Computationally Assisted Design of Polarizing Agents for Dynamic Nuclear Polarization Enhanced NMR: The AsymPol Family.
Computationally Assisted Design of Polarizing Agents for Dynamic Nuclear Polarization Enhanced NMR: The AsymPol Family.
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动态核极化增强核磁共振偏振剂的计算辅助设计：AsymPol系列。
DOI：
10.1021/jacs.8b04911
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发表时间：
2018-09-05
影响因子：
15
通讯作者：
De Paëpe G
中科院分区：
文献类型：
--
作者：
Mentink-Vigier F;Marin-Montesinos I;Jagtap AP;Halbritter T;van Tol J;Hediger S;Lee D;Sigurdsson ST;De Paëpe G
我们介绍了一个新的家庭的动态核极化（DNP）增强核磁共振（NMR）的应用程序，由不对称的双氮氧化物，其中哌啶基自由基和吡咯烷氧基或乙酰基自由基连接在一起的高效极化剂。AsymPol系列的设计是通过使用先进的模拟来指导的，这些模拟允许计算自由基结构对DNP效率的影响。这些模拟表明，使用一个相对较短的连接器的目的是产生一个相当大的分子内电子偶极耦合/J-交换相互作用，同时避免平行的氮氧化物取向。AsymPol的特性被进一步调整，例如在5元环中添加共轭碳-碳双键以提高刚性并提供有利的相对取向，用螺环己醇基取代甲基以减缓电子自旋弛豫，以及引入磷酸基团以产生高度水溶性的掺杂剂。本文对该家族的两个成员AsymPol和AsymPolPOK进行了深入的实验和理论研究。我们在9.4和18.8 T下报告了显著的灵敏度增益。通过使用18.8 T的快速样品旋转对重要工业催化剂进行高分辨率表面表征，进一步证明了该新系列的强大效率。这项工作突出了一个新的方向极化代理设计和计算在这个过程中的至关重要性。
We introduce a new family of highly efficient polarizing agents for dynamic nuclear polarization (DNP)-enhanced nuclear magnetic resonance (NMR) applications, composed of asymmetric bis-nitroxides, in which a piperidine-based radical and a pyrrolinoxyl or a proxyl radical are linked together. The design of the AsymPol family was guided by the use of advanced simulations that allow computation of the impact of the radical structure on DNP efficiency. These simulations suggested the use of a relatively short linker with the intention to generate a sizable intramolecular electron dipolar coupling/J-exchange interaction, while avoiding parallel nitroxide orientations. The characteristics of AsymPol were further tuned, for instance with the addition of a conjugated carbon–carbon double bond in the 5-membered ring to improve the rigidity and provide a favorable relative orientation, the replacement of methyls by spirocyclohexanolyl groups to slow the electron spin relaxation, and the introduction of phosphate groups to yield highly water-soluble dopants. An in-depth experimental and theoretical study for two members of the family, AsymPol and AsymPolPOK, is presented here. We report substantial sensitivity gains at both 9.4 and 18.8 T. The robust efficiency of this new family is further demonstrated through high-resolution surface characterization of an important industrial catalyst using fast sample spinning at 18.8 T. This work highlights a new direction for polarizing agent design and the critical importance of computations in this process.
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影响因子：
15
作者：
Lesage, Anne;Lelli, Moreno;Emsley, Lyndon
通讯作者：
Emsley, Lyndon
DOI：
10.1039/c6cp00839a
发表时间：
2016-04-21
期刊：
Physical chemistry chemical physics : PCCP
影响因子：
--
作者：
Chaudhari SR;Berruyer P;Gajan D;Reiter C;Engelke F;Silverio DL;Copéret C;Lelli M;Lesage A;Emsley L
通讯作者：
Emsley L
影响因子：
15
作者：
Hu, KN;Yu, HH;Griffin, RG
通讯作者：
Griffin, RG
影响因子：
4.9
作者：
Kathirvelu, Velavan;Smith, Christopher;Eaton, Gareth R.
通讯作者：
Eaton, Gareth R.
影响因子：
1.6
作者：
Morley, Gavin W.;Brunel, Louis-Claude;van Tol, Johan
通讯作者：
van Tol, Johan