Molecular Design and Reaction Mechanisms
There are four areas of research under the umbrella of this title, which range across synthetic and mechanistic aspects of inorganic coordination chemistry and organic chemistry.
1. Energetic materials ? electrochemical studies toward environmental remediation.
2. Macrocyles- synthetic organic, coordination chemistry and metallo-supramolecular chemistry.
3. Supramolecular construction ? molecular host-guest chemistry of cucurbit[n]uril and associated assembly processes and physical properties.
4. An analysis of the reaction processes in the above areas, with a view toward mechanistic understanding and the implementation of synthetic techniques in molecular design.
Members of the Molecular Design and Reaction Mechanisms Research Group:
Academic Staff:
Dr Lynne Wallace (l.wallace@adfa.edu.au ) BSc Edin., PhD ANU
Dr Anthony Day (a.day@adfa.edu.au ) BSc, PhD ANU
Dr Mokhlesur Rahman (m.rahman@adfa.edu.au ) MSc Rajsh., Dipl Chem, Dr rer nat Regensburg, MRACI, CChem
Emeritus Professor:
Emeritus Professor Greg Jackson BSc (Hons), PhD Melb., DSc UNSW, FRACI, CChem
Research Assistants:
Dr Damian Buck (part time, Feb-Jul 2009) BSc PhD ANU
Dr T.D. Suja (part-time, Jul-Dec 2009) BSc, MSc Calicut , PhD Kerala
Research Students:
Lubna Alrawashdeh - Research Topic - A development of fingerprint and explosive residue detection through luminescent developers by using Iridium(III) complex
CAPT Mark Bali - Research Topic - Rapid neutralisations of organic peroxides such as TATP and DADP.
Michael Cronin - Research Topic -The chemical interactions of of iridium complexes, dinuclear complexes of iridium and mixed metal systems.
Fanfei Li -
Research Topic - Dinuclear ruthenium complexes as therapeutic agents. Fanfei Li is jointly supervised by A. Day and G. Collins (Biological Chemistry group).
Kirsten Randle - Research Topic - Detection of peroxide based explosives.
Feng Wu - Research Topic - Cucurbit[n]uri as Biomimetic - Catalysts and Supramolecular.
Wenjing Wu - Research Topic - Cucurbit[n]uril as an Artificial Muscle Component.
Research Collaborators:
Dr D. Armitt (DSTO, Weapons Systems Division)
Assoc. Prof. G. Collins (PEMS, UNSW@ADFA)
Assoc. Prof. C. Harb (SEIT, UNSW@ADFA)
Dr P. Kirkbride (Australian Federal Police)
Prof. C. Lennard ( University of Canberra )
Dr A. Provatas (DSTO Weapons Systems Division)
Prof. T. Zhu (Key Laboratory of Macrocyclic and Supramolecular Chemistry of Guizhou Province, University of Guizhou , Guiyang , PR China)
PhD Opportunities and Scholarships
If you are interested in a PhD or Masters by Research in molecular design and reaction mechanisms:
Contact:
Dr Lynne Wallace (l.wallace@adfa.edu.au)
Dr Anthony Day (a.day@adfa.edu.au)
Dr Mokhlesur Rahman (m.rahman@adfa.edu.au)
Current Research
Aspects of supramolecular chemistry utilizing cucurbit[n]uril
Dr Anthony Day - cross collaboration on some topics with Dr Lynne Wallace and/or Assoc. Prof. Grant Collins
Development of new methods for explosives and contraband detection based on host-guest interactions
Dr Anthony Day, Dr Lynne Wallace, Kirsten Randle, Prof. Chris Lennard, Dr Paul Kirkbride
Electrochemical remediation processes for treatment of wastewater from explosives manufacturing
Dr Lynne Wallace & Dr Anthony Day
NTO (nitrotriazolone) is a new insensitive explosive that may replace RDX, the current military standard, in some applications. Due to its high water solubility, the wastewater from its manufacture cannot be treated by conventional means. We have been investigating alternative remediation methods based on electrochemical treatment for NTO, which may also be applicable for other organic explosives. These electrochemical methods are more environmentally friendly, since no additional chemical loading is required, and the only input is electricity.
Organic power in organic packaging
Dr Anthony Day & Dr T.D. Suja
Synthesis and characterization of new high nitrogen compounds
Dr Lynne Wallace, Dr Anthony Day, Dr Arthur Provatas
Insensitive high explosives (IHEs) are an important area of research, due to the increased requirement for safer energetic materials in industrial and defence sectors. Azoxytriazolone (AZTO) is a new chemical species discovered by our research group, and preliminary results indicate it may possess potential as a new IHE. We are studying methods of synthesis of AZTO and other related compounds, and also investigating their solid-state and solution properties.
Synthesis and study of new iridium complexes for use in supramolecular and medicinal applications
Dr Lynne Wallace
Many molecular devices and pharmaceuticals contain components based on transition metals such as iridium or platinum. These transition metal complexes, consisting of organic units bonded to a central metal atom, can be structurally modified to fulfill different purposes. In this project, different synthetic approaches are used to prepare new iridium complexes, and these are studied, using a range of spectroscopic and electrochemical techniques, for their potential in light-activated molecular devices and to determine their interaction with biomolecules.
Synthesis, study and characterization of mono- and di- nuclear cobalt complexes to isolate metallo rotaxanes (a mechanically interlocked metalo architectures)
Dr Mokhlesur Rahman, Dr Anthony Day
Rotaxanes are of interest for their potential use as molecular switch, nano-shuttles, molecular electronics and molecular muscles. Transition metal complexes as stoppers also offer the possibility for synthesis of metallo polyrotaxane. Moreover, having a transition metal within this supramolecular architecture furnishes it with specific photonic, electric and magnetic properties.
Recent Achievements
CAPT Mark Bali is the recipient of the Chief of Defence Force Scholarship for 2010. The prestigious Chief of Defence Force Scholarship is awarded annually to one officer in the ADF for postgraduate research in a field that has strong military relevance. CAPT Bali is due to start an MSc in Feb 2010 ( A. Day and L. Wallace are his supervisors & Dr D Armitt (DSTO) is co-supervisor). Mark has just been appointed as a Visiting Fellow in the meantime (covering the period from Sept 2009-Feb 2010). His research topic will be ?Neutralisation of Explosives?.
Kirsten Randle was winner of the best oral research presentation at UNSW@ADFA Research Day 2008.
Student Research
Detection of peroxide based explosives
Kirsten Randle (k.randle@student.adfa.edu.au) PhD
Field of Study: Forensic Science/Counter Terrorism
Improvised explosive devices created from peroxide containing materials have increasingly been utilised in recent years by a number of terrorist organizations, particularly in Israel , as well as in the UK and the USA . Peroxide-based explosives can be easily ?home-made? using inexpensive, readily available starting materials which can be obtained in most hardware stores. My aim is to develop a sensitive and reliable field test for the detection of these peroxide based explosives and others as Tri-Acetone Tri-Peroxide (TATP) and HexaMethylene Triperoxide Diamine (HMTD). This research focuses on the development of an enhanced visual detection kit using sensitive metal catalysts in conjunction with the ABTS + radical cation and organic colour changing reagent Syringaldazine (SYAZ) in addition to the family of molecules know as cucurbit[n]uril (n=6-10), which have the potential to enhance visual detection.
Development of new cucurbiturils and biomimetic catalytic processes
Feng Wu (f.wu@student.adfa.edu.au) PhD
Field of Study: Chemistry
Recent Publications
2011 publications
Li, F., Mulyana, Y., Feterl, M., Warner, J., Collins, J.G. & Keene, F.R., 2011, The antimicrobial activity of inert oligonuclear polypyridylruthenium(ii) complexes against pathogenic bacteria, including MRSA, Dalton Transactions, 40(18), 5032-5038. http://dx.doi.org/10.1039/c1dt10250h
2010 publications
Journal - Refereed
Pisani, M.J. Zhao, Y., Wallace, L., Woodward, C.E., Keene, F.R., Day, A.I. and Collins, J.G. 2010, Cucurbit[10]uril binding of dinuclear platinum(II) and ruthenium(II) complexes: Association/dissociation rates from seconds to hours, Dalton Transactions, 39, 2078-2086, doi:10.1039/B921172A.
Uzunova, V.D., Cullinane, C., Brix, K., Nau, W.M., & Day, A.I., 2010, Toxicity of cucurbit[7]uril and cucurbit[8]uril: An exploratory in vitro and in vivo study, Organic and Biomolecular Chemistry, 8(9), 2037-2042, doi:10.1039/B925555A .
Xiao, X., He, L., Tao, Z., Xue, S., Zhu, Q. & Day, A.I., 2010, Supramolecular assemblies and modes of binding of the 1,6-hexanedipyridinium ion and the HCl salt of N,N '-bis(3-pyridylmethyl)-diaminoethane, with the symmetrically substituted tetramethylcucurbit[6]uril, Supramolecular Chemistry, 22, 194-201, doi:10.1080/10610270903262368.
Zhao, Y., Pourgholami, M.H., Morris, D.L., Collins, J.G., & Day, A.I., 2010, Enhanced cytotoxicity of benzimidazole carbamate derivatives and solubilisation by encapsulation in cucurbit[n]uril, Organic and Biomolecular Chemistry, 8(14), 3328-3337, 10.1039/C003732J.
2009 publications
Journal - Refereed
Wallace, L., Cronin, M.P., Day, A.I. & Buck, D.P., 2009, Electrochemical method applicable to treatment of wastewater from Nitrotriazolone production, Environmental Science and Technology, 43(6), 1993-1998, doi: 10.1021/es8028878.
Zhao, Y., Bali, M.S., Cullinane, C., Day, A.I., & Collins, J.G., 2009, Synthesis, cytotoxicity and cucurbituril binding of triamine linked dinuclear platinum complexes, Dalton Transactions, 26, 5190-5198, doi:10.1039/B905112K .
Conference ? Full Paper, non refereed
Underwood, C., Wall, C., Day, A., Provatas, A. & Wallace, L., 2009, Electrolytic treatment of nitroazole solutions in the synthesis of new high-nitrogen compounds, PARARI 2009 (9th Australian Explosives Ordnance Symposium), 10-12 Nov 2009, Adelaide, Australia, accepted.
2008 publications
Journal - Refereed
Limei, Z., Jiannan, Z., Yunqian, Z., Zhu, Q., Xue, S., Tao, Z., Zhang, J., Xin, Z., Wei, Z., Long, L. & Day, A.I., 2008, Opposing substitution in cucurbit[6]urils forms ellipsoid cavities: the symmetrical dicyclohexanocucurbit[6]uril is no exception highlighted by inclusion and exclusion complexes, Supramolecular Chemistry, 20(8) , 709-716, doi: 10.1080/10610270701747602.
Ni, X., Lin, J., Zheng, Y., Wu, W., Zhang, Y.B., Xue, S., Zhu, Q., Tao, Z. & Day, A.I., 2008, Supramolecular bracelets and interlocking rings elaborated through the interrelationship of neighboring chemical environments of alkyl-substitution on cucurbit[5]uril, Crystal Growth and Design, 8(9) , 3446-3450, doi: 10.1021/cg800451z.
Zhao, Y., Buck, D.P., Morris, D.L., Pourgholami, M.H., Day, A.I. & Collins, J.G., 2008, Solubilisation and cytotoxicity of albendazole encapsulated in cucurbit[n]uril, Organic & Biomolecular Chemistry, 6(24) , 4509-4515, doi: 10.1039/b813759e.
Conference Presentations
Ni, X.-L., Lin, J.-X., Zheng, Y.-Y., Wu, W,-S., Zhang, Y.-Q., Xue, S.-F., Zhu, Q.-J., Zhu, T. & Day, A., 2009, Partially substituted cucurbit[ n ]uril to new supramolecular forms, International Symposium on Macrocyclic & Supramolecular Chemistry , 21-25 June 2009, Maastricht, Netherlands.
Zhao, Y., Pisani, M., Wallace, L., Collins, J.G., & Day, A., 2009, New supramolecular forms to partially substituted cucurbit[ n ]uril, 1st International Conference on Cucurbituril, 10-11 July 2009, Pohang, Republic of Korea.
Randle, K., Day, A., Wallace, L., Kirkbride, P. & Lennard, C., 2008, Cucurbituril enhanced detection of peroxide-based explosives, Australian and New Zealand Forensic Science Society (ANZFSS) Symposium, 6-9 October 2008, Melbourne, Australia ? oral presentation.
Randle, K. , Day, A.I. , Wallace, L., Kirkbride, P. & Lennard, C., 2008, Detection of peroxide-based explosives, Australian Energetic Materials Symposium: Abstracts, December 2008, Flinders University, Adelaide, SA, Australia ? oral presentation.
Underwood, C., Day, A.I. & Wallace, L., 2008, Electrosynthetic routes to new high-nitrogen compounds based on triazoles and triazolones, Australian Energetic Materials Symposium: Abstracts , December 2008, Flinders University, Adelaide, SA, Australia. Slide presentation available at:
http://www.flinders.edu.au/shadomx/apps/fms/fmsdownload.cfm?file_uuid=B26F92D6-E4C5-3F41-996C-17D3526381B2&siteName=science_engineering