Research Guides

 

Research

My interests are concerned with the application of organic chemistry to the synthesis of biologically relevant compounds and the functionalisation of materials.

Synthesis of Bioactive Compound Libraries

Natural products exhibit wide biological activities, and therefore provide inspiration for the development of new drugs and medicinally active compounds.  An important subset contain pyrrolidine and piperidine rings as a core structure, and are of considerable importance because of their antibiotic, antibacterial, antifungal and anticancer properties. We have developed synthetic methodology allowing simple, short, efficient and versatile access to such heterocycles based upon the manipulation of bicyclic ring templates, which allows control of both relative and absolute stereochemistry, and moreover gives several points of diversity on the ring periphery for further derivatisation. Current efforts focus on the application of this methodology for the rapid preparation of chiral heterocyclic libraries for the identification of new antibacterials and anticancer agents.

Functionalisation of Materials

We have developed technology for the chemical modification of material surfaces under mild conditions; it permits the introduction of useful functionality on to what would otherwise be considered to be inert materials and gives a chemically irreversible modification to the polymer. We have shown that highly reactive diarylcarbene intermediates, easily generated under thermolytic or photolytic conditions, can be used for the modification of a wide variety of polymers, including natural (cotton) as well as synthetic materials (polystyrene, polyethylene, polyethyleneterephthalate, nylon as well as low surface energy materials such as polypropylene and PTFE), to introduce a range of surface activity, including colour, fluorescence, hydrophilicity/hydrophobicity, antibacterial function and adhesive modifications. The methodology is intrinsically flexible, being applicable to powders, beads, films and sheets, as well as woven and non-woven fabrics. The modification leads to a surface coverage of 5-20% of the surface area, but is not a simple molecular monolayer; rather it extends to the nano-dimension, but does not lead to surface film formation, surface degradation or other visible change in the material surface. Current research effort is focused on elaboration on the technology for different macroscopic effects, and for the control of the material interface with biological systems, suitable for application in biomedical devices, sensors and implants.

 

Selected Publications

Publications related to bioactive compounds:

 “A detailed study of antibiotic 3-acyltetramic acids and 3-acylpiperidine-2,4-diones”, Y.-C. Jeong, M. Anwar, M. G. Moloney, Z. Bikadi and E. Hazai, ChemMedChem, 2014, 9, 1826 – 1837 (DOI: 10.1002/cmdc.201402093).

 “Direct Synthesis of Mimics of Pramanicin from Pyroglutamic acid, and an Evaluation of their Antibacterial Activity”, S.W.B. Tan, C. Chai and M. G. Moloney, J. Org. Chem., 2015, 80 (5), 2661–2675.

“Stereoselectivity in the Reduction of Bicyclic Tetramates, and an Evaluation of their Antibacterial Activity”, L.J. Cullere and M. G. Moloney, and Amber Thompson, Synlett., 2016, 27, 1677-1681 (DOI: 10.1055/s-0035-1561942).

 “Chemoselectivity and Stereoselectivity of Cyclisation Pathways leading to Bicyclic Tetramates Controlled by Ring-Chain Tautomerisation”, T.D. Panduwawala, S. Iqbal, R. Tirfoin and M.G. Moloney, Org. Biomol. Chem., 2016, 14, 4464-4478. (DOI: 10.1039/c6ob00557h)

"Fused Ring Oxazolopyrrolopyridopyrimidine Systems with Selective Gram Negative Activity”, Y. Chen, J. G. Moloney, K.E. Christensen, and M.G. Moloney, Antibiotics, 2017, 6, 2-11 (doi:10.3390/antibiotics6010002).

“Mimics of Pramanicin derived from Pyroglutamic acid and their Antibacterial Activity”, S.W.B. Tan, C. Chai and M. G. Moloney, Org. Biol. Chem., 2017, 15, 1889 (DOI: 10.1039/C6OB02828D).

Publications related to functional materials:

“Post-Polymerization Modification of Materials using Diaryldiazomethanes: Changes to Surface Macroscopic Properties", C.L. Bagwell, D.M.L. Leonard, J.-P. Griffiths, M.G. Moloney, N.J. Stratton, D.P. Travers, Macromolecular Reaction Engineering, 2014, 8, 170–180 [Invited submission].

In vitro angiogenesis by human umbilical vein endothelial cells (HUVECs) induced by surface modification of polystyrene-based microcarriers”, T.T.T. Yang, Y. Liu, J.S. Foord, J.-P. Griffiths, E.M. Parker, G.M. Xiong, M.G. Moloney and C. Choong, J. Mol. Eng. Mater., 2014, 2(3) 1450003.

“Surface characterization and in situ protein adsorption studies on a carbene-modified polymer surface”, G.W. Nelson, E.M. Parker, K. Singh, C.F. Blanford, M.G. Moloney, and J.S. Foord, Langmuir, 2015, 31, 11086-11096

“New Routes to Functionalize Carbon Black for Polypropylene Nanocomposites”, C. Shepherd, E. Hadzifejzovic, F. Shkal, K. Jurkschat, J. Moghal, E.M. Parker, M. Sawangphruk, D. R. Slocombe, J. Foord, M.G. Moloney,  Langmuir, 2016, 32 (31) 7917–7928 (DOI: 10.1021/acs.langmuir.6b02013).

Surface modification of polymers with bis(arylcarbene)s from bis(diazomethane)s: preparation, dyeing and characterization”, P. Yang and M. G. Moloney, RSC Advances, 2016, 6, 111276-111290 (DOI: 10.1039/C6RA24392D)
“Particulate polyaryletherketones with amine end functionalisation by a Friedel Crafts dispersion polymerisation”, K.J. Smith, I.D.H. Towle, J.F. Pratte, R.K Maskell and M.G. Moloney, European Polymer Journal, 2016, 84, 538-549

"Non-destructive functionalization of graphene by surface initiated atom transfer radical polymerization: an ideal nanofiller for poly(p-phenylene benzobisoxazole) fibers",  Z. Hu, Q. Shao, M.G. Moloney, X. Xu, D. Zhang, J.  Li, C. Zhang, Y. Huang, Macromolecules, 2017, 50, 1422–1429.

 

 

 

Professor M.G. Moloney

Professor of Chemistry

mark.moloney@chem.ox.ac.uk

Telephone: 44 (0) 1865 275 656

Research Group Website

http://research.chem.ox.ac.uk/mark-moloney.aspx