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Article history: The effect of silicon-coated gold nanoparticles with different gold core diameter and silica shell thickness on the
Received 2 March 2017 fluorescence emission of CdTe quantum dots (QDs) was investigated. For gold nanoparticles with a diameter of
Received in revised form 9 June 2017 15 nm, silica coating can only results in fluorescence recover of the bare gold nanoparticle-induced quenching of
Accepted 30 June 2017
QDs. However, when the size of gold nanoparticle is increased to 60 nm, fluorescence enhancement of the QDs
Available online 30 June 2017
could be obtained by silica coating. Because of the isolation of the silica shell-reduced quenching effect and
Keywords:
local electric field effect, the fluorescence of QDs gets intense firstly and then decreases. The maximum fluores-
Silicon-coated gold nanoparticles cence enhancement takes place as the silica shell has a thickness of 30 nm. This enhanced fluorescence from sil-
CdTe quantum dots (QDs) icon-coated gold nanoparticles is demonstrated for sensing of Hg2+. Under optimal conditions, the enhanced
Fluorescent quenching fluorescence intensity decreases linearly with the concentration of Hg2+ ranging from 0 to 200 ng/mL. The
Fluorescent enhancement limit of detection for Hg2+ is 1.25 ng/mL. Interference test and real samples detection indicate that the influence
Mercury ions from other metal ions could be neglected, and the Hg2+ could be specifically detected.
Fluorescent probe © 2017 Elsevier B.V. All rights reserved.
1. Introduction quenching occurs [12,13]. Whereas when the distance between the
metal surface and fluorescent emitter has been enlarged, the
In recent years, much attention has been focused on the modulation nonradiative energy transformation-induced quenching fades down
of fluorescence emission from dye molecule or quantum dots (QDs) rapidly, and then the local field enhancement will take the dominating
using noble metallic nanoparticles [1,2]. The main physical origin is effect and the fluorescence enhancement occurs. However, the local
based on the non-radiative energy transfer-induced fluorescence field enhancement is also a kind of local effect, thus the fluorescence en-
quenching or local field effect-induced fluorescence enhancement [3, hancement will be weakened as the distance is too large [14]. Therefore,
4]. Because of the localized surface plasmon resonance (LSPR), which the maximum fluorescence enhancement only takes place when the
is kind of collective oscillation of conduction-band electrons on the par- distance has an appropriate value. In order to modulate the distance be-
ticle surface, gold and silver nanostructure can concentrate optical elec- tween the fluorescent emitter and metal surface, a dielectric separate
tromagnetic field into subwavelength regions close to the surface of the layer, such as a silicon shell, has been coated on the metal nanoparticles
particles [5]. Thus intense resonance light absorption and local electric [15]. In the report of Jia et al., Au/Ag@SiO2 nanoparticles with different
field enhancement could be generated. When a single quantum emitter, silica layer thicknesses have been used to modulate the emission of
such as a fluorescent dye molecule or a quantum dot, is coupled to a CdSe/CdS quantum dots [16]. Their experimental results demonstrated
plasmonic nanostructure, the resonance absorption-induced quenching that the fluorescent emission of CdSe/CdS QD can be either obviously
and local field effect-induced enhancement will greatly affect the fluo- quenched or enhanced, depending on the spectral overlap and local dis-
rescence emission [6,7]. tance control between QDs and Au/Ag nanoparticles. Using the dye-
In the competition between non-radiative energy transfer-induced doped silica-coated silver nanoparticles with shell thicknesses ranging
quenching and local field effect-induced fluorescence enhancement, from 8.6 to 75.4 nm, Blake-Hedges et al. studied the plasmon-enhanced
the distance between the metal surface and fluorescent emitter plays fluorescence [17]. It has been found the fluorescence enhancement is
an important role in tuning the fluorescence intensity [8–11]. When positively correlated to the dye-metal distance, with ~19 nm separation
the fluorescent emitter is directly contacted with the metal particle, producing the greatest fluorescence enhancement. In the report of Niu
the nonradiative decay is the dominating effect and the fluorescence et al., silica-doated gold nanobipyramids with distance-dependent plas-
mon-enhanced fluorescence has been studied and been applied in bio-
logic sensing [8]. In their study, silica shell was chosen as the rigid spacer
⁎ Corresponding authors. to regulate the distance between the metal surface and dyes. Maximum
E-mail addresses: nanoptzj@163.com (J. Zhu), nanoptzhao@163.com (J.-W. Zhao). fluorescence enhancement was observed at a distance of approximately
http://dx.doi.org/10.1016/j.saa.2017.06.038
1386-1425/© 2017 Elsevier B.V. All rights reserved.
J. Zhu et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 188 (2018) 170–178 171
17 nm. Recently, silica-shell isolated Au-Ag alloy nanoparticle has also 2.2. Synthesis of Citrate-Stabilized Gold Nanoparticles
been used for investigating the metal-enhanced fluorescence effect
[3]. They found the fluorescence enhancement effect is separation- Gold Nanoparticles were synthesized using the seeded growth
layer sensitive, and the optimal phenomenon occurs for the surface en- method according to the literature with a slight modification [27]. First-
hancement effect when the shell thickness is at around 8 nm. ly, we prepared the Au seeds. Typically, 150 mL 2.2 mM sodium citrate
Besides the separation distance, the size of metal particle and the was heated to boiling under vigorous stirring. Then 1 mL HAuCl4
overlap between the emission spectrum and LSPR also greatly affect (25 mM) was injected. The colour of the solution changed from yellow
the fluorescence modulation [18–20]. In the study of Lin and Chen, var- to soft pink and then to wine red. Afterwards, deionized water was
ied sizes of gold nanoparticles with controlled thickness of silica shell added to make the whole volume of the solution 150 mL. Immediately
were synthesized to investigate the effects on metal-enhanced fluores- after the synthesis of the Au seeds, the seeds solution was heated to
cence of rose bengal fluorophores [11]. The maximum fluorescence en- boiling in the same process, then 1 mL 25 mM HAuCl4 solution was
hancement factor is 2.4, 3.8, 4.6, and 5.5 at spacer separation ~ 10 nm added into the boiled seeds solution. After 15 min, another 1 mL
when the diameters of silica-coated gold nanoparticles are 45, 65, 80, 25 mM HAuCl4 solution was added, and the reaction was finished
and 100 nm, respectively. Thus, the fluorescence enhancement could after 15 min. After that, the sample was diluted to 152 mL using deion-
be obtained more easily when the gold core has a larger size. Could fluo- ized water. Afterwards, a new seeds solition was synthesized by
rescence enhancement always been observed from gold nanoparticles extracting 55 mL of the above sample and adding 53 mL deionized
by silica coating? The spectral overlap between the emission bands of water and 2 mL 60 mM sodium citrate. Then the whole process was re-
the fluorophores and the plasmon band of the metal nanoparticles is peated again. Greater sizes of Gold Nanoparticles were obtained by ad-
the other important factor affecting the intensity of fluorescence. A dition of the times of the seeded growth.
strong correlation between the fluorescence intensity of the emitter
and the degree of spectral overlap with the LSPR of the metal nanopar-
ticle has already been observed [19]. Thus the metal nanoparticles or 2.3. The Preparation of Silicon-Coated Gold Nanoparticles
fluorescence emitter with tunable peak wavelength contributes to the
spectral overlap of the emission of fluorophore with the absorption of Au@SiO2 NPs were synthesized via a modified method reported [28].
the metal nanoparticle. QDs have size-dependent fluorescence emission Typically, 10 mL freshly prepard gold nanoparticles were centrifuged
wavelength. Therefore, by changing the particle size, we can obtain suit- and redispersed in 10 mL deionized water. An ethanolic solution of
able fluorescence wavelength to match the LSPR of metal nanoparticles MHA (400 μL, 4 mM) was added into the colloidal solution, and the mix-
in this study. ture was reacted for 15 min under vigorous stirring. The obtained solu-
Ultra-sensitive Hg2+ detection based on fluorescent QDs is also a hot tion was then centrifuged and resuspended in 10 mL anhydrous
topic in recent years [21–25]. In these detection methods for Hg2+, the ethanol. Subsequently, the TEOS in anhydrous ethanol (10 vt%) was
fluorescence of QDs can usually be quenched by Hg2+ through an effec- added followed by the addition of dimethylamine (40 wt%, 1.1 mL). Fi-
tive electron energy transfer process. The mechanism of the remarkable nally, it was allowed to stir for 12 h at room temperature before being
quenching effect of Hg2+ could be attributed to the electron transfer centrifuged and redispersed into ethanol. Silica shells of varied thick-
process between the capping ligands and mercury ions, and the non-ra- ness were obtained by controlled TEOS addition.
diation recombination of holes and excitation electrons [21,26]. The de-
tection limit and linear range depend on the fluorescence intensity 2.4. Preparation of Amino-Functionalized Au@SiO2 Nanoparticles
decrease of the QDs. So we think, could the detection sensitivity be im-
proved by increasing the fluorescence intensity of the QDs? In this Au@SiO2 nanoparticles with different silica shell thickness were
paper, by using gold nanoparticles with large diameter and optimal sil- functionalized with amino groups. Briefly, 20 μL APTES was added to
ica shell thickness, and CdTe QDs with appropriate size and wavelength, 10 mL Au@SiO2 nanoparticles solution dissolved in anhydrous ethanol,
which is coupled with the SPR of silica-coated gold nanoparticles, the and the mixture was shaken at room temperature for 12 h followed
enhanced fluorescence of CdTe QDs has been obtained. Then this en- by heating at 70 °C for 1 h. The resulting amino-modified Au@SiO2
hanced fluorescence has been used to detect Hg2 +, which improves nanoparticles were purified by centrifugation at 10000 rpm for 10 min
the quenching range and the corresponding sensing ability. This fluores- and redispersed with 10 mL ethanol three times. Eventually, the
cent probe based on silica-coated gold nanoparticles could be used for amino-modified Au@SiO2 nanoparticles were dispersed in 10 mL
selective detection of Hg2+ with a linear range of 0–200 ng/mL and a water for further use.
detection limit of 1.25 ng/mL.
2.1. Materials and Chemicals Firstly, TGA-coated CdTe QDs were synthesized according to the pre-
vious approach [29]. To activate the carboxyl group of TGA on the sur-
Chloroauric acid (HAuCl4) was purchased from Sinopharm Chemical faces of CdTe QDs, the mixed solution containing 1 mL freshly
Reagent Co., Ltd., China. Sodium citrate, Te powder, cadmiumchloride, prepared CdTe solution and 3 mL anhydrous ethanol were centrifuged
sodium hydroxide, sodium borohydride, tetraethyl orthosilicate at 5000 rpm for 5 min and then the precipitate was redispersed in
(TEOS) and (3-aminopropyl)-trimethoxysilane (APTES) were obtained 1 mL deionized water. Whereafter, 0.5 mL 40 mg/mL EDC and 0.5 mL
from Aladdin Industrial Corporation. 16-mercaptohexadecanoic acid 40 mg/mL NHS solution was respectively added into the QDs solution,
(MHA) was purchased from Sigma. Anhydrous ethanol was purchased and the mixture was stired for 20 min at room temperature. Then
from Tianjin Hedong Hongyan Reagent Factory. Dimethylamine 6 mL anhydrous ethanol was added into the reaction solution and the
(40 wt%) was obtained from Tianjin Kemiou Reagent Co., Ltd. 1-ethyl- centrifugation was operated to remove the excess EDC and NHS, and
3-(3-dimethylaminopropyl)-carbodiimide (EDC) was purchased from the precipitate was redispersed in 10 mL deionized water. Finally,
Bio Basic Inc.. N-hydroxysuccinimide (NHS) was purchased from Beijing amino-functionalized Au@SiO2 colloidal solution was mixed with
lark technology Co., Ltd. All chemicals used in this work were analytical 0.1 mL the above QDs solution. The solution was shaken in ultrasonic
grade and deionized water (18.0 MΩ·cm) was used throughout the cleaner at room temperature for 4 h and finally the QDs were attached
experiments. to the surface of Au@SiO2 nanoparticles.
172 J. Zhu et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 188 (2018) 170–178
Fig. 1. TEM images of small gold nanoparticles with different thickness of SiO2 coating. (a) The silicon shell has a thickness of 10 nm; (b) The silicon shell has a thickness of 20 nm. The gold
nanoparticles have a diameter of 15 nm. (c) FTIR spectra of gold nanoparticles and Au@SiO2 nanoparticles.
J. Zhu et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 188 (2018) 170–178 173
The overlap between the emission bands of the QDs and the SPR
band of the gold nanoparticles is an important factor affecting the inten-
sity of fluorescence [6]. In this section, CdTe QDs with three different
sizes (the corresponding emission wavelength takes place at 520, 575
and 615 nm respectively) have been used to test the fluorescence recov-
er ability of the Au@SiO2 nanoparticles. Fig. 4 shows the effect of silicon-
coated gold nanoparticles on the fluorescence recover of CdTe QDs with
different emission wavelength. In this test, the silicon shell has a thick-
ness of 20 nm. The spectral comparison in Fig. 4 indicates that the
greatest fluorescence quenching and recover take place when the QDs
have an emission at 520 nm. Whereas both the fluorescence quenching
and recover has been weakened when the emission wavelength of the
QDs is increased to 575 and 615 nm. This result could be attributed to
the wavelength overlap between the emission of the QDs and the plas-
monic absorption of the gold nanoparticles. The SPR band takes place at
528 nm, which is coupled with the CdTe QDs with a fluorescence emis-
sion at 520 nm. As we know, the overlap between absorption spectrum
of gold nanoparticles and emission spectrum of QDs is necessary for the
Fig. 2. Absorption spectra of small gold nanoparticles with different thickness of SiO2
energy transfer system. The more spectrum overlap creates the greater
coating. The inset shows the dependence of absorption peak wavelength on the silica
shell thickness. energy transfer efficiency. Similarly, less overlap only weaken the ener-
gy transfer efficiency, but the energy transfer between gold nanoparti-
cles and QDs still takes place. A key point in this study is the effect of
particle size and spectrum overlap degree on the fluorescence intensity
In this section, we study the effect of small gold nanoparticles with of QDs. When the gold core diameter of Au@SiO2 is 15 nm, the fluores-
SiO2 coating on the fluorescence emission of CdTe QDs. Because of the cence quenching effect plays the dominant role. From the Fig. 4, we can
modification of amino group on the Au@SiO2 nanoparticles and the car- see when QDs with different sizes combine respectively with bare gold
boxyl activation of QDs, CdTe QDs have been attached to the surface of nanoparticles, the fluorescence intensity of QDs is weakened, and the
Au@SiO2 nanoparticles when the Au@SiO2 colloid has been added to greater overlap degree cause the weaker fluorescence emission, which
the CdTe QDs solution. Fig. 3 shows the fluorescence emission spectra is resulted from the intense FRET induced fluorescence quenching.
of CdTe QDs-modified Au@SiO2 core-shell nanoparticles with different When gold nanoparticles have been coated with silica shell, the fluores-
silica shell thickness keeping the concentrations of the Au@SiO2 nano- cence intensity of QDs will gradually restore, and the fluorescence re-
particles and QDs constant. For pure CdTe QDs solution, one can find covery degree shows an increase tendency with the increase of
an intense fluorescence peak at 620 nm. After attaching to bare gold spectral overlap degree. Therefore, whether the fluorescence quenching
nanoparticles, the fluorescence of QDs has been greatly quenched. The resulted from bare AuNPs or the fluorescence recovery resulted from
origin could be attributed to the fluorescence resonance energy transfer Au@SiO2, the increase of overlap degree creates greater effect.
(FRET) from the QDs to the SPR of gold nanoparticles [31]. The similar
results and corresponding energy transfer mechanism have also been
reported in the references [32,33] However, when the QDs have been 3.2. Tuning the Fluorescence Enhancement of CdTe QDs Using Large Gold
attached to the silicon-coated gold nanoparticles, the quenched fluores- Nanoparticles with Silicon Coating
cence gets intense again. Therefore, the isolation of the silica shell pre-
vents the quenching effect of gold nanoparticle on CdTe QDs [5]. As Besides silicon shell thickness, the size of inner gold nanoparticle
the thickness of the silica shell is increased, the distance between QDs also affects the fluorescence enhancement of the Au@SiO2 core-shell
and gold surface further increases, thus the quenching effect is further nanoparticles. Here, large gold nanoparticles have been synthesized
prevented and the fluorescence recover is further enhanced. and used to modify the fluorescence of CdTe QDs. Fig. 5a–c show the
TEM images of large gold nanoparticles with SiO2 coating. It has been
Fig. 3. The effect of small gold nanoparticles with different thickness of SiO2 coating on the Fig. 4. The effect of silicon-coated gold nanoparticles on the fluorescence recover of CdTe
fluorescence spectra of CdTe QDs. QDs with different emission wavelength.
174 J. Zhu et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 188 (2018) 170–178
Fig. 5. TEM images of large gold nanoparticles with different thickness of SiO2 coating. (a) The silicon shell has a thickness of 10 nm; (b) The silicon shell has a thickness of 30 nm; (c) The
silicon shell has a thickness of 50 nm. The gold nanoparticles have a diameter of 60 nm. (d) TEM image of Au@SiO2 nanoparticles including added CdTe QDs.
found the as-prepared quasi-spherical gold nanoparticles display an in- obtained when the inner gold core has large diameter. As the silicon
homogeneous distribution and have a large diameter of 60 nm. Gold shell thickness is increased to 30 nm, we can obtain the maximum fluo-
nanoparticles with different thickness of silicon coating could also rescence enhancement, which is about two times of the fluorescence in-
been obtained by changing the amount of TEOS. When the amount of tensity of pure QDs. However, the fluorescence peak will not
added TEOS is set as 10, 20 and 30 μL, the silicon shell has a thin thick- monotonously get intense as the silicon shell thickness is further in-
ness of approximately 10, 30 and 50 nm respectively. The formation of creased. The inset of Fig. 7 displays the plots of fluorescence emission in-
core-shell structures and uniform silicon coating thickness could be tensity verse the silica thickness. It indicates that the fluorescence
confirmed by the TEM images in Fig. 5a–c. Fig. 5d shows the TEM intensity of CdTe QDs-modified Au@SiO2 nanoparticles strongly de-
image of Au@SiO2 nanoparticles including added CdTe QDs. A thin pends on the silica shell thickness, i.e., the spacer distance between
layer outside the silicon shell could be observed from the TEM image,
which indicates the CdTe QDs are combined effectively with the surface
of Au@SiO2 nanoparticles.
The absorption spectra of core-shell Au@SiO2 nanoparticles with in-
creasing silicon thickness have been compared in Fig. 6. As the thickness
of the silica shell increased, the plasmonic absorption peak of Au@SiO2
nanoparticles gradually red shifted toward a longer wavelength. The
inset shows the dependence of absorption peak wavelength on the
thickness of the silica shell. As the silica shell is increased from 10 to
50 nm, the absorption peak red shifts from 553 to 558 nm. This red
shift of the plasmonic absorption peak also indicates that the silica
shell is coated on the gold nanoparticles. Although the increase of silica
shell is larger than that of Fig. 2, the ratio of the silica shell enhancement
to the diameter of the gold particle has not changed. Therefore, the red
shift of the SPR band is similar to that of Fig. 2.
The effect of large gold nanoparticles with SiO2 coating on the fluo-
rescence emission of CdTe QDs has been studied in Fig. 7. In this test,
the pure CdTe QDs also have an intense fluorescence peak at 620 nm.
When the QDs have been attached to the silicon-coated gold nanoparti-
cles, the fluorescence peak has been enhanced distinctly, which is much
different from the result in Fig. 3. Thus the size of inner gold nanoparti-
cle greatly affects the fluorescence enhancement of the Au@SiO2 core- Fig. 6. Absorption spectra of large gold nanoparticles with different thickness of SiO2
shell nanoparticles. The fluorescence enhancement could be more easily coating.
J. Zhu et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 188 (2018) 170–178 175
Fig. 7. The effect of large gold nanoparticles with different thickness of SiO2 coating on the Fig. 8. The effect of silicon-coated large gold nanoparticles on the fluorescence
fluorescence spectra of CdTe QDs. enhancement of CdTe QDs with different emission wavelength.
gold nanoparticles and QDs. As the silica shell thickness is increased, the
fluorescence emission changes non-monotonously, and reaches the nanoparticles, the absorption of which is dominant, which results in
maximum at 30 nm thickness of silica shell. When the silicon shell fluorescence quenching of the CdTe QDs. However, the scattering inten-
thickness is increased to 50 nm, the fluorescence peak fades down, sity increases gradually with the size increase of gold nanoparticles,
which could be attributed to the too large distance between QDs and therefore large colloidal gold nanoparticles produce fluorescence en-
gold surface induced decrease of local electric field [34,35]. As we hancement effect.
know, the distance between metal nanoparticles and fluorescent mole-
cules plays a dominant role in the fluorescence enhancement based on 3.3. The Detection of Hg2+ Using CdTe QDs-Modified Au@SiO2 Nanoparti-
the competition between local field effect and FRET. When fluorescent cles Fluorescence Probe
molecules are too close to metal nanoparticles, FRET-induced fluores-
cence quenching takes the main effect. When distance is too far, there In recent years, quantum dots-based fluorescence probe for chemi-
is no interaction between them, thus the effect of metal nanoparticles cal and biologic detection have become a hot topic of nano-optics and
on the fluorescent molecular is too weak to be observed. Only when analytical chemistry [40]. Because of the high quantum yield, narrow
the distance has an appropriate value, the fluorescence enhancement emission wavelengths and size-dependent fluorescence frequency, the
can take place. Indeed, a large number of literature show that the dis- fluorescence properties of CdTe QDs have also been used in the detec-
tance between the metal nanoparticles and fluorophore is an important tion of Hg2+ [21–23]. In these detection methods, the fluorescence of
factor that affect the fluorescence intensity of fluorescence material QDs has been effectively quenched by the adsorption of Hg2 +. The
[36–38]. quenching mechanism could be attributed to the non-radiation recom-
The overlap between the emission bands of the QDs and the SPR bination and effective electrons transformation from surface traps of
band of the gold nanoparticles also affects the fluorescence of CdTe QDs to Hg2 +. As we know, an intensity decrease of QDs fluorescence
QDs-modified Au@SiO2 nanoparticles with large inner core. In this emission can be observed when an electron acceptor or a surface mod-
test, CdTe QDs with three different sizes (the corresponding emission ifier is adsorbed onto the QDs surface. According to the reports in the lit-
wavelength takes place at 525, 560 and 625 nm respectively) have erature [21,26], Hg2+ has been bound to the surface of the CdTe QDs,
been used to study the fluorescence enhancement of the Au@SiO2 nano- which facilitate non-radiative electron/hole recombination annihila-
particles. Fig. 8 shows the effect of silicon-coated gold nanoparticles on tion. Besides, the quenching of CdTe QDs could also be achieved through
the fluorescence enhancement of CdTe QDs with different emission electron transfer from surface traps of QDs to Hg2+ [41,21]. Although
wavelength. In this experiment, the silicon shell has the optimized both electron transfer and ion-binding can lead to the decrease of QDs
thickness of 30 nm. The spectral comparison in Fig. 8 indicates that fluorescence emission, but the electron transfer may play a leading
the greatest fluorescence enhancement (which is three times of the role [26]. In this study, the fluorescence intensity of CdTe QDs has
fluorescence intensity of the pure QDs) take place when the QDs have been enhanced by the silicon-coated gold nanoparticles, which im-
an emission at 560 nm, which is different from the result in Fig. 4. This proves the quenching range and the corresponding sensing ability. Fig.
result could also be attributed to the wavelength overlap. The SPR 9a shows the fluorescence spectra of CdTe QDs-modified Au@SiO2
band of silica-coated gold nanoparticles takes place at 557 nm, which nanoparticles with the addition of Hg2+ with different concentrations.
is coupled with the CdTe QDs with a fluorescence emission at 560 nm. In this study, the CdTe QDs have a fluorescence emission peak of
When the emission peak of fluorescent molecular is matched with the 560 nm, which is coupled with the plasmonics absorption of the Au@
metal plasmon resonance peak, exciton and plasmon will couple SiO2 nanoparticles. When the concentration of Hg2+ is increased from
strongly and the energy will rapidly pass between them. Therefore, 0 to 5 ng/mL, the fluorescence intensity decreases from 590,000 to
the degree of overlap between the emission spectrum of fluorescent 560,000 (CPS). Thus Hg2+ could be detected by measuring the intensity
molecules and absorption spectrum of metal nanoparticles has great ef- decrease of the fluorescence peak. As the concentration of Hg2+ is fur-
fect on the energy transfer efficiency. According to Mie theory, the size ther increased, the fluorescence intensity continues to decrease monot-
of the metal nanoparticles affect the scattering and absorption cross sec- onously. Fig. 9b shows the dependence of (F0-F)/F0 on the
tion, the part of absorption is proportional to the third power of radius concentrations of Hg2+ ions, here F0 and F are the fluorescence intensity
of the nanoparticles and the part of scattering is proportional to the in the absence and presence of the Hg2+. One can find a good linear re-
sixth power of radius of the nanoparticles [39]. For small colloidal gold lationship between the fluorescence quenching and the Hg2 +
176 J. Zhu et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 188 (2018) 170–178
Fig. 9. (a) The effect of Hg2+ with different concentrations on the fluorescence quenching of CdTe QDs-modified Au@SiO2 nanoparticles, (b) The dependence of (F0-F)/F0 from CdTe QDs-
modified Au@SiO2 nanoparticles on the concentrations of Hg2+ ions. (c) The effect of Hg2+ with different concentrations on the fluorescence quenching of CdTe QDs without Au@SiO2
nanoparticles, (d) The dependence of (F0-F)/F0 from CdTe QDs on the concentrations of Hg2+ ions.
concentration in a region from 0 to 200 ng/mL. The calibration curve can response to the system. So we completed entire experimental process
be expressed as (F0-F)/F0 = 0.0036Cmercury ions (ng/mL) + 0.0599 (R2 = in a neutral environment.
0.99026). And the corresponding detection limit (S/N = 3) is A performance comparison of this method with other reported
1.25 ng/mL. This detection linear range is wider than that of the sensing nano-chemosensors for Hg2+ detection is shown in Table 1. Although
method based on CdTe QDs in the absence of Au@SiO2 nanoparticles some methods have better detection limit, the linear range is relatively
(0.5 to 40 ng/mL) [42], and based on the graphitic carbon nitride QDs narrow. For example, in the report of Gong et al. [42], where nano-
without Au@SiO2 nanoparticles (0.25 to 10 ng/mL) [43]. In order to il- chemosensor is based on CdTe QDs without Au@SiO2 nanoparticles,
lustrate the role of Au@SiO2 nanoparticles in the fluorescence detection the detection linear range is 0.5–40 ng/mL. In addition, the sensing sys-
of Hg2+, a control experiment using CdTe QDs to directly detect Hg2+ tem includes gold nanoparticles in the work of Huang et al. [49], the de-
was also performed for comparison. The procedure for the detection tection limit and detection range are all poor compared with our work.
of Hg2+ was similar to that for CdTe − Au@SiO2 system. The fluores- The results clearly indicate that the presented system has competitive
cence spectra of the CdTe QDs with different concentrations of Hg2+ detection limit and more wide detection range than the other reported
are shown in Fig. 9c, and the plot of the (F0-F)/F0 versus the concentra- sensing systems.
tion of added Hg2+ is shown in Fig. 9d. The calibration equation is (F0- In order to test the selectivity of this fluorescence quenching method
F)/F0 = 0.0152C mercury ions (ng/mL) - 0.0517 in the range from 10 to in the detection of Hg2+, the fluorescence spectra of CdTe QDs in the
50 ng/mL with a correlation coefficient of 0.997. The corresponding de- presence of different metal ions are compared in Fig. 10a. In this exper-
tection limit (S/N = 3) is 6.2 ng/mL. It is clear that the detection limit of iment, the Hg2 +, Fe2 +, Cr3 +, Mg2 +, Pb2 +, Fe3 +, Al3 +, Mn2 +, Zn2 +,
CdTe-Au@SiO2 system to Hg2+ is lower than that of CdTe system. The Cu2+, Cd2+ have a concentration of 70 ng/mL. It has been found the in-
linear detection range was also wider, suggesting that CdTe-Au@SiO2 tense fluorescence emission peak of CdTe QDs has been quenched dis-
system for Hg2+ detection is better than CdTe system. These improved tinctly by Hg2 +. However, other metal ions can't quench the
analytical performances could be attributed to the Au@SiO2 nanoparti-
cles-induced fluorescence enhancement of CdTe QDs. In this experi-
Table 1
ment system, pH has a value of 7.4. The reasons of using neutral
Performance comparison with other reported nano-chemosensors for Hg(II) detection.
environment in our experiment are listed as follows. First, the surface
structure of QDs will be destroyed in acidic environment [44], which Nano-chemosensor Detection limit Detection linear range Reference
makes QDs unstable and the fluorescence intensity of QDs decrease. L-Cysteine-CdTeQDs 0.063 ng/mL 0.5–40 ng/mL [42]
Next, it helps to combination of QDs and Au@SiO2 nanoparticles in a me- g-CNQDs–K3Fe(CN)6 0.08 ng/mL 0.25–10 ng/mL [43]
dium environment [45–47]. At last, the effect of pH on QDs-Hg2+ detec- Carbon nanoparticle 2 ng/mL 0–50 ng/mL [48]
tion system had been studied in the report of Xia et al. [21], their results RB–AuNP–MPA 2 ng/mL 3–50 ng/mL [49]
Au@SiO2-CdTe QDs 1.25 ng/mL 0–200 ng/mL This work
showed that the neutral experimental conditions produced the best
J. Zhu et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 188 (2018) 170–178 177
Table 2
Determination of Hg2+ in tap water.
4. Conclusions
Acknowledgement
Fig. 10. The fluorescence spectra (a) and fluorescence emission intensity (b) of CdTe QDs This work was supported by the National Natural Science Founda-
in the presence of different metal ions. The concentration of Hg2+, Fe2+, Cr3+, Mg2+,
Pb2+, Fe3+, Al3+, Mn2+, Zn2+, Cu2+, Cd2+ is 70 ng/mL.
tion of China under grant No. 61675162, and the Natural Science Basic
Research Plan in Shaanxi Province of China under grant No.
2017JM6023 and 2017JM8064.
fluorescence of CdTe QDs obviously. On the contrary, One can observe
intensity increase of the fluorescence emission when Fe2 +, Cr3 +,
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