Wilson John C, Wu Gang, Tsai Ah-lim, Gerfen Gary J
Department of Physiology and Biophysics, Albert Einstein College of Medicine, Bronx, NY 10461, USA.
J Am Chem Soc. 2005 Feb 16;127(6):1618-9. doi: 10.1021/ja043853q.
The catalytically active tyrosyl radical which gives rise to the "wide doublet" (WD1) signal in ovine Prostaglandin H2 Synthase-1 has been studied using high frequency (HF) pulsed ENDOR and EPR. A hydrogen-bonded deuteron was directly detected in HFENDOR (130 GHz) spectra of 1H2O/2H2O-exchanged samples. The HFENDOR spectral simulations required a distribution in hydrogen bond distances to achieve proper fits. This range of distances was consistent with that used to model the distribution in gX values detected in pulsed HFEPR spectra. Possible hydrogen-bonding partners, as well as implications regarding the mechanism of self-inactivation for PGHS, are discussed.
利用高频(HF)脉冲电子核双共振(ENDOR)和电子顺磁共振(EPR)对在绵羊前列腺素H2合酶-1中产生“宽双峰”(WD1)信号的催化活性酪氨酸自由基进行了研究。在1H2O/2H2O交换样品的HFENDOR(130 GHz)光谱中直接检测到了一个氢键氘核。HFENDOR光谱模拟需要氢键距离的分布来实现合适的拟合。这个距离范围与用于模拟脉冲HFEPR光谱中检测到的gX值分布的范围一致。讨论了可能的氢键伙伴以及关于PGHS自失活机制的影响。