Quantitative structure-property relationships for direct photolysis of polybrominated diphenyl ethers.
Using semiempirical quantum chemical descriptors, by partial least squares (PLS) regression, quantitative structure-property relationships (QSPRs) were established for direct photolysis quantum yields (Phi) and rate constants (k) of polybrominated diphenyl ether congeners dissolved in water/methanol and methanol solutions, respectively, and irradiated by artificial ultraviolet A light. Q(cum)(2), a parameter indicating robustness and predictive abilities of PLS models, for the significant QSPR models is larger than 0.702. The gap of frontier molecular orbital energies (E(LUMO)-E(HOMO)) and the most positive Mulliken atomic charges on a hydrogen atom (q(H+)) are two main molecular structural factors governing the logPhi values. logPhi increases with increasing E(LUMO)-E(HOMO) and q(H+) values. logk is mainly related to bromination degree and pattern which can be characterized by molecular weight (Mw), average molecular polarizability (alpha), and average Mulliken atomic charges on bromine atoms (q(Br)). logk increases with bromination degree (Mw, alpha) and q(Br).
Department of Environmental Science and Technology, Dalian University of Technology, Linggong Road 2, Dalian 116024, People's Republic of China. jwchen@dlut.edu.cn
Jingwen
J
Chen
Degao
D
Wang
Shuanglin
S
Wang
Xianliang
X
Qiao
Liping
L
Huang
D016018:Least-Squares Analysis; D000432:Methanol / Q000737:chemistry; D010647:Phenyl Ethers / Q000528:radiation effects*; D010782:Photolysis; D011075:Polybrominated Biphenyls / Q000528:radiation effects*; D021281:Quantitative Structure-Activity Relationship; D012997:Solvents / Q000737:chemistry; D014466:Ultraviolet Rays; D014867:Water / Q000737:chemistry
D010647:Phenyl Ethers; D011075:Polybrominated Biphenyls; D012997:Solvents; D014867:Water; D000432:Methanol