EPR Spectroscopy: Applications in Chemistry and Biology

246 Pages·2012·4.45 MB·English

by  Sabine Van Doorslaer, Damien M. Murphy (auth.), Malte Drescher, Gunnar Jeschke (eds.)

321
Topics in Current Chemistry
Editorial Board:
K.N. Houk C.A. Hunter M.J. Krische J.-M. Lehn
l l l
S.V. Ley M. Olivucci J. Thiem M. Venturi P. Vogel
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C.-H. Wong H. Wong H. Yamamoto
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EPR Spectroscopy
Applications in Chemistry and Biology
(cid:1)
Volume Editors: Malte Drescher Gunnar Jeschke
With Contributions by
E. Bordignon (cid:1) M. Drescher (cid:1) B. Endeward (cid:1) D. Hinderberger (cid:1)
I. Krstic´ (cid:1) D. Margraf (cid:1) A. Marko (cid:1) D.M. Murphy (cid:1) T.F. Prisner (cid:1)
E. Schleicher (cid:1) S. Van Doorslaer (cid:1) J. van Slageren (cid:1) S. Weber
Editors
Dr.MalteDrescher Dr.GunnarJeschke
DepartmentofChemistry LaboratoryofPhysicalChemistry
UniversityofKonstanz ETHZurich
Konstanz Zurich
Germany Switzerland
ISSN0340-1022 e-ISSN1436-5049
ISBN978-3-642-28346-8 e-ISBN978-3-642-28347-5
DOI10.1007/978-3-642-28347-5
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Preface
Electron paramagnetic resonance (EPR) spectroscopy [1-3] is the most selective,
best resolved, and a highly sensitive spectroscopy for the characterization of
speciesthatcontainunpairedelectrons.AfterthefirstexperimentsbyZavoiskyin
1944[4]mainlycontinuous-wave(CW)techniquesintheX-bandfrequencyrange
(9-10 GHz) were developed and applied to organic free radicals, transition metal
complexes,andrareearthions.Manyoftheseapplicationswererelatedtoreaction
mechanismsandcatalysis,asspecieswithunpairedelectronsareinherentlyunsta-
ble and thus reactive. This period culminated in the 1970s, when CW EPR had
become a routine technique in these fields. The best resolution for the hyperfine
couplingsbetweentheunairedelectronandnucleiinthevicinitywasobtainedwith
CWelectronnucleardoubleresonance(ENDOR)techniques[5].
Startinginthe1960s,stablefreeradicalsofthenitroxidetypeweredevelopedas
spinprobesthatcouldbeadmixedtoamorphousorweaklyorderedmaterialsandas
spinlabelsthatcouldbecovalentlyattachedtomacromoleculesatsitesofinterest
[6,7].Inparallel,theorywasdevelopedforanalyzinglinewidthsandlineshapesin
CWEPRspectraintermsofmoleculardynamics[8-10].Ataboutthesametimea
fewselectgroupsintheSovietUnionandtheUSAworkedonpulseexperiments,
using spin echo phenomena to measure electron spin relaxation [11], to detect
hyperfine couplings by electron spin echo envelope modulation (ESEEM) techni-
ques[12],toacquireENDORspectrainabroadertemperaturerangethanwithCW
methods[13],andtomeasuredistancesbetween electronspins[14].Thesedevel-
opments were pursued by physicists, were heavily focused on methodology, and
werehardlyrecognizedbymainstreamchemistsevenbytheendofthe1980swhen
thegroundworkwasalldone.Asaresult,EPRspectroscopyacquiredthereputation
ofanold-fashioned,somewhatobscuretechniqueapplicabletoonlyasmallrange
ofcompounds.Manychemistrydepartmentsconsidereditasdispensable.
Severaldevelopmentsinthe1990spreparedthestagefortherenaissanceofEPR
spectroscopythatwenowexperience.ConceptsofpulseNMRwereintroducedinto
pulse EPR [15,16], which lead to a zoo of new experiments for the separation of
different interactions of the electron spin with its environment [3]. After an
ix
x Preface
induction period a new generation of EPR spectroscopists started using these
techniques in the established application fields of transition metal catalysis and
metalloenzymes.Withinthesamedecadetheapplicationfieldinstructuralbiology
wasextendedtremendouslybytheintroductionofsite-directedspinlabeling[17],
which made diamagnetic proteins accessible to EPR spectroscopy, among them
many that were difficult to study by x-ray crystallography or NMR spectroscopy.
The third major development of the 1990s was the systematic combination of
EPR measurements at multiple frequencies (multi-frequency EPR) to study more
complexproblems,and,inparticular,theextensiontohigherfieldsandfrequencies,
madepossiblebynewmicrowavetechnologyandbythesuperconductingmagnet
technologydevelopedforNMRspectroscopy[18,19].
ThisvolumeofTopicsinCurrentChemistryisdevotedtotheconsequencesthat
these three parallel developments have had on the application field of EPR spec-
troscopy. It is no exaggeration to state that the major part of the systems studied
nowadaysbyEPRspectroscopywasinaccessibletwodecadesagoandthatforthe
remaining systems information can be obtained, which was inaccessible at that
time.ThescopeofEPRspectroscopyarisingfromthiscombinationhasbeenhardly
realizedevenbythemostadvancedpractitioners.
This volume starts with three chapters that illustrate the wealth of information
which can now be obtained in some of the traditional application fields of EPR
spectroscopy.Chapter1byS.VanDoorslaerandD.Murphyisanin-depthreview
onworkincatalysisfocusingonthemechanisticinformationthatcanbeobtained
from EPR spectra. Work on radical enzymes is exemplified in Chapter 2 by
S. Weber and E. Schleicher on the example of flavoproteins which play a role in
both chemically and light-activated electron transfer processes. Chapter 3 on
synthetic polymers by D. Hinderberger argues that careful analysis of mundane
nitroxidespinlabelorspinprobeCWEPRspectracanrevealalotofinformation
whichishardtoobtainbyanyothercharacterizationtechnique.
Thefollowingthreechaptersexploretheopportunitiesprovidedbysite-directed
spin labeling of diamagnetic biomacromolecules. Intrinsically disordered proteins
areoneclassofsuchbiomacromoleculesthatishardtocharacterizebyestablished
techniques. Chapter 4 by M. Drescher discusses how EPR spectroscopy can con-
tribute to better understanding of these proteins. The main application of site-
directedspinlabelingtechniquesisonmembraneproteins,whicharemoredifficult
to study by crystallography and high-resolution NMR spectroscopy than soluble
proteins.EPRonmembraneproteinsistreatedinChapter5byE.Bordignon,with
an emphasis on the nuts and bolts of the approach. During the past few years
application of spin label EPR to nucleic acids has emerged, and Chapter 6 by
I. Krstic´, B. Endeward, D. Margraf, A. Marko, and T. Prisner provides a compre-
hensiveoverviewofbothspinlabelingandEPRtechniquesappliedinthisfieldand
ontheinformationthatcanbeobtained.
Finally,anemergingapplicationfieldisdiscussed.Theapplicationtomolecular
magnetsisaresultofparalleldevelopmentofnewapproachesininorganicchem-
istryandnewhigh-fieldandhigh-frequencyEPRtechnologies.InChapter7J.van
Slageren discusses the newly emerging technologies of frequency-domain