Elliot A J, Wilkinson F, Armstrong D A
Int J Radiat Biol Relat Stud Phys Chem Med. 1980 Jul;38(1):1-10. doi: 10.1080/09553008014550901.
Reactions of eaq with zinc(II)-insulin at pH 6.6 and 9.0 yielded relatively low disulphide anion absorptions, suggesting eaq reacts at other sites than S-S. A similar conclusion was reached for the reation of CO2 where an even lower yield of disulphide anion was found. However, here the disulphide anion yield increased with 'prepulsing'. Simultaneously the rate constant decreased, implying that a more reactive site was 'cleaned up'. While no reaction of Br2 with insulin was observed, both OH and Cl2 reacted rapidly and predominantly at the tyrosine residues. The second order rate constants, calculated in terms of insulin monomer concentrations, are reported for eaq, CO2 and Cl2. The transient spectra qualitatively support evidence regarding the accessibility of S-S bonds and tryosine residues in the various forms of insulin as predicted from earlier studies.
在pH值为6.6和9.0的条件下,水合电子(eaq)与锌(II)-胰岛素反应产生的二硫阴离子吸收相对较低,这表明水合电子在除S-S键以外的其他位点发生反应。对于二氧化碳的反应也得出了类似的结论,在该反应中发现二硫阴离子的产率更低。然而,在这里二硫阴离子产率随着“预脉冲”而增加。同时速率常数降低,这意味着一个更具反应性的位点被“清理”了。虽然未观察到溴与胰岛素的反应,但羟基(OH)和氯气(Cl2)都迅速反应,且主要在酪氨酸残基处发生反应。报告了根据胰岛素单体浓度计算得出的水合电子、二氧化碳和氯气的二级速率常数。瞬态光谱从定性上支持了关于不同形式胰岛素中S-S键和酪氨酸残基可及性的证据,这与早期研究预测的一致。