Dalla Cort Antonella, De Bernardin Paolo, Schiaffino Luca
Dipartimento di Chimica and IMC-CNR, Università La Sapienza, 00185 Roma, Italy.
Chirality. 2009 Jan;21(1):104-9. doi: 10.1002/chir.20614.
A new water soluble zinc-salophen complex with appended D-glucose moieties was synthesized and characterized. Its binding properties toward six aminoacids were investigated by UV-vis spectrophotometric titrations. Association constants showed to be unfavorably affected by increasing steric hindrance of the side chain. Quite surprisingly, different association constants were measured for the L and D enantiomers. These data suggest that aminoacids are bound via two interactions, zinc-carboxylate coordination and two hydrogen bonds between the ammonium group of the aminoacid and two oxygen atoms of one D-glucose moiety. Such conclusion is supported by the result of semiempirical (PM3) calculations. Notably, the K(L)/K(D) value of 9.6 observed for the association of phenylalanine rivals with the highest values found for the chiral recognition of aminoacids in water.
合成并表征了一种新的带有附加D-葡萄糖部分的水溶性锌-萨罗芬配合物。通过紫外可见分光光度滴定法研究了其对六种氨基酸的结合特性。缔合常数显示出受侧链空间位阻增加的不利影响。非常令人惊讶的是,对L和D对映体测得的缔合常数不同。这些数据表明,氨基酸通过两种相互作用结合,即锌-羧酸盐配位以及氨基酸铵基团与一个D-葡萄糖部分的两个氧原子之间的两个氢键。半经验(PM3)计算结果支持了这一结论。值得注意的是,苯丙氨酸缔合观察到的K(L)/K(D)值为9.6,可与水中氨基酸手性识别的最高值相媲美。