A Multidisciplinary Research Centre for Advanced Electron Paramagnetic Resonance
Lead Research Organisation:
University of Oxford
Department Name: Oxford Chemistry
Abstract
Electron Paramagnetic Resonance (EPR) is a powerful technique in the study of a wide variety of chemical and biological systems that contain so-called paramagnetic species (ie, systems with unpaired electrons). Within the last decade, the technological advances in the area of high-field and pulsed EPR have equipped the chemist and physicist with fantastic new methods for the study of new materials as well as the potential to develop new technologies such as EPR-based quantum computing algorithms. The technological advances have been accompanied furthermore by the development of sophisticated assays for site directed mutagenesis (which allows the incorporation of paramagnetic spin-labels into any chemical or biochemical system almost at will) which has made EPR exceptionally versatile in many biochemical contexts. It is the major objective of this proposal to use the impressive armory of pulsed and high-field EPR methods to advance our understanding of fundamental chemical and biological processes on the molecular scale and to exploit and develop further EPR in advancing the field of quantum computing research. The 11 investigators propose a variety of projects which can be broadly classified into two major areas, namely (i) Materials Research and (ii) Chemical Biology Research.The development of EPR-based spin manipulation methodology on self-assembling, interacting nanoscale structures such as fullerenes and nanotubes containing atomic nitrogen and other paramagnetic species is driven by the desire to establish new quantum information applications and falls clearly in the first category. Further projects in the Materials Section concentrate on the study of paramagnetic centres crucial for the hydrogen sorption/desorption processes in hydrogen-storage materials such as carbon nanostructures, the investigation of transparent conductors and finally the application of pulsed EPR methods in the elucidation of processes involving the solvated electron in electronic solutions such as the Na-NH3 system.The majority of projects in the biochemical section of this research proposal are based on an exploitation of the ability of EPR to provide information on long-range interactions (up to 8nm) between paramagnetic centres and are focussed on extracting conformational information which are difficult to obtain by other technologies (such as NMR, X-ray crystallography). The paramagnetic sites will typically be introduced to the biochemical system by site-directed mutagenesis (spin-labels) or existing paramagnetic species (such as transition metal ions or organic radicals) will be exploited to deliver this long-range distance information. Pathogen-host interactions in viral complexes as well as protein-protein recognition pathways in enzymatic processes will be elucidated with pulsed EPR techniques. Model systems (such as metal-metal-rulers) will be designed and calibrated to facilitate and guide these biochemical studies. Another application of EPR will be to support an extensive program of research now underway to identify suitable enzymes and characterise modified enzymes for the development of novel fuel-cell catalysts. This project involves hydrogenases (hydrogen cycling) from a diverse range of organisms, and laccases (O2-reduction) that are being modified for attachment to electrodes. EPR is the method of choice for examining the redox centres and catalytic intermediates in these enzymes.
Publications
Stich TA
(2014)
Paramagnetic intermediates generated by radical S-adenosylmethionine (SAM) enzymes.
in Accounts of chemical research
Zaka M
(2010)
Electron paramagnetic resonance investigation of purified catalyst-free single-walled carbon nanotubes.
in ACS nano
Bell SG
(2012)
Structure and function of CYP108D1 from Novosphingobium aromaticivorans DSM12444: an aromatic hydrocarbon-binding P450 enzyme.
in Acta crystallographica. Section D, Biological crystallography
Hong C
(2009)
Purification, crystallization and preliminary X-ray analysis of cytochrome P450 219A1 from Novosphingobium aromaticivorans DSM 12444.
in Acta crystallographica. Section F, Structural biology and crystallization communications
Blackburn OA
(2015)
Spectroscopic and Crystal Field Consequences of Fluoride Binding by [Yb·DTMA](3+) in Aqueous Solution.
in Angewandte Chemie (International ed. in English)
Farrington BJ
(2012)
Chemistry at the nanoscale: synthesis of an N@C60-N@C60 endohedral fullerene dimer.
in Angewandte Chemie (International ed. in English)
Orwick MC
(2012)
Detergent-free formation and physicochemical characterization of nanosized lipid-polymer complexes: Lipodisq.
in Angewandte Chemie (International ed. in English)
Puschmann FF
(2010)
Electromeric rhodium radical complexes.
in Angewandte Chemie (International ed. in English)
Tait C
(2015)
HYSCORE on Photoexcited Triplet States
in Applied Magnetic Resonance
Weis C
(2012)
Electrical activation and electron spin resonance measurements of implanted bismuth in isotopically enriched silicon-28
in Applied Physics Letters
Lo C
(2014)
Stark shift and field ionization of arsenic donors in 28Si-silicon-on-insulator structures
in Applied Physics Letters
Abe E
(2011)
Electron spin ensemble strongly coupled to a three-dimensional microwave cavity
in Applied Physics Letters
Bell SG
(2007)
P450 enzymes from the bacterium Novosphingobium aromaticivorans.
in Biochemical and biophysical research communications
Myers WK
(2013)
Double electron-electron resonance probes Ca²?-induced conformational changes and dimerization of recoverin.
in Biochemistry
Bolivar JH
(2016)
Interaction of lipids with the neurotensin receptor 1.
in Biochimica et biophysica acta
Oates J
(2012)
The role of cholesterol on the activity and stability of neurotensin receptor 1.
in Biochimica et biophysica acta
Di Valentin M
(2014)
Evidence for water-mediated triplet-triplet energy transfer in the photoprotective site of the peridinin-chlorophyll a-protein.
in Biochimica et biophysica acta
Sun Y
(2015)
Pulse dipolar ESR of doubly labeled mini TAR DNA and its annealing to mini TAR RNA.
in Biophysical journal
Wong LL
(2011)
P450(BM3) on steroids: the Swiss Army knife P450 enzyme just gets better.
in Chembiochem : a European journal of chemical biology
Whitehouse CJ
(2009)
A highly active single-mutation variant of P450BM3 (CYP102A1).
in Chembiochem : a European journal of chemical biology
Moro F
(2014)
Coherent electron spin manipulation in a dilute oriented ensemble of molecular nanomagnets: pulsed EPR on doped single crystals.
in Chemical communications (Cambridge, England)
Maeda K
(2011)
Spin-selective recombination kinetics of a model chemical magnetoreceptor.
in Chemical communications (Cambridge, England)
Whitehouse CJ
(2008)
Evolved CYP102A1 (P450BM3) variants oxidise a range of non-natural substrates and offer new selectivity options.
in Chemical communications (Cambridge, England)
Seel AG
(2014)
Low energy structural dynamics and constrained libration of Li(NH3)4, the lowest melting point metal.
in Chemical communications (Cambridge, England)
Dodson CA
(2015)
Fluorescence-detected magnetic field effects on radical pair reactions from femtolitre volumes.
in Chemical communications (Cambridge, England)
Xu J
(2010)
Size dependent oxygen buffering capacity of ceria nanocrystals.
in Chemical communications (Cambridge, England)
Zhou S
(2015)
Synthesis of the first completely spin-compatible N@C60 cyclopropane derivatives by carefully tuning the DBU base catalyst.
in Chemical communications (Cambridge, England)
Jones J
(2011)
Reply to Comment on 'Spin-selective reactions of radical pairs act as quantum measurements'
in Chemical Physics Letters
Jones J
(2011)
Reaction operators for spin-selective chemical reactions of radical pairs
in Chemical Physics Letters
Liu G
(2011)
Photochemical stability of N@C60 and its pyrrolidine derivatives
in Chemical Physics Letters
Plant S
(2013)
A two-step approach to the synthesis of N@C60 fullerene dimers for molecular qubits
in Chemical Science
Whitehouse CJ
(2008)
Desaturation of alkylbenzenes by cytochrome P450(BM3) (CYP102A1).
in Chemistry (Weinheim an der Bergstrasse, Germany)
Zhou B
(2010)
Studies on the reactivity of [Ge9]4- towards [Fe(cot)(CO)3]: synthesis and characterization of [Ge8Fe(CO)3]3- and of the anionic organometallic species [Fe(cot)(CO)3]-.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Krämer T
(2013)
Structural trends in ten-vertex endohedral clusters, M@E(10) and the synthesis of a new member of the family, [Fe@Sn10]3-.
in Dalton transactions (Cambridge, England : 2003)
Hiney RM
(2010)
Using EPR to follow reversible dihydrogen addition to paramagnetic clusters of high hydride count: [Rh(6)(PCy(3))(6)H(12)](+) and [Rh(6)(PCy(3))(6)H(14)](+).
in Dalton transactions (Cambridge, England : 2003)
Laidlaw WM
(2013)
Solvent and metal dependent (1)H NMR hyperfine shifts in paramagnetic pentaamminemetal cyanide-bridged mixed-valence complexes.
in Dalton transactions (Cambridge, England : 2003)
Donati N
(2008)
Rhodium and Iridium Amino, Amido, and Aminyl Radical Complexes
in European Journal of Inorganic Chemistry
Parkin A
(2012)
How Salmonella oxidises H(2) under aerobic conditions.
in FEBS letters
Spielberg ET
(2015)
A spin-frustrated trinuclear copper complex based on triaminoguanidine with an energetically well-separated degenerate ground state.
in Inorganic chemistry
Laidlaw WM
(2013)
140 H/D isotopomers identified by long-range NMR hyperfine shifts in ruthenium(III) ammine complexes. Hyperconjugation in Ru-NH3 bonding.
in Inorganic chemistry
Denning MS
(2008)
Synthesis and characterization of the 4,4'-bipyridyl dianion and radical monoanion. A structural study.
in Inorganic chemistry
Gore-Randall E
(2009)
Synthesis and characterization of alkali-metal salts of 2,2'- and 2,4'-bipyridyl radicals and dianions.
in Inorganic chemistry
Binding SC
(2015)
Synthesis, Structure, and Bonding for Bis(permethylpentalene)diiron.
in Inorganic chemistry
Evans EW
(2013)
Magnetic field effects in flavoproteins and related systems.
in Interface focus
Ardavan A
(2009)
Storing quantum information in chemically engineered nanoscale magnets
in J. Mater. Chem.
Hinderberger D
(2008)
Coordination and binding geometry of methyl-coenzyme M in the red1m state of methyl-coenzyme M reductase.
in Journal of biological inorganic chemistry : JBIC : a publication of the Society of Biological Inorganic Chemistry
Bell SG
(2010)
Protein recognition in ferredoxin-P450 electron transfer in the class I CYP199A2 system from Rhodopseudomonas palustris.
in Journal of biological inorganic chemistry : JBIC : a publication of the Society of Biological Inorganic Chemistry
Description | The technique of Electron Spin Resonance(ESR) was first discovered close to the end of World War II. Immensely powerful for probing the microscopic aspects of nature, its widespread application to leading problems in science and technology was severely limited. With the advent of of user-friendly instrumentation, its user base broadened considerably. Thus in 2006 the Center for Advanced Electron Spin Resonance (CAESR) was founded in Oxford,involving a collaboration of researchers from the departments of Chemistry, Physics,Materials, Biochemistry and Pathology with substantial support from EPSRC,BBSRC and ERC and the University to provide modern equipment and focus for Oxford's multi-disciplinary research and development in ESR. CAESR has been spectacularly successful in numerous application-orientated challenges including, quantum computing, protein structure determination, bird migration, hydrogen storage materials and advanced optoelectronic materials. Since its establishment, CAESR has been at the centre of many of the key developments in the field of ESR. For example, seminal contributions have been made by CAESR to the subjects of long range distance measurements using Double Electron Electron Resonance (DEER), and ESR quantum information methodologies. These subjects attracted over 1300 citations and over 700 citations respectively worldwide in 2012; in 1999 there were none at all in either subject. We believe that CAESR has made substantial contributions to propelling these research areas into lively and productive fields. |
Exploitation Route | Major international interactions have included collaborations with colleagues in the USA Cornell (National Biomedical Center for Advanced ESR Technology (ACERT); Princeton University , ETH Zurich (Switzerland) , Bielefeld (Germany), Hiroshima (Japan). The centre has attracted a multitude of industrial collaborators. In addition to the founding EPSRC grant, the Oxford CAESR community has won multiple external grants incorporating work at CAESR from UK agencies including EPSRC, EMFBRT, Wellcome, BBSRC and MRC, international funding sources including DARPA, NSF, EU and UKIERI, and several industrial sources, totalling over £7M. In 2015 a new state-of-the-art spectrometer was funded by EPSRC through a Strategic Equipment grant and has now attracted many UK and international collaborators. The centre has been highlighted in articles in the Oxford Blueprint, Chemistry and Industry and Chemistry World as a model modern multidisciplinary research centre. The number of ESR users within Oxford itself has grown immensely over the last years following the establishment of CAESR - a lively community of researcher from over 20 groups within Oxford use the centre frequently (and yet more scientists require the services of CAESR on a somewhat less frequent basis). |
Sectors | Aerospace, Defence and Marine,Agriculture, Food and Drink,Chemicals,Digital/Communication/Information Technologies (including Software),Electronics,Energy,Environment,Healthcare,Manufacturing, including Industrial Biotechology,Pharmaceuticals and Medical Biotechnology,Security and Diplomacy,Transport |
URL | http://caesr-web.chem.ox.ac.uk/ |
Description | Developments arising from research at CAESR have allowed close interactions with Bruker, a world-leading spectroscopic equipment manufacturer , in their further development of advanced instrumentation in ESR. This instrument manufacturer has been a very strong supporter of CAESR and through this interaction Bruker has received continuous ,first-hand feedback on instrument capability and limitations. because of these valued interactions, CAESR has enjoyed preferential technical assistance in operating its instrumentation beyond normal-use cases. We have established several industrial links which are still ongoing and are funding our Centre. Oxford has a service agreement with the National EPR service and we offer our expertise and advise as well as our spectrometers to the whole UK scientific community via this route. |
First Year Of Impact | 2006 |
Sector | Agriculture, Food and Drink,Chemicals,Digital/Communication/Information Technologies (including Software),Electronics,Energy,Environment,Manufacturing, including Industrial Biotechology,Culture, Heritage, Museums and Collections,Pharmaceuticals and Medical Biotechnology,Transport |
Impact Types | Cultural,Economic |
Description | BBSRC Grouped |
Amount | £16,533 (GBP) |
Funding ID | DMRWIS0 |
Organisation | Biotechnology and Biological Sciences Research Council (BBSRC) |
Sector | Public |
Country | United Kingdom |
Start | 05/2012 |
End | 06/2015 |
Description | BBSRC Grouped |
Amount | £16,533 (GBP) |
Funding ID | DMRWIS0 |
Organisation | Biotechnology and Biological Sciences Research Council (BBSRC) |
Sector | Public |
Country | United Kingdom |
Start | 05/2012 |
End | 06/2015 |