臺灣博碩士論文加值系統

本研究利用Hg(II)對金奈米粒子（Gold Nanoparticles，Au NPs）生長的阻礙作用，開發了Hg(II)的無標記比色奈米傳感器，並結合表面增強拉曼散射（Surface-Enhanced Raman Scattering，SERS）做更深一步的測定。探討Au NPs對於不同濃度Hg(II)在SERS訊號中對於4-巰基苯甲酸（4-Mercaptobenzoic acid，4-MBA）探針分子之拉曼訊號強度的影響。在最佳化條件下，使用紫外-可見分光光譜法（Ultraviolet-visible spectroscopy，UV-Vis）能夠檢測到10 nM〜100 μM的Hg(II)濃度範圍，偵測極限為7 nM，顯示出對Hg(II)測定的良好選擇性和靈敏度。
SERS於粗糙金屬表面電場增強出現的局部表面等離子體共振（Localized Surface Plasmon Resonance，LSPR）。利用SERS訊號增強效果取決於奈米顆粒的尺寸、形狀與聚集程度，如果金屬奈米粒子具有更大的尺寸，則吸收峰將朝向更長波長區域移動，這可能在Laser激發下於1590 cm-1產生更強的LSPR。在優化條件下，本研究能夠檢測到Hg(II)之線性範圍為0.1 nM〜1.0 μM，偵測極限為0.06 nM。本研究結果顯示使用所開發的方法對不同Hg(II)濃度進行定量分析的可能性。具SERS活性的Au NPs用4-MBA修飾後得知，不論是靈敏度或偵測極限與UV-Vis吸收光譜相比，皆有較佳的效果，而且偵測極限值相差近100倍。
另外在SERS檢測上使用疏水端試紙，與無疏水端的試紙相比， Au NPs會集中在試紙的中心，這不但可以控制Au NPs的分布範圍使其分布密度均勻，也會使訊號峰更穩定，也使光譜積分面積值範圍擴大，獲得更佳的靈敏度。最後於真實水樣的應用，使用UV-Vis吸收光譜與SERS所測結果分別為64〜126%和75〜117%，皆有不錯的回收率，未來希望對此材料進行更進一步研究，提高對Hg(II)的偵測靈敏度，且將其延伸應用於生物成像、藥物載體以及抗菌實驗等面向，利用其優勢發展更全面性的應用。

In this study, Hg(II) label-free colorimetric nanosensor was researched and developed by using Hg(II) versus the growth of gold nanoparticles (Au NPs) obstruction and integrated Surface-Enhanced Raman Scattering (SERS) for further determination.
The study of the effect of Au NPs on the Raman signal strength of 4-Mercaptobenzoic acid (4-MBA) probe molecules in SERS signals for different concentrations of Hg(II). Under optimal conditions, Ultraviolet-visible spectroscopy (UV-Vis) can be used to detect the Hg(II) concentration range of 10 nM~100 μM with a detection limit of 7 nM, showing good selectivity and sensitivity for Hg(II) test.
The electric field of SERS on the rough metal surface enhances the Localized Surface Plasmon Resonance (LSPR) that occurs. The effect of enhancing the SERS signal depends on the size, shape and aggregation of the nanoparticles. If the metal nanoparticles have a larger size, the absorption peak will move toward the longer wavelength region, which may produce a stronger LSPR at 1590 cm-1 under Laser excitation. Under optimized conditions, this study was provided with detecting a linear range of Hg(II) from 0.1 nM to 1.0 μM with a detection limit of 0.06 nM. The results of this study show the possibility of quantitative analysis of different Hg(II) concentrations using the developed method.
With SERS activity of the Au NPs were modified by 4-MBA, no matter the sensitivity or on the detection limitation was with better effect while in comparison with the UV-Vis absorption spectrum, and the detection limitation of SERS was nearly 100 times more than that of UV-Vis.
In addition, the SERS test was conducted by using hydrophobic test paper in comparison with the test paper without the hydrophobic field, the Au NPs were concentrated in the center of the test paper. This not only controls the distribution range of the Au NPs, to make the distribution density uniformly but also makes the signal peak more stable, to expand the range of spectral integral area values for better sensitivity. Finally, in the application of real water samples, the measurements of UV-Vis and SERS are 64~126% and 75~117%, respectively, and both are with good recovery percentage. In the future, we hope to further study this material, improve the detection sensitivity of Hg(II), and extend it to the aspects of bio-imaging, drug carriers and antibacterial experiments, and use its advantages to develop more comprehensive applications.

目錄
摘要 I
Abstract II
目錄 IV
圖目錄 VI
表目錄 IX
一、 序論 1
1-1 前言 1
1-2 拉曼光譜 3
1-3 表面增強拉曼散射 5
1-4 表面增強拉曼散射的應用 7
1-5 邏輯閘介紹 9
1-6 研究動機與目的 11
二、 實驗藥品與儀器 14
2-1 實驗藥品 14
2-2 實驗儀器 16
三、 實驗方法 17
3-1 金奈米粒子合成 17
3-2 汞離子感測器 19
3-3 邏輯閘分析 20
3-4 循環伏安法 20
3-4-1 邏輯閘分析電極預氧化處理 20
3-4-2 合成基材粗糙表面積之測定(Roughness Factor) 21
3-5 真實樣品之測定 22
四、 結果與討論 23
4-1 金奈米粒子偵測汞離子機制 23
4-2 最佳化參數探討 28
4-3 不同濃度汞離子對UV-Vis的探討 39
4-3-1 靈敏度 39
4-3-2 選擇性 41
4-3-3 容忍度 43
4-4 邏輯閘統整及分類 44
4-5 不同拉曼基材探討 48
4-6 探討合成基材的EF值 53
4-7 不同濃度汞離子對SERS的探討 54
4-7-1 靈敏度 54
4-7-2 選擇性 56
4-7-3 容忍度 57
4-8 拉曼檢測之試紙探討 58
4-9 真實水樣之測定 63
五、 討論與未來展望 68
六、 參考文獻 70

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