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Study of Adenine and Guanine Oxidation Mechanism by Surface-Enhanced Raman Spectroelectrochemistry

机译:表面增强拉曼光谱电化学研究腺嘌呤和鸟嘌呤氧化机理

摘要

Metal nanoparticles are systems largely employed in surface-enhanced Raman spectroscopy (SERS). In particular, gold nanoparticles are one of the best substrates used in this field. In this work, the optimal conditions for gold nanoparticles electrodeposition on single-walled carbon nanotubes electrodes have been established to obtain the best SERS response. Using this substrate and analyzing the changes of in situ Raman spectra obtained at different potentials, we have been able to explain simultaneously the oxidation mechanism of purine bases, differentiating the oxidation intermediates and their orientation during the different oxidation steps. Adenine orientation hardly changes during the whole oxidation; the molecule maintains a parallel configuration and only shows a slightly tilted orientation after the first oxidation step. On the other hand, guanine orientation changes completely during its oxidation. Initially, guanine is perpendicular respect to gold nanoparticles, changing its orientation after the first oxidation process when the molecule shows a slightly tilted orientation, and it finishes parallel respect to the electrode surface after the second oxidation step.
机译:金属纳米颗粒是主要用于表面增强拉曼光谱(SERS)的系统。特别地,金纳米颗粒是该领域中使用的最好的基底之一。在这项工作中,已经建立了在单壁碳纳米管电极上电沉积金纳米颗粒的最佳条件,以获得最佳的SERS响应。使用这种底物并分析在不同电势下获得的原位拉曼光谱的变化,我们已经能够同时解释嘌呤碱的氧化机理,区分氧化中间体及其在不同氧化步骤中的取向。在整个氧化过程中,腺嘌呤取向几乎不变;该分子保持平行构型,并且在第一步氧化步骤后仅显示出略微倾斜的取向。另一方面,鸟嘌呤的取向在其氧化过程中完全改变。最初,鸟嘌呤相对于金纳米颗粒垂直,在第一氧化过程之后,当分子显示出略微倾斜的取向时,鸟嘌呤会改变其取向;在第二氧化步骤之后,它相对于电极表面平行完成。

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