β-lactam antibiotics.: Spectroscopy and molecular orbital (MO) calculations -: Part I:: IR studies of complexation in penicillin-transition metal ion systems and semi-empirical PM3 calculations on simple model compounds

被引:30
作者
Kupka, T
机构
[1] Silesian Univ, Inst Phys, Dept Med Phys, PL-40997 Katowice, Poland
[2] Polish Acad Sci, Inst Polymer Chem, PL-41800 Zabrze, Poland
关键词
beta-lactam antibiotics; metal ion complexation; IR; PM3 semi-empirical calculations;
D O I
10.1016/S1386-1425(97)00146-7
中图分类号
O433 [光谱学];
学科分类号
0703 ; 070302 ;
摘要
IR studies were preformed to determine possible transition metal ion binding sites of penicillin. the observed changes in spectral position and shape of characteristic IR bands of cloxacillin in the presence of transition metal ions (both in solutions and in the solid state) indicate formation of M-L complexes with engagement of -COO- and/or -CONH- functional groups. The small shift of nu(C=O) towards higher frequencies rules out direct M-L interaction via beta-lactam carbonyl. PM3 calculations on simple model compounds (substituted formamide, cyclic ketones, lactams and substituted monocyclic beta-lactams) have been performed. All structures were fully optimized and the calculated bond lengths, angles, heats of formation and C=O stretching frequencies were discussed to determine the beta-lactam binding sites and to explain its susceptibility towards nucleophilic attack (hydrolysis in vitro) and biological activity. The relative changes of calculated values were critically compared with available experimental data and same correlation between structural parameters and in vivo activity was shown. (C) 1997 Elsevier Science B.V.
引用
收藏
页码:2649 / 2658
页数:10
相关论文
共 41 条
[1]  
Bellamy L.J., 1975, INFRA RED SPECTRA CO
[3]  
BOYD DB, 1982, CHEM BIOL BETA LACTA, V1
[4]  
BOYD DB, 1980, J AM CHEM SOC, V102, P3902
[5]  
BOYD DB, 1977, INT J QUANTUM CHEM, V4, P161
[6]   APPLICATION OF H-1 NUCLEAR-MAGNETIC-RESONANCE SPECTROSCOPY TO THE ANALYSIS OF BETA-LACTAM ANTIBIOTICS AND THEIR COMMON DEGRADATION PRODUCTS [J].
BRANCH, SK ;
CASY, AF ;
OMINDE, EMA .
JOURNAL OF PHARMACEUTICAL AND BIOMEDICAL ANALYSIS, 1987, 5 (02) :73-103
[7]   MICROWAVE SPECTRUM AND MOLECULAR STRUCTURE OF FORMAMIDE [J].
COSTAIN, CC ;
DOWLING, JM .
JOURNAL OF CHEMICAL PHYSICS, 1960, 32 (01) :158-165
[8]   THE DEVELOPMENT AND USE OF QUANTUM-MECHANICAL MOLECULAR-MODELS .76. AM1 - A NEW GENERAL-PURPOSE QUANTUM-MECHANICAL MOLECULAR-MODEL [J].
DEWAR, MJS ;
ZOEBISCH, EG ;
HEALY, EF ;
STEWART, JJP .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (13) :3902-3909
[9]   A NON-EMPIRICAL STUDY OF HYDROGEN BONDING IN DIMER OF FORMAMIDE [J].
DREYFUS, M ;
MAIGRET, B ;
PULLMAN, A .
THEORETICA CHIMICA ACTA, 1970, 17 (02) :109-&
[10]   METAL-ION COORDINATION BY SOME PENICILLIN AND CEPHALOSPORIN ANTIBIOTICS [J].
FAZAKERLEY, GV ;
JACKSON, GE .
JOURNAL OF INORGANIC & NUCLEAR CHEMISTRY, 1975, 37 (11) :2371-2375