α-phenyl-N-tert-butylnitrone-type derivatives bound to β-cyclodextrins:: Syntheses, thermokinetics of self-inclusion and application to superoxide spin-trapping
α-phenyl-N-tert-butylnitrone-type derivatives bound to β-cyclodextrins:: Syntheses, thermokinetics of self-inclusion and application to superoxide spin-trapping
复制标题
DOI：
10.1002/chem.200700369
复制
发表时间：
2007-01-01
影响因子：
4.3
通讯作者：
Tordo, Paul
中科院分区：
文献类型：
--
作者：
Bardelang, David;Charles, Laurence;Tordo, Paul
已经合成了与β-环糊精衍生物结合的α-苯基-N-叔丁基硝酮(PBN)衍生物。 PBN 基团纳入 P-环糊精部分取决于宿主和温度。在硝酮与全甲基化环糊精 (Me3CD-PBN) 连接的情况下，热动力学参数有利于紧密和松散复合物之间的缓慢化学交换。相比之下，2,6-二-O-Me-β-环糊精接枝PBN (Me2CD-PBN) 要么以快速交换形式存在，要么以强自缔合复合物的形式存在。共价环糊精-PBN 化合物已被用来捕获以碳和氧为中心的自由基。 P-CD-自旋陷阱的自缔合形式与有效的自旋捕获相容，相对于非共价CD-硝酮系统或单独的硝酮，提供具有增强的EPR信号强度的自旋加合物。这种环糊精结合的硝酮是第一种共价超分子自旋陷阱，应该为体内生物自由基的研究开辟新的可能性。
alpha-Phenyl-N-tert-butylnitrone (PBN) derivatives bound to beta-cyclodextrin derivatives have been synthesized. Inclusion of the PBN group into the P-cyclodextrin moiety is host- and temperature- dependent. In the case of the nitrone linked to permethylated cyclodextrin (Me3CD-PBN), the thermokinetic parameters are in favour of a slow chemical exchange between a tight and a loose complex. In contrast, 2,6-di-O-Me-beta-cyclodextrin-grafted PBN (Me2CD-PBN) exists either in a fast exchange or as a strongly self-associated complex. The covalent cyclodextrin-PBN compounds have been used to trap carbon and oxygen-centred free radicals. The self-associated forms of the P-CD-spin-traps are compatible with effective spin-trapping, affording spin-adducts with enhanced EPR signal intensities relative to noncovalent CD-nitrone systems or the nitrone alone. This kind of cyclodextrin-bound nitrone is the first type of covalent supramolecular spin-trap and should open new possibilities for the study of biological free radicals in vivo.