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How do molecules interact with nanoparticles?


   Department of Chemistry

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  Prof Victor Chechik  No more applications being accepted  Competition Funded PhD Project (UK Students Only)

About the Project

Background

Nanoparticles are used in many different areas including catalysis, drug delivery, sensing. Their applications critically depend on the interactions with small molecules. For instance, in nanoparticle catalysis, reagent molecules need to adsorb on the catalyst surface prior to the reaction. In drug delivery, the therapeutic cargo must bind to the nanoparticle until the release is triggered. In sensing, the interaction between the molecule and the nanoparticle results in a detectable signal.

 Thanks to the developments in supramolecular chemistry, much is already known about non-covalent interactions in well-defined small molecule systems (e.g., host-guest interactions). In larger well-defined systems such as proteins or other biomacromolecules, intermolecular interactions have also been studied in detail. However, there is very little knowledge on the interactions in less well-defined materials such as nanoparticles, and the flexibility of these systems is likely to significantly affect their interactions. How strongly do small molecules bind to nanoparticles, and can we rationally tune this interaction by altering the properties of the organic shell on the nanoparticles? How fast is the binding, is it reversible, and how does this reversibility depend on the properties of the organic shell? These are the types of questions which are the focus of the current project.

 Objectives and Novelty

The aim of this project is to observe and quantify the interactions between small molecules and functionalised nanoparticles. The project will start with developing a methodology for studying such interactions, and will then apply it to a range of well-characterised systems. Understanding these interactions will help us rationally design better drugs, sensors and catalysts.

 Experimental Approach

The main method we will use to probe interactions with nanoparticles is EPR spectroscopy. We will label nanoparticles and/or small molecules with stable free radicals (nitroxides). EPR spectroscopy is ideally suited for studying interactions in complex nanosized systems, as only free radical labels contribute to the spectra. EPR is sensitive to a number of key parameters affected by intermolecular interactions, such as rate of tumbling, distance between adjacent labels, collisions between the labels. The changes of these parameters can be monitored in situ in fluid solutions making it possible to probe weak reversible interactions.

 We will use several model nanoparticle systems complementary to the existing projects in our group. In the first instance, we will functionalise silica nanoparticles with an organic shell, and investigate binding of labelled guest molecules. The organic shell will be varied to change its thickness (e.g., using polymers with different chain length), and the properties of the functional groups in the shell (e.g., polarity, hydrogen-bonding ability etc). We are particularly interested in understanding the strength and rate of binding and selectivity. The project will then expand to look at other nanoparticle systems including magnetic and semiconductor nanoparticles. With some of these materials, shape and size can be easily controlled, and we will aim to understand their impact on intermolecular interactions.

 While EPR is likely to be the main tool for this study, other in situ methods will also be used as appropriate, (e.g., NMR, other types of spectroscopy, calorimetry).

 Training

The project is very interdisciplinary and will provide ample opportunities for learning new techniques for which training will be provided. At the start of the project, some organic and nanoparticle synthesis and characterization will be needed. Later in the project, training in advanced EPR spectroscopy and other analytical techniques will be provided. All Chemistry research students have access to our innovative Doctoral Training in Chemistry (iDTC): cohort-based training to support the development of scientific, transferable and employability skills: https://www.york.ac.uk/chemistry/postgraduate/cdts/

The Department of Chemistry holds an Athena SWAN Gold Award and is committed to supporting equality and diversity for all staff and students. The Department strives to provide a working environment which allows all staff and students to contribute fully, to flourish, and to excel: https://www.york.ac.uk/chemistry/ed/.

For more information about the project, click on the supervisor's name above to email the supervisor. For more information about the application process or funding, please click on email institution

This PhD will formally start on 1 October 2022. Induction activities may start a few days earlier.

To apply for this project, submit an online PhD in Chemistry application:

https://www.york.ac.uk/study/postgraduate/courses/apply?course=DRPCHESCHE3

You should hold or expect to achieve the equivalent of at least a UK upper second class degree in Chemistry or a related subject.  


Funding Notes

Fully funded for 3 years by the Department of Chemistry and covers: (i) a tax-free annual stipend at the standard Research Council rate (£15,609 for 2021-22), (ii) tuition fees at the Home rate, (iii) funding for consumables. See guidance for further details: https://www.york.ac.uk/chemistry/postgraduate/research/dept-stud/
Studentships are available to any student who is eligible to pay tuition fees at the home rate: https://www.york.ac.uk/study/postgraduate-research/fees/status/
Not all projects will be funded; candidates will be appointed via a competitive process.

References

Recent examples of how EPR was used to characterize interactions in supramolecular and nanoscale systems include work from our lab (J. D. Nicholas, V. Chechik, J. Phys. Chem. B 2020, 124, 5646) and elsewhere (R. Krzyminiewski, B. Dobosz, G. Schroeder, J. Kurczewska, Sci. Rep. 2019, 9, 18733).
Candidate selection process:
• You should hold or expect to receive at least an upper second class degree in chemistry or a chemical sciences related subject
• Applicants should submit a PhD application to the University of York by 28 February 2022
• Supervisors may contact candidates either by email, telephone or web-chat
• Supervisors can nominate up to 2 candidates to be interviewed for the project
• The interview panel will shortlist candidates for interview from all those nominated
• Shortlisted candidates will be invited to a panel interview on 30th or 31st March or 1stApril
• The awarding committee will award studentships following the panel interviews
• Candidates will be notified of the outcome of the panel’s decision by email

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