Developments and applications of cavity ring-down polarimetry for the detection and characterisation of optically active biological compounds.

用于检测和表征光学活性生物化合物的腔衰荡旋光法的开发和应用。

• 批准号: 2890146
• 金额: --
• 依托单位: University of Oxford
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2023
• 资助国家: 英国
• 起止时间: 2023 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2890146
• 关键词: Developments; applications; cavity; ring; down

This project will employ a bow-tie cavity arrangement to conduct high-sensitivity continuous-wave polarimetry on both gas- and solution-phase samples. The development of a continuous-flow solution-phase microfluidic setup will also facilitate the study of enantioselective adsorption mechanisms on the surfaces of substances such as magnetite, homochiral quartz, and vermiculite clays. This selective adsorption and the resulting chiral amplification have been posited as potential sources of biomolecular homochirality. Correspondingly, their study could help reveal new insights into the evolution of the chemicals of life on Earth.The increased sensitivity afforded by cavity-enhanced techniques allows for the detailed analysis of conformationally flexible molecules possessing small-magnitude optical rotations. Amino acids are good examples of such molecules and are of extreme interest, not only for probing the evolution of life, but also for understanding the chemistry occurring within our bodies on a cellular level. The observed optical rotation of an amino acid will vary depending on its charge state, as well as its state of aggregation, i.e., whether it exists in monomeric or polymeric form. Using the experimental setup detailed above, this project will seek to quantify the origins of phenomena such as the Clough-Lutz-Jirgensons rule, which describes the variation of an amino acid's optical rotation with pH, in addition to non-linear optical rotations observed for certain amino acids, the origin of which is thought to lie in dimerization processes in solution. To compliment the laser-based methodologies employed in the Ritchie Group, this project will also leverage the NMR and computational expertise of the Baldwin and Tew groups at the University of Oxford, respectively. Utilisation of quantitative NMR experiments will shed light on the underlying solution composition of the samples under study, while theoretical analyses are required to determine the conformational dependence of the optical rotation of each molecular species.In addition to the biological applications of this promising technique, this project will also investigate the utility of cavity ring-down polarimetry in real-time analysis and characterisation of industrially and synthetically relevant reactions in which chiral substrates are consumed and destroyed. Bearing in mind the prevalence of asymmetric synthetic methodologies in both Inorganic and Organic Chemistry, and the ever-increasing demand for chiral selectivity in catalytic processes, the real-time, non-destructive analysis that this technique provides has relevance across the Physical and Life Science. The dynamics of reactions containing chiral substrates will also be studied. In summary, the overall objective of this project is to employ cavity-enhanced polarimetric techniques in the study, characterisation and rationalisation of both optically-active substances and reactions across the gas and solution phases. As is evident from the above outline, this work falls within the EPSRC's broad research themes of healthcare technologies and the physical sciences, in addition to the corresponding strategic priorities of developing a physical and mathematical sciences powerhouse as well as the transformation of health and healthcare through greater understanding of the molecular complexity governing human biology.

该项目将采用弓形领域的排列，以对气体和溶液相样样品进行高敏性连续波偏光法。连续流溶液相微流体设置的开发还将促进对磁铁矿，磁铁矿，同粒病石英和肉虫粘土等物质表面上的对映射吸附机制的研究。这种选择性的吸附和由此产生的手性放大已被认为是二分子同源性的潜在来源。相应地，他们的研究可能有助于揭示对地球生命化学物质进化的新见解。腔体增强技术提供的灵敏度提高，可以详细分析具有小稳定的光学旋转的构型柔性分子。氨基酸是这种分子的好例子，并且具有极大的兴趣，不仅是用于探测生命的演变，而且还用于理解我们体内在细胞水平上发生的化学反应。观察到的氨基酸的光学旋转将根据其电荷状态及其聚集状态而变化，即其是否以单体或聚合物形式存在。使用上面详细列出的实验设置，该项目将寻求量化现象的起源，例如Clough-Lutz-Jirgensons规则，该规则描述了氨基酸与pH的光学旋转的变化，此外，除了对某些氨基酸观察到的非线性光学旋转外，该氨基酸旋转的某些氨基酸的变化，其原状是在Dimerization in dimerization in dimerization in Soluse in Solution in Solution in corese in dimeration in corese in Solution in corese。为了补充Ritchie组中使用的基于激光的方法，该项目还将分别利用牛津大学Baldwin和TEW组的NMR和计算专业知识。定量NMR实验的利用将阐明所研究样本的基础溶液组成，而理论分析需要确定每个分子物种的光学旋转的构象依赖性。在此前景技术的生物学应用中，该项目还将调查为为为为为行业环的偏光分析和特征的实用性分析和特征，以实现型号，并构成了实际的分析和特征。手性底物被消耗和破坏。考虑到无机和有机化学中不对称合成方法的普遍性，以及对催化过程中手性选择性的不断增长的需求，这项技术提供的实时，无损的分析是在物理和生命科学之间具有相关性的。还将研究包含手性底物的反应的动力学。总而言之，该项目的总体目标是在研究中采用腔体增强的极化技术，对气体和溶液阶段的光学活性物质以及反应的表征和合理化。从上述大纲中可以明显看出，这项工作还属于EPSRC的广泛研究主题，除了发展物理和数学科学强大的功能室的相应战略优先级外，还通过对人类生物学的分子复杂性进行更多的了解，以及对健康和医疗保健的转变。