Honours in Chemistry 2017 · 2017-03-29 · Honours in Chemistry 2017 . 2 ... At the completion of the year you will present a thesis detailing the background, aims, ... describing

3972 BSc Advanced Science 3992 BSc Medicinal Chemistry

4500 BSc Chemistry

Honours in Chemistry 2017

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Table of Contents

Part A: Welcome ………………………………… 3

1. Overview ………………………………… 4

2. Admission ………………………………… 6

3. How to Apply / Useful Information …………………………………. 7

4. Assessment …………………………………. 8

Part B: Honours Supervisors ………………………………….. 11

Part C: Alternatives for Honours 62

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WELCOME The School of Chemistry at UNSW is one of the leading centres of chemistry research in Australia. Composed of over 20 well-funded research teams, we are located in three connected buildings: Dalton (F12) Chemical Sciences Building (F10NA), and in the Chemical Engineering Building (F10) with state of the art research facilities that enable research spanning the entire breadth of chemistry. The UNSW Mark Wainwright Analytical Centre (MWAC) is co-located adjacent to the School of Chemistry (F10NA) and provides major research facilities that are unsurpassed internationally. Research in the School of Chemistry is focused on four strategic areas:

Nanoscience Energy & Environment Medicinal Chemistry Catalysis & Industry

In each area our School has world-renowned scientists that make significant impact on international research, making an impact in areas diverse as medicine, the molecular sciences, chemical industry and materials science. The School of Chemistry at UNSW has strong links to Australia’s professional body for chemists, the Royal Australian Chemical Institute (RACI) and the International Union of Pure and Applied Chemistry (IUPAC). It also has close ties with the American Chemical Society (ACS). Several research team leaders hold senior positions in the RACI, and the NSW state branch is located in the School. Professor David Black was the Secretary General of IUPAC from 2004 – 2011, and is the current Secretary General of the International Council for Science (ICSU). The School welcomes applicants for Honours from students throughout the world, acknowledging that the Honours year is an outstanding introduction to research. We are confident that the wide range of research undertaken in the School provides applicants with a rewarding Honours year. Professor Scott Kable (Head of School) Associate Professor John Stride (Chemistry Honours Coordinator)

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OVERVIEW OF HONOURS This booklet provides details for students interested in undertaking an Honours year with a major in chemistry or undertaking a BSc Medicinal Chemistry (3992). If you are a BSc Nanotechnology (3617) student, please consult the specialised Honours booklet for your degree. Is the Honours year worth the extra year it takes? The answer is certainly “Yes!” for many people.

The response from potential employers in industry and the public sector is that they will employ a good Honours graduate over someone with a pass degree.

Honours is necessary for anyone contemplating postgraduate study in chemistry. Honours gives you “hands-on” experience in tackling projects, and provides a

rewarding finishing quality to your education. Honours provides you with experience at managing your own project,

independence and time management skills. Most important of all, the Honours year allows you to work closely with the staff in

the School of Chemistry, and it transforms the University for you into a very human organisation that has people who support you.

HONOURS IN THE SCHOOL OF CHEMISTRY In 2017 the School of Chemistry offers Honours programs that are suitable for students enrolled in Science, Advanced Science, Medicinal Chemistry and Environmental Science. All programs involve coursework and are of equal standing. BSc. Advanced Science students majoring in Chemistry enrol in Advanced Chemistry Honours. BSc. Science students with a major in Chemistry enrol in Chemical Sciences Honours. Assessment is based entirely on your record during the Honours year, during which students have the opportunity to demonstrate skills in both research and coursework. The course codes for Advanced Chemistry Honours are CHEM4003 for students starting in session 1 of 2017, and CHEM4004 for students starting in Session 2 of 2017. The course code for students undertaking Chemical Sciences Honours is CHEM4500 irrespective of which session you commence.

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WHAT DOES AN HONOURS YEAR ENTAIL? The aim of the Honours year is to continue your development into a well rounded chemist and research scientist by exposing you to independent research, advanced courses in Chemistry and a broad range of fields in chemistry through your attendance at research seminars. The original research project forms the main component of the Honours year. Staff members offer numerous projects in their field of research, some of which are suitable for Chemistry Honours. Students nominate supervisors in research areas that interest them. They then work on a project under the close supervision of an allocated supervisor for the duration of the Honours year. Student-supervisor allocations are made on the basis of student WAM and demand for specific supervisors. Every attempt is made to allocate students their preferred supervisor or supervisors. Basic research skills are developed in the 6 units of credit course CHEM4501 to prepare you for your research project; areas covered include writing a research proposal, presentation skills and modern occupational health and safety requirements. Advanced level lecture courses are designed to extend your knowledge and broaden your understanding of key branches of chemistry. Honours students must take 6 units of credit (CHEM4502), which is equivalent to three four-week courses, during their Honours year. These take place as components of the Topics in Contemporary Chemistry A and B courses. Details are available from the Honours Coordinator (Associate Professor John Stride). Research seminars are conducted throughout the year and are an important means of exposing Honours students to research conducted in the School and at national and international institutions. Attendance is compulsory and unsatisfactory attendance will result in reduction of your Honours grade.

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ADMISSION ELIGIBILITY For admission to Honours in the School of Chemistry, it is expected that a student will have achieved a credit average of WAM over 65 and have a BSc major in chemistry. Students with qualifications in other disciplines may also be eligible for admission. The prerequisite for admission to Advanced Chemistry Honours (Program 3972, BSc. Advanced Science students) is the completion of an approved plan leading to a major in Chemistry in the BSc. Advanced Science degree. The prerequisite for admission to Chemical Sciences Honours (Program 4500, BSc. Students) is the completion of an approved plan leading to a major in Chemistry in the 3 year BSc. Degree. Students who have completed pass degree requirements at a University other than UNSW, or who have already graduated with a pass degree from UNSW or elsewhere, may be eligible to undertake an Honours year in the School of Chemistry. In such cases, please contact the Honours Coordinator ([email protected]) for clarification.

In all cases, admission is subject to the formal approval of the Head of School.

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HOW TO APPLY

If you are eligible to enrol (see previous page), approximately 3 – 6 months before you intend to start Honours, consult the School of Chemistry Research Booklet (distributed upon request – email the Honours Coordinator) to determine which areas of research interest you and discuss these with the relevant academic member of staff. It is strongly recommended that you talk to all prospective supervisors in your area of interest (i.e. at least 3 potential supervisors).

A good working relationship with your supervisor is paramount for the success of your Honours year. The choice of project is also important, and you are advised to obtain as much information as possible before making your decision. Find out what exactly is involved and what would be expected of you if you were to undertake a particular project.

By 30th June 2017 submit your intention to commence Honours form via the on-line portal with at least three supervisor preferences. Rank your order of preference. You must have spoken to and been given permission by at least three supervisors prior to nominating them (note: a cross-check will be made with all nominated academics).

The School will contact you via email by 21st November 2016 to advise the outcome of your application for Honours.

For further information and assistance, contact: Honours Coordinator, Associate Professor John Stride:

[email protected]

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ASSESSMENT The Honours degree is graded into Class 1, Class 2 Division 1, Class 2 Division 2, Class 3 or Honours may not be awarded (see below for grade boundaries). Assessment is on the basis of performance in the various components of the course, including the research project and the formal course work. Note that in order to be awarded Honours, you must achieve a satisfactory performance (>50%) in each component (coursework and research). 6 UoC Coursework 6 UoC research skills 36 UoC Research

! Thesis Grading Committee’s assessment of Thesis ! Thesis Grading Committee’s assessment of the Final Seminar Defence ! Attendance at School Research Seminars

Course Work (6 UoC – 12.5%): You are required to take three different four-week courses during your Honours year. These take place as components of the Topics in Contemporary Chemistry A and B courses and will form the basis of CHEM4502. Details are available from the Honours Coordinator (Associate Professor John Stride). Each year the topics change and a list will be made available for you to choose from at the beginning of the Honours year. Research skills (6 UoC – 12.5%): In order to adequately equip yourself for your research project, you are required to take CHEM4501 which will cover how to write a research proposal, presentation skills, managing your research and occupational health and safety. Research Component (36 UoC - 75%): The research project is the distinctive feature of the Honours year. It is the major undertaking of the year and is both the most challenging and rewarding aspect of Honours. Students work on original research projects conceived and overseen by a member of staff. While you will be instructed by your supervisor on the nature of the project and will be given guidance in how to conduct the project, it is expected that you will perform all experimental work independently. You will be expected to prepare and

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analyse experimental results and work with your supervisor to identify and overcome any problems. At the completion of the year you will present a thesis detailing the background, aims, experimental procedures, results and future directions of your project. Research Proposal: To assist in the preparation of your thesis and to allow your writing style to be improved, you will also be required to submit a research report describing your chosen research project and a review of pertinent literature.

Thesis Submission: You will write your thesis and submit it approximately on the 15th May 2018. Your thesis is a significant portion of your Honours mark and should be read and edited by numerous people including your supervisor. You are required to submit a final version of your thesis that incorporates the Thesis Committee’s comments to your supervisor and the School by 30th June 2018. Failure to do so will result in your Honours grade being withheld. The thesis accounts for 60% of your research mark.

Honours Seminar: You will be expected to present your work at two seminars during your Honours year; one will be a short overview of your project in the first 2 months of your enrolment and will be graded within your research skills component. A longer seminar detailing your results to be presented after submitting your thesis; this seminar is typically 15 minutes long plus up to 10 minutes for questions. It is comprises 15% of your research mark. Oral thesis defence (viva-voce): The thesis defence will be in the weeks after you have submitted your Honours thesis and presented your final seminar and will be a closed examination of around 20-30 minutes. It will comprise 25% of your research mark. Attendance at School Research Seminars: Attendance at School Research Seminars is compulsory.

HONOURS DEGREE GRADE BOUNDARIES (%) Class 1 85+ Class 2 Division 1 75 – 84 Class 2 Division 2 65 – 74 Class 3 50 – 64

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HONOURS SUPERVISORS

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DR GRAHAM BALL Level 1, Dalton Building (F12)

T: 9385 4720 E: [email protected]

NMR SPECTROSCOPY AND COMPUTATIONAL CHEMISTRY: APPLICATIONS TO ORGANOMETALLIC AND BIOLOGICAL CHEMISTRY

Our research focuses on applying NMR spectroscopy to shed light on important chemical problems, often in the areas of organometallic and biological chemistry. NMR spectroscopy is probably the most powerful technique available to the chemist and the Mark Wainwright Analytical Centre is bristling with state-of-the-art instruments eagerly awaiting YOU to run experiments that push the boundaries!

Our experimental work is complemented and enriched by using computational techniques. We model small chemical systems with ab initio and DFT methods and biolmolecular systems with molecular mechanics and QM/MM methods. This is a superb way to get detailed information about your molecules and their reactivity without all the risk assessments!

(a) Short-lived metal complexes and reactive intermediates

What should we do with petrol? Mostly it is just burned as fuel leading to damaging CO2 and a rapid dwindling of this precious resource that took millions of years to form. Recently, chemists around the globe have been working on ways of converting relatively unreactive alkanes found in petroleum into useful compounds. A process known as C-H activation is at the core of these conversions, and we are studying the key short lived intermediates in this chemistry, which have an intact alkane molecule bound to a metal, to aid design of new catalysts.

These intermediates, known as alkane complexes, are generated by hitting precursor complexes with light while they are in the NMR spectrometer. Low temperatures are used to stabilise these reactive intermediates, permitting their characterization. With this strategy, we have observed several types of alkane complex1,2,3 including the JACS cover above1 and even complexes where xenon acts as a ligand.4 Alkanes contain no lone pairs for binding to the metal centre. Instead they bind using the electrons in the C-H sigma bond. This is why they are poor ligands and their complexes are so short-lived (~100 ms maximum lifetime at 25 °C).

Designing new exotic molecules: Computational investigations of alkane and noble gas complexes

We employ computational methods (DFT, ab initio) to aid the design and understanding of these fascinating compounds. For example, the recently observed cationic alkane complexes shown here were designed computationally prior to observation. Current projects are aimed at answering

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questions such as: Can we make more stable alkane complexes? Can we do chemistry with the alkanes when they are bound? What exchange processes do the alkane ligands undergo? Can we observe complexes with ligands that bind even more weakly? Projects in this area can be primarily synthetically based (making new alkane complex precursors), NMR spectroscopy based (observing the new complexes and their reactions) or computationally based (designing new compounds and predicting their reactivity). The 3 components can be blended to suit the interests of students tackling the project. 1 Young, R.D.; Lawes, D.J.; Hill, A.F.; Ball, G.E. J. Am. Chem. Soc., 2012, 134, 8294.

Podcast at http://pubs.acs.org/JACSbeta/coverartpodcasts/ #38. 2 Yau, H.M; McKay, A.I; Hesse, H.; Xu, R.; He, M.; Holt, C.E.; Ball, G.E. J. Am. Chem. Soc. 2016, 138, 281. 3 Young, R.D.; Hill, A.F.; Hillier, W.; Ball, G.E. J. Am. Chem. Soc., 2011, 133, 13806. 4 Ball, G.E.; Darwish, T.A; Geftakis, S.; George, M.W.; Lawes, D.J.; Portius, P.; Rourke, J.P. Proc. Natl. Acad. Sci.

USA., 2005, 102, 1853.

(b) Anti-cancer drug-DNA interactions (in collaboration with A/Prof Larry Wakelin, School of Medical Sciences and Dr Don Thomas, NMR Facility)

DNA presents one of the most logical and practical targets for anti cancer therapeutics. We are investigating the binding of several bis-intercalating molecules that show promise as next generation anti-cancer drugs and also the binding of clinically established drugs such as mitoxantone. The solution structures of the DNA-ligand adducts are obtained via a suite of 2D NMR techniques coupled with NOE-constrained molecular dynamics simulations employing the AMBER forcefield. Our recent results have lead to a re-evaluation of how these bis-intercalators interact with DNA.5

The project involves a fusion of NMR spectroscopy and molecular modelling, at the molecular mechanics or QM/MM level. The project can be tailored to focus solely on NMR studies, solely molecular modelling or a balanced amount of both. We have a number of drugs synthesised that are ready for investigation.

5. Serobian, A.; Thomas, D. S.; Ball, G. E.; Denny, W. A.; Wakelin, L. P. G. Biopolymers 2014, 101, 1099.

(c) In silico studies of catalytic reductions (with A/Prof S. Colbran)

Building on the empirical results from A/Prof Colbran’s group, we are modelling catalytic cycles of reductions of key small molecules such as CO2. Using density functional theory (DFT) allows us to get at the nitty-gritty of the mechanism of the catalysis and inform rational design of the next generation of reduction catalysts in this ARC funded project.

6. McSkimming, A.; Chan, B.; Bhadbhade, M. M.; Ball, G. E.; Colbran, S. B. Chem. - Eur. J. 2015, 21, 2821.

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DR. JON BEVES Level 2, Dalton Building (F12)


SUPRAMOLECULAR AND COORDINATION CHEMISTRY

• Supramolecular Chemistry • Coordination Chemistry • Molecular Machines

The use of weak, non-covalent interactions to form functional self-assembled architectures is core to my research interests, with a focus on metal-ligand bonds to direct the assembly of large multifunctional molecules, and light as a tool for chemical control.

It would be great to work with Honours students on the following projects:

(a) Photoactive molecular cages

(in collaboration with Dr Evan Moore, UQ)

Molecular cages are ‘small’ molecules with cavities capable of binding small molecules and anions. Within the confines of these cavities, usual reactivities can result, similar to the function of the binding pockets of nature’s enzymes. This project will involve using metal complexes as building blocks for cages capable of using natural visible light to catalyse reactions of bound substrates, the first example of which we published in 2015.[1]

Skills involved: organic and inorganic synthesis, multidimensional NMR, mass spectrometry, cyclic voltammetry, X-ray crystallography, photophysical measurements

(b) Photoswitchable molecules

(in collaboration with A/Prof Joakim Andreasson, Chalmers Institute of Technology, Sweden).

Some types of organic molecules can be isomerised between two forms using light. These two forms typically have very different properties, such as polarity, pKa and reactivity. We are looking to use visible light switchable molecules to control molecular reactions, such as driving pH changes or switching

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ON/OFF catalytic activities. One example are spiropyran molecules, which act as ‘photoacids’, being switched between stable acidic and non-acidic states using light stimulus. Photoacids based on spriopyran may be directly incorporated into molecular and supramolecular systems for applications in stimulus-responsible switching with applications ranging from synthetic catalysis to in-situ drug release. New photoacidic molecules are required which are suitable for building into larger structures and membranes, and the tuning their photoswitching properties will be studied using a combination of spectroscopic techniques.

Skills: organic synthesis, multidimensional NMR spectrometry, mass spectrometry

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H+ (c) Novel ruthenium(II) complexes

Ruthenium(II) complexes are extremely useful complexes with applications ranging from energy storage and light harvesting, to catalysis and drug applications. This project will develop new types of chiral ruthenium(II) complexes which are responsive to their environments to allow these useful properties to be controlled by external stimuli (eg, temperature, chemical reagents, light, redox etc).

Skills: organic and inorganic synthesis, multidimensional NMR spectrometry, mass spectrometry, X-ray crystallography, cyclic voltammetry, X-ray crystallography, photophysical measurements

(d) Molecular rotors (in collaboration with Dr Jason Harper)

Being able to control motion at the molecular level is a fundamental challenge facing science. Nature uses controlled molecular motion, so called ‘molecular machines’ to control virtually every process in biology. So far, chemists use molecular machines to control nothing! This project involves the synthesis of molecular ‘rotors’ with a ‘propeller’ which can spin spontaneously when appropriate energy is supplied.

Skills: Organic synthesis, multidimensional NMR spectrometry

(e) …or other projects tailored to your interests!

1. Yang, J.; Bhadbhade, M.; Donald, W. A.; Iranmanesh, H.; Moore, E. G.; Yan, H.; Beves, J. E. Chem. Commun. 2015, 51, 4465-4468.

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DR ROBERT CHAPMAN Room 124, Level 1, Dalton Building (F12)


POLYMER THERAPEUTICS BY COMBINATORIAL DESIGN

• Clustering receptor proteins on the cell membrane can be used to control a range of cell behaviours. In my research I aim to design macromolecular architectures that can act as cancer therapeutics by clustering death receptor proteins on the cell surface.

• Because effective architectures are difficult to find by a rational design approach, I use combinatorial polymer synthesis to prepare and screen libraries of structures. Projects are therefore focussed both on the development of these combinatorial synthesis techniques, and on the use of them to design macromolecular therapeutics.

• I am a Vice Chancellor’s research fellow within the school and work closely with the group of Prof. Martina Stenzel in the Centre for Advanced Macromolecular Design (CAMD). Please contact me for more information or to discuss any of the following projects.


(a) Combinatorial synthesis of star peptide-polymer conjugates for death receptor clustering (with Prof. Martina Stenzel)

In recent years, triggering apoptosis through cell receptor clustering has emerged as one of the main targets for cancer chemotherapy, and a number of protein therapeutics that work through this mechanism are in clinical trials. However, natural proteins are not ideal therapeutics due to the difficulties in finding the right protein for any given application, their capacity to trigger immune detection

and drug resistance, as well as their high cost and poor stability. Peptides that can bind to the relevant cell receptors are known and by presenting these on the surface of a scaffold it is hoped that it will be possible to design synthetic materials capable of clustering cell receptors with similar efficacy.

Polymers are attractive scaffolds to use for the presentation of these peptides as they allow precise control over architecture, density, and rigidity, as well as the position and number of binding moieties present. By synthesising

libraries different architectures and measuring the relationship between their structure and biological

Enz-RAFT polymer synthesis in a 384 plate

Apoptosis of cancer cells induced by the clustering of

TRAIL receptors. Adapted from Lemke et al.[1]

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efficacy, this project aims to design synthetic polymer-peptide conjugates for the clustering of death receptors on breast cancer cell lines. The project will make use of a new method for combinatorial polymer synthesis (termed Enz-RAFT) on microtitre plates that was recently developed in my work.[2]

The project will involve the synthesis of several chain transfer agents required to generate the different polymer architectures, the synthesis of peptides for receptor binding, and subsequent polymerisation and polymer analysis by NMR, GPC and associated techniques. Screening of biological activity will be performed in collaboration with Dr Adam Gormley at Rutgers University in the USA.

(b) Stabilisation of glucose oxidase enzymes in nanocapsules (with Prof. Martina Stenzel)

Despite their extensive use in a range of synthetic, biosensing, and therapeutic applications, enzymes are often highly unstable to heat, pH, and the presence of organic solvents. However, several recent studies have shown that it is possible to protect enzymes against degredation by such environmental factors by encapsulating them within nanocapsules.

We recently developed a new methodology for the combinatorial synthesis of well-defined polymers (Enz-RAFT) that relies on the enzyme glucose oxidase (GOx). This enzyme consumes the oxygen that would otherwise inhibit the polymerisation. With this technique, large arrays of polymer structures can be prepared very rapidly, and in a format appropriate for high throughput screening of structure-activity relationships, enabling a more systematic approach to the design of polymer structures in biological applications. However, because the enzyme is sensitive to temperature and the presence of organic solvents, the technique only works at temperatures below 55°C, and in a limited range of alcohol / water mixtures. This project will investigate the stabilisation of glucose oxidase in crosslinked acrylamide nanogels, and in inverse micelles with the aim of both expanding the scope of the Enz-RAFT technique and of providing general platforms for the stabilisation of therapeutic enzymes.

The project will involve controlled polymer synthesis and self assembly techniques to prepare the enzyme nanocapsules, characterisation by light scattering and electron microscopy, and the use of enzyme activity assays to measure their activity under a range of environmental stresses. 1. J. Lemke, S. von Karstedt, J. Zinngrebe and H. Walczak, Cell Death Differ., 2014, 21, 1350–64.

2. R. Chapman, A. J. Gormley, M. H. Stenzel and M. M. Stevens, Angew. Chemie Int. Ed., 2016, 128, 4576–4579.

2. A. Beloqui, S. Baur, V. Trouillet, A. Welle, J. Madsen, M. Bastmeyer, G. Delaittre; Small, 2016, 12, 1716–1722

Preparation of single enzyme nanogels. Adapted from Beloqui et al [3]

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A/PROF. STEVE COLBRAN Level 2, Dalton Building (F12)


TRANSITIONAL METAL CHEMISTRY AND CATALYSIS

• Synthesis. My group makes new, ‘never-seen-before’, metal-containing molecules: exciting stuff! • Spectroscopy and electrochemistry. We zap the new molecules with light and electricity —

because extreme conditions create highly reactive species. • Reactivity and catalysis. Highly reactive species exhibit unmatched, extraordinary, chemical

properties — we hunt for useful, important, reactions and energy-efficient catalyses.


(a) A bio-inspired sustainable approach to chemical reduction

In recent breakthrough research, we’ve proved that cleverly designed organo�transition metal–organo-

hydride conjugates are exceptionally effective catalysts for energy�efficient chemical reductions of unsaturated substrates under benign conditions (in air at ambient temperature and pressure).1-3 In the following research projects, you’ll use our conceptually new approach to chemical reduction to make chiral drug precursors or to produce methanol sustainably from carbon dioxide.

Saving the world: Advanced transition metal–organohydride catalysts for CO2 to methanol conversion (with Professor Les Field, School of Chemistry) In this research project you’ll investigate sophisticated conjugates of transition metal complexes and multifunctional organo-hydride ligands — ligands that can store and donate hydride ion — as catalysts for reduction of carbon dioxide beyond the two-electron level.1-3 In particular, you’ll target catalysts for the selective, energy-efficient electro-conversion of CO2 to methanol, a widely sought alternative fuel. In this research, you’ll also be assisted by the deep experience of Prof. Field and his research team in the chemistry of highly reactive organo-transition metal complexes that bind and activate CO2.

Making drugs better, more efficiently: Chiral transition metal–organohydride catalysts for efficient asymmetric reduction (with Dr Graham Ball, School of Chemistry) In this research, you’ll advance and apply our new catalytic methodology for chemical reduction1-3 to the asymmetric hydrogenations of prochiral unsaturated organic substrates, including imine, carbonyl and alkene precursors to chiral drugs suggested by a commercial partner. There is scope to undertake DFT studies on the new catalytic processes — supervised by the redoubtable Dr. Ball.

1. A. McSkimming, M. Bhadbhade, S. Colbran, Bio-inspired catalysis of imine reduction by rhodium complexes with tethered Hantzsch pyridinium groups, Angew. Chem. Int. Ed. 2013, 52, 3411 (FRONT COVER, IMPACT FACTOR 13.7).

2. A. McSkimming, S. Colbran, The coordination chemistry of organo-hydride donors: new prospects for efficient multi-electron reduction, Chem. Soc. Rev. 2013, 42, 5439 (50 pages, IMPACT FACTOR 24.8). 3. Britney Spears New Video: Catalysis in a teacup, http://britneyspearsnewvideo.tiaexposed.com/1897/catalyst-in-a-teacup-new-approach-to-chemical-reduction/ (accessed 1 May, 2013).

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4. M. Rosenzweig (Editor in Chief), Chemical Processing (US chemical industry trade magazine), http://www.chemical processing.com/articles/2013/bio-inspired-approach-suits-chemical-reduction/ (online version accessed 17 May, 2013).

(b) Chemistry and applications of a new large-ring macrocycle: bis(phenanthroline-pyrrole)

Large-ring oligo(pyridyl-pyrrole) macrocycles are used as discotic materials for liquid crystal displays, as dyes and photosensitizers, and as ligands for macrocyclic encapsulation of lanthanide or actinide ions. We’ve invented the world’s shortest and most convenient preparation of a large-ring rigid macrocycle, namely the bis(phenanthroline-pyrrole), H2LMC. We make H2LMC on a large (multi-gram) scale by stirring commercial reagents in ethanol overnight.

Better TVs: Magnetic discotic materials for liquid crystalline displays (with Associate Professor John Stride, School of Chemistry) Discotic liquid crystals are formed from molecules with flexible alkyl substituents bound to a planar, rigid and π-electron-rich core. Direct (one-pot) transesterification and ester-to-amide conversions will be used to afford derivatives of H2LMC with varying (long) alkyl chain lengths. The liquid crystallinity and opto-electronic properties of these novel materials will be investigated. You’ll also investigate complexation with metal ions to form metallomesogens, which should exhibit useful electrical- and/or magnetic-switching between mesophases.

Into the unknown: The unexplored chemistry and applications of H2LMC and its metal complexes We created H2LMC late in 2012. So far we’ve only skimmed the surface of the chemistry of H2LMC. The discoveries are remarkable. Two examples. H2LMC is not only highly fluorescent, it’s an amazingly potent photosensitizer that photo-dehydrochlorinates chlorinated solvents — so, is it a catalyst for clean up of environmental chlorohydrocarbon contamination? H2LMC is also a superb ligand that produces incredible metal complexes: e.g., the fluorescence and magnetism of the unique Eu(III)2(μ-OH) dimer shown is exquisitely sensitive to its surroundings suggesting diverse applications for the complex ranging from nano-electronics to intra-cellular imaging. A rich and diverse chemistry awaits discovery and development.

(c) Other projects

Other projects involving transition metal chemistry, spectroscopy and/or (spectro)electrochemistry are available. Projects will be tailored to you and your abilities and interests. Please feel free to come and chat about possible research projects.

Schematic of columnar packing for H2LMC

[(NO3)(LMC)Eu(μ-OH)Eu(LMC)(H2O)2].2py

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A/PROF. MARCUS COLE Level 2, Dalton Building (F12)

E: [email protected]

ORGANOMETALLICS AND METALLOHYDRIDES

Our research interests span the organometallic and hydride chemistries of the p- and f-block, with a view to developing syntheses for rare low oxidation state metal complexes and heavy metal hydrides. These species may be kinetically stabilised by bulky, sterically hindered ligands. Our research is driven by scientific curiosity, with a view to downstream applications in areas as diverse as H2 storage, metal film deposition and catalysis. Students receive training in the manipulation and characterisation of ultra-air sensitive compounds with an emphasis on NMR and IR spectroscopies, and crystallography.

a) New paths to low oxidation state aluminium and silicon

The principal oxidation states of light group 13 and 14 metals are +3 and +4 respectively. The preparation of low oxidation state species, e.g. Al(I) and Si(II), represents a significant synthetic challenge. These species exhibit bonding that frequently challenges accepted bonding theories. Examples include multiple bonding between non-2nd period elements, mixed oxidation state cluster complexes, and so-called umpolung (polarity inversion) reactivity.

Current routes to low oxidation state group 13 and 14 species utilize extremes of temperature and pressure to prejudice redox equilibria, or a strong non-stoichiometric reducing agent such as potassium. These are hazardous, non-selective and expensive to reproduce. In this project you will prepare several hydride complexes of aluminium and silicon and use these as gateways to low oxidation state species via catalytic, chemical and photochemical dehydrogenation (see above).

(b) Catalysis using frustrated 3rd period Lewis pairs

Frustrated Lewis pairs (FLPs) contain a sterically hindered Lewis acid and base that cannot form an adduct due to steric buttressing. This leads to high, potentially catalytic, reactivity with small molecules like H2 and cyclic ethers, albeit with low turnover. We have unparalleled expertise in the design of sterically hindered ligands and their application to the stabilisation of frail chemical functions (see projects a and c). In this project you will develop sterically frustrated aluminium Lewis acids and silicon Lewis bases and apply them to the FLP hydrogenation of sterically hindered imines (see image).

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(c) Heavy group 13 hydrides

We have an interest in the preparation of 5th and 6th period hydride complexes. These are unstable due to the size mismatch of the hydrogen 1s orbital with the heavy metal valence orbitals. Australia has vast mineral deposits of aluminium, gallium, indium and thallium ores, many of which essential for the fabrication of microelectronics. Hydride compounds offer promise in this regard as they are typically volatile, available in high purity, exhibit low deposition temperatures and do so without the deleterious inclusion of carbonaceous material. They are ideal for the development of single source precursors.

The hydride chemistry of thallium is currently non-existent and that of indium is nascent. In this project you will prepare low oxidation state compounds of indium and thallium supported by stabilising ligands as precursor materials for the oxidative addition of dihydrogen or low polarity Si-H and B-H bonds (see above). Particular emphasis will be placed on in situ monitoring of oxidative addition reactions using multinuclear NMR spectroscopy.

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Where does the drug bind? Methods for rapidly pinpointing where small molecules bind to druggable targets are urgently needed for discovering the next generation classes of bioactive molecules.

DR. ALEX DONALD Level 2, Dalton Building (F12)


BIOLOGICAL MASS SPECTROMETRY AND BIOPHYSICAL CHEMISTRY

Mass spectrometry is a core enabling technology that is used in many emerging and existing scientific fields. ARC Discovery Early Career Research Award fellow Alex Donald and his team are developing and applying experimental methodologies in mass spectrometry with a focus on problems in chemistry and biology. We are looking for students who are interested in developing a valuable skillset in mass spectrometry and allied topics.

(a) Rapid, ultra-sensitive protein structure elucidation by mass spectrometry

Potential drugs, pesticides, and antibiotics often fail because they bind to many proteins, leading to safety issues. Pesticides and antibiotics can fail because of resistance resulting from changes to binding sites. This project will develop a method for rapidly discovering classes of molecules that bind to unique sites on proteins. This will provide scientists with novel starting points for designing new bioactive molecules aimed at improving effectiveness, safety, and preventing resistance.

The development of new pharmaceuticals is frequently delayed by the time and resources required to identify the sites that new chemical entities bind to protein targets. A recent breakthrough discovery in our laboratory has resulted in the ability to completely characterise large protein sequences directly from single mass spectra. This project aims to leverage this breakthrough by developing a rapid new approach for revealing ligand-protein binding sites using whole-protein mass spectrometry. The success of this project will enable novel sites of interactions between molecules and protein targets to be discovered rapidly with high sensitivity. This will allow the efficient design of next-generation classes of bioactive molecules.

(b) Cancer breathalyser

Imagine a breathalyser test that can sniff out cancer and other diseases. The ultimate goal would be a personalised and highly accurate warning system for diagnosing disease in the earliest possible stages to maximise the possibility of recovery. This will require (i) high sensitivity, (ii) reliable detection, (iii) rapid sampling, and (iv) selective detection of many different types of molecules that are indicative of disease.

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Portable mass spectrometer for personal chemical analysis: The ultimate device for preventative medicine? New and improved field deployable ionisation methods are urgently required to enable complex mixtures to be directly analysed (e.g., for early detection of cancer and other diseases). J. Am. Soc. Mass Spectrom. 2008, 19, 1442-48.

Single-cell mass spectrometry: What makes a cancer cell a cancer cell? Powerful analytical methods must be developed to enable the contents of single cells to be identified and quantified with unprecedented sensitivity and selectivity.

We have recently developed a compact ionisation method, called “surface enhanced ionisation,” that can be used to directly ionise analytes from highly complex chemical mixtures without sample preparation for rapid detection by mass spectrometry. This is important because it enables chromatographic instrumentation to be eliminated, which will significantly improve the performance of portable hand-held mass spectrometers by (i) reducing size and power requirements and (ii) increasing sensitivity and tolerance for complex mixtures.

In this project, you will use surface enhanced ionisation mass spectrometry to rapidly detect volatile organic molecules in breath and saliva that are “signatures” for lung and breast cancer with ultrahigh sensitivity. This project is part of a longer-term thrust towards developing a high performance portable, handheld, and personal mass spectrometer for monitoring/detecting disease and detecting harmful substances in your vicinity.

(c) Single-cell chemical analysis by mass spectrometry (w/ Scientia Prof. J. Justin Gooding)

We are interested in answering the fundamental question of what makes a cancer cell a cancer cell? Why are some cells drug-resistant while others are susceptible? Why do some metastasize while others do not? Not every cell was created equal. Individual cells within a population can be as dissimilar as the members of human families. Thus, we need to be able to perform chemical analysis on the contents of single cells, which requires the development of powerful analytical methods that have unprecedented sensitivity and selectivity.

For single-cell chemical analysis, mass spectrometry is one of the most promising analytical techniques because it enables many different types of molecules to be rapidly detected and identified nearly simultaneously from exceedingly small sample volumes. However, matrix ion suppression is a key challenge that hinders the ability of scientists to detect the vast majority of metabolites and biomolecules in human cells. Recently, we

have developed a novel, surface-selective ionization approach that enables trace chemicals to be rapidly detected from complex mixtures with minimal ion suppression using mass spectrometry.

In this project, you will take this research to the next level by fabricating novel surface-enhanced microprobes to sample and analyse the contents of single cells by a range of mass spectrometry techniques to target important disease biomarkers. The success of this project will provide a rapid, high-throughput platform to characterise a wide variety of important biomarkers expressed uniquely in each cell, with the goal of understanding how cellular heterogeneity leads to disease states and drug resistance.

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PROF. LES FIELD Level 10, Chemical Sciences Building (F10)


SYNTHETIC ORGANOMETALLIC CHEMISTRY • Research in the Field group is centred around synthetic organometallic chemistry:

o Development of organometallic catalysts that are able to activate small molecules (such as N2, CO2, etc), functionalise organic hydrocarbons to make value-added products, and perform specific organic transformations.

o Development of organometallic polymers for application in areas such as molecular electronics.

• Skills you will learn in the Field group: o Manipulation of air and moisture sensitive compounds. o Structure elucidation and determination of reaction mechanisms. o Heteronuclear NMR spectroscopy (31P, 15N, 29Si, 19F), 2D NMR spectroscopy, IR

spectroscopy and X-Ray diffraction.


(a) Organometallic Polymers

Organometallic compounds containing complexed metals linked by bridging groups have many potential applications in materials science. We are particularly interested in the use of alkyne groups as the bridging unit, and are developing new methods for forming metal complexes where the metal centres are bridged by organic acetylides. Acetylide-bridged organometallic complexes show interesting electrochemical behaviour, and electronic communication between the two metal centres is often observed.

We recently discovered a straightforward route to an iron acetylide dimer

where two iron centres are linked by a single C≡C bridge. We are interested in extending the chemistry to ruthenium and exploring the

chemistry of C≡C bridged complexes. In particular, we are interested in extending the -M-C≡C-M-C≡C-M- chain to build up metal-acetylene polymers (seen in the figure below).

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Alternative Bridging Groups for Organometallic Polymers

The majority of alkyne-bridged organometallic polymers use linear aromatic spacer units, such as 1,4-diethynylbenzene, as the bridge between metal centres. Non-aromatic bridges such as 1,12-diethynyl-p-carborane (C6H12B10) have been described as “3D aromatic systems”. We are interested in the effect of aromatic bridges, as well as non-aromatic bridges such as 1,3-diethynylbenzene, on the chemical and electrochemical behaviour of organometallic polymers.

(b) The Organometallic Chemistry of Carbon Dioxide

Carbon dioxide reacts with many organometallic compounds to give products in which the CO2 is incorporated into the metal complex. A greater understanding of the ways in which CO2 binds and reacts with metal compounds may provide new ways to capture CO2 and utilise this wasted and environmentally dangerous compound.

Our previous work has focused on the stoichiometric insertion of CO2 into metal-hydride and metal-carbon bonds, to give metal formates and acetates, respectively. There have been many reports in the literature of catalytic activation of CO2 to yield formic acid (by hydrogenation), acrylates (by reaction of CO2 with ethylene), and carbonates (by reaction of CO2 with epoxides). We are interested in exploring the ability of novel iron(II) and ruthenium(II) complexes that we have prepared in the lab to catalytically activate CO2.

(c) The Chemistry of ‘CP3’ Complexes

We have recently developed a new type of polydentate ligand for transition metals, which binds to metal centres using three phosphorus donors and an anionic carbon donor. To date, we have only explored the chemistry of this ligand on ruthenium(II). We anticipate that this ligand will form complexes with a wide range of transition metals, and are particularly interested in investigating the synthesis and catalytic properties of new rhodium and iridium complexes.

Selected publications from the group: 1. L. D. Field, A. M. Magill, T. K. Shearer, S. J. Dalgarno, M. M. Bhadbhade, Eur. J. Inorg. Chem., 2011, 23, 3503-3510.

2. L. D. Field, P. M. Jurd, A. M. Magill, M. M. Bhadbhade, Organometallics, 2013, 32, 636-642.

3. O. R. Allen, L. D. Field, A. M. Magill, K. Q. Voung, M. M. Bhadbhade, S. J. Dalgarno, Organometallics, 2011, 30, 6433-6440.

4. L. D. Field N. Hazari, H. L. Li, Inorg. Chem., 2015, 54, 4768-4776.

Ru

PR2

PR2L

R2P

HXCO2 + H2 + Et3N + ROH HCOOR

cat.cat. =

C M C

L L

L L

CRC C M C

L L

L L

CRC

Potential Spacer Groups

L = CO, NC-C6H4-4-Me, PnBu3, N2, tBuNC

Ru

PPh2

PPh2L

Ph2P

HC

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SCIENTIA PROF. J. JUSTIN GOODING Level 1, Dalton Building (F12)


Australian Centre for NanoMedicine

BIOSENSORS, NANOMATERIAL, AND NANOMEDICINE Our research group specializes in using self assembled monolayer or other surface modification technique to provide surfaces with unique functionality. The surfaces are the base upon which we build functional devices from nanscale component including polymer, protein, nanoparticles, and porous material. The three major programs in which these surfaces are applied are, biomaterials, biosensor, and drug delivery. The multidisciplinary nature of our research means we need people with interest in medicinal chemistry, surface chemistry, polymer chemistry, nanotechnology or analytical chemistry. All new members of the group will be looked after by a post-doctoral fellows as well as Prof. Gooding. Specific projects are:

Digital assays - Sensitive Biosensors for the Digital Age (in collaboration with Professor Richard Tilley) The detection of disease biomarkers (such as proteins, DNA fragments and RNAs) in biological fluid is essential for the early detection of diseases. One of the primary challenges is the low concentration (typically in the femtomolar range) of the biomarkers. We are looking into new approaches to construct digital biosensors based on plasmonic nanoparticles. With the help of a dark-field optical microscope, we can look at the scattering arising from individual nanoparticles. The wide field nature of this measurement allows for the simultaneous characterization of thousand nanoparticles. When a biochemical sensing reaction is performed, the optical signature of the nanoparticle is altered thereby leading to change in the colour of the nanoparticle. By setting a threshold, we digitalize the data to 0 (unreacted) and 1 (reacted) nanoparticles. Our aim is to push this approach for the detection of individual biomarkers on individual nanoparticles.

Detection of Biomolecules using Au nanoparticle clusters (in collaboration with Professor Richard Tilley) A typical nanoparticle based biosensors consists biomolecule that can specifically bind to the target molecule and the nanoparticle plays the role of a signal transducer. The signal transduction is achieved by exploiting a change in the optical response of the nanoparticle. Gold nanoparticles are attractive for this application, as gold nanoparticles of different sizes and shapes can be

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synthesized in a straightforward manner. The optical properties of gold nanoparticles are dependent on its size, shape and the dielectric environment surrounding the nanoparticle. In this project, we propose the synthesis of functionalized gold structures which can specifically disassemble in the presence of the target analyte. A typical functionalization scheme involves the use of biomolecules (such as cyclodextrins) which can undergo degradation in the presence of target molecule. The experimental techniques in the project include the synthesis and functionalization of Au nanoparticles. The nanoparticle dimers will be characterized using various microscopy and spectroscopy methods.

3D printing of cells for improved tumour models and drug assays (in collaboration with Australian Centre for Nanomedicine)

Our current understanding of cancerous tumours is heavily based on in vivo experiments in animals or in vitro experiments on tissue culture plates. To date, few techniques exist that can satisfactorily recreate the tumour environment in vitro in 3-Dimensions. Such models would allow biologists to better understand the effect of spatial organisation of biomolecules on cell behaviour. Of particular interest are molecules that trigger cancer cell metastasis, or invasion, to other parts of the body. In our lab we are developing materials that can recreate the 3D tumour environment, made from polymers that provide a matrix for cells to attach to (see figure). In the proposed project, the polymers will be modified to include a peptide (protein-based) crosslink that stabilises the structure. Such protein-based regions are susceptible to degradation by specific types of enzymes (proteases) released by cancer cells when they invade surrounding tissue. The new materials developed in this project will be used as an extracellular matrix for the 3D printing of cells in collaboration with a 3D printing start-up company.

The synthesis of well defined gold nanorods for drug delivery, photothermal therapy and the detection of single bacteria (with Professor Richard Tilley)

Gold nanorods have unique optical and thermal properties that make them ideal for a range of applications such as drug delivery, being a drug and in sensing. For many applications gold nanorods of well defined size are required. The project will focus on the synthesis of these rods as models for understanding the role of size, shape and surface chemistry on the transport of drug delivery nanoparticles through a cell to the nucleus. This will be achieved using state of the art optical microscopy. The successful applicant for this project will learn nanoparticle synthesis and characterisation using electron microscope as well as some basic cell biology and optical microscopy.

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DR. JASON HARPER Level 2, Dalton Building (F12)


MECHANISTIC AND PHYSICAL ORGANIC CHEMISTRY

Our research is focussed on understanding how organic processes happen and what affects reaction outcomes. Particularly this encompasses examining how structural features in both the reagents themselves and the solvent used can change how a reaction proceeds. This knowledge can then be applied to a range of fields, including bioorganic, synthetic, analytical and environmental chemistry. Being particularly interdisciplinary, there is extensive opportunity for collaboration and this is currently underway in the areas of catalysis, reaction kinetics, synthesis and molecular dynamics simulations.

(a) Ionic liquid effects on organic reactions: getting the reaction outcomes you want1 (in collaboration with Dr Anna Croft, University of Nottingham, UK; Dr Ron Haines, University of New South Wales; and Dr James Hook, Mark Wainwright Analytical Centre)

Ionic liquids are salts that melt below 100°C. They have potential as replacements for volatile organic solvents but outcomes of reactions in ionic liquids are often unexpectedly different to those in traditional molecular solvents. The focus of this project is to extend the understanding of ionic liquid solvent effects we have already developed and to use this knowledge to demonstrate that ionic liquids can be used to control reaction outcome. The project would involve using NMR spectroscopy to monitor reactions and kinetic analyses of these results, along with synthetic organic and analytical chemistry. The project can be readily tailored for students with more interest in the physical and analytical aspects, with the opportunity to develop new methods for following reaction progress and undertake molecular dynamics simulations, or to the more synthetic aspects, by focussing on designing new ionic liquids, increasing reaction yield and optimising isolation. That is, to get the reaction outcome you want!

(b) Non-planar aromatic hydrocarbons: different reactivity based on structure2 (in collaboration with Prof. Lawrence Scott, Boston College, USA)

Aromatic hydrocarbons are meant to be planar – right? Yet the synthesis of carbon nanotubes and related structures relies on the reactivity of curved aromatic systems. This project focuses on the different reactivities of these systems

AcCl, AlCl3DCM, -78oC less reactive

than similar flat systems

Cl

MeO

pyridine

ionic liquidN

MeO

Cl

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relative to 'normal' aromatics and how it might be controlled and exploited. It will predominantly involve synthesis and reactivity of systems, such as those shown below, with the opportunity for some kinetic studies to interpret the reactivity. Ultimately, understanding and exploiting these differences will allow the rational synthesis of these curved polyarenes.

(c) Catalysis using N-heterocyclic carbenes: understanding structure/activity relationships3 (in collaboration with Assoc. Prof. Marcus Cole, University of New South Wales)

N-Heterocyclic carbenes, have significant roles in organo- and organometallic catalysis, however some carbenes are effective for some processes but not for others; the origin of this is not well understood. This project aims to relate structure and chemical properties of carbenes to catalytic efficacy, along with observing any solvent effects – this requires a series of chosen carbenes that vary in one way only (steric bulk, electronics, heteroatoms). Along with making the precursors to the carbenes, this project involves the opportunity to utilise various characterisation techniques and to undertake evaluation of catalytic systems; the latter can vary from simple screening of catalysts through to detailed kinetic analyses. The ultimate goal is to be able to rationally choose an NHC catalyst for a given process.

(d) Solvent-solute interactions in ionic liquids: can we design better solvents?4 (in collaboration with Drs Leigh Aldous and Ron Haines, University of New South Wales; and Assoc. Prof. Anna Croft, University of Nottingham, UK)

We have previously made use of molecular dynamics simulations to understand interactions between a solute and the components of an ionic liquid; this can be used to explain why benzene is so soluble in ionic liquids and why certain reactions proceed faster on moving to ionic solvents. This project aims to extend this and to model - both with simple compounds and simulations – which ionic liquid would be better solvents for a given solute. In order to do this both physical measurements of solubility and molecular dynamics would be undertaken to highlight key solute-solvent interactions. The outcome would be a better understanding of what interactions are required to confer good solubility giving us the opportunity to 'design' appropriate properties into ionic liquids – and these could then be made!

For recent examples of our work in the above areas see:

1. R. R. Hawker et al., ChemPlusChem 2016, 81, 574; B. J. Butler et al., Magn, Reson. Chem. 2016, 54, 423; S. T. Keaveney et al., Org. Biomol. Chem. 2016, 14, 2572 & 2015, 13, 8925.

2. S. R. D. George et al., Org. Biomol. Chem. 2015, 13, 9035 &10745.

3. M. H. Dunn, M. L. Cole and Jason B. Harper, RSC Adv. 2012, 2, 10160 & J. Org. Chem. 2016, submitted.

4. W. E. S. Hart, J. B. Harper and L. Aldous, Green Chem. 2015, 17, 214.

N NR R

NN NR R

N SR

Cl

H

O O

OH

Cl

Cl

Cl

H

O

+O

Cl

N SR

✔!

✗!

✗!

✔!

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DR. LUKE HUNTER Level 1, Dalton Building (F12)


FLUORINE IN MEDICINAL AND ORGANIC CHEMISTRY

• Fluorine is a small atom that packs a big punch. When incorporated into organic molecules, fluorine can have a dramatic impact on molecular properties such as pKa, metabolic stability, 3D conformation, and binding affinity for protein targets.

• In the Hunter group, we are harnessing such effects to optimise the properties of a variety of bioactive molecules. We collaborate extensively to evaluate the biological properties of the fluorinated molecules that we create.

Here are some of the broad research areas within the Hunter group:

(a) Fine-tuning the shapes of cyclic peptides

Cyclic peptides are promising lead compounds for the treatment of a variety of diseases including cancer and malaria. However, there are two major limitations of cyclic peptides: (i) their synthesis via head-to-tail cyclisation is often inefficient; (ii) it is difficult to fine-tune the shapes of cyclic peptides to optimise their target binding. In this project, we are using fluorine chemistry to solve both of these problems. The key is to synthesise stereoselectively fluorinated amino acids, which are valuable shape-controlled building blocks.

Collaborators: Prof Maria Kavallaris, A/Prof Shelli McAlpine, A/Prof Renate Griffith, Dr Eddy Pasquier, Prof Vicky Avery

(b) Next-generation enzyme inhibitors Aspartic proteases are enzymes that cleave other proteins in a sequence-specific manner. Aspartic proteases are involved in the life-cycles of several diseases including cancer, malaria and HIV, and thus they are potential drug targets. In this project, we are designing a new class of aspartic protease inhibitors. The key is to incorporate fluorine atoms into our inhibitors at very precise locations, in order to mimic the electron distribution of the activated intermediate of peptide hydrolysis.

Collaborators: A/Prof Renate Griffith, Dr Nady Braidy

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(c) Towards a novel treatment for stroke

Stroke is a leading cause of death and disability in Australia, and the treatment options are extremely limited. To try to solve this problem, we are investigating a medicinal mushroom called the “veiled lady.” This mushroom has been used as a traditional remedy for nervous disorders; it produces an alkaloid that protects nerve cells against the types of damage incurred by stroke. In this project, we are optimising the properties of this alkaloid, by various means including incorporating fluorine substituents at key locations within the molecule.

Collaborator: Dr Nicole Jones

(d) Editing the undesirable activity out of illegal drugs Gamma-Hydroxybutyrate (GHB) is a molecule with a bad reputation. It binds to neurotransmitter receptors in the brain, and it has previously been prescribed to treat a variety of ailments including alcoholism and depression. Unfortunately however, GHB also has sedative/hypnotic activity, which has led to its abuse as a “date-rape” drug. We believe that the bewildering variety of GHB’s effects can be attributed to the molecule’s conformational flexibility, which allows it to bind to many different neurotransmitter receptors. In this project, we are creating conformationally-restricted fluorinated analogues of GHB, in order to preserve the desirable activity while editing out the undesirable activity.

Collaborator: Prof Mary Collins

(e) A weight loss wonder drug? Certain molecules called “mitochondrial uncouplers” are able to transport H+ ions across the inner mitochondrial membrane. This bypasses ATP synthase and sends the cell into metabolic overdrive. Thus, mitochondrial uncouplers can potentially be used as weight-loss drugs, as well as being valuable biochemical diagnostic tools. In this project, we are optimising the properties of a novel mitocondrial uncoupler. The key is to incorporate fluorine atoms at strategic locations within the molecule, in order to maximise solubility in the inner mitochondrial membrane and to optimise affinity for H+ ions.

Collaborator: Dr Kyle Hoehn

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PROF. SCOTT KABLE Level 1, Dalton Building (F12)


LASER PROBES OF CHEMICAL REACTIONS

• Use laser spectroscopy to characterise new free radicals; • Discover new chemical reaction mechanisms that cannot be explained by current theories; • Contribute to international atmospheric models to test hypothesized atmospheric processes; • Projects on chemistry education available.


(a) Weird chemistry – reactions that just don’t go where they should. (Collaborators: Meredith Jordan, Sydney Univ., David Osborn, Sandia National Labs, USA)

Since the 1930’s, the concept of a transition state (TS) has formed the bedrock of chemical reaction theory. When the activation energy is very near the TS energy, the reaction becomes very slow and other unsuspected processes become competitive, even dominant. Over the past few years we have identified new chemical pathways never previously described.

The “Roaming” reaction: When a reaction is initiated near the energetic threshold, the products barely have enough energy to escape each other’s influence. Here, they “roam” around each other and re-collide, forming new, unexpected products. This project will seek roaming products from a variety of photochemical reactions and to explore whether these new products play a role in the chemistry of the atmosphere.

(b) Atmospheric Chemistry (Collaborators: Meredith Jordan, Sydney Univ., Dwayne Heard, Univ. of Leeds)

In the 1950s, the only volatile organic compounds (VOCs) known to be in the atmosphere were H2CO and CH4. Between 104 and 105 VOCs have now been measured. This complexity makes developing a predictive model of the atmosphere very challenging. However, such models are essential if we are to understand the role of different chemical species on air quality, ozone depletion and climate change.

Photo-isomerization is completely absent in atmospheric models. The Master Chemical Mechanism (MCM), one of the standard atmospheric models, includes 17,000 reactions – but no photo-isomerization. Recently, we discovered that photo-tautomerization occurs in at least one important atmospheric compound under atmospheric conditions, yielding an enol. Including this reaction into the MCM doubles the predicted yield of formic acid. We hypothesize that photo-isomerization is a general mechanism and its omission is the cause of the discrepancy between modeled and observed concentrations of

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organic acids generally. In this project you will discover new photo-isomerization mechanisms in the lab and test their effect in the MCM.

(c) Radicals in the atmosphere and combustion (Collaborator: Tim Schmidt)

Free radicals are key intermediates in all complex chemical reactions. OH radical attack is the first step in the “processing” of nearly all atmospheric compounds. Processing can reduce the molecular weight, leading to fully oxidized products (CO2 and H2O) or increase the MW, reducing the volatility and leading to harmful aerosol formation. The processing of either biogenic emissions (e.g. terpenes) or anthropogenic emissions (e.g. toluenes) is largely unknown. We have developed laser-based techniques and built custom instruments to create and isolate a wide variety of radicals. Different types of laser spectroscopy are used to probe their structure. There are several projects on offer for 2017, for example:

Radicals from OH attack on atmospheric species: OH can attack unsaturated hydrocarbons in two

different ways: abstracting H to form H2O and a radical, or adding across a π-bond to form an OH-adducted radical. The OH-adducted radicals have been scarcely measured in the literature. In this

project you will investigate either a typical biogenic compound (e.g. α-pinene) or anthropogenic compound (e.g. cyclohexene) and react it with OH. The ensuing OH-adducted or abstracted radical will be isolated in vacuum and probed using laser spectroscopy to determine where the OH adds or attacks and the isomeric and electronic structure of the radical product. This will provide the first firm evidence for the assumed initial step in atmospheric processing of these compounds.

H-atom addition/loss from common fuels and biofuels: Hydrogen atoms can be lost from or gained by aromatic fuels, in both cases making radicals. In this project you will choose such a fuel, and use a custom-built reactor to make it gain or lose H. The resulting radical, the first intermediate in combustion, will be mass selected and probed by laser spectroscopy.

All projects above can be tailored to have a significant computational chemistry component, or tailored to be almost exclusively experimental in nature, or anywhere in between.

(d) Science Education (Collaborators: Steve Colbran, Ron Haines, Luke Hunter, Scott Sulway, Kim Lapere)

I have a long-standing interest in chemistry education, especially in how students learn in the laboratory. There are a variety of potential Honours projects that would suit a science student from any discipline with an interest in education (e.g. interested in becoming a teacher).

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PROF. NARESH KUMAR Level 2, Dalton Building (F12)

T: 9385 4698 E: [email protected]. au

SYNTHETIC ORGANIC and MEDICINAL CHEMISTRY

The main focus of the research undertaken in my group is the discovery and development of novel bioactive molecules. Naturally produced chemicals are of fundamental importance in biological systems. Such chemicals are used to mediate interactions across all levels of biological hierarchy. Very often such diverse molecules are produced only in minute quantities. New or innovative organic syntheses not only provide access to sufficient quantities of these molecules but also their analogues. The access to various structurally-related analogues allows full assessment of their biological activity and mode of action, and offers opportunities to develop new therapeutic leads. The research is multi-disciplinary in nature and involves a combination of synthetic organic chemistry, molecular modelling and biological screening.

(a) DESIGN AND SYNTHESIS OF NOVEL ANTIMICROBIAL AGENTS

Quorum Sensing Inhibitors

The emergence of multi-drug resistance in common human pathogens has highlighted the need to develop novel classes of antimicrobials for the treatment of human disease. A number of projects are available in this area focussing on a combination of organic synthesis, molecular modelling, and in vitro and in vivo antimicrobial screening. This project will develop novel antagonists of bacterial signalling pathways, which inhibit the regulatory quorum sensing communication pathways of bacteria, and will model the receptor-ligand interaction using the X-ray crystal structures of bacterial signal receptors e.g. AHL receptor LasR. This represents a non-growth inhibition strategy that is less likely to result in the development of drug resistance1. In particular, this proposal will investigate the design and synthesis of a range of novel heterocyclic compounds with antimicrobial activity.

New scaffolds for antimicrobial discovery

(in collaboration with Prof. David StC Black)

The majority of conventional antibiotics used today share a common feature in that they act on specific molecular targets. Having very well-defined targets, these drugs act with a high degree of selectivity, minimizing unwanted side effects. However, a major limitation of antibiotics targeting a single receptor is the ease with which resistance can be developed. The central aim of this project is to design novel small molecular antimicrobial peptide (SMAMP) mimics based on glyoxylamides2, which disrupt the normal functioning of the membranes of the bacterial cell, and as a consequence allow the development of antimicrobial agents with enhanced activity and the ability to bypass resistance mechanisms used by bacteria against other antibiotic types.

NO O

O

NH

H

Cationicgroups

Hydrophobic groups

Backbone

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Inhibitors of Bacterial Transcription Initiation

(in collaboration with A/Prof. Renate Griffith, UNSW and Prof. Peter Lewis, University of Newcastle)

The enzyme RNA polymerase (RNAP) that transcribes DNA into RNA is highly conserved across species. However, the factors that regulate the activity of RNAP are target-specific. Therefore, the unique interaction of sigma factors with RNAP in bacteria represents an ideal target for the development of small molecules that can specifically inhibit this interaction3. In this project new molecules that target these essential protein-protein interactions will be rationally designed and synthesized, and evaluated for their antimicrobial efficacy. These new small molecules would represent lead compounds for the development of new antibiotics.

(b) DEVELOPING ANTICANCER COMPOUNDS THAT ACTIVATE GLUCOSE OXIATION

(in collaboration with Dr Kyle Hoehn, BABS, UNSW) Cancer is a major burden of disease, affecting the lives of tens of millions on a global scale. A hallmark feature of nearly all cancer cells is their altered metabolism of glucose compared to non-cancerous cells. Relative to most normal cells, cancer cells use a greater proportion of incoming glucose for non-oxidative purposes including the production of building blocks for cell division (lipid, DNA and protein), rather than oxidative pathways that produce carbon dioxide (CO2) in mitochondria. The goal of this proposal is to develop anticancer molecules that change cancer cell glucose metabolism to be more like that of non-cancerous cells. We have identified a small molecule that increases glucose oxidation and selectively kills cancer cells in vitro and in mice. The aim of this project is to generate new derivatives with enhanced activity and drug-like properties. The new compounds will be evaluated for anticancer activity in various cancer cell lines.

(c) DESIGN AND SYNTHESIS OF NOVEL ANTIMALARIAL AGENTS

(in collaboration with Prof David Black)

Flavones and isoflavones are two structurally related large and diverse groups of natural compounds with broad spectra of biological activities including antioxidant, anticancer, antiviral and anti-inflammatory properties. They are recognized as “privileged” medicinal chemistry molecular frameworks because they are commonly found in biologically active compounds that show drug-like characteristics. Dependensin is a dimeric flavonoid isolated from the rootbark of a Tanzanian medicinal plant, Uvaria dependens. The crude extract of this plant shows potent antimalarial activity. Our group has reported the successful synthesis of dependensin via the acid-catalyzed reaction of 5,7,8-trimethoxyflavene. A number of projects are available in this area focussing on the design, synthesis and evaluation of antimalarial activity of new azaflavone analogues in which the ring oxygen atoms are replaced by nitrogen atoms.

1. Org. Biomol. Chem., 2015,13, 9850-9861

2. Org. Biomol. Chem., 2016,14, 680-693

3. Org. Biomol. Chem., 2014,12, 2882-2894

O

O

OMeMeO

OMe

MeO OMe

OMeH H

H

H

NH

N

O

O

ClO

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DR. HONGXU LU Level 5, Chemical Science Building (F10)


DRUG DELIVERY VIA NANO CARRIERS IN IN VITRO CELLULAR MODELS

• Nano drug carriers provide a promising tool for cancer therapies via precise and effective tumor-targeted drug delivery. As a DECRA research fellow, my current research focuses on cellular internalisation, trafficking and drug delivery efficacy of nanocarriers in in vitro two- and three-dimensional cellular models. • I am also interested in investigating cell-biomaterials interaction and tissue engineering using three-dimensional scaffolds. • The research is aiming for the development of functional tools to overcome the limitations of traditional therapies.


(a) Drug delivery via nano carriers in 3D multicellular tumor spheroids (MCTS)

The drug delivery systems powered by nanocarriers enable the preferential delivery of drugs to tumors owing to the enhanced permeability and retention (EPR) effect and overcome the inherent multidrug resistant (MDR) of tumors in chemotherapeutics. Multicellular tumour spheroids (MCTS) have recently gained increasing recognition as an important 3D tumour model for the evaluation of nano drug delivery systems to bridge the gap between 2D cell-based assays and animal studies. The nanocarriers can penetrate deeper into the MCTS and enhance drug delivery and killing efficiency compared to drugs alone. Detailed knowledge of the relationship between nano drug carriers and MCTS is invaluable as this information could be used to develop functional and efficient of nano drug carriers. This research will use various nanocarriers to treat MCTS obtained from different tumor cells (pancreatic, breast, lung, prostate) and investigate the key parameters to improve nano carrier penetration, drug delivery, and MCTS dissociation.

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(b) Development of tumor histoids for drug and nanoparticle screening

Development of reliable in vitro evaluation systems remains a difficulty, together with the disparities in the experimental conditions used to screen drugs and/or to study nano carrier efficacy. Although most MCTS exhibit higher similarity to real tissues than monolayer cells, the technical aspects of MCTS remain challenging with respect to their 1) morphology that could mimic the tissue-like microenvironment and 2) cellular heterogeneity of normal and tumour cells. This project aims to fabricate a tissue-like tumour model - histoids and to mimic the tumors in different classifications. Nano drug carriers will be applied to treat these histoids and to compare the efficacy of nano carriers on different type of tumors. The cancer histoids may also be applied in other fields such as nanotoxicity studies and pharmaceutical researches.

(c) Cellular uptake of nano drug carriers in novel 2D cellular models

The mechanisms underlying cell-nanoparticle interactions remain largely unknown. It has hampered the design and development of innovative nano devices to be used for drug delivery, biomarkers and diagnostics. This project explores the influences of size, density, geometry, intercellular communication and substrate properties on cell-nanoparticle interactions. A micropatterning technology is applied to precisely control cell behaviours. The endocytosis, exocytosis, intracellular trafficking and drug release of nanoparticles will be investigated using this precisely-controlled in vitro cellular model. This project is aiming to improve the understanding of cell-nanoparticle interactions which will provide new insight into nanoparticle design and improve the efficacy of nano devices.

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Dr Adam Martin Level 1 (Room 126), Dalton Building (F12)


SUPRAMOLECULAR CHEMISTRY & NANOTECHNOLOGY

• Design of biomimetic hydrogels which recreate the native extracellular matrix • Synthesis of responsive short peptides • Controlling the self-assembly of hydrogels across pH ranges • Bioconjugation of reporter molecules to probe the cellular environment


(a) Using hydrogels to recreate the extracellular matrix of the brain (collaboration with Prof. Lars Ittner, School of Medical Sciences, UNSW)

The extracellular matrix (ECM) is a vital part of the cellular microenvironment, providing both physical and chemical support for cell growth, proliferation and in some cases, differentiation. To accurately mimic the ECM of the body, an appropriate three dimensional ECM mimic must be developed, as current products suffer from a range of detrimental issues. Hydrogels are composed of small fibres which encapsulate solvent and accurately mimic the structure of the extracellular matrix. This work involves designing, synthesising and characterising hydrogels composed of short peptides which can support the growth of neuronal cells and control cell growth by varying hydrogel properties. In this way the effect of the ECM on cell growth, differentiation and even the progression of disease can be examined in a controllable manner.

(b) Controlling the self-assembly of hydrogels through metal incorporation

Hydrogels are composed of fibres which cross-link to form a network that encapsulate a chosen solvent. Hydrogels composed of short peptides have potential uses in drug delivery, regenerative medicine and sensors, due to their biocompatibility and tunability.1 However, the mechanism of self-assembly for short peptide hydrogels is poorly understood, limiting their real world applications. A greater control of the self-assembly process is required to design the next

39

generation of responsive hydrogels. Recent work shows that self-assembly can be controlled by selecting which metal cation is chosen to trigger gelation in these materials2 – in this project we will exploit this to push the limits of self-assembly and work towards examining the origin of gel formation.

(c) Luminescent, flexible metal organic frameworks that selectively sense guest molecules

Metal organic frameworks (MOFs) are porous, crystalline materials with applications in gas adsorption (including hydrogen and CO2), sensing and separation of structurally similar compounds. MOFs synthesised using dipeptides and transition metal centres have been shown to be useful materials which can alter their structure in response to guest uptake.3 In this project, simple di and tripeptides will be synthesised and combined with lanthanides in order to obtain luminescent MOFs whose spectral properties are altered upon the incorporation of guest molecules.

(d) Conjugation of responsive molecules for probing cellular environments (collaboration with A/Prof. Pall Thordarson, UNSW)

This project focuses upon the generation of responsive materials for probing the cellular environment. Here, short peptides will be designed that contain a “handle”, allowing for the attachment of a reporter molecule that is responsive to changes in the intracellular or extracellular space. This project allows a range of bioconjugation strategies to be explored, with the end goal focused on creating materials that are able to support cell growth and then exhibit a dynamic response upon an applied stimulus.

1. A. D. Martin, A. B. Robinson, P. Thordarson, J. Mater. Chem. B., 2015, 3, 2277

2. J. Shi, Y. Gao, Y. Zhang, B. Xu, Langmuir, 2011, 27, 14425.

3. C. Marti-Gastaldo, M. J. Rosseinsky, et al., Nat. Chem., 2014, 6, 343.

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A/PROF. SHELLI R. MCALPINE Level 2, Dalton Building (F12)

T: 0416-728-896 E: [email protected]

SYNTHETIC ORGANIC AND MEDICINAL CHEMISTRY

• Synthesis: develop new anticancer molecules that target heat shock proteins • Biology: understand the role that heat shock proteins play in cancer cell growth • Medicinal Chemistry: identify the binding site for anti cancer molecules

We have the following projects available for Honours students:

(a) Developing new molecules that target cancer: heat shock protein 70 (Hsp70) inhibitors

Cancer cells overexpress heat shock proteins (hsps), and specifically high levels of heat shock protein 70 (up to 10 fold) in order to rapidly grow into tumours. Hsp70 helps cancer cells to grow and it also protects them from cell death pathways, which allows them to thrive in high stress conditions. Hsp70 inhibitors are still in preclinical development and are not well understood. This project will involve designing and synthesizing heat shock protein inhibitors that bind to Hsp70’s IEEVD region (green in figure below). These inhibitors should stop unfolded proteins from being folded and produce cell death because of the unfolded proteins accumulating. The main goal is to identify inhibitors of Hsp70 (TPR1 mimics), and test them for their ability to inhibit Hsp70’s protein folding function and cell death.

(b) Design probes to evaluate inhibitors of Heat shock proteins 70 and 90. This project would produce a set of unique tools useful for proving whether molecules bind to Hsp90 or Hsp70 or both. They would be the first of their kind and would play in important role in our group in evaluating current inhibitors. These molecules could also become tools offered to other research groups since they would be one of a kind for evaluating whether molecules bind to Hsp70 and/or Hsp90. You would learn peptide synthesis, HPLC, LCMS, NMR as well as several types of binding assays. The goal would be to complete the probes by June, and spend several months running proof of principle biological assays.

Hsp90Hsp70

MEEVD

HOP

TPR1 TPR2A

TPR1 mimicIEEVD

unfolded client protein

folded client protein Cell death

Goal •  Synthesize Heat shock protein 70 (hsp70) inhibitors •  Evaluate the molecules ability to block protein folding, and cause cancer cell death

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(c) Structure-activity studies of molecules that target heat shock protein 27

Heat shock protein Hsp27 plays an important role in many diseases. When Hsp27 is over-active it facilitates cancer cell growth. When it is not functioning properly it can lead to Parkinson’s, Huntington’s, and Alzheimer’s disease. Hsp27’s main cellular role is to fold proteins. The goal of this project is to synthesize molecules that target Hsp27 and test these compounds for their ability to either inhibit Hsp27’s function (a potential new cancer lead) or increase Hsp27’s protein folding function (a potential new lead for Parkinsons, Huntington or Alzheimers). If there is time, we will also investigate where molecules bind to Hsp27 and how they impact Hsp27’s mechanism of action.

Goal •  Synthesize peptides that mimic the IEEVD region of Hsp70 or MEEVD

region of Hsp90 •  Test probes that mimic Hsp70 or Hsp90 using inhibitors

Hsp90Hsp70

MEEVD

IEEVD

HOP

TPR1 TPR2A

Unfolded Protein Folded Protein

IEEVD MEEVD TagTag

Peptideor

peptideSignal

Goals of Proposal

HSP27

HSP27

HSP27

Hsp27

HSP27

Hsp27 Hsp27

Hsp27

27 binder

Oligomers HSP27

Trapped Monomer

HSP27

Hsp27

Inactive

27 binder

HSP27

HSP27

stress Unfolded Protein

accumulation

Cell death

OR

folded protein

Hsp27 binder Increased live

facilitates

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A/PROF. JONATHAN MORRIS Room 227, Level 2, Dalton Building (F12) T: 9385 4733 E: [email protected]

SYNTHETIC AND MEDICINAL CHEMISTRY

• Natural products deliver novel leads for pharmaceuticals in a diverse array of therapeutic areas and offer an excellent starting point for medicinal chemistry programs. A major focus of A/Prof Morris’s research interests are on the development of natural products as biomedical agents.

• Being able to synthesise new molecules in an efficient manner is critical and as such, the focus is on developing strategies to prepare these valuable materials and generate analogs that have improved potency and selectivity.

• The expertise gained from working on these areas leads to a number of collaborations with biomedical researchers where students can become involved in the understanding the biology.


(a) Total Synthesis of Biologically Active Natural Products

The development of efficient syntheses of biologically active natural products continues to be a major activity of the Morris group, with recent targets including ancistrotanzanine A, embellistatin and coproverdine. As syntheses of these targets are completed, work is initiated on their mode of action and their suitability as therapeutic agents. Total synthesis is one of chemistry's most exciting and challenging dimensions, providing you with excellent and broad training in synthetic chemistry. It will develop and hone skills in planning, retrosynthetic analysis, determining mechanisms, and structure elucidation.

Coproverdine

OHOMe

Me

N

OMe

Me

Me

Ancistrotanzanine A

MeOMeMe O

HMeMe

O

Me Me

CO2H

Embellistatin

N

O

OHCHO

MeO2C OH

(b) Developing Inhibitors of RNA Splicing Kinases

The control of the fundamental biological process of alternative splicing is an emerging method for treating diseases such as aged macular degeneration and cancer. It has been established that by controlling the phosphorylation of key proteins in the spliceosome it is possible to switch alternative splicing and generate particular protein isoforms.

The Morris group is actively engaged in the development of small molecules that can do this, and this is achieved by targeting the protein kinases that mediate the phosphorylation. This work originated from earlier work on the

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synthesis of a natural product. Variolin B is a member of a unique class of marine alkaloids isolated from an extremely rare Antarctic sponge. It is no longer available from its natural source. The Morris group have devised a synthesis of variolin B that has restored access to the material and allowed further biological studies to be carried out. From this work it has been established that variolin B is a potent kinase inhibitor and represents an important scaffold for the development of kinase inhibitors. A range of analogs have been developed that are more selective inhibitors of certain kinases, as well as have better properties (such as solubility). However, more work is required to develop molecules that can impact on the control of these kinases.

As part of this program, there exists the possibility of carrying out a joint project with A/Prof. Renate Griffith, where the project would consist of a combination of molecular modelling and synthesis.

(c) Medicinal Chemistry Projects

• Developing the AAL(S) Scaffold for Therapeutic Applications (collaborations with Assoc Prof Nigel Turner (SOMS), Dr Anthony Don (Lowy Cancer Centre), Dr Nikki Verrills/Dr Matt Dun (Newcastle)

Ceramide synthase (CerS) and pyrophosphatase 2A (PP2A) are two enzymes that play a critical role in the regulation of multiple cellular signalling processes. The malfunctioning of these two enzymes has been found to have implications in diseases such as cancer, diabetes, asthma and neurological diseases including Alzheimer’s disease and stroke. Little is known about the biological mechanism of these enzymes and in particular, how they cause such diseases. To gain insight into these biological processes, the CerS and PP2A binders, FTY720 and AAL(S), will be used to explore the binding site of both enzymes and allow the identification of chemical probes which can be used to develop an understanding of the biological mechanisms of these complex diseases.

Development of the AAL(S) scaffold will allow for analog production which along with key biological testing will provide important SAR information towards CerS and key information towards revealing the biochemical pathways and proteins involved regulating both enzymes at a molecular level.

• Controlling the Production of β III−Tubulin (collaboration with Prof Maria Kavallaris, Lowy Cancer Centre/Children’s Cancer Institute Australia)

Evidence suggests that microtubule proteins namely, �-tubulins are dysregulated in tumor cells and are involved in regulating chemosensitivity. Data from the Kavallaris group has demonstrated that �III-tubulin is a key player in promoting cancer growth and survival, and silencing its expression may be a potential therapeutic strategy to increase the long-term survival of cancer patients. Identification of small molecules that can control the production of �III-tubulin is an important step in understanding how this critical protein operates.

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DR. VINH NGUYEN Level 2, Dalton Building (F12)


ORGANOCATALYSIS: A NEW HORIZON FOR SYNTHESIS OF ORGANIC STRUCTURES

Nguyen’s group has several Honours projects focusing on the development of novel organocatalytic systems and applications of those in synthetic organic chemistry. Organocatalysis, chemical processes catalyzed by small non-metallic organic compounds, has recently emerged as one of the most promising fields in organic chemistry. It can be employed in diverse synthetic cascade sequences to quickly construct complex bonds, stereocenters and polycyclic frameworks. Organocatalysts are less expensive, less toxic, more stable and exhibit superior solubility in both organic and aqueous solutions compared to organometallic/bioorganic analogues. Most importantly, organocatalysis generally gives rise to outstanding stereoselectivity, which is significantly valuable and useful at the structural engineering stage of bioactive compounds and pharmaceutical agents.

(a) Project NTV1 - Development and Application of Novel Brønsted SUPER-BASES

The focus of Brønsted base organocatalysts has recently shifted from normal amines towards organic compounds with enhanced proton affinity, termed superbases. Known superbase compounds include amidines, guanadines, phosphazenes and cyclopropenimines. This project aims to develop a new family of hexaaminocycloheptatrienimine superbases with unique structural properties, which allow strong stabilization of the positive charge on its conjugated acid form due to seven nitrogen atoms and the aromatic cation tropylium system (see scheme below).[1-4] These hexaaminocycloheptatrienimines, expected to be the STRONGEST ORGANIC BASES ever, can be used to facilitate important Brønsted-base catalyzed chemical processes, including asymmetric Brønsted-base catalysis. Students are encouraged to discuss with Vinh in person about this project.

(b) Project NTV2 - N-Heterocyclic Olefins as Novel Organocatalysts

Recently, N-Heterocyclic Olefins (NHOs, see scheme) have emerged as a new class of valuable reaction promoters with interesting action mechanisms. These compounds can be conveniently produced from commercially available precursors in one step. NHOs were originally targeted as a

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series of active agrochemicals in the 1970s, but they slowly revealed to be a far more interesting compound family. Due to the donating ability of the two nitrogen atoms, the exocyclic C-C double bond is very electron-rich and strongly polarized. This interesting feature of NHOs offers multinucleophilic

reactivity over the ketene aminal frameworks.[5] Due to the strong nucleophilicity of the α-carbon, NHOs can act as strong Lewis/Bronsted bases.[6-7] This project will focus on synthesizing a family of NHOs, estimating their basicity and applying them as organocatalysts to promote environmentally friendly chemical processes. Students are encouraged to discuss with Vinh in person about this project.

(c) Tropylium-Based Host-Guest (collaboration with A/Prof Pall Thordarson)

Tropylium is a π-electron poor 7-membered aromatic cation.[4] Recent synthetic advances by our group have made this unusual structural much more accessible,[1-3] allowing us now to start to explore their potential in host-guest chemistry in collaboration with A/Prof Pall Thordarson’s group. Their electron-deficient nature makes them particularly attractive for the binding and sensing of small and medium-sized biologically important anions such as chloride, phosphate and carbonates. We propose the synthesis of tropylium-based macrocycles (see figure) as the starting point for this project, which will represent a new platform in supramolecular chemistry. Please also see Thordarson’s Honours projects for more details.

References

[1] T. V. Nguyen,* A. Bekensir, Org. Lett. 2014, 16, 1720-1723. http://dx.doi.org/10.1021/ol5003972 [2] T. V. Nguyen,* M. Hall, Tetrahedron Lett. 2014, 55, 6895-6898. http://dx.doi.org/10.1016/j.tetlet.2014.10.100 [3] T. V. Nguyen,* D. J. M. Lyons, Chem. Commun. 2015, 51, 3131-3134. http://dx.doi.org/10.1039/C4CC09539A

[4] D. J. M. Lyons, R. D. Crocker, M. Blümel, T. V. Nguyen,* Angew. Chem. Int. Ed. 2016, in press, DOI = 10.1002/anie.201605979. http://dx.doi.org/10.1002/anie.201605979

[5] R. D. Crocker, T. V. Nguyen,* Chem. Eur. J. 2016, 22, 2208-2213. http://dx.doi.org/10.1002/chem.201503575

[6] M. Blümel, J.-M. Noy, D. Enders, M. H. Stenzel, T. V. Nguyen,* Org. Lett. 2016, 18, 2208-2211.

http://dx.doi.org/10.1021/acs.orglett.6b00835

[7] M. Blümel, R. D. Crocker, J. B. Harper, D.Enders, T. V. Nguyen,* Chem. Commun. 2016, 52, 7958-7961.

http://dx.doi.org/10.1039/c6cc03771b

N

NR1

R2R3 N

NR1

R2R3 N

NR1

R2R3

N-Heterocyclic Olefins (NHOs)

(NHOs)

N

NR1

R2R3

very strongLewis/Bronsted base

positive chargestabilized by aromaticity

NHOs = NOVEL CATALYSTSon organocatalytic chemistry

n = 5, 6, 7R = Alkyl

Potential guests: Cl, HnPO4(3-n), ArCO2, ArSO3, ArPO32

π-electron poor cavity (binds anions)

aniontropylium

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DR. PU XIAO Level 5, Chemical Science Building (F10)


LIGHT-INDUCED POLYMERIZATION

• The projects will be carried out in the Centre for Advanced Macromolecular Design (CAMD) which is a world-class research centre for polymer synthesis. CAMD has a range of state of the art equipments to service all the research steps in the projects. Moreover, a full set of household LEDs that can emit blue to red lights are available in the CAMD for the eco-friendly LED-induced polymerization technique.

• From the projects, excellent training on light-induced polymerization reactions, photopolymerization kinetics, and various photochemical mechanisms will be provided. All new Honours students in the group will be supervised by Dr. Pu Xiao and Prof. Martina Stenzel as well.


(a) Novel photoinitiating systems of polymerization under visible LED Irradiation

Light-induced polymerization is one of the most promising approaches for the fabrication of various polymeric materials, particularly for biological applications, due to its environmental (e.g. low VOCs), economical (e.g. low energy consumption) and production benefits (e.g. spatial and temporal control). 1 In this technique, initiating species (e.g. radicals or cations) are produced by a photochemical reaction in a photoinitiating system under light irradiation at room temperature and then react with monomer units.2 Light-induced polymerization is thus well-suited to producing 3D polymer networks at ambient temperature by rapidly transforming specially-formulated reactive liquids [e.g. (meth)acrylate- or epoxide- based monomers] into solids. Even though this approach is favourable for biological applications such as cell encapsulation due to the cytocompatible reaction temperature and the ease of maintaining sterile conditions, it still poses several challenges such as thick samples are difficult to fabricate due to the low penetration ability of UV light typically required for photoinitiation. To address the aforementioned issues, it is necessary to develop novel nontoxic high-performance photoinitiating systems that allow clean radical (or cation) generation under mild conditions (benign visible light) for the elaboration of polymeric materials.

This project aims to design and develop novel photoinitiating systems applicable to green technology – visible LED-induced polymerization in green chemistry circumstance (e.g. without the usage of organic

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solvents or in aqueous conditions, etc.) – which will expand the photochemistry field and provide a new environmentally-friendly method for producing advanced materials which is relevant to many sectors of the polymer industry.

(b) Non-toxic coinitiators of photopolymerization for dental materials

Camphorquinone (CQ)/amine photoinitiating systems have been widely used in clinical restorative formulation since the introduction of visible-light-activated resin composites._ENREF_4 Although tertiary amines, especially tertiary aromatic amines with para electron-donating substituents, are highly effective hydrogen donors and act as coinitiators, they are both toxic and mutagenic.3

In this project, amino acid-based coinitiators will be developed and their efficiency for the fabrication of dental materials under the irradiation of blue LED will be estimated. The relevant photochemical mechanisms will also be investigated.

(c) Waterborne photoinitiating systems in sequence-controlled photopolymerization in aqueous conditions

Sequence-controlled polymers are attracting increasing attention as their properties can be finely tuned and find various potential applications in biotechnology, nanotechnology and materials science.4 Even though several strategies have been developed for preparing sequence-controlled polymers including biological or chemical methods, they still suffer from drawbacks such as limited applicability of monomers (for biological method) or complicated purification procedures (for chemical method).4 Therefore, it is a challenge and highly interesting to develop a versatile approach for synthesizing sequence-controlled polymers especially in green chemistry environment such as at ambient temperature and in aqueous conditions.

Very recently, it has been reported that sequence-controlled multi-block copolymers can be prepared with a photoinduced approach.5 But it was carried out in organic solvent (DMSO) under UV irradiation which is not environmentally friendly. In this project, the preparation of multiblock copolymers based on amino acid inspired structures and glycol-monomers [e.g. poly(ethylene glycol) monomethyl ether methacylate] will be investigated in detail using RAFT photopolymerization under irradiation of visible light from LEDs in aqueous conditions, and the developed waterborne photoinitiating systems will be used in combination with RAFT agent [e.g. 2-(2-cyanopropyl) dithiobenzoate] to initiate the photopolymerization.

(1) Fouassier, J. P.; Lalevée, J., Photoinitiators for Polymer Synthesis-Scope, Reactivity, and Efficiency. Weinheim: Wiley-VCH Verlag GmbH & Co KGaA, , 2012.

(2) Xiao, P.; Zhang, J.; Dumur, F.; Tehfe, M. A.; Morlet-Savary, F.; Graff, B.; Gigmes, D.; Fouassier, J. P.; Lalevée, J. Prog. Polym. Sci. 2015, 41, 32-66.

(3) Shi, S.; Xiao, P.; Wang, K.; Gong, Y.; Nie, J. Acta Biomater. 2010, 6, 3067-3071.

(4) Lutz, J.-F.; Ouchi, M.; Liu, D. R.; Sawamoto, M. Science 2013, 341, 1238149.

(5) Anastasaki, A.; Nikolaou, V.; McCaul, N. W.; Simula, A.; Godfrey, J.; Waldron, C.; Wilson, P.; Kempe, K.; Haddleton, D. M. Macromolecules 2015, 48, 1404-1411.

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PROF. TIMOTHY SCHMIDT Level 2, Dalton Building (F12)

T: 04 39 386 109 E: [email protected]

MOLECULAR SPECTROSCOPY AND SOLAR ENERGY

My research group investigates how molecules interact with light, and the consequences, with applications ranging from studying radicals and ions of astrophysical and atmospheric interest, to renewable energy. Our principal tools are femtosecond and nanosecond lasers, with sophisticated detection schemes, vacuum chambers and mass spectrometers.

(a) Photochemical Upconversion for Improved Solar Energy Conversion

Light from the sun reaches us as a continuous spectrum. But, to generate a photovoltage in a solar cell, we usually neglect that part of the spectrum with photon energies below the band gap. Such a strategy limits the energy conversion efficiency of solar cells to about 33% (UNSW Si cells have reached 25%). Photochemical upconversion (PUC) can be harnessed to convert long wavelength into shorter wavelength light, increasing the photocurrent of the device.

Recently, we have applied PUC to amorphous silicon, organic polymer and dye-sensitized solar cells. But, efficiencies are still too low for application. To concentrate the absorption of light and increase upconversion efficiencies, we are currently exploring a range of nanostructured architectures incorporating biomimetic light harvesting materials.

(b) New Materials for Luminescence Solar Concentration (with A/Prof. Pall Thordarson)

One strategy to slash the cost of solar energy is to use a small area of solar cell and a large solar collector. However, usually such systems rely on geometric concentration of sunlight using mirrors. Such systems are expensive and cumbersome, and cannot concentrated diffuse light. The luminescence solar concentrator is promising way to do this using passive molecules.

When light falls on a slab of material containing fluorophores, light is absorbed but re-emitted isotropically. About 75% of this light is trapped in the slab by total internal reflection, and guided towards solar cells on the edge of the slab. Until now, such systems have been plagued by reabsorption effects. We will couple fluorescent dyes to light-absorbing nanomaterials to separate the roles of absorption and emission, and reduce reabsorption. Further improvements have been shown by us to be possible by clever design of the orientation of transition dipole moments.

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(c) Laser Spectroscopy of Isolated Radicals and Ions (with Prof. Scott Kable)

The new Molecular Photonics Laboratory houses sophisticated lasers and equipment with which we can discover new transient chemical species of importance in the gas phase chemistries of our atmosphere and the interstellar medium.

Atmospheric Radicals One of the greatest scientific challenges of our time is to understand the complex chemistry of the atmosphere. Plants and human activity are responsible for >1000 Tg (1012 kg) of volatile organic compounds being emitted into the atmosphere each year. These molecules are processed into less volatile compounds which then find their way into secondary organic aerosols, which are a major natural impactor on public health and climate. In this project, we will develop laser-based spectroscopic methods to detect and characterize intermediates formed on the way from the plant to the aerosol particle.

Interstellar Molecules and Ions

As stars die, they eject complex organic molecules into the interstellar medium, where they live out millennia before being incorporated into new stars and planetary systems. These organic molecules are the seeds of life, but, as yet, we do not know the chemical make up of the interstellar medium from which planetary systems are formed.

Using a star as a lamp, we can peer into this medium using telescopes by observing molecular absorption spectra. However, despite there being hundreds of nibbles taken out of the visible stellar spectra of stars occluded by diffuse clouds, only a few molecules have been unambiguously detected by their visible spectra. The unidentified features are known as the diffuse interstellar bands, and are the longest standing mystery in astrophysical spectroscopy.

In this project, we will develop techniques to capture the spectra of isolated, never-seen-before aromatic cations which the leading candidates for carrying the DIBs, and (hopefully) solve this long standing problem.

(d) Advanced Spectroscopy for Complex Functional Materials (with Dr Dane McCamey, School of Physics)

Complex functional materials are employed in a range of applications, the development of which is motivated by the future technological needs of society. Organic solar cells, organic light emitting diodes and organic electronics all employ materials characterized by a complex relationship between morphology and function which can only be elucidated by advanced spectroscopic techniques.

Combining lasers and magnetic resonance, we will develop and apply new advanced spectroscopic techniques to complex functional materials, revealing the dynamical behaviour of charge carriers and excited states.

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DR. NEERAJ SHARMA Level 2, Dalton Building (F12)


SOLID STATE AND MATERIALS CHEMISTRY

• We chemically tune the atomic arrangement (crystal structure) of solid state materials to enhance their physical properties such as energy storage capacity, ionic conductivity or thermal expansion.

• We use a combination of techniques to characterise our materials, including but not limited to X-ray and neutron diffraction (at the Australian Synchrotron and ANSTO), solid state NMR, electrochemical and impedance analysis, and electron microscopy.

• Our goal is to fully characterise materials, place them into real-world devices such as batteries and solid oxide fuel cells, and then characterise how they work in these devices.


(a) Towards the next generation of batteries: Sodium-ion batteries

Lithium-ion batteries are ubiquitous in our daily lives, e.g. mobile phones and laptop computers, but their limitations have restricted wide-scale use in applications requiring higher power, e.g. electric vehicles and energy storage of renewable energy. This project will target new battery chemistries, in particular sodium-ion batteries, by developing and characterising new electrode and electrolyte materials. We will work to develop a reliable and affordable room-temperature sodium-ion battery to provide sufficient power for large-scale energy storage from intermittent renewable power sources. Students will work on one of the following parts of a battery and test their component in idealized batteries.

Positive electrode materials

These electrodes provide the source of the sodium-ions and represent the largest cost and energy limitations for lithium-ion batteries. Here, new sodium-containing transition metal oxides, phosphates or sulfates will be synthesized and characterized to determine the relationship between crystal structure and battery performance. We are working towards scaffolding layered electrode materials in order to dramatically improve performance.

Electrolytes

Sodium-ion conducting ceramics or glassy-ceramics are known to be excellent electrolytes at high

temperatures (>300°C). This project works towards making materials with sufficient sodium-ion conduction at room temperature.

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Negative electrode materials

Negative electrodes are the least investigated component in a sodium-ion battery and the compounds used for lithium-ion batteries show poor performance in sodium-ion batteries. By developing new negative electrodes and understanding their limitations towards reversible sodium insertion/extraction we will be enable the next generation of devices.

(b) Tuning negative thermal expansion to produce zero thermal expansion materials

The majority of materials expand during heating via thermal expansion and this process is responsible for billions of dollars per year in maintenance, re-manufacture and replacement costs due to wear and tear on both moving parts (e.g. in aircraft gas turbines), and components that are designed to be static (e.g. in optics, coatings, electronics). If a zero thermal expansion (ZTE) material can be made, a material that neither expands nor contracts upon heating, this could dramatically reduce industrial costs. In order to achieve this, the opposite extreme of materials are considered in this project - negative thermal expansion (NTE) is a property exhibited by a small group of materials predominantly due to transverse vibrations of atom groups or cooperative rotations of units (e.g. –CN- or WO6). These materials typically feature large crystallographic voids and cations with variable oxidation states. So why not use a battery as a synthesis tool? In this project we will controllably insert Li and Na into the voids of the NTE materials, via a battery, in order to tune the cooperative rotations to produce ZTE materials.

(c) Improving solid-state electrolytes by understanding their formation characteristics and phase evolution

Safety is an important aspect of high power batteries. Using a solid-state electrolyte has significant advantages to the highly flammable liquid electrolytes that are commercially available. Unfortunately the ionic conductivities of solid-state compounds are generally lower than the liquid counterparts, especially under ambient conditions. At the other extreme, solid oxide fuels cells often operate at

approximately 1000°C as the operating temperatures are essentially determined by the ionic conductivity of the electrolyte. In both examples, electrolyte ionic conductivity is a critical hurdle in preventing further development and use of these technologies. The ionic conductivity is directly related to the crystal structures adopted by the electrolytes and how they evolve with temperature. In this project lithium-ion and oxide-ion conducting materials will be synthesized and their ionic conductivities characterized. Importantly, variable temperature time-resolved neutron powder diffraction will be used to study the formation (from starting reagents) of these ionic conductors under varied conditions. This will shed light on the formation processes and optimal conditions required for synthesis.

(d) Other projects

Depending on your interests, other solid state projects, e.g. making new superconductors, can be designed. Please consult with Neeraj for further details.

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SCIENTIA PROF. MARTINA STENZEL Level 2, Dalton Building (F12)


NANOPARTICLES AND TAILORED POLYMERS FOR CANCER TREATMENT

• The delivery of drugs can be improved by packaging the drug into nanoparticles. Nanoparticles for drug delivery have typically sizes below 100 nm and can be prepared using various materials including polymers. In our group, we synthesize various polymers to create core-shell nanoparticles – the core holds the drug, mainly anti-cancer drugs, while the shell makes the particles soluble and determines the interaction with cells.

• In our group, we work on different aspects starting from organic synthesis to polymer nanoparticle preparation to testing these particles on cancer cell lines. We have meeting with clinicians and we discuss their drug delivery problems.


(a) Imitating viruses with polymers: Learning from the success of viruses

Most drug carriers described in literature are spherical nanoparticles. Interestingly, nature’s own highly successful nano-objects, viruses, have often elongated structures. Example is the by now well-known Ebola virus with its worm-like morphology. In addition, viruses carry bioactive groups that allow fast recognition of the host and quick entry. In this project, we will prepare elongated nanoparticles that will simulate the shape of viruses. To gain more understanding of the entry of these nanoparticles into cells, we will make nanoparticles of different softness as we have found that this could be a key parameter. The student will therefore spend some

time with microscopy techniques such as AFM to evaluate the properties of the nanoparticle before studying cell uptake

(b) Drug carriers inspired by nature: Nanoparticles with sugar antennae Carbohydrates have become a hot topic for research within the scientific community. This is due to the myriad number of biological communication events, including: cellular recognition, inflammation, signal transmission and infection by pathogens displayed by them. To improve the distribution of drugs in a biological system, the use of a ligand (e.g. carbohydrate and peptide targeted therapeutics for the recognition of malignant cells), could be an important step towards the improved treatment of cancer and other diseases.

Uptake of nanoparticles with sugar polymers by cancer cells

Different nanoparticles prepared from ABC triblock terpolymers

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Synthesis of glycopolymers has been one of our core activities over the last few years. The polymers are prepared either by direct RAFT polymerization of glycomonomers or by post-functionalization of active polymers. We are aiming at preparing mannose-based nanoparticles that will be used as a potential carrier for TB treatment.

c) Drug delivery carriers for peptides and proteins Protein and peptide drugs are increasingly common in modern medical care. The rise in protein drugs compared to more traditional low molecular weight drugs stem from their increased selectiveness and therefore increased effectiveness. Targeted therapies using proteins are particularly attractive in cancer therapy where chemo- and radio therapy are known to be potentially very harmful to healthy cells. The main barrier in delivery proteins for therapeutic purposes stem from their intrinsic properties such as their large size, their surface charge and most of all their hydrolytic instability. To combat these shortcomings, a range of techniques have been developed, which include the formation of polymer-protein conjugates or the encapsulation of proteins into polymer nanoparticles. The mode of interaction between protein and polymer can be either by the formation of a covalent bond, electrostatic forces or by simple van der Waals forces among others. In our lab, we investigate solutions depending on the type of protein we want to deliver. The main focus is on the question of how the nature of the underlying polymer affects the performance of the drug. We therefore synthesize libraries of polymers that can either interact with the protein via electrostatic forces or bind the peptide to help us understand what makes a good carrier.

(d) Solid state NMR analysis of self-assembled materials (in collaboration with Dr Aditya Rawal from the analytical center)

When block copolymers self-assemble into micelles, it is widely assumed that the aggregate has a core-shell structure with a sharp transition between both phases. However, the interface can sometimes be diffuse while the core is often filled with water. These properties will affect how drugs or catalysts that are loaded into the micelle perform. To gain more understanding about the physio-chemical properties of micelles, we will perform solid state NMR studies on loaded micelles. These investigations will reveal how tightly the drugs are packed inside the micelles. In vitro experiments with cancer cells will then show if there is any effect of the micelle properties on the drug activity.

Polymer with charges (polyelectrolyte) binds to proteins to form polyion complex micelles

protein

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A/PROF. JOHN STRIDE Level 1, Dalton Building (F12)


MATERIALS CHEMISTRY AT THE NANOSCALE

My group focuses on making and understanding new materials that are usually focused on some of the major challenges facing us today: energy, water and sustainability. We make use of a range of techniques that include X-ray and neutron scattering in truly multi-disciplinary projects. Key to these studies is the notion of hierarchical emergent properties and complexity - the world around us derives from simple inter-molecular interactions; we aim for a greater understanding of these fundamental processes in order to deliver new materials displaying novel properties. It would be great to work with Honours students on the following projects:

(a) Metal organic frameworks (MOFs): coordination chemistry of the 21st century

Over the last 15-20 years, inorganic chemistry has taken on board a number of new concepts and approaches that have reinvigorated the subject – one area showing particular promise is polymeric coordination compounds or MOFs. These topologically beautiful materials display intimate long range ordering and immense compositional flexibility, along with structural rigidity; they are ideal hosts for a range of molecular guests, opening up many potential applications.1

Sorting and storing molecules - how to select for one molecule over another This research project is specifically targeted at very real challenges faced in industry - effective separations of mixed gas streams and facile storage of gaseous fuels such as H2. Highly porous MOFs make excellent host materials for small molecules such as CH4 or H2. By tuning their properties MOFs can become efficient storage vessels or effective gas-selective membranes such as the H2 selcting MOF shown here.

New magnetic materials: fundamental insights Magnetic materials have revolutionised the way in which we store information and use information, they

have also been a navigational aid for centuries and are even pretty useful at securing notes to the fridge door. It is fascinating therefore that we still do not fully understand the behaviour of such materials, especially when dimensionality is constrained. MOFs can have single chains (1D) or sheets (2D) of metal ions embedded into a non-magnetic matrix, making them ideal materials in which to study the effects of magnetic quantum confinement.

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(b) Organic electronics: new materials, new technologies

Organic alternatives to many conventional technological materials offer solutions to some important issues; (i) they are low density materials and so are attractive in the realm of incorporation into portable devices; (ii) organic materials are readily processable from the solution phase, providing a low cost, low energy alternative to solid oxides and ceramics; (iii) end of life processing of organics is far less arduous than that of many inorganic materials, providing a more environmentally sustainable solution.

Room temperature organic ferroelectrics as non-volatile memories? Ferroelectric materials have the intrinsic property of undergoing a change in polarisation in applied electric fields; mostly inorganic in nature, they are of great interest for applications such as sensors, communications and non-volatile data storage technologies. Organic ferroelectric materials are an emerging class of ferroelectrics that share the technologically relevant response to electric fields, but have greater flexibility in material processing, thereby offering lightweight and solution dispersible alternatives to traditional ferroelectrics. Recent advances in such materials have greatly increased the potential to deliver truly low-density, wholly organic ferroelectric devices that are fully interfaced to organic, flexible, easily processed electronic circuitry.2 This project aims to synthesise new ferroelectric materials based upon the recognised modalities of mixed-stack and hydrogen-bonded systems.

Donor-Acceptor stacks: heterojunction photovoltaics to molecular magnets The intermolecular interactions between efficient electron donors (D) and acceptors (A) yield optically active charge transfer materials that can act as organic semiconductors, photovoltaics, ferroelectrics and light emitting diodes. Complete electron transfers can result in bulk magnetic materials. We aim to investigate the interactions of simple D…A stacks whilst modifying the peripheral functional groups, known to contribute to molecular packing. In this way, self-healing semi-conducting liquid crystalline materials can be produced that show remarkable anisotropy, enabling uniaxial conduction under greater load. With the wide range of suitable D and A molecules available, these materials have tremendous promise in their capacity to be tuned for specific applications, whether it be for emission in the visible spectrum (OLEDs) or broad-range absorption (OPVs). Being relatively small molecules, they are also suited to computational studies that

are highly informative in terms of the electronic interactions and π-π stacking interactions.3

(c) Other projects Other projects involving materials-based chemistry, nanotechnology, crystallography and spectroscopy are available and can be tailored to your interests. Feel free to come and discuss possible research projects. 1. A flexible copper based microporous metal-organic framework displaying selective adsorption of hydrogen over nitrogen; M.A. Nadeem, A.W. Thornton, M.R. Hill & J.A. Stride, Dalton Trans., 2011, 40,

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2. Room-temperature ferroelectricity in supramolecular networks of charge-transfer complexes; A.S. Tayi, A.K. Shveyd, A.C.-H. Sue, J.M. Szarko, B.S. Rolczynski, D. Cao, T.J. Kennedy, A.A. Sarjeant, C.L. Stern, W.F. Paxton, W. Wu, S.K. Dey, A.C. Fahrenbach, J.R. Guest, H. Mohseni, L.X. Chen, K.L. Wang, J.F. Stoddart, S.I. Stupp, Nature 488, 485 (2012).

3. Dispersive kinetics in discotic liquid crystals; O. Kruglova, F.M. Mulder, G.J. Kearley, S.J. Picken, J.A. Stride, I. Paraschiv and H. Zuilhof, Phys. Rev. E, 2010, 82, 051703.

www.rsc.org/crystengcomm

CrystEngComm

PAPERJohn A. StrideUnderstanding the packing in the 1!:!1 molecular complex 1,3,5-tricyanobenzene–hexamethylbenzene by probing lattice modes

Volume 17 Number 20 28 May 2015 Pages 3719–3878

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A/PROF. PALL (PALLI) THORDARSON Level 1 (Room 133), Dalton Building (F12)


NANOMEDICINE & SUPRAMOLECULAR CHEMISTRY

• Synthesis of novel peptides for nanomedicine, including drug delivery and tissue engineering • Development of 3D Cell Culture materials for use in medical research and stem cell therapies • Protein Chemistry and Self-assembly for better understanding of functional biological systems • Light-harvesting arrays for the capture and use of solar energy • Systems Chemistry and the Origin of Life


(a) Nanomedicine: Smart soft peptide-based nanomaterials for medical applications (collaboration with Prof. Maria Mariallaris, Children’s Cancer Institute Australia).

This work is aimed at designing and synthesising peptide-based smart soft nanomaterials for application in medicine, focusing on cancer-targeting peptides and peptide based materials for drug delivery and for use in 3D-cell cultures. models to regenerative medicine and stem cell therapy. In collaboration with medical researchers at the Children’s Cancer Institute Australia we are actively developing these systems as a potential tool in the treatment of brain cancers. One aspect of this work includes the synthesis of tumour-targeting peptide-drug hybrids.

(b) Novel donor-acceptor dyes for applications in solar energy research (collaboration with Clockwerk Pty Ltd, Prof. Timothy Schmidt, Prof. Richard Tilley and Dr. Justin Hodgkiss, Victoria U. Wellington).

In this project we focus on the synthesis of aromatic dyes such as perylenes and linear acenes (benzene, naphthalene, anthracene, tetracene, pentacene…). We tailor the design of these molecules with the photophysical properties desired (e.g. emission at a particular wavelength). The photophysical properties of these molecules are then measurement to optimise further their properties for applications in cutting-edge solar energy research such as solar concentrators, upconversion and singlet-fission. Ultimately, the aim of this work is to generate new materials for industry to address the ever-growing need for renewable energy.

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(c) Tropylium-based host-guest (collaboration with Dr. Vinh Nguyen).

Tropylium is a π-electron poor 7-membered aromatic cation. Recent synthetic advances by the Nguyen group have made this unusual structural much more accessible, allowing us now to start to explore their potential in supramolecular host-guest. Their electron-deficient nature makes then particularly attractive for the binding and sensing of small and medium-sized biologically important anions such as chloride, phosphate and carbonates. We propose the synthesis of tropylium-based macrocycles (see figure) as the starting point for this project which will represent a new platform in supramolecular chemistry. Please also see Nguyen’s Honours projects for more details..

(d) Systems chemistry – Far-from-equilibrium self-assembly (collaboration with Prof. Martina Stenzel and Prof. Jan van Esch Delft U. Technology, Netherlands).

What is the difference between life and “not a life”? One of the hallmarks of biology is not just how molecules self-assembly into functional structures (e.g., the cytoskeleton) but that self-assembly requires energy. In other words, it operates at conditions that are far-from-equilibrium thermodynamically – in stark contrast to nearly every man-made (non-living) self-assembled system known to date that are either at thermodynamic equilibrium or kinetically trapped. Better understanding of far-from-equilibrium self-assembly may therefore give us important clues towards understanding better how small molecules self-assembled to form functional life-like system that then evolved in complexity until life as we now it emerged. In this project we will focus on synthesising systems that require light (photosynthesis) to drive self-assembly in a confined environment, e.g. polymersomes.

(e) Novel peptides for immunotherapy (Joint Honours Project with Dr. Angela Finch, SOMS, UNSW).

C5a is a potent inflammatory mediator generated by the activation of the complement system and has been implicated in the pathogenesis of as diverse range of inflammatory disorders. Cyclic C5a antagonists were developed based on the C-terminus of C5a. The most potent of these AcF[OPdChaWR] (PMX53) has nanomolar affinity for the C5a receptor (C5aR). PMX53 inhibits the activation of the C5aR in a non-competitive manner. The molecular basis of this non-competitive antagonism has not been established. To elucidate the mechanism of action of PMX53 fluorescent C5aR ligands need to be developed for use in kinetics binding assays. An understanding of the molecular basis of the actions of PMX53 will provide information for subsequent drug development.

n = 5, 6, 7R = Alkyl

Potential guests: Cl, HnPO4(3-n), ArCO2, ArSO3, ArPO32

π-electron poor cavity (binds anions)

aniontropylium

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PROF. RICHARD TILLEY B89, Chemical Sciences Building (F10)


NANOPARTICLE SYNTHESIS & ELECTRON MICROSCOPY

Nanoparticles have unique properties controlled by their size and shape. In my research team, we focus on the solution chemical synthesis of nanoparticles with a focus of controlling nanoparticle shape and size. The nanoparticles we develop are novel, cutting edge materials with tuneable chemical and physical properties for use in a wide range of applications including MRI contrast agents, catalysts and solar cells. As Director of the Electron Microscope Unit here at UNSW, we have aparticular emphasis is placed on the characterisation of nanoparticle sizes, shapes, and crystallography using state-of-the-art high resolution electron microscopy.


(a) Magnetic Nanoparticles for Biomedical Applications with Prof Justin Gooding

Magnetic nanoparticles are currently the subject of intense research worldwide and hold a strong interest in the field of nanoscience for their numerous applications including contrast enhancement in magnetic resonance imaging (MRI), magnetic hyperthermia, and drug delivery. However, strict control on nanoparticle size needs to be achieved. Previous work in the group has focused on the development of strongly magnetic single-crystal core/shell iron/iron oxide nanoparticles enabling unambiguous detection of small tumours using MRI.

This project will investigate magnetic nanoparticles as new and more effective MRI contrast and hyperthermia agents for the treatment of diseases, in particular cancer. Experience in a variety of techniques will be gained, including nanoparticle solution synthesis and morphology characterisation using UNSW’s state-of-the-art electron microscopy unit.

(b) Earth Abundant Non-Toxic Quantum dots for Next Generation Solar Solutions

The most successful solar cells are based on light absorbing materials that are either highly toxic (CdTe), or weakly absorbing (Si). Cu2ZnSnS4 nanocrystals (CZTS NCs) are highly suitable candidates for next generation solar cells due to their unique optical properties, low toxicity, and earth abundant composition, however to increase their efficiency, synthesis methods to strictly control their composition and phase must be developed.

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Cou

nts

(a.u

.)

30 40 50 60 2θ (degrees)

This project will develop solution based methods to control the size, phase, and composition of CZTS NCs characterized by a wide array of analytical techniques at the leading edge of nanoscience. UNSW’s state-of-the-art electron microscope facility will be used to characterise the shape of the nanocrystals. With the school of photovoltaic and renewable energy engineering to test and produce working solar cell devices.

(c) Synthesis & Characterisation of Cobalt-Ruthenium Nanoparticles as Magnetic Catalysts with Prof Justin Gooding

Due to the rising shortage of fossil fuels, ruthenium nanocatalysts have recently emerged as a new synthetic strategy for generating ‘synfuel’ hydrocarbons via the thermal treatment of simple CO and H2 gases (the Fischer-Tropsch process). However, for this process to be viable at the industrial level, expensive materials and high processing costs need to be reduced. Hybrid magnetic-catalytic nanoparticles address these problems by reducing costly precursor amounts and enabling magnetic heating of the nanoparticles without the need for an external heat source.

This project will focus on the synthesis and characterisation of cobalt-ruthenium bimetallic nanoparticles for application as efficient catalysts for the Fischer-Tropsch reaction. This work will involve the use of UNSW’s state-of-the-art electron microscope facility in order to characterise the morphology of the metallic surfaces and interfaces, which are critical to the efficiency of the magnetic nanocatalysts.

(d) Synthesis of Ruthenium-Palladium Nanoparticles & Analysis of their Catalytic Properties

Ruthenium-palladium bimetallic nanoparticles have been shown to be promising catalysts and electrocatalysts for a number of important reactions, including selective hydrogenation of aromatic compounds to yield precursors to nylon, polyester paints and resins, etc., electrooxidation of ethanol and formic acid in direct alcohol fuel cells (DAFCs) and direct formic acid fuel cells (DFAFCs).

Our group has previously synthesised the highly controlled hourglass shaped ruthenium nanoparticles with well-defined facets and active sites for catalysis. This project will extend the synthetic strategy by developing novel ruthenium-palladium nanoparticles with controlled size, shape and composition, and will explore the catalytic properties of these nanoparticles as the next generation of catalysts.

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A/PROF. CHUAN ZHAO Level 1, Room 127, Dalton Building (F12)


ELECTROCHEMICAL TECHNOLOGY FOR CLEAN ENERGY

AND SMART SENSORS

Clean, renewable energy has enormous implications for the future prosperity of humankind. As creatures, living better and longer has been our instinctive pursuit, and advanced biomedical technology is therefore always highly demanded. Research in our lab addresses these problems by using electrochemical technology, nanotechnology and biotechnology. Our research areas include solar water splitting, CO2 reduction, gas sensors and Cochlear implants.


(a). Solar Hydrogen Fuel Product From Seawater Production of hydrogen fuels from water using electricity generated from renewable energy sources such as solar and wind can provide a sustainable and clean fuel supply for human use. Conventional water splitting is typically carried out in freshwater containing an added supporting electrolyte to conduct electricity, such as potassium hydroxide. However, freshwater only represents a microcosm of the total forms of water found on Earth. The vast majority of water on Earth is seawater (approximately 97%), which contains naturally present salts, predominately sodium chloride. Current hurdles in seawater electrolysis lies in the release of toxic chlorine gas due to the kinetically favoured chlorine evolution over oxygen evolution. The project will develop novel electrodes made of Earth-abundant materials and a prototype water splitting cell for hydrogen production directly from seawater without chlorine evolution.

(b). Nanostructured Carbon Electrocatalysts for CO2 Reduction to Fuels

Fossil fuels have historically been the primary feedstock for petroleum based products and industrial chemicals. Apart from the impact that fossil fuels pose on the environment, they are generally mined in remote locations and require massive infrastructure for processing and distribution before they are even refined. One promising solution is to reduce CO2 itself to petrochemical feedstock, which could cater to the unprecedented consumerism of society and simultaneously reduce the anthropogenic emissions of CO2 in the atmosphere to restore the natural carbon cycle. To improve the CO2 reduction efficiency,

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advanced catalysts that are efficient, selective, stable, and low cost need to be developed. This project will design a class of inexpensive, non-metallic electrocatalysts based on nanoporous graphene. The electrocatalysts will be integrated into a prototype device for converting CO2 into useful fuels.

(c). Smart Ionic Liquids–Based Microarray Gas Sensors

Ionic liquids (ILs) are attractive “green” (environmentally friendly) solvents and have a number of unique chemical and physical properties, such as negligible vapour pressure (they will never evaporate), wide electrochemical window, thermal stability, and wide range of solubilities. Microcontact printing is a simple, elegant technique which can be used to create patterns of micron-sized features on gold surfaces over relatively large areas by utilizing alkanethiolates and the strong gold-sulfur interaction. This project will combine these two technologies to fabricate gold chips printed with large arrays of IL microdroplets which will then be applied as gas sensors for detect of gaseous coumpounds released from numerous anthropogenic sources including waste water, sewage treatment, farms and industry. These sensors will be small, specific to the target gas, sensitive, fast in response and portable.

(d). Bionic Eyes and Ears - Neural Prostheses (in collaboration with Cochlear Ltd)

Neural prostheses are a series of devices that can substitute a motor, sensory or cognitive modality that might have been damaged as a result of an injury or a disease. The design of next-generation high-resolution and site-specific neural prostheses requires greater numbers of microelectrode array. However for a fixed charge, reduction in electrode size increases charge density. If charge density exceeds the reversible charge injection limit, undesirable and irreversible electrochemical reactions occur which damage both stimulating electrodes and neural tissues. In this project, we’ll develop an effective way to increase the surface roughness and charge injection limit of electrodes, and maintain low resistance of the microelectrodes.

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HONOURS ALTERNATIVES

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PROF. SCOTT KABLE, DR. LUKE HUNTER, DR. RON HAINES, DR. SCOTT SULWAY, DR. KIM LAPERE & DR.

SHANNAN MAISEY Level 1, Dalton Building (F12)

T: 9385 4713 E: [email protected] T: 9385 4474 E: [email protected] T: 9385 4718 E: [email protected] T: 9385 5236 E: [email protected] T: 9385 5967 E: [email protected] T: 9385 5967 E: [email protected]

The UNSW Chemical Education Group

• In the ever evolving world of education research we seek to undertake projects that make a real and lasting difference to the way we educate our students

• We want to create, we want to innovate, we want to provide the best possible educational experience for all of our students

• So if you share a passion for chemical education like we do, contact one of the group


(a) Using Chemistry in the wider world

The School of Chemistry is currently undertaking a potentially paradigm shifting project in the way that we teach and assess content knowledge in Chemistry. We want to create a set of threshold concepts in all of our courses that students must master in order to obtain a passing grade. We have already had great success doing this with the skills in our first year undergraduate laboratory program and would like to extend this to the lecture material too. This is your opportunity to get involved with this innovative and exciting project, by investigating what knowledge, skills and techniques student have learnt in our courses and then utilised in other courses around UNSW. This study could focus on direct transfer of specific knowledge, skills and techniques or on more indirect skills that were acquired (such as problem solving skills). The results of this study will influence key decisions in the project and ultimately could shape or change the direction of the said project.

(b) Preparing for Chemistry

Lectures, tutorials and laboratory practicals are the three modes of delivery that we utilise in our chemistry courses. Although very little preparation needs to be performed by a student in order to engage with the content in a lecture, proper preparation is essential if a student wants to maximise their educational experience during both tutorials and laboratory classes. Preparation allows a student to fully engage with the content in an active learning environment, which leads to a more productive learning episode with greater retention of knowledge. We wish to gain a greater understanding of how

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students prepare for these active learning activities (via their use of online resources, reading texts, listening to lecture recordings etc.) so that we can further tailor our resources to meet the needs of the students in our courses. This project would involve contacting students, investigating their preferred preparation methods, resources etc. and correlating this with students’ performance and engagement in the learning episodes.

(c) Have your own idea(s)?

If you have your own idea for a project that aligns with our philosophy then we would like to hear from you. Get in contact with us and we can discuss your project idea(s).

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Honours Exchange at King's College London As part of the PLuS Alliance, we are now able to offer the possibility of completing an Honours projects at King's College London (http://www.kcl.ac.uk/nms/depts/chemistry/index.aspx). With a pedigree as one of the oldest Chemistry Departments in England, King’s Chemistry enshrines the rigour of the discipline in a progressive context. Continuing an illustrious tradition at the University, epitomised by the discoveries of Rosalind Franklin and Maurice Wilkins in the structure of DNA, the department has a distinct focus on understanding the chemistry of life and the interface with Biology. King’s provides a vibrant environment in which to study 21st century Chemistry in the heart of London.

Students will be enrolled in Honours at UNSW, but will complete their projects in London under local supervision. Grades will be transferred to UNSW and students will graduate with Honours from UNSW. The exchange program provides the opportunity for those keen to extend themselves in both their research project and life beyond the lab. Students interested in this opportunity should speak to A/Prof. John Stride after exploring the King's College website and identifying potential supervisor(s).

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Honours at UNSW, Canberra School of Physical Environmental and Mathematical Sciences

Research into chemistry is also conducted within the School of Physical, Environmental and Mathematical Sciences at the Canberra campus of UNSW. Co-located with the Australian Defence Force Academy, UNSW Canberra maintains a diverse research program and is home to many research students. It is straight-forward for current UNSW Bachelor of Science students to transition to the Honours program at UNSW Canberra.

A selection of the chemistry research areas being actively pursued at UNSW Canberra are listed below, organised by research group leader. A range of Honours projects are available within each group, which can be adjusted to fit a student’s interest. Group leaders may also be available for collaborative projects with research groups within the School of Chemistry, on a case-by-case basis.

Students with an undergraduate Weighted Average Mark (WAM) of 85 or higher are eligible for an $8000 Honours scholarship if enrolled at UNSW Canberra.

Students who complete their Honours degree within the School of Chemistry should also consider the possibility of higher degree research at UNSW Canberra, as the research at this campus extends into areas complementary to those actively pursued within the School of Chemistry. PhD scholarships for study at UNSW Canberra are generally available to all UNSW students who achieve First Class Honours.

Bio-inorganic Chemistry — Prof Grant Collins The current focus of our work is in the development of new, and very promising, classes of multinuclear ruthenium complexes as antimicrobial agents. The emergence of drug-resistant populations of microorganisms means there is clearly a need for the development of new antimicrobials — but more importantly, there is the need for the development of new classes of antimicrobials. Complementing the antimicrobial studies has been research on the toxicity and the biological processing of the ruthenium complexes in eukaryotic cells. Emerging directions include utilising ruthenium complexes more broadly as anti-parasite agents, particularly in the treatment of schistosomiasis.

Supramolecular Chemistry — Dr Anthony Day The research interests of the Supramolecular Chemistry group are based in organic chemistry synthetic design and the development of new synthetic techniques – in particular molecular host/guest chemistry. The family of molecular hosts known as cucurbit[n]uril and derivatives of this family are a particular target. Specific areas of research interest involve drug delivery vehicles, sensors and supramolecular materials.

The group has a secondary research area involving energetic materials, including insensitive munitions, detection, deactivation and environmental aspects. Applied aspects of this work with the Australian Defence Force and the Australian Federal Police are supported by strong links within the research team.

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Theoretical Chemistry — Dr Terry Frankcombe The group’s research activities fall broadly under the umbrella of theoretical and computational chemistry, extending into chemical physics. Four main research themes are currently being pursued: Gaussian-based quantum dynamics methods, gas–surface dynamics, dielectric materials, and the structure and mechanism of photosystem II. Secondary areas of investigation are processes occurring on the surfaces of spacecraft, simulating condensed matter spectroscopies, and “divide-and-conquer” strategies. Our research can be computationally intensive and involves the combination of chemistry, physics, mathematics and computer science.

Beyond these focus areas the group maintains active expertise in quantum chemistry in general, in molecular, condensed phase and surface adsorbate contexts.

Optical and Laser Spectroscopy of the Solid State — Prof Hans Riesen The research of the Riesen group has been mostly focused on laser spectroscopy of transition metal ion doped insulators/wide band gap semiconductors. We are particularly interested in light-induced

changes in the solid state that have potential applications in ultra-high density optical data storage and optical signal processing. Very recently Hans and some of his team have studied the generation of slow and fast light by transient hole-burning.

With the advent of the Australian Synchrotron, Hans has also become a user and strong supporter of synchrotron science. In recent years, the group have discovered a novel X-ray storage technology with

applications in personal and clinical dosimetry, and medical imaging.

Inorganic Chemistry and Electrochemistry — Dr Lynne Wallace The Wallace group research interests include the synthesis and study of redox-active and luminescent transition metal complexes, and applications of such complexes in sensor systems, light-activated molecular devices, supramolecular assemblies and therapeutic approaches. Electrosynthesis of green energetic materials is also a research focus.

Statistical Mechanics — Assoc Prof Cliff Woodward The Woodward group conducts research in the field of statistical mechanical theories of condensed matter and complex fluids.

Some highlights of our research program include density functional theory and simulations of room temperature ionic liquids and polymer mediated interactions in polymer/particle mixtures, including many-body effects close to criticality. We have also used intensive simulations and theory to investigate biological systems, in particular, the riddle of “arginine magic”; the poorly understood mechanism that allows arginine-rich peptides to easily penetrate cell membranes. While most of the theoretical work carried out in the group is not reliant on massively large computational platforms, potential candidates should have a strong background in computational methods, physics or physical chemistry and mathematics.

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Figure 1. Textured silicon surface after ps UV laser ablation.

JOINT PROJECTS WITH SCHOOL OF PHOTOVOLTAIC AND RENEWABLE ENERGY ENGINEERING (SPREE)

Renewable energy research can present some very interesting chemical science problems. SPREE researchers would like to offer some joint Honours projects with Chemistry. These projects will give you the opportunity to apply your chemical sciences knowledge and skills to solving practical photovoltaics and renewable energy engineering problems. Students will be required to have a primary supervisor in Chemistry who will work in coordination with the SPREE supervisor(s).

Short Pulse Laser Structuring for Adherent Metal-Plated Electrodes for Silicon Solar Cells Assoc. Prof. Alison Lennnon – Room 127, TETB (H6) T: 9385 7942 E: [email protected] Background

Photovoltaics (PV) is predicted to provide 20% of the world’s electricity need by 2050. This represents a very different energy scenario from what we have today where electricity generation is dominated by fossil fuel resources and where solar photovoltaics contributes only ~ 1% to the global energy market and renewable energy, in general, contributes ~14%. Solar PV’s annual growth rate since 1990 is ~ 46%, the largest for all forms of renewable energy. The challenge is therefore to be able to continue to reduce the cost of PV. Silicon PV accounts for ~ 90% of the solar PV market and one of the key challenges for that industry is to “wean” itself off the use of silver for the metal electrodes of individual cells. Although plated copper has been proposed as a viable replacement for screen-printed silver, concerns regarding the adhesion of plated copper to silicon have limited uptake of plating.

Project Details

It has been recently demonstrated that picosecond UV laser ablation of surface dielectrics from silicon solar cells can result in adherent plated metal electrodes, however the reason for this significant increase adhesion is not well understood. Inorganic dielectric layers (e.g., silicon nitride) are ablated from silicon using ps UV laser through a process of spallation where a very thin surface layer of silicon is excited into a plasma which then “lifts-off” the overlying dielectric layer [1]. The exposed silicon surface exhibits a series of periodic ripples (see Figure 1), the nanoscale roughness of which has been proposed to contribute to the improved plated metal adhesion. However, it is not clear that surface roughness is the entire story. In this project you will investigate the relationships between laser ablation conditions (i.e., pulse length and wavelength), surface morphology, surface wettability and interface adhesion.

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Through this project you will have the chance to learn about short pulse laser ablation (using lasers provided at Optofab at Macquarie University) and will gain experience in:

! Contact angle measurements for silicon surface wettability; ! Light-induced nickel plating of laser-ablated silicon surfaces; ! Inductively-coupled plasma MS for plated metal mass quantification; and ! Interface adhesion using an in-house build scratch tester (see Figure 2; [2, 3])

Figure 2. (a) Measurement of horizontal force required to dislodge metal fingers from the solar cell surface; (b) photo of the adhesion testing equipment at SPREE.

Chemically Synthesized Nanomaterials for Photovoltaic Cells and Renewable Energy Rob Patterson – Rm 210 WS 17/Rm 246, Level 2, TETB (H6) T: 0404280905 E: [email protected]

Background

Materials with low embodied energy, those that take very little energy to make, are attractive for renewable energy devices since they minimize the energy input required to make a device that is meant to function as an energy source. Chemically synthesized materials, such as colloidal quantum dots, fall into this category since they can be fabricated at low temperatures, often from standard laboratory chemicals. It is critically important that we learn how to make functional devices from materials of this type to be prepared for the significant transition to industrial processes with greatly reduced energy intensity, particularly in the energy sector.

Project Details

To date, the group has been working with lead chalcogenide (PbX, X=S, Se) quantum dots (QDs) [4] and the new perovskite material CsPbY3 (Y=I, Br) [5]. Additional materials of interest include non-toxic (Pb-free) nanomaterials such CuIn(S,Se)2 and Cs2SnI6. It is a challenge to find and develop new materials that perform as well in optoelectronic applications, such as photovoltaic cells, as those containing Pb and Cd. However, it remains a priority to move away from these elements, particularly for photovoltaic cells that will be deployed over large areas and in urban environments.

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Developing new materials and measuring the properties relevant to optoelectronic applications to assess their potential in future energy technologies is a large part of the activity of the group. The other focus is to take existing materials and make high efficiency devices. Currently the group makes the most efficient PbSe QD solar cells in the world.

Figure 1. Atomic resolution TEM image of PbS Quantum dots, showing atomic fringes.

In this project the student will have the opportunity to:

• Fabricate solution processable materials, such as colloidal nanoparticles

• Measure essential material properties such as crystallinity, light absorption and photoluminescence

• Learn to make thin films of nanomaterials using spin coating and other wet-chemical techniques

• Make photovoltaic devices and measure their performance

Research in this area is highly interdisciplinary, employing concepts from chemistry, physics, materials science and electrical engineering. This leads to exciting and highly educational projects on emerging technologies in responsible and sustainable areas of science.

Additional work in catalysis/photocatalysis, biochemistry/bioenergy is also available.

[1] E.L. Gurevich, S.V. Gurevich, Laser Induced Periodic Surface Structures induced by surface plasmons coupled via roughness, Appl. Surf. Sci., 302 (2014) 118-123.

[2] T. Young, K. Khee, A. Lennon, R. Egan, O. Wilkie, Y. Yao, Design and characterization of an adhesion strength tester for evaluating metal contacts on solar cells, in: 40th IEEE Photovoltaics Specialist Conference, Denver, CO, USA, 2014, pp. 2550-2553.

[3] R. Chen, W. Zhang, X. Wang, X. Wang, A. Lennon, Failure Modes Identified during Adhesion Testing of Metal Fingers on Silicon Solar Cells, Energy Procedia, 67 (2015) 194-202.

[4] X. Lan, S. Masala, and E. H. Sargent, “Charge-extraction strategies for colloidal quantum dot photovoltaics,” Nat. Mater., vol. 13, no. 3, pp. 233–240, Feb. 2014.

[5] L. Protesescu, S. Yakunin, M. I. Bodnarchuk, F. Krieg, R. Caputo, C. H. Hendon, R. X. Yang, A. Walsh, and M. V. Kovalenko, “Nanocrystals of Cesium Lead Halide Perovskites (CsPbX 3 , X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut,” Nano Lett., vol. 15, no. 6, pp. 3692–3696, Jun. 2015.

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