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Anal. Chem. 2010, 82, 6830–6837<br />

Colorimetric Sensing of Silver(I) and Mercury(II)<br />

Ions Based on an Assembly of Tween 20-Stabilized<br />

Gold Nanoparticles<br />

Cheng-Yan Lin, † Cheng-Ju Yu, † Yen-Hsiu Lin, † and Wei-Lung Tseng* ,†,‡<br />

Department of <strong>Chemistry</strong>, National Sun Yat-sen University, Taiwan, and National Sun Yat-sen University-Kaohsiung<br />

Medical University Joint Research Center, Kaohsiung, Taiwan<br />

We have developed a rapid and homogeneous method for<br />

the highly selective detection of Hg 2+ and Ag + using<br />

Tween 20-modified gold nanoparticles (AuNPs). Citrate<br />

ions were found to still be adsorbed on the Au<br />

surface when citrate-capped AuNPs were modified with<br />

Tween 20, which stabilizes the citrate-capped AuNPs<br />

against conditions of high ionic strength. When citrate<br />

ions had reduced Hg 2+ and Ag + to form Hg-Au alloys<br />

and Ag on the surface of the AuNPs, Tween 20 was<br />

removed from the NP surface. As a result, the AuNPs<br />

were unstable under a high-ionic-strength solution,<br />

resulting in NP aggregation. The formation of Hg-Au<br />

alloys or Ag on the surface of the AuNPs was demonstrated<br />

by means of inductively coupled plasma mass<br />

spectroscopy and energy-dispersive X-ray spectroscopy.<br />

Tween 20-AuNPs could selectively detect Hg 2+ and<br />

Ag + at concentrations as low as 0.1 and 0.1 µM inthe<br />

presence of NaCl and EDTA, respectively. Moreover,<br />

the probe enables the analysis of AgNPs with a minimum<br />

detectable concentration that corresponds to 1<br />

pM. This probe was successfully applied to detect Hg 2+<br />

in drinking water and seawater, Ag + in drinking water,<br />

and AgNPs in drinking water.<br />

Interest in monitoring toxic metal ions in aquatic ecosystems<br />

continues because these contaminants adversely affect the environment<br />

and have serious medical effects. 1 Silver and mercury<br />

are two of the most hazardous metal pollutants, and they are<br />

widely distributed in ambient air, water, soil, and even food. 2,3<br />

For example, silver can inactivate sulfhydryl enzymes and accumulate<br />

in the body, 4 and mercury exposure can damage a<br />

variety of organs and the immune system. 5 Current approaches<br />

to detecting these two metal ions include inductively coupled<br />

* To whom correspondence should be addressed. Fax: 011-886-7-3684046.<br />

E-mail: tsengwl@mail.nsysu.edu.tw.<br />

† Department of <strong>Chemistry</strong>, National Sun Yat-sen University.<br />

‡ National Sun Yat-sen University-Kaohsiung Medical University Joint Research<br />

Center.<br />

(1) Campbell, L.; Dixon, D. G.; Hecky, R. E. J. Toxicol. Environ. Health, Part B<br />

2003, 6, 325–356.<br />

(2) Wood, C. M.; McDonald, M. D.; Walker, P.; Grosell, M.; Barimo, J. F.;<br />

Playle, R. C.; Walsh, P. J. Aquat. Toxicol. 2004, 70, 137–157.<br />

(3) Boening, D. W. Chemosphere. 2000, 40, 1335–1351.<br />

(4) Ratte, H. T. Environ. Toxicol. Chem. 1999, 18, 89–108.<br />

(5) Holmes, P.; James, K. A.; Levy, L. S. Sci. Total Environ. 2009, 408, 171–<br />

182.<br />

6830 <strong>Analytical</strong> <strong>Chemistry</strong>, Vol. 82, No. 16, August 15, 2010<br />

plasma mass spectrometry (ICP-MS), 6,7 atomic absorption<br />

spectrometry, 8,9 and stripping voltammetry. 10,11 Although these<br />

methods offer excellent sensitivity and multielement analysis, they<br />

are rather costly, time-consuming, complex, and nonportable.<br />

In response to these shortcomings, various sensors using small<br />

organic molecules, 12,13 oligonucleotides, 14,15 DNAzymes, 16,17 and<br />

semiconductor quantum dots 18,19 have been investigated for<br />

the selective detection of Ag + or Hg 2+ in aqueous solutions.<br />

Unfortunately, most of these methods suffer from low water<br />

solubility, a complex synthesis procedure, and time-consuming<br />

DNA probe preparation. Recently, gold nanoparticles (AuNPs)<br />

have become another emerging material for sensing Hg 2+ or<br />

Ag + , because they have a high extinction coefficient in the<br />

visible region and behavior that depends on the interparticle<br />

distance. When the distances between the AuNPs become less<br />

than the average particle diameter, the color of the AuNPs<br />

changes from red to purple. Because of the coordination<br />

between the carboxyl groups of thiols and Hg 2+ , thiol-capped<br />

AuNPs have been used for colorimetric sensing of Hg 2+ . 20-22<br />

Also, Hg 2+ can selectively coordinate thymine (T) bases and<br />

forms stable T-Hg 2+ -T complexes. The melting temperature<br />

of cDNA containing T-Hg 2+ -T complexes is higher than that<br />

(6) Karunasagar, D.; Arunachalam, J.; Gangadharan, S. J. Anal. At. Spectrom.<br />

1998, 13, 679–682.<br />

(7) Barriada, J. L.; Tappin, A. D.; Evans, E. H.; Achterberg, E. P. TrAC, Trends<br />

Anal. Chem. 2007, 26, 809–817.<br />

(8) Li, Y.; Chen, C.; Li, B.; Sun, J.; Wang, J.; Gao, Y.; Zhao, Y.; Chai, Z. J. Anal.<br />

At. Spectrom. 2006, 21, 94–96.<br />

(9) Chamsaz, M.; Arbab-Zavar, M. H.; Akhondzadeh, J. Anal. Sci. 2008, 24,<br />

799–801.<br />

(10) Kim, H. J.; Park, D. S.; Hyun, M. H.; Shim, Y. B. Electroanalysis 1998, 10,<br />

303–306.<br />

(11) Mikelova, R.; Baloun, J.; Petrlova, J.; Adam, V.; Havel, L.; Petrek, J.; Horna,<br />

A.; Kizek, R. Bioelectrochemistry 2007, 70, 508–518.<br />

(12) Chatterjee, A.; Santra, M.; Won, N.; Kim, S.; Kim, J. K.; Kim, S. B.; Ahn,<br />

K. H. J. Am. Chem. Soc. 2009, 131, 2040–2041.<br />

(13) Zhan, X. Q.; Qian, Z. H.; Zheng, H.; Su, B. Y.; Lan, Z.; Xu, J. G. Chem.<br />

Commun. 2008, 1859–1861.<br />

(14) Lin, Y.-H.; Tseng, W.-L. Chem. Commun. 2009, 6619–6621.<br />

(15) Wang, J.; Liu, B. Chem. Commun. 2008, 4759–4761.<br />

(16) Li, T.; Shi, L.; Wang, E.; Dong, S. <strong>Chemistry</strong> 2009, 15, 3347–3350.<br />

(17) Hollenstein, M.; Hipolito, C.; Lam, C.; Dietrich, D.; Perrin, D. M. Angew.<br />

Chem., Int. Ed. 2008, 47, 4346–4350.<br />

(18) Koneswaran, M.; Narayanaswamy, R. Sens. Actuators, B 2009, 139, 91–<br />

96.<br />

(19) Chen, J.-L.; Zhu, C.-Q. Anal. Chim. Acta 2005, 546, 147–153.<br />

(20) Huang, C.-C.; Chang, H.-T. Anal. Chem. 2006, 78, 8332–8338.<br />

(21) Yu, C.-J.; Tseng, W.-L. Langmuir 2008, 24, 12717–12722.<br />

(22) Darbha, G. K.; Singh, A. K.; Rai, U. S.; Yu, E.; Yu, H.; Chandra Ray, P.<br />

J. Am. Chem. Soc. 2008, 130, 8038–8043.<br />

10.1021/ac1007909 © 2010 American <strong>Chemical</strong> Society<br />

Published on Web 07/16/2010

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