کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
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1192344 | 1492317 | 2011 | 9 صفحه PDF | دانلود رایگان |
![عکس صفحه اول مقاله: Generation and characterization of distonic dehydrophenoxide radical anions under electrospray and atmospheric pressure chemical ionizations Generation and characterization of distonic dehydrophenoxide radical anions under electrospray and atmospheric pressure chemical ionizations](/preview/png/1192344.png)
We have explored the possibilities of generating radical anions under electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) conditions. By using different sets of ortho-, meta-, and para-isomers of nitrobenzoic acids, methylphenols, and nitrophenols, and m-, and p-isomers of hydroxybenzaldehydes and hydroxyacetophenones as the precursor molecules, we have successfully generated the isomeric distonic dehydrophenoxide radical anions (m/z 92) using the ESI process by applying relatively high capillary voltages, the in-source dissociation (ISD) condition. Under the same conditions, the o-hydroxybenzaldehyde and the o-hydroxyacetophenone yielded the even-electron dehydrophenoxide anion (m/z 93) due to the well-known ortho-effect. The distonic phenoxide radical anions at m/z 92 were also generated under APCI-ISD conditions by using m- and p-isomers of nitrobenzaldehydes and nitroacetophenones. While the o-nitrobenzaldehyde and the o-nitroacetophenone mainly yielded the phenoxide anion at m/z 93, due to the ortho-effect. The collision-induced dissociation (CID) experiments of all the anionic precursor molecules formed from either ESI or APCI produced comparable mass spectra as those observed in the ESI-ISD or the APCI-ISD experiments. The radical anions at m/z 92 reacted with CO2 and O2 to form the CO2 adduct and the oxygen atom abstraction product, respectively, revealing the dual-character of the distonic radical anions, the phenide ion and the phenyl radical. Computational studies support the results of the ion-molecule reactions.
Figure optionsDownload high-quality image (123 K)Download as PowerPoint slideResearch highlights▶ Distonic phenoxide radical anions at m/z 92 are generated via ESI or APCI process. ▶ Substituted aromatic compounds are suitable precursor molecules. ▶ CID experiments and ion-molecule reactions are performed. ▶ The radical anions exhibit dual characteristics, phenide ion and phenoxyl radical. ▶ Certain ortho-substituted compounds produce the phenoxide anion at m/z 93.
Journal: International Journal of Mass Spectrometry - Volume 299, Issues 2–3, 15 January 2011, Pages 169–177