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Abstract

A series of N-(1,3-diphenylallyl)benzenamine derivatives (M) were investigated by electrospray ionization mass spectrometry in the positive-ion mode. Both the anomalous [M−H]⁺ and the regular [M+H]⁺ were observed in the ESI mass spectra. The occurrence of [M−H]⁺ has been supported by accurate mass spectrometry, liquid chromatography mass spectrometry, and tandem mass spectrometry analysis. Calculation results indicated that formation of [M−H]⁺ is attributed to the ion-molecule reaction of M with the protonated ESI solvent molecule (e.g. CH₃OH₂⁺) via hydride abstraction from a tertiary C_sp3−H. The competing ionization processes leading to [M−H]⁺ or [M+H]⁺ were significantly affected by the concentration of formic acid in the electrospray ionization solvent and the proton affinity of the N atom.

Keywords

3-diphenylallyl)benzenamine electrospray ionization mass spectrometry two competing ionization processes

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References

Cheng

Wong

Wang

et al.

Identification and characterization of molecular targets of natural products by mass spectrometry. Mass Spectrom Rev 2010; 29: 126.

Fang

Miao

Tidswell

et al.

Mass spectrometry analysis of new chemical entities for pharmaceutical discovery. Mass Spectrom Rev 2008; 27: 20.

Lattová

Perreault

. The usefulness of hydrazine derivatives for mass spectrometric analysis of carbohydrates. Mass Spectrom Rev 2013; 32: 366.

Zhang

et al.

On the origin of the methyl radical loss from deprotonated ferulic and isoferulic acids: Electronic excitation of a transient structure. J Am Soc Mass Spectrom 2013; 24: 941.

Vestal

. Methods of ion generation. Chem Rev 2001; 101: 361.

Crotti

AEM

Vessecchi

Lopes

JLC

et al.

Electrospray ionization mass spectrometry: Chemical processes involved in the ion formation from low molecular weight organic compounds. Quim Nova 2006; 29: 287.

Kebarle

Verkerk

. Electrospray: From ions in solution to ions in the gas phase, what we know now? Mass Spectrom Rev 2009; 28: 898.

Wang

Chai

et al.

Formation of [M + 15]⁺ ions from aromatic aldehydes by use of methanol: In-source aldolization reaction in electrospray ionization mass spectrometry. J Mass Spectrom 2011; 46: 1203.

Zhang

Jiang

Bai

et al.

Observation of the intermediates of in-source aldolization reaction in electrospray ionization mass spectrometry analysis of heteroaromatic aldehydes. Eur J Mass Spectrom 2015; 21: 51.

10.

Van Berkel

Kertesz

. Using the electrochemistry of the electrospray ion source. Anal Chem 2007; 79: 5510.

11.

De laMora

Van Berkel

Enke

et al.

Electrochemical processes in electrospray ionization mass spectrometry. J Mass Spectrom 2000; 35: 939.

12.

Vessecchi

Crotti

AEM

Guaratini

et al.

Radical ion generation processes of organic compounds in electrospray ionization mass spectrometry. Mini-Rev Org Chem 2007; 4: 75.

13.

Hou

Yuan

W-C

Fang

D-M

et al.

Unexpected [M−H +Na]⁺ radical ions in 3-isothiocyanato oxindoles detected by electrospray mass spectrometry. J Mass Spectrom 2013; 48: 344. DOI: 10.1002/jms.3144.

14.

Zhang

Jiang

Zou

et al.

Two competing ionization processes in electrospray mass spectrometry of indolyl benzo[b]carbazoles: Formation of M^+• versus [M + H]⁺. Rapid Commun Mass Spectrom 2015; 29: 263.

15.

Berkel

GJV

Kertesz

. Redox buffering in an electrospray ion source using a copper capillary emitter. J Mass Spectrom 2001; 36: 1125.

16.

Chai

Sun

Wan

et al.

Hydride abstraction in positive-ion electrospray interface: Oxidation of 1, 4-dihydropyridines in electrospray ionization mass spectrometry. Analyst 2011; 136: 4667.

17.

G-Y

X-Y

Fang

D-M

et al.

Unexpected [M−H]⁺ ions in cyclopenta[b]indoles detection by electrospray ionization mass spectrometry. J Mass Spectrom 2013; 48: 1266.

18.

Guo

Z-Q

Fang

D-M

Wang

J-H

et al.

[M−H]⁺ ions in 3-alkyl substituted indoles detected by electrospray mass spectrometry. Int J Mass Spectrom 2014; 361: 54.

19.

Kertesz

Van Berkel

. Surface-assisted reduction of aniline oligomers, N-phenyl-1,4-phenylenediimine and thionin in atmospheric pressure chemical ionization and atmospheric pressure photoionization. J Am Soc Mass Spectrom 2002; 13: 109.

20.

Karancsi

Slegel

. Reliable molecular mass determination of aromatic nitro compounds: Elimination of gas-phase reduction occurring during atmospheric pressure chemical ionization. J Mass Spectrom 1999; 34: 975.

21.

Benassi

Nefliu

et al.

Redox transformations in desorption electrospray ionization. Int J Mass Spectrom 2009; 280: 235.

22.

Qian

Nefliu

et al.

Ambient analysis of saturated hydrocarbons using discharge-induced oxidation in desorption electrospray ionization. J Am Soc Mass Spectrom 2010; 21: 261. https://doi.org/10.1016/j.jasms.2009.10.006 .

23.

Pasilis

Kertesz

Van Berkel

. Unexpected analyte oxidation during desorption electrospray ionization-mass spectrometry. Anal Chem 2008; 80: 1208.

24.

Xie

Yin

Sun

et al.

Extraction and derivatization in single drop coupled to MALDI-FTICR-MS for selective determination of small molecule aldehydes in single puff smoke. Anal Chim Acta 2009; 638: 198.

25.

Zhou

et al.

Treatment of cerebral ischemia by disrupting ischemia-induced interaction of nNOS with PSD-95. Nat Med 2010; 16: 1439.

26.

Jones

. Stroke: Disruption of the nNOS–PSD-95 complex is neuroprotective in models of cerebral ischemia. Nat Rev Neur 2011; 16: 1439.

27.

Florio

Loh

Huang

et al.

Disruption of nNOS-PSD95 protein-protein interaction inhibits acute thermal hyperalgesia and chronic mechanical allodynia in rodents. Br J Pharmacol 2009; 158: 494.

28.

J-X

Yea

Bai

X-F

et al.

Fei-Phos ligand-controlled asymmetric palladium-catalyzed allylic substitutions with structurally diverse nucleophiles: Scope and limitation. RSC Adv 2016; 6: 45495.

29.

Liu

Q-L

Chen

Jiang

Q-Y

et al.

A d-Camphor-based Schiff base as a highly efficient N,P ligand for enantioselective palladium-catalyzed allylic substitutions. Chem Inform 2016; 47: 1495.

30.

Frisch

Trucks

Schlegel

et al.

Gaussian 03, Revision B.03, Wallingford, CT: Gaussian, Inc., 2004.

31.

Wang

H-Y

Zhu

et al.

Gas phase decarbonylation and cyclization reactions of protonated N-methyl-N-phenylmethacrylamide and its derivatives via an amide Claisen rearrangement. J Am Soc Mass Spectrom 2012; 23: 2149.

32.

Wang

H-Y

Guo

Y-L

. Studies of rearrangement reactions of protonated and lithium cationized 2-pyrimidinyloxy-N-arylbenzylamine derivatives by MALDI -FTICR MS. J Am Soc Mass Spectrom 2004; 15: 1820.

33.

George

Sebastian

Reddy

et al.

Gas-phase nazarov cyclization of protonated 2-methoxy and 2-hydroxychalcone: An example of intramolecular proton-transport catalysis. J Am Soc Mass Spectrom 2009; 20: 805.

34.

Horning

Carroll

et al.

New picogram detection system based on a mass spectrometer with an external ionization source at atmospheric pressure. Anal Chem 1973; 45: 935.

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Two competing ionization processes in ESI-MS analysis of N -(1,3-diphenylallyl)benzenamines: formation of the unusual [M−H] + ion versus the regular [M+H] + ion

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