SiO2-HA/PNIPAm核壳温敏微凝胶的合成及其溶胀性能

doi:10.6023/A14040273

摘要/Abstract

以SiO₂纳米颗粒为核，以透明质酸（HA）和聚异丙基丙烯酰胺（PNIPAm）的杂化凝胶（HA/PNIPAm）为壳制备了一系列无机-有机杂化核壳结构单分散微凝胶.该微凝胶具有很好的温度敏感性，其最低临界转变温度（LCST）在34 ℃附近；该微凝胶具有负触变性，且温度高于LCST时负触变性更明显.用动态光散射（DLS）测定了微凝胶颗粒的水动力学粒径随温度的变化关系，实验数据可以用我们早前建立的硬核高分子凝胶分子热力学模型进行关联计算，结果表明只需较少的模型参数就可较好地描述温度响应的核壳结构高分子凝胶的溶胀行为.

关键词: 温度敏感性, 核壳微凝胶, 溶胀性能, 透明质酸, 二氧化硅

A series of thermoresponsive core-shell microgels were synthesized using SiO₂ as core and hybrid gel (hyaluronate/poly(N-isopropylacrylamide) (HA/PNIPAm)) as shell.SiO₂ particles were modified by KH550 to get -NH₂ groups, which could be protonized in acid condition.So that they could be covered by HA chains through electrostatic force.Then, HA was grafted using glycidyl methacrylate (GMA) to obtain C=C groups for the next synthesis of HA/PNIPAm hybrid gel.The modification degree of C=C was determined through ¹H nuclear magnetic resonance spectroscopy (¹H NMR).Fourier-transform infrared spectra (FT-IR) were used to monitor each synthesis step.Transmission electron microscopy (TEM) images showed that SiO₂-HA/PNIPAm microgels were almost monodispersed and possessed perfect core-shell structures.Thermoresponsive behaviors of microgels were investigated using micro-differential scanning calorimetry (Micro-DSC), which showed that the lower critical solution temperature (LCST) values were almost the same, around 34±0.1 ℃, regardless of the synthetic parameters.The thixotropy of SiO₂-HA/PNIPAm microgels was studied using rheometer.It turned out that the microgels possessed negative thixotropy.Moreover, when the temperature was higher than LCST, the thixotropy was better than that of lower temperature.The swelling behaviors of SiO₂-HA/PNIPAm microgels were evaluated by combining experiment methods and theoretical calculation.Dynamic light scattering (DLS) was used to analyze the swelling behavior of microgels with the increase of temperature.The DLS results showed that microgels possessed good thermoresponsive behavior with a LCST at about 34 ℃, which was in accordance with that determined by Micro-DSC.The hydrodynamic diameter (d) was found to be dependent on the size of core, the M_w of HA and the amount of PNIPAm.Theoretical calculation was carried out using a lattice molecular thermodynamic model based on our previous works, it showed that the calculated results were in good agreement with the experimental data.The results indicated that the model could predict the swelling behavior of thermoresponsive core-shell structured microgel using fewer model parameters.This work will provide fundamental reference for further research.

Key words: thermoresponsive, core-shell microgel, swelling behavior, hyaluronic acid, SiO₂

引用此文

李相晔, 练成, 支东彦, 徐首红, 刘洪来. SiO₂-HA/PNIPAm核壳温敏微凝胶的合成及其溶胀性能[J]. 化学学报, 2014, 72(6): 689-696.

Li Xiangye, Lian Cheng, Zhi Dongyan, Xu Shouhong, Liu Honglai. Synthesis and Swelling Behavior of SiO₂-HA/PNIPAm Core-shell Structured Thermoresponsive Microgels[J]. Acta Chimica Sinica, 2014, 72(6): 689-696.

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SiO₂-HA/PNIPAm核壳温敏微凝胶的合成及其溶胀性能

Synthesis and Swelling Behavior of SiO₂-HA/PNIPAm Core-shell Structured Thermoresponsive Microgels

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