Yang Xiaodi, Miao Qiang, Yu Tsing, Hu Jun, Yang Zhengbiao, Bi Shuping
State Key Laboratory of Coordination Chemistry, Department of Chemistry, Nanjing University, 22 Hankou Road, Nanjing 210093, People's Republic of China.
Spectrochim Acta A Mol Biomol Spectrosc. 2003 Sep;59(11):2655-65. doi: 10.1016/s1386-1425(03)00035-0.
The complex-formation equilibria between aluminum(III) ion and L-(+)-ascorbic acid (AA) in 0.1 M KCl ionic medium at 25 degrees C and 0.15 M NaCl ionic medium at 37 degrees C were studied by glass electrode pH-metric measurements. The obtained experimental results were explained by the formation of the following complexation species: a weak mononuclear 1:1 species AlL(2+) together with two trinuclear mixed-hydroxo species Al(3)H(-5)L(4) and Al(3)H(-5)L(3+) in acidic aqueous solutions. Meanwhile, the formation of the complexes and structures of Al with AA were proved by multinuclear (1H, 13C, 27Al) NMR spectra in the pH range 2.0-5.0. It is supposed that Al directly coordinates with AA at O-3 moiety; also, Al can coordinate with the O-1 and O-2 moieties of ascorbate ion through the weakly binding and the intramolecular hydrogen bonding in acidic aqueous solutions.
通过玻璃电极pH测量法研究了25℃下0.1 M KCl离子介质以及37℃下0.15 M NaCl离子介质中铝(III)离子与L-(+)-抗坏血酸(AA)之间的络合形成平衡。通过形成以下络合物种来解释所获得的实验结果:在酸性水溶液中,一种弱单核1:1物种AlL(2+)以及两种三核混合羟基物种Al(3)H(-5)L(4)和Al(3)H(-5)L(3+)。同时,通过2.0 - 5.0 pH范围内的多核(1H、13C、27Al)NMR光谱证明了Al与AA形成的络合物及其结构。据推测,Al在O-3部分直接与AA配位;此外,在酸性水溶液中,Al可以通过弱结合和分子内氢键与抗坏血酸离子的O-1和O-2部分配位。