http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/83234 Mon, 09 Mar 2026 17:32:59 GMT 2026-03-09T17:32:59Z http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/91986 標題: 開發微流體製程用於水相合成金屬有機骨架及其碳材衍生物在環境之應用; Water-based and Microfluidic Synthesis of Metal-Organic Frameworks and their Carbon Derivates for Environmental Applications 作者: 吳希彥; Hsi-Yen Wu 摘要: 金屬有機骨架(MOFs)在發明後，受到學術界大量的注目以及研究，因為其高比表面積、可調控的孔徑，對於催化、吸附、氣體分離領域都有重大的潛力。但目前要在工業上應用仍有許多需要克服的困難，主要是因為生產過程困難，且需要批次合成，以及使用大量有機溶劑。對此，我們提出一套新穎的”微流體液滴水相合成系統”來連續快速合成金屬有機骨架。此外，我們利用生質發酵生產酒精後的廢棄沼渣進行碳化造孔，得到的高比表面積多孔碳並進行了多項環境汙染物的移除及捕捉測試，更應用此材料在超級電容器上，以評估此材料的最佳應用。綜合以上金屬有機骨架合成及碳化造孔技術，我們開發一種金屬有機骨架所衍生的包裹奈米碳管之多孔碳材，並透過其優良的導電性進行超級電容器測試。 第一章中，我們將介紹金屬有機骨架及其多孔碳材衍生物，並介紹多種合成方法以及相關文獻的整理。接著介紹本文中所測試的應用，包含了染料移除、金屬離子吸附、二氧化碳捕捉以及超級電容測試。 第二章主要介紹微流體液滴水相合成系統，此系統透過連續式生成ZIF-8以及MIL-100兩種不同的MOFs以取代批次合成，以達到高達50280 kg m-3 g-1的ZIF-8時空產率(space-time yield, STY)。此章中也對於精準控制MOFs合成的溫度及時間進行詳盡的探討，並發現比起批次合成，我們能在此系統中合成時間24秒下，達到批次合成5小時的結晶程度。同時，我們也利用一種新穎的合成方法”原位合成法(de novo approach)”去將異金屬於ZIF-8合成的過程中同步包覆於孔洞結構中，得到Au@ZIF-8。 第三章中，我們將介紹由生質酒精發酵後的稻稈沼渣生質廢棄物進行碳化造孔，所得到的高比表面積多孔碳材(476.05 m2 g-1)在多種應用上的評估。首先我們對染料的移除效率進行評估，得到比擬文獻(217.39 mg g-1)的高移除效率。重金屬吸附我們選用銅離子作為範例，得到高達169.93 mg g-1的高吸附率。二氧化碳的捕捉在0℃下可以得到2.21 mmol g-1的優異表現。最後將此材料應用在超級電容器上測試比電容值，在5 mV s-1得到的比電容值為36.83 F g-1，也跟文獻中所報導的相關生質廢棄物擁有可比擬的數值。 第四章，綜合了上述的MOFs合成技術以及碳化造孔技術，我們提出一種新穎的包裹奈米碳管於MOFs衍生多孔碳材內的方法。首先，合成同時包含Zn及Co的多金屬MOF，並利用原位合成法搭載Ni於MOF中，得到多金屬的MOF(M-ZIF)，在高溫鍛燒的過程中，MZIF骨架會崩解，且其配體做為生成奈米碳管的碳源，能使奈米碳管在鍛燒過程中同步生長於MOF的孔洞內(CZIF)。對CZIF進行電性相關測試，能得到在5 mV s-1得到的比電容值為36.83 F g-1，且擁有良好的材料穩定性。 於第五章中，我們對本文的內容進行整理以及總結，同時對文中探討的技術進行未來的前景規劃。; Metal-organic frameworks (MOFs) have received a lot of attention in the academic field in the last decades because of their high specific surface area and regulatory pores offering significant potential for catalysis, adsorption, and gas separation. Furthermore, pyrolysis of MOFs provides a simple approach to obtaining high conductive and porous carbon materials suitable for energy applications such as supercapacitors, novel battery systems, and capacitive deionization. Currently, MOF synthesis is usually conducted with organic solvents in a batch system at elevated temperatures. Although the batch system is simple, low mass and heat transfer, inefficient usage of metal precursors and organic linkers, and the requirement for a large number of organic solvents are disadvantages that need to be improved with respect to mass production for practical applications. In this Ph.D. dissertation, two novel MOF synthesis techniques are developed. The first technique is a water-based droplet microfluidic technique for continuous MOF synthesis to solve the mass production problems encountered in conventional batch systems with organic solvents. The second technique is the de novo synthesis of multi-metal MOFs followed by their subsequent pyrolysis to obtain porous carbon materials with carbon nanotube inside their web structure for electrochemical applications. Both developed techniques have a significant impact on MOFs practical application. In Chapter 1, the basic structure, properties, and variety of synthetic methods of MOFs and MOF-derived porous carbon materials are introduced as well as their applications tested in this dissertation including dye removal, metal ion adsorption, carbon dioxide capture, and supercapacitor. In Chapter 2, a water-based droplet microfluidic system is introduced for the continuous synthesis of three kinds of MOFs including ZIF-8, MIL-100, and Au@ZIF-8. A plot regarding the water flow rate versus the oil flow rate of this two-phase droplet system is established to understand the relative water and oil flow rate range for the generation of the stable droplet. ZIF-8 and MIL-100 are synthesized first to compare the difference between the droplet microfluidic system and the batch system as well as the key advantages of the former. Based on SEM and XRD analysis, a droplet microfluidic system can generate MOFs with narrower size distribution and better crystallinity in a shorter time and at lower temperatures. The droplet microfluidic system is further tested for the synthesis of gold particles embedded in the structure of ZIF-8 via the de novo approach. Compared with the conventional incipient wetness impregnation approach, the de novo approach offers efficient usage of gold precursors as indicated by the high gold signal inside ZIF-8 as shown in SEM-EDX analysis. In Chapter 3, biomass residue from the acid-catalyzed steam explosion of rice straw followed by anaerobic fermentation is used as carbon precursors for the synthesis of biomass-derived porous carbon materials via carbonization and KOH-activation process. The BET specific surface area of biomass-derived porous carbon material is 476.5 m2 g-1, which is much higher than the original biomass residue (4.8 m2 g-1). Three applications are tested to show the practical applications of the porous carbon material including methylene blue dye removal, copper ion removal, and CO2 capture. All three cases show comparable adsorption and absorption behavior to other biomass-derived carbon materials. In addition, the specific capacitance is measured and a value of 36.83 F g-1 at 5 mV s-1 indicates the potential of the biomass-derived porous carbon materials as supercapacitance material for energy storage. In Chapter 4, de novo synthesis of multi-metal MOFs combined with pyrolysis to obtain porous carbon materials with carbon nanotubes (CNT) inside the web structure is developed based on the techniques established in the previous two chapters. Three metal ions including Co2+, Zn2+, and Ni2+ are used as metal precursors, while 2- methylimidazole is used as organic linkers for MOF synthesis. The main structure of the resulting multi-MOFs is ZIF-8 (Zn2+) accompanied by some ZIF-67 (Co2+) and Ni ion precursor inside. Ni ions are reduced to Ni nanoparticles during pyrolysis, and porous carbon materials with embedded nickel nanoparticles attached by carbon nanotubes are formed. BET specific surface area of the resulting porous carbon is around 246.36 m2 g-1 when pyrolysis at 600oC. The organic linkers provide a carbon source for CNT growing while Ni nanoparticles act as CNT growing catalysts. The electrochemical measurement at 5 mV s-1 is performed as well, and a value of 36.83 F g-1 indicates the porous carbon materials with CNT inside have the potential for energy application. In Chapter 5, the experimental results of Chapter 2~4 are summarized and the prospects of these two developed MOF-related techniques, water-based droplet microfluidic technique for continuous MOF synthesis and de novo synthesis of multi-metal MOFs combined with pyrolysis for porous carbon materials with carbon nanotube will be discussed as well. Sat, 01 Jan 2022 00:00:00 GMT http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/91986 2022-01-01T00:00:00Z http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/99498 標題: 纖維濾材3D模擬於空氣過濾效能之研究; A Study on Air Filtration Performance via 3D Simulation of Fibrous Filter Media 作者: 翁仲正; Jung-Jeng Weng 摘要: 熔噴不織布是由超細纖維堆疊構成，具有多孔性及孔徑分布範圍廣泛的特性，且其流動孔道相互連通，可減緩因孔洞阻塞造成壓差增加的情形。由大量纖維組成的結構，可供捕集顆粒的表面積廣大，具備有效捕捉汙染物的能力。對於濾材的效能通常考量兩個重要參數，分別是滲透度及過濾效率，過去已有許多研究預測纖維濾材在這兩方面的過濾效能，考量不同纖維排列型態推導理論模型，其中許多理論模型會再經由實驗數據進行優化。 數值模擬則是另一種可用於預測纖維濾材滲透度及過濾效率的方式，但其準確性受模型的結構特性影響。根據規格所列熔噴不織布的結構參數，發現選定建立模型的參數具有難度。本研究藉由不同結構參數之熔噴不織布，提出使用GeoDict®軟體建立對應模型的流程，並透過軟體提供的模組與建立的濾材模型進行數值模擬，預測熔噴不織布的滲透度、最易穿透粒徑(MPPS)及過濾效率。有關滲透度的預測，本研究比較多個無量綱滲透度的理論預測與數值模擬計算之結果。由於使用的熔噴不織布具有多分散纖維直徑，本研究進一步探討適用於濾材模型的等效直徑，數值模擬搭配3種等效直徑計算的無量綱滲透度與部分理論預測結果相近。針對過濾效率及最易穿透粒徑的預測，藉由單根纖維過濾效率和等效直徑計算纖維濾材的過濾效率，與數值模擬所得的數據點進行比較。除纖維體積占比較高的模型外，其餘模型的最易穿透粒徑之數值模擬結果與理論預測接近；數值模擬所得的過濾效率變化趨勢與理論預測曲線相符。由理論預測與數值模擬進行比較分析的結果，說明本研究方法建立的模型具準確性，使數值模擬可有效預測過濾效能，達成降低實驗成本的目標。最後，藉由這些濾材模型進行相關應用分析與討論。; Melt-blown nonwoven fabric consists of stacked ultrafine fibers. It exhibits porosity with a broad pore size distribution, and its interconnected flow channels can help mitigate the increase in pressure drop caused by pore blockage. The structure composed of a large number of fibers provides an extensive surface area for particle collection, making it effective in capturing contaminants. Two critical parameters commonly considered in evaluating the performance of filter media are permeability and filtration efficiency. In the past, numerous studies have predicted the filtration performance of fibrous filter media in these two aspects by deriving theoretical models that consider various fiber arrangement structures. Many of these models were further refined using experimental data. Numerical simulation is an alternative method for predicting the permeability and filtration efficiency of fibrous filter media. However, its accuracy is influenced by the structural characteristics of models. Given the structural parameters of the melt-blown nonwoven fabrics outlined in the specifications, it was found that selecting appropriate parameters for the model construction presented difficulties. Based on the melt-blown nonwoven fabrics with varying structural parameters, this study proposes a procedure for constructing corresponding models via GeoDict® software. Numerical simulations are then performed using the software’s modules and these constructed filter media models to predict the permeability, most penetrating particle size (MPPS), and filtration efficiency of the melt-blown nonwoven fabrics. In terms of permeability prediction, this study compares various theoretical predictions of dimensionless permeability with results obtained from the numerical simulations. Because the melt-blown nonwoven fabrics employed exhibit polydisperse fiber diameters, this study further investigates the equivalent diameters applicable to the filter media models. The dimensionless permeability calculated through the numerical simulations in conjunction with three of these equivalent diameters shows good agreement with certain theoretical predictions. To predict the filtration efficiency and the most penetrating particle size, the filtration efficiency of the fibrous filter media is calculated based on the single fiber filtration efficiency and the equivalent diameters. It is then compared with data points obtained from the numerical simulations. Except for the models with the high fiber volume fraction, the numerical simulation results of the most penetrating particle sizes for the other models are close to the theoretical predictions. The trends in the filtration efficiency obtained from the numerical simulations agree with the theoretical prediction curves. The results of the comparative analysis between the theoretical predictions and the numerical simulations demonstrate the accuracy of the models constructed using the procedure proposed in this study, thereby enabling numerical simulations to predict filtration performance effectively and achieving the objective of reducing experimental costs. Finally, these filter media models are utilized to analyze and discuss related applications. Wed, 01 Jan 2025 00:00:00 GMT http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/99498 2025-01-01T00:00:00Z http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/98055 標題: 幾丁聚醣-聚胺酯功能性水凝膠結合針灸於退化性疾病之神經與組織再生應用; Development of chitosan–polyurethane functional hydrogel combined with acupuncture in neural and tissue regeneration for degenerative diseases 作者: 陳哉羽; Tsai-Yu Chen 摘要: 隨著全球人口老化速度加劇，與老年化相關的慢性退化性疾病已成為威脅人類健康的重大挑戰。發炎老化為一種隨著年齡增長，逐漸累積的低度慢性發炎現象，導致免疫系統功能退化，不僅削弱個體對病原的防禦能力，亦與慢性發炎、組織修復障礙及自體免疫失衡密切相關。近年研究指出，免疫老化與多種退化性疾病的病理機轉密切相關，包括糖尿病慢性傷口、骨關節炎與軟硬骨結構退化，以及神經系統退化如帕金森氏症等疾病。這些疾病不僅導致患者生活品質嚴重下降，也造成龐大的社會醫療負擔，已成為全球公共衛生與再生醫療領域亟待突破的關鍵議題。因此，本論文致力於開發一種結合新型生醫材料與現代針灸的跨領域治療策略，應用於三種與免疫老化密切相關的退化性疾病：糖尿病慢性傷口、軟硬骨缺損及帕金森氏症。本研究之材料研發以創新設計為核心，特別著重於開發具生物可降解性、自癒合能力與導電特性的智慧型水凝膠系統，並經由不同製程與功能性設計，針對不同疾病需求進行材料特性的最佳化。本研究所開發之幾丁聚醣-聚胺酯水凝膠，以聚胺酯奈米交聯劑為架構核心，透過動態席夫鹼鍵結與幾丁聚醣形成高穩定性三維網絡，展現優異的機械強度與自癒合特性，並具促進幹細胞增生、遷移、分化及組織重建等生物活性。本研究進一步將幾丁聚醣-聚胺酯水凝膠應用於多種疾病模型中，並結合針灸進行治療，期望透過生醫材料與針灸治療的協同作用，達成免疫調節、幹細胞活化動員與組織再生之多重目標。第一部分探討幾丁聚醣-聚胺酯水凝膠/冷凍凝膠在糖尿病慢性傷口癒合中的應用，發現其不僅具備與幹細胞良好的交互作用與抗菌性，搭配針灸後可顯著上調血清中促再生因子(如基質細胞衍生因子-1與轉化生長因子-β1)，抑制慢性發炎反應並促進皮膚組織再生。組織染色與分子標誌分析結果顯示，傷口區域有較佳的血管新生與膠原蛋白沉積，傷口癒合速率亦明顯優於對照組。第二部份則開發三層結構的冷凍凝膠作為藥物載體，應用於兔膝關節軟硬骨缺損模型。該材料透過交聯程度差異與冷凍製程的調整製備不同孔洞大小的三層網絡結構，並搭載不同藥物使其具備分層導引幹細胞定向分化之功能，上層負載Y27632促進軟骨分化，中層提供細胞遷移通道，下層負載地塞米松誘導成骨分化，成功引導脂肪間質幹細胞朝軟骨與骨組織定向分化，並有效重建關節結構與功能。此外，搭配腦部對應區域針灸治療後，可進一步活化動員體內幹細胞遷移至患處與幾丁聚醣-聚胺酯水凝膠進行交互作用調節微環境進而達到軟硬骨組織修復。第三部份聚焦於神經退化疾病，開發了一種新型導電聚多巴胺塗佈包覆聚胺酯奈米粒子作為交聯劑，該交聯劑可透過動態席夫鹼鍵結，與水溶性乙二醇幾丁聚醣交聯形成具導電性、可注射性與自癒合能力的生物活性水凝膠，並將此幾丁聚醣-聚胺酯導電水凝膠應用於帕金森氏症大鼠模型，證實該材料具抗氧化、促分化與調控神經微環境之能力。幾丁聚醣-聚胺酯導電水凝膠可有效清除自由基，減緩神經發炎反應，並透過導電特性改善多巴胺神經元訊號傳導。經頭皮針灸輔助治療後，神經幹細胞功能顯著提升，並可改善帕金森氏症大鼠的行為表現與神經電生理異常。組織切片結果顯示，在黑質緻密部與紋狀體中，酪胺酸羥化酶陽性神經元密度明顯恢復，並且M2型小膠質細胞比例大幅上升，呈現有利於神經修復的免疫環境。綜上所述，相較於傳統生醫材料，本研究所提出之幾丁聚醣-聚胺酯水凝膠以水相合成方式製備，具有高適配性與臨床應用潛力，為再生醫學材料領域開創全新可能。本研究更進一步地整合材料科學、生醫工程與現代醫學，提出一種具備高度臨床轉譯潛力的再生醫療策略。幾丁聚醣-聚胺酯水凝膠結合針灸所展現之免疫調節、幹細胞動員及組織再生功能，為未來應用於退化性疾病及神經損傷治療提供新契機，並為中西醫融合與智慧材料臨床應用開啟嶄新篇章。; As the global population continues to age at an accelerating pace, age-related chronic degenerative diseases have emerged as major challenges to human health. Inflammaging, a progressive low-grade systemic inflammation associated with aging, leads to immune system decline, thereby impairing host defense mechanisms and contributing to chronic inflammation, impaired tissue repair, and immune dysregulation. Recent studies have demonstrated that inflammaging is a key pathological driver of various degenerative conditions, including chronic diabetic wounds, osteoarthritis and osteochondral degradation, and neurodegenerative disorders such as Parkinson’s disease. These diseases not only severely diminish patient quality of life but also impose heavy burdens on global healthcare systems, making them urgent targets in public health and regenerative medicine. In response, this study proposes an interdisciplinary therapeutic strategy combining innovative biomaterials with modern acupuncture to address three representative degenerative diseases associated with immune aging: chronic diabetic wounds, osteochondral defects, and Parkinson’s disease. Central to this approach is the development of smart, biodegradable, self-healing, and conductive hydrogels, tailored through optimized fabrication and functional modification to meet disease-specific therapeutic demands. The proposed chitosan–polyurethane hydrogel, constructed using polyurethane-based nanocrosslinkers and dynamic Schiff base bonding with glycol chitosan, forms a stable 3D network with good mechanical properties, self-healing ability, and key biological activities such as promoting stem cell proliferation, migration, differentiation, and tissue regeneration. This hydrogel system was further evaluated across disease models in combination with acupuncture, aiming to synergistically regulate immune responses, mobilize endogenous stem cells, and restore tissue function. In the first part of the study, the chitosan–polyurethane hydrogel and its cryogel form were applied to chronic diabetic wounds. The hydrogel demonstrated robust antibacterial properties and favorable stem cell interactions. When combined with acupuncture, it significantly increased serum levels of regenerative cytokines (e.g., stromal cell-derived factor 1 and transforming growth factor beta), suppressed chronic inflammation, and enhanced skin regeneration. Histological and molecular analyses revealed improved angiogenesis, collagen deposition, and accelerated wound closure compared to controls. In the second part, a three-layer cryogel scaffold was developed as a drug carrier for osteochondral defect repair in a rabbit knee model. By tuning crosslinking densities and cryo-gelation processes, a hierarchical porous structure was created. The top layer delivered Y27632 to promote chondrogenesis, the middle layer provided a conduit for cell migration, and the bottom layer released dexamethasone to induce osteogenesis. This design successfully directed adipose-derived stem cells toward layer-specific differentiation, effectively regenerating both cartilage and subchondral bone. In combination with acupuncture targeting brain-associated regions, enhanced stem cell mobilization and microenvironment modulation further promoted osteochondral repair. The third part focused on neurodegeneration, specifically Parkinson’s disease. A conductive hydrogel system was developed using polydopamine-coated polyurethane nanoparticles as dynamic crosslinkers, forming an injectable, self-healing, and conductive hydrogel via Schiff base bonding with water-soluble glycol chitosan. In a rat model of Parkinson’s disease, this conductive chitosan–polyurethane hydrogel exhibited antioxidant, anti-inflammatory, and neuromodulatory effects. It effectively scavenged reactive oxygen species, reduced neuroinflammation, and enhanced dopaminergic signaling. Combined with scalp acupuncture, the treatment significantly improved neural stem cell activity, motor performance, and electrophysiological outcomes. Histological analysis showed restoration of tyrosine hydroxylase (TH)-positive neurons in the substantia nigra pars compacta (SNpc) and striatum, along with increased polarization of M2-type microglia, indicating a neuroprotective immune environment. In summary, the chitosan–polyurethane hydrogel developed in this study offers high adaptability and strong potential for clinical application in regenerative medicine. By integrating materials science, biomedical engineering, and modern medical practice, this research presents a clinically translatable regenerative therapy. The synergistic combination of intelligent hydrogel systems and acupuncture demonstrates potent capabilities in immune modulation, stem cell mobilization, and tissue regeneration, opening new avenues for treating degenerative diseases and advancing the integration of traditional Chinese medicine with modern biomedical innovation. Wed, 01 Jan 2025 00:00:00 GMT http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/98055 2025-01-01T00:00:00Z