温敏性二氧化硅—透明质酸微凝胶的制备与表征
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摘要
无机-透明质酸(HA)核壳纳米颗粒融合了无机纳米材料和HA的优异性能,甚至可能具有原组分不具备的特殊性质。若在无机-HA核壳颗粒的壳层引入N-异丙基丙烯酰胺,并聚合交联成凝胶,则壳层既保持HA的生物相容性、高保水性、高粘性等特点,又具有PNIPAM的温度敏感性。
本论文采用纳米SiO2作为核材料,通过溶胶-凝胶法原位改性纳米SiO2后得到表面带正电的纳米SiO2颗粒(SiN),利用静电作用在其表面吸附HA形成核壳结构颗粒(SiNHA),进一步以SiNHA为核,在其表面聚合NIPAM形成温敏性核壳结构微凝胶(SiNHA-PNIPAM).通过扫描电镜(SEM)、透射电镜(TEM)以及傅立叶红外光谱(FTIR)表征了纳米SiO2、SiNHA、SiNHA-PNIPAM的形貌和结构组成,动态光散射(DLS)表征了其相应的粒径和zeta电位变化,最后用AFM表征微凝胶成膜性。结果表明,纳米SiO2经过KH550修饰后分散性良好,吸附HA形成表面带负电的无机-有机核壳结构颗粒,加入NIPAM后壳层聚合成温敏性微凝胶,临界温度为32℃,发现在25℃时,微凝胶在云母表面呈球形颗粒,温度升高到临界温度以上(37℃)时,微凝胶在云母表面发生相变化沉淀成膜,有望成为一种新型的可注射生物体软、组织修复的替代材料。
Inorganic-hyaluronic acid (HA) core-shell nano-particles posses the excellent properties of both inorganic nano-materials and HA, and may even have the special properties which the original components do not have. N-isopropyl acrylamide was introduced into the core-shell nano-particles and this caused the shell to be cross-linked resulting in the formation of microgels. These microgels maintained the properties of HA, such as the biocompatibility, good water retention, high-viscosity and had a temperature sensitivity of PNIPAM.
In this paper, the nano-SiN particles, whose surface were positively charged, were fabricated by modifying nano-SiO2 through the sol-gel method in situ. HA was coated onto the particles by electrostatic adsorption to form core-shell nanoparticles (SiNHA), which were selected as nuclear. Furthermore, N-isopropylacylamide was polymerized on the surface to form thermo-sensitive core-shell microgels (SiNHA-PNIPAM). The shape and conformation of SiO2, SiNHA and SiNHA-PNIPAM was determined by Scanning electron microscope(SEM), Transmission electron micrograph(TEM) and Fourier transform infrared spectroscopy(FTIR). The corresponding changes in particle size and zeta potential were characterized by Dynamic light scattering (DLS). At last the AFM was used to observe the film-forming of microgel above the critical temperature. The results indicated that nano-SiO2 had good dispersion after modifiying by KH550 and the core-shell nanoparticles(SiNHA-PNIPAM) was negatively charged. By polymerizing NIPAM onto the shell of particles, the thermo-sensitive core-shell microgels were formed and their critical temperature was 32℃. AFM and SEM observation revealed that the microgels were spherical on the mica surface at 25℃, but there was a phase-change and a film was depositing on the mica surface above the critical temperature (37℃). These nano-particles are hoped to be used in the soft and hard tissue replacement implants.
本论文采用纳米SiO2作为核材料,通过溶胶-凝胶法原位改性纳米SiO2后得到表面带正电的纳米SiO2颗粒(SiN),利用静电作用在其表面吸附HA形成核壳结构颗粒(SiNHA),进一步以SiNHA为核,在其表面聚合NIPAM形成温敏性核壳结构微凝胶(SiNHA-PNIPAM).通过扫描电镜(SEM)、透射电镜(TEM)以及傅立叶红外光谱(FTIR)表征了纳米SiO2、SiNHA、SiNHA-PNIPAM的形貌和结构组成,动态光散射(DLS)表征了其相应的粒径和zeta电位变化,最后用AFM表征微凝胶成膜性。结果表明,纳米SiO2经过KH550修饰后分散性良好,吸附HA形成表面带负电的无机-有机核壳结构颗粒,加入NIPAM后壳层聚合成温敏性微凝胶,临界温度为32℃,发现在25℃时,微凝胶在云母表面呈球形颗粒,温度升高到临界温度以上(37℃)时,微凝胶在云母表面发生相变化沉淀成膜,有望成为一种新型的可注射生物体软、组织修复的替代材料。
Inorganic-hyaluronic acid (HA) core-shell nano-particles posses the excellent properties of both inorganic nano-materials and HA, and may even have the special properties which the original components do not have. N-isopropyl acrylamide was introduced into the core-shell nano-particles and this caused the shell to be cross-linked resulting in the formation of microgels. These microgels maintained the properties of HA, such as the biocompatibility, good water retention, high-viscosity and had a temperature sensitivity of PNIPAM.
In this paper, the nano-SiN particles, whose surface were positively charged, were fabricated by modifying nano-SiO2 through the sol-gel method in situ. HA was coated onto the particles by electrostatic adsorption to form core-shell nanoparticles (SiNHA), which were selected as nuclear. Furthermore, N-isopropylacylamide was polymerized on the surface to form thermo-sensitive core-shell microgels (SiNHA-PNIPAM). The shape and conformation of SiO2, SiNHA and SiNHA-PNIPAM was determined by Scanning electron microscope(SEM), Transmission electron micrograph(TEM) and Fourier transform infrared spectroscopy(FTIR). The corresponding changes in particle size and zeta potential were characterized by Dynamic light scattering (DLS). At last the AFM was used to observe the film-forming of microgel above the critical temperature. The results indicated that nano-SiO2 had good dispersion after modifiying by KH550 and the core-shell nanoparticles(SiNHA-PNIPAM) was negatively charged. By polymerizing NIPAM onto the shell of particles, the thermo-sensitive core-shell microgels were formed and their critical temperature was 32℃. AFM and SEM observation revealed that the microgels were spherical on the mica surface at 25℃, but there was a phase-change and a film was depositing on the mica surface above the critical temperature (37℃). These nano-particles are hoped to be used in the soft and hard tissue replacement implants.
引文
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