Chemistry, Centre for Chemical Biology, The University of Newcastle, Callaghan, NSW 2308, Australia.
Org Biomol Chem. 2013 Jul 28;11(28):4646-56. doi: 10.1039/c3ob27168d. Epub 2013 Jun 10.
Effective fragment potential (EFP) molecular modeling approaches have been applied for the first time to the rational design of molecularly imprinted polymers for the group recognition of selected polychlorinated biphenyls (PCBs). EFP calculations were benchmarked using the S22 compound test set and returned energies within 1 kcal mol(-1) of the reported gold standard CCSD(T) approach, but without the computational cost. EFP allowed the rapid identification of trimethylstyrene (TMS) and pentafluorostyrene (PFS) as the functional monomers of choice for the templates (T) 1,2,3,4,5-pentachlorobenzene (4) and for 1,2,3-trichlorobenzne (5) respectively. Ethyleneglycol dimethacrylate was the cross linker (CL) of choice. Using a 1 : 2 : 10 (T : FM : CL) ratio for 4 (TMS as the FM; MIP(4-TMS)) gave imprinting factors (IF) of 2.1; and a 15 : 6 : 29 ratio for 5 gave an IF of 3.66 (PFS as FM; MIP(5-PFS)). MIP(4-TMS) and MIP(5-PFS) showed low levels recognition for non-chlorinated templates with IF values ranging of 1.05, 1.17 and 1.13, 1.54 for toluene (14) and 2,6-dimethylaniline (12) respectively. Higher levels of recognition were observed for the chlorinated analogues 1,3,5-trichlorobenzene (11) and 2,4,6-trichloroaniline (12) with IF values of 1.20, 1.64 and 1.89, 2.66 for MIP(4-TMS) and MIP(5-PFS) respectively suggesting these MIPs were suitable for fragment imprinting of PCBs. Fragment imprinting of 2,2',3,5'-tetrachlorobiphenyl (15), 2,3,3',4,4'-pentachlorobiphenyl (16) and 2,2',3,3',4,5,6'-heptachlorobiphenyl (17) with MIP(4-TMS) gave IF values of 1.38, 1.38 and 1.41 respectively. MIP(5-PFS) performed significantly better with IF values of 6.57, 3.46 and 5.80 for 15-17 respectively. Moreover MIP(5-PFS) displayed a higher binding capacity than MIP(4-TMS) and was less susceptible to non-specific binding influences.
有效片段势（EFP）分子建模方法首次被应用于选择的多氯联苯（PCBs）的基团识别的分子印迹聚合物的合理设计。使用 S22 化合物测试集对标 EFP 计算，其返回的能量与报道的金标准 CCSD(T)方法相差 1 kcal mol(-1)以内，但计算成本更低。EFP 允许快速识别三甲苯（TMS）和五氟苯乙烯（PFS）作为模板（T）1,2,3,4,5-五氯苯（4）和 1,2,3-三氯苯（5）的功能单体的选择。乙二醇二甲基丙烯酸酯是交联剂（CL）的选择。对于 4（TMS 作为 FM；MIP(4-TMS)），使用 1:2:10（T:FM:CL）的比例，得到印迹因子（IF）为 2.1；对于 5，使用 15:6:29 的比例得到 IF 为 3.66（PFS 作为 FM；MIP(5-PFS)）。MIP(4-TMS)和 MIP(5-PFS)对非氯化模板的识别水平较低，IF 值范围为 1.05、1.17 和 1.13、1.54，分别为甲苯（14）和 2,6-二甲基苯胺（12）。对于氯化类似物 1,3,5-三氯苯（11）和 2,4,6-三氯苯胺（12），观察到更高的识别水平，IF 值分别为 1.20、1.64 和 1.89、2.66，MIP(4-TMS)和 MIP(5-PFS)分别表明这些 MIP 适合于 PCBs 的片段印迹。用 MIP(4-TMS)对 2,2',3,5'-四氯联苯（15）、2,3,3',4,4'-五氯联苯（16）和 2,2',3,3',4,5,6'-七氯联苯（17）进行片段印迹，得到的 IF 值分别为 1.38、1.38 和 1.41。MIP(5-PFS)的 IF 值分别为 6.57、3.46 和 5.80，对 15-17 的性能明显更好。此外，MIP(5-PFS)显示出比 MIP(4-TMS)更高的结合能力，并且不易受到非特异性结合的影响。
