Research Groups‎ > ‎

Bioinorganic Chemistry and mass spectometry (CHIM/03)

Head of Laboratory: Simonetta Fornarini and Crestoni Elisa
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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 manipulatethese species, allowing to obtain 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:

1) Relevant species that are responsible for the biological effects of cisplatin, cis-PtII(NH3)2Cl2, anticancer drug widely used in the clinic for the treatment of a broad spectrum of solid tumors with a focus on (i) platinated amino acid residues and small peptides that are involved in cisplatin transport and adverse effects, (ii) platinated fragments of DNA, (iii) platinated intermediates from next generation drugs such as oxaliplatin and carboplatin.

2) 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

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

National and International Collaborations:

Collaborations 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 (Université dEvry Val dEssonne); O. Dopfer (Technische Universitaet Berlin); S. Piccirillo (Università Roma2); S. de Visser and P. Barran (University of Manchester); T. B. McMahon (University of Waterloo, Canada); L. Guidoni (Università dell’Aquila); R. Sinha (Manipal University).


(i) FT-ICR mass spectrometer (MS) (Bruker Apex II) for HiRes MS; (ii) triple quadrupole MS (Applied Biosystems 2000) (shared with prof. A. Filippi); (iii) OPO/OPA laser system - ion trap MS (Esquire 6000+, Bruker) for IRMPD spectroscopy (shared with prof. A. Filippi); (iv) ion trap MS (Esquire 3000+).

ERC panels:

PE4_2 - Physical chemistry
PE4_11 - Physical chemistry of biological systems
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).

EU project: European Network of Fourier-Transform IonCyclotron-Resonance Mass Spectrometry Centers — EU_FT-ICR_MS 2018-2021 (Activity: INFRAIA-02-2017 - Integrating Activities for Starting Communities). 

Laboratory Members:  

Chiavarino Barbara (R)
Corinti Davide (PhD student)
Maccelli Alessandro (PhD student)

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. A. P. Sobolev, L. Mannina, D. Capitani, G. Sanzò, C. Ingallina, B. Botta, S. Fornarini, M. E. Crestoni, B. Chiavarino, S. Carradori, M. Locatelli, A. M. Giusti, G. Simonetti, G. Vinci, R. Preti, C. Toniolo, M. Reverberi, M. Scarpari, A. Parroni, L. Abete, F. Natella, A. Di Sotto. 
A multi-methodological approach in the study of Italian PDO "Cornetto di Pontecorvo" red sweet pepper
Food Chemistry, 2018, 255, 120-131. DOI:

4. 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

5. 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

6. 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.

7. M. Mori, L. Tottone, D. Quaglio, N. Zhdanovskaya, C. Ingallina, M. Fusto, F. Ghirga, G. Peruzzi, M. E. Crestoni, F. Simeoni, F. Giulimondi, C. Talora, B. Botta, I. Screpanti, R. Palermo
Identification of a novel chalcone derivative that inhibits Notch signaling in T-cell acute lymphoblastic leukemia
Scientific Reports, 2017, 7, 2213. DOI:10.1038/s41598-017-02316-9

8. 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

9. 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.

10. 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.

11. 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.

12. F. Scazzocchio, L. Mondì, M. G. Ammendolia, P. Goldoni, A. Comanducci, M. Marazzato, M. Pia Conte, F. Rinaldi, M. E. Crestoni, C. Fraschetti, C. Longhi
Coriander (Coriandrum sativum) Essential Oil: Effect on Multidrug Resistant Uropathogenic Escherichia coli
Natural Product Communications, 2017, 12, 623-626.

13. C. Fraschetti, M. Montagna, M. E. Crestoni, A. Calcaterra, F. Aiello, L. Santi, A. Filippi
Kinetic enantioselectivity of a protonated bis(diamido)-bridged basket resorcin[4]arene towards alanine peptides.
Organic and Biomolecular Chemistry,2017, 15, 1183-1189. DOI: 10.1039/c6ob02734b

14. 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

15. 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

16. A. Filippi, M. E. Crestoni, C. Fraschetti, M. Montagna, L. Guarcini, E. Marcantoni, M. Glucini, M. Speranza
Reactivity of Contact Ion Pairs in a Charged Monotopic Receptor.
Int. J. Mass Spectrom. 2017, 418, 198-203.

17. A. Ciavardini, S. Fornarini, A. Dalla Cort, S. Piccirillo, D. Scuderi, E. Bodo
Experimental and Computational investigation of Salophen-Zn Gas Phase Complexes with Cations: Possible Cationic Interference in Anionic Recognition
J. Phys. Chem. A, 2017, 121, 7042-7050. DOI: 10.1021/acs.jpca.7b05825

18. A. Ciavardini, A. Dalla Cort, S. Fornarini, D. Scuderi, A. Giardini, G. Forte, E. Bodo, S. Piccirillo
Adenosine monophosphate recognition by zinc–salophen complexes: IRMPD spectroscopy and quantum modeling study
Journal of Molecular Spectroscopy335 (2017) 108–116. DOI: 10.1016/j.jms.2017.02.014

19. 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

20. 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

21. 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

22. C. Fraschetti, A. Filippi, M. E. Crestoni, E. Marcantoni, M. Glucini, L. Guarcini, M. Montagna, L. Guidoni, M.Speranza
Contact Ion Pairs on a Protonated Azamacrocycle: The Role of the Anion Basicity
J. Am. Soc. Mass Spectrom.2016, 27, 615-621.

23. 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

24. 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

25. 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

26. 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

27. 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

28. 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

29. 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

30. C. Fraschetti, A. Filippi, M. E. Crestoni, E. Marcantoni, M. Glucini, L. Guarcini, M. Montagna, L. Guidoni, M. Speranza
Protonated hexaazamacrocycles as selective K+receptors.
J. Am. Soc. Mass Spectrom. 2015, 26, 1186-1190. DOI:10.1007/s13361-015-1104-3

31. 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

32. 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

33. 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