Synthesis of 2,5-Bis(spirocyclohexane)-Substituted Nitroxides of Pyrroline and Pyrrolidine Series, Including Thiol-Specific Spin Label: An Analogue of MTSSL with Long Relaxation Time

被引：68

作者：

Kirilyuk, Igor A. ^{[1
]}

Polienko, Yuliya F. ^{[1
]}

Krumkacheva, Olesya A. ^{[2
]}

Strizhakov, Rodion K. ^{[2
]}

Gatilov, Yurii V. ^{[1
]}

Grigor'ev, Igor A. ^{[1
]}

Bagryanskaya, Elena G. ^{[1
,2
]}

机构：

[1] RAS, NN Vorozhtsov Novosibirsk Inst Organ Chem Sb, Novosibirsk 630090, Russia

[2] RAS, Int Tomog Ctr SB, Novosibirsk 630090, Russia

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2012年 / 77卷 / 18期

基金：

俄罗斯基础研究基金会;

关键词：

ELECTRON DOUBLE-RESONANCE; CONTRAST-ENHANCING AGENTS; PULSED EPR SPECTROSCOPY; DISTANCE MEASUREMENTS; FREE-RADICALS; PARAMAGNETIC-RESONANCE; IN-VITRO; REDUCTION; ASCORBATE; PELDOR;

D O I：

10.1021/jo301235j

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The nitroxides of 7-azadispiro[5.1.5.2]-pentadecane and 7-azadispiro[5.1.5.2]pentadeca-14-ene series have been prepared, including thiol-specific methane thiosulfonate spin label for site-directed spin labeling. The effect of spirocyclohexane moieties on chemical and spectral properties has been studied. The obtained temperature dependencies of electron spin relaxation parameters demonstrate that new nitroxides may be suitable for PELDOR distance measurements at 80-120 K. Moreover, the new nitroxides demonstrated much higher stability toward reduction by ascorbate than spirocyclohexane-substituted nitroxides of piperidine series and showed 1.3-3.14 times lower reduction rates compared to corresponding 2,2,5,5-tetramethyl nitroxides.

引用

页码：8016 / 8027

页数：12

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