Computational Studies on the Decarboxylation of 2-(1-Carboxy-1-hydroxyethyl)-3,4-dimethylthiazolium Dipolar Ion, an Analog of the Complex of Pyruvic Acid and Coenzyme of Pyruvate Decarboxylase

Y. Nakajima, Y. Sakagishi, M. Shiibashi, Y. Suzuki, H. Kato

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

We have obtained the optimized geometrical structure of 2-(1-carboxy-1-hydroxyethyl)-3,4-dimethylthiazolium dipolar ion and investigated its geometric and electric changes during decarboxylation process by the MNDO-PM3 method, a molecular orbital method. The salient features of the optimized structure are that the dihedral angle of C4-C1-C2-S3 is 5.4° and the distance between thiazolium S3 and carboxyl O6 is about 1.8Å (the bond order between S3 and O6 is about 0.4). The lowest energy decarboxylation profile is the following process. First the dihedral angle of C4-C1-C2-S3 becomes about 90°, then the distance between C1-C2 increases while the dihedral angle holds about 90°, and finally the C1-C2 bond disappears. The most remarkable change caused by the 90° rotation is the disappearance of the S3-O6 bond, and this disappearance causes electric changes that prompt the decarboxylation.

Original languageEnglish
Pages (from-to)449-454
Number of pages6
JournalBiochemical and Biophysical Research Communications
Volume195
Issue number1
DOIs
Publication statusPublished - 1993 Aug 31

Fingerprint

Pyruvate Decarboxylase
Decarboxylation
Coenzymes
Dihedral angle
Pyruvic Acid
Ions
Molecular orbitals

ASJC Scopus subject areas

  • Molecular Biology
  • Biophysics
  • Biochemistry

Cite this

Computational Studies on the Decarboxylation of 2-(1-Carboxy-1-hydroxyethyl)-3,4-dimethylthiazolium Dipolar Ion, an Analog of the Complex of Pyruvic Acid and Coenzyme of Pyruvate Decarboxylase. / Nakajima, Y.; Sakagishi, Y.; Shiibashi, M.; Suzuki, Y.; Kato, H.

In: Biochemical and Biophysical Research Communications, Vol. 195, No. 1, 31.08.1993, p. 449-454.

Research output: Contribution to journalArticle

@article{64471a73158e4171803e8263458cf3d8,
title = "Computational Studies on the Decarboxylation of 2-(1-Carboxy-1-hydroxyethyl)-3,4-dimethylthiazolium Dipolar Ion, an Analog of the Complex of Pyruvic Acid and Coenzyme of Pyruvate Decarboxylase",
abstract = "We have obtained the optimized geometrical structure of 2-(1-carboxy-1-hydroxyethyl)-3,4-dimethylthiazolium dipolar ion and investigated its geometric and electric changes during decarboxylation process by the MNDO-PM3 method, a molecular orbital method. The salient features of the optimized structure are that the dihedral angle of C4-C1-C2-S3 is 5.4° and the distance between thiazolium S3 and carboxyl O6 is about 1.8{\AA} (the bond order between S3 and O6 is about 0.4). The lowest energy decarboxylation profile is the following process. First the dihedral angle of C4-C1-C2-S3 becomes about 90°, then the distance between C1-C2 increases while the dihedral angle holds about 90°, and finally the C1-C2 bond disappears. The most remarkable change caused by the 90° rotation is the disappearance of the S3-O6 bond, and this disappearance causes electric changes that prompt the decarboxylation.",
author = "Y. Nakajima and Y. Sakagishi and M. Shiibashi and Y. Suzuki and H. Kato",
year = "1993",
month = "8",
day = "31",
doi = "10.1006/bbrc.1993.2064",
language = "English",
volume = "195",
pages = "449--454",
journal = "Biochemical and Biophysical Research Communications",
issn = "0006-291X",
publisher = "Academic Press Inc.",
number = "1",

}

TY - JOUR

T1 - Computational Studies on the Decarboxylation of 2-(1-Carboxy-1-hydroxyethyl)-3,4-dimethylthiazolium Dipolar Ion, an Analog of the Complex of Pyruvic Acid and Coenzyme of Pyruvate Decarboxylase

AU - Nakajima, Y.

AU - Sakagishi, Y.

AU - Shiibashi, M.

AU - Suzuki, Y.

AU - Kato, H.

PY - 1993/8/31

Y1 - 1993/8/31

N2 - We have obtained the optimized geometrical structure of 2-(1-carboxy-1-hydroxyethyl)-3,4-dimethylthiazolium dipolar ion and investigated its geometric and electric changes during decarboxylation process by the MNDO-PM3 method, a molecular orbital method. The salient features of the optimized structure are that the dihedral angle of C4-C1-C2-S3 is 5.4° and the distance between thiazolium S3 and carboxyl O6 is about 1.8Å (the bond order between S3 and O6 is about 0.4). The lowest energy decarboxylation profile is the following process. First the dihedral angle of C4-C1-C2-S3 becomes about 90°, then the distance between C1-C2 increases while the dihedral angle holds about 90°, and finally the C1-C2 bond disappears. The most remarkable change caused by the 90° rotation is the disappearance of the S3-O6 bond, and this disappearance causes electric changes that prompt the decarboxylation.

AB - We have obtained the optimized geometrical structure of 2-(1-carboxy-1-hydroxyethyl)-3,4-dimethylthiazolium dipolar ion and investigated its geometric and electric changes during decarboxylation process by the MNDO-PM3 method, a molecular orbital method. The salient features of the optimized structure are that the dihedral angle of C4-C1-C2-S3 is 5.4° and the distance between thiazolium S3 and carboxyl O6 is about 1.8Å (the bond order between S3 and O6 is about 0.4). The lowest energy decarboxylation profile is the following process. First the dihedral angle of C4-C1-C2-S3 becomes about 90°, then the distance between C1-C2 increases while the dihedral angle holds about 90°, and finally the C1-C2 bond disappears. The most remarkable change caused by the 90° rotation is the disappearance of the S3-O6 bond, and this disappearance causes electric changes that prompt the decarboxylation.

UR - http://www.scopus.com/inward/record.url?scp=0027227313&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0027227313&partnerID=8YFLogxK

U2 - 10.1006/bbrc.1993.2064

DO - 10.1006/bbrc.1993.2064

M3 - Article

C2 - 8363620

AN - SCOPUS:0027227313

VL - 195

SP - 449

EP - 454

JO - Biochemical and Biophysical Research Communications

JF - Biochemical and Biophysical Research Communications

SN - 0006-291X

IS - 1

ER -