, the gas-phase chemistry of MDA with OH radicals using a newly built Teflon chamber in our group will also be presented.

  17. Formation of the carboxamidine precursor of cyanuric acid from guanine oxidative lesion dehydro-guanidinohydantoin.

    PubMed

    Irvoas, Joris; Trzcionka, Jérôme; Pratviel, Geneviève

    2014-09-01

    DNA damage under oxidative stress leads to oxidation of guanine base. The identification of the resulting guanine lesions in cellular DNA is difficult due to the sensitivity of the primary oxidation products to hydrolysis and/or further oxidation. We isolated dehydroguanidino-hydantoin (DGh) (or oxidized guanidinohydantoin), a secondary oxidation product of guanine, and showed that this lesion reacts readily with nucleophiles such as asymmetric peroxides and transforms to 2,4,6-trioxo-1,3,5-triazinane-1-carboxamidine residue. Further hydrolysis of this intermediate leads to cyanuric acid and finally to urea residue. This work demonstrates a new possible pathway for the formation of the well-known carboxamidine precursor of cyanuric acid lesion.

  18. Formation of an artifact of diclofenac during acidic extraction of environmental water samples.

    PubMed

    Reddersen, K; Heberer, Th

    2003-09-05

    Solid-phase extraction at an acidic pH is used as a common sample preparation method for analyzing residues of the analgesic drug diclofenac (2-[(2,6-dichlorophenyl)amino] benzeneacetic acid) in environmental water samples. This paper describes the matrix-dependent formation of an artifact of diclofenac during sample preparation resulting in an up to 40% underestimation of diclofenac concentrations especially in matrix-prone samples such as sewage effluents or surface water. The artifact most likely being formed during acidification of the sample was unequivocally identified as 1-(2,6-dichlorophenyl)indolin-2-one by capillary gas chromatography-mass spectrometry. To avoid an underestimation of the analytical results quantification of both diclofenac and its artifact is recommended.

  19. Hydrophobic amino acids as a new class of kinetic inhibitors for gas hydrate formation

    PubMed Central

    Sa, Jeong-Hoon; Kwak, Gye-Hoon; Lee, Bo Ram; Park, Da-Hye; Han, Kunwoo; Lee, Kun-Hong

    2013-01-01

    As the foundation of energy industry moves towards gas, flow assurance technology preventing pipelines from hydrate blockages becomes increasingly significant. However, the principle of hydrate inhibition is still poorly understood. Here, we examined natural hydrophobic amino acids as novel kinetic hydrate inhibitors (KHIs), and investigated hydrate inhibition phenomena by using them as a model system. Amino acids with lower hydrophobicity were found to be better KHIs to delay nucleation and retard growth, working by disrupting the water hydrogen bond network, while those with higher hydrophobicity strengthened the local water structure. It was found that perturbation of the water structure around KHIs plays a critical role in hydrate inhibition. This suggestion of a new class of KHIs will aid development of KHIs with enhanced biodegradability, and the present findings will accelerate the improved control of hydrate formation for natural gas exploitation and the utilization of hydrates as next-generation gas capture media. PMID:23938301

  20. Effects of chemical and enzymatic modifications on starch-linoleic acid complex formation.

    PubMed

    Arijaje, Emily Oluwaseun; Wang, Ya-Jane

    2017-02-15

    This study investigated the complexation yield and physicochemical properties of soluble and insoluble starch complexes with linoleic acid when a β-amylase treatment was applied to acetylated and debranched potato starch. The degree of acetylation was generally higher in the soluble complexes than in the insoluble ones. The insoluble complexes from the acetylated starch displayed the V-type pattern, whereas, the soluble complexes displayed a mixture of either the A-/V-type or the B-/V-type pattern. Acetylation decreased onset and peak melting temperatures for the insoluble complexes, whereas no melting endotherm was observed in the soluble complexes. Acetylation substantially increased the amount of complexed linoleic acid in the insoluble complexes, but had little positive effect on the formation of the soluble complexes. The β-amylase treatment significantly increased the complexed linoleic content in both soluble and insoluble complexes for the low acetylated starch, but not for the high acetylated starch.

  1. The formation of 2-hydroxypropylmercapturic acid from 1-halogenopropanes in the rat

    PubMed Central

    Barnsley, E. A.

    1966-01-01

    1. 2-Hydroxypropylmercapturic acid, i.e. N-acetyl-S-(2-hydroxypropyl)-l-cysteine, has been isolated, as the dicyclohexylammonium salt, from the urine of rats dosed with 1-bromopropane. 2. The formation of the same metabolite from 1-chloropropane, 1-iodopropane, 1,2-epoxypropane and 1-chloropropan-2-ol has been demonstrated by chromatographic examination of the urine excreted by rats after they had been dosed with these compounds. 3. (+)- and (−)-Dicyclohexylammonium 2-hydroxypropylmercapturate have been prepared by fractional crystallization of the mixture of isomers obtained by two methods: the reaction of 1,2-epoxypropane with l-cysteine followed by acetylation, and the reduction of 2-oxopropylmercapturic acid. 4. The following compounds have also been prepared: S-(3-hydroxypropyl)-l-cysteine, (+)- and (−)-S-(2-hydroxypropyl)-l-cysteine, dicyclohexylammonium 3-hydroxypropylmercapturate, (+)- and (−)-dicyclohexylammonium 2-hydroxy-1-methylethylmercapturate, and (+)- and (−)-dicyclohexylammonium 1-(ethoxycarbonyl)ethylmercapturate. PMID:5968536

  2. Formation of [b3 - 1 + cat]+ ions from metal-cationized tetrapeptides containing beta-alanine, gamma-aminobutyric acid or epsilon-aminocaproic acid residues.

    PubMed

    Osburn, Sandra M; Ochola, Sila O; Talaty, Erach R; Van Stipdonk, Michael J

    2008-11-01

    The presence and position of a single beta-alanine (betaA), gamma-aminobutyric acid (gammaABu) or epsilon-aminocaproic acid (Cap) residue has been shown to have a significant influence on the formation of b(n)+ and y(n)+ product ions from a series of model, protonated peptides. In this study, we examined the effect of the same residues on the formation of analogous [b3 - 1 + cat]+ products from metal (Li+, Na+ and Ag+)-cationized peptides. The larger amino acids suppress formation of b3+ from protonated peptides with general sequence AAXG (where X = beta-alanine, gamma-aminobutyric acid or epsilon-aminocaproic acid), presumably because of the prohibitive effect of larger cyclic intermediates in the 'oxazolone' pathway. However, abundant [b3 - 1 + cat]+ products are generated from metal-cationized versions of AAXG. Using a group of deuterium-labeled and exchanged peptides, we found that formation of [b3 - 1 + cat]+ involves transfer of either amide or alpha-carbon position H atoms, and the tendency to transfer the atom from the alpha-carbon position increases with the size of the amino acid in position X. To account for the transfer of the H atom, a mechanism involving formation of a ketene product as [b3 - 1 + cat]+ is proposed.

  3. Enhancing Skin Permeation of Biphenylacetic Acid (BPA) Using Salt Formation with Organic and Alkali Metal Bases

    PubMed Central

    Pawar, Vijay; Naik, Prashant; Giridhar, Rajani; Yadav, Mange Ram

    2015-01-01

    In the present study, a series of organic and alkali metal salts of biphenylacetic acid (BPA) have been prepared and evaluated in vitro for percutaneous drug delivery. The physicochemical properties of BPA salts were determined using solubility measurements, DSC, and IR. The DSC thermogram and FTIR spectra confirmed the salt formation with organic and alkali metal bases. Among the series, salts with organic amines (ethanolamine, diethanolamine, triethanolamine, and diethylamine) had lowered melting points while the alkali metal salt (sodium) had a higher melting point than BPA. The in vitro study showed that salt formation improves the physicochemical properties of BPA, leading to improved permeability through the skin. Amongst all the prepared salts, ethanolamine salt (1b) showed 7.2- and 5.4-fold higher skin permeation than the parent drug at pH 7.4 and 5.0, respectively, using rat skin. PMID:26839810

  4. Ultraviolet-induced effects on chloramine and cyanogen chloride formation from chlorination of amino acids.

    PubMed

    Weng, ShihChi; Blatchley, Ernest R

    2013-05-07

    Ultraviolet (UV)-based treatment is commonly used to augment chlorination in swimming pools. However, the effects of combined application of UV254/chlorine on disinfection byproduct (DBP) formation are incompletely defined. To examine this issue, experiments were conducted with amino acids (l-arginine, l-histidine, and glycine) that are representative of those introduced to swimming pools via human body fluids. For each precursor, stepwise experiments were conducted with chlorination and UV254 exposure, with/without post-chlorination. Net formation and decomposition of chloramines and cyanogen chloride (CNCl) were measured for a range of chlorine/precursor (Cl/P) molar ratios and UV254 doses. Substantial production of NH2Cl from l-arginine and l-histidine was observed at Cl/P = 1.0 and 2.0 when post-chlorination was applied to UV254-irradiated samples. These results suggested a mechanism of rapid N-chlorination, followed by cleavage of NH3 by UV254 irradiation. CNCl formation was observed from UV254-irradiated samples of l-arginine and l-histidine when Cl/P = 2.0 and 3.0, as well as from glycine for Cl/P ≤ 1. Structurally related precursor compounds were examined for CNCl formation potential in chlorination/UV experiments. CNCl formation was promoted by UV254 exposure of chlorinated imidazole and guanidine compounds, which suggested that these groups contributed to CNCl formation. The results have implications with respect to the application of chlorine and UV for water treatment in swimming pools and other settings, such as water reuse and advanced oxidation processes.

  5. Formation of C21 bile acids from plant sterols in the rat

    SciTech Connect

    Boberg, K.M.; Lund, E.; Olund, J.; Bjoerkhem, I. )

    1990-05-15

    Formation of bile acids from sitosterol in bile-fistulated female Wistar rats was studied with use of 4-14C-labeled sitosterol and sitosterol labeled with 3H in specific positions. The major part (about 75%) of the 14C radioactivity recovered as bile acids in bile after intravenous administration of (4-14C)sitosterol was found to be considerably more polar than cholic acid, and only trace amounts of radioactivity had chromatographic properties similar to those of cholic acid and chenodeoxycholic acid. It was shown that polar metabolites were formed by intermediate oxidation of the 3 beta-hydroxyl group (loss of 3H from 3 alpha-3H-labeled sitosterol) and that the most polar fraction did not contain a hydroxyl group at C7 (retention of 3H in 7 alpha,7 beta-3H2-labeled sitosterol). Furthermore, the polar metabolites had lost at least the terminal 6 or 7 carbon atoms of the side chain (loss of 3H from 22,23-3H2- and 24,28-3H2-labeled sitosterol). Experiments with 3H-labeled 7 alpha-hydroxysitosterol and 4-14C-labeled 26-hydroxysitosterol showed that none of these compounds was an efficient precursor to the polar metabolites. By analysis of purified most polar products of (4-14C) sitosterol by radio-gas chromatography and the same products of 7 alpha,7 beta-(2H2)sitosterol by combined gas chromatography-mass spectrometry, two major metabolites could be identified as C21 bile acids. One metabolite had three hydroxyl groups (3 alpha, 15, and unknown), and one had two hydroxyl groups (3 alpha, 15) and one keto group. Considerably less C21 bile acids were formed from (4-14C)sitosterol in male than in female Wistar rats. The C21 bile acids formed in male rats did not contain a 15-hydroxyl group. Conversion of a (4-14C)sitosterol into C21 bile acids did also occur in adrenalectomized and ovariectomized rats, indicating that endocrine tissues are not involved.

  6. Vanillin formation from ferulic acid in Vanilla planifolia is catalysed by a single enzyme

    PubMed Central

    Gallage, Nethaji J.; Hansen, Esben H.; Kannangara, Rubini; Olsen, Carl Erik; Motawia, Mohammed Saddik; Jørgensen, Kirsten; Holme, Inger; Hebelstrup, Kim; Grisoni, Michel; Møller, Birger Lindberg

    2014-01-01

    Vanillin is a popular and valuable flavour compound. It is the key constituent of the natural vanilla flavour obtained from cured vanilla pods. Here we show that a single hydratase/lyase type enzyme designated vanillin synthase (VpVAN) catalyses direct conversion of ferulic acid and its glucoside into vanillin and its glucoside, respectively. The enzyme shows high sequence similarity to cysteine proteinases and is specific to the substitution pattern at the aromatic ring and does not metabolize caffeic acid and p-coumaric acid as demonstrated by coupled transcription/translation assays. VpVAN localizes to the inner part of the vanilla pod and high transcript levels are found in single cells located a few cell layers from the inner epidermis. Transient expression of VpVAN in tobacco and stable expression in barley in combination with the action of endogenous alcohol dehydrogenases and UDP-glucosyltransferases result in vanillyl alcohol glucoside formation from endogenous ferulic acid. A gene encoding an enzyme showing 71% sequence identity to VpVAN was identified in another vanillin-producing plant species Glechoma hederacea and was also shown to be a vanillin synthase as demonstrated by transient expression in tobacco. PMID:24941968

  7. Vanillin formation from ferulic acid in Vanilla planifolia is catalysed by a single enzyme.

    PubMed

    Gallage, Nethaji J; Hansen, Esben H; Kannangara, Rubini; Olsen, Carl Erik; Motawia, Mohammed Saddik; Jørgensen, Kirsten; Holme, Inger; Hebelstrup, Kim; Grisoni, Michel; Møller, Birger Lindberg

    2014-06-19

    Vanillin is a popular and valuable flavour compound. It is the key constituent of the natural vanilla flavour obtained from cured vanilla pods. Here we show that a single hydratase/lyase type enzyme designated vanillin synthase (VpVAN) catalyses direct conversion of ferulic acid and its glucoside into vanillin and its glucoside, respectively. The enzyme shows high sequence similarity to cysteine proteinases and is specific to the substitution pattern at the aromatic ring and does not metabolize caffeic acid and p-coumaric acid as demonstrated by coupled transcription/translation assays. VpVAN localizes to the inner part of the vanilla pod and high transcript levels are found in single cells located a few cell layers from the inner epidermis. Transient expression of VpVAN in tobacco and stable expression in barley in combination with the action of endogenous alcohol dehydrogenases and UDP-glucosyltransferases result in vanillyl alcohol glucoside formation from endogenous ferulic acid. A gene encoding an enzyme showing 71% sequence identity to VpVAN was identified in another vanillin-producing plant species Glechoma hederacea and was also shown to be a vanillin synthase as demonstrated by transient expression in tobacco.

  8. XAS and RIXS study of acetic acid and methyl formate in liquid

    NASA Astrophysics Data System (ADS)

    Takahashi, O.; Nishida, N.; Kanai, S.; Horikawa, Y.; Tokushima, T.

    2016-05-01

    Structure of acetic acid (AA) and methyl formate (MF) in the liquid phase is studied using X-ray absorption spectroscopy (XAS) and X-ray emission spectroscopy (XES) experimentally and theoretically. Two distinct XES spectra are observed by tuning photon energy for both molecules. Model structure in the liquid phase is constructed using the classical and first principle molecular dynamics simulations, and XES spectra are calculated using density functional theory. Calculated XES spectra are consistent with experimental ones. The effect of core-hole induced excited state molecular dynamics are discussed.

  9. Effect of caffeic acid phenethyl ester on bone formation in the expanded inter-premaxillary suture

    PubMed Central

    Kazancioglu, Hakki Oguz; Aksakalli, Sertac; Ezirganli, Seref; Birlik, Muhammet; Esrefoglu, Mukaddes; Acar, Ahmet Hüseyin

    2015-01-01

    Background Narrow maxilla is a common problem in orthodontics and dentofacial orthopedics. To solve this problem, a procedure called rapid maxillary expansion (RME) has been used. However, relapse tendency is a major problem of RME. Although relapse tendency is not clearly understood, various treatment procedures and new applications have been investigated. The present study aimed to investigate the possible effectiveness of caffeic acid phenethyl ester (CAPE) on new bone formation in rat midpalatal suture after RME. Materials and methods Twenty male Sprague Dawley rats were used in this study. The animals were randomly divided into two groups as control and CAPE group. In the CAPE group, CAPE was administered systemically via intraperitoneal injection. RME procedure was performed on all animals. For this purpose, the springs were placed on the maxillary incisors of rats and activated for 5 days. After then, the springs were removed and replaced with short lengths of rectangular retaining wire for consolidation period of 15 days. At the end of the study, histomorphometric analysis was carried out to assess new bone formation. Results New bone formation was significantly greater in the CAPE group than the control group (P<0.05). CAPE enhances new bone formation in midpalatal suture after RME. Conclusion These results show that CAPE may decrease the time needed for retention. PMID:26730181

  10. Gas-phase hydrolysis of triplet SO2: A possible direct route to atmospheric acid formation

    NASA Astrophysics Data System (ADS)

    Donaldson, D. James; Kroll, Jay A.; Vaida, Veronica

    2016-07-01

    Sulfur chemistry is of great interest to the atmospheric chemistry of several planets. In the presence of water, oxidized sulfur can lead to new particle formation, influencing climate in significant ways. Observations of sulfur compounds in planetary atmospheres when compared with model results suggest that there are missing chemical mechanisms. Here we propose a novel mechanism for the formation of sulfurous acid, which may act as a seed for new particle formation. In this proposed mechanism, the lowest triplet state of SO2 (3B1), which may be accessed by near-UV solar excitation of SO2 to its excited 1B1 state followed by rapid intersystem crossing, reacts directly with water to form H2SO3 in the gas phase. For ground state SO2, this reaction is endothermic and has a very high activation barrier; our quantum chemical calculations point to a facile reaction being possible in the triplet state of SO2. This hygroscopic H2SO3 molecule may act as a condensation nucleus for water, giving rise to facile new particle formation (NPF).

  11. Gas-phase hydrolysis of triplet SO2: A possible direct route to atmospheric acid formation

    PubMed Central

    Donaldson, D. James; Kroll, Jay A.; Vaida, Veronica

    2016-01-01

    Sulfur chemistry is of great interest to the atmospheric chemistry of several planets. In the presence of water, oxidized sulfur can lead to new particle formation, influencing climate in significant ways. Observations of sulfur compounds in planetary atmospheres when compared with model results suggest that there are missing chemical mechanisms. Here we propose a novel mechanism for the formation of sulfurous acid, which may act as a seed for new particle formation. In this proposed mechanism, the lowest triplet state of SO2 (3B1), which may be accessed by near-UV solar excitation of SO2 to its excited 1B1 state followed by rapid intersystem crossing, reacts directly with water to form H2SO3 in the gas phase. For ground state SO2, this reaction is endothermic and has a very high activation barrier; our quantum chemical calculations point to a facile reaction being possible in the triplet state of SO2. This hygroscopic H2SO3 molecule may act as a condensation nucleus for water, giving rise to facile new particle formation (NPF). PMID:27417675

  12. Shock wave synthesis of amino acids from solutions of ammonium formate and ammonium bicarbonate

    NASA Astrophysics Data System (ADS)

    Suzuki, Chizuka; Furukawa, Yoshihiro; Kobayashi, Takamichi; Sekine, Toshimori; Nakazawa, Hiromoto; Kakegawa, Takeshi

    2015-07-01

    The emergence of life's building blocks, such as amino acids and nucleobases, on the prebiotic Earth was a critical step for the beginning of life. Reduced species with low mass, such as ammonia, amines, or carboxylic acids, are potential precursors for these building blocks of life. These precursors may have been provided to the prebiotic ocean by carbonaceous chondrites and chemical reactions related to meteorite impacts on the early Earth. The impact of extraterrestrial objects on Earth occurred more frequently during this period than at present. Such impacts generated shock waves in the ocean, which have the potential to progress chemical reactions to form the building blocks of life from reduced species. To simulate shock-induced reactions in the prebiotic ocean, we conducted shock-recovery experiments on ammonium bicarbonate solution and ammonium formate solution at impact velocities ranging from 0.51 to 0.92 km/s. In the products from the ammonium formate solution, several amino acids (glycine, alanine, ß-alanine, and sarcosine) and aliphatic amines (methylamine, ethylamine, propylamine, and butylamine) were detected, although yields were less than 0.1 mol % of the formic acid reactant. From the ammonium bicarbonate solution, smaller amounts of glycine, methylamine, ethylamine, and propylamine were formed. The impact velocities used in this study represent minimum cases because natural meteorite impacts typically have higher velocities and longer durations. Our results therefore suggest that shock waves could have been involved in forming life's building blocks in the ocean of prebiotic Earth, and potentially in aquifers of other planets, satellites, and asteroids.

  13. Formation and fate of haloacetic acids (HAAs) within the water treatment plant.

    PubMed

    Rodriguez, Manuel J; Serodes, Jean; Roy, Danielle

    2007-10-01

    Most research on the occurrence of chlorinated disinfection by-products (DBPs) in drinking water has focused on trihalomethane (THM) formation and evolution, in particular within distribution systems. In this research, we investigated the variability of the occurrence of haloacetic acids (HAAs) during the treatment process in two facilities where surface water is pre-chlorinated before being treated by conventional physico-chemical processes. The investigation focused on both seasonal and point-to-point fluctuations of HAAs. In both facilities, samples were collected weekly during 1 complete year at four points in order to generate robust data on HAAs and on complementary parameters. The results showed that the initial formation of HAAs was the highest and the most variable in the plant where levels of DBP precursor indicators and the pre-chlorination dose were both higher and more variable. Subsequent formation of HAAs from the pre-chlorination point until the settled water occurred due to remaining levels of residual chlorine and DBP precursors. However, HAA levels and in particular dichloroacetic acid (DCAA) (the preponderant HAA species in the waters under study) decreased dramatically during filtration, very probably because of biodegradation within the filter. The effect of filtration on DCAA fate was season-dependant, with the highest degradation in warm water periods and practically no variation during winter. Statistical modeling was applied to empirically identify the operational factors responsible for HAA formation and fate. Model performance to identify HAA variability in waters following pre-chlorination was much better than for water following filtration, which is due to the lack of information on mechanisms and conditions favoring DCAA degradation.

  14. Formation of titanium phosphate composites during phosphoric acid decomposition of natural sphene

    SciTech Connect

    Maslova, Marina V.; Rusanova, Daniela Naydenov, Valeri; Antzutkin, Oleg N.; Gerasimova, Lidia G.

    2008-12-15

    Decomposition of mineral sphene, CaTiOSiO{sub 4}, by H{sub 3}PO{sub 4} is investigated in detail. During the dissolution process, simultaneous calcium leaching and formation of titanium phosphate (TiP) take place. The main product of decomposition is a solid titanium phosphate-silica composite. The XRD, solid-sate NMR, IR, TGA, SEM and BET data were used to identify and characterize the composite as a mixture of crystalline Ti(HPO{sub 4}){sub 2}.H{sub 2}O and silica. When 80% phosphoric acid is used the decomposition degree is higher than 98% and calcium is completely transferred into the liquid phase. Formation of Ti(HPO{sub 4}){sub 2}.H{sub 2}O proceeds via formation of meta-stable titanium phosphate phases, Ti(H{sub 2}PO{sub 4})(PO{sub 4}).2H{sub 2}O and Ti(H{sub 2}PO{sub 4})(PO{sub 4}). The sorption affinities of TiP composites were examined in relation to caesium and strontium ions. A decrease of H{sub 3}PO{sub 4} concentration leads to formation of composites with greater sorption properties. The maximum sorption capacity of TiP is observed when 60% H{sub 3}PO{sub 4} is used in sphene decomposition. The work demonstrates a valuable option within the Ti(HPO{sub 4}){sub 2}.H{sub 2}O-SiO{sub 2} composite synthesis scheme, to use phosphoric acid flows for isolation of CaHPO{sub 4}.2H{sub 2}O fertilizer. - Graphical abstract: A new synthesis scheme for preparation of composite titanium phosphate (TiP) ion-exchangers upon one-stage decomposition process of natural sphene with phosphoric acid is presented. Syntheses of {alpha}-TiP-silica composites proceed via formation of meta-stable titanium phosphate phases. The concentration of H{sub 3}PO{sub 4} determines the porosity of final products and their sorption affinities.

  15. Biodegradation of dimethylphenols by bacteria with different ring-cleavage pathways of phenolic compounds.

    PubMed

    Viggor, Signe; Heinaru, Eeva; Loponen, Jyrki; Merimaa, Merike; Tenno, Toomas; Heinaru, Ain

    2002-01-01

    The biodegradation of 3,4, 2,4, 2,3, 2,6 and 3,5-dimethylphenol in combination with phenol and p-cresol by axenic and mixed cultures of bacteria was investigated. The strains, which degrade phenol and p-cresol through different catabolic pathways, were isolated from river water continuously polluted with phenolic compounds of leachate of oil shale semicoke ash heaps. The proper research of degradation of 2,4 and 3,4-dimethylphenol in multinutrient environments was performed. The degradation of phenolic compounds from mixtures indicated a flux of substrates into different catabolic pathways. Catechol 2,3-dioxygenase activity was induced by dimethylphenols in Pseudomonas mendocina PC1, where meta cleavage pathway was functional during the degradation of p-cresol. In the case of strains PC18 and PC24 of P. fluorescens, the degradation of p-cresol occurred via the protocatechuate ortho pathway and the key enzyme of this pathway, p-cresol methylhydroxylase, was also induced by dimethylphenols. 2,4 and 3,4-dimethylphenols were converted into the dead-end products 4-hydroxy-3-methylbenzoic acid and 4-hydroxy-2-methylbenzoic acid. In the degradation of 3,4-dimethylphenol, the transient accumulation of 4-hydroxy-2-methylbenzaldehyde repressed the consumption of phenol from substrate mixtures. A mixed culture of strains with different catabolic types made it possible to overcome the incompatibilities at degradation of studied substrate mixtures.

  16. Formation of Amino Acid Precursors by Bombardment of Interstellar Ice Analogs with High Energy Heavy Ions

    NASA Astrophysics Data System (ADS)

    Kobayashi, Kensei; Mita, Hajime; Yoshida, Satoshi; Shibata, Hiromi; Enomoto, Shingo; Matsuda, Tomoyuki; Fukuda, Hitoshi; Kondo, Kotaro; Oguri, Yoshiyuki; Kebukawa, Yoko

    2016-07-01

    A wide variety of organic compounds have been detected in extraterrestrial bodies. It has been recognized that carbonaceous chondrites contain pristine amino acids [1]. There are several scenarios of the formation of such extraterrestrial amino acids or their precursors. Greenberg proposed a scenario that complex organic compounds were formed in interstellar ices in dense clouds, which were brought into solar system small bodies when the solar system was formed [2]. The ice mantles of interstellar dust particles (ISDs) in dense clouds are composed of H2O, CO, CH3OH, CH4, CO2, NH3, etc. In order to verify the scenario, a number of laboratory experiments have been conducted where interstellar ice analogs were irradiated with high-energy particles [3,4] or UV [5,6], and formation of complex organic compounds including amino acid precursors were detected in the products. Though ion-molecular reactions in gaseous phase and surface reactions on the ice mantles have been studied intensively, much less works on cosmic rays-induced reaction have been reported. In order to study possible formation of complex molecules in interstellar ices, frozen mixtures of water, methanol and ammonia with various mixing ratios were irradiated with high-energy heavy ions such as carbon ions (290 MeV/u) and neon ions (400 MeV/u) from HIMAC, NIRS, Japan. For comparison, gaseous mixtures of water, ammonia, carbon monoxide, carbon dioxide, and/or methane were irradiated with protons (2.5 MeV) from a Tandem accelerator, Tokyo Tech, Japan. Amino acids in the products were determined by cation exchange HPLC after acid hydrolysis. Products, both before and after acid hydrolysis, were also characterized by FT-IR and other techniques. Amino acids were detected in the hydrolyzed products after mixture of CH3OH, NH3 and H2O with various mixing ratios were irradiated with heavy ions, including when their mixing ratio was set close to the reported value of the interstellar ices (10:1:37). In the HIMAC

  17. Titan's Primordial Soup: Formation of Amino Acids via Low Temperature Hydrolysis of Tholins

    NASA Astrophysics Data System (ADS)

    Neish, Catherine; Somogyi, Á.; Smith, M. A.

    2009-09-01

    Titan, Saturn's largest moon, is a world rich in the "stuff of life". Reactions occurring in its dense nitrogen-methane atmosphere produce a wide variety of organic molecules, which subsequently rain down onto its surface. Water - thought to be another important ingredient for life - is likewise abundant on Titan. Theoretical models of Titan's formation predict that its interior consists of an ice I layer several tens of kilometers thick overlying a liquid ammonia-rich water layer several hundred kilometers thick (Tobie et al., 2005). Though its surface temperature of 94K dictates that Titan is on average too cold for liquid water to persist at its surface, melting caused by impacts and/or cryovolcanism may lead to its episodic availability. Impact melt pools on Titan would likely remain liquid for 102 - 104 years before freezing (O'Brien et al., 2005). The combination of complex organic molecules and transient locales of liquid water make Titan an interesting natural laboratory for studying prebiotic chemistry. In this work, we sought to determine what biomolecules might be formed under conditions analogous to those found in transient liquid water environments on Titan. We hydrolyzed Titan organic haze analogues, or "tholins", in 13 wt. % ammonia-water at 253K and 293K for a year. Using a combination of high resolution mass spectroscopy and tandem mass spectroscopy fragmentation techniques, four amino acids were identified in the hydrolyzed tholin sample. These four species have been assigned as the amino acids asparagine, aspartic acid, glutamine, and glutamic acid. This represents the first detection of biologically relevant molecules created under conditions similar to those found in impact melt pools and cryolavas on Titan. Future missions to Titan should therefore carry instrumentation capable of detecting amino acids and other prebiotically relevant molecules on its surface This work was supported by the NASA Exobiology Program.

  18. Eicosapentaenoic acid reduces membrane fluidity, inhibits cholesterol domain formation, and normalizes bilayer width in atherosclerotic-like model membranes.

    PubMed

    Mason, R Preston; Jacob, Robert F; Shrivastava, Sandeep; Sherratt, Samuel C R; Chattopadhyay, Amitabha

    2016-12-01

    Cholesterol crystalline domains characterize atherosclerotic membranes, altering vascular signaling and function. Omega-3 fatty acids reduce membrane lipid peroxidation and subsequent cholesterol domain formation. We evaluated non-peroxidation-mediated effects of eicosapentaenoic acid (EPA), other TG-lowering agents, docosahexaenoic acid (DHA), and other long-chain fatty acids on membrane fluidity, bilayer width, and cholesterol domain formation in model membranes. In membranes prepared at 1.5:1 cholesterol-to-phospholipid (C/P) mole ratio (creating pre-existing domains), EPA, glycyrrhizin, arachidonic acid, and alpha linolenic acid promoted the greatest reductions in cholesterol domains (by 65.5%, 54.9%, 46.8%, and 45.2%, respectively) compared to controls; other treatments had modest effects. EPA effects on cholesterol domain formation were dose-dependent. In membranes with 1:1 C/P (predisposing domain formation), DHA, but not EPA, dose-dependently increased membrane fluidity. DHA also induced cholesterol domain formation without affecting temperature-induced changes in-bilayer unit cell periodicity relative to controls (d-space; 57Å-55Å over 15-30°C). Together, these data suggest simultaneous formation of distinct cholesterol-rich ordered domains and cholesterol-poor disordered domains in the presence of DHA. By contrast, EPA had no effect on cholesterol domain formation and produced larger d-space values relative to controls (60Å-57Å; p<0.05) over the same temperature range, suggesting a more uniform maintenance of lipid dynamics despite the presence of cholesterol. These data indicate that EPA and DHA had different effects on membrane bilayer width, membrane fluidity, and cholesterol crystalline domain formation; suggesting omega-3 fatty acids with differing chain length or unsaturation may differentially influence membrane lipid dynamics and structural organization as a result of distinct phospholipid/sterol interactions.

  19. Turing pattern formation in the chlorine dioxide-iodine- malonic acid reaction-diffusion system

    NASA Astrophysics Data System (ADS)

    Setayeshgar, Sima

    The formation of localized structures in the chlorine dioxide-idodine-malonic acid (CDIMA) reaction-diffusion system is investigated numerically using a realistic model of this system. We analyze the one-dimensional patterns formed along the gradients imposed by boundary feeds, and study their linear stability to symmetry- breaking perturbations (the Turing instability) in the plane transverse to these gradients. We establish that an often-invoked simple local linear analysis which neglects longitudinal diffusion is inappropriate for predicting the linear stability of these patterns. Using a fully nonuniform analysis, we investigate the structure of the patterns formed along the gradients and their stability to transverse Turing pattern formation as a function of the values of two control parameters: the malonic acid feed concentration and the size of the reactor in the dimension along the gradients. The results from this investigation are compared with existing experimental results. We also verify that the two-variable reduction of the chemical model employed in the linear stability analysis is justified. Finally, we present numerical solution of the CDIMA system in two dimensions which is in qualitative agreement with experiments. This result also confirms our linear stability analysis, while demonstrating the feasibility of numerical exploration of realistic chemical models.

  20. Phs1 and the Synthesis of Very Long Chain Fatty Acids Are Required for Ballistospore Formation

    PubMed Central

    Ianiri, Giuseppe; Abhyankar, Ritika; Kihara, Akio; Idnurm, Alexander

    2014-01-01

    The production and dissemination of spores by members of the fungal kingdom is a major reason for the success of this eukaryotic lineage in colonizing most terrestrial ecosystems. Ballistospores are a type of spore produced by basidiomycete fungi, such as the mushrooms and plant pathogenic rusts. These spores are forcefully discharged through a unique liquid-drop fusion mechanism, enabling the aerosolization of these particles that can contribute to plant disease and human allergies. The genes responsible for this process are unknown due to technical challenges in studying many of the fungi that produce ballistospores. Here, we applied newly-developed techniques in a forward genetic screen to identify genes required for ballistospore formation or function in a tractable red yeast, a species of Sporobolomyces. One strain bearing a mutation in the PHS1 gene was identified as a mirror mutant. PHS1 encodes 3-hydroxyacyl-CoA dehydratase required for the third step in very long chain fatty acid biosynthesis. The Sporobolomyces PHS1 gene complements the essential functions of a S. cerevisiae phs1 mutant. The Sporobolomyces phs1 mutant strain has less dehydratase activity and a reduction in very long chain fatty acids compared to wild type. The mutant strain also exhibits sensitivity to cell wall stress agents and loss of shooting due to a delay in ballistospore formation, indicating that the role of Phs1 in spore dissemination may be primarily in cellular integrity. PMID:25148260

  1. [Effects of ascorbic acid on the free radical formations of isoniazid and its metabolites].

    PubMed

    Matsuki, Y; Akazawa, M; Tsuchiya, K; Sakurai, H; Kiwada, H; Goromaru, T

    1991-10-01

    By the use of electron spin resonance (ESR) spectroscopy and of spin-trapping technique, the effects of ascorbic acid on the formation of the free radical intermediates due to isoniazid (INAH) and its metabolites were investigated with a microsomal system. When alpha-(4-pyridyl 1-oxide)-N-tert butylnitrone (4-POBN) was used as a spin trapping agent, the ESR signal due to hydrazine (Hy) was formed to be most intensive among others. Therefore, it was presumed that Hy is a potent intermediate to cause an INAH-induced hepatic injury. In the presence of ascorbic acid (AA), the free radical formation of Hy, INAH and acetyl hydrazine was significantly inhibited, suggesting that AA may affect the INAH-hepatitis. By the addition of inhibitors of cytochrome P-450 like metyrapone and CO, the generation of the radical from Hy decreased, confirming that the radical is formed by the cytochrome P-450 dependent microsome systems. The 4-POBN-trapped radical species generated from Hy was presumed to be the hydrazyl radical by the results of mass spectrometry.

  2. Observation of nitrous acid (HONO) in Beijing, China: Seasonal variation, nocturnal formation and daytime budget.

    PubMed

    Wang, Jiaqi; Zhang, Xiaoshan; Guo, Jia; Wang, Zhangwei; Zhang, Meigen

    2017-02-23

    Seasonal characteristics of atmospheric nitrous acid (HONO) were investigated with high time-resolution field measurements at an urban site of Beijing in four select months (representing four different seasons) from September 2015 to July 2016. The HONO concentrations displayed a pronounced seasonal profile with a maximum in autumn (2.27±1.82ppb) and a minimum in winter (1.05±0.89ppb). Significant diurnal cycles were also observed during the whole campaign. We found that the nighttime build-up of HONO was attributed to the heterogeneous conversion of NO2 on wet surface. The calculated NO2 to HONO conversion frequencies varied from 0.005h(-1) in spring to 0.010h(-1) in summer, with an average value of 0.008h(-1). The seasonality of these conversion frequencies was closely related to the RH levels in different seasons. During daytime, large additional HONO sources were calculated. The noontime additional source was the highest in autumn 3.82ppbh(-1), followed by summer 3.05ppbh(-1), spring 2.63ppbh(-1) and winter 1.30ppbh(-1). Correlation studies between the additional HONO source and related parameters demonstrated that the controlling processes responsible for HONO daytime formation varied in different seasons, and that the photo-enhanced formation on wet surface or the photolysis of adsorbed nitric acid and nitrate could be potential HONO sources in Beijing.

  3. Photochemical reactions of divalent mercury with thioglycolic acid: formation of mercuric sulfide particles.

    PubMed

    Si, Lin; Ariya, Parisa A

    2015-01-01

    Mercury (Hg) is a key toxic global pollutant. Studies in aquatic environment have suggested that thiols could be important for mercury speciation. Thioglycolic acid has been detected in various natural water systems and used as a model compound to study the complicated interaction between mercury and polyfunctional dissolved organic matter (DOM). We herein presented the first evidence for mercury particle formation during kinetic and product studies on the photochemistry of divalent mercury (Hg(2+)) with thioglycolic acid at near environmental conditions. Mercuric sulfide (HgS) particles formed upon photolysis were identified by high-resolution transmission electron microscopy coupled with energy dispersive spectrometry and select area electron diffraction. Kinetic data were obtained using UV-visible spectrophotometry and cold vapour atomic fluorescent spectrometry. The apparent first-order reaction rate constant under our experimental conditions was calculated to be (2.3±0.4)×10(-5) s(-1) at T=296±2 K and pH 4.0. It was found that (89±3)% of the reactants undergo photoreduction to generate elemental mercury (Hg(0)). The effects of ionic strengths, pH and potassium ion were also investigated. The formation of HgS particles pointed to the possible involvement of heterogeneous processes. Our kinetic results indicated the importance of weak binding sites on DOM to Hg in photoreduction of Hg(2+) to Hg(0). The potential implications of our data on environmental mercury transformation were discussed.

  4. Inhibitory effect of glutamic acid on the scale formation process using electrochemical methods.

    PubMed

    Karar, A; Naamoune, F; Kahoul, A; Belattar, N

    2016-08-01

    The formation of calcium carbonate CaCO3 in water has some important implications in geoscience researches, ocean chemistry studies, CO2 emission issues and biology. In industry, the scaling phenomenon may cause technical problems, such as reduction in heat transfer efficiency in cooling systems and obstruction of pipes. This paper focuses on the study of the glutamic acid (GA) for reducing CaCO3 scale formation on metallic surfaces in the water of Bir Aissa region. The anti-scaling properties of glutamic acid (GA), used as a complexing agent of Ca(2+) ions, have been evaluated by the chronoamperometry and electrochemical impedance spectroscopy methods in conjunction with a microscopic examination. Chemical and electrochemical study of this water shows a high calcium concentration. The characterization using X-ray diffraction reveals that while the CaCO3 scale formed chemically is a mixture of calcite, aragonite and vaterite, the one deposited electrochemically is a pure calcite. The effect of temperature on the efficiency of the inhibitor was investigated. At 30 and 40°C, a complete scaling inhibition was obtained at a GA concentration of 18 mg/L with 90.2% efficiency rate. However, the efficiency of GA decreased at 50 and 60°C.

  5. Trihalomethane formation potential of aquatic and terrestrial fulvic and humic acids: Sorption on activated carbon.

    PubMed

    Abouleish, Mohamed Y Z; Wells, Martha J M

    2015-07-15

    Humic substances (HSs) are precursors for the formation of hazardous disinfection by-products (DBPs) during chlorination of water. Various surrogate parameters have been used to investigate the generation of DBPs by HS precursors and the removal of these precursors by activated carbon treatment. Dissolved organic carbon (DOC)- and ultraviolet absorbance (UVA254)-based isotherms are commonly reported and presumed to be good predictors of the trihalomethane formation potential (THMFP). However, THMFP-based isotherms are rarely published such that the three types of parameters have not been compared directly. Batch equilibrium experiments on activated carbon were used to generate constant-initial-concentration sorption isotherms for well-characterized samples obtained from the International Humic Substances Society (IHSS). HSs representing type (fulvic acid [FA], humic acid [HA]), origin (aquatic, terrestrial), and geographical source (Nordic, Suwannee, Peat, Soil) were examined at pH6 and pH9. THMFP-based isotherms were generated and compared to determine if DOC- and UVA254-based isotherms were good predictors of the THMFP. The sorption process depended on the composition of the HSs and the chemical nature of the activated carbon, both of which were influenced by pH. Activated carbon removal of THM-precursors was pH- and HS-dependent. In some instances, the THMFP existed after UVA254 was depleted.

  6. Formation of haloacetic acids from dissolved organic matter fractions during chloramination.

    PubMed

    Hong, Ying; Song, Hocheol; Karanfil, Tanju

    2013-03-01

    The objective of this study was to investigate the roles of dissolved organic matter (DOM) fractions, pH and bromide concentration in the formation of haloacetic acids (HAA) during chloramination. DOM from two surface waters with a low (2.9 L/mg-m) and high (5.1 L/mg-m) specific UV absorbance (SUVA(254)) values was isolated and fractionated into three fractions based on the hydrophobicity [i.e., hydrophobic (HPO), transphilic (TPH) and hydrophilic (HPI)]. DOM mass balances and DBP reactivity checks were performed to characterize the effects of isolation and fractionation steps. The fractions were chloraminated at three pHs and three bromide concentrations. The results showed that pH was the most important factor controlling HAA formation and speciation. The HAA yields significantly decreased with increase in pH from 6.3 to 9.0. The impact of bromide in the formation of brominated HAA species also became less important with increasing pH, and no brominated specie was detectable at pH 9. HPO fractions of the two source waters consistently showed higher HAA yields than TPH and HPI fractions. On the other hand, HPI fractions showed higher bromine incorporation than HPO and TPH fractions. To maintain higher and relatively stable combined chlorine residuals while reducing HAA formation, water utilities may consider keeping pH above 7.5 as one strategy. This will also lower the formation of brominated HAA species which have been shown to be more cyto- and geno-toxic than their chlorinated analogs.

  7. Tube formation in the first trimester placental trophoblast cells: Differential effects of angiogenic growth factors and fatty acids.

    PubMed

    Pandya, Abhilash D; Das, Mrinal K; Sarkar, Arnab; Vilasagaram, Srinivas; Basak, Sanjay; Duttaroy, Asim K

    2016-06-01

    The study aims to investigate whether cytosolic fatty acid-binding protein-4 (FABP4) is involved in angiogenic growth factors- and fatty acid-induced tube formation in first trimester placental trophoblast cells, HTR8/SVneo. We determined the tube formation both at basal as well as stimulated levels in the absence and presence of inhibitors of FABP4 and VEGF signaling pathways. Basal level of tube formation was maximally reduced in the presence of 50 µM of FABP4 inhibitor compared with those by VEGF signaling pathway inhibitors (rapamycin, L-NAME, and p38 MAP kinase inhibitor). Whereas docosahexaenoic acid, 22:6n-3 (DHA)-, and VEGF-induced tube formation was maximally inhibited by p38 MAP kinase inhibitor (63.7 and 34.5%, respectively), however, leptin-induced tube formation was inhibited maximally by FABP4 inhibitor (50.7%). ANGPTL4 and oleic acid (OA)-induced tube formation was not blocked by any of these inhibitors. The FABP4 inhibitor inhibited cell growth stimulated by DHA, leptin, VEGF, and OA (P < 0.05) but was not affected by ANGPTL4. VEGF, leptin, and OA also increased FABP4 protein level in these cells, though the uptake of fatty acids by these cells was not affected by the presence of FABP4 inhibitor. Our data demonstrate that FABP4 may be involved in part in the basal level, and stimulated tube formation by VEGF, DHA, and leptin, whereas it has little or no effect in ANGPTL4- and OA-induced tube formation in these cells. Thus, FABP4 may play a differential role in fatty acids and angiogenic growth factors-mediated tube formation in the first trimester trophoblast cells in vitro.

  8. Angiotensin II induces phosphatidic acid formation in neonatal rat cardiac fibroblasts: evaluation of the roles of phospholipases C and D.

    PubMed

    Booz, G W; Taher, M M; Baker, K M; Singer, H A

    1994-12-21

    Phosphatidic acid has been proposed to contribute to the mitogenic actions of various growth factors. In 32P-labeled neonatal rat cardiac fibroblasts, 100 nM [Sar1]angiotensin II was shown to rapidly induce formation of 32P-phosphatidic acid. Levels peaked at 5 min (1.5-fold above control), but were partially sustained over 2 h. Phospholipase D contributed in part to phosphatidic acid formation, as 32P- or 3H-phosphatidylethanol was produced when cells labeled with [32P]H3PO4 or 1-O-[1,2- 3H]hexadecyl-2-lyso-sn-glycero-3-phosphocholine were stimulated in the presence of 1% ethanol. [Sar1]angiotensin II-induced phospholipase D activity was transient and mainly mediated through protein kinase C (PKC), since PKC downregulation reduced phosphatidylethanol formation by 68%. Residual activity may have been due to increased intracellular Ca2+, as ionomycin also activated phospholipase D in PKC-depleted cells. Phospholipase D did not fully account for [Sar1]angiotensin II-induced phosphatidic acid: 1) compared to PMA, a potent activator of phospholipase D, [Sar1]angiotensin II produced more phosphatidic acid relative to phosphatidylethanol, and 2) PKC downregulation did not affect [Sar1]angiotensin II-induced phosphatidic acid formation. The diacylglycerol kinase inhibitor R59949 depressed [Sar1]angiotensin II-induced phosphatidic acid formation by only 21%, indicating that activation of a phospholipase C and diacylglycerol kinase also can not account for the bulk of phosphatidic acid. Thus, additional pathways not involving phospholipases C and D, such as de novo synthesis, may contribute to [Sar1]angiotensin II-induced phosphatidic acid in these cells. Finally, as previously shown for [Sar1]angiotensin II, phosphatidic acid stimulated mitogen activated protein (MAP) kinase activity.(ABSTRACT TRUNCATED AT 250 WORDS)

  9. Particle size distributions in Arctic polar stratospheric clouds, growth and freezing of sulfuric acid droplets, and implications for cloud formation

    NASA Technical Reports Server (NTRS)

    Dye, James E.; Baumgardner, D.; Gandrud, B. W.; Kawa, S. R.; Kelly, K. K.; Loewenstein, M.; Ferry, G. V.; Chan, K. R.; Gary, B. L.

    1992-01-01

    The paper uses particle size and volume measurements obtained with the forward scattering spectrometer probe model 300 during January and February 1989 in the Airborne Arctic Stratospheric Experiment to investigate processes important in the formation and growth of polar stratospheric cloud (PSC) particles. It is suggested on the basis of comparisons of the observations with expected sulfuric acid droplet deliquescence that in the Arctic a major fraction of the sulfuric acid droplets remain liquid until temperatures at least as low as 193 K. It is proposed that homogeneous freezing of the sulfuric acid droplets might occur near 190 K and might play a role in the formation of PSCs.

  10. Ultrafast formation of the benzoic acid triplet upon ultraviolet photolysis and its sequential photodissociation in solution

    SciTech Connect

    Yang Chunfan; Su Hongmei; Sun Xuezhong; George, Michael W.

    2012-05-28

    Time-resolved infrared (TR-IR) absorption spectroscopy in both the femtosecond and nanosecond time domain has been applied to examine the photolysis of benzoic acid in acetonitrile solution following either 267 nm or 193 nm excitation. By combining the ultrafast and nanosecond TR-IR measurements, both the excited states and the photofragments have been detected and key mechanistic insights were obtained. We show that the solvent interaction modifies the excited state relaxation pathways and thus the population dynamics, leading to different photolysis behavior in solution from that observed in the gas phase. Vibrational energy transfer to solvents dissipates excitation energy efficiently, suppressing the photodissociation and depopulating the excited S{sub 2} or S{sub 3} state molecules to the lowest T{sub 1} state with a rate of {approx}2.5 ps after a delayed onset of {approx}3.7 ps. Photolysis of benzoic acid using 267 nm excitation is dominated by the formation of the T{sub 1} excited state and no photofragments could be detected. The results from TR-IR experiments using higher energy of 193 nm indicate that photodissociation proceeds more rapidly than the vibrational energy transfer to solvents and C-C bond fission becomes the dominant relaxation pathway in these experiments as featured by the prominent observation of the COOH photofragments and negligible yield of the T{sub 1} excited state. The measured ultrafast formation of T{sub 1} excited state supports the existence of the surface intersections of S{sub 2}/S{sub 1}, S{sub 2}/T{sub 2}, and S{sub 1}/T{sub 1}/T{sub 2}, and the large T{sub 1} quantum yield of {approx}0.65 indicates the importance of the excited state depopulation to triplet manifold as the key factor affecting the photophysical and photochemical behavior of the monomeric benzoic acid.

  11. Sialic Acid on the Glycosylphosphatidylinositol Anchor Regulates PrP-mediated Cell Signaling and Prion Formation*

    PubMed Central

    Bate, Clive; Nolan, William; Williams, Alun

    2016-01-01

    The prion diseases occur following the conversion of the cellular prion protein (PrPC) into disease-related isoforms (PrPSc). In this study, the role of the glycosylphosphatidylinositol (GPI) anchor attached to PrPC in prion formation was examined using a cell painting technique. PrPSc formation in two prion-infected neuronal cell lines (ScGT1 and ScN2a cells) and in scrapie-infected primary cortical neurons was increased following the introduction of PrPC. In contrast, PrPC containing a GPI anchor from which the sialic acid had been removed (desialylated PrPC) was not converted to PrPSc. Furthermore, the presence of desialylated PrPC inhibited the production of PrPSc within prion-infected cortical neurons and ScGT1 and ScN2a cells. The membrane rafts surrounding desialylated PrPC contained greater amounts of sialylated gangliosides and cholesterol than membrane rafts surrounding PrPC. Desialylated PrPC was less sensitive to cholesterol depletion than PrPC and was not released from cells by treatment with glimepiride. The presence of desialylated PrPC in neurons caused the dissociation of cytoplasmic phospholipase A2 from PrP-containing membrane rafts and reduced the activation of cytoplasmic phospholipase A2. These findings show that the sialic acid moiety of the GPI attached to PrPC modifies local membrane microenvironments that are important in PrP-mediated cell signaling and PrPSc formation. These results suggest that pharmacological modification of GPI glycosylation might constitute a novel therapeutic approach to prion diseases. PMID:26553874

  12. Resistance to benzalkonium chloride, peracetic acid and nisin during formation of mature biofilms by Listeria monocytogenes.

    PubMed

    Saá Ibusquiza, P; Herrera, J J R; Cabo, M L

    2011-05-01

    Increase of resistance to the application of benzalkonium chloride (BAC), peracetic acid (PA) and nisin during biofilm formation at 25 °C by three strains of Listeria monocytogenes (CECT 911, CECT 4032, CECT 5873 and BAC-adapted CECT 5873) in different scenarios was compared. For this purpose, resistance after 4 and 11-days of biofilm formation was quantified in terms of lethal dose 90% values (LD(90)), determined according with a dose-response logistic mathematical model. Microscopic analyses after 4 and 11-days of L. monocytogenes biofilm formation were also carried out. Results demonstrated a relation between the microscopic structure and the resistance to the assayed biocides in matured biofilms. The worst cases being biofilms formed by the strain 4032 (in both stainless steel and polypropylene), which showed a complex "cloud-type" structure that correlates with the highest resistance of this strain against the three biocides during biofilm maturation. However, that increase in resistance and complexity appeared not to be dependent on initial bacterial adherence, thus indicating mature biofilms rather than planctonic cells or early-stage biofilms must be considered when disinfection protocols have to be optimized. PA seemed to be the most effective of the three disinfectants used for biofilms. We hypothesized both its high oxidizing capacity and low molecular size could suppose an advantage for its penetration inside the biofilm. We also demonstrated that organic material counteract with the biocides, thus indicating the importance of improving cleaning protocols. Finally, by comparing strains 5873 and 5873 adapted to BAC, several adaptative cross-responses between BAC and nisin or peracetic acid were identified.

  13. Potential origin and formation for molecular components of humic acids in soils

    NASA Astrophysics Data System (ADS)

    Hatcher, Patrick; DiDonato, Nicole; Waggoner, Derek

    2016-04-01

    Humification is defined as the process by which plant and microbial debris are transformed in to humic substances. Proposed pathways for the formation of humic substances, include the lignin and lignin decomposition theories, the lignin-polyphenol theory as well as the melanoidin pathway. It is generally accepted that a combination of several of these pathways with some modifications may be responsible for producing humic substances. The current study examines humic acids from numerous soil samples to demonstrate their molecular composition. In addition we provide an explanation for the formation of these molecules that introduces a new perspective of the humification process. Our work utilizes advanced analytical techniques such as ESI-FTICR-MS and solid state NMR to more completely characterize humic acids at the molecular level. Methods Humic acids were extracted from soils using 0.5 M NaOH followed by treatment with a Dowex™ ion-exchange resin to remove sodium ions. Solid State 13C NMR spectra were obtained on a Bruker 400 MHz Avance II spectrometer equipped with a 4 mm solid state MAS probe. ESI-FTICR-MS analysis was conducted in the negative ion mode on a Bruker Daltonics 12 Tesla Apex Qe FTICR-MS instrument equipped with an Apollo II ESI source. Results: Soil humic acids from numerous soils were investigated in this study. The molecular formulas calculated from ultrahigh resolution mass spectra of well humified soils fall clearly into two predominant regions consisting of condensed aromatic molecules as well as high H/C, low O/C carboxyl-containing aliphatic molecules (CCAM). In contrast, the spectral data for humic acids from a poorly humified spodosol soil show a less dramatic separation of these regions, with relatively more molecular formula plotting in the lignin-like region and relatively fewer condensed aromatic molecules. From the mass spectral observations made for the humic acids, we can readily discern a relationship based on degree of

  14. Enigmatic Isovaline: Investigating the Stability, Racemization, and Formation of a Non-biological Meteoritic Amino Acid

    NASA Technical Reports Server (NTRS)

    Hudson, Reggie; Moore, Marla; Lewis, Ariel; Dworkin, Jason

    2008-01-01

    Among the Murchison meteoritic amino acids, isovaline stands out as being both nonbiological (non-protein) and having a relatively high abundance. While approximately equal amounts of D- and L-isovaline have been reported in Murchison and other CM meteorites, the molecule's structure appears to prohibit its racemization in aqueous solutions. We recently have investigated the low-temperature solid-phase chemistry of both isovaline and valine with an eye toward each molecule's formation, stability, and possible interconversions of D and L enantiomers. Ion-irradiated isovaline- and valinecontaining ices were examined by IR spectroscopy and highly-sensitive liquid chromatography/time-of-flight mass spectral methods to assess both amino acid destruction and racemization. Samples were studied in the presence and in the absence of water-ice, and the destruction of both isovaline and valine was measured as a function of radiation dose. In addition, we have undertaken experiments to synthesize isovaline, valine, and their amino acid isomers by solid-phase radiation-chemical pathways other than the oft-invoked Strecker process. This presentation will review and summarize some of our recent findings. -- Our work has been supported by a grant to the Goddard Center for Astrobiology through the NASA Astrobiology Institute. Experiments were performed in the Cosmic Ice Laboratory (RLH, MHM, AL) and the Astrobiology Analytical Laboratory (JPD, DPG) at the NASA Goddard Space Flight Center.

  15. Contribution of natural and anthropogenic emissions to acid precipitation formation in the Mexico City Metropolitan Area

    SciTech Connect

    Garcia, L.; Barrera, G.; Castellanos, L.; Moreno, D.

    1996-12-31

    The emissions of precursor compounds that contribute significantly the formation of acid precipitation in urban areas are associated with the burning of fossils fuels from mobile, area and point sources. In Mexico City, these include services, institutions and residences aggregated as area sources, as well as industrial point sources, including smelting, refinement of petroleum and power generation. In addition, dusts from soil erosion and lack of vegetation in the urban landscape contribute to modification of natural rain water. It is common knowledge that acid precipitation characterizes a large variety of compounds, as much related to precursor emissions as to prevailing environmental factors. This study attempts to establish the contribution of natural and anthropogenic emissions and meteorological conditions during the rainy season by analysis of spatial and temporal distributions, as of different ions in solution with rain water, as well as the modeling of wind patterns, as represented by using the arc/info software. This study`s results also show the geographic areas impacted by the acid rain phenomenon and the acidification rates in the Mexico City Metropolitan Area during the past 3 years.

  16. Detection and formation scenario of citric acid, pyruvic acid, and other possible metabolism precursors in carbonaceous meteorites.

    PubMed

    Cooper, George; Reed, Chris; Nguyen, Dang; Carter, Malika; Wang, Yi

    2011-08-23

    Carbonaceous meteorites deliver a variety of organic compounds to Earth that may have played a role in the origin and/or evolution of biochemical pathways. Some apparently ancient and critical metabolic processes require several compounds, some of which are relatively labile such as keto acids. Therefore, a prebiotic setting for any such individual process would have required either a continuous distant source for the entire suite of intact precursor molecules and/or an energetic and compact local synthesis, particularly of the more fragile members. To date, compounds such as pyruvic acid, oxaloacetic acid, citric acid, isocitric acid, and α-ketoglutaric acid (all members of the citric acid cycle) have not been identified in extraterrestrial sources or, as a group, as part of a "one pot" suite of compounds synthesized under plausibly prebiotic conditions. We have identified these compounds and others in carbonaceous meteorites and/or as low temperature (laboratory) reaction products of pyruvic acid. In meteorites, we observe many as part of three newly reported classes of compounds: keto acids (pyruvic acid and homologs), hydroxy tricarboxylic acids (citric acid and homologs), and tricarboxylic acids. Laboratory syntheses using (13)C-labeled reactants demonstrate that one compound alone, pyruvic acid, can produce several (nonenzymatic) members of the citric acid cycle including oxaloacetic acid. The isotopic composition of some of the meteoritic keto acids points to interstellar or presolar origins, indicating that such compounds might also exist in other planetary systems.

  17. Formation of stable radicals in catechin/nitrous acid systems: participation of dinitrosocatechin.

    PubMed

    Morina, Filis; Takahama, Umeo; Mojović, Miloš; Popović-Bijelić, Ana; Veljović-Jovanović, Sonja

    2016-03-01

    Catechins are transformed into dinitrosocatechins (diNOcats) and then oxidized to the quinones by salivary nitrite under conditions simulating the stomach. This manuscript deals with formation of stable radicals in the NO group of diNOcat during nitrite-induced oxidation of (+)-catechin and diNOcat at pH 2. We postulated two mechanisms for the stable radical formation; one is nitrous acid-induced oxidation of diNOcat in the A-ring, and the other intermolecular charge transfer from the A-ring of diNOcat and/or diNOcat quinone to the quinone moiety of the B-ring of diNOcat quinone. In addition, an unstable phenoxyl radical, which might be transformed into quinone, was also produced, accompanying the formation of the stable radical on the NO group. Taking the above results into account, we mainly focus on the adverse effects of the radicals and quinone, which may be produced from (+)-catechin in the stomach under the conditions of high salivary nitrite concentrations.

  18. Peptide bond formation does not involve acid-base catalysis by ribosomal residues.

    PubMed

    Bieling, Peter; Beringer, Malte; Adio, Sarah; Rodnina, Marina V

    2006-05-01

    Ribosomes catalyze the formation of peptide bonds between aminoacyl esters of transfer RNAs within a catalytic center composed of ribosomal RNA only. Here we show that the reaction of P-site formylmethionine (fMet)-tRNA(fMet) with a modified A-site tRNA substrate, Phelac-tRNA(Phe), in which the nucleophilic amino group is replaced with a hydroxyl group, does not show the pH dependence observed with small substrate analogs such as puromycin and hydroxypuromycin. This indicates that acid-base catalysis by ribosomal residues is not important in the reaction with the full-size substrate. Rather, the ribosome catalyzes peptide bond formation by positioning the tRNAs, or their 3' termini, through interactions with rRNA that induce and/or stabilize a pH-insensitive conformation of the active site and provide a preorganized environment facilitating the reaction. The rate of peptide bond formation with unmodified Phe-tRNA(Phe) is estimated to be >300 s(-1).

  19. Effects of gaseous sulphuric acid on diesel exhaust nanoparticle formation and characteristics.

    PubMed

    Rönkkö, Topi; Lähde, Tero; Heikkilä, Juha; Pirjola, Liisa; Bauschke, Ulrike; Arnold, Frank; Schlager, Hans; Rothe, Dieter; Yli-Ojanperä, Jaakko; Keskinen, Jorma

    2013-10-15

    Diesel exhaust gaseous sulphuric acid (GSA) concentrations and particle size distributions, concentrations, and volatility were studied at four driving conditions with a heavy duty diesel engine equipped with oxidative exhaust after-treatment. Low sulfur fuel and lubricant oil were used in the study. The concentration of the exhaust GSA was observed to vary depending on the engine driving history and load. The GSA affected the volatile particle fraction at high engine loads; higher GSA mole fraction was followed by an increase in volatile nucleation particle concentration and size as well as increase of size of particles possessing nonvolatile core. The GSA did not affect the number of nonvolatile particles. At low and medium loads, the exhaust GSA concentration was low and any GSA driven changes in particle population were not observed. Results show that during the exhaust cooling and dilution processes, besides critical in volatile nucleation particle formation, GSA can change the characteristics of all nucleation mode particles. Results show the dual nature of the nucleation mode particles so that the nucleation mode can include simultaneously volatile and nonvolatile particles, and fulfill the previous results for the nucleation mode formation, especially related to the role of GSA in formation processes.

  20. A chamber study of the influence of boreal BVOC emissions and sulfuric acid on nanoparticle formation rates at ambient concentrations

    NASA Astrophysics Data System (ADS)

    Dal Maso, M.; Liao, L.; Wildt, J.; Kiendler-Scharr, A.; Kleist, E.; Tillmann, R.; Sipilä, M.; Hakala, J.; Lehtipalo, K.; Ehn, M.; Kerminen, V.-M.; Kulmala, M.; Worsnop, D.; Mentel, T.

    2016-02-01

    Aerosol formation from biogenic and anthropogenic precursor trace gases in continental background areas affects climate via altering the amount of available cloud condensation nuclei. Significant uncertainty still exists regarding the agents controlling the formation of aerosol nanoparticles. We have performed experiments in the Jülich plant-atmosphere simulation chamber with instrumentation for the detection of sulfuric acid and nanoparticles, and present the first simultaneous chamber observations of nanoparticles, sulfuric acid, and realistic levels and mixtures of biogenic volatile compounds (BVOCs). We present direct laboratory observations of nanoparticle formation from sulfuric acid and realistic BVOC precursor vapour mixtures performed at atmospherically relevant concentration levels. We directly measured particle formation rates separately from particle growth rates. From this, we established that in our experiments, the formation rate was proportional to the product of sulfuric acid and biogenic VOC emission strength. The formation rates were consistent with a mechanism in which nucleating BVOC oxidation products are rapidly formed and activate with sulfuric acid. The growth rate of nanoparticles immediately after birth was best correlated with estimated products resulting from BVOC ozonolysis.

  1. Mutual Amino Acid Catalysis in Salt-Induced Peptide Formation Supports this Mechanism's Role in Prebiotic Peptide Evolution

    NASA Astrophysics Data System (ADS)

    Suwannachot, Yuttana; Rode, Bernd M.

    1999-10-01

    The presence of some amino acids and dipeptides under the conditions of the salt-induced peptide formation reaction (aqueous solution at 85 °C, Cu(II) and NaCl) has been found to catalyze the formation of homopeptides of other amino acids, which are otherwise produced only in traces or not at all by this reaction. The condensation of Val, Leu and Lys to form their homodipeptides can occur to a considerable extent due to catalytic effects of other amino acids and related compounds, among which glycine, histidine, diglycine and diketopiperazine exhibit the most remarkable activity. These findings also lead to a modification of the table of amino acid sequences preferentially formed by the salt-induced peptide formation (SIPF) reaction, previously used for a comparison with the sequence preferences in membrane proteins of primitive organisms

  2. Formation of Amino Acids on the Sonolysis of Aqueous Solutions Containing Acetic Acid, Methane, or Carbon Dioxide, in the Presence of Nitrogen Gas.

    PubMed

    Dharmarathne, Leena; Grieser, Franz

    2016-01-21

    The sonolysis of aqueous solutions containing acetic acid, methane, or carbon dioxide in the presence of nitrogen gas was found to produce a number of different amino acids at a rate of ∼1 to 100 nM/min, using ultrasound at an operating power of 70 W and 355 kHz. Gas-phase elementary reactions are suggested, and discussed, to account for the formation of the complex biomolecules from the low molar mass solutes used. On the basis of the results, a new hypothesis is presented to explain the formation of amino acids under primitive atmospheric conditions and how their formation may be linked to the eventual abiotic genesis of life on Earth.

  3. Effects of irradiation on trans fatty acids formation in ground beef

    NASA Astrophysics Data System (ADS)

    Brito, Mônica S.; Villavicencio, Anna Lúcia C. H.; Mancini-filho, Jorge

    2002-03-01

    In order to give the consumer the assurance that meat processed by irradiation is a safe product, a great deal of research has been developed in the world. The effect of irradiation on the hygienic quality of meat and meat products is considered as related to the control of meat-borne parasites of humans; elimination of pathogens from fresh meat and poultry; and elimination of pathogens from processed meat. Lipid oxidation and associated changes are the major causes of the quality deterioration of meat during storage. Irradiation of lipids induces the production of free radicals, which react with oxygen, leading to the formation of carbonyls, responsible for alterations in food nutritional and sensorial characteristics. Trans fatty acids are present in ground beef and can also be formed during its processing. Interestingly, the trans fatty acids, due to their chemical and physical characteristics, show more resistance to the oxidizing process. This property motivated us to investigate the level of the trans fatty acids, as well as the level of oxidation in irradiated ground beef. Irradiation of ground beef was performed by gamma rays from a 60Co source. The applied radiation doses were 0; 1.0; 2.0; 3.0; 4.0; 5.0; 6.0; 7.0 and 8.0 kGy. Lipid peroxidation in terms of TBA number and carbonyl content was monitored during storage. The sample characteristics and trans fatty acids composition were measured, following irradiation and after 60 and 90 days of storage at -10°C.

  4. Boric Acid Reduces the Formation of DNA Double Strand Breaks and Accelerates Wound Healing Process.

    PubMed

    Tepedelen, Burcu Erbaykent; Soya, Elif; Korkmaz, Mehmet

    2016-12-01

    Boron is absorbed by the digestive and respiratory system, and it was considered that it is converted to boric acid (BA), which was distributed to all tissues above 90 %. The biochemical essentiality of boron element is caused by boric acid because it affects the activity of several enzymes involved in the metabolism. DNA damage repair mechanisms and oxidative stress regulation is quite important in the transition stage from normal to cancerous cells; thus, this study was conducted to investigate the protective effect of boric acid on DNA damage and wound healing in human epithelial cell line. For this purpose, the amount of DNA damage occurred with irinotecan (CPT-11), etoposide (ETP), doxorubicin (Doxo), and H2O2 was determined by immunofluorescence through phosphorylation of H2AX((Ser139)) and pATM((Ser1981)) in the absence and presence of BA. Moreover, the effect of BA on wound healing has been investigated in epithelial cells treated with these agents. Our results demonstrated that H2AX((Ser139)) foci numbers were significantly decreased in the presence of BA while wound healing was accelerated by BA compared to that in the control and only drug-treated cells. Eventually, the results indicate that BA reduced the formation of DNA double strand breaks caused by agents as well as improving the wound healing process. Therefore, we suggest that boric acid has important therapeutical effectiveness and may be used in the treatment of inflammatory diseases where oxidative stress and wound healing process plays an important role.

  5. 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.

  6. Retinoic Acid Signaling Is Essential for Valvulogenesis by Affecting Endocardial Cushions Formation in Zebrafish Embryos.

    PubMed

    Li, Junbo; Yue, Yunyun; Zhao, Qingshun

    2016-02-01

    Retinoic acid (RA) plays important roles in many stages of heart morphogenesis. Zebrafish embryos treated with exogenous RA display defective atrio-ventricular canal (AVC) specification. However, whether endogenous RA signaling takes part in cardiac valve formation remains unknown. Herein, we investigated the role of RA signaling in cardiac valve development by knocking down aldh1a2, the gene encoding an enzyme that is mainly responsible for RA synthesis during early development, in zebrafish embryos. The results showed that partially knocking down aldh1a2 caused defective formation of primitive cardiac valve leaflets at 108 hpf (hour post-fertilization). Inhibiting endogenous RA signaling by 4-diethylaminobenzal-dehyde revealed that 16-26 hpf was a key time window when RA signaling affects the valvulogenesis. The aldh1a2 morphants had defective formation of endocardial cushion (EC) at 76 hpf though they had almost normal hemodynamics and cardiac chamber specification at early development. Examining the expression patterns of AVC marker genes including bmp4, bmp2b, nppa, notch1b, and has2, we found the morphants displayed abnormal development of endocardial AVC but almost normal development of myocardial AVC at 50 hpf. Being consistent with the reduced expression of notch1b in endocardial AVC, the VE-cadherin gene cdh5, the downstream gene of Notch signaling, was ectopically expressed in AVC of aldh1a2 morphants at 50 hpf, and overexpression of cdh5 greatly affected the formation of EC in the embryos at 76 hpf. Taken together, our results suggest that RA signaling plays essential roles in zebrafish cardiac valvulogenesis.

  7. On the composition of ammonia-sulfuric-acid ion clusters during aerosol particle formation

    NASA Astrophysics Data System (ADS)

    Schobesberger, S.; Franchin, A.; Bianchi, F.; Rondo, L.; Duplissy, J.; Kürten, A.; Ortega, I. K.; Metzger, A.; Schnitzhofer, R.; Almeida, J.; Amorim, A.; Dommen, J.; Dunne, E. M.; Ehn, M.; Gagné, S.; Ickes, L.; Junninen, H.; Hansel, A.; Kerminen, V.-M.; Kirkby, J.; Kupc, A.; Laaksonen, A.; Lehtipalo, K.; Mathot, S.; Onnela, A.; Petäjä, T.; Riccobono, F.; Santos, F. D.; Sipilä, M.; Tomé, A.; Tsagkogeorgas, G.; Viisanen, Y.; Wagner, P. E.; Wimmer, D.; Curtius, J.; Donahue, N. M.; Baltensperger, U.; Kulmala, M.; Worsnop, D. R.

    2015-01-01

    The formation of particles from precursor vapors is an important source of atmospheric aerosol. Research at the Cosmics Leaving OUtdoor Droplets (CLOUD) facility at CERN tries to elucidate which vapors are responsible for this new-particle formation, and how in detail it proceeds. Initial measurement campaigns at the CLOUD stainless-steel aerosol chamber focused on investigating particle formation from ammonia (NH3) and sulfuric acid (H2SO4). Experiments were conducted in the presence of water, ozone and sulfur dioxide. Contaminant trace gases were suppressed at the technological limit. For this study, we mapped out the compositions of small NH3-H2SO4 clusters over a wide range of atmospherically relevant environmental conditions. We covered [NH3] in the range from < 2 to 1400 pptv, [H2SO4] from 3.3 × 106 to 1.4 × 109 cm-3 (0.1 to 56 pptv), and a temperature range from -25 to +20 °C. Negatively and positively charged clusters were directly measured by an atmospheric pressure interface time-of-flight (APi-TOF) mass spectrometer, as they initially formed from gas-phase NH3 and H2SO4, and then grew to larger clusters containing more than 50 molecules of NH3 and H2SO4, corresponding to mobility-equivalent diameters greater than 2 nm. Water molecules evaporate from these clusters during sampling and are not observed. We found that the composition of the NH3-H2SO4 clusters is primarily determined by the ratio of gas-phase concentrations [NH3] / [H2SO4], as well as by temperature. Pure binary H2O-H2SO4 clusters (observed as clusters of only H2SO4) only form at [NH3] / [H2SO4] < 0.1 to 1. For larger values of [NH3] / [H2SO4], the composition of NH3-H2SO4 clusters was characterized by the number of NH3 molecules m added for each added H2SO4 molecule n (Δm/Δ n), where n is in the range 4-18 (negatively charged clusters) or 1-17 (positively charged clusters). For negatively charged clusters, Δ m/Δn saturated between 1 and 1.4 for [NH3] / [H2SO4] > 10. Positively

  8. On the composition of ammonia-sulfuric acid clusters during aerosol particle formation

    NASA Astrophysics Data System (ADS)

    Schobesberger, S.; Franchin, A.; Bianchi, F.; Rondo, L.; Duplissy, J.; Kürten, A.; Ortega, I. K.; Metzger, A.; Schnitzhofer, R.; Almeida, J.; Amorim, A.; Dommen, J.; Dunne, E. M.; Ehn, M.; Gagné, S.; Ickes, L.; Junninen, H.; Hansel, A.; Kerminen, V.-M.; Kirkby, J.; Kupc, A.; Laaksonen, A.; Lehtipalo, K.; Mathot, S.; Onnela, A.; Petäjä, T.; Riccobono, F.; Santos, F. D.; Sipilä, M.; Tomé, A.; Tsagkogeorgas, G.; Viisanen, Y.; Wagner, P. E.; Wimmer, D.; Curtius, J.; Donahue, N. M.; Baltensperger, U.; Kulmala, M.; Worsnop, D. R.

    2014-05-01

    The formation of particles from precursor vapors is an important source of atmospheric aerosol. Research at the Cosmics Leaving OUtdoor Droplets (CLOUD) facility at CERN tries to elucidate which vapors are responsible for this new particle formation, and how in detail it proceeds. Initial measurement campaigns at the CLOUD stainless-steel aerosol chamber focused on investigating particle formation from ammonia (NH3) and sulfuric acid (H2SO4). Experiments were conducted in the presence of water, ozone and sulfur dioxide. Contaminant trace gases were suppressed at the technological limit. For this study, we mapped out the compositions of small NH3-H2SO4 clusters over a wide range of atmospherically relevant environmental conditions. We covered [NH3] in the range from <2 to 1400 pptv, [H2SO4] from 3.3 × 106 to 1.4 × 109 cm-3, and a temperature range from -25 to +20 °C. Negatively and positively charged clusters were directly measured by an atmospheric pressure interface time-of-flight (APi-TOF) mass spectrometer, as they initially formed from gas-phase NH3 and H2SO4, and then grew to larger clusters containing more than 50 molecules of NH3 and H2SO4, corresponding to mobility-equivalent diameters greater than 2 nm. Water molecules evaporate from these clusters during sampling and are not observed. We found that the composition of the NH3-H2SO4 clusters is primarily determined by the ratio of gas-phase concentrations [NH3] / [H2SO4], as well as by temperature. Pure binary H2O-H2SO4 clusters (observed as clusters of only H2SO4) only form at [NH3] / [H2SO4]<0.1 to 1. For larger values of [NH3] / [H2SO4], the composition of NH3-H2SO4 clusters was characterized by the number of NH3 molecules m added for each added H2SO4 molecule n (Δm / Δn), where n is in the range 4-18 (negatively charged clusters) or 1-17 (positively charged clusters). For negatively charged clusters, Δm / Δn saturated between 1 and 1.4 for [NH3] / [H2SO4]>10. Positively charged clusters grew on

  9. Ilex paraguariensis and its main component chlorogenic acid inhibit fructose formation of advanced glycation endproducts with amino acids at conditions compatible with those in the digestive system.

    PubMed

    Bains, Yasmin; Gugliucci, Alejandro

    2017-03-01

    We have previously shown that Ilex paraguariensis extracts have potent antiglycation actions. Associations of excess free fructose consumption with inflammatory diseases have been proposed to be mediated through in situ enteral formation of fructose AGEs, which, after being absorbed may contribute to inflammatory diseases via engagement of RAGE. In this proof of principle investigation we show fluorescent AGE formation between amino acids (Arg, Lys, Gly at 10-50mM) and fructose (10-50mM) under time, temperature, pH and concentrations compatible with the digestive system lumen and its inhibition by Ilex paraguariensis extracts. Incubation of amino acids with fructose (but not glucose) leads to a time dependent formation of AGE fluorescence, already apparent after just 1h incubation, a time frame well compatible with the digestive process. Ilex paraguariensis (mate tea) inhibited AGE formation by 83% at 50μl/ml (p<0.001). Its main phenolics, caffeic acid and cholorogenic acid were as potent as aminoguanidine-a specific antiglycation agent: IC50 of 0.9mM (p<0.001). Our results suggest that AGE adducts form between fructose and amino acids at times and concentrations plausibly found in the intestines. The reaction is inhibited by mate tea and its individual phenolics (caffeic acid and chlorogenic acids). The study provides the first evidence for the proposed mechanism to explain epidemiological correlations between excess fructose consumption and inflammatory diseases. Enteral fructose-AGE formation would be inhibited by co-intake of Ilex paraguariensis, and potentially other beverages, fruits and vegetables that contain comparable concentrations of phenolics as in IP (mate tea).

  10. Gas-phase enthalpies of formation and enthalpies of sublimation of amino acids based on isodesmic reaction calculations.

    PubMed

    Dorofeeva, Olga V; Ryzhova, Oxana N

    2014-05-15

    Accurate gas-phase enthalpies of formation (ΔfH298°) of 20 common α-amino acids, seven uncommon amino acids, and three small peptides were calculated by combining G4 theory calculations with an isodesmic reaction approach. The internal consistency over a set of ΔfH298°(g) values was achieved by sequential adjustment of their values through the isodesmic reactions. Four amino acids, alanine, β-alanine, sarcosine, and glycine, with reliable internally self-consistent experimental data, were chosen as the key reference compounds. These amino acids together with about 100 compounds with reliable experimental data (their accuracy was supported by G4 calculations) were used to estimate the enthalpies of formation of remaining amino acids. All of the amino acids with the previously established enthalpies of formation were later used as the reference species in the isodesmic reactions for the other amino acids. A systematic comparison was made of 14 experimentally determined enthalpies of formation with the results of calculations. The experimental enthalpies of formation for 10 amino acids were reproduced with good accuracy, but the experimental and calculated values for 4 compounds differed by 11–21 kJ/mol. For these species, the theoretical ΔfH298°(g) values were suggested as more reliable than the experimental values. On the basis of theoretical results, the recommended values for the gas-phase enthalpies of formation were also provided for amino acids for which the experimental ΔfH298°(g) were not available. The enthalpies of sublimation were evaluated for all compounds by taking into account the literature data on the solid-phase enthalpies of formation and the ΔfH298°(g) values recommended in our work. A special attention was paid to the accurate prediction of enthalpies of formation of amino acids from the atomization reactions. The problems associated with conformational flexibility of these compounds and harmonic treatment of low frequency torsional

  11. Foam-stabilizing effects and cling formation patterns of iso-alpha-acids and reduced iso-alpha-acids in lager beer.

    PubMed

    Kunimune, Takeshi; Shellhammer, Thomas H

    2008-09-24

    Foam-stabilizing properties and cling formation patterns of iso-alpha-acids and reduced iso-alpha-acids were investigated using an unhopped lager beer. Unhopped beer was dosed with iso-alpha-acid (Iso), rho-iso-alpha-acid (Rho), tetrahydro-iso-alpha-acid (Tetra), and hexahydro-iso-alpha-acid (Hexa), separately, over a range of concentrations from 2 to 10 ppm. A uniform foam was created by Inpack 2000 Flasher Head and was measured by a NIBEM Foam Stability Tester (NIBEM-TPH) followed by a NIBEM Cling Meter (NIBEM-CLM) to determine the relationship between the concentration and NIBEM-30 and the cling formation ability of each compound. The foam-stabilizing power was determined to be Tetra, Hexa, Iso, and Rho from the strongest to weakest. Linear regression models were created using the NIBEM-TPH data set, and on the basis of 95% confidence intervals, the foam stability of Tetra or Hexa became significantly larger than that of Iso when 2.4 or 4.2 ppm of Tetra or Hexa was used as a replacement for Iso, respectively. Cling formation patterns could be categorized into three groups: "ring", "mesh", and "powdery". The control beer had the lowest foam stability and did not yield any foam cling.

  12. Modeling the effect of relative humidity on nitrous acid formation in the Houston area

    NASA Astrophysics Data System (ADS)

    Diao, Lijun; Roy, Anirban; Czader, Beata; Pan, Shuai; Jeon, Wonbae; Souri, Amir Hossein; Choi, Yunsoo

    2016-04-01

    The field and laboratory based relative humidity (RH) impact on nitrous acid (HONO) heterogeneous reaction has not been considered in chemical transport models. This study parameterized this dependency into the Community Multiscale Air Quality (CMAQ) model. In view of the positive linear correlation between the reaction rate and RH, the HONO heterogeneous reaction rate constants were respectively scaled by the factors of RH/30 and RH/40. Two corresponding sensitivity tests were carried out in the period of September 2013 in Houston. Both tests significantly improved modeled HONO concentrations and reduced the bias for NO2 in comparison with observations. However, the model is still not capable of reproducing the high HONO concentrations in the morning rush hours. Further work is needed to explore the underlying mechanisms for the early morning HONO formation.

  13. Gas-Phase Formation Rates of Nitric Acid and Its Isomers Under Urban Conditions

    NASA Technical Reports Server (NTRS)

    Okumura, M.; Mollner, A. K.; Fry, J. L.; Feng, L.

    2005-01-01

    Ozone formation in urban smog is controlled by a complex set of reactions which includes radical production from photochemical processes, catalytic cycles which convert NO to NO2, and termination steps that tie up reactive intermediates in long-lived reservoirs. The reaction OH + NO2 + M -4 HONO2 + M (la) is a key termination step because it transforms two short-lived reactive intermediates, OH and NO2, into relatively long-lived nitric acid. Under certain conditions (low VOC/NOx), ozone production in polluted urban airsheds can be highly sensitive to this reaction, but the rate parameters are not well constrained. This report summarizes the results of new laboratory studies of the OH + NO2 + M reaction including direct determination of the overall rate constant and branching ratio for the two reaction channels under atmospherically relevant conditions.

  14. Experimental particle formation rates spanning tropospheric sulfuric acid and ammonia abundances, ion production rates, and temperatures

    NASA Astrophysics Data System (ADS)

    Kürten, Andreas; Bianchi, Federico; Almeida, Joao; Kupiainen-Määttä, Oona; Dunne, Eimear M.; Duplissy, Jonathan; Williamson, Christina; Barmet, Peter; Breitenlechner, Martin; Dommen, Josef; Donahue, Neil M.; Flagan, Richard C.; Franchin, Alessandro; Gordon, Hamish; Hakala, Jani; Hansel, Armin; Heinritzi, Martin; Ickes, Luisa; Jokinen, Tuija; Kangasluoma, Juha; Kim, Jaeseok; Kirkby, Jasper; Kupc, Agnieszka; Lehtipalo, Katrianne; Leiminger, Markus; Makhmutov, Vladimir; Onnela, Antti; Ortega, Ismael K.; Petäjä, Tuukka; Praplan, Arnaud P.; Riccobono, Francesco; Rissanen, Matti P.; Rondo, Linda; Schnitzhofer, Ralf; Schobesberger, Siegfried; Smith, James N.; Steiner, Gerhard; Stozhkov, Yuri; Tomé, António; Tröstl, Jasmin; Tsagkogeorgas, Georgios; Wagner, Paul E.; Wimmer, Daniela; Ye, Penglin; Baltensperger, Urs; Carslaw, Ken; Kulmala, Markku; Curtius, Joachim

    2016-10-01

    Binary nucleation of sulfuric acid and water as well as ternary nucleation involving ammonia are thought to be the dominant processes responsible for new particle formation (NPF) in the cold temperatures of the middle and upper troposphere. Ions are also thought to be important for particle nucleation in these regions. However, global models presently lack experimentally measured NPF rates under controlled laboratory conditions and so at present must rely on theoretical or empirical parameterizations. Here with data obtained in the European Organization for Nuclear Research CLOUD (Cosmics Leaving OUtdoor Droplets) chamber, we present the first experimental survey of NPF rates spanning free tropospheric conditions. The conditions during nucleation cover a temperature range from 208 to 298 K, sulfuric acid concentrations between 5 × 105 and 1 × 109 cm-3, and ammonia mixing ratios from zero added ammonia, i.e., nominally pure binary, to a maximum of 1400 parts per trillion by volume (pptv). We performed nucleation studies under pure neutral conditions with zero ions being present in the chamber and at ionization rates of up to 75 ion pairs cm-3 s-1 to study neutral and ion-induced nucleation. We found that the contribution from ion-induced nucleation is small at temperatures between 208 and 248 K when ammonia is present at several pptv or higher. However, the presence of charges significantly enhances the nucleation rates, especially at 248 K with zero added ammonia, and for higher temperatures independent of NH3 levels. We compare these experimental data with calculated cluster formation rates from the Atmospheric Cluster Dynamics Code with cluster evaporation rates obtained from quantum chemistry.

  15. Effect of Different Omega-6/Omega-3 Polyunsaturated Fatty Acid Ratios on the Formation of Monohydroxylated Fatty Acids in THP-1 Derived Macrophages.

    PubMed

    Keeren, Kathrin; Huang, Dan; Smyl, Christopher; Fischer, Andreas; Rothe, Michael; Weylandt, Karsten-H

    2015-04-09

    Omega-6 and omega-3 polyunsaturated fatty acids (n-6 and n-3 PUFA) can modulate inflammatory processes. In western diets, the content of n-6 PUFA is much higher than that of n-3 PUFA, which has been suggested to promote a pro-inflammatory phenotype. The aim of this study was to analyze the effect of modulating the n-6/n-3 PUFA ratio on the formation of monohydroxylated fatty acid (HO-FAs) derived from the n-6 PUFA arachidonic acid (AA) and the n-3 PUFAs eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) in THP-1 macrophages by means of LC-MS. Lipid metabolites were measured in THP-1 macrophage cell pellets. The concentration of AA-derived hydroxyeicosatetraenoic acids (HETEs) was not significantly changed when incubated THP-1 macrophages in a high AA/(EPA+DHA) ratio of 19/1 vs. a low ratio AA/(EPA+DHA) of 1/1 (950.6 ± 110 ng/mg vs. 648.2 ± 92.4 ng/mg, p = 0.103). Correspondingly, the concentration of EPA-derived hydroxyeicosapentaenoic acids (HEPEs) and DHA-derived hydroxydocosahexaenoic acids (HDHAs) were significantly increased (63.9 ± 7.8 ng/mg vs. 434.4 ± 84.3 ng/mg, p = 0.012 and 84.9 ± 18.3 ng/mg vs. 439.4 ± 82.7 ng/mg, p = 0.014, respectively). Most notable was the strong increase of 18-hydroxyeicosapentaenoic acid (18-HEPE) formation in THP-1 macrophages, with levels of 170.9 ± 40.2 ng/mg protein in the high n-3 PUFA treated cells. Thus our data indicate that THP-1 macrophages prominently utilize EPA and DHA for monohydroxylated metabolite formation, in particular 18-HEPE, which has been shown to be released by macrophages to prevent pressure overload-induced maladaptive cardiac remodeling.

  16. Biofilm formation by lactic acid bacteria and resistance to environmental stress.

    PubMed

    Kubota, Hiromi; Senda, Shouko; Nomura, Nobuhiko; Tokuda, Hajime; Uchiyama, Hiroo

    2008-10-01

    We investigated the formation of biofilms by 3 type strains of lactic acid bacteria (LAB), Lactobacillus plantarum, Lactobacillus brevis and Lactobacillus fructivorans, as representatives of LAB that cause food deterioration or contamination. Lactobacillus plantarum subsp. plantarum JCM1149 and Lactobacillus brevis JCM1059 appeared to adhere and accumulate on glass cover slips. Lactobacillus fructivorans JCM1117 cells made thin cellophane-like biofilms, and most of the biofilm cells became longer than the planktonic cells. We tested the resistance of biofilm and planktonic L. plantarum subsp. plantarum JCM1149 cells to acetic acid and ethanol, which strongly inhibit the growth of bacteria and are important in food preservation. The biofilm cells were more resistant than the planktonic cells and the surfaces of the treated planktonic cells were badly damaged, whereas those of the biofilm cells were only slightly damaged. We isolated 43 LAB from onions and the biofolm cells of an isolate, L. plantarum M606 also had high resistance. These results demonstrate the significance of studying biofilms of LAB in the food industry.

  17. Jasmonic acid is a crucial signal transducer in heat shock induced sesquiterpene formation in Aquilaria sinensis.

    PubMed

    Xu, Yan-Hong; Liao, Yong-Cui; Zhang, Zheng; Liu, Juan; Sun, Pei-Wen; Gao, Zhi-Hui; Sui, Chun; Wei, Jian-He

    2016-02-23

    Agarwood, a highly valuable resinous and fragrant heartwood of Aquilaria plants, is widely used in traditional medicines, incense and perfume. Only when Aquilaria trees are wounded by external stimuli do they form agarwood sesquiterpene defensive compounds. Therefore, understanding the signaling pathway of wound-induced agarwood formation is important. Jasmonic acid (JA) is a well-characterized molecule that mediates a plant's defense response and secondary metabolism. However, little is known about the function of endogenous JA in agarwood sesquiterpene biosynthesis. Here, we report that heat shock can up-regulate the expression of genes in JA signaling pathway, induce JA production and the accumulation of agarwood sesquiterpene in A. sinensis cell suspension cultures. A specific inhibitor of JA, nordihydroguaiaretic acid (NDGA), could block the JA signaling pathway and reduce the accumulation of sesquiterpene compounds. Additionally, compared to SA and H2O2, exogenously supplied methyl jasmonate has the strongest stimulation effect on the production of sesquiterpene compounds. These results clearly demonstrate the central induction role of JA in heat-shock-induced sesquiterpene production in A. sinensis.

  18. Jasmonic acid is a crucial signal transducer in heat shock induced sesquiterpene formation in Aquilaria sinensis

    PubMed Central

    Xu, Yan-Hong; Liao, Yong-Cui; Zhang, Zheng; Liu, Juan; Sun, Pei-Wen; Gao, Zhi-Hui; Sui, Chun; Wei, Jian-He

    2016-01-01

    Agarwood, a highly valuable resinous and fragrant heartwood of Aquilaria plants, is widely used in traditional medicines, incense and perfume. Only when Aquilaria trees are wounded by external stimuli do they form agarwood sesquiterpene defensive compounds. Therefore, understanding the signaling pathway of wound-induced agarwood formation is important. Jasmonic acid (JA) is a well-characterized molecule that mediates a plant’s defense response and secondary metabolism. However, little is known about the function of endogenous JA in agarwood sesquiterpene biosynthesis. Here, we report that heat shock can up-regulate the expression of genes in JA signaling pathway, induce JA production and the accumulation of agarwood sesquiterpene in A. sinensis cell suspension cultures. A specific inhibitor of JA, nordihydroguaiaretic acid (NDGA), could block the JA signaling pathway and reduce the accumulation of sesquiterpene compounds. Additionally, compared to SA and H2O2, exogenously supplied methyl jasmonate has the strongest stimulation effect on the production of sesquiterpene compounds. These results clearly demonstrate the central induction role of JA in heat-shock-induced sesquiterpene production in A. sinensis. PMID:26902148

  19. Formation of hierarchical molecular assemblies from poly(oxypropylene)-segmented amido acids under AFM tapping.

    PubMed

    Lin, Jiang-Jen; Tsai, Wei-Cheng; Wang, Chi-He

    2007-04-10

    Molecular self-aligning of amphiphilic molecules into bundles with a constant width of 7-13 nm was observed under tapping-mode atomic force microscopy (TM-AFM). The requisite amphiphile, a poly(oxypropylene)-trimellitic amido acid sodium salt, is constituted of a symmetric amido acid structure with potential noncovalent forces of ionic charges, hydrogen bonds, pi-pi aromatic stacking, and hydrophobic interactions for intermolecular interaction. The amphiphiles are able to self-align into orderly hierarchical assemblies after simply being dissolved in water and dried under spin-coated evaporation. Under the TM-AFM tapping process, the bundles increased their length from an initial 20 to 600 nm. A sequential TM-AFM scanning and interval heating process was designed to probe the morphological transformations from the molecular bundles to lengthy strips (nearly micrometer scale) and to columns (with 5-7 nm spacing between the parallel strips). The formation of hierarchical arrays via molecular stretching, aligning, and connecting to each other was simultaneously observed and accelerated under the TM-AFM vibration energy. The molecular self-alignment caused by vibrations is envisioned to be a potential methodology for manipulating molecules into assembled templates, sensors, and optoelectronic devices.

  20. Formation of flavor components by the reaction of amino acid and carbonyl compounds in mild conditions.

    PubMed

    Pripis-Nicolau, L; de Revel, G; Bertrand, A; Maujean, A

    2000-09-01

    This work describe products of reactions between four alpha-dicarbonyl compounds (diacetyl, pentan-2,3-dione, glyoxal, and methylglyoxal) or two alpha-hydroxy ketones, (acetoine and acetol) and amino acids present in wines. The results shows the formation of odorous products or strong-smelling additives resulting from the Maillard and Strecker reaction in a primarily aqueous medium, at low temperature and low pH ( approximately pH 3.5) of the wine. GC/FID, GC/FPD, GC/NPD and GC/MS techniques were used. The olfactive characteristics of the products are described. In the presence of sulfur amino acids and in particular cysteine, many products were formed with a heterocycle production such as pyrazines and methylpyrazines, methylthiazoles, acetylthiazoles, acetylthiazolines, acetylthiazolidines, trimethyloxazole, and dimethylethyloxazoles. These various compounds present odors of sulfur, cornlike, pungent, nut, popcorn, roasted hazelnut, toasted, roasted, and ripe fruits. The chemical conditions of the model reactions are specified. The influence of temperature and pH on the reactions in the presence of cysteine were also studied.

  1. Weathering processes and pickeringite formation in a sulfidic schist: a consideration in acid precipitation neutralization studies

    SciTech Connect

    Parnell, R.A. Jr.

    1983-01-01

    Extremely low abrasion pH values (2.8-3.3) characterize the weathering products of the Partridge Formation, a Middle-Ordovician metamorphosed, black, sulfidic shale. The local occurrence is observed of two sulfates that are rare in the Northeast: pickeringite and jarosite. X-ray diffraction studies of the weathering residues and the sulfate efflorescences have also identified dioctahedral and trioctahedral illite, kaolinite, vermiculite, and an 11-12 Angstrom phase, thought to be a type of randomly-interstratified biotite-vermiculite. From the mineralogical studies, qualitative weathering processes for the schist are formulated. A probable mechanism for the intense chemical weathering of the schist appears to be oxidation of iron sulfides to form iron oxide-hydroxides, sulfates, and sulfuric acid. This natural weathering process is proposed as an analog to anthropogenic low pH rock weathering resulting from acid precipitation. In the Northeast, natural weathering rates, may, in places, significantly affect the water chemistry and mineralogy used to quantify total (natural plus anthropogenic) weathering and leaching rates. 27 references, 4 figures.

  2. Effect of etching with cysteamine assisted phosphoric acid on gallium nitride surface oxide formation

    NASA Astrophysics Data System (ADS)

    Wilkins, S. J.; Paskova, T.; Ivanisevic, A.

    2013-08-01

    In-situ functionalization of polar GaN was performed by adding cysteamine to a phosphoric acid etchant in order to study its effect on photoluminescence and oxide formation on the surfaces. The functionalization was characterized by atomic force microscopy, x-ray photoelectron spectroscopy, photoluminescence (PL), and water contact angle measurements. Two sets of polar GaN samples with different dislocation densities were evaluated, thin GaN layers residing on sapphire and thick free-standing GaN separated from sapphire substrate aiming to reveal the effect of material quality on in-situ functionalization. The addition of cysteamine to the phosphoric acid solution was found to result in: (i) decreased surface roughness, (ii) no change to hydrophobicity, (iii) decreased oxygen content especially at high-temperature treatments. The effect of the in-situ functionalization on the PL efficiency was more pronounced in the free-standing sample than in the film residing on the sapphire, which was attributed to a higher crystal quality free from strain.

  3. EtfA catalyses the formation of dipicolinic acid in Clostridium perfringens.

    PubMed

    Orsburn, Benjamin C; Melville, Stephen B; Popham, David L

    2010-01-01

    Dipicolinic acid (DPA) is a major component of bacterial endospores, comprising 5-15% of the spore dry weight, and is important for spore stability and resistance properties. The biosynthetic precursor to DPA, dihydro-dipicolinic acid (DHDPA), is produced by DHDPA synthase within the lysine biosynthesis pathway. In Bacillus subtilis, and most other bacilli and clostridia, DHDPA is oxidized to DPA by the products of the spoVF operon. Analysis of the genomes of the clostridia in Cluster I, including the pathogens Clostridium perfringens, Clostridium botulinum and Clostridium tetani, has shown that no spoVF orthologues exist in these organisms. DPA synthase was purified from extracts of sporulating C. perfringens cells. Peptide sequencing identified an electron transfer flavoprotein, EtfA, in this purified protein fraction. A C. perfringens strain with etfA inactivated is blocked in late stage sporulation and produces < or = 11% of wild-type DPA levels. C. perfringens EtfA was expressed in and purified from Escherichia coli, and this protein catalysed DPA formation in vitro. The sequential production of DHDPA and DPA in C. perfringens appears to be catalysed by DHDPA synthase followed by EtfA. Genome sequence data and the taxonomy of spore-forming species suggest that this may be the ancestral mechanism for DPA synthesis.

  4. Investigation of metal ion extraction and aggregate formation combining acidic and neutral organophosphorous reagents

    SciTech Connect

    Braatz, A.D.; Nilsson, M.; Ellis, R.; Antonio, M.

    2013-07-01

    In the present study, we investigate how varying mixtures of tri-n-butyl phosphate (TBP) and dibutyl phosphate (HDBP) results in enhanced extraction of lanthanum(III), La{sup 3+}, and dysprosium(III), Dy{sup 3+}. Water and metal ion extraction were carefully monitored as a function of TBP:HDBP mole ratio.In addition to these techniques, EXAFS was used to determine the coordination environment of the metal ion in this system. To produce the necessary signal, a concentration of 1.25*10{sup -3} M La{sup 3+} and Dy{sup 3+} was used. Although previous studies of synergistic extraction of metal cations using combinations of neutral and acidic reagents explain the enhanced extraction by increased dehydration of the metal ion and the formation of mixed extractant complexes, our evidence for the increased water extraction coupled with the aggregate formation suggests a reverse micellar aspect to synergism in the system containing TBP and HDBP. It is quite possible that both of these phenomena contribute to our system behavior. The EXAFS data shows that, based on coordination numbers alone, several possible structures may exist. From this study, we cannot provide a definitive answer as to the nature of extraction in this system or the exact complex formed during extraction.

  5. Inhibition of Gallic Acid on the Growth and Biofilm Formation of Escherichia coli and Streptococcus mutans.

    PubMed

    Shao, Dongyan; Li, Jing; Li, Ji; Tang, Ruihua; Liu, Liu; Shi, Junling; Huang, Qingsheng; Yang, Hui

    2015-06-01

    New strategies for biofilm inhibition are becoming highly necessary because of the concerns to synthetic additives. As gallic acid (GA) is a hydrolysated natural product of tannin in Chinese gall, this research studied the effects of GA on the growth and biofilm formation of bacteria (Escherichia coli [Gram-negative] and Streptococcus mutans [Gram-positive]) under different conditions, such as nutrient levels, temperatures (25 and 37 °C) and incubation times (24 and 48 h). The minimum antimicrobial concentration of GA against the two pathogenic organisms was determined as 8 mg/mL. GA significantly affected the growth curves of both test strains at 25 and 37 °C. The nutrient level, temperature, and treatment time influenced the inhibition activity of GA on both growth and biofim formation of tested pathogens. The inhibition effect of GA on biofilm could be due to other factors in addition to the antibacterial effect. Overall, GA was most effective against cultures incubated at 37 °C for 24 h and at 25 °C for 48 h in various concentrations of nutrients and in vegetable wash waters, which indicated the potential of GA as emergent sources of biofilm control products.

  6. Heterogeneous formation of polar stratospheric clouds - Part 1: Nucleation of nitric acid trihydrate (NAT)

    NASA Astrophysics Data System (ADS)

    Hoyle, C. R.; Engel, I.; Luo, B. P.; Pitts, M. C.; Poole, L. R.; Grooß, J.-U.; Peter, T.

    2013-03-01

    Satellite based observations during the Arctic winter of 2009/2010 provide firm evidence that, in contrast to the current understanding, the nucleation of nitric acid trihydrate (NAT) in the polar stratosphere does not only occur on preexisting ice particles. In order to explain the NAT clouds observed over the Arctic in mid December 2009, a heterogeneous nucleation mechanism is required, occurring via immersion freezing on the surface of solid particles, likely of meteoritic origin. For the first time, a detailed microphysical modelling of this NAT formation pathway has been carried out. Heterogeneous NAT formation was calculated along more than sixty thousand trajectories, ending at Cloud Aerosol Lidar with Orthogonal Polarisation (CALIOP) observation points. Comparing the optical properties of the modelled NAT with these observations enabled the thorough validation of a newly developed NAT nucleation parameterisation, which has been built into the Zurich Optical and Microphysical box Model (ZOMM). The parameterisation is based on active site theory, is simple to implement in models and provides substantial advantages over previous approaches which involved a constant rate of NAT nucleation in a given volume of air. It is shown that the new method is capable of reproducing observed PSCs very well, despite the varied conditions experienced by air parcels travelling along the different trajectories. In a companion paper, ZOMM is applied to a later period of the winter, when ice PSCs are also present, and it is shown that the observed PSCs are also represented extremely well under these conditions.

  7. Heterogeneous formation of polar stratospheric clouds - Part 1: Nucleation of nitric acid trihydrate (NAT)

    NASA Astrophysics Data System (ADS)

    Hoyle, C. R.; Engel, I.; Luo, B. P.; Pitts, M. C.; Poole, L. R.; Grooß, J.-U.; Peter, T.

    2013-09-01

    Satellite-based observations during the Arctic winter of 2009/2010 provide firm evidence that, in contrast to the current understanding, the nucleation of nitric acid trihydrate (NAT) in the polar stratosphere does not only occur on preexisting ice particles. In order to explain the NAT clouds observed over the Arctic in mid-December 2009, a heterogeneous nucleation mechanism is required, occurring via immersion freezing on the surface of solid particles, likely of meteoritic origin. For the first time, a detailed microphysical modelling of this NAT formation pathway has been carried out. Heterogeneous NAT formation was calculated along more than sixty thousand trajectories, ending at Cloud Aerosol Lidar with Orthogonal Polarization (CALIOP) observation points. Comparing the optical properties of the modelled NAT with these observations enabled a thorough validation of a newly developed NAT nucleation parameterisation, which has been built into the Zurich Optical and Microphysical box Model (ZOMM). The parameterisation is based on active site theory, is simple to implement in models and provides substantial advantages over previous approaches which involved a constant rate of NAT nucleation in a given volume of air. It is shown that the new method is capable of reproducing observed polar stratospheric clouds (PSCs) very well, despite the varied conditions experienced by air parcels travelling along the different trajectories. In a companion paper, ZOMM is applied to a later period of the winter, when ice PSCs are also present, and it is shown that the observed PSCs are also represented extremely well under these conditions.

  8. Heterogeneous Formation of Polar Stratospheric Clouds- Part 1: Nucleation of Nitric Acid Trihydrate (NAT)

    NASA Technical Reports Server (NTRS)

    Hoyle, C. R.; Engel, I.; Luo, B. P.; Pitts, M. C.; Poole, L. R.; Grooss, J.-U.; Peter, T.

    2013-01-01

    Satellite-based observations during the Arctic winter of 2009/2010 provide firm evidence that, in contrast to the current understanding, the nucleation of nitric acid trihydrate (NAT) in the polar stratosphere does not only occur on preexisting ice particles. In order to explain the NAT clouds observed over the Arctic in mid-December 2009, a heterogeneous nucleation mechanism is required, occurring via immersion freezing on the surface of solid particles, likely of meteoritic origin. For the first time, a detailed microphysical modelling of this NAT formation pathway has been carried out. Heterogeneous NAT formation was calculated along more than sixty thousand trajectories, ending at Cloud Aerosol Lidar with Orthogonal Polarization (CALIOP) observation points. Comparing the optical properties of the modelled NAT with these observations enabled a thorough validation of a newly developed NAT nucleation parameterisation, which has been built into the Zurich Optical and Microphysical box Model (ZOMM). The parameterisation is based on active site theory, is simple to implement in models and provides substantial advantages over previous approaches which involved a constant rate of NAT nucleation in a given volume of air. It is shown that the new method is capable of reproducing observed polar stratospheric clouds (PSCs) very well, despite the varied conditions experienced by air parcels travelling along the different trajectories. In a companion paper, ZOMM is applied to a later period of the winter, when ice PSCs are also present, and it is shown that the observed PSCs are also represented extremely well under these conditions.

  9. Free radical mediated formation of 3-monochloropropanediol (3-MCPD) fatty acid diesters.

    PubMed

    Zhang, Xiaowei; Gao, Boyan; Qin, Fang; Shi, Haiming; Jiang, Yuangrong; Xu, Xuebing; Yu, Liangli Lucy

    2013-03-13

    The present study was conducted to test the hypothesis that a free radical was formed and mediated the formation of 3-monochloropropanediol (3-MCPD) fatty acid diesters, a group of food contaminants, from diacylglycerols at high temperature under a low-moisture condition for the first time. The presence of free radicals in a vegetable oil kept at 120 °C for 20 min was demonstrated using an electron spin resonance (ESR) spectroscopy examination with 5,5-dimethylpyrroline-N-oxide (DMPO) as the spin trap agent. ESR investigation also showed an association between thermal treatment degree and the concentration of free radicals. A Fourier transform infrared spectroscopy (FT-IR) analysis of sn-1,2-stearoylglycerol (DSG) at 25 and 120 °C suggested the possible involvement of an ester carbonyl group in forming 3-MCPD diesters. On the basis of these results, a novel free radical mediated chemical mechanism was proposed for 3-MCPD diester formation. Furthermore, a quadrupole-time of flight (Q-TOF) MS/MS investigation was performed and detected the DMPO adducts with the cyclic acyloxonium free radical (CAFR) and its product MS ions, proving the presence of CAFR. Furthermore, the free radical mechanism was validated by the formation of 3-MCPD diesters through reacting DSG with a number of organic and inorganic chlorine sources including chlorine gas at 120 and 240 °C. The findings of this study might lead to the improvement of oil and food processing conditions to reduce the level of 3-MCPD diesters in foods and enhance food safety.

  10. Identification of Key Amino Acid Residues Modulating Intracellular and In vitro Microcin E492 Amyloid Formation.

    PubMed

    Aguilera, Paulina; Marcoleta, Andrés; Lobos-Ruiz, Pablo; Arranz, Rocío; Valpuesta, José M; Monasterio, Octavio; Lagos, Rosalba

    2016-01-01

    Microcin E492 (MccE492) is a pore-forming bacteriocin produced and exported by Klebsiella pneumoniae RYC492. Besides its antibacterial activity, excreted MccE492 can form amyloid fibrils in vivo as well as in vitro. It has been proposed that bacterial amyloids can be functional playing a biological role, and in the particular case of MccE492 it would control the antibacterial activity. MccE492 amyloid fibril's morphology and formation kinetics in vitro have been well-characterized, however, it is not known which amino acid residues determine its amyloidogenic propensity, nor if it forms intracellular amyloid inclusions as has been reported for other bacterial amyloids. In this work we found the conditions in which MccE492 forms intracellular amyloids in Escherichia coli cells, that were visualized as round-shaped inclusion bodies recognized by two amyloidophilic probes, 2-4'-methylaminophenyl benzothiazole and thioflavin-S. We used this property to perform a flow cytometry-based assay to evaluate the aggregation propensity of MccE492 mutants, that were designed using an in silico prediction of putative aggregation hotspots. We established that the predicted amino acid residues 54-63, effectively act as a pro-amyloidogenic stretch. As in the case of other amyloidogenic proteins, this region presented two gatekeeper residues (P57 and P59), which disfavor both intracellular and in vitro MccE492 amyloid formation, preventing an uncontrolled aggregation. Mutants in each of these gatekeeper residues showed faster in vitro aggregation and bactericidal inactivation kinetics, and the two mutants were accumulated as dense amyloid inclusions in more than 80% of E. coli cells expressing these variants. In contrast, the MccE492 mutant lacking residues 54-63 showed a significantly lower intracellular aggregation propensity and slower in vitro polymerization kinetics. Electron microscopy analysis of the amyloids formed in vitro by these mutants revealed that, although with

  11. Identification of Key Amino Acid Residues Modulating Intracellular and In vitro Microcin E492 Amyloid Formation

    PubMed Central

    Aguilera, Paulina; Marcoleta, Andrés; Lobos-Ruiz, Pablo; Arranz, Rocío; Valpuesta, José M.; Monasterio, Octavio; Lagos, Rosalba

    2016-01-01

    Microcin E492 (MccE492) is a pore-forming bacteriocin produced and exported by Klebsiella pneumoniae RYC492. Besides its antibacterial activity, excreted MccE492 can form amyloid fibrils in vivo as well as in vitro. It has been proposed that bacterial amyloids can be functional playing a biological role, and in the particular case of MccE492 it would control the antibacterial activity. MccE492 amyloid fibril’s morphology and formation kinetics in vitro have been well-characterized, however, it is not known which amino acid residues determine its amyloidogenic propensity, nor if it forms intracellular amyloid inclusions as has been reported for other bacterial amyloids. In this work we found the conditions in which MccE492 forms intracellular amyloids in Escherichia coli cells, that were visualized as round-shaped inclusion bodies recognized by two amyloidophilic probes, 2-4′-methylaminophenyl benzothiazole and thioflavin-S. We used this property to perform a flow cytometry-based assay to evaluate the aggregation propensity of MccE492 mutants, that were designed using an in silico prediction of putative aggregation hotspots. We established that the predicted amino acid residues 54–63, effectively act as a pro-amyloidogenic stretch. As in the case of other amyloidogenic proteins, this region presented two gatekeeper residues (P57 and P59), which disfavor both intracellular and in vitro MccE492 amyloid formation, preventing an uncontrolled aggregation. Mutants in each of these gatekeeper residues showed faster in vitro aggregation and bactericidal inactivation kinetics, and the two mutants were accumulated as dense amyloid inclusions in more than 80% of E. coli cells expressing these variants. In contrast, the MccE492 mutant lacking residues 54–63 showed a significantly lower intracellular aggregation propensity and slower in vitro polymerization kinetics. Electron microscopy analysis of the amyloids formed in vitro by these mutants revealed that, although

  12. The Effects of Topically Applied Glycolic Acid and Salicylic Acid on Ultraviolet Radiation-Induced Erythema, DNA Damage and Sunburn Cell Formation in Human Skin

    PubMed Central

    Kornhauser, Andrija; Wei, Rong-Rong; Yamaguchi, Yuji; Coelho, Sergio G.; Kaidbey, Kays; Barton, Curtis; Takahashi, Kaoruko; Beer, Janusz Z.; Miller, Sharon A.; Hearing, Vincent J.

    2009-01-01

    Background α-Hydroxy acids (αHA) are reported to reduce signs of aging in the skin and are widely used cosmetic ingredients. Several studies suggest that αHA can increase the sensitivity of skin to ultraviolet radiation. More recently, β-hydroxy acids (βHA), or combinations of αHA and βHA have also been incorporated into antiaging skin care products. Concerns have also arisen about increased sensitivity to ultraviolet radiation following use of skin care products containing β-HA. Objective To determine whether topical treatment with glycolic acid, a representative αHA, or with salicylic acid, a βHA, modifies the short-term effects of solar simulated radiation (SSR) in human skin. Methods Fourteen subjects participated in this study. Three of the four test sites on the mid-back of each subject were treated daily Monday - Friday, for a total of 3.5 weeks, with glycolic acid (10%), salicylic acid (2%), or vehicle (control). The fourth site received no treatment. After the last treatment, each site was exposed to SSR, and shave biopsies from all 4 sites were obtained. The endpoints evaluated in this study were erythema (assessed visually and instrumentally), DNA damage and sunburn cell formation. Results Treatment with glycolic acid resulted in increased sensitivity of human skin to SSR, measured as an increase in erythema, DNA damage and sunburn cell formation. Salicylic acid did not produce significant changes in any of these biomarkers. Conclusions Short-term topical application of glycolic acid in a cosmetic formulation increased the sensitivity of human skin to SSR, while a comparable treatment with salicylic acid did not. PMID:19411163

  13. Effect of Indoleacetic Acid and Related Indoles on Lactobacillus sp. Strain 11201 Growth, Indoleacetic Acid Catabolism, and 3-Methylindole Formation

    PubMed Central

    Honeyfield, D. C.; Carlson, J. R.

    1990-01-01

    A study was conducted to determine the activity of the 3-methylindole (3MI)-forming enzyme in Lactobacillus sp. strain 11201. Cells were incubated anaerobically with 17 different indolic and aromatic compounds. Indoleacetic acid (IAA), 5-hydroxyindoleacetic acid, 5-methoxy-3-indoleacetic acid, indole-3-pyruvate, or indole-3-propionic acid induced 3MI-forming activity. The highest total enzyme activity induced by IAA was observed in cells incubated with an initial concentration of 1.14 mM IAA. Peak activity of the 3MI-forming enzyme occurred 4 h after bacteria were incubated with either 0.114 or 1.14 mM IAA. Enzyme activity peaked earlier (2 h) and disappeared more rapidly at 5.7 mM IAA than at other concentrations of IAA. The effects of IAA and 3MI on the growth of Lactobacillus sp. strain 11201 and formation of 3MI from IAA also were determined. Bacterial growth and 3MI formation from IAA were reduced in medium containing exogenous 3MI. The growth depression observed in medium containing 5.7 mM IAA appears to be due to the toxicity of 3MI rather than IAA. The formation of 3MI in this ruminal Lactobacillus sp. is mediated by an inducible enzyme, and as 3MI accumulates, bacterial growth and rates of 3MI formation from IAA are reduced. PMID:16348189

  14. Involvement of glutathione peroxidase 1 in growth and peroxisome formation in Saccharomyces cerevisiae in oleic acid medium.

    PubMed

    Ohdate, Takumi; Inoue, Yoshiharu

    2012-09-01

    Saccharomyces cerevisiae is able to use some fatty acids, such as oleic acid, as a sole source of carbon. β-oxidation, which occurs in a single membrane-enveloped organelle or peroxisome, is responsible for the assimilation of fatty acids. In S. cerevisiae, β-oxidation occurs only in peroxisomes, and H(2)O(2) is generated during this fatty acid-metabolizing pathway. S. cerevisiae has three GPX genes (GPX1, GPX2, and GPX3) encoding atypical 2-Cys peroxiredoxins. Here we show that expression of GPX1 was induced in medium containing oleic acid as a carbon source in an Msn2/Msn4-dependent manner. We found that Gpx1 was located in the peroxisomal matrix. The peroxisomal Gpx1 showed peroxidase activity using thioredoxin or glutathione as a reducing power. Peroxisome biogenesis was induced when cells were cultured with oleic acid. Peroxisome biogenesis was impaired in gpx1∆ cells, and subsequently, the growth of gpx1∆ cells was lowered in oleic acid-containing medium. Gpx1 contains six cysteine residues. Of the cysteine-substituted mutants of Gpx1, Gpx1(C36S) was not able to restore growth and peroxisome formation in oleic acid-containing medium, therefore, redox regulation of Gpx1 seems to be involved in the mechanism of peroxisome formation.

  15. Molecular Structures, Acid-Base Properties, and Formation of Group 6 Transition Metal Hydroxides

    SciTech Connect

    Li, Shenggang; Guenther, Courtney L.; Kelley, Matthew S.; Dixon, David A.

    2011-04-28

    Density functional theory (DFT) and coupled cluster theory (CCSD(T)) were used to study the group 6 metal (M = Cr, Mo, W) hydroxides: MO3-m(OH)2m (m = 1-3), M2O6-m(OH)2m (m = 1-5), M3O9-m(OH)2m (m = 1, 2), and M4O11(OH)2. The calculations were done up to the complete basis set (CBS) limit for the CCSD(T) method. Molecular structures of many low-energy conformers/isomers were located. Brønsted acidities in the gas phase and pKa values in aqueous solution were predicted for MO3-m(OH)2m (m = 1-3) and MnO3n-1(OH)2 (n = 2-4). In addition, Brønsted basicities and Lewis acidities (fluoride affinities) were predicted for MO3-m(OH)2m (m = 1-3) as well as the metal oxide clusters MnO3n (n = 1-3). The metal hydroxides were predicted to be strong Brønsted acids and weak to modest Brønsted bases and Lewis acids. The pKa values can have values as negative as -31. Potential energy surfaces for the hydrolysis of the MnO3n (n = 1-4) clusters were calculated. Heats of formation of the metal hydroxides were predicted from the calculated reaction energies, and the agreement with the limited available experimental data is good. The first hydrolysis step leading to the formation of MnO3n-1(OH)2 was predicted to be exothermic, with the exothermicity becoming less negative as n increases and essentially converged at n = 3. Reaction rate constants for the hydrogen transfer steps were calculated using transition state theory and RRKM theory. Further hydrolysis of MnO3n-1(OH)2 tends to be endothermic especially for M = Cr. Fifty-five DFT exchange-correlation functionals were benchmarked for the calculations of the reaction energies, complexation energies, and reaction barriers by comparing to our CCSD(T) results. Overall, the DFT results for the potential energy surfaces are semiquantitatively correct, but no single functional works for all processes and all three metals. Among the functionals benchmarked, the wB97, wB97X, B1B95, B97-1, mPW1LYP, and X3LYP functionals have the best

  16. Ginkgolic acids and Ginkgo biloba extract inhibit Escherichia coli O157:H7 and Staphylococcus aureus biofilm formation.

    PubMed

    Lee, Jin-Hyung; Kim, Yong-Guy; Ryu, Shi Yong; Cho, Moo Hwan; Lee, Jintae

    2014-03-17

    Infection by enterohemorrhagic Escherichia coli O157:H7 (EHEC) is a worldwide problem, and there is no effective therapy. Biofilm formation is closely related to EHEC infection and is also a mechanism of antimicrobial resistance. Antibiofilm screening of 560 purified phytochemicals against EHEC showed that ginkgolic acids C15:1 and C17:1 at 5μg/ml and Ginkgo biloba extract at 100μg/ml significantly inhibited EHEC biofilm formation on the surfaces of polystyrene and glass, and on nylon membranes. Importantly, at their working concentrations, ginkgolic acids and G. biloba extract did not affect bacterial growth. Transcriptional analyses showed that ginkgolic acid C15:1 repressed curli genes and prophage genes in EHEC, and these findings were in-line with reduced fimbriae production and biofilm reductions. Interestingly, ginkgolic acids and G. biloba extract did not inhibit the biofilm formation of a commensal E. coli K-12 strain. In addition, ginkgolic acids and G. biloba extract inhibited the biofilm formation of three Staphylococcus aureus strains. The findings of this study suggest that plant secondary metabolites represent an important resource for biofilm inhibitors.

  17. Influences of Operating Parameters on the Formation of Furan During Heating Based on Models of Polyunsaturated Fatty Acids.

    PubMed

    Shen, Mingyue; Liu, Qian; Jiang, Yujie; Nie, Shaoping; Zhang, Yanan; Xie, Jianhua; Wang, Sunan; Zhu, Fan; Xie, Mingyong

    2015-06-01

    Furan, a possible carcinogen, is commonly produced by thermal processing in a number of heated foods. The existence of furan levels in foods has attracted considerable attention worldwide. Recent research of furan in food has focused on the possible influences of operating parameters on the furan formation during heat processing. The aim of our study was to investigate the impacts of multiple factors (pH, temperature, heating time, ferric, and glutamic acid) on furan formation using linolenic and linoleic acids-based model systems in which furan was analyzed by headspace gas chromatography-mass spectrometry (HS-GC-MS). The results revealed that the content of furan increased rapidly when the heating temperature was elevated, with the highest levels of furan in neutral buffer solutions, the furan levels were also found to be related to heating time in all model systems. Ferric promoted furan formation from polyunsaturated fatty acids, conversely glutamic acid with an optimum concentration suppressed the furan formation. The minimal level of furan in foods during thermal treatment could be achieved via adding furan formation suppressors, and/or avoidance of furan forming promoter.

  18. α-Gel formation by amino acid-based gemini surfactants.

    PubMed

    Sakai, Kenichi; Ohno, Kiyomi; Nomura, Kazuyuki; Endo, Takeshi; Sakamoto, Kazutami; Sakai, Hideki; Abe, Masahiko

    2014-07-08

    Ternary mixtures being composed of surfactant, long-chain alcohol, and water sometimes form a highly viscous lamellar gel with a hexagonal packing arrangement of their crystalline hydrocarbon chains. This molecular assembly is called "α-crystalline phase" or "α-gel". In this study, we have characterized α-gels formed by the ternary mixtures of amino acid-based gemini surfactants, 1-hexadecanol (C16OH), and water. The surfactants used in this study were synthesized by reacting dodecanoylglutamic acid anhydride with alkyl diamines and abbreviated as 12-GsG-12 (s: the spacer chain length of 2, 5, and 8 methylene units). An amino acid-based monomeric surfactant, dodecanoylglutamic acid (12-Glu), was also used for comparison. At a fixed water concentration the melting point of the α-gel increased with increasing C16OH concentration, and then attained a saturation level at the critical mole ratio of 12-GsG-12/C16OH = 1/2 under the normalization by the number of hydrocarbon chains of the surfactants. This indicates that, to obtain the saturated α-gel, a lesser amount of C16OH is required for the gemini surfactants than for the monomeric one (the critical mole ratio of 12-Glu/C16OH = 1/3). Small- and wide-angle X-ray scattering measurements demonstrated an increase in the long-range d-spacing of the saturated α-gels in the order 12-Glu <12-G8G-12 < 12-G5G-12 < 12-G2G-12. In the three gemini surfactant systems, the decreased spacer chain length resulted in the increased maximum viscosity and elastic modulus of the saturated α-gels at a given water concentration. This is caused by the decreased amount of excess water being present outside the α-gel structure (or the increased amount of water incorporated between the surfactant-alcohol bilayers). To the best of our knowledge, this is the first report focusing on the formation of α-gel in gemini surfactant systems.

  19. Freezing of sulfuric and nitric acid solutions: Implications for polar stratospheric cloud formation

    NASA Astrophysics Data System (ADS)

    Salcedo Gonzalez, Dara

    2000-12-01

    Polar Stratospheric Clouds (PSCs) play an important role in ozone chemistry during the polar winter. The magnitude of their effect depends on their phase, composition and formation mechanism, which are not fully understood yet. In order to understand how liquid PSCs freeze, two apparatus were designed to study the freezing behavior of small drops using a Fourier transform infrared (FTIR) spectrometer and an optical microscope. Sulfuric acid aqueous drops with composition of 10 to 50 wt % were studied with the FTIR apparatus. The surface on which the drops stand caused heterogeneous nucleation of ice, but not of the sulfuric acid hydrates. The more concentrated solutions (>40 wt %) supercooled to 130 K without freezing. Below 150 K these solutions formed an amorphous solid, which liquefied upon warming. Drops with composition of 40 to 64 wt % HNO3 were prepared and their phase transitions were detected with the optical microscope apparatus. Freezing temperatures of the drops were determined and homogeneous nucleation rates of nitric acid dihydrate (JNAD) and nitric acid trihydrate (JNAT) between 170 and 190 K were calculated. JNAT and JNAD depend predominantly on the saturation of the solid in the liquid solution: higher saturation ratios correspond to higher nucleation rates. Classical nucleation theory was used to parameterize this relation. Since the saturation ratios of NAD and NAT vary with temperature and composition in different ways, NAT or NAD can form preferentially under different conditions. Evidence was found that NAD catalyzes the nucleation of NAT below ~183 K. Mullite, cristobalite and alumina were tested as possible heterogeneous nuclei of volcanic origin for PSCs. They catalyze freezing of NAD and NAT at temperatures below 179 K, which are too low to be stratospherically important. The results suggest that the largest drops in a PSC will freeze homogeneously if the stratospheric temperature remains below the NAT condensation temperature for more

  20. Formation of Fe/mg Smectite Under Acidic Conditions from Synthetic Adirondack Basaltic Glass: an Analog to Fe/mg Smectite Formation on Mars

    NASA Technical Reports Server (NTRS)

    Sutter, B.; Peretyazhko, T.; Morris, R. V.; Ming, D. W.

    2014-01-01

    Smectite has been detected as layered material hundreds of meters thick, in intracrater depositional fans, in plains sediments, and deposits at depth on Mars. If early Mars hosted a dense CO2 atmosphere, then extensive carbonate should have formed in the neutral/alkaline conditions expected for smectite formation. However, large carbonate deposits on Mars have not been discovered. Instead of neutral to moderately alkaline conditions, early Mars may have experienced mildly acidic conditions that allowed for Fe/Mg smectite formation but prevented widespread carbonate formation. The objective of this work is to demonstrate that Fe(II)/Mg saponite and nontronite can form in mildly acidic solutions (e.g., pH 4). Synthetic basaltic glass (< 53 microns) of Adirondack rock class composition was exposed to pH 4 (acetic acid buffer) and N2 purged (anoxic) solutions amended with 0 and 10 mM Mg or Fe(II). Basaltic glass in these solutions was heated to 200 C in batch reactors for 1, 7, and 14 days. X-ray diffraction analysis of reacted materials detected the presence of phyllosilicates as indicated by a approx. 15.03-15.23Angstroms (001) peak. Smectite was confirmed as the phyllosilicate after treatments with glycerol and KCl and heating to 550 C. Trioctahedral saponite was confirmed by the presence of a 4.58 to 4.63 Angstroms (02l) and 1.54Angstroms (060) peaks. Saponite concentration was highest, as indicated by XRD peak intensity, in the 10 mM Mg treatment followed by the 0 mM and then 10 mM Fe(II) treatments. This order of sapontite concentration suggests that Fe(II) additions may have a role in slowing the kinetics of saponite formation relative to the other treatments. Nontronite synthesis was attempted by exposing Adirondack basaltic glass to pH 4 oxic solutions (without N2 purge) at 200 C for 14 days. X-ray diffraction analysis indicated that mixtures of trioctahedral (saponite) and dioctahedral (nontronite) may have formed in these experiments based on the 02l and 060

  1. Formation of Fe/Mg Smectite under acidic conditions from synthetic Adirondack Basaltic Glass: An Analog to Fe/Mg Smectite Formation on Mars.

    NASA Astrophysics Data System (ADS)

    Sutter, B.; Peretyazhko, T.; Morris, R. V.; Ming, D. W.

    2014-12-01

    Smectite has been detected as layered material hundreds of meters thick, in intracrater depositional fans, in plains sediments, and deposits at depth on Mars. If early Mars hosted a dense CO2 atmosphere, then extensive carbonate should have formed in the neutral/alkaline conditions expected for smectite formation. However, large carbonate deposits on Mars have not been discovered. Instead of neutral to moderately alkaline conditions, early Mars may have experienced mildly acidic conditions that allowed for Fe/Mg smectite formation but prevented widespread carbonate formation. The objective of this work is to demonstrate that Fe(II)/Mg-saponite and nontronite can form in mildly acidic solutions (e.g., pH 4). Synthetic basaltic glass (< 53 μm) of Adirondack rock class composition was exposed to pH 4 (acetic acid buffer) and N2 purged (anoxic) solutions amended with 0 and 10 mM Mg or Fe(II). Basaltic glass in these solutions was heated to 200ºC in batch reactors for 1, 7, and 14 days. X-ray diffraction analysis of reacted materials detected the presence of phyllosilicates as indicated by a ~15.03-15.23Ǻ (001) peak. Smectite was confirmed as the phyllosilicate after treatments with glycerol and KCl and heating to 550°C. Trioctahedral saponite was confirmed by the presence of a 4.58 to 4.63 Ǻ (02l) and 1.54Ǻ (060) peaks. Saponite concentration was highest, as indicated by XRD peak intensity, in the 10 mM Mg treatment followed by the 0 mM and then 10 mM Fe(II) treatments. This order of sapontite concentration suggests that Fe(II) additions may have a role in slowing the kinetics of saponite formation relative to the other treatments. Nontronite synthesis was attempted by exposing Adirondack basaltic glass to pH 4 oxic solutions (without N2 purge) at 200ºC for 14 days. X-ray diffraction analysis indicated that mixtures of trioctahedral (saponite) and dioctahedral (nontronite) may have formed in these experiments based on the 02l and 060 peaks. Mössbauer analysis

  2. Formation and Fragmentation of Unsaturated Fatty Acid [M - 2H + Na]- Ions: Stabilized Carbanions for Charge-Directed Fragmentation

    NASA Astrophysics Data System (ADS)

    Thomas, Michael C.; Kirk, Benjamin B.; Altvater, Jens; Blanksby, Stephen J.; Nette, Geoffrey W.

    2013-12-01

    Fatty acids are long-chain carboxylic acids that readily produce [M - H]- ions upon negative ion electrospray ionization (ESI) and cationic complexes with alkali, alkaline earth, and transition metals in positive ion ESI. In contrast, only one anionic monomeric fatty acid-metal ion complex has been reported in the literature, namely [M - 2H + FeIICl]-. In this manuscript, we present two methods to form anionic unsaturated fatty acid-sodium ion complexes (i.e., [M - 2H + Na]-). We find that these ions may be generated efficiently by two distinct methods: (1) negative ion ESI of a methanolic solution containing the fatty acid and sodium fluoride forming an [M - H + NaF]- ion. Subsequent collision-induced dissociation (CID) results in the desired [M - 2H + Na]- ion via the neutral loss of HF. (2) Direct formation of the [M - 2H + Na]- ion by negative ion ESI of a methanolic solution containing the fatty acid and sodium hydroxide or bicarbonate. In addition to deprotonation of the carboxylic acid moiety, formation of [M - 2H + Na]- ions requires the removal of a proton from the fatty acid acyl chain. We propose that this deprotonation occurs at the bis-allylic position(s) of polyunsaturated fatty acids resulting in the formation of a resonance-stabilized carbanion. This proposal is supported by ab initio calculations, which reveal that removal of a proton from the bis-allylic position, followed by neutral loss of HX (where X = F- and -OH), is the lowest energy dissociation pathway.

  3. Photo-induced formation of nitrous acid (HONO) on protein surfaces

    NASA Astrophysics Data System (ADS)

    Meusel, Hannah; Elshorbany, Yasin; Bartels-Rausch, Thorsten; Selzle, Kathrin; Lelieveld, Jos; Ammann, Markus; Pöschl, Ulrich; Su, Hang; Cheng, Yafang

    2014-05-01

    The study of nitrous acid (HONO) is of great interest, as the photolysis of HONO leads to the OH radical, which is the most important oxidant in the troposphere. HONO is directly emitted by combustion of fossil fuel and from soil biogenic nitrite (Su et al., 2011), and can also be formed by gas phase reactions of NO and OH and heterogeneous reactions of NO2. Previous atmospheric measurements have shown unexpectedly high HONO concentrations during daytime. Measured mixing ratios were about one order of magnitude higher than model simulations (Kleffmann et al. 2005, Vogel et al. 2003). The additional daytime source of HONO might be attributed to the photolysis of adsorbed nitric acid or heterogeneous photochemistry of NO2 on organic substrates, such as humic acids or polyphenolic compounds (Stemmler et al., 2006), or indirectly through nitration of phenols and subsequent photolysis of nitrophenols (Sosedova et al., 2011, Bejan et al., 2006). An important reactive surface for the heterogeneous formation of HONO could involve proteins, which are ubiquitous in the environment. They are part of coarse biological aerosol particles like pollen grains, fine particles (fragments of pollen, microorganism, plant debris) and dissolved in rainwater, soil and road dust (Miguel et al. 1999). In this project a thin film of bovine serum albumin (BSA), a model protein with 67 kDa and 21 tyrosine residues per molecule, is irradiated and exposed to nitrogen dioxide in humidified nitrogen. The formation of HONO is measured with long path absorption photometry (LOPAP). The generated HONO is in the range of 100 to 1100 ppt depending on light intensity, NO2 concentration and film thickness. Light induced HONO formation on protein surfaces is stable over the 20-hours experiment of irradiation and exposure. On the other hand, light activated proteins reacting with NO2 form nitrated proteins, as detected by liquid chromatography (LC-DAD). Our experiments on tetranitromethane (TNM) nitrated

  4. Structure and kinetics of formation of interphase layers of synthetic fatty acid aluminum soap at the water/oil interface

    SciTech Connect

    Chalykh, A.E.; Matveev, V.V.; Mityuk, D.Y.; Shal't, S.Y.; Tarasevich, B.N.

    1986-02-01

    The authors investigate the kinetics of formation of interphase layers (IL) at the interface between the phases: a 0.15% solution of aluminum soap of synthetic fatty acids (SFA) (fraction C/sub 17/-C/sub 21/) in n-decane/distilled water. The structure and the morphological properties of IL were investigated by transmission electron spectroscopy. The electron micrographs of the interphase layer of the soap at different stages of its formation show that the formation of a new phase starts with the appearance of small dispersed particles with spherical and fibrillar shapes. The results obtained supplement the authors' concepts about the mechanism of spontaneous microemulsification.

  5. Formation of lipid bodies and changes in fatty acid composition upon pre-akinete formation in Arctic and Antarctic Zygnema (Zygnematophyceae, Streptophyta) strains

    PubMed Central

    Pichrtová, Martina; Arc, Erwann; Stöggl, Wolfgang; Kranner, Ilse; Hájek, Tomáš; Hackl, Hubert; Holzinger, Andreas

    2016-01-01

    Filamentous green algae of the genus Zygnema (Zygnematophyceae, Streptophyta) are key components of polar hydro-terrestrial mats where they face various stressors including UV irradiation, freezing, desiccation and osmotic stress. Their vegetative cells can develop into pre-akinetes, i.e. reserve-rich, mature cells. We investigated lipid accumulation and fatty acid (FA) composition upon pre-akinete formation in an Arctic and an Antarctic Zygnema strain using transmission electron microscopy and gas chromatography coupled with mass spectrometry. Pre-akinetes formed after 9 weeks of cultivation in nitrogen-free medium, which was accompanied by massive accumulation of lipid bodies. The composition of FAs was similar in both strains, and α-linolenic acid (C18:3) dominated in young vegetative cells. Pre-akinete formation coincided with a significant change in FA composition. Oleic (C18:1) and linoleic (C18:2) acid increased the most (up to 17- and 8-fold, respectively). Small amounts of long-chain polyunsaturated FAs were also detected, e.g. arachidonic (C20:4) and eicosapentaenoic (C20:5) acid. Pre-akinetes exposed to desiccation at 86% relative humidity were able to recover maximum quantum yield of photosystem II, but desiccation had no major effect on FA composition. The results are discussed with regard to the capability of Zygnema spp. to thrive in extreme conditions. PMID:27170362

  6. Biofilm formation and indole-3-acetic acid production by two rhizospheric unicellular cyanobacteria.

    PubMed

    Ahmed, Mehboob; Stal, Lucas J; Hasnain, Shahida

    2014-08-01

    Microorganisms that live in the rhizosphere play a pivotal role in the functioning and maintenance of soil ecosystems. The study of rhizospheric cyanobacteria has been hampered by the difficulty to culture and maintain them in the laboratory. The present work investigated the production of the plant hormone indole-3-acetic acid (IAA) and the potential of biofilm formation on the rhizoplane of pea plants by two cyanobacterial strains, isolated from rice rhizosphere. The unicellular cyanobacteria Chroococcidiopsis sp. MMG-5 and Synechocystis sp. MMG-8 that were isolated from a rice rhizosphere, were investigated. Production of IAA by Chroococcidiopsis sp. MMG-5 and Synechocystis sp. MMG-8 was measured under experimental conditions (pH and light). The bioactivity of the cyanobacterial auxin was demonstrated through the alteration of the rooting pattern of Pisum sativum seedlings. The increase in the concentration of L-tryptophan and the time that this amino acid was present in the medium resulted in a significant enhancement of the synthesis of IAA (r > 0.900 at p = 0.01). There was also a significant correlation between the concentration of IAA in the supernatant of the cyanobacteria cultures and the root length and number of the pea seedlings. Observations made by confocal laser scanning microscopy revealed the presence of cyanobacteria on the surface of the roots and also provided evidence for the penetration of the cyanobacteria in the endorhizosphere. We show that the synthesis of IAA by Chroococcidiopsis sp. MMG-5 and Synechocystis sp. MMG-8 occurs under different environmental conditions and that the auxin is important for the development of the seedling roots and for establishing an intimate symbiosis between cyanobacteria and host plants.

  7. Formation of calcium carbonate films on chitosan substrates in the presence of polyacrylic acid

    SciTech Connect

    He, Linghao; Xue, Rui; Song, Rui

    2009-05-15

    In this investigation, chitosan membranes with different surface average degrees of deacetylation (DA) are prepared and then are employed as the support matrix to culture calcium carbonate (CaCO{sub 3}). In the presence of high concentration of polyacrylic acid (PAA), the CaCO{sub 3} films obtained on the surface of all chitosan films mainly consisted of vaterite, which suggests the presence of bulk PAA plays an overwhelming part in stabilizing the vaterite. As a comparison, the influences of active groups indicate that only in case of low concentration PAA the thin CaCO{sub 3} films grown on chitosan with 8% DA mainly consisted of vaterite owing to the strong nucleation ability of -NH{sub 2} group, whereas, for those grown on chitosan with 80% DA the CaCO{sub 3} films mainly consisted of aragonite. A more complex scenario revealed that in the case of intermediate concentration of PAA the formed polymorphs behave as mixtures of vaterite and aragonite. - Graphical abstract: Chitosan membranes with different degrees of deacetylation (DA) are employed as support to culture calcium carbonate (CaCO{sub 3}). In high concentration of polyacrylic acid (PAA), the CaCO{sub 3} films obtained consisted of vaterite. However, the CaCO{sub 3} film grown on chitosan with 8% DA mainly consisted of vaterite as opposed to aragonite for chitosan with 8% DA. The schematic presentation of the formation of calcium carbonate on chitosan films with different degrees of acetylation in the presence of PAA with low-, mid- and high concentrations.

  8. Heating of vegetable oils influences the activity of enzymes participating in arachidonic acid formation in Wistar rats.

    PubMed

    Stawarska, Agnieszka; Białek, Agnieszka; Tokarz, Andrzej

    2015-10-01

    Dietary intake of lipids and their fatty acids profile influence many aspects of health. Thermal processing changes the properties of edible oils and can also modify their metabolism, for example, eicosanoids formation. The aim of our study was to verify whether the activity of desaturases can be modified by lipids intake, especially by the fatty acids content. The experimental diets contained rapeseed oil, sunflower oil, and olive oil, both unheated and heated (for 10 minutes at 200 °C each time before administration), and influenced the fatty acids composition in serum and the activity of enzymes participating in arachidonic acid (AA) formation. The activity of desaturases was determined by measuring the amounts of AA formed in vitro derived from linoleic acid as determined in liver microsomes of Wistar rats. In addition, the indices of ∆(6)-desaturase (D6D) and ∆(5)-desaturase (D5D) have been determined. To realize this aim, the method of high-performance liquid chromatography has been used with ultraviolet-visible spectrophotometry detection. Diet supplementation with the oils rich in polyunsaturated fatty acids affects the fatty acids profile in blood serum and the activity of D6D and ∆(5)-desaturase in rat liver microsomes, the above activities being dependent on the kind of oil applied. Diet supplementation with heated oils has been found to increase the amount of AA produced in hepatic microsomes; and in the case of rapeseed oil and sunflower oil, it has also increased D6D activity.

  9. 37 CFR 1.824 - Form and format for nucleotide and/or amino acid sequence submissions in computer readable form.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... nucleotide and/or amino acid sequence submissions in computer readable form. 1.824 Section 1.824 Patents... And/or Amino Acid Sequences § 1.824 Form and format for nucleotide and/or amino acid sequence... readable form may be created by any means, such as word processors, nucleotide/amino acid sequence...

  10. 37 CFR 1.824 - Form and format for nucleotide and/or amino acid sequence submissions in computer readable form.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... nucleotide and/or amino acid sequence submissions in computer readable form. 1.824 Section 1.824 Patents... And/or Amino Acid Sequences § 1.824 Form and format for nucleotide and/or amino acid sequence... readable form may be created by any means, such as word processors, nucleotide/amino acid sequence...

  11. 37 CFR 1.824 - Form and format for nucleotide and/or amino acid sequence submissions in computer readable form.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... nucleotide and/or amino acid sequence submissions in computer readable form. 1.824 Section 1.824 Patents... And/or Amino Acid Sequences § 1.824 Form and format for nucleotide and/or amino acid sequence... readable form may be created by any means, such as word processors, nucleotide/amino acid sequence...

  12. Acetic acid-catalyzed formation of N-phenylphthalimide from phthalanilic acid: a computational study of the mechanism.

    PubMed

    Takahashi, Ohgi; Kirikoshi, Ryota; Manabe, Noriyoshi

    2015-05-28

    In glacial acetic acid, phthalanilic acid and its monosubstituents are known to be converted to the corresponding phthalimides in relatively good yields. In this study, we computationally investigated the experimentally proposed two-step (addition-elimination or cyclization-dehydration) mechanism at the second-order Møller-Plesset perturbation (MP2) level of theory for the unsubstituted phthalanilic acid, with an explicit acetic acid molecule included in the calculations. In the first step, a gem-diol tetrahedral intermediate is formed by the nucleophilic attack of the amide nitrogen. The second step is dehydration of the intermediate to give N-phenylphthalimide. In agreement with experimental findings, the second step has been shown to be rate-determining. Most importantly, both of the steps are catalyzed by an acetic acid molecule, which acts both as proton donor and acceptor. The present findings, along with those from our previous studies, suggest that acetic acid and other carboxylic acids (in their undissociated forms) can catalyze intramolecular nucleophilic attacks by amide nitrogens and breakdown of the resulting tetrahedral intermediates, acting simultaneously as proton donor and acceptor. In other words, double proton transfers involving a carboxylic acid molecule can be part of an extensive bond reorganization process from cyclic hydrogen-bonded complexes.

  13. Sialic acid transporter NanT participates in Tannerella forsythia biofilm formation and survival on epithelial cells.

    PubMed

    Honma, Kiyonobu; Ruscitto, Angela; Frey, Andrew M; Stafford, Graham P; Sharma, Ashu

    2016-05-01

    Tannerella forsythia is a periodontal pathogen implicated in periodontitis. This gram-negative pathogen depends on exogenous peptidoglycan amino sugar N-acetylmuramic acid (NAM) for growth. In the biofilm state the bacterium can utilize sialic acid (Neu5Ac) instead of NAM to sustain its growth. Thus, the sialic acid utilization system of the bacterium plays a critical role in the growth and survival of the organism in the absence of NAM. We sought the function of a T. forsythia gene annotated as nanT coding for an inner-membrane sugar transporter located on a sialic acid utilization genetic cluster. To determine the function of this putative sialic acid transporter, an isogenic nanT-deletion mutant generated by allelic replacement strategy was evaluated for biofilm formation on NAM or Neu5Ac, and survival on KB epithelial cells. Moreover, since T. forsythia forms synergistic biofilms with Fusobacterium nucleatum, co-biofilm formation activity in mixed culture and sialic acid uptake in culture were also assessed. The data showed that the nanT-inactivated mutant of T. forsythia was attenuated in its ability to uptake sialic acid. The mutant formed weaker biofilms compared to the wild-type strain in the presence of sialic acid and as co-biofilms with F. nucleatum. Moreover, compared to the wild-type T. forsythia nanT-inactivated mutant showed reduced survival when incubated on KB epithelial cells. Taken together, the data presented here demonstrate that NanT-mediated sialic transportation is essential for sialic acid utilization during biofilm growth and survival of the organism on epithelial cells and implies sialic acid might be key for its survival both in subgingival biofilms and during infection of human epithelial cells in vivo.

  14. Site-specific dynamics of amyloid formation and fibrillar configuration of Aβ(1-23) using an unnatural amino acid.

    PubMed

    Liu, Haiyang; Lantz, Richard; Cosme, Patrick; Rivera, Nelson; Andino, Carlos; Gonzalez, Walter G; Terentis, Andrew C; Wojcikiewicz, Ewa P; Oyola, Rolando; Miksovska, Jaroslava; Du, Deguo

    2015-04-25

    We identify distinct site-specific dynamics over the time course of Aβ1-23 amyloid formation by using an unnatural amino acid, p-cyanophenylalanine, as a sensitive fluorescent and Raman probe. Our results also suggest the key role of an edge-to-face aromatic interaction in the conformational conversion to form and stabilize β-sheet structure.

  15. Boronic acid-modified alginate enables direct formation of injectable, self-healing and multistimuli-responsive hydrogels.

    PubMed

    Pettignano, Asja; Grijalvo, Santiago; Häring, Marleen; Eritja, Ramon; Tanchoux, Nathalie; Quignard, Françoise; Díaz Díaz, David

    2017-03-16

    One-step functionalization of alginate with boronic acid groups allowed spontaneous formation of biocompatible hydrogels under basic conditions without additional complementary molecules or crosslinking agents. The dynamic nature of boronate ester bonds formed with vicinal diols present on alginate pyranose rings provided remarkable self-healing, injectable and multi-stimuli responsive properties to the material.

  16. Inhibition of methane and natural gas hydrate formation by altering the structure of water with amino acids

    PubMed Central

    Sa, Jeong-Hoon; Kwak, Gye-Hoon; Han, Kunwoo; Ahn, Docheon; Cho, Seong Jun; Lee, Ju Dong; Lee, Kun-Hong

    2016-01-01

    Natural gas hydrates are solid hydrogen-bonded water crystals containing small molecular gases. The amount of natural gas stored as hydrates in permafrost and ocean sediments is twice that of all other fossil fuels combined. However, hydrate blockages also hinder oil/gas pipeline transportation, and, despite their huge potential as energy sources, our insufficient understanding of hydrates has limited their extraction. Here, we report how the presence of amino acids in water induces changes in its structure and thus interrupts the formation of methane and natural gas hydrates. The perturbation of the structure of water by amino acids and the resulting selective inhibition of hydrate cage formation were observed directly. A strong correlation was found between the inhibition efficiencies of amino acids and their physicochemical properties, which demonstrates the importance of their direct interactions with water and the resulting dissolution environment. The inhibition of methane and natural gas hydrate formation by amino acids has the potential to be highly beneficial in practical applications such as hydrate exploitation, oil/gas transportation, and flow assurance. Further, the interactions between amino acids and water are essential to the equilibria and dynamics of many physical, chemical, biological, and environmental processes. PMID:27526869

  17. Inhibition of methane and natural gas hydrate formation by altering the structure of water with amino acids.

    PubMed

    Sa, Jeong-Hoon; Kwak, Gye-Hoon; Han, Kunwoo; Ahn, Docheon; Cho, Seong Jun; Lee, Ju Dong; Lee, Kun-Hong

    2016-08-16

    Natural gas hydrates are solid hydrogen-bonded water crystals containing small molecular gases. The amount of natural gas stored as hydrates in permafrost and ocean sediments is twice that of all other fossil fuels combined. However, hydrate blockages also hinder oil/gas pipeline transportation, and, despite their huge potential as energy sources, our insufficient understanding of hydrates has limited their extraction. Here, we report how the presence of amino acids in water induces changes in its structure and thus interrupts the formation of methane and natural gas hydrates. The perturbation of the structure of water by amino acids and the resulting selective inhibition of hydrate cage formation were observed directly. A strong correlation was found between the inhibition efficiencies of amino acids and their physicochemical properties, which demonstrates the importance of their direct interactions with water and the resulting dissolution environment. The inhibition of methane and natural gas hydrate formation by amino acids has the potential to be highly beneficial in practical applications such as hydrate exploitation, oil/gas transportation, and flow assurance. Further, the interactions between amino acids and water are essential to the equilibria and dynamics of many physical, chemical, biological, and environmental processes.

  18. Inhibition of methane and natural gas hydrate formation by altering the structure of water with amino acids

    NASA Astrophysics Data System (ADS)

    Sa, Jeong-Hoon; Kwak, Gye-Hoon; Han, Kunwoo; Ahn, Docheon; Cho, Seong Jun; Lee, Ju Dong; Lee, Kun-Hong

    2016-08-01

    Natural gas hydrates are solid hydrogen-bonded water crystals containing small molecular gases. The amount of natural gas stored as hydrates in permafrost and ocean sediments is twice that of all other fossil fuels combined. However, hydrate blockages also hinder oil/gas pipeline transportation, and, despite their huge potential as energy sources, our insufficient understanding of hydrates has limited their extraction. Here, we report how the presence of amino acids in water induces changes in its structure and thus interrupts the formation of methane and natural gas hydrates. The perturbation of the structure of water by amino acids and the resulting selective inhibition of hydrate cage formation were observed directly. A strong correlation was found between the inhibition efficiencies of amino acids and their physicochemical properties, which demonstrates the importance of their direct interactions with water and the resulting dissolution environment. The inhibition of methane and natural gas hydrate formation by amino acids has the potential to be highly beneficial in practical applications such as hydrate exploitation, oil/gas transportation, and flow assurance. Further, the interactions between amino acids and water are essential to the equilibria and dynamics of many physical, chemical, biological, and environmental processes.

  19. Electrocatalytic Oxidation of Formate with Nickel Diphosphane Dipeptide Complexes. Effect of Ligands Modified with Amino Acids

    SciTech Connect

    Galan, Brandon R.; Reback, Matthew L.; Jain, Avijita; Appel, Aaron M.; Shaw, Wendy J.

    2013-09-03

    A series of nickel bis-diphosphine complexes with dipeptides appended to the ligands were investigated for the catalytic oxidation of formate. Typical rates of ~7 s-1 were found, similar to the parent complex (~8 s-1), with amino acid size and positioning contributing very little to rate or operating potential. Hydroxyl functionalities did result in lower rates, which were recovered by protecting the hydroxyl group. The results suggest that the overall dielectric introduced by the dipeptides does not play an important role in catalysis, but free hydroxyl groups do influence activity suggesting contributions from intra- or intermolecular interactions. These observations are important in developing a fundamental understanding of the affect that an enzyme-like outer coordination sphere can have upon molecular catalysts. This work was funded by the US DOE Basic Energy Sciences, Chemical Sciences, Geoscience and Biosciences Division (BRG, AJ, AMA, WJS), the US DOE Basic Energy Sciences, Physical Bioscience program (MLR). Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  20. Identification of the amino acid residues responsible for stable nucleosome formation by histone H3.Y.

    PubMed

    Kujirai, Tomoya; Horikoshi, Naoki; Xie, Yan; Taguchi, Hiroyuki; Kurumizaka, Hitoshi

    2017-01-24

    Histone H3.Y is conserved among primates. We previously reported that exogenously produced H3.Y accumulates around transcription start sites, suggesting that it may play a role in transcription regulation. The H3.Y nucleosome forms a relaxed chromatin conformation with flexible DNA ends. The H3.Y-specific Lys42 residue is partly responsible for enhancing the flexibility of the nucleosomal DNA. To our surprise, we found that H3.Y stably associates with chromatin and nucleosomes in vivo and in vitro. However, the H3.Y residues responsible for its stable nucleosome incorporation have not been identified yet. In the present study, we performed comprehensive mutational analyses of H3.Y, and determined that the H3.Y C-terminal region including amino acid residues 124-135 is responsible for its stable association with DNA. Among the H3.Y C-terminal residues, the H3.Y Met124 residue significantly contributed to the stable DNA association with the H3.Y-H4 tetramer. The H3.Y M124I mutation substantially reduced the H3.Y-H4 association in the nucleosome. In contrast, the H3.Y K42R mutation affected the nucleosome stability less, although it contributes to the flexible DNA ends of the nucleosome. Therefore, these H3.Y-specific residues, Lys42 and Met124, play different and specific roles in nucleosomal DNA relaxation and stable nucleosome formation, respectively, in chromatin.

  1. Formation of an 8-hydroxyguanine moiety in deoxyribonucleic acid on gamma-irradiation in aqueous solution

    SciTech Connect

    Dizdaroglu, M.

    1985-07-30

    Isolation and characterization of a novel radiation-induced product, i.e., the 8-hydroxyguanine residue, produced in deoxyribonucleic acid (DNA), 2'-deoxyguanosine, and 2'-deoxyguanosine 5'-monophosphate by gamma-irradiation in aqueous solution, are described. For this purpose, gamma-irradiated DNA was first hydrolyzed with a mixture of four enzymes, i.e., DNase I, spleen and snake venom exonucleases, and alkaline phosphatase. Analysis of the resulting mixture by capillary gas chromatography-mass spectrometry after trimethylsilylation revealed the presence of a product, which was identified as 8-hydroxy-2'-deoxyguanosine on the basis of the typical fragment ions of its trimethylsilyl (Me3Si) derivative. This product was then isolated by using reversed-phase high-performance liquid chromatography. The UV and proton nuclear magnetic resonance spectra taken from the isolated product confirmed the structure suggested by the mass spectrum of its Me3Si derivative. The yield of 8-hydroxyguanine was also measured. Its mechanism of formation is believed to involve OH radical addition to the C-8 position of guanine followed by oxidation of the radical adduct.

  2. Latitudinal distributions of atmospheric dicarboxylic acids, oxocarboxylic acids, and α-dicarbonyls over the western North Pacific: Sources and formation pathways

    NASA Astrophysics Data System (ADS)

    Bikkina, Srinivas; Kawamura, Kimitaka; Miyazaki, Yuzo

    2015-05-01

    The present study aims to assess the molecular distributions of water-soluble dicarboxylic acids (diacids: C2-C12), oxocarboxylic acids (C2-C9), and α-dicarbonyls (glyoxal and methylglyoxal) in aerosols collected over the western North Pacific (WNP) during a summer cruise (August to September 2008). The measured water-soluble organics show pronounced latitudinal distributions with higher concentrations in the region of 30°N-45°N (average 63 ng m-3) than 10°N-30°N (18 ng m-3). Mass fraction of oxalic acid (C2) in total aliphatic diacids (ΣC2-C12) showed higher values (72 ± 10%) in lower latitude (10°N-30°N) than that (56 ± 16%) in higher latitude (30°N-45°N), suggesting a photochemical production of C2 due to an increased insolation over the tropical WNP. A similar trend was found in other diagnostic ratios such as oxalic to succinic (C2/C4) and oxalic to glyoxylic acid (C2/ωC2), which further corroborate an enhanced photochemical aging over the WNP. In addition, relative abundances of oxalic acid in total diacids showed a marked increase as a function of ambient temperature, supporting their photochemical production. Constantly low concentration ratios of adipic and phthalic acids relative to azelaic acid suggest a small contribution of anthropogenic sources and an importance of oceanic sources during the study period. Significant production of C2 through oxidation of biogenic volatile organic compounds emitted from the sea surface is also noteworthy, as inferred from the strong linear correlations among water-soluble organic carbon, methanesulphonic acid, and oxalic acid. Sea-to-air emission of unsaturated fatty acids also contributes to formation of diacids over the WNP.

  3. Field Observation of Heterogeneous Formation of Dicarboxylic acids, Keto-carboxylic acids, α-Dicarbonyls and Nitrate in Xi'an, China during Asian dust storm periods

    NASA Astrophysics Data System (ADS)

    Wang, G.; Wang, J.; Ren, Y.; Li, J.

    2015-12-01

    To understand the formation mechanism of secondary organic aerosols (SOA) on dust surfaces, this study investigated the concentrations and compositions of dicarboxylic acids (C2-C11), keto-carboxylic acids (C3-C7), α-dicarbonyls and inorganic ions in size-segregated aerosols (9-stages) collected in Xi'an, China during the nondust storm and dust storm periods of 2009 and 2011. During the events the ambient particulate dicarboxylic acids were 932-2240 ng m-3, which are comparable and even higher than those in nondust periods. Molecular compositions of the above SOA are similar to those in nondust periods with oxalic acid being the leading species. In the presence of the dust storms, all the above mentioned SOA species in Xi'an were predominantly enriched on the coarse particles (>2.1μm), and oxalic acid well correlated with NO3- (R2=0.72, p<0.001) rather than SO42-.This phenomenon differs greatly from the SOA in any other nondust period that is characterized by an enrichment of oxalic acid in fine particles and a strong correlation of oxalic acid with SO42-. Our results further demonstrate that NO3- in the dust periods in Xi'an was mostly derived from secondary oxidation, whereas SO42- during the events was largely derived from surface soil of Gobi deserts. We propose a formation pathway to explain these observations, in which nitric acid and/or nitrogen oxides react with dust to produce Ca(NO3)2 and form a liquid phase on the surface of dust aerosols via water vapor-absorption of Ca(NO3)2, followed by a partitioning of the gas-phase water-soluble organic precursors (e.g.,glyoxal and methylglyoxal) into the aqueous-phase and a subsequent oxidation into oxalic acid. To the best of our knowledge, we found for the first time the enrichment of glyoxal and methylglyoxal on dust surface. Our data suggest an important role of nitrate in the heterogeneous formation process of SOA on the surface of Asian dust.

  4. Evaluation of accelerated UV and thermal testing for benzene formation in beverages containing benzoate and ascorbic acid.

    PubMed

    Nyman, Patricia J; Wamer, Wayne G; Begley, Timothy H; Diachenko, Gregory W; Perfetti, Gracia A

    2010-04-01

    Under certain conditions, benzene can form in beverages containing benzoic and ascorbic acids. The American Beverage Assn. (ABA) has published guidelines to help manufacturers mitigate benzene formation in beverages. These guidelines recommend accelerated testing conditions to test product formulations, because exposure to ultraviolet (UV) light and elevated temperature over the shelf life of the beverage may result in benzene formation in products containing benzoic and ascorbic acids. In this study, the effects of UVA exposure on benzene formation were determined. Benzene formation was examined for samples contained in UV stabilized and non-UV stabilized packaging. Additionally, the usefulness of accelerated thermal testing to simulate end of shelf-life benzene formation was evaluated for samples containing either benzoic or ascorbic acid, or both. The 24 h studies showed that under intense UVA light benzene levels increased by as much as 53% in model solutions stored in non-UV stabilized bottles, whereas the use of UV stabilized polyethylene terephthalate bottles reduced benzene formation by about 13% relative to the non-UV stabilized bottles. Similar trends were observed for the 7 d study. Retail beverages and positive and negative controls were used to study the accelerated thermal testing conditions. The amount of benzene found in the positive controls and cranberry juice suggests that testing at 40 degrees C for 14 d may more reliably simulate end of shelf-life benzene formation in beverages. Except for cranberry juice, retail beverages were not found to contain detectable amounts of benzene (<0.05 ng/g) at the end of their shelf lives.

  5. Efficient and specific conversion of 9-lipoxygenase hydroperoxides in the beetroot. Formation of pinellic acid.

    PubMed

    Hamberg, Mats; Olsson, Ulrika

    2011-09-01

    The linoleate 9-lipoxygenase product 9(S)-hydroperoxy-10(E),12(Z)-octadecadienoic acid was stirred with a crude enzyme preparation from the beetroot (Beta vulgaris ssp. vulgaris var. vulgaris) to afford a product consisting of 95% of 9(S),12(S),13(S)-trihydroxy-10(E)-octadecenoic acid (pinellic acid). The linolenic acid-derived hydroperoxide 9(S)-hydroperoxy-10(E),12(Z),15(Z)-octadecatrienoic acid was converted in an analogous way into 9(S),12(S),13(S)-trihydroxy-10(E),15(Z)-octadecadienoic acid (fulgidic acid). On the other hand, the 13-lipoxygenase-generated hydroperoxides of linoleic or linolenic acids failed to produce significant amounts of trihydroxy acids. Short-time incubation of 9(S)-hydroperoxy-10(E),12(Z)-octadecadienoic acid afforded the epoxy alcohol 12(R),13(S)-epoxy-9(S)-hydroxy-10(E)-octadecenoic acid as the main product indicating the sequence 9-hydroperoxide → epoxy alcohol → trihydroxy acid catalyzed by epoxy alcohol synthase and epoxide hydrolase activities, respectively. The high capacity of the enzyme system detected in beetroot combined with a simple isolation protocol made possible by the low amounts of endogenous lipids in the enzyme preparation offered an easy access to pinellic and fulgidic acids for use in biological and medical studies.

  6. Bacterial Formation of As(V) and As(III) Ferric Oxyhydroxides in Acid Mine Drainage.

    NASA Astrophysics Data System (ADS)

    Morin, G.; Juillot, F.; Lebrun, S.; Casiot, C.; Elbaz-Poulichet, F.; Bruneel, O.; Personne, J.; Leblanc, M.; Ildefonse, P.; Calas, G.

    2002-12-01

    The oxidation of dissolved Fe(II) which is often promoted by acidophilic bacteria in acid mine drainage (AMD) and some hot springs, leads to the precipitation of Fe(III) oxy-hydroxides which incorporate toxic elements within their structure or adsorb them at their surface, thus limiting their mobility. In such complex natural systems, synchrotron-based techniques as X-ray absorption spectroscopy offer the opportunity to monitor surface/solution interactions as well as redox changes affecting the mobility and toxicity of trace elements as arsenic. Spatial and seasonal variations of the (bio-) oxidation of Fe(II) and As(III), and the subsequent precipitation of As-Fe gels, were followed by XANES, XRD, and SEM along the CarnoulŠs AMD (Gard, France). Chemical and mineralogical data collected on sediments, stromatolite, and bioassay samples showed that some indigenous bacteria living in the As-rich CarnoulŠs water ([As] = up to 350 mg.l-1) play an important role in the nature and composition of the solid phases that sequester arsenic at the site. The formation of nano-crystalline and amorphous As(III) ferric oxy-hydroxides has been related to the presence of bacteria able to oxidize Fe(II) but not As(III), which are only present in winter in the upstream area. A rare ferric arsenite sulfate oxy-hydroxide mineral was discovered in this context. Other types of bacteria, occurring in the downstream area whatever the season, are able to catalyze As(III) to As(V) oxidation and, provided that enough Fe(II) oxidizes, promote the formation of amorphous As(V) rich ferric oxy-hydroxides. These bacterially mediated reactions significantly reduce the concentration of dissolved As(III), which is more toxic and mobile than As(V), and might thus be helpful for designing As-removal processes. This work was supported by the French PEVS and ACI Ecologie Quantitative Programs and the PIRAMID EC program. ?Deceased, 26 October 1999 Juillot F., Ildefonse Ph., Morin G., Calas G., De

  7. Lauric acid-induced formation of a lyotropic nematic phase of disk-shaped micelles.

    PubMed

    Colafemmina, Giuseppe; Recchia, Raffaella; Ferrante, Andrea S; Amin, Samiul; Palazzo, Gerardo

    2010-06-03

    Addition of small amounts of lauric acid (LA) to a micellar solution of sodium dodecyl sulfate (SDS, 11.5 wt %) and cocamidopropyl betaine (CAPB, 3 wt %) has a dramatic effect on the rheological properties and phase behavior of the system. The viscosity increases by more than 1 order of magnitude up to a weight ratio LA/SDS = 0.17 and decreases for further LA loading. The decrease in viscosity is associated with the formation of a birefringent liquid crystalline phase. The evolution of the system from isotropic micelles in the absence of LA to lyotropic liquid crystals up to a weight ratio LA/SDS = 0.30 was probed by a combination of (23)Na NMR quadrupolar splitting, measurements of water and surfactant self-diffusion coefficients via (1)H-PGSE-NMR, and rheology. The evolution of the water self-diffusion coefficients indicates that LA induced a dramatic increase in the anisotropy of disk-shaped micelles. Birefringent samples always showed a well developed (23)Na quadrupolar splitting with a line shape typical of monodomain samples. This suggests that the whole sample is easily oriented within the spectrometer electromagnet, as usually observed for nematic liquid crystals. Sample spinning first destroys the alignment (only a single peak is discernible in the (23)Na NMR spectrum). Then, upon prolonged spinning, the alignment develops again. This indicates that the system is composed by disklike micelles aligning themselves with their normal perpendicular to the magnetic field. On the other hand, the linear viscoelastic response close to the nematic transition shows features usually observed in wormlike micellar systems (e.g., nearly Maxwellian behavior). To reconciliate the rheological data and the NMR evidence of disklike micelles, the formation of columnar stacks of disklike micelles is proposed. The rheology of the isotropic phase can therefore be interpreted in terms of entanglements of "living columnar stacks" of disklike micelles, and the nematic phase observed

  8. Formation of Aldehydic Phosphatidylcholines during the Anaerobic Decomposition of a Phosphatidylcholine Bearing the 9-Hydroperoxide of Linoleic Acid.

    PubMed

    Onyango, Arnold N

    2016-01-01

    Lipid oxidation-derived carbonyl compounds are associated with the development of various physiological disorders. Formation of most of these products has recently been suggested to require further reactions of oxygen with lipid hydroperoxides. However, in rat and human tissues, the formation of 4-hydroxy-2-nonenal is greatly elevated during hypoxic/ischemic conditions. Furthermore, a previous study found an unexpected result that the decomposition of a phosphatidylcholine (PC) bearing the 13-hydroperoxide of linoleic acid under a nitrogen atmosphere afforded 9-oxononanoyl-PC rather than 13-oxo-9,11-tridecadienoyl-PC as the main aldehydic PC. In the present study, products of the anaerobic decomposition of a PC bearing the 9-hydroperoxide of linoleic acid were analysed by electrospray ionization mass spectrometry. 9-Oxononanoyl-PC (ONA-PC) and several well-known bioactive aldehydes including 12-oxo-9-hydroperoxy-(or oxo or hydroxy)-10-dodecenoyl-PCs were detected. Hydrolysis of the oxidized PC products, methylation of the acids obtained thereby, and subsequent gas chromatography-mass spectroscopy with electron impact ionization further confirmed structures of some of the key aldehydic PCs. Novel, hydroxyl radical-dependent mechanisms of formation of ONA-PC and peroxyl-radical dependent mechanisms of formation of the rest of the aldehydes are proposed. The latter mechanisms will mainly be relevant to tissue injury under hypoxic/anoxic conditions, while the former are relevant under both normoxia and hypoxia/anoxia.

  9. Formation of Aldehydic Phosphatidylcholines during the Anaerobic Decomposition of a Phosphatidylcholine Bearing the 9-Hydroperoxide of Linoleic Acid

    PubMed Central

    2016-01-01

    Lipid oxidation-derived carbonyl compounds are associated with the development of various physiological disorders. Formation of most of these products has recently been suggested to require further reactions of oxygen with lipid hydroperoxides. However, in rat and human tissues, the formation of 4-hydroxy-2-nonenal is greatly elevated during hypoxic/ischemic conditions. Furthermore, a previous study found an unexpected result that the decomposition of a phosphatidylcholine (PC) bearing the 13-hydroperoxide of linoleic acid under a nitrogen atmosphere afforded 9-oxononanoyl-PC rather than 13-oxo-9,11-tridecadienoyl-PC as the main aldehydic PC. In the present study, products of the anaerobic decomposition of a PC bearing the 9-hydroperoxide of linoleic acid were analysed by electrospray ionization mass spectrometry. 9-Oxononanoyl-PC (ONA-PC) and several well-known bioactive aldehydes including 12-oxo-9-hydroperoxy-(or oxo or hydroxy)-10-dodecenoyl-PCs were detected. Hydrolysis of the oxidized PC products, methylation of the acids obtained thereby, and subsequent gas chromatography-mass spectroscopy with electron impact ionization further confirmed structures of some of the key aldehydic PCs. Novel, hydroxyl radical-dependent mechanisms of formation of ONA-PC and peroxyl-radical dependent mechanisms of formation of the rest of the aldehydes are proposed. The latter mechanisms will mainly be relevant to tissue injury under hypoxic/anoxic conditions, while the former are relevant under both normoxia and hypoxia/anoxia. PMID:27366754

  10. Effects of strong and weak hydrogen bond formation on VCD spectra: a case study of 2-chloropropionic acid.

    PubMed

    Góbi, Sándor; Vass, Elemér; Magyarfalvi, Gábor; Tarczay, György

    2011-08-21

    The vibrational circular dichroism (VCD) spectrum of S-(-) and R-(+)-2-chloropropionic acid is thoroughly analyzed. Besides the VCD spectrum of the monomer, the dimers (stabilized by strong hydrogen bonds) and the 2-chloropropionic acid-CHCl(3) complexes (stabilized by a weak hydrogen bond) are studied both experimentally (in solution and in low-temperature Ar matrix) and by quantum chemical computations. It is shown that dimer formation drastically changes, and even weak complex formation can also substantially affect the overall shape of the VCD spectrum. The present and previous results can be generalized for the practice of absolute configuration determination of carboxylic acids by VCD spectroscopy. For these measurements, if bulky groups do not block dimer formation, comparison of the computed spectra of the dimers with the experimental spectra recorded in relatively concentrated (∼0.1 mol dm(-3)) solutions is suggested. Our study also shows that due to the stabilization of monomers and/or the formation of weak complexes, the VCD spectrum recorded in CHCl(3) is more complex and, like in the present case, can have a lower intensity than that of the spectrum recorded in CCl(4). Therefore, if solubility allows, CCl(4) is a much preferred solvent over CHCl(3).

  11. A high performance liquid chromatography system for quantification of hydroxyl radical formation by determination of dihydroxy benzoic acids.

    PubMed

    Owen, R W; Wimonwatwatee, T; Spiegelhalder, B; Bartsch, H

    1996-08-01

    The hypoxanthine/xanthine oxidase enzyme system is known to produce the superoxide ion and hydrogen peroxide during the hydroxylation of hypoxanthine via xanthine to uric acid. When chelated iron is included in this system, superoxide reduces iron (III) to iron(II) and the iron(II)-chelate further reacts with hydrogen peroxide to form the highly reactive hydroxyl radical. Because of the limitations of colourimetric and spectrophotometric techniques by which, to date, the mechanisms of hydroxyl radical formation in the hypoxanthine/xanthine oxidase system have been monitored, a high performance liquid chromatography method utilizing the ion-pair reagent tetrabutylammonium hydroxide and salicylic acid as an aromatic probe for quantification of hydroxyl radical formation was set up. In the hypoxanthine/xanthine oxidase system the major products of hydroxyl radical attack on salicylic acid were 2,5-dihydroxy benzoic acid and 2,3-dihydroxy benzoic acid in the approximate ratio of 5:1. That the hydroxyl radical is involved in the hydroxylation of salicylic acid in this system was demonstrated by the potency especially of dimethyl sulphoxide, butanol and ethanol as scavengers. Phytic acid, which is considered to be an important protective dietary constituent against colorectal cancer, inhibited hydroxylation of salicylic acid at a concentration one order of magnitude lower than the classical scavengers, but was only effective in the absence of EDTA. The method has been applied to the study of free radical generation in faeces, and preliminary results indicate that the faecal flora are able to produce reactive oxygen species in abundance.

  12. Formation of Linear Polyenes in Thermal Dehydration of Polyvinyl Alcohol, Catalyzed by Phosphotungstic Acid

    NASA Astrophysics Data System (ADS)

    Tretinnikov, O. N.; Sushko, N. I.

    2015-01-01

    In order to obtain linear polyenes in polyvinyl alcohol films via acid-catalyzed thermal dehydration of the polyvinyl alcohol, we used phosphotungstic acid as the catalyst: a safe and heat-stable solid chemical compound. We established that phosphotungstic acid, introduced as solid nanoparticles into polyvinyl alcohol films, is a more effective dehydration catalyst than hydrochloric acid, since in contrast to HCl it does not evaporate from the film during heat treatment.

  13. High molecular weight hyaluronic acid limits astrocyte activation and scar formation after spinal cord injury

    NASA Astrophysics Data System (ADS)

    Khaing, Zin Z.; Milman, Brian D.; Vanscoy, Jennifer E.; Seidlits, Stephanie K.; Grill, Raymond J.; Schmidt, Christine E.

    2011-08-01

    A major hurdle for regeneration after spinal cord injury (SCI) is the ability of axons to penetrate and grow through the scar tissue. After SCI, inflammatory cells, astrocytes and meningeal cells all play a role in developing the glial scar. In addition, degradation of native high molecular weight (MW) hyaluronic acid (HA), a component of the extracellular matrix, has been shown to induce activation and proliferation of astrocytes. However, it is not known if the degradation of native HA actually enhances glial scar formation. We hypothesize that the presence of high MW HA (HA with limited degradation) after SCI will decrease glial scarring. Here, we demonstrate that high MW HA decreases cell proliferation and reduces chondroitin sulfate proteoglycan (CSPG) production in cultured neonatal and adult astrocytes. In addition, stiffness-matched high MW HA hydrogels crosslinked to resist degradation were implanted in a rat model of spinal dorsal hemisection injury. The numbers of immune cells (macrophages and microglia) detected at the lesion site in animals with HA hydrogel implants were significantly reduced at acute time points (one, three and ten days post-injury). Lesioned animals with HA implants also exhibited significantly lower CSPG expression at ten days post-injury. At nine weeks post-injury, animals with HA hydrogel implants exhibited a significantly decreased astrocytic response, but did not have significantly altered CSPG expression. Combined, these data suggest that high MW HA, when stabilized against degradation, mitigates astrocyte activation in vitro and in vivo. The presence of HA implants was also associated with a significant decrease in CSPG deposition at ten days after SCI. Therefore, HA-based hydrogel systems hold great potential for minimizing undesired scarring as part of future repair strategies after SCI.

  14. Role of Criegee Intermediates in Formation of Sulfuric Acid at BVOCs-rich Cape Corsica Site

    NASA Astrophysics Data System (ADS)

    Kukui, A.; Dusanter, S.; Sauvage, S.; Gros, V.; Bourrianne, T.; Sellegri, K.; Wang, J.; Colomb, A.; Pichon, J. M.; Chen, H.; Kalogridis, C.; Zannoni, N.; Bonsang, B.; Michoud, V.; Locoge, N.; Leonardis, T.

    2015-12-01

    Oxidation of SO2 in reactions with stabilised Criegee Intermediates (sCI) was suggested as an additional source of gaseous sulfuric acid (H2SO4) in the atmosphere, complementary to the conventional H2SO4 formation in reaction of SO2 with OH radicals. Evaluation of the importance of this additional source is complicated due to large uncertainty in the mechanism and rate constants for the reactions of different sCI with SO2, water vapor and other atmospheric species. Here we present an evaluation of the role of sCI in H2SO4 production at remote site on Cape Corsica near the North tip of Corsica Island (Ersa station, Western Mediterranean). In July 2013 comprehensive field observations including gas phase (OH and RO2 radicals, H2SO4, VOCs, NOx, SO2, others) and aerosol measurements were conducted at this site in the frame of ChArMEx project. During the field campaign the site was strongly influenced by local emissions of biogenic volatile compounds (BVOCs), including isoprene and terpenes, forming different sCI in reactions with ozone and, hence, presenting additional source of H2SO4 via sCI+SO2. However, this additional source of H2SO4 at the Ersa site was found to be insignificant. The observed concentrations of H2SO4 were found to be in good agreement with those estimated from the H2SO4 condensation sink and the production of H2SO4 only in the reaction of OH with SO2, without accounting for any additional H2SO4 source. Using the BVOCs observations we present estimation of the upper limit for the rate constants of H2SO4 production via reactions of different sCI with SO2.

  15. Formation of 4(5)-Methylimidazole in Aqueous d-Glucose-Amino Acids Model System.

    PubMed

    Karim, Faris; Smith, J Scott

    2016-01-01

    The International Agency for Research on Cancer (IRAC) has classified 4(5)-methylimidazole (4-MeI) as a group 2B possible human carcinogen. Thus, how 4-MeI forms in a D-glucose (Glu) amino acids (AA) model system is important, as it is how browning is affected. An aqueous solution of Glu was mixed individually in equimolar amounts at 3 concentrations (0.05, 0.1, and 0.15 M) with aqueous solutions of L-Alanine (Ala), L-Arginine (Arg), Glycine (Gly), L-Lysine (Lys), and L-Serine (Ser). The Glu-AA mixtures were reacted at 60, 120, and 160 °C for 1 h. The 4-MeI levels were measured by gas chromatography-mass spectrometry after derivatization with isobutylchloroformate. No 4-MeI was formed at 60 °C for any treatment combination; however, at 120 °C and 0.05 M, Glu-Arg and Glu-Lys produced 0.13 and 0.14 mg/kg of 4-MeI. At 160 °C and 0.05 M all treatment combinations formed 4-MeI. At 160 °C and 0.15 M, the observed levels of Glu-Ala, Glu-Arg, Glu-Gly, Glu-Lys, and Glu-Ser were 0.21, 1.00, 0.15, 0.22, and 0.16 mg/kg. The AA type, reactant concentrations, and temperature significantly affected (P < 0.001) formation of 4-MeI as well as browning. Glu-Lys treatment in all combinations produced the most browning, but Glu-Arg produced the most 4-MeI. This method showed that foods processed using low temperatures may have reduced levels of 4-MeI.

  16. Enhanced mossy fiber sprouting and synapse formation in organotypic hippocampal cultures following transient domoic acid excitotoxicity.

    PubMed

    Pérez-Gómez, Anabel; Tasker, R Andrew

    2014-05-01

    We have previously reported evidence of BDNF upregulation and increased neurogenesis in rat organotypic hippocampal slice cultures (OHSC) after a transient excitotoxic injury to the hippocampal CA1 area induced by low concentrations of the AMPA/kainate receptor agonist domoic acid (DOM). The changes observed in OHSC were consistent with observations in vivo, where low concentrations of DOM administered to rats during perinatal development caused increased BDNF and TrkB expression in the resulting adult animals. The in vivo low dose-DOM treatment also results in permanent alterations in hippocampal structure and function, including abnormal formation of dentate granule cell axons projecting to area CA3 (mossy fiber sprouting). Our objective in the current study is to determine if low concentrations of DOM induce mossy fiber sprouting and/or synaptogenesis in OHSC in order to facilitate future studies on the mechanisms of structural hippocampal plasticity induced by DOM. We report herein that application of a low concentration of DOM (2 μM) for 24 h followed by recovery induced a significant increase in the expression of the mossy fiber marker ZnT3 that progressed over time in culture. The DOM insult (2 μM, 24 h) also resulted in a significant upregulation of both the presynaptic marker synaptophysin and the postsynaptic marker PSD-95. All of the observed effects were fully antagonized by co-administration of the AMPA/kainate antagonists CNQX or NBQX but only partly by the NMDA antagonist CPP and not by the calcium channel blocker nifedipine. We conclude that exposure of OHSC to concentrations of DOM below those required to induce permanent neurotoxicity can induce a progressive change in hippocampal structure that can effectively model DOM effects in vivo.

  17. Keto-Mycolic Acid-Dependent Pellicle Formation Confers Tolerance to Drug-Sensitive Mycobacterium tuberculosis

    PubMed Central

    Sambandan, Dhinakaran; Dao, Dee N.; Weinrick, Brian C.; Vilchèze, Catherine; Gurcha, Sudagar S.; Ojha, Anil; Kremer, Laurent; Besra, Gurdyal S.; Hatfull, Graham F.; Jacobs, William R.

    2013-01-01

    ABSTRACT The chronic nature of tuberculosis (TB), its requirement of long duration of treatment, its ability to evade immune intervention, and its propensity to relapse after drug treatment is discontinued are reminiscent of other chronic, biofilm-associated bacterial diseases. Historically, Mycobacterium tuberculosis was grown as a pellicle, a biofilm-like structure, at the liquid-air interface in a variety of synthetic media. Notably, the most widely administered human vaccine, BCG, is grown as a pellicle for vaccine production. However, the molecular requirements for this growth remain ill defined. Here, we demonstrate that keto-mycolic acids (keto-MA) are essential for pellicle growth, and mutants lacking in or depleted of this MA species are unable to form a pellicle. We investigated the role of the pellicle biofilm in the reduction of antibiotic sensitivity known as drug tolerance using the pellicle-defective ΔmmaA4 mutant strain. We discovered that the ΔmmaA4 mutant, which is both pellicle defective and highly sensitive to rifampicin (RIF) under planktonic growth, when incorporated within the wild-type pellicle biofilm, was protected from the bactericidal activity of RIF. The observation that growth within the M. tuberculosis pellicle biofilm can confer drug tolerance to a drug-hypersensitive strain suggests that identifying molecular requirements for pellicle growth could lead to development of novel interventions against mycobacterial infections. Our findings also suggest that a class of drugs that can disrupt M. tuberculosis biofilm formation, when used in conjunction with conventional antibiotics, has the potential to overcome drug tolerance. PMID:23653446

  18. Conserved valproic-acid-induced lipid droplet formation in Dictyostelium and human hepatocytes identifies structurally active compounds.

    PubMed

    Elphick, Lucy M; Pawolleck, Nadine; Guschina, Irina A; Chaieb, Leila; Eikel, Daniel; Nau, Heinz; Harwood, John L; Plant, Nick J; Williams, Robin S B

    2012-03-01

    Lipid droplet formation and subsequent steatosis (the abnormal retention of lipids within a cell) has been reported to contribute to hepatotoxicity and is an adverse effect of many pharmacological agents including the antiepileptic drug valproic acid (VPA). In this study, we have developed a simple model system (Dictyostelium discoideum) to investigate the effects of VPA and related compounds in lipid droplet formation. In mammalian hepatocytes, VPA increases lipid droplet accumulation over a 24-hour period, giving rise to liver cell damage, and we show a similar effect in Dictyostelium following 30 minutes of VPA treatment. Using (3)H-labelled polyunsaturated (arachidonic) or saturated (palmitic) fatty acids, we shown that VPA treatment of Dictyostelium gives rise to an increased accumulation of both types of fatty acids in phosphatidylcholine, phosphatidylethanolamine and non-polar lipids in this time period, with a similar trend observed in human hepatocytes (Huh7 cells) labelled with [(3)H]arachidonic acid. In addition, pharmacological inhibition of β-oxidation in Dictyostelium phenocopies fatty acid accumulation, in agreement with data reported in mammalian systems. Using Dictyostelium, we then screened a range of VPA-related compounds to identify those with high and low lipid-accumulation potential, and validated these activities for effects on lipid droplet formation by using human hepatocytes. Structure-activity relationships for these VPA-related compounds suggest that lipid accumulation is independent of VPA-catalysed teratogenicity and inositol depletion. These results suggest that Dictyostelium could provide both a novel model system for the analysis of lipid droplet formation in human hepatocytes and a rapid method for identifying VPA-related compounds that show liver toxicology.

  19. Regulating the Skin Permeation Rate of Escitalopram by Ion-pair Formation with Organic Acids.

    PubMed

    Song, Tian; Quan, Peng; Xiang, Rongwu; Fang, Liang

    2016-12-01

    In order to regulate the skin permeation rate (flux) of escitalopram (ESP), ion-pair strategy was used in our work. Five organic acids with different physicochemical properties, benzoic acid (BA), ibuprofen (IB), salicylic acid (SA), benzenesulfonic acid (BSA), and p-aminobenzoic acid (PABA), were employed as counter-ions to regulate the permeation rate of ESP across the rabbit abdominal skin in vitro. The interaction between ESP and organic acids was characterized by FTIR and (13)C NMR spectroscopy. Results showed that all organic acids investigated in this study performed a controlling effect on ESP flux. To further analyze the factors concerned with the permeation capability of ESP-acid complex, a multiple linear regression model was used. It is concluded that the steady-state flux (J) of ESP-acid complexes had a positive correlation with log K o/w (the n-octanol/water partition coefficient of ion-pair complex) and pK a (the acidity of organic acid counter-ion), but a negative correlation with MW (the molecular weight of ion-pair complex). The logK o/w of ion-pair complex is the primary one in all the factors that influence the skin permeation rate of ESP. The results demonstrated that organic acid with appropriate physicochemical properties can be considered as suitable candidate for the transdermal drug delivery of escitalopram.

  20. Investigations of the pore formation in the lead selenide films using glacial acetic acid- and nitric acid-based electrolyte

    PubMed Central

    2012-01-01

    We report a novel synthesis of porous PbSe layers on Si substrates by anodic electrochemical treatment of PbSe/CaF2/Si(111) epitaxial structures in an electrolyte solution based on glacial acetic acid and nitric acid. Electron microscopy, X-ray diffractometry, and local chemical microanalysis investigation results for the porous layers are presented. Average size of the synthesized mesopores with approximately 1010 cm−2 surface density was determined to be 22 nm. The observed phenomenon of the active selenium redeposition on the mesopore walls during anodic treatment is discussed. PMID:22726822

  1. Investigations of the pore formation in the lead selenide films using glacial acetic acid- and nitric acid-based electrolyte.

    PubMed

    Zimin, Sergey P; Gorlachev, Egor S; Naumov, Viktor V; Skok, Fedor O

    2012-01-01

    We report a novel synthesis of porous PbSe layers on Si substrates using anodic electrochemical treatment of PbSe/CaF2/Si(111) epitaxial structures in an electrolyte solution based on glacial acetic acid and nitric acid. Electron microscopy, x-ray diffractometry, and local chemical microanalysis investigations results for the porous layers are presented. Average size of the synthesized mesopores with ~1010 cm-2 surface density was determined to be 22 nm. The observed phenomenon of the active selenium redeposition on the mesopore walls during anodic treatment is discussed.

  2. The effect of particle acidity on secondary organic aerosol formation from α-pinene photooxidation under atmospherically relevant conditions

    NASA Astrophysics Data System (ADS)

    Han, Yuemei; Stroud, Craig A.; Liggio, John; Li, Shao-Meng

    2016-11-01

    Secondary organic aerosol (SOA) formation from photooxidation of α-pinene has been investigated in a photochemical reaction chamber under varied inorganic seed particle acidity levels at moderate relative humidity. The effect of particle acidity on SOA yield and chemical composition was examined under high- and low-NOx conditions. The SOA yield (4.2-7.6 %) increased nearly linearly with the increase in particle acidity under high-NOx conditions. In contrast, the SOA yield (28.6-36.3 %) was substantially higher under low-NOx conditions, but its dependency on particle acidity was insignificant. A relatively strong increase in SOA yield (up to 220 %) was observed in the first hour of α-pinene photooxidation under high-NOx conditions, suggesting that SOA formation was more effective for early α-pinene oxidation products in the presence of fresh acidic particles. The SOA yield decreased gradually with the increase in organic mass in the initial stage (approximately 0-1 h) under high-NOx conditions, which is likely due to the inaccessibility to the acidity over time with the coating of α-pinene SOA, assuming a slow particle-phase diffusion of organic molecules into the inorganic seeds. The formation of later-generation SOA was enhanced by particle acidity even under low-NOx conditions when introducing acidic seed particles after α-pinene photooxidation, suggesting a different acidity effect exists for α-pinene SOA derived from later oxidation stages. This effect could be important in the atmosphere under conditions where α-pinene oxidation products in the gas-phase originating in forested areas (with low NOx and SOx) are transported to regions abundant in acidic aerosols such as power plant plumes or urban regions. The fraction of oxygen-containing organic fragments (CxHyO1+ 33-35 % and CxHyO2+ 16-17 %) in the total organics and the O / C ratio (0.52-0.56) of α-pinene SOA were lower under high-NOx conditions than those under low-NOx conditions (39-40, 17-19, and

  3. Heat-induced formation of mepiquat by decarboxylation of pipecolic acid and its betaine derivative. Part 1: Model system studies.

    PubMed

    Yuan, Yuan; Tarres, Adrienne; Bessaire, Thomas; Stadler, Richard H; Delatour, Thierry

    2017-07-15

    This study describes, for the first time, the role of pipecolic acid betaine and pipecolic acid, naturally present in some foods, in the formation of the plant growth regulator N,N-dimethylpiperidinium (mepiquat) under dry thermal conditions. The formation of mepiquat and intermediate compounds was investigated in model systems using high performance liquid chromatography-quadrupole/time-of-flight mass spectrometry. Mepiquat is released with a yield of up to 0.66mol% after thermal treatment (>150°C) of pipecolic acid betaine. Similar conversion rates are attained with the congener piperidine-2-carboxylic acid (dl-pipecolic acid), albeit in the presence of alkylating agents, such as choline, glycine betaine or trigonelline, that are fairly widespread in food crops. These new pathways to mepiquat indicate that the occurrence of low levels of this thermally induced compound is probably more widespread in processed foods than initially suspected (see Part 2 of this study on the occurrence of mepiquat in selected foodstuffs).

  4. Formation pathways and opioid activity data for 3-hydroxypyridinium compounds derived from glucuronic acid and opioid peptides by Maillard processes.

    PubMed

    Horvat, Stefica; Roscić, Maja; Lemieux, Carole; Nguyen, Thi M-D; Schiller, Peter W

    2007-07-01

    The kinetics of formation and identity of the reaction products of the glucuronic acid with three representative opioid peptides were investigated in vitro. Peptides were conjugated with glucuronic acid either in solution or under dry-heating conditions. From the incubations performed in solution N-(1-deoxy-D-fructofuranos-1-yluronic acid)-peptide derivatives (Amadori compounds) were isolated, whereas from the dry-heated reactions products containing the 3-hydroxypyridinium moiety at the N-terminal of the peptide chain were obtained. Experiments performed under mild dry-heating conditions (40 degrees C) in model systems based on Leu-enkephalin and glucuronic acid, and in environment of either 40% or 75% relative humidity, revealed that the higher level of humidity promoted a process that enhanced 3-hydroxypyridinium compound generation. The mechanism of 3-hydroxypyridinium formation is discussed. In comparison with their respective parent peptides, the N-(1-deoxy-D-fructofuranosyl-uronic acid) derivatives of the opioid peptides showed three- to 11-fold lower mu- and delta-receptor-binding affinities and agonist potencies in the functional assays, likely as a consequence of the steric bulk introduced at the N-terminal amino group. The further decrease in opioid activity observed with the 3-hydroxypyridinium-containing peptides may be due to the lower pK(a) of the 3-hydroxypyridinium moiety and to delocalization of the positive charge in the pyridinium ring system.

  5. Radiation-sensitive indicator based on radiation-chemical formation of acids in polyvinyl butyral films containing chloral hydrate

    NASA Astrophysics Data System (ADS)

    Abdel-Fattah, Atef A.; El-Kelany, M.

    1998-03-01

    Radiation-sensitive indicators based on dyed polyvinyl butyral (PVB) containing acid-sensitive dye (bromophenol blue, BPB) and chloral hydrate (CCl 3CH(OH) 2, 2,2,2-trichloroethane-1, 1-diol) have been developed. These plastic film dosimeters undergo colour change from blue (the alkaline form of BPB) to yellow (the acidic form of BPB), indicating acid formation. The concentration of radiation-formed acids in the films containing different concentrations of chloral hydrate was calculated at different doses. The kinetics of the acid-formation reaction is discussed, indicating a half-order reaction with respect to chloral hydrate concentration. These films can be used as dosimeters for food irradiation applications where the maxima of the useful dose ranges are between 1 and 4 kGy depending on chloral hydrate concentration in the film. The response of these films depends on temperature during irradiation; therefore a correction should be applied. These films have the advantage of negligible humidity effects on response in the intermediate range of relative humidity from 10 to 70% as well as good post-irradiation stability when stored in the dark at room temperature.

  6. The dynamics of complex formation between amylose brushes on gold and fatty acids by QCM-D.

    PubMed

    Cao, Zheng; Tsoufis, Theodoros; Svaldo-Lanero, Tiziana; Duwez, Anne-Sophie; Rudolf, Petra; Loos, Katja

    2013-10-14

    Amylose brushes were synthesized by enzymatic polymerization with glucose-1-phosphate as monomer and rabbit muscle phosphorylase b as catalyst on gold-covered surfaces of a quartz crystal microbalance. Fourier transform infrared (FT-IR) spectra confirmed the presence of the characteristic absorption peaks of amylose between 3100 cm(-1) and 3500 cm(-1). The thickness of the amylose brushes-measured by Spectroscopic Ellipsometry--can be tailored from 4 to 20 nm, depending on the reaction time. The contour length of the stretched amylose chains on gold surfaces has been evaluated by single molecule force spectroscopy, and a total chain length of about 20 nm for 16.2 nm thick amylose brushes was estimated. X-ray photoelectron spectroscopy (XPS) was employed to characterize the amylose brushes before and after the adsorption of fatty acids. The dynamics of inclusion complex formation between amylose brushes and two fatty acids (octanoic acid and myristic acid) with different chain length was investigated as a function of time using a quartz crystal microbalance with dissipation monitoring (QCM-D) immersed in the liquid phase. QCM-D signals including the frequency and dissipation shifts elucidated the effects of the fatty acid concentration, the solvent types, the chain length of the fatty acids and the thickness of the amylose brushes on the dynamics of fatty acid molecule adsorption on the amylose brush-modified sensor surfaces.

  7. Vitamin C (ascorbic acid) induced hydroxyl radical formation in copper contaminated household drinking water: role of bicarbonate concentration.

    PubMed

    Jansson, Patric J; Asplund, Klara U M; Mäkelä, Johanna C; Lindqvist, Christer; Nordström, Tommy

    2003-08-01

    We have previously shown that Vitamin C (ascorbic acid) can trigger hydroxyl radical formation in copper contaminated household drinking water. We report here that the capacity of ascorbic acid to catalyze hydroxyl radical generation in the drinking water samples is strongly dependent on the bicarbonate concentration (buffer capacity and pH) of the samples. We found that at least 50 mg/l bicarbonate was required in the water samples to maintain the pH over 5.0 after ascorbic acid addition. At this pH, that is higher than the pKa1 4.25 of ascorbic acid, a hydroxyl radical generating redox cycling reaction involving the mono-anion of vitamin C and copper could take place. The ascorbic acid induced hydroxyl radical generating reaction could easily be mimicked in Milli-Q water by supplementing the water with copper and bicarbonate. Our results demonstrate that ascorbic acid can induce a pH dependent hydroxyl radical generating reaction in copper contaminated household tap water that is buffered with bicarbonate. The impact of consuming ascorbic acid together with copper and bicarbonate containing drinking water on human health is discussed.

  8. Role of extra-cellular fatty acids in vancomycin induced biofilm formation by vancomycin resistant Staphylococcus aureus.

    PubMed

    Mirani, Zulfiqar Ali; Jamil, Nusrat

    2013-03-01

    In the present study a vancomycin resistant Staphylococcus aureus (S. aureus) (VRSA) (Labeled as CP2) was isolated from the blood of a post-operative cardiac patient is described. It harbors a plasmid which carry vanA gene and exhibited low-level vancomycin resistance (MIC 16μg/mL), was sensitive to teicoplanin. It has been observed that sub-lethal dose of vancomycin induced biofilm formation by CP2 on nylon and silicon indwelling. The results divulge new insights into associations between vancomycin induced biofilms and extra-cellular fatty acids. Gas chromatography coupled with mass spectrometry (GC-MS) revealed that biofilm matrix of CP2 contains a variety of saturated and un-saturated fatty acids, especially, diverse species of octadecanoic (C18:0) and octadecenoic acids (C18:1). A large difference in fatty acids composition was noticed in biofilms, isolated from hydrophobic and hydrophilic surfaces. CP2 produced thicker layer of biofilms on hydrophobic silicon and nylon surfaces which contains variety of saturated, un-saturated and cyclic fatty acids. Contrary to this on hydrophilic glass surfaces it produced thinner layer of biofilm which contains only straight chain saturated fatty acids. These fatty acid components seem to play a crucial role in cell-cell communication and in the establishment of biofilms, consequently, advantageous for pathogens to survive in hospital environment under enormous antibiotics pressure.

  9. Change in haloacetic acid formation potential during UV and UV/H2O2 treatment of model organic compounds.

    PubMed

    Sakai, Hiroshi; Autin, Olivier; Parsons, Simon

    2013-07-01

    Haloacetic acids (HAAs) are disinfection by-products produced by the chlorination of organic matter, including amino acids. Advanced oxidation processes are expected to be effective for the destruction of HAA precursors; however, recent studies have reported the possible failure of these processes to reduce HAA formation potential. This study examined HAA formation potential during the course of UV or UV/H2O2 treatment of three organic compounds: leucine, serine, and resorcinol. HAA formation potential decreased in the treatment of resorcinol, while the potential increased slightly in the treatment of serine and greatly increased for leucine. The chemical structure required for HAA formation was assumed to be produced during the course of UV/H2O2 treatment of leucine and serine. Also, H abstraction from the δ carbon was assumed to result from the initial degradation of leucine by the hydroxyl radical during the UV/H2O2 treatment. The hydroxyl radical may have further reacted with leucine moiety to shorten its carbon chain. This would have produced a chemical structure capable of forming HAA, thus increasing HAA formation potential.

  10. A Single Amino Acid Mutation in the Carnation Ringspot Virus Capsid Protein Allows Virion Formation but Prevents Systemic Infection

    PubMed Central

    Sit, Tim L.; Haikal, Patrick R.; Callaway, Anton S.; Lommel, Steven A.

    2001-01-01

    A Carnation ringspot virus (CRSV) variant (1.26) was identified that accumulates virions but is incapable of forming a systemic infection. The 1.26 capsid protein gene possesses a Ser→Pro mutation at amino acid 282. Conversion of 1.26 amino acid 282 to Ser restored systemic infection, while the reciprocal mutation in wild-type CRSV abolished systemic infection. Similar mutations introduced into the related Red clover necrotic mosaic virus capsid protein gene failed to induce the packaging but nonsystemic movement phenotype. These results provide additional support for the theory that virion formation is necessary but not sufficient for systemic movement with the dianthoviruses. PMID:11533217

  11. Stereoselective formation of trisubstituted vinyl boronate esters by the acid-mediated elimination of α-hydroxyboronate esters.

    PubMed

    Guan, Weiye; Michael, Alicia K; McIntosh, Melissa L; Koren-Selfridge, Liza; Scott, John P; Clark, Timothy B

    2014-08-01

    The copper-catalyzed diboration of ketones followed by an acid-catalyzed elimination leads to the formation of 1,1-disubstituted and trisubstituted vinyl boronate esters with moderate to good yields and selectivity. Addition of tosic acid to the crude diboration products provides the corresponding vinyl boronate esters upon elimination. The trisubstituted vinyl boronate esters are formed as the (Z)-olefin isomer, which was established by subjecting the products to a Suzuki-Miyaura coupling reaction to obtain alkenes of known geometry.

  12. Organosulfate Formation through the Heterogeneous Reaction of Sulfur Dioxide with Unsaturated Fatty Acids and Long-Chain Alkenes.

    PubMed

    Passananti, Monica; Kong, Lingdong; Shang, Jing; Dupart, Yoan; Perrier, Sébastien; Chen, Jianmin; Donaldson, D James; George, Christian

    2016-08-22

    The heterogeneous reaction between SO2 and unsaturated compounds results in the efficient production of organosulfates for several fatty acids and long-chain alkenes. The presence of an acid group, the physical state of the reactants (solid or liquid), the nature of the double bond (cis, trans, terminal), and the use of light irradiation all have an impact on the reaction rate. The reaction was investigated using different set-ups (coated flow tube, aerosol flow tube, and diffuse reflectance infrared Fourier transform cell). The reaction products were identified by high-resolution mass spectrometry and the impact of this reaction on organosulfate formation in the atmosphere is discussed.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  14. Influence of selected fatty acids upon plaque formation and caries in the rat.

    PubMed

    Williams, K A; Schemehorn, B R; McDonald, J L; Stookey, G K; Katz, S

    1982-01-01

    Weanling rats were given high-sucrose cariogenic diets containing 2 per cent lauric acid, linoleic acid, nonanoic acid or monolaurin. Plaque accumulation was determined on the incisors of half the animals during only the last 3 days of the study and on the remaining animals at the conclusion of a 21-day test period when both sulcal and smooth-surface caries were assessed. No significant differences between the test groups in food consumption were observed nor were there any differences in body weight gain. The least amount of plaque was observed in the animals given monolaurin; the other fatty acids exerted no significant effect upon plaque accumulation. The smooth-surface caries data indicated that the least number of lesions occurred in the animals on the diet containing monolaurin. Nonanoic acid was significantly more effective in limiting sulcal caries than any of the other fatty acids studied. Thus both monolaurin and nonanoic acid have significant cariostatic activity in the rat.

  15. Formation of water-soluble dicarboxylic acids, oxoacids and a-dicarbonyls by ozone oxidation of isoprene

    NASA Astrophysics Data System (ADS)

    Kawamura, K.; Tachibana, E.; Sakamoto, Y.; Hirokawa, J.

    2014-12-01

    Water-soluble dicarboxylic acids such as oxalic acid (C2) are the dominant organic compound class in atmospheric aerosols. They can act as cloud condensation nuclei and affect on the Earth climate. Diacids can be primary emitted from fossil fuel combustion and biomass burning and secondarily produced by photochemical oxidations of biogenic and anthropogenic hydrocarbons. However, their sources and formation processes are still not well understood. Recently model and observation studies suggested the importance of isoprene as a precursor of oxalic acid. Isoprene is the most abundant BVOC emitted from terrestrial plants and can serve as important precursors of diacids. We conducted a laboratory oxidation of isoprene (2.0 ppm) with ozone (4.3 ppm) in a Teflon bag for 10 to 480 min. The formed particles were collected with quartz fiber filters and analyzed for diacids, oxoacids and a-dicarbonyls employing water extraction and butyl ester derivatization and using GC and GC/MS techniques. Here, we report the analytical results to better understand the formation process of diacids and related compounds from isoprene. We detected homologous series of saturated diacids (C2-C6), unsaturated diacids (maleic and methylmaleic acids), w-oxocarboxylic acids (C2-C9), pyruvic acid, glyoxal and methylglyoxal. We found that oxalic acid (3000-9700 ngm-3) is the most abundant diacid followed by succinic (C4) or malonic (C3) acid. Their concentrations increased with reaction time showing a maximum in 4 hours. Interestingly, C3/C4 ratios increased with time. The second most abundant species after oxalic acid was generally methylglyoxal (3600-9600 ngm-3), except for the 30 min. sample where methylglyoxal was more abundant than oxalic acid. Glyoxylic acid (wC2) was found as the most abundant oxoacid (1600-3800 ngm-3) followed by wC3 and wC4. Although the concentrations of diacids and related compounds are 1-2 orders magnitude higher than those reported in ambient aerosols, this study

  16. Electrochemical formation of hydroxide for enhancing carbon dioxide and acid gas uptake by a solution

    DOEpatents

    Rau, Gregory Hudson [Castro Valley, CA

    2012-05-15

    A system is described for forming metal hydroxide from a metal carbonate utilizing a water electrolysis cell having an acid-producing anode and a hydroxyl-producing cathode immersed in a water solution of sufficient ionic content to allow an electric current to pass between the hydroxyl-producing cathode and the acid-producing anode. A metal carbonate, in particular water-insoluble calcium carbonate or magnesium carbonate, is placed in close proximity to the acid-producing anode. A direct current electrical voltage is provided across the acid-producing anode and the hydroxyl-producing cathode sufficient to generate acid at the acid-producing anode and hydroxyl ions at the hydroxyl-producing cathode. The acid dissolves at least part of the metal carbonate into metal and carbonate ions allowing the metal ions to travel toward the hydroxyl-producing cathode and to combine with the hydroxyl ions to form the metal hydroxide. The carbonate ions travel toward the acid-producing anode and form carbonic acid and/or water and carbon dioxide. Among other uses, the metal hydroxide formed can be employed to absorb acid gases such as carbon dioxide from a gas mixture. The invention can also generate hydrogen and oxidative gases such as oxygen or chlorine.

  17. Standard enthalpies of formation of perfluoro(2-methyl-3-oxa)hexanoic and perfluoro(2,5-dimethyl-3,6-dioxa)nonanoic acids

    NASA Astrophysics Data System (ADS)

    Lukyanova, V. A.; Papina, T. S.

    2013-02-01

    The energies of combustion of perfluoro(2-methyl-3-oxa)hexanoic and perfluoro(2,5-dimethyl-3,6-dioxa)nonanoic acids are for the first time measured in a calorimeter with a rotating platinized bomb and used to calculate the standard enthalpies of formation of these compounds in the liquid state. Based on the enthalpies of formation, the contribution from the [-CF2OCF(CF3)-] group to the enthalpies of formation of perfluoro acids is calculated.

  18. Occurrence and formation kinetics of pyranomalvidin-procyanidin dimer pigment in Merlot red wine: impact of acidity and oxygen concentrations.

    PubMed

    Pechamat, Laurent; Zeng, Liming; Jourdes, Michael; Ghidossi, Rémy; Teissedre, Pierre-Louis

    2014-02-19

    Once released from red grape skins, anthocyanins undergo various chemical reactions leading to the formation of more stable pigments such as pyranoanthocyanin, as well as other derivatives. Among these pigments, pyranoanthocyanins linked directly to flavanol dimers have been detected and identified in aged Port wine but not in dry red wine. These pigments are very important with regard to the wine color evolution since they are involved in wine color evolution and stabilization. During this investigation, the occurrence in dry red wine of two pyranomalvidin-procyanidin dimer has been established by low and high resolution HPLC-UV-MS analysis. Moreover, the impact of acidity and oxygen levels on their formation in red wine has been estimated. After four months of evolution, the results showed that, for the same pH, the quantity of this pigment was correlated with oxygen concentrations. Moreover, for the same quantity of oxygen, the concentration of this pigment was related to the acidity level.

  19. Polyene Formation Catalyzed by Phosphotungstic Acid and Aluminum Chloride in Thin Films of Poly(Vinyl Alcohol)

    NASA Astrophysics Data System (ADS)

    Tretinnikov, O. N.; Sushko, N. I.; Maly, A. B.

    2016-01-01

    Formation of linear polyenes -(CH=CH) n - during thermal dehydration of thin layers (9-20 μm) of poly(vinyl alcohol) containing phosphotungstic-acid and aluminum-chloride catalysts was investigated. It was found that the concentration of long-chain ( n ≥ 8) polyenes in films containing phosphotungstic acid increased smoothly with increasing annealing time although the kinetics of the dehydration were independent of the film thickness. The polyene ( n ≥ 8) formation rate in films containing aluminum chloride dropped quickly with decreasing film thickness and increasing annealing time. As a result, long-chain polyenes practically did not form regardless of the annealing time for a film thickness of 11 μm.

  20. The 2005 catastrophic acid crater lake drainage, lahar, and acidic aerosol formation at Mount Chiginagak volcano, Alaska, USA: Field observations and preliminary water and vegetation chemistry results

    NASA Astrophysics Data System (ADS)

    Schaefer, Janet R.; Scott, William E.; Evans, William C.; Jorgenson, Janet; McGimsey, Robert G.; Wang, Bronwen

    2008-07-01

    A mass of snow and ice 400-m-wide and 105-m-thick began melting in the summit crater of Mount Chiginagak volcano sometime between November 2004 and early May 2005, presumably owing to increased heat flux from the hydrothermal system, or possibly from magma intrusion and degassing. In early May 2005, an estimated 3.8 × 106 m3 of sulfurous, clay-rich debris and acidic water, with an accompanying acidic aerosol component, exited the crater through a tunnel at the base of a glacier that breaches the south crater rim. Over 27 km downstream, the acidic waters of the flood inundated an important salmon spawning drainage, acidifying Mother Goose Lake from surface to depth (approximately 0.5 km3 in volume at a pH of 2.9 to 3.1), killing all aquatic life, and preventing the annual salmon run. Over 2 months later, crater lake water sampled 8 km downstream of the outlet after considerable dilution from glacial meltwater was a weak sulfuric acid solution (pH = 3.2, SO4 = 504 mg/L, Cl = 53.6 mg/L, and F = 7.92 mg/L). The acid flood waters caused severe vegetation damage, including plant death and leaf kill along the flood path. The crater lake drainage was accompanied by an ambioructic flow of acidic aerosols that followed the flood path, contributing to defoliation and necrotic leaf damage to vegetation in a 29 km2 area along and above affected streams, in areas to heights of over 150 m above stream level. Moss species killed in the event contained high levels of sulfur, indicating extremely elevated atmospheric sulfur content. The most abundant airborne phytotoxic constituent was likely sulfuric acid aerosols that were generated during the catastrophic partial crater lake drainage event. Two mechanisms of acidic aerosol formation are proposed: (1) generation of aerosol mist through turbulent flow of acidic water and (2) catastrophic gas exsolution. This previously undocumented phenomenon of simultaneous vegetation-damaging acidic aerosols accompanying drainage of an acidic

  1. The 2005 catastrophic acid crater lake drainage, lahar, and acidic aerosol formation at Mount Chiginagak volcano, Alaska, USA: Field observations and preliminary water and vegetation chemistry results

    USGS Publications Warehouse

    Schaefer, J.R.; Scott, W.E.; Evans, William C.; Jorgenson, J.; McGimsey, R.G.; Wang, B.

    2008-01-01

    A mass of snow and ice 400-m-wide and 105-m-thick began melting in the summit crater of Mount Chiginagak volcano sometime between November 2004 and early May 2005, presumably owing to increased heat flux from the hydrothermal system, or possibly from magma intrusion and degassing. In early May 2005, an estimated 3.8??106 m3 of sulfurous, clay-rich debris and acidic water, with an accompanying acidic aerosol component, exited the crater through a tunnel at the base of a glacier that breaches the south crater rim. Over 27 km downstream, the acidic waters of the flood inundated an important salmon spawning drainage, acidifying Mother Goose Lake from surface to depth (approximately 0.5 km3 in volume at a pH of 2.9 to 3.1), killing all aquatic life, and preventing the annual salmon run. Over 2 months later, crater lake water sampled 8 km downstream of the outlet after considerable dilution from glacial meltwater was a weak sulfuric acid solution (pH = 3.2, SO4 = 504 mg/L, Cl = 53.6 mg/L, and F = 7.92 mg/L). The acid flood waters caused severe vegetation damage, including plant death and leaf kill along the flood path. The crater lake drainage was accompanied by an ambioructic flow of acidic aerosols that followed the flood path, contributing to defoliation and necrotic leaf damage to vegetation in a 29 km2 area along and above affected streams, in areas to heights of over 150 m above stream level. Moss species killed in the event contained high levels of sulfur, indicating extremely elevated atmospheric sulfurcontent. The most abundant airborne phytotoxic constituent was likely sulfuric acid aerosols that were generated during the catastrophic partial crater lake drainage event. Two mechanisms of acidic aerosol formation are proposed: (1) generation of aerosol mist through turbulent flow of acidic water and (2) catastrophic gas exsolution. This previously undocumented phenomenon of simultaneous vegetationdamaging acidic aerosols accompanying drainage of an acidic crater

  2. Formation and reduction of 5-hydroxymethylfurfural at frying temperature in model system as a function of amino acid and sugar composition.

    PubMed

    Kavousi, Parviz; Mirhosseini, Hamed; Ghazali, Hasanah; Ariffin, Abdul Azis

    2015-09-01

    5-Hydroxymethylfurfural (HMF) is formed during heat treatment of carbohydrate-containing foods, especially in a deep-fat frying process. This study aimed to investigate the effect of amino acids on the formation and reduction of HMF from glucose, fructose and sucrose at frying temperature in model systems containing binary mixtures of an amino acid and a sugar in equal concentrations (0.3M). The results revealed that the formation of HMF from sugars accelerated in the presence of acidic amino acids (i.e. glutamic and aspartic acids). Conversely, the presence of basic amino acids (i.e. lysine, arginine and histidine) led to reduced concentrations of HMF to non-detectable levels in model systems. The results showed that both pH and heating time significantly affected the formation of HMF from fructose in the presence of glutamic acid. In this regard, a higher amount of HMF was formed at lower pH.

  3. Vascular peroxidase 1 catalyzes the formation of hypohalous acids: characterization of its substrate specificity and enzymatic properties.

    PubMed

    Li, Hong; Cao, Zehong; Zhang, Guogang; Thannickal, Victor J; Cheng, Guangjie

    2012-11-15

    The heme-containing peroxidase family comprises eight members in humans. The physiological and pathophysiological roles of heme-containing peroxidases are not well understood. Phagocyte-derived myeloperoxidase (MPO) utilizes chloride and bromide, in the presence of hydrogen peroxide (H(2)O(2)), to generate hypochlorous acid and hypobromous acid, potent oxidizing species that are known to kill invading pathogens. Vascular peroxidase 1 (VPO1) is a new member of the heme-containing peroxidase family; VPO1 is highly expressed in the cardiovascular system, lung, liver, pancreas, and spleen. However, functional roles of VPO1 have not been defined. In this report, we demonstrate the capacity for VPO1 to catalyze the formation of hypohalous acids, and characterize its enzymatic properties. VPO1, like MPO but unlike lactoperoxidase, is able to generate hypochlorous acid, hypobromous acid, and hypothiocyanous acid in the presence of H(2)O(2). Under physiological pH and concentrations of halides (100μM KBr, 100μM KSCN, and 100mM NaCl), VPO1 utilizes approximately 45% of H(2)O(2) for the generation of hypobromous acid, 35% for hypothiocyanous acid, and 18% for hypochlorous acid. The specific activity of VPO1 is ∼10- to 70-fold lower than that of MPO, depending on the specific substrate. These studies demonstrate that the enzymatic properties and substrate specificity of VPO1 are similar to MPO; however, significantly lower catalytic rate constants of VPO1 relative to MPO suggest the possibility of other physiologic roles for this novel heme-containing peroxidase.

  4. Mean-field interactions between nucleic-acid-base dipoles can drive the formation of the double helix

    PubMed Central

    He, Yi; Maciejczyk, Maciej; Ołdziej, Stanisław; Scheraga, Harold A.; Liwo, Adam

    2013-01-01

    A proposed coarse-grained model of nucleic acids demonstrates that average interactions between base dipoles, together with chain connectivity and excluded-volume interactions, are sufficient to form double-helical structures of DNA and RNA molecules. Additionally, local interactions determine helix handedness and direction of strand packing. This result, and earlier research on reduced protein models, suggest that mean-field multipole-multipole interactions are the principal factors responsible for the formation of regular structure of biomolecules. PMID:23496746

  5. Formation of amino acids by cobalt-60 irradiation of hydrogen cyanide solutions

    NASA Technical Reports Server (NTRS)

    Sweeney, M. A.; Toste, A. P.; Ponnamperuma, C.

    1976-01-01

    Experiments were conducted to study the pathway for the prebiotic origin of amino acids from hydrogen cyanide (HCN) under the action of ionizing radiation considered as an effective source of energy on the primitive earth. The irradiations were performed in a cobalt-60 source with a dose rate of 200,000 rad/hr. Seven naturally occurring amino acids are identified among the products formed by the hydrolysis of gamma-irradiated solutions of HCN: glycine, alanine, valine, serine, threonine, aspartic acid, and glutamic acid. The identity of these amino acids is established by gas chromatography and mass spectrometry. Control experiments provided evidence that the amino acids are not the result of contamination.

  6. Factors affecting the formation of nitrogenous disinfection by-products during chlorination of aspartic acid in drinking water.

    PubMed

    Chen, Wei; Liu, Zhigang; Tao, Hui; Xu, Hang; Gu, Yanmei; Chen, Zhaolin; Yu, Jingjing

    2017-01-01

    The formation of emerging nitrogenous disinfection by-products (N-DBPs) from the chlorination of aspartic acid (Asp) was investigated. The yield of dichloroacetonitrile (DCAN) was higher than other N-DBPs, such as dichloroacetamide(DCAcAm) and chloropicrin (TCNM) during the chlorination of Asp. The formation of DCAN, DCAcAm, and TCNM all showed a trend of first increasing and then decreasing during the chlorination of Asp with increasing contact time. The dosage of chlorine had an impact on the formation of DCAN, DCAcAm, and TCNM. The highest yields of DCAN and DCAcAm appeared when the Cl2/Asp molar ratio was about 20, the yield of TCNM increased with increasing the Cl2/Asp molar ratio from 5 to 30 and TCNM was not produced when the ratio was less than 5. Cyanogen chloride (CNCl) was detected when the Cl2/Asp molar ratio was lower than 5. N-DBPs formation was influenced by pH. DCAN formation increased with increasing pH from 5 to 6 and then decreased with increasing pH from 6 to 9, but DCAcAm and TCNM increased with increasing pH from 5 to 8 and then decreased. Higher temperatures reduced the formation of DCAN and DCAcAm, but increased TCNM formation. DCAN and DCAcAm formation decreased, and relatively stable TCNM formation increased, with increasing free chlorine contact time during chloramination. N-nitrosodimethylamine (NDMA) was produced during chloramination of Asp and increased with prolonged chloramination contact time. The presence of bromide ions enhanced the yields of haloacetonitriles and shifted N-DBPs to more brominated species.

  7. Formation of iodoacetic acids during cooking: interaction of iodized table salt with chlorinated drinking water.

    PubMed

    Becalski, A; Lau, B P-Y; Schrader, T J; Seaman, S W; Sun, W F

    2006-10-01

    Iodoacetic and chloroiodoacetic acids were formed when municipal chlorinated tap water was allowed to react with iodized (with potassium iodide) table salt or with potassium iodide itself. Iodoacetic acid was recently shown to be a potent cytotoxic and genotoxic agent. For analysis, samples were extracted with t-amyl methyl ether and converted to the corresponding methyl esters using methanol and sulfuric acid. The concentration of iodoacetic acid was determined by gas chromatography-mass spectrometry (GC-MS) using an authentic standard. The identities of iodoacetic and chloroiodoacetic acids were further confirmed by gas chromatography-high-resolution mass spectrometry (GC-HRMS). Certain influences of sodium hypochlorite and humic acid as well as the concentration of potassium iodide on the yields of these acids were investigated. The concentration of iodoacetic acid in tap water samples boiled with 2 g l-1 of iodized table salt was found to be in the 1.5 microg l-1 range, whilst the concentration of chloroiodoacetic acid was estimated to be three to five times lower.

  8. Electrochemical formation of hydroxide for enhancing carbon dioxide and acid gas uptake by a solution

    SciTech Connect

    Rau, Gregory Hudson

    2014-07-01

    A system for forming metal hydroxide from a metal carbonate utilizes a water electrolysis cell having an acid-producing anode and a hydroxyl-producing cathode immersed in a water solution of sufficient ionic content to allow an electric current to pass between the hydroxyl-producing cathode and the acid-producing anode. A metal carbonate is placed in close proximity to the acid-producing anode. A direct current electrical voltage is provided across the acid-producing anode and the hydroxyl-producing cathode sufficient to generate acid at the acid-producing anode and hydroxyl ions at the hydroxyl-producing cathode. The acid dissolves at least part of the metal carbonate into metal and carbonate ions allowing the metal ions to travel toward the hydroxyl-producing cathode and to combine with the hydroxyl ions to form the metal hydroxide. The carbonate ions travel toward the acid-producing anode and form carbonic acid and/or water and carbon dioxide.

  9. Compound-Specific Isotopic Analysis of Meteoritic Amino Acids as a Tool for Evaluating Potential Formation Pathways

    NASA Technical Reports Server (NTRS)

    Elsila, Jamie E.; Burton, Aaron S.; Callahan, Michael C.; Charnley, Steven B.; Glavin, Daniel P.; Dworkin, Jason P.

    2012-01-01

    Measurements of stable hydrogen, carbon, and nitrogen isotopic ratios (delta D, delta C-13, delta N-15) of organic compounds can reveal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may point towards the most likely of these proposed pathways. The technique of gas chromatography coupled with mass spectrometry and isotope ratio mass spectrometry provides compound-specific structural and isotopic information from a single splitless injection, enhancing the amount of information gained from small amounts of precious samples such as carbonaceous chondrites. We have applied this technique to measure the compound-specific C, N, and H isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites. We are using these measurements to evaluate predictions of expected isotopic enrichments from potential formation pathways and environments, leading to a better understanding of the origin of these compounds.

  10. Effect of dietary acids on the formation of aflatoxin B2a as a means to detoxify aflatoxin B1.

    PubMed

    Rushing, Blake R; Selim, Mustafa I

    2016-09-01

    Aflatoxin B1 (AFB1) is a class 1 carcinogen and a common food contaminant worldwide with widely uncontrolled human exposure. The ability of organic acids to transform AFB1 into a known detoxified form, aflatoxin B2a (AFB2a), was investigated using high performance liquid chromatography-electrospray ionisation-time of flight mass spectrometry (HPLC/ESI/TOF/MS). The identity of the transformation product was confirmed by accurate mass measurement, chromatographic separation from other aflatoxins, H(1)-nuclear magnetic resonance (NMR) and infrared (IR) spectroscopy. Of the weak acids tested, citric acid was found to be the most effective for AFB2a formation. At room temperature, 1 M citric acid was able to convert > 97% of AFB1 to AFB2a over 96 h of treatment. Up to 98% transformation was achieved by boiling AFB1 in the presence of citric acid for 20 min. AFB1 hydration after ingestion was explored by spiking AFB1 into simulated gastric fluid containing citric acid. Under these conditions, > 71% of AFB1 was hydrated to AFB2a and did not show any reversion to the parent compound after being transferred to a neutral solution. These results provide a basis for a practical and effective method for detoxification of AFB1 in contaminated foods.

  11. Formation of Guaiacol by Spoilage Bacteria from Vanillic Acid, a Product of Rice Koji Cultivation, in Japanese Sake Brewing.

    PubMed

    Ito, Toshihiko; Konno, Mahito; Shimura, Yoichiro; Watanabe, Seiei; Takahashi, Hitoshi; Hashizume, Katsumi

    2016-06-08

    The formation of guaiacol, a potent phenolic off-odor compound in the Japanese sake brewing process, was investigated. Eight rice koji samples were analyzed, and one contained guaiacol and 4-vinylguaiacol (4-VG) at extraordinarily high levels: 374 and 2433 μg/kg dry mass koji, respectively. All samples contained ferulic and vanillic acids at concentrations of mg/kg dry mass koji. Guaiacol forming microorganisms were isolated from four rice koji samples. They were identified as Bacillus subtilis, B. amyloliquefaciens/subtilis, and Staphylococcus gallinarum using 16S rRNA gene sequence. These spoilage bacteria convert vanillic acid to guaiacol and ferulic acid to 4-VG. However, they convert very little ferulic acid or 4-VG to guaiacol. Nine strains of koji fungi tested produced vanillic acid at the mg/kg dry mass koji level after cultivation. These results indicated that spoilage bacteria form guaiacol from vanillic acid, which is a product of koji cultivation in the sake brewing process.

  12. Arachidonic acid release and prostaglandin F(2alpha) formation induced by anandamide and capsaicin in PC12 cells.

    PubMed

    Someya, Akiyoshi; Horie, Syunji; Murayama, Toshihiko

    2002-08-23

    Anandamide, an endogenous agonist of cannabinoid receptors, activates various signal transduction pathways. Anandamide also activates vanilloid VR(1) receptor, which was a nonselective cation channel with high Ca(2+) permeability and had sensitivity to capsaicin, a pungent principle in hot pepper. The effects of anandamide and capsaicin on arachidonic acid metabolism in neuronal cells have not been well established. We examined the effects of anandamide and capsaicin on arachidonic acid release in rat pheochromocytoma PC12 cells. Both agents stimulated [3H]arachidonic acid release in a concentration-dependent manner from the prelabeled PC12 cells even in the absence of extracellular CaCl(2). The effect of anandamide was neither mimicked by an agonist nor inhibited by an antagonist for cannabinoid receptors. The effects of anandamide and capsaicin were inhibited by phospholipase A(2) inhibitors, but not by an antagonist for vanilloid VR(1) receptor. In PC12 cells preincubated with anandamide or capsaicin, [3H]arachidonic acid release was marked and both agents were no more effective. Co-addition of anandamide or capsaicin synergistically enhanced [3H]arachidonic acid release by mastoparan in the absence of CaCl(2). Anandamide stimulated prostaglandin F(2alpha) formation. These findings suggest that anandamide and capsaicin stimulated arachidonic acid metabolism in cannabinoid receptors- and vanilloid VR(1) receptor-independent manner in PC12 cells. The possible mechanisms are also discussed.

  13. SIRT1 prevents pulmonary thrombus formation induced by arachidonic acid via downregulation of PAF receptor expression in platelets.

    PubMed

    Kim, Yun Hak; Bae, Jin Ung; Kim, In Suk; Chang, Chulhun L; Oh, Sae Ock; Kim, Chi Dae

    2016-12-01

    SIRT1, a class III histone deacetylase, is critically involved in cellular response to stress and modulates cardiovascular risk factors. However, its role in thrombus formation is largely unknown. Thus, this study investigated the effect of SIRT1 on pulmonary thrombus formation, and then identified its role in the modulation of platelet aggregation. In isolated human platelets, cell aggregation was increased by various platelet activators, such as platelet activating factor (PAF), arachidonic acid (AA), ADP, and thrombin. AA- and PAF-mediated platelet aggregations were suppressed by WEB2086, a PAF receptor (PAFR) antagonist. Pulmonary thrombus formation induced by PAF or AA was also attenuated by WEB2086, suggesting that PAFR plays a key role in AA-induced platelet aggregation. In platelets isolated from SIRT1-TG mice as well as in platelets treated with resveratrol or reSIRT1, PAFR expression was decreased, whereas this expressional downregulation by SIRT1 activators was inhibited in platelets treated with MG132 (a proteasome inhibitor) or NH4Cl (a lysosome inhibitor). Furthermore, platelet aggregation induced by AA was markedly attenuated by resveratrol and reSIRT1. Likewise, the increased pulmonary thrombus formation in mice treated with AA was also attenuated by SIRT1 activators. In line with these results, pulmonary thrombus formation was markedly attenuated in SIRT1-TG mice. Taken together, this study showed that SIRT1 downregulates PAFR expression on platelets via proteasomal and lysosomal pathways, and that this downregulation inhibits platelet aggregation in vitro and pulmonary thrombus formation in vivo.

  14. Boric acid solution concentration influencing p-type emitter formation in n-type crystalline Si solar cells

    NASA Astrophysics Data System (ADS)

    Singha, Bandana; Singh Solanki, Chetan

    2016-09-01

    Boric acid (BA) is a spin on dopant (BSoD) source which is used to form p+ emitters in n-type c-Si solar cells. High purity boric acid powder (99.99% pure) when mixed with deionized (DI) water can result in high quality p-type emitter with less amount of surface defects. In this work, we have used different concentrations of boric acid solution concentrations to fabricate p-type emitters with sheet resistance values < 90 Ω/□. The corresponding junction depths for the same are less than 500 nm as measured by SIMS analysis. Boron rich layer (BRL), which is considered as detrimental in emitter performance is found to be minimal for BA solution concentration less than 2% and hence useful for p-type emitter formation.

  15. Studies on the formation by rat brain preparations of CDP-diglyceride from CTP and phosphatidic acids of varying fatty acid compositions.

    PubMed

    Bishop, H H; Strickland, K P

    1976-03-01

    The enzyme, CTP:phosphatidate cytidylyltransferase (EC2.7.7.41) which catalyses formation of CDP-diglyceride from CTP and phosphatidic acid has been studied in rat brain preparations and other tissues. Improvement, as judged by the higher tissue activities obtained, in the assay method for this enzyme was achieved through use of phosphatidic acids sonicated in buffer-detergent solution saturated with ether and containing bovine serum albumin and use of short incubation times which essentially provided a measure of initial rates. The enzyme of rat brain microsomes yielded with 1,2-dioleolphosphatidic acid as substrate a pH optimum of 6.8 with maleate buffer and optimal concentrations of 60mM for MG2+, 6MM for CTP and 250 mug per 0.8 ml for phosphatidic acid. Enzyme activity was mainly located in the 90,000 X g fraction (microsomal) with small but significant activity in the 12,000 X g fraction. Comparison of activities (nanomoles CTP incorporated per milligram protein per minute) amongst tissues showed the following order: brain, 1.87; liver, 1.32; lung, 1.19; small intestine, 1.00; kidney, 0.69; heart, 0.41; diaphragm, 0.07; skeletal muscle, 0.02. Examination of the effect of varying the fatty acid composition in the phosphatidic acids added exogenously gave the following order (activities in parentheses); 1-stearoyl-2-oleoyl- (5.58), 1-oleoyl-2-stearoyl- (5.37), 1,2-dioleoyl- (4.49) 1-palmitoyl-2-oleoyl-(3.85), 1-stearoyl-2-arachidonoyl-(3.31), 1-arachidonoyl-2-stearoyl-(3.16), 1,2-diarachidonoyl-(0.72), 1,2-dicaproyl-(0.67), 1,2-dipalmitoyl-(0.67) and 1,2-distearoyl-(0.18). The single bis- and lysophosphatidic acids tested were inactive as substrates. Apart from a possible preference for one or more unsaturated fatty acids the transferase enzyme showed no selectivity in respect to the fatty acid distribution of phosphatidic acids.

  16. An attempt to theoretically predict third-phase formation in the dimethyldibutyltetradecylmalonamide (DMDBTDMA)/dodecane/water/nitric acid extraction system

    SciTech Connect

    LeFrancois, L.; Tondre, C.; Belnet, F.; Noel, D.

    1999-03-01

    The formation of a third phase in solvent extraction (due to splitting of the organic phase into two layers) often occurs when the aqueous phase is highly concentrated in acids. This has been reported with the extraction system dimethyldibutyltetradecylmalonamide (DMDBTDMA)/n-dodecane/water/nitric acid, both in the presence and absence of metal ions. Whereas many experimental efforts have been made to investigate the effects of different parameters on third-phase formation, very few attempts have been made to predict this phenomenon on theoretical grounds. Because the part played by aggregation of the extractant molecules is recognized, the authors propose a new predictive approach based on the use of the Flory-Huggins theory of polymer solutions, which had been successfully applied for the prediction of phase separation phenomena in nonionic surfactant solutions. The authors show that this model can provide an excellent prediction of the demixing curve (in the absence of metal ions) when establishing the relation between the interaction parameter {chi}{sub 12} calculated from this theory and the nitric acid content of the aqueous phase. Apparent values of the solubility parameter {delta}{sub 2} of the diamide extractant at different acid loadings have been calculated, from which the effect of the nature of the diluent can also be very nicely predicted.

  17. Simplified mechanism for new particle formation from methanesulfonic acid, amines, and water via experiments and ab initio calculations

    PubMed Central

    Dawson, Matthew L.; Varner, Mychel E.; Perraud, Véronique; Ezell, Michael J.; Gerber, R. Benny; Finlayson-Pitts, Barbara J.

    2012-01-01

    Airborne particles affect human health and significantly influence visibility and climate. A major fraction of these particles result from the reactions of gaseous precursors to generate low-volatility products such as sulfuric acid and high-molecular weight organics that nucleate to form new particles. Ammonia and, more recently, amines, both of which are ubiquitous in the environment, have also been recognized as important contributors. However, accurately predicting new particle formation in both laboratory systems and in air has been problematic. During the oxidation of organosulfur compounds, gas-phase methanesulfonic acid is formed simultaneously with sulfuric acid, and both are found in particles in coastal regions as well as inland. We show here that: (i) Amines form particles on reaction with methanesulfonic acid, (ii) water vapor is required, and (iii) particle formation can be quantitatively reproduced by a semiempirical kinetics model supported by insights from quantum chemical calculations of likely intermediate clusters. Such an approach may be more broadly applicable in models of outdoor, indoor, and industrial settings where particles are formed, and where accurate modeling is essential for predicting their impact on health, visibility, and climate. PMID:23090988

  18. Modulating weak intramolecular interactions through the formation of beryllium bonds: complexes between squaric acid and BeH2.

    PubMed

    Montero-Campillo, M Merced; Lamsabhi, Al Mokhtar; Mó, Otilia; Yáñez, Manuel

    2013-07-01

    The electronic structure of the two most stable isomers of squaric acid and their complexes with BeH2 were investigated at the B3LYP/6-311 + G(3df,2p)// B3LYP/6-31 + G(d,p) level of theory. Squaric acid forms rather strong beryllium bonds with BeH2, with binding energies of the order of 60 kJ mol(-1). The preferential sites for BeH2 attachment are the carbonyl oxygen atoms, but the global minima of the potential energy surfaces of both EZ and ZZ isomers are extra-stabilized through the formation of a BeH···HO dihydrogen bond. More importantly, analysis of the electron density of these complexes shows the existence of significant cooperative effects between the beryllium bond and the dihydrogen bond, with both becoming significantly reinforced. The charge transfer involved in the formation of the beryllium bond induces a significant electron density redistribution within the squaric acid subunit, affecting not only the carbonyl group interacting with the BeH2 moiety but significantly increasing the electron delocalization within the four membered ring. Accordingly the intrinsic properties of squaric acid become perturbed, as reflected in its ability to self-associate.

  19. Phosphatidic acid formation is required for extracellular ATP-mediated nitric oxide production in suspension-cultured tomato cells.

    PubMed

    Sueldo, Daniela J; Foresi, Noelia P; Casalongué, Claudia A; Lamattina, Lorenzo; Laxalt, Ana M

    2010-03-01

    *In animals and plants, extracellular ATP exerts its effects by regulating the second messengers Ca(2+), nitric oxide (NO) and reactive oxygen species (ROS). In animals, phospholipid-derived molecules, such as diacylglycerol, phosphatidic acid (PA) and inositol phosphates, have been associated with the extracellular ATP signaling pathway. The involvement of phospholipids in extracellular ATP signaling in plants, as it is established in animals, is unknown. *In vivo phospholipid signaling upon extracellular ATP treatment was studied in (32)P(i)-labeled suspension-cultured tomato (Solanum lycopersicum) cells. *Here, we report that, in suspension-cultured tomato cells, extracellular ATP induces the formation of the signaling lipid phosphatidic acid. Exogenous ATP at doses of 0.1 and 1 mM induce the formation of phosphatidic acid within minutes. Studies on the enzymatic sources of phosphatidic acid revealed the participation of both phospholipase D and C in concerted action with diacylglycerol kinase. *Our results suggest that extracellular ATP-mediated nitric oxide production is downstream of phospholipase C/diacylglycerol kinase activation.

  20. A study of the formation and self-lubrication mechanisms of boric acid films on boric oxide coatings

    SciTech Connect

    Erdemir, A.; Fenske, G.R.; Erck, R.A.

    1990-01-01

    An investigation was made of the formation and self-lubrication mechanisms of boric acid films on boric oxide coatings prepared by vacuum evaporation. Measured friction coefficients of a steel ball sliding on a boric-oxide-coated-steel disk and a sapphire ball sliding on a boric-oxide-coated-alumina disk were 0.025 to 0.05 at steady state, depending on load and substrate material. This low friction was correlated with the formation of a lubricious boric acid film on boric oxide coatings exposed to open air. For the mechanism of self-lubrication, the layered-triclinic-crystal structure of boric acid was proposed. The atoms constituting each boric acid molecule are arrayed in closely packed and strongly bonded layers that are 0.318 nm apart and held together by weak forces, such as van der Waals. It is hypothesized that during sliding, these layers can align themselves parallel to the direction of relative motion, and once so aligned,, can slide over one another with relative ease to provide low friction. Structural and chemical findings were included to substantiate the proposed solid lubrication mechanism. 15 refs., 5 figs.

  1. Deoxycholic acid formation in gnotobiotic mice associated with human intestinal bacteria.

    PubMed

    Narushima, Seiko; Itoha, Kikuji; Miyamoto, Yukiko; Park, Sang-Hee; Nagata, Keiko; Kuruma, Kazuo; Uchida, Kiyohisa

    2006-09-01

    In humans and animals, intestinal flora is indispensable for bile acid transformation. The goal of our study was to establish gnotobiotic mice with intestinal bacteria of human origin in order to examine the role of intestinal bacteria in the transformation of bile acids in vivo using the technique of gnotobiology. Eight strains of bile acid-deconjugating bacteria were isolated from ex-germ-free mice inoculated with a human fecal dilution of 10(-6), and five strains of 7alpha-dehydroxylating bacteria were isolated from the intestine of limited human flora mice inoculated only with clostridia. The results of biochemical tests and 16S rDNA sequence analysis showed that seven out of eight bile acid-deconjugating strains belong to a bacteroides cluster (Bacteroides vulgatus, B. distasonis, and B. uniformis), and one strain had high similarity with Bilophila wadsworthia. All five strains that converted cholic acid to deoxycholic acid had greatest similarity with Clostridium hylemonae. A combination of 10 isolated strains converted taurocholic acid into deoxycholic acid both in vitro and in the mouse intestine. These results indicate that the predominant bacteria, mainly Bacteroides, in human feces comprise one of the main bacterial groups for the deconjugation of bile acids, and clostridia may play an important role in 7aplha-dehydroxylation of free-form primary bile acids in the intestine although these strains are not predominant. The gnotobiotic mouse with bacteria of human origin could be a useful model in studies of bile acid metabolism by human intestinal bacteria in vivo.

  2. First online measurements of sulfuric acid gas in modern heavy-duty diesel engine exhaust: implications for nanoparticle formation.

    PubMed

    Arnold, F; Pirjola, L; Rönkkö, T; Reichl, U; Schlager, H; Lähde, T; Heikkilä, J; Keskinen, J

    2012-10-16

    To mitigate the diesel particle pollution problem, diesel vehicles are fitted with modern exhaust after-treatment systems (ATS), which efficiently remove engine-generated primary particles (soot and ash) and gaseous hydrocarbons. Unfortunately, ATS can promote formation of low-vapor-pressure gases, which may undergo nucleation and condensation leading to formation of nucleation particles (NUP). The chemical nature and formation mechanism of these particles are only poorly explored. Using a novel mass spectrometric method, online measurements of low-vapor-pressure gases were performed for exhaust of a modern heavy-duty diesel engine operated with modern ATS and combusting low and ultralow sulfur fuels and also biofuel. It was observed that the gaseous sulfuric acid (GSA) concentration varied strongly, although engine operation was stable. However, the exhaust GSA was observed to be affected by fuel sulfur level, exhaust after-treatment, and driving conditions. Significant GSA concentrations were measured also when biofuel was used, indicating that GSA can be originated also from lubricant oil sulfur. Furthermore, accompanying NUP measurements and NUP model simulations were performed. We found that the exhaust GSA promotes NUP formation, but also organic (acidic) precursor gases can have a role. The model results indicate that that the measured GSA concentration alone is not high enough to grow the particles to the detected sizes.

  3. Eukaryotic stromatolite builders in acid mine drainage: Implications for Precambrian iron formations and oxygenation of the atmosphere?

    NASA Astrophysics Data System (ADS)

    Brake, S. S.; Hasiotis, S. T.; Dannelly, H. K.; Connors, K. A.

    2002-07-01

    Biological activity of Euglena mutabilis, an acidophilic, photosynthetic protozoan, contributes to the formation of Fe-rich stromatolites in acid mine drainage systems. E. mutabilis is the dominant microbe in bright green benthic mats (biofilm), coating drainage channels at abandoned coal mine sites in Indiana. It builds biolaminates through phototactic and aerotactic behavior, similar to prokaryotes, by moving through precipitates that periodically cover the mats. E. mutabilis also contributes to formation of Fe-rich stromatolites by (1) intracellularly storing Fe compounds released after death, contributing to the solid material of stromatolites and acting as nucleation sites for precipitation of authigenic Fe minerals, and (2) generating O2 via photosynthesis that further facilitates precipitation of reduced Fe, any excess O2 not consumed by Fe precipitation being released to the atmosphere. Recognition of E. mutabilis dominated biofilm in acidic systems raises a provocative hypothesis relating processes involved in formation of Fe-rich stromatolites by E. mutabilis to those responsible for development of Precambrian stromatolitic Fe formations and oxygenation of the early atmosphere.

  4. Formation of a Stabilized Cysteine Sulfinic Acid Is Critical for the Mitochondrial Function of the Parkinsonism Protein DJ-1*

    PubMed Central

    Blackinton, Jeff; Lakshminarasimhan, Mahadevan; Thomas, Kelly J.; Ahmad, Rili; Greggio, Elisa; Raza, Ashraf S.; Cookson, Mark R.; Wilson, Mark A.

    2009-01-01

    The formation of cysteine-sulfinic acid has recently become appreciated as a modification that links protein function to cellular oxidative status. Human DJ-1, a protein associated with inherited parkinsonism, readily forms cysteine-sulfinic acid at a conserved cysteine residue (Cys106 in human DJ-1). Mutation of Cys106 causes the protein to lose its normal protective function in cell culture and model organisms. However, it is unknown whether the loss of DJ-1 protective function in these mutants is due to the absence of Cys106 oxidation or the absence of the cysteine residue itself. To address this question, we designed a series of substitutions at a proximal glutamic acid residue (Glu18) in human DJ-1 that alter the oxidative propensity of Cys106 through changes in hydrogen bonding. We show that two mutations, E18N and E18Q, allow Cys106 to be oxidized to Cys106-sulfinic acid under mild conditions. In contrast, the E18D mutation stabilizes a cysteine-sulfenic acid that is readily reduced to the thiol in solution and in vivo. We show that E18N and E18Q can both partially substitute for wild-type DJ-1 using mitochondrial fission and cell viability assays. In contrast, the oxidatively impaired E18D mutant behaves as an inactive C106A mutant and fails to protect cells. We therefore conclude that formation of Cys106-sulfinic acid is a key modification that regulates the protective function of DJ-1. PMID:19124468

  5. N-N bond formation in Ugi processes: from nitric acid to libraries of nitramines.

    PubMed

    Mercalli, Valentina; Nyadanu, Aude; Cordier, Marie; Tron, Gian Cesare; Grimaud, Laurence; El Kaim, Laurent

    2017-02-09

    The Ugi reaction has drawn considerable attention over the years leading to numerous libraries of heterocycles and various extensions changing the nature of the components of the coupling. We report here the use of nitric acid as carboxylic acids surrogates, displaying the first aminative Ugi-type reaction leading to nitramines.

  6. Influence of Aerosol Acidity on the Formation of Secondary Organic Aerosol from Biogenic Precursor Hydrocarbons

    EPA Science Inventory

    Secondary organic aerosol (SOA) formation and dynamics may be important factors for the role of aerosols in adverse health effects, visibility and climate change. Formation of SOA occurs when a parent volatile organic compound is oxidized to create products that form in a conden...

  7. Titan's primordial soup: formation of amino acids via low-temperature hydrolysis of tholins.

    PubMed

    Neish, Catherine D; Somogyi, Arpád; Smith, Mark A

    2010-04-01

    Titan organic haze analogues, or "tholins," produce biomolecules when hydrolyzed at low temperature over long timescales. By using a combination of high-resolution mass spectroscopy and tandem mass spectrometry fragmentation techniques, four amino acids were identified in a tholin sample that had been hydrolyzed in a 13 wt % ammonia-water solution at 253 + or - 1 K and 293 + or - 1 K for 1 year. These four species have been assigned as the amino acids asparagine, aspartic acid, glutamine, and glutamic acid. This represents the first detection of biologically relevant molecules created under conditions thought to be similar to those found in impact melt pools and cryolavas on Titan, which are at a stage of chemical evolution not unlike the "primordial soup" of the early Earth. Future missions to Titan should therefore carry instrumentation capable of, but certainly not limited to, detecting amino acids and other prebiotic molecules on Titan's surface.

  8. Titan's Primordial Soup: Formation of Amino Acids via Low-Temperature Hydrolysis of Tholins

    NASA Astrophysics Data System (ADS)

    Neish, Catherine D.; Somogyi, Árpád; Smith, Mark A.

    2010-04-01

    Titan organic haze analogues, or "tholins," produce biomolecules when hydrolyzed at low temperature over long timescales. By using a combination of high-resolution mass spectroscopy and tandem mass spectrometry fragmentation techniques, four amino acids were identified in a tholin sample that had been hydrolyzed in a 13 wt % ammonia-water solution at 253 ± 1 K and 293 ± 1 K for 1 year. These four species have been assigned as the amino acids asparagine, aspartic acid, glutamine, and glutamic acid. This represents the first detection of biologically relevant molecules created under conditions thought to be similar to those found in impact melt pools and cryolavas on Titan, which are at a stage of chemical evolution not unlike the "primordial soup" of the early Earth. Future missions to Titan should therefore carry instrumentation capable of, but certainly not limited to, detecting amino acids and other prebiotic molecules on Titan's surface.

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

    SciTech Connect

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

    2011-01-20

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

  10. A systematic investigation and insight into the formation mechanism of bilayers of fatty acid/soap mixtures in aqueous solutions.

    PubMed

    Xu, Wenlong; Song, Aixin; Dong, Shuli; Chen, Jingfei; Hao, Jingcheng

    2013-10-08

    Vesicles are the most common form of bilayer structures in fatty acid/soap mixtures in aqueous solutions; however, a peculiar bilayer structure called a "planar sheet" was found for the first time in the mixtures. In the past few decades, considerable research has focused on the formation theory of bilayers in fatty acid/soap mixtures. The hydrogen bond theory has been widely accepted by scientists to explain the formation of bilayers. However, except for the hydrogen bond, no other driving forces were proposed systematically. In this work, three kinds of weak interactions were investigated in detail, which could perfectly demonstrate the formation mechanism of bilayer structures in the fatty acid/soap mixtures in aqueous solutions. (i) The influence of hydrophobic interaction was detected by changing the chain length of fatty acid (C(n)H(2n+1)COOH), in which n = 10 to 18, the phase behavior was investigated, and the phase region was presented. With the help of cryogenic transmission electron microscopy (cryo-TEM) observations, deuterium nuclear magnetic resonance ((2)H NMR), and X-ray diffraction (XRD) measurements, the vesicles and planar sheets were determined. The chain length of C(n)H(2n+1)COOH has an important effect on the physical state of the hydrophobic chain, resulting in an obvious difference in the viscoelasticity of the solution samples. (ii) The existence of hydrogen bonds between fatty acids and their soaps in aqueous solutions was demonstrated by Fourier transform infrared (FT-IR) spectroscopy and molecule dynamical simulation. From the pH measurements, the pH ranges of the bilayer formation were at the pKa values of fatty acids, respectively. (iii) Counterions can be embedded in the stern layer of the bilayers and screen the electrostatic repulsion between the COO(-) anionic headgroups. FT-IR characterization demonstrated a bidentate bridging coordination mode between counterions and carboxylates. The conductivity measurements provided the degree

  11. Sulfuric acid measurements in the exhaust plume of a jet aircraft in flight: Implications for the sulfuric acid formation efficiency

    NASA Astrophysics Data System (ADS)

    Curtius, J.; Arnold, F.; Schulte, P.

    2002-04-01

    Sulfuric acid concentrations were measured in the exhaust plume of a B737-300 aircraft in flight. The measurements were made onboard of the German research aircraft Falcon using the Volatile Aerosol Component Analyzer (VACA). The VACA measures total H2SO4, which is the sum of gaseous H2SO4 and aerosol H2SO4. Measurements took place at distances of 25-200 m behind the B737 corresponding to plume ages of about 0.1-1 seconds. The fuel sulfur content (FSC) of the fuel burned by the B737 engines was alternatively 2.6 and 56 mg sulfur per kilogram fuel (ppmm). H2SO4 concentrations measured in the plume for the 56 ppmm sulfur case were up to ~600 pptv. The average concentration of H2SO4 measured in the ambient atmosphere outside the aircraft plume was 88 pptv, the maximum ambient atmospheric H2SO4 was ~300 pptv. Average efficiencies ɛΔCO2 = 3.3 +/- 1.8% and ɛΔT = 2.9 +/- 1.6% for fuel sulfur conversion to sulfuric acid were inferred when relating the H2SO4 data to measurements of the plume tracers ΔCO2 and ΔT.

  12. Dicarboxylic acids, ω-oxocarboxylic acids, α-dicarbonyls, WSOC, OC, EC, and inorganic ions in wintertime size-segregated aerosols from central India: Sources and formation processes.

    PubMed

    Deshmukh, Dhananjay K; Kawamura, Kimitaka; Deb, Manas K

    2016-10-01

    The size distributions of aerosols can provide evidences for their sources and formation processes in the atmosphere. Size-segregated aerosols (9-sizes) were collected in urban site (Raipur: 21.2°N and 82.3°E) in central India during winter of 2012-2013. The samples were analyzed for dicarboxylic acids (C2-C12), ω-oxocarboxylic acids (ωC2-ωC9), pyruvic acid and α-dicarbonyls (C2-C3) as well as elemental carbon (EC), organic carbon (OC), water-soluble OC (WSOC) and inorganic ions. Diacids showed a predominance of oxalic acid (C2) followed by succinic and azelaic acid whereas ω-oxoacids exhibited a predominance of glyoxylic acid and glyoxal was more abundant than methylglyoxal in all the sizes. Diacids, ω-oxoacids and α-dicarbonyls showed bimodal size distribution with peaks in fine and coarse modes. High correlations of fine mode diacids and related compounds with potassium and levoglucosan suggest that they were presumably due to a substantial contribution of primary emission from biomass burning and secondary production from biomass burning derived precursors. High correlations of C2 with higher carbon number diacids (C3-C9) suggest that they have similar sources and C2 may be produced via the decay of its higher homologous diacids in fine mode. Considerable portions of diacids and related compounds in coarse mode suggest that they were associated with mineral dust particles by their adsorption and photooxidation of anthropogenic and biogenic precursors via heterogeneous reaction on dust surface. This study demonstrates that biomass burning and dust particles are two major factors to control the size distribution of diacids and related compounds in the urban aerosols from central India.

  13. Alteration of Basaltic Glass to Mg/Fe-Smectite under Acidic Conditions: A Potential Smectite Formation Mechanism on Mars

    NASA Technical Reports Server (NTRS)

    Peretyazhko, Tanya; Sutter, Brad; Ming, Douglas W.

    2014-01-01

    Phyllosilicates of the smectite group including Mg- and Fe-saponite and Fe(III)-rich nontronite have been identified on Mars. Smectites are believed to be formed under neutral to alkaline conditions that prevailed on early Mars. This hypothesis is supported by the observation of smectite and carbonate deposits in Noachian terrain on Mars. However, smectite may have formed under mildly acidic conditions. Abundant smectite formations have been detected as layered deposits hundreds of meters thick in intracrater depositional fans and plains sediments, while no large deposits of carbonates are found. Development of mildly acidic conditions at early Mars might allow formation of smectite but inhibit widespread carbonate precipitation. Little is known regarding the mechanisms of smectite formation from basaltic glass under acidic conditions. The objective of this study was to test a hypothesis that Mars-analogue basaltic glass alters to smectite minerals under acidic conditions (pH 4). The effects of Mg and Fe concentrations and temperature on smectite formation from basaltic glass were evaluated. Phyllosilicate synthesis was performed in batch reactors (Parr acid digestion vessel) under reducing hydrothermal conditions at 200 C and 100 C. Synthetic basaltic glass with a composition similar to that of the Gusev crater rock Adirondack (Ground surface APXS measurement) was used in these experiments. Basaltic glass was prepared by melting and quenching procedures. X-ray diffraction (XRD) analysis indicated that the synthesized glass was composed of olivine, magnetite and X-ray amorphous phase. Samples were prepared by mixing 250 mg Adirondack with 0.1 M acetic acid (final pH 4). In order to study influence of Mg concentration on smectite formation, experiments were performed with addition of 0, 1 and 10 mM MgCl2. After 1, 7 and 14 day incubations the solution composition was analyzed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and the altered glass and formed

  14. Acidity and complex formation studies of 3-(adenine-9-yl)-propionic and 3-(thymine-1-yl)-propionic acids in ethanol-water media

    NASA Astrophysics Data System (ADS)

    Hammud, Hassan H.; El Shazly, Shawky; Sonji, Ghassan; Sonji, Nada; Bouhadir, Kamal H.

    2015-05-01

    The ligands 3-(adenine-9-yl)propionic acid (AA) and 3-(thymine-1-yl)propionic acid (TA) were prepared by N9-alkylation of adenine and N1-alkylation of thymine with ethylacrylate in presence of a base catalyst, followed by acid hydrolysis of the formed ethyl esters to give the corresponding propionic acid derivatives. The products were characterized by spectral methods (FTIR, 1H NMR and 13C NMR), which confirm their structures. The dissociation constants of ligands, were potentiometrically determined in 0.3 M KCl at 20-50 °C temperature range. The work was extended to study complexation behavior of AA and TA with various biologically important divalent metal ions (Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Mn2+ and Pb2+) in 50% v/v water-ethanol medium at four different temperatures, keeping ionic strength constant (0.3 M KCl). The order of the stability constants of the formed complexes decreases in the sequence Cu2+ > Pb2+ > Zn2+ > Ni2+ > Co2+ > Mn2+ > Cd2+ for both ligands. The effect of temperature was also studied and the corresponding thermodynamic functions (ΔG, ΔH, ΔS) were derived and discussed. The formation of metal complexes has been found to be spontaneous, and the stability constants were dependant markedly on the basicity of the ligands.

  15. The Formation and Stability of Carbonic Acid on Outer Solar System Bodies

    NASA Technical Reports Server (NTRS)

    Peeters, Z.; Hudson, R. L.; Moore, M. H.; Lewis, Ariel

    2009-01-01

    The radiation chemistry, thermal stability, and vapor pressure of solid-phase carbonic acid (H2CO3) have been studied with mid-infrared spectroscopy. A new procedure for measuring this molecule's radiation stability has been used to obtain intrinsic IR band strengths and half-lives for radiolytic destruction. Results are compared to literature values. We report, for the first time, measurements of carbonic acid's vapor pressure and its heat of sublimation. We also report the first observation of a chemical reaction involving solid-phase carbonic acid. Possible applications of these findings are discussed, with an emphasis on the outer Solar System.

  16. The Formation of Racemic Amino Acids by UV Photolysis of Interstellar Ice Analogs

    NASA Technical Reports Server (NTRS)

    Bernstein, Max P.; Dworkin, Jason P.; Sandford, Scott A.; Cooper, George; Allamandola, Louis J.; DeVincenzi, Donald (Technical Monitor)

    2001-01-01

    Small biologically relevant organic molecules including the amino acids glycine, alanine, and marine were formed in the laboratory by the UV (Ultraviolet) photolysis of realistic interstellar ice analogs, composed primarily of H2O, and including CH3OH, NH3, and HCN, under interstellar conditions. N-formyl glycine, cycloserine (4-amino-3-isoxazolidinone), and glycerol were detected before hydrolysis, and glycine, racemic alanine, racemic marine, glycerol, ethanolamine, and glyceric acid were found after hydrolysis. This suggests that some meteoritic amino acids (and other molecules) may be the direct result of interstellar ice photochemistry, expanding the current paradigm that they formed by reactions in liquid water on meteorite parent bodies.

  17. Formation of varanic acid, 3 alpha, 7 alpha, 12 alpha, 24-tetrahydroxy-5 beta-cholestanoic acid from 3 alpha, 7 alpha, 12 alpha-trihydroxy-5 beta-cholestanoic acid in Bombina orientalis.

    PubMed

    Une, M; Inoue, A; Hoshita, T

    1996-11-01

    Varanic acid (3 alpha, 7 alpha, 12 alpha, 24-tetrahydroxy-5 beta-cholestanoic acid; 24-OH-THCA) is almost the sole component of bile acids in the bile of Bombina orientalis. To examine in the mechanism of the formation of 24-OH-THCA, radiolabeled (25R)- and (25S)-3 alpha, 7 alpha, 12 alpha-trihdroxy-5 beta-cholestanoic acids [(25R)- and (25S)-THCA] and (24E)-3 alpha, 7 alpha, 12 alpha-trihdroxy-5 beta-cholest-24-enoic acid (delta 24-THCA) were administered intraperitoneally to B. orientalis, gallbladder bile was collected after 24 h, and bile acids were subsequently extracted. Then the bile acids were analyzed by means of radio thin-layer chromatography and radio high-performance liquid chromatography after conversion to p-bromophenacyl ester derivatives. Although delta 24-THCA was not converted to 24-OH-THCA, (25R)-THCA and (25S)-THCA were transformed to (24R,25R)-24-OH-THCA and (24R,25S)-24-OH-THCA, respectively. These results strongly suggest that 24-OH-THCA was transformed via direct hydroxylation of the saturated side chain of THCA, not via hydration to an alpha, beta-unsaturated acid, delta 24-THCA, in B. orientalis.

  18. The Synthesis of an Amino Acid Derivative and Spectroscopic Monitoring of Dipeptide Formation.

    ERIC Educational Resources Information Center

    Simmonds, Richard J.

    1987-01-01

    Described are experiments to give students experience in the synthesis of peptides from amino acids and to use visible spectroscopy to measure a rate of reaction. The activities were designed for undergraduate courses. (RH)

  19. Enhanced comedo formation in rabbit ear skin by squalene and oleic acid peroxides.

    PubMed

    Motoyoshi, K

    1983-08-01

    The comedogenicity of UVA-irradiated and non-irradiated substances (squalene, oleic acid, tetradecane, isopropyl myristate, squalane and liquid paraffin) was evaluated by surface microscopy and histological examination after treating the ventral skin of rabbit ears with these substances. The lipid peroxide levels of these substances were also measured. Squalene itself was scarcely comedogenic but squalene peroxides were highly comedogenic. Both oleic acid and its peroxides were able to induce fairly large comedones and there was a good correlation between the lipid peroxide levels and the size of the comedones. The specimens biopsied from these comedones showed marked hyperplasia and hyperkeratosis of the epithelium in the follicular infundibulum and marked proliferation of the sebaceous glands. Although free fatty acids might play a role in the pathogenesis of acne, it is proposed that squalene and free fatty acids in sebum may be less comedogenic than their peroxides.

  20. Elucidating pH-dependent collagen triple helix formation through interstrand hydroxyproline-glutamic acid interactions.

    PubMed

    Chen, Liwei; Cai, Shuting; Lim, Jaehong; Lee, Su Seong; Lee, Song-Gil

    2015-02-09

    Here, we describe systematic explorations into the molecular basis underlying hydroxyproline-mediated interstrand interactions on the triple-helical stability of collagen-mimetic peptides containing glutamic acid residues. Our studies reveal that the triple-helical stability of these peptides relies on the existence of interstrand interactions between hydroxyprolines and glutamic acid residues that are pH dependent. These unique interactions have been used to engineer collagen peptides that form triple helices on demand through pH control.

  1. Structure and energy of formation of β- and γ-cyclodextrin complexes with amino acid enantiomers

    NASA Astrophysics Data System (ADS)

    Borisov, Yu. A.; Kiselev, S. S.

    2016-09-01

    The interaction between cyclodextrins (CyD), β-CyD, and γ-CyD, and the L- and D-optical isomers of several amino acids (Ala, Leu, His, Phe) are calculated using DFT. It is found that the L-forms of the investigated amino acids bond more strongly to CyD, due to the different numbers of hydrogen bonds that form. The structures of the resulting complexes are analyzed.

  2. Sulfuric Acid droplet formation and growth in the stratosphere after the 1982 eruption of el chichon.

    PubMed

    Hofmann, D J; Rosen, J M

    1983-10-21

    The eruption of El Chichón Volcano in March and April 1982 resulted in the nucleation of large numbers of new sulfuric acid droplets and an increase by nearly an order of magnitude in the size of the preexisting particles in the stratosphere. Nearly 10(7) metric tons of sulfuric acid remained in the stratosphere by the end of 1982, about 40 times as much as was deposited by Mount St. Helens in 1980.

  3. A comparative study of fatty acid profile and formation of biofilm in Geobacillus gargensis exposed to variable abiotic stress.

    PubMed

    Al-Beloshei, Noor Essa; Al-Awadhi, Husain; Al-Khalaf, Rania A; Afzal, Mohammad

    2015-01-01

    Understanding bacterial fatty acid (FA) profile has a great taxonomic significance as well as clinical importance for diagnosis issues. Both the composition and nature of membrane FAs change under different nutritional, biotic and (or) abiotic stresses, and environmental stress. Bacteria produce both odd-carbon as well as branched-chain fatty acids (BCFAs). This study was designed to examine the effect of abiotic pressure, including salinity, temperature, pH, and oxinic stress on the growth, development, and FA profile in thermophilic Geobacillus gargensis. Under these stresses, 3 parametric ratios, 2-methyl fatty acids/3-methyl fatty acids (iso-/anteiso-FAs), BCFAs/straight-chain saturated fatty acids (SCSFA), and SCSFAs/straight-chain unsaturated fatty acids (SCUFA), in addition to total lipids affected by variable stresses were measured. Our results indicate that the ratio of total iso-/anteiso-FAs increased at the acidic pH range of 4.1-5.2 and decreased with increasing pH. The reverse was true for salt stress when iso-/anteiso-FAs ratio increased with salt concentration. The BCFAs/SCSFAs and SCSFAs/SCUFAs ratios increased at neutral and alkaline pH and high salt concentration, reduced incubation time, and comparatively high temperature (55-65 °C) of the growth medium. The bacterial total lipid percentage deceased with increasing salt concentration, incubation period, but it increased with temperature. The formation of extracellular polymeric substances was observed under all stress conditions and with the addition of sodium dodecyl sulfate (2 and 5 mmol/L) to the growth medium. The membrane phospholipid composition of the bacterium was analyzed by thin-layer chromatography.

  4. Very-long-chain fatty acids restrict regeneration capacity by confining pericycle competence for callus formation in Arabidopsis.

    PubMed

    Shang, Baoshuan; Xu, Chongyi; Zhang, Xixi; Cao, Huifen; Xin, Wei; Hu, Yuxin

    2016-05-03

    The already differentiated organs in plants have a remarkable capacity to regenerate new individuals under culture conditions. Plant in vitro regeneration practically starts with the induction of a pluripotent cell mass, the callus, from detached organs on auxin-rich callus-inducing medium (CIM), which is generally required for subsequent regeneration of new bodies. Recent studies show that CIM-induced callus formation occurs from the pericycle or pericycle-like cells through a root developmental pathway, whereas the signals involved in governing callus-forming capacity of pericycle cells remain unknown. Here we report that very-long-chain fatty acids (VLCFAs) play a critical role in confining the pericycle competence for callus formation and thus the regeneration capacity of Arabidopsis By genetic screening, we identified the callus formation-related 1 (cfr1) mutant, which bypasses the inhibition of callus-forming capacity in roots by solitary-root (slr/iaa14). We show that CFR1 encodes 3-ketoacyl-CoA synthase 1 (KCS1), which catalyzes a rate-limiting step of VLCFA biosynthesis. Our biochemical and genetic analyses demonstrate that VLCFAs restrict the pericycle competence for callus formation, at least in part, by regulating the transcription of Aberrant Lateral Root Formation 4 (ALF4). Moreover, we provide evidence that VLCFAs act as cell layer signals to mediate the pericycle competence for callus formation. Taken together, our results identify VLCFAs or their derivatives as the confining signals for mediating the pericycle competence for callus formation and thus the regeneration capacity of plant organs.

  5. Very-long-chain fatty acids restrict regeneration capacity by confining pericycle competence for callus formation in Arabidopsis

    PubMed Central

    Shang, Baoshuan; Xu, Chongyi; Zhang, Xixi; Cao, Huifen; Xin, Wei; Hu, Yuxin

    2016-01-01

    The already differentiated organs in plants have a remarkable capacity to regenerate new individuals under culture conditions. Plant in vitro regeneration practically starts with the induction of a pluripotent cell mass, the callus, from detached organs on auxin-rich callus-inducing medium (CIM), which is generally required for subsequent regeneration of new bodies. Recent studies show that CIM-induced callus formation occurs from the pericycle or pericycle-like cells through a root developmental pathway, whereas the signals involved in governing callus-forming capacity of pericycle cells remain unknown. Here we report that very-long-chain fatty acids (VLCFAs) play a critical role in confining the pericycle competence for callus formation and thus the regeneration capacity of Arabidopsis. By genetic screening, we identified the callus formation-related 1 (cfr1) mutant, which bypasses the inhibition of callus-forming capacity in roots by solitary-root (slr/iaa14). We show that CFR1 encodes 3-ketoacyl-CoA synthase 1 (KCS1), which catalyzes a rate-limiting step of VLCFA biosynthesis. Our biochemical and genetic analyses demonstrate that VLCFAs restrict the pericycle competence for callus formation, at least in part, by regulating the transcription of Aberrant Lateral Root Formation 4 (ALF4). Moreover, we provide evidence that VLCFAs act as cell layer signals to mediate the pericycle competence for callus formation. Taken together, our results identify VLCFAs or their derivatives as the confining signals for mediating the pericycle competence for callus formation and thus the regeneration capacity of plant organs. PMID:27092001

  6. Effects of operational conditions on sludge degradation and organic acids formation in low-critical wet air oxidation.

    PubMed

    Chung, Jinwook; Lee, Mikyung; Ahn, Jaehwan; Bae, Wookeun; Lee, Yong-Woo; Shim, Hojae

    2009-02-15

    Wet air oxidation processes are to treat highly concentrated organic compounds including refractory materials, sludge, and night soil, and usually operated at supercritical water conditions of high temperature and pressure. In this study, the effects of operational conditions including temperature, pressure, and oxidant dose on sludge degradation and conversion into subsequent intermediates such as organic acids were investigated at low critical wet oxidation conditions. The reaction time and temperature in the wet air oxidation process was shown an important factor affecting the liquefaction of volatile solids, with more significant effect on the thermal hydrolysis reaction rather than the oxidation reaction. The degradation efficiency of sludge and the formation of organic acids were improved with longer reaction time and higher reaction temperature. For the sludge reduction and the organic acids formation under the wet air oxidation, the optimal conditions for reaction temperature, time, pressure, and oxidant dose were shown approximately 240 degrees C, 30min, 60atm, and 2.0L/min, respectively.

  7. Effect of heating/reheating of fats/oils, as used by Asian Indians, on trans fatty acid formation.

    PubMed

    Bhardwaj, Swati; Passi, Santosh Jain; Misra, Anoop; Pant, Kamal K; Anwar, Khalid; Pandey, R M; Kardam, Vikas

    2016-12-01

    Heating/frying and reuse of edible fats/oils induces chemical changes such as formation of trans fatty acids (TFAs). The aim of this study was to investigate the effect of heating/frying on formation of TFAs in fats/oils. Using gas chromatography with flame ionisation detector, TFA was estimated in six commonly used fat/oils in India (refined soybean oil, groundnut oil, olive oil, rapeseed oil, clarified butter, partially hydrogenated vegetable oil), before and after subjecting them to heating/frying at 180°C and 220°C. All six fats/oils subjected to heating/frying demonstrated an increase in TFAs (p<0.001), saturated fatty acids (p<0.001) and decrease in cis-unsaturated fatty acids (p<0.001). The absolute increase in TFA content of edible oils (after subjecting to heating/reheating) ranged between 2.30±0.89g/100g and 4.5±1.43g/100g; amongst edible fats it ranged between 2.60±0.38g/100g and 5.96±1.94g/100g. There were no significant differences between the two treatment groups (heating and frying; p=0.892). Considering the undesirable health effects of TFA, appropriate guidelines for heating/re-frying of edible fats/oils by Asian Indians should be devised.

  8. Comparison of hydroxyl radical formation in aqueous solutions at different ultrasound frequencies and powers using the salicylic acid dosimeter.

    PubMed

    Milne, Louise; Stewart, Isobel; Bremner, David H

    2013-05-01

    Ultrasonic frequencies of 20kHz, 382kHz, 584kHz, 862kHz (and 998kHz) have been compared with regard to energy output and hydroxyl radical formation utilising the salicylic acid dosimeter. The 862kHz frequency inputs 6 times the number of Watts into water, as measured by calorimetry, with the other frequencies having roughly the same value under very similar conditions. A plausible explanation involving acoustic fountain formation is proposed although enhanced coupling between this frequency and water cannot be discounted. Using the salicylic acid dosimeter and inputting virtually the same Wattages it is established that 862kHz is around 10% more efficient at generating hydroxyl radicals than the 382kHz but both of these are far more effective than the other frequencies. Also, it is found that as temperature increases to 42°C then the total dihydroxybenzoic acid (Total DHBA) produced is virtually identical for 382kHz and 862kHz, though 582kHz is substantially lower, when the power levels are set at approximately 9W for all systems. An equivalent power level of 9W could not be obtained for the 998kHz transducer so a direct comparison could not be made in this instance. These results have implications for the optimum frequencies chosen for both Advanced Oxidation Processes (AOPs) and organic synthesis augmented by ultrasound.

  9. Somatic pain sensitivity during formation and healing of acetic acid-induced gastric ulcers in conscious rats.

    PubMed

    Yarushkina, Natalya; Bogdanov, Anatoly; Filaretova, Ludmila

    2006-06-30

    A classical feature of visceral pain is its referring to somatic locations. Gastric ulcer is a source of visceral pain. In the present study we investigated whether gastric ulcers may trigger the changes in somatic nociception. For this aim somatic pain sensitivity was estimated under conditions of gastric ulcer development and healing. Gastric ulcers were induced by luminal application of 60% acetic acid under surgical conditions. Control rats were subjected to the same surgical procedure, but with the application of saline instead of the acid. Somatic pain sensitivity (tail flick latency), plasma corticosterone level, adrenal and thymus weight were investigated under conditions of the formation and the healing of gastric ulcers. The application of the acid resulted in the formation of kissing gastric ulcers, the increase of somatic pain sensitivity (the decrease of tail flick latency) as well as the appearance of typical signs of chronic stress: long-lasting increase of plasma corticosterone level, adrenal gland hypertrophy and thymus gland involution. Natural healing of gastric ulcers was accompanied by restoration of pain sensitivity as well as attenuation of the signs of chronic stress. Delay of ulcer healing by the daily indomethacin administration (2 mg/kg, s.c.) prevented the restoration of somatic pain sensitivity. The results suggest that chronic gastric ulcers may trigger somatic hypersensitivity.

  10. Apicoplast fatty acid synthesis is essential for pellicle formation at the end of cytokinesis in Toxoplasma gondii.

    PubMed

    Martins-Duarte, Érica S; Carias, Maira; Vommaro, Rossiane; Surolia, Namita; de Souza, Wanderley

    2016-09-01

    The apicomplexan protozoan Toxoplasma gondii, the causative agent of toxoplasmosis, harbors an apicoplast, a plastid-like organelle with essential metabolic functions. Although the FASII fatty acid biosynthesis pathway located in the apicoplast is essential for parasite survival, the cellular effects of FASII disruption in T. gondii had not been examined in detail. Here, we combined light and electron microscopy techniques - including focused ion beam scanning electron microscopy (FIB-SEM) - to characterize the effect of FASII disruption in T. gondii, by treatment with the FASII inhibitor triclosan or by inducible knockdown of the FASII component acyl carrier protein. Morphological analyses showed that FASII disruption prevented cytokinesis completion in T. gondii tachyzoites, leading to the formation of large masses of 'tethered' daughter cells. FIB-SEM showed that tethered daughters had a mature basal complex, but a defect in new membrane addition between daughters resulted in incomplete pellicle formation. Addition of exogenous fatty acids to medium suppressed the formation of tethered daughter cells and supports the notion that FASII is essential to generate lipid substrates required for the final step of parasite division.

  11. Inhibition of Nucleic Acid Biosynthesis Makes Little Difference to Formation of Amphotericin B-Tolerant Persisters in Candida albicans Biofilm

    PubMed Central

    Sun, Jing; Liu, Xiaohua

    2014-01-01

    Candida albicans persisters constitute a small subpopulation of biofilm cells and play a major role in recalcitrant chronic candidiasis; however, the mechanism underlying persister formation remains unclear. Persisters are often described as dormant, multidrug-tolerant, nongrowing cells. Persister cells are difficult to isolate and study not only due to their low levels in C. albicans biofilms but also due to their transient, reversible phenotype. In this study, we tried to induce persister formation by inducing C. albicans cells into a dormant state. C. albicans cells were pretreated with 5-fluorocytosine (planktonic cells, 0.8 μg ml−1; biofilm cells, 1 μg ml−1) for 6 h at 37°C, which inhibits nucleic acid and protein synthesis. Biofilms and planktonic cultures of eight C. albicans strains were surveyed for persisters after amphotericin B treatment (100 μg ml−1 for 24 h) and CFU assay. None of the planktonic cultures, with or without 5-fluorocytosine pretreatment, contained persisters. Persister cells were found in biofilms of all tested C. albicans strains, representing approximately 0.01 to 1.93% of the total population. However, the persister levels were not significantly increased in C. albicans biofilms pretreated with 5-fluorocytosine. These results suggest that inhibition of nucleic acid synthesis did not seem to increase the formation of amphotericin B-tolerant persisters in C. albicans biofilms. PMID:25547355

  12. Formation and alteration of complex amino acid precursors in cosmic dusts and their relevance to origins of life

    NASA Astrophysics Data System (ADS)

    Kobayashi, Kensei; Kaneko, Takeo; Mita, Hajime; Obayashi, Yumiko; Kawamoto, Yukinori; Kanda, Kazuhiro; Takayama, Ken; Shibata, Hiromi

    A wide variety of organic compounds including many kinds of amino acids have been detected in carbonaceous chondrites. It has been known that comets also bring complex organic compounds. The relevance of extraterrestrial organics to the origin of life is extensively discussed. There have been many scenarios of the origin of amino acids found in meteorites or comets, including the Strecker synthesis in the parent bodies of meteorites, the Fischer-Tropsch type reaction in the solar nebula and reactions in cosmic dusts. We examined possible formation of amino acids or their precursors in interstellar dust environments. When possible interstellar media (a mixture of carbon monoxide, ammonia and water) was irradiated with high energy protons, complex organic compounds whose molecular weights are thousands were formed [1], which gave amino acids after acid hydrolysis: Hereafter we will refer them simulated interstellar organics. It was suggested that complex amino acid precursors could be formed in ice mantles of interstellar dust particles in prior to the formation of the solar system. We are planning to irradiate simulated interstellar ices with high-energy heavy ions from the Digital Accelerator (KEK) to confirm the scenario. The simulated interstellar oraganics were so hydrophilic that they were easy to dissolve in water. Complex organics found in meteorites are generally so hydrophobic and are insoluble to water. Organics found in cometary dusts sampled by the Stardust Mission contains organics with various hydrophobicity. We irradiated the simulated interstellar organics with UV and/or soft X-rays. Soft X-rays irradiation of the simulated interstellar organics resulted in the formation of more hydrophobic compounds as seen in some of cometary dusts. It was suggested that organics of interstellar origin on dusts were altered when the solar system was being formed with soft X-rays from the young Sun in prior to the incorporation to planetesimals or comets. Dusts have

  13. Retrobiosynthetic NMR studies with 13C-labeled glucose. Formation of gallic acid in plants and fungi.

    PubMed

    Werner, I; Bacher, A; Eisenreich, W

    1997-10-10

    The biosynthesis of gallic acid was studied in cultures of the fungus Phycomyces blakesleeanus and in leaves of the tree Rhus typhina. Fungal cultures were grown with [1-13C]glucose or with a mixture of unlabeled glucose and [U-13C6]glucose. Young leaves of R. typhina were kept in an incubation chamber and were supplied with a solution containing a mixture of unlabeled glucose and [U-13C6]glucose via the leaf stem. Isotope distributions in isolated gallic acid and aromatic amino acids were analyzed by one-dimensional 1H and 13C NMR spectroscopy. A quantitative analysis of the complex isotopomer composition of metabolites was obtained by deconvolution of the 13C13C coupling multiplets using numerical simulation methods. This approach required the accurate analysis of heavy isotope chemical shift effects in a variety of different isotopomers and the analysis of long range 13C13C coupling constants. The resulting isotopomer patterns were interpreted using a retrobiosynthetic approach based on a comparison between the isotopomer patterns of gallic acid and tyrosine. The data show that both in the fungus and in the plant all carbon atoms of gallic acid are biosynthetically equivalent to carbon atoms of shikimate. Notably, the carboxylic group of gallic acid is derived from the carboxylic group of an early intermediate of the shikimate pathway and not from the side chain of phenylalanine or tyrosine. It follows that the committed precursor of gallic acid is an intermediate of the shikimate pathway prior to prephenate or arogenate, most probably 5-dehydroshikimate. A formation of gallic acid via phenylalanine, the lignin precursor, caffeic acid, or 3,4, 5-trihydroxycinnamic acid can be ruled out as major pathways in the fungus and in young leaves of R. typhina. The incorporation of uniformly 13C-labeled glucose followed by quantitative NMR analysis of isotopomer patterns is suggested as a general method for biosynthetic studies. As shown by the plant experiment, this

  14. Formation of hydrocarbons from acid-Clay suspensions by gamma irradiation

    SciTech Connect

    Cruz-Castaneda, J.; Negron-Mendoza, A.; Ramos-Bernal, S.

    2013-07-03

    The adsorption of certain organic compounds by clays gives rise to the transformation of the adsorbate through the action of the clays. This phenomenon can be enhanced using ionizing radiation. In this context, these kinds of reactions play an important role in many natural and industrial processes. For example, in oil and gas exploration, the source and trap of petroleum hydrocarbons is frequently clay-rich rocks. Clay-water-based muds are also seen as environmentally friendly alternatives to toxic oil-based fluids. The principal processes that occur in sediments are usually held to be of bacterial action and thermal transformation, which may include thermally induced catalytic alteration of the organic debris. On the other hand, radioactive materials are widely distributed throughout Earth. They were more abundant in the past, but are present in petroleum reservoirs. Their presence induced radioactive bombardment, which may have altered these sediments. This important subject has not been extensively studied. The aim of this work is to study the behavior of fatty acids-like behenic acid-and dicarboxylic acids-like fumaric acid-as model compounds, which are adsorbed in a clay mineral (Na-montmorillonite) and exposed to gamma radiation. The results show that the radiation-induced decomposition of the clay-acid system goes along a definitive path (oxidation), rather than following several modes of simultaneous decomposition, as happens in radiolysis without clay or by heating the system. The main radiolytic products for fatty acids are their corresponding hydrocarbons, with one C-atom less than the original acid.

  15. Ozone sensitivity in hybrid poplar correlates with insensitivity to both salicylic acid and jasmonic acid. The role of programmed cell death in lesion formation.

    PubMed

    Koch, J R; Creelman, R A; Eshita, S M; Seskar, M; Mullet, J E; Davis, K R

    2000-06-01

    Our earlier studies demonstrated that the ozone-sensitive hybrid poplar clone NE-388 displays an attenuated level of ozone-, wound-, and phytopathogen-induced defense gene expression. To determine if this reduced gene activation involves signal transduction pathways dependent on salicylic acid (SA) and/or jasmonic acid (JA), we compared the responses of NE-388 and an ozone-tolerant clone, NE-245, to these signal molecules. JA levels increased in both clones in response to ozone, but only minimal increases in SA levels were measured for either clone. Treatment with SA and methyl jasmonate induced defense gene expression only in NE-245, indicating that NE-388 is insensitive to these signal molecules. DNA fragmentation, an indicator of programmed cell death (PCD), was detected in NE-245 treated with either ozone or an avirulent phytopathogen, but was not detected in NE-388. We conclude that these clones undergo two distinct mechanisms of ozone-induced lesion formation. In NE-388, lesions appear to be due to toxic cell death resulting from a limited ability to perceive and subsequently activate SA- and/or JA-mediated antioxidant defense responses. In NE-245, SA-dependent PCD precedes lesion formation via a process related to the PCD pathway activated by phytopathogenic bacteria. These results support the hypothesis that ozone triggers a hypersensitive response.

  16. Diamine-sulfuric acid reactions are a potent source of new particle formation

    NASA Astrophysics Data System (ADS)

    Jen, Coty N.; Bachman, Ryan; Zhao, Jun; McMurry, Peter H.; Hanson, David R.

    2016-01-01

    Atmospheric nucleation from sulfuric acid depends on the concentrations and the stabilizing effect of other trace gases, such as ammonia and amines. Diamines are an understudied class of atmospherically relevant compounds, and we examine how they affect sulfuric acid nucleation in both flow reactor experiments and the atmosphere. The number of particles produced from sulfuric acid and diamines in the flow reactor was equal to or greater than the number formed from monoamines, implying that diamines are more effective nucleating agents. Upper limits of diamine abundance were also monitored during three field campaigns: Lamont, OK (2013); Lewes, DE (2012); and Atlanta, GA (2009). Mixing ratios were measured as high as tens of parts per trillion by volume (GA and OK). Laboratory results suggest that diamines at these levels are important for atmospheric nucleation. Diamines likely participate in atmospheric nucleation and should be considered in nucleation measurements and models.

  17. Understanding Particle Formation: Solubility of Free Fatty Acids as Polysorbate 20 Degradation Byproducts in Therapeutic Monoclonal Antibody Formulations.

    PubMed

    Doshi, Nidhi; Demeule, Barthélemy; Yadav, Sandeep

    2015-11-02

    The purpose of this work was to determine the aqueous solubilities at 2-8 °C of the major free fatty acids (FFAs) formed by polysorbate 20 (PS20) degradation and identify possible ways to predict, delay, or mitigate subsequent particle formation in monoclonal antibody (mAb) formulations. The FFA solubility limits at 2-8 °C were determined by titrating known amounts of FFA in monoclonal antibody formulations and identifying the FFA concentration leading to visible and subvisible particle formation. The solubility limits of lauric, myristic, and palmitic acids at 2-8 °C were 17 ± 1 μg/mL, 3 ± 1 μg/mL, and 1.5 ± 0.5 μg/mL in a formulation containing 0.04% (w/v) PS20 at pH 5.4 and >22 μg/mL, 3 ± 1 μg/mL, and 0.75 ± 0.25 μg/mL in a formulation containing 0.02% (w/v) PS20 at pH 6.0. For the first time, a 3D correlation between FFA solubility, PS20 concentration, and pH has been reported providing a rational approach for the formulator to balance these with regard to potential particle formation. The results suggest that the lower solubilities of the longer chain FFAs, generated from degradation of the stearate, palmitate, and myristate fraction of PS20, is the primary cause of seeding and subsequent FFA precipitation rather than the most abundant lauric acid.

  18. Formation of Crystalline δ-Endotoxin or Poly-β-Hydroxybutyric Acid Granules by Asporogenous Mutants of Bacillus thuringiensis

    PubMed Central

    Wakisaka, Yoshiharu; Masaki, Emiko; Nishimoto, Yoji

    1982-01-01

    Parental strains and asporogenous mutants of Bacillus thuringiensis subspp. kurstaki and aizawai produced high yields of δ-endotoxin on M medium, which contained 330 μg of potassium per ml, but not on ST and ST-a media, each of which contained only 11 μg of potassium per ml. On ST and ST-a media, refractile granules were formed instead. These granules had no insecticidal activity against silkworms and were isolated and identified as poly-β-hydroxybutyric acid. Supplementation of the potassium-deficient ST-a medium with 0.1% KH2PO4 (3.7 mM) led to the formation of crystalline δ-endotoxin. The replacement of KH2PO4 with equimolar amounts of KCl, KNO3, and potassium acetate or an equivalent amount of K2SO4 had a similar effect, whereas the addition of an equimolar amount of NaH2PO4 or NH4H2PO4 did not cause the endotoxin to form. An asporogenous mutant, B. thuringiensis subsp. kurstaki strain 290-1, produced δ-endotoxin on ST-a medium supplemented with 3 mM or more potassium but formed only poly-β-hydroxybutyric acid granules on the media containing ≤1 mM potassium. These results clearly indicate that a certain concentration of potassium is essential for the fermentative production of δ-endotoxin by these isolates of B. thuringiensis. Manganese could not be substituted for potassium. Phosphate ions stimulated poly-β-hydroxybutyric acid formation by strain 290-1. The sporulation of B. thuringiensis and several other Bacillus strains was suppressed on the potassium-deficient ST medium. This suggests that potassium plays an essential role not only in Bacillus cell growth and δ-endotoxin formation but also in sporulation. Images PMID:16346040

  19. Formation of molecular complexes of salicylic acid, acetylsalicylic acid, and methyl salicylate in a mixture of supercritical carbon dioxide with a polar cosolvent

    NASA Astrophysics Data System (ADS)

    Petrenko, V. E.; Antipova, M. L.; Gurina, D. L.; Odintsova, E. G.

    2015-08-01

    The solvate structures formed by salicylic acid, acetylsalicylic acid, and methyl salicylate in supercritical (SC) carbon dioxide with a polar cosolvent (methanol, 0.03 mole fractions) at a density of 0.7 g/cm3 and a temperature of 318 K were studied by the molecular dynamics method. Salicylic and acetylsalicylic acids were found to form highly stable hydrogen-bonded complexes with methanol via the hydrogen atom of the carboxyl group. For methyl salicylate in which the carboxyl hydrogen is substituted by a methyl radical, the formation of stable hydrogen bonds with methanol was not revealed. The contribution of other functional groups of the solute to the interactions with the cosolvent was much smaller. An analysis of correlations between the obtained data and the literature data on the cosolvent effect on the solubility of the compounds in SC CO2 showed that the dissolving ability of SC CO2 with respect to a polar organic substance in the presence of a cosolvent increased only when stable hydrogen-bonded complexes are formed between this substance and the cosolvent.

  20. N-carbamoyl-alpha-amino acids rather than free alpha-amino acids formation in the primitive hydrosphere: a novel proposal for the emergence of prebiotic peptides.

    PubMed

    Taillades, J; Beuzelin, I; Garrel, L; Tabacik, V; Bied, C; Commeyras, A

    1998-02-01

    Our previous kinetic and thermodynamic studies upon the reactional system HCHO/HCN/NH3 in aqueous solutions are completed. In the assumed prebiotic conditions of the primitive earth ([HCHO] and [HCN] near 1 g L-1, T = 25 degrees C, pH = 8, [NH3] very low), this system leads to 99.9% of alpha-hydroxyacetonitrile and 0.1% of alpha-aminoacetonitrile (precursor of the alpha-amino acid). The classical base-catalyzed hydration of nitriles, slow and not selective, can not modify significantly this proportion. On the contrary, we found two specific and efficient reactions of alpha-aminonitriles which shift the initial equilibrium in favor of the alpha-aminonitrile pathway. The first reaction catalyzed by formaldehyde generates alpha-aminoamides, precursors of alpha-aminoacids. The second reaction catalyzed by carbon dioxide affords hydantoins, precursors of N-carbamoyl-alpha-aminoacids. In the primitive hydrosphere, where the concentration in carbon dioxide was estimated to be higher than that of formaldehyde, the formation of hydantoins was consequently more efficient. The rates of hydrolysis of the alpha-aminoacetamide and of the hydantoin at pH 8 being very similar, the synthesis of the N-carbamoyl-alpha-amino acid seems then to be the fatal issue of the HCHO/HCN/NH3 system that nature used to perform its evolution. These N-protected alpha-amino acids offer new perspectives in prebiotic chemistry, in particular for the emergence of peptides on the prebiotic earth.

  1. Effect of the solvatation shell exchange on the formation of malvidin-3-O-glucoside-ellagic acid complexes.

    PubMed

    Kunsagi-Maté, Sandor; Ortmann, Erika; Kollar, Laszló; Nikfardjam, Martin Pour

    2007-10-11

    The interaction of malvidin-3-O-glucoside with ellagic acid was studied in aqueous solutions in dependence of the ethanol content of the samples. The results show significant changes of the thermodynamic parameters when the ethanol content exceeds 8%vol. The quantum chemical calculations and the solvent relaxation measurements validate that the solvatation shell of the malvidin-ellagic acid complexes changes from water to ethanol around this critical alcoholic concentration. The change of the solvate shell is accompanied by increasing copigmentation; i.e., higher "multi-sandwich" complexes are formed. According to the considerable role of this interaction (namely copigmentation) in the formation of color in red wines, our results have several consequences for the winemaking process with regard to the stabilization of wine color.

  2. Flavin-induced photodecomposition of sulfur-containing amino acids is decisive in the formation of beer lightstruck flavor.

    PubMed

    Huvaere, Kevin; Andersen, Mogens L; Storme, Michael; Van Bocxlaer, Jan; Skibsted, Leif H; De Keukeleire, Denis

    2006-10-01

    Photooxidation of sulfur-containing amino acids and derivatives readily occurs upon visible-light irradiation in the presence of flavins. The sulfur moiety seems pivotal for interaction, as was determined from kinetic analyses using laser flash photolysis spectroscopy. After photooxidation, the resulting radical intermediates were characterized by addition to a spin trap, followed by electron paramagnetic resonance spectroscopy and evaluation of the coupling constants. The presence of the proposed radical intermediates was strongly supported by the identification of the reaction products using mass spectrometry. Accordingly, feasible degradation pathways for various sulfur-containing amino acids and derivatives were proposed. It was finally proven that flavin-induced photoproduction of sulfhydryl radicals and recombination with a 3-methylbut-2-enyl radical, derived from the photodegradation of hop-derived isohumulones, are decisive in the formation of beer lightstruck flavor.

  3. Factors influencing the formation of histaminol, hydroxytyrosol, tyrosol, and tryptophol in wine: Temperature, alcoholic degree, and amino acids concentration.

    PubMed

    Bordiga, M; Lorenzo, C; Pardo, F; Salinas, M R; Travaglia, F; Arlorio, M; Coïsson, J D; Garde-Cerdán, T

    2016-04-15

    The validation of a HPLC-PDA-MS/MS chromatographic method for the quali/quantitative characterization of histaminol, hydroxytyrosol, tyrosol, and tryptophol in wine has been described and discussed. Four standards showed a good linearity with high correlation coefficient values (over 0.9989) and LOD and LOQ were 0.001-0.015 mg/L and 0.004-0.045 mg/L, respectively. Furthermore, this study reported how factors such as temperature, alcoholic degree, and amino acids concentration are able to influence the formation of these four alcohols in Monastrell wines. The quantification values of these alcohols has been detected both at the half and end of alcoholic fermentation, and at the end of malolactic fermentation. In relation to interactions between factors, several significant variations emerged (p ⩽ 0.001). The impact of amino acids supplementation in Monastrell must it has been demonstrated, mainly in regards to histaminol and tryptophol.

  4. Removal of hexenuronic acid by xylanase to reduce adsorbable organic halides formation in chlorine dioxide bleaching of bagasse pulp.

    PubMed

    Nie, Shuangxi; Wang, Shuangfei; Qin, Chengrong; Yao, Shuangquan; Ebonka, Johnbull Friday; Song, Xueping; Li, Kecheng

    2015-11-01

    Xylanase-aided chlorine dioxide bleaching of bagasse pulp was investigated. The pulp was pretreated with xylanase and followed a chlorine dioxide bleaching stage. The ATR-FTIR and XPS were employed to determine the surface chemistry of the control pulp, xylanase treated and chlorine dioxide treated pulps. The hexenuronic acid (HexA) could obviously be reduced after xylanase pretreatment, and the adsorbable organic halides (AOX) were reduced after chlorine dioxide bleaching. Compared to the control pulp, AOX could be reduced by 21.4-26.6% with xylanase treatment. Chlorine dioxide demand could be reduced by 12.5-22% to achieve the same brightness. The ATR-FTIR and XPS results showed that lignin and hemicellulose (mainly HexA) were the main source for AOX formation. Xylanase pretreatment could remove HexA and expose more lignin, which decreased the chlorine dioxide demand and thus reduced formation of AOX.

  5. Humic acid inhibits HBV-induced autophagosome formation and induces apoptosis in HBV-transfected Hep G2 cells

    PubMed Central

    Pant, Kishor; Yadav, Ajay K.; Gupta, Parul; Rathore, Abhishek Singh; Nayak, Baibaswata; Venugopal, Senthil K.

    2016-01-01

    Hepatitis B Virus (HBV) utilizes several mechanisms to survive in the host cells and one of the main pathways being autophagosome formation. Humic acid (HA), one of the major components of Mineral pitch, is an Ayurvedic medicinal food, commonly used by the people of the Himalayan regions of Nepal and India for various body ailments. We hypothesized that HA could induce cell death and inhibit HBV-induced autophagy in hepatic cells. Incubation of Hep G2.2.1.5 cells (HepG2 cells stably expressing HBV) with HA (100 μM) inhibited both cell proliferation and autophagosome formation significantly, while apoptosis induction was enhanced. Western blot results showed that HA incubation resulted in decreased levels of beclin-1, SIRT-1 and c-myc, while caspase-3 and β-catenin expression were up-regulated. Western blot results showed that HA significantly inhibited the expression of HBx (3-fold with 50 μM and 5-fold with 100 μM) compared to control cells. When HA was incubated with HBx-transfected Hep G2 cells, HBx-induced autophagosome formation and beclin-1 levels were decreased. These data showed that HA induced apoptosis and inhibited HBV-induced autophagosome formation and proliferation in hepatoma cells. PMID:27708347

  6. Kinetics and mechanism of the electrochemical formation of iron oxidation products on steel immersed in sour acid media.

    PubMed

    Hernández-Espejel, Antonio; Palomar-Pardavé, Manuel; Cabrera-Sierra, Román; Romero-Romo, Mario; Ramírez-Silva, María Teresa; Arce-Estrada, Elsa M

    2011-03-03

    From electrochemical techniques (cyclic voltammetry, potential steps, and EIS), XRD, and SEM-EDX, the kinetics and mechanism of anodic film formation applying anodic potential steps on steel immersed in sour acid media was determined. It was found, from a thermodynamic analysis, based on equilibrium phase diagrams of the system considered in this work, that iron oxidation may produce different new solid phases, depending on the applied potential, the first being the iron oxidation associated with formation of FeS((c)) species, which in turn can be reoxidized to FeS(2(c)) or even to Fe(2)O(3(c)) at higher potential values. From analysis of the corresponding experimental potentiostatic current density transients, it was concluded that the electrochemical anodic film formation involves an E(1)CE(2) mechanism, whereby the first of the two simultaneous processes were the Fe electrochemical oxidation (E(1)) followed by FeS precipitation (C) that occurs by 3D nucleation and growth limited by mass transfer reaction and FeS oxidation (E(2)) forming a mix of different stoichiometry iron sulphides and oxides. From EIS measurements, it was revealed that the anodic film's charge transfer resistance diminishes as the potential applied for its formation becomes more anodic, thus behaving poorly against corrosion.

  7. Investigation on the reactivity of α-azidochalcones with carboxylic acids: Formation of α-amido-1,3-diketones and highly substituted 2-(trifluoromethyl)oxazoles

    PubMed Central

    Rajaguru, Kandasamy; Mariappan, Arumugam; Suresh, Rajendran; Manivannan, Periasamy

    2015-01-01

    Summary The reaction of α-azidochalcones with carboxylic acids has been investigated resulting in the formation of α-amido-1,3-diketones under microwave irradiation via in situ formation of 2H-azirine intermediates. An interesting reaction is described wherein, with trifluoroacetic acid at lower temperature, it affords highly substituted 2-(trifluoromethyl)oxazoles. These flexible transformations proceed under solvent free conditions in good to excellent yields without any catalyst. PMID:26664623

  8. The retinaldehyde reductase DHRS3 is essential for preventing the formation of excess retinoic acid during embryonic development

    PubMed Central

    Billings, Sara E.; Pierzchalski, Keely; Butler Tjaden, Naomi E.; Pang, Xiao-Yan; Trainor, Paul A.; Kane, Maureen A.; Moise, Alexander R.

    2013-01-01

    Oxidation of retinol via retinaldehyde results in the formation of the essential morphogen all-trans-retinoic acid (ATRA). Previous studies have identified critical roles in the regulation of embryonic ATRA levels for retinol, retinaldehyde, and ATRA-oxidizing enzymes; however, the contribution of retinaldehyde reductases to ATRA metabolism is not completely understood. Herein, we investigate the role of the retinaldehyde reductase Dhrs3 in embryonic retinoid metabolism using a Dhrs3-deficient mouse. Lack of DHRS3 leads to a 40% increase in the levels of ATRA and a 60% and 55% decrease in the levels of retinol and retinyl esters, respectively, in Dhrs3−/− embryos compared to wild-type littermates. Furthermore, accumulation of excess ATRA is accompanied by a compensatory 30–50% reduction in the expression of ATRA synthetic genes and a 120% increase in the expression of the ATRA catabolic enzyme Cyp26a1 in Dhrs3−/− embryos vs. controls. Excess ATRA also leads to alterations (40–80%) in the expression of several developmentally important ATRA target genes. Consequently, Dhrs3−/− embryos die late in gestation and display defects in cardiac outflow tract formation, atrial and ventricular septation, skeletal development, and palatogenesis. These data demonstrate that the reduction of retinaldehyde by DHRS3 is critical for preventing formation of excess ATRA during embryonic development.—Billings, S. E., Pierzchalski, K., Butler Tjaden, N. E., Pang, X.-Y., Trainor, P. A., Kane, M. A., Moise, A. R. The retinaldehyde reductase DHRS3 is essential for preventing the formation of excess retinoic acid during embryonic development. PMID:24005908

  9. Dithiolopyrrolone antibiotic formation induced by adding valeric acid to the culture broth of Saccharothrix algeriensis.

    PubMed

    Merrouche, Rabiâa; Bouras, Noureddine; Coppel, Yannick; Mathieu, Florence; Monje, Marie-Carmen; Sabaou, Nasserdine; Lebrihi, Ahmed

    2010-06-25

    Three new antibiotics were isolated from the fermentation broth of Saccharothrix algeriensis NRRL B-24137 and characterized as the dithiolopyrrolone derivatives valerylpyrrothine (1), isovalerylpyrrothine (2), and formylpyrrothine (3) as well as the known antibiotic aureothricin. The production of the dithiolopyrrolone derivatives was induced by adding valeric acid to the culture medium. The compounds exhibited moderate antimicrobial activity in vitro.

  10. Formation of elastic whey protein gels at low pH by acid equilibration.

    PubMed

    Vardhanabhuti, Bongkosh; Khayankan, Worarat; Foegeding, E Allen

    2010-06-01

    Whey protein gels have a weak/brittle texture when formed at pH acid solutions caused gel swelling and lowered pH because of the diffusion of water and H(+) into the gels. The type and concentration of acid, and presence of other ions, in the equilibrating solutions influenced pH, swelling ratio, and fracture properties of the gels. Swelling of gels decreased fracture stress (because of decreased protein network density) but caused little change to fracture strain, thus maintaining a desirable strong/elastic fracture pattern. We have shown that whey protein isolate gels can be made at pH acid type, acid concentration, pH of equilibrating solution, and equilibrating time.

  11. Preferential Enrichment of DL-Leucine Using Cocrystal Formation With Oxalic Acid Under Nonequilibrium Crystallization Conditions.

    PubMed

    Manoj, Kochunnoonny; Takahashi, Hiroki; Morita, Yoko; Gonnade, Rajesh G; Iwama, Sekai; Tsue, Hirohito; Tamura, Rui

    2015-07-01

    By utilizing the preferential enrichment (PE) technique, we achieved an improved enantiomeric resolution of DL-leucine (Leu) using a 1:1 cocrystal (DL-) of DL-Leu and oxalic acid. The crystal structure analysis of DL- indicated the occurrence of a novel type of phase transition and subsequent preferential redissolution of one enantiomer from the resulting crystals into solution.

  12. Docosapentaenoic acid (DPA) is a critical determinant of cubic membrane formation in amoeba Chaos mitochondria.

    PubMed

    Deng, Yuru; Almsherqi, Zakaria A; Shui, Guanghou; Wenk, Markus R; Kohlwein, Sepp D

    2009-09-01

    Very long-chain polyunsaturated fatty acids (VLC-PUFAs), such as docosahexaenoic acid (DHA) and docosapentaenoic acid (DPA), have recently made it to the realm of "magical molecules" based on their multiple presumably beneficial effects in biological systems, making these PUFAs particularly interesting in biomedicine. Their specific biological functions, however, remain enigmatic. Here we provide evidence derived from studies in the amoeba Chaos that indicates a structural role for omega-6 DPA in cell membrane organization, which may help to explain the multiple diverse effects of VLC-PUFA in healthy and diseased states. Amoeba Chaos mitochondria undergo a remarkable and reversible morphological transition into cubic morphology on starvation. This morphological transition is reflected in major changes in fatty acid and lipid composition, as determined by gas liquid chromatography and mass spectrometry, in particular by a drastic increase in C22:5 modified phosphatidylcholine plasmalogen, phosphatidylethanolamine plasmalogen, and phosphatidylinositol species. Liposomes produced in vitro from lipids of starved amoeba cells show a high propensity to form hexagonal tubular and cubic morphologies. Addition of omega-6 DPA, but not of omega-3 DPA, to the cell culture also induced mitochondrial membrane transformation into cubic morphology in fed cells, demonstrating for the first time an important structural role of omega-6 DPA-containing lipids in cell membrane organization.

  13. Lewis acid-catalysed formation of two-dimensional phthalocyanine covalent organic frameworks.

    PubMed

    Spitler, Eric L; Dichtel, William R

    2010-08-01

    Covalent organic frameworks (COFs) offer a new strategy for assembling organic semiconductors into robust networks with atomic precision and long-range order. General methods for COF synthesis will allow complex building blocks to be incorporated into these emerging materials. Here we report a new Lewis acid-catalysed protocol to form boronate esters directly from protected catechols and arylboronic acids. This transformation also provides crystalline boronate ester-linked COFs from protected polyfunctional catechols and bis(boronic acids). Using this method, we prepared a new COF that features a square lattice composed of phthalocyanine macrocycles joined by phenylene bis(boronic acid) linkers. The phthalocyanines stack in an eclipsed fashion within the COF to form 2.3 nm pores that run parallel to the stacked chromophores. The material's broad absorbance over the solar spectrum, potential for efficient charge transport through the stacked phthalocyanines, good thermal stability and the modular nature of COF synthesis, show strong promise for applications in organic photovoltaic devices.

  14. THE ROLE OF SELECTED CATIONS IN THE FORMATION OF PSEUDOMICELLES IN AQUEOUS HUMIC ACID (R822832)

    EPA Science Inventory

    The fluorescence intensity enhancement of a pyrene probe in aqueous humic acid solutions was assessed in terms of added lanthanide and thorium cations. Among the trivalent ions it was found that size played a role, with the small Lu3+ ion producing the greatest increase in pyrene...

  15. Formation of amino acid precursors in the Solar System small bodies using Aluminium-26 as an energy source

    NASA Astrophysics Data System (ADS)

    Kebukawa, Yoko; Kobayashi, Kensei; Kawai, Jun; Mita, Hajime; Tachibana, Shogo; Yoda, Isao; Misawa, Shusuke

    2016-07-01

    Carbonaceous chondrites contain various organic matter including amino acids that may have played an important role for origin of life on the early Earth. The parent bodies of the chondritic meteorites likely formed from silicate dust grains containing some water ice and organic compounds. These planetesimals are known to contain short-lived radio isotopes such as ^{26}Al, and the heat generated from the decay of ^{26}Al was considered to be used for melting ice. The liquid water, for example, changed anhydrous silicates into hydrous silicates, i.e., aqueous alteration. The liquid water would act also as an ideal reaction medium for various organic chemistry. Cody et al. [1] proposed IOM formation via formose reaction starting with formaldehyde and glycolaldehyde during aqueous activity in the small bodies. Additional hydrothermal experiments showed that ammonia enhanced the yields of IOM like organic solids [2]. Formaldehyde and ammonia are ubiquitous in the Solar System and beyond, e.g., comets contain H _{2}CO : NH _{3} : H _{2}O = 0.4-4 : 0.5-1.5 : 100 [3]. Thus these molecules can be expected to have existed in some Solar System small bodies. We study the liquid phase chemistry of the formaldehyde and ammonia, including formations of amino acid precursor molecules, via hydrothermal experiments at isothermal temperatures of 90 °C to 200 °C. We also evaluate the effects of gamma-ray which is released from the decay of ^{26}Al with gamma-ray irradiation experiments using a ^{60}Co gamma-ray source at Tokyo Institute of Technology. Amino acids were detected mostly after acid hydrolysis of heated or irradiated solutions, indicating that most of the amino acids in the products exist as precursors. Some samples contained 'free' amino acids that were detected without acid hydrolysis, but much lower abundance than after acid hydrolysis. Kendrick mass defect (KMD) analyses of High resolution mass spectra obtained using ESI-MS revealed that various CHO and CHNO

  16. Compound-specific carbon, nitrogen, and hydrogen isotopic ratios for amino acids in CM and CR chondrites and their use in evaluating potential formation pathways

    NASA Astrophysics Data System (ADS)

    Elsila, Jamie E.; Charnley, Steven B.; Burton, Aaron S.; Glavin, Daniel P.; Dworkin, Jason P.

    2012-09-01

    Stable hydrogen, carbon, and nitrogen isotopic ratios (δD, δ13C, and δ15N) of organic compounds can reveal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may indicate the most likely of these pathways. We have applied gas chromatography with mass spectrometry and combustion isotope ratio mass spectrometry to measure the compound-specific C, N, and H stable isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites: CM1/2 Allan Hills (ALH) 83100, CM2 Murchison, CM2 Lewis Cliff (LEW) 90500, CM2 Lonewolf Nunataks (LON) 94101, CR2 Graves Nunataks (GRA) 95229, CR2 Elephant Moraine (EET) 92042, and CR3 Queen Alexandra Range (QUE) 99177. We compare the isotopic compositions of amino acids in these meteorites with predictions of expected isotopic enrichments from potential formation pathways. We observe trends of decreasing δ13C and increasing δD with increasing carbon number in the α-H, α-NH2 amino acids that correspond to predictions made for formation via Strecker-cyanohydrin synthesis. We also observe light δ13C signatures for β-alanine, which may indicate either formation via Michael addition or via a pathway that forms primarily small, straight-chain, amine-terminal amino acids (n-ω-amino acids). Higher deuterium enrichments are observed in α-methyl amino acids, indicating formation of these amino acids or their precursors in cold interstellar or nebular environments. Finally, individual amino acids are more enriched in deuterium in CR chondrites than in CM chondrites, reflecting different parent-body chemistry.

  17. Compound-Specific Carbon, Nitrogen, and Hydrogen Isotopic Ratios for Amino Acids in CM and CR Chondrites and their use in Evaluating Potential Formation Pathways

    NASA Technical Reports Server (NTRS)

    Elsila, Jamie E.; Charnley, Steven B.; Burton, Aaron S.; Glavin, Daniel P.; Dworkin, Jason P.

    2012-01-01

    Stable hydrogen, carbon, and nitrogen isotopic ratios (oD, 013C, and olSN) of organic compounds can revcal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may indicate the most likely of these pathways. We have applied gas chromatography with mass spectrometry and combustion isotope ratio mass spectrometry to measure the compound-specific C, N, and H stable isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites: CM1I2 Allan Hills (ALH) 83100, CM2 Murchison, CM2 Lewis Cliff (LEW) 90500, CM2 Lonewolf Nunataks (LON) 94101, CRZ Graves Nunataks (GRA) 95229, CRZ Elephant Moraine (EET) 92042, and CR3 Queen Alexandra Range (QUE) 99177. We compare the isotopic compositions of amino acids in these meteorites with predictions of expected isotopic enrichments from potential formation pathways. We observe trends of decreasing ODC and increasing oD with increasing carbon number in the aH, (l-NH2 amino acids that correspond to predictions made for formation via Streckercyanohydrin synthesis. We also observe light ODC signatures for -alanine, which may indicate either formation via Michael addition or via a pathway that forms primarily small, straight-chain, amine-terminal amino acids (n-ro-amino acids). Higher deuterium enrichments are observed in amethyl amino acids, indicating formation of these amino acids or their precursors in cold interstellar or nebular environments. Finally, individual amino acids are more enriched in deuterium in CR chondrites than CM chondrites, reflecting different parent-body chemistry.

  18. UV Spectra of Amino Acid Immobilized at Nanoparticles Formation through Nanosphere Lithography (NSL) by Plasma Treatment

    SciTech Connect

    Mohamad, Farizan; Agam, Mohd Arif; Nur, Hadi

    2011-05-25

    The modifying of nanospheres structures by plasma treatments to the fabricated nanoparticles arrays by Nanosphere Lithography (NSL) techniques to create Periodic Particles Arrays (PPAs) with different size, shape and orientation. Spectra of amino acid that immobilized to the nanoparticles arrays under Ultra Violet (UV) spectrums were studied. The PPAs with different sizes, shapes and orientation were fabricated by plasma treatment of 5 sec, 7 sec and 10 sec to the Polystyrene Nanosphere (PSN). Plasma treatment will effect to the PSN including etching part of the PSN to produce a much bigger channel to the single layer template of the PSN. Metal was deposited at interstitial sites between of the polymer balls and later removed by dissolving them in organic solvent, leaving a hexagonal pattern of metal structures at the interstitial sites. The nanoparticles immobilized with the standard amino acid, which later investigated under UV spectrums. The spectrums shows the possibilities use as biosensor devices.

  19. Conjugated linoleic acid (CLA) formation in edible oils by photoisomerization: a review.

    PubMed

    Gangidi, Rahul Reddy; Lokesh, Belur Ramaswamy

    2014-05-01

    Conjugated linoleic acid (CLA) that is commonly found in dairy and ruminant fats, is geometrical and positional isomer of linoleic acid (LA). Edible oils are not good sources of CLA. Attempts have been made to generate CLA in edible oils through photoisomerization procedures. CLA isomers have several proven health benefits. This article reviews procedures for producing CLA containing edible oils by photoisomerization approach and applications of photoisomerized oils for food uses. The article reviews (1) the photoisomerized production of CLA containing oils on lab scale, with customized equipment, at pilot plant scale; (2) the effects of iodine content, photoisomerization time, refining, interference from minor components of oils, efficacy of different edible oils containing LA, interference from antioxidants; (3) the chemical kinetics, oxidative stability; and (4) photoisomerized oils for frying oils and as drying oils.The review also briefly covers methods of measurement of CLA.

  20. On the Temperature Dependence of the Formation Constant of Thiocyanatopentaaquochromium (III) in Acidic Solution.

    DTIC Science & Technology

    1983-04-01

    constants for metal ion complexes Bflandamer’s method Chromium (III) complexes Heat capacity of activation Equilibrium and kinetics of reactions in solution...20 ABSTRACT (Continue on reveree aide if neceetary and Identify by block number) The equilibrium constants for the ionization of carboxylic acids in...water pass through a maximum as temperature changes. If the equilibrium constant repre- sents a one-step process, then the attendant thermodynamic

  1. Hydrochloric acid aerosol formation by the interaction of hydrogen chloride with humid air

    NASA Technical Reports Server (NTRS)

    Rhein, R. A.

    1973-01-01

    The conditions in which hydrochloric acid aerosol is predicted by the interaction of hydrogen chloride gas with the water vapor in humid air are analyzed. The liquid gas phase equilibrium for the HCL-H2O system is expressed in terms of relative humidity and hydrogen chloride concentration as parts per million, units commonly used in pollution studies. Presented are the concentration (wt %) of HC1 in the aerosol and the concentration of aerosol (ppm) predicted.

  2. Formation Sequences of Iron Minerals in the Acidic Alteration Products and Variation of Hydrothermal Fluid Conditions

    NASA Astrophysics Data System (ADS)

    Isobe, H.; Yoshizawa, M.

    2008-12-01

    Iron minerals have important role in environmental issues not only on the Earth but also other terrestrial planets. Iron mineral species related to alteration products of primary minerals with surface or subsurface fluids are characterized by temperature, acidity and redox conditions of the fluids. We can see various iron- bearing alteration products in alteration products around fumaroles in geothermal/volcanic areas. In this study, zonal structures of iron minerals in alteration products of the geothermal area are observed to elucidate temporal and spatial variation of hydrothermal fluids. Alteration of the pyroxene-amphibole andesite of Garan-dake volcano, Oita, Japan occurs by the acidic hydrothermal fluid to form cristobalite leaching out elements other than Si. Hand specimens with unaltered or weakly altered core and cristobalite crust show various sequences of layers. XRD analysis revealed that the alteration degree is represented by abundance of cristobalite. Intermediately altered layers are characterized by occurrence including alunite, pyrite, kaolinite, goethite and hematite. A specimen with reddish brown core surrounded by cristobalite-rich white crust has brown colored layers at the boundary of core and the crust. Reddish core is characterized by occurrence of crystalline hematite by XRD. Another hand specimen has light gray core, which represents reduced conditions, and white cristobalite crust with light brown and reddish brown layers of ferric iron minerals between the core and the crust. On the other hand, hornblende crystals, typical ferrous iron-bearing mineral of the host rock, are well preserved in some samples with strongly decolorized cristobalite-rich groundmass. Hydrothermal alteration experiments of iron-rich basaltic material shows iron mineral species depend on acidity and temperature of the fluid. Oxidation states of the iron-bearing mineral species are strongly influenced by the acidity and redox conditions. Variations of alteration

  3. Ameliorating the Formation of Fullerene Complexes with Amino Acids:. a Theoretical Study

    NASA Astrophysics Data System (ADS)

    Jalbout, Abraham F.

    The present study is geared towards investigating methods to increase the tendency of fullerene structures to aggregate with biological systems. To accomplish this task, the encapsulation of metals inside a fullerene structure was performed. The calculations performed demonstrate that the Ca@C60 structure leads to stronger interactions with amino acids at the DFT-BLYP/DND level of theory. Correlations of the dissociation energies, HOMO/LUMO band gaps and hardness are discussed.

  4. Salicylic acid alleviates adverse effects of heat stress on photosynthesis through changes in proline production and ethylene formation.

    PubMed

    Khan, M Iqbal R; Iqbal, Noushina; Masood, Asim; Per, Tasir S; Khan, Nafees A

    2013-11-01

    We investigated the potential of salicylic acid (SA) in alleviating the adverse effects of heat stress on photosynthesis in wheat (Triticum aestivum L.) cv WH 711. Activity of ribulose 1,5-bisphosphate carboxylase (Rubisco), photosynthetic-nitrogen use efficiency (NUE), and net photosynthesis decreased in plants subjected to heat stress (40 °C for 6 h), but proline metabolism increased. SA treatment (0.5 mM) alleviated heat stress by increasing proline production through the increase in γ-glutamyl kinase (GK) and decrease in proline oxidase (PROX) activity, resulting in promotion of osmotic potential and water potential necessary for maintaining photosynthetic activity. Together with this, SA treatment restricted the ethylene formation in heat-stressed plants to optimal range by inhibiting activity of 1-aminocyclopropane carboxylic acid (ACC) synthase (ACS). This resulted in improved proline metabolism, N assimilation and photosynthesis. The results suggest that SA interacts with proline metabolism and ethylene formation to alleviate the adverse effects of heat stress on photosynthesis in wheat.

  5. Formation mechanisms of monochloropropanediol (MCPD) fatty acid diesters in refined palm (Elaeis guineensis) oil and related fractions.

    PubMed

    Destaillats, Frédéric; Craft, Brian D; Sandoz, Laurence; Nagy, Kornél

    2012-01-01

    Monochloropropanediol (MCPD) fatty acid esters are process contaminants generated during the deodorisation of edible oils. In particular, MCPD diesters are found in higher abundance in refined palm oil than other edible oils. In the present study, a series of model reactions mimicking palm oil deodorisation has been conducted with pure acylglycerols in the presence or absence of either organic or inorganic chlorine-containing compounds. Results showed that the bulk of MCPD diesters are formed above 200°C through the reaction of organochlorines with triacylglycerols (TAG). Additional experiments confirmed that this reaction can be initiated during palm oil deodorisation by hydrogen chloride (HCl) gas evolved through the thermal degradation of organochlorines present in the oil. Therein, the majority of the ultimately produced MCPD diesters are the result of HCl reacting with TAG, via protonation, followed by the elimination of a fatty acid residue. Two possible MCPD diester formation mechanisms are highlighted, both of which involve acyloxonium ion reactive intermediates. Investigations with pure TAG regio-isomers showed that MCPD ester formation is regioselective and the sn-1(3) position of the glycerol backbone is favoured.

  6. Contact ion pair formation between hard acids and soft bases in aqueous solutions observed with 2DIR spectroscopy.

    PubMed

    Sun, Zheng; Zhang, Wenkai; Ji, Minbiao; Hartsock, Robert; Gaffney, Kelly J

    2013-12-12

    The interaction of charged species in aqueous solution has important implications for chemical, biological, and environmental processes. We have used 2DIR spectroscopy to study the equilibrium dynamics of thiocyanate chemical exchange between free ion (NCS(-)) and contact ion pair configurations (MNCS(+)), where M(2+) = Mg(2+) or Ca(2+). Detailed studies of the influence of anion concentration and anion speciation show that the chemical exchange observed with the 2DIR measurements results from NCS(-) exchanging with other anion species in the first solvation shell surrounding Mg(2+) or Ca(2+). The presence of chemical exchange in the 2DIR spectra provides an indirect, but robust, determinant of contact ion pair formation. We observe preferential contact ion pair formation between soft Lewis base anions and hard Lewis acid cations. This observation cannot be easily reconciled with Pearson's acid-base concept or Collins' Law of Matching Water Affinities. The anions that form contact ion pairs also correspond to the ions with an affinity for water and protein surfaces, so similar physical and chemical properties may control these distinct phenomena.

  7. Unexpected Formation of Low Amounts of (R)-Configurated anteiso-Fatty Acids in Rumen Fluid Experiments

    PubMed Central

    Abdurahman, Halima; Ruoff, Tanja; Kaffarnik, Stefanie; Steingass, Herbert; Vetter, Walter

    2017-01-01

    Anteiso-fatty acids (aFA) with odd carbon number are a class of branched-chain fatty acids (BCFA) mainly produced by bacteria. Bacterial sources are also made responsible for their occurrence in the low percent-range in lipids of ruminants (meat and milk) and fish. aFAs are chiral molecules and typically occur predominantly in form of (S)-enantiomers, and their primary precursor has been noted to be isoleucine. Yet, low proportions of (R)-aFAs were also detected in fish and cheese samples. Here we investigated the potential formation of (R)-aFAs by means of incubation experiments with rumen fluid from fistulated cows. Supplementation of rumen fluid with both L- and DL-isoleucine, resulted in a significant (α <0.05) increase of the aFA concentrations but in both cases enantiopure (S)-aFAs were observed. By contrast, incubations without addition of any isoleucine lead to a significant (α <0.05) formation of small proportions of (R)-aFAs similarly to those previously observed in fish and cheese. These results were consistently reproduced in three different years with rumen fluid from different cows fed different diets. All findings point to the existence of a further biosynthesis pathway of aFAs with different stereospecificity than the classic one using isoleucine as primer. PMID:28129363

  8. Effect of monoacyl phosphatidylcholine content on the formation of microemulsions and the dermal delivery of flufenamic acid.

    PubMed

    Hoppel, Magdalena; Juric, Sonja; Ettl, Hanna; Valenta, Claudia

    2015-02-01

    The choice of appropriate excipients is crucial for the success of a dermal drug delivery system. Especially surfactants should be chosen carefully, because of their possible interactions with the skin or the applied drug. Since monoacyl phosphatidylcholine (MAPL) exhibits great emulsification properties and can be derived from natural sources, it is of great interest as surfactant in microemulsions. Therefore, the aim of the present study was to investigate the effect of the MAPL content on the formation of microemulsions. The great emulsification power of MAPL was confirmed by increased isotropic areas with increasing MAPL content. Moreover, a decrease in particle size, particle size distribution and viscosity with increasing MAPL content was determined. Besides its effects on microemulsion structure, MAPL exhibited a significant influence on the skin permeation of flufenamic acid. Interestingly, the higher the MAPL content, the lower was the skin permeation of flufenamic acid. A possible explanation might be that the hydrophilic MAPL could hinder the permeation of the lipophilic drug. In contrast, the skin permeation enhancing effects of the microemulsion with the lowest MAPL content might be attributed to formation of a patch-like structure and therefore better contact between the formulation and the skin.

  9. Deterioration of the seventeenth-century warship Vasa by internal formation of sulphuric acid.

    PubMed

    Sandström, Magnus; Jalilehvand, Farideh; Persson, Ingmar; Gelius, Ulrik; Frank, Patrick; Hall-Roth, Ingrid

    2002-02-21

    The seventeenth-century Swedish warship, Vasa, was recovered in good condition after 333 years in the cold brackish water of Stockholm harbour. After extensive treatment to stabilize and dry the ship's timbers, the ship has been on display in the Vasa Museum since 1990. However, high acidity and a rapid spread of sulphate salts were recently observed on many wooden surfaces, which threaten the continued preservation of the Vasa. Here we show that, in addition to concentrations of sulphate mostly on the surface of oak beams, elemental sulphur has accumulated within the beams (0.2-4 per cent by mass), and also sulphur compounds of intermediate oxidation states exist. The overall quantity of elemental sulphur could produce up to 5,000 kg of sulphuric acid when fully oxidized. We suggest that the oxidation of the reduced sulphur--which probably originated from the penetration of hydrogen sulphide into the timbers as they were exposed to the anoxic water--is being catalysed by iron species released from the completely corroded original iron bolts, as well as from those inserted after salvage. Treatments to arrest acid wood hydrolysis of the Vasa and other wooden marine-archaeological artefacts should therefore focus on the removal of sulphur and iron compounds.

  10. Inhibition of Myeloperoxidase- and Neutrophil-Mediated Hypochlorous Acid Formation in Vitro and Endothelial Cell Injury by (-)-Epigallocatechin Gallate.

    PubMed

    Tian, Rong; Ding, Yun; Peng, Yi-Yuan; Lu, Naihao

    2017-04-10

    Myeloperoxidase (MPO) plays important roles in various diseases through its unique chlorinating activity to catalyze excess hypochlorous acid (HOCl) formation. Epidemiological studies indicate an inverse correlation between plant polyphenol consumption and the incidence of cardiovascular diseases. Here we showed that (-)-epigallocatechin gallate (EGCG), the main flavonoid present in green tea, dose-dependently inhibited MPO-mediated HOCl formation in vitro (chlorinating activities of MPO: 50.2 ± 5.7% for 20 μM EGCG versus 100 ± 5.6% for control, P < 0.01). UV-vis spectral and docking studies indicated that EGCG bound to the active site (heme) of MPO and resulted in the accumulation of compound II, which was unable to produce HOCl. This flavonoid also effectively inhibited HOCl generation in activated neutrophils (HOCl formation: 65.0 ± 5.6% for 20 μM EGCG versus 100 ± 6.2% for control, P < 0.01) without influencing MPO and Nox2 release and superoxide formation, suggesting that EGCG specifically inhibited MPO but not NADPH oxidase activity in activated neutrophils. Moreover, EGCG inhibited MPO (or neutrophil)-mediated HOCl formation in human umbilical vein endothelial cells (HUVEC) culture and accordingly protected HUVEC from MPO (or neutrophil)-induced injury (P < 0.05, all cases), although it did not induce cytotoxicity to HUVEC (P > 0.05, all cases). Our results indicate that dietary EGCG is an effective and specific inhibitor of MPO activity and may participate in the regulation of immune responses at inflammatory sites.

  11. Evidence for coupling of Clostridium perfringens alpha-toxin-induced hemolysis to stimulated phosphatidic acid formation in rabbit erythrocytes.

    PubMed Central

    Sakurai, J; Ochi, S; Tanaka, H

    1993-01-01

    When rabbit erythrocytes were exposed to low concentrations of Clostridium perfringens alpha-toxin, hot-cold hemolysis was observed. The toxin induced production of phosphatidic acid (PA) in a dose-dependent manner when incubated with erythrocytes at 37 degrees C. When erythrocyte membranes were incubated with the toxin and [gamma-32P]ATP in the presence or absence of ethanol, [32P]PA formation was maximal within 30 s, then sharply decreased, and began again after 5 min of incubation. Ethanol had no effect on the early appearance (at approximately 5 min) of PA formation induced by the toxin but significantly inhibited formation of PA over 10 min of incubation. Treatment of erythrocyte membranes with alpha-toxin resulted in the biphasic formation of 1,2-diacylglycerol and PA as well as an increase of inositol-1,4,5-trisphosphate (IP3) and decrease of phosphatidylinositol-4,5-bisphosphate (PIP2) within 30 s. Neomycin inhibited the toxin-induced increase in turbidity of egg yolk suspensions but did not inhibit the toxin-induced hemolysis of intact erythrocytes. On the other hand, neomycin inhibited the toxin-induced hemolysis of saponin-treated erythrocytes. In addition, neomycin inhibited PA formation induced by the toxin in erythrocyte membranes. IP3 was released by incubation of PIP2 with erythrocyte membranes but not by incubation of PIP2 with the toxin. The toxin stimulated the membrane-induced release of IP3 from PIP2. These data suggest that the toxin-induced hemolysis is dependent on the action of phospholipase C in erythrocyte membranes. PMID:8395469

  12. Gibberellin-Abscisic Acid Balances during Arbuscular Mycorrhiza Formation in Tomato.

    PubMed

    Martín-Rodríguez, José A; Huertas, Raúl; Ho-Plágaro, Tania; Ocampo, Juan A; Turečková, Veronika; Tarkowská, Danuše; Ludwig-Müller, Jutta; García-Garrido, José M

    2016-01-01

    Plant hormones have become appropriate candidates for driving functional plant mycorrhization programs, including the processes that regulate the formation of arbuscules in arbuscular mycorrhizal (AM) symbiosis. Here, we examine the role played by ABA/GA interactions regulating the formation of AM in tomato. We report differences in ABA and GA metabolism between control and mycorrhizal roots. Active synthesis and catabolism of ABA occur in AM roots. GAs level increases as a consequence of a symbiosis-induced mechanism that requires functional arbuscules which in turn is dependent on a functional ABA pathway. A negative interaction in their metabolism has been demonstrated. ABA attenuates GA-biosynthetic and increases GA-catabolic gene expression leading to a reduction in bioactive GAs. Vice versa, GA activated ABA catabolism mainly in mycorrhizal roots. The negative impact of GA3 on arbuscule abundance in wild-type plants is partially offset by treatment with ABA and the application of a GA biosynthesis inhibitor rescued the arbuscule abundance in the ABA-deficient sitiens mutant. These findings, coupled with the evidence that ABA application leads to reduce bioactive GA1, support the hypothesis that ABA could act modifying bioactive GA level to regulate AM. Taken together, our results suggest that these hormones perform essential functions and antagonize each other by oppositely regulating AM formation in tomato roots.

  13. Gibberellin–Abscisic Acid Balances during Arbuscular Mycorrhiza Formation in Tomato

    PubMed Central

    Martín-Rodríguez, José A.; Huertas, Raúl; Ho-Plágaro, Tania; Ocampo, Juan A.; Turečková, Veronika; Tarkowská, Danuše; Ludwig-Müller, Jutta; García-Garrido, José M.

    2016-01-01

    Plant hormones have become appropriate candidates for driving functional plant mycorrhization programs, including the processes that regulate the formation of arbuscules in arbuscular mycorrhizal (AM) symbiosis. Here, we examine the role played by ABA/GA interactions regulating the formation of AM in tomato. We report differences in ABA and GA metabolism between control and mycorrhizal roots. Active synthesis and catabolism of ABA occur in AM roots. GAs level increases as a consequence of a symbiosis-induced mechanism that requires functional arbuscules which in turn is dependent on a functional ABA pathway. A negative interaction in their metabolism has been demonstrated. ABA attenuates GA-biosynthetic and increases GA-catabolic gene expression leading to a reduction in bioactive GAs. Vice versa, GA activated ABA catabolism mainly in mycorrhizal roots. The negative impact of GA3 on arbuscule abundance in wild-type plants is partially offset by treatment with ABA and the application of a GA biosynthesis inhibitor rescued the arbuscule abundance in the ABA-deficient sitiens mutant. These findings, coupled with the evidence that ABA application leads to reduce bioactive GA1, support the hypothesis that ABA could act modifying bioactive GA level to regulate AM. Taken together, our results suggest that these hormones perform essential functions and antagonize each other by oppositely regulating AM formation in tomato roots. PMID:27602046

  14. Effect of Exogenous Indole-3-Acetic Acid and Indole-3-Butyric Acid on Internal Levels of the Respective Auxins and Their Conjugation with Aspartic Acid during Adventitious Root Formation in Pea Cuttings

    PubMed Central

    Nordström, Ann-Caroline; Jacobs, Fernando Alvarado; Eliasson, Lennart

    1991-01-01

    The influence of exogenous indole-3-acetic acid (IAA) and indole-3-butyric acid (IBA) on the internal levels of these auxins was studied during the first 4 days of adventitious root formation in cuttings of Pisum sativum L. The quantitations were done by high performance liquid chromatography with spectrofluorometric detection. IBA, identified by combined gas chromatography-mass spectrometry (GC-MS), was found to naturally occur in this plant material. The root inducing ability of exogenous IBA was superior to that of IAA. The IAA level in the tissue increased considerably on the first day after application of IAA, but rapidly decreased again, returning to a level twice the control by day 3. The predominant metabolic route was conjugation with aspartic acid, as reflected by the increase in the level of indole-3-acetylaspartic acid. The IBA treatment resulted in increases in the levels of IBA, IAA, and indole-3-acetylaspartic acid. The IAA content rapidly returned to control levels, whereas the IBA level remained high throughout the experimental period. High amounts of indole-3-butyrylaspartic acid were found in the tissue after feeding with IBA. The identity of the conjugate was confirmed by 1H-nuclear magnetic resonance and GC-MS. IBA was much more stable in solution than IAA. No IAA was detected after 48 hours, whereas 70% IBA was still recovered after this time. The relatively higher root inducing ability of IBA is ascribed to the fact that its level remained elevated longer than that of IAA, even though IBA was metabolized in the tissue. Adventitious root formation is discussed on the basis of these findings. PMID:16668265

  15. In vivo and vitro studies on formation of bile acids in patients with Zellweger syndrome. Evidence that peroxisomes are of importance in the normal biosynthesis of both cholic and chenodeoxycholic acid.

    PubMed Central

    Kase, B F; Pedersen, J I; Strandvik, B; Björkhem, I

    1985-01-01

    The last step in bile acid formation involves conversion of 3 alpha,7 alpha,12 alpha-trihydroxy-5 beta-cholestanoic acid (THCA) into cholic acid and 3 alpha,7 alpha-dihydroxy-5 beta-cholestanoic acid (DHCA) into chenodeoxycholic acid. The peroxisomal fraction of rat and human liver has the highest capacity to catalyze these reactions. Infants with Zellweger syndrome lack liver peroxisomes, and accumulate 5 beta-cholestanoic acids in bile and serum. We recently showed that such an infant had reduced capacity to convert a cholic acid precursor, 5 beta-cholestane-3 alpha,7 alpha,12 alpha-triol into cholic acid. 7 alpha-Hydroxy-4-cholesten-3-one is a common precursor for both cholic acid and chenodeoxycholic acid. Intravenous administration of [3H]7 alpha-hydroxy-4-cholesten-3-one to an infant with Zellweger syndrome led to a rapid incorporation of 3H into biliary THCA but only 10% of 3H was incorporated into cholic acid after 48 h. The incorporation of 3H into DHCA was only 25% of that into THCA and the incorporation into chenodeoxycholic acid approximately 50% of that in cholic acid. The conversion of intravenously administered [3H]THCA into cholic acid in another infant with Zellweger syndrome was only 7%. There was a slow conversion of THCA into 3 alpha,7 alpha,12 alpha-trihydroxy-5 beta-C29-dicarboxylic acid. The pool size of both cholic- and chenodeoxycholic acid was markedly reduced. Preparations of liver from two patients with Zellweger syndrome had no capacity to catalyze conversion of THCA into cholic acid. There was, however, a small conversion of DHCA into chenodeoxycholic acid and into THCA. It is concluded that liver peroxisomes are important both for the conversion of THCA into cholic acid and DHCA into chenodeoxycholic acid. PMID:4077985

  16. Palmitic Acid Reduces Circulating Bone Formation Markers in Obese Animals and Impairs Osteoblast Activity via C16-Ceramide Accumulation.

    PubMed

    Alsahli, Ahmad; Kiefhaber, Kathryn; Gold, Tziporah; Muluke, Munira; Jiang, Hongfeng; Cremers, Serge; Schulze-Späte, Ulrike

    2016-05-01

    Obesity and impaired lipid metabolism increase circulating and local fatty acid (FA) levels. Our previous studies showed that a high high-saturated -fat diet induced greater bone loss in mice than a high high-unsaturated-fat diet due to increased osteoclast numbers and activity. The impact of elevated FA levels on osteoblasts is not yet clear. We induced obesity in 4 week old male mice using a palmitic acid (PA)- or oleic acid (OA)-enriched high fat high-fat diet (HFD) (20 % of calories from FA), and compared them to mice on a normal (R) caloric diet (10 % of calories from FA). We collected serum to determine FA and bone metabolism marker levels. Primary osteoblasts were isolated; cultured in PA, OA, or control (C) medium; and assessed for mineralization activity, gene expression, and ceramide levels. Obese animals in the PA and OA groups had significantly lower serum levels of bone formation markers P1NP and OC compared to normal weight animals (*p < 0.001), with the lowest marker levels in animals on an PA-enriched HFD (*p < 0.001). Accordingly, elevated levels of PA significantly reduced osteoblast mineralization activity in vitro (*p < 0.05). Elevated PA intake significantly increased C16 ceramide accumulation. This accumulation was preventable through inhibition of SPT2 (serine palmitoyl transferase 2) using myriocin. Elevated levels of PA reduce osteoblast function in vitro and bone formation markers in vivo. Our findings suggest that saturated PA can compromise bone health by affecting osteoblasts, and identify a potential mechanism through which obesity promotes bone loss.

  17. The application of multiple analyte adduct formation in the LC-MS(3) analysis of valproic acid in human serum.

    PubMed

    Dziadosz, Marek

    2017-01-01

    LC-MS using electrospray ionisation (negative ion mode) and low-energy collision-induced dissociation tandem mass spectrometric (CID-MS/MS) analysis, together with the multiple analyte adduct formation with the components of the mobile phase, were applied to analyse valproic acid in human serum with LC-MS(3). The CID-fragmentation of the precursor analyte adduct [M+2CH3COONa-H](-) was applied in the method validation (307.1/225.1/143.0). Chromatographic separation was performed with a Luna 5μm C18 (2) 100A, 150mm×2mm column and the elution with a mobile phase consisting of A (H2O/methanol=95/5, v/v) and B (H2O/methanol=3/97, v/v), both with 10mM ammonium acetate and 0.1% acetic acid. A binary flow pumping mode with a total flow rate of 0.400mL/min was used. The calculated limit of detection/quantification of the method calibrated in the range of 10-200μg/mL was 0.31/1.0μg/mL. The sample preparation based on protein precipitation with 1mL of H2O/methanol solution (3/97, v/v) with 10mM sodium acetate and 100mM acetic acid. On the basis of the experiments performed could be demonstrated, that multiple analyte adduct formation can be applied to generate MS(3) quantitation of analytes with problematic fragmentation. The presented new strategy makes the analysis of small drugs, which do not produce any stable product ions at all, on the basis of LC-MS(3) possible.

  18. Deficiency of PdxR in Streptococcus mutans affects vitamin B6 metabolism, acid tolerance response and biofilm formation.

    PubMed

    Liao, S; Bitoun, J P; Nguyen, A H; Bozner, D; Yao, X; Wen, Z T

    2015-08-01

    Streptococcus mutans, a key etiological agent of the human dental caries, lives primarily on the tooth surface in tenacious biofilms. The SMU864 locus, designated pdxR, is predicted to encode a member of the novel MocR/GabR family proteins, which are featured with a winged helix DNA-binding N-terminal domain and a C-terminal domain highly homologous to the pyridoxal phosphate-dependent aspartate aminotransferases. A pdxR-deficient mutant, TW296, was constructed using allelic exchange. PdxR deficiency in S. mutans had little effect on cell morphology and growth when grown in brain heart infusion. However, when compared with its parent strain, UA159, the PdxR-deficient mutant displayed major defects in acid tolerance response and formed significantly fewer biofilms (P < 0.01). When analyzed by real-time polymerase chain reaction, PdxR deficiency was found to drastically reduce expression of an apparent operon encoding a pyridoxal kinase (SMU865) and a pyridoxal permease (SMU866) of the salvage pathway of vitamin B6 biosynthesis. In addition, PdxR deficiency also altered the expression of genes for ClpL protease, glucosyltransferase B and adhesin SpaP, which are known to play important roles in stress tolerance and biofilm formation. Consistently, PdxR-deficiency affected the growth of the deficient mutant when grown in defined medium with and without vitamin B6 . Further studies revealed that although S. mutans is known to require vitamin B6 to grow in defined medium, B6 vitamers, especially pyridoxal, were strongly inhibitory at millimolar concentrations, against S. mutans growth and biofilm formation. Our results suggest that PdxR in S. mutans plays an important role in regulation of vitamin B6 metabolism, acid tolerance response and biofilm formation.

  19. Physical defect formation in few layer graphene-like carbon on metals: influence of temperature, acidity, and chemical functionalization.

    PubMed

    Schumacher, Christoph M; Grass, Robert N; Rossier, Michael; Athanassiou, Evagelos K; Stark, Wendelin J

    2012-03-06

    A systematical examination of the chemical stability of cobalt metal nanomagnets with a graphene-like carbon coating is used to study the otherwise rather elusive formation of nanometer-sized physical defects in few layer graphene as a result of acid treatments. We therefore first exposed the core-shell nanomaterial to well-controlled solutions of altering acidity and temperature. The release of cobalt into these solutions over time offered a simple tool to monitor the progress of particle degradation. The results suggested that the oxidative damage of the graphene-like coatings was the rate-limiting step during particle degradation since only fully intact or entirely emptied carbon shells were found after the experiments. If ionic noble metal species were additionally present in the acidic solutions, the noble metal was found to reduce on the surface of specific, defective particles. The altered electrochemical gradients across the carbon shells were however not found to lead to a faster release of cobalt from the particles. The suggested mechanistic insight was further confirmed by the covalent chemical functionalization of the particle surface with chemically inert aryl species, which leads to an additional thickening of the shells. This leads to reduced cobalt release rates as well as slower noble metal reduction rates depending on the augmentation of the shell thickness.

  20. Preserving ground water samples with hydrochloric acid does not result in the formation of chloroform

    USGS Publications Warehouse

    Squillace, Paul J.; Pankow, James F.; Barbash, Jack E.; Price, Curtis V.; Zogorski, John S.

    1999-01-01

    Water samples collected for the determination of volatile organic compounds (VOCs) are often preserved with hydrochloric acid (HCl) to inhibit the biotransformation of the analytes of interest until the chemical analyses can he performed. However, it is theoretically possible that residual free chlorine in the HCl can react with dissolved organic carbon (DOC) to form chloroform via the haloform reaction. Analyses of 1501 ground water samples preserved with HCl from the U.S. Geological Survey's National Water-Quality Assessment Program indicate that chloroform was the most commonly detected VOC among 60 VOCs monitored. The DOC concentrations were not significantly larger in samples with detectable chloroform than in those with no delectable chloroform, nor was there any correlation between the concentrations of chloroform and DOC. Furthermore, chloroform was detected more frequently in shallow ground water in urban areas (28.5% of the wells sampled) than in agricultural areas (1.6% of the wells sampled), which indicates that its detection was more related to urban land-use activities than to sample acidification. These data provide strong evidence that acidification with HCl does not lead to the production of significant amounts of chloroform in ground water samples. To verify these results, an acidification study was designed to measure the concentrations of all trihalomethanes (THMs) that can form as a result of HCl preservation in ground water samples and to determine if ascorbic acid (C6H8O6) could inhibit this reaction if it did occur. This study showed that no THMs were formed as a result of HCl acidification, and that ascorbic acid had no discernible effect on the concentrations of THMs measured.

  1. Effect of sewage sludge on formation of acidic ground water at a reclaimed coal mine

    USGS Publications Warehouse

    Cravotta, C.A.

    1998-01-01

    Data on rock, ground water, vadose water, and vadose gas chemistry were collected for two years after sewage sludge was applied at a reclaimed surface coal mine in Pennsylvania to determine if surface-applied sludge is an effective barrier to oxygen influx, contributes metals and nutrients to ground water, and promotes the acidification of ground water. Acidity, sulfate, and metals concentrations were elevated in the ground water (6- to 21-m depth) from spoil relative to unmined rock because of active oxidation of pyrite and dissolution of aluminosilicate, carbonate, and Mn-Fe-oxide minerals in the spoil. Concentrations of acidity, sulfate, metals (Fe, Mn, Al, Cd, Cu, Cr, Ni, Zn), and nitrate, and abundances of iron-oxidizing bacteria were elevated in the ground water from sludge-treated spoil relative to untreated spoil having a similar mineral composition; however, gaseous and dissolved oxygen concentrations did not differ between the treatments. Abundances of iron-oxidizing bacteria in the ground water samples were positively correlated with concentrations of ammonia, nitrate, acidity, metals, and sulfate. Concentrations of metals in vadose water samples (<5-m depth) from sludge-treated spoil (pH 5.9) were not elevated relative to untreated spoil (pH 4.4). In contrast, concentrations of nitrate were elevated in vadose water samples from sludge-treated spoil, frequently exceeding 10 mg/L. Downgradient decreases in nitrate to less than 3 mg/L and increases in sulfate concentrations in underlying ground water could result from oxidation of pyrite by nitrate. Thus, sewage sludge added to pyritic spoil can increase the growth of iron-oxidizing bacteria, the oxidation of pyrite, and the acidification of ground water. Nevertheless, the overall effects on ground water chemistry from the sludge were small and probably short-lived relative to the effects from mining only.

  2. Formation of substrate-based gold nanocage chains through dealloying with nitric acid

    PubMed Central

    Yan, Ziren; Wu, Ying

    2015-01-01

    Summary Metal nanocages have raised great interest because of their new properties and wide applications. Here, we report on the use of galvanic replacement reactions to synthesize substrate-supported Ag–Au nanocages from silver templates electrodeposited on transparent indium tin oxide (ITO) film coated glass. The residual Ag in the composition was dealloyed with 10% nitric acid. It was found that chains of Au nanocages were formed on the substrate surface during dealloying. When the concentration of HNO3 increased to 20%, the structures of nanocages were damaged and formed crescent or semi-circular shapes. The transfer process on the substrate surface was discussed. PMID:26199839

  3. Inhibition by polyphenolic phytochemicals and sulfurous compounds of the formation of 8-chloroguanosine mediated by hypochlorous acid, human myeloperoxidase, and activated human neutrophils.

    PubMed

    Nakano, Toshiki; Masuda, Mitsuharu; Suzuki, Toshinori; Ohshima, Hiroshi

    2012-01-01

    Hypochlorous acid (HOCl) produced by myeloperoxidase (MPO) of activated neutrophils can react with nucleic acid bases to form chlorinated nucleosides such as 8-chloroguanosine (Cl-Guo). Chlorination is enhanced by nicotine. We investigated the effects of various natural antioxidants including polyphenolic phytochemicals on the formation of Cl-Guo by HOCl in the presence and the absence of nicotine. Polyphenols, including catechins, curcumin, resveratrol, silibinin, and sulfurous compound α-lipoic acid, were found to inhibit both HOCl- and human MPO-induced Cl-Guo formation dose-dependently. Among the test compounds, (-)-epigallocatechin gallate (EGCG) showed the strongest inhibitory effect. Cl-Guo formation, mediated by activated human neutrophils in the presence of nicotine, was inhibited by EGCG, silibinin, and α-lipoic acid. These results suggest that polyphenols and sulfurous compounds have the potential to inhibit the induction of nucleobase damage mediated by chlorination, with possible application to reducing DNA damage associated with inflammation and cigarette-smoke inhalation.

  4. Diffusion and reaction of pollutants in stratus clouds: application to nocturnal acid formation in plumes

    SciTech Connect

    Seigneur, C.; Saxena, P.; Mirabella, V.A.

    1985-09-01

    A mathematical model is presented that describes the transport, turbulent diffusion, and chemical reactions of air pollutants in stratus clouds. The chemical kinetic mechanism treats 97 gaseous, heterogeneous, and aqueous reactions between 54 species. The dispersion and night-time chemistry of a power plant plume in a stratus cloud is simulated. The contributions of various chemical pathways to the formation of sulfate and nitrate, the differences between plume and background concentrations, and the effect of reduced primary emissions on secondary pollutants are discussed. Calculated sulfate and nitrate concentrations are commensurate with measured atmospheric concentrations.

  5. Photochemistry of methane and the formation of hydrocyanic acid (HCN) in the earth's early atmosphere

    NASA Technical Reports Server (NTRS)

    Zahnle, K. J.

    1986-01-01

    A one-dimensional photochemical model is used to analyze the photochemistries of CH4 and HCN in the primitive terrestrial atmosphere. CH4, N2, and HCN photolysis are examined. The background atmosphere and boundary conditions applied in the analysis are described. The formation of HCN as a by-product of N2 and CH4 photolysis is investigated; the effects of photodissociation and rainfall on HCN is discussed. The low and high CH4 mixing ratios and radical densities are studied.

  6. Effects of combined oleic acid and fluoride at sub-MIC levels on EPS formation and viability of Streptococcus mutans UA159 biofilms.

    PubMed

    Cai, Jian-Na; Kim, Mi-A; Jung, Ji-Eun; Pandit, Santosh; Song, Kwang-Yeob; Jeon, Jae-Gyu

    2015-01-01

    Despite the widespread use of fluoride, dental caries, a biofilm-related disease, remains an important health problem. This study investigated whether oleic acid, a monounsaturated fatty acid, can enhance the effect of fluoride on extracellular polysaccharide (EPS) formation by Streptococcus mutans UA159 biofilms at sub-minimum inhibitory concentration levels, via microbiological and biochemical methods, confocal fluorescence microscopy, and real-time PCR. The combination of oleic acid with fluoride inhibited EPS formation more strongly than did fluoride or oleic acid alone. The superior inhibition of EPS formation was due to the combination of the inhibitory effects of oleic acid and fluoride against glucosyltransferases (GTFs) and GTF-related gene (gtfB, gtfC, and gtfD) expression, respectively. In addition, the combination of oleic acid with fluoride altered the bacterial biovolume of the biofilms without bactericidal activity. These results suggest that oleic acid may be useful for enhancing fluoride inhibition of EPS formation by S. mutans biofilms, without killing the bacterium.

  7. Energetics of oxo- and thio-dipeptide formation via amino acid condensation: a systematic computational analysis.

    PubMed

    Torsello, Mauro; Orian, Laura; De Zotti, Marta; Saini, Roberta; Formaggio, Fernando; Polimeno, Antonino

    2014-09-07

    Oxo-dipeptides and thio-dipeptides are built via condensation between couples of amino acids and amino thioacids, the latter with the carbonyl oxygen replaced by an sp(2) sulfur. We explored via in silico methods (PBE0/6-31G(d,p) and PBE0/6-311G(d,p)) all the possible combinations and built 800 dipeptides, whose structures were fully optimized. Maps of condensation energies are presented to highlight optimal partners leading to stable dipeptides and critical situations for which lower stability or instability is predicted in terms of Gibbs reaction free energies. To validate the feasibility of our computational investigation, we synthesized and compared the stabilities of two thionated dimers, namely -Gly[Ψ(CSNH)]Gly- and -Phe[Ψ(CSNH)]Phe-, characterized by diverging physico-chemical properties. To the best of our knowledge, this is the first systematic analysis reported for dipeptides built from natural amino acids as well as for their corresponding thio-analogs.

  8. Coordinate covalent C --> B bonding in phenylborates and latent formation of phenyl anions from phenylboronic Acid.

    PubMed

    Glaser, Rainer; Knotts, Nathan

    2006-02-02

    The results are reported of a theoretical study of the addition of small nucleophiles Nu(-) (HO(-), F(-)) to phenylboronic acid Ph-B(OH)(2) and of the stability of the resulting complexes [Ph-B(OH)(2)Nu](-) with regard to Ph-B heterolysis [Ph-B(OH)(2)Nu](-) --> Ph(-) + B(OH)(2)Nu as well as Nu(-)/Ph(-) substitution [Ph-B(OH)(2)Nu](-) + Nu(-) --> Ph(-) + [B(OH)(2)Nu(2)](-). These reactions are of fundamental importance for the Suzuki-Miyaura cross-coupling reaction and many other processes in chemistry and biology that involve phenylboronic acids. The species were characterized by potential energy surface analysis (B3LYP/6-31+G*), examined by electronic structure analysis (B3LYP/6-311++G**), and reaction energies (CCSD/6-311++G**) and solvation energies (PCM and IPCM, B3LYP/6-311++G*) were determined. It is shown that Ph-B bonding in [Ph-B(OH)(2)Nu](-) is coordinate covalent and rather weak (<50 kcal.mol(-1)). The coordinate covalent bonding is large enough to inhibit unimolecular dissociation and bimolecular nucleophile-assisted phenyl anion liberation is slowed greatly by the negative charge on the borate's periphery. The latter is the major reason for the extraordinary differences in the kinetic stabilities of diazonium ions and borates in nucleophilic substitution reactions despite their rather similar coordinate covalent bond strengths.

  9. Pattern formation in fatty acid-nanoparticle and lipid-nanoparticle mixed monolayers at water surface

    NASA Astrophysics Data System (ADS)

    Choudhuri, M.; Datta, A.; Iyengar, A. N. Sekar; Janaki, M. S.

    2015-06-01

    Dodecanethiol-capped gold nanoparticles (AuNPs) are self-organized in two different amphiphilic monolayers one of which is a single-tailed fatty acid Stearic acid (StA) and the other a double-tailed lipid 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC). In the StA-AuNP film the AuNPs self-organize to form an interconnected network of nanoclusters on compression while in the DMPC-AuNP film the AuNPs aggregate to form random, isolated clusters in the film. The long time evolution of the films at constant surface pressure reveals ring structures in the former and diffusion limited aggregates in the latter that with time evolve into an irregular porous maze of AuNPs in the DMPC film. The difference in structure of the AuNP patterns in the two films can be attributed to a difference in the lipophilic interactions between the NPs and the amphiphilic molecules. The mean square intensity fluctuations f(ln) calculated along a typical line for the 2D structures in both the films at initial and final stages of long time evolution reflect the structural changes in the films over time.

  10. Development of artificial nucleic acid that recognizes a CG base pair in triplex DNA formation.

    PubMed

    Hari, Yoshiyuki

    2013-01-01

    An oligonucleotide that can form a triplex with double-stranded DNA is called a triplex-forming oligonucleotide (TFO). TFOs have gained considerable attention because of their potential as gene targeting tools. However, triplex DNA formation involves inherent problems for practical use. The most important problem is that natural nucleotides in TFO do not have sufficient affinity and base pair-selectivity to pyrimidine-purine base pair, like a CG or TA base pair, within dsDNA. This suggests that dsDNA region including a CG or TA base pair cannot be targeted. Therefore, artificial nucleotides, especially with non-natural nucleobases, capable of direct recognition of a CG or TA base pair via hydrogen bond formation have been developed; however, nucleotides with better selectivity and stronger affinity are necessary for implementing this dsDNA-targeting technology using TFOs. Under such a background, we considered that facile and efficient synthesis of various nucleobase derivatives in TFOs would be useful for finding an ideal nucleobase for recognition of a CG or TA base pair because detailed and rational exploration of nucleobase structures is facilitated. Recently, to develop a nucleobase recognizing a CG base pair, we have used post-elongation modification, i.e., modification after oligonucleotide synthesis, for the facile synthesis of nucleobase derivatives. This review mainly summarizes our recent findings on the development of artificial nucleobases and nucleotides for recognition of a CG base pair in triplexes formed between dsDNA and TFOs.

  11. Nitrogen conservation and acidity control during food wastes composting through struvite formation.

    PubMed

    Wang, Xuan; Selvam, Ammaiyappan; Chan, Manting; Wong, Jonathan W C

    2013-11-01

    One of the main problems of food waste composting is the intensive acidification due to initial rapid fermentation that retards decomposition efficiency. Lime addition overcame this problem, but resulted in significant loss of nitrogen as ammonia that reduces the nutrient contents of composts. Therefore, this study investigated the feasibility of struvite formation as a strategy to control pH and reduce nitrogen loss during food waste composting. MgO and K2HPO4 were added to food waste in different molar ratios (P1, 1:1; P2, 1:2), and composted in 20-L composters. Results indicate that K2HPO4 buffered the pH in treatment P2 besides supplementing phosphate into the compost. In P2, organic decomposition reached 64% while the formation of struvite effectively reduced the nitrogen loss from 40.8% to 23.3% during composting. However, electrical conductivity of the compost increased due to the addition of Mg and P salts that requires further investigation to improve this technology.

  12. Prevention of Histamine Formation in Cheese by Bacteriocin-Producing Lactic Acid Bacteria

    PubMed Central

    Joosten, H.; Nunez, M.

    1996-01-01

    The susceptibility of 13 amine-forming lactobacilli to several bacteriocins was investigated by an agar diffusion assay. All strains were susceptible to nisin and to five bacteriocins of enterococcal origin. Pediocin PA-1, bavaricin A, lactococcin A, and a bacteriocin from Enterococcus faecalis 1061 did not show inhibitory activity. Two bacteriocin-producing enterococci and a nisin-producing Lactococcus lactis strain were employed as starters in separate cheese-making experiments. Outgrowth of histamine producer Lactobacillus buchneri St2A, which was added to the milk at levels of up to 190 CFU/ml, was almost completely inhibited. No histamine formation was detected in the cheeses made with bacteriocin-producing starters. In the control cheese without bacteriocin, St2A reached levels of 1.1 x 10(sup8) CFU/g, and 200 mg of histamine per kg was found after 4 months of ripening. To our knowledge, this is the first report of bacteriocin-mediated inhibition of histamine formation in foods. PMID:16535285

  13. Phenolic acids inhibit the formation of advanced glycation end products in food simulation systems depending on their reducing powers and structures.

    PubMed

    Chen, Hengye; Virk, Muhammad Safiullah; Chen, Fusheng

    2016-06-01

    The concentration of advanced glycation end products (AGEs) in foods, which are formed by Maillard reaction, has demonstrated as risk factors associated with many chronic diseases. The AGEs inhibitory activities of five common phenolic acids (protocatechuic acid, dihydroferulic acid, p-coumaric acid, p-hydroxybenzoic acid and salicylic acid) with different chemical properties had been investigated in two food simulation systems (glucose-bovine serum albumin (BSA) and oleic acid-BSA). The results substantiated that the AGEs inhibitory abilities of phenolic acids in the oleic acid BSA system were much better than the glucose-BSA system for their strong reducing powers and structures. Among them, dihydrogenferulic acid showed strong inhibition of AGEs formation in oleic acid-BSA system at 0.01 mg/mL compared to nonsignificant AGEs inhibitory effect in oleic acid-BSA system at 10-fold higher concentration (0.1 mg/mL). This study suggests that edible plants rich in phenolic acids may be used as AGEs inhibitor during high-fat cooking.

  14. Tribological properties of boric acid and boric-acid-forming surfaces: Part 2, Formation and self-lubrication mechanisms of boric acid films on boron- and boric-oxide-containing surfaces

    SciTech Connect

    Erdemir, A.; Fenske, G.R.; Erck, R.A.; Nichols, F.A.; Busch, D.

    1990-01-01

    This paper describes the formation and self-lubricating mechanisms of boric acid films on boron- and boric oxide-containing surfaces. As reported in part I, boric acid, owing to a layered triclinic crystal structure and weak interlayer bonds, enjoys an unusual lubrication capability. RF-magnetron sputtering and vacuum evaporation techniques were used to produce thin coatings of boron and boric oxides on steel substrates. The results of tribological experiments indicate that the room temperature friction coefficient of tribosystems that include boron and/or boric oxide coatings ranges from 0.05 to 0.07, depending on the coating type. Laser-Raman spectroscopy of these surfaces revealed that this low friction is associated with a thin boric acid film that forms on the surfaces of these coatings. The fabrication and potential importance of boric acid and boric acid-forming surfaces for practical applications are enumerated. Surface engineering of tribomaterials, such as these demonstrated in this paper, is suggested as a new lubrication concept for use in present and future tribological industries. 16 refs.

  15. Nanopore formation on the surface oxide of commercially pure titanium grade 4 using a pulsed anodization method in sulfuric acid.

    PubMed

    Williamson, R S; Disegi, J; Griggs, J A; Roach, M D

    2013-10-01

    Titanium and its alloys form a thin amorphous protective surface oxide when exposed to an oxygen environment. The properties of this oxide layer are thought to be responsible for titanium and its alloys biocompatibility, chemical inertness, and corrosion resistance. Surface oxide crystallinity and pore size are regarded to be two of the more important properties in establishing successful osseointegration. Anodization is an electrochemical method of surface modification used for colorization marking and improved bioactivity on orthopedic and dental titanium implants. Research on titanium anodization using sulphuric acid has been reported in the literature as being primarily conducted in molarity levels 3 M and less using either galvanostatic or potentiostatic methods. A wide range of pore diameters ranging from a few nanometers up to 10 μm have been shown to form in sulfuric acid electrolytes using the potentiostatic and galvanostatic methods. Nano sized pores have been shown to be beneficial for bone cell attachment and proliferation. The purpose of the present research was to investigate oxide crystallinity and pore formation during titanium anodization using a pulsed DC waveform in a series of sulfuric acid electrolytes ranging from 0.5 to 12 M. Anodizing titanium in increasing sulfuric acid molarities showed a trend of increasing transformations of the amorphous natural forming oxide to the crystalline phases of anatase and rutile. The pulsed DC waveform was shown to produce pores with a size range from ≤0.01 to 1 μm(2). The pore size distributions produced may be beneficial for bone cell attachment and proliferation.

  16. Retinoic acid signaling controls the formation, proliferation and survival of the blastema during adult zebrafish fin regeneration.

    PubMed

    Blum, Nicola; Begemann, Gerrit

    2012-01-01

    Adult teleosts rebuild amputated fins through a proliferation-dependent process called epimorphic regeneration, in which a blastema of cycling progenitor cells replaces the lost fin tissue. The genetic networks that control formation of blastema cells from formerly quiescent stump tissue and subsequent blastema function are still poorly understood. Here, we investigated the cellular and molecular consequences of genetically interfering with retinoic acid (RA) signaling for the formation of the zebrafish blastema. We show that RA signaling is upregulated within the first few hours after fin amputation in the stump mesenchyme, where it controls Fgf, Wnt/β-catenin and Igf signaling. Genetic inhibition of the RA pathway at this stage blocks blastema formation by inhibiting cell cycle entry of stump cells and impairs the formation of the basal epidermal layer, a signaling center in the wound epidermis. In the established blastema, RA signaling remains active to ensure the survival of the highly proliferative blastemal population by controlling expression of the anti-apoptotic factor bcl2. In addition, RA signaling maintains blastema proliferation through the activation of growth-stimulatory signals mediated by Fgf and Wnt/β-catenin signaling, as well as by reducing signaling through the growth-inhibitory non-canonical Wnt pathway. The endogenous roles of RA in adult vertebrate appendage regeneration are uncovered here for the first time. They provide a mechanistic framework to understand previous observations in salamanders that link endogenous sources of RA to the regeneration process itself and support the hypothesis that the RA signaling pathway is an essential component of vertebrate tissue regeneration.

  17. Regulation of the hemA gene during 5-aminolevulinic acid formation in Pseudomonas aeruginosa.

    PubMed Central

    Hungerer, C; Troup, B; Römling, U; Jahn, D

    1995-01-01

    The general tetrapyrrole precursor 5-aminolevulinic acid is formed in bacteria via two different biosynthetic pathways. Members of the alpha group of the proteobacteria use 5-aminolevulinic acid synthase for the condensation of succinyl-coenzyme A and glycine, while other bacteria utilize a two-step pathway from aminoacylated tRNA(Glu). The tRNA-dependent pathway, involving the enzymes glutamyl-tRNA reductase (encoded by hemA) and glutamate-1-semialdehyde-2,1-aminomutase (encoded by hemL), was demonstrated to be used by Pseudomonas aeruginosa, Pseudomonas putida, Pseudomonas stutzeri, Comamonas testosteroni, Azotobacter vinelandii, and Acinetobacter calcoaceticus. To study the regulation of the pathway, the glutamyl-tRNA reductase gene (hemA) from P. aeruginosa was cloned by complementation of an Escherichia coli hemA mutant. The hemA gene was mapped to the SpeI A fragment and the DpnIL fragment of the P. aeruginosa chromosome corresponding to min 24.1 to 26.8. The cloned hemA gene, coding for a protein of 423 amino acids with a calculated molecular mass of 46,234 Da, forms an operon with the gene for protein release factor 1 (prf1). This translational factor mediates the termination of the protein chain at the ribosome at amber and ochre codons. Since the cloned hemA gene did not possess one of the appropriate stop codons, an autoregulatory mechanism such as that postulated for the enterobacterial system was ruled out. Three open reading frames of unknown function transcribed in the opposite direction to the hemA gene were found. hemM/orf1 and orf2 were found to be homologous to open reading frames located in the 5' region of enterobacterial hemA genes. Utilization of both transcription start sites was changed in a P. aeruginosa mutant missing the oxygen regulator Anr (Fnr analog), indicating the involvement of the transcription factor in hemA expression. DNA sequences homologous to one half of an Anr binding site were detected at one of the determined

  18. Prevention of formation of acid drainage from high-sulfur coal refuse by inhibition of iron- and sulfur-oxidizing microorganisms. I. Preliminary experiments in controlled shaken flasks.

    PubMed

    Dugan, P R

    1987-01-01

    Changes of pH and sulfate concentration in high-sulfur coal refuse slurries are used as measurements of microbial pyrite oxidation in the laboratory. Sodium lauryl sulfate (SLS), alkylbenzene sulfonate (ABS), benzoic acid (BZ) and combinations of SLS plus BZ and ABS plus BZ effectively inhibited formation of sulfate and acid when added in concentrations greater than 50 mg/L to inoculated 20 or 30% coal refuse slurries. Here 25 mg/L concentrations of SLS, ABS, and ABS + BZ stimulated acid production. Formic, hexanoic, oxalic, propionic, and pyruvic