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Facile Synthesis of Dopa-Functional Polycarbonates viaThiol-Ene-Coupling Chemistry towards Self-Healing Gels
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.ORCID iD: 0000-0003-0319-6494
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.ORCID iD: 0000-0002-9200-8004
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.ORCID iD: 0000-0002-9372-0829
2016 (English)In: Journal of Polymer Science Part A: Polymer Chemistry, ISSN 0887-624X, E-ISSN 1099-0518, Vol. 54, no 15Article in journal (Refereed) Published
Abstract [en]

Since extraction of the naturally occurring mussel-foot proteins is expensive and time-consuming, routes towards synthetic analogues are continuously being explored. Often, these methods involve several protection and deprotection steps, making the synthesis of synthetic analogues time-consuming and expensive as well. Herein, we show that UV-initiated thiol-ene coupling between a thiol-functional dopamine derivative and an allyl-functional aliphatic polycarbonate can be used as a fast and facile route to dopa-functional materials. Different thiol-to-allyl ratios and irradiation protocols were used and it was found that nearly 50% of the allyl groups could be functionalized with dopa within short reaction times, without the need of protecting the catechol. It is also demonstrated herein that the dopa-functional polymers can be used to form self-healing gels through complexation with Fe3+ ions at increased pH.

Place, publisher, year, edition, pages
Wiley-Blackwell, 2016. Vol. 54, no 15
Keyword [en]
Dopa, Photochemistry, Post-polymerization functionalization, Ring-opening-polymerization, Synthetic methods, Thiol-ene coupling
National Category
Polymer Technologies
URN: urn:nbn:se:kth:diva-180887DOI: 10.1002/pola.28111ISI: 000381302400013OAI: diva2:897401

QC 20160601

Available from: 2016-01-25 Created: 2016-01-25 Last updated: 2016-09-20Bibliographically approved
In thesis
1. Thiol-Ene CHemistry and Dopa-Functional Materials towards Biomedical Applications
Open this publication in new window or tab >>Thiol-Ene CHemistry and Dopa-Functional Materials towards Biomedical Applications
2016 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Thiol-ene chemistry is versatile and efficient and can be used as a powerful tool in polymer synthesis. In this thesis, the concept of thiol-ene chemistry has been central, where it has been explored as a tool for the synthesis of well-defined hydrogels and dopa-functional materials towards biomedical applications; such as hydrogels, primers for adhesive fixation of bone fractures, self-healing gels, and micelles for drug-delivery.

Using thiol-ene chemistry, well-defined hydrogels were realized in order to study how the structure influences properties such as swelling, stiffness and hydrolytic degradation. It was found that all these characteristics are related to each other, as a more loosely crosslinked hydrogel experiences higher swelling, lower stiffness and higher degradation rates.

Dopa-functional materials have gained a lot of interest throughout the years due to the remarkable adhesive properties they possess in wet environments. In the pursuit of new primers towards thiol-ene functional crosslinked bone adhesives, compounds with dopa moieties were proposed. Primers derived from dopamine were found to enhance the adhesion towards bone, and it was concluded that addition of NaOH was essential to achieve good adhesion. The strongest adhesion was achieved when thiol and ene-functional primers were used in combination.

Most synthetic routes to dopa-functional polymers involve several protection and deprotection steps and a more simplistic synthetic route is therefore desired. The possibility of using UV-initiated thiol-ene chemistry to produce dopa-functional polymers was therefore investigated. The resulting polymers were shown to exhibit self-healing properties upon complexation with Fe3+ ions.

Finally, the developed synthetic route was used to produce dopa and allyl-functional triblock-co-polymers. These triblock-co-polymers were then used to form micelles and evaluated as drug-delivery vehicles for the cancer-drug doxorubicin. The micelles were found to have high drug-loading capacities and slow release profiles and showed promising results when evaluated against breast-cancer cells.

Abstract [sv]

Reaktioner mellan tioler och omättade kemiska föreningar utgör ett mångsidigt och effektivt redskap inom polymersyntes. I denna avhandling har begreppet tiol-en kemi varit centralt och kemin har använts för syntes av såväl väldefinierade hydrogeler som dopa-funktionella material. Dessa material har sedan utvärderats mot biomedicinska tillämpningar såsom hydrogeler, primers för fixering av benfrakturer, självläkande geler och kontrollerad läkemedelsleverans.

Tiol-en-kemi har i denna avhandling använts för att framställa väldefinierade hydrogeler som sedan utvärderats med avseende på hur strukturen påverkar egenskaper såsom svällningsgrad, styvhet och nedbrytningshastighet. Det visade sig att alla dessa egenskaper är relaterade till varandra och att lösare tvärbundna hydrogeler uppvisar högre svällning, lägre styvhet och högre nedbrytningshastigheter.

Marina musslor har en exceptionell förmåga att fästa mot olika ytor och på grund av detta har det visats en hel del intresse för dopa-funktionella material genom åren. På jakt efter en primer för att öka vidhäftningen hos benlim proponerades därför föreningar med dopafunktionella grupper. Det visade sig att dopaminderivat kunde förbättra vidhäftningen mot ben och det visade sig även att tillsats av natriumhydroxid var viktigt för att uppnå god vidhäftningsförmåga. Den starkaste vidhäftning uppnåddes när derivat med tiol och omättade bindningar användes i kombination.

Syntes av dopafunktionella material involverar ofta flera reaktionssteg och en förenklad syntesväg är därför att eftersträva. UV-initierad tiol-en-kemi undersöktes därför som en möjlig syntesväg för att framställa dopafunktionella polymerer. Polymererna visade sig ha självläkande egenskaper vid komplexbildning med järnjoner.

Slutligen användes denna syntesväg för att framställa blocksampolymerer. Dessa blocksampolymerer användes sedan för att bilda miceller med lovande resultat vid utvärdering för leverans av läkemedel mot bröstcancer.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2016. 52 p.
TRITA-CHE-Report, ISSN 1654-1081 ; 2016:3
Thiol-ene chemistry, DOPA, biomedical, UV
National Category
Polymer Chemistry
Research subject
Fibre and Polymer Science
urn:nbn:se:kth:diva-180716 (URN)978-91-7595-811-8 (ISBN)
Public defence
2016-02-19, F3, Lindstedtsvägen 26, KTH, Stockholm, 09:00 (English)

QC 20160125

Available from: 2016-01-25 Created: 2016-01-21 Last updated: 2016-01-29Bibliographically approved

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Olofsson, KristinaMalkoch, MichaelHult, Anders
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