Property-Enhanced Porphyrins
Lead Research Organisation:
University of Sheffield
Department Name: Chemistry
Abstract
In natural photosynthesis, the sun light is directly collected and conveyed to a pair of precisely organised porphyrins, the special pair, which undergoes charge separation. The liberated electron is then translated into chemical energy that is used to develop the living organism. In brief, photosynthesis consumes carbon dioxide and water to produce energy-rich molecules and delivers Oxygen as a by-product. While the efficiency of natural photosynthesis is questionable, its molecular building blocks are self-assembled, made from common non-toxic elements and its waste and by-products are environmentally favourable. In relation to our most pressing environmental challenges and ever-increasing energy consumption, photosynthesis thus represents the perfect solution.
However, the complexity of the molecular architecture involved in photosynthesis renders it difficult to reproduce artificially. Nevertheless, it is possible to mimic specific aspects of photosynthesis and researchers have concentrated their efforts in the development of carbon capture, bio-fuel production, water splitting and photovoltaic solar cells. Each of these approaches to artificial photosynthesis includes an antenna system to harvest the sun light. Alike in natural photosynthesis, the role of the antenna in these artificial systems can be played by a porphyrin.
Within femto- to picoseconds after absorbing the incoming sun light energy, the porphyrin undergoes specific mechanisms. Of particular interest to this project, we will investigate the following mechanisms: internal conversion, inter-system crossing and direct charge separation. Each of these relaxation pathways dictates the overall device's conversion efficiency. It is therefore crucial to understand the factors that can enhance these specific pathways to develop more efficient devices.
We propose use the latest laser technology to investigate these mechanisms that are ultrafast by nature. More precisely, we will systematically study the effect of atom substitution, ring bending, and ring expansion in series of unique single-porphyrins that differs from one-another by a single constituent. Similarly, to investigate the effect of host electronegativity, we will investigate porphyrin-embedded complexes (called cytochromes) that differs from one another by the nature of their ligand, and thus electrostatic environment.
The outcome of this project is to generate a list of physical characteristics that enhance either internal conversion, inter-system crossing or charge separation. With such list in hand we would then be able to design improved porphyrins for specific applications.
However, the complexity of the molecular architecture involved in photosynthesis renders it difficult to reproduce artificially. Nevertheless, it is possible to mimic specific aspects of photosynthesis and researchers have concentrated their efforts in the development of carbon capture, bio-fuel production, water splitting and photovoltaic solar cells. Each of these approaches to artificial photosynthesis includes an antenna system to harvest the sun light. Alike in natural photosynthesis, the role of the antenna in these artificial systems can be played by a porphyrin.
Within femto- to picoseconds after absorbing the incoming sun light energy, the porphyrin undergoes specific mechanisms. Of particular interest to this project, we will investigate the following mechanisms: internal conversion, inter-system crossing and direct charge separation. Each of these relaxation pathways dictates the overall device's conversion efficiency. It is therefore crucial to understand the factors that can enhance these specific pathways to develop more efficient devices.
We propose use the latest laser technology to investigate these mechanisms that are ultrafast by nature. More precisely, we will systematically study the effect of atom substitution, ring bending, and ring expansion in series of unique single-porphyrins that differs from one-another by a single constituent. Similarly, to investigate the effect of host electronegativity, we will investigate porphyrin-embedded complexes (called cytochromes) that differs from one another by the nature of their ligand, and thus electrostatic environment.
The outcome of this project is to generate a list of physical characteristics that enhance either internal conversion, inter-system crossing or charge separation. With such list in hand we would then be able to design improved porphyrins for specific applications.
Planned Impact
Fossil fuels has been driving the British national economy and international policies for the past century. Unfortunately, the environmental changes associated with the extensive consumption of fossil fuels have now become a threat to the international and national social and economic equilibrium as we know it today. Consequently, the adaptation of UK's industries to a more sustainable energy production will be the key factor for the country's competitiveness in the next decades. In the particular case of the UK, the EPSRC has been one of the major driver for this adaptation by investing in its Solar Technologies research area portfolio. Indeed, it is agreed that solar energy is the one sustainable energy source that, if harvested adequately, has the potential to respond to the ever-demanding energy needs of our society. This project, is directly aligned with EPSRC's effort in developing its Energy sector, and has the potential to impact the society at large.
Energy and environment are subjects that affect our daily lives. This project, because it aims at fostering the development of more efficient ways to generate renewable energy, will impact, in the mid- and long-term, all aspect of our lives, indiscriminately. If solar energy comes to liberate us from our oil dependences, as it is expected in the next decades, then this project would be an integral part of this transition.
Knowledge of a more efficient way to convert sunlight into chemical or electrical energy is a determinant step toward sustainable prosperity. An in-depth understanding and subsequent ability to control the relaxation pathways of photo-excited porphyrins will lead to the development of a cleaner energy production. This project thus comes right in time to foster technological innovations in renewable and sustainable energies.
The project's aims are also directly aligned with those of the Grantham Centre for Sustainable Futures; a joint project between the University of Sheffield and the Grantham Foundation. Through this collaboration, the output of the project will inform policy and the development of products for industrial application. Both of which will in turn affect the wider society by building fairer societies and preserve our natural resources for the future generations.
In economic terms, since the output of the project is to provide with a systematic approach in synthetizing porphyrins for specific applications, it will therefore participate in reducing the overall cost of research. For example, under better guidance, the research in the fields of Dye-Sensitized Solar Cell will be more effective. Consequently, this project will help maximizing the impact that governmental research funding has in a key investment area such as Solar Energy.
While in this section is only concerned with a summary of impacts, the pathways to achieve these impacts are detailed in the attached Pathway to Impact document.
Energy and environment are subjects that affect our daily lives. This project, because it aims at fostering the development of more efficient ways to generate renewable energy, will impact, in the mid- and long-term, all aspect of our lives, indiscriminately. If solar energy comes to liberate us from our oil dependences, as it is expected in the next decades, then this project would be an integral part of this transition.
Knowledge of a more efficient way to convert sunlight into chemical or electrical energy is a determinant step toward sustainable prosperity. An in-depth understanding and subsequent ability to control the relaxation pathways of photo-excited porphyrins will lead to the development of a cleaner energy production. This project thus comes right in time to foster technological innovations in renewable and sustainable energies.
The project's aims are also directly aligned with those of the Grantham Centre for Sustainable Futures; a joint project between the University of Sheffield and the Grantham Foundation. Through this collaboration, the output of the project will inform policy and the development of products for industrial application. Both of which will in turn affect the wider society by building fairer societies and preserve our natural resources for the future generations.
In economic terms, since the output of the project is to provide with a systematic approach in synthetizing porphyrins for specific applications, it will therefore participate in reducing the overall cost of research. For example, under better guidance, the research in the fields of Dye-Sensitized Solar Cell will be more effective. Consequently, this project will help maximizing the impact that governmental research funding has in a key investment area such as Solar Energy.
While in this section is only concerned with a summary of impacts, the pathways to achieve these impacts are detailed in the attached Pathway to Impact document.
Organisations
- University of Sheffield (Lead Research Organisation)
- Federal University of Rio de Janeiro (Collaboration)
- Swiss Federal Institute of Technology in Lausanne (EPFL) (Collaboration)
- University of Sheffield (Collaboration)
- Liverpool John Moores University (Collaboration)
- University of Connecticut (Collaboration)
- University of Silesia (Collaboration)
- University of Tennessee (Collaboration)
Publications
A.P. Chauvet A
(2019)
Fourier Transforms - Century of Digitalization and Increasing Expectations
Auty A
(2022)
Ultrafast Transient Absorption Spectroscopy of Inkjet-Printed Graphene and Aerosol Gel Graphene Films: Effect of Oxygen and Morphology on Carrier Relaxation Dynamics
in The Journal of Physical Chemistry C
Bhattacharya S
(2023)
Photophysical Exploration of Two Isomers of Octaethyltrioxopyrrocorphin
in The Journal of Physical Chemistry A
Bhattacharya S
(2022)
Tailoring the Intersystem Crossing and Triplet Dynamics of Free-Base Octaalkyl-ß-oxo-Substituted Porphyrins: Competing Effects of Spin-Vibronic and NH Tautomerism Relaxation Channels.
in The journal of physical chemistry. A
Brückner C
(2021)
Structural and Photophysical Characterization of All Five Constitutional Isomers of the Octaethyl-ß,ß'-dioxo-bacterio- and -isobacteriochlorin Series.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Saeed HK
(2023)
From Chemotherapy to Phototherapy - Changing the Therapeutic Action of a Metallo-Intercalating RuII -ReI Luminescent System by Switching its Sub-Cellular Location.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Smitten K
(2023)
Clearing an ESKAPE Pathogen in a Model Organism; A Polypyridyl Ruthenium(II) Complex Theranostic that Treats a Resistant Acinetobacter baumannii Infection in Galleria mellonella
in Chemistry - A European Journal
Title | Periodic Table of Poetry |
Description | We supported an outreach project organised for the International Year of the Periodic Table. The goal is to create an interactive periodic table with a poem associated to every element. These poems are written by academic staff, student and pupils. It will be made available online hoping that it will promote a liking for the field of science (in particular, chemistry). This project fits within the grant as we are taking particular attention to the effect of specific element on the overall electronic dynamics of porphyrins. |
Type Of Art | Creative Writing |
Year Produced | 2019 |
Impact | The website is created but needs polishing. After completion, it will be made available online. |
Description | We have monitored for the first time the electron dynamics of newly synthesised light-absorbing molecules. This corresponds to the first step of the project. The goal being to understand how they behave, then to cross check all data and find trends to build a set of guidelines for the synthesis of purpose-build molecules. (Jan 2020 update). We have completed the analysis of the first OEP-series. A manuscript is in preparation. |
Exploitation Route | Through publication and conferences first, then through direct contact with stakeholders. |
Sectors | Chemicals Electronics Energy Pharmaceuticals and Medical Biotechnology |
Description | The findings have been used for outreach purposes. Benefitting from the outcome of this project, I am invited to present in schools and to participate to local outreach event (e.g. Pint of Science) on a yearly basis. |
First Year Of Impact | 2019 |
Sector | Education |
Impact Types | Cultural Societal |
Description | EPSRC Capital Award for Core Equipment |
Amount | £549,334 (GBP) |
Funding ID | EP/T024526/1 |
Organisation | Engineering and Physical Sciences Research Council (EPSRC) |
Sector | Public |
Country | United Kingdom |
Start | 02/2020 |
End | 08/2021 |
Description | KE with Metallobio |
Amount | £4,500 (GBP) |
Organisation | University of Sheffield |
Sector | Academic/University |
Country | United Kingdom |
Start | 09/2021 |
End | 01/2022 |
Title | Long-time TA |
Description | In partnership with Dr. Jenny Clark, the PDRA helped develop a transient absorption spectroscopy setup with time window spanning the ns-ms range. |
Type Of Material | Improvements to research infrastructure |
Year Produced | 2020 |
Provided To Others? | No |
Impact | Publications are to come |
Title | Transient absorption in reflection mode |
Description | Enabling transient absorption in reflection mode for opaque samples. |
Type Of Material | Improvements to research infrastructure |
Year Produced | 2022 |
Provided To Others? | Yes |
Impact | It enables us to characterise a wider range of samples |
Description | Christian Brückner: Sample provider |
Organisation | University of Connecticut |
Country | United States |
Sector | Academic/University |
PI Contribution | We are characterising the ultrafast electron dynamics of the unique porphyrins that the collaborator has synthesised. He send us a couple of prophyrin series in 2016 and again in 2020. This collaboration was the basis of this grant. Hence, while it started before the grant was allocated, the grant enabled the collaboration to develop. |
Collaborator Contribution | Prof Bruckner has provided us with unique set of porphyrins. |
Impact | The first set of data are acquired and analysed. Publication is to come |
Start Year | 2016 |
Description | Fyaz Ismail: antimalarial drug |
Organisation | Liverpool John Moores University |
Country | United Kingdom |
Sector | Academic/University |
PI Contribution | We will provide with characterisation of the synthetized drug. The objective is to study it mode of operation, to possibly evaluate their efficiency. |
Collaborator Contribution | Provided with samples |
Impact | The first molecules have been characterised; data analysis is still to be finalized. |
Start Year | 2020 |
Description | George Sutherland (Sample provider) |
Organisation | University of Sheffield |
Country | United Kingdom |
Sector | Academic/University |
PI Contribution | We provided ultrafast and steady-state characterisation of the samples. |
Collaborator Contribution | The partner provided us with unique protein maquette for characterisation. |
Impact | Analysis of the data is still on-going. |
Start Year | 2020 |
Description | Jacek Nycz: Proton transfer |
Organisation | University of Silesia |
Country | Poland |
Sector | Academic/University |
PI Contribution | We are investigating the light induced proton transfers in the model proteins provided |
Collaborator Contribution | Provided with quinine-derivatives samples |
Impact | Frist sample received. Characterisation is to come |
Start Year | 2020 |
Description | Jenny Clark: Tuning of the ISC |
Organisation | University of Sheffield |
Country | United Kingdom |
Sector | Academic/University |
PI Contribution | Scientific contribution to develop a sub-project aimed at exploring the effect of host medium on porphyrin's inter-system crossing. |
Collaborator Contribution | Knowledge, expertise, access to equipment and further collaborators. |
Impact | Through this collaboration, we developed a long-time transient absorption (up to micro-second) to observe the more physiologically relevant processes. |
Start Year | 2019 |
Description | Jenny Clark: Tuning of the ISC |
Organisation | University of Sheffield |
Country | United Kingdom |
Sector | Academic/University |
PI Contribution | Scientific contribution to develop a sub-project aimed at exploring the effect of host medium on porphyrin's inter-system crossing. |
Collaborator Contribution | Knowledge, expertise, access to equipment and further collaborators. |
Impact | Through this collaboration, we developed a long-time transient absorption (up to micro-second) to observe the more physiologically relevant processes. |
Start Year | 2019 |
Description | Jim Thomas, Ru complexes |
Organisation | University of Sheffield |
Country | United Kingdom |
Sector | Academic/University |
PI Contribution | Provided with photodynamic characterisations, looking at phototoxicity. |
Collaborator Contribution | Provided with Ru-complexes |
Impact | Hopefully, a publication will come out of the analysis. |
Start Year | 2021 |
Description | Sami Rtimi: antibacterial thin film metal oxides |
Organisation | Swiss Federal Institute of Technology in Lausanne (EPFL) |
Country | Switzerland |
Sector | Public |
PI Contribution | Provided with electron dynamic characterisation. While the collaboration started before this award, the award enabled the collaboration to develop further. |
Collaborator Contribution | Provided with samples |
Impact | One paper already published. And we have the data for two more publications. |
Start Year | 2015 |
Description | Thiago Cardozo: Theoretical support |
Organisation | Federal University of Rio de Janeiro |
Department | Institute of Chemistry |
Country | Brazil |
Sector | Academic/University |
PI Contribution | We have provided with steady-state and kinetic data on particular porphyrins. |
Collaborator Contribution | They have provided with modelling that will help interpret our data. |
Impact | A first set of porphyrins have been modelled; modelling it now to be refined based on the data we provided and publication is to come. |
Start Year | 2018 |
Description | Viktor Nemykin, theoretical support |
Organisation | University of Tennessee |
Country | United States |
Sector | Academic/University |
PI Contribution | Provide photodynamic characterisation. |
Collaborator Contribution | Provides DFT modelling of porphyrins. |
Impact | 1 publication, and another submitted manuscript. 1 more to come in 2022. |
Start Year | 2021 |
Description | I'm a Scientist, Get me out of here! |
Form Of Engagement Activity | Engagement focused website, blog or social media channel |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Schools |
Results and Impact | Outreach online platform where (registered) students can ask science-related questions. |
Year(s) Of Engagement Activity | 2020 |
URL | https://imascientist.org.uk/ |
Description | Invited seminar |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Postgraduate students |
Results and Impact | Invited to give a seminar at the collaborator's research group, at Universidade Federal do Rio de Janeiro. |
Year(s) Of Engagement Activity | 2019 |
Description | Postgraduate 1st year talk |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | Local |
Primary Audience | Postgraduate students |
Results and Impact | This is a local event organised to give PhD students the opportunity to show their work to the wider student and staff within the university. |
Year(s) Of Engagement Activity | 2018 |
Description | Postgraduate Poster Showcase |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | Local |
Primary Audience | Postgraduate students |
Results and Impact | This is a local event organised to give PhD students the opportunity to showcase the group's research. |
Year(s) Of Engagement Activity | 2019 |
Description | Tapton Secondary School |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | Local |
Primary Audience | Schools |
Results and Impact | Outreach talk |
Year(s) Of Engagement Activity | 2021 |