Green diesel production via catalytic hydrogenation/decarboxylation of triglycerides and fatty acids of vegetable oil and brown grease

Science.gov (United States)

Sari, Elvan

Increase in the petroleum prices, projected increases in the world's energy demand and environmental awareness have shifted the research interest to the alternative fuel technologies. In particular, green diesel, vegetable oil/animal fat/waste oil and grease derived hydrocarbons in diesel boiling range, has become an attractive alternative to biodiesel---a mixture of fatty acid methyl esters, particularly due to its superior fuel properties that are similar to petroleum diesel. Hence, green diesel can be used as a drop-in fuel in the current diesel engines. The current technology for production of green diesel-hydrodeoxygenation of triglycerides and fatty acids over conventional hydrotreating catalysts suffers from fast catalyst deactivation in the absence of hydrogen combined with high temperatures and high fatty acid content in the feedstock. Additionally, excess hydrogen requirement for hydrodeoxygenation technique leads to high production costs. This thesis proposes a new technology-selective decarboxylation of brown grease, which is a mixture of fats and oils collected from waste water trap and rich in fatty acids, over a supported noble metal catalyst that overcomes the green diesel production challenges. In contrast to other feedstocks used for liquid biofuel production, brown grease is inexpensive and non-food competing feedstock, therefore the process finds solution to waste management issues, reduces the renewable fuel production cost and does not add to the global food shortage problems. Special catalyst formulations were developed to have a high activity and stability in the absence of hydrogen in the fatty acid decarboxylation process. The study shows how catalyst innovations can lead to a new technology that overcomes the process challenges. First, the effect of reaction parameters on the activity and the selectivity of brown grease decarboxylation with minimum hydrogen consumption over an activated carbon supported palladium catalyst were

Rapid Access to Ortho-Alkylated Vinylarenes from Aromatic Acids by Dearomatization and Tandem Decarboxylative C-H Olefination/Rearomatization.

Science.gov (United States)

Tsai, Hung-Chang; Huang, Yen-Hsiang; Chou, Chih-Ming

2018-03-02

A two-step straightforward method for the preparation of ortho-alkylated vinylarenes from readily available benzoic acids is described. The synthetic route involves the dearomatization of benzoic acids by Birch reduction providing alkylated cyclohexa-2,5-dienyl-1-carboxylic acids. The diene subsequently undergoes a decarboxylative C-H olefination followed by rearomatization to deliver ortho-alkylated vinylarene. Mechanistic studies suggest that a Pd/Ag bimetallic catalytic system is important in the tandem decarboxylative C-H olefination/rearomatization step.

Generation of a proton motive force by histidine decarboxylation and electrogenic histidine/histamine antiport in Lactobacillus buchneri.

Science.gov (United States)

Molenaar, D; Bosscher, J S; ten Brink, B; Driessen, A J; Konings, W N

1993-05-01

Lactobacillus buchneri ST2A vigorously decarboxylates histidine to the biogenic amine histamine, which is excreted into the medium. Cells grown in the presence of histidine generate both a transmembrane pH gradient, inside alkaline, and an electrical potential (delta psi), inside negative, upon addition of histidine. Studies of the mechanism of histidine uptake and histamine excretion in membrane vesicles and proteoliposomes devoid of cytosolic histidine decarboxylase activity demonstrate that histidine uptake, histamine efflux, and histidine/histamine exchange are electrogenic processes. Histidine/histamine exchange is much faster than the unidirectional fluxes of these substrates, is inhibited by an inside-negative delta psi and is stimulated by an inside positive delta psi. These data suggest that the generation of metabolic energy from histidine decarboxylation results from an electrogenic histidine/histamine exchange and indirect proton extrusion due to the combined action of the decarboxylase and carrier-mediated exchange. The abundance of amino acid decarboxylation reactions among bacteria suggests that this mechanism of metabolic energy generation and/or pH regulation is widespread.

Cyclic aldimines as superior electrophiles for Cu-catalyzed decarboxylative Mannich reaction of β-ketoacids with a broad scope and high enantioselectivity.

Science.gov (United States)

Zhang, Heng-Xia; Nie, Jing; Cai, Hua; Ma, Jun-An

2014-05-02

A novel Cu-catalyzed enantioselective decarboxylative Mannich reaction of cyclic aldimines with β-ketoacids is described. The cyclic structure of these aldimines, in which the C═N bond is constrained in the Z geometry, appears to be important, allowing Mannich condensation to proceed in high yields with excellent enantioselectivities. A chiral chroman-4-amine was synthesized from the decarboxylative Mannich product in several steps without loss of enantioselectivity.

Mechanism and stem-cell activity of 5-carboxycytosine decarboxylation determined by isotope tracing.

Science.gov (United States)

Schiesser, Stefan; Hackner, Benjamin; Pfaffeneder, Toni; Müller, Markus; Hagemeier, Christian; Truss, Matthias; Carell, Thomas

2012-06-25

Eraserhead: Stem cells seem to erase epigenetic information by decarboxylation of the newly discovered epigenetic base 5-carboxycytosine (caC; see picture). This reaction is likely to involve a nucleophilic attack of the C5-C6 double bond. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Unusual differences in the reactivity of glutamic and aspartic acid in oxidative decarboxylation reactions

NARCIS (Netherlands)

But, Andrada; Wijst, van der Evie; Notre, le Jerome; Wever, Ron; Sanders, Johan P.M.; Bitter, Johannes H.; Scott, Elinor L.

2017-01-01

Amino acids are potential substrates to replace fossil feedstocks for the synthesis of nitriles via oxidative decarboxylation using vanadium chloroperoxidase (VCPO), H₂O₂ and bromide. Here the conversion of glutamic acid (Glu) and aspartic acid (Asp) was investigated. It was

Technoeconomic analysis of jet fuel production from hydrolysis, decarboxylation, and reforming of camelina oil

KAUST Repository

Natelson, Robert H.; Wang, Weicheng; Roberts, William L.; Zering, Kelly D.

2015-01-01

The commercial production of jet fuel from camelina oil via hydrolysis, decarboxylation, and reforming was simulated. The refinery was modeled as being close to the farms for reduced camelina transport cost. A refinery with annual nameplate capacity of 76,000 cubic meters hydrocarbons was modeled. Assuming average camelina production conditions and oil extraction modeling from the literature, the cost of oil was 0.31$kg-1. To accommodate one harvest per year, a refinery with 1 year oil storage capacity was designed, with the total refinery costing 283 million dollars in 2014 USD. Assuming co-products are sold at predicted values, the jet fuel break-even selling price was 0.80$kg-1. The model presents baseline technoeconomic data that can be used for more comprehensive financial and risk modeling of camelina jet fuel production. Decarboxylation was compared to the commercially proven hydrotreating process. The model illustrated the importance of refinery location relative to farms and hydrogen production site.

Technoeconomic analysis of jet fuel production from hydrolysis, decarboxylation, and reforming of camelina oil

KAUST Repository

Natelson, Robert H.

2015-04-01

The commercial production of jet fuel from camelina oil via hydrolysis, decarboxylation, and reforming was simulated. The refinery was modeled as being close to the farms for reduced camelina transport cost. A refinery with annual nameplate capacity of 76,000 cubic meters hydrocarbons was modeled. Assuming average camelina production conditions and oil extraction modeling from the literature, the cost of oil was 0.31$kg-1. To accommodate one harvest per year, a refinery with 1 year oil storage capacity was designed, with the total refinery costing 283 million dollars in 2014 USD. Assuming co-products are sold at predicted values, the jet fuel break-even selling price was 0.80$kg-1. The model presents baseline technoeconomic data that can be used for more comprehensive financial and risk modeling of camelina jet fuel production. Decarboxylation was compared to the commercially proven hydrotreating process. The model illustrated the importance of refinery location relative to farms and hydrogen production site.

Decarboxylation of oxalacetate to pyruvate by purified avian liver phosphoenolpyruvate carboxykinase

Energy Technology Data Exchange (ETDEWEB)

Noce, P S; Utter, M F

1975-01-01

Phosphoenolpyruvate carboxykinase, which has been isolated from chicken liver mitochondria in essentially homogenous form, carries out the irreversible decarboxylation of oxalacetate to pyruvate in the presence of catalytic amounts of GDP or IDP, as well as the reversible decarboxylation of oxalacetate to phosphoenolpyruvate in the presence of substrate amounts of GTP or ITP. The pyruvate- and phosphoenolpyruvate-forming reactions are similar in their nucleoside specificity and appear to be carried out by the same protein. However, the two activities vary markedly in their response to added metal ions and sulfhydryl reagents. Phosphoenolpyruvate formation is completely dependent on the presence of a divalent metal ion, with Mn/sup 2 +/ the most effective species. This reaction is also stimulated by sulfhydryl reagents such as 2-mercaptoethanol. In contrast, the pyruvate-forming reaction is strongly inhibited by divalent metal ions, including Mn/sup 2 +/, and also by moderate concentrations of sulfhydryl reagents. These observations and the demonstration that pyruvate kinase-like activity is very low or absent make it unlikely that pyruvate formation proceeds via phosphoenolpyruvate as an intermediate. Although the pyruvate-forming reaction is inhibited by added metal ions, the reaction is also inhibited by metal-chelating agents such as 8-hydroxyquinoline and o-phenanthroline, suggesting that the reaction is dependent on the presence of a metal ion. It has not been possible, however, to demonstrate that the enzyme is a metalloprotein.

Decarboxylative Aminomethylation of Aryl- and Vinylsulfonates through Combined Nickel- and Photoredox-Catalyzed Cross-Coupling

KAUST Repository

Fan, Lulu

2016-09-23

A mild approach for the decarboxylative aminomethylation of aryl sulfonates by the combination of photoredox and nickel catalysis through C−O bond cleavage is described for the first time. A wide range of aryl triflates as well as aryl mesylates, tosylates and alkenyl triflates afford the corresponding products in good to excellent yields.

Decarboxylative Aminomethylation of Aryl- and Vinylsulfonates through Combined Nickel- and Photoredox-Catalyzed Cross-Coupling

KAUST Repository

Fan, Lulu; Jia, Jiaqi; Hou, Hong; Lefebvre, Quentin; Rueping, Magnus

2016-01-01

A mild approach for the decarboxylative aminomethylation of aryl sulfonates by the combination of photoredox and nickel catalysis through C−O bond cleavage is described for the first time. A wide range of aryl triflates as well as aryl mesylates, tosylates and alkenyl triflates afford the corresponding products in good to excellent yields.

Hydrocarbon fuels from gas phase decarboxylation of hydrolyzed free fatty acid

KAUST Repository

Wang, Weicheng

2012-01-01

Gas phase decarboxylation of hydrolyzed free fatty acid (FFA) from canola oil has beeninvestigated in two fix-bed reactors by changing reaction parameters such as temperatures,FFA feed rates, and H 2-to-FFA molar ratios. FFA, which contains mostly C 18 aswell as a few C 16, C 20, C 22, and C 24 FFA, was fed into the boiling zone, evaporated, carriedby hydrogen flow at the rate of 0.5-20 ml/min, and reacted with the 5% Pd/C catalystin the reactor. Reactions were conducted atmospherically at 380-450 °C and the products,qualified and quantified through gas chromatography-flame ionization detector(GC-FID), showed mostly n-heptadecane and a few portion of n-C 15, n-C 19, n-C 21, n-C 23 as well as some cracking species. Results showed that FFA conversion increased withincreasing reaction temperatures but decreased with increasing FFA feed rates and H 2-to-FFA molar ratios. The reaction rates were found to decrease with higher temperatureand increase with higher H 2 flow rates. Highly selective heptadecane was achieved byapplying higher temperatures and higher H 2-to-FFA molar ratios. From the results, ascatalyst loading and FFA feed rate were fixed, an optimal reaction temperature of 415 °C as well as H 2-to-FFA molar ratio of 4.16 were presented. These results provided goodbasis for studying the kinetics of decarboxylation process. © 2012 American Society of Mechanical Engineers.

Weissella halotolerans W22 combines arginine deiminase and ornithine decarboxylation pathways and converts arginine to putrescine

NARCIS (Netherlands)

Pereira, C. I.; San Romao, M. V.; Lolkema, J. S.; Barreto Crespo, M. T.; Baretto Crespo, M.

2009-01-01

Aims: To demonstrate that the meat food strain Weissella halotolerans combines an ornithine decarboxylation pathway and an arginine deiminase (ADI) pathway and is able to produce putrescine, a biogenic amine. Evidence is shown that these two pathways produce a proton motive force (PMF). Methods and

Clarification on the decarboxylation mechanism in KasA based on the protonation state of key residues in the acyl-enzyme state.

Science.gov (United States)

Lee, Wook; Engels, Bernd

2013-07-11

The β-ketoacyl ACP synthase I (KasA) is a promising drug target because it is essential for the survival of Mycobacterium tuberculosis , a causative agent of tuberculosis. It catalyzes a condensation reaction that comprises three steps. The resulting elongated acyl chains are subsequently needed for the cell wall construction. While the mechanism of the first step (acylation of Cys171 in the active site) is straightforward already, the second step (decarboxylation of malonyl substrate) has been controversial due to the difficulty in determining the correct protonation states of the involved residues (His311, His345, Lys340, Glu354). Available experimental data suggest three possible mechanisms which differ considerably. They are not consistent with each other because these studies could not be performed for KasA at the beginning of decarboxylation step (acyl-enzyme state of KasA). Instead, different mutants had to be used which are expected to resemble this situation. In this first computational study about this topic, we use the free energy perturbation (FEP) method to compute the relevant pKa values in the acyl-enzyme state of KasA and use molecular dynamics (MD) simulations to rationalize the results. Subsequent density functional theory (DFT)-based quantum mechanical/molecular mechanical (QM/MM) MD simulations and umbrella samplings have been used to disentangle the close relationships between the protonation states of the involved residues. By these simulations, we can address the preferred protonation states and roles of the residues involved in decarboxylation reaction, thereby suggesting the possible mechanism for the decarboxylation step.

Visible-Light Photocatalytic Decarboxylation of α,β-Unsaturated Carboxylic Acids: Facile Access to Stereoselective Difluoromethylated Styrenes in Batch and Flow

Science.gov (United States)

2017-01-01

The development of synthetic methodologies which provide access to both stereoisomers of α,β-disubstituted olefins is a challenging undertaking. Herein, we describe the development of an operationally simple and stereoselective synthesis of difluoromethylated styrenes via a visible-light photocatalytic decarboxylation strategy using fac-Ir(ppy)3 as the photocatalyst. Meta- and para-substituted cinnamic acids provide the expected E-isomer. In contrast, ortho-substituted cinnamic acids yield selectively the less stable Z-product, whereas the E-isomer can be obtained via continuous-flow processing through accurate control of the reaction time. Furthermore, our protocol is amenable to the decarboxylative difluoromethylation of aryl propiolic acids. PMID:29109904

Solvent effects and secondary isotope effects for probing diradical character in the thermal decarboxylation of β-peroxylactones

International Nuclear Information System (INIS)

Adam, W.; Cueto, O.; Guedes, L.N.; Rodriguez, L.O.

1978-01-01

The lack of solvent effects in the activation parameters and product distribution and the lack of secondary deuterium isotope effects at the α-carbon and β-alkyl migrant substantiates that the thermal decarboxylation of β-peroxy lactones proceeds via a 1,5-diradical

Quantum Chemical Modeling of Enzymatic Reactions: The Case of Decarboxylation.

Science.gov (United States)

Liao, Rong-Zhen; Yu, Jian-Guo; Himo, Fahmi

2011-05-10

We present a systematic study of the decarboxylation step of the enzyme aspartate decarboxylase with the purpose of assessing the quantum chemical cluster approach for modeling this important class of decarboxylase enzymes. Active site models ranging in size from 27 to 220 atoms are designed, and the barrier and reaction energy of this step are evaluated. To model the enzyme surrounding, homogeneous polarizable medium techniques are used with several dielectric constants. The main conclusion is that when the active site model reaches a certain size, the solvation effects from the surroundings saturate. Similar results have previously been obtained from systematic studies of other classes of enzymes, suggesting that they are of a quite general nature.

PhI(OAc)2-mediated one-pot oxidative decarboxylation and aromatization of tetrahydro-β-carbolines: synthesis of norharmane, harmane, eudistomin U and eudistomin I.

Science.gov (United States)

Kamal, Ahmed; Tangella, Yellaiah; Manasa, Kesari Lakshmi; Sathish, Manda; Srinivasulu, Vunnam; Chetna, Jadala; Alarifi, Abdullah

2015-08-28

Iodobenzene diacetate was employed as a mild and efficient reagent for one-pot oxidative decarboxylation of tetrahydro-β-carboline acids and dehydrogenation of tetrahydro-β-carbolines to access the corresponding aromatic β-carbolines. To the best of our knowledge this is the first synthesis of β-carbolines via a one-pot oxidative decarboxylation at ambient temperature. The utility of this protocol has been demonstrated in the synthesis of β-carboline alkaloids norharmane (2o), harmane (2p), eudistomin U (9) and eudistomin I (12).

Carbon-13 and oxygen-18 isotope effects in the decarboxylation of nicotinic acid of natural isotopic composition

International Nuclear Information System (INIS)

Zielinski, M.; Zielinska, A.; Papiernik-Zielinska, H.; McKenzie, J.A.; Bernasconi, S.; Paul, H.

1998-01-01

Carbon-13 and oxygen-18 isotope effects in the decarboxylation of nicotinic acid of natural isotopic composition above and below its melting temperature have been studied and compared with the primary (PKIE) and secondary kinetic isotope effects (SKIE) of 13 C and 18 O, respectively, in the decarboxylation of other heterocyclic acids. The temperature dependence of the secondary oxygen-18 isotope effects is negative in the total 221-255 deg C temperature interval investigated initially. The 13 C KIE measured above melting point of N.A. (temperature interval 235-270 deg C) are located in the range 1.007-1.009. Below melting point of nicotinic acid the 13 C KIE are larger and reveal the negative temperature dependence ( 13 C KIE decreases with decreasing the reaction temperature from 1.013/at 230 deg C to 1.0114/at 221 deg C). A discussion of the above isotopic results is presented. (author)

The mechanism of the tyrosine transporter TyrP supports a proton motive tyrosine decarboxylation pathway in Lactobacillus brevis

NARCIS (Netherlands)

Wolken, WAM; Lucas, PM; Lonvaud-Funel, A; Lolkema, JS; Wolken, Wout A.M.; Lucas, Patrick M.

The tyrosine decarboxylase operon of Lactobacillus brevis IOEB9809 contains, adjacent to the tyrosine decarboxylase gene, a gene for TyrP, a putative tyrosine transporter. The two genes potentially form a proton motive tyrosine decarboxylation pathway. The putative tyrosine transporter gene of L.

Formation of Ketenimines via the Palladium-Catalyzed Decarboxylative π-Allylic Rearrangement of N-Alloc Ynamides.

Science.gov (United States)

Alexander, Juliana R; Cook, Matthew J

2017-11-03

A new approach for the formation of ketenimines via a decarboxylative allylic rearrangement pathway that does not require strong stabilizing or protecting groups has been developed. The products can be readily hydrolyzed into their corresponding secondary amides or reacted with sulfur ylides to perform an additional [2,3]-Wittig process. Mechanistic studies suggest an outer-sphere process in which reductive alkylation is rate-limiting.

Nano-catalysts for upgrading bio-oil: Catalytic decarboxylation and hydrodeoxygenation

Science.gov (United States)

Uemura, Yoshimitsu; Tran, Nga T. T.; Naqvi, Salman Raza; Nishiyama, Norikazu

2017-09-01

Bio-oil is a mixture of oxygenated chemicals produced by fast pyrolysis of lignocellulose, and has attracted much attention recently because the raw material is renewable. Primarily, bio-oil can be used as a replacement of heavy oil. But it is not highly recommended due to bio-oil's inferior properties: high acidity and short shelf life. Upgrading of bio-oil is therefore one of the important technologies nowadays, and is categorized into the two: (A) decrarboxylation/decarbonylation by solid acid catalysts and (B) hydrodeoxygenation (HDO) by metallic catalysts. In our research group, decarboxylation of bio-oil by zeolites and HDO of guaiacol (a model compound of bio-oil) have been investigated. In this paper, recent developments of these upgrading reactions in our research group will be introduced.

Palladium-Catalyzed Decarboxylative γ-Olefination of 2,5-Cyclohexadiene-1-carboxylic Acid Derivatives with Vinyl Halides.

Science.gov (United States)

Chang, Chi-Hao; Chou, Chih-Ming

2018-04-06

This study explores a Pd-catalyzed decarboxylative Heck-type Csp 3 -Csp 2 coupling reaction of 2,5-cyclohexadiene-1-carboxylic acid derivatives with vinyl halides to provide γ-olefination products. The olefinated 1,3-cyclohexadienes can be further oxidized to produce meta-alkylated stilbene derivatives. Additionally, the conjugated diene products can also undergo a Diels-Alder reaction to produce a bicyclo[2.2.2]octadiene framework.

Synthesis of bio-based methacrylic acid by decarboxylation of itaconic acid and citric acid catalyzed by solid transition-metal catalysts.

Science.gov (United States)

Le Nôtre, Jérôme; Witte-van Dijk, Susan C M; van Haveren, Jacco; Scott, Elinor L; Sanders, Johan P M

2014-09-01

Methacrylic acid, an important monomer for the plastics industry, was obtained in high selectivity (up to 84%) by the decarboxylation of itaconic acid using heterogeneous catalysts based on Pd, Pt and Ru. The reaction takes place in water at 200-250 °C without any external added pressure, conditions significantly milder than those described previously for the same conversion with better yield and selectivity. A comprehensive study of the reaction parameters has been performed, and the isolation of methacrylic acid was achieved in 50% yield. The decarboxylation procedure is also applicable to citric acid, a more widely available bio-based feedstock, and leads to the production of methacrylic acid in one pot in 41% selectivity. Aconitic acid, the intermediate compound in the pathway from citric acid to itaconic acid was also used successfully as a substrate. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Decarboxylation of indole-3-acetic acid and inhibition of growth in Avena sativa seedlings by plant-derived photosensitizers

Energy Technology Data Exchange (ETDEWEB)

Brennan, T.M. [Dickinson Coll., Carlisle, PA (United States). Dept. of Biology

1996-12-01

A number of plant phototoxins, when supplemented with UVA (320-400 nm) radiation, are capable of sensitizing the decomposition of indole-3-acetic acid (IAA), as measured by release of {sup 14}CO{sub 2} from carboxyl-labeled IAA. Alpha-terthienyl ({alpha}T) and harmine caused significant rates of IAA decarboxylation at concentrations as low as 1 nM and were approximately 80% as effective as riboflavin and flavin mononucleotide. Partial inhibition by sodium azide indicates that the {alpha}T-induced decarboxylation of IAA is predominately, but not entirely, a type II reaction mediated by singlet oxygen. Based on changes in UV absorption spectra, it appears that the hormones gibberellic acid, abscisic acid and 6-benzylaminopurine (a cytokinin) are less susceptible to photosensitized decomposition than is IAA. Alpha-terthienyl plus UVA also inhibited elongation growth and reduced endogenous IAA levels in Avena sativa L. coleoptile sections and promoted senescence in intact Avena seedlings. These results confirm the alelopathic potential of plant photosensitizers such as {alpha}T and indicate that the phytohormone IAA may represent an additional target for the action of photosensitizers. (Author).

High-Throughput Screening of the Asymmetric Decarboxylative Alkylation Reaction of Enolate-Stabilized Enol Carbonates

KAUST Repository

Stoltz, Brian

2010-06-14

The use of high-throughput screening allowed for the optimization of reaction conditions for the palladium-catalyzed asymmetric decarboxylative alkylation reaction of enolate-stabilized enol carbonates. Changing to a non-polar reaction solvent and to an electron-deficient PHOX derivative as ligand from our standard reaction conditions improved the enantioselectivity for the alkylation of a ketal-protected,1,3-diketone-derived enol carbonate from 28% ee to 84% ee. Similar improvements in enantioselectivity were seen for a β-keto-ester derived- and an α-phenyl cyclohexanone-derived enol carbonate.

High-Throughput Screening of the Asymmetric Decarboxylative Alkylation Reaction of Enolate-Stabilized Enol Carbonates

KAUST Repository

Stoltz, Brian; McDougal, Nolan; Virgil, Scott

2010-01-01

The use of high-throughput screening allowed for the optimization of reaction conditions for the palladium-catalyzed asymmetric decarboxylative alkylation reaction of enolate-stabilized enol carbonates. Changing to a non-polar reaction solvent and to an electron-deficient PHOX derivative as ligand from our standard reaction conditions improved the enantioselectivity for the alkylation of a ketal-protected,1,3-diketone-derived enol carbonate from 28% ee to 84% ee. Similar improvements in enantioselectivity were seen for a β-keto-ester derived- and an α-phenyl cyclohexanone-derived enol carbonate.

Inhibition of mammalian nitric oxide synthases by agmatine, an endogenous polyamine formed by decarboxylation of arginine.

OpenAIRE

Galea, E; Regunathan, S; Eliopoulos, V; Feinstein, D L; Reis, D J

1996-01-01

Agmatine, decarboxylated arginine, is a metabolic product of mammalian cells. Considering the close structural similarity between L-arginine and agmatine, we investigated the interaction of agmatine and nitric oxide synthases (NOSs), which use L-arginine to generate nitric oxide (NO) and citrulline. Brain, macrophages and endothelial cells were respectively used as sources for NOS isoforms I, II and III. Enzyme activity was measured by the production of nitrites or L-citrulline. Agmatine was ...

Synthesis of bio-based methacrylic acid by decarboxylation of itaconic acid and citric acid catalyzed by solid transition-metal catalysts

NARCIS (Netherlands)

Notre, le J.E.L.; Witte-van Dijk, S.C.M.; Haveren, van J.; Scott, E.L.; Sanders, J.P.M.

2014-01-01

Methacrylic acid, an important monomer for the plastics industry, was obtained in high selectivity (up to 84%) by the decarboxylation of itaconic acid using heterogeneous catalysts based on Pd, Pt and Ru. The reaction takes place in water at 200–2508C without any external added pressure, conditions

Generation of a Proton Motive Force by Histidine Decarboxylation and Electrogenic Histidine/Histamine Antiport in Lactobacillus buchneri

OpenAIRE

Molenaar, Douwe; Bosscher, Jaap S.; Brink, Bart ten; Driessen, Arnold J.M.; Konings, Wil N.

1993-01-01

Lactobacillus buchneri ST2A vigorously decarboxylates histidine to the biogenic amine histamine, which is excreted into the medium. Cells grown in the presence of histidine generate both a transmembrane pH gradient, inside alkaline, and an electrical potential (delta psi), inside negative, upon addition of histidine. Studies of the mechanism of histidine uptake and histamine excretion in membrane vesicles and proteoliposomes devoid of cytosolic histidine decarboxylase activity demonstrate tha...

Domino-Fluorination-Protodefluorination Enables Decarboxylative Cross-Coupling of α-Oxocarboxylic Acids with Styrene via Photoredox Catalysis.

Science.gov (United States)

Zhang, Muliang; Xi, Junwei; Ruzi, Rehanguli; Li, Nan; Wu, Zhongkai; Li, Weipeng; Zhu, Chengjian

2017-09-15

Domino-fluorination-protodefluorination decarboxylative cross-coupling of α-keto acids with styrene has been developed via photoredox catalysis. The critical part of this strategy is the formation of the carbon-fluorine (C-F) bond by the capture of a carbon-centered radical intermediate, which will overcome side reactions during the styrene radical functionalization process. Experimental studies have provided evidence indicating a domino-fluorination-protodefluorination pathway with α-keto acid initiating the photoredox cycle. The present catalytic protocol also affords a novel approach for the construction of α,β-unsaturated ketones under mild conditions.

Decarboxylation of furfural on Pd(111): Ab initio molecular dynamics simulations

Science.gov (United States)

Xue, Wenhua; Dang, Hongli; Shields, Darwin; Liu, Yingdi; Jentoft, Friederike; Resasco, Daniel; Wang, Sanwu

2013-03-01

Furfural conversion over metal catalysts plays an important role in the studies of biomass-derived feedstocks. We report ab initio molecular dynamics simulations for the decarboxylation process of furfural on the palladium surface at finite temperatures. We observed and analyzed the atomic-scale dynamics of furfural on the Pd(111) surface and the fluctuations of the bondlengths between the atoms in furfural. We found that the dominant bonding structure is the parallel structure in which the furfural plane, while slightly distorted, is parallel to the Pd surface. Analysis of the bondlength fluctuations indicates that the C-H bond is the aldehyde group of a furfural molecule is likely to be broken first, while the C =O bond has a tendency to be isolated as CO. Our results show that the reaction of decarbonylation dominates, consistent with the experimental measurements. Supported by DOE (DE-SC0004600). Simulations and calculations were performed on XSEDE's and NERSC's supercomputers.

Decarboxylation of Malate in the Crassulacean Acid Metabolism Plant Bryophyllum (Kalanchoe) fedtschenkoi (Role of NAD-Malic Enzyme).

Science.gov (United States)

Cook, R. M.; Lindsay, J. G.; Wilkins, M. B.; Nimmo, H. G.

1995-01-01

The role of NAD-malic enzyme (NAD-ME) in the Crassulacean acid metabolism plant Bryophyllum (Kalanchoe) fedtschenkoi was investigated using preparations of intact and solubilized mitochondria from fully expanded leaves. Intact, coupled mitochondria isolated during the day or night did not differ in their ability to take up [14C]malic acid from the surrounding medium or to respire using malate or succinate as substrate. However, intact mitochondria isolated from plants during the day decarboxylated added malate to pyruvate significantly faster than mitochondria isolated from plants at night. NAD-ME activity in solubilized mitochondrial extracts showed hysteretic kinetics and was stimulated by a number of activators, including acetyl-coenzyme A, fructose-1,6-bisphosphate, and sulfate ions. In the absence of these effectors, reaction progress curves were nonlinear, with a pronounced acceleration phase. The lag period before a steady-state rate was reached in assays of mitochondrial extracts decreased during the photoperiod and increased slowly during the period of darkness. However, these changes in the kinetic properties of the enzyme could not account for the changes in the rate of decarboxylation of malate by intact mitochondria. Gel-filtration experiments showed that mitochondrial extracts contained three forms of NAD-ME with different molecular weights. The relative proportions of the three forms varied somewhat throughout the light/dark cycle, but this did not account for the changes in the kinetics behavior of the enzyme during the diurnal cycle. PMID:12228671

Oxidative decarboxylation of glycolic and phenylacetic acids with cerium(4) catalyzed by silver ions in the sulfuric acid media

International Nuclear Information System (INIS)

Venkatesvar Rao, G.; Nagardzhun Rao, Ch.; Sajprakash, P.K.

1981-01-01

Oxidative decarboxylation of glycolic and phenylacetic acids by cerium (4) in the presence of Ag + ions is studied. The Ce(4) order equals 1, glycolic acid order in the absence of a catalyst also equals 1 and is fractional (0.5) for a catalytic reaction. The phenylacetic acid order is fractional (0.75). The Ag + ion reaction order is fractional and constitutes 0.32 for glycolic and 0.36 for phenylacetic acids. The reaction mechanism is proposed [ru

Terminal Alkene Formation by the Thioesterase of Curacin A Biosynthesis: Structure of a Decarboxylating Thioesterase

Energy Technology Data Exchange (ETDEWEB)

Gehret, Jennifer J.; Gu, Liangcai; Gerwick, William H.; Wipf, Peter; Sherman, David H.; Smith, Janet L. (Pitt); (Michigan); (UCSD)

2011-11-07

Curacin A is a polyketide synthase (PKS)-non-ribosomal peptide synthetase-derived natural product with potent anticancer properties generated by the marine cyanobacterium Lyngbya majuscula. Type I modular PKS assembly lines typically employ a thioesterase (TE) domain to off-load carboxylic acid or macrolactone products from an adjacent acyl carrier protein (ACP) domain. In a striking departure from this scheme the curacin A PKS employs tandem sulfotransferase and TE domains to form a terminal alkene moiety. Sulfotransferase sulfonation of {beta}-hydroxy-acyl-ACP is followed by TE hydrolysis, decarboxylation, and sulfate elimination (Gu, L., Wang, B., Kulkarni, A., Gehret, J. J., Lloyd, K. R., Gerwick, L., Gerwick, W. H., Wipf, P., Hakansson, K., Smith, J. L., and Sherman, D. H. (2009) J. Am. Chem. Soc. 131, 16033-16035). With low sequence identity to other PKS TEs (<15%), the curacin TE represents a new thioesterase subfamily. The 1.7-{angstrom} curacin TE crystal structure reveals how the familiar {alpha}/{beta}-hydrolase architecture is adapted to specificity for {beta}-sulfated substrates. A Ser-His-Glu catalytic triad is centered in an open active site cleft between the core domain and a lid subdomain. Unlike TEs from other PKSs, the lid is fixed in an open conformation on one side by dimer contacts of a protruding helix and on the other side by an arginine anchor from the lid into the core. Adjacent to the catalytic triad, another arginine residue is positioned to recognize the substrate {beta}-sulfate group. The essential features of the curacin TE are conserved in sequences of five other putative bacterial ACP-ST-TE tridomains. Formation of a sulfate leaving group as a biosynthetic strategy to facilitate acyl chain decarboxylation is of potential value as a route to hydrocarbon biofuels.

Enantioselective construction of quaternary N-heterocycles by palladium-catalysed decarboxylative allylic alkylation of lactams

KAUST Repository

Behenna, Douglas C.

2011-12-18

The enantioselective synthesis of nitrogen-containing heterocycles (N-heterocycles) represents a substantial chemical research effort and resonates across numerous disciplines, including the total synthesis of natural products and medicinal chemistry. In this Article, we describe the highly enantioselective palladium-catalysed decarboxylative allylic alkylation of readily available lactams to form 3,3-disubstituted pyrrolidinones, piperidinones, caprolactams and structurally related lactams. Given the prevalence of quaternary N-heterocycles in biologically active alkaloids and pharmaceutical agents, we envisage that our method will provide a synthetic entry into the de novo asymmetric synthesis of such structures. As an entry for these investigations we demonstrate how the described catalysis affords enantiopure quaternary lactams that intercept synthetic intermediates previously used in the synthesis of the Aspidosperma alkaloids quebrachamine and rhazinilam, but that were previously only available by chiral auxiliary approaches or as racemic mixtures. © 2012 Macmillan Publishers Limited. All rights reserved.

Rhodium(III)-Catalyzed ortho-Alkylation of Phenoxy Substrates with Diazo Compounds via C-H Activation: A Case of Decarboxylative Pyrimidine/Pyridine Migratory Cyclization Rather than Removal of Pyrimidine/Pyridine Directing Group.

Science.gov (United States)

Ravi, Manjula; Allu, Srinivasarao; Swamy, K C Kumara

2017-03-03

An efficient Rh(III)-catalyzed ortho-alkylation of phenoxy substrates with diazo compounds has been achieved for the first time using pyrimidine or pyridine as the directing group. Furthermore, bis-alkylation has also been achieved using para-substituted phenoxypyrimidine and 3 mol equiv of the diazo ester. The ortho-alkylated derivatives of phenoxy products possessing the ester functionality undergo decarboxylative pyrimidine/pyridine migratory cyclization (rather than deprotection of pyrimidine/pyridine group) using 20% NaOEt in EtOH affording a novel class of 3-(pyrimidin-2(1H)-ylidene)benzofuran-2(3H)-ones and 6-methyl-3-(pyridin-2(1H)-ylidene)benzofuran-2(3H)-one. The ortho-alkylated phenoxypyridine possessing ester functionality also undergoes decarboxylative pyridine migratory cyclization using MeOTf/NaOMe in toluene providing 6-methyl-3-(1-methylpyridin-2(1H)-ylidene)benzofuran-2(3H)-one.

Spectral and Mechanistic Investigation of Oxidative Decarboxylation of Phenylsulfinylacetic Acid by Cr(VI)

International Nuclear Information System (INIS)

Subramaniam, Perumal; Selvi, Natesan Thamil; Devi, Soundarapandian Sugirtha

2014-01-01

The oxidative decarboxylation of phenylsulfinylacetic acid (PSAA) by Cr(VI) in 20% acetonitrile . 80% water (v/v) medium follows overall second order kinetics, first order each with respect to [PSAA] and [Cr(VI)] at constant [H + ] and ionic strength. The reaction is acid catalysed, the order with respect to [H + ] is unity and the active oxidizing species is found to be HCrO 3 + . The reaction mechanism involves the rate determining nucleophilic attack of sulfur atom of PSAA on chromium of HCrO 3 + forming a sulfonium ion intermediate. The intermediate then undergoes α,β-cleavage leading to the liberation of CO 2 . The product of the reaction is found to be methyl phenyl sulfone. The operation of substituent effect shows that PSAA containing electron-releasing groups in the meta- and para-positions accelerate the reaction rate while electron withdrawing groups retard the rate. An excellent correlation is found to exist between log k 2 and Hammett σ constants with a negative value of reaction constant. The ρ value decreases with increase in temperature evidencing the high reactivity and low selectivity in the case of substituted PSAAs

Analysis of cannabinoids in commercial hemp seed oil and decarboxylation kinetics studies of cannabidiolic acid (CBDA).

Science.gov (United States)

Citti, Cinzia; Pacchetti, Barbara; Vandelli, Maria Angela; Forni, Flavio; Cannazza, Giuseppe

2018-02-05

Hemp seed oil from Cannabis sativa L. is a very rich natural source of important nutrients, not only polyunsaturated fatty acids and proteins, but also terpenes and cannabinoids, which contribute to the overall beneficial effects of the oil. Hence, it is important to have an analytical method for the determination of these components in commercial samples. At the same time, it is also important to assess the safety of the product in terms of amount of any psychoactive cannabinoid present therein. This work presents the development and validation of a highly sensitive, selective and rapid HPLC-UV method for the qualitative and quantitative determination of the main cannabinoids, namely cannabidiolic acid (CBDA), tetrahydrocannabinolic acid (THCA), cannabidiol (CBD), tetrahydrocannabinol (THC), cannabinol (CBN), cannabigerol (CBG) and cannabidivarin (CBDV), present in 13 commercial hemp seed oils. Moreover, since decomposition of cannabinoid acids generally occurs with light, air and heat, decarboxylation studies of the most abundant acid (CBDA) were carried out in both open and closed reactor and the kinetics parameters were evaluated at different temperatures in order to evaluate the stability of hemp seed oil in different storage conditions. Copyright © 2017 Elsevier B.V. All rights reserved.

The differences between NAD-ME and NADP-ME subtypes of C4 photosynthesis: more than decarboxylating enzymes

Directory of Open Access Journals (Sweden)

Xiaolan Rao

2016-10-01

Full Text Available As an adaptation to changing climatic conditions that caused high rates of photorespiration, C4 plants have evolved to display higher photosynthetic efficiency than C3 plants under elevated temperature, high light intensities and drought. The C4 plants independently evolved more than 60 times in 19 families of angiosperms to establish similar but not uniform C4 mechanisms to concentrate CO2 around the carboxylating enzyme Rubisco. C4 photosynthesis is divided into at least two basic biochemical subtypes based on the primary decarboxylating enzymes, NAD-dependent malic enzyme (NAD-ME and NADP-dependent malic enzyme (NADP-ME. The multiple polygenetic origins of these subtypes raise questions about the association of C4 variation between biochemical subtypes and diverse lineages. This review addresses the differences in evolutionary scenario, leaf anatomy, and especially C4 metabolic flow, C4 transporters and cell-specific function deduced from recently reported cell-specific transcriptomic, proteomic and metabolic analyses of NAD-ME and NADP-ME subtypes. Current omic analysis has revealed the extent to which component abundances differ between the two biochemical subtypes, leading to a better understanding of C4 photosynthetic mechanisms in NAD-ME and NADP-ME subtypes.

Effects of adrenergic agents on intracellular ca(2+) homeostasis and metabolism of glucose in astrocytes with an emphasis on pyruvate carboxylation, oxidative decarboxylation and recycling

DEFF Research Database (Denmark)

Obel, Linea Lykke Frimodt; Andersen, Karen M H; Bak, Lasse Kristoffer

2012-01-01

and oxidative decarboxylation in astrocytic glucose metabolism. Importantly, pyruvate carboxylation was best visualized at 10 min of incubation. The abundance and pattern of labeling in lactate and alanine indicated not only an extensive activity of malic enzyme (initial step for pyruvate recycling) but also...... a high degree of compartmentalization of the pyruvate pool. Stimulating with 1 µM NE had no effect on labeling patterns and glycogen metabolism, whereas 100 µM NE increased glutamate labeling and decreased labeling in alanine, the latter supposedly due to dilution from degradation of non-labeled glycogen....... It is suggested that further experiments uncovering the correlation between adrenergic and glutamatergic pathways should be performed in order to gain further insight into the role of astrocytes in brain function and dysfunction, the latter including excitotoxicity....

Catalytic effect of different reactor materials under subcritical water conditions: decarboxylation of cysteic acid into taurine

Science.gov (United States)

Faisal, M.

2018-03-01

In order to understand the influence of reactor materials on the catalytic effect for a particular reaction, the decomposition of cysteic acid from Ni/Fe-based alloy reactors under subcritical water conditions was examined. Experiments were carried out in three batch reactors made of Inconel 625, Hastelloy C-22 and SUS 316 over temperatures of 200 to 300 °C. The highest amount of eluted metals was found for SUS 316. The results demonstrated that reactor materials contribute to the resulting product. Under the tested conditions, cysteic acid decomposes readily with SUS 316. However, the Ni-based materials (Inconel 625 and Hastelloy C-22) show better resistance to metal elution. It was found that among the materials used in this work, SUS 316 gave the highest reaction rate constant of 0.1934 s‑1. The same results were obtained at temperatures of 260 and 300 °C. Investigation of the Arrhenius activation energy revealed that the highest activation energy was for Hastelloy C-22 (109 kJ/mol), followed by Inconel 625 (90 kJ/mol) and SUS 316 (70 kJ/mol). The decomposition rate of cysteic acid was found to follow the results for the trend of the eluted metals. Therefore, it can be concluded that the decomposition of cysteic acid was catalyzed by the elution of heavy metals from the surface of the reactor. The highest amount of taurine from the decarboxylation of cysteic acid was obtained from SUS 316.

Reductive decarboxylation of bicyclic prolinic systems: a new approach to the enantioselective synthesis of the Geissman-Waiss lactone. X-ray structure determination of a key lactone intermediate

Directory of Open Access Journals (Sweden)

Ambrósio João Carlos L.

2003-01-01

Full Text Available Two concise and enantioselective syntheses of the necine base precursors (1R,5R-N-Cbz and N-Boc-2-oxa-6-azabicyclo[3.3.0]octan-3-ones (Geissman-Waiss lactones were carried out from two enantiomerically pure endocyclic five-membered enecarbamates with overall yields of 23% and 26%, respectively. The synthetic strategy made use of a highly effective and stereoselective [2+2]cycloaddition of enantiomerically pure endocyclic enecarbamates with dichloroketene, as well as an efficient decarboxylation step of a bicyclic alpha-amino acid employing Boger's acyl selenide protocol employing tributyltin hydride. Interesting aspects concerning the regiochemical outcome of Baeyer-Villiger oxidations of bicyclic cyclobutanones are also reported, in which the usual stereoelectronic bias of Baeyer-Villiger oxidation seems to be counterbalanced by steric effects on the putative Criegee intermediate.

De Novo Biosynthesis of Glutarate via α-Keto Acid Carbon Chain Extension and Decarboxylation Pathway in Escherichia coli.

Science.gov (United States)

Wang, Jian; Wu, Yifei; Sun, Xinxiao; Yuan, Qipeng; Yan, Yajun

2017-10-20

Microbial based bioplastics are promising alternatives to petroleum based synthetic plastics due to their renewability and economic feasibility. Glutarate is one of the most potential building blocks for bioplastics. The recent biosynthetic routes for glutarate were mostly based on the l-lysine degradation pathway from Pseudomonas putida that required lysine either by feeding or lysine overproduction via genetic manipulations. Herein, we established a novel glutarate biosynthetic pathway by incorporation of a "+1" carbon chain extension pathway from α-ketoglutarate (α-KG) in combination with α-keto acid decarboxylation pathway in Escherichia coli. Introduction of homocitrate synthase (HCS), homoaconitase (HA) and homoisocitrate dehydrogenase (HICDH) from Saccharomyces cerevisiae into E. coli enabled "+1" carbon extension from α-KG to α-ketoadipate (α-KA), which was subsequently converted into glutarate by a promiscuous α-keto acid decarboxylase (KivD) and a succinate semialdehyde dehydrogenase (GabD). The recombinant E. coli coexpressing all five genes produced 0.3 g/L glutarate from glucose. To further improve the titers, α-KG was rechanneled into carbon chain extension pathway via the clustered regularly interspersed palindromic repeats system mediated interference (CRISPRi) of essential genes sucA and sucB in tricarboxylic acid (TCA) cycle. The final strain could produce 0.42 g/L glutarate, which was increased by 40% compared with the parental strain.

Practical synthesis of aryl-2-methyl-3-butyn-2-ols from aryl bromides via conventional and decarboxylative copper-free Sonogashira coupling reactions

Directory of Open Access Journals (Sweden)

Andrea Caporale

2014-02-01

Full Text Available Two efficient protocols for the palladium-catalyzed synthesis of aryl-2-methyl-3-butyn-2-ols from aryl bromides in the absence of copper were developed. A simple catalytic system consisting of Pd(OAc2 and P(p-tol3 using DBU as the base and THF as the solvent was found to be highly effective for the coupling reaction of 2-methyl-3-butyn-2-ol (4 with a wide range of aryl bromides in good to excellent yields. Analogously, the synthesis of aryl-2-methyl-3-butyn-2-ols was performed also through the decarboxylative coupling reaction of 4-hydroxy-4-methyl-2-pentynoic acid with aryl bromides, using a catalyst containing Pd(OAc2 in combination with SPhos or XPhos in the presence of tetra-n-butylammonium fluoride (TBAF as the base and THF as the solvent. Therefore, new efficient approaches to the synthesis of terminal acetylenes from widely available aryl bromides rather than expensive iodides and using 4 or propiolic acid rather than TMS-acetylene as inexpensive alkyne sources are described.

A thiamin-bound, pre-decarboxylation reaction intermediate analogue in the pyruvate dehydrogenase E1 subunit induces large scale disorder-to-order transformations in the enzyme and reveals novel structural features in the covalently bound adduct.

Science.gov (United States)

Arjunan, Palaniappa; Sax, Martin; Brunskill, Andrew; Chandrasekhar, Krishnamoorthy; Nemeria, Natalia; Zhang, Sheng; Jordan, Frank; Furey, William

2006-06-02

The crystal structure of the E1 component from the Escherichia coli pyruvate dehydrogenase multienzyme complex (PDHc) has been determined with phosphonolactylthiamin diphosphate (PLThDP) in its active site. PLThDP serves as a structural and electrostatic analogue of the natural intermediate alpha-lactylthiamin diphosphate (LThDP), in which the carboxylate from the natural substrate pyruvate is replaced by a phosphonate group. This represents the first example of an experimentally determined, three-dimensional structure of a thiamin diphosphate (ThDP)-dependent enzyme containing a covalently bound, pre-decarboxylation reaction intermediate analogue and should serve as a model for the corresponding intermediates in other ThDP-dependent decarboxylases. Regarding the PDHc-specific reaction, the presence of PLThDP induces large scale conformational changes in the enzyme. In conjunction with the E1-PLThDP and E1-ThDP structures, analysis of a H407A E1-PLThDP variant structure shows that an interaction between His-407 and PLThDP is essential for stabilization of two loop regions in the active site that are otherwise disordered in the absence of intermediate analogue. This ordering completes formation of the active site and creates a new ordered surface likely involved in interactions with the lipoyl domains of E2s within the PDHc complex. The tetrahedral intermediate analogue is tightly held in the active site through direct hydrogen bonds to residues His-407, Tyr-599, and His-640 and reveals a new, enzyme-induced, strain-related feature that appears to aid in the decarboxylation process. This feature is almost certainly present in all ThDP-dependent decarboxylases; thus its inclusion in our understanding of general thiamin catalysis is important.

Process simulation and techno economic analysis of renewable diesel production via catalytic decarboxylation of rubber seed oil - A case study in Malaysia.

Science.gov (United States)

Cheah, Kin Wai; Yusup, Suzana; Gurdeep Singh, Haswin Kaur; Uemura, Yoshimitsu; Lam, Hon Loong

2017-12-01

This work describes the economic feasibility of hydroprocessed diesel fuel production via catalytic decarboxylation of rubber seed oil in Malaysia. A comprehensive techno-economic assessment is developed using Aspen HYSYS V8.0 software for process modelling and economic cost estimates. The profitability profile and minimum fuels selling price of this synthetic fuels production using rubber seed oil as biomass feedstock are assessed under a set of assumptions for what can be plausibly be achieved in 10-years framework. In this study, renewable diesel processing facility is modelled to be capable of processing 65,000 L of inedible oil per day and producing a total of 20 million litre of renewable diesel product per annual with assumed annual operational days of 347. With the forecasted renewable diesel retail price of 3.64 RM per kg, the pioneering renewable diesel project investment offers an assuring return of investment of 12.1% and net return as high as 1.35 million RM. Sensitivity analysis conducted showed that renewable diesel production cost is most sensitive to rubber seed oil price and hydrogen gas price, reflecting on the relative importance of feedstock prices in the overall profitability profile. Copyright © 2017 Elsevier Ltd. All rights reserved.

Biosynthesis of firefly luciferin in adult lantern: decarboxylation of L-cysteine is a key step for benzothiazole ring formation in firefly luciferin synthesis.

Science.gov (United States)

Oba, Yuichi; Yoshida, Naoki; Kanie, Shusei; Ojika, Makoto; Inouye, Satoshi

2013-01-01

Bioluminescence in fireflies and click beetles is produced by a luciferase-luciferin reaction. The luminescence property and protein structure of firefly luciferase have been investigated, and its cDNA has been used for various assay systems. The chemical structure of firefly luciferin was identified as the D-form in 1963 and studies on the biosynthesis of firefly luciferin began early in the 1970's. Incorporation experiments using (14)C-labeled compounds were performed, and cysteine and benzoquinone/hydroquinone were proposed to be biosynthetic component for firefly luciferin. However, there have been no clear conclusions regarding the biosynthetic components of firefly luciferin over 30 years. Incorporation studies were performed by injecting stable isotope-labeled compounds, including L-[U-(13)C3]-cysteine, L-[1-(13)C]-cysteine, L-[3-(13)C]-cysteine, 1,4-[D6]-hydroquinone, and p-[2,3,5,6-D]-benzoquinone, into the adult lantern of the living Japanese firefly Luciola lateralis. After extracting firefly luciferin from the lantern, the incorporation of stable isotope-labeled compounds into firefly luciferin was identified by LC/ESI-TOF-MS. The positions of the stable isotope atoms in firefly luciferin were determined by the mass fragmentation of firefly luciferin. We demonstrated for the first time that D- and L-firefly luciferins are biosynthesized in the lantern of the adult firefly from two L-cysteine molecules with p-benzoquinone/1,4-hydroquinone, accompanied by the decarboxylation of L-cysteine.

Separation of chlorinated diastereomers of decarboxy-betacyanins in myeloperoxidase catalyzed chlorinated Beta vulgaris L. extract.

Science.gov (United States)

Wybraniec, Sławomir; Starzak, Karolina; Szneler, Edward; Pietrzkowski, Zbigniew

2016-11-15

A comparative chromatographic evaluation of chlorinated decarboxylated betanins and betanidins generated under activity of hypochlorous acid exerted upon these highly antioxidative potent decarboxylated pigments derived from natural sources was performed by LC-DAD-ESI-MS/MS. Comparison of the chromatographic profiles of the chlorinated pigments revealed two different directions of retention changes in relation to the corresponding substrates. Chlorination of all betacyanins that are decarboxylated at carbon C-17 results in an increase of their retention times. In contrast, all other pigments (the non-decarboxylated betacyanins as well as 2-decarboxy- and 15-decarboxy-derivatives) exhibit lower retention after chlorination. During further chromatographic experiments based upon chemical transformation of the related pigments (decarboxylation and deglucosylation), the compounds' structures were confirmed. The elaborated method for determination of chlorinated pigments enabled analysis of a chlorinated red beet root extract that was submitted to the MPO/H 2 O 2 /Cl - system acting under inflammation-like conditions (pH 5). This indicates a promising possibility for measurement of these chlorinated pigments as indicators of specific inflammatory states wherein betacyanins and decarboxylated betacyanins act as hypochlorite scavengers. Copyright © 2016 Elsevier B.V. All rights reserved.

Deoxygenation of Palmitic and Lauric Acids over Pt/ZIF-67 Membrane/Zeolite 5A Bead Catalysts.

Science.gov (United States)

Yang, Liqiu; Carreon, Moises A

2017-09-20

The deoxygenation of palmitic and lauric acids over 0.5 wt % Pt/ZIF-67 membrane/zeolite 5A bead catalysts is demonstrated. Almost complete conversion (% deoxygenation of ≥95%) of these two fatty acids was observed over both fresh and recycled catalyst after a 2 h reaction time. The catalysts displayed high selectivity to pentadecane and undecane via decarboxylation reaction pathway even at low 0.5 wt % Pt loading. Selectivity to pentadecane and undecane as high as ∼92% and ∼94% was observed under CO 2 atmosphere when palmitic and lauric acids were used respectively as reactants. Depending on the reaction gas atmosphere, two distinctive reaction pathways were observed: decarboxylation and hydrodeoxygenation. Specifically, it was found that decarboxylation reaction pathway was more favorable in the presence of helium and CO 2 , while hydrodeoxygenation pathway strongly competed against the decarboxylation pathway when hydrogen was employed during the deoxygenation reactions. Esters were identified as the key reaction intermediates leading to decarboxylation and hydrodeoxygenation pathways.

Crystal Structures of Apo and Liganded 4-Oxalocrotonate Decarboxylase Uncover a Structural Basis for the Metal-Assisted Decarboxylation of a Vinylogous β-Keto Acid.

Science.gov (United States)

Guimarães, Samuel L; Coitinho, Juliana B; Costa, Débora M A; Araújo, Simara S; Whitman, Christian P; Nagem, Ronaldo A P

2016-05-10

The enzymes in the catechol meta-fission pathway have been studied for more than 50 years in several species of bacteria capable of degrading a number of aromatic compounds. In a related pathway, naphthalene, a toxic polycyclic aromatic hydrocarbon, is fully degraded to intermediates of the tricarboxylic acid cycle by the soil bacteria Pseudomonas putida G7. In this organism, the 83 kb NAH7 plasmid carries several genes involved in this biotransformation process. One enzyme in this route, NahK, a 4-oxalocrotonate decarboxylase (4-OD), converts 2-oxo-3-hexenedioate to 2-hydroxy-2,4-pentadienoate using Mg(2+) as a cofactor. Efforts to study how 4-OD catalyzes this decarboxylation have been hampered because 4-OD is present in a complex with vinylpyruvate hydratase (VPH), which is the next enzyme in the same pathway. For the first time, a monomeric, stable, and active 4-OD has been expressed and purified in the absence of VPH. Crystal structures for NahK in the apo form and bonded with five substrate analogues were obtained using two distinct crystallization conditions. Analysis of the crystal structures implicates a lid domain in substrate binding and suggests roles for specific residues in a proposed reaction mechanism. In addition, we assign a possible function for the NahK N-terminal domain, which differs from most of the other members of the fumarylacetoacetate hydrolase superfamily. Although the structural basis for metal-dependent β-keto acid decarboxylases has been reported, this is the first structural report for that of a vinylogous β-keto acid decarboxylase and the first crystal structure of a 4-OD.

Kinetics and mechanism of aquation and formation reactions of carbonato complexes. XII. Deuterium solvent isotope effect on the rate of acid-catalyzed decarboxylation of the carbonatobis (ethylenediamine) cobalt(III) complex ion. A mechanistic reappraisal

International Nuclear Information System (INIS)

Harris, G.M.; Hyde, K.E.

1978-01-01

A recent study of the acid-catalyzed decarboxylation of the carbonatotetrakis(pyridine)cobalt(III) complex ion showed there to be rate acceleration in D 2 O solvent, consistent with a proton-preequilibration mechanism. This observation directly contradicts the results of a similar study made some years ago of the analogous ion, carbonatobis(ethylenediamine)cobalt(III), for which there appeared to be deceleration in D 2 O solvent. A reinvestigation of the latter reaction over a much wider acidity range has now shown the earlier work to be in error. The previously proposed generalized mechanism for aquation of chelated carbonato complex ions of the form CoN 4 CO 3 + (N 4 identical with various tetramine ligand groupings of uni-, bi-, or quadridentate type) has thus been revised to include a proton equilibration step. An unexpected complication arises in the interpretation of the data for the bis(ethylenediamine) complex ion in the acidity range 0.1 + ] + ] term, overtakes and exceeds the true first-order rate constant for CO 2 release. The interesting implications of this unusual first-order successive reaction system are fully explored in the context of the present study

Uptake and fate of IAA in apple callus tissue using IAA-1-14C

International Nuclear Information System (INIS)

Epstein, E.; Lavee, S.

1975-01-01

Incubation of young growing and older non-growing apple callus tissues in a medium containing IAA-1- 14 C resulted in rapid disappearance of the IAA. In old calluses (3 months), the major portion of IAA was lost by decarboxylation (90% after 4 hr) and very little (1.4%) was maintained by the tissue. In young calluses, after 4 hr in light, decarboxylation reached 20% and absorption 35% of the labelled IAA. Some decomposition of IAA was caused by photolysis and autoclaving (19% and 3%, respectively) but the final distribution of radioactivity was not affected. Factors such as sucrose concentration in the incubation medium, distilled water as incubation medium, and cutting of the callus did not affect tissue behavior. Special precautions were taken to eliminate non-biological decomposition of IAA. Therefore, we believe that the rapid CO 2 evolution is of enzymatic nature. This theory is supported by the drop in decarboxylation after killing of the callus, and the increase of decarboxylation with age. No enzyme was secreted by the callus into the medium after 24 hr of incubation, and IAA decomposition in old tissues is done probably on the surface. Absorption of IAA increased with increasing callus size and decarboxylation decreased. (auth.)

Decarboxylative Hydroalkylation of Alkynes.

Science.gov (United States)

Till, Nicholas A; Smith, Russell T; MacMillan, David W C

2018-05-02

The merger of open- and closed-shell elementary organometallic steps has enabled the selective intermolecular addition of nucleophilic radicals to unactivated alkynes. A range of carboxylic acids can be subjected to a CO 2 extrusion, nickel capture, migratory insertion sequence with terminal and internal alkynes to generate stereodefined functionalized olefins. This platform has been further extended, via hydrogen atom transfer, to the direct vinylation of unactivated C-H bonds. Preliminary studies indicate that a Ni-alkyl migratory insertion is operative.

The enantioselective total synthesis of (+)-clusianone.

Science.gov (United States)

Horeischi, Fiene; Guttroff, Claudia; Plietker, Bernd

2015-02-11

(+)-Clusianone, an exo-type B PPAP with reported anti-HIV and chemoprotective activities, was synthesized in eleven steps with 97% ee starting from acetylacetone. An enantioselective decarboxylative Tsuji-Trost-allylation and a Ru-catalyzed ring-closing metathesis-decarboxylative allylation were used to control both diastereo- and enantioselectivity.

Formation of sulphite, cysteic acid and taurine from sulphate by the egg embryo; Formation de sulfite, d'acide cysteique et de taurine a partir de sulfate par l'oeuf embryonne

Energy Technology Data Exchange (ETDEWEB)

Chapeville, F; Fromageot, P [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires

1959-07-01

It is shown that the formation of taurine from sulphate by the chicken embryo involves the reduction of sulphate to sulphite (I), the synthesis of cysteic acid (II) and its decarboxylation (Ill). The reaction (I) takes place in the vitellin sac. The reaction (II) results from the condensation of the sulphite with a-amino-acrylic acid and is carried out by the yolk. The enzymes responsible for the decarboxylation (III) are distributed both in the embryo and in its appendages. (author) [French] On demontre que la formation de taurine a partir de sulfate par l'embryon de poulet implique la reduction du sulfate en sulfite (1), la synthese de l'acide cysteique (Il) et sa decarboxylation (III). La reaction (I) a lieu dans le sac vitellin. La reaction (II) resulte de la condensation du sulfite avec l'acide a-amino-acrylique et est realisee par le jaune. Les enzymes assurant la decarboxylation (III) sont repartis aussi bien dans l'embryon que dans ses annexes. (auteur)

Kinetic and mechanistic studies of reactive intermediates in photochemical and transition metal-assisted oxidation, decarboxylation and alkyl transfer reactions

Science.gov (United States)

Carraher, Jack McCaslin

leads to the dissociation of H2O2 from Cr(III), while in the H+-independent reaction, CraqOOH2+ is transformed to Cr(V). Both scavengers rapidly remove Cr(V) and simplify both the kinetics and products by impeding formation of Cr(IV, V, VI). Syntheses, Reactivity, and Thermodynamic Considerations LRhR2+. Macrocyclic rhodium(II) complexes LRh(H 2O)2+ (L = L1= cyclam and L2 = meso-Me6-cyclam) react with alkyl hydroperoxides R(CH3)2COOH to generate the corresponding rhodium(III) alkyls LRh(H2O)R2+ (R = CH3, C2 H5, PhCH2). Methyl and benzyl complexes can also be prepared by bimolecular group transfer from alkyl cobaloximes (dmgX) 2(H2O)CoR (where R = CH3, CH2Ph and dmgX is either dimethylglyoxime or a BF2-capped derivative of dmg) to LRh(H2O)2+. When R = C2H5, C3H7 or C4H9, the mechanism changes from group transfer to hydrogen atom abstraction from the coordinated alkyl and produces LRh(H2O)H2+ and an a-olefin. The new LRh(H2O)R2+ complexes were characterized by solution NMR and by crystal structure analysis. They exhibit great stability in aqueous solution at room temperature, but undergo efficient Rh-C bond cleavage upon photolysis. 'Green' Model for Decarboxylation of Biomass Derived Acids via Photolysis of in situ formed Metal-Carboxylate Complexes. Photolysis of aqueous solutions containing propionic acid and Fe 3+ aq in the absence of oxygen generates a mixture of hydrocarbons (ethane, ethylene and butane), carbon dioxide, and Fe2+. Photolysis in the presence of O2 yields catalytic amounts of hydrocarbon products. When halide ions are present during photolysis; nearly quantitative yields of ethyl halides are produced via extraction of a halide atom from FeX2+ by ethyl radical. The rate constants for ethyl radical reactions with FeCl2+ (k = 4.0 (+/- 0.5) x 106 M-1s-1) and with FeBr 2+ (k = 3.0 (+/- 0.5) x 107 M-1s -1) were determined via competition reactions. Irradiation of solutions containing aqueous Cu2+ salts and linear carboxylic acids yield alpha

Isotope effect studies of chicken liver NADP malic enzyme: role of the metal ion and viscosity dependence

International Nuclear Information System (INIS)

Grissom, C.B.; Cleland, W.W.

1988-01-01

The role of the metal ion in the oxidative decarboxylation of malate by chicken liver NADP malic enzyme and details of the reaction mechanism have been investigated by 13 C isotope effects. With saturating NADP and the indicated metal ion at a total concentration 10-fold higher than its K/sub m/, the following primary 13 C kinetic isotope effects at C 4 of malate [ 13 (VK/sub mal/)] were observed at pH 8.0: Mg 2+ , 1.0336; Mn 2+ , 1.0365; Cd 2+ , 1.0366; Zn 2+ , 1.0337; Co 2+ , 1.0283; Ni 2+ , 1.025. Knowing the partitioning of the intermediate oxalacetate between decarboxylation to pyuvate and reduction to malate allows calculation of the intrinsic carbon isotope effect for decarboxylation to pyuvate and reduction to malate allows calculation of the intrinsic carbon isotope effect for decarboxylation. For Mg 2+ as activator, this was 1.049 with NADP and 1.046 with 3-acetylpyridine adenine dinucleotide phosphate, although the intrinsic primary deuterium isotope effects on dehydrogenation were 5.6 and 4.2, and the partition ratios of the oxalacetate intermediate for decarboxylation as opposed to hydride transfer were 0.11 and 3.96. It was not possible to calculate reasonable intrinsic carbon isotope effects with the other metal ions by use of the partitioning ratio of oxalacetate because of decarboxylation by another mechanism. The variation of 13 (VK/sub mal/) with pH was used to dissect the total forward and external components. When the authors attempted to use the variation of 13 (VK/sub mal/) with solution viscosity to determine the internal and external commitments, incorrect values were obtained because of a specific effect of the viscosogen in decreasing the K/sub m/ for malate, so that VK/sub mal/ actually increased with viscosity instead of decreasing, as theory predicts

Benzoylformate analogues exhibit differential rate-determining steps in the benzoylformate decarboxylase reaction

International Nuclear Information System (INIS)

Garcia, G.A.; Weiss, P.M.; Cook, P.F.; Kenyon, G.L.; Cleland, W.W.

1987-01-01

Benzoylformate decarboxylase from Pseudomonas putida is a thiamine pyrophosphate (TPP)-dependent enzyme which converts benzoylformate to benzaldehyde and CO 2 . The rate-determining step(s) in the benzoylformate decarboxylase reaction for a series of substituted benzoylformates (p-CH 3 O, p-CH 3 , p-Cl, and m-F) were studied using solvent deuterium and 13 C kinetic isotope effects. The normal substrate was found to have two partially rate-determining steps; initial tetrahedral adduct formation (D 2 O-sensitive) and decarboxylation ( 13 C-sensitive). D 2 O and 13 C isotope effects indicate that electron-withdrawing substituents (p-Cl and m-F) remove the rate dependence upon decarboxylation such that only a D 2 O effect on (V/K) is observed. Conversely, electron-donating substituents increase the rate-dependence upon decarboxylation such that a larger 13 (V/K) is seen while the D 2 O effects on (V) and (V/K) are not dramatically different from those for benzoylformate. All of the data are consistent with substituent stabilization or destabilization of the carbanionic intermediate formed upon decarboxylation

Structures of the N47A and E109Q mutant proteins of pyruvoyl-dependent arginine decarboxylase from Methanococcus jannaschii

International Nuclear Information System (INIS)

Soriano, Erika V.; McCloskey, Diane E.; Kinsland, Cynthia; Pegg, Anthony E.; Ealick, Steven E.

2008-01-01

The crystal structures of two arginine decarboxylase mutant proteins provide insights into the mechanisms of pyruvoyl-group formation and the decarboxylation reaction. Pyruvoyl-dependent arginine decarboxylase (PvlArgDC) catalyzes the first step of the polyamine-biosynthetic pathway in plants and some archaebacteria. The pyruvoyl group of PvlArgDC is generated by an internal autoserinolysis reaction at an absolutely conserved serine residue in the proenzyme, resulting in two polypeptide chains. Based on the native structure of PvlArgDC from Methanococcus jannaschii, the conserved residues Asn47 and Glu109 were proposed to be involved in the decarboxylation and autoprocessing reactions. N47A and E109Q mutant proteins were prepared and the three-dimensional structure of each protein was determined at 2.0 Å resolution. The N47A and E109Q mutant proteins showed reduced decarboxylation activity compared with the wild-type PvlArgDC. These residues may also be important for the autoprocessing reaction, which utilizes a mechanism similar to that of the decarboxylation reaction

Radiation damage to polypeptides and proteins in the solid state. Pt. 2

International Nuclear Information System (INIS)

Soeylemez, T.; Baumeister, W.; Herbertz, L.M.

1981-01-01

For the transformation of glutamic acid into α-aminobutyric acid upon irradiation a decarboxylation mechanism involving the formation of CO 2 has been proposed previously. Here we present further experimental evidence in favour of this mechanism. Additionally the formation of CO as a decarboxylation product has been detected; a radical anion mechanism for its formation is proposed. (orig.)

Thermal decomposition of dilute aqueous formic acid solutions

DEFF Research Database (Denmark)

Bjerre, A.B.; Sørensen, E.

1992-01-01

or a decarboxylation. In particular the second one is dependent on the reactor vessel used. It is shown to be catalyzed by a mixture of oxides of stainless steel components. The presence of CH3COOH or CH3CHO promotes the decomposition of HCOOH by way of both decarboxylation and oxidation. In any case formic acid...

Search for new ways of production of diesel fuels from fats and oils on the basis of renewable raw materials; Suche nach neuen Wegen zur Gewinnung von Dieselkraftstoffen aus Fetten und Oelen auf der Basis von nachwachsenden Rohstoffen

Energy Technology Data Exchange (ETDEWEB)

Paetzold, Eckhard [Leibniz-Institut fuer Katalyse an der Universitaet Rostock e.V., Rostock (Germany); Schuemann, Ulrike [Rostock Univ. (Germany). Lehrstuhl fuer Kolbenmaschinen und Verbrennungsmotoren; Kragl, Udo [Leibniz-Institut fuer Katalyse an der Universitaet Rostock e.V., Rostock (Germany); Rostock Univ. (Germany). Inst. fuer Chemie

2012-07-01

Fats and oils are one of the oldest classes of chemical compounds used by humans. Natural fats consist of a hydrocarbon chain with double bonds and carboxylic/ester functions. They can be converted by hydrogenation and decarboxylation using heterogeneous catalysts at high temperature (450 C) and high hydrogen pressure (150 bar). Conversion of fats and oils by hydrogenation and decarboxylation with homogeneous noble metal catalysts at essential milder conditions for different applications as hydrotreated vegetable oil is possible as well. The reactions were studied by model compounds for the hydrogenation of double bonds e.g. linolenic acid and the decarboxylation of stearic acid. It was found that palladium nanoparticles can be used as catalyst in a two phase reaction. (orig.)

Improved Processes to Remove Naphthenic Acids

Energy Technology Data Exchange (ETDEWEB)

Aihua Zhang; Qisheng Ma; Kangshi Wang; Yongchun Tang; William A. Goddard

2005-12-09

In the past three years, we followed the work plan as we suggested in the proposal and made every efforts to fulfill the project objectives. Based on our large amount of creative and productive work, including both of experimental and theoretic aspects, we received important technical breakthrough on naphthenic acid removal process and obtained deep insight on catalytic decarboxylation chemistry. In detail, we established an integrated methodology to serve for all of the experimental and theoretical work. Our experimental investigation results in discovery of four type effective catalysts to the reaction of decarboxylation of model carboxylic acid compounds. The adsorption experiment revealed the effectiveness of several solid materials to naphthenic acid adsorption and acidity reduction of crude oil, which can be either natural minerals or synthesized materials. The test with crude oil also received promising results, which can be potentially developed into a practical process for oil industry. The theoretical work predicted several possible catalytic decarboxylation mechanisms that would govern the decarboxylation pathways depending on the type of catalysts being used. The calculation for reaction activation energy was in good agreement with our experimental measurements.

Singlet oxygen-induced oxidation of alkylthiocarboxylic acids

International Nuclear Information System (INIS)

Celuch, M.; Pogocki, D.; Enache, M.

2006-01-01

Singlet oxygen ( 1 O 2 ) could be generated in biological systems by endogenous and exogenous processes (e.g. enzymatic and chemical reactions, UV or visible light in the presence of a sensitizer). Numerous data show that proteins are the major targets of 1 O 2 -induced damage in the living cells. In particular, reaction of 1 O 2 with thioether sulphur of methionine (Met) leads to the formation of persulphoxide >S (+) O-O (-) which is in equilibrium with superoxide radical-anion (O 2 ·- ) and respective sulphur-centered-radical-cation >S ·+ . In presented work, investigation the mechanisms of deprotonation and decarboxylation of the S ·+ - the irreversible processes, which competes with the formation of sulphoxide. Using thioethers dissevering by the number and positions of carboxylate groups it has been shown that efficiency of both decarboxylation and deprotonation could be influenced by various factors such as neighbouring group participation and environmental effects. The observed influence of carboxylate groups in β-position relative to the sulphur on the efficiency of decarboxylation suggests furthermore that they may also catalyze decarboxylation of α-positioned carboxylate in a manner similar to hydroxide anion

Disentangling the Origin of the Kok Effect Using Position Specific Glucose Labeling in Sunflower Leaves

Science.gov (United States)

Gauthier, P. P.; Bender, M. L.; Saenz, N.

2015-12-01

In plants, leaf mitochondrial respiratory CO2 release is inhibited by light. Bessel Kok first demonstrated this inhibition in 1948. Based on curves of CO2 assimilation vs irradiance, it is understood that respiration is maximal in the dark. It then frequently decreases linearly with irradiance until reaching some value around the compensation point, beyond which it is constant. CO2 released by mitochondrial respiration is the result of decarboxylation through pyruvate dehydrogenase (PDH), the tricarboxylic acid pathway (TCAP) and the oxydative pentose phosphate pathway (OPPP). The overall activity of these three reactions is reduced by light. However, their individual contributions to the Kok effect are unknown. We measured the rate of decarboxylation of glucose, position-specifically labeled with 13C, to evaluate the participation of PDH, TCAP and OPPP in the Kok effect of sunflower. Leaves were fed with labeled glucose through their transpiration stream. The δ13C of the CO2 released by the leaf was then measured as a function of irradiance. The results showed that the inhibition of the decarboxylation of carbon positions 3 and 4 in glucose is at the origin of the Kok effect. These are the positions of carbon atoms decarboxylated by PDH. In addition, the rate of decarboxylation of position 1 was not different in the light and in the dark. Thus OPPP plays no role in the Kok effect in sunflower leaves. This work improves our current understanding of leaf mitochondrial respiratory metabolism in the light. Invoking the Kok effect in plant physiology models should improve our ability to simulate carbon fluxes of terrestrial ecosystems.

Medicinal Cannabis: In Vitro Validation of Vaporizers for the Smoke-Free Inhalation of Cannabis.

Science.gov (United States)

Lanz, Christian; Mattsson, Johan; Soydaner, Umut; Brenneisen, Rudolf

2016-01-01

Inhalation by vaporization is a promising application mode for cannabis in medicine. An in vitro validation of 5 commercial vaporizers was performed with THC-type and CBD-type cannabis. Gas chromatography/mass spectrometry was used to determine recoveries of total THC (THCtot) and total CBD (CBDtot) in the vapor. High-performance liquid chromatography with photodiode array detection was used for the quantitation of acidic cannabinoids in the residue and to calculate decarboxylation efficiencies. Recoveries of THCtot and CBDtot in the vapor of 4 electrically-driven vaporizers were 58.4 and 51.4%, 66.8 and 56.1%, 82.7 and 70.0% and 54.6 and 56.7% for Volcano Medic®, Plenty Vaporizer®, Arizer Solo® and DaVinci Vaporizer®, respectively. Decarboxylation efficiency was excellent for THC (≥ 97.3%) and CBD (≥ 94.6%). The gas-powered Vape-or-Smoke™ showed recoveries of THCtot and CBDtot in the vapor of 55.9 and 45.9%, respectively, and a decarboxylation efficiency of ≥ 87.7 for both cannabinoids. However, combustion of cannabis was observed with this device. Temperature-controlled, electrically-driven vaporizers efficiently decarboxylate inactive acidic cannabinoids and reliably release their corresponding neutral, active cannabinoids. Thus, they offer a promising application mode for the safe and efficient administration of medicinal cannabis.

Medicinal Cannabis: In Vitro Validation of Vaporizers for the Smoke-Free Inhalation of Cannabis.

Directory of Open Access Journals (Sweden)

Christian Lanz

Full Text Available Inhalation by vaporization is a promising application mode for cannabis in medicine. An in vitro validation of 5 commercial vaporizers was performed with THC-type and CBD-type cannabis. Gas chromatography/mass spectrometry was used to determine recoveries of total THC (THCtot and total CBD (CBDtot in the vapor. High-performance liquid chromatography with photodiode array detection was used for the quantitation of acidic cannabinoids in the residue and to calculate decarboxylation efficiencies. Recoveries of THCtot and CBDtot in the vapor of 4 electrically-driven vaporizers were 58.4 and 51.4%, 66.8 and 56.1%, 82.7 and 70.0% and 54.6 and 56.7% for Volcano Medic®, Plenty Vaporizer®, Arizer Solo® and DaVinci Vaporizer®, respectively. Decarboxylation efficiency was excellent for THC (≥ 97.3% and CBD (≥ 94.6%. The gas-powered Vape-or-Smoke™ showed recoveries of THCtot and CBDtot in the vapor of 55.9 and 45.9%, respectively, and a decarboxylation efficiency of ≥ 87.7 for both cannabinoids. However, combustion of cannabis was observed with this device. Temperature-controlled, electrically-driven vaporizers efficiently decarboxylate inactive acidic cannabinoids and reliably release their corresponding neutral, active cannabinoids. Thus, they offer a promising application mode for the safe and efficient administration of medicinal cannabis.

Preparation of 9-vinylanthracene

International Nuclear Information System (INIS)

Dhane, D.L.; Noras, K.A.; Gaiki, G.M.

1975-01-01

Two convenient methods for synthesising 9-vinylanthracene (I) which can be used a solute in liquid scintillation counting are described. One involves the decarboxylation of β-(9-anthracene) - acrylic acid (II) and the other a coupling reaction between 9-anthraldehyde and methylene iodide to presence of magnesium amalgam. The effect of temperature, acids and bases on the decarboxylation has been studied and the theoretical explanation provided for the behaviour of the reaction. NMR and fluorescence data have been recorded (author)

Formation of sulphite, cysteic acid and taurine from sulphate by the egg embryo

International Nuclear Information System (INIS)

Chapeville, F.; Fromageot, P.

1959-01-01

It is shown that the formation of taurine from sulphate by the chicken embryo involves the reduction of sulphate to sulphite (I), the synthesis of cysteic acid (II) and its decarboxylation (Ill). The reaction (I) takes place in the vitellin sac. The reaction (II) results from the condensation of the sulphite with a-amino-acrylic acid and is carried out by the yolk. The enzymes responsible for the decarboxylation (III) are distributed both in the embryo and in its appendages. (author) [fr

Copper-Catalyzed Synthesis of Trifluoroethylarenes from Benzylic Bromodifluoroacetates.

Science.gov (United States)

Ambler, Brett R; Zhu, Lingui; Altman, Ryan A

2015-08-21

Trifluoroethylarenes are found in a variety of biologically active molecules, and strategies for accessing this substructure are important for developing therapeutic candidates and biological probes. Trifluoroethylarenes can be directly accessed via nucleophilic trifluoromethylation of benzylic electrophiles; however, current catalytic methods do not effectively transform electron-deficient substrates and heterocycles. To address this gap, we report a Cu-catalyzed decarboxylative trifluoromethylation of benzylic bromodifluoroacetates. To account for the tolerance of sensitive functional groups, we propose an inner-sphere mechanism of decarboxylation.

Rhodium-catalyzed regioselective olefination directed by a carboxylic group.

Science.gov (United States)

Mochida, Satoshi; Hirano, Koji; Satoh, Tetsuya; Miura, Masahiro

2011-05-06

The ortho-olefination of benzoic acids can be achieved effectively through rhodium-catalyzed oxidative coupling with alkenes. The carboxylic group is readily removable to allow ortho-olefination/decarboxylation in one pot. α,β-Unsaturated carboxylic acids such as methacrylic acid also undergo the olefination at the β-position. Under the rhodium catalysis, the cine-olefination of heteroarene carboxylic acids such as thiophene-2-carboxylic acid proceeds smoothly accompanied by decarboxylation to selectively produce the corresponding vinylheteroarene derivatives. © 2011 American Chemical Society

Naphthenic acid removal from HVGO by alkaline earth metal catalysts

Energy Technology Data Exchange (ETDEWEB)

Ding, L.; Rahimi, P.; Hawkins, R.; Bhatt, S.; Shi, Y. [National Centre for Upgrading Technology, Devon, AB (Canada); Natural Resources Canada, Devon, AB (Canada). CanmetENERGY

2009-07-01

This poster highlighted a study that investigated naphthenic acid removal from bitumen-derived heavy vacuum gas oil (HVGO) by thermal cracking and catalytic decarboxylation over alkaline earth-metal oxides and ZnO catalysts in a batch reactor and a continuous fixed-bed reactor. X-ray diffraction (XRD), thermogravimetric-differential thermal analysis (TG-DTA) temperature-programmed desorption (TPD) of carbon dioxide (CO{sub 2}-TPD), and scanning electron microscopy were used to characterize the fresh and spent catalysts. With MgO and ZnO, naphthenic acid removal proceeded via catalytic decarboxylation. No crystalline phase changes were observed after reaction. With CaO, multiple pathways such as catalytic decarboxylation, neutralization, and thermal cracking were responsible for naphthenic acid conversion. The spent catalysts contained Ca(OH){sub 2} and CaCO{sub 3}. With BaO, naphthenic acid conversion occurred through neutralization. All BaO was converted to Ba(OH){sub 2} during the reaction. tabs., figs.

Decarboxylative Trifluoromethylation of Aliphatic Carboxylic Acids.

Science.gov (United States)

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

2018-05-14

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

PICOLINIC ACID PROMOTED OXIDATIVE DECARBOXYLATION OF ...

African Journals Online (AJOL)

enthalpy of activation, ∆H≠ calculated for the PA promoted Cr(VI) reaction of PSAA are. -112.38 ± 6.6 J K-1 mol-1 and 53.17 ± 1.9 KJ mol-1 respectively .... neutralization of positive charge on sulfur atom as a result of ligand coupling with oxygen atom. Such a ligand coupling pathway has already been suggested by the ...

Picolinic acid promoted oxidative decarboxylation of ...

African Journals Online (AJOL)

The kinetics and mechanism of picolinic acid promoted reaction of phenylsulfinylacetic acid (PSAA) with Cr(VI) was carried out in aqueous acetonitrile medium under pseudo first order conditions. The reaction follows Michaelis-Menten type of kinetics with respect to PSAA. The catalytic activity by picolinic acid can be ...

Characterization of Phosphoenolpyruvate Carboxykinase from Pineapple Leaves Ananas comosus (L.) Merr. 1

Science.gov (United States)

Daley, Laurence S.; Ray, Thomas B.; Vines, H. Max; Black, Clanton C.

1977-01-01

Phosphoenolpyruvate carboxykinase has been partially purified from pineapple (Ananas comosus [L.]) leaves. Specific activities obtained show it to be a major activity in this tissue. Above 15 C, the respective activation energies for decarboxylation and carboxylation are 13 and 12 kcal/mol. Below 15 C, there are discontinuities in Arrhenius plots with an associated large increase in activation energy. The adenine nucleotides are preferred to other nucleotides as substrates. The apparent Km values in the carboxylation direction are: ADP 0.13 mm, HCO3- 3.4 mm, and phosphoenolpyruvate 5 mm. In the decarboxylation direction, the apparent Km values are: ATP 0.02 mm, ADP 0.05 mm, and oxaloacetate 0.4 mm. The decarboxylation activity had an almost equal velocity with either ADP or ATP. The pH optima are between 6.8 and 7. Inhibition of the carboxylation reaction by ATP, pyruvate, and carbonic anhydrase was demonstrated. Decarboxylase specific activities are over twice carboxylation activities. The data support a model in which phosphoenolpyruvate carboxykinase is of physiological significance only during the light period and then only as a decarboxylase. PMID:16659905

Characterization of Phosphoenolpyruvate Carboxykinase from Pineapple Leaves Ananas comosus (L.) Merr.

Science.gov (United States)

Daley, L S; Ray, T B; Vines, H M; Black, C C

1977-04-01

Phosphoenolpyruvate carboxykinase has been partially purified from pineapple (Ananas comosus [L.]) leaves. Specific activities obtained show it to be a major activity in this tissue. Above 15 C, the respective activation energies for decarboxylation and carboxylation are 13 and 12 kcal/mol. Below 15 C, there are discontinuities in Arrhenius plots with an associated large increase in activation energy. The adenine nucleotides are preferred to other nucleotides as substrates. The apparent Km values in the carboxylation direction are: ADP 0.13 mm, HCO(3) (-) 3.4 mm, and phosphoenolpyruvate 5 mm. In the decarboxylation direction, the apparent Km values are: ATP 0.02 mm, ADP 0.05 mm, and oxaloacetate 0.4 mm. The decarboxylation activity had an almost equal velocity with either ADP or ATP. The pH optima are between 6.8 and 7. Inhibition of the carboxylation reaction by ATP, pyruvate, and carbonic anhydrase was demonstrated. Decarboxylase specific activities are over twice carboxylation activities. The data support a model in which phosphoenolpyruvate carboxykinase is of physiological significance only during the light period and then only as a decarboxylase.

Blood-brain transfer and metabolism of 6-[18F]fluoro-L-dopa in rat

International Nuclear Information System (INIS)

Reith, J.; Dyve, S.; Kuwabara, H.; Guttman, M.; Diksic, M.; Gjedde, A.

1990-01-01

In a study designed to reveal the rates of blood-brain transfer and decarboxylation of fluoro-L-3,4-dihydroxyphenylalanine (FDOPA), we discovered a major discrepancy between the DOPA decarboxylase activity reported in the literature and the rate of FDOPA decarboxylation measured in the study. Donor rats received intravenous injections of 6 mCi fluorine-18-labeled FDOPA. The donor rats synthesized methyl-FDOPA. Arterial plasma, containing both FDOPA and methyl-FDOPA, was sampled from the donor rats at different times and reinjected into recipient rats in which it circulated for 20 s. The blood-brain clearance of the mixture of labeled tracers in the plasma was determined by an integral method. The individual permeabilities were determined by linear regression analysis, according to which the average methyl-FDOPA permeability in the blood-brain barrier was twice that of FDOPA, which averaged 0.037 ml g-1 min-1. The permeability ratio was used to determine the fractional clearance from the brain of FDOPA (and hence of methyl-FDOPA), which averaged 0.081 min-1. In the striatum, the measured average FDOPA decarboxylation rate constant (kD3) was 0.010 min-1, or no more than 1% of the rate of striatal decarboxylation of DOPA measured in vitro and in vivo. We interpreted this finding as further evidence in favor of the hypothesis that striatum has two dopamine (DA) pools, of which only DA in the large pool is protected from metabolism. Hence, no more than 1% of the quantity of fluoro-DA theoretically synthesized was actually retained in striatum

Biocatalytic Synthesis of Vanillin

Science.gov (United States)

Li, Tao; Rosazza, John P. N.

2000-01-01

The conversions of vanillic acid and O-benzylvanillic acid to vanillin were examined by using whole cells and enzyme preparations of Nocardia sp. strain NRRL 5646. With growing cultures, vanillic acid was decarboxylated (69% yield) to guaiacol and reduced (11% yield) to vanillyl alcohol. In resting Nocardia cells in buffer, 4-O-benzylvanillic acid was converted to the corresponding alcohol product without decarboxylation. Purified Nocardia carboxylic acid reductase, an ATP and NADPH-dependent enzyme, quantitatively reduced vanillic acid to vanillin. Structures of metabolites were established by 1H nuclear magnetic resonance and mass spectral analyses. PMID:10653736

Direct Production of Propene from the Thermolysis of Poly(β-hydroxybutyrate) (PHB). An Experimental and DFT Investigation.

Science.gov (United States)

Clark, Jared M; Pilath, Heidi M; Mittal, Ashutosh; Michener, William E; Robichaud, David J; Johnson, David K

2016-01-28

We demonstrate a synthetic route toward the production of propene directly from poly(β-hydroxybutyrate) (PHB), the most common of a wide range of high-molecular-mass microbial polyhydroxyalkanoates. Propene, a major commercial hydrocarbon, was obtained from the depolymerization of PHB and subsequent decarboxylation of the crotonic acid monomer in good yields (up to 75 mol %). The energetics of PHB depolymerization and the gas-phase decarboxylation of crotonic acid were also studied using density functional theory (DFT). The average activation energy for the cleavage of the R'C(O)O-R linkage is calculated to be 163.9 ± 7.0 kJ mol(-1). Intramolecular, autoacceleration effects regarding the depolymerization of PHB, as suggested in some literature accounts, arising from the formation of crotonyl and carboxyl functional groups in the products could not be confirmed by the results of DFT and microkinetic modeling. DFT results, however, suggest that intermolecular catalysis involving terminal carboxyl groups may accelerate PHB depolymerization. Activation energies for this process were estimated to be about 20 kJ mol(-1) lower than that for the noncatalyzed ester cleavage, 144.3 ± 6.4 kJ mol(-1). DFT calculations predict the decarboxylation of crotonic acid to follow second-order kinetics with an activation energy of 147.5 ± 6.3 kJ mol(-1), consistent with that measured experimentally, 146.9 kJ mol(-1). Microkinetic modeling of the PHB to propene overall reaction predicts decarboxylation of crotonic acid to be the rate-limiting step, consistent with experimental observations. The results also indicate that improvements made to enhance the isomerization of crotonic acid to vinylacetic acid will improve the direct conversion of PHB to propene.

A general enantioselective route to the chamigrene natural product family

KAUST Repository

White, David E.; Stewart, Ian C.; Seashore-Ludlow, Brinton A.; Grubbs, Robert H.; Stoltz, Brian M.

2010-01-01

Described in this report is an enantioselective route toward the chamigrene natural product family. The key disconnections in our synthetic approach include sequential enantioselective decarboxylative allylation and ring-closing olefin metathesis to form the all-carbon quaternary stereocenter and spirocyclic core present in all members of this class of compounds. The generality of this strategy is demonstrated by the first total syntheses of elatol and the proposed structure of laurencenone B, as well as the first enantioselective total syntheses of laurencenone C and α-chamigrene. A brief exploration of the substrate scope of the enantioselective decarboxylative allylation/ring-closing metathesis sequence with fully substituted vinyl chlorides is also presented.

A general enantioselective route to the chamigrene natural product family

KAUST Repository

White, David E.

2010-06-01

Described in this report is an enantioselective route toward the chamigrene natural product family. The key disconnections in our synthetic approach include sequential enantioselective decarboxylative allylation and ring-closing olefin metathesis to form the all-carbon quaternary stereocenter and spirocyclic core present in all members of this class of compounds. The generality of this strategy is demonstrated by the first total syntheses of elatol and the proposed structure of laurencenone B, as well as the first enantioselective total syntheses of laurencenone C and α-chamigrene. A brief exploration of the substrate scope of the enantioselective decarboxylative allylation/ring-closing metathesis sequence with fully substituted vinyl chlorides is also presented.

Simple purification for E. coli putrescine aminopropyl-transferase

International Nuclear Information System (INIS)

Gavagan, J.E.; Anton, D.L.

1986-01-01

Putrescine aminopropyltransferase transfers an aminopropyl group from decarboxylated S-adenosylmethionine to putrescine forming spermidine. They have recently developed a rapid assay based on the separation of the spermidine product from the unreacted [ 14 C-met] labeled decarboxylated S-adenosylmethionine substrate by charcoal adsorption. Using this assay they have developed a simple protocol for the purification of putrescine aminopropyltransferase from E. coli HT 527. The procedure involves ammonium sulfate fractionation, phenyl Sepharose chromatography, and FPLC. The enzyme is greater than 80% pure as judged by SDS-PAGE and has an apparent subunit molecular weight of 35,000. The kinetics of this enzyme are being reinvestigated

Aspartate beta-decarboxylase from Alcaligenes faecalis: carbon-13 kinetic isotope effect and deuterium exchange experiments

International Nuclear Information System (INIS)

Rosenberg, R.M.; O'Leary, M.H.

1985-01-01

The authors have measured the 13 C kinetic isotope effect at pH 4.0, 5.0, 6.0, and 6.5 and in D 2 O at pH 5.0 and the rate of D-H exchange of the alpha and beta protons of aspartic acid in D 2 O at pH 5.0 for the reaction catalyzed by the enzyme aspartate beta-decarboxylase from Alcaligenes faecalis. The 13 C kinetic isotope effect, with a value of 1.0099 +/- 0.0002 at pH 5.0, is less than the intrinsic isotope effect for the decarboxylation step, indicating that the decarboxylation step is not entirely rate limiting. The authors have been able to estimate probable values of the relative free energies of the transition states of the enzymatic reaction up to and including the decarboxylation step from the 13 C kinetic isotope effect and the rate of D-H exchange of alpha-H. The pH dependence of the kinetic isotope effect reflects the pKa of the pyridine nitrogen of the coenzyme pyridoxal 5'-phosphate but not that of the imine nitrogen. A mechanism is proposed for the exchange of aspartate beta-H that is consistent with the stereochemistry suggested earlier

In-vitro evaluation of limitations and possibilities for the future use of intracorporeal gas exchangers placed in the upper lobe position.

Science.gov (United States)

Schumer, Erin; Höffler, Klaus; Kuehn, Christian; Slaughter, Mark; Haverich, Axel; Wiegmann, Bettina

2018-03-01

The lack of donor organs has led to the development of alternative "destination therapies", such as a bio-artificial lung (BA) for end-stage lung disease. Ultimately aiming at a fully implantable BA, general capabilities and limitations of different oxygenators were tested based on the model of BA positioning at the right upper lobe. Three different-sized oxygenators (neonatal, paediatric, and adult) were tested in a mock circulation loop regarding oxygenation and decarboxylation capacities for three respiratory pathologies. Blood flows were imitated by a roller pump, and respiration was imitated by a mechanical ventilator with different FiO 2 applications. Pressure drops across the oxygenators and the integrity of the gas-exchange hollow fibers were analyzed. The neonatal oxygenator proved to be insufficient regarding oxygenation and decarboxylation. Despite elevated pCO 2 levels, the paediatric and adult oxygenators delivered comparable sufficient oxygen levels, but sufficient decarboxylation across the oxygenators was ensured only at flow rates of 0.5 L min. Only the adult oxygenator indicated no significant pressure drops. For all tested conditions, gas-exchange hollow fibers remained intact. This is the first study showing the general feasibility of delivering sufficient levels of gas exchange to an intracorporeal BA via patient's breathing, without damaging gas-exchange hollow fiber membranes.

Biobased synthesis of acrylonitrile from glutamic acid

NARCIS (Netherlands)

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

2011-01-01

Glutamic acid was transformed into acrylonitrile in a two step procedure involving an oxidative decarboxylation in water to 3-cyanopropanoic acid followed by a decarbonylation-elimination reaction using a palladium catalyst

Involvement of the agmatinergic system in the depressive-like phenotype of the Crtc1 knockout mouse model of depression

KAUST Repository

Meylan, E M; Breuillaud, L; Seredenina, T; Magistretti, Pierre J.; Halfon, O; Luthi-Carter, R; Cardinaux, J-R

2016-01-01

Recent studies implicate the arginine-decarboxylation product agmatine in mood regulation. Agmatine has antidepressant properties in rodent models of depression, and agmatinase (Agmat), the agmatine-degrading enzyme, is upregulated in the brains

Involvement of the ornithine decarboxylase gene in acid stress response in probiotic Lactobacillus delbrueckii UFV H2b20.

Science.gov (United States)

Ferreira, A B; Oliveira, M N V de; Freitas, F S; Paiva, A D; Alfenas-Zerbini, P; Silva, D F da; Queiroz, M V de; Borges, A C; Moraes, C A de

2015-01-01

Amino acid decarboxylation is important for the maintenance of intracellular pH under acid stress. This study aims to carry out phylogenetic and expression analysis by real-time PCR of two genes that encode proteins involved in ornithine decarboxylation in Lactobacillus delbrueckii UFV H2b20 exposed to acid stress. Sequencing and phylogeny analysis of genes encoding ornithine decarboxylase and amino acid permease in L. delbrueckii UFV H2b20 showed their high sequence identity (99%) and grouping with those of L. delbrueckii subsp. bulgaricus ATCC 11842. Exposure of L. delbrueckii UFV H2b20 cells in MRS pH 3.5 for 30 and 60 min caused a significant increase in expression of the gene encoding ornithine decarboxylase (up to 8.1 times higher when compared to the control treatment). Increased expression of the ornithine decarboxylase gene demonstrates its involvement in acid stress response in L. delbrueckii UFV H2b20, evidencing that the protein encoded by that gene could be involved in intracellular pH regulation. The results obtained show ornithine decarboxylation as a possible mechanism of adaptation to an acidic environmental condition, a desirable and necessary characteristic for probiotic cultures and certainly important to the survival and persistence of the L. delbrueckii UFV H2b20 in the human gastrointestinal tract.

Establishment of callus from Opuntia robusta Wendl., a wild and ...

African Journals Online (AJOL)

coco santos

2013-04-22

Apr 22, 2013 ... plants produce tender cladodes, consumed as vegetable and fruits (prickly pear) .... The highest callus amount was obtained in media supplemented ... CO2 during carboxylation and decarboxylation reactions, improves the ...

Prebiotic chemistry: Ribozyme takes its vitamins

Science.gov (United States)

Burrows, Cynthia J.

2013-11-01

Selection of an RNA catalyst that can use the vitamin thiamin to catalyse a key metabolic decarboxylation reaction has broad implications for understanding the role of RNA in the early stages of chemical evolution.

Synthesis and reactivity of aliphatic sulfur pentafluorides from substituted (pentafluorosulfanyl)benzenes

Czech Academy of Sciences Publication Activity Database

Vida, N.; Václavík, Jiří; Beier, P.

2016-01-01

Roč. 12, JAN 20 2016 (2016), s. 110-116 ISSN 1860-5397 Institutional support: RVO:67985840 Keywords : dearomatization * decarboxylation * Diels-Alder reaction Subject RIV: EE - Microbiology, Virology Impact factor: 2.337, year: 2016

Formation and utilization of acetoin, an unusual product of pyruvate metabolism by Ehrlich and AS30-D tumor mitochondria.

Science.gov (United States)

Baggetto, L G; Lehninger, A L

1987-07-15

[14C]Pyruvate was rapidly non-oxidatively decarboxylated by Ehrlich tumor mitochondria at a rate of 40 nmol/min/mg of protein in the presence or absence of ADP. A search for decarboxylation products led to significant amounts of acetoin formed when Ehrlich tumor mitochondria were incubated with 1 mM [14C] pyruvate in the presence of ATP. Added acetoin to aerobic tumor mitochondria was rapidly utilized in the presence of ATP at a rate of 65 nmol/min/mg of protein. Citrate has been found as a product of acetoin utilization and was exported from the tumor mitochondria. Acetoin has been found in the ascitic liquid of Ehrlich and AS30-D tumor-bearing animals. These unusual reactions were not observed in control rat liver mitochondria.

Sub- T g Cross-Linking of a Polyimide Membrane for Enhanced CO 2 Plasticization Resistance for Natural Gas Separation

KAUST Repository

Qiu, Wulin; Chen, Chien-Chiang; Xu, Liren; Cui, Lili; Paul, Donald R.; Koros, William J.

2011-01-01

Decarboxylation-induced thermal cross-linking occurs at elevated temperatures (∼15 °C above glass transition temperature) for 6FDA-DAM:DABA polyimides, which can stabilize membranes against swelling and plasticization in aggressive feed streams

Thermal analysis and its application in evaluation of fluorinated polyimide membranes for gas separation

KAUST Repository

Qiu, Wulin; Chen, Chien-Chiang; Kincer, Matthew R.; Koros, William J.

2011-01-01

by reaction with acetic anhydride to produce polyimide (PI). The resulting polymers were characterized using thermal analysis techniques including TGA, derivative weight analysis, TGA-MS, and DSC. The decarboxylation-induced thermal cross-linking, ester cross

Chemistry Notes

Science.gov (United States)

School Science Review, 1976

1976-01-01

Described are eight chemistry experiments and demonstrations applicable to introductory chemistry courses. Activities include: measure of lattice enthalpy, Le Chatelier's principle, decarboxylation of soap, use of pocket calculators in pH measurement, and making nylon. (SL)

A specific radioenzymatic assay for dihydroxyphenylalanine (DOPA). Plasma DOPA may be the precursor of urine free dopamine

International Nuclear Information System (INIS)

Brown, M.J.; Dollery, C.T.

1981-01-01

A sensitive radioenzymatic assay was developed, in which DOPA is enzymatically decarboxylated to dopamine and the latter converted to [ 3 H]-methoxytryamine in the presence of [ 3 H]-S-adenosyl-L-methionine and catechol-o-methyltransferase. The assay was specific for DOPA, and was sensitive to 50 pg/ml. Endogenous DOPA was found to be present in the plasma of eight human volunteers at a concentration of 10.46 +- 2.42 nmol/l. Simultaneous urine collections in the same subjects showed a free dopamine excretion of 68.88 +- 17.70 nmol/h. There was a significant correlation (P < 0.01) between plasma DOPA concentration and urine free dopamine excretion (r = 0.84). After the oral administration of 250 mg levodopa, plasma DOPA and urine dopamine both increased by a similar proportion (98 +- 8.4-fold, and 93.4 +- 6.9-fold respectively). These compare with an increase in plasma dopamine of only 26 +- 15-fold (P<0.01). Following the oral dose of DOPA, the increase in plasma DOPA, but not plasma dopamine, could account for the increase in urine dopamine. The calculated clearance of plasma DOPA by renal decarboxylation to dopamine was 114 +- 20 ml/min. This is not significantly different from the apparent clearance of endogenous DOPA by renal decarboxylation to dopamine, and suggests that there is adequate renal decarboxylase activity for DOPA to be the precursor for renal dopamine formation. (author)

Sequencing and transcriptional analysis of the Streptococcus thermophilus histamine biosynthesis gene cluster: factors that affect differential hdcA expression

DEFF Research Database (Denmark)

Calles-Enríquez, Marina; Hjort, Benjamin Benn; Andersen, Pia Skov

2010-01-01

to produce histamine. The hdc clusters of S. thermophilus CHCC1524 and CHCC6483 were sequenced, and the factors that affect histamine biosynthesis and histidine-decarboxylating gene (hdcA) expression were studied. The hdc cluster began with the hdcA gene, was followed by a transporter (hdcP), and ended...... with the hdcB gene, which is of unknown function. The three genes were orientated in the same direction. The genetic organization of the hdc cluster showed a unique organization among the lactic acid bacterial group and resembled those of Staphylococcus and Clostridium species, thus indicating possible...... acquisition through a horizontal transfer mechanism. Transcriptional analysis of the hdc cluster revealed the existence of a polycistronic mRNA covering the three genes. The histidine-decarboxylating gene (hdcA) of S. thermophilus demonstrated maximum expression during the stationary growth phase, with high...

Biological roles of crop NADP-malic enzymes and molecular ...

African Journals Online (AJOL)

刘增辉

2011-06-08

Jun 8, 2011 ... catalyze the oxidative decarboxylation of malate to produce pyruvate, CO2 and .... causes dryness of soil and atmosphere, which can limit the plant ... closing through regulate the degradation of malic in day. In addition, there ...

Uptake kinetics and biodistribution of C-14-D-luciferin-a radiolabeled substrate for the firefly luciferase catalyzed bioluminescence reaction : impact on bioluminescence based reporter gene imaging

NARCIS (Netherlands)

Berger, Frank; Paulmurugan, Ramasamy; Bhaumik, Srabani; Gambhir, Sanjiv Sam

2008-01-01

Purpose Firefly luciferase catalyzes the oxidative decarboxylation of D-luciferin to oxyluciferin in the presence of cofactors, producing bioluminescence. This reaction is used in optical bioluminescence-based molecular imaging approaches to detect the expression of the firefly luciferase reporter

Self-assembly in mixtures of sodium alkyl sulfates and alkyltrimethylammonium bromides : Aggregation behavior and catalytic properties

NARCIS (Netherlands)

Talhout, Reinskje; Engberts, BFN

1997-01-01

Two aqueous mixtures of cationic and anionic surfactants have been studied by means of conductometry, transmission electron microscopy, and microcalorimetry. Their catalytic effects on the decarboxylation of the kinetic probe 6-nitrobenzisoxazole-3-carboxylate (6-NBIC) were also examined in some

PDH regulation in skeletal muscle

DEFF Research Database (Denmark)

Kiilerich, Kristian

Pyruvate dehydrogenase (PDH) decarboxylates pyruvate into acetyl-CoA and links glycolysis with the Krebs cycle. Because PDH is the only step where carbohydrate-derived substrate can enter the mitochondria and become completely oxidized, PDH activity can potentially determine if glycogen / glucose...

Solution structures of lipoyl domains of the 2-oxo acid dehydrogenase complexes from Azotobacter vinelandii : implications for molecular recognition

NARCIS (Netherlands)

Berg, A.

1997-01-01

The 2-oxo acid dehydrogenase complexes are large multienzyme complexes that catalyse the irreversible oxidative decarboxylation of a specific 2-oxo acid to the corresponding acyl-CoA derivative. The pyruvate dehydrogenase complex (PDHC) converts the product of the glycolysis, pyruvate, to

The Relationship among Tyrosine Decarboxylase and Agmatine Deiminase Pathways in Enterococcus faecalis

NARCIS (Netherlands)

Perez, Marta; Ladero, Victor; del Rio, Beatriz; Redruello, Begona; de Jong, Anne; Kuipers, Oscar; Kok, Jan; Martin, M. Cruz; Fernandez, Maria; Alvarez, Miguel A.

2017-01-01

Enterococci are considered mainly responsible for the undesirable accumulation of the biogenic amines tyramine and putrescine in cheeses. The biosynthesis of tyramine and putrescine has been described as a species trait in Enterococcus faecalis. Tyramine is formed by the decarboxylation of the amino

Pathophysiological and pharmacotherapeutic aspects of serotonin and serotonergic drugs

NARCIS (Netherlands)

van Zwieten, P. A.; Blauw, G. J.; van Brummelen, P.

1990-01-01

A survey shall be given on the physiological, pathophysiological and pharmacotherapeutic backgrounds of the biogenic amine 5-hydroxytryptamine (serotonin; 5HT), to be preceded by a few historical remarks. 5HT is biosynthesized from L-tryptophan via hydroxylation and subsequent decarboxylation. 5HT

Biosynthesis of iridoids lacking C-10 and the chemotaxonomic implications of their distribution

DEFF Research Database (Denmark)

Frederiksen, Lotte Boe; Damtoft, Søren; Jensen, Søren Rosendal

1999-01-01

Continuing earlier experiments in which deoxyloganic acid proved to be a precursor of the doubly decarboxylated iridoids in Thunbergia alata, we have now shown that deuterium labelled 6-deoxyretzioside was incorporated into stilbericoside in this plant. In the same experiment labelled retzioside...

In vitro radiation and chemotherapy sensitivity of established cell lines of human small cell lung cancer and its large cell morphological variants

International Nuclear Information System (INIS)

Carney, D.N.; Mitchell, J.B.; Kinsella, T.J.

1983-01-01

The in vitro response to radiation and chemotherapeutic drugs of cell lines established from 7 patients with small cell (SC) lung cancer were tested using a soft agarose clonogenic assay. Five cell lines retained the typical morphological and biochemical amine precursor uptake decarboxylation characteristics of SC, while two cell lines had undergone ''transformation'' to large cell (LC) morphological variants with loss of amine precursor uptake decarboxylation cell characteristics of SC. The radiation survival curves for the SC lines were characterized by D0 values ranging from 51 to 140 rads and extrapolation values (n) ranging from 1.0 to 3.3. While the D0 values of the radiation survival curves of the LC variants were similar (91 and 80 rads), the extrapolation values were 5.6 and 11.1 In vitro chemosensitivity testing of the cell lines revealed an excellent correlation between prior treatment status of the patient and in vitro sensitivity or resistance. No correlation was observed between in vitro chemosensitivity and radiation response. These data suggest that transformation of SC to LC with loss of amine precursor uptake and decarboxylation characteristics is associated with a marked increase in radiation resistance (n) in vitro. The observation of a 2- to 5-fold increase in survival of the LC compared to the SC lines following 200 rads suggests that the use of larger daily radiation fractions and/or radiation-sensitizing drugs might lead to a significantly greater clinical response in patients with LC morphology. This clinical approach may have a major impact on patient response and survival

Remediation of Cu metal-induced accelerated Fenton reaction by potato peels bio-sorbent.

Science.gov (United States)

Azmat, Rafia; Moin, Sumeira; Saleem, Ailyan

2016-12-01

This article has allied exposure to Ecological Particulate Matter (EPM) and its remediation using potato peel surface (PPC) bio-sorbent on two important edible crops Spinacia oleracea and Luffa acutangula. Fenton reaction acceleration was one of the major stress oxidation reactions as a consequence of iron and copper toxicity, which involve in the formation of hydroxyl radical (OH) through EPM. Results showed that the oxidative stress encouraged by Cu in both species that recruits the degradation of photosynthetic pigments, initiating decline in growth, reduced leaf area and degrade proteins. The plants were cultivated in natural environmental condition in three pots with three replicates like (a) control, (b) Cu treated and (c) treated water. Oxidative stress initiated by metal activity in Cu accumulated plant (b) were controlled, through bio-sorption of metal from contaminated water using PPC; arranged at laboratory scale. The acceleration of Fenton reaction was verified in terms of OH radical generation. These radicals were tested in aqueous extract of leaves of three types of plants via benzoic acid. The benzoic acid acts as a scavenger of OH radical due to which the decarboxylation of benzoic acid cured. Observation on (b) showed more rapid decarboxylation as compared to other plants which showed that Cu activity was much higher in (b) as compared to (a) and (c). The rapid decarboxylation of benzoic acid and lower chlorophyll contents in (b) suggest that Fenton reaction system was much enhanced by Cu-O and Fe-O chemistry that was successfully controlled by PPC which results in restoring the metabolic pathway and nullifying oxidative stress in (c).

Decarboxylation Of Palm And Groundnut Oils In Medium Uv ...

African Journals Online (AJOL)

denise

INTRODUCTION. Vegetable oils undergo appreciable deterioration during processing and storage. The residual free fatty acid (FFA) concentration of vegetable oils is a function of the processing and storage conditions. Vegetable oils spoilage, usually defined as rancidity, is the result of fatty acid moity has been recognized ...

[Research of imidazo[1,2-a]benzimidazole derivatives. XXX. Synthesis and properties of (imidazo[1,2-a]benzimidazolyl-2)acetic acid derivatives].

Science.gov (United States)

Anisimova, V A; Tolpygin, I E; Spasov, A A; Serdiuk, T S; Sukhov, A G

2011-01-01

Ethyl esters of (9-subtituted-imidazo[1,2-a]benzimidazolyl-2)acetic acids were synthesized. The chemical properties of these esters (hydrolysis, decarboxylation, hydrazinolysis) and biological activity (fungicidal, antimicrobial, antiarrhythmic activity, and also affects on the brain rhythmogenesis) of the prepared compounds were studied.

Genome Sequence of Lactobacillus saerimneri 30a (Formerly Lactobacillus sp. Strain 30a), a Reference Lactic Acid Bacterium Strain Producing Biogenic Amines

NARCIS (Netherlands)

Romano, Andrea; Trip, Hein; Campbell-Sills, Hugo; Bouchez, Olivier; Sherman, David; Lolkema, Juke S.; Lucas, Patrick M.

2013-01-01

Lactobacillus sp. strain 30a (Lactobacillus saerimneri) produces the biogenic amines histamine, putrescine, and cadaverine by decarboxylating their amino acid precursors. We report its draft genome sequence (1,634,278 bases, 42.6% G+C content) and the principal findings from its annotation, which

Conditions allowing the formation of biogenic amines in cheese

NARCIS (Netherlands)

Joosten, H.M.L.J.

1988-01-01

A study was undertaken to reveal the conditions that allow the formation of biogenic amines in cheese.

The starters most commonly used in the Dutch cheese industry do not have decarboxylative properties. Only if the milk or curd is contaminated with non-starter bacteria, amine

A REVIEW ON ACRYLAMIDE IN FOODS: SOURCES AND ...

African Journals Online (AJOL)

JONATHAN

The acrolein pathway and enzymatic decarboxylation of asparagine, as well as ... suggested that both molecular mobility and sugar reactivity would determine the ... It decomposes non-thermally to form ammonia, and thermal decomposition produces ..... Evaluation of Acrylamide in Food from China by a LC/MS/MS Method.

Synthesis of neurotransmitter GABA via the neuronal tricarboxylic acid cycle is elevated in rats with liver cirrhosis consistent with a high GABAergic tone in chronic hepatic encephalopathy

DEFF Research Database (Denmark)

Leke, Renata; Bak, Lasse Kristoffer; Iversen, Peter

2011-01-01

J. Neurochem. (2011) 117, 824-832. ABSTRACT: Hepatic encephalopathy (HE) is a neuropsychiatric complication to liver disease. It is known that ammonia plays a role in the pathogenesis of HE and disturbances in the GABAergic system have been related to HE. Synthesis of GABA occurs by decarboxylation...

Thermodynamic properties and cloud droplet activation of a series of oxo-acids

Directory of Open Access Journals (Sweden)

M. Frosch

2010-07-01

Full Text Available We have investigated the thermodynamic properties of four aliphatic oxo-dicarboyxlic acids identified or thought to be present in atmospheric particulate matter: oxosuccinic acid, 2-oxoglutaric acid, 3-oxoglutaric acid, and 4-oxopimelic acid. The compounds were characterized in terms of their cloud condensation nuclei (CCN activity, vapor pressure, density, and tendency to decarboxylate in aqueous solution. We deployed a variety of experimental techniques and instruments: a CCN counter, a Tandem Differential Mobililty Analyzer (TDMA coupled with a laminar flow-tube, and liquid chromatography/mass spectrometry (LC/MS. The presence of the oxo functional group in the α-position causes the vapor pressure of the compounds to diminish by an order of magnitude with respect to the parent dicarboxylic acid, while the CCN activity is similar or increased. Dicarboxylic acids with an oxo-group in the β-position decarboxylate in aqueous solution. We studied the effects of this process on our measurements and findings.

Does exercise stimulate protein breakdown in humans? Isotopic approaches to the problem

International Nuclear Information System (INIS)

Wolfe, R.R.

1987-01-01

Protein metabolism in exercise has been investigated for 100 yr, yet it is still unclear if exercise induces an increased rate of protein breakdown. We have recently addressed this general question in a series of experiments in human subjects using stable isotopic tracers. In this paper, the results of those studies are reviewed. We have found that in light exercise the de-carboxylation of leucine is increased. However, urea production is not increased correspondingly, nor is the rate of incorporation into urea of nitrogen from either leucine or lysine. Further complicating the picture is the fact that lysine de-carboxylation is not markedly elevated in exercise. From these studies, we must conclude that isotopic techniques which have achieved general acceptance in other circumstances cannot reliably be used to answer the question of whether exercise stimulates protein breakdown in humans. However, these methods do provide results which enable a better understanding of the metabolism of the individual amino acids in exercise

Carbon isotope effects in carbohydrates and amino acids of photosynthesizing organisms

International Nuclear Information System (INIS)

Ivlev, A.A.; Kaloshin, A.G.; Koroleva, M.Ya.

1982-01-01

The analysis of the carbon isotope distribution in carbohydrates and amino acids of some photosynthesizing organisms revealed the close relationship between distribution and the pathways of biosynthesis of the molecules. This relationship is explained on the basis of the previously proposed mechanism of carbon isotope fractionation in a cell, in which the chief part is played by kinetic isotope effects in the pyruvate decarboxylation reaction progressively increased in the conjugated processes of gluconeogenesis. Isotope differences of C 2 and C 3 fragments arising in decarboxylation of pyruvate, as well as isotope differences of biogenic acceptor and environmental CO 2 appearing in assimilation are the main reasons of the observed intramolecular isotopic heterogeneity of biomolecules. The heterogeneity is preserved in metabolites owing to an incomplete mixing of carbon atoms in biochemical reactions. The probable existence of two pools of carbohydrates in photosynthesizing organisms different in isotopic composition is predicted. Two types of intramolecular isotope distribution in amino acids are shown. (author)

Carbon isotope effects in carbohydrates and amino acids of photosynthesizing organisms

Energy Technology Data Exchange (ETDEWEB)

Ivlev, A.A.; Kaloshin, A.G.; Koroleva, M.Ya. (Ministerstvo Geologii SSR, Moscow)

1982-02-10

The analysis of the carbon isotope distribution in carbohydrates and amino acids of some photosynthesizing organisms revealed the close relationship between distribution and the pathways of biosynthesis of the molecules. This relationship is explained on the basis of the previously proposed mechanism of carbon isotope fractionation in a cell, in which the chief part is played by kinetic isotope effects in the pyruvate decarboxylation reaction progressively increased in the conjugated processes of gluconeogenesis. Isotope differences of C/sub 2/ and C/sub 3/ fragments arising in decarboxylation of pyruvate, as well as isotope differences of biogenic acceptor and environmental CO/sub 2/ appearing in assimilation are the main reasons of the observed intramolecular isotopic heterogeneity of biomolecules. The heterogeneity is preserved in metabolites owing to an incomplete mixing of carbon atoms in biochemical reactions. The probable existence of two pools of carbohydrates in photosynthesizing organisms different in isotopic composition is predicted. Two types of intramolecular isotope distribution in amino acids are shown.

Influence of Solvent on Liquid Phase Hydrodeoxygenation of Furfural-Acetone Condensation Adduct using Ni/Al2O3-ZrO2 Catalysts

Science.gov (United States)

Ulfa, S. M.; Mahfud, A.; Nabilah, S.; Rahman, M. F.

2017-02-01

Influence of water and acidic protic solvent on hydrodeoxygenation (HDO) of the furfural-acetone adduct (FAA) over Ni/Al2O3-ZrO2 (NiAZ) catalysts were investigated. The HDO of FAA was carried out in a batch reactor at 150°C for 8 hours. The NiAZ catalysts were home-made catalysts which were prepared by wet impregnation method with 10 and 20% nickel loading. The HDO reaction of FAA using 10NiAZ in water at 150°C gave alkane and oxygenated hydrocarbons at 31.41% with selectivity over tridecane (C13) in 6.67%. On the other hand, a reaction using acetic acid:water (1:19 v/v) in similar reaction condition gave only oxygenated compounds and hydrocracking product (C8-C10). The formation of tridecane (C13) was proposed by hydrogenation of C=O and C=C followed by decarboxylation without hydrocracking process. The presence of water facilitated decarboxylation mechanism by stabilized dehydrogenated derivatives of FAA.

Benzalacetone Synthase

Directory of Open Access Journals (Sweden)

Ikuro eAbe

2012-03-01

Full Text Available Benzalacetone synthase, from the medicinal plant Rheum palmatum (Polygonaceae (RpBAS, is a plant-specific chalcone synthase (CHS superfamily of type III polyketide synthase (PKS. RpBAS catalyzes the one-step, decarboxylative condensation of 4-coumaroyl-CoA with malonyl-CoA to produce the C6-C4 benzalacetone scaffold. The X-ray crystal structures of RpBAS confirmed that the diketide-forming activity is attributable to the characteristic substitution of the conserved active-site "gatekeeper" Phe with Leu. Furthermore, the crystal structures suggested that RpBAS employs novel catalytic machinery for the thioester bond cleavage of the enzyme-bound diketide intermediate and the final decarboxylation reaction to produce benzalacetone. Finally, by exploiting the remarkable substrate tolerance and catalytic versatility of RpBAS, precursor-directed biosynthesis efficiently generated chemically and structurally divergent, unnatural novel polyketide scaffolds. These findings provided a structural basis for the functional diversity of the type III PKS enzymes.

Kinetic determinations of accurate relative oxidation potentials of amines with reactive radical cations.

Science.gov (United States)

Gould, Ian R; Wosinska, Zofia M; Farid, Samir

2006-01-01

Accurate oxidation potentials for organic compounds are critical for the evaluation of thermodynamic and kinetic properties of their radical cations. Except when using a specialized apparatus, electrochemical oxidation of molecules with reactive radical cations is usually an irreversible process, providing peak potentials, E(p), rather than thermodynamically meaningful oxidation potentials, E(ox). In a previous study on amines with radical cations that underwent rapid decarboxylation, we estimated E(ox) by correcting the E(p) from cyclic voltammetry with rate constants for decarboxylation obtained using laser flash photolysis. Here we use redox equilibration experiments to determine accurate relative oxidation potentials for the same amines. We also describe an extension of these experiments to show how relative oxidation potentials can be obtained in the absence of equilibrium, from a complete kinetic analysis of the reversible redox kinetics. The results provide support for the previous cyclic voltammetry/laser flash photolysis method for determining oxidation potentials.

Tyramine-O-sulfate is produced and secreted by human hepatoma cells, line HepG2

International Nuclear Information System (INIS)

Liu, M.C.; Yu, S.; Suiko, M.

1987-01-01

Human hepatoma cells, line HepG2, were metabolically labeled with [ 35 S]sulfate. The spent medium separated following 24 hr labeling was subjected to ultrafiltration using an Amicon Centricon unit. The filtrate obtained was analyzed by a two-dimensional separation procedure combining high-voltage electrophoresis and thin-layer chromatography. The autoradiograph taken from the cellulose thin-layer plate following the analysis revealed the presence of tyramine-O-[ 35 ]sulfate in addition to tyrosine-O-[ 35 ]sulfate. Using adenosine, 3'-phosphate, 5'-phospho[ 35 S]sulfate as the sulfate donor, it was shown that tyramine was actively sulfated to form tyramine-O-[ 35 S]sulfate as catalyzed by the sulfotransferase(s) present in dog liver homogenate. Attempts to decarboxylate tyrosine-O-sulfate to tyramine-O-sulfate using intrinsic p-tyrosine decarboxylase present in dog liver homogenate, however, were unsuccessful. Employing purified Streptococcus faecalis tyrosine decarboxylase, it was shown that L-tyrosine was actively decarboxylated to tyramine, whereas tyrosine-O-sulfate could not serve as a substrate

Deuterium labelling studies with unsaturated acids and nitriles

International Nuclear Information System (INIS)

Desai, U.V.; Mane, R.B.

1986-01-01

α-Deuteriated α,β-unsaturated acids have been prepared by Knoevenagel condensation of aldehydes with deuteriated malonic acid. The decarboxylation of α,β-unsaturated cyano acid with pyridine/D 2 O yields α- and γ-labelled nitriles. The deuterium incorporation is studied by pmr spectroscopy. (author). 8 refs

Rapid synthesis of polyprenylated acylphloroglucinol analogs via dearomative conjunctive allylic annulation.

Science.gov (United States)

Grenning, Alexander J; Boyce, Jonathan H; Porco, John A

2014-08-20

Polyprenylated acylphloroglucinols (PPAPs) are structurally complex natural products with promising biological activities. Herein, we present a biosynthesis-inspired, diversity-oriented synthesis approach for rapid construction of PPAP analogs via double decarboxylative allylation (DcA) of acylphloroglucinol scaffolds to access allyl-desoxyhumulones followed by dearomative conjunctive allylic alkylation (DCAA).

A Multistep Synthesis Featuring Classic Carbonyl Chemistry for the Advanced Organic Chemistry Laboratory

Science.gov (United States)

Duff, David B.; Abbe, Tyler G.; Goess, Brian C.

2012-01-01

A multistep synthesis of 5-isopropyl-1,3-cyclohexanedione is carried out from three commodity chemicals. The sequence involves an aldol condensation, Dieckmann-type annulation, ester hydrolysis, and decarboxylation. No purification is required until after the final step, at which point gravity column chromatography provides the desired product in…

Transcriptomic profile of aguR deletion mutant of Lactococcus lactis subsp. cremoris CECT 8666

NARCIS (Netherlands)

Del Rio, Beatriz; Linares, Daniel M; Redruello, Begoña; Martin, Maria Cruz; Fernandez, Maria; de Jong, Anne; Kuipers, Oscar P; Ladero, Victor; Alvarez, Miguel A

2015-01-01

Lactococcus lactis subsp. cremoris CECT 8666 (formerly GE2-14) is a dairy strain that catabolizes agmatine (a decarboxylated derivative of arginine) into the biogenic amine putrescine by the agmatine deiminase (AGDI) pathway [1]. The AGDI cluster of L. lactis is composed by five genes aguR, aguB,

Potential risks from UV/H2O2 oxidation and UV photocatalysis: A review of toxic, assimilable, and sensory-unpleasant transformation products.

Science.gov (United States)

Wang, Wen-Long; Wu, Qian-Yuan; Huang, Nan; Xu, Zi-Bin; Lee, Min-Yong; Hu, Hong-Ying

2018-05-15

UV based advanced oxidation processes (UV-AOPs) that efficiently eliminate organic pollutants during water treatment have been the subject of numerous investigations. Most organic pollutants are not completely mineralized during UV-AOPs but are partially oxidized into transformation products (TPs), thereby adding complexity to the treated water and posing risks to humans, ecological systems, and the environment. While the degradation kinetics and mechanisms of pollutants have been widely documented, there is little information about the risks associated with TPs. In this review, we have collated recent knowledge about the harmful TPs that are generated in UV/H 2 O 2 and UV photocatalysis, two UV-AOPs that have been studied extensively. Toxic and assimilable TPs were ubiquitously observed in more than 80% of UV-AOPs of organic pollutants, of which the toxicity and assimilability levels changed with variations in the reaction conditions, such as the UV fluence and oxidant dosage. Previous studies and modeling assessments showed that toxic and assimilable TPs may be generated during hydroxylation, dealkylation, decarboxylation, and deamination. Among various reactions, TPs generated from dealkylation and decarboxylation were generally less and more toxic than the parent pollutants, respectively; TPs generated from decarboxylation and deamination were generally less and more assimilable than the parent pollutants, respectively. There is also potential concern about the sensory-unpleasant TPs generated by oxidations and subsequent metabolism of microorganisms. In this overview, we stress the need to include both the concentrations of organic pollutants and the evaluations of the risks from TPs for the quality assessments of the water treated by UV-AOPs. Copyright © 2018 Elsevier Ltd. All rights reserved.

In Vivo Testing of Extracorporeal Membrane Ventilators: iLA-Activve Versus Prototype I-Lung.

Science.gov (United States)

Kischkel, Sabine; Bergt, Stefan; Brock, Beate; von Grönheim, Johan; Herbst, Anne; Epping, Marc-Jonas; Matheis, Georg; Novosel, Esther; Schneider, Joerg; Warnke, Philipp; Podbielski, Andreas; Roesner, Jan P; Lelkes, Peter I; Vollmar, Brigitte

A side-by-side comparison of the decarboxylation efficacy of two pump-driven venovenous extracorporeal lung assist devices, i.e., a first prototype of the new miniaturized ambulatory extracorporeal membrane ventilator, I-lung versus the commercial system iLA-activve for more than a period of 72 hours in a large animal model. Fifteen German Landrace pigs were anesthetized and underwent mechanical hypoventilation to induce severe hypercapnia. Decarboxylation was accomplished by either the I-lung or the iLA-activve via a double lumen catheter in the jugular vein. Sham-operated pigs were not connected to extracorporeal devices. Cardiovascular, respiratory, and metabolic parameters were continuously monitored, combined with periodic arterial blood sampling for subsequent clinical blood diagnostics, such as gas exchange, hemolysis, coagulation parameters, and cytokine profiles. At the termination of the studies, lung tissue was harvested and examined histologically for pulmonary morphology and leukocyte tissue infiltration. Both extracorporeal devices showed high and comparable efficacy with respect to carbon dioxide elimination for more than 72 hours and were not associated with either bleeding events or clotting disorders. Pigs of both groups showed cardiovascular and hemodynamic stability without marked differences to sham-operated animals. Groups also did not differ in terms of inflammatory and metabolic parameters. We established a preclinical in vivo porcine model for comparative long-term testing of I-lung and iLA-activve. The I-lung prototype proved to be safe and feasible, providing adequate decarboxylation without any adverse events. Once translated into the clinical treatment, the new miniaturized and transportable I-lung device might represent a promising tool for treating awake and mobilized patients with decompensated pulmonary disorders.

Extensive Literature Search on the “Effects of Copper intake levels in the gut microbiota profile of target animals, in particular piglets"

DEFF Research Database (Denmark)

Jensen, Bent Borg

74%, the urease activity in the colon, and decarboxylation and deamination of amino acidsin the small intestine. No effect of Cu as CuSO4 on the population of streptococci and on ureaseactivity is seen in piglets. Supplementing piglet diets with 100 to 250 mg/kg Cu as CuSO4 significantlychange...

Synthesis and reactivity of aliphatic sulfur pentafluorides from substituted (pentafluorosulfanyl)benzenes

Czech Academy of Sciences Publication Activity Database

Vida, Norbert; Václavík, Jiří; Beier, Petr

2016-01-01

Roč. 12, Jan 20 (2016), s. 110-116 ISSN 1860-5397 Institutional support: RVO:61388963 Keywords : dearomatization * decarboxylation * Diels-Alder reaction * oxidation * pentafluorosulfanyl group Subject RIV: CC - Organic Chemistry Impact factor: 2.337, year: 2016 http://www.beilstein-journals.org/bjoc/single/articleFullText.htm?publicId=1860-5397-12-12

Process for conversion of levulinic acid to ketones

Energy Technology Data Exchange (ETDEWEB)

Dagle, Vanessa M.; Dagle, Robert A.

2017-05-30

A method for generating desired platform chemicals from feedstocks such as cellulosic biomass feedstocks containing levulinic acid by decarboxylating a feed stock comprising levulinic acid to generate ketones. This is done by passing a feed stock comprising levulinic acid in a gas phase over a non-precious metal catalyst on a neutral support.

Topology of AspT, the aspartate:alanine antiporter of Tetragenococcus halophilus, determined by site-directed fluorescence labeling.

Science.gov (United States)

Nanatani, Kei; Fujiki, Takashi; Kanou, Kazuhiko; Takeda-Shitaka, Mayuko; Umeyama, Hideaki; Ye, Liwen; Wang, Xicheng; Nakajima, Tasuku; Uchida, Takafumi; Maloney, Peter C; Abe, Keietsu

2007-10-01

The gram-positive lactic acid bacterium Tetragenococcus halophilus catalyzes the decarboxylation of L-aspartate (Asp) with release of L-alanine (Ala) and CO(2). The decarboxylation reaction consists of two steps: electrogenic exchange of Asp for Ala catalyzed by an aspartate:alanine antiporter (AspT) and intracellular decarboxylation of the transported Asp catalyzed by an L-aspartate-beta-decarboxylase (AspD). AspT belongs to the newly classified aspartate:alanine exchanger family (transporter classification no. 2.A.81) of transporters. In this study, we were interested in the relationship between the structure and function of AspT and thus analyzed the topology by means of the substituted-cysteine accessibility method using the impermeant, fluorescent, thiol-specific probe Oregon Green 488 maleimide (OGM) and the impermeant, nonfluorescent, thiol-specific probe [2-(trimethylammonium)ethyl]methanethiosulfonate bromide. We generated 23 single-cysteine variants from a six-histidine-tagged cysteineless AspT template. A cysteine position was assigned an external location if the corresponding single-cysteine variant reacted with OGM added to intact cells, and a position was assigned an internal location if OGM labeling required cell lysis. The topology analyses revealed that AspT has a unique topology; the protein has 10 transmembrane helices (TMs), a large hydrophilic cytoplasmic loop (about 180 amino acids) between TM5 and TM6, N and C termini that face the periplasm, and a positively charged residue (arginine 76) within TM3. Moreover, the three-dimensional structure constructed by means of the full automatic modeling system indicates that the large hydrophilic cytoplasmic loop of AspT possesses a TrkA_C domain and a TrkA_C-like domain and that the three-dimensional structures of these domains are similar to each other even though their amino acid sequences show low similarity.

Topology of AspT, the Aspartate:Alanine Antiporter of Tetragenococcus halophilus, Determined by Site-Directed Fluorescence Labeling▿ †

Science.gov (United States)

Nanatani, Kei; Fujiki, Takashi; Kanou, Kazuhiko; Takeda-Shitaka, Mayuko; Umeyama, Hideaki; Ye, Liwen; Wang, Xicheng; Nakajima, Tasuku; Uchida, Takafumi; Maloney, Peter C.; Abe, Keietsu

2007-01-01

The gram-positive lactic acid bacterium Tetragenococcus halophilus catalyzes the decarboxylation of l-aspartate (Asp) with release of l-alanine (Ala) and CO2. The decarboxylation reaction consists of two steps: electrogenic exchange of Asp for Ala catalyzed by an aspartate:alanine antiporter (AspT) and intracellular decarboxylation of the transported Asp catalyzed by an l-aspartate-β-decarboxylase (AspD). AspT belongs to the newly classified aspartate:alanine exchanger family (transporter classification no. 2.A.81) of transporters. In this study, we were interested in the relationship between the structure and function of AspT and thus analyzed the topology by means of the substituted-cysteine accessibility method using the impermeant, fluorescent, thiol-specific probe Oregon Green 488 maleimide (OGM) and the impermeant, nonfluorescent, thiol-specific probe [2-(trimethylammonium)ethyl]methanethiosulfonate bromide. We generated 23 single-cysteine variants from a six-histidine-tagged cysteineless AspT template. A cysteine position was assigned an external location if the corresponding single-cysteine variant reacted with OGM added to intact cells, and a position was assigned an internal location if OGM labeling required cell lysis. The topology analyses revealed that AspT has a unique topology; the protein has 10 transmembrane helices (TMs), a large hydrophilic cytoplasmic loop (about 180 amino acids) between TM5 and TM6, N and C termini that face the periplasm, and a positively charged residue (arginine 76) within TM3. Moreover, the three-dimensional structure constructed by means of the full automatic modeling system indicates that the large hydrophilic cytoplasmic loop of AspT possesses a TrkA_C domain and a TrkA_C-like domain and that the three-dimensional structures of these domains are similar to each other even though their amino acid sequences show low similarity. PMID:17660287

Mechanistic photodecarboxylation of pyruvic acid: Excited-state proton transfer and three-state intersection

Science.gov (United States)

Chang, Xue-Ping; Fang, Qiu; Cui, Ganglong

2014-10-01

Photodissociation dynamics of pyruvic acid experimentally differs from that of commonly known ketones. We have employed the complete active space self-consistent field and its multi-state second-order perturbation methods to study its photodissociation mechanism in the S0, T1, and S1 states. We have uncovered four nonadiabatic photodecarboxylation paths. (i) The S1 system relaxes via an excited-state intramolecular proton transfer (ESIPT) to a hydrogen-transferred tautomer, near which an S1/S0 conical intersection funnels the S1 to S0 state. Then, some trajectories continue completing the decarboxylation reaction in the S0 state; the remaining trajectories via a reverse hydrogen transfer return to the S0 minimum, from which a thermal decarboxylation reaction occurs. (ii) Due to a small S1 -T1 energy gap and a large S1/T1 spin-orbit coupling, an efficient S1 → T1 intersystem crossing process happens again near this S1/S0 conical intersection. When decaying to T1 state, a direct photodecarboxylation proceeds. (iii) Prior to ESIPT, the S1 system first decays to the T1 state via an S1 → T1 intersystem crossing; then, the T1 system evolves to a hydrogen-transferred tautomer. Therefrom, an adiabatic T1 decarboxylation takes place due to a small barrier of 7.7 kcal/mol. (iv) Besides the aforementioned T1 ESIPT process, there also exists a comparable Norrish type I reaction in the T1 state, which forms the ground-state products of CH3CO and COOH. Finally, we have found that ESIPT plays an important role. It closes the S1-T1 and S1-S0 energy gaps, effecting an S1/T1/S0 three-state intersection region, and mediating nonadiabatic photodecarboxylation reactions of pyruvic acid.

Fatty acid synthesis by spinach chloroplasts, 2

International Nuclear Information System (INIS)

Yamada, Mitsuhiro; Nakamura, Yasunori

1975-01-01

By incorporation of 3 H 2 O into the fatty acid chain in the presence of unlabelled precursor, we showed that fatty acids are synthesized from PGA, PEP and pyruvate by intact spinach chloroplasts in the light. 13 C-tracer experiments confirmed that 1-C of pyruvate is decarboxylated and 2-C is incorporated into fatty acids by the chloroplasts. The patterns of fatty acids synthesized from PGA and pyruvate were the same as that from acetate. The highest rate of fatty acid synthesis was reached at the physiological concentration of PGA (3 mM) and pyruvate (1 mM). These results indicate the operation of the following path in the chloroplasts in light: PGA→PEP→pyruvate→acetylCoA→fatty acids. Since citrate and OAA were much less active and malate and glyoxylate were inert as precursors for fatty acid synthesis, PEP or pyruvate carboxylation, citrate lyase reaction and malate synthetase reaction are not involved in the formation of acetylCoA and fatty acids. Since pyruvate was much more effective as a substrate for fatty acid synthesis than lactate, acetaldehyde or acetate, direct decarboxylation path is considered to be the primary path from pyruvate to acetylCoA. The insignificant effect of chloroplast-washing on fatty acid synthesis from PGA and pyruvate indicates that the glycolytic path from PGA to pyruvate is associated with the chloroplasts. Since pyruvate was more effectively incorporated into fatty acids than acetylCoA, it is unlikely that pyruvate decarboxylation to acetylCoA is due to mitochondria contaminating the chloroplast preparation. On the basis of measurements of 3 H 2 O incorporation in the light and dark, the activity of fatty acid synthesis in spincah leaves appears to be shared by the activities in chloroplasts (87%) and other organelles (13%). (author)

Tetrahydrocannabinolic acid is a potent PPARγ agonist with neuroprotective activity.

Science.gov (United States)

Nadal, Xavier; Del Río, Carmen; Casano, Salvatore; Palomares, Belén; Ferreiro-Vera, Carlos; Navarrete, Carmen; Sánchez-Carnerero, Carolina; Cantarero, Irene; Bellido, Maria Luz; Meyer, Stefan; Morello, Gaetano; Appendino, Giovanni; Muñoz, Eduardo

2017-12-01

Phytocannabinoids are produced in Cannabis sativa L. in acidic form and are decarboxylated upon heating, processing and storage. While the biological effects of decarboxylated cannabinoids such as Δ 9 -tetrahydrocannabinol have been extensively investigated, the bioactivity of Δ 9 -tetahydrocannabinol acid (Δ 9 -THCA) is largely unknown, despite its occurrence in different Cannabis preparations. Here we have assessed possible neuroprotective actions of Δ 9 -THCA through modulation of PPARγ pathways. The effects of six phytocannabinoids on PPARγ binding and transcriptional activity were investigated. The effect of Δ 9 -THCA on mitochondrial biogenesis and PPARγ coactivator 1-α expression was investigated in Neuro-2a (N2a) cells. The neuroprotective effect was analysed in STHdh Q111/Q111 cells expressing a mutated form of the huntingtin protein and in N2a cells infected with an adenovirus carrying human huntingtin containing 94 polyQ repeats (mHtt-q94). The in vivo neuroprotective activity of Δ 9 -THCA was investigated in mice intoxicated with the mitochondrial toxin 3-nitropropionic acid (3-NPA). Cannabinoid acids bind and activate PPARγ with higher potency than their decarboxylated products. Δ 9 -THCA increased mitochondrial mass in neuroblastoma N2a cells and prevented cytotoxicity induced by serum deprivation in STHdh Q111/Q111 cells and by mutHtt-q94 in N2a cells. Δ 9 -THCA, through a PPARγ-dependent pathway, was neuroprotective in mice treated with 3-NPA, improving motor deficits and preventing striatal degeneration. In addition, Δ 9 -THCA attenuated microgliosis, astrogliosis and up-regulation of proinflammatory markers induced by 3-NPA. Δ 9 -THCA shows potent neuroprotective activity, which is worth considering for the treatment of Huntington's disease and possibly other neurodegenerative and neuroinflammatory diseases. © 2017 The British Pharmacological Society.

Correlation between citric acid and nitrate metabolisms during CAM cycle in the atmospheric bromeliad Tillandsia pohliana.

Science.gov (United States)

Freschi, Luciano; Rodrigues, Maria Aurineide; Tiné, Marco Aurélio Silva; Mercier, Helenice

2010-12-15

Crassulacean acid metabolism (CAM) confers crucial adaptations for plants living under frequent environmental stresses. A wide metabolic plasticity can be found among CAM species regarding the type of storage carbohydrate, organic acid accumulated at night and decarboxylating system. Consequently, many aspects of the CAM pathway control are still elusive while the impact of this photosynthetic adaptation on nitrogen metabolism has remained largely unexplored. In this study, we investigated a possible link between the CAM cycle and the nitrogen assimilation in the atmospheric bromeliad Tillandsia pohliana by simultaneously characterizing the diel changes in key enzyme activities and metabolite levels of both organic acid and nitrate metabolisms. The results revealed that T. pohliana performed a typical CAM cycle in which phosphoenolpyruvate carboxylase and phosphoenolpyruvate carboxykinase phosphorylation seemed to play a crucial role to avoid futile cycles of carboxylation and decarboxylation. Unlike all other bromeliads previously investigated, almost equimolar concentrations of malate and citrate were accumulated at night. Moreover, a marked nocturnal depletion in the starch reservoirs and an atypical pattern of nitrate reduction restricted to the nighttime were also observed. Since reduction and assimilation of nitrate requires a massive supply of reducing power and energy and considering that T. pohliana lives overexposed to the sunlight, we hypothesize that citrate decarboxylation might be an accessory mechanism to increase internal CO₂ concentration during the day while its biosynthesis could provide NADH and ATP for nocturnal assimilation of nitrate. Therefore, besides delivering photoprotection during the day, citrate might represent a key component connecting both CAM pathway and nitrogen metabolism in T. pohliana; a scenario that certainly deserves further study not only in this species but also in other CAM plants that nocturnally accumulate citrate

Fatty acid synthesis by spinach chloroplasts, 2. The path from PGA to fatty acids

Energy Technology Data Exchange (ETDEWEB)

Yamada, Mitsuhiro; Nakamura, Yasunori [Tokyo Univ. (Japan). Coll. of General Education

1975-02-01

By incorporation of /sup 3/H/sub 2/O into the fatty acid chain in the presence of unlabelled precursor, we showed that fatty acids are synthesized from PGA, PEP and pyruvate by intact spinach chloroplasts in the light. /sup 13/C-tracer experiments confirmed that 1-C of pyruvate is decarboxylated and 2-C is incorporated into fatty acids by the chloroplasts. The patterns of fatty acids synthesized from PGA and pyruvate were the same as that from acetate. The highest rate of fatty acid synthesis was reached at the physiological concentration of PGA (3 mM) and pyruvate (1 mM). These results indicate the operation of the following path in the chloroplasts in light: PGA..-->..PEP..-->..pyruvate..-->..acetylCoA..-->..fatty acids. Since citrate and OAA were much less active and malate and glyoxylate were inert as precursors for fatty acid synthesis, PEP or pyruvate carboxylation, citrate lyase reaction and malate synthetase reaction are not involved in the formation of acetylCoA and fatty acids. Since pyruvate was much more effective as a substrate for fatty acid synthesis than lactate, acetaldehyde or acetate, direct decarboxylation path is considered to be the primary path from pyruvate to acetylCoA. The insignificant effect of chloroplast-washing on fatty acid synthesis from PGA and pyruvate indicates that the glycolytic path from PGA to pyruvate is associated with the chloroplasts. Since pyruvate was more effectively incorporated into fatty acids than acetylCoA, it is unlikely that pyruvate decarboxylation to acetylCoA is due to mitochondria contaminating the chloroplast preparation. On the basis of measurements of /sup 3/H/sub 2/O incorporation in the light and dark, the activity of fatty acid synthesis in spincah leaves appears to be shared by the activities in chloroplasts (87%) and other organelles (13%).

Behavior of ellagitannins, gallic acid, and ellagic acid under alkaline conditions

Science.gov (United States)

Richard W. Hemingway; W.E. Hillis

1971-01-01

Examination of the rates of hydrolysis of different ellagitannins under conditions comparable with cold soda and alkaline-groundwood pulping processes showed that some ellagitannins are notably resistant to hydrolysis. The rate of hydrolysis was dependent upon the pH and tempemture of the solution and particularly upon the structure of the compound. Decarboxylation of...

Determination of Trichloroacetic Acid in Environmental Studies Using Carbon 14 and Chlorine 36

Czech Academy of Sciences Publication Activity Database

Matucha, Miroslav; Rohlenová, Jana; Forczek, Sándor; Uhlířová, H.; Gryndler, Milan; Fuksová, Květoslava; Schröder, P.

2006-01-01

Roč. 63, č. 11 (2006), s. 1924-1932 ISSN 0045-6535 R&D Projects: GA ČR GA522/02/0874; GA ČR GA526/05/0636 Institutional research plan: CEZ:AV0Z50380511 Keywords : decarboxylation method * forest ecosystem * TCA extraction Subject RIV: DF - Soil Science Impact factor: 2.442, year: 2006

Branched-chain amino acid metabolism in rat muscle: abnormal regulation in acidosis

International Nuclear Information System (INIS)

May, R.C.; Hara, Y.; Kelly, R.A.; Block, K.P.; Buse, M.G.; Mitch, W.E.

1987-01-01

Branched-chain amino acid (BCAA) metabolism is frequently abnormal in pathological conditions accompanied by chronic metabolic acidosis. To study how metabolic acidosis affects BCAA metabolism in muscle, rats were gavage fed a 14% protein diet with or without 4 mmol NH 4 Cl x 100 g body wt -1 x day -1 . Epitrochlearis muscles were incubated with L-[1- 14 C]-valine and L-[1- 14 C]leucine, and rates of decarboxylation, net transamination, and incorporation into muscle protein were measured. Plasma and muscle BCAA levels were lower in acidotic rats. Rates of valine and leucine decarboxylation and net transamination were higher in muscles from acidotic rats; these differences were associated with a 79% increase in the total activity of branched-chain α-keto acid dehydrogenase and a 146% increase in the activated form of the enzyme. They conclude that acidosis affects the regulation of BCAA metabolism by enhancing flux through the transaminase and by directly stimulating oxidative catabolism through activation of branched-chain α-keto acid dehydrogenase

Branched-chain amino acid metabolism in rat muscle: abnormal regulation in acidosis

Energy Technology Data Exchange (ETDEWEB)

May, R.C.; Hara, Y.; Kelly, R.A.; Block, K.P.; Buse, M.G.; Mitch, W.E.

1987-06-01

Branched-chain amino acid (BCAA) metabolism is frequently abnormal in pathological conditions accompanied by chronic metabolic acidosis. To study how metabolic acidosis affects BCAA metabolism in muscle, rats were gavage fed a 14% protein diet with or without 4 mmol NH/sub 4/Cl x 100 g body wt/sup -1/ x day/sup -1/. Epitrochlearis muscles were incubated with L-(1-/sup 14/C)-valine and L-(1-/sup 14/C)leucine, and rates of decarboxylation, net transamination, and incorporation into muscle protein were measured. Plasma and muscle BCAA levels were lower in acidotic rats. Rates of valine and leucine decarboxylation and net transamination were higher in muscles from acidotic rats; these differences were associated with a 79% increase in the total activity of branched-chain ..cap alpha..-keto acid dehydrogenase and a 146% increase in the activated form of the enzyme. They conclude that acidosis affects the regulation of BCAA metabolism by enhancing flux through the transaminase and by directly stimulating oxidative catabolism through activation of branched-chain ..cap alpha..-keto acid dehydrogenase.

Cover picture: Difluoroacetic Acid as a New Reagent for Direct C−H Difluoromethylation of Heteroaromatic Compounds

DEFF Research Database (Denmark)

Thanh Tung, Truong; Christensen, Søren Brøgger; Nielsen, John

2017-01-01

Direct C−H difluoromethylation of electron-deficient positions in nitrogen-containing heterocycles is attained by difluoromethyl radicals generated in-situ from difluoroacetic acid under silver-catalyzed oxidative decarboxylation. Control of the reaction temperature permits either mono- or disubs......- or disubstitution. More information can be found in the Communication by J. Nielsen et al. (DOI: 10.1002/chem.201704261)....

A Catalytic, Asymmetric Formal Synthesis of (+)-Hamigeran B

KAUST Repository

Mukherjee, Herschel

2011-03-04

A concise asymmetric, formal synthesis of (+)-hamigeran B is reported. A Pd-catalyzed, decarboxylative allylic alkylation, employing a trifluoromethylated derivative of t-BuPHOX, is utilized as the enantioselective step to form the critical quaternary carbon center in excellent yield and enantioselectivity. The product is converted in three steps to a late-stage intermediate previously used in the synthesis of hamigeran B.

A Catalytic, Asymmetric Formal Synthesis of (+)-Hamigeran B

KAUST Repository

Mukherjee, Herschel; McDougal, Nolan T.; Virgil, Scott C.; Stoltz, Brian M.

2011-01-01

A concise asymmetric, formal synthesis of (+)-hamigeran B is reported. A Pd-catalyzed, decarboxylative allylic alkylation, employing a trifluoromethylated derivative of t-BuPHOX, is utilized as the enantioselective step to form the critical quaternary carbon center in excellent yield and enantioselectivity. The product is converted in three steps to a late-stage intermediate previously used in the synthesis of hamigeran B.

Aerobic Oxidation of Xylose to Xylaric acid in Water over Pt Catalysts.

Science.gov (United States)

Saha, Basudeb; Sadula, Sunitha

2018-05-02

Energy-efficient catalytic conversion of biomass intermediates to functional chemicals can enable bio-products viable. Herein, we report an efficient and low temperature aerobic oxidation of xylose to xylaric acid, a promising bio-based chemical for the production of glutaric acid, over commercial catalysts in water. Among several heterogeneous catalysts investigated, Pt/C exhibits the best activity. Systematic variation of reaction parameters in the pH range of 2.5 to 10 suggests that the reaction is fast at higher temperatures but high C-C scission of intermediate C5-oxidized products to low carbon carboxylic acids undermines xylaric acid selectivity. The C-C cleavage is also high in basic solution. The oxidation at neutral pH and 60 C achieves the highest xylaric acid yield (64%). O2 pressure and Pt-amount have significant influence on the reactivity. Decarboxylation of short chain carboxylic acids results in formation of CO2, causing some carbon loss; however such decarboxylation is slow in the presence of xylose. The catalyst retained comparable activity, in terms of product selectivity, after five cycles with no sign of Pt leaching. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Simultaneous recovery of benzene-rich oil and metals by steam pyrolysis of metal-poly(ethylene terephthalate) composite waste.

Science.gov (United States)

Kumagai, Shogo; Grause, Guido; Kameda, Tomohito; Yoshioka, Toshiaki

2014-03-18

The possibility of simultaneous recovery of benzene and metals from the hydrolysis of poly(ethylene terephthalate) (PET)-based materials such as X-ray films, magnetic tape, and prepaid cards under a steam atmosphere at a temperature of 450 °C was evaluated. The hydrolysis resulted in metal-containing carbonaceous residue and volatile terephthalic acid (TPA). The effects of metals and additives on the recovery process were also investigated. All metals were quantitatively recovered, and silver, maghemite (γ-Fe2O3), and anatase (TiO2) were recovered without any changes in their crystal structures or compositions. In a second step, TPA was decarboxylized in the presence of calcium oxide (CaO) at 700 °C, producing benzene with an average yield of 34% and purity of 76%. Maghemite (γ-Fe2O3) incorporated in magnetic tape and prepaid cards could decarboxylate TPA. Aluminum present in the prepaid cards produced hydrogen by the reaction with steam. However, the presence of metals had no adverse influence on the recovery of benzene-rich oil in the presence of CaO. Therefore, this method can be applied to PET-based materials containing inorganic substances, which cannot be recycled effectively otherwise.

Deoxygenation of Plant Fatty Acid using NiSnK/ SiO2 as Catalyst

International Nuclear Information System (INIS)

Chiam, L.T.; Tye, C.T.

2013-01-01

Environmental friendly bio-oil which offers supply reliability as a potential alternative fuel, has spurred to rapid development of bio fuels technology. Palm oil is a potential renewable energy source for bio fuels production in the future and Malaysia is one of the world largest palm oil producers. However, undesired oxygen content in the plant fatty acid that contributes to low energy density, high viscosity, and low stability, makes the palm oil not effective to be used as bio fuels directly. In the present study, the performance of silica supported trimetal catalyst, NiSnK/ SiO 2 , on deoxygenation of used palm oil was evaluated. In addition, the effects of operating parameters, such as reaction temperature and weight hourly space velocity were investigated. Conversion of palmitic acid as high as 90 % was achieved in deoxygenation of used palm oil at reaction temperature 350 degree Celsius. In order to have a better understanding on the deoxygenation reaction, model compound system using the major saturated fatty acid in the used palm oil, palmitic acid was also carried out. Palmitic acid was found mainly decarboxylated into n-pentadecane with some decarboxylation and isomerization products. (author)

Free radicals in dicarboxylic acids: an e.s.r. study of radical conversions in γ-irradiated single crystals of glutaric acid and glutaric-2,2,4,4-d4 acid

International Nuclear Information System (INIS)

Bergene, R.; Minegishi, A.; Riesz, P.

1980-01-01

The γ-radiation-induced free radicals in single crystals of glutaric acid and glutaric-2,2,4,4-d 4 acid were studied in the temperature range 77-300 K by e.s.r. techniques. At 77 K the decarboxylation radical and the anion are stabilized. At higher temperatures the decarboxylation radical is found to be converted into a hydrogen abstraction radical with an activation energy of 6.3 +- 0.5 kcal/mole for the non-deuterated crystal. This radical is stable at room temperature. The anion seems to be converted to a unidentified intermediate radical which in turn is converted to the σ-acyl radical. An analysis of the g-value anisotropy and of the 13 C hyperfine splitting variation for this radical in the deuterated crystal is consistent with the assigned radical structure. By heat treatment the σ-acyl radical is converted to another form of the hydrogen abstraction radical with an activation energy of 9.6 +- 0.6 kcal/mole in the deuterated crystal. U.V.-light (lambda= 254 nm) transforms one of the room temperature radicals into the other. (author)

Enantioselective Decarboxylative Alkylation Reactions: Catalyst Development, Substrate Scope, and Mechanistic Studies

Science.gov (United States)

Behenna, Douglas C.; Mohr, Justin T.; Sherden, Nathaniel H.; Marinescu, Smaranda C.; Harned, Andrew M.; Tani, Kousuke; Seto, Masaki; Ma, Sandy; Novák, Zoltán; Krout, Michael R.; McFadden, Ryan M.; Roizen, Jennifer L.; Enquist, John A.; White, David E.; Levine, Samantha R.; Petrova, Krastina V.; Iwashita, Akihiko; Virgil, Scott C.; Stoltz, Brian M.

2012-01-01

α-Quaternary ketones are accessed through novel enantioselective alkylations of allyl and propargyl electrophiles by unstabilized prochiral enolate nucleophiles in the presence of palladium complexes with various phosphinooxazoline (PHOX) ligands. Excellent yields and high enantiomeric excesses are obtained from three classes of enolate precursors: enol carbonates, enol silanes, and racemic β-ketoesters. Each of these substrate classes functions with nearly identical efficiency in terms of yield and enantioselectivity. Catalyst discovery and development, the optimization of reaction conditions, the exploration of reaction scope, and applications in target-directed synthesis are reported. Experimental observations suggest that these alkylation reactions occur through an unusual inner-sphere mechanism involving binding of the prochiral enolate nucleophile directly to the palladium center. PMID:22083969

Enantioselective Decarboxylative Alkylation Reactions: Catalyst Development, Substrate Scope, and Mechanistic Studies

KAUST Repository

Behenna, Douglas C.; Mohr, Justin T.; Sherden, Nathaniel H.; Marinescu, Smaranda C.; Harned, Andrew M.; Tani, Kousuke; Seto, Masaki; Ma, Sandy; Nová k, Zoltá n; Krout, Michael R.; McFadden, Ryan M.; Roizen, Jennifer L.; Enquist, John A.; White, David E.; Levine, Samantha R.; Petrova, Krastina V.; Iwashita, Akihiko; Virgil, Scott C.; Stoltz, Brian M.

2011-01-01

α-Quaternary ketones are accessed through novel enantioselective alkylations of allyl and propargyl electrophiles by unstabilized prochiral enolate nucleophiles in the presence of palladium complexes with various phosphinooxazoline (PHOX) ligands. Excellent yields and high enantiomeric excesses are obtained from three classes of enolate precursor: enol carbonates, enol silanes, and racemic β-ketoesters. Each of these substrate classes functions with nearly identical efficiency in terms of yield and enantioselectivity. Catalyst discovery and development, the optimization of reaction conditions, the exploration of reaction scope, and applications in target-directed synthesis are reported. Experimental observations suggest that these alkylation reactions occur through an unusual inner-sphere mechanism involving binding of the prochiral enolate nucleophile directly to the palladium center.

Enantioselective Decarboxylative Alkylation Reactions: Catalyst Development, Substrate Scope, and Mechanistic Studies

KAUST Repository

Behenna, Douglas C.

2011-11-14

α-Quaternary ketones are accessed through novel enantioselective alkylations of allyl and propargyl electrophiles by unstabilized prochiral enolate nucleophiles in the presence of palladium complexes with various phosphinooxazoline (PHOX) ligands. Excellent yields and high enantiomeric excesses are obtained from three classes of enolate precursor: enol carbonates, enol silanes, and racemic β-ketoesters. Each of these substrate classes functions with nearly identical efficiency in terms of yield and enantioselectivity. Catalyst discovery and development, the optimization of reaction conditions, the exploration of reaction scope, and applications in target-directed synthesis are reported. Experimental observations suggest that these alkylation reactions occur through an unusual inner-sphere mechanism involving binding of the prochiral enolate nucleophile directly to the palladium center.

Alpha-amino acid derivatives and alpha-fluoro ketones by enantioselective decarboxylation

OpenAIRE

Baur, Markus A.

2003-01-01

Die Methode der enantioselektiven Decarboxylierung wurde angewendet, um Enantiomeren-angereicherte alpha-Aminosäurederivate und alpha-Fluorketone zu erhalten. Als Substrate wurden 2-N-Acetylamino-2-alkylmalonsäuremonoethylester beziehungsweise beta-Keto-benzylester verwendet. China-Alkaloide und Derivate davon wurden als Katalysatoren eingesetzt. Die besten erhaltenen Ergebnisse waren N-Acetyl-L-phenylalaninethylester mit 70% Enantiomerenüberschuß unter Verwendung der katalytisch aktiven Base...

Synthesis and Activity of Grape Wood Phytotoxins and Related Compounds

OpenAIRE

S. Perrin-Cherioux; E. Abou-Mansour; R. Tabacchi

2004-01-01

The synthesis of analogues and derivatives of two o-hydroxyphenylacetylenes, eutypine and sterehirsutinal, the main phytotoxins isolated from the culture medium of Eutypa lata and Stereum hirsutum, is reported. Two means of synthesis are described, based on cyclisation, oxidation, oxidative decarboxylation or reduction reactions, and producing o-hydroxyphenylacetylene or benzofuran derivatives. Some of these synthetic compounds were tested on grapevine callus in order to compare t...

Mechanistic photodecarboxylation of pyruvic acid: Excited-state proton transfer and three-state intersection

Energy Technology Data Exchange (ETDEWEB)

Chang, Xue-Ping; Fang, Qiu, E-mail: fangqiu917@bnu.edu.cn; Cui, Ganglong, E-mail: ganglong.cui@bnu.edu.cn [Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875 (China)

2014-10-21

Photodissociation dynamics of pyruvic acid experimentally differs from that of commonly known ketones. We have employed the complete active space self-consistent field and its multi-state second-order perturbation methods to study its photodissociation mechanism in the S{sub 0}, T{sub 1}, and S{sub 1} states. We have uncovered four nonadiabatic photodecarboxylation paths. (i) The S{sub 1} system relaxes via an excited-state intramolecular proton transfer (ESIPT) to a hydrogen-transferred tautomer, near which an S{sub 1}/S{sub 0} conical intersection funnels the S{sub 1} to S{sub 0} state. Then, some trajectories continue completing the decarboxylation reaction in the S{sub 0} state; the remaining trajectories via a reverse hydrogen transfer return to the S{sub 0} minimum, from which a thermal decarboxylation reaction occurs. (ii) Due to a small S{sub 1} −T{sub 1} energy gap and a large S{sub 1}/T{sub 1} spin-orbit coupling, an efficient S{sub 1} → T{sub 1} intersystem crossing process happens again near this S{sub 1}/S{sub 0} conical intersection. When decaying to T{sub 1} state, a direct photodecarboxylation proceeds. (iii) Prior to ESIPT, the S{sub 1} system first decays to the T{sub 1} state via an S{sub 1} → T{sub 1} intersystem crossing; then, the T{sub 1} system evolves to a hydrogen-transferred tautomer. Therefrom, an adiabatic T{sub 1} decarboxylation takes place due to a small barrier of 7.7 kcal/mol. (iv) Besides the aforementioned T{sub 1} ESIPT process, there also exists a comparable Norrish type I reaction in the T{sub 1} state, which forms the ground-state products of CH{sub 3}CO and COOH. Finally, we have found that ESIPT plays an important role. It closes the S{sub 1}-T{sub 1} and S{sub 1}-S{sub 0} energy gaps, effecting an S{sub 1}/T{sub 1}/S{sub 0} three-state intersection region, and mediating nonadiabatic photodecarboxylation reactions of pyruvic acid.

5-(2-18F-fluoroethoxy)-L-tryptophan as a substrate of system L transport for tumor imaging by PET.

Science.gov (United States)

Krämer, Stefanie D; Mu, Linjing; Müller, Adrienne; Keller, Claudia; Kuznetsova, Olga F; Schweinsberg, Christian; Franck, Dominic; Müller, Cristina; Ross, Tobias L; Schibli, Roger; Ametamey, Simon M

2012-03-01

Large neutral l-amino acids are substrates of system L amino acid transporters. The level of one of these, LAT1, is increased in many tumors. Aromatic l-amino acids may also be substrates of aromatic l-amino acid decarboxylase (AADC), the level of which is enhanced in endocrine tumors. Increased amino acid uptake and subsequent decarboxylation result in the intracellular accumulation of the amino acid and its decarboxylation product. (18)F- and (11)C-labeled neutral aromatic amino acids, such as l-3,4-dihydroxy-6-(18)F-fluorophenylalanine ((18)F-FDOPA) and 5-hydroxy-l-[β-(11)C]tryptophan, are thus successfully used in PET to image endocrine tumors. However, 5-hydroxy-l-[β-(11)C]tryptophan has a relatively short physical half-life (20 min). In this work, we evaluated the in vitro and in vivo characteristics of the (18)F-labeled tryptophan analog 5-(2-(18)F-fluoroethoxy)-l-tryptophan ((18)F-l-FEHTP) as a PET probe for tumor imaging. (18)F-l-FEHTP was synthesized by no-carrier-added (18)F fluorination of 5-hydroxy-l-tryptophan. In vitro cell uptake and efflux of (18)F-l-FEHTP and (18)F-FDOPA were studied with NCI-H69 endocrine small cell lung cancer cells, PC-3 pseudoendocrine prostate cancer cells, and MDA-MB-231 exocrine breast cancer cells. Small-animal PET was performed with the respective xenograft-bearing mice. Tissues were analyzed for potential metabolites. (18)F-l-FEHTP specific activity and radiochemical purity were 50-150 GBq/μmol and greater than 95%, respectively. In vitro cell uptake of (18)F-l-FEHTP was between 48% and 113% of added radioactivity per milligram of protein within 60 min at 37°C and was blocked by greater than 95% in all tested cell lines by the LAT1/2 inhibitor 2-amino-2-norboranecarboxylic acid. (18)F-FDOPA uptake ranged from 26% to 53%/mg. PET studies revealed similar xenograft-to-reference tissue ratios for (18)F-l-FEHTP and (18)F-FDOPA at 30-45 min after injection. In contrast to the (18)F-FDOPA PET results, pretreatment with the

Submerged fermentation of Lactobacillus rhamnosus YS9 for γ-aminobutyric acid (GABA) production

OpenAIRE

Lin,Qian

2013-01-01

γ-Aminobutyric acid (GABA) is a major inhibitory neurotransmitter in central nervous system, and its application in drugs and functional foods has attracted great attention. To enhance production of y-aminobutyric acid, Lactobacillus rhamnosus YS9, a strain isolated from Chinese traditional fermented food pickled vegetable, was grown under submerged fermentation. Its cultivation conditions were investigated. When culture pH condition was adjusted to the optimal pH of glutamate decarboxyl...

Benchtop Fluorination of Fluorescent Nanodiamonds on a Preparative Scale: Toward Unusually Hydrophilic Bright Particles

Czech Academy of Sciences Publication Activity Database

Havlík, Jan; Raabová, Helena; Gulka, Michal; Petráková, Vladimíra; Krečmarová, M.; Mašek, V.; Louša, Petr; Štursa, Jan; Boyen, H. G.; Nesládek, M.; Cígler, Petr

2016-01-01

Roč. 26, č. 23 (2016), s. 4134-4142 ISSN 1616-301X R&D Projects: GA MZd(CZ) NV15-33094A; GA MŠk(CZ) LM2011019; GA MŠk(CZ) LO1304; GA ČR(CZ) GA16-16336S Institutional support: RVO:61388963 ; RVO:68378271 ; RVO:61389005 Keywords : nitrogen-vacancy centers * catalyzed decarboxylative fluorination * surface modification Subject RIV: CC - Organic Chemistry Impact factor: 12.124, year: 2016

Development of a Pseudomonas aeruginosa Agmatine Biosensor

OpenAIRE

Gilbertsen, Adam; Williams, Bryan

2014-01-01

Agmatine, decarboxylated arginine, is an important intermediary in polyamine production for many prokaryotes, but serves higher functions in eukaryotes such as nitric oxide inhibition and roles in neurotransmission. Pseudomonas aeruginosa relies on the arginine decarboxylase and agmatine deiminase pathways to convert arginine into putrescine. One of the two known agmatine deiminase operons, aguBA, contains an agmatine sensitive TetR promoter controlled by AguR. We have discovered that this pr...

A practical and improved synthesis of (3S,5S)-3-[(tert-butyloxycarbonyl)methyl]- 5-[(methanesulfonyloxy)methyl]-2- pyrrolidinone.

Science.gov (United States)

Yee, Nathan K; Dong, Yong; Kapadia, Suresh R; Song, Jinhua J

2002-11-29

A practical and improved synthesis of (3S,5S)-3-[(tert-butyloxycarbonyl)methyl]-5-[(methanesulfonyloxy)methyl]-2-pyrrolidinone (1) is described. The key transformations involve a highly efficient reaction sequence consisting of ethoxycarbonylation, alkylation, hydrolysis, and decarboxylation to produce compound 10. The process described herein is practical, robust, and cost-effective, and it has been successfully implemented in a pilot plant to produce a multikilogram quantity of mesylate 1.

Radiation-induced catalysis of fatty acids adsorbed onto clay minerals

International Nuclear Information System (INIS)

Negron-Mendoza, A.; Ramos-Bernal, S.; Colin-Garcia, M.; Mosqueira, F.G.

2015-01-01

We studied the behavior of small fatty (acetic acid) and dicarboxylic acids (succinic and malonic acids) adsorbed onto Na + -montmorillonite (a clay mineral) and exposed to gamma radiation. A decarboxylation reaction was found to predominate when the clay was present. This preferential synthesis promoted the formation of a compound with one less carbon atom than its target compound. In the system without clay, dimerization was the predominate outcome following radiolysis. (author)

Synthesis and Antimicrobial Activity of Novel Substituted Ethyl 2-(Quinolin-4-yl-propanoates

Directory of Open Access Journals (Sweden)

Yong Zhou

2013-03-01

Full Text Available Substituted 4-hydroxyquinolines were synthesized from anilines and diethyl 2-(ethoxymethylenemalonate by the Gould-Jacobs reaction via cyclization of the intermediate anilinomethylenemalonate followed by hydrolysis and decarboxylation. The 4-hydroxyquinolines reacted with phosphorous oxychloride to form 4-chloroquinolines, which reacted on heating with diethyl sodiomethylmalonate in DMF to yield moderate yields of substituted ethyl 2-(quinolin-4-ylpropanoates, many of which showed potent antimicrobial activity against Helicobacter pylori.

Oxidation of diclofenac by aqueous chlorine dioxide: identification of major disinfection byproducts and toxicity evaluation.

Science.gov (United States)

Wang, Yingling; Liu, Haijin; Liu, Guoguang; Xie, Youhai

2014-03-01

Diclofenac (DCF), a synthetic non-steroidal anti-inflammatory drug, is one of the most frequently detected pharmaceuticals in the aquatic environment. In this work, the mechanism and toxicity of DCF degradation by ClO2 under simulated water disinfection conditions were investigated. Experimental results indicate that rapid and significant oxidation of DCF occurred within the first few minutes; however, its mineralization process was longer than its degradation process. UPLC-MS and (1)H NMR spectroscopy were performed to identify major disinfection byproducts that were generated in three tentative degradation routes. The two main routes were based on initial decarboxylation of DCF on the aliphatic chain and hydroxylation of the phenylacetic acid moiety at the C-4 position. Subsequently, the formed aldehyde intermediates were the starting point for further multistep degradation involving decarboxylation, hydroxylation, and oxidation reactions of CN bond cleavage. The third route was based on transient preservation of chlorinated derivatives resulting from electrophilic attack by chlorine on the aromatic ring, which similarly underwent CN bond cleavage. Microtox bioassay was employed to evaluate the cytotoxicity of solutions treated by ClO2. The formation of more toxic mid-byproducts during the ClO2 disinfection process poses a potential risk to consumers. Copyright © 2013 Elsevier B.V. All rights reserved.

Efficient Production of Enantiopure d-Lysine from l-Lysine by a Two-Enzyme Cascade System

Directory of Open Access Journals (Sweden)

Xin Wang

2016-10-01

Full Text Available The microbial production of d-lysine has been of great interest as a medicinal raw material. Here, a two-step process for d-lysine production from l-lysine by the successive microbial racemization and asymmetric degradation with lysine racemase and decarboxylase was developed. The whole-cell activities of engineered Escherichia coli expressing racemases from the strains Proteus mirabilis (LYR and Lactobacillus paracasei (AAR were first investigated comparatively. When the strain BL21-LYR with higher racemization activity was employed, l-lysine was rapidly racemized to give dl-lysine, and the d-lysine yield was approximately 48% after 0.5 h. Next, l-lysine was selectively catabolized to generate cadaverine by lysine decarboxylase. The comparative analysis of the decarboxylation activities of resting whole cells, permeabilized cells, and crude enzyme revealed that the crude enzyme was the best biocatalyst for enantiopure d-lysine production. The reaction temperature, pH, metal ion additive, and pyridoxal 5′-phosphate content of this two-step production process were subsequently optimized. Under optimal conditions, 750.7 mmol/L d-lysine was finally obtained from 1710 mmol/L l-lysine after 1 h of racemization reaction and 0.5 h of decarboxylation reaction. d-lysine yield could reach 48.8% with enantiomeric excess (ee ≥ 99%.

Molecular hijacking of siroheme for the synthesis of heme and d1 heme.

Science.gov (United States)

Bali, Shilpa; Lawrence, Andrew D; Lobo, Susana A; Saraiva, Lígia M; Golding, Bernard T; Palmer, David J; Howard, Mark J; Ferguson, Stuart J; Warren, Martin J

2011-11-08

Modified tetrapyrroles such as chlorophyll, heme, siroheme, vitamin B(12), coenzyme F(430), and heme d(1) underpin a wide range of essential biological functions in all domains of life, and it is therefore surprising that the syntheses of many of these life pigments remain poorly understood. It is known that the construction of the central molecular framework of modified tetrapyrroles is mediated via a common, core pathway. Herein a further branch of the modified tetrapyrrole biosynthesis pathway is described in denitrifying and sulfate-reducing bacteria as well as the Archaea. This process entails the hijacking of siroheme, the prosthetic group of sulfite and nitrite reductase, and its processing into heme and d(1) heme. The initial step in these transformations involves the decarboxylation of siroheme to give didecarboxysiroheme. For d(1) heme synthesis this intermediate has to undergo the replacement of two propionate side chains with oxygen functionalities and the introduction of a double bond into a further peripheral side chain. For heme synthesis didecarboxysiroheme is converted into Fe-coproporphyrin by oxidative loss of two acetic acid side chains. Fe-coproporphyrin is then transformed into heme by the oxidative decarboxylation of two propionate side chains. The mechanisms of these reactions are discussed and the evolutionary significance of another role for siroheme is examined.

Oxidation of benzoic acid by heat-activated persulfate: Effect of temperature on transformation pathway and product distribution.

Science.gov (United States)

Zrinyi, Nick; Pham, Anh Le-Tuan

2017-09-01

Heat activates persulfate (S 2 O 8 2- ) into sulfate radical (SO 4 - ), a powerful oxidant capable of transforming a wide variety of contaminants. Previous studies have shown that an increase in temperature accelerates the rates of persulfate activation and contaminant transformation. However, few studies have considered the effect of temperature on contaminant transformation pathway. The objective of this study was to determine how temperature (T = 22-70 °C) influences the activation of persulfate, the transformation of benzoic acid (i.e., a model compound), and the distribution of benzoic acid oxidation products. The time-concentration profiles of the products suggest that benzoic acid was transformed via decarboxylation and hydroxylation mechanisms, with the former becoming increasingly important at elevated temperatures. The pathway through which the products were further oxidized was also influenced by the temperature of persulfate activation. Our findings suggest that the role of temperature in the persulfate-based treatment systems is not limited only to controlling the rates of sulfate and hydroxyl radical generation. The ability of sulfate radical to initiate decarboxylation reactions and, more broadly, fragmentation reactions, as well as the effect of temperature on these transformation pathways could be important to the transformation of a number of organic contaminants. Copyright © 2017 Elsevier Ltd. All rights reserved.

Structural basis of enzymatic activity for the ferulic acid decarboxylase (FADase from Enterobacter sp. Px6-4.

Directory of Open Access Journals (Sweden)

Wen Gu

Full Text Available Microbial ferulic acid decarboxylase (FADase catalyzes the transformation of ferulic acid to 4-hydroxy-3-methoxystyrene (4-vinylguaiacol via non-oxidative decarboxylation. Here we report the crystal structures of the Enterobacter sp. Px6-4 FADase and the enzyme in complex with substrate analogues. Our analyses revealed that FADase possessed a half-opened bottom β-barrel with the catalytic pocket located between the middle of the core β-barrel and the helical bottom. Its structure shared a high degree of similarity with members of the phenolic acid decarboxylase (PAD superfamily. Structural analysis revealed that FADase catalyzed reactions by an "open-closed" mechanism involving a pocket of 8 × 8 × 15 Å dimension on the surface of the enzyme. The active pocket could directly contact the solvent and allow the substrate to enter when induced by substrate analogues. Site-directed mutagenesis showed that the E134A mutation decreased the enzyme activity by more than 60%, and Y21A and Y27A mutations abolished the enzyme activity completely. The combined structural and mutagenesis results suggest that during decarboxylation of ferulic acid by FADase, Trp25 and Tyr27 are required for the entering and proper orientation of the substrate while Glu134 and Asn23 participate in proton transfer.

Identification and in vitro cytotoxicity of ochratoxin A degradation products formed during coffee roasting.

Science.gov (United States)

Cramer, Benedikt; Königs, Maika; Humpf, Hans-Ulrich

2008-07-23

The mycotoxin ochratoxin A is degraded by up to 90% during coffee roasting. In order to investigate this degradation, model heating experiments with ochratoxin A were carried out, and the reaction products were analyzed by HPLC-DAD and HPLC-MS/MS. Two ochratoxin A degradation products were identified, and their structure and absolute configuration were determined. As degradation reactions, the isomerization to 14-(R)-ochratoxin A and the decarboxylation to 14-decarboxy-ochratoxin A were identified. Subsequently, an analytical method for the determination of these compounds in roasted coffee was developed. Quantification was carried out by HPLC-MS/MS and the use of stable isotope dilution analysis. By using this method for the analysis of 15 coffee samples from the German market, it could be shown that, during coffee roasting, the ochratoxin A diastereomer 14-(R)-ochratoxin A was formed in amounts of up to 25.6% relative to ochratoxin A. The decarboxylation product was formed only in traces. For toxicity evaluations, first preliminary cell culture assays were performed with the two new substances. Both degradation products exhibited higher IC50 values and caused apoptotic effects with higher concentrations than ochratoxin A in cultured human kidney epithelial cells. Thus, these cell culture data suggest that the degradation products are less cytotoxic than ochratoxin A.

Amixicile, a novel strategy for targeting oral anaerobic pathogens.

Science.gov (United States)

Hutcherson, Justin A; Sinclair, Kathryn M; Belvin, Benjamin R; Gui, Qin; Hoffman, Paul S; Lewis, Janina P

2017-09-05

The oral microflora is composed of both health-promoting as well as disease-initiating bacteria. Many of the disease-initiating bacteria are anaerobic and include organisms such as Porphyromonas gingivalis, Prevotella intermedia, Fusobacterium nucleatum, and Tannerella forsythia. Here we investigated a novel therapeutic, amixicile, that targets pyruvate:ferredoxin oxidoreductase (PFOR), a major metabolic enzyme involved in energy generation through oxidative decarboxylation of pyruvate. PFOR is present in these anaerobic pathogenic bacteria and thus we hypothesized that amixicile would effectively inhibit their growth. In general, PFOR is present in all obligate anaerobic bacteria, while oral commensal aerobes, including aerotolerant ones, such as Streptococcus gordonii, use pyruvate dehydrogenase to decarboxylate pyruvate. Accordingly, we observed that growth of the PFOR-containing anaerobic periodontal pathogens, grown in both monospecies as well as multispecies broth cultures was inhibited in a dose-dependent manner while that of S. gordonii was unaffected. Furthermore, we also show that amixicile is effective against these pathogens grown as monospecies and multispecies biofilms. Finally, amixicile is the first selective therapeutic agent active against bacteria internalized by host cells. Together, the results show that amixicile is an effective inhibitor of oral anaerobic bacteria and as such, is a good candidate for treatment of periodontal diseases.

Determination of ketone bodies in blood by headspace gas chromatography-mass spectrometry

DEFF Research Database (Denmark)

Holm, Karen Marie Dollerup; Linnet, Kristian; Rasmussen, Brian Schou

2010-01-01

A gas chromatography-mass spectrometry (GC-MS) method for determination of ketone bodies (ß-hydroxybutyrate, acetone, and acetoacetate) in blood is presented. The method is based on enzymatic oxidation of D-ß-hydroxybutyrate to acetoacetate, followed by decarboxylation to acetone, which...... was quantified by the use of headspace GC-MS using acetone-(13)C(3) as an internal standard. The developed method was found to have intra- and total interday relative standard deviations

Stereoselective Synthesis of(Z)-4-(2-Bromovinyl)benzenesulfonyl Azide and Its Synthetic Utility for the Transformation to(2)-N-[4-(2-Bromovinyl)benzenesulfonyl]imidates

Institute of Scientific and Technical Information of China (English)

ZHANG Wensheng; KUANG Chunxiang; YANG Qing

2009-01-01

A novel method for the stereoselective synthesis of(Z)-4-(2-bromovinyl)benzenesulfonyl azide by simultaneous azidation and debrorninative decarboxylation of anti-2,3-dibromo-3-(4-chlorosulfonylphenyl)propanoic acid using NaN3 only was developed.Facile transformation of(Z)-4-(2-bromovinyl)benzenesulfonyl azide to(Z)-N-[4(2-bromovinyl)benzenesulfonyl]imidates was also achieved by Cu-catalyzed three-component coulping of (Z)-4-(2-bromovinyi)benzenesulfonyl azide,terminal alkynes and alcohols/phenols.

Rapid synthesis and purification of carbon-11 labelled DOPA: a potential agent for brain studies

International Nuclear Information System (INIS)

Reiffers, S.; Beerling-van der Molen, H.D.; Vaalburg, W.; Hoeve, W. ten; Paans, A.M.J.; Korf, J.; Woldring, M.G.; Wynberg, H.

1977-01-01

A rapid method for preparation and purification of β-(3,4-dihydroxyphenyl)-D,L-α-alanine-1- 11 C( 11 C-DOPA), using 11 CO 2 as the radioactive precursor is described. Carboxylation of an α-lithioisocyanide, containing protected hydroxylic groups, was followed by a three-step hydrolysis of the intermediate αioscyano carboxylic acid. Preliminary experiments in rats indicate that the compound is preferentially decarboxylated in brain areas rich in dopamine containing neurons. (author)

Development and validation of an LC?MS/MS method for the determination of biogenic amines in wines and beers

OpenAIRE

Nalazek-Rudnicka, Katarzyna; Wasik, Andrzej

2017-01-01

Abstract Biogenic amines are group of organic, basic, nitrogenous compounds that naturally occur in plant, microorganism, and animal organisms. Biogenic amines are mainly produced through decarboxylation of amino acids. They are formed during manufacturing of some kind of food and beverages such as cheese, wine, or beer. Histamine, cadaverine, agmatine, tyramine, putrescine, and ?-phenylethylamine are the most common biogenic amines found in wines and beers. This group of compounds can be tox...

Carbon–carbon bond cleavage for Cu-mediated aromatic trifluoromethylations and pentafluoroethylations

Directory of Open Access Journals (Sweden)

Tsuyuka Sugiishi

2015-12-01

Full Text Available This short review highlights the copper-mediated fluoroalkylation using perfluoroalkylated carboxylic acid derivatives. Carbon–carbon bond cleavage of perfluoroalkylated carboxylic acid derivatives takes place in fluoroalkylation reactions at high temperature (150–200 °C or under basic conditions to generate fluoroalkyl anion sources for the formation of fluoroalkylcopper species. The fluoroalkylation reactions, which proceed through decarboxylation or tetrahedral intermediates, are useful protocols for the synthesis of fluoroalkylated aromatics.

Synthesis and Activity of Grape Wood Phytotoxins and Related Compounds

Directory of Open Access Journals (Sweden)

S. Perrin-Cherioux

2004-04-01

Full Text Available The synthesis of analogues and derivatives of two o-hydroxyphenylacetylenes, eutypine and sterehirsutinal, the main phytotoxins isolated from the culture medium of Eutypa lata and Stereum hirsutum, is reported. Two means of synthesis are described, based on cyclisation, oxidation, oxidative decarboxylation or reduction reactions, and producing o-hydroxyphenylacetylene or benzofuran derivatives. Some of these synthetic compounds were tested on grapevine callus in order to compare their toxicity with the natural analogues.

Agmatine Modulates the Phenotype of Macrophage Acute Phase after Spinal Cord Injury in Rats

OpenAIRE

Kim, Jae Hwan; Kim, Jae Young; Mun, Chin Hee; Suh, Minah; Lee, Jong Eun

2017-01-01

Agmatine is a decarboxylated arginine by arginine decarboxylase. Agmatine is known to be a neuroprotective agent. It has been reported that agmatine works as a NMDA receptor blocker or a competitive nitric oxide synthase inhibitor in CNS injuries. In spinal cord injury, agmatine showed reduction of neuropathic pain, improvement of locomotor function, and neuroprotection. Macrophage is a key cellular component in neuroinflammation, a major cause of impairment after spinal cord injury. Macropha...

Decarboxylative alkylation for site-selective bioconjugation of native proteins via oxidation potentials

Science.gov (United States)

Bloom, Steven; Liu, Chun; Kölmel, Dominik K.; Qiao, Jennifer X.; Zhang, Yong; Poss, Michael A.; Ewing, William R.; MacMillan, David W. C.

2018-02-01

The advent of antibody-drug conjugates as pharmaceuticals has fuelled a need for reliable methods of site-selective protein modification that furnish homogeneous adducts. Although bioorthogonal methods that use engineered amino acids often provide an elegant solution to the question of selective functionalization, achieving homogeneity using native amino acids remains a challenge. Here, we explore visible-light-mediated single-electron transfer as a mechanism towards enabling site- and chemoselective bioconjugation. Specifically, we demonstrate the use of photoredox catalysis as a platform to selectivity wherein the discrepancy in oxidation potentials between internal versus C-terminal carboxylates can be exploited towards obtaining C-terminal functionalization exclusively. This oxidation potential-gated technology is amenable to endogenous peptides and has been successfully demonstrated on the protein insulin. As a fundamentally new approach to bioconjugation this methodology provides a blueprint toward the development of photoredox catalysis as a generic platform to target other redox-active side chains for native conjugation.

Decarboxylative alkylation for site-selective bioconjugation of native proteins via oxidation potentials.

Science.gov (United States)

Bloom, Steven; Liu, Chun; Kölmel, Dominik K; Qiao, Jennifer X; Zhang, Yong; Poss, Michael A; Ewing, William R; MacMillan, David W C

2018-02-01

The advent of antibody-drug conjugates as pharmaceuticals has fuelled a need for reliable methods of site-selective protein modification that furnish homogeneous adducts. Although bioorthogonal methods that use engineered amino acids often provide an elegant solution to the question of selective functionalization, achieving homogeneity using native amino acids remains a challenge. Here, we explore visible-light-mediated single-electron transfer as a mechanism towards enabling site- and chemoselective bioconjugation. Specifically, we demonstrate the use of photoredox catalysis as a platform to selectivity wherein the discrepancy in oxidation potentials between internal versus C-terminal carboxylates can be exploited towards obtaining C-terminal functionalization exclusively. This oxidation potential-gated technology is amenable to endogenous peptides and has been successfully demonstrated on the protein insulin. As a fundamentally new approach to bioconjugation this methodology provides a blueprint toward the development of photoredox catalysis as a generic platform to target other redox-active side chains for native conjugation.

Step changes and deactivation behaviour in the continuous decarboxylation of stearic acid

DEFF Research Database (Denmark)

Madsen, Anders Theilgaard; Rozmyslowicz, B.; Simakova, I.

2011-01-01

% conversion of pure stearic acid. Deactivation took place in H-2-deficient gas atmosphere, probably as a result of the formation of unsaturated products and coking in the pore system. Transient experiments with step changes were performed: 1 h was required for the step change to be visible in liquid sampling...

Step Changes and Deactivation Behavior in the Continuous Decarboxylation of Stearic Acid

DEFF Research Database (Denmark)

Madsen, Anders Theilgaard; Rozmysłowicz, Bartosz; Simakova, Irina L.

2011-01-01

Deoxygenation of dilute and concentrated stearic acid over 2% Pd/C beads was performed in a continuous reactor at 300 °C and 20 bar pressure of Ar or 5% H2/Ar. Stable operation was obtained in 5% H2 atmosphere, with 95% conversion of 10 mol % dilute stearic acid in dodecane and 12% conversion...... of pure stearic acid. Deactivation took place in H2-deficient gas atmosphere, probably as a result of the formation of unsaturated products and coking in the pore system. Transient experiments with step changes were performed: 1 h was required for the step change to be visible in liquid sampling, whereas...

Bio-based methacrylic acid via catalytic decarboxylation of itaconic and citric acids

Science.gov (United States)

Methacrylic acid is an important commodity monomer for the plastics industry that is produced industrially from acetone, hydrogen cyanide and concentrated sulfuric acid via the acetone cyanohydrin (ACH) process. Disadvantages to the ACH process include nonrenewable starting materials, stoichiometric...

Rhodium-catalyzed chemo- and regioselective decarboxylative addition of β-ketoacids to alkynes.

Science.gov (United States)

Li, Changkun; Grugel, Christian P; Breit, Bernhard

2016-04-30

A highly efficient rhodium-catalyzed chemo- and regioselective addition of β-ketoacids to alkynes is reported. Applying a Rh(i)/(S,S)-DIOP catalyst system, γ,δ-unsaturated ketones were prepared with exclusively branched selectivity under mild conditions. This demonstrates that readily available alkynes can be an alternative entry to allyl electrophiles in transition-metal catalyzed allylic alkylation reactions.

Production of 1-carbon units from glycine is extensive in healthy men and women.

Science.gov (United States)

Lamers, Yvonne; Williamson, Jerry; Theriaque, Douglas W; Shuster, Jonathan J; Gilbert, Lesa R; Keeling, Christine; Stacpoole, Peter W; Gregory, Jesse F

2009-04-01

Glycine undergoes decarboxylation in the glycine cleavage system (GCS) to yield CO(2), NH(3), and a 1-carbon unit. CO(2) also can be generated from the 2-carbon of glycine by 10-formyltetrahydrofolate-dehydrogenase and, after glycine-to-serine conversion by serine hydroxymethyltransferase, from the tricarboxylic acid cycle. To evaluate the relative fates of glycine carbons in CO(2) generation in healthy volunteers (3 male, 3 female, aged 21-26 y), primed, constant infusions were conducted using 9.26 micromol x h(-1) x kg(-1) of [1,2-(13)C]glycine and 1.87 micromol x h(-1) x kg(-1) of [5,5,5-(2)H(3)]leucine, followed by an infusion protocol using [1-(13)C]glycine as the glycine tracer. The time period between the infusion protocols was >6 mo. In vivo rates of whole-body glycine and leucine flux were nearly identical in protocols with [1,2-(13)C]glycine and [5,5,5-(2)H(3)]leucine and with [1-(13)C]glycine and [5,5,5-(2)H(3)]leucine tracers, which showed high reproducibility between the tracer protocols. Using the [1-(13)C]glycine tracer, breath CO(2) data showed a total rate of glycine decarboxylation of 96 +/- 8 micromol x h(-1) x kg(-1), which was 22 +/- 3% of whole-body glycine flux. In contrast, infusion of [1,2-(13)C]glycine yielded a glycine-to-CO(2) flux of 146 +/- 37 micromol x h(-1) x kg(-1) (P = 0.026). By difference, this implies a rate of CO(2) formation from the glycine 2-carbon of 51 +/- 40 micromol x h(-1) x kg(-1), which accounts for approximately 35% of the total CO(2) generated in glycine catabolism. These findings also indicate that approximately 65% of the CO(2) generation from glycine occurs by decarboxylation, primarily from the GCS. Further, these results suggest that the GCS is responsible for the entry of 5,10-methylenetetrahydrofolate into 1-carbon metabolism at a very high rate ( approximately 96 micromol x h(-1) x kg(-1)), which is approximately 20 times the demand for methyl groups for homocysteine remethylation.

Multiple roles of mobile active center loops in the E1 component of the Escherichia coli pyruvate dehydrogenase complex - Linkage of protein dynamics to catalysis

Science.gov (United States)

Jordan, Frank; Arjunan, Palaniappa; Kale, Sachin; Nemeria, Natalia S.; Furey, William

2009-01-01

The region encompassing residues 401–413 on the E1 component of the pyruvate dehydrogenase multienzyme complex from Escherichia coli comprises a loop (the inner loop) which was not seen in the X-ray structure in the presence of thiamin diphosphate, the required cofactor for the enzyme. This loop is seen in the presence of a stable analogue of the pre-decarboxylation intermediate, the covalent adduct between the substrate analogue methyl acetylphosphonate and thiamin diphosphate, C2α-phosphonolactylthiamin diphosphate. It has been shown that the residue H407 and several other residues on this loop are required to reduce the mobility of the loop so electron density corresponding to it can be seen once the pre-decarboxylation intermediate is formed. Concomitantly, the loop encompassing residues 541–557 (the outer loop) appears to work in tandem with the inner loop and there is a hydrogen bond between the two loops ensuring their correlated motion. The inner loop was shown to: a) sequester the active center from carboligase side reactions; b) assist the interaction between the E1 and the E2 components, thereby affecting the overall reaction rate of the entire multienzyme complex; c) control substrate access to the active center. Using viscosity effects on kinetics it was shown that formation of the pre-decarboxylation intermediate is specifically affected by loop movement. A cysteine-less variant was created for the E1 component, onto which cysteines were substituted at selected loop positions. Introducing an electron spin resonance spin label and an 19F NMR label onto these engineered cysteines, the loop mobility was examined: a) both methods suggested that in the absence of ligand, the loop exists in two conformations; b) line-shape analysis of the NMR signal at different temperatures, enabled estimation of the rate constant for loop movement, and this rate constant was found to be of the same order of magnitude as the turnover number for the enzyme under the

Rh(III)-Catalyzed C-H Activation of Benzoylacetonitriles and Tandem Cyclization with Diazo Compounds to Substituted Benzo[ de]chromenes.

Science.gov (United States)

Fang, Feifei; Zhang, Chunmei; Zhou, Chaofan; Li, Yazhou; Zhou, Yu; Liu, Hong

2018-04-06

Rh (III)-catalyzed C-H activation of benzoylacetonitriles in coupling with diazo compounds was developed to synthesize diversified substituted benzo[ de]chromenes via a formal (4 + 2) cycloaddition with a diazo compound and subsequent tandem (4 + 2) cycloaddition with another diazo compound. Intriguingly, synthesis of substituted benzo[ de]chromenes and their decarboxylation products could be realized by controlling the reaction conditions. These reactions have a broad range of substrates, moderate to good yields, and high regioselectivity.

Inclined fluidized bed system for drying fine coal

Science.gov (United States)

Cha, Chang Y.; Merriam, Norman W.; Boysen, John E.

1992-02-11

Coal is processed in an inclined fluidized bed dryer operated in a plug-flow manner with zonal temperature and composition control, and an inert fluidizing gas, such as carbon dioxide or combustion gas. Recycled carbon dioxide, which is used for drying, pyrolysis, quenching, and cooling, is produced by partial decarboxylation of the coal. The coal is heated sufficiently to mobilize coal tar by further pyrolysis, which seals micropores upon quenching. Further cooling with carbon dioxide enhances stabilization.

2′-Methyl-2′-nitro-1′-phenyl-2′,3′,5′,6′,7′,7a'-hexahydrospiro[indoline-3,3′-1′H-pyrrolizin]-2-one

Directory of Open Access Journals (Sweden)

Yaghoub Sarrafi

2008-08-01

Full Text Available The title compound, C21H21N3O3, was synthesized by a multi-component 1,3-dipolar cycloaddition of azomethine ylide, derived from isatin and proline by a decarboxylative route, and (E-1-phenyl-2-nitropropene. In the molecule, the spiro junction links a planar oxindole ring and a pyrrolidine ring in an envelope conformation. The molecular packing is stabilized by an intermolecular N—H...N interaction of the oxindole and pyrrolizidine rings.

Method of preparation of tritiated benzene for measuring in hydrology low level tritium in a liquid scintillator; Methode de preparation de benzene tritie pour la mesure par scintillation en hydrologie de faibles teneurs en tritium

Energy Technology Data Exchange (ETDEWEB)

Pichat, L; Sharefkin, D; Herbert, M

1962-07-01

It is given a preliminary account of the preparation of tritiated benzene by decarboxylation of calcium mellitate (calcium benzene-hexa-carboxylate) at 500 deg C by an excess of tritiated barium or calcium hydroxide yield is 64-72 pour cent based on used calcium mellitate. Benzene obtained after a single distillation is free from seriously quenching impurities. It is obtained 10-15 g benzene per batch. It remains to determine the occurrence of an isotope effect during the reaction. Various improvements and modifications are still necessary to increase the size of the sample to be treated. (authors) [French] On donne une description preliminaire de la preparation de benzene tritie par decarboxylation du mellitate de calcium (benzenehexacarboxylate de calcium) a 500 deg C par la chaux ou la baryte tritiee en exces. Le rendement est de 64 a 72 % base sur le mellitate de calcium mis en oeuvre. Le benzene obtenu apres une simple distillation dans une colonne Vigreux ne contient pas d'impuretes pouvant, en scintillation, eteindre la fluorescence. En une operation, on peut obtenir 10-15 g de benzene. Il reste a determiner, si au cours de la reaction, il y a un effet isotopique. Diverses ameliorations et modifications sont encore indispensables en vue d'accroitre l'echelle sur laquelle l'operation peut etre conduite. (auteurs)

Crystal Structure and Substrate Specificity of Drosophila 3,4-Dihydroxyphenylalanine Decarboxylase

Energy Technology Data Exchange (ETDEWEB)

Han, Q.; Ding, H; Robinson, H; Christensen, B; Li, J

2010-01-01

3,4-Dihydroxyphenylalanine decarboxylase (DDC), also known as aromatic L-amino acid decarboxylase, catalyzes the decarboxylation of a number of aromatic L-amino acids. Physiologically, DDC is responsible for the production of dopamine and serotonin through the decarboxylation of 3,4-dihydroxyphenylalanine and 5-hydroxytryptophan, respectively. In insects, both dopamine and serotonin serve as classical neurotransmitters, neuromodulators, or neurohormones, and dopamine is also involved in insect cuticle formation, eggshell hardening, and immune responses. In this study, we expressed a typical DDC enzyme from Drosophila melanogaster, critically analyzed its substrate specificity and biochemical properties, determined its crystal structure at 1.75 Angstrom resolution, and evaluated the roles residues T82 and H192 play in substrate binding and enzyme catalysis through site-directed mutagenesis of the enzyme. Our results establish that this DDC functions exclusively on the production of dopamine and serotonin, with no activity to tyrosine or tryptophan and catalyzes the formation of serotonin more efficiently than dopamine. The crystal structure of Drosophila DDC and the site-directed mutagenesis study of the enzyme demonstrate that T82 is involved in substrate binding and that H192 is used not only for substrate interaction, but for cofactor binding of drDDC as well. Through comparative analysis, the results also provide insight into the structure-function relationship of other insect DDC-like proteins.

Technological factors affecting biogenic amine content in foods: a review

Directory of Open Access Journals (Sweden)

Fausto Gardini

2016-08-01

Full Text Available Biogenic amines (BAs are molecules which can be present in foods and, due to their toxicity, can cause adverse effects on the consumers. BAs are generally produced by microbial decarboxylation of amino acids in food products. The most significant BAs occurring in foods are histamine, tyramine, putrescine, cadaverine, tryptamine, 2-phenylethylamine, spermine, spermidine and agmatine. The importance of preventing the excessive accumulation of BAs in food is related to their impact on human health and food quality. Quality criteria in connection with the presence of BAs in food and food products are necessary from a toxicological point of view. This is particularly important in fermented foods in which the massive microbial proliferation required for obtaining specific products is often relater with BA accumulation. In this review, up-to-date information and recent discoveries about technological factors affecting biogenic amine content in foods are reviewed. Specifically, BA forming-microorganism and decarboxylation activity, genetic and metabolic organization of decarboxylases, risk associated to BAs (histamine, tyramine toxicity and other BAs, environmental factors influencing BA formation (temperature, salt concentration, pH. In addition, the technological factors for controlling BA production (use of starter culture, technological additives, effects of packaging, other non-thermal treatments, metabolising BA by microorganisms, effects of pressure treatments on BA formation and antimicrobial substances are addressed.

Investigation of the enzymatic mechanism of yeast orotidine-5'-monophosphate decarboxylase using 13C kinetic isotope effects

International Nuclear Information System (INIS)

Smiley, J.A.; Bell, J.B.; Jones, M.E.; Paneth, P.; O'Leary, M.H.

1991-01-01

Orotidine-5'-monophosphate decarboxylase (ODCase) from Saccharomyces cerevisiae displays an observed 13 C kinetic isotope effect of 1.0247 ± 0.0008 at 25 C, pH 6.8. The observed isotope effect is sensitive to changes in the reaction medium, such as pH, temperature, or glycerol content. The value of 1.0494 ± 0.0006 measured at pH 4.0, 25 C, is not altered significantly by temperature or glycerol, and thus the intrinsic isotope effect for the reaction is apparently being observed under these conditions and decarboxylation is almost entirely rate-determining. These data require a catalytic mechanism with freely reversible binding and one in which a very limited contribution to the overall rate is made by chemical steps preceding decarboxylation; the zwitterion mechanism of Beak and Siegel, which involves only protonation of the pyrimidine ring, is such a mechanism. With use of an intrinsic isotope effect of 1.05, a partitioning factor of less than unity is calculated for ODCase at pH 6.0, 25 C. A quantitative kinetic analysis using this result excludes the possibility of an enzymatic mechanism involving covalent attachment of an enzyme nucleophile to C-5 of the pyrimidine ring. These data fit a kinetic model in which an enzyme proton necessary for catalysis is titrated at high pH, thus providing evidence for the catalytic mechanism of Beak and Siegal

Adsorption of Streptococcus faecalis on diatomite carriers for use in biotransformations.

Science.gov (United States)

Anderson, W A; Bay, P; Legge, R L; Moo-Young, M

1990-01-01

Adsorption of cells on particulate carriers is potentially one of the most cost-effective immobilization techniques available. Diatomite carriers, such as Celite, have desirable physical properties, are inexpensive, and are suitable for both mycelial and bacterial systems. This work investigated the use of diatomite carriers as a biocatalyst support in a packed-bed reactor where L-tyrosine was enzymatically decarboxylated using adsorbed, non-growing cells of Streptococcus faecalis. Composition of microbial adsorption on different Celite types, with mean pore sizes ranging from 0.55 to 22 microns, showed there was no significant difference in biomass loading capacity under the conditions used. Using Celite 560, biomass loadings in a packed-bed reactor varied from 10 to 30 g dm-3 of reactor volume, which compares favourably with other adsorption methods. When used to decarboxylate L-tyrosine, the reactor was found to have a half-life of 15-20 h. A combination of enzyme activity loss and slow leakage of biomass from the packed-bed reactor was responsible for the decline in conversion. Treatment of the S. faecalis cells with glutaraldehyde significantly reduced the enzyme activity loss and extended the reactor half-life to 65 h, but had little effect on the rate of cell leakage from the reactor. Further work on reduction of cell leakage rate seems necessary for evaluation of the system's practicality.

Two phosphoenolpyruvate carboxykinases coexist in the Crassulacean Acid Metabolism plant Ananas comosus. Isolation and characterization of the smaller 65 kDa form.

Science.gov (United States)

Martín, Mariana; Rius, Sebastián Pablo; Podestá, Florencio Esteban

2011-06-01

Two phosphoenolpyruvate carboxykinase (PEPCK, EC 4.1.1.49) isoforms of 74 and 65 kDa were found to coexist in vivo in pineapple leaves, a constitutive Crassulacean Acid Metabolism plant. The 65 kDa form was not the result of proteolytic cleavage of the larger form since extraction methods reported to prevent PEPCK proteolysis in other plant tissues failed to yield a single immunoreactive PEPCK polypeptide in leaf extracts. In this work, the smaller form of 65 kDa was purified to homogeneity and physically and kinetically characterized and showed parameters compatible with a fully active enzyme. The specific activity was nearly twice higher for decarboxylation of oxaloacetate when compared to carboxylation of phosphoenolpyruvate. Kinetic parameters fell within the range of those estimated for other plant PEPCKs. Its activity was affected by several metabolites, as shown by inhibition by 3-phosphoglycerate, citrate, malate, fructose-1,6-bisphosphate, l-asparagine and activation of the decarboxylating activity by succinate. A break in the Arrhenius plot at about 30°C indicates that PEPCK structure is responsive to changes in temperature. The results indicate that pineapple leaves contain two PEPCK forms. The biochemical characterization of the smaller isoform performed in this work suggests that it could participate in both carbon and nitrogen metabolism in vivo by acting as a decarboxylase. Copyright © 2011 Elsevier Masson SAS. All rights reserved.

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

International Nuclear Information System (INIS)

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

1996-02-01

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

Structure of a Prokaryotic Virtual Proton Pump at 3.2 Astroms Resolution

Energy Technology Data Exchange (ETDEWEB)

Fang, Y.; Jayaram, H; Shane, T; Partensky, L; Wu, F; williams, C; Xiong, Y; Miller, C

2009-01-01

To reach the mammalian gut, enteric bacteria must pass through the stomach. Many such organisms survive exposure to the harsh gastric environment (pH 1.5-4) by mounting extreme acid-resistance responses, one of which, the arginine-dependent system of Escherichia coli, has been studied at levels of cellular physiology, molecular genetics and protein biochemistry. This multiprotein system keeps the cytoplasm above pH 5 during acid challenge by continually pumping protons out of the cell using the free energy of arginine decarboxylation. At the heart of the process is a 'virtual proton pump' in the inner membrane, called AdiC, that imports L-arginine from the gastric juice and exports its decarboxylation product agmatine. AdiC belongs to the APC superfamily of membrane proteins, which transports amino acids, polyamines and organic cations in a multitude of biological roles, including delivery of arginine for nitric oxide synthesis, facilitation of insulin release from pancreatic beta-cells, and, when inappropriately overexpressed, provisioning of certain fast-growing neoplastic cells with amino acids. High-resolution structures and detailed transport mechanisms of APC transporters are currently unknown. Here we describe a crystal structure of AdiC at 3.2 A resolution. The protein is captured in an outward-open, substrate-free conformation with transmembrane architecture remarkably similar to that seen in four other families of apparently unrelated transport proteins.

Structure of a prokaryotic virtual proton pump at 3.2 Å resolution

Energy Technology Data Exchange (ETDEWEB)

Fang, Yiling; Jayaram, Hariharan; Shane, Tania; Kolmakova-Partensky, Ludmila; Wu, Fang; Williams, Carole; Xiong, Yong; Miller, Christopher; (Yale); (Brandeis)

2009-09-15

To reach the mammalian gut, enteric bacteria must pass through the stomach. Many such organisms survive exposure to the harsh gastric environment (pH 1.5-4) by mounting extreme acid-resistance responses, one of which, the arginine-dependent system of Escherichia coli, has been studied at levels of cellular physiology, molecular genetics and protein biochemistry. This multiprotein system keeps the cytoplasm above pH 5 during acid challenge by continually pumping protons out of the cell using the free energy of arginine decarboxylation. At the heart of the process is a 'virtual proton pump' in the inner membrane, called AdiC, that imports L-arginine from the gastric juice and exports its decarboxylation product agmatine. AdiC belongs to the APC superfamily of membrane proteins, which transports amino acids, polyamines and organic cations in a multitude of biological roles, including delivery of arginine for nitric oxide synthesis, facilitation of insulin release from pancreatic {beta}-cells, and, when inappropriately overexpressed, provisioning of certain fast-growing neoplastic cells with amino acids. High-resolution structures and detailed transport mechanisms of APC transporters are currently unknown. Here we describe a crystal structure of AdiC at 3.2 {angstrom} resolution. The protein is captured in an outward-open, substrate-free conformation with transmembrane architecture remarkably similar to that seen in four other families of apparently unrelated transport proteins.

Photochemical exchange reactions of thymine, uracil and their nucleosides with selected amino acids

International Nuclear Information System (INIS)

Shetlar, M.D.; Taylor, J.A.; Hom, K.

1984-01-01

The photoinduced exchange reactions of thymine with lysine at basic pH, using 254 nm light, have been studied. Three products have been isolated, namely, 6-amino-2-(1-thyminyl)hexanoic acid (Ia), 2-amino-6-(1-thyminyl)hexanoic acid (IIa) and 1-amino-5-(1-thyminyl)pentane (IIIa). Compound IIIa was shown to be a secondary product, produced by photochemical decarboxylation of Ia. Photochemical reaction of thymine with glycine and alanine at basic pH led, respectively, to formation of 2-(1-thyminyl)acetic acid (Ic) and 2-(1-thyminyl)propionic acid (Id). Compounds Ic and Id underwent photolysis to produce the decarboxylated secondary products 1-methylthymine and 1-ethylthymine, respectively. Thymidine reacts photochemically with glycine and alanine to produce the same products. Irradiation of DNA in the presence of lysine at basic pH led to the formation of the same products formed in the thymine-lysine system, namely Ia, IIa and IIIa. Uracil was found to undergo analogous photochemical exchange reactions with lysine to form 6-amino-2-(1-uracilyl)hexanoic acid (Ib), and 2-amino-6-(1-uracilyl)hexanoic acid (IIb). Compound Ib was found to undergo photodecarboxylation to form 1-amino-5-(1-uracilyl)pentane (IIIb), analogous to the secondary photoreaction of Ia. Photoreaction of uracil with 1,5-diaminopentane (cadaverine) likewise led to formation of IIIb. (author)

Direct Production of Propene from the Thermolysis of Poly(..beta..-hydroxybutyrate)

Energy Technology Data Exchange (ETDEWEB)

Mittal, Ashutosh; Pilath, Heidi M.; Johnson, David K.

2015-03-22

To transform biomass components into hydrocarbon fuels it is clear that there are two main transformations that need to occur, i.e., deoxygenation and carbon chain extension. The potential routes for decreasing the oxygen content of biomass intermediates include dehydration, hydrodeoxygenation and decarboxylation. One route that is examined here is the conversion of polyhydroxyalkanoates (PHA) to alkenes that would be intermediates to hydrocarbon fuels.Thermal breakdown of PHA proceeds via an intermediate carboxylic acid, which can then be decarboxylated to an alkene. Oligomerization of alkenes by well-known commercial technologies would permit production of a range of hydrocarbon fuels from a carbohydrate derived intermediate. Moreover, polyhydroxybutyrate (PHB) can be produced in Cupriavidus necator (formerly known as Ralstonia eutropha) and Alcaligenes eutrophus on a variety of carbon sources including glucose, fructose and glycerol with PHB accumulation reaching 75 percent of dry cell mass. We conducted thermal conversion of PHB and pure crotonic acid (CA), the intermediate carboxylic acid produced by thermal depolymerization of PHB, in a flow-through reactor. The results of initial experiments on the thermal conversion of CA showed that up to 75 mole percent yields of propene could be achieved by optimizing the residence time and temperature of the reactor. Further experiments are being investigated to optimize the reactor parameters and enhance propene yields via thermal conversion of PHB.

Crystal structure and substrate specificity of Drosophila 3,4-dihydroxyphenylalanine decarboxylase.

Directory of Open Access Journals (Sweden)

Qian Han

2010-01-01

Full Text Available 3,4-Dihydroxyphenylalanine decarboxylase (DDC, also known as aromatic L-amino acid decarboxylase, catalyzes the decarboxylation of a number of aromatic L-amino acids. Physiologically, DDC is responsible for the production of dopamine and serotonin through the decarboxylation of 3,4-dihydroxyphenylalanine and 5-hydroxytryptophan, respectively. In insects, both dopamine and serotonin serve as classical neurotransmitters, neuromodulators, or neurohormones, and dopamine is also involved in insect cuticle formation, eggshell hardening, and immune responses.In this study, we expressed a typical DDC enzyme from Drosophila melanogaster, critically analyzed its substrate specificity and biochemical properties, determined its crystal structure at 1.75 Angstrom resolution, and evaluated the roles residues T82 and H192 play in substrate binding and enzyme catalysis through site-directed mutagenesis of the enzyme. Our results establish that this DDC functions exclusively on the production of dopamine and serotonin, with no activity to tyrosine or tryptophan and catalyzes the formation of serotonin more efficiently than dopamine.The crystal structure of Drosophila DDC and the site-directed mutagenesis study of the enzyme demonstrate that T82 is involved in substrate binding and that H192 is used not only for substrate interaction, but for cofactor binding of drDDC as well. Through comparative analysis, the results also provide insight into the structure-function relationship of other insect DDC-like proteins.

Origin of the pKa shift of the catalytic lysine in acetoacetate decarboxylase.

OpenAIRE

Ishikita, Hiroshi

2010-01-01

The pKa value of Lys115, the catalytic residue in acetoacetate decarboxylate, was calculated using atomic coordinates of the X-ray crystal structure with consideration of the protonation states of all titratable sites in the protein. The calculated pKa value of Lys115 (pKa(Lys115)) was unusually low (approximately 6) in agreement with the experimentally measured value. Although charged residues impact pKa(Lys115) considerably in the native protein, the significant pKa(Lys115) downshift in the...

Transformación de biomasa a productos químicos de interés y carburantes mediante descarboxilación cetónica e hidrodesoxigenación

OpenAIRE

Oliver Tomás, Borja

2017-01-01

The purpose of the present thesis was the use and valorisation of biomass platform molecules or their derivatives, applying the principles of sustainable chemistry. The reaction of ketonic decarboxylation of carboxylic acids was studied in the presence of metal oxides. ZrO2 was shown to be an excellent catalyst for the reaction, reasonably stable with time on stream and reusable. The reactivity of different substrates over ZrO2 was investigated with respect to the degree of substitution of...

Decarboxilase activity and biosynthetic processes in Saccharomyces carlsbergenesis upon the action of light

International Nuclear Information System (INIS)

Chebotarev, L.N.; Shaburova, G.V.; Licyuk, G.M.

1983-01-01

It is established that visible light of 410-520 nm wave-- lengths stimulated decarboxylase activity, protein biosynthesis and increase in the number of cells in the Saccharomyces carlsbergenesis yeast culture. A limiting link of these yeast metabolism is decarboxylizing of pyuvate providing the formation of a substrate for functioning of the di- and pericarboxilic acid cycle. The light effect can activate this process thus eliminating substrate deficiency of the Krebs cycle which results in the increase of anabolic processes intensity

The purification and steady-state kinetic behaviour of rabbit heart mitochondrial NAD(P)+ malic enzyme.

OpenAIRE

Davisson, V J; Schulz, A R

1985-01-01

The mitochondrial NAD(P)+ malic enzyme [EC 1.1.1.39, L-malate:NAD+ oxidoreductase (decarboxylating)] was purified from rabbit heart to a specific activity of 7 units (mumol/min)/mg at 23 degrees C. A study of the reductive carboxylation reaction indicates that this enzymic reaction is reversible. The rate of the reductive carboxylation reaction appears to be completely inhibited at an NADH concentration of 0.92 mM. A substrate saturation curve of this reaction with NADH as the varied substrat...

Influence of Thawing Methods and Storage Temperatures on Bacterial Diversity, Growth Kinetics, and Biogenic Amine Development in Atlantic Mackerel

DEFF Research Database (Denmark)

Onyang, S.; Palmadottir, H.; Tomason, T.

2016-01-01

Limited knowledge is currently available on the influence of fish thawing and subsequent storage conditions on bacterial growth kinetics, succession, and diversity alongside the production of biogenic amines. This study aimed to address these factors during the thawing and subsequent storage of m...... amine producing bacteria, with the exception of the genus Proteus, which was 8.6% in fast-thawed mackerel during storage at ambient temperature. This suggests that the decarboxylation potential is dependent on both microbial load and microbial community structure....

Synthesis and characterization of Co3O4 and its performance for the detachment reaction of oxygen

International Nuclear Information System (INIS)

Morales G, P.; Fernandez V, S.M.

2001-01-01

The cobaltous cobaltic oxide was synthesized by the sol-gel technique. Therefore first the cobalt maleate was synthesized. The temperature of decarboxylation was determined by thermogravimetry. The obtained compound was characterized by X-ray diffraction, scanning electron microscopy Sem and the X-ray dispersive energy. The electrochemical tests were realized with a 273A potensiostate galvanostate, by using an electrochemical cell of three electrodes. The cobaltous cobaltic oxide prepared by this method, presented a major activity for the oxide detachment that those reported in the literature. (Author)

Studies on some important secondary metabolites from marine organisms

Digital Repository Service at National Institute of Oceanography (India)

Parvatkar, R.R.

-(2,4- dibromo-5-methoxyphenyl)ethanamine (15) from this species suggest that amathamides and amathaspiramides are biosynthesized from phenylalanine by a series of aromatic substitution reactions and a decarboxylation giving the amines of the type 15, which... an aldehyde with HCN. HCN is generated in situ from cyanide salt such as NaCN, KCN, etc by treatment with a mineral acid. It is not safe to use HCN or its salts owing to its toxic effects that are fatal. Moreover, the yields of these reactions are poor...

Efficient Synthesis of β-Aryl-γ-lactams and Their Resolution with (S-Naproxen: Preparation of (R- and (S-Baclofen

Directory of Open Access Journals (Sweden)

Iris J. Montoya-Balbás

2015-12-01

Full Text Available An efficient synthesis of enantiomerically-pure β-aryl-γ-lactams is described. The principal feature of this synthesis is the practical resolution of β-aryl-γ-lactams with (S-Naproxen. The procedure is based on the Michael addition of nitromethane to benzylidenemalonates, which was easily obtained, followed by the reduction of the γ-nitroester in the presence of Raney nickel and the subsequent saponification/decarboxylation reaction. The utility of this methodology was highlighted by the preparation of enantiomerically-pure (R- and (S-Baclofen hydrochloride.

Low-temperature side-chain cleavage and decarboxylation of polythiophene esters by acid catalysis

DEFF Research Database (Denmark)

Søndergaard, Roar; Norrman, Kion; Krebs, Frederik C

2012-01-01

Solubility switching of polymers is very useful in thin layer processing of conjugated polymers, as it allows for multilayer processing and increases the stability of the polymer. Acid catalyzed thermocleavage of ester groups from thiophene polymers carrying primary, secondary, and tertiary subst...

Surface interactions and degradation of a fluoroquinolone antibiotic in the dark in aqueous TiO{sub 2} suspensions

Energy Technology Data Exchange (ETDEWEB)

Peterson, Jonathan W., E-mail: peterson@hope.edu [Department of Geological & Environmental Sciences, Hope College, P.O. Box 9000, Holland, MI 49422-9000 (United States); Gu, Baohua [Environmental Sciences Division, Oak Ridge National Laboratory, P.O. Box 2008, Oak Ridge, TN 37831 (United States); Seymour, Michael D. [Department of Chemistry, Hope College, P.O. Box 9000, Holland, MI 49422-9000 (United States)

2015-11-01

Fluoroquinolone antibiotics (FQs) are important drugs used in human and veterinary medicine. Their detection in natural waters and waste water treatment plants, along with increased resistance to FQs among some bacteria, have generated an increased interest in the fate of these drugs in the environment. Partitioning of FQs between an aqueous solution and attendant substrates depends, in part, on the surface reactivity of the adsorbent, commonly a function of particle size, surface charge, and functional groups. This study investigated the surface interactions between the FQ drug ofloxacin (OFL) and titanium oxide (TiO{sub 2}), a common catalyst and widely-observed constituent in many consumer products. Raman and fluorescence spectroscopic techniques, as well as LC/MS, were used to determine the OFL moieties present on TiO{sub 2} surfaces and in attendant solutions. Raman spectra indicate that the C=O (ketone) group of the quinolone core, the NH{sup +} of the piperazinyl ring, and CH{sub 3} of benzoxazine core are the most active in sorption onto the TiO{sub 2} surface. Raman spectra also show that the sorbed benzoxazine–quinolone core and piperazinyl moieties are readily desorbed from the surface by re-suspending samples in water. Importantly, we found that OFL could be degraded by reacting with TiO{sub 2} even in the dark. Complementary LC/MS analysis of the attendant supernatants indicates the presence of de-piperazinylated and de-carboxylated OFL breakdown products in supernatant solutions. Together, both Raman and LC/MS analyses indicate that TiO{sub 2} breaks the compound into piperazinyl and carboxylate groups which attach to the surface, whereas de-carboxylated and hydroxylated quinolone moieties remain in solution. The present study thus identifies the sorption mechanisms and breakdown products of OFL during dark reactions with TiO{sub 2}, which is critically important for understanding the fate and transport of OFL as it enters the soil and aquatic

A Mononuclear Iron-Dependent Methyltransferase Catalyzes Initial Steps in Assembly of the Apratoxin A Polyketide Starter Unit.

Science.gov (United States)

Skiba, Meredith A; Sikkema, Andrew P; Moss, Nathan A; Tran, Collin L; Sturgis, Rebecca M; Gerwick, Lena; Gerwick, William H; Sherman, David H; Smith, Janet L

2017-12-15

Natural product biosynthetic pathways contain a plethora of enzymatic tools to carry out difficult biosynthetic transformations. Here, we discover an unusual mononuclear iron-dependent methyltransferase that acts in the initiation steps of apratoxin A biosynthesis (AprA MT1). Fe 3+ -replete AprA MT1 catalyzes one or two methyl transfer reactions on the substrate malonyl-ACP (acyl carrier protein), whereas Co 2+ , Fe 2+ , Mn 2+ , and Ni 2+ support only a single methyl transfer. MT1 homologues exist within the "GNAT" (GCN5-related N-acetyltransferase) loading modules of several modular biosynthetic pathways with propionyl, isobutyryl, or pivaloyl starter units. GNAT domains are thought to catalyze decarboxylation of malonyl-CoA and acetyl transfer to a carrier protein. In AprA, the GNAT domain lacks both decarboxylation and acyl transfer activity. A crystal structure of the AprA MT1-GNAT di-domain with bound Mn 2+ , malonate, and the methyl donor S-adenosylmethionine (SAM) reveals that the malonyl substrate is a bidentate metal ligand, indicating that the metal acts as a Lewis acid to promote methylation of the malonyl α-carbon. The GNAT domain is truncated relative to functional homologues. These results afford an expanded understanding of MT1-GNAT structure and activity and permit the functional annotation of homologous GNAT loading modules both with and without methyltransferases, additionally revealing their rapid evolutionary adaptation in different biosynthetic contexts.

Mechanism of degradation and discoloration reaction of L-ascorbic acid

International Nuclear Information System (INIS)

Kurata, Tadao

1976-01-01

The mechanisms of decomposition and coloration reaction of L-ascorbic acid are reviewed. At the initial stage of the decomposition, it can be classified roughly into oxidative and non-oxidative processes of decomposition. ASA forms furfural by being heated and decomposed in strong acid. The mechanism of the production of furfural at varying pH in acidic region was discussed. Furfural was produced through the enol form of 3-deoxy-L-pentosulose(3DP). 3DP seemed to be produced by two different routes: the one route consists of successive reactions from ASA through lactone ring-opening, dehydration, decarboxylation, to 3DP, and the other consists of reactions from the 3-keto form of ASA, through lactone ring-opening, decarboxylation, and dehydration, to the enol form of 3DP. ASA is easily reduced and decomposed through dehydro-ASA(DHA) by the presence of an oxidizing agent. The decomposition of DHA is discussed in cases of the systems of DHA alone, DHA and α-aminoacid, and DHA and amine. DHA was decomposed by the same reaction scheme as the decomposition of ASA and yielded 2-furoic acid. In the presence of an amino acid, DHA was decomposed by the Strecker decomposition, and yielded a red compound and a radical. In the presence of an amine, the discoloration reaction seemed to take place through radical reaction mechanism. The coloration reaction of ASA occurs in an acidic medium, and is accelerated by the oxidative process of decomposition. (Nishino, S.)

Prokaryotic Heme Biosynthesis: Multiple Pathways to a Common Essential Product.

Science.gov (United States)

Dailey, Harry A; Dailey, Tamara A; Gerdes, Svetlana; Jahn, Dieter; Jahn, Martina; O'Brian, Mark R; Warren, Martin J

2017-03-01

The advent of heme during evolution allowed organisms possessing this compound to safely and efficiently carry out a variety of chemical reactions that otherwise were difficult or impossible. While it was long assumed that a single heme biosynthetic pathway existed in nature, over the past decade, it has become clear that there are three distinct pathways among prokaryotes, although all three pathways utilize a common initial core of three enzymes to produce the intermediate uroporphyrinogen III. The most ancient pathway and the only one found in the Archaea converts siroheme to protoheme via an oxygen-independent four-enzyme-step process. Bacteria utilize the initial core pathway but then add one additional common step to produce coproporphyrinogen III. Following this step, Gram-positive organisms oxidize coproporphyrinogen III to coproporphyrin III, insert iron to make coproheme, and finally decarboxylate coproheme to protoheme, whereas Gram-negative bacteria first decarboxylate coproporphyrinogen III to protoporphyrinogen IX and then oxidize this to protoporphyrin IX prior to metal insertion to make protoheme. In order to adapt to oxygen-deficient conditions, two steps in the bacterial pathways have multiple forms to accommodate oxidative reactions in an anaerobic environment. The regulation of these pathways reflects the diversity of bacterial metabolism. This diversity, along with the late recognition that three pathways exist, has significantly slowed advances in this field such that no single organism's heme synthesis pathway regulation is currently completely characterized. Copyright © 2017 American Society for Microbiology.

Radical formation of irradiated α-alanine and N-acetyl alanine with heavy ion beams. Effects of the irradiation temperature

International Nuclear Information System (INIS)

Minegishi, Atsuko; Nagasaki, Jun; Mori, Wasuke; Amano, Chikara; Takagi, Shinji; Murakami, Takeshi; Kanai, Tatsuaki; Furusawa, Yoshiya; Iwata, Yoshiyuki

2003-01-01

The characteristics of irradiation with C290 MeV/u ion beams were investigated using X-band electron spin resonance (ESR) spectroscopy for a polycrystalline powder of L-α-alanine at from 77K to 310K. The formed main radicals at 190K∼310K were the deamino radical and the decarboxyl radical. Because of the first-derivative ESR, decarboxyl radical showed an expanded spectral width and a lower peak height because of its amino hydrogen and nitrogen than that of the same amount of deamino radical. The ESR of irradiated L-α-alanine predominantly indicates the spectrum of the deamino radical. On the irradiated, L-α-alanine at from 77K to 310K ESR showed 1:4:6:4:1 lines at 220K and at room temperature, which indicate that the methyl group of the radical was rotating. On the other hand, at 77K ESR the spectrum showed nearly 1:5:5:5:1 lines, like the teeth of a saw, on samples irradiated at 270K∼350K (range IV), and 1:4:6:4:1 lines for those irradiated at 180K∼260K (range II and III), respectively. It is considered that the radical conformation of the deamino radical is planar (most stable conformation) on an irradiated sample in range IV, and a pyramidal structure on the irradiated sample in ranges II and III. (author)

Deoxygenation of methyl laurate over Ni based catalysts: Influence of supports

Science.gov (United States)

Xia, Xiaoqiang; Chen, Hui; Bi, Yadong; Hu, Jianli

2017-10-01

The use of a series of nickel based catalysts supported over HZSM-5, Al2O3, C and ZrO2 in the deoxygenation of methyl laurate shows that the deoxygenation activity and deoxygenation pathway of nickel based catalysts can be affected by properties of catalysts. In the absence of H2, β-elimination of methyl laurate is the dominant reaction and a small amount of laurate acid is converted into undecane by direct decarboxylation. At the same time, the highly acidic support HZSM-5 gave higher conversion and C11 alkane selectivity. In the presence of H2, Ni/HZSM-5 catalyst showed a significantly high deoxygenation activity, producing 71% alkanes by methyl laurate conversion at 280 °C and 4MPa H2. While as on mildly acidic (Al2O3) and neutral (C) supports, a restricted hydrodeoxygenation activity was achieved but more oxygenate products were yielded. According to the analysis of intermediate product, the deoxygenation reaction of methyl laurate follows three distinct pathways: in the absence of H2, decarboxylation: C11H23COOCH3→C11H23COOH→C11H24; in the presence of H2, decarbonylation: C11H23COOCH3→C11H23COOH→C11H23CHO→C11H24; and hydrodeoxygenation: C11H23COOCH3 →C11H23COOH→C11H23CHO→C12H25OH→C12H26

Activities of arginine and ornithine decarboxylases in various plant species.

Science.gov (United States)

Birecka, H; Bitonti, A J; McCann, P P

1985-10-01

In extracts from the youngest leaves of Avena sativa, Hordeum vulgare, Zea Mays, Pisum sativum, Phaseolus vulgaris, Lactuca sativa, and four pyrrolizidine alkaloid-bearing species of Heliotropium, the activities of ornithine decarboxylase, close to V(max), ranged between traces and 1.5 nanomoles per hour per gram fresh weight when based on putrescine formed during incubation with labeled ornithine. The arginine decarboxylase activities in the same extracts ranged between 8 and 8000 nanomoles per hour per gram fresh weight being lowest in the borages and highest in oat and barley. alpha-Difluoromethylornithine and alpha-difluoromethylarginine inhibited ornithine and arginine decarboxylases, respectively, in all species. Agmatine, putrescine, spermidine, and spermine were found in all, diaminopropane in eight, and cadaverine in three species.No correlation was observed between arginine or ornithine decarboxylase level and the levels of total polyamines. The in vitro decarboxylase activities found in the borages cannot explain the high accumulation of putrescine-derived pyrrolizidines in their youngest leaves if the pyrrolizidines are produced in situ from arginine and/or ornithine as precursors; other possibilities are discussed.In assays of ornithine decarboxylase, an interference of decarboxylation not due to this enzyme was observed in extracts from all species. In arginine decarboxylase assays, the interfering decarboxylation as well as the interference of arginase were apparent in two species. Addition of aminoguanidine was needed to suppress oxidative degradation of putrescine and agmatine during incubation of extracts from pea, bean, lettuce, Heliotropium angiospermum, and Heliotropium indicum.

Activities of Arginine and Ornithine Decarboxylases in Various Plant Species 1

Science.gov (United States)

Birecka, Helena; Bitonti, Alan J.; McCann, Peter P.

1985-01-01

In extracts from the youngest leaves of Avena sativa, Hordeum vulgare, Zea Mays, Pisum sativum, Phaseolus vulgaris, Lactuca sativa, and four pyrrolizidine alkaloid-bearing species of Heliotropium, the activities of ornithine decarboxylase, close to Vmax, ranged between traces and 1.5 nanomoles per hour per gram fresh weight when based on putrescine formed during incubation with labeled ornithine. The arginine decarboxylase activities in the same extracts ranged between 8 and 8000 nanomoles per hour per gram fresh weight being lowest in the borages and highest in oat and barley. α-Difluoromethylornithine and α-difluoromethylarginine inhibited ornithine and arginine decarboxylases, respectively, in all species. Agmatine, putrescine, spermidine, and spermine were found in all, diaminopropane in eight, and cadaverine in three species. No correlation was observed between arginine or ornithine decarboxylase level and the levels of total polyamines. The in vitro decarboxylase activities found in the borages cannot explain the high accumulation of putrescine-derived pyrrolizidines in their youngest leaves if the pyrrolizidines are produced in situ from arginine and/or ornithine as precursors; other possibilities are discussed. In assays of ornithine decarboxylase, an interference of decarboxylation not due to this enzyme was observed in extracts from all species. In arginine decarboxylase assays, the interfering decarboxylation as well as the interference of arginase were apparent in two species. Addition of aminoguanidine was needed to suppress oxidative degradation of putrescine and agmatine during incubation of extracts from pea, bean, lettuce, Heliotropium angiospermum, and Heliotropium indicum. PMID:16664442

Synthesis of carbon-14 labelled (5Z)-4-bromo-5-(bromomethylene)-2(5H)-furanone:

DEFF Research Database (Denmark)

Persson, T.; Johansen, S.K.; Martiny, L.

2004-01-01

The potent quorum sensing inhibitor (5Z)-4-bromo-5-(bromomethylene)-2(5H)-[2-C-14]furanone has been prepared in five steps in 7.7% overall yield starting from bromo[1-C-14]acetic acid. Condensation of ethyl bromo[1-C-14]acetate with ethyl acetoacetate followed by decarboxylation was accelerated...... by microwave heating to afford [1-C-14]levulinic acid. Subsequently, bromination and oxidation gave the targeted furan-2-one with a radiochemical purity of > 97% and a specific activity of 57 mCi/mmol....

Degradation of amino acids to short-chain fatty acids in humans. An in vitro study

DEFF Research Database (Denmark)

Rasmussen, H S; Holtug, K; Mortensen, P B

1988-01-01

Short-chain fatty acids (SCFA) originate mainly in the colon through bacterial fermentation of polysaccharides. To test the hypothesis that SCFA may originate from polypeptides as well, the production of these acids from albumin and specific amino acids was examined in a faecal incubation system....... Albumin was converted to all C2-C5-fatty acids, whereas amino acids generally were converted to specific SCFA, most often through the combination of a deamination and decarboxylation of the amino acids, although more complex processes also took place. This study indicates that a part of the intestinal...

Long term stability of cannabis resin and cannabis extracts

DEFF Research Database (Denmark)

Lindholst, Christian

2010-01-01

at room temperature, 4 °C and - 20 °C for up to 4 years. Acidic THC degrades exponentially via decarboxylation with concentration halve-lives of approximately 330 and 462 days in daylight and darkness, respectively. The degradation of neutral THC seems to occur somewhat slower. When cannabinoids were...... stored in extracted form at room temperature the degradation rate of acidic THC increased significantly relative to resin material with concentration halve-lives of 35 and 91 days in daylight and darkness, respectively. Once cannabis material is extracted into organic solvents, care should be taken...

Effect of thiamine deficiency, pyrithiamine and oxythiamine on pyruvate metabolism in rat liver and brain in vivo

International Nuclear Information System (INIS)

Meghal, S.K.; O'Neal, R.M.; Koeppe, R.E.

1977-01-01

Rats were fed either a thiamine-deficient diet or diets containing pyrithiamine or oxythiamine. When symptoms of thiamine deficiency appeared, the animals were injected intraperitoneally with [2- 14 C] pyruvate six to twelve minutes prior to sacrifice. Free glutamic and aspartic acids were isolated from liver and brain and degraded. The results indicate that, in thiamine-deficient or oxythiamine-treated rats, pyruvate metabolism in liver and brain is similar to that in normal animals. In contrast, pyrithinamine drastically decreases the oxidative decarboxylation of pyruvate by rat liver. (auth.)

New degradation compounds from lignocellulosic biomass pretreatment: routes for formation of potent oligophenolic enzyme inhibitors

DEFF Research Database (Denmark)

Rasmussen, H.; Tanner, David Ackland; Sørensen, H. R.

2017-01-01

-condensation reactions involving aldol condensations, 1,4 additions to α,β unsaturated carbonyl compounds, 3-keto acid decarboxylations and oxidations. Furthermore, pentose reactions with phenolic lignin components are suggested. The identification of the central role of xylose in the reaction routes for oligophenolic...... inhibitor formation led to the solution to protect the reactive anomeric center in xylose. It is shown that protection of the anomeric center in in situ generated xylose with ethylene glycol monobutyl ether, during pretreatment of wheat straw, reduces the level of oligophenols by 73%. The results pave...

Studies on the key aroma compounds in raw (unheated) and heated Japanese soy sauce.

Science.gov (United States)

Kaneko, Shu; Kumazawa, Kenji; Nishimura, Osamu

2013-04-10

An investigation using the aroma extract dilution analysis (AEDA) technique of the aroma concentrate from a raw Japanese soy sauce and the heated soy sauce revealed 40 key aroma compounds including 7 newly identified compounds. Among them, 5(or 2)-ethyl-4-hydroxy-2(or 5)-methyl-3(2H)-furanone and 3-hydroxy-4,5-dimethyl-2(5H)-furanone exhibited the highest flavor dilution (FD) factor of 2048, followed by 3-(methylthio)propanal, 4-ethyl-2-methoxyphenol, and 4-hydroxy-2,5-dimethyl-3(2H)-furanone having FD factors from 128 to 512 in the raw soy sauce. Furthermore, comparative AEDAs, a quantitative analysis, and a sensory analysis demonstrated that whereas most of the key aroma compounds in the raw soy sauce were common in the heated soy sauce, some of the Strecker aldehydes and 4-vinylphenols contributed less to the raw soy sauce aroma. The model decarboxylation reactions of the phenolic acids during heating of the raw soy sauce revealed that although all reactions resulted in low yields, the hydroxycinnamic acid derivatives were much more reactive than the hydroxybenzoic acid derivatives due to the stable reaction intermediates. Besides the quantitative analyses of the soy sauces, the estimation of the reaction yields of the phenolic compounds in the heated soy sauce revealed that although only the 4-vinylphenols increased during heating of the raw soy sauce, they might not mainly be formed as decarboxylation products from the corresponding hydroxycinnamic acids but from the other proposed precursors, such as lignin, shakuchirin, and esters with arabinoxylan.

Suppression of LFA-1 expression by spermine is associated with enhanced methylation of ITGAL, the LFA-1 promoter area.

Directory of Open Access Journals (Sweden)

Yoshihiko Kano

Full Text Available Spermine and spermidine, natural polyamines, suppress lymphocyte function-associated antigen 1 (LFA-1 expression and its associated cellular functions through mechanisms that remain unknown. Inhibition of ornithine decarboxylase, which is required for polyamine synthesis, in Jurkat cells by 3 mM D,L-alpha-difluoromethylornithine hydrochloride (DFMO significantly decreased spermine and spermidine concentrations and was associated with decreased DNA methyltransferase (Dnmt activity, enhanced demethylation of the LFA-1 gene (ITGAL promoter area, and increased CD11a expression. Supplementation with extracellular spermine (500 µM of cells pretreated with DFMO significantly increased polyamine concentrations, increased Dnmt activity, enhanced methylation of the ITGAL promoter, and decreased CD11a expression. It has been shown that changes in intracellular polyamine concentrations affect activities of -adenosyl-L-methionine-decaroboxylase, and, as a result, affect concentrations of the methyl group donor, S-adenosylmethionine (SAM, and of the competitive Dnmt inhibitor, decarboxylated SAM. Additional treatments designed to increase the amount of SAM and decrease the amount of decarboxylated SAM-such as treatment with methylglyoxal bis-guanylhydrazone (an inhibitor of S-adenosyl-L-methionine-decaroboxylase and SAM supplementation-successfully decreased CD11a expression. Western blot analyses revealed that neither DFMO nor spermine supplementation affected the amount of active Ras-proximate-1, a member of the Ras superfamily of small GTPases and a key protein for regulation of CD11a expression. The results of this study suggest that polyamine-induced suppression of LFA-1 expression occurs via enhanced methylation of ITGAL.

A Unique (3+2) Annulation Reaction between Meldrum's Acid and Nitrones: Mechanistic Insight by ESI-IMS-MS and DFT Studies.

Science.gov (United States)

Lespes, Nicolas; Pair, Etienne; Maganga, Clisy; Bretier, Marie; Tognetti, Vincent; Joubert, Laurent; Levacher, Vincent; Hubert-Roux, Marie; Afonso, Carlos; Loutelier-Bourhis, Corinne; Brière, Jean-François

2018-03-15

The fragile intermediates of the domino process leading to an isoxazolidin-5-one, triggered by unique reactivity between Meldrum's acid and an N-benzyl nitrone in the presence of a Brønsted base, were determined thanks to the softness and accuracy of electrospray ionization mass spectrometry coupled to ion mobility spectrometry (ESI-IMS-MS). The combined DFT study shed light on the overall organocatalytic sequence that starts with a stepwise (3+2) annulation reaction that is followed by a decarboxylative protonation sequence encompassing a stereoselective pathway issue. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A new radiochemical assay for fructose-1,6-diphosphatase in human leucocytes

International Nuclear Information System (INIS)

Janssen, A.J.M.; Trijbels, F.J.M.

1982-01-01

Fructose-1,6-diphosphatase (D-fructose-1,6-diphosphate 1-phosphohydrolase, EC 3.1.3.11, FDPase) is one of the key enzymes of the gluconeogenic pathway. Measuring the activity both in the presence and in the absence of AMP yields the true FDPase activity, corrected for non-specific phosphatase activity. In this paper the authors introduce a new radiochemical assay for FDPase, based on the decarboxylating activity of 6-phosphogluconate dehydrogenase. One molecule [U- 14 C]fructose-1,6-diphosphate yields one molecule 14 CO 2 which can be captured in strongly basic solutions and counted in a liquid scintillation counter. (Auth.)

The action of piracetam on 14C-glucose metabolism in normal and posthypoxic rat cerebral cortex slices

International Nuclear Information System (INIS)

Domanska-Janik, K.; Zaleska, M.

1977-01-01

The stimulating effect of piracetam on the respiration and glycolysis was observed in rat brain cortex slices incubated under oxygen atmosphere. After preincubation of the slices under pure nitrogen atmosphere, piracetam influenced also decarboxylation of the C 1 -glucose carbon, indicating stimulation of the pentose cycle. Any significant effect of piracetam on the lowered by anoxia incorporation of 14 C from U- 14 C-glucose into macromolecular fractions was not observed. The results have supported a protective effect of piracetam against oxygen deficiency, caused mainly by stimulation of metabolic glucose pathways, connected with energy production in CNS. (author)

Method of preparation of tritiated benzene for measuring in hydrology low level tritium in a liquid scintillator

International Nuclear Information System (INIS)

Pichat, L.; Sharefkin, D.; Herbert, M.

1962-01-01

It is given a preliminary account of the preparation of tritiated benzene by decarboxylation of calcium mellitate (calcium benzene-hexa-carboxylate) at 500 deg C by an excess of tritiated barium or calcium hydroxide yield is 64-72 pour cent based on used calcium mellitate. Benzene obtained after a single distillation is free from seriously quenching impurities. It is obtained 10-15 g benzene per batch. It remains to determine the occurrence of an isotope effect during the reaction. Various improvements and modifications are still necessary to increase the size of the sample to be treated. (authors) [fr

Increased receptor density of α2 adrenoceptors and GABAA α5 receptors in limbic brain regions in the domoic acid rat model of epilepsy

DEFF Research Database (Denmark)

Thomsen, Majken; Lillethorup, Thea Pinholt; Wegener, Gregers

Background: The presymptomatic events involved in epilepsy remain elusive but represent a chance to understand disease development and stop the pathogenic processes leading to chronic epilepsy. Previous studies have found increased levels of α2 adrenoceptors and decreased levels of glutamic acid...... decarboxylase, a catalyst of the decarboxylation of glutamate to GABA. Methods: Male Sprague-Dawley rats (N=3) were injected (s.c.) daily from postnatal day 8-14 with saline or sub-convulsive doses of the glutamate agonist DOM (20µg/kg). At ~120 days of age the rats were decapitated. The brains were removed...

Kinetics of formation of acrylamide and Schiff base intermediates from asparagine and glucose

DEFF Research Database (Denmark)

Hedegaard, Rikke Susanne Vingborg; Frandsen, Henrik; Skibsted, Leif H.

2008-01-01

From the concentration of glucose and asparagine as reactants and of acrylamide as product each determined by LC-MS during reaction in an acetonitrile/water (68:32) model system at pH 7.6 (0.04 M phosphate buffer) and from the relative concentration of the Schiff base intermediate, the decarboxyl......From the concentration of glucose and asparagine as reactants and of acrylamide as product each determined by LC-MS during reaction in an acetonitrile/water (68:32) model system at pH 7.6 (0.04 M phosphate buffer) and from the relative concentration of the Schiff base intermediate...

Requirement of a Functional Flavin Mononucleotide Prenyltransferase for the Activity of a Bacterial Decarboxylase in a Heterologous Muconic Acid Pathway in Saccharomyces cerevisiae.

Science.gov (United States)

Weber, Heike E; Gottardi, Manuela; Brückner, Christine; Oreb, Mislav; Boles, Eckhard; Tripp, Joanna

2017-05-15

Biotechnological production of cis , cis -muconic acid from renewable feedstocks is an environmentally sustainable alternative to conventional, petroleum-based methods. Even though a heterologous production pathway for cis , cis -muconic acid has already been established in the host organism Saccharomyces cerevisiae , the generation of industrially relevant amounts of cis , cis -muconic acid is hampered by the low activity of the bacterial protocatechuic acid (PCA) decarboxylase AroY isomeric subunit C iso (AroY-C iso ), leading to secretion of large amounts of the intermediate PCA into the medium. In the present study, we show that the activity of AroY-C iso in S. cerevisiae strongly depends on the strain background. We could demonstrate that the strain dependency is caused by the presence or absence of an intact genomic copy of PAD1 , which encodes a mitochondrial enzyme responsible for the biosynthesis of a prenylated form of the cofactor flavin mononucleotide (prFMN). The inactivity of AroY-C iso in strain CEN.PK2-1 could be overcome by plasmid-borne expression of Pad1 or its bacterial homologue AroY subunit B (AroY-B). Our data reveal that the two enzymes perform the same function in decarboxylation of PCA by AroY-C iso , although coexpression of Pad1 led to higher decarboxylase activity. Conversely, AroY-B can replace Pad1 in its function in decarboxylation of phenylacrylic acids by ferulic acid decarboxylase Fdc1. Targeting of the majority of AroY-B to mitochondria by fusion to a heterologous mitochondrial targeting signal did not improve decarboxylase activity of AroY-C iso , suggesting that mitochondrial localization has no major impact on cofactor biosynthesis. IMPORTANCE In Saccharomyces cerevisiae , the decarboxylation of protocatechuic acid (PCA) to catechol is the bottleneck reaction in the heterologous biosynthetic pathway for production of cis , cis -muconic acid, a valuable precursor for the production of bulk chemicals. In our work, we demonstrate

Reaction pathway and oxidation mechanisms of dibutyl phthalate by persulfate activated with zero-valent iron

Energy Technology Data Exchange (ETDEWEB)

Li, Huanxuan [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China); Wan, Jinquan, E-mail: ppjqwan@scut.edu.cn [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China); State Key Lab Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640 (China); Ma, Yongwen [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China); State Key Lab Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640 (China); Wang, Yan [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China)

2016-08-15

This study investigated reaction pathway and oxidation mechanisms of dibutyl phthalate (DBP) by persulfate (PS) activated with zero-valent iron (ZVI). The DBP degradation was studied at three pH values (acidic, neutral and basic) in the presence of different organic scavengers. Using a chemical probe method, both sulfate radical (SO{sub 4}·{sup −}) and hydroxyl radical (·OH) were found to be primary oxidants at pH 3.0 and pH 7.0, respectively while ·OH was the major specie to oxidize DBP at pH 11.0. A similar result was found in an experiment of Electron Spin Resonance spin-trapping where in addition to ·OH, superoxide radical (O{sub 2}·{sup −}) was detected at pH 11.0. The transformation of degradation products including dimethyl phthalate (DMP), diethyl phthalate (DEP), phthalic anhydride, and acetophenone exhibited diverse variation during the reaction processes. The phthalic anhydride concentration appeared to be maximum at all pHs. Another eleven intermediate products were also found at pH 3.0 by GC–MS and HPLC analysis, and their degradation mechanisms and pathways were proposed. It was suggested that dealkylation, hydroxylation, decarboxylation and hydrogen extraction were the dominant degradation mechanisms of DBP at pH 3.0. - Highlights: • Both SO{sub 4}{sup −}· and ·OH were found to be the major active species at pH 3.0 and pH 7.0. • ·OH and ·O2– were the primary oxidants pH 11.0. • The intermediate products were investigated as well as the degradation pathway. • Dealkylation, hydroxylation, decarboxylation, H-extraction were the major mechanisms.

Magnesium stearine production via direct reaction of palm stearine and magnesium hydroxide

Science.gov (United States)

Pratiwi, M.; Ylitervo, P.; Pettersson, A.; Prakoso, T.; Soerawidjaja, T. H.

2017-06-01

The fossil oil production could not compensate with the increase of its consumption, because of this reason the renewable alternative energy source is needed to meet this requirement of this fuel. One of the methods to produce hydrocarbon is by decarboxylation of fatty acids. Vegetable oil and fats are the greatest source of fatty acids, so these can be used as raw material for biohydrocarbon production. From other researchers on their past researchs, by heating base soap from divalent metal, those metal salts will decarboxylate and produce hydrocarbon. This study investigate the process and characterization of magnesium soaps from palm stearine by Blachford method. The metal soaps are synthesized by direct reaction of palm stearine and magnesium hydroxide to produce magnesium stearine and magnesium stearine base soaps at 140-180°C and 6-10 bar for 3-6 hours. The operation process which succeed to gain metal soaps is 180°C, 10 bar, for 3-6 hours. These metal soaps are then compared with commercial magnesium stearate. Based on Thermogravimetry Analysis (TGA) results, the decomposition temperature of all the metal soaps were 250°C. Scanning Electron Microscope with Energy Dispersive X-ray (SEM-EDX) analysis have shown the traces of sodium sulphate for magnesium stearate commercial and magnesium hydroxide for both type of magnesium stearine soaps. The analysis results from Microwave Plasma-Atomic Emission Spectrometry (MP-AES) have shown that the magnesium content of magnesium stearine approximate with magnesium stearate commercial and lower compare with magnesium stearine base soaps. These experiments suggest that the presented saponification process method could produced metal soaps comparable with the commercial metal soaps.

[Progress and prospect of bio-jet fuels industry in domestic and overseas].

Science.gov (United States)

Qiao, Kai; Fu, Jie; Zhou, Feng; Ma, Huixia

2016-10-25

We reviewed the progress of the bio-jet fuels industry in recent years and systematically analyzed the technical routes that have been approved or in the pipeline for approval by ASTM D7566. In addition, we highlighted a novel pathway to produce drop-in fuel by near-critical hydrolysis of waste cooking oils or algal oils followed by catalytic decarboxylation. Also, we introduced the source of oils and fats feedstock and the domestic bio-jet fuel industry status during the 12th Five-Year-Plan period. Based on our own research, we discussed the prospect of the bio-jet fuel industry and future research needs.

Control of Biogenic Amines in Fermented Sausages: Role of Starter Cultures

Science.gov (United States)

Latorre-Moratalla, M.L.; Bover-Cid, Sara; Veciana-Nogués, M.T.; Vidal-Carou, M.C.

2012-01-01

Biogenic amines show biological activity and exert undesirable physiological effects when absorbed at high concentrations. Biogenic amines are mainly formed by microbial decarboxylation of amino acids and thus are usually present in a wide range of foods, fermented sausages being one of the major biogenic amine sources. The use of selected starter cultures is one of the best technological measures to control aminogenesis during meat fermentation. Although with variable effectiveness, several works show the ability of some starters to render biogenic amine-free sausages. In this paper, the effect of different starter culture is reviewed and the factors determining their performance discussed. PMID:22586423

Control of biogenic amines in fermented sausages: role of starter cultures

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Mariluz eLatorre-Moratalla

2012-05-01

Full Text Available Biogenic amines show biological activity and exert undesirable physiological effects when absorbed at high concentrations. Biogenic amines are mainly formed by microbial decarboxylation of amino acids and thus are usually present in a wide range of foods, fermented sausages being one of the major biogenic amine sources. The use of selected starter cultures is one of the best technological measures to control aminogenesis during meat fermentation. Although with variable effectiveness, several works show the ability of some starters to render biogenic amine-free sausages. In this paper, the effect of different starter culture is reviewed and the factors determining their performance discussed.

The Impact of a Mild Sub-Critical Hydrothermal Carbonization Pretreatment on Umbila Wood. A Mass and Energy Balance Perspective

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Carlos Alberto Cuvilas

2015-03-01

Full Text Available Over the last years, the pretreatment of biomass as a source of energy has become one of the most important steps of biomass conversion. In this work the effect of a mild subcritical hydrothermal carbonization of a tropical woody biomass was studied. Results indicate considerable change in carbon content from 52.78% to 65.1%, reduction of oxygen content from 41.14% to 28.72% and ash slagging and fouling potential. Even though decarboxylation, decarbonylation and dehydration reactions take place, dehydration is the one that prevails. The mass and energy balance was affected by the treatment conditions than the severity of the treatment.

Non-gaseous radiolysis products of procaine benzylpenicillin and Na salt 3-ortho-chloro-5-methyl-4-isoxasolyl penicillin

International Nuclear Information System (INIS)

Dziegielewski, J.; Jezowska-Trzebiatowska, B.

1974-01-01

Radiolysis products of procaine benzylpenicillin and Na salt 3-ortho-chlorophenyl-5-methyl-4-isoxasolyl penicillin were isolated and spectroscopic studies were made over the NMR, IR, UV and mass spectrometric ranges. On the basis of the results obtained, the bond breakage sites resulting from irradiation were determined and the modes of radiolysis decomposition were suggested. Irradiation of penicillins has been found to result in decomposition of the β-lactam and thiazolidine rings. Besides, decarboxylation of penicillins and bond cleavages within the amide group were observed as well as dehydrogenation and abstraction of simple hydrocarbons. The role of procaine and crystallization water in the radiolysis of penicillins was determined. (author)

Influence of the Annealing Temperature on the Photovoltaic Performance and Film Morphology Applying Novel Thermocleavable Materials

DEFF Research Database (Denmark)

Petersen, Martin Helgesen; Bjerring, Morten; Nielsen, Niels Chr.

2010-01-01

efficiencies of up to 1.92% were observed for polymers bearing ester groups on the 4-positions of the thienyl groups (T2), but shifting them to the 3-positions (T1) reduced the efficiency significantly to 0.18%. The thermal behavior of the polymers was studied with thermogravimetric analysis (TGA) that showed...... a weight loss around 200 °C corresponding to elimination of the ester side chains followed by a second weight loss around 300 °C corresponding to loss of CO2 via decarboxylation. The temperature of thermocleavage of the active layer films was optimized to 265 °C whereby the T2:PCBM solar cells maintained...

Protein and peptide alkoxyl radicals can give rise to C-terminal decarboxylation and backbone cleavage

DEFF Research Database (Denmark)

Davies, Michael Jonathan

1996-01-01

Previous studies have demonstrated that gamma-irradiation of some free amino acids in the presence of oxygen gives high yields of side-chain hydroperoxides. It is shown in the present study that N-acetyl amino acids and peptides also give high levels of hydroperoxides on gamma-irradiation, even...

Catalytic transformations of fatty acids derivatives for food, oleochemicals and fuels over carbon supported platinum group metals

Energy Technology Data Exchange (ETDEWEB)

Simakova, I.

2010-07-01

The main focus of the research is in the development of an alternative harmless Pd-based hydrogenation technology compared to the traditional one based on Ni. Pd counterparts could be recycled, is more active and resistant to acids and form less trans isomers. In order to be economically viable and competitive this technology has to be based on the best catalyst that means an optimized combination of high activity, high life-time and high selectivity. Therefore, the engineering aspects were closely taken into account and much effort was directed into the design of Pd on a mesoporous carbon support as well as in establishing the correlation between catalyst characteristics and its activity in the C=C hydrogenation and isomerization. Detailed characterization (TEM, XRD, XPS, TPR, CO TPD, physisorption and CO chemisorption) of the tested catalysts was carried out. In addition, the influence of temperature, hydrogen pressure, catalytic concentration on the fatty-acid and isomeric composition of hydrogenated oils were determined in the absence of mass transfer limitations. Deoxygenation by full decarboxylation of -COOH function of fatty acid is the best way to make green diesel because paraffins are produced and utilization of expensive hydrogen is not required. Deoxygenation was systematically investigated over Pd/C (Sibunit) using saturated fatty acids C16 - C20 and C22, as feeds, producing one less carbon containing, diesel-like hydrocarbons. The same decarboxylation rates were obtained for pure saturated fatty acids. Comparison of deoxygenation rate for stearic, oleic or linoleic acids as a feedstock at 300 deg C under 1 vol% hydrogen over mesoporous Pd/C (Sibunit) catalyst revealed that catalyst activity and selectivity increased with less unsaturated feedstock. The main products in the case of stearic acid were desired C17 hydrocarbons, whereas the amounts of C17 aromatic compounds increased in case of oleic and linoleic acids. Catalyst deactivation was relatively

Activated Persulfate Oxidation of Perfluorooctanoic Acid (PFOA in Groundwater under Acidic Conditions

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Penghua Yin

2016-06-01

Full Text Available Perfluorooctanoic acid (PFOA is an emerging contaminant of concern due to its toxicity for human health and ecosystems. However, successful degradation of PFOA in aqueous solutions with a cost-effective method remains a challenge, especially for groundwater. In this study, the degradation of PFOA using activated persulfate under mild conditions was investigated. The impact of different factors on persulfate activity, including pH, temperature (25 °C–50 °C, persulfate dosage and reaction time, was evaluated under different experimental conditions. Contrary to the traditional alkaline-activated persulfate oxidation, it was found that PFOA can be effectively degraded using activated persulfate under acidic conditions, with the degradation kinetics following the pseudo-first-order decay model. Higher temperature, higher persulfate dosage and increased reaction time generally result in higher PFOA degradation efficiency. Experimental results show that a PFOA degradation efficiency of 89.9% can be achieved by activated persulfate at pH of 2.0, with the reaction temperature of 50 °C, molar ratio of PFOA to persulfate as 1:100, and a reaction time of 100 h. The corresponding defluorination ratio under these conditions was 23.9%, indicating that not all PFOA decomposed via fluorine removal. The electron paramagnetic resonance spectrometer analysis results indicate that both SO4−• and •OH contribute to the decomposition of PFOA. It is proposed that PFOA degradation occurs via a decarboxylation reaction triggered by SO4−•, followed by a HF elimination process aided by •OH, which produces one-CF2-unit-shortened perfluoroalkyl carboxylic acids (PFCAs, Cn−1F2n−1COOH. The decarboxylation and HF elimination processes would repeat and eventually lead to the complete mineralization all PFCAs.

Genes involved in long-chain alkene biosynthesis in Micrococcus luteus

Energy Technology Data Exchange (ETDEWEB)

Beller, Harry R.; Goh, Ee-Been; Keasling, Jay D.

2010-01-07

Aliphatic hydrocarbons are highly appealing targets for advanced cellulosic biofuels, as they are already predominant components of petroleum-based gasoline and diesel fuels. We have studied alkene biosynthesis in Micrococcus luteus ATCC 4698, a close relative of Sarcina lutea (now Kocuria rhizophila), which four decades ago was reported to biosynthesize iso- and anteiso branched, long-chain alkenes. The underlying biochemistry and genetics of alkene biosynthesis were not elucidated in those studies. We show here that heterologous expression of a three-gene cluster from M. luteus (Mlut_13230-13250) in a fatty-acid overproducing E. coli strain resulted in production of long-chain alkenes, predominantly 27:3 and 29:3 (no. carbon atoms: no. C=C bonds). Heterologous expression of Mlut_13230 (oleA) alone produced no long-chain alkenes but unsaturated aliphatic monoketones, predominantly 27:2, and in vitro studies with the purified Mlut_13230 protein and tetradecanoyl-CoA produced the same C27 monoketone. Gas chromatography-time of flight mass spectrometry confirmed the elemental composition of all detected long-chain alkenes and monoketones (putative intermediates of alkene biosynthesis). Negative controls demonstrated that the M. luteus genes were responsible for production of these metabolites. Studies with wild-type M. luteus showed that the transcript copy number of Mlut_13230-13250 and the concentrations of 29:1 alkene isomers (the dominant alkenes produced by this strain) generally corresponded with bacterial population over time. We propose a metabolic pathway for alkene biosynthesis starting with acyl-CoA (or -ACP) thioesters and involving decarboxylative Claisen condensation as a key step, which we believe is catalyzed by OleA. Such activity is consistent with our data and with the homology (including the conserved Cys-His-Asn catalytic triad) of Mlut_13230 (OleA) to FabH (?-ketoacyl-ACP synthase III), which catalyzes decarboxylative Claisen condensation during

Genealogy profiling through strain improvement by using metabolic network analysis: metabolic flux genealogy of several generations of lysine-producing corynebacteria.

Science.gov (United States)

Wittmann, Christoph; Heinzle, Elmar

2002-12-01

A comprehensive approach of metabolite balancing, (13)C tracer studies, gas chromatography-mass spectrometry, matrix-assisted laser desorption ionization-time of flight mass spectrometry, and isotopomer modeling was applied for comparative metabolic network analysis of a genealogy of five successive generations of lysine-producing Corynebacterium glutamicum. The five strains examined (C. glutamicum ATCC 13032, 13287, 21253, 21526, and 21543) were previously obtained by random mutagenesis and selection. Throughout the genealogy, the lysine yield in batch cultures increased markedly from 1.2 to 24.9% relative to the glucose uptake flux. Strain optimization was accompanied by significant changes in intracellular flux distributions. The relative pentose phosphate pathway (PPP) flux successively increased, clearly corresponding to the product yield. Moreover, the anaplerotic net flux increased almost twofold as a consequence of concerted regulation of C(3) carboxylation and C(4) decarboxylation fluxes to cover the increased demand for lysine formation; thus, the overall increase was a consequence of concerted regulation of C(3) carboxylation and C(4) decarboxylation fluxes. The relative flux through isocitrate dehydrogenase dropped from 82.7% in the wild type to 59.9% in the lysine-producing mutants. In contrast to the NADPH demand, which increased from 109 to 172% due to the increasing lysine yield, the overall NADPH supply remained constant between 185 and 196%, resulting in a decrease in the apparent NADPH excess through strain optimization. Extrapolated to industrial lysine producers, the NADPH supply might become a limiting factor. The relative contributions of PPP and the tricarboxylic acid cycle to NADPH generation changed markedly, indicating that C. glutamicum is able to maintain a constant supply of NADPH under completely different flux conditions. Statistical analysis by a Monte Carlo approach revealed high precision for the estimated fluxes, underlining the

Identification of the Products of Oxidation of Quercetin by Air Oxygenat Ambient Temperature

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Viktor A Utsal

2007-03-01

Full Text Available Oxidation of quercetin by air oxygen takes place in water and aqueous ethanol solutions under mild conditions, namely in moderately-basic media (pH ∼ 8-10 at ambient temperature and in the absence of any radical initiators, without enzymatic catalysis or irradiation of the reaction media by light. The principal reaction products are typical of other oxidative degradation processes of quercetin, namely 3,4-dihydroxy-benzoic (proto-catechuic and 2,4,6-trihydroxybenzoic (phloroglucinic acids, as well as the decarboxylation product of the latter – 1,3,5-trihydroxybenzene (phloroglucinol. In accordance with the literature data, this process involves the cleavage of the γ-pyrone fragment (ring C of the quercetin molecule by oxygen, with primary formation of 4,6-dihydroxy-2-(3,4-dihydroxybenzoyloxybenzoic acid (depside. However under such mild conditions the accepted mechanism of this reaction (oxidative decarbonylation with formation of carbon monoxide, CO should be reconsidered as preferably an oxidative decarboxylation with formation of carbon dioxide, CO2. Direct head-space analysis of the gaseous components formed during quercetin oxidation in aqueous solution at ambient temperature indicates that the ratio of carbon dioxide/carbon monoxide in the gas phase after acidification of the reaction media is ca. 96:4 %. Oxidation under these mild conditions is typical for other flavonols having OH groups at C3 (e.g., kaempferol, but it is completely suppressed if this hydroxyl group is substituted by a glycoside fragment (as in rutin, or a methyl substituent. An alternative oxidation mechanism involving the direct cleavage of the C2-C3 bond in the diketo-tautomer of quercetin is proposed.

A new biological method for preparing certain sulphurated substances labelled with S{sup 35}; Methode nouvelle de preparation par voie biologique de quelques substances soufrees marquees au soufre-35

Energy Technology Data Exchange (ETDEWEB)

Chapeville, F; Maier-Huser, H; Fromageot, P [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1962-07-01

Previous investigations have shown that the yolk-sac of embryonic bird's eggs can be used to produce the following reactions: (a) reduction of sulphate to sulphite; (b) fixation of the sulphite on the carbon chain produced by the desulf-hydration of l-cysteine, with formation of l-cysteic acid; (c) decarboxylation of the l-cysteine acid into taurine. The enzymatic system which causes reaction (b) has been purified. It also acts as a catalyst in the sulphur-exchange between the cysteine and the mineral sulphide. The authors have utilized these data in preparing sulphurated substances labelled with S{sup 35}: taurine S{sup 35}, l-cysteine S{sup 35} and l-cysteic acid S{sup 35}. For each of the three, they discuss the chemical reactions involved, the methods of preparation, the experimental conditions of extraction and purity-control, together with the yields and specific activities obtained. (authors) [French] Des travaux anterieurs ont montre l'aptitude du sac vitellin d'oeufs embryonn d'oiseaux a realiser les reactions suivantes: a) reduction du sulfate en sulfite, b) fixation du sulfite sur la chaine carbonee issue de la desulfhydration de la L-cysteine avec formation de l'acide L-cysteique. c) decarboxylation de l 'acide L-cysteique en taurine. Le systeme enzymatique responsable de la reaction b a ete purifie; il catalyse aussi l'echange du soufre de la cysteine avec celui du sulfure mineral. Les auteurs ont utilise ces donnees pour la preparation de substances soufrees marquees au {sup 35}S: taurine {sup 35}S, L-cysteine{sup 35} et acide L-cysteique {sup 35}S. Pour chacun de ces trois corps, ils decrivent les reactions chimiques mises en jeu, les modes operatoires de fabrication, les conditions experimentales d'extraction et de controle de la purete, ainsi que les resultats obtenus tant pour les rendements que pour les activites specifiques obtenues. (auteurs)

Structure and mechanism of a cysteine sulfinate desulfinase engineered on the aspartate aminotransferase scaffold.

Science.gov (United States)

Fernandez, Francisco J; de Vries, Dominique; Peña-Soler, Esther; Coll, Miquel; Christen, Philipp; Gehring, Heinz; Vega, M Cristina

2012-02-01

The joint substitution of three active-site residues in Escherichia coli (L)-aspartate aminotransferase increases the ratio of l-cysteine sulfinate desulfinase to transaminase activity 10(5)-fold. This change in reaction specificity results from combining a tyrosine-shift double mutation (Y214Q/R280Y) with a non-conservative substitution of a substrate-binding residue (I33Q). Tyr214 hydrogen bonds with O3 of the cofactor and is close to Arg374 which binds the α-carboxylate group of the substrate; Arg280 interacts with the distal carboxylate group of the substrate; and Ile33 is part of the hydrophobic patch near the entrance to the active site, presumably participating in the domain closure essential for the transamination reaction. In the triple-mutant enzyme, k(cat)' for desulfination of l-cysteine sulfinate increased to 0.5s(-1) (from 0.05s(-1) in wild-type enzyme), whereas k(cat)' for transamination of the same substrate was reduced from 510s(-1) to 0.05s(-1). Similarly, k(cat)' for β-decarboxylation of l-aspartate increased fromcat)' for transamination was reduced from 530s(-1) to 0.13s(-1). l-Aspartate aminotransferase had thus been converted into an l-cysteine sulfinate desulfinase that catalyzes transamination and l-aspartate β-decarboxylation as side reactions. The X-ray structures of the engineered l-cysteine sulfinate desulfinase in its pyridoxal-5'-phosphate and pyridoxamine-5'-phosphate form or liganded with a covalent coenzyme-substrate adduct identified the subtle structural changes that suffice for generating desulfinase activity and concomitantly abolishing transaminase activity toward dicarboxylic amino acids. Apparently, the triple mutation impairs the domain closure thus favoring reprotonation of alternative acceptor sites in coenzyme-substrate intermediates by bulk water. Copyright © 2011 Elsevier B.V. All rights reserved.

Carbohydrates stimulate ethylene production in tobacco leaf discs : I. Interaction with auxin and the relation to auxin metabolism.

Science.gov (United States)

Meir, S; Philosoph-Hadas, S; Epstein, E; Aharoni, N

1985-05-01

Various naturally occurring carbohydrates, applied at a concentration range of 1 to 100 mm, stimulated ethylene production for several days in indoleacetic acid (IAA)-treated or untreated tobacco (Nicotiana tabacum L. cv ;Xanthi') leaf discs. The lag period for this sugar-stimulated ethylene production was 8 to 12 hours after excision in the untreated leaf discs, but less than 2 hours in the IAA-treated ones. Among the tested carbohydrates, 12 were found to increase synergistically ethylene production, with d-galactose, sucrose, and lactose being the most active; mannitol and l-glucose had no effect. The extent and duration of the increased ethylene production was dependent upon the type of sugar applied, the tissue's age, and the existence of both exogenous IAA and sugar in the medium. Sucrose appeared to elicit a continuous IAA effect for 48 hours, as expressed by increased ethylene production, even when IAA was removed from the medium after a 4-hour pulse. Sucrose stimulated both the uptake and decarboxylation of [1-(14)C]IAA, as well as the hydrolysis of the esteric and amide IAA conjugates formed in the tissue after application of free IAA. This gradual hydrolysis was accompanied by a further accumulation of a third IAA metabolite. Moreover, synthetic indole-3-acetyl-l-alanine increased ethylene production mainly with sucrose, and this effect was accompanied by its increased decarboxylation and turnover pattern suggesting that release of free IAA was involved. An esteric IAA conjugate, tentatively identified by GC retention time was found to be the major component (84%) of the naturally occurring IAA conjugates in tobacco leaves. Accordingly the sucrose-stimulated ethylene production in tobacco leaves can be ascribed mainly to the sucrose-stimulated hydrolysis of the esteric IAA conjugate.

Photodegradation of ethyl paraben using simulated solar radiation and Ag{sub 3}PO{sub 4} photocatalyst

Energy Technology Data Exchange (ETDEWEB)

Frontistis, Zacharias [Department of Chemical Engineering, University of Patras, Caratheodory 1, University Campus, GR-26504 Patras (Greece); Antonopoulou, Maria [Department of Environmental & Natural Resources Management, University of Patras, 2 Seferi St., GR-30100 Agrinio (Greece); Petala, Athanasia [Department of Chemical Engineering, University of Patras, Caratheodory 1, University Campus, GR-26504 Patras (Greece); Venieri, Danae [School of Environmental Engineering, Technical University of Crete, Polytechneioupolis, GR-73100 Chania (Greece); Konstantinou, Ioannis [Department of Environmental & Natural Resources Management, University of Patras, 2 Seferi St., GR-30100 Agrinio (Greece); Department of Chemistry, University of Ioannina, GR-45110 Ioannina (Greece); Kondarides, Dimitris I. [Department of Chemical Engineering, University of Patras, Caratheodory 1, University Campus, GR-26504 Patras (Greece); Mantzavinos, Dionissios, E-mail: mantzavinos@chemeng.upatras.gr [Department of Chemical Engineering, University of Patras, Caratheodory 1, University Campus, GR-26504 Patras (Greece)

2017-02-05

Highlights: • Ag{sub 3}PO{sub 4} with a bandgap of 2.4 eV is a photocatalyst highly responsive to visible. • Factorial design was used to assess important factors for ethyl paraben degradation. • Ethyl paraben and Ag{sub 3}PO{sub 4} concentration, time, water matrix are significant factors. • Dealkylated and decarboxylated transformation by-products have been identified. • All parabens are slightly estrogenic compared to estradiol. - Abstract: In this work, the solar light-induced photocatalytic degradation of ethyl paraben (EP), a representative of the parabens family, was studied using silver orthophosphate, a relatively new photocatalytic material. The catalyst was synthesized by a precipitation method and had a primary crystallite size of ca 70 nm, specific surface area of 1.4 m{sup 2}/g and a bandgap of 2.4 eV. A factorial design methodology was implemented to evaluate the importance of EP concentration (500–1500 μg/L), catalyst concentration (100–500 mg/L), reaction time (4–30 min), water matrix (pure water or 10 mg/L humic acid) and initial solution pH (3–9) on EP removal. All individual effects but solution pH were statistically significant and so were the second-order interactions of EP concentration with reaction time or catalyst concentration. The water matrix effect was negative (all other effects were positive) signifying the role of humic acid as scavenger of the oxidant species. Liquid chromatography-time of flight mass spectrometry revealed the formation of methyl paraben, 4-hydroxybenzoic acid, benzoic acid and phenol as primary transformation by-products; these are formed through dealkylation and decarboxylation reactions initiated primarily by the photogenerated holes. Estrogenicity assays showed that methyl paraben was more estrogenic than EP; however, parabens are slightly estrogenic compared to 17β-estradiol.

Photodegradation of lambda-cyhalothrin and cypermethrin in aqueous solution as affected by humic acid and/or copper: intermediates and degradation pathways.

Science.gov (United States)

Xie, Jimin; Wang, Pingli; Liu, Jun; Lv, Xiaomeng; Jiang, Deli; Sun, Cheng

2011-11-01

The influence of coexisting humic acids (HA) or Cu²⁺ on the photodegradation of pesticides lambda-cyhalothrin (λ-CHT) and cypermethrin (CPM) in aqueous solution was studied under xenon lamp irradiation. The removal efficiency of pesticides λ-CHT and CPM were enhanced in the presence of either Cu²⁺ or HA but restrained in the presence of both Cu²⁺ and HA. The photodegradation of λ-CHT and CPM followed first-order reaction kinetics. The photodegradation intermediates of λ-CHT and CPM were determined using gas chromatography/mass spectrometry. Possible photodegradation pathways included decarboxylation, ester bond cleavage, dechlorination, and phenyl group removal. Copyright © 2011 SETAC.

The Sonodegradation of Caffeic Acid under Ultrasound Treatment: Relation to Stability

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Yujing Sun

2013-01-01

Full Text Available The degradation of caffeic acid under ultrasound treatment in a model system was investigated. The type of solvent and temperature were important factors in determining the outcome of the degradation reactions. Liquid height, ultrasonic intensity and duty cycle only affected degradation rate, but did not change the nature of the degradation. The degradation rate of caffeic acid decreased with increasing temperature. Degradation kinetics of caffeic acid under ultrasound fitted a zero-order reaction from −5 to 25 °C. Caffeic acid underwent decomposition and oligomerization reactions under ultrasound. The degradation products were tentatively identified by FT-IR and HPLC-UV-ESIMS to include the corresponding decarboxylation products and their dimers.

In-Situ Measurements of the Radiation Stability of Amino Acids at 15-140 K

Science.gov (United States)

Gerakines, Perry A.; Hudson, Reggie L.; Moore, Marla H.; Bell, Jan-Luca

2012-01-01

We present new kinetics data on the radiolytic destruction of amino acids measured in situ with infrared spectroscopy. Samples were irradiated at 15, 100, and 140 K with D.8-MeV protons, and amino-acid decay was followed at each temperature with and without H2O present. Observed radiation products included CO2 and amines, consistent with amino-acid decarboxylation. The half-lives of glycine, alanine, and phenylalanine were estimated for various extraterrestrial environments. Infrared spectral changes demonstrated the conversion from the non-zwitterion structure NH2-CH2(R)-COOH at 15 K to the zwitterion structure +NH3-CH2(R)-COO- at 140 K for each amino acid studied.

Experimental ‏review ‏of ‏cobalt ‏induced cardiomyopathy

Directory of Open Access Journals (Sweden)

Igor ‏V. Zadnipryany

2017-03-01

The primary morphological alteration is mitochondrial damage that possibly reflects an enzymatic block of oxidative decarboxylation at pyruvate and ketogluterate levels. Due to that myofibrils of the myocardial cells were affected highlighting that the main cause of myofibril reduction could be a lower oxygen intake in the perinuclear area. The reduction of the contractile support of myocardial cells can explain the possible myocardial dysfunction. Nuclear changes were consistent with sarcoplasmic alterations, our study showing deformed, twisted, hyperchromatic nuclei with heterogeneous chromatin and even disintegrating nuclei. Changes of the interstitial connective tissue were sometimes extensive and sometimes barely noticeable. The most common alteration of this structure was the onset and development of a mainly perivascular collagen fibrillogenetic process.

Short-time maximum entropy method analysis of molecular dynamics simulation: Unimolecular decomposition of formic acid

Science.gov (United States)

Takahashi, Osamu; Nomura, Tetsuo; Tabayashi, Kiyohiko; Yamasaki, Katsuyoshi

2008-07-01

We performed spectral analysis by using the maximum entropy method instead of the traditional Fourier transform technique to investigate the short-time behavior in molecular systems, such as the energy transfer between vibrational modes and chemical reactions. This procedure was applied to direct ab initio molecular dynamics calculations for the decomposition of formic acid. More reactive trajectories of dehydrolation than those of decarboxylation were obtained for Z-formic acid, which was consistent with the prediction of previous theoretical and experimental studies. Short-time maximum entropy method analyses were performed for typical reactive and non-reactive trajectories. Spectrograms of a reactive trajectory were obtained; these clearly showed the reactant, transient, and product regions, especially for the dehydrolation path.

Palladium-catalyzed asymmetric alkylation in the synthesis of cyclopentanoid and cycloheptanoid core structures bearing all-carbon quaternary stereocenters

KAUST Repository

Hong, Allen Y.

2011-12-01

General catalytic asymmetric routes toward cyclopentanoid and cycloheptanoid core structures embedded in numerous natural products have been developed. The central stereoselective transformation in our divergent strategies is the enantioselective decarboxylative alkylation of seven-membered β-ketoesters to form α-quaternary vinylogous esters. Recognition of the unusual reactivity of β-hydroxyketones resulting from the addition of hydride or organometallic reagents enabled divergent access to γ-quaternary acylcyclopentenes through a ring contraction pathway or γ-quaternary cycloheptenones through a carbonyl transposition pathway. Synthetic applications of these compounds were explored through the preparation of mono-, bi-, and tricyclic derivatives that can serve as valuable intermediates for the total synthesis of complex natural products. This work complements our previous work with cyclohexanoid systems.

Biosynthesis of polybrominated aromatic organic compounds by marine bacteria

Science.gov (United States)

Agarwal, Vinayak; El Gamal, Abrahim A.; Yamanaka, Kazuya; Poth, Dennis; Kersten, Roland D.; Schorn, Michelle; Allen, Eric E.; Moore, Bradley S.

2014-01-01

Polybrominated diphenyl ethers (PBDEs) and polybrominated bipyrroles are natural products that bioaccumulate in the marine food chain. PBDEs have attracted widespread attention due to their persistence in the environment and potential toxicity to humans. However, the natural origins of PBDE biosynthesis are not known. Here we report marine bacteria as producers of PBDEs and establish a genetic and molecular foundation for their production that unifies paradigms for the elaboration of bromophenols and bromopyrroles abundant in marine biota. We provide biochemical evidence of marine brominase enzymes revealing decarboxylative-halogenation enzymology previously unknown among halogenating enzymes. Biosynthetic motifs discovered in our study were used to mine sequence databases to discover unrealized marine bacterial producers of organobromine compounds. PMID:24974229

Chemical stability of {gamma}-butyrolactone-based electrolytes for aluminium electrolytic capacitors

Energy Technology Data Exchange (ETDEWEB)

Ue, Makoto [Mitsubishi Chemical Corp., Tsukuba Research Center, Ibaraki (Japan); Takeda, Masayuki [Mitsubishi Chemical Corp., Tsukuba Research Center, Ibaraki (Japan); Suzuki, Yoko [Mitsubishi Chemical Corp., Tsukuba Research Center, Ibaraki (Japan); Mori, Shoichiro [Mitsubishi Chemical Corp., Tsukuba Research Center, Ibaraki (Japan)

1996-06-01

{gamma}-Butyrolactone-based electrolytes have been used as the operating electrolytes for aluminum electrolytic capacitors. The chemical stability of these electrolytes at elevated temperatures has been examined by monitoring the decrease in their electrolytic conductivities. The deteriorated electrolytes were analyzed by gas and liquid chromatography and the conductivity decrease was directly correlated with the loss of acid components. In quaternary ammonium hydrogen maleate/{gamma}-butyrolactone electrolytes, the maleate anion decomposed by decarboxylation resulting in a complex polymer containing polyester and polyacrylate structures. Quaternary ammonium benzoate/{gamma}-butyrolactone electrolytes decomposed by SN2 reactions giving alkyl benzoates and trialkylamines. The deterioration of the carboxylate salt/{gamma}-butyrolactone electrolytes was accelerated by electrolysis. (orig.)

Enzymatic approaches to rare sugar production.

Science.gov (United States)

Zhang, Wenli; Zhang, Tao; Jiang, Bo; Mu, Wanmeng

Rare sugars have recently attracted much attention because of their potential applications in the food, nutraceutical, and pharmaceutical industries. A systematic strategy for enzymatic production of rare sugars, named Izumoring, was developed >10years ago. The strategy consists of aldose-ketose isomerization, ketose C-3 epimerization, and monosaccharide oxidation-reduction. Recent development of the Izumoring strategy is reviewed herein, especially the genetic approaches to the improvement of rare sugar-producing enzymes and the applications of target-oriented bioconversion. In addition, novel non-Izumoring enzymatic approaches are also summarized, including enzymatic condensation, phosphorylation-dephosphorylation cascade reaction, aldose epimerization, ulosonic acid decarboxylation, and biosynthesis of rare disaccharides. Copyright © 2017 Elsevier Inc. All rights reserved.

Phytanic acid alpha-oxidation: decarboxylation of 2-hydroxyphytanoyl-CoA to pristanic acid in human liver

NARCIS (Netherlands)

Verhoeven, N. M.; Wanders, R. J.; Schor, D. S.; Jansen, G. A.; Jakobs, C.

1997-01-01

The degradation of the first intermediate in the alpha-oxidation of phytanic acid, 2-hydroxyphytanoyl-CoA, was investigated. Human liver homogenates were incubated with 2-hydroxyphytanoyl-CoA or 2-hydroxyphytanic acid, after which formation of 2-ketophytanic acid and pristanic acid were studied.

Catalytic conversion of cellulose to liquid hydrocarbon fuels by progressive removal of oxygen to facilitate separation processes and achieve high selectivities

Energy Technology Data Exchange (ETDEWEB)

Dumesic, James A.; Ruiz, Juan Carlos Serrano; West, Ryan M.

2015-06-30

Described is a method to make liquid chemicals. The method includes deconstructing cellulose to yield a product mixture comprising levulinic acid and formic acid, converting the levulinic acid to .gamma.-valerolactone, and converting the .gamma.-valerolactone to pentanoic acid. Alternatively, the .gamma.-valerolactone can be converted to a mixture of n-butenes. The pentanoic acid can be decarboxylated yield 1-butene or ketonized to yield 5-nonanone. The 5-nonanone can be hydrodeoxygenated to yield nonane, or 5-nonanone can be reduced to yield 5-nonanol. The 5-nonanol can be dehydrated to yield nonene, which can be dimerized to yield a mixture of C.sub.9 and C.sub.18 olefins, which can be hydrogenated to yield a mixture of alkanes.

Catalytic conversion of cellulose to liquid hydrocarbon fuels by progressive removal of oxygen to facilitate separation processes and achieve high selectivities

Energy Technology Data Exchange (ETDEWEB)

Dumesic, James A [Verona, WI; Ruiz, Juan Carlos Serrano [Madison, WI; West, Ryan M [Madison, WI

2014-01-07

Described is a method to make liquid chemicals. The method includes deconstructing cellulose to yield a product mixture comprising levulinic acid and formic acid, converting the levulinic acid to .gamma.-valerolactone, and converting the .gamma.-valerolactone to pentanoic acid. Alternatively, the .gamma.-valerolactone can be conveted to a mixture of n-butenes. The pentanoic acid can be decarboxylated yield 1-butene or ketonized to yield 5-nonanone. The 5-nonanone can be hydrodeoxygenated to yield nonane, or 5-nonanone can be reduced to yield 5-nonanol. The 5-nonanol can be dehydrated to yield nonene, which can be dimerized to yield a mixture of C.sub.9 and C.sub.18 olefins, which can be hydrogenated to yield a mixture of alkanes.

Radiation damage mechanisms in single crystals of creatine monohydrate

International Nuclear Information System (INIS)

Wells, J.W.; Ko, C.

1978-01-01

ENDOR spectroscopy is utilized to define the temperature dependent sequence of molecular fragmentation processes occuring in x-irradiated single crystals of creatine monohydrate. Two conformations of the primary reduction product =OOC--C(H 2 ) --N(CH) 3 --C(NH 2 ) 2 + are found to undergo a series of subtle changes before deamination. The resultant radical -OOC--CH 2 then induces hydrogen abstraction to form a final room temperature product - OOC--CH--N(CH 3 ) --C(NH 2 ) + . An unknown initial oxidation species is found to decarboxylate forming the radical H 2 C--N(CH 3 ) --C(NH 2 ) 2 + which, although similar to the deamination product, exists at room temperature. The stability of this species is attributed to a delocalization of spin indicated by calculation and measurement

Influence of gas-generation on melt/concrete interaction

International Nuclear Information System (INIS)

Powers, D.A.

1979-01-01

Gases formed during the interaction of a high-temperature melt with concrete are shown to stem from the thermal dehydration and decarboxylation of the concrete. The kinetics of these decomposition reactions are described. Gases within the melt cause an apparent swelling of the melt. The observed swelling is not easily correlated to the rate of gas evolution. Metallic melts cause CO 2 /CO and H 2 O liberated from the melt to be reduced to CO and hydrogen. When these gases escape from the melt they assist in aerosol formation. As the gases cool they react along a pathway whose oxygen fugacity is apparently buffered by the iron-Wuestite equilibrium. Methane is a product of the gas-phase reaction. (orig./HP) [de

Role of agmatine in neurodegenerative diseases and epilepsy.

Science.gov (United States)

Moretti, Morgana; Matheus, Filipe C; de Oliveira, Paulo A; Neis, Vivian B; Ben, Juliana; Walz, Roger; Rodrigues, Ana Lucia S; Prediger, Rui Daniel

2014-06-01

Agmatine, a cationic polyamine synthesized after decarboxylation of L-arginine by the enzyme arginine decarboxylase, is an endogenous neuromodulator that emerges as a potential agent to manage diverse central nervous system (CNS) disorders. Consistent with its neuromodulatory and neuroprotective properties, there is increasing number of preclinical studies demonstrating the beneficial effects of exogenous agmatine administration on depression, anxiety, hypoxic ischemia, nociception, morphine tolerance, memory, Parkinson`s disease, Alzheimer`s disease, traumatic brain injury related alterations/disorders and epilepsy. The aim of this review is to summarize the knowledge about the effects of agmatine in CNS and point out its potential as new pharmacological treatment for diverse neurological and neurodegenerative diseases. Moreover, some molecular mechanisms underlying the neuroprotective effects of agmatine will be discussed.

Local CC2 response method based on the Laplace transform: Analytic energy gradients for ground and excited states

Energy Technology Data Exchange (ETDEWEB)

Ledermüller, Katrin; Schütz, Martin, E-mail: martin.schuetz@chemie.uni-regensburg.de [Institute of Physical and Theoretical Chemistry, University of Regensburg, Universitätsstraße 31, D-93040 Regensburg (Germany)

2014-04-28

A multistate local CC2 response method for the calculation of analytic energy gradients with respect to nuclear displacements is presented for ground and electronically excited states. The gradient enables the search for equilibrium geometries of extended molecular systems. Laplace transform is used to partition the eigenvalue problem in order to obtain an effective singles eigenvalue problem and adaptive, state-specific local approximations. This leads to an approximation in the energy Lagrangian, which however is shown (by comparison with the corresponding gradient method without Laplace transform) to be of no concern for geometry optimizations. The accuracy of the local approximation is tested and the efficiency of the new code is demonstrated by application calculations devoted to a photocatalytic decarboxylation process of present interest.

Local CC2 response method based on the Laplace transform: analytic energy gradients for ground and excited states.

Science.gov (United States)

Ledermüller, Katrin; Schütz, Martin

2014-04-28

A multistate local CC2 response method for the calculation of analytic energy gradients with respect to nuclear displacements is presented for ground and electronically excited states. The gradient enables the search for equilibrium geometries of extended molecular systems. Laplace transform is used to partition the eigenvalue problem in order to obtain an effective singles eigenvalue problem and adaptive, state-specific local approximations. This leads to an approximation in the energy Lagrangian, which however is shown (by comparison with the corresponding gradient method without Laplace transform) to be of no concern for geometry optimizations. The accuracy of the local approximation is tested and the efficiency of the new code is demonstrated by application calculations devoted to a photocatalytic decarboxylation process of present interest.

Local CC2 response method based on the Laplace transform: Analytic energy gradients for ground and excited states

International Nuclear Information System (INIS)

Ledermüller, Katrin; Schütz, Martin

2014-01-01

A multistate local CC2 response method for the calculation of analytic energy gradients with respect to nuclear displacements is presented for ground and electronically excited states. The gradient enables the search for equilibrium geometries of extended molecular systems. Laplace transform is used to partition the eigenvalue problem in order to obtain an effective singles eigenvalue problem and adaptive, state-specific local approximations. This leads to an approximation in the energy Lagrangian, which however is shown (by comparison with the corresponding gradient method without Laplace transform) to be of no concern for geometry optimizations. The accuracy of the local approximation is tested and the efficiency of the new code is demonstrated by application calculations devoted to a photocatalytic decarboxylation process of present interest

Discovery of enzymes for toluene synthesis from anoxic microbial communities

DEFF Research Database (Denmark)

Beller, Harry R.; Rodrigues, Andria V.; Zargar, Kamrun

2018-01-01

Microbial toluene biosynthesis was reported in anoxic lake sediments more than three decades ago, but the enzyme catalyzing this biochemically challenging reaction has never been identified. Here we report the toluene-producing enzyme PhdB, a glycyl radical enzyme of bacterial origin that catalyzes...... phenylacetate decarboxylation, and its cognate activating enzyme PhdA, a radical S-adenosylmethionine enzyme, discovered in two distinct anoxic microbial communities that produce toluene. The unconventional process of enzyme discovery from a complex microbial community (>300,000 genes), rather than from...... a microbial isolate, involved metagenomics- and metaproteomics-enabled biochemistry, as well as in vitro confirmation of activity with recombinant enzymes. This work expands the known catalytic range of glycyl radical enzymes (only seven reaction types had been characterized previously) and aromatic...

A new biological method for preparing certain sulphurated substances labelled with S{sup 35}; Methode nouvelle de preparation par voie biologique de quelques substances soufrees marquees au soufre-35

Energy Technology Data Exchange (ETDEWEB)

Chapeville, F.; Maier-Huser, H.; Fromageot, P. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1962-07-01

Previous investigations have shown that the yolk-sac of embryonic bird's eggs can be used to produce the following reactions: (a) reduction of sulphate to sulphite; (b) fixation of the sulphite on the carbon chain produced by the desulf-hydration of l-cysteine, with formation of l-cysteic acid; (c) decarboxylation of the l-cysteine acid into taurine. The enzymatic system which causes reaction (b) has been purified. It also acts as a catalyst in the sulphur-exchange between the cysteine and the mineral sulphide. The authors have utilized these data in preparing sulphurated substances labelled with S{sup 35}: taurine S{sup 35}, l-cysteine S{sup 35} and l-cysteic acid S{sup 35}. For each of the three, they discuss the chemical reactions involved, the methods of preparation, the experimental conditions of extraction and purity-control, together with the yields and specific activities obtained. (authors) [French] Des travaux anterieurs ont montre l'aptitude du sac vitellin d'oeufs embryonn d'oiseaux a realiser les reactions suivantes: a) reduction du sulfate en sulfite, b) fixation du sulfite sur la chaine carbonee issue de la desulfhydration de la L-cysteine avec formation de l'acide L-cysteique. c) decarboxylation de l 'acide L-cysteique en taurine. Le systeme enzymatique responsable de la reaction b a ete purifie; il catalyse aussi l'echange du soufre de la cysteine avec celui du sulfure mineral. Les auteurs ont utilise ces donnees pour la preparation de substances soufrees marquees au {sup 35}S: taurine {sup 35}S, L-cysteine{sup 35} et acide L-cysteique {sup 35}S. Pour chacun de ces trois corps, ils decrivent les reactions chimiques mises en jeu, les modes operatoires de fabrication, les conditions experimentales d'extraction et de controle de la purete, ainsi que les resultats obtenus tant pour les rendements que pour les activites specifiques obtenues. (auteurs)

Genes involved in long-chain alkene biosynthesis in Micrococcus luteus.

Science.gov (United States)

Beller, Harry R; Goh, Ee-Been; Keasling, Jay D

2010-02-01

Aliphatic hydrocarbons are highly appealing targets for advanced cellulosic biofuels, as they are already predominant components of petroleum-based gasoline and diesel fuels. We have studied alkene biosynthesis in Micrococcus luteus ATCC 4698, a close relative of Sarcina lutea (now Kocuria rhizophila), which 4 decades ago was reported to biosynthesize iso- and anteiso-branched, long-chain alkenes. The underlying biochemistry and genetics of alkene biosynthesis were not elucidated in those studies. We show here that heterologous expression of a three-gene cluster from M. luteus (Mlut_13230-13250) in a fatty acid-overproducing Escherichia coli strain resulted in production of long-chain alkenes, predominantly 27:3 and 29:3 (no. carbon atoms: no. C=C bonds). Heterologous expression of Mlut_13230 (oleA) alone produced no long-chain alkenes but unsaturated aliphatic monoketones, predominantly 27:2, and in vitro studies with the purified Mlut_13230 protein and tetradecanoyl-coenzyme A (CoA) produced the same C(27) monoketone. Gas chromatography-time of flight mass spectrometry confirmed the elemental composition of all detected long-chain alkenes and monoketones (putative intermediates of alkene biosynthesis). Negative controls demonstrated that the M. luteus genes were responsible for production of these metabolites. Studies with wild-type M. luteus showed that the transcript copy number of Mlut_13230-13250 and the concentrations of 29:1 alkene isomers (the dominant alkenes produced by this strain) generally corresponded with bacterial population over time. We propose a metabolic pathway for alkene biosynthesis starting with acyl-CoA (or-ACP [acyl carrier protein]) thioesters and involving decarboxylative Claisen condensation as a key step, which we believe is catalyzed by OleA. Such activity is consistent with our data and with the homology (including the conserved Cys-His-Asn catalytic triad) of Mlut_13230 (OleA) to FabH (beta-ketoacyl-ACP synthase III), which

In situ ligand synthesis with the UO22+ cation under hydrothermal conditions

International Nuclear Information System (INIS)

Frisch, Mark; Cahill, Christopher L.

2007-01-01

A novel uranium (VI) coordination polymer, (UO 2 ) 2 (C 2 O 4 )(C 5 H 6 NO 3 ) 2 (1), has been prepared under the hydrothermal reaction of uranium nitrate hexahydrate and L-pyroglutamic acid. Compound 1 (monoclinic, C2/c, a=22.541(6) A, b=5.7428(15) A, c=15.815(4) A, β=119.112(4) o , Z=4, R 1 =0.0237, wR 2 =0.0367) consists of uranium pentagonal bipyramids linked via L-pyroglutamate and oxalate anions to form an overall two-dimensional (2D) structure. With the absence of oxalic acid within the starting materials, the oxalate anions are hypothesized to form in situ whereby decarboxylation of L-pyroglutamic acid occurs followed by coupling of CO 2 to form the oxalate linkages as observed in the crystal structure. Addition of copper (II) to this system appears to promote oxalate formation in that synthetic moolooite (Cu(C 2 O 4 ).nH 2 O; 0≤n≤1) and a known uranyl oxalate [(UO 2 ) 2 (C 2 O 4 )(OH) 2 (H 2 O) 2 .H 2 O], co-crystallize in significant quantity. Compound 1 exhibits the characteristic uranyl emission spectrum upon either direct uranyl excitation or ligand excitation, the latter of which shows an increase in relative intensity. This subsequent increase in the intensity indicates an energy transfer from the ligand to the uranyl cations thus illustrating an example of the antenna effect in the solid state. - Graphical abstract: A novel homometallic coordination polymer (UO 2 ) 2 (C 2 O 4 )(C 5 H 6 NO 3 ) 2 , in the uranium-L-pyroglutamic acid system has been synthesized under hydrothermal conditions. The title compound consists of uranium pentagonal bipyramids bridged through both L-pyroglutamate and oxalate linkages to produce a 3D crystal structure. The oxalate anions are theorized to result from decarboxylation of L-pyroglutamic acid followed by subsequent coupling of CO 2

VID22 is required for transcriptional activation of the PSD2 gene in the yeast Saccharomyces cerevisiae.

Science.gov (United States)

Miyata, Non; Miyoshi, Takuya; Yamaguchi, Takanori; Nakazono, Toshimitsu; Tani, Motohiro; Kuge, Osamu

2015-12-15

Phosphatidylethanolamine (PE) in the yeast Saccharomyces cerevisiae is synthesized through decarboxylation of phosphatidylserine (PS), catalysed by PS decarboxylase 1 (Psd1p) and 2 (Psd2p) and the cytidine 5'-diphosphate (CDP)-ethanolamine (CDP-Etn) pathway. PSD1 null (psd1Δ) and PSD2 null (psd2Δ) mutants are viable in a synthetic minimal medium, but a psd1Δ psd2Δ double mutant exhibits Etn auxotrophy, which is incorporated into PE through the CDP-Etn pathway. We have previously shown that psd1Δ is synthetic lethal with deletion of VID22 (vid22Δ) [Kuroda et al. (2011) Mol. Microbiol. 80: , 248-265]. In the present study, we found that vid22Δ mutant exhibits Etn auxotrophy under PSD1-depressed conditions. Deletion of VID22 in wild-type and PSD1-depressed cells caused partial defects in PE formation through decarboxylation of PS. The enzyme activity of PS decarboxylase in an extract of vid22Δ cells was ∼70% of that in wild-type cells and similar to that in psd2Δ cells and the PS decarboxylase activity remaining in the PSD1-depressed cells became almost negligible with deletion of VID22. Thus, the vid22Δ mutation was suggested to cause a defect in the Psd2p activity. Furthermore, vid22Δ cells were shown to be defective in expression of the PSD2 gene tagged with 6×HA, the defect being ameliorated by replacement of the native promoter of the PSD2 gene with a CYC1 promoter. In addition, an α-galactosidase reporter assay revealed that the activity of the promoter of the PSD2 gene in vid22Δ cells was ∼5% of that in wild-type cells. These results showed that VID22 is required for transcriptional activation of the PSD2 gene. © 2015 Authors; published by Portland Press Limited.

Versatile solvent systems for the separation of betalains from processed Beta vulgaris L. juice using counter-current chromatography.

Science.gov (United States)

Spórna-Kucab, Aneta; Ignatova, Svetlana; Garrard, Ian; Wybraniec, Sławomir

2013-12-15

Two mixtures of decarboxylated and dehydrogenated betacyanins from processed red beet roots (Beta vulgaris L.) juice were fractionated by high performance counter-current chromatography (HPCCC) producing a range of isolated components. Mixture 1 contained mainly betacyanins, 14,15-dehydro-betanin (neobetanin) and their decarboxylated derivatives while mixture 2 consisted of decarboxy- and dehydro-betacyanins. The products of mixture 1 arose during thermal degradation of betanin/isobetanin in mild conditions while the dehydro-betacyanins of mixture 2 appeared after longer heating of the juice from B. vulgaris L. Two solvent systems were found to be effective for the HPCCC. A highly polar, high salt concentration system of 1-PrOH-ACN-(NH4)2SO4 (satd. soln)-water (v/v/v/v, 1:0.5:1.2:1) (tail-to-head mode) enabled the purification of 2-decarboxy-betanin/-isobetanin, 2,17-bidecarboxy-betanin/-isobetanin and neobetanin (all from mixture 1) plus 17-decarboxy-neobetanin, 2,15,17-tridecarboxy-2,3-dehydro-neobetanin, 2-decarboxy-neobetanin and 2,15,17-tridecarboxy-neobetanin (from mixture 2). The other solvent system included heptafluorobutyric acid (HFBA) as ion-pair reagent and consisted of tert-butyl methyl ether (TBME)-1-BuOH-ACN-water (acidified with 0.7% HFBA) (2:2:1:5, v/v/v/v) (head-to-tail mode). This system enabled the HPCCC purification of 2,17-bidecarboxy-betanin/-isobetanin and neobetanin (from mixture 1) plus 2,15,17-tridecarboxy-2,3-dehydro-neobetanin, 2,17-bidecarboxy-2,3-dehydro-neobetanin and 2,15,17-tridecarboxy-neobetanin (mixture 2). The results of this research are crucial in finding effective isolation methods of betacyanins and their derivatives which are meaningful compounds due their colorant properties and potential health benefits regarding antioxidant and cancer prevention. The pigments were detected by LC-DAD and LC-MS/MS techniques. Copyright © 2013 Elsevier B.V. All rights reserved.

Degradation kinetics and mechanism of β-lactam antibiotics by the activation of H2O2 and Na2S2O8 under UV-254 nm irradiation

International Nuclear Information System (INIS)

He, Xuexiang; Mezyk, Stephen P.; Michael, Irene; Fatta-Kassinos, Despo; Dionysiou, Dionysios D.

2014-01-01

Graphical abstract: - Highlights: • Removal efficiency was comparable at different UV fluence rates but same fluence. • Reducing pH to 3 or 2 did not inhibit the removal of nitrobenzene by UV/S 2 O 8 2− . • 1.84 × 10 −14 M [HO • ] ss and 3.10 × 10 −13 M [SO 4 • − ] ss in UV/S 2 O 8 2− were estimated. • HO • reacted faster with the β-lactams than SO 4 • − but sharing similar byproducts. • Transformation pathways included hydroxylation, hydrolysis and decarboxylation. - Abstract: The extensive production and usage of antibiotics have led to an increasing occurrence of antibiotic residuals in various aquatic compartments, presenting a significant threat to both ecosystem and human health. This study investigated the degradation of selected β-lactam antibiotics (penicillins: ampicillin, penicillin V, and piperacillin; cephalosporin: cephalothin) by UV-254 nm activated H 2 O 2 and S 2 O 8 2− photochemical processes. The UV irradiation alone resulted in various degrees of direct photolysis of the antibiotics; while the addition of the oxidants improved significantly the removal efficiency. The steady-state radical concentrations were estimated, revealing a non-negligible contribution of hydroxyl radicals in the UV/S 2 O 8 2− system. Mineralization of the β-lactams could be achieved at high UV fluence, with a slow formation of SO 4 2− and a much lower elimination of total organic carbon (TOC). The transformation mechanisms were also investigated showing the main reaction pathways of hydroxylation (+16 Da) at the aromatic ring and/or the sulfur atom, hydrolysis (+18 Da) at the β-lactam ring and decarboxylation (–44 Da) for the three penicillins. Oxidation of amine group was also observed for ampicillin. This study suggests that UV/H 2 O 2 and UV/S 2 O 8 2− advanced oxidation processes (AOPs) are capable of degrading β-lactam antibiotics decreasing consequently the antibiotic activity of treated waters

Improving methodological aspects of the analysis of five regulated haloacetic acids in water samples by solid-phase extraction, ion-pair liquid chromatography and electrospray tandem mass spectrometry.

Science.gov (United States)

Prieto-Blanco, M C; Alpendurada, M F; López-Mahía, P; Muniategui-Lorenzo, S; Prada-Rodríguez, D; Machado, S; Gonçalves, C

2012-05-30

Haloacetic acids (HAAs) are organic pollutants originated from the drinking water disinfection process, which ought to be controlled and minimized. In this work a method for monitoring haloacetic acids (HAAs) in water samples is proposed, which can be used in quality control laboratories using the techniques most frequently available. Among its main advantages we may highlight its automated character, including minimal steps of sample preparation, and above all, its improved selectivity and sensitivity in the analysis of real samples. Five haloacetic acids (HAA5) were analyzed using solid-phase extraction (SPE) combined with ion-pair liquid chromatography and tandem mass spectrometry. For the optimization of the chromatographic separation, two amines (triethylamine, TEA and dibutylamine, DBA) as ion pair reagents were compared, and a better selectivity and sensitivity was obtained using DBA, especially for monohaloacetic acids. SPE conditions were optimized using different polymeric adsorbents. The electrospray source parameters were studied for maximum precursor ion accumulation, while the collision cell energy of the triple quadrupole mass spectrometer was adjusted for optimum fragmentation. Precursor ions detected were deprotonated, dimeric and decarboxylated ions. The major product ions formed were: ionized halogen atom (chloride and bromide) and decarboxylated ions. After enrichment of the HAAs in Lichrolut EN adsorbent, the limits of detection obtained by LC-MS/MS analysis (between 0.04 and 0.3 ng mL(-1)) were comparable to those obtained by GC-MS after derivatization. Linearity with good correlation coefficients was obtained over two orders of magnitude irrespective of the compound. Adequate recoveries were achieved (60-102%), and the repeatability and intermediate precision were in the range of 2.4-6.6% and 3.8-14.8%, respectively. In order to demonstrate the usefulness of the method for routine HAAs monitoring, different types of water samples were

An improved method for the assay of platelet pyruvate dehydrogenase

International Nuclear Information System (INIS)

Schofield, P.J.; Griffiths, L.R.; Rogers, S.H.

1980-01-01

An improved method for the assay of human platelet pyruvate dehydrogenase is described. By generating the substrate [1- 14 C]pyruvate in situ from [1- 14 C]lactate plus L-lactate dehydrogenase, the rate of spontaneous decarboxylation is dramatically reduced, allowing far greater sensitivity in the assay of low activities of pyruvate dehydrogenase. In addition, no special precautions are required for the storage and use of [1- 14 C]lactate, in contrast to those for [1- 14 C]pyruvate. These factors allow a 5-10-fold increase in sensitivity compared with current methods. The pyruvate dehydrogenase activity of normal subjects as determined by the [1- 14 C]lactate system was 215+-55 pmol min -1 mg -1 protein (n=18). The advantages of this assay system are discussed. (Auth.)

Hydrothermal liquefaction of biomass

DEFF Research Database (Denmark)

Toor, Saqib; Rosendahl, Lasse; Rudolf, Andreas

2011-01-01

This article reviews the hydrothermal liquefaction of biomass with the aim of describing the current status of the technology. Hydrothermal liquefaction is a medium-temperature, high-pressure thermochemical process, which produces a liquid product, often called bio-oil or bi-crude. During...... the hydrothermal liquefaction process, the macromolecules of the biomass are first hydrolyzed and/or degraded into smaller molecules. Many of the produced molecules are unstable and reactive and can recombine into larger ones. During this process, a substantial part of the oxygen in the biomass is removed...... by dehydration or decarboxylation. The chemical properties of bio-oil are highly dependent of the biomass substrate composition. Biomass constitutes of various components such as protein; carbohydrates, lignin and fat, and each of them produce distinct spectra of compounds during hydrothermal liquefaction...

Nucleotide sequence alignment of hdcA from Gram-positive bacteria.

Science.gov (United States)

Diaz, Maria; Ladero, Victor; Redruello, Begoña; Sanchez-Llana, Esther; Del Rio, Beatriz; Fernandez, Maria; Martin, Maria Cruz; Alvarez, Miguel A

2016-03-01

The decarboxylation of histidine -carried out mainly by some gram-positive bacteria- yields the toxic dietary biogenic amine histamine (Ladero et al. 2010 〈10.2174/157340110791233256〉 [1], Linares et al. 2016 〈http://dx.doi.org/10.1016/j.foodchem.2015.11.013〉〉 [2]). The reaction is catalyzed by a pyruvoyl-dependent histidine decarboxylase (Linares et al. 2011 〈10.1080/10408398.2011.582813〉 [3]), which is encoded by the gene hdcA. In order to locate conserved regions in the hdcA gene of Gram-positive bacteria, this article provides a nucleotide sequence alignment of all the hdcA sequences from Gram-positive bacteria present in databases. For further utility and discussion, see 〈http://dx.doi.org/ 10.1016/j.foodcont.2015.11.035〉〉 [4].

The features of nucleophilic substitution of the nitro group in 4-alkyl-6-nitro-1,2,4-triazolo[5,1-c][1,2,4]triazines

Directory of Open Access Journals (Sweden)

E. N. Ulomsky

2017-05-01

Full Text Available The nucleophilic substitution of the nitro group of 4-alkyl-6-nitro-4,7-dihydro-1,2,4-triazolo[5,1-c][1,2,4]triazine-7-ones on the example of interactionwith morpholine was studied. It is established that under the action of excess cycloalkylimine at room temperature the unusual easy disclosure of triazine cycle with the formation of sterically hindered hydrazones occurs which are the key intermediates for further transformations. The carrying of reaction at elevated temperatures leads to the formation of products of substitution of the nitro group with the amine and also with morpholyl hydrazones which are the products of hydrolysis of amides of hydrazones and subsequent decarboxylation. Thus, the nucleophilic substitution of the nitro group in the described triazolotriazines flows through the ANRORC mechanism.

Conversion of kraft lignin over hierarchical MFI zeolite.

Science.gov (United States)

Kim, Seong-Soo; Lee, Hyung Won; Ryoo, Ryong; Kim, Wookdong; Park, Sung Hoon; Jeon, Jong-Ki; Park, Young-Kwon

2014-03-01

Catalytic pyrolysis of kraft lignin was carried out using pyrolysis gas chromatography/mass spectrometry. Hierarchical mesoporous MFI was used as the catalyst and another mesoporous material Al-SBA-15 was also used for comparison. The characteristics of mesoporous MFI were analyzed by X-ray diffraction patterns, N2 adsorption-desorption isotherms, and temperature programmed desorption of NH3. Two catalyst/lignin mass ratios were tested: 5/1 and 10/1. Aromatics and alkyl phenolics were the main products of the catalytic pyrolysis of lignin over mesoporous MFI. In particular, the yields of mono-aromatics such as benzene, toluene, ethylbenzene, and xylene were increased substantially by catalytic upgrading. Increase in the catalyst dose enhanced the production of aromatics further, which is attributed to decarboxylation, decarbonlyation, and aromatization reactions occurring over the acid sites of mesoporous MFI.

Electrochemistry for biofuel generation: transformation of fatty acids and triglycerides to diesel-like olefin/ether mixtures and olefins.

Science.gov (United States)

dos Santos, Tatiane R; Harnisch, Falk; Nilges, Peter; Schröder, Uwe

2015-03-01

Electroorganic synthesis can be exploited for the production of biofuels from fatty acids and triglycerides. With Coulomb efficiencies (CE) of up to 50 %, the electrochemical decarboxylation of fatty acids in methanolic and ethanolic solutions leads to the formation of diesel-like olefin/ether mixtures. Triglycerides can be directly converted in aqueous solutions by using sonoelectrochemistry, with olefins as the main products (with a CE of more than 20 %). The latter reaction, however, is terminated at around 50 % substrate conversion by the produced side-product glycerol. An energy analysis shows that the electrochemical olefin synthesis can be an energetically competitive, sustainable, and--in comparison with established processes--economically feasible alternative for the exploitation of fats and oils for biofuel production. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Agmatine: clinical applications after 100 years in translation.

Science.gov (United States)

Piletz, John E; Aricioglu, Feyza; Cheng, Juei-Tang; Fairbanks, Carolyn A; Gilad, Varda H; Haenisch, Britta; Halaris, Angelos; Hong, Samin; Lee, Jong Eun; Li, Jin; Liu, Ping; Molderings, Gerhard J; Rodrigues, Ana Lúcia S; Satriano, Joseph; Seong, Gong Je; Wilcox, George; Wu, Ning; Gilad, Gad M

2013-09-01

Agmatine (decarboxylated arginine) has been known as a natural product for over 100 years, but its biosynthesis in humans was left unexplored owing to long-standing controversy. Only recently has the demonstration of agmatine biosynthesis in mammals revived research, indicating its exceptional modulatory action at multiple molecular targets, including neurotransmitter systems, nitric oxide (NO) synthesis and polyamine metabolism, thus providing bases for broad therapeutic applications. This timely review, a concerted effort by 16 independent research groups, draws attention to the substantial preclinical and initial clinical evidence, and highlights challenges and opportunities, for the use of agmatine in treating a spectrum of complex diseases with unmet therapeutic needs, including diabetes mellitus, neurotrauma and neurodegenerative diseases, opioid addiction, mood disorders, cognitive disorders and cancer. Copyright © 2013 Elsevier Ltd. All rights reserved.

One-step simultaneous differential scanning calorimetry-FTIR microspectroscopy to quickly detect continuous pathways in the solid-state glucose/asparagine Maillard reaction.

Science.gov (United States)

Hwang, Deng-Fwu; Hsieh, Tzu-Feng; Lin, Shan-Yang

2013-01-01

The stepwise reaction pathway of the solid-state Maillard reaction between glucose (Glc) and asparagine (Asn) was investigated using simultaneous differential scanning calorimetry (DSC)-FTIR microspectroscopy. The color change and FTIR spectra of Glc-Asn physical mixtures (molar ratio = 1:1) preheated to different temperatures followed by cooling were also examined. The successive reaction products such as Schiff base intermediate, Amadori product, and decarboxylated Amadori product in the solid-state Glc-Asn Maillard reaction were first simultaneously evidenced by this unique DSC-FTIR microspectroscopy. The color changed from white to yellow-brown to dark brown, and appearance of new IR peaks confirmed the formation of Maillard reaction products. The present study clearly indicates that this unique DSC-FTIR technique not only accelerates but also detects precursors and products of the Maillard reaction in real time.

Thermal effects of carbonated hydroxyapatite modified by glycine and albumin

Science.gov (United States)

Gerk, S. A.; Golovanova, O. A.; Kuimova, M. V.

2017-01-01

In this work calcium phosphate powders were obtained by precipitation method from simulated solutions of synovial fluid containing glycine and albumin. X-ray diffraction and IR spectroscopy determined that all samples are single-phase and are presented by carbonate containing hydroxyapatite (CHA). The thermograms of solid phases of CHA were obtained and analyzed; five stages of transformation in the temperature range of 25-1000°C were marked. It is shown that in this temperature range dehydration, decarboxylation and thermal degradation of amino acid and protein connected to the surface of solid phase occur. The tendency of temperature lowering of the decomposition of powders synthesized from a medium containing organic substances was determined. Results demonstrate a direct dependence between the concentration of the amino acid in a model solution and its content in the solid phase.

Characterized hydrochar of algal biomass for producing solid fuel through hydrothermal carbonization.

Science.gov (United States)

Park, Ki Young; Lee, Kwanyong; Kim, Daegi

2018-06-01

The aim of this work was to study the characterized hydrochar of algal biomass to produce solid fuel though hydrothermal carbonization. Hydrothermal carbonization conducted at temperatures ranging from 180 to 270 °C with a 60 min reaction improved the upgrading of the fuel properties and the dewatering of wet-basis biomasses such as algae. The carbon content, carbon recovery, energy recovery, and atomic C/O and C/H ratios in all the hydrochars in this study were improved. These characteristic changes in hydrochar from algal biomass are similar to the coalification reactions due to dehydration and decarboxylation with an increase in the hydrothermal reaction temperature. The results of this study indicate that hydrothermal carbonization can be used as an effective means of generating highly energy-efficient renewable fuel resources using algal biomass. Copyright © 2018 Elsevier Ltd. All rights reserved.

Quantification of N-acetylcysteamine activated methylmalonate incorporation into polyketide biosynthesis

Directory of Open Access Journals (Sweden)

Stephan Klopries

2013-04-01

Full Text Available Polyketides are biosynthesized through consecutive decarboxylative Claisen condensations between a carboxylic acid and differently substituted malonic acid thioesters, both tethered to the giant polyketide synthase enzymes. Individual malonic acid derivatives are typically required to be activated as coenzyme A-thioesters prior to their enzyme-catalyzed transfer onto the polyketide synthase. Control over the selection of malonic acid building blocks promises great potential for the experimental alteration of polyketide structure and bioactivity. One requirement for this endeavor is the supplementation of the bacterial polyketide fermentation system with tailored synthetic thioester-activated malonates. The membrane permeable N-acetylcysteamine has been proposed as a coenzyme A-mimic for this purpose. Here, the incorporation efficiency into different polyketides of N-acetylcysteamine activated methylmalonate is studied and quantified, showing a surprisingly high and transferable activity of these polyketide synthase substrate analogues in vivo.

Thermal analysis and its application in evaluation of fluorinated polyimide membranes for gas separation

KAUST Repository

Qiu, Wulin

2011-08-01

Seven polyimides based on (4,4′-hexafluoroisopropylidene) diphthalic anhydride, 6FDA, with different chemical structures were synthesized in a single pot two-step procedure by first producing a high molecular weight polyamic acid (PAA), followed by reaction with acetic anhydride to produce polyimide (PI). The resulting polymers were characterized using thermal analysis techniques including TGA, derivative weight analysis, TGA-MS, and DSC. The decarboxylation-induced thermal cross-linking, ester cross-linking through a diol, and ion-exchange reactions of selected polyimide membranes were investigated. Cross-linking of polymer membranes was confirmed by solubility tests and CO 2 permeability measurements. The thermal analysis provides simple and timesaving opportunities to characterize the polymer properties, the ability to optimize polymer cross-linking conditions, and to monitor polymer functionalization to develop high performance polymeric membranes for gas separations. © 2011 Elsevier Ltd. All rights reserved.

Electronic nose as an innovative tool for the diagnosis of grapevine crown gall

Energy Technology Data Exchange (ETDEWEB)

Blasioli, S., E-mail: sonia.blasioli@unibo.it [Dipartimento di Scienze e Tecnologie Agroambientali, Universita di Bologna, V.le Fanin, 44, 40127 Bologna (Italy); Biondi, E., E-mail: erbiondi@tin.it [Dipartimento di Scienze e Tecnologie Agroambientali, Universita di Bologna, V.le Fanin, 44, 40127 Bologna (Italy); Braschi, I., E-mail: ilaria.braschi@unibo.it [Dipartimento di Scienze e Tecnologie Agroambientali, Universita di Bologna, V.le Fanin, 44, 40127 Bologna (Italy); Mazzucchi, U., E-mail: umberto.mazzucchi@unibo.it [Dipartimento di Scienze e Tecnologie Agroambientali, Universita di Bologna, V.le Fanin, 44, 40127 Bologna (Italy); Bazzi, C., E-mail: carlo.bazzi@unibo.it [Dipartimento di Scienze e Tecnologie Agroambientali, Universita di Bologna, V.le Fanin, 44, 40127 Bologna (Italy); Gessa, C.E., E-mail: carloemanuele.gessa@unibo.it [Dipartimento di Scienze e Tecnologie Agroambientali, Universita di Bologna, V.le Fanin, 44, 40127 Bologna (Italy)

2010-07-05

For the first time, a portable electronic nose was used to discriminate between healthy and galled grapevines, experimentally inoculated with two tumourigenic strains of Agrobacterium vitis. The volatile profile of target cutting samples was analysed by headspace solid phase microextraction coupled with gas chromatography-mass spectrometry. Spectra from tumoured samples revealed the presence of styrene which is compatible with decarboxylation of cinnamic acid involved in secondary metabolism of plants. Principal Component Analysis confirmed the difference in volatile profiles of infected vines and their healthy controls. Linear Discriminant Analysis allowed the correct discrimination between healthy and galled grapevines (83.3%, cross-validation). Although a larger number of samples should be analysed to create a more robust model, our results give novel interesting clues to go further with research on the diagnostic potential of this innovative system associated with multi-dimensional chemometric techniques.

Extraction of intracellular protein from Glaciozyma antarctica for proteomics analysis

Science.gov (United States)

Faizura, S. Nor; Farahayu, K.; Faizal, A. B. Mohd; Asmahani, A. A. S.; Amir, R.; Nazalan, N.; Diba, A. B. Farah; Muhammad, M. Nor; Munir, A. M. Abdul

2013-11-01

Two preparation methods of crude extracts of psychrophilic yeast Glaciozyma antarctica were compared in order to obtain a good recovery of intracellular proteins. Extraction with mechanical procedures using sonication was found to be more effective for obtaining good yield compare to alkaline treatment method. The procedure is simple, rapid, and produce better yield. A total of 52 proteins were identified by combining both extraction methods. Most of the proteins identified in this study involves in the metabolic process including glycolysis pathway, pentose phosphate pathway, pyruyate decarboxylation and also urea cyle. Several chaperons were identified including probable cpr1-cyclophilin (peptidylprolyl isomerase), macrolide-binding protein fkbp12 and heat shock proteins which were postulate to accelerate proper protein folding. Characteristic of the fundamental cellular processes inferred from the expressed-proteome highlight the evolutionary and functional complexity existing in this domain of life.

Discovery and characterization of gut microbiota decarboxylases that can produce the neurotransmitter tryptamine.

Science.gov (United States)

Williams, Brianna B; Van Benschoten, Andrew H; Cimermancic, Peter; Donia, Mohamed S; Zimmermann, Michael; Taketani, Mao; Ishihara, Atsushi; Kashyap, Purna C; Fraser, James S; Fischbach, Michael A

2014-10-08

Several recent studies describe the influence of the gut microbiota on host brain and behavior. However, the mechanisms responsible for microbiota-nervous system interactions are largely unknown. Using a combination of genetics, biochemistry, and crystallography, we identify and characterize two phylogenetically distinct enzymes found in the human microbiome that decarboxylate tryptophan to form the β-arylamine neurotransmitter tryptamine. Although this enzymatic activity is exceedingly rare among bacteria more broadly, analysis of the Human Microbiome Project data demonstrate that at least 10% of the human population harbors at least one bacterium encoding a tryptophan decarboxylase in their gut community. Our results uncover a previously unrecognized enzymatic activity that can give rise to host-modulatory compounds and suggests a potential direct mechanism by which gut microbiota can influence host physiology, including behavior. Copyright © 2014 Elsevier Inc. All rights reserved.

Neonatal domoic acid increases receptor density of α2 adrenoceptors and GABAA α5 receptors in limbic brain regions of adult rats

DEFF Research Database (Denmark)

Thomsen, Majken; Lillethorup, Thea Pinholt; Wegener, Gregers

Background: The presymptomatic events involved in neurological disorders such as epilepsy remain elusive but represent an opportunity to understand disease development and stop the pathogenic processes leading to chronic epilepsy. Previous studies using Western blot and immunohistochemistry have...... found increased levels of α2 adrenoceptors in the hippocampal membrane of adult rats treated neonatally with low-dose domoic acid (DOM) along with decreased levels of both isoforms of glutamic acid decarboxylase (GAD), a catalyst of the decarboxylation of glutamate to GABA, indicating a reduction...... in GABAergic interneurons. Objectives: The aim of the present study was to investigate the expression of GABAA α5 and α2 adrenoceptors in limbic brain regions in a DOM rat model of epilepsy using autoradiography. Methods: Male Sprague-Dawley rats (N=3) were injected (s.c.) daily from postnatal day 8...

Production of acetone and conversion of acetone to acetate in the perfused rat liver

International Nuclear Information System (INIS)

Gavino, V.C.; Somma, J.; Philbert, L.; David, F.; Garneau, M.; Belair, J.; Brunengraber, H.

1987-01-01

The utilization of millimolar concentrations of [2- 14 C]acetone and the production of acetone from acetoacetate were studied in perfused livers from 48-h starved rats. We devised a procedure for determining, in a perfused liver system, the first-order rate constant for the decarboxylation of acetoacetate (0.29 +/- 0.09 h-1, S.E., n = 8). After perfusion of livers with [2- 14 C]acetone, labeled acetate was isolated from the perfusion medium and characterized as [1- 14 C]acetate. No radioactivity was found in lactate or 3-hydroxybutyrate. After 90 min of perfusion with [2- 14 C]acetone, the specific activity of acetate was 30 +/- 4% (n = 13) of the initial specific activity of acetone. We conclude that, in perfused livers from 2-day starved rats, acetone metabolism occurs for the most part via free acetate

One-pot non-enzymatic formation of firefly luciferin in a neutral buffer from p-benzoquinone and cysteine.

Science.gov (United States)

Kanie, Shusei; Nishikawa, Toshio; Ojika, Makoto; Oba, Yuichi

2016-04-21

Firefly luciferin, the substrate for the bioluminescence reaction of luminous beetles, possesses a benzothiazole ring, which is rare in nature. Here, we demonstrate a novel one-pot reaction to give firefly luciferin in a neutral buffer from p-benzoquinone and cysteine without any synthetic reagents or enzymes. The formation of firefly luciferin was low in yield in various neutral buffers, whereas it was inhibited or completely prevented in acidic or basic buffers, in organic solvents, or under a nitrogen atmosphere. Labelling analysis of the firefly luciferin using stable isotopic cysteines showed that the benzothiazole ring was formed via the decarboxylation and carbon-sulfur bond rearrangement of cysteine. These findings imply that the biosynthesis of firefly luciferin can be developed/evolved from the non-enzymatic production of firefly luciferin using common primary biosynthetic units, p-benzoquinone and cysteine.

EFFECT OF AERO-/ANAEROBIOSIS ON DECARBOXYLASE ACTIVITY OF SELECTED LACTIC ACID BACTERIA

Directory of Open Access Journals (Sweden)

Stanislav Kráčmar

2010-05-01

Full Text Available Biogenic amines are undesirable compounds produced in foods mainly through bacterial decarboxylase activity. The aim of this study was to investigate some environmental conditions (particularly aero/anaerobiosis, sodium chloride concentration (0–2% w/w, and amount of lactose (0–1% w/w on the activity of tyrosine decarboxylase enzymes of selected six technological important Lactococcus lactis strains. The levels of parameters tested were chosen according to real situation in fermented dairy products technology (especially cheese-making. Tyramine was determined by the ion-exchange chromatography with post-column ninhydrine derivatization and spectrophotometric detection. Tyrosine decarboxylation occurred during the active growth phase. Under the model conditions used, oxygen availability had influence on tyramine production, anaerobiosis seemed to favour the enzyme activity because all L. lactis strains produced higher tyramine amount. doi:10.5219/43

Conversion of p-tyrosine to p-tyramine in the isolated perfused rat kidney: Modulation by perfusate concentrations of p-tyrosine

International Nuclear Information System (INIS)

Brier, M.E.; Bowsher, R.R.; Henry, D.P.; Mayer, P.R.

1991-01-01

The authors used the isolated perfused rat kidney to evaluate the role of renal decarboxylation of p-tyrosine as the source of urinary p-tyramine. Kidneys were perfused with concentrations of p-tyrosine ranging from 0.02 mM to 2.0 mM. p-Tyramine was measured by a sensitive and specific radioenzymatic assay. An increase in the perfusate concentration of p-tyrosine resulted in a significant increase in p-tyramine production that was blocked by the addition of NSD-1015, an inhibitor of aromatic-1-amino decarboxylase (AADC). They conclude p-tyrosine is the precursor for the renal production of p-tyramine, renal AADC catalyzes the formation of urinary p-tyramine, synthesized p-tyramine is predominantly excreted in the urine, and p-tyramine synthesis is modulated by the arterial delivery of p-tyrosine to the kidney

Spin-trapping and ESR studies of the direct photolysis of aromatic amino acids, dipeptides, tripeptides and polypeptides in aqueous solutions-II. Tyrosine and related compounds

Energy Technology Data Exchange (ETDEWEB)

Lion, Y; Kuwabara, M; Riesz, P [National Cancer Inst., Bethesda, MD (USA)

1982-01-01

The UV-photolysis of peptides containing tyrosine (Tyr) was investigated in aqueous solutions at room temperature at 220 and 265 nm. The short-lived free radicals formed during photolysis were spin-trapped by t-nitrosobutane and identified by electron spin resonance. For N-acetyl-and N-formyl-L-Tyr and for peptides containing L-Tyr as the middle residue, photolysis at 265 nm under neutral conditions produced mainly spin-adducts due to the scission between the alpha carbon and the methylene group attached to the aromatic ring, while at 220 nm decarboxylation radicals were spin-trapped. Photolysis of di- and tripeptides at 275 nm in alkaline solutions predominantly generated deamination radicals. The radicals produced in the photolysis of the oxidized A chain of insulin were tentatively characterized by comparison with the results for di- and tripeptides.

Cysteic acid and taurine synthesis from sulphate in the chick embryo; Synthese de l'acide cysteique et de la taurine a partir du sulfate dans l'oeuf embryonne de poule

Energy Technology Data Exchange (ETDEWEB)

Chapeville, F [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1960-07-01

The formation of taurine from sulphate was studied in the chick embryo using the radioisotopes of: sulphur, carbon and hydrogen. The following reactions occur: 1) reduction of sulphate to sulphite; 2) fixation of the sulphite on a carbon chain with an amino group, resulting from desulphydration of L-cysteine, which leads to the formation of L-cysteic acid; 3) decarboxylation of L-cysteic acid. Reaction (1) takes place only in the endo-dermal cells of the yolk sac; reaction (2) in these same cells and in the yolk; reaction (3) is general, localized in the yolk sac, in the yolk as well as in the tissues of the embryo itself. The enzyme which catalyses reaction (2) has been purified; the coenzyme is pyridoxal phosphate. The desulphydration of cysteine by this enzyme is a reversible reaction. In non-physiological conditions of concentration and temperature, pyridoxal phosphate catalyses in the presence of metallic ions, the desulphydration of cysteine and the formation of cysteic acid from sulphite. (author) [French] On a montre que la formation de taurine a partir de sulfate dans I'oeuf embryonne de poule, etudiee a l'aide des radioisotopes, du soufre, du carbone et de l'hydrogene, correspond aux reactions suivantes: 1) reduction du sulfate en sulfite; 2) fixation du sulfite sur une chaine tricarbonee et aminee provenant de la desulfhydration de la L-cysteine, fixation conduisant a la formation d'acide L-cysteique; 3) decarboxylation de l'acide L-cysteique. La reaction (1) a lieu uniquement dans les cellules de l'endoderme du sac vitellin; la reaction (2) dans les memes cellules et dans le vitellus; la reaction (3) est plus generale, elle est localisee dans le sac vitellin, dans le vitellus et dans les tissus de l'embryon. L'enzyme qui catalyse la reaction (2) a ete purifie; il possede le phosphate de pyridoxal comme coenzyme. La desulfhydration de la cysteine par cet enzyme est une reaction reversible. Dans les conditions non physiologiques de concentration et de

Evaluation of cannabinoids concentration and stability in standardized preparations of cannabis tea and cannabis oil by ultra-high performance liquid chromatography tandem mass spectrometry.

Science.gov (United States)

Pacifici, Roberta; Marchei, Emilia; Salvatore, Francesco; Guandalini, Luca; Busardò, Francesco Paolo; Pichini, Simona

2017-08-28

Cannabis has been used since ancient times to relieve neuropathic pain, to lower intraocular pressure, to increase appetite and finally to decrease nausea and vomiting. The combination of the psychoactive cannabis alkaloid Δ9-tetrahydrocannabinol (THC) with the non-psychotropic alkaloids cannabidiol (CBD) and cannabinol (CBN) demonstrated a higher activity than THC alone. The Italian National Institute of Health sought to establish conditions and indications on how to correctly use nationally produced cannabis to guarantee therapeutic continuity in individuals treated with medical cannabis. The evaluation of cannabinoids concentration and stability in standardized preparations of cannabis tea and cannabis oil was conducted using an easy and fast ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) assay. Extraction efficiency of oil was significantly higher than that of water with respect to the different cannabinoids. This was especially observed in the case of the pharmacologically active THC, CBD and their acidic precursors. Fifteen minutes boiling was sufficient to achieve the highest concentrations of cannabinoids in the cannabis tea solutions. At ambient temperature, a significant THC and CBD decrease to 50% or less of the initial concentration was observed over 3 and 7 days, respectively. When refrigerated at 4 °C, similar decreasing profiles were observed for the two compounds. The cannabinoids profile in cannabis oil obtained after pre-heating the flowering tops at 145 °C for 30 min in a static oven resulted in a complete decarboxylation of cannabinoid acids CBDA and THCA-A. Nevertheless, it was apparent that heat not only decarboxylated acidic compounds, but also significantly increased the final concentrations of cannabinoids in oil. The stability of cannabinoids in oil samples was higher than that in tea samples since the maximum decrease (72% of initial concentration) was observed in THC coming from unheated flowering

Degradation kinetics and mechanism of β-lactam antibiotics by the activation of H{sub 2}O{sub 2} and Na{sub 2}S{sub 2}O{sub 8} under UV-254 nm irradiation

Energy Technology Data Exchange (ETDEWEB)

He, Xuexiang [Environmental Engineering and Science Program, University of Cincinnati, Cincinnati, OH 45221-0012 (United States); Department of Civil and Environmental Engineering and Nireas-International Water Research Centre, School of Engineering, University of Cyprus, PO Box 20537, 1678 Nicosia (Cyprus); Mezyk, Stephen P. [Department of Chemistry and Biochemistry, California State University Long Beach, 1250 Bellflower Blvd., Long Beach, CA 90840 (United States); Michael, Irene; Fatta-Kassinos, Despo [Department of Civil and Environmental Engineering and Nireas-International Water Research Centre, School of Engineering, University of Cyprus, PO Box 20537, 1678 Nicosia (Cyprus); Dionysiou, Dionysios D., E-mail: dionysios.d.dionysiou@uc.edu [Environmental Engineering and Science Program, University of Cincinnati, Cincinnati, OH 45221-0012 (United States); Department of Civil and Environmental Engineering and Nireas-International Water Research Centre, School of Engineering, University of Cyprus, PO Box 20537, 1678 Nicosia (Cyprus)

2014-08-30

Graphical abstract: - Highlights: • Removal efficiency was comparable at different UV fluence rates but same fluence. • Reducing pH to 3 or 2 did not inhibit the removal of nitrobenzene by UV/S{sub 2}O{sub 8}{sup 2−}. • 1.84 × 10{sup −14} M [HO{sup •} ]{sub ss} and 3.10 × 10{sup −13} M [SO{sub 4}{sup •} {sup −}]{sub ss} in UV/S{sub 2}O{sub 8}{sup 2−} were estimated. • HO{sup •} reacted faster with the β-lactams than SO{sub 4}{sup •} {sup −} but sharing similar byproducts. • Transformation pathways included hydroxylation, hydrolysis and decarboxylation. - Abstract: The extensive production and usage of antibiotics have led to an increasing occurrence of antibiotic residuals in various aquatic compartments, presenting a significant threat to both ecosystem and human health. This study investigated the degradation of selected β-lactam antibiotics (penicillins: ampicillin, penicillin V, and piperacillin; cephalosporin: cephalothin) by UV-254 nm activated H{sub 2}O{sub 2} and S{sub 2}O{sub 8}{sup 2−} photochemical processes. The UV irradiation alone resulted in various degrees of direct photolysis of the antibiotics; while the addition of the oxidants improved significantly the removal efficiency. The steady-state radical concentrations were estimated, revealing a non-negligible contribution of hydroxyl radicals in the UV/S{sub 2}O{sub 8}{sup 2−} system. Mineralization of the β-lactams could be achieved at high UV fluence, with a slow formation of SO{sub 4}{sup 2−} and a much lower elimination of total organic carbon (TOC). The transformation mechanisms were also investigated showing the main reaction pathways of hydroxylation (+16 Da) at the aromatic ring and/or the sulfur atom, hydrolysis (+18 Da) at the β-lactam ring and decarboxylation (–44 Da) for the three penicillins. Oxidation of amine group was also observed for ampicillin. This study suggests that UV/H{sub 2}O{sub 2} and UV/S{sub 2}O{sub 8}{sup 2−} advanced

Degradation of the Alternaria mycotoxins alternariol, alternariol monomethyl ether, and altenuene upon bread baking.

Science.gov (United States)

Siegel, David; Feist, Michael; Proske, Matthias; Koch, Matthias; Nehls, Irene

2010-09-08

The stability of the Alternaria mycotoxins alternariol, alternariol monomethyl ether, and altenuene upon bread baking was investigated by model experiments using a spiked wholemeal wheat flour matrix. For alternariol and alternariol monomethyl ether, but not for altenuene, degradation products, formed through a sequence of hydrolysis and decarboxylation, could be identified in pilot studies. The simultaneous quantification of alternariol, alternariol monomethyl ether, altenuene, and the degradation products was achieved by a newly developed high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) multimethod. The obtained quantitative data indicate that the Alternaria mycotoxins are barely degraded during wet baking, while significant degradation occurs upon dry baking, with the stability decreasing in the order alternariol monomethyl ether>alternariol>altenuene. The novel degradation products could be detected after the wet baking of flour spiked with alternariol and in a sample survey of 24 commercial cereal based baking products.

Acrylamide and 5-hydroxymethylfurfural formation during biscuit baking. Part II: Effect of the ratio of reducing sugars and asparagine.

Science.gov (United States)

Nguyen, Ha T; van der Fels-Klerx, H J Ine; van Boekel, M A J S

2017-09-01

This study investigated acrylamide and 5-hydroxymethylfurfural (HMF) formation during biscuit baking. Four types of wheat flour with different molar ratios of total fructose and glucose to asparagine were investigated. Nevertheless, the molar ratio in all four biscuit doughs exceeded one after proofing due to enzyme action. Data obtained after baking were used to develop a mechanistic model, based on the asparagine-related pathway, for acrylamide and HMF formation in the four baked biscuit types. Asparagine reacted with fructose to form a Schiff base before decarboxylation to produce acrylamide without Amadori rearrangement product and sugar fragmentation. Fructose contributed considerably to acrylamide formation and to HMF formation via caramelization in all four biscuit types. No clear correlation was found between acrylamide and HMF in baked biscuits, nor between asparagine and the sum of glucose and fructose concentrations in the wheat flour. Copyright © 2017 Elsevier Ltd. All rights reserved.

Acrylamide and 5-hydroxymethylfurfural formation during baking of biscuits: Part I: Effects of sugar type.

Science.gov (United States)

Nguyen, Ha T; Van der Fels-Klerx, H J Ine; Peters, Ruud J B; Van Boekel, Martinus A J S

2016-02-01

This study aimed to investigate the effects of sugar type on the reaction mechanism for formation of acrylamide and 5-hydroxymethylfurfural (HMF) during the baking of biscuits at 200°C using multiresponse modelling. Four types of biscuits were prepared: (1) with sucrose, (2) with glucose and fructose, (3) with fructose only and (4) with glucose only. Experimental data showed that HMF concentration was highest in biscuits with glucose and fructose, whereas acrylamide concentration was highest in biscuits with glucose, also having the highest asparagine concentration. Proposed mechanistic models suggested that HMF is formed via caramelisation and that acrylamide formation follows the specific amino acid route, i.e., reducing sugars react with asparagine to form the Schiff base before decarboxylation, to generate acrylamide without the Amadori rearrangement product and sugar fragmentation. Study results contribute to understanding chemical reaction pathways in real food products. Copyright © 2015 Elsevier Ltd. All rights reserved.

A new biological method for preparing certain sulphurated substances labelled with S35

International Nuclear Information System (INIS)

Chapeville, F.; Maier-Huser, H.; Fromageot, P.

1962-01-01

Previous investigations have shown that the yolk-sac of embryonic bird's eggs can be used to produce the following reactions: (a) reduction of sulphate to sulphite; (b) fixation of the sulphite on the carbon chain produced by the desulf-hydration of l-cysteine, with formation of l-cysteic acid; (c) decarboxylation of the l-cysteine acid into taurine. The enzymatic system which causes reaction (b) has been purified. It also acts as a catalyst in the sulphur-exchange between the cysteine and the mineral sulphide. The authors have utilized these data in preparing sulphurated substances labelled with S 35 : taurine S 35 , l-cysteine S 35 and l-cysteic acid S 35 . For each of the three, they discuss the chemical reactions involved, the methods of preparation, the experimental conditions of extraction and purity-control, together with the yields and specific activities obtained. (authors) [fr

Plasticization-resistant hollow fiber membranes for CO2/CH4 separation based on a thermally crosslinkable polyimide

KAUST Repository

Chen, Chien-Chiang

2011-10-01

Decarboxylation-induced thermal crosslinking has been demonstrated to be effective for stabilizing membranes against plasticization in dense films. This study extends this promising crosslinking approach from dense films to industrially relevant asymmetric hollow fiber membranes. Crosslinkable asymmetric hollow fiber membranes were spun from a carboxylic acid containing polyimide, 6FDA-DAM:DABA. Dope and spinning conditions were optimized to obtain fibers with a defect-free selective skin layer. It is found that slightly defective fibers suffered severe selectivity loss after thermal crosslinking, suggesting that defect-free property is essential to the performance of the resulting crosslinked hollow fiber membranes. The crosslinked fibers were tested for CO 2/CH 4 separation. The excellent plasticization resistance under high pressure feeds (with highest CO 2 partial pressure of 400psia) suggests that these robust membranes are promising for aggressive natural gas purification. © 2011 Elsevier B.V.

2,4-dichlorophenoxyacetic acid degradation in soils

International Nuclear Information System (INIS)

Bellinck, Celine; Batistic, L.; Mayaudon, J.

1979-01-01

The mineralization of 2,4-D (carboxyl 14 C) applied at 10 ppm was beginning immediately after its application in the soil. At higher concentrations a lag period appeared. The quantity of residual 14 C in the soil after 100 days incubation time reached 8.30 and 90% for initial concentrations of 10, 50 and 500 ppm of 2,4-D. The biostable 14 C which was extractable by water was exclusively constituted of 2,4-D. The mineral amendments P-K and PK inhibited 2,4-D mineralization, while the combination CaMg and also those containing nitrogen activated it. When 500 ppm of 2,4-D were applied one observed the formation of a zymogenous flora which was very active in the decarboxylation of the herbicide but unable to cleave the aromatic ring. These microorganisms probably belong to the genus Arthobacter and Pseudomonas [fr

Modeling Enzymatic Transition States by Force Field Methods

DEFF Research Database (Denmark)

Hansen, Mikkel Bo; Jensen, Hans Jørgen Aagaard; Jensen, Frank

2009-01-01

The SEAM method, which models a transition structure as a minimum on the seam of two diabatic surfaces represented by force field functions, has been used to generate 20 transition structures for the decarboxylation of orotidine by the orotidine-5'-monophosphate decarboxylase enzyme. The dependence...... of the TS geometry on the flexibility of the system has been probed by fixing layers of atoms around the active site and using increasingly larger nonbonded cutoffs. The variability over the 20 structures is found to decrease as the system is made more flexible. Relative energies have been calculated...... by various electronic structure methods, where part of the enzyme is represented by a force field description and the effects of the solvent are represented by a continuum model. The relative energies vary by several hundreds of kJ/mol between the transition structures, and tests showed that a large part...

Loss of metabolites from monkey striatum during PET with FDOPA

DEFF Research Database (Denmark)

Cumming, P; Munk, O L; Doudet, D

2001-01-01

diffusion of [(18)F]fluorodopamine metabolites from brain. Consequently, time-radioactivity recordings of striatum are progressively influenced by metabolite loss. In linear analyses, the net blood-brain clearance of FDOPA (K(D)(i), ml g(-1) min(-1)) can be corrected for this loss by the elimination rate...... constant k(Lin)(cl) (min(-1)). Similarly, the DOPA decarboxylation rate constant (k(D)(3), min(-1)) calculated by compartmental analysis can also be corrected for metabolite loss by the elimination rate constant k(DA)(9) (min(-1)). To compare the two methods, we calculated the two elimination rate...... of the estimate was substantially improved upon correction for metabolite loss. The rate constants for metabolite loss were higher in MPTP-lesioned monkey striatum than in normal striatum. The high correlation between individual estimates of k(Lin)(cl) and k(DA)(9) suggests that both rate constants reveal loss...

InP/ZnS nanocrystals: coupling NMR and XPS for fine surface and interface description.

Science.gov (United States)

Virieux, Héloïse; Le Troedec, Marianne; Cros-Gagneux, Arnaud; Ojo, Wilfried-Solo; Delpech, Fabien; Nayral, Céline; Martinez, Hervé; Chaudret, Bruno

2012-12-05

Advanced (1)H, (13)C, and (31)P solution- and solid-state NMR studies combined with XPS were used to probe, at the molecular scale, the composition (of the core, the shell, and the interface) and the surface chemistry of InP/ZnS core/shell quantum dots prepared via a non-coordinating solvent strategy. The interface between the mismatched InP and ZnS phases is composed of an amorphous mixed oxide phase incorporating InPO(x) (with x = 3 and predominantly 4), In(2)O(3), and InO(y)(OH)(3-2y) (y = 0, 1). Thanks to the analysis of the underlying reaction mechanisms, we demonstrate that the oxidation of the upper part of the InP core is the consequence of oxidative conditions brought by decarboxylative coupling reactions (ketonization). These reactions occur during both the core preparation and the coating process, but according to different mechanisms.

Plasticization-resistant hollow fiber membranes for CO2/CH4 separation based on a thermally crosslinkable polyimide

KAUST Repository

Chen, Chien-Chiang; Qiu, Wulin; Miller, Stephen J.; Koros, William J.

2011-01-01

Decarboxylation-induced thermal crosslinking has been demonstrated to be effective for stabilizing membranes against plasticization in dense films. This study extends this promising crosslinking approach from dense films to industrially relevant asymmetric hollow fiber membranes. Crosslinkable asymmetric hollow fiber membranes were spun from a carboxylic acid containing polyimide, 6FDA-DAM:DABA. Dope and spinning conditions were optimized to obtain fibers with a defect-free selective skin layer. It is found that slightly defective fibers suffered severe selectivity loss after thermal crosslinking, suggesting that defect-free property is essential to the performance of the resulting crosslinked hollow fiber membranes. The crosslinked fibers were tested for CO 2/CH 4 separation. The excellent plasticization resistance under high pressure feeds (with highest CO 2 partial pressure of 400psia) suggests that these robust membranes are promising for aggressive natural gas purification. © 2011 Elsevier B.V.

Alternate substrates and isotope effects as a probe of the malic enzyme reaction

International Nuclear Information System (INIS)

Gavva, S.R.

1988-01-01

Dissociation constants for alternative dinucleotide substrates and competitive inhibitors suggest that the dinucleotide binding site of the Ascaris suum NAD-malic enzyme is hydrophobic in the vicinity of the nicotinamide ring. Changes in the divalent metal ion activator from Mg 2+ to Mn 2+ or Cd 2+ results in a decrease in the dinucleotide affinity and an increase in the affinity for malate. Primary deuterium and 13 C isotope effects obtained with the different metal ions suggest either a change in the transition state structure for the hydride transfer or decarboxylation steps or both. Deuterium isotope effects are finite whether reactants are maintained at saturating or limiting concentrations with all the metal ions and dinucleotide substrates used. For the native enzyme, primary deuterium isotope effects increase with a concomitant decrease in the 13 C effects when NAD is replaced by an alternate dinucleotide substrate different in redox potential

Visible-Light Photoredox-Catalyzed Giese Reaction: Decarboxylative Addition of Amino Acid Derived α-Amino Radicals to Electron-Deficient Olefins

KAUST Repository

Millet, Anthony

2016-06-20

A tin- and halide-free, visible-light photoredox-catalyzed Giese reaction was developed. Primary and secondary α-amino radicals were generated readily from amino acids in the presence of catalytic amounts of an iridium photocatalyst. The reactivity of the α-amino radicals has been evaluated for the functionalization of a variety of activated olefins. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Visible-Light Photoredox-Catalyzed Giese Reaction: Decarboxylative Addition of Amino Acid Derived α-Amino Radicals to Electron-Deficient Olefins

KAUST Repository

Millet, Anthony; Lefebvre, Quentin; Rueping, Magnus

2016-01-01

A tin- and halide-free, visible-light photoredox-catalyzed Giese reaction was developed. Primary and secondary α-amino radicals were generated readily from amino acids in the presence of catalytic amounts of an iridium photocatalyst. The reactivity of the α-amino radicals has been evaluated for the functionalization of a variety of activated olefins. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Kinetic and mechanistic studies of reactive intermediates in photochemical and transition metal-assisted oxidation, decarboxylation and alkyl transfer reactions

Energy Technology Data Exchange (ETDEWEB)

Carraher, Jack McCaslin [Iowa State Univ., Ames, IA (United States)

2014-01-01

Reactive species like high-valent metal-oxo complexes and carbon and oxygen centered radicals are important intermediates in enzymatic systems, atmospheric chemistry, and industrial processes. Understanding the pathways by which these intermediates form, their relative reactivity, and their fate after reactions is of the utmost importance. Herein are described the mechanistic detail for the generation of several reactive intermediates, synthesis of precursors, characterization of precursors, and methods to direct the chemistry to more desirable outcomes yielding ‘greener’ sources of commodity chemicals and fuels.

(Per)chlorate reduction by an acetogenic bacterium, Sporomusa sp., isolated from an underground gas storage.

KAUST Repository

Balk, Melike

2010-08-03

A mesophilic bacterium, strain An4, was isolated from an underground gas storage reservoir with methanol as substrate and perchlorate as electron acceptor. Cells were Gram-negative, spore-forming, straight to curved rods, 0.5-0.8 microm in diameter, and 2-8 microm in length, growing as single cells or in pairs. The cells grew optimally at 37 degrees C, and the pH optimum was around 7. Strain An4 converted various alcohols, organic acids, fructose, acetoin, and H(2)/CO(2) to acetate, usually as the only product. Succinate was decarboxylated to propionate. The isolate was able to respire with (per)chlorate, nitrate, and CO(2). The G+C content of the DNA was 42.6 mol%. Based on the 16S rRNA gene sequence analysis, strain An4 was most closely related to Sporomusa ovata (98% similarity). The bacterium reduced perchlorate and chlorate completely to chloride. Key enzymes, perchlorate reductase and chlorite dismutase, were detected in cell-free extracts.

Conversion of sweet potato waste to solid fuel via hydrothermal carbonization.

Science.gov (United States)

Chen, Xinfei; Ma, Xiaoqian; Peng, Xiaowei; Lin, Yousheng; Yao, Zhongliang

2018-02-01

Hydrothermal carbonization (HTC) of sweet potato waste was performed to investigate the effect of process parameters including reaction temperature (180-300 °C) and residence time (0-120 min) on the characteristics of hydrochars. The results showed that the increase of reaction temperature and residence time both decreased the yield of hydrochars. With the increase of reaction temperature and residence time, the carbon content of hydrochars increased, while the hydrogen and oxygen contents decreased. The lower H/C and O/C ratios indicated that dehydration and decarboxylation reactions occurred during HTC. The occurrence of aromatization reaction was found in FTIR spectra. Thus, the fixed carbon content, higher heating value, and energy density of hydrochars increased. SEM analysis indicated that HTC developed rough surface with crack on the hydrochars. The thermogravimetric experiments displayed the increase trend in combustion ignition temperature, burnout temperature and activation energy as reaction temperature and time increase, which showed better combustion characteristics. Copyright © 2017 Elsevier Ltd. All rights reserved.

Density functional theory prediction of pKa for carboxylated single-wall carbon nanotubes and graphene

Science.gov (United States)

Li, Hao; Fu, Aiping; Xue, Xuyan; Guo, Fengna; Huai, Wenbo; Chu, Tianshu; Wang, Zonghua

2017-06-01

Density functional calculations have been performed to investigate the acidities for the carboxylated single-wall carbon nanotubes and graphene. The pKa values for different COOH-functionalized models with varying lengths, diameters and chirality of nanotubes and with different edges of graphene were predicted using the SMD/M05-2X/6-31G* method combined with two universal thermodynamic cycles. The effects of following factors, such as, the functionalized position of carboxyl group, the Stone-Wales and single vacancy defects, on the acidity of the functionalized nanotube and graphene have also been evaluated. The deprotonated species have undergone decarboxylation when the hybridization mode of the carbon atom at the functionalization site changed from sp2 to sp3 both for the tube and graphene. The knowledge of the pKa values of the carboxylated nanotube and graphene could be of great help for the understanding of the nanocarbon materials in many diverse areas, including environmental protection, catalysis, electrochemistry and biochemistry.

(Per)chlorate reduction by an acetogenic bacterium, Sporomusa sp., isolated from an underground gas storage.

KAUST Repository

Balk, Melike; Mehboob, Farrakh; van Gelder, Antonie H; Rijpstra, W Irene C; Damsté , Jaap S Sinninghe; Stams, Alfons J M

2010-01-01

A mesophilic bacterium, strain An4, was isolated from an underground gas storage reservoir with methanol as substrate and perchlorate as electron acceptor. Cells were Gram-negative, spore-forming, straight to curved rods, 0.5-0.8 microm in diameter, and 2-8 microm in length, growing as single cells or in pairs. The cells grew optimally at 37 degrees C, and the pH optimum was around 7. Strain An4 converted various alcohols, organic acids, fructose, acetoin, and H(2)/CO(2) to acetate, usually as the only product. Succinate was decarboxylated to propionate. The isolate was able to respire with (per)chlorate, nitrate, and CO(2). The G+C content of the DNA was 42.6 mol%. Based on the 16S rRNA gene sequence analysis, strain An4 was most closely related to Sporomusa ovata (98% similarity). The bacterium reduced perchlorate and chlorate completely to chloride. Key enzymes, perchlorate reductase and chlorite dismutase, were detected in cell-free extracts.

Utilization of barley or wheat bran to bioconvert glutamate to γ-aminobutyric acid (GABA).

Science.gov (United States)

Jin, Wen-Jie; Kim, Min-Ju; Kim, Keun-Sung

2013-09-01

This study deals with the utilization of agro-industrial wastes created by barley and wheat bran in the production of a value-added product, γ-aminobutyric acid (GABA). The simple and eco-friendly reaction requires no pretreatment or microbial fermentation steps but uses barley or wheat bran as an enzyme source, glutamate as a substrate, and pyridoxal 5'-phosphate (PLP) as a cofactor. The optimal reaction conditions were determined on the basis of the temperatures and times used for the decarboxylation reactions and the initial concentrations of barley or wheat bran, glutamate, and PLP. The optimal reactions produced 9.2 mM of GABA from 10 mM glutamate, yielding a 92% GABA conversion rate, when barley bran was used and 6.0 mM of GABA from 10 mM glutamate, yielding a 60% GABA conversion rate, when wheat bran was used. The results imply that barley bran is more efficient than wheat bran in the production of GABA. © 2013 Institute of Food Technologists®

Overexpression of the NADP+-specific isocitrate dehydrogenase gene (icdA) in citric acid-producing Aspergillus niger WU-2223L.

Science.gov (United States)

Kobayashi, Keiichi; Hattori, Takasumi; Hayashi, Rie; Kirimura, Kohtaro

2014-01-01

In the tricarboxylic acid (TCA) cycle, NADP(+)-specific isocitrate dehydrogenase (NADP(+)-ICDH) catalyzes oxidative decarboxylation of isocitric acid to form α-ketoglutaric acid with NADP(+) as a cofactor. We constructed an NADP(+)-ICDH gene (icdA)-overexpressing strain (OPI-1) using Aspergillus niger WU-2223L as a host and examined the effects of increase in NADP(+)-ICDH activity on citric acid production. Under citric acid-producing conditions with glucose as the carbon source, the amounts of citric acid produced and glucose consumed by OPI-1 for the 12-d cultivation period decreased by 18.7 and 10.5%, respectively, compared with those by WU-2223L. These results indicate that the amount of citric acid produced by A. niger can be altered with the NADP(+)-ICDH activity. Therefore, NADP(+)-ICDH is an important regulator of citric acid production in the TCA cycle of A. niger. Thus, we propose that the icdA gene is a potentially valuable tool for modulating citric acid production by metabolic engineering.

The influences of fish infusion broth on the biogenic amines formation by lactic acid bacteria

Directory of Open Access Journals (Sweden)

Esmeray Küley

2013-01-01

Full Text Available The influences of fish infusion decarboxylase broth (IDB on biogenic amines (BA formation by lactic acid bacteria (LAB were investigated. BA productions by single LAB strains were tested in five different fish (anchovy, mackerel, white shark, sardine and gilthead seabream IDB. The result of the study showed that significant differences in ammonia (AMN and BA production were observed among the LAB strains in fish IDB (p < 0.05. The highest AMN and TMA production by LAB strains were observed for white shark IDB. The all tested bacteria had decarboxylation activity in fish IDB. The uppermost accumulated amines by LAB strains were tyramine (TYM, dopamine, serotonin and spermidine. The maximum histamine production was observed in sardine (101.69 mg/L and mackerel (100.84 mg/L IDB by Leuconostoc mesenteroides subsp. cremoris and Pediococcus acidophilus, respectively. Lactobacillus delbrueckii subsp. lactis and Pediococcus acidophilus had a high TYM producing capability (2943 mg/L and 1157 mg/L in sardine IDB.

Co-hydrothermal treatment of fallen leaves with iron sludge to prepare magnetic iron product and solid fuel.

Science.gov (United States)

Gu, Lin; Li, Binglian; Wen, Haifeng; Zhang, Xin; Wang, Liang; Ye, Jianfeng

2018-06-01

The hydrothermal carbonization (HTC) was performed on Metasequoia Leaves (ML) in the presence of iron sludge, both of which were generated as solid residuals. The relations between sludge, char's properties and operating conditions were systemically investigated. Iron sludge primarily catalyzed the efficient formation of char with higher heating value (HHV) becoming 1.15-1.65 times of ML (18.21 MJ/kg) and was meanwhile reduced to magnetite. The hydrated Fe ions in octahedron crystals acted as nucleophiles facilitating the dehydration and decarboxylation reactions. The increased HHV is found strong temperature dependent while prolonging the residence time is more preferable for low organic acids generation. Thermogravimetric analysis confirmed the iron sludge enhanced conversion of volatile to fixed carbon. The as-prepared solid char showed better stability after catalytic HTC treatment, having ignition temperature increased from 253 to 426 °C as compared to the char prepared without iron sludge addition. Copyright © 2018 Elsevier Ltd. All rights reserved.

Metagenomic insight into methanogenic reactors promoting direct interspecies electron transfer via granular activated carbon.

Science.gov (United States)

Park, Jeong-Hoon; Park, Jong-Hun; Je Seong, Hoon; Sul, Woo Jun; Jin, Kang-Hyun; Park, Hee-Deung

2018-07-01

To provide insight into direct interspecies electron transfer via granular activated carbon (GAC), the effect of GAC supplementation on anaerobic digestion was evaluated. Compared to control samples, the GAC supplementation increased the total amount of methane production and its production rate by 31% and 72%, respectively. 16S rDNA sequencing analysis revealed a shift in the archaeal community composition; the Methanosarcina proportion decreased 17%, while the Methanosaeta proportion increased 5.6%. Metagenomic analyses based on shotgun sequencing demonstrated that the abundance of pilA and omcS genes belonging to Geobacter species decreased 69.4% and 29.4%, respectively. Furthermore, the analyses suggested a carbon dioxide reduction pathway rather than an acetate decarboxylation pathway for methane formation. Taken together, these results suggest that GAC improved methane production performance by shifting the microbial community and altering functional genes associated with direct interspecies electron transfer via conductive materials. Copyright © 2018 Elsevier Ltd. All rights reserved.

H3PO4/Al2O3 catalysts: characterization and catalytic evaluation of oleic acid conversion to biofuels and biolubricant

Directory of Open Access Journals (Sweden)

Lucia Regina Raddi de Araujo

2006-06-01

Full Text Available Al2O3 and H3PO4/Al2O3 catalysts were investigated in the conversion of oleic acid to biofuels and biolubricant at 1 atm and at 623 K. The catalytic tests were performed in a fixed bed and continuous flow reactor, using an oleic acid-catalyst ratio of 4 and N2 as the carrier gas. The reaction products were analyzed by gas chromatography and acidity measurements. N2 adsorption-desorption, X ray diffraction, 31P nuclear magnetic resonance and FT-IR spectroscopy were also employed to evaluate the textural, structural and acidic properties of the catalysts. The results showed that phosphoric acid impregnation improved the alumina decarboxylation activities, generating hydrocarbons in the range of gasoline, diesel oil and lubricant oil. The best catalytic performance was achieved with the highest surface area alumina impregnated with H3PO4, which was the solid that allied high total acidity with a large quantity of mesopores.

Additional synthesis of starch from sucrose in leaves of arabidopsis in the light

International Nuclear Information System (INIS)

Keerberg, O.; Ivanova, H.; Keerberg, H.; Paernik, T.

2005-01-01

Full text: Accumulating during daytime starch is converted in the night into sucrose and consumed in respiratory, biosynthetic and transport processes. However in the light the degradation and conversion of starch are blocked. In pulse chase experiments with wild type plants and starchless mutants pgm or adg1 of arabidopsis an increase of starch radioactivity during chase in nonradioactive medium in the light was detected. These findings suggest that starch was additionally synthesized from labeled cytosolic soluble photosynthates, preferentially from sucrose. Radiogasometric studies of gas exchange have revealed that sucrose is consumed also in photorespiratory decarboxylations. To be involved in photorespiration the products of sucrose degradation must be transported from cytosol into chloroplast. We presume that derived from sucrose hexoses are transported into chloroplast by hexose transporter and phosphorylated there in hexokinase reaction. The phosphorylated hexoses may be consumed either for additional synthesis of starch or incorporated into the reductive pentose phosphate cycle and, via this cycle, into the glycolate cycle. (author)

Palladium(II)-catalyzed desulfitative synthesis of aryl ketones from sodium arylsulfinates and nitriles: scope, limitations, and mechanistic studies.

Science.gov (United States)

Skillinghaug, Bobo; Sköld, Christian; Rydfjord, Jonas; Svensson, Fredrik; Behrends, Malte; Sävmarker, Jonas; Sjöberg, Per J R; Larhed, Mats

2014-12-19

A fast and efficient protocol for the palladium(II)-catalyzed production of aryl ketones from sodium arylsulfinates and various organic nitriles under controlled microwave irradiation has been developed. The wide scope of the reaction has been demonstrated by combining 14 sodium arylsulfinates and 21 nitriles to give 55 examples of aryl ketones. One additional example illustrated that, through the choice of the nitrile reactant, benzofurans are also accessible. The reaction mechanism was investigated by electrospray ionization mass spectrometry and DFT calculations. The desulfitative synthesis of aryl ketones from nitriles was also compared to the corresponding transformation starting from benzoic acids. Comparison of the energy profiles indicates that the free energy requirement for decarboxylation of 2,6-dimethoxybenzoic acid and especially benzoic acid is higher than the corresponding desulfitative process for generating the key aryl palladium intermediate. The palladium(II) intermediates detected by ESI-MS and the DFT calculations provide a detailed understanding of the catalytic cycle.

Precursors and metabolic pathway for guaiacol production by Alicyclobacillus acidoterrestris.

Science.gov (United States)

Cai, Rui; Yuan, Yahong; Wang, Zhouli; Guo, Chunfeng; Liu, Bin; Liu, Laping; Wang, Yutang; Yue, Tianli

2015-12-02

Alicyclobacillus acidoterrestris has recently received much attention due to its implication in the spoilage of pasteurized fruit juices, which was manifested by the production of guaiacol. Vanillic acid and vanillin have been accepted as the biochemical precursors of guaiacol in fruit juices. The purpose of this study was to try to find other precursors and elucidate details about the conversion of vanillic acid and vanillin to guaiacol by A. acidoterrestris. Four potential substrates including ferulic acid, catechol, phenylalanine and tyrosine were analyzed, but they could not be metabolized to guaiacol by all the thirty A. acidoterrestris strains tested. Resting cell studies and enzyme assays demonstrated that vanillin was reduced to vanillyl alcohol by NADPH-dependent vanillin reductase and oxidized to vanillic acid by NAD(P)(+)-dependent vanillin dehydrogenases in A. acidoterrestris DSM 3923. Vanillic acid underwent a nonoxidative decarboxylation to guaiacol. The reversible vanillic acid decarboxylase involved was oxygen insensitive and pyridine nucleotide-independent. Copyright © 2015. Published by Elsevier B.V.

Isolation and Biosynthetic Analysis of Haliamide, a New PKS-NRPS Hybrid Metabolite from the Marine Myxobacterium Haliangium ochraceum

Directory of Open Access Journals (Sweden)

Yuwei Sun

2016-01-01

Full Text Available Myxobacteria of marine origin are rare and hard-to-culture microorganisms, but they genetically harbor high potential to produce novel antibiotics. An extensive investigation on the secondary metabolome of the unique marine myxobacterium Haliangium ochraceum SMP-2 led to the isolation of a new polyketide-nonribosomal peptide hybrid product, haliamide (1. Its structure was elucidated by spectroscopic analyses including NMR and HR-MS. Haliamide (1 showed cytotoxicity against HeLa-S3 cells with IC50 of 12 μM. Feeding experiments were performed to identify the biosynthetic building blocks of 1, revealing one benzoate, one alanine, two propionates, one acetate and one acetate-derived terminal methylene. The biosynthetic gene cluster of haliamide (hla, 21.7 kbp was characterized through the genome mining of the producer, allowing us to establish a model for the haliamide biosynthesis. The sulfotransferase (ST-thioesterase (TE domains encoded in hlaB appears to be responsible for the terminal alkene formation via decarboxylation.

Oxidative damage to collagen and related substrates by metal ion/hydrogen peroxide systems

DEFF Research Database (Denmark)

Hawkins, C L; Davies, Michael Jonathan

1997-01-01

. In this study electron paramagnetic resonance spectroscopy with spin trapping has been used to identify radicals formed on collagen and related materials by metal ion-H2O2 mixtures. Attack of the hydroxyl radical, from a Fe(II)-H2O2 redox couple, on collagen peptides gave signals from both side chain (.CHR...... are similar to those from the alpha-carbon site of peptides and the side-chain of lysine. Enzymatic digestion of the large, protein-derived, species releases similar low-molecular-weight adducts. The metal ion employed has a dramatic effect on the species observed. With Cu(I)-H2O2 or Cu(II)-H2O2 instead of Fe(II)-H......2O2, evidence has been obtained for: i) altered sites of attack and fragmentation, ii) C-terminal decarboxylation, and iii) hydrogen abstraction at N-terminal alpha-carbon sites. This altered behaviour is believed to be due to the binding of copper ions to some substrates and hence site...

SadA-Expressing Staphylococci in the Human Gut Show Increased Cell Adherence and Internalization.

Science.gov (United States)

Luqman, Arif; Nega, Mulugeta; Nguyen, Minh-Thu; Ebner, Patrick; Götz, Friedrich

2018-01-09

A subgroup of biogenic amines, the so-called trace amines (TAs), are produced by mammals and bacteria and can act as neuromodulators. In the genus Staphylococcus, certain species are capable of producing TAs through the activity of staphylococcal aromatic amino acid decarboxylase (SadA). SadA decarboxylates aromatic amino acids to produce TAs, as well as dihydroxy phenylalanine and 5-hydroxytryptophan to thus produce the neurotransmitters dopamine and serotonin. SadA-expressing staphylococci were prevalent in the gut of most probands, where they are part of the human intestinal microflora. Furthermore, sadA-expressing staphylococci showed increased adherence to HT-29 cells and 2- to 3-fold increased internalization. Internalization and adherence was also increased in a sadA mutant in the presence of tryptamine. The α2-adrenergic receptor is required for enhanced adherence and internalization. Thus, staphylococci in the gut might contribute to gut activity and intestinal colonization. Copyright © 2017 The Author(s). Published by Elsevier Inc. All rights reserved.

Probing chemistry within the membrane structure of wood with soft X-ray spectral microscopy

International Nuclear Information System (INIS)

Cody, George D.

2000-01-01

Scanning Transmission Soft X-ray spectral microscopy on Carbon's 1s absorption edge reveals the distribution of structural biopolymers within cell membrane regions of modern cedar and oak. Cellulose is extremely susceptible to beam damage. Spectroscopic studies of beam damage reveals that the chemical changes resulting from secondary electron impact may be highly selective and is consistent with hydroxyl eliminations and structural rearrangement of pyranose rings in alpha-cellulose to hydroxyl substituted γ pyrones. A study of acetylated cellulose demonstrates significantly different chemistry; principally massive decarboxylation. Defocusing the beam to a 2 μm spot size allows for the acquisition of 'pristine' cellulose spectra. Spectral deconvolution is used to assess the distribution of lignin and cellulose in the different regions of the cell membrane. Using the intensity of the hydroxylated aromatic carbons 1s-π * transition, the ratio of coniferyl and syringyl based lignin within the middle lamellae and secondary cell wall of oak, an angiosperm can be determined

Measurement of activity for S-adenosylmethionine decarboxylase using radioisotope 14C

International Nuclear Information System (INIS)

Ko, Kyong Cheol; Park, Sang Hyun; Kamio, Yoshiyuku

2007-01-01

Polyamines are essential for normal cell growth and have important physiological function. They are polycationic compounds that are present in all biological materials. Also, they have been implicated in a wide variety of biological reactions. Generally, putrescine and spermidine are contained high amount in prokaryote, but spermidine and spermine are in eukaryote, respectively. However, S. ruminantium cells contain the polyamins such as spermidine and spermine. Addition of an aminopropyl group to putrescine conducts to the synthesis of spermidine. Aminopropyl group is derived from the dcSAM, a decarboxylation of S-adenosylmethionine, through action of S-adenosylmethionine decarboxylase (SAMDC). We suggested that S. ruminantium has a different pathway compare with prokaryote for polyamine synthesis. Assay for SAMDC activity was used 14 C labeled substrate. Key enzyme in the biosynthesis of polyamines, SAMDC, was purified from S. ruminantium and characterized. The enzyme was purified about 1,259-fold to electrophoretic homogeneity with a specific activity of 1.89×10 -5 kat kg'- 1 of protein

On the Diels-Alder approach to solely biomass-derived polyethylene terephthalate (PET): conversion of 2,5-dimethylfuran and acrolein into p-xylene.

Science.gov (United States)

Shiramizu, Mika; Toste, F Dean

2011-10-24

Polyethylene terephthalate (PET) is a polymeric material with high global demand. Conventionally, PET is produced from fossil-fuel-based materials. Herein, we explored the feasibility of a sustainable method for PET production by using solely bio-renewable resources. Specifically, 2,5-dimethylfuran (derived from lignocellulosic biomass through 5-(hydroxymethyl)furfural) and acrolein (produced from glycerol, a side product of biodiesel production) were converted into the key intermediate p-xylene (a precursor of terephthalic acid). This synthesis consists of a sequential Diels-Alder reaction, oxidation, dehydration, and decarboxylation. In particular, the pivotal first step, the Diels-Alder reaction, was studied in detail to provide useful kinetic and thermodynamic data. Although it was found that this reaction requires low temperature to proceed efficiently, which presents a limitation on economic feasibility on an industrial scale, the concept was realized and bio-derived p-xylene was obtained in 34% overall yield over four steps. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cysteic acid and taurine synthesis from sulphate in the chick embryo

International Nuclear Information System (INIS)

Chapeville, F.

1960-01-01

The formation of taurine from sulphate was studied in the chick embryo using the radioisotopes of: sulphur, carbon and hydrogen. The following reactions occur: 1) reduction of sulphate to sulphite; 2) fixation of the sulphite on a carbon chain with an amino group, resulting from desulphydration of L-cysteine, which leads to the formation of L-cysteic acid; 3) decarboxylation of L-cysteic acid. Reaction (1) takes place only in the endo-dermal cells of the yolk sac; reaction (2) in these same cells and in the yolk; reaction (3) is general, localized in the yolk sac, in the yolk as well as in the tissues of the embryo itself. The enzyme which catalyses reaction (2) has been purified; the coenzyme is pyridoxal phosphate. The desulphydration of cysteine by this enzyme is a reversible reaction. In non-physiological conditions of concentration and temperature, pyridoxal phosphate catalyses in the presence of metallic ions, the desulphydration of cysteine and the formation of cysteic acid from sulphite. (author) [fr

Hydrodeoxygenation of methyl esters on sulphided NiMo/{gamma}-Al{sub 2}O{sub 3} and CoMo/{gamma}-Al{sub 2}O{sub 3} catalysts

Energy Technology Data Exchange (ETDEWEB)

Senol, O.I; Viljava, T.R.; Krause, A.O.I. [Laboratory of Industrial Chemistry, Helsinki University of Technology, P.O. Box 6100, FIN-02015 Hut (Finland)

2005-02-28

Wood-derived bio-oil contains high amounts of compounds with different oxygen-containing functional groups that must be removed to improve the fuel characteristics. Elimination of oxygen from carboxylic groups was studied with model compounds, methyl heptanoate and methyl hexanoate, on sulphided NiMo/{gamma}-Al{sub 2}O{sub 3} and CoMo/{gamma}-Al{sub 2}O{sub 3} catalysts in a flow reactor. Catalyst performances and reaction schemes were addressed. Aliphatic methyl esters produced hydrocarbons via three main paths: The first path gave alcohols followed by dehydration to hydrocarbons. Deesterification yielded an alcohol and a carboxylic acid in the second path. Carboxylic acid was further converted to hydrocarbons either directly or with an alcohol intermediate. Decarboxylation of the esters led to hydrocarbons in the third path. No oxygen-containing compounds were detected at complete conversions. However, the product distributions changed with time, even at complete conversions, indicating that both catalysts deactivated under the studied conditions.

Chemical, structural and combustion characteristics of carbonaceous products obtained by hydrothermal carbonization of palm empty fruit bunches.

Science.gov (United States)

Parshetti, Ganesh K; Kent Hoekman, S; Balasubramanian, Rajasekhar

2013-05-01

A carbon-rich solid product, denoted as hydrochar, was synthesized by hydrothermal carbonization (HTC) of palm oil empty fruit bunch (EFB), at different pre-treatment temperatures of 150, 250 and 350 °C. The conversion of the raw biomass to its hydrochar occurred via dehydration and decarboxylation processes. The hydrochar produced at 350 °C had the maximum energy-density (>27 MJ kg(-1)) with 68.52% of raw EFB energy retained in the char. To gain a detailed insight into the chemical and structural properties, carbonaceous hydrochar materials were characterized by FE-SEM, FT-IR, XRD and Brunauer-Emmett-Teller (BET) analyses. This work also investigated the influence of hydrothermally treated hydrochars on the co-combustion characteristics of low rank Indonesian coal. Conventional thermal gravimetric analysis (TGA) parameters, kinetics and activation energy of different hydrochar and coal blends were estimated. Our results show that solid hydrochars improve the combustion of low rank coals for energy generation. Copyright © 2012 Elsevier Ltd. All rights reserved.

Fatty acid biosynthesis. VIII. The fate of malonyl-CoA in fatty acid biosynthesis by purified enzymes from lactating-rabbit mammary gland

DEFF Research Database (Denmark)

Hansen, Heinz Johs. Max; Carey, E.M.; Dils, R.

1971-01-01

- 1. We have investigated the formation and utilization of malonyl-CoA in fatty acid synthesis catalysed by preparations of partially purified acetyl-CoA carboxylase and purified fatty acid synthetase from lactating-rabbit mammary gland. - 2. Carboxylation of [1-14C]acetyl-CoA was linked to fatty...... acid synthesis by the presence of fatty acid synthetase and NADPH. The rate of fatty acid formation was equal to that of acetyl-CoA carboxylation, without the accumulation of free malonyl-CoA to a concentration required to obtain the same rate of fatty acid synthesis from added [1,3-14C2]malonyl......-CoA. - 3. The preparations of acetyl-CoA carboxylase and fatty acid synthetase were each able to decarboxylate [1,3-14C2]malonyl-CoA. - 4. Both enzyme preparations acted as competitive inhibitors of 14CO2 fixation into acetyl-CoA catalysed by acetyl-CoA carboxylase in the absence of NADPH...

Agmatine Ameliorates High Glucose-Induced Neuronal Cell Senescence by Regulating the p21 and p53 Signaling.

Science.gov (United States)

Song, Juhyun; Lee, Byeori; Kang, Somang; Oh, Yumi; Kim, Eosu; Kim, Chul-Hoon; Song, Ho-Taek; Lee, Jong Eun

2016-02-01

Neuronal senescence caused by diabetic neuropathy is considered a common complication of diabetes mellitus. Neuronal senescence leads to the secretion of pro-inflammatory cytokines, the production of reactive oxygen species, and the alteration of cellular homeostasis. Agmatine, which is biosynthesized by arginine decarboxylation, has been reported in previous in vitro to exert a protective effect against various stresses. In present study, agmatine attenuated the cell death and the expression of pro-inflammatory cytokines such as IL-6, TNF-alpha and CCL2 in high glucose in vitro conditions. Moreover, the senescence associated-β-galatosidase's activity in high glucose exposed neuronal cells was reduced by agmatine. Increased p21 and reduced p53 in high glucose conditioned cells were changed by agmatine. Ultimately, agmatine inhibits the neuronal cell senescence through the activation of p53 and the inhibition of p21. Here, we propose that agmatine may ameliorate neuronal cell senescence in hyperglycemia.

Agmatine deiminase pathway genes in Lactobacillus brevis are linked to the tyrosine decarboxylation operon in a putative acid resistance locus

NARCIS (Netherlands)

Lucas, Patrick M.; Blancato, Victor S.; Claisse, Olivier; Magni, Christian; Lolkema, Juke S.; Lonvaud-Funel, Aline

In lactic acid bacteria (LAB), amino acids and their derivatives may be converted into amine-containing compounds designated biogenic amines, in pathways providing metabolic energy and/ or acid resistance to the bacteria. In a previous study, a pathway converting tyrosine to tyramine was detected in

Distribution of radiolabeled L-glutamate and D-aspartate from blood into peripheral tissues in naive rats: Significance for brain neuroprotection

International Nuclear Information System (INIS)

Klin, Yael; Zlotnik, Alexander; Boyko, Matthew; Ohayon, Sharon; Shapira, Yoram; Teichberg, Vivian I.

2010-01-01

Research highlights: → Blood glutamate has a half-life time of 2-3 min. → Blood glutamate is submitted to rapid decarboxylation. → Blood glutamate and its metabolites are mainly absorbed in skeletal muscle and liver. → The skeletal muscle and liver are now targets for potential drugs affording brain neuroprotection. -- Abstract: Excess L-glutamate (glutamate) levels in brain interstitial and cerebrospinal fluids (ISF and CSF, respectively) are the hallmark of several neurodegenerative conditions such as stroke, traumatic brain injury or amyotrophic lateral sclerosis. Its removal could prevent the glutamate excitotoxicity that causes long-lasting neurological deficits. As in previous studies, we have established the role of blood glutamate levels in brain neuroprotection, we have now investigated the contribution of the peripheral organs to the homeostasis of glutamate in blood. We have administered naive rats with intravenous injections of either L-[1- 14 C] Glutamic acid (L-[1- 14 C] Glu), L-[G- 3 H] Glutamic acid (L-[G- 3 H] Glu) or D-[2,3- 3 H] Aspartic acid (D-[2,3- 3 H] Asp), a non-metabolized analog of glutamate, and have followed their distribution into peripheral organs. We have observed that the decay of the radioactivity associated with L-[1- 14 C] Glu and L-[G- 3 H] Glu was faster than that associated with glutamate non-metabolized analog, D-[2,3- 3 H] Asp. L-[1- 14 C] Glu was subjected in blood to a rapid decarboxylation with the loss of 14 CO 2 . The three major sequestrating organs, serving as depots for the eliminated glutamate and/or its metabolites were skeletal muscle, liver and gut, contributing together 92% or 87% of total L-[U- 14 C] Glu or D-[2,3- 3 H] Asp radioactivity capture. L-[U- 14 C] Glu and D-[2,3- 3 H] Asp showed a different organ sequestration pattern. We conclude that glutamate is rapidly eliminated from the blood into peripheral tissues, mainly in non-metabolized form. The liver plays a central role in glutamate metabolism

Hydrothermal chemistry of Th(IV) with aromatic dicarboxylates: New framework compounds and in situ ligand syntheses

International Nuclear Information System (INIS)

Ziegelgruber, Kate L.; Knope, Karah E.; Frisch, Mark; Cahill, Christopher L.

2008-01-01

A novel thorium (IV) coordination polymer, Th(C 5 H 2 N 2 O 4 ) 2 (H 2 O) 2 (1), has been prepared under the hydrothermal reaction of thorium nitrate tetrahydrate and 3,5-pyrazoledicarboxylic acid (H 3 pdc). Compound 1 (orthorhombic, P2 1 2 1 2 1 , a=6.9362(5) A, b=10.7806(8) A, c=17.9915(14) A, Z=2, R 1 =0.0210, wR 2 =0.0470) consists of thorium metal centers connected via H 3 pdc linkages to form an overall three-dimensional structure containing π-π interactions between the pyrazole rings. 2,3-Pyrazinedicarboxylic acid (H 2 pzdc) was explored as well to (1) study the effect of the location of the carboxylic groups around the aromatic ring and (2) produce heterometallic compounds. Thorium (IV) and copper (II) were combined with H 2 pzdc, resulting in an interesting decomposition reaction characterized though the isolation of Th(C 2 O 4 ) 2 (H 2 O) 2 .2H 2 O (2) (monoclinic, C2/c, a=13.8507(12) A, b=7.8719(7) A, c=10.7961(16) A, β=118.0310(10) o , Z=2, R 1 =0.0160, wR 2 =0.0349), Cu(C 6 H 2 N 2 O 4 ) (3) (monoclinic, C2/c, a=11.499(3) A, b=7.502(2) A, c=7.402(2) A, β=93.892(5) o , Z=4, R 1 =0.0472, wR 2 =0.0745) and Cu(C 5 H 3 N 2 O 2 )(NO 3 )(H 2 O) (4). The capture of these species provides mechanistic evidence for the formation of the oxalate anions observed in 2 via the decarboxylation of H 2 pzdc to yield the linker in 4: 2-pyrazinecarboxylate anions. - Graphical abstract: 3,5-Pyrazoledicarboxylic and 2,3-pyridinedicarboxylic acid were utilized in synthesizing two novel thorium (IV) coordination polymers. Attempts to synthesize a Th-Cu bimetallic compound with 2,3-pyridinedicarboxylic acid resulted in a triphasic mixture (2, 3 and 4, respectively). The oxalate anion observed in Th(C 2 O 4 ) 2 (H 2 O) 2 .2H 2 O (2) is theorized to result from decarboxylation of 2,3-pyridinedicarboxylic acid as supported by the organic linker, 2-pyrazinecarboxylate, observed in Cu(C 5 H 3 N 2 O 2 )(NO 3 )(H 2 O) (4)

Distribution of radiolabeled L-glutamate and D-aspartate from blood into peripheral tissues in naive rats: Significance for brain neuroprotection

Energy Technology Data Exchange (ETDEWEB)

Klin, Yael [Department of Neurobiology, The Weizmann Institute of Science, Rehovot 76100 (Israel); Zlotnik, Alexander; Boyko, Matthew; Ohayon, Sharon; Shapira, Yoram [The Division of Anesthesiology, Soroka Medical Center and Ben Gurion University of the Negev, Beer-Sheva (Israel); Teichberg, Vivian I., E-mail: Vivian.teichberg@weizmann.ac.il [Department of Neurobiology, The Weizmann Institute of Science, Rehovot 76100 (Israel)

2010-09-03

Research highlights: {yields} Blood glutamate has a half-life time of 2-3 min. {yields} Blood glutamate is submitted to rapid decarboxylation. {yields} Blood glutamate and its metabolites are mainly absorbed in skeletal muscle and liver. {yields} The skeletal muscle and liver are now targets for potential drugs affording brain neuroprotection. -- Abstract: Excess L-glutamate (glutamate) levels in brain interstitial and cerebrospinal fluids (ISF and CSF, respectively) are the hallmark of several neurodegenerative conditions such as stroke, traumatic brain injury or amyotrophic lateral sclerosis. Its removal could prevent the glutamate excitotoxicity that causes long-lasting neurological deficits. As in previous studies, we have established the role of blood glutamate levels in brain neuroprotection, we have now investigated the contribution of the peripheral organs to the homeostasis of glutamate in blood. We have administered naive rats with intravenous injections of either L-[1-{sup 14}C] Glutamic acid (L-[1-{sup 14}C] Glu), L-[G-{sup 3}H] Glutamic acid (L-[G-{sup 3}H] Glu) or D-[2,3-{sup 3}H] Aspartic acid (D-[2,3-{sup 3}H] Asp), a non-metabolized analog of glutamate, and have followed their distribution into peripheral organs. We have observed that the decay of the radioactivity associated with L-[1-{sup 14}C] Glu and L-[G-{sup 3}H] Glu was faster than that associated with glutamate non-metabolized analog, D-[2,3-{sup 3}H] Asp. L-[1-{sup 14}C] Glu was subjected in blood to a rapid decarboxylation with the loss of {sup 14}CO{sub 2}. The three major sequestrating organs, serving as depots for the eliminated glutamate and/or its metabolites were skeletal muscle, liver and gut, contributing together 92% or 87% of total L-[U-{sup 14}C] Glu or D-[2,3-{sup 3}H] Asp radioactivity capture. L-[U-{sup 14}C] Glu and D-[2,3-{sup 3}H] Asp showed a different organ sequestration pattern. We conclude that glutamate is rapidly eliminated from the blood into peripheral tissues

Substituent effects on the photolysis of methyl 2-carboxylate substituted aliphatic 2 H-azirines

Science.gov (United States)

Gómez-Zavaglia, Andrea; Kaczor, Agnieszka; Cardoso, Ana L.; Pinho e Melo, Teresa M. V. D.; Fausto, Rui

2007-05-01

In this study, the UV induced photochemical reactions of two 2 H-azirines - methyl 2-chloro-3-methyl-2 H-azirine-2-carboxylate (MCMAC) and methyl 3-methyl-2 H-azirine-2-carboxylate (MMAC) - isolated in argon matrices are compared. For both compounds, irradiation with λ > 235 nm led to observation of two primary photoprocesses: (a) C sbnd C bond cleavage, with production of nitrile ylides (P1-type products), and (b) C sbnd N bond cleavage, with production of methylated ketene imines (P2-type products). However, subsequent photoprocesses were found to be different in the two cases. In MCMAC, both primary photoproducts were shown to undergo further reactions: P1-type products decarboxylate, giving [(1-chloroethylidene)imino]ethanide, which bears a C dbnd N +dbnd C - group (P3-type product); P2-type products decarbonylate, yielding a substituted ylidene methanamine (P4-type product). In MMAC, only P2-type primary photoproducts appeared to react, undergoing decarbonylation or decarboxylation (both reactions leading to P4-type products), whereas P1-type products were found to be non-reactive. The non-observation of any secondary photoproduct resulting from photolysis of P1-MMAC revealed the higher photostability of this species when compared with the corresponding photoproduct obtained from MCMAC. The C sbnd N photochemical cleavage is an unusual process in aliphatic 2 H-azirines. In the studied compounds, its preference over the commonly observed C sbnd C azirine-ring bond photocleavage is attributed to the presence of electron withdrawing substituents (methylcarboxy group in both azirines and also the chlorine atom in MCMAC), which accelerates intersystem crossing towards the triplet state from where the cleavage of the C sbnd N bond takes place. The lack of the chlorine atom in MMAC may be partially compensated by the significantly higher stabilization of the P2-type photoproduct derived from this molecule ( ca. -52 kJ mol -1) relatively to the reactant, when

Kinetics and Mechanistic Study of the Ruthenium(III Catalysed Oxidative Decarboxylation of L-Proline by Alkaline Heptavalent Manganese (Stopped flow technique

Directory of Open Access Journals (Sweden)

R. S. Shettar

2005-01-01

Full Text Available The kinetics of ruthenium(III catalysed oxidation of L-Proline by permanganate in alkaline medium at a constant ionic strength has been studied spectrophotometrically using a rapid kinetic accessory. The reaction between permanganate and L-Proline in alkaline medium exhibits 2:1 stoichiometry (KMnO4: L-Proline. The reaction shows first order dependence on [permanganate] and [ruthenium(III] and apparent less than unit order dependence each in L-Proline and alkali concentrations. Reaction rate increases with increase in ionic strength and decrease in solvent polarity of the medium. Initial addition of reaction products did not affect the rate significantly. A mechanism involving the formation of a complex between catalyst and substrate has been proposed. The activation parameters were computed with respect to the slow step of the mechanism and discussed

Characterization of galactomannan derivatives in roasted coffee beverages.

Science.gov (United States)

Nunes, Fernando M; Reis, Ana; Domingues, M Rosário M; Coimbra, Manuel A

2006-05-03

In this work, the galactomannans from roasted coffee infusions were purified by 50% ethanol precipitation, anion exchange chromatography, and phenylboronic acid-immobilized Sepharose chromatography. Specific enzymatic hydrolysis of the beta-(1-->4)-D-mannan backbone allowed us to conclude that the galactomannans of roasted coffee infusions are high molecular weight supports of low molecular weight brown compounds. Also, the molecular weight of the brown compounds linked to the galactomannan increases with the increase of the coffee degree of roast. The reaction pathways of galactomannans during the coffee roasting process were inferred from the detection of specific chemical markers by gas chromatography-electron impact mass spectrometry and/or electrospray ionization tandem mass spectrometry. Maillard reaction, caramelization, isomerization, oxidation, and decarboxylation pathways were identified by detection of Amadori compounds, 1,6-beta-anhydromannose, fructose, glucose, mannonic acid, 2-ketogluconic acid, and arabinonic acid in the reducing end of the obtained oligosaccharides. The implication of the several competitive reaction pathways is discussed and related to the structural changes of the galactomannans present in the roasted coffee infusions.

Biomass Gasification Research and Development Project

Energy Technology Data Exchange (ETDEWEB)

Ahring, Birgitte K. [Washington State Univ., Pullman, WA (United States)

2014-07-22

The overall objective of the BioChemCat project was to demonstrate the feasibility of using Advanced Wet Oxidation Steam-Explosion (AWEx) process to open and solubilize lignocellulosic biomass (LBM) coupled to an innovative mixed culture fermentation technology capable of producing a wide range of volatile fatty acids (VFAs) from all sugars present in LBM. The VFAs will then be separated and converted to hydrocarbon biofuel through catalytic upgrading. By continuously removing VFAs as they are produced (extractive fermentation), we were able to recover the VFAs while both eliminating the need for pH adjustment and increasing the fermentation productivity. The recovered VFAs were then esterified and upgraded to hydrocarbon fuels through a parallel series of hydrogenolysis/decarboxylation and dehydration reactions. We also demonstrated that a portion of the residual lignin fraction was solubilized and converted into VFAs, also improving the yields of VFAs. The remaining lignin fraction was then shown to be available (after dewatering and drying) for use as a lignin-enriched fuel pellet or as a feedstock for further processing.

Differences between flocculating yeast and regular industrial yeast in transcription and metabolite profiling during ethanol fermentation

Directory of Open Access Journals (Sweden)

Lili Li

2017-03-01

Full Text Available Objectives: To improve ethanolic fermentation performance of self-flocculating yeast, difference between a flocculating yeast strain and a regular industrial yeast strain was analyzed by transcriptional and metabolic approaches. Results: The number of down-regulated (industrial yeast YIC10 vs. flocculating yeast GIM2.71 and up-regulated genes were 4503 and 228, respectively. It is the economic regulation for YIC10 that non-essential genes were down-regulated, and cells put more “energy” into growth and ethanol production. Hexose transport and phosphorylation were not the limiting-steps in ethanol fermentation for GIM2.71 compared to YIC10, whereas the reaction of 1,3-disphosphoglycerate to 3-phosphoglycerate, the decarboxylation of pyruvate to acetaldehyde and its subsequent reduction to ethanol were the most limiting steps. GIM2.71 had stronger stress response than non-flocculating yeast and much more carbohydrate was distributed to other bypass, such as glycerol, acetate and trehalose synthesis. Conclusions: Differences between flocculating yeast and regular industrial yeast in transcription and metabolite profiling will provide clues for improving the fermentation performance of GIM2.71.

Transglutaminase-catalyzed amination of pea protein peptides using the biogenic amines histamine and tyramine.

Science.gov (United States)

Lu, Xinyao; Hrynets, Yuliya; Betti, Mirko

2017-06-01

Biogenic amines (BAs) are produced by the enzymatic decarboxylation of amino acids, and are well-known for their toxicity to humans. This study describes a new method using microbial transglutaminase (MTGase) to covalently link BAs such as histamine (HIS) and tyramine (TYR) to the glutamine residues of alcalase-hydrolyzed pea protein (PPH). The incubation of PPH and HIS and TYR in the presence of MTGase at 37 °C led to the formation of conjugates, as determined by liquid chromatography, after derivatization with dansyl chloride. Seventy-six % of HIS and 65% of TYR were covalently incorporated to PPH by MTGase. The incubation of PPH and TYR in the presence of MTGase exhibited a 52% DPPH radical scavenging activity at 10 mg mL -1 . Conjugation via MTGase improved the antioxidant status by reducing lipid peroxidation. This study emphasizes that the application of MTGase can effectively reduce histamine and tyramine content while simultaneously enhancing antioxidative capacity of PPH. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Renal ornithine decarboxylase activity, polyamines, and compensatory renal hypertrophy in the rat

International Nuclear Information System (INIS)

Humphreys, M.H.; Etheredge, S.B.; Lin, Shanyan; Ribstein, J.; Marton, L.J.

1988-01-01

The authors determined the role of ornithine decarboxylase (ODC) in compensatory renal hypertrophy (CRH) by relating renal ODC activity and polyamine content to kidney size, expressed as a percent of body weight, 1 wk after unilateral nephrectomy (UN). In normal rats, renal ODC activity increased after UN; 1 wk later the remaining kidney weight had increased. Renal concentration of putrescine, the product of ODC's decarboxylation of ornithine, was increased 3, 8, and 48 h after UN, but concentrations of polyamines synthesized later in the pathway, spermidine and spermine, were not appreciably affected. Pretreatment with difluoromethylornithine (DFMO), an irreversible inhibitor of ODC inhibited both base-line renal ODC activity and putrescine concentration as well as increases stimulated by UN, although concentrations of spermidine and spermine were not decreased. In hypophysectomized rats, both increased renal ODC activity and CRH occurred as well, indicating that these two consequences of UN do not require intact pituitary function. Thus stimulation of renal ODC activity and putrescine content do not appear critical to the process of CRH after UN

Influence of Long-Tailed Alcohols on the Solubilisation of Cationic DHAB Bilayers

Directory of Open Access Journals (Sweden)

Jan B.F.N. Engberts

2005-01-01

Full Text Available Abstract: The effects of n-decanol and cetyl alcohol incorporated into cationic di-n-hexadecyldimethylammonium bromide (DHAB bilayers on the packing and the resistance against solubilisation by Triton X-100 have been investigated. Solubilisation experiments revealed that the mismatch between the C10-tail of n-decanol with the DHAB-tails does not affect the structural integrity of the vesicles. On the contrary, upon increasing amounts of cetyl alcohol, of which the tail matches in size with the DHAB-tails, breakdown of the vesicles is promoted, whereas complete solubilisation is strongly hampered. The system is further investigated by DSC and cryo-EM experiments. In addition, the effects of n-decanol and cetyl alcohol embedded into DHAB bilayers on the vesicular rate constants for the decarboxylation of 6-nitrobenzisoxazole-3-carboxylate (6-NBIC suggest that both alcohols affect the structure of the Stern region in an equal manner, leading to a decrease in the catalysis. Therefore, it is concluded that addition of the alcohols leads to changes in properties of the interior of the bilayer, rather than the polar-apolar interface.

Biosynthesis of t-Butyl in Apratoxin A: Functional Analysis and Architecture of a PKS Loading Module.

Science.gov (United States)

Skiba, Meredith A; Sikkema, Andrew P; Moss, Nathan A; Lowell, Andrew N; Su, Min; Sturgis, Rebecca M; Gerwick, Lena; Gerwick, William H; Sherman, David H; Smith, Janet L

2018-04-27

The unusual feature of a t-butyl group is found in several marine-derived natural products including apratoxin A, a Sec61 inhibitor produced by the cyanobacterium Moorea bouillonii PNG 5-198. Here we determine that the apratoxin A t-butyl group is formed as pivaloyl acyl carrier protein (ACP) by AprA, the polyketide synthase (PKS) loading module of the apratoxin A biosynthetic pathway. AprA contains an inactive "pseudo" GCN5-related N-acetyltransferase domain (ΨGNAT) flanked by two methyltransferase domains (MT1 and MT2) that differ distinctly in sequence. Structural, biochemical, and precursor incorporation studies reveal that MT2 catalyzes unusually coupled decarboxylation and methylation reactions to transform dimethylmalonyl-ACP, the product of MT1, to pivaloyl-ACP. Further, pivaloyl-ACP synthesis is primed by the fatty acid synthase malonyl acyltransferase (FabD), which compensates for the ΨGNAT and provides the initial acyl-transfer step to form AprA malonyl-ACP. Additionally, images of AprA from negative stain electron microscopy reveal multiple conformations that may facilitate the individual catalytic steps of the multienzyme module.

Inhibition of photosynthesis by sodium fluoride. I. The sodium fluoride-induced carbon dioxide burst from Chlorella

Energy Technology Data Exchange (ETDEWEB)

Bishop, N I; Gaffron, H

1958-01-01

An attempt has been made to investigate the influence of fluorine compounds on the mechanism of photosynthesis using the acid-tolerant alga, Chlorella. Experimental results have verified that a burst of CO/sub 2/ expelled by NaF and the chlorophyll concentration. Contrary to the findings of another researcher, the amount of CO/sub 2/ released can be varied at will according to the conditions chosen. The yield when expressed in equivalence to the chlorophyll present in the algae may vary from values of zero to more than four. A simple experiment proved that in its precursor form, the CO/sub 2/ released by NaF is not a substrate for the photochemical reaction. The source appears to be some organic acid whose decarboxylation can be inhibited by cyanide, and it is more closely linked to respiration and fermentation than to photosynthesis. The authors observed that the effects can vary from a strong inhibition to no inhibition at all, even in cases where a CO/sub 2/ gush was evident.

Occurrence and distribution of monomethylalkanes in the freshwater wetland ecosystem of the Florida Everglades.

Science.gov (United States)

He, Ding; Simoneit, Bernd R T; Jara, Blanca; Jaffé, Rudolf

2015-01-01

A series of mono-methylalkanes (MMAs) with carbon numbers from C10 to C23 and C29 were detected in freshwater wetlands of the Everglades. A decrease in concentration and molecular complexity was observed in the order from periphyton and floc, to surface soil and deeper soil horizons. These compounds were present in varying amounts up to 27 μg gdw(-1) in periphyton, 74 μg gdw(-1) in floc, 1.8 μg gdw(-1) in surface soil, <0.03 μg gdw(-1) in deeper soils (12-15 cm). A total of 46 MMAs, including three iso and three anteiso-alkanes, were identified. Compound specific carbon isotopes values were determined for some dominant MMAs, and suggest that they originate from microbial sources, including cyanobacteria. Potential decarboxylation from fatty acids could also potentially contribute to the MMAs detected. Early diagenetic degradation was suggested to affect the accumulation of MMAs in soils and further studies are needed to address their applications as biomarkers. Copyright © 2014 Elsevier Ltd. All rights reserved.

Cytosolic NADP(+)-dependent isocitrate dehydrogenase protects macrophages from LPS-induced nitric oxide and reactive oxygen species.

Science.gov (United States)

Maeng, Oky; Kim, Yong Chan; Shin, Han-Jae; Lee, Jie-Oh; Huh, Tae-Lin; Kang, Kwang-il; Kim, Young Sang; Paik, Sang-Gi; Lee, Hayyoung

2004-04-30

Macrophages activated by microbial lipopolysaccharides (LPS) produce bursts of nitric oxide and reactive oxygen species (ROS). Redox protection systems are essential for the survival of the macrophages since the nitric oxide and ROS can be toxic to them as well as to pathogens. Using suppression subtractive hybridization (SSH) we found that cytosolic NADP(+)-dependent isocitrate dehydrogenase (IDPc) is strongly upregulated by nitric oxide in macrophages. The levels of IDPc mRNA and of the corresponding enzymatic activity were markedly increased by treatment of RAW264.7 cells or peritoneal macrophages with LPS or SNAP (a nitric oxide donor). Over-expression of IDPc reduced intracellular peroxide levels and enhanced the survival of H2O2- and SNAP-treated RAW264.7 macrophages. IDPc is known to generate NADPH, a cellular reducing agent, via oxidative decarboxylation of isocitrate. The expression of enzymes implicated in redox protection, superoxide dismutase (SOD) and catalase, was relatively unaffected by LPS and SNAP. We propose that the induction of IDPc is one of the main self-protection mechanisms of macrophages against LPS-induced oxidative stress.

Formation of Emerging Disinfection By-products by Chlorination/Chloramination of Seawater Impacted by Algal Organic Matter

KAUST Repository

Nihemaiti, Maolida; Le Roux, Julien; Croue, Jean-Philippe

2015-01-01

The aim of this work was to study the formation of haloacetamides (HAcAms) and other DBPs during chlorination and chloramination of algal organic matter (AlOM). The HAcAms formation potentials of different precursors (amino acids, simulated algal blooms grown in the Red Sea) were evaluated. Experiments with simulated algal blooms were conducted in the presence of bromide ion (synthetic seawater containing 800 μg/L Br−) to assess the formation of brominated analogues of HAcAms in conditions close to the disinfection of real seawater. Chlorination produced more HAcAms than chloramination from real algae (Synecococcus sp.), thus indicating that the nitrogen of HAcAms comes predominantly from DON through the decarboxylation of amino acids rather than from NH2Cl. Dibrominated species of DBPs (i.e., DBAcAm, DBAA and DBAN) were the dominant species formed by both chlorination and chloramination of algal bloom samples. Chloramination of the amino acid asparagine produced an important amount of DCAcAm as compared to chlorination, indicating the existence of a specific reaction pathway.

Formation of Emerging Disinfection By-products by Chlorination/Chloramination of Seawater Impacted by Algal Organic Matter

KAUST Repository

Nihemaiti, Maolida

2015-08-31

The aim of this work was to study the formation of haloacetamides (HAcAms) and other DBPs during chlorination and chloramination of algal organic matter (AlOM). The HAcAms formation potentials of different precursors (amino acids, simulated algal blooms grown in the Red Sea) were evaluated. Experiments with simulated algal blooms were conducted in the presence of bromide ion (synthetic seawater containing 800 μg/L Br−) to assess the formation of brominated analogues of HAcAms in conditions close to the disinfection of real seawater. Chlorination produced more HAcAms than chloramination from real algae (Synecococcus sp.), thus indicating that the nitrogen of HAcAms comes predominantly from DON through the decarboxylation of amino acids rather than from NH2Cl. Dibrominated species of DBPs (i.e., DBAcAm, DBAA and DBAN) were the dominant species formed by both chlorination and chloramination of algal bloom samples. Chloramination of the amino acid asparagine produced an important amount of DCAcAm as compared to chlorination, indicating the existence of a specific reaction pathway.

MICOS and phospholipid transfer by Ups2-Mdm35 organize membrane lipid synthesis in mitochondria.

Science.gov (United States)

Aaltonen, Mari J; Friedman, Jonathan R; Osman, Christof; Salin, Bénédicte; di Rago, Jean-Paul; Nunnari, Jodi; Langer, Thomas; Tatsuta, Takashi

2016-06-06

Mitochondria exert critical functions in cellular lipid metabolism and promote the synthesis of major constituents of cellular membranes, such as phosphatidylethanolamine (PE) and phosphatidylcholine. Here, we demonstrate that the phosphatidylserine decarboxylase Psd1, located in the inner mitochondrial membrane, promotes mitochondrial PE synthesis via two pathways. First, Ups2-Mdm35 complexes (SLMO2-TRIAP1 in humans) serve as phosphatidylserine (PS)-specific lipid transfer proteins in the mitochondrial intermembrane space, allowing formation of PE by Psd1 in the inner membrane. Second, Psd1 decarboxylates PS in the outer membrane in trans, independently of PS transfer by Ups2-Mdm35. This latter pathway requires close apposition between both mitochondrial membranes and the mitochondrial contact site and cristae organizing system (MICOS). In MICOS-deficient cells, limiting PS transfer by Ups2-Mdm35 and reducing mitochondrial PE accumulation preserves mitochondrial respiration and cristae formation. These results link mitochondrial PE metabolism to MICOS, combining functions in protein and lipid homeostasis to preserve mitochondrial structure and function. © 2016 Aaltonen et al.

Factors Influencing Biogenic Amines Accumulation in Dairy Products

Science.gov (United States)

Linares, Daniel M.; del Río, Beatriz; Ladero, Victor; Martínez, Noelia; Fernández, María; Martín, María Cruz; Álvarez, Miguel A.

2012-01-01

Fermented foods are among the food products more often complained of having caused episodes of biogenic amines (BA) poisoning. Concerning milk-based fermented foods, cheese is the main product likely to contain potentially harmful levels of BA, specially tyramine, histamine, and putrescine. Prompted by the increasing awareness of the risks related to dietary uptake of high biogenic amine loads, in this review we report all those elaboration and processing technological aspects affecting BA biosynthesis and accumulation in dairy foods. Improved knowledge of the factors involved in the synthesis and accumulation of BA should lead to a reduction in their incidence in milk products. Synthesis of BA is possible only when three conditions converge: (i) availability of the substrate amino acids; (ii) presence of microorganisms with the appropriate catabolic pathway activated; and (iii) environmental conditions favorable to the decarboxylation activity. These conditions depend on several factors such as milk treatment (pasteurization), use of starter cultures, NaCl concentration, time, and temperature of ripening and preservation, pH, temperature, or post-ripening technological processes, which will be discussed in this chapter. PMID:22783233

Methyl 3-[3',4'-(methylenedioxy)phenyl]-2-methyl glycidate: an ecstasy precursor seized in Sydney, Australia.

Science.gov (United States)

Collins, Michael; Heagney, Aaron; Cordaro, Frank; Odgers, David; Tarrant, Gregory; Stewart, Samantha

2007-07-01

Five 44 gallon drums labeled as glycidyl methacrylate were seized by the Australian Customs Service and the Australian Federal Police at Port Botany, Sydney, Australia, in December 2004. Each drum contained a white, semisolid substance that was initially suspected to be 3,4-methylenedioxymethylamphetamine (MDMA). Gas chromatography-mass spectroscopy (GC/MS) analysis demonstrated that the material was neither glycidyl methacrylate nor MDMA. Because intelligence sources employed by federal agents indicated that this material was in some way connected to MDMA production, suspicion fell on the various MDMA precursor chemicals. Using a number of techniques including proton nuclear magnetic resonance spectroscopy ((1)H NMR), carbon nuclear magnetic resonance spectroscopy ((13)C NMR), GC/MS, infrared spectroscopy, and total synthesis, the unknown substance was eventually identified as methyl 3-[3',4'(methylenedioxy)phenyl]-2-methyl glycidate. The substance was also subjected to a published hydrolysis and decarboxylation procedure and gave a high yield of the MDMA precursor chemical, 3,4-methylenedioxyphenyl-2-propanone, thereby establishing this material as a "precursor to a precursor."

Behaviors of rice straw two-step liquefaction with sub/supercritical ethanol in carbon dioxide atmosphere.

Science.gov (United States)

Yang, Tianhua; Wang, Jian; Li, Bingshuo; Kai, Xingping; Xing, Wanli; Li, Rundong

2018-06-01

This study extended previous work investigating two-step liquefaction by supercritical ethanol of rice straw under CO 2 atmosphere at temperatures of 270-345 °C. Subcritical CO 2 -subcritical ethanol (SubCO 2 -SubEtOH) pretreatment decreased the content of lignin in the rice stalk from 22.94 to 21.43 wt%. The results showed that although oxygen-transfer reaction, transesterification, carbonylation, and other reactions may occur with the supercritical CO 2 -supercritical ethanol (ScCO 2 -ScEtOH) liquefaction reactions, transesterification was the main reaction. The "de-oxygen-transfer" reaction mainly comprised de-oxygenation and decarboxylation. For temperatures exceeding 320 °C, the bio-oil yield decreased because the effects of esters decreased. The residence time affected the H/C and O/C ratios to a minor extent. It was shown that the nucleophilic and hydrolytic functions of ethanol might be strengthened, generating higher amounts of ester, phenolic, acidic, and hydrocarbon derivatives in the bio-oil fraction. Copyright © 2018 Elsevier Ltd. All rights reserved.

Functionalised Oximes: Emergent Precursors for Carbon-, Nitrogen- and Oxygen-Centred Radicals

Directory of Open Access Journals (Sweden)

John C. Walton

2016-01-01

Full Text Available Oxime derivatives are easily made, are non-hazardous and have long shelf lives. They contain weak N–O bonds that undergo homolytic scission, on appropriate thermal or photochemical stimulus, to initially release a pair of N- and O-centred radicals. This article reviews the use of these precursors for studying the structures, reactions and kinetics of the released radicals. Two classes have been exploited for radical generation; one comprises carbonyl oximes, principally oxime esters and amides, and the second comprises oxime ethers. Both classes release an iminyl radical together with an equal amount of a second oxygen-centred radical. The O-centred radicals derived from carbonyl oximes decarboxylate giving access to a variety of carbon-centred and nitrogen-centred species. Methods developed for homolytically dissociating the oxime derivatives include UV irradiation, conventional thermal and microwave heating. Photoredox catalytic methods succeed well with specially functionalised oximes and this aspect is also reviewed. Attention is also drawn to the key contributions made by EPR spectroscopy, aided by DFT computations, in elucidating the structures and dynamics of the transient intermediates.

Development and validation of an LC-MS/MS method for the determination of biogenic amines in wines and beers.

Science.gov (United States)

Nalazek-Rudnicka, Katarzyna; Wasik, Andrzej

2017-01-01

Biogenic amines are group of organic, basic, nitrogenous compounds that naturally occur in plant, microorganism, and animal organisms. Biogenic amines are mainly produced through decarboxylation of amino acids. They are formed during manufacturing of some kind of food and beverages such as cheese, wine, or beer. Histamine, cadaverine, agmatine, tyramine, putrescine, and β -phenylethylamine are the most common biogenic amines found in wines and beers. This group of compounds can be toxic at high concentrations; therefore, their control is very important. Analysis of biogenic amines in alcoholic drinks (beers and wines) was carried out by HPLC-MS/MS after their derivatization with p -toluenesulfonyl chloride (tosyl chloride). The developed method has been applied for analysis of seventeen biogenic amines in twenty-eight samples of lager beers and in twelve samples of different homemade wines (white grape, red grape, strawberry, chokeberry, black currant, plum, apple, raspberry, and quince). The developed method is sensitive and repeatable for majority of the analytes. It is versatile and can be used for the determination of biogenic amines in various alcoholic beverages.

Synthesis and Antiangiogenic Properties of Tetrafluorophthalimido and Tetrafluorobenzamido Barbituric Acids.

Science.gov (United States)

Ambrożak, Agnieszka; Steinebach, Christian; Gardner, Erin R; Beedie, Shaunna L; Schnakenburg, Gregor; Figg, William D; Gütschow, Michael

2016-12-06

The development of novel thalidomide derivatives as immunomodulatory and anti-angiogenic agents has revived over the last two decades. Herein we report the design and synthesis of three chemotypes of barbituric acids derived from the thalidomide structure: phthalimido-, tetrafluorophthalimido-, and tetrafluorobenzamidobarbituric acids. The latter were obtained by a new tandem reaction, including a ring opening and a decarboxylation of the fluorine-activated phthalamic acid intermediates. Thirty compounds of the three chemotypes were evaluated for their anti-angiogenic properties in an ex vivo assay by measuring the decrease in microvessel outgrowth in rat aortic ring explants. Tetrafluorination of the phthalimide moiety in tetrafluorophthalimidobarbituric acids was essential, as all of the nonfluorinated counterparts lost anti-angiogenic activity. An opening of the five-membered ring and the accompanying increased conformational freedom, in case of the corresponding tetrafluorobenzamidobarbituric acids, was well tolerated. Their activity was retained, although their molecular structures differ in torsional flexibility and possible hydrogen-bond networking, as revealed by comparative X-ray crystallographic analyses. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The metabolism of biphenyl

International Nuclear Information System (INIS)

Meyer, T.; Aarbakke, J.; Scheline, R.R.

1976-01-01

The metabolic disposition of 14 C-biphenyl in the rat was studied by liquid scintillation counting. The rats were given an oral dose of 14 C-biphenyl (100 mg/kg, 0.7-1.0 μci) and the total excretion of radioactivity after 96 hrs was 92.2% of the dose. Urinary excretion accounted for 84.8% and faecal excretion for 7.3% of the dose. Most of this radioactivity, 75.8% and 5.8% respectively, was excreted within 24 hrs. Only trace amounts of 14 CO 2 were detected in the expired air and 0.6% of the dose was found to be still present in the rats 96 hrs after biphenyl administration. Extraction and fractionation of the 24 hrs urine samples showed that the largest fraction (nearly 30% of the dose) consisted of conjugated phenolic metabolites. Acidic metabolites accounted for a quarter of the dose and the low levels of expired 14 CO 2 indicated that these were not products resulting from extensive degradation and decarboxylation. (author)

Immobilization of metal-humic acid complexes in anaerobic granular sludge for their application as solid-phase redox mediators in the biotransformation of iopromide in UASB reactors.

Science.gov (United States)

Cruz-Zavala, Aracely S; Pat-Espadas, Aurora M; Rangel-Mendez, J Rene; Chazaro-Ruiz, Luis F; Ascacio-Valdes, Juan A; Aguilar, Cristobal N; Cervantes, Francisco J

2016-05-01

Metal-humic acid complexes were synthesized and immobilized by a granulation process in anaerobic sludge for their application as solid-phase redox mediators (RM) in the biotransformation of iopromide. Characterization of Ca- and Fe-humic acid complexes revealed electron accepting capacities of 0.472 and 0.556milli-equivalentsg(-1), respectively. Once immobilized, metal-humic acid complexes significantly increased the biotransformation of iopromide in upflow anaerobic sludge blanket (UASB) reactors. Control UASB reactor (without humic material) achieved 31.6% of iopromide removal, while 80% was removed in UASB reactors supplied with each metal-humic acid complex. Further analyses indicated multiple transformation reactions taking place in iopromide including deiodination, N-dealkylation, decarboxylation and deacetylation. This is the first successful application of immobilized RM, which does not require a supporting material to maintain the solid-phase RM in long term operation of bioreactors. The proposed redox catalyst could be suitable for enhancing the redox conversion of different recalcitrant pollutants present in industrial effluents. Copyright © 2016 Elsevier Ltd. All rights reserved.

The first proton sponge-based amino acids: synthesis, acid-base properties and some reactivity.

Science.gov (United States)

Ozeryanskii, Valery A; Gorbacheva, Anastasia Yu; Pozharskii, Alexander F; Vlasenko, Marina P; Tereznikov, Alexander Yu; Chernov'yants, Margarita S

2015-08-21

The first hybrid base constructed from 1,8-bis(dimethylamino)naphthalene (proton sponge or DMAN) and glycine, N-methyl-N-(8-dimethylamino-1-naphthyl)aminoacetic acid, was synthesised in high yield and its hydrobromide was structurally characterised and used to determine the acid-base properties via potentiometric titration. It was found that the basic strength of the DMAN-glycine base (pKa = 11.57, H2O) is on the level of amidine amino acids like arginine and creatine and its structure, zwitterionic vs. neutral, based on the spectroscopic (IR, NMR, mass) and theoretical (DFT) approaches has a strong preference to the zwitterionic form. Unlike glycine, the DMAN-glycine zwitterion is N-chiral and is hydrolytically cleaved with the loss of glycolic acid on heating in DMSO. This reaction together with the mild decarboxylative conversion of proton sponge-based amino acids into 2,3-dihydroperimidinium salts under air-oxygen was monitored with the help of the DMAN-alanine amino acid. The newly devised amino acids are unique as they combine fluorescence, strongly basic and redox-active properties.

Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal-Organic Frameworks.

Science.gov (United States)

Feng, Liang; Yuan, Shuai; Zhang, Liang-Liang; Tan, Kui; Li, Jia-Luo; Kirchon, Angelo; Liu, Ling-Mei; Zhang, Peng; Han, Yu; Chabal, Yves J; Zhou, Hong-Cai

2018-02-14

Sufficient pore size, appropriate stability, and hierarchical porosity are three prerequisites for open frameworks designed for drug delivery, enzyme immobilization, and catalysis involving large molecules. Herein, we report a powerful and general strategy, linker thermolysis, to construct ultrastable hierarchically porous metal-organic frameworks (HP-MOFs) with tunable pore size distribution. Linker instability, usually an undesirable trait of MOFs, was exploited to create mesopores by generating crystal defects throughout a microporous MOF crystal via thermolysis. The crystallinity and stability of HP-MOFs remain after thermolabile linkers are selectively removed from multivariate metal-organic frameworks (MTV-MOFs) through a decarboxylation process. A domain-based linker spatial distribution was found to be critical for creating hierarchical pores inside MTV-MOFs. Furthermore, linker thermolysis promotes the formation of ultrasmall metal oxide nanoparticles immobilized in an open framework that exhibits high catalytic activity for Lewis acid-catalyzed reactions. Most importantly, this work provides fresh insights into the connection between linker apportionment and vacancy distribution, which may shed light on probing the disordered linker apportionment in multivariate systems, a long-standing challenge in the study of MTV-MOFs.

Soft X-ray-induced decomposition of amino acids: An XPS, mass spectrometry, and NEXAFS study

International Nuclear Information System (INIS)

Zubavichus, Yan; Fuchs, Oliver; Weinhardt, Lothar; Heske, Clemens; Umbach, Eberhard; Denlinger, Jonathan D.; Grunze, Michael

2003-01-01

Decomposition of five amino acids, alanine, serine, cysteine, aspartic acid, and asparagine, under irradiation with soft X-rays (magnesium Ka X-ray source) in ultra-high vacuum was studied by means of X-ray photoelectron spectrometry (XPS) and mass spectrometry. A comparative analysis of changes in XPS line shapes, stoichiometry and residual gas composition indicates that the molecules decompose by several pathways. Dehydration, decarboxylation, decarbonylation,deamination and desulfurization of pristine molecules accompanied by desorption of H2, H2O, CO2, CO, NH3and H2S are observed with rates depending on the specific amino acid. NEXAFS spectra of cysteine at the carbon, oxygen and nitrogen K-shell and sulfur L2,3 edges complement the XPS and mass spectrometry data and show that the exposure of the sample to an intense soft X-ray synchrotron beam results in the formation of C-C and C-N double and triple bonds. Qualitatively, the amino acids studied can be arranged in the following ascending order of radiation stability:serine< alanine< aspartic acid< cysteine< asparagine

Measurement of activity for S-adenosylmethionine decarboxylase using radioisotope {sup 14}C

Energy Technology Data Exchange (ETDEWEB)

Ko, Kyong Cheol; Park, Sang Hyun [Radiation Research Center for Biotechnology, Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, Jeongeup (Korea, Republic of); Kamio, Yoshiyuku [Division of Bioscience and Biotechnology for Future Bioindustries, Graduate School of Agricultural Science, Tohoku University (Japan)

2007-05-15

Polyamines are essential for normal cell growth and have important physiological function. They are polycationic compounds that are present in all biological materials. Also, they have been implicated in a wide variety of biological reactions. Generally, putrescine and spermidine are contained high amount in prokaryote, but spermidine and spermine are in eukaryote, respectively. However, S. ruminantium cells contain the polyamins such as spermidine and spermine. Addition of an aminopropyl group to putrescine conducts to the synthesis of spermidine. Aminopropyl group is derived from the dcSAM, a decarboxylation of S-adenosylmethionine, through action of S-adenosylmethionine decarboxylase (SAMDC). We suggested that S. ruminantium has a different pathway compare with prokaryote for polyamine synthesis. Assay for SAMDC activity was used {sup 14}C labeled substrate. Key enzyme in the biosynthesis of polyamines, SAMDC, was purified from S. ruminantium and characterized. The enzyme was purified about 1,259-fold to electrophoretic homogeneity with a specific activity of 1.89×10{sup -5} kat kg'-{sup 1} of protein.

Agmatine attenuates methamphetamine-induced hyperlocomotion and stereotyped behavior in mice.

Science.gov (United States)

Kitanaka, Nobue; Kitanaka, Junichi; Hall, F Scott; Uhl, George R; Watabe, Kaname; Kubo, Hitoshi; Takahashi, Hitoshi; Tanaka, Koh-ichi; Nishiyama, Nobuyoshi; Takemura, Motohiko

2014-04-01

We investigated whether pretreatment with the neurotransmitter/neuromodulator agmatine (decarboxylated L-arginine) affected methamphetamine (METH)-induced hyperlocomotion and stereotypy in male ICR mice. Agmatine pretreatment alone had no effects on locomotion or stereotypy, but it produced a dose-dependent attenuation of locomotion and the total incidence of stereotyped behavior induced by a low dose of METH (5 mg/kg). The stereotypy induced by this dose was predominantly characterized by stereotyped sniffing. By contrast, agmatine did not affect the total incidence of stereotypy induced by a higher dose of METH (10 mg/kg). However, the nature of stereotypy induced by this dose of METH was substantially altered; agmatine pretreatment significantly reduced stereotyped biting but significantly increased stereotyped sniffing and persistent locomotion. Agmatine pretreatment therefore appears to produce a rightward shift in the dose-response curve for METH. Pretreatment of mice with piperazine-1-carboxamidine (a putative agmatinase inhibitor) had no effect on locomotion or stereotypy induced by a low dose of METH, suggesting that endogenous agmatine may not regulate the METH action.

Agmatine: multifunctional arginine metabolite and magic bullet in clinical neuroscience?

Science.gov (United States)

Laube, Gregor; Bernstein, Hans-Gert

2017-07-26

Agmatine, the decarboxylation product of arginine, was largely neglected as an important player in mammalian metabolism until the mid-1990s, when it was re-discovered as an endogenous ligand of imidazoline and α 2 -adrenergic receptors. Since then, a wide variety of agmatine-mediated effects have been observed, and consequently agmatine has moved from a wallflower existence into the limelight of clinical neuroscience research. Despite this quantum jump in scientific interest, the understanding of the anabolism and catabolism of this amine is still vague. The purification and biochemical characterization of natural mammalian arginine decarboxylase and agmatinase still are open issues. Nevertheless, the agmatinergic system is currently one of the most promising candidates in order to pharmacologically interfere with some major diseases of the central nervous system, which are summarized in the present review. Particularly with respect to major depression, agmatine, its derivatives, and metabolizing enzymes show great promise for the development of an improved treatment of this common disease. © 2017 The Author(s); published by Portland Press Limited on behalf of the Biochemical Society.

Production of bio-hydrogenated diesel by catalytic hydrotreating of palm oil over NiMoS2/γ-Al2O3 catalyst.

Science.gov (United States)

Srifa, Atthapon; Faungnawakij, Kajornsak; Itthibenchapong, Vorranutch; Viriya-Empikul, Nawin; Charinpanitkul, Tawatchai; Assabumrungrat, Suttichai

2014-04-01

Catalytic hydrotreating of palm oil (refined palm olein type) to produce bio-hydrogenated diesel (BHD) was carried out in a continuous-flow fixed-bed reactor over NiMoS2/γ-Al2O3 catalyst. Effects of dominant hydrotreating parameters: temperature: 270-420°C; H2 pressure: 15-80 bar; LHSV: 0.25-5.0 h(-1); and H2/oil ratio: 250-2000 N(cm(3)/cm(3)) on the conversion, product yield, and a contribution of hydrodeoxygenation (HDO) and decarbonylation/decarboxylation (DCO/DCO2) were investigated to find the optimal hydrotreating conditions. All calculations including product yield and the contribution of HDO and DCO/DCO2 were extremely estimated based on mole balance corresponding to the fatty acid composition in feed to fully understand deoxygenation behaviors at different conditions. These analyses demonstrated that HDO, DCO, and DCO2 reactions competitively occurred at each condition, and had different optimal and limiting conditions. The differences in the hydrotreating reactions, liquid product compositions, and gas product composition were also discussed. Copyright © 2014 Elsevier Ltd. All rights reserved.

Microwave-enhanced pyrolysis of natural algae from water blooms.

Science.gov (United States)

Zhang, Rui; Li, Linling; Tong, Dongmei; Hu, Changwei

2016-07-01

Microwave-enhanced pyrolysis (MEP) of natural algae under different reaction conditions was carried out. The optimal conditions for bio-oil production were the following: algae particle size of 20-5 mesh, microwave power of 600W, and 10% of activated carbon as microwave absorber and catalyst. The maximum liquid yield obtained under N2, 10% H2/Ar, and CO2 atmosphere was 49.1%, 51.7%, and 54.3% respectively. The energy yield of bio-products was 216.7%, 236.9% and 208.7% respectively. More long chain fatty acids were converted into hydrocarbons by hydrodeoxygenation under 10% H2/Ar atmosphere assisted by microwave over activated carbon containing small amounts of metals. Under CO2 atmosphere, carboxylic acids (66.6%) were the main products in bio-oil because the existence of CO2 vastly inhibited the decarboxylation. The MEP of algae was quick and efficient for bio-oil production, which provided a way to not only ameliorate the environment but also obtain fuel or chemicals at the same time. Copyright © 2016 Elsevier Ltd. All rights reserved.

Characterisation of a thiamine diphosphate-dependent alpha-keto acid decarboxylase from Proteus mirabilis JN458.

Science.gov (United States)

Wang, Biying; Bai, Yajun; Fan, Taiping; Zheng, Xiaohui; Cai, Yujie

2017-10-01

Alpha-keto acid decarboxylases can convert keto acids to their corresponding aldehydes, which are often volatile aroma compounds. The gene encoding α-keto acid decarboxylase in Proteus mirabilis JN458 was cloned, and the enzyme overexpressed in Escherichia coli BL21 (DE3), purified in high yield, and characterised. The molecular weight is 62.291kDa by MALDI-TOF MS, and optimum activity at pH 6.0 and 40-50°C. The enzyme is a typical decarboxylase, dependent on thiamine diphosphate and Mg 2+ as cofactors. For the decarboxylation reaction, the enzyme displayed a broad substrate range. Kinetic parameters were determined using 4-methyl-2-oxopentanoic acid, phenyl pyruvate and 3-methyl-2-oxopentanoic acid as substrates. K m and k cat values for phenyl pyruvate were 0.62mM and 77.38s -1 , respectively, and the k cat /K m value was 124.81mM -1 s -1 . The enzyme properties suggest it may act effectively under cheese ripening conditions. Copyright © 2017. Published by Elsevier Ltd.

A Dopa Decarboxylase Modulating the Immune Response of Scallop Chlamys farreri

Science.gov (United States)

Zhou, Zhi; Yang, Jialong; Wang, Lingling; Zhang, Huan; Gao, Yang; Shi, Xiaowei; Wang, Mengqiang; Kong, Pengfei; Qiu, Limei; Song, Linsheng

2011-01-01

Background Dopa decarboxylase (DDC) is a pyridoxal 5-phosphate (PLP)-dependent enzyme that catalyzes the decarboxylation of L-Dopa to dopamine, and involved in complex neuroendocrine-immune regulatory network. The function for DDC in the immunomodulation remains unclear in invertebrate. Methodology The full-length cDNA encoding DDC (designated CfDDC) was cloned from mollusc scallop Chlamys farreri. It contained an open reading frame encoding a polypeptide of 560 amino acids. The CfDDC mRNA transcripts could be detected in all the tested tissues, including the immune tissues haemocytes and hepatopancreas. After scallops were treated with LPS stimulation, the mRNA expression level of CfDDC in haemocytes increased significantly (5.5-fold, PDDC inhibitor methyldopa, the ROS level in haemocytes of scallops was decreased significantly to 0.41-fold (PDDC in scallop, modulated the immune responses such as haemocytes encapsulation as well as the ROS level through its catalytic activity, functioning as an indispensable immunomodulating enzyme in the neuroendocrine-immune regulatory network of mollusc. PMID:21533240

Temperature dependence of carbon isotope fractionation in CAM plants

International Nuclear Information System (INIS)

Deleens, E.; Treichel, I.; O'Leary, M.H.

1985-01-01

The carbon isotope fractionation associated with nocturnal malic acid synthesis in Kalanchoë daigremontiana and Bryophyllum tubiflorum was calculated from the isotopic composition of carbon-4 of malic acid, after appropriate corrections. In the lowest temperature treatment (17 degrees C nights, 23 degrees C days), the isotope fractionation for both plants is -4 per thousand (that is, malate is enriched in (13)C relative to the atmosphere). For K. daigremontiana, the isotope fractionation decreases with increasing temperature, becoming approximately 0 per thousand at 27 degrees C/33 degrees C. Detailed analysis of temperature effects on the isotope fractionation indicates that stomatal aperture decreases with increasing temperature and carboxylation capacity increases. For B. tubiflorum, the temperature dependence of the isotope fractionation is smaller and is principally attributed to the normal temperature dependences of the rates of diffusion and carboxylation steps. The small change in the isotopic composition of remaining malic acid in both species which is observed during deacidification indicates that malate release, rather than decarboxylation, is rate limiting in the deacidification process

Temperature dependence of carbon isotope fractionation in CAM plants

Energy Technology Data Exchange (ETDEWEB)

Deleens, E.; Treichel, I.; O' Leary, M.H.

1985-09-01

The carbon isotope fractionation associated with nocturnal malic acid synthesis in Kalanchoe daigremontiana and Bryophyllum tubiflorum was calculated from the isotopic composition of carbon-4 of malic acid, after appropriate corrections. In the lowest temperature treatment (17/sup 0/C nights, 23/sup 0/C days), the isotope fractionation for both plants is -4% per thousand (that is, malate is enriched in /sup 13/C relative to the atmosphere). For K. daigremontiana, the isotope fractionation decreases with increasing temperature, becoming approximately 0% per thousand at 27/sup 0/C/33/sup 0/C. Detailed analysis of temperature effects on the isotope fractionation indicates that stomatal aperture decreases with increasing temperature and carboxylation capacity increases. For B. tubiflorum, the temperature dependence of the isotope fractionation is smaller and is principally attributed to the normal temperature dependences of the rates of diffusion and carboxylation steps. The small change in the isotopic composition of remaining malic acid in both species which is observed during deacidification indicates that malate release, rather than decarboxylation, is rate limiting in the deacidification process. 28 references, 1 figure, 4 tables.

Multiple Syntrophic Interactions in a Terephthalate-Degrading Methanogenic Consortium

Energy Technology Data Exchange (ETDEWEB)

Lykidis, Athanasios; Chen, Chia-Lung; Tringe, Susannah G.; McHardy, Alice C.; Copeland, Alex 5; Kyrpides, Nikos C.; Hugenholtz, Philip; Liu, Wen-Tso

2010-08-05

Terephthalate (TA) is one of the top 50 chemicals produced worldwide. Its production results in a TA-containing wastewater that is treated by anaerobic processes through a poorly understood methanogenic syntrophy. Using metagenomics, we characterized the methanogenic consortium tinside a hyper-mesophilic (i.e., between mesophilic and thermophilic), TA-degrading bioreactor. We identified genes belonging to dominant Pelotomaculum species presumably involved in TA degradation through decarboxylation, dearomatization, and modified ?-oxidation to H{sub 2}/CO{sub 2} and acetate. These intermediates are converted to CH{sub 4}/CO{sub 2} by three novel hyper-mesophilic methanogens. Additional secondary syntrophic interactions were predicted in Thermotogae, Syntrophus and candidate phyla OP5 and WWE1 populations. The OP5 encodes genes capable of anaerobic autotrophic butyrate production and Thermotogae, Syntrophus and WWE1 have the genetic potential to oxidize butyrate to COsub 2}/H{sub 2} and acetate. These observations suggest that the TA-degrading consortium consists of additional syntrophic interactions beyond the standard H{sub 2}-producing syntroph ? methanogen partnership that may serve to improve community stability.

Effect of ultrasonic frequency on the mechanism of formic acid sono-lysis

International Nuclear Information System (INIS)

Chave, T.; Nikitenko, S.I.; Navarro, N.M.; Pochon, P.; Bisel, I.

2011-01-01

The kinetics and mechanism of formic acid sono-chemical degradation were studied at ultrasonic frequencies of 20, 200, and 607 kHz under argon atmosphere. Total yield of HCOOH sono-chemical degradation increases approximately 6-8-fold when the frequency increased from 20 to 200 or to 607 kHz. At low ultrasonic frequencies, HCOOH degradation has been attributed to oxidation with OH . radicals from water sono-lysis and to the HCOOH decarboxylation occurring at the cavitation bubble-liquid interface. With high-frequency ultrasound, the sono-chemical reaction is also influenced by HCOOH dehydration. Whatever the ultrasonic frequency, the sono-lysis of HCOOH yielded H 2 and CO 2 in the gas phase as well as trace, amounts of oxalic acid and formaldehyde in the liquid phase. However, CO and CH 4 formations were only detected under high frequency ultrasound. The most striking difference between low frequency and high frequency ultrasound is that the sono-lysis of HCOOH at high ultrasonic frequencies initiates Fischer-Tropsch hydrogenation of carbon monoxide. (authors)

Unimolecular decomposition of formic and acetic acids: A shock tube/laser absorption study

KAUST Repository

Elwardany, A.; Nasir, E.F.; Es-sebbar, Et-touhami; Farooq, Aamir

2014-01-01

The thermal decomposition of formic acid (HCOOH) and acetic acid (CH3COOH), two carboxylic acids which play an important role in oxygenate combustion chemistry, were investigated behind reflected shock waves using laser absorption. The rate constants of the primary decomposition pathways of these acids:(HCOOH → CO + H2 O (R 1); HCOOH → CO2 + H2 (R 2); CH3 COOH → CH4 + CO2 (R 3); CH3 COOH → CH2 CO + H2 O (R 4)) were measured using simultaneous infrared laser absorption of CO, CO2 and H2O at wavelengths of 4.56, 4.18 and 2.93 microns, respectively. Reaction test conditions covered temperatures from 1230 to 1821 K and pressures from 1.0 to 6.5 atm for dilute mixtures of acids (0.25-0.6%) in argon. The rate constants of dehydration (R1) and decarboxylation (R2) reactions of formic acid were calculated by fitting exponential functions to the measured CO, CO2 and H2O time-history profiles. These two decomposition channels were found to be in the fall-off region and have a branching ratio, k1/k2, of approximately 20 over the range of pressures studied here. The best-fit Arrhenius expressions of the first-order rates of R1 and R2 were found to be:(k1 (1 atm) = 1.03 × 1011 exp (- 25651 / T) s- 1 (± 37 %); k1 (6.5 atm) = 9.12 × 1012 exp (- 30275 / T) s- 1 (± 32 %); k2 (1 atm) = 1.79 × 108 exp (- 21133 / T) s- 1 (± 41 %); k2 (6.5 atm) = 2.73 × 108 exp (- 20074 / T) s- 1 (± 37 %)). The rate constants for acetic acid decomposition were obtained by fitting simulated profiles, using an acetic acid pyrolysis mechanism, to the measured species time-histories. The branching ratio, k4/k3, was found to be approximately 2. The decarboxylation and dehydration reactions of acetic acid appear to be in the falloff region over the tested pressure range:(k3 (1 atm) = 3.18 × 1011 exp (- 28679 / T) s- 1 (± 30 %); k3 (6 atm) = 3.51 × 1012 exp (- 31330 / T) s- 1 (± 26 %); k4 (1 atm) = 7.9 × 1011 exp (- 29056 / T) s- 1 (± 34 %); k4 (6 atm) = 6.34 × 1012 exp (- 31330 / T) s

Unimolecular decomposition of formic and acetic acids: A shock tube/laser absorption study

KAUST Repository

Elwardany, A.

2014-07-16

The thermal decomposition of formic acid (HCOOH) and acetic acid (CH3COOH), two carboxylic acids which play an important role in oxygenate combustion chemistry, were investigated behind reflected shock waves using laser absorption. The rate constants of the primary decomposition pathways of these acids:(HCOOH → CO + H2 O (R 1); HCOOH → CO2 + H2 (R 2); CH3 COOH → CH4 + CO2 (R 3); CH3 COOH → CH2 CO + H2 O (R 4)) were measured using simultaneous infrared laser absorption of CO, CO2 and H2O at wavelengths of 4.56, 4.18 and 2.93 microns, respectively. Reaction test conditions covered temperatures from 1230 to 1821 K and pressures from 1.0 to 6.5 atm for dilute mixtures of acids (0.25-0.6%) in argon. The rate constants of dehydration (R1) and decarboxylation (R2) reactions of formic acid were calculated by fitting exponential functions to the measured CO, CO2 and H2O time-history profiles. These two decomposition channels were found to be in the fall-off region and have a branching ratio, k1/k2, of approximately 20 over the range of pressures studied here. The best-fit Arrhenius expressions of the first-order rates of R1 and R2 were found to be:(k1 (1 atm) = 1.03 × 1011 exp (- 25651 / T) s- 1 (± 37 %); k1 (6.5 atm) = 9.12 × 1012 exp (- 30275 / T) s- 1 (± 32 %); k2 (1 atm) = 1.79 × 108 exp (- 21133 / T) s- 1 (± 41 %); k2 (6.5 atm) = 2.73 × 108 exp (- 20074 / T) s- 1 (± 37 %)). The rate constants for acetic acid decomposition were obtained by fitting simulated profiles, using an acetic acid pyrolysis mechanism, to the measured species time-histories. The branching ratio, k4/k3, was found to be approximately 2. The decarboxylation and dehydration reactions of acetic acid appear to be in the falloff region over the tested pressure range:(k3 (1 atm) = 3.18 × 1011 exp (- 28679 / T) s- 1 (± 30 %); k3 (6 atm) = 3.51 × 1012 exp (- 31330 / T) s- 1 (± 26 %); k4 (1 atm) = 7.9 × 1011 exp (- 29056 / T) s- 1 (± 34 %); k4 (6 atm) = 6.34 × 1012 exp (- 31330 / T) s

Role of L-alanine for redox self-sufficient amination of alcohols.

Science.gov (United States)

Klatte, Stephanie; Wendisch, Volker F

2015-01-23

In white biotechnology biocatalysis represents a key technology for chemical functionalization of non-natural compounds. The plasmid-born overproduction of an alcohol dehydrogenase, an L-alanine-dependent transaminase and an alanine dehydrogenase allows for redox self-sufficient amination of alcohols in whole cell biotransformation. Here, conditions to optimize the whole cell biocatalyst presented in (Bioorg Med Chem 22:5578-5585, 2014), and the role of L-alanine for efficient amine functionalization of 1,10-decanediol to 1,10-diaminodecane were analyzed. The enzymes of the cascade for amine functionalization of alcohols were characterized in vitro to find optimal conditions for an efficient process. Transaminase from Chromobacterium violaceum, TaCv, showed three-fold higher catalytic efficiency than transaminase from Vibrio fluvialis, TaVf, and improved production at 37°C. At 42°C, TaCv was more active, which matched thermostable alcohol dehydrogenase and alanine dehydrogenase and improved the 1,10-diaminodecane production rate four-fold. To study the role of L-alanine in the whole cell biotransformation, the L-alanine concentration was varied and 1,10.diaminodecane formation tested with constant 10 mM 1,10- decanediol and 100 mM NH4Cl. Only 5.6% diamine product were observed without added L-alanine. L-alanine concentrations equimolar to that of the alcohol enabled for 94% product formation but higher L-alanine concentrations allowed for 100% product formation. L-alanine was consumed by the E. coli biocatalyst, presumably due to pyruvate catabolism since up to 16 mM acetate accumulated. Biotransformation employing E. coli strain YYC202/pTrc99a-ald-adh-ta Cv, which is unable to catabolize pyruvate, resulted in conversion with a selectivity of 42 mol-%. Biotransformation with E. coli strains only lacking pyruvate oxidase PoxB showed similar reduced amination of 1,10-decanediol indicating that oxidative decarboxylation of pyruvate to acetate by PoxB is primarily

Fate and behaviour of diclofenac during hydrothermal carbonization.

Science.gov (United States)

vom Eyser, C; Schmidt, T C; Tuerk, J

2016-06-01

Hydrothermal carbonization (HTC) has become an esteemed method to convert sewage sludge into biochar. Besides dewatering and disinfection the process is suggested to reduce the micropollutant load, which would be beneficial for the use of biochar as fertilizer. This study was designed to examine reduction of micropollutants and formation of transformation products during HTC using the example of diclofenac. We investigated compounds' removal at HTC conditions in inert experiments and in real samples. Results showed that HTC temperature (>190 °C) and pressure (∼15 bar) have the potential to fully degrade diclofenac in inert experiments and spiked sewage sludge (>99%) within 1 h. However, interfering effects hinder full removal in native samples resulting in 44% remaining diclofenac. Additionally, a combination of suspected-target and non-target analysis using LC-MS/MS and LC-HRMS resulted in the determination of six transformation products. These products have been reported in biochar from HTC for the first time, although other studies described them for other processes like advanced oxidation. Based on the detected transformation products, we proposed a degradation mechanism reflecting HTC reactions such as dehydroxylation and decarboxylation. Copyright © 2016 Elsevier Ltd. All rights reserved.

Deletion of genes involved in glutamate metabolism to improve poly-gamma-glutamic acid production in B. amyloliquefaciens LL3.

Science.gov (United States)

Zhang, Wei; He, Yulian; Gao, Weixia; Feng, Jun; Cao, Mingfeng; Yang, Chao; Song, Cunjiang; Wang, Shufang

2015-02-01

Here, we attempted to elevate poly-gamma-glutamic acid (γ-PGA) production by modifying genes involved in glutamate metabolism in Bacillus amyloliquefaciens LL3. Products of rocR, rocG and gudB facilitate the conversion from glutamate to 2-oxoglutarate in Bacillus subtillis. The gene odhA is responsible for the synthesis of a component of the 2-oxoglutarate dehydrogenase complex that catalyzes the oxidative decarboxylation of 2-oxoglutarate to succinyl coenzyme A. In-frame deletions of these four genes were performed. In shake flask experiments the gudB/rocG double mutant presented enhanced production of γ-PGA, a 38 % increase compared with wild type. When fermented in a 5-L fermenter with pH control, the γ-PGA yield of the rocR mutant was increased to 5.83 g/L from 4.55 g/L for shake flask experiments. The gudB/rocG double mutant produced 5.68 g/L γ-PGA compared with that of 4.03 g/L for the wild type, a 40 % increase. Those results indicated the possibility of improving γ-PGA production by modifying glutamate metabolism, and identified potential genetic targets to improve γ-PGA production.

Elucidating Direct Photolysis Mechanisms of Different Dissociation Species of Norfloxacin in Water and Mg2+ Effects by Quantum Chemical Calculations.

Science.gov (United States)

Wang, Se; Wang, Zhuang

2017-11-11

The study of pollution due to combined antibiotics and metals is urgently needed. Photochemical processes are an important transformation pathway for antibiotics in the environment. The mechanisms underlying the effects of metal-ion complexation on the aquatic photochemical transformation of antibiotics in different dissociation forms are crucial problems in science, and beg solutions. Herein, we investigated the mechanisms of direct photolysis of norfloxacin (NOR) in different dissociation forms in water and metal ion Mg 2+ effects using quantum chemical calculations. Results show that different dissociation forms of NOR had different maximum electronic absorbance wavelengths (NOR 2+ direct photolysis pathways were de-ethylation (N7-C8 bond cleavage) and decarboxylation (C2-C5 bond cleavage). Furthermore, the presence of Mg 2+ changed the order of the wavelength at maximum electronic absorbance (NOR⁺-Mg 2+ direct photolysis of NOR⁰, NOR⁺, and NOR 2+ . The calculated TS results indicated that the presence of Mg 2+ increased E a for most direct photolysis pathways of NOR, while it decreased E a for some direct photolysis pathways such as the loss of the piperazine ring and the damage of the piperazine ring of NOR⁰ and the defluorination of NOR⁺.

In Folio Respiratory Fluxomics Revealed by 13C Isotopic Labeling and H/D Isotope Effects Highlight the Non-cyclic Nature of the Tricarboxylic Acid 'Cycle' in Illuminated Leaves

International Nuclear Information System (INIS)

Tcherkez, G.; Mahe, A.; Gauthier, P.; Hodges, M.; Tcherkez, G.; Mauve, C.; Cornic, G.; Gout, E.; Bligny, R.

2009-01-01

While the possible importance of the tricarboxylic acid (TCA) cycle reactions for leaf photosynthesis operation has been recognized, many uncertainties remain on whether TCA cycle biochemistry is similar in the light compared with the dark. It is widely accepted that leaf day respiration and the metabolic commitment to TCA decarboxylation are down-regulated in illuminated leaves. However, the metabolic basis (i.e. the limiting steps involved in such a down-regulation) is not well known. Here, we investigated the in vivo metabolic fluxes of individual reactions of the TCA cycle by developing two isotopic methods, 13 C tracing and fluxomics and the use of H/D isotope effects, with Xanthium strumarium leaves. We provide evidence that the TCA 'cycle' does not work in the forward direction like a proper cycle but, rather, operates in both the reverse and forward directions to produce fumarate and glutamate, respectively. Such a functional division of the cycle plausibly reflects the compromise between two contrasted forces: (1) the feedback inhibition by NADH and ATP on TCA enzymes in the light, and (2) the need to provide pH-buffering organic acids and carbon skeletons for nitrate absorption and assimilation. (authors)

In Folio Respiratory Fluxomics Revealed by {sup 13}C Isotopic Labeling and H/D Isotope Effects Highlight the Non-cyclic Nature of the Tricarboxylic Acid 'Cycle' in Illuminated Leaves

Energy Technology Data Exchange (ETDEWEB)

Tcherkez, G; Mahe, A; Gauthier, P; Hodges, M [Institut de Biotechnologie des Plantes, Plateforme Metabolisme-Metabolome IFR87, Batiment 630, Universite Paris-Sud 11, 91405 Orsay cedex (France); Tcherkez, G; Mauve, C; Cornic, G [Laboratoire d' Ecophysiologie Vegetale, Ecologie Systematique Evolution (G.C.), Batiment 630, Universite Paris-Sud 11, 91405 Orsay cedex (France); Gout, E; Bligny, R [Laboratoire de Physiologie Cellulaire Vegetale, Commissariat a l' Energie Atomique-Grenoble, 38054 Grenoble cedex 9 (France)

2009-07-01

While the possible importance of the tricarboxylic acid (TCA) cycle reactions for leaf photosynthesis operation has been recognized, many uncertainties remain on whether TCA cycle biochemistry is similar in the light compared with the dark. It is widely accepted that leaf day respiration and the metabolic commitment to TCA decarboxylation are down-regulated in illuminated leaves. However, the metabolic basis (i.e. the limiting steps involved in such a down-regulation) is not well known. Here, we investigated the in vivo metabolic fluxes of individual reactions of the TCA cycle by developing two isotopic methods, {sup 13}C tracing and fluxomics and the use of H/D isotope effects, with Xanthium strumarium leaves. We provide evidence that the TCA 'cycle' does not work in the forward direction like a proper cycle but, rather, operates in both the reverse and forward directions to produce fumarate and glutamate, respectively. Such a functional division of the cycle plausibly reflects the compromise between two contrasted forces: (1) the feedback inhibition by NADH and ATP on TCA enzymes in the light, and (2) the need to provide pH-buffering organic acids and carbon skeletons for nitrate absorption and assimilation. (authors)

In Folio Respiratory Fluxomics Revealed by 13C Isotopic Labeling and H/D Isotope Effects Highlight the Noncyclic Nature of the Tricarboxylic Acid “Cycle” in Illuminated Leaves1[W

Science.gov (United States)

Tcherkez, Guillaume; Mahé, Aline; Gauthier, Paul; Mauve, Caroline; Gout, Elizabeth; Bligny, Richard; Cornic, Gabriel; Hodges, Michael

2009-01-01

While the possible importance of the tricarboxylic acid (TCA) cycle reactions for leaf photosynthesis operation has been recognized, many uncertainties remain on whether TCA cycle biochemistry is similar in the light compared with the dark. It is widely accepted that leaf day respiration and the metabolic commitment to TCA decarboxylation are down-regulated in illuminated leaves. However, the metabolic basis (i.e. the limiting steps involved in such a down-regulation) is not well known. Here, we investigated the in vivo metabolic fluxes of individual reactions of the TCA cycle by developing two isotopic methods, 13C tracing and fluxomics and the use of H/D isotope effects, with Xanthium strumarium leaves. We provide evidence that the TCA “cycle” does not work in the forward direction like a proper cycle but, rather, operates in both the reverse and forward directions to produce fumarate and glutamate, respectively. Such a functional division of the cycle plausibly reflects the compromise between two contrasted forces: (1) the feedback inhibition by NADH and ATP on TCA enzymes in the light, and (2) the need to provide pH-buffering organic acids and carbon skeletons for nitrate absorption and assimilation. PMID:19675152

Transphosphatidylation and base-exchange in the membranes of clostridium butyricum

International Nuclear Information System (INIS)

Walton, P.A.; Goldfine, H.

1987-01-01

Membrane particles from C. butyricum, incubated with phosphatidylserine (PS) and Triton X-100, produced three labelled phospholipids in addition to phosphatidylethanolamine (PE) formed by decarboxylation. These lipid were also formed when PE or phosphatidylglycerol (PG) was employed as substrate. 2D-TLC of intact lipids and their deacylation products showed that these lipids are phosphatidic acid, cardiolipid (CL), and previously unreported phosphatidyltriton (PT). Triton X-100 acts as both activator and substrate of the reaction. With radiolabel in different portions of the substrate phospholipid we demonstrated that the phosphatidyl moiety was transferred with the loss of the head-group in a phospholipase D-like manner. The acceptor molecule can be water or primary alcohols. Addition of exogenous unlabelled PG resulted in the formation of CL with concomitant decrease in the level of PT formed. Labelled PS, PE, and PG could also be formed upon addition of their corresponding alcoholic head group to incubations containing a labelled phosphatidyl donor and Triton X-100. These results indicate that, in C. butyricum, enzymic steps exists that would allow remodelling of the membrane phospholipids, without requiring de novo biosynthesis

IDH Mutation Analysis in Ewing Sarcoma Family Tumors

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Ki Yong Na

2015-05-01

Full Text Available Background: Isocitrate dehydrogenase (IDH catalyzes the oxidative decarboxylation of isocitrate to yield α-ketoglutarate (α-KG with production of reduced nicotinamide adenine dinucleotide (NADH. Dysfunctional IDH leads to reduced production of α-KG and NADH and increased production of 2-hydroxyglutarate, an oncometabolite. This results in increased oxidative damage and stabilization of hypoxia-inducible factor α, causing cells to be prone to tumorigenesis. Methods: This study investigated IDH mutations in 61 Ewing sarcoma family tumors (ESFTs, using a pentose nucleic acid clamping method and direct sequencing. Results: We identified four cases of ESFTs harboring IDH mutations. The number of IDH1 and IDH2 mutations was equal and the subtype of IDH mutations was variable. Clinicopathologic analysis according to IDH mutation status did not reveal significant results. Conclusions: This study is the first to report IDH mutations in ESFTs. The results indicate that ESFTs can harbor IDH mutations in previously known hot-spot regions, although their incidence is rare. Further validation with a larger case-based study would establish more reliable and significant data on prevalence rate and the biological significance of IDH mutations in ESFTs.

Mitochondrial control through nutritionally regulated global histone H3 lysine-4 demethylation.

Science.gov (United States)

Soloveychik, Maria; Xu, Mengshu; Zaslaver, Olga; Lee, Kwanyin; Narula, Ashrut; Jiang, River; Rosebrock, Adam P; Caudy, Amy A; Meneghini, Marc D

2016-11-29

Histone demethylation by Jumonji-family proteins is coupled with the decarboxylation of α-ketoglutarate (αKG) to yield succinate, prompting hypotheses that their activities are responsive to levels of these metabolites in the cell. Consistent with this paradigm we show here that the Saccharomyces cerevisiae Jumonji demethylase Jhd2 opposes the accumulation of H3K4me3 in fermenting cells only when they are nutritionally manipulated to contain an elevated αKG/succinate ratio. We also find that Jhd2 opposes H3K4me3 in respiratory cells that do not exhibit such an elevated αKG/succinate ratio. While jhd2∆ caused only limited gene expression defects in fermenting cells, transcript profiling and physiological measurements show that JHD2 restricts mitochondrial respiratory capacity in cells grown in non-fermentable carbon in an H3K4me-dependent manner. In association with these phenotypes, we find that JHD2 limits yeast proliferative capacity under physiologically challenging conditions as measured by both replicative lifespan and colony growth on non-fermentable carbon. JHD2's impact on nutrient response may reflect an ancestral role of its gene family in mediating mitochondrial regulation.

Pyridoxine Supplementation Improves the Activity of Recombinant Glutamate Decarboxylase and the Enzymatic Production of Gama-Aminobutyric Acid.

Directory of Open Access Journals (Sweden)

Yan Huang

Full Text Available Glutamate decarboxylase (GAD catalyzes the irreversible decarboxylation of L-glutamate to the valuable food supplement γ-aminobutyric acid (GABA. In this study, GAD from Escherichia coli K12, a pyridoxal phosphate (PLP-dependent enzyme, was overexpressed in E. coli. The GAD produced in media supplemented with 0.05 mM soluble vitamin B6 analog pyridoxine hydrochloride (GAD-V activity was 154.8 U mL-1, 1.8-fold higher than that of GAD obtained without supplementation (GAD-C. Purified GAD-V exhibited increased activity (193.4 U mg-1, 1.5-fold higher than that of GAD-C, superior thermostability (2.8-fold greater than that of GAD-C, and higher kcat/Km (1.6-fold higher than that of GAD-C. Under optimal conditions in reactions mixtures lacking added PLP, crude GAD-V converted 500 g L-1 monosodium glutamate (MSG to GABA with a yield of 100%, and 750 g L-1 MSG with a yield of 88.7%. These results establish the utility of pyridoxine supplementation and lay the foundation for large-scale enzymatic production of GABA.

Detection of free radicals in gamma-irradiated soybean paste and model system by electron spin resonance spectroscopy

International Nuclear Information System (INIS)

Lee, E.-J.; Volkov, Vitaly I.; Byun, M.-W.; Lee, C.-H.

2002-01-01

We have investigated ESR spectra of fermented soybean paste irradiated at 77 K and compared with those of soybean protein isolate and soybean oil. The influences of irradiation dose, moisture content and heating after irradiation on the free radical concentration and species were examined. Four different carbon type free radicals, FR1-FR4, were identified as the product of amino acid decomposition. In the case of FR1, the doublet line arises from the hydrogen atom on the β-carbon adjacent to the carbonyl free radical. It disappeared at 150 K. FR2 was most abundant and disappeared at 190 K in wet soybean paste (WSP) and at 210 K in dry soybean paste (DSP), respectively. The radical FR4 originated from decarboxylation and deamination of amino acids, which disappeared at 210 K in both WSP and DSP. FR3 was assumed to be formed by the damage of amino acid side chains. The radical · OH was originated from water molecules, and was not observed in dry system. Sulfur radical was stable even at room temperature observed in both wet and dry systems. Aldehyde radical must be originated from the chemical reactions of enzymatic hydrolysates of soybean

The regulation and catalytic mechanism of the NADP-malic enzyme from tobacco leaves

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VERONIKA DOUBNEROVÁ

2009-08-01

Full Text Available The non-photosynthetic NADP-malic enzyme EC 1.1.1.40 (NADP-ME, which catalyzes the oxidative decarboxylation of L-malate and NADP+ to produce pyruvate and NADPH, respectively, and which could be involved in plant defense responses, was isolated from Nicotiana tabacum L. leaves. The mechanism of the enzyme reaction was studied by the initial rate method and was found to be an ordered sequential one. Regulation possibilities of purified cytosolic NADP-ME by cell metabolites were tested. Intermediates of the citric acid cycle (a-ketoglutarate, succinate, fumarate, metabolites of glycolysis (pyruvate, phosphoenolpyruvate, glucose-6-phosphate, compounds connected with lipogenesis (coenzyme A, acetyl-CoA, palmitoyl-CoA and some amino acids (glutamate, glutamine, aspartate did not significantly affect the NADP-ME activity from tobacco leaves. In contrast, macroergic compounds (GTP, ATP and ADP were strong inhibitors of NADP-ME; the type of inhibition and the inhibition constants were determined in the presence of the most effective cofactors (Mn2+ or Mg2+, required by NADP-ME. Predominantly non-competitive type of inhibitions of NADP-ME with respect to NADP+ and mixed type to L-malate were found.

Effect of salt-tolerant yeast of Candida versatilis and Zygosaccharomyces rouxii on the production of biogenic amines during soy sauce fermentation.

Science.gov (United States)

Qi, Wei; Hou, Li-Hua; Guo, Hong-Lian; Wang, Chun-Ling; Fan, Zhen-Chuan; Liu, Jin-Fu; Cao, Xiao-Hong

2014-06-01

This study aimed to enhance and improve the quality and safety of soy sauce. In the present work, the change of biogenic amines, such as histamine, tyramine, cadaverine, spermidine, was examined by the treatment of Candida versatilis and Zygosaccharomyces rouxii, and the influence of salt-tolerant yeast on biogenic amines was analysed during the whole fermentation process. The results showed that the content of biogenic amines was elevated after yeast treatment and the content of biogenic amines was influenced by using yeast. The dominating biogenic amine in soy sauce was tyramine. At the end of fermentation, the concentrations of biogenic amines produced by Zygosaccharomyces rouxii and Candida versatilis in the soy mash were 122.71 mg kg(-1) and 69.96 mg kg(-1) . The changes of biogenic amines in high-salt liquid soy mash during fermentation process indicated that a variety of biogenic amines were increased in the fermentation ageing period, which may be due to amino acid decarboxylation to form biogenic amines by yeast decarboxylase. The fermentation period of soy sauce should be longer than 5 months because biogenic amines began to decline after this time period. © 2013 Society of Chemical Industry.

Enhancement of the catalytic activity of ferulic acid decarboxylase from Enterobacter sp. Px6-4 through random and site-directed mutagenesis.

Science.gov (United States)

Lee, Hyunji; Park, Jiyoung; Jung, Chaewon; Han, Dongfei; Seo, Jiyoung; Ahn, Joong-Hoon; Chong, Youhoon; Hur, Hor-Gil

2015-11-01

The enzyme ferulic acid decarboxylase (FADase) from Enterobacter sp. Px6-4 catalyzes the decarboxylation reaction of lignin monomers and phenolic compounds such as p-coumaric acid, caffeic acid, and ferulic acid into their corresponding 4-vinyl derivatives, that is, 4-vinylphenol, 4-vinylcatechol, and 4-vinylguaiacol, respectively. Among various ferulic acid decarboxylase enzymes, we chose the FADase from Enterobacter sp. Px6-4, whose crystal structure is known, and produced mutants to enhance its catalytic activity by random and site-directed mutagenesis. After three rounds of sequential mutations, FADase(F95L/D112N/V151I) showed approximately 34-fold higher catalytic activity than wild-type for the production of 4-vinylguaiacol from ferulic acid. Docking analyses suggested that the increased activity of FADase(F95L/D112N/V151I) could be due to formation of compact active site compared with that of the wild-type FADase. Considering the amount of phenolic compounds such as lignin monomers in the biomass components, successfully bioengineered FADase(F95L/D112N/V151I) from Enterobacter sp. Px6-4 could provide an ecofriendly biocatalytic tool for producing diverse styrene derivatives from biomass.

Orotidine-5'-monophosphate decarboxylase catalysis: Kinetic isotope effects and the state of hybridization of a bound transition-state analogue

Energy Technology Data Exchange (ETDEWEB)

Acheson, S.A.; Bell, J.B.; Jones, M.E.; Wolfenden, R. (Univ. of North Carolina School of Medicine, Chapel Hill (USA))

1990-04-03

The enzymatic decarboxylation of orotidine 5'-monophosphate may proceed by an addition-elimination mechanism involving a covalently bound intermediate or by elimination of CO2 to generate a nitrogen ylide. In an attempt to distinguish between these two alternatives, 1-(phosphoribosyl)barbituric acid was synthesized with 13C at the 5-position. Interaction of this potential transition-state analogue inhibitor with yeast orotidine-5'-monophosphate decarboxylase resulted in a small (0.6 ppm) downfield displacement of the C-5 resonance, indicating no rehybridization of the kind that might have been expected to accompany 5,6-addition of an enzyme nucleophile. When the substrate orotidine 5'-monophosphate was synthesized with deuterium at C-5, no significant change in kcat (H/D = 0.99 +/- 0.06) or kcat/KM (H/D = 1.00 +/- 0.06) was found to result, suggesting that C-5 does not undergo significant changes in geometry before or during the step that determines the rate of the catalytic process. These results are consistent with a nitrogen ylide mechanism and offer no support for the intervention of covalently bound intermediates in the catalytic process.

In Folio Respiratory Fluxomics Revealed by {sup 13}C Isotopic Labeling and H/D Isotope Effects Highlight the Non-cyclic Nature of the Tricarboxylic Acid 'Cycle' in Illuminated Leaves

Energy Technology Data Exchange (ETDEWEB)

Tcherkez, G.; Mahe, A.; Gauthier, P.; Hodges, M. [Institut de Biotechnologie des Plantes, Plateforme Metabolisme-Metabolome IFR87, Batiment 630, Universite Paris-Sud 11, 91405 Orsay cedex (France); Tcherkez, G.; Mauve, C.; Cornic, G. [Laboratoire d' Ecophysiologie Vegetale, Ecologie Systematique Evolution (G.C.), Batiment 630, Universite Paris-Sud 11, 91405 Orsay cedex (France); Gout, E.; Bligny, R. [Laboratoire de Physiologie Cellulaire Vegetale, Commissariat a l' Energie Atomique-Grenoble, 38054 Grenoble cedex 9 (France)

2009-07-01

While the possible importance of the tricarboxylic acid (TCA) cycle reactions for leaf photosynthesis operation has been recognized, many uncertainties remain on whether TCA cycle biochemistry is similar in the light compared with the dark. It is widely accepted that leaf day respiration and the metabolic commitment to TCA decarboxylation are down-regulated in illuminated leaves. However, the metabolic basis (i.e. the limiting steps involved in such a down-regulation) is not well known. Here, we investigated the in vivo metabolic fluxes of individual reactions of the TCA cycle by developing two isotopic methods, {sup 13}C tracing and fluxomics and the use of H/D isotope effects, with Xanthium strumarium leaves. We provide evidence that the TCA 'cycle' does not work in the forward direction like a proper cycle but, rather, operates in both the reverse and forward directions to produce fumarate and glutamate, respectively. Such a functional division of the cycle plausibly reflects the compromise between two contrasted forces: (1) the feedback inhibition by NADH and ATP on TCA enzymes in the light, and (2) the need to provide pH-buffering organic acids and carbon skeletons for nitrate absorption and assimilation. (authors)

Evaluation of Brachypodium distachyon L-Tyrosine Decarboxylase Using L-Tyrosine Over-Producing Saccharomyces cerevisiae.

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Shuhei Noda

Full Text Available To demonstrate that herbaceous biomass is a versatile gene resource, we focused on the model plant Brachypodium distachyon, and screened the B. distachyon for homologs of tyrosine decarboxylase (TDC, which is involved in the modification of aromatic compounds. A total of 5 candidate genes were identified in cDNA libraries of B. distachyon and were introduced into Saccharomyces cerevisiae to evaluate TDC expression and tyramine production. It is suggested that two TDCs encoded in the transcripts Bradi2g51120.1 and Bradi2g51170.1 have L-tyrosine decarboxylation activity. Bradi2g51170.1 was introduced into the L-tyrosine over-producing strain of S. cerevisiae that was constructed by the introduction of mutant genes that promote deregulated feedback inhibition. The amount of tyramine produced by the resulting transformant was 6.6-fold higher (approximately 200 mg/L than the control strain, indicating that B. distachyon TDC effectively converts L-tyrosine to tyramine. Our results suggest that B. distachyon possesses enzymes that are capable of modifying aromatic residues, and that S. cerevisiae is a suitable host for the production of L-tyrosine derivatives.

Fed-batch production of vanillin by Bacillus aryabhattai BA03.

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Paz, Alicia; Outeiriño, David; Pinheiro de Souza Oliveira, Ricardo; Domínguez, José Manuel

2018-01-25

Bacillus aryabhattai BA03, a strain isolated in our laboratory, has interesting properties related to the production of natural aromas and flavors. Specifically, we have found that it was able to produce vanillin from ferulic acid (FA). Furthermore, this strain produces high amounts of 4-vinylguaiacol in only 14h, this being the only intermediate metabolite observed in the process. FA is an inexpensive feedstock for the production of natural value-added compounds when extracted from lignocellulosic wastes. In this study, we optimized the operational conditions (temperature, pH and agitation), medium composition and bioconversion technology (batch or fed-batch) to produce vanillin. In a fed-batch process conducted with just one additional supplementation after 24h, the maximal concentration of vanillin (147.1±0.9mg/L) was observed after 216h (Q V =0.681mg/Lh; Y V/fFA =0.082mg/mg) after degrading 90.3% FA. In view of our data, we postulate that Bacillus aryabhattai BA03 carries out a decarboxylation of ferulic acid as a metabolic pathway. Copyright © 2017 Elsevier B.V. All rights reserved.

Polyketide family of novel antibacterial 7-O-methyl-5'-hydroxy-3'-heptenoate-macrolactin from seaweed-associated Bacillus subtilis MTCC 10403.

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Chakraborty, Kajal; Thilakan, Bini; Raola, Vamshi Krishna

2014-12-17

Seaweed-associated heterotrophic bacterial communities were screened to isolate potentially useful antimicrobial strains, which were characterized by phylogenetic analysis. The bacteria were screened for the presence of metabolite genes involved in natural product biosynthetic pathway, and the structural properties of secondary metabolites were correlated with the genes. Bioactivity-guided isolation of polyene antibiotic 7-O-methyl-5'-hydroxy-3'-heptenoate-macrolactin from Bacillus subtilis MTCC10403 associated with seaweed Anthophycus longifolius using mass spectrometry and extensive 2D-NMR studies was carried out. The newly isolated macrolactin compound is a bactericidal antibiotic with broad spectrum activity against human opportunistic clinical pathogens. The biosynthetic pathway of 7-O-methyl-5'-hydroxy-3'-heptenoate-macrolactin by means of a stepwise, decarboxylative condensation pathway established the PKS-assisted biosynthesis of the parent macrolactin and the side-chain 5-hydroxyhept-3-enoate moiety attached to the macrolactin ring system at C-7. Antimicrobial activity analysis combined with the results of amplifying genes encoding for polyketide synthetase and nonribosomal peptide synthetase showed that seaweed-associated bacteria had broad-spectrum antimicrobial activity. The present work may have an impact on the exploitation of macrolactins for pharmaceutical and biotechnological applications.

Structure-activity relationship studies on a Trp dendrimer with dual activities against HIV and enterovirus A71. Modifications on the amino acid.

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Martínez-Gualda, Belén; Sun, Liang; Rivero-Buceta, Eva; Flores, Aida; Quesada, Ernesto; Balzarini, Jan; Noppen, Sam; Liekens, Sandra; Schols, Dominique; Neyts, Johan; Leyssen, Pieter; Mirabelli, Carmen; Camarasa, María-José; San-Félix, Ana

2017-03-01

We have recently described a new class of dendrimers with tryptophan (Trp) on the surface that show dual antiviral activities against HIV and EV71 enterovirus. The prototype compound of this family is a pentaerythritol derivative with 12 Trps on the periphery. Here we complete the structure-activity relationship studies of this family to identify key features that might be significant for the antiviral activity. With this aim, novel dendrimers containing different amino acids (aromatic and non-aromatic), tryptamine (a "decarboxylated" analogue of Trp) and N-methyl Trp on the periphery have been prepared. Dendrimer with N-Methyl Trp was the most active against HIV-1 and HIV-2 while dendrimer with tyrosine was endowed with the most potent antiviral activity against EV71. This tyrosine dendrimer proved to inhibit a large panel of EV71 clinical isolates (belonging to different clusters) in the low nanomolar/high picomolar range. In addition, a new synthetic procedure (convergent approach) has been developed for the synthesis of the prototype and some other dendrimers. This convergent approach proved more efficient (higher yields, easier purification) than the divergent approach previously reported. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Effect of ionizing radiation on solid and water solution Penicillin G

International Nuclear Information System (INIS)

Ben Salem, I.; Amine, Kh.M.; Mabrouk, Y.; Saidi, M.; Mezni, M; Boulila, N; Hafez, E

2015-01-01

Penicillin G is a conventional antibiotic used for treatment of different kinds of infectious diseases. Due to its huge quantity production and resistance to biodegradability, this molecule has been a serious concern for clinicians and environmentalists. In this study, the effect of ionizing radiation on the penicillin G powder and in water solution was investigated. The Nuclear Magnetic Resonance (NMR) and fourier transform infrared spectroscopy (FTIR) analysis showed that the ionizing radiation at 50 kGy has no effect on the integrity of solid Penicillin G. The anti-microbial assays revealed that the activity of irradiated solid Penicillin G did not reduce and was stable after storage for one month. Ionizing radiation at 50 kGy led to degradation of water solution Penicillin G. The complete disappear of peaks observed in the control sample confirmed the broken of β-lactam ring, the decarboxylation and cleavage of the thiazolidine ring. The product issued from the irradiation of Penicillin G, was completely removed by the bacterium Cupriavidus.metallidurans. Thus, the ionizing irradiation followed by a biological treatment was very effective method for removing of Penicillin G antibiotics residuals from water solution.

Organic tanks safety program FY95 waste aging studies

International Nuclear Information System (INIS)

Camaioni, D.M.; Samuels, W.D.; Clauss, S.A.; Lenihan, B.D.; Wahl, K.L.; Campbell, J.A.; Shaw, W.J.

1995-09-01

This report gives the second year's findings of a study of how thermal and radiological processes may change the composition of organic compounds in the underground tanks at Hanford. Efforts were focused on the global reaction kinetics in a simulated waste exposed to γ rays and the reactions of organic radicals with nitrite ion. The gas production is predominantly radiolytic. Decarboxylation of carboxylates is probably an aging pathway. TBP was totaly consumed in almost every run. Radiation clearly accelerated consumption of the other compounds. EDTA is more reactive than citrate. Oximes and possibly organic nitro compounds are key intermediates in the radiolytic redox reactions of organic compounds with nitrate/nitrite. Observations are consistent with organic compounds being progressively degraded to compounds with greater numbers of C-O bonds and fewer C-H and C-C bonds, resulting in an overall lower energy content. If the radwaste tanks are adequately ventilated and continually dosed by radioactivity, their total energy content should have declined. Level of risk depends on how rapidly carboxylate salts of moderate energy content (including EDTA fragments) degrade to low energy oxalate and formate

Uptake of 14C-labelled chloroquine and an 125I-labelled chloroquine analogue in some polypeptide hormone producing cell systems

International Nuclear Information System (INIS)

Dencker, L.; Lindquist, N.G.; Tjaelve, H.

1976-01-01

After the injection of 14 C-labelled chloroquine and the 125 I-labelled chloroquine analogue 4-(3 1 -dimethylaminopropylamino)-7-iodoquinoline [ 125 I]DAPQ into mice, rats and a monkey the distribution of the radioactivity was studied by autoradiographical methods. A high and persistent uptake occurred in some endocrine cell systems, such as the pancreatic islets, the hypophysis, the adrenal medulla and the thyroid (in cells that were probably identical with the parafollicular cells). The melanin-containing tissues were the only ones which showed a higher uptake and retention of radioactivity. The above mentioned endocrine cells and the melanocytes have a common embryological origin and common morphological and cytochemical characteristics. They have been called the APUD (Amine Precursor Uptake and Decarboxylation)-cell series. It is proposed that the polypeptide hormone producing cells and the melanocytes may use a similar mechanism for accumulating chloroquine and (as shown earlier) also some other drugs such as nicotine, alprenolol, local anesthetics and atropine. These drugs however, accumulate stronger within the melanocytes and become bound to the melanin for a long time. The ability to accumulate these drugs may be considered another characteristic of the APUD-cell series. (author)

[Medicinal chemistry and pharmacology focused on cannabidiol, a major component of the fiber-type cannabis].

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Takeda, Shuso

2013-01-01

Considerable attention has focused on cannabidiol (CBD), a major non-psychotropic constituent of fiber-type cannabis plant, and it has been reported to possess diverse biological activities. Although CBD is obtained from non-enzymatic decarboxylation of its parent molecule, cannabidiolic acid (CBDA), several studies have investigated whether CBDA itself is biologically active. In the present report, the author summarizes findings indicating that; 1) CBDA is a selective cyclooxygenase-2 (COX-2) inhibitor, and ii) CBDA possesses an anti-migrative potential for highly invasive cancer cells, apparently through a mechanism involving inhibition of cAMP-dependent protein kinase A, coupled with an activation of the small GTPase, RhoA. Further, the author introduces recent findings on the medicinal chemistry and pharmacology of the CBD derivative, CBD-2',6'-dimethyl ether (CBDD), that exhibits inhibitory activity toward 15-lipoxygenase (15-LOX), an enzyme responsible for the production of oxidized low-density lipoprotein (LDL). These studies establish CBD as both an important experimental tool and as a lead compound for pharmaceutical development. In this review, the author further discusses the potential uses of CBD and its derivatives in future medicines.

Identification and characterization of phenylacetonitrile as a nitrogenous disinfection byproduct derived from chlorination of phenylalanine in drinking water.

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Ma, Xiaoyan; Deng, Jing; Feng, Jiao; Shanaiah, Narasimhamurthy; Smiley, Elizabeth; Dietrich, Andrea M

2016-10-01

Unregulated disinfection byproducts (DBPs), including nitrogenous disinfection byproducts (N-DBPs), originating from chlorination of the precursor amino acid phenylalanine in aqueous systems, were identified in laboratory reactions and distributed tap. The major N-DBP identified was phenylacetonitrile, and minor DBPs of benzyl chloride, phenylacetaldehyde, 2-chlorobenzyl cyanide, and 2, 6-diphenylpyridine were also formed. Phenylacetonitrile was generated through decarboxylation, dechlorination and/or hydrolysis processes. With an aromatic structure, phenylacetonitrile has an unpleasant odor of various descriptors and an odor threshold concentration of 0.2 ppt-v as measured through gas chromatography-olfactometry. The half-life of phenylacetonitrile in reagent water and chlorinated water at 19 °C were 121 h and 792 h, respectively. The occurrence of phenylacetonitrile as an N-DBP in tap water was investigated for the first time; the results revealed that μg/L concentrations were present in nine different distributed drinking waters in China and the United States. Phenylacetonitrile deteriorates the aesthetic quality of drinking water and may present risk due to its prolonged existence in drinking water, especially in the presence of residual chlorine. Copyright © 2016 Elsevier Ltd. All rights reserved.

Characterization of naphthalene degradation by Streptomyces sp. QWE-5 isolated from active sludge.

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Xu, Peng; Ma, Wencheng; Han, Hongjun; Hou, Baolin; Jia, Shengyong

2014-01-01

A bacterial strain, QWE-5, which utilized naphthalene as its sole carbon and energy source, was isolated and identified as Streptomyces sp. It was a Gram-positive, spore-forming bacterium with a flagellum, with whole, smooth, convex and wet colonies. The optimal temperature and pH for QWE-5 were 35 °C and 7.0, respectively. The QWE-5 strain was capable of completely degrading naphthalene at a concentration as high as 100 mg/L. At initial naphthalene concentrations of 10, 20, 50, 80 and 100 mg/L, complete degradation was achieved within 32, 56, 96, 120 and 144 h, respectively. Kinetics of naphthalene degradation was described using the Andrews equation. The kinetic parameters were as follows: qmax (maximum specific degradation rate) = 1.56 h⁻¹, Ks (half-rate constant) = 60.34 mg/L, and KI (substrate-inhibition constant) = 81.76 mg/L. Metabolic intermediates were identified by gas chromatography and mass spectrometry, allowing a new degradation pathway for naphthalene to be proposed. In this pathway, monooxygenation of naphthalene yielded naphthalen-1-ol. Further degradation by Streptomyces sp. QWE-5 produced acetophenone, followed by adipic acid, which was produced as a combination of decarboxylation and hydroxylation processes.

Establishment of Radiolabelling Method for the Development of Neurodegenerative Disease Imaging Agent Using 5-HT{sub 1A} Subtype of Receptor Anatagonist

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Choi, Sun Ju; Choi, Sang Mu; Kim, On Hee; Hong, Young Don; Park, Kyung Bae [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

2005-07-01

The 5-HT1A subtype of receptors for the neurotransmitter serotonin is predominantly located in the limbic forebrain. And it is involved in the modulation of emotion and the function of the hypothalamus. Since 5-HT1A receptors are implicated in the pathogenesis of anxiety, depression, hallucinogenic behaviour, motion sickness and eating disorders, they are an important target for drug therapy and diagnosis of diseases. Serotonin is synthesized from the amino acid L-tryptophan by sequential hydroxylation and decarboxylation. It is stored in presynaptic vesicles and released from nerve terminals during neuronal firing. One of the best-characterised binding sites for serotonin is the 5-HT1A receptor. This is mainly due to the relatively early discovery of a selective ligand, 8-hydroxy-2-(di-n-propylamino)tetralin (8-OH-DPAT) for this subpopulation. Thus, many researchers have tried to develop a radioligand capable of assessing in vivo changes in 5-HT1A receptors in depressed subjects, people with anxiety disorders, patients with Alzheimer's disease and schizophrenics. In present study, we studied the radioligands which would play a role in visualization and quantification of this important neuroreceptor for single-photon emission tomography (SPET)

Stereochemical course of enzyme-catalyzed aminopropyl transfer: spermidine synthase

International Nuclear Information System (INIS)

Kullberg, D.W.; Orr, G.R.; Coward, J.K.

1986-01-01

The R and S enantionmers of S-adenosyl-3-[ 2 H]3-(methylthio)-1-propylamine (decarboxylated S-adenosylmethionine), previously synthesized in this laboratory, were incubated with [1,4- 2 H 4 ]-putrescine in the presence of spermidine synthase from E. coli. The resulting chiral [ 2 H 5 ]spermidines were isolated and converted to their N 1 ,N 7 -dibocspermidine-N 4 -(1S,4R)-camphanamides. The derivatives were analyzed by 500 MHz 1 H-NMR and the configuration of the chiral center assigned by correlation with the spectra of synthetic chiral [ 2 H 3 ]dibocspermidine camphanamide standards. The enzyme-catalyzed aminopropyl transfer was shown to occur with net retention of configuration, indicative of a double-displacement mechanism. This result concurs with that of a previous steady-state kinetics study of spermidine synthase isolated from E. coli, but contradicts the single-displacement mechanism suggested by a stereochemical analysis of chiral spermidines biosynthesized in E. coli treated with chirally deuterated methionines. It also indicates that this aminopropyltransferase is mechanistically distinct from the methyltransferases, which have been shown to act via a single-displacement mechanism (net inversion at -CH 3 ) in all cases studied to date

Aminopropyltransferases involved in polyamine biosynthesis localize preferentially in the nucleus of plant cells.

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Borja Belda-Palazón

Full Text Available Plant aminopropyltransferases consist of a group of enzymes that transfer aminopropyl groups derived from decarboxylated S-adenosyl-methionine (dcAdoMet or dcSAM to propylamine acceptors to produce polyamines, ubiquitous metabolites with positive charge at physiological pH. Spermidine synthase (SPDS uses putrescine as amino acceptor to form spermidine, whereas spermine synthase (SPMS and thermospermine synthase (TSPMS use spermidine as acceptor to synthesize the isomers spermine and thermospermine respectively. In previous work it was shown that both SPDS1 and SPDS2 can physically interact with SPMS although no data concerning the subcellular localization was reported. Here we study the subcellular localization of these enzymes and their protein dimer complexes with gateway-based Bimolecular Fluorescence Complementation (BiFC binary vectors. In addition, we have characterized the molecular weight of the enzyme complexes by gel filtration chromatography with in vitro assembled recombinant enzymes and with endogenous plant protein extracts. Our data suggest that aminopropyltransferases display a dual subcellular localization both in the cytosol and nuclear enriched fractions, and they assemble preferably as dimers. The BiFC transient expression data suggest that aminopropyltransferase heterodimer complexes take place preferentially inside the nucleus.

Physiological regulation of isocitrate dehydrogenase and the role of 2-oxoglutarate in Prochlorococcus sp. strain PCC 9511.

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María Agustina Domínguez-Martín

Full Text Available The enzyme isocitrate dehydrogenase (ICDH; EC 1.1.1.42 catalyzes the oxidative decarboxylation of isocitrate, to produce 2-oxoglutarate. The incompleteness of the tricarboxylic acids cycle in marine cyanobacteria confers a special importance to isocitrate dehydrogenase in the C/N balance, since 2-oxoglutarate can only be metabolized through the glutamine synthetase/glutamate synthase pathway. The physiological regulation of isocitrate dehydrogenase was studied in cultures of Prochlorococcus sp. strain PCC 9511, by measuring enzyme activity and concentration using the NADPH production assay and Western blotting, respectively. The enzyme activity showed little changes under nitrogen or phosphorus starvation, or upon addition of the inhibitors DCMU, DBMIB and MSX. Azaserine, an inhibitor of glutamate synthase, induced clear increases in the isocitrate dehydrogenase activity and icd gene expression after 24 h, and also in the 2-oxoglutarate concentration. Iron starvation had the most significant effect, inducing a complete loss of isocitrate dehydrogenase activity, possibly mediated by a process of oxidative inactivation, while its concentration was unaffected. Our results suggest that isocitrate dehydrogenase responds to changes in the intracellular concentration of 2-oxoglutarate and to the redox status of the cells in Prochlorococcus.

Agmatine attenuates brain edema through reducing the expression of aquaporin-1 after cerebral ischemia

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Kim, Jae Hwan; Lee, Yong Woo; Park, Kyung Ah; Lee, Won Taek; Lee, Jong Eun

2010-01-01

Brain edema is frequently shown after cerebral ischemia. It is an expansion of brain volume because of increasing water content in brain. It causes to increase mortality after stroke. Agmatine, formed by the decarboxylation of -arginine by arginine decarboxylase, has been shown to be neuroprotective in trauma and ischemia models. The purpose of this study was to investigate the effect of agmatine for brain edema in ischemic brain damage and to evaluate the expression of aquaporins (AQPs). Results showed that agmatine significantly reduced brain swelling volume 22 h after 2 h middle cerebral artery occlusion in mice. Water content in brain tissue was clearly decreased 24 h after ischemic injury by agmatine treatment. Blood–brain barrier (BBB) disruption was diminished with agmatine than without. The expressions of AQPs-1 and -9 were well correlated with brain edema as water channels, were significantly decreased by agmatine treatment. It can thus be suggested that agmatine could attenuate brain edema by limitting BBB disruption and blocking the accumulation of brain water content through lessening the expression of AQP-1 after cerebral ischemia. PMID:20029450

Characterization and inactivation of an agmatine deiminase from Helicobacter pylori

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Jones, Justin E.; Causey, Corey P.; Lovelace, Leslie; Knuckley, Bryan; Flick, Heather; Lebioda, Lukasz; Thompson, Paul R. (SC)

2010-11-12

Helicobacter pylori encodes a potential virulence factor, agmatine deiminase (HpAgD), which catalyzes the conversion of agmatine to N-carbamoyl putrescine (NCP) and ammonia - agmatine is decarboxylated arginine. Agmatine is an endogenous human cell signaling molecule that triggers the innate immune response in humans. Unlike H. pylori, humans do not encode an AgD; it is hypothesized that inhibition of this enzyme would increase the levels of agmatine, and thereby enhance the innate immune response. Taken together, these facts suggest that HpAgD is a potential drug target. Herein we describe the optimized expression, isolation, and purification of HpAgD (10-30 mg/L media). The initial kinetic characterization of this enzyme has also been performed. Additionally, the crystal structure of wild-type HpAgD has been determined at 2.1 {angstrom} resolution. This structure provides a molecular basis for the preferential deimination of agmatine, and identifies Asp198 as a key residue responsible for agmatine recognition, which has been confirmed experimentally. Information gathered from these studies led to the development and characterization of a novel class of haloacetamidine-based HpAgD inactivators. These compounds are the most potent AgD inhibitors ever described.

Effects of prolonged agmatine treatment in aged male Sprague-Dawley rats.

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Rushaidhi, M; Zhang, H; Liu, P

2013-03-27

Increasing evidence suggests that altered arginine metabolism contributes to cognitive decline during ageing. Agmatine, decarboxylated arginine, has a variety of pharmacological effects, including the modulation of behavioural function. A recent study demonstrated the beneficial effects of short-term agmatine treatment in aged rats. The present study investigated how intraperitoneal administration of agmatine (40mg/kg, once daily) over 4-6weeks affected behavioural function and neurochemistry in aged Sprague-Dawley rats. Aged rats treated with saline displayed significantly reduced exploratory activity in the open field, impaired spatial learning and memory in the water maze and object recognition memory relative to young rats. Prolonged agmatine treatment improved animals' performance in the reversal test of the water maze and object recognition memory test, and significantly suppressed age-related elevation in nitric oxide synthase activity in the dentate gyrus of the hippocampus and prefrontal cortex. However, this prolonged supplementation was unable to improve exploratory activity and spatial reference learning and memory in aged rats. These findings further demonstrate that exogenous agmatine selectively improves behavioural function in aged rats. Copyright © 2013 IBRO. Published by Elsevier Ltd. All rights reserved.

Establishment of Radiolabelling Method for the Development of Neurodegenerative Disease Imaging Agent Using 5-HT1A Subtype of Receptor Anatagonist

International Nuclear Information System (INIS)

Choi, Sun Ju; Choi, Sang Mu; Kim, On Hee; Hong, Young Don; Park, Kyung Bae

2005-01-01

The 5-HT1A subtype of receptors for the neurotransmitter serotonin is predominantly located in the limbic forebrain. And it is involved in the modulation of emotion and the function of the hypothalamus. Since 5-HT1A receptors are implicated in the pathogenesis of anxiety, depression, hallucinogenic behaviour, motion sickness and eating disorders, they are an important target for drug therapy and diagnosis of diseases. Serotonin is synthesized from the amino acid L-tryptophan by sequential hydroxylation and decarboxylation. It is stored in presynaptic vesicles and released from nerve terminals during neuronal firing. One of the best-characterised binding sites for serotonin is the 5-HT1A receptor. This is mainly due to the relatively early discovery of a selective ligand, 8-hydroxy-2-(di-n-propylamino)tetralin (8-OH-DPAT) for this subpopulation. Thus, many researchers have tried to develop a radioligand capable of assessing in vivo changes in 5-HT1A receptors in depressed subjects, people with anxiety disorders, patients with Alzheimer's disease and schizophrenics. In present study, we studied the radioligands which would play a role in visualization and quantification of this important neuroreceptor for single-photon emission tomography (SPET)

Environmental implications of jatropha biofuel from a silvi-pastoral production system in central-west Brazil.

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Bailis, Rob; Kavlak, Goksin

2013-07-16

We present a life cycle assessment of synthetic paraffinic kerosene produced from Jatropha curcas. The feedstock is grown in an intercropping arrangement with pasture grasses so that Jatropha is coproduced with cattle. Additional innovations are introduced including hybrid seeds, detoxification of jatropha seedcake, and cogeneration. Two fuel pathways are examined including a newly developed catalytic decarboxylation process. Sensitivities are examined including higher planting density at the expense of cattle production as well as 50% lower yields. Intercropping with pasture and detoxifying seedcake yield coproducts that are expected to relieve pressure on Brazil's forests and indirectly reduce environmental impacts of biofuel production. Other innovations also reduce impacts. Results of the baseline assessment indicate that innovations would reduce impacts relative to the fossil fuel reference scenario in most categories including 62-75% reduction in greenhouse gas emissions, 64-82% reduction in release of ozone depleting chemicals, 33-52% reduction in smog-forming pollutants, 6-25% reduction in acidification, and 60-72% reduction in use of nonrenewable energy. System expansion, which explicitly accounts for avoided deforestation, results in larger improvements. Results are robust across allocation methodologies, improve with higher planting density, and persist if yield is reduced by half.

POTENTIAL OF LIVESTOCK MANURE FOR COAL ACTIVATION

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EllIN HARlIA HARlIA

2017-06-01

Full Text Available The natural methane formed by bacteria in anaerobic conditions is known as biogenic gas. Gas trapped in coal, formed through thermogenesis as well as biogenesisis known as coal-bed methane (CBM. The availability of organic material as decomposition of this material into methane is continuously required for the production of methane in the coal aquifer. The aim of this research was to investigate whether or not cattle feces bacteria were able to grow and produce methane in coal. Parameters measured were Volatile Fatty Acids (VFA and the production of biogas, such as nitrogen, hydrogen, carbon dioxide, and methane. Explorative method was used and data obtained was analyzed by descriptive approach. The results showed that the bacteria found in the feces survived in the coal and produce biogas. On day 2 when the process was at the acidogenesis phase, it produced VFA with the largest component of acetic acid. Acetic acid would undergo decarboxylation and reduction of CO2 followed by reactions of H2and CO2 to produce methane (CH4 and carbon dioxide (CO2 as the final products. ,

Differential Contribution of Malic Enzymes during Soybean and Castor Seeds Maturation.

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Mariel Claudia Gerrard Wheeler

Full Text Available Malic enzymes (ME catalyze the decarboxylation of malate generating pyruvate, CO2 and NADH or NADPH. In some organisms it has been established that ME is involved in lipids biosynthesis supplying carbon skeletons and reducing power. In this work we studied the MEs of soybean and castor, metabolically different oilseeds. The comparison of enzymatic activities, transcript profiles and organic acid contents suggest different metabolic strategies operating in soybean embryo and castor endosperm in order to generate precursors for lipid biosynthesis. In castor, the malate accumulation pattern agrees with a central role of this metabolite in the provision of carbon to plastids, where the biosynthesis of fatty acids occurs. In this regard, the genome of castor possesses a single gene encoding a putative plastidic NADP-ME, whose expression level is high when lipid deposition is active. On the other hand, NAD-ME showed an important contribution to the maturation of soybean embryos, perhaps driving the carbon relocation from mitochondria to plastids to support the fatty acids synthesis in the last stages of seed filling. These findings provide new insights into intermediary metabolism in oilseeds and provide new biotechnological targets to improve oil yields.

Biological Production of a Hydrocarbon Fuel Intermediate Polyhydroxybutyrate (PHB) from a Process Relevant Lignocellulosic Derived Sugar (Poster)

Energy Technology Data Exchange (ETDEWEB)

Wang, W.; Mittal, A.; Mohagheghi, A.; Johnson, D. K.

2014-04-01

PHAs are synthesized by many microorganisms to serve as intracellular carbon storage molecules. In some bacterial strains, PHB can account for up to 80% of cell mass. In addition to its application in the packaging sector, PHB also has great potential as an intermediate in the production of hydrocarbon fuels. PHB can be thermally depolymerized and decarboxylated to propene which can be upgraded to hydrocarbon fuels via commercial oligomerization technologies. Cupriavidus necator is the microorganism that has been most extensively studied and used for PHB production on an industrial scale; However the substrates used for producing PHB are mainly fructose, glucose, sucrose, fatty acids, glycerol, etc., which are expensive. In this study, we demonstrate production of PHB from a process relevant lignocellulosic derived sugar stream, i.e., saccharified slurry from pretreated corn stover. The strain was first investigated in shake flasks for its ability to utilize glucose, xylose and acetate. In addition, the strain was also grown on pretreated lignocellulose hydrolyzate slurry and evaluated in terms of cell growth, sugar utilization, PHB accumulation, etc. The mechanism of inhibition in the toxic hydrolysate generated by the pretreatment and saccharification process of biomass, was also studied.

Biochemical approaches to C4 photosynthesis evolution studies: the case of malic enzymes decarboxylases.

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Saigo, Mariana; Tronconi, Marcos A; Gerrard Wheeler, Mariel C; Alvarez, Clarisa E; Drincovich, María F; Andreo, Carlos S

2013-11-01

C4 photosynthesis enables the capture of atmospheric CO2 and its concentration at the site of RuBisCO, thus counteracting the negative effects of low atmospheric levels of CO2 and high atmospheric levels of O2 (21 %) on photosynthesis. The evolution of this complex syndrome was a multistep process. It did not occur by simply recruiting pre-exiting components of the pathway from C3 ancestors which were already optimized for C4 function. Rather it involved modifications in the kinetics and regulatory properties of pre-existing isoforms of non-photosynthetic enzymes in C3 plants. Thus, biochemical studies aimed at elucidating the functional adaptations of these enzymes are central to the development of an integrative view of the C4 mechanism. In the present review, the most important biochemical approaches that we currently use to understand the evolution of the C4 isoforms of malic enzyme are summarized. It is expected that this information will help in the rational design of the best decarboxylation processes to provide CO2 for RuBisCO in engineering C3 species to perform C4 photosynthesis.

Elucidation of cladofulvin biosynthesis reveals a cytochrome P450 monooxygenase required for anthraquinone dimerization.

Science.gov (United States)

Griffiths, Scott; Mesarich, Carl H; Saccomanno, Benedetta; Vaisberg, Abraham; De Wit, Pierre J G M; Cox, Russell; Collemare, Jérôme

2016-06-21

Anthraquinones are a large family of secondary metabolites (SMs) that are extensively studied for their diverse biological activities. These activities are determined by functional group decorations and the formation of dimers from anthraquinone monomers. Despite their numerous medicinal qualities, very few anthraquinone biosynthetic pathways have been elucidated so far, including the enzymatic dimerization steps. In this study, we report the elucidation of the biosynthesis of cladofulvin, an asymmetrical homodimer of nataloe-emodin produced by the fungus Cladosporium fulvum A gene cluster of 10 genes controls cladofulvin biosynthesis, which begins with the production of atrochrysone carboxylic acid by the polyketide synthase ClaG and the β-lactamase ClaF. This compound is decarboxylated by ClaH to yield emodin, which is then converted to chrysophanol hydroquinone by the reductase ClaC and the dehydratase ClaB. We show that the predicted cytochrome P450 ClaM catalyzes the dimerization of nataloe-emodin to cladofulvin. Remarkably, such dimerization dramatically increases nataloe-emodin cytotoxicity against mammalian cell lines. These findings shed light on the enzymatic mechanisms involved in anthraquinone dimerization. Future characterization of the ClaM enzyme should facilitate engineering the biosynthesis of novel, potent, dimeric anthraquinones and structurally related compound families.

Direct Functionalization of an Acid-Terminated Nanodiamond with Azide: Enabling Access to 4-Substituted-1,2,3-Triazole-Functionalized Particles.

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Kennedy, Zachary C; Barrett, Christopher A; Warner, Marvin G

2017-03-21

Azides on the periphery of nanodiamond materials (ND) are of great utility because they have been shown to undergo Cu-catalyzed and Cu-free cycloaddition reactions with structurally diverse alkynes, affording particles tailored for applications in biology and materials science. However, current methods employed to access ND featuring azide groups typically require either harsh pretreatment procedures or multiple synthesis steps and use surface linking groups that may be susceptible to undesirable cleavage. Here we demonstrate an alternative single-step approach to producing linker-free, azide-functionalized ND. Our method was applied to low-cost, detonation-derived ND powders where surface carbonyl groups undergo silver-mediated decarboxylation and radical substitution with azide. ND with directly grafted azide groups were then treated with a variety of aliphatic, aromatic, and fluorescent alkynes to afford 1-(ND)-4-substituted-1,2,3-triazole materials under standard copper-catalyzed cycloaddition conditions. Surface modification steps were verified by characteristic infrared absorptions and elemental analyses. High loadings of triazole surface groups (up to 0.85 mmol g -1 ) were obtained as determined from thermogravimetric analysis. The azidation procedure disclosed is envisioned to become a valuable initial transformation in numerous future applications of ND.

Structure of the Cyanuric Acid Hydrolase TrzD Reveals Product Exit Channel.

Science.gov (United States)

Bera, Asim K; Aukema, Kelly G; Elias, Mikael; Wackett, Lawrence P

2017-03-27

Cyanuric acid hydrolases are of industrial importance because of their use in aquatic recreational facilities to remove cyanuric acid, a stabilizer for the chlorine. Degradation of excess cyanuric acid is necessary to maintain chlorine disinfection in the waters. Cyanuric acid hydrolase opens the cyanuric acid ring hydrolytically and subsequent decarboxylation produces carbon dioxide and biuret. In the present study, we report the X-ray structure of TrzD, a cyanuric acid hydrolase from Acidovorax citrulli. The crystal structure at 2.19 Å resolution shows a large displacement of the catalytic lysine (Lys163) in domain 2 away from the active site core, whereas the two other active site lysines from the two other domains are not able to move. The lysine displacement is proposed here to open up a channel for product release. Consistent with that, the structure also showed two molecules of the co-product, carbon dioxide, one in the active site and another trapped in the proposed exit channel. Previous data indicated that the domain 2 lysine residue plays a role in activating an adjacent serine residue carrying out nucleophilic attack, opening the cyanuric acid ring, and the mobile lysine guides products through the exit channel.

Mitochondrial control through nutritionally regulated global histone H3 lysine-4 demethylation

Science.gov (United States)

Soloveychik, Maria; Xu, Mengshu; Zaslaver, Olga; Lee, Kwanyin; Narula, Ashrut; Jiang, River; Rosebrock, Adam P.; Caudy, Amy A.; Meneghini, Marc D.

2016-01-01

Histone demethylation by Jumonji-family proteins is coupled with the decarboxylation of α-ketoglutarate (αKG) to yield succinate, prompting hypotheses that their activities are responsive to levels of these metabolites in the cell. Consistent with this paradigm we show here that the Saccharomyces cerevisiae Jumonji demethylase Jhd2 opposes the accumulation of H3K4me3 in fermenting cells only when they are nutritionally manipulated to contain an elevated αKG/succinate ratio. We also find that Jhd2 opposes H3K4me3 in respiratory cells that do not exhibit such an elevated αKG/succinate ratio. While jhd2∆ caused only limited gene expression defects in fermenting cells, transcript profiling and physiological measurements show that JHD2 restricts mitochondrial respiratory capacity in cells grown in non-fermentable carbon in an H3K4me-dependent manner. In association with these phenotypes, we find that JHD2 limits yeast proliferative capacity under physiologically challenging conditions as measured by both replicative lifespan and colony growth on non-fermentable carbon. JHD2’s impact on nutrient response may reflect an ancestral role of its gene family in mediating mitochondrial regulation. PMID:27897198

Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal-Organic Frameworks

KAUST Repository

Feng, Liang

2018-01-18

Sufficient pore size, appropriate stability and hierarchical porosity are three prerequisites for open frameworks designed for drug delivery, enzyme immobilization and catalysis involving large molecules. Herein, we report a powerful and general strate-gy, linker thermolysis, to construct ultra-stable hierarchically porous metal−organic frameworks (HP-MOFs) with tunable pore size distribution. Linker instability, usually an undesirable trait of MOFs, was exploited to create mesopores by generating crystal defects throughout a microporous MOF crystal via thermolysis. The crystallinity and stability of HP-MOFs remain after thermolabile linkers are selectively removed from multivariate metal-organic frameworks (MTV-MOFs) through a decarboxyla-tion process. A domain-based linker spatial distribution was found to be critical for creating hierarchical pores inside MTV-MOFs. Furthermore, linker thermolysis promotes the formation of ultra-small metal oxide (MO) nanoparticles immobilized in an open framework that exhibits high catalytic activity for Lewis acid catalyzed reactions. Most importantly, this work pro-vides fresh insights into the connection between linker apportionment and vacancy distribution, which may shed light on prob-ing the disordered linker apportionment in multivariate systems, a long-standing challenge in the study of MTV-MOFs.

Development of a Pseudomonas aeruginosa Agmatine Biosensor

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Adam Gilbertsen

2014-10-01

Full Text Available Agmatine, decarboxylated arginine, is an important intermediary in polyamine production for many prokaryotes, but serves higher functions in eukaryotes such as nitric oxide inhibition and roles in neurotransmission. Pseudomonas aeruginosa relies on the arginine decarboxylase and agmatine deiminase pathways to convert arginine into putrescine. One of the two known agmatine deiminase operons, aguBA, contains an agmatine sensitive TetR promoter controlled by AguR. We have discovered that this promoter element can produce a titratable induction of its gene products in response to agmatine, and utilized this discovery to make a luminescent agmatine biosensor in P. aeruginosa. The genome of the P. aeruginosa lab strain UCBPP-PA14 was altered to remove both its ability to synthesize or destroy agmatine, and insertion of the luminescent reporter construct allows it to produce light in proportion to the amount of exogenous agmatine applied from ~100 nM to 1mM. Furthermore it does not respond to related compounds including arginine or putrescine. To demonstrate potential applications the biosensor was used to detect agmatine in spent supernatants, to monitor the development of arginine decarboxylase over time, and to detect agmatine in the spinal cords of live mice.

Molecular mechanism of pH-dependent substrate transport by an arginine-agmatine antiporter.

Science.gov (United States)

Wang, Sheng; Yan, Renhong; Zhang, Xi; Chu, Qi; Shi, Yigong

2014-09-02

Enteropathogenic bacteria, exemplified by Escherichia coli, rely on acid-resistance systems (ARs) to survive the acidic environment of the stomach. AR3 consumes intracellular protons through decarboxylation of arginine (Arg) in the cytoplasm and exchange of the reaction product agmatine (Agm) with extracellular Arg. The latter process is mediated by the Arg:Agm antiporter AdiC, which is activated in response to acidic pH and remains fully active at pH 6.0 and below. Despite our knowledge of structural information, the molecular mechanism by which AdiC senses acidic pH remains completely unknown. Relying on alanine-scanning mutagenesis and an in vitro proteoliposome-based transport assay, we have identified Tyr74 as a critical pH sensor in AdiC. The AdiC variant Y74A exhibited robust transport activity at all pH values examined while maintaining stringent substrate specificity for Arg:Agm. Replacement of Tyr74 by Phe, but not by any other amino acid, led to the maintenance of pH-dependent substrate transport. These observations, in conjunction with structural information, identify a working model for pH-induced activation of AdiC in which a closed conformation is disrupted by cation-π interactions between proton and the aromatic side chain of Tyr74.

A wide diversity of bacteria from the human gut produces and degrades biogenic amines.

Science.gov (United States)

Pugin, Benoit; Barcik, Weronika; Westermann, Patrick; Heider, Anja; Wawrzyniak, Marcin; Hellings, Peter; Akdis, Cezmi A; O'Mahony, Liam

2017-01-01

Background : Biogenic amines (BAs) are metabolites produced by the decarboxylation of amino acids with significant physiological functions in eukaryotic and prokaryotic cells. BAs can be produced by bacteria in fermented foods, but little is known concerning the potential for microbes within the human gut microbiota to produce or degrade BAs. Objective : To isolate and identify BA-producing and BA-degrading microbes from the human gastrointestinal tract. Design : Fecal samples from human volunteers were screened on multiple growth media, under multiple growth conditions. Bacterial species were identified using 16S rRNA sequencing and BA production or degradation was assessed using ultra-performance liquid chromatography. Results : In total, 74 BA-producing or BA-degrading strains were isolated from the human gut. These isolates belong to the genera Bifidobacterium , Clostridium , Enterococcus , Lactobacillus , Pediococcus , Streptococcus , Enterobacter , Escherichia , Klebsiella , Morganella and Proteus . While differences in production or degradation of specific BAs were observed at the strain level, our results suggest that these metabolic activities are widely spread across different taxa present within the human gut microbiota. Conclusions : The isolation and identification of microbes from the human gut with BA-producing and BA-degrading metabolic activity is an important first step in developing a better understanding of how these metabolites influence health and disease.

Validation of histamine determination Method in yoghurt using High Performance Liquid Chromatography

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M Jahedinia

2014-02-01

Full Text Available Biogenic amines are organic, basic nitrogenous compounds of low molecular weight that are mainly generated by the enzymatic decarboxylation of amino acids by microorganisms. Dairy products are among the foods with the highest amine content. A wide variety of methods and procedures for determination of histamine and biogenic amines have been established. Amongst, HPLC method is considered as reference method. The aim of this study was to validate Reversed Phase HPLC method determination of histamine in yoghurt. The mobile phase consisted of acetonitrile/water (18:88 v/v and the flow rate was set at 0.5 ml/min using isocratic HPLC. Detection was carried out at 254 nm using UV-detector. Calibration curve that was constructed using peak area of standards was linear and value of correlation coefficient (r2 was estimated at 0.998. Good recoveries were observed for histamine under investigation at all spiking levels and average of recoveries was 84%. The RSD% value from repeatability test was found to be %4.4. Limit of detection and limit of quantitation were 0.14 and 0.42 µ/ml, respectively. The results of validation tests showed that the method is reliable and rapid for quantification of histamine in yoghurt.

Topotactic Transformation of Metal-Organic Frameworks to Graphene-Encapsulated Transition-Metal Nitrides as Efficient Fenton-like Catalysts.

Science.gov (United States)

Li, Xuning; Ao, Zhimin; Liu, Jiayi; Sun, Hongqi; Rykov, Alexandre I; Wang, Junhu

2016-12-27

Innovation in transition-metal nitride (TMN) preparation is highly desired for realization of various functionalities. Herein, series of graphene-encapsulated TMNs (Fe x Mn 6-x Co 4 -N@C) with well-controlled morphology have been synthesized through topotactic transformation of metal-organic frameworks in an N 2 atmosphere. The as-synthesized Fe x Mn 6-x Co 4 -N@C nanodices were systematically characterized and functionalized as Fenton-like catalysts for catalytic bisphenol A (BPA) oxidation by activation of peroxymonosulfate (PMS). The catalytic performance of Fe x Mn 6-x Co 4 -N@C was found to be largely enhanced with increasing Mn content. Theoretical calculations illustrated that the dramatically reduced adsorption energy and facilitated electron transfer for PMS activation catalyzed by Mn 4 N are the main factors for the excellent activity. Both sulfate and hydroxyl radicals were identified during the PMS activation, and the BPA degradation pathway mainly through hydroxylation, oxidation, and decarboxylation was investigated. Based on the systematic characterization of the catalyst before and after the reaction, the overall PMS activation mechanism over Fe x Mn 6-x Co 4 -N@C was proposed. This study details the insights into versatile TMNs for sustainable remediation by activation of PMS.

Emerging infections: Shewanella - A series of five cases

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Krishna Kanchan Sharma

2010-01-01

Full Text Available Background : Shewanella spp. are unusual cause of disease in humans; however, reports of Shewanella infections have been increasing. Shewanella is a ubiquitous organism that has been isolated from many foods, sewage, and both from fresh and salt water. Earlier it was named as Pseudomonas putrefaciens or Shewanella putrefaciens. There are several reports describing this organism causing human infections such as cellulitis, abscesses, bacteremia, wound infection, etc. It is oxidase and catalase-positive non-fermenter gram-negative rod that produces hydrogen sulfide. Aims : The study was conducted to identify Shewanella spp., which was wrongly reported as Pseudomonas spp. Materials and Methods : Clinical samples were cultured as per standard clinical laboratory procedure. We tested the non-lactose-fermenting colonies for oxidase positivity. Oxidase-positive colony was inoculated in triple sugar iron slant (TSI to know the hydrogen sulfide production. Hydrogen sulfide positive colonies were further tested for citrate, urease, indole, and amino acid decarboxylation and acid and gas production from sugars. Results : Five isolates identified as Pseudomonas spp. during preliminary testing were proved to be Shewanella spp. on further testing. Conclusions : It will help in better understanding the epidemiology, pathogenesis and risk factors associated with these and prevention of the rare pathogenic organisms.

Production of gaba (γ - aminobutyric acid by microorganisms: a review

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Radhika Dhakal

2012-12-01

Full Text Available GABA (γ-aminobutyric acid is a four carbon non-protein amino acid that is widely distributed in plants, animals and microorganisms. As a metabolic product of plants and microorganisms produced by the decarboxylation of glutamic acid, GABA functions as an inhibitory neurotransmitter in the brain that directly affects the personality and the stress management. A wide range of traditional foods produced by microbial fermentation contain GABA, in which GABA is safe and eco-friendly, and also has the possibility of providing new health-benefited products enriched with GABA. Synthesis of GABA is catalyzed by glutamate decarboxylase, therefore, the optimal fermentation condition is mainly based on the biochemical properties of the enzyme. Major GABA producing microorganisms are lactic acid bacteria (LAB, which make food spoilage pathogens unable to grow and act as probiotics in the gastrointestinal tract. The major factors affecting the production of GABA by microbial fermentation are temperature, pH, fermentation time and different media additives, therefore, these factors are summarized to provide the most up-dated information for effective GABA synthesis. There has been a huge accumulation of knowledge on GABA application for human health accompanying with a demand on natural GABA supply. Only the GABA production by microorganisms can fulfill the demand with GABA-enriched health beneficial foods.

Production of gaba (γ – Aminobutyric acid) by microorganisms: a review

Science.gov (United States)

Dhakal, Radhika; Bajpai, Vivek K.; Baek, Kwang-Hyun

2012-01-01

GABA (γ-aminobutyric acid) is a four carbon non-protein amino acid that is widely distributed in plants, animals and microorganisms. As a metabolic product of plants and microorganisms produced by the decarboxylation of glutamic acid, GABA functions as an inhibitory neurotransmitter in the brain that directly affects the personality and the stress management. A wide range of traditional foods produced by microbial fermentation contain GABA, in which GABA is safe and eco-friendly, and also has the possibility of providing new health-benefited products enriched with GABA. Synthesis of GABA is catalyzed by glutamate decarboxylase, therefore, the optimal fermentation condition is mainly based on the biochemical properties of the enzyme. Major GABA producing microorganisms are lactic acid bacteria (LAB), which make food spoilage pathogens unable to grow and act as probiotics in the gastrointestinal tract. The major factors affecting the production of GABA by microbial fermentation are temperature, pH, fermentation time and different media additives, therefore, these factors are summarized to provide the most up-dated information for effective GABA synthesis. There has been a huge accumulation of knowledge on GABA application for human health accompanying with a demand on natural GABA supply. Only the GABA production by microorganisms can fulfill the demand with GABA-enriched health beneficial foods. PMID:24031948

Production of gaba (γ - Aminobutyric acid) by microorganisms: a review.

Science.gov (United States)

Dhakal, Radhika; Bajpai, Vivek K; Baek, Kwang-Hyun

2012-10-01

GABA (γ-aminobutyric acid) is a four carbon non-protein amino acid that is widely distributed in plants, animals and microorganisms. As a metabolic product of plants and microorganisms produced by the decarboxylation of glutamic acid, GABA functions as an inhibitory neurotransmitter in the brain that directly affects the personality and the stress management. A wide range of traditional foods produced by microbial fermentation contain GABA, in which GABA is safe and eco-friendly, and also has the possibility of providing new health-benefited products enriched with GABA. Synthesis of GABA is catalyzed by glutamate decarboxylase, therefore, the optimal fermentation condition is mainly based on the biochemical properties of the enzyme. Major GABA producing microorganisms are lactic acid bacteria (LAB), which make food spoilage pathogens unable to grow and act as probiotics in the gastrointestinal tract. The major factors affecting the production of GABA by microbial fermentation are temperature, pH, fermentation time and different media additives, therefore, these factors are summarized to provide the most up-dated information for effective GABA synthesis. There has been a huge accumulation of knowledge on GABA application for human health accompanying with a demand on natural GABA supply. Only the GABA production by microorganisms can fulfill the demand with GABA-enriched health beneficial foods.

Light-regulated phosphorylation of maize phosphoenolpyruvate carboxykinase plays a vital role in its activity.

Science.gov (United States)

Chao, Qing; Liu, Xiao-Yu; Mei, Ying-Chang; Gao, Zhi-Fang; Chen, Yi-Bo; Qian, Chun-Rong; Hao, Yu-Bo; Wang, Bai-Chen

2014-05-01

Phosphoenolpyruvate carboxykinase (PEPCK)-the major decarboxylase in PEPCK-type C4 plants-is also present in appreciable amounts in the bundle sheath cells of NADP-malic enzyme-type C4 plants, such as maize (Zea mays), where it plays an apparent crucial role during photosynthesis (Wingler et al., in Plant Physiol 120(2):539-546, 1999; Furumoto et al., in Plant Mol Biol 41(3):301-311, 1999). Herein, we describe the use of mass spectrometry to demonstrate phosphorylation of maize PEPCK residues Ser55, Thr58, Thr59, and Thr120. Western blotting indicated that the extent of Ser55 phosphorylation dramatically increases in the leaves of maize seedlings when the seedlings are transferred from darkness to light, and decreases in the leaves of seedlings transferred from light to darkness. The effect of light on phosphorylation of this residue is opposite that of the effect of light on PEPCK activity, with the decarboxylase activity of PEPCK being less in illuminated leaves than in leaves left in the dark. This inverse relationship between PEPCK activity and the extent of phosphorylation suggests that the suppressive effect of light on PEPCK decarboxylation activity might be mediated by reversible phosphorylation of Ser55.

Photodegradation kinetics, transformation, and toxicity prediction of ketoprofen, carprofen, and diclofenac acid in aqueous solutions.

Science.gov (United States)

Li, Jian; Ma, Li-Yun; Li, Lu-Shuang; Xu, Li

2017-12-01

Photodegradation of 3 commonly used nonsteroidal anti-inflammatory drugs, ketoprofen, carprofen, and diclofenac acid, was conducted under ultraviolet (UV) irradiation. The kinetic results showed that the 3 pharmaceuticals obeyed the first-order reaction with decreasing rate constants of 1.54 × 10 -4 , 5.91 × 10 -5 , and 7.78 × 10 -6  s -1 for carprofen, ketoprofen, and diclofenac acid, respectively. Moreover, the main transformation products were identified by ion-pair liquid-liquid extraction combined with injection port derivatization-gas chromatography-mass spectrometry and high-performance liquid chromatography-quadrupole-time of flight mass spectrometric analysis. There were 8, 3, and 6 transformation products identified for ketoprofen, carprofen, and diclofenac acid, respectively. Decarboxylation, dechlorination, oxidation, demethylation, esterification, and cyclization were proposed to be associated with the transformation of the 3 pharmaceuticals. Toxicity prediction of the transformation products was conducted on the EPI Suite software based on ECOSAR model, and the results indicate that some of the transformation products were more toxic than the parent compounds. The present study provides the foundation to understand the transformation behavior of the studied pharmaceuticals under UV irradiation. Environ Toxicol Chem 2017;36:3232-3239. © 2017 SETAC. © 2017 SETAC.

Transcriptomic profile of aguR deletion mutant of Lactococcus lactis subsp. cremoris CECT 8666

Science.gov (United States)

del Rio, Beatriz; Linares, Daniel M.; Redruello, Begoña; Martin, Maria Cruz; Fernandez, Maria; de Jong, Anne; Kuipers, Oscar P.; Ladero, Victor; Alvarez, Miguel A.

2015-01-01

Lactococcus lactis subsp. cremoris CECT 8666 (formerly GE2-14) is a dairy strain that catabolizes agmatine (a decarboxylated derivative of arginine) into the biogenic amine putrescine by the agmatine deiminase (AGDI) pathway [1]. The AGDI cluster of L. lactis is composed by five genes aguR, aguB, aguD, aguA and aguC. The last four genes are responsible for the deamination of agmatine to putrescine and are co-transcribed as a single policistronic mRNA forming the catabolic operon aguBDAC[1]. aguR encodes a transmembrane protein that functions as a one-component signal transduction system that senses the agmatine concentration of the medium and accordingly regulates the transcription of aguBDAC[2], which is also transcriptionally regulated by carbon catabolic repression (CCR) via glucose, but not by other sugars such as lactose and galactose [1], [3]. Here we report the transcriptional profiling of the aguR gene deletion mutant (L. lactis subsp. cremoris CECT 8666 ∆aguR) [2] compared to the wild type strain, both grown in M17 medium with galactose as carbon source and supplemented with agmatine. The transcriptional profiling data of AguR-regulated genes were deposited in the Gene Expression Omnibus (GEO) database under accession no. GSE59514. PMID:26697381

Studies on the nature of intermediates in enzyme mechanisms

International Nuclear Information System (INIS)

Clark, J.D.

1988-01-01

The reaction pathway followed by malate synthase has been studied by the double isotope fractionation method to determine whether the reaction is stepwise or concerted. A primary deuterium kinetic isotope effect ( D V/K) of 1.3 ± 0.1 has been found using [ 2 H 3 ]acetyl-CoA as substrate. The 13 C isotope effect at the aldehydic carbon of glyoxylate has also been measured. For this determination, the malate product was quantitatively transformed into a new sample of malate having the carbon of interest at C-4. This material was decarboxylated to produce the appropriate CO 2 for isotope ratio mass spectrometric analysis. If the essential Zn(II) ion of yeast aldolase interacts with the carbonyl groups of bound substrates, we can expect that these will be more reactive toward reduction by borohydrides than those free in solution. Tritiated sodium borohydride was therefore used to reduce the substrates of yeast aldolase in the presence and absence of enzyme, and the enantiomeric and diastereomeric ratios of the products were analyzed. Experiments were conducted in an effort to distinguish between endocyclic and exocyclic cleavage in the hydrolysis catalyzed by lysozyme. Tritiated sodium borohydride was used in an attempt to trap the putative oxocarbonium intermediate

Influence of physical damage and freezing on histamine concentration and microbiological quality of yellowfin tuna during processing

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Gonzalo García-Tapia

2013-09-01

Full Text Available Yellowfin tuna has a high level of free histidine in their muscle, which can lead to histamine formation by microorganisms if temperature abuse occurs during handling and further processing. The objective of this study was to measure levels of histamine in damaged and undamaged thawed muscle to determine the effect of physical damage on the microbial count and histamine formation during the initial steps of canning processing and to isolate and identify the main histamine-forming microorganisms present in the flesh of yellowfin tuna. Total mesophilic and psicrophilic microorganisms were determined using the standard plate method. The presence of histamine-forming microorganisms was determined in a modified Niven's agar. Strains were further identified using the API 20E kit for enterobacteriaceae and Gram-negative bacilli. Physically damaged tuna did not show higher microbiological contamination than that of undamaged muscle tuna. The most active histamine-forming microorganism present in tuna flesh was Morganella morganii. Other decarboxylating microorganisms present were Enterobacter agglomerans and Enterobacter cloacae. Physical damage of tune during catching and handling did not increase the level of histamine or the amount of microorganisms present in tuna meat during frozen transportation, but they showed a higher risk of histamine-forming microorganism growth during processing.

Direct Functionalization of an Acid-Terminated Nanodiamond with Azide: Enabling Access to 4-Substituted-1,2,3-Triazole-Functionalized Particles

International Nuclear Information System (INIS)

Kennedy, Zachary C.; Barrett, Christopher A.; Warner, Marvin G.

2017-01-01

Azides on the periphery of nanodiamond materials (ND) are of great utility because they have been shown to undergo Cu-catalyzed and Cu-free cycloaddition reactions with structurally diverse alkynes, affording particles tailored for applications in biology and materials science. However, current methods employed to access ND featuring azide groups typically require either harsh pretreatment procedures or multiple synthesis steps and use surface linking groups that may be susceptible to undesirable cleavage. Here in this paper we demonstrate an alternative single-step approach to producing linker-free, azide-functionalized ND. Our method was applied to low-cost, detonation-derived ND powders where surface carbonyl groups undergo silver-mediated decarboxylation and radical substitution with azide. ND with directly grafted azide groups were then treated with a variety of aliphatic, aromatic, and fluorescent alkynes to afford 1-(ND)-4-substituted-1,2,3-triazole materials under standard copper-catalyzed cycloaddition conditions. Surface modification steps were verified by characteristic infrared absorptions and elemental analyses. High loadings of triazole surface groups (up to 0.85 mmol g –1 ) were obtained as determined from thermogravimetric analysis. The azidation procedure disclosed is envisioned to become a valuable initial transformation in numerous future applications of ND.

BCAA Metabolism and NH3 Homeostasis.

Science.gov (United States)

Conway, M E; Hutson, S M

2016-01-01

The branched chain amino acids (BCAA) are essential amino acids required not only for growth and development, but also as nutrient signals and as nitrogen donors to neurotransmitter synthesis and glutamate/glutamine cycling. Transamination and oxidative decarboxylation of the BCAAs are catalysed by the branched-chain aminotransferase proteins (BCATm, mitochondrial and BCATc, cytosolic) and the branched-chain α-keto acid dehydrogenase enzyme complex (BCKDC), respectively. These proteins show tissue, cell compartmentation, and protein-protein interactions, which call for substrate shuttling or channelling and nitrogen transfer for oxidation to occur. Efficient regulation of these pathways is mediated through the redox environment and phosphorylation in response to dietary and hormonal stimuli. The wide distribution of these proteins allows for effective BCAA utilisation. We discuss how BCAT, BCKDC, and glutamate dehydrogenase operate in supramolecular complexes, allowing for efficient channelling of substrates. The role of BCAAs in brain metabolism is highlighted in rodent and human brain, where differential expression of BCATm indicates differences in nitrogen metabolism between species. Finally, we introduce a new role for BCAT, where a change in function is triggered by oxidation of its redox-active switch. Our understanding of how BCAA metabolism and nitrogen transfer is regulated is important as many studies now point to BCAA metabolic dysregulation in metabolic and neurodegenerative conditions.

Biological implications of the Viking mission to Mars

International Nuclear Information System (INIS)

Mazur, P.; Barghoorn, E.S.; Jukes, T.H.; Margulis, L.

1978-01-01

A central purpose of Viking was to search for evidence that life exists on Mars or may have existed in the past. The missions carried three biology experiments the prime purpose of which was to seek for existing microbial life. They produced clear evidence of chemical reactivity in soil samples, but it is becoming increasingly clear that the chemical reactions were nonbiological in origin. The unexpected release of oxygen by soil moistened with water vapor in the Gas Exchange experiment together with the negative findings of the organic analysis experiment lead to the conclusion that the surface contains powerful oxidants. This conclusion is consistent with models of the atmosphere. The oxidants appear also to have been responsible for the decarboxylation of the organic nutrients that were introduced in the Label Release experiment. The major results of the GEX and LR experiments have been simulated at least qualitatively on Earth. The third, Pyrolytic Release, experiment obtained evidence for organic synthesis by soil samples. Although the mechanism of the synthesis is obscure, the thermal stability of the reaction makes a biological explanation most unlikely. Furthermore, the response of soil samples in all three experiments to the addition of water is not consistent with a biological interpretation. (Auth.)

Separation and analysis techniques for bound and unbound alkyl ketene dimer (AKD in paper: A review

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Sunil Kumar

2016-11-01

Full Text Available Alkyl ketene dimer (AKD is the reactive synthetic sizing agent that is used in alkaline or neutral papermaking conditions to provide certain level of hydrophobicity to the paper and board. The sizing mechanism of AKD involves its reaction with the hydroxyl groups on cellulose. However, all of AKD does not chemically react with fibers; some of it may undergo hydrolysis in water to form unstable β-keto acids, which decarboxylate to the corresponding ketone. This portion of AKD remains non-reacted (unbound and adsorbs onto fibers. The sizing effect depends mainly on the quantity of chemically reacted (bound AKD in paper, while the role of unbound forms, that is ketone and oligomer, is still not clear. Both bound and unbound portions of AKD have their own effect on paper. It is important to know the proportion of bound and unbound form of AKD in paper. The different techniques have been adopted for the separation and analysis of bound and unbound AKD present in paper. The aim of this paper is to review and summarize the various techniques provided by the researchers to separate the different forms of AKD and highlight the most important aspects for their separation.

SadA-Expressing Staphylococci in the Human Gut Show Increased Cell Adherence and Internalization

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Arif Luqman

2018-01-01

Full Text Available Summary: A subgroup of biogenic amines, the so-called trace amines (TAs, are produced by mammals and bacteria and can act as neuromodulators. In the genus Staphylococcus, certain species are capable of producing TAs through the activity of staphylococcal aromatic amino acid decarboxylase (SadA. SadA decarboxylates aromatic amino acids to produce TAs, as well as dihydroxy phenylalanine and 5-hydroxytryptophan to thus produce the neurotransmitters dopamine and serotonin. SadA-expressing staphylococci were prevalent in the gut of most probands, where they are part of the human intestinal microflora. Furthermore, sadA-expressing staphylococci showed increased adherence to HT-29 cells and 2- to 3-fold increased internalization. Internalization and adherence was also increased in a sadA mutant in the presence of tryptamine. The α2-adrenergic receptor is required for enhanced adherence and internalization. Thus, staphylococci in the gut might contribute to gut activity and intestinal colonization. : Luqman et al. examine the sadA gene and argue that it contributes to TAs. They found that neuromodulator-producing staphylococci were present in the gut of most probands. The produced neuromodulators enhanced the adherence and internalization of staphylococci to cells in culture. Keywords: adherence, aromatic amino acid decarboxylase, gut microbiota, internalization, neuromodulator, neurotransmitter, staphylococcus

Determination of gluconeogenesis in vivo with 14C-labeled substrates

International Nuclear Information System (INIS)

Katz, J.

1985-01-01

A mitochondrial model of gluconeogenesis and the tricarboxylic acid cycle, where pyruvate is metabolized via pyruvate carboxylase and pyruvate dehydrogenase, and pyruvate kinase is examined. The effect of the rate of tricarboxylic acid flux and the rates of the three reactions of pyruvate metabolism on the labeling patterns from [ 14 C]pyruvate and [ 14 C]acetate are analyzed. Expressions describing the specific radioactivities and 14 C distribution in glucose as a function of these rates are derived. Specific radioactivities and isotopic patterns depend markedly on the ratio of the rates of pyruvate carboxylation and decarboxylation to the rate of citrate synthesis, but the effect of phosphoenolpyruvate hydrolysis is minor. The effects of these rates on 1) specific radioactivity of phosphoenolpyruvate, 2) labeling pattern in glucose, and 3) contribution of pyruvate, acetyl-coenzyme A, and CO 2 to glucose carbon are illustrated. To determine the contribution of lactate or alanine to gluconeogenesis, experiments with two compounds labeled in different carbons are required. Methods in current use to correct for the dilution of 14 C in gluconeogenesis from [ 14 C]pyruvate are shown to be erroneous. The experimental design and techniques to determine gluconeogenesis from 14 C-labeled precursors are presented and illustrated with numerical examples

Positron emission tomographic studies on aromatic L-amino acid decarboxylase activity in vivo for L-dopa and 5-hydroxy-L-tryptophan in the monkey brain

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Hartvig, P; Tedroff, J; Lindner, K J; Bjurling, P; Chang, C W; Laangstroem, B [Uppsala Univ. (Sweden); Tsukada, H [Central Research Lab., Hamamatsu Photonics Shizuoka, Osaka (Japan); Watanabe, Y [Dept. of Neuroscience, Osaka Bioscience Inst., Osaka (Japan)

1993-01-01

The regional brain kinetics following 5-hydroxy-L-([beta]-11 C)tryptophan and L-([beta]-11 C)DOPA intravenous injection was measured in twelve Rhesus monkeys using positron emission tomography (PET). The radiolabelled compounds were also injected together with various doses of unlabelled 5-hydroxy-L-tryptophan or L-DOPA. The radioactivity accumulated in the striatal region and the rate of increased utilization with time was calculated using a graphical method with back of the brain as a reference region. The rate constants for decarboxylation were 0.0070 [+-] 0.0007 (S. D) and 0.0121 [+-] 0.0010 min[sup -1] for 5-hydroxy-L-([beta]-11 C)tryptophan and L-([beta]-11 C)DOPA, respectively. After concomitant injection with unlabelled 5-hydroxy-L-tryptophan, the rate constant of 5-hydroxy-L-([beta]-11 C)tryptophan decreased dose-dependently and a 50 percent reduction was seen with a dose of about 4 mg/kg of unlabelled compound. A decreased utilization rate of L-([beta]-11 C)DOPA was seen only after simultaneous injection of 30 mg/kg of either L-DOPA or 5-hydroxy-L-tryptophan. This capacity limitation was most likely interpreted as different affinity of the striatal aromatic amino acid decarboxylase for L-DOPA and 5-hydroxy-L-tryptophan, respectively.

Postillumination burst of carbon dioxide in crassalacean Acid metabolism plants.

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Crews, C E; Vines, H M; Black, C C

1975-04-01

Immediately following exposure to light, a postillumination burst of CO(2) has been detected in Crassulacean acid metabolism plants. A detailed study with pineapple (Ananas comosus) leaves indicates that the postillumination burst changes its amplitude and kinetics during the course of a day. In air, the postillumination burst in pineapple leaves generally is exhibited as two peaks. The postillumination burst is sensitive to atmospheric CO(2) and O(2) concentrations as well as to the light intensity under which plants are grown. We propose that the CO(2) released in the first postillumination burst peak is indicative of photorespiration since it is sensitive to either O(2) or CO(2) concentration while the second CO(2) evolution peak is likely due to decarboxylation of organic acids involved in Crassulacean acid metabolism.In marked contrast to other higher plants, the postillumination burst in Crassulacean acid metabolism plants can be equal to or greater than the rate of photosynthesis. Photosynthesis in pineapple leaves also varies throughout a day. Both photosynthesis and the postillumination burst have a daily variation which apparently is a complex function of degree of leaf acidity, growth light intensity, ambient gas phase, and the time a plant has been exposed to a given gas.

Study of non-catalytic thermal decomposition of triglyceride at hydroprocessing condition

International Nuclear Information System (INIS)

Palanisamy, Shanmugam; Gevert, Borje S.

2016-01-01

Highlights: • Thermolysis of triglycerides occurs above 300 °C and cracking intensify above 350 °C. • Decomposition of carboxylic group observed, and β-H abstraction gives radical. • Product contains aldehyde, ketonic, saturated/unsaturated, cyclic, glycerol group. • Gasoline fraction contains lighter, cyclic and unsaturated hydrocarbons. • Residues contain ester, dimer and carboxylic groups. - Abstract: Non-catalytic thermal decomposition of triglyceride is studied between 300 and 410 °C at 0.1 and 5 MPa in the presence of H 2 or inert gas. This test is carried in tubular reactor filled with inert material (borosilicate glass pellet). The qualitative and analytical results showed that n-alkanes and alkenes with oxygenated olefins were primary products, consistent with thermal cracking to lighter hydrocarbons. The resulting outlet fuel gas obtained mainly from the radical reaction and had high concentration of CO, ethylene and methane. The decomposition forms a large number of radical compounds containing acids, aldehydes, ketones, aliphatic and aromatic hydrocarbon groups. Lighter fraction contains mostly naphthenic group, and heavy fraction contains straight chain paraffinic hydrocarbons. When H 2 partial pressure raised, the cracking of heavy fractions is low, and products contain low concentration of the lighter and gasoline fractions. Here, the thermal decomposition of triglyceride yields lighter fractions due to cracking, decarboxylation and decarbonylation.

A systematic review on aromatic L-amino acid decarboxylase (5-hydroxytryptophan decarboxylase)

International Nuclear Information System (INIS)

Rahman, M.K.; Nagatsu, T.

1988-11-01

Aromatic L-amino acid decarboxylase (AADC, EC. 4.1.1.28) with L-5-hydroxytryptophan as a substrate (also called L-5-hydroxytryptophan decarboxylase, 5-HTPDC) decarboxylates L-5-hydroxytryptophan to serotonin (5-HT), an important neurotransmitter that involved in the regulation of neuronal functions, behaviour and emotion of higher animals. As it is an important enzyme, many researchers are now working on its physiological functions and properties and also on its isolation, purification and characterization from mammalian tissues. But up to now no systematic review studies have been done on this enzyme. We made systematic studies on this enzyme in tissues and brains of rats, and human subjects. We also developed highly sensitive assay methods of the enzyme. This new method led us to discover the enzyme in the sera of various animals. We examined the developmental changes of 5-HTPDC in the sera of animals. We discovered an endogenous inhibitor of the enzyme in the monkey blood. The purification of the enzyme were performed by us and other researches from the sera, brains, adrenals, liver and kidneys of mammals. These and other results of up to date research papers on 5-HTPDC have been reviewed in this paper. (author). 71 refs, 10 figs, 14 tabs

Supraspinally-administered agmatine attenuates the development of oral fentanyl self-administration

Science.gov (United States)

Wade, Carrie L.; Schuster, Daniel J.; Domingo, Kristine M.; Kitto, Kelley F.; Fairbanks, Carolyn A.

2009-01-01

The decarboxylation product of arginine, agmatine, has effectively reduced or prevented opioid-induced tolerance and dependence when given either systemically (intraperitoneally or subcutaneously) or centrally (intrathecally or intracerebroventricularly). Systemically administered agmatine also reduces the escalation phase of intravenous fentanyl self-administration in rats. The present study assessed whether centrally (intracerebroventricular, i.c.v.) delivered agmatine could prevent the development of fentanyl self-administration in mice. Mice were trained to respond under a fixed-ratio 1 (FR1) schedule for either fentanyl (0.7 μg/70 μl, p.o.) or food reinforcement. Agmatine (10 nmol/5 μl), injected i.c.v. 12-14h before the first session and every other evening (12-14h before session) for 2 weeks, completely attenuated oral fentanyl self-administration (but not food-maintained responding) compared to saline-injected controls. When agmatine was administered after fentanyl self-administration had been established (day 8) it had no attenuating effects on bar pressing. This dose of agmatine does not decrease locomotor activity as assessed by rotarod. The present findings significantly extend the previous observation that agmatine prevents opioid-maintained behavior to a chronic model of oral fentanyl self-administration as well as identifying a supraspinal site of action for agmatine inhibition of drug addiction. PMID:18495108

Transcriptomic profile of aguR deletion mutant of Lactococcus lactis subsp. cremoris CECT 8666

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Beatriz del Rio

2015-12-01

Full Text Available Lactococcus lactis subsp. cremoris CECT 8666 (formerly GE2-14 is a dairy strain that catabolizes agmatine (a decarboxylated derivative of arginine into the biogenic amine putrescine by the agmatine deiminase (AGDI pathway [1]. The AGDI cluster of L. lactis is composed by five genes aguR, aguB, aguD, aguA and aguC. The last four genes are responsible for the deamination of agmatine to putrescine and are co-transcribed as a single policistronic mRNA forming the catabolic operon aguBDAC [1]. aguR encodes a transmembrane protein that functions as a one-component signal transduction system that senses the agmatine concentration of the medium and accordingly regulates the transcription of aguBDAC [2], which is also transcriptionally regulated by carbon catabolic repression (CCR via glucose, but not by other sugars such as lactose and galactose [1,3]. Here we report the transcriptional profiling of the aguR gene deletion mutant (L. lactis subsp. cremoris CECT 8666 ∆aguR [2] compared to the wild type strain, both grown in M17 medium with galactose as carbon source and supplemented with agmatine. The transcriptional profiling data of AguR-regulated genes were deposited in the Gene Expression Omnibus (GEO database under accession no. GSE59514.

Evidence for oral agmatine sulfate safety--a 95-day high dosage pilot study with rats.

Science.gov (United States)

Gilad, Gad M; Gilad, Varda H

2013-12-01

Agmatine, decarboxylated arginine, exerts beneficial effects in various experimental disease models. Clinical trials indicate the safety and effectiveness of short-term (up to 21 days) high dose regimens of oral agmatine sulfate, but longer term studies are lacking. This pilot study undertook to assess the safety of a longer term high dosage oral agmatine sulfate in laboratory rats. Adult Wistar rats consumed 5.3 g/l agmatine sulfate in their drinking water for 95 days, a regimen estimated to result in a daily dosage of absorbed agmatine of about 100mg/kg. Animals' body weight, water consumption and blood pressure were periodically measured, and general cage behavior, fur appearance, urination and feces appearance monitored. These parameters were also determined at 20 days after treatment cessation (day 115). On days 95 and 115, animals were euthanized for gross necropsy assessment. Agmatine-treated rats showed slight, but significant reductions in body weight and blood pressure, and reduced water consumption during treatment, which recovered completely within 20 days after treatment cessation. Otherwise, no abnormal behaviors or organ pathologies were observed. These findings are first to suggest apparent safety of sub-chronic high dosage dietary agmatine sulfate in laboratory rats, thus lending further support to the therapeutic applications of agmatine. Copyright © 2013 Elsevier Ltd. All rights reserved.

Agmatine protects against zymosan-induced acute lung injury in mice by inhibiting NF-κB-mediated inflammatory response.

Science.gov (United States)

Li, Xuanfei; Liu, Zheng; Jin, He; Fan, Xia; Yang, Xue; Tang, Wanqi; Yan, Jun; Liang, Huaping

2014-01-01

Acute lung injury (ALI) is characterized by overwhelming lung inflammation and anti-inflammation treatment is proposed to be a therapeutic strategy for ALI. Agmatine, a cationic polyamine formed by decarboxylation of L-arginine, is an endogenous neuromodulator that plays protective roles in diverse central nervous system (CNS) disorders. Consistent with its neuromodulatory and neuroprotective properties, agmatine has been reported to have beneficial effects on depression, anxiety, hypoxic ischemia, Parkinson's disease, and gastric disorder. In this study, we tested the effect of agmatine on the lung inflammation induced by Zymosan (ZYM) challenge in mice. We found that agmatine treatment relieved ZYM-induced acute lung injury, as evidenced by the reduced histological scores, wet/dry weight ratio, and myeloperoxidase activity in the lung tissue. This was accompanied by reduced levels of TNF-α, IL-1β, and IL-6 in lung and bronchoalveolar lavage fluid and decreased iNOS expression in lung. Furthermore, agmatine inhibited the phosphorylation and degradation of IκB and subsequently blocked the activation of nuclear factor (NF)-κB induced by Zymosan. Taken together, our results showed that agmatine treatment inhibited NF-κB signaling in lungs and protected mice against ALI induced by Zymosan, suggesting agmatine may be a potential safe and effective approach for the treatment of ALI.

Anti-Atherosclerotic Action of Agmatine in ApoE-Knockout Mice.

Science.gov (United States)

Wiśniewska, Anna; Olszanecki, Rafał; Totoń-Żurańska, Justyna; Kuś, Katarzyna; Stachowicz, Aneta; Suski, Maciej; Gębska, Anna; Gajda, Mariusz; Jawień, Jacek; Korbut, Ryszard

2017-08-04

Atherosclerosis is an inflammatory disease in which dysfunction of mitochondria play an important role, and disorders of lipid management intensify this process. Agmatine, an endogenous polyamine formed by decarboxylation of arginine, exerts a protective effect on mitochondria and modulates fatty acid metabolism. We investigated the effect of exogenous agmatine on the development of atherosclerosis and changes in lipid profile in apolipoprotein E knockout (apoE-/-) mice. Agmatine caused an approximate 40% decrease of atherosclerotic lesions, as estimated by en face and cross-section methods with an influence on macrophage but not on smooth muscle content in the plaques. Agmatine treatment did not changed gelatinase activity within the plaque area. What is more, the action of agmatine was associated with an increase in the number of high density lipoproteins (HDL) in blood. Real-Time PCR analysis showed that agmatine modulates liver mRNA levels of many factors involved in oxidation of fatty acid and cholesterol biosynthesis. Two-dimensional electrophoresis coupled with mass spectrometry identified 27 differentially expressed mitochondrial proteins upon agmatine treatment in the liver of apoE-/- mice, mostly proteins related to metabolism and apoptosis. In conclusion, prolonged administration of agmatine inhibits atherosclerosis in apoE-/- mice; however, the exact mechanisms linking observed changes and elevations of HDL plasma require further investigation.

Participation of hippocampal agmatine in spatial learning: an in vivo microdialysis study.

Science.gov (United States)

Rushaidhi, Madihah; Jing, Yu; Zhang, Hu; Liu, Ping

2013-02-01

Agmatine, decarboxylated arginine, is widely distributed in mammalian brains and is considered as a novel putative neurotransmitter. Recent research demonstrates spatial learning-induced increases in agmatine in memory-related structures at the tissue and presynaptic terminal levels. By using the in vivo microdialysis technique coupled with highly sensitive liquid chromatography/mass spectrometry assay, we investigated dynamic changes of extracellular agmatine in the rat dorsal hippocampus before, during and after water maze training to find a fixed hidden platform on the first and forth day of testing. It was firstly noted that the basal level of extracellular agmatine was significantly elevated on day 4. While swimming per se had no effect, a rapid rise (2-6 folds) in extracellular agmatine was observed during water maze training regardless of testing day. Such learning-induced rise was found to successively lessen across the multiple blocks of training on day 1. However, this pattern was reversed on day 4 when the platform was removed during the final training trial. The present study, for the first time, demonstrates water maze training-induced increase of extracellular agmatine in the dorsal hippocampus. The results suggest a role of endogenous agmatine in the encoding and retrieval of spatial information. Copyright © 2012 Elsevier Ltd. All rights reserved.

Characterization of C₃--C₄ intermediate species in the genus Heliotropium L. (Boraginaceae): anatomy, ultrastructure and enzyme activity.

Science.gov (United States)

Muhaidat, Riyadh; Sage, Tammy L; Frohlich, Michael W; Dengler, Nancy G; Sage, Rowan F

2011-10-01

Photosynthetic pathway characteristics were studied in nine species of Heliotropium (sensu lato, including Euploca), using assessments of leaf anatomy and ultrastructure, activities of PEP carboxylase and C₄ acid decarboxylases, and immunolocalization of ribulose 1·5-bisphosphate carboxylase/oxygenase (Rubisco) and the P-subunit of glycine decarboxylase (GDC). Heliotropium europaeum, Heliotropium calcicola and Heliotropium tenellum are C₃ plants, while Heliotropium texanum and Heliotropium polyphyllum are C₄ species. Heliotropium procumbens and Heliotropium karwinskyi are functionally C₃, but exhibit 'proto-Kranz' anatomy where bundle sheath (BS) cells are enlarged and mitochondria primarily occur along the centripetal (inner) wall of the BS cells; GDC is present throughout the leaf. Heliotropium convolvulaceum and Heliotropium greggii are C₃--C₄ intermediates, with Kranz-like enlargement of the BS cells, localization of mitochondria along the inner BS wall and a loss of GDC in the mesophyll (M) tissue. These C₃--C₄ species of Heliotropium probably shuttle photorespiratory glycine from the M to the BS tissue for decarboxylation. Heliotropium represents an important new model for studying C₄ evolution. Where existing models such as Flaveria emphasize diversification of C₃--C₄ intermediates, Heliotropium has numerous C₃ species expressing proto-Kranz traits that could represent a critical initial phase in the evolutionary origin of C₄ photosynthesis. © 2011 Blackwell Publishing Ltd.

A NEXAFS and mass spectrometry study of cysteine, cystine and insulin irradiated with intermediate energy (0.8 keV) electrons

Energy Technology Data Exchange (ETDEWEB)

Simões, G., E-mail: simoes.grazieli@gmail.com [Instituto de Química, Universidade Federal do Rio de Janeiro, Cidade Universitária, 21941-909 Rio de Janeiro (Brazil); Rodrigues, F.N. [Instituto de Química, Universidade Federal do Rio de Janeiro, Cidade Universitária, 21941-909 Rio de Janeiro (Brazil); Instituto Federal de Educação, Ciência e Tecnologia do Rio de Janeiro, Maracanã, 20270-021 Rio de Janeiro (Brazil); Bernini, R.B. [Instituto de Química, Universidade Federal do Rio de Janeiro, Cidade Universitária, 21941-909 Rio de Janeiro (Brazil); Instituto Federal de Educação, Ciência e Tecnologia do Rio de Janeiro, Duque de Caxias, 25050-100 Rio de Janeiro (Brazil); Castro, C.S.C. [Instituto Nacional de Metrologia, Qualidade e Tecnologia – Inmetro, 25250-020 Rio de Janeiro (Brazil); Souza, G.G.B. de, E-mail: gerson@iq.ufrj.br [Instituto de Química, Universidade Federal do Rio de Janeiro, Cidade Universitária, 21941-909 Rio de Janeiro (Brazil)

2014-03-01

Highlights: • Structural modifications in sulfur containing biomolecules were investigated. • Significant modifications were observed in insulin irradiated NEXAFS spectra. • Degradation of insulin can be observed even at low temperature. • Alterations in insulin spectrum were characterized according to the state of sulfur. - Abstract: We have performed a NEXAFS (S 1s) and mass spectrometry study of solid samples of cysteine, cystine and insulin irradiated with 0.8 keV electrons. The measured mass spectra point out to processes of desulfurization, deamination, decarbonylation and decarboxylation in the irradiated biomolecules. Electron beam irradiation was also conducted at low temperatures in order to evaluate the possible contribution from thermal degradation processes. The NEXAFS spectra of irradiated cysteine and cystine did not show substantial changes when compared to the same spectra obtained using non-irradiated samples. The sulfur K-edge photoabsorption spectrum of irradiated insulin, however, showed clear modifications when compared to the spectrum of the non-irradiated protein, even when the irradiation was conducted at low temperature. Using an empirical combination of the photoabsorption spectra of cysteine and cystine (which are associated respectively with reduced and oxidized forms of sulfur) we have been able to reproduce the absorption spectrum of irradiated insulin.

Biological Production of a Hydrocarbon Fuel Intermediate Polyhydroxybutyrate (Phb) from a Process Relevant Lignocellulosic Derived Sugar

Energy Technology Data Exchange (ETDEWEB)

Wang, Wei; Mohagheghi, Ali; Mittal, Ashutosh; Pilath, Heidi; Johnson, David K.

2015-03-22

PHAs are synthesized by many microorganisms to serve as intracellular carbon storage molecules. In some bacterial strains, PHB can account for up to 80% of cell mass. In addition to its application in the packaging sector, PHB also has great potential as an intermediate in the production of hydrocarbon fuels. PHB can be thermally depolymerized and decarboxylated to propene which can be upgraded to hydrocarbon fuels via commercial oligomerization technologies. In recent years a great effort has been made in bacterial production of PHB, yet the production cost of the polymer is still much higher than conventional petrochemical plastics. The high cost of PHB is because the cost of the substrates can account for as much as half of the total product cost in large scale fermentation. Thus searching for cheaper and better substrates is very necessary for PHB production. In this study, we demonstrate production of PHB by Cupriavidus necator from a process relevant lignocellulosic derived sugar stream, i.e., saccharified hydrolysate slurry from pretreated corn stover. Good cell growth was observed on slurry saccharified with advanced enzymes and 40~60% of PHB was accumulated in the cells. The mechanism of inhibition in the toxic hydrolysate generated by pretreatment and saccharification of biomass, will be discussed.

Biological implications of the Viking mission to Mars

Energy Technology Data Exchange (ETDEWEB)

Mazur, P [Oak Ridge National Lab., TN (USA); Barghoorn, E S [Harvard Univ., Cambridge, MA (USA). Dept. of Biology; Halvorson, H O [Brandeis Univ., Waltham, MA (USA); Jukes, T H [California Univ., Berkeley (USA). Space Sciences Lab.; Kaplan, I R [California Univ., Los Angeles (USA); Margulis, L [Boston Univ., MA (USA)

1978-06-01

A central purpose of Viking was to search for evidence that life exists on Mars or may have existed in the past. The missions carried three biology experiments the prime purpose of which was to seek for existing microbial life. They produced clear evidence of chemical reactivity in soil samples, but it is becoming increasingly clear that the chemical reactions were nonbiological in origin. The unexpected release of oxygen by soil moistened with water vapor in the Gas Exchange experiment together with the negative findings of the organic analysis experiment lead to the conclusion that the surface contains powerful oxidants. This conclusion is consistent with models of the atmosphere. The oxidants appear also to have been responsible for the decarboxylation of the organic nutrients that were introduced in the Label Release experiment. The major results of the GEX and LR experiments have been simulated at least qualitatively on Earth. The third, Pyrolytic Release, experiment obtained evidence for organic synthesis by soil samples. Although the mechanism of the synthesis is obscure, the thermal stability of the reaction makes a biological explanation most unlikely. Furthermore, the response of soil samples in all three experiments to the addition of water is not consistent with a biological interpretation.

A reassessment of the role of serotonergic system in the control of feeding behavior

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Medeiros Magda A.

2005-01-01

Full Text Available The role of serotonergic system in the feeding behaviorwas appraised by electrolytic lesions in the dorsal raphe nucleus (DRN and administration of para-chlorophenylalanine (PCPA, 3 mg/5 mul, icv. Chronic evaluations were accomplished through 120 and 360 days in PCPA-injected and DRN-lesioned rats, respectively. Acute food intake was evaluated in fasted rats and submitted to injection of PCPA and hydroxytryptophan (LHTP, 30 mg/kg, ip. DRN-lesioned rats exhibited 22-80% increase in food intake up to sixth month, whereas the obesity was evident and sustained by whole period. In PCPA-injected rats was observed an initial increase in the food intake followed by hypophagy from 25th to 30th day and a transitory increase of body weight from 5th to 60th day. In the acute study, the LHTP reverted partially the PCPA-induced increase in food intake of fasted rats suggesting a sustained capacity of decarboxylation of precursor by serotonergic neurons. Slow restoration of the levels of food intake in DRN-lesioned rats reveals a neuroplasticity in the systems that regulate feeding behavior. A plateau on the body weight curve in lesioned rats possibly represents the establishment of a new and higher set point of energetic balance.

L-Dopa decarboxylase expression profile in human cancer cells.

Science.gov (United States)

Chalatsa, Ioanna; Nikolouzou, Eleftheria; Fragoulis, Emmanuel G; Vassilacopoulou, Dido

2011-02-01

L-Dopa decarboxylase (DDC) catalyses the decarboxylation of L-Dopa. It has been shown that the DDC gene undergoes alternative splicing within its 5'-untranslated region (UTR), in a tissue-specific manner, generating identical protein products. The employment of two alternative 5'UTRs is thought to be responsible for tissue-specific expression of the human DDC mRNA. In this study, we focused on the investigation of the nature of the mRNA expression in human cell lines of neural and non-neural origin. Our results show the expression of a neural-type DDC mRNA splice variant, lacking exon 3 in all cell lines studied. Co-expression of the full length non-neural DDC mRNA and the neural-type DDC splice variant lacking exon 3 was detected in all cell lines. The alternative DDC protein isoform, Alt-DDC, was detected in SH-SY5Y and HeLa cells. Our findings suggest that the human DDC gene undergoes complex processing, leading to the formation of multiple mRNA isoforms. The study of the significance of this phenomenon of multiple DDC mRNA isoforms could provide us with new information leading to the elucidation of the complex biological pathways that the human enzyme is involved in.

Heat-induced formation of mepiquat by decarboxylation of pipecolic acid and its betaine derivative. Part 2: Natural formation in cooked vegetables and selected food products.

Science.gov (United States)

Yuan, Yuan; Tarres, Adrienne; Bessaire, Thomas; Rademacher, Wilhelm; Stadler, Richard H; Delatour, Thierry

2017-08-01

Mepiquat (N,N-dimethylpiperidinium) is a plant growth regulator registered for use as its chloride salt in many countries on cereals and other crops. Recent model system studies have shown that natural chemicals present in crop plants, such as pipecolic acid and pipecolic acid betaine, may furnish mepiquat through different chemical pathways, when subjected to temperatures in the range of 200°C. In this study, we cooked raw vegetables that did not contain mepiquat to a palatable state using different traditional cooking methods, and detected mepiquat in 9 out of 11 oven-cooked vegetables, reaching up to 189μg/kg dry wt in oven-cooked broccoli. Commercial oven potato fries generated mepiquat during cooking, typically in the range of 20-60μg/kg. Only traces of mepiquat (cooked vegetables, including potatoes. Copyright © 2017 Elsevier Ltd. All rights reserved.

A two-dimensional microscale model of gas exchange during photosynthesis in maize (Zea mays L.) leaves.

Science.gov (United States)

Retta, Moges; Ho, Quang Tri; Yin, Xinyou; Verboven, Pieter; Berghuijs, Herman N C; Struik, Paul C; Nicolaï, Bart M

2016-05-01

CO2 exchange in leaves of maize (Zea mays L.) was examined using a microscale model of combined gas diffusion and C4 photosynthesis kinetics at the leaf tissue level. Based on a generalized scheme of photosynthesis in NADP-malic enzyme type C4 plants, the model accounted for CO2 diffusion in a leaf tissue, CO2 hydration and assimilation in mesophyll cells, CO2 release from decarboxylation of C4 acids, CO2 fixation in bundle sheath cells and CO2 retro-diffusion from bundle sheath cells. The transport equations were solved over a realistic 2-D geometry of the Kranz anatomy obtained from light microscopy images. The predicted responses of photosynthesis rate to changes in ambient CO2 and irradiance compared well with those obtained from gas exchange measurements. A sensitivity analysis showed that the CO2 permeability of the mesophyll-bundle sheath and airspace-mesophyll interfaces strongly affected the rate of photosynthesis and bundle sheath conductance. Carbonic anhydrase influenced the rate of photosynthesis, especially at low intercellular CO2 levels. In addition, the suberin layer at the exposed surface of the bundle sheath cells was found beneficial in reducing the retro-diffusion. The model may serve as a tool to investigate CO2 diffusion further in relation to the Kranz anatomy in C4 plants. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Mechanistic investigations of novel photoinitiators for radical polymerization

International Nuclear Information System (INIS)

Griesser, M.

2012-01-01

Nowadays, there is a wide variety of photoinitiators (PIs) available for radical polymerizations. A common example are two-component (Type II) systems such as benzophenone and tertiary amines. However these systems also suffer from problems due to bimolecularity. These include the possible back electron transfer (BET) leading to deactivation, as well as the solvent cage effect, occurring in highly viscous media. The aim of this thesis was to investigate the reaction mechanism of several photoinitiating systems, which show superior performance. Moreover, they exhibit additional benefits such as circumvention of oxygen inhibition by decarboxylation. Thereby this work helps to understand the molecular basis of the performance of different PI systems. In vestigated PIs included benzaldoxime esters, covalently linked benzophenone and N-phenylglycine as well as derivatives of both systems. Furthermore a PI based on benzophenone extended by ethynyl moeities is discussed. The main tool in this investigation was photo-CIDNP (chemically induced dynamic nuclear polarization), an NMR based technique for studying radical reactions. A complementary view was obtained with TR-EPR (time-resolved electron paramagnetic resonance), which provides direct information about the active radical species. The results were further compared with quantum mechanical calculations (DFT) of the magnetic properties of the radicals. The theoretical approach was further applied to other paramagnetic species such as donor-acceptor systems. (author) [de

Use of molecular modeling to determine the interaction and competition of gases within coal for carbon dioxide sequestration

Energy Technology Data Exchange (ETDEWEB)

Jeffrey D. Evanseck; Jeffry D. Madura; Jonathan P. Mathews

2006-04-21

Molecular modeling was employed to both visualize and probe our understanding of carbon dioxide sequestration within a bituminous coal. A large-scale (>20,000 atoms) 3D molecular representation of Pocahontas No. 3 coal was generated. This model was constructed based on a the review data of Stock and Muntean, oxidation and decarboxylation data for aromatic clustersize frequency of Stock and Obeng, and the combination of Laser Desorption Mass Spectrometry data with HRTEM, enabled the inclusion of a molecular weight distribution. The model contains 21,931 atoms, with a molecular mass of 174,873 amu, and an average molecular weight of 714 amu, with 201 structural components. The structure was evaluated based on several characteristics to ensure a reasonable constitution (chemical and physical representation). The helium density of Pocahontas No. 3 coal is 1.34 g/cm{sup 3} (dmmf) and the model was 1.27 g/cm{sup 3}. The structure is microporous, with a pore volume comprising 34% of the volume as expected for a coal of this rank. The representation was used to visualize CO{sub 2}, and CH{sub 4} capacity, and the role of moisture in swelling and CO{sub 2}, and CH{sub 4} capacity reduction. Inclusion of 0.68% moisture by mass (ash-free) enabled the model to swell by 1.2% (volume). Inclusion of CO{sub 2} enabled volumetric swelling of 4%.

Optimisation of trans-cinnamic acid and hydrocinnamyl alcohol production with recombinant Saccharomyces cerevisiae and identification of cinnamyl methyl ketone as a by-product.

Science.gov (United States)

Gottardi, Manuela; Grün, Peter; Bode, Helge B; Hoffmann, Thomas; Schwab, Wilfried; Oreb, Mislav; Boles, Eckhard

2017-12-01

Trans-cinnamic acid (tCA) and hydrocinnamyl alcohol (HcinOH) are valuable aromatic compounds with applications in the flavour, fragrance and cosmetic industry. They can be produced with recombinant yeasts from sugars via phenylalanine after expression of a phenylalanine ammonia lyase (PAL) and an aryl carboxylic acid reductase. Here, we show that in Saccharomyces cerevisiae a PAL enzyme from the bacterium Photorhabdus luminescens was superior to a previously used plant PAL enzyme for the production of tCA. Moreover, after expression of a UDP-glucose:cinnamate glucosyltransferase (FaGT2) from Fragaria x ananassa, tCA could be converted to cinnamoyl-D-glucose which is expected to be less toxic to the yeast cells. Production of tCA and HcinOH from glucose could be increased by eliminating feedback-regulated steps of aromatic amino acid biosynthesis and diminishing the decarboxylation step of the competing Ehrlich pathway. Finally, an unknown by-product resulting from further metabolisation of a carboligation product of cinnamaldehyde (cinALD) with activated acetaldehyde, mediated by pyruvate decarboxylases, could be identified as cinnamyl methyl ketone providing a new route for the biosynthesis of precursors, such as (2S,3R) 5-phenylpent-4-ene-2,3-diol, necessary for the chemical synthesis of specific biologically active drugs such as daunomycin. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Catalytic conversion of cellulose to liquid hydrocarbon fuels by progressive removal of oxygen to facilitate separation processes and achieve high selectivities

Energy Technology Data Exchange (ETDEWEB)

Dumesic, James A [Verona, WI; Ruiz, Juan Carlos Serrano [Madison, WI; West, Ryan M [Madison, WI

2012-04-03

Described is a method to make liquid chemicals, such as functional intermediates, solvents, and liquid fuels from biomass-derived cellulose. The method is cascading; the product stream from an upstream reaction can be used as the feedstock in the next downstream reaction. The method includes the steps of deconstructing cellulose to yield a product mixture comprising levulinic acid and formic acid, converting the levulinic acid to .gamma.-valerolactone, and converting the .gamma.-valerolactone to pentanoic acid. Alternatively, the .gamma.-valerolactone can be converted to a mixture of n-butenes. The pentanoic acid so formed can be further reacted to yield a host of valuable products. For example, the pentanoic acid can be decarboxylated yield 1-butene or ketonized to yield 5-nonanone. The 5-nonanone can be hydrodeoxygenated to yield nonane, or 5-nonanone can be reduced to yield 5-nonanol. The 5-nonanol can be dehydrated to yield nonene, which can be dimerized to yield a mixture of C.sub.9 and C.sub.18 olefins, which can be hydrogenated to yield a mixture of alkanes. Alternatively, the nonene may be isomerized to yield a mixture of branched olefins, which can be hydrogenated to yield a mixture of branched alkanes. The mixture of n-butenes formed from .gamma.-valerolactone can also be subjected to isomerization and oligomerization to yield olefins in the gasoline, jet and Diesel fuel ranges.

Structural Characterization of the Molecular Events during a Slow Substrate-Product Transition in Orotidine 5'-Monophosphate Decarboxylase

Energy Technology Data Exchange (ETDEWEB)

Fujihashi, Masahiro; Wei, Lianhu; Kotra, Lakshmi P; Pai, Emil F; (TGRI); (Toronto); (Kyoto)

2009-04-06

Crystal structures of substrate-product complexes of Methanobacterium thermoautotrophicum orotidine 5'-monophosphate decarboxylase, obtained at various steps in its catalysis of the unusual transformation of 6-cyano-uridine 5'-monophosphate (UMP) into barbituric acid ribosyl monophosphate, show that the cyano substituent of the substrate, when bound to the active site, is first bent significantly from the plane of the pyrimidine ring and then replaced by an oxygen atom. Although the K72A and D70A/K72A mutants are either catalytically impaired or even completely inactive, they still display bending of the C6 substituent. Interestingly, high-resolution structures of the D70A and D75N mutants revealed a covalent bond between C6 of UMP and the Lys72 side chain after the -CN moiety's release. The same covalent bond was observed when the native enzyme was incubated with 6-azido-UMP and 6-iodo-UMP; in contrast, the K72A mutant transformed 6-iodo-UMP to barbituric acid ribosyl 5'-monophosphate. These results demonstrate that, given a suitable environment, native orotidine 5'-monophosphate decarboxylase and several of its mutants are not restricted to the physiologically relevant decarboxylation; they are able to catalyze even nucleophilic substitution reactions but consistently maintain distortion on the C6 substituent as an important feature of catalysis.

Studies on the Simultaneous Formation of Aroma-Active and Toxicologically Relevant Vinyl Aromatics from Free Phenolic Acids during Wheat Beer Brewing.

Science.gov (United States)

Langos, Daniel; Granvogl, Michael

2016-03-23

During the brewing process of wheat beer, the desired aroma-active vinyl aromatics 2-methoxy-4-vinylphenol and 4-vinylphenol as well as the undesired and toxicologically relevant styrene are formed from their respective precursors, free ferulic acid, p-coumaric acid, and cinnamic acid, deriving from the malts. Analysis of eight commercial wheat beers revealed high concentrations of 2-methoxy-4-vinylphenol and 4-vinylphenol always in parallel with high concentrations of styrene or low concentrations of the odorants in parallel with low styrene concentrations, suggesting a similar pathway. To better understand the formation of these vinyl aromatics, each process step of wheat beer brewing and the use of different strains of Saccharomyces cerevisiae were evaluated. During wort boiling, only a moderate decarboxylation of free phenolic acids and formation of desired and undesired vinyl aromatics were monitored due to the thermal treatment. In contrast, this reaction mainly occurred enzymatically catalyzed during fermentation with S. cerevisiae strain W68 with normal Pof(+) activity (phenolic off-flavor) resulting in a wheat beer eliciting the typical aroma requested by consumers due to high concentrations of 2-methoxy-4-vinylphenol (1790 μg/L) and 4-vinylphenol (937 μg/L). Unfortunately, also a high concentration of undesired styrene (28.3 μg/L) was observed. Using a special S. cerevisiae strain without Pof(+) activity resulted in a significant styrene reduction (beer aroma.

Novel thermally cross-linked polyimide membranes for ethanol dehydration via pervaporation

KAUST Repository

Xu, Sheng

2015-12-01

© 2015 Elsevier B.V. In this work, two novel carboxyl-containing polyimides, 2,2\\'-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride-4,4\\'-diaminodiphenylmethane/3,5-diaminobenzoic acid (6FDA-MDA/DABA, FMD) and 3,3\\',4,4\\'-benzophenone tetracarboxylic dianhydride-4,4\\'-diaminodiphenylmethane/3,5-diaminobenzoic acid (BTDA-MDA/DABA, BMD), are synthesized via chemical and thermal imidization methods, respectively, and employed as pervaporation membranes for ethanol dehydration. Chemical structures of the two polyimides are examined by FTIR and TGA to confirm the successful synthesis. A post thermal treatment of the polyimide membranes with the temperature range of 250 to 400. °C is applied, and its effects on the membrane morphology and separation performance are studied and characterized by FTIR, TGA, WXRD, solubility and sorption test. It is believed that the thermal treatment of the carboxyl-containing polyimide membrane at a relative low temperature only leads to the physical annealing, while it may cause the decarboxylation-induced cross-linking at a higher temperature. In addition, the operation temperature in pervaporation is also varied and shown to be an important factor to affect the final membrane performance. Performance benchmarking shows that the developed polyimide membranes both have superior pervaporation performance to most other flat-sheet dense membranes. This work is believed to shed useful insights on polyimide membranes for pervaporation applications.

Agmatine Protects against Zymosan-Induced Acute Lung Injury in Mice by Inhibiting NF-κB-Mediated Inflammatory Response

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Xuanfei Li

2014-01-01

Full Text Available Acute lung injury (ALI is characterized by overwhelming lung inflammation and anti-inflammation treatment is proposed to be a therapeutic strategy for ALI. Agmatine, a cationic polyamine formed by decarboxylation of L-arginine, is an endogenous neuromodulator that plays protective roles in diverse central nervous system (CNS disorders. Consistent with its neuromodulatory and neuroprotective properties, agmatine has been reported to have beneficial effects on depression, anxiety, hypoxic ischemia, Parkinson’s disease, and gastric disorder. In this study, we tested the effect of agmatine on the lung inflammation induced by Zymosan (ZYM challenge in mice. We found that agmatine treatment relieved ZYM-induced acute lung injury, as evidenced by the reduced histological scores, wet/dry weight ratio, and myeloperoxidase activity in the lung tissue. This was accompanied by reduced levels of TNF-α, IL-1β, and IL-6 in lung and bronchoalveolar lavage fluid and decreased iNOS expression in lung. Furthermore, agmatine inhibited the phosphorylation and degradation of IκB and subsequently blocked the activation of nuclear factor (NF-κB induced by Zymosan. Taken together, our results showed that agmatine treatment inhibited NF-κB signaling in lungs and protected mice against ALI induced by Zymosan, suggesting agmatine may be a potential safe and effective approach for the treatment of ALI.

Cellular pharmacodynamics of the cytotoxic guanidino-containing drug CHS 828. Comparison with methylglyoxal-bis(guanylhydrazone).

Science.gov (United States)

Ekelund, S; Sjöholm, A; Nygren, P; Binderup, L; Larsson, R

2001-04-20

N-(6-(4-chlorophenoxy)hexyl)-N'-cyano-N"-4-pyridylguanidine (CHS 828) is a new guanidino-containing compound with antitumoral activity both in vitro and in vivo. Its activity profile differs from those of standard cytotoxic drugs but the mechanism of action is not yet fully understood. CHS 828 is presently in early phase I and II clinical trials. In the present study, the pharmacodynamic effects at the cellular level of CHS 828 was compared to another compound containing two guanidino groups, methylglyoxal-bis(guanylhydrazone) (MGBG). MGBG is known to inhibit the synthesis of polyamines, which are important in, e.g., proliferation and macromolecular synthesis. The concentration-response relationship of CHS 828 closely resembled that of MGBG and the drugs were similar with respect to inhibition of DNA and protein synthesis. On the other hand, CHS 828 induced a significant increase in cellular metabolism while MGBG did not. The cytotoxic effect of MGBG was reversed by the addition of exogenous polyamines, while that of CHS 828 was unaffected. Unlike MGBG, there was also no effect of CHS 828 on the levels of decarboxylating enzymes in the polyamine biosynthesis. In conclusion, CHS 828 does not appear to share any major mechanisms of action with the polyamine synthesis inhibitor MGBG. Further studies will be required to define the exact mechanism of action of CHS 828.

ASI: Dunaliella marine microalgae to drop-in replacement liquid transportation fuel

KAUST Repository

Wang, Weicheng

2013-09-11

Microalgae are a promising biofuels feedstock, theoretically yielding concentrations of triacylglycerides (TAGs) per unit area that are far higher than traditional feedstocks due to their rapid growth. Dunaliella is particularly advantageous as a feedstock because it is currently commercially mass cultured, thrives in salt water, and has no cell wall. Fourteen strains of Dunaliella have been investigated for growth rates and lipid production in mass culture and tested for enhanced lipid production under a range of environmental stressors including salinity, pH, nitrogen and phosphorus limitation, and light regime. The nuclear genome has been sequenced for four of these strains, with the objective of increasing carbon flux through genetic engineering. Electroflocculation followed by osmotic membrane rupturing may be a very energy and cost efficient means of harvesting the lipid bodies from Dunaliella. A technically feasible and scalable thermo-catalytic process to convert the lipids into replacements for liquid transportation fuels has been developed. The lipids were converted into long-chain alkanes through continuous thermal hydrolysis followed by fed-batch thermo-catalytic decarboxylation. These alkanes can be reformed into renewable diesel via conventional catalytic hydrocarbon isomerization reactions to improve cold flow properties, if desired. © 2013 American Institute of Chemical Engineers Environ Prog, 32: 916-925, 2013 Copyright © 2013 American Institute of Chemical Engineers Environ Prog.

Cryptic color change in a crab spider (Misumena vatia): identification and quantification of precursors and ommochrome pigments by HPLC.

Science.gov (United States)

Riou, Mickaël; Christidès, Jean-Philippe

2010-04-01

Mimicry is used widely by arthropods to survive in a hostile environment. Often mimicry is associated with the production of chemical compounds such as pigments. In crab spiders, the change of color is based on a complex physiological process that still is not understood. The aim of this study was to identify and quantify the ommochrome pigments and precursors responsible for the color change in the mimetic crab spider Misumena vatia (Thomisidae). A modified high performance reverse phase ion-pair chromatography technique enabled us to separate and quantify the ommochrome pigments, their precursors, and related metabolites in individual spiders. Compounds such as tryptophan, kynurenine, and kynurenic acid occurred only or mainly in white crab spiders. In contrast, compounds such as 3-hydroxy-kynurenine, xanthommatin, and ommatin D occurred only or mainly in yellow crab spiders. Factor analysis ranked the different color forms in accordance with their metabolites. The biochemical results enabled us to associate the different phases of formation of pigment granules with specific metabolites. Yellow crab spiders contain many unknown ommochrome-like compounds not present in white crab spiders. We also found large quantities of decarboxylated xanthommatin, whose role as precursor of new pathways in ommochrome synthesis needs to be assessed. The catabolism of ommochromes, a process occurring when spiders revert from yellow to white, warrants further study.

Unveiling the Mechanism of Arginine Transport through AdiC with Molecular Dynamics Simulations: The Guiding Role of Aromatic Residues.

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Eva-Maria Krammer

Full Text Available Commensal and pathogenic enteric bacteria have developed several systems to adapt to proton leakage into the cytoplasm resulting from extreme acidic conditions. One such system involves arginine uptake followed by export of the decarboxylated product agmatine, carried out by the arginine/agmatine antiporter (AdiC, which thus works as a virtual proton pump. Here, using classical and targeted molecular dynamics, we investigated at the atomic level the mechanism of arginine transport through AdiC of E. coli. Overall, our MD simulation data clearly demonstrate that global rearrangements of several transmembrane segments are necessary but not sufficient for achieving transitions between structural states along the arginine translocation pathway. In particular, local structural changes, namely rotameric conversions of two aromatic residues, are needed to regulate access to both the outward- and inward-facing states. Our simulations have also enabled identification of a few residues, overwhelmingly aromatic, which are essential to guiding arginine in the course of its translocation. Most of them belong to gating elements whose coordinated motions contribute to the alternating access mechanism. Their conservation in all known E. coli acid resistance antiporters suggests that the transport mechanisms of these systems share common features. Last but not least, knowledge of the functional properties of AdiC can advance our understanding of the members of the amino acid-carbocation-polyamine superfamily, notably in eukaryotic cells.

ASI: Dunaliella marine microalgae to drop-in replacement liquid transportation fuel

KAUST Repository

Wang, Weicheng; Allen, Elle H.; Campos, Andrew A.; Cade, Rushyannah Killens; Dean, Lisa L.; Dvora, Mia; Immer, Jeremy G.; Mixson, Stephanie M.; Srirangan, Soundarya; Sauer, Marie Laure; Schreck, Steven D.; Sun, Keyi; Thapaliya, Nirajan; Wilson, Cameron W.; Burkholder, Joann M M; Grunden, Amy M.; Lamb, Henry Henry; Winter, Heike Winter; Stikeleather, Larry F.; Roberts, William L.

2013-01-01

Microalgae are a promising biofuels feedstock, theoretically yielding concentrations of triacylglycerides (TAGs) per unit area that are far higher than traditional feedstocks due to their rapid growth. Dunaliella is particularly advantageous as a feedstock because it is currently commercially mass cultured, thrives in salt water, and has no cell wall. Fourteen strains of Dunaliella have been investigated for growth rates and lipid production in mass culture and tested for enhanced lipid production under a range of environmental stressors including salinity, pH, nitrogen and phosphorus limitation, and light regime. The nuclear genome has been sequenced for four of these strains, with the objective of increasing carbon flux through genetic engineering. Electroflocculation followed by osmotic membrane rupturing may be a very energy and cost efficient means of harvesting the lipid bodies from Dunaliella. A technically feasible and scalable thermo-catalytic process to convert the lipids into replacements for liquid transportation fuels has been developed. The lipids were converted into long-chain alkanes through continuous thermal hydrolysis followed by fed-batch thermo-catalytic decarboxylation. These alkanes can be reformed into renewable diesel via conventional catalytic hydrocarbon isomerization reactions to improve cold flow properties, if desired. © 2013 American Institute of Chemical Engineers Environ Prog, 32: 916-925, 2013 Copyright © 2013 American Institute of Chemical Engineers Environ Prog.

Gluconeogenesis in Leishmania mexicana

Science.gov (United States)

Rodriguez-Contreras, Dayana; Hamilton, Nicklas

2014-01-01

Gluconeogenesis is an active pathway in Leishmania amastigotes and is essential for their survival within the mammalian cells. However, our knowledge about this pathway in trypanosomatids is very limited. We investigated the role of glycerol kinase (GK), phosphoenolpyruvate carboxykinase (PEPCK), and pyruvate phosphate dikinase (PPDK) in gluconeogenesis by generating the respective Leishmania mexicana Δgk, Δpepck, and Δppdk null mutants. Our results demonstrated that indeed GK, PEPCK, and PPDK are key players in the gluconeogenesis pathway in Leishmania, although stage-specific differences in their contribution to this pathway were found. GK participates in the entry of glycerol in promastigotes and amastigotes; PEPCK participates in the entry of aspartate in promastigotes, and PPDK is involved in the entry of alanine in amastigotes. Furthermore, the majority of alanine enters into the pathway via decarboxylation of pyruvate in promastigotes, whereas pathway redundancy is suggested for the entry of aspartate in amastigotes. Interestingly, we also found that l-lactate, an abundant glucogenic precursor in mammals, was used by Leishmania amastigotes to synthesize mannogen, entering the pathway through PPDK. On the basis of these new results, we propose a revision in the current model of gluconeogenesis in Leishmania, emphasizing the differences between amastigotes and promastigotes. This work underlines the importance of studying the trypanosomatid intracellular life cycle stages to gain a better understanding of the pathologies caused in humans. PMID:25288791

Cytochemical identification of endocrine thymus of chicken in relation to aging

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Uma Kanta Mishra

2013-09-01

Full Text Available Age related cytochemical changes of thymic endocrine cells were studied in 78 day old chicks at five day interval to age of day 60 employing a panel of cytochemical stains. Methenamine silver revealed cell morphology including cell processes distinctly while diamine silver revealed a stronger argentaffinity in these cells. The cells had greater affinity for diamine silver compared to methenamine silver (Argentaffin, followed by formaldehyde induced auto- fluorescence, argyrophilia, lead hematoxylin and HCl-toluidine. The chromaffin reaction was the weakest. Cytochemically, three different endocrine cell populations i.e. argentaffin cells, argyrophilic cells and amine precursor uptake and decarboxylation series (APUD/chromaffin cells, formed the resident population of thymic endocrine cells. Occurrence of numerous serotonin storing cells, moderately frequent APUD cells, and fewer chromaffin as well as mast cells suggests for a conspicuous reservoir of amine storing cells in thymus. Morphologically argentaffin cells were of four types i.e. the peripherally granulated spherical cells (Type-I, densely granulated oval cells (Type-II, pyramidal argentaffin cells (Type-III and diffusely granulated elongated cells (Type-IV. The type-II argentaffin cells were most frequent in the medulla followed by the type-I cells and the type-III cells. The type-IV cells were least in frequency. The age related changes in frequency of these cells are also discussed.

Improving the productivity of S-adenosyl-l-methionine by metabolic engineering in an industrial Saccharomyces cerevisiae strain.

Science.gov (United States)

Zhao, Weijun; Hang, Baojian; Zhu, Xiangcheng; Wang, Ri; Shen, Minjie; Huang, Lei; Xu, Zhinan

2016-10-20

S-Adenosyl-l-methionine (SAM) is an important metabolite having prominent roles in treating various diseases. In order to improve the production of SAM, the regulation of three metabolic pathways involved in SAM biosynthesis were investigated in an industrial yeast strain ZJU001. GLC3 encoded glycogen-branching enzyme (GBE), SPE2 encoded SAM decarboxylase, as well as ERG4 and ERG6 encoded key enzymes in ergosterol biosynthesis, were knocked out in ZJU001 accordingly. The results indicated that blocking of either glycogen pathway or SAM decarboxylation pathway could improve the SAM accumulation significantly in ZJU001, while single disruption of either ERG4 or ERG6 gene had no obvious effect on SAM production. Moreover, the double mutant ZJU001-GS with deletion of both GLC3 and SPE2 genes was also constructed, which showed further improvement of SAM accumulation. Finally, SAM2 was overexpressed in ZJU001-GS to give the best SAM-producing recombinant strain ZJU001-GS-SAM2, in which 12.47g/L SAM was produced by following our developed pseudo-exponential fed-batch cultivation strategy, about 81.0% increase comparing to its parent strain ZJU001. The present work laid a solid base for large-scale SAM production with the industrial Saccharomyces cerevisiae strain. Copyright © 2016 Elsevier B.V. All rights reserved.

Structural analysis of Bacillus pumilus phenolic acid decarboxylase, a lipocalin-fold enzyme

International Nuclear Information System (INIS)

Matte, Allan; Grosse, Stephan; Bergeron, Hélène; Abokitse, Kofi; Lau, Peter C. K.

2010-01-01

The crystal structure of phenolic acid decarboxylase from B. pumilus strain UI-670 has been determined and refined at 1.69 Å resolution. The enzyme is a dimer, with each subunit adopting a β-barrel structure belonging to the lipocalin fold. The decarboxylation of phenolic acids, including ferulic and p-coumaric acids, to their corresponding vinyl derivatives is of importance in the flavouring and polymer industries. Here, the crystal structure of phenolic acid decarboxylase (PAD) from Bacillus pumilus strain UI-670 is reported. The enzyme is a 161-residue polypeptide that forms dimers both in the crystal and in solution. The structure of PAD as determined by X-ray crystallography revealed a β-barrel structure and two α-helices, with a cleft formed at one edge of the barrel. The PAD structure resembles those of the lipocalin-fold proteins, which often bind hydrophobic ligands. Superposition of structurally related proteins bound to their cognate ligands shows that they and PAD bind their ligands in a conserved location within the β-barrel. Analysis of the residue-conservation pattern for PAD-related sequences mapped onto the PAD structure reveals that the conservation mainly includes residues found within the hydrophobic core of the protein, defining a common lipocalin-like fold for this enzyme family. A narrow cleft containing several conserved amino acids was observed as a structural feature and a potential ligand-binding site

Evolution of the key alkaloid enzyme putrescine N-methyltransferase from spermidine synthase.

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Anne eJunker

2013-07-01

Full Text Available Putrescine N-methyltransferases (PMTs are the first specific enzymes of the biosynthesis of nicotine and tropane alkaloids. PMTs transfer a methyl group onto the diamine putrescine from S-adenosyl-L-methionine (SAM as coenzyme. PMT proteins have presumably evolved from spermidine synthases (SPDSs, which are ubiquitous enzymes of polyamine metabolism. SPDS use decarboxylated SAM as coenzyme to transfer an aminopropyl group onto putrescine. In an attempt to identify possible and necessary steps in the evolution of PMT from SPDS, homology based modeling of Datura stramonium SPDS1 and PMT was employed to gain deeper insight in the preferred binding positions and conformations of the substrate and the alternative coenzymes. Based on predictions of amino acids responsible for the change of enzyme specificities, sites of mutagenesis were derived. PMT activity was generated in Datura stramonium SPDS1 after few amino acid exchanges. Concordantly, Arabidopsis thaliana SPDS1 was mutated and yielded enzymes with both, PMT and SPDS activities. Kinetic parameters were measured for enzymatic characterization. The switch from aminopropyl to methyl transfer depends on conformational changes of the methionine part of the coenzyme in the binding cavity of the enzyme. The rapid generation of PMT activity in SPDS proteins and the wide-spread occurrence of putative products of N-methylputrescine suggest that PMT activity is present frequently in the plant kingdom.