Multicomponent Supramolecular Hydrogels
Lead Research Organisation:
University of Glasgow
Department Name: School of Chemistry
Abstract
The vision of this fellowship is to develop the requisite understanding of multicomponent low molecular weight gels such that they can be used for practical applications in energy, complementing the growing body of work on the use of these systems in medicine and drug delivery. Multicomponent gels offer significant new opportunities in terms of generating useful and exciting new structures. Specifically in this fellowship, we will develop conductive materials, as well as bulk heterojunctions, using low molecular weight gelators. This requires specific assembly of multiple components with careful control over the assembly across many length-scales. The aim here is to develop effective solar cells in an unprecedented way.
Currently, multicomponent systems are rare and introduce significant complexity and questions: for example, do the components mix, specifically or randomly, or do they self-sort, to create assemblies of one pure component co-existing with pure assemblies of the other? Also, once the primary assembly has occurred, how are these structures distributed in space? Do they interact randomly, or can specific, higher-order structures be formed? Such questions are fundamental to the development of technology such as solar cells, where energy transfer between the molecular components is core to their function. A particular challenge here is to guide multicomponent self-assembling systems across many length-scales, precisely positioning individual molecules or assemblies within well organised, highly-ordered structures in order to achieve a reproducible, highly-controlled network.
Here, I focus on a class of low molar mass gelators with which I have significant experience. I will develop a thorough understanding of the conditions under which gelation occurs for each component to prepare gels where components are specifically located. For success, I will develop systems consisting of two LMWG containing aromatic groups whose spectral adsorptions complement each other with appropriate HOMO and LUMO levels. I will develop methods to ensure that well-ordered self-sorted structures are formed, which entangle to form structures with a suitable interface. This requires control over assembly across multiple length-scales. The main challenges here focus on ensuring the microstructure is correct and that the percolation paths are ideal. There is limited understanding for single LMWG systems, let alone for two-component systems. As such, this work will take the area significantly beyond the current state of the art and also provides a new application for these materials through their development for solar cell technology.
Currently, multicomponent systems are rare and introduce significant complexity and questions: for example, do the components mix, specifically or randomly, or do they self-sort, to create assemblies of one pure component co-existing with pure assemblies of the other? Also, once the primary assembly has occurred, how are these structures distributed in space? Do they interact randomly, or can specific, higher-order structures be formed? Such questions are fundamental to the development of technology such as solar cells, where energy transfer between the molecular components is core to their function. A particular challenge here is to guide multicomponent self-assembling systems across many length-scales, precisely positioning individual molecules or assemblies within well organised, highly-ordered structures in order to achieve a reproducible, highly-controlled network.
Here, I focus on a class of low molar mass gelators with which I have significant experience. I will develop a thorough understanding of the conditions under which gelation occurs for each component to prepare gels where components are specifically located. For success, I will develop systems consisting of two LMWG containing aromatic groups whose spectral adsorptions complement each other with appropriate HOMO and LUMO levels. I will develop methods to ensure that well-ordered self-sorted structures are formed, which entangle to form structures with a suitable interface. This requires control over assembly across multiple length-scales. The main challenges here focus on ensuring the microstructure is correct and that the percolation paths are ideal. There is limited understanding for single LMWG systems, let alone for two-component systems. As such, this work will take the area significantly beyond the current state of the art and also provides a new application for these materials through their development for solar cell technology.
Planned Impact
The outputs of this fellowship will be (i) the first thorough understanding of multicomponent gel materials, (ii) new methods for the generation of patterned and structured gels, (iii) new methods for the directed self-assembly of multicomponent gels to give bulk heterojunctions, (iv) solar cells incorporating multicomponent bulk heterojunctions, (v) new methods which will enable potential applications in optical materials and sensors, (vi) three scientists trained in rational molecule design, structural characterization, electrochemistry, and device preparation, (vii) protection of relevant IP and, (viii) a descriptor-based approach to predicting the molecular gelation ability.
The ultimate output of the project will be new soft functional materials for photovoltaic devices, prepared by 'bottom-up' self-assembly methods, rather than, for example, 'top down' methods such as microlithography. Such devices could provide long-term benefits by contributing to generating energy to help satisfy future demands. More generally, society will benefit from the understanding of the self-assembly of multicomponent systems for advanced functional materials and their large range of potential applications. This leads from the understanding we will generate; without the ability to rationally design materials, it is extremely difficult to harness their capabilities. Society will also benefit from the trained personnel emerging from the programme equipped to contribute to UK industry technology intensive and high value manufacturing sectors.
We will work with the University Research Office and the KCMC (an applied materials chemistry collaboration between the Universities of Bolton, Liverpool, Manchester and STFC Daresbury Laboratories) to ensure the widest possible dissemination of relevant developments to UK chemicals-using and broader industry sectors. KCMC has supported 71 companies, generating over £6M of industrial funding since March 2009. KCMC has extensive links to the Knowledge Transfer networks (KTNs) and also runs the Materials Chemistry Special Interest Group (MC SIG) with funding from the TSB. These networks provide direct links with companies in multiple sectors providing a platform for disseminations and collaborative partner identification.
Economic beneficiaries will be companies and/or IP groups who wish to take the technology developed during the project further. We have achieved this before, with direct transfer of technology into two SMEs as well as setting up a CASE studentship with Unilever. 2Bio, a specialist innovation support company and the KCMC will provide technology assessment and market analysis in the PV sector and additional sectors based on specific research outputs. The KCMC network of industry partners and collaborators will be engaged to maximise the uptake of the developed technology and future collaboration.
Liverpool is currently developing the Materials Innovation Factory (MIF), a revolutionary £50million project by the University, Unilever and HEFCE. The MIF will house >£10 million worth of measurement and testing instrumentation, including high-throughput techniques, high-end analytical techniques and other unique capabilities to greatly accelerate research times. Industry and academic partners will work and innovate together within a shared, bespoke environment to foster both fundamental and applied research innovation in materials chemistry and formulation science.
All these mechanisms will ensure that the science emerging from the project will be disseminated and evaluated and exploited with many UK-based companies, via individual discussions and themed industry days, using summaries of emerging materials and methodologies prepared by the KT team. We will also disseminate information using the EPSRC Directed Assembly Network and via two targeted multidisciplinary conferences aimed at both academic and industrial scientists.
The ultimate output of the project will be new soft functional materials for photovoltaic devices, prepared by 'bottom-up' self-assembly methods, rather than, for example, 'top down' methods such as microlithography. Such devices could provide long-term benefits by contributing to generating energy to help satisfy future demands. More generally, society will benefit from the understanding of the self-assembly of multicomponent systems for advanced functional materials and their large range of potential applications. This leads from the understanding we will generate; without the ability to rationally design materials, it is extremely difficult to harness their capabilities. Society will also benefit from the trained personnel emerging from the programme equipped to contribute to UK industry technology intensive and high value manufacturing sectors.
We will work with the University Research Office and the KCMC (an applied materials chemistry collaboration between the Universities of Bolton, Liverpool, Manchester and STFC Daresbury Laboratories) to ensure the widest possible dissemination of relevant developments to UK chemicals-using and broader industry sectors. KCMC has supported 71 companies, generating over £6M of industrial funding since March 2009. KCMC has extensive links to the Knowledge Transfer networks (KTNs) and also runs the Materials Chemistry Special Interest Group (MC SIG) with funding from the TSB. These networks provide direct links with companies in multiple sectors providing a platform for disseminations and collaborative partner identification.
Economic beneficiaries will be companies and/or IP groups who wish to take the technology developed during the project further. We have achieved this before, with direct transfer of technology into two SMEs as well as setting up a CASE studentship with Unilever. 2Bio, a specialist innovation support company and the KCMC will provide technology assessment and market analysis in the PV sector and additional sectors based on specific research outputs. The KCMC network of industry partners and collaborators will be engaged to maximise the uptake of the developed technology and future collaboration.
Liverpool is currently developing the Materials Innovation Factory (MIF), a revolutionary £50million project by the University, Unilever and HEFCE. The MIF will house >£10 million worth of measurement and testing instrumentation, including high-throughput techniques, high-end analytical techniques and other unique capabilities to greatly accelerate research times. Industry and academic partners will work and innovate together within a shared, bespoke environment to foster both fundamental and applied research innovation in materials chemistry and formulation science.
All these mechanisms will ensure that the science emerging from the project will be disseminated and evaluated and exploited with many UK-based companies, via individual discussions and themed industry days, using summaries of emerging materials and methodologies prepared by the KT team. We will also disseminate information using the EPSRC Directed Assembly Network and via two targeted multidisciplinary conferences aimed at both academic and industrial scientists.
People |
ORCID iD |
| Dave Adams (Principal Investigator / Fellow) |
Publications
Akhtar R
(2018)
Oscillatory nanoindentation of highly compliant hydrogels: A critical comparative analysis with rheometry
in Journal of Materials Research
Angelerou MGF
(2018)
Supramolecular Nucleoside-Based Gel: Molecular Dynamics Simulation and Characterization of Its Nanoarchitecture and Self-Assembly Mechanism.
in Langmuir : the ACS journal of surfaces and colloids
Ardoña HAM
(2017)
Kinetically Controlled Coassembly of Multichromophoric Peptide Hydrogelators and the Impacts on Energy Transport.
in Journal of the American Chemical Society
Aviño F
(2017)
Stabilizing bubble and droplet interfaces using dipeptide hydrogels.
in Organic & biomolecular chemistry
Bhavsar R
(2018)
Ultrahigh-permeance PIM-1 based thin film nanocomposite membranes on PAN supports for CO2 separation
in Journal of Membrane Science
Cameron J
(2022)
Amino acid functionalised perylene bisimides for aqueous solution-deposited electron transporting interlayers in organic photovoltaic devices
in Journal of Materials Chemistry C
Cardoso AZ
(2016)
Linking micellar structures to hydrogelation for salt-triggered dipeptide gelators.
in Soft matter
Cariello M
(2022)
A Self-Assembling Flavin for Visible Photooxidation.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Castilla AM
(2016)
On the syneresis of an OPV functionalised dipeptide hydrogel.
in Soft matter
Castilla AM
(2017)
Self-sorted Oligophenylvinylene and Perylene Bisimide Hydrogels.
in Scientific reports
Castilla AM
(2018)
Using Aggregation-Induced Emission to Understand Dipeptide Gels.
in Gels (Basel, Switzerland)
Colquhoun C
(2017)
Controlling the network type in self-assembled dipeptide hydrogels.
in Soft matter
Cross E
(2018)
Controlled Tuning of the Properties in Optoelectronic Self-Sorted Gels
in Journal of the American Chemical Society
Cross ER
(2020)
Tuning the antimicrobial activity of low molecular weight hydrogels using dopamine autoxidation.
in Chemical communications (Cambridge, England)
Cross ER
(2019)
Probing the self-assembled structures and pKa of hydrogels using electrochemical methods.
in Soft matter
Draper E
(2017)
Opening a Can of Worm(-like Micelle)s: The Effect of Temperature of Solutions of Functionalized Dipeptides
in Angewandte Chemie
Draper E
(2017)
pH-Directed Aggregation to Control Photoconductivity in Self-Assembled Perylene Bisimides
in Chem
Draper E
(2016)
Reversible Photoreduction as a Trigger for Photoresponsive Gels
in Chemistry of Materials
Draper E
(2017)
Low-Molecular-Weight Gels: The State of the Art
in Chem
Draper ER
(2018)
Controlling Photoconductivity in PBI Films by Supramolecular Assembly.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Draper ER
(2016)
Self-sorted photoconductive xerogels.
in Chemical science
Draper ER
(2017)
Opening a Can of Worm(-like Micelle)s: The Effect of Temperature of Solutions of Functionalized Dipeptides.
in Angewandte Chemie (International ed. in English)
Draper ER
(2019)
Controlling the Assembly and Properties of Low-Molecular-Weight Hydrogelators.
in Langmuir : the ACS journal of surfaces and colloids
Draper ER
(2018)
How should multicomponent supramolecular gels be characterised?
in Chemical Society reviews
Draper ER
(2018)
P-Type Low-Molecular-Weight Hydrogelators.
in Macromolecular rapid communications
Draper ER
(2018)
Aligning self-assembled perylene bisimides in a magnetic field.
in Chemical communications (Cambridge, England)
Draper ER
(2017)
Nonlinear Effects in Multicomponent Supramolecular Hydrogels.
in Langmuir : the ACS journal of surfaces and colloids
Draper ER
(2016)
Aligning self-assembled gelators by drying under shear.
in Chemical communications (Cambridge, England)
Draper ER
(2016)
Photoresponsive gelators.
in Chemical communications (Cambridge, England)
Fuentes E
(2020)
PAINT-ing Fluorenylmethoxycarbonyl (Fmoc)-Diphenylalanine Hydrogels.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Fuentes-Caparrós AM
(2019)
Annealing multicomponent supramolecular gels.
in Nanoscale
Fuentes-Caparrós AM
(2021)
Mechanical Characterization of Multilayered Hydrogels: A Rheological Study for 3D-Printed Systems.
in Biomacromolecules
Fuentes-Caparrós AM
(2019)
On the Mechanical Properties of N-Functionalised Dipeptide Gels.
in Molecules (Basel, Switzerland)
Giuri D
(2021)
Understanding gel-to-crystal transitions in supramolecular gels.
in Soft matter
Gonzalez L
(2018)
Transparent-to-dark photo- and electrochromic gels
in Communications Chemistry
Gupta JK
(2016)
Will it gel? Successful computational prediction of peptide gelators using physicochemical properties and molecular fingerprints.
in Chemical science
Maklad O
(2022)
A technical note on large normal-stress differences observed in a novel self-assembling functionalized dipeptide surfactant solution
in Rheologica Acta
McAulay K
(2020)
Isotopic Control over Self-Assembly in Supramolecular Gels.
in Langmuir : the ACS journal of surfaces and colloids
McAulay K
(2020)
Controlling the properties of the micellar and gel phase by varying the counterion in functionalised-dipeptide systems.
in Chemical communications (Cambridge, England)
McAulay K
(2019)
Using chirality to influence supramolecular gelation.
in Chemical science
McDowall D
(2020)
Controlling Photocatalytic Activity by Self-Assembly - Tuning Perylene Bisimide Photocatalysts for the Hydrogen Evolution Reaction
in Advanced Energy Materials
Mears LLE
(2017)
Drying Affects the Fiber Network in Low Molecular Weight Hydrogels.
in Biomacromolecules
Nolan M
(2017)
pH dependent photocatalytic hydrogen evolution by self-assembled perylene bisimides
in Journal of Materials Chemistry A
Nolan MC
(2017)
Optimising low molecular weight hydrogels for automated 3D printing.
in Soft matter
Okesola BO
(2019)
Supramolecular Self-Assembly To Control Structural and Biological Properties of Multicomponent Hydrogels.
in Chemistry of materials : a publication of the American Chemical Society
Panja S
(2019)
Maintaining homogeneity during a sol-gel transition by an autocatalytic enzyme reaction
in Chemical Communications
Panja S
(2021)
Mimicking evolution of 'mini-homeostatic' modules in supramolecular systems
in Giant
Panja S
(2019)
Gel to gel transitions by dynamic self-assembly
in Chemical Communications
| Description | We have developed a range of new methods for the preparation of multicomponent gels. These are formed when two molecules form different types of networks. We have also developed a range of new methods for analysing these gels. As part of this, we have learned how to make gels with mixed or self-sorted self-assembled fibres. We have recently developed new methods to characterise these systems as well as used these in optoelectronic applications. Recent data shows that we have interestign optoelectronic properties that can be tuned by self-sorting protocols as originally in the objectives. This will be published in due course. |
| Exploitation Route | A large number of other research groups are now using our methods, including Smith (York), Thordarson (University of New South Wales), Lloyd (Heriot-Watt University), Tovar (Johns Hopkins University). We have had visitors from different groups learning to use our techniques. |
| Sectors | Chemicals,Energy |
| Description | We are in discussion with an industrial partner who wishes to make use of some of the information we have gathered during this programme for 3D printing gels. The aim is for there to be a transfer of materials in the near future. On top of this, we were awarded a knowledge exchange voucher to enable transfer of knowledge into another company. This was successful, with the PDRA spending time in the company. The work has also led to a patent, we have provided demonstrator models to a key industrial partner and we have just been awarded and IAA to look into collecting extra data and information with the view to applying for funding from Scottish Enterprise to start a spin-out company. A further IAA was awarded in Feb 2021 to further exploit this work. As part of this, we are building a large scale demonstrator model and intend to show this an technology events. |
| First Year Of Impact | 2016 |
| Sector | Digital/Communication/Information Technologies (including Software),Healthcare |
| Impact Types | Economic |
| Title | PHOTOCHROMIC AND ELECTROCHROMIC COMPOUNDS |
| Description | Provided are novel naphthalene diimide (NDI) compound of Formula 1. The compounds may exhibit colour change from substantially transparent to substantially black upon electrochemical or photochemical stimulus and may be useful in smart windows. |
| IP Reference | WO2020043895 |
| Protection | Patent application published |
| Year Protection Granted | 2020 |
| Licensed | No |
| Impact | We are in discussion with a company and are in the process of preparing effective demonstrator models using an IAA award to enable this. |