Terminal Diazirines Enable Reverse Polarization Transfer from 15 N 2 Singlets
Terminal Diazirines Enable Reverse Polarization Transfer from 15 N 2 Singlets
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末端二氮丙啶可实现 15 N 2 单峰的反向极化转移
DOI：
10.1002/anie.201904026
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发表时间：
2019
期刊：
影响因子：
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通讯作者：
Warren, Warren S.
中科院分区：
文献类型：
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作者：
Zhang, Guannan;Colell, Johannes F. P.;Glachet, Thomas;Lindale, Jacob R.;Reboul, Vincent;Theis, Thomas;Warren, Warren S.
双氮嘧啶部分具有化学稳定性，并已被纳入生物分子而不妨碍生物活性。15n2标记的重氮嘧啶是具有长寿命的超极化支持弛缓保护态的有吸引力的基序。本文研究的（‐CH15N2）重氮基团是甲基的类似物，这提供了将储存在弛豫保护（‐CH15N2）部分上的极化转移到1h的机会，从而将15n极化的长寿命优势与1h检测的高灵敏度结合起来。尽管重氮部分的1h和15n核接近，但观察到15nt1倍的（4.6±0.4）min和单线态寿命sts高达（17.5±3.8）min。此外，我们发现末端双氮嘧啶支持手性分子2基团的超极化单重态。1h单线态的单线态寿命可达（9.2±1.8）min，超过1ht1弛豫时间（8.45 T）约100倍。
Diazirine moieties are chemically stable and have been incorporated into biomolecules without impediment of biological activity. The15N2labeled diazirines are appealing motifs for hyperpolarization supporting relaxation protected states with long‐lived lifetimes. The (‐CH15N2) diazirine groups investigated here are analogues to methyl groups, which provides the opportunity to transfer polarization stored on a relaxation protected (‐CH15N2) moiety to1H, thus combining the advantages of long lifetimes of15N polarization with superior sensitivity of1H detection. Despite the proximity of1H to15N nuclei in the diazirine moiety,15NT1times of up to (4.6±0.4) min and singlet lifetimesTsof up to (17.5±3.8) min are observed. Furthermore, we found terminal diazirines to support hyperpolarized1H2singlet states in CH2groups of chiral molecules. The singlet lifetime of1H singlets is up to (9.2±1.8) min, thus exceeding1HT1relaxation time (at 8.45 T) by a factor of ≈100.