Center for Intelligent Chemical
Instrumentation (CICI)
Department of Chemistry, Clippinger Laboratories, Ohio
University, Athens, OH 45701-2979
April 28, 2008
Analytical
chemistry is a discipline that has realized great benefits from the growth in
power and availability of laboratory computers. The decade of the 1980's
produced a generation of general-purpose laboratory microcomputers that could
be used routinely for the control of chemical instrumentation and the analysis
of data arising from chemical measurements. The combination of computational
and control capabilities offered by these computer systems has made possible
the development of a variety of automated analytical instruments for use in
dedicated monitoring scenarios such as patient monitoring in hospitals, process
monitoring and control in the chemical industry, and environmental monitoring.
For the
1990's and beyond, the focus of research in combining computational and instrumental
methods is turning to the development of "intelligent" chemical
instrumentation. The term, "intelligent instrument", refers to a new
generation of analytical instrument with advanced capabilities for data
interpretation, self-optimization, and decision-making. Building upon these
concepts, researchers at CICI are conducting basic research in the development
of new methods and instrumentation for a variety of chemical analyses. Work is
currently underway in each of the areas of electrochemistry, spectroscopy, and
chromatography.
CICI presently
has a core working group in forensic analysis specializing in mass and ion
mobility spectrometry. CICI members
administer a wide range of instruments including an isotope ratio mass
spectrometer and several different ion trap mass analyzers. Coupled with chemometrics techniques, standard
methods such as gas chromatography/mass spectrometry can reach new levels of
discrimination ability.
Hao
Chen, Assistant Professor of Chemistry & Biochemistry
*Fundamental study
of gas-phase ion chemistry
*Novel application to bioanalytical
chemistry using ambient mass spectrometry
*Ambient ion thermal dissociation in
proteomics
*Protein footprinting
using fast photolytic oxidation of protein (FPOP) method with various oxidants
Peter de B.
Harrington,
Professor of Chemistry & Biochemistry
* Intelligent chemical instrument design
* Biological and forensic analysis using ion and differential mobility
spectrometries
* New methods for chromatographic fingerprinting
* Forensic and biomaterial characterization by mass spectrometry
Glen
P. Jackson, Assistant Professor of Chemistry & Biochemistry
* Fast GC-ECD and Fast GC-MS of explosives
* Fast tandem mass spectrometry using custom-programmed ion traps
* LC-MS of ceramides, cholesterols, and fatty acids
* Mass spectrometry instrumentation and novel approaches to tandem mass
spectrometry
* Isotope ratio mass spectrometry
CICI offers
a unique environment for students who are interested in working with
instrumentation, computers, and software. There is a large demand for
doctoral students with expertise in chemometrics. Chemometrics is
emphasized throughout the OU analytical chemistry curriculum. Chemometrics
includes the topics of systematic design and statistical interpretation of
experiments, signal processing, calibration, modeling, and machine
intelligence. A burgeoning area of research is adapting chemometric
methods to be used in bioinformatic applications of proteomic and genomic
experiments.
Prospective
graduate students interested in forensic science should consider exploring
graduate work in analytical or bioanalytical chemistry with a forensic emphasis
at Ohio University. You will have the advantage of receiving financial
aid in the form of teaching or research assistantships and a full tuition
waiver. Most graduate programs in forensic science do not have assistantships
and are not research based degrees. Our program provides the strong scientific
and research background lab directors are looking for.
As you work
towards a PhD, you can take classes in forensic chemistry, DNA typing, and
toxicology as well as taking traditional graduate coursework in analytical
chemistry, biochemistry, and chemometrics. In addition, you will work
closely with a member of our faculty performing research in one of several
areas in forensic science including remote sensing, DNA typing, toxicology,
explosives analysis, and hazardous materials detection. Researchers in our
department have received major funding for forensic based projects from the
National Institute of Justice, the US Army, and various counter-terrorism
agencies.
CICI and
Homeland Security
The Ohio
University Center for Intelligent Chemical Instrumentation has a history of
research related to Homeland Security that spans a decade. The US Army
has sponsored Prof. Harrington’s research which was focused on chemical weapons
detection. Prof. Harrington’s group has worked on real-time modeling and
compression methods of ion mobility spectrometry (IMS) data. He is
currently funded by the Army for wavelet compression of IMS spectra acquire
from an unmanned aerial vehicle (UAV) that is used for remote detection of chemical
weapons. Prof. Harrington has worked on biological weapons
detection and developed advanced algorithms for pattern recognition of microbes
with mass spectrometry (MS). He presently has a microbiology lab with a BioSafety Level 2 capability for analysis of microbes by
IMS and MS. Prof. Peter Harrington is also working with detection of
food-borne pathogens and there is concern of a biological attack on the
national food supply using pathogenic organisms. Prof. Peter Harrington is a
pioneer in the area of real-time chemometric modeling of sensor data.
Prof. Glen Jackson’s
group is working on rapid methods of explosives detection with fast-GC/fast-MS. He also is developing low cost miniaturized mass
spectrometers using novel ion filters. Prof.
Hao Chen is developing new methods for selectively sampling drugs and
explosives for mass spectrometric detection.
Intelligent
instrumentation is of paramount importance for Homeland Security because
analytical instrumentation that is field employed cannot require operators with
sophisticated knowledge in analytical chemistry. Some sensors may not
have an operator, but may be stand alone monitors or propelled in robotic
vehicles (e.g., the IMS detector in the UAV). These smart instruments
must encode analytical knowledge so that they display an alarm or perform a
required action when a target analyte is detected. Consider IMS that is
used in virtually every US airport for detecting explosive residues on
hand-luggage and has been recently been installed in the Pentagon. The
IMS instruments have a green light that illuminates if no explosives are
detected and a red light for detection. Therefore, the algorithms
embedded in the instrument must make the accurate decision that a spectroscopic
signature attributed to an explosive occurs amidst a large range of potential
interfering compounds.
Selected Publication
List of CICI Members Related to Forensic/Analytical Chemistry
Chen
Chen, H.; Eberlin,
L.S.; Cooks, R.G. Neutral Fragment Mass
Spectra via Ambient Thermal Dissociation of Peptide/Protein Ions. J. Am.
Chem. Soc. 2007, 129, 5880-5886.
Chen, H.; Ouyang,
Z.; Cooks, R.G. Thermal Production and Reactions of Organic Ions at Atmospheric
Pressure. Angew. Chem. Int. Ed., 2006,
3656-3660.
Cooks, R.G.; Chen, H.; Eberlin, M.N.; Zheng, X.; Tao, W.A. Polar Acetalization and Transacetalization
in the Gas Phase: The Eberlin Reaction. Chem. Rev. 2006, 106, 188-211.
Chen, H.; Cotte-Rodriguez,
I.; Cooks, R.G. cis-Diol Functional Group Recognition
by Reactive Desorption Electrospray Ionization. Chem. Commun. 2006,
597-599.
Chen, H.; Justes,
D.R.; Cooks, R.G. Proton Affinities of N-Heterocyclic Carbene
Super Bases. Org. Lett. 2005, 7, 3949-3952.
Harrington
Chen, P.; Harrington, P. B.
Discriminant analysis of fused positive and negative ion mobility spectra using
multivariate self-modeling mixture analysis and neural networks. Applied Spectroscopy 2008, 62, 133-141.
Chen, P.; Lu, Y.; Harrington, P.
B. Biomarker profiling and reproducibility study of MALDI-MS measurements of
Escherichia coli by analysis of variance-principal component analysis. Analytical
Chemistry 2008, 80, 1474-1481.
O'Donnell, R. M.; Sun, X. B.; Harrington, P. D.
Pharmaceutical applications of ion mobility spectrometry. Trac-Trends in
Analytical Chemistry 2008, 27, 44-53.
Lu, Y.; Harrington, P. B. Forensic application of gas
chromatography - Differential mobility spectrometry with two-way classification
of ignitable liquids from fire debris. Analytical
Chemistry 2007, 79, 6752-6759.
Rearden, P.; Harrington, P. B.;
Karnes, J. J.; Bunker, C. E. Fuzzy rule-building expert system classification
of fuel using solid-phase microextraction two-way gas chromatography
differential mobility spectrometric data. Analytical Chemistry 2007,
79, 1485-1491.
Zhang, Z. Y.; Wang, Y. M.; Fan, G. Q.; Harrington, P. D. B. A comparative study of multilayer
perceptron neural networks for the identification of rhubarb samples. Phytochemical Analysis 2007, 18,
109-114.
P.B. Harrington; Laurent, C.;
Levinson, D. F.; Markey, P. L. S. P. Bootstrap Classification and Point-Based
Feature Selection from Age-Staged Mouse Cerebellum Tissues of Matrix Assisted
Laser Desorption/Ionization Mass Spectra using a Fuzzy Rule-Building Expert
System. Analytica Chimica Acta 2007, 599, 219-231.
Rearden, P.; Harrington, P. B. Detection
of VOCs Using Gas Chromatography-Differential Mobility Spectrometry (GC-DMS). LabPlus International
2006, 20(1), 20-24.
Bota, G. M.; Harrington, P .B. Direct Detection of
Trimethylamine in Meat Food Products Using Ion Mobility Spectrometry. Talanta 2006, 68(3), 629-635.
Fox, R. V.; Ball, R. D.;
Harrington, P. B.; Rollins, H. W.; Wai, C. M. Holmium Nitrate Complexation with Tri-n-butyl
Phosphate in Supercritical Carbon Dioxide.
Journal of Supercritical Fluids
2005, 36(2), 137-144.
Zhang, Z. Y.; Chen, G.;
Harrington, P. B. Detection of Trace Organic
Compounds by Using Ion Mobility Spectrometry and SIMPLISMA. Spectroscopy
and Spectral Analysis 2005, 25(9), 1530-1533.
Laurent, C.; Levinson, D. F.;
Schwartz, S. A.; Harrington, P. B.;
Markey, S. P.; Caprioli, R. M.; Levitt,
P. Direct Profiling of the Cerebellum by
MALDI MS: A Methodological Study in Postnatal and Adult Mouse. Journal
of Neuroscience Research 2005, 81(5), 613-621.
Zhang, Z.; Harrington, P. B. Recent
Studies on Artificial Neural Networks and Their Application. Current
Topics in Analytical Chemistry 2005,
5,
24-41.
Ochoa, M.L.; Harrington, P. B. Immunomagnetic
Isolation of Enterohemorrhagic Escherichia
coli O157:H7 from Ground Beef and Identification by Matrix-Assisted Laser
Desorption/Ionization Time-of-Flight Mass Spectrometry and Database
Searches. Analytical Chemistry 2005,
77, 5258-5267.
Rainsberg, M. R.; Harrington,
P. B. Thermal
Desorption Solid-Phase Microextraction Inlet for Differential Mobility
Spectrometry. Applied Spectroscopy 2005, 59, 754-762.
Rearden, P.; Harrington, P. B. Rapid
Screening of Precursor and Degradation Products of Chemical Warfare Agents in
Soil by Solid-Phase Microextraction Ion Mobility Spectrometry (SPME-IMS). Analytica
Chimica Acta 2005, 545, 13-20.
Harrington, P. B.; Vieira, N. E.;
Espinoza, J.; Nien, J. K.; Romero, R.; Yergey, A. L. Analysis of Variance-Principal Component
Analysis: A Soft Tool for Proteomic
Discovery. Analytica Chimica Acta 2005,
544, 118-127.
Cao, L.; Harrington, P. B.;
Liu, J. SIMPLISMA and ALS Applied to Two-dimensional
Nonlinear Wavelet Compressed Ion Mobility Spectra of Chemical Warfare Agent Simulants. Analytical Chemistry 2005, 77(8), 2575-2586.
Ochoa, M. L.; Harrington, P .B. Chemometric Studies
for the Characterization and Differentiation of Microorganisms Using in Situ
Derivatization and Thermal Desorption Ion Mobility Spectrometry. Analytical
Chemistry 2005, 77, 854-863.
Cui, X. J.; Zhang, Z. Y.;
Harrington, P. B.; Ren, Y. L. Quality control of the powder pharmaceutical
samples of metronidazole based on near infrared
reflectance spectra with temperature-constrained cascade correlation neural
networks. Chemical Journal of Chinese Universities 2004, 25(7), 1251-1253.
Cui, X. J.; Zhang, Z. Y.; Ren,
Y. L.; Harrington, P. B. Quality control of the powder pharmaceutical
samples of sulfaguanidine by using NIR reflectance spectrometry and
temperature-constrained cascade correlation networks. Talanta
2004, 64(4), 943-948.
Fox, R. V.; Ball, R. D.;
Harrington, P. B.; Rollins, H. W.; Jolley, J. J.; Wai, C. M. Praseodymium Nitrate and Neodymium Nitrate Complexation with
Organophosphorus Reagents in Supercritical Carbon Dioxide Solvent. Journal
of Supercritical Fluids 2004, 31, 273-286.
Zhang, Z.; Wang, D.;
Harrington, P. B.; Voorhees, K. J.; Rees, J.
Forward Selection Radial Basis Function Networks Applied to Bacterial
Classification Based on MALDI-TOF-MS. Talanta 2004, 63, 527-532.
Cao, L.; Harrington, P. B. Two-dimensional
Nonlinear Wavelet Compression (NLWC) of Ion Mobility Spectra of Chemical
Warfare Agent Simulants. Analytical Chemistry 2004, 76, 2859-2868.
Ochoa, M.; Harrington, P. B. Detection
of Methamphetamine in the Presence of Nicotine Using In Situ Chemical
Derivatization and Ion Mobility Spectrometry. Analytical
Chemistry 2004, 76, 985-991.
Cao, L.; Harrington, P. B.;
Harden, C. S.; McHugh, V. M.; Thomas, M. A.
Nonlinear Wavelet Compression of Ion Mobility Spectra from Ion Mobility
Spectrometers Mounted in an Unmanned Aerial Vehicle. Analytical
Chemistry 2004, 76,
1069-1077.
Jackson
Jackson, G. P.; Hyland, J. J.;
Laskay, U. A. Energetics and efficiencies of
collision-induced dissociation achieved during the mass acquisition scan in a
quadrupole ion trap. Rapid Communications in Mass Spectrometry 2005,
19, 3555-3563.
Collin, O. L.; Niegel,
C.; DeRhodes, K. E.; McCord, B. R.; Jackson, G. P. Fast gas chromatography of
explosive compounds using a pulsed-discharge electron capture detector. Journal
of Forensic Sciences 2006, 51, 815-818.
Collin, O. L.; Beier, M.; Jackson,
G. P. Dynamic collision-induced dissociation of peptides in a quadrupole ion
trap mass spectrometer. Analytical Chemistry 2007,
79, 5468-5473.
Laskay, Ü. A.; Hyland, J. J.;
Jackson, G. P. Dynamic collision-induced dissociation (DCID) in a quadrupole
ion trap using a two-frequency excitation waveform: I. Effects of excitation
frequency and phase angle. Journal of the American Society for Mass
Spectrometry 2007, 18, 749-761.
Laskay, Ü. A.; Collin, O. L.;
Hyland, J. J.; Nichol, B.; Jackson, G. P.; Pasilis,
S. P.; Duckworth, D. C. Dynamic Collision-Induced Dissociation (DCID) in a
quadrupole ion trap using a two-frequency excitation waveform: II. Effects of frequency spacing and scan rate. Journal of
the American Society for Mass Spectrometry 2007, 18,
2017-2025.