Bioinorganic Chemistry and mass spectrometry (CHIM/03)

Attività di ricerca

Main research topics:

Chemical and biochemical processes of fundamental importance occur in solution and frequently proceed by ionic species behaving as fleeting intermediates. Mass spectrometry offers a powerful tool to intercept and manipulate these species, which thus allows one to gain insight into their role. Structural information and resolution can be gained using collision induced dissociation (CID) experiments, ion-molecule reactions and vibrational spectroscopy of the sampled gaseous ionic species as attained by IRMPD spectroscopy. Specific research topics:

-Relevant species that are responsible for the biological effects of metallo-drugs including cisplatin (cis-PtII(NH3)2Cl2, anticancer drug widely used in the clinic for the treatment of a broad spectrum of solid tumors), platinum(IV) complexes (behaving as prodrugs, more easily deliverable than the active species cisplatin), binuclear copper complexes and CO releasing carbonyl complexes. Ionic complexes and reaction intermediates can be delivered by electrospray ionization to be isolated and thoroughly sampled in the ion trap of the mass spectrometer.

- Intermediates involved in post-translational modifications, in particular those activated by reactive oxygen and nitrogen species, with a view towards identifying new methods for detection and characterization

- Untargeted analyses of complex mixtures such as those related to specimens of nutritional value from the plant realm.

Collaborazioni nazionali e internazionali

Several collaborations are ongoing with colleagues from the department and the university. At national and international level with the following scientists: N. Re and C. Coletti (Università Chieti-Pescara); P. Maitre, D. Scuderi and N. Shafizadeh (Université Paris Sud); J.-Y. Salpin and R. Spezia (Université d'Evry); O. Dopfer (Technische Universitaet Berlin); E. Gabano and D. Osella (Università Piemonte Orientale); E. Sicilia and N. Russo (Università della Calabria); R. Sinha (Manipal University); A. Tintaru (Aix Marseille Univ).

  • FT-ICR mass spectrometer (MS) (Bruker Apex II) for HiRes MS
  • LTQ-XL linear ion trap mass spectrometer equipped with U-FAIMS ion mobility device
  • triple quadrupole MS (Applied Biosystems 2000) (shared with prof. A. Filippi)
  • OPO/OPA laser system - ion trap MS (Esquire 6000+, Bruker) for IRMPD spectroscopy (shared with prof. A. Filippi)
  • ion trap MS (Esquire 3000+
Settori ERC


  • PE4_2 - Physical chemistry
  • PE4_11 - Physical chemistry of biological systems
  • PE4_12
  • PE5_9 - Analytical chemistry



Grants (2015-2018):

  • CLIO projects (funded by the EU): IC15-007, IC16-007 (principal investigator, PI, Fornarini), IC15-0013 (PI Chiavarino), IC17-002 (PI Crestoni)
  • FILAS project funded by the Regione Lazio: 2015-18 e-Alierb (PI prof.ssa Luisa Mannina)
  • Research grants funded by Sapienza University of Rome:
    • 2015, prot. N. C26H15MHLB 20.000€ (PI Fornarini)
    • 2016, DR n. 3210/16 del 16/12/2016, 11.000€ (PI Crestoni)
    • 2016 Avvio ricerca, 1.000€ (PI Corinti)
    • 2017 Avvio ricerca prot. N.AR11715C7E1E1E6A, 1.800€ (PI Corinti); 2017, 4.000€ (PI Crestoni)
    • 2017, 3.000€ (PI Chiavarino); FFABR 2017, 3.000 € (Crestoni)
    • FFABR 2017, 3.000 € (Chiavarino).

Pubblicazioni (2019-2021):

1. D. Corinti, B. Chiavarino, M. Spano, A. Tintaru, S. Fornarini, M.E. Crestoni
Molecular Basis for the Remarkably Different Gas-Phase Behavior of Deprotonated Thyroid Hormones Triiodothyronine (T3) and Reverse Triiodothyronine (rT3): A Clue for Their Discrimination?
Anal. Chem. 2021, 93, 14869–14877

2. M. Spano, A. Maccelli, G. Di Matteo, C. Ingallina, M. Biava, M. E. Crestoni, J.-X. Bardaud, A. M. Giusti, A. Scotto D’Abusco, A. P. Sobolev, A. Lasalvia, S. Fornarini, L. Mannina
Metabolomic profiling of fresh Goji (Lycium barbarum L.) berries from two cultivars grown in Center Italy: a multi-methodological approach
Molecules 2021, 26, 5412 (1-23)

3. R. Paciotti, D.Corinti, P. Maitre, C. Coletti, N. Re, B. Chiavarino, M. E. Crestoni, S. Fornarini
From preassociation to chelation: a survey of cisplatin interaction with methionine at molecular level by IR ion spectroscopy and computations
J. Am. Soc. Mass Spectrom. 2021, 32, 2206−2217

4. D. Corinti, B. Chiavarino, D. Scuderi, P. Maitre, C. Fraschetti, A. Filippi, S. Fornarini, M. E. Crestoni
Molecular properties of bare and microhydrated vitamin B5 - calcium complexes
Int. J. Molecular Sciences 2021, 22, 692 (pp. 1-19)

5. B. Chiavarino, R. K. Sinha, M. E. Crestoni, D. Corinti, A. Filippi, C. Fraschetti, D. Scuderi, P. Maitre, S. Fornarini
Binding motifs in the naked complexes of target amino acids with an excerpt of antitumor active biomolecule. An ion vibrational spectroscopy assay
Chem. Eur. J. 2021, 27, 2348-2360.

6. C. Ingallina, A. Maccelli, M. Spano, G. Di Matteo, A. Di Sotto, A. M. Giusti, G. Vinci, S. Di Giacomo, M. Rapa, S. Ciano, C. Fraschetti, A. Filippi, G. Simonetti, C. Cordeiro, M. Sousa Silva, M. E. Crestoni , A. P. Sobolev, S. Fornarini, L. Mannina
Chemico-biological characterization of Torpedino di Fondi® tomato fruits: a comparison with San Marzano cultivar at two ripeness stages
Antioxidants 2020, 9, 1027 (1-29).   

7. D. Corinti, G. Frison, B. Chiavarino, E. Gabano, D. Osella, M. E. Crestoni, S. Fornarini
Can an elusive Pt(III) oxidation state be exposed in an isolated complex ?
Angew. Chem. Int. Ed. 2020, 59, 15595-15598.

8. A. Maccelli, S. Cesa, F. Cairone, D. Secci, L. Menghini, B. Chiavarino, S. Fornarini, M. E. Crestoni, M. Locatelli
Metabolic profiling of different wild and cultivated Allium species based on high resolution mass spectrometry, HPLC-PDA and color analysis
J. Mass Spectrom. 2020, 55, 2020e4525.

9. D. Corinti, M. E. Crestoni, S. Fornarini, E. Dabbish, E. Sicilia, E. Gabano, E. Perin, D. Osella
A multi-methodological inquiry of the behavior of cisplatin-based Pt(IV) derivatives in the presence of bioreductants with a focus on the isolated encounter complexes
J. Biol. Inorg. Chem. 2020, 25, 655-670.

10. D. Corinti, M. E. Crestoni, B. Chiavarino, S. Fornarini, D. Scuderi, J.-Y. Salpin
Insights into Cisplatin Binding to Uracil and Thiouracils from IRMPD Spectroscopy and Tandem Mass Spectrometry
J. Am. Soc. Mass Spectrom. 2020, 31, 946-960.

11. B. Chiavarino, O. Dopfer, M. E. Crestoni, D. Corinti, P. Maître, S. Fornarini
IRMPD spectra of protonated hydroxybenzaldehydes: Evidence of torsional barriers in carboxonium ions ChemPhysChem 2020, 21, 749-761.

12. P. Maitre, D. Scuderi, D. Corinti, B. Chiavarino, M. E. Crestoni, S. Fornarini
Applications of IRMPD to the detection of post translational modifications
Chem. Rev. 2020, 120, 3261-3295.

13. A. Maccelli, L. Vitanza, A. Imbriano, C. Fraschetti, A. Filippi, P. Goldoni, L. Maurizi, M. G. Ammendolia, M. E. Crestoni, S. Fornarini, L. Menghini, C. Marianecci, M. Carafa, C. Longhi, F. Rinaldi
Satureja montana L. essential oils: chemical profiles/phytochemical screening, antimicrobial activity and O/W NanoEmulsion formulations
Pharmaceutics 2020, 12, 7 pp. 1-20    

14. C. Ingallina; D. Capitani; S. Carradori; M. Locatelli; A. Di Sotto; S. Di Giacomo; C. Toniolo; G. Pasqua; A. Valletta; G. Simonetti; A. Parroni; M. Beccaccioli; G. Vinci; M. Rapa; A. M. Giusti; C. Fraschetti; A. Filippi; A. Maccelli; M. E. Crestoni; S. Fornarini; A. P. Sobolev; L. Mannina
Phytochemical and biological characterization of Italian "sedano bianco di Sperlonga" Protected Geographical Indication celery ecotype: a multimethodological approach
Food Chemistry 2020, 309, article 125649, pp. 1-15   

15. D. Corinti, R. Paciotti, N. Re, C. Coletti, B. Chiavarino, M. E. Crestoni, S. Fornarini
Binding motifs of cisplatin interaction with simple biomolecules and aminoacid targets probed by IR ion spectroscopy
Pure Appl. Chem. 2020, 92, 3-13.

16. D. Corinti, A. Maccelli, M. E. Crestoni, S. Cesa, D. Quaglio, B. Botta, C. Ingallina, L. Mannina, A, Tintaru, B. Chiavarino, S. Fornarini
IR ion spectroscopy in a combined approach with MS/MS and IM-MS to discriminate epimeric anthocyanin glycosides (cyanidin 3-O-glucoside and -galactoside)
Int. J. Mass Spectrom. 2019, 444, article 116179

17. D. Corinti, M. E. Crestoni, S. Fornarini, F. Ponte, N. Russo, E. Sicilia, E. Gabano, D. Osella
Elusive intermediates in the breakdown reactivity patterns of prodrug platinum(IV) complexes
J. Am. Soc. Mass Spectrom. 2019, 30, 1881-1894    

18. V. Macaluso, D. Scuderi, M. E. Crestoni, S. Fornarini, D. Corinti, E. Dalloz, E. Martínez-Núñez, W. Hase, R. Spezia
L-Cysteine Modified by S-Sulfation: Consequence on Fragmentation Processes Elucidated by Tandem Mass Spectrometry and Chemical Dynamics Simulations
J. Phys. Chem. A 2019, 123, 3685-3696.    

19. D. Corinti, A. Maccelli, B. Chiavarino, P. Maitre, D. Scuderi, E. Bodo, S. Fornarini, M. E. Crestoni
Vibrational Signatures of Curcumin's Chelation in copper(II) complexes: an appraisal by IRMPD spectroscopy
J. Chem. Phys. 150, 165101/1-12 (2019)

20. A. Ciavardini, M. Coreno, C. Callegari, C. Spezzani, G. De Ninno, B. Ressel, C. Grazioli, M. de Simone, A. Kivimäki, P. Miotti, F. Frassetto, L. Poletto, C. Puglia, S. Fornarini, E. Bodo, S. Piccirillo
Ultra-fast -VUV photoemission study of UV excited 2-nitrophenol
J. Phys. Chem. A, 2019, 123, 1295–1302.

21. D. Corinti, M. E. Crestoni, S. Fornarini, M. Pieper, K. Niehaus, M. Giampà
An integrated approach to study novel properties of a MALDI matrix (4-maleicanhydridoproton sponge) for MS imaging analyses
Analytical and Bioanalytical Chemistry (2019) 411:953–964   

22. D. Corinti, C. Coletti, N. Re, R. Paciotti, P. Maitre, B. Chiavarino, M. E. Crestoni, S. Fornarini
Short-lived intermediates (encounter complexes) in cisplatin ligand exchange elucidated by infrared ion spectroscopy
Int. J. Mass Spectrom. 2019, 435, 7–17.   

23. L. Vitanza, A. Maccelli, M. Marazzato, F. Scazzocchio, A. Comanducci, S. Fornarini, M. E. Crestoni, A. Filippi, C. Fraschetti, F. Rinaldi, M. Aleandri, P. Goldoni, M. P. Conte, M. G. Ammendolia, C. Longhi  
Satureja montana L. essential oil and its antimicrobial activity alone or in combination with gentamicin
Microbial Pathogenesis 126 (2019) 323–331


Publications (2015-2018):

1. M. E. Crestoni
Radiopharmaceuticals for Diagnosis and Therapy
Reference Module in Chemistry, Molecular Sciences and Chemical Engineering, Elsevier, 2018

2. F. G. Cantú Reinhard, S. Fornarini, M. E. Crestoni, S. P. de Visser
Hydrogen atom versus hydride transfer in cytochrome P450 oxidations: A combined mass spectrometry and computational study Eur. J. Inorg. Chem.2018, DOI: 10.1002/ejic.201800273

3. D. Corinti, B. Gregori, L. Guidoni, D. Scuderi, T. McMahon, B. Chiavarino, S. Fornarini, M. E. Crestoni Complexation of halide ions to tyrosine: role of non-covalent interactions evidenced by IRMPD spectroscopy Phys. Chem. Chem. Phys. 2018, 20, 4429-4441. DOI: 10.1039/c7cp06657k

4. R. Paciotti, D. Corinti, A. De Petris, A. Ciavardini, S. Piccirillo, C. Coletti, N. Re, P. Maitre, B. Bellina, P. Barran, B. Chiavarino, M. E. Crestoni, S. Fornarini. Cisplatin and transplatin interaction with methionine: bonding motifs assayed by vibrational spectroscopy in the isolated ionic complexes. Phys.Chem.Chem.Phys. 2017, 19, 26697-26707. DOI: 10.1039/c7cp05203k

5. C. Coletti, D. Corinti, R. Paciotti, N. Re, M. E. Crestoni, S. Fornarini
Structure and dynamics of gas phase ions: Interplay between experiments and computations in IRMPD spectroscopy
AIP Conference Proceedings, 2017, 1906, 030011.

6. N. Shafizadeh, S. Soorkia, G.Grégoire, M. Broquier, M. E. Crestoni, B. Soep
Dioxygen Binding to Protonated Heme in the Gas Phase, an Intermediate Between Ferric and Ferrous Heme
Chem. Eur. J.2017, 54, 13493-13500. DOI: 10.1002/chem.201702615

7. B.Chiavarino, M. E. Crestoni, S. Fornarini, D. Scuderi, J.-Y. Salpin
Undervalued N3-coordination revealed in the cisplatin complex with 2′-Deoxyadenosine-5′-monophosphate by a combined IRMPD and theoretical study.
Inorganic Chemistry, 2017, 56, 8793-8801.

8. D. Corinti, C. Coletti, N. Re, S. Piccirillo, M. Giampà, M. E. Crestoni, S. Fornarini
Hydrolysis of cis- and transplatin: structure and reactivity of the aqua complexes in a solvent free Environment
RSC Adv., 2017, 7, 15877–15884.

9. B. Gregori, L. Guidoni, M. E. Crestoni, P. de Oliveira, C. Houée-Levin, Debora Scuderi
One-Electron Oxidation of Methionine-Containing Dipeptides of Reverse Sequence: Sulfur versus Sulfoxide Characterized by IRMPD Spectroscopy and Static and Dynamics DFT Simulations,
J. Phys. Chem. B2017, 121, 2083−2094.

10. D. Corinti,A. De Petris,C. Coletti,N. Re,B. Chiavarino,M. E. Crestoni,S. Fornarini
Cisplatin primary complex with L-histidine target revealed by IRMPD spectroscopy
ChemPhysChem2017, 18, 318-325. DOI: 10.1002/cphc.201601172

11. B. Chiavarino, M. E. Crestoni, S. Fornarini
Vibrational signatures of gaseous Meisenheimer complexes bonded at carbon and nitrogen
Int. J. Mass Spectrom.,2017, 418, 173-179. DOI:10.1016/j.ijms.2016.09.012

12. D. Scuderi, E. Bodo, B. Chiavarino, S. Fornarini, M. E. Crestoni
Amino-acids oxidation: a combined study of cysteine oxo forms by IRMPD spectroscopy and simulations
Chem. Eur. J.2016, 22, 17239–17250. DOI : 1 0.1002/chem.201603298

13. F. G. Cantú Reinhard, M. A. Sainna, P. Upadhayay, G. A. Balan,D. Kumar, S. Fornarini,
M. E. Crestoni, S. P. de Visser
A systematic account on aromatic hydroxylation by a cytochrome P450 model Compound I: low-pressure mass spectrometry and computational study
Chem. Eur. J.2016, 22, 18608 –18619. DOI : 10.1002/chem.201604361

14. M. Schütz, A. Bouchet, B. Chiavarino, M. E. Crestoni, S. Fornarini, O. Dopfer
Effects of Aromatic Fluorine Substitution on Protonated Neurotransmitters: The Case of 2-Phenylethylamine
Chem. Eur. J.2016, 22, 8124-8136. DOI: 10.1002/chem.201600798

15. D. Corinti, C. Coletti, N. Re, B. Chiavarino, M. E. Crestoni, S. Fornarini
Cisplatin Binding to Biological Ligands Revealed at the Encounter Complex Level by IR Action Spectroscopy
Chem. Eur. J.2016, 22, 3794–3803. DOI: 10.1002/chem.201504521

16. D. Corinti, L. Mannina, B. Chiavarino, V. Steinmetz,S. Fornarini, M. E. Crestoni
IRMPD signature of protonated pantothenic acid, an ubiquitous nutrient
Chem. Phys. Letters, 2016, 646, 162–167. DOI:10.1016/j.cplett.2016.01.032

17. R. Paciotti, C. Coletti, N. Re, D. Scuderi, B. Chiavarino, S. Fornarini, M. E. Crestoni
Serine O-sulfation probed by IRMPD spectroscopy
PhysChemChemPhys2015, 17, 25891-25904. DOI:10.1039c5cp01409c

18. R. Sinha, D. Scuderi, P. Maitre, B. Chiavarino, M. E. Crestoni, S. Fornarini
Elusive Sulfurous Acid: Gas Phase Basicity and IR Signature of the Protonated Species
J. Phys. Chem. Lett. 2015, 6, 1605-1610.DOI:10.1021/acs.jpclett.5b00450

19. A. Bouchet, M. Schutz, B. Chiavarino, M. E. Crestoni, S. Fornarini, O. Dopfer
Infrared spectrum of the protonated neurotransmitter 2-phenylethylamine: dispersion and anharmonicity in the NH3+-π interaction.
PhysChemChemPhys, 2015, 17, 25742-25754. DOI: 10.1039/C5CP00221d

20. B. Chiavarino, M. E. Crestoni, S. Fornarini, D. Scuderi, J.-Y. Salpin
Interaction of Cisplatin with 5’-dGMP: A combined IRMPD and Theoretical Study
Inorg. Chem. 2015, 54, 3513-3522. DOI:10.1021/acs.inorgchem.5b00070

21. A. De Petris, M. E. Crestoni, A. Pirolli, C. Rovira, J. Iglesias-Fernandez, B. Chiavarino, R. Ragno, S. Fornarini
Binding of azole drugs to heme: a combined MS/MS and computational approach
Polyedron2015, 90, 245-251. DOI:10.1016/j.poly.2015.02.011

22. M. E. Crestoni, B. Chiavarino, S. Fornarini
Nitrosyl-heme and anion-arene complexes: structure, reactivity and spectroscopy.
Pure and Applied Chemistry, 2015, 87, 379-390. DOI:10.1016/j.poly.2015.02.011

23. A. De Petris, B. Chiavarino, M. E. Crestoni, C. Coletti, N. Re, S. Fornarini
Exploring the Conformational Variability in the Heme b Propionic Acid Side Chains through the Effect of a Biological Probe: A Study on the Isolated Ions
J. Phys. Chem. B, 2015, 119, 1919-1929. DOI:10.1021/jp5113476

24. M. A. Sainna, S. Kumar, D. Kumar, S. Fornarini, M. E. Crestoni, S. P. de Visser
A comprehensive test set of epoxidation rate constants by iron(IV)-oxo porphyrin cation radical complexes
Chemical Science, 2015, 6, 1516-1529. DOI: 10.1039/c4sc02717e

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