RAFT copolymerization of oppositely charged monomers and its use to tailor the composition of nonfouling polyampholytes with an UCST behaviour
Synthetic polyampholytes are attracting significant interest due to the possibility that they offer of combining oppositely charged repeating units in the same copolymer chain. This peculiar structure makes them appealing for the understanding of biological processes such as protein folding and DNA...
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Published in | Reaction chemistry & engineering Vol. 4; no. 2; pp. 436 - 446 |
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Main Authors | , , , |
Format | Journal Article |
Language | English |
Published |
Cambridge
Royal Society of Chemistry
04.02.2019
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Subjects | |
Online Access | Get full text |
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Summary: | Synthetic polyampholytes are attracting significant interest due to the possibility that they offer of combining oppositely charged repeating units in the same copolymer chain. This peculiar structure makes them appealing for the understanding of biological processes such as protein folding and DNA condensation as well as for application as pH- and salt-responsive gels. In addition, the alternation at the molecular level of charges with opposite signs holds promise in avoiding the fouling of proteins, bacteria, and marine organisms. Indeed, polymer reaction engineering assumes an important role in ensuring such charge alternation and in turn the efficacy of the polyampholyte coating. In this work, the reversible addition-fragmentation chain transfer (RAFT) copolymerization of the electrolyte monomers 3-sulfopropyl methacrylate potassium salt (anionic, SPMAK) and [2-(methacryloyloxy)ethyl]trimethylammonium chloride (cationic, MADQUAT) was studied in detail to highlight the influence of both the monomer and chain transfer agent (CTA) concentrations on the polymerization rate and copolymer composition. By analysing the residual monomer mixture composition
via in situ
nuclear magnetic resonance (
1
H NMR), the reactivity ratios for the two monomers were calculated. Interestingly, the values obtained in the case of RAFT copolymerization (
i.e. r
SPMAK
= 0.51 ± 0.03 and
r
MADQUAT
= 0.31 ± 0.03) are valid in the case of a conventional free-radical copolymerization under similar conditions. The optimized polyampholytes showed interesting aqueous properties, including an upper critical solution temperature (UCST), which was studied as a function of the salt concentration and polymer molecular weight. Finally, as a proof of concept, the efficacy of the synthesized polyampholytes as nonfouling coatings was assessed in the case of A375-P cells.
The RAFT copolymerization of oppositely-charged monomers is studied to optimize the composition of polyampholytes with an UCST behaviour and nonfouling properties. |
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Bibliography: | Davide Moscatelli received his Laurea cum laude in Chemical Engineering from Politecnico di Milano in 2002, and his PhD in Chemical Engineering in 2006. He is a full professor of Applied Physical Chemistry at Politecnico di Milano and he has been collaborating with ETH Zurich since 2007. His main research interests lie in material synthesis for technological applications, with particular emphasis on polymer materials, nanomaterials and chemical compounds for biomedical and oil & gas applications. The general aim of his research is the development of new approaches to synthesize and functionalize innovative, efficient, and tunable smart materials. He is a co-author of more than 120 papers on international journals and more than 10 patents, with an H-index of 26. He also serves as a lecturer of the Petroleum Technologies and Refining Processes course at Politecnico di Milano. He has supervised more than 100 Bachelor thesis students in Chemical Engineering, more than 100 Master thesis students in Chemical Engineering and Materials Engineering, and more than 10 PhD theses in Industrial Chemistry and Chemical Engineering. He is Vice Director of the PhD course of Industrial Chemistry and Chemical Engineering at Politecnico di Milano (http://phd.chem.polimi.it/staff/) and, since 2017, he has been a member of the Faculty Committee for the strategic plan Polimi2040 at Politecnico di Milano. Davide Moscatelli is a member of the editorial board and advisory panel of several international scientific journals. He is a co-founder of Captive Systems srl, a spin-off company of Politecnico di Milano active in the use of smart nanomaterials for wastewater treatments. Electronic supplementary information (ESI) available. See DOI 10.1039/c8re00221e |
ISSN: | 2058-9883 2058-9883 |
DOI: | 10.1039/c8re00221e |