臺灣博碩士論文加值系統

本研究主要利用三崁段團聯塊式高分子F127所建構之軟模板，合成一系列新穎Au、Pt、Pd三元金屬奈米粒子自組裝之三維懸浮陣列(Three-dimensional floating arrays; 3DFAs )，並利用其表面增強拉曼散射(Surface enhanced Raman scattering; SERS)效應作為微量農藥感測之用。在Pt-Pd二元金屬奈米粒子3DFAs之技術基礎上，本研究進一步導入Au奈米粒子，成功合成創新之Au奈米粒子修飾Pt-Pd 3DFAs三元奈米結構。藉由調控Au前驅物與F127之含量，可得到包括球型組裝與類花瓣組裝結構在內之二種代表性形態三元3DFAs奈米結構。以Au奈米粒子作為Pt-Pd 3DFAs表層修飾，除可保有原本獨特之3DFAs結構特徵，有效增強粒子耦合效應，提高SERS熱點密度。此外，Au奈米粒子修飾Pt-Pd 3DFAs具有極為均一之組裝尺寸，有利於提供穩定之SERS訊號，其可在液態及固態下維持三維組裝結構。而塊式高分子本身具有溶液可穿透性，能有效吸附檢測對象分子，進而提升SERS感測器之性能。研究結果顯示，類花瓣狀組裝結構於孔雀石綠草酸鹽之檢測極限濃度可低於50 ppb，且對於農藥腐絕亦呈顯著之表面增強效應。最後，成功於蔬果皮上檢測出腐絕，展現其極具即時快篩之應用潛力。此新穎貴金屬奈米粒子組裝之高感度三維懸浮陣列SERS感測器，克服了傳統「孤立金屬奈米粒子膠體溶液」之低熱點密度，以及「固態二維奈米粒子陣列基板」之繁複製程，可有效改善現有分子偵測的極限值，亦可應用於生物化學、化學分析、食物安全及環境監控上。

In this work, a series of novel ternary metallic nanoparticles (Au, Pt, and Pd) self-assembled three-dimensional floating arrays (3DFAs) have been successfully synthesized via a facial solution approach with tri-block copolymer F127 as soft templates, and applied as surface enhanced Raman scattering (SERS) chemical sensors for detecting trace amount of pesticides. On the basis of our previously developed techniques used for synthesizing Pt-Pd binary nanoparticles 3DFAs, in this work, we further introduced the 3rd metallic element, Au nanoparticles, and have successfully synthesized innovative Au nanoparticles decorated Pt-Pd 3DFAs. By adjusting the amounts of the Au precursors and F127, two unique presentative styles of ternary 3DFA nanoarchitectures including the spherical and petal-like 3DFA were obtained. The decoration of the Au nanoparticles on the surface layers of Pt-Pd 3DFAs would effectively enhance the SERS hot spots via increasing coupling modes for generating enormous local electromagnetic fields without crushing the special 3D architectures. Besides, the synthesized Au decorated Pt-Pd 3DFA exhibits an extremely uniform dimension and morphology for having steady SRES signals, and can be maintained in dry or wet states. In addition, the liquid penetrable copolymer networks in 3DFAs could effectively enhance the ability of absorbing target molecules and thus the SERS performance. It was found that the petal-like 3DFAs exhibit a lower limitation approaching 50 ppb in detecting malachite green oxalate (MGO) and show promising potential in sensing pesticides such as thiabendazole. The inspiring result of the detection of thiabendazole directly on apple skins has demonstrated great potential for fast real-time screening pesticides. The highly sensitive SERS sensors consisted of novel ternary Au decorated Pt-Pd 3DFAs obviously could not only overcome disadvantages of the very-low hot-spot density of the suspended colloidal metallic nanoparticles and complicated procedures for fabricating conventional 2-dimensional ordered nanoparticles arrays, but significantly improve the molecular detection limitation in the fields of biochemistry, chemical analysis, food safety and environmental monitoring.

摘要 I
Abstract III
誌謝 V
目錄 VI
圖目錄 VIII
表目錄 XI
第一章 前言 1
第二章 文獻回顧 2
2.1貴金屬奈米粒子之表面增強拉曼散射現象 2
2.2 SERS感測應用 6
2.2.1貴金屬膠體溶液直接檢測對象分子 6
2.2.2貴金屬固態基板(無序)檢測對象分子 9
2.2.3規則排列之基板檢測對象分子 11
2.3塊式高分子與貴金屬奈米粒子之合成 13
2.3.1塊式高分子結構與特性 14
2.3.2塊式高分子合成貴金屬奈米粒子 16
2.4研究動機 22
第三章 研究方法與步驟 24
3.1實驗藥品 24
3.2實驗設備 25
3.3塊式高分子F127合成有序之三維懸浮陣列(3DFAs)結構 26
3.4奈米結構分析與SERS檢測 28
3.5拉曼試片之製作及性質量測 29
第四章 結果與討論 30
4.1 Pluronic F127塊式高分子合成三維懸浮陣列結構 30
4.1.1 Pluronic F127合成Au-Pt-Pd三元金屬3DFAs結構 31
4.1.2 Au前驅物的修飾量對3DFAs結構之影響 34
4.1.3 Pluronic F127濃度對3DFAs結構之影響 36
4.2三維懸浮陣列結構之生長機制 40
4.3表面增強拉曼散射感測應用 44
4.3.1孔雀石綠草酸鹽之SERS感測 45
4.3.2農藥腐絕之SERS感測 49
第五章 結論 51
參考文獻 52

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