摘要
贵金属纳米簇(NCs),如金纳米簇(AuNCs)、银纳米簇(AgNCs),是一类很有用的纳米材料。最近几年,高荧光强度,高稳定性的金属纳米簇被密集的报道作为荧光纳米簇探针,用于检测很多种类的目标物。大多数这些检测方法是基于金属纳米簇的荧光增敏或猝灭。在本论文中,我们以目标物对贵金属簇荧光的猝灭效应,建立了多种传感体系。
本论文第一部分实验中,我们合成了牛血清白蛋白(BSA)包裹的银纳米簇,研究了BSA-AgNCs荧光探针对金属离子的响应,以荧光猝灭的方式建立了一种检测Cu2+的方法。并利用组氨酸对铜离子荧光猝灭的抑制的效应,建立了间接检测组氨酸的传感器。
本论文第二部分实验我们建立了一种提高金纳米簇对Hg2+和Cu2+检测选择性的方法。BSA包裹的金纳米簇以荧光猝灭的方式对这两种离子产生响应。EDTA和NaBH4分别加入到相应的体系中作为掩蔽剂,EDTA能与Cu2+络合,NaBH4能把Hg2+还原为Hg0。这两种离子都能抑制相应的离子与纳米簇的相互作用,排除相应的猝灭效应,从而能够检测另一种离子。即使在这两种离子共存的情况下,纳米簇对这两种离子的相应也能有很好的选择性。
Noble metal nanocluster(NCs), such as gold and silver ones, are a type of useful nanomaterials. In recent years, highly luminescence and stable NCs are intensively reported as fluorescence probes for a wide range of targets. Most of these detections are based on either the enhancement or the queching of the fluorescence. In this paper, based on the fluorescence quenching from targets, we developed a variety of sensing systems.
In the first part, we synthesised silver nanoclusters stabibized by bovine serum albumin, and we studied the response of silver nanocluster fluorescent probe toward metal ions, developed a method to detect Cu2+through fluorescence quenching. Furtherly, the complexation of histidine toward copper ion was adopted for an indirect detection of histidine.
In the second part, we developed a method that improved the selectivity of gold nanoclusters toward copper and mercury ions. Bovine serum albumin stabilized gold nanocluster responded to both these two ions through fluorescence quenching. EDTA and sodium borohydride were added respectively as the "masking" reagents, in which EDTA complexed with Cu2+, and borohydride reduced Hg2+into HgO. Both these reactions inhibited the ions'interaction with the nanocluster and eliminated related quenching effect, thus detection of the other ion was achieved. Good selectivity of the nanocluster over these two ions was obtained enabling sensitive detection even under their coexistence.
引文
1. Roco, M.C. Curr. Opin. Biotechnol.,2003,14,337
2. Cao, Y.C. Nanomedicine,.2008,3,467
3. Wang, F.; Tan, W.B.; Zhang, Y.; Fan, X.; Wang, M. Nanotechnology.,2006,17, R1.
4. Baker, M. Nat. Methods.,2010,7,957
5. Michalet, X.; Pinaud, F.; Bentolila, L.; Tsay, J.; Doose, S.; Li, J.; Sundarcsan. G..; Wu, A.; Gambhir, S.; Weiss, S. Science.,2005,307,538
6. Yan, J.; Estevez, M.C; Smith, J.E.; Wang, K.; He, X.; Wang, L.; Tan, W. Nano Today., 2007,2,44
7. Chatterjee, D.K.; Gnanasammandhan, M.K.; Zhang, Y. Small.,2010,6,2781
8. Baker, S.N.; Baker, G.A. Angew. Chem. Int. Ed.,2010,49,6726
9. Zheng, J.; Nicovich, P.R.; Dickson, R.M. Ann. Rev. Phys. Chem.,2007,58,409
10. Muhammed, M.A.H.; Pradeep, T.; Demchenko (Ed.), in:A.P. Advanced Fluorescence Reporters in Chemistry and Biology H, Springer, Berlin, Heidelberg.,2010,333
11. Diez, I.; Ras, R. Advanced Fluorescence Reporters in Chemistry and Biology H, Springer.,2010, pp.307
12. Lin, C.; Lee, C.; Hsieh, J.; Wang, H.; Li, J.; Shen, J.; Chan, W.; Yeh, H.; Chang, W. J. Med. Biol. Eng.,2009,29,276
13. Mooradian, A. Phys. Rev. Lett.,1969,22,185
14. Link, S.; Beeby, A.; FitzGerald, S.; El-Sayed, M.; Schaaff, T.; Whetten, R. J. Phys. Chem. B.,2002,106,3410
15. Zhou, T.; Rong, M.; Cai, Z.; Yang, C. J.; Chen, X. Nanoscale.,2012,4,4013
16. Adhikari, B.; Banerjee, A. Chem. Mater.,2010,22,4364
17. Shang, L.; Yang, L.; Stockmar, R.; Popescu, R.; Trouillet, V.; Bruns, M.; Gerthsen, D.; Nienhaus, G. U. Nanoscale.,2012,4,4155
18. Udaya Bhaskara Rao, T.; Pradeep, T. Angew. Chem. Int. Ed.,2010,49,3925
19. Le Guevel, X.; Trouillet, V.; Spies, C.; Jung, G.; Schneider, M. J. Phys. Chem, C.,2012, 116,6047
20. Zheng, J.; Petty, J.T.; Dickson, R.M. J. Am. Chem. Soc.,2003,125,7780
21. Zheng, J.; Zhang, C.; Dickson, R.M. Phys. Rev. Lett.,2004,93,077402
22. Bao, Y.P.; Zhong, C.; Vu, D.M.; Temirov, J.P.; Dyer, R.B.; Martinez, J.S. J. Phys. Chem. C.,2007,111,12194
23. Jao, Y.-C.; Chen, M.-K.; Lin, S.-Y. Chem. Commun.,2010,46,2626
24. Zhang, J.G.; Xu, S.Q.; Kumacheva, E. Adv. Mater.,2005,17,2336
25. Shang, L.; Dong, S.J. Chem. Commun.,2008,1088
26. Tao, Y.; Lin, Y.; Huang, Z.; Ren, J.; Qu, X. Talanta.,2012,88,290
27. Duan, H.; Nie, S. J. Am. Chem. Soc.,2007,129,2412
28. Muhammed, M.A.H.; Aldeek, F.; Palui, G.; Trapiella-Alfonso, L.; Mattoussi, H. ACS Nano.,2012,6,8950
29. Dattagupta, N.; Crothers, D.M.; Nucl. Acids Res.,1981,9,2971
30. Luk, K.F.S.; Maki, A.H.; Hoover, R.J. J. Am. Chem. Soc.,1975,97,1241
31. Petty, J.T.; Zheng, J.; Hud, N.V.; Dickson, R.M. J. Am. Chem. Soc.,2004,126,5207
32. Sengupta, B.; Ritchie, C.M.; Buckman, J.G.; Johnsen, K.R.; Goodwin, P.M.; Petty, J.T. J. Phys. Chem. C.,2008,112,18776
33. Gwinn, E.G.; O'Neill, P.; Guerrero, A.J.; Bouwmeester, D.; Fygenson, D.K. Adv. Mater.,2008,20,279
34. Richards, C.I.; Choi, S.; Hsiang, J.C.; Antoku, Y.; Vosch, T.; Bongiorno, A.; Tzeng, Y.L.; Dickson, R.M. J. Am. Chem. Soc.,2008,130,5038
35. Yang, X.; Gan, L.; Han, L.; Wang, E.; Wang, J. Angew. Chem.,2013,125,2076
36. Zhou, R.; Shi, M.; Chen, X.; Wang, M.; Chen, H. Chem. Eur. J.,2009,15,4944
37. Liu, G.; Shao, Y.; Wu, F.; Xu, S.; Peng, J.; Liu, L. Nanotechnology.,2013,24,015503
38. Yu, J.; Patel, S.A.; Dickson, R.M. Angew. Chem. Int. Ed.,2007,46,2028
39. Wang, Y.; Cui, Y.; Zhao, Y.; Liu, R.; Sun, Z.; Li, W.; Gao, X. Chem. Commun.,2012, 48,871
40. Xie, J.; Zheng, Y.; Ying, J.Y J. Am. Chem. Soc.,2009,131,888
41. Xavier, P.L.; Chaudhari, K.; Verma, P.K.; Pal, S.K.; Pradeep, T. Nanoscale.,2010,2, 2769
42.Guevel.X.L.:Daum,N.;Schneider,M.Nanotechnology.,2011,22,275103.
43.Wen,F.;Dong,Y.;Feng,L.;Wang,S.;Zhang,S.;Zhang,X.Anal.Chcm.,2011,83, 1193
44.Kawasaki,H.;Hamaguchi,K.;Osaka,I.;Arakawa,R.Adv.Funct.Mater.,2011,21, 3508
45.Kong,Y.;Chen,J.;Gao,F.;Brydson,R.;Johnson,B.;Heath,G.;Zhang,Y.;Wu,L. Zhou,D.Nanoscale.,2013,5,1009
46.Muhammed,M.;Verma,P.;Pal,S.;Kumar,R.;Paul,S.;Omku-mar,R.;Pradeep,T. Chem.Eur.J.,2009,15,1010
47.Zhu,M.;Aikens,C.M.;Hollander,F.J.;Schatz,G.C.;Jin,R.J.Am.Chem.Soc., 2008.130.5883
48.Negishi,Y.;Nobusada,K.;Tsukuda,T.J.Am.Chem.Soc.,2005,127,5261
49.Giepmans,B.N.G.;Adams,S.R.;Ellisman,M.H.;Tsien,R.Y.Science.,2006,312,217
50.Wiedenmann,J.;Nienhaus,G.U.Expert Rev.Proteom.,2006,3,361
51.Nienhaus,G.U.;Wiedenmann,J.ChemPhysChem.,2009,10,1369
52.Huang,T.; Murray,R.J.Phys.Chem.B.,2001,105,12498
53,Huang,C.-C.;Hung,Y.-L.;Shiang,Y.-C.;Lin,T.-Y.;Lin,Y.-S.;Chen,C.-T.;Chang, H.-T.Chem.Asian J.,2010,5,334
54.Wu,Z.;Jin,R.Nano Lett.,2010,10,2568
55.Diez,I.;Pusa,M.;Kulmala,S.:Jiang,H.;Walther,A.;Goldmann,A.S.;Muller, A.H.E.;Ikkala,O.;Ras,R.H.A.Angew.Chem.Int.Ed.,2009,48,2122
56.So,P.T.C.;Dong,C.Y.;Masters,B.R.;Berland,K.M,Annu.Rev.Biomed.Eng.,2000, 2,399
57.Ramakrishna,G.;Varnavski,O.;Kim,J.;Lee,D.;Goodson,T.J.Am.Chem. Soc.,2008,130,5032
58.Patel,S.A.;Richards,C.I.;Hsiang,J.-C.;Dickson,R.M.J.Am.Chem.Soc.,2008,130, 11602
59.Yin,X.-B.;Dong,S.;Wang,E.Trends Anal.Chem.,2004,23,432
60.Fang,Y.M.;Song,J.;Li,J.:Wang,Y.W.;Yang,H.H.;Sun.J.J.;Chen,G.N.Chem. Commun.,2011,47,2369
61.Li,L.;Liu,H.;Shen,Y;Zhang,J.;Zhu,J.-J.Anal.Chem.,2011,83,661
62.Chen,Y.;Shen,Y;Sun,D.;Zhang,H.;Tian,D.;Zhang,J.;Zhu,J.J.Chem.Commun., 2011,47,11733
63.Holmes,P.;James,K.A.F.;Levy,L.S.Sci.Total Environ.,2009,408,171
64.Guo,W.;Yuan,J.;Wang,E.Chem.Commun.,2009,0,3395
65.Xie,J.;Zheng,Y;Ying,J.Y Chem.Commun.,2010,46,961
66.Guo,C.;Irudayaraj,J.Anal.Chem.,2011,83,2883
67.Wei,H.;Wang,Z.;Yang,L.;Tian,S.;Hou,C.;Lu,Y Analyst.,2010,135,1406
68.Guo,W.;Yuan,J.;Wang,E.Chem.Commun.,2009,3395
69.Chen,W.;Tu,X.;Guo,X.Chem.Commun.,2009,1736
70.Durgadas,C.V.;Sharma,C.P.;Sreenivasan,K.Analyst.,2011,136,933
71.Lin,Z.;Luo,F.;Dong,T.;Zheng,L.;Wang,Y.;Chi,Y.;Chen,G.Analyst.,2012,137, 2394
72.Lan,G.-Y.;Huang,C.-C.;Chang,H.-T.Chem.Commun.,2010,46,1257
73.Su,Y.-T.;Lan,G.-Y.;Chen,W.-Y.;Chang,H.-T.Anal.Chem.,2010,82,8566
74.Liu,S.;Lu,F.;Zhu,J.J.Chem.Commun.,2011,47,2661
75.Chen,X.;Zhou,Y.;Peng,X.;Yoon,J.Chem.Soc.Rev.,2010,39,2120
76.Han,B.;Wang,E.Biosens.Bioelectron.,2011,26,2585
77.Huang,Z.;Pu,F.;Lin,Y.;Ren,J.;Qu,X.Chem.Commun.,2011,47,3487
78.Yu,X.;Wang,Q.;Liu,X.;Luo,X.Microchim Acta.,2012,179,323
79.Shang,L.;Chen,H.;Deng,L.;Dong,S.Biosens.Bioelectron.,2008,23,1180
80.Shang,L.;Dong,S.J.Anal.Chem.,2009,81,1465
81.Jin,L.;Shang,L.;Guo,S.;Fang,Y.;Wen,D.;Wang,L.;Yin,J.;Dong,S.Biosens. Bioelectron.,2011,26,1965
82.Zhang,M.;Guo,S.M.;Li,Y.R.;Zuo,P.;Ye,B.C.Chem.Commun.,2012,48,5488
83.Wang,X.;Wu,P.:Hou,X.;Lv,Y.Analyst.,2013,138,229
84.Han,S.;Zhu.S.;Liu.Z.;Hu,L.;Parvecn,S.:Xu,G.Biosens.Bioelectron.,2012,36 267
85.Sharma,J.;Yeh,H.-C.:Yoo,H.;Werner,J.H.;Martinez,J.S.Chem.Commun.,2011. 47,2294
86.Li,J.;Zhong,X.;Zhang,H.;Le,X.C.;Zhu,J.J.Anal.Chem.,2012,84,5170
87.Hu,L.;Han,S.;Parveen,S.;Yuan,Y.;Zhang,L.;Xu,G.Biosens.Bioelectron.,2012, 32.297
88.Lin,H.;Li,L.;Lei,C.;Xu,X.;Nie,Z.;Guo,M.;Huang,Y.;Yao,S.Biosens. Bioelectron.,2013,41,256
89.Guo,W.;Yuan,J.;Dong,Q.;Wang,E.;J.Am.Chem.Soc.,2010,132,932
90.Yeh, H.-C.;Sharma,J.;Han,J.J.;Martinez,J.S.;Werner,J.H.Nano Lett.,2010,10, 3106
91.Yang,S.W.;Vosch,T.Anal.Chem.,2011,83,6935
92.Tao,Y.:Lin,Y.;Huang,Z.:Ren,J.;Qu,X.Analyst.,2012,137,2588
93.Merian,J.;Gravier,J.;Navarro,F.;Texier,I.Molecules.,2012,17,5564
94.Fernandez-Suarez,M.; Ting,A.Y. Nature Reviews Molecular Cell Biology.,2008,9, 929
95.Baker,M.Nature Methods.,2010,7,957
96.Chen,H.;Li,B.;Wang,C.;Zhang,X.;Cheng,Z.;Dai,X.;Zhu,R.;Gu,Y.2013 Nanotechnology.,24,055704
97.Kong,Y;Chen,J.;Gao,F.;Brydson,R.;Johnson,B.;Heath,G.:Zhang,Y;Wu,L Zhou,D.Nanoscale.,2013,5,1009
98.Wang,Y.;Chen,J.T.;Yan,X.P.Anal.Chem.,2013,85,2529
99.Polavarapu,L.;Manna,M.;Xu,Q.-H.Nanoscale.,2011,3,429
100.Shang,L.;Dorlich,R.M.;Brandholt,S.;Schneider,R.;Trouillet,V.;Bruns,M.; Gerthsen.D.;Nienhaus,G.U.Nanoseale.,2011,3,2009
1. Shang, L.; Dong, S.J.; Nienhaus, G.U. Nano Today.,2011,6,401
2. Xie, J.P.; Zheng, Y.G; Ying, J.Y. J. Am. Chem. Soc.,2009,131,888
3. Lu, Y.Z.; Chen, W. Chem. Soc. Rev.,2012,41,3594
4. Guo, Y.M.; Wang, Z.; Shao, H.W.; Jiang. X.Y. Analyst.,2012,137,301
5. Shang, L.; Dong, S.J. J. Mater. Chem.,2008,18,4636
6. Zhang, M.; Ye, B.C. Analyst.,2011,136,5139
7. Liu, X.J.; Zong, C.H.; Lu, L.H. Analyst.,2012,137,2406
8. Deng, L.; Zhou, Z.X.; Li, J.; Li, T.; Dong, S.J. Chem. Commun.,2011,47,11065
9. Yuan, X.; Yeow, T.J.; Zhang, Q.B.; Lee, J.Y.; Xie, J.P. Nanoscale,2012,4,1968
10. Hu, D.H.; Sheng, Z.H.; Gong, P.; Zhang, P.P.; Cai, L.T. Analyst.,2010,135,1411
11. Lin, Y.H.; Tseng, W.L. Anal. Chem.,2010,82,9194
12. Kawasaki, H.; Yoshimura, K.; Hamaguchi, K.; Arakawa, R. Analytical Sciences.,2011, 27,591
13. Guo,W.W.; Yuan, J.P.; Wang, E.K. Chem. Commun.,2009,45,3395
14. Xie, J.P.; Zheng, Y.G.; Ying, J.Y. Chem. Commun.,2010,46,961
15. Su, Y.T.; Lan, G.Y.; Chen, W.Y.; Chang, H.T. Anal. Chem.,2010,82,8566
16. Roy, S.; Palui, G.; Banerjee, A. Nanoscale.,2012,4,2734
17. Liu, Y.L.; Ai, K.L.; Cheng, X.L.; Huo, L.H.; Lu, L.H. Adv. Funct. Mater.,2010,20, 951
18. Huang, Z.Z.; Pu, F.; Lin, Y.H.; Ren, J.S.; Qu, X.G. Chem. Commun.,2011,47,3487
19. Han, B.Y.; Wang, E.K. Biosens. Bioelectron.,2011,26,2585
20. Wen, F.; Dong, Y.H.; Feng, L.; Wang, S.; Zhang, S.C.; Zhang, X.R. Anal. Chem.,2011, 83,1193.
21. Hussain, A.M.P.; Sarangi, S.N.; Kesarwanic, J.A.; Sahu, S.N. Biosens. Bioelectron., 2011,29,60
22. Jin, L.H.; Shang, L.; Guo, S.J.; Fang, Y.X.; Wen, D.; Wang, L.; Yin, J.Y.; Dong, S.J. Biosens. Bioelectron.,2011,26,1965
23. Wang, M.; Mei, Q.S.; Zhang, K.; Zhang, Z.P. Analyst.,2012,137,1618
24. Yeh, H.C.; Sharma, J.; Han, J.J.; Martinez, J.S.; Werner, J.H. Nano Lett.,2010,10, 3106
25.Guo,W.W.;Yuan,J.P.;Dong,Q.Z.;Wang,E.K.J.Am.Chem.Soc.,2010,132,932
26.Liu,YQ.;Zhang,M.;Yin,B.C.;Ye,B.C.Anal.Chem.,2012,84,5165
27.Hu,L.Z.;Han,S.;Parveen,S.;Yuan,Y.L.;Zhang,L.;Xu,G.B.Biosens.Bioelectron., 2012,32,297
28.Wang,Y.L.;Cui,Y.Y.;Zhao,Y. L.;Liu,R.;Sun,Z.P.;Li,W.;Gao,X.Y Chem. Commun.,2012,48,871
29.Li,J.J.;Zhong,X.Q.;Cheng,F.F.;Zhang,J.R.;Jiang,L.P.;Zhu,J.J.Anal.Chem.2012, 84,4140
30.Mathew,Ammu.;Sajanlal,P.R.;Pradeep,T.J.Mater.Chem.,2011,21,11205
31.Durgadas,C.V.;Sharma,C.P.;Sreenivasan,K.Analyst.,2011,136,933
32.Lin,Z.;Luo,F.;Dong,T.;Zheng,L.;Wang,Y.;Chi,Y.;Chen,G. Analyst..2012,137, 2394
1. Lu, Y.Z.; Chen, W. Chem. Soc. Rev.,2012,41,3594
2. Guo,W.W.; Yuan, J.P.; Wang, E.K. Chem. Commun.,2009,45,3395
3. Kawasaki, H.; Yoshimura, K.; Hamaguchi, K.; Arakawa, R. Analytical Sciences.,2011, 27,591
4. Guo, Y.M.; Wang, Z.; Shao, H.W.; Jiang, X.Y. Analyst.,2012,137,301
5. Hu, D.H.; Sheng, Z.H.; Gong, P.; Zhang, P.P.; Cai, L.T. Analyst.,2010,135,1411
6. Durgadas, C.V.; Sharma, C.P.; Sreenivasan, K. Analyst.,2011,136,933
7. Xie, J.P.; Zheng, Y.G.; Ying, J.Y. Chem. Commun.,2010,46,961
8. Xie, J.P.; Zheng, Y.G.; Ying, J.Y. J. Am. Chem. Soc.,2009,131,888 Liu, X.J.; Zong, C.H.; Lu, L.H. Analyst.,2012,137,2406