JudithAnn R. Hartman
Ph.D., Harvard University
U.S. Naval Academy
572M Holloway Road
Annapolis, MD 21402-5026
My current research interests span both inorganic and analytical chemistry. Inorganic projects involve synthesizing new ligands that place transition metals in unusual electronic environments; and in studying the resulting complexes with techniques such as x-ray crystallography, epr, electrochemistry, and magnetic measurements. My analytical chemistry projects involve applying analytical chemistry techniques to current problems in fire science in collaboration with Dr. Craig Beyler at Hughes Associates, Baltimore,MD.
In the 1980's, metals were constrained into forming complexes with weak functional groups (such as thioethers) or into complexes with unusual geometries by the use of crown or cryptand ligands. Unfortunately, these highly constrained ligands are often difficult or tedious to prepare. It has now been shown that "crown-like" behavior can be observed with "open" ligands such as podants (branched ligands such as tripods) and even with linear polymers such as polyethylethers. Our previous work with copper and nickel complexes of polydentate aminopyridine ligands containing linked chelating rings has supported with Hancock’s conclusions that many of the unusual properties found in the macrocyclic complexes are actually due to the linked chelate rings and not to the macrocycle structure1-4. The DIPNEN-pyr ligand (1,14-bis(2-pyridyl)-2,6,9,13-tetraazatetradecane) in particular was found to form very stable Cu(II) and Ni(III) complexes, presumably due to it’s ability to span the tetragonally elongated octahedral geometry needed for these Jahn-Teller ions3,4. We are extending this work by synthesizing the thiophene analogue of DIPNEN-pyr as well as other amino-thiophene ligands with linked chelating rings in order to explore the binding characteristics of the thiophene group with first row transition metals.
The objective of this research is to develop methods and scientific bases for the use of smoke deposition analysis as a forensic tool. This objective will be pursued through a program of experimental and analytical work beginning with small scale testing and progressing through full scale testing over a period of two years. Specifically, there are three component objectives to the project:
- Develop a scientific understanding of the physics and chemistry of smoke deposition.
- Develop practical methods for documenting smoke deposition patterns and collecting smoke deposition samples
- Develop practical analytical chemistry methods for smoke deposition samples that can be carried out in forensic chemical analysis laboratories.
The soot samples will be generated in apparatus built and used in Hughes Associates’ laboratory and the chemical characteristics of the deposits will be determined at the Naval Academy using methods and equipment currently available in forensic laboratories. These methods include sample extraction methods for soluble fraction as well as analysis via TGA, DSC, GS-MS, MALDI, IR, Raman, and various microscopy methods.
Note: midshipman co-authors are underlined.
1. Estimation of kinetic parameters by TGA and DSC for the self heating of virgin plywood and plywood subjected to prolonged heating. J.H. Swann, J.R. Hartman, C.L. Beyler. Submitted to Tenth Symposium of the International Association of Fire Safety Science, 2008.
2. An evaluation of the self-heating hazards of cerium (IV) nitrated treated towels using differential scanning calorimetry and thermogravimetric analysis. J.R. Hartman, C.A. Waters, C.L. Beyler, Fire and materials, 2007, 31, 359-371.
3. Ignition Studies of Cerium Nitrate Treated Towels. C.L. Beyler, T. Fay, M. Gratkowski, B. Campbell, and J.R. Hartman, Fire and materials, 2006, 30, 223-240.
4. A comparison of the gas, solution, and solid state coordination environments for the Cu(II) complexes of a series of linear aminopyridine ligands with varying ratios of 5- and 6-membered chelate rings. J.R. Hartman, A.L. Kammier, Robert J. Spracklin, Wayne H. Pearson, M.Y. Combariza, and R.W. Vachet, Inorg. Chim. Acta, 2004, 357, 1141-1151.
5. A comparison of the gas, solution, and solid state coordination environments for the Ni(II) complexes of a series of linear penta- and hexadentate aminopyridine ligands with accessible Ni(III) oxidation states. J.R. Hartman, M.Y. Combariza, and R.W. Vachet, Inorg. Chim.Acta, 2004, 357, 51-58.
6. A Comparison of the Gas, Solution, and SolidState Coordination Environments for the Copper(II) Complexes of a Series of Aminopyridine Ligands of Varying Coordination Number. J.R. Hartman, R.W. Vachet, W. Pearson, R. Jeremy Wheat, and J.H. Callahan, Inorg. Chim.Acta, 2003, 343, 119-132.
7. Elucidation of Metal Complex Coordination Structure Using Collision-Induced Dissociation and Ion-Molecule Reactions in a Quadrupole Ion Trap Mass Spectrometer. R.W. Vachet, J. R. Hartman, J.W. Gertner, J.H. Callahan, Int. J. of Mass. Spec., 2001, 204, 101-112.
8. Gas, Solution, and SolidState Coordination Environments for the Nickel(II) Complexes of a Series of Aminopyridine Ligands of Varying Coordination Number. J.R. Hartman, R.W. Vachet, and J.H. Callahan, Inorg. Chem. Acta, 2000, 297(1-2), 79-87.
9. Ion-Molecule Reactions in a Quadrupole Ion Trap as a Probe of the Gas-Phase Structure of Metal Complexes. R.W. Vachet, J.R. Hartman, and J.H. Callahan, Journal of Mass Spectrometry, 33 (1998) 1209-25.