ESI-mass spectrometry analysis of unsubstituted and disubstituted beta-cyclodextrins: fragmentation mode and identification of the AB, AC, AD regioisomers.
The study of unsubstituted and disubstituted beta-cyclodextrins (beta-CDs) by ESI-mass spectrometry is reported, applying a cone-induced fragmentation in the presence of a twofold excess of sodium chloride, in order to gain information about the fragmentation of the different regioisomers. On the basis of the fragmentation pattern observed for the unsusbstituted beta-CD, a statistical model shows that the fragments generated by every regioisomer of a disubstituted CD (AB, AC, and AD) are expected to differ in their relative intensity and, therefore, they can be used for correctly identifying the three different regioisomers. The model was tested on the three regioisomeric (AB, AC, and AD) diamino-beta-CDs and ditosyl-beta-CD and on the AC and AD regioisomers of dimesitylenesulphonyl-beta-CD, allowing in every case through statistical analysis of the fragmentation pattern the correct assignment of every regioisomer on the basis of an ESI mass spectrum (single quadrupole analyzer, high cone voltage) of the pure compounds. The absolute intensities of the fragmentation peaks were voltage-dependent but their ratios was voltage-independent, indicating that no mass bias in peak ratios is introduced by the analyzer. Given the fast time of analysis and its general applicability, independently from the substituents, we propose our method as an easy way to identify the regioisomers of disubstituted beta-CDs.
Sforza
Stefano
S
Department of Organic and Industrial Chemistry, University of Parma, Parma, Italy. stefano.sforza@unipr.it
Galaverna
Gianni
G
Corradini
Roberto
R
Dossena
Arnaldo
A
Marchelli
Rosangela
R
D003505:Cyclodextrins / Q000138:chemical synthesis / Q000737:chemistry*; D007536:Isomerism; D015394:Molecular Structure; D010446:Peptide Fragments / Q000138:chemical synthesis / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D013329:Structure-Activity Relationship; D047392:beta-Cyclodextrins
D003505:Cyclodextrins; D010446:Peptide Fragments; D047392:beta-Cyclodextrins; C031215:betadex