光谱学与光谱分析, 2011, 31 (12): 3273, 网络出版: 2012-01-05
银岛膜表面胸腺嘧啶吸附行为的表面增强拉曼光谱和表面增强红外光谱研究
Thymine on Silver Island Films: Surface-Enhanced Raman Scattering and Surface-Enhanced Infrared Absorption Studies
胸腺嘧啶 银岛膜 表面增强拉曼光谱 表面增强红外光谱 Thymine Silver island films Surface-enhanced Raman scattering Surface-enhanced infrared absorption
摘要
利用激光刻蚀法制备了具有“化学纯净” 表面的银岛膜, 该岛膜有很好的表面增强特性。 利用表面增强拉曼光谱和表面增强红外光谱对胸腺嘧啶分子在银岛膜表面的吸附状态进行了对比研究。 表面增强拉曼光谱中CN和C—O伸缩振动模式的出现表明胸腺嘧啶分子由原来的酮式结构变成了烯醇式结构; C(4)O伸缩振动谱带明显增强和N(3)的去质子化异构体特征峰的存在证明胸腺嘧啶分子是通过O(8)和N(3) 的共同作用倾斜地吸附在银岛膜表面。 对10-5 mol·L-1胸腺嘧啶在银岛膜表面上的红外光谱利用欧米采样器进行了反射法测量, 发现其红外吸收增强了200倍。 红外信号分析的结果支持了胸腺嘧啶分子通过O(8)与银表面发生相互作用的论断, 同时也可得出胸腺嘧啶倾斜地吸附在银岛膜表面的结论。
Abstract
Thymine, being one of the four nucleobases in the nucleic acid of DNA, has received an increasing interest due to its potential importance in genetics and possible applications in medical science. In the present study, adsorption of thymine on laser-ablated silver island films was comparatively analyzed by means of surface-enhanced Raman scattering (SERS) and surface-enhanced infrared absorption (SEIRA). Two new bands at 1 305 and 1 573 cm-1 appeared in the SERS spectrum of thymine on silver island films and represented that the molecule configuration of thymine hydrolyzed ion compound changed its structure from a keto form to an enol one. The greater enhancements of in-plane ring breath vibration bands and of 1 649 cm-1 band associated with C(4)O stretching vibration clearly suggested that the thymine molecules were adsorbed on the silver surface via O(8). The interaction of N(3) with silver surface could be inferred by the emergence of a stronger peak at 773 cm-1, which was assigned to the ring breath caused by the stretching vibration of the C(6)—N(3)—C(2). The blue shift of ring breath vibration from 749 to 773 cm-1 indicated that thymine ring should have some weak interaction with silver surface, i.e., there was a certain angle between the thymine ring and the silver surface. To sum up, the SERS spectrum indicated that thymine adsorbed on the silver surface as enolate through the O(8) and N(3) atoms. The molecular plane assumed a tilted orientation with respect to the silver surface. Laser-ablated silver island films also exhibited a good surface enhancement to infrared absorption for thymine. Enhancement factor was estimated to be about 200 under our experimental condition. There was no shift of C(2)O stretching vibration in SEIRA spectrum, revealing that O (7) was not involved in the adsorption process. Consistent with our SERS spectrum, the greater enhancement of the thymine ring deformation vibration (1 730 cm-1) in SEIRA agreed a tilted orientation of thymine on silver surface.
郭浩, 毕立恒, 丁丽, 莫育俊. 银岛膜表面胸腺嘧啶吸附行为的表面增强拉曼光谱和表面增强红外光谱研究[J]. 光谱学与光谱分析, 2011, 31(12): 3273. GUO Hao, BI Li-heng, DING Li, MO Yu-jun. Thymine on Silver Island Films: Surface-Enhanced Raman Scattering and Surface-Enhanced Infrared Absorption Studies[J]. Spectroscopy and Spectral Analysis, 2011, 31(12): 3273.