Electrospray Ionization Mass Spectrometry of Palladium(II) Quinolinylaminophosphonate Complexes

Juribašić, Marina; Bellotto, Lisa; Traldi, Pietro; Tušek-Božić, Ljerka

doi:10.1007/s13361-011-0186-9

Cited by 5 publications

(4 citation statements)

References 39 publications

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“…Figure also shows two peaks appearing at m / z 225.1 and 227.1, which are most likely due to the elimination of NaCl and HCl from sodiated and protonated cyclophosphamide, respectively, and labeled as [PCP – HCl] + . The loss of NaCl in CID experiments employing positive mode ESI was previously reported , and also shown in the MS/MS spectrum of [CP + Na] + obtained in this work and supported by computational elucidation of the suggested mechanism (see Figures S2 and S3 in the SI). The loss of HCl from protonated cyclophosphamide was also previously reported by Busker et al…”

Section: Resultssupporting

confidence: 87%

Analysis of the Fragmentation Pathways for the Collision-Induced Dissociation of Protonated Cyclophosphamide: A Mass Spectrometry and Quantum Mechanical Study

Korany

Ritacco

Dabbish

et al. 2022

J. Chem. Inf. Model.

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Cyclophosphamide is a well-known anticancer agent acting by means of DNA alkylation. Associated with its tumor selectivity, it also possesses a wide spectrum of toxicities. As the requirement of metabolic activation before cyclophosphamide exerts either its therapeutic or toxic effects is well recognized, research aiming at elucidating the pathways that lead to the activation of this drug is of key importance. This has created the necessity for developing an effective analytical method for detecting cyclophosphamide and its breakdown products. In this paper, an Acquity TQ tandem quadrupole mass spectrometer equipped with electrospray ionization in positive-ion mode was employed for detecting cyclophosphamide in its protonated form. The full-scan mass spectrum of cyclophosphamide shows two ion clusters displaying the characteristic isotopic pattern of two chlorine atoms and assigned as sodiated cyclophosphamide, [CP + Na]+, and protonated cyclophosphamide, [CP + H]+ or PCP. With the aid of quantum mechanical DFT calculation, free energy differences in the gas phase among PCP protomers were computed with respect to the most stable protomer being protonated on the 2-oxide oxygen of the 1,3,2-oxazaphosphorine-2-oxide ring. In addition, the interconversion mechanisms among the different protomers were also proposed by intercepting the corresponding transition states in the gas phase. Collision-induced dissociation (CID) of PCP generated six characteristic product ions. Fragmentation mechanisms were proposed and supported by computation. The calculated energy barriers for all of the located transition states were found to be accessible under the reported experimental conditions.

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Section: Resultssupporting

confidence: 87%

Analysis of the Fragmentation Pathways for the Collision-Induced Dissociation of Protonated Cyclophosphamide: A Mass Spectrometry and Quantum Mechanical Study

Korany

Ritacco

Dabbish

et al. 2022

J. Chem. Inf. Model.

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“…These ions can be conceived as species with two non-covalently interacting aminophosphonate molecules, presumably hydrogen-bonded through the P=O and NH groups. Interesting to note here is the observation of similar dimeric species and their fragments in the mass spectra of palladium(II) complexes of the studied aminophosphonate diesters 1-6 [40]. Hydrogen bonding N-HÁÁÁO=P in structures of these complexes was again found to be the main interaction that determines the crystal packing [11].…”

Section: Molecular Structures Of Quinolin-3-ylaminophosphonatesmentioning

confidence: 67%

N–H···O=P hydrogen-bonded dimers as the main structural motif of aminophosphonate diesters

2011

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Crystal and molecular structures of three aminophosphonate diesters, diethyl and dibutyl [a-(quinolin-3-ylamino)-N-benzyl]phosphonates (1 and 2) and dibutyl [a-anilino-(quinolin-3-yl)methyl]phosphonate (3) were reported and comparatively discussed. Characteristic structural features for these compounds are strong N-HÁÁÁO=P hydrogen bonds that connect two organophosphorus molecules in cyclic centrosymmetric dimer. Phosphoryl oxygen forms additional interaction with a C-H donor from the nearby aromatic group. Dimer formation in solution was also confirmed using electrospray ionization mass spectrometry. Mass spectra of six structurally similar aminophosphonate derivatives, 1-3 along with diethyl [a-anilino-(quinolin-3-yl)methyl]phosphonate (4), diethyl and dibutyl [a-anilino-(quinolin-2-yl)methyl]phosphonates (5 and 6) were studied and dimolecular ions [2M ? Na] ? and [2M ? H] ? were observed.Keywords Aminophosphonate Á Hydrogen-bonded dimers Á X-ray structure analysis Á ESI mass spectrometry Electronic supplementary material The online version of this article (

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“…ESI‐MS is a powerful and versatile technique for structural identification of metal‐containing aqueous solutions. A variety of platinum and palladium complexes containing various ligands have been previously investigated by using ESI‐MS . Nevertheless, only limited mass spectral data regarding the hydrolysis of cisplatin are available in the literature .…”

Section: Introductionmentioning

confidence: 99%

Electrospray ionization mass spectrometry for the hydrolysis complexes of cisplatin: implications for the hydrolysis process of platinum complexes

2017

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Non-enzyme-dependent hydrolysis of the drug cisplatin is important for its mode of action and toxicity. However, up until today, the hydrolysis process of cisplatin is still not completely understood. In the present study, the hydrolysis of cisplatin in an aqueous solution was systematically investigated by using electrospray ionization mass spectrometry coupled to liquid chromatography. A variety of previously unreported hydrolysis complexes corresponding to monomeric, dimeric and trimeric species were detected and identified. The characteristics of the Pt-containing complexes were investigated by using collision-induced dissociation (CID). The hydrolysis complexes demonstrate distinctive and correlative CID characteristics, which provides tools for an informative identification. The most frequently observed dissociation mechanism was sequential loss of NH , H O and HCl. Loss of the Pt atom was observed as the final step during the CID process. The formation mechanisms of the observed complexes were explored and experimentally examined. The strongly bound dimeric species, which existed in solution, are assumed to be formed from the clustering of the parent compound and its monohydrated or dihydrated complexes. The role of the electrospray process in the formation of some of the observed ions was also evaluated, and the electrospray ionization-related cold clusters were identified. The previously reported hydrolysis equilibria were tested and subsequently refined via a hydrolysis study resulting in a renewed mechanistic equilibrium system of cisplatin as proposed from our results. Copyright © 2017 John Wiley & Sons, Ltd.

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Electrospray Ionization Mass Spectrometry of Palladium(II) Quinolinylaminophosphonate Complexes

Cited by 5 publications

References 39 publications

Analysis of the Fragmentation Pathways for the Collision-Induced Dissociation of Protonated Cyclophosphamide: A Mass Spectrometry and Quantum Mechanical Study

Analysis of the Fragmentation Pathways for the Collision-Induced Dissociation of Protonated Cyclophosphamide: A Mass Spectrometry and Quantum Mechanical Study

N–H···O=P hydrogen-bonded dimers as the main structural motif of aminophosphonate diesters

Electrospray ionization mass spectrometry for the hydrolysis complexes of cisplatin: implications for the hydrolysis process of platinum complexes

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