Phd in MOLECULAR DESIGN AND CHARACTERIZATION FOR THE
PROMOTION OF HEALTH AND WELL-BEING: FROM DRUG TO FOOD

email: barbara.chiavarino@uniroma1.it
phone: 0649913151
building: Chimica Farmaceutica (CU019)- Facoltà di Farmacia
room: 153

Education
• Laurea (Master Degree) in Pharmaceutical Chemistry and Technology (110/110).
• PhD in Pharmaceutical Sciences (VIII ciclo).

Academic Appointments
• 1-03-2019-today : Associate Professor in General and Inorganic Chemistry at the University of Rome “La Sapienza” in the Department of Chimica e Tecnologie del Farmaco.
• 1-10-1998 -28-02-2019: Assistant Professor , in Inorganic Chemistry at the University of Rome “La Sapienza” in the Department of Chimica e Tecnologie del Farmaco.
• 2018: National Scientific Qualification (ASN) as full professor (Professore di I fascia per il settore 03/B1 “Fondamenti delle Scienze Chimiche e Sistemi Inorganici”)
• 2013: National Scientific Qualification (ASN) as Associate Professor (Professore Associato (II fascia) per il settore 03/B1 “Fondamenti delle Scienze Chimiche e Sistemi Inorganici” )
• 2012 National Scientific Qualification (ASN) as Associate Professor ( Professore Associato (II fascia) per il settore 03/B2 “Fondamenti Chimici delle Tecnologie” )

Formal assignment fellowships (teaching or research) from qualified foreign or supranational universities and research institutes:
• November 2018: Invited Lecturer at the University of Paris Sud, Orsay. Lecture in “Méthodes avancées de spectroscopie” for the M2 degree in Physical Chemistry at the Facultè des Sciences d’Orsay
• November 2017: Invited Lecturer at the University of Paris Sud, Orsay. Lecture in “Méthodes avancées de spectroscopie” for the M2 degree in Physical Chemistry at the Facultè des Sciences d’Orsay
• 1997: Short term visit (two months) at the laboratory of Professor Hans-Friedrich Grützmacher and Professor Dietmar Kuck., Universität Bielefeld, in Germany
• 01/04/1996-31/03/1997: Winner of a Grant in Chemical Sciences of the C.N.R (Italian National Research Council )
• 1994: Short term visit (six months) at the Eurofins Industry and at the laboratory of Professor Prof. G. Martin, Université de Sciences et Tecnologies of Nantes , in France as winner of a Comett Grant , (European exchange programme between university and enterprise training partnerships)

Teaching experience:
• 2018- today: “General and Inorganic Chemistry”, (canale M-Z), for degree in Scienze Farmaceutiche Applicate at the University of Rome “La Sapienza” . ( 9 CFU – 84 hours)
• 2017- today: “General and Inorganic Chemistry”, (canale A-L), for degree in Scienze Farmaceutiche Applicate, at the University of Rome “La Sapienza” . (9 CFU – 84 hours)
• 2017-oggi: “General and Inorganic Chemistry”, (canale A-L, lezioni a piccoli gruppi) for master degree in Chimica e Tecnologia Farmaceutiche at the University of Rome “La Sapienza”. (3 CFU- 30 hours)
• 2010-2016: “General and Inorganic Chemistry”, (canale A-Z), for degree in Scienze Farmaceutiche Applicate at the University of Rome “La Sapienza. ( 9 CFU – 84 hours)
• 2001- General and Inorganic Chemistry”, (canale A-L), for degree in Informazione Scientifica sul Farmaco at the University of Rome “La Sapienza. (10 CFU - 80 hours).
• 1999-2002 Coordination Compounds Chemistry, for master degree in Chimica e Tecnologia Farmaceutiche at the University of Rome “La Sapienza”.

Awards and Honors:
• 2016: Scuderi, D., Bodo, E., Chiavarino, B., Fornarini, S., Crestoni, M.E. “Amino Acid Oxidation: A Combined Study of Cysteine Oxo Forms by IRMPD Spectroscopy and Simulations” Chemistry - A European Journal (2016), 22 (48), pp. 17239-17250 – Cover of the issue
• 2016: Corinti, D., Crestoni M. E., Fornarini, S., Chiavarino, B. “Distinction between cyanidine 3-O-glucoside and cyanidine 3-O-galactoside by mass spectrometry combined with IRMPD spectroscopy” Convegno Massa 2016, Istituto Superiore di Sanità, Roma, 6-8 settembre, 2016. – Best Poster award
• 2015: Corinti, D., Coletti, C., Re, N., Chiavarino, B., Crestoni, M. E., Fornarini, S. “Cisplatin reactions with model biological ligands monitored by IR multiphoton dissociation spectroscopy” - XLIII Congresso Nazionale della Divisione di Chimica Inorganica della Società Chimica Italiana – Camerino, 9-12 settembre 2015. – Best Poster award
• 2007: Chiavarino, B., Crestoni, M.E., Fornarini, S., Lanucara, F., Lemaire, J., Maître, P. “Meisenheimer complexes positively characterized as stable intermediates in the gas phase” Angewandte Chemie - International Edition, (2007) 46 (12), pp. 1995-1998.- Very Important paper mention
• 1999: Chiavarino, B., Crestoni, M.E., Di Marzio, A., Fornarini, S., Rosi, M. “Electrophilic substitution of gaseous borazine” Journal of the American Chemical Society, (1999), 121 (11), pp. 2619-2620. - special mention in Chemical & Engineering News (C&EN) MARCH 22,1999

Research Activities:
The main issue in my research activity regards the study of the structure and reactivity of ionic species in the gas phase. The advantage of carrying out an investigation in the gas phase is related to the dilute environment lacking solvation and ion pairing effects, typical of the condensed phase. Thereby, it becomes possible to highlight the intrinsic reactivity of ions, thus offering a valid reference for theoretical calculations and an insight into the influence of the solvent in solution. This approach has relevance for the understanding of complex processes occurring in interstellar space, in flames ending, up to the hydrophobic environment of some enzymatic sites. The studies that I am presenting here have been carried out exploiting, and often combining, two complementary methodologies, namely the Fourier transform ion-cyclotron resonance mass spectrometry (FT-ICR MS) and the InfraRed Multiple Photon Dissociation (IRMPD) spectroscopy.
FT-ICR mass spectrometry operates in a very low-pressure regime, in the range of 1-10 × 10-8 mbar, where the initial energy content of the reaction partners can be considered constant and the bimolecular reactions take place in a single collision regimen. This tool allows to mass-select a specific ion of interest from a very complex ionic population, identify its molecular formula by high resolution mass measurements and distinguish among isomeric compounds with same integer mass, but different chemical formulas. In addition, the ion trapping ability of FT-ICR MS enables the reactivity behavior towards selected neutrals to be investigated. In this way, isomeric species can be kinetically characterized and distinguished. FT-ICR MS does also allow to determine: i) the rate constants of ion-molecule reactions occurring through multiple parallel or consecutive channels; ii) fundamental thermodynamic parameters, such as enthalpies and Gibbs free reaction energies and the heat of formation of ionic and neutral species, through the attainments of equilibrium constants.
IRMPD spectroscopy is a powerful tool to perform structural characterization of ionic species in the isolated state. The direct spectroscopic assay of bare species has become possible after the coupling of a bright IR laser source with a modified mass spectrometer (FT-ICR or Paul trap). This combination overcomes the difficulty related to the low density of gaseous ions stored inside the ion trap. The studies presented here have taken advantage of two different experimental platforms. For the mid-IR (600-2000 cm-1), the intense and tunable IR radiation of the free electron laser (FEL) beamline at the Centre Laser Infrarouge d’Orsay (CLIO) at Université Paris XI was used. The experiments were carried out in collaboration with Philippe Maître and his team and allowed us to record IR spectra of gaseous ions, in the absence of perturbations due to solvent, matrix or counter-ions. The second, more recent coupling has been achieved at Sapienza Università di Roma and uses a benchtop optical parametric oscillator/amplifier (OPO/A) laser associated with an ion-trap. This apparatus allows to record IR spectra of mass-selected ions in the X-H stretching range (X = C, N, O) (2800 -4000 cm-1). The non-coherent absorption of multiple IR photons may induce fragmentation of the selected ion within the ion trap. IR induced fragmentation is only observed on resonance with an IR active vibrational mode of the selected ion. IRMPD spectra are obtained by plotting the photofragmentation yield as a function of the frequency of the IR radiation in the two spectral ranges. Experimental studies are backed by ab initio theoretical calculations. The comparison between the IRMPD spectra and the IR absorption spectra calculated for the most stable structures may allow the structural assignment of the sampled ions and highlight the preferred conformations in the gas phase. This result is unprecedented and has been exploited to address the characterization of metal cation binding patterns, natural and modified amino acids and peptides, halide complexes, simple (in)organic species of fundamental interest. In most cases, the ionic species are formed in solution and then driven in the gas phase by electrospray ionization.

Main achievements:
(a) Reactivity and structural issues regarding a Platinum-based anticancer drug
(b) Fundamentals ions: (1) Protonated aromatics. (2) Cation- interactions (3) Interaction of anions with -acidic aromatics (4) Protonated inorganic acids. (5) Silyl cation.
(c) Structural and functional consequence of post- translational modifications (PTMs) of amino acids and peptides.
(d) Reactivity of iron porphyrin complexes, FeIII-heme+ and FeII-HemeH+
(e) Untargeted analysis of foodstuff

Keywords:
• Tandem mass spectrometry
• Infrared spectroscopy of gaseous ions
• Structural characterization
• Intermolecular interactions (ion-ligand interactions, hydrogen bonds, ion-pi interactions, molecular recognition of biological systems
• Kinetics, energetics, and chemical reaction mechanisms of ionic intermediates
• Ion-molecule reactions
Expertise
• Expertise in mass spectrometry (MS): ion traps, triple quadrupole, GC-MS, FT-ICR
• Expertise in measurements with free-electron laser systems and table-top laser systems.
• Expertise in other means for studying gas phase ion chemistry, such as radiolytic techniques and kinetics measurements in ion molecule reactions.