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Highly selective uorescent sensors for Hg2+ based on bovine serum albumin-capped gold nanoclusters
Dehong Hu,a Zonghai Sheng,b Ping Gong,a Pengfei Zhanga and Lintao Cai*a
Received 11th January 2010, Accepted 15th March 2010 First published as an Advance Article on the web 26th April 2010 DOI: 10.1039/c000589d In this paper, we report a new homogeneous assay for rapid, highly selective and sensitive detection of Hg2+ in aqueous solution based on the induced photoluminescence (PL) quenching of BSA-modied gold nanoclusters (BSA-Au NCs). There was a linear correlation between the expression (I0 I)/I0 and the concentrations of Hg2+ over the ranges of 0.443.2 mM, and the corresponding limit of detection (LOD) was 80 nM. The relative standard deviation of 5 replicate measurements was 1.4% for 1.0 105 mol L1 Hg2+. Moreover, this method has excellent selectivity over metal ions and anions. The feasibility of the BSA-Au NCs sensor for Hg2+ in different aqueous samples was demonstrated with satisfactory results. Moreover, the possible sensing Hg2+ mechanism was also discussed.

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Introduction
Heavy metal pollution is a global problem that is a growing threat to the environment and humanity. Among them, mercury (Hg2+) pollution has received increasing attention due to its highly toxic and bioaccumulative properties.1 The U.S. Environmental Protection Agency (EPA) estimate of annual total global mercury emission from all natural and human-generated sources is ca. 7500 tons per year.2 Thus, the development of a simple, rapid, sensitive and selective method for the detection of Hg2+ is important to protect our environment and health. At present, several analytical methods have been developed for the determination of Hg2+.3 Gold nanoparticles (NPs)-based assays have attracted much attention. One reason is that gold NPs have extremely high extinction coefcients and strongly distance-dependent surface plasmon resonance (SPR) absorption.4 Therefore, functional gold NPs can be used as a colorimetric sensor for Hg2+.5 In these assays, gold NPs solution generally exhibits a color change because of the shift of the SPR band to longer wavelength when the gold NPs are in the aggregated state.6 On the other hand, gold NPs have excellent photoluminescence (PL) properties. Hence, a PL quenching assay for the detection of Hg2+ has also been developed based on PL gold NPs.5b,7 Compared with PL gold NPs, gold nanoclusters (Au NCs) have smaller particle size and higher PL quantum yield (PLQY). Due to the smaller size of the conduction electrons to the Fermi wavelength (less than 1 nm), Au NCs exhibit discreet electronic states and size-dependent PL.8 However, exploration of gold NCs-based PL sensors remains at a very early stage. In this paper, we developed a novel method for rapid, sensitive and selective detection of Hg2+. Bovine serum albumin (BSA) capped Au NCs (BSA-Au NCs) with high PLQY (6%) were
a Key Laboratory for Biomedical informatics and Health Engineering, Institute of Biomedical and Health Engineering, Shenzhen Institutes of Advanced Technology, Chinese Academy of Sciences, Shenzhen, 518055, PR China. E-mail: lt.cai@siat.ac.cn; Fax: +86 755 86392210; Tel: +86 755 86392299 b College of Science, State Key Laboratory of Agricultural Microbiology, Huazhong Agricultural University, Wuhan, 430070, China

prepared and their PL signal was gradually decreased with increasing of Hg2+ concentrations, and the corresponding limit of detection (LOD) was 80 nM. The relative standard deviation of 5 replicate measurements was 1.4% for 1.0 105 mol L1 Hg2+. Moreover, the PL quenching assay for monitoring Hg2+ using BSA-Au NCs has excellent selectivity over metal ions and anions. The feasibility of the method for the analysis of Hg2+ in different aqueous samples was demonstrated with satisfactory results. The PL quenching mechanism of BSA-Au NCs was also discussed.

Experimental
Apparatus UV-Vis absorption spectra were recorded on a PerkinElmer Lambda 25 UV-Vis absorption spectrophotometer. The PL spectra and the PL lifetime measurements were obtained by PL spectrometer (F900, Edinburgh Instruments Ltd.). Surface charge measurements were performed on a Zeta Potential Analyzer (DelsaNano, Beckman, Coulter). The fourier transform infrared spectra (FTIR) were performed on a Thermo Nicolet Corporation Model avatar 330 spectrometer. Reagents HAuCl4$4H2O and BSA (66 000 Da) were obtained from Sinopharm Chemical Reagent Co., Ltd (Shanghai, China). All other chemicals used in this study were of analytical reagent grade and used without further purication. Superpure water (18.25 MU.cm, 25  C) was used to prepare all solutions. Synthesis of BSA-Au NCs BSA-Au NCs were synthesized using BSA as soft templates to grow highly luminescent NCs following the procedure of Xie et al. with some modications.9 All glassware was washed with aqua regia (HCl: HNO3 volume ratio 3: 1), and rinsed with ethanol and superpure water, respectively. In a typical experiment, HAuCl4$4H2O aqueous solution (25 mL, 10 mM, 37  C)
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was added to BSA solution (25 mL, 50 mg mL1, 37  C) under vigorous stirring. NaOH solution (0.5 mL, 1 M) was introduced 2 min later, and the reaction was allowed to proceed under vigorous stirring at 37  C. The color of the solution changed from light yellow to light brown, and then to deep brown. The reaction was completed in 12 h, and the solution was stored at 4  C. The as-prepared BSA-Au NCs have relatively high PLQY ($6%), which was obtained according to ref. 10. Assay of Hg2+ Aliquots (3 mL) of 20 mM phosphate solution (PBS) buffer (pH 7.4) solutions containing the BSA-Au NCs probe and Hg2+ (080 mM) were equilibrated at room temperature prior to measurement of the PL with an excitation wavelength at 334 nm. Safety considerations As Hg and most of the tested metal ions are highly toxic and have adverse effects on human health, all experiments involving heavy metal ions should be performed with protective eyeglasses, chemical safety gloves and protective clothing to prevent skin exposure. The waste solutions containing heavy metal ions should be collectively reclaimed to avoid polluting the environment.
2+

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Fig. 2 The photographs of as-prepared BSA-Au NCs solution under the visible light (a) and UV light (b).

group and Chen et al.7,12 Moreover, the as-prepared BSA-Au NCs showed long PL lifetimes (11 ms, Fig. 8a), and should have great potential for use in sensing molecules of interest through monitoring of their time-resolved PL.13 Effect of Hg2+ on the BSA-Au NCs The effect of Hg2+ on the UV-Vis absorption and PL spectra were investigated. As indicated in Fig. 3, upon the addition of Hg2+ to a solution of BSA-Au NCs, the UV-Vis absorbance of BSA-Au NCs was slightly enhanced, on the contrary, the PL intensity of BSA-Au NCs was effectively quenched by Hg2+. So the PL quenching of BSA-Au NCs was chosen to sense Hg2+. Effect of reaction time on the BSA-Au NCs To understand the response rate of the PL signal upon addition of Hg2+, we have measured the I/I0 at different time intervals. Herein, I and I0 represented PL intensity in the presence and absence of the Hg2+, respectively. The results indicated that the reaction of BSA-Au NCs and Hg2+ was completed rapidly (Fig. 4). The reaction time was shorter in this method than in

Results and discussion

Characterization of as-prepared BSA-Au NCs The as-prepared BSA-Au NCs were detected by UV-Vis absorbance spectroscopy, PL spectroscopy and PL lifetime measurement. As shown in Fig. 1b, the absorption spectrum of BSA-Au NCs exhibited a strong and broad absorption band at 500 nm, which indicated that the particle size of BSA-Au NCs was smaller than 2.5 nm.11 The maximum emission peak of BSA-Au NCs was observed at 654 nm (Fig. 1c), and the maximum absorption wavelength of excitation spectrum was 334 nm (Fig. 1a). The Stokes shift of BSA-Au NCs was 320 nm, which was favorable to prevent spectral cross-talk and enhance the detection signal. The BSA-Au NCs solution was deep brown in color under visible light (Fig. 2a), and an intense red PL (Fig. 2b) under UV light (365 nm). The maximum PLQY of as-prepared BSA-Au NCs was 6%, which was higher than PL gold NPs reported by Changs

Fig. 1 The excitation (a), UV-Vis absorbance (b) and PL spectra (c) of BSA-Au NCs solution.

Fig. 3 Effect of Hg2+ on the UV-Vis absorption and PL spectra of BSAAu NCs. (Hg2+ concentration: 10 mM; curve a and c are in the absence of Hg2+; curve b and d are in the presence of Hg2+).

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Fig. 4 Evolution of the I/I0 over time, recorded after the addition of 5 mM Hg2+ to BSA-Au NCs in 20 mM PBS (pH 7.4).

colorimetric detection of gold NPs.14 So, this method would be a promising candidate for rapid Hg2+ testing. Calibration and sensitivity As shown in Fig. 5, with the increasing concentration of Hg2+, the PL intensity of BSA-Au-NCs was decreased. Meanwhile, the

spectral wavelength maximum was blue-shifted about 8 nm with an obvious change of PL spectrum proles, which indicates the change of surface states of BSA-Au NCs since Hg2+ ions bind onto the particle surface. As shown in Fig. 6, there was a linear correlation between the expression (I0 I)/I0 and the concentrations of Hg2+ over the ranges of 0.443.2 mM (R 0.998) and the LOD was 80 nM (S/N > 3). In order to measure the reproducibility of the system, ve same standard solutions containing 1.0 105 M Hg2+ were added to BSA-Au NCs, the result was evaluated by considering PL intensity. The amount of Hg2+ was found to be (0.99 0.014) 105 mol L1 with its R.S.D. of 1.4%. These values implied that the proposed method possessed the high reproducibility for Hg2+ analysis. In comparison with other detection methods as shown in Table 1, the distinct advantages of this proposed Au NCs-PL method were facile and high selectivity, although the sensitivity of this probe to Hg2+ was not comparable to the others.5a,5g Moreover, Hg2+ could be detected directly without modication by other species, such as DNA probes, rhodamine, to recognize Hg2+ or give out PL signal, and this probe can also be utilized for the detection of Hg2+ in environments with high salinity.5a,5c,5e,5f,5g,15

Interference studies PL quenching of the BSA-Au NCs was studied with the addition of the same concentration of ions (Na+, K+, Mg2+, Ca2+, Ba2+, Pb2+, Mn2+, Fe3+, Ni3+, Zn2+, Cd2+, Al3+, Cr3+, Cu2+, Br, I, NO3, SO3, Ac) as the Hg2+ concentrations in the linear regions (0.2 mM). As shown in Fig. 7, Cd2+, Zn2+, and I led to increases in the (I0 I)/I value to slight degrees; Cu2+ and Ni3+ led to decreases in the (I0 I)/I value to slight degrees; whereas the other ions exhibited no signicant effects under identical conditions. These features contributed to the excellent selectivity toward Hg2+, rendering the BSA-Au NCs highly suitable for the analysis of environmental samples containing other metal ions and anions at high concentrations.
Fig. 5 PL response of BSA-Au NCs upon addition of Hg2+ ions (a: 0, b: 0.4, c: 1.2, d: 5.2, e: 9.2, f: 13.2, g: 23.2, h: 33.2, i: 43.2 and j: 80 mM).

Preliminary analytical application From the above described results it can be deduced that the BSAAu NCs are more useful for the analysis of Hg2+ in terms of selectivity. For this reason this sensor has been chosen for the analysis of Hg2+ in real samples. The determination of Hg2+ concentrations in water is currently the best way of monitoring environmental pollution of Hg2+. For this reason, recovery of spiked Hg2+ in different aqueous samples was studied with the prepared method. Different aqueous samples were simply ltered and the results showed that no Hg2+ existed. Thus, using standard addition method, different concentrations of Hg2+ were respectively spiked in ltered aqueous samples and then analyzed with the method. Table 2 shows the results obtained in additional experiments concerning recovery studies on samples spiked with known amounts of Hg2+. One can see that the recovery study of spiked Hg2+ determined by the BSA-Au NCs-based optical determination exhibited satisfactory results.
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Fig. 6 Quenching efciency plotted with respect to the Hg2+ concentration. Error bars represent the standard deviation of ve measurements.

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Table 1 Comparison of BSA-Au NCs with gold NPs-based sensors for the detection of Hg2+a NPs gold NPs gold NPs gold NPs gold NPs gold NPs gold NPs gold NPs gold NPs gold NPs Au NCs
a

Surface modication agent alkanethiol ligands thiolated single-strand DNA single-stranded DNA single-stranded DNA TGA and R6G MPA homocysteine and MPA MPA and AMP R6G, MPA, and AMP No

Detection PL absorption absorption absorption absorption absorption HRS absorption FRET PL

Masking agent PDCA no no no no PDCA PDCA no no no

Sample matrix sodium tetraborate deionized water deionized water deionized water deionized water deionized water deionized water PBS PBS PBS

LOD/nM 5 100 250 1000 0.06 200 25 500 50 80

Real sample no no no no (river, tap, pond) water no no N.A. urine (river, tap, mineral) water

Ref. 5a 5c 5e 5f 5g 15a 15b 15c 15c this study

HRS, hyper-Rayleigh scattering; FRET, uorescence resonance energy transfer; PDAC, pyridinedicarboxylic acid.

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[Hg2+   BSA-Au NCs] + hv / [Hg2+   BSA-Au NCs*] (2) [Hg2+   BSA-Au NCs*] / [Hg+   BSA-Au NCs] (3)

BSA-Au NCs and Hg2+ form a complex by SHg bond. The electrons within the BSA-Au NCs are rstly excited to the excited state under photo-irradiation, Hg2+ can directly intercept one of the charge carriers and is reduced to Hg+, which can disrupt the

Fig. 7 Effect of different metal ions and anions on the (I0 I)/I0.

Table 2 Determination of Hg2+ in different water samples Sample Hg2+ spiked/mol L1 Hg2+ recovered/mol L1 Recovery (%) River water 1 1.0 107 2 4.0 106 3 2.0 105 Tap water 1 8.0 107 2 4.0 106 3 1.0 105 Mineral water 1 5.0 107 2 4.0 106 3 3.0 105
a

(0.97a 0.15b) 107 (3.85a 0.17b) 106 (2.02a 0.23b) 105 (7.89a 0.29b) 107 (4.11a 0.28b) 106 (0.96a 0.22b) 105 (5.27a 0.29b) 107 (4.26a 0.34b) 106 (2.85a 0.27b) 105

97.0 96.3 101.0 98.6 102.8 96.0 105.4 106.5 95.0

Fig. 8 PL decay proles of BSA-Au NCs in the absence (a) and presence (b) of Hg2+ ions.

Average calculated n 3. b Standard deviation.

Possible reaction mechanisms The selective metal ion response (Fig. 7) of BSA-Au NCs is correlated to the relative metal-sulde bond strength, determined by their respective Ksp value.16 A strong decrease of the PL was observed in the presence of Hg2+, which could be explained in terms of a complex of BSA-Au NCs and Hg2+ by HgS bond (via the 35 Cys residues in BSA). The mechanism can be explained using a photo-induced electron transfer process:17 BSA-Au NCs + Hg
2+

/ [Hg

2+

  BSA-Au NCs]

(1)

Fig. 9 The FTIR spectra of BSA-Au NCsHg2+ (a), BSA-Au NCs (b), and BSA (c) solutions.

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radiative recombination of the holes and the excited electrons, and further quench the PL of the BSA-Au NCs. This assumption is supported by the following facts. Firstly, an increase in the PL lifetime (Fig. 8) and a reduction in the zeta potential are observed after adding Hg2+ to BSA-Au NCs solution, which indicated that a new complexation was formed and some of the surface BSA molecules were integrated with Hg2+. Moreover, the results of FTIR spectra (Fig. 9) show that the hard base of BSA had negligible variations. To further verify the complexation between BSA and Hg2+, a competition test was examined. In this test, ethylenediaminetetraacetate (EDTA), a strong metal ion chelator, was used in competition with BSA-Au NCs for Hg2+. Correspondingly, the quenched PL of BSA-Au NCs was not recovered. In a control experiment, EDTA showed no inuence on the PL of BSA-Au NCs in the absence of Hg2+, which conrmed that the complex formation occurred between BSA and Hg2+ by SHg bond. In addition, the excitation spectrum of the BSA-Au NCs in the presence of Hg2+ was red-shifted, which conrmed that the ground and excited state energies of BSA-Au NCs were changed and the PL of the BSA-Au NCs was quenched. Based on these ndings, we concluded that the complex of BSA-Au NCs and Hg2+ and a photo-induced electron transfer process were the primary mechanism for PL quenching.

References
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Conclusions
A rapid, highly sensitive and selective Hg2+ PL sensor based on a novel BSA-Au NCs has been developed. The NCs were modied by BSA and can be dispersed uniformly in solution. When excited at 334 nm, the NCs yield a distinct emission at 652 nm. The PL intensity of BSA-Au NCs was sensitive to Hg2+ and decreased as the concentration of Hg2+ increased. The calibration graphs were linear over the range of 0.443.2 mM, and the corresponding LOD was 80 nM. The relative standard deviation of 5 replicate measurements was 1.4% for 1.0 105 mol L1 Hg2+. This novel material also possessed a high selectivity toward Hg2+ analysis. The high sensitivity and selectivity response for Hg2+ might be attributed to the excellent sensitivity of PL spectroscopy of BSA-Au NCs and the high complexation constant of the BSA with Hg2+ which was larger than that with other metal ions and anions. Therefore, this strategy can be extended to PL sensors for other metal ions by the modication of the BSA-Au NCs with selective binding groups in principle. The feasibility of the method for the analysis of Hg2+ in different aqueous samples was demonstrated with satisfactory results. Our approach demonstrated such novel BSA-Au NCs nanosensor was quite useful for rapid determination of Hg2+ in aqueous environmental samples. The mechanism for PL intensity change can be explained using a photo-induced electron transfer process.

Acknowledgements
The authors gratefully acknowledge support for this research from the Hundred Talents Program of Chinese Academy of Sciences (No. 277), the National Natural Science Foundation of China (Grant No. 20875062), and the Science and Technology Foundation of Shenzhen City (No. SY200806300225A). The rst two authors contributed equally to this work.
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