Machalska Ewa, Halat Monika, Tani Takumi, Fujisawa Tomotsumi, Unno Masashi, Kudelski Andrzej, Baranska Malgorzata, Zając Grzegorz
Jagiellonian Centre for Experimental Therapeutics (JCET), Jagiellonian University, Bobrzynskiego 14, 30-348 Krakow, Poland.
Laboratory for Spectroscopy, Molecular Modeling and Structure Determination, Institute of Nuclear Chemistry and Technology, Dorodna 16, 03-195 Warsaw, Poland.
J Phys Chem Lett. 2024 May 9;15(18):4913-4919. doi: 10.1021/acs.jpclett.4c00270. Epub 2024 Apr 29.
Raman optical activity (ROA) spectroscopy exhibits significant potential in the study of (bio)molecules as it encodes information on their molecular structure, chirality, and conformations. Furthermore, the method reveals details on excited electronic states when applied under resonance conditions. Here, we present a combined study of the far from resonance (FFR)-ROA and resonance ROA (RROA) of a single relatively small molecular system. Notably, this study is the first to employ the density functional theory (DFT) analysis of both FFR-ROA and RROA spectra. This is illustrated for cobalamin derivatives using near-infrared and visible light excitation. Although the commonly observed monosignate RROA spectra lose additional information visible in bisignate nonresonance ROA spectra, the RROA technique acts as a complement to nonresonance ROA spectroscopy. In particular, the combination of these methods integrated with DFT calculations can reveal a complete spectral picture of the structural and conformational differences between tested compounds.
拉曼光学活性（ROA）光谱在（生物）分子研究中展现出巨大潜力，因为它能编码有关分子结构、手性和构象的信息。此外，该方法在共振条件下应用时能揭示激发电子态的细节。在此，我们展示了对单个相对较小分子体系的非共振（FFR）-ROA和共振ROA（RROA）的联合研究。值得注意的是，本研究首次对FFR-ROA和RROA光谱进行密度泛函理论（DFT）分析。这通过使用近红外和可见光激发的钴胺素衍生物得以说明。尽管常见的单符号RROA光谱丢失了双符号非共振ROA光谱中可见的额外信息，但RROA技术可作为非共振ROA光谱的补充。特别是，这些方法与DFT计算相结合，能够揭示测试化合物之间结构和构象差异的完整光谱图。
