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A novel functionalized silver nanoparticles solid

Cite this: Dalton Trans., 2014, 43,
chemosensor for detection of Hg(II) in aqueous
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4762 media
ZhuHong Cheng, Gang Li,* Na Zhang and Hai-ou Liu

Received 15th September 2013,
Accepted 3rd December 2013
DOI: 10.1039/c3dt52540f
www.rsc.org/dalton
We report a simple strategy for the fabrication of a highly selective and sensitive Hg(II) chemosensor
based on HMS-Ag composite functionalized rhodamine derivative (R). The prepared chemosensor
HMS-Ag-R was characterized by transmission electron microscopy (TEM), X-ray powder diffraction (XRD),
UV-vis spectrum and Fourier transform infrared spectroscopy (FT-IR). HMS-Ag-R has both fluorescence
and colorimetry performance, and it can realize onsite and real-time detection of Hg(II) with a high sensi-
tivity (0.7 ppb) in aqueous solution. In high concentration of mercury ions, the fluorescence intensity of
HMS-Ag-R against Hg(II) sufficiently showed a typical sigmoidal shape. Moreover, HMS-Ag-R presents
excellent anti-disturbance ability when exposed to a series of competitive cations such as Ag(I), K(I), Li(I),
Na(I), Ba(II), Ca(II), Cd(II), Co(II), Cu(II), Mg(II), Mn(II), Ni(II), Pb(II) and Zn(II). It can be applied to the determi-
nation of Hg(II) in aqueous media. The interaction between HMS-Ag-R and Hg(II) could occur in a short
time (90 s). Importantly, HMS-Ag-R could be regenerated with tetrapropyl ammonium hydroxide (TPAOH)
solution.

1 Introduction
Hg(II) is considered to be one of the most toxic and highly
dangerous metal ions, because both elemental and ionic
mercury can be converted into methyl mercury by bacteria in
the environment, and the mercury subsequently bioaccumu-
lates through the food chain.1–3 However, current main
approaches for monitoring Hg(II) in waste water are costly,
time-consuming methods like atomic absorption/emission
spectroscopy or inductively coupled plasma mass
spectrometry.4–6 These methods are not very convenient for
onsite and real-time detection. Fortunately, the use of chemo-
sensors is a good choice for the detection of Hg(II).
In order to expand the application of chemosensors, the
most efficient method is to improve their hydrophilicity and
recycling performance. Recently, the use of organic–inorganic
hybrid materials has attracted considerable interest.7–23 The
receptor-immobilized inorganic materials such as SiO2,
MCM-41, SBA-15 and HMS have some important
advantages24–30 as a solid chemosensor. However, most of
these chemosensors were synthesized by introducing silane
agents as connectors, which could easily destroy the pore
structure of the inorganic materials.
State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian
University of Technology, Dalian, 116024, P. R. China. E-mail: liganghg@dlut.edu.cn;
Fax: +86-411-8498-6113; Tel: +86-411-8498-6113
During the past few decades, noble metal nanoparticles (Au
NPs or Ag NPs) have received great attention for colorimetric
sensing31–33 owing to their efficient integration of the unique
optical properties, the well-defined nanostructure and the
excellent surface/interface recognition ability.34–37 It has been
proven that the fluorescence can be enhanced several fold by a
metal nanoparticle.38–42 Such a fluorescence enhancement
phenomenon is well-known as the metal-enhanced fluo-
rescence (MEF) effect. In our previous work, we used gold
nanoparticles instead of silane agents as connectors to prepare
an Au-HMS-probe chemosensor, and excellent hydrophilicity
and selectivity for Hg(II) in aqueous media could be achieved.43
However, this chemosensor exhibited a higher detection limit.
To the best of our knowledge, there is not yet a report about
the metal-surface fluorescence enhancement effect for this
kind of chemosensor. Here, as shown in Scheme 1, we report a
new highly selective and sensitive fluorescence platform for
onsite and real-time monitoring Hg(II), and the metal-
enhanced fluorescence effect for this chemosensor was
studied. Firstly, the nanocomposite HMS-Ag was prepared by
adding Ag NPs in the synthesis process of mesoporous
material HMS. Then, the templating agent dodecylamine was
removed by extraction. Last, this new chemosensor was esta-
blished by tethering the rhodamine derivative (R) on the Ag
NPs based on HMS through Ag–N bonds. This chemosensor
HMS-Ag-R exhibited excellent performance for detection of
Hg(II) due to the following advantages: the selectivity for Hg(II)

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Scheme 1 Schematic illustration of the preparation of chemosensor HMS-Ag-R and plausible binding mechanism of HMS-Ag-R with Hg(II).
offered by R, the metal-surface fluorescence enhancement
effect in virtue of Ag NPs and the channels for complexation of
R with Hg(II) enabled by mesoporous material HMS.
2 Experimental
2.1 Reagents
Rhodamine B, tris(2-aminoethyl)amine were purchased from
J&K. Anhydrous sodium sulphate (Na2SO4), dichloromethane,
ethanol, methanol and toluene were purchased from Tianjin
Kemiou Chemical Reagent Co., Ltd. Tetraethylorthosilicate
(TEOS), dodecylamine (DDA) and H2O2 (30 wt%) were pur-
chased from Sinopharm Chemical Reagent Beijing Co., Ltd.
AgNO3 was purchased from Shanghai Chemical Reagent Co.,
Ltd. All chemicals were used as received from the suppliers
without further purification.
2.2 Characterization
Transmission electron microscopy (TEM) images were taken
on a FEI Company Tecnai G2 20 Stwin instrument with an
acceleration voltage of 300 kV. Scanning electron microscopy
(SEM) images were obtained on an HITACHI FE-SEM S-4800
scanning electron microscope. The specimen was prepared by
first dispersing the chemosensor material in ethanol through
supersonic, then placing the drop onto a carbon-coated copper
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grid. X-Ray diffraction (XRD) patterns were obtained at room
temperature on a Rigaku D/MAX-2400 X-ray powder diffraction
(Japan) using Cu Kα radiation, operating at 40 kV and 100 mA.
N2 physical adsorption–desorption isotherms were measured
at 77 K using a Quantachrome AUTOSORB-1 physical adsorp-
tion apparatus. The samples were outgassed in vacuum at
573 K before measurement. The specific surface area and pore-
size distribution were calculated by the Brunauer–Emmett–
Teller (BET) method based on the adsorption data and
Barrett–Joyner–Halenda (BJH) adsorption model. FT-IR spectra
were recorded on a Bruker EQUINOX 55 spectrometer, using
the KBr pellet technique. UV-vis spectra were measured on a
Jasco UV-550 spectrophotometer. Fluorescence spectra
measurements were performed on a Hitachi F-7000 fluo-
rescence spectrophotometer at room temperature. Spectra were
recorded with excitation and emission slit widths of 5 nm,
600 V of voltage and excitation at 520 nm. The absorption
spectra were acquired on a PE Lambda 750 s spectrometer.
1
H NMR spectra were measured on a Varian INOVA 400 MHz
spectrometer (in CDCl3, TMS as internal standard). Mass
spectra were carried out on a TSQ Quantum Ultra spectrometer
using methanol–water (1 : 1) as mobile phase.
2.3 Preparation of HMS-Ag
HMS-Ag metal-nanocomposite was synthesized following the
reported method with proper modifications.43 The
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nanocomposite HMS-Ag was prepared by a one step synthesis
process. Phase A: 5 mL solution of Ag(NH3)2+ (0.024 M) was
mixed with 10 mL of ice-cold hydrogen peroxide solution
(0.3 wt%) under vigorous stirring for 30 min. Phase B: 1.25 g
DDA was dissolved in 9.6 mL ethanol. Then Phase A was added
slowly to Phase B under vigorous stirring. After that, 2.9 mL
diluent HCl solution (0.48 M) was added. 30 minutes later,
5.6 mL TEOS was dropwise added into the mixed system, and
then aged for 18 h. DDA was extracted by ethanol at ambient
temperature. After washing with deionized water and drying at
353 K for 6 h, HMS-Ag composite was obtained finally.
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2.4 Synthesis of rhodamine derivative
According to the literature.11 To a 100 mL flask, under nitro-
gen, 1 g rhodamine B and 5 mL tris(2-aminoethyl)amine dis-
solved in methanol (60 mL) was kept at 353 K for several hours
until the solution color turned to yellow from pink. After
cooling to room temperature, the solvent was evaporated in
vacuo. CH2Cl2 (100 mL) and deionized water (200 mL) were
added into the residue after evaporation and the organic layer
was separated. The CH2Cl2 layer was washed several times with
deionized water followed by drying with anhydrous Na2SO4
overnight. After filtration of sodium sulphate, a yellow oil
denoted as R was obtained after evaporating the solvent in
vacuo. 1H NMR (400 MHz, CDCl3): δ = 7.90–7.88 (m, 1H),
7.45–7.43 (m, 2H), 7.1–7.08 (m, 1H), 6.42–6.39 (m, 4H),
6.29–6.26 (m, 2H), 5.30 (s, 4H), 3.37–3.32 (m, 8H), 3.18–3.14
(m, 2H), 2.55–2.50 (m, 6H), 2.34 (t, J = 8.0 Hz, 4H), 1.17 (t, J =
8.0 Hz, 12H). MS (TSQ Quantum Ultra) calcd for [C34H46N6O2]+
m/z = 570.37, found m/z = 571.39 [M + H]+; calcd for
[C34H46N6O2]2+ m/z = 285.19, found m/z = 286.24 [M + 2H]2+.
2.5 Synthesis of HMS-Ag-R chemosensor
Under nitrogen atmosphere, HMS-Ag (1 g) and R (0.57 g) were
dissolved in anhydrous toluene (50 mL) and stirred for 48 h at
ambient temperature. The collected powder was washed
several times with toluene to remove excess R. After washing
and drying HMS-Ag-R chemosensor was obtained. The detailed
synthetic route of HMS-Ag-R was illustrated in Scheme 1.
2.6 Fluorescent detection of metal ions
Concentration of stock solutions of the aqueous nitric acid
salts (Ag(I), K(I), Li(I), Na(I), Ba(II), Ca(II), Cd(II), Co(II), Cu(II),
Mg(II), Mn(II), Ni(II), Pb(II), Zn(II) and Hg(II)) was 1.25 ×
10−4 M. The suspension solutions of HMS-Ag-R (0.1 g L−1) were
prepared in aqueous solution. Each time, a 2 mL suspension
solution of HMS-Ag-R was added to a quartz cuvette of 1 cm
optical path length, and different stock solutions were gradually
added into the quartz cuvette by micro-syringe.
3. Results and discussion
3.1 Characteristics of HMS-Ag-R chemosensor
The SEM and TEM images of HMS-Ag and HMS-Ag-R were
shown in Fig. 1. SEM image of HMS-Ag exhibited irregular
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Fig. 1 SEM image of HMS-Ag (a) and HMS-Ag-R (b), TEM images of
HMS-Ag (c, d).
spherical particles with diameters of ∼300 nm (Fig. 1a). The
surface of the particles became a little rough after immobiliz-
ing the rhodamine derivative (R) on the Ag NPs (Fig. 1b). The
TEM study was carried out in order to detect the porous struc-
ture of HMS-Ag, as well as the size distribution of the Ag nano-
particles. HMS-Ag sample presented typical wormhole-like
mesopores. The silver nanoparticles size distributed within the
scope of 5–15 nm (Fig. 1c). Ag nanoparticles located in both
the channel wall (Fig. 1d) and the outer surface of the nano-
composite (Fig. 1d inset). These silver nanoparticles provide
active sites for immobilizing rhodamine derivatives (R) which
could go through the mesoporous channels.
The small angle and wide angle powder X-ray diffraction
patterns of HMS-Ag nanocomposite and HMS-Ag-R chemosen-
sor are given in Fig. 2. HMS-Ag nanocomposite presented a
strong reflection peak at 2.3°, which is a characteristic peak of
the wormhole mesoporous structure.44 For HMS-Ag-R, the
peak became weaker and wider, which meant the order of the
mesoporous structure decreased. The possible reason is the
introduction of R. In the wide angle XRD patterns, both
samples presented intense X-ray reflections at 2θ = 38.1°,
44.3°, 64.4° and 77.4°, which correspond to the (111), (220),
(200) and (311) planes of the Ag NPs.
Fig. 3 showed the nitrogen adsorption–desorption isotherm
and the BJH pore size distribution (Fig. 3 inset) of HMS-Ag
nanocomposite. We could observe that HMS-Ag exhibited type
IV isotherm with a H1-type hysteresis loop and a sharp step at
a relative pressure of 0.4. According to the IUPAC classifi-
cation,45 this type of hysteresis loop indicated the presence of
textural mesoporous cylindrical pores, which clearly indicated
that HMS-Ag exhibited uniform textural porosity (Fig. 3). This
result was consistent with the small angle XRD result (Fig. 2a).
The texture parameters of the nanocomposite HMS-Ag are
shown in Table 1, the specific surface area of the HMS-Ag was
540.6 m2 g−1 and the cumulative pore volume was 0.44 cm3 g−1.
The FT-IR spectra of HMS-Ag and HMS-Ag-R are shown in
Fig. 4. Compared with the FT-IR spectrum of HMS-Ag, new
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Table 1 Structural properties of HMS-Ag

Pore Wall BET Pore

d100 a a0 b diameterc thicknessd surface area volumee
(nm) (nm) (nm) (nm) (m2 g−1) (cm3 g−1)

3.9 4.5 2.7 1.8 540.6 0.44

a b 1/2 c
Calculated from XRD analysis. a0 = 2d100/3 . Calculated from
adsorption branch of nitrogen isotherm using BJH model. d Wall
thickness = a0 − pore diameter. e Calculated from the volume adsorbed
of P/P0 at 0.99.
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Fig. 4 FT-IR spectra of HMS-Ag and HMS-Ag-R.

Fig. 2 The Small angle (a) and wide angle (b) X-ray diffraction patterns
of HMS-Ag and HMS-Ag-R.
The diffuse reflectance UV-vis spectra were used to confirm
the existence of Ag nanoparticles and R. The spectrum of
HMS-Ag-R exhibited a significant peak at a wavelength
∼400 nm (Fig. 5 inset), which did not exist in the spectrum of
HMS and could be attributed to the Plasmon resonance absor-
bance of the Ag nanoparticles. This was another valid evidence
that the Ag nanoparticles existed in the composite. Fig. 5
further showed that R anchored on the surface of Ag nanopar-
ticles. A series of characteristic bands at 240, 280 and 320 nm
emerged in the spectra of both R and HMS-Ag-R, which
implied the successful incorporation of R onto the surface of
Ag nanoparticles. These bands could be attributed to the
typical electronic transition of the aromatic ring.11,14 In the
spectrum of HMS-Ag-R, a slight blue shift for the intense

Fig. 3 N2 adsorption–desorption isotherm of HMS-Ag. Inset: the BJH

pore size distribution of HMS-Ag.

transmission bands 2973 and 2924 cm−1 were observed in the

spectrum of HMS-Ag-R, which were assigned to the asym-
metric and symmetric stretching vibrations of the methylene
group (CH2) in the alkyl chain. New bands centered at around
1200–1700 cm−1 were attributed to the C–H stretching and the
aromatic stretching vibrations of the rhodamine group. These
features also appeared in the FT-IR spectrum of R, suggesting
successful grafting of R onto the HMS-Ag composite. Fig. 5 UV-vis spectra of HMS, HMS-Ag, HMS-Ag-R and R.

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absorption band at 320 nm could also be seen. These obser-
vations indicated that the organic group was covalently grafted
onto the composite HMS-Ag. Moreover, the weak peak cen-
tered at ∼550 nm in Fig. 5 was due to the existence of a little
fraction of the rhodamine group in an opening-Spirolactam
form, which gave a slightly pink color.
3.2 HMS-Ag-R responses to Hg(II)
Metal-enhanced fluorescence spectra are shown in Fig. 6. Com-
pared with HMS + R which was a mixture of HMS and R, a
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fluorescence intensity enhancement was observed in the fluo-
rescence spectrum of HMS-Ag-R (at 584 nm) without Hg(II).
Moreover, in the presence of Hg(II), the fluorescence intensity
of HMS-Ag-R was also significantly enhanced compared to
HMS + R (at 584 nm), which was induced by the metal-
enhanced fluorescence (MEF) effect of Ag nanoparticles.
Taking the fluorescence quantum yield of rhodamine B (Φf =
0.31) in water as a reference, HMS-Ag-R showed a higher fluo-
rescence quantum yield of 0.25 in water compared with that of
the mixture of HMS + R (Φ = 0.11).
Fig. 7 showed the fluorescence changes of HMS-Ag-R with
Hg(II) in 2 mM aqueous HEPES buffer medium. Free HMS-Ag-
Fig. 6 Metal-enhanced fluorescence spectra of HMS + R and HMS-Ag-R.
Fig. 7 Fluorescence spectra of HMS-Ag-R (0.1 g L−1 pH = 7.0) with
different concentrations of Hg(II) (0–5 ppm) in 2 mM aqueous HEPES
buffer medium. Inset: the fluorescence change (a) HMS-Ag-R (b)
HMS-Ag-R + 5 ppm Hg(II).
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Fig. 8 UV-vis absorption spectra of HMS-Ag-R with different concen-
trations of Hg(II) (0–5 ppm) in 2 mM aqueous HEPES buffer medium.
Inset: the color change (a) HMS-Ag-R (b) HMS-Ag-R + 5 ppm Hg(II).
R solution showed very weak fluorescence intensity at about
584 nm (excited at 520 nm). Upon addition of Hg(II), a signifi-
cant enhancement of fluorescence intensity at 584 nm was
observed. Meanwhile, the solution showed an orange fluo-
rescence change (Fig. 7 inset). Such changes of fluorescence
were reasonably attributed to the spirolactam (nonfluorescent)
to ring opened amide (fluorescent) equilibrium, which was
induced by the complexation of Hg(II).46,47
The absorption spectra of HMS-Ag-R with varying Hg(II)
concentrations in 2 mM aqueous HEPES buffered medium are
shown in Fig. 8. Free HMS-Ag-R was colorless and exhibited
almost no absorption peak in the visible wavelength range
(>450 nm) due to the closed spirolactam ring. In the presence
of Hg(II), the absorbance was enhanced obviously and a new
peak at 562 nm was observed. Meanwhile, the color of
HMS-Ag-R changed from colorless to pink (Fig. 8 inset). This
result demonstrated that HMS-Ag-R could serve as a “naked-
eye” chemosensor for Hg(II).
The limit of detection (LOD) was calculated by the equation
LOD = 3S0/k, where 3 was the factor at the 99% confidence
level, S0 was the standard deviation of the blank measure-
ments (n = 10), and k was the slope of the calibration curve.
The detection limit of HMS-Ag-R for Hg(II) was determined to
be as low as 0.7 ppb (Fig. 9). This result demonstrated that
determination of trace amounts of Hg(II) at the parts per
billion level was feasible with HMS-Ag-R chemosensor.
HMS-Ag-R had a much lower detection limit than the solid
chemosensor reported in our previous work.43 Furthermore,
the curve of the fluorescence intensity of HMS-Ag-R against
high Hg(II) concentration in the aqueous media sufficiently
showed a typical sigmoidal shape (Fig. 10). This means that a
mercury ion concentration can be obtained based on the fluo-
rescence intensity from this sigmoidal curve. At the same
time, with the increase of mercury ions, the color of the
HMS-Ag-R suspension gradually deepened (Fig. 10 inset).
Response time is an important analytical feature for the
chemosensor. Fig. 11 showed the fluorescence intensity
(584 nm) of HMS-Ag-R at different time intervals after adding
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Fig. 9 Linear calibration plot for Hg(II) in low concentration. The fluor-
escence intensity was measured at an excitation wavelength of 520 nm,
and monitored at a wavelength of 584 nm.
Fig. 10 Plot of the fluorescence intensity (584 nm) of HMS-Ag-R sus-
pension (0.1 g L−1 pH = 7.0) with Hg(II) in high concentration. Inset: the
color change of HMS-Ag-R with different concentrations of Hg(II).
Fig. 11 Response time of HMS-Ag-R with Hg(II).
3 ppm Hg(II). The fluorescence intensity increased quickly
within 90 s and then remained constant with time, which
showed that the Hg(II) complexation process has completed.
So HMS-Ag-R could provide fast detection of Hg(II) within 90 s.
We also investigated the competition-based fluorescence
emission changes of HMS-Ag-R, upon addition of various
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Fig. 12 Fluorescence of HMS-Ag-R to other metal ions (30 ppm, the
black bar) and to Hg(II) or the mixture of other metal ions with Hg(II)
(3 ppm, the red bar).
biologically and environmentally relevant metal ions such as
Ag(I), K(I), Li(I), Na(I), Ba(II), Ca(II), Cd(II), Co(II), Cu(II), Mg(II),
Mn(II), Ni(II), Pb(II) and Zn(II) ions (Fig. 12). Typically, 30 ppm
of competing metal ions were added into the HMS-Ag-R sus-
pension (0.1 g L−1, pH = 7.0). After 2 min incubation, the fluo-
rescence intensities of the resulting solutions were measured.
Then, 3 ppm of Hg(II) was added to the former solution for
another measurement. The fluorescence intensities of
HMS-Ag-R showed no significant changes in the presence of
competitive metal ions. After adding Hg(II) an obvious fluo-
rescence response was induced, indicating the chemosensor
had a high selectivity for Hg(II). The special selectivity was
probably due to the following factors: the suitable coordi-
nation geometry conformation of the receptor, the larger
radius of the Hg(II), the nitrogen-affinity of Hg(II) and the
amide deprotonation ability of the Hg(II).48
Furthermore, the reusability and reproducibility of an excel-
lent chemosensor are of particular interest in developing
recyclable hybrid optical sensors, which could highlight their
important characteristic features and desirability for industrial
applications. The repeated detection/regeneration cycles were
extensively studied. In these procedures, the use of specific
concentrations of TPAOH made the removal of Hg(II) (decom-
plexation) possible. The regeneration ability of HMS-Ag-R was
shown in Fig. 13. It was found that free HMS-Ag-R in 2 mM
aqueous HEPES buffer medium without Hg(II) displayed a very
weak fluorescence, while a significant increase of fluorescence
was observed with the addition of Hg(II). However, the addition
of TPAOH to the HMS-Ag-R-Hg solution caused an immediate
fluorescence decrease. Subsequently, addition of Hg(II) into
the suspension of HMS-Ag-R gave increased fluorescence
again, and the analytical process was entirely visualized by the
naked eye (Fig. 13 inset). HMS-Ag-R could reversibly bind with
Hg(II) and could be used repeatedly at least for four cycles with
a slight decrease in sensitivity.
Finally, this chemosensor was applied to the determination
of Hg(II) in tap water. Because there was no Hg(II) contained in
the tap water as determined by inductively coupled plasma
mass spectrometry (ICP-MS), Hg(II) was deliberately added to
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Fig. 13 Reversibility of HMS-Ag-R with the addition of Hg(II) (3 ppm)
and TPAOH. Inset: the color change of HMS-Ag-R in the regeneration
process.
Fig. 14 Fluorescence spectra of HMS-Ag-R (0.1 g L−1) with different
concentrations of Hg(II) (0–5 ppm) in tap water. Inset: the fluorescence
(top) and color (bottom) change (a) HMS-Ag-R (b) HMS-Ag-R + 5 ppm
Hg(II).
simulate contaminated water. As shown in Fig. 14, the fluo-
rescence intensity of HMS-Ag-R in tap water showed a remark-
able enhancement with addition of Hg(II) (0–5 ppm) and the
fluorescent color changed to bright yellow finally (Fig. 14 inset
(top)). More importantly, the color of the sample also visibly
changed from colorless to red (Fig. 14 inset (bottom)). The
result indicated the suitability of HMS-Ag-R for the determi-
nation of Hg(II) in a natural water sample.
4. Conclusion
In conclusion, a novel metal-enhanced fluorescence chemo-
sensor HMS-Ag-R for Hg(II) has been prepared via a simple
and effective method. The output signals include color and
fluorescence, which were reversibly transduced through simply
opening the spirolactam ring upon Hg(II) complexation. In the
presence of competitive metal ions, HMS-Ag-R exhibited high
selectivity for Hg(II) sensing in aqueous media. We believe that
this metal-enhanced fluorescence platform could be explored
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for many practical applications in chemical, environmental
and biological systems.
Acknowledgements
The authors acknowledge the financial support from the
Program for New Century Excellent Talents in University
(NCET-04-0270) and Central University basic research fund
(DUT10LK11).
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