Reaction mechanism and stereochemistry of
gamma-hexachlorocyclohexane dehydrochlorinase LinA

J 2001

Reaction mechanism and stereochemistry of gamma-hexachlorocyclohexane dehydrochlorinase LinA

TRANTÍREK, Lukáš; Kamila HYNKOVÁ; Yuji NAGATA; Alexey MURZIN; Alena ANSORGOVÁ et al.

Základní údaje

Originální název

Reaction mechanism and stereochemistry of gamma-hexachlorocyclohexane dehydrochlorinase LinA

Autoři

TRANTÍREK, Lukáš; Kamila HYNKOVÁ; Yuji NAGATA; Alexey MURZIN; Alena ANSORGOVÁ; Vladimír SKLENÁŘ a Jiří DAMBORSKÝ

Vydání

Journal of Biological Chemistry, 2001

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10600 1.6 Biological sciences

Stát vydavatele

Spojené státy

Utajení

není předmětem státního či obchodního tajemství

Odkazy

URL

Označené pro přenos do RIV

Ano

Kód RIV

RIV/00216224:14310/01:00004145

Organizační jednotka

Přírodovědecká fakulta

UT WoS

000167474900011

Změněno: 28. 5. 2003 22:04, prof. Mgr. Jiří Damborský, Dr.

Anotace

V originále

g-hexachlorocyclohexane dehydrochlorinase (LinA) catalyses the initial steps in the biotransformation of the important insecticide g-hexachlorocyclohexane (g-HCH) by the soil bacterium Sphingomonas paucimobilis UT26. Stereochemical analysis of the reaction products formed during conversion of g-HCH by LinA was investigated by GC-MS, NMR, CD and molecular modeling. The NMR spectra of 1,3,4,5,6-pentachlorocyclohexene (PCCH) produced from g-HCH using either enzymatic dehydrochlorination or alkaline dehydrochlorination were compared and found to be identical. Both enantiomers present in the racemate of synthetic g-PCCH were converted by LinA, each at a different rate. 1,2,4-trichlorobenzene (1,2,4-TCB) was detected as the only product of the biotransformation of biosynthetic g-PCCH. 1,2,4-TCB and 1,2,3-TCB were identified as the dehydrochlorination products of racemic g-PCCH. d-PCCH was detected as the only product of dehydrochlorination of d-HCH. LinA requires the presence of a 1,2-biaxial HCl pair on a substrate molecule. LinA enantiotopologically differentiates two 1,2-biaxial HCl pairs present on g-HCH and gives rise to a single PCCH enantiomer 1,3(R),4(S),5(S),6(R)-PCCH. Furthermore, LinA enantiomerically differentiates 1,3(S),4(R),5(R),6(S)-PCCH and 1,3(R),4(S),5(S),6(R)-PCCH. The proposed mechanism of enzymatic biotransformation of g-HCH to 1,2,4-TCB by LinA consists of two 1,2-anti conformationally dependent dehydrochlorinations followed by 1,4-anti dehydrochlorination.

Návaznosti

GA203/97/P149, projekt VaV

Název: Studium molekulárních mechanismů biodegradačních reakcí - konstrukce QSBR modelů a proteinové inženýrství dehalogenas

Investor: Grantová agentura ČR, Studium molekulárních mechanismů biodegradačních reakcí - konstrukce QSBR modelů a proteinové inženýrství dehalogenas

LN00A016, projekt VaV

Název: BIOMOLEKULÁRNÍ CENTRUM

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, Biomolekulární centrum

ME 276, projekt VaV

Název: Racionální re-design mikrobiálních enzymů podílejících se na degradaci toxických organických polutantů

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, Racionální re-design mikrobiálních enzymů podílejících se na degradaci toxických organických polutantů

Citovat

TRANTÍREK, Lukáš; Kamila HYNKOVÁ; Yuji NAGATA; Alexey MURZIN; Alena ANSORGOVÁ; Vladimír SKLENÁŘ a Jiří DAMBORSKÝ. Reaction mechanism and stereochemistry of gamma-hexachlorocyclohexane dehydrochlorinase LinA. Journal of Biological Chemistry. 2001, roč. 276, č. 11, s. 7734-7740.

@article{360452,
   author = {Trantírek, Lukáš and Hynková, Kamila and Nagata, Yuji and Murzin, Alexey and Ansorgová, Alena and Sklenář, Vladimír and Damborský, Jiří},
   article_number = {11},
   language = {eng},
   journal = {Journal of Biological Chemistry},
   title = {Reaction mechanism and stereochemistry of gamma-hexachlorocyclohexane dehydrochlorinase LinA},
   url = {http://www.ncbr.chemi.muni.cz/~jiri/ABSTRACTS/jbc01.html},
   volume = {276},
   year = {2001}
}

TY  - JOUR
ID  - 360452
AU  - Trantírek, Lukáš - Hynková, Kamila - Nagata, Yuji - Murzin, Alexey - Ansorgová, Alena - Sklenář, Vladimír - Damborský, Jiří
PY  - 2001
TI  - Reaction mechanism and stereochemistry of gamma-hexachlorocyclohexane dehydrochlorinase LinA
JF  - Journal of Biological Chemistry
VL  - 276
IS  - 11
SP  - 7734
EP  - 7734
UR  - http://www.ncbr.chemi.muni.cz/~jiri/ABSTRACTS/jbc01.html
N2  - g-hexachlorocyclohexane dehydrochlorinase (LinA) catalyses the initial steps in the biotransformation of the important insecticide g-hexachlorocyclohexane (g-HCH) by the soil bacterium Sphingomonas paucimobilis UT26. Stereochemical analysis of the reaction products formed during conversion of g-HCH by LinA was investigated by GC-MS, NMR, CD and molecular modeling. The NMR spectra of 1,3,4,5,6-pentachlorocyclohexene (PCCH) produced from g-HCH using either enzymatic dehydrochlorination or alkaline dehydrochlorination were compared and found to be identical. Both enantiomers present in the racemate of synthetic g-PCCH were converted by LinA, each at a different rate. 1,2,4-trichlorobenzene (1,2,4-TCB) was detected as the only product of the biotransformation of biosynthetic g-PCCH. 1,2,4-TCB and 1,2,3-TCB were identified as the dehydrochlorination products of racemic g-PCCH. d-PCCH was detected as the only product of dehydrochlorination of d-HCH. LinA requires the presence of a 1,2-biaxial HCl pair on a substrate molecule. LinA enantiotopologically differentiates two 1,2-biaxial HCl pairs present on g-HCH and gives rise to a single PCCH enantiomer 1,3(R),4(S),5(S),6(R)-PCCH. Furthermore, LinA enantiomerically differentiates 1,3(S),4(R),5(R),6(S)-PCCH and 1,3(R),4(S),5(S),6(R)-PCCH. The proposed mechanism of enzymatic biotransformation of g-HCH to 1,2,4-TCB by LinA consists of two 1,2-anti conformationally dependent dehydrochlorinations followed by 1,4-anti dehydrochlorination.
ER  -

TRANTÍREK, Lukáš; Kamila HYNKOVÁ; Yuji NAGATA; Alexey MURZIN; Alena ANSORGOVÁ; Vladimír SKLENÁŘ a Jiří DAMBORSKÝ. Reaction mechanism and stereochemistry of gamma-hexachlorocyclohexane dehydrochlorinase LinA. \textit{Journal of Biological Chemistry}. 2001, roč.~276, č.~11, s.~7734-7740.

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