使用乙烯基、烯丙基和炔丙基酯的侧链氢化反应实现1-C-乙酸酯和1-C-丙酮酸酯的仲氢诱导极化
Parahydrogen-Induced Polarization of 1-C-Acetates and 1-C-Pyruvates Using Sidearm Hydrogenation of Vinyl, Allyl, and Propargyl Esters.
作者信息
Salnikov Oleg G, Chukanov Nikita V, Shchepin Roman V, Manzanera Esteve Isaac V, Kovtunov Kirill V, Koptyug Igor V, Chekmenev Eduard Y
机构信息
International Tomography Center SB RAS, Institutskaya Street 3A, Novosibirsk 630090, Russia.
Novosibirsk State University, Pirogova Street 2, Novosibirsk 630090, Russia.
出版信息
J Phys Chem C Nanomater Interfaces. 2019 May 23;123(20):12827-12840. doi: 10.1021/acs.jpcc.9b02041. Epub 2019 Apr 19.
C-hyperpolarized carboxylates, such as pyruvate and acetate, are emerging molecular contrast agents for MRI visualization of various diseases, including cancer. Here we present a systematic study of H and C parahydrogen-induced polarization of acetate and pyruvate esters with ethyl, propyl and allyl alcoholic moieties. It was found that allyl pyruvate is the most efficiently hyperpolarized compound from those under study, yielding 21% and 5.4% polarization of H and C nuclei, respectively, in CDOD solutions. Allyl pyruvate and ethyl acetate were also hyperpolarized in aqueous phase using homogeneous hydrogenation with parahydrogen over water-soluble rhodium catalyst. C polarization of 0.82% and 2.1% was obtained for allyl pyruvate and ethyl acetate, respectively. C-hyperpolarized methanolic and aqueous solutions of allyl pyruvate and ethyl acetate were employed for in vitro MRI visualization, demonstrating the prospects for translation of the presented approach to biomedical in vivo studies.
C-超极化羧酸盐，如丙酮酸和乙酸盐，正成为用于包括癌症在内的各种疾病MRI可视化的新型分子造影剂。在此，我们对具有乙基、丙基和烯丙基醇部分的乙酸酯和丙酮酸酯的氢和碳仲氢诱导极化进行了系统研究。结果发现，在所研究的化合物中，烯丙基丙酮酸是超极化效率最高的化合物，在CDOD溶液中，其氢核和碳核的极化率分别为21%和5.4%。使用水溶性铑催化剂在水相中将烯丙基丙酮酸和乙酸乙酯与仲氢进行均相氢化，也可实现它们在水相中的超极化。烯丙基丙酮酸和乙酸乙酯的碳极化率分别为0.82%和2.1%。烯丙基丙酮酸和乙酸乙酯的C-超极化甲醇溶液和水溶液用于体外MRI可视化，证明了将所提出的方法转化为生物医学体内研究的前景。
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