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Long-Lived States of Magnetically Equivalent Spins Populated by Dissolution-DNP and Revealed by Enzymatic Reactions

机译:溶解-DNP填充并通过酶促反应揭示的磁当量自旋的长寿命状态

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摘要

Hyperpolarization by dissolution dynamic nuclear polarization (D-DNP) offers a way of enhancing NMR signals by up to five orders of magnitude in metabolites and other small molecules. Nevertheless, the lifetime of hyperpolarization is inexorably limited, as it decays toward thermal equilibrium with the nuclear spin-lattice relaxation time. This lifetime can be extended by storing the hyperpolarization in the form of long-lived states (LLS) that are immune to most dominant relaxation mechanisms. Levitt and co-workers have shown how LLS can be prepared for a pair of inequivalent spins by D-DNP. Here, we demonstrate that this approach can also be applied to magnetically equivalent pairs of spins such as the two protons of fumarate, which can have very long LLS lifetimes. As in the case of para-hydrogen, these hyperpolarized equivalent LLS (HELLS) are not magnetically active. However, a chemical reaction such as the enzymatic conversion of fumarate into malate can break the magnetic equivalence and reveal intense NMR signals.
机译:通过溶解动态核极化(D-DNP)进行的超极化提供了一种在代谢物和其他小分子中将NMR信号增强多达五个数量级的方法。然而,超极化的寿命无可避免地受到限制,因为它随着核自旋晶格弛豫时间朝着热平衡衰减。可以通过以不受大多数​​主要弛豫机制影响的长寿命状态(LLS)形式存储超极化来延长此寿命。 Levitt及其同事展示了如何通过D-DNP为一对不等价的自旋制备LLS。在这里,我们证明了这种方法也可以应用于磁性等效的自旋对,例如富马酸酯的两个质子,它们的寿命很长。与对氢一样,这些超极化等效LLS(HELLS)也不具有磁性。但是,化学反应(例如富马酸酯酶促转化为苹果酸)会破坏磁当量并显示出强烈的NMR信号。

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