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Micromolar Hg(II) induced the morphology of gold

nanoparticles: a novel luminescent sensor for
Cite this: J. Mater. Chem. A, 2013, 1,
4475 femtomolar Hg(II) using triazole capped gold
nanoparticles as a fluorophore†
N. Vasimalai and S. Abraham John*

In this paper, we report the morphological changes of gold nanoparticles induced by micromolar Hg(II) and
the determination of femtomolar Hg(II) by a luminescent method. 3,5-Diamino-1,2,4-triazole capped gold
nanoparticles (DAT-AuNPs) were synthesized by a wet chemical method. The HR-TEM images show that the
spherical structure of DAT-AuNPs was changed into a chain-like structure after the addition of micromolar
Hg(II) due to the strong coordination of DAT-AuNPs with Hg(II). The binding of Hg(II) with DAT-AuNPs was
confirmed by XPS. The XPS of Hg5p shows two peaks at 69.3 eV for 5p1 and 74.35 eV for 5p3, suggesting
that mercury was present as Hg(II), coordinated with DAT-AuNPs. The DAT-AuNPs show the emission
maximum at 776 nm while exciting at 520 nm and the emission intensity was enhanced after the
addition of even nanomolar Hg(II). The quantum yield estimated for DAT-AuNPs in the presence of Hg(II)
was 1.5-fold higher than that of free DAT-AuNPs. This suggests that Hg(II) induced the fluorescence
properties of DAT-AuNPs due to photoinduced electron transfer and metal binding-induced
conformational restriction upon complexation. Based on the enhancement of emission intensity, the
concentration of Hg(II) was determined. Further, the DAT-AuNPs showed an extreme selectivity towards
Received 1st January 2013
Accepted 4th February 2013
the determination of 10 nM Hg(II) in the presence of a 50 000-fold higher concentration of common
interferents. The emission intensity increases linearly in the concentration range of 1
107 to 5

DOI: 10.1039/c3ta00003f
1013 M Hg(II) and the detection limit was found to be 0.75 fM L1 Hg(II) (S/N ¼ 3). This method was
www.rsc.org/MaterialsA successfully utilized for the determination of Hg(II) in environmental samples.

1 Introduction Agency guidelines, the concentration of Hg(II) must be 2 mg L1

in drinking water.4 Because of its serious toxic effects to the
Heavy metal pollution is a global problem and is a threat to the environment and human health, the determination of trace
environment and humanity.1–3 Among the different heavy amounts of Hg(II) in environmental and other water bodies, soil
metals, mercury is the most ubiquitous and has high toxic and and food samples is highly essential.
bioaccumulative properties.1,2 Mercuric ions are considered A variety of detection methods have been used to determine
highly hazardous because both elemental and ionic mercury the concentration of Hg(II).5–8 These methods require either
can be converted into methylmercury by bacteria in the envi- expensive equipment and special reagents or trained technicians
ronment, which subsequently bioaccumulates through the food besides low sensitivity, selectivity and complicated sample
chain.1–3 High exposure of Hg(II) affects the brain and its asso- preparation processes.5,6 Hence, they may be unsuitable for
ciated functions, resulting in symptoms such as irritability, routine analysis. On the other hand, the spectrouorimetry
nervousness, tremors, vision problems, deafness and the loss of method is highly effective in terms of ease of handling, high
muscle coordination, sensation and memory. In addition to the sensitivity, selectivity and simplicity of equipment.9,10 It has been
brain, methylmercury can damage the kidney, stomach, heart shown to be a versatile method for the detection of Hg(II) based
and intestines.1–4 According to Environmental Protection on the strong emittive properties of organic dyes.11–14 However,
many of these organic dyes are insoluble in water and therefore
unsuitable for real sample analysis.11–14 It is well known that
Centre for Nanoscience and Nanotechnology, Department of Chemistry, Gandhigram
Rural Institute, Gandhigram-624 302, Dindigul, Tamilnadu, India. E-mail:
organic solvents are harmful to the environment. Further, these
[email protected]; Fax: +91 4512453031; Tel: +91 4512452371 conventional organic uorescent dye molecules usually suffer
† Electronic supplementary information (ESI) available: Stability of DAT-AuNPs; from notorious limitations such as low signal intensities and
XRD; UV-visible spectra of DAT-AuNPs in different micromolar concentrations photobleaching and most of them tend to have narrow excitation
of Hg(II); emission spectra of DAT-AuNPs in different nanomolar concentrations spectra and exhibit a broad emission band with red tailing.11–14
of Hg(II); and interference study bar diagram. See DOI: 10.1039/c3ta00003f

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2.2 Instrumentation
Absorption spectra were measured by using a JASCO V-550 UV-
visible spectrophotometer. Fluorescence spectral measure-
ments were performed on a JASCO FP-6500 spectrouorimeter
equipped with a xenon discharge lamp, 1 cm quartz cell at room
temperature. High resolution transmission electron microscopy
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(HR-TEM) images of AuNPs were obtained from a JEOL JEM

3010 operating at 200 kV. For TEM measurements, the sample
was prepared by dropping 2 mL of a DAT-AuNPs colloidal solu-
tion onto a carbon-coated copper grid. A large volume (250 mL)
of DAT-AuNPs was synthesized and centrifuged (10 000 rpm)
Chart 1 Tautomeric forms of 3,5-diamino-1,2,4-triazole.
and the particles were separated. They were repeatedly washed
with water and dried in a vacuum. The dried AuNP powder was
used for XPS and XRD measurements. XPS measurements were
Recently, it has been shown that the colloidal solution of carried out by using Shimadzu Axis 1165 high performance
AuNPs is an alternative candidate to overcome the above multi-technique analysis using an Al Ka source with a pass
problems. Thus, considerable effort has been exerted to develop energy of 80 eV. XRD analysis was carried out with a Rigaku
Hg(II) sensors using AuNPs as a uorophore.9,15–20 In particular, X-ray diffraction unit using Ni-ltered Cu Ka (l ¼ 1.5406)
the distinctive optical properties of AuNPs encouraged the radiation. The ICP-AES was measured by using a thermo-elec-
researchers to exploit them for a variety of applications.15–20 tron IRIS intrepid II XSP DUO model.
Based on the change in the uorescence properties of AuNPs,
several papers were reported for Hg(II) detection.9,15–20 Even
though the reported AuNPs detect Hg(II) in micromolar and 2.3 Synthesis of DAT-AuNPs
nanomolar levels, they failed to achieve high selectivity.9,15–20 All glassware were thoroughly cleaned with freshly prepared
3,5-Diamino-1,2,4-triazole (DAT) is an interesting heterocy- aquaregia (3 : 1, HCl/HNO3) and rinsed comprehensively with
clic compound and it exists in three different tautomeric forms Millipore water prior to use. DAT-AuNPs were synthesized by a
(anionic, cationic and neutral) (Chart 1).21–23 This compound is wet chemical method using the following procedure. 0.5 mL of
extensively used in the elds of organometallics and medicinal DAT (1 mM) was added to 46 mL of Millipore water in a
chemistry.21–23 It is non-toxic and used for the treatment of round bottom ask with constant stirring. Then, 0.5 mL of
tumour cells with cytostatic drugs that are known to induce HAuCl4$3H2O (0.0317 M) was added to the stirred solution of
apoptosis of tumor cells in all phases of the cell cycle.21–23 It is DAT followed by a slow addition of 3 mL of NaBH4 (0.5%). The
also strongly uorescent in nature and shows the emission color of the solution immediately turns red. The stirring was
maximum at 310 nm while exciting at 259 nm. continued for another 30 min and the solution was stored in a
The present work describes the morphological changes of refrigerator.
DAT-AuNPs from a spherical to a chain-like structure induced
by Hg(II) and the determination of femtomolar Hg(II) by the 3 Results and discussion
spectrouorimetric method. The emission intensity of DAT-
AuNPs was increased even in the presence of 0.5 pM Hg(II). 3.1 Spectral characterization and stability of DAT-AuNPs
Based on the enhancement of emission intensity, the UV-visible spectrophotometry is an important tool for the
concentration of Hg(II) was determined. Further, the present preliminary examination of metal nanoparticles because they
uorophore showed an extreme selectivity towards the deter- have free electrons and the combined vibration of electrons of
mination of 10 nM Hg(II) in the presence of a 50 000-fold higher metal nanoparticles in resonance with the light wave gives rise
concentration of common interferents including transition to a SPR band.24,25 Fig. 1 shows the absorption spectra recorded
metal ions. The proposed method was successfully utilized for DAT, HAuCl4 and a mixture of DAT and HAuCl4 in the
to determine the concentration of Hg(II) in environmental presence and absence of NaBH4. DAT shows an absorption
samples. maximum at 259 nm (curve a) whereas HAuCl4 in water exhibits
an absorption maximum at 291 nm (curve b). Addition of
2 Experimental HAuCl4 solution to an aqueous solution of DAT causes the
absorption band characteristics of DAT to vanish while the
2.1 Materials absorption intensity at 291 nm was increased (curve c). The
Hydrogen tetrachloroaurate(III) trihydrate (HAuCl4$3H2O) and observed increase in intensity at 291 nm was ascribed to
3,5-diamino-1,2,4-triazole were purchased from Sigma-Aldrich. the complex formation between DAT and HAuCl4. When 3.0 mL
Sodium borohydride and mercuric nitrate were purchased from of 0.5% NaBH4 was slowly added to a mixture of DAT and
Merck (India) and were used as received. All other chemicals HAuCl4 solution, the colorless solution becomes wine red
used in this investigation were of analytical grade and used immediately (inset of Fig. 1a) and shows a new absorption band
directly without further purication. Millipore water (18 MU at 520 nm (curve d). This new band corresponds to the SPR band
cm) was used to prepare the solutions in the present work. of the AuNPs, conrming the successful formation of AuNPs.

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3.3 Determination of concentration of AuNPs and surface

coverage of DAT ligands
We have estimated the concentration of AuNPs from the
number of atoms per particles “N” using the following
equation26

N ¼ prD3NA/6M
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(1)

where ‘r’ is the density of gold (19.3 g cm3), ‘D’ is the average
diameter of AuNPs, ‘NA’ is the Avogadro number (6.023
1023)
and ‘M’ is the atomic mass of gold (196.96 g). Then, we have
calculated the concentration of DAT-AuNPs using the value of
the number of atoms per particles “N”27

C ¼ NT/N
V
NA (2)
Fig. 1 UV-visible spectra of (a) DAT, (b) HAuCl4 and (c) after the addition of
where ‘C’ is the concentration of AuNPs, ‘NT’ is the total number
HAuCl4 to DAT and (d) NaBH4 to a mixture of HAuCl4 and DAT. Inset: photograph
of freshly prepared DAT-AuNPs. of gold atoms added to HAuCl4, and ‘V’ is the volume of the
reaction solution in litre. The concentration of DAT-AuNPs was
found to be 1.9 mM. Further, we have estimated the number of
The stability of the AuNPs was usually checked from the DAT molecules on the surface of AuNPs. It was found that 295
changes in their absorption characteristics such as shi in the DAT molecules covered a single AuNP. The surface area of DAT
absorption maximum and decrease in the absorbance. In molecules was found to be 2.61 nm2.28
contrast to freshly prepared DAT-AuNPs, no change in the
absorption characteristics of six months aged DAT-AuNPs was
3.4 Characterization of AuNPs by XRD and XPS
observed (Fig. S1, ESI†). Further, the wine red color of the solu-
tion also remains the same (inset of Fig. S1, ESI†). These results The crystalline nature of DAT-AuNPs was conrmed from the
indicate that the synthesized DAT-AuNPs were highly stable. XRD analysis (Fig. S2, ESI†). It shows the diffraction features
appearing at 38.17 , 44.43 , 64.52 , 77.48 and 82.10 corre-
sponding to (111), (200), (220), (311) and (222), respectively.29
3.2 HR-TEM study
The peak corresponding to the (111) plane is more intense than
The size and morphology of the synthesized DAT-AuNPs were the other planes. The ratio between the intensity of the (200)
examined by HR-TEM. Fig. 2 shows the HR-TEM images of DAT- and (111) diffraction peaks was much lower (0.5), suggesting
AuNPs taken at different magnications. The HR-TEM images that the (111) plane is a predominant orientation. The width of
show that the DAT-AuNPs were roughly spherical in shape with the (111) peak was employed to calculate the average crystalline
a size of 7 nm and have a narrow size distribution (Fig. 2B). size of the DAT-AuNPs using the Scherrer equation.29 The
The high magnication HR-TEM image of a single DAT-AuNP calculated average size of the AuNPs is 7.0 nm, which closely
originating from a single crystal shows the lattice images matches with the particle size obtained from HR-TEM.
(Fig. 2C). Fig. 2D shows the selected area diffraction pattern Further, the DAT-AuNPs were characterized by XPS. Fig. 3
(SAED) of DAT-AuNPs. The SAED of DAT-AuNPs illustrates the shows the XPS obtained for DAT-AuNPs. The survey spectrum of
crystalline nature of AuNPs. DAT-AuNPs (Fig. 3A) indicates the presence of Au, C and N
species. The XPS of Au4f shows two peaks at 85.75 eV for 4f7/2
and 89.45 eV for 4f5/2 (Fig. 3B). The position and q difference
between the two peaks (3.7 eV) exactly match with the value
reported for Au0.30 The absence of a peak at 84.9 eV corre-
sponding to Au(III) indicates that the gold atoms are present as
Au0.31–33 The C1s spectrum shows a binding energy at 284.75 eV
(Fig. 3C), suggesting that DAT remains on the surface of AuNPs.
The N1s spectrum shows a binding energy at 401 eV (Fig. 3D)
which is assigned to a free amine group (–NH2) on the surface of
AuNPs.33 The obtained XPS results for DAT-AuNPs clearly
conrmed the presence of DAT molecules on the surface of
AuNPs and the absence of Au ions.

3.5 Spectrophotometric determination of Hg(II)

Fig. 2 HR-TEM images of different magnifications (A–C) and selected area The absorption spectra of DAT-AuNPs in the presence of
diffraction (D) of DAT-AuNPs. different concentrations of Hg(II) are shown in Fig. 4. The

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AuNPs. This was conrmed by HR-TEM. It has been well

established that when the spherical structure of AuNPs was
changed, a new absorption band would appear at higher
wavelength.28,34 Fig. 5 shows the HR-TEM images of DAT-AuNPs
recorded at different magnications aer the addition of 7 mM
Hg(II). In contrast to the image of DAT-AuNPs (Fig. 2), the HR-
TEM images recorded at different magnications in the pres-
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ence of Hg(II) show that the spherical morphology of the

DAT-AuNPs was changed into a chain-like structure (Fig. 5).
The changes in the morphology of DAT-AuNPs may be
explained as follows. While adding Hg(II) into DAT-AuNPs, the
monodispersed spherical AuNPs come closer due to the decrease
in electrostatic repulsion and they coordinate with Hg(II). This
leads to the formation of a chain-like structure. It is to be noted
here that the size of the nanoparticles remains unchanged (Fig. 2
and 5). While adding Hg(II) to DAT-AuNPs solution, Hg(II) coor-
dinates with the free amine groups of the DAT-AuNPs.34 The
Fig. 3 XPS of DAT-AuNPs: (A) survey spectrum and enlarged XPS spectra for DAT- results obtained from the UV-visible and HR-TEM have good
AuNPs in the (B) Au4f, (C) C1s and (D) N1s regions. agreement with Mie theory.35 According to Mie theory, when the
distance between the two nanoparticles becomes smaller than
the sum of their radii, the UV-visible spectra show a broad band
DAT-AuNPs show the absorption band at 520 nm (curve a). Aer
at a higher wavelength region.34,35 The changes in the absorption
the addition of 1 mM Hg(II) to DAT-AuNPs, a small shoulder
characteristics of AuNPs aer the addition of Hg(II) may be used
band appeared at 650 nm whereas the SPR band at 520 nm
to determine the concentration of Hg(II). However, the spectral
remains unchanged (curve b). Further, the red color of the DAT-
changes were observed only in the micromolar concentration
AuNPs solution immediately changed to purple while adding
range of Hg(II). This indicates that the spectrophotometric
1 mM Hg(II) (inset of Fig. 4).34 While increasing the concentra-
method was not suitable to determine less than micromolar
tion of Hg(II) into DAT-AuNPs, the SPR band at 520 nm
concentrations of Hg(II) using DAT-AuNPs. Therefore, an attempt
remained constant whereas the shoulder band absorbance was
is made to employ the spectrouorimetry method to determine
increased; it becomes a major band and appears at higher
the concentration of Hg(II).
wavelength (curves c–h). Aer the addition of 7 mM Hg(II), the
absorbance of both peaks (520 and 710 nm) was decreased
(Fig. S3, ESI†) and the solution became turbid. A purple 3.6 Spectrouorimetric determination of Hg(II)
precipitate settled down at the bottom of the quartz cell aer
The spectrouorimetry method is an important tool to deter-
the addition of 12 mM Hg(II). We presumed that the observed
mine several toxic metal ions because of its simple experimental
visible color change and appearance of a new peak at a higher
setup and high selectivity and sensitivity.9–13,15–20,36 Before
wavelength region may be due to the structural changes of DAT-
examining the use of DAT-AuNPs for the determination of
Hg(II), we have examined the emission properties of DAT alone

Fig. 4 UV-visible spectra of DAT-AuNPs in different concentrations of Hg(II): (a) 0,

(b) 1, (c) 2, (d) 3, (e) 4, (f) 5, (g) 6 and (h) 7
106 mol L1. Inset: photographs of Fig. 5 HR-TEM images of different magnifications of DAT-AuNPs after the
(A) DAT-AuNPs and (B) DAT-AuNPs in the presence of 1
106 mol L1 Hg(II). addition of 7 mM Hg(II).

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in the presence and absence of Hg(II). DAT shows the emission AuNPs, the emission intensity was increased to 6-fold at 776 nm
maximum at 310 nm while exciting at 259 nm. While adding while exciting at 520 nm. Further increasing the nanomolar
Hg(II) to DAT, the emission intensity at 310 nm was enhanced. concentration of Hg(II), the emission intensity was signicantly
The obtained enhanced emission intensity encouraged us to enhanced (curves b–k). The observed emission intensity
use DAT as a capping agent for the AuNPs. As mentioned above, enhancement can be rationalized in terms of photoinduced
295 molecules will be coordinated on the surface of AuNPs. It electron transfer40 and metal binding-induced conformational
is obvious that more Hg(II) will be expected to coordinate with restriction upon complexation.41 On the other hand, the DAT-
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DAT which was three dimensionally chemisorbed on the AuNPs aggregation can reduce their vibration and rotation
surface of AuNPs. The DAT-AuNPs show the emission maximum speed. Weakness of the Brownian movement and decrease of
at 776 nm while exciting at 520 nm (SPR band) (Fig. 6, curve a). collision probability between the AuNPs result in the increase of
We have excited both DAT capped and DAT free AuNPs at the external energy rate and this leads to the enhancement
259 nm. The DAT capped AuNPs show a very weak emission of the uorescence intensity of DAT-AuNPs.
band at 310 nm whereas the DAT free AuNPs do not show any Since we obtained signicant enhancement in the emission
emission band at 310 nm (inset of Fig. S4, ESI†). Since the intensity at 776 nm even in the presence of 10 nM Hg(II) (Fig. S4,
uorescence of DAT was quenched by AuNPs due to the uo- ESI (curve b)†), we have extended the emission studies in the
rescence resonance energy transfer (FRET) interaction between presence of the picomolar range of Hg(II). Fig. 6 shows the
the DAT and AuNPs, no emission band was observed. A similar emission spectra of DAT-AuNPs in the presence of different
type of quenching has already been reported for several mole- picomolars of Hg(II). The emission intensity was increased while
cules capped with AuNPs.37–39 Since excitation of DAT-AuNPs at increasing picomolar Hg(II) into DAT-AuNPs (Fig. 6, curves c–l).
259 nm shows a weak emission at 310 nm, we have recorded the Interestingly, even in the presence of 0.5 pM Hg(II), the emission
emission spectrum of DAT-AuNPs at different excitation wave- intensity at 776 nm was increased (Fig. 6, inset A). The emission
lengths from 260 to 600 nm (each excitation with 5 nm differ- spectrum of Hg(II) does not show any emission band at 776 nm
ence). We observed the maximum emission intensity at 776 nm (curve m). A good linearity was observed in the emission
upon excitation at 520 nm. The obtained emission intensity intensity against 1
107 to 5
1013 concentrations of Hg(II)
maximum at 776 nm originates from the SPR of AuNPs. Thus, (R2 ¼ 0.9983) (Fig. 6, inset B). The lowest detection limit (LOD)
we have chosen the excitation wavelength of 520 nm for further was found to be 0.75 fM L1 (S/N ¼ 3).
studies.
The observed large stock shi (lem  lex ¼ 256 nm) 3.7 Hg(II) binding studies by XPS
conrmed the highly uorescent nature of DAT-AuNPs.10,28
First, we have recorded the emission spectra of DAT-AuNPs in XPS is a very sensitive and surface specic analytical tool and it
the presence of different nanomolar concentrations of Hg(II) is widely used to characterize the electronic environment of the
(Fig. S4, ESI†). Aer the addition of 10 nM Hg(II) into DAT- chemical species. XPS was performed to understand the
chemical nature of DAT-AuNPs before and aer the addition of
Hg(II). Fig. 7 shows the XPS spectra of DAT-AuNPs aer the
addition of 100 nM Hg(II). In contrast to the survey spectrum of
DAT-AuNPs (Fig. 2), two new peaks appeared for DAT-AuNPs
aer added with Hg(II) (Fig. 7A). The XPS of Hg5p shows two
peaks at 69.3 eV for 5p1 and 74.35 eV for 5p3 (Fig. 7B),32

Fig. 6 Emission spectra of DAT-AuNPs in the presence of different concentra-

tions of Hg(II): (a) 0, (b) 0.5, (c) 10, (d) 20, (e) 30, (f) 40, (g) 50, (h) 60, (i) 70, (j) 80,
(k) 90 and (l) 100
1012 mol L1. (m) 100
1012 mol L1 of Hg(II) in the
absence of DAT-AuNPs (lex: 520 nm, lem: 776 nm). Inset A: magnified emission
spectra of curves a and b. Inset B: linearity plot of emission intensity against the Fig. 7 XPS of Hg(II)-DAT-AuNPs. (A) Survey spectrum and enlarged spectra in the
concentrations of Hg(II). (B) Hg5p and (C) Au4f regions.

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suggesting that the mercury was present as Hg(II) and it was

coordinated with DAT-AuNPs.31,32 The absence of peaks at 100.6
and 101.4 eV indicates the absence of Hg(0) and Hg(I), respec-
tively. This strongly suggests that mercury was present as
Hg(II).31,32 The spectrum of Au4f shows two peaks at 85.75 eV for
4f7/2 and 89.45 eV for 4f5/2 (Fig. 7C). The C1s spectrum shows a
binding energy at 284.15 eV (Fig. 7C), which again indicates the
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presence of DAT on the surface of AuNPs. In contrast to DAT-

AuNPs (Fig. 3A), the XPS of DAT-AuNPs in the presence of Hg(II)
(Fig. 7A) shows the absence of free amine binding energy at
400 eV, suggesting that it binds with Hg(II). Furthermore, the
N1s spectrum shows a binding energy of 370 eV (Fig. 7A) which
is assigned to the amine group bound to AuNPs (HN–Au).30,33

3.8 Binding constant and quantum yield

The binding constant (KA) and binding site numbers (n) can be
calculated by using the following double logarithm equation.42 Fig. 8 Selectivity of DAT-AuNPs towards Hg(II). The emission response of Hg(II)
(10
109 mol L1) in DAT-AuNPs (curve t) in the presence of 0.5
103 mol L1
log[F  F0/F0] ¼ log KA + nlog[Q] (3) of Na+, K+, Ca2+, Mg2+, Fe2+, Cd2+, Cr3+, Mn2+, Zn2+, Co2+, Ni2+, Fe3+, SO42, Cl,
NO3 ions and EDTA (curves a–p) and 6, 5 and 1
106 mol L1 of Pb2+, Cu2+ and
Ag+ (curves q–s), respectively.
where “F” is the uorescence intensity aer the addition of
Hg(II) into DAT-AuNPs and “F0” is the uorescence intensity of
DAT-AuNPs. “KA” is the binding constant, “n” is the number
of binding sites and “Q” is the concentration of Hg(II). Appar- uorescence spectra of DAT-AuNPs in the absence and presence
ently, the KA and n can be measured, from the intercept and of different metal ions are shown in Fig. 8. Curve a in Fig. 8
slope obtained through plotting log[F  F0/F0] against log[Q]. shows the emission spectrum of DAT-AuNPs and the curves b–p
The binding constant value was calculated as KA ¼ 7.6190
show the uorescence spectra of DAT-AuNPs in the presence of
1014 mol1 L, suggesting the presence of a strong binding force 0.5 mM of Na+, K+, Ca2+, Mg2+, Fe2+, Cd2+, Cr3+, Mn2+, Zn2+, Co2+,
between DAT-AuNPs and Hg(II). Ni2+, EDTA, Fe3+, SO42, Cl, and NO3 ions. Curves q–s show the
The determination of quantum yield is generally accom- uorescence spectra of DAT-AuNPs in the presence of 6, 5 and 1
plished by a comparison of the wavelength-integrated intensity mM Pb2+, Cu2+ and Ag+ ions, respectively. The uorescence
of the unknown sample with the standard. Fluorescent spectrum of DAT-AuNPs in the presence of 10 nM Hg2+ is shown
quantum yield values (fF) of DAT-AuNPs in the presence and as curve t. As shown in Fig. 8, the emission intensity was not
the absence of Hg(II) were calculated by using the comparative altered in the presence of 50 000-fold of common interferents.
William's method.43 For this purpose, we used rhodamine as a This indicates that the DAT-AuNPs selectively bind with 10 nM
reference quantum yield standard.43 The integrated uores- Hg(II) even in the presence of 50 000-fold concentration of Na+,
cence intensities of DAT-AuNPs and Hg(II) added DAT-AuNPs K+, Ca2+, Mg2+, Fe2+, Cd2+, Cr3+, Mn2+, EDTA, Zn2+, Co2+, Ni2+,
were plotted against the absorbance for the reference standard. Fe3+, SO42, Cl and NO3 ions. Further, no interference was
The gradients of the plot were proportional to the quantity of
the quantum yield of the standard molecules. The fF value was
Table 1 Determination of Hg(II) in different water samplesa
calculated by using the following equation.
Hg(II) Hg(II) Recovery
fF(x) ¼ (GradX/GradST)(nX2/nST2) (4) Samples added (ng L1) found (ng L1) RSD (%)

where “ST” and “X” denote standard and sample, respectively. River water
“Grad” is the gradient from the plot and “n” is the refractive 1 — — — —
index of the solvent. Based on the values obtained from eqn (4), 2 10 9.8  0.07 1.24 98.7
3 20 20  0.26 0.56 101.3
the uorescence quantum yield of DAT-AuNPs and DAT-AuNP–
Hg(II) was found to be 0.6519 and 0.8701, respectively. The Tap water
addition of Hg(II) to DAT-AuNPs increases the emission inten- 1 — — — —
sity and thereby increased the quantum yield. 2 10 9.9  0.30 0.84 99.3
3 20 20  0.14 0.16 100.7
3.9 Effect of interferences
I.W. water
The effect of various interfering ions on the determination of 1 — 50  0.08 0.65 —
Hg(II) was investigated for the sample containing 10 nM Hg(II). 2 10 60  0.06 0.24 99.8
3 20 70  0.26 1.06 100.9
Interfering ions of a 50 000-fold concentration (0.5 mM) were
added into DAT-AuNPs containing 10 nM Hg(II). The a
I.W. water ¼ Industrial Waste water.

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Paper Journal of Materials Chemistry A

Table 2 Comparison of the present method of determination of Hg(II) with the

ICP-AES method
Notes and references
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Hg(II) found (mg L1)
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3 I. Onyido, A. R. Norris and E. Buncel, Chem. Rev., 2004, 104,
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0.05 0.05  0.02 0.05  0.03 100.8 0.6345 1.0

0.1 0.09  0.61 0.1  0.05 99.5 0.4792 1.0
5911.
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