Collaborative Computational Project in NMR Crystallography

Lead Research Organisation: University of Oxford
Department Name: Materials

Abstract

Solid-state nuclear magnetic resonance (NMR) is capable of providing extremely detailed insights into the structure and dynamics of a wide range of materials - from organic systems such as pharmaceutical compounds and supramolecular arrays to inorganic materials for next-generation batteries and safe storage of nuclear waste. Such information is crucial for harnessing the properties of increasingly complex new materials, needed to address major challenges across the physical sciences. However, the true potential of this experimental technique is only realized through combination with advanced computational methods. These range from first-principles electronic structure predictions of the key NMR interaction tensors through to the simulation of nuclear spin interactions for direct comparison with experimental spectra. In tackling challenging problems, the emerging field of NMR Crystallography also benefits from close interaction with the related methods of powder X-ray diffraction and crystal structure prediction.

The Collaborative Computational Project for NMR Crystallography supports a multidisciplinary community of NMR spectroscopists, crystallographers, materials modellers and application scientists, both within academia and industry. We develop overarching software tools enabling a largely experimentally focused community to deploy advanced computational techniques.

Planned Impact

We have identified a number of pathways by which the outputs of the proposed research will impact more widely than the more obvious academic research implications (which is detailed in the "Academic Beneficiaries" section). These additional routes include both economic and educational impact.

A direct impact is to companies who use solid-state NMR in-house for characterisation of solid forms. For example, the pharmaceutical companies such as GSK, AZ, Sanofi-Avensis all have in-house solid-state NMR spectrometers with experienced personnel as does Johnson Matthey in the field of catalysis.

A direct economic impact of this research is the potential for commercialisation of the outputs, particularly related to the developments in the CASTEP software. Accelrys Inc. (see www.accelrys.com) provide a commercially supported version of the CASTEP software to Industrial users which is licensed from the CASTEP Developers Group. Sales of the NMR-CASTEP program have now exceeded $1.8M including many international companies in the pharmaceutical and catalysis sectors.

In the longer term outputs of the project will also have indirect impact on researchers in Materials, Chemical and Life Sciences who use information derived from NMR. These consist of both academics and industrial companies interested in developing new or better materials for a wide range of applications, e.g. for energy storage, fuel cell and battery related materials, for nuclear waste disposal, as catalysts, new bioactive materials.

The integrated NMR Crystallography software can be used for educational purposes. Many universities include courses on molecule/materials modelling at the undergraduate level, and the CCP-NC software enables linking to spectroscopy topics. The project will involve the training of post-graduate students and PDRA some of whom will go on to use these skills in industry (previous students and PDRA with the Investigators are carrying out NMR work at companies such as GSK, Johnson Matthey, and Agilent Technologies)

All of the investigators' institutions already have well established outreach programmes; for example, summer schools for high-school students. The wide areas of application touched by this proposal will feedback into these presentations, and we can use our expertise to further inform and inspire young people in science.

Publications

10 25 50
publication icon
Lau S (2019) Drug orientations within statin-loaded lipoprotein nanoparticles by F solid-state NMR. in Chemical communications (Cambridge, England)

publication icon
Hooper TN (2019) The partial dehydrogenation of aluminium dihydrides. in Chemical science

publication icon
Camacho PS (2018) Polymorphism, Weak Interactions and Phase Transitions in Chalcogen-Phosphorus Heterocycles. in Chemistry (Weinheim an der Bergstrasse, Germany)

publication icon
Bühl M (2016) Paramagnetic NMR of Phenolic Oxime Copper Complexes: A Joint Experimental and Density Functional Study. in Chemistry (Weinheim an der Bergstrasse, Germany)

 
Description In its second funded period, CCP-NC has established itself, both within the UK and on the wider international stage, as the recognised body providing leadership and direction for computation in NMR crystallography:

(a) developed and release new tools for visualisation and processing of NMR parameters - linking together ab-initio calculations of NMR parameters with density matrix simulations of experimental spectra (MagresView, MagresPython);

(b) provide well attended workshops for the training of graduate students and postdoctoral researchers (in the past 3 years, 210 participants from 30 countries);

(c) We strengthened the use of NMR Crystallography in industry through secondments which produced extensive guidance on best practice.
Exploitation Route Through the guidance we have published, industries can apply NMR Crystallography techniques 'in-house' to address materials characterisation challenges.
Sectors Chemicals,Energy,Pharmaceuticals and Medical Biotechnology

URL http://www.ccpnc.ac.uk
 
Description Use of NMR Crystallography software in drug discovery.
First Year Of Impact 2017
Sector Pharmaceuticals and Medical Biotechnology
Impact Types Societal

 
Description Collaborative Computational Project in NMR Crystallography
Amount £273,143 (GBP)
Funding ID EP/T026642/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 05/2020 
End 05/2025
 
Description eCSE
Amount £80,000 (GBP)
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Department ARCHER Service
Sector Academic/University
Country United Kingdom
Start 01/2016 
End 12/2016
 
Title A Picture of Disorder in Hydrous Wadsleyite - Under the Combined Microscope of Solid-State NMR Spectroscopy and Ab Initio Random Structure Searching (dataset) 
Description  
Type Of Material Database/Collection of data 
Year Produced 2018 
Provided To Others? Yes  
 
Title An NMR Crystallographic Investigation of the Relationships Between the Crystal Structure and 29Si Isotropic Chemical Shift in Silica Zeolites (dataset) 
Description  
Type Of Material Database/Collection of data 
Year Produced 2017 
Provided To Others? Yes  
 
Title Calculation and Experimental Measurement of Paramagnetic NMR Parameters of Phenolic Oximate Cu(II) Complexes (dataset) 
Description  
Type Of Material Database/Collection of data 
Year Produced 2017 
Provided To Others? Yes  
 
Title Data underpinning - A Multinuclear NMR Study of Six Forms of AlPO-34: Structure and Motional Broadening 
Description  
Type Of Material Database/Collection of data 
Year Produced 2017 
Provided To Others? Yes  
 
Title Data underpinning - Hunting for Hydrogen: Random Structure Searching and Prediction of NMR Parameters of Hydrous Wadsleyite 
Description  
Type Of Material Database/Collection of data 
Year Produced 2016 
Provided To Others? Yes  
 
Title Data underpinning - Investigating unusual homonuclear intermolecular "Through-Space" J couplings in organochalcogen systems 
Description  
Type Of Material Database/Collection of data 
Year Produced 2016 
Provided To Others? Yes  
 
Title Data underpinning - Phase Composition and Disorder in La2(Sn,Ti)2O7 Ceramics: New Insights from NMR Crystallography 
Description  
Type Of Material Database/Collection of data 
Year Produced 2016 
Provided To Others? Yes  
 
Title Data underpinning research article: Paramagnetic NMR of phenolic oxime copper complexes - a joint experimental and density functional study 
Description Data and metadata for the experimental and NMR part, as well as all inputs and outputs for the computational part. 
Type Of Material Database/Collection of data 
Year Produced 2016 
Provided To Others? Yes  
 
Title Determination of a Complex Crystal Structure in the Absence of Single Crystals: Analysis of Powder X-ray Diffraction Data, Guided by Solid-State NMR and Periodic DFT Calculations, Reveals A New 2'-Deoxyguanosine Structural Motif 
Description Derivatives of guanine exhibit diverse supramolecular chemistry, with a variety of distinct hydrogen-bonding motifs reported in the solid state, including ribbons and quartets, which resemble the G-quadruplex found in nucleic acids with sequences rich in guanine. Reflecting this diversity, the solid-state structural properties of 3',5'-bis-O-decanoyl-2'-deoxyguanosine, reported in this paper, reveal a hydrogen-bonded guanine ribbon motif that has not been observed previously for 2'-deoxyguanosine derivatives. In this case, structure determination was carried out directly from powder X-ray diffraction (XRD) data, representing one of the most challenging organic molecular structures (a 90-atom molecule) that has been solved to date by this technique. While specific challenges were encountered in the structure determination process, a successful outcome was achieved by augmenting the powder XRD analysis with information derived from solid-state NMR data and with dispersion-corrected periodic density functional theory (DFT) calculations for structure optimization. The synergy of experimental and computational methodologies demonstrated in the present work is likely to be an essential feature of strategies to further expand the application of powder XRD as a technique for structure determination of organic molecular materials of even greater complexity in the future. The dataset consists of the powder XRD data, with data provided in both the raw format, as generated by the Bruker D8 Diffractometer, and in the cpi format, together with three magres files generated by the program CASTEP when calculating NMR parameters from our crystal structure. 
Type Of Material Database/Collection of data 
Year Produced 2017 
Provided To Others? Yes  
 
Title Ensemble-Based Modelling of the NMR Spectra of Solid Solutions: Cation Disorder in Y2(Sn,Ti)2O7 (dataset) 
Description  
Type Of Material Database/Collection of data 
Year Produced 2019 
Provided To Others? Yes  
 
Title NMR chemical shifts of urea loaded copper benzoate. A joint solid-state NMR and DFT study (dataset) 
Description  
Type Of Material Database/Collection of data 
Year Produced 2019 
Provided To Others? Yes  
 
Title Polymorphism, Weak Interactions and Phase Transitions in Chalcogen-Phosphorus Heterocycles (dataset) 
Description  
Type Of Material Database/Collection of data 
Year Produced 2018 
Provided To Others? Yes  
 
Title The Ambient Hydration of the Aluminophosphate JDF-2 to AlPO-53(A): Insights from NMR Crystallography (dataset) 
Description  
Type Of Material Database/Collection of data 
Year Produced 2017 
Provided To Others? Yes  
 
Title CASTEP 
Description CASTEP is a leading code for calculating the properties of materials from first principles. Using density functional theory, it can simulate a wide range of properties of materials proprieties including energetics, structure at the atomic level, vibrational properties, electronic response properties etc. In particular it has a wide range of spectroscopic features that link directly to experiment, such as infra-red and Raman spectroscopies, NMR, and core level spectra 
Type Of Technology Software 
Year Produced 2018 
Impact NMR functionality widely used in pharmaceutical and catalysis industries. 
URL http://www.castep.org
 
Title MagresView 
Description MagresView enables the visualisation of the output of the first principles calculation of NMR parameters. It also enables a user to compute euler angles, dipoler couplings. It provides 1-D and 2-D spectral simulations and provides an easy link to spin simulations for more sophisticated experiments. 
Type Of Technology Software 
Year Produced 2018 
Open Source License? Yes  
Impact Used in 20 publications to date. Paper describing software available at https://doi.org/10.1016/j.ssnmr.2016.05.004 
URL https://doi.org/10.1016/j.ssnmr.2016.05.004
 
Title Soprano 
Description Soprano is a Python library to aid in general crystallography tasks, including NMR parameter manipulation, using among other things simple machine learning algorithms 
Type Of Technology Software 
Year Produced 2017 
Open Source License? Yes  
Impact Used in high throughput studies of NMR parameters. 
URL https://ccp-nc.github.io/soprano/