Yang Xiaodi, Tang Yongzheng, Bi Shuping, Yang Gaosheng, Hu Jun
State Key Laboratory of Coordination Chemistry, Department of Chemistry, Nanjing University, Nanjing, 210093, P. R. China.
Anal Sci. 2003 Jan;19(1):133-8. doi: 10.2116/analsci.19.133.
Complex formation studies of L-glutamate with aluminum(III) ion were conducted in acidic aqueous solutions (pH 2.0 - 5.5) by means of pH-metric titration and multinuclear (1H, 13C and 27Al) NMR techniques. The following results were obtained: (1) Al could weakly coordinate with Glu to form various mononuclear 1:1 (AlLH2+, AlL+, AlLH(-1)) species and dinuclear 2:1 (Al2L4+) species in acidic aqueous solutions, which somewhat agreed with previous findings. (2) The multi-NMR spectra of Al-Glu and Al-Asp strongly suggest that, besides negatively charged carboxylate donors (-COO(-), -COO(-)), the amino group of Glu can participate in the binding of Al in the AlL+ and AlLH(-1) species in the case of its deprotonation, which rather agreed with the case of Al-Asp. (3) These tridentate five-+seven-membered joint chelate (-COO(-), -NH2, -COO(-)) complexes exhibit an enhanced stability, which can help to better understand the biological studies that Al-Glu could cross the erythrocyte membrane and the blood-brain barrier (BBB) and be deposited selectively in various brain regions, particularly in the cortex. It will also help to intrinsically understand the Al's role in the biological transamination system, which is a very important process in all living things.
通过pH滴定法和多核(1H、13C和27Al)核磁共振技术,在酸性水溶液(pH 2.0 - 5.5)中对L-谷氨酸与铝(III)离子的络合物形成进行了研究。得到以下结果:(1)在酸性水溶液中,铝能与谷氨酸弱配位形成各种单核1:1(AlLH2+、AlL+、AlLH(-1))物种和双核2:1(Al2L4+)物种,这与先前的研究结果有一定程度的相符。(2)Al-Glu和Al-Asp的多核磁共振谱强烈表明,除了带负电荷的羧酸盐供体(-COO(-)、-COO(-))外,在谷氨酸的氨基去质子化的情况下,它可以参与AlL+和AlLH(-1)物种中铝的结合,这与Al-Asp的情况较为一致。(3)这些三齿五元+七元联合螯合物(-COO(-)、-NH2、-COO(-))配合物表现出增强的稳定性,这有助于更好地理解关于Al-Glu可以穿过红细胞膜和血脑屏障(BBB)并选择性沉积在各个脑区,特别是皮层的生物学研究。这也将有助于从本质上理解铝在生物转氨系统中的作用,这是所有生物中一个非常重要的过程。