Spectroscopic Signatures of Chirality Recognition, Transfer and Amplification: from the Gas Phase to Solution and Interfaces

手性识别、传递和放大的光谱特征：从气相到溶液和界面

• 批准号: RGPIN-2018-04944
• 负责人: Xu, Yunjie
• 金额: $ 6.85万
• 依托单位: University of Alberta
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2020
• 资助国家: 加拿大
• 起止时间: 2020-01-01 至 2021-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=712615
• 关键词: Spectroscopic; Signatures; Chirality; Recognition; Transfer

A molecule is chiral if its mirror image cannot be superimposed onto itself, just like our right and left hands. Because of the similarity of a pair of mirror images, replacing one with its mirror image, may, in many instances, introduce little or no change in the properties of the associated system. In a chirality recognition event when a chiral molecule interacts with another chiral molecule or chiral light, however, the effect of chirality is prominent, just as in the case of a human handshake (i.e. how different a right/right versus a left/right handshake feels). More generally, chirality is ubiquitous in biological systems and essential for life. Chirality recognition is at the heart of many biological processes including those involving pharmaceuticals and is of chief importance in stereoselective chemistry. We aim to understand the effects of solvent and light radiation on chirality recognition and transfer events at the molecular level in order to formulate rigorous chirality recognition and transfer models with predictive power and to develop new strategies to control these events with light. We will pursue innovative research activities in four core directions which are unified under the central theme of chirality and chirality recognition in the next funding cycle: 1) In order to follow the first few crucial steps of aggregation and solvation in unprecedented detail, we will apply chirped-pulse microwave spectroscopy to study clusters of chiral molecules and solvent molecules with increasing number of subunits. Such larger clusters have rarely been investigated before. 2) We will utilize two powerful chiroptical tools, namely vibrational circular dichroism and Raman optical activity spectroscopy to probe non-covalent interactions and chirality transfer in solution. We will focus on mechanisms of chirality transfer/amplification under (near) resonance which have hardly been explored before. 3) Building on our prior success in instrument development, we will further develop our hybrid mass-laser spectroscopic instrument by coupling it to a helium nanodroplet isolation spectrometer. The hybrid laser-mass instruments will allow us not only to probe chirality recognition in aggregates of amino acids and peptides at room temperature and at 0.4 K, but also to access reaction intermediates by utilizing the gentle helium matrix to stabilize them. 4) We will explore chirality recognition and induction at liquid-liquid interfaces, a new research direction we initiated. The outcome of the proposed research will be valuable to many subfields in chemistry, physics, and biology where chirality plays a significant role. The fundamental knowledge gained will be important for developing a broad range of chiral technologies from sensors for pharmaceutical processes and environmental monitoring to novel catalysts for chiral drug syntheses.

如果一个分子的镜像不能像我们的右手和左手那样叠加在自己身上，那么它就是手性的。由于一对镜像的相似性，在许多情况下，用其镜像替换一个镜像可能对关联系统的属性带来很小或没有变化。然而，在手性识别事件中，当一个手性分子与另一个手性分子或手性光相互作用时，手性的影响是突出的，就像人类握手的情况一样(即右/右握手与左/右握手的感觉有多么不同)。更广泛地说，手性在生物系统中无处不在，对生命是必不可少的。手性识别是包括药物在内的许多生物过程的核心，在立体选择性化学中具有重要意义。 我们的目标是在分子水平上了解溶剂和光辐射对手性识别和转移事件的影响，以便建立具有预测能力的严格的手性识别和转移模型，并开发用光控制这些事件的新策略。在下一个资金周期，我们将在手性和手性识别这一中心主题下，在四个核心方向上进行创新的研究活动：1)为了以前所未有的细节跟踪最初几个关键的聚集和溶剂化步骤，我们将应用啁啾脉冲微波光谱来研究亚基数量不断增加的手性分子和溶剂分子簇。这样大的星系团以前很少被研究过。2)我们将利用两个强大的手性工具，即振动圆二色谱和拉曼光学活性光谱来探测溶液中的非共价相互作用和手性转移。我们将集中讨论在(近)共振下的手性转移/放大机制，这些机制以前几乎没有被探索过。3)在以往仪器开发成功的基础上，我们将进一步开发我们的混合质量-激光光谱仪，将其耦合到氦纳米液滴隔离光谱仪上。激光-质量混合仪器不仅可以在室温和0.4K下探测氨基酸和多肽聚集体的手性识别，还可以利用温和的氦基质来稳定它们，从而获得反应中间产物。4)探索我们开创的一个新的研究方向--液-液界面手性识别与诱导。 拟议的研究结果将对化学、物理和生物学中手性起重要作用的许多子领域具有价值。所获得的基础知识将对开发从用于制药过程和环境监测的传感器到用于手性药物合成的新型催化剂等广泛的手性技术具有重要意义。