Journal
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY
Volume 54, Issue 21, Pages 3425-3435Publisher
WILEY
DOI: 10.1002/pola.28230
Keywords
phase behavior; ring-opening polymerization; stimuli-sensitive polymers; structure-property relations; synthesis
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Funding
- Hunan Provincial Natural Science Foundation of China [2016JJ3110]
- National Natural Science Foundation of China [21204075]
- Scientific Research Fund of Hunan Provincial Education Department [14B175]
- Xiangtan University [12QDZ06]
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A series of thermoresponsive polypeptides bearing 1-butyl, 1-hexyl, or 1-dodecyl side-chains (i.e., 6a-6c) were synthesized by copper-mediated 1,3-dipolar cycloaddition with high grafting efficiency (> 95%) between side-chain clickable polypeptide, namely poly(gamma-4-(propargoxycarbonyl)benzyl-L-glutamate) (5) and 1-azidoalkanes. 5 with different degree of polymerization (DP=48-86) were prepared from triethylamine initiated ring-opening polymerization of gamma-4-(propargoxycarbonyl) benzyl-L-glutamic acid based N-carboxyanhydride (4). H-1 NMR, FTIR, and GPC results revealed the successful preparation of the resulting polypeptides. 6a-6c showed reversible UCST-type phase behaviors in methanol, ethanol, and ethanol/water solvent mixtures depending on the polymermain-chain length, alkyl side-chain length, weight percentage of ethanol (f(vv)) in the binary solvent, and so forth. FTIR analysis revealed the presence of the van der Waals interaction between the alkyl pendants of polypeptides and alkyl groups of alcoholic solvents. Variable-temperature UV-vis spectroscopy revealed that the UCST-type phase transition temperature (T-pt) increased as polymer main-chain length or concentration increased. In ethanol/water solvent mixtures, polypeptide with short alkyl pendant (i.e., 1-butyl group) and shortmain-chain length (DP=41) showed the widest f(vv) range and T(pt)s in the range of 61.0-71.1 degrees C. (C) 2016 Wiley Periodicals, Inc.
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