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Polymers exhibiting an abnormal thermoresponsive behaviour, in which increase in the polymer concentration in water leads to an increase in the phase transition temperature, are few, and no plausible strategy has been addressed to prepare these polymers. For illuminating a feasible common strategy to prepare polymers with an abnormal thermoresponsive behaviour, in this study, we systematically prepared a series of hyperbranched polyglycerol (HPG) derivatives through a facile esterification reaction between HPG and aliphatic acids having different carbon numbers (X). Turbidimetry measurements demonstrate that thermoresponsive HPGs can be obtained only when HPGs are conjugated with aliphatic units of X ≤ 8. The conjugation of HPG with aliphatic units of X ≤ 4 resulted in thermoresponsive HPGs with a normal thermoresponsive behaviour. For the preparation of thermoresponsive HPGs with an abnormal thermoresponsive behaviour, X should be controlled in the range of 5-8. Fluorescence measurements with nile red as the fluorescent probe demonstrate that the existence of relatively strong hydrophobic interaction is a key factor to ensure that the polymer exhibits an abnormal thermoresponsive behaviour in water. Moreover, turbidimetry and fluorescence techniques are complementary for measuring the phase transition behaviour and suitable for different polymer concentration regions.


Yao Zhang, Rui-Cong Wang, Hua-Ji Liu, Yu Chen. Hyperbranched polyglycerol derivatives exhibiting normal or abnormal thermoresponsive behaviours in water: facile preparation and investigation by turbidimetry and fluorescence techniques. Soft matter. 2017 Nov 15;13(44):8136-8143

PMID: 29075702

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