Contrasting behavior of tetracene and perylene in collision-induced dissociation: a theoretical interpretation

Fleurat‐Lessard, Paul; Pointet, Karine; Milliet, A.

doi:10.1002/(sici)1096-9888(199907)34:7<768::aid-jms833>3.0.co;2-3

Cited by 4 publications

(3 citation statements)

References 22 publications

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“…The charge on either position leads to cleavage of the bond between the 9,10-carbon atoms because the 10-carbon atom is the most branched and strained; concurrent formation of the phenyl ring is energetically favored. The charge-induced ␤ bond cleavage and concurrent formation of a double-bond, such as the fragmentation step from 2b or c to d in Scheme 2 are reasonable [13,21]. The ␥-position chargetransfer from the 9-carbon atom (Scheme 2d) to the 6-carbon atom (Scheme 2g) is driven by stabilization of the charge at the 6-carbon atom (similar to benzyl cation).…”

Section: Boldenone and Methandrostenolonementioning

confidence: 99%

Collision-induced dissociation pathways of anabolic steroids by electrospray ionization tandem mass spectrometry

Guan

Soma

Luo

et al. 2006

J. Am. Soc. Mass Spectrom.

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Anabolic steroids are structurally similar compounds, and their product-ion spectra obtained by tandem mass spectrometry under electrospray ionization conditions are quite difficult to interpret because of poly-ring structures and lack of a charge-retaining center in their chemical structures.In the present study, the fragmentation of nine anabolic steroids of interest to the racing industry was investigated by using triple quadrupole mass spectrometer, Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer, and a linear ion trap instrument. With the aid of an expert system software (Mass Frontier version 3.0), accurate mass measurements, and multiple stage tandem mass spectrometric (MS n ) experiments, fragmentation pathways were elucidated for boldenone, methandrostenolone, tetrahydrogestrinone (THG), trenbolone, normethandrolone and mibolerone. Small differences in the chemical structures of the steroids, such as an additional double-bond or a methyl group, result in significantly different fragmentation pathways. The fragmentation pathways proposed in this paper allow interpretation of major product ions of other anabolic steroids reported by other researchers in a recent publication [19]. The proposed fragmentation pathways are helpful for characterization of new steroids. The approach used in this study for elucidation of the fragmentation pathways is helpful in interpretation of complicated product-ion spectra of other compounds, drugs and their metabolites. (J Am Soc Mass Spectrom 2006, 17, 477-489)

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Section: Boldenone and Methandrostenolonementioning

confidence: 99%

Collision-induced dissociation pathways of anabolic steroids by electrospray ionization tandem mass spectrometry

Guan

Soma

Luo

et al. 2006

J. Am. Soc. Mass Spectrom.

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“…These findings were in contrast to a previous report in which perylene commonly generated molecular ions and did not readily form protonated analytes due to its notably low proton affinity. 35 The findings provide empirical support for the exceptional protonation capabilities exhibited by the AESI source.…”

Section: ■ Results and Discussionmentioning

confidence: 70%

“…Perylene and 1-nitropyrene exhibited radical cations at m / z 252.2 (Figure E) and 247.3 (Figure S9), respectively, and protonated analytes ([M + H] + ) at m / z 253.2 (Figure E) and 248.1 (Figure S9), respectively. These findings were in contrast to a previous report in which perylene commonly generated molecular ions and did not readily form protonated analytes due to its notably low proton affinity . The findings provide empirical support for the exceptional protonation capabilities exhibited by the AESI source.…”

Section: Resultsmentioning

confidence: 99%

Arc-Induced Electrospray Ionization Mass Spectrometry

Huang,

Zeng,

et al. 2023

Anal. Chem.

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Arc-induced electrospray ionization mass spectrometry (AESI-MS) was developed during which alternating current electrospray is simply achieved through the arc plasma. The AESI source exploits the arc's temperature and charge properties to generate aerosols consisting of charged microdroplets. The electrospray region, in which organic molecules are contained within microdroplets, partially overlaps with the arc plasma region. Guided by the electric field, these molecules undergo ionization, yielding ionic target analytes. AESI represents a soft ionization method that combines the mechanisms of atmospheric pressure chemical ionization and electrospray ionization, facilitating the ionization of analytes with wide ranging polarities. The precisely targeted spraying area enhances ion entry into the mass analyzer, thereby enabling excellent ionization efficiency. The AESI source exhibits several notable advantages over the electrospray ionization source, including an elevated but comparable level of active species concentrations and types, simplified mass spectra for direct amino acid analysis, high salt tolerance, versatile analysis of compounds with varying polarities, and reliable quantitative analysis of amino acids in complex matrices. Overall, AESI broadens the methodologies employed to generate microdroplets, providing a technological and scientific framework for creating distinctive electrospray ionization techniques.

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Diastereomeric differentiation of peptides with CuII and FeII complexation in an ion trap mass spectrometer

Lagarrigue¹,

Bossée²,

Afonso³

et al. 2006

J. Mass Spectrom.

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Complexation by transition metal ions (CuII and FeII) was successfully used to differentiate the diastereomeric YAGFL, YDAGFL and Y(D)AGF(D)L pentapeptides by electrospray ionization-ion trap mass spectrometry in the positive ion mode using low-energy collision conditions. This distinction was allowed by the stereochemical effects due to the (D)Leu/(L)Leu and the (D)Ala/(L)Ala residues yielding various steric interactions which direct relative dissociation rate constants of the binary [(M - H) + MeII]+ complexes (Me = Cu or Fe) subjected to low-energy, collision-induced dissociation processes. The interpretation of the collision-induced dissociation spectra obtained from the diastereomeric cationized peptides allowed the location of the deprotonated site(s), leading to the postulation of ion structures and fragmentation pathways for both the [(M - H) + CuII]+ and [(M - H) + FeII]+ complexes, which differed significantly. With CuII, consecutive fragmentations, initiated by the decarboxylation at C-terminus, were favored relative to sequence product ions. On the other hand, with FeII, competitive fragmentations resulting in abundant sequence product ions and significant internal losses were preferred. This could be explained by different localizations of the negative charge, which directs the orientation of both the [(M - H) + CuII]+ and [(M - H) + FeII]+ binary complexes fragmentations. Indeed, the free negative charge of the [(M - H) + CuII]+ ions was mainly located at one oxygen atom: either at the C-terminal carboxylic group or, to a minor extent, at the Tyr phenol group (i.e. zwitterionic forms). On the other hand, the negative charge of the [(M - H) + FeII]+ ions was mainly located at one of the nitrogen atoms of the peptide backbone and coordinated to FeII (i.e. salt non-zwitterionic form).Moreover, this study reveals the particular behavior of CuII reduced to CuI, which promotes radical losses not observed from the peptide-FeII complexes. Finally, this study shows the analytical potentialities of the complexation of transition metal ions with peptides providing structural information complementary to that obtained from low-energy, collision-induced dissociation processes of protonated or deprotonated peptides.

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Contrasting behavior of tetracene and perylene in collision-induced dissociation: a theoretical interpretation

Cited by 4 publications

References 22 publications

Collision-induced dissociation pathways of anabolic steroids by electrospray ionization tandem mass spectrometry

Collision-induced dissociation pathways of anabolic steroids by electrospray ionization tandem mass spectrometry

Arc-Induced Electrospray Ionization Mass Spectrometry

Diastereomeric differentiation of peptides with CuII and FeII complexation in an ion trap mass spectrometer

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