Grafting efficiency of synthetic polymers onto biomaterials: A comparative study of grafting- from versus grafting- to

Hansson, S., Trouillet, V., Tischer, T., Goldmann, A.S., Carlmark, A., Barner-Kowollik, C., & Malmström, E. (2013) Grafting efficiency of synthetic polymers onto biomaterials: A comparative study of grafting- from versus grafting- to. Biomacromolecules, 14(1), pp. 64-74.

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In the present study, the two grafting techniques grafting-from - by activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) - and grafting-to - by copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) - were systematically compared, employing cellulose as a substrate. In order to obtain a meaningful comparison, it is crucial that the graft lengths of the polymers that are grafted from and to the substrates are essentially identical. Herein, this was achieved by utilizing the free polymer formed in parallel to the grafting-from reaction as the polymer for the grafting-to reaction. Four graft lengths were investigated, and the molar masses of the four free polymers (21 ≤ Mn ≤ 100 kDa; 1.07 ≤ M ≤ 1.26), i.e. the polymers subsequently employed in the grafting-to reaction, were shown to be in the same range as the molar masses of the polymers grafted from the surface (23 ≤ Mn ≤ 87 kDa; 1.08 ≤ M ≤ 1.31). The molecular weights of the chains grafted from the surface were established after cleavage from the cellulose substrates via size exclusion chromatography (SEC). High-resolution Fourier transform infrared microscopy (FT-IRM) was employed as an efficient tool to study the spatial distribution of the polymer content on the grafted substrates. In addition, the functionalized substrates were analyzed by X-ray photoelectron spectroscopy (XPS), contact angle (CA) measurements, and field-emission scanning electron microscopy (FE-SEM). For cellulose substrates modified via the grafting-from approach, the content of polymer on the surfaces increased with increasing graft length, confirming the possibility to tailor not only the length of the polymer grafts but also the polymeric content on the surface. In comparison, for the grafting-to reaction, the grafted content could not be controlled by varying the length of the preformed polymer: the polymer content was essentially the same for the four graft lengths. Consequently, the obtained results, when employing cellulose as a substrate and under these conditions, suggest that the grafting-from approach is superior to the grafting-to technique with respect to controlling the distribution of the polymeric content on the surface. © 2012 American Chemical Society.

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ID Code: 99351
Item Type: Journal Article
Refereed: Yes
Keywords: Activators regenerated by electron transfers, ARGET ATRP, Azide-alkyne cycloaddition, Cellulose substrates, Comparative studies, Field emission scanning electron microscopy, Fourier transform infrared microscopies, Free polymers, Functionalized substrates, Grafting efficiency, Grafting techniques, Grafting-to, High resolution, Polymer content, Polymer grafts, Synthetic polymers, Acetylene, Atom transfer radical polymerization, Biological materials, Cellulose, Contact angle, Enamels, Photoelectrons, Polymers, Substrates, X ray photoelectron spectroscopy, Grafting (chemical), biomaterial, copper, polymer, article, catalysis, chemical modification, chemical reaction, comparative study, cycloaddition, deprotection reaction, electron transfer atom transfer radical polymerization, electron transport, flow rate, gel permeation chromatography, hydrophobicity, molecular weight, polymerization, priority journal, surface property, synthesis, Biocompatible Materials, Chemistry, Pharmaceutical
DOI: 10.1021/bm3013132
ISSN: 1525-7797
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 17 May 2017 00:41

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