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利用氢气使胺类、酰胺类、羧酸类、醇类、磷酸盐和碳酸盐超极化。

Using hydrogen to hyperpolarize amines, amides, carboxylic acids, alcohols, phosphates, and carbonates.

作者信息

Iali Wissam, Rayner Peter J, Duckett Simon B

机构信息

Department of Chemistry, University of York, Heslington, York YO10 5DD, UK.

出版信息

Sci Adv. 2018 Jan 5;4(1):eaao6250. doi: 10.1126/sciadv.aao6250. eCollection 2018 Jan.

DOI:10.1126/sciadv.aao6250
PMID:29326984
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5756661/
Abstract

Hyperpolarization turns weak nuclear magnetic resonance (NMR) and magnetic resonance imaging (MRI) responses into strong signals, so normally impractical measurements are possible. We use hydrogen to rapidly hyperpolarize appropriate H, C, N, and P responses of analytes (such as NH) and important amines (such as phenylethylamine), amides (such as acetamide, urea, and methacrylamide), alcohols spanning methanol through octanol and glucose, the sodium salts of carboxylic acids (such as acetic acid and pyruvic acid), sodium phosphate, disodium adenosine 5'-triphosphate, and sodium hydrogen carbonate. The associated signal gains are used to demonstrate that it is possible to collect informative single-shot NMR spectra of these analytes in seconds at the micromole level in a 9.4-T observation field. To achieve these wide-ranging signal gains, we first use the signal amplification by reversible exchange (SABRE) process to hyperpolarize an amine or ammonia and then use their exchangeable NH protons to relay polarization into the analyte without changing its identity. We found that the H signal gains reach as high as 650-fold per proton, whereas for C, the corresponding signal gains achieved in a H-C refocused insensitive nuclei enhanced by polarization transfer (INEPT) experiment exceed 570-fold and those in a direct-detected C measurement exceed 400-fold. Thirty-one examples are described to demonstrate the applicability of this technique.

摘要

超极化将微弱的核磁共振(NMR)和磁共振成像(MRI)响应转化为强信号,从而使通常不切实际的测量成为可能。我们利用氢快速超极化分析物(如NH)以及重要胺类(如苯乙胺)、酰胺类(如乙酰胺、尿素和甲基丙烯酰胺)、从甲醇到辛醇的醇类和葡萄糖、羧酸的钠盐(如乙酸和丙酮酸)、磷酸钠、二磷酸腺苷5'-三磷酸以及碳酸氢钠的适当H、C、N和P响应。相关的信号增益用于证明在9.4-T观测场中,在微摩尔水平下,数秒内收集这些分析物的信息丰富的单次NMR谱图是可行的。为了实现这些广泛的信号增益,我们首先使用可逆交换信号放大(SABRE)过程使胺或氨超极化,然后利用它们可交换的NH质子将极化传递到分析物中而不改变其特性。我们发现,每个质子的H信号增益高达650倍,而对于C,在H-C重聚焦极化转移增强的非灵敏核(INEPT)实验中实现的相应信号增益超过570倍,在直接检测的C测量中超过400倍。描述了31个实例以证明该技术的适用性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/705b/5756661/884b5d710cb3/aao6250-F4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/705b/5756661/c142d81959b8/aao6250-S1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/705b/5756661/c5d2d4240f8e/aao6250-F1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/705b/5756661/44d433b7f2f8/aao6250-F2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/705b/5756661/1e1a5c3dafd3/aao6250-F3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/705b/5756661/884b5d710cb3/aao6250-F4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/705b/5756661/c142d81959b8/aao6250-S1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/705b/5756661/c5d2d4240f8e/aao6250-F1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/705b/5756661/44d433b7f2f8/aao6250-F2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/705b/5756661/1e1a5c3dafd3/aao6250-F3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/705b/5756661/884b5d710cb3/aao6250-F4.jpg

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