Control of 2-Dimensional Molecular Self-Organisation: Towards Designed Surfaces

Lead Research Organisation: University of Liverpool
Department Name: Chemistry

Abstract

Organic molecular monolayers at surfaces often constitute the central working component in nanotechnologies such as sensors, molecular electronics, smart coatings, organic solar cells, catalysts, medical devices, etc. A central challenge in the field is to achieve controlled creation of desired 2D molecular architectures at surfaces. Within this context, the past decade has witnessed a real and significant step-change in the 'bottom-up' self-organisation of 2D molecular assemblies at surfaces. The enormous variety and abundance of molecular structures formed via self-oeganisation has now critically tipped the argument strongly in favour of a 'bottom-up' construction strategy, which harnesses two powerful attributes of nanometer-precision (inaccessible to top-down methods) and highly parallel fabrication (impossible with atomic/molecular manipulation). Thus, bottom-up molecular assembly at surfaces holds the real possibility of becoming a dominating synthesis protocol in 21st century nanotechnologies

Uniquely, the scope and versatility of these molecular architectures at 2D surfaces have been directly captured at the nanoscale via imaging with scanning probe microscopies and advanced surface spectroscopies. At present, however, the field is largely restricted to a 'make and see' approach and there is scarce understanding of any of the parameters that ultimately control molecular surface assembly. For example: (1) molecular assemblies at surfaces show highly polymorphic behaviour, and a priori control of assembly is practically non-existent; (2) little is understood of the influence and balance of the many interactions that drive molecular recognition and assembly (molecule-molecule interactions including dispersion, directional H-bonding and strong electrostatic and covalent interactions); (3) the role of surface-molecule interactions is largely uncharted even though they play a significant role in the diffusion of molecules and their subsequent assembly; (4), there is ample evidence that the kinetics of self-assembly is the major factor in determining the final structure, often driving polymorphic behaviour and leading to widely varied outcomes, depending on the conditions of formation; (5) a gamut of additional surface phenomena also also influence assembly e.g. chemical reactions between molecules, thermally activated internal degrees of freedom of molecules, surface reconstructions and co-assembly via coordinating surface atoms.

The main objective of this project is to advance from experimental phenomena-reporting to knowledge-based design, and its central goal is to identify the role played by thermodynamic, entropic, kinetic and chemical factors in dictating molecular organisation at surfaces under given experimental conditions. To address this challenge requires a two-pronged approach in which ambitious and comprehensive theory development is undertaken alongside powerful imaging and spectroscopic tools applied to the same systems. This synergy of experiment and theory is absolutely essential to develop a fundamental understanding, which would enable a roadmap for controlled and engineered self-assembly at surfaces to be proposed that would, ultimately, allow one to 'dial up' a required structure at will. Four important and qualitatively different classes of assembly at surfaces will be studied: Molecular Self-Assembly; Hierarchical Self-Assembly; Metal-Organic Self Assembly; and, on-surface Covalent Assembly.

Planned Impact

Dissemination: Research outputs will be published in high impact journals and presented at international conferences, increasing the profile of UK science.

Industry impact:
Results of significance to technology and society will be disseminated to industry, government and public bodies via the dedicated UoL publication 'Research Intelligence'. Key breakthroughs will be publicised through the press offices of KCL and UoL, which have direct links to the media and to all learned societies (e.g. the Royal Society, the RSc, IoP, and the IoM). Work of the project will also be presented at 'Industry Days' being planned by RR, where invited industrial delegates and members of Knowledge Transfer Networks (KTN) in Nanotechnology, Materials, Chemistry and Health will engage with academic researchers and discuss collaboration and partnership. Theoretical advances, relevant to industry, will be disseminated with the help of KCL Business, a gateway for society and businesses to access research outputs at KCL, and the Thomas Young Centre (TYC), where LK is on the Executive Committee. TYC enjoys close contacts with National Physics Laboratory and also with Samsung, UK Defence Industry and BP.

Knowledge Transfer (KT) capability:
The research outputs will be scrutinised by the PIs for possible exploitation, patent protection and commercialisation, aided by the Business divisions from each institution. Both Universities are members of the Russell Group, are strongly committed to staying at the forefront of innovation and research, have a long-established track records of impact resulting from research, and strong cultures for Knowledge Exchange (KE) activities. UoL topped the Russell Group in 2007 for income per academic from KE, is the best performer in KT Partnerships in the northwest of England, and holds an EPSRC KT Account (KTA) to increase the impact and Technology Readiness Level of EPSRC funded research. RR is the KE coordinator for the School of Physical Sciences, has strong experience in engaging with the private sector in her previous role as the Associate Director of the Leverhulme Centre for Innovative Catalysis at UoL and is a member of European research networks with active industrial partnership and has secured international patents. She has also been actively engaged with UoL Business Gateway team regarding IP protection, shareholding agreements and spin-outs.

Public Engagement and Outreach:
RR is PI on a major EPSRC public partnership grant 'Giants of the Infinitesimal' that has created an exhibition on nanoscience for school children (launched in October 2011 at the Manchester Museum of Science and Industry). Additional funds are requested to expand the exhibition to describe self-assembly at surfaces and how such systems could underpin new nanotechnologies, and allow the exhibition to travel to new sites. The Societal Impact of this exhibition will be to make the public aware of the potential of nanoscience, the future applications of research and the responsibilities involved. The topic of self-assembly will form a dedicated zone and will include applications such as organic solar cells, smart displays, electronic paper, etc. At KCL, results of wider significance to technology and society will be disseminated by a dedicated science media liaison person, who will communicate our outcomes to wider mainstream media. There will also be dissemination at weekly Maxwell lectures, hosted by KCL, which are open to the general public. The Physics Department has an active outreach committee, which will ensure that our results become available to several London based secondary schools via seminars and invited lectures. LK has been invited by Highgate School to give presentations about his research. Specifically, London schools from deprived areas will be targeted to increase interest in science, and we request funding to cover the cost for them to visit the Departmen

Publications

10 25 50
 
Description Significant new knowledge on the use of C-H synthons to drive clean covalent coupling at surfaces.

Significant New Knowledge Created on the mechanisms that drive self-assembly and covalent coupling of complex molecules in 2-dimensional systems at surfaces.

Important new research questions on the nature of molecular motion at surfaces, and how it may be directed unidirectionally, with implications for molecular motors and molecular separations.

Demonstration that simple molecular structures can be used as directional molecular walkers at surfaces. Important platform knowledge to create complex functional interfaces that can be applied for anti-microbial and anti-biofouling interfaces. This has led to the establishment of a new research area of Antimicrobial Surfaces in my group. This capability is also core within the newly launched BBSRC/Innovate UK National Biofilms Innovation Centre.
Exploitation Route Knowledge generated in this project will impact on a range of scientific fields in nano-, surface and materials science. Specifically, the ability to control 2D assembly of molecular components at surfaces will impact on research in smart materials, catalysis, information storage, molecular electronics and nanolocomotion. The capability to create complex building blocks at a surface has led to the establishment of a new research area of Antimicrobial Surfaces in my group. This capability is also core within the newly launched BBSRC/Innovate UK National Biofilms Innovation Centre.
Sectors Aerospace, Defence and Marine,Agriculture, Food and Drink,Chemicals,Education,Electronics,Energy,Healthcare

 
Description Understanding molecular assembly at surfaces provides a way to create novel coatings for the marine, biomedical and healthcare industries. Understanding covalent molecular coupling at surfaces provides a way to create robust coatings for biomedical and energy industries. This knowledge base has been instrumental in establishing a new research area on antimicrobial and anti-biofouling surfaces, which has led to follow on finding from Innovate UK, BBSRC and EPSRC.
First Year Of Impact 2013
Sector Aerospace, Defence and Marine,Energy,Healthcare,Manufacturing, including Industrial Biotechology
Impact Types Economic

 
Description BBSRC
Amount £12,500,000 (GBP)
Funding ID BB/R012415/1 
Organisation Biotechnology and Biological Sciences Research Council (BBSRC) 
Sector Public
Country United Kingdom
Start 12/2017 
End 11/2022
 
Description EPSRC
Amount £413,000 (GBP)
Funding ID EP/N51004X/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 01/2016 
End 12/2017
 
Description ERDF
Amount £1,995,198 (GBP)
Funding ID X03168PR 
Organisation Government of the UK 
Department Department for Communities & Local Government (DCLG)
Sector Public
Country United Kingdom
Start 10/2013 
End 06/2015
 
Description Innovate UK
Amount £320,000 (GBP)
Funding ID TS/L007932/1 
Organisation Innovate UK 
Sector Public
Country United Kingdom
Start 09/2014 
End 08/2016
 
Description Innovate UK
Amount £493,000 (GBP)
Funding ID TS/L004925/1 
Organisation Innovate UK 
Sector Public
Country United Kingdom
Start 04/2014 
End 02/2016
 
Description Innovate UK
Amount £334,000 (GBP)
Funding ID TS/L001985/1 
Organisation Innovate UK 
Sector Public
Country United Kingdom
Start 12/2013 
End 02/2016
 
Description Innovate UK
Amount £668,000 (GBP)
Funding ID TS/N005600/1 
Organisation Innovate UK 
Sector Public
Country United Kingdom
Start 03/2016 
End 08/2018
 
Description Innovate UK
Amount £521,000 (GBP)
Funding ID TS/P004512/1 
Organisation Innovate UK 
Sector Public
Country United Kingdom
Start 03/2017 
End 02/2019
 
Description Innovate UK
Amount £668,000 (GBP)
Funding ID £145,762 
Organisation Innovate UK 
Sector Public
Country United Kingdom
Start 03/2016 
End 02/2019
 
Description Innovate UK
Amount £350,000 (GBP)
Funding ID TS/P013716/1 
Organisation Innovate UK 
Sector Public
Country United Kingdom
Start 04/2017 
End 09/2019
 
Description Innovate UK
Amount £333,000 (GBP)
Funding ID TS/L00190X/1 
Organisation Innovate UK 
Sector Public
Country United Kingdom
Start 02/2014 
End 07/2016
 
Description Dr Per Uvdal 
Organisation Lund University
Country Sweden 
Sector Academic/University 
PI Contribution Surface science experiments of self-assembly systems.
Collaborator Contribution Modelling vibrational data.
Impact publications: doi:10.1063/1.4907721
Start Year 2014
 
Description Dr Yousoo Kim 
Organisation RIKEN
Country Japan 
Sector Public 
PI Contribution Jointly funded studentship. Co-Design of experiments. Self-assembly of complex molecules at surfaces.
Collaborator Contribution Jointly funded studentship. Co-Design of experiments. Low Temperature STM experiments
Impact Publications: doi:10.1039/c7cc01310h Joint memorandum of understanding signed between Riken and University of Liverpool. Multidisciplinary research: Surface chemistry; Surface Physics; Surface Dynamics; Theoretical modelling
Start Year 2014
 
Description Jeanne Crassous 
Organisation University of Rennes 1
Country France 
Sector Academic/University 
PI Contribution Co-Design of experiments. Undertaking chiral surface assembly experiments.
Collaborator Contribution Co-Design of experiments. Synthesis of molecules.
Impact Participation in specialist conferences.
Start Year 2014
 
Description Prof David Amabilino 
Organisation University of Nottingham
Country United Kingdom 
Sector Academic/University 
PI Contribution Co-Design of experiments. Undertaking surface science experiments on synthesized molecules.
Collaborator Contribution Co-Design of experiments. Synthesis of molecules
Impact Joint Publications see DOIs below: doi: 10.1039/C7FD90077E doi: 10.1039/C7FD90076G doi: 10.1039/c7fd90074k doi: 10.1021/nn502388u doi: 10.1002/anie.201502153 Multidisciplinary: Synthetic Organic Chemistry, Surface Science, Theoretical Modelling
Start Year 2014
 
Description Prof L Grill University of Graz 
Organisation University of Graz
Country Austria 
Sector Academic/University 
PI Contribution Conducting a joint research project on novel coupling reactions at surfaces. Our team conducted room temperature STM experiments, data analysis, provided input intoDFT calculations and co-wrote the paper.
Collaborator Contribution The Graz team conducted low temperature STM experiments, data analysis, provided input intoDFT calculations and co-wrote the paper.
Impact Seufert, K., McBride, F., Jaekel, S., Wit, B., Haq, S., Steiner, A., . . . Grill, L. (2019). Porphine Homocoupling on Au(111). JOURNAL OF PHYSICAL CHEMISTRY C, 123(27), 16690-16698. doi:10.1021/acs.jpcc.9b02770 Multidisciplinary collaborations between Physics, Chemistry and theory.
Start Year 2018
 
Description Geneva Day 18th 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 Invited Talk on 'What molecules do at Surfaces' to postgraduate students during the Geneva Chemistry and Biochemistry Days, University of Geneva January 17-18, 2019. Attended by 100 postgraduate students drawn from a chemistry and biochemistry background.
Year(s) Of Engagement Activity 2019
URL http://www.unige.ch/sciences/chimie/Conferences/posters/ConfPost2357.pdf
 
Description Invited presentation at the "In The Know" breakfast event on Infection and Disease at Liverpool Science Park, 30 Mar 2017 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Industry/Business
Results and Impact Invited presentation at the "In The Know" breakfast event on Infection and Disease at Liverpool Science Park, 30 Mar 2017 to highlight research and innovation in the region.
A number of interactions with regional institutes and national/global industry were initiated.
Year(s) Of Engagement Activity 2017
 
Description Launch of book ' NANOSCIENCE Giants of the Infinitesimal' By Peter Forbes and Tom Grimsey, 2014 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Public/other audiences
Results and Impact Book Launch of "NANOSCIENCE: Giants of the Infinitesimal" By Peter Forbes and Tom Grimsey, 2014
(Papadakis 2014 | 192pp ISBN 9781906506230)

on Tuesday, 3rd June 2014 at
The Smith Centre,
The Science Museum
Entrance on Imperial College Road
South Kensington
London SW7 2DD
Year(s) Of Engagement Activity 2014
URL https://www.facebook.com/events/328088314006037/
 
Description Launch of the National Biofilm Innovation Centre, The Royal Society London, 28th November 2017. 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Policymakers/politicians
Results and Impact Official launch of the £26M National Biofilm Innovation Centre (NBIC), The Royal Society London, November 2017, as part of the the award of the BBSRC IKC and Government's Industry Strategy.
NBIC was launched to restructure Biofilms research and innovation in the UK and will drive a national agenda to this effect. It is led by the 4 co-leads:
Prof J Webb (U of Southampton); Prof R Raval (U of Liverpool), M. Camara (U of Nottingham) and C. MacPhee (U of Edinburgh) who represent a multi- and inter-disciplinary team.
Year(s) Of Engagement Activity 2017