Sensors and Actuators B 241 (2017) 73–79

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Sensors and Actuators B: Chemical

journal homepage: www.elsevier.com/locate/snb

One-step synthesis of self-doped carbon dots with highly

photoluminescence as multifunctional biosensors for detection of
iron ions and pH
Runxia Wang a,c , Xiufang Wang b,∗ , Yimin Sun a,∗
a
College of Chemistry and Materials Science, Anhui Normal University, Wuhu, Anhui, 241000, China
b
Anhui Key Laboratory of Advanced Building Materials, Anhui Jianzhu University, Hefei, Anhui, 230601 China
c
Pharmacy department, Anhui Medical College, Hefei, Anhui, 230601, China

a r t i c l e i n f o a b s t r a c t

Article history: The nitrogen doped carbon dots (C-dots) with highly photoluminescence (PL) are synthesized using m-
Received 22 June 2016 aminobenzoic acid (MAC) as the only precursor by a simple, one-step hydrothermal method. The NH2
Received in revised form 7 October 2016 groups of MAC have been used as nitrogen source to dope C-dots. The synthesized nitrogen doped (N-
Accepted 8 October 2016
doped) C-dots present an unexpectedly large quantum yield of 30.7% and possess an essentially crystalline
Available online 13 October 2016
nature and desirable functional groups. More important, the C-dots can serve as multifunctional fluores-
cence nanosensors to detect pH and Fe3+ . The fluorescent intensity of the C-dots increases dramatically
Keywords:
as pH increases from 2 to 10. The fluorescent paper with C-dots coated for visual detection of pH by
Carbon dots
Photoluminescence
naked eyes has been successfully prepared. Moreover, the C-dots are employed for assaying Fe3+ based
Nitrogen doped on direct interactions between Fe3+ and COOH and NH2 groups of C-dots. Under the optimal condi-
M-aminobenzoic acid tion, a linear relationship between the decreased fluorescence intensity of C-dots and the concentration
Sensor of Fe3+ is established in the range from 0 to 1.6 ␮M. The detection limit is as low as 0.05 ␮M, suggesting
a promising assay for Fe3+ . The results reported here provide a new approach for the design of N-doped
multifunctional florescent sensor.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction resultant C-dots usually show low photoluminescence quantum

yields, typically less than 10%, and the unfavorably low fluorescence
In recent years, photoluminescent C-dots have attracted con- quantum yield of C-dots inhibits their widespread use.
siderable attention due to their excellent optical properties, good Basically, the photoluminescence behaviors of C-dots are related
biocompatibility, high chemical stability as well as low toxicity to their sizes, morphologies, compositions and crystalline degrees,
compared to the semiconductor quantum dots and organic dyes which are decided by both the starting materials and the fabri-
[1–3]. As new-generation photoluminescent nanomaterials, they cation methods. Different pathways such as surface passivation,
have extensive potential applications in bioimaging, optoelectron- functionalization, and heteroatom doping have been proposed to
ics, photocatalysis and solar energy harvesting [4–7]. So, great adjust the surface features, the fluorescent behaviors, as well as
efforts have been exerted on the preparation of C-dots from a vari- the electrochemical performance of the resulting C-dots [14–17].
ety of carbon precursors by various methods, such as arc-discharge, Among all these strategies, heteroatom-doping gained signiflcant
electrochemical oxidation, combustion, thermal decomposition research attention owing to its facile and easy manipulating nature.
or oxidation, and microwave-assisted pyrolysis [8–13]. However, Especially, the doping of nitrogen atoms in C-dots provides the
most of these routes suffer from expensive equipments, harsh syn- opportunities to adjust the structure and property of the C-dots.
thetic conditions, and tedious processes, leading to manufacturing The various synthesis methods have been developed to fabricate
difficulties and high costs for large scale production. Moreover, the N-doped C-dots, which generally can be categorized as two types:
one is treating the as-made C-dots with N sources. But multiple
steps are involved in such strategies, which will inevitably reduce
the controllability over the compositions and the morphologies of
∗ Corresponding authors. the resulting N-doped C-dots. The other route is to directly uti-
E-mail addresses: [email protected] (R. Wang), [email protected] lize N containing molecules as the precursors of C-dots, which
(X. Wang), [email protected] (Y. Sun).

http://dx.doi.org/10.1016/j.snb.2016.10.043
0925-4005/© 2016 Elsevier B.V. All rights reserved.
74 R. Wang et al. / Sensors and Actuators B 241 (2017) 73–79

thus provides more options to adjust the structure and property were redispersed in water with the concentration of 2 mg/mL for
of the N-doped C-dots. Yang et al. reported a facile method to pre- the further application.
pare nitrogen-doped C-dots using citric acid and ethylenediamine
as precursors under hydrothermal condition, which were applied
in sensors and bioimaging [18]. Liu et al. successfully prepared 2.3. Quantum yields measurements
C-dots with strongly yellow fluorescence through a microwave-
assisted facile method using o-phenylenediamine as the carbon The QY of the as-synthesized N-doped C-dots was measured
precursor. The as-prepared C-dots exhibited excitation-dependent using quinine sulfate as the standard based on the following equa-
photoluminescent behavior and excellent water-solubility due to tion: QYC = QYR . (IC /AC ) .(AR /IR ) .(␩C /␩R )2
some amino or hydroxy functional groups on the surface [19]. Yang
et al. synthesized phosphorus and nitrogen doped carbon dots by
carbonization of adenosine-5 -triphosphate using a hydrothermal 1C AR
QC = QR . .
treatment, and the carbon dots were used as a novel sensing plat- 1R AC
form for live cell imaging of reactive oxygen species and reactive
nitrogen species, including ClO− , ONOO− , and NO in macrophages where QY stands for the quantum yield, I is the measured inten-
[20]. Liu et al. fabricated highly photoluminescent nitrogen-rich sity of luminescent spectra, A is the optical density at excitation
carbon dots from melamine and citric acid for the selective detec- wavelength. Q was measured using quinine sulfate in 0.05 M sulfu-
tion of iron (III) ion [21]. Messina et al. used a multi-technique ric acid solution (literature quantum yield 0.54 at 310 nm ␩ = 1.33)
approach to study heavily nitrogen-doped C-dots synthesized by as a standard for C-dots. The subscript “R” refers to standard with
a simple bottom-up approach and capable of bright and color- known quantum yield and “C” for the sample in this equation. The ␩
tunable fluorescence in the visible region [22]. Huang et al. is the refractive index of the solvent. In order to minimize reabsorp-
synthesized a series of C-dots with excitation-dependent emission tion effects, absorbance in the 10 mm fluorescence cuvette were
and excitation-independent emission properties by controlling the kept under 0.05 at the excitation wavelength.
content of nitrogen elements, confirming that the characteristic
optical properties of C-dots originate from their energy levels [23].
Despite great efforts having been made, it is critical to search for
2.4. Detection of Fe3+
new carbon sources to synthesize N-doped C-dots with highly pho-
toluminescence using a simple strategy.
A typical procedure for the detection of Fe3+ is described as fol-
M-aminobenzoic acid with COOH and NH2 groups on the sur-
lows: the fluorescence spectrum of 2 mL C-dots suspension was
face is an ideal precursor for the synthesis of C-dots. In the present
recorded subsequently and the fluorescence intensity was set as
work, MAC is employed as the sole precursor in the preparation
F0 . Then, different concentrations of Fe3+ (0, 0.2, 0.4, 0.6, 0.8, 1,
of N-doped C-dots. The resulting C-dots are highly crystalline and
1.2, 1.6, 2.0, 2.4, and 2.8 ␮M) were mixed with the above solution
the quantum yield of C-dots has been significantly improved to
under gentle shaking. The corresponding fluorescence spectra were
be 30.7%, much higher than the values of most reported doping-
recorded and a series of I/I0 values were obtained. The other metal
free and N-doped C-dots. The strategy is realized through a simple
ions, such as Na+ , Cu2+ , Fe2+ , Cd2+ , Mn2+ , Zn2+ , Ni2+ , Hg2+ , Co2+ ,
hydrothermal approach. It is remarkable that the C-dots can act
and Pb2+ , etc., were also measured. All the detection experiments
as multifunctional fluorescence nanosensor to detect pH and Fe3+
were carried out under the same conditions at room temperature.
ions in aqueous solution. Importantly, a portable paper based sen-
To evaluate the C-dots-based sensor for Fe3+ detection in a prac-
sor has been prepared by simply coating the N-doped C-dots on
tical application, the performance of the present method for real
the commercial filter paper, and visual fluorescence detection of
water sample analysis was examined by lake water samples. The
pH by naked eyes is achieved under a UV lamp. The linear response
lake water samples were filtered through a 0.20 ␮m filtered mem-
range of Fe3+ detection is from 0 to 1.6 ␮M, and the detection limit
brane and centrifuged at 10,000 rpm for 10 min to get rid of any
is 0.05 ␮M. Moreover, the feasibility of C-dots for Fe3+ assay in local
insolubles. The Fe3+ at different concentration levels were added to
lake water is presented.
lake water samples and analyzed with the proposed method.

2. Experimental
2.5. Characterization
2.1. Materials
Ultraviolet–visible (UV–vis) absorption spectra of C-dots were
M-aminobenzoic acid is all analytical-grade reagents (Shanghai obtained using TU-1800PC spectrophotometer. The excitation and
Chemical Reagent Co. Ltd., China). The other reagents were used as emission spectra of C-dots were recorded in a microcell with
received without further purification. Double distilled water was 1 cm path length using an F-7000 fluorescence spectrophotome-
used throughout the experiment to prepare the solutions. ter (Hitachi) with a quartzcell (1 mm). The band pass for excitation
and emission was set as 5 nm. Fourier transform infrared (FT-IR)
2.2. Synthesis of N-doped C-dots spectra were obtained using a NEXUS-870 spectrophotometer with
KBr pellet. Transmission electron microscopy (TEM) images were
The N-doped C-dots were synthesized from MAC through a performed by using a JEM-2100F instrument with a field emis-
simple, convenient and one-step hydrothermal method. Briefly, sion gun operating at 200 kV. The TEM specimens were prepared
MAC (0.2 g) and water (20 mL) were sealed into a Teflon equipped by placing one drop of the C-dots solution on carbon coated cop-
stainless steel autoclave, which was then placed in a drying oven per grid and were dried at room temperature. X-ray diffraction
(DHG-9123A, Shanghai Yiheng Scientific Instrument Limited Com- (XRD) pattern was recorded with a Shimadu XRD-6000 powder X-
pany) followed by hydrothermal treatment at 180 ◦ C for 12 h. After ray diffractometer with Cu Kaı́ radiation (1.54056A◦ ). The X-ray
the reaction, the autoclave was cooled to room temperature. The photoelectron spectra (XPS) of C-dots were obtained with an X-ray
purification of the C-dots was conducted through a dialysis tube photoelectron spectrometer (ESCALAB 250Xi, Thermo Scientific).
(1000 Da, molecular weight cutoff) for about 24 h. The final C-dots Photographs were taken with a canon 350D digital camera.
 R. Wang et al. / Sensors and Actuators B 241 (2017) 73–79 75

35 c d
30
Percentage(%)

25

20
Intensity(a.u)

15

10

0
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 20 24 28 32

Diameter (nm) 2 θθ(degree)

Fig. 1. (a) TEM and (b) HRTEM images, (c) size distribution, and (d) XRD pattern of synthesized N-doped C-dots.

3. Results and discussion Fig. 2a illustrates the UV–vis and PL spectra of the resultant
N-doped C-dots in aqueous solution. It is observed that two char-
3.1. Synthesis and characterization of the N-doped C-dots acteristic UV–vis absorption peaks are located at 300 and 407 nm.
The optical absorption peak at 300 nm is typically assigned to the
The N-doped C-dots were prepared by a simple, one-step ␲–␲* transition of aromatic sp2 domains from the carbon core. The
hydrothermal method without further modification steps at 180 ◦ C peak observed at 407 nm is ascribed to the n–␲* transition and the
for 12 h. The purification of C-dots was through dialysis. The only contribution of surface moieties. The as-prepared N-doped C-dots
reagent is m-aminobenzoic acid with amino and carboxyl groups, are faint yellow under daylight and emit a brighter blue fluores-
acting as the carbon source, which makes this method fascinat- cence under the excitation of 365 nm UV light (inset of Fig. 2a). The
ing when compared with other N-doped C-dots preparations. The quantum yield of the C-dots is 30.7% using quinine sulfate in 0.1 M
transmission electron microscopy (TEM) images are recorded to H2 SO4 as a reference, which is higher than that obtained using other
analyze the morphology and structure of the N-doped C-dots. additions as nitrogen source to dope C-dots [20,24]. In the prepared
Fig. 1a indicates that the C-dots appear relatively uniform in size. C-dots, the electron-rich nature of N atoms changes the charge den-
The average diameter of the C-dots is 3 nm, and the size distri- sity of C-dots, resulting in the energy transfer to the excited ␲* state
bution accords well with Gaussian distribution by measuring 300 of the sp2 cluster of C-dots. In the process of electron transfer from
nanoparticles (Fig. 1c). The homogeneity of the C-dots, apparent ␲* to ␲, higher energy is released, which causes a higher quantum
in Fig. 1a, is notable since the synthesis strategy does not involve yield. Upon excitation at the maximum excitation wavelength of
any purification or annealing steps, which is usually required in 310 nm, the PL spectrum exhibits a strong peak at 415 nm.
solution-based procedures in order to attain uniform size and shape The emission peaks of N-doped C-dots at various excitation
distributions of N-doped C-dots. HRTEM image (Fig. 1b) shows clear wavelengths do not shift, indicating the uniformity of size and
lattice fringes, corresponding to spacing value of 0.28 nm which is surface states (Fig. 2b). The constant emission wavelength also indi-
close to the value for the (020) plane of graphitic carbon, indicat- cates that the as-prepared N-doped C-dots contain a single emitter
ing high crystallinity of the N-doped C-dots. XRD pattern (Fig. 1d) only, which can avoid autofluorescence and is favorable for the
exhibits a typical broad peak at about 24.9◦ , associated with the application of C-dots in quantitative assays. The maximum emis-
graphitic structure, which further confirms their crystalline nature. sion wavelength at different excitation wavelengths remains at
All these structural characterizations indicate that the C-dots have 415 nm. The N-doped C-dots display the highest fluorescent inten-
been successfully prepared.
76 R. Wang et al. / Sensors and Actuators B 241 (2017) 73–79

Fig. 2. (a) PL and UV–vis absorption spectra of as-prepared C-dots. Inset: photograph of C-dots aqueous solution taken under UV and visible light, and (b) PL spectra of C-dots
excited by different wavelength.

a b
Transmittance

C1s

CPS
755
1180 1709
616 1630 O1s
1110
3150 N1s
1400

3430

500 1000 1500 2000 2500 3000 3500 0 100 200 300 400 500 600 700
Wavenumber(cm-1) B.E. /eV

c d
C=C/C-C N-H
CPS
CPS

C-N C-N

C-O
C=O

292 290 288 286 284 282 280 278 408 404 400 396 392
B.E. / eV B.E. / eV
Fig. 3. FTIR spectrum (a), XPS scans of N-doped C-dots: (b) survey spectrum, (c) C 1s, and (d) N 1s.

sity when they are excited at 310 nm. Therefore, we select 310 nm that the synthesized N-doped C-dots are co-functionalized by both
as the excitation wavelength for the following experiments. amine and carboxylic groups.
The elemental composition of the N-doped C-dots is character- XPS survey spectrum (Fig. 3b) displays three dominant peaks
ized by FTIR and XPS. The FTIR spectrum of the N-doped C-dots at 285.0, 400.0 and 532.9 eV, which are attributed to C1s, N1 s and
is shown in Fig. 3a. Remarkably, the peak emerges at 3430 cm−1 , O1s, suggesting the existence of C, N and O elements. The C 1 s
which corresponds to the stretching vibrations of O H. The peak XPS spectrum (Fig. 3c) can be resolved into four distinct carbon
at 1709 cm−1 is attributed to C O stretching vibrations, and the states at 284.6, 285.4, 286.2, and 288.4 eV, which are attributed to
stretching vibration bands of C O at 1110 and 755 cm−1 indicate C C, C N, C O, and C O, respectively [25]. The high-resolution
the presence of carboxylic acid and other oxygen-containing func- N 1 s spectrum reveals the signals of NH2 at 399.6 eV and N C at
tional groups. The absorbance at 1630 and 3150 cm−1 is assigned to 401.1 eV (Fig. 3d) [26], indicating that C-dots are functionalized by
N H bending vibration and N H stretching vibration, respectively, NH2 groups. The XPS results are consistent well with the FTIR data
suggesting the existence of amino-containing functional groups. and also indicate that the high degree of functionalization of the
Moreover, two obvious absorption peaks at 1400 and 755 cm−1 are surface enables the N-doped C-dots particles to interact with the
assigned to C H bending vibrations. These peaks suggest that the surface of many different kinds of materials.
N-doped C-dots have reasonable hydrophilic properties as well as
considerable stability and dispersibility in water. This result reveals
 R. Wang et al. / Sensors and Actuators B 241 (2017) 73–79 77

2800 a 3000 b
2400 2500

PL Intensity(a.u.)
PL Intensity(a.u.) 2000 11
2000
1600
1500
1200 2

800 pH 1000
400 500
0
0
350 400 450 500 550 600 2 4 6 8 10 12
Wavelength(nm) pH

Fig. 4. (a) PL spectra of the N-doped C-dots dispersed in solutions with different pH values (from 2 to 11), (b) PL intensity at the peak position of the N-doped C-dots dispersed
in solutions with different pH values, and (c) Photographs of filter paper with C-dots coating (below), and the pH values of the solutions dripped on the paper are 2, 4, 6 and
10 (up).

3.2. Fluorescence response of N-doped C-dots toward pH

3200 pH=9
PL Intensity(a.u.)

Interestingly, the resultant N-doped C-dots are highly sensitive

2400
to the pH values and possess a pH-sensitive PL feature. As illustrated
in Fig. 4a and b, at lower pH, C-dots show low fluorescence intensity
1600
(pH < 3). But the intensity increases rapidly as pH increases from 3
to 10, and when pH is above 10, the fluorescence intensity of N-
800
doped C-dots does not change obviously. In the experiments, the
amine moieties are protonated to ammonium salt (−NH3 + ) at low
pH, and the passivation effective of the amino group may be sus- 0
pH=3
ceptible. On the other hand, the results may be attributed to the
presence of the carboxyl groups. The carboxyl groups may be pro- -800
0 2 4 6 8 10
tonated in acidic solutions, which will lead to the aggregation of
C-dots, resulting also in the fluorescence quenching [27]. This phe-
Cycle number
nomenon further confirms that the amine and carboxyl groups are
Fig. 5. The reversible PL intensity of N-doped C-dots dispersion when the pH value
present on the surface of N-doped C-dots, which endows the C-dots alternates between 3 and 9.
with reasonable hydrophilic properties, stability and dispersibility
in water. of fluorescence brightness on the paper can also indicate the rough
We have made a C-dots coated paper for visual fluorescence pH values with naked eyes.
detection of pH. A piece of filter paper is immersed into a C-dots To evaluate the reversible behavior of the resultant C-dots upon
solution for 1 h. Then, the paper is removed from the solution and switching between acid and base media, the pH-reversibility of the
placed in an oven at 40 ◦ C for 1 h. Under UV-lamp, this paper emits C-dots is shown in Fig. 5. It can be seen that the C-dots show a
blue fluorescence (Fig. 4c, below), while the raw paper without any remarkable pH-switching PL property with no visible perturbation
treatment is nonluminous, demonstrating the successful prepara- even after five cycles from pH 3 to pH 9, which indicates the high
tion of C-dots coated paper. The solutions with pH values of 2, 4, pH-reversibility. In short, we deem that the above observation and
6 and 10 are dripped on four pieces of fluorescent paper and air- chemical structure analysis have connected the important variation
dried for 20 min (Fig. 4c, up). Under UV light, the paper dripped of PL intensity to the protonation and deprotonation of the amino
with the acidic solution (pH = 2) is apparently white, and the paper groups on the surface of the as-prepared N-doped C-dots.
with pH = 3 presents a faint light blue. When pH is 6, the paper
is apparently blue, and the region dripped with the alkaline solu- 3.3. Sensitive and selective detection of Fe3+
tion (pH = 10) exhibits an extra-bright blue fluorescence. The raw
paper with alkaline solution (sodium hydroxide solution, pH = 10) Iron is of great importance for organisms and their biological
treatment after drying is nonluminous, which demonstrates the systems and plays an important role in life. Thus, the detection of
sodium hydroxide deposited on filter paper does not lead to dis- this transition metal ion is highly coveted due to the deepening cri-
tinct characteristic of fluorescence, and it does not interfere with sis of industrial pollution. We have explored the feasibility of using
our experimental result. Although the accurate pH assay using the the as-prepared N-doped C-dots for Fe3+ detection. Because the N-
C-dots coated paper has not been achieved, the distinct variation doped C-dots still have the strong PL intensity and robust chemical
stability under acidic conditions reflected above, an acidic condi-
78 R. Wang et al. / Sensors and Actuators B 241 (2017) 73–79

80
[Fe3+] a 1.0 b

PL Intensity(a.u.)
60 0.8
2
0.6 R =0.9976
40

I/I0
0.4
20
0.2
0
0.0
350 400 450 500 550 0.0 0.5 1.0 1.5 2.0 2.5 3.0
3+
Wavelength(nm) [Fe ]/μ M

Fig. 6. (a) Evolution of fluorescence spectra of the C-dots in the presence of different concentrations of Fe3+ (from top to bottom: 0, 0.1, 0.2, 0.6, 0.8, 1, 1.2, 1.6, 2.0, 2.4, and
2.8 ␮M), and (b) plots of the fluorescence intensity against the concentration of Fe3+, I and I0 are the fluorescence intensity of C-dots in the presence and absence of Fe3+,
respectively.

Table 1 1.0
Comparison of sensing performance of C-dots from different precursors for
Fe3+ detection.

Carbon source LOD (␮M) Fe3+ Ref. 0.8

Melamine and citric acid 0.142 [21]
Alginic acid and ethanediamine 10.98 [26]

(I 0 -I)/I 0
Asparticacid and NH4 HCO3 0.260 [28] 0.6
Graphene 0.090 [30]
M-aminobenzoic acid 0.050 This work
0.4
tion (pH = 4.0) is adopted for detecting the metal ions. To study
the sensitivity of C-dots for Fe3+ detection, different concentrations
0.2
of Fe3+ are added to the aqueous solution of C-dots, and the fluo-
rescence intensities are measured. As shown in Fig. 6a, with the
increase of the concentration of Fe3+ , the fluorescence intensity 0.0 3+ +
+ 2+ 2+ 2+ 2+ 2+
of C-dots decreases gradually. Fig. 6b shows the plot of fluores- Fe Na Cu Fe2 Cd Mn2+ Zn2+ Ni2+Hg Co Pb
cence decreasing percentage vs the concentration of Fe3+ . A nice
linear response concentration range of Fe3+ is from 0 to 1.6 ␮M,
Analytes
while the quantification of Fe3+ can be achieved with standard Fig. 7. Selectivity investigation of the N-doped C-dots sensor for Fe3+ detection (ions
deviation R2 = 0.9976, and the lowest detection limit (LOD) is about concentration: 10 ␮M).
0.05 ␮M based on the standard deviation of the response (␴) and
the slope of the calibration curve (S) at levels approximating the
LOD according to the formula: LOD = 3.3(␴/S), which is lower than to be coordinated with amino, carboxyl groups on the surface of
the previously reported results [21,26,28–30]. The comparison of C-dots, and the radiative transition is disrupted and thus leads to
LOD of Fe3+ using C-dots from different carbon source has been the PL quenching [21]. Moreover, the fluorescence decay dynam-
listed in Table 1. Notably, the ultrasensitive detection of Fe3+ using ics are evaluated to prove the fluorescence quenching mechanism.
the N-doped C-dots can be achieved in the aqueous solution. According to fluorescence lifetime curves, the average lifetimes
The C-dots based fluorescent sensing platform for Fe3+ assay of C-dots and C-dots/Fe3+ are 8.02 ns and 7.90 ns, which present
in river water samples is also explored in this work. The stan- a slight change, while their PL spectra have changed obviously
dard Fe3+ solutions with different concentrations are added to (Fig. 6a). This indicates that the quenching mechanism of C-dots
the pretreated water sample, and then analyze with the proposed in the presence of Fe3+ is static quenching.
method. Fig. S1 of Supplementary information in the online version
at DOI: http://dx.doi.org/10.1016/j.snb.2016.10.043 shows the flu- 4. Conclusion
orescence response of C-dots in presence of river water containing
different concentrations of Fe3+ ions and the corresponding rela- In conclusion, we have successfully synthesized highly
tionship between fluorescence intensity and the concentrations fluorescent N-doped C-dots by hydrothermal method with m-
of Fe3+ . Similar to the above results, the PL intensities of C-dots aminobenzoic acid as the precursor and nitrogen source. The
show a trend of decreasing with the increase of the concentration synthesized N-doped C-dots present large quantum yield, crys-
of Fe3+ . A good linear correlation has also been obtained in the range talline nature and desirable functional groups. The C-dots can serve
of 0–1.2 ␮M for the river water (R2 = 0.9890). The results demon- as fluorescent nanosensors to detect pH. A fluorescent paper with
strate that the proposed sensor is capable of detecting Fe3+ in real C-dots coated for visual detection of pH by naked eyes has been
environmental samples. successfully prepared. Moreover, the N-doped C-dots are employed
To evaluate the selectivity of this sensing system, we have exam- for assaying Fe3+ , and a linear relationship between the decreased
ined the PL intensity change in the presence of representative metal fluorescence intensity of C-dots and the concentration of Fe3+ is
ions under the same conditions including Na+ , Cu2+ , Fe2+ , Cd2+ , established in the range from 0 to 1.6 ␮M. The detection limit is
Mn2+ , Zn2+ , Ni2+ , Hg2+ , Co2+ , and Pb2+ . As shown in Fig. 7, only as low as 0.05 ␮M, suggesting a promising assay for Fe3+ . The C-
Fe3+ ions can significantly quench the ratiometric luminescence dots applied for Fe3+ assay in real water samples is achieved. This
output of the C-dots. These results suggest that the N-doped C- work provides a new route for low-cost synthesis of ultrabright
dots sensor exhibits a high selectivity to Fe3+ . Fe3+ is considered N-doped C-dots from cheap precursors. We believe that the pro-
 R. Wang et al. / Sensors and Actuators B 241 (2017) 73–79 79

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dots for sensitive and selective detection of iron (III), RSC Adv. 5 (2015)
Xiufang Wang is an associate professor at School of Materials and Chemical Engi-
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ions, Talanta 142 (2015) 131–139. interests focus on material science.