通过子弹动态核极化实现脂肪链中质子长寿命态的超极化,通过自旋锁定诱导交叉实时揭示。
Hyperpolarization of Long-Lived States of Protons in Aliphatic Chains by Bullet Dynamic Nuclear Polarization, Revealed on the Fly by Spin-Lock-Induced Crossing.
作者信息
Razanahoera Aiky, Sonnefeld Anna, Sheberstov Kirill, Narwal Pooja, Minaei Masoud, Kouřil Karel, Bodenhausen Geoffrey, Meier Benno
机构信息
Laboratoire des Biomolécules, LBM, Département de Chimie, École Normale Supérieure, PSL University, Sorbonne Université, CNRS, 75005 Paris, France.
Institute of Biological Interfaces 4, Karlsruhe Institute of Technology, Eggenstein-Leopoldshafen 76344, Germany.
出版信息
J Phys Chem Lett. 2024 Sep 5;15(35):9024-9029. doi: 10.1021/acs.jpclett.4c01457. Epub 2024 Aug 27.
It is shown that proton spins highly polarized by dynamic nuclear polarization (DNP) retain substantial polarization upon the rapid transfer of frozen bullets from a polarizer to an NMR spectrometer. After injection in solution, the resulting hyperpolarization in aliphatic chains comprises population imbalances between singlet and triplet states of geminal protons and combinations thereof. These hyperpolarized long-lived states (LLSs) can be reconverted into observable transverse magnetization by polychromatic spin-lock-induced crossing (poly-SLIC). This reconversion can be achieved simultaneously in several molecules. Consecutive partial reconversion steps can be carried out to determine the lifetimes on the fly in a single experiment. The enhancement factors of hyperpolarized LLS-derived signals in our experiments are at least 2 orders of magnitude. These methods extend applications of bullet-DNP to protons in molecules containing short aliphatic chains and may be useful for drug screening.
结果表明,通过动态核极化(DNP)高度极化的质子自旋在将冷冻“子弹”从极化器快速转移到核磁共振波谱仪时仍保持大量极化。注入溶液后,脂肪链中产生的超极化包括偕偶质子单重态和三重态之间的布居不平衡及其组合。这些超极化的长寿命态(LLS)可通过多色自旋锁定诱导交叉(poly-SLIC)重新转换为可观测的横向磁化。这种重新转换可在几个分子中同时实现。可以进行连续的部分重新转换步骤,以便在单个实验中即时确定寿命。我们实验中超极化LLS衍生信号的增强因子至少为2个数量级。这些方法将“子弹”DNP的应用扩展到含有短脂肪链分子中的质子,可能对药物筛选有用。
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