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Electron capture dissociation, electron detachment dissociation, and collision-induced dissociation of polyamidoamine (PAMAM) dendrimer ions with amino, amidoethanol, and sodium carboxylate surface groups.

Kaczorowska MA, Cooper HJ - J. Am. Soc. Mass Spectrom. (2008)

Bottom Line: ECD and EDD of the PAMAM dendrimers resulted in simple mass spectra, which are straightforward to interpret, whereas CID produced complex mass spectra.CID of the PAMAM dendrimers showed a strong dependence on the nature of the surface group and occurred mostly in the outer generation.The results demonstrate the potential utility of ECD and EDD as a tool for the structural analysis of PAMAM dendrimers.

View Article: PubMed Central - PubMed

Affiliation: School of Biosciences, University of Birmingham, Edgbaston, Birmingham, United Kingdom.

ABSTRACT
Here, we investigate the effect of the structure (generation) and nature of the surface groups of different polyamidoamine (PAMAM) dendrimers on electron-mediated dissociation, either electron capture dissociation (ECD) or electron detachment dissociation (EDD), and compare the fragmentation with that observed in collision-induced dissociation (CID). ECD and EDD of the PAMAM dendrimers resulted in simple mass spectra, which are straightforward to interpret, whereas CID produced complex mass spectra. The results show that electron-mediated dissociation (ECD and EDD) of PAMAM dendrimers does not depend on the nature of the surface group but tends to occur within the innermost generations. CID of the PAMAM dendrimers showed a strong dependence on the nature of the surface group and occurred mostly in the outer generation. The results demonstrate the potential utility of ECD and EDD as a tool for the structural analysis of PAMAM dendrimers.

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Related in: MedlinePlus

ECD FT-ICR mass spectrum (top) and CID FT-ICR mass spectrum (bottom) of [M + 6H]6+ ions of PAMAMG2OH.
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fig1: ECD FT-ICR mass spectrum (top) and CID FT-ICR mass spectrum (bottom) of [M + 6H]6+ ions of PAMAMG2OH.

Mentions: The ECD MS/MS spectrum of [M + 6H]6+ precursor ions is shown in Figure 1 (top). All fragments detected are described in Supplementary Table S-1, which can be found in the electronic version of this article. The most abundant peaks correspond to y fragments from generation 1 and generation zero. No b(•) ions were observed. The mass spectrum shows peaks corresponding to triply charged fragments G1(in)3+, G0(in)3+ singly charged Gcore(in)+, and quadruply charged G1(in)4+. These four fragments result from cleavage at tertiary amines. In addition, G(out) fragments, which also result from cleavage at tertiary amines but with the charge retained toward the surface of the dendrimer, were observed. These fragments also undergo secondary fragmentations, resulting in singly charged fragment ions [G1(out)G2(a)]+ at m/z 160.1205, [G0(out)G1(a)]+ at m/z 389.2624, and [G0(out)G1(out)]+ at m/z 459.2915. The c/z• cleavages that are the most abundant in the ECD of peptides/proteins were found here only as minor channels: G1(z)+ at m/z 274.1757 and G0(z)+ at m/z 732.4592.


Electron capture dissociation, electron detachment dissociation, and collision-induced dissociation of polyamidoamine (PAMAM) dendrimer ions with amino, amidoethanol, and sodium carboxylate surface groups.

Kaczorowska MA, Cooper HJ - J. Am. Soc. Mass Spectrom. (2008)

ECD FT-ICR mass spectrum (top) and CID FT-ICR mass spectrum (bottom) of [M + 6H]6+ ions of PAMAMG2OH.
© Copyright Policy
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC2571976&req=5

fig1: ECD FT-ICR mass spectrum (top) and CID FT-ICR mass spectrum (bottom) of [M + 6H]6+ ions of PAMAMG2OH.
Mentions: The ECD MS/MS spectrum of [M + 6H]6+ precursor ions is shown in Figure 1 (top). All fragments detected are described in Supplementary Table S-1, which can be found in the electronic version of this article. The most abundant peaks correspond to y fragments from generation 1 and generation zero. No b(•) ions were observed. The mass spectrum shows peaks corresponding to triply charged fragments G1(in)3+, G0(in)3+ singly charged Gcore(in)+, and quadruply charged G1(in)4+. These four fragments result from cleavage at tertiary amines. In addition, G(out) fragments, which also result from cleavage at tertiary amines but with the charge retained toward the surface of the dendrimer, were observed. These fragments also undergo secondary fragmentations, resulting in singly charged fragment ions [G1(out)G2(a)]+ at m/z 160.1205, [G0(out)G1(a)]+ at m/z 389.2624, and [G0(out)G1(out)]+ at m/z 459.2915. The c/z• cleavages that are the most abundant in the ECD of peptides/proteins were found here only as minor channels: G1(z)+ at m/z 274.1757 and G0(z)+ at m/z 732.4592.

Bottom Line: ECD and EDD of the PAMAM dendrimers resulted in simple mass spectra, which are straightforward to interpret, whereas CID produced complex mass spectra.CID of the PAMAM dendrimers showed a strong dependence on the nature of the surface group and occurred mostly in the outer generation.The results demonstrate the potential utility of ECD and EDD as a tool for the structural analysis of PAMAM dendrimers.

View Article: PubMed Central - PubMed

Affiliation: School of Biosciences, University of Birmingham, Edgbaston, Birmingham, United Kingdom.

ABSTRACT
Here, we investigate the effect of the structure (generation) and nature of the surface groups of different polyamidoamine (PAMAM) dendrimers on electron-mediated dissociation, either electron capture dissociation (ECD) or electron detachment dissociation (EDD), and compare the fragmentation with that observed in collision-induced dissociation (CID). ECD and EDD of the PAMAM dendrimers resulted in simple mass spectra, which are straightforward to interpret, whereas CID produced complex mass spectra. The results show that electron-mediated dissociation (ECD and EDD) of PAMAM dendrimers does not depend on the nature of the surface group but tends to occur within the innermost generations. CID of the PAMAM dendrimers showed a strong dependence on the nature of the surface group and occurred mostly in the outer generation. The results demonstrate the potential utility of ECD and EDD as a tool for the structural analysis of PAMAM dendrimers.

Show MeSH
Related in: MedlinePlus