Collaborative Research: Continuous-Flow Hyperpolarization of Liquids Utilizing Parahydrogen and Heterogeneous Catalysis

合作研究：利用仲氢和多相催化的液体连续流超极化

• 批准号: 2108306
• 负责人: Clifford Bowers
• 金额: $ 30万
• 依托单位: University of Florida
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-08-01 至 2024-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2108306&HistoricalAwards=false
• 关键词: Collaborative; Research; Continuous; Flow; Hyperpolarization

With support from the Chemical Measurement and Imaging (CMI) Program in the Division of Chemistry (CHE), and partial co-funding from two other CHE programs, Chemical Structures, Dynamics, and Mechanisms - A (CSDM-A) , and Chemical Catalysis (CAT) and also from the Molecular Biophysics Cluster in the Molecular and Cellular Biosciences (MCB) Division, Professors Clifford R. Bowers at the University of Florida and Wenyu Huang at Iowa State University seek to develop new instrumentation and protocols for enhancing the sensitivity of nuclear magnetic resonance (NMR) spectroscopy, an important method for characterizing the composition and structure of chemical structures and the foundation of magnetic resonance imaging – a major tool for medical diagnostics. The team is developing continuous-flow methods and advanced intermetallic nanoparticle catalysts in efforts to improve the sensitivity of NMR spectroscopy by more than a factor of 10,000. The research will provide research experiences for high school and undergraduate students coordinated through the Center for Pre-collegiate Education and Training (CPET) at the University of Florida and several NSF Research Experiences for Undergraduates (REU) programs. In Ames, Iowa, outreach activities additionally include science shows and involvement of undergraduates and high school students in research activities and demonstrations incorporating project concepts.Nuclear Magnetic Resonance (NMR) relies on population differences among nuclear spin energy levels (i.e. spin polarization) in a molecule. In conventional NMR, spin polarization is induced by placing the sample in a high static magnetic field. However, even at the highest available magnetic fields, thermal equilibrium spin polarizations near ambient temperature are no greater than about 0.01%, and hence the NMR transition intensities are inherently weak. Parahydrogen-based hyperpolarization can provide a robust and cost-effective method that is scalable and compatible with rapid and continuous production of molecules in fluids with polarizations approaching 100%. For production of hyperpolarized liquids from parahydrogen, heterogeneous catalysis offers key benefits: the solid catalysts can provide consistent activity (under appropriate conditions) and the catalyst material can be easily separated from dissolved hyperpolarization products. Advancement of solution-state hyperpolarization from parahydrogen and heterogeneous catalysis requires a clear understanding of the catalytic mechanism and parahydrogen spin dynamics after dissociation of the molecule. The development of parahydrogen-enhanced polarization by continuous-flow heterogeneous catalysis will facilitate fundamental studies of the underlying mechanisms and spin dynamics of hyperpolarization from hydrogenation reactions as well as non-hydrogenative processes such as surface-mediated hyperpolarization from parahydrogen.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.

在化学部（CHE）的化学测量和成像（CMI）计划的支持下，以及其他两个CHE计划，化学结构，动力学和机制- A（CSDM-A）和化学催化（CAT）以及分子和细胞生物科学（MCB）部门的分子生物物理学集群的部分共同资助，Clifford R.佛罗里达大学的Bowers和爱荷华州州立大学的Wenyu Huang寻求开发新的仪器和协议，以提高核磁共振（NMR）光谱的灵敏度，这是表征化学结构组成和结构的重要方法，也是磁共振成像的基础-医学诊断的主要工具。该团队正在开发连续流方法和先进的金属间纳米颗粒催化剂，以提高NMR光谱的灵敏度超过10，000倍。该研究将通过佛罗里达大学预科教育和培训中心（CPET）和几个NSF本科生研究经验（REU）计划为高中和本科生提供研究经验。在爱荷华州的艾姆斯，外展活动还包括科学展览和大学生和高中生参与研究活动和结合项目概念的演示。核磁共振（NMR）依赖于分子中核自旋能级（即自旋极化）之间的总体差异。在常规NMR中，通过将样品置于高静磁场中来诱导自旋极化。然而，即使在最高可用磁场下，接近环境温度的热平衡自旋极化也不大于约0.01%，因此NMR跃迁强度固有地较弱。基于仲氢的超极化可以提供一种稳健且具有成本效益的方法，该方法是可扩展的并且与在具有接近100%的极化的流体中快速且连续地产生分子相容。对于从仲氢生产超极化液体，多相催化提供了关键的好处：固体催化剂可以提供一致的活性（在适当的条件下），催化剂材料可以很容易地从溶解的超极化产物中分离出来。从仲氢和多相催化的溶液态超极化的进步需要一个清晰的理解的催化机制和仲氢分子解离后的自旋动力学。通过连续流动多相催化的仲氢增强极化的发展将促进对氢化反应以及非氢化过程（如表面氢化）的超极化的基本机制和自旋动力学的基础研究。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响进行评估，被认为值得支持审查标准。

项目成果

Perpetual hyperpolarization of allyl acetate from parahydrogen and continuous flow heterogeneous hydrogenation with recycling of unreacted propargyl acetate

仲氢中乙酸烯丙酯的永久超极化和连续流非均相氢化以及回收未反应的乙酸炔丙酯

• DOI: 10.1016/j.jmro.2022.100076
• 发表时间: 2022
• 期刊: Journal of Magnetic Resonance Open
• 作者: Zhao, Tommy Yunpu;Lapak, Michelle P.;Behera, Ranjan;Zhao, Hanqin;Ferrer, Maria-Jose;Weaver, Helena E.;Huang, Wenyu;Bowers, Clifford R.
• 通讯作者: Bowers, Clifford R.

Adiabatic Passage through Level Anticrossings in Systems of Chemically Inequivalent Protons Incorporating Parahydrogen: Theory, Experiment, and Prospective Applications.

• DOI: 10.1021/jacs.2c09000
• 发表时间: 2022-11-16
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Ferrer, Maria-Jose;Kuker, Erin L.;Semenova, Evgeniya;Gangano, Anghelo Josh;Lapak, Michelle P.;Grenning, Alexander J.;Dong, Vy M.;Bowers, Clifford R.
• 通讯作者: Bowers, Clifford R.

Ultrasmall amorphous zirconia nanoparticles catalyse polyolefin hydrogenolysis

• DOI: 10.1038/s41929-023-00910-x
• 发表时间: 2023-02
• 期刊: Nature Catalysis
• 影响因子: 37.8
• 作者: Shaojiang Chen;A. Tennakoon;Kyung-Eun You;A. L. Paterson;Ryan D. Yappert;S. Alayoglu;Lingzhe Fang;Xun Wu;T. Y. Zhao;Michelle P. Lapak;Mukunth Saravanan;Ryan A. Hackler;Yi-Yu Wang;Long Qi;M. Delferro;Tao Li;Byeongdu Lee;B. Peters;K. Poeppelmeier;S. C. Ammal;C. Bowers;Frédéric A. Perras;Andreas Heyden;A. Sadow;Wenyu Huang

Instrumentation for Hydrogenative Parahydrogen-Based Hyperpolarization Techniques.

• DOI: 10.1021/acs.analchem.1c04863
• 发表时间: 2022-01-11
• 期刊: Analytical chemistry
• 影响因子: 7.4
• 作者: Schmidt AB;Bowers CR;Buckenmaier K;Chekmenev EY;de Maissin H;Eills J;Ellermann F;Glöggler S;Gordon JW;Knecht S;Koptyug IV;Kuhn J;Pravdivtsev AN;Reineri F;Theis T;Them K;Hövener JB
• 通讯作者: Hövener JB

Silica-Encapsulated Intermetallic Nanoparticles for Highly Active and Selective Heterogeneous Catalysis

• DOI: 10.1021/accountsmr.1c00153
• 发表时间: 2021-11-17
• 期刊: ACCOUNTS OF MATERIALS RESEARCH
• 影响因子: 14.6
• 作者: Chen, Minda;Bowers, Clifford R.;Huang, Wenyu
• 通讯作者: Huang, Wenyu