Dynamic Nuclear Polarization Solid-state Nuclear Magnetic Resonance Spectroscopy of Insensitive Nuclear Spins.

Lead Research Organisation: University of Liverpool
Department Name: Chemistry

Abstract

The physical properties of molecules or materials are a direct consequence of the intimate arrangement of the atoms together. Therefore, the availability of scientific methods to directly see the connectivity between these atoms is essential. Atoms are extremely small objects, in the order of 10-10 meter or equivalent to try to see a single house on the Earth from the Sun. They are smaller than the wavelength of visible light and therefore too small to be seen by the naked eye. Scientists rely on the use of indirect methods to observe these atoms. Nuclear Magnetic Resonance (NMR) spectroscopy is the most powerful technique to see these atoms. NMR is commonly related to Magnetic Resonance Imaging, often abbreviated to MRI, and is a medical imaging technique used in radiology to investigate the anatomy of a body.
The power of NMR spectroscopy relies on its sensitivity of the atomic length scale, and is used in addition to medicine, across the sciences, and especially in biology, chemistry and physics to determine the structure of matter. In particular, solid-state NMR spectroscopy, or NMR spectroscopy of solid-state samples, is becoming increasingly powerful to determine the structure of materials involved in a very wide range of applications, such as batteries, pharmaceuticals drugs and proteins responsible for diseases.
However, the main limitation of the NMR technique in general, and solid-state NMR in particular, is the sensitivity, i.e. the intensity of signals with respect to the noise level, preventing fast acquisition of the NMR signals in seconds. One very important method to dramatically enhance the NMR signals is dynamic nuclear polarization. This technique permits a sensitivity enhancement factor of several hundred leading to reduction in experimental times of up to five orders of magnitude. For example, an NMR experiment lasting 10 min with dynamic nuclear polarization will require more than 1 year without dynamic nuclear polarization to obtain identical signal to noise ratio. This changes completely the type of atomic solid-state structures that could be determined and studied by NMR. Dynamic nuclear polarization relies on a transfer of polarization from the highly sensitive electron spins to the low sensitive nuclear spins at cryogenic temperatures. Dynamic nuclear polarization instruments capable of performing these experiments have only been available commercially since 2010. There are none in the United Kingdom today. Hence, this proposal aims at funding overseas travel to countries (such as France and the United States) to access a range of dynamic nuclear polarization hardware with various capabilities, and investigate some fundamental aspects of dynamic nuclear polarization enhanced solid-state NMR spectroscopy.
Of particular interest to this proposal is that the work will exclusively target nuclei that are difficult (or nearly impossible) to detect by normal solid-state NMR, either due to a low natural abundance (e.g. 17O, 43Ca) or a low resonance frequency (25Mg, 39K, 107Ag, 183W) or a combination of both, and is therefore a clear and natural application of a dramatic sensitive enhancement technique such as dynamic nuclear polarization. This will be the source of immediate innovations in a very wide range of areas across science such as in materials science, catalysis and nanotechnology. It has the potential to completely revolutionize approaches to the determination of the atomic scale structure of materials, thereby driving the development of new high performance materials.

Planned Impact

The proposed to be conducted is multi-disciplinary and the beneficiaries from the research are large, and include:
- Members of the wider public, including schools and interested public groups,
- UK and EU government departments and agencies,
- UK chemical Industries and broader industry sectors, such as health and energy sectors,
and will be made aware of this work with outreach activities and media coverage.

UK economic and competitiveness in chemistry and analytical chemistry will be enhanced by:
- Scientific excellence and expertise in analytical chemistry with the UK 850 MHz national solid-state NMR facility at the University of Warwick, the UK solid-state NMR service infrastructure at the University of Durham, and the recently funded UK dynamic nuclear polarization enhanced solid-state NMR facility at the University of Nottingham,
- Technical overlap and alignment with the Center for Materials Discovery, Materials Innovation Factory, Stephenson Institute for Renewable Energy at the University of Liverpool, and the dynamic nuclear polarization facility at the University of Nottingham.
- Dissemination through Liverpool Centres of excellence, Institute of Physics Nuclear Magnetic Resonance group, and chemicals-using industry sectors.

The following strategies will be implemented to ensure maximal impact of project outputs, and carried out by Dr. Frédéric Blanc (with the students taking part in the project):
- Develop joint impact activities between the University of Liverpool and other UK universities involved in dynamic nuclear polarization research (Nottingham, Southampton and Warwick).
- Outreach activities in schools, for example using the University of Liverpool 'Professor Fluffy's' adventure program or contributing to the annual Salter's Festival of Chemistry.
- Holding events to maximize outreach with the public (Widnes SciBar seminars, Catalyst Science Discovery Center events in the UK, and in the Grenoble and Boston locations where the overseas travel research work will be carried out) as well as wider dissemination by active media engagement.

Publications

10 25 50
 
Description Through this funded research, we have developed an approach that permits the NMR detection of nuclear spins that are usually below the sensitivity limit of NMR; we have illustrated the research with 17O at natural abundance (0.037%) and very low receptive nucleus such as 89Y.
Exploitation Route Our published findings have already been taken forward by others who have exploited the results to quantity the strenght of Bronsted acidity in silica alumina materials.
Sectors Chemicals,Energy

 
Description Response to the House of Commons Science and Technology Committee inquiry regarding the implications and opportunities for science and research of leaving the EU.
Geographic Reach National 
Policy Influence Type Participation in a national consultation
URL https://www.parliament.uk/business/committees/committees-a-z/commons-select/science-and-technology-c...
 
Description EPSRC Institutional Sponsorship
Amount £20,000 (GBP)
Funding ID EP/P511353/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 11/2016 
End 04/2017
 
Title Fast Dynamic Nuclear Polarisation Hyperpolarisation Nuclear Magnetic Resonance at Very High Field 
Description Fast Dynamic Nuclear Polarisation Hyperpolarisation Nuclear Magnetic Resonance at Very High Field 
Type Of Material Improvements to research infrastructure 
Year Produced 2016 
Provided To Others? Yes  
Impact New Fast Method of Characterisation in Chemistry 
 
Description Bruker DNP 
Organisation Bruker Corporation
Department Bruker BioSpin
Country Germany 
Sector Private 
PI Contribution Performing DNP experiments at Bruker
Collaborator Contribution Provide access to DNP spectrometer
Impact Publications outputs
Start Year 2015
 
Description CEA DNP 
Organisation French Alternative Energies and Atomic Energy Commission
Country France 
Sector Public 
PI Contribution DNP experiments at CEA
Collaborator Contribution Access to DNP spectrometer
Impact Publications outputs
Start Year 2013
 
Description Newsletter to the industrial sector 
Form Of Engagement Activity A magazine, newsletter or online publication
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Industry/Business
Results and Impact Article in the Knowledge Center for Materials Discovery newsletter
Year(s) Of Engagement Activity 2016
URL http://materialschemistry.org.uk/wp-content/uploads/2016/10/KCMC-Newsletter-October-High-Res.pdf
 
Description Newsletter to the industrial sector 
Form Of Engagement Activity A magazine, newsletter or online publication
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Industry/Business
Results and Impact Newsletter in the industrial sector (Bruker company, manufacturer of scientific instrumentation)
Year(s) Of Engagement Activity 2017
 
Description Outreach at school 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Schools
Results and Impact Outreach event
Year(s) Of Engagement Activity 2016
 
Description Pint of Science Outreach Event 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Public/other audiences
Results and Impact Outreach even to the general public highlighting recent research output in Chemistry at Liverpool
Year(s) Of Engagement Activity 2018
URL https://pintofscience.co.uk/event/invisible-science