Electron Paramagnetic Resonance: Volume 25

246 Pages·2016·8.767 MB·English

by  Bagryanskaya, Elena, Barone, Vincenzo, Chechik, Victor, Klare, Johann, Lovett, Janet E., Murphy, Damien M., Sproules, Stephen

Electron Paramagnetic Resonance
Volume 25
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A Specialist Periodical Report
Electron Paramagnetic Resonance
Volume 25
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29 A Review of the Recent Literature.
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8 Editors
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9/ Victor Chechik, University of York, UK
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10 Damien M. Murphy, Cardiff University, Cardiff, UK
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d Authors
org | Edward A. Anderson, University of Oxford, UK
sc. Elena Bagryanskaya, N. N. Vorozhtsov Novosibirsk Institute of
bs.r OrganicChemistrySBRASandNovosibirskStateUniversity,Novosibirsk,
u
p://p Russian Federation
htt Vincenzo Barone, Scuola Normale Superiore, Pisa, Italy
on Jerryman Appiahene Gyamfi, Scuola Normale Superiore, Pisa, Italy
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1 Marius M. Haugland, University of Oxford, UK
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er Johann P. Klare, University of Osnabru¨ck, Germany
mb Olesya Krumkacheva, N. N. Vorozhtsov Novosibirsk Institute of Organic
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ov Chemistry SB RAS, Novosibirsk State University and International
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0 Tomography Center SB RAS, Novosibirsk, Russian Federation
n 3 Janet E. Lovett, St Andrews University, UK
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ed S.R.A.Marque,N.N.VorozhtsovNovosibirskInstituteofOrganicChemistry
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blis SB RAS, Novosibirsk, Russian Federation and Aix-Marseille Universite´,
Pu France
Andrea Piserchia, Scuola Normale Superiore, Pisa, Italy
Stephen Sproules, University of Glasgow, UK
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or ISBN: 978-1-78262-857-6
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s.rs PDF eISBN: 978-1-78262-943-6
ub EPUB eISBN: 978-1-78801-089-4
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p:// DOI: 10.1039/9781782629436
htt ISSN: 1464-4622
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0 A catalogue record for this book is available from the British Library
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n 30 All rights reserved
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he Apart from any fair dealing for the purpose of research or private study for
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Copyrightand Related Rights Regulations 2003, thispublication may not be
reproduced,storedortransmitted,inanyformorbyanymeans,withoutthe
priorpermissioninwritingofTheRoyalSocietyofChemistry,orinthecaseof
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the terms of the licences issued by the appropriate Reproduction Rights
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terms stated here should be sent to The Royal Society of Chemistry at the
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Published by The Royal Society of Chemistry,
Thomas Graham House, Science Park, Milton Road,
Cambridge CB4 0WF, UK
Registered Charity Number 207890
For further information see our web site at www.rsc.org
Preface
DOI: 10.1039/9781782629436-FP005
In recent years, the field of Electron Paramagnetic Resonance (EPR)
spectroscopy has witnessed considerable developments in instru-
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6-F the study of system bearing unpaired electrons. Noted developments in
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4 high field EPR instrumentation or improvements in smaller bench-top
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6 spectrometers, have ensured that the technique is finding wider appli-
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7 cationsinfieldsasdiverseasqualitycontrolandadvancedmaterials.The
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7 informationthatEPRcanprovideisnotsimplybasedonthedetectionof
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39/ afreeradicalorparamagneticion,butdetailedinformationonstructure,
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0.1 conformation and dynamics on length/time scales not easily accessible
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oi: by other techniques, can be readily obtained. Both pulsed and continu-
g | d ous wave (CW) EPR measurements contribute to this bountiful abun-
or danceofinformationthatcanbeextractedonanyparamagneticspecies.
c.
s.rs Moreover,theutilityofthetechniquecanbeenhanced,fromachemical
ub perspective, by the use of ancillary spin probes, labels or traps that pro-
p
p:// vide vital additional information on the spin system.
htt Thereforeinthisvolume,wehavedrawntogetheranumberofexperts
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o inthefieldofEPRtopresentthekeytrends,themesandtopicsofcurrent
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01 relevanceandinterestsinthefield.Notablytheuseofnitroxidesasspin
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er labels inEPR tostudythestructureanddynamicsofcomplex molecular
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m systems remains extremely important, so we present a number of
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o Chaptersfocussingonnitroxides asprobes, labels orguests.Inthe field
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0 ofadvancedmaterialsandquantumphysics,thespinqubitisbecoming
on 3 more and more topical, so we also present the reader with a timely
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e ChapteronthecontributionsofEPRtothisgrowingfieldofresearch.We
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bli have also continued our coverage on the role of computational and
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spectra.
The use of nitroxide spin labels continues to be widespread in EPR
spectroscopy, and Lovett et al., presents a timely review Chapter dem-
onstratinghowthepropertiesoftheselabelscanbetunedandhowthey
can be incorporated into biomolecules for structural investigations. The
theme of spin labels is continued in the Chapter by Krumkacheva and
Bagryanskaya, with a focus on the use of trityl radicals. Whilst these
radicals have been used for oxymetry and tomography in the past, their
use as spin labels for determining the structure of proteins and nucleic
acid is relatively new, and these authors provide a comprehensive over-
viewofthelatestdevelopmentsinthisfield.Theareaofsitedirectedspin
labellingforstudyingtheconformationalchangesinthecatalyticcycleof
GTP-hydrolyzingproteinsisthentreatedindetailintheChapterbyKlare.
In this Chapter, the ability of EPR to analyse the conformational equi-
libriumdynamicsandcharacterizationofconformationalchangesinthe
functions of a protein is covered. The field of host–guest chemistry is
then treated in the Chapter by Bagryanskaya and Marque, where the
ElectronParamag.Reson.,2017,25,v–vi | v
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authors consider the EPR analysis of nitroxides as guests within several
different hosts including cyclodextrins, calixarenes and cucurbiturils,
providing a comprehensive review of the literature over the past
seven years.
Onaverydifferenttopic,theChapterbySprouleshighlightstherecent
developments in the design and testing of new spin qubits in the chal-
lenging field of quantum computing, and provides illustrative examples
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6 Unquestionably theoretical calculations are vital to the modern EPR
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7 spectroscopist in order to compute reliable magnetic parameters, and
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7 even potentially simulate the entire spectrum from first principles,
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39/ andthisChapterprovidesaglimpseintothelatestexcitingdevelopments
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0.1 andimplementationsunderpinningthe‘virtualmolecularspectrometer’,
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oi: focusing on nitroxide radicals as the exemplar spin system.
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g | As always, we hope that both the expert EPR reader and novice prac-
or titioner will value these timely reviews, offering a broad perspective on
c.
s.rs the latestdevelopmentsin the field. Finally, we would also like to thank
ub all of our reporters for their expert, prompt and efficient cooperation in
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p:// the production of these Chapters and the staff at the Royal Society of
htt Chemistry for their editorial support and patience.
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vi | ElectronParamag.Reson.,2017,25,v–vi
CONTENTS
Cover
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on Preface v
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e Tuning the properties of nitroxide spin labels for use in electron 1
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No paramagnetic resonance spectroscopy through chemical
n 30 modification of the nitroxide framework
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d Marius M. Haugland, Edward A. Anderson and Janet E. Lovett
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bli 1 Introduction 1
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3 Synthetic routes to nitroxide spin labels 8
4 Recent advances in applications of spin labels 19
5 Summary 26
References 26
Trityl radicals as spin labels 35
Olesya Krumkacheva and Elena Bagryanskaya
1 Introduction 35
2 TAM radicals: structure and properties 36
3 Synthesis of TAM radicals and TAM labeling of proteins 39
and nucleic acids
4 Electron spin relaxation of TAM radicals 44
5 Peculiarities of PD EPR approaches to distance 46
measurement using TAM spin labels
ElectronParamag.Reson.,2017,25,vii–ix | vii
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6 Distance measurements at physiologically relevant 50
temperatures
7 Conclusion 56
Acknowledgements 56
References 57
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2 1 Introduction 61
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1 2 Quantum hardware 62
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org | Acknowledgements 92
sc. References 92
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20 Vincenzo Barone, Jerryman Appiahene Gyamfi and Andrea Piserchia
er
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7 Conclusions 150
Acknowledgements 151
References 151
Application of site-directed spin labelling for studying 157
conformational changes in the catalytic cycle of
G proteins activated by dimerization
Johann P. Klare
1 Introduction 157
2 Site-directed spin labelling and EPR spectroscopy 163
3 Conformational changes in the catalytic cycle of GADs 165
4 Discussion 174
Acknowledgements 177
References 177
viii | ElectronParamag.Reson.,2017,25,vii–ix
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Nitroxides in host–guest chemistry: 2010–2016 180
E. G. Bagryanskaya and S. R. A. Marque
1 Introduction 180
2 Cyclodextrins as hosts 181
3 Cucurbituril as a host 195
4 Miscellaneous 211
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