TY - JOUR
T1 - Mechanism-based quantitative structure-biodegradability relationships for hydrolytic dehalogenation of chloro- and bromo-alkenes
AU - Damborský, Jiří
AU - Berglund, Anders
AU - Kutý, Michal
AU - Ansorgová, Alena
AU - Nagata, Yuji
AU - Sjöström, Michael
PY - 1998/10
Y1 - 1998/10
N2 - Quantitative Structure-Biodegradability Relationships (QSBRs) have been developed for microbial hydrolytic dehalogenation of small chlorinated and brominated alkenes. Two different reaction mechanisms, S(N)2 and S(N)2', were considered for the dehalogenation of small haloalkenes by hydrolytic dehalogenases. Multivariate QSBRs based on quantum-chemically calculated descriptors were used to distinguish between these dehalogenation mechanisms. A QSBR based on atom valence and partial atomic charge on electrophilic site, together with the energy of the lowest unoccupied molecular orbital, molecular weight and dipole moment were able to explain 92% (81% cross-validated) of the quantitative variance in the dehalogenation rates. This QSBR supported a S(N)2 reaction mechanism. This reaction mechanism was also confirmed by GC-MS identification of the reaction products for the compounds which should give discriminating reaction products depending on mechanism. The substrate specificity of hydrolytic dehalogenases for unsaturated halogenated substrates is discussed in the light of chemical structure and properties of the substrate molecules.
AB - Quantitative Structure-Biodegradability Relationships (QSBRs) have been developed for microbial hydrolytic dehalogenation of small chlorinated and brominated alkenes. Two different reaction mechanisms, S(N)2 and S(N)2', were considered for the dehalogenation of small haloalkenes by hydrolytic dehalogenases. Multivariate QSBRs based on quantum-chemically calculated descriptors were used to distinguish between these dehalogenation mechanisms. A QSBR based on atom valence and partial atomic charge on electrophilic site, together with the energy of the lowest unoccupied molecular orbital, molecular weight and dipole moment were able to explain 92% (81% cross-validated) of the quantitative variance in the dehalogenation rates. This QSBR supported a S(N)2 reaction mechanism. This reaction mechanism was also confirmed by GC-MS identification of the reaction products for the compounds which should give discriminating reaction products depending on mechanism. The substrate specificity of hydrolytic dehalogenases for unsaturated halogenated substrates is discussed in the light of chemical structure and properties of the substrate molecules.
KW - Degradation mechanism
KW - Haloalkenes
KW - Hydrolytic dehalogenation
KW - Partial least squares
KW - QSBR
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U2 - 10.1002/(sici)1521-3838(199810)17:05<450::aid-qsar450>3.3.co;2-v
DO - 10.1002/(sici)1521-3838(199810)17:05<450::aid-qsar450>3.3.co;2-v
M3 - Article
AN - SCOPUS:0031723004
VL - 17
SP - 450
EP - 458
JO - Molecular Informatics
JF - Molecular Informatics
SN - 1868-1743
IS - 5
ER -