title: Advanced functionalization of polyhydroxyalkanoate via the UV-initiated thiol-ene click reaction.
abstract: 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. (1)H 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.
authors.affiliation: Division of Applied Chemistry, Faculty of Engineering, Hokkaido University, N13W8, Kita-ku, Sapporo, 060-8628, Japan. ktajima@eng.hokudai.ac.jp.
authors.forename: Kenji
authors.initials: K
authors.lastname: Tajima
authors.affiliation: Division of Applied Chemistry, Faculty of Engineering, Hokkaido University, N13W8, Kita-ku, Sapporo, 060-8628, Japan.
authors.forename: Kosuke
authors.initials: K
authors.lastname: Iwamoto
authors.affiliation: Division of Applied Chemistry, Faculty of Engineering, Hokkaido University, N13W8, Kita-ku, Sapporo, 060-8628, Japan.
authors.forename: Yasuharu
authors.initials: Y
authors.lastname: Satoh
authors.affiliation: Division of Applied Chemistry, Faculty of Engineering, Hokkaido University, N13W8, Kita-ku, Sapporo, 060-8628, Japan.|Department of Materials Chemistry, Asahikawa National College of Technology, Asahikawa, 071-8142, Japan.
authors.forename: Ryosuke
authors.initials: R
authors.lastname: Sakai
authors.affiliation: Division of Applied Chemistry, Faculty of Engineering, Hokkaido University, N13W8, Kita-ku, Sapporo, 060-8628, Japan.
authors.forename: Toshifumi
authors.initials: T
authors.lastname: Satoh
authors.affiliation: Division of Applied Chemistry, Faculty of Engineering, Hokkaido University, N13W8, Kita-ku, Sapporo, 060-8628, Japan. dairi@eng.hokudai.ac.jp.
authors.forename: Tohru
authors.initials: T
authors.lastname: Dairi
mesh_terms: D015097:3-Mercaptopropionic Acid / Q000737:chemistry; D057930:Click Chemistry / Q000379:methods*; D003543:Cysteamine / Q000737:chemistry; D005353:Fibronectins / Q000737:chemistry; D019793:Fluorescein / Q000737:chemistry; D061307:Human Umbilical Vein Endothelial Cells; D006801:Humans; D009682:Magnetic Resonance Spectroscopy; D008970:Molecular Weight; D011091:Polyesters / Q000737:chemistry; D054813:Polyhydroxyalkanoates / Q000737:chemistry*; D014466:Ultraviolet Rays
chemical_list: D005353:Fibronectins; D011091:Polyesters; D054813:Polyhydroxyalkanoates; C033616:poly(lactide); D003543:Cysteamine; D015097:3-Mercaptopropionic Acid; D019793:Fluorescein
keywords: Click chemistry; Double bond; Ene-thiol click reaction; Medium-chain length; Polyhydroxyalkanoate