Barbara Marchetti
Education
Ph.D. Chemistry, 2016
University of Bristol, Bristol, UK.
Advisor: Prof. Michael Ashfold. Thesis entitled: Gas-Phase Photochemistry of (Bio)Molecules and Metal Complexes
M.Sci. Chemistry with Honors, 2012
University of Perugia, Italy.
Student Research/Collaboration
As well as teaching commitments, I also run an active research group. My research involves experimental studies of the spectroscopy and photochemistry of (bio)molecules in bulk complex environments. We are particularly interested in the ultrafast and long-timescale dynamics of electronically excited chromophores and how such processes apply to atmospheric and biological systems.
Our ongoing research projects are reported below.
Photochemistry of simple aromatic and heteroaromatic molecules. Spectral evolution and kinetics of photoirradiation of aromatic and heteroaromatic building blocks can be acquired at different excitation wavelengths using our set-up: the studies are aimed at exploring how well the organic molecules cope with prolonged exposure to UV-Vis light. Deep insights into the mechanism of photoreactions (including the role of the solvent) are provided by computation of reaction pathways.
Synthesis and characterization of new sunscreen prototypes. The project is an extension of previous studies and is carried out in collaboration with the synthetic organic chemistry group (Dr. Gallo) and computational chemistry group (Dr. Karsili). The project relies on the synthesis of new compounds from naturally occurring precursors. Such compounds are carefully tailored to be highly stable under sustained and prolonged UV-Vis irradiation, in order to be potential candidates as active ingredients in sunscreen formulations. Spectroscopic characterization of the synthesized molecules are carried out prior photoirradiation studies to test photostability. The effects of solvent, temperature and chemical substitution on the photostability of the prototypes are also explored. As a last step, the effect of synergistic photostability-enhancing compounds, such as radical scavengers and excited state quenchers, is also a central part of this project.
Photo-oxidative potential of dissolved organic matter in the coastal environments of Louisiana. Dissolved organic matter (DOM) is a highly composite mixture of organic materials found in water environments. They mostly derive from the decay of organic tissues. DOM has vital importance for recycling of essential nutrients as well as participating in the transport and reactivity of many organic components dissolved in rivers, basins and sea waters. An important sub-set of such reactions include the production of extremely reactive intermediates (e.g. singlet oxygen and hydroxyl radicals) following absorption of UV-Vis light on ocean surfaces and estuarian waters. We aim at investigating the photochemical and photophysical processes involved in the photoexcitation of DOM and/or its various components in pure water and saline solutions, including their dependence on the irradiation wavelengths and chemical environment on the photochemistry of DOM.
Photodynamic therapy via organometallic complex sensitization. Organometallic complexes have been at the focus of chemical research in the past decades for their pronounced ability of facilitating chemical reactions. Here, our focus is on the ways in which organometallic compounds promote the formation of singlet oxygen via sensitization. The ultimate goal is the development of efficient light activated prodrugs for the effective damage of DNA and protein structures - which may then be used in future cancer therapy. In this project, we collaborate with the group of Dr. Radhey Srivastava who are experts on the synthesis of highly chiral and ordered organometallic frameworks for asymmetric catalysis.
Publications
- M. F. Vansco, B. Marchetti, T. Bhagde, G. Wang, N. Trongsiriwat, P. J. Walsh, S. J. Klippenstein, and Marsha I. Lester, Synthesis, Electronic Spectroscopy, and Photochemistry of Methacrolein Oxide: A Four-Carbon Unsaturated Criegee Intermediate from Isoprene Ozonolysis, J. Am. Chem. Soc,, 2019, 141, 15058.
- B. Marchetti, T. Karsili and M. N. R. Ashfold, Exploring Norrish Type I and Type II Reactions: An ab initio Mechanistic Study Highlighting Singlet- State Mediated chemistry, Phys. Chem. Chem. Phys., 2019, 21, 14418.
- M. F. Vansco, B. Marchetti and M. I. Lester, Electronic spectroscopy of methyl vinyl ketone oxide: A four-carbon unsaturated Criegee intermediate from isoprene ozonolysis, J. Chem. Phys., 2018, 149, 244309.
- B. Marchetti, T. N. V. Karsili and M. N. R. Ashfold, The Role of ps* States in the Formation of Adenine Radical-Cations in DNA Duplexes, Chemical Physics, 2018, 515, 464.
- P. Chakraborty, T. N. V. Karsili, B. Marchetti and S. Matsika, Mechanistic insights into photoinduced damage of DNA and RNA nucleobases in the gas phase and in bulk solution, Faraday Discussions, 2018, 207, 329.
- T. N. V. Karsili, B. Marchetti and S. Matsika, Journal of Physical Chemistry A, Origins of Photodamage in Pheomelanin Constituents: Photochemistry of 4-Hydroxybenzothiazole, J. Phys. Chem. A, 2018, 122, 1986.
- M. N. R. Ashfold, M. Bain, C. Hansen, R. A. Ingle, T. N. V. Karsili, B. Marchetti and D. Murdock, Exploring the Dynamics of the Photoinduced Ring-Opening of Heterocyclic Molecules, J. Phys. Chem. Letts, 2017, 8, 34403451.
- L. A. Baker, B. Marchetti, T. N. V. Karsili, V. G. Stavros and M. N. R. Ashfold, Photoprotection: Extending lessons learned from studying natural sunscreens to the design of artificial sunscreen constituents, Chemical Society Reviews, 2017, 46, 3770. B. Marchetti, T. N. V. Karsili, M. Cipriani, C. S. Hansen and M. N. R. Ashfold, The near ultraviolet photodissociation dynamics of 2- and 3-substituted thiophenols: Geometric vs. electronic structure effects, J. Chem. Phys., 2017, 147, 013923.
- T. N. V. Karsili, B. Marchetti and M. N. R. Ashfold, Mechanistic Insights into Excited State Intramolecular Proton Transfer in Isolated and Metal Chelated Supramolecular Chemosensors, Dalton Transactions, 2016, 45, 18921.
- B. Marchetti and T. N. V. Karsili, An Exploration of the Reactivity of Singlet Oxygen with Biomolecular Constituents, ChemComm, 2016, 52, 10996.
- B. Marchetti, T. N. V. Karsili, M. N. R. Ashfold and W. Domcke, A ‘bottom up’, ab initio approach to understanding fundamental photophysical processes in nitrogen containing heterocycles, DNA bases and base pairs. Phys. Chem. Chem. Phys. 2016, 18, 20007 (Invited Review).
- B. Marchetti and T. N. V. Karsili, Theoretical insights into the photo-protective mechanisms of natural biological sunscreens: building blocks of eumelanin and pheomelanin, Phys. Chem. Chem. Phys., 2016, 18, 3644.
- B. Marchetti, T. N. V. Karsili, O. Kelly, P. Kapetanopoulos and M. N. R. Ashfold, Near ultraviolet photochemistry of 2-bromo- and 2-iodothiophene: Revealing photoinduced ring opening in the gas phase?, J. Chem. Phys., 2015, 142, 224303.
- A. M. Wenge, T. N. V. Karsili, J. Rodriguez Diaz, M. I. Cotterell, B. Marchetti, R. N. Dixon and M. N. R. Ashfold, Tuning photochemistry: substituent effects on ps* state mediated bond fission in thioanisoles., Phys. Chem. Chem. Phys., 2015, 17, 16246.
- T. N. V. Karsili, B. Marchetti, M. N. R. Ashfold and W. Domcke, Ab Initio Study of Potential Ultrafast Internal Conversion Routes in Oxybenzone, Caffeic Acid and Ferulic Acid: Implications for Sunscreens, J. Phys. Chem. A, 2014, 118, 11999.
- S. E. Greenough, M. D. Horbury, J. O. F. Thompson, G. M. Roberts, T. N. V. Karsili, B. Marchetti, D. Townsend and V. G. Stavros, Solvent Induced Conformer Specific Photochemistry of Guaiacol, Phys. Chem. Chem. Phys., 2014, 16, 16187.
- T. N. V. Karsili, A. M. Wenge, B. Marchetti and M. N. R. Ashfold, Symmetry Matters: Photodissociation Dynamics of Symmetrically versus Asymmetrically Substituted Phenols, Phys. Chem. Chem. Phys., 2014, 16, 588.
- T. N. V. Karsili, B. Marchetti, R. Moca, M. N. R. Ashfold, UV Photodissociation of Pyrroles; Symmetry and Substituent Effects, J. Phys. Chem. A., 2013, 117, 12067
Awards & Recognition
- Marie-Skłodowska-Curie Global Post-Doctoral Fellowship. PhARRAO: Photo- and Radical- induced Reactivity of Atmospheric Oxidants. 2016. Grant Amount: $280,000.
- Technical University of Munich Foundation Fellowship. 2016. Grant Amount: 35,000 Euros.