Dr Stephen Blanksby

Research Interests

Mass Spectrometry (MS): Applications and Fundamentals

The mass spectrometry laboratory at UOW has 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® roofing panels! In addition to these analytical applications, the mass spectrometer provides the ideal gas phase "test tube" for probing the structure and reactivity of molecular ions and neutral radicals.

Biomolecular Mass Spectrometry Laboratory

Applications: phospholipid 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 (Biomedical 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. We have also developed two new tools for structure elucidation of lipids by mass spectrometry. Known as OzESI and OzID, these methods can precisely locate double bonds within a lipid molecule giving unique insight into its structure and biological function.

Applications: keeping colorbond® 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® . 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 technology called Desorption Electrospray Ionisation (DESI) to identify anti-oxidants in steel coating systems.

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.

Using the latest in ion-trap mass spectrometry equipment (the ThermoFinnigan LTQ) we are developing a range of methods for producing distonic peroxyl radical anions in the gas phase using electrospray ionization. Distonic anions 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 methods for reacting our charge tagged peroxyl radicals with a range of neutral substrates in the gas phase. 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.

Representative Publications

Thomas, M. C., Mitchell, T. W., Harman, D. G., Deeley, J. M., Nealon, J. R., and Blanksby, S. J., "Ozone Induced Dissociation (OzID): a novel method for the elucidation of double bond position within mass-selected lipid ions" Analytical Chemistry 2008, 80, 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.

Searchable Publication List

Current Students

PhD:

Huong (Nicole) Pham Characterisation of triacylglycerols in lipoproteins

Martin Paine New additives for surface coatings

Michael Thomas Structural characterisation of phospholipids by mass spectrometry”

Jane Deeley Changes in the lens phospholidome with aging and cataract

Jessica Nealon Diet induced changes in the lens phospholipidome

Benjamin Kirk Investigation of free radical reactivity using a distonic ion approach

Jennifer Saville Exploration of the lipid composition in tears and the effect of contact lens wear

David Marshall Investigations of the role of Hindered Amine Light-Stabilisers (HALS) in the protection of surface coatings

Shane Ellis Coupling inkjet printing technologies with desoprtion electrospray ionization analysis

Suggested Topics for Future Students

Synthesis and reactivity of distonic anions in the gas phase

Structural characterisation of phospholipids by mass spectrometry

Gas phase reaction mechanisms: experiment and theory

Abbreviated CV

1996-1999 Ph.D. student at University of Adelaide Supervisor Professor John Bowie

1999 Visiting Researcher with Professor Helmut Schwarz, Institut für Organishe Chemie, Technische Universität Berlin, Berlin, Germany.

2000-2002 Postdoctoral Researcher with Professor G. Barney Ellison and W. Carl Lineberger, Department of Chemistry, University of Colorado, Boulder CO.

2002-2004 Lecturer in Chemistry, Department of Chemistry, University of Wollongong, Wollongong.

2005-present Senior Lecturer in Chemistry, Department of Chemistry, University of Wollongong, Wollongong, Australia.

Last reviewed: 15 April, 2009