Prof. Stephen Blanksby
Phone No: +61 2 42 21 5484
Lab phone: +61 2 42 21 5943
Mass Spectrometry (MS): Applications and Fundamentals
The Mass Spectrometry User Resource and Research Facility (MSURRF) at UOW houses a range of sophisticated instrumentation for the detection and characterization of molecular species based on their mass/charge ratio. These state-of-the-art technologies can be employed for applications as diverse as determining the lipid profile of cellular membranes in biological tissue samples or probing the oxidation products from weathered colorbond steel®! In addition to these analytical applications, the mass spectrometer provides the ideal gas phase "test tube" for probing the structure, reactivity and photolysis behavior of molecular ions and neutral radicals.
Applications: lipid mass spectrometry
My group is currently involved in the rapidly expanding field of lipidomic research. Using modern MS techniques we are able to observe subtle changes in the lipid composition of cell membranes. These changes in the membrane lipid profile can associated with a range of factors including; diet, exercise, illness or age. For example, in collaboration with Dr Todd Mitchell (Health and Behavioural Science) and Prof Roger Truscott (Save Sight Institute) we are probing changes in the lipid profile of the human lens that may be associated with the onset of cataract. In another collaboration we have been working with Professor Mark Willcox at the Brien Holden Vision Institute on understanding how the tear lipdome changes with dry eye and contact lens wear. We have also developed two novel tools for structure elucidation of lipids by mass spectrometry. Known as ozone electrospray ionization mass spectrometry (OzESI-MS) and ozone induced dissociation (OzID), these methods can precisely locate double bonds within a lipid molecule giving unique insight into its structure and biological function.
Applications: keeping colourbond® colourful
In collaboration with Dr Philip Barker at Bluescope Steel Research we are using the complementary technologies of electron spin resonance (ESR) and electrospray ionization mass spectrometry (ESI-MS) to elucidate oxidation processes that occur within the polymer coating of Bluescope's flagship sheet steel product, colorbond steel®. ESR readily identifies free radicals formed by these oxidation processes, while ESI-MS provides structural information about both radical and non-radical species formed by these processes. These studies are directed towards improving the longevity of colorbond under the harsh oxidizing conditions encountered on the typical Australian roof! Recently we have employed a new technologies including desorption electrospray ionisation (DESI-MS) and liquid extraction surface analysis (LESA) to identify anti-oxidants in steel coating systems. This work is a part of the ARC Centre of Excellence for Free Radical Chemistry and Biotechnology.
Fundamentals: perxoyl radicals and peroxide anions in the gas phase
The advantage of gas phase studies, using mass spectrometers, over traditional "wet-chemistry" is that the former allow us to understand the fundamental reactivity of ions and molecules without interference from either solvent or counter-ions. Furthermore, some critically important ions and molecules are so reactive that they can only be studied in the isolation of the vacuum inside the mass spectrometer. The results of these fundamental studies contribute to our understanding of complex applied problems in biological, atmospheric, interstellar and combustion chemistries. Selected projects currently under investigation are outlined below.
In a collaboration with Dr Adam Trevitt (Chemistry) and Professor Richard O'Hair (University of Melbourne), we have modified a linear ion-trap mass spectrometer (ThermoFinnigan LTQ) to allow the observation of ion-molecule reactions and the irradiation of trapped ions with lasers. Using this equipment we are developing a range of methods for producing distonic peroxyl radical anions in the gas phase using electrospray ionization. Distonic ions have a separated charge and radical center and can thus act as "charge-tagged radicals" where the charge does not significantly perturb the reactivity of the radical but simply provides us with a convenient handle with which to isolate it in the ion trap mass spectrometer. We are currently investigating the reactions of alkyl and aryl peroxyl radicals using this approach and also elucidating their photodissociation behaviours. This new methodology will provide unique insight into the chemistry of peroxyl radicals in the gas phase and thus the role of peroxyl radical intermediates in biochemical and atmospheric processes.
Ly, T., Kirk, B. B., Hettiarachchi, P. I., Poad, B. L. J., Trevitt, A. J., da Silva, G. and Blanksby, S. J. "Reactions of Simple and Peptidic alpha-Carboxylate Radical Anions with Dioxygen in the Gas Phase" Physical Chemistry Chemical Physics, 2011, 13, 16314–16323. [Cover Article].
Paine, M. R. L., Barker, P. J. and Blanksby, S. J. "Desorption Electrospray Ionisation Mass Spectrometry Reveals In Situ Modification of a Hindered Amine Light Stabiliser Resulting From Direct N-OR bond cleavage" Analyst 2011, 136 (5), 904-912. [Cover Article]
Poad, B. L. P., Pham, H. T., Thomas, M. C., Nealon, J. R., Campbell, J. L., Mitchell, T. W. and Blanksby, S. J. "Ozone-induced dissociation on a modified tandem linear ion-trap: observations of different reactivity for isomeric lipids" Journal of the American Society for Mass Spectrometry 2010, 21, 1989-1999. [Cover Article]
Deeley, J. M., Hankin, J. A., Friedrich, M. G., Murphy, R. C., Truscott, R. J. W., Mitchell, T. W. and Blanksby, S. J. "Sphingolipid distribution changes with age in the human lens" Journal of Lipid Research 2010, 51(9), 2753-2760.
Ichino, T., Villano, S. M., Gianola, A. J., Goebbert, D. J., Verlade, L., Sanov, A., Blanksby, S. J., Zhou, X., Hrovat, D. A., Borden , W. T., Lineberger, W. C., "The Lowest Singlet and Triplet States of the Oxylallyl Diradical" Angewandte Chemie-International Edition 2009, 48, 8509-8511. [Cover Article]
McAnoy, A. M., Paine, M. R. L., and Blanksby, S. J., "Reactions of the hydroperoxide anion with dimethyl methylphosphonate in an ion trap mass spectrometer: evidence for a gas phase alpha-effect." Organic & Biomolecular Chemistry 2008, 6(13), 2316-2326. [Inside Cover Article]
Thomas, M. C., Mitchell, T. W., Harman, D. G., Deeley, J. M., Nealon, J. R., and Blanksby, S. J., "Ozone Induced Dissociation: elucidation of double bond position within mass-selected lipid ions" Analytical Chemistry 2008, 80(1), 303-311.
Mitchell, T. W., Ekroos, K., Blanksby, S. J., Hulbert, A. J., and Else, P. L., "Differences in membrane acyl phospholipid composition between an endothermic mammal and an ectothermic reptile are not limited to any phospholipid class" Journal Of Experimental Biology 2007, 210(19), 3440-3450.
Thomas, M. C., Mitchell, T. W., Deeley, J. M., Harman, D. G., Murphy, R. C., and Blanksby, S. J., "Elucidation of Double Bond Position in Unsaturated Lipids by Ozone Electrospray Ionization Mass Spectrometry (OzESI-MS)" Analytical Chemistry 2007, 79 (13), 5013-5022.
Blanksby, S. J., Ellison, G. B., Bierbaum, V. M., and Kato, S., "Superoxide Does React with Peroxides: Direct Observation of the Haber-Weiss Reaction in the Gas Phase" Angewandte Chemie-International Edition 2007, 46, 4948-4950.
Thomas, M. C., Mitchell, T. W.; Blanksby, S. J. "Ozonolysis of phospholipid double bonds during electrospray ionization: A new tool for structure determination" Journal of the American Chemical Society 2006, 128 (1), 58-59.
Harman, D. G.; Blanksby, S. J., "Trapping of a tert-adamantyl peroxyl radical in the gas phase" Chemical Communications 2006, 8, 859-861.
Blanksby, S. J.; Ellison, G. B. "Bond Dissociation Energies of Organic Molecules." Accounts of Chemical Research 2003 , 36 , 255-263.
Blanksby, S. J.; Ellison, G. B.; Bierbaum, V. M.; Kato, S. "Direct Evidence for Base-Mediated Decomposition of Alkyl Hydroperoxides (ROOH) in the Gas Phase" Journal of the American Chemical Society 2002 , 124 , 3196-3197.
Blanksby, S. J.; McAnoy, A. M.; Dua, S.; Bowie, J. H. "Cumulenic and Heterocumulenic Anions: Potential Interstellar Species?" Monthly Notices of the Royal Astronomical Society 2001, 328 , 89-100.
Blanksby, S. J.; Schroeder, D.; Dua, S.; Bowie, J. H.; Schwarz, H. "Conversion of Linear to Rhombic C 4 in the Gas Phase: A Joint Experimental and Theoretical Study." Journal of the American Chemical Society 2000, 122 , 7105-7113.
Cover art gallery
Nicole Pianegona "Detection and identification of micro-organisms by surface analysis mass spectrometry"
Jo Seng "Characterisation of the Human lens lipidome"
Jennifer Saville "Exploration of the lipid composition in tears and the effect of contact lens wear"
Martin Paine "Development of new additives for surface coatings"
David Marshall "Mechanisms of HALS degradation in surface coatings"
Rachel Kozlowski "Coupling chromatography with advanced mass spectrometric methods for lipidomics"
Chris Hansen "Photodissociation of ions in a modified linear ion trap mass spectrometer"
Current Postdoctoral Fellows
Dr Alan Maccarone (PhD, University of Colorado, Boulder)
2010-present Professor, School of Chemistry, University of Wollongong.
2005-2009 Senior Lecturer, School of Chemistry, University of Wollongong.
2002-2004 Lecturer, School of Chemistry, University of Wollongong.
2000-2002 Postdoctoral Researcher with Professor G. Barney Ellison and W. Carl Lineberger, Department of Chemistry, University of Colorado, Boulder CO.
1999 Visiting Researcher with Professor Helmut Schwarz, Institut für Organishe Chemie, Technische Universität Berlin, Berlin, Germany.
1996-1999 Ph.D. student at University of Adelaide Supervisor Professor John Bowie.
Awards and recognition:
2011 Vice Chancellor's Commendation for Excellence in Research Supervision University of Wollongong
2010 Vice Chancellor's Award for Interdisciplinary Research (with Dr Todd Mitchell), University of Wollongong for "outstanding contribution to research by a team of UOW researchers collaborating across discipline boundaries."
2009 LeFèvre Memorial Prize, Australian Academy of Science and Royal Australian Chemical Institute for "outstanding basic research in chemistry by scientists under 40 years"
2009 Bowie Medal, Australian and New Zealand Society for Mass Spectrometry for "excellence in research in any area of mass spectrometry by a young Australia or New Zealand researcher"
2007 Rennie Memorial Medal, Royal Australian Chemical Institute for "a financial member of the RACI with less than 8 years of professional experience...[who]....has contributed most towards the development of some branch of chemical science"
Speaker: Prof. Mick Sherburn
Affiliation: Research School of Chemistry, ANU
Title: Unveilling the True Synthetic Potential of Polyenes
Date: Tuesday 21st May, 2013