Probing the Origins of Intrinsic Chiroptical Response and the Roles of Extrinsic Perturbations
探讨内在手性光学响应的起源和外在扰动的作用
基本信息
- 批准号:2154840
- 负责人:
- 金额:$ 52.5万
- 依托单位:
- 依托单位国家:美国
- 项目类别:Standard Grant
- 财政年份:2022
- 资助国家:美国
- 起止时间:2022-08-01 至 2025-07-31
- 项目状态:未结题
- 来源:
- 关键词:
项目摘要
With support from the Chemical Structure, Dynamics, and Mechanisms-A (CSDM-A) program in the Division of Chemistry, Professor Patrick Vaccaro of Yale University is exploring spectroscopic signatures of molecular chirality to understand their fundamental origins and facilitate their practical applications. Molecules are chiral when their chemical structure is not identical to their mirror image, much in the same way that one's left and right hands are not superimposable. When chiral molecules interact with light, they can rotate its polarization, with molecules of opposite handedness rotating the polarization in opposite directions. However, using this polarization rotation to characterize chirality is challenging, as samples are often a mixture of left- and right-handed molecules, and the degree of rotation can be affected by the vibration of atoms in the molecule and interaction with surrounding solvent molecules. Professor Vaccaro and his group will address this challenge by combining experimental measurements with theoretical analyses to study how the atomic motions and surrounding solvent affect chiroptical properties of molecules. Their discoveries could have relevance to the study of chiral systems in biology as well as advance approaches to asymmetric catalysis. The project will also provide multidisciplinary research opportunities for individuals destined to become our next generation of scientists and educators, as well as engage pupils and teachers from regional K-12 schools in various aspects of scientific research.The electronic circular birefringence (ECB) of species possessing diverse structural and electronic motifs will be probed under solvated and isolated conditions, with the latter work relying on variants of ultrasensitive cavity ring-down polarimetry (CRDP). Aside from generating solvent-free benchmarks for validating theoretical predictions of dispersive optical activity, the putative roles played by nuclear degrees of freedom will be dissected systematically through temperature-dependent and optical-pumping probes of vibrational dynamics, as well as by the unique spectral signatures arising from isotopically engendered chirality (IEC). In additional to unraveling the intimate coupling among achiral-electronic and chiral-nuclear degrees of freedom that must be responsible for IEC optical activity, vibronic paradigms will be elaborated to engineer isotopic circular-differential response properties. The crucial link between isolated and solvated chiroptical response will be forged by conducting studies in tunable supercritical fluids that allow the physicochemical properties of a medium to be varied without altering the basic nature of intermolecular forces. Guided by parallel quantum-chemical analyses and molecular-dynamics simulations, such efforts will describe optical activity in solitary species while simultaneously exploring complex chiral solvation phenomena.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.
在化学系化学结构、动力学和机理(CSDM-A)项目的支持下,耶鲁大学的Patrick Vaccaro教授正在探索分子手性的光谱特征,以了解它们的基本起源并促进它们的实际应用。当分子的化学结构与其镜像不同时,分子就是手性的,就像一个人的左手和右手不能重叠一样。当手性分子与光相互作用时,它们可以旋转光的偏振,而反手分子则以相反的方向旋转偏振。然而,使用这种极化旋光来表征手性是具有挑战性的,因为样品通常是左旋和右旋分子的混合物,旋光的程度会受到分子中原子的振动以及与周围溶剂分子的相互作用的影响。瓦卡罗教授和他的团队将通过将实验测量与理论分析相结合来解决这一挑战,以研究原子运动和周围溶剂如何影响分子的手性属性。他们的发现可能与生物学中手性系统的研究以及不对称催化的先进方法有关。该项目还将为注定成为我们下一代科学家和教育工作者的个人提供多学科的研究机会,并让来自地区K-12学校的学生和教师参与到各个方面的科学研究中。具有不同结构和电子基元的物种的电子圆双折射(ECB)将在溶剂化和孤立的条件下进行探索,后者的工作依赖于超灵敏腔衰荡偏振(CRDP)的变体。除了生成用于验证色散光学活性的理论预测的无溶剂基准之外,还将通过振动动力学的温度依赖和光学泵浦的探头,以及由同位素产生的手性(IEC)产生的独特光谱特征,系统地剖析核自由度所起的假定作用。除了解开必须负责IEC光学活性的非手性-电子和手性-核自由度之间的紧密耦合之外,还将详细阐述振动范例以设计同位素循环差示响应特性。分离的和溶剂化的手势反应之间的关键联系将通过在可调超临界流体中进行研究来形成,这种超临界流体允许在不改变分子间力的基本性质的情况下改变介质的物理化学性质。在并行量子化学分析和分子动力学模拟的指导下,这些努力将描述孤立物种中的光学活动,同时探索复杂的手性溶剂化现象。这一奖项反映了NSF的法定使命,并通过使用基金会的智力优势和更广泛的影响审查标准进行评估,被认为值得支持。
项目成果
期刊论文数量(2)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Isolated and solvated chiroptical behavior in conformationally flexible butanamines
构象柔性丁胺中的分离和溶剂化手性光学行为
- DOI:10.1002/chir.23570
- 发表时间:2023
- 期刊:
- 影响因子:2
- 作者:Lemler, Paul M.;Craft, Clayton L.;Pollok, Corina H.;Regan, Thomas P.;Vaccaro, Patrick H.
- 通讯作者:Vaccaro, Patrick H.
{{
item.title }}
{{ item.translation_title }}
- DOI:
{{ item.doi }} - 发表时间:
{{ item.publish_year }} - 期刊:
- 影响因子:{{ item.factor }}
- 作者:
{{ item.authors }} - 通讯作者:
{{ item.author }}
数据更新时间:{{ journalArticles.updateTime }}
{{ item.title }}
- 作者:
{{ item.author }}
数据更新时间:{{ monograph.updateTime }}
{{ item.title }}
- 作者:
{{ item.author }}
数据更新时间:{{ sciAawards.updateTime }}
{{ item.title }}
- 作者:
{{ item.author }}
数据更新时间:{{ conferencePapers.updateTime }}
{{ item.title }}
- 作者:
{{ item.author }}
数据更新时间:{{ patent.updateTime }}
Patrick Vaccaro其他文献
Infection d'endoprothèse se présentant comme une rupture d'anévrysme aortique
- DOI:
10.1016/j.acvfr.2010.05.007 - 发表时间:
2009-11-01 - 期刊:
- 影响因子:
- 作者:
Jean Starr;Gregory Walker;Patrick Vaccaro - 通讯作者:
Patrick Vaccaro
Treatment Comparisons in Management of Localized Groin Wound Prosthetic Graft Infection
- DOI:
10.1016/j.jvs.2021.07.147 - 发表时间:
2021-10-01 - 期刊:
- 影响因子:
- 作者:
Thomas Joseph Perry;Simon Fraser;Kristine Orion;Mounir Haurani;Bryan Tillman;Patrick Vaccaro;Michael Go;Timur Sarac - 通讯作者:
Timur Sarac
29 (CR). Axillary-Femoral Bypass May Provide Inadequate Distal Perfusion Compared To In-Line Large Diameter Aortic Reconstruction
- DOI:
10.1016/j.avsg.2015.04.031 - 发表时间:
2015-05-01 - 期刊:
- 影响因子:
- 作者:
Loren L. Masterson;Patrick Vaccaro;Michael R. Go - 通讯作者:
Michael R. Go
Treatment Comparisons in Management of Localized Groin Wound Prosthetic Graft Infection
- DOI:
10.1016/j.jvs.2021.06.425 - 发表时间:
2021-09-01 - 期刊:
- 影响因子:
- 作者:
Thomas J. Perry;Kristine Orion;Mounir Haurani;Bryan Tillman;Patrick Vaccaro;Michael R. Go;Timur P. Sarac - 通讯作者:
Timur P. Sarac
Extra-Anatomic Bypass and Excision is Superior to Graft Salvage Attempts with Antibiotic Beads to Treat Vascular Graft Infections in the Groin
- DOI:
10.1016/j.avsg.2022.08.008 - 发表时间:
2023-01-01 - 期刊:
- 影响因子:
- 作者:
Thomas J. Perry;Simon Fraser;Kristine Orion;Mounir Haurani;Bryan Tillman;Patrick Vaccaro;Michael R. Go;Timur P. Sarac - 通讯作者:
Timur P. Sarac
Patrick Vaccaro的其他文献
{{
item.title }}
{{ item.translation_title }}
- DOI:
{{ item.doi }} - 发表时间:
{{ item.publish_year }} - 期刊:
- 影响因子:{{ item.factor }}
- 作者:
{{ item.authors }} - 通讯作者:
{{ item.author }}
{{ truncateString('Patrick Vaccaro', 18)}}的其他基金
Spectroscopic Probes of Molecular Structure and Dynamics
分子结构和动力学的光谱探针
- 批准号:
1464957 - 财政年份:2015
- 资助金额:
$ 52.5万 - 项目类别:
Continuing Grant
Spectroscopic Probes of Molecular Structure and Dynamics
分子结构和动力学的光谱探针
- 批准号:
1112239 - 财政年份:2011
- 资助金额:
$ 52.5万 - 项目类别:
Continuing Grant
Spectroscopic Probes of Molecule Structure and Dynamics
分子结构和动力学的光谱探针
- 批准号:
0809856 - 财政年份:2008
- 资助金额:
$ 52.5万 - 项目类别:
Continuing Grant
Spectroscopic Probes of Molecular Structure and Dynamics
分子结构和动力学的光谱探针
- 批准号:
0447567 - 财政年份:2005
- 资助金额:
$ 52.5万 - 项目类别:
Continuing Grant
Linear and Nonlinear Spectroscopy of Unimolecular Dynamics
单分子动力学的线性和非线性光谱
- 批准号:
9975428 - 财政年份:1999
- 资助金额:
$ 52.5万 - 项目类别:
Continuing Grant
Resonant Four-Wave Mixing Probes of Molecular Structure and Dynamics
分子结构与动力学的共振四波混合探针
- 批准号:
9523286 - 财政年份:1995
- 资助金额:
$ 52.5万 - 项目类别:
Continuing Grant
Coherent Light Scattering Spectroscopy: A New Probe for Vibrationally Excited Species
相干光散射光谱:振动激发物种的新探针
- 批准号:
9207835 - 财政年份:1992
- 资助金额:
$ 52.5万 - 项目类别:
Continuing Grant
Presidential Young Investigator Award: Chemical Dynamics of Rovibrationally Excited Molecules
总统青年研究员奖:旋转激发分子的化学动力学
- 批准号:
9158107 - 财政年份:1991
- 资助金额:
$ 52.5万 - 项目类别:
Continuing Grant
相似海外基金
Norway. Neuropeptide origins; study of neuropeptide functions in choanoflagellates
挪威。
- 批准号:
BB/X018512/1 - 财政年份:2024
- 资助金额:
$ 52.5万 - 项目类别:
Research Grant
Leveraging the synergy between experiment and computation to understand the origins of chalcogen bonding
利用实验和计算之间的协同作用来了解硫族键合的起源
- 批准号:
EP/Y00244X/1 - 财政年份:2024
- 资助金额:
$ 52.5万 - 项目类别:
Research Grant
Collaborative Research: Uncovering the adaptive origins of fossil apes through the application of a transdisciplinary approach
合作研究:通过应用跨学科方法揭示类人猿化石的适应性起源
- 批准号:
2316612 - 财政年份:2024
- 资助金额:
$ 52.5万 - 项目类别:
Standard Grant
Collaborative Research: Uncovering the adaptive origins of fossil apes through the application of a transdisciplinary approach
合作研究:通过应用跨学科方法揭示类人猿化石的适应性起源
- 批准号:
2316615 - 财政年份:2024
- 资助金额:
$ 52.5万 - 项目类别:
Standard Grant
The developmental and evolutionary origins of vertebrate fins and limbs.
脊椎动物鳍和四肢的发育和进化起源。
- 批准号:
DP240102156 - 财政年份:2024
- 资助金额:
$ 52.5万 - 项目类别:
Discovery Projects
Origins and implications of cosmic explosions
宇宙爆炸的起源和影响
- 批准号:
DE240100433 - 财政年份:2024
- 资助金额:
$ 52.5万 - 项目类别:
Discovery Early Career Researcher Award
ORIGINS - Organic molecular generation of protocells on iron minerals
起源 - 在铁矿物上有机分子生成原始细胞
- 批准号:
NE/Z000041/1 - 财政年份:2024
- 资助金额:
$ 52.5万 - 项目类别:
Research Grant
Collaborative Research: Uncovering the adaptive origins of fossil apes through the application of a transdisciplinary approach
合作研究:通过应用跨学科方法揭示类人猿化石的适应性起源
- 批准号:
2316614 - 财政年份:2024
- 资助金额:
$ 52.5万 - 项目类别:
Standard Grant
NSF PRFB FY23: Linking genotypes, phenotypes, and ecology to elucidate the origins of parasite resistance
NSF PRFB FY23:将基因型、表型和生态学联系起来,阐明寄生虫抗性的起源
- 批准号:
2305974 - 财政年份:2024
- 资助金额:
$ 52.5万 - 项目类别:
Fellowship Award