Citation: Xiao Jiang, Li Min-jie, Tang Hao-yu. Synthesis and Thermoresponsive Properties of Polypeptides Bearing Phosphonium Pendants[J]. Acta Polymerica Sinica, ;2018, (1): 56-62. doi: 10.11777/j.issn1000-3304.2018.17154 shu

Synthesis and Thermoresponsive Properties of Polypeptides Bearing Phosphonium Pendants

Key Laboratory of Polymeric Materials and Application Technology of Hunan Province, College of Chemistry, Xiangtan University, Xiangtan 411105

Corresponding author: Tang Hao-yu, htang@xtu.edu.cn
Received Date: 14 June 2017
Revised Date: 24 July 2017

A series of polypeptides bearing phosphonium pendants and chloride counter anions (P1-Cl -P5-Cl) were synthesized by nucleophilic substitution between poly(γ-3-chloropropyl-L-glutamate) (PCPLG) and tributyl phosphine and/or triphenyl phosphine. Their molecular structures were verified by ¹H nuclear magnetic resonance (¹H-NMR)and Fourier transform infrared (FTIR). From ¹H-NMR spectra, the molar content and grafting efficiency of tributyl phosphonium and/or triphenyl phosphonium moieties were calculated by integration of the characteristic proton peaks. All resulting polypeptides showed high grafting efficiency (≥ 87%). Polypeptides bearing phosphonium pendants and iodide (P1-I -P5-I) or tetrafluoroborate counter anions (P1-BF₄ -P5-BF₄) were synthesized by ion exchange. All polypeptides with chloride counter-anions were readily soluble in water. Nevertheless, P1-X (X = I, BF₄) with exclusive tributyl phosphonium and P5-X (X = I, BF₄) with exclusive triphenyl phosphonium showed poor solubility in water. It is interesting to observe that P2-I and P2-BF₄ samples with appropriate molar content of tributyl phosphonium moieties (x = 0.89) showed reversible thermo-responsiveness of UCST (upper critical solution temperature). This phenomenon suggested that co-grafting or copolymerization of the two non-thermoresponsive ionic liquid moieties led to UCST type thermoresponsivenes. To the best of our knowledge, this is the first example of thermoresponsive polypeptides bearing phosphonium pendants. Variable temperature UV-Vis spectroscopy was used to study the UCST type solution phase transition behaviors of P2-I and P2-BF₄. In a cooling/heating cycle, UV-Vis spectra revealed good reversibility of the UCST type phase transitions. Yet, a noticeable hysteresis was also observed. The UCST type phase transition temperature (T_pt) was also determined by UV-Vis spectroscopy at different temperatures. In DI water, the values of T_pt of P2-I and P2-BF₄ were in the temperature range of 11.5 -60.2 ℃ and 45.5 -71.0 ℃, respectively, and highly dependent on counter anions, polymer concentration, nature of salts and salt concentration. Under the same experimental condition, P2-BF₄ with more hydrophobic tetrafluoroborate counter anions showed higher T_pt than P2-I with iodide counter anions. Furthermore, T_pt increased with increased polymer concentration, sodium iodide or sodium tetrafluoroborate concentration. Yet, it decreased with increased sodium chloride concentration.
- Polypeptide (poly(amino acid)),
- Ionic polymer,
- UCST,
- Themoresponsiveness
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沈阳化工大学材料科学与工程学院沈阳 110142

Synthesis and Thermoresponsive Properties of Polypeptides Bearing Phosphonium Pendants

南开大学师唯/华北电力大学（保定）刘景维：二维配位聚合物中有序的亲锂冠醚位点用于无枝晶锂沉积

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通讯作者: 陈斌, bchen63@163.com