Chemistry Scholarships

Advancing the Metal-Organic Chemistry of the Heavy Alkaline Earth Metals.

Contacts: Phil Andrews and Glen Deacon

Chemical synthesis directed at new and/or improved materials and biologically relevant compounds requires constant innovation in the design and application of the chemical tools that allow compound construction. Traditional organometallic reagents have been drawn from a relatively small pool of active metals, thus constraining the diversity of application. The use of magnesium, while ubiquitous, has considerable limitations, and it is in the heavier alkaline earth metals (calcium, strontium and barium), an almost untapped resource, that new reactions, applications and outcomes will be discovered. These projects will focus on synthesis, ligand design, structural chemistry and applications in organic synthesis.

Bioconjugates for Application in Neuroscience – Detection of Alzheimer’s Disease.

Contact:  Leone Spiccia

As the Australian population ages, the prevalence of Alzheimer’s disease is set to reach epidemic proportions. It is predicted that by 2040, 500,000 Australians will have Alzheimer’s Disease, a disorder characterized by the progressive loss of memory and other faculties. Already, dementia costs $6.6 billion per year in Australia. This project aims to develop new biomarkers for Alzheimer’s disease. This will confer a number of benefits, allowing patients to be diagnosed and staged, and allowing pre-symptomatic identification of patients and monitoring of treatment effects. The characteristic pathologic feature of Alzheimer’s disease is the neuritic plaque comprising Aβ amyloid and neurofibrillary tangles made of paired helical fragment (PHF)-tau aggregates. The aim of this project is to develop biomarkers which can be labeled with relatively long half-life radioisotopes.

The current view is that the amyloid precursor protein (APP) contains an Aβ region which, if metabolized incorrectly by enzymes, generates a β–amyloid peptide (Aβ) consisting of 39-42 amino acids that can aggregate into fibrils. The Aβ peptide contains a histidine rich region which can bind strongly to metal ions, such as copper(II) and  zinc(II), and this process may promote aggregation. The fact that copper(II) binds strongly to the Aβ peptide will be used to advantage in this project, which aims to develop new organic molecules that: (i) bind rapidly to copper(II) ions so that radiolabelling with Cu-64 is achieved quickly; (ii) are able to cross the blood brain barrier and to reach the region of interest; and (iii) are able to bind to the Aβ peptide or fibrils.

BioNanoEngineering PhD studentships

Contacts: Prof Milton Hearn, Prof. Dan Nicolau
More details: www.bionanoeng.com.
Location: Clayton Campus

CGC recently won a European-Australia grant related to bio-applications of nanotechnology and is seeking applications for two PhD scholars.  Candidates should have a good BEng/BSc (Hons) or Masters degree in Engineering or Physical/Chemical Sciences.

Further details on specific projects can be gained by contacting the Director. Applications, preferably as pdf files, should be forwarded to Professor Milton Hearn, Director, Centre for Green Chemistry, at Milton.Hearn@sci.monash.edu.au or by mail to Building 75, Monash University Vic 3800.  Applications should include a list of publications, curriculum vitae and the names (preferably with email addresses) of three referees.

Brønsted Acid Activated Brønsted Base Catalysis In The Total Synthesis Of Biologically Active Natural Products

(2 PhD Scholarships for a 2008 start)

Contact: Dr David W. Lupton
Web: http://users.monash.edu.au/~dwlupton/index.html

Acid catalysis has long played an important role in mediating chemical transformations. Nature’s enzymatic processes often utilise simple acid catalysts, while in the chemical manufacturing industry the use of acid catalysis is ubiquitous. Reflecting the central role of acid catalysis in synthesis has been the application of chiral transition metal complexes as Lewis acid catalysts for asymmetric transformations. While these catalysts have proven extraordinarily powerful, issues relating to handling, chemoselectivity, and ecological impact place some constraints on their efficacy. Recently, the range of acid catalysts useful for enantioselective synthesis has been increased with the introduction of organicchiral Brønsted acids which, in a short space of time, have been applied to a range of enantioselective transformations. An alternate approach that is far less developed involves the generation of catalysts by Brønsted acid activation of chiral Brønsted basic molecules. In this project we will develop a range of Brønsted acid activated Brønsted bases catalysts and explore their use in the synthesis of natural products recently isolated from the Australian rainforest tree Elaeocarpus Grandis, see structure.

Development of Non-iodinated, Non Ionic, Water-Soluble Metal Based Compounds for Radiographic Contrast Media.

Contacts: Peter Junk and Phil Andrews

Almost one million CT scans are performed on patients in Australia every year, growing at an annual rate of 5%. To allow visualisation of pathological problems large volumes of iodine based contrast imaging agents are injected into the patient. Unfortunately, 1% of the population is allergic to these (with moderate and sometimes severe cardiovascular, anaphylactic and pain reactions) and 1 in 20,000 people die after intravenous administration. This proposal will develop new non-toxic contrast agents based on stable bismuth and rare earth metal oxide/hydroxide cluster molecules, leading to greater patient comfort and safety, and improved diagnoses through significantly enhanced contrast.

Forms of Organic Nitrogen is Soil.

Contact: Dr Tony Patti

The project would be suitable for a student with a background in Chemistry and Microbiology and will involve a chemical investigation into the forms of organic nitrogen in a range of Victorian soils, with a particular focus on identifying proteins and glycoproteins. The project will be associated with the Centre for Green Chemistry.

Frontiers in Synthetic and Structural Rare Earth Chemistry.

Contacts: Peter Junk and Glen Deacon

Rare earth elements are a major under-utilised Australian resource. Their commercial development requires knowledge and progression of their chemistry. Advancing the chemistry of highly reactive, air-sensitive metal organics will provide the breakthrough science to underpin future applications in chemical manufacture, catalysis and new materials. Transformation of rare earth chemistry to achieve behaviour hitherto atypical of these elements by steric and electronic modulation of attached groups will value-add to their properties.

Inorganic Molecular Magnetic Materials of the Nanosized Cluster and Extended Framework Types

Contacts: Keith Murray, Stuart Batten

This project deals with the design, synthesis, crystal structures and detailed magnetic properties of molecular based magnetic materials of two general kinds. The first type deals with medium to large clusters of manganese, iron or vanadium that display single molecule magnetism (SMM), the first such reported example being the oxo-/carboxylato-bridged {Mn(III)/Mn(IV)}12-acetate. These materials display unique, quantum type behaviour in their DC magnetization loops and their AC susceptibility frequency-dependent behaviour. They are much studied in the context of nanomagnetic materials and offer scope in future data storage applications. Recently we discovered tetranuclear Mn(II)/Mn(III) SMMs that contained flexible triethanolamine chelating ‘outer’ ligands.1 The present project aims to make new clusters SMMs of Mn, Fe or V, sometimes combined with lanthanide ions, using a variety of new bridging and terminal ligand groups.
It will suit candidates that enjoy inorganic coordination chemistry synthesis, structural and physicochemical studies (we have access to EPR and Mössbauer methods with colleagues in Physics).

The other area is the very topical one of d-block coordination polymers of the extended framework type, some displaying functions such as nanoporosity and, in a separate project, spin-crossover. Our work on metal dicyanamide frameworks,2 [M(N(CN)2)2], gave rise to a worldwide study of such long-range magnetically ordered compounds and allowed comparisons to be made with the much studied CN- and C2O42- -bridged materials. The present project will concentrate on designing and synthesizing new or little studied types of bridged species, with emphasis on organopolynitriles3 and carbonate and related anions, some being free radical in character.

The work is supported by a new ARC Discovery grant. It is possible that two scholarships will be available

1. L. M. Wittick, K. S. Murray, B. Moubaraki, S. R.  Batten, L. Spiccia, K. J. Berry, Dalton Trans. 2004, 1003.
2. S. R. Batten, K. S. Murray, Coord. Chem. Rev. 2003,246, 103.
3. A. S. R. Chesman, D. R. Turner, D.J. Price, B. Moubaraki, K. S. Murray, G. B. Deacon, S. R. Batten, Chem. Commun., 2007, 3541.
   

Modern Main Group Chemistry

Contact: Prof. Cameron Jones

In the past 5 years remarkable progress has been made in the chemistry of low oxidation state and low coordination number p-block compounds.  It is now possible to prepare and investigate the fascinating reactivity of compounds that were thought incapable of existence until a few years ago.  This area is rapidly expanding in the US and Europe but is under-studied in Australia.  In January 2007 we transferred our internationally leading research group from Cardiff to Monash to continue our investigations into this fundamentally interesting, yet highly applicable field.  Professor Jones has funding to start several PhD students this year and would be very interested to hear from you if you would like to explore the possibility of carrying out a PhD in my group. Briefly, we are involved in the field of Modern Main Group Chemistry.  For some more information, please see my Cardiff websites:

• http://www.cf.ac.uk/chemy/cfamgc
• http://www.cf.ac.uk/chemy/staff/jones.html

It is also of note that if you joined the group, you would have the opportunity of spending 6 months working in one of our collaborators groups in Europe or North America.

Peptide Nucleic Acid -Metal Complex Hybrids as Biological Sensors.

Contact:  Leone Spiccia

Our PNA studies include PNA-ferrocene and ruthenium(II) complex hybrids that can be applied as biosensors. In these systems, the PNA chain, which directs the conjugate to the DNA/RNA target, is covalently attached to the redox active complexes or photo-active Ru(II) complex, which detect or manipulate the DNA/RNA (redox sensors or ‘light-up probes’). For example, ferrocenyl biomolecule hybrids are currently being synthesized with the aim of sensing specific RNA/DNA sequences via electrochemical methods. With this in mind, a ferrocenyl derivative (1) has been prepared and the complexation of this assembly with Zn²⁺ and subsequent binding of thymine to the Zn²⁺ complex (Figure 1) studied by electrochemistry (G. Gasser, A. M. Bond, B. Graham, Z. Kosowski and L. Spiccia, NSTI Technical Proceedings of 2005 Nanotechnology Conference and Trade Show, Volume 1, Ch 8.2, Bio MicroSensors, 2005, p. 412 – 415.

Figure 1: Receptor 1 complexed with Zn2+ and thymine.

We are optimizing the ligand structure in order to maximize the response upon the addition of thymine. At the same time, we are investigating the detection of nucleosides such as thymidine (dT) by our redox active ferrocenyl derivative. We are also developing methods for incorporating these redox active assemblies into oligonucleotide sequences with a view to producing sequence-specific redox sensors.

Total Synthesis Of Biologically Active Natural Products Using Cascade 1,4-Silyl Addition/Aldol Reactions

(1 PhD Scholarship for a 2008 start)

Contact: Dr David W. Lupton
Web: http://users.monash.edu.au/~dwlupton/index.html