Prof Victor Chechik, Prof Deborah O'Connell, Prof P O'Brien
No more applications being accepted
Competition Funded PhD Project (European/UK Students Only)
About the Project
Free radicals are key intermediates in many industrially-important reactions, including polymerisations, oxidations and reductions. Recent development of new methodology (e.g., photoredox catalysis) has reinvigorated interest in free radical chemistry, and many new synthetic procedures have emerged. Contrary to common belief, free radical reactions are often very selective, they proceed under very mild reaction conditions and show excellent functional group tolerance.
All radical reactions need to be initiated, which is commonly done using thermal or photochemical initiators, such as azo derivatives (e.g., well-known AIBN) or organic peroxides. These initiators, however, are hazardous compounds. The use of transition metals for radical initiation also has drawbacks, as their separation from the reaction mixture can be difficult. Therefore, there is great demand for alternative ways of initiating radical chemistry, which would avoid the use of UV irradiation and hazardous or toxic compounds.
This project is based on our preliminary results, which demonstrated that non-thermal plasmas can be used as a green alternative to initiate free radical chain reactions. Non-thermal plasmas are basically electrical discharges that operate at room temperature and atmospheric pressure. They can be readily ignited and maintained thanks to recent technological developments. Non-thermal plasmas produce many reactive species (including free radicals!) and are currently finding applications in many areas including antimicrobial treatment in food processing, sterilisation and bleaching of teeth, in wound healing and tissue regeneration, in treatment of cancerous cells. Their use in Chemistry, however, has been largely overlooked, and our project aims to fill this gap.
In this project, we will develop a non-thermal plasma set-up that could be used to initiate radical chemistry with conventional laboratory equipment. In order to optimise plasma parameters, we will carry out a mechanistic study of free radical intermediates and build a parameter-reactivity relationship. This mechanistic part of the project will benefit from our established expertise in characterisation and monitoring of free radical intermediates (including EPR spectroscopy).
In the second part of the project, we will use non-thermal plasmas to initiate a range of industrially-relevant, synthetically-useful free radical reactions. Some examples are shown in Figure 1. We will compare the efficiency, selectivity and timescale of these reactions to those initiated by conventional initiators. We hope that the results of this project will lead to the development of plasma initiation methodology to the level where it can be taken up by both academic and industrial communities.
The project is a collaboration with Dr Deborah O’Connell (York Plasma Institute) who will provide expertise in plasma technology. The project also includes collaboration with Prof Peter O’Brien whose expertise in organic synthesis will be invaluable for the second part of the project.
Shortlisting will take place as soon as possible after the closing date and successful applicants will be notified promptly. Shortlisted applicants will be invited for an interview to take place at the University of York on either the 13 or 15 February 2018. Candidates will be asked to give a short presentation prior to their interview by an academic panel.
All research students follow our innovative Doctoral Training in Chemistry (iDTC): cohort-based training to support the development of scientific, transferable and employability skills. The project is highly interdisciplinary and will provide an excellent opportunity to learn many new techniques. The genuine complementarity of research expertise of the three supervisors will ensure that the student receives training in all relevant areas. This includes hands-on training in designing and building plasma set-up which will enhance the students’ problem-solving and engineering skills. The student will also receive extensive training in mechanistic chemistry and organic synthesis. We hope to include student placement in industry, to facilitate knowledge transfer and dissemination, and make the student appreciate the issues related to the scale-up and the adoption of a new technology by the industry.
The Department of Chemistry holds an Athena SWAN Gold Award and is committed to supporting equality and diversity for all staff and students. This PhD project is available to study full-time or part-time (50%).
Funding Notes
Studentships are fully funded either by the EPSRC or a Department of Chemistry Teaching Studentship, and cover: (i) a tax-free annual stipend at the standard Research Council rate (£14,553 for 2017-18), (ii) tuition fees at the UK/EU rate. EPSRC studentships are available to UK and EU students who meet the UK residency requirements. Students from EU countries who do not meet the residency requirements may still be eligible for a fees-only award. Chemistry Teaching Studentships are available to any student who is eligible to pay tuition fees at the home rate.
References
Y. Gorbanev, D. O’Connell, V. Chechik, Chem. Eur. J. 2016, 22(10), 3496-3505.
Y. Gorbanev, N. Stehling, D. O’Connell, V. Chechik, Plasma Sources Sci. Technol. 2016, 25(5), 055017.
Y. Gorbanev, D. Leifert, A. Studer, D. O’Connell, V. Chechik, Chem. Comm. 2017, 53(26), 3685-3688.