Generational, skeletal and substitutional diversities in generation one poly(amidoamine) dendrimers

Xiangyang Shi, I. Bányai, Mohammad T. Islam, Wojciech Lesniak, Denzel Z. Davis, James R. Baker, Lajos P. Balogh

Research output: Contribution to journalArticle

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Abstract

Structural deviations of ethylenediamine core polyamidoamine (PAMAM) dendrimers and derivatives can be defined as skeletal and/or substitutional diversities. Detailed analysis of dendrimer starting materials and derivatives is necessary to understand the intrinsic characteristics of commercial dendrimer materials and their variations related to subsequent surface modifications. In this paper, structural deviations of ethylenediamine core generation 1 PAMAM dendrimers (PAMAM_E1 or E1) are studied and determined in a frame of a systematic investigation using combined characterization techniques. A primary amine-terminated PAMAM dendrimer of generation 1 (E1.NH2) was used as a starting material to synthesize glycidol (E1.N(Gly)OH) and acetamide-terminated (E1.NHAc) dendrimers. The purity and homogeneity of these dendrimers were extensively characterized by polyacrylamide gel electrophoresis (PAGE), capillary electrophoresis (CE), gel permeation chromatography (GPC), acid-base titration, nuclear magnetic resonance (NMR), matrix-assisted laser desorption ionization-time of flight (MALDI-TOF) and electrospray ionization (ESI) mass spectrometry. PAGE and CE studies showed that electrophoretic mobilities at pH 2.5 are in the order of E1.NH2>E1.N(Gly)OH>E1. NHAc. Mass spectrometry and NMR investigations (1H, 13C DEPT-135, and 13C NMR, COSY, HETCOR, NOESY) suggested that (a) the studied E1 dendrimers were generationally pure, (b) E1.NHAc and E1.N(Gly)OH dendrimers, and essentially had the same defects and skeletal diversity as E1.NH2 did. The broad distribution of the main peak in the CE electropherogram of E1.N(Gly)OH revealed the incomplete hydroxylation of E1.NH2 resulting in additional substitutional diversity between the dendrimer molecules. Potentiometric titration studies proved that overall numbers of terminal and tertiary amine groups also deviated from the theoretical values. NMR spectroscopy was applied for both qualitative and quantitative analysis of the structural defects of dendrimers and derivatives. E1.NH 2 and E1.NHAc exhibited only minor deviations from ideal structures and, respectively, displayed a narrow distribution; while E1.N(Gly)OH had a much broader distribution centered around 14±3 glycidol substituents. The study of structural variations in generation 1 PAMAMs provides new insights for the characterization of higher generation PAMAM dendrimers and derivatives both in terms of the skeletal deviations as well as other resulting diversities related to dendrimer surface functionalization.

Original languageEnglish
Pages (from-to)3022-3034
Number of pages13
JournalPolymer (United Kingdom)
Volume46
Issue number9
DOIs
Publication statusPublished - Apr 15 2005

Fingerprint

Dendrimers
ethylenediamine
glycidol
Capillary electrophoresis
Derivatives
Nuclear magnetic resonance
Polyacrylates
Electrophoresis
Titration
Poly(amidoamine)
Amines
Mass spectrometry
Gels
Electrospray ionization
Electrophoretic mobility
Hydroxylation
Defects
Gel permeation chromatography
Nuclear magnetic resonance spectroscopy
Ionization

Keywords

  • Characterization
  • Dendrimer
  • Distribution

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics

Cite this

Generational, skeletal and substitutional diversities in generation one poly(amidoamine) dendrimers. / Shi, Xiangyang; Bányai, I.; Islam, Mohammad T.; Lesniak, Wojciech; Davis, Denzel Z.; Baker, James R.; Balogh, Lajos P.

In: Polymer (United Kingdom), Vol. 46, No. 9, 15.04.2005, p. 3022-3034.

Research output: Contribution to journalArticle

Shi, Xiangyang ; Bányai, I. ; Islam, Mohammad T. ; Lesniak, Wojciech ; Davis, Denzel Z. ; Baker, James R. ; Balogh, Lajos P. / Generational, skeletal and substitutional diversities in generation one poly(amidoamine) dendrimers. In: Polymer (United Kingdom). 2005 ; Vol. 46, No. 9. pp. 3022-3034.
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