Rapidly formed quinalphos complexes with transition metal ions characterized by electrospray ionization mass spectrometry

Keller, Bernd O.; Esbata, Abdelhamid A.; Buncel, Erwin; Loon, Gary W. van

doi:10.1002/rcm.6570

Cited by 4 publications

(8 citation statements)

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“…Fragmentations of [L + Ag] + complexes, where L are aromatic amino acids: Phe, Tyr, Trp, or His, have been exhaustively studied through CID and through deuterium labeling. The CID of [His + Ag] + gives the histidine radical cation, His +• , from the loss of the silver atom Ag • 13,41a–41e. The dissociation of these amino acid complexes is comparable with the fragmentation process of the [AgL] + complexes with ligands 1 to 12 in this study.…”

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confidence: 72%

Electrospray mass spectrometry and molecular modeling study of formation and stability of silver complexes with diazaperylene and bisisoquinoline

et al. 2018

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The complex formation of the following diazaperylene ligands (L) 1,12-diazaperylene 1, 1,1'-bisisoquinoline 2, 2,11-disubstituted 1,12-diazaperylenes (alkyl = methyl, ethyl, isopropyl, 3, 5, 7), 3,3'-disubstituted 1,1'-bisisoquinoline (alkyl = methyl, ethyl, isopropyl, 4, 6, 8 and with R = phenyl, 11 and with pyridine 12), and the 5,8-dimethoxy-substituted diazaperylene 9, 6,6'-dimethoxy-substituted bisisoquinoline 10 with AgBF4 was investigated. Collision-induced dissociation measurements were used to evaluate the relative stabilities of the ligands themselves and for the [1:1] complexes as well as for the homoleptic and heteroleptic silver [1:2] complexes in the gas phase. This method is very useful in rapid screening of the stabilities of new complexes in the gas phase. The influence of the spatial arrangement of the ligands and the type of substituents employed for the complexation were examined. The effect of the preorganization of the diazaperylene on the threshold activation voltages and thus of the relative binding energies of the different complexes are discussed. Density functional theory calculations were used to calculate the optimized structures of the silver complexes and compared with the stabilities of the complexes in the gas phase for the first time.

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Section: Resultssupporting

confidence: 72%

Electrospray mass spectrometry and molecular modeling study of formation and stability of silver complexes with diazaperylene and bisisoquinoline

et al. 2018

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“…The increase in S/B observed in positive‐ion mode upon addition of either Cu 2+ or Ag + to the pesticide solution is likely because formation of the pesticide–metal complex is more likely to occur than H + adduction. Both Cu 2+ and Ag + have been reported to form stable complexes with phosphorothioate pesticides …”

Section: Resultsmentioning

confidence: 99%

“…Both Cu 2+ and Ag + have been reported to form stable complexes with phosphorothioate pesticides. [8,16] The formation of a metal-pesticide complex generally depends on the favorable interaction between the metal and an active site on the pesticide molecule. The active site for the phosphorothioate pesticides has been established to be the 'soft' thiophosphoryl S-atom ( Fig.…”

Section: Resultsmentioning

confidence: 99%

“…[15] A recent study showed that the OP-metal complex can be investigated using ESI/MS before the onset of degradation. [16] In that study, ESI/MS was used to characterize Ag + , Cu 2+ , and Hg 2+ complexes with the OP quinalphos in order to gain insight into the solution complexes formed between quinalphos and these transition metal ions. The 1 : 1 metal-quinalphos complexes were observed for Ag + and Cu 2+ , while a 2 : 3 complex was observed for Hg 2+ .…”

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confidence: 99%

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Gas-phase copper and silver complexes with phosphorothioate and phosphorodithioate pesticides investigated using electrospray ionization mass spectrometry

Mustapha

Pasilis

2015

J. Mass Spectrom.

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Efforts to improve agricultural productivity have led to a growing dependency on organophosphorus pesticides. Phosphorothioate and phosphorodithioate pesticides are organophosphorus pesticide subclasses with widespread application for the control of insects feeding on vegetables and fruits. However, even low doses of these pesticides can cause neurological problems in humans; thus, their determination and monitoring in agricultural foodstuffs is important for human health. Phosphorothioate and phosphorodithioate pesticides may be poorly ionized during electrospray, adversely affecting limits of detection. These pesticides can form complexes with Cu(2+) and Ag(+) , however, potentially improving ionization. In the present work, we used electrospray ionization/mass spectrometry (ESI/MS) to study fenitrothion, parathion, diazinon, and malathion coordination complexes with silver and copper ions. Stable 1 : 1 and 1 : 2 metal/pesticide complexes were detected. Mass spectra acquired from pesticide solutions containing Ag(+) or Cu(2+) showed a significant increase in signal-to-background ratio over those acquired from solutions containing only the pesticides, with Ag(+) improving detection more effectively than Cu(2+). Addition of Ag(+) to a pesticide solution improved the limit of detection by ten times. The relative affinity of each pesticide for Ag(+) was related to complex stability, following the order diazinon > malathion > fenitrothion > parathion. The formation of Ag(+)-pesticide complexes can significantly improve the detection of phosphorothioate and phosphorodithioate pesticides using ESI/MS. The technique could potentially be used in reactive desorption electrospray ionization/mass spectrometry to detect phosphorothioate and phosphorodithioate pesticides on fruit and vegetable skins.

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“…For positive ion mode the analyte solution was acidified to guarantee protonation. 28,29 The ESI-MS spectrum and its fragmentation pattern is shown in…”

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Silver ion binding to the organophosphorus pesticide diazinon and hydrolytic pathways revealed by mass spectrometric and NMR studies

et al. 2015

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This paper describes the first study of the interactions of Ag + with the organophosphorus (OP) insecticide, diazinon, 1. Electrospray ionization mass spectrometry (ESI-MS) with corroborative collision-induced dissociation-mass spectrometry (CID-MS), demonstrates that 1 forms a bidentate chelate with Ag + . The hydrolysis products of 1, the pyrimidinol (PY) and O,Odiethylphosphorothioic acid (PA), are also found to bind to Ag + via N (PY) and S (PA) Lewis base sites, respectively. 31 P and 1 H nuclear magnetic resonance (NMR) spectra in solution, followed over time with varying ratios of Ag + to 1, confirm the MS evidence and show Ag + catalysis of hydrolysis (e.g. complete hydrolysis of 1 in ca. 5 minutes (first-order half-life = 3 x 10 -4 day; k obs = 2 x 10 3 day -1 ) with equimolar Ag + ; this represents an approximate 150,000-fold enhancement in hydrolysis with Ag + as compared to its absence. A mechanism for the enhanced hydrolysis is proposed in which bidentate binding of Ag + to S of the P=S electrophilic site in tandem with binding to N of the leaving group stabilizes the S N 2(P) transition state relative to the ground state; this effect is described by qualitative energy profiles.Keywords: Electrospray ionization mass spectrometry (ESI-MS), Collision-induced dissociation (CID), P-31 and H-1 nuclear magnetic resonance (NMR) spectrometry, Silver ion catalysis

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Rapidly formed quinalphos complexes with transition metal ions characterized by electrospray ionization mass spectrometry

Cited by 4 publications

References 46 publications

Electrospray mass spectrometry and molecular modeling study of formation and stability of silver complexes with diazaperylene and bisisoquinoline

Electrospray mass spectrometry and molecular modeling study of formation and stability of silver complexes with diazaperylene and bisisoquinoline

Gas-phase copper and silver complexes with phosphorothioate and phosphorodithioate pesticides investigated using electrospray ionization mass spectrometry

Silver ion binding to the organophosphorus pesticide diazinon and hydrolytic pathways revealed by mass spectrometric and NMR studies

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