Synthesis and mass spectrometry analysis of quaternary cryptando-peptidic conjugates.
The bicyclic amines in the form of cryptands, the crown ether analogs, were used in the synthesis of cryptando-peptidic conjugates with simultaneous formation of quaternary ammonium nitrogen moiety. A series of model cryptando-peptidic conjugates at the peptide N-terminus was efficiently prepared by the standard Fmoc solid phase synthesis. Tandem mass spectrometric analysis of the obtained conjugates has shown the specific fragmentation pattern during MS/MS experiment. The obtained cryptandic quaternary ammonium group undergoes the Hofmann elimination during collision-induced dissociation fragmentation followed by the ethoxyl group elimination. The presented quaternization of cryptands by iodoacetylated peptides is relatively easy and compatible with standard solid-phase peptide synthesis. Additionally, the applicability of such peptide derivatives and their isotopologues selectively deuterated at the α-carbon in the quantitative LC-MS analysis was analyzed.
Faculty of Chemistry, University of Wrocław, F. Joliot-Curie 14, Wroclaw, Poland.
Remigiusz
R
Bąchor
Faculty of Chemistry, University of Wrocław, F. Joliot-Curie 14, Wroclaw, Poland.
Alicja
A
Kluczyk
Faculty of Chemistry, University of Wrocław, F. Joliot-Curie 14, Wroclaw, Poland.
Piotr
P
Stefanowicz
Faculty of Chemistry, University of Wrocław, F. Joliot-Curie 14, Wroclaw, Poland.
Zbigniew
Z
Szewczuk
D000588:Amines / Q000737:chemistry; D004988:Ethers, Cyclic / Q000737:chemistry*; D015394:Molecular Structure; D010455:Peptides / Q000138:chemical synthesis* / Q000737:chemistry; D000644:Quaternary Ammonium Compounds / Q000737:chemistry; D012545:Schiff Bases / Q000737:chemistry*; D060327:Solid-Phase Synthesis Techniques / Q000379:methods*; D053719:Tandem Mass Spectrometry / Q000379:methods
D000588:Amines; D004988:Ethers, Cyclic; D010455:Peptides; D000644:Quaternary Ammonium Compounds; D012545:Schiff Bases; C444241:cryptand
ESI-MS/MS; HDX; cryptands; fixed charge tags; quantitative analysis