Analytical Chemistry Chemical Cytometry Quantitates Superoxide
Analytical Chemistry Chemical Cytometry Quantitates Superoxide
Analytical Chemistry Chemical Cytometry Quantitates Superoxide
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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 />
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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 />
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10.1021/ac1007909 © 2010 American <strong>Chemical</strong> Society<br />
Published on Web 07/16/2010