刚性正交双 TEMPO 双自由基，改善了动态核极化的溶解性。
Rigid orthogonal bis-TEMPO biradicals with improved solubility for dynamic nuclear polarization.
机构信息
Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, USA.
出版信息
J Org Chem. 2012 Feb 17;77(4):1789-97. doi: 10.1021/jo202349j. Epub 2012 Feb 6.
Abstract
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.
摘要
报道了一种新型的氧化双硫缩酮三螺环二硝酮双自由基，该双自由基以刚性的、近似正交的几何结构固定了硝酮基团的取向。与不具有约束几何结构的双自由基相比，这些双自由基在动态核极化（DNP）NMR 实验中作为极化剂表现出更好的性能。此外，由于存在极性砜基，双自由基在水相中的溶解度也得到了提高。结果表明，自由基的取向并不受双自由基中硫原子氧化态的显著影响，我们得出结论，含有混合氧化态的双自由基极化剂可以在不影响性能的情况下，提高溶解度。
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