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Analytical,
Surface, and Materials Chemistry Barbara Womack LSU Alumni
Professor (b.
1964)
B.A. Lake Forest College, Lake Forest, IL, 1986;
Ph.D., University
of North Carolina, 1990;
National Science Foundation Postdoctoral
Fellow, University of Texas, 1990-1992;
Society for Analytical Chemists of Pittsburgh Award,
1993; LSU
College of Basic Sciences Research Award, 1998;
LSU College of Basic Sciences Award of Excellence in Undergraduate
Teaching, 2002
LSU Distinguished Faculty Award, 2003
The general theme of the research that is carried out in our
laboratories is the chemistry of supramolecular systems in solution and on
surfaces. Our desire is to be able to control the properties of materials
by manipulating the structure of the materials on the molecular scale.
For
instance, our group is
interested in constructing stimuli-sensitive molecular architectures
based on dendrimers, surfactants, and polymers that
can be used to trap, contain, and release molecules; through the use of redox-responsive
and temperature-responsive
functionalities at the exterior of dendrimers, we are able
to regulate the transport of materials from the interior of the
dendrimer to the exterior, surrounding solution. In addition,
other redox-responsive or temperature-responsive moieties can be
placed on a variety of materials for use in chemical sensing
applications; see a recent Chemical and Engineering News
article highlighting our work in this area. This
NSF-funded project involves the use of a variety of analytical
methods, such as NMR methods, fluorescence
spectroscopy, and infrared spectroscopy, and synthetic strategies
for making the host systems. Recent results indicate that such
materials will be useful in the delivery of molecules in the body
and in miniaturized analytical systems. In addition, we have
been exploring the properties of the stimuli-responsive moeities
using MALDI-MS, in particular, their end groups and molecular
weight. Yuming
Yang, Warren Solfiell,
Jerimiah Forsythe,
Nicole Hollabaugh,
Fabi Mendoza,
Thy Nguyen, and
Dr. Sreelatha Balamurugan will be happy to discuss this project. In another area,
we are interested
in controlling the surface properties of polymer substrates used in
the fabrication of microanalytical devices by immobilizing
nanometer-thick layers of organic and biological molecules on the
surface of the plastic substrate; such surface modification
protocols are of great importance to microanalytical devices geared
towards genomic, proteomic, and environmental analyses. This
project is funded through the National Institutes of Health and NSF and is a
collaborative effort with the
Soper Group in Chemistry, as well
as groups in Mechanical Engineering. In addition, we are
working with several groups in physics, biology, and engineering to
build nanoscopic sensors and pumps/actuators. For more information from a
student perspective, contact
Jowell Bolivar or
Jenny Macalindong. Another
postdoctoral fellow will soon be joining us on this project. In addition to
these more applied directions, we are interested in understanding
the fundamentals of adsorbate interactions (alkanethiols,
isocyanides) with metal surfaces (Pt, Au, Ag, Cu) and the
interactions of metals (evaporated, electrolessly deposited,
nanoclusters) with "sticky" (chemically modified so as to
present a binding ligand to the depositing metal) surfaces.
For example, we are looking at ways to photopattern surfaces so that
metal deposition is confined to a given area (micrometer to
nanometer square areas). Both areas are of interest to the
microelectronics industry, as well as the microanalytical device and
sensor communities. Related
to this binding of metals on surfaces is the template-assisted
formation of metal nanoclusters using dendrimers as the
template. We have recently shown that ~1 nm diameter Cu
nanoclusters can be made by reduction of Cu(II)-amine-dendrimer
complexes. By varying the Cu(II):dendrimer ratio, we have been
able to make extremely monodisperse metal and metal oxide nanoclusters. This work
will be used to lay the groundwork for future studies of bi-metallic clusters
and metal oxide nanoparticles that can be used for
catalysis applications, including those associated with
environmental concerns. This project is a collaborative effort
with Professors
Dellinger,
Poliakoff,
Hall
from chemistry and his
students and involves the use of our synchrotron radiation source,
CAMD.
Please feel free to contact Eli
Mitran about this work. Undergraduate researchers on this
project include
Jill Taylor
(spectroscopy work).
Students within the McCarley Group gain a great deal of
experience in a number of areas in chemistry, biology, and materials science due to the diverse,
interdisciplinary nature of the research efforts. For example, you are apt
to find someone doing organic synthesis on a surface or solution one day, and
then discover them carrying out surface infrared spectroscopy, scanning probe
microscopy, X-ray spectroscopy, or mass spectrometry the next day! Or you
might find someone making a microdevice, and then a few minutes later see that
they are performing photopatterning of the plastic surface to immobilize
proteins or DNA. In addition, Professor McCarley is an associate of the Macromolecular
Studies Group at LSU, and a participant in the NSF-funded Craft
for Macromolecular Creativity IGERT. Thus, the student who carries out research in the
McCarley Group will become well-versed in a variety of topics related to
analytical, physical, inorganic, macromolecular, biological, and organic chemistries.
As a
result of their training, students in the McCarley Group have gone on to outstanding
careers in chemistry and materials science.
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Dr.
John Peanasky is a scientist at Corning
in Corning,
NY and is carrying out work on optically based biosensors.
-
Dr.
Robert Willicut ('97) is a scientist in the Health and Beauty Care
Division at Proctor and Gamble, Cincinnati, OH, and is working on
polymer rheology and surface analysis of non-traditional
materials.
-
Dr.
Tamara Nauman has been an Instructor at LSU since 1997.
-
Dr.
Song Lin ('00) is currently employed in the Baton Rouge area.
-
Dr.
Cory Schomburg ('00) is on the staff of Columbian
Chemicals Company in Marietta,
Georgia, where he researches support materials for fuel cells.
-
Dr.
Pierre
Floriano ('01) is a postdoctoral fellow with Professor John
McDevitt at the Beckman
Center for Sensing at the University of Texas.
-
Dr.
Sonya
Caston-Pierre ('01) is a faculty member at Dillard
University in New Orleans.
-
Dr.
Alyssa
Henry ('01) is a staff scientist at the National Institutes of
Health where she is working on research with miniaturized
analytical devices.
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Dr.
Charles
O. Noble ('01) is currently at Hermes Biosciences in San
Francisco, CA. He was a postdoctoral researcher at the
University of California in San Francisco, CA where he worked on
liposome-based drug release agents.
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Dr.
Jed
Aucoin ('04) is a scientist at Lockheed-Martin Space Systems
Company in their Michoud Assembly Facility in New Orleans, where
he is working on materials characterization for the US Space
Shuttle Project.
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Dr.
Bikas Vaidya is
currently a scientist at Lynntech at their facility in Bryan, TX
where is working on a variety of projects dealing with fuel
cells. He received his Ph.D. under the direction of Marc D.
Porter at Iowa State University.
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Dr.
Amy Donaldson Morara ('05) is a
Lead Chemist at the Pine Bluff Arsenal in Arkansas.
-
Dr.
Mariah J. McMasters ('06) is an Instructor of Analytical
Chemistry at Louisiana State University.
-
Dr.
Suying Wei ('06) is now a postdoctoral fellow with Professor
Michael Sailor at the University of California at San Diego
working in biomaterials.
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Dr.
Eden Pacsial-Ong (PD, 2005-2006) worked as a Senior Scientist at
Vegrandis, LLC in
Fayetteville, AR in the area of clinical diagnostics and has
recently relocated to Boston, MA.
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Dr.
Sreelatha Balamurugan (PD,
2003-2006) is a potdoctoral fellow working with Professor Paul
Russo at LSU.
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Dr.
Rebecca Brauch
('06) is a Scientist at the Clorox Company in Pleasanton, CA
working on mass spectrometry.
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Dr.
Henry Wiggins ('07) is a Scientist at Halliburton in Oklahoma
where he is working on analysis methods applied to the
petrochemical industry.
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Dr.
Guofang Chen (PD, 2004-2007)
is a postdoctoral researcher at Lawrence Berkeley National
Laboratory and will become a faculty member at St. John's
University in January 2008.
-
Dr.
Winston Ong (PD,
2004-2007) is now a
Scientist
at Transform Pharmaceuticals
(a Johnson and Johnson Company) working on nworking
on early drug development.
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Dr.
C.J.
Dubois, Jr. (BS at LSU, '98) is a scientist at DuPont Central Research
in Wilmington, DE working
on a variety of polymeric display projects. He received his
Ph.D. under the direction of Professor John Reynolds at the University
of Florida, and was an LSU undergraduate researcher.
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Dr. Stefanie
M. Chaplin was in the chemical, bio-, and materials
engineering department at Arizona State University from 1998 to
2004 (PhD, 2004) where she studied Si wafer processing techniques.
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Benjamin
Boussert (BS at LSU, '99) was a graduate student in the group of Paul Alivisatos at the University of California at Berkeley.
Tragically, Ben perished in an automobile accident on July 16,
2005 after participating in the graduation exercises in May of
2005.
Recent Publications from the McCarley Laboratories
G. Chen, S.A. Soper and R.L. McCarley,
Free-Standing, Erect Ultra-high-aspect-ratio Polymer Nanopillar and
Nanotube Ensembles,
Langmuir, 2007, Accepted for publication.
G. Chen, R.L. McCarley, S.A. Soper, C. Situma
and J. Bolivar,
Functional Template-Derived Poly(methyl methacrylate) Nanopillars for
Solid-Phase Biological Reactions,
Chem. Mater., 2007, 19(16), 3855-3857.
DOI:
10.1021/cm0702870
M.A. Etienne, N.J. Edwin, J.P. Aucoin, P.S.
Russo, R.L. McCarley, R.P. Hammer,
b-Amyloid
Protein Aggregation. Methods in Molecular Biology (Totowa, NJ, United
States) 2007, 386(Peptide Characterization and Application
Protocols), 203-225.
E. Pacsial-Ong, W. Wang, R.M. Strongin and R.L.
McCarley,
Electrochemical Detection of Glutathione Using Redox Indicators,
Anal. Chem., 2006, 78(21), 7577-7581;
DOI:
10.1021/ac061451q
W. Ong and R.L.
McCarley,
Chemically- and Electrochemically-Mediated Release of Dendrimer End Groups,
Macromolecules, 2006, 39(21), 7295-7301;
DOI:
10.1021/ma061341l
M.A. Witek, S.D. Llopis, A.
Wheatley, R.L. McCarley and S.A. Soper,
Purification and preconcentration of genomic DNA from whole cell lysates using
photoactivated polycarbonate (PPC) microfluidic chips,
Nucl. Acids Res. 2006, 34(10), e74.
DOI:
10.1093/nar/gkl146
S. Balamurugan, A. Obubuafo,
S.A. Soper, R.L. McCarley, and D.A. Spivak,
Designing Highly Specific
Biosensing Surfaces Using Aptamer Monolayers on Gold,
Langmuir 2006;
22(14), 6446-6453. DOI:
10.1021/la060222w
A.D.
Morara and R.L. McCarley,
TEO-Pyrrole-Terminated Dendrimer Hosts – Synthesis and Characterization,
Org. Lett. 2006, 8(10),
1999-2002. DOI:
10.1021/ol060288i
G.B. Bantchev, P.S.
Russo, R.L. McCarley, and R.P. Hammer,
A Simple, Multi-angle, Multi-correlator Depolarized Dynamic Light Scattering
Apparatus,
Rev. Sci. Inst. 2006, 77(4), 043902/1-043902/6.
DOI: 10.1063/1.2186807
X. S. Wu, P. W. Adams, Y.
Yang, and R. L. McCarley,
Interface Spin-Orbit Coupling in a Non-centrosymmetric
Thin-Film Superconductor,
Phys. Rev. Lett. 2006, 96(12),
127002/1-127002/4. DOI:
10.1103/PhysRevLett.96.127002
R.P. Hammer, M.A. Etienne,
Jed P. Aucoin, and R.L. McCarley,
Stoichiometric Inhibition of
Amyloid b-Protein
Aggregation with Peptides Containing Alternating
a,a-Disubstituted
Amino Acids,
J. Am. Chem. Soc. 2006,
128, 3522-3523.
DOI:
10.1021/ja0600678
S.A. Soper, M. Hashimoto,
C. Situma, M.C. Murphy, and
R.L. McCarley,
Fabrication of DNA Microarrays onto Polymer Substrates Using UV
Modification Protocols with Integration into Microfluidic Platforms for the
Sensing of Low-Abundant DNA Point Mutations,
Methods
2005,
37,
103-113.
DOI:
10.1016/j.ymeth.2005.07.004
N.J. Edwin, G.B. Bantchev,
P.S. Russo, Robert P. Hammer, and R.L. McCarley,
Elucidating the Kinetics of
b-Amyloid Fibril
Formation In New Polymeric Materials; L.S.
Korugic-Karasz, W.J. MacKnight, and E. Martuscelli, Eds.; ACS Symposium Series
916; American Chemical Society: Washington, D.C., 2005, pp. 106-118.
W. Ong and R.L. McCarley,
Redox-driven
Shaving of Dendrimers
Chem.
Comm. 2005,
(37),
4699-4701. DOI:
10.1039/b506724c
S. Wei, B. Vaidya, A.B. Patel, S.A. Soper, and
R.L. McCarley,
Photochemically Patterned Poly(methyl methacrylate) Microanalytical Devices
J. Phys. Chem. B.
2005,
109(35),
16988-16996.
DOI:
10.1021/jp051550s
***S.S. Balamurugan, G.B. Bantchev, Y. Yang, and
R.L. McCarley,
Highly
Water-Soluble Thermally Responsive Poly(thiophene)-based Brushes,
Angewandte Chemie
2005,
44,
4872-4876. DOI:
10.1002/anie.200500867
M. J. McMasters, R.P. Hammer and R.L. McCarley,
Surface-Induced Aggregation of Beta Amyloid Peptide by
-Substituted Alkanethiol Monolayers Supported on Gold,
Langmuir 2005, 21(10), 4464-4470.
DOI:
10.1021/la047044w
C. Situma, Y. Wang, M. Hupert, F. Barany, R.L. McCarley and S.A. Soper,
Fabrication of DNA microarrays onto poly(methyl methacrylate) with
ultraviolet patterning and microfluidics for the detection of low-abundant
point mutations,
Anal. Biochem. 2005, 340(1),123-135.
W. Ong and R.L. McCarley,
Positive Dendritic Effects on the Electron-Donating Potencies of
Poly(propylene imine) Dendrimers,
Organic Letters 2005, 7(7), 1287-1290.
DOI:
10.1021/ol0500564
R.L. McCarley, B. Vaidya, S. Wei, A.F. Smith, A.B. Patel, J. Feng, M.C. Murphy
and S.A. Soper,
Resist-free Patterning of Surface Architectures in Polymer-based
Microanalytical Devices,
J. Am. Chem. Soc. 2005, 127, 842-843.
DOI:
10.1021/ja0454135
M.A. Witek, S.Wei, B. Vaidya, A.A. Adams, L. Zhu, W. Stryjewski, R.L. McCarley
and S.A. Soper,
Cell Transport via Electromigration in Polymer-based Microfluidic Devices,
Lab on a Chip 2004, 4, 464-472.
E.E. Doomes, R.W. Zurales, R.L. McCarley, and
E.D. Poliakoff,
Correlations Between Heterocycle Ring Size and X-ray Spectra,
J. Chem. Phys. 2003, 119, 4399-4404.
E.E. Doomes, P.N. Floriano, R.W. Tittsworth, R.L. McCarley, and E.D. Poliakoff,
Anomalous XANES Spectra of Octadecanethiol Adsorbed on Ag(111),
J. Phys. Chem. B, 2003
107,
10193-10197.
DOI:
10.1021/jp021510d
B. Vaidya,
S.A. Soper, and R.L. McCarley, Surface Modification and Characterization of
Microfabricated Poly(carbonate) Devices: Manipulation of Electroosmotic Flow,
The Analyst 2002, 127, 1289-1292.
S.A. Soper, A.C. Henry,
B. Vaidya,
M. Galloway, M. Wabuyele, and R.L. McCarley, Surface Modification of
Polymer-Based Microfluidic Devices,
Anal. Chim. Acta. 2002, 470, 87-99.
S.L. Caston and R.L. McCarley,
Characteristics of Nanoscopic Band Electrodes,
J. Electroanal. Chem. 2002, 529, 124-134.
M.
Galloway, W. Stryjewski,
A. Henry,
S.M. Ford, S. Llopis, R.L. McCarley,
S.A.
Soper,
Contact Conductivity Detection in Poly(methyl methacylate)-Based
Microfluidic Devices for Analysis of Mono- and Polyanionic Molecules,
Anal. Chem. 2002, 74, 2407-2415.
P.N. Floriano,
C.O. Noble, IV,
J.M. Schoonmaker, E.D. Poliakoff,
and R.L. McCarley,
Cu(0) Nanoclusters Derived from Poly(propylene imine) Dendrimer Complexes
of Cu(II),
J. Am. Chem. Soc. 2001, 123, 10545-10553.
T.D. McCarley, C.J. Dubois, Jr., C.O. Noble,
IV, and R.L. McCarley, MALDI-MS of Poly(3-hexylthiophene) Synthesized by
Chemical Oxidative with FeCl3,
Macromolecules 2001, 34, 7999-8004.
A.C. Henry and R.L. McCarley, Selective
Deposition of Metals on Plastics Used in the Construction of Microanalytical
Devices—Photo-Directed Formation of Metal Features on PMMA,
J. Phys. Chem. B 2001, 105, 8755-8761.
I.I. Negulescu, R.L.
McCarley, C.C. Delatte, P. N. Floriano, and J. Jiechao, Coloration of
Natural and Synthetic Fibers with Metallic Nanoparticles,
Polymeric Materials: Science & Engineering 2001, 84,
471-472.
S. Hasegawa, T. Horigome,
K. Yakushi, H. Inokuchi, K. Okudaira-Kamiya, N. Ueno, K. Seki, R.J. Willicut,
R.L. McCarley, E. Morikawa and V. Saile, Angle-Resolved Photoemission
Measurements of Omega-(N-pyrrolyl)alkanethiol Self-Assembled Monolayers Using
In-Situ Sample Preparation Apparatus,
J. Electron. Spectrosc. 2001, 113, 101-107.
K. Cory Schomburg and R.L.
McCarley, Surface-Confined Monomers on Electrode Surfaces. 11.
Electrochemical and Infrared Spectroscopic Characteristics of
Aniline-Terminated Alkanethiol Monolayers on Au Electrochemically Treated in
Non-aqueous Media,
Langmuir 2001, 17, 1993-1998.
K. Cory Schomburg and R.L.
McCarley, Surface-Confined Monomers on Electrode Surfaces. 10.
Electrochemical and Infrared Spectroscopic Characteristics of
Aniline-Terminated Alkanethiol Monolayers on Au Electrochemically Treated in
Aqueous Solution,
Langmuir 2001, 17, 1983-1992.
K.C. Schomburg and R.L.
McCarley. Electrochemical and Infrared Analysis of Alkoxyaniline
Derivative Monolayers on Gold. In Interfacial Properties on the
Submicron Scale, Jane Frommer and Rene Overney, Eds.; ACS Symposium Series
781; American Chemical Society:Washington, DC; 2001, pp 306-320.
A.C. Henry, T.J. Tutt, C.S. McWhorter, Y.
Davidson, S.A.
Soper, and R.L. McCarley, Chemical Modification of
Poly(methyl methacrylate) Used in the Construction of Microanalytical Devices,
Anal. Chem. 2000 72, 5331-5337.
S.A.
Soper, S.M. Ford, S.
Qi, R.L.
McCarley, K. Kelly, and
M.C. Murphy, Microelectromechanical Systems
Fabricated in Polymeric Materials: Applications in Chemistry and Life Sciences,
Anal. Chem. 2000 72, 643A-651A.
C.O. Noble, IV and R. L. McCarley, Pyrrole-Terminated
Diaminobutane (DAB) Dendrimer Monolayers on Gold—Oligomerization of
Peripheral Groups and Adhesion Promotion of Poly(pyrrole) Films,
J. Am. Chem. Soc., 2000, 127, 6518-6519.
P.N. Floriano, O.
Schlieben, E.E. Doomes,
I. Klein, J. Janssen, J. Hormes, E.D. Poliakoff and R.L. McCarley, A
Grazing Incidence Surface X-ray Absorption Fine Structure (GIXFAS) Study of
Alkanethiols Adsorbed on Au, Ag, and Cu,
Chem. Phys. Lett., 2000, 321, 175-181.
C.O. Noble, IV
and R. L.
McCarley, Surface-Confined Monomers on Electrode Surfaces. 7. Synthesis of
Pyrrole-Terminated Poly(propylene imine) Dendrimers,
Organic Letters, 1999, 1, 1021-1023.
A.C. Henry, R. L. McCarley, S. S. Das,
and C. G. Khan Malek, Characteristics of Commercial PMMA Sheets Used in the
Fabrication of Extreme High-Aspect-Ratio Microstructures,
J. Electrochem. Soc., 1999,
146, 2631-2636.
S. Lin and R. L.
McCarley, Surface-Confined Monomers on Electrode Surfaces. 6. Adsorption
and Polymerization of 1,6-Diisocyanohexane on Au and Pt,
Langmuir, 1999, 15, 151-159.
T.D. McCarley, M.
W. Lufaso, L. S. Curtin, and R. L. McCarley, Multiply Charged Redox-Active
Oligomers in the Gas Phase: Electrolytic Electrospray Ionization Mass
Spectrometry of Metallocenes,
J. Phys. Chem. B, 1998, 103, 10078-10086.
T.D. McCarley, P.A.
Limbach, and R. L. McCarley, Electron-Transfer Ionization in
Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry,
Anal. Chem. 1998, 70, 4376-4379.
C.J.
DuBois and R. L.
McCarley, Characterization of Polymeric Films Derived from a-
and b-Substituted N-Vinylpyrroles,
J. Electroanal. Chem. 1998, 454, 99-105.
R. L. McCarley and
R.J. Willicut, Tethered Monolayers of Poly(N-pyrrolyl)alkanethiol) on Au,
J. Am. Chem. Soc. 1998, 120, 9296-9304.
A.C.
Henry, R.L. McCarley D.S. Poche, Sudipta Das, and C. Khan Malek, Structural Changes in
PMMA Under Hard X-ray Irradiation and the Interfacial Consequences of Enhanced
PMMA Adhesion,
Microsystem Technologies 1998, 4, 104-109.
J. S. Peanasky and R. L.
McCarley, Surface-Confined Monomers on Electrode Surfaces. 4.
Electrochemical and Spectroscopic Characterization of Undec-10-ene-1-thiol
Self-Assembled Monolayers on Au,
Langmuir 1998, 14, 113-123.
P. Moberg and R. L.
McCarley Electroless Deposition of Metals onto Organosilane Monolayers,
J. Electrochem. Soc. 1997, 144, L151-153.
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