Measuring electrostatic fields in both hydrogen-bonding and non-hydrogen-bonding environments using carbonyl vibrational probes.
Measuring electrostatic fields in both hydrogen-bonding and non-hydrogen-bonding environments using carbonyl vibrational probes.
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DOI：
10.1021/ja403917z
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发表时间：
2013-07-31
影响因子：
15
通讯作者：
Boxer, Steven G.
中科院分区：
文献类型：
--
作者：
Fried, Stephen D.;Bagchi, Sayan;Boxer, Steven G.
振动探针可以直接读出复杂分子环境中的局部静电场，如蛋白质结合部位和酶活性部位。这些信息为探索重要生物分子过程的潜在物理原因提供了实验方法，如结合和催化。然而，特定的化学相互作用，如氢键，可能会对振动探针产生复杂的影响，并混淆对其频移的简单静电解释。我们使用振动斯塔克光谱和红外光谱对不同溶剂环境和核糖核酸酶S中的羰基探针进行了研究，以了解羰基频率对静电场的敏感性，包括由氢键引起的频率。此外，我们还对溶剂和核糖核酸酶S中的系综平均电场进行了分子动力学模拟，发现计算场与振动频率之间有很好的相关性。这些数据使得能够为C=O振动构建一条健壮的场频校准曲线。目前的结果表明，羰基探针能够定量评估氢键的静电作用，这使它们有望在未来的蛋白质功能研究中发挥作用。
Vibrational probes can provide a direct read-out of the local electrostatic field in complex molecular environments, such as protein binding sites and enzyme active sites. This information provides an experimental method to explore the underlying physical causes of important biomolecular processes such as binding and catalysis. However, specific chemical interactions such as hydrogen bonds can have complicated effects on vibrational probes and confound simple electrostatic interpretations of their frequency shifts. We employ vibrational Stark spectroscopy along with infrared spectroscopy of carbonyl probes in different solvent environments and in Ribonuclease S to understand the sensitivity of carbonyl frequencies to electrostatic fields, including those due to hydrogen bonds. Additionally, we carried out molecular dynamics simulations to calculate ensemble-averaged electric fields in solvents and in Ribonuclease S, and found excellent correlation between calculated fields and vibrational frequencies. These data enabled the construction of a robust field-frequency calibration curve for the C=O vibration. The present results suggest that carbonyl probes are capable of quantitatively assessing the electrostatics of hydrogen bonding, making them promising for future study of protein function.
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影响因子：
5.5
作者：
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通讯作者：
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DOI：
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影响因子：
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作者：
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作者：
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影响因子：
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作者：
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