title: Cisplatin Primary Complex with l-Histidine Target Revealed by IR Multiple Photon Dissociation (IRMPD) Spectroscopy.
abstract: The primary complex obtained from cisplatin and l-histidine in water has been detected and isolated by electrospray ionization. The so-obtained cis-[PtCl(NH3)2(histidine)]+complex has been characterized in detail by high-resolution mass spectrometry (MS), tandem MS, IR multiple photon dissociation (IRMPD) spectroscopy, and by quantum chemical calculations. The structural features revealed by IRMPD spectroscopy indicate that platinum binds to the imidazole group, which presents tautomeric forms. Thus, depending on the position of the amino acid pendant on the imidazole ring, isomeric complexes are formed that are remarkably different with respect to the ease with which they undergo fragmentation when activated either by energetic collisions or by multiple IR photon absorption. It is shown here how IRMPD kinetics can allow their relative proportions to be estimated.
authors.affiliation: Dipartimento di Chimica e Tecnologie del Farmaco, Università degli Studi di Roma La Sapienza, P.le A. Moro 5, 00185, Roma, Italy.
authors.forename: Davide
authors.identifier: http://orcid.org/0000-0001-8064-3492
authors.initials: D
authors.lastname: Corinti
authors.affiliation: Dipartimento di Chimica e Tecnologie del Farmaco, Università degli Studi di Roma La Sapienza, P.le A. Moro 5, 00185, Roma, Italy.
authors.forename: Alberto
authors.initials: A
authors.lastname: De Petris
authors.affiliation: Dipartimento di Farmacia, Università G. D'Annunzio, Via dei Vestini 31, 66100, Chieti, Italy.
authors.forename: Cecilia
authors.identifier: http://orcid.org/0000-0002-3609-290X
authors.initials: C
authors.lastname: Coletti
authors.affiliation: Dipartimento di Farmacia, Università G. D'Annunzio, Via dei Vestini 31, 66100, Chieti, Italy.
authors.forename: Nazzareno
authors.identifier: http://orcid.org/0000-0002-0957-4049
authors.initials: N
authors.lastname: Re
authors.affiliation: Dipartimento di Chimica e Tecnologie del Farmaco, Università degli Studi di Roma La Sapienza, P.le A. Moro 5, 00185, Roma, Italy.
authors.forename: Barbara
authors.identifier: http://orcid.org/0000-0002-1585-7061
authors.initials: B
authors.lastname: Chiavarino
authors.affiliation: Dipartimento di Chimica e Tecnologie del Farmaco, Università degli Studi di Roma La Sapienza, P.le A. Moro 5, 00185, Roma, Italy.
authors.forename: Maria E
authors.identifier: http://orcid.org/0000-0002-0991-5034
authors.initials: ME
authors.lastname: Crestoni
authors.affiliation: Dipartimento di Chimica e Tecnologie del Farmaco, Università degli Studi di Roma La Sapienza, P.le A. Moro 5, 00185, Roma, Italy.
authors.forename: Simonetta
authors.identifier: http://orcid.org/0000-0002-6312-5738
authors.initials: S
authors.lastname: Fornarini
mesh_terms: D002945:Cisplatin / Q000032:analysis*; D006639:Histidine / Q000032:analysis*; D007700:Kinetics; D013058:Mass Spectrometry; D017785:Photons; D011789:Quantum Theory; D013055:Spectrophotometry, Infrared
chemical_list: D006639:Histidine; D002945:Cisplatin
keywords: antitumor agents; cisplatin; isomers; mass spectrometry; structure elucidation