EPSRC-Royal Society fellowship engagement (2012): Biomimetic Guest-Selective Metal-Organic Frameworks: Catalysis and Self-Assembly
Lead Research Organisation:
University of Glasgow
Department Name: School of Chemistry
Abstract
Please refer to attached Royal Society Application
Planned Impact
Please refer to attached Royal Society Application
Organisations
- University of Glasgow (Fellow, Lead Research Organisation)
- EPSRC Centre for Innovative Manufacturing for Continuous Manufacturing and Crystallisation (CMAC) (Collaboration)
- UNIVERSITY OF GLASGOW (Collaboration)
- University of Western Australia (Collaboration)
- University of New Brunswick (Collaboration)
- UNIVERSITY OF EDINBURGH (Collaboration)
- UNIVERSITY OF CAMBRIDGE (Collaboration)
Publications
Angioni E
(2019)
Implementing fluorescent MOFs as down-converting layers in hybrid light-emitting diodes
in Journal of Materials Chemistry C
Forgan R
(2015)
Structure-directing factors when introducing hydrogen bond functionality to metal-organic frameworks
in CrystEngComm
Hobday C
(2016)
A Computational and Experimental Approach Linking Disorder, High-Pressure Behavior, and Mechanical Properties in UiO Frameworks
in Angewandte Chemie
Hobday CL
(2016)
A Computational and Experimental Approach Linking Disorder, High-Pressure Behavior, and Mechanical Properties in UiO Frameworks.
in Angewandte Chemie (International ed. in English)
Jennings CS
(2021)
Immobilising giant unilamellar vesicles with zirconium metal-organic framework anchors.
in Soft matter
Marshall R
(2018)
Controlling interpenetration through linker conformation in the modulated synthesis of Sc metal-organic frameworks
in Journal of Materials Chemistry A
Marshall R
(2016)
Postsynthetic Modification of Zirconium Metal-Organic Frameworks
in European Journal of Inorganic Chemistry
Marshall R
(2017)
Crystallographic investigation into the self-assembly, guest binding, and flexibility of urea functionalised metal-organic frameworks
in Supramolecular Chemistry
Marshall R
(2016)
Amino acids as highly efficient modulators for single crystals of zirconium and hafnium metal-organic frameworks
in Journal of Materials Chemistry A
Marshall RJ
(2016)
Postsynthetic bromination of UiO-66 analogues: altering linker flexibility and mechanical compliance.
in Dalton transactions (Cambridge, England : 2003)
| Description | The aim of the project was to introduce bespoke functionality into porous materials to allow selective binding and activation of guests in a manner mimicking the way biological enzymes catalyse chemical reactions. These porous materials - metal-organic frameworks (MOFs) - are coordination polymers where metal clusters link organic compounds into three dimensional structures. This has proven significantly more difficult than envisaged, as the chemical functionality introduced into the materials has instead directed the formation of new structures rather than formed specific binding sites for selected guests. As such, we began investigating MOFs linked by zirconium, as these tend to have rigid, highly predictable structures which do not change on introduction of chemical functionality. We also intended to introduce functionality through controlling the extent and chemical identity of defects within these structures as a new route to modifying their binding properties. In investigating zirconium MOFs, we have developed enhanced synthetic methodologies to allow access to materials that cannot be prepared through conventional means. We introduce small quantities of amino acids into syntheses which allows us to control the size of the particles we prepare and improve their crystallinity and thus guest binding properties. These methodologies have been applied to MOFs linked by Scandium and Yttrium, and have also been applied to MOFs linked by Iron and Chromium in subsequent projects whereby other funding has been achieved. We have used the enhanced materials properties which we can now obtain to examine the effect of mechanical stress on Zr MOFs. Whilst we are interested in MOFs for catalytic applications, they are also being examined for carbon capture and storage, which requires the MOFs (synthesised as powders) to be post-processed into pellets, or columns, or other forms. To do so, they must survive mechanical stress (i.e. high pressure). We have elucidated the key role of the organic linking component in tuning the response to pressure, and prepared a MOF that survives up to 50,000 bar through chemically modifying the organic linker. Our investigations into guest binding in Zr MOFs have allowed us to develop a new mode of trapping toxic molecules - through chemical reaction with the organic linkers, rather than simply absorbing the molecules like a sponge, which is the conventional approach. This has been made possible by the chemical stability of our materials and also their mechanical stability, assessed in tandem, which allows them to contract upon reacting with guests. Finally, we have begun to develop Zr MOFs for drug delivery applications, where we use our control of particle size to prepare nanoparticles which can bind guests, such as drugs, and deliver them into cells. Some of the materials developed during this project have found use in early stage drug delivery applications, and we have developed new projects which are investigating these materials and methods for their further functionalisation in more detail. This has also led to acquisition of new funding and formation of new collaborations. |
| Exploitation Route | Many of the new techniques developed for Zr MOFs are being taken forward by academics in the field, as evidenced by the citations the manuscripts have received and two papers which directly follow on from our own work. Particularly the new methods for synthesis and functionalisation of Zr MOFs are being adopted internationally by other researchers. Our work into understanding synthesis and crystallisation of MOFs has led to collaboration with the Continuous Manufacture and Crystallisation (CMAC) EPSRC Future Manufacturing Hub, which has many members from the pharmaceutical industry interested in the synthesis of advanced functional materials. I now supervise a student through the CMAC Centre for Doctoral Training and we are preparing future grant applications in collaboration with industrial partners to develop new continuous manufacturing methods. The methods to sequester toxic gases through chemical reaction have resulted in a nascent collaboration with Johnson Matthey, who are interested in this technology. A proposal for an EPSRC CASE studentship was submitted but was unfortunately unsuccessful. We are currently examining the potential routes to develop this collaboration in future. The use of Zr MOFs in drug delivery applications is very early stage but very promising, and may have impact in the healthcare industry, which we are assessing as work continues. |
| Sectors | Chemicals,Healthcare,Manufacturing, including Industrial Biotechology,Pharmaceuticals and Medical Biotechnology |
| URL | http://www.forganlab.com |
| Description | The project laid the groundwork for subsequent research applying nanoparticulate MOFs in drug delivery, leading to my group becoming world leaders in this field. As such, I have been appointed as a scientific advisor for NovoMOF, a MOF manufacturer, and am now able to direct their output to new applications and generate new industrial interest in MOFs. The RA employed by the project, Dr Ross Marshall, has since become a School teacher in the city of Glasgow. We maintain links and offer opportunities for his school pupils to visit Glasgow and learn about research chemistry. In doing so, we hope to encourage more students to study chemistry and develop new outreach opportunities. |
| First Year Of Impact | 2019 |
| Sector | Chemicals,Education |
| Impact Types | Societal,Economic |
| Description | EPSRC IRC in Targeted Delivery for Hard-to-Treat Cancers |
| Amount | £10,275,035 (GBP) |
| Funding ID | EP/S009000/1 |
| Organisation | Engineering and Physical Sciences Research Council (EPSRC) |
| Sector | Public |
| Country | United Kingdom |
| Start | 10/2018 |
| End | 09/2024 |
| Description | Pump Priming Award |
| Amount | £12,900 (GBP) |
| Funding ID | PP 14 05 03 |
| Organisation | Engineering and Physical Sciences Research Council (EPSRC) |
| Sector | Public |
| Country | United Kingdom |
| Start | 08/2014 |
| End | 03/2015 |
| Description | Royal Society Research Fellows Enhancement Award |
| Amount | £101,639 (GBP) |
| Funding ID | RGF/EA/180077 |
| Organisation | The Royal Society |
| Sector | Charity/Non Profit |
| Country | United Kingdom |
| Start | 01/2018 |
| End | 10/2021 |
| Title | Amino acids as highly efficient modulators for single crystals of Zirconium and Hafnium metal-organic frameworks. |
| Description | |
| Type Of Material | Database/Collection of data |
| Year Produced | 2016 |
| Provided To Others? | Yes |
| Title | Controlling Interpenetration Through Linker Conformation in the Modulated Synthesis of Sc Metal-Organic Frameworks |
| Description | Experimental datasets |
| Type Of Material | Database/Collection of data |
| Year Produced | 2018 |
| Provided To Others? | Yes |
| Impact | Public availability |
| Title | Correlating pressure-induced emission modulation with linker rotation in a photoluminescent MOF |
| Description | Experimental data in excel format |
| Type Of Material | Database/Collection of data |
| Year Produced | 2020 |
| Provided To Others? | Yes |
| URL | http://researchdata.gla.ac.uk/id/eprint/983 |
| Title | Functional Versatility of a Series of Zr Metal-Organic Frameworks Probed by Solid-State Photoluminescence Spectroscopy |
| Description | Experimental dataset. |
| Type Of Material | Database/Collection of data |
| Year Produced | 2017 |
| Provided To Others? | Yes |
| Impact | Public availability |
| Title | Implementing fluorescent MOFs as down-converting layers in hybrid light-emitting diodes |
| Description | |
| Type Of Material | Database/Collection of data |
| Year Produced | 2018 |
| Provided To Others? | Yes |
| Title | Photophysics of azobenzene constrained in a UiO metal-organic framework: effects of pressure, solvation and dynamic disorder |
| Description | |
| Type Of Material | Database/Collection of data |
| Year Produced | 2021 |
| Provided To Others? | Yes |
| URL | http://researchdata.gla.ac.uk/id/eprint/1181 |
| Title | Postsynthetic Bromination of UiO66 Analogues Altering Linker Flexibility and Mechanical Compliance |
| Description | |
| Type Of Material | Database/Collection of data |
| Year Produced | 2015 |
| Provided To Others? | Yes |
| Title | Single-crystal to single-crystal mechanical contraction of metal-organic frameworks through stereoselective post-synthetic bromination. |
| Description | |
| Type Of Material | Database/Collection of data |
| Year Produced | 2015 |
| Provided To Others? | Yes |
| Title | Stereoselective halogenation of integral unsaturated C-C bonds in chemically and mechanically robust Zr and Hf MOFs |
| Description | |
| Type Of Material | Database/Collection of data |
| Year Produced | 2016 |
| Provided To Others? | Yes |
| Description | Continuous Crystallisation of Zr MOFs |
| Organisation | EPSRC Centre for Innovative Manufacturing for Continuous Manufacturing and Crystallisation (CMAC) |
| Country | United Kingdom |
| Sector | Public |
| PI Contribution | The PI has joined the CMAC centre as a PI and now supervises a CDT student examining the crystallisation and manufacture of Zr MOFs. The PI has brought additional skills and knowledge of advanced functional materials into the CMAC CDT, which has been traditionally more pharmaceutically focused. The PI collaborates with a number of members and is writing a grant application with one. |
| Collaborator Contribution | The CDT has provided funds to support the studentship and allowed the PhD student to participate in the CDT learning activities, developing their skillset and knowledge base. CMAC have also allowed the PI and the new PhD student access to equipment to study crystallisation which is otherwise unavailable, and also knowledge and expertise in crystallisation and manufacturing. The PhD studentship is still in an early stage but results are promising. |
| Impact | There are no outputs as yet as the collaboration is still in the development stage. A publication is being drafted which introduces the collaboratoin between the PI (synthesis of advanced functional materials) and CMAC (continuous manufacture and investigation of crystallisation mechanisms). A grant application is also being drafted. |
| Start Year | 2015 |
| Description | Luminescent MOFs for Sensing and Electronics |
| Organisation | University of Glasgow |
| Department | MRC - University of Glasgow Centre for Virus Research |
| Country | United Kingdom |
| Sector | Academic/University |
| PI Contribution | We have prepared MOFs containing intrinsically luminescent ligands which have a broad range of applications. This has led to development of sensors and hybrid LEDs. Our group uses enhanced synthetic methodology developed in the project to prepare the MOFs |
| Collaborator Contribution | Our partners in New Brunswick have characterised the vapour sensing abilities of our MOFs, and our collaborators at Glasgow have incorporated them into hybrid LEDs. |
| Impact | Two publications have been the main outcomes to date. |
| Start Year | 2016 |
| Description | Luminescent MOFs for Sensing and Electronics |
| Organisation | University of Glasgow |
| Department | MRC - University of Glasgow Centre for Virus Research |
| Country | United Kingdom |
| Sector | Academic/University |
| PI Contribution | We have prepared MOFs containing intrinsically luminescent ligands which have a broad range of applications. This has led to development of sensors and hybrid LEDs. Our group uses enhanced synthetic methodology developed in the project to prepare the MOFs |
| Collaborator Contribution | Our partners in New Brunswick have characterised the vapour sensing abilities of our MOFs, and our collaborators at Glasgow have incorporated them into hybrid LEDs. |
| Impact | Two publications have been the main outcomes to date. |
| Start Year | 2016 |
| Description | Luminescent MOFs for Sensing and Electronics |
| Organisation | University of New Brunswick |
| Country | Canada |
| Sector | Academic/University |
| PI Contribution | We have prepared MOFs containing intrinsically luminescent ligands which have a broad range of applications. This has led to development of sensors and hybrid LEDs. Our group uses enhanced synthetic methodology developed in the project to prepare the MOFs |
| Collaborator Contribution | Our partners in New Brunswick have characterised the vapour sensing abilities of our MOFs, and our collaborators at Glasgow have incorporated them into hybrid LEDs. |
| Impact | Two publications have been the main outcomes to date. |
| Start Year | 2016 |
| Description | Luminescent MOFs for Sensing and Electronics |
| Organisation | University of New Brunswick |
| Country | Canada |
| Sector | Academic/University |
| PI Contribution | We have prepared MOFs containing intrinsically luminescent ligands which have a broad range of applications. This has led to development of sensors and hybrid LEDs. Our group uses enhanced synthetic methodology developed in the project to prepare the MOFs |
| Collaborator Contribution | Our partners in New Brunswick have characterised the vapour sensing abilities of our MOFs, and our collaborators at Glasgow have incorporated them into hybrid LEDs. |
| Impact | Two publications have been the main outcomes to date. |
| Start Year | 2016 |
| Description | Mechanical Properties of MOFs |
| Organisation | University of Cambridge |
| Department | University of Cambridge, BBSRC IGF Drosophila Genomics Facility |
| Country | United Kingdom |
| Sector | Academic/University |
| PI Contribution | We are preparing MOFs with fine control over physical properties (such as particle size) to allow the partner to fully characterise their thermomechanical properties. We intend to prepare new hybrid ceramics containing the MOFs which must be monodisperse and regular - this requires our synthetic methodology developed in the project. |
| Collaborator Contribution | The partner is characterising thermomechanical stability of the MOFs and aiming to incoporate the most stable into hybrid ceramics. |
| Impact | None as yet. An application to EPSRC is being drafted. |
| Start Year | 2018 |
| Description | Pressure Studies of Metal-Organic Frameworks |
| Organisation | University of Edinburgh |
| Department | School of Engineering |
| Country | United Kingdom |
| Sector | Academic/University |
| PI Contribution | We have developed a collaboration with scientists at the University of Edinburgh, whereby we prepare crystalline samples of our materials which are then examined under high pressure X-ray crystallography. These experiments have been carried out at Diamond Light Source through winning of beamtime through peer-reviewed applications written by myself and my collaborators. |
| Collaborator Contribution | The partner organisation provides us with some experimental time and equipment, and also assists in the preparation of peer-reviewed beamtime applications. |
| Impact | We have won numerous beamtime sessions at Diamond Light Source, been awarded a pump-priming award of £12,900 from the EPSRC Directed Assembly Network and published one paper together to date. We are currently drafting a new grant application. |
| Start Year | 2014 |
| Description | Pressure Studies of Metal-Organic Frameworks |
| Organisation | University of Western Australia |
| Department | School of Primary Aboriginal and Rural Health Care |
| Country | Australia |
| Sector | Academic/University |
| PI Contribution | We have developed a collaboration with scientists at the University of Edinburgh, whereby we prepare crystalline samples of our materials which are then examined under high pressure X-ray crystallography. These experiments have been carried out at Diamond Light Source through winning of beamtime through peer-reviewed applications written by myself and my collaborators. |
| Collaborator Contribution | The partner organisation provides us with some experimental time and equipment, and also assists in the preparation of peer-reviewed beamtime applications. |
| Impact | We have won numerous beamtime sessions at Diamond Light Source, been awarded a pump-priming award of £12,900 from the EPSRC Directed Assembly Network and published one paper together to date. We are currently drafting a new grant application. |
| Start Year | 2014 |
| Description | PInt of Science Festival Talk |
| Form Of Engagement Activity | A talk or presentation |
| Part Of Official Scheme? | No |
| Geographic Reach | Local |
| Primary Audience | Public/other audiences |
| Results and Impact | I gave a public talk on the use of molecular machines and nanotechnology in medicine. It was attended by around 100 people, and sparked discussions on the topic regarding technology and ethics. |
| Year(s) Of Engagement Activity | 2015 |