Department of Chemistry, Syracuse University, Syracuse, New York.
Chirality. 2020 May;32(5):667-692. doi: 10.1002/chir.23191. Epub 2020 Feb 21.
Vibrational optical activity (VOA) consisting of infrared vibrational circular dichroism (VCD) and vibrational Raman optical activity (ROA) was predicted, discovered, and confirmed between 1971 and 1975. My path to VOA was mentored by three pioneers of chirality and vibrational spectroscopy: Professors Albert Moscowitz, Warner L. Peticolas, and Philip J. Stephens, and while they are no longer alive today, the Chirality Medal, my award address, and this paper are dedicated to each of them. Since the discovery of VOA, a number of key advances have made possible the current era of widespread applications. The principal instrumental advances were Fourier-transform VCD (FT-VCD) and multichannel charge coupled detector (CCD) ROA. Computational advances include the first complete quantum chemistry formulation of VCD leading to the magnetic field perturbation (MFP) and the nuclear velocity perturbation (NVP) theories. The strength of VOA is the comparison between measured and calculated spectra that enables the determination of absolute configuration and solution-state conformations. More recently, VCD has uncovered supramolecular chirality in amyloid fibrils and ROA to high-order protein structure. Future challenges for VOA include describing the effects of weak intermolecular interactions, transfer of chirality, solvent effects, supramolecular chirality, and the generation of nuclear velocity electron current density.
振动旋光活性（VOA）包括红外振动圆二色性（VCD）和振动拉曼旋光活性（ROA），它在 1971 年至 1975 年间被预测、发现并得到证实。我在研究 VOA 的过程中得到了三位手性和振动光谱学先驱的指导：教授阿尔伯特·莫斯科维茨（Albert Moscowitz）、华纳·L·佩蒂科拉斯（Warner L. Peticolas）和菲利普·J·斯蒂芬斯（Philip J. Stephens）。虽然他们今天已经不在人世，但我获得的手性奖章、我的获奖演讲和这篇论文都是献给他们每一个人的。自 VOA 被发现以来，许多关键的进展使得它在当前得到了广泛的应用。主要的仪器进展是傅里叶变换 VCD（FT-VCD）和多通道电荷耦合检测器（CCD）ROA。计算方面的进展包括 VCD 的第一个完整量子化学公式，导致磁场微扰（MFP）和核速度微扰（NVP）理论。VOA 的优势在于对测量和计算光谱进行比较，从而确定绝对构型和溶液构象。最近，VCD 揭示了淀粉样纤维中的超分子手性和 ROA 对高级蛋白质结构的作用。VOA 的未来挑战包括描述弱分子间相互作用、手性转移、溶剂效应、超分子手性和核速度电子电流密度的产生。
