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Universal Two-Step Approach to Degradable and Electroactive Block Copolymers and Networks from Combined Ring-Opening Polymerization and Post-Functionalization via Oxidative Coupling Reactions
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.ORCID iD: 0000-0002-1922-128X
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
2011 (English)In: Macromolecules, ISSN 0024-9297, E-ISSN 1520-5835, Vol. 44, no 13, 5227-5236 p.Article in journal (Refereed) Published
Abstract [en]

We present a universal strategy for the facile synthesis of degradable and electroactive block copolymers and organogels (DEBCGs) based on aniline oligomers and polyesters in a two-step approach, here exemplified by the preparation of a series of DECBCGs based on aniline tetramer (AT) and poly(e-caprolactone) (PCL). Polyesters with an aniline dimer (AD) segment were first obtained by controlled ring-opening polymerization (ROP) of e-caprolactone initiated by the amine group of AD with or without 2,2-bis(epsilon-caprolactone-4-yl) propane (BCP). The postpolymerization modification via an oxidative coupling reaction between AD and a polyester was then used to form the electroactive segment AT in the copolymers or organogels. The molecular weight and conductivity of the block copolymers and organogels were controlled by the AT content. The chemical structure, electroactivity, and thermal properties of DEBCGs were investigated by FT-IR, NMR, SEC, UV, cyclic voltammetry, TGA, and DSC. Our general strategy for the synthesis of DECBCGs avoids the multiple step reactions and low efficiency involved in previous work.

Place, publisher, year, edition, pages
2011. Vol. 44, no 13, 5227-5236 p.
National Category
Chemical Sciences
URN: urn:nbn:se:kth:diva-37154DOI: 10.1021/ma2009595ISI: 000292417800022ScopusID: 2-s2.0-79959959355OAI: diva2:432431
Available from: 2011-08-03 Created: 2011-08-02 Last updated: 2011-11-23Bibliographically approved
In thesis
1. degradable electroactive polymers: Synthesis, Macromolecular architecture and scaffold design
Open this publication in new window or tab >>degradable electroactive polymers: Synthesis, Macromolecular architecture and scaffold design
2011 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Electrically conducting polymers induce specific cellular responses at the molecular level. One of the crucial limitations of the use of conducting polymers in tissue engineering is their inability to degrade. The incorporation of conductivity into degradable polymers to obtain materials that are both electroactive and degradable is therefore highly anticipated. Architecture plays an important role in the performance of polymers. To be able to achieve the optimal mechanical, degradation, thermal and biological properties for a particular biomedical application, it is desirable to promote architectural diversity.

 In the first part, by combining the electroactivity of conducting polymers and the degradability of aliphatic polyesters, we have designed and synthesized a series of linear, star-shaped, hyperbranched, and crosslinked degradable and electrically conducting polymers and hydrogels based on polylactide (PLA), polycaprolactone (PCL), and aniline oligomers such as aniline trimer, aniline tetramer, and aniline pentamer. The polymers and hydrogels obtained have good electroactivity, as indicated by their ultraviolet spectra and by cyclic voltammetry. The conductivities of the polymers and hydrogels are tuned by the content of the aniline oligomer and the macromolecular architecture. The hydrophilicity of the polymers was greatly increased after doping the aniline oligomer with acid, which overcomes the hydrophobicity of the PLA and PCL. Thermogravimetric analysis and differential scanning calorimetry studies show that these copolymers and hydrogels have good thermal properties compared to PLA and PCL. The swelling ratios of these hydrogels covered a wide range and were controlled by the degree of crosslinking, the oligoaniline content, and the pH of the surrounding solution.

 In the next part, methods for the facile synthesis of degradable conducting polymers and hydrogels were presented to avoid the multi-step reaction used in the earlier work. We developed a one-pot reaction for the synthesis of degradable conducting polysaccharide hydrogels based on chitosan and aniline tetramer. These hydrogels can form free-standing and flexible conducting films. This overcomes the drawback of polyaniline which could not be easily fabricated into a thin film in common organic solvents. We also presented a universal two-step approach to create degradable conductive diblock or triblock copolymers based on a polyester and aniline tetramer or aniline pentamer by a combination of ring opening polymerization and post-functionalization via an oxidative coupling reaction. The self-assembly behavior of the triblock copolymer consisting of a middle aniline pentamer segment and two bilateral polycaprolactone segments in chloroform as a selective solvent (selective for PCL segment) were also investigated by transmission electron microscopy and dynamic light scattering. The size of the nanoparticles from the assembly of the triblock copolymers depends on the molecular weight of the copolymer and on the aniline pentamer state.

 In the last part, electroactive degradable non-toxic porous tubular scaffolds were fabricated from a polymer blend of hyperbranched degradable conductive copolymer and PCL by a modified solution-casting/particle-leaching technique. The porous structure of the tubular scaffolds was investigated by scanning electron microscope and microcomputed tomography. The hydrophilicity of the blend films was greatly improved by doping with (±)-10-camphorsulfonic acid. The conductivity of the films was tuned by adjusting the ratio of hyperbranched degradable conducting copolymer to PCL. The cytotoxicity test with HaCaT keratinocytes indicated that the materials were non-toxic.

 These degradable electroactive copolymers and hydrogels with different architectures and properties have a great potential for meeting the requirements of biomedical application.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2011. 87 p.
Trita-CHE-Report, ISSN 1654-1081 ; 2011:55
Poly(lactide), poly(ε-caprolactone), ring-opening polymerization, carboxyl-capped aniline trimer, carboxyl-capped aniline pentamer, phenyl amino-capped aniline tetramer, coupling reaction, DCC/DMAP system, degradability, electroactivity, conductivity, macromolecular architecture, chitosan, hydrogel, block copolymer, functionalization, oxidative coupling reaction, self-assembly, toxicity, tubular porous scaffold, neural tissue engineering.
National Category
Engineering and Technology
urn:nbn:se:kth:diva-48171 (URN)978-91-7501-136-3 (ISBN)
Public defence
2011-12-07, F3, Lindstedsvägen 26, KTH,, Stockholm, 10:00 (English)
QC 20111123Available from: 2011-11-23 Created: 2011-11-16 Last updated: 2011-11-23Bibliographically approved

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