Adaptable Porous Materials
Lead Research Organisation:
University of Liverpool
Department Name: Chemistry
Abstract
Porous materials find widespread application in storage, separation and catalytic technologies. The sorption of a guest molecule by a rigid porous material such as a zeolite or active carbon is controlled by the fixed size and shape of the pores.
Nature catalyses chemical processes and manipulates molecules using proteins. Proteins are characterised by an adaptable response to their environment, produced by conformational selection of an appropriate functional structure (e.g. for enzyme catalysis, or pore opening of the mechanosensitive channel of small conductance in an ion channel) from a large ensemble of energetically low-lying and kinetically accessible states. This is enabled by the manifold torsions available to polypeptide chains, which allow folding into the required structures.
The project team have recently (Rabone et al Science 2010) used a simple dipeptide linker to assemble a crystalline porous framework through metal-binding. The resulting material combines pre-formed pores with the degrees of freedom from a peptide linker required for conformational selection. This peptide-based open framework displays adaptable porosity that evolves continuously from an open to a partially disordered closed structure in response to the guest content. The functional porous behavior is unconventional, displaying cooperative feedback characteristic of cooperative interactions as the pore topography changes in response to the number of guests occupying the pore volume of the host. The peptide-based material displays adaptable porosity. It undergoes dynamical structural changes on guest loading because there are many accessible sorption states with low energy barriers between them. This energy landscape arises because of the low energies required for torsional changes to the structure of the peptide linker.
This opens up the possibility of designed adaptable porous materials which respond to guests in a manner analogous to that of a biomolecule undergoing conformational selection, produced by the modular assembly of multiple amino acid residues around several metal centres to access large and functionally diverse unit cells. This vision cannot be presently realized due to the large numbers of potential chemical constituents of such materials and the absence of computational tools to understand and predict how they would respond to guests. Such materials would though be unprecedented and offer new and potentially useful sorption and catalysis functionality.
The proposed research aims to develop the tools to allow the isolation of such materials by focussing on adaptable porous materials derived from chemically simple di- and tripeptide linkers containing two and three amino acid residues respectively. We will identify the characteristics of both individual peptide linkers and metal-based units which give adaptable porous behaviour. This will allow the development of second-generation systems in which multiple peptide and metal units are used, making the key advance of demonstrating modular amino acid residue assembly in a functional porous solid. Rigid linkers will be introduced together with the peptides to produce structures where rigid sub-units are repositioned by the flexible peptide-based units, in a manner analogous to the repositioning of rigid helix and sheet units in protein folding.
Given the diversity of possible peptide components, descriptor-based computational methods including machine-learning will be developed as a complementary approach to the selection of synthetic targets in the second- and third-generation families.
The response of adaptable porous materials to guests does not follow classical models, and will be evaluated from experimental sorption, dynamics and structural data coupled with computational models appropriate to the dynamical restructuring of the adaptable porous host around a guest, to move beyond the current static view of host-guest interactions in synthetic porous materials.
Nature catalyses chemical processes and manipulates molecules using proteins. Proteins are characterised by an adaptable response to their environment, produced by conformational selection of an appropriate functional structure (e.g. for enzyme catalysis, or pore opening of the mechanosensitive channel of small conductance in an ion channel) from a large ensemble of energetically low-lying and kinetically accessible states. This is enabled by the manifold torsions available to polypeptide chains, which allow folding into the required structures.
The project team have recently (Rabone et al Science 2010) used a simple dipeptide linker to assemble a crystalline porous framework through metal-binding. The resulting material combines pre-formed pores with the degrees of freedom from a peptide linker required for conformational selection. This peptide-based open framework displays adaptable porosity that evolves continuously from an open to a partially disordered closed structure in response to the guest content. The functional porous behavior is unconventional, displaying cooperative feedback characteristic of cooperative interactions as the pore topography changes in response to the number of guests occupying the pore volume of the host. The peptide-based material displays adaptable porosity. It undergoes dynamical structural changes on guest loading because there are many accessible sorption states with low energy barriers between them. This energy landscape arises because of the low energies required for torsional changes to the structure of the peptide linker.
This opens up the possibility of designed adaptable porous materials which respond to guests in a manner analogous to that of a biomolecule undergoing conformational selection, produced by the modular assembly of multiple amino acid residues around several metal centres to access large and functionally diverse unit cells. This vision cannot be presently realized due to the large numbers of potential chemical constituents of such materials and the absence of computational tools to understand and predict how they would respond to guests. Such materials would though be unprecedented and offer new and potentially useful sorption and catalysis functionality.
The proposed research aims to develop the tools to allow the isolation of such materials by focussing on adaptable porous materials derived from chemically simple di- and tripeptide linkers containing two and three amino acid residues respectively. We will identify the characteristics of both individual peptide linkers and metal-based units which give adaptable porous behaviour. This will allow the development of second-generation systems in which multiple peptide and metal units are used, making the key advance of demonstrating modular amino acid residue assembly in a functional porous solid. Rigid linkers will be introduced together with the peptides to produce structures where rigid sub-units are repositioned by the flexible peptide-based units, in a manner analogous to the repositioning of rigid helix and sheet units in protein folding.
Given the diversity of possible peptide components, descriptor-based computational methods including machine-learning will be developed as a complementary approach to the selection of synthetic targets in the second- and third-generation families.
The response of adaptable porous materials to guests does not follow classical models, and will be evaluated from experimental sorption, dynamics and structural data coupled with computational models appropriate to the dynamical restructuring of the adaptable porous host around a guest, to move beyond the current static view of host-guest interactions in synthetic porous materials.
Planned Impact
Who will benefit?
Adaptable porous materials have the potential to expand the applications of porous solids. This programme has long-term benefits in sorption (analytical and preparative selective sorption; clean-up of gas streams; energy-intensive separations) and catalysis for processes of relevance to the chemical and pharmaceutical industries. The industrial beneficiaries will be catalyst and sorbent manufacturers (in this project we engage initially with Johnson Matthey (JM)) and users (Defence Science and Technology Laboratory (Dstl)), and pharmaceutical and speciality chemicals companies. JM will benefit from the impact of chiral naturally-derived adaptable porous materials on catalysis and separation technologies - sorption-based separations reduce energy requirements, and metal-organic frameworks are now under pilot plant evaluation for several key separations. The public sector research organization Dstl will benefit through the development of new sorption mechanisms as their personnel protection technologies largely depend on sorption removal and catalytic destruction of hazards.
Society will benefit from the trained personnel emerging from the programme equipped to contribute to UK industry in a high-tech sector. Longer term benefits will arise from the scientific advances enabling reduced energy use for processes such as separations, the development of new sensors (either through applications of the materials themselves or the understanding of adaptable host response to guests) with associated health and environmental benefits, and through the generic impact of enhanced control of the assembly of highly chemically-functionalised molecules in effect materials.
What will be done to ensure they have the opportunity to benefit?
Day 1 partners JM and Dstl will receive regular six-monthly project updates for discussion with the project team, leading to personnel exchange and materials evaluation where appropriate. Beyond this day 1 group, we will work with the Knowledge Centre for Materials Chemistry (KCMC) to ensure the widest possible dissemination of relevant developments to UK chemicals-using and broader industry sectors. MJR is the Liverpool lead and founder member of KCMC, which is an applied materials chemistry collaboration between the Universities of Bolton, Liverpool (UoL), Manchester and STFC Daresbury Laboratories - 50% of the KCMC partners are involved in the present proposal. KCMC has supported 71 companies in over 100 projects, generating over £6M of industrial funding since March 2009. KCMC thus has strong collaborative relationships with many UK-based chemical companies, providing a mechanism for advances in science emerging from the project to be evaluated and where appropriate taken forward for exploitation through engagement of the KCMC Knowledge Transfer (KT) team via individual discussion with companies and themed industry days, using case-study type summaries of both materials and methodologies emerging from the programme prepared by the KT team to maximize impact on potential users. IP will be protected by Business Gateway at UoL. The team currently has 8 patents filed via this mechanism from EPSRC-funded research in the past 3 years.
Project advances of societal interest will be disseminated via the UoL press office, working with EPSRC as appropriate. The new modelling methodology will be showcased on the UoL chemtube3d.com website (>160,000 visitors from >180 countries spending >2.5 mins per visit), and together with experimental advances, incorporated in new experiments for the UoL Schools Lab. Policymaker engagement is key to societal benefit and KCMC will enable this through events such as the 2 year Anniversary event at the Houses of Parliament in May 2011.
The skills and contact network of the two project RAs will be strongly enhanced by close experiment/theory co-working in an emerging science area, and engagement with JM, Dstl and the industry network of KCMC.
Adaptable porous materials have the potential to expand the applications of porous solids. This programme has long-term benefits in sorption (analytical and preparative selective sorption; clean-up of gas streams; energy-intensive separations) and catalysis for processes of relevance to the chemical and pharmaceutical industries. The industrial beneficiaries will be catalyst and sorbent manufacturers (in this project we engage initially with Johnson Matthey (JM)) and users (Defence Science and Technology Laboratory (Dstl)), and pharmaceutical and speciality chemicals companies. JM will benefit from the impact of chiral naturally-derived adaptable porous materials on catalysis and separation technologies - sorption-based separations reduce energy requirements, and metal-organic frameworks are now under pilot plant evaluation for several key separations. The public sector research organization Dstl will benefit through the development of new sorption mechanisms as their personnel protection technologies largely depend on sorption removal and catalytic destruction of hazards.
Society will benefit from the trained personnel emerging from the programme equipped to contribute to UK industry in a high-tech sector. Longer term benefits will arise from the scientific advances enabling reduced energy use for processes such as separations, the development of new sensors (either through applications of the materials themselves or the understanding of adaptable host response to guests) with associated health and environmental benefits, and through the generic impact of enhanced control of the assembly of highly chemically-functionalised molecules in effect materials.
What will be done to ensure they have the opportunity to benefit?
Day 1 partners JM and Dstl will receive regular six-monthly project updates for discussion with the project team, leading to personnel exchange and materials evaluation where appropriate. Beyond this day 1 group, we will work with the Knowledge Centre for Materials Chemistry (KCMC) to ensure the widest possible dissemination of relevant developments to UK chemicals-using and broader industry sectors. MJR is the Liverpool lead and founder member of KCMC, which is an applied materials chemistry collaboration between the Universities of Bolton, Liverpool (UoL), Manchester and STFC Daresbury Laboratories - 50% of the KCMC partners are involved in the present proposal. KCMC has supported 71 companies in over 100 projects, generating over £6M of industrial funding since March 2009. KCMC thus has strong collaborative relationships with many UK-based chemical companies, providing a mechanism for advances in science emerging from the project to be evaluated and where appropriate taken forward for exploitation through engagement of the KCMC Knowledge Transfer (KT) team via individual discussion with companies and themed industry days, using case-study type summaries of both materials and methodologies emerging from the programme prepared by the KT team to maximize impact on potential users. IP will be protected by Business Gateway at UoL. The team currently has 8 patents filed via this mechanism from EPSRC-funded research in the past 3 years.
Project advances of societal interest will be disseminated via the UoL press office, working with EPSRC as appropriate. The new modelling methodology will be showcased on the UoL chemtube3d.com website (>160,000 visitors from >180 countries spending >2.5 mins per visit), and together with experimental advances, incorporated in new experiments for the UoL Schools Lab. Policymaker engagement is key to societal benefit and KCMC will enable this through events such as the 2 year Anniversary event at the Houses of Parliament in May 2011.
The skills and contact network of the two project RAs will be strongly enhanced by close experiment/theory co-working in an emerging science area, and engagement with JM, Dstl and the industry network of KCMC.
Organisations
Publications
Carraro F
(2017)
Catalysis in MOFs: general discussion.
in Faraday discussions
Gladysiak A
(2017)
A Recyclable Metal-Organic Framework as a Dual Detector and Adsorbent for Ammonia.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Gladysiak A
(2018)
Shedding Light on the Protonation States and Location of Protonated N Atoms of Adenine in Metal-Organic Frameworks.
in Inorganic chemistry
Katsoulidis AP
(2014)
Guest-adaptable and water-stable peptide-based porous materials by imidazolate side chain control.
in Angewandte Chemie (International ed. in English)
Katsoulidis AP
(2019)
Chemical control of structure and guest uptake by a conformationally mobile porous material.
in Nature
Martí-Gastaldo C
(2015)
Sponge-Like Behaviour in Isoreticular Cu(Gly-His-X) Peptide-Based Porous Materials.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Martí-Gastaldo C
(2014)
Side-chain control of porosity closure in single- and multiple-peptide-based porous materials by cooperative folding.
in Nature chemistry
Navarro-Sánchez J
(2017)
Peptide Metal-Organic Frameworks for Enantioselective Separation of Chiral Drugs
in Journal of the American Chemical Society
Description | We have discovered porous materials that can adopt different ordered structures in response to the particular guests that occupy their internal pore space by the selection of specific peptide conformations. As proteins respond to guests by the same chemical changes, the resulting understanding, produced by computational and experimental approaches working together, this will enable the development of new classes of porous materials that respond extremely specifically to the guest species in their pore space. A key part of the project was identifying chemistry that allowed this flexibility to be combined with stability to a range of chemical environments. This had led to the chemical control of the conformational response of a crystalline porous material to produce responses analogous to the conformational selection and induced fit that are important concepts in the function of proteins. |
Exploitation Route | In the design of new sorbent and catalyst systems for highly specific separations and catalytic transformations at low temperatures. |
Sectors | Aerospace Defence and Marine Chemicals |
Description | The findings regarding the restructuring of solids upon guest loading, particularly the role of the chemical functionality and molecular flexibility associated with peptide and peptide-like linkers, have informed development of sorbents (for example for toxic chemical uptake) with the defence and chemicals sectors. This has led to follow-on projects with these sectors involving the incorporation of catalytic functionality to amplify the sorption-only response of the materials developed in this project. The discovery tools for porous materials developed in this project have informed engagement with UK materials companies to enable digital transformation of their research programmes. The project has defined for the first time protein-like guest response in a synthetic porous material. |
First Year Of Impact | 2016 |
Sector | Aerospace, Defence and Marine,Chemicals |
Impact Types | Economic |
Title | Stable and Ordered Amide Frameworks Synthesised Under Reversible Conditions which Facilitate Error Checking |
Description | Covalent Organic Frameworks (COFs) are network polymers with long-range positional order whose properties can be tuned using the isoreticular chemistry approach. Making COFs from strong bonds is challenging because irreversible rapid formation of the network produces amorphous materials with locked-in disorder. Reversibility in bond formation is essential to generate ordered networks, as it allows the error-checking that permits the network to crystallise, and so candidate network-forming chemistries such as amide that are irreversible under conventional low temperature bond-forming conditions have been underexplored. Here we show that we can prepare two- and three-dimensional Covalent Amide Frameworks (CAFs) by devitrification of amorphous polyamide network polymers using high-temperature and -pressure reaction conditions. In this way we have accessed reversible amide bond formation that allows crystalline order to develop. This strategy permits the direct synthesis of practically irreversible ordered amide networks that are stable thermally and under both strong acidic and basic hydrolytic conditions |
Type Of Material | Database/Collection of data |
Year Produced | 2017 |
Provided To Others? | Yes |
Impact | No known impacts |
URL | http://datacat.liverpool.ac.uk/id/eprint/386 |
Title | Compound, Synthesis Method Thereof, and Separation and Recovery Agent Thereof |
Description | wherein Ln represents a lanthanide selected from Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, and Lu. |
IP Reference | US2018050920 |
Protection | Patent application published |
Year Protection Granted | 2018 |
Licensed | No |
Impact | No impact to date |
Description | Prof Rosseinsky gave a plenary lecture at EuroMOF, Paris, October 2019 |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Presented on the topic of "Porous materials and rotation about single bonds" for dissemination of results and academic discussion |
Year(s) Of Engagement Activity | 2020 |
Description | Prof Rosseinsky gave an invited lecture at Cardiff Catalysis Institute Conference (CCI) , Cardiff, 14 - 16 Jan 2019 |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Presented on the topic of "New directions in porous materials" for dissemination of results and academic discussion |
Year(s) Of Engagement Activity | 2019 |
Description | Prof Rosseinsky gave an invited lecture at FlexMOF, Dresden, Germany, December 2019 |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Presented on the subject of "Porous materials and rotation about single bonds" for dissemination of results and academic discussion |
Year(s) Of Engagement Activity | 2020 |
Description | Prof Rosseinsky gave an invited lecture at KAUST Research Conference: Advanced Materials for Energy Efficient Separations: Addressing Vision 2030 and Beyond, 2-4 March 2020, King Abdullah University of Science and Technology, Thuwal, Saudi Arabia |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Presented on the topic of "Porous materials and rotation about single bonds" for dissemination of results and academic discussion |
Year(s) Of Engagement Activity | 2020 |
Description | Prof Rosseinsky gave an invited lecture at the Directed Assembly Network Meeting, Enabling Reactivity in the Crystalline State, Magdalen College, Oxford 17 - 18 Jan 2019 |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Professional Practitioners |
Results and Impact | Presented on the topic of "Porous materials and rotation about single bonds" for dissemination of results and academic discussion |
Year(s) Of Engagement Activity | 2019 |
Description | Prof. Rosseinsky gave an invited lecture at 3rd Annual UK Metal-Organic Framework and Porous Organics Conference, 2018 |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Presentation on "New framework forming chemistry and heterogeneous catalysis - control of molecular organometallic catalysts by cation exchange into metal-organic framework", for the dissemination of results for academic discussion |
Year(s) Of Engagement Activity | 2018 |
Description | Prof. Rosseinsky gave an invited lecture at ACS Conference 2018 |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Presentation on "Porous materials from new framework-forming chemistries", for the dissemination of results for academic discussion |
Year(s) Of Engagement Activity | 2018 |
Description | Prof. Rosseinsky gave an invited lecture at Cardiff Catalysis Institute Conference (CCI) , 2019 |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Presentation on "New directions in porous materials", for the dissemination of results for academic discussion |
Year(s) Of Engagement Activity | 2019 |
Description | Prof. Rosseinsky gave an invited lecture at Directed Assembly Network Meeting, Enabling Reactivity in the Crystalline State, 2019 |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Professional Practitioners |
Results and Impact | Presentation on "Porous materials and rotation about single bonds", for the dissemination of results for academic discussion |
Year(s) Of Engagement Activity | 2019 |
Description | Prof. Rosseinsky gave an invited lecture at MOF 2018 Conference |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Presentation on "Porous materials with dynamic guest response from single bond rotations", for the dissemination of results for academic discussion |
Year(s) Of Engagement Activity | 2018 |
Description | Prof. Rosseinsky gave an invited lecture at UK Catalysis Hub conference, 2017 |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Presentation on "New porous materials and heterogenieous catalysis - control of molecular organometallic catalysts by cation exchange into a metal-organic framework", for the dissemination of results for academic discussion |
Year(s) Of Engagement Activity | 2017 |