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Structural characterization of chelator-terminated dendrimers and their synthetic intermediates by mass spectrometry.
J Mass Spectrom. 2005 Sep; 40(9):1203-14.JM

Abstract

Herein, we report the structural analysis of a novel family of iron-chelating dendrimers and their synthetic intermediates utilizing matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) and electrospray ionization ion trap (ESI IT) MS. These dendrimers share a benzene tricarbonyl core moiety attached to three tripodal branching units, each linking to three terminal groups, ranging from carboxyl, catechol and 3-hydroxy-6-methyl-pyran-4-one moieties and their protected analogs. In order to monitor the progression of dendrimer synthesis, all intermediates and final products were mass analyzed by conventional MALDI-TOF MS with and without alkali metal spiking. For structural characterization, interpretable post-source decay (PSD) and electrospray ionization ion trap MS/MS spectra were obtained from proton, sodium and potassium adducts of the dendrimers. One major route of dendrimer fragmentation was at or adjacent to the amide bonds either of the terminal chelating groups or near the core moiety. Fragmentation in the latter case was primarily at the N-terminal side of the amide bond and was directed by the proximity of a tertiary carbon of the branching unit. Furthermore, it was found that terminal ester, ether and amide linkages to the protecting and chelating groups could be sequentially broken in a single MS/MS spectrum through multiple cleavages resulting in product ions of decreasing intensity. Moreover, such cleavages could also be induced in a stepwise manner in a multistage ion trap MS(n) experiment.

Authors+Show Affiliations

Department of Medicinal-Pharmaceutical Chemistry, Faculty of Life Sciences, University of Vienna, Vienna, Austria.No affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

16127663

Citation

Berndt, Ursula E C., et al. "Structural Characterization of Chelator-terminated Dendrimers and Their Synthetic Intermediates By Mass Spectrometry." Journal of Mass Spectrometry : JMS, vol. 40, no. 9, 2005, pp. 1203-14.
Berndt UE, Zhou T, Hider RC, et al. Structural characterization of chelator-terminated dendrimers and their synthetic intermediates by mass spectrometry. J Mass Spectrom. 2005;40(9):1203-14.
Berndt, U. E., Zhou, T., Hider, R. C., Liu, Z. D., & Neubert, H. (2005). Structural characterization of chelator-terminated dendrimers and their synthetic intermediates by mass spectrometry. Journal of Mass Spectrometry : JMS, 40(9), 1203-14.
Berndt UE, et al. Structural Characterization of Chelator-terminated Dendrimers and Their Synthetic Intermediates By Mass Spectrometry. J Mass Spectrom. 2005;40(9):1203-14. PubMed PMID: 16127663.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Structural characterization of chelator-terminated dendrimers and their synthetic intermediates by mass spectrometry. AU - Berndt,Ursula E C, AU - Zhou,Tao, AU - Hider,Robert C, AU - Liu,Zu D, AU - Neubert,Hendrik, PY - 2005/8/30/pubmed PY - 2005/12/21/medline PY - 2005/8/30/entrez SP - 1203 EP - 14 JF - Journal of mass spectrometry : JMS JO - J Mass Spectrom VL - 40 IS - 9 N2 - Herein, we report the structural analysis of a novel family of iron-chelating dendrimers and their synthetic intermediates utilizing matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) and electrospray ionization ion trap (ESI IT) MS. These dendrimers share a benzene tricarbonyl core moiety attached to three tripodal branching units, each linking to three terminal groups, ranging from carboxyl, catechol and 3-hydroxy-6-methyl-pyran-4-one moieties and their protected analogs. In order to monitor the progression of dendrimer synthesis, all intermediates and final products were mass analyzed by conventional MALDI-TOF MS with and without alkali metal spiking. For structural characterization, interpretable post-source decay (PSD) and electrospray ionization ion trap MS/MS spectra were obtained from proton, sodium and potassium adducts of the dendrimers. One major route of dendrimer fragmentation was at or adjacent to the amide bonds either of the terminal chelating groups or near the core moiety. Fragmentation in the latter case was primarily at the N-terminal side of the amide bond and was directed by the proximity of a tertiary carbon of the branching unit. Furthermore, it was found that terminal ester, ether and amide linkages to the protecting and chelating groups could be sequentially broken in a single MS/MS spectrum through multiple cleavages resulting in product ions of decreasing intensity. Moreover, such cleavages could also be induced in a stepwise manner in a multistage ion trap MS(n) experiment. SN - 1076-5174 UR - https://www.unboundmedicine.com/medline/citation/16127663/Structural_characterization_of_chelator_terminated_dendrimers_and_their_synthetic_intermediates_by_mass_spectrometry_ L2 - https://doi.org/10.1002/jms.899 DB - PRIME DP - Unbound Medicine ER -