含奈米粒子複合凝膠材料之製備與性質研究

STUDIES ON THE PREPARATION AND PROPERTIES OF COMPOSITE HYDROGELS CONTAINING NANOPARTICLES

曹開泰(Kai-Tai Tsao)

指導教授 ： 李文福

大同大學/工程學院/化學工程學系所/碩士(2005年)

摘要

本文第一部分透過化學移位還原奈米銀粒後摻合入生物黏著劑水膠中。而生物黏著劑水膠由AA、PEGMEA作為單體共聚合而成，利用ascorbic acid 還原硝酸銀水溶液控制在狹窄的粒徑分佈內。將奈米銀粒摻合入生物黏著劑水膠中，探討摻合奈米銀粒於生物黏著劑膠體性質之影響，包含平衡膨潤性質、機械性質、導電度、大腸桿菌之殺菌效果。結果顯示，平衡膨潤方面，奈米銀粒摻合於膠體內部堵塞膠體孔洞使膠體吸水較不流暢；交聯密度與shear modulus，對於兩種膠體皆不隨著銀的導入量而增加；黏著力方面，水膠黏著力則無明顯變化；APECAg 系列膠體則表現出良好之抗菌效能。
本文第二部分生物黏著劑水膠由AA、PEGMEA及奈米銀粒藉由光聚合進行原位還原，探討影響奈米銀粒粒徑大小分佈原因，包含反應溫度、反應攪拌速率、前驅液之濃度及螯合劑與前驅液的濃度比，其中影響最大的原因為螯合劑濃度比。結果顯示，照光還原奈米銀粒於水膠表面，粒徑可微小化至72.4nm；導電度方面，隨著銀的導入量增加而增加；交聯密度與shear-stress，則不隨著銀的導入量而增加；黏著力隨著銀的導入量而下降；抗菌效能則是隨著銀含量增加有顯著效果，這是因為銀粒成功還原於生物黏著劑水膠之表面。
本文第三部分以溶液聚合法將NIPAAm、插層雲母、TMAAI，及使用NMBA作為交聯劑製備成一系列不同電性、電量之水膠。本篇文章中以TMAAI以不同離子交換倍率插層雲母，探討使用不同插層劑量的雲母對於膠體膨潤度、機械性質和藥物釋放性質的影響，微結構的鑑定使用XRD及SEM。結果顯示出在NIM系列中隨著插層劑量的增加膠體表面電位也逐漸提升(從-11mV到–6mV)，但對於NTIM系列膠體是隨著插層劑量的增加而表面電位呈現遞減(從+36 mV到+28 mV)。在平衡膨潤方面，NIM系列膠體膨潤度低於NTIM系列膠體。在膠體強度及交聯密度方面，NIM系列大於NTIM系列。但擴散係數與滲透速率中，NIM系列低於NTIM系列。最後藥物釋放行為在本文中探討之。

關鍵字

生物黏著劑 ； 水膠 ； UV照光還原 ； 移位還原聚合 ； 原位還原聚合 ； 抗菌 ； 奈米銀粒

並列摘要

A series of composite hydrogels containing silver nanoparticle used for bioadhesive were prepared from acrylic acid (AA), poly (ethylene glycol) methyl ether acrylate (PEGMEA) and silver nanoparticles through the ex-situ polymerization. The silver nanoparticles with narrow size distribution were prepared by reducing silver nitrate solution with ascorbic acid. The influence of the content of silver nanoparticles into bioadhesive hydrogel on the equilibrium swelling ratio, mechanical property, electrical conductivity and inactivation of Escherichia coli (E. coli) was investigated in this study. Results showed that the swelling ratios of the composite gels were decreased by silver nanoparticles into the gels, but not decreased with an increase of the content of silver nanoparticles. In addition, the crosslinking density and shear modulus of these hydrogels do not increase with an increase of the content of silver nanoparticles. The adhesive force of the present (APECAg series) hydrogels was not obviously changed. Finally, the initial rate of E. coli inactivation for APECAg series hydrogels showed excellent antibacterial properties.
A series of nanocomposite hydrogels used for bioadhesive were prepared from acrylic acid (AA), poly (ethylene glycol) methyl ether acrylate (PEGMEA) and silver nanoparticles through UV irradiation in-situ polymerization. The factors that affect the silver nanoparticles size include reaction temperature, stirring rate, the concentration of precursor solution and the concentration ratio of the chelating agent and the precursor solution (AgNO3(aq)). The most important factor is the concentration ratio of the chelating agent and the precursor solution. Results showed that the silver nanoparticles dispersed onto hydrogel surface and the mean silver particle size is 72.4 nm. The electrical conductivities of the nanocomposite hydrogels increase with increasing the silver nanoparticle content. The crosslinking density and shear modulus have no alteration with increasing the silver nanoparticle content. The adhesive force gradually decreases with increasing the silver nanoparticle content. And, the initial rate of E. coli inactivation also increases with the silver nanoparticle content. This is because silver nanoparticles were successfully reduced on the hydrogel surface.
Two series of different charge nanocomposite hydrogels were prepared from N-isopropylacrylamide (NIPAAm), intercalated mica (IM) and N, N'-methylene-bis-acrylamide (NMBA) (NIM-series); NIPAAm, IM, trimethyl (acrylamido propyl) ammonium iodide (TMAAI) (NTIM-series), respectively, in this study. The mica was intercalated with different contents of intercalant, trimethylammonium chloride (TMAACl), based on the anion exchange capacity (AEC) of mica. The swelling behaviors, mechanical properties and drug-release behaviors were compared from these two series gels. Their microstructures and morphologies were also examined by X-ray diffraction (XRD) and scanning electronic microscopy (SEM). Results showed that zeta potentials for the NIM series gels increase with increase in intercalation content of mica, (from –11 mV to –6 mV), but the zeta potentials for NTIM series gels decrease with increase in intercalation content of mica, (from +36 mV to +28 mV). The swelling ratios for the NIM gels are lower than those for NTIM series gels. The gel strengths and crosslinking densities for NIM series gels are higher than corresponding NTIM series gels. But the diffusion coefficient and penetration velocity for NIM series gels are lower than corresponding NTIM series gels. The drug-release behaviors for these two series gels are also investigated in this study.

並列關鍵字

Antibacterial ； Bioadhesive ； Ex-Situ Polymerization ； Hydrogel ； In-situ Polymerization ； Irradiation Reduction ； Silver Nanoparticle

參考文獻

5. Chou, K. S.; Ren, C. Y. Mater Chem Phy 2000, 64, 241.

6. Zhang, Z.; Zhang, L.; Wang, S.; Chen, W.; Lei, Y. Polymer 2001, 42, 8315.

8. Sondi, I.; Goia, D. V.; Matijevic, E. J Colloid Inter Sci 2003, 260, 75.

9. Mortazavi, S. A. Int J Pharm 1995, 124, 173.

10. Chickering, D. E.; Mathiowitz E. J Control Release 1995, 34, 251.