This proposal seeks to examine the physicochemical molecular-level origin of macroscopic viscosity and friction.
Background: Viscosity and friction influence the operation of all macroscopic mechanical devices, from the smallest electric motors, to motor engines and the giant turbines found within generators. However, establishing links between molecular-level processes and macroscopic friction and viscosity remains challenging. The equilibrium thermodynamics associated with molecular interactions are well understood from both a theoretical and experimental perspective.1 However, equilibrium thermodynamics do not necessarily relate to viscosity and friction, which are kinetic processes. Furthermore, modelling solvent dynamics associated with kinetic processes remains in its infancy due to the enormous computational processing demands required, particularly when solvents are involved. This challenge is further compounded by a lack of experimental, molecular-level data with which to benchmark emerging methods. It is also worthy of note that mechanochemistry and the study of nanomechanical processes is a particularly hot topic within chemistry following the award of the 2016 Nobel prizes for chemistry to the development of molecular machines.2,3
Experimental methodology: Here we propose to perform an empirical investigation of the kinetics of molecular-level processes and solvent effects that govern macroscopic viscosity and friction. The Cockroft group are experts in molecular recognition phenomenon in solution through the combined use of experiment and theory.4-9 We propose to expand our investigations from the measurement of equilibrium thermodynamics to now encompass the kinetics of molecular interactions. Due to the relevance in engineering contexts, we propose to examine the kinetics of molecular-level processes that contribute to friction and viscosity. The student working on this project will receive training in a range of modern experimental and analytical techniques associated with physical organic chemistry including:
• organic synthesis
• theoretical background in molecular recognition
• NMR spectroscopy
• X-ray crystallography
• quantitative structure activity relationships
• computational modelling
Previous research experience in synthetic chemistry is required. Applicants must be in possession of (or expecting to obtain) a first class or upper-second class degree (or equivalent) in Chemistry or other cognate discipline before the start of the PhD. Applicants MUST be either be EU or UK nationals. To apply, email a copy of your CV to [email protected]
. Please include a brief description of your previous research experience and current research interests. Applications will be considered on a first-come, first-served basis and the post will be filled as soon as a suitable candidate is identified, thus, prompt applications are encouraged.
Further information: http://homepages.ed.ac.uk/scockrof/research.php
The School of Chemistry holds a Silver Athena SWAN award in recognition of our commitment to advance gender equality in higher education. The University is a member of the Race Equality Charter and is a Stonewall Scotland Diversity Champion, actively promoting LGBT equality. The University has a range of initiatives to support a family friendly working environment. See our University Initiatives website for further information. University Initiatives website: https://www.ed.ac.uk/equality-diversity/help-advice/family-friendly
(1) Hunter, C. A., Quantifying Intermolecular Interactions: Guidelines for the Molecular Recognition Toolbox. Angew. Chem. Int. Ed. 2004, 43, 5310-5324.
(2) Leigh, D. A., Genesis of the Nanomachines: The 2016 Nobel Prize in Chemistry. Angew. Chem. Int. Ed. 2016, 55, 14506-14508.
(3) Panman, M. R.; Bakker, B. H.; den Uyl, D.; Kay, E. R.; Leigh, D. A.; Buma, W. J.; Brouwer, A. M.; Geenevasen, J. A. J.; Woutersen, S., Water Lubricates Hydrogen-Bonded Molecular Machines. Nature Chem. 2013, 5, 929-934
(4) T. A. Hubbard, A. J. Brown, I. A. W. Bell, S. L. Cockroft. The limit of intramolecular H-bonding. J. Am. Chem. Soc., 2016, 138, 15114-15117.
(5) Yang, L.; Adam, C.; Nichol, G. S.; Cockroft, S. L., How Much Do Van Der Waals Dispersion Forces Contribute to Molecular Recognition in Solution? Nature Chem. 2013, 5, 1006-1010.
(6) Dominelli-Whiteley, N.; Brown, J. J.; Muchowska, K. B.; Mati, I. K.; Adam, C.; Hubbard, T. A.; Elmi, A.; Brown, A. J.; Bell, I. A. W.; Cockroft, S. L., Strong Short-Range Cooperativity in Hydrogen-Bond Chains. Angew. Chem. Int. Ed. 2017, 56, 7658-7662.
(7) Adam, C.; Yang, L.; Cockroft, S. L., Partitioning Solvophobic and Dispersion Forces in Alkyl and Perfluoroalkyl Cohesion. Angew. Chem. Int. Ed. 2015, 54, 1164-1167.
(8) Yang, L.; Adam, C.; Cockroft, S. L., Quantifying Solvophobic Effects in Nonpolar Cohesive Interactions. J. Am. Chem. Soc. 2015, 137, 10084-10087.
(9) Muchowska, K. B.; Adam, C.; Mati, I. K.; Cockroft, S. L., Electrostatic Modulation of Aromatic Rings Via Explicit Solvation of Substituents. J. Am. Chem. Soc. 2013, 135, 9976-9979.