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Dr Allan McKinley
 | A.J McKinleyB.Sc. Ph.D (Canterbury) Graduate Research Coordinator | Phone: Fax: Email: | (61 8) 6488 3165 (61 8) 6488 7111 allan.mckinley@uwa.edu.au |
Postdoc. Fellow, Univ. of Texas (Austin), 1987-1990 Assistant Professor/Dreyfus Fellow 1991-1993 Furman University, Greenville, SC, USA
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RESEARCH INTEREST
My research interests involve: applications of spectroscopy
for the detection and characterization of reactive
intermediates, theoretical modeling of the bonding in radicals,
analysis and remediation of conatminated groundwater, and
biological applications of Electron Spin Resonance
spectroscopy. For more information on ESR/EPR spectroscopy at
UWA see the WAEPR
page.
1.1 Matrix Isolation Studies of Reactive Intermediates
In room G125 we have built a state-of-the-art apparatus for
measuring the ESR spectra of molecules trapped in solid neon at
4 K. There are less than half a dozen labs with this type of
equipment in the world, no other in Australia. This project
would involve using this equipment to synthesize new molecules
and characterize their bonding and structure. This is cutting
edge work and some of our recent successes CdCH3 [1], ZnCH3 [2]
and MgCH3 [3], are published in top international chemistry
journals. The results of our studies are important to improve
the understanding of models of chemical bonding as well as the
chemical mechanisms involved in manufacturing computer chips,
wear-resistant coatings, and even the chemical processes
occurring in circumstellar dust clouds. Projects in this area
could be experimental or involve theoretical calculations or
both.
Environmental Chemistry of Contaminated Groundwater.
For some years now we have had a collaboration with Drs Greg
Davis and Brad Patterson at the Land and Water division of
CSIRO at Floreat. In Australia, water is a key resource. In WA
much of our water reserves are underground and very vulnerable
to pollution. We have studied the degradation in groundwater of
BTEX hydrocarbons (from leaking petrol stations), the mobility
of pesticides such as atrazine and fenamiphos in soils and this
year we have been evaluating the possibility of employing a new
method for remediation of contaminated groundwater using
polymer-mats to introduce gaseous reagents into groundwater to
promote microbial consumption of the pollutants. We have a
provisional patent on this new process. As well as remediation
groundwater contamined by BTEX and other votatile organics [4]
we have studied denitrification of ammonium contaminated
groundwater[5]. There are still many issues to clarify here and
we want to extend this work to other pollutants. Projects in
this area would involve either the analysis of the chemistry
occurring in, or the mathematical modeling of the mass
transport phenomena involved with, pilot scale test-rigs for
groundwater remediation which are set up at CSIRO in
Floreat.
Biological Applications of ESR Spectroscopy.
Radicals play a very important role in biology. It is
thought damage from radicals could be responsible for processes
such as aging and cancer. We have collaborated with Dr Rob
Tuckey in Biochemistry and employed ESR on frozen samples to
quantitate the redox state of the adrenodoxin in mitochondria
derived from human placenta [6]. A joint project with Dr Tuckey
of Biochemistry could be arranged. Also this year we have
collaborated with Associate Professor Boris Martinac from
Pharmacology and we have developed a new apparatus to measure
the ESR spectra of proteins that have been labeled with a
nitroxide radical. The label is introduced onto a specific
position of the protein backbone by incorporating a cysteine
residue at that position using site-directed mutagenesis then
binding the nitroxide label selectively to the cycteine
residues. By observing the effect on the ESR signals of adding
a relaxation agents to the aqueous or lipid phase we can infer
the tertiary structure of the protein. This work is only
preformed by about three groups in the world [7]. We now have
the technology and Associate Professor Martinac has a new ion
channel protein that could be interrogated. This project would
be best performed as a joint Honours project with the
Department of Pharmacology.
1.2 References
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Karakyriakos, E.; Davis, J. R.; Wilson, C. J.;
Yates, S. A.; McKinley, A. J.; Knight, L. B. Jr.; Babb R.;
Tyler, D. J. (1999) Neon and argon
matrix ESR and theoretical studies of the
12CH3Cd,
12CD3Cd,
13CH3Cd,
12CH3111Cd, and
12CH3113Cd Radicals. J. Chem. Phys.,
3398-3410
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McKinley, A. J.; Karakyriakos, E.; Knight, L. B.
Jr.; Babb, R.; Williams, A. (1999)
Matrix isolation ESR studies of the various
isotopomers of the CH3Zn and ZnH radicals;
comparisons with ab initio theoretical calculations. J. Phys. Chem. A., 104,
3528-3536
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McKinley, A. J.; Karakyriakos, E.
Neon matrix isolation ESR and theoretical studies of
the various isotopomers of the CH3Mg radical.
J. Phys. Chem. A.
accepted for publication. 10 pages.
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Patterson, B. M.; Grassi, M. E.; Brill, M.; Davis,
G. B.; McKinley, A. J. (2000) In situ
bioremediation of ammonium-contaminated groundwater using a
sequential oxygen/reductant gas delivery system: laboratory
evaluation. accepted as a conference
paper for the 2000 Contaminated Site Remediation
Conference, Melbourne, 4-8 December
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Petterson, B. M.; Davis, G. B.; McKinley, A.
J. Polymer mats to remove selected
VOCs, PAHs and pesticides from groundwater: laboratory
column experiments. in preparation.
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Tuckey, R. C.; McKinley, A. J.; Headlam, M.
J. Oxidised adrenodoxin acts as a
competitive inhibitor of cytochrome P450scc in mitochondria
from human placenta. submitted.
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See for instance, Perozo, E.; Cortes, D. M.;
Cuello, L. G. (1998) Three-
dimensional architecture and gating mechanism of a K+
channel studied by EPR spectroscopy. Nature Structural Biology, 5,
459-469
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