Toward Cleavable Metabolic/pH Sensing "Double Agents" Hyperpolarized by NMR Signal Amplification by Reversible Exchange

利用可逆交换进行核磁共振信号放大,实现可裂解代谢/pH传感“双效试剂”的超极化

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Abstract

We show the simultaneous generation of hyperpolarized (13) C-labeled acetate and (15) N-labeled imidazole following spin-relay of hyperpolarization and hydrolysis of the acetyl moiety on 1-(13) C-(15) N(2) -acetylimidazole. Using SABRE-SHEATH (Signal Amplification by Reversible Exchange in SHield Enables Alignment Transfer to Heteronuclei), transfer of spin order occurs from parahydrogen to acetylimidazole (15) N atoms and the acetyl (13) C site (≈263-fold enhancement), giving rise to relatively long hyperpolarization lifetimes at 0.3 T (T(1) ≈52 s and ≈149 s for (13) C and (15) N, respectively). Immediately following polarization transfer, the (13) C-labeled acetyl group is hydrolytically cleaved to produce hyperpolarized (13) C-acetate/acetic acid (≈140-fold enhancement) and (15) N-imidazole (≈180-fold enhancement), the former with a (13) C T(1) of ≈14 s at 0.3 T. Straightforward synthetic routes, efficient spin-relay of SABRE hyperpolarization, and facile bond cleavage open a door to the cheap and rapid generation of long-lived hyperpolarized states within a wide range of molecular targets, including biologically relevant carboxylic acid derivatives, for metabolic and pH imaging.

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