Rigid Orthogonal Bis-TEMPO Biradicals with Improved Solubility for Dynamic Nuclear Polarization

被引：73
作者：
Dane, Eric L. [1 ]
Corzilius, Bjoern [1 ,2 ]
Rizzato, Egon [3 ]
Stocker, Pierre [3 ]
Maly, Thorsten [1 ,2 ]
Smith, Albert A. [1 ,2 ]
Griffin, Robert G. [1 ,2 ]
Ouari, Olivier [3 ]
Tordo, Paul [3 ]
Swagert, Timothy M. [1 ]
机构：
[1] MIT, Dept Chem, Cambridge, MA 02139 USA
[2] MIT, Francis Bitter Magnet Lab, Cambridge, MA 02139 USA
[3] Aix Marseille Univ, SREP LCP UMR 6264, Fac St Jerome, F-13013 Marseille, France
来源：
JOURNAL OF ORGANIC CHEMISTRY | 2012年 / 77卷 / 04期
基金：
美国国家卫生研究院;
关键词：
ELECTRON-PARAMAGNETIC-RESONANCE; CRYSTAL-STRUCTURE; MAS SPECTRA; NMR; OXIDATION; 1,3-DITHIANE; SPECTROSCOPY; ALDEHYDES; PROTEINS; SULFIDES;
D O I：
10.1021/jo202349j
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
The synthesis and characterization of oxidized bis-thioketal-trispiro dinitroxide biradicals that orient the nitroxides in a rigid, approximately orthogonal geometry are reported. The biradicals show better performance as polarizing agents in dynamic nuclear polarization (DNP) NMR experiments as compared to biradicals lacking the constrained geometry. In addition, the biradicals display improved solubility in aqueous media due to the presence of polar sulfoxides. The results suggest that the orientation of the radicals is not dramatically affected by the oxidation state of the sulfur atoms in the biradical, and we conclude that a biradical polarizing agent containing a mixture of oxidation states can be used for improved solubility without a loss in performance.
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页码：1789 / 1797
页数：9
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