• Title/Summary/Keyword: Decarboxylation

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Structural determination of triterpenic acids in Prunellae Spica by fast atom bombardment tandem mass spectrometry (하고초의 생리활성 성분 Triterpenic Acids의 FAB-MS를 이용한 구조 규명)

  • Ahn, Young Min;Lee, Kang Ro;Hong, Jongki
    • Analytical Science and Technology
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    • v.21 no.4
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    • pp.245-258
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    • 2008
  • Five triterpenic acids as marker compounds were extracted and isolated from Prunellae Spica by column chromatography and reversed-phase high-performance liquid chromatography (HPLC), and their purity was determinated by HPLC (purity ${\geq}90%$). Molecular weight and elemental compositions of the five marker compounds were determined by fast atom bombardment high-resolution mass spectrometry (FAB-HRMS). The structural determination of the five marker compounds was carried out fast atom bombardment collision-induced dissociation tandem mass spectrometry (FAB-CID-MS/MS). The collision-induced dissociation (CID) of protonated molecules $[M+H]^+$ and deprotonated molecules $[M-H]^-$ produced diverse product ions due mainly to retro Diels-Alder reaction (RDA), dehydration and decarboxylation. Moreover, the CID-MS/MS spectra of the $[M-H]^-$ ions were observed charge-remote fragmentation (CRF) patterns. On the basis of interpretation of CID-MS/MS spectra, structural elucidation of triterpenic acids isolated from Prunellae Spica was clearly performed.

Synthesis of 2,2'-Dipyrryl Ketones from Pyrrole-2-carboxylic Acids with Trifluoroacetic Anhydride

  • Kim, Se Hee;Lim, Jin Woo;Yu, Jin;Kim, Jae Nyoung
    • Bulletin of the Korean Chemical Society
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    • v.34 no.9
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    • pp.2604-2608
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    • 2013
  • An efficient synthesis of 2,2'-dipyrryl ketones has been carried out from pyrrole-2-carboxylic acids using trifluoroacetic anhydride (TFAA). Simultaneous generation of both mixed anhydride and 2-unsubstituted pyrrole, via facile decarboxylation with in-situ generated TFA, made their cross reaction (intermolecular Friedel-Crafts acylation) possible and efficient.

Synthesis of $(\pm)-\alpha-Hydroxy-\alpha$-(p-Chlorobiphenyl)Acetic Acid and its Resolution ($(\pm)-\alpha-Hydroxy-\alpha$-(p-Chlorobiphenyl)acetic acid 합성과 분할)

  • 권순경
    • YAKHAK HOEJI
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    • v.39 no.4
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    • pp.433-437
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    • 1995
  • Optically pure(-)-and (+)-$\alpha$-hydroxy-$\alpha$-(p-chlorobiphenyl)acetic acids were prepared. The racemate was synthesized through three steps. By condensation of p-cnorobiphenyl with diethyl ketomalonate in the presence of SnCl$_{4}$, diethyl $\alpha$-hydroxy-$\alpha$-(p-chlorobiphenyl)malonate (1) was formed and subsequently ($\pm$)-$\alpha$-hydroxy-$\alpha$-(p-chlorobiphenyl)acetic acid (3) was obtained through hydrolysis and decarboxylation. For the separation of the racemate the classical resolution method, derivatization of a racemate by reaction with an optically pure compound was employed. In this case the optically pure compound were [R]-(+)-$\alpha$-methylbenzylamine and [S]-(-)-$\alpha$-methylbenzylamine. Diastereomeric salts between acids and bases could be easily separated by crystallization in absolute ethanol.

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Bioconversion of Gamma-Aminobutyric Acid from Monosodium Glutamate by Lactobacillus brevis Bmb5

  • Jeong, Anna;Yong, Cheng Chung;Oh, Sejong
    • Journal of Microbiology and Biotechnology
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    • v.29 no.11
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    • pp.1745-1748
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    • 2019
  • Gamma-aminobutyric acid (GABA) plays important roles in host physiology. However, the effects of GABA are greatly restricted due to its low bioavailability in the human body. Here, a high acid-tolerance GABA-producing strain, Lactobacillus brevis Bmb5, was isolated from kimchi. Bmb5 converted glutamate to GABA (7.23 ± 0.68 ㎍/μl) at a rate of 72.3%. The expression of gadB gene, encoding the enzyme involved in the decarboxylation of glutamate to GABA, was decreased upon incubation. Our findings indicate GABA production in Bmb5 is not directly correlated with gadB gene expression, providing new insight into the mechanisms underlying GABA production in Lactobacillus.

Modulation of Branched-Chain Amino Acid Metaolism by Exercise in Rats

  • Kim, Hyun-Sook
    • Journal of Nutrition and Health
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    • v.27 no.9
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    • pp.892-900
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    • 1994
  • A variety of important roles for branched-chain amino acids in metabolic regulation has been suggested. Branched-chain $\alpha$-keto acid dehydrogenase(BCKAD) complex is a rate limiting enzyme in branched-chain amino acid metabolism. The purpose of this study was to examine the effects of exercise on the activity and activity state of branched-chain $\alpha$-keto acid dehydrogenase in rat hert and liver thssues. Forty-eight Sprague-Dawley rats were assigned into three experimental groups : sedentary control, exercised, or exercised-rested. Submaximal exercise(running) for two hours significantly increased basal activity without a change in total activity in both tissues, with a concomitiant increase in activity state of the enzyme complex. At 10 min post-exercise, heart enzyme activity significantly decreased, though not to the control level, while liver enzyme activity remained unchanged. These data suggested that the exercise-induced increase in branched-chain $\alpha$-keto acid decarboxylation in rat tissues may not be the result of enzyme synthesis, but rather is due to increased activity of the BCKAD.

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Determination of Branched-Chain α-Keto Acid Dehydrogenase Activity in Rat Tissues

  • Kim, Hyun-Sook;Johnson, Wayne A.
    • BMB Reports
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    • v.28 no.1
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    • pp.12-16
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    • 1995
  • The branched-chain ${\alpha}$-keto acid dehydrogenase (BCKAD) complex is a rate limiting enzyme which catalyzes the oxidative decarboxylation of branched-chain ${\alpha}$-keto acids. Numerous studies have suggested that BCKAD is subject to covalent modification in vitro via phosphorylation and dephosphorylation, which are catalyzed by a specific kinase and phosphatase, respectively. The biggest difficulty in the assay of BCKAD activity is to arrest the interconversion between the active and inactive forms. BCKAD activity was determined from fresh rat heart and liver tissues using homogenizing and assay buffers containing inhibitors of phosphatase and kinase. The results suggest that a radiochemical assay using ${\alpha}$-keto[1-$^{14}C$]-isovalerate as a substrate for the enzyme can be applied as a reliable method to determine in vitro enzyme activity with arrested interconversion between the active and inactive forms of the BCKAD complex.

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Single Electron Transfer Promoted Photocyclization Reactions of ($\omega$-Phthalimidoalkylthio) acetic Acids

  • Yoon, Ung-Chan;Lee, Sang-Jin;Oh, Sun-Wha;Cho, Dae-Won
    • Journal of Photoscience
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    • v.8 no.3_4
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    • pp.99-104
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    • 2001
  • Studies have been conducted to explore single electron transfer (SET) promoted photocyclization reactions of ($\omega$-phthalimidoalkylthio)acetic acids (alkyl=ethyl, n-propyl, n-butyl, n -hexyl and n-nonyl). Photocyclizations occur in methanol in modest yields to produce cyclized products in which phthalimide carbonyl carbon is bonded to the carbon of side chain in place of the carboxylic group. The initially formed cyclized products undergo efficient water eliminations to produce enthiol ethers in secondary ground state reactions.

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Effects and Utilization of GABA (GABA의 효능과 이용)

  • Lim, Sang-Dong;Kim, Kee-Sung
    • Journal of Dairy Science and Biotechnology
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    • v.27 no.1
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    • pp.45-51
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    • 2009
  • $\gamma$-aminobutyric acid (GABA) is a ubiquitous nonprotein amino acid that is produced primarily by $\alpha$-decarboxylation of L-glutamic acid (Glu) catalyzed by the enzyme glutamate decarboxylase (GAD). It is well known as a neurotransmitter that regulates inhibitory neurotransmission in the mammalian central nervous system. In addition, GABA has been proved to be effective for lowering blood pressure in mammals. This paper is intended to provide basic information about GABA, including the functional and biological activity of GABA, GABA production by lactic acid bacteria, and the utilization of GABA in the production of dairy products.

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Identification of Amino Acid Residues in the Carboxyl Terminus Required for Malonate-Responsive Transcriptional Regulation of MatR in Rhizobium leguminosarum bv. trifolii

  • Lee, Hwan-Young;Kim, Yu-Sam
    • BMB Reports
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    • v.34 no.4
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    • pp.305-309
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    • 2001
  • MatR in Rhizobium trifolii is a malonate-responsive transcription factor that regulates the expression of genes, matABC, enabling decarboxylation of malonyl-CoA into acetyl-CoA, synthesis of malonyl-CoA from malonate and CoA, and malonate transport. According to an analysis of the amino acid sequence homology, MatR belongs to the GntR family The proteins of this family have two-domain folds, the N-terminal helix-turn-helix DNA-binding domain and the C-terminal ligand-binding domain. In order to End the malonate binding site and amino acid residues that interact with RNA polymerase, a site-directed mutagenesis was performed. Analysis of the mutant MatR suggests that Arg-160 might be involved in malonate binding, whereas Arg-102 and Arg-174 are critical for the repression activity by interacting with RNA polymerase.

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Oxidative Characteristics of Norditerpene Alkaloids (노르디테르펜 알칼로이드류의 산화적 특성)

  • Song, In-Sung;Kim, Hye-Kyung;Heo, Kyong-Hee;Lee, Chung-Kyu
    • Korean Journal of Pharmacognosy
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    • v.37 no.1 s.144
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    • pp.60-66
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    • 2006
  • Norditerpene alkaloids are the main toxic principles of traditional oriental herb 'chuawu(bu-shi),' which have been used in Chinese materia medica mainly for the treatment of musculoskeletal disorders. They are biosynthesized via cyclization of geranylgeranyl pyrophosphate, incoration of 2-aminoethanol and decarboxylation not via amino acid pathway, and the structural characteristics have tempted several oxidative reactions. In this study various norditerpene alkaloids were subjected to react active manganese dioxide and oxoammonium salt as oxidants. The oxidation was proceeded as dealkylation with aconitine type and dehydrogenations with lycoctonin and heteratisine type.