Lukáš Tomaník, Michele Pugini, Karen Mudryk, Stephan Thürmer, Dominik Stemer, Bruno BC Credidio, Florian Trinter, Bernd Winter, Petr Slavicek
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引用次数: 0
摘要
液体喷射光发射光谱(LJ-PES)可直接探测溶质和溶剂的电子结构。它也是探索水溶液中化学结构的一种新工具,但这种方法的适用范围还有待研究。在此,我们介绍了抗坏血酸(维生素 C)的 pH 值依赖性液体喷射光电子能谱研究。我们结合了核心级光电子能谱和 ab initio 计算,从而能够针对特定位点探索生物大分子的酸碱化学性质。我们首次展示了该方法同时分配分子内两个去质子化位点的能力。我们表明,即使是与化学修饰基团相距几个键的原子,其化学位移也会发生很大变化。此外,我们还介绍了一种基于单一结构的高效、精确计算方案,该方案使用最大重叠法对水环境中的核心级光电子能谱进行建模。这项工作提出了一个更广泛的问题:LJ-PES 能在多大程度上对核磁共振等成熟的结构技术起到补充作用?鉴于已发表的大量错误分子结构,回答这一问题具有重要意义。
Liquid-Jet Photoemission Spectroscopy as a Structural Tool: Site-Specific Acid-Base Chemistry of Vitamin C
Liquid-jet photoemission spectroscopy (LJ-PES) directly probes the electronic structure of solutes and solvents. It also emerges as a novel tool to explore chemical structure in aqueous solutions, yet the scope of the approach has to be examined. Here, we present a pH-dependent liquid-jet photoelectron spectroscopic investigation of ascorbic acid (vitamin C). We combine core-level photoelectron spectroscopy and ab initio calculations, allowing us to site-specifically explore the acid-base chemistry of the biomolecule. For the first time, we demonstrate the capability of the method to simultaneously assign two deprotonation sites within the molecule. We show that a large change in chemical shift appears even for atoms distant several bonds from the chemically modified group. Furthermore, we present a highly efficient and accurate computational protocol based on a single structure using the maximum overlap method for modeling core-level photoelectron spectra in aqueous environments. This work poses a broader question: To what extent can LJ-PES complement established structural techniques such as nuclear magnetic resonance? Answering this question is highly relevant in view of the large number of incorrect molecular structures published.
期刊介绍:
Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions.
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