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

基本信息

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：
2022
资助国家：
加拿大
起止时间：
2022-01-01 至 2023-12-31
项目状态：
已结题

来源：
https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=748165
关键词：
Spectroscopic Signatures Chirality Recognition Transfer

项目摘要

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.

如果分子不能将其镜像叠加到自身上，就像我们的右手和左手一样。由于一对镜像的相似性，在许多情况下，用镜像映像替换为镜像，很少引入相关系统的属性。在手性识别事件中，手性分子与另一个手性分子或手性光相互作用时，手性的效果很突出，就像在人握手的情况下一样（即右/右/右/右手的感觉如何不同，右/右手感觉如何）。更一般而言，手性在生物系统中无处不在，对生活至关重要。手性识别是许多生物学过程的核心，包括涉及药物的生物过程，在立体选择性化学中至关重要。我们旨在了解溶剂和光辐射对分子水平上手性识别和转移事件的影响，以便以预测能力来制定严格的手性识别和转移模型，并制定新的策略以光线控制这些事件。 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.如此较大的群集以前很少进行调查。 2）我们将利用两种强大的手性手学工具，即振动圆二色性和拉曼光学活性光谱，以探测溶液中非共价相互作用和手性转移。我们将重点关注手性转移/扩增的机制（近）共振，这些机制几乎没有探索过。 3）在我们先前在仪器开发方面取得成功的建立，我们将通过将其耦合到氦纳米环分离光谱仪来进一步开发混合质量激光光谱仪。混合激光质量仪器不仅可以使我们不仅可以在室温和0.4 K处探测氨基酸和肽聚集体中的手性识别，还可以通过利用柔和的氦基质来稳定它们，从而访问反应中间体。 4）我们将探索液体液体界面的手性识别和归纳，这是我们引发的新研究方向。拟议的研究的结果对手学起着重要作用的化学，物理学和生物学的许多子领域来说都是有价值的。获得的基本知识对于开发从传感器的药物过程和环境监测的传感器到手性药物合成的新型催化剂至关重要。