Chemical modification of functionalized polyhydroxyalkanoates via 'Click' chemistry: A proof of concept
| Autor: | Samuel Nkrumah-Agyeefi, Carmen Scholz |
|---|---|
| Rok vydání: | 2017 |
| Předmět: |
Azides
Halogenation Triazole Alkyne 02 engineering and technology Acetates 010402 general chemistry 01 natural sciences Biochemistry Catalysis chemistry.chemical_compound Structural Biology Polymer chemistry Molecular Biology chemistry.chemical_classification Chemistry Polyhydroxyalkanoates General Medicine 021001 nanoscience & nanotechnology Cycloaddition 0104 chemical sciences Alkynes Propargyl Click chemistry Proton NMR Sodium azide Click Chemistry Azide 0210 nano-technology Copper |
| Zdroj: | International Journal of Biological Macromolecules. 95:796-808 |
| ISSN: | 0141-8130 |
| DOI: | 10.1016/j.ijbiomac.2016.11.118 |
| Popis: | A novel approach to the post-biosynthetic chemical modification of bromo and alkyne functionalized poly(3-hydroxyalkanoates), (PHAs), via copper-catalyzed azide-alkyne cycloaddition (CuAAC) and strain promoted azide alkyne cycloaddition (SPAAC) is reported. Optimum conditions for the biosynthesis of the PHA copolymers, poly(3-hydroxynonanoate-co-3-hydroxy-11-bromoundecanoate) (PHNUBr) and poly(3-hydroxynonanoate-co-3-hydroxy-10-undecynoate) (PHNUD), using Pseudomonas oleovorans as cell factories were 20 h of fermentation time and a total carbon substrate concentration of 40 mM. Percent incorporation of brominated repeat units and alkyne repeat units were 38.5% and 50% respectively, as determined by 1H NMR. PHNUBr was converted into an azido-terminated precursor for the polymer analogous “click” reactions via SN2 nucleophilic substitution reaction using sodium azide with a yield of 96.7% and analyzed by FTIR and 1H NMR. CuAAC reactions were used to attach propargyl benzoate and methyl-2-azidoacetate to the PHAs with terminal azido and alkyne functional side groups respectively, with yields of 78.2% and 65.4% respectively. FTIR analysis of the products showed the disappearance of the azide peak at 2093.5 cm−1 and the alkynyl C C H stretch at 3292 cm−1. 1H NMR analysis confirmed the formation of the expected triazole linkage; showing the expected proton chemical shift corresponding to the triazole proton at 7.73 and 7.47 ppm respectively. A strain promoted azide-alkyne reaction was used to attach (1R,8S,9s)-Bicyclo[6.1.0]non-4-yn-9-ylmethanol (BCN-OH) to the azido-terminated PHA with an average yield of 94.5%. Products were analyzed by FTIR and 1H NMR. |
| Databáze: | OpenAIRE |
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