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標題: | 合成規則樹枝狀高分子複合奈米粒子陣列於SERS檢測之應用 Preparation of Dendritic Polymers for Versatile Silver Nanoparticles Containing Substrates in the SERS Detection of Dye Analytes |
作者: | Yu-Wei Cheng 鄭有為 |
指導教授: | 鄭如忠 |
共同指導教授: | 劉定宇 |
關鍵字: | 表面增強拉曼散射檢測,銀奈米粒子,石墨烯奈米片,樹枝狀高分子,蜂窩狀孔洞結構,陽離子界面活性劑, surface-enhanced Raman scattering detection,silver nanoparticles,graphene nanosheets,dendritic polymers,honeycomb-like structure,cationic surfactant, |
出版年 : | 2019 |
學位: | 博士 |
摘要: | 本研究合成規則樹枝狀高分子,並使用化學接枝法或靜電交換法,將銀奈米粒子規則吸附於樹枝狀高分子,形成一高分子奈米複合陣列,應用於表面增強拉曼(SERS)之檢測。利用化學接枝法,將樹枝狀高分子接枝氧化石墨烯與還原氧化石墨烯奈米片,製備一浮動性之表面增強拉曼散射基板,藉由樹枝狀高分子均勻控制銀奈米粒子之排列於石墨烯奈米片,將提供拉曼訊號之偵測靈敏度及穩定性,應用於快速檢測微量環境汙染物(孔雀石綠)。本研究利用具反應選擇性單體4-isocyanato-4'-(3,3-dimethyl-2,4-dioxo-azetidino)-diphenylmethane (IDD)作為建築單元,重複單元逐步反應製備出不同代數末端具十八長碳鏈的樹枝狀poly(urea/malonamides)高分子(G0.5-G2.5)並接枝於石墨烯奈米片。石墨烯奈米片上之不同代數樹枝狀高分子能有效控制銀奈米粒子的粒徑大小(particle size, W)與間距(interparticle gap, D),結果顯示還原氧化石墨烯奈米片接枝G1.5之複合物具有穩定、良好分散性與排列銀奈米粒子,並擁有最低的W/D比(0.8±0.6)和粒子之間距(7.6±5.3 nm),於環境汙染物(孔雀石綠)之表面增強拉曼光譜檢測具有穩定、強大與隨代測物濃度線性關係之增強效果,偵測極限可達2.7×10-11 M (0.01 ppb)。此具浮動性與可撓性SERS基板除了能快速與穩定放大極微量待測物的拉曼訊號以利檢測,未來亦可更廣闊的用於不同化合物分子的偵測。除此之外,將不同代數之樹枝狀高分子,經由改質形成一系列的陽離子界面活性劑,並利用靜電作用力(eletrostatic interaction)使樹枝狀高分子的陽離子型界面活性劑與帶負電的氧化石墨烯形成複合材料,再利用界面活性劑作為成核點還原銀奈米粒子形成有機無機複合材料,透過breath figure法製備大面積的蜂窩狀孔洞結構薄膜,探討不同代數與型態對於蜂窩狀孔洞薄膜的差異,並應用於表面增強拉曼檢測。當製備成蜂窩狀孔洞結構薄膜後,形成蜂窩狀孔洞結構比原始複合材料的SERS增強效果優異,可歸因於當複合材料經由breath figure法製備形成蜂窩狀孔洞結構與銀奈米粒子的排列有加成效果,且複合材料經由自組裝程序可使銀奈米粒子更進一步的分散排列達到更巨大的熱點效應,造成具有更好的電磁場增強效果。 In this study, dendritic polymers with silver nanoparticle were developed as polymer nanoparticle arrays for surface enhanced Raman scattering (SERS) detection. By using a chemical grafting method, we have successfully prepared a floating-typed surface-enhanced Raman scattering (SERS) substrate with the uniform nanoparticle arrays of silver nanoparticles (AgNPs) immobilized on the dendron-exfoliated graphene oxide (GO) and reduced graphene oxide (rGO) nanosheets. These poly(urea/malonamide) dendrons were synthesized, and then grafted on the dendron-exfoliated rGO nanosheets based on a building block of dual functional 4-isocyanato-4’-(3,3-dimethyl-2,4-dioxo-azetidino)-diphenylmethane (IDD). By using dendron-rGO nanosheets as templates for hosting AgNPs, the particle size (D) and interparticle gap (W) of AgNPs could be manipulated by the incorporation of dendrons of various generations (0.5, 1.5, and 2.5 generations), evaluated by transmission electron microscopy. The results indicate that the nanohybrids with 1.5 generation-dendron exhibited stable, enormous, and linear-quantitative Raman enhancement in malachite green detection (1-100 ppm), due to the presence of the lowest W/D ratio (0.8±0.6) and interparticle gap (7.6±5.3 nm). The limit of detection (LOD) of malachite green is lower than 2.7×10-11 M (0.01 ppb). AgNPs@rGO-dendritic derivative nanohybrids as floating and flexible SERS substrates provide ultrasensitive and stable SERS detection in the solutions, exhibiting great potential for practical applications in detecting environmental pollutants. Furthermore, a series of cationic dentritic type poly (urea/malonamide) surfactants were successfully developed. These cationic surfactants were chosen to electrostatically adsorb on the negatively charged GO to form nanocomposites, whereas the AgNPs were reduced on the nanocomposites. Subsequently, the honeycomb-like films with AgNPs were prepared by the breath figure method. As compared with the flat samples of AgNPs@GO-cationic surfactant nanocomposites, the honeycomb-like films with AgNPs could effectively enhance Raman signal in R6G detection. This could be attributed to the additional effects of honeycomb-like structure and well-distributed AgNPs. It is concluded that the honeycomb-like SERS substrates were successfully achieved with great potential of enhancing SERS effect significantly. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/73365 |
DOI: | 10.6342/NTU201900879 |
全文授權: | 有償授權 |
顯示於系所單位: | 高分子科學與工程學研究所 |
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