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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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ECD FT-ICR mass spectrum (top) and CID FT-ICR mass spectrum (bottom) of [M + 4H]4+ ions of PAMAMG1NH2.
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fig2: ECD FT-ICR mass spectrum (top) and CID FT-ICR mass spectrum (bottom) of [M + 4H]4+ ions of PAMAMG1NH2.

Mentions: Electrospray ionization of the generation 1 PAMAM dendrimer, containing ethylenediamine core, two tertiary amine branches (generations 0 and 1), and eight primary amino surface groups, results in the formation of multiply protonated molecular ions [M + 2H]2+ through [M + 4H]4+. The fragmentation for each charge state was very similar. Mass spectra shown here were obtained from the most abundant charge state, i.e., [M + 4H]4+ ions. The ECD mass spectrum of the [M + 4H]4+ ions of PAMAMG1NH2 is shown in Figure 2 (top) and the fragments observed are detailed in Supplementary Table S-2. The dominant fragments originate from the inner generation (G0). The peaks at m/z 592.9225 and 289.2342 can be assigned to G0(in)2+ and G0(y)+ fragments, respectively. The c/z• cleavages are found only as a minor channel. Other abundant fragment ions at m/z 388.3021 and 159.1366 are attributed to secondary fragmentation and can be assigned to [Gcore(out)G0(a)]+ and [G0(out)G1(a)]+, respectively. These fragments are presumably the result of cleavage of the amide bond followed by loss of CO, together with cleavage at the tertiary amine. Secondary fragmentation reactions involving a cleavages were seen for both PAMAMG1NH2 and PAMAMG2OH.


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 + 4H]4+ ions of PAMAMG1NH2.
© Copyright Policy
Related In: Results  -  Collection

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

fig2: ECD FT-ICR mass spectrum (top) and CID FT-ICR mass spectrum (bottom) of [M + 4H]4+ ions of PAMAMG1NH2.
Mentions: Electrospray ionization of the generation 1 PAMAM dendrimer, containing ethylenediamine core, two tertiary amine branches (generations 0 and 1), and eight primary amino surface groups, results in the formation of multiply protonated molecular ions [M + 2H]2+ through [M + 4H]4+. The fragmentation for each charge state was very similar. Mass spectra shown here were obtained from the most abundant charge state, i.e., [M + 4H]4+ ions. The ECD mass spectrum of the [M + 4H]4+ ions of PAMAMG1NH2 is shown in Figure 2 (top) and the fragments observed are detailed in Supplementary Table S-2. The dominant fragments originate from the inner generation (G0). The peaks at m/z 592.9225 and 289.2342 can be assigned to G0(in)2+ and G0(y)+ fragments, respectively. The c/z• cleavages are found only as a minor channel. Other abundant fragment ions at m/z 388.3021 and 159.1366 are attributed to secondary fragmentation and can be assigned to [Gcore(out)G0(a)]+ and [G0(out)G1(a)]+, respectively. These fragments are presumably the result of cleavage of the amide bond followed by loss of CO, together with cleavage at the tertiary amine. Secondary fragmentation reactions involving a cleavages were seen for both PAMAMG1NH2 and PAMAMG2OH.

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