本論文係有關六硼化鑭奈米粒子的製備、表面二氧化矽修飾、及溫感性高分子聚(氮-異丙基丙烯醯胺)(PNIPAAm)的接枝以形成高分子複合微粒作為新型奈米生醫載體與熱治療材料。
關於六硼化鑭奈米粒子的製備，係利用濕式研磨分散技術將六硼化鑭微粉研磨分散於2-丙醇溶劑中而達成。由X射線繞射儀(XRD)與穿透式電子顯微鏡(TEM)分析得知，所得六硼化鑭奈米粒子具有立方體結構，平均粒徑為65 nm。又以UV-VIS-NIR光譜儀分析得知，六硼化鑭奈米粒子因自由電子電漿共振，在近紅外光區有明顯的吸收，在近紅外光雷射照射下具有顯著的光熱轉換效應。
關於二氧化矽被覆之六硼化鑭奈米粒子的製備，係以溶凝膠法將二氧化矽被覆於六硼化鑭奈米粒子表面，藉由改變前趨物TEOS濃度來控制二氧化矽殼層的厚度。由TEM分析得知，隨著TEOS量的增加，其殼層厚度可由10nm增加至40nm。此殼核型結構可藉由高解析TEM之元素能量分析、傅立葉轉換紅外線(FTIR)光譜儀與界面電位儀分析予以確認。又由UV-VIS-NIR光譜分析得知，六硼化鑭奈米粒子表面被覆二氧化矽後依然具有強度相近的近紅外線吸收特性，且在近紅外光雷射照射下，亦保有良好的光熱轉換效應。
關於被覆二氧化矽之六硼化鑭奈米粒子表面接枝PNIPAAm高分子的研究，係先以3-(Trimethoxysilyl)propyl methacrylate (MPS)作為改質劑，使二氧化矽表面具有C=C官能基，再以自由基共聚合法將PNIPAAm接枝於表面被覆二氧化矽之六硼化鑭奈米粒子表面，形成蘊含六硼化鑭奈米粒子之高分子複合微粒。由TEM與熱重分析(TGA)得知，此高分子複合微粒平均粒徑570nm，六硼化鑭被覆二氧化矽含量為20wt%。以FTIR光譜儀與界面電位儀分析，可證實高分子確實包覆在複合微粒表面。此外，由UV-VIS-NIR光譜分析得知，此高分子複合微粒較不含六硼化鑭奈米粒子之高分子微粒有較高的近紅外光吸收。在近紅外光雷射照射下，也具有光熱轉換效應。
關於蘊含六硼化鑭奈米粒子之高分子複合微粒作為藥物釋放載體的應用，係將異菸鹼硫胼(INH)抗肺炎藥物包覆於PNIPAAm高分子殼層內。INH在溫度高於六硼化鑭高分子複合微粒之低臨界溶解溫度(LCST)時的釋放速率較低於LCST時為快，溫度在 LCST間變化時，可觀察到可逆的熱敏感釋放行為。在近紅外線雷射照射下，六硼化鑭高分子複合微粒的溫度會上升，進而釋放出藥物。

This thesis concerns the fabrication of lanthanum hexaboride nanoparticles (LaB6 NPs), silica-coated LaB6 nanoparticles (LaB6@SiO2 NPs) and thermoresponsive poly(N-isopropylacrylamide) (PNIPAAm)-grafted LaB6 nanoparticles. These composite nanoparticles can be used as novel nanocarriers for biomedicine and the materials for thermotherapy.
LaB6 NPs were obtained by a bead milling process. Their morphology, structure, and optical property were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), and UV-VIS-NIR spectrophotometer. It was found that the LaB6 NPs have a cubic structure with a mean diameter of 65 nm. Also, they showed a significant absorption in near infrared (NIR) region owing to the free electron plasmon resonance and exhibited an excellent photothermal conversion property under the irradiation of a NIR laser.
LaB6@SiO2 NPs were prepared by the sol-gel coating of SiO2 on the surface LaB6 NPs. The thickness of SiO2 shells was tuned by varying the concentration of precursor TEOS. By TEM analysis, the thickness of SiO2 shells varied from 10 to 40nm with increasing the TEOS. By analyses of HRTEM EDS, FTIR and Zeta potential, the core-shell structure has been demonstrated. From UV-VIS-NIR spectra, LaB6@SiO2 NPs still showed a significant absorption in NIR region as LaB6 NPs did. Also, their excellent photothermal conversion property under the irradiation of an NIR laser was retained.
Thermoresponsive PNIPAAm-grafted LaB6 NPs (i.e., LaB6 microgels) were prepared by the following two steps. Firstly, the surface of LaB6@SiO2 NPs were modified by 3-(trimethoxysilyl)propyl methacrylate (MPS) to generate C=C bonds on the particle surface. Secondly, PNIPAAm was grafted onto the surface of LaB6@SiO2 NPs to yield the LaB6@SiO2 NPs-impregnated microgels via the radical copolymerization. From the analyses of TEM and TGA, it was found that LaB6 microgels had a mean diameter of 570nm and contained about 20 wt% LaB6@SO2 NPs. By FTIR and Zeta potential analyses, the grafting on the surface of LaB6@SiO2 NPs was confirmed. Furthermore, the UV-VIS-NIR spectra revealed that the LaB6 microgels had stronger absorption in NIR region than PNIPAAm microgels. Also, they exhibited photothermal conversion property under the irradiation of a NIR laser.
For the use of LaB6 microgels as the carrier for drug release, isoniazid (INH) was adsorbed in the PNIPAAm shells. The INH release rate was faster above the lower critical solution temperature (LCST) of the LaB6 microgels than below the LCST. When the temperature changed across the LCST, reversible and thermoresponsive release behavior was observed. By the exposure to a NIR laser, the temperature of LaB6 microgels increased and led to the drug release.

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