Bohrer Denise, Polli Vania Gabbi, Cícero do Nascimento Paulo, Mendonça Jean Karlo A, de Carvalho Leandro Machado, Pomblum Solange Garcia
Departamento de Química, Universidade Federal de Santa Maria, 97111-970, Santa Maria, RS, Brazil.
J Biol Inorg Chem. 2006 Nov;11(8):991-8. doi: 10.1007/s00775-006-0156-z. Epub 2006 Aug 24.
The interaction between aluminium and cysteine and cystine was evaluated by means of ion-exchange experiments and potentiometry. Ion-exchange experiments included other ligands with affinity for aluminium and two kinds of resins, either a Na+ -form or an Al3+ -form exchanger. The ability of the ligands to keep aluminium in solution in the presence of the Na+ exchanger or to withdraw it from the Al3+ -form resin was evaluated. Aluminium quantification was carried out by either graphite-furnace or flame atomic absorption spectrometry. Aluminium extraction isotherms were linearised using the Scatchard plot, and stability constants were obtained from the curves' slopes. The experiments showed that the ability of the ligands to withdraw aluminium from the Al3+ -form resin increased following the order cysteine < oxalate < citrate = cystine < nitrilotriacetic acid < ethylenediaminetetraacetic acid. Potentiometric titrations, carried out in aqueous solution with constant ionic strength and temperature, showed that the predominant species in solution have a metal-ligand proportion of 1:1 for both amino acids. The main species are Al(OH)3L, with log K of 6.2 for cysteine, and AlL and Al(OH)L, with log K of 10.3 and 1.7, respectively, for cystine. Stability constants obtained from the Scatchard plots showed a linear correlation with the stability constants obtained by potentiometry for cystine and cysteine in this work and those collected from the literature for the other ligands. These results show that cysteine and cystine extract and maintain aluminium in solution, which may explain elevated concentrations of aluminium in parenteral nutrition solutions containing these amino acids.
通过离子交换实验和电位滴定法评估了铝与半胱氨酸和胱氨酸之间的相互作用。离子交换实验包括其他对铝有亲和力的配体以及两种树脂,即Na⁺型或Al³⁺型交换剂。评估了配体在存在Na⁺交换剂的情况下使铝保持在溶液中的能力,或从Al³⁺型树脂中提取铝的能力。通过石墨炉或火焰原子吸收光谱法进行铝的定量分析。使用Scatchard图将铝萃取等温线线性化,并从曲线斜率获得稳定常数。实验表明,配体从Al³⁺型树脂中提取铝的能力按以下顺序增加:半胱氨酸<草酸盐<柠檬酸盐 = 胱氨酸<次氮基三乙酸<乙二胺四乙酸。在具有恒定离子强度和温度的水溶液中进行的电位滴定表明,对于这两种氨基酸,溶液中的主要物种的金属 - 配体比例均为1:1。主要物种是Al(OH)₃L,半胱氨酸的log K为6.2,对于胱氨酸,主要物种是AlL和Al(OH)L,log K分别为10.3和1.7。从Scatchard图获得的稳定常数与本工作中通过电位滴定法获得的胱氨酸和半胱氨酸的稳定常数以及从文献中收集的其他配体的稳定常数呈线性相关。这些结果表明,半胱氨酸和胱氨酸能提取并使铝保持在溶液中,这可能解释了含有这些氨基酸的肠外营养液中铝浓度升高的原因。