Theoretical Investigation on the Structure and Vibration Spectrum of D-Luciferin
ZHU Yuan-qiang1, 2, ZHANG Li2, GUO Jian-chun1
1. State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation，Southwest Petroleum University, Chengdu 610500, China 2. School of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500, China
Abstract：In the present study, the geometry of D-Luciferin was fully optimized by the density functional theory at the B3LYP/6-311++G** and B3PW91/6-311++G** level, and the Cartesian coordinate force constant was calculated at the same level. The scaled quantum mechanism force field (SQM) method was performed to analyze the vibration spectrum. The local internal symmetry coordinates were defined using the method given by Pulay. The theoretical force field matrix, which was obtained through molecular vibration calculation programs, was transformed from Cartesian coordinates into the local internal coordinates. A normal coordinate analysis was carried out using GF matrix method developed by Wilson to give the scaled vibration frequencies and the potential energy distributions (PEDs). In order to make the vibration frequencies in good agreement with the experimental values, we empirically scale the theoretical force fields. According to PEDs, all vibration modes were assigned reliably to certain vibration frequencies. The calculated results show that the D-Luciferin molecule belongs to the point group C1 and involves 66 free degrees of vibration. All vibration modes are infrared and Raman activity. In the Infrared spectrum, the vibration frequency of the strongest absorption peak is 1 780 cm-1, and the absorption intensity is 507 KM·mol-1, which is mainly contributed by the stretching vibration mode of the C21O22 double bond with the PEDs of 93%. In the Raman spectrum, the vibration frequency in the range of 1 200～1 700 cm-1 presented strong Raman activity, the frequency of the strongest absorption peak is 1 573 cm-1, and the absorption intensity is 297 KM·mol-1, which is mainly contributed by the stretching vibration mode of the C21N22 double bond in the five-membered ring. The results are helpful to further studying the structure and the luminescence activity of Luciferin derivatives in experiment and theory.
[1] Robertson J B, Stowers C C, Boczko E, et al. Proc. Natl. Acad. Sci. USA, 2008, 105(46): 17988. [2] Kesarwala A H, Samrakandi M M, Piwnica-Worms D. Cancer Res., 2009, 69(9): 967. [3] LI Zuo-sheng, ZOU Lu-yi, REN Ai-min, et al(李作盛，邹陆一，任爱民，等). Chemical Journal of Chinese Universities(高等学校化学学报), 2012, 33(12): 2757. [4] White E H, McCapra F, Field G F, et al. J. Am. Chem. Soc., 1961, 83(10): 2402. [5] HU Bo, LIU Zi-li(胡 波，刘子立). Journal of Molecular Science(分子科学学报), 2006, 22(5): 354. [6] Presiado I, Erez Y, Huppert D J. Phys. Chem. A，2010, 114(36): 9471. [7] Stochkel K, Milne B F, Nielsen S B. J. Phys. Chem. A, 2011, 115(12): 2155. [8] Frisch M J, Trucks G W, Schlegel H B, et al. Gaussian 09, Revision D.01, Pittsburgh PA: Gaussian Inc, 2013. [9] Pulay P, Fogarasi G, Pang F, et al. J. Am. Chem. Soc., 1979, 101(10): 2550. [10] XUE Ying, XIE Dai-qian, YAN Guo-sen(薛 英，谢代前，鄢国森). Chemical Journal of Chinese Universities(高等学校化学学报), 1999, 20(7): 1102. [11] Wilson E B, Decius J C, Cross P C. Molecular Vibrations. New York: McGraw-Hill, 1955. [12] Pulay P, Fogarasi G, Pongor G. J. Am. Chem. Soc., 1983, 105(24): 7037. [13] Andersson M P, Uvdal P. J. Phys. Chem. A, 2005, 109(11): 2937.
