用新的路径定位指数和神经网络研究多溴联苯醚理化性质

doi:10.3969/j.issn.0438-1157.2014.04.003

摘要/Abstract

摘要： 基于溴取代基及共轭母体的结构特征，定义一种新的路径定位指数^mP，并计算了209种多溴联苯醚分子的电性拓扑状态指数E₉和电性距离矢量M₂₆，这3个指数对有机污染物呈现出良好的结构选择性。采用多元回归方法对多溴联苯醚（PBDEs）的色谱保留时间（t_R）、正辛醇/空气分配系数（lgK_OA）、超冷流体蒸气压（lgP_L）及其毒性等性质与分子结构指数进行关联，建立的4个预测模型的相关系数分别达到0.991、0.997、0.998和0.904，标准偏差分别为0.031、0.104、0.100和0.358。将3个指数作为BP神经网络的输入层神经元，采用不同的网络体系结构，获得了令人满意的预测理化性质的神经网络模型，所得结果明显优于多元回归方法，结果显示多溴联苯醚的理化性质与⁰P、E₉和M₂₆具有良好的非线性关系。

关键词: 多溴联苯醚, 神经网络, 算法, 模型, 电性拓扑状态指数, 路径定位指数, 理化性质

Abstract: Based on the structure characteristics of bromine substituents and conjugated matrix, a new path location index ^mP is defined. The electrotopological state indices (E₉) and electronegativity distance vector (M₂₆) of 209 polybrominated diphenyl ethers (PBDEs) are calculated. It shows that ^mP, E₉ and M₂₆ have good structural selectivity for organic pollutant. Then, the multiple regression method is used to establish relationships between the molecular structure of PBDEs and four parameters: gas-chromatographic relative retention time (t_R), n-octanol pair partition coefficient (lgK_OA), supercooled liquid vapour pressures (lgP_L) and toxicity (lgI). With the four predictive models, the correlation coefficients are 0.991, 0.997, 0.998 and 0.904 with the standard deviation of 0.031, 0.104, 0.100 and 0.358, respectively. Three structural parameters are used as the input neurons of the BP neural network and different network architectures to get several satisfying neural network models for predicting t_R, lgK_OA, and lgP_L. The results are better than those by the multiple regression method, which shows significant nonlinear relationships between the physicochemical properties of PBDEs and the three structural parameters.

Key words: polybrominated diphenyl ethers, neural networks, algorithm, model, electrotopological state indices, path location index, physicochemical property

中图分类号:

X131
O625

堵锡华. 用新的路径定位指数和神经网络研究多溴联苯醚理化性质[J]. CIESC Journal, 2014, 65(4): 1169-1178.

DU Xihua. Physicochemical property of polybrominated diphenyl ethers by new path location index and neural network[J]. , 2014, 65(4): 1169-1178.

参考文献

[1] Li Xiaolin, Ye Li, Wang Xiaoxiang, et al. Combined 3D-QSAR, molecular docking and molecular dynamics study on thyroid hormone activity of hydroxylated polybrominated diphenyl ethers to thyroid receptors β[J]. Toxicology and Applied Pharmacology，2012，265(3): 300-307
[2] Liang Shuxuan(梁淑轩)，Gao Hongxia(高红霞)，Li Liyong(李立勇). Research progress on the investigation of toxicology of polybrominated diphenyl ethers[J]. Journal of Toxicology (毒理学杂志)，2010，24(1): 76-79
[3] Danon-Schaffer M N，Mahecha-Botero A，Grace J R，Ikonomou M. Mass balance evaluation of polybrominated diphenyl ethers in landfill leachate and potential for transfer from e-waste[J]. Science of the Total Environment，2013，461/462: 290-301
[4] Xu Huiying，Zou Jianwei，Hu Guixiang，Wang Wei. QSPR/QSAR models for prediction of the physico-chemical properties and biological activity of polychlorinated diphenyl ethers (PCDEs)[J]. Chemosphere，2010，80(6): 665-670
[5] Gu Chenggang，Ju Xuehai，Jiang Xin，Yu Kai，Yang Shaogui，Sun Cheng. Improved 3D-QSAR analyzes for the predictive toxicology of polybrominated diphenyl ethers with CoMFA/CoMSIA and DFT[J]. Ecotoxicology and Environmental Safety，2010，73(6): 1470-1479
[6] Xiao Fangzhu(肖方竹)，Peng Guowen(彭国文)，Nie Changming(聂长明)，Yang Shengyuan(杨胜园). Prediction of thermodynamic properties of PCDEs with quantum topological indices[J]. CIESC Journal (化工学报)，2011，62(7): 1808-1816
[7] Liu Wanqiang(刘万强)，Cao Chenzhong(曹晨忠). Quantitative structure-property relationship of normal boiling point of aliphatic oxygen-containing organic compounds[J]. CIESC Journal (化工学报)，2012，63(12): 3739-3746
[8] Zhang Ji(张骥)，Shen Peng(申鹏)，Lu Tao(陆涛)，Yu Danni（余丹妮），Li Hui（李卉），Yang Guozhong（杨国忠）. Theoretical studies on quantitative structure-activity relationship and structural modification for the inhibition of MMP-9 by flavonoids[J]. Acta Chimica Sinica(化学学报)，2011，69(4): 383-392
[9] Su Limin, Zhang Xujia, Yuan Xing, Zhao Yuanhui, Zhang Dongmei, Qin Weichao. Evaluation of joint toxicity of nitroaromatic compounds and copper to photobacterium phosphoreum and QSAR analysis[J]. Journal of Hazardous Materials，2012，241/242: 450-455
[10] Kar S，Roy K. QSAR modeling of toxicity of diverse organic chemicals to Daphnia magna using 2D and 3D descriptors[J]. Journal of Hazardous Materials，2010，177(1/2/3): 344-351
[11] Xu Huiying(许惠英), Zhang Jianying(张建英), Wang Yanhua(王艳花), Li Li(李立). QSPR studies on the physicochemical properties of polybrominated diphenyl ethers using theoretical descriptors derived from electrostatic potentials on molecular surface[J]. Environmental Science(环境科学)，2008，29(2) 398-408
[12] Niu Junfeng，Shen Zhenyao，Yang Zhifeng，Long Xingxing，Yu Gang. Quantitative structure-property relationships on photodegradation of polybrominated diphenyl ethers[J]. Chemosphere，2006，64(4): 658-665
[13] Zhang Jin(张瑾)，Dai Youyuan(戴猷元). Quantitative structure-property relationship study on physicochemical properties of polychlorinated diphenyl ethers and polybrominated diphenyl ethers[J]. Chemical Engineering(China)（化学工程），2012，40(9): 42-47
[14] Li Linnan, Xie Shaodong, Cai Hao, Bai Xuetao, Xue Zhao. Quantitative structure-property relationships for octanol-water partition coefficients of polybrominated diphenyl ethers[J]. Chemosphere，2008，72(10): 1602-1606
[15] Chetouani Y. A neural network approach for the real-time detection of faults[J]. Stochastic Environmental Research and Risk Assessment，2008，22(3): 339-349
[16] Nuovo A G D，Nuovo S D，Buono S. Intelligent quotient estimation of mental retarded people from different psychometric instruments using artificial neural networks[J]. Artificial Intelligence in Medicine，2012，54(2): 135-145
[17] Prado-Prado F J，García-Mera X，González-Díaz H. Multi-target spectral moment QSAR versus ANN for antiparasitic drugs against different parasite species[J]. Bioorganic & Medicinal Chemistry，2010，18(6): 2225-2231
[18] Feng Changjun(冯长君)，Mu Lailong(沐来龙)，Yang Weihua(杨伟华)，Cai Keying(蔡可迎). Research on the bioconcentration factors of organic pollutants with topological indices and artificial neural network[J]. Acta Chimica Sinica(化学学报)，2008，66(19): 2093-2098
[19] D’Archivio A A，Giannitto A，Maggi M A. Cross-column prediction of gas-chromatographic retention of polybrominated diphenyl ethers[J]. Journal of Chromatography A，2013，1298: 118-131
[20] Du Xihua(堵锡华). QSPR research of thermodynamic properties of polychlorinated biphenyl[J]. Journal of Chemical Industry and Engineering（China）(化工学报)，2007，58(10): 2432-2436
[21] Du Xihua(堵锡华). QSPR study on thermodynamic properties of polybrominated dibenzofurans and polybrominated dibenzothiophenes [J]. CIESC Journal (化工学报)，2010，61(12): 3059-3066
[22] Wang Zunyao，Zeng Xiaolan，Zhai Zhicai. Prediction of supercooled liquid vapor pressures and n-octanol/air partition coefficients for polybrominated diphenyl ethers by means of molecular descriptors from DFT method[J]. Science of the Total Environment，2008，389(2/3): 296-305
[23] Chen G S，Konstantinov A D，Chittim B G，Joyce E M，Bols N C，Bunce N J. Synthesis of polybrominated diphenyl ethers and their capacity to induce CYP1A by the Ah receptor mediated pathway[J]. Environmental Science & Technology , 2001, 35(18): 37490-3756
[24] Hall L H, Kier L B. Electrotopological state indices for atom types: a novel combination of electronic, topological and valence state information [J]. Journal of Chemical Information and Modeling, 1995, 35(6): 1039-1045
[25] Hall L H, Kier L B, Brown B B. Molecular similarity based on novel atom- type electrotopological state indices[J]. Journal of Chemical Information and Modeling，1995，35(6): 1074-1080
[26] Zhou Lulu(周璐璐), Jiang Juncheng(蒋军成), Pan Yong(潘勇), Wang Rui(王睿). Prediction of the electrostatic sensitivity of nitro compounds with electrotopological state indices[J]. Chinese Journal of Energetic Materials(含能材料)，2011，19(6): 616-620
[27] Liu Shushen(刘树深)，Liu Yan(刘堰)，Li Zhiliang(李志良)，Cai Shaoxi(蔡绍皙). A novel molecular electronegativity – distance vector(MEDV)[J]. Acta Chimica Sinica(化学学报)，2000，58(11): 1353-1357
[28] Zeng X，Freeman P K，Vasilev Y V，Voinov V G， Simonich S L， Barofsky D F．Theoretical calculation of thermodynamic properties of polybrominated diphenyl ethers[J]．Journal of Chemical & Engineering Data，2005，50(5): 1548-1556
[29] Xu Lu(许禄), Shao Xueguang(邵学广). Methods of Chemometrics（化学计量学方法）[M]. Beijing：Science Press, 2004: 441