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研究生: 歐陽愛雁
Ai-Nhan Au-Duong
論文名稱: 嵌有金屬有機骨架之細菌纖維複合膜及兒茶酚聚乙烯吡咯烷酮的製備分析與應用
Metal Organic Frameworks Embedded Bacterial Cellulose Pellicle and Catechol Functionalized Poly (N-vinylpyrrolidone): Preparation, Characterization and Application
指導教授: 李振綱
Cheng-Kang Lee
口試委員: 今榮東洋子
Toyoko Imae
李振綱
Cheng-Kang Lee
王勝仕
Steven S.-S. Wang
王孟菊
Meng-Jiy Wang
邱昱誠
Yu-Cheng Chiu
學位類別: 博士
Doctor
系所名稱: 工程學院 - 化學工程系
Department of Chemical Engineering
論文出版年: 2017
畢業學年度: 105
語文別: 英文
論文頁數: 114
外文關鍵詞: ZIF-8, nanocomposite based on bacterial cellulose, iodine treatment, bioinspired PVP, anti-fouling, protein resistance, eversible Addition Fragmentation chain Transfer (RAFT) polymerization
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本論文主要討論金屬骨架結構嵌入細菌纖維素薄膜形成之功能性奈米複合膜及接有兒茶酚之聚乙烯吡咯烷酮(PVP)的合成和性質分析。並應用此奈米複合膜於環境保護上,兒茶酚PVP於材料表面塗佈產生抗生物污垢之功能。
沸石咪唑酸酯骨架-8 (ZIF-8)是一較容易獲得的金屬有機骨架的材料之一,已經被證明可以吸附多種活性物質,且具有極高之容量。細菌纖維素(BC)則為機械性質良好具超細三維(3-D)網絡結構之高含水量膜材,可用作ZIF-8沉積的理想基質。而氧化自聚合的多巴胺可以容易且緊密地在BC纖維表面上形成聚多巴胺。聚多巴胺塗層不僅可以作為ZIF-8形成的成核位點,而且可以防止鋅離子和纖維素之間的複合物形成,使鋅離子能充分參與與配體2-IM的反應而形成ZIF-8奈米顆粒。經 SEM觀察,所形成之ZIF-8奈米顆粒(~127nm)均勻地嵌入BC薄膜內,成為 BC@Dopa-ZIF奈米複合材料,其中約73%(w/w)是ZIF-8奈米顆粒。 BC@Dopa-ZIF可以非常有效地吸附碘蒸氣(1.87±0.18g I2/g納米複合材料)及碘溶液(1.31±0.02g I2/g納米複合材料)。由於聚多巴胺在近紅外線照射下可非常有效地產生熱,所以BC@Dopa-ZIF捕獲的碘在通過808nm激光的照射,可有效地被釋放出來,而使BC@Dopa-ZIF再生。光熱再生的BC@Dopa-ZIF於第二次使用時可維持99%的碘吸附能力,第六次使用仍可維持87%的能力。
使用由可逆加成斷裂鏈轉移(RAFT)聚合合成的羧基PVP,與咖啡酸一起可接附於聚賴氨酸(ε-PLL)結構上,製備出具兒茶酚官能基之聚乙烯吡咯烷酮(CA-PLL-PVP),可用於材料表面塗層防止生物結垢。 CA-PLL-PVP可以有效地塗附在玻璃,組織培養聚苯乙烯(TCPS)和聚丙烯多孔膜表面上,使得表面變得更加親水和耐蛋白吸附,在塗有CA-PLL-PVP的多孔PP膜上蛋白質的吸附量可減少約50%以上。


This thesis mainly investigates the synthesis and characterization of a metal organic frameworks embedded bacterial cellulose pellicle and catechol functionalized poly (N-vinylpyrrolidone) (PVP). The attempts to develop functional bionanocomposites and anti-biofouling surface for environmental and biomedical applications are reported.
Zeolitic imidazolate framework-8 (ZIF-8) is one of easily available metal organic frameworks and has been demonstrated to accommodate various active compounds in its mesoporous structure with very good capacity. Bacterial cellulose (BC) has a natural ultrafine three-dimensional (3-D) network structure with sufficiently high porosity, excellent biocompatibility, and mechanical stability, was used as a matrix to embed the in situ formed ZIF-8 nanoparticles. Polydopamine, oxidatively self-polymerized dopamine, could be easily and tightly coated on the surface of BC nanofibers. The polydopamine coating not only can act as a nucleation site for ZIF-8 formation but also prevents the complex formation between zinc ions and cellulose that leads to all the employed zinc ions participate the coordination reaction with ligand 2-IM for ZIF-8 formation. ZIF-8 was well embedded inside BC pellicle with uniform shape and size about 127 nm as observed by SEM. Approximately, 73% (w/w) of the BC-based nanocomposite (BC@Dopa-ZIF) is ZIF-8 nanoparticles. BC@Dopa-ZIF was demonstrated to have very good performance in capturing iodine from its vapor (1.87±0.18 g I2/g nanocomposite) and I2/KI solution (1.31±0.02 g I2/g nanocomposite). Since polydopamine is a good photothemal conversion agent under near-infrared irradiation, iodine captured by BC@Dopa-ZIF was effectively released by radiation of laser light of 808 nm. The photo -thermally regenerated BC@Dopa-ZIF maintained 99 % of its iodine adsorption capacity for the second use and 87 % for sixth use.
Catechol functionalized poly(N-vinylpyrrolidone) (CA-PLL-PVP) prepared from -PLL, caffeic acid, and carboxylic PVP synthesized by reversible addition fragmentation chain transfer (RAFT) polymerization was employed for facile biofouling resistant surface coating. CA-PLL-PVP could be securely and effectively coated on glass, tissue culture polystyrene (TCPS) and polypropylene surfaces under a mild condition as characterized by ATR-FTIR and iodine complexation. The CA-PLL-PVP coated surfaces became more hydrophilic and protein resistant due to the present of PVP. The amount of protein adsorbed on CA-PLL-PVP coatings was about 50% less than that observed on pristine and PVP coated microporous PP membrane.

Chapter 1 Introduction 1 1.1 Preface 1 1.2 Bacterial cellulose (BC) pellicles based nanocomposite 1 1.2.1 General introduction of ZIF-8 1 1.2.2 Structural features and properties of BC 4 1.2.3 Trend in the development of nanocomposite based BC 6 1.3 Catechol functionalized Poly (N-vinyl pyrrolidone) (CA-PVP) 7 1.3.1 Overview of PVP 7 1.3.2 Reversible Addition Fragmentation chain Transfer (RAFT) polymerization 8 1.3.3 Mussel-inspired polymer 8 1.3.3.1 Catechol chemistry and recent biomimetic polymers 8 1.3.3.2 Application of adhesive polymer 9 1.3.3.3 Bioinspired PVP 11 1.4 Motivation and research objective 12 1.4.1 Metal organic frameworks embedded bacterial cellulose pellicle 12 1.4.2 Novel catechol functionalized Poly (N-vinylpyrrolidone) 14 1.5 The outline of thesis 17 1.6 References 18 Chapter 2 Theory 34 2.1.2 Attachment mechanism 35 2.3.1 Mechanism of RAFT 38 2.3.2 RAFT agents 40 Chapter 3 Experimental Section 46 3.1 Materials 46 3.2 Methods 46 3.2.1 Preparation and characterization of ZIF-8 46 3.2.2 Preparation and characterization of BC pellicle based nanocomposite 47 3.2.3 Preparation and characterization of CA-PLL-PVP polymer 48 3.3 Measurements 50 3.3.1 UV-Vis spectroscopy 50 3.3.2 X-ray diffraction (XRD) 50 3.3.3 Brunauer–Emmett–Teller (BET) 50 3.3.4 Thermogravimetric analyzer (TGA) 50 3.3.5 1H NMR spectroscopy 51 3.3.6 Mechanical analysis 51 3.3.7 Field Emission Scanning Electron Microscopy (FE-SEM) 51 3.3.8 Attenuated reflection-Fourier transform infrared spectra (ATR-FTIR) 51 3.3.9 Contact angle measurement 51 3.4 Reference 52 Chapter 4 Metal organic framework embedded bacterial cellulose pellicle for iodine waste treatment 53 4.1 Introduction 53 4.2 Result and discussion 53 4.2.1 Preparation and characterization of ZIF-8 53 4.2.2 Deposition and Characterization of nanocomposite membrane 59 4.2.3 Adsorption/desorption of BC@Dopa-ZIF 64 4.2.4 Regenerate of Iodine uptaking 69 4.3 Conclusion 71 4.4 Reference 72 Chapter 5 Protein Resistant Surface Coating Based-on Catechol functionalized Poly (N-vinylpyrrolidone) 73 5.1 Introduction 73 5.2 Result and discussion 74 5.2.1 Preparation and characterization of CA-PLL-PVP 74 5.2.2 Preparation and characterization of CA-PVP 79 5.3.3.1 CA-PVP for surface modifications 79 5.3.3.2 Anti-biofouling property of CA-PVP coating 82 5.2.3 Preparation and characterization of CA-PLL-PVP 86 5.2.3.1 CA-PLL-PVP for surface modification 86 5.2.3.2 Anti-biofouling property of CA-PVP coating 90 5.3 Conclusion 91 5.4 Reference 92 Chapter 6 Summary 93 6.1 Summary 93 6.2 Reference 94

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