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The transformation from 2°‐amine to 3°‐amine of cyclam ring alters the fragmentation patterns of 1‐tosylcytosine‐cyclam conjugates

Kobetić, Renata; Ključarić, Valentina; Saftić, Dijana; Matić, Josipa; Ban, Željka; Kazazić, Snježana; Žinić, Biserka (2018) The transformation from 2°‐amine to 3°‐amine of cyclam ring alters the fragmentation patterns of 1‐tosylcytosine‐cyclam conjugates. Journal of Mass Spectrometry, 53 . pp. 655-664. ISSN 1076-5174

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The novel N‐1‐sulfonylcytosine‐cyclam conjugates 1 and 2 conjugates are ionized by electrospray ionization mass spectrometry (ESI MS) in positive and negative modes (ES+ and ES−) as singly protonated/deprotonated species or as singly or doubly charged metal complexes. Their structure and fragmentation behavior is examined by collision induced experiments. It was observed that the structure of the conjugate dictated the mode of the ionization: 1 was analyzed in ES− mode while 2 in positive mode. Complexation with metal ions did not have the influence on the ionization mode. Zn2+ and Cu2+ complexes with ligand 1 followed the similar fragmentation pattern in negative ionization mode. The transformation from 2°‐amine to 1 to 3°‐amine of cyclam ring in 2 leads to the different fragmentation patterns due to the modification of the protonation priority which changed the fragmentation channels within the conjugate itself. Cu2+ ions formed complexes practically immediately, and the priority had the cyclam portion of the ligand 2. The structure of the formed Zn2+ complexes with ligand 2 depended on the number of 3° amines within the cyclam portion of the conjugate and the ratio of the metal:ligand used. The cleavage of the cyclam ring of metal complexes is driven by the formation of the fragment that suited the coordinating demand of the metal ions and the collision energy applied. Finally, it was shown that the structure of the cyclam conjugate dictates the fragmentation reactions and not the metal ions.

Item Type: Article
Additional Information: Croatian Science Foundation, Grant/Award Numbers: 1447 and HRZZ 1447; Croatian Ministry of Science, Education and Sport, Grant/Award Number: 098-0982914-2935
Uncontrolled Keywords: Cu2+ and Zn2+ complexes; cyclam conjugate; ESI‐MS; fragmentation reactions; N‐1‐ tosylcytosine ring stability
Subjects: NATURAL SCIENCES > Chemistry
Divisions: Division of Organic Chemistry and Biochemistry
Division of Physical Chemistry
Project titleProject leaderProject codeProject type
Višenamjensko očitavanje DNA / RNA sekundarne strukture molekularnim kemijskim senzorima-DNA/RNA-MolSenseIvo PiantanidaIP-2013-11-1477HRZZ
Sinteza novih biološki aktivnih derivata nukleobaza i nukleotida-Biserka Žinić098-0982914-2935MZOS
Depositing User: Dijana Pavlović Saftić
Date Deposited: 11 Dec 2019 11:15
DOI: 10.1002/jms.4197

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