Kiselev G V
Biokhimiia. 1978 Jul;43(7):1328-34.
Dependency of optical rotation of di- and triphosphoinositide water solutions on pH is investigated. The inversion of myo-inosite ring in triphosphoinositide molecule is found to take place at pH range corresponding to the transition of phosphomonoesters from monoanionic into dianionic form. Stabilization of optical rotation is observed at pH range, where one monoester phosphate group is in monoanionic form and the other--in dianionic form. Probably, triphosphoinositide is in the conformation (distorted boat) at this pH range. Diphosphoinositide does not change its optical rotation under pH changes of water or organic solutions. A contribution is estimated of free conformational energy into standard free energy of splitting triphosphoinositide phosphate group depending on pH value. It is concluded that low energy phosphate bond becomes high energy bond due to the free electrostatic interaction of dianionic phosphate group with other negatively charged group in sin-clynal conformation.
研究了二磷酸肌醇和三磷酸肌醇水溶液的旋光度对pH的依赖性。发现三磷酸肌醇分子中肌醇环的翻转发生在pH范围内,该范围对应于磷酸单酯从单阴离子形式转变为双阴离子形式。在一个磷酸单酯基团为单阴离子形式而另一个为双阴离子形式的pH范围内观察到旋光度的稳定。在该pH范围内,三磷酸肌醇可能处于(扭曲船型)构象。二磷酸肌醇在水或有机溶液的pH变化下其旋光度不变。根据pH值估计了自由构象能对三磷酸肌醇磷酸基团断裂标准自由能的贡献。得出结论,由于双阴离子磷酸基团与顺式构象中其他带负电荷基团的自由静电相互作用,低能磷酸键变成了高能键。