用加氢PHIP提高丙酮酸衍生物超极化催化效率。

IF 3.4 4区 医学 Q2 CHEMISTRY, MEDICINAL
ChemMedChem Pub Date : 2025-09-12 DOI:10.1002/cmdc.202500379
Ginevra Di Matteo, Oksana Bondar, Carla Carrera, Eleonora Cavallari, Sumit Mishra, Francesca Reineri
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引用次数: 0

摘要

超极化丙酮酸是磁共振(MR)代谢成像中应用最广泛的探针。对氢诱导的极化侧臂加氢可以通过丙酮酸酯的催化加氢产生它。由于MR超极化的瞬态性质以及在体内应用需要大量的超极化底物,因此必须在几秒钟内获得浓缩的产物溶液,因此需要高浓度的催化剂。用于反应的均相铑催化剂可被加氢产物(或底物)失活,并且底物与催化剂的比率变得更低,特别是对于丙酮酸酯。在加氢混合物中加入三苯基膦可以防止催化剂失活,此时由于加氢产物丙酮酸烯丙酯和获得浓批超极化丙酮酸酯所需的催化剂量已显著减少。在水相中水解提取丙酮酸钠后,超极化代谢物的浓度增加到约60 mM,并在水中使用不同稀释度的超极化代谢物进行了13C-MRI实验。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Improving the Catalyst Efficiency for Hyperpolarization of Pyruvate Derivatives by Means of Hydrogenative PHIP.

Hyperpolarized pyruvate is the most widely used probe for metabolic imaging in magnetic resonance (MR). Parahydrogen induced polarization- side arm hydrogenation allows to generate it through the catalytic hydrogenation of pyruvate esters. Due to the transient nature of MR hyperpolarization and to the fact that in vivo applications require a high amount of hyperpolarized substrate, a concentrated product solution must be obtained in a few seconds, therefore a high catalyst concentration is needed. The homogeneous rhodium catalyst used for the reaction can be deactivated by the hydrogenation products (or substrates) and the substrate-to-catalyst ratio becomes even lower, especially for pyruvate esters. The addition of tris-phenyl phosphine to the hydrogenation mixture prevents the catalyst deactivation, when it is due to the hydrogenation product allyl pyruvate and the amount of catalyst needed to obtain a concentrated batch of hyperpolarized pyruvate ester has been reduced significantly. Following to hydrolysis and extraction of sodium pyruvate in aqueous phase, the concentration of the hyperpolarized metabolite has been increased to about 60 mM and 13C-MRI experiments have been carried out using different dilution of the hyperpolarized metabolite in water.

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来源期刊
ChemMedChem
ChemMedChem 医学-药学
CiteScore
6.70
自引率
2.90%
发文量
280
审稿时长
1 months
期刊介绍: Quality research. Outstanding publications. With an impact factor of 3.124 (2019), ChemMedChem is a top journal for research at the interface of chemistry, biology and medicine. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies. ChemMedChem publishes primary as well as critical secondary and tertiary information from authors across and for the world. Its mission is to integrate the wide and flourishing field of medicinal and pharmaceutical sciences, ranging from drug design and discovery to drug development and delivery, from molecular modeling to combinatorial chemistry, from target validation to lead generation and ADMET studies. ChemMedChem typically covers topics on small molecules, therapeutic macromolecules, peptides, peptidomimetics, and aptamers, protein-drug conjugates, nucleic acid therapies, and beginning 2017, nanomedicine, particularly 1) targeted nanodelivery, 2) theranostic nanoparticles, and 3) nanodrugs. Contents ChemMedChem publishes an attractive mixture of: Full Papers and Communications Reviews and Minireviews Patent Reviews Highlights and Concepts Book and Multimedia Reviews.
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