a Department of Chemistry and Biochemistry , University of Denver , Denver , CO , USA.
b Department of Chemistry , University of Nebraska , Lincoln , NE , USA.
Free Radic Res. 2018 Mar;52(3):319-326. doi: 10.1080/10715762.2017.1384954. Epub 2017 Nov 16.
An iodoacetamide azaadamantyl spin label was studied in fluid solution and in 9:1 trehalose:sucrose glass. In 9:1 toluene:CHCl solution at 293 K, the isotropic nitrogen hyperfine coupling is 19.2 G, T is 0.37 µs and T is 0.30-0.35 µs. Between about 80 and 150 K 1/T in 9:1 trehalose:sucrose is approximately independent of temperature demonstrating that the absence of methyl groups decreases 1/T relative to that which is observed in spin labels with methyl groups on the alpha carbons. Spin lattice relaxation rates between about 80 and 293 K in 9:1 trehalose:sucrose are similar to those observed for other nitroxide spin labels, consistent with the expectation that relaxation is dominated by Raman and local mode processes. Although complexation of the azaadamantyl spin label with β-cyclodextrin slows tumbling in aqueous solution by about a factor of 10, it has little impact on 1/T or 1/T in 9:1 trehalose:sucrose between 80 and 293 K.
碘乙酰胺氮杂金刚烷基自旋标记物在溶液中和 9:1 海藻糖/蔗糖玻璃中进行了研究。在 293 K 的 9:1 甲苯:CHCl 溶液中,各向同性氮超精细耦合为 19.2 G,T 为 0.37 µs,T 为 0.30-0.35 µs。在约 80 至 150 K 之间,9:1 海藻糖/蔗糖中的 1/T 几乎与温度无关,表明与在 α 碳原子上具有甲基的自旋标记物相比,甲基的缺失降低了 1/T。在 9:1 海藻糖/蔗糖中,约 80 至 293 K 之间的自旋晶格弛豫率与其他氮氧化物自旋标记物观察到的相似,这与弛豫主要由拉曼和局部模式过程主导的预期一致。尽管氮杂金刚烷基自旋标记物与β-环糊精的络合使水溶液中的旋转翻滚速度减慢了约 10 倍,但在 80 至 293 K 之间,它对 9:1 海藻糖/蔗糖中的 1/T 或 1/T 几乎没有影响。