Distance geometry and molecular dyndrics are currently employed in determining molecular structures with interatondc distances from NMR NOESY experiment.Because of the flexibility of peptide, distances obtained from N...Distance geometry and molecular dyndrics are currently employed in determining molecular structures with interatondc distances from NMR NOESY experiment.Because of the flexibility of peptide, distances obtained from NMR are usually not sufficient to coallne its structure. Both distance geometry and molecular dynamics will biasin the cocformational space at this circumstance. Constraint Monte Carlo simulated annealing was established to solve this problem. Distance constraints were included into the ECEPP/2 force field by introducing a harmonic energy term. Conformational analysis of a pentapeptide with eight interatodric distances from NMR was carried out as a test. By comparison of the 100 conformers obtained from constraint simulated annealing and the 100 conformers from distance geometry calculation, it was found that constraint sirnulated armealing can cover the outcomes of distance geometry and at the same time give more con-formers fitting to the experimental data. The result shows that constraint Monte-Carlo simulated aunealing is more valid in constructing peptide structures from NMR distances than currently employed methods when no swhcient distances from NMR are available.展开更多
作为系统研究大环硫氮杂冠醚结构的一部分,合成了1,4,10,13-四硫-7,16-二氮杂环十八冠醚的硝酸盐[H_2(C_(12)H_(26)N_2S_4)(NO_3)_2]1和镍配合物[Ni(C_(12)H_(26)N_2S_4)Cl_2·4H_2O]2,并测定和计算了它们的晶体结构和电子结构.化合...作为系统研究大环硫氮杂冠醚结构的一部分,合成了1,4,10,13-四硫-7,16-二氮杂环十八冠醚的硝酸盐[H_2(C_(12)H_(26)N_2S_4)(NO_3)_2]1和镍配合物[Ni(C_(12)H_(26)N_2S_4)Cl_2·4H_2O]2,并测定和计算了它们的晶体结构和电子结构.化合物1属单斜晶系,空间群 P2_1/c,a=7.936(5),b=8.866(7),c=14.756(5),β=95.33(4)°,V=1033.7~3,Z=2,D_o=1.45g·cm^(-3),μ=43.7cm^(-1),F(000)=480,最终偏离因子 R=0.059,R_w=0.059.化合物2属三斜晶系,空间群 PI,a=6.941(4),b=9.862(3),c=16.507(3)(?),α=98.78(2),β=95.52(3),γ=93.48(3)°,V=1108.3~3,Z=2,D_o=1.58g·cm^(-3),μ=14.9cm^(-1),F=(000)=556,最终偏离因子 R=0.060,R_w=0.065.晶体结构测定结果表明:化合物1与自由配体 L 相比较,N 原子的构型变化最大,在氯化镍配合物2中,四硫二氮大环发生严重扭曲,其中四个 S 和两个 N 原子在 Ni 原子周围形成八面体配位,Ni—N 距离从2.109到2.140(?),Ni—S 距离从2.370到2.435.同时,量化计算结果说明,S、N 原子与 Ni^(2+)配位时均为电子授体,且 S 对 Ni^(2+)的授电子能力,似略大于 N 原子.展开更多
文摘Distance geometry and molecular dyndrics are currently employed in determining molecular structures with interatondc distances from NMR NOESY experiment.Because of the flexibility of peptide, distances obtained from NMR are usually not sufficient to coallne its structure. Both distance geometry and molecular dynamics will biasin the cocformational space at this circumstance. Constraint Monte Carlo simulated annealing was established to solve this problem. Distance constraints were included into the ECEPP/2 force field by introducing a harmonic energy term. Conformational analysis of a pentapeptide with eight interatodric distances from NMR was carried out as a test. By comparison of the 100 conformers obtained from constraint simulated annealing and the 100 conformers from distance geometry calculation, it was found that constraint sirnulated armealing can cover the outcomes of distance geometry and at the same time give more con-formers fitting to the experimental data. The result shows that constraint Monte-Carlo simulated aunealing is more valid in constructing peptide structures from NMR distances than currently employed methods when no swhcient distances from NMR are available.
文摘作为系统研究大环硫氮杂冠醚结构的一部分,合成了1,4,10,13-四硫-7,16-二氮杂环十八冠醚的硝酸盐[H_2(C_(12)H_(26)N_2S_4)(NO_3)_2]1和镍配合物[Ni(C_(12)H_(26)N_2S_4)Cl_2·4H_2O]2,并测定和计算了它们的晶体结构和电子结构.化合物1属单斜晶系,空间群 P2_1/c,a=7.936(5),b=8.866(7),c=14.756(5),β=95.33(4)°,V=1033.7~3,Z=2,D_o=1.45g·cm^(-3),μ=43.7cm^(-1),F(000)=480,最终偏离因子 R=0.059,R_w=0.059.化合物2属三斜晶系,空间群 PI,a=6.941(4),b=9.862(3),c=16.507(3)(?),α=98.78(2),β=95.52(3),γ=93.48(3)°,V=1108.3~3,Z=2,D_o=1.58g·cm^(-3),μ=14.9cm^(-1),F=(000)=556,最终偏离因子 R=0.060,R_w=0.065.晶体结构测定结果表明:化合物1与自由配体 L 相比较,N 原子的构型变化最大,在氯化镍配合物2中,四硫二氮大环发生严重扭曲,其中四个 S 和两个 N 原子在 Ni 原子周围形成八面体配位,Ni—N 距离从2.109到2.140(?),Ni—S 距离从2.370到2.435.同时,量化计算结果说明,S、N 原子与 Ni^(2+)配位时均为电子授体,且 S 对 Ni^(2+)的授电子能力,似略大于 N 原子.
