Sievers C, Deters D, Hartmann H J, Weser U
Physiologisch-Chemisches Institut, Universität Tübingen, Germany.
J Inorg Biochem. 1996 May 15;62(3):199-205. doi: 10.1016/0162-0134(95)00153-0.
It was of interest to obtain long-lived thiyl radicals embedded in organic matrices. Solid thiol compounds including penicillamine, glutathione, and cysteine were UV irradiated under anaerobic conditions at 293 K for 60 min. The formed radicals were identified by electron paramagnetic resonance (EPR) (g = 2.0265 +/- 0.0015) at 293 K as thiyl radicals. The blue-colored radical species were subjected to reflection spectrometry (lambda max = 601 +/- 3 nm). The color and the EPR signal remained unchanged for six months. At the same time, the UV irradiation of lyophilisized yeast Cu(I)6-thionein generated stable EPR detectable thiyl was seen when the Cu(I)-thiolate was used. No EPR detectable thiyl radicals radicals at a g-value of 2.026 +/- 0.001. Unlike irradiated cysteine, a five times higher concentration of thiyl radicals were measured in the Cu(I)-thiolates of penicillamine, glutathione, and thiophenole, indicating that the hexanuclear copper arrangement in Cu(I)-thionein is most suitable for both the formation and stabilization of this sulfur radical species.
获得嵌入有机基质中的长寿命硫自由基是很有意义的。包括青霉胺、谷胱甘肽和半胱氨酸在内的固体硫醇化合物在293K的厌氧条件下用紫外线照射60分钟。在293K下通过电子顺磁共振（EPR）（g = 2.0265 +/- 0.0015）将形成的自由基鉴定为硫自由基。对蓝色自由基物种进行反射光谱分析（最大波长 = 601 +/- 3nm）。颜色和EPR信号在六个月内保持不变。同时，当使用Cu（I）-硫醇盐时，冻干酵母Cu（I）6-硫蛋白的紫外线照射产生了稳定的可通过EPR检测到的硫自由基。在g值为2.026 +/- 0.001时未检测到EPR可检测的硫自由基。与照射的半胱氨酸不同，在青霉胺、谷胱甘肽和苯硫酚的Cu（I）-硫醇盐中测得的硫自由基浓度高五倍，这表明Cu（I）-硫蛋白中的六核铜排列最适合这种硫自由基物种的形成和稳定。
