Orientation-Selective DEER Using Rigid Spin Labels, Cofactors, Metals, and Clusters

Chapter
Part of the Structure and Bonding book series (STRUCTURE, volume 152)

Abstract

The dipolar interaction between two paramagnetic centres depends upon their spin–spin distance and relative orientation. Generally most experiments are carried out under conditions where the DEER signal only reports on the spin–spin distances and, for this type of data, sophisticated analysis methods for obtaining distance distributions have been developed. Recently there have been an increasing number of studies on systems where the DEER signals depend upon both distance and spin pair orientation. These investigations have relied on the use of rigid spin labels (those with a well-defined spatial position) and/or spectrometers operating at Q-band frequencies and above capable of performing DEER experiments with high resolution and sensitivity. In this article we discuss in detail orientation-selective DEER experiments for which the modulation depth and the dipolar frequencies depend on the relative orientation of the two paramagnetic centres and the distance. Analysis of the data in the presence of distance and orientation distributions is discussed, and representative examples from the literature are given for systems containing spin labels, organic cofactors, metals, and metal clusters.

Keywords

Distance measurement DEER EPR ESR Metal Metal cluster Orientation selection PELDOR Spin label Structural information 

Abbreviations

DEER

Double electron—electron resonance

DQC

Double–quantum coherence

ENDOR

Pulsed electron—nuclear double resonance

EPR

Electron paramagnetic resonance

f.w.h.m

Full width half maximum

Fe-S

Iron-Sulphur

HYSCORE

Hyperfine sublevel correlation

MTSL

1-Oxyl-2,2,5,5-tetramethylpyrrolinyl-3-methyl)-methanethiosulphonate

mw

Microwave

os-DEER

Observer-selective DEER

PELDOR

Pulsed electron—electron double resonance

RIDME

Relaxation-induced dipole modulation enhancement

TWTA

Travelling wave tube amplifier

ZFS

Zero-field splitting

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Copyright information

© Springer-Verlag Berlin Heidelberg 2013

Authors and Affiliations

  1. 1.Department of Chemistry, Centre for Advanced Electron Spin ResonanceUniversity of OxfordOxfordUK
  2. 2.Centre for Advanced ImagingUniversity of QueenslandSt LuciaAustralia

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