Towards excited state dynamics in nucleosides
Lead Research Organisation:
University of Warwick
Department Name: Chemistry
Abstract
The objective of this proposal is to study ultrafast UV-laser-induced dynamics in the DNA bases adenine and guanine as a stepping stone towards the nucleosides adenosine and guanosine. Funding will enable the PI to implement laser desorption into his laboratory so that these nucleosides can be brought into vacuum without decomposition and hence their ultrafast photochemistry studied in the gas-phase for the first time. Complementary high level calculations will provide critical guidance to interpreting the experimental results whilst posing new challenges to theoreticians as these studies will explore the complex interplay between multiple reaction paths and the ways these paths are coupled with one another with increasing molecular complexity. The PI, CoI and RCoI are ideally placed to undertake this exciting and ambitious research, which will begin to bridge the gap between the photochemistry of the DNA bases and that of nucleosides, and ultimately help elucidate the 'molecular mechanisms of the photostability of life'.
Planned Impact
The research proposed here will impact the following: Experimentalists working in the field. Whilst understanding the photochemistry of these important biomolecules has received considerable interest since the seminal paper of Kim et al., (JCP, 113 (2000) 10051), advances in extending these investigations to larger, more realistic systems has been hindered due to experimental limitations. This works aims to facilitate this transition through the incorporation of laser desorption to the PI's setup; Theoretical Chemists. These measurements will go some way to validating calculations but will also pose new challenges to theoreticians as these studies will explore the complex interplay between multiple reaction pathways and the ways these paths are coupled with one another with increasing molecular size; Experimentalists working in related areas. The potential for knowledge transfer from these experiments is particularly extensive and interdisciplinary, spanning across chemistry, physics and biology. For example, the work may prove invaluable to experimentalists working in related areas of molecular dynamics such as energy transfer processes in larger biomolecules and light harvesting in cell biology, thus bridging the gap between chemical physics with biochemistry and biophysics; The RCoI employed on this grant. The RCoI will be extending his training in a highly interdisciplinary area which spans experimental chemical physics with high level ab initio calculations. These sets of skills are in high demand, especially in an academic environment to which the RCoI aspires towards. The ability to perform experiments and compliment these with such detailed calculations will undoubtedly provide the RCoI with an invaluable toolbox that potential academic Departments hiring will value highly.
The proposed research will trigger new collaborations in related areas involving both experiment and theory: The experiments on adenosine and guanosine proposed here will aim to validate previous speculation by de Vries's group (e.g. Int. J. Mass Spec., 219 (2002) 133). As a result, links will undoubtedly be forged between the complimentary areas of high resolution spectroscopy and ultrafast spectroscopy; The CoI is extending his expertise in non-adiabatic dynamics to the field of ultrafast dynamics in DNA bases and nucleosides, giving him an invaluable opportunity to contribute to the field and diversify his research interests, igniting further collaborations with other experimental groups world-wide; The RCoI intends to pursue an academic career following this project and successful funding of this proposal will undoubtedly help spring-board his career.
There is potential for immediate exploitation of these results by both experimentalists and theoreticians. Thus far, the ability to bridge the gap between studying small subunits of biomolecules (e.g. adenine) and larger units (e.g. adenosine) in the time domain has been hindered by experimental complications. The successful merger of time-resolved velocity map ion imaging with laser desorption has the potential to trigger a vast plethora of new experiments, which ultimately seeks to connect the micro and macro in such molecular studies. Similarly, extending the application of theoretical methodologies to larger scale molecular systems will also spark interest to theorists world-wide, for example in the use of quantum mechanics/molecular mechanics methods for excited states one encounters several new challenges compared to the ground state, and at present such applications are in their relative infancy. One specific application of this research will be ascertaining the extent to which pisigma* states potentially contribute to larger polymeric forms of the units to be studied. The result of this can have a major impact on general studies on dynamics of small gas-phase molecules and the extension of knowledge gained from these isolated molecules to more realistic systems such as those in vivo.
The proposed research will trigger new collaborations in related areas involving both experiment and theory: The experiments on adenosine and guanosine proposed here will aim to validate previous speculation by de Vries's group (e.g. Int. J. Mass Spec., 219 (2002) 133). As a result, links will undoubtedly be forged between the complimentary areas of high resolution spectroscopy and ultrafast spectroscopy; The CoI is extending his expertise in non-adiabatic dynamics to the field of ultrafast dynamics in DNA bases and nucleosides, giving him an invaluable opportunity to contribute to the field and diversify his research interests, igniting further collaborations with other experimental groups world-wide; The RCoI intends to pursue an academic career following this project and successful funding of this proposal will undoubtedly help spring-board his career.
There is potential for immediate exploitation of these results by both experimentalists and theoreticians. Thus far, the ability to bridge the gap between studying small subunits of biomolecules (e.g. adenine) and larger units (e.g. adenosine) in the time domain has been hindered by experimental complications. The successful merger of time-resolved velocity map ion imaging with laser desorption has the potential to trigger a vast plethora of new experiments, which ultimately seeks to connect the micro and macro in such molecular studies. Similarly, extending the application of theoretical methodologies to larger scale molecular systems will also spark interest to theorists world-wide, for example in the use of quantum mechanics/molecular mechanics methods for excited states one encounters several new challenges compared to the ground state, and at present such applications are in their relative infancy. One specific application of this research will be ascertaining the extent to which pisigma* states potentially contribute to larger polymeric forms of the units to be studied. The result of this can have a major impact on general studies on dynamics of small gas-phase molecules and the extension of knowledge gained from these isolated molecules to more realistic systems such as those in vivo.
Organisations
People |
ORCID iD |
Vasilios Stavros (Principal Investigator) |
Publications
Baker LA
(2016)
Ultrafast Photoprotecting Sunscreens in Natural Plants.
in The journal of physical chemistry letters
Baker LA
(2015)
Broadband ultrafast photoprotection by oxybenzone across the UVB and UVC spectral regions.
in Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology
Baker LA
(2015)
Probing the Ultrafast Energy Dissipation Mechanism of the Sunscreen Oxybenzone after UVA Irradiation.
in The journal of physical chemistry letters
Chatterley A
(2014)
Time-resolved photoelectron imaging of the isolated deprotonated nucleotides
in Chem. Sci.
Chatterley AS
(2014)
Mapping the Ultrafast Dynamics of Adenine onto Its Nucleotide and Oligonucleotides by Time-Resolved Photoelectron Imaging.
in The journal of physical chemistry letters
Greenough SE
(2014)
Ultrafast photo-induced ligand solvolysis of cis-[Ru(bipyridine)2(nicotinamide)2](2+): experimental and theoretical insight into its photoactivation mechanism.
in Physical chemistry chemical physics : PCCP
Greenough SE
(2014)
Solvent induced conformer specific photochemistry of guaiacol.
in Physical chemistry chemical physics : PCCP
Harris SJ
(2015)
A Multipronged Comparative Study of the Ultraviolet Photochemistry of 2-, 3-, and 4-Chlorophenol in the Gas Phase.
in The journal of physical chemistry. A
Horbury MD
(2015)
Bridging the Gap between the Gas Phase and Solution Phase: Solvent Specific Photochemistry in 4-tert-Butylcatechol.
in The journal of physical chemistry. A
Quan WD
(2016)
Retaining individualities: the photodynamics of self-ordering porphyrin assemblies.
in Chemical communications (Cambridge, England)
Staniforth M
(2015)
Probing Rotational Motion in 4-tert-Butylcatechol through H Atom Photofragmentation: Deviations from Axial Recoil.
in The journal of physical chemistry. A
Staniforth M
(2014)
Ultrafast excited-state dynamics of 2,4-dimethylpyrrole.
in The journal of physical chemistry. A
Staniforth M
(2017)
First Step toward a Universal Fluorescent Probe: Unravelling the Photodynamics of an Amino-Maleimide Fluorophore.
in The journal of physical chemistry. A
Young JD
(2014)
Towards Understanding Photodegradation Pathways in Lignins: The Role of Intramolecular Hydrogen Bonding in Excited States.
in The journal of physical chemistry letters
Young JD
(2015)
Torsional Motion of the Chromophore Catechol following the Absorption of Ultraviolet Light.
in Physical review letters
Young JD
(2014)
Relaxation dynamics of photoexcited resorcinol: internal conversion versus H atom tunnelling.
in Physical chemistry chemical physics : PCCP
Yu H
(2014)
Tunneling dynamics of the NH3 (Ã) state observed by time-resolved photoelectron and H atom kinetic energy spectroscopies.
in The journal of physical chemistry. A
Description | The work was able to contribute towards an understanding of the photostability of biological building blocks, namely DNA bases and amino acids. |
Exploitation Route | The work can be taken by academic groups studying the photochemistry of much larger biological building blocks to assist them in understanding the photoprotection mechanisms of their systems. |
Sectors | Education |
URL | http://www.go.warwick.ac.uk/teamstavros |
Description | The work involved two teams establishing links with local schools in the Athens district, where the University of Georgia is located. Physics majors studying and UG regularly attend local schools to carry out science shows to inspire the young towards further education. |
First Year Of Impact | 2011 |
Sector | Education |
Impact Types | Societal |
Description | Leverhulme Trust |
Amount | £298,670 (GBP) |
Funding ID | RPG-2015-190 |
Organisation | The Leverhulme Trust |
Sector | Charity/Non Profit |
Country | United Kingdom |
Start | 11/2015 |
End | 09/2018 |