Autumn Research Publication Update

The School of Chemistry has published a large number of papers this summer, despite the on-going pandemic – the details of which are below.

Synthesis and Catalysis

  • Fluorinations of unsymmetrical diaryliodonium salts containing ortho-sidearms; influence of sidearm on selectivity: A. M. H. Abudken, E. G. Hope, K. Singh and A. M. Stuart,* Org. Biomol. Chem., 2020, 18, 6140-6146. DOI: https://doi.org/10.1039/D0OB01401J

This paper describes a convenient two-step synthesis of para-fluorinated aromatics.  In the first step the activated aromatic was reacted with a new fluoroiodane reagent via an SEAr reaction to form exclusively the para-substituted diaryliodonium salt containing an ortho-styrene sidearm.  The para-fluorinated aromatics were delivered in good yields in the second step by a copper-catalysed fluorination of the unsymmetrical diaryliodonium salts.

  • Physicochemical surface-structure studies of highly active zirconocene polymerisation catalysts on solid polymethylaluminoxane activating supports: A. F. R. Kilpatrick, N. H. Rees, Z. R. Turner, J.-C. Buffet and D. O'Hare* Mater. Chem. Front., 2020, DOI: 10.1039/D0QM00482K

Part of SK’s postdoctoral work with O’Hare group (Oxford) in partnership with SCG Chemicals (Thailand), investigating the activation of supported metallocene polymerisation catalysts by solid methylaluminoxane, using a range of spectroscopic techniques including 91Zr solid state NMR.

  • Understanding metal synergy in heterodinuclear catalysts for CO2/epoxide copolymerisation: A. C. Deacy, A. F. R. Kilpatrick, A. Regoutz and C. K. Williams*, Nat. Chem., 2020, 12, 372. DOI: 10.1038/s41557-020-0450-3

Collaboration with Williams group (Oxford) reporting a heterodinuclear MgCo catalyst that is highly active for the copolymerization of CO2 and epoxides under low CO2pressures. Its performance arises from the intramolecular synergy between the two metals, which adopt distinct roles and mediate each other’s reactivity during catalysis. SK carried out the magnetometry and cyclic voltammetry experiments.

  • Realising the electrochemical stability of graphene: scalable synthesis of an ultra-durable platinum catalyst for the oxygen reduction reaction: G. M. A. Angel, N. Mansor, R. Jervis, Z. Rana, C. Gibbs, A. Seel, A. F. R. Kilpatrick, P. R. Shearing, C. A. Howard, D. J. L. Brett* and P. L. Cullen*, Nanoscale, 2020, 12, 16113–16122. DOI: 10.1039/D0NR03326J

Highly collaborative project with groups of Brett (UCL) and Cullen (QMUL) reporting a scalable synthesis of Pt nanoparticle-coated graphene whereby PtCl2 is reduced directly by negatively charged single layer graphene sheets in solution. The resultant nanoparticles show high catalytic activity for the oxygen reduction reaction and remarkable stability compared with a commercial catalyst. SK carried out syntheses of graphite intercalation compounds.

  • Ethene activation and catalytic hydrogenation by a low-valent uranium pentalene complex: N. Tsoureas, L. Maron, A. F. R. Kilpatrick, R. A. Layfield, F. G. N. Cloke*, J. Am. Chem. Soc., 2020, 142, 89. DOI: 10.1021/jacs.9b11929

Collaboration with Cloke group (Sussex) reporting a rare example of a uranium complex that allows coordination and activation of ethylene, and its subsequent hydrogenation under mild catalytic conditions. SK carried out the magnetometry and solid state NMR experiments.

Learning Enhancement / Pedagogy

  • “Inspirational Chemists: A Student Conference Activity to Raise Awareness of Diversity and Inclusion in the Chemical Sciences”, Dylan P. Williams* and Khalku Karim, J. Chem. Educ. https://doi.org/10.1021/acs.jchemed.0c00462

This paper provides an overview of a year one student poster conference activity based diversity and inclusion. The activity forms part of our year one Problem Based Learning programme. Students work in teams to research and present the work of chemists with a particular focus of work by chemists from underrepresented demographic groups. The aim of the activity is to facilitate student-student and student-instructor discussions about inclusion and diversity in our subject. The majority of students who participated in this activity reported that it was an effective way to raise their awareness of diversity and inclusion in the subject by initiating discussions of these themes with their peers.

  • 3D Printing Workshop Activity That Aids Representation of Molecules and Student Comprehension of Shape and Chirality: Dickenson, C. E.; Blackburn, R. A. R.; Britton, R. G. J. Chem. Educ. 2020.https://doi.org/10.1021/acs.jchemed.0c00457.

We have created and evaluated a 3D printing workshop activity suitable, but not limited to, small-group undergraduate teaching of stereochemistry. The activity blends question and answer tasks with a complete workflow for students to draw a chiral molecule and prepare it for 3D printing as part of their class time. Comparing data collected before and after the workshop highlights that this activity has led to improvements in student confidences in drawing chiral centers and increases in perceived competences in understanding, representing, and assigning chirality.

  • Go Fischer: An Introductory Organic Chemistry Card Game; Battersby, G. L.; Beeley, C.; Baguley, D. A.; Barker, H. D.; Broad, H. D.; Carey, N. C.; Chambers, E. S.; Chodaczek, D.; Blackburn, R. A. R.; Williams, D. P. J. Chem. Educ. 2020https://doi.org/10.1021/acs.jchemed.0c00504

This contribution describes the student-led development of an introductory organic chemistry card game based on the classic party game Go Fish. The game has been designed to help students practice applying the rules of organic nomenclature, to recognize key functional groups, and to familiarize themselves with simple examples of reactivity of molecules containing these functional groups. Evaluation of the activity shows that students enjoyed playing the game, found it easy to play, and that they found it a useful learning experience.

Spectroscopy and Dynamics

Dr Yang and his co-workers in the NanoChemistry Group discovered single gold atoms within van der Waals complexes can serve as catalysts for the first time.

  • IR Spectroscopy of the Cesium Iodide–Water Complex: Julia A. Davies, Martin Mugglestone, Shengfu Yang, and Andrew M. Ellis, J. Phys. Chem. A 2020, 124, 6528-6535 DOI: https://doi.org/10.1021/acs.jpca.0c05224

This study uses IR laser spectroscopy to determine how a simple salt, CsI, in the form of a single molecule and trapped inside a liquid helium nanodroplet, interacts with a single molecule of water.

  • Assessing visible aerosol generation during vitrectomy in the era of Covid-19. Sidath Liyanage, Pathma Ramasamy, Omar Elhaddad, Kieren Darcy, Andrew Hudson, and Johannes Keller. Nature Eye doi:10.1038/s41433-020-1052-4.

    Chemical Biology

  • Kaur P, Johnson A, Northcote-Smith J, Lu C, Suntharalingam K*, “Immunogenic Cell Death of Breast Cancer Stem Cells by an Endoplasmic Reticulum‐Targeting Copper(II) Complex” ChemBioChem, 2020https://doi.org/10.1002/cbic.202000553

Here we report the first metal complex to display both cytotoxic and immunogenic effects towards breast cancer stem cells in vitro.

  • HDAC3 deacetylates the DNA mismatch repair factor MutSβ to stimulate triplet repeat expansions, G.M. Williams, V. Paschalis, J. Ortega, F. W. Muskett, J.T. Hodgkinson, G. Li, J.W.R. Schwabe, R.S. Lahue. Proc. Natl. Acad. Sci. U.S.A.2020, 117, 23597-23605,  https://doi.org/10.1073/pnas.2013223117

Biotechnology

  • Piletska E. V., Mirkes E., Piletsky S. S., Abosoglu H., Cassim A., Chu E., Doughty S., Eganda S.‐J., Fuchigami H., Hussein A., Olickal M., Parmar N., Sebastian A., Piletsky S. A. (2020). Combinatorial screening of polymer nanoparticles for their ability to recognize epitopes of AAV‐neutralizing antibodies. J Mol. Recogn., 33, e2824.
  • Caro N., Bruna T., Guerreiro A., Alvarez-Tejos P., Garretón V., Piletsky S., González-Casanova J., Rojas-Gómez D., Eherenfeld N. (2020). Florfenicol binding to molecularly imprinted polymer nanoparticles in model and real samples. Nanomaterials10, 306.
  • Cowen T., Stefanucci E., Piletska E., Marrazza G., Canfarotta F., Piletsky S. A. (2020). Synthetic mechanism of molecular imprinting at the solid phase. Macromolecules53, 1435-1442.
  • Kassem S., Mohamed M., Sayour H., Canfarotta F., Piletsky S., Soliman M. A. M. (2020). Functionalized core-shell yttrium oxide nanoparticles as antioxidants agents in heat stressed rats. Biol. Trace Element Res., 1-9.
  • Bottari F., Moro G., Sleegers N., Florea A., Cowen T., Piletsky S., van Nuijs A. L. N., De Wael K. (2020). Electropolymerized o‐phenylenediamine on graphite promoting the electrochemical detection of nafcillin. Electroanalysis32, 135-141.
  • Munawar H., Garcia-Cruz A., Majewska M., Karim K., Kutner W., Piletsky S. A. (2020). Electrochemical determination of fumonisin B1 using a chemosensor with a recognition unit comprising molecularly imprinted polymer nanoparticles. Sens. Actuat. B: Chemical321, 128552.
  • Garcia-Cruz A., Haq I., Di Masi S., Trivedi S., Alanazi K., Cowen T., Piletska E., Adnan M., Piletsky S. A. (2020). Design and fabrication of a smart sensor using in silico epitope mapping and electro-responsive imprinted polymer nanoparticles for determination of insulin levels in human plasma. Biosens. & Bioelectron., 112536.
  • Garcia-Cruz A., Cowen T., Voorhaar A., Piletska E., Piletsky S. A. (2020). Molecularly imprinted nanoparticles-based assay (MINA)-detection of leukotrienes and insulin. Analyst145, 4224-4232.
  • Guha A., Ahmad O. S., Guerreiro A., Karim K., Sandström N., Ostanin V. P., van der Wijngaart W., Piletsky S. A., Ghosh S. K. (2020). Direct detection of small molecules using a nano-molecular imprinted polymer receptor and a quartz crystal resonator driven at a fixed frequency and amplitude. Biosens. & Bioelectron., 112176.
  • Wu B. B., Muhammad T., Aihebaier S., Karim K., Hu Y. T., Piletsky S. A. (2020). Molecularly imprinted polymer based monolith pipette tip for solid-phase extraction of 2, 4-dichlorophenoxyacetic acid in aqueous sample. Anal. Methods, in press.
  • Sergeyeva T., Yarynka D., Dubey L., Dubey I., Piletska E., Linnik R., Antonyuk M., Ternovska T., Brovko O., Piletsky S., El’skaya A. (2020). Sensor based on molecularly imprinted polymer membranes and smartphone for detection of fusarium contamination in cereals. Sensors20, 4304.
  • Piletska E. V., Guerreiro A., Mersiyanova M., Cowen T., Canfarotta F., Piletsky S., Karim K., Piletsky S. (2020). Probing peptide sequences on their ability to generate affinity sites in molecularly imprinted polymers. Langmuir36, 279-283.
  • Canfarotta F., Piletsky S. A., Turner N. W. (2020). Generation of high-affinity molecularly imprinted nanoparticles for protein recognition via a solid-phase synthesis protocol. Pp.183-194, in: Protein Nanotechnology, Humana, New York.
  • Piletsky S., Canfarotta F., Poma A., Bossi A. M., Piletsky S. (2020). Molecularly imprinted polymers for cell recognition. Trends Biotechnol., 38, 368-387.
  • Brahmbhatt H. A., Surtees A., Tierney C., Ige O. A., Piletska E. V., Swift T., Turner N. W. Effect of Polymerisation by Microwave on the Physical Properties of Molecularly Imprinted Polymers (MIPs) Specific for Caffeine. Polymer Chemistry, 10.1039/d0py00921k.
  • Hand R. A., Piletska E., Bassindale T., Morgand G., Turner N. (2020) Application of molecularly imprinted polymers in the anti-doping field: sample purification and compound analysis. Analyst, 145, 4716-4736.

Materials and Interfaces

  • Gamma-phase Zn-Ni Alloy Deposition by Pulse-electroplating from a Modified Deep Eutectic Solution”, Chunhong Lei, Hasan F. Alesary, Farrah Khan, Andrew P. Abbott 1 and Karl S. Ryder , Surf. Coat. Technol.2020, 403, 126434.

This article describes the electroplating of ZneNi alloy from a modified deep eutectic solvent (DES), a mixture of choline chloride (ChCl) and ethylene glycol (EG) commonly known by its commercial name Ethaline.  We demonstrate that it is possible to produce dense, thick and adherent coatings of a γ-phase Zn/Ni alloy with 81–85% Zn on mild steel substrates using either potentiostatic deposition or controlled current pulse-plating techniques.

  • “Effects of additives on the electrodeposition of Zn-Sn alloys from choline chloride/ethylene glycol- based deep eutectic solventEffects of additives on the electrodeposition of Zn-Sn alloys from choline chloride/ethylene glycol-based deep eutectic solvent, Hasan F. Alesary, Hani K. Ismail, Nagham M. Shiltagh,d, Rawaa A. Alattar, Luma M. Ahmed, Mark J. Watkins and Karl S. Ryder, J. Electroanal. Chem., 2020, 874, 114517.

The effects of additives on the electrodeposition of ZnSn alloy from aqueous electrolyte have been the subject of con- siderable interest in the literature; however, to date there has been little consideration of their effects on alloy electro- deposition from Deep Eutectic Solvents (DESs). This work will show, for the first time, the effects of boric acid, ammonium chloride and nicotinic acid on the electrodeposition of ZnSn alloys on copper from a DES consisting of a stoichiometric 1:2 mix of choline chloride and ethylene glycol (Ethaline 200).

  • “Separation of iron(III), zinc(II) and lead(II) from a choline chloride-ethylene glycol deep eutectic solvent by solvent extraction”, Sofia Riano, Stylianos Spathariotis, Nand Peeters, Karl S. Ryder, Andrew P. Abbott, and Koen Binnemans, RSC Advances, 2020, 10, 33161.

Deep eutectic solvents (DESs) were used as alternatives to the aqueous phase in solvent extraction of iron(III), zinc(II) and lead(II). The selective extraction of iron(III) and zinc(II) was studied from a feed of ethaline (1 : 2 molar ratio of choline chloride : ethylene glycol) and lactiline (1 : 2 molar ratio of choline chloride:lactic acid), with the former DES being more selective.  An efficient solvometallurgical flowsheet is proposed for the separation and recovery of iron(III), lead(II) and zinc(II) from ethaline using commercial extractants. Moreover, the process was upscaled in a countercurrent mixer-settler set-up resulting in successful separation and purification.

  • “Evidence supporting an emulsion polymerisation mechanism for the formation of polyaniline”, Sahar S. M. Alabdullah, Hani K. Ismail, Karl. S. Ryder and Andrew P. Abbott, Electrochim Acta, 2020, 354, 136737.

The electropolymerisation of aniline is a well-studied and often used technology. While the mechanism has been investigated in a variety of media these have all concentrated on understanding the process on a molecular level. Anomalies in the electropolymerisation of aniline in four deep eutectic solvents, DESs, using urea, ethylene glycol, glycerol and oxalic acids as hydrogen bond donors with choline chloride led to an investigation of the aniline phase behaviour. This provides the first evidence that polyaniline grows by an emulsion polymerisation mechanism even in aqueous solutions.

  • J.S. Terreblanche, D.L. Thompson, I.M. Aldous, J. Hartley, A.P. Abbott, and K.S. Ryder Experimental Visualization of Commercial Lithium Ion Battery Cathodes: Distinguishing Between the Microstructure Components Using Atomic Force Microscopy J. Phys. Chem. C, 2020, 124, 27, 14622–14631.
  • I. M. Pateli, D. Thompson, S. S. M. Alabdullah, A. P. Abbott, G. R. T. Jenkin, J. M. Hartley The effect of pH and hydrogen bond donor on the dissolution of metal oxides in deep eutectic solvents, Green Chem. 2020, 22,
  • A. Al-Taie, J. Pan P. Polak, M. R. Barer, X. Han, A. P. Abbott, Mechanical properties of 3-D printed polyvinyl alcohol matrix for detection of respiratory pathogens, Journal of the Mechanical Behavior of Biomedical Materials 112 (2020) 104066

Development of techniques from our forensic science colleagues.

Atmospheric Chemistry

  • Panagi, M., Fleming, Z. L., Monks, P. S., Ashfold, M. J., Wild, O., Hollaway, M., Zhang, Q., Squires, F. A., and Vande Hey, J. D.: Investigating the regional contributions to air pollution in Beijing: a dispersion modelling study using CO as a tracer, Atmos. Chem. Phys., 20, 2825-2838, 10.5194/acp-20-2825-2020, 2020.

 

  • Ruiz Villena, C., Anand, J. S., Leigh, R. J., Monks, P. S., Parfitt, C. E., and Vande Hey, J. D.: Discrete-wavelength DOAS NO2 slant column retrievals from OMI and TROPOMI, Atmos. Meas. Tech., 13, 1735-1756, 10.5194/amt-13-1735-2020, 2020.

 

  • Sommariva, R., Cox, S., Martin, C., Borońska, K., Young, J., Jimack, P. K., Pilling, M. J., Matthaios, V. N., Nelson, B. S., Newland, M. J., Panagi, M., Bloss, W. J., Monks, P. S., and Rickard, A. R.: AtChem (version 1), an open-source box model for the Master Chemical Mechanism, Geosci. Model Dev., 13, 169-183, 10.5194/gmd-13-169-2020, 2020.

 

  • Wyche, K. P., Cordell, R. L., Smith M, L., Smallbone, K. L., Lyons, P., Hama, S. M. L., Monks, P. S., Staelens, J., Hofman, J., Stroobants, C., Roekens, E., Kos, G. P. A., Weijers, E. P., Panteliadis, P., and Dijkema, M. B. A.: The spatio-temporal evolution of black carbon in the North-West European ‘air pollution hotspot’, Atmos Environ, 117874, https://doi.org/10.1016/j.atmosenv.2020.1178

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University of Leicester
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Email: chemistry@le.ac.uk

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