Unraveling Hydration Shell Dynamics and Viscosity Effects Around Cyanamide Probes via 2D IR Spectroscopy

IF 14.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Christopher J. Mallon, Majid Hassani, Ellia H. Osofsky, Savannah B. Familo, Edward E. Fenlon, Matthew J. Tucker
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Abstract

Hydration dynamics and solvent viscosity play critical roles in the structure and function of biomolecules. An overwhelming body of evidence suggests that protein and membrane fluctuations are closely linked to solvent fluctuations. While extensive research exists on the use of vibrational probes to detect local interactions and solvent dynamics, fewer studies have explored how the behavior of these reporters changes in response to bulk viscosity. To address this gap, two-dimensional infrared spectroscopy (2D IR) was employed in this study to investigate the ultrafast hydration dynamics around a cyanamide (NCN) probe attached to a nucleoside, deoxycytidine, in aqueous solutions with varying glycerol content. The use of a small vibrational probe on a targeted nucleic acid offers the potential to capture more localized hydration dynamics than alternative methods. The time scales for the frequency correlation decays were found to increase linearly with bulk viscosity, ranging from 0.9 to 11.4 ps over viscosities of 0.96–49.1 cP. Additionally, molecular dynamics (MD) simulations were performed to model the local hydration dynamics around the NCN probe. Interestingly, increasing the glycerol content did not significantly alter the hydration of the deoxycytidine. The MD simulations further suggested that the NCN probe’s frequency fluctuations were primarily influenced by the dynamics of water in the second solvation shell. Cage correlation functions, which measure the movement of water molecules in and out of the second solvation shell, exhibited decays that closely matched those of the frequency-fluctuation correlation function (FFCF). These findings offer new insights into hydration dynamics and the impact of viscosity on biological systems.

Abstract Image

利用二维红外光谱研究氰酰胺探针的水化壳动力学和黏度效应
水合动力学和溶剂粘度对生物大分子的结构和功能起着至关重要的作用。大量证据表明,蛋白质和膜的波动与溶剂波动密切相关。虽然利用振动探针检测局部相互作用和溶剂动力学的研究已经非常广泛,但探讨这些探针的行为如何随体积粘度而变化的研究却较少。为了填补这一空白,本研究采用二维红外光谱(2D IR)来研究甘油含量不同的水溶液中连接到核苷脱氧胞苷上的氰酰胺(NCN)探针周围的超快水合动力学。与其他方法相比,在目标核酸上使用小型振动探针有可能捕捉到更局部的水合动力学。研究发现,频率相关衰减的时间尺度随体积粘度的增加而线性增加,在 0.96-49.1 cP 的粘度范围内从 0.9 到 11.4 ps 不等。此外,还进行了分子动力学(MD)模拟,以模拟 NCN 探针周围的局部水合动力学。有趣的是,增加甘油含量并没有明显改变脱氧胞苷的水合作用。MD 模拟进一步表明,NCN 探针的频率波动主要受第二溶壳中水的动力学影响。测量水分子进出第二溶胶壳运动的笼相关函数的衰减与频率波动相关函数的衰减非常接近。这些发现为水合动力学和粘度对生物系统的影响提供了新的见解。
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来源期刊
CiteScore
24.40
自引率
6.00%
发文量
2398
审稿时长
1.6 months
期刊介绍: The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.
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