PhD Studentship - Light-coupled NMR Spectroscopy as a Tool for Mechanistic Studies of Photo-driven Chemistry

Research theme: Fundamental science

This project is funded by EPSRC DTG. The PhD studentship is available for home (UK) candidates only and will cover home fees and provide a tax free stipend set at the UKRI rate (£18,622 in 2023/24). The start date is 1st October 2024. The PhD is 4 years in duration.

The whole life of the planet depends on the light that drives photosynthetic chemical reactions, ultimately supplying food, capturing carbon dioxide from the atmosphere, and creating fuels that produce heating and electric energy. In recent years, light has been increasingly harnessed to produce energy directly, e.g. in solar cells, to split water-producing hydrogen, to trigger the targeted release of drugs in the human body, control the properties of new smart materials, and drive a multitude of photoredox reactions. Therefore, developing analytical techniques that capture the diverse effects of light on matter is required for the development of new platforms across chemistry, material science, biochemistry, biotechnology, synthetic biology, and physics.

One of the most universal analytical techniques to study the structure and properties of matter is nuclear magnetic resonance (NMR) spectroscopy, which allows the observation of signals from individual atoms, thus reporting on matter with atomic-level precision. NMR is a workhorse method in chemistry, but until recently it has proven challenging to record NMR spectra in situ under illuminated conditions; arrangements being cumbersome, involving complex and fragile optical fibers, potentially dangerous lasers, and sample illumination being non-uniform. We recently reported a solution to this problem using a novel NMRtorch approach [1-3], where a special NMR tube itself acts as both a light guide and a sample container, allowing to illuminate the sample efficiently and uniformly at different wavelengths simultaneously, with full control. This pioneering approach opens a way to study a variety of photoresponsive systems and conduct sophisticated experiments, where chemical reactions are monitored live.

The project is a collaboration with Dr. Aaron Trowbridge, on studies of photoredox catalysis, and Dr. Louise Nartajan on photoswitchable molecules for smart materials, as typical areas where the benefits of light-coupled NMR spectroscopy can be immediately explored and realized. The PhD Student, who will be jointly supervised, will work further on developing the NMRtorch approach and applying it to study a range of existing and new photo-switchable dyes (organic azobenzenes, stilbenes, spiroxazines and their transition metal complexes), thus creating working prototypes for smart materials’ applications, and to study the mechanism of formation of versatile iminium ion intermediates in the photocatalytic oxidation of alkylamines[4], developing a roadmap for chemists to choose appropriate photocatalysts and conditions for specific amine classes and desired regioselectivities. Application of NMRtorch to study such diverse photochemical processes would provide a breakthrough in the research field and will suit a candidate with a strong interest in photochemistry or material science, wishing to participate in cutting-edge developments.

Applicants should have, or expect to achieve, at least a 2.1 honours degree or a master’s (or international equivalent) in a relevant science or engineering related discipline.

We strongly recommend that you contact the supervisor(s) for this project before you apply. Contact Dr. Alexander Golovanov [email protected] .