Adiabatic Passage through Level Anticrossings in Systems of Chemically Inequivalent Protons Incorporating Parahydrogen: Theory, Experiment, and Prospective Applications.
Adiabatic Passage through Level Anticrossings in Systems of Chemically Inequivalent Protons Incorporating Parahydrogen: Theory, Experiment, and Prospective Applications.
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DOI：
10.1021/jacs.2c09000
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发表时间：
2022-11-16
影响因子：
15
通讯作者：
Bowers, Clifford R.
中科院分区：
文献类型：
--
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.
能级反交叉（拉克）在量子系统中普遍存在，并已被用于超极化核磁共振谱中的自旋序转移。本文探讨了绝热通过一个特定类型的LAC中发现的化学不等价耦合质子结合仲氢（pH 2）homopoly系统的表现。绝热通过这样的LAC引起翻译的pH2自旋顺序。作为一个例子，在生物医学中的应用前景，质子自旋极化的至少在亚甲基质子和乙烯基质子的选择性氘代烯丙基丙酮酸酯的实验证明。在将含有丙酮酸炔丙酯和溶解的Rh催化剂的前体溶液超声喷雾注射到用99%对位富集的H2加压的室中之后，收集产物并将其输送到高磁场用于NMR检测。LAC介导的亚甲基质子的超极化是显着的，因为更强的自旋耦合到丙酮酸羰基13 C，建立了一个理想的初始条件，随后通过选择性INEPT的相干转移。此外，炔丙基侧臂的选择性氘化提高了效率和偏振水平。LAC介导的仲氢自旋顺序的翻译完成了通过仲氢侧臂氢化增强丙酮酸13C NMR信号的新的高效途径的第一步。
Level anticrossings (LACs) are ubiquitous in quantum systems and have been exploited for spin-order transfer in hyperpolarized nuclear magnetic resonance spectroscopy. This paper examines the manifestations of adiabatic passage through a specific type of LAC found in homonuclear systems of chemically inequivalent coupled protons incorporating parahydrogen (pH2). Adiabatic passage through such a LAC is shown to elicit translation of the pH2 spin order. As an example, with prospective applications in biomedicine, proton spin polarizations of at least on the methylene protons and on the vinylic protons of selectively deuterated allyl pyruvate ester are demonstrated experimentally. After ultrasonic spray injection of a precursor solution containing propargyl pyruvate and a dissolved Rh catalyst into a chamber pressurized with 99% para-enriched H2, the products are collected and transported to a high magnetic field for NMR detection. The LAC-mediated hyperpolarization of the methylene protons is significant because of the stronger spin coupling to the pyruvate carbonyl 13C, setting up an ideal initial condition for subsequent coherence transfer by selective INEPT. Furthermore, the selective deuteration of the propargyl side arm increases the efficiency and polarization level. LAC-mediated translation of parahydrogen spin order completes the first step toward a new and highly efficient route for the 13C NMR signal enhancement of pyruvate via side-arm hydrogenation with parahydrogen.
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影响因子：
--
作者：
HAAKE, M;BARKEMEYER, J;BARGON, J
通讯作者：
BARGON, J
影响因子：
7.4
作者：
Joalland, Baptiste;Schmidt, Andreas B.;Chekmenev, Eduard Y.
通讯作者：
Chekmenev, Eduard Y.
影响因子：
2.8
作者：
PRAVICA, MG;WEITEKAMP, DP
通讯作者：
WEITEKAMP, DP
DOI：
10.1002/mrc.4642
发表时间：
2018-06
期刊：
Magnetic resonance in chemistry : MRC
影响因子：
--
作者：
Bengs C;Levitt MH
通讯作者：
Levitt MH
影响因子：
16.6
作者：
Reineri, Francesca;Boi, Tommaso;Aime, Silvio
通讯作者：
Aime, Silvio