Making hyperfine selection in Mims ENDOR independent of deadtime

Making hyperfine selection in Mims ENDOR independent of deadtime
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DOI:
10.1016/s0009-2614(97)00293-5
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发表时间:
1997-05-02
影响因子:
2.8
通讯作者:
Hoffman, BM
Hoffman, BM
中科院分区:
化学4区
文献类型:
--
作者:
Doan, PE;Hoffman, BM

文献摘要

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一种形式的远程回波检测Endor可以通过将附加的pi脉冲添加到MIMS三脉冲刺激回声Endor实验的检测阶段来执行。由此产生的四脉冲实验,称为重聚焦MIMS(ReMims)Endor,保留了MIMS技术的超精细选择性,但使获得与光谱仪死区无关的任意短的准备间隔tau(1)成为可能。因此,不需要重新设计谐振器,就有可能研究范围更广的超精细值,而不会因“盲点”而失真。在铜(甘氨酸)(2)单晶的H-1和N-14 Endor谱上证明了ReMims Endor序列的超精细选择性。使用ReMims协议来增加基本MIMS和Davies Endor序列在两种不同类型的情况下被示出:9 MHz耦合质子的符号是通过使用氰基水合酶的质子Endor谱中的隐式三重效应来指定的;荧光肌红蛋白的质子Endor谱的真实线形是在没有盲点失真的情况下确定的。
A form of remote echo-detected ENDOR can be performed by adding an additional pi pulse to the detection phase of a Mims three-pulse, stimulated-echo ENDOR experiment. The resulting four-pulse experiment, denoted refocused Mims (ReMims) ENDOR, retains the hyperfine selectivity of the Mims technique, but makes it possible to obtain arbitrarily short preparation intervals, tau(1), independent of the spectrometer deadtime. As a result, without resonator redesign, it is possible to study a wider range of hypefine values without distortions from ''blind-spots''. The hyperfine selectivity of the ReMims ENDOR sequence is demonstrated on the H-1 and N-14 ENDOR spectra from a single crystal of Cu(glycine)(2). Use of the ReMims protocol to augment the basic Mims and Davies ENDOR sequences is shown in two different types of situation: the sign of a 9 MHz coupled proton is assigned by the use of the implicit-TRIPLE effect in the proton ENDOR spectrum of nitrile hydratase; the true lineshape of the proton ENDOR spectrum of fluorometmyoglobin is determined without distortions by blindspots.