研究领域

Organic Chemistry

The Toscano group’s main interests have focused on the application of nanosecond time-resolved infrared (TRIR) spectroscopy to the study of organic reactive intermediates and the development of novel photochemical precursors to nitric oxide (NO). More recently, our research activities have turned to study of the fundamental chemistry and biochemistry of nitroxyl (HNO). This one-electron reduced and protonated congener of NO has recently received significant attention, especially as a potential alternative to current treatments of cardiac failure.

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"Curtailing the Hydroxylaminobarbituric Acid - Hydantoin Rearrangement to Favor HNO Generation" Guthrie, D. A.; Nourian, S.; Takahashi, C. G.; Toscano, J. P. J. Org. Chem. 2014, submitted. "The "Catch-and-Release" of HNO with Pyrazolones" Guthrie, D. A.; Ho, A.; Takahashi, C. G.; Collins, A.; Morris, M.; Toscano, J. P. J. Org. Chem. 2014, submitted. "Comparison of HNO reactivity with tryptophan and cysteine in small peptides" Keceli, G.; Moore, C. D.; Toscano, J. P. Bioorg. Med. Chem. Lett. 2014, 24, 3710-3713. "Reactivity of C-terminal cysteines with HNO" Keceli, G.; Toscano, J. P. Biochemistry 2014, 53, 3689-3698. "Post-study caffeine administration enhances memory consolidation in humans" Borota, D.; Murray, E.; Keceli, G.; Chang, A.; Watabe, J. M.; Ly, M.; Toscano, J. P.; Yassa, M. A. Nat. Neurosci. 2014, 17, 201-203. "NMR detection and study of hydrolysis of HNO-derived sulfinamides" Keceli, G.; Moore, C. D.; Labonte, J. W.; Toscano, J. P. Biochemistry 2013, 52, 7387-7396. "HNO enhances SERCA2a activity and cardiomyocyte function by promoting redox-dependent phospholamban oligomerization" Sivakumaran, V.; Stanley, B. A.; Tocchetti, C. G.; Ballin, J. D.; Caceres, V.; Zhou, L.; Keceli, G.; Rainer, P. P.; Lee, D. I.; Huke, S.; Ziolo, M. T.; Kranias, E. G.; Toscano, J. P.; Wilson, G. M.; O'Rourke, B.; Kass, D. A.; Mahaney, J. E.; Paolocci, N. Antioxid. Redox Signal. 2013, 19, 1185-1197. Invited Article for a special issue of Journal of Inorganic Biochemistry on the Bioinorganic Chemistry of HNO: "Oxidation of N-hydroxy-L-arginine by Hypochlorous Acid to Form Nitroxyl (HNO)" Cline, M. R.; Chavez, T.A.; Toscano, J. P. J. Inorg. Biochem. 2013, 118, 148-154. Invited Article for a special issue of Physical Chemistry Chemical Physics on New Insights Into Organic Chemistry from Forefront Physical Measurements: "Nanosecond Time-Resolved IR Study of Thiobenzoylnitrene" Liu, Y.; Evans, A. S.; Toscano, J. P. Phys. Chem. Chem. Phys. 2012, 14, 10438-10444. "Reactivity of Nitroxyl-Derived Sulfinamides" Keceli, G.; Toscano, J. P. Biochemistry 2012, 51, 4206-4216. "Development of N-Substituted Hydroxylamines as Efficient Nitroxyl (HNO) Donors" Guthrie, D. A.; Kim, N. Y.; Siegler, M. A.; Moore, C. D.; Toscano, J. P. J. Am. Chem. Soc. 2012, 134, 1962-1965. "Optimization of HNO Production from N,O-bis-Acylated Hydroxylamine Derivatives" Sutton, A. D.; Williamson, M.; Weismiller, H.; Toscano, J. P. Org. Lett. 2012, 14, 472-475. "The Chemistry of NO- and HNO-Producing Diazeniumdiolates" Evans, A. S.; Toscano, J. P. in The Chemistry of Hydroxylamines, Oximes, and Hydroxamic Acids, Vol. 2; Rappoport, Z.; Liebman, J. F., Eds.; John Wiley & Sons, 2011, 917-932. "Detection of Nitroxyl (HNO) by a Prefluorescent Probe" Cline, M. R.; Toscano, J. P. J. Phys. Org. Chem. 2011, 24, 993-998. "Detection of Nitroxyl (HNO) by Membrane Inlet Mass Spectrometry" Cline, M. R.; Tu, C.; Silverman, D. N.; Toscano, J. P. Free Rad. Biol. Med., 2011, 50, 1274-1279. "Weinreb Amides in Carbene Chemistry: A Time-Resolved IR Investigation into a Potential Intramolecular Stabilization Mechanism" Evans, A. S.; Sundaram, G. S. M.; Sabmannshausen, J.; Toscano, J. P.; Tippmann, E. M. Org. Lett., 2010, 12, 4616-4619. "Photogeneration and Reactivity of Acyl Nitroso Compounds" Evans, A. S.; Cohen, A. D.; Gurard-Levin, Z. A.; Kebede, N.; Celius, T. C.; Miceli, A. P.; Toscano, J. P. Can. J. Chem. 2010, 89, 130-138. "Phospholamban Thiols Play a Central Role in Activation of the Cardiac Muscle Sarcoplasmic Reticulum Calcium Pump by Nitroxyl" Froehlich, J. P.; Mahaney, J. E.; Keceli, G.; Pavlos, C. M.; Goldstein, R.; Redwood, A. J.; Sumbilla, C.; Lee, D. I.; Tocchetti, C. G.; Kass, D. A.; Paolocci, N.; Toscano, J. P. Biochemistry 2008, 47, 13150-13152. "2-Hydroxy-5-nitrobenzyl as a Diazeniumdiolate Protecting Group: Application in NO-Releasing Polymers with Enhanced Biocompatibility" Xu, H.; Reynolds, M. M.; Cook, K. E.; Evans, A. S.; Toscano, J. P. Org. Lett. 2008, 10, 4593-4596. "Photochemistry of N-Acetyl-, N-Trifluoroacetyl-, N-Mesyl-, and N-Tosyldibenzothiophene Sulfilimines" Desikan, V.; Liu, Y.; Toscano, J. P.; Jenks, W. S. J. Org. Chem. 2008, 73, 4398-4414. "Photochemistry of Sulfilimine-Based Nitrene Precursors: Generation of Both Singlet and Triplet Benzoylnitrene" Desikan, V.; Liu, Y.; Toscano, J. P.; Jenks, W. S. J. Org. Chem. 2007, 72, 6848-6859. "Time-Resolved Infrared (TRIR) Studies of Organic Reactive Intermediates" Toscano, J. P. in Reviews of Reactive Intermediate Chemistry; Platz, M. S.; Moss, R. A.; Jones, M., Jr., Eds.; John Wiley & Sons, 2007. "Nitroxyl Improves Cellular Heart function by Directly Enhancing Cardiac Sarcoplasmic Reticulum Ca2+ Cycling" Tocchetti, C. G.; Wang, W.; Froehlich, J. P.; Huke, S.; Aon, M. A.; Wilson, G. M.; Di Benedetto, G.; O’Rourke, B.; Gao, W. D.; Wink, D. A.; Toscano, J. P.; Zaccolo, M.; Bers, D. M.; Valdivia, H. H.; Cheng, H.; Kass, D. A.; Paolocci, N. Circ. Res. 2007, 100, 96-104. "Generation of Oxynitrenes and Confirmation of Their Triplet Ground States" Wasylenko, W. A.; Kebede, N.; Showalter, B. M.; Matsunaga, N.; Miceli, A. P.; Liu, Y.; Ryzhkov, L. R.; Hadad, C. M.; Toscano, J. P. J. Am. Chem. Soc. 2006, 128, 13142-13150. "8-Bromo-7-hydroxyquinoline as a Photoremovable Protecting Group for Physiological Use: Mechanism and Scope" Zhu, Y.; Pavlos, C. M.; Toscano, J. P.; Dore, T. M. J. Am. Chem. Soc. 2006, 128, 4267-4276. "Crystal Lattice Effects on the Orientation and Orbital Degeneracy of Nitric Oxide Trapped in Nitramine Single Crystals" Ryzhkov, L. R.; Toscano, J. P. Cryst. Growth Des. 2005, 5, 2066-2072. "Donors of HNO" Miranda, K. M.; Nagasawa, H. T.; Toscano, J. P. Current Topics Med. Chem. 2005, 5, 649-664. "Photosensitive Precursors to Nitric Oxide" Pavlos, C. M.; Xu, H.; Toscano, J. P. Current Topics Med. Chem. 2005, 5, 637-647. "The Mechanism of Photoinduced Acylation of Amines by N-Acyl-5,7-dinitroindoline as Determined by TRIR Spectrosopy" Cohen, A. D.; Helgen, C.; Bochet, C. G.; Toscano, J. P. Org. Lett. 2005, 7, 2845-2848. "Caged Nitric Oxide" Pavlos, C. M.; Xu, H.; Toscano, J. P. in Phototriggers, Photoswitches, and Caged Compounds, Dynamic Studies in Biology; Goelder, M; Givens, R. S., Eds.; Wiley-VCH: Weinheim, 2005. "Photoinduced Carbon Monoxide Migration in a Synthetic Heme-Copper Complex" Fry, H. C.; Cohen, A. D.; Toscano, J. P.; Meyer, G. J.; Karlin, K. D. J. Am. Chem. Soc. 2005, 127, 6225-6230. "The Triplet State of a Platinum Acetylide Chromophore Examined by Time-Resolved IR Spectroscopy and Density Functional Theory" Cooper, T. M.; Blaudeau, J.-P.; Hall, B. C.; Rogers, J. E.; McLean, D. G.; Liu, Y.; Toscano, J. P. Chem. Phys. Lett. 2004, 400, 239-244. "Controlled Photochemical Release of Nitric Oxide from Diazeniumdiolates" Pavlos, C. M.; Xu, H.; Toscano, J. P. Free Radical Biol. Med., 2004, 37, 745-752. "Time-Resolved IR Studies of α-Lactones" Showalter, B. M.; Toscano, J. P. J. Phys. Org. Chem. 2004, 17, 743-748. "Time-Resolved IR Detection and Study of an Iminooxirane Intermediate" Cohen, A. D.; Showalter, B. M.; Toscano, J. P. Org. Lett. 2004, 6, 401-403. "Photochemistry of 1-(N,N-Diethylamino)diazen-1-ium-1,2-diolate: An Experimental and Computational Investigation" Pavlos, C. M.; Cohen, A. D.; D'Sa, R. A.; Sunoj, R. B.; Wasylenko, W. A.; Kapur, P.; Relyea, H. A.; Kumar, N. A.; Hadad, C. M.; Toscano, J. P. J. Am. Chem. Soc. 2003, 125, 14934-14940. "The Photochemistry of Diazirines" Celius, T. C.; Toscano, J. P. In CRC Handbook of Organic Photochemistry and Photobiology, 2nd Edition; Horspool, W.; Lenci, F., Eds.; CRC Press: Boca Raton, FL, 2003, 92-1 – 92-10. "Photochemical Reactivity of α-Diazocarbonyl Compounds" Celius, T. C.; Wang, Y.; Toscano, J. P. In CRC Handbook of Organic Photochemistry and Photobiology, 2nd Edition; Horspool, W.; Lenci, F., Eds.; CRC Press: Boca Raton, FL, 2003, 90-1 – 90-16. "Time-Resolved IR Studies of Cyclic Enone Triplet Excited States and their Reactions with Alkenes" Cohen, A. D.; Showalter, B. M.; Brady, D. A.; Kenesky, C. A.; Toscano, J. P. Phys. Chem. Chem. Phys. 2003, 5, 1059-1063. "Matrix Isolation, Time-Resolved IR, and Computational Study of the Photochemistry of Benzoyl Azide" Pritchina, E. A.; Gritsan, N. P.; Maltsev, A.; Bally, T.; Autrey, T.; Liu, Y.; Wang, Y.; Toscano, J. P. Phys. Chem. Chem. Phys. 2003, 5, 1010-1018. "Direct Observation of an Acyl Nitroso Species in Solution by Time-Resolved IR Spectroscopy" Cohen, A. D.; Zeng, B.-B.; King, S. B.; Toscano, J. P. J. Am. Chem. Soc. 2003, 125, 1444-1445. "Energetics of Aqueous Oxyanions of Nonmetals and Metalloids" Toscano, J. P.; Deakyne, C. A.; Liebman, J. F. Struct. Chem. 2003, 14, 315-320. "Preparation and Reactivity of O2-Sulfonated Diazeniumdiolates" D’Sa, R. A.; Wang, Y.; Ruane, P. H.; Showalter, B. M.; Saavedra, J. E.; Davies, K. M.; Citro, M. L.; Booth, M. N.; Keefer, L. K.; Toscano, J. P. J. Org. Chem. 2003, 68, 656-657. "The Energetics of Nitric Oxide Generation Upon Protonation of Diazeniumdiolates" Hammad, L. A.; Ruane, P. H.; Kumar, N. A.; Toscano, J. P.; Wenthold, P. G Int. J. Mass. Spec., 2003, 222, 269-279. "The Fragmentation of Alkoxychlorocarbenes in Hydrocarbon Solvents and in Low-Temperature Argon Matrices" Moss, R. A.; Ma, Y.; Zeng, F.; Sauers, R.; Bally, T.; Maltsev, A.; Toscano, J. P.; Showalter, B. M. J. Phys. Chem. A 2002, 106, 12280-12291. "Controlled Photochemical Release of Nitric Oxide from O2-Naphthylmethyl- and O2-Naphthylallyl-Substituted Diazeniumdiolates" Bushan, K. M.; Xu, H.; Ruane, P. H.; D’Sa, R. A.; Pavlos, C. M.; Smith, J. A.; Celius, T. C.; Toscano, J. P. J. Am. Chem. Soc., 2002, 124, 12640-12641. "Controlled Photochemical Release of Nitric Oxide from O2-Benzyl Substituted Diazeniumdiolates" Ruane, P. H.; Bushan, K. M.; Pavlos, C. M.; D’Sa, R. A.; Toscano, J. P. J. Am. Chem. Soc. 2002, 124, 9806-9811. "Computational and Experimental Studies of the Effect of Substituents on the Singlet- Triplet Energy Gap in Phenyl(carbomethoxy)carbene" Geise, C. M.; Wang, Y.; Mykhaylova, O.; Frink, B. T.; Toscano, J. P.; Hadad, C. M. J. Org. Chem. 2002, 67, 3079-3088. "Bridgehead Carbocations via Carbene Fragmentation: Erasing a 1010 Kinetic Preference" Moss, R. A.; Zheng, F.; Fede, J.-M.; Ma, Y.; Sauers, R. R.; Toscano, J. P.; Showalter, B. M. J. Am. Chem. Soc. 2002, 124, 5258-5259. "Solvent Dependence of the 2-Napthyl(carbomethoxy)carbene Singlet-Triplet Energy Gap" Wang, Y.; Hadad, C. M.; Toscano, J. P. J. Am. Chem. Soc. 2002, 124, 1761-1767. "Reversible Carbon Monoxide Photodissociation from Cu(I) Coordination Compounds" Scaltrito, D. V.; Fry, H. C.; Showalter, B. M.; Thompson, D. W.; Liang, H.-C.; Zhang, C. X.; Kim, E.; Toscano, J. P.; Karlin, K. D.; Meyer, G. J. Inorg. Chem. 2001, 40, 4514-4515. "The 2-Norbornyl Cation via the Fragmentation of exo- and endo-2-Norbornyloxychloro-carbenes: Distinction Without Much Difference" Moss, R. A.; Zheng, F.; Sauers, R. R.; Toscano, J. P. J. Am. Chem. Soc. 2001, 123, 8109-8116. "Identification of a Vibrational Frequency Corresponding to H-Atom Translocation in Hypericin" Showalter, B. M.; Datta, A.; Chowdury, P. K.; Park, J.; Bandyopadhyay, P.; Kesavan, S.; Zeng, Y.; Kraus, G. A.; Gordon, M. S.; Toscano, J. P.; Petrich, J. W. Photochem. Photobiol. 2001, 74, 157-163. Invited Review: "Structure and Reactivity of Organic Intermediates as Revealed by Time-Resolved IR Spectroscopy" Toscano, J. P. in Advances in Photochemistry, Neckers, D. C; von Bünau, G.; Jenks, W. S., Eds., John Wiley & Sons, New York, 2001, Vol. 26, pp. 41-91. "Chemistry of the Diazeniumdiolates. 3. Photoreactivity" Srinivasan, A.; Kebede, N.; Saavedra, J. E.; Nikolaitchik, A. V.; Brady, D. A.; Yourd, E.; Davies, K. M.; Keefer, L. K.; Toscano, J. P. J. Am. Chem. Soc. 2001, 123, 5465-5472. "New Kinetics Methodologies Applied To Carbene Fragmentation Reactions" Moss, R. A.; Johnson, L. A.; Yan, S.; Toscano, J. P.; Showalter, B. M. J. Am. Chem. Soc. 2000, 122, 11256-11257. "Structures of Reactive Nitrenium Ions: Time-Resolved Infrared Laser Flash Photolysis and Computational Studies of Substituted N-Methyl-N-arylnitrenium Ions" Srivastava, S.; Ruane, P. H.; Toscano, J. P.; Sullivan, M. B.; Cramer, C. J.; Chiapperino, D.; Reed, E. C.; Falvey, D. E. J. Am. Chem. Soc. 2000, 122, 8271-8278. "Time-Resolved IR Studies of Triplet 1,3-Cyclopentanediyl" Showalter, B. M.; Bentz, T. C.; Ryzhkov, L. R.; Hadad, C. M.; Toscano, J. P. J. Phys. Org. Chem. 2000, 13, 309-312. "Time-Resolved IR Studies of 4-Diazo-3-Isochromanone: Direct Kinetic Evidence for a Non-Carbene Route to Ketene" Wang, Y.; Toscano, J. P. J. Am. Chem. Soc. 2000, 122, 4512-4513. "Time-Resolved IR Studies of 2-Naphthyl(carbomethoxy)carbene: Reactivity and Direct Experimental Estimate of the Singlet/Triplet Energy Gap" Wang, Y.; Yuzawa, T.; Hamaguchi, H.; Toscano, J. P. J. Am. Chem. Soc. 1999, 121, 2875-2882. "Generation and Study of Benzylchlorocarbene from a Phenanthridene Precursor" Nigam, M.; Platz, M. S.; Showalter, B. M.; Toscano, J. P.; Johnson, R. J. Am. Chem. Soc. 1998, 120, 8055-8059. "Structural Differences between pp* and np* Acetophenone Triplet Excited States as Revealed by Time-Resolved IR Spectroscopy" Srivastava, S.; Yourd, E.; Toscano, J. P. J. Am. Chem. Soc. 1998, 120, 6173-6174.