Applied Microbiology and Biotechnology

, Volume 100, Issue 10, pp 4375–4383 | Cite as

Advanced functionalization of polyhydroxyalkanoate via the UV-initiated thiol-ene click reaction

Biotechnological products and process engineering


Polyhydroxyalkanoates (PHAs) incorporating vinyl-bearing 3-hydroxyalkanoates were prepared in 8.5–12.9 g L−1 yield. The molar ratios (0–16 mol%) of the vinyl-bearing 3-hydroxyalkanoate derivatives were controlled by the continuous feeding of undecylenate at various concentrations. Subsequently, the PHAs were functionalized by UV-initiated thiol-ene click reaction and chemical modification. 1H NMR spectra suggested that 3-mercaptopropionic acid and 2-aminoethanethiol were successfully introduced into the vinyl-bearing PHA. Subsequently, chemical modification using fluorescein or a fibronectin active fragment (GRGDS) was attempted. The former yielded a PHA derivative capable of emitting fluorescence under UV irradiation, which was useful for determining the miscibility of PHA in a composite film comprising poly-ʟ-lactic acid (PLLA) and PHA. In the latter case, PHA bearing GRGDS peptides exhibited cell adhesiveness, suggesting that its biocompatibility was improved upon peptide introduction. Taken together, the UV-initiated thiol-ene click reaction was demonstrated to be useful in PHA modification.


Polyhydroxyalkanoate Medium-chain length Click chemistry Double bond Ene-thiol click reaction 



We thank Mr. Eiji Yamada and Mr. Naoya Nakagawa of Hokkaido University for their technical support in NMR measurements.

Compliance with ethical standards


This work was supported by Grant-in-Aid for Scientific Research (No. 21310060 and 21760632) from the Ministry of Education, Culture, Sports, Science, and Technology, Japan.

Conflict of interest

The authors declare that they have no competing interests.

Ethical approval

This article does not contain any studies with human participants or animals performed by any of the authors.


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Copyright information

© Springer-Verlag Berlin Heidelberg 2016

Authors and Affiliations

  1. 1.Division of Applied Chemistry, Faculty of EngineeringHokkaido UniversitySapporoJapan
  2. 2.Department of Materials ChemistryAsahikawa National College of TechnologyAsahikawaJapan

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