Collaborative Research: DNP-Enhanced Nuclear-Spin Optical-Rotation Spectroscopy

CHE-1404529和CHE-1404548：合作研究：DNP增强核自旋光学旋转光谱在这个由化学部化学测量和成像计划资助的项目中，新墨西哥州财团的Igor Savukov博士和Christian B教授。Hilty的合作开发核自旋旋光方法学，以提高光学和核磁共振光谱学中的信息含量。 该技术通过动态矢量极化率将核自旋态和电子结构关联起来。有意义的应用的严重障碍是，测量的效果通常是非常小的，需要大量的时间来检测，即使在水中具有非常大的质子浓度。核自旋旋光在化学中应用的进展关键取决于信号增强的策略。与目前的方法相比，在稀样品或具有多个峰的样品中的光谱应用需要大的改进。在这里，动态核极化被用来产生非平衡核自旋态。超极化样品可以增加100- 100，000倍的核自旋旋光信号，这取决于核和实验条件，并使该方法能够应用于各种化合物的表征。这种新的光谱技术分三步开发。首先，证明了动态核极化超极化样品的核自旋旋光。其次，增强效应的特点是各种以前无法访问的核和分子，并与理论的结果进行比较。第三，将该技术应用于染料分子电子结构的表征。从长远来看，这种新光谱的实现为液体中光-物质相互作用的基础研究提供了一种强有力的分析方法。分子的电子结构，无论是在基态还是激发态，都决定了其基本的分子性质和反应活性。电子结构的测量对于理解分子在化学反应和其他相互作用中的行为是必要的。在这个项目中，一种新型的光谱学正在开发中，这种光谱学是唯一适合于探测电子的空间局部激发态配置的。这种光谱学是基于通过最近发现的核自旋旋光效应与分子中特定原子相关的光学信号的测量。 该项目包括通过新墨西哥州联合会和得克萨斯州农工大学之间的伙伴关系开展教育活动。包括研究生和本科生在内的早期职业科学家正在接受指导，这项研究的结果被纳入讲座课程中。

CHE-1404529 and CHE-1404548: Collaborative Research: DNP-Enhanced Nuclear-Spin Optical-Rotation SpectroscopyIn this project funded by the Chemical Measurement and Imaging Program of the Chemistry Division, Dr. Igor Savukov of the New Mexico Consortium and Professor Christian B. Hilty of Texas A & M University are collaboratively developing nuclear-spin optical rotation methodology for enhancing the information content in optical and nuclear magnetic resonance spectroscopy. The technique correlates nuclear spin states and electronic structure through dynamic vector polarizability. The severe obstacle for meaningful application is that the measured effect is normally extremely small, requiring substantial time for detection, even in water with very large concentration of protons. Progress in the application of nuclear-spin optical rotation to chemistry critically depends on strategies for signal enhancement. Compared to current methods, large improvements are needed for spectroscopy applications in dilute samples or samples with multiple peaks. Here, dynamic nuclear polarization is used to generate non-equilibrium nuclear spin states. Hyperpolarized samples can increase the nuclear-spin optical rotation signal 100-100,000 times, depending on the nuclei and experimental conditions and enable application of the method for the characterization of various chemical compounds. This new spectroscopic technique is being developed in three steps. First, nuclear-spin optical rotation of samples hyperpolarized by dynamic nuclear polarization is demonstrated. Second, the enhancement effect is characterized for various previously inaccessible nuclei and molecules, and results are compared with theory. Third, the technique is applied to the characterization of electronic structure in dye molecules. In the long term, the realization of this new spectroscopy offers a powerful analytical method for fundamental studies of light-matter interaction in liquids. The electronic structure of a molecule, both in ground and excited states, determines its basic molecular properties and reactivity. Measurements of electronic structure are necessary to understand the behavior of molecules in chemical reactions and other interactions. In this project, a new type of spectroscopy is being developed that is uniquely suited to probe spatially localized excited-state configurations of electrons. This spectroscopy is based on the measurement of an optical signal that is correlated to specific atoms in the molecule via the recently discovered nuclear-spin optical rotation effect. The project includes educational activities through a partnership between the New Mexico Consortium and Texas A&M University. Early-career scientists, including graduate an undergraduate students are being mentored, and the results from this research are incorporated into lecture classes.