臺灣博碩士論文加值系統

本研究主要是利用Rhodamine 6G (R6G)與3-mercaptopropionic acid (MPA)修飾金奈米粒子(Au nanoparticles; Au NPs)感測器(R6G/MPA-Au NPs)來偵測高鹽樣品中的Hg(II)。R6G分子吸附在 Au NPs 表面上(R6G-Au NPs)，會因螢光共振能量轉換(fluorescence resonance energy transfer; FRET)及電子轉移，導致R6G螢光被消光(quenching) 98%。存在Hg(II)離子(10 MicroM)可以取代Au NPs表面上R6G而使溶液螢光上升800倍。在最佳條件下，90 nM R6G, 1 nM Au NPs , 1250 nM 3-mercaptopropionic acid (MPA)及5 mM pH 5.0之磷酸鈉，製備的R6G/MPA-Au NPs對Hg(II)有良好選擇性與靈敏度，且溶液螢光上升與Hg(II)濃度(10-250 nM)有良好的線性關係(R2 = 0.98)，偵測極限可達到10 nM。另外，利用BSA (bovine serum albumin)修飾R6G/MPA- Au NPs所得到BSA@R6G/MPA-Au NPs 感測器，可以穩定存在高達1 M NaCl 條件下。在稀釋2倍的海水樣品基質裡，BSA@R6G/MPA-Au NPs溶液螢光強度上升與添加Hg(II)濃度(10-250 nM)亦有良好的線性關係(R2 = 0.95)，偵測極限可達到10 nM。而我們也證明BSA@ R6G/MPA-Au NPs 感測器偵測電池、海水中的Hg(II)是可行的。我們開發此Hg(II)偵測器具備了便宜、簡易、不需螢光物質衍生化，並具有良好的靈敏度與選擇性等優點。

Gold nanoparticles (Au NPs) modified with Rhodamine 6G (R6G) and 3-mercaptopropionic acid (MPA) was developed to determine Hg(II) in high salinity sample. Adsorption of R6G onto Au NPs surface results in fluorescence quenching due to fluorescence resonance energy transfer and electron transfer. In the presence of metal ions such as Hg(II), R6G molecules are released from the Au NP surface and restore the fluorescence of R6G. The modulation of the fluorescence quenching efficiency of R6G-AuNPs in the presence of 10 μM Hg(II) ions can achieve a large turn-on fluorescence enhancement (800-fold). Under the optimum conditions, 90 nM R6G, 1 nM Au NPs, 1250 nM 3-mercaptopropionic acid (MPA) and 5 mM sodium phosphate (pH = 5.0), the R6G/MPA-Au NPs sensor shows good sensitivity and selectivity for Hg(II) over other metal ions. The plot of fluorescence intensity versus the concentration of Hg(II) is linear over the range of 10 to 250 nM (R2 = 0.98) and the limit of detection can be as low as 10 nM. Further modification of R6G/MPA-Au NPs with BSA (bovine serum albumin) obtains BSA@R6G/MPA-Au NPs , which don’t aggregate even under 1 M NaCl. Apply BSA@R6G/MPA- Au NPs to the determination of Hg(II) in spiked half-diluted seawater, the calibration curve shows good linearity (R2 = 0.95) over the range 10-250 nM. The LOD for Hg(II) in this matrix is 10 nM. The feasibility of BSA@R6G/MPA-Au NPs for the determination of Hg(II) in seawater was also demonstrated. The developed Hg(II) sensors have the advantages of low cost, easy to use, no need of fluorescence derivation, good sensitivity and good selectivity.

目錄

第一章 前言 1
1. 1 汞對人體的危害 1
1. 2 汞偵測方法之發展 4
1. 3 奈米粒子之發展與應用 6
1. 4 金奈米感測器開發與應用 6
1. 5 Au NPs合成及光學感測器 7
1. 6 金奈米粒子作為重金屬感測器 10
1. 6. 1 Cu(II)測定 10
1. 6. 2 Pb(II)測定 11
1. 6. 3 Hg(II)測定 12
1. 7 研究動機 19
第二章 材料與方法 21
2. 1 實驗藥品 21
2. 2 儀器設備 22
2. 3 溶液配製 23
2. 3. 1 Rhodamine溶液 23
2. 3. 2 磷酸鹽溶液 23
2. 3. 3 金屬離子溶液 23
2. 3. 4 硫醇溶液 24
2. 3. 5 BSA (bovine serum albumin)溶液 24
2. 3. 6 NaCl溶液 24
2. 3. 7 NaOH溶液 25
2. 3. 8 HCl溶液 25
2. 3. 9實際樣品處理 25
2. 3. 9. 1 電池樣品處理 25
2. 3. 9. 2 海水處理 26
2. 4 金奈米粒子製備 26
2. 5 偵測條件 27
2. 5. 1 磷酸鹽pH值調配 27
2. 5. 2 樣品汞離子分析 27
2. 5. 3 硫醇溶液修飾金奈米粒子 27
2. 5. 4 偵測汞離子之線性 28
2. 5. 5 BSA飽和吸附量測定(Flocculation) 28
2. 5. 6 BSA修飾金奈米粒子 29
2. 5. 7 NaCl存在下BSA@R6G/MPA-Au NPs之穩定性 29
2. 5. 8 海水中BSA@R6G/MPA-Au NPs測定汞離子線性 29
2. 5. 9 真實樣品電池偵測 30
第三章 結果與討論 31
3. 1 Rhodamine dye-Au NPs對各種金屬離子選擇性 31
3. 2 Rhodamine dye-Au NPs偵測Hg(II)離子 32
3. 3 R6G-Au NPs偵測Hg(II)離子 33
3. 4 Rhodamine 6G-Au NPs對各種金屬離子選擇性 34
3. 5 R6G/MPA-Au NPs偵測汞離子 35
3. 6 NaCl存在下BSA@R6G/MPA-Au NPs之穩定性 37
3. 7 BSA@R6G/MPA- Au NPs偵測汞離子 39
3. 8 海水中BSA@R6G/MPA-Au NPs測定汞離子線性 39
3. 9 BSA@R6G/MPA-Au NPs應用於市售鹼性錳電池中Hg(II)的偵測 40
第四章 結論 41
參考文獻 42
圖目錄

圖一. RB-Au NPs、R6G-Au NPs系統對金屬離子之選擇性 46
圖二. pH影響六種Rhodamine dye-Au NPs系統對Hg(II)離子之偵測 47
圖三. R6G-Au NPs偵測Hg(II)螢光光譜圖 48
圖四. R6G-Au NPs系統對金屬離子之選擇性 49
圖五. R6G濃度對R6G/MPA-Au NPs系統偵測Hg(II)靈敏度之影響 50
圖六. 3-mercaptopropionic acid (MPA)濃度對R6G/MPA-Au NPs聚集程度之影響 51
圖七. R6G濃度對R6G/MPA-Au NPs系統偵測Hg(II)之線性的影響 52
圖八. (A) BSA@R6G/MPA-Au NPs 奈米感測器耐高鹽示意圖(B) 53
BSA濃度對200 mM NaCl濃度下R6G/MPA-Au NPs聚集之影響 53
圖九. BSA濃度對不同NaCl濃度下R6G/MPA-Au NPs聚集之影響 54
圖十. BSA對不同NaCl濃度下R6G/MPA-Au NPs系統之螢光值影響 55
圖十一. BSA@R6G/MPA-Au NPs (0.6 nM)系統偵測(A)純水中與(B) 0.5x海水基質中Hg(II)之線性關係 56
表目錄

表一. BSA@ R6G/MPA-Au NPs 和ICP-MS應用於四種市售鹼性錳電池中Hg(II)的偵測 57

[1] Morel, F. M. M.; Kraepiel, A. M. L.; and Amyot, M. Annu. Rev. Ecol. Syst. 1998, 29, 543.
[2] Tchounwou, P. B.; Ayensu, W. K.; Ninashvili, N.; and Sutton, D. Environ. Toxicol. 2003, 18, 149.
[3]http://ejournal.stpi.org.tw/NSC_INDEX/Journal/EJ0001/9709/9709 -11.
[4] Zahir, F.; Rizwi, S. J.; Haq, S. K.; and Khan, R. H. Environ. Toxicol. Pharmacol. 2005, 20, 351.
[5] Stern, A. H. Environ. Res. 2005, 98, 133.
[6] http://www.iosh.gov.tw/data/f16/shp8_1_2.pdf.
[7] http://www.niea.gov.tw/niea/WATER/W33150B.htm.
[8] http://www.niea.gov.tw/niea/pdf/REFSOIL/M10500B.
[9] El-Sayed, M. A. Acc. Chem. Res. 2001, 34, 257.
[10] Schmid, G., Corain, B. Eur. J. Inorg. Chem. 2003, 2003, 3081.
[11] Link, S.; El-Sayed, M. A. Annu. Rev. Phys. Chem. 2003, 54, 331.
[12] Huang, Y. F.; Lin, Y. W.; Chang, H. T. Nanotechnology. 2006, 17, 4885.
[13] Yang, Z.; Lin, Y. W.; Tseng, W. L.; Chang, H. T. J. Mater. Chem. 2005, 15, 2450.
[14] Dubertret, B.; Calame, M.; Libchaber, A. J. J. Nat. Biotechnol. 2001, 19, 365.
[15] http://tw.knowledge.yahoo.com/question/question?qid=10071112
10410.
[16] http://tw.knowledge.yahoo.com/question/question?qid=15080614
10951.
[17] Storhoff, J. J.; Elghanian, R.; Mucic, R. C.; Mirkin, C. A.; Letsinger, R. L. J. Am. Chem. Soc. 1998, 120, 1959.
[18] Huang, C. C.; Huang, Y. F.; Cao, Z.; Tan, W.; Chang, H. T. Anal. Chem. 2005, 77, 5735.
[19] Maxwell, D. J.; Taylor, J. R.; Nie, S. J. Am. Chem. Soc. 2002, 124, 9606.
[20] Ao, L.; Gao, F.; Pan, B.; He, R.; Cui, D. Anal. Chem. 2006, 78, 1104.
[21] Chen, S. J.; Chang H. T. Anal. Chem. 2004, 76, 3727.
[22] Tseng, W. L.; Lee, K. H.; Chang, H. T. Langmuir. 2005, 21, 10676.
[23] Liu, B.; Sun, x.; He, F. Thin Solid Films. 2008, 516, 2213.
[24] Kim, Y.; Johnson, R. C.; Hupp J. T. Nano Lett . 2001, 1, 165.
[25] Liu, J.; Lu, Y. J. Am. Chem. Soc. 2003, 125, 6642.
[26] Huang, C. C.; Chang, H. T. Chem. Commun. 2007, 12, 1215.
[27] Huang, C. C.; Chang, H. T. Anal. Chem. 2006, 78, 8332.
[28] Liu, C. W.; Huang, C. C.; Chang, H. T. Langmuir, 2008, 24, 8346.
[29] Huang, C.-C.; Yang, Z.; Lee, K.-H.; and Chang, H.-T. Angew. Chem. Int. Ed., 2007, 46, 6824.
[30] Liu, C. W.; Hsieh, Y. T.; Huang, C. C.; Lin, Z. H.; and Chang, H. T. Chem. Commun. 2008, 19, 2242.
[31] Chiang, C. K.; Huang, C. C.; Chang, H. T. Anal. Chem. 2008, 80, 3716.
[32] Slocik, J. M.; Stone, M. O.; Naik, R. R. Small. 2005, 11, 1048.
[33] Lee, J.-S.; Han, M. S,; Mirkin, C. A. Angew Chem; Int Ed. 2007, 46,4093.
[34] Lee, J.-S.; Mirkin C. A. Anal Chem. 2008, 80, 6805.
[35] Darbha, G. K.; Ray, A.; Ray, P. C. ACS Nano. 2007, 1, 208.
[36] Darbha, G. K.; Singh, A. K.; Rai, U. S.; Yu, E.; Yu, H.; Ray, P. C. J. Am. Chem. Soc. 2008, 130, 8038.
[37] Chen, J.; Zheng, A. F.; Chen, A. H.; Gao, Y.; He, C.; Kai, X.; Wu, G.; Chen, Y. Anal.Chim.Acta. 2007, 599, 134.
[38] Yu, C. J.; Tseng, W. L. Langmuir. 2008, 24, 12717.
[39] Butler, O. T.; Cook, J. M.; Harrington, C. F.; Hill, S. J.; Rieuwerts, J.; Miles, D. L. J. Anal. At. Spectrom. 2006, 21, 217.
[40] Nolan, E. M.; Lippard, S. J. J. Am. Chem. Soc, 2003, 125, 14270.
[41] Thomas, J. M.; Ting, R.; Perrin, D. M. Org. Biomol. Chem. 2004, 2, 307.
[42] Kim, I. B.; Bunz, U. H. F. J. Am. Chem. Soc. 2006, 128, 2818.
[43] Ono, A.; Togashi, H. Angew. Chem. Int. Ed. 2004, 43, 4300.
[44] Huang, C. C.; Huang,Y. F.; Cao, Z.; Tan, W.; Chang, H. T. Anal. Chem. 2005, 77, 5735.
[45] Tseng, W. L.; Lee, K. H.; Chang, H. T. Langmuir, 2005, 21, 10676.