Excited state dynamics of shape-shifting molecules
Lead Research Organisation:
University of East Anglia
Department Name: Chemistry
Abstract
Molecules that change shape (isomerise) in response to light are essential in numerous light-controlled technological applications including optical memory registers, advanced materials and nanotechnological molecular machines capable of performing specific tasks at the microscopic level. In addition to their technological applications, shape-changing 'photoswitch' molecules have widespread biological importance, including roles in vision, phototropism and photosynthesis in bacteria, and ion channel switches. The shape-shifting properties of these photoswitch molecules stems from the existence of two or more distinct isomers that can be toggled following exposure to different colours of light. Each isomer may have unique properties, including molecular volume, colour, solubility, and conductivity.
Improving our molecular-level understanding of the actinic mechanistic details of photoswitching - the so-called excited state dynamics - is critical for the rational design of improved derivatives. Harnessing this knowledge is becoming increasingly important due to the widespread adoption of photoswitches into everyday life, requiring new spectroscopic methodologies that offer increased selectivity and information content. In particular, the spectroscopic toolkit must have the capacity to independently probe the excited state dynamics associated with each isomer, which invariably occurs over the ultrafast femtosecond (0.000000000000001 second) timescale, and also the capacity to characterise branching to multiple photoswitch forms or degradation pathways. It is often difficult or impossible to characterise the inherent photoswitching properties of each isomer using conventional analytical or physical chemistry techniques, particularly when there are several isomers, rapid interconversion and strong environmental influences. This research program will develop new vacuum-based instrumentation and methodology to help address these deficiencies and will focus on applying the toolkit to characterising two classes of molecular photoswitches important in optoelectronics and optical control of biotechnological molecules.
Building on our unique expertise gained from multiple world-leading laboratories, this research program will establish long-term research infrastructure in the UK, permitting study of shape-selected molecules and their ultrafast shape-shifting dynamics. The instrumentation and methodology will provide a distinctive new approach and offer end capabilities that are not possible by any other single research group.
Improving our molecular-level understanding of the actinic mechanistic details of photoswitching - the so-called excited state dynamics - is critical for the rational design of improved derivatives. Harnessing this knowledge is becoming increasingly important due to the widespread adoption of photoswitches into everyday life, requiring new spectroscopic methodologies that offer increased selectivity and information content. In particular, the spectroscopic toolkit must have the capacity to independently probe the excited state dynamics associated with each isomer, which invariably occurs over the ultrafast femtosecond (0.000000000000001 second) timescale, and also the capacity to characterise branching to multiple photoswitch forms or degradation pathways. It is often difficult or impossible to characterise the inherent photoswitching properties of each isomer using conventional analytical or physical chemistry techniques, particularly when there are several isomers, rapid interconversion and strong environmental influences. This research program will develop new vacuum-based instrumentation and methodology to help address these deficiencies and will focus on applying the toolkit to characterising two classes of molecular photoswitches important in optoelectronics and optical control of biotechnological molecules.
Building on our unique expertise gained from multiple world-leading laboratories, this research program will establish long-term research infrastructure in the UK, permitting study of shape-selected molecules and their ultrafast shape-shifting dynamics. The instrumentation and methodology will provide a distinctive new approach and offer end capabilities that are not possible by any other single research group.
People |
ORCID iD |
James Bull (Principal Investigator) |
Publications
Addison K
(2023)
Photophysics of the red-form Kaede chromophore.
in Chemical science
Ashworth E
(2023)
Protomers of the green and cyan fluorescent protein chromophores investigated using action spectroscopy
in Physical Chemistry Chemical Physics
Ashworth EK
(2022)
Excited-State Barrier Controls E ? Z Photoisomerization in p-Hydroxycinnamate Biochromophores.
in The journal of physical chemistry letters
Ashworth EK
(2022)
Cryogenic Fluorescence Spectroscopy of Ionic Fluorones in Gaseous and Condensed Phases: New Light on Their Intrinsic Photophysics.
in The journal of physical chemistry. A
Ashworth EK
(2023)
Alkylated green fluorescent protein chromophores: dynamics in the gas phase and in aqueous solution.
in Physical chemistry chemical physics : PCCP
Ashworth EK
(2022)
Complexation of Green and Red Kaede Fluorescent Protein Chromophores by a Zwitterion to Probe Electrostatic and Induction Field Effects.
in The journal of physical chemistry. A
Bull J
(2023)
Autoionization from the plasmon resonance in isolated 1-cyanonaphthalene
in The Journal of Chemical Physics
Lee J
(2023)
Cooling dynamics of energized naphthalene and azulene radical cations
in The Journal of Chemical Physics
Navarro Navarrete JE
(2023)
Experimental radiative cooling rates of a polycyclic aromatic hydrocarbon cation.
in Faraday discussions
Stockett MH
(2022)
Statistical vibrational autodetachment and radiative cooling rates of para-benzoquinone.
in Physical chemistry chemical physics : PCCP
Title | Gas-phase instrumentation for isomer-selected action spectroscopy of molecular anions |
Description | A new lab-based instrument at UEA combining several ion sources (electrospray ionization, hard and soft plasmas) coupled with ion mobility spectrometry, ion trapping, time-of-flight mass spectrometry and velocity-map imaging. Can be interfaced with a range of tunable wavelength lasers and femtosecond lasers allowing for pump-probe spectroscopy. |
Type Of Material | Improvements to research infrastructure |
Year Produced | 2022 |
Provided To Others? | No |
Impact | This research infrastructure provides new invstigative capabilities that are not available anywhere else in the world. This innovation thus allows new types of experiments on the fundamental photophysics of gas-phase molecules. |
Description | UEA-Aarhus |
Organisation | Aarhus University |
Country | Denmark |
Sector | Academic/University |
PI Contribution | Collaborative experiments on target molecules as part of grant. |
Collaborator Contribution | Offered access to unique instrumental techniques not possible anywhere else in the world. |
Impact | Complexation of green and red Kaede fluorescent protein chromophores by a zwitterion to probe electrostatic and induction field effects [doi: 10.1021/acs.jpca.1c10628] Cryogenic fluorescence spectroscopy of ionic fluorones in gaseous and condensed phases: New light on their intrinsic photophysics [doi: 10.1021/acs.jpca.2c07231] |
Start Year | 2022 |
Description | UEA-Marseille |
Organisation | Aix-Marseille University |
Country | France |
Sector | Academic/University |
PI Contribution | Joint experiments and theoretical studies on some of our target molecules to study. |
Collaborator Contribution | Access to specialised instrumentation and techniques, which complement our experiments. |
Impact | Joint manuscript due to be submitted in late-march 2023. |
Start Year | 2022 |
Description | UEA-Stockholm Physics |
Organisation | Stockholm University |
Country | Sweden |
Sector | Academic/University |
PI Contribution | Collaborative published research, several successful beamtime applications on international facilities, e.g. synchrotrons, many data sets in preparation for publication |
Collaborator Contribution | Specialised expertise and access to unique equipment/instrumentation. |
Impact | Efficient stabilization of cyanonaphthalene by fast radiative cooling and implications for the resilience of small PAHs in interstellar clouds Experimental radiative cooling rates of a Polycyclic Aromatic Hydrocarbon cation Complexation of green and red Kaede fluorescent protein chromophores by a zwitterion to probe electrostatic and induction field effects Cryogenic fluorescence spectroscopy of ionic fluorones in gaseous and condensed phases: New light on their intrinsic photophysics Radiative cooling of polyyne anions: C4H- and C6H- Radiative cooling rates of substituted PAH ions Statistical vibrational autodetachment and radiative cooling rates of para-benzoquinone |
Start Year | 2019 |
Description | UEA-Waterloo |
Organisation | University of Waterloo |
Country | Canada |
Sector | Academic/University |
PI Contribution | Joint experiments on some of the target molecules in the grant. |
Collaborator Contribution | Access to custom instrumentation not avaialble anywhere else in the world. |
Impact | Excited-state barrier controls E ? Z photoisomerization in p-hydroxycinnamate biochromophores (doi: 10.1021/acs.jpclett.2c02613) |
Start Year | 2022 |