A study on ATR-FUV spectroscopy for investigation of electronic structure and transitions of various biological molecules

Kosuke Hashimoto, Y. Morisawa, H. Sato, M. Tortora, B. Rossi, Y. Ozaki
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Abstract

This study aims at exploring the potential of ATR-far-ultraviolet (FUV) spectroscopy in investigating electronic structure and transitions of various kinds of biological molecules. For this purpose, ATR-FUV spectra were measured for several kinds of proteins with the different secondary structures, several kinds of carbohydrates, nucleic acids, and lipids. Band assignments have been made for all kinds of biological molecules investigated based on our previous ATR-FUV studies on n-alkanes, alcohols, esters, and amides. For example, the proteins show a characteristic band near 200 nm due to π-π* transition of amide groups. The position of this band varies a little with the secondary structure of proteins but its intensity changes significantly depending on the secondary structure and solutions. All the carbohydrates studied yielded a band near 170 nm due to n-Rydberg transition of ether. In addition, acetylcarbohydrates give an additional band near 190 nm originating from π-π* transition of amide at 2’ carbon. The present study has demonstrated that ATR-FUV spectroscopy is a new powerful technique in exploring electronic structure and transitions of biological molecules, in general. It is also possible to use ATR-FUV spectroscopy for quantitative and qualitative analysis of biological molecules. Moreover, it is of note that information regarding electronic transitions collected by ATR-FUV spectroscopy is useful for UV resonance Raman (UVRR) spectroscopy studies of biological molecules. A combined ATR-FUV spectroscopy and UVRR spectroscopy method may provide a novel analytical tool for molecular and electronic structure of biological molecules.
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ATR-FUV光谱用于研究各种生物分子的电子结构和跃迁的研究
本研究旨在探索atr -远紫外(FUV)光谱在研究各种生物分子的电子结构和跃迁方面的潜力。为此,测定了几种具有不同二级结构的蛋白质、几种碳水化合物、核酸和脂类的ATR-FUV光谱。基于我们之前对正构烷烃、醇类、酯类和酰胺类的ATR-FUV研究,已经对各种生物分子进行了带分配。例如,由于酰胺基团的π-π*跃迁,蛋白质在200 nm附近显示出特征带。该条带的位置随蛋白质的二级结构变化不大,但其强度随二级结构和溶液的不同而变化很大。由于乙醚的n-里德堡跃迁,所研究的所有碳水化合物都在170 nm附近产生了一个带。此外,乙酰碳水化合物在190 nm附近有一个额外的波段,这是由酰胺在2′碳上的π-π*跃迁引起的。目前的研究表明,ATR-FUV光谱在探索生物分子的电子结构和跃迁方面是一种强有力的新技术。ATR-FUV光谱也可用于生物分子的定量和定性分析。此外,值得注意的是,ATR-FUV光谱收集的电子跃迁信息对生物分子的紫外共振拉曼(UVRR)光谱研究是有用的。ATR-FUV光谱和UVRR光谱相结合的方法可能为研究生物分子的分子结构和电子结构提供一种新的分析工具。
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