The Stability of Cα Peptide Radicals: Why Glycyl Radical Enzymes?

被引：37

作者：

Hioe, Johnny ^{[1
]}

Savasci, Goekcen ^{[1
]}

Brand, Harald ^{[1
]}

Zipse, Hendrik ^{[1
]}

机构：

[1] LMU Munchen, Dept Chem, D-81377 Munich, Germany

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2011年 / 17卷 / 13期

关键词：

ab initio calculations; conformational space; peptides; radicals; thermodynamic stability; BOND-DISSOCIATION ENERGIES; AB-INITIO; CONFORMATIONAL-ANALYSIS; MOLECULAR-STRUCTURES; AMINO-ACIDS; GEOMETRIES; REARRANGEMENTS; DIPEPTIDE; NHME; ALA;

D O I：

10.1002/chem.201002620

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The conformational space of dipeptide models derived from glycine, alanine, phenylalanine, proline, tyrosine, and cysteine has been searched extensively and compared with the corresponding C-alpha dipeptide radicals at the (MP2)-RAD level of theory. The results indicate that the (least-substituted) glycine dipeptide radical is the thermochemically most stable of these species. Analysis of the structural parameters indicates that this is due to repulsive interactions between the C-alpha substituents and peptide units in the radical. A comparison of the conformational preferences of dipeptide radicals and their closed-shell parents also indicates that radical stability is a strongly conformation-dependent property.

引用

页码：3781 / 3789

页数：9

共 45 条

[1] Gaussian-3 theory using density functional geometries and zero-point energies
Baboul, AG
Curtiss, LA
Redfern, PC
Raghavachari, K
[J]. JOURNAL OF CHEMICAL PHYSICS, 1999, 110 (16) : 7650 - 7657
[2] Radical carbon skeleton rearrangements:: Catalysis by coenzyme B12-dependent mutases
Banerjee, R
[J]. CHEMICAL REVIEWS, 2003, 103 (06) : 2083 - 2094
[3] Inhibition of peptidylglycine α-amidating monooxygenase by exploitation of factors affecting the stability and ease of formation of glycyl radicals
Barratt, BJW
Easton, CJ
Henry, DJ
Li, IHW
Radom, L
Simpson, JS
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (41) : 13306 - 13311
[4] Conformational analysis of small peptides of the type Ac-X-NHMe, where X = Gly, Ala, Aib and Cage
Bisetty, K
Catalan, JG
Kruger, H
Perez, JJ
[J]. JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM, 2005, 731 (1-3): : 127 - 137
[5] Radical enzymes in anaerobes
Buckel, Wolfgang
Golding, Bernard T.
[J]. ANNUAL REVIEW OF MICROBIOLOGY, 2006, 60 : 27 - 49
[6] COOTE ML, 2010, WILEY SERIES REACTIV, V3, P83
[7] Cornell WD, 1997, J MOL STRUC-THEOCHEM, V392, P101
[8] Strategic use of amino acid N-substituents to limit α-carbon-centered radical formation and consequent loss of stereochemical integrity
Croft, AK
Easton, CJ
Kociuba, K
Radom, L
[J]. TETRAHEDRON-ASYMMETRY, 2003, 14 (19) : 2919 - 2926
[9] Design of radical-resistant amino acid residues: A combined theoretical and experimental investigation
Croft, AK
Easton, CJ
Radom, L
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (14) : 4119 - 4124
[10] Free-radical reactions in the synthesis of alpha-amino acids and derivatives
Easton, CJ
[J]. CHEMICAL REVIEWS, 1997, 97 (01) : 53 - 82

← 1 2 3 4 5 →