Details of Grant 

EPSRC Reference:	EP/P010253/1
Title:	Exploring Delocalised Energy Transport in Bacterial Reaction Centres
Principal Investigator:	Oliver, Dr T
Other Investigators:
Researcher Co-Investigators:
Project Partners:
Department:	Chemistry
Organisation:	University of Bristol
Scheme:	First Grant - Revised 2009
Starts:	01 February 2017	Ends:	31 July 2018	Value (£):	100,963
EPSRC Research Topic Classifications:	Analytical Science Biological & Medicinal Chem. Biophysics Gas & Solution Phase Reactions
EPSRC Industrial Sector Classifications:	No relevance to Underpinning Sectors
Related Grants:
Panel History:	Panel Date Panel Name Outcome 13 Sep 2016 EPSRC Physical Sciences - September 2016 Announced
Summary on Grant Application Form
Photosynthetic organisms such as plants, algae and bacteria, harness the energy from sunlight to drive all downstream processes such as synthesis of carbohydrates, which are essential for cell growth, function, and repair. Reaction centres (RCs) play the pivotal role of accepting energy absorbed by 1000s of light absorbing carotenoid and (bacterio)chlorophyll molecules and use it to induce charge separation, generating electrons (and holes). Electrons are then used to form a vital concentration gradient of protons that drive adenosine triphosphate synthesis. The process of initial light capture in light harvesting antenna, rapid energy transfer between (bacterio)chlorophyll molecules and charge separation in RCs is, remarkably, 100% efficient under low light intensities. Despite many prior studies of RCs, several important factors underling the high yield of chemical charge separation have yet to be directly experimentally determined. RCs of Rhodobacter sphaeroides contain seven tightly packed light absorbing molecules: four bacteriochlorophylls-a, two bacteriopheophytins-a (both bacteriochlorin pigments) and a 15,15'-cis-spheroidene carotenoid moiety. Energy transfer between adjacent RC pigments takes place on ~100 fs timescales (1 fs = one millionth billionth of a second). The rate of energy transfer, which underpins the yield of eventual charge-separation, is dictated by the electronic structure of RCs, and the extent to which photoexcited molecules share electrons (delocalisation). In the regime of spatially separated molecules, the interaction between chormophores is minimal and electrons remain localised on their respective molecules. However, in RCs the distances between pigments ranges between 5 and 10 Angstroms and through inter-molecular interactions electrons can become delocalised over multiple pigments. To date, no experiment has been able to directly measure the delocalisation of RC excited states. Ultrafast laser spectroscopies using pulses of light shorter than the dynamical processes involved can be used to take snapshots of the system and infer the route(s) and associated timescales of energy flow through the system. One such emerging technique, two-dimensional electronic-vibrational spectroscopy will be used to investigate the spatial location of excited states in RCs as a function of time, and transform our knowledge of the inter-molecular interactions and of the RC electronic structure. Carotenoid pigments play a dual role in photosynthesis, acting as both accessory light harvesting pigments and regulatory elements that can protect plants from damage caused by excessive sunlight. In their light harvesting capacity, they can absorb parts of the solar spectrum where (bacterio)chlorophyll absorption is weak. Carotenoids increase the total coverage of the solar spectrum by transferring energy to (bacterio)chlorophyll molecules. The carotenoid to bacteriochlorin energy transfer mechanisms for RCs have not been fully characterised and may involve pathways that have hitherto been ignored. Two-dimensional electronic spectroscopy will be used to follow the energy transfer between carotenoid and different bacteriochlorin pigments, revealing the energy transfer pathways and associated timescales that enhance the light harvesting capability of RCs. The proposed experiments seek to transform our current description of the electronic structure of Rhodobacter sphaeroides RCs and how energy is transferred between constituent light absorbing molecules, preparing the system for one of nature's most efficient charge-carrier generation events. The study will provide key design principles of inter-molecular couplings in RCs, and unravel the blueprint for the efficient energy transduction. These design principles will be key for engineering bio-inspired molecular solar cell technology or water splitting catalysts.
Key Findings
This information can now be found on Gateway to Research (GtR) http://gtr.rcuk.ac.uk
Potential use in non-academic contexts
This information can now be found on Gateway to Research (GtR) http://gtr.rcuk.ac.uk
Impacts
Description This information can now be found on Gateway to Research (GtR) http://gtr.rcuk.ac.uk Summary Date Materialised
Sectors submitted by the Researcher
This information can now be found on Gateway to Research (GtR) http://gtr.rcuk.ac.uk
Project URL:
Further Information:
Organisation Website:	http://www.bris.ac.uk