B.A., Magna cum Laude, Rice University, 1960
Ph.D., California Institute of Technology, 1964
Department of Chemistry
Florida State University
Tallahassee, FL 32306-4390
e-mail: jsaltiel@chemmail.chem.fsu.edu
tel: (850) 644-5405
Dr. Saltiel was a recipient of an NSF Postdoctoral Fellowship at the University of California at Berkeley, an R. A. Welch Foundation Lectureship, the 1998 Florida Award from the Florida Sections of the American Chemical Society, and is an Alfred P. Sloan Foundation Fellow. He was honored for his work in Photochemistry in a Symposium at the 1998 National ACS meeting in Boston and in a special issue of the Journal of Physical Chemistry [J. Phys. Chem. A, 1998, 102, 5320-5321].
Photochemistry of organic molecules; elucidation of the mechanisms of selected photochemical reactions by chemical and spectroscopic means.
We aim to determine the role, multiplicity and geometry of key electronically excited and ground state intermediates applying both chemical and spectroscopic means. We are guided by the premise that a detailed understanding of simple photochemical reactions establishes the proper foundation for the study of more complex photochemical and photobiological systems. Our methods include quantitative measurements of product quantum yields, determination of rate constants by employing steady-state and transient emission and absorption spectroscopy, use of triplet excitation transfer to sensitize or quench triplet reaction pathways, and studies of the effects of medium and temperature on the photochemical and photophysical events. An important goal is the integration of all the information into a self-consistent kinetics model for each reaction. Much of this work depends on the use of computers.
A connecting thread that runs through much of our research is the elucidation of the various pathways that lead to the cis-trans photoisomerization of olefins. We continue to extend our well-recognized studies on stilbenes and 1,3-dienes to the diphenylpolyenes and the styrylarenes, molecules that combine properties of both systems. We have developed the method of principal component analysis with self-modeling (PCA-SM) to resolve the spectra of such systems into the separate contributions from distinct conformers. The ability to define conformer specific photochemistry and photophysics has led to several unambiguous validations of Havinga's (non-equilibrating excited rotamers) NEER principle. For instance, the pronounced excitation wavelength dependence of the cis-trans photoisomerization and photocyclization of cis-1-(2-naphthyl)-2-phenylethene (c-NPE, Scheme 1) is analogous to that in previtamin D and is quantitatively explained in terms of selective conformer excitation. This is strong evidence that recent challenges to Havinga's NEER principle explanation of vitamin D related photochemistry are incorrect.
Scheme 1
Our work on the photochemistry of derivatives in the vitamin D field, supported in part by an industrial grant (Monsanto/Pharmacia/Roche Vitamins), has uncovered hitherto unknown conformer specific photochemistry that should have a significant impact on the industrial production of the vitamin Ds.
We are applying the methods developed in our conformer work (PCA-SM and the related singular value decomposition - SM) to the resolution of spectral matrices describing the time evolution of the intermediates in the photocycles of bacteriorhodopsin (BR) and selected site-specific mutants of BR. The advantage of our approach is that it yields extremely accurate intermediate spectra and their time evolution as an initial step and relegates selection of a kinetics model for their interconversion to the final stage of the analysis. Fruitful research collaborations are in progress with research groups worldwide.
SELECTED PUBLICATIONS
Saltiel, J.; Mace, J. M.; Watkins, L. P.; Gormin, D. A.; Clark, R. J.; Dmitrenko, O. "Biindanylidenes: Role of Central Bond Torsion in Nonvertical Triplet Excitation Transfer to the Stilbenes" J. Am. Chem. Soc. Published on the Web on December 3, 2003.
Saltiel, J.; Krishnamoorthy, G.; Sears, D. F., Jr. “The Effect of Solvent Polarizability on the Fluorescence of trans-1-(2-Naphthyl)-2-phenylethene Conformers. Conformer-specific Fluorescence from the Cis Isomer” Photochem. Photobiol. Sci. 2003, 2, 1162–1168. Invited contribution; published on the Web on August 8, 2003.
Saltiel, J.; Krishnamoorthy, G.; Huang, Z; Ko, D.-H.; Wang, S. “Stereoselective O2-Induced Photoisomerization of all-trans-1,6-Diphenyl-1,3,5-hexatriene” Can. J. Chem. 2003, 81, 673-679, Invited contribution.
Saltiel, J.; Liu, R. S. H. “Special Issue Honoring George S. Hammond and Michael Kasha” J. Phys. Chem. A 2003, 107, 3147-3148.
Hochstrasser, R.; Saltiel, J. “Research Career of Michael Kasha” J. Phys. Chem. A 2003, 107, 3161-3162.
Saltiel, J.; Cires, L.; Turek, A. M. "Conformer Specific Photoconversion of 25-Hydroxytachysterol to 25-Hydroxyprevitamin D3: Role in the Production of Vitamin Ds" J. Am. Chem. Soc. 2003, 125, 2866-2867.
Aguiar, M.; Akcelrud, L.; Pinto, M. R.; Atvars, T. D. Z.; Karasz, F. E.; Saltiel, J. "Spectroscopic Evidence for Aggregation of Stilbene Derivatives in Solution" J. Photosci. 2003, 10, 149-155.
Saltiel, J.; Cires, L.; Turek, A. M. "Conformer Specific Photochemistry in the Vitamin D Field" in Handbook of Organic Photochemistry and Photobiology; 2nd Edition, Horspool, W. M. Ed.; CRC Press: London. Invited contribution; in press.
Saltiel, J.; Krishnamoorthy, G.; Huang, Z; Ko, D.-H.; Wang, S. "The Photoisomerization of all-trans-1,6-Diphenyl-1,3,5-hexatriene. Temperature and Deuterium Isotope Effects” J. Phys. Chem. A 2003, 107, 3178-3186.
del Valle, J. C.; Turek, A. M.; Tarkalanov, N. D.; Saltiel, J. “Distortion of the Fluorescence Spectrum of Anthracene with Increasing Laser Pulse Excitation Energy" J. Phys. Chem. A 2002, 106, 5101-5104.
Fedorova, O. A.: Fedorov, Y. V.; Vedernikov, A. I.; Gromov, S. P.; Yescheulova, O. V.; Alfimov, M. V.; Woerner, M.; Bossmann, S.; Braun, A.; Saltiel, J. "Thiacrown Ether Substituted Styryl Dyes: Synthesis, Complex Formation and Multiphotochromic Properties" J. Phys. Chem. A 2002, 106, 6213-6222.
Turek, A. M.; Krishnamoorthy, G.; Phipps, K.; Saltiel, J. "Resolution of Benzophenone Delayed Fluorescence and Phosphorescence with Compensation for Thermal Broadening" J. Phys. Chem. A 2002, 106, 6044-6052.
Saltiel, J. "Photochemistry Becomes More Complex: A Symposium Honoring George S. Hammond On His 80th Birthday" Inter-American Photochemical Society Newsletter 2001, 24, 5-9.
Saltiel, J.; Sears, D. F., Jr.; Turek, A. M. "UV Spectrum of the High Energy Conformers of 1,3-Butadiene in the Gas Phase" J. Phys. Chem. A 2001, 105, 7569-7578.
Catalán, J.; Saltiel, J. "On the Origin of Nonvertical Triplet Excitation Transfer. The Relative Role of Double-Bond and Phenyl-Vinyl Torsions in the Stilbenes" J. Phys. Chem. A 2001, 105, 6273-6276.
Saltiel, J.; Dmitrenko, O.; Reischl, W.; Bach, R. D. "The Triplet Potential Energy Surface of s-trans-2,4-Hexadiene. A Comparison of Theory and Experiment" J. Phys. Chem. A 2001, 105, 3934-3939.
Kulcsár, Á.; Saltiel, J.; Zimanyi, L. "Dissecting the Photocycle of the Bacteriorhodopsin E204Q Mutant from Kinetic Multichannel Difference Spectra. Extension of the Method of Singular Value Decomposition with Self-Modeling to Five Components" J. Am. Chem. Soc. 2001, 123, 3332-3340.
Saltiel, J.; Wang, S.; Watkins, L. P.; Ko, D.-H. "Direct Photoisomerization of the 1,6-Diphenyl-1,3,5-hexatrienes. Medium Effect on Triplet and Singlet Contributions" J. Phys. Chem. A, 2000, 104, 11443-11450.
Catalán, J.; Zimányi, L.; Saltiel, J. "Medium-Controlled Aggregation of trans-Stilbene" J. Am. Chem. Soc., 2000, 122, 2377-2378.
Alfimov, M. V.; Gromov, S. P.; Fedorov, Y. V.; Fedorova, O. A.; Vedernikov, A. I.; Churakov, V.; Kuz'mina, L. G.; Howard, J. A. K.; Bossman, S.; Braun, A.; Woerner, M.; Sears, Jr., D. F.; Saltiel, J. "Synthesis, Structure and Ion Selective Complexation of Trans and Cis Isomers of Photochromic Dithia-18-crown-6 Ethers" J. Am. Chem. Soc., 1999, 121, 4992-5000.
Zimányi, L.; Kulcsár, Á.; Lanyi, J.K.; Sears, Jr., D. F.; Saltiel, J. "Intermediate spectra and photocycle kinetics of the Asp96 => Asn mutant bacteriorhodopsin determined by singular value decomposition with self-modeling" Proc. Natl. Acad. Sci. USA, 1999, 96, 4414-4419.
Saltiel, J.; Zimányi, L.; Kulcsár, Á.; Lanyi, J.K.; Sears, Jr., D. F. "Singular value decomposition with self-modeling applied to determine bacteriorhodopsin intermediate spectra. Analysis of simulated data" Proc. Natl. Acad. Sci. USA, 1999, 96, 4408-4413.
Saltiel, J.; Crowder, J. M.; Wang, S. "Mapping the Potential Energy Surfaces of the 1,6-Diphenyl-1,3,5-hexatriene Ground and Triplet States" J. Am. Chem. Soc., 1999, 121, 895-902, 5352.
Saltiel, J.; "Reversible Association of Free Radicals with Benzene. The Seed of an Idea" Inter-American Photochemical Society Newsletter 1998, 21(2), 50-55; reprinted in The Spectrum, 1998, 11, 13-16.
Saltiel, J.; Wang, S.; Ko, D.-H.; Gormin, D. "Cis-Trans Photoisomerization of the 1,6-Diphenyl-1,3,5-hexatrienes in the Triplet State. The Quantum Chain Mechanism and the Structure of the Triplet State" J. Phys. Chem. 1998, 102, 5383-5392.
Saltiel, J.; Zhang, Y.; Sears, Jr. "The Temperature Dependence of the Photoisomerization of cis-1-(2-Anthryl)-2-phenylethene. Conformer-Specificity, Torsional Energetics and Mechanism" J. Am. Chem. Soc. 1997, 119, 11209-11210.
Saltiel, J.; Zhang, Y.; Sears, Jr. "Dependence of trans-1-(2-Anthryl)-2-phenylethene Conformer-Specific Fluorescence Spectra and Fumaronitrile Quenching Rate Constants on Temperature" J. Phys. Chem. 1997, 101A, 7053-7060.
Steinbock, O.; Neumann, B.; Cage, B.; Saltiel, J.; Muller, S. C.; Dalal, N. D. "A Demonstration of Principal Component Analysis for EPR Spectroscopy: Identifying Pure Component Spectra from Complex Spectra" Anal. Chem. 1997, 69, 3708-3713.
Saltiel, J.; Choi, J.-O.; Sears, Jr., D. F.; Eaker, D. W.; O'Shea, K. E.; Garcia, I. "Resolution of trans-1-(2-Naphthyl)-2-phenylethene Fluorescence in the Presence of tri-n-Butylamine into Pairs of Monomer and Exciplex Spectra. Selectivity in Conformer Quenching" J. Am. Chem. Soc. 1996, 118, 7474-7485.
Saltiel, J.; Zhang, Y.; Sears, Jr., D. F. "Highly Efficient Conformer Specific Adiabatic Cis => Trans Photoisomerization of cis-1-(2-Anthryl)-2-phenylethene in S1" J. Am. Chem. Soc. 1996, 118, 2811-2817.
Hilinski, E. F.; McGowan, W. M.; Sears, Jr., D. F.; Saltiel, J. "Evolutions of Singlet Excited State Absorption and Fluorescence of all-trans-1,6-Diphenyl-1,3,5-hexatriene in the Picosecond Time Domain" J. Phys. Chem. 1996, 100, 3308-3311.
Saltiel, J.; Dabestani, R.; Sears, Jr., D. F.; McGowan, W. M.; Hilinski, E. F. "Photocycloaddition of 9,10-Dichloroanthracene to 2,5-Dimethyl-2,4-hexadiene. The Singlet Pathway for [4+2]-Adduct Formation in Benzene" J. Am. Chem. Soc. 1995, 117, 9129-9138.
Saltiel, J.; Wang, S. "Absorption and Fluorescence Spectra of a Rigid Analogue of all-trans-1,6-Diphenyl-1,3,5-hexatriene. Solvent Controlled Order Inversion of 21Ag and 11Bu Energy Levels" J. Am. Chem. Soc. 1995, 117, 10761-10762.
Saltiel, J.; Dabestani, R.; Sears, Jr., D. F.; McGowan, W. M.; Hilinski, E. F. "Photocycloaddition of 9,10-Dichloroanthracene to 2,5-Dimethyl-2,4-hexadiene. The Singlet Pathway for [4+2]-Adduct Formation in Benzene" J. Am. Chem. Soc. 1995, 117, 9129-9138.
Saltiel, J.; Tarkalanov, N.; Sears, Jr., D. F. "Conformer Specific Adiabatic cis => trans Photoisomerization of cis-1-(2-Naphthyl)-2-phenylethene. A Striking Application of the NEER Principle" J. Am. Chem. Soc. 1995, 117, 5586-5587.
Saltiel, J.; Sears, Jr., D. F.; Ko, D.-H.; Park, K.-M. "Cis-Trans Isomerization of Alkenes" in Handbook of Organic Photochemistry and Photobiology; Horspool, W. M. and Song, P.-O., Eds.; CRC Press: London, 1995, Section 1, 3-15.
Saltiel, J.; Zhang, Y.; Sears, Jr., D. F.; Choi, J.-O. "Fluorescence, Fluorescence-Excitation and Absorption Spectra of trans-1-(2-Anthryl)-2-phenylethene Conformers" Res. Chem. Intermed. 1995, 21, 899-921.
Saltiel, J.; Choi, J.-O.; Sears, Jr., D. F.; Eaker, D. W.; Mallory, F. B.; Mallory, C. W. "Effect of Spectral Shifts on the Resolution of trans-1-(2-Naphthyl)-2-phenylethene Conformer UV Spectra Based on Principal Component Analysis with Self-Modeling" J. Phys Chem. 1994, 98, 13162-13170.
Saltiel, J.; Waller, A. S.; Sears, Jr., D. F.; Hoburg, E. A.; Zeglinski, D. M.; Waldeck, D. H. "Fluorescence Quantum Yields and Lifetimes of Substituted Stilbenes in n-Alkanes. A Reexamination of the Relationship between Solute Size and Medium Effect on Torsional Relaxation" J. Phys. Chem. 1994, 98, 10689-10698.
Saltiel, J.; Ko, D.-H.; Fleming, S. A. "Differential Medium Effects on the Trans => Cis Photoisomerization of all-trans-1,6-Diphenyl- 1,3,5-hexatriene. Competing Diradicaloid vs Zwitterionic Pathways" J. Am. Chem. Soc. 1994, 116, 4099-4100.
Saltiel, J.; Sears, Jr., D. F.; Choi, J.-O.; Sun, Y.-P.; Eaker, D. W. "The Fluorescence, Fluorescence-Excitation and UV Absorption Spectra of trans-1-(2-Naphthyl)-2-phenylethene Conformers" J. Phys. Chem. 1994, 98, 35-46.
This material is based upon work supported by the National Science Foundation under Grant Nos. CHE 9612316, 9985895 and 0314784. Any opinions, findings and conclusions or recomendations expressed in this material are those of the author and do not necessarily reflect the views of the National Science Foundation (NSF).