Envelope modulation

The electron-spm echo envelope modulation (ESEEM) phenomenon [37, 38] is of primary interest in pulsed EPR of solids, where anisotropic hyperfme and nuclear quadnipole interactions persist. The effect can be observed as modulations of the echo intensity in two-pulse and three-pulse experiments in which x or J is varied. In liquids the modulations are averaged to zero by rapid molecular tumbling. The physical origin of ESEEM can be understood in tenns of the four-level spin energy diagram for the S = I = model system... 

Rowan L G, Hahn E L and Mims W B 1965 Electron-spin echo envelope modulation Phys. Rev. 137 A61-A71... 

Mims W B 1972 Envelope modulation in spin-echo experiments Phys. Rev. B 5 2409-19... 

Merks R P J and de Beer R 1979 Two-dimensional Fourier transform of electron spin-echo envelope modulation. An alternative for ENDOR J. Phys. Chem. 83 3319-22... 

Riedel A, S Fetzner, M Rampp, F Lingens, U Liebl, J-L Zrmmermann, W Nitschke (1995) EPR, electron spin echo envelope modulation, and electron nuclear double resonance studies of the 2Ee-2S centers of the 2-halobenzoate 1,2-dioxygenase from Burkholderia (Pseudomonas) cepacia 2CBS. J Biol Chem 270 30869-30873. 

Advanced EPR techniques such as CW and pulsed ENDOR, electron spin-echo envelope modulation (ESEEM), and two-dimensional (2D)-hyperfine sublevel correlation spectroscopy (HYSCORE) have been successfully used to examine complexation and electron transfer between carotenoids and the surrounding media in which the carotenoid is located. 

G.R. Eaton and S.S. Eaton, Electron-nuclear double resonance spectroscopy and electron spin echo envelope modulation spectroscopy, Comprehensive Coordination Chemistry II, Elsevier, Boston, 2004, 49. 

Y. Deligiannakis, M. Louloudi and N. Hadjiliadis, Electron spin echo envelope modulation (ESEEM) spectroscopy as a tool to investigate the coordination environment of metal centers, Coord. Chem. Rev., 2000, 204, 1. 

Double-resonance spectroscopy involves the use of two different sources of radiation. In the context of EPR, these usually are a microwave and a radiowave or (less common) a microwave and another microwave. The two combinations were originally called ENDOR (electron nuclear double resonance) and ELDOR (electron electron double resonance), but the development of many variations on this theme has led to a wide spectrum of derived techniques and associated acronyms, such as ESEEM (electron spin echo envelope modulation), which is a pulsed variant of ENDOR, or DEER (double electron electron spin resonance), which is a pulsed variant of ELDOR. The basic principle involves the saturation (partially or wholly) of an EPR absorption and the subsequent transfer of spin energy to a different absorption by means of the second radiation, leading to the detection of the difference signal. The requirement of saturability implies operation at close to liquid helium, or even lower, temperatures, which, combined with long experimentation times, produces a... 

Since the phenoxyls possess an S = ground state, they have been carefully studied by electron paramagnetic spectroscopy (EPR) and related techniques such as electron nuclear double resonance (ENDOR), and electron spin-echo envelope modulation (ESEEM). These powerful and very sensitive techniques are ideally suited to study the occurrence of tyrosyl radicals in a protein matrix (1, 27-30). Careful analysis of the experimental data (hyperfine coupling constants) provides experimental spin densities at a high level of precision and, in addition, the positions of these tyrosyls relative to other neighboring groups in the protein matrix. 

ESEEM Electron spin-echo envelope modulation... 

ESE envelope modulation. In the context of the present paper the nuclear modulation effect in ESE is of particular interest110, mi. Rowan et al.1 1) have shown that the amplitude of the two- and three-pulse echoes1081 does not always decay smoothly as a function of the pulse time interval r. Instead, an oscillation in the envelope of the echo associated with the hf frequencies of nuclei near the unpaired electron is observed. In systems with a large number of interacting nuclei the analysis of this modulated envelope by computer simulation has proved to be difficult in the time domain. However, it has been shown by Mims1121 that the Fourier transform of the modulation data of a three-pulse echo into the frequency domain yields a spectrum similar to that of an ENDOR spectrum. Merks and de Beer1131 have demonstrated that the display in the frequency domain has many advantages over the parameter estimation procedure in the time domain. 

The two techniques, ENDOR and ESE envelope modulation, supplement each other. ESE envelope modulation seems to be more sensitive in detecting nuclear transitions at very low frequencies but is limited in the frequency range by yeB , where ye denotes the gyromagnetic ratio of the electron and Bj the microwave pulse amplitude. ENDOR, whose sensitivity increases with frequency, suffers on the other hand from the small transition probability at low frequencies. 

The applicability of the ESE envelope modulation technique has been extended by two recent publications115,1161. Merks and de Beer1151 introduced a two-dimensional Fourier transform technique which is able to circumvent blind spots in the one-dimensional Fourier transformed display of ESE envelope modulation spectra, whereas van Ormondt and Nederveen1161 could enhance the resolution of ESE spectroscopy by applying the maximum entropy method for the spectral analysis of the time domain data. 

ESE envelope modulation studies of a number of Cu(II) compounds have been reviewed by Peisach1171. The aim of these investigations was to characterize the chemical environment of the metal binding site in Cu(II) proteins by comparison of the nuclear modulation pattern with those for Cu(II) complexes of known composition. 

Fig. 27a-c. Electron spin echo envelope modulation of Co(acacen), temperature 4K. a) Nuclear modulation pattern of Co(acacen) diluted into a Ni(acacen) 1/2 H20 single crystal. Crystal setting rotation axis I,

Fourier transform of the nuclear modulation pattern (From R. de Beer1 4)) c) Stick spectrum ENDOR frequencies (AmN = 1, 2) calculated from the hfs and quadruple tensors in Ref. 59 dashed lines ms = - 1/2, full lines ms = 1/2... 

We do not know exactly where the hydrogen binds at the active site. We would not expect it to be detectable by X-ray diffraction, even at 0.1 nm resolution. EPR (Van der Zwaan et al. 1985), ENDOR (Fan et al. 1991b) and electron spin-echo envelope modulation (ESEEM) (Chapman et al. 1988) spectroscopy have detected hyperfine interactions with exchangeable hydrous in the NiC state of the [NiFe] hydrogenase, but have not so far located the hydron. It could bind to one or both metal ions, either as a hydride or H2 complex. Transition-metal chemistry provides many examples of hydrides and H2 complexes (see, for example. Bender et al. 1997). These are mostly with higher-mass elements such as osmium or ruthenium, but iron can form them too. In order to stabilize the compounds, carbonyl and phosphine ligands are commonly used (Section 6). 

ESEEM See electron spin echo envelope modulation. e,sem or e es e e em eserine See physostigmine. es-3,ren ... 

Electron Nuclear Double Resonance (ENDOR) and Electron Spin-Echo Envelope Modulation (ESEEM)... 

Electron nuclear double resonance (ENDOR) and electron spin-echo envelope modulation (ESEEM) are two of a variety of pulsed EPR techniques that are used to study paramagnetic metal centers in metalloenzymes. The techniques are discussed in Chapter 4 of reference la and will not be discussed in any detail here. The techniques can define electron-nuclear hyperfine interactions too small to be resolved within the natural width of the EPR line. For instance, as a paramagnetic transition metal center in a metalloprotein interacts with magnetic nuclei such as H, H, P, or these... 

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