A New Ir-NHC Catalyst for Signal Amplification by Reversible Exchange in D2 O.

A New Ir-NHC Catalyst for Signal Amplification by Reversible Exchange in D2 O.
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DOI:
10.1002/chem.201601211
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发表时间:
2016-06-27
影响因子:
4.3
通讯作者:
Feiters, Martin C.
Feiters, Martin C.
中科院分区:
化学2区
文献类型:
--
作者:
Spannring, Peter;Reile, Indrek;Emondts, Meike;Schleker, Philipp P. M.;Hermkens, Niels K. J.;van der Zwaluw, Nick G. J.;van Weerdenburg, Bram J. A.;Tinnemans, Paul;Tessari, Marco;Bluemich, Bernhard;Rutjes, Floris P. J. T.;Feiters, Martin C.

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使用新型催化剂 [Ir(Cl)(IDEG)(COD)],观察到 D2O 中的吡啶、烟酸甲酯、N-甲基烟酰胺和烟酰胺通过可逆交换 (SABRE) 进行 NMR 信号放大 (IDEG=1,3-双(3,4,5-三(二甘醇)苄基)咪唑-2-亚基)。在激活和超极化步骤中,仅使用 D2O,从而产生了第一个完全生物相容的 SABRE 系统。在接近地球磁场的情况下用仲氢对溶液加压,在产生几乎检测不到的热信号的浓度下,在 42.5 MHz 下观察到超极化 1H 底物信号。此外,在传统的 300 MHz 研究中,烟酰胺、吡啶、烟酸甲酯和 N-甲基烟酰胺分别观察到 42 倍、26 倍、22 倍和 9 倍的增强。这项研究为 SABRE 迄今为止主要在 CD3OD 中进行的领域开辟了新的机遇。该系统使用简单的硬件,保持基板不变,并表明 SABRE 可能适合临床用途。
NMR signal amplification by reversible exchange (SABRE) has been observed for pyridine, methyl nicotinate, N‐methylnicotinamide, and nicotinamide in D2O with the new catalyst [Ir(Cl)(IDEG)(COD)] (IDEG=1,3‐bis(3,4,5‐tris(diethyleneglycol)benzyl)imidazole‐2‐ylidene). During the activation and hyperpolarization steps, exclusively D2O was used, resulting in the first fully biocompatible SABRE system. Hyperpolarized 1H substrate signals were observed at 42.5 MHz upon pressurizing the solution with parahydrogen at close to the Earth's magnetic field, at concentrations yielding barely detectable thermal signals. Moreover, 42‐, 26‐, 22‐, and 9‐fold enhancements were observed for nicotinamide, pyridine, methyl nicotinate, and N‐methylnicotinamide, respectively, in conventional 300 MHz studies. This research opens up new opportunities in a field in which SABRE has hitherto primarily been conducted in CD3OD. This system uses simple hardware, leaves the substrate unaltered, and shows that SABRE is potentially suitable for clinical purposes.
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