亮氨酸与异亮氨酸太赫兹光谱的振动模式分析

doi:10.3964/j.issn.1000-0593(2024)05-1255-07

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Abstract As organic compounds containing an alkaline amino group and acidic carboxyl group, an amino acid is the basic unit of protein, whose type, quantity and arrangement directly affect the biological function of protein with great significance to maintain the body function. Most amino acid intermolecular vibrational modes (torsion, hydrogen bonding and collective vibrations) occur in the THz band and exhibit unique absorption characteristics. Consequently, THz spectroscopic studies of amino acids can give a more comprehensive understanding of biological properties. It was a summary of the absorption spectra of leucine and isoleucine located in the 0.2~2.6 THz band measured by previous authors, and, at the same time, the formation mechanism was explained using quantum chemical calculations. Using Gaussian09 software for single-molecule configuration simulations, the simulations were performed by semi-empirical method (PM6), ab initio method (HF, MP2) and density functional theory (B3LYP, M06-2X) combined with 6-311+G(d,p) Gaussian basis groups. Materials Studio 2019 software was used to calculate the cell configuration simulations for four density generalized gradient approximations such as PBE, PBEsol, RPBE and WC combined with plane wave basis groups. The results indicated that the single-molecule configuration simulations lacked absorption peak positions, and the peak positions were calculated differently for the same vibrational mode by different methods. So, for structures with strong intermolecular interactions, the simulation of this configuration by a single method did not correctly match the vibrational modes to a large extent and was influenced by the linear combination of atomic orbitals method. Compared to the input structure, the output structure changed from COO^- and NH⁺₃ groups to COOH and NH₂, which did not reflect the actual vibrational mode. The intra and intermolecular vibrational modes were described by the cell configuration simulation. The absorption peak positions matched well with the measured values without proton transfer. The vibrational modes of the measured peak positions were better identified. The closest results of leucine and isoleucine calculations using the PBEsol general function to the measured values indicated that full consideration needs to be given to the matching of structure and general function in the simulation, i.e., the description of the structure exchange association energy and showed the universality of the same general function for the isomers. In addition, the difference after structural optimization cannot be used as the criterion to judge functional applicability. The results of cell configuration calculation include the intermolecular vibration mode, which cannot be obtained with a single molecular configuration. Moreover, the full width at half maximum fitting leads to the difference in the vibration mode of the two configuration results at a measured peak position.

Key words：Terahertz absorption spectroscopy;Amino acids;Quantum chemical calculations;Vibrational modes;Isomers

Received: 2022-11-24 Accepted: 2023-09-06

ZTFLH:

O433.1

Corresponding Authors: ZHAO Guo-zhong E-mail: guozhong-zhao@163.com

Cite this article:

LIU Xiao-song,ZHAO Guo-zhong,QU Yuan. Vibrational Mode Analysis of Leucine and Isoleucine Terahertz Spectra[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2024, 44(05): 1255-1261.

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https://www.gpxygpfx.com/EN/10.3964/j.issn.1000-0593(2024)05-1255-07 OR https://www.gpxygpfx.com/EN/Y2024/V44/I05/1255

[1] Vidal-Carou M C, Izquierdo-Pulido M L, Mariné-Font A. Journal of the Association of Official Analytical Chemists, 1989, 72(3): 412.
[2] Beil D, Kinder H, Paschke A, et al. Journal of Chromatographic Science，1998，36(6): 284.
[3] Beljaars P, Van Dijk R, Jonker K, et al. Journal of AOAC International, 1998, 81(5): 991.
[4] WANG Wei-ning, LI Hong-qi, ZHANG Yan, et al(王卫宁, 李洪起, 张岩, 等). Acta Physico-Chimica Sinica(物理化学学报), 2009, 25(10): 2074.
[5] HUANG Li-juan, ZHANG Xin, WANG Guo, et al(黄丽娟, 张欣, 王果, 等). Spectroscopy and Spectral Analysis(光谱学与光谱分析), 2017, 37(8): 2462.
[6] Williams M R C, Aschaffenburg D J, Ofori-Okai B K, et al. Journal of Physical Chemistry B, 2013, 117(36): 10444.
[7] Taday P F, Bradley I V, Arnone D D. Journal of Biological Physics, 2003, 29(2-3): 109.
[8] Yamaguchi M, Miyamaru F, Yamamoto K, et al. Temperature Dependence of Low-Frequency Vibrational Modes in Crystalline Amino Acids Studied by Terahertz Time-Domain Spectroscopy. In Conference on Lasers and Electro-Optics, 2003.
[9] Nishizawa J, Sasaki T, Suto K, et al. International Journal of Infrared and Millimeter Waves, 2006, 27: 779.
[10] Jensen F. Introduction to Computation Chemistry. 3rd ed. New York: John Wiley & Sons, 2016.
[11] Pauling L, Wilson Jr E B. Introduction to Quantum Mechanics with Application to Chemistry, Dover Publications, 1985. 82.
[12] Levine Ira N. Quantum Chemistry. 4th ed. Prentice Hall, 1991.
[13] Born M, Oppenheimer R. Annalen der Physik., 1927, 389(20)：457.
[14] Perdew J P，Burke K. Physics Review Letters, 1996, 77: 3865.
[15] Sagvolden E, Perdew J P. Physical Review A, 2008, 77: 012517.
[16] Hammer B, Hansen L B, Norskov J K. Physical Review B, 1999，59: 7413.
[17] Wu Zhigang, Cohen Ronald E. Physical Review B, 2006, 73: 235116.
[18] Becke A D. Physical Review A, 1986, 33(4): 2786.
[19] Zhao Yan, Truhlar Donald G. Theoretical Chemistry Accounts, 2008, 120: 215.
[20] Shen Y C, Upadhya P C, Linfield E H, et al. Vibrational Spectroscopy, 2004，35(1-2)：111.