Toward Cleavable Metabolic/pH Sensing "Double Agents" Hyperpolarized by NMR Signal Amplification by Reversible Exchange.
Toward Cleavable Metabolic/pH Sensing "Double Agents" Hyperpolarized by NMR Signal Amplification by Reversible Exchange.
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DOI：
10.1002/chem.201802622
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发表时间：
2018-07-25
期刊：
影响因子：
--
通讯作者：
Goodson BM
中科院分区：
文献类型：
--
作者：
Kidd BE;Mashni JA;Limbach MN;Shi F;Chekmenev EY;Hou Y;Goodson BM
我们表明，同时产生的超极化13 C-标记的乙酸和15 N-标记的咪唑自旋中继超极化和水解的乙酰基部分1- 13 C-15 N2-acetylimidazole。通过SABRE-SHEATH（通过SHield中的可逆交换实现对准转移到异核的信号放大），从仲氢到乙酰基咪唑15 N原子和乙酰基13 C位点发生自旋顺序转移（~263倍增强），在0.3 T下产生相对较长的超极化寿命（13 C和15 N的T1分别为~52 s和~149 s）。极化转移后，13 C标记的乙酰基立即水解裂解，产生超极化的13 C-乙酸盐/乙酸（~140倍增强）和15 N-咪唑（~180倍增强），前者在0.3 T下的13 C T1为~14 s。简单的合成路线，有效的自旋中继的SABRE超极化，和轻松的键裂解打开了一扇门，以廉价和快速生成长寿命的超极化状态内的广泛的分子靶标，包括生物相关的羧酸衍生物，代谢和pH成像。一个有两个主人的“自旋间谍”：当与催化剂结合时，一个分子“双重代理人”从仲氢借用核自旋顺序。分子的更远的13 C自旋通过“自旋中继”从更接近催化剂的15 N自旋极化，利用标量耦合。水解裂解产生两个独立的超极化剂-13 C-乙酸/乙酸和15 N2-咪唑-其增强的NMR信号可以分别报告代谢和局部pH值。
We show the simultaneous generation of hyperpolarized 13C-labeled acetate and 15N-labeled imidazole following spin-relay of hyperpolarization and hydrolysis of the acetyl moiety on 1-13C-15N2-acetylimidazole. Through SABRE-SHEATH (Signal Amplification by Reversible Exchange in SHield Enables Alignment Transfer to Heteronuclei), transfer of spin order occurs from parahydrogen to acetylimidazole 15N atoms and the acetyl 13C site (~263-fold enhancement), giving rise to relatively long hyperpolarization lifetimes at 0.3 T (T1 ~52 s and ~149 s for 13C and 15N, respectively). Immediately following polarization transfer, the 13C-labeled acetyl group is hydrolytically cleaved to produce hyperpolarized 13C-acetate/acetic acid (~140-fold enhancement) and 15N-imidazole (~180-fold enhancement), the former with a 13C T1 of ~14 s at 0.3 T. Straight-forward 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. A “spin-spy” with two masters: While bound to a catalyst, a molecular “double agent” borrows nuclear spin order from parahydrogen. The molecule’s more-distant 13C spin is polarized via “spin relay” from a 15N spin closer to the catalyst, exploiting scalar coupling. Hydrolytic cleavage yields two separate hyperpolarized agents-—13C-acetate/acetic acid and 15N2-imidazole-—whose enhanced NMR signals can report on metabolism and local pH, respectively.
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影响因子：
4.6
作者：
Fekete M;Bayfield OW;Duckett SB;Hart S;Mewis RE;Pridmore N;Rayner PJ;Whitwood A
通讯作者：
Whitwood A
影响因子：
15
作者：
Colell JFP;Emondts M;Logan AWJ;Shen K;Bae J;Shchepin RV;Ortiz GX Jr;Spannring P;Wang Q;Malcolmson SJ;Chekmenev EY;Feiters MC;Rutjes FPJT;Blümich B;Theis T;Warren WS
通讯作者：
Warren WS
影响因子：
3.7
作者：
Kovtunov, Kirill V.;Kidd, Bryce E.;Koptyug, Igor V.
通讯作者：
Koptyug, Igor V.
影响因子：
2.9
作者：
Lai, Marta;Gruetter, Rolf;Lanz, Bernard
通讯作者：
Lanz, Bernard
DOI：
10.1002/asia.201800551
发表时间：
2018-05-23
期刊：
Chemistry, an Asian journal
影响因子：
--
作者：
Kovtunov KV;Pokochueva EV;Salnikov OG;Cousin SF;Kurzbach D;Vuichoud B;Jannin S;Chekmenev EY;Goodson BM;Barskiy DA;Koptyug IV
通讯作者：
Koptyug IV