Conformer-selective photoelectron spectroscopy of α-lactalbumin derived multianions in the gas phase.

Conformer-selective photoelectron spectroscopy of α-lactalbumin derived multianions in the gas phase.
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气相中α-乳清蛋白衍生的多阴离子的构象选择性光电子能谱

DOI:
10.1039/c3cp54596b
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发表时间:
2014
期刊:
Physical chemistry chemical physics : PCCP
影响因子:
--
通讯作者:
M.M. Kappes
M.M. Kappes
中科院分区:
--
文献类型:
--
作者:
M. Vonderach;M.-O. WinghartL. MacAleese;F. Chirot;R. Antoine;Ph. Dugourd;P. Weis;O. Hampe;M.M. Kappes

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我们记录了α-乳清蛋白衍生的多阴离子的共形选择性气相光电子能谱,这些多阴离子是由天然蛋白质及其变性形式(通过化学还原断裂硫-硫键制备)的电喷雾溶液产生的。三组不同的气相多阴离子构象已被观察和表征。从天然蛋白质的溶液中获得高度折叠和部分未折叠的结构。在电喷雾变性蛋白质时仅观察到高度伸长的构象异构体。绝热剥离能确定在几个负电荷状态下的每个构象组。与高度伸长的构象相比,高度折叠的结构显示出随着负电荷的增加电子结合能的急剧降低。通过比较实验的高度细长的结构与一个简单的静电模型计算的预测分离能,我们已经确定了有效的介电屏蔽常数。
We have recorded conformer-selective, gas-phase photoelectron spectra of α-lactalbumin derived multianions generated by electrospraying solutions of both the native protein and its denatured form (as prepared by breaking the sulfur–sulfur bonds by chemical reduction). Three different groups of gas-phase multianion conformers have been observed and characterized. Highly-folded and partially-unfolded structures are obtained from solutions of the native protein. Only highly-elongated conformers are observed upon electrospraying the denatured protein. Adiabatic detachment energies were determined at several negative charge states for each conformer group. In comparison to highly-elongated conformations, highly-folded structures show a steeper decrease of electron binding energy with increasing negative charge. By comparing experimental detachment energies for highly-elongated structures with the predictions of a simple electrostatic model calculation, we have determined the effective dielectric shielding constant.
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