Department of Chemistry, Oregon State University, Corvallis, Oregon 97331, USA; email:
Annu Rev Phys Chem. 2020 Apr 20;71:239-265. doi: 10.1146/annurev-physchem-071119-040154. Epub 2020 Feb 19.
The structure-function relationships of biomolecules have captured the interest and imagination of the scientific community and general public since the field of structural biology emerged to enable the molecular understanding of life processes. Proteins that play numerous functional roles in cellular processes have remained in the forefront of research, inspiring new characterization techniques. In this review, we present key theoretical concepts and recent experimental strategies using femtosecond stimulated Raman spectroscopy (FSRS) to map the structural dynamics of proteins, highlighting the flexible chromophores on ultrafast timescales. In particular, wavelength-tunable FSRS exploits dynamic resonance conditions to track transient-species-dependent vibrational motions, enabling rational design to alter functions. Various ways of capturing excited-state chromophore structural snapshots in the time and/or frequency domains are discussed. Continuous development of experimental methodologies, synergistic correlation with theoretical modeling, and the expansion to other nonequilibrium, photoswitchable, and controllable protein systems will greatly advance the chemical, physical, and biological sciences.
生物分子的结构-功能关系自结构生物学领域出现以来，一直吸引着科学界和公众的兴趣和想象力，使人们能够从分子水平上理解生命过程。在细胞过程中发挥众多功能作用的蛋白质一直是研究的前沿领域，激发了新的表征技术。在这篇综述中，我们介绍了使用飞秒受激拉曼光谱（FSRS）来绘制蛋白质结构动力学的关键理论概念和最新实验策略，重点介绍了超快时间尺度上的灵活发色团。特别是，可调谐波长的 FSRS 利用动态共振条件来跟踪随瞬态物种变化的振动运动，从而能够进行合理设计来改变功能。讨论了在时间和/或频率域中捕获激发态发色团结构快照的各种方法。实验方法的不断发展、与理论建模的协同关联以及对其他非平衡、光致开关和可控蛋白质系统的扩展将极大地推动化学、物理和生物科学的发展。
