Spring/Summer Research Publication Update

The School of Chemistry at University of Leicester has published in excess of 25 papers in the first half of 2020. These are listed below according to their research groupings.

Synthesis and Catalysis

  • B(C6F5)3-Catalyzed Direct C3 Alkylation of Indoles and Oxindoles: Shyam Basak, Ana Alvarez-Montoya, Laura Winfrey, Rebecca L. Melen, Louis C. Morrill, and Alexander P. Pulis, ACS Catalysis 10 (8), 4835-4840 DOI: 10.1021/acscatal.0c01141

Indoles and oxindoles are prevalent motifs in biologically active molecules that are used to study and treat disease. Yet, the direct C3 alkylation of indoles and oxindoles remains a significant challenge. Utilizing underexplored reactivity of triaryl boranes, we have developed a catalytic approach for the direct C3 alkylation of a wide range of indoles and oxindoles.

  • Strangely attractive: Collaboration and feedback in the field of molecular magnetism: C.A.P. Goodwin, F. Ortu,* D. Reta, Int. J. Quantum Chem., 202014, e26248 DOI: 10.1002/qua.26248.

Short perspective article on the collaboration between physicist, theoreticians and experimental chemists in the field of molecular magnetism, focusing on some of the research FO carried out over the last 5 years.

  • Understanding magnetic relaxation in single-ion magnets with high blocking temperature: A. Chiesa, F. Cugini, R. Hussain, E. Macaluso, G. Allodi, E. Garlatti, M. Giansiracusa, C. A. P. Goodwin, F. Ortu, D. Reta, J. M. Skelton, T. Guidi, P. Santini, M. Solzi, R. De Renzi, D. P. Mills, N. F. Chilton, S. Carretta, Phys. Rev. B2020101, 174402, DOI: 10.1103/PhysRevB.101.174402.

Multidisciplinary study on the physical phenomena that govern Single Molecule Magnets.

  • Probing relaxation dynamics in five-coordinate dysprosium single-molecule magnets: V. S. Parmar, F. Ortu, X. Ma, N.F. Chilton, R. Clerac, D. P. Mills, R. E. P. Winpenny, Chem. Eur. J.202035, 7774, DOI: 10.1002/chem.202001235.

Another magnetism paper.

  • A double-dysprosocenium single-molecule magnet bound together with neutral ligands: P. Evans, D. Reta. C. A. P. Goodwin, F. Ortu, N. F. Chilton, D. P. Mills, Chem. Commun.202056, 5677, DOI: 10.1039/C9CC08945D.

Another magnetism paper.

  • Dimerized p-Semiquinone Radical Anions Stabilized by a Pair of Rare-Earth Metal Ions: T. Han, J. B. Petersen, Z.-H. Li, Y.-Q. Zhai, A. Kostopoulos, F. Ortu, E. J. L. McInnes, R. E. P. Winpenny, Y.-Z. Zheng, Inorg. Chem.202059, 7371 DOI: 10.1021/acs.inorgchem.0c00503.
Another magnetism paper.
  • Synthesis and characterisation of light lanthanide bis-phospholyl borohydride complexes: J. Liu, L. Nodaraki, P. Cobb, M. Giansiracusa, F. Ortu, F. Tuna, D. P. Mills, Dalton Trans202049, 6504 DOI: 10.1039/D0DT01241F.

Collaborative paper working on the organometallic chemistry and physical properties of unusual phospholyl lanthanide complexes.

  • 2-Acetyloxymethyl-substituted 5,6,7-trihydroquinolinyl-8-ylideneamine-Ni(II) chlorides and their application in ethylene dimerization/trimerization. J. Li, Q. Zhang, X. Hu, Y. Ma, G. A. Solan, Y. Sun and W.-H. Sun, Appl. Organomet. Chem., 2020, 34, e5254. [DOI: 10.1002/aoc.5254]

Selectivity for converting ethylene to uniquely 1-butene or 1-hexene represents a major challenge in catalysis. Herein, structural variations to the nickel catalyst and conditions are shown to be influential.

  • Probing the effect of ortho-cycloalkyl ring size on activity and thermostability in cycloheptyl-fused N,N,N-iron ethylene polymerization catalysts. J. Guo, W. Zhang, I. I. Oleynik, G. A. Solan, I. V. Oleynik and W.-H. Sun, Dalton Trans., 2020, 49, 136-146. [DOI: 10.1039/C9DT04325J]

The balancing of high catalytic activity with good thermal stability represents a key challenge in iron-promoted alkene polymerization. We manage this through strategic ligand design.

  • Recent advancements in N-ligated group IV metal catalysts for the (co polymerization of ethylene. S.-F. Yuan, Y. Yan, G. A. Solan, Y. Ma and W.-H. Sun, Coord. Chem. Rev., 2020, 411, 213254. [DOI: 10.1016/j.ccr.2020.213254] For a Virtual Special Issue of Coordination Chemistry Reviews entitled “Early Transition Metal Coordination Chemistry: From Design to Application”.

The review covers cutting-edge developments in the field group IV (Zr, Ti, Hf) catalysts for the polymerisation and copolymerization of ethylene.

  • High molecular weight polyethylenes of narrow dispersity promoted using bis(arylimino)-5,6,7,8-tetrahydrocycloheptapyridine-cobalt catalysts ortho-substituted with benzhydryl & cycloalkyl groups. M. Han, Q. Zhang, I. I. Oleynik, H. Suo, G. A. Solan, I. V. Oleynik, Y. Ma, T. Lianga and W.-H. Sun, 2020, Dalton Trans., 2020, 49, 4774-4784 [DOI: 10.1039/D0DT00576B]

The control of the intrinsic properties of a polyethylene through catalyst design has been achieved through systematic variation to the ligand structure of a cobalt catalyst.

  • Ruthenium-catalyzed Hydrogenation of CO2 as a Route to Methyl Esters for use as Biofuels or fine Chemicals. Z. Wang, Z. Zhao, Y. Li, Y. Zhong, Q. Zhang, Q. Liu, G. A. Solan, Y. Ma and W.-H. Sun, 2020, Chem. Sci., Advance Article, DOI: 0.1039/D0SC02942D.

A sustainable process has been developed for the first time that converts carbon dioxide to highly prized products like biodiesel and fine chemicals.

  • Bis-cycloheptyl-fused bis(imino)pyridine-cobalt catalysts for PE wax formation: positive effects of fluoride substitution on catalytic performance and thermal stability. Q. Zhang, N. Wu, J Xiang, G. A. Solan, H. Suo, Y. Ma, T. Liang and W.-H. Sun, Dalton Trans., Advance Article, DOI: 10.1039/d0dt01876g.

The beneficial effect of fluoride substitution on the catalytic activity and thermal stability of a cobalt ethylene polymerization catalyst is demonstrated.

Materials and Interfaces

  • Experimental Vizualisation of Commercial Lithium Ion Battery Cathodes: Distinguishing Between the Microstructure Components Using Atomic Force Microscopy”, J.S. Terreblanche, D.L. Thompson, I.M. Aldous, J. Hartley, A.P. Abbott and K.S. Ryder, J. Phys. Chem C, 2020, (in press) .

We have been able to, identify the mechanism by which the active material in lithium-ion batteries binds together and how the conductive network is formed.  These insights re vital to the manufacture, use and recycling of battery materials.  The work is funded by the Faraday Institution.

  • S. Higashino, A. P. Abbott, M. Miyake, T. Hirato, Iron(III) chloride and acetamide eutectic for the electrodeposition of iron and iron based alloys, Electrochim. Acta, 2020, 351, 1364144 DOI 10.1016/j.electacta.2020.136414

The electrodeposition of iron and iron-based alloys is important for a variety of coating technologies. This study demonstrates that eutectics of ferric chloride and acetamide are easily formed and a 1:4 molar mixture gives a liquid at ambient temperature. This eutectic mixture has a higher conductivity resulting from a lower viscosity than comparable eutectics formed from either aluminium or zinc chloride. Ferric chloride disproportionates to form both anionic and cationic iron containing species and these were identified using a variety of spectroscopic methods. The electrodeposition of iron and iron-nickel alloys was demonstrated and it was shown that the iron-nickel alloys demonstrated improved anti-corrosion properties.

  • I. Korolev, S. Spathariotis, K. Yliniemi, B. P. Wilson, A. P. Abbott and M. Lundström,  Mechanism of selective gold extraction from multi-metal chloride solutions by electrodeposition-redox replacement, Green Chem., 2020, 22, 3615-3625. DOI 10.1039/D0GC00985G

******* selected by Editors and featured as a 2020 HOT Green Chemistry article************

The detailed reaction mechanisms of the EDRR in Cu-Au systems, as well as the effect of the reaction medium are elucidated in this article. Electrogravimetric studies show that the EDRR process comprises of three distinct stages: 1) deposition of Cu at a constant applied potential; 2) dissolution of deposited Cu at open circuit conditions in reaction with dissolved species in solution; 3) reduction of Au to elemental form in reaction with various Cu species. Therefore, the EDRR enables energy and resource efficient selective extraction of Au from multi-metal industrial solutions even when it is present at low concentrations.

Spectroscopy and Dynamics

  • “Shifting Formic Acid Dimers into Perspective: Vibrational Scrutiny in Helium Nanodroplets” K. A. E. Meyer, J. A. Davies, A. M. Ellis, Phys. Chem. Chem. Phys. 22, 9637- 9646 (2020). DOI 10.1039/D0CP01060J

This was a piece of work involving a visiting PhD student from the University of Gottingen, Katharina Meyer and a University of Leicester postdoc, Julia Davies, in AME research group. It provides new information about the hydrogen bonding between two molecules of the simple carboxylic acid, formic acid, explored using a technique which traps those molecules in liquid helium nanodroplets.

Chemical Biology

  • Adoption of a Turn Conformation Drives the Binding Affinity of p53 C-Terminal Domain Peptides to 14-3-3σ, A. Kuusk, J. F. Neves, K. B. Rodriguez, A. Gunnarsson., Y. B. Ruiz-Blanco, M. Ehrmann, H. Chen, I. Landrieu, E.Sanchez-Garcia, H. Boyd, C. Ottmann, R. G. Doveston* – ACS Chem. Bio. 2020, 262-271. DOI 10.1021/acschembio.9b00893

Our study contributes to elucidate the molecular mechanism of the 14-3-3-p53 binding and provides useful insight into how conformation properties of a ligand influence protein binding

  • Fragment-based Differential Targeting of PPI Stabilizer Interfaces, X. Guillory, M. Wolter, S. Leysen, J. F. Neves, A. Kuusk, S. Genet, B. Somsen, J. Morrow, E. Rivers, L. van Beek, J. Patel, R. Goodnow, H. Schoenherr, N. Fuller, Q. Cao, R. G. Doveston, L. Brunsveld, M. R. Arkin, M. P. Castaldi, H. Boyd, I. Landrieu, H. Chen, C. Ottmann, J. Med. Chem. 2020, In Press, DOI: 10.1021/acs.jmedchem.9b01942.

This X-ray crystallography driven study shows that the rim of the interface of individual 14-3-3 complexes can be targeted in a differential manner with fragments that represent promising starting points for the development of specific 14-3-3 PPI stabilizers.

  • Elucidation of an Allosteric Mode-of-Action for a Thienopyrazole RORgt Inverse Agonist, R. M. J. M. de Vries, F. A. Meijer, R. G. Doveston, L. Brunsveld – ChemMedChem 2020, 561-565. DOI 10.1002/cmdc.202000044

Using a combination of biochemical and X-ray crystallography studies, here the allosteric mechanism for the inverse agonism for the most potent compound, classified in the patent as "example 13", is reported, providing a strongly desired additional example of allosteric nuclear receptor targeting.

  • Ligand-based Design of Allosteric RORγt Inverse Agonists, F. A. Meijer, R.G. Doveston, R. M. J. M. de Vries, G. Vos, A. Vos, M. Scheepstra, S. Leysen, C. Ottmann, L.-G. Milroy and L. Brunsveld J. Med. Chem. 2020, 241-259. DOI 10.1021/acsjmedchem.9b01372

The isoxazole compounds have promising pharmacokinetic properties comparable to other allosteric ligands but with a more diverse chemotype. The efficient ligand-based design approach adopted demonstrates its versatility in generating chemical diversity for allosteric targeting of RORγt.

  • PROTAC-mediated degradation of class I histone deacetylase enzymes in corepressor complexes, J. P. Smalley, G. E. Adams, C. J. Millard, Y. Song, J. K. S. Norris,  J. W. R. Schwabe, S. M. Cowley, J. T. Hodgkinson, Chem. Commun. 2020, 56, 4476-4479. DOI 10.1039/D0CC01485K

We have identified a proteolysis targeting chimera (PROTAC) of class I HDACs 1, 2 and 3. The most active degrader consists of a benzamide HDAC inhibitor, an alkyl linker, and the von Hippel-Lindau E3 ligand. Our PROTAC increased histone acetylation levels and compromised colon cancer HCT116 cell viability, establishing a degradation strategy as an alternative to class I HDAC inhibition.

  • Robin P, Singh K, Suntharalingam K*, “Gallium(III)-polypyridyl complexes as anti-osteosarcoma stem cell agents” Chemical Communications, 2020, 56, 1509-1512. DOI 10.1039/C9CC08962D

  • Eskandari A, Kundu A, Johnson A, Karmakar S, Ghosh S, Suntharalingam K*, “A tri-metallic palladium complex with breast cancer stem cell potency” Dalton Transactions, 2020, 49, 4211-4215. DOI 10.1039/D0DT00006J

  • Eskandari A, Flamme M, Xiao Z, Suntharalingam K*, “The Bulk Osteosarcoma and Osteosarcoma Stem Cell Activity of a Necroptosis‐Inducing Nickel(II)–Phenanthroline Complex” ChemBioChem, 2020, DOI: 10.1002/cbic.202000231.

  • Feld C, Johnson A, Xiao Z, Suntharalingam K*, “Breast cancer stem cell potency of nickel(II)‐polypyridyl complexes containing non‐steroidal anti‐inflammatory drugs” Chemistry - A European Journal, 2020, DOI: 10.1002/chem.202001578.

Atmospheric Chemistry

  • Nitrous acid (HONO) emissions under real-world driving conditions from vehicles in a UK road tunnel: Louisa J. Kramer, Leigh R. Crilley, Thomas J. Adams, Stephen M. Ball, Francis D. Pope, and William J. Bloss, Atmos. Chem. Phys., 20, 5231–5248, 2020, DOI: 10.5194/acp-20-5231-2020

We measured HONO and NOx inside the Queensway road tunnel under central Birmingham. We found that the ratio of HONO to NOx emissions averaged 0.85%, with higher HONO fractions emitted when more diesel vehicles were using the tunnel. Interestingly, our result is close to the 0.8% HONO to NOx ratio found by a widely-cited study that made measurements in a road tunnel in Germany some 20 years ago. This similarity shows that, although substantial improvements have been made in vehicle emission technology, the overall HONO to NOx emission ratio remains largely unchanged, most likely due to the higher percentage of diesel vehicles on today’s roads.

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Department of Chemistry
University of Leicester
Leicester, LE1 7RH, UK

Email: chemistry@le.ac.uk

Tel: [+44] (0)116 252 2100

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