Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3899
標題: 高分子與奈米矽片複合材料特性暨抗菌性與生物相容性之探討
Characterization, antimicrobial activity and biocompatibility evaluation of polymer/nano silicate platelet nanocomposites
作者: 王明鍵
Wang, Ming-Chien
關鍵字: Montmorillonite;蒙脫土;chitosan;clay;antimicrobial;polyurethane;biocompatibility;nanocomposite;幾丁聚醣;黏土;抗菌性;聚胺酯;生物相容性;奈米複合材料
出版社: 化學工程學系所
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Macromolecules. 2004;38:230-3. [7] Chu C-C, Chiang M-L, Tsai C-M, Lin J-J. Exfoliation of Montmorillonite Clay by Mannich Polyamines with Multiple Quaternary Salts. Macromolecules. 2005;38:6240-3. [8] Lin J-J, Chu C-C, Chiang M-L, Tsai W-C. First Isolation of Individual Silicate Platelets from Clay Exfoliation and Their Unique Self-Assembly into Fibrous Arrays. The Journal of Physical Chemistry B. 2006;110:18115-20. [9] Hsu SH, Tseng HJ, Hung HS, Wang MC, Hung CH, Li PR, et al. Antimicrobial activities and cellular responses to natural silicate clays and derivatives modified by cationic alkylamine salts. ACS Appl Mater Interfaces. 2009;1:2556-64. [10] Lin JJ, Chu CC, Chiang ML, Tsai WC. Manipulating Assemblies of High-Aspect-Ratio Clays and Fatty Amine Salts to Form Surfaces Exhibiting a Lotus Effect. Advanced Materials. 2006;18:3248-52. [11] Teow Y, Asharani PV, Hande MP, Valiyaveettil S. Health impact and safety of engineered nanomaterials. Chemical Communications. 2011. 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Controlling cell-material interactions with polymer nanocomposites by use of surface modifying additives. Applied Surface Science. 2008;255:519-22. [18] Styan KE, Martin DJ, Poole-Warren LA. In vitro fibroblast response to polyurethane organosilicate nanocomposites. Journal of Biomedical Materials Research Part A. 2008;86A:571-82. [19] Nigmatullin R, Gao F, Konovalova V. Permanent, Non-Leaching Antimicrobial Polyamide Nanocomposites Based on Organoclays Modified with a Cationic Polymer. Macromolecular Materials and Engineering. 2009;294:795-805. [20] Nigmatullin R, Gao F, Konovalova V. Polymer-layered silicate nanocomposites in the design of antimicrobial materials. Journal of Materials Science. 2008;43:5728-33. [21] Lin J-J, Chen Y-M. Amphiphilic Properties of Poly(oxyalkylene)amine-Intercalated Smectite Aluminosilicates. Langmuir. 2004;20:4261-4. [22] Lai Y-H, Chiu C-W, Chen J-G, Wang C-C, Lin J-J, Lin K-F, et al. Enhancing the performance of dye-sensitized solar cells by incorporating nanosilicate platelets in gel electrolyte. Solar Energy Materials and Solar Cells. 2009;93:1860-4. [23] Rojo L, Barcenilla JM, Vazquez B, Gonzalez R, San Roman J. Intrinsically antibacterial materials based on polymeric derivatives of eugenol for biomedical applications. Biomacromolecules. 2008;9:2530-5. [24] Benefield LD, Judkins J, Joseph F., Weand BL. Process chemistry for water and wastewater treatmen. Englewood Cliffs, N.J.: Prentice-Hall; 1982. [25] Piret J, Lamontagne J, Bestman-Smith J, Roy S, Gourde P, Desormeaux A, et al. In vitro and in vivo evaluations of sodium lauryl sulfate and dextran sulfate as microbicides against herpes simplex and human immunodeficiency viruses. J Clin Microbiol. 2000;38:110-9. [26] Ding S-J, Shie M-Y, Hoshiba T, Kawazoe N, Chen G, Chang H-C. Osteogenic Differentiation and Immune Response of Human Bone-Marrow-Derived Mesenchymal Stem Cells on Injectable Calcium-Silicate-Based Bone Grafts. Tissue Engineering Part A. 2010;16:2343-54. [27] Dalby M. Increasing Fibroblast Response to Materials Using Nanotopography: Morphological and Genetic Measurements of Cell Response to 13-nm-High Polymer Demixed Islands. Experimental Cell Research. 2002;276:1-9. [28] Dalby MJ, Giannaras D, Riehle MO, Gadegaard N, Affrossman S, Curtis ASG. Rapid fibroblast adhesion to 27nm high polymer demixed nano-topography. Biomaterials. 2004;25:77-83. [29] Sinha Ray S, Yamada K, Okamoto M, Ueda K. Polylactide-Layered Silicate Nanocomposite:  A Novel Biodegradable Material. Nano Letters. 2002;2:1093-6. [30] Decker H, Ryan M, Jaenicke E, Terwilliger N. SDS-induced phenoloxidase activity of hemocyanins from Limulus polyphemus, Eurypelma californicum, and Cancer magister. J Biol Chem. 2001;276:17796-9. [31] Christenson EM, Anderson JM, Hiltner A. 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摘要: 
奈米矽片(NSP)以層狀黏土(蒙脫土)為材料,利用高分子型界面活性劑,只需一個步驟即可將層狀黏土脫層而得。從幾何觀點來看,NSP屬於一維奈米材料,其可均勻分散於水中,故可與溶解於水中的高分子進行混摻。為使NSP亦能混摻於溶劑型高分子中,則使用三種(陽離子、中性與陰離子)界面活性劑對其進行改質,此即為NSQ。在NSQ的測試方面,則對介達電位、抗菌性與生物相容性進行初步研究。結果發現僅NSQa的介達電位是正的,其餘樣品(NSP、NSQb及NSQc)皆為負。所有的NSQ皆呈現低細胞毒性,相對而言NSP則有較高的細胞毒性。NSQa與NSQc對金黃葡萄球菌與大腸桿菌亦呈現出較佳的抗菌性。在第一部份的研究中,則利用NSP與幾丁聚醣(chitosan, CS)醋酸溶液進行混摻,形成CS/NSP奈米複合材料。結果發現NSP在CS中具有良好分散性,並與CS產生正負電荷間的作用力。CS/NSP與純CS相較之下,呈現較佳的動態機械性質。此外,當NSP含量>103 ppm時,NSP則會暴露在CS/NSP奈米複合材料表面,並降低表面接觸角。纖維母細胞在CS/NSP 103 ppm表面的生長量則顯著高於其他濃度樣品,而抗菌性則隨NSP的濃度增加而增加。低濃度的NSP水溶液,在大鼠皮下沒有顯著的發炎反應。當NSP水溶液>103 ppm時,才有顯著的發炎反應。在大鼠體內的生物相容性測試則發現,CS/NSP的分解速率高於純的CS。在第二部份的研究,則以NSQ與聚氨酯(polyurethane, PU)進行混摻,產生PU/NSQ奈米複合材料。進而對PU/NSQ奈米複合材料進行表面與機械性質測試、細胞貼附與生長、體外抗菌性與生物體內生物相容性測試。結果發現界面活性劑含量比例較高之NSQ,在PU中具有較佳的分散性。所有的PU/NSQ的機械性質皆呈現顯著增加。而三種NSQ中,只有觀察到NSQa暴露在複合材料的表面。在內皮細胞與纖維母細胞的貼附與生長測試則發現在1% PU/NSQa的表面的效果最好。而同時1% PU/NSQa與PU/NSQc表面的抗菌性亦皆超過99%。以上這些結果顯示出生物可分解與生物穩定型高分子/NSP奈米複合材料,尤其是0.1%CS/NSP與1% PU/NSQa未來在應用上的安全性與作為抗菌生醫材料的潛力與發展。

A novel method to exfoliate the montmorillonite clay was developed previously to generate random nano silicate platelets (NSP). They are one kind of delaminated montmorillonite particles (DMtP) and one-dimensional nanomaterials in geometry. NSP were dispersed in water and mixed with waterborne polymer. To improve their dispersion in a polymer, NSP were modified by three types of surfactants (cationic Qa, nonionic Qb and anionic Qc) in this study. The zeta potential, antimicrobial ability and biocompatibility of NSQ were characterized. It was found that the zeta potential of NSQa was positive while those of NSP and the other two NSQ (NSQb and NSQc) were negative. All NSQ presented less cytotoxicity than NSP. NSQa and NSQc showed excellent antimicrobial activities against S. aureus (Gram-positive strain) and E. coli (Gram-negative strain). NSP and these surfactant modified NSP (abbreviated “NSQ”) were further used to prepare polymer nanocomposites in this study. In the first part, water dispersible NSP were mixed with Chitosan (CS) acetic acid solution to form CS/SNP nanocomposites. The dispersion of NSP in the CS matrix was good, probably as a result of the charge interaction between the two components. The CS/NSP demonstrated better dynamic mechanical moduli. NSP were found to be enriched on the surface of the nanocomposites when the amount of NSP was > 103 ppm. This was accompanied by a decrease of the contact angle. The proliferation of fibroblasts on CS/NSP 103 ppm was significantly greater than on other materials. The antimicrobial activity was enhanced markedly with the increased amount of NSP in CS/NSP. The inflammatory responses of NSP in vitro and in subcutaneous rats were not obvious until the concentration of NSP was > 103 ppm. The biocompatibility of CS/NSP 103 ppm was even better than that of CS. The biodegradation rate of the CS/NSP nanocomposite was much faster than that of the pure CS polymer. In the second part, organic solvent dispersible NSQ were mixed with polyurethane (PU) in dimethylacetamide to form PU/NSQ nanocomposites. The nanocomposites were then characterized for surface and mechanical properties, cell attachment and proliferation, antimicrobial activity in vitro and biocompatibility in vivo. A higher surfactant to NSP ratio was found to improve the dispersion of NSQ in PU matrix. The mechanical properties of all PU/NSQ nanocomposites were significantly enhanced. Among various NSQ, only NSQa were observed to migrate to the composite surface. The attachment and proliferation of endothelial cells and fibroblasts in vitro as well as biocompatibility in vivo were significantly better for PU/NSQa containing 1% of NSQa than other materials. The microbiostasis ratios of PU/NSQ nanocomposites containing 1% NSQa or NSQc were over 99%. Taken together, these results suggested safety and potential antimicrobial applications of biodegradable or biodurable polymer/NSP nanocomposites, especially 0.1% CS/NSP and 1% PU/NSQa nanocomposites.
URI: http://hdl.handle.net/11455/3899
其他識別: U0005-1601201216054200
Appears in Collections:化學工程學系所

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